JPH0971615A - Ethylene-based copolymer, composition containing the copolymer, and ethylene-based copolymer film - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] In addition to having narrow molecular weight distribution and branching degree distribution, the composition distribution shape is controlled, and in particular, mechanical properties such as tear strength, impact strength, heat sealability, and environmental stress crack resistance. An ethylene-based copolymer that gives a film with excellent properties. SOLUTION: Mw / Mn measured by GPC method is 1.
5 to 4.0, Mw of 3,000 to 1,000,000, half-width at half maximum W / 2 of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to the Gaussian distribution, and the average number of short-chain branches of the polymer n The ethylene-based copolymer having a relationship with the formula 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n and a resin density of 0.85 to 0.95 g / cm ³ .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene-based copolymer, an ethylene-based polymer composition and an ethylene-based copolymer film, and more specifically, it has a narrow molecular weight distribution and a branching degree distribution and a composition distribution shape of Controlled,
In particular, mechanical properties such as tear strength, heat sealability,
The present invention relates to an ethylene-based copolymer which gives a film excellent in environmental stress crack resistance (ESCR property), an ethylene-based polymer composition containing the polymer, and an ethylene-based copolymer film having the above-mentioned excellent properties. is there.

[0002]

2. Description of the Related Art Hitherto, ethylene copolymers such as ethylene-α-olefin copolymers have been widely used in many fields as general-purpose resins. This ethylene-based copolymer has been conventionally produced by a heterogeneous catalyst. The ethylene-based copolymer obtained by using this heterogeneous catalyst has a wide molecular weight distribution and a wide branching degree distribution. , High branching degree A large amount of low molecular weight components are contained. As a result, it is known that the film obtained from this ethylene-based copolymer is inferior in impact strength, heat sealability, ESCR performance and the like. However, since the film has little anisotropy (the longitudinal and lateral strengths are unbalanced), it has an advantage of excellent tear strength, which is important as a physical property of the film.
On the other hand, in recent years, homogeneous metallocene catalysts having high catalytic activity and excellent copolymerizability have been developed. The ethylene-based copolymer obtained by using this metallocene catalyst has a narrow molecular weight distribution, and accordingly a narrow branching degree distribution (uniform branching number distribution), and has a low number of low molecular weight components having highly branched components. The heat sealability of the film obtained from
It is known that impact strength and ESCR property are improved. As an example of an ethylene-based copolymer obtained by using such a metallocene catalyst (also referred to as a single-site catalyst), for example, US Pat. No. 5,272,236 discloses ethylene-α-obtained by a metallocene catalyst.
Although an olefin copolymer is disclosed, this composition has a narrow composition distribution, so that the impact strength and ES of the obtained film are
Although the physical properties such as CR property are improved, it has a drawback that the tear strength is low due to the large anisotropy. In addition, commercially available single-site linear low-density polyethylene (manufactured by Exxon, trade name Exact) and the like have a narrow composition distribution and use hexene-1 or an α-olefin having a smaller number of carbon atoms as a comonomer. Therefore, although the obtained film has improved heat sealability, the tear strength is not improved as expected. For this reason, attempts have been made to control these physical properties by controlling the branching degree distribution and the molecular weight distribution by blending, etc., but regarding the relationship between tear strength and impact strength, improving one of them reduces the other. The reality is that none of these have been obtained yet. That is, as such a composition, for example, JP-A-3-502710 discloses a composition using an ethylene-based copolymer obtained by a homogeneous catalyst.
Although the improvement of tear strength is mentioned here, the impact strength is not mentioned at all. Also,
In JP-A-6-136195, JP-A-6-136196, and JP-A-6-207057, copolymers having a narrow composition distribution and being characterized by melt tension have different densities and MFRs (melt flow rates). Compositions having improved film impact by blending seeds are described. However, these are characterized by blending those having different molecular weights, and as a result, the molecular weight distribution is widened and mechanical strength such as tensile strength is lowered. Therefore, the molecular weight distribution and branching degree distribution is narrow, and the shape of the composition distribution is arbitrarily controlled, and an ethylene-based copolymer and a composition thereof which give a film excellent in both tensile strength and impact strength regardless of the molecular weight distribution are provided. Was wanted.

[0003]

Under the circumstances, the present invention has a narrow molecular weight distribution and branching degree distribution, and the composition distribution shape is controlled, and in particular, mechanical properties such as tear strength, heat sealability, By blending an ethylene-based copolymer that gives a film having excellent ESCR properties, and an ethylene-based copolymer that has a narrow molecular weight distribution and a wide composition distribution and provides excellent tear strength, without reducing the impact strength, Improves tear strength,
It is an object of the present invention to provide an ethylene-based copolymer composition which gives a film excellent in both impact strength and tear strength, and further an ethylene-based copolymer film having the above-mentioned excellent properties.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that (a) ethylene and (b) an α-olefin or diene compound having 3 to 20 carbon atoms. And an ethylene-based copolymer obtained by copolymerization with at least one selected from cyclic olefins and having specific properties, and an ethylene-based copolymer composition containing the same achieves the object. I found that The present invention has been completed based on such findings.

That is, the present invention provides (1) (a) ethylene and (b) α-C3 to C20.
In an ethylene-based copolymer obtained from at least one selected from olefins, diene compounds, and cyclic olefins, (1) polyethylene-equivalent weight average molecular weight (Mw) and number average molecular weight measured by gel permeation chromatography (Mn) ratio Mw /
Mn is in the range of 1.5 to 4, and the weight average molecular weight (M
w) is in the range of 3000-1,000,000,
(2) The half-width at half maximum [W /] of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to Gaussian distribution
2] and the average number of short-chain branches n (number / 1000 carbons) of the polymer satisfy the formula 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n, and (3) Resin Density is 0.85-0.95
an ethylene-based copolymer (I) characterized by being in the range of g / cm ³ .

(2) (a) ethylene and (b) carbon number 3
To an ethylene-based copolymer obtained from at least one selected from α-olefins, diene compounds, and cyclic olefins of 20 to 20 in terms of polyethylene equivalent weight average molecular weight (Mw) and number measured by gel permeation chromatography method. The ratio Mw / Mn with the average molecular weight (Mn) is in the range of 1.5 to 4 and the resin density is 0.85 to 0.
In the composition distribution curve obtained by the temperature rising fractionation method in the range of 95 g / cm ³ , the area of the region surrounded by the curve obtained by approximating the main peak by Gaussian distribution and the base line is A,
The area of the region on the low temperature side where the elution temperature exceeds 32 ° C., surrounded by the curve obtained by approximating the Gaussian distribution of the main distribution peak and the main peak, and the elution temperature exceeds 32 ° C., the area of the high temperature side region is C, the composition When the area of the region at the elution temperature of 25 to 32 ° C surrounded by the distribution curve and the base line is D, the tear strength (TS, kg
f / cm) is expressed by the formula TS ≧ 131.5-155 × log [{(B + C + D) /
A} +0.1] and the equation 0.1 ≦ (B + C + D) / A ≦ 1 are satisfied, the ethylene-based copolymer (II)
,

(3) An ethylene-based copolymer obtained from (A) (a) ethylene and (b) an α-olefin having 3 to 20 carbon atoms was measured by (1) gel permeation chromatography method. The ratio Mw / Mn of polyethylene-equivalent weight average molecular weight (Mw) to number average molecular weight (Mn) is in the range of 1.5 to 4, and the weight average molecular weight (Mw) is 3,000 to 1,000,000. (2) Half-width at half maximum [W of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to a Gaussian distribution
/ 2] and the average number of short-chain branches n (number / 1000 carbons) of the polymer satisfy the formula 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n, and (3) Resin density is 0.85-0.95
An ethylene copolymer in the range of g / cm ³ and (B) an ethylene copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms, which is measured by a gel permeation chromatography method. Polyethylene equivalent weight average molecular weight (Mw) is 3,000 to 1.0
It is in the range of 0,000 and the resin density is 0.85-0.9.
An ethylene copolymer in the range of 5 g / cm ³ , and an ethylene copolymer composition (I) containing

(4) The ethylene copolymer as the component (A) is an ethylene copolymer obtained from (a) ethylene and (b) an α-olefin having 3 to 20 carbon atoms,
The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography is in the range of 1.5 to 4 and the resin density is 0.85 to 0.95 g. / in the range of cm ^3, and heated in the composition distribution curve obtained by the fractionation method, the area of the region surrounded with the curve and the base line obtained by Gaussian approximation of the main peak a, the main and composition distribution curve The area of the region on the low temperature side where the elution temperature exceeds 32 ° C. is surrounded by the curve obtained by approximating the Gaussian distribution and the baseline, and B is the area of the region on the high temperature side, and the composition distribution curve and the baseline. The tear strength (TS, kgf / cm) is expressed by the formula TS ≧ 131.5-155 × log [{(B + C + D) /
A} +0.1] and the formula 0.1 ≦ (B + C + D) / A ≦ 1 are satisfied, the ethylene copolymer composition (II) according to (3) above. And (5) an ethylene-based copolymer according to (1) or (2) above, or an ethylene-based copolymer obtained by forming a film of the ethylene-based copolymer composition according to (3) or (4) above. the film,
Is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylene-based copolymers (I) and (II) of the present invention include (i) ethylene and (b) α-olefins having 3 to 20 carbon atoms, diene compounds and cyclic olefins. It is a copolymer with at least one selected from In this copolymer, examples of the α-olefin having 3 to 20 carbon atoms used as the comonomer of the component (b) include propylene, 1-butene, 1-pentene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Octadecene, 1-eicosene and the like. As the diene compound, a conjugated diolefin or a non-conjugated diolefin can be used. Examples of conjugated diolefins include 1,3-butadiene; isoprene; chloroprene; 1,3-cyclohexadiene; 1,3-cyclooctadiene. Furthermore, examples of non-conjugated diolefins include 1,5-hexadiene; 1,7
-Α, ω-diene compounds such as octadiene and derivatives thereof, norbornadiene; dicyclopentadiene; 5-
Examples thereof include vinyl norbornene; cyclic diolefins such as ethylidene norbornene and derivatives thereof.

On the other hand, examples of the cyclic olefin include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; -Trimethylnorbornene;
5-phenylnorbornene; 5-benzylnorbornene; 1,4,5,8-dimetano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene; 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene; 2-cyclohexyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene;
2,3-dichloro-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-isobutyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,2-dihydrodicyclopentadiene; 5
5,5-dichloronorbornene; 5-fluoronorbornene; 5,5,6-trifluoro-6-trifluoromethylnorbornene; 5-chloromethylnorbornene; 5-methoxynorbornene;
5,6-dicarboxyl norbornene anhydrate;
5-dimethylaminonorbornene; 5-cyanonorbornene; 2-ethyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; 2,3-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-hexyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene; 2-fluoro-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,5-dimethyl-1,4,5 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned.

The comonomer of the component (b) may be used alone or in combination of two or more kinds.
Particularly, an α-olefin having 3 to 20 carbon atoms is preferable. When the ethylene-based copolymers (I) and (II) of the present invention are copolymers of ethylene and α-olefins and / or cyclic olefins, the content of all comonomer units is preferably the above-mentioned copolymer. In order to have the above property, the range of 1 to 20 mol% is preferable. Further, ethylene-based copolymers (I), (II)
When at least a diene compound is used as the comonomer, the content of the diene compound unit in the ethylene copolymer is preferably 1 mol% or less. If the content of the diene compound unit exceeds 1 mol%, the copolymer may gel due to crosslinking. From the viewpoint of preventing gelation, the content of the diene compound unit is more preferably 0.8.
It is at most mol%, more preferably at most 0.6 mol%, particularly preferably at most 0.4 mol%. Further, the total content of the other comonomer units is preferably in the range of 0.01 to 20 mol% so that the copolymer has desired properties. The ethylene copolymer (I) of the present invention has the following properties.

First, (1) a weight average molecular weight (Mw) and a number average molecular weight (M) in terms of polyethylene measured by gel permeation chromatography method (GPC method).
n) and the ratio Mw / Mn is in the range of 1.5 to 4, and M
It is necessary that w is in the range of 3000 to 1000000. If the Mw / Mn ratio is less than 1.5, the moldability is poor, and if it exceeds 4.0, physical properties such as impact strength are reduced. From the viewpoint of the balance between molding processability and physical properties, preferable Mw /
Mn is in the range of 1.8 to 3.8, and particularly preferably in the range of 2.0 to 3.5. Further, if Mw is less than 3,000, sufficient mechanical properties cannot be obtained, and if it exceeds 1,000,000, the moldability is deteriorated. From the viewpoint of the balance between mechanical properties and moldability, Mw is preferably in the range of 10,000 to 800,000, and particularly preferably in the range of 15,000 to 60,000. Note that the above Mw and Mn are as follows: device: Waters ALC / GPC150C, column: TSK HM +
GMH 6 × 2, flow rate: 1.0 ml / min, solvent:
1,2,4-trichlorobenzene, measurement temperature: 135 ° C
Is a value in terms of polyethylene obtained by the GPC method under the conditions described above.

(2) Half-width at half maximum [W / 2] of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to the Gaussian distribution and the average number of short-chain branches of the polymer n
It is necessary that the relationship with (number / 1000 carbons) satisfies the expression 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n. The W / 2 is (0.704+
When the value is smaller than 0.147n), the moldability is poor.
When / 2 is larger than (-0.055 + 0.577n), the physical properties of the obtained film are reduced. From the viewpoint of the balance between the molding processability and the physical properties of the obtained film, the relationship between W / 2 and n is preferably 1.0 + 0.147n ≦ W / 2 ≦ −0.08 + 0.577n, more preferably 1. 5 + 0.147n ≦ W / 2 ≦ −0.1 + 0.577n Particularly preferred is 2.0 + 0.147n ≦ W / 2 ≦ −0.2 + 0.577n.

The above W / 2 is a value obtained by the temperature rising fractionation method described below. That is, a column having an inner diameter of 10 mm and a length of 250 mm packed with Chromosorb PPAN (80/100 mesh) as a column filler was adjusted to a concentration of about 6 g / liter at 135 ° C.
The polymer solution of dichlorobenzene is injected with a metering pump. The temperature is lowered to 30 ° C. at a rate of 10 ° C./hour, and the polymer is adsorbed and crystallized on the filler. Then, at 20 ° C /
O-dichlorobenzene at 2 cc /
Feed at a rate of minutes. The concentration of the eluted polymer is measured with an infrared detector (apparatus: 1-A Fox Boro CVF, cell: CaF ₂ ), and a composition distribution curve with respect to the elution temperature is obtained. Next, a curve obtained by approximating the main peak of this composition distribution curve by Gaussian distribution is created, and its half-width at half maximum W
/ 2. The average number of short-chain branches n was measured by ¹ H-NMR using JSK-400 manufactured by JEOL (JNM) (400 MHz, measurement temperature: 130 ° C., solvent: 1,
2,4-trichlorobenzene / deuterated benzene)
It can be determined from the peak intensity ratio of a methyl group and a methylene group.

Further, (3) the resin density is 0.85 to 0.95 g.
/ Cm ³ . The resin density can be arbitrarily controlled within the above range by increasing or decreasing the content of the comonomer unit. Resin density 0.8
A copolymer in the range of 5 to 0.90 g / cm ³ can be suitably used as an olefin-based modifier. The resin density exceeds 0.90 g / cm ³ and 0.95 g / cm ³
/ Cm ³ or less is suitable as a base material for a highly functional film having excellent strength. The density is 190
This is a value obtained by preparing a press film at a temperature of ° C. and quenching the film to measure the density by a density gradient tube method. On the other hand, the ethylene copolymer (II) of the present invention is required to have the following properties. That is, like the ethylene copolymer (I), Mw / Mn is in the range of 1.5 to 4, preferably 1.8 to 3.8, more preferably 2.0 to 3.5. Moreover, the resin density is in the range of 0.85 to 0.95 g / cm ³ . Further, in the composition distribution curve obtained by the temperature rising fractionation method, the area of the region surrounded by the curve obtained by approximating the main peak by the Gaussian distribution and the base line is A, and the composition distribution curve and the main peak are approximated by the Gaussian distribution. The area of the region on the low temperature side and the elution temperature exceeding 32 ° C. surrounded by the obtained curve and the base line is B, and the area of the region on the high temperature side is C, and the elution temperature surrounded by the composition distribution curve and the base line is The area of the region of 25 to 32 ° C is D
And the tear strength (TS, kgf / cm) is
Formula TS ≧ 131.5-155 × log [{(B + C + D) /
A} +0.1] and the equation 0.1 ≦ (B + C + D) / A ≦ 1.

The area of each of the areas A, B, C and D is
It is a value obtained as shown below. First, in the same manner as in the case of the ethylene copolymer (I), the composition distribution curve as shown in FIG. 1 is obtained by the temperature rising fractionation method. Next, a curve obtained by approximating the main peak of this composition distribution curve with a Gaussian distribution is created as shown in FIG. A is the area of a region surrounded by a curve and a curve obtained by approximating this main peak by a Gaussian distribution. B is the area of the region on the low temperature side surrounded by the curve obtained by approximating the Gaussian distribution of the composition distribution curve and the main peak and the base line, and the elution temperature exceeds 32 ° C. Also, C is
The area of a high temperature side region surrounded by a curve obtained by approximating a composition distribution curve and a main peak by a Gaussian distribution and a base line, and shows the amount of a component having high crystallinity. Here the Gaussian distribution approximation is
It is approximated by fitting to the high temperature elution side of the main peak. Further, D is the area of the region surrounded by the composition distribution curve and the base line and having an elution temperature of 25 to 32 ° C., which indicates the amount of highly branched contained components. Tear strength TS is
(131.5-155 x log [{(B + C + D) / A}
If it is smaller than +0.1]), the performance of the obtained film is poor. From the viewpoint of the performance of the obtained film, the tear strength TS is expressed by the formula TS ≧ 135.5-160 × log [{(B + C + D) /
A} +0.1] is preferable, and in particular, the expression TS ≧ 141.5-170 × log [{(B + C + D) /
It is preferable to satisfy the relationship of A} +0.1].

Tear strength TS (kgf / cm)
Is a value measured by the following method. That is,
Using a 50 ton press, the temperature is 230 ° C., the pressurizing time is 4 minutes, and the pressure is 30 to 50 kg / cm ² , and the thickness is 60.
A sheet (20 cm × 20 cm) of ˜70 μm is prepared. Next, from this sheet, a portion with a uniform thickness 10c
Cut out in a size of mx 10 cm, JIS K-712
In accordance with No. 8, perform the Elemendorff tear test. The tear strength is a value measured as an average value on four sheets.

The ethylene-based copolymer (II) is
In addition to satisfying the above conditions, ethylene-based copolymer (I)
Similarly, Mw of 3,000 to 1,000,000, preferably 1,000,000 to 80,000, more preferably 15,000.
It is in the range of 0 to 60,000 and the half width at half maximum [W /
2] and the average number of short chain branches n (number / 1000 carbons) of the polymer are expressed by the formula: 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n, preferably 1.0 + 0.147n ≦ W2 /≦−0.08+0.577n More preferably, 1.5 + 0.147n ≦ W / 2 ≦ −0.1 + 0.577n Particularly preferably, 2.0 + 0.147n ≦ W / 2 ≦ −0.2 + 0.577n is satisfied. What is done is advantageous in terms of processability and physical properties of the obtained film.

The ethylene-based copolymers (I) and (I
The production method of I) is not particularly limited as long as it has the above-mentioned properties, and various methods can be used. A method of copolymerizing the desired comonomers is advantageous. This polymerization catalyst includes (A) general formula (Ia)

[0020]

Embedded image

[Wherein M¹Is the periodic table group 3-10 or
Lanthanoid series metal elements, X¹Is M¹Σ combined with
Represents a binding ligand, X¹If there are multiple Xs
¹May be the same or different, or may be an indenyl ring or
Y¹And may be crosslinked. Y ¹Is Lewis base,
Y¹If there is more than one, more than one Y¹Are the same but different
May be an indenyl ring or X¹May be crosslinked with
Yes. A represents a crosslinking group, p is an integer of 1 to 20, and q is 1
An integer of 5 [(M¹Valence of -2], r is an integer of 0 to 3
Indicates a number. R¹~ R⁸Are hydrogen atom and halogen respectively
Atom, hydrocarbon group having 1 to 20 carbon atoms, carbon group having 1 to 20 carbon atoms
Halogen-containing hydrocarbon group, silicon-containing group or hetero atom-containing group
Represents a group, whether they are the same or different
Or, it may form a ring with an adjacent group. Also,
Three R^FourThey may be the same or different, 3
R⁸They may be the same or different. 〕so
Represented transition metal compound, (B) transition gold of the component (A)
Reacts with genus compounds or their derivatives to form ionic complexes
Compounds that can be formed and, if necessary, (C) Organic aluminum
Polymerization catalyst (I) or (A ') containing a phosphorus compound
Formula (Ib)

CpM ² E ¹ E ² E ³ ... (Ib) [wherein, M ² represents titanium, zirconium or hafnium, and C _P is a carbon number having a cyclopentadienyl or substituted cyclopentadienyl skeleton. 5 to 30 cyclic compound groups are shown. E ¹ , E ² and E ³ each represent a σ ligand, which may be the same or different. ] The transition metal compound represented by, (B ') the compound which can react with the transition metal compound of said (A') component or its derivative, and can form an ionic complex, and (D) phenolic compound and / Or a polymerization catalyst (II) containing water, or (A ′) a transition metal compound represented by the above general formula (Ib),
(B ') a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A') or a derivative thereof, and (E) (a) a reaction product of an organoaluminum compound and a phenolic compound And / or (b) organoaluminum compound and general formula (Ic)

[0023]

Embedded image

[In the formula, X, Y and D each represent a sulfur atom or an oxygen atom, which may be the same or different from each other. ] The polymerization catalyst (III) containing a reaction product with a boron compound represented by the following can be preferably used. In the polymerization catalyst (I), the transition metal compound used as the component (A) has the general formula (Ia)

[0025]

Embedded image

It has a structure represented by the above
In the general formula (Ia), M¹Is the 3rd to 10th group of the periodic table
Represents a metal element of the lanthanoid series, and specific examples include
Titanium, zirconium, hafnium, yttria
Mu, vanadium, chromium, manganese, nickel, cobal
, Palladium and lanthanoid metals
However, among these, as a catalyst for the polymerization of ethylene copolymers
And group 4 elements such as titanium, zirconium and
Hafnium is preferred. X¹Is M¹Σ bond
Represents a sex ligand, X¹If there are multiple Xs¹Is
They may be the same or different, and also an indenyl ring or Y
¹And may be crosslinked. This X¹As a specific example of
Hydrogen atom, halogen atom, hydrocarbon having 1 to 20 carbon atoms
Group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, amide group having 1 to 20 carbon atoms, carbon number
1-20 silicon-containing groups, phosphides having 1-20 carbons
Group, sulfide group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Examples thereof include an acyl group.

[0027] Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different and may be cross-linked with indenyl ring or X ^1. This Y ¹
Examples thereof include amines, ethers, phosphines, thioethers and the like. Specific examples of Y ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-pentylamine, methyldiphenylamine, pyridine. , P-bromo-N, N
-Amines such as dimethylaniline and p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, acetonitrile, Examples thereof include nitriles such as benzonitrile.

[0028] A represents a bridging group, as a specific structure, represented by the formula (R _'n Q). Where Q is 13,
An atom selected from the groups 14, 15 and 16 and n is 2, when the group 14 is Q, 1 when the group is 13, 13 and 15 and 0 when Q is the group 16. These _{structures, R '2 C, R'} 2 Si, R '2 G
_{e, R '2 Sn, R'Al} , R'P, R'N, oxygen (-O
-), Sulfur (-S-), selenium (-Se-) [where R'is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or silicon] It is a containing group or a hetero atom-containing group, and when R ′ is 2, they may be the same or different. And the like.

(A) _p [p represents an integer of 1 to 20] ]
As specific examples of, methylene, ethylene, ethylidene,
Isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisilylene silylene, dimethyl gel Mi Ren, dimethyl stannyl Ren, methyl Helsingborg isopropylidene (CH ₃ -B =), methylaluminoxane isopropylidene (CH ₃ -Al = ), Phenylphosphylidene (Ph-
P =), phenyl phosphorylase den (PhPO =), ethylene (-CH = CH -), 1,2- phenylene, vinylene, vinylidene, ethenylidene (CH ₂ = C =), methylimide, oxygen (-O-), There are sulfur (-S-), selenium (-Se-), and the like. Among these, methylene,
Ethylene, ethylidene and isopropylidene are preferable in terms of easiness of synthesis and yield. q is an integer of 1 to 5 [(M
^{1 has} a valence of -2], and r represents an integer of 0 to 3.
R ^{1 to} R ⁸ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group, and these are May be the same or different,
It may form a ring with an adjacent group. Also 3 R
⁴ may be the same or different and 3 R ⁸
They may be the same or different.

Specific examples of R ', R ^{1 to} R ⁸ include hydrogen atoms, halogen atoms such as Cl, Br, F and I, methyl, ethyl, n-propyl, n-butyl, isopropyl, 1 to 1 carbon atoms such as isobutyl and n-decyl
20 hydrocarbon groups, halogen-containing hydrocarbon groups such as trifluoromethyl, silicon-containing groups such as trimethylsilyl, dimethyl (t-butyl) silyl, methoxy, ethoxy,
Examples thereof include a hetero atom-containing group such as dimethylamino.

Specific examples of the transition metal compound represented by the general formula (Ia) include rac- [1,2-ethylenebis (7- (4-t-butylindenyl))] zirconium dichloride, rac- [1,2-ethylenebis (7-
(4-Methylindenyl))] zirconium dichloride, rac- [1,2-ethylenebis (7- (2,4-
Dimethylindenyl))] zirconium dichloride, r
ac- [1,2-ethylenebis (7- (1,4-dimethylindenyl))] zirconium dichloride, rac-
[Isopropylidene bis (7- (4-t-butylindenyl))] zirconium dichloride, rac- [Isopropylidene bis (7- (4-methylindenyl))] zirconium dichloride, rac- [Isopropylidene bis (7 -(2,4-Dimethylindenyl))] zirconium dichloride, rac- [isopropylidene bis (7
-(1,4-Dimethylindenyl))] zirconium dichloride, rac- [methylenebis (7- (4-t-butylindenyl))] zirconium dichloride, rac
-[Methylenebis (7- (4-methylindenyl))]
Zirconium dichloride, rac- [methylenebis (7
-(2,4-Dimethylindenyl))] zirconium dichloride, rac- [methylenebis (7- (1,4-dimethylindenyl))] zirconium dichloride, ra
c- [1,2-ethylenebis (7- (2-phenyl-4
-Methylindenyl))] zirconium dichloride, r
ac- [isopropylidene bis (7- (2-phenyl-
4-methylindenyl))] zirconium dichloride,
rac- [methylenebis (7- (2-phenyl-4-methylindenyl))] zirconium dichloride, rac
-[1,2-Ethylenebis (7- (2-phenylindenyl))] zirconium dichloride, rac- [dimethylsilylenebis (7- (4-t-butylindenyl))] zirconium dichloride, rac- [dimethyl Silylenebis (7- (4-methylindenyl))] zirconium dichloride, rac- [dimethylsilylenebis (7- (2,4-dimethylindenyl))] zirconium dichloride, rac- [1,2-ethylenebis ( 7-
Indenyl)] zirconium dichloride, rac- [t
trans-1,2-cyclohexylene bis (7- (4-
t-butylindenyl))] zirconium dichloride,
rac- [trans-1,2-cyclohexylenebis (7- (4-methylindenyl))] zirconium dichloride, rac- [trans-1,2-cyclohexylenebis (7- (2,4-dimethylindenyl) ))] Zirconium dichloride, rac- [trans-1,2
-Cyclohexylenebis (7- (1,4-dimethylindenyl))] zirconium dichloride, rac- [1,
2-ethylenebis (4-fluorenyl)] zirconium dichloride, rac- [1,2-ethylenebis (4-
(1-methylfluorenyl))] zirconium dichloride and the like, and those in which the racemic body in these compounds is substituted with a meso body, and those in which zirconium in these compounds is substituted with titanium or hafnium. Of course, it is not limited to these. Further, it may be a compound similar to a metal element of another group or lanthanoid series.

The transition metal compound as the component (A) may be used alone or in combination of two or more kinds. Examples of the component (B) in the polymerization catalyst (I) include (B-
1) An ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, (B-2) aluminoxane, and (B-3) Lewis acid. (B
As the component (-1), any ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex can be used, but the following general formula (II) , (III) ([L ¹ -R ⁹ ] ^{k +} ) _a ([Z] ^- ) _b ... [II] ([L ² ] ^{k +} ) _a ([Z] ^- ) _b ... [III]

[However, L²Is M^Four, R^TenR¹¹M^Five, R
¹² _Three C or R¹³M^FiveIt is. ] [(II), (III) in the formula, L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-Or [Z²]^-This
Here [Z¹]^-Is an anion in which multiple groups are bonded to an element
In other words, [M^ThreeG¹G²... G^f]^-(Where M^ThreeIs
Group 5 to 15 element of the periodic table, preferably 13 of the periodic table
Group 15 elements are shown. G¹~ G^fAre hydrogen atoms,
Halogen atom, C1-20 alkyl group, C2
~ 40 dialkylamino group, C1-20 alco
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group of 7 to 40 carbon atoms
Group, arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
~ 20 halogen-substituted hydrocarbon groups, C 1-20
Syloxy group, organic metalloid group, or 2 to 20 carbon atoms
Represents a hetero atom-containing hydrocarbon group. G¹~ G^fOut of
Two or more may form a ring. f is [(center metal
M^ThreeValence of +1)]. ), [Z²]
^-Means that the logarithm (pKa) of the reciprocal of the acid dissociation constant is -10 or less
Of Bronsted acid alone or Brønsted acid and Louis
Conjugated bases in combination with succinic acids, or generally with super strong acids
Shows the conjugate base defined. Also, the Lewis base coordinates
May be. Also, R⁹Is a hydrogen atom, having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group;^TenAnd R
¹¹Are cyclopentadienyl group and substituted cyclopenes, respectively.
Tadienyl group, indenyl group or fluorenyl group, R¹²
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
It represents an aryl group or an arylalkyl group. R¹³Is Tet
Macrocyclic compounds such as laphenylporphyrin and phthalocyanine
Indicates a ligand. k is [L¹-R⁹], [L²] Ion value
An integer of 1 to 3 in number, a is an integer of 1 or more, b = (k × a)
It is. M^FourAre periodic table Nos. 1-3, 11-13, and 17
It contains a group element, M^FiveAre the 7th to 12th periodic tables
Indicates a group element. ] Is preferably used
Can be.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile. Specific examples of R ⁹ include hydrogen, methyl group, ethyl group, benzyl group, trityl group, and the like, and specific examples of R ¹⁰ and R ¹¹ include cyclopentadienyl group, methylcyclopentadienyl group. Group, ethylcyclopentadienyl group,
Examples thereof include a pentamethylcyclopentadienyl group. Specific examples of R ¹² include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ¹³ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. it can. Further, as a specific example of M ⁴ , Li, N
a, K, Ag, Cu, Br, I, I _{3 and the} like, and specific examples of M ⁵ include Mn, Fe, Co and N.
Examples thereof include i and Zn.

[Z ¹ ] ^- , that is, [M ³ G ¹ G
² ... G ^f ], specific examples of M ³ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group or an aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. Iodine, p-fluorophenyl group as a hydrocarbon group containing a hetero atom, 3,5
-Difluorophenyl group, pentachlorophenyl group,
3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as organic metalloid group pentamethylantimony group, trimethylsilyl group, trimethyl Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or a combination of conjugate base of a Bronsted acid and Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{-, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyl diphenyl ammonium tetraphenyl borate, triphenyl (methyl) ammonium tetraphenyl borate, trimethylanilinium tetraphenyl borate, methyl pyridinium tetraphenyl borate, benzyl pyridinium tetraphenyl borate, methyl tetraphenyl borate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

As the component (B-1), one type of ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex may be used, or two or more types may be used in combination. You may use. On the other hand, as the aluminoxane of the component (B-2), the general formula (IV)

[0039]

Embedded image

[Wherein R ¹⁴ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and w represents a degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40. Each R ¹⁴ may be the same or different. Represented by the chain aluminoxane,
And the general formula (V)

[0041]

Embedded image

[In the formula, R ¹⁴ and w are the same as defined above. And a cyclic aluminoxane represented by the following formula: Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be toluene-insoluble. These aluminoxanes may be used alone or in combination of two or more.

The Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. The organic compound is a boron compound or an aluminum compound, the inorganic compound is a magnesium compound,
Aluminum compounds and the like are preferably used. Examples of the aluminum compound include aluminum oxide and aluminum chloride, and examples of the magnesium compound include magnesium chloride and diethoxymagnesium.
Examples of the boron compound include triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron. , Tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5) -Difluorophenyl) boron, tris [3,5
-Bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron and n-butyldifluoroboron. These Lewis acids may be used alone or in combination of two or more.

The ratio of the (A) catalyst component and the (B) catalyst component used in this polymerization catalyst (I) is a molar ratio when the (B-1) compound is used as the (B) catalyst component. Preferably 10: 1 to 1: 100, more preferably 2: 1.
Is preferably in the range of 1:10, and when the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1:10.
00000, more preferably 1:10 to 1: 10000
The range of is desirable. The (A) catalyst component and (B-3) catalyst component are used in a molar ratio of preferably 1: 0.1.
˜1: 2000, more preferably 1: 0.2 to 1: 100
The range of 0, more preferably 1: 0.5 to 1: 500 is desirable. Further, as the catalyst component (B), (B-1),
(B-2), (B-3) and the like can be used alone or in combination of two or more kinds. The polymerization catalyst (I) is
It may contain the above-mentioned components (A) and (B) as main components, or may contain the above-mentioned components (A), (B) and (C) organoaluminum compounds as main components. May be Here, the organoaluminum compound as the component (C) is represented by the general formula (VI) R ¹⁵ _v AlJ _{3 -v} (VI) [wherein, R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, preferably Is an alkyl group having 1 to 10, J is a hydrogen atom, and has 1 to 2 carbon atoms.
It represents an alkoxy group of 0, an aryl group having 6 to 20 carbon atoms or a halogen atom, and v is an integer of 1 to 3. ] The compound shown by these is used.

Specific examples of the compound represented by the general formula (VI) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The (A) catalyst component and (C) catalyst component are preferably used in a molar ratio of 1: 1 to 1: 100.
00, more preferably 1: 5 to 1: 2000, further preferably 1:10 to 1: 1000. By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In this polymerization catalyst (I), at least one catalyst component can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO and Z.
rO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Z
Examples thereof include nO, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite and glass fiber. Among these, especially SiO ₂ ,
Al ₂ O ₃ is preferred. The inorganic oxide carrier is
It may contain a small amount of carbonates, nitrates, sulfates and the like.
On the other hand, as carriers other than the above, MgCl ₂ , Mg (OC
Examples thereof include magnesium compounds represented by the general formula MgR ¹⁶ _X X ² _y represented by magnesium compounds such as ₂ H ₅ ) ₂ and complex salts thereof. Here, R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ² represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0
2, y is 0 to 2, and x + y = 2. Each R ¹⁶ and each X ² may be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. The carrier used in the present invention is MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ ,
SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). reference). Furthermore, it is desirable that the above-mentioned carrier is usually calcined at 150 to 1000 ° C., preferably 200 to 800 ° C. before use.

When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably (A) catalyst component and (B).
It is desirable to support both catalyst components. In the carrier,
The method of supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, an organoaluminum compound as a carrier. After treatment with, a method of mixing with at least one of the component (A) and the component (B) in an inert solvent, a method of reacting the carrier with the component (A) and / or (B) and the organoaluminum compound, A method in which the component (A) or the component (B) is supported on a carrier and then mixed with the component (B) or the component (A), and a contact reaction product of the component (A) and the component (B) is mixed with the carrier. A method, a method of allowing a carrier to coexist in the contact reaction between the component (A) and the component (B), and the like can be used. In addition, in the reaction of the above, and (C)
It is also possible to add the component organoaluminum compound.

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the polymerization system. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 20 kg / cm ² to obtain −20 to 200. It is possible to use a method in which catalyst particles are produced by carrying out prepolymerization at a temperature of 1 minute to 2 hours.

In the present invention, the above compound (B-1)
The ratio of the component to the carrier used is preferably 1: 5 by weight.
˜1: 10000, more preferably 1:10 to 1:50
0 is desirable, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight.
More preferably, the ratio is 1: 1 to 1:50,
The weight ratio of the component (B-3) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10.
It is desirable to be set to about 1: 500. When two or more kinds of catalyst components (B) are mixed and used, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of component (A) to the carrier is preferably 1: 5 to 1: 10000 by weight, more preferably 1:10 to 1: 500 by weight.

Component (B) [Component (B-1), (B-
If the ratio of the component (2) or the component (B-3)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. The average particle size of the polymerization catalyst (I) thus prepared is usually 2 to 200 μm.
m, preferably 10 to 150 μm, particularly preferably 20
To 100 μm, and the specific surface area is usually 20 to 1000.
m ² / g, preferably from 50 to 500 m ² / g. If the average particle diameter is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. Also,
In the polymerization catalyst (I), the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, and particularly preferably 0.1 to 2 g. If the amount of transition metal is out of the above range, the activity may decrease.

By thus supporting on a carrier, a copolymer having a high bulk density industrially advantageous and an excellent particle size distribution can be obtained. Next, in the polymerization catalyst (II), the transition metal compound used as the component (A ′) is
It is represented by the general formula (Ib) CpM ² E ¹ E ² E ³ ... (Ib).

In the above general formula (Ib), M²Is Titani
Indicates um, zirconium or hafnium. Especially preferred
M²Is titanium. Cp is M²And η^Five-Bond
In the formula, cyclopentadienyl or position coordinated by a π bond
C5-C30 having a substituted cyclopentadienyl skeleton
A cyclic compound group, E¹E²And E^ThreeRespectively σ
By binding the M²Is a sigma ligand that coordinates to. This σ distribution
Examples of the rank include R^'', OR^'', SR^'', SO_Three
R^'', NR^''R^''', PR^''R^''', NO₂,halogen
Atom, 1-pyrrolyl and 1-pyrrolidinyl are preferred.
I can do it. Here, R ″ and R ′ ″ are carbon atoms 1
20 hydrocarbon groups or silyl groups containing hydrocarbon groups.
You. At least one of the σ ligands is a halogen source.
Child, OR ", NR" R '"or PR" R' "
Is preferred. Also, E¹E²And E ^ThreeIdentical to each other
May also be different. Said M²And η^Five-In a binding fashion
Cyclopentadienyl coordinated by π bond or substituted silane
C5-C30 cyclic having a clopentadienyl skeleton
The group consisting of the compound is one, and the substituted cyclopentene
Substituents on the tadienyl skeleton bond to each other to create new
It does not matter even if it forms a simple annular structure. That is,
Indenyl skeleton, substituted indenyl skeleton, fluorenyl bone
And a group having a substituted fluorenyl skeleton is also a cyclic compound.
Included in the group.

In the above R ^" and R ^'" , examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
A butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group; and a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; Examples of the group include a phenyl group and a tolyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the silyl group containing a hydrocarbon group include a trimethylsilyl group,
And a triphenylsilyl group. OR
^As specific examples of ^'' , methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group, Examples thereof include an alkoxy group such as a cyclohexoxy group and an aryloxy group such as a phenoxy group. Specific examples of SR ^″ include a methylthio group, an ethylthio group, a cyclohexylthio group and a phenylthio group. Then, specific examples of SO ₃ R ^″ include methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n-butanesulfonyl group, sec-butanesulfonyl group, t-butanesulfonyl group, Examples thereof include an alkylsulfonyl group such as an isobutanesulfonyl group and an arylsulfonyl group such as a benzenesulfonyl group. Furthermore, NR ^'' R
Specific examples of ^"" include dimethylamino group, diethylamino group, di (n-propyl) amino group, diisopropylamino group, di (n-butyl) amino group, diisobutylamino group, di (sec-butyl) amino group. , Di (t-butyl) amino group, dipentylamino group, dihexylamino group, dioctylamino group, diphenylamino group, dibenzylamino group, methylethylamino group, (t-butyl)
Examples thereof include a trimethylsilylamino group and a methyltrimethylsilylamino group. Also, PR ^" R ^'"
As specific examples of, a dimethylphosphido group, a diethylphosphido group, a di (n-propyl) phosphido group,
Diisopropylphosphido group, di (n-butyl) phosphido group, diisobutylphosphido group, di (sec
-Butyl) phosphido group, di (t-butyl) phosphido group, dipentylphosphido group, dihexylphosphido group, dioctylphosphido group, diphenylphosphido group, dibenzylphosphido group, methylethylphosphido group, (t- Butyl) trimethylsilylphosphido group, methyltrimethylsilylphosphido group and the like can be mentioned. Further, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the transition metal compound represented by the general formula (Ib) include cyclopentadienyl titanium trimethyl; cyclopentadienyl titanium triethyl; cyclopentadienyl titanium tri (n-propyl); cyclopentadiene. Cyclopentadienyl titanium tri (n-butyl); cyclopentadienyl titanium triisobutyl; cyclopentadienyl titanium tri (sec-butyl); cyclopentadienyl titanium tri (t-butyl); methyl 1,2-dimethylcyclopentadienyl titanium trimethyl; 1,2,4-trimethylcyclopentadienyl titanium trimethyl; 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl; Pentamethylcyclope Pentamethylcyclopentadienyl titanium triethyl; pentamethylcyclopentadienyl titanium tri (n-propyl); pentamethylcyclopentadienyl titanium triisopropyl; pentamethylcyclopentadienyl titanium tri (n-butyl) ); Pentamethylcyclopentadienyl titanium triisobutyl; pentamethyl cyclopentadienyl titanium tri (sec-butyl); pentamethyl cyclopentadienyl titanium tri (t-butyl); cyclopentadienyl titanium trimethoxide; cyclo Pentadienyl titanium triethoxide; Cyclopentadienyl titanium tri (n-propoxide); Cyclopentadienyl titanium triisopropoxide; Cyclopentadienyl titanium triphenoxide; Methylcyclo Pentadienyl titanium trimethoxide; (n-butyl) cyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium triethoxide; dimethylcyclopentadienyl titanium tri ( n-propoxide); dimethylcyclopentadienyl titanium triisopropoxide; dimethyl cyclopentadienyl titanium triphenoxide; di (t
-Butyl) cyclopentadienyl titanium trimethoxide; di (t-butyl) cyclopentadienyl titanium triethoxide; di (t-butyl) cyclopentadienyl titanium tri (n-propoxide); di (t- Butyl) cyclopentadienyl titanium triisopropoxide; di (t
-Butyl) cyclopentadienyl titanium triphenoxide; bis (trimethylsilyl) cyclopentadienyl titanium trimethoxide; bis (trimethylsilyl) cyclopentadienyl titanium triethoxide; bis (trimethylsilyl) cyclopentadienyl titanium tri (n- Propoxide); bis (trimethylsilyl) cyclopentadienyl titanium triisopropoxide; bis (trimethylsilyl) cyclopentadienyl titanium triphenoxide; trimethylcyclopentadienyl titanium trimethoxide; trimethylcyclopentadienyl titanium triethoxide; Trimethylcyclopentadienyl titanium tri (n-propoxide); Trimethylcyclopentadienyl titanium triisopropoxide; Trimethylcyclopentadienyl titanium tri Enoxide; triethylcyclopentadienyl titanium trimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium trimethoxide; [di (t-butyl, methyl)] cyclopentadienyl titanium triethoxide; tetra Methylcyclopentadienyl titanium trimethoxide; Tetramethylcyclopentadienyl titanium triethoxide; Tetramethylcyclopentadienyl titanium tri (n-propoxide); Tetramethylcyclopentadienyl titanium triisopropoxide; Tetramethyl Cyclopentadienyl titanium tri (n-butoxide); Tetramethylcyclopentadienyl titanium triisobutoxide; Tetramethyl cyclopentadienyl titanium tri (sec-butoxide); Tetramethyl cyclopentadienyl tita Tri (t-butoxide); tetramethylcyclopentadienyl titanium triphenoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium trimethoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri Ethoxide; [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4- Methoxyphenyl] cyclopentadienyl titanium triphenoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium Tri (n-propoxide); [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, benzyl] Cyclopentadienyl titanium trimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, benzyl]
Cyclopentadienyl titanium triisopropoxide;
[Tetramethyl, benzyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 2-
Methoxyphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, ethyl] cyclopentadioxide Phenyl titanium tri (n-propoxide); [tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide; [tetramethyl, n
-Butyl] cyclopentadienyl titanium triethoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium tri (n-propoxide); [tetramethyl,
[n-butyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, phenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, phenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, trimethylsilyl] Cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide;
Pentamethylcyclopentadienyl titanium tri (n-propoxide); pentamethylcyclopentadienyl titanium triisopropoxide; pentamethylcyclopentadienyl titanium tri (n-butoxide); pentamethylcyclopentadienyl titanium triiso Butoxide; pentamethylcyclopentadienyl titanium tri (sec-butoxide); pentamethylcyclopentadienyl titanium tri (t-butoxide); pentamethylcyclopentadienyl titanium tri (cyclohexoxide); pentamethylcyclopentadienyl Titanium triphenoxide; cyclopentadienyl titanium tribenzyl; indenyl titanium trimethoxide; indenyl titanium triethoxide; indenyl titanium trimethyl; indenyl titanium tribenzyl; cyclopen Dienyl titanium tri (methanesulfonyl); trimethyl cyclopentadienyl titanium (tri benzenesulfonyl); tetramethylcyclopentadienyl titanium tri (ethanesulfonyl); pentamethylcyclopentadienyltitanium tri (methanesulfonyl);
Cyclopentadienyl titanium tris (dimethylamide); trimethylcyclopentadienyl titanium tris (dimethylamide); pentamethylcyclopentadienyl titanium tris (dibenzylamide); pentamethylcyclopentadienyl titanium tris (dimethylamide);
Pentamethylcyclopentadienyl titanium tris (diethylamide); cyclopentadienyl titanium tri (nitro); pentamethylcyclopentadienyl titanium tri (nitro), etc., and compounds in which titanium in these compounds is replaced with zirconium or hafnium Can be mentioned.

Further, cyclopentadienyl titanium dimethyl monochloride; cyclopentadienyl titanium monoethyl dichloride; cyclopentadienyl titanium di (n
-Propyl) monochloride; cyclopentadienyl titanium diisopropyl monochloride; cyclopentadienyl titanium di (n-butyl) monochloride; cyclopentadienyl titanium diisobutyl monochloride; cyclopentadienyl titanium di (sec-butyl) mono Chloride; cyclopentadienyl titanium di (t-butyl) monochloride; 1,2-dimethylcyclopentadienyl titanium dimethyl monochloride; 1,2,4-trimethylcyclopentadienyl titanium dimethyl monochloride; 3,
4-tetramethylcyclopentadienyltitanium dimethylmonochloride; pentamethylcyclopentadienyltitanium dimethylmonochloride; cyclopentadienyltitanium monochlorodimethoxide; cyclopentadienyltitaniumdichloromonomethoxide; cyclopentadienyltitaniumdichloromono Ethoxide; cyclopentadienyltitanium monochlorodioxide (n-propoxide); cyclopentadienyltitanium monochlorodithiopropoxide; cyclopentadienyltitanium monochlorodiphenoxide; dimethylcyclopentadienyltitanium monochlorodimethoxide;
Dimethylcyclopentadienyl titanium monochlorodioxide; dimethylcyclopentadienyl titanium monochlorodioxide (n-propoxide); dimethylcyclopentadienyl titanium monochlorodiisopropoxide; dimethylcyclopentadienyl titanium monochlorodiphenoxide;
Di (t-butyl) cyclopentadienyl titanium monochlorodimethoxide; Bis (trimethylsilyl) cyclopentadienyl titanium monochlorodimethoxide; Trimethylcyclopentadienyl titanium monochlorodimethoxide;
Trimethylcyclopentadienyl titanium monochlorodiphenoxide; triethylcyclopentadienyl titanium monochlorodimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium monochlorodimethoxide; tetramethylcyclopentadienyl titanium monochlorodimethoxide; tetra Methylcyclopentadienyl titanium dichloromonomethoxide; Tetramethylcyclopentadienyl titanium monochlorodi (n-butoxide);
Tetramethylcyclopentadienyl titanium monochloroisobutoxide; Tetramethylcyclopentadienyl titanium monochlorolog (sec-butoxide); Tetramethylcyclopentadienyl titanium monochlorolog (t-butoxide); [Tetramethyl, 4-methoxyphenyl ] Cyclopentadienyl titanium monochlorodimethoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodiphenoxide; [Tetra Methyl, 2-methoxyphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl , N-Butyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl, n-butyl] cyclopentadienyl titanium monochlorodiethyl (n-propoxide); [Tetramethyl, n-butyl ] Cyclopentadienyl titanium monochlorodiisopropoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl titanium monochloro Dimethoxide;
Pentamethylcyclopentadienyl titanium dichloromonomethoxide; pentamethylcyclopentadienyl titanium monochlorodiethoxide; pentamethylcyclopentadienyl titanium monochlorodioxide (cyclohexoxide); pentamethylcyclopentadienyl titanium monochlorodiphenoxide; Indenyl titanium monochlorodimethoxide; cyclopentadienyl titanium monochlorodimethane (methanesulfonyl); pentamethylcyclopentadienyl titanium monochlorobis (diethylamide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) amide] Pentamethylcyclopentadienyl titanium dichloro (dimethylamide); pentamethylcyclopentadienyl titanium dichloro (diphenylamide);
Pentamethylcyclopentadienyl titanium dichloro (methylethylamide); Pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamide); Pentamethylcyclopentadienyl titanium dimethoxy (diphenylamide); Pentamethylcyclopentadienyl titanium Monochlorobis (diethylphosphide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide]; pentamethylcyclopentadienyl titanium dichloro (dimethylphosphide); pentamethylcyclopentadienyl titanium dimethoxy ( Dimethyl phosphide); pentamethylcyclopentadienyl titanium dichloro (diphenyl phosphide); pentamethyl cyclopentadienyl titanium dichloro (methyl ethyl) Osufido); pentamethylcyclopentadienyl titanium dichloro (t-butyl trimethylsilyl phosphinothricin de); pentamethylcyclopentadienyl titanium dimethoxy (diphenyl phosphinate de); cyclopentadienyl titanium trichloride; n-
Butylcyclopentadienyl titanium trichloride; Tetramethyl cyclopentadienyl titanium trichloride; Pentamethyl cyclopentadienyl titanium trichloride;
Pentaethylcyclopentadienyl titanium trichloride; [Tetramethyl, n-butyl] cyclopentadienyl titanium trichloride; Tetraisopropylcyclopentadienyl titanium trichloride; Tetraphenylcyclopentadienyl titanium trichloride; Novornacyclopenta Dienyl titanium trichloride; indenyl titanium trichloride; 4,5,6,7-tetrahydroindenyl titanium trichloride; [1,2,3-trimethyl, 4,
5,6,7-Tetrahydro] indenyl titanium trichloride; [1,2,3,4,5,6,7-heptamethyl]
Indenyl titanium trichloride; pentamethylcyclopentadienyl titanium trifluoride; pentamethylcyclopentadienyl titanium tribromide; pentamethylcyclopentadienyl titanium triiodide, and the like, and titanium in the compound In place of, corresponding compounds containing zirconium and hafnium are mentioned. In the polymerization catalyst (II), one kind of the transition metal compound as the component (A ′) may be used, or two or more kinds thereof may be used in combination.

As the component (B ') in the polymerization catalyst (II), an ionic compound which reacts with the transition metal compound of the component (A') to form an ionic complex, an aluminoxane or a Lewis acid is used. To be These are the same as those described as the component (B) in the polymerization catalyst (I). These (B ′) components may be used alone or in combination of two or more, and aluminoxane is particularly preferable. The ratio of the (A ′) catalyst component and the (B ′) catalyst component used in the polymerization catalyst (II) is the ratio of the (A) component and the (B) component used in the polymerization catalyst (I). Is the same as. In the polymerization catalyst (II), a phenolic compound and / or water can be used as the component (D) for the purpose of further improving the activity, and the phenolic compound is particularly preferable. As the phenolic compound, for example, a hydrogen atom bonded to an aromatic ring such as a benzene ring or a naphthalene ring is substituted with at least one hydroxyl group or at least one hydroxyl group and at least one substituent other than hydroxyl group. The compounds mentioned above can be mentioned.

Here, examples of the substituent other than the hydroxyl group include
For example, R¹⁷, OR¹⁷, SR¹⁷, NR¹⁷R¹⁸， Halogen source
Child, nitro group, etc. R¹⁷, R¹⁸Is 1 carbon
~ 20 hydrocarbon groups, alkyl groups, cycloalkyl
Groups, aryl groups, aralkyl groups and the like. Alkyl group
Are, for example, methyl group, ethyl group, n-propyl
Group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, t-butyl group, pentyl group, hexyl
Group, octyl group, decyl group, dodecyl group, etc.
Examples of the alkyl group include a cyclopentyl group and a cyclo group.
An aryl group such as a lohexyl group is, for example,
Examples of aralkyl groups such as phenyl and tolyl are
Examples include benzyl and phenethyl groups.
Wear. OR¹⁷As specific examples of, methoxy group, ethoxy
Group, n-propoxy group, isopropoxy group, n-butoxy group
Si group, isobutoxy group, sec-butoxy group, t-but
Xy group, pentoxy group, hexoxy group, octoxy group,
Alkoxy group such as cyclohexoxy group, phenoxy group
And an aryloxy group. NR
¹⁷R¹⁸Specific examples of are dimethylamino group, diethyl
Amino group, di (n-propyl) amino group, diisopropyi
Ruamino group, di (n-butyl) amino group, diisobutyl
Amino group, di (sec-butyl) amino group, di (t-butyl)
Cyl) amino group, dipentylamino group, dihexylamido
Group, dioctylamino group, diphenylamino group, dibe
And the like. Also halo
Examples of the gen atom include chlorine, bromine, iodine and fluorine.
Can be

As the component (D), a phenolic compound and / or water is used. Here, the phenolic compound is preferably a phenolic compound substituted with a hydrocarbon group having 1 to 20 carbon atoms, and particularly α, α'- of the hydroxyl group.
A phenolic compound whose position is substituted with a hydrocarbon group having 1 to 20 carbon atoms is preferable. Specific examples of the phenolic compound include phenol; 2-methylphenol; 2-
Ethylphenol; 2-n-Propylphenol; 2-
Isopropylphenol; 2-n-butylphenol;
2-sec-butylphenol; 2-tert-butylphenol; 3-tert-butylphenol; 4-t
4-tert-octylphenol; 2-n-dodecylphenol; 2-phenylphenol; 4-phenylphenol; 2,6-dimethylphenol; 2,6-diethylphenol; 2,6-
Di-tert-butylphenol; 2,4-di-ter
2-tert-butyl-4-methylphenol; 2-tert-butyl-5-methylphenol; 2-tert-butyl-6-methylphenol; 2-n-dodecyl-4-methylphenol; 4- n
-Dodecyl-2-methylphenol; 2,6-diphenylphenol; 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-
Ethylphenol; 2,4,6-tri-tert-butylphenol; 2,2'-methylenebis (4-methyl-)
6-tert-butylphenol); 2,2'-methylenebis (4-ethyl-6-tert-butylphenol); 4,4'-methylenebis (2,6-di-tert.
-Butylphenol); 4,4'-butylidenebis (6
-Tert-butyl-m-cresol); 4,4'-thiobis (6-tert-butyl-m-cresol); α
-Naphthol; β-naphthol; 2-fluorophenol; 3-fluorophenol; 4-fluorophenol; 2,4-difluorophenol; 2,5-difluorophenol; 2,6-difluorophenol; 2-methoxyphenol; 3- Methoxyphenol; 4-methoxyphenol; 2,6-di-tert-butyl-4-
Methoxyphenol; N, N-dimethyl-3-aminophenol; N, N-diethyl-3-aminophenol;
N, N-di-n-butyl-3-aminophenol; 2,
6-di-tert-butyl-4-dimethylaminophenol; 2-nitrophenol; 3-nitrophenol;
4-nitrophenol; 2-nitro-4-methylphenol; 3-nitro-4-methylphenol; 4-nitro-3-methylphenol; 5-nitro-2-methylphenol; catechol; resorcinol; hydroquinone;
3-methylcatechol; 4-methylcatechol; 4-t
ert-Butylcatechol; 2-methylresorcinol; 5-methylresorcinol; methylhydroquinone;
tert-butylhydroquinone; 2,5-di-tert
-Butylhydroquinone; 1,2-dihydroxynaphthalene; 1,4-dihydroxynaphthalene; 1,5-dihydroxynaphthalene; 1,6-dihydroxynaphthalene;
1,7-Dihydroxynaphthalene; 2,3-Dihydroxynaphthalene; 2,7-Dihydroxynaphthalene; Pyrogallol; Phloroglucinol; 1,2,4-Trihydroxybenzene; Hexahydroxybenzene; 4,4 '
-Thiobis (2,6-di-tert-butylphenol); 3,5-di-tert-butyl-4-hydroxybenzyl chloride and the like. These phenolic compounds may be used alone or in combination of two or more.

In this polymerization catalyst (II), the phenolic compound and / or water as the component (D) are the hydroxyl group / (B 'in the component (D) when aluminoxane is used as the component (B'). ) Component aluminoxane (aluminum equivalent)
It is preferable to use it so that the molar ratio is in the range of 0.001 to 0.8. If this molar ratio is less than 0.001, the activity improving effect is insufficient, and if it exceeds 0.8, the activity tends to decrease. From the viewpoint of improving the activity, a more preferable molar ratio is in the range of 0.01 to 0.6, and particularly 0.05 to 0.5.
Is preferred. The calculation was made on the assumption that one mole of water had 2 moles of hydroxyl groups. Further, the order of contacting each catalyst component is not particularly limited, but after contacting the component (B ') and the component (D), the component (A') is contacted, or the component (B ') and ( It is preferable from the viewpoint of catalytic activity that the component (D) is contacted after the component A ′) is contacted. In the polymerization catalyst (II), other than the above-mentioned (A ′) component, (B ′) component and (D) component, other catalyst components may be used, if desired, within a range not impairing the object of the present invention. May be included.
If desired, as in the case of the polymerization catalyst (I), each catalyst component may be brought into contact with an appropriate carrier to be supported on the carrier.

On the other hand, in the polymerization catalyst (III),
The components (A ') and (B') and their proportions are the same as in the case of the polymerization catalyst (II). This polymerization catalyst
In (III), for the purpose of further improving the catalytic activity and copolymerizability, as the component (E), a reaction product of (a) an organoaluminum compound and a phenolic compound and / or (b) an organoaluminum compound The reaction product of the boron compound with a boron compound is used. Examples of the organoaluminum compound used as the raw material for the component (a) include the same organoaluminum compounds described as the component (C) in the polymerization catalyst (I), and trialkylaluminum is particularly preferable. The phenolic compound may be the same as the phenolic compound described as the component (D) in the polymerization catalyst (II).

The ratio of the phenolic compound to the organoaluminum compound used is preferably a phenolic compound / organoaluminum compound molar ratio of 0.1 to 2.5,
More preferably 0.5 to 2.2, particularly preferably 1.0 to 2.0.
It is selected in the range of. The reaction conditions are not particularly limited, but a method of mixing and reacting them in a suitable inert solvent such as benzene, toluene, hexane and heptane at a temperature of 40 ° C. or less while stirring is advantageous. is there. As the reaction product of the organoaluminum compound and the phenolic compound thus obtained,
In particular, general formula (VII) R ¹⁹ _m Al (OAr) _3-m ... (VII) [In the formula, R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. , Ar has 6 to 20 carbon atoms
M represents a real number of 1 to 2, and when there are a plurality of OArs, the plurality of OArs may be the same or different. ] Are preferred.

Specific examples of the organoaluminum compound represented by the general formula (VII) include dimethylaluminum phenoxide, methylaluminum diphenoxide, dimethylaluminum (2-methylphenoxide), dimethylaluminum (2-ethylphenoxide) and dimethyl. Aluminum (2-n-propylphenoxide), dimethylaluminum (2-tert-butylphenoxide), dimethylaluminum (4-tert-butylphenoxide), dimethylaluminum (2,6-di-t).
tert-butylphenoxide), methylaluminummudi (2,6-di-tert-butylphenoxide), dimethylaluminum (2,4-di-tert-butylphenoxide), methylaluminum di (2,4-di-te)
rt-butylphenoxide), dimethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), methylaluminum di (2,6-di-tert)
-Butyl-4-methylphenoxide), dimethylaluminum (2,6-di-tert-butyl-4-ethylphenoxide), methylaluminum di (2,6-di-t)
tert-butyl-4-ethylphenoxide), dimethylaluminum (2,4,6-tri-tert-butylphenoxide), methylaluminum di (2,4,6-tri-tert-butylphenoxide), dimethylaluminum (2 6-dimethylphenoxide), methylaluminum di (2,6-dimethylphenoxide), dimethylaluminum (2,6-diphenylphenoxide),
Methyl aluminum di (2,6-diphenylphenoxide), dimethyl aluminum (2,6-difluorophenoxide), methyl aluminum di (2,6-difluorophenoxide), methyl aluminum di (1,1-bi-2-naphthoxide), etc. And, in addition to these compounds, a methyl group bonded to aluminum in the compound is an ethyl group, an n-propyl group, an isopropyl group,
And compounds substituted with -butyl group, isobutyl group, n-hexyl group, n-octyl group and the like.

On the other hand, as the organoaluminum compound used as the raw material of the reaction product of the component (b), the same organoaluminum compound used as the raw material of the reaction product of the component (a) can be mentioned. Further, as the boron compound, a compound represented by the general formula (Ic)

[0065]

[Chemical 6]

[In the formula, X, Y and D each represent a sulfur atom or an oxygen atom, which may be the same or different from each other. ] The compound represented by these is used. Examples of the compound represented by the general formula (Ic) include trihydroxyboron (boric acid), dihydroxyhydrothioxyborone, hydroxydihydrothioxyboron, trihydrothioxyboron and the like. Among these, trihydroxyboron, dihydroxyhydrothioxyboron and hydroxydihydrothioxyboron are preferable, and trihydroxyboron is particularly preferable.

The boron compound and the organoaluminum compound have a substantially stoichiometric amount, that is, a substantially molar ratio of 1: 3.
Used in proportion. The reaction of both components is usually carried out in an inert solvent under an inert gas atmosphere. Further, the contacting method of both components is not particularly limited, and various methods such as (1) adding and dissolving a boron compound in a toluene solvent and then dissolving the organoaluminum compound as it is or toluene of the organoaluminum compound A method of adding a suspension little by little, (2) a method of adding a hexane diluted solution of a boron compound to a hexane diluted solution of an organoaluminum compound, and (3) a method of diluting a boron compound and an organoaluminum compound in toluene. It is possible to use a method such as dropping at a constant speed into another container to cause a reaction. In this case, the reaction temperature and the reaction time are not particularly limited, but both components are generally low temperature, for example, -78 to.
After mixing at a temperature of 30 ° C., preferably −78 to 10 ° C., it is desirable that the temperature be gradually raised to a temperature of about −10 to 80 ° C. At this time, the temperature may be raised to the boiling point of the reaction solvent, if necessary. The reaction time is usually 2 to 48.
It's about time.

The reaction product of the organoaluminum compound and the boron compound thus obtained is particularly represented by the general formula (VIII) (R ²⁰ R ²¹ AlO) ₃ B (VIII) ²⁰ and R ²¹ each represent a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, which may be the same or different.
The two R ²⁰ R ²¹ AlO may be the same or different. ]
An organoaluminum compound represented by is preferable. Specific examples of the organoaluminum compound represented by the general formula (VIII) include tris (dimethylaluminoxy) borane, tris (diethylaluminoxy) borane, tris (di-n-propylaluminoxy) borane, tris (diisopropyl). Aluminoxy) borane, tris (diisobutylaluminoxy) borane, tris (di-n-hexylaluminoxy) borane, tris (di-n-octylaluminoxy) borane, tris (methylethylaluminoxy) borane, tris (ethylisobutyl) Aluminoxy)
Examples include borane.

In this polymerization catalyst (III), (E)
As the component, the component (a) may be used alone or in combination of two or more. Further, the component (b) may be used alone or in combination of two or more. Furthermore, one or more components (a) and one or more components (b) may be used in combination. The catalyst component (A ') and (E)
From the viewpoint of catalytic activity, etc., the molar ratio of the catalyst component used is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2,000, and further preferably 1:10.
A range of 1: 1000 is desirable. This polymerization catalyst (III)
In addition, in addition to the above-mentioned components (A ′), (B ′) and (E), other catalyst components may be contained, if desired, within a range that does not impair the object of the present invention. Further, if desired, each catalyst component may be brought into contact with an appropriate carrier to be carried on the carrier. Examples of the carrier include inorganic oxides such as silica and alumina, inorganic halides such as magnesium chloride, inorganic alkoxides such as diethoxymagnesium, and polymers such as polystyrene.

The ethylene copolymers (I) and (I
I) is the above-mentioned polymerization catalyst (I), (II) or (III)
In the presence of, (i) ethylene and (b) at least one selected from an α-olefin having 3 to 20 carbon atoms, a diene compound, and a cyclic olefin can be copolymerized to produce. In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Phase polymerization is particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
0 to 250 ° C, preferably -50 to 200 ° C, more preferably
It is preferably 0 to 130 ° C. Also, for the reaction raw materials
The ratio of catalyst used is as follows: raw material monomer / transition metal compound (mode
Ratio) is preferably 1-10 ⁸, Especially from 10 to 10^FiveWhen
It is preferable that Further, the polymerization time is usually 5 minutes to 1
0 hours, reaction pressure is preferably normal pressure to 200 kg / cm
²G, particularly preferably normal pressure to 100 kg / cm²G
You. As a method for adjusting the molecular weight of the polymer,
Selection of type, amount, polymerization temperature, and even in the presence of hydrogen
There is a polymerization of. When a polymerization solvent is used, for example,
Benzene, toluene, xylene, ethylbenzene, etc.
Aromatic hydrocarbons, cyclopentane, cyclohexane, methyl
Cycloaliphatic hydrocarbons such as cyclohexane, pentane,
Aliphatic hydrocarbons such as xane, heptane, octane,
Halogenated hydrocarbons such as loroform and dichloromethane
Etc. can be used. These solvents are one type
Can be used together, or two or more types can be combined.
Yes. Also, using a monomer such as α-olefin as a solvent
You may use. In addition, depending on the polymerization method, it is performed without solvent.
be able to. Molecules of the copolymer thus obtained
The amount is not particularly limited, but the intrinsic viscosity [η]
(Measured in decalin at 135 ° C) is 0.1 deciliter /
g or more is preferable, and 0.2 deciliter / g or more is particularly preferable.
Good.

In the present invention, preliminary polymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited,
A known method can be used. The olefin used for the prepolymerization is not particularly limited, and ethylene and the same ones as those exemplified above, for example, α having 3 to 20 carbon atoms can be used.
-Olefin, or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as that used in the polymerization. The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 1
It is 30 ° C, more preferably 0 to 80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (135) of the prepolymerized product is
C. decalin) of 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, transition metal component 1 in the catalyst 1
The amount of prepolymerized product per millimole is 1 to 10
It is desirable to adjust the conditions so that the amount is 000 g, particularly 10 to 1000 g. In this way, the ethylene copolymers (I) and (II) of the present invention can be efficiently obtained.

The present invention also comprises, as the component (A), any one of the above ethylene copolymers (I) and (II),
(B) a component using an α-olefin having 3 to 20 carbon atoms, and (B) a component containing ethylene and 3 carbon atoms
.About.20 .alpha.-olefin, and the weight average molecular weight (Mw) in terms of polyethylene measured by gel permeation chromatography is 3,000 to 1.00.
It has a resin density of 0.85 to 0.95 g /
The present invention relates to an ethylene-based copolymer composition (I, II) containing an ethylene-based copolymer in the cm ³ range, and such composition improves tear strength without lowering impact strength. It is possible to obtain a film excellent in both impact strength and tear strength. The content of the component (A) in the ethylene copolymer composition of the present invention is preferably 20% by weight or more based on the entire composition. If the content is less than 20% by weight, the effect of the present invention cannot be sufficiently obtained. From the viewpoint of such effects, the content is more preferably 50% by weight or more.

In the above ethylene-based copolymer composition,
The ethylene-based copolymer used as the component (B) is obtained from ethylene and an α-olefin having 3 to 20 carbon atoms, and has a polyethylene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography.
Is in the range of 3,000 to 1,000,000, and the resin density is
Although it is in the range of 0.85 to 0.95 g / cm ³ ,
As the C3-C20 α-olefin used here, the same ones as those used for the component (A) can be used. Also, its Mw is 3,000 to 1,0.
Although it is in the range of 0,000, if Mw is less than 3,000, sufficient mechanical properties cannot be obtained, and if it exceeds 1,, 000,000, the moldability is deteriorated. From the viewpoint of the balance of mechanical properties and molding processability, the preferable Mw is 10,000 to 800,0.
The range is 00, and the range of 15,000 to 60,000 is particularly preferable. Further, the ethylene copolymer has a resin density in the range of 0.85 to 0.95 g / cm ³ , and the resin density is arbitrarily controlled in the above range by increasing or decreasing the content of the comonomer unit. can do.

The method for producing the ethylene copolymer as the component (B) is not particularly limited, and in the presence of a catalyst usually used for producing an ethylene copolymer, ethylene and the α having 3 to 20 carbon atoms are used. -It can be obtained by copolymerizing with an olefin. The catalyst includes the catalyst used for producing the ethylene copolymer as the component (A), and either a supported catalyst or a homogeneous catalyst can be used. The polymerization conditions are also not particularly limited, but the polymerization can be carried out, for example, under the conditions used for producing the ethylene copolymer of the component (A). The ethylene-based copolymer composition of the present invention can be prepared by homogeneously mixing the ethylene-based copolymer as the component (A) and the ethylene-based copolymer as the component (B). As the mixing method, various methods that are commonly used can be used, and for example, any method such as mixing with a mixer or an extruder in a molten state or mixing in a solution state can be used.

The ethylene-based copolymer (II) or the ethylene-based copolymer composition (II) of the present invention having the above-mentioned properties is used, for example, in ordinary air-cooled inflation molding, air-cooled two-stage inflation molding, water-cooled inflation molding. The film of the present invention can be obtained by molding by a melt extrusion method such as T-die casting. The film of the present invention may have either a single-layer structure or a multi-layer structure, and the thickness thereof is not particularly limited, but is usually in the range of 10 μm to 3 mm. Therefore, the film of the present invention includes so-called sheets. The film formed in this manner is subjected to, for example, a dry laminating method or an extrusion laminating method (sandwich laminating method), nylon, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, or the like, or a barrier material metal such as aluminum (a vapor-deposited film). Or foil)
It can be used as a composite film such as a laminated film or a laminated film after being laminated with an adhesive or a polyolefin resin. At this time, the film of the present invention is preferably used as a heat seal layer.

The ethylene-based copolymer (II) of the present invention
Alternatively, when an ethylene-based copolymer composition (II) is formed into a film, various additives usually used in film formation such as an antioxidant, an ultraviolet absorber, a light stabilizer, and a heat stabilizer are added to the copolymer. A stabilizer, a neutralizing agent, a lubricant, an antiblocking agent, an antistatic agent, a coloring agent, etc. may be added as necessary to form a film. The thus-obtained film of the present invention is excellent in mechanical properties such as tear strength and impact strength, and is also excellent in heat sealability, ESCR property, etc., and is used in inflation film field, cast film field, sealant field, It is preferably used in the film packaging field such as the lamination field.

[0078]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Aluminum Catalyst Component A methylaluminoxane toluene solution (manufactured by Albemarle) having a concentration of 1.4 mol / liter (as Al atom) was mixed with A
Using 4.2 mol as 1 atom, while stirring in a nitrogen atmosphere at room temperature, 2,6-di-t-butylphenol was added thereto in an amount of 0.2 times the mol of Al atom of methylaluminoxane for 1 hour. It dripped gradually over it. Then one more
The reaction was carried out over time to obtain an aluminum catalyst component. (2) Production of ethylene / octene-1 copolymer n-hexane was added to a continuous polymerization reactor having an internal volume of 1 liter.
6.0 l / h, ethylene at 700 g / h, hydrogen at 0.27 g / h and octene-1 at 900 g / h were fed. Next, the catalyst solution of pentamethylcyclopentadienyl titanium trimethoxide was converted into 1.
67 mmol / hour, and the methylaluminoxane solution prepared in (1) above was supplied from another supply line at 72 mmol / hour in terms of Al atom. Polymerization reaction was performed at 186 ° C. to obtain an ethylene / octene-1 copolymer. (3) Evaluation of Copolymer The copolymer obtained in (2) above was evaluated. The results are shown in Table 1.

Example 2 (1) Preparation of Aluminum Catalyst Component A methylaluminoxane toluene solution (manufactured by Albemarle) having a concentration of 1.4 mol / liter (as Al atom) was added to A
0.2 mol was used as 1 atom, and nitrogen containing water was introduced into this while stirring at room temperature. The introduction was gradually performed over 16 hours, and 0.16 times mol of water was introduced with respect to Al atoms. Then, the reaction was carried out for 5 hours to obtain an aluminum catalyst component. (2) Production of ethylene / octene-1 copolymer In a pressure resistant autoclave with an internal volume of 4 liters equipped with a stirrer,
Under a nitrogen atmosphere, 1560 ml of toluene, 40 ml of octene-1 and 4 mmol (as Al atom) of the methylaluminoxane prepared in the above (1) were added, and the temperature was raised to 60 ° C with stirring. After maintaining this state for 5 minutes, a catalyst solution of pentamethylcyclopentadienyltitanium trimethoxide was added in an amount of 40 μmol in terms of Ti atom, and the temperature was raised to 65 ° C. Hydrogen
1.0 kg / cm ² G was charged, and ethylene was added at 4 kg /
It was introduced continuously while maintaining a constant pressure of cm ² G at 65 ° C.
The copolymerization reaction was carried out for 30 minutes. After completion of the reaction, the reaction mixture was depressurized, deactivated with alcohol, and the copolymer was recovered and dried to obtain 76 g of an ethylene-octene-1 copolymer. (3) Evaluation of Copolymer The copolymer obtained in (2) above was evaluated. The results are shown in Table 1.

Example 3 A continuous polymerization reactor having an internal volume of 1 liter was charged with n-hexane.
5.5 liter / hour, 700 g / hour of ethylene and 900 g / hour of octene-1 were added, and further 2 hydrogen was supplied.
It was supplied at a pressure of 8 kg / cm ² . Further, as catalyst components, 1.33 mmol / hour of pentamethylcyclopentadienyltitanium trichloride, 72 mmol / hour of methylaluminoxane in terms of aluminum and 2 mmol of methylaluminum bis (2,6-di-t-butylphenoxide). / Hour after contacting and supplied. The polymerization reaction was carried out under the conditions of a polymerization temperature of 185 ° C. and a reaction pressure of 70 kg / cm ² to obtain an ethylene-1-octene copolymer A-1. The copolymer obtained above was evaluated. The results are shown in Table 1.

[0081]

[Table 1]

Comparative Example 1 Ethylene / octene-1 copolymer sample A (octene-1 unit content 2.7 mol%), ethylene / octene-1 copolymer sample B (octene-1 unit content) And an ethylene / octene-1 copolymer Sample C (octene-1 unit content 4.6 mol%). Table 2 shows the results.

[0083]

[Table 2]

Examples 4 and 5 and Reference Examples 1 to 3 The ethylene type copolymer compositions were prepared by mixing in the combinations and proportions shown in Table 3. Mixing is carried out by Toyo Seiki Seisakusho Labo Plastomill at 170 ° C for 30c.
Melting and kneading were carried out at 20 rpm for 5 minutes using the mixer of c. The obtained composition was press-molded to have a thickness of 60 to 70 μm for measuring tear strength and tensile impact strength.
A sheet of m, 20 cm × 20 cm was prepared. All presses are North Cross 50 ton presses, 230 ℃,
Press at 50kg / cm ² for 5 minutes, then 50 minutes in 3 minutes
The cooling was performed at such a rate that the temperature became ℃. Using these sheets, see J.
The test was conducted according to ISK-7128. The tensile impact strength was tested according to ASTM D1822. The MI of the composition is 190 ° C. and the load is 2.
It was measured under the condition of 16 kg. The compositions were evaluated. The results are shown in Table 3.

[0085]

[Table 3]

[0086]

The ethylene-based copolymer of the present invention has a narrow molecular weight distribution and branching degree distribution, and its composition distribution shape is controlled. An excellent film can be given. Further, the ethylene-based copolymer composition of the present invention, the molecular weight distribution is narrow, the composition distribution is wide, by blending the ethylene-based copolymer excellent in tensile strength, without lowering the impact strength, tear strength And a film excellent in both impact strength and tear strength can be provided.

[Brief description of drawings]

FIG. 1 is a diagram showing a composition distribution curve obtained by a temperature rising fractionation method for obtaining a composition distribution of an ethylene-based copolymer and a curve obtained by approximating its main peak by a Gaussian distribution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Kurokawa 1280, Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (10)

[Claims] (1) ethylene and (b) a carbon number of 3 to 2.
In an ethylene-based copolymer obtained from at least one α-olefin, a diene compound, and a cyclic olefin of 0, (1) a weight average molecular weight (Mw) in terms of polyethylene measured by gel permeation chromatography method The ratio Mw / Mn between the number average molecular weight (Mn) and the number average molecular weight (Mn) is in the range of 1.5 to 4, and the weight average molecular weight (Mw) is in the range of 3,000 to 1,000,000, (2) The half-width at half maximum [W / 2] of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to the Gaussian distribution and the average number of short-chain branches of the polymer n (pieces / 100
0 carbon number) satisfies the formula 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n, and (3) the resin density is 0.85 to 0.95.
An ethylene copolymer characterized by being in the range of g / cm ³ . 2. The ethylene copolymer according to claim 1, which is a copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms. 3. (a) ethylene and (b) a carbon number of 3 to 2
In an ethylene-based copolymer obtained from at least one selected from α-olefins, diene compounds and cyclic olefins of 0, the weight average molecular weight (Mw) and number average in terms of polyethylene measured by gel permeation chromatography method and number average Ratio Mw with molecular weight (Mn)
/ Mn range from 1.5 to 4 and resin density from 0.85 to 0.95
In the composition distribution curve obtained by the temperature rising fractionation method in the range of g / cm ³ , the area of the region surrounded by the curve obtained by approximating the Gaussian distribution of the main peak and the base line is A, and the composition distribution curve is The area of the region on the low temperature side where the elution temperature exceeds 32 ° C. is surrounded by the curve obtained by approximating the main peak by the Gaussian distribution and the base line is B, the area of the region on the high temperature side is C, the composition distribution curve and the baseline line. Tear strength (TS, kgf
/ Cm) is the expression TS ≧ 131.5-155 × log [{(B + C + D) /
A} +0.1] and the formula 0.1 ≦ (B + C + D) / A ≦ 1. 4. The ethylene-based copolymer according to claim 3, which is a copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms. 5. The weight average molecular weight (Mw) in terms of polyethylene measured by gel permeation chromatography is in the range of 3,000 to 1,000,000,
And the half-width at half maximum [W / 2] of the curve obtained by approximating the main peak of the composition distribution curve obtained by the temperature rising fractionation method to the Gaussian distribution
And the average number of short-chain branches of polymer n (number / 1000 carbons)
The ethylene-based copolymer according to claim 3 or 4, wherein the relationship with the formula is 0.704 + 0.147n≤W / 2≤-0.055 + 0.577n. 6. An ethylene copolymer obtained from (A) (a) ethylene and (b) an α-olefin having 3 to 20 carbon atoms, wherein (1) polyethylene measured by gel permeation chromatography. Ratio Mw of reduced weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn is in the range of 1.5 to 4 and the weight average molecular weight (Mw) is in the range of 3,000 to 1,000,000, (2) of the composition distribution curve obtained by the temperature rising fractionation method. Half-width at half maximum of the curve obtained by approximating the main peak by Gaussian distribution [W
/ 2] and the average number of short-chain branches n (number / 1000 carbons) of the polymer satisfy the formula 0.704 + 0.147n ≦ W / 2 ≦ −0.055 + 0.577n, and (3) Resin density is 0.85-0.95
An ethylene copolymer in the range of g / cm ³ and (B) an ethylene copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms, which is measured by a gel permeation chromatography method. Polyethylene equivalent weight average molecular weight (Mw) is 3,000 to 1.0
It is in the range of 0,000 and the resin density is 0.85-0.9.
An ethylene-based copolymer composition containing an ethylene-based copolymer in the range of 5 g / cm ³ . 7. An ethylene-based copolymer of component (A)
The ethylene-based copolymer composition according to claim 6, wherein the ethylene-based copolymer composition is contained in an amount of at least wt%. 8. The (A) component ethylene-based copolymer comprises:
(B) an ethylene-based copolymer obtained from ethylene and (b) an α-olefin having 3 to 20 carbon atoms, which has a weight-average molecular weight (Mw) in terms of polyethylene measured by gel permeation chromatography. The composition distribution curve obtained by the temperature rising fractionation method, in which the ratio Mw / Mn with the number average molecular weight (Mn) is in the range of 1.5 to 4 and the resin density is in the range of 0.85 to 0.95 g / cm ^3. At
The area of the region surrounded by the curve obtained by approximating the main peak with a Gaussian distribution and the base line is A, and the area of the composition distribution curve and the curve obtained by approximating the main peak with the Gaussian distribution and the base line are on the low temperature side. When the area of the region where the elution temperature exceeds 32 ° C is B, the area of the high temperature side is C, and the area of the region where the elution temperature is 25 to 32 ° C surrounded by the composition distribution curve and the base line is D, The tear strength (TS, kgf / cm) is calculated by the formula TS ≧ 131.5-155 × log [{(B + C + D) /
A} +0.1] and the formula 0.1 ≦ (B + C + D) / A ≦ 1 are satisfied, and the ethylene copolymer composition according to claim 6 or 7. 9. A film obtained by forming the ethylene copolymer according to claim 1 into a film. 10. A film obtained by forming the ethylene copolymer composition according to any one of claims 6 to 8.