JPH10310607A - Resin composition for electrical insulation material, and electric wire and cable insulated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrical insulation material comprising an ethylene (co)polymer having a broad molecular weight distribution, excellent processability and excellent electrical insulation properties. SOLUTION: This invention provides an electrical insulation material comprising an ethylene (co)polymer satisfying the requirements (I) to (III) or a blend of 100-2 wt.% this (co)polymer with 0-98 wt.% another olefin polymer and an electrical wire or cable insulated therewith. (I): the components insoluble in a solvent prepared by mixing butylcellosolve with paraxylene in a volume ratio of 50/50 at 126 deg.C contains at least 0.2 long-chain branch (6C or higher branch) per 10,000 carbon atoms, (II) the MFR is 0.001-100 g/10 min, and (III) the electrical activation energy is 0.4 eV or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ethylene having a wide molecular weight distribution, excellent workability and excellent electrical insulation.
(Co) A resin composition for an electrical insulating material composed of a polymer, and an electric wire or cable using the resin as an electric insulating material (in the present specification, "electric wire or cable" is abbreviated as "electric wire or cable"). About.

[0002]

2. Description of the Related Art In recent years, with the advent of so-called metallocene catalysts, strong ethylene polymers have been obtained. At the same time, it is known that an ethylene polymer having low electric activation energy and suitable for an electric insulating material can be obtained (Japanese Patent Application Laid-Open No. 9-17235). However, these have a narrow molecular weight distribution and insufficient fluidity, and have low melt tension and are not necessarily excellent in processability such as wire coating. Means for improving these include methods such as blending components having different molecular weights and multi-stage polymerization.

[0003] However, the molecular weight distribution of the ethylene-based polymer produced by using these catalysts is not sufficiently high. Furthermore, there is a method of blending an ethylene-based polymer produced using a Ziegler-based catalyst or a Phillips catalyst, which has a different molecular weight from an ethylene-based polymer produced using a metallocene catalyst. Gazette, JP-A-1-292009, JP-A-3-203903, JP-A-4-220405, JP-A-6-1222719, JP-A-7-
No. 17329, JP-A-8-41118, JP-A-8-100018, JP-B-8-13856), electrical insulation deteriorates,
In addition, the wire coating processability is still insufficient, and there is a disadvantage that dispersion failure is apt to occur, resulting in melt fracture or reduction in strength.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an electrically insulating material comprising an ethylene (co) polymer having a wide molecular weight distribution, excellent workability, and excellent electrical insulation. .

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned objects, and as a result, have found that an ethylene (co) polymer or a blend thereof with another olefin polymer satisfying specific parameters. Product is excellent in electric wire covering property, and it is found that it is an electric insulation material with good electric insulation.
The present invention has been reached.

That is, a first aspect of the present invention is the following (I)
To (III), preferably the conditions (I) to (V),
More preferably, it is a resin composition for an electrical insulating material comprising an ethylene (co) polymer (A) which satisfies all of the conditions (I) to (VI). (I) a component insoluble at 126 ° C. in a solvent in which butyl cellosolve and para-xylene are mixed at a volume fraction of 50:50,
Contains 0.2 long chain branches (C6 or more branches) / 10,000C or more. (II) MFR is 0.001 to 100 g / 10 min. (III) The electric activation energy is 0.4 eV or less. (IV) In the frequency ω dependency of the complex viscosity η ^* (ω),
When ω is between 10 ⁻² rad / sec and 10 ⁴ rad / sec, there is at least one inflection point. (V) At least one of the following equations (1) and (2) is satisfied.

HLMFR swell ratio (%)> 50 + 25 × log (HLMFR) (1)

MT (g)> 4.8−12.1 × log (MFR) (2) (VI) Gel permeation chromatography (GP
C) Mz / Mw obtained by measurement is 6.0 or more, and a molecular weight distribution parameter (GDI) obtained by approximating a certain region of the molecular weight distribution curve by Gaussian distribution is 5.0 or less.

A second aspect of the present invention is the above-mentioned ethylene (co) polymer.
(A) 100 to 2% by weight of other olefin polymer (B) 0
It is a resin composition for an electrical insulating material, characterized in that the resin composition comprises about 98% by weight.

A third aspect of the present invention is the above-mentioned ethylene (co) polymer.
A wire / cable using a resin composition containing (A) or another olefin-based polymer (B) as an electrical insulating material.

Hereinafter, the present invention will be described in detail. The ethylene (co) polymer (A) in the present invention is a homopolymer of ethylene,
Alternatively, it is a copolymer of ethylene and another α-olefin, and has a density of 0.88 to 0.97 g / cm ³ .

The ethylene (co) polymer (A) is composed of (I) a component insoluble in a solvent in which butylcellosolve and para-xylene are mixed at a volume fraction of 50 to 50 at 126 ° C. is a long-chain branched (C6
The above branch) is 0.2 or more than 10,000C. That is, the high molecular weight component (weight average molecular weight (Mw) of 1,000,000 or more) of the ethylene (co) polymer (A) used in the present invention is:
It has long chain branches. In addition, in this specification, the number of long-chain branches represents a C6 or more branch measured by ¹³ C-NMR.

A component insoluble at 126 ° C. in a solvent in which butyl cellosolve and para-xylene are mixed at a volume ratio of 50 to 50 can be obtained, for example, as follows. That is, after dissolving the polymer in para-xylene at a temperature of 130 ° C., celite is added, the temperature is lowered to 30 ° C. at a rate of 10 ° C./hour, and the polymer is attached to the celite. Next, after the slurry-like celite is packed in a column, the solvent is replaced at 23 ° C. with butyl cellosolve which is a poor solvent. After heating to 126 ° C,
As a developing solution, paraxylene is gradually added from 100% of butyl cellosolve, and the solubility is gradually increased, and the components are sequentially fractionated from low molecular weight components. The insoluble component is a component that is not collected when a solvent in which butyl cellosolve and para-xylene are mixed at a volume ratio of 50 to 50 is used as a developing solution. This component is, for example, para-xylene 1
Separation can be performed by using 00% as a developing solution.

The ethylene (co) polymer (A) has an insoluble component having a long-chain branch number (C6 or higher branch number) of 0.2 / 10,000C.
It is necessary to be above. Heretofore, a resin having a wide molecular weight distribution and a high molecular weight component containing a long chain branch and having excellent electrical insulation properties has not been obtained. If the number of long-chain branches in the insoluble component (high-molecular-weight component) is less than 0.2 / 10,000 C, the long-term relaxation component decreases, resulting in a decrease in the melt elasticity of the ethylene (co) polymer. Excellent moldability cannot be obtained. The preferred number of long chain branches is at least 0.3 / 10,000C, more preferably at least 0.4 / 10,000C.

The ethylene (co) polymer (A) is (II) M
FR is in the range of 0.001 to 100 g / 10 min, preferably 0.1 to 100 g / 10 min, more preferably 0.2 to 5 g / min.
0 g / 10 minutes. If the MFR is less than 0.001 g / 10 minutes, the moldability is poor, and if it is 100 g / 10 minutes or more, mechanical strength such as impact resistance is reduced. Here, MFR is J
It is measured at a temperature of 190 ° C. and a load of 2.16 kgf according to IS-K7210 condition 4.

The ethylene (co) polymer (A) further comprises (II)
I) The electric activation energy is 0.4 eV or less, preferably 0.3 eV or less, more preferably 0.25 eV or less. When the electric activation energy exceeds 0.4 eV,
As the temperature increases, the amount or mobility of charge carriers such as ions or electrons greatly increases, and thermal stability and chemical stability decrease. This value is very small as compared with the conventional polyethylene material, and the ethylene (co) polymer used in the present invention has a special property that the amount and mobility of the charge carrier contained therein are not easily affected by temperature. It has a simple structure.

The activation energy is one of the constants included in the Arrhenius equation representing the temperature change of the rate constant in the process of transport phenomena. The electrical activation energy is used in the Arrhenius equation showing the temperature dependence of the current. A small electric activation energy indicates that the current has low temperature dependence.

In the present invention, the electric activation energy can be determined by using the Arrhenius equation shown in equation (3) and substituting the current values at room temperature (20 ° C.) and 90 ° C., for example.

I∝exp (−U / kT) (3) where U is the electrical activation energy, k is the Boltzmann constant, T is the absolute temperature, and I is the current value.

The ethylene (co) polymer (A) in the present invention
Is further (IV) dependent on the frequency ω that ω is 10 ⁻²
Preferably, there is at least one inflection point between rad / sec and 10 ⁴ rad / sec. ω is 10 ^-2 ra
between d / sec and 10 ⁴ rad / sec, the complex viscosity η ^* (ω)
Does not exist, that is, ω is 10 ⁻² rad /
Logη ^* (ω) in all regions from 10 to 10 ⁴ rad / sec
If the inflection point does not exist, the compatibility of fluidity and high melt tension, which are the characteristics of the polymer of the present invention, cannot be achieved, and the stability at the time of covering the electric wire becomes insufficient.

As a method of quantitatively describing the behavior of the molten state of a polymer, there are a method of obtaining linear viscoelasticity and a method of examining the melting behavior during steady shear fluidization. The principle and the measuring method are described in detail in, for example, Chapter 2 of "Lecture / Rheology" (edited by the Society of Rheology of Japan, published by the Society of Polymer Publishing, 1992). The frequency omega dependence of complex viscosity η ^* (ω) in the present invention, in addition to those being strictly defined by linear viscoelastic, Cox - complex viscosity by Merz (Cox-Merz) law eta ^* (omega ) Is considered equivalent to shear viscosity η (γ)
, Which is converted from the shear rate γ dependence regarded as equivalent to the frequency ω.

The frequency dependence of the complex viscosity used in the present invention is such that when the frequency ω is in the range of 10 ⁻² rad / sec to 10 ² rad / sec, a parallel plate having a diameter of 2.5 mm is measured with RMS-800 manufactured by Rheometrics. And the complex viscosity η ^* (ω) is measured at a set temperature of 190 ° C. Further, the frequency ω is from 10 ² rad / sec to 10 ⁴
The frequency dependency of the complex viscosity η ^* (ω) in the range of rad / sec was determined by using a Capillograph IC manufactured by Toyo Seiki Seisaku-Sho, Ltd., with a nozzle orifice diameter of 0.76 mm and a length of 25.40.
It can be obtained by measurement under the conditions of mm and a temperature of 190 ° C. by the method described in JIS-K7199.

In general, the complex viscosity η ^* (ω) of a polymer decreases as the frequency ω increases. When the frequency dependence of the complex viscosity η ^* (ω) is expressed by the relationship between log η ^* (ω) and log ω, the conventional polyethylene-based polymer has log η
^* The degree of decrease of (ω) gradually increases as ω increases, and becomes a constant value. The degree of decrease is dlogη ^* (ω) /
dlogω (first derivative of logη ^* (ω) with respect to logω), so that dlogη ^* (ω) / dlogω
Gradually decreases (the absolute value increases). That is, log
There is usually no inflection point in the dependence of η ^* (ω) and logω.

Since the ethylene (co) polymer used in the present invention has a special relaxation time distribution, when ω is between 10 ⁻² rad / sec and 10 ⁴ rad / sec, a decrease in log η ^* (ω) with respect to log ω There is at least one region in which the degree of decrease is large. The existence of the inflection point is determined by the first-order differential dlogη ^* (ω) / dlog of the frequency dependence of the complex viscosity, which is easily calculated by using the analysis software RH10S attached to the RMS-800.
It is more clearly indicated that ω has a local maximum. The existence of the inflection point indicates that the frequency ω of the complex viscosity η ^* (ω) calculated using the same analysis software is used.
This means that there is a region where the second derivative of the dependence is positive. That is, ω is from 10 ⁻² rad / sec to 10 ⁴ rad.
Between d / sec, there is a region satisfying the following expression (4).

[0022]

D ² (logη ^* (ω)) / d (logω) ² > 0 (4)

The ethylene (co) polymer (A) further comprises (V)
It is preferable that at least one of the following expressions (1) and (2) is satisfied.

[0024]

HLMFR swell ratio (%)> 50 + 25 × log (HLMFR) (1)

MT (g)> 4.8−12.1 × log (MFR) (2)

Equation (1) must be satisfied in a region where MFR cannot be measured, and Expression (2) must be satisfied in a region where HLMFR cannot be measured. Each of these formulas indicates that the melt tension of the resin is high, and those that do not satisfy these conditions make the moldability at the time of covering the electric wire unstable. In particular, it is preferable that the formula (2) is satisfied from the viewpoint of molding stability when covering the electric wire.

In the above formula (1), HLMFR means J
Melt flow rate (unit: g) measured at a temperature of 190 ° C. and a load of 21.6 kgf in accordance with Condition 7 of IS-K7210
/ 10 minutes). In addition, HLMFR swell ratio (%)
And using the THERMISTOR X416 of TAKARA (Ltd.), a capillary nozzle (diameter D ₀ = 1.0 mm, length L = 10.0 mm,
L / D = 10, inflow angle = 90 °), the load is 21.6kg,
The value obtained by measuring the diameter of a strand obtained by extruding at a temperature of 190 ° C. with a micrometer as D (mm) is a value obtained by the following equation (5).

[0027]

HLMFR swell ratio (%) = (D−D ₀ ) × 100 / D ₀ (5)

In the above formula (2), MT indicates a melt tension. Here, the melt tension MT refers to a capillarographic IC manufactured by Toyo Seiki Seisaku-sho, Ltd.
5mm, length 8mm, temperature 190 ° C, extrusion speed 15mm
/ Min, a value measured at a take-up speed of 6.5 m / min. The MFR is JIS-K as described above.
Based on condition 4 of 7210, temperature 190 ° C, load 2.16k
It is measured under the condition of gf.

The ethylene (co) polymer (A) used in the present invention
Further, (VI) Mz / Mw obtained by gel permeation chromatography (GPC) measurement is 6.0 or more, and a molecular weight distribution parameter (GD) obtained by approximating a specific region of a molecular weight distribution curve by Gaussian distribution approximation.
It is desirable that I) is 5.0 or less.

The Mz / Mw of the ethylene (co) polymer (A) and the molecular weight parameter (GDI) obtained by approximating a specific region of the molecular weight distribution curve by Gaussian distribution in the present invention are:
It can be determined by GPC. Specifically, GPC
As a device, 150C manufactured by Waters was used, and 2,6
1,2,4-trichlorobenzene containing 0.1% of -di-t-butyl-p-cresol (BHT) as an antioxidant was used as a mobile phase, and a column manufactured by Showa Denko KK was used as a column.
x HT-G and Shodex HT-806M
A total of three tubes are connected in series, and a measurement can be performed at a measurement temperature of 140 ° C. using a differential refractometer as a detector.

Mz / Mw is represented by the ratio between the Z-average molecular weight (Mz) and the weight-average molecular weight (Mw), and is determined as follows. The peak height detected by the differential refractometer is recorded at regular time intervals T, and the elution time is plotted on the horizontal axis and the peak height (arbitrary unit) is plotted on the vertical axis, and a chromatogram is created. A base line is drawn horizontally between the peak start point and the end point, and the peak height Hi from the base line between them (i means the i-th data, counted from the earlier elution time (higher molecular weight)) ). The elution time is determined by a calibration curve determined in advance from a series of monodisperse polystyrene samples having different molecular weights.
Means the i-th data), and Mw and Mz in terms of polystyrene are obtained by the following equations (6) and (7), respectively.

[0032]

Mw = Σ (Mi · Hi) / ΣHi (6) Mz = Σ (Mi · Mi · Hi) / Σ (Mi · Hi) (7)

Mz / Mw can be determined from the ratio of Mz and Mw determined in this way. Note that the above M
The method for calculating w and Mz and the method for preparing a calibration curve are described in detail, for example, in Sadao Mori; size exclusion chromatography (published by Kyoritsu Shuppan).

GDI in the present invention can be obtained as follows using GPC data. As shown in FIG. 1, in the molecular weight distribution curve defined by expressing the natural logarithm ln (Mi) of the molecular weight on the horizontal axis and Hi on the vertical axis, the maximum point (Hm) of Hi and the molecular weight lower than the maximum point And its peak value Hi is 95% of the maximum value.
Gaussian distribution approximation is performed using data that is less than and equal to or greater than 30%. Specifically, first, for all data in the above-described approximate area, Si defined by the following equation is obtained (i means the i-th data).

[0035]

Equation 11] Hi = Hm · exp (- ( Xi-Xm) 2 / (2Si 2)) (8) symbols in formula represents the following meaning. Hm: the peak height at the peak maximum point; Xm: the natural logarithm of the molecular weight at the peak maximum point (ln (molecular weight)); Xi: the natural logarithm of the molecular weight of the approximate data; Hi: the peak height of the approximate data.

By arithmetically averaging the Si thus calculated, GDI can be obtained by the following equation (9).

GDI = exp (S ² ) (9) where S is the average value of Si.

In order to accurately determine the Mz / Mw and GDI of the ethylene (co) polymer (A) in the present invention, GPC
It is necessary that the number of data from the peak start point to the end point in the data is 50 or more.

Mz / Mw of the ethylene (co) polymer (A) in the present invention must be 6.0 or more. Preferably it is 6.5 or more, more preferably 7.0 or more. Mz /
When the Mw is less than 6.0, the stability in covering the electric wire is poor, which may be undesirable. The GDI is preferably 5.0 or less, more preferably 4.5 or less, and still more preferably 3.5 or less. If the GDI exceeds 5.0, the change in the molecular weight and molecular weight distribution of the (co) polymer is so poor that the required properties may not be sufficiently satisfied.

The ethylene (co) polymer (A) of the present invention may be any one of ethylene homopolymers or copolymers of ethylene and α-olefins having 3 to 12 carbon atoms which satisfy the above parameters. Although there is no particular limitation, the most preferred polymerization catalyst for producing these is a chromium compound (a-1), a carrier (a-2), an aluminoxane (a-3),
It is composed of a transition metal compound (a-4) having a group having a conjugated π electron as a ligand and, if desired, an organometallic compound.

The chromium compound of the catalyst component (a-1) may be converted to chromium oxide by firing in the presence of oxygen, or may be used without firing in the presence of oxygen.

When converted to chromium oxide by firing in the presence of oxygen, the chromium compound is represented by the general formula (1)
0) or chromium carboxylate represented by (11), chromium-1,3-diketo compound represented by general formula (12), chromate ester represented by general formula (13), chromium ester represented by general formula (14) or ( Chromamide compounds represented by 15), organic chromium compounds represented by general formulas (16) to (18), chromium trioxide, or chromium oxides, halides, oxyhalides, nitrates, sulfates, acetates, oxalic acids Any chromium compound that can be converted to chromium oxide by firing in the presence of oxygen such as a salt is included. At least a portion of the chromium atoms after firing in the presence of oxygen must be in a hexavalent state.

[0042]

[0043]

[0044]

Embedded image CrY _e Z ¹ _f Z ² _g (12)

[0045]

[0046]

[0047]

[0048]

(Cp ¹ ) _k (R ⁴² ) _2-k Cr (16)

(Cp ¹ ) (R ⁴² ) _m (R ⁴³ ) _2-m Cr (L ² ) _n (17)

Embedded image (R ⁴⁴ ) _p Cr (18)

In the above formula, R ^{1 to} R ⁴¹ may be the same or different, each is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ⁴² and R ⁴³ are the same or different. Well, each having an aryl group having 1 to 20 carbon atoms, an alkyl group,
An alkenyl group, an alkylaryl group, an arylalkyl group, an allyl group, a silylalkyl group or an alkoxy group, and R ⁴⁴ represents an aryl group having 1 to 20 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group, An allyl group or a silylalkyl group, and Y is
1,3-diketo chelating ligands Z ¹ and Z
² may be the same or different and each is a halogen atom, an alkoxy, an aryloxy, an alkyl, an aryl or an amide group, M ¹ to M ¹² are a carbon atom or a silicon atom, and L ¹ and L ² are Ether, nitrile,
Ligands such as pyridine and tetrahydrofuran;
p ¹ is an alkyl-substituted or unsubstituted cyclopentadienyl group, an alkylsilyl-substituted cyclopentadienyl group, an alkylgermyl-substituted cyclopentadienyl group, or an indenyl group having or not having a substituent, a cycloalkyl group such as a fluorenyl group. A ligand having a pentadienyl skeleton, e is 1 to 3, e + f + g = 3, and h is 0 to 2
Where k is 1-2, m is 1-2, and n is 0
Or 1, and p is 2-4.

Preferred chromium compounds are organic chromium compounds, chromium trioxide or chromium oxides, halides, oxyhalides, nitrates, sulfates, acetates, oxalates, and more preferably chromium trioxide. Or chromium oxides, halides, oxyhalides, nitrates, sulfates, acetates, oxalates,
Specific examples include chromium trioxide, chromium trichloride, chromyl chloride, chromium nitrate, chromium sulfate, chromium acetate, chromium oxalate, and ammonium chromate.

Examples of the chromium compound to be used without firing in the presence of oxygen include the above-mentioned chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, organic chromium compound and the like. Preferably, a chromate ester, a chromamide compound,
Specific examples include bis (tert-butyl) chromate, bis (triphenylsilyl) chromate, and tris (bistrimethylsilylamide) chromium (III).

The carrier of the catalyst component (a-2) may be an oxide of an element belonging to Group 2, 4, 13, or 14 of the periodic table (the group is based on the inorganic chemical nomenclature 1990 rules; the same applies hereinafter), or an element belonging to Group 13 It is commonly used as a component of a catalyst for ethylene-based polymerization, such as a phosphate of the present invention. Examples of oxides of Group 2, 4, 13 or 14 elements and phosphates of Group 13 elements include magnesia, titania, zirconia, alumina, silica, silica-titania, silica-zirconia, silica-alumina, phosphorus Examples include aluminum acid, gallium phosphate, and mixtures thereof.
The specific surface area is 50 to 1000 m ² / g, particularly 200 to 800 m ²
/ G, pore volume of 0.5 to 3.0 cm ³ / g, especially 1.0 to 2.5 c
m ³ / g, average particle size of 10 to 200 μm, especially 30 to 1
Those having a size of 50 μm are preferably used.

When the chromium compound (a-1) is used without calcining, the carrier (a-2) can be used at a temperature of 100 to 900 ° C. for 10 minutes under a stream of molecular sieves and a stream of dry nitrogen gas. Those dried by heating for 24 hours are preferably used. It is preferable to heat and dry under a solid flow state in a sufficient amount of nitrogen gas flow.

When the chromium compound (a-1) is converted to chromium oxide by firing in the presence of oxygen, the chromium compound (a-1) is first supported on a carrier (a-2), After being changed to chromium oxide by baking in the presence, aluminoxane described below is supported. The term "calcination" as used herein means that the calcination is carried out at a temperature in the range of 300 to 1000C for 1 to 48 hours in a state of fluidization with a dry gas containing oxygen.

Examples of the aluminoxane as the catalyst component (a-3) include compounds represented by the following general formula (19) or (20).

[0056]

[0057]

In the formula, R ⁴⁵ is a hydrocarbon group such as methyl, ethyl, propyl, n-butyl and isobutyl;
Preferably, they are a methyl group and an isobutyl group. r is 1 to
100, preferably 4 or more, particularly preferably 8 or more.

The method for producing this type of compound is known, and examples thereof include salts having water of crystallization (such as copper sulfate hydrate and aluminum sulfate hydrate) such as pentane, hexane, heptane, cyclohexane, decane, benzene and toluene. Examples thereof include a method in which a trialkylaluminum is added to a suspension of an inert hydrocarbon solvent, and a method in which solid, liquid or gaseous water is allowed to act on the trialkylaluminum in a hydrocarbon solvent.

Further, an aluminoxane represented by the following general formula (21) or (22) may be used.

[0061]

[0062]

Wherein R ⁴⁶ is a hydrocarbon group such as methyl, ethyl, propyl, n-butyl, isobutyl, etc.
Preferably, methyl group, isobutyl group, R ⁴⁷ is selected from methyl, ethyl, propyl, n- butyl, hydrocarbon groups such as isobutyl or chlorine, halogen atom or a hydrogen atom such as bromine, the hydroxyl group,, R ⁴⁶ And a different group. Further, a plurality of R ⁴⁷ in the general formula (21) may be the same or different. s is usually 1 to 100, preferably 3 or more, and s + t is 2 to 100, preferably 6 or more.

In the general formula (21) or (22), two units May be combined in blocks or may be combined regularly or irregularly at random.

The method for producing such an aluminoxane is the same as that for the above-mentioned aluminoxane of the general formula. Instead of using one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used or one or more kinds of trialkylaluminum are used. And at least one kind of dialkylaluminum monohalide or dialkylaluminum monohydride.

The ligand in the transition metal compound having a group having a conjugated π electron of the catalyst component (a-4) as a ligand is one having a cyclopentadienyl skeleton, an amidinato skeleton or an allyl skeleton. . As the ligand having a cyclopentadienyl skeleton, for example, a cyclopentadienyl group, an alkyl-substituted cyclopentadienyl group, an alkylsilyl-substituted cyclopentadienyl group, an alkylgermyl-substituted cyclopentadienyl group, or the like Examples thereof include an indenyl group and a fluorenyl group having or not having a substituent. Examples of the ligand having an amidinato skeleton include an amidinato group, an alkyl-substituted amidinato group, an alkylsilyl-substituted amidinato group, an aryl-substituted amidinato group, and an amidinato group having a plurality of substituents. In addition, examples of the ligand having an allyl skeleton include allyl groups having or not having the same substituent as described above.

The transition metal is a transition metal element belonging to Group 3, 4, 5, or 6 of the periodic table, and is preferably selected from transition metal elements belonging to Group 4 of the periodic table, ie, titanium, zirconium and hafnium. Those are preferred, and zirconium or hafnium is particularly preferred.

Specific examples of the component (a-4) include transitions represented by the following general formulas (23), (24), (25), (26), (27), (28) and (29). Metal compounds.

(Cp ² ) (Cp ³ ) _u Me (Q ¹ ) _3-u (23)

Embedded image R ⁵¹ (Cp ² ) (Cp ³ ) Me (Q ¹ ) (Q ² ) (24)

Embedded image R ⁵¹ (Cp ² ) (Y) Me (Q ¹ ) (Q ² ) (25)

[0069]

[0070]

[0071]

[0072]

In the above formula, Cp ² and Cp ³ may be the same or different and each is a ligand having the above-mentioned cyclopentadienyl skeleton, and R ^{48 to} R ⁵⁰ may be the same or different. A hydrogen atom, an alkyl having 1 to 20 carbon atoms,
A hydrocarbon group such as alkenyl, aryl, araryl, aralkyl and alicyclic, an alkylsilyl group or an alkylgermyl group, and R ⁵¹ has 1 to 20 carbon atoms.
X ¹ and X ² may be the same or different, each is a carbon atom or a nitrogen atom, and Q ¹ and Q ² are the same or different. Often a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an allyloxy group, a siloxy group or a halogen atom, and Y is -O
-, - S -, - NR 52 -, - PR 52 - (R 52 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl or halogenated aryl.) Electron donor ligand represented by And Me is a transition metal and u is 0 or 1.

Preferred are the transition metal compounds represented by the general formulas (23), (24) and (25), specifically, bis (methylcyclopentadienyl) zirconium dichloride and bis (n-propylcyclohexane). (Pentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-
Butylcyclopentadienyl) zirconium dimethyl,
Ethylene bis (indenyl) zirconium dichloride,
Dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) titanium dibenzyl and the like can be exemplified. These transition metal compounds may be used alone or in combination.
More than one species can be used in combination.

The catalyst system of the present invention is formed by bringing the chromium compound (a-1), the carrier (a-2), the aluminoxane (a-3) and the transition metal compound (a-4) into contact with each other. You.

When the chromium compound (a-1) is changed to chromium oxide by firing in the presence of oxygen, the chromium compound (a-1) is first supported on a carrier (a-2), After being converted to chromium oxide by calcination, it is preferable to carry an aluminoxane (a-3) to obtain a solid catalyst component, and to bring the solid catalyst component into contact with the transition metal compound (a-4). If the chromium compound and the aluminoxane are supported on a carrier and calcined in the presence of oxygen, the effects of the present invention cannot be obtained.

As a method of supporting the chromium compound (a-1) on the carrier, a method of impregnating and supporting the chromium compound in an aqueous system or a hydrocarbon solvent such as pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene is preferably used. Can be The supporting temperature is generally 100 ° C or lower, preferably 0 to 40 ° C. The calcination in the presence of oxygen is performed at 300 to 1000 ° C. for 1 to 48 hours using a dry gas. Preferably, it is carried out in a state fluidized by a dry gas containing oxygen after removing the solvent.

The method for supporting the aluminoxane (a-3) is as follows: isobutane, pentane, hexane, heptane,
After suspending a carrier (a-2) supporting a chromium compound (a-1) converted to chromium oxide by baking in the presence of oxygen, in an inert hydrocarbon solvent such as cyclohexane, decane, benzene, and toluene. And the above-mentioned inert hydrocarbon solution of aluminoxane (a-3). Contact temperature is 0-1
20 ° C, preferably 10 to 100 ° C, contact time is 1 minute to
For 10 hours, preferably 1 minute to 5 hours, the amount of the solvent per 1 g of the carrier is 5 to 800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst component.

When the chromium compound (a-1) is used without firing in the presence of oxygen, the order of loading the chromium compound (a-1) and the aluminoxane (a-3) on the carrier (a-2) is arbitrary. It is.

The method of supporting the chromium compound (a-1) and the aluminoxane (a-3) is carried out by first using a carrier (a) in an inert hydrocarbon solvent such as isobutane, pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene. -
After suspending 2), the above-mentioned inert hydrocarbon solution of the chromium compound (a-1) and the aluminoxane (a-3) is brought into contact. The contact temperature is 0 to 120 ° C, preferably 10 to 100
° C, the contact time is 1 minute to 10 hours, preferably 1 minute to 5 hours, and the amount of the solvent per 1 g of the carrier (a-2) is 5 to 800 m.
l. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst component. Transition metal compound (a-
4) may be supported on the carrier (a-2) simultaneously with the chromium compound (a-1) and the aluminoxane (a-3), or may be brought into contact with the obtained solid catalyst component.

The ratio of the chromium compound (a-1), the carrier (a-2), the aluminoxane (a-3) and the transition metal compound (a-4) can be determined by changing the chromium compound (a-1) in the presence of oxygen. In the case of changing to chromium oxide by calcination in the step (a), and also in the case of not performing the calcination in the presence of oxygen, the carrier (a-2) 1
The content of chromium atoms in the chromium compound (a-1) is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, and the amount of aluminoxane ( a-3) a chromium compound (a-1) in which 1 to 600 mol, preferably 5 to 400 mol, of aluminum atoms are contained;
Transition metal compound (a-4) per mole of chromium atom
Is from 0.01 mmol to 10 mol, preferably from 0.1 mmol to
5 moles.

In the present invention, an organometallic compound can be used together with the above-mentioned catalyst. In this case, it is effective in improving the polymerization activity and preventing the polymer from adhering to the reactor wall. The organometallic compound that can be used is an organometallic compound of a Group 1, 2 or 3 element of the periodic table, and preferably an organometallic compound in which the metal is lithium, magnesium or aluminum. Specifically, n-butyl lithium, n-
Butylethylmagnesium, triethylaluminum,
Tri-n-butylaluminum, triisobutylaluminum and the like. These organometallic compounds can be used alone or in combination of two or more.
The amount of the organometallic compound is such that the total amount of metal atoms in the organometallic compound is usually 1 to 2000 mol, preferably 1 to 1500 mol, per 1 mol of the metal atom in the transition metal compound (a-4). Used in

Ethylene (co) polymer used in the present invention
(A) can be polymerized by a liquid phase polymerization method such as slurry polymerization or solution polymerization or a gas phase polymerization method. The liquid phase polymerization method is usually carried out in a hydrocarbon solvent, and as the hydrocarbon solvent, propane, butane, isobutane, hexane, cyclohexane, heptane, benzene, toluene,
A single or a mixture of inert hydrocarbon solvents such as xylene is used. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. The polymerization temperature is generally from 0 to 3
00 ° C., and practically 20 to 200 ° C. The polymerization pressure is normal pressure to 100 kg / cm ² , preferably 2 to 6 kg / cm ² .
It is 0 kg / cm ² . The molecular weight of the obtained polymer can be adjusted by controlling the polymerization temperature or by allowing hydrogen or the like to coexist in the polymerization reactor. Further, the molecular weight distribution of the obtained polymer can be controlled by controlling the amount of the catalyst component. In addition, if necessary, propylene,
Α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene alone or 2
More than one kind can be introduced into a polymerization reactor to copolymerize. The content of α-olefin in the obtained ethylene polymer is preferably at most 20 mol%, particularly preferably at most 15 mol%.

Ethylene (co) polymer (A) in the present invention
Is obtained by blending the following ethylene (co) polymer (A1) with the following ethylene (co) polymer (A2) in addition to polymerizing using a catalyst consisting of the components (a-1) to (a-4). Can also be obtained.

The ethylene (co) polymer (A1) is obtained by a catalyst system comprising a transition metal compound belonging to Groups 4 to 6 of the Periodic Table having a group having a conjugated π electron as a ligand.
It is an ethylene (co) polymer having an FR of 0.001 to 100 g / 10 minutes and is composed of a homopolymer of ethylene or a copolymer of ethylene and another α-olefin. Examples of other α-olefins include unsaturated hydrocarbons having 3 to 15 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, vinylcyclohexene, and styrene. Can be. Among such α-olefins, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene are particularly preferred. The content of the α-olefin is 20 mol%, preferably 15 mol%.

As the transition metal compounds of Groups 4 to 6 of the periodic table having a group having a conjugated π electron as a ligand, those described above can be used. These may be used alone or in combination of two or more. Can be. Other catalyst components in this catalyst system include aluminoxane. If necessary, the above-mentioned transition metal compound and / or aluminoxane can be supported on a carrier. As the aluminoxane and the carrier, those similar to the above can be used. Preferably, the aluminoxane is used by being supported on a carrier. The amount of aluminoxane supported on the carrier is preferably in the range of 5 × 10 ^{−4 to} 0.05 g atom, and more preferably 5 × 10 ⁻³ to 0.
Preferably it is in the range of 01 gram atoms.

At the time of polymerization, an organometallic compound can be further used. As the organometallic compound, those described above can be used, and the used amount thereof is 0.05 to 5 mol / liter,
Preferably it is 0.1-1 mol / l.

The contact between the transition metal compound and the aluminoxane may be carried out in the presence or absence of a monomer before the polymerization, or may be introduced into the polymerization system without contact in advance. As the polymerization method, any of solution polymerization, slurry polymerization, and gas phase polymerization is possible, and preferably, slurry polymerization or gas phase polymerization is used. Also, multi-stage polymerization is possible. The amount of the catalyst used is 10 ⁻⁸ to 10 ⁻² mol / L in terms of the concentration of the transition metal compound in the polymerization reaction system. Although the olefin pressure of the reaction system can be used in a wide range, it is preferably in the range of normal pressure to 50 kg / cm ³ . The polymerization temperature can be used in a wide range, and is in a range of -30 to 200C, preferably in a range of 0 to 120C. The molecular weight can be adjusted by known means, for example, by selecting a polymerization temperature or introducing hydrogen.

The ethylene (co) polymer (A2) has an MFR obtained from a chromium-based catalyst of 0.001 to 100 g / 10
Minute ethylene (co) polymer, comprising a homopolymer of ethylene or a copolymer of ethylene and another α-olefin. Other α-olefins may have 3 to 1 carbon atoms.
And 8 unsaturated hydrocarbons such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, vinylcyclohexene and styrene. Among such α-olefins,
Particularly, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene are preferred. The content of α-olefin is 20 mol% or less.

The chromium-based catalyst can be prepared using the chromium compound described above. When the chromium compound is used without being calcined, a catalyst comprising a chromium compound and optionally an aluminoxane supported on a carrier is desirable. A catalyst that comes into contact is desirable. As the carrier and the aluminoxane, those described above can be used.

As a method for obtaining a solid catalyst component by supporting a chromium compound on a carrier, the carrier is previously suspended in an inert hydrocarbon such as pentane, hexane, heptane, cyclohexane, decane, benzene or toluene, and then suspended in chromium. There is a method in which the above-mentioned inert hydrocarbon solution of the compound is added to carry out a supporting reaction and the solvent is removed by vacuuming, or a method in which the solvent is separated by filtration after the reaction. The amount of the chromium compound supported on the carrier is preferably such that the chromium atoms are 0.1 to 0.2 wt% relative to the carrier. Reaction temperature is -78 ° C
To the boiling point of the solvent, preferably 0 to 60 ° C, and the reaction time is 10 minutes to 24 hours, preferably 30 minutes to 5 hours.

Using the chromium-based catalyst, ethylene was (co)
As a polymerization method, a liquid phase polymerization method such as slurry polymerization or solution polymerization, or a gas phase polymerization method can be used. Liquid phase polymerization is usually carried out in a hydrocarbon solvent,
As hydrocarbon solvents, butane, isobutane, hexane,
Inert hydrocarbons such as cyclohexane, heptane, benzene and toluene are used. The polymerization temperature is generally 0
-300 ° C, and practically 20-200 ° C.
In addition, hydrogen or the like can coexist in the polymerization system for controlling the molecular weight.

In the present invention, the ethylene (co) polymer (A)
Is obtained by blending the component (A1) and the component (A2), the composition ratio of the components (A) to (III), preferably (I) to (V), and more preferably (I) to (I) (V
There is no particular limitation as long as it satisfies I), but specifically, it is selected within the range of 1 to 99% by weight and 99 to 1% by weight, respectively. The blending method may be performed by kneading the component (A1) and the component (A2) by a known method. Melt blending.

The above ethylene (co) polymer (A) has processability,
It has excellent electrical insulation properties and is used as a resin composition component for electrical insulation materials of the present invention. In the present invention, a resin composition for an electrical insulating material can be prepared by blending another olefin polymer (B). The olefin polymer (B) that can be used is a polyolefin different from the component (A), for example, polyethylene, polypropylene, polybutene, polypentene, poly-4-methyl-1-pentene, ethylene-propylene copolymer rubber (EPR) And the like. Among these, an ethylene (co) polymer obtained by high-pressure radical polymerization, a high-medium density polyethylene and a linear low-density polyethylene are particularly preferable.

An ethylene (co) polymer obtained by high-pressure radical polymerization refers to a density of 0.91 to 0.94 g /
cm ^3, MFR0.01~100g / 10 min ethylene (co)
A polymer, ethylene homopolymer, ethylene / vinyl ester copolymer, ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / unsaturated dicarboxylic acid (or anhydride) copolymer, ethylene • α, β-unsaturated carboxylic acid ester / unsaturated dicarboxylic acid (or anhydride) copolymer.

The density by the high-pressure radical polymerization method of 0.91 to
The 0.94 g / cm ³ ethylene homopolymer is a low-density polyethylene obtained by a known high-pressure method.

The above-mentioned ethylene / vinyl ester copolymer is mainly composed of ethylene produced by a high pressure radical polymerization method, and is mainly composed of vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, It is a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Preferred among these are ethylene-vinyl acetate copolymers, particularly ethylene 50 to 99.5% by weight, vinyl acetate 0.5 to 50% by weight.
Is preferred.

The above-mentioned ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / unsaturated dicarboxylic acid (or anhydride) copolymer, and ethylene / α, β-
As the unsaturated carboxylic acid ester / unsaturated dicarboxylic acid (or anhydride) copolymer, ethylene / methyl (meth) acrylate copolymer produced by a high-pressure radical polymerization method, ethylene / ethyl (meth) acrylate Copolymers, ethylene / methyl (meth) acrylate / maleic anhydride copolymer, ethylene / ethyl (meth) acrylate / maleic anhydride copolymer, ethylene / maleic anhydride copolymer, etc. . Among these, ethylene is preferably 50 to 99.5% by weight, (meth) acrylate 0.5
It is an ethylene / (meth) acrylate copolymer comprising up to 50% by weight.

The high-medium density polyethylene and the linear low-density polyethylene are ethylene homopolymers or ethylene / α-olefin copolymers having a density of 0.86 to 0.97 g / cm ³ , and are Ziegler type, Phillips type or Kaminski type. An ethylene homopolymer and a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms obtained by a high, medium, low pressure method and other known methods using a system catalyst. Specific α-olefins used for polymerization include propylene, 1-butene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-dodecene, and the like. Preferred among these are 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene,
Particularly preferred is 1-butene. The α-olefin content in the ethylene copolymer is preferably 0.5 to 40 mol%.

When another olefin polymer (B) is used, its compounding amount is 98% by weight or less based on the total amount of component (A) and component (B) (2% by weight of component (A)). Above).
When it is desired to maintain the excellent electrical properties of the ethylene (co) polymer (A), the content of the component (A) should be 70% by weight or more (the content of the component (B) should be 30% or more).
(% By weight or less), and if it is desired to utilize the processability and economical efficiency of the other olefin-based polymer (B), the component (B) should be 30 to 98% by weight (the component (A) should be 70 to 2
% By weight). When crosslinking is performed as described below, the ethylene (co) polymer (A) may be used in an amount of 30 to 1
It is desirable to mix 0% by weight and 70 to 90% by weight of another olefin polymer (B).

The component (A) and the component (B) can be blended by a blending method in which both components are kneaded by a known method. Specifically, as in the above, it can be carried out by a method of melt blending using a single screw extruder, a twin screw extruder, a Brabender, a Banbury mixer, a kneader blender or the like.

The above-mentioned resin composition can be used as it is as an electrical insulating material. However, in order to further improve heat resistance and mechanical strength, the resin composition can be crosslinked and used. The crosslinking method is not particularly limited, and the crosslinking can be performed by a radical generator such as an organic peroxide, electron beam crosslinking, silane crosslinking, or the like. Preference is given to cross-linking using a radical generator such as an organic peroxide because it is economically inexpensive.

Examples of usable radical generators include benzoyl peroxide, lauryl peroxide, dicumyl peroxide, t-butyl hydroperoxide, α, α-bis (t-butylperoxydiisopropyl) benzene, di-t- Butyl peroxide, 2,5
Peroxides such as -di- (t-butylperoxy) hexane, 2,5-di- (t-butylperoxy) hexyne, azobisisobutyronitrile, and 2,3-dimethyl-2,3-
Diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-di (p-methylphenyl) butane, 2,3-diethyl-2,3-di (bromophenyl) Butane and the like.

Among these radical generators, dicumyl peroxide, 2,5-di- (t-butylperoxy)
Hexane, 2,5-di- (t-butylperoxy) hexyne and the like are preferred. The radical generator is used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total composition.

The resin composition for an electrical insulating material of the present invention includes:
If necessary, inorganic fillers, organic fillers, antioxidants, lubricants, antistatic agents, antiblocking agents, organic or inorganic pigments, ultraviolet inhibitors, light stabilizers, dispersants, copper damage inhibitors, neutralizing agents , A plasticizer, a nucleating agent, and the like.

The resin composition for an electrical insulating material of the present invention can be used for insulation of electric wires / cables, capacitors, insulation of high voltage parts such as X-ray generators, and power distribution cords. The electric wire / cable of the present invention is an electric wire / cable composed of the resin composition for an electrical insulating material or an insulating layer obtained by crosslinking the resin composition.

A specific example of the electric wire / cable is an electric cable in which at least a conductor is coated with the resin composition for electric insulation of the present invention to constitute an insulating layer.
The conductor portion can be a collective wire, a semiconductive layer can be provided between the conductor and the insulating layer, or a flame-retardant resin layer can be formed outside the insulating layer. Further, a wire made of a copper collective wire is coated with a resin composition obtained by adding conductive carbon or metal powder to form a semiconductive layer, and an insulating layer is formed by coating the resin composition for electrical insulation of the present invention thereon. Further, a metal sheet is coated thereon or a semiconductive layer is provided thereon, and a cable formed by coating a flame-retardant resin or a rat repellent resin on the outermost side, and a resin composition obtained by adding carbon or metal powder to a single copper wire. To form an insulating layer by coating the resin composition for electrical insulation of the present invention thereon, further providing a metal film layer thereon, and combining several to several tens of such copper wire coatings. Examples include a cable coated with a flame-retardant resin or a mouse repellent resin on the outside, and the resin composition for electrical insulation of the present invention is particularly effective for high-voltage electricity, and has a large capacity cable and a DC cable. It is preferably used as

[0108]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The measurement of physical properties and the like in the following examples were performed by the following methods.

Number of long-chain branches : long-chain branches correspond to nuclear magnetic resonance apparatus ¹³
It is a C6 or higher branch measured by C-NMR, and a nuclear magnetic resonance apparatus is EX-400 type ¹³ C-NMR manufactured by JEOL Ltd.
The temperature was measured at 120 ° C. and the solvent was 1,2,4-trichlorobenzene.

Pretreatment of polymer for measurement of physical properties : Using a plastograph manufactured by Toyo Seiki Co., Ltd., 0.2% by weight of B225 manufactured by Ciba Geigy was added as an additive, and 190% under nitrogen.
And kneaded for 7 minutes.

HLMFR swell ratio (%) : TAKARA CORPORATION
From a capillary nozzle (diameter D ₀ = 1.0 mm, length L = 10.0 mm, L / D = 10, inflow angle = 90 °) using a THERMISTOR X416 manufactured under the conditions of a load of 21.6 kg and 190 ° C. When the value obtained by measuring the diameter of the obtained strand with a micrometer was D (mm), it was determined by the following equation.

HLMFR swell ratio (%) = (D−D ₀ ) × 100 / D ₀ (5)

HLMFR : Condition 7 of JIS-K7210
And the measured value at a temperature of 190 ° C. and a load of 21.6 kg was shown as HLMFR.

MFR : Measured at 190 ° C. under a load of 2.16 kg in accordance with JIS-K7210 condition 4.

Frequency dependence of dynamic viscosity : RMS-800 manufactured by Rheometrics Co., Ltd., using a parallel plate having a diameter of 2.5 mm, at a set temperature of 190 ° C. and a frequency ω of 10 ⁻² r.
complex viscosity η in the range from ad / sec to 10 ² rad / sec
^* (ω) is measured, and the frequency ω is 10 ² rad / sec to 1
0 ⁴ rad / sec complex viscosity of η ^* (ω) is, Toyo Seiki Co., Ltd.
Orifice diameter of nozzle using Capillograph IC
It was measured under the conditions of 0.76 mm, a length of 25.40 mm, and a temperature of 190 ° C. by the method described in JIS-K7199, and the presence or absence of an inflection point in the viscosity curve was examined.

Melt tension (MT) : Capillograph IC manufactured by Toyo Seiki Co., Ltd., nozzle orifice diameter 2.095 m
m, length 8mm, temperature 190 ° C, extrusion speed 15mm /
And a take-up speed of 6.5 mm / min.

Density : Measured according to JIS-K7112.

Mz / Mw and GDI : • Preparation of calibration curve 1,2,4-trichlorobenzene 1 containing 0.1% BHT
In 0 ml, add 2 mg of each of three kinds of standard polystyrene samples (manufactured by Showa Denko KK) having different molecular weights, dissolve at room temperature and in a dark place for 1 hour, and then elute the peak top by GPC measurement under the following conditions. The time was measured. This measurement is repeated, and a total of 12 points (molecular weight: 580 to 8,500,000)
A calibration curve was prepared by the cubic approximation based on the molecular weight of and the elution time of the peak top. -Measurement of sample 1,2,4-trichlorobenzene 5 containing 0.1% BHT
2 mg of the sample was placed in each ml, and dissolved while stirring at 160 ° C. for 2 hours. Thereafter, the measurement was performed in the same manner as described above. Mz / Mw and GDI were calculated from the obtained chromatogram and calibration curve. Other measurement conditions are as follows.

GPC measurement conditions: Apparatus: 150C manufactured by Waters, mobile phase: 1,2,4-trichlorobenzene (BHT 0.1
%), Column: 1 Shodex HT-G made by Showa Denko KK + Shodex HT
-806M 2 tubes, measurement temperature: 140 ° C, sample injection volume: 0.5 ml, sample injection waiting time in the device: 30 minutes (5 minutes for polystyrene), flow rate: 1.0 ml / minute.

Preparation of Sample for Volume Resistance Measurement : The blend was prepared by kneading with a plast mill at 160 ° C. for 5 minutes. It was formed into a sheet having a thickness of 0.3 mm by hot pressing.
The sample was formed by sandwiching the sample between aluminum sheets under the following conditions. 1) Preheat sample at 140 ° C for 5 minutes. 2) Pressing at 140 ° C. and 100 kg / cm ² for 5 minutes. 3) Cool under pressure from 140 ° C to 30 ° C in 5 minutes.

Volume resistance measurement : FIG. 2A is a plan view, FIG.
The measurement was performed using an electrode system whose side sectional view is shown in (b). The electrode material of the main electrode 21, the guard electrode 22, and the high-voltage electrode 24 used a stainless steel plate, and the surface in contact with the sample was polished to a mirror state by a buff polisher. The measurement was performed at room temperature and at 90 ° C. in a nitrogen atmosphere. The measurement is
Sample 23 was placed in an electrode system, and the upper and lower electrodes were short-circuited for 5 minutes to remove charges charged on the surface of sample 23, and then performed. 9
The sample measured at 0 ° C. was short-circuited for 7 minutes so that the temperature in the sample was uniformly 90 ° C. The applied voltage is DC 3300
V. As a measuring device, a vibration capacitance type ammeter (TR8411 manufactured by Advantest) was used. The cable connecting the measuring instrument and the electrodes was a pipe cable to remove extraneous noise. In this measurement system, 3 × 10 ¹⁷ Ω at room temperature, 90 ° C.
Can stably measure up to 3 × 10 ¹⁶ Ω. The thickness of the sample 23 was about 0.3 mm, and each sample was measured to two decimal places or less and used. The polar electrode area is 19.6 cm ² . According to the investigation of the current-time characteristics, it is found that the current can be measured stably after the voltage is applied because the absorption current does not decrease.
After 10 minutes, the current value 10 minutes after voltage application was taken as the measured value. If the current is not stable after 10 minutes,
The measurement was waited for about 2 minutes to stabilize, but any measurement longer than that was removed from the measurement. The volume resistance was determined based on the current value obtained from the measurement. The measurement was performed 10 times, and the average value was used as data.

Water tree measurement : 10 kV, 10 k at room temperature for 30 days using a water tree apparatus whose schematic sectional view is shown in FIG.
A voltage of Hz was applied, and after the application was completed, the water tree was stained, observed with a microscope, and evaluated according to the following criteria. Notable: ×, Notable: △, Notable: ○.

The workability as an electric wire / cable material was evaluated by evaluating the electric wire manufacturability by high-speed coating and the manufacturability of a power cable having an inner / outer semiconductive layer. High-speed electric wire coating test : Coating on a copper wire and evaluation of formability.
The coating conditions are: core wire 0.9mm, die diameter 2.5mm, nipple diameter 0.95mm, die / nipple clearance 5.3mm,
The finished outer diameter is 2.45 mm and the take-off speed is 100 m / min. After the molding, the wire was visually observed, and the wire covering property was evaluated according to the following criteria. Those with a rough surface and those that cannot be molded: ×, those that are insignificant enough for practical use: ○.

Production of power cable : FIG.
Was manufactured, and cable manufacturability was evaluated according to the following criteria. No molding due to increased extrusion pressure or knitting during molding: ×, knitting, good cable without irregularities at the interface between insulator and semiconductive layer: ○.

Preparation of Solid Catalyst Component (1) A 20-liter autoclave purged with nitrogen was placed at 400 ° C.
1.14 kg of silica (grade CARiACT P-3) manufactured by Fuji Silysia Co., Ltd., which was calcined in nitrogen for 8 hours, and 8 liters of hexane were added to form a slurry. In this slurry,
0.59 l of a 58 g / l tris (bistrimethylsilylamide) chromium (III) hexane solution was added so that the carried amount of chromium atoms became 0.3 wt%,
Stirred at C for 1 hour. To this slurry, 162 g / liter of a toluene solution of methylaluminoxane manufactured by Tosoh Akzo Co., Ltd. was added in an amount of 1.9 liters such that the molar ratio of aluminum atoms to chromium atoms in methylaluminoxane was 80, and the mixture was stirred at 40 ° C for 2 hours. The solvent was removed under vacuum to obtain 1.5 kg (1) of a solid catalyst component.

Preparation of Solid Catalyst Component (2) A 20-liter autoclave purged with nitrogen was placed at 400 ° C.
1.14 kg of silica (grade CARiACT P-3) manufactured by Fuji Silysia Co., Ltd., which was calcined in nitrogen for 8 hours, and 8 liters of hexane were added to form a slurry. To this slurry, 1.9 l of a toluene solution of 162 g / l of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) was added.
Stirred for hours. The solvent was removed under vacuum to obtain 1.4 kg of a solid catalyst component (2).

Example 1 Polymerization of Sample A-1 A 290-liter loop reactor filled with a polymerization solution was charged with 100-liter / h of isobutane, 7 g / h of a solid catalyst component (1), and a transition metal compound bis (normal butyl). Cyclopentadienyl) zirconium dichloride (BC
Z) Continuous polymerization was carried out at 0.1 g / h (feed as a hexane solution), ethylene 18.0 kg / cm ² · h, hydrogen amount 0.22 g / h, and polymerization temperature of 80 ° C. Further, n-butylethylmagnesium (n-BuEtMg) was used as the organometallic compound, and the concentration was 0.6 mmol / l. The contents are
The polymer was continuously recovered by continuously discharging and releasing the content gas. The average residence time of this polymer is
2.1h, polymer recovery 16.0kg / h, MFR 2.5g / 10
Min and a density of 0.941 g / cm ³ .

Example 2 : Polymerization of sample A-2 n-butylethylmagnesium (n-BuEtMg) as an organometallic compound, solid catalyst (1), and bis (normalbutylcyclopentadienyl) zirconium dichloride (as a transition metal compound) BCZ) and 1-hexene as a comonomer was polymerized in the same manner as in Sample A-1.

Example 3 Blend 1 kg of a chromium-based homopolymer (sample A-3a) obtained by polymerizing with solid catalyst component (1) and n-butylethylmagnesium as an organometallic compound without using a transition metal compound
And a solid catalyst component (2), a transition metal compound bis (normalbutylcyclopentadienyl) zirconium dichloride (BCZ), n-butylethylmagnesium (n-BuEtMg) as an organometallic compound, and a comonomer as 1-hexene. The obtained Zr-based homopolymer (sample A-3)
b) 4 kg of 40 mmφ co-axial single screw extruder KTX manufactured by Nakatani
Using 37, the blending was performed under the conditions of a set temperature of 160 to 220 ° C, a screw rotation speed of 100 rpm, and a discharge rate of 5 kg / h.

Example 4 Polymerization of Sample A-4 An inner volume of 3.9 containing 140 kg of polyethylene seed polymer
The m ³ gas phase reactor was sufficiently purged with nitrogen and heated to 70 ° C. Then, ethylene was supplied at a rate of 30 kg / h, and the total pressure in the reactor was maintained at 21 kg / cm ² . Further, 6 g / h of the solid catalyst component (1) and 16 g of a hexane solution (0.8 g / liter) of bis (normal butylcyclopentadienyl) zirconium dichloride (BCZ) were added.
3 ml / h, hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 0.3 / 1, total concentration 0.5 mol / l)
Was continuously supplied at a rate of 240 ml / h to perform gas phase polymerization. At this time, the residence time of the polymer was 5 hours, and the amount of produced polymer was 30 kg / h. MFR of polymer
Is 2.6 g / 10 min, HLMFR is 49.1 g / 10 min, and density is 0.9.
It was 42 g / cm ³ .

Comparative Example 1 : Polymerization of Sample B-1 A transition metal compound was not used, and n-butylethylmagnesium (n-BuEtMg) was used as an organometallic compound. Polymerization was performed.

Comparative Example 2 : Polymerization of sample B-2 Solid catalyst component (2), transition metal compound bis (normal butyl cyclopentadienyl) zirconium dichloride (BCZ), n-butylethyl magnesium (n- Using BuEtMg), polymerization was carried out in the same manner as in Sample A-1.

Comparative Examples 3 to 5 : Comparative Example 3 is a commercially available metallocene LLDPE (AFFINITY PL1880), and Comparative Example 4 is
LLDPE (J-Lex LL AR3410, Japan Polyolefin Co., Ltd.) using a Ziegler catalyst, and Comparative Example 5 is a high-pressure radical method LDPE (J-Lex LD W2000, Japan Polyolefin Co., Ltd.).

HLMFR (190 ° C., 21.6 kg load), HLMFR of polymers of Examples 1 to 7 and Comparative Examples 1 to 5
Swell ratio, MFR (190 ° C, 2.16 kg load), MT,
Existence of inflection point of viscosity curve, number of long chain branches (LCB number) of high molecular weight component, Mz / Mw, Mz / of low molecular weight distribution component
Mw, density, volume resistance at room temperature and 90 ° C. (electrical activation energy), water tree resistance, wire covering property, and cable manufacturability were measured and evaluated. The results are summarized in Tables 1 and 2.

[0134]

[0135]

Examples 1 to 4 are the results of Samples A-1 to A-4, respectively. Comparative Examples 1 to 5 correspond to Sample B-1.
To the result of Sample B-5. Examples 5 and 6
Is the result of the Bunred product of Sample A-1 and Sample B-5, and the blend ratio is (Sample A-1) / (Sample B
-5) = 50/50, 10/90. Example 7
In the result of the blended product of Sample A-2 and Sample B-5, the blend ratio is 10/90. As is clear from Table 1,
Comparative Examples 1 and 2 have high volume resistance but are inferior in wire covering property and cable manufacturability, Comparative Examples 3 and 4 are inferior in wire covering property, cable manufacturability and volume resistance, and Comparative Example 5 has poor volume resistivity. . In contrast, ethylene
In Examples 1 to 4, which are the (co) polymer (A) alone, they are excellent in wire covering properties, cable manufacturability, volume resistance, and water tree resistance, and have a high pressure with ethylene (co) polymer (A). Also in Examples 5 to 7 which are blends of polyethylene (B) by a method radical polymerization, the electric wire covering property and the cable productivity are good. Also, it has a sufficiently high volume resistance and excellent water tree resistance.

[0137]

According to the present invention, there is provided a resin composition for an electrically insulating material comprising an ethylene (co) polymer having a wide molecular weight distribution, excellent workability, and excellent electrical insulation.
The composition of the present invention can be widely used as an insulating material in various electric appliances, transportation equipment, plants, factories, etc., or as an electric wire / cable or DC cable.

[Brief description of the drawings]

FIG. 1: Molecular weight parameters defining the composition of the invention
FIG. 4 is an explanatory diagram of a Gaussian distribution approximate curve for calculating (GDI).

FIG. 2 is a plan view (a) and a side sectional view (b) of an electrode system for measuring volume resistance used in an example of the present invention.

FIG. 3 is an apparatus for measuring a water tree used in an embodiment of the present invention.

FIG. 4 is a sectional view of a cable used in the embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 21 Main electrode 22 Guard electrode 23 Sample 24 High voltage electrode 31 Water tree measurement sample 32 Conductive plate 33 Water 34 Ground electrode 35 Container whose bottom is a sample 36 Applied electrode 41 Conductive member composed of a collection line of conductive metal 42 Internal semiconductive Layer 43 Insulating resin composition 44 External semiconductive layer 45 Aluminum foil 46 Protective material (polyolefin containing inorganic flame retardant)

Claims (6)

[Claims] 1. A resin composition for an electrical insulating material comprising an ethylene (co) polymer (A) satisfying the following conditions (I) to (III): (I) 50 parts by weight of butylcellosolve and paraxylene. A component insoluble at 126 ° C. in a solvent mixed at a volume fraction of 50,
Contains 0.2 long chain branches (C6 or more branches) / 10,000 C or more; (II) MFR is 0.001 to 100 g / 10 min; (III) Electrical activation energy is 0.4 eV or less. 2. The resin composition for an electrical insulating material according to claim 1, wherein the ethylene (co) polymer (A) further satisfies the following conditions (IV) and (V): (IV) complex viscosity In the frequency ω dependence of the rate η ^* (ω),
At least one inflection point exists when ω is between 10 ⁻² rad / sec and 10 ⁴ rad / sec; (V) At least one of the following equations (1) and (2) is satisfied. HLMFR swell ratio (%)> 50 + 25 × log (HLMFR) (1) MT (g)> 4.8−12.1 × log (MFR) (2) 3. An ethylene (co) polymer (A) further comprising (V
I) Gel permeation chromatography (GPC)
The electrical insulation according to claim 1 or 2, wherein Mz / Mw obtained by measurement is 6.0 or more, and a molecular weight distribution parameter (GDI) obtained by approximating a specific region of the molecular weight distribution curve by Gaussian distribution is 5.0 or less. Resin composition for materials. 4. The ethylene (co) polymer (A) has a chromium compound (a-1), a carrier (a-2), an aluminoxane (a-3) and a group having a conjugated π electron as a ligand. 4. The resin composition for an electrical insulating material according to claim 1, which is obtained from a catalyst system comprising a transition metal compound (a-4). 5. The method according to claim 1, comprising 100 to 2% by weight of an ethylene (co) polymer (A) and 0 to 98% by weight of another olefin-based polymer (B). The resin composition for an electrical insulating material according to the above. 6. An electric wire or cable using the resin composition for an electrical insulating material according to claim 1 as an insulating material.