JPH10310667A - Resin composition for electrical insulation material, electrical insulation material and electric wire and cable insulated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for high-voltage cables, excellent in electrical insulation performances and processability by using an ethylene copolymer resin component having a specified amount of content insoluble in a butylcellosolve/p-xylene mixed solvent, having long-chain branches, having a specified MFR and a specified electrical activation energy and containing a specified amount of units derived from a carbonyl-containing monomer or the like. SOLUTION: The ethylene (co)polymer satisfies the following requirements (I) to (III), contains 5×10<-7> to 5×10<-3> mol, per g of the resin composition, of units derived from a carbonyl (derivative)containing monomer, a hydroxyl- containing monomer, an aromatic-ring-containing monomer, etc., or containing units derived from a compound having at least two ethylene bonds and having a specified number of ethylene bonds: (I) the number of long-chain branches insoluble in a bulylcellosolve/p-xylene 1/1 vol. mixed solvent at 120 deg.C is 0.2 pieces /10,000 C or above, (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.
The present invention relates to a resin composition for an electrical insulating material comprising a (co) polymer. More specifically, a resin composition having excellent electrical insulation properties such as volume resistance, space charge characteristics, and dielectric strength, or a resin composition which does not cause a decrease in electrical properties such as volume resistance, space charge properties, and dielectric strength even when crosslinked. And an electric wire or cable having an insulating layer composed of a resin composition or a cross-linked product thereof (in the present specification, an “electric wire or cable”
Cable ". ) And DC cables.

[0002]

2. Description of the Related Art Conventionally, insulating materials for electric wires and cables are basically required to have a high volume resistance and a high breakdown voltage, a small dielectric constant and a small dielectric loss tangent, and generally polyethylene is used. In addition, oil-filled insulating materials (OF) are used in large-capacity power transmission cables, etc., although OF has good insulation performance,
There is a disadvantage that oil leaks and oil needs to be constantly replenished. In recent years, a crosslinked polyethylene or the like, which is obtained by crosslinking a polyolefin such as polyethylene to increase heat resistance and strength, has been used.

[0003] One of the problems with high-voltage power cables is power loss during high-voltage transmission, and reducing this is an important issue. One means of reducing the power loss can be achieved by increasing the electrical characteristics of the insulating material, particularly the volume resistance. However, simply increasing the volume resistance at room temperature or at a constant temperature causes another problem.
For example, in the case of a power cable insulator, the temperature near the inner conductor is 90 ° C. due to Joule heat due to current, but the temperature near the outer conductor is high. Here, in conventional polyethylene, whose volume resistance decreases significantly with temperature rise, the volume resistance in the vicinity of the inner conductor through which the current flows significantly decreases, so that the electric field concentrates near the interface between the outer conductor and the insulator, causing dielectric breakdown. Strength decreases. This phenomenon is a serious problem particularly in DC power cables. Therefore, it is desired to reduce the temperature dependence of the volume resistance.

As a method for improving the high voltage characteristics of an insulating material, a method has been proposed in which maleic anhydride is grafted onto low-pressure polyethylene (for example, Japanese Patent Application Laid-Open No. 2-10610). However, the use of low-pressure polyethylene as a high-voltage cable insulator has a problem that its flexibility is inferior to conventional power cables.

[0005] Also, low-density polyethylene 100 parts by weight, specific gravity 0.91~0.94g / cm ³ of linear low density polyethylene made by blending 0.5 to 20 parts by weight insulators specific gravity 0.92 g / cm ³ is disclosed (Japanese Unexamined Patent Publication No. H5-266723). However, since the above composition has a large temperature dependency, the effect of improving the volume resistance near the internal conductor is not satisfactory.

[0006] Polyolefins such as polyethylene are
When used as an insulator for a cable, it is cross-linked to increase heat resistance and mechanical strength. Examples of the crosslinking method include an electron beam crosslinking method and a chemical crosslinking method such as a peroxide. However, the electron beam crosslinking method has a problem that the equipment becomes large-scale and the cost is high. Further, although the chemical crosslinking method is economically inexpensive, the crosslinking agent remains, and the residue causes problems such as a decrease in volume resistance, deterioration of space charge characteristics, and generation of water trees.

On the other hand, as a method for improving the electric insulation properties, a method has been proposed in which a polyolefin modified with maleic anhydride to introduce a hydrophilic group is introduced into polyethylene (Japanese Patent Publication No. 5-15007). Further, attempts have been made to improve the electrical insulation performance by introducing a double bond into the cross-linked polyolefin in advance to reduce the amount of the cross-linking agent (JP-A-4-11646). It does not fully satisfy both electrical insulation performance and heat resistance.

On the other hand, a technique has been proposed in which a carboxylic acid compound or an aromatic compound is mixed with a polyolefin for the purpose of improving the electrical insulation properties. For example, one that improves the impulse fracture strength by grafting polystyrene to polyolefin (Japanese Patent Publication No. 2-165506), one that improves the impulse fracture strength by blending polystyrene with polyethylene (Japanese Unexamined Patent Publication No. Sho 63 (1988)).
-301427), a polyolefin modified with maleic anhydride is blended with polyethylene to improve the insulation properties (Japanese Patent Laid-Open No. 62-100909), and a dielectric breakdown property is obtained by blending an aromatic carboxylic acid with the polyolefin. (JP-A-60-23904) have been proposed.

However, none of these methods has sufficiently improved both the volume resistance and the dielectric breakdown strength at practical levels. In addition, the electrical insulation performance after crosslinking is not sufficiently satisfactory.

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 a low electric activation energy and suitable for an electric insulating material can be obtained.
(JP-A-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.

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.

[0012]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition having a wide molecular weight distribution, excellent workability, and excellent electrical insulation properties such as volume resistance, space charge characteristics, and dielectric breakdown strength, or rich in crosslinkability. The present invention provides a resin composition having excellent electrical insulation performance such as volume resistance, space charge characteristics, and dielectric breakdown strength even after cross-linking, and an electric wire, a cable, and a DC cable having an insulating layer formed of the resin composition or the cross-linked product. is there.

[0013]

Under such circumstances, the present inventors have conducted intensive studies, and as a result, introduced a specific functional group-containing monomer and / or a unit derived from an ethylene bond into a specific ethylene (co) polymer. It has been found that the obtained resin composition has excellent suitability as an electrical insulating material, and the present invention has been completed.

That is, a first aspect of the present invention is the following (I)
To (III), preferably the conditions (I) to (V),
More preferably, in the resin component composed of the ethylene (co) polymer (A) satisfying all of the conditions (I) to (VI), the unit (M) derived from at least one monomer selected from the following M1 to M6 And when the concentration is based on M1 to M5, 5 × 10 ^{−7 to} 5 × 10 5 per 1 g of the resin composition
^The resin composition for an electrical insulating material is characterized by having a number of ethylene bonds of 0.8 or more per 1,000 carbon atoms of the resin component when ^-3 mol and M6 are used.

(I) A component insoluble at 126 ° C. in a solvent in which butyl cellosolve and para-xylene are mixed at a volume ratio of 50:50 has a long-chain branch (branch of C6 or more) of 0.2 / 10.
Contains 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.

M1: carbonyl group or carbonyl derivative-containing monomer; M2: hydroxyl group-containing monomer; M3: nitro group-containing monomer; M4: nitrile group-containing monomer; M5: aromatic ring-containing monomer; M6: two or more ethylene bonds Or a compound having the formula:

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 comprising from about 98% by weight.

A third aspect of the present invention is an electric insulating material obtained by crosslinking the resin composition. A fourth aspect of the present invention is an electric wire or cable using the electric insulating material as an insulating layer.

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 a long-chain branched (C6) component which is insoluble at 126 ° C. in a solvent in which (I) butyl cellosolve and para-xylene are mixed at a volume fraction of 50:50
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 50:50 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 (branch of C6 or more) 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 course of the transport phenomenon. The activation energy is the transition state from the original system to the production system. 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 electrical 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 for quantitatively describing the behavior of the molten state of the polymer, there are a method for obtaining linear viscoelasticity and a method for 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 in the range of 10 ⁻² rad / sec to 10 ⁴ rad / sec, the log η ^* (ω) is reduced 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).

[0032]

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.

[0034]

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 JLM
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).

[0037]

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.

[0042]

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

Mz / Mw can be obtained from the ratio of Mz and Mw thus obtained. 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).

[0045]

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.

It is necessary that Mz / Mw of the ethylene (co) polymer (A) in the present invention is not less than 6.0. 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 calcination 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.

[0052]

[0053]

[0054]

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

[0055]

[0056]

[0057]

[0058]

(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, aryl groups having 1 to 20 carbon atoms, alkyl groups,
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 used without firing in the presence of oxygen include the above-mentioned chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, and organic chromium compound. Preferably, a chromate ester, a chromamide compound,
Specific examples include bis (tert-butyl) chromate, bis (triphenylsilyl) chromate, and tris (bistrimethylsilylamide) chromium (III).

The support of the catalyst component (a-2) may be an oxide of an element of Groups 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 of 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 into 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).

[0066]

[0067]

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.

[0071]

[0072]

In the formula, R ⁴⁶ is a hydrocarbon group such as methyl, ethyl, propyl, n-butyl and isobutyl;
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 the 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)

[0079]

[0080]

[0081]

[0082]

In the above formula, Cp ² and Cp ³ may be the same or different, 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 transition metal compounds represented by the general formulas (23), (24) and (25). Specifically, bis (methylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclo) (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 above-mentioned chromium compound (a-1), carrier (a-2), aluminoxane (a-3) and transition metal compound (a-4) into contact. 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.

The method of supporting the chromium compound (a-1) on the carrier is preferably 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 or toluene. 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 in which the chromium compound (a-1) and the aluminoxane (a-3) are supported 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 previously setting the 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 proportions of the chromium compound (a-1), the carrier (a-2), the aluminoxane (a-3) and the transition metal compound (a-4) are 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 aforementioned 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%.

The 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 the 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 of 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, and toluene. 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 reaction is separated by filtration. 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 resin component of the present invention comprises the ethylene (co) polymer (A) as a main component, and at least (M) M1: a carbonyl group or carbonyl group derivative-containing monomer;
2: hydroxyl group-containing monomer, M3: nitro group-containing monomer, M4: nitrile group-containing monomer, M5: monomer unit derived from one of aromatic ring-containing monomers is 5 × 10 ^{−7 to} 5 × per 1 g of the resin component. 10 ^-3
Molar or M6: 0.1 per 1000 carbon atoms.
Either eight or more ethylene bonds must be present.

Specific examples of (M1) a monomer containing a carbonyl group and a carbonyl group derivative include unsaturated carboxylic acids derived from α, β-unsaturated carboxylic acids and α, β-unsaturated carboxylic acid esters. Examples include unsaturated carboxylic acid esters, vinyl ester monomers, unsaturated dicarboxylic anhydrides, and the like. Specific examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and acrylic acid-n.
-Butyl, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, monomethyl maleate, monoethyl maleate, diethyl maleate, Examples include unsaturated carboxylic esters such as fumaric acid monomethyl ester, glycidyl acrylate, and glycidyl methacrylate.

Specific examples of vinyl esters include vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate.
Of these, vinyl acetate is preferred.

Specific examples of unsaturated dicarboxylic anhydrides include maleic anhydride, itaconic anhydride, hymic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride, Maleic anhydride, dichloromaleic anhydride,
Fluoro maleic anhydride, difluoro maleic anhydride,
Bromomaleic anhydride, dibromomaleic anhydride and the like can be mentioned. Of these, maleic anhydride is particularly preferred.

Examples of other monomers include carbon monoxide,
Examples thereof include methyl vinyl ketone, isopropenyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, t-butyl vinyl ketone, isopropyl vinyl ketone, methyl propenyl ketone, methyl isopropenyl ketone, and cyclohexyl vinyl ketone.

(M2) Examples of the hydroxyl group-containing monomer include vinyl alcohol and 1-hydroxypropyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like can be mentioned.

(M3) As the nitro group-containing monomer,
2,4-dinitrophenyl acrylate, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, p
-Nitrophenyl methacrylate, m-nitrophenyl methacrylate, 2,4-dinitrophenyl methacrylate, 2,4,6-trinitrophenyl methacrylate and the like.

(M4) As the nitrile group-containing monomer,
Acrylonitrile, methacrylonitrile, α-methoxyacrylonitrile, vinylidene cyanide, cinnamonitrile, crotononitrile, α-phenylcrotononitrile, fumaronitrile, allylacetonitrile, 2-butenenitrile, 3-butenenitrile and the like can be mentioned.

(M5) The aromatic ring-containing monomer is a compound having a monocyclic or polycyclic aromatic ring and having an ethylene bond. The aromatic ring-containing monomer is preferably an aromatic compound having 1 to 3 rings, specifically, styrene or a derivative thereof, allylbenzene, allylbiphenyl, methylstyrene, allyl benzoate, vinylnaphthalene, 4-phenyl -1-butene, benzyl methacrylate, 1,1-diphenylethylene, 1
-Phenyl-1-tolylethylene, 1-phenyl-1-
Styrylethane, 1-tolyl-1-styrylethane,
2,4-diphenyl-1-butene, 2,4-diphenyl-1-pentene, 2,4-diphenyl-4-methyl-1
-Pentene and the like. Among these, styrene is preferred because of its good electrical performance and economical.

The amount of the monomers M1 to M5 is in the range of 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per 1 g of the resin composition. Is essential. In particular, if the amount of the M1-M4 functional group-containing monomer such as maleic anhydride is less than 5 × 10 ^-7 mol, the effect of improving the volume resistance is not exhibited, and the amount of the M5 aromatic ring-containing monomer is less than 5 × 10 ^-7 mol. In this case, the effect of improving the dielectric breakdown strength is not exhibited. On the other hand, if it exceeds 5 × 10 ⁻³ mol, the moldability deteriorates and the volume resistance decreases.

The method for introducing the monomers M1 to M5 into the resin component can be specifically carried out by the method shown in the following (C) or (D). (C): Component containing (C1), or (C2) to (C3)
Is mixed with the resin component containing the ethylene (co) polymer (A). (C1) a graft copolymer obtained by modifying the ethylene (co) polymer (A) with at least one monomer of M1 to M4, (C2)
An olefin polymer (B) different from the component (A) is
A graft copolymer modified with at least one monomer of 4, a random copolymer of (C3) ethylene or ethylene and other olefins, and at least one monomer of M1 to M4;

(D): at least one component selected from (D5) to (D6) or at least one component selected from (D1) to (D4) is ethylene (co) polyethylene It is blended with the resin component containing the union (A). (D1) a (co) polymer of an aromatic ring-containing monomer of M5,
2) a random copolymer of ethylene or ethylene and another olefin, at least one monomer of M1 to M4, and a monomer of an aromatic ring-containing monomer of M5; (D3) an ethylene-based polymer containing an aromatic ring; Merge M1
A graft copolymer modified with at least one monomer of M4 to M4, a random copolymer of (D4) ethylene or ethylene and another olefin, and at least one monomer of M1 to M4 containing an aromatic ring of M5 Graft copolymer modified with monomer, (D5) ethylene (co) polymer
(A) a graft copolymer obtained by modifying the aromatic ring-containing monomer of M5; (D6) an ethylene (co) polymer (A) of M1 to M4
And a graft copolymer modified with at least one kind of monomer and an aromatic ring-containing monomer of M5.

Specific examples of the graft copolymer (C1) obtained by modifying the ethylene (co) polymer (A) with at least one functional group-containing monomer of M1 to M4 include maleic anhydride and acrylic acid. Modified graft copolymers are exemplified.

A graft copolymer obtained by modifying the olefin-based polymer (B) different from the component (A) in the above (C2) with at least one monomer of M1 to M4; ethylene or ethylene and ethylene and (C3) in the (C3) M1 to M4 with other olefins
Specific examples of the random copolymer with at least one monomer include acrylic or maleic anhydride-modified linear low-density polyethylene, acrylic acid or maleic anhydride-modified high / medium-density polyethylene, ethylene and acrylic acid or anhydride. Maleic acid copolymer, ethylene and carbon monoxide copolymer, ethylene-methyl vinyl ketone copolymer, ethylene-ethyl vinyl ketone copolymer, ethylene-methyl isopropenyl ketone copolymer, ethylene-hydroxyethyl ( (Meth) acrylate copolymer, ethylene-2-nitrostyrene copolymer, ethylene-m-nitrostyrene copolymer, ethylene-p-nitrophenyl methacrylate copolymer, ethylene- (meth) acrylonitrile copolymer, ethylene- Allyl acetonitrile copolymer, modified with styrene High pressure method low density polyethylene and the like.

The aromatic ring-containing monomer M5 of the above (D1)
The (co) polymer is a homopolymer of an aromatic ring-containing monomer of M5, a copolymer with an olefin, or a copolymer with a functional group-containing monomer. Specifically, styrene or a derivative thereof, allylbenzene, allylbiphenyl, methylstyrene, allylbenzoate, vinylnaphthalene,
Phenyl-1-butene, benzyl methacrylate, 1,1
-Diphenylethylene, 1-phenyl-1-tolylethylene, 1-phenyl-1-styrylethane, 1-tolyl-1-styrylethane, 2,4-diphenyl-1-butene, 2,4-diphenyl-1-pentene , 2,4-diphenyl-4-methyl-1-pentene and the like, a homopolymer using an aromatic ring-containing monomer, a copolymer with an olefin or a copolymer with a functional group-containing monomer. Ethylene-styrene random copolymer,
Styrene-maleic anhydride copolymer is preferred.

Specific examples of the random copolymer (D2) of ethylene or ethylene and other olefins, at least one monomer of M1 to M4, and an aromatic ring-containing monomer of M5 include ethylene- Examples include a styrene-maleic anhydride random copolymer and a maleic anhydride-modified ethylene-allylbenzene copolymer. Specific examples of the copolymer of at least one of the monomers containing a styrene derivative and ethylene include ethylene / vinyl acetate / styrene copolymer, ethylene / vinyl acetate / α-methylstyrene copolymer, ethylene / acrylic acid Ethyl / styrene copolymer, ethylene / ethyl acrylate / α-methylstyrene copolymer and the like can be mentioned.

Specific examples of the graft copolymer (D3) obtained by modifying the ethylene polymer containing an aromatic ring with at least one monomer of M1 to M4 include maleic anhydride-modified ethylene-styrene copolymer. Examples include a polymer, a maleic anhydride-modified ethylene-benzyl methacrylate copolymer, and a maleic anhydride-modified ethylene-allyl styrene copolymer.

Specific examples of the graft copolymer (D4) obtained by modifying a random copolymer of ethylene or ethylene and other olefins with at least one monomer of M1 to M4 with an aromatic ring-containing monomer of M5. An example is a styrene-modified ethylene-maleic anhydride copolymer.

Specific examples of the graft copolymer (D5) obtained by modifying the ethylene (co) polymer (A) with the aromatic ring-containing monomer of M5 include a styrene-modified ethylene (co) polymer. .

Specific examples of the graft copolymer (D6) obtained by modifying the ethylene (co) polymer (A) with at least one monomer of M1 to M4 and an aromatic ring-containing monomer of M5 are described below. Ethylene (co) polymers modified with maleic acid and styrene.

In the present invention, (D1) a (co) polymer of an aromatic ring-containing monomer (M5), (D2) ethylene or ethylene and another olefin, at least one monomer of M1 to M4, A random copolymer with an aromatic ring-containing monomer, (D3) a graft copolymer obtained by modifying an ethylene-based polymer containing an aromatic ring with at least one monomer of M1 to M4, (D4) ethylene or ethylene and Another olefin and at least one of M1 to M4
Graft copolymers obtained by modifying a random copolymer with various kinds of monomers with an M5 aromatic ring-containing monomer, and graft copolymers obtained by modifying the (D5) ethylene (co) polymer (A) with an M5 aromatic ring-containing monomer Polymer, (D6) ethylene (co) polymer (A)
In the introduction method (D) using at least one selected from the group consisting of at least one monomer of M1 to M4 and a graft copolymer modified with M5, the above (D1) to (D6)
The amount of the aromatic ring-containing monomer M5 in the composition is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per 1 g of the resin composition,
Preferably, it is adjusted to be in the range of 1 × 10 ^-6 to 1 × 10 ^-4 mol. If the concentration of the monomer is less than 5 × 10 ⁻⁷ mol, the dielectric breakdown strength may not be sufficiently improved.

The compound or monomer (M6) having two or more ethylene bonds of the present invention can be introduced into the resin component by the following method (E). (E): At least one component selected from (E1) to (E5) is mixed with the resin component containing the ethylene (co) polymer (A). (E1) a homopolymer composed of a monomer containing two or more ethylene bonds or a copolymer with ethylene, and (E2) a homopolymer composed of a monomer containing two or more ethylene bonds or a copolymer with ethylene. (E3) a random copolymer of a monomer containing two or more ethylene bonds and at least one monomer of M1 to M5; (E4) a graft copolymer modified with at least one monomer of M1 to M5; ) A monomer containing two or more ethylene bonds, ethylene, and at least one of M1 to M5.
(E5) A compound having two or more ethylene bonds.

The homopolymer comprising a monomer containing two or more ethylene bonds (E1) or a copolymer with ethylene needs to have sufficient ethylene bonds after polymerization. The crosslinking property can be sufficiently exhibited by the presence of the ethylene bond. As the component (E1), a polymer or the like from a liquid or oligomer having an average molecular weight of 1,000 to 200,000 can be used.

The homopolymer comprising a monomer containing two or more ethylene bonds of the component (E1) is a diene polymer having 4 to 10 carbon atoms, and the diene may be any one as long as the ethylene bond is involved in the polymerization. It may be either cyclic or linear. Among these, a butadiene oligomer or polybutadiene having an average molecular weight of about 1,000 to 200,000 is most preferable in terms of excellent electrical insulation performance and crosslinking efficiency after crosslinking.
Specific examples of dienes include 1,3-butadiene, 1,3
-Pentadiene, 1,4-pentadiene, 2-methyl-
1,3-butadiene, 1,3-hexadiene, 1,4-
Hexadiene, 1,5-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-
Ethyl-1,3-butadiene, 1,3-heptadiene,
Examples thereof include 1,4-heptadiene, 3- (2-propenyl) -cyclopentene, and 2- (cyclopentyl) -1,3-butadiene. It is also possible to use a triene or tetraene polymerized from a diene. Among these, a homopolymer of 1,3-butadiene is preferably used because of its excellent crosslinking properties.

Specific examples of the random copolymer of ethylene of the above-mentioned component (E1) and a monomer containing two or more ethylene bonds include ethylene-allyl (meth) acrylate copolymer and ethylene- (meth) acrylic copolymer. And acid vinyl copolymers. These copolymers may be used as a mixture of two or more.

The above-mentioned (E2) a graft copolymer obtained by modifying a homopolymer of a monomer containing two or more ethylene bonds or a copolymer with ethylene with at least one of M1 to M5 monomers, (E3 ) Ethylene bond 2
(E4) a monomer containing two or more ethylene bonds, ethylene and at least one monomer of M1 to M5 Specific examples of the random copolymer with acrylic acid or maleic anhydride-modified polybutadiene, maleic anhydride-modified ethylene- (meth) acrylate allyl copolymer, maleic anhydride-modified ethylene- (meth) vinyl acrylate copolymer Examples thereof include a polymer, a maleic anhydride-butadiene copolymer, and an ethylene-butadiene-maleic anhydride copolymer. Of these, maleic anhydride-modified polybutadiene is preferred.

Specific examples of the compound having two or more ethylene bonds of the above (E5) include polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., and triallyl. Polyfunctional vinyl monomers represented by isocyanurate, diallyl phthalate, vinyl butyrate, etc., N, N '
-M-phenylenebismaleimide, bismaleimides represented by N, N'-ethylenebismaleimide, dioximes such as P-quinonedioxime, divinylbenzene,
1,5-hexadiene-3-yne, hexatriene, divinyl ether, divinyl compounds such as divinylsulfone, allylstyrene, 2,6-diacrylphenol,
And diallyl compounds such as diallyl carbinol.

In the present invention, (E1) a homopolymer composed of a monomer containing two or more ethylene bonds or a copolymer with ethylene, or (E2) a homopolymer composed of a monomer containing two or more ethylene bonds or A graft copolymer obtained by modifying a copolymer with ethylene with at least one monomer of M1 to M5, (E3) an ethylene bond 2
(E4) a monomer containing two or more ethylene bonds, ethylene, and at least one of M1 to M5. Introduction method using at least one selected from a random copolymer with a monomer and (E5) a compound having two or more ethylene bonds
In (E), the compounding amount of the above (E1) to (E5) is such that the number of ethylene bonds present before crosslinking in the resin composition is 0.8 or more per 1,000 carbon atoms, preferably 0.8 to 4.0. Adjust so that For example, in the case of high-pressure low-density polyethylene or the like, a large number of these ethylene bonds are generally present even without blending the component (M6). Thus, these ethylene bonds are their total number.

Ethylene of the monomers (M1) to (M6)
When the ethylene (co) polymer is blended with the component (A1) and the component (A2) in the introduction into the (co) polymer (A), the component (A2) is introduced after the monomer is introduced into the component (A1). A method of introducing the monomer into the component (A2) and then blending the component (A1) with the component (A1)
A method of introducing the monomer into the blend with (A2), a method of blending the component (A1) into which the monomer is introduced and the component (A2) into which the monomer is introduced, and the like. Introduction methods can also be used.

The above-mentioned ethylene bond is used for crosslinking treatment.
It acts as a crosslinking point to improve crosslinking efficiency. At the time of crosslinking, the crosslinking residue of the crosslinking agent is incorporated into the main chain. Crosslinking residues floating in the polymer component are ion-decomposed by heat and electric field,
Since it becomes a charge and becomes a factor that lowers the volume resistance,
Incorporation of this cross-linking residue into the main chain has the effect of preventing this and improving the volume resistance.

The number of the ethylene bonds is 0.1 per 1000 carbon atoms.
If it is less than 8, the crosslinking efficiency will not be improved, and if it exceeds 4.0, the crosslinking will be excessive and the mechanical properties will deteriorate and the workability will decrease. Further, among these ethylene bonds, it is particularly desirable that the number of vinyl terminals is in the range of 0.5 to 3.0 to increase the crosslinking efficiency.

In introducing the component (M), when a graft-modified (co) polymer is used, its production is performed by reacting the (co) polymer with a reactive monomer in an extruder in the presence of a radical initiator. It is graft-modified by a method or a solution method of reacting in a solution.

Examples of the radical initiator include organic peroxides,
Examples thereof include dihydroaromatics and dicumyl compounds. As the organic peroxide, for example, hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl peroxide, Benzoyl peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di- (t-butylperoxy) hexyne, t-butyloisiacetate, t-butylperoxyisobutyrate and the like are preferably used. Examples of the dihydroaromatic include hydroquinoline or a derivative thereof, dihydrofuran,
-Dihydrobenzene, 1,2-dihydronaphthalene,
9,10-dihydrophenanthrene and the like. Examples of the dicumyl compound include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-di (p-methylphenyl) butane, Examples thereof include 2,3-diethyl-2,3-di (bromophenyl) butane, and in particular, 2,3-dimethyl-2,3-diphenylbutane is preferably used.

In the above ethylene (co) polymer (A), the unit
The resin composition containing (M) is excellent in workability, electric insulation and the like, and is used as the resin composition component for electric 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.

The 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)
It is a polymer, ethylene homopolymer, ethylene / vinyl ester copolymer, ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / unsaturated dicarboxylic acid
(Or anhydride thereof) copolymers, and ethylene / α, β-unsaturated carboxylic acid ester / unsaturated dicarboxylic acid (or anhydride) copolymers.

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 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 the components (A) and (B) (2% by weight of the 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.

Preferred specific combinations of the present invention are shown below. A first preferred example is an ethylene (co) polymer (A)
Is a graft copolymer (C11) modified with a functional group-containing monomer of M1, specifically, a composition of a maleic anhydride-modified ethylene (co) polymer (A).

A second preferred example is an ethylene (co) polymer
(A), a graft copolymer (C11) obtained by modifying the ethylene (co) polymer (A) with a functional group-containing monomer of M1, and / or
Alternatively, this is a combination with a graft copolymer (C21) obtained by modifying another olefin-based polymer (B) with a functional group-containing monomer of M1. Specifically, an ethylene (co) polymer (A)
And maleic anhydride-modified (A) ethylene (co) polymer and / or maleic anhydride-modified low-density polyethylene composition.

A third preferred example is a combination of another olefin polymer (B) with a graft copolymer (C11) obtained by modifying an ethylene (co) polymer (A) with an M1 functional group-containing monomer. Specific examples thereof include a low-density polyethylene and a maleic anhydride-modified (A) ethylene (co) polymer composition.

A fourth preferred example is an ethylene (co) polymer
(A), another olefin polymer (B), and ethylene (co)
A graft copolymer (C11) obtained by modifying the polymer (A) with the M1 functional group-containing monomer and / or a graft copolymer (C21) obtained by modifying another olefin-based polymer (B) with the M1 functional group-containing monomer ), Specifically, ethylene (co) polymer (A), low-density polyethylene,
Examples of the composition include maleic anhydride-modified (A) ethylene (co) polymer and / or maleic anhydride-modified low-density polyethylene.

A fifth preferred example is an ethylene (co) polymer
(A) and a combination of a graft copolymer (E21) obtained by modifying a homopolymer composed of a monomer containing two or more ethylene bonds with a functional group-containing monomer of M1, specifically, an ethylene polymer ( A) and a composition of maleic anhydride-modified liquid polybutadiene.

A sixth preferred example is an ethylene (co) polymer
(A), another olefin-based polymer (B), and a homopolymer comprising a monomer containing two or more ethylene bonds
(E) a graft copolymer (E
21), specifically, ethylene
Examples of the composition include (co) polymer (A), low-density polyethylene, and maleic anhydride-modified liquid polybutadiene.

A seventh preferred example is an ethylene (co) polymer
It is a combination of a graft copolymer (C11) obtained by modifying (A) with a functional group-containing monomer of M1 and a homopolymer (E11) composed of a monomer containing two or more ethylene bonds. A composition of maleic acid-modified (A) ethylene (co) polymer and liquid polybutadiene is exemplified.

An eighth preferred example is an ethylene (co) polymer
(A), a graft copolymer (E21) obtained by modifying a homopolymer comprising a monomer containing two or more ethylene bonds with a functional group-containing monomer of M1, and an ethylene (co) polymer (A)
Is modified with a functional group-containing monomer of M1 (C11) and / or another olefin-based polymer (B)
And a graft copolymer (C21) modified with a functional group-containing monomer of M1.
Examples of the composition include (co) polymer (A), maleic anhydride-modified liquid polybutadiene, and maleic anhydride-modified (A) ethylene (co) polymer and / or maleic anhydride-modified low-density polyethylene.

The ninth preferred example is an ethylene (co) polymer
(A), another olefin-based polymer (B), and a homopolymer comprising a monomer containing two or more ethylene bonds
(E) a graft copolymer (E
21) and a graft copolymer (C11) obtained by modifying the ethylene (co) polymer (A) with a functional group-containing monomer of M1 and / or
Or a combination of another olefin-based polymer (B) with a graft copolymer (C21) modified with a functional group-containing monomer of M1, specifically, an ethylene (co) polymer (A);
Examples of the composition include low-density polyethylene, maleic anhydride-modified liquid polybutadiene, and maleic anhydride-modified (A) ethylene (co) polymer and / or maleic anhydride-modified low-density polyethylene.

A tenth preferred example is that an ethylene (co) polymer (A) and a compound (E5) having two or more ethylene bonds
And a graft copolymer (C11) obtained by modifying the ethylene (co) polymer (A) with a functional group-containing monomer of M1 and / or another olefin-based polymer (B) modified by a functional group-containing monomer of M1. A combination with a graft copolymer (C21), specifically, an ethylene (co) polymer (A), divinylbenzene, a maleic anhydride-modified (A) ethylene (co) polymer and / or maleic anhydride. Compositions of acid-modified low density polyethylene are included.

An eleventh preferred example is an ethylene (co) polymer (A), another olefin polymer (B), a compound (E5) having two or more ethylene bonds, and an ethylene (co) polymer. A graft copolymer (C11) obtained by modifying the union (A) with the M1 functional group-containing monomer and / or a graft copolymer (C21) obtained by modifying another olefin-based polymer (B) with the M1 functional group-containing monomer Specifically, ethylene (co) polymer (A), low-density polyethylene, divinylbenzene, maleic anhydride-modified (A) ethylene (co)
Examples include compositions of polymers and / or maleic anhydride-modified low density polyethylene.

A twelfth preferred example is a combination of an ethylene (co) polymer (A) and an aromatic ring-containing polymer (D1). Specifically, the ethylene (co) polymer (A) ) And an ethylene-styrene random copolymer composition.

A thirteenth preferred example is a graft copolymer (E) obtained by modifying a homopolymer composed of an ethylene (co) polymer (A) and a monomer containing two or more ethylene bonds with an M1 functional group-containing monomer. E21) and a polymer (D1) containing an aromatic ring.
Examples of the composition include a (co) polymer (A), a maleic anhydride-modified liquid polybutadiene, and an ethylene-styrene random copolymer.

A fourteenth preferred example is a graft copolymer (C11) obtained by modifying an ethylene (co) polymer (A) with a functional group-containing monomer of M1, and a polymer (D1) containing an aromatic ring.
Or a combination of a graft copolymer (C21) obtained by modifying an olefin-based polymer with a functional group-containing monomer of M1, specifically, a maleic anhydride-modified (A)
Examples of the composition include an ethylene (co) polymer and an ethylene-styrene random copolymer.

A fifteenth preferred example is that an ethylene (co) polymer (A), an aromatic ring-containing polymer (D1), and an aromatic ring-containing olefin polymer have a functional group containing M1. It is a combination with a graft copolymer (D31) modified with a monomer, specifically, an ethylene (co) polymer (A), an ethylene-styrene random copolymer, and an ethylene-styrene-maleic anhydride graft copolymer. Polymer compositions are included.

In the present invention, the above-mentioned resin composition can be used as it is as an electrical insulating material, but it can also be cross-linked for further improving heat resistance and mechanical strength. 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. Among them, crosslinking with a radical generator such as an organic peroxide is preferable because it is economically inexpensive. At this time, it is particularly preferable that the ethylene bond is present in the resin component, whereby the crosslinking efficiency is increased.

Examples of the radical generator include benzoyl peroxide, lauryl peroxide, dicumyl peroxide, t-butyl hydroperoxide, α, α-bis (t-butylperoxydiisopropyl) benzene, di-t-butyl peroxide. , 2,5-dimethyl-2,
Peroxides such as 5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne and azobisisobutyronitrile;
-Dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-
Examples thereof include 2,3-di (p-methylphenyl) butane and 2,3-diethyl-2,3-di (bromophenyl) butane. Among these, dicumyl peroxide, 2,5
-Dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne and the like are preferably used. The crosslinking agent 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.

In the crosslinking, the components (E1) to (E1)
(E5) It is extremely effective to mix at least one selected from (E5) with a predetermined amount of the resin component and then to crosslink using the radical generator. The electrical insulation performance such as resistance is also improved. As the crosslinking agent, the monomers (M1) to
The same radical generators as used when graft-modifying (M5) to the resin component can be used. in this case,
At least one of monomers (M1) to (M5) and component (E1)
It is also possible to simultaneously mix at least one selected from (E5) to (E5) with the resin component, heat-mix in the presence of a radical generator, and carry out a crosslinking treatment simultaneously with the grafting.

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 insulating materials for electric wires and cables, capacitors, insulating 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 form 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

[0166]

The present invention relates to a resin composition for an electrical insulating material having an ethylene bond and / or a specific functional group-containing monomer in a composition containing a specific ethylene (co) polymer (A). By containing the ethylene (co) polymer, workability and mechanical strength can be improved, and the temperature dependence of volume resistance can be reduced. The functional groups act as trap sites and prevent charge transfer. Further, injection of electric charge from the outside is suppressed. Thus, the volume resistance and space charge characteristics are improved. The aromatic ring has an effect of taking in high-energy electrons, dissipating the energy of the electrons as heat, and releasing them as low-energy electrons (electron energy absorption effect). As a result, the energy of electrons that trigger dielectric breakdown is reduced, and the dielectric breakdown strength is improved. The ethylene bond acts as a crosslinking point and improves crosslinking efficiency. At the time of crosslinking, the decomposition residue of the crosslinking agent is incorporated into the main chain. The cross-linking residue floating in the bulk is ion-decomposed by heat and electric field and becomes an electric charge, which causes a decrease in volume resistance.Therefore, incorporating this cross-linking residue into the main chain prevents this and increases the volume resistance. it can. By utilizing these effects, not only the improvement of the volume resistance and the breaking strength and the deterioration of the electrical properties after the crosslinking are prevented, but also the volume resistance and the dielectric breakdown strength are dramatically improved before the crosslinking.

[0167]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples. The methods for measuring and evaluating the catalysts, various components and physical properties used in the following examples are as follows.

[0168] the number of long chain branches: long chain branching 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.

[0169] Before polymers for physical property measurement processing: using a plastograph manufactured by Toyo Seiki Co., Ciba-Geigy B225 was added 0.2% by weight as an additive, under nitrogen, 190
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 under the condition 4 of JIS-K7210 at a temperature of 190 ° C. and a load of 2.16 kg.

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., orifice diameter of nozzle at 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 Three kinds of standard polystyrene samples (manufactured by Showa Denko KK) having different molecular weights were respectively added to 10 ml of 1,2,4-trichlorobenzene containing 0.1% BHT. After dissolving 2 mg in a dark place at room temperature for 1 hour, the elution time of the peak top was measured by GPC measurement under the following conditions. This measurement was repeated, and a calibration curve was prepared from the molecular weights at a total of 12 points (molecular weight of 580 to 8,500,000) and the elution time of the peak top in a cubic approximation. -Measurement of sample 2 mg of a sample was put into 5 ml of 1,2,4-trichlorobenzene containing 0.1% of BHT, dissolved at 160 ° C for 2 hours with stirring, and then measured 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): Shodex HT-G x 1 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 / min.

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 uncrosslinked sample was formed by sandwiching the sample between aluminum sheets under the following conditions. 1) Preheat the sample at 140 ° C for 5 minutes. 2) Pressurization at 140 ° C and 100 kg / cm ² for 5 minutes. 3) Cool under pressure from 140 ° C to 30 ° C in 5 minutes.

A crosslinked sample was prepared using two types of peroxides. When dicumyl peroxide (abbreviated as DCP) is used as the cross-linking agent, the cross-linked
A sample obtained by kneading 2 parts by weight of DCP with respect to parts by weight was sandwiched between Teflon sheets and molded under the following conditions. 1) Preheat the sample at 120 ° C for 5 minutes. 2) Pressing at 120 ° C. and 100 kg / cm ² for 5 minutes. 3) Cool under pressure from 120 ° C. to 30 ° C. in 5 minutes, at which point voided samples are excluded. 4) Preheat again at 120 ° C for 5 minutes. 5) Pressurization at 120 ° C. and 100 kg / cm ² for 5 minutes. 6) The temperature is increased from 120 ° C to 160 ° C under pressure. 7) Crosslinking at 160 ° C. under pressure for 30 minutes. 8) Cool from 160 ° C to 30 ° C under pressure for 5 minutes.

The crosslinking agent was 2,5-dimethyl-2,5-di
When (t-butylperoxy) hexine (abbreviated as PH) was used, a sample prepared by mixing 1 part by weight of PH with respect to 100 parts by weight of a sample at 140 ° C. was sandwiched between Teflon sheets and molded under the following conditions. 1) Preheat the sample at 140 ° C for 5 minutes. 2) Pressurization at 140 ° C and 100 kg / cm ² for 5 minutes. 3) Cool under pressure from 140 ° C. to 30 ° C. in 5 minutes, at which point voided samples are excluded. 4) Preheat again at 140 ° C for 5 minutes. 5) Pressurization at 140 ° C. and 100 kg / cm ² for 5 minutes. 6) Temperature rise from 140 ° C to 180 ° C under pressure. 7) Crosslinking at 180 ° C. under pressure for 30 minutes. 8) Cool under pressure from 180 ° C to 30 ° C in 5 minutes.

Volume resistance measurement : FIG. 2 (a) 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 was performed after the sample 23 was placed on the electrode system, the upper and lower electrodes were short-circuited for 5 minutes, and the charge charged on the surface of the sample 23 was removed. 90
The sample measured at ° C was short-circuited for 7 minutes so that the temperature in the sample was uniformly 90 ° C. Applied voltage is DC 3300V by battery
It is. 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, can be measured stably up to 3 × 10 ¹⁶ Ω at 90 ° C.. 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 . Current-
From the examination of the time characteristics, it was found that the current was not reduced by the absorption current after the voltage was applied and the current could be stably measured after 10 minutes. Therefore, the current value after 10 minutes from the voltage application was taken as the measured value. If the current is not stable after 10 minutes, 2
Measurements were waited for a minute to stabilize, but more were 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.

A fixed electrode shown in FIG. 4, a so-called Mackeon electrode, was used for the impulse breakdown electric field electrode system. The substrate 1 of the electrode system is made of polymethyl methacrylate, and has a hole having a diameter of 1/2 inch at the center thereof. The electrode 2 was a 1/2 inch stainless steel ball.
Sample 3 was cut into approximately 8 to 10 mm square with a thickness of 50 μm and sandwiched between the electrodes. The space between the sample and the electrode was filled with degassed epoxy resin 4 and cured. Such a MacKeon electrode was immersed in a container filled with silicone oil, placed in a thermostat, and measured at 90 ° C. The voltage waveform used for the destruction was a negative polarity, impulse waveform of 1.2 / 50 μs. The waveform was observed with an oscilloscope, and the destruction at the wave front was adopted as data, and the average value of 20 points or more was obtained.

Space Charge Characteristics The space charge characteristics were evaluated by the pulse electrostatic stress method. After applying a direct current of 15 kV to a sheet having an electrode diameter of 30 mmφ and a thickness of 0.3 mm for 60 minutes, the measurement was performed in a short-circuit state. The quality of the space charge characteristic was determined from the state of charge accumulation near the electrodes that caused distortion such as electric field enhancement and relaxation. It was assumed that almost no charge was observed, accumulation of the same charge as that of the electrode was the same polarity, and different charge was the opposite polarity.

(1) Preparation of Catalyst Preparation of solid catalyst component (1) : Silica (grade CARiACT P) manufactured by Fuji Silysia Ltd. calcined in a nitrogen-substituted 20 liter autoclave at 400 ° C. for 8 hours under nitrogen.
-3) 1.14 kg and 8 liters of hexane were added to form a slurry. A 58 g / liter solution of tris (bistrimethylsilylamide) chromium (III) in hexane was added to the slurry.
0.59 liter was added so that the loading amount of chromium atoms became 0.3 wt%, and the mixture was stirred at 45 ° 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) ; nitrogen-substituted 2
In a 0-liter autoclave, Fuji Silysia silica (grade CAR) calcined at 400 ° C. for 8 hours in nitrogen
iACT P-3) 1.14 kg and 8 liters of hexane were added to form a slurry. 1.9 g of a toluene solution of 162 g / l of methylaluminoxane manufactured by Tosoh Akzo was added to the slurry, and the mixture was stirred at 45 ° C. for 1 hour. The solvent was removed under vacuum to obtain 1.4 kg of a solid catalyst component (2).

Preparation of sample A-1 ; internal volume 2 filled with liquid
Isobutane 10 in a 90 liter loop reactor
0 liter / h, solid catalyst component (1) 8.4 g / h, transition metal compound bis (n-butylcyclopentadienyl) zirconium dichloride (hereinafter abbreviated as BCZ) 0.09 g / h.
(Feed as hexane solution), ethylene 11.80kg
/ Cm ² · h, no hydrogen amount, 13.4 l / h of 1-hexene was fed, and continuous polymerization was carried out at a polymerization temperature of 70 ° C. Also, n-butylethylmagnesium was used as the organometallic compound, and the concentration was 0.6 mmol / l. The contents were continuously discharged, and the polymer was continuously recovered by releasing the contents gas. The average residence time of this polymer was 2.1 hours, the amount of polymer recovered was 14.0 kg / h,
The MFR was 0.66 g / 10 minutes, and the density was 0.925 g / cm ³ .
Table 1 shows the results of the polymerization and the measurement of the physical properties of the polymer.

Preparation of sample A-2 ; internal volume 2 filled with liquid
Isobutane 10 in a 90 liter loop reactor
0 liter / h, solid catalyst component (1) 7 g / h, transition metal compound BCZ 0.1 g / h (feed as a hexane solution), ethylene 18.0 kg / cm ² · h, hydrogen amount 0.22 g / h
h, Continuous polymerization was carried out at a polymerization temperature of 80 ° C. Also, n-butylethylmagnesium was used as the organometallic compound, and the concentration was 0.6 mmol / l. The contents were continuously discharged, and the polymer was continuously recovered by discharging the contents gas. The average residence time of this polymer is 2.
1 hour, polymer recovery 16.0kg / h, MFR 2.5g / 1
At 0 minute, the density was 0.941 g / cm ³ . Table 1 shows the results of the polymerization and the measurement of the physical properties of the polymer.

Preparation of Sample A-3 : A gas-phase reactor having an internal volume of 3.9 m ³ containing 140 kg of polyethylene seed polymer was sufficiently purged with nitrogen, and heated to 70 ° C. Next, ethylene was supplied at a rate of 30 kg / h, and the total pressure in the reactor was increased to 21 kg / h.
kg / cm ² . Further, 6 g / h of the solid catalyst component (1) and 16 g of a hexane solution of BCZ (0.8 g / l) were added.
3 ml / h, hexane suspension of a mixture of n-butyllithium and triisobutylaluminum (mixing molar ratio [Li]
/[Al]=0.3/1, total concentration 0.5mol / l) 240m
The mixture was continuously supplied at a rate of 1 / h to perform gas phase polymerization.
At this time, the residence time of the polymer was 5 hours, and the amount of the produced polymer was 30 kg / h. The MFR of the polymer is 2.6 g / 1
0 min, HLMFR 49.1 g / 10 min, density 0.942 g /
cm ³ . Table 1 shows the results of the polymerization and the measurement of the physical properties of the polymer.

Preparation and Blend of Sample A-4 : Solid catalyst component (2), transition metal compound BCZ, n-butylethylmagnesium as organometallic compound, Zr homopolymer obtained by polymerizing comonomer as 1-hexene ( Sample A
-4a) 4 kg of a chromium-based homopolymer obtained by polymerizing with solid catalyst component (1) and n-butylethylmagnesium as an organometallic compound without using a transition metal compound (sample A
-4b) 1 kg was blended using a Nakatani 40 mmφ co-axial single screw extruder KTX37 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. The physical properties of the polymer obtained by this blend are shown in Table 1.

[0191]

Component (B): Olefin polymer different from component (A) B-1: High pressure radical method polyethylene (LD) [Density = 0.919 g / cm ³ , MI = 1.0 g / 10 min, trade name: J Rex LD W2000, Japan Polyolefin Co., Ltd.
B-2: Linear low-density polyethylene (LL) [Density = 0.921 g / cm ³ , MI = 1.0 g / 10 min, trade name: J Rex LL AF3280, Nippon Polyolefin
B-3: Polypropylene (PP) [Density = 0.905 g / cm ³ , MI = 1.5 g / 10 min, trade name: J-Aroma F120K, Japan Polyolefin Co., Ltd.]
Made

(C) Component C1-1: Maleic anhydride-modified ethylene (co) polymer [Maleic anhydride was added to 100 parts by weight of sample (A-1).
After preliminarily mixing 7 parts by weight and 0.05 parts by weight of 2,5-dimethyl-2,5-di (tert-butyl peroxide) with a Henschel mixer, the mixture was reacted at 230 ° C. using a twin-screw extruder. As a result of an infrared spectroscopic analysis, the content of maleic anhydride in 1 g of the polymer was 2.6 × 10 ⁻⁵ mol. ]

C1-2: maleic anhydride-modified ethylene
(Co) polymer [Maleic anhydride was reacted with sample (A-2) in the same manner as described above. As a result of examination by infrared spectroscopy, 1 g of polymer was obtained.
Medium, the maleic anhydride content was 2.6 × 10 ^-5 mol. ]

C1-3: Acrylic acid-modified ethylene (co) polymer [Sample A-1 was mixed with acrylic acid and dicumyl peroxide, and then reacted at 200 ° C. using an extruder. As a result of examination by infrared spectroscopy, the acrylic acid content was 3.7 × 10 ⁻⁶ mol per 1 g of the polymer. ]

C1-4: Maleic anhydride-modified ethylene
(Co) polymer [Maleic anhydride was added to 100 parts by weight of sample (A-4a).
After 0.7 parts by weight and 0.05 parts by weight of 2,5-dimethyl-2,5-di (tert-butyl peroxide) were premixed with a Henschel mixer, the reaction was carried out at 230 ° C. using a twin-screw extruder. As a result of an infrared spectroscopic analysis, the content of maleic anhydride in 1 g of the polymer was 2.6 × 10 ⁻⁵ mol. ]

C1-5: Maleic anhydride-modified ethylene
(Co) polymer [Maleic anhydride was added to 100 parts by weight of sample (A-4b).
After 0.7 parts by weight and 0.05 parts by weight of 2,5-dimethyl-2,5-di (tert-butyl peroxide) were premixed with a Henschel mixer, the reaction was carried out at 230 ° C. using a twin-screw extruder. As a result of an infrared spectroscopic analysis, the content of maleic anhydride in 1 g of the polymer was 2.6 × 10 ⁻⁵ mol. ]

C2-1: Maleic anhydride-modified high-pressure radical method polyethylene [Maleic anhydride was added to 100 parts by weight of sample (B-1).
After premixing 7 parts by weight and 0.05 parts by weight of 2,5-dimethyl-2,5-di (tert-butyl peroxide) with a Henschel mixer, a reaction was carried out at 230 ° C. using a twin screw extruder. As a result of an infrared spectroscopic analysis, the content of maleic anhydride in 1 g of the polymer was 2.6 × 10 ⁻⁵ mol. ]

C2-2: Acrylic acid-modified high-pressure radical method polyethylene [Acrylic acid and dicumyl peroxide were added to Sample (B-1), and the mixture was reacted at 200 ° C. using an extruder. As a result of an infrared spectroscopic analysis, the acrylic acid content was 3.4 × 10 ^-6 mol per 1 g of the polymer. ]

C3-1: Ethylene-maleic anhydride random copolymer [In a 3.8-liter autoclave with a stirrer purged with nitrogen, 380 g of n-hexane and 11 g of a maleic anhydride-acetone solution (0.11% as maleic anhydride)
g), and 2,5-dimethyl-2,2,
After 5-di (tert-butyl peroxide) was added and 1700 g of ethylene was charged, the mixture was polymerized at 1600 kgf / cm ^{2 at} a temperature of 190 ° C. for a polymerization time of 1 hour to obtain an ethylene-maleic anhydride copolymer. As a result of examination by infrared spectroscopy, the content of maleic anhydride in 1 g of the polymer was 1.6 × 10
^-3 mol. ]

C3-2: Ethylene-vinyl alcohol copolymer (Et-VAl) [Prepared in the same manner as in (C3-1) above. As a result of examination by infrared spectroscopy, the content of alcohol group in 1 g of the polymer was
It was 2.4 × 10 ^-4 mol. ]

C3-3: Ethylene-nitrostyrene copolymer (Et-NSt) [Prepared in the same manner as in the above (C3-1). As a result of examination by infrared spectroscopy, the content of nitro group in 1 g of the polymer was 2.4.
× 10 ^-4 mol. ]

C3-4: Ethylene-acrylonitrile copolymer (Et-AN) [Prepared in the same manner as in the above (C3-1). As a result of examination by infrared spectroscopy, the content of nitrile group in 1 g of the polymer was 2.
It was 3 × 10 ^-4 mol. ]

(D) Component D1-1: Ethylene-styrene random copolymer (Et)
-St) [Prepared by a high-pressure radical polymerization method. As a result of examination by infrared spectroscopy, the styrene content was 1.6 × 1 in 1 g of the polymer.
0 was ^-3 mol. ]

D1-2: polystyrene

D2-1: Ethylene-styrene-maleic anhydride random copolymer [In an autoclave equipped with a stirrer, styrene monomer,
After maleic anhydride was introduced and ethylene was charged, polymerization was carried out. As a result of examination by infrared spectroscopy, the content of styrene was 1.2 × 10 ^-3 mol and the content of maleic anhydride in 1 g of the polymer.
1.1 × 10 ^-3 mol. ]

D3-1: Maleic anhydride-modified ethylene-
Styrene copolymer [Ethylene-styrene copolymer produced by high-pressure radical polymerization method was reacted with maleic anhydride using dicumyl peroxide. As a result of examination by infrared spectroscopy, the content of styrene was 1.5 × 10 ⁻³ mol and the content of maleic anhydride was 2.0 × 10 ⁻⁵ mol in 1 g of the polymer. ]

D4-1: Styrene-modified ethylene-maleic anhydride random copolymer [Ethylene-maleic anhydride polymer produced by a high-pressure radical polymerization method was reacted with styrene using dicumyl peroxide. As a result of examination by infrared spectroscopy, the content of styrene was 1.5 × 10 ⁻³ mol and the content of maleic anhydride was 1.6 × 10 ⁻³ mol in 1 g of the polymer. ]

D5-1: Styrene-modified ethylene (co) polymer [Sample (A-1) was reacted with styrene using dicumyl peroxide. As a result of examination by infrared spectroscopy, the styrene content was 1.2 × 10 ⁻³ mol per 1 g of the polymer. ]

D6-1: Styrene, maleic anhydride-modified ethylene (co) polymer [Sample (A-1) was reacted with styrene and maleic anhydride using dicumyl peroxide. As a result of examination by infrared spectroscopy, the styrene content was 6.9 × 1 in 1 g of the polymer.
The content was 0 ^-4 mol and the content of maleic anhydride was 1.9 × 10 ^-5 mol. ]

(E) Component E1-1: Liquid polybutadiene [Average molecular weight 3000, specific gravity 0.89 g / cm ³ , trade name: Nisseki polybutadiene B-3000, manufactured by Nippon Petrochemical Co., Ltd.]

E1-2: Butadiene resin [specific gravity 0.89 g / cm ³ , trade name: JSR RB820,
Nippon Synthetic Rubber Co., Ltd.]

E1-3: Liquid polyisoprene [Average molecular weight: 29,000, 740 poise / 38 ° C., trade name:
Claprene LIR-30, manufactured by Kuraray Co., Ltd.]

E2-1: Maleic anhydride-modified liquid polybutadiene [average molecular weight: 3,000, specific gravity: 0.89 g / cm ³ , and the result of infrared spectroscopic analysis showed that the content of maleic anhydride in 1 g of polymer was:
1.4 × 10 ^-3 mol. Product name: Nisseki polybutadiene M-2000, manufactured by Nippon Petrochemical Co., Ltd.

E2-2: Acrylic acid-modified liquid polybutadiene [average molecular weight: 2,000, specific gravity: 0.91 g / cm ³ , and the result of infrared spectroscopic analysis showed that the acrylic acid content was 2.2 in 1 g of the polymer.
× 10 ^-4 mol. Product name: Nisseki polybutadiene M
AC-2000, manufactured by Nippon Petrochemical Co., Ltd.]

E2-3: Maleic anhydride-modified butadiene resin [Modified by heating in a single screw extruder. As a result of examination by infrared spectroscopy, the content of maleic anhydride in 1 g of the polymer was 3.4 × 10
^-4 mol. ]

E2-4: Maleic anhydride-modified liquid polyisoprene [Modified by heating in an autoclave. As a result of examination by infrared spectroscopy, the content of maleic anhydride in 1 g of the polymer was 2.9.
× 10 ^-4 mol. ]

E3-1: Copolymer of maleic anhydride butadiene [Modified by heating in an autoclave. As a result of examination by infrared spectroscopy, the content of maleic anhydride in 1 g of the polymer was 9.0.
× 10 ^-5 mol. ]

E4-1: Ethylene and vinyl alcohol were copolymerized and then hydrolyzed to produce an ethylene / vinyl alcohol copolymer (1.1 × 10 ⁻³ mol of alcohol residue in 1 g) and polybutadiene (E1- A mixture with 2).

B5-1: Divinylbenzene

Examples 1 to 82 and Comparative Examples 1 to 16 The above components (A) to (E) were used in the proportions shown in Tables 2 to 6, and crosslinking was carried out as necessary to obtain a resin composition. The electrical properties (volume resistance at room temperature and 90 ° C.,
(Impulse breakdown electric field, space charge characteristics) were measured and evaluated. The results are shown in Tables 7-9.

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

(1) Examples 1 to 3 are the first preferred examples of the graft copolymer (C11) obtained by modifying the ethylene (co) polymer (A) with the functional group-containing monomer of M1. This is an example in which samples (C1-1), (C1-2), and (C1-3) were used, and it can be seen that the volume resistance and space charge characteristics were improved.

(2) Examples 4 to 16 were the second preferred examples, in which the ethylene (co) polymer (A) and the ethylene (co) polymer (A1) were modified with the M1 functional group-containing monomer. It is a composition comprising a graft copolymer (C21) obtained by modifying the graft copolymer (C11) and / or another olefin-based polymer (B) with a functional group-containing monomer of M1. Specifically, samples (A-1) to (A-4), (C1-1) to (C1-3),
The composition is a combination of (C2-1) and (C2-2). (2) ′ Examples 17 to 21 are ethylene (co) polymers.
(A) A composition comprising a random copolymer (C3) of an olefin and at least one monomer of M1 to M4, specifically, samples (A-1), (A-2), and (C3-1) )-(C3-
This is a composition obtained by combining 4). All of these have improved volume resistance and space charge characteristics.

(3) Examples 22 to 25 are the third preferred examples, in which another olefin polymer (B) and ethylene
A composition comprising the (co) polymer (A) and a graft copolymer (C11) modified with a functional group-containing monomer of M1, specifically, samples (A2-1) to (A2-3), (C1) -1), (C1-
It can be seen that the composition obtained by combining 3) has improved volume resistance and space charge characteristics.

(4) Examples 26 to 28 are the fourth preferred examples of the ethylene (co) polymer (A), the other olefin polymer (B) and the ethylene (co) polymer (A). A) a graft copolymer (C11) obtained by modifying a M1 functional group-containing monomer and / or a graft copolymer (C21) obtained by modifying an olefin polymer with an M1 functional group-containing monomer. Are samples (A-1), (A-2), (B-1),
The composition is a combination of (C2-1) and (C2-2). (4) ′ Examples 29 to 32 are ethylene (co) polymers.
A composition comprising (A), another olefin polymer (B), and a random copolymer (C3) of an olefin and at least one monomer of M1 to M4, specifically, a sample (A-
1), (B-1), and a composition obtained by combining (C3-1) to (C3-4). All of these have improved volume resistance and space charge characteristics.

(5) Examples 33 to 38 are a fifth preferred example, in which an ethylene (co) polymer (A) and an ethylene bond 2
Graft copolymer (E2) obtained by modifying a homopolymer composed of a monomer containing
1), specifically, samples (A-1) to (A-
4) A composition obtained by combining (E2-1) and (E2-2), which has high volume resistance even after crosslinking and has improved space charge characteristics.

(6) Examples 39 to 43 are the sixth preferred examples, which contain an ethylene (co) polymer (A), another olefin polymer (B), and two or more ethylene bonds. A composition comprising: a graft copolymer (E21) obtained by modifying a homopolymer comprising a monomer with a functional group-containing monomer of M1;
Specifically, samples (A-1), (B-1), (E2-1) to (E2-1)
It is a composition obtained by combining 2-4). (6) ′ Examples 44 to 47 are ethylene (co) polymers.
(A), another olefin polymer (B), a random copolymer (E3) of a monomer containing two or more ethylene bonds and at least one monomer of M1 to M5, and two or more ethylene bonds And a monomer containing ethylene and M1
To a composition comprising at least one random copolymer (E4) with at least one monomer of M5, specifically, samples (A-1), (A-2), (B-1), (B-2), (E
It is a composition obtained by combining 3-1) and (E4-1). These have high volume resistance after crosslinking and have improved space charge properties. In particular, the volume resistance increases as the proportion of E2-1 increases.

(7) Example 48 is a seventh preferred example of a graft copolymer (C11) obtained by modifying an ethylene (co) polymer (A) with a monomer having a functional group of M1, and two ethylene bonds. A homopolymer (E
11), specifically, the sample (E1-1)
It is a composition comprising (C1-1). (7) ′ Examples 49 to 50 are ethylene (co) polymers.
A graft copolymer (C11) obtained by modifying (A) with an M1 functional group-containing monomer, and a graft copolymer obtained by modifying a homopolymer comprising a monomer containing two or more ethylene bonds with an M1 functional group-containing monomer A composition comprising (E21), specifically, a composition obtained by combining sample (E2-1) with (C1-1) or (C1-2). They have high volume resistance after crosslinking and have improved space charge properties.

(8) Examples 51 to 52 are the eighth preferred examples in which the ethylene (co) polymer (A) and the ethylene bond 2
Graft copolymer (E2) obtained by modifying a homopolymer composed of a monomer containing
1) and a graft copolymer (C11) obtained by modifying the ethylene (co) polymer (A) with the M1 functional group-containing monomer and / or a graft copolymer obtained by modifying the olefin polymer with the M1 functional group-containing monomer. The composition comprising the union (C21), specifically, the samples (A-1), (E2-1), (C1-1),
It is a composition obtained by combining 2-1). (8) ′ In Example 53, the other olefin polymer (B)
A graft copolymer (E21) obtained by modifying a homopolymer composed of a monomer containing two or more ethylene bonds with a functional group-containing monomer of M1, and an ethylene (co) polymer (A).
Graft copolymer modified with one functional group-containing monomer
A composition comprising (C11), specifically, sample (B-1);
It is a composition comprising (E2-1) and (C1-1). They have high volume resistance after crosslinking and have improved space charge properties.

(9) Example 54 is a ninth preferred example in which an ethylene (co) polymer (A), another olefin polymer (B), and a monomer containing two or more ethylene bonds are used. (E21) a homopolymer modified with a functional group-containing monomer of M1 and a graft copolymer modified with an olefin-based polymer with a functional group-containing monomer of M1
(C21), specifically, the sample (A-1),
It is a composition comprising (B-1), (E2-1) and (C2-1). (9) ′ Examples 55 to 58 are ethylene (co) polymers.
(A), another olefin polymer (B), and a homopolymer (E1) comprising a monomer containing two or more ethylene bonds.
1) and a composition comprising a graft copolymer (C21) obtained by modifying an olefin polymer with a functional group-containing monomer of M1, specifically, samples (A-1), (A-3), B-
1) A composition obtained by combining (E1-1) to (E1-3) and (C2-1). These have high volume resistance after crosslinking and have improved space charge properties.

(10) Examples 59 to 60 are tenth preferred examples, wherein an ethylene (co) polymer (A), a compound (E5) having two or more ethylene bonds, and an ethylene (co) polymer
A composition comprising a graft copolymer (C11) obtained by modifying (A) with a functional group-containing monomer of M1 or a graft copolymer (C21) obtained by modifying an olefin-based polymer with a functional group-containing monomer of M1; Are samples (A-1) and (E5-1)
And (C1-1) or (C2-1). They have a high volume resistivity after crosslinking and have improved breakdown electric field and space charge properties.

(11) Example 61 is an eleventh preferred example comprising an ethylene (co) polymer (A), another olefin polymer (B), and a compound having two or more ethylene bonds. A composition comprising the composition (E5) and a graft copolymer (C21) obtained by modifying an olefin-based polymer with a functional group-containing monomer of M1, specifically, samples (A-1), (B-1),
It is a composition comprising (E5-1) and (C2-1). They have a high volume resistivity after crosslinking and have improved breakdown electric field and space charge properties.

(12) Examples 62 to 64 are twelfth preferred examples of compositions comprising an ethylene (co) polymer (A) and a polymer (D1) containing an aromatic ring. Specifically, it is a composition comprising sample (A-1) and (D1-1) or (D1-2), and has improved volume resistance, breakdown electric field, and space charge characteristics.

(13) Example 65 is a thirteenth preferred example in which a homopolymer composed of an ethylene (co) polymer (A) and a monomer containing two or more ethylene bonds is prepared as a functional group-containing monomer of M1. -Modified graft copolymer (E21)
And a polymer (D1) containing an aromatic ring. Specifically, samples (A-1), (E2-1), (D1-
1) which has a high volume resistance even after crosslinking and has improved breakdown electric field and space charge characteristics.

(14) In Example 66, a graft copolymer (C11) obtained by modifying an ethylene (co) polymer (A) with a functional group-containing monomer of M1 and an aromatic ring were used as a fourteenth preferred example. A composition comprising the polymer (D1) contained therein, specifically, a composition comprising the samples (C1-1) and (D1-1). (14) ′ Further, Example 67 is a graft copolymer obtained by modifying an ethylene (co) polymer (A) with an M1 functional group-containing monomer.
(C11) and a composition comprising a graft copolymer (D5) obtained by modifying the ethylene (co) polymer (A) with an aromatic ring-containing monomer of M5, specifically, a sample (C1-1) and D5-1). These have improved volume resistance, breakdown electric field and space charge characteristics.

(15) Example 68 is a fifteenth preferred example of the ethylene (co) polymer (A), the polymer (D1) containing an aromatic ring, and the olefin-based polymer containing an aromatic ring. A composition comprising a graft copolymer (D31) obtained by modifying a polymer with a functional group-containing monomer of M1, specifically, a sample (A-
1) a composition comprising (D1-1) and (D3-1),
Volume resistance, breakdown field and space charge properties are improved.

(15) ′ Examples 69 to 73 are ethylene (co)
Polymer (A), olefin and at least one of M1 to M4
Random copolymer (D2) with the same type of monomer and an aromatic ring-containing monomer of M5, and a graft copolymer (D3) obtained by modifying an olefin polymer containing an aromatic ring with at least one of M1 to M4 monomers ), Olefin and M1 to M
Graft copolymer (D4) obtained by modifying a random copolymer with at least one monomer of No. 4 with an aromatic ring-containing monomer of M5, and an ethylene (co) polymer (A) with an aromatic ring-containing monomer of M5 At least one of a modified graft copolymer (D5) and a graft copolymer (D6) obtained by modifying the ethylene (co) polymer (A) with at least one monomer of M1 to M4 and an aromatic ring-containing monomer of M5. One kind of a composition. Specifically, samples (A-1) and (D2-
1) a composition comprising one of (D6-1) and
Volume resistance, breakdown electric field, and space charge characteristics are improved.

(16) In Examples 74 to 75, ethylene (co)
Graft copolymer (D5) obtained by modifying polymer (A) with an aromatic ring-containing monomer of M5, or ethylene (co) polymer (A)
Is modified with at least one monomer of M1 to M4 and an aromatic ring-containing monomer of M5 (D)
6). Specifically, it is a composition comprising samples (D5-1) and (D6-1), and has improved volume resistance, breakdown electric field, and space charge characteristics.

(17) In Examples 76 to 77, ethylene (co)
A graft copolymer (D5) or an ethylene (co) polymer (A) obtained by modifying the polymer (A) with an M5 aromatic ring-containing monomer, wherein at least one monomer of M1 to M4 and an aromatic ring of M5 are contained. Graft copolymer modified with monomer (D6)
And a homopolymer (E11) comprising a monomer containing two or more ethylene bonds. Specifically, it is a composition comprising the sample (E1-1) and (D5-1) or (D6-1), has a high volume resistance even after crosslinking, and has improved breakdown electric field and space charge characteristics. ing.

(18) In Examples 78 to 79, ethylene (co)
It is a composition comprising a polymer (A), a homopolymer (E11) comprising a monomer containing two or more ethylene bonds, and a polymer (D1) further containing an aromatic ring. Specifically, it is a composition comprising the samples (A-1) and (E1-1) and further (D1-1), has a high volume resistance even after crosslinking, and has improved space charge characteristics. The addition of the sample (D1-1) also improves the breakdown electric field.

(19) In Examples 80 to 81, the ethylene (co) polymer (A1) comprising a metallocene catalyst system and the ethylene (co) polymer (A2) comprising a chromium compound catalyst system were blended. (Co) In the polymer (A), the component (A1)
An ethylene (co) polymer (A) prepared by modifying either the component (A2) with the functional group-containing monomer of M1
Graft copolymer modified with one functional group-containing monomer
It is a composition which is (C11). Specifically, the sample (A-4
A composition comprising (a) and (C1-5), (A-4b) and (C1-4), having improved volume resistance, breakdown electric field, and space charge characteristics.

(19) 'Example 82 is a composition obtained by blending the composition material of Example 81 with another olefin polymer (B). Specifically, the samples (A-4a) and (B- 1) and (C1-5)
A composition comprising: It can be seen that the volume resistance, breakdown electric field, and space charge characteristics are improved.

Comparative Examples 1 to 5 show other olefin polymers.
It is an uncrosslinked and crosslinked type (B), has low volume resistance and breakdown electric field, and has poor space charge. Comparative Examples 6 to 11
Are uncrosslinked and crosslinked types of the ethylene (co) polymer (A), and the results of other olefin-based polymers (B) (Comparative Example 1)
Although the characteristics are better than those of (5) to (5), they are not satisfactory. Comparative Examples 12 to 14 are uncrosslinked and crosslinked types of a blend of an ethylene (co) polymer (A) and another olefin-based polymer (B), but the ethylene (co) polymer (A) alone In the case of (Comparative Examples 6 to 11), the properties are better than the results (Comparative Examples 1 to 5) of the other olefin polymer (B),
Not satisfactory. Comparative Examples 15 to 16 are ethylene (co) polymer (A) and (C11) ethylene (co) polymer (A)
Is modified with a functional group-containing monomer of M1 or (D6) an ethylene (co) polymer (A) with M1 to M4
(A-1) and (C1-1) or (D6-1) a blend of a graft copolymer modified with at least one kind of monomer and an aromatic ring-containing monomer of M5.
But the content of the monomer is 1 g of the composition.
Per 5 × 10 ^-7 mol / volume, the volume resistance, breakdown electric field and space charge characteristics are not improved.

Wire Covering Examples The compositions of Examples 4, 10, 33, 51 and 62 were coated with copper wires, and the moldability was evaluated. The coating conditions are
0.9mm, Die diameter 2.5mm, Nipple diameter 0.95mm, Die: Nipple clearance 5.3mm, Finish outer diameter 2.45
mm and the take-up speed was 100 m / min. After molding,
As a result of visual observation, the surface roughness was small and could be put to practical use.

Using the compositions of Examples 4, 10, 33, 51 and 62, a cable having a cross-sectional structure shown in FIG. 4 was manufactured. As a result, when any of the compositions was used, the manufacturability and the performance as a cable were good.

[0254]

Industrial Applicability The present invention provides a composition containing an ethylene (co) polymer having a wide molecular weight distribution, excellent processability, a mechanical strength, and excellent electrical insulation. Or a resin composition for an electrical insulating material having a specific monomer, which is excellent in electrical insulation performance such as volume resistance and dielectric breakdown strength, or is rich in crosslinkability, and has electrical insulation such as volume resistance and dielectric breakdown strength even after crosslinking. Excellent performance. Further, the present invention provides an electric wire or cable having an insulating layer formed of a resin composition and a crosslinked product thereof. INDUSTRIAL APPLICABILITY The present invention can be widely used as an insulating material in various electric appliances, transportation equipment, plants, factories, and the like, or as electric wires, cables, and DC cables.

[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 cross-sectional view (b) of an electrode system for measuring volume resistance used in Examples of the present invention.

FIG. 3 is a schematic cross-sectional view of a measuring device for a breakdown voltage test used in an example 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 Stainless steel ball 32 Sample 33 Epoxy resin 34 Substrate made of polymethyl methacrylate 41 Conductive member made of conductive metal assembly line 42 Internal semiconductive layer 43 Insulating resin composition 44 External semiconductive Layer 45 Aluminum foil 46 Protective material (Polyolefin with inorganic flame retardant)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 29/02 C08L 29/02 31/00 31/00 33/00 33/00 35/00 35/00 47/00 47/00 51/00 51/00 H01B 3/44 H01B 3/44 F

Claims (8)

[Claims] 1. A resin component comprising an ethylene (co) polymer (A) satisfying the following conditions (I) to (III):
When a unit (M) derived from at least one monomer selected from 1 to M6 is contained and the concentration is from M1 to M5, 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per 1 g of the resin composition, In this case, 0 per 1000 carbon atoms in the resin component.
A resin composition for an electrical insulating material, wherein the resin composition has 8 or more ethylene bonds; (I) insoluble at 126 ° C. in a solvent in which butylcellosolve and para-xylene are mixed at a volume fraction of 50:50. The ingredients are
Contains 0.2 long chains (C6 or more branches) / 10,000 C or more; (II) MFR is 0.001 to 100 g / 10 min; (III) Electric activation energy is 0.4 eV or less; M1: M2: Monomer containing a carbonyl group; M3: Monomer containing a nitro group; M4: Monomer containing a nitrile group; M5: Monomer containing an aromatic ring; M6: Compound or monomer having two or more ethylene bonds . 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 electrical insulating material using the resin composition according to claim 1. 7. The electrical insulating material according to claim 6, wherein the resin composition according to claim 1 is crosslinked. 8. An electric wire or cable comprising the electric insulating material according to claim 6 or 7 as an insulating layer.