JP2003313235A - Covering material for electric wire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a covering material for electric wires, having excellent electrical insulation, flexibility, abrasion resistance and scuff resistance and to provide an electric wire, a power cable and a telecommunication cable covered with the same. <P>SOLUTION: This covering material for the electric wires is composed of a hydrogenated copolymer obtained by hydrogenating a copolymer consisting of a conjugated diene and a vinylaromatic compound, and the hydrogenated copolymer (1) is specified by following (a)-(d): (a) a content of the vinylaromatic compound in the hydrogenated copolymer is >50 wt.% and ≤90 wt.%; (b) an amount of a vinylaromatic compound polymer block in the hydrogenated copolymer is ≤40 wt.%; (c) a weight average molecular weight of the hydrogenated copolymer is 50,000-1,000,000; and (d) at least 75% of the double bonds based on the conjugated diene compound in the hydrogenated copolymer are hydrogenated. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sufficient electric insulating property,
The present invention relates to an electric wire coating material having excellent flexibility, abrasion resistance, and scratch resistance, and further relates to an electric wire, a power cable, and a communication cable coated with this coating material.

[0002]

2. Description of the Related Art The 600V vinyl-insulated vinyl sheath cable flat type, which is widely used for household and residential assembled wires, is a typical low-voltage power cable, which is mainly composed of polyvinyl chloride. The insulator is excellent in flexibility and peeling property and is easy to construct.
However, since a vinyl chloride resin contains a large amount of chlorine in its molecule, it is feared that the vinyl chloride resin has a large load on the environment, and an effective alternative material is required. Polyethylene is used for electrical insulators such as wire coverings that use non-vinyl chloride resin.
Particularly, a cross-linked product of low-density polyethylene is used (for example, see Patent Document 1). However, the coating layer using such a polyethylene-based resin is inferior in flexibility, printability, filler dispersibility, and flame retardant dispersibility as compared with a conventional coating layer made of polyvinyl chloride. There was a disadvantage in such cases and improvements were required.

[0003]

[Patent Document 1] Japanese Patent Laid-Open No. 10-212377

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, that is, a resin having sufficient electric insulation, flexibility, abrasion resistance and scratch resistance, and a resin thereof. An object of the present invention is to provide an electric wire coating material comprising the composition, and an electric wire, an electric power cable and a communication cable coated with the coating material.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that a copolymer of a conjugated diene having a specific vinyl aromatic compound content and a vinyl aromatic compound is obtained. The inventors have found that hydrogenated products effectively solve the above problems, and have completed the present invention.

That is, the present invention is as follows: Electric wire coating which is a hydrogenated copolymer obtained by adding hydrogen to a copolymer made of a conjugated diene and a vinyl aromatic compound, and which is made of the hydrogenated copolymer (1) which is the following (a) to (d): It is a material. (A) The content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less. (B) The amount of the vinyl aromatic compound polymer block in the hydrogenated copolymer is 40% by weight or less. (C) The weight average molecular weight of the hydrogenated copolymer is 50,000 to 100.
Ten thousand. (D) 75% or more of the double bond based on the conjugated diene compound in the hydrogenated copolymer is hydrogenated.

2. From a composition containing 99 to 1 part by weight of the hydrogenated copolymer component (1) and at least one component (2) from 1 to 99 parts by weight selected from the group consisting of a thermoplastic resin and a rubbery polymer. Wire coating material The hydrogenated copolymer (1) was analyzed by differential scanning calorimetry (DS
In C), the crystalline peak is in the range of -50 ° C to 100 ° C.
3. The electric wire coating material as described in 1 or 2 above, characterized in that it is substantially absent. 4. The electric wire coating material as described in any one of 1 to 3 above, wherein the amount of the vinyl aromatic compound polymer block of the hydrogenated copolymer (1) is less than 10% by weight. The amount of the vinyl aromatic compound polymer block of the hydrogenated copolymer (1) is 10 to 40% by weight, the electric wire coating material as described in any one of 1 to 3 above,

6. The hydrogenated copolymer (1) is a hydrogenated copolymer obtained by adding hydrogen to a copolymer having at least one structure selected from the following general formulas (1) to (5). (1) B (2) B-A (3) B-A-B (4) (B-A) _m -X (5) (B) -A) _n -X-A _p (where B is a random copolymer block of a conjugated diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, and m is an integer of 2 or more. And n
And p are integers of 1 or more. X represents a coupling agent residue. )

7. 7. The electric wire coating material as described in any one of 1 to 6 above, wherein the hydrogenated copolymer (1) has a crosslinked structure. The volume resistivity of the hydrogenated copolymer (1) is 10 ¹⁵ Ω.
8. The electric wire coating material as described in any one of 1 to 7 above, wherein the electric wire coating material is cm or more. 10. The electric wire coating material as described in any one of 1 to 8 above, wherein the hydrogenated copolymer (1) contains a flame retardant. The electric wire coating material as described in 9 above, wherein the flame retardant is a non-halogen flame retardant,

11. 12. An electric wire coated with the electric wire coating material according to any one of 1 to 10 above, 12. 13. A power cable coated with the electric wire coating material according to any one of 1 to 10 above, and 13. A communication cable, which is coated with the electric wire coating material according to any one of 1 to 10 above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The content of the vinyl aromatic compound in the hydrogenated copolymer (1) used in the present invention depends on the blocking resistance, handleability,
It is more than 50% by weight from the viewpoint of scratch resistance and 90% by weight or less from the viewpoint of flexibility when used as a wire coating material. It is preferably more than 60% by weight and 88% by weight or less, and more preferably 62 to 86% by weight. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer (1) is
It may be grasped by the content of the vinyl aromatic compound in the copolymer before hydrogenation.

In the hydrogenated copolymer (1) used in the present invention, the content of the vinyl aromatic compound polymer block (A) is 4 from the viewpoint of flexibility when used as a wire coating material.
It is 0% by weight or less, preferably 3 to 40% by weight, more preferably 5 to 35% by weight. In order to obtain the electric wire coating material of the present invention, when a more flexible one is preferable, the vinyl aromatic compound polymer block is less than 10% by weight, preferably less than 8% by weight, more preferably less than 5% by weight. Is recommended. Further, in obtaining the electric wire coating material of the present invention, when the hydrogenated copolymer (1) is preferably excellent in blocking resistance, the vinyl aromatic compound polymer block is 10 to 40% by weight, preferably 13%. ~ 37
It is recommended to be wt%, more preferably 15-35 wt%.

Vinyl aromatic compound polymer block (A)
Is measured by, for example, a method of oxidatively decomposing the copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KO
LTHOFF, et al. J. Polym. Sci.
1,429 (1946)) by weight of the vinyl aromatic hydrocarbon polymer block component obtained (however, the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). Can be obtained from the following equation. Block weight of vinyl aromatic hydrocarbon (wt%) = (weight of vinyl aromatic hydrocarbon polymer block (A) in copolymer before hydrogenation / weight of copolymer before hydrogenation) × 1
00

The content of the vinyl aromatic polymer block (A) in the hydrogenated copolymer is determined by using a nuclear magnetic resonance apparatus (NMR) for the polymer after hydrogenation (Y. Tanaka,
et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1
The method described in 981) can be directly measured, but in the present invention, the value obtained by the osmium tetroxide decomposition method described above is the content of the vinyl aromatic polymer block (A). Content of vinyl aromatic polymer block (A) of copolymer before hydrogenation measured by osmium tetroxide decomposition method (referred to as "Os value") and copolymerization weight after hydrogenation measured by NMR method Between the contents of the combined vinyl aromatic polymer block (A) (referred to as “Ns value”),
There is a correlation.

As a result of studying various copolymers having different contents of the vinyl aromatic polymer block (A), the relationship can be represented by the following formula. Os value = -0.012 (Ns value) 2 + 1.8 (Ns
Value) -13.0 Therefore, in the present invention, when the content of the vinyl aromatic polymer block (A) of the polymer after hydrogenation is determined by the NMR method, the Ns value is set to the Os value based on the above formula. The vinyl aromatic polymer block (A) content was calculated. Also,
In the present invention, the block ratio of the vinyl aromatic compound in the hydrogenated copolymer (the block ratio means the ratio of the content of the vinyl aromatic compound polymer block to the total amount of the vinyl aromatic compound in the copolymer) Is less than 50% by weight,
Preferably 20% by weight or less, more preferably 18% by weight
The following is recommended in order to obtain a composition having better flexibility.

The weight average molecular weight of the hydrogenated copolymer (1) used in the present invention is 50,000 or more from the viewpoint of blocking resistance, mechanical strength and the like, and 100 from the viewpoint of molding processability.
It is less than 10,000. It is preferably 100,000 to 800,000, and more preferably 13 to 500,000. When a hydrogenated copolymer having a vinyl aromatic compound polymer block content of 10 to 40% by weight is used, its weight average molecular weight exceeds 100,000 and less than 500,000, preferably 130,000 to 400,000, and more preferably Is recommended to be 150,000 to 300,000. In the present invention, the molecular weight distribution of the hydrogenated copolymer is 1.5 in terms of moldability.
To 5.0 are preferable, more preferably 1.6 to 4.5,
More preferably, it is recommended to be 1.8-4.

Hydrogenated copolymer (1) used in the present invention
Is a hydrogenated copolymer obtained by adding hydrogen to a copolymer composed of a conjugated diene and a vinyl aromatic compound, and the hydrogenation rate of double bonds based on the conjugated diene compound in the hydrogenated copolymer is From the viewpoint of blocking resistance and scratch resistance of the hydrogenated copolymer used as the electric wire coating material, it is 75% or more, preferably 90% or more, more preferably 92% or more, and particularly preferably 95% or more.

The hydrogenated copolymer (1) of the present invention is a hydrogenated product having substantially no crystallization peak in the range of -50 to 100 ° C. in the DSC chart obtained by differential scanning calorimetry (DSC). Is preferred. here,
"There is substantially no crystallization peak in the range of -50 to 100 ° C" means that no peak due to crystallization appears in this temperature range, or a peak due to crystallization is observed, The crystallization peak calorific value due to the crystallization is less than 3 J / g, preferably less than 2 J / g,
It is more preferably less than 1 J / g, and most preferably has no crystallization peak calorific value. The hydrogenated copolymer having a crystallization peak becomes a polymer having extremely poor flexibility, and is not suitable for the purpose of the present invention, which is to develop a use of a soft vinyl chloride resin. In order to obtain a hydrogenated copolymer having substantially no crystallization peak in the range of −50 to 100 ° C. as described above, a vinyl bond amount adjusting agent as described below is used and conditions as described below are used. The non-hydrogenated copolymer obtained by carrying out the polymerization reaction may be used.

In the present invention, the structure of the hydrogenated copolymer is not particularly limited, and any structure can be used.
Particularly recommended is a copolymer having at least one structure selected from the following general formulas (1) to (5),
It is a hydrogenated copolymer obtained by adding hydrogen. The hydrogenated copolymer (1) used in the present invention may be an arbitrary mixture of a hydrogenated copolymer obtained by adding hydrogen to a copolymer having a structure represented by the following general formula. Further, a vinyl aromatic compound polymer may be mixed with the hydrogenated copolymer. (1) B (2) B-A (3) B-A-B (4) (B-A) _m- X (5) (B-A) _n- X-A _p (where B is a conjugate) It is a random copolymer block of a diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n is
And p are integers of 1 or more. X represents a coupling agent residue. )

In the general formula, the vinyl aromatic hydrocarbons in the random copolymer block B may be distributed uniformly or in a taper shape. In the copolymer block B, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed may coexist. Further, m is an integer of 2 or more, preferably 2 to 10, and n and p are 1 or more, preferably an integer of 1 to 10.

In the present invention, the difference between the maximum value and the minimum value of the vinyl bond content based on the conjugated diene in the copolymer chain before hydrogenation is less than 10%, preferably 8% or less, more preferably 6%. % Or less is recommended.
The vinyl bonds in the copolymer chain may be evenly distributed or tapered. Here, the difference between the maximum value and the minimum value of the vinyl bond content is the maximum value and the minimum value of the vinyl amount determined by the polymerization conditions, that is, the type and amount of the vinyl amount modifier and the polymerization temperature. The difference between the maximum value and the minimum value of the vinyl bond content in the copolymer chain can be controlled, for example, by the polymerization temperature during the polymerization of the conjugated diene or the copolymerization of the conjugated diene and the vinyl aromatic compound. For a given type and amount of vinyl modifier, such as a tertiary amine compound or ether compound, the vinyl bond content incorporated into the polymer chain during polymerization depends on the polymerization temperature.
Therefore, the polymer polymerized isothermally becomes a polymer in which vinyl bonds are uniformly distributed.

On the other hand, the polymers polymerized at elevated temperature have a heavy vinyl bond content such that the initial (polymerization at low temperature) has a high vinyl bond content and the latter half (polymerization at high temperature) has a low vinyl bond content. Be united. By adding hydrogen to the copolymer having such a structure, a hydrogenated copolymer having a specific structure can be obtained. In the present invention, the content of the vinyl aromatic compound can be known by using an ultraviolet spectrophotometer. The amount of the vinyl aromatic compound polymer block can be determined by the above-mentioned KOLTHOFF method or the like. The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation can be known using an infrared spectrophotometer (Hampton method). The hydrogenation rate of the hydrogenated copolymer can be known by using a nuclear magnetic resonance apparatus (NMR). In addition, in the present invention, the molecular weight of the hydrogenated copolymer is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring the standard curve of a commercially available polystyrene (standard curve). It is the weight average molecular weight obtained by using (prepared using the peak molecular weight of polystyrene). Similarly, the molecular weight distribution of the hydrogenated copolymer can be determined from the measurement by GPC.

In the hydrogenated copolymer (1) used in the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene and 2-methyl-1,3. -Butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,
2-Methyl-1,3-pentadiene, 1,3-hexadiene and the like, but particularly common ones are 1,3-
Butadiene and isoprene may be mentioned. These may be used alone or in combination of two or more. Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-
Examples thereof include diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, etc. These may be used alone or in combination of two or more.

In the copolymer before hydrogenation used in the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion can be arbitrarily changed by using a polar compound described later, and particularly, There is no limit. Generally, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is 5 to 80%, preferably 1
0-60%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used together, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally 3 to 75. %, Preferably 5-60% is recommended.

In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, if 1,3-butadiene is used as the conjugated diene,
-Vinyl bond content) is hereinafter referred to as vinyl bond content. In the present invention, the copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include n-butane, isobutane, n-pentane, n
Aliphatic hydrocarbons such as hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene Is.

As the initiator, an aliphatic hydrocarbon alkali metal compound or aromatic hydrocarbon alkali metal compound which is generally known to have anionic polymerization activity with respect to a conjugated diene compound and a vinyl aromatic compound is used. , Organic amino alkali metal compounds and the like are included, and the alkali metal is lithium, sodium, potassium and the like. Suitable organic alkali metal compound has 1 to 20 carbon atoms.
Is an aliphatic and aromatic hydrocarbon lithium compound of
A compound containing one lithium in one molecule, a dilithium compound containing a plurality of lithium in one molecule, a trilithium compound, and a tetralithium compound are included. Specifically, n
-Propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, reaction product of sec-butyllithium with diisopropenylbenzene object,
Further, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene may be mentioned.

Further, 1- (t-butoxy) propyllithium disclosed in US Pat. No. 5,708,092 and a lithium compound having 1 to several molecules of isoprene monomer inserted therein to improve its solubility, 1- (t disclosed in British Patent 2,241,239
-Butyldimethylsiloxy) hexyllithium and other siloxy group-containing alkyllithium, US Pat. No. 5,527,7
Amino lithiums such as the amino group-containing alkyl lithium, lithium diisopropylamide and lithium hexamethyldisilazide disclosed in the specification of No. 53 can also be used.

In the present invention, when a conjugated diene compound and a vinyl aromatic compound are copolymerized with an organic alkali metal compound as a polymerization initiator, a vinyl bond (1, 2, or 3,) resulting from the conjugated diene compound incorporated in the polymer is obtained. A tertiary amine compound or an ether compound may be added as an adjusting agent in order to adjust the content of (4 bonds) and the random copolymerizability of the conjugated diene compound and the vinyl aromatic compound. As the tertiary amine compound, a general formula R1R2R3N (wherein R1, R2 and R3 have 1 to 2 carbon atoms) is used.
0 hydrocarbon group or a hydrocarbon group having a tertiary amino group). For example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'- Tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine and the like. .

The ether compound is selected from linear ether compounds and cyclic ether compounds, and the linear ether compounds are dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether. And diethylene ether dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Further, as the cyclic ether compound, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, an alkyl of furfuryl alcohol. Examples include ether.

In the present invention, the method of copolymerizing the conjugated diene compound and the vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. May be. In particular, a continuous polymerization method is recommended in order to adjust the molecular weight distribution within a preferable appropriate range. The polymerization temperature is generally 0 ° C to
180 ° C, preferably 30 ° C to 150 ° C. Although the time required for the polymerization varies depending on the conditions, it is usually 48 hours or less, and particularly preferably 0.1 to 10 hours. or,
The atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a range of pressure sufficient to maintain the monomer and the solvent in the liquid phase within the above-mentioned polymerization temperature range. Further, it is necessary to take care so that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

In the present invention, the coupling reaction can be carried out by adding a required amount of a bifunctional or higher functional coupling agent at the end of the polymerization. The bifunctional coupling agent may be any known one and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. The trifunctional or higher polyfunctional coupling agent may be any known one and is not particularly limited. For example, trihydric or higher polyalcohols, epoxidized soybean oil, diglycidyl bisphenol A, 1,
Polyvalent epoxy compounds such as 3-bis (N, N'-diglycidylaminomethyl) cyclohexane, general formula R4-tSi
Yt (where R is a hydrocarbon group having 1 to 20 carbon atoms, Y
Is a halogen, and t is a silicon halide compound represented by 3 or 4), such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and bromides thereof, and the general formula R4-tSnYt (where R is A hydrocarbon group having 1 to 20 carbon atoms, Y is halogen, and t is 3 or 4)
And a polyvalent halogen compound such as methyltin trichloride, t-butyltin trichloride, tin tetrachloride and the like. Dimethyl carbonate or diethyl carbonate can also be used.

In the present invention, a terminal-modified copolymer in which a polar group-containing atomic group is bonded to at least one polymer chain end of the polymer can be used as the copolymer. As the polar group-containing atomic group, for example, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group , Amide group, sulfonic acid group, sulfonic acid ester group,
Phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group,
An atomic group containing at least one polar group selected from an alkoxysilicon group, a tin halide group, an alkoxytin group, a phenyltin group and the like can be mentioned. The terminal-modified copolymer is obtained by reacting a compound having these polar group-containing atomic groups at the end of the polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, a terminal modification treatment agent described in JP-B-4-39495 can be used.

By hydrogenating the copolymer obtained above, the hydrogenated copolymer used in the present invention can be obtained.
The hydrogenation catalyst is not particularly limited, and conventionally known metals (1) such as Ni, Pt, Pd and Ru are carbon,
A supported heterogeneous hydrogenation catalyst supported on silica, alumina, diatomaceous earth, etc., (2) Organic acid salts such as Ni, Co, Fe and Cr or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum. And a so-called Ziegler type hydrogenation catalyst, and (3) a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh and Zr. As a specific hydrogenation catalyst, Japanese Patent Publication No. 4
No. 2-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041.
The hydrogenation catalysts described in the publication can be used.
Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.

As the titanocene compound, Japanese Patent Application Laid-Open No. 8-1
The compounds described in Japanese Patent Publication No. 09219 can be used,
Specific examples include at least one or more ligands having a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds.
Further, as the reducing organic metal compound, an organic alkali metal compound such as organic lithium, an organic magnesium compound,
Examples thereof include organic aluminum compounds, organic boron compounds and organic zinc compounds.

In the present invention, the hydrogenation reaction is generally 0 to
It is carried out in a temperature range of 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is 0.1
~ 15.0 MPa, preferably 0.2-10.0 MP
a, and more preferably 0.3 to 5.0 MPa is recommended. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used as a batch process, a continuous process, or a combination thereof.

The solution of the hydrogenated copolymer obtained as described above can be separated from the solution by removing the catalyst residue if necessary. As a method for separating the solvent, for example, a method in which a polar solvent which is a poor solvent for the hydrogenated copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer, and the reaction solution is stirred Examples thereof include a method in which the solvent is removed by steam stripping to remove the solvent, and a method in which the polymer solution is directly heated to distill off the solvent. still,
The hydrogenated copolymer of the present invention includes various phenolic stabilizers,
Stabilizers such as phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added.

The hydrogenated copolymer used in the present invention comprises α,
It may be modified with a β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride thereof, an esterified product, an amidated product, or an imidized product. Specific examples of the α, β-unsaturated carboxylic acid or its derivative include maleic anhydride, maleic anhydride imide, acrylic acid or its ester, methacrylic acid or its ester, endo-cis-bicyclo [2,2,2].
1] -5-heptene-2,3-dicarboxylic acid or its anhydride. The addition amount of α, β-unsaturated carboxylic acid or its derivative is generally 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the hydrogenated polymer.
10 parts by weight.

Hydrogenated copolymer (1) used in the present invention
Is 1 to 99 parts by weight of the hydrogenated copolymer component (1), preferably 2 to 90 parts by weight, more preferably 5 to 70 parts by weight,
Component (2) 99-1 parts by weight, preferably 98-10 parts by weight, selected from a thermoplastic resin and / or a rubber-like polymer,
More preferably, it may be used as a composition containing 95 to 30 parts by weight. Among the components (2), as the thermoplastic resin, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound and a hydrogenated product thereof (provided that the hydrogenated copolymer of the present invention <component (1)> Polymers of the above vinyl aromatic compounds, other vinyl monomers of the above vinyl aromatic compounds, such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylic methyl such as acrylmethyl. Examples thereof include acid esters, methacrylic acid esters such as methacrylic acid and methyl methacrylate, and copolymer resins with acrylonitrile, methacrylonitrile and the like.

Rubber-modified styrene resin (HIP
S), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylic acid ester-butadiene-
Styrene copolymer resin (MBS), polyethylene, copolymer of ethylene containing 50% by weight or more of ethylene and other monomer copolymerizable therewith, for example, ethylene-propylene copolymer, ethylene-butylene copolymer , Ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolysates, polyethylene-polyethylene resins such as ethylene-acrylic acid ionomer and chlorinated polyethylene, polypropylene, 50% by weight of propylene Copolymers of propylene and the other monomer copolymerizable therewith, for example, propylene-ethylene copolymer, propylene-ethyl acrylate copolymer or polypropylene resin such as chlorinated polypropylene, ethylene-norbornene Cyclic olefin resin such as resin, polyb Resins, polyvinyl chloride resins, polyvinyl acetate resins and their hydrolysates, polymers of acrylic acid and its esters and amides, polyacrylate resins, polymers of acrylonitrile and / or methacrylonitrile, and these A nitrile resin that is a copolymer with another copolymerizable monomer containing 50% by weight or more of an acrylonitrile-based monomer can be used.

Furthermore, nylon-46, nylon-
6, nylon-66, nylon-610, nylon-1
1, polyamide-12 resin such as nylon-12, nylon-6 nylon-12 copolymer, polyester resin, thermoplastic polyurethane resin, poly-4,4'-dioxydiphenyl-2,2'-propane carbonate, etc. Polycarbonate polymer, thermoplastic polysulfone such as polyether sulfone and polyallyl sulfone, polyoxymethylene resin, poly (2,6-dimethyl-1,4-)
Polyphenylene ether resin such as phenylene ether, polyphenylene sulfide, polyphenylene sulfide resin such as poly 4,4'-diphenylene sulfide, polyarylate resin, polyetherketone polymer or copolymer, polyketone resin, fluorine resin Resin, polyoxybenzoyl polymer, polyimide resin, 1,
Examples thereof include polybutadiene resins such as 2-polybutadiene and trans polybutadiene.

The number average molecular weight of these thermoplastic resins is 1
000 or more, more preferably 5000 to 50
It is 0,000, and more preferably 10,000 to 1,000,000. Two or more of these thermoplastic resins may be used in combination. Of the component (2), the rubbery polymer includes butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product (however, the hydrogenated copolymer of the present invention <component (1)
>), Isoprene rubber, acrylonitrile-
Butadiene rubber and its hydrogenated products, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethiene-hexene rubber, ethylene-
Olefin elastomer such as octene rubber, butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β
-Styrene such as unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and hydrogenated product thereof, styrene-isoprene block copolymer and hydrogenated product thereof Examples include elastomers and natural rubber.
These rubbery polymers may be modified rubbers having functional groups.

The hydrogenated copolymer or composition used in the present invention contains a filler, a stabilizer, an antiaging agent, a light resistance improver, an ultraviolet absorber, a plasticizer, a softening agent, depending on the purpose.
Lubricants, processing aids, colorants, pigments, antistatic agents, flame retardants,
Antifogging agents, antiblocking agents, crystal nucleating agents, foaming agents and the like can be added. These can be used alone or in combination. Among the above, there is no particular limitation on the added amount of the stabilizer, the antiaging agent, the light resistance improver, the ultraviolet absorber, the lubricant, the colorant, the pigment, the antiblocking agent, the crystal nucleating agent, etc. From the viewpoint of balance, it is preferably 5 parts by weight or less.

Examples of the flame retardant that can be added to the composition used in the present invention include phosphorus type and inorganic type flame retardants. When used in the present invention, a flame retardant containing substantially no halogen is preferable, and the following are exemplified. As a phosphorus-based flame retardant, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol-bis-
(Diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethylmethyl phosphate, triallyl phosphate and the like and their condensates, ammonium and its condensate, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, red phosphorus and the like. It can be illustrated.

As the inorganic flame retardant, metal hydroxide such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide, zinc borate, barium borate, kaolin clay, calcium carbonate, alumite, basic magnesium carbonate, etc. Examples of the metal compounds include antimony-based flame retardants such as antimony trioxide, antimony pentaoxide, antimony pentaoxide, and sodium antimonate. Examples of other non-halogen flame retardants include nitrogen flame retardants such as guanidine compounds and melamine compounds, and silicone flame retardants such as silicone resins. Among these non-halogen flame retardants, metal oxides such as magnesium hydroxide are preferable from the viewpoint of improving flame retardancy.

Among the above flame retardants, there is also a so-called flame retardant aid, which has a low flame retardancy-developing effect by itself, but exhibits a synergistically superior effect when used in combination with another flame retardant. included. As the filler and flame retardant, it is possible to use a type in which surface treatment is performed in advance with a surface treatment agent such as a silane coupling agent. Further, the hydrogenated copolymer used in the present invention can also be used in a crosslinked state. In the crosslinked product, the decrease in the dielectric breakdown voltage due to the repeated impulses is further improved as compared with that before the crosslinking, and the number of times the repeated impulses are applied until the dielectric breakdown is further extended. As a method of crosslinking the hydrogenated copolymer used in the present invention, a known method can be adopted, and examples thereof include a method of irradiating with γ-rays and electron beams, and a method of using organic peroxide.

Specific examples of the above organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5. -Dimethyl-2,5
-Di- (tert-butylperoxy) hexyne-3,
1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis (tert-butylperoxy)
Valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate,
Examples thereof include tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and tert-butyl cumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (tert-) is preferable in terms of odor and scorch stability.
Butylperoxy) hexane, 2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-
3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
n-Butyl-4,4-bis (tert-butylperoxy) valerate is preferred, among which 1,3-bis (te
Most preferred is rt-butylperoxyisopropyl) benzene.

When the above organic peroxide is used for crosslinking, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene. Peroxy crosslinking aids such as diphenylguanidine, trimethylolpropane-N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be used in combination.

As a method for producing the electric wire coating material or the composition constituting the electric wire coating material of the present invention, a known method can be used. For example, it is possible to perform dry blending with various mixers, and a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a kneader, a multi-screw extruder, or a roll is used. A melt-kneading method, a method of dissolving or dispersing and mixing each component, and then removing the solvent by heating are used. In the present invention, the melt mixing method using an extruder is preferable from the viewpoint of productivity and good kneading property. The shape of the obtained electric wire coating material or the composition constituting the electric wire coating material is not particularly limited, and examples thereof include pellets, sheets, strands, and chips. Also,
It is also possible to directly form a molded product after melt-kneading.

The hydrogenated copolymers and crosslinked products thereof used in the present invention are used as electrical insulators having sufficiently improved electrical insulation properties, flexibility, abrasion resistance and scratch resistance. Specifically, it can be used as a covering material for electric wires, and in this case, it can be used as a covering material for electric wires used for both AC and DC power transmission cables. The electric wire of the present invention has a conductor coated with the electric wire coating material of the present invention, and can be used as a power cable, a communication cable, an AC power transmission cable, a DC power transmission cable, and the like. The electric wire coating material of the present invention preferably has a volume resistivity of 10 ¹⁵ Ω · cm or more.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, the structure and physical properties of polymers were measured as follows. 1) Styrene content It was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450) using the copolymer before hydrogenation.

2) Block content of styrene Using the copolymer before hydrogenation, I.M.Kolthoff, et al., J. Pol
ym.Sci.1, 429 (1946). 3) Vinyl bond content It was measured using an infrared spectrophotometer (FT / IR-230, manufactured by JASCO Corporation) using the copolymer before hydrogenation. In the case of a copolymer, it was calculated by the Hampton method, and in the case of a homopolymer, it was calculated by the Morello method.

4) Hydrogenation rate nuclear magnetic resonance apparatus (BRPXER, DPX-400)
Was measured using. 5) Molecular weight and molecular weight distribution GPC [apparatus manufactured by Waters] was used for measurement. Tetrahydrofuran was used as a solvent, and the measurement conditions were a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram. The molecular weight when there are a plurality of peaks in the chromatogram means the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram). The molecular weight distribution is the ratio of the obtained weight average molecular weight and number average molecular weight.

6) Crystallization peak and heat of crystallization peak The crystallization peak and the heat of crystallization peak of the hydrogenated copolymer are D
It was measured by SC (manufactured by Mac Science Co., Ltd., DSC3200S). Presence or absence of crystallization peak by raising the temperature from room temperature to 150 ° C. at a rate of 30 ° C./min and then decreasing the temperature to −100 ° C. at a rate of 10 ° C./min to measure the crystallization curve. It was confirmed. When there is a crystallization peak, the temperature at which the peak appears is taken as the crystallization peak temperature, and the heat of crystallization peak is measured.

7) Hardness According to JIS K6253, 1 with durometer type A
The value after 0 seconds was measured. 8) Tensile stress, tensile strength, elongation at break Measured according to JIS K6251 with a No. 3 dumbbell and a crosshead speed of 500 mm / min. 9) Measured at 23 ° C. according to Dunlop impact resilience BS903.

10) Scratch resistance Gakushin type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (glossy mirror surface) was rubbed 100 times with a friction cloth Kanakin No. 3 cotton and a load of 500 g, and the change in glossiness before and after rubbing was measured with a gloss meter. It was judged. ◎: Change in glossiness is within 0 to -5 ○: 〃 -5 over -10 within △: 〃 -10 over -50 within ×; 〃 -50 over

11) Abrasion resistance dynamic vibration type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (textured surface),
Friction cloth Kanakin No. 3 cotton was rubbed with a load of 500 g, and the volume reduction amount after rubbing was used to make a judgment according to the following criteria. ◎: Volume reduction amount is 0.01 ml or less after 10,000 times of friction ○: 〃 0.01 ml or more and 0.05 ml or less △; 〃 0.05 ml or more and 0.10 ml or less ×; 〃 0.10 ml or more What I did

12) Flame retardancy A flammability test according to UL94 was conducted, and ranked according to the UL94 criteria. 13) Heat Deformability A heat deformation test was performed according to JIS K6723.
The smaller the deformation rate (%), the better the heat resistance.

14) Compression set A compression set test was carried out in accordance with JIS K6262. The measurement conditions are a temperature of 70 ° C. and 22 hours. 15) Flex resistance A crack initiation test was performed in accordance with JIS K6260.
A dent having a radius of 2.38 mm was put in a strip piece having a length of 150 mm × a width of 25 mm and a thickness of 6.3 mm, and the crack length (mm) after bending 100,000 times was measured. Measurement temperature is 23 ℃
Is. Moreover, each compounded component is as follows.

<Component (1) -1> A hydrogenated copolymer was prepared by the following method. The hydrogenation catalyst used in the hydrogenation reaction in the following examples was prepared by the following method. A reaction vessel purged with nitrogen was charged with 1 liter of dried and purified cyclohexane, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. Then, the mixture was reacted at room temperature for about 3 days to obtain a hydrogenated catalyst.

Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and two tank reactors with jackets. From the bottom of the first reactor, a cyclohexane solution having a butadiene concentration of 24% by weight was fed at a feed rate of 4.51 L / hr,
A cyclohexane solution having a styrene concentration of 24% by weight was added to 5.
At a feed rate of 97 L / hr and at a feed rate of 2.0 L / hr, cyclohexane solution prepared by adjusting the concentration of n-butyllithium to 0.077 g per 100 g of monomer was further added. A cyclohexane solution of ', N'-tetramethylethylenediamine was supplied at a supply rate of 0.44 mol per mol of n-butyllithium, and continuous polymerization was performed at 90 ° C. The reaction temperature is adjusted by the jacket temperature, and the temperature near the bottom of the reactor is about 8
The temperature in the vicinity of the upper portion of the reactor was 8 ° C, and the temperature was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, the conversion of butadiene was almost 100%, and the conversion of styrene was 99%.

The polymer solution discharged from the first unit was fed from the bottom of the second unit, and at the same time, a cyclohexane solution having a styrene concentration of 24% by weight was fed at a feed rate of 2.38 L / hr.
It was fed to the bottom of the base and continuously polymerized at 90 ° C. The conversion rate of styrene at the outlet of the second unit was 98%. Next, the above hydrogenation catalyst is added to the polymer 1 obtained by continuous polymerization.
100 ppm of Ti was added per 100 parts by weight, and hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.

The hydrogenated copolymer obtained had a molecular weight of 200,
000, the molecular weight distribution was 1.9, the styrene content was 67% by weight, the block styrene content was 20% by weight, the vinyl bond content in the butadiene part was 14% by weight, and the hydrogenation rate was 99%.
From the analysis values of the styrene content and the block styrene content, the block ratio of styrene is 30%. As a result of DSC measurement, there was no crystallization peak.

<Component (1) -2> The supply amount of the styrene solution supplied to the first unit is changed to 2.06 L / hr, and the supply amount of the styrene solution supplied to the second unit is 1.37 L / hr. Continuous polymerization was carried out in the same manner as in the component (1) -1 except that it was changed, and then the hydrogenation reaction was carried out in the same manner as in the component (1) -1. The obtained hydrogenated polymer was analyzed and found to have a molecular weight of 20.
The content was 2,000, the molecular weight distribution was 1.9, the styrene content was 45% by weight, the block styrene content was 18% by weight, the vinyl bond content in the butadiene part was 15% by weight, and the hydrogenation rate was 98%. From the analysis values of the styrene content and the block styrene content, the block ratio of styrene was 33%.

<Component (1) -3> A cyclohexane solution containing 6.5 parts by weight of styrene (concentration: 24% by weight) was prepared by using the same reactor as that used for preparing the component (1) -1. Was thrown in. Then, n-butyllithium and tetramethylethylenediamine were added and polymerized at 50 ° C. for 1 hour, and then a cyclohexane solution containing 87 parts by weight of butadiene (concentration 24% by weight) was added and polymerized at 50 ° C. for 1 hour. A cyclohexane solution (concentration: 24% by weight) containing 6.5 parts by weight was added and polymerization was carried out at 50 ° C. for 1 hour.
Next, the obtained polymer was hydrogenated in the same manner.
The obtained hydrogenated copolymer had a molecular weight of 210,000, a molecular weight distribution of 1.1, a styrene content of 13% by weight, a block styrene content of 13% by weight, and a vinyl bond content of 7 parts in the butadiene part.
It was 3% by weight and the hydrogenation rate was 99%. From the analysis values of the styrene content and the block styrene content, the block ratio of styrene was 100%.

<Component (1) -4> Using the same reactor as that used for preparing the component (1) -1, a cyclohexane solution having a butadiene concentration of 24% by weight and cyclohexane of n-butyllithium. Solution and N, N, N ', N'
-Tetramethylethylenediamine in cyclohexane was continuously fed to the reactor to carry out continuous polymerization. The reaction temperature was adjusted by the jacket temperature, and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, and the conversion of butadiene was almost 100%. Next, the polymer obtained by continuous polymerization was subjected to hydrogenation reaction in the same manner. The obtained hydrogenated polymer had a molecular weight of 180,000, a molecular weight distribution of 1.9, a styrene content of 0% by weight, and a vinyl bond content of a butadiene portion of 22.
% By weight. <Component (1) -5> Polyvinyl chloride elastomer, Sumiflex K580
CF1 (Sumitomo Bakelite).

<Component (2) -1> Polypropylene resin <Homo PP>, PM801A (manufactured by Sun Allomer) MFR (230 ° C., 2.16 kg); 13 g / min. <Component (2) -2> As the polyphenylene ether resin, poly (2,6-dimethyl-1,4-phenylene) ether and reduced viscosity: 0.54 were used. <Component (2) -3> Polypropylene resin <Random PP>, PC630A
(Manufactured by Sun Allomer) MFR (230 ° C., 2.16 kg); 7.5 g / min.

<Component (2) -4> Hydrogenated product of styrene / butadiene block copolymer,
Tuftec H1221 (manufactured by Asahi Kasei) <Component (2) -5> Polystyrene resin <HIPS>, 475D (manufactured by A & M styrene) <Component (3) -1> Magnesium hydroxide, Kisuma 5A (manufactured by Kyowa Chemical Industry) <Component (3 ) -2> Triphenyl phosphate (manufactured by Daihachi Chemical Industry) <Component (4) -1> Organic peroxide, Perhexin 25B (manufactured by NOF Corporation) <Component (4) -2> Organic peroxide Object, Per Hexa 25B (Made by NOF Corporation)

[0069]

Example 1 Using component (1) -1 as a hydrogenated copolymer, rolling was performed with a 3.5 inch roll at 200 ° C., and then press molding was performed with a hydraulic press at 200 ° C. and 9.8 MPa. Then, a molded sheet having a thickness of 2 mm was prepared. The physical properties are shown in Table 1.

[0070]

Comparative Example 1 A molded sheet having a thickness of 2 mm was prepared in the same manner as in Example 1 except that the component (1) -2 was used as the hydrogenated copolymer. The physical properties are shown in Table 1.

[0071]

Examples 2 to 6 Component (1) -1 was used as a hydrogenated copolymer, and after mixing the components shown in Table 1 with a Henschel mixer, a twin screw extruder having a diameter of 30 mm was used to obtain 230 ° C (Example 2). ，
4 to 6) and 270 ° C. (Example 3) under melt kneading,
A pellet of the composition was obtained. Example 1 using this composition
A 2 mm-thick molded sheet was prepared in the same manner as in. The physical properties are shown in Table 1. Further, in Example 6, a strip (127 mm × 12.7 mm) was cut out from the molding sheet,
A flammability test according to UL94 was also performed. It is of V-0 rank and can be advantageously used particularly for wire coating materials that require flame retardancy.

[0072]

Comparative Examples 2 to 6 Component (1) -2 as a hydrogenated copolymer,
Using the components (1) -3 and (1) -4, the components shown in Table 2 were mixed in a Henschel mixer, and then melt-kneaded at 230 ° C. in a 30 mm diameter twin-screw extruder to obtain a composition. Pellets were obtained. Using this composition, a 2 mm thick molded sheet was prepared in the same manner as in Example 1. The physical properties are shown in Table 1.
Shown in.

[0073]

[Comparative Example 7] The procedure of Example 1 was repeated except that the component (1) -5 was used as the polyvinyl chloride elastomer.
A mm-thick molded sheet was prepared. The physical properties are shown in Table 1. From these results, it was found that the electric wire coating material of the present invention was excellent in strength, scratch resistance, abrasion resistance, flexibility, and peeling property. Further, it has been found that it exhibits almost the same behavior as the tensile stress of a polyvinyl chloride elastomer of the same hardness, has a feeling very similar to that of a polyvinyl chloride elastomer, and is effective as a substitute for it.

[0074]

Examples 7 to 9 Component (1) -1 was used as a hydrogenated copolymer, the components shown in Table 2 were mixed in a Henschel mixer, and then melted in a twin screw extruder having a diameter of 30 mm at 230 ° C. The mixture was kneaded to obtain pellets of the composition. Using this composition, a 2 mm thick molded sheet was prepared in the same manner as in Example 1. The physical properties are shown in Table 2.

[0075]

Example 10 Component (1) -1 was used as a hydrogenated copolymer in an amount of 5
0% by weight, 40% by weight of PPE of component (2) -2, and 10% by weight of triphenyl phosphate of component (3) -2 were mixed with a Henschel mixer, and then 270 with a twin-screw extruder having a diameter of 30 mm. Melt kneading was carried out under the condition of ° C to obtain pellets of the composition. When a flammability test was conducted using this composition,
It was V-0 rank.

[0076]

Example 11 In Example 10, 40 parts by weight of component (1) -1 was used, and instead of this, HIP of component (2) -5 was used.
A composition containing 10 parts by weight of S was prepared. Example 10
When a flammability test was conducted in the same manner as in 1., it was V-0 rank.

[0077]

Examples 12 and 13 Using the organic peroxide of the component 4 as a crosslinking agent, the hydrogenated copolymer was dynamically crosslinked to produce a crosslinked hydrogenated copolymer. The hydrogenated copolymer and the organic peroxide were mixed at the ratios shown in Table 3 and then melted and kneaded by a twin-screw extruder to obtain crosslinked hydrogenated copolymer pellets. The kneading temperature was the same as in Example 12.
220 ° C. in Example 13 and 210 ° C. in Example 13. The crosslinked hydrogenated copolymer was compression molded to prepare a 2 mm thick molding sheet, which was used as a test piece. In addition, a sheet with a thickness of 6.3 mm was separately prepared and used as a test piece for a bending resistance test. The physical properties of the test pieces were measured, and the results are shown in Table 3.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an electric wire coating material excellent in electric insulation, flexibility, abrasion resistance and scratch resistance. Further, it is possible to provide an electric wire, a power cable, and a communication cable coated with this coating material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01B 3/44 H01B 3/44 K N P F term (reference) 4J002 BB12X BB14X BB15X BC03X BP01W BP01X CH07X DE076 EW046 FD016 FD136 GQ01 4J026 HA06 HA15 HA16 HA20 HA26 HA32 HA39 HB06 HB15 HB16 HB20 HB26 HB32.

Claims (13)

[Claims] 1. A hydrogenated copolymer obtained by adding hydrogen to a copolymer of a conjugated diene and a vinyl aromatic compound,
An electric wire coating material comprising the hydrogenated copolymer (1) which is the following (a) to (d). (A) The content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less. (B) The amount of the vinyl aromatic compound polymer block in the hydrogenated copolymer is 40% by weight or less. (C) The weight average molecular weight of the hydrogenated copolymer is 50,000 to 100.
Ten thousand. (D) 75% or more of the double bond based on the conjugated diene compound in the hydrogenated copolymer is hydrogenated. 2. A composition comprising 1 to 99 parts by weight of the hydrogenated copolymer component (1) and at least one component (2) selected from the group consisting of thermoplastic resins and rubber-like polymers. Wire coating material. 3. The hydrogenated copolymer (1) is characterized by having substantially no crystalline peak in the range of −50 ° C. to 100 ° C. in differential scanning calorimetry (DSC). The electric wire coating material according to claim 1 or 2. 4. The hydrogenated copolymer (1) according to claim 1, wherein the amount of the vinyl aromatic compound polymer block (A) is less than 10% by weight. Wire coating material. 5. The hydrogenated copolymer (1) according to any one of claims 1 to 3, wherein the amount of the vinyl aromatic compound polymer block (A) is 10 to 40% by weight. The electric wire coating material described. 6. A hydrogenated copolymer obtained by adding hydrogen to the hydrogenated copolymer (1) having at least one structure selected from the following general formulas (1) to (5). The electric wire coating material according to any one of claims 1 to 5, wherein (1) B (2) B-A (3) B-A-B (4) (B-A) _m- X (5) (B-A) _n- X-A _p (where B is a conjugate) It is a random copolymer block of a diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n is
And p are integers of 1 or more. X represents a coupling agent residue. ) 7. The electric wire coating material according to claim 1, wherein the hydrogenated copolymer (1) has a crosslinked structure. 8. The volume resistivity of the hydrogenated copolymer (1) is
It is 10 ¹⁵ Ω · cm or more.
7. The electric wire coating material according to any one of 7. 9. The electric wire coating material according to claim 1, wherein the hydrogenated copolymer (1) contains a flame retardant. 10. The electric wire coating material according to claim 9, wherein the flame retardant is a halogen-free flame retardant. 11. An electric wire coated with the electric wire coating material according to any one of claims 1 to 10. 12. A power cable coated with the electric wire coating material according to any one of claims 1 to 10. 13. A communication cable coated with the electric wire coating material according to any one of claims 1 to 10.