JP2001093340A - Electric wire and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric wire and its manufacturing method, improving in bonding performance between a core wire and a coating resin. SOLUTION: A method of manufacturing an electric wire comprise previously coating a core wire with an alkoxysilane compound and coating the surface thereof with a thermoplastic polyester based resin or its composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric wire having improved adhesion between a core wire and a covering resin, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resins, cross-linked polyethylene, and the like have been used as wire covering materials.

[0003] In the case of vinyl chloride resin, because of its excellent flexibility and flame retardancy, in recent years, environmental pollution with harmful substances generated at the time of disposal after use of materials has been seriously discussed. The negative effects of environmental pollution are more closely watched than the merits of vinyl chloride resin. Further, since the long-term heat resistance is insufficient, a change from vinyl chloride resin to another material has been strongly demanded.

On the other hand, crosslinked polyethylene is chemically crosslinked with conventional polyethylene to improve heat resistance, but it is difficult to impart flame retardancy and mechanical properties are insufficient, so that it is difficult to change to another material. There is a strong demand.

As an alternative to these, recently, the use of a thermoplastic polyester resin, which is excellent in heat resistance, mechanical strength, and relatively easy to impart flame retardancy as a wire covering material, has been studied. The adhesiveness to the core wire was poor, and the wire was insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide an electric wire having a core wire and an electric wire covering material excellent in adhesion, and a method for producing the same.

[0007]

The above object is achieved by an electric wire and a method for producing the same, wherein a core wire is previously coated with an alkoxysilane compound and then the surface is coated with a thermoplastic polyester resin or a composition thereof. Is done.

[Embodiment of the present invention]

The core wire used in the present invention is a conductor used for an electric wire, and usually includes, but is not limited to, a copper wire or a copper wire plated with nickel, for example.

The present invention is characterized in that the core wire is surface-coated with an alkoxysilane compound and then used for extrusion coating.

As the alkoxysilane compound, one or more of aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, vinylalkoxysilane, and allylalkoxysilane are used.

Examples of the aminoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl ) -Γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

Examples of the epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.
Glycidoxypropyltriethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Examples of the mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane.
And mercaptopropyltriethoxysilane.

Examples of the vinylalkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-Vinylpropyltrimethoxysilane and the like.

Examples of the allylalkoxysilane include γ-allylaminopropyltrimethoxysilane, γ-allylthiopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane and the like.

The alkoxysilane compounds that can be used in the present invention are not limited to the above-listed substances.
γ-aminopropyl trialkoxysilane, γ-glycidoxypropyl trialkoxysilane, γ-mercaptopropyl trialkoxysilane and the like are preferred. Particularly preferred is γ-glycidoxypropyl trialkoxysilane.

These alkoxysilane compounds may be directly applied to the surface of the core wire, but are preferably used in the form of a solution dissolved in a suitable solvent, for example, an aqueous solution or an alcohol solution. From the viewpoint of productivity, the surface treatment is preferably carried out by immersing the core wire in a solution, drying and removing the solvent after application, and using the resultant for extrusion coating, but is not particularly limited.

In the present invention, the thermoplastic polyester resin as a resin material for coating the core wire surface is preferably an aromatic polyester resin in view of heat resistance. Aromatic polyester is a polyester having an aromatic ring in a chain unit of a polymer, and is obtained by a condensation reaction containing aromatic dicarboxylic acid (or its ester-forming derivative) and diol (or its ester-forming derivative) as main components. The resulting polymer or copolymer.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 2,2 ' -Biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,
4'-diphenylisopropylidene dicarboxylic acid, 1,
2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,5-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-bipyridinecarboxylic acid Acid, and terephthalic acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, adipic acid, azelaic acid, sebacic acid, along with these aromatic dicarboxylic acids,
One or more dicarboxylic acids such as dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid can be used in combination.

The diol component includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
Preferred are dimer acid diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and mixtures thereof.

Specific preferred aromatic polyester resins include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and poly-1,4-cyclohexane dimethylene terephthalate. Other examples include dimer acid copolymerized polybutylene terephthalate, polytetramethylene glycol copolymerized polybutylene terephthalate, and the like.

Further, polybutylene terephthalate copolymerized with polybutylene terephthalate and polycaprolactone can also be mentioned.

The thermoplastic resin composition that can be used in the present invention includes the above aromatic polyester resin containing a flame retardant, an antioxidant, a heat stabilizer, a pigment, a crystal nucleating agent, a lubricant, a crosslinking agent and the like. It refers to a blended one, but is not limited to these additives.

As a method for coating the core material coated with the alkoxysilane compound with the thermoplastic resin composition, a conventionally known general resin coating method may be used.

In the manufacturing method of the present invention, the core wire is made of, for example, Ni-
It can also be applied to Ti-based (shape memory alloy) portable telephone antennas.

[0027]

Industrial Applicability The present invention relates to an electric wire having excellent adhesion between a core wire and an electric wire covering material and a method for producing the same, and is useful for automobiles, electric trains, electric appliances and the like.

[0028]

Embodiments will be described below with reference to embodiments. The evaluation of physical properties was performed according to the following methods. Adhesion between core wire and electric wire covering material: Of the covering length of 10 cm, 5 cm was peeled off to expose the copper wire, and copper was exposed to the remaining 5 cm of the covering layer at a tensile speed of 5 mm / min using a tensile tester. The adhesive strength was defined as the resistance when the wire was pulled out.

(Production example of polybutylene terephthalate copolymer obtained by copolymerizing dimer acid) 41 kg of 1,4-butanediol, 70 g of tetra-n-butyl titanate as a transesterification catalyst and 54 k of dimethyl terephthalate
g was charged into a transesterification tank and heated to 210 ° C. at a heating rate of 40 ° C. per hour, and the generated methanol was distilled out of the system to carry out a transesterification reaction. After almost complete distillation of methanol, tetra-
70 g of n-butyl titanate and dimer acid (PRIP
(OL1009, manufactured by Unichema)
The esterification reaction was carried out by heating to 230 ° C. at a rate of 20 ° C. per hour. Next, the reaction product was transferred to a polymerization machine, and the temperature was 250 ° C. and the degree of vacuum was 0.5 mmHg over 1 hour.
Then, polycondensation was carried out for 3 hours to obtain a polybutylene terephthalate copolymer obtained by copolymerizing 10 mol% of dimer acid.

Examples 1 to 12 and Comparative Examples 1 to 4 Using the thermoplastic polyester resin shown in Table 1, using a one-layer extrusion molding line for wire coating (screw diameter 30φ, copper core wire diameter 0.7φ), A coating test was performed to obtain a coated electric wire. The copper core wire was immersed in a solution prepared by dissolving the alkoxysilane shown in Table 1 in methanol and then dried to remove methanol before use.

The obtained coated electric wire was subjected to the evaluation of the adhesion between the core wire and the electric wire covering material. The results are also shown in Table 1.

[0032]

[Table 1]

(Notes in Table 1) 1: Composition of thermoplastic polyester resin: dimer acid copolymerized polyethylene terephthalate copolymer: see production examples. Polyethylene terephthalate: PBT124 PTMG copolymerized polyethylene terephthalate copolymer manufactured by Kanebo Gosen Co., Ltd. Polymer: Polypropylene P-280B caprolactone copolymer manufactured by Toyobo Co., Ltd. Polyethylene terephthalate-based copolymer: Polypropylene S-2001 manufactured by Toyobo Co. ) -Mercaptoalkoxysilane: γ-mercaptopropyltrimethoxysilane (SH6062, manufactured by Toray Industries, Inc.) Epoxyalkoxysilane: γ-crystalline hydroxypropyltrimethoxysilane (SH6040, Toray Corporation Koninku Bu Co., Ltd.)

Examples 13 to 15 and Comparative Example 5 A brominated acrylate oligomer (FR-0125, Dead) was added to 100 parts by weight of the polybutylene terephthalate copolymer obtained by copolymerizing the dimer acid obtained in the above production.
A composition obtained by blending 15 parts by weight of Sea Bromine (manufactured by Sea Bromine) and 5 parts by weight of antimony trioxide (ATOX-B, manufactured by Nippon Seimitsu Co., Ltd.) and using a 30φ screw diameter co-rotating rotary kneading extruder is used. An electric wire covering test was performed in the same manner as in Example 1 to obtain a covered electric wire.

The obtained coated electric wire was subjected to the evaluation of the adhesion between the core wire and the electric wire covering material. The results are also shown in Table 1.

Comparative Examples 6 and 7 Using the dimer acid copolymerized polybutylene terephthalate copolymer obtained in the production example, a coating test was performed on a copper core wire treated with the coupling agent shown in Table 2 in the same manner as in Example 1. Do
A covered electric wire was obtained.

The obtained coated electric wire was subjected to the evaluation of the adhesion between the core wire and the electric wire covering material. The results are also shown in Table 2.

[0038]

[Table 2]

As described above, when the electric wire coated with the alkoxysilane compound was coated with the thermoplastic polyester resin or its composition, the adhesion was improved.

Continuing from the front page (72) Inventor Masaki Yamamoto 4-1 Kanebocho, Hofu-shi, Yamaguchi Kanebo Gosen Co., Ltd. F-term (reference) 5G305 AA02 AB24 AB34 BA12 CA11 CB26 CD06 DA22 DA23 5G309 LA20 5G315 CA02 CA04 CB02 CC05 CC08 CD08 CD17 5G325 JA09 JC01

Claims (2)

[Claims] 1. An electric wire, wherein a core wire is coated with an alkoxysilane compound, and further coated with a thermoplastic polyester resin or a composition thereof. 2. A method for producing an electric wire, comprising: coating a core wire with an alkoxysilane compound in advance and coating the surface with a thermoplastic polyester resin or a composition thereof.