JPS6041802B2 - insulated wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insulated wire, and more particularly to an insulated wire coated with an aromatic polyetheramide having good heat resistance, mechanical properties, and electrical properties.

Conventionally, thermosetting resins have been mainly used as coating materials for thin-walled insulated wires, and for coating, the thermosetting resin is dissolved in a solvent and the electrical wires that become conductors are passed through the resulting solution. A method has been adopted in which a film of solution is formed on the conductor surface and then the solvent is removed. However, when such a thermosetting resin is used as a coating material, there are drawbacks in the manufacturing process, such as difficulty in removing the solvent and a poor working environment. In contrast, thermoplastic resins can be coated onto conductors by heating and melting and extrusion molding without using solvents, so there is no need to remove the solvent as in the case of thermosetting resins. In addition, the manufacturing process can be simplified *(--()----) and they may be the same or different, and R and R6 represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and they are the same as each other. They may be present or different, and Ar is a p-phenylene group,
It has advantages such as m-hue door.

By the way, thin insulated wires are required to have excellent properties such as heat resistance, mechanical properties, electrical properties, chemical resistance, and abrasion resistance.

As a thermoplastic resin that satisfies these various properties,
Examples include fluororesins represented by tetrafluoroethylene-ethylene copolymers.

However, fluororesins generally have low surface hardness and insufficient cut-through resistance, which has been a major drawback. J The present invention was made in view of the current situation, and its purpose is to provide an insulated wire with excellent heat resistance, mechanical properties, and electrical properties, and especially excellent cut-through resistance. be.

In order to achieve the above object, the present invention has the following configuration.

That is, the insulated wire of the present invention is characterized in that a conductor is coated with an aromatic polyetheramide having a repeating unit represented by the following general formula. 0-
-NH''-Ar-'')-(I) Represents a nylene group, diphenylene ether group, diphenylene group or naphthylene group.

) In the present invention, the aromatic polyether amide having the repeating unit represented by the above general formula (I) is coated on a conductor with an aromatic dicarboxylic acid or its reactive acid derivative by general molding. Insulated wire as described in Range 1.

5. The insulated wire according to any one of claims 1 to 4, which is obtained by heat-melting an aromatic polyether amide having a repeating unit represented by the following formula and coating it on a conductor by extrusion molding.

(However, the carbonyl groups in the formula are mutually bonded to the benzene nucleus at the meta or rose position, and the carbonyl groups in the formula
20%, but the variation is 20-80%). DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insulated wire, and particularly to an insulated wire coated with aromatic polyetheramide having good heat resistance, mechanical properties, and electrical properties.

Conventionally, thermosetting resins have been mainly used as coating materials for thin-walled insulated wires, and for coating, the thermosetting resin is dissolved in a solvent and the electrical wires that become conductors are passed through the resulting solution. A method has been adopted in which a film of solution is formed on the conductor surface and then the solvent is removed. However, when such a thermosetting resin is used as a coating material, there are drawbacks in the manufacturing process, such as difficulty in removing the solvent and a poor working environment. On the other hand, thermoplastic resins
Since it can be heated and melted and coated on the conductor by extrusion molding without using a solvent, there is no need to remove the solvent as in the case of thermosetting resin, and the manufacturing process is also simplified. It has advantages such as: By the way, thin insulated wires are required to have excellent properties such as heat resistance, mechanical properties, electrical properties, chemical resistance, and abrasion resistance.

Examples of thermoplastic resins that satisfy these properties include fluororesins such as tetrafluoroethylene-ethylene copolymers.

However, fluororesins generally have low surface hardness and insufficient cut-through resistance, which has been a major drawback. The present invention has been made in view of the current situation, and its purpose is to provide an insulated wire with excellent heat resistance, mechanical properties, and electrical properties, and especially excellent cut-through resistance. .

In order to achieve the above object, the present invention has the following configuration.

That is, the insulated wire of the present invention is characterized in that a conductor is coated with an aromatic polyetheramide having a repeating unit represented by the following general formula. (However, R1 to R4 in the formula represent hydrogen, lower alkyl group, lower alkoxy group, chlorine, or bromine, and they may be the same or different, and R5 and R6 are hydrogen, methyl group, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different, and Ar represents p-phenylene group, m-phenylene group, diphenylene ether group. group, diphenylene group or naphthylene group.

) In the present invention, the aromatic polyether amide having a repeating unit represented by the above general formula (・) is composed of aromatic dicarboxylic acid or its reactive acid derivative and the general formula
1 to R6 mean the same as R1 to R6 in the general formula (1) above), the aromatic diamine having an ether bond is prepared by solution polymerization, melt polymerization, or
It can be obtained by condensation polymerization using a known method for producing aromatic polyamides, such as the method disclosed in Japanese Patent No. 23198.

As the aromatic diamine having an ether bond represented by the above general formula (■), for example, 2,2-bis[4-(4
-aminophenoxy)phenyl]propane, 2・2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2●2-bis[3-chloro4-(4-
aminophenoxy)phenyl]propane, 2,2-bis[3-bromo4-(4-aminopheninoxy)pheny,l]propane, 2●2-bis[3-ethyl-4-(4
-aminophenoxy)phenyl]propane, 2,2-bis[3-propyl-4-(4-aminophenoxy)phenyl]propane, 2●2-bis[3-isopropyl-4
-(4-aminophenoxy)phenyl]propane, 2●
2-bis[3-butyl-4-(4-aminophenoxy)
Phenyl]propane, 2●2-bis[3-Sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methoxy4-(4-aminophenoxy)phenyl]propane, 2● 2-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]propane, 2●2-bis[3●5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3
・5-dichloro4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]propane, 2,2
-bis[3,5-dimethoxy4-(4-aminophenoxy)phenyl]propane, 2●2-bis[3-chloro4-(4-aminophenoxy)-5-methylphenyl]propane, 1●1-bis[ 4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4
-(4-aminophenoxy)phenyl]ethane, 1●1
monobis[3-chloro4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-bromo4-(4
-aminophenoxy)phenyl]ethane, 1,1-bis[3-ethyl-4-(4-aminophenoxy)phenyl]ethane, 1●1-bis[3-propyl-4-(4-aminophenoxy)phenyl]ethane, 1・1-bis [3
-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 11-bis[3-butyl-4-(4-aminophenoxy)phenyl]ethane, 1●1-bis(3-
Sec-Butyl-4-(4-aminophenoxy)phenyl]ethane, 1●1-bis[3-methoxy4-(4-
aminophenoxy)phenyl]ethane, 1,1-bis[
3-ethoxy4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dimethyl-4-(4
-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro4-(4-aminophenoxy)phenyl]ethane, 1●1-bis[3●5-dibromo4
-(4-aminophenoxy)phenyl]ethane, 1.1
-bis[3,5-dimethoxy4-(4-aminophenoxy)phenyl]ethane, 1◆1-bis[3-chloro4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4- (4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro4-(4-aminophenoxy)phenyl]methane, bis[3-bromo4 -(4-aminophenoxy)phenyl]methane, bis[3-ethyl-4-(4-aminophenoxy)phenyl]methane, bis[3-propyl-4not(4-aminophenoxy)phenyl]methane, bis[
3-isopropyl-4-(4-aminophenoxy)phenyl]methane, bis[3-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-Sec-butyl-4-(4-aminophenoxy)phenyl] methane,
Bis[3-methoxy4-(4-aminophenoxy)phenyl]methane, bis[3-ethoxy4-(4-aminophenoxy)phenyl]methane, bis[3●5-dimethyl-4-(4-aminophenoxy)phenyl] Methane, bis[3,5-dichloro4-(4-aminophenoxy)phenyl]methane, bis[3,5-dibromo4-
(4-aminophenoxy)phenyl]methane, bis[3
●5-dimethoxy4-(4-aminophenoxy)phenyl]methane, bis[3-chloro4-(4-aminophenoxy)-5-methylphenyl]methane, 11●1◆
3◆3●3-hexafluoro2●2-bis[4-(4
-aminophenoxy)phenyl]propane, 1.1.1
・3,3,3-hexachloro2,2-bis[4-(4
-aminophenoxy)phenyl]propane, 3●3-bis[4-(4-aminophenoxy)phenyl]pentane, 1●1-bis[4-(4-aminophenoxy)phenyl]propane, 1◆1●1● 3●3●3-hexafluoro2,2-bis[3●5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.
3,3-hexachloro-2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 3●3-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane, 11-Bis [3.5
-dimethyl-4-(4-aminophenoxy)phenyl]
Propane, 1,1,1,3,3,3-hexafluoro2,2-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]propane, 1●1◆1●3.3◆
3-hexachloro2◆2-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]propane, 3
・3-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]pentane, 1●1-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]propane, 2◆2-bis[4 -(4-aminophenoxy)
phenyl]butane, 2,2-bis[3-methyl-4-(
4-aminophenoxy)phenyl]butane, 22-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dibromo4
-(4-aminophenoxy)phenyl]butane, 1.1
・1,3,3,3-hexafluoro2,2-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]propane and the like.

Furthermore, in the present invention, known diamines such as 4.4"
-Diaminodiphenyl ether, 4,4-diaminodiphenylsulfone, metaphenylenediamine, 4●4″-
At least one of di(4-hydroxyphenoxy) phenyl sulfone or 4◆4'-di(31-hydroxyphenoxy) phenyl sulfone can be used in combination.

Examples of aromatic dicarboxylic acids in the present invention include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid-4●4', diphenylsulfondicarboxylic acid-4.4''-1, and naphthalene dicarboxylic acid-1.5. However, terephthalic acid and isophthalic acid are commonly produced and can be preferably used.

In particular, a mixture of terephthalic acid and isophthalic acid is desirable from the viewpoint of fluidity of the resulting resin. In addition, the reactive acid derivative of aromatic dicarboxylic acid in the present invention means dichloride, dipromide, diester, etc. of the above-mentioned aromatic dicarboxylic acid. In the present invention, when a mixture of terephthalic acid and isophthalic acid is used, the mixing ratio of isophthalic acid having a carboxyl group at the meta position of the benzene nucleus and terephthalic acid having a carboxyl group at the distal position of the benzene nucleus is the former. 20-80% vs. the latter 80-80%
It is desirable to keep the content within the range of 20%, especially from the viewpoint of fluidity and processability.

Further, the reduced viscosity of the aromatic polyetheramide in the present invention (measured at 0.2y1dt130°C in dimethylformamide) is 0.4 to 1.8d11f11, preferably 0.
It is appropriate to set it within the range of 6 to 1.0d11y.

Such a resin has excellent fluidity during extrusion molding (coating) and can provide an insulated wire with good mechanical properties. The aromatic polyether amide in the present invention melts when heated and exhibits fluidity, so it can be made into pellets by extrusion molding, and the pellets are then used to form core wires using an extruder equipped with a crosshead.
conductor wire), approximately 0.15 to 0.2 TI$
A thin coated insulated wire with a thickness of t can be easily obtained.

In addition, aromatic polyether amide is dissolved in a suitable solvent,
It is also possible to apply this solution onto the conductor wire and remove the solvent by heating to form a coating. The insulated wire of the present invention has significantly superior cut-through resistance compared to conventional insulated wire coated with fluororesin, and also has excellent mechanical properties such as tensile strength, heat resistance, electrical properties and It also has excellent flame retardancy.

In addition, in the present invention, in order to improve the heat resistance and weather resistance of the insulated wire, a thermal decomposition inhibitor, an antioxidant, an ultraviolet absorber, etc. are mixed with the aromatic polyether amide of the present invention and coated on the conductor. or can be applied, and also a plasticizer,
A coloring agent, a lubricant, a flame retardant, etc. can also be used in combination.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way.

Example 1 (a) Production of aromatic polyether amide A stirring bar, thermometer, and dropping container were set in a 10' volume separable flask, and 154.8 q of sodium hydroxide was added.
A solution of 800 mt of water was put into a flask.

Next, 656y of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added to 3.4k of cyclohexanone.
9 was injected into the flask and cooled to -2°C. On the other hand, a solution of terephthalic acid dichloride 164q and isophthalic acid dichloride 164y dissolved in cyclohexanone 2.4k9 was added to the solution at a reaction temperature of 1.
The injection was made so that the temperature did not exceed 0°C. 3 hours after the start of dropping, 16.9q of benzoyl chloride was added to 50q of cyclohexanone.
After 2 hours, the reaction solution was poured into methanol to isolate the polymer. Reduced viscosity of the obtained polymer (0.2 qId in dimethylformamide
t (measured at 130°C) was 0.75d11y. (b
) Manufacture of insulated wire The aromatic polyether amide obtained in (a) was pelletized, and an extruder with a screw diameter of 28 φ equipped with a cross head was used to produce silver-plated copper wire with a diameter of 0.26 wr! A coating with a thickness of 0.5 to 0.2 wL was formed on the surface of the n core wire.

The properties of the obtained insulated wire are shown in the table below. Example 2 An aromatic polyether amide with a reduced viscosity of 0.75 d1Iy was produced in the same manner as in Example 1, except that the weight ratio of terephthalic acid dichloride and isophthalic acid dichloride was 3:7. An insulated wire was manufactured using the insulated wire.

Its characteristics are shown in the table below. Example 3 2● Instead of 2-bis[4-(4-aminophenoxy)phenyl]propane, bis[3,5-dimethyl-4-(
An aromatic polyetheramide having a reduced viscosity of 0.70 was produced in the same manner as in Example 1, except that 4-aminophenoxy)phenyl]methane was used, and an insulated wire was produced using this.

Its characteristics are shown in the table below. Comparative Example An insulated wire was produced in the same manner as in Example 1 using an ethylene-tetrafluoroethylene copolymer resin (Tefzelu 200, manufactured by Dapon Co., Ltd.).

Its characteristics are shown in the table below. Note: Tensile strength is ASTM-
Measured by D256, cut-through resistance is UL-S
ub? Measured with Ct758 at 3I1111R1155°C, and wear resistance was measured with 3mi1R1400y.

As is clear from the table, the insulated wire of the present invention has superior properties compared to conventional wires.

Example 4 A stirring bar, thermometer and dropping funnel were set in a 10f separable flask, and 171 liters of sodium hydroxide was added.
．． A solution of 8V dissolved in 800 ml of water was placed in a flask.

Next, 2,2-bis[4-(4-aminophnoenoxy)
A solution of 594 g of phenyl]propane and 66 da of 44''-diaminodiphenyl ether dissolved in 3.4 k9 of cyclohexanone was poured into the flask and cooled to -2°C.Meanwhile, 182 y of terephthalic acid dichloride and 182 y of isophthalic acid dichloride were dissolved in 2.4 k9 of cyclohexanone.
When the reaction temperature was 10% from the dropwise loading of the solution dissolved in 4kg
The injection was made so that the temperature did not exceed ℃. 3 hours after the start of dripping,
18.9q of benzoyl chloride to 500y of cyclohexanone
After a further 2 hours, the reaction solution was poured into methanol to isolate the polymer. The obtained polymer was granulated using an extruder to obtain pellets with a reduced viscosity of 0.78 dL1q. Using this, an insulated wire was manufactured in the same manner as in Example 1. Tensile strength is 9.8k91i, elongation 80
%, cut-through resistance was 3.0k9, and abrasion resistance was 550 times. As explained above, according to the present invention, heat resistance,
It is possible to provide an insulated wire with excellent mechanical properties and electrical properties, and especially excellent cut-through resistance.

Claims (1)

[Scope of Claims] 1. An insulated wire formed by coating a conductor with aromatic polyetheramide having a repeating unit represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 to R_4 in the formula represent hydrogen, lower alkyl group, lower alkoxy group, chlorine, or bromine, and they may be the same or different from each other. Further, R_5 and R_6 represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and they may be the same or different from each other, and Ar represents a p-phenylene group, m- Indicates a phenylene group, diphenylene ether group, diphenylene group, or naphthylene group.)2 A conductor is coated with an aromatic polyether amide in which R_1 to R_4 are water and R_5 and R_6 are methyl groups. An insulated wire according to claim 1. 3. The insulated wire according to claim 1 or 2, wherein the conductor is coated with an aromatic polyetheramide in which Ar is p-phenylene group and/or m-phenylene group. 4. The insulated wire according to claim 1, which is obtained by heat-melting aromatic polyether amide and coating the conductor by extrusion molding. 5. The insulated wire according to any one of claims 1 to 4, which is obtained by heat-melting an aromatic polyether amide having a repeating unit represented by the following formula and coating it on a conductor by extrusion molding. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, the carbonyl groups in the formula are mutually bonded to the benzene nucleus at the meta or para position, and 80 to 20% of the total repeating units are at the meta position and 20 to 80% are at the para position. ).