JPS6166314A - Method of producing magnet wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method of manufacturing magnet wire by a melt extrusion coating method, and specifically, K has excellent adhesion to conductive wires and K itself has excellent heat deterioration resistance. The present invention relates to a method of manufacturing a magnet wire having a coating layer.

[Conventional technology]

BACKGROUND OF THE INVENTION Polyester copper wire and polyester imide steel wire are known as coverings for magnet wires used for winding wires in electrical equipment, electronic communication equipment, electronic equipment, and the like. These magnet wires are often manufactured by a method in which a resin such as polyester or polyester copper wire is dissolved in a solvent, and the solution is applied onto a conductive wire and baked (so-called baking method).

However, in the baking method, the danger of fire and deterioration of the working environment due to the volatilization of the solvent cannot be avoided, and there are safety and occupational health problems, and the implementation of the baking method has been avoided in recent years.

Therefore, studies have been conducted on methods of forming a resin coating layer on conductive wires without using solvents.For example, a method of melt-extrusion coating with crystalline thermoplastic resin has been proposed; The obtained magnet wire has disadvantages such as poor heat resistance because it uses thermoplastic resin, and because the resin is crystalline, minute cracks are likely to occur in the coating layer when bending deformation is applied to the wire. However, the various characteristics required for a magnet wire could not be fully satisfied.

Under these circumstances, various studies have been conducted on methods of manufacturing wires that can satisfy the characteristic values of magnet wires without using solvents, and several improved methods have been developed (Japanese Patent Publication No. 10804/1983).

Japanese Patent Publication No. 58-46805 and Japanese Patent Publication No. 59-17486) have been proposed.

[Problem that the invention seeks to solve]

The present invention aims to solve the problem of environmental pollution caused by solvent volatilization in the same manner as the above-mentioned improvement method, and in particular, while adopting a solvent-free coating method, it sufficiently maintains the characteristics as a magnet wire. The aim is to provide a method that can produce a satisfactory wire. The present invention aims to provide a magnet wire that is particularly excellent in adhesion and heat deterioration resistance among the required characteristics of a magnet wire.

[Means for solving problems]

The present invention is a saturated linear polyester or a saturated linear polyamide in which the constituent units represented by the following general formula CI) are contained per 100 moles of all ester bonds or all amide bonds. A polymer containing 0.01 to 50 mol of a polymer is melt-extruded and coated onto a conductive wire to a thickness of 1 to 200 μm, and then irradiated with actinic rays to ensure good adhesion to the conductive wire and resistance to heat deterioration. Polyester or polyamide with good properties (Rsm(Rt)TI (However, R1 and R2 represent substituents to the benzene nucleus, and 1
organic residues of different valences, which may be the same or different. m,
n represents the number of substituents, and is a number of θ to 3, which may be the same or different. ) [Function] In the present invention, 90.01 to 50 moles of the above general formula (
The most important point is that the polymer composition containing the structural unit represented by I) and added with a crosslinking agent is used as the conductive wire coating resin. That is, the crosslinking agent is a compound with extremely high photochemical activity, and when a conductive wire is melt-extruded and coated with a polymer composition containing the crosslinking agent and then irradiated with actinic rays, the crosslinking reaction rapidly proceeds, resulting in a three-dimensional A tough coating layer consisting of a structure can be obtained.

The coating layer thus obtained has the characteristics that a magnet wire coating layer should have (flexibility, heat deterioration resistance).

The polymer not only satisfies all of the requirements (softening resistance, chemical resistance, dielectric breakdown voltage, etc.), but also has a strong affinity for the metals (CutAltAglAu, etc.) that make up the conductive wire, so it is highly conductive. Excellent adhesion between wire and coating layer,
Coupled with the toughness of the three-dimensional structure after photo-crosslinking, it exhibits excellent heat deterioration resistance. The reason why the above polymer exhibits a strong affinity for metals is that the N atom of the structural unit represented by formula (I) contained in the polymer has a tendency to easily participate in complex formation with the above metal. It is thought that.

In the saturated linear polyester or saturated linear polyamide used in the present invention, the structural unit of formula (I) is contained in an amount of 90.01 to 90.01 per 100 moles of total ester bonds or total amide bonds.
It is necessary to contain 50 moles. If it is less than 0.01 mole,
Cross-linking and/or polymerization due to light irradiation is unlikely to occur,
On the other hand, it is not necessary to exceed 50 moles. The preferred range is 0
．． The range is from 1 to 20 mol, particularly preferably from 0.5 to 10 mol.

Furthermore, when coating the conductive wire with the above polymer, the coating thickness should be 1 to 200 μm; if the coating thickness is less than 1 μm, it may be too thin and some or all of the above properties may be lost. On the other hand, if the coating thickness exceeds 200 μm, the light transmittance will be poor because it is too thick, and the light irradiation time cannot be increased unnecessarily from the viewpoint of productivity. The crosslinking state becomes non-uniform.

As a result, variations occur in the physical properties of the coating layer.

The present invention will be explained in more detail below.

First, regarding the polymer forming the coating layer, the saturated linear polyester constituting the polymer is, for example, the following dicarboxylic acid (or its ester-forming derivative) (C) and glycol or aromatic diol (or its ester-forming derivative). (6) by any conventionally known method, or by polymerizing lactone or oxycarboxylic acid (or its ester-forming derivative) (E) by any conventionally known method.

Examples of (C) above in acid form include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, (5-sodium sulfo)isophthalic acid, succinic acid,
In addition to adipic acid, sepathic acid, dodecanedioic acid, etc., dicarboxylic acids containing an imide ring in the molecule are also used.

Examples of Q)) above in the form of glycol or aromatic diol include ethylene glycol, trimethylene glycol, 1,2-, 'robylene glycol, tetramethylene glycol, hexamethylene glycol, neohentyl glycol, 1,4 -cyclohexanediol, 1.4
- Cyclohexane dimetatool, diethylene glycol, triethylene glycol, polyethylene glycol (
Polytetramethylene glycol (molecular weight 10.000 or less) resorcinol, hydroquinone, 2,2-his-(4,4'-hydroxyphenyl)propane, and the like.

Examples of (g) above include β-propiolactone, ε-caprolactone, m- or p-hydroxybenzoic acid, N-
Examples include hydroxyethyl trimellitic acid imide.

In addition, the saturated linear polyester used in the present invention (before processing) does not contain trifunctional or higher functional units, such as residues of glycerin, pentaerythritol, trimellitic acid, pyromellitic acid, etc., to the extent that it can be substantially melt-molded. It's okay to stay.

On the other hand, the following compounds are used as the monomer or its precursor (ie, crosslinking agent) for introducing the structural unit of formula (I) into the saturated linear polyester.

That is, benzophenonetetracarboxylic acid containing or not containing a substituent in the aromatic nucleus, and/or its derivative (preferably an acid anhydride), and one primary amino group and at least one ester forming property in the molecule. It is produced from a compound (B) having a functional group and is represented by the general formula (■).

Here, R3 and R4 are aliphatic, alicyclic, or aromatic divalent residues having 1 or more carbon atoms, usually 1 to 20, and include ether bonds, ester bonds, amide bonds, imide bonds, etc. (, R3 and R4 may be the same or different. x and Y are a hydroxyl group (or/and an ester thereof) or a carboxyl group (or/and an ester thereof, an acid hashide, etc.) , X and Y may be the same or different.R2,HR represents a substituent to the benzene nucleus and is a monovalent organic residue, preferably a fatty acid having 1 or more carbon atoms, usually 1 to 10 carbon atoms. monovalent group, aromatic or alicyclic residues, which may be the same or different. m.

n represents the number of substituents, each representing a number of '0 to 3, and may be the same or different. In order to explain formula (■) more specifically, raw material (6) is given as a specific example. Alkanolamines having 2 to 10 carbon atoms, such as monoethanolamine, propatool amine, butanolamine, etc. Amino acids such as glycine, β-alanine, γ-amino n-
Examples include butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, and the like.

The polymer forming the coating layer is produced by adding a crosslinking agent represented by formula (111) to the above (C) and (2) [or/and (E)]. For example, an ester-forming derivative such as a dicarboxylic acid or a lower alkyl ester thereof and an alkylene glycol are heated together with a catalyst to form a glycol ester, which is then heated under high vacuum at a high temperature above the melting point. The compound of formula (Vm) can be added and reacted at any stage of the above reaction. However, when the compound of formula (Vl) contains a carboxyl group, it goes without saying that it is preferably added after the transesterification reaction between dialkyl carboxylate and alkylene glycol has been completed. Formula (
When adding the compound 111), it is heated sufficiently at a temperature higher than the melting point of the resin to carry out the transesterification reaction (including acidolysis and alcoholysis), and then heated again usually at high temperature and under high vacuum. Polymerize.

In addition, in addition to using the compound of general formula (Wl), it is also possible to react the above-mentioned compound as a raw material, a mixture of (8), or an amic acid as an addition compound during the polymerization step. In addition, after melt polycondensation, resin chips and/or
Alternatively, the powder can be further subjected to solid phase polymerization by a conventionally known method.

In the present invention, when producing a saturated linear polyester, metals or their compounds (such as oxides, hydroxides, carboxylates, alcoholades, halides,
complex salts, double salts, etc.) are used as catalysts. Ca as a transesterification catalyst.

Carboxylate salts (e.g. acetate, butyrate), alcolade complex salts, double salts, etc. of Sr%Ba%Zn, Mn, Pb, Ti, etc. are used, but especially calcium acetate, zinc acetate,
Manganese acetate, potassium oxalate titanate, and the like are preferred.

Examples of the polycondensation catalyst include antimony trioxide, germanium dioxide, lead dioxide, potassium oxalate titanate, and the like. In addition, amines (triethylamine, pyridine, morpholine, etc.) can be used as ether bond formation inhibitors.
, alkali metal carboxylates (eg, potassium terephthalate, sodium acetate, lithium acetate, etc.), phosphoric acid, phosphorous acid, phosphonic acid, and esters thereof can also be used as stabilizers. The amount of the catalyst used is usually 0.001 to 0.1 mole based on the total acid components, preferably o, oo
s~o,'os morchi.

The intrinsic viscosity of the saturated linear polyester obtained as described above is phenol/sym-tetrachloroethane=60/
Measured at 30℃ in 40 (weight ratio), usually 0.3 to L5
dl/g.

- The saturated linear polyamide constituting the aromatic polymer is, for example, the dicarboxylic acid shown below (or its amide-forming derivative)
(G) and diamine (or amide-forming derivative thereof) (
6) by any conventionally known method, or by polymerizing lactone or amino acid (J) by any conventionally known method.

Examples of the above (G) in the form of acids include terephthalic acid, isophthalic acid, 7-thalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, (6-sodium sulfo)isophthalic acid, succinic acid,
In addition to adipic acid, heptapathic acid, dodecanedioic acid, etc., dicarboxylic acids containing an imide ring in the molecule are also used.

Examples of (6) above in the form of diamines include ethylene diamine, propylene diamine, tetramethylene diamine, hequinamethylene diamine, bolier, ethylene oxide diamine, polytetramethylene oxide diamine, p
(or O-or m-)xylene diamine, p-
(or 0-or m) phenylenediamine, 4.
Examples include 4'-diaminodiphenylmethane.

The above (for example, C-caglolactam, glycine,
Examples include β-alanine, r-amino-n-butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, and the like.

On the other hand, the following compounds are used as monomers or amic acid precursors thereof (i.e., crosslinking agents) for introducing the structural unit of formula (I) into the saturated linear polyamide. That is, the formation of substituted or unsubstituted pen siphenotetracarboxylic acid or/and its derivative (preferably an acid anhydride) (A) and at least one primary amino group and at least one amide bond in the molecule. It is produced from a compound (F) having a sexual functional group and is represented by the general formula (ff).

Here, R1 and Ra are aliphatic, alicyclic, or aromatic divalent residues having 1 or more carbon atoms, usually 1 to 20 carbon atoms, and include ether bonds, ester bonds, amide bonds, imide bonds, etc. R8 and R6 may be the same or different. X', Y' are -grade or secondary amino groups (or/and amides thereof) or carboxyl groups (or/and esters, amides, acid halides, etc. thereof), and
' and Y' may be the same or different. R1 and R2 represent substituents to the benzene nucleus and have 1 or more carbon atoms, usually 1 to 1
0 aliphatic, aromatic or alicyclic monovalent residues which may be the same or different. m and n represent the number of substituents and indicate the number of each O to 3, which may be the same or different, and to be more specific, to explain the formula (ff), the number of carbon atoms is indicated by the raw material (F) Diamines having 2 to 10 carbon atoms, such as ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, etc., amino acids having 2 to 10 carbon atoms, such as glycine, β-alanine, γ-amino-n-butyric acid,
Examples include p-aminobenzoic acid and 1m-aminobenzoic acid.

The polymer forming the coating layer is produced by adding a crosslinking agent represented by formula (W) to the above (G) and (6) [or/and (J)]. For example, a nylon salt of a dicarboxylic acid and a diamine is synthesized, heated under pressure in the coexistence of water to form a low polymer, and then the pressure is gradually released to perform polycondensation to increase the molecular weight. Since the compound represented by the formula (IK) contains an amino group and/or a carboxyl group at the terminal, the same operations as those for ordinary amine compounds and carboxylic acids may be performed. In the case of lactams, ring-opening polymerization can usually be carried out in the presence of water (if necessary in the presence of an alkali metal or alkaline earth metal), and is usually carried out by heating under normal pressure. An amine salt of the compound (IK) can be added at any stage to copolymerize.

The relative viscosity of the saturated linear polyamide obtained as described above is usually 2.0 to 3.0 when measured at 20 DEG C. in a concentrated sulfuric acid solution of POV amide 1.

The polyester or polyamide for producing the magnet wire according to the present invention is not a saturated linear polyester or a saturated linear polyamide containing the structural unit of formula (I) in its molecular chain, but a polyester or polyamide of the formula Does not contain (or contains) the structural unit of (I)
It may also be a mixture with other polyesters or polyamides.

In the polyester or polyamide polymer of the present invention,
Lubricants, ultraviolet absorbers, antioxidants, antistatic agents, glass fibers, carrier fibers, foaming agents, other resins (e.g. polyolefins (polyethylene, polypropylene, etc.), rubber polymers 1 [polyisoprene, (polyacrylonitrile/butadiene) ), polybutadiene, poly(styrene/butadiene), etc.], polyamide resin (nylon 6,
nylon 6, 6, nylon 11, nylon 12, etc.)
Thermoplastic polyester elastomer (polyethylene terephthalate-polyethylene glycol block copolymer, polyethylene terephthalate-polybutylene glycol block copolymer, polybutylene terephthalate-polyethylene glycol block copolymer, polybutylene terephthalate-polybutylene glycol block copolymer) Thermoplastic elastomers such as thermoplastic polyurethane distomers and polypropylene oxides, polycarbonate resins, polyorganosiloxanes, fluorine-based polymers, pigments, dyes, flame retardants, etc. can be included.

In the present invention, the polymer forming the coating layer is constructed as described above, but in manufacturing the magnet wire, the molten polymer is extruded and coated onto the conductive wire, and the resulting coated wire is exposed to actinic light. irradiation to crosslink the coating layer.

Incidentally, the light irradiation can be carried out by a method known per se, and as a light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, sunlight, etc. is used, and the wavelength is usually 200 mμ.
~400mμ ultraviolet light (particularly preferably 310~400mμ)
m, u,' are preferred, but other electromagnetic waves can be used as well. There are no particular limitations on the conditions for light irradiation in the present invention, ie, the irradiation time, irradiation atmosphere, etc. Does the irradiation time depend on the physical properties required for the product? , can be arbitrarily determined between 0.1 seconds and 30 minutes. Even under an oxygen atmosphere, the crosslinking and/or polymerization reactions of the present invention are not significantly inhibited. In terms of irradiation efficiency, it is preferable to conduct the irradiation at a temperature that is higher than the glass transition temperature and lower than the melting point of the molded product before irradiation.

The irradiation amount is usually 1O~500W/mfi, preferably 5
0 to 300 W/m".

It is convenient for the process to carry out the light irradiation online during the extrusion coating process. After the polymer is melt-extruded and coated onto the conductive wire, the light irradiation is carried out to crosslink the coating layer before the wire is wound up.・Can be cured and rolled up.

〔Example〕

Examples 1-3 30.6 kg (493.0 mol) of ethylene glycol.

Terephthalic acid 4 x-okg (246.8 mol), antimony trioxide 18.0 g (0,0617 mol), triethylamine 74.9 g (0,7404 mol), trimethyl 7-Ox-okg (0,0321 mol) mol) into a reaction vessel, and at a temperature of 220 to 240°C, 3.5
Esterification reaction was carried out for 2 hours while pressurizing to kg/ctl. After returning to normal pressure, insert the screws (N, N'
-(β-hydroxyethyl))benzophenone tetracarboxylic acid imide 3.036 kg (7.43 mol), antioxidant (Ciba Geigy, Ionox 330) 10
After adding 1.364 kg (22.0 mol) of ethylene glycol and stirring at the same temperature for 10 minutes, the mixture was transferred to a polymerization pot. Then at 260°C and 300 T for 12 minutes.
After the pressure was reduced to 5 Torr over 49 minutes, the initial polycondensation reaction was carried out for 15 minutes while maintaining the temperature at 260° C. under the same reduced pressure. Next, the temperature was raised to 280°C and the pressure was reduced to 0.3 Torr to carry out a polycondensation reaction for 50 minutes, resulting in a melting point of 249°C, phenol/1
, 1,2.2-tetrachloroethane = 6/4 (weight ratio)
Intrinsic viscosity measured at 30°C in a mixed solvent of: 0
．． A copolymerized polyester of 648 d//g was obtained.

The above copolymerized polyester was processed using a melt extruder.
A 5 mmφ Cu wire was extrusion coated and rapidly cooled in water at 20° C. to produce an insulated wire having a resin coating with a thickness of 20 It m. This insulated wire was irradiated with ultraviolet rays under the following conditions.

Irradiation conditions Light source = 7 Eugene D-pulp lamps were installed in parallel on both sides of the insulated wire.

Distance from the light source to the insulated wire: 103 meters Running speed of the insulated wire during irradiation: 1 m/min, 2 m/min, 3 m/min Then, each of the above insulated wires was wound around a round bar with a diameter of 7.5 cm. It was placed in an oven at 130°C and crystallized for 16 hours. Table 1 shows the results of measuring the characteristics of each magnet wire thus obtained according to JIS-C-3211 (polyurethane copper wire).

Comparative Example 1 Table 1 shows the results of the same measurements performed on the insulated wire that was not subjected to ultraviolet irradiation and crystallization treatment in the above example.

Example 4 Bis-(N,N'
Examples 1 to 3 using 3.659 g of -(i-carboxypropyl))benzophenone tetracarboxylic acid imide.
Copolymerized polyester (intrinsic viscosity 0.660
de/g) was obtained. This copolymerized polyester was coated on a 0.5-φ Cu wire in the same manner as in Examples 1 to 3, and the properties of a magnet wire obtained by applying ultraviolet ray irradiation and crystallization treatment were measured in the same manner. Shown in the table.

As shown in Table 1, among Examples 1 to 3, those with slower running speeds (in other words, the longer the irradiation time), the more the photocrosslinking reaction progressed and the better the heat deterioration resistance. In addition, in Example 4 using a different type of crosslinking agent, although the gel fraction was lower than in Example 1, the same excellent heat deterioration resistance was obtained.

Furthermore, Examples 1 to 4 all exhibit excellent chemical resistance and dielectric breakdown voltage. In contrast, Comparative Example 1 has heat deterioration resistance,
Both chemical resistance and dielectric breakdown voltage were not satisfactory.

〔Effect of the invention〕

The present invention is constructed as described above and is flexible.

Magnet wires that satisfy all the characteristics that magnet wires should have, such as deterioration resistance, softening resistance, chemical resistance, and dielectric breakdown voltage, can be manufactured without using solvents, contributing to pollution prevention. can do.

Claims (1)

[Scope of Claims] A saturated linear polyester or a saturated linear polyamide containing 0.01 to 50 structural units represented by the following general formula (I) per 100 moles of total ester bonds or total amide bonds. A conductive wire is melt-extruded and coated with a polymer containing a molar ratio of 1 to 200 μm in thickness, and then irradiated with actinic rays. A method for producing a magnet wire, comprising forming a polyamide coating layer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R^1 and R^2 represent substituents to the benzene nucleus, are monovalent organic residues, and may be the same or different. ,
n represents the number of substituents, is a number from 0 to 3, and may be the same or different. )