JPS6027127B2 - insulated wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an insulated wire having a novel crosslinked insulating film, particularly an insulated wire for winding.

Prior art and its problems At present, windings are made by using an insulating paint made by dissolving a polymer or prepolymer in an organic solvent, squeezing it onto a conductor with a die or felt, applying it, and baking it.

Continuing to manufacture winding wires using large amounts of organic solvents at the current pace is becoming increasingly difficult year by year due to problems such as air pollution, and it is important to manufacture winding wires without using solvents as much as possible. desired. Furthermore, attempts are always being made to manufacture insulated wires at high speed in order to reduce costs.
A chemical consideration of manufacturing windings at high speeds using conventional solvent-based paints reveals the following major problems. That is, when an electric wire is run through the furnace at high speed, the electric wire can only stay in the furnace for a very short time. It is extremely difficult to heat the wire to the clumping temperature within such a short period of time while evaporating the solvent, and to properly cure the film at that temperature. At the same time, cracks, foaming, and scratches on the wire coating
There shall be no defects. In particular, conventional coatings for winding wires are cured by heating through polycondensation reactions and/or polyaddition reactions, and it is difficult to cure them in a short period of time due to reaction rate constraints. On the other hand, demands for the price and characteristics of insulated wires are becoming increasingly strong, and for example, there is a strong desire for insulated wires that can be manufactured at high speed and require fewer draws, and that have low material costs.

Furthermore, the problem of air pollution has become serious, and it has become increasingly difficult to use conventional paints that use large amounts of solvents in the production of insulated wires. Structure of the Invention and Its Effects The present inventor has completed the present invention as a result of intensive study on these points.

That is, the present invention provides a high molecular weight linear polyesterimide having a polymerizable unsaturated bond in the molecule, wherein at least one molecule of the polyesterimide has two or more unsaturated bonds. A cross-linked insulation obtained by coating an insulating composition containing polyesterimide as a main component on a conductor directly or through another insulator, and reacting the polymerizable unsaturated bonds of the polyesterimide. Insulated wire with a coating.

Since the insulating composition used in the present invention is crosslinked and cured by a radical reaction, it can be cured in a shorter time than conventional insulating compositions for wire windings which are thermally cured by polycondensation or polyaddition reactions. It can also be cured by irradiation with radiation such as ultraviolet rays, electron beams, etc.

That is, when thermal energy is used, a reaction initiator for polymerizable unsaturated bonds is added in advance to the insulating composition of the present invention. The reaction initiator is activated by thermal energy, and the generated radicals cleave the unsaturated bonds of the high molecular weight linear polyesterimide having polymerizable unsaturated bonds and the monomer or prepolymer, and crosslinking progresses by radical addition reaction. This can be expressed as a general formula as follows.

Reaction initiator: R・R energy wave. (Generation of radicals) (1) Insulating composition of the present invention: In addition, when radiation irradiation such as ultraviolet rays or electron beams is used, the polymerizable unsaturated bonds of the insulating composition are activated by the energy of the radiation, and radicals are generated. , crosslinking progresses through an addition reaction.

That is, since the present invention uses a polymer having an imide group in its molecule, it has better heat resistance than unsaturated polyesters conventionally known for use in impregnated varnishes. Furthermore, since the polymer is linear, it is melted by heating before crosslinking and curing.
Therefore, not only can it be used as a paint by dissolving it in a solvent as in the past, but it can also be coated onto a conductor using an extruder or the like without using a paint. The insulated wire of the present invention has excellent properties not only for winding but also for other insulated wire applications.

The reason why high molecular weight linear polyesterimide, which always has a polymerizable unsaturated bond, is used as one of the basic materials in the present invention is that the insulating composition of the present invention is coated on a conductor, and the conductor is coated with the insulating composition of the present invention, and is This is because the insulating film can withstand mechanical force when passing through guide rollers or the like or bending during the manufacturing process without being torn. Another reason is that it has favorable effects on the heat resistance and manufacturing process of insulated wires. The good mechanical properties of high-molecular-weight linear polymers mean that they can be used, for example, as an upper layer for double-coated insulated wires, such as polyesters such as polyethylene terephthalate, polyamides such as 6-6 nylon, or single-coated polyamideimides, double-coated insulated wires, etc. This fact is clear from examples such as heavily coated polyamideimide. Good mechanical properties have become one of the essential factors for insulated wires in today's situation where the use of high-speed automatic winding machines has become commonplace. Furthermore, the purpose of using at least one kind of monomer or prepolymer having a polymerizable unsaturated bond is to improve the reaction time in the crosslinking process and the properties of the obtained crosslinked insulating film while taking advantage of the above characteristics. .

On the insulated wire of the present invention, an insulating layer of polyethylene terephthalate, 6,6-nylon, polyamideimide, etc. may be further provided by a known method to obtain a double-coated insulated wire, or phenoxy resin, polyvinyl butyral resin, copolymer, etc. Of course, it is also possible to provide a self-fusing layer typified by polyester resin, copolymerized polyamide resin, etc. by a known method to make a self-fusing insulated wire.

The insulating composition used in the present invention can also be used as the resin for the self-bonding layer. In this case, a self-bonding insulated wire is made using a non-reactive composition that does not contain a reactive initiator, which will be described later, and then a reaction initiator is added to the self-bonding layer, and crosslinking is carried out at the same time as fusion during heating. With this, a product with excellent fusing strength at high temperatures can be obtained. The high molecular weight polyesterimide having a polymerizable unsaturated bond in the molecule used in the present invention is a dicarboxylic acid component or a dicarboxylic acid component or one or more of its derivatives (a part or may be replaced entirely with oxycarboxylic acid or its derivative) and one or more diols or derivatives thereof as the diol component, at least one of these dicarboxylic acid components or diol components It is obtained by always using a compound having a polymerizable unsaturated bond in the molecule and at least one imide group in the molecule.

The synthesis reaction of a high molecular weight esterimide having one or more polymerizable unsaturated bonds in the molecule used in the present invention can be expressed by the following general formula using dicarboxylic acid as the dicarboxylic component and diol as the diol component. .

However, RA represents a carboxylic acid residue.

i.e. one or more dicarboxylic acid residues, R.A.
1, RA2,..., RAn. RB represents a diol residue. That is, it represents a general term for one or more diol residues, RB1, RB2, . . . , RBn. Here, at least one of RA or RB, that is, at least one of RA1,..., RAn, RB1,...RBn has a polymerizable unsaturated bond in the molecule, and at least one has an imide group in the molecule. has. Among divalent carboxylic acid components, examples of saturated dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, suberic acid, azelaic acid, sebacic acid,
Brassylic acid, phthalic acid, isophthalic acid, terephthalic acid, benzophenone 2,4'-dicarboxylic acid, benzophenone 4,4'-dicarboxylic acid, diphenic acid, naphthalene dicarboxylic acid, dinaphthyl ketone 2,2 dicarboxylic acid, pentadecane dicarboxylic acid, tetracosane dicarboxylic acid Carboxylic acids, cyclohexanedicarboxylic acid, hexahydrorthophthalic acid, and their anhydrides and their esters, hydroxyalkyl esters and halogen transfers are used.

Among divalent dicarboxylic brewing ingredients, examples of unsaturated dicarboxylic brewing ingredients include maleic acid, fumaric acid, glutaconic acid, Q-hydromuconic acid, itaconic acid, 8-hydromuconic acid,
Tetrahydrophthalic acid, citraconic acid, methaconic acid, furoic acid, 1,6-hexene-3-diolic acid, hexadecanediolic acid, diphenylmethane y-ketocrotonic acid, 4,4', diphenylethane y-ketocrotonic acid 4,4', linoleic acid Dimers and their anhydrides and their esters and halogen derivatives are used.

Among divalent diols, examples of saturated diol components include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4 butylene glycol, 1,5 pentanediol, 1,6 hexanediol, and 2-ethyl 1 , 3-pentanediol,
2,4-dimethyl-1,3-pentanediol, 2,2-diethyl-1,3-propanediol, 2-isopropyl-2-methyl-1,3-pro/gundiol, 2-isobutyl-2methyl-1,3-bropane Diol, 2-
Tertiary-butyl-2-methyl-1,3-pro/gundiol, 2-ethyl-2isopropyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-isopropyl-1,3-bentanediol, 2-ethyl 4
Methyl-1,3-pentanediol, 2,5-dimethyl-1,3-hexanediol, 2-methyl-1,3-octanediol, 2-ethyl-1,3-hebutanediol, 2-isopropyl-1,3-hexane Diol, 2-
Ethyl-2-tert-butyl-1,3-propanediol, 2-methyl-2-neoben-1,3-propanediol, 2-amyl-2-ethyl-1,3-propanediol, 2-tert-butyl-2-isopropylene -1,3-propanediol, 2-isopropyl-4,4-dimethyl-1,3-bentanediol, 2-methyl-2-propyl-1,3-o/gundiol, 2,2-dimethyl-
1,3-propanediol, 3-methyl-bentanediol-1. 1,3-butylene glycol, 2-hexyl-2-methyl-1,3-propanediol, triethylene glycol, 1,4-cyclohexanediol, 1
, 4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and its esters. Among the divalent diol components, examples of unsaturated diol components include 3-butene-1,2-
Diol, 1,3-butenediol and its esters are used. A compound having an imide group may be prepared in advance, or a compound capable of producing a compound having an imide group may be combined with at least one other dicarbonate brewing component or diol component. It is also possible to react in one step.

These imide group-containing bifunctional compounds are represented by the following structural formula:

These compounds can be obtained, for example, by the reaction between the following two types of compounds.

a. In addition to the five-membered carboxyl anhydride group, at least one
Aromatic carboxylic acid anhydrides containing several other reactive groups. This latter reactive group can be a carboxyl group, as well as a carboxylic anhydride group or a hydroxyl group. In place of the first-mentioned cyclic carboxylic acid anhydride group, two carboxyl groups bonded to adjacent carbon atoms or their esters or half-esters, as well as those listed in b below, to the extent that they can form an imide group. Half-amides with primary amines may also be used. b a primary amine which, besides the primary amino group, also contains at least one other reactive group, this latter reactive group being a carboxyl group, a hydroxyl group or even a primary amino group; I can do it. Instead of primary amines, salts, amides, lactams or polyamides of the amines can also be used, insofar as the primary amino groups to which they are attached can form imides. Examples of the compound a having a cyclic carboxylic anhydride group and other functional groups include tricarboxylic anhydride, such as trimellitic anhydride, hemimellitic anhydride, 1.2.5-naphthalenetricarboxylic anhydride, 2. 3.6-naphthalenetricarboxylic anhydride, 1.8
．． 4-Naphthalenetricarboxylic anhydride, 3.4.4-
diphenylmethanetricarboxylic anhydride, 3.4.4'
- diphenylmethanetricarboxylic anhydride, 3.4.
4'-diphenyl ether tricarboxylic anhydride, 3
．． 4.4'-penzophenonetricarboxylic anhydride, tetracarboxylic dianhydride such as pyromellitic dianhydride, merophanic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, 1.8.4.5-Naphthalene tetracarboxylic dianhydride, 1.2.5.6 Naphthalene tetracarboxylic dianhydride, 3.3'. 4.4'-diphenyltetracarboxylic dianhydride, 2.2.3.
3'-diphenyltetracarboxylic dianhydride, 3.3
．． 4.4-diphenyl ether tetracarboxylic dianhydride, 3.3'. 4.4'-diphenylmethanetetracarboxylic dianhydride and 3.3.4.4'-penzophenetetracarboxylic dianhydride are particularly preferred.
It is trimellitic acid anhydride.

Compound b having a primary amino group and other functional groups
Examples are 4.4'-diaminodiphenylmethane, 4.
4-diaminodiphenyl ether, benzidine, 3.
3-diaminodiphenyl, 1,4-diaminonaphthalene, m-phenylenediamine, P-phenylenediamine, Q. -nonamethylene diamine, 1,7-dimethylheptamethylene diamine, 4,4'-diaminodiphenyl ketone, bis-(4-aminophenyl)-Q. B'-P-xylene, toluylene diamine, xylene diamine, xylylene diamine, hexamethylene diamine,
Ethylenediamine, 4,4'-dicyclohexylmethanediamine, diamine/. Diphenyl. Primary diamines (particularly preferred are aromatic diamines), such as sulfones, penzoguanamine, and also amino alcohols, such as monoethanolamine, molepropanolamine or dimethylethanolamine, as well as, for example, glycocols, Aminocarboxylic acids such as aminopropionic acid, aminocaproic acid or aminobenzoic acid may also be used. When a) and b) are reacted, the ratio of use of both is, when a) is a tetracarboxylic dianhydride, b) is an amino alcohol alone, an aminocarboxylic acid alone, or both in an appropriate ratio. In this case, b) is used in an amount of 2 moles or more per 1 mole of a), preferably 2.0 moles, and when a) is a tricarboxylic anhydride, b) is a diamine. In the case of b
2 or more moles of a) are used, preferably 2.0 moles, per 1 mole of a).b) is an amino alcohol alone, an aminocarboxylic acid alone, or an appropriate ratio of amino alcohol and aminocarboxylic acid. In the case of a mixture, it is preferable to use 1 mol of b) for 1 mol of a),
Among these, particularly often used is the case where tricarboxylic acid anhydride is used as a) and aromatic diamine is used as b) in a molar ratio of a):b) = 2:1,
Most preferred is 2 moles of trimellitic anhydride and 4.
A polyhydric carboxylic acid having the formula (R: 1 C string- or 10-) obtained from 1 mole of 4'-diamino diphenyl methane or 4.4-diamino diphenyl ether, and then the above a ) and c) m-phenylene, diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenyl ether-4,4-diisocyanate, diphenylmethane-4,4- Diisocyanate, diphenyl sulfone-4
．． 4-diisocyanate, diphenyl sulfone 4.4
-Diisocyanate, diphenylthioether 4.4
- A condensate obtained by reacting with a diisocyanate, such as diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, or xylene diisocyanate.

As a), tricarboxylic acid anhydride is used,
For 2 moles of this, c) is used in an amount of 1 mole or more and 2 moles, preferably 1 mole or around 1 mole, and trimellitic anhydride is particularly often used as a), c) as diphenyl methane-4.4
-diisocyanate, diphenyl ether 4.4'-
It is a condensate obtained using diisocyanate. Now, the reaction initiator for polymerizable unsaturated bonds referred to in the present invention includes, for example, one or more organic peroxides, or one or more organic peroxides in combination with one or more promoters. is used, but any initiator for the cleavage reaction of polymerizable unsaturated bonds may be used.

Examples of organic peroxides include ■ Diacyl peroxides such as acetyl peroxide, benzoyl peroxide,
Caprylic peroxide, P-chlorobenzoyl/gu oxide, 2.4-dichlorobenzoyl/di-oxide, lauroyl/gu oxide, heragonyl peroxide, propionyl peroxide, di-isopropyl peroxydicarbonate, di-isopropyl peroxydicarbonate.

2. Ethyl'hexyl peroxy.

Dicarbonate, isobutyryl peroxide, octanoyl peroxide, decanoyl/gu oxide, stearoyl peroxide, 3.5.5 trimethylhexanoyl/gu oxide, succinic amide peroxide, etc. ■ As ketone peroxide , for example, methyl ethyl ketone/gu oxide,
These include cyclohexanone/gu oxide, ketone/gu oxide, etc.

■ Peroxyesters such as tertiary butyl nof-oxyacetate, tertiary butyl peroxybenzoate, tertiary butyl peroxy (2-ethylhexanoate), tertiary butyl peroxy isobutyrate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy benzoate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy isobutyrate
J-Butyl peroxyisopropyl carbonate, tertiary butyl peroxy bivalate, 2.5-dimethyl hexyl 2.5 di(peroxy benzoate)
, 2.5-dimethylhexyl, 2.5-di(peroxy.
2-ethyl hexanoate), tertiary-butyl diperoxyphthalate, tertiary-butyl peroxymaleic acid, and tertiary-butyl peroxy laurate.

■ Di-alkyl oxides such as y-butyl 4.4-bis(tert-butyl peroxy)valerate, di-tert-butyl/gu oxide.
Dicumyl/gu oxide ~ 2.5 dimethyl 2.5 bis(tert-butyl peroxy) hexane, di-
Tarsia leaf chill cumyl peroxide, Q. Q
'Bis(tersia 1'-butyl peroxy)hexane '2,5 dimethyl 2,5 bis(tersia-butyl peroxy)
(peroxy) hexin-3, etc.

■ Hydroperoxides such as tert-butyl hydroperoxide, 2,5
dimethylhexane 2,5 dihydroperoxide,
Cumene hydroperoxide, di iso fu.

Lopyl benzene hydroperoxide, P-menthane hydroperoxide, etc. ■Acetyl.

These include cyclohexyl, sulfonyl, peroxide, etc. Other examples of reaction initiators for polymerizable unsaturated bonds include: ■ Inorganic, peroxides For example, persulfates ■
Azopisnitriles For example, 2:2'azobisisobutyronitrile, 2.2azobispropionitrile, 2.2azobisvaleronitrile, etc.

■ Azo and diazo compounds such as diazoamino benzene, nitroso acyl allyl amines, azothioethers, P-nitrobenzene diazonium salts, etc.

■ Examples of sulfinic acids include aromatic sulfinic acids, toalkanesulfinic acids, and sulfur.

Examples of accelerators used in combination with organic peroxides include lauryl mercaptan, N-butylsulfite diphenyl disulfide, tetramethyl, thiuram disulfide, /latluenesulfonic acid, and mono- and quaternary ammonium sodium todecylsulfonate. salts, 3
Diketones, peracetic acid type epoxy compounds, sulfonium salts, metal oxides or hydroxides, metal soaps such as cobalt naphthenate, cobalt octoate, manganese naphthenate, vanadium octoate, copper naphthenate, calcium naphthenate, naphthenic acid Barium, naphthenic acid, zinc zirconium naphthenate, metal chelate compounds such as vanadium acetylacetonate cobalt acetyl
acetonate, iron acetylacetonate, aluminum acetyl acetonate, titanium tetrabutyrate,
Phosphorus-containing compounds such as phenylphosphinic acid, dimethylcosphine sulfur-containing compounds such as 1.3 dibutylthiourea, etc. are used.

These reaction initiators may be included in the insulating composition used in the present invention from the beginning, or they may be added to the insulated wire by first obtaining a non-crosslinked insulated wire without being included in the insulating composition. It is also possible to obtain a crosslinked insulated wire by treating an uncrosslinked insulated wire with a reaction initiator by the method described below and cleaving the polymerizable unsaturated bond by post-heating or the like. As a method for treating this reaction initiator, for example, L. Even if these polymerizable unsaturated bond reaction initiators are added to an uncrosslinked insulated wire as is, they can be melted at a temperature higher than the melting point of the peroxide and added to the wire. It may be applied to an insulating film and allowed to penetrate through it, or it may be dissolved in a suitable diluent solvent and added to an insulated wire. The above accelerator is
It may be used in direct combination with peroxide, or it may be added in advance during the synthesis of high molecular weight polyesterimide having polymerizable unsaturated bonds in the molecule, or it may be added to the insulating composition.

Monomers and prepolymers with polymerizable unsaturated bonds used as crosslinking aids include, for example, acrylonitrile,
Divinylbenzene, ethylene glycol diacrylate, ethylene glycol methacrylate, glycerol trimethacrylate, diethylene glycol divinylable, diallylitaconute, triallylaconute, triallyl dianurate, diallyl maleate, diallyl fumarate , triallyl phosphonate, vinyl methacrylate, allyl acrylate, diallyl citraconate, diisoprobenyl diphenyl, diallyl carbonate of ethylene glycol, diallyl carbonate of tetramethylene glycol, diallyl carbonate of diethylene glycol, diallyl carbonate of polyethylene glycol, Diallyl carbonate of P-phenylene diol, diallyl carbonate of xylylene diol, diallyl carbonate of bis(4-hydroxyphenyl)methane, triflyl cyanurate, compound of the formula triallyl isocyanurate diallyl phthalate, trimethylolpropane trimethacrylate and bleed polymers of these monomers.

Any other monomer or prepolymer having a polymerizable unsaturated bond in the molecule may be used. For example, there are monomers or prepolymers containing a polymerizable unsaturated bond, an ester bond, a polymerizable unsaturated bond, an ester bond, and an imide group in the molecule. In order to better explain the features of the present invention, implementation will be shown and specifically explained.

Remarks 1 Unless otherwise specified, the coating and baking of the electric wires used in the comparative examples and examples of the present invention was carried out using a vertical furnace with an effective furnace length of 4.5 mm, and the furnace temperature was 41,000 mm in the upper part, 40,000 mm in the middle, and 2,500 mm in the lower part.
Under the condition of 0, the wire diameter is 1. Baked on Hiro◇ copper wire.

2 A 4-tower flask was used as a reaction apparatus for synthesizing the unsaturated polyester and unsaturated polyesterimide resins of the comparative and reference examples of the present invention.

The 4-tube flask is equipped with: ■Nitrogen inlet pipe, ■Communication pipe with pressure reducing device, ■Side pipe that can distill off reaction products and excess reaction components, and ■Inlet for introducing raw materials and stirring the reactor. It is equipped with a machine.

3 The intrinsic viscosity of the synthetic polyesters and polyesterimides used in the comparative and reference examples of the present invention was measured at 3000 using reagent grade m-cresol as a solvent using an Ostwid viscometer.

4 The melting points of the polyeste and polyesterimide resins were measured using a Shimadzu melting point apparatus model M-M-2.

5 Pinhole test (no treatment method) Flexibility test, thermal shock resistance (wrapping method), dielectric breakdown voltage, and abrasion resistance (reciprocating method, directional method) were conducted in accordance with the method shown in JIS-C-3003. . The NEMA formula was used for the thermal softening test. Comparative Example 1 Dimethyl terephthalate (DMT) 582.6 grams (3.0 mol) Dimethyl isophthalate (DMI) 582.6 grams (3.0 mol) Maleic anhydride (MAN) 294.0 grams (3.0 mol) ) Ethylene glycol (EG) 1162.5 grams (18.75 moles) Lead acetate (Pb(OAc)2・mother LO) 1.3 grams Hydroquinone 0.13 grams The above amounts of each substance were weighed.

EG lead acetate was added into the reaction vessel. The temperature was gradually raised from room temperature and stirred at 120 qC or less for about 30 minutes. Next, DMTD
MI was added into the container, and while the temperature was raised at a rate of 20° C./hour, the methanol that gradually distilled out was distilled off through a side pipe. Distillation of methanol was achieved almost quantitatively up to 180° C. At this point, hydroquinone was added into the reaction vessel, and then the reaction vessel was purged with nitrogen gas. MAN in this container
added. The temperature of this reaction vessel was raised to 200 qo in batches of about 1 powder, and reflux was performed within the reaction vessel. Next, a distillate side pipe was attached and kept at 20 psi for about 1 hour to remove the distillate. Next, the reaction vessel was heated to 220° C. in 1 hour while reducing the pressure, and the reaction was completed while maintaining this temperature.

Decompression was initially 150 ribs Hg, then 30 ribs Hg, and finally 1. It has reached the point where it was made in the past. Vacuuming was carried out for 5 hours until the reaction was completed. During this time, the distillate was distilled off to obtain a resin. The melting point of this resin was approximately 110 pm, and the ri was 0.55. Dimethylformamide was added to this resin as a solvent, and triallylysocyanurate (TMC) diallylphthalate prepolymer (
DAP prebolimer) and dicumyl peroxide, a cleavage initiator for the polymerization reaction, were blended in the proportions shown in the table below to obtain each composition. These compositions were applied onto copper wires at a temperature of 410 mm and a temperature of 400 mm.
The crosslinking was carried out in a furnace at 25,000 mph at a linear speed of 8 m/min to a film thickness of 40 m/min.

The characteristics of the resulting wire are shown in the table below. Next, using Composition Nos. 7 and 8, the obtained electric wires having the same structure as the electric wire of Composition 4.6 were sequentially and continuously added to an acetone solution containing 20% dicumyl peroxide by weight. Soak,
The acetone was then evaporated, and the wire was then continuously placed in a heating oven for a crosslinking reaction.

This electric wire had pinholes, flexibility, and other properties similar to those of Composition No. 4.6. Comparative Example 2 Dimethyl terephthalate 776.8 grams (4.0 mol) Fumaric acid 464.4 grams (4.0 mol)
1055.7 grams (17.0 moles) of ethylene glycol and 2.2 grams of cadmium acetate were weighed out and the same procedure as in Comparative Example 1 was carried out to prepare an unsaturated polyester resin.

This resin was ground in a mortar. This powder was added to 424.8 g (8.0 mol) of acrylonitrile monomer to which 0.22 g of hydroquinone had been added in advance.
The mixture was added while being gradually dissolved while keeping the temperature below 0, and the entire amount was dissolved to obtain an unsaturated polyester resin paint. Further, 98.5 grams of diallyl phthalate brepolymer was added to this coating material, and 44 grams of 50% penzoyl peroxide paste as an initiator were added to obtain a solvent-free insulating composition. This paint was applied late using a furnace at exactly the same temperature as in Comparative Example 1 to obtain an insulated wire having the following characteristics at the following wire speed.

In addition, when the above-mentioned solvent-free insulating composition that does not contain the initiator penzoyl peroxide 50% paste was coated on a copper wire of 1.0 ribs and irradiated with an electron beam, the composition cured and became flexible. An insulated wire with excellent properties and comparable properties was obtained.

Comparative Example 3 Dimethyl terephthalate 776.8 grams (4.0 moles) Fumaric acid 371.5 grams (3.2 moles)
993.6 grams (16 moles) of ethylene glycol and 2.1 grams of cadmium acetate were weighed and the same procedure as in Comparative Example 1 was carried out to prepare an unsaturated polyester resin.

This resin was ground in a mortar. This powder was added to 339.8 grams (6.4 moles) of acrylonitrile monomer* to which 0.21 grams of hydroquinone had been added in advance.
The mixture was added while being kept at a temperature below 0.degree. C. and gradually dissolved, and the entire amount was dissolved to obtain an unsaturated polyester resin paint. Further, 271.0 grams of triallylysocyanurate was added to this paint, and 44 grams of initiator penzoyl peroxide 50% paste was added.
gram to obtain a solvent-free Zetmakutake composition. This paint was phosphorized in a furnace at the same temperature as in Comparative Example 1 to obtain insulated wires having the following characteristics. Reference example 1 Dimethyl terephthalate (D.M.T.) Total 8.4 grams (2 moles) Diphenylmethane-4.4'-ditrimellitic imide (1.D.A.) 273.0 grams ( 0.5 mole)
Ethylene glycol (E.G) 583.3 grams (9
．． 5 moles) Maleic anhydride (MAN) 171.5 grams (1.75 moles) Lead acetate (Pb(OAc)2.XLO) 2.0 grams The above amounts of each substance were weighed.

E.G and lead acetate were added to the reaction vessel. I stirred it for about 30 minutes at less than 12,000.

Next, D. M. Add T and overflow at a rate of 20°C/hour.
The distilled methanol was distilled off. Methanol was distilled off almost quantitatively by the time the temperature reached 200°C.

1 for 200oo. D. A was added to effect esterification, and the reaction product was distilled off for about 1.5 hours.

Thereafter, distillation was stopped and the inside of the reactor was refluxed at 200q0. The inside of the reaction vessel became transparent in 1 to 2 hours.

This reaction vessel was sufficiently purged with nitrogen gas. During that time, the internal temperature of the container was lowered to 180°C, and 180°C MAN was added into the container.

Furthermore, while blowing nitrogen, the temperature inside the container was raised to 220° C. in 20 minutes. Attach a side tube and apply vacuum to the vessel to remove the reaction products and excess E. G was distilled off. The degree of decompression was 12 degrees Hg in the initial stage, 15 to 1 degrees Hg in the middle stage, and finally 1. It reached the level of the shipping company. The reaction was terminated by heating under reduced pressure for 3 hours. The melting point of the resulting resin was about 100 qo. (ri) is 0. It was total. Reference example 2 Dimethyl terephthalate (D.M.T) 97.1 grams (0.5 mol) Diphenylmethane-4.4'-ditrimeritic imide (1.D.A) 546.0 grams (1 .0 mol)
Ethylene glycol (E.G) 214.9 grams (3.
5 moles) Maleic anhydride (M.AN) 171.5 grams (1.75 moles) Lead acetate (PbAc2) 2.0 grams The above amounts of each substance were weighed.

Using this substance, a reaction was carried out in exactly the same manner as in Reference Example 1 to obtain a polyesterimide resin. Resin melting point 1370
, [ri]=0.46. Reference example 3 Dimethyl terephthalate (DMT) 352.0 grams (1.81 mol) Dimethyl isophthalate (DMI) 352.0 grams (1.81 mol) Diphenylmethane-4.4'-ditrimellitic imide (mA) 203 .1 g (0.37 mol) Maleic anhydride (MAN) 49.0 g (0.50 mol) Ethylene glycol (EG) 559.5 g (9.11 mol) Lead acetate (Pb(OAc)2.XLO ) 0.76 grams Hydroquinone 0.08 grams Each of the above substances was weighed.

Using these materials, a reaction was carried out using almost the same equipment as in Reference Example 1. The melting point of the esterimide produced from this reaction was 94° C. and 0.37. *Example: Diaryl phthalate prepolymer (abbreviated as DAP-P) and triallyl isocyanurate (TAIC) were added to the unsaturated linear polyesterimide obtained in Reference Example 1, Reference Example 2, and Reference Example 3 as a crosslinking aid. , dicumyl peroxide (DCP) as a peroxide as an initiator for the polymerization reaction.
, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (DTPH-3) and cresylic acid as a solvent were blended as shown in the following table to obtain an insulating paint.

(The numbers in the table are the total amount in grams) These paints are heated in a furnace at a furnace temperature of 410°C at a linear speed of 5 parts per coat. The copper wire was bonded by applying bran eight times to obtain an electric wire with the characteristics shown in the table below.

In the present invention, since a linear polymer having an imide group in the molecule is used, an insulated wire with superior heat resistance (thermal softening temperature, heat shock resistance) and abrasion resistance can be obtained compared to comparative examples. Ta.

Claims (1)

[Claims] 1. A high molecular weight linear polyesterimide having a polymerizable unsaturated bond in the molecule, at least one molecule of which has as a main component a high molecular weight linear polyesterimide having two or more unsaturated bonds. An insulated wire having a crosslinked insulating film obtained by coating an insulating composition directly on a conductor or through another insulator and reacting the polymerizable unsaturated bonds of the polyesterimide.