JPS59151704A - Method of producing electric device - 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 The present invention relates to a method for manufacturing electrical equipment with excellent heat resistance.

Recently, in order to reduce the size and weight of electrical equipment, there has been a demand for electrical equipment with good heat resistance, freon resistance, and the like.

A polyamide-imide coated wire is an A-line that satisfies all of these requirements.

However, electrical equipment using Boria S toimide coated wire,
Polynisole, poly+7 ester imide.

Electrical insulation is achieved by treatment with an impregnated varnish such as epoxy resin or N-methyl-2-pyrrolidone solvent-based polyamide-imide, but impregnated varnishes other than polyamide-imide have poor heat resistance.

There is a problem that heat resistance decreases due to varnish treatment.

Also, N-methyl-2-pyrrolidone solvent type polyamitoy S
When used as an impregnating varnish.

Because a part of the coating of the boria S toimide wire is eluted into N-methyl-2-pyrrolidone during face treatment, P! ,
It may have an adverse effect on insulating materials used in machines, machines, and other electrical equipment with reduced kneading properties. For this reason,
There is a need for an impregnating varnish that is compatible with polyamide-imide coated wire.

As a result of studying the development of an impregnated varnish that is compatible with polyamide-imide coated wire, the present inventors have found that by combining polyamide-imide soluble in cresol solvent as an impregnated varnish with polyamide-imide coated wire, a material with good heat resistance can be obtained. It was discovered that an electrical device can be obtained, leading to the present invention.

The present invention provides electrical equipment using polyamide-imide transverse wires such as lactams, aromatic diisocyanates), #t! Cedar treated with a varnish containing polyamideimide obtained by reacting a polycarboxylic acid having an anhydride group and an incyanurate ring-containing polyisocyanate and a cresol solvent, and cured by heating! Concerning the manufacturing method of electrical equipment.

The polyamide-imide used in the polyamide-imide coated wire used in the present invention is not particularly limited as long as it is obtained by reacting a commonly used polycarboxylic acid having an acid anhydride group with an aromatic diisocyanate. As the polycarboxylic acid having an acid anhydride group, trimellitic anhydride is used.

Examples include butanetricarboxylic anhydride.

Preferred aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and the like. Of course, within the known range, a part of the polycarboxylic acid/acid having an acid anhydride group is converted to benzophenonetetracarboxylic dianhydride.

M may be replaced with pyromellitic dianhydride, etc.

Further, a part of the aromatic diisocyanate may be replaced with a polyinsyanate such as tolylene diinocyanate. There are no particular restrictions on the conditions for synthesizing the polyamide-imide and the baking of the boria S toimide coated wire, and they may be within the range that provides the properties commonly known as polyamide-imide coated wires.

Examples of electrical devices using Boria S toimide coated wires include motors and transformers used in coolers, refrigerators, power tools, electrical components, microwave ovens, and the like.

Incyanurate ring-containing polyiso 7 used in the present invention
Anates are obtained by tri-composition of polyisocyanate compounds, and this reaction is carried out in the presence of a solvent that does not react with inocyanate groups and without adding any components that react with incyanate groups, such as phenol or lactams. In order to proceed effectively, it is desirable to use a trimerization catalyst of a polyisocyanate compound.

The solvent may be aliphatic and aromatic hydrocarbons, etc. as long as it dissolves the polyisocyanate compound as a raw material.
Rodanized aromatic hydrocarbons.

Ester-based, ketone-based, ether-based, ethylene glycol monoalkyl monoacetate-based solvents.

It can be arbitrarily selected from dimethyl sulfoxide and the like.

Trimerization catalysts for polyisocyanate compounds include ``alkali metal acetate, iron, magnesium, nickel, zinc, tin, lead, sodium ζ, metal salts and organometallic compounds of titanium, N-methylmorpholine, 1,8-diazabicyclo( Mannich bases of phenols such as 5,4,0) undecene-7,2-(dimethylaminomethyl)-4,6-dimethylphenol, tertiary amines such as 2-dimethylaminoethanol, etc. can be used, and there are no particular restrictions. do not have.

The reaction temperature for converting the polyisocyanate compound is, for example, in the range of 50 to 160°C.

The actual trimerization reaction of polyincyanate compounds is complex, and it is not necessarily the case that only an adduct of incyanate containing only one isocyanurate ring per molecule is selectively formed, and unreacted incyanate and incyanurate A mixture with an incyanate adduct containing two or more nurate rings in one molecule is obtained. This mixture can also be used in the present invention.

There are no particular restrictions on the amount of catalyst and the reaction temperature. Raw materials for the isocyanurate ring-containing polyisocyanate include aliphatic,
Either alicyclic or aromatic diisocyanate compounds may be used, but aromatic diisocyanates, particularly 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate.

xylylene diisocyanate, 4. Diphenyl ether diisocyanate and the like are preferred.

In-7 annulate ring-containing polyinsyanate is -9I
From the viewpoint of TS thermal properties and malleability, the content of residual inocyanate groups is preferably in the range of 10 to 70% (assuming the content of inocyanate groups in the raw material diisocyanate is 100).

The incyanurate ring-containing polyisocyanate is
．． It is preferable to use 0.01 to 0.30 equivalent in terms of heat resistance and reliability.

Lactam, which is an important raw material for solubilization in cresol solvents, can generally be anything as long as it reacts with incyanate groups or acid anhydride groups in cresol solvents and is soluble in cresol solvents. Considering solubility, reactivity and cost, ξ-caprolactam is preferred.

The amount of lactam used is 0.30 to 0.80 equivalents per 1.0 equivalent of polycarboxylic acid/acid having an acid anhydride group based on heat resistance, flexibility, and solubility (lactam is considered to be difunctional).
is preferred.

Preferred aromatic diisocyanates include H,4,4'-diphenylmethane isocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, and xylylene diisocyanate.

As the polycarboxylic acid having an acid anhydride group, trimellitic anhydride, butanetricarboxylic anhydride, etc. are used, but trimellitic anhydride is preferable from the viewpoint of characteristics 1 and price.

The amount of incyanate component and acid component to be used is such that the sum of equivalents of aromatic diincyanate and isocyanurate ring-containing polyisocyanate is 0.80 to 1.50 equivalents per 1 equivalent of polycarboxylic acid having an acid anhydride group. Select randomly.

In order to obtain a high molecular weight resin, incyanate groups are added to carboxyl groups and acid anhydride groups.

It is particularly preferable that the ratio is around 1.0.

As the cresol solvent, in addition to cresol, phenol, xylenol, etc. can be used, and a mixed solvent may also be used. High-boiling aromatic organic solvents such as xylene, NOIZO-LU 100 (Nippon Petrochemicals KK), ethylene glycol monoethyl monoacetate, etc. can also be used as part of the synthesis solvent.

The reaction of a lactam, an aromatic diisocyanate, a polycarboxylic acid having an acid anhydride group, and a polyisocyanate containing an in7 annulate ring is carried out at a synthesis temperature of about 160 DEG to 240 DEG C., for example, in the presence of a cresol solvent.

The obtained polyamide-imide solution may be diluted with the above-mentioned cresol solvent until it reaches an appropriate viscosity. that time,
Xylene as a co-solvent.

There is no problem in using aromatic hydrocarbons such as toluene in combination. Also, as a curing agent, an epoxy resin such as Epicoat 562.815°828.1001,1 manufactured by Shell Chemical
007. Alkoxy modified 79 resins such as Hitachi Chemical's ML-20° ML-28, phenol formaldehyde resins such as Hitachi Chemical's PR-208
Thermosetting resins such as 0, PR-2084, and VP-51NG may also be used together. The amount of curing agent added is
It is preferably 1 to 50 parts by weight based on 100 parts of heavy acid of Boria S toimide.

The pheno treatment of electrical equipment using polyamide-imide coated wires in the present invention is carried out by a commonly used method, such as a dipping method or a dropping method.

The present invention will be explained below using comparative examples and examples. ``Part'' means weight part, and ``chi'' means heavy weight part.

Comparative Example 1 Production of polyamide-imide horizontal wires N-methyl-2-pyrrolidone solvent-based polyamide-imide varnish HI-405 manufactured by Hitachi Chemical Co., Ltd. was used at a furnace temperature of 40
A type 1 finish enamelled copper wire with a diameter of 1+ m was obtained in a vertical furnace at 0° C. and a furnace length of 4 m.

Comparative example 2 Synthesis of polyester for impregnation varnish Maleic anhydride 9.8F (1 mol), phthalic anhydride.

Acid 141L (1 mol), Flopylene Gelicol 170.
6F (2.zs mol) was charged into four flasks, stirred while blowing nitrogen gas, kept at 180℃ for 1 hour, and then reacted at 210-220℃. Next, unsaturated polyester with an acid value of 18.0 Obtained.

Add 0.05% hydroquinone to the reaction product.

diallylphthale) e65 (1/- charged, dissolved.

A pale yellow, uniform resin liquid was created. Varnish A was obtained by adding 1% benzoyl peroxide and 0.1% cobalt octenoate to this resin solution.

Comparative Example 3 Synthesis of polyesterimide for impregnated varnish Trimellitic anhydride 38.45M (0.2 mol), 4°4'-diaminodiphenylmethane 19.8F (0.1 mol), N-methylpyrrolidone 110? was charged into a fourth flask, and while blowing nitrogen gas, the temperature was raised from room temperature to 150°C to dissolve, and then the mixture was reacted at 150°C to 180°C for 2 hours to form a uniform solution containing imide acid. Cool this solution to room temperature,
The reaction product was added dropwise to 5 times the volume of methanol with stirring, separated, and then collected, optically washed with methanol, and dried under vacuum heating to obtain a compound represented by the secondary formula.

This compound 51.8P (0.1 mol), isophthalic acid 7
4.7P (0.45 mol), neopentyl glycol 6
2.4P (0.6 mol), propylene glycol 26.
610.35 mol) was charged into a fourth flask, and the temperature was raised to 160 °C by blowing nitrogen gas (after reacting for 7.1 hours, the temperature was raised to 211) °C in 3 hours, and the temperature was raised to 210 °C.
Continuing the reaction, the acid value was measured every hour, and when the acid value became 5 or more F, the temperature was lowered to 160'C, and 44.1y-(0.45 mol) of maleic anhydride and diglobylene were added. Glycol 26.8y-(0.2 mol) was charged, and 1
After time react.

Raise the temperature to 210°C in 1 hour, continue the reaction at 210°C,
An unsaturated polyester having an acid value of 29 was obtained. Add 0.05% hydroquinone to this reaction product.

Diallyl phthalate 6109-added and dissolved. The viscosity of this resin liquid was 290 centipoise at 25°C.

To 100 parts of this resin liquid, 1.0 part of benzoyl peroxide and 0.1 part of cobalt octenoate (metal content: 8g) were added and stirred well to obtain a uniform solution, varnish B.

Example 1 1) Synthesis of isocyanurate ring-containing polyisocyanate Tolylene diisocyanate 600. %, Hysol 10
0 600y-,2-dimethylaminoethanol 1.8
1 was placed in a flask, the temperature was raised to 140'C, and the reaction was allowed to proceed until the residual isocyanate content reached 50%.

2) Preparation of Boria S toimide varnish using cresol solvent Incyanurate term-containing polyincyanate solution synthesized in Example 1 (1) 37.010.11 equivalents), trimellitic anhydride 1o o, sy-(t, os insurance)
, c-caprolactam 33.810.60 equivalents), 4.
4'-Shifethermethane diisocyanate 113.3
Four pieces of F (0.91 equivalent) and Cresol 3001 were placed in a flask, and the temperature was adjusted to 21°C while blowing nitrogen gas.
0' and kept warm for 10 hours. This was diluted with cresol to obtain a solution with a non-volatile content of 20%. To this was added 3 parts to 100 parts of Boria S toimide resin.

Epoxy resin Epikote 828 was added to prepare Boria S toimide varnish C.

Example 2 Incyanure ring-containing polyisocyanate solution synthesized in Example 1 (1) 47. I P (0.14 equivalents t3゜trimellitic anhydride 100.8ψ (1.05 equivalents).

ε-caprolactam 28.3y-(per 0.50, 4°4'-diphenylmethane diisocyanate 107.5F
(4 cresol 180 F/0.86) was charged into a flask, and the temperature was raised to 205° C. while blowing nitrogen gas, and the temperature was kept for 10 hours. This was diluted with a solution of cresol/xylene=8/2 (weight ratio) to obtain a solution with a nonvolatile content of 20%. To this, alkoxy-modified amine resin ML was added at a ratio of 1.5 parts to 100 parts of polyamide-imide resin.
-20 was added to prepare polyamide varnish D.

Using the polyamide-imide coated wire obtained in Comparative Example 1,
Twist pef 1 is manufactured according to JISC3003. Next, the twisted pair was immersed in varnishes A and B, taken out and heated at 120°C for 3 hours, and the twisted pair was immersed in varnish C and D.
The sample was immersed in water, taken out, and heated at 240°C for 1 hour. The obtained insulated product was left in a constant temperature box at 260° C. for 14 days and then cooled, and the dielectric breakdown voltage was measured to determine the residual ratio with respect to the initial value, which is shown in Table 1. For comparison, tests were also conducted on polyamide-imide coated wires that were not treated with varnish, and the results are also listed in Table 1.

Table 1: Comparison of properties As is clear from Table 1, the electrically insulated products in the Examples were more efficient than the electrically insulated products in the Comparative Examples.

The residual rate of P3m breakdown voltage is extremely high and is equivalent to the untreated value without treatment with impregnated varnish, and exhibits excellent heat resistance without reducing heat resistance due to impregnated varnish.

The method of manufacturing electrical equipment according to the present invention is extremely effective in the field of electrical insulation, which requires heat resistance, and is industrially significant.

21-

Claims (1)

[Claims] 1. An electrical device using a boria S toimide wire is obtained by reacting a lactam, an aromatic diisocyanate, a polycarboxylic acid having an acid anhydride group, and a polyisocyanate containing an incyanurate group. A method for manufacturing electrical equipment, characterized by treating it with a face containing polyamide-imide and a cresol solvent, and curing it by heating. 2. The method for manufacturing electrical equipment according to claim 1, wherein the amount of lactam used is 0.30 to 0.80 equivalents per 1.0 equivalent of polycarboxylic acid having an acid anhydride group.