JPS59127313A - Insulated 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 (Technical Field of the Invention) The present invention relates to an electric wire having excellent heat resistance, abrasion resistance, and excellent blistering properties.

(Technical Background of the Invention) An insulated wire with excellent fluorocarbon resistance is a polyvinyl formal insulated wire in which a thin polyamide-imide film is provided on a conductor, and a polyvinyl formal film of a predetermined thickness made of a fluorocarbon resistant composition is formed on top of this. Are known.

This type of electric wire has a polyvinyl formal insulated wire with a fluorocarbon-resistant composition, which cannot prevent the concentration of fluorocarbons penetrating into areas with poor adhesion between the conductor and the coating, and the cracking of the coating due to the gasification pressure of this concentrated fluorocarbon. This type of wire is mainly used for the winding of the mode of hermetic refrigerators, but the heat resistance class is classified as class E (maximum allowable temperature of 90°C), so it is classified as B, which is higher than this. There was a problem in applying it to the heat-resistant categories of species (130°C) and F class (155°C).

On the other hand, polyamide-imide resin wire has heat resistance of 0 types (180℃ or higher), thermal shock resistance, mechanical properties,
It has excellent chemical resistance and well-balanced properties, but it is not widely used because it is expensive due to poor wire manufacturing processability, and the workability of removing the coating with chemicals at the end of the wire is poor. .

In recent years, with the desire to make equipment smaller and lighter, heat resistance characteristics,
It is desired to develop an enameled wire with high reliability in terms of mechanical properties, resistance to organic solvents and inorganic chemicals, etc. associated with high-speed self-winding.

(Purpose of the Invention) The present inventor has provided heat resistance, refrigerant resistance, and abrasion resistance by providing a polyamideimide resin film on the outer layer of a phenolic solvent-soluble polyamideimide resin film that uses citric acid as one of the starting components. It was discovered that it can improve sexual performance.

The present invention has been made based on this knowledge, and its purpose is to provide an insulated wire with excellent heat resistance and good refrigerant resistance.

(Summary of the invention) That is, the insulated wire of the present invention has at least 5
A phenolic bath agent-soluble polyamide-imide resin obtained by reacting a tricarboxylic acid and/or its derivative containing citric acid of more than 10% and a diisocyanate and/or its derivative in a phenolic solvent! The coating and baking process is characterized in that it further forms a layer (A).

The citric acid used in the present invention can be used with or without water of crystallization, but since the reaction with diincyanate and/or its derivatives involves dehydration, the reaction efficiency is low. It is preferable to use all anhydrous citric acid which does not contain water of crystallization.

Tricarboxylic acids and/or derivatives thereof other than citric acid include, for example, aromatic tricarboxylic acids, aromatic tricarboxylic acid esters, aromatic tricarboxylic acid anhydrides, etc. represented by formulas (1) and (n), used alone or in mixtures. It will be done.

R2-(COORI)a R50O-RJ <
c8>0(I)(■) Generally, litrimellitic anhydride is preferred from the viewpoints of heat resistance, high reactivity, economic efficiency, etc.

In addition, in order to increase the imide bond ratio and improve heat resistance, a part of the tricarboxylic acid was replaced with pyromellitic anhydride, 3.3'
, 4.4'-benzophenonetetracarboxylic anhydride,
Substitution with a tetracarboxylic acid such as butanetetracarboxylic acid or a derivative thereof is also possible.

On the other hand, if you want to increase the number of amide bonds from the standpoint of balancing the properties of a multi-component system, use terephthalic acid, isophthalic acid, system
Aromatic or aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, etc. can also be used as part of the total tricarboxylic acid.

The proportion of citric acid in the tricarboxylic acid and/or its derivative is required to be 5 moles or more in view of solubility in organic solvents.

If the amount is less than 5 molti, the solubility in organic solvents, especially phenolic solvents will decrease, making it impossible to obtain a practical resin composition.

As the ratio of citric acid increases, the solubility in organic solvents increases, so the ratio of citric acid can be arbitrarily changed within the above range depending on the form in which the resin composition of the present invention is used.

As the diisocyanate and/or its derivative used in the present invention, any aliphatic, alicyclic, or aromatic diisocyanate and/or its derivative can be used. Suitable diinsyanates include ethylene diisocyanate, trimethine diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate,
Hesamethylene diisocyanate, hegutamethylene isocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, trimethylhexamethylene diisocyanate, morpholine diisocyanate, cycloxane diisocyanate, 3.9-bis(3-incyanate) acid probilf,
2,4,8,10 Tetone oxasbiro[5.5]Aliphatic and alicyclic diincyanates such as undecane, 4,4
'-Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenylsulfone diisocyanate, 3,3'-diphenylsulfone diisocyanate, -t, 4 ,4'-diphenylsulfite diisocyanate, 3,3'-dimethyl-
4,4'-diphenylmethane diisocyanate, 3,3
'-dichloro-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4゜4'-bisphenyl diincyanate 3,3/,)methoxy-4,
4'-bisphenyl diisocyanate -), 4.4'- and sphenyl diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2',
4-tolylene diisocyanate, 2.6-)lylene diisocyanate, m-xylylene diisocyanate, p~
There are aromatic diisocyanates of roxylylene diisocyanate, which can be used alone or in mixtures.

Further, diisocyanate derivatives in which the isocyanate group of diisocyanate is masked with phenol, cresol, xylenol, etc. can also be used.

Diisocyanate/and some of its derivatives 4
, 4', 4''-1 lysocyanate triphenylmethane, 2.2', 5.5'-tetrine cyano-)-4
, 4'-dimethylphenylmethane and the like can also be substituted with trivalent or higher polyincyanates.

Heat resistance among the incyanate compounds? In terms of mechanical properties and economic efficiency of Hj film, 4,4'-diphenylmethane diisocyanate, 14-)! JL/N diisocyanate, 2,6-)lylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,
It is particularly preferable to use 4,4'-diphenyl ether diynecyate or the like alone or in combination.

The reaction temperature and reaction time for the reaction of tricarboxylic acids and/or their derivatives, including citric acid, with diincyanates and/or their derivatives differ depending on the starting materials and the reaction type, bath liquid reaction or solvent-free reaction. However, in general, the reaction temperature is 60 to 350°C and the reaction time is several hours to several tens of degrees.
It will be done in 0 hours.

In the case of a solution reaction, it is affected by many factors such as the solvent used, the solid content when charging the starting materials, and the catalyst.
Considering that the decarboxylation reaction between carboxylic acid or its derivative and diincyanate starts at around 70°C, and considering the boiling point range of the solvent commonly used in this reaction, the preferred reaction temperature range is 70°C to 70°C. The temperature is 250°C.

If the reaction time is extremely long, the incyanate group and the solvent,
This is not preferable because side reactions such as reactions between insia K-1 groups occur, and several hours to 30 hours is preferable.

As the solvent used in the solution reaction, since the resin composition of the present invention has excellent solubility, many organic solvents can be used, but those that react with the starting materials are not preferred.

Phenolic solvents used in the present invention include phenol, 0-cresol, m-cresol, p-cresol, various xylenolic acids, and various chlorophenols, and examples of solvents that can be used in combination with these include benzene. , toluene, xylene, high boiling point aromatic hydrocarbons (e.g. Maruzen Sekiyu Taiswazol 1000, Cresol 150)
0, Nippon Oil Co., Ltd. Hysol IOO, 8 Stone Hysol 150, etc.), ethylene glycol monomethyl ether acetate, etc.

The solid content concentration during the reaction is not particularly limited, but if it is less than 35%, the reaction takes a long time, side reactions are likely to occur, and a highly polymerized resin composition cannot be obtained, so it should be set to 35% or more. More preferred.

- The reaction of the present invention can be promoted by a catalyst commonly used for isocyanate reactions.

Examples of suitable catalysts include - metal salts of heptathenic acids such as lead oxide, boric acid, lead naphthenate, zinc, organotitanium compounds such as phosphoric acid, polyphosphoric acid, dibutyl titanate, triethanolamine titanate, etc. , triethylamine, 1
・8-Diaza-bicyclo(5,4,0) undecene-7
(including this acid adduct), etc.

A suitable amount to be used is 0.01 to 5 g per solid content at the time of preparation, and the method of addition is not particularly limited.

The molar ratio of tricarboxylic acid and/or its derivatives including citric acid to diincyanate and/or its derivatives is preferably tlYl:1.

However, an excess of about 10 mole or less of either one is within an acceptable range.

Tricarboxylic acids and/or derivatives thereof, including citric acid, and diisocyanates and/or derivatives thereof may be charged simultaneously before the start of the reaction, or one may be dissolved in a solvent and the other may be added at once or in several batches. It can also be prepared, and there are no particular restrictions on the preparation method.

The reaction is controlled within an appropriate range by observing the degree of bubbling of generated carbon dioxide gas and distillation of reaction water, as well as the viscosity of the solution.

The resin composition of the present invention can also be blended with other resins if necessary.

Also other functional compounds such as polyols, polyamines,
A modified polyamideimide resin composition can be produced by adding polycarboxylic acid and further reacting.

Further, as organic polar solvents, N-methyl-2-pyrrolidone and N,N'-dimethylformamide are used.

Examples include N'-dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, and mixtures thereof may also be used. Xylene, aromatic hydrocarbon solvents, etc. may be used in combination as a co-solvent.

Here, the aromatic polyamideimide resin obtained by the reaction in an organic polar solvent is synthesized from an aromatic diamine and an acid component containing an acid anhydride and an acid chloride group in an N-methyl-2-pyrrolidone solution, for example. A resin synthesized from an aromatic diisocyanate and a polycarboxylic acid containing an acid anhydride group can be used. It does not matter if it partially contains a polyimide component.

Moreover, the ratio of (A) # and (B) layer in the present invention is (B)
/(k)=can be changed within the range of 1/9 to 9. Here, 1
If it is less than /9, sufficient wear resistance will not be obtained, and if it exceeds 9, sufficient heat resistance will not be obtained.

In particular, a range of 1/9 to 1/2 is preferred. The reason is 1/2
(Embodiments of the invention) Synthesis example 1 (Production method of phenolic solvent-soluble polyamide-imide resin used in the present invention) Thermometer, stirrer , anhydrous citric acid 19.2P (0.1 mol) in a 314 Tulo flask equipped with a cooling tube and a nitrogen introduction tube.
, trimellitic anhydride 172.8f (0.9 mol)
, diphenylmethane diincyane) 250.3F (1
, 0 mol) and m-cresol (400 V) were charged, and the temperature was raised in a 200-ton trench over about 1 hour in a nitrogen stream.

Significant foaming was observed near 70°C, and slight oozing and foaming were observed from 160 to 170°C.

The reaction was continued for 22 hours while distilling a small amount of cresol at the reflux temperature of cresol (200-210°C).

The reacted resin solution was clear.

The total amount of cresol distilled was 100 tons.

Next, 800 fTh of m-cresol was added and stirred thoroughly to reduce the nonvolatile content (200°C
A reddish-brown transparent resin solution with 55 voids (5°C) was obtained.
.

Further, the resin solution, and 37.5f (0°15 mol) of cresol-stabilized diphenylmethane diincyanate
was heated and melted and added.

Synthesis Example 2 (Production method of aromatic polyamideimide resin used in the present invention) Using the same apparatus as in Synthesis Example 1, 1.92r (1.0 mol) of trimellitic anhydride and diphenylmethane diisocyanin 250.3? (1.0 mol) Total N-methyl-2
- 500 tk of pyrrolidone was charged, and the temperature was raised to 140° C. in a trench for about 2 hours in a nitrogen stream.

The solution turned reddish brown and its viscosity increased significantly. 100 fk of dimethylacetamide was added to the diluent and the reaction was stopped.

The resulting polymer solution had a resin content of 25% by weight and a viscosity of 34 voids (20°C).

Examples of the present invention will be shown below.

[Examples 1 to 3] The resin paint obtained in Synthesis Example 1 and the resin paint obtained in Synthesis Example 2 were coated on a copper wire with a core wire diameter of 1.0 m in the proportions shown in the table by a conventional method and baked, and the finished diameter was A 1.08 m insulated wire was obtained.

[Comparative Example 1] On a copper wire with a core wire diameter of 1.0 mm, polyester resin paint (Toshiba Chemical Co., Ltd.'JA TV E 5325 F) color composition i + l + 2 (D paint k, at the ratio shown in 43) was applied and baked in the usual manner. An insulated wire with a finished diameter of 1.076 mm was obtained.

[Comparison Example 2] The paint obtained in Synthesis Example 2 and the polyester resin paint ('rV manufactured by Toshiba Chemical Co., Ltd.) were applied to a copper wire with a core wire diameter of 1.0 mm.
E5325F) was sequentially applied to the shell in the proportion shown in the conventional method and baked to obtain an insulated wire with a finished diameter of 1.076 then.

[Comparative Example 3] The paint obtained in Synthesis Example 1 was coated and baked to a thickness of 0.037 layers on a copper wire with a core wire diameter of 1.0 mm using a conventional method, and the finished diameter was 1.0 mm.
An insulated wire of 074m+n was obtained.

[Comparative Example 4] A polyester resin pigment (Toshiba Chemical Co., Ltd. 9TVE5325F) and a polyimide resin paint (ML manufactured by DuPont) were sequentially applied to a copper wire with a core wire diameter of 1.0 m in the proportions shown in the table and baked and finished. An insulated wire with a diameter of 1.074wn was obtained.

[Comparative Example 5] A polyesterimide resin paint (Isomyd RH manufactured by Schenectady Chemical Co.) and the paint obtained in Synthesis Example 2 were sequentially applied and baked in the proportions shown in the table on a copper wire with a core wire diameter of 1.0 mm, and baked. An insulated wire with a finished diameter of 1.0'74 mm was obtained.

Examples 1 to 3 and Comparative Examples 1 to 5 obtained as above
The table shows the characteristics test results of the enamel heddle.

Table note 1: NEMA MWI 000 Part 3.
55 IC'le-'m Note 2: NEMA MWlo
Compliant with oOPart 3.56 Presence or absence of foaming (effect of the invention) In the table, the insulated wires of each example of the present invention are Comparative Examples 1 to 5
As is clear from the comparison with , the present invention provides an insulated wire with excellent heat resistance, abrasion resistance, and good refrigerant resistance.

Representative Patent Attorney Yama 1) Akinobu

Claims (1)

[Claims] 1. A phenolic compound obtained by reacting a tricarboxylic acid and/or its derivative containing at least 5 molar oleic acid with a diisocyanate and/or its derivative in a phenolic solvent on a conductor core. The imide-based resin of solvent-soluble polyamide is coated and baked as layer (A), and the aromatic polyamide-imide resin body obtained by reaction in an organic polar solvent is coated and baked on the upper layer as layer (B). An insulated wire characterized by comprising: