JP3173828B2 - Self-lubricating insulated wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-lubricating insulated wire having excellent lubricity.

[0002]

2. Description of the Related Art Conventionally, in an electric maker or the like using an enameled wire, in order to speed up the manufacturing process of equipment,
Uses a high-speed automatic winding machine. Recently, in order to increase the efficiency of the motor, it is required to insert more enamel wires into narrow slots to increase the space factor.
However, the conventional enameled wire lacks lubricity and cannot be inserted even if an attempt is made to insert more enameled wire into the slot. Further, even if it is forcibly inserted with a large force, the coating is mechanically damaged due to friction or the like, and layer shorts increase. From such a thing,
In order to improve workability when inserting an enamel wire in a slot and reduce mechanical damage, an enamel wire having excellent lubricity has been demanded. As a means for solving this problem, a paint made of a polyester containing a modified polyester having a linear alkyl group having 21 or more carbon atoms added to the terminal of a molecular chain is coated on a conductor directly or via another insulator at least in the outermost layer. A coating consisting of a self-lubricating insulated wire coated and baked to form a coating, or a polyamide containing a modified polyamide in which a linear alkyl group having at least 21 carbon atoms is added to the terminal of the molecular chain, directly or on a conductor. There is a self-lubricating insulated wire coated with at least the outermost layer through another insulator, baked, and formed with a coating.

[0003]

However, this is considerably superior in lubricity as compared with a self-lubricating insulated wire using a lubricating layer made of polyamide or the like, but is used for applications requiring more excellent lubricity. However, there is a need for a self-lubricating insulated wire having much better lubricity than this self-lubricating insulated wire.

[0004] Therefore, an object of the present invention is to provide a self-lubricating insulated wire having extremely excellent lubricity.

[0005]

According to the present invention, at least one of the molecules is a straight-chain perfluoroalkyl group having 9 or more carbon atoms. It is applied and baked so as to constitute the outermost layer. By coating and baking at least on the outermost layer, an insulated wire having excellent lubricity as the object of the present invention can be obtained.

[0006] The paint used in the present invention is applied and baked directly on a conductor or via another insulating material. Coating ・
The resin film obtained by baking shows very good lubricity even when thin, and excellent resistance to thermal and mechanical damage, so it can be applied and baked on another insulating material with poor lubricity. It is effective to use it as.

As the other insulator, any insulator may be used, for example, polyurethane, polyvinyl formal, polyester, polyesterimide, polyhydantoin, polyamideimide, polyesteramideimide,
Examples include polyhydantoin esters and polyester amides.

When considering the application of the insulated wire of the present invention to the field of refrigerator motors and the like, polyester, polyesterimide, polyesteramide imide used as an insulator for refrigerant-resistant insulated wire among these various insulators. It is desirable to use.

The polyester resin used in the present invention wherein at least one molecule has a linear perfluoroalkyl group having 9 or more carbon atoms is a polyhydric alcohol (hereinafter referred to as component (I)), a polyhydric carboxylic acid or a polycarboxylic acid or a polycarboxylic acid thereof. Derivatives (hereinafter referred to as component (II)), compounds having a linear perfluoroalkyl group having 9 or more carbon atoms in the molecule and having a functional group capable of reacting with component (I) or component (II) (hereinafter referred to as component (II)) (Referred to as (III)).

The amount of the linear perfluoroalkyl group having 9 or more carbon atoms in the resin is most preferably 0.05 to 10% by weight.

[0011]

Hereinafter, the present invention will be described in more detail. The modified polyester or modified polyamide in which a linear fluoroalkyl group having 9 or more carbon atoms is added to the terminal of the molecular chain used in the present invention is represented by the following general formula (i) or (ii), The modified polyester or the modified polyamide in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to at least one of the following general formulas (i), (ii) and (iii): Means one or the other. R- [P] -R (i) R- [P]-... (ii)-[P]-... (iii) (where [P] is a polyester constituting the main chain) Or a polyamide, R represents a linear perfluoroalkyl group having 9 or more carbon atoms.)

A linear fluoroalkyl group having 9 or more carbon atoms is represented by the following general formula (iv). CF ₃ (CF ₂ ) _n-1 − (iv) (in the formula, n ≧ 9) Further, the above-mentioned general formula (iv) in which a part of fluorine is replaced by hydrogen. Which may be represented by the following general formula (v). CF ₃ (CF ₂ ) _n-1 (CH ₂ ) _m − (v) (where n + m ≧ 9)

The number of carbon atoms of the linear perfluoroalkyl group bonded to the terminal of the main chain must be 9 or more in order to obtain good lubricity, and if less than 9, lubricity is not sufficient. That is, when the linear perfluoroalkyl group is represented by the general formula (iv), n ≧ 9. Also,
The chain of the linear perfluoroalkyl group is desirably completely linear, but may be a slightly branched perfluoroalkyl group as long as the linear portion has 9 or more carbon atoms.

In the present invention, the ratio of the terminal linear perfluoroalkyl group occupied by the modified polyester or the modified polyamide having a linear perfluoroalkyl group having 9 or more carbon atoms added to the terminal of the molecular chain is 0.05% by weight or more. And more preferably 0.05% by weight or more.
10% by weight. The ratio of the terminal linear perfluoroalkyl group in this polyester or polyamide is 0.5.
If it is less than 05% by weight, the lubricity of the coating film is poor, and
If it is larger than the weight%, the storage stability as a paint,
It adversely affects the appearance and mechanical properties of the wire.
In the above range, 0.1 to 5% by weight is more preferable in terms of storage stability as a paint and appearance as an electric wire.

Examples of the polyhydric alcohol (component (I)) used for obtaining the polyester resin used in the present invention include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-
Propylene glycol, 1,8-propanediol, various butane-, pentane-, or hexanediols,
For example, butanediol-1,3, butanediol-1,
4, pentanediol-1,5, butyne-2-diol-1,4 or 2,2-dimethylpropanediol-1,3,
3-ethyl-2-butyl-propanediol-1,3,
1,4-dimethylolcyclohexane, butenediol-1,4, hydrogenated bisphenol (ie, hydrogenated P, P'-dihydroxydiphenylpropane or a homolog thereof) cyclic glycol, for example, 2,2,4,4-tetra Methyl-1,3-cyclobutanediol, hydroquinone-
Di-β-hydroxyethyl ether, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol and the like. As trivalent or higher, glycerin, pentaerythritol 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, sorbitol, mannitol, dipentaerythritol, diglycerol, tris- (hydroxyalkyl ) -Isocyanurate, for example tris- (β-hydroxyethyl) -isocyanurate, tris- (β-hydroxypropyl)
-Isocyanurate and the like, and others obtained by reacting isocyanuric acid with an epoxy (for example, alkylene oxide, styrene oxide, shrimp chlorohydrin, etc.), and these can be used alone or in combination.
Among these, preferred in terms of the flexibility and heat resistance of the insulated wire obtained are ethylene glycol, glycerin,
In this case, tris- (β-hydroxyethyl) -isocyanurate is mainly used.

Next, polyvalent carboxylic acids and derivatives thereof (for example, aromatic, alicyclic and aliphatic polycarboxylic acids are examples of component (II), such as terephthalic acid, and general formula (A)

[0017]

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A phenylindanedicarboxylic acid (for example, 3- (4-carboxyphenyl) -5-indanecarboxylic acid, wherein R is selected from the group consisting of hydrogen and an alkyl group containing 1 to 3 carbon atoms); -(3-carboxyphenyl) -5-indanecarboxylic acid, 3-carboxyphenyl-1,1,3-triethyl-6-indanecarboxylic acid, 3- (4-carboxyphenyl) -1-methyl-1,3- Dipropyl-5-indancarboxylic acid, 3
-(4-carboxyphenyl) -1-methyl-1,3-
Diethyl-6-indanecarboxylic acid, etc.), phthalic acid, phthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, adipic acid, phthalic acid, succinic acid, maleic acid, sebacic acid, isosebacic acid, dimer Acid, tetrachlorophthalic acid, hexachloroendmethylenetetrahydrophthalic acid, 4,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylpropane, benzophenonedicarboxylic acid, trimellitic acid, trimellitic anhydride, hemi-meritic Acids, hemi-mellitic anhydride, trimesic acid, trimesic anhydride and the like.

The derivatives of polyvalent carboxylic acids include
For example, in the case of lower dialkyl esters of these aforementioned acids, for example terephthalic acid, dimethyl terephthalate,
Diethyl terephthalate, propyl terephthalate, butyl terephthalate, amyl terephthalate, hexyl terephthalate, octyl terephthalate or their half esters, for example, monomethyl terephthalate, etc., as well as arylesters, for example, diphenyl terephthalate, monophenyl trimellitate, etc., and acids There are halides such as terephthalic acid dichloride, isophthalic acid dichloride, trimellitic acid monochloride and the like, and these can be used alone or as a mixture.

Among them, terephthalic acid, isophthalic acid, or a derivative thereof or a part thereof is preferably a polyvalent carboxylic acid having a 5-membered ring imide described below in view of the heat resistance of the insulated wire obtained. This is the case when replacing.
The polyvalent carboxylic acid having a 5-membered ring imide can be obtained, for example, by a reaction between the following two compounds.

(A): An aromatic carboxylic acid anhydride containing at least one other reactive group in addition to a 5-membered carboxylic acid anhydride group. This latter reactive group can be a carboxyl group, as well as a carboxylic anhydride group or a hydroxyl group. Instead of the cyclic carboxylic acid anhydride group mentioned first, a divalent carboxyl group or an ester or half ester thereof bonded to an adjacent carbon atom, and an imide group as far as possible to form an imide group. Half amides with primary amines provided may also be used.

(B): primary amine containing at least one other reactive group in addition to the primary amino group. This latter reactive group can be a carboxyl group, a hydroxyl group or even a primary amino group. Instead of a primary amine, salts, amides, lactams or polyamides of the amine may also be used, so long as the attached primary amino group can form an imide.

Examples of the compound (a) having a cyclic carboxylic acid anhydride group and other functional groups include tricarboxylic acid anhydrides, for example, trimellitic anhydride, hemi-mellitic anhydride, 1,2,5-naphthalene Tricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,
8,4-naphthalenetricarboxylic anhydride, 3,4,4 '
-Diphenyltricarboxylic anhydride, 3,4,4'-diphenylmethanetricarboxylic anhydride, 3,4,4'-diphenylether tricarboxylic anhydride, 3,4,4'-benzophenone tricarboxylic anhydride, tetracarboxylic dianhydride Anhydrides such as pyromellitic dianhydride, merofaniic dianhydride, 2,3,8,7-naphthalenetetracarboxylic dianhydride, 1,3,4,5-naphthalenetetracarboxylic dianhydride, 1 2,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3'4,
There is 4'-benzophenonetetracarboxylic dianhydride. Particularly preferred is trimellitic anhydride. As other examples of the polycarboxylic acid providing an imide group, aliphatic polycarboxylic acids such as butanetetracarboxylic acid and maleic anhydride can also be used.

The compound (b) having a primary amino group and another functional group includes, for example, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, pentidine, 3,3'-diaminodiphenyl,
1,4-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, α, ω-nonamethylenediamine, 1,7-dimethylheptamethylenediamine, 4,
4'-diaminodiphenyl ketone, bis- (4-aminophenyl) -α, α-p-xylene, toluylenediamine, xylenediamine, xylylenediamine, hexamethylenediamine, ethylenediamine, 4,4'-dicyclohexylmethanediamine, Primary diamines such as diaminodiphenylsulfonebenzoguanamine (particularly preferred are aromatic diamines) and also amino alcohols such as, for example, monoethanolamine, monopropanolamine or dimethylethanolamine, and also for example glycine, aminopropionic acid, aminocapron Acids, aminocarboxylic acids such as aminobenzoic acid may also be used.

When reacting the compound (a) and the compound (b), the ratio of the two used is such that when the compound (a) is a tricarboxylic anhydride and the compound (b) is a diamine, Compound (b) is used in an amount of 0.1 to 1.0 mol, preferably 0.5 to 1.0 mol, per 1 mol. In this case, 0.5 mol or more of the compound (b) is
Reacts with the carboxyl group of the tricarboxylic anhydride to form an amide bond. When the compound (a) is a tetracarboxylic dianhydride and the compound (b) is a diamine, the compound (b) is used in an amount of 0.1 mol per 1 mol of the compound (a).
Mole to 1.0 mole. When the compound (a) is a tricarboxylic anhydride and the compound (b) is a monoamine, the compound (b) is used in an amount of 0.1 to 2 mol per 1 mol of the compound (a). , Preferably between 1 and 2 moles. However, an amount exceeding 1 mol of the compound (b) forms an amide bond, an ester bond and the like.

It is particularly frequently used that tricarboxylic anhydride is used as compound (a) and aromatic diamine is used as compound (b) in a molar ratio of (a) :( b) = 1: 0.5 to 1. This is the case when used. More preferably, the compound of the formula (B) obtained from 2 mol of trimellitic anhydride and 1 mol of 4,4'-diaminodiphenylmethane or 4,4'-diaminodiphenyl ether is used.

[0027]

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A polyvalent carboxylic acid having (R: -CH _2- or -O-). In addition, formula (C) obtained by using 1 to 2 mol of 4,4'-diaminophenylmethane or 4,4'-diaminodiphenyl ether per 2 mol of tricarboxylic anhydride

[0029]

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(The value of n is preferably n ≦ 4 on average.)
R: -CH ₂ -, or -C-) is polycarboxylic acid having. (C): m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2,5-triisocyanate benzene, diphenyl ether-4,4'-diisocyanate, diphenylmethane-4, 4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylthioether-4,4'-diisocyanate, naphthalene diisocyanate, polymethylene polyphenylene, polyisocyanate, hexamethylene diisocyanate, xylene Compound (a) is obtained by mixing a polyisocyanate such as diisocyanate with an acid anhydride compound such as compound (a).
Is a polyvalent carboxylic acid obtained by reacting the compound (c) with 0.1 to 2 mol, preferably 1.0 to 3.0 mol with respect to 2 mol of the compound (c).

When a tricarboxylic anhydride is used as the compound (a), polycarboxylic acids having an amide bond and a five-membered imide bond can be obtained. Particularly frequently used is a case where tricarboxylic anhydride is used as the compound (a). More preferably, trimellitic anhydride is used as the compound (a), and diphenylmethane-4,4 is used as the compound (c). It is obtained using 4'-diisocyanate, diphenylether-4,4'-diisocyanate.

The reaction between the compound (a) and the compound (b) or the reaction between the compound (a) and the compound (c) is carried out without a solvent or in the presence of a solvent. When obtaining an imide-modified polyester-based resin, in the case of a combination of the compound (a) and the compound (b), the compound (a) can be formed at once without preparing a polyvalent carboxylic acid having a five-membered imide bond. It is also possible to react a) with compound (b) with a polyhydric alcohol.
Further, in the compound (a), a part of the aromatic carboxylic anhydride may be replaced with a polyvalent carboxylic acid to form an amide bond, and further, a polyvalent carboxylic acid or a derivative thereof (an acid halide) may be formed. A diamine is reacted with a diamine at a molar ratio of 1: 0.5 to 1 to obtain a diamine having an amino group at a terminal and used as the compound (b), or a diamine having an amide group in the molecule is used as a compound. An imide or amide-modified polyester resin can also be obtained by using it as (b).

The method for producing these polyvalent carboxylic acids having a 5-membered ring imide is described in Japanese Patent Publication No. 38-2150.
No. 0, No. 40-9018, No. 42-27071, No. 45-18816, Japanese Patent Application No. 42-43547, Japanese Patent Application No. 42-43548, Japanese Patent Application No. 43-89689, Japanese Patent Application No. 44-44. No. 67497, U.S. Pat. No. 3,426,098, and French Patent 20099052.

When synthesizing a polyvalent carboxylic acid having a 5-membered ring imide in the molecule, alkylene carbonate may be added as a part of a reaction component and a solvent. This production method is described in detail in JP-B-48-17837 and JP-B-48-17838. Also useful as a carboxylic acid raw material in the synthesis of the polymer of the present invention among the hetero rings other than the imide ring are acids containing a lactam ring.
3, 2821,517, 3793,250 and JP-B-48-12198.

Any examples of the polyamide resin used in the present invention may be used. For example, 6,6-nylon, 6
-Nylon, 6,10-nylon, 6,12-nylon,
In addition to 11-nylon, 12-nylon, and the like, there are copolymerized nylons obtained by appropriately combining and copolymerizing these respective monomer components. Among these, 6,6-nylon and 6-nylon are preferable when the polyamide resin is used for the purpose of the protective layer, and a unit of 12-nylon is used when the polyamide resin is used for the purpose of the self-fusion coating layer. It is preferable to use copolymerized nylon.

The monomer components used to obtain the polyamide resin constituting the main chain include lactams such as ε-caprolactam and ω-lauryl lactam, and polyvalents such as adipic acid, sebacic acid, dodecandioic acid and dimer acid. Carboxylic acids, polyamines such as tetramethylenediamine, hexamethylenediamine, ε-aminocaproic acid, ω
-Amino acids such as aminododecanoic acid;

On the other hand, examples of the compound used to introduce a linear perfluoroalkyl group having 9 or more carbon atoms into the molecular terminal of a polyester resin or a polyamide resin include fatty acids and alkyl esters, higher alcohols and amines. Examples of fatty acids include perfluorodocosanoic acid,
There are perfluorooctadecanoic acid and the like, and derivatives of these fatty acids include esters and the like. Examples of higher alcohols include perfluorodocosanol, perfluorodecanol, and the like. Examples of amines include perfluorotocosylamine, perfluorooctadecasylamine, and the like.

Of course, when introducing a long-chain perfluoroalkyl group at the molecular terminal of a polyester or polyamide using these compounds, the reaction with the various raw materials used for obtaining the main chain polyester or polyamide described above is required. It is necessary to select one having a functional group that can be used. These compounds do not need to be used alone, and may be a mixture.

The polyester resin containing a modified polyester resin having a linear perfluoroalkyl group added to the terminal of the molecular chain or the polyamide resin containing a modified polyamide resin used in the present invention constitutes the main chain of the polyester or polyamide described above. And a compound for introducing a linear perfluoroalkyl group into the terminal of the molecule described above.

In the present invention, the main component is a polyester containing a modified polyester having a linear perfluoroalkyl group having 9 or more carbon atoms added to the end of the molecular chain, or a linear perfluoroalkyl having 9 or more carbon atoms at the end of the molecular chain. The main component is a polyamide containing a modified polyamide to which a group is added, and the ratio of this linear perfluoroalkyl group is 0.0
5% by weight or more of the above polymer solution, if necessary,
One or more of other thermoplastic resins, thermosetting resins, fillers, pigments, dyes, etc. may be added to the polymer solution as long as the properties are not impaired.

As described above, in order to obtain a self-lubricating insulated wire having extremely excellent lubricity, a modified polyester group having a linear perfluoroalkyl group having 9 or more carbon atoms added to the terminal of the molecular chain. A paint containing polyester as a main component or a paint containing polyamide containing modified polyamide as a main component is applied to at least the outermost layer on a conductor directly or via another insulating material, and baked to form a film. This coating has excellent lubricity and excellent resistance to mechanical damage even when it is thin, so it is particularly effective to apply it as a protective film on other insulators with poor lubrication. It is.

The other insulator may be any insulator, for example, polyester, polyesterimide, polyhydantoin, polyamideimide, modified amideimide,
Examples include polyhydantoin esters, polyurethane, polyvinyl formal, and the like. When considering the application of the self-lubricating insulated wire of the present invention to the field of refrigerator motors and the like, among these various insulators, polyester, polyesterimide, and polyesteramide used as insulators of insulated wires for refrigerant resistance are used. Preference is given to imides, more preferably polyesters and polyesterimides. In addition, carbon number 9
As a resin for adding the above perfluoroalkyl group,
Epoxy, polyvinyl formal and the like are used in addition to polyester and polyamide.

[0043]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited thereto. In the following Reference Examples, the reaction was carried out in a two-liter four-necked flask using a reaction vessel equipped with a cooling tube equipped with a calcium chloride tube, a thermometer, a nitrogen introduction tube, and a stirrer. Used a mantle heater. Further, the coating and baking of the polymer solution in Examples and Comparative Examples were performed using a rigid furnace having a furnace length of 7.6 m, and the furnace temperature was 500 ° C. in the upper part, 500 ° C. in the middle part, and 4 in the lower part.
The test was carried out at 50 ° C. at a linear velocity of 20 m / min.

The characteristics of the self-lubricating insulated wire obtained were as described in JIS C 3003 or NEMA except for the coefficient of static friction.
It measured according to MW-1000. The coefficient of static friction is a measurement of the coefficient of static friction between self-lubricating insulated wires. The measuring method is as follows. Two self-lubricating insulated wires are attached in parallel to a metal block, and the two self-lubricating insulated wires are fixed on a plane and two self-lubricating insulated wires are placed on each other. Are placed at right angles, and the minimum load required to move the former metal block along the two self-lubricating insulated wires on the plane is divided by the load of the metal block.

((Example of polyester)) (Reference Example 1) Dimethyl terephthalate 388.4 g (2.0 mol) Ethylene glycol 93.1 g (1.5 mol) Glycerin 92.1 g (1.0 mol) Acetic acid 0.8 g of lead and 300.0 g of xylene were charged into a flask, and the temperature was gradually increased while stirring.
After reacting at 40 ° C. for 2 hours, the temperature was further increased at a rate of 20 ° C./hour.

During this time, xylene and reaction by-products were distilled out of the system through a cooling pipe. The viscosity of the contents gradually increased. When the temperature reached 240 ° C, the system was depressurized while maintaining the temperature, and the reaction was further continued. The viscosity of the contents further increased. After 30 minutes from the start of the depressurization, the inside of the system was returned to normal pressure, the heating was stopped, and cresol was added so that the resin content became 40%, and the resin was heated and dissolved. Thereafter, tetrabutyl titanate and zinc octylate were added to the resin component for 2 times each.
% By weight to give a polyester coating. The viscosity of the obtained paint was 72 poise. This paint is 1.0mm in diameter
The coating and baking were repeated six times on the copper wire of Example 1 to obtain an insulated wire. Table 1 shows the properties of the obtained insulated wires.

Comparative Example 1 Dimethyl terephthalate 388.4 g (2.0 mol) Ethylene glycol 93.1 g (1.5 mol) Glycerin 92.1 g (1.0 mol) Octacosanoic acid 3.9 g Lead acetate 0.9 g 8 g of xylene and 300.0 g of xylene were charged into a flask, and a polyester paint was obtained in the same manner as in Reference Example 1 to obtain an insulated wire. Table 1 shows the properties of the obtained insulated wires.

Comparative Example 2 A polyester paint was obtained in the same manner as in Comparative Example 1 except that 3.9 g of octacosanoic acid was replaced with 3.9 g of perfluorocaprylic acid, and then an insulated wire was obtained. Table 1 shows the properties of the obtained insulated wires.

Comparative Example 3 A polyester paint was obtained in the same manner as in Comparative Example 1 except that 3.9 g of octacosanoic acid was replaced by 19.5 g of perfluorocaprylic acid, and then an insulated wire was obtained. Table 1 shows the properties of the obtained insulated wires.

Example 1 A polyester coating was obtained in the same manner as in Comparative Example 1, except that 3.9 g of octacosanoic acid was replaced by 3.9 g of perfluorooctadecanoic acid, and then an insulated wire was obtained. Table 1 shows the properties of the obtained insulated wires.

Example 2 A polyester paint was obtained in the same manner as in Comparative Example 1 except that 3.9 g of octacosanoic acid was replaced with 0.2 g of perfluorooctadecanoic acid, and then an insulated wire was obtained. Table 1 shows the properties of the obtained insulated wires.

Example 3 A polyester paint was obtained in the same manner as in Comparative Example 1 except that 3.9 g of octacosanoic acid was replaced with 0.4 g of perfluorooctadecanoic acid, and then an insulated wire was obtained. Table 1 shows the properties of the obtained insulated wires.

Example 4 In Comparative Example 1, 3.9 g of octacosanoic acid was replaced by 19.5 g of perfluorooctadecanoic acid.
Polyester paint was obtained in the same manner as in Comparative Example 1 except that the above was replaced with Comparative Example 1, and then an insulated wire was obtained. Table 2 shows the characteristics of the obtained insulated wires.

Example 5 In Comparative Example 1, 3.9 g of octacosanoic acid was replaced by 39.0 g of perfluorooctadecanoic acid.
Polyester paint was obtained in the same manner as in Comparative Example 1 except that the above was replaced with Comparative Example 1, and then an insulated wire was obtained. Table 2 shows the characteristics of the obtained insulated wires.

Example 6 In Comparative Example 1, 3.9 g of octacosanoic acid was replaced with 78.0 g of perfluorooctadecanoic acid.
Polyester paint was obtained in the same manner as in Comparative Example 1 except that the above was replaced with Comparative Example 1, and then an insulated wire was obtained. Table 2 shows the characteristics of the obtained insulated wires.

Example 7 A polyester coating was obtained in the same manner as in Comparative Example 1, except that 3.9 g of octacosanoic acid was replaced by 3.9 g of perfluorodecanoic acid, and then an insulated wire was obtained. Table 2 shows the characteristics of the obtained insulated wires.

Comparative Example 4 388.4 g (2.0 mol) of dimethyl terephthalate 186.0 g (3.0 mol) of ethylene glycol 184.2 g (2.0 mol) of glycerin 0.8 g of lead acetate 300.0 g of xylene Charge the flask and stir well until the contents are 140
After raising the temperature to ℃ and reacting at that temperature for 1.5 hours, the temperature was further raised at a rate of 20 ° C./hour. When the temperature reached 200 ° C., the reaction was carried out at that temperature for 1 hour. During this time, xylene and methanol as a reaction by-product were distilled out of the system through a cooling tube. Thereafter, the temperature of the content was cooled to 110 ° C., and 396.5 g (2.0 mol) of 4,4′-diaminodiphenylmethane 768.5 g (4.0 mol) of trimellitic anhydride was added to the system. When the temperature of the contents is raised again,
In the vicinity, a yellow precipitate was formed in the contents, and the contents solidified.

The stirring was stopped once, the temperature was kept at 140 ° C. for 30 minutes, and the temperature was raised to 180 ° C. over about 1 hour. During this time, water as a reaction by-product was distilled out of the system through a cooling pipe. Since the contents became fluid, stirring was started again, and the contents became transparent and the viscosity gradually increased while the temperature was raised to 230 ° C. over one hour. 2 at 230 ° C
After continuing the reaction for a period of time, the pressure in the system was reduced and the reaction was carried out for another 1 hour.
Cresol was added to stop the reaction, and the contents were dissolved in cresol. Here, resin 10
2 parts by weight of tetrabutyl titanate and 2 parts by weight of zinc octylate were added and mixed with 0 part by weight to obtain a polyesterimide paint. Apply this paint on a copper wire with a diameter of 1.0 mm.
Repeated baking was repeated to obtain an insulated wire. Table 2 shows the characteristics of the obtained insulated wires.

Example 8 388.4 g (2.0 mol) of dimethyl terephthalate 186.0 g (3.0 mol) of ethylene glycol 184.2 g (2.0 mol) of glycerin 15.8 g of perfluorooctadecanoic acid 0.1 g of lead acetate 8 g of xylene, 300.0 g, was charged to the flask, and the content was reduced to 140 with good stirring.
After raising the temperature until the temperature reached 200 ° C., the temperature was further raised at a rate of 20 ° C./hour, and when the temperature reached 200 ° C., the reaction was carried out at that temperature for 1 hour. During this time, xylene and methanol as a reaction by-product were distilled out of the system through a cooling tube. Thereafter, the temperature of the contents was cooled to 110 ° C., and 396.5 g (2.0 mol) of 4,4′-diaminodiphenylmethane 768.5 g (4.0 mol) of trimellitic anhydride was added to the system. When the temperature of the contents is raised again,
In the vicinity, a yellow precipitate was formed in the contents, and the contents solidified.

The stirring was stopped once, the temperature was kept at 140 ° C. for 30 minutes, and the temperature was raised to 180 ° C. over about 1 hour. During this time, water as a reaction by-product was distilled out of the system through a cooling pipe. Since the contents became fluid, stirring was started again, and the contents became transparent and the viscosity gradually increased while the temperature was raised to 230 ° C. over one hour. 2 at 230 ° C
After continuing the reaction for a period of time, the pressure in the system was reduced and the reaction was carried out for another 1 hour.
The reaction was stopped by adding cresol so as to obtain the solution, and the contents were dissolved in cresol. Here, 2 parts by weight of tetrabutyl titanate and 2 parts by weight of zinc octylate were added to and mixed with 100 parts by weight of the resin to obtain a paint.
The viscosity of the thus obtained polyester imide resin paint having at least one molecule terminated with a linear perfluoroalkyl group having 17 carbon atoms was 44 poise. Table 2 shows the characteristics of the obtained insulated wires.

[0061]

[Table 1]

[0062]

[Table 2]

As is apparent from Tables 1 and 2, the insulated wire of the present invention using a polyester resin having at least one molecule terminated with a linear perfluoroalkyl group having 9 or more carbon atoms (Examples 1 to 8) It is clear that the coefficient of static friction is much lower than that of the conventional insulated wires (Comparative Examples 1, 2 and 3), and that it is extremely excellent in lubricity. When the number of carbon atoms in the linear perfluoroalkyl group bonded to the molecular terminal is less than 9 (Comparative Example 2), the lubricating property is not sufficient, and the composition of the components used for introducing the linear alkyl group is not sufficient. Even when the amount was increased (Comparative Example 3), the lubricity could hardly be improved.

If the amount of the linear perfluoroalkyl group is less than 0.05% by weight, the lubricity can hardly be improved, and if it is more than 10% by weight, the appearance and the stability of the varnish deteriorate.

((Example of polyamide)) (Reference Example 2) 6,6-nylon (CM300I manufactured by Toray)
N) 100 g of m-cresol and 400 g of m-cresol were charged into a 1-liter flask, heated while stirring, and dissolved at 185 ° C. for 8 hours to obtain a polyamide paint. A commercially available polyester paint (Telebec E-1150 manufactured by Dainichi Seika Co., Ltd.) was repeatedly applied and baked five times on a copper wire having a diameter of 1.0 mm, and then the polyamide paint was applied and baked once thereon to obtain an insulated wire. Table 3 shows the properties of the obtained insulated wires.

Comparative Example 5 1.0 g of octacosanoic acid was added to the polyamide paint of Reference Example 2, and the temperature was increased while stirring.
The reaction was carried out at 185 ° C. for 8 hours to obtain a polyamide paint. A commercially available polyester paint (Telebec E-1150 manufactured by Dainichi Seika Co., Ltd.) was repeatedly applied and baked five times on a copper wire having a diameter of 1.0 mm, and then the polyamide paint was applied and baked once thereon to obtain an insulated wire. Table 3 shows the properties of the obtained insulated wires.

Example 9 A polyamide paint was obtained in the same manner as in Comparative Example 5 except that perfluorooctadecanoic acid was used instead of octacosanoic acid in Comparative Example 5. A commercially available polyester paint (Telebec E-1150 manufactured by Dainichi Seika Co., Ltd.) was repeatedly applied and baked five times on a copper wire having a diameter of 1.0 mm, and then the polyamide paint was applied and baked once thereon to obtain an insulated wire. Table 3 shows the properties of the obtained insulated wires.

Example 10 A polyamide coating material was obtained in the same manner as in Comparative Example 5 except that perfluorodecanoic acid was used instead of octacosanoic acid in Comparative Example 5. Commercially available polyester paint (Telebeck E manufactured by Dainichi Seika Co., Ltd.) on a copper wire with a diameter of 1.0 mm
-1150) was repeatedly applied and baked five times, and then the polyamide paint was applied and baked once thereon to obtain an insulated wire. Table 3 shows the properties of the obtained insulated wires.

Example 11 Comparative Example 5 was repeated except that perfluorocaprylic acid was used in place of octacosanoic acid of Comparative Example 5.
A polyamide paint was obtained in the same manner as described above. A commercially available polyester paint (Telebec E-1150 manufactured by Dainichi Seika Co., Ltd.) was repeatedly applied and baked five times on a copper wire having a diameter of 1.0 mm, and then the polyamide paint was applied and baked once thereon to obtain an insulated wire. Table 3 shows the properties of the obtained insulated wires.

[0070]

[Table 3]

From Table 3, it can be seen that the insulated wires of the present invention (Examples 9 to 1) using a polyamide resin in which at least one molecule is terminated with a linear perfluoroalkyl group having 9 or more carbon atoms.
No. 0) has a very low coefficient of static friction and is extremely excellent in lubricity as compared with the conventional insulated wire (Reference Example 2, Comparative Examples 5 and 6).

[0072]

According to the self-lubricating insulated wire of the present invention, the outermost layer comprises a coating mainly composed of a polyamide resin or a polyester resin in which at least one molecule is a straight-chain perfluoroalkyl group having 9 or more carbon atoms. It is applied and baked, has remarkably excellent lubricating properties, and the insulating paint used in the present invention is chemically stable and therefore has excellent storage stability. Good appearance and mechanical properties. Therefore, more electric wires can be inserted into the slot without being damaged, so that the space factor can be increased and the efficiency of the motor can be increased. In addition, the resin film obtained by coating and baking has very good lubricity even when it is thin, and exhibits excellent properties to withstand thermal and mechanical damage. Therefore, it can be applied on other insulators with poor lubricity.・ It can also be used as a baking protection layer.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI H01B 7/18 H01B 7/18 B (72) Inventor Kazuo Hanaoka 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Teruo Yamazawa 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. (56) References JP-A-57-209967 (JP, A) JP-A-58-17179 (JP, A) JP-A Sho 61-34074 (JP, A) JP-A-62-154408 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01B 7/00 303 C09D 5/00 C09D 167/00 C09D 177 / 00 H01B 3/30 H01B 7/18

Claims (6)

(57) [Claims] An insulated wire obtained by applying and baking an insulating paint on a conductor directly or via another insulating material, wherein at least one molecule has a terminal with a straight-chain perfluoroalkyl group having 9 or more carbon atoms. A coating mainly composed of a certain polyamide resin or polyester resin is applied to the outermost layer.
Self-lubricating insulated wire characterized by being baked. 2. The self-lubricating insulated wire according to claim 1, wherein the proportion of the linear perfluoroalkyl group in the polyamide resin or the polyester-based resin is 0.01 to 10% by weight. Insulated wires. 3. The self-lubricating insulated wire according to claim 1, wherein the polyamide resin is a copolymerized nylon containing a 12-nylon unit. 4. The self-lubricating insulated wire according to claim 1, wherein the terminal of at least one molecule has 9 carbon atoms.
Component (I): Polyhydric alcohol Component (II): Polycarboxylic acid or its derivative Component (III): Linear perfluoroalkyl having 9 or more carbon atoms in the molecule A self-lubricating insulated wire characterized by being a resin obtained by reacting a compound having an alkyl group and having a functional group capable of reacting with the component (I) or the component (II). 5. The self-lubricating insulated wire according to claim 4, wherein the polyhydric alcohol contains ethylene glycol and glycerin and / or tris-2-hydroxyethyl isocyanurate as a main component. Insulated wires. 6. The self-lubricating insulated wire according to claim 4, wherein the polycarboxylic acid is an aromatic polycarboxylic acid.