JPH05205533A - Self adhesive insulated wire - Google Patents

Abstract

PURPOSE:To improve smoothness and surface lubricity of an adhesive coat, reduce static and dynamic friction coefficient of the eliminate coat, flaws caused by a guide pulley or the like upon coil processing, enhance the space factor of a wound coil, and improve mold releasing performance of the wound coil in a self adhesive insulated wire. CONSTITUTION:An adhesive resin paint mainly composed of such a resin that a straight chain perufluoroalkyl group, whose carbon number is 9 or more is added at the end of a molecular chain or of such a resin that the straight chain perufluoroalkyl group whose carbon number is 9 or more, being copolymerized into a molecule, is applied on the outermost layer, at least, on a conductor, directly or via other insulator, followed by baking so as to form an adhesive film. The ratio of the straight chain perufluoroalkyl group, whose carbon number is 9 or more relative to a main component resin in the adhesive resin paint ranges from 0.05 to 20wt%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-adhesive insulated electric wire used for a wide range of purposes as an electric wire for equipment coils of electric / communication equipment and the like. The static and dynamic friction coefficient of the coil is reduced, scratches due to guide pulleys, etc. are eliminated during winding processing, the space factor of the winding coil is increased, and the mold release property of the winding coil is improved. Is.

[0002]

2. Description of the Related Art Conventionally, a self-adhesive insulated wire has an insulating coating made of, for example, polyurethane, polyvinyl formal, polyester, polyesterimide, polyhydantoin, polyamideimide, polyesteramideimide, polyhydantoin ester, polyesteramide on the conductor. An insulating film is formed by coating and baking, and one or more of polyamide, polyvinyl butyral, epoxy resin, polyester, polyhydroxy ether, or a resin in which two or more kinds are combined on the insulating film, or an amino resin, stable. An adhesive coating formed by applying and baking an adhesive coating composed of a composition obtained by mixing one or more of a polyisocyanate, a triazine resin, a phenol resin, and a phenol formaldehyde resin. In, since the securing work of the winding coil is simplified so resin varnish impregnation treatment after coiling is required, it is widely used.

By the way, such a self-adhesive insulated wire is damaged by a nozzle, a pulley or the like in a winding process in manufacturing a winding coil, which causes a layer short circuit or a ground failure. It was In particular, in recent years, since the electric wire is subjected to severe conditions as the winding speed increases, the above phenomenon tends to occur frequently, and a solution to this problem has been desired. As a means for preventing such a problem, it is necessary to reduce the friction coefficient and increase the abrasion resistance of the self-adhesive insulated wire. Therefore, conventionally, a self-adhesive insulated wire coated with lubricating oil, wax, wax or the like has been used.

However, in the case where lubricating oil or the like is applied to the adhesive coating of the self-adhesive insulated wire, the fixing force (adhesive force) when wound in a coil is significantly reduced and the nozzle and pulley are soiled with lubricating oil and the like. There was a problem. Further, when the winding coil is fixed, it is easy to take out the coil from the mold, so that there is a disadvantage that the mold must be coated with a release agent in advance.

[0005]

Therefore, an object of the present invention is to improve the smoothness and surface lubricity of an adhesive coating,
It is possible to reduce the static and dynamic friction coefficient of the coating, eliminate scratches due to guide pulleys during winding processing, increase the space factor of the winding coil, and improve the mold release property of the winding coil. To obtain a self-adhesive insulated wire.

[0006]

This problem is solved by copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in a resin or a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to the end of a molecular chain. Adhesive resin paint mainly composed of resin, directly on the conductor or through another insulator,
It is solved by applying at least the outermost layer, baking, and forming an adhesive coating to obtain a self-adhesive insulated wire.

[0007]

In the self-adhesive insulated wire according to the present invention, the adhesive resin paint is applied and baked on the conductor directly or through another insulating coating, so that the adhesive coating itself has lubricity and mold releasing property.

The present invention will be described in detail below. First,
The adhesive resin paint used in the present invention will be described. This adhesive resin coating is mainly composed of a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to the end of a molecular chain or a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is copolymerized in the molecule. Is.

The resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to the end of the molecular chain means a resin in which the linear perfluoroalkyl group is added to either end of the molecular chain or directly to both ends of the molecular chain. It means a resin containing at least one of the resins with a chain perfluoroalkyl group added, and various raw materials for obtaining the resin of the main chain are reacted with a compound for adding a linear perfluoroalkyl group having 9 or more carbon atoms. Is obtained.

As the main chain resin to which a linear perfluoroalkyl group having 9 or more carbon atoms is added, one or a combination of resins such as polyvinyl butyral, epoxy, phenoxy, polyester, polyhydroxy ether, polyvinyl formal and polyamide is used. Resin composition,
Alternatively, there is a resin composition in which one or more of amino resin, isocyanate, trihydroxyethyl isocyanate, triazine resin, phenol resin, and phenol formaldehyde resin are mixed.

The linear perfluoroalkyl group having 9 or more carbon atoms is represented by the following general formula (I). CF ₃ (CF ₂ ) _n-1 − (I) (where n ≧ 9 in the formula) In addition, a part of the fluorine in the general formula (I) is replaced with hydrogen. May be used, which is represented by the following general formula (II)
It is represented by. CF ₃ (CF ₂ ) _n-1 (CH ₂ ) _m − (II) (where, n + m ≧ 9).

The number of carbon atoms of the linear perfluoroalkyl group bonded to the end of the resin of the main chain must be 9 or more in order to obtain good lubricity, and if it is less than 9, the lubricity is not sufficient. .. That is, when the linear perfluoroalkyl group is represented by the general formula (I), n ≧ 9. Further, the chain of the straight chain perfluoroalkyl group is preferably a completely straight chain, but even the number of carbon atoms in the straight chain portion is 9
If it is above, it may be a slightly branched perfluoroalkyl group.

The main chain resin and the terminal linear perfluoroalkyl group having 9 or more carbon atoms are amide bond, imide bond,
They are linked by ester bond, urethane bond, urea bond and the like.

Examples of compounds used to add a linear perfluoroalkyl group to the terminal of the molecule of the resin of the main chain include fatty acids and their perfluoroalkyl esters and acid halides, as well as perfluoro higher alcohols, amines, epoxies, There are fatty acid amides and the like. Examples of fatty acids include perfluororhodocosanoic acid and perfluorooctadecanoic acid, and derivatives of these fatty acids include esters. Examples of perfluoro higher alcohols include perfluorodocosanol, perfluorodecanol, 1,8-bis (hydroxymethyl) perfluorooctane, and the like. Examples of amines include perfluorotocosylamine, perfluorooctadecylamine and the like. Further, polytetrafluoroethylene having a terminal functional group can also be used. of course,
When a linear perfluoroalkyl group is added to the end of the molecule of the resin of the main chain using these compounds, those having a functional group capable of reacting with various raw materials used to obtain the resin of the main chain are selected. There is a need. Further, these compounds do not have to be used alone and may be a mixture.

The resin obtained by copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in the molecule includes various raw materials for obtaining a resin for copolymerizing the linear perfluoroalkyl group and a linear perfluoroalkyl group having 9 or more carbon atoms. Is obtained by reacting a compound for adding.

As a resin for copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in the molecule, nylon 6-
6, nylon 6, nylon 6-10, nylon 6-1
2, polyamide such as nylon 11 and nylon 12, polyvinyl butyral, epoxy, phenoxy, polyester, polyvinyl formal and the like.

The resin for copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in the molecule and the linear perfluoroalkyl group having 9 or more carbon atoms are amide bond, imide bond,
They are linked by ester bond, urethane bond, urea bond and the like.

Examples of compounds used for copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in the molecule include 1,8-bis (hydroxymethyl) perfluorooctane and perfluorodecanedioic acid. When 1,8-bis (hydroxymethyl) perfluorooctane is used as a compound used for copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms in polyamide, this and the polyamide are bonded by an ester bond, It is represented by the following general formula (III). -[PA] -R- [PA] -... (III) (In the formula, [PA] represents polyamide, and R represents 1,8-bis (hydroxymethyl) perfluorooctane.)

When 1,8-bis (hydroxymethyl) perfluorooctane or the like is used as the compound used for copolymerizing a linear perfluoroalkyl group having 9 or more carbon atoms with polyester or the like, these compounds and the above resin are not used. They are linked by an ester bond to form a copolymer.

In the self-adhesive insulated wire of the present invention,
In order to provide good lubricity, the proportion of the linear perfluoroalkyl group having 9 or more carbon atoms in the main resin in the adhesive resin coating composition is 0.05% by weight or more and 20% by weight or less. preferable. If the proportion of the linear perfluoroalkyl group having 9 or more carbon atoms in the main component resin is more than 20% by weight, the storage stability as a paint and the appearance and mechanical properties as an electric wire are adversely affected. Further, if it is less than 0.05% by weight, the lubricity of the adhesive coating is poor, and in the above range, the storage stability as a paint,
Further, in terms of appearance as an electric wire, more preferable is
It is 0.1 to 5.0% by weight.

In the present invention, the number of carbon atoms is 9 at the end of the molecular chain.
The above adhesive resin coating containing a resin having a linear perfluoroalkyl group added thereto or a resin having a linear perfluoroalkyl group having a carbon number of 9 or more copolymerized in the molecule as a main component means having 9 or more carbon atoms at the end of the molecular chain. A resin solution having a linear perfluoroalkyl group added thereto or a resin having a linear perfluoroalkyl group having 9 or more carbon atoms copolymerized in the molecule itself, or to the extent that the characteristics of the polymer solution are not impaired, The thermoplastic resin, the thermosetting resin, the filler, the pigment, the dye, etc., or one or more kinds thereof are added.

A self-adhesive insulated electric wire is obtained by applying such an adhesive resin coating composition onto at least the outermost layer directly on the conductor or through another insulating material, baking it, and forming an adhesive coating.

Any other insulating material may be used, and examples thereof include polyurethane, polyvinyl formal, polyester, polyester imide, polyhydantoin, polyamide imide, polyester amide imide, polyhydantoin ester and polyester amide. ..

The application and baking of the above adhesive resin paint can be carried out using a conventional enamel baking furnace.
The baking temperature is appropriately set depending on the type of resin in the adhesive resin paint. The film thickness of the adhesive coating after baking is not particularly limited, but it is usually preferably 1 to several tens of μm.

As described above, the self-adhesive insulated wire of the present invention is a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to the end of a molecular chain or a linear perfluoroalkyl having 9 or more carbon atoms in the molecule. An adhesive resin coating containing a resin having a base copolymerized as a main component is applied to at least the outermost layer directly on a conductor or through another insulating material, and baked to form an adhesive coating. The smoothness and surface lubricity of the wire are improved, the static and dynamic friction coefficient of the coating is reduced, scratches due to the guide pulley during winding processing are eliminated, and the space factor of the winding coil is increased. It is possible to improve the mold releasability of.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following Reference Examples, Examples, and Comparative Examples, the reaction was carried out in a 2-liter four-necked flask equipped with a reaction vessel equipped with a cooling tube equipped with a calcium chloride tube, a thermometer, a nitrogen introduction tube, and a stirrer. A heating mantle was used to heat the reaction vessel. The baking conditions of the varnish, which is the adhesive resin coating material in Reference Examples, Examples, and Comparative Examples, were those using a horizontal furnace having a furnace length of 3.0 m at a furnace temperature of 300 ° C. and a linear velocity of 50 m / min.

The characteristics of the obtained self-adhesive insulated wire are the same as JIS C 3003 or NEMA M except for the static friction coefficient.
It was measured according to W-1000. The coefficient of static friction is a measure of the coefficient of static friction between self-adhesive insulated wires. The method of measurement is to attach two self-adhesive insulated wires in parallel to a metal block and place them on a flat surface. Place the wires on the parallel self-adhesive insulated wires so that each wire makes a right angle, and set the minimum load required to move the former metal block along the two self-adhesive insulated wires on a plane.
It is divided by the load of the metallic block.

Reference Example 1 Denka Butyral # 3000
-K (manufactured by Denki Kagaku Kogyo) 210 g and cresol 600 g
After dissolving it in cresol and xylene 2: 1
Butyral varnish was obtained by adding 1800 g of thinner which is the ratio. The viscosity of this butyral varnish is 30 ° C.
It was 0.25 poise. Then, this butyral varnish was applied onto a polyester enameled wire having a diameter of about 0.5 mm, which is an insulator, and baked to obtain a self-adhesive insulated electric wire.

Example 1 Denka Butyral # 3000
-K (manufactured by Denki Kagaku Kogyo) 210 g and cresol 600 g
Then, 2.0 g of lead acetate and 2.0 g of perfluorooctadecanoic acid were gradually heated in a reaction vessel while stirring and reacted at 80 ° C. for 3 hours. After this, 60 ℃
The mixture was cooled to 1800 g, and 1800 g of a thinner containing cresol and xylene in a ratio of 2: 1 was added thereto to obtain a perfluorooctadecanoic acid-modified butyral varnish. The viscosity of this perfluorooctadecanoic acid-modified butyral varnish is
It was 0.41 poise at 30 ° C. Then, this butyral varnish was obtained in the same manner as in Reference Example 1 to obtain a self-adhesive insulated wire.

Reference Example 2 Phenoxy resin YP-50
200 g (manufactured by Tohto Kasei) was dissolved in 800 g cresol to obtain phenoxy varnish. The viscosity of this phenoxy varnish was 5 poise at 30 ° C. Then, this phenoxy varnish was obtained in the same manner as in Reference Example 1 to obtain a self-adhesive insulated wire.

(Example 2) Phenoxy resin YP-50
After dissolving 200 g (manufactured by Toto Kasei) in 800 g of cresol, 2.0 g of lead acetate and 2.0 g of perfluorooctadecanoic acid were gradually heated in a reaction vessel while stirring,
The reaction was carried out at 190 ° C. for 5 hours to obtain perfluorooctadecanoic acid-modified phenoxy varnish. The viscosity of this perfluorooctadecanoic acid-modified phenoxy varnish is 30 ° C.
It was 6.3 poise. Then, this perfluorooctadecanoic acid-modified phenoxy varnish was obtained in the same manner as in Reference Example 1 to obtain a self-adhesive insulated wire.

Reference Example 3 Nylon 6-6 (Toray CM
100 g of 3001N) was dissolved in 900 g of cresol to obtain a 10% nylon varnish. The viscosity of this 10% nylon varnish was 2 poise at 30 ° C. And
Using this 10% nylon varnish, a self-adhesive insulated electric wire was obtained in the same manner as in Reference Example 1.

(Example 3) Nylon 6-6 (CM by Toray)
3001N) 100 g was dissolved in 900 g of cresol, 1.0 g of perfluorooctadecanoic acid was gradually heated in a reaction vessel while stirring, and reacted at 190 ° C. for 5 hours to react with perfluorooctadecanoic acid-modified 10% nylon varnish. Got The viscosity of this 10% nylon varnish modified with perfluorooctadecanoic acid was 3 poises at 30 ° C. Then, this 10% nylon varnish modified with perfluorooctadecanoic acid was processed in the same manner as in Reference Example 1 to obtain a self-adhesive insulated wire.

(Examples 4 to 7) In Example 1, 0.1 g of perfluorooctadecanoic acid, 1.0 g of 10.
A self-adhesive insulated wire was obtained in the same manner except that the amounts were 0 g and 40.0 g. (Example 8) A self-adhesive insulated wire was obtained in the same manner as in Example 1 except that perfluorooctadecanoic acid was replaced with perfluorodecanoic acid.

Comparative Example 1 A self-adhesive insulated wire was obtained in the same manner as in Example 1, except that the amount of perfluorooctadecanoic acid was changed to 0.02 g. (Comparative Example 2) A self-adhesive insulated electric wire was obtained in the same manner as in Example 1, except that perfluorooctadecanoic acid was replaced with perfluorocaprylic acid.

The characteristics of these self-adhesive insulated wires are shown in Tables 1, 2 and 3 below.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

As is clear from the above Tables 1 to 3, a resin having a linear perfluoroalkyl group having 9 or more carbon atoms added to the end of the molecular chain is used as a main component, and a direct resin having 9 or more carbon atoms in this main component resin is used. The self-adhesive insulated wires of Examples 1 to 8 in which the adhesive resin paint having a preferable ratio of the chain perfluoroalkyl group of 0.05% by weight or more to 20% by weight or less was applied on the polyester enamel wire and baked were Reference Examples 1 to 3 in which an adhesive resin coating containing a resin not having a linear perfluoroalkyl group added at its end as a main component was applied onto a polyester enamel wire and baked,
Comparative Example 1 in which the ratio of the linear perfluoroalkyl group having 9 or more carbon atoms occupying in the main component resin was not applied in a preferable ratio and baked, and the linear perfluoroalkyl group having 9 or more carbon atoms was added to the end of the molecular chain. The static friction coefficient is about 1/5 times to 4/5 times smaller than that of the self-adhesive insulated wire of Comparative Example 2 in which an adhesive resin paint containing a resin not added as a main component is applied and baked on a polyester enamel wire, It had excellent lubricity.

[0041]

As described above, the self-adhesive insulated wire of the present invention is a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is added to the end of the molecular chain or a linear chain having 9 or more carbon atoms in the molecule. An adhesive resin coating containing a perfluoroalkyl group-copolymerized resin as a main component is applied to at least the outermost layer directly on a conductor or through another insulator, and baked to form an adhesive coating. Improves the smoothness and surface lubricity of the adhesive coating, reduces the static and dynamic friction coefficient of the coating, eliminates scratches due to guide pulleys during winding processing, increases the space factor of the winding coil, and It is possible to improve the mold releasability of the wire coil.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsutaka Yata 1-5-1 Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. (72) Kazuo Hanaoka 1-5-1 Kiba, Koto-ku, Tokyo Fujikura (72) Inventor Teruo Yamazawa 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Line Co., Ltd.

Claims (3)

[Claims] 1. An adhesive resin coating containing a resin having a linear perfluoroalkyl group having a carbon number of 9 or more added to the end of a molecular chain as a main component, at least on the outermost layer directly on a conductor or through another insulator. A self-adhesive insulated wire coated on, baked, and formed with an adhesive coating. 2. An adhesive resin coating containing, as a main component, a resin in which a linear perfluoroalkyl group having 9 or more carbon atoms is copolymerized in the molecule is applied to at least the outermost layer directly on a conductor or through another insulator. A self-adhesive insulated wire coated, baked and coated with an adhesive coating. 3. The proportion of the linear perfluoroalkyl group having 9 or more carbon atoms in the main resin in the adhesive resin coating is
The self-adhesive insulated electric wire according to claim 1 or 2, wherein the content is 0.05% by weight or more and 20% by weight or less.