JPS5818723B2 - Hakuriseisetsuendensen - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insulated wire having an insulating layer formed by fabric baking that can be easily peeled off and having excellent electrical, thermal, mechanical, and chemical properties. It is.

Conventionally, insulated wires used for equipment wiring for purposes other than winding have been required to be able to easily peel off the insulating layer with simple tools to expose the conductor when connecting terminals. There is.

For these applications, extruded coated wires made from melt-extrudable materials such as polyethylene, vinyl chloride, polyamide, and fluorinated ethylene propylene copolymers have conventionally been used.

However, in recent years, there has been a strong demand for these extruded coated wires to be thinner to reduce the space factor, and to improve thermal, electrical, mechanical, and chemical properties to improve reliability. There is.

As an example of this, when we look at insulated wires for internal wiring of equipment (for example, for computers, electronic exchanges, etc.), the electronic circuits are converted to transistors, ICs, and LS.
With the introduction of I-type wires, there has been a severe demand for a reduction in the space factor of insulated wires, as well as a reduction in the conductor diameter and a thinner insulating layer.

In addition, impedance matching is required between the circuit and the insulated wire, and there is a particularly strong demand for lower impedance.
In this case, it is necessary to make the insulating layer thinner in order to lower the characteristic impedance of the insulated wire, and if the conductor diameter becomes thinner due to the above space factor, it is necessary to make the insulating layer even thinner, resulting in an overall reduction in the conductor diameter and insulation. There is a growing demand for extremely thin layers.

Moreover, in order to further improve reliability even though the film is thinner,
Requirements for thermal, mechanical, and electrical properties are becoming more stringent than ever.

Also, among these uses, when looking at insulated wires for internal wiring for computers and hardware, the cost of wires for hardware is about 0.7%, and in the future it will increase by about 0.5 to 0.4 more. It is estimated that the ratio will decrease to 1,000,000, and the ratio is extremely small.

Therefore, computer manufacturers are currently focusing on reducing wiring costs, eliminating wiring errors, and improving reliability rather than reducing wire costs.

Particularly in order to reduce wiring costs and eliminate incorrect wiring, automatic wiring machines are being widely used, and about 80 wiring jobs are currently being done using the wrapping method.

However, in this case, the mechanical damage that the insulated wire receives becomes very large, and unless the mechanical strength of the insulating layer is improved, it is becoming difficult to improve the reliability or even maintain it.

The same situation applies to the use of such automatic wiring machines for wiring inside devices other than computers.

Another example is an insulated wire for a harness.

Among these, let's take the automotive harness as an example in particular.

BACKGROUND ART Conventionally, there has been a strong effort to reduce the size of equipment in automobiles in order to reduce their weight and increase the usable space.

Moreover, due to the problem of air pollution, more equipment has been added than before to purify exhaust gas, and the surrounding wiring used to attach this equipment is also required to be heat resistant to temperatures of 200°C or higher, for example. be.

Under these circumstances, there is a strong desire for automotive wiring to reduce the space factor and improve heat resistance compared to conventional wiring.

In order to meet these demands, it has become necessary to reduce the core wire diameter of the insulated wires for harnesses currently in use and to make the insulation coating thinner.

Regarding heat resistance, even with the core wire diameter and insulation coating thickness of conventional insulated wires, it is difficult to withstand heat resistance of 200°C or higher, for example, but thinning the insulation coating is difficult. It is a very difficult problem to improve the heat resistance of insulated wires while doing so.

Moreover, automobiles require a high degree of safety, and therefore, insulated wires, which are the nerve of automobiles, will be required to have an even higher degree of reliability in the future. It becomes necessary to improve chemical properties.

These circumstances are more or less the same for insulated wires for harnesses other than those for automobiles.

In addition, improvements in heat resistance have become an absolute requirement for communication cables for disaster prevention-related equipment, etc. due to amendments to the Fire Service Act.

The properties that will be required in the future in the fields where extruded coated wire is currently used as described above are that the insulating film can be easily peeled off with a simple tool as before, and that the insulating layer can be removed to reduce the space factor. A thin film is an absolutely necessary condition.

Currently, insulated wires have a peelable thin film insulation layer, or insulated wires whose peelable thin film insulation layer has one or more of thermal, mechanical, electrical, and chemical properties. Its appearance is strongly desired.

Now, in response to these demands, extruded coated wires are currently used as insulated wires used for equipment wiring and the like.

However, in the insulation coating method using extrusion, there is a limit to the reduction in the thickness of the insulation coating.

Various methods are currently being studied to reduce the thickness of the insulation coating formed by extrusion coating.

However, when the insulation thickness is less than 100 microns, it is currently technically very difficult to industrially and stably and continuously manufacture insulated wires by extrusion coating due to problems such as film breakage.

In addition, even when the core wire becomes thinner, the extrusion coating method causes various problems such as wire breakage.

In addition, even if the insulating layer is made thinner by extrusion, or even if it is thinned to the extent that is currently industrially possible, the insulating layer formed by extrusion coating with conventional materials is not only for the purpose of insulation. The thickness of the insulating film used to compensate for thermal and mechanical properties, but as the insulating layer becomes thinner, it becomes extremely difficult to maintain thermal and mechanical properties.

In addition, thermal and mechanical properties should be maintained (even if a material different from conventional materials is used, as long as the extrusion coating method is used, the coating material has thermoplasticity, melts, and It must be stable for long periods of time at melting temperatures, which severely limits the range of materials that can be selected.

Therefore, the fact that there are restrictions on material selection means that it is important not only to make the insulated wire coated by extrusion using the material thinner, but also to improve thermal (e.g. heat resistance, heat softening resistance, etc.) and mechanical properties (e.g. resistance). This indicates that there are limits to the electrical properties (e.g., abrasion resistance, etc.), electrical properties (e.g., characteristic impedance, etc.), and chemical properties.

Moreover, when using a material with the best thermal and mechanical properties within the available material selection range, the conditions are naturally harsher than when extruding with conventional materials, making it even more difficult to achieve a thin insulating film. Become.

For these reasons, it is no exaggeration to say that it is impossible to meet the above-mentioned severe requirements for insulated wires, both in terms of manufacturing and properties, using the current extrusion coating method. .

Now, let's change our perspective and consider another method of manufacturing insulated wires, which involves applying and baking an insulating paint.

Insulated wires obtained by coating and baking insulating paint are used only in the field called magnet wires or windings.

For use in this field, it is necessary to make the insulation film as thin as possible and to have extremely high levels of thermal, mechanical, electrical, and chemical properties. The requirements for uniformity of properties are very strict.

Moreover, while insulated wires for equipment wiring must be easily peelable, magnet wires require high adhesion and adhesion between the conductor and the insulating film due to their required characteristics. It is completely impractical for the film to peel off easily under these conditions.

For this reason, important test items include twisting releasability and adhesion between the conductor and insulating film after rapid cutting.

Moreover, even with magnet wires that are said to have poor adhesion, the insulating film only slightly deteriorates when subjected to the above-mentioned severe test, i.e., after being subjected to a mechanical load that is so great that it cannot be used as an insulated wire. It only floats and cannot be easily peeled off with a simple tool.

In this way, insulated wires and magnet wires for device wiring using conventional extrusion-coated wires have the following characteristics: 1) insulation level, film thickness,
2) Materials used, 3) Peelability, and 4) Manufacturing methods are at two extremes, and they are also completely different in price, characteristics, and fields of use. No consideration was given to the use of wires or the possibility of such use.

Therefore, in order to improve the heat resistance of insulated wires for equipment wiring, for example, studies have focused on methods of causing a crosslinking reaction in polyethylene or polyvinyl chloride wires by irradiating them with peroxide or electron beams.

However, the heat resistance of these materials is still not comparable to that of insulation and coatings for magnet wires.

However, in view of the recent demands in the field of extruded coated insulated wires for equipment wiring, etc., the inventors of the present invention have made the following as a result of intensive study.
It was discovered that the requirements could be met by using an insulator for magnet wires and adopting a manufacturing method for magnet wires, which had never been thought of before.

That is, the present invention provides an insulated wire in which the insulating layer formed by coating and baking can be easily peeled off, the surface exhibits a smooth and uniform appearance, and the wire has excellent electrical, thermal, mechanical, and chemical properties. It gives

The insulated wire according to the present invention has a thin insulation film thickness that could not be obtained with conventional extrusion coated wires, and has good electrical, thermal, mechanical, and chemical properties at the thin insulation film thickness, Furthermore, it has peelability that was neither possible nor possible to obtain with insulated wires conventionally obtained by coating and baking.
Furthermore, the insulated wire has a smooth surface and a uniform appearance, and new uses for the insulated wire obtained by coating and baking, such as equipment wiring, can be found.

The characteristics of the insulated wire obtained by the present invention will be explained in more detail.

First, regarding the insulation film thickness, since the present invention uses a coating and baking method, the insulation film thickness from one coating and baking process is approximately several microns, and the characteristics of the insulation film are very uniform, and the insulation film thickness is approximately several microns. By applying and baking several times to several dozen times, it is possible to control the film thickness very precisely, and it is not only possible to achieve thin films that cannot be achieved with extrusion coating methods, but also to meet strict requirements for electrical properties such as characteristic impedance. It is also possible to create thin films with sufficient precision.

Furthermore, regarding the range of selection of materials that have a significant effect on thermal and mechanical properties, the present invention uses a method of applying and baking an insulating paint, so it does not matter whether the insulating material is soluble in a solvent or uniformly dispersed. Any material can be used, and there is no restriction that the coating material be thermoplastic, melt, and be stable at its melt temperature for long periods of time, as is the case with extrusion coating methods.

Therefore, in the insulated wire obtained according to the present invention, the selection range of materials used as the insulating film is much wider due to the extrusion coating method, and various materials can be selected depending on the application.

For example, if a material with excellent mechanical properties is required, polyvinyl formal or polyamide-imide materials are desirable, and if a material with excellent thermal properties is required, a polymer containing an imide group is desirable, particularly If both thermal and mechanical properties are required, polyamide-imide materials are preferred.

The example shown here is just one example, and even if other characteristics are desired, it is possible to select a material that corresponds to that, and you are also free to select materials after considering the balance between characteristics and material cost. can be done.

Regarding removability, there are methods to remove the insulation film of insulated wires using the conventional simple coating and baking method, such as mechanically scraping it off, decomposing the film with chemicals, or burning it with a flame. No matter which method is used, it is troublesome to remove the coating, and it cannot be expected that the coating can be easily removed using a simple tool, such as a wire strike IJ tube, such as extruded insulated wires.

However, in order to simply obtain peelability, the purpose can be achieved even if a peeling layer mainly made of silicone is provided on the conductor, and an insulating layer coated and baked with the insulating paint conventionally used for enamelled wire is placed on top of that.3 However, when ordinary insulating paint is directly applied and baked on a release layer mainly made of silicone, it is difficult to industrially stably and continuously obtain a removable insulated wire with good appearance due to repellency or foaming.

If the surface of the insulated wire is not smooth or uniform, it goes without saying that sufficient confidence cannot be placed in the characteristics of the insulated wire, and therefore the demands of customers cannot be met.

Therefore, obtaining an insulated wire with a smooth and uniform surface, that is, an insulated wire with good workability, is a major challenge for wire manufacturers.

Moreover, even if an insulated wire with a partially smooth and uniform surface is obtained, unless a sufficiently long one is obtained continuously, it is industrially meaningless and virtually impossible to manufacture.

However, in the present invention, a peeling layer mainly made of silicone is provided on the conductor, and an insulating layer made by coating and baking an insulating paint made by adding and mixing solid fine powder directly on the peeling layer, thereby creating a smooth and uniform surface. It is possible to obtain a peelable insulated wire that can be produced industrially stably and continuously while exhibiting the following conditions.

Let us now consider the reason why an insulating paint containing fine solid powder as in the present invention is not repelled when applied and baked on a release layer mainly made of silicone.

Originally, silicone and insulating paint do not mix well with each other and are extremely repellent.

Looking back at the process of applying and baking insulating paint onto a release layer mainly made of silicone, we can see that first, in the application process, insulating paint is forcibly applied continuously, and usually at room temperature. The solution viscosity is high, the flow of the insulating paint is slow, and there is no sudden repelling.

However, since the temperature during the baking process is high, the viscosity of the solution of the applied insulating paint becomes low and it flows easily, making it extremely difficult to break off.

Once the viscosity of the insulating paint has decreased, in a high-temperature atmosphere, the solvent evaporates and, depending on the paint, a curing reaction occurs, the viscosity increases, and eventually an insulating film is formed, making it no longer repellent.

Therefore, it is thought that repelling and foaming occur when the viscosity of the insulating paint decreases in the furnace.

Therefore, in order to prevent repelling, the viscosity should not decrease after application, and an insulating film should be formed immediately.

However, baking is an unavoidable process in insulating paints.

That is, since baking creates a high-temperature atmosphere in the furnace, it is inevitable that the viscosity of the insulating paint will once decrease, resulting in repellency.

When solid fine powder is added to insulating paint, the viscosity of the insulating paint decreases in a high-temperature atmosphere, and even when it tries to flow, the flow around the solid particles is disturbed and extra work is done, so the flow resistance is large and the viscosity decreases. few.

During this time, the evaporation of the solvent progresses, and an insulating film is formed, so that the viscosity does not decrease enough to cause rapid repelling, and before repelling occurs, the viscosity rises and a film is formed, making it no longer repellent.

Therefore, during the coating and baking process, an insulating film with a smooth and uniform surface is likely to be formed without any repelling.

In the present invention, the insulating paint to which solid fine powder is added is mainly used to prevent repelling by a peeling layer made of silicone, and immediately above the peeling layer is an insulating layer in which an insulating paint coated with solid fine powder is coated and baked. Once formed, this upper layer will no longer repel, no matter what type of insulating paint is applied and baked.

Therefore, it is possible to select an insulating paint depending on the application.

Applications of the insulated wire obtained by the present invention include wires for wiring inside electronic devices, wires for harnesses, and the like.

Wrapping wires are used for wiring inside electronic devices, such as computers and electronic exchangers.

Wrapping wire has traditionally been manufactured by extrusion coating.

In recent years, as electronic circuits have become transistorized ICs and LSIs, there has been a growing demand for a reduction in the space factor for wrapping wires, a reduction in the conductor diameter, and a reduction in the thickness of the insulating layer.

Also, impedance matching is required between the circuit and the insulated wire, and there is a particularly strong demand for lowering the impedance, and in this case, it is necessary to make the insulating layer thinner in order to lower the characteristic impedance of the wrapping wire.

Moreover, in order to further improve reliability while thinning the film, the requirements for thermal, mechanical, electrical, and chemical properties are becoming more stringent than in the past.

Although there is a demand for thinning the insulation layer, it is very difficult to industrially and stably and continuously manufacture thin insulation coatings, especially those with a thickness of 100 microns or less, for extruded coated wires due to the problem of membrane breakage. It is.

Moreover, even if it can be manufactured, the thermal and mechanical properties that have been able to be maintained until now will only be inferior due to the thinning of the film.

However, the insulated wire obtained according to the present invention has the film removability required for wrapping wires, can be manufactured with a thin insulating layer that meets the requirements, and has excellent thermal and mechanical properties.

Another example is an insulated wire for a harness. Among these, let us take a harness for an automobile as an example.

BACKGROUND ART Conventionally, there has been a strong effort to reduce the size of equipment in automobiles in order to reduce their weight and increase the usable space.

Moreover, recently, due to the problem of air pollution, more equipment has been added than before to purify exhaust gas, and the surrounding wiring used to attach this device is sometimes required to have heat resistance of, for example, 200° C. or higher.

Under these circumstances, there is a strong desire for automotive wiring to reduce the space factor and improve heat resistance compared to conventional wiring.

In order to meet these demands, it has become necessary to reduce the core wire diameter of the insulated wires for harnesses currently in use and to make the insulation coating thinner.

Regarding heat resistance, even with the core wire diameter and insulation coating thickness of conventional insulated wires, it is difficult to withstand heat resistance of 200℃ or higher, for example, but by making the insulation coating thinner. However, improving the heat resistance of insulated wires is a very difficult problem.

Moreover, automobiles require a high degree of safety, and therefore insulated wires, which are the nerve of automobiles, will be required to have an even higher degree of reliability in the future. Therefore, it is necessary to improve the physical characteristics.

These circumstances are more or less the same for insulated wires for harnesses other than those for automobiles.

In order to meet this demand, enamelled wires have been introduced for harnesses in recent years, but it is difficult to peel off the ends, which poses a serious problem in work.

The insulated wire of the present invention has characteristics equivalent to those of conventional enamelled wire, and the ends can be easily peeled off, so that the working time can be significantly shortened.

The examples mentioned above are just a few, and are insulated wires that have a thin insulating layer, can be easily peeled off, and require excellent electrical, thermal, mechanical, and chemical properties. All can be used effectively.

In FIGS. 1 and 2, layer 2 is a release layer mainly made of silicone.

The silicone used to form layer 2 is generally used as a mold release agent.

Examples of silicone include KF96 manufactured by Shin-Etsu Chemical Co., Ltd.
KF965, KS700, KS701.

KP301, KP321, KP330, KP34
0゜KP354, KR282, KC88, KS705
F.

KS706, KS709, KS709S, KS71
There is 1.

In silicone, KF96. It is preferable to use a solvent that forms a film when the solvent that dissolves the silicone is dried, rather than an oil such as KF965.If the silicone reacts with the solvent and forms a hardened film during the process of drying the solvent, use a trace amount. It is preferable to add a curing agent of.

An example of a curing agent is catalys manufactured by Shin-Etsu Chemical Co., Ltd.
tPS.

Examples include catalyst PD.

In the present invention, the layer 3 shown in FIG. 1 is an insulating layer coated with an insulating paint containing fine solid powder and baked to prevent repelling by the release layer 2 mainly made of silicone. should be directly above layer 2.

Once layer 3 is formed, no matter what kind of insulating paint is applied and baked on top of it, repellency will no longer occur, so the insulating paint can be selected depending on the application.

That is, any insulating paint may be used to form layer 4.

If layer 4 is exactly the same as layer 3, then Figure 2 is obtained.

The solid fine powder used in this application is aluminum oxide (A
1203), silicon oxide (SiO2), titanium oxide (T
102), magnesium oxide (MgO), zinc oxide (
ZnO), aluminum hydroxide<hi(OH)3).

In the present invention, the insulating paint to which solid fine powder has been added is mainly used to prevent repellency by the release layer made of silicone, so in order to improve compatibility with the release layer, silicone is further added to the insulating paint to which solid fine powder has been added. It is also preferable to add a supplement.

The layer 3 is formed by applying and baking an insulating paint to which fine solid powder is added, and the insulating paint to which fine solid powder is added is the insulating paint conventionally used for enamelled wire.

゛This insulating paint includes polyvinyl formal polyurethane, acrylic, epoxy, thermoplastic polyester,
Selected from Type 8 thermosetting polyester, Type H thermosetting polyester, Type F polyesterimide, Type H polyesterimide, polyamide, polyesteramideimide, polyhydantoin, polyamideimide, and an insulating coating containing polyimide as a main component.

The insulating paint used to form layer 4 is the insulating paint conventionally used for enamelled wire.

Examples of this insulating paint include polyvinyl formal, polyurethane, acrylic, epoxy, thermoplastic polyester,
Class B thermosetting polyester, Class H thermosetting polyester,
Examples include insulating paints whose main components are F-type polyesterimide, H-type polyesterimide, polyamide, polyesteramideimide, polyhydantoin, silicone, polyamideimide, polyimide, and the like.

The polyamide-imide insulating paint in the present invention is an insulating paint whose main component is polyamide-imide resin or polyamide-imide precursor resin, and a part of it is generally made of epoxy resin, phenol resin, polyisocyanate, stabilized polyisocyanate, etc. It includes each of the resins used as additives for insulating paints, or a combination thereof.

A typical example of a method for producing polyamide-imide resin or its resin solution, or polyamide-imide precursor resin or its resin solution, which is the main component of polyamide-imide insulating paint, is to use at least one tricarboxylic acid anhydride acid chloride and at least one tricarboxylic acid anhydride acid chloride. Some react with diamines.

Further, a part of the acid chloride of the tricarboxylic anhydride may be replaced with at least one dicarboxylic dichloride, at least one tetracarboxylic dianhydride, or at least one dicarboxylic dichloride and at least one tetracarboxylic dianhydride. It may be replaced with carboxylic dianhydride.

Further, a part of the above diamine may be replaced with at least one kind of triamine,
Alternatively, at least one type of tetramine may be replaced with at least one triamine and at least one type of tetramine.

Examples of the acid chloride of tricarboxylic anhydride include 4-acid chloride of trimellitic anhydride.

Examples of dicarboxylic acid dichloride include terephthalic acid dichloride, isophthalic acid dichloride, adipic acid dichloride, and the like.

Examples of diamines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether m-phenylenediamine, and the like.

Examples of triamines include 3,4,4'-triamino diphenyl ether.

Examples of tetramine include 3,3', 4,4'-tetraaminodiphenyl ether and the like.

Another typical manufacturing method involves reacting at least one tricarboxylic anhydride with at least one diisocyanate.

Further, a part of the above tricarboxylic anhydride may be at least one dicarboxylic acid, or at least one tetracarboxylic dianhydride, or at least one dicarboxylic acid and at least one tetracarboxylic dianhydride. You can replace it with

Further, a part of the above diisocyanate may be replaced with at least one type of trivalent or higher polyisocyanate.

Examples of tricarboxylic anhydrides include trimellitic anhydride.

Examples of dicarboxylic acids include isophthalic acid, terephthalic acid, adipic acid, and the like.

Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and the like.

Examples of diisocyanates include diphenylmethane-4
, 4'-diisocyanate, diphenyl ether-4,
4'-diisocyanate, tolylene diisocyanate,
Examples include xylylene diisocyanate and hexamethylene diisocyanate.

Examples of polyisocyanates include polymethylene polyphenylene polyisocyanate.

The polyimide-based insulating paint as used in the present invention is a general term that includes imidacypyrrolone insulating paint.

That is, the polyimide-based insulating paint as used in the present invention is an insulating paint whose main component is polyimide (including imidazopyrrolone) resin or polyimide (including imidazopyrrolone) precursor resin, and a part of which is epoxy resin, Polyimide (imidazo), which is the main component of polyimide-based insulating paints, includes resins modified with phenol resins, polyisocyanates, stabilized polyisocyanates, and other resins commonly used as additives for insulating paints, or a combination of these. Typical manufacturing methods for resins (including pyrolone) or their resin solutions, or polyimide (including imidazopyrrolone) precursor resins or resin solutions include at least one type of tetracarboxylic dianhydride and at least one type of polyamine. There are things that cause a reaction.

Examples of tetracarboxylic dianhydrides used here include:
Examples include pyromellitic anhydride and pensiveenonetetracarboxylic dianhydride.

In addition, diamines, triamines, and tetramines are mainly used as polyamines, and as triamines, it is preferable that two of the three amine groups are in ortho positions, and as tetraamines, it is preferable that two of the three amine groups are in the ortho position. It is preferable that these are in the ortho position to each other.

Examples of diamines include 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane.

Examples of triamines include 3,4,4'-triaminodiphenyl ether, 3-amine benzine, and the like.

Examples of tetramine include 3,3',4,4'-tetraamino diphenyl ether, 3,3'-diaminobenzidine, and the like.

The insulating paint used to form layer 4 may be selected depending on the required characteristics.

For example, if thermal properties are required, polyesterimide,
Preferred are polyesteramideimide, polyamideimide, polyhydantoin, polyimide, and the like.

Polyamideimide is most preferred as it has thermal, mechanical, electrical, and chemical properties.

Of course, a multilayer structure in which two or more types of insulating layers are combined is also preferable, and for example, from the viewpoint of cost and characteristics, it is also preferable to use polyamideimide as the outermost layer.

In order to lower the coefficient of friction of the insulating layer, it is also preferable to apply and bake an insulating paint containing at least one layer of silicone on the outermost layer of the insulating layer.

Furthermore, it is also preferable to use a mixture of two or more types of insulating paints depending on requirements.

It is also preferable that the insulating layer consists of only three layers as shown in FIG.

Even when the thickness of the insulating layer of the insulated wire of the present invention exceeds 100 microns, it exhibits properties superior to those of an insulated wire obtained by extrusion coating.

However, the insulated wire obtained by the present invention is most effective when the thickness of the insulating layer is 100 microns or less.

This is because, as mentioned above, in the extrusion coating method, the
This is because it is practically impossible to manufacture particles smaller than microns, and even if it were possible, the required characteristics would not be fully satisfied.

The present invention will be explained in detail in the following examples, but the present invention is not limited to these examples.

The following reference examples show insulating paints used in comparative examples and examples.

Reference example 1 192.1 g (1.0 mol) of trimellitic anhydride and 25 o of diphenylmethane-4,4'-diisocyanate
, 3 g (1,0 mol) were added to a mixed solvent of 770 g of N-methyl-2-pyrrolidone and solvent naphtha (Maruzen Petrochemical Swazol≠11000) 330.
After reacting at .degree. C. for 3 hours, the temperature was raised to 165.degree. C. over 6 hours, and the reaction was continued at this temperature for 2 hours to obtain a polyamide-imide insulation coating.

The reduced specific viscosity of the resin was 0.54.

Reference example 2 4.4'-diaminodiphenyl ether 200.2g
(1,0 mol) to N-methyl-2-pyrrolidone 1500
g and cooled on ice.

Next, 218.1 g of pyromellitic anhydride (1,
During this time, the reaction vessel was water-cooled, and a viscous polymer solution was obtained.

500 g of N,N-dimethylacetamide was further added to dilute the mixture.

The reduced specific viscosity of the resin was 1.58.

Reference example 3 A thermosetting polyester insulation coating was obtained as follows.

1) Dimethyl terephthalate 388g2) Ethylene glycol 81g3) Glycerin 93g
A thermal reaction was carried out at 30 to 140°C for 5 hours to distill off the low boiling point distillate, and then the temperature was gradually raised to 240°C while distilling the low boiling point distillate. When the reaction product became viscous, Bresol was added to give a solution containing 40% solids.

Solvent naphtha (manufactured by Maruzen Petrochemical Co., Ltd., Swazol = # = 1000) is added to this solution to make a solution containing 30% solids, and 1.5% of tetrabutyl is added to this solution based on the weight of the total solid resin. Titanate and 4% Desmodur CT Stable (manufactured by Bayer, Germany) were added and mixed and stirred to form a uniform solution.

Reference Example 4 5iO was added to the polyamide-imide insulation paint obtained in Reference Example 1.
2 (Erosil 200 manufactured by Nippon Erosil Co., Ltd.) was added to the solid resin content of a polyamide-imide insulating coating by 5 weights and thoroughly stirred and dispersed.

Reference Example 5 11' was applied to the polyamide-imide insulation paint obtained in Reference Example 1.
203 (manufactured by Egussa GmbH, West Germany) was added in an amount of 6% by weight based on the solid resin content of a polyamide-imide insulating paint, and the mixture was thoroughly stirred and dispersed.

Reference Example 6 Ti0 was added to the polyamide-imide insulation paint obtained in Reference Example 1.
2 (manufactured by Sakai Chemical Industry Co., Ltd.) in an amount of 7% by weight based on the solid resin content of a polyamide-imide insulating paint and thoroughly stirred and dispersed.

Reference Example 7 5iO was applied to the polyamide-imide insulation paint obtained in Reference Example 1.
2 (Erosil 200 manufactured by Nihon Erosil Co., Ltd.) was added in an amount of 5% by weight based on the resin solid content of the polyamide-imide insulation paint, and KS701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the resin solid content of the polyamide-imide insulation paint. 1% by weight
Insulating paint that has been added and thoroughly stirred and dispersed.

Reference Example 8 An insulating paint obtained by adding 5in2 (Erosil 200 manufactured by Nippon Erosil Co., Ltd.) to the insulating paint obtained in Reference Example 2 in an amount of 7% by weight based on the solid resin content of the insulating paint, and thoroughly stirring and dispersing the mixture.

Reference Example 9 To the insulating paint obtained in Reference Example 2, 7% by weight of S i02 (Erosil 200 manufactured by Nihon Erosil Co., Ltd.) was added to the resin solid content of the insulating paint, and KS700 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was added. ) is added by weight to the solid resin content of the insulating paint and thoroughly stirred to disperse it.

Reference Example 10 Polyamide-imide insulation paint obtained in Reference Example 1? , :K
2.5% by weight of P321 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) based on the solid resin content of the polyamide-imide insulation paint.
Insulating paint that has been added and thoroughly stirred and dispersed.

In addition, S i 02 (Erosil 20 manufactured by Nippon Erosil Co., Ltd.
0) has an average particle diameter of 16 mμ, and A1203 (manufactured by Degussa, West Germany) has a particle diameter of 5 to 30 mμ.

Comparative Example 1 The polyamide-imide insulating paint obtained in Reference Example 1 was repeatedly applied and baked on a silver-plated copper alloy wire having a diameter of 0.26 mm several times to obtain a polyamide-imide insulated wire.

The obtained insulated wire had a smooth and uniform surface.

The characteristics of this insulated wire are shown in Table 1. Comparative Example 2 KS on a silver-plated copper alloy wire with a diameter of 0.26 mm
701 (a silicone solution sold by Shin-Etsu Chemical Co., Ltd.) was coated and baked, a release layer was provided, and Reference Example 1 was applied on top of this.
The polyamide-imide insulating paint obtained in step 1 was coated and baked several times to obtain a polyamide-imide insulated wire.

The resulting insulated wire had cracks and foaming everywhere.

The characteristics of this insulated wire are shown in Table 1.

Comparative Example 3 A vinyl chloride mixture containing 100 parts by weight of vinyl chloride resin, 50 parts by weight of dioctyl phthalate, and 5 parts by weight of tribasic lead sulfate was coated on a silver-plated copper alloy wire having a diameter of 26,771 m by extrusion, and then chlorinated. A vinyl-coated electric wire was obtained.

Table 1 shows the characteristics of the obtained insulated wire.

Example I Q, KS on a silver-plated copper alloy wire with a diameter of 26 mm
701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked, a peeling layer was provided, the insulating paint of Reference Example 4 was applied and baked, and the insulating paint of Reference Example 1 was further applied and baked on top of that to obtain an insulated wire. Ta.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of the insulated wire.

Example 2 KS on a silver-plated copper alloy wire with a diameter of 0.26 mm
701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked, a peeling layer was provided, and on top of that, the insulating paint of Reference Example 5 was applied and baked, and then the insulating paint of Reference Example 3 was further applied and baked to form an insulated wire. Obtained.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 3 Q, KS701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) on a silver-plated copper alloy wire having a diameter of 26 mrrt.
A peeling layer was provided by coating and baking, and the insulating paint of Reference Example 6 was coated and baked on top of the peeling layer to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 4 KS on a silver-plated copper alloy wire with a diameter of 0.26 mm
701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked, and then the insulating paint of Reference Example 7 was applied and baked. Further, the insulating paint of Reference Example 2 was further applied and baked to form an insulated wire. Obtained.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 5 KS on a silver-plated copper alloy wire with a diameter of 0.26 mm
701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked, a peeling layer was formed, and then the insulating paint of Reference Example 8 was applied and baked. Further, the insulating paint of Reference Example 1 was further applied and baked to obtain an insulated wire. Ta.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 6 KS on a silver-plated copper alloy wire with a diameter of 0.26 mm
701 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) is applied and baked, a release layer is provided, the insulating paint of Reference Example 9 is applied and baked, and the insulating paint of Reference Example 1 is further applied and baked on top of that to form an insulated wire. I got it.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this wire.

Example 7 The insulating paint of Reference Example 10 was applied and baked on the insulated wire obtained in Example 1 to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 8 KP on a silver-plated copper alloy wire with a diameter of 0.26 mm
330 (silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked, a peeling layer was provided, the insulating paint of Reference Example 4 was applied and baked, and then the insulating paint of Reference Example 1 was further applied and baked to form an insulated wire. Obtained.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 9 Q: On a copper wire with a diameter of 3 mm, a release layer was provided by applying and baking KS701 (a silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.), and on top of that, the insulating paint of Reference Example 5 was applied and baked. The insulating paint of Reference Example 1 was applied and baked to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 10 Q, KP330 (
A release layer was provided by applying and baking a silicone solution (manufactured by Shin-Etsu Chemical Co., Ltd.), and the insulating paint of Reference Example 4 was applied and baked thereon to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 11 Q: On a copper wire having a diameter of 3 mm, a release layer was formed by applying and baking KP330 (a silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.), and on top of that, the insulating paint of Reference Example 8 was applied and baked, and further on top of that, the insulating paint of Reference Example 8 was applied and baked. The insulating paint of Reference Example 2 was applied and baked to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 12 A release layer was provided on a copper wire having a diameter of 0.3 mm by applying and baking KP330 (a silicone solution manufactured by Shin-Etsu Chemical Co., Ltd.), and then the insulating paint of Reference Example 9 was applied and baked on top of it. The insulating paint of Reference Example 1 was applied and baked to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

Example 13 The insulating paint of Reference Example 1 was applied and baked on the insulated wire obtained in Example 11 to obtain an insulated wire.

The obtained insulated wire had a smooth and uniform surface.

Table 1 shows the characteristics of this insulated wire.

3 is an insulating layer coated and baked with an insulating paint supplemented with fine solid powder; 4 is an insulating layer coated with one or more types of insulating paint and baked.

Claims (1)

[Claims] 1 A release layer mainly made of silicone provided on a conductor and solid fine powder selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zinc oxide, and aluminum hydroxide are combined with polyvinyl formal, polyurethane, acrylic, and epoxy thermoplastic polyester. , Type 8 thermosetting polyester, Type H thermosetting polyester, Type F polyesterimide, Type H polyesterimide, polyamide polyesteramide imide, polyhydantoin, polyamideimide, and polyimide. 1. A peelable insulated wire, comprising: an insulating layer obtained by coating and baking an insulating paint containing an added mixture on the peelable layer.