JP2709593B2 - Heat-resistant insulated wire - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant insulated wire particularly suitably used as a winding of an electric device. 2. Description of the Related Art Hitherto, as heat-resistant insulated wires, polyimide wires, polyamide-imide wires, and the like are known, but since the constituent material of the insulating layer is an organic material, there is a natural limit to heat resistance. Is usually up to about 250 ° C. Recently, there is a demand for a winding capable of withstanding a high temperature of 300 ° C. or more for use in nuclear power, geothermal power, and other special environments. In response to this requirement, various inorganic-containing paints have been studied for use as a constituent material of the insulating layer. However, since the obtained inorganic insulated wires are generally hard and brittle, they have poor flexibility and thus have poor flexibility during coil winding. Cracks occur or the film peels. Problems to be Solved By the way, recently developed polytitanocarbosilane resins have the property of gradually becoming ceramic under a high-temperature atmosphere. It has the advantage of maintaining excellent heat resistance.
However, the baked film has a disadvantage that it is brittle and has poor flexibility. An object of the present invention is to solve the above-mentioned problems of the baked film of polytitanocarbosilane resin and to provide a heat-resistant insulated wire having excellent film retention even in a high-temperature atmosphere. Means for Solving the Problems In order to solve the above problems, in the present invention,
We propose a heat-resistant insulated wire characterized in that a paint composed of a polytitanocarbosilane resin, a silicone resin that can be turned into a ceramic, and an inorganic filler is applied and baked on a conductor. The silicone resin which can be ceramized used in the present invention has the property of being cured at high temperature to be ceramized, but is cured at about the temperature and time conditions at the time of baking in ordinary enamel wire production. Shows good flexibility even after curing. The coordination of this property of the silicone resin which can be ceramicized and the effect of improving the heat resistance of the inorganic filler improves the flexibility of the polytitanocarbosilane resin without impairing its excellent heat resistance. Therefore, the heat-resistant insulated wire of the present invention can meet the requirements for use in nuclear power generation, geothermal power generation, and other special high-temperature environments. The polytitanocarbosilane resin used in the present invention is, for example, polydimethyldisiloxane synthesized by dechlorination polycondensation reaction of dimethyldichlorosilane, polyborodiphenylsiloxane obtained by polycondensation of diphenyldichlorosilane and boric acid, and a titanium compound. And heat condensation. As a commercial product of the resin paint, there is, for example, Tyrannocoat (concentration: 50% by weight) manufactured by Ube Industries. Examples of the silicon resin that can be made into a ceramic (hereinafter simply abbreviated to silicon resin) used in the present invention include, for example, a composition composed of the following five components (1) to (5). An example of a commercially available product of such a composition is AY49-208 (trade name: 85% by weight) manufactured by Toray Silicon Co., Ltd. (1) a silicone copolymer having at least two olefinically unsaturated bond-containing groups in one molecule and at least two alkoxy groups in one molecule; and (2) at least two olefinically unsaturated groups in one molecule. (3) an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule; (4) a ceramic material such as talc, aluminum oxide, talc, mica, oxidized Boric acid, clay minerals (glass, asbestos, kaolinite, montmorillonite, etc.), zirconium oxide, lead oxide, zinc oxide, magnesium oxide, tungsten, titanium carbide, molybdenum carbide, silicone carbide, titanium zirconia, nitroboron, boron nitride, aluminate Sodium, titanium Potassium, potassium silicate, aluminum silicate, magnesium silicate, zinc silicate, zirconium silicate, titanium silicate, calcium aluminum silicate, lithium aluminum silicate, etc. (5) Addition reaction catalyst, (as the addition reaction catalyst Are various catalysts effective for the addition reaction of hydrogen atoms bonded to the olefinically unsaturated group-containing silicon atom, for example, finely divided elemental platinum, finely divided platinum dispersed on carbon powder, chloroplatinic acid,
Coordination compounds of chloroplatinic acid and olefins, coordination compounds of chloroplatinic acid and vinylsiloxane, tetrakis (triphenylphosphine) palladium, a mixture of palladium black and triphenylphosphine, and a rhodium catalyst are exemplified. ) Inorganic fillers include aluminum oxide, talc,
Examples thereof include mica, boric acid, clay minerals (glass, asbestos, kaolinite, etc.) or the above-mentioned ceramic substances, or a ceramic frit obtained by mixing and melting several kinds of metal oxides.
These may be used alone or as a mixture of two or more. These may be natural products or synthetic products, but in any case, the average particle size is 50 μm or less, particularly 10 μm or less.
Fine powder having a size of not more than μm is desirable. In the present invention, the compounding ratio of the polytitanocarbosilane resin and the silicone resin is
The silicone resin is used in an amount of 10 to 500 parts by weight, preferably 15 to 400 parts by weight, per 100 parts by weight. The amount of the inorganic filler used is 10 to 250 parts by weight, preferably 15 to 250 parts by weight, per 100 parts by weight of the total amount of the polytitanocarbosilane resin and the silicone resin.
A range of 200 parts by weight is good. If the compounding amount of the silicone resin is less than 10 parts by weight per 100 parts by weight of the polytitanocarbosilane resin, the flexibility of the baked coating film, the coil winding processability deteriorates, and if it exceeds 500 parts by weight, Even in the presence of an inorganic filler, the baked coating film becomes soft and the coil winding processability deteriorates. On the other hand, if the compounding amount of the inorganic filler is less than 10 parts by weight per 100 parts by weight of the total amount of the polytitanocarbosilane resin and the silicone resin, the heating loss increases and conversely, if the amount exceeds 300 parts by weight, Flexibility and coil winding workability decrease. The polytitanocarbosilane resin, the silicone resin and the inorganic filler may be dissolved or dispersed in an appropriate organic solvent in the ratio shown above, for example, or the components may be uniformly mixed without using an organic solvent to form a coating. In addition, the heat-resistant insulated wire of the present invention is obtained by coating the paint thus obtained on a copper wire, an aluminum wire, preferably a Ni-plated copper wire, an Ag-plated copper wire, or a plated copper wire such as a stainless-clad copper wire. It can be manufactured by coating and baking. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, phenol solvents, N
A polar solvent such as -methyl-2-pyrrolidone is used. If necessary, a curing agent for the silicone resin, a coloring pigment, a baking curing catalyst, or other additives may be added to the coating composed of the polytitanocarbosilane resin, the silicone resin and the inorganic filler. In the present invention, it is preferable to further provide an insulating layer made of an organic resin on a layer formed by applying and baking a coating made of a polytitanocarbosilane resin, a silicone resin, and an inorganic filler, and thus, at least the electric wire at room temperature. And the coil winding processability are further improved. Of course, the above organic resin is preferably as heat resistant as possible, and examples thereof include polyester, polyesterimide, polyimide, and polyamideimide. Commercial products of these heat-resistant organic resin paints include DE220G manufactured by Nitto Denko Corporation.
T1 (45% by weight), Isomid manufactured by Eclipse Schenectady
40VH (concentration 42% by weight), Toray's Treenice # 3000
(Concentration 22% by weight), Hitachi Chemical HI405-30 (concentration 30
% By weight). The height of the resin insulating layer of the container is preferably about 1 to 30 μm, and if it is less than 1 μm, the above-mentioned effect of improving the flexibility and coil winding property cannot be expected. The heat resistance of the wire may be adversely affected, and the space factor of the wire decreases. Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 500 g of a polytitanocarbosilane resin (manufactured by Ube Industries, trade name Tyrannocoat, concentration 50% by weight), 500 g of a silicone resin (manufactured by Toray Silicone Co., trade name AY49-208, concentration 50% by weight) Nikkei Kakosha Co., Ltd., product name LS23) 400 g of the paint obtained by uniformly mixing the mixture onto a nickel-plated (1.0 mm thick plating) copper wire with an outer diameter of 1.0 mm.
Apply and bake six times at 00 ° C and a baking speed of 3.5 m / min.
A μm heat-resistant electric wire was obtained. Example 2 500 g of polytitanocarbosilane resin (manufactured by Ube Industries, trade name: Tyrannocoat, concentration: 50% by weight) and silicone resin (manufactured by Toray Silicone Co., trade name: AY49-208, concentration: 85)
%) 400 g of magnesium oxide and 350 g of magnesium oxide are uniformly mixed, and the resulting coating is nickel-plated with an outer diameter of 1.0 mm (plating thickness 1.0 mm).
μm) 6 on a copper wire at a baking temperature of 400 ° C and a baking speed of 3.5 m / min.
The coating was baked twice to obtain a heat-resistant electric wire having a baked layer thickness of 40 μm. Example 3 A baking temperature of a polyimide resin (Trenice # 3000, concentration 22% by weight, manufactured by Toray Co., Ltd.) on the heat-resistant electric wire obtained in Example 1.
Baking twice at 400 ° C and baking speed of 3.5m / min.
A heat-resistant electric wire having a total film thickness of 45 μm was obtained. Example 4 A polyamideimide resin (HI405-30, manufactured by Hitachi Chemical Co., Ltd., concentration: 30% by weight) was applied twice on the heat-resistant electric wire obtained in Example 2 at a baking temperature of 400 ° C. and a baking speed of 3.5 m / min. It was baked to obtain a heat-resistant electric wire having a total film thickness of 48u. Comparative Example 1 A polytitanocarbosilane resin (trade name: Tyrancoat, manufactured by Ube Industries, concentration: 50% by weight) was baked onto a nickel-plated (1.0 mm thick plating) copper wire having a diameter of 1.0 mm at a baking temperature of 400 ° C. and a baking speed of 3.5 m / Apply and bake 6 times under min condition, baking layer thickness 40
A μm heat-resistant copper wire was obtained. COMPARATIVE EXAMPLE 2 A polyimide resin (Trenice # 3000, concentration: 22% by weight) was applied onto the heat-resistant electric wire obtained in Comparative Example 1 twice at a baking temperature of 400 ° C. and a baking speed of 3.5 m / min. Thus, a heat-resistant electric wire having a total film thickness of 45 μm was obtained. Comparative Example 3 Silicone resin (trade name: AY49, manufactured by Toray Silicone Co., Ltd.)
-208, concentration 85% by weight) Nickel Micke (plating thickness 1.0μm) copper wire with a diameter of 1.0mm, baking temperature 400 ° C, baking speed
The coating was baked six times under the condition of 3.5 m / min to obtain a heat-resistant electric wire having a baked layer thickness of 40 μm. Comparative Example 4 A polyimide resin (Trenice # 3000, concentration 22% by weight, manufactured by Toray Industries Co., Ltd.) was applied and baked twice on the heat-resistant wire obtained in Comparative Example 3 at a baking temperature of 400 ° C. and a baking speed of 3.5 m / min. Thus, a heat-resistant electric wire having a total film thickness of 45 μm was obtained. The characteristics of the insulated wires of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in the table below.

   ────────────────────────────────────────────────── ─── Continuation of front page    (56) References JP-A-63-12672 (JP, A)                 JP-A-60-120755 (JP, A)                 JP-A-62-138574 (JP, A)                 JP-A-62-48773 (JP, A)                 JP-A-58-4209 (JP, A)                 JP-A-59-16210 (JP, A)                 JP-A-62-29781 (JP, A)                 JP-A-62-168376 (JP, A)                 JP-A-62-219486 (JP, A)

Claims (1)

(57) [Claims] A heat-resistant insulated wire, characterized in that a paint comprising a polytitanocarbosilane resin, a silicone resin that can be turned into a ceramic, and an inorganic filler is applied and baked on a conductor. 2. The amount of the silicone resin that can be ceramized per 100 parts by weight of the polytitanocarbosilane resin is 10 to 500 parts by weight, and the inorganic filler per 100 parts by weight of the total amount of the polytitanocarbosilane resin and the silicone resin that can be ceramized 2. The heat-resistant insulated wire according to claim 1, wherein the amount of the agent used is 10 to 250 parts by weight. 3. 3. The method according to claim 1, wherein an insulating layer made of an organic resin is provided on an applied and baked layer of a paint made of a polytitanocarbosilane resin, a silicone resin capable of being ceramized, and an inorganic filler. Heat-resistant insulated wires.