JPS5922322B2 - insulation paint - Google Patents

Description

[Detailed Description of the Invention] The present invention prevents smoke accidents from occurring when electrical equipment such as transformers or motors (particularly small transformers or small motors) manufactured using the enameled wire of the present invention burns out. If necessary, the insulating layer of the enamelled wire can easily melt when it reaches a certain temperature, causing a short circuit between the wires, causing the wire to melt at the point where there is no short circuit, and causing smoke and fire caused by electrical equipment. Alternatively, the present invention relates to an enameled wire that is characterized by being able to prevent electric shock accidents.

In recent years, smoke accidents caused by home appliances such as televisions,
The frequency of occurrence of fire accidents and electric shock accidents is increasing, and it is strongly desired to prevent these accidents.

In response to this, safety standards for electrical and electronic equipment are becoming increasingly strict in each country. Among these devices, problems may be relatively easy to solve for those that use low voltage and low power, but television receivers, microwave ovens, etc. that use high voltage and high power may cause smoke accidents, fire accidents, or electric shocks. There are many weaknesses in terms of accident prevention, and there is a strong demand for a design that overcomes these weaknesses. Looking at statistics on television receivers in the United States as an example of fire and smoke accidents caused by parts of these devices, transformers account for approximately 30% of the accidents, and fires and smoke accidents occur from transformers and high-voltage circuits. About half of them do so.

For this reason, it is strongly desired not only to make these devices and parts flame retardant, but also to automatically cut off the circuit in the event of an abnormal condition before a fire or electric shock occurs, and also to not generate smoke. There is. In order to deal with this, the transformer industry is considering inserting a fuse system such as a bimetal system as a protection device into the transformer to ensure reliability in a fault condition. If the selling price of a small transformer is 100 yen, the value of this fuse is approximately 30 to 100 yen, which leads to a significant increase in cost and is also undesirable in terms of the space factor of the equipment. However, in order to cope with the trend of strengthening safety standards, the cost increase is unavoidable, and the current situation is that the trend is towards adopting this method. Similar problems occur with small motors used in tape recorders and the like, and it is strongly desired to prevent smoke and fire accidents when abnormal temperatures rise due to overload or the like. The present invention incorporates the fuse function as described above into the enameled wire itself, so that there is no structural change from conventional electric/electronic equipment parts such as transformers and small motors, and the impact on price is minimized. The object of the present invention is to provide an enameled wire that can solve the above-mentioned problems.

In other words, the insulating coating of the enamelled wire is designed to prevent electrical or electronic equipment parts such as transformers or small motors from burning out, causing smoke accidents, fire accidents, or electric shock accidents, and furthermore, so that they can be cut dynamically by circuit forces. By applying and baking an insulating paint whose main component is thermoplastic linear polyurethane obtained from a specific diol and a specific diisocyanate, the insulating film melts at a constant temperature and creates line-to-line insulation. We have discovered that this purpose can be achieved by eliminating the . In this case, the characteristics required of the enamelled wire are very delicate and difficult. In other words, under normal operating conditions, the enameled wire has sufficient insulation, and has excellent properties such as heat resistance, impregnation varnish resistance, solderability, thermal shock resistance, chemical resistance, adhesion, processing deterioration resistance, and baking workability. Although it is not inferior to the enamelled wire used in the past, it has characteristics that are difficult to reconcile with these characteristics.When a certain temperature is reached, it is extremely sensitive and there is little variation in the sensitive temperature, so the insulating film melts and the wire There needs to be a short circuit between them. Moreover, in the United States, it is required that the cheesecloth placed on the surface of the transformer not burn or burn in the event of a burnout, and to meet this requirement, it is considered necessary to keep the surface temperature below 250°C. Therefore, taking into account the insulation properties during normal operation, the internal temperature should be 150~
It is thought that it is necessary for the film to melt at about 250°C, most preferably at about 170 to 230°C, and to short-circuit the wires. This is a very low hardness compared to the common sense of conventional enamelled wires, and the direction of research and development of new enameled wires is toward heat resistance, so it is natural that materials with as high a heat softening temperature as possible are sought. This is the complete opposite of the conventional enamelled wire, and is contrary to common sense regarding conventional enamelled wire, and conventional enamelled wire has never been endowed with such characteristics. In addition, as shown in the reference example, it has been found that simply having a low thermal softening temperature or melting point does not necessarily result in short circuits near that temperature, nor does it prevent smoke from burning out, so the selection range of insulating materials may vary. It was also found that the
It is assumed that only very specific materials can be used for these purposes. As a result of intensive studies regarding the above points, the present inventor found that the enameled wire of the present invention has good heat resistance, impregnation varnish resistance, solderability, thermal shock resistance, chemical resistance, adhesion, processing deterioration resistance, It has excellent properties such as baking workability, and is extremely sensitive to melting of the insulation film and melting of the wire, not only at the beginning of use, but also after long-term thermal deterioration, when abnormal temperatures are reached due to burnout, etc. Moreover, it was found that almost no smoke was observed.

The enamelled wire of the present invention can be used in any way, but its characteristics can be particularly demonstrated in small transformers (transformers) used in television receivers, stereos, radios, etc., tape recorders, stereos, measurements, etc. This is a case where it is applied to small motors used in equipment, etc. For these uses, the wire size is 0.05 to 0.41 in diameter! The most common one is about l. In order to obtain the enameled wire of the present invention, the insulating paint used in the present invention may be coated and baked on the conductor directly or through another insulator, or the insulating paint used in the present invention may be coated on the conductor. After baking, another layer of insulation may be placed over this. Examples of other insulators mentioned here include nylon 6, nylon 6,6, nylon 6,10, and nylon 1.
1. It is preferable to use thermoplastic materials such as nylon 12, copolymerized nylon, thermoplastic polyester, and polyvinyl formal. In particular, when another insulating layer having a melting point lower than that of the insulating layer obtained from the insulating paint used in the present invention is used as an upper layer, it can also be used as a self-bonding enameled wire. In the present invention, an insulating coating mainly composed of thermoplastic linear polyurethane refers to the polymer solution of thermoplastic linear polyurethane itself, or in addition to linear polyurethane and a solvent within a range that does not impair its properties. other thermoplastics,
Alternatively, it refers to a product in which one or more of thermosetting additive resins, fillers, pigments, dyes, silicone compounds, fluorine compounds, etc. are added.

The thermoplastic linear polyurethane used to obtain the insulating coating of the present invention is obtained by reacting one or more diisocyanates selected from the group consisting of diisocyanates and masked diisocyanates with one or more diols. It is a linear polyurethane that can be obtained at least.

In producing this linear polyurethane, the reaction can be carried out in the absence of a solvent or in the presence of a solvent, but in terms of reaction control it is best to carry out the reaction in the presence of a solvent. preferable. The solvent is preferably an organic solvent which does not react with the components under the reaction conditions under which the reaction is carried out, or which only forms loosely bound adducts or further reacting compounds; It is preferable to use one that dissolves the polymer produced by the process. Suitable solvents include hydrocarbons, halogenated hydrocarbons, phenols, esters, ketones, ethers, substituted amides, sulfoxides and sulfones, such as toluene, xylene, o-dichlorobenzene, phenols, Cresylic acid, o-cresol m-cresol, p
-Cresol, various xylenol, acetophenone,
Benzophenone, ethylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N,N
-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-
Pyrrolidone, N-acetyl-2-pyrrolidone, N-methyl-caprolactam, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, hexamethylphosphoramide, formamide, N-methylformamide, γ-butyrolactone, and mixtures thereof. be. Preferred are solvents containing phenols or substituted amides as a main component. Most preferred are solvents based on substituted amides, especially those based on N,N dimethylacetamide and N-methyl-2-pyrrolidone. The raw material for producing the thermoplastic linear polyurethane used in the present invention is a method in which diisocyanates are reacted in the presence of the diol component of the final product.

The reaction for producing the thermoplastic linear polyurethane used in the present invention can be accelerated by using a suitable catalyst.

Examples include those commonly used in the reaction of isocyanates, such as boron fluoride, its adducts, mineral acids, carboxylic acids, zinc chloride, and also triethylamine, N-alkylmorpholines, triethylenediamine, 1,8-diaza There are tertiary amines such as bicyclo(5.4.0) undecene-7 (including this acid adduct), trialkylphosphines, and dialkyltin diazines such as potassium acetate, zinc octoate, and dibutyltin dilaurate. Salt, lithium linoleate, sodium oleate, sodium methoxide, and potassium ethoxide are any alkali metal salts, or heavy metal salts such as cobalt acetate and cobalt naphthenate. Further, there are titanium-based catalysts such as titanium tetraalkoxides such as titanium isopropoxide, titanium tetrabutoxide, and titanium tetraphenolade, or their chelate compounds, tetraalkyl titanium anlate compounds, and titanium bischelate compounds. Among these, preferred are tertiary amines, tin-based compounds, and titanium-based compounds, and particularly preferred are titanium-based catalysts such as 1,8-diazabicyclo(5.4.0)undecene-7 (this acid adduct). ). In the following Examples and Comparative Examples, the enamelled wire was made by coating and baking an insulating paint on the conductor using a conventional method, and the fusing temperature was measured using a body diameter of 18111 and a brim diameter of 40.
m11L1 If the core wire diameter is 0.3 mm, wrap an enamelled wire around a plastic bobbin with a body length of 911 mm, 150 turns, sandwich a CA thermocouple with a diameter of 0.3110 mm in the center, and wrap an additional 150 turns of enameled wire on top of this. If the core wire diameter is 0.211, wind the enamelled wire 200 turns and make a wire with a diameter of 0.3111 (
7) Sandwich the CA thermocouple and add one more enameled wire on top of it.
The sample was prepared by winding it with 50 turns.

A large current was applied to this sample to generate heat, and the temperature at which the enameled wire melted due to the heat generation was measured using an inserted CA thermocouple. The characteristics test method for enameled wire is heat softening resistance,
Other than the thermal melting temperature, JISC3OO3 was followed. The reduced specific viscosity of the resin was measured by dissolving 0.59 of the resin in 100w11 of N,N-dimethylacetamide at 30°C. Example 11,6-hexanediol, 591.09 (5
．． 0 mol) and diphenylmethane-4,4! -diisocyanate 1251.39 (5.0 mol) and N-methyl-2
-2 Pyrrolidone 27609 was stirred in a reaction vessel, and after a while it generated heat, and as the temperature rose to about 85°C due to the heat of reaction, it gradually became viscous.

Next, the oil bath was heated to raise the temperature of the reaction system to 120° C. in 1 hour, and the reaction was completed at this temperature for 1.5 hours. N-methyl-2-pyrrolidone 23989 and solvent naphtha 22109 were added to dilute the solution to obtain a transparent polymer solution. The solution viscosity was 2200 Cps (30°C). The reduced specific viscosity of the polymer was 0.86. This polymer solution has a diameter of 0.311! An enamelled wire was obtained by coating and baking it on a copper wire. The characteristics of this enameled wire are shown in Table 1. Example 2 The polymer solution obtained in Example 1 was made to have a solution viscosity of 200 cps using N-methyl-2-pyrrolidone and solvent naphtha, and this was applied and baked on a copper wire having a diameter of 0.2 mm to obtain an enameled wire.

The characteristics of this enameled wire are shown in Table 1. Example 3 1,6-hexanediol 236.49 (2.0 mol)
and diphenylmethane-4,4'-diisocyanate 49
When 0.59 (1.96 mol), N-methyl-2-pyrrolidone 7909, and xylene 3009 are stirred in a reaction vessel, heat is generated after a while, and the temperature is raised to about 95°C due to the heat of reaction.
It gradually became viscous.

Next, heat the oil bath to heat the reaction system to 120% in 1.5 hours.
The temperature was raised to .degree. C., and the reaction was completed at this temperature for 2 hours. N-methyl-2-pyrrolidone 15109 and xylene 3909 were added to dilute the solution to obtain a transparent polymer solution.
The solution viscosity was 1700 cps (30° C.), and the reduced specific viscosity of the polymer was 0.61. This polymer solution was
200c with methyl-2-pyrrolidone and solvent naphtha
The solution was diluted to PS and coated on a copper wire having a diameter of 0.2 and baked to obtain an enamelled wire. Table 1 shows the characteristics of this enameled wire.
It was shown to. Example 416-hexanediol 236.
When 475.59 (1.9 mol) of diphenylmethane-4,4'-diisocyanate and 10,709 dimethylacetamide were stirred in a reaction vessel, heat was generated after a while and the temperature rose to about 85°C due to the heat of reaction. The temperature rose and it gradually became viscous.

Next, the oil bath was heated to raise the temperature of the reaction system to 123° C. in 1 hour, and the reaction was completed at this temperature for 2 hours.
N-methyl-2-pyrrolidone 1749 and xylene 5339 were added to dilute the solution to obtain a transparent polymer solution. The solution viscosity was 750 cps (3'C). The reduced specific viscosity of the polymer was 0.40. This polymer solution was mixed with N-methyl-2-pyrrolidone and xylene at 200 cps (300 cps).
C) was diluted and coated on a copper wire having a diameter of 0.211 mm and baked to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. Example 5 1,6-hexanediol 236.49 (2.0 mol)
and diphenylmethane-4,4'-diisocyanate 47
When 0.59 (1.88 mol) and 1060 g of N-methyl-2-pyrrolidone were stirred in a reaction vessel, heat was generated for a while and the temperature rose to about 80°C due to the heat of reaction)) The mixture gradually became viscous. .

Next, the oil bath was heated to raise the temperature of the reaction system to 120°C in 1 hour, and the reaction was allowed to proceed at this temperature for 1.5 hours. A polymer solution was obtained. The reduced specific viscosity of the polymer is 0.3
It was 6. This polymer solution was diluted to 200 cps (300 C) with N-methyl-2-pyrrolidone, and this was applied and baked onto a copper wire having a diameter of 0.2 ml to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. Example 61
,6-hexanediol 236.49 (2.0 mol) and diphenylmethane-4,4'-diisocyanate 465
．． When 59 (1.86 mol) and N-methyl-2-pyrrolidone 10539 were stirred in a reaction vessel, heat was generated after a while, and as the temperature rose to about 80°C due to the heat of reaction, the mixture gradually became viscous.

Next, the oil bath was heated to raise the temperature of the reaction system to 120°C in 1 hour, and the reaction was allowed to proceed at this temperature for 1.5 hours. A polymer solution was obtained. The reduced specific viscosity of the polymer is 0.3
It was 4. This polymer solution was diluted with N-methyl-2-pyrrolidone and xylene to 200 cps (30°C),
This was coated and baked on a copper wire with a diameter of 0.211 mm to obtain an enamelled wire. The characteristics of this enameled wire are shown in Table 1. Example 7 1,6-hexanediol 425.59 (3,6 mol)
and 1,4-butanediol 81.19 (0.9 mol) and diphenylmethane-4,4'-diisocyanate 110
When 3.69 (4.41 mol) and N-methyl 2-pyrrolidone 37351 were stirred in a reaction vessel, heat was generated after a while, the temperature rose to about 70°C due to the heat of reaction, and the mixture gradually became viscous.

Next, the oil bath was heated to raise the temperature of the reaction system to 120° C. in 1 hour, and the reaction was allowed to proceed at this temperature for 2 hours. Thereafter, xylene 13659 was added to dilute the reaction system to obtain a transparent polymer solution.
The solution viscosity was 1300 cps (30 C). The reduced specific viscosity of the polymer was 0.60. This polymer solution was mixed with N-methyl-2-pyrrolidone and xylene at 200 cps.
(3'C) and applied and baked on a copper wire with a diameter of 0.2 mm to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. Example 8 1,6-hexanediol 319.19 (2.7 mol)
and 1,4-butanediol 162.29 (1.8 mol)
and diphenylmethane-4,4'-diisocyanate 11
03.69 (4.

When N-methyl-2-pyrrolidone (23809) and N-methyl-2-pyrrolidone (23809) were stirred in a reaction vessel, heat was generated after a while, the temperature rose to about 85° C. due to the heat of reaction, and the mixture gradually became viscous.

Next, the oil bath was heated to raise the temperature of the reaction system to 120°C in 1 hour, the reaction was continued at this temperature for 1.5 hours, and then N
-Methyl-2-pyrrolidone 5609, xylene 1260
9 was added to dilute the solution to obtain a transparent polymer solution. The solution viscosity was 2000 cps (30 body C), and the reduced specific viscosity of the polymer was 0.53. This polymer solution was mixed with N-methyl-
200cps (302C) with 2-pyrrolidone and xylene
The enameled wire was diluted to 100% and coated and baked on a copper wire with a diameter of 0.211 mm to obtain an enamelled wire. The characteristics of this enameled wire are shown in Table 1. Example 9 1,6-hexanediol 236.49 (2.0 mol)
and diphenylmethane-4,4'-diisocyanate 39
2.49 (1.568 mol) and tolylene diisocyanate (80:20 mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate) 68.3
9 (0.392 mol) and N-methyl-2-pyrrolidone 1
When 0509 is stirred in a reaction vessel, heat is generated after a while,
The temperature rose to about 75°C due to the heat of reaction and gradually became viscous.

Next, heat the oil bath to raise the reaction system to 120℃ in 1 hour, react at this temperature for 2 hours, and then add N-methyl-2-pyrrolidone 909 and xylene 4909 to dilute it and make it transparent. A polymer solution was obtained. Solution viscosity is 1900
cps (300C). The reduced specific viscosity of the polymer is 0
．． It was 62. This polymer solution was diluted to 200 cps (30 AC) with N,N-dimethylacetamide and xylene, and this was applied and baked on a copper wire with a diameter of 0.2 ml to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. Example 10 1,6-hexanediol 236.49 (2.0 mol)
and diphenylmethane-4,4'-diisocyanate 34
3.39 (1.372 mol) and tolylene diisocyanate (80:20 mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate) 102.
When 49 (0.588 mol) and N-methyl-2-pyrrolidone 10209 were stirred in a reaction vessel, heat was generated after a while, the temperature rose to about 88° C. due to the heat of reaction, and the mixture gradually became viscous.

Next, heat the oil bath and carry out the reaction at 120°C for 1.5 hours.
The temperature was raised to 1.5 hours, and the reaction was carried out at this temperature for 1.5 hours.
4 g was added and diluted to obtain a transparent polymer solution. The reduced specific viscosity of the polymer was 0.55. This polymer solution was mixed with N,
200cps (30NC) with N-dimethylacetamide
The enameled wire was diluted to 100% and coated and baked on a copper wire with a diameter of 0.211 mm to obtain an enamelled wire. The characteristics of this enameled wire are shown in Table 1. Example 11 1,6-hexanediol 236.49 (2.0 mol)
and diphenylmethane-4,1-diisocyanate 392
．． When N-methyl-2-pyrrolidone 10409 and N-methyl-2-pyrrolidone 10409 were stirred in a reaction vessel, heat was generated after a while and the temperature was raised to about 80°C.

Next, here is hexamethylene diisocyanate 65.9f
! (Add 0.392 mono(c) and 0.2f! of dibutyltin dilaurate!, heat the oil bath, raise the temperature of the reaction system to 120℃ in 1 hour, react at this temperature for 2 hours, and add N -Methyl-2-pyrrolidone 90f! and xylene 4909 were added to dilute to obtain a transparent polymer solution.
The reduced specific viscosity of the polymer is 0.59, and the solution viscosity is 1700.
It was cps. This polymer solution was diluted to 200 cps (30 DEG C.) with N-methyl-2-pyrrolidone, and this was coated and baked on a copper wire with a diameter of 0.2 ml to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. Example 1
2 1,6-hexanediol 118.29 (1.0 mol)
and diphenyl ether-4,4'-diisocyanate 2
When 47.29 (0.98 mol), N,N-dimethylacetamide 5979, and xylene 256 g are stirred in a reaction vessel, heat is generated after a while, the temperature rises to about 80°C due to the heat of reaction, and it gradually becomes viscous. Ta.

Next, heat the oil bath to heat the reaction system to 120% in 1.5 hours.
The temperature was raised to ℃ and reacted at this temperature for 2 hours, after which N was added.
, N-dimethylacetamide 2989, xylene 128
9 was added to dilute the solution to obtain a transparent polymer solution. The reduced specific viscosity of the polymer was 0.55. This polymer solution has a diameter of 0
．． The enameled wire was coated and baked on a No. 311 copper wire to obtain an enamelled wire. The characteristics of this enameled wire are shown in Table 1. Example 13 The polymer solution obtained in Example 12 was diluted to 200 cps (30° C.) with N,N-dimethylacetamide, and this was applied and baked on a copper wire with a diameter of 0.2 mm to obtain an enameled wire.

The characteristics of this enameled wire are shown in Table 1. Example 14 1,4-butanediol 180.29 (2.07 L) and diphenylmethane-4,4'-diisocyanate 500
．． 59 (2.0 mol) and N-methyl-2-pyrrolidone 1
When 0219 is stirred in a reaction vessel, heat is generated after a while,
The temperature rose to about 88°C due to the heat of reaction and gradually became viscous.

Next, heat the oil bath to heat the reaction system to 120% in 1.5 hours.
℃, react at this temperature for 1 hour, and then add N.
-1021 g of methyl-2-pyrrolidone was added to dilute the solution to obtain a transparent polymer solution. The reduced specific viscosity of the polymer is 0.96
It was hot. This polymer solution was diluted with N-methyl-2-pyrrolidone and xylene to 200 cps (30° C.), and this was applied and baked on a copper wire having a diameter of 0.211 mm to obtain an enameled wire. The characteristics of this enameled wire are shown in Table 1. In addition, each enamelled wire of Examples 1 to 14 all had the following properties in the thermal melting test:
Only a very small amount of smoke was emitted during thermal melting.

Furthermore, the wire coating after thermal cutting was not discolored at all. Comparative Example 1 6,10-nylon (CM2OOl manufactured by Toray), 6-nylon (CMlOOl manufactured by Toray), 6,6-nylon (CM3OOl manufactured by Toray), and phenoxy (PKHH85OO manufactured by Union Carbide, USA) were each dissolved in cresol. Obtained insulation paint.

Claims (1)

[Claims] 1 diphenylmethane-4,4'-diisocyanate,
Diphenyl ether-4,4'-diisocyanate, 2
, 4-tolylene diisocyanate, and 2,6-tolylene diisocyanate, and 1,4-butanediol and/or 1,6-hexanediol. The molar ratio of diisocyanates is 0.9
~1.1 A fuse function characterized by being obtained by applying and baking an insulating paint mainly composed of thermoplastic linear polyurethane obtained by reacting as described in 1.1 onto a conductor, either directly or through another insulator. Enamelled wire.