JP3461111B2 - Thermosetting resin composition and coil for rotating equipment using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition and a coil for rotating equipment such as a generator or a driving motor used in an automobile which is insulation-treated with the thermosetting resin composition.

[0002]

2. Description of the Related Art Conventionally, an insulating varnish for an electric device such as a rotating machine or the like, which is greatly vibrated during operation of a motor for a vehicle, a generator, etc., has a mechanical characteristic at a high temperature, an electric insulating property, a high voltage characteristic (an arc resistance). The acid anhydride curing type epoxy varnish, which has excellent properties and tracking resistance, is often used. In recent years, these electric devices have become smaller and lighter, and performance and reliability have been required to be improved more than ever before. In particular, measures to dissipate heat generated from operating devices cannot be performed well, and high temperature It was difficult to reduce the size of the equipment because of the importance of fixing performance and heat deterioration resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a thermosetting resin composition having improved thermal conductivity and excellent heat resistance, and a coil for a rotating machine using the same.

[0004]

The present invention provides (A) UL1
In the life of heat resistance evaluation test as defined in 446, containing F species (155 ° C.) or more thermosetting tree Abura及 beauty having heat lifetime (B) inorganic filler, the components (A) and component (B) After mixing, the cured product has a thermal conductivity of 5 × 10 ^-4 cal /
The present invention relates to a thermosetting resin composition having a temperature of cm · s · ° C. or higher, and a coil for a rotating device, which is insulation-treated with the composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin used as the component (A) in the present invention has a heat resistance life of at least F type (155 ° C.) in the heat resistance life evaluation test specified by UL1446 as described above. If so, there is no particular limitation,
After the components (A) and (B) have been mixed, the cured product must have a thermal conductivity of 5 × 10 ⁻⁴ cal / cm · s · ° C. or higher. When the thermal conductivity is less than 5 × 10 ⁻⁴ cal / cm · s · ° C., it becomes difficult to dissipate the heat generated from the equipment in operation.
Examples of the inorganic filler used as the component (B) in the present invention include hydrated alumina, fused silica, crystalline silica, magnesium oxide, calcium carbonate, talc, zirconium silicate, and the type thereof is not particularly limited.

In the thermosetting resin composition of the present invention,
The viscosity of the mixture of the component (A) and the component (B) measured at 25 ° C. with a rotary viscometer at a rotation speed of 30 to 60 rpm is 0.
It is preferably in the range of 05 to 1.5 Pa · s. If this viscosity is less than 0.05 Pa · s, the amount of varnish attached to the coil tends to decrease, and sticking tends to decrease. If it exceeds 1.5 Pa · s, the permeability of the varnish into the coil decreases. , A gap is generated between the coils, and the thermal conductivity tends to decrease. Further, it is preferable that the glass transition temperature of the cured product after the components (A) and (B) are mixed is 120 ° C. or higher. If the glass transition temperature is lower than 120 ° C, the cured product may be softened and deformed due to heat generated when the device is in operation. Furthermore, it is preferable that the cured product obtained by mixing the component (A) and the component (B) has an adhesive force of the lacquer at 155 ° C. of 200 N or more. If the adhesive strength of the tracker is less than 200 N, heat generated during the operation of the device tends to lower the coil fixing force.

In the thermosetting resin composition of the present invention,
The amount of the inorganic filler used as the component (B) is preferably in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the thermosetting resin. If it is less than this, the thermal conductivity cannot be improved and the heat dissipation of the device cannot be improved. On the other hand, if it is more than this, the adhesive strength of the lacquer at 155 ° C. will be reduced, and it will not be able to withstand the vibration generated by the equipment in operation, and the enamel wire will move.

Examples of the thermosetting resin in the present invention include unsaturated polyester resin compositions and acid-curable epoxy resin compositions.

The unsaturated polyester resin composition used in the present invention is an unsaturated polyester resin dissolved in a crosslinkable monomer. The unsaturated polyester resin used in the present invention is obtained by reacting an acid component containing an unsaturated dibasic acid as an essential component with an alcohol component. As the unsaturated dibasic acid, maleic anhydride, maleic acid, fumaric acid and the like are used, and these may be used alone or in combination. As the acid component, usually, a saturated acid in addition to the unsaturated dibasic acid is used in combination to adjust the amount of the unsaturated group contained and impart properties such as flexibility, heat resistance, and chemical resistance. It Saturated acids include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahitrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. Dibasic acid etc. are mentioned.
These may be used alone or in combination. The amount of unsaturated acid is preferably selected in the range of 50 to 90 equivalent% based on the total acid components.

As the alcohol component, a polyhydric alcohol having an ether bond such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol or polypropylene glycol is preferably used. These may be used alone or in combination. As the alcohol component, in addition to the alcohol component having an ether bond, an alcohol component having no ether bond may be used.
Such alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol,
Neopentyl glycol, glycerin, 1,6-hexanediol and the like are used. These may be used alone or in combination. The use of an alcohol having an ether bond is preferable because it can improve flexibility. Therefore, the amount of the alcohol component having an ether bond is preferably in the range of 30 to 100 equivalent%, particularly preferably 70 to 90 equivalent% based on the total alcohol components.

The unsaturated polyester resin used in the present invention is prepared by mixing an acid component and an alcohol component with each other at 190 to 22.
It can be obtained by heating to 0 ° C. and conducting a dehydration condensation reaction. The total alcohol component is 1 to 1 equivalent of the total acid component
It is preferable to use it in a range of 1.3 equivalents, and dicyclopentadienyl monomerate is used in an amount of 3 to 3 in the total acid component.
It is preferably used in the range of 30 equivalent%, and dicyclopentadiene is used in an amount of 0.1 to 0.1 mol per 1 mol of all acid components.
It is preferable to use 0.6 mol. Although heat resistance can be imparted to the resin by using dicyclopentadienyl monomerate or dicyclopentadiene,
If it is too large, flexibility tends to decrease.

Examples of the crosslinkable monomer used in the present invention include styrene, vinyltoluene, acrylic acid esters and methacrylic acid esters. The compounding ratio of the unsaturated polyester resin and the crosslinkable monomer is such that the total amount of the unsaturated polyester resin and the crosslinkable monomer is 100.
As the parts by weight, it is preferable to use 20 to 80 parts by weight of the unsaturated polyester resin and 80 to 20 parts by weight of the crosslinkable monomer, and particularly 30 to 60 parts by weight of the unsaturated polyester resin and 70 to 40 parts by weight of the crosslinkable monomer. preferable.

As the curing agent, for example, commonly used organic peroxides such as benzoyl peroxide, tertiary butyl peroxide, and methyl ethyl ketone peroxide are used. When the amount of the curing agent is small, it takes a long time to cure, and when it is large, the curing is too fast and the workability is deteriorated (the tank life is shortened). Therefore, the total amount of the unsaturated polyester resin and the crosslinkable monomer is 0. It is appropriately selected within the range of 2 to 4% by weight.

The acid-curable epoxy resin composition contains an acid anhydride and an epoxy resin. The acid anhydride used in the present invention is not particularly limited, but those which are liquid at room temperature are preferable, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenephthalic anhydride and dodecenylsuccinic anhydride. Acid etc. are mentioned. Commercially available products are HN-5500 and HN-220.
0, MHAC-P (trade name, manufactured by Hitachi Chemical Co., Ltd.), Q
H-200 (manufactured by Nippon Zeon Co., Ltd., trade name) and the like. These may be used alone or in combination of two or more.

Examples of the acid anhydride curing accelerator include:
2-ethyl-4-methylimidazole, 1-cyanoethyl-4-methylimidazole, imidazole such as 1-benzyl-2-ethylimidazole and its derivatives, and tertiary amines such as trisdimethylaminophenol and benzyldimethylamine Can be mentioned. Commercially available products are 2E4MZ (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), BD
MA (trade name, manufactured by Kao Corporation) and the like. The curing accelerator is used alone or in combination of two or more kinds. The compounding amount of these curing accelerators is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and 0.1 to 3 parts by weight per 100 parts by weight of acid anhydride. Is particularly preferable.

As the epoxy resin contained in the epoxy resin composition, a compound having at least two epoxy groups in one molecule is used, but the epoxy equivalent is 100 to 100.
4000 is preferable, and epoxy equivalent is 150 to 1.
000 is more preferable, and especially, the epoxy equivalent is 1
Those of 70 to 500 are preferable. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, and trimethylolpropane. Polyglycidyl ether of polyhydric alcohol, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, sebacic acid, polyglycidyl ester of polycarboxylic acid such as dodecanedioic acid, polyepoxide of polybutadiene and the like are used. These resins are not particularly limited, but those that are liquid at room temperature are preferable, and commercially available products are Epicoat 828 (Yukaka Shell Epoxy Co., Ltd., trade name), GY-260 (Ciba Geigy Co., trade name) ), DER-331 (trade name, manufactured by Dow Chemical Japan Co., Ltd.) and the like. These can be used alone or in combination.

When a low molecular weight epoxy resin which is a reactive diluent such as polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, butanediol diglycidyl ether is used as the epoxy resin, a higher molecular weight epoxy resin is used. It is preferable to use them in combination. Furthermore, as an epoxy resin,
It may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 40% by weight, and more preferably 0 to 20% by weight based on the total amount of the epoxy resin. Such epoxy compounds include n
-Butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromo cresyl glycidyl ether and the like. Further, an alicyclic epoxy compound such as methyl (3,4-epoxycyclohexane) carboxylate can also be used.

The compounding amount of these epoxy resins is preferably 70 to 100 parts by weight, more preferably 90 to 150 parts by weight, and 100 to 100 parts by weight with respect to 100 parts by weight of the acid anhydride.
140 parts by weight is more preferred. If the amount of the epoxy resin is too small or too large, the balance between the acid anhydride and the epoxy resin is lost and the curing does not proceed sufficiently.

The thermosetting resin composition of the present invention may be used in combination with a colorant, an anti-settling agent for an inorganic filler, and the like. Since the thermosetting resin composition of the present invention has excellent heat resistance and high thermal conductivity, insulation treatment using this composition can provide an electric device having sufficient heat dissipation and coil fixing force. . Examples of the electric equipment include a stator coil and an armature coil which are components of a generator or a driving motor used in an automobile, and examples of the treatment method include immersion impregnation and drop impregnation.
There are no particular restrictions on the processing conditions.

[0020]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. In addition, "part" in the following examples means "part by weight" unless otherwise specified.

Example 1 8 mol of dicyclopentadiene and 8 mol of maleic acid were charged into a synthesis kettle, 0.02% by weight of hydroquinone was added to the total weight of the above two substances, the temperature was raised to 70 ° C., and water was adjusted to 0.
4 mol was added. While paying attention to the heat of reaction, the temperature was raised to 140 ° C and then to 90 ° C. Furthermore, 0.4 mol of water was added, and the temperature was raised to 140 ° C while paying attention to the heat of reaction, and 1
After reacting at 40 ° C for 1 hour, the temperature was lowered to 100 ° C or lower. Next, 1 mol of ethylene glycol, 10 mol of 2,2′-oxydiethanol, 1 mol of phthalic anhydride and 5 mol of maleic anhydride were charged, and the mixture was synthesized at 205 ° C. for 9 hours and reacted when the acid value became 25 or less. Was completed and an unsaturated polyester resin was obtained. 100 parts of the obtained unsaturated polyester resin and 45 parts of styrene were mixed at 80 ° C. for 1 hour to obtain an unsaturated polyester resin A. In a heat resistance life evaluation test specified by UL1446, T.P. of twisted pair combined with ester imide wire was used. I. Is 193 [deg.] C. of unsaturated polyester resin A, and crystalline silica as an inorganic filler (trade name M1N- manufactured by Boxis Brown).
U-SIL 30 and 40 parts of average particle diameter 5 to 15 micron) were mixed to obtain a uniform resin composition. The viscosity of the obtained resin composition, the thermal conductivity of the cured product, the glass transition temperature, and the adhesive strength of the tracker were measured by the following methods, and the results are shown in Table 1.

Test Method Viscosity A BL type rotational viscometer was used for testing at a rotation speed of 60 rpm. Heat conductivity A cured product having a diameter of 50 × 5 mm was prepared, and a heat flow type heat conductivity meter was used to calculate the value T1 (mV) of the heating plate 1 and the value T2 of the heating plate 2.
(MV), the numerical value Q (mV) of the test piece, and the thickness d (mm) of the test piece from the thickness gauge. The thermal conductivity was calculated from the obtained numerical values using the following formula.

[Equation 1] A cured product having a glass transition temperature thickness of 0.3 mm and a size of 2 to 3 mm square was prepared, and the relationship between the temperature and the displacement at a temperature rising rate of 10 ° C./min with a constant load of 8 g using a penetration probe of a thermophysical tester. Get the curve. The inflection point of the displacement of the obtained curve was obtained by drawing a tangent line, and the temperature was taken as the glass transition temperature.

Adhesion of Stracker The test was conducted according to the adhesion test of Stracker of JIS C-2105. However, 1.2mm diameter piano wire to 2.0mm diameter amide-imide wire, and test piece length 100mm
And 50 mm were changed to 80 mm and 40 mm to obtain test pieces. This test piece was applied with a resin composition and heat-treated to give a test piece. 5 tests at 155 ℃,
The average value was taken. Furthermore, the obtained resin composition was used to insulate a coil, and the temperature rise of the coil when energized and the coil sticking property were tested by the following method, and the results are shown in Table 1.
Shown in. Using the coil temperature increasing resin composition, a coil portion of a condenser motor (stator coil) having a diameter of 90 mm and a stacking thickness of 50 mm was subjected to a drop impregnation treatment and heat-cured to prepare a test piece. The test piece was energized at 100 V to measure the temperature rise of the coil. Coil sticking property A test piece prepared for measuring a rise in coil temperature was left in an atmosphere of 155 ° C. for 3 hours, and then the sticking state of the coil was evaluated.

Example 2 The content of crystalline silica used as an inorganic filler was 40%.
A resin composition was prepared in the same manner as in Example 1 except that the number of parts was changed to 20 parts, and the same tests as in Example 1 were performed. The results are shown in Table 1.

Example 3 100 parts of Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd., trade name), 80 parts of acid anhydride curing agent MHAC-P (produced by Hitachi Chemical Co., Ltd., trade name) 2-ethyl 2 parts of -4-methylimidazole was added and mixed uniformly to obtain an acid anhydride-curable epoxy resin. (A) In a heat resistance life evaluation test specified by UL1446, T. of a twisted pair combined with an amide-imide wire was used. I. Of 163 ° C. acid anhydride curing type epoxy resin 10
0 part and crystalline silica as an inorganic filler (trade name: MIN-U-SIL30, manufactured by Bokusui Brown Co., average particle size: 5)
˜15 μm) was mixed to obtain a uniform resin composition. The same test as in Example 1 was conducted using the obtained resin composition, and the results are shown in Table 1.

Comparative Example 1 The resin composition obtained by removing the inorganic filler from the resin composition of Example 1 was used as the resin composition, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

Comparative Example 2 The resin composition obtained by removing the inorganic filler from the resin composition of Example 3 was used as the resin composition, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

Comparative Example 3 341 parts (5.5 mol) of ethylene glycol, 296 parts (2.0 mol) of phthalic anhydride, 196 parts (2.0 mol) of maleic anhydride, and 560 parts (2.0 parts) of soybean oil fatty acid. Mol)
And 0.24 part of hydroquinone were placed in a four-necked flask and heated and condensed at 200 ° C. for about 10 hours to synthesize an unsaturated polyester resin having an acid value of 20.8. 40 parts of this unsaturated polyester resin, 60 parts of styrene, and 0.5 parts of 8% manganese naphthenate were dissolved by stirring to obtain unsaturated polyester resin B. In the heat resistance life evaluation test specified by UL1446, T.P. of twisted pair combined with polyester wire was used. I. Unsaturated polyester resin B1 with a temperature of 152 ° C
00 parts and 40 parts of crystalline silica (trade name: MIN-U-SIL30, manufactured by Bokusui Brown Co., average particle size 5 to 15 microns) as an inorganic filler are mixed to obtain a uniform resin composition. The same test as in Example 1 was conducted using the obtained resin composition, and the results are shown in Table 1.

[0029]

[Table 1]

[0030]

Since the thermosetting resin composition of the present invention has a large thermal conductivity and excellent heat resistance, the rotating equipment treated with this resin composition is self-heated by the miniaturization of the equipment. Can be dissipated and the reliability at high temperature is improved, so that the size of the rotating device can be further reduced.

Claims (5)

(57) [Claims] 1. A (A) UL1446 life of heat resistance evaluation test as defined in, containing F species (155 ° C.) or more thermosetting tree Abura及 beauty having heat lifetime (B) inorganic filler, (A A thermosetting resin composition having a thermal conductivity of 5 × 10 ⁻⁴ cal / cm · s · ° C. or more after being cured after mixing the component (4) and the component (B). 2. A mixture of a component (A) and a component (B), 2
The thermosetting resin composition according to claim 1, wherein the viscosity at a rotation speed of 30 to 60 rpm measured by a rotary viscometer at 5 ° C is in the range of 0.05 to 1.5 Pa · s. 3. The glass transition temperature of the cured product is 120.
The thermosetting resin composition according to claim 1, which has a temperature of not less than ° C. 4. The thermosetting resin composition according to claim 1, wherein the cured product has an adhesive force of the stlacker at 155 ° C. of 200 N or more. 5. A coil for a rotating device, which is insulation-treated with the thermosetting resin composition according to claim 1.