JPS6022444B2 - Laminated mica materials, laminated mica prepreg materials and laminated mica products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite mica material, a composite mica prepreg material, and a composite mica product.

Conventionally, laminated mica is produced by heating muscovite to around 800°C to make it crystallized, and then pulverizing it in water using a water jet or a grain of about 0.2 to 1. Mica foil, so-called calcined laminated mica, is generally used, which is made from slurry of mica flakes as small as the size of a bow. Mica foil was made from slurry made from mica flakes as small as an enemy, and so-called soft laminated mica was used.

Calcined mica cannot be industrially pulverized to a thin thickness with an elevation angle of 5 to IQ, and the strength of the mica scale is low because microscopic cracks occur inside the scale when mica crystal water is released. In addition, the density of fired laminated mica is 1.3 to 1. For example, in order to make a prepreg material, a large amount of thermosetting resin composition is required, and as a result, the resin of the product obtained by heating and pressure molding the prepreg material The mechanical properties and fin comfort were poor.

Further, in order to make heat-resistant laminated mica, a large amount of heat-resistant thermosetting resin composition is required, resulting in disadvantages such as poor heat resistance and significant long-term deterioration. On the other hand, although phlogopite has slightly better heat resistance than muscovite, its electrical properties are inferior, so it cannot be used for insulation in generators, etc.

On the other hand, unfired mica that has been crushed into smaller pieces can reduce the amount of adhesive used when processing into laminated mica products compared to finely crushed fired laminated mica.
The mechanical properties and electrical properties were inadequate compared to peelable mica products.

In order to solve these shortcomings, American Samaica Corporation (U.S.
S. SAMICA Corporation),
An unfired laminated mica called MicanitoD has been developed. Micaite mica is obtained by crushing unfired muscovite flakes in water using ultrasonic energy, and its particle size distribution is shown in Table 1 along with the values of commonly used aggregate mica. Table 1 *1 The numbers in the table are expressed as weight percentages.

*2 Source, U. S. SAMICA Corporation
Kata of on.

Although it is an unfired laminated mica, its tensile strength is 0.
It is strong at ~1.3k9f/ground, and the density of mica foil is also 1
．． 6-1.

Although it has a high value of 7g/ground, it has a drawback due to the particle size distribution shown in Table 1.

Since Mica Night D uses large particles, the reinforcing effect of the mica particles is large, and the mechanical properties of mica products processed with it are improved. After deterioration, its properties, particularly its electrical properties, were inferior to those of peelable mica products.

Peeling mica products are approximately 5 mm in diameter or more and 3 mm in thickness.
Mica is hand-peeled with a size of 0 to 50 meters, and due to its large size, it is similar to laminated mica (it cannot be made using a wet paper machine and is pasted by hand or using semi-automated machines). It is.

Peelable mica products are more expensive than laminated mica products because peelable mica is expensive and cannot be mass-produced by machines. The product's properties were excellent even after long-term deterioration, as it used larger scale pieces than conventional laminated mica, and the large scale pieces continued to act as an insulator even after the adhesive had deteriorated.

In order to take advantage of the features of peel-off mica and laminated mica, consideration has been given to using them in combination.

For example, products such as Samurai Seki Sho 53-Mura No. 500, in which laminated mica sheets are pasted on both sides of a T-peel mica sheet, have better thickness accuracy than peel-off mica products, but their characteristics, especially after long-term deterioration. , which was closer than peeling mica alone. The present invention overcomes these drawbacks.

The present invention is based on the particle size of 1. 30 to 7 parts by weight of mica flakes with an aspect ratio of 150 or more, and 20 to 4 parts by weight of mica flakes with a grain size of 0.25 ribs or more and 1.0 ribs or more. A laminated mica material obtained by milling a slurry containing 10 to 3 parts by weight of mica flakes less than skin size, and a particle size obtained by crushing uncalcined mica with a particle diameter of 1.2 cm or more and an aspect ratio of 150.
30 to 70 parts by weight of the above mica flakes, particle size 0.25
A thermosetting resin is added to the composite mica material obtained by paper-making a slurry containing 20 to 4 parts by weight of mica scales having a rib size or more and less than 1.0 legs, and 10 to 30 parts by weight of mica scales having a size less than 0.25. Particle size obtained by crushing unfired mica and a composite mica pre-preg material impregnated with the composition, adhered to bag batting material as necessary, and semi-cured. 30 to 7 pieces of mica lime that are Q or above and have an aspect ratio of 150 or more.
0 parts by weight, 20 to 40 parts by weight of mica scale pieces with a particle size of 0.25 to 1.0 scale, and 10 to 3 parts by weight of mica scales with a particle size of less than 0.25 scale. After impregnating or coating the composite mica material with a thermosetting resin composition or an inorganic composition. This invention relates to a laminated mica product formed by molding under heat and pressure. The aspect ratio in the present invention is ≧Imo Mi U Kishi Koto Sui Hajime, and the particle size distribution was calculated by wet classification using a standard analytical sieve and then measuring the weight after drying.

There was no conventional method for pulverizing unfired mica to the particle size distribution of the present invention;
This became possible for the first time through methods such as Banpaygo.

Since these methods integrate crushing equipment and classification equipment, they are excellent methods that allow a large aspect ratio and easily obtain the desired particle size distribution. If the proportion of mica flakes with a particle size of 1.0 or more is less than 30 parts by weight, the reinforcing effect of the mica flakes is small, and the mechanical properties of the mica laminated product processed from them will deteriorate; on the other hand, if the proportion exceeds 7 parts by weight. Although the reinforcing effect is large, the voids in the paper-made mica sheet become large, resulting in a decrease in electrical properties. Further, if the aspect ratio of the mica flakes having a grain size exceeding one rib is less than 150, this is not desirable because the mechanical and electrical properties are deteriorated.

In addition, if less than 1 part by weight of mica flakes with a particle size of less than 0.25 feet is contained, 1. It is not possible to sufficiently fill the voids in the mica flakes, which are larger than the ribs, and not only requires a large amount of adhesive, but also deteriorates the electrical properties after long-term deterioration.
Moreover, if the amount exceeds 3 parts by weight, the mechanical properties and electrical properties are deteriorated, which is not desirable. When only mica scale pieces with a grain size of less than 0.25 feet and mica scale pieces with a particle size of 1.0 scales or more are combined, the settling speed of the mica scale pieces differs by more than 1 inch between the former and the latter, so wet paper making is not possible. When making paper using a machine, there will be large pieces of lime on one side and small pieces on the other side, making it impossible to pack them tightly. 20～
Use 4 parts by weight.

If the amount is less than 2 parts by weight, the addition has no effect, that is, it does not provide technical filling, and if it exceeds 4 parts by weight, the mechanical properties deteriorate.

In the present invention, there are no particular restrictions on the method of paper-making the slurry, and any conventional method may be employed.

For example, this is carried out using a paper machine such as a wire-mesh type paper machine or a circular-mesh type paper machine.
There are no restrictions on the paper-making conditions, etc. For the backing material, known materials are used, for example, woven fabrics, non-woven fabrics, films, etc. made of organic or inorganic materials such as polyester, polyamide, glass, etc. are used in combination if necessary, and these are used in combination with glass yarn, There is no problem in combining polyester fiber yarn, etc. As the thermosetting resin composition, an epoxy resin composition containing a curing agent, a surfactant, a solvent, etc., an unsaturated polyester resin composition, a silicon IJ cone resin composition, etc. are used.

Inorganic compositions, aluminum phosphate compositions, etc. used in composite mica products are used. The method of impregnating or coating a thermosetting resin composition when obtaining a composite mica prepreg material and a composite mica product is to dissolve the thermosetting resin composition in a solvent such as methyl ethyl ketone, acetone, or methanol, and then spray it. The mica material is impregnated or coated using a general coating machine such as a nozzle or brush coating machine.

After impregnation or coating, drying with hot air, infrared rays, etc.
Solvent is removed. For impregnation of the thermosetting resin composition into the composite mica material or semi-curing after coating, normal conditions are employed and there are no particular limitations. In order to obtain a composite mica product, molding is carried out under heat and pressure, but the heating temperature should be at least the temperature at which the thermosetting resin composition softens, and the pressure to be applied should be as long as the molded product is integrated. It may be added until the resin composition is hardened and shaped.

Unfired mica refers to mica that is not subjected to firing treatment, paper contained in mica such as scrap mica, cut mica, etc.
This refers to mica in which organic components such as wood and fibers have been completely removed by combustion in the air at a temperature that does not dehydrate the mica crystal water (approximately 600oC or less) to a temperature that dehydrates the mica crystal water to 1/s. . If calcined mica is used instead of coagulated and calcined mica, the mechanical properties of the composite mica material, the composite mica prepreg material, and the composite mica product, especially the bending strength and flexural modulus, are significantly reduced.

The present invention will be explained below with reference to Examples.

Parts are parts by weight.

Example 1 Table 2 Table 3 Table 3 of aggregate mica material 1 described in Table 2 heated to 60 qo
Composition 1 described above was coated 10 times a day, and a glass cloth (3-years-old) was laminated as a backing material, and heated at 80 qC for 1 hour to semi-cure to obtain a laminated mica prepreg material.

After cutting this into 3 enemy width tape, 9.5 fence x 3
6.5 Wrap it around a conductor (made of copper) with a thickness of 1 inch, half overlapping, 8 times, heat it to 10,000 degrees Celsius, press it, and raise the temperature to 170 degrees Celsius while flowing the adhesive 1 in the laminated mica prepreg material. This was cured (for 3 hours) to form an insulating layer with a thickness of 3 ribs, and a coil was obtained. Four coils were manufactured, two were tested under normal conditions, and two were tested after thermal deterioration. The bending strength of this coil is determined by the 4-point method (outer span: 55 mm, inner span: 250 mm).
The dielectric breakdown test was performed at a voltage increase rate of V/sec. In addition, after heat deterioration at 130 qo for 100 hours, the dielectric breakdown voltage was measured.

The results are shown in Table 4 as average values.

Example 2 The same adhesive, rainbow skin, and bag material as in Example 1 were applied to Material 2 listed in Table 2 under the same conditions as in Example 1, and the materials were bonded together and further semi-cured to obtain a laminated mica prepreg material. .

This was used to make a coil by the method described in Example 1, and the characteristics of the coil were evaluated. Comparative Example 1 The same adhesive and the same hair batting material as in Example 1 were applied to Material 3 shown in Table 2 under the same conditions as in Example 1, the materials were bonded together, and further heated and semi-cured to obtain a laminated mica prepreg material. .

Using this, make a coil by the method described in Example 1,
The characteristics of the coil were evaluated. The results are shown in Table 4 as average values.

Comparative Example 2 The same adhesive and the same hair batting material as in Example 1 were applied to Material 5 shown in Table 2 under the same conditions as in Example 1, the materials were bonded together, and further semi-cured to obtain a laminated mica prepreg material.

This was used to make a coil by the method described in Example 1, and the characteristics of the coil were evaluated. The results are shown in Table 4 as average values. Table 4 Example 3 Adhesive 2 listed in Table 3 was added to Material 1 listed in Table 2 for 17 minutes (
Non-volatile content: 1% by weight) was applied and dried at 8,000 for 30 minutes to obtain a semi-cured prepreg Mica sheet.

Layer 8 of these mica sheets, use a press heated to 150℃, and heat at 20℃ for 20 minutes at a pressure of 9F/ground, then raise the temperature to 200℃ while keeping the pressure constant, and heat and press for 2 hours to produce a heat-resistant mica product. I got it. The bending strength of this heat-resistant mica product (3-point method, span 5 enemies, test speed 1 rib/min), 500
After heating for q02 hours, the test piece was cut into a 60 x 14 piece, and a nichrome wire (13.20/m) was wrapped 17 times at AC 115-120V for 3. Table 5 shows the results of examining the smoke generation property by applying a current of 5 minutes. Example 4 Adhesive 2 listed in Table 3 was added to Material 2 listed in Table 2 at 17 points (
(wt % of non-volatile content) was coated and dried at 8000 for 3 minutes to obtain a semi-cured prepreg mica sheet.

This mica sheet was laminated and pressed under the same conditions as in Example 3 to obtain a heat-resistant mica product. Characteristics were evaluated under the same conditions as in Example 3 and are shown in Table 5. Comparative Example 3 Material 4 listed in Table 2
Adhesive 2 listed in Table 3 was coated to 1 form/final (non-volatile content 1% by weight) and dried at 80 oo for 30 minutes to obtain a semi-cured prepreg mica sheet.

This mica sheet was laminated and pressed under the same conditions as in Example 3 to obtain a heat-resistant mica product. Characteristics were evaluated under the same conditions as in Example 3 and are shown in Table 5. Ratio comparison example 4 Add 247 g of adhesive 2 listed in Table 3 to material 5 listed in Table 2 ((non-volatile content 1
% by weight) and dried at 80 qo for 3 minutes to form a semi-cured prepreg mica sheet.

This mica sheet was laminated under the same conditions as in Example 3, and then pressed to obtain a heat-resistant mica product. Characteristics were evaluated under the same conditions as in Example 3 and are shown in Table 5. Table 5 Example 5 Glass cloth (35g/) is layered on material 1 listed in Table 2 as a diamond-shaped material, and adhesive 3 listed in Table 3 is applied on top of the material 1 listed in Table 2.
Wa ((non-volatile content 20% by weight) coated, 30% at 100qo
After drying for a minute and cutting into 30-foot-wide tapes, 9.5
Sails x 36.5 length 1. After wrapping the conductor (copper) 8 times with half overlap, it was heated to 0.1 skin H at 100℃.
It was degassed for 2 hours and then impregnated with adhesive 1 according to Table 3, which had been heated to 8000 g in vacuum.

With the coil immersed in the adhesive, return the pressure to normal pressure, and
After some time, take out the coil and wrap it with 2 mil Mylar film (made by Toray) to prevent the adhesive 1 from dripping.
Cured at 000 for 4 hours and then at 20,000 for 1 hour.
An insulating layer with a foot-thickness was formed. Four coils were manufactured, two were tested under normal conditions, and two were tested after thermal deterioration. The characteristics of the coil were evaluated under the same conditions as in Example 1. The results are shown in Table 6 as average values. Example 6 Material 2 listed in Table 2 was made into a laminated mica tape under the same conditions as in Example 5, and into a coil under the same conditions as in Example 5. The characteristics of the coil were evaluated under the same conditions as in Example 1.
The results are shown in Table 6 as average values. Comparative Example 5 Material 3 listed in Table 2 was made into a laminated mica tape under the same conditions as in Example 5, and into a coil under the same conditions as in Example 5.

Characteristic evaluation of the coil was conducted under the same conditions as in Example 1, and the results are shown in Table 6 as average values. Comparative Example 6 Material 5 listed in Table 2 was made into a laminated mica tape under the same conditions as in Example 5, and into a coil under the same conditions as in Example 5.

The characteristics of the coil were evaluated under the same conditions as in Example 1, and the results are shown in Table 6 as average values. Table 6 Example 7 Material 1 listed in Table 2 and Adhesive 4 listed in Table 3 were applied 24 times per coat, dried at 120°C for 5 minutes, and then three semi-cured laminated mica sheets were laminated. 300q0100k9
A mica laminate having a thickness of 0.3 ribs was obtained by heating and pressing for 1 hour under the conditions of f/ground.

Table 7 shows the properties of the obtained mica laminate. Example
8. Adhesive 4 shown in Table 3 was coated at 247 g/last on Material 2 shown in Table 2, and a mica laminate was prepared under the same conditions as Example 7.

Table 7 shows the properties of the obtained mica laminate. Comparative example
7 Materials listed in Table 2 3 Adhesives 4 listed in Table 3 were coated at 247 g/l to produce a mica laminate under the same conditions as in Example 7.

Table 7 shows the properties of the obtained mica laminate. Comparative example
8. Adhesive 4 shown in Table 3 was applied 27 coats/coating to Material 5 shown in Table 2 under the same conditions as Example 7 to obtain a mica laminate.

The properties of the falsified mica laminate are shown in Table 7. Table ``' *1 3-point method, span 5 ships, test speed 1 sail/min *2
Measurement after immersion in boiling water for 20 minutes As described in detail in the examples above, the laminated mica material of the present invention uses mica flakes with a large aspect ratio, so no adhesive is used. The strength of the sheet is so strong that it can be rolled up even when it is used, and the laminated mica prepreg material manufactured by processing this sheet also has improved mechanical properties because it uses mica prepreg pieces with a large particle size. Electrical properties can also be improved by filling the gaps between large mica particles with small-sized mica particles to achieve close packing.

Claims (1)

[Claims] 1. Mica flakes with a particle size of 1.0 mm or more and an aspect ratio of 150 or more obtained by crushing uncalcined mica.
0 to 70 parts by weight, 20 to 40 parts by weight of mica lime pieces with a particle size of 0.25 mm or more and less than 1.0 mm, and a particle size of 0.25 mm.
A laminated mica material obtained by paper-making a slurry containing 10 to 30 parts by weight of mica flakes. 2. The laminated mica material according to claim 1, which is formed by adhering the backing material and a thermosetting resin composition. 3 Mica flakes with a particle size of 1.0 mm or more and an aspect ratio of 150 or more obtained by crushing unfired mica are 3
0 to 70 parts by weight, 20 to 40 parts by weight of mica lime pieces with particle size of 0.25 mm or more and less than 1.0 mm, particle size of 0.25 m
A composite mica material obtained by paper-making a slurry containing 10 to 30 parts by weight of mica scale pieces of less than Laminated mica prepreg material. 4 Mica flakes with a particle size of 1.0 mm or more and an aspect ratio of 150 or more obtained by crushing unfired mica are 3
0 to 70 parts by weight, 20 to 40 parts by weight of mica lime pieces with a particle size of 0.25 mm or more and less than 1.0 mm, and a particle size of 0.25 mm.
After impregnating or coating a thermosetting resin composition or an inorganic composition into a composite mica material obtained by paper-making a slurry containing 10 to 40 parts by weight of mica flakes of less than A laminated mica product.