JPS6172016A - Thermosetting resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] Non-exploitable BA relates to thermosetting resin compositions. For more information,
:Can be used as a material for electronic parts such as file parts, and can be used as an insulation casting impregnation material with excellent impregnation properties and heat resistance in addition to thermal shock resistance, adhesion, dielectric properties, and flame retardance. The present invention relates to thermosetting resin compositions that can be used.

[Background of the invention]

Conventionally, 1,4-polygetadiene-based resins have been used as mg products for insulation casting impregnation of electronic parts such as high-voltage coil parts, for example, resin compositions for flyback transformers for televisions (hereinafter abbreviated as "n"). Tsuretan is used.That is.

This is because this resin has excellent heat-shock resistance, row contact properties, and dielectric properties. The reactivity of this resin can be controlled by combining it with an isocyanate represented by the chemical formula below, and it is also possible to obtain an excellent impregnating property between the coils.

By combining aluminum hydroxide and red phosphorus, a product with excellent flammability can be obtained.

OCN+4'77t+40H-NCO C-O+C group+RNCO However, this type of resin has insufficient heat resistance, and FB
When applied to T, etc., leave it at high temperature (for example, 100° to 1
Thermal deterioration may be observed after 20°C and 100oA3. In such cases, flexibility is lost, so heat shock resistance is required! The abrasion properties were lowered, and cracks were generated in the heat shock test after thermal deterioration, which could lead to dielectric breakdown, resulting in problems with the reliability of the product.

[@Ming's purpose]

The purpose of the present invention is to solve the above-mentioned problems of the prior art,
The cured resin composition has excellent thermal shock resistance, and also has good adhesion between the cured product and the components of the demon part such as FETs using it.

And vj1! It is an object of the present invention to provide a thermosetting resin composition which has good L properties, flame retardancy, impregnation of liquid resin between coils, etc., and has excellent heat resistance.

[Essentials of the invention]

The above purpose is to combine a flexible polyol represented by the following chemical formula (1) and an isocyanate represented by the following chemical formula (2J), to form a polyol that is HO+CH, -C1l, f-5CH, -Cf, OH-<
1) R' (However, R and R' are an alkyl group having 1 to 3 carbon atoms.

The ratio of m and le is r1/F&=1 to 4 @) OCR+c
M, S, CM-NCO C-0-f CH, +rNCO-+21 This is achieved by further blending surface-treated aluminum hydroxide powder and red phosphorus powder as an aromatic viscosity reducer and flame retardant.

The present invention is preferably implemented in the following manner. That is.

(α1 Copolymer of ethylene and α,α di-substituted olefin represented by the following chemical formula (1) with a molecular weight of 200 to 000 and having hydroxyl groups at both ends of the molecule...100 parts by weight HO + cH, -CB, power r0 scraps -C9OH・+1)R' [However, in formula 1, R and R' are methyl<CHs)-ethyl (
Indicates the q group, in7a pyl (CH(礪), ) group.

The ratio between swear and le shall be 1,000 to 4. ]iAl
Iso-cyanate OCN + can CH-NCO C-0+ CB, ±NCO-(27) shown by the chemical formula (21). (This is a child selected to fall within the range of the 3L formula.

(C) Aromatic cinnabar oil with boiling point of 300°C or higher and viscosity at 25°C of 50 poise or lower...50-100
Parts by weight (di sodium chloride (#at α25 wt
% or less.

The adhering moisture is α2wt% or less of water-based aluminum S powder surface treated with disilane in r-methacrylic acid xyglopyltrimet - 30 to 160 parts by weight (-) Red phosphorus powder 10 to 50] [[From i It is desirable that the ingredients are mixed in a certain ratio.

Next, we will explain the materials that can be used in the present invention. A copolymer of ethylene and α,α didirectly converted olefin, which is a polyol, has a molecular weight of 1 or 200 to 000, has hydroxyl groups on both end layers of the molecule, and has the following chemical formula (1 ) are valid.

However, in formula 1, R and R' are methyl (CHs)-ethyl (
Qhs)-isoya pill (CHCCHs)*)
The basic one is valid. If either R or R' is a hydrogen atom, heat resistance is insufficient due to the presence of tertiary carbon, and the viscosity of the resin increases, resulting in poor impregnation properties.

It was. If either R or R' is a long group longer than butyl (group '4), the heat resistance will decrease.
A ratio of n÷1 to 4 is preferable; if it is smaller than 1, the heat resistance of the resin will decrease, and if it is larger than 4, the viscosity will be high and the impregnating property will be rapid. .

The isocyanate represented by the following chemical formula (2) has a slow reaction rate of 21 degrees and is poor in impregnating properties.

The blending amount is 1YCO in the isocyanate represented by the chemical formula (2J) per 1lC of active hydrogen in the above polymer.
It is desirable to blend an appropriate amount of 1L6 to t3 from the viewpoint of property saturation. If the amount of qh is less than α6 equivalent, there will be problems with thermal shock resistance, i-layer properties, 1-layer property, etc. due to the hardening non-light content, and if it is more than 13 equivalents, the reaction will be questionable and the impregnating property will deteriorate.

It is effective as a viscosity reducing agent because it is an aromatic V-based oil with a boiling point of 300℃ or higher and a viscosity of 50 poise or lower at 25℃. 1 Isol 5AS-LH, etc. The blend t is 30 to 100 parts by weight based on the polyol 101001k, and if it is less than 30 parts by weight, the effect of reducing viscosity is small;
Impregnation between the coils becomes opaque, and if the amount exceeds 100 JU Dobe, thermal shock resistance, adhesion, mechanical properties, flame retardance, and dielectric properties deteriorate.

As water year 1 hyaluminum powder, Al2 false 5B
, 07z. In particular, from the viewpoint of dielectric properties after moisture absorption, sodium acid (NatO) content is less than α23wt%, and the layer moisture is less than α2wt-t, r-methacryloxy. Surface treated with propyltrimethoxysilane is effective. For example, there is a product that has been surface-treated with the above-mentioned straining agent on Showa@Kinzoku (Hijirai) H-521. This stuff is effective against burning.

The blending amount of this surface-treated water-tested aluminum is preferably 30 to 160 parts by weight based on the base of the polyol 100.
If it is more than 0Xshato, it is d electric rate.

In addition to deteriorating the dielectric loss tangent, coil impregnation and workability decreased due to increased viscosity. The average particle size of monosialuminum hydroxide powder is preferably 2 to 35 tun. .

Red phosphorus powder is effective for giving a can stick, but it is especially effective in the above 1) when used in combination with water molten aluminum powder. shows. By checking the red @, you can adjust the amount of water-converted aluminum to the specified amount with low electricity.

(It is possible to impart flame retardancy without reducing the dielectric constant and dielectric constant of the carbon.) The blending amount is 100% of the above polyol.
1) If the amount of iox is less than 0 to 50%, the flame retardant effect will be less. The viscosity caused the impregnation of the coil to deteriorate, and the resin only became more expensive. The average particle size of the red phosphorus powder is preferably 1 to 150 μm. Also, it is better to use a surface treated with phenol resin or the like. others.

Furthermore, if necessary, other inorganic fillers,
A silane coupling agent, an antifoaming agent, a coloring agent, etc. can be added.

[Embodiments of the invention]

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

A method for measuring each property of the resin will be explained, and then some examples will be explained along with comparative examples.

I will first describe the measurement method.

(1) Thermal shock resistance of cured resin product: A mild steel C-shaped washer is embedded in a resin composition to make a test piece, and this test piece is cycled for one cycle starting from a constant upper limit temperature of 100°C and a lower limit temperature of 40°C. A heat shock test was conducted while lowering the temperature by 10°C for each test piece, and the temperature at which cracks occurred in the test piece was determined for 10 test pieces, and the average value was taken as the temperature at which 2 cracks occurred.

Shown as thermal shock resistance. In other words, the lower the temperature, the better the thermal shock resistance of the resin.

Adhesion: Adhesion summary between polyglylene terephthalate convex contact test pieces (covered area i cm”) 50
The resin composition is applied to a thickness of μm.

It was heat-cured and made into a sample piece. The measured value after the tensile test is 2
It was determined at 5°C and is shown as the average value of 10 values.

(2) Molding characteristics after moisture absorption: The sample was boiled in ion-exchanged water at three thresholds, left in the air at 25°C for 1 hour, and JIS 6
9n at 25°C and 1) 1 KHz. In addition, the measured values are the average value of three values, and the dielectric constant is 4.
Hereinafter, those with a dielectric loss tangent of 3% or less are referred to as "O", and the others are referred to as rXJ. “○” means pass, and “×” means fail.

m Flame retardancy: Determined using a 1/16 inch thick test piece according to the UL94 standard. Those that pass UL94V-0 are designated as -V-OJ, and those that fail are designated as "combustion". Impregnability: The ti property of the resin between the coil windings is as follows: The coil winding machine section was cut and the cross section was observed under a microscope at a magnification of about 50 times, and the ratio of the resin impregnated into the coil-coil bar to the coil open area/area was investigated.

〇 (v1) IN fever with 95% or more passing: 120℃/1c 1 after 100OA
After 200 cycles at 00°C/2A to -50°C/2A, the operating characteristics were examined, the first winding was cut, and the presence or absence of cracks was examined. Those with no cracks and good operating characteristics were marked as "○" to pass, and the others were marked as "x" and failed. All resin curing conditions are 60℃ 75 hours ±
The temperature was set at 100℃/2mm.

Next, an example will be described.

Example 1 Table 1 shows Examples 41-1). In each example, as shown in the lower column of the table, as a polymer that is a polyol, the above (1)
A compound with a molecular weight of about 1500, in which R and R' in the formula were methyl groups and Vl was 2, was used. The isocyanate is a substance of Formula 21, and the actual percentage of each compound is shown in the table.In the comparative example, 1.
For comparison, 4-boriatadiene glycol or aluminum hydroxide without surface treatment was used. The ratio of compounding storage is also shown in the first column.

(Left below) Implementation layers 1 to 1) and comparative layer 1 shown in Table 1
The crack initiation temperature, adhesion,
Dielectric properties after moisture absorption, flame retardancy.

When impregnation and heat resistance were measured, I! The results shown in 2 tables were obtained. Casting resin for FBT cannot be used unless its crack generation temperature is lower than 150°C. Regarding this point, Examples/1t1 to 1) are lower than -70℃, and comparative examples are also lower than -70℃, with the exception of 44, and the thermal shock resistance is satisfactory. Example 4 has poor thermal shock resistance.In terms of adhesion, it is possible to implement 1.
~1) is higher than 50kp/c-, and 50ψ is higher than the comparative example except for shoulder 4, which is satisfactory. However, Comparative Example 44, in which the viscosity reducing agent was added in an excessive amount, had insufficient adhesion. From the perspective of dielectric properties after moisture absorption of the resin, the interlocking shoulders 1 to 1
) is satisfactory, and the comparative example is satisfactory except for the 44j shoulder of 6.49. However, Comparative Example 44 with an excessive amount of viscosity reducing agent, Comparative Layer 6 with excessive aluminum hydroxide powder, and Comparative Layer 9 with aluminum hydroxide powder other than the present invention.
Both have poor dielectric properties after moisture absorption.

Flame retardancy is also an important characteristic of FETK.

Only resins that pass UL94V-OKm can be used. Comparative inversion 4 with excessive viscosity reducing agent content
．． Comparative example with low aluminum hydroxide content/W-5. Red phosphorus blend Red phosphorus blend - Comparative layer 7 both failed in terms of flame retardancy.

However, both Examples and other comparative examples satisfied the flammability.

From the point of view of impregnating properties, 1. Comparative examples using isocyanates other than those of the present invention; 2. Comparative example 3 with a small amount of viscosity reducing agent. Comparison of excessive amount of aluminum hydroxide 6.
Comparative Layer 8 with an excessive amount of red phosphorus was rejected. but.

The 6 non-inventive examples and the other comparative examples had good impregnating properties. Note that FBT also requires X life characteristics, and in terms of heat resistance, 1.4-polygetadiene glycol was used. Comparative example genus 1 was rejected.

Both Examples and Comparative Examples other than 1) used the polyol of the present invention and passed the test.

Resin compositions that can satisfy all of the above characteristics are those of practical layers 1 to 1).

Example 2 10rILd! In the vacuum container, a primary bobbin 2.a secondary bobbin 3.as shown in the attached drawings are installed. A FET containing a diode 4°, a primary coil 5, a secondary coil 6, a focus resistor 7, and a capacitor 8 housed in a case 9 was placed, and the following examples were prepared as shown in Table 1, Examples A1 to 1). Comparative Examples A1 to 9 The resin compositions shown in Fc were poured and cured under the curing conditions of f and Pfr, which were returned to normal pressure. The drawing shows a cross-sectional view of FBT after casting. In the figure, 1 is a cast resin. As a result, Comparative Example A2
．． FBT using 3.6.8 has poor impregnability into the darkness (, a dielectric breakdown occurred in a poem. Comparative circuit layer 4 was used)
B T kZ , 100'C/2A To-50'
After 20 cycles of C/2A cooling and heating cycles, cracks appeared near the secondary bobbin, and dielectric breakdown occurred in the jI21 production test.

FBTs using 4 and 5.7 in the ratio 42 direction] failed in the combustion test according to the electric charge method.

In addition, the dielectric properties of the resins of FBTs using comparative fJ genus 4 and 6.9 deteriorated significantly after the moisture absorption test.

The performance of FBT was significantly degraded. Comparative Example/FHT using I61 deteriorated in operating characteristics after the heat resistance life test, and failed at #A.

10,000, FBTK using the resin composition of Table 1 Example/61-1): No abnormalities were observed.

[Effect of enlightenment]

As described above, the heat-stimulating resin composition according to the present invention has excellent heat impact resistance of the cured resin composition,
Not only are the brocade properties and flammability significantly improved, but the impregnability of the liquid resin between the layers and the heat resistance of the resin compound have also been improved.

For example, % better FBT when using FBT(/cA)
is the dielectric strength characteristic, dielectric strength! properties, flame retardancy and reliability. Therefore, Koto's value 1) N is large.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments specifically described above.

[Brief explanation of drawings]

The drawing is a sectional view of a flyback transformer using a thermosetting resin composition according to an example of the present invention as a resin for insulation casting and impregnation. 1.- Casting reciprocating part 2-. Primary bobbin 3... Secondary bobbin 4... Diode 5... Primary coil
6...Second; Il 7...Focus i anti 8.
- Capacitor 9...Case substitute, AJf Shioshi Akio Takagi

Claims (1)

[Claims] 1. A polyol represented by the following chemical formula (1) and an isocyanate represented by the following chemical formula (2) are combined, ▲There are numerical formulas, chemical formulas, tables, etc.▼...(1) [ However, in the formula, R and R^1 represent an alkyl group having 1 to 3 carbon atoms, and the ratio of m and n is m/n=1 to 4. 〕 ▲Contains mathematical formulas, chemical formulas, tables, etc.▼…(2) A thermosetting product made by blending an aromatic viscosity reducing agent, surface-treated aluminum hydroxide powder as a flame retardant, and red phosphorus powder. Resin composition. 2. A thermosetting resin composition according to claim 1, which comprises the following substances (a) to (e) in the proportions described below. (a) It is represented by the chemical formula (1) above, and R and R^1 in the formula are methyl (CH_3), ethyl (C_2H
_3), a polyol that is a copolymer of ethylene and α,α di-substituted olefin, which has an isoprobyl (CH(CH_3)_2) group, has a molecular weight of 200 to 3,000, and has hydroxyl groups at both ends of the molecule: 100 Weight part. (b) The amount of the isocyanate represented by the above chemical formula (2) is selected so that the blending ratio of the copolymer of the above (a) and the isocyanate of the above (b) falls within the range of the following formula (3) in terms of equivalent ratio. . Active hydrogen groups in copolymers/NCO in isocyanates
Group = 1/0.5 to 3 (3) (c) Aromatic oil having a boiling point of 300°C or higher and a viscosity of 50 poise or lower at 25°C: 30 to 100 parts by weight. (d) Sodium oxide (Na_2O) is 0.23wt%
In the following, aluminum hydroxide powder with adhering moisture of 0.2 wt% or less was surface-treated with γ-methacryloxypropyltrimethoxysilane: 30 to 160 parts by weight. (e) Red phosphorus powder: 10 to 50 parts by weight.