JPS60208008A - Electrically insulating material - 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 The present invention relates to a photocurable electrical insulating material that is cured by ultraviolet rays, electron beams, etc.

Electrical short-edge materials are widely used in fields such as light and strong electrical appliances, home appliances, and communications.Recently, as electronic components become smaller and more highly integrated, the demand for materials with higher performance has increased. .

In other words, in addition to electrical properties such as insulation, it is required to have excellent mechanical strength, heat resistance, oil resistance, moisture resistance, water resistance, etc. Especially as an insulating material for electronic components. In order to protect devices from external environments such as water and humidity, there is an increasing demand for water resistance and moisture resistance.

On the other hand, instead of the heat curing method that consumes a large amount of energy or the room temperature curing method that requires a long drying time, a photocuring method that cures in a short time by irradiating it with light such as ultraviolet rays or electron beams has recently been introduced. Electrical insulating materials are attracting attention. However, epoxy acrylate, polyurethane acrylate, and
Materials such as polyester acrylate-based materials generally have poor water resistance and moisture resistance, and cannot necessarily be said to be sufficient as electrical insulating materials. Furthermore, these photocurable resins are often used in combination with a photocurable diluent for viscosity adjustment, but in such cases the above-mentioned drawbacks are further aggravated.

Therefore, the present inventors conducted intensive studies to improve such drawbacks of the conventional technology, and as a result, the inventors of the present invention developed a method using a known photocurable component.
Conventionally, it was known as an ω material for resin molded products and a photocurable component for printing ink (Japanese Patent Application Laid-Open No. 56-2357,
No. 57-164163) It was discovered that tricyclodecane dimethylol-based materials have particularly excellent performance, and the present invention was completed.

Thus, according to the present invention, there is provided a photocurable electrical insulating material characterized by containing tricyclodecane dimethylols and a diester of α,β-unsaturated carpinic acid as a photocurable component.

The above tricyclodecane dimethylols are obtained by oxo reaction of dicyclointadiene or its lower alkyl substituted product, and specifically, 3,8-bis(
hydroxymethyl)tricycloCFl, 2.1.0”6
] decane, 4,9-bis(hydroxymethyl)tricyclo[5,2,1,02·6]decane, and the like.

On the other hand, the above α,β-unsaturated Cal? Specific examples of phosphoric acids include acrylic acid, methacrylic acid, and crotonic acid, but acrylic acid is most preferred in terms of curing speed.

The tricyclodecane dimethylol diester used in the present invention can be synthesized according to conventional methods. For example, α, β- for the hydroxyl group of tricyclodecanedimethylol
Unsaturated Cal? Using 1 to 3 times the molar amount of sulfuric acid, p-
80~ in the presence of an acid catalyst such as toluenesulfonic acid etc.
At a reaction temperature of 120°C, hydroquinone, if necessary,
It can be easily obtained by reacting with the addition of a polymerization inhibitor such as hydroquinone monomethyl ether.

In the present invention, such tricyclodecane dimethylol diester is used as a photocurable component of an electrically insulating material. When used, such tricyclodecane dimethylol diester may be used alone or in combination with other commonly used photocurable resins. Specific examples of photocurable resins that can be used in combination include acrylate-modified and methacrylate-modified products based on epoxy resin, I-urethane, polyester, silicone resin, I-liptadiene, alkyd resin, phenol resin, petroleum resin, etc. is exemplified. Although the ratio of the combined use can be selected as appropriate, it is appropriate that tricyclodecane dimethylol diester be used in an amount of usually 10% by weight or more, preferably 15% by weight, based on the total curable components.

Since the tricyclodecane dimethylol diester used in the present invention has an extremely low viscosity, it does not necessarily require other photocurable diluents; If necessary, a commonly used photocurable diluent can be added to the diluent, such as methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate,
Tricyclodecane monomethylol acrylate, 1.4
-butanediol diacrylate, 1,6-hexaneol diacrylate, neointyl glycol diacrylate, zv ethylene glycol diacrylate, trimethylolpropane triacrylate, interaerythritol triacrylate, diintaerythritol hexaacrylate, these Examples of the compound include methacrylate and N-vinylpyrrolidone. However, even in this case, it is appropriate that the amount of tricyclodecane dimethylol diester be 10% by weight or more, preferably 15% by weight or more based on the total curable components.

In the present invention, a commonly used photopolymerization initiator is blended to promote photocuring by isobaric ultraviolet rays.

Specific examples of such photopolymerization initiators are -ct;j: Example L
if' Hensifhenone, benzoin, benzine methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl, dimethyl ketal, hydroxycyclohexylphenyl ketone, diacetyl, acetophenone, jetoxyacetophenone, anthraquinone, etc. Examples include sulfide compounds such as nyl compounds and diphenyl disulfide, and halodane compounds such as pentachlorobutadiene.
It is usually used in a proportion of 0.1 to 10 parts by weight relative to 0 parts by weight.

Further, if necessary, a photosensitizer can be added. Specific examples thereof include n-butylamine, non-n-ditylamine, triethylamine, 2-dimethylaminoethanol, N-methyljetanolamine, and triethanolamine. For example, other additives such as fillers such as inorganic fillers, pigments, plasticizers, adhesion agents, thermal polymerization initiators, etc. may be added as necessary.

The photocurable electrical insulating material of the present invention is suitable for use in high-density composite products such as ICs, electronic components such as diodes, capacitors, transformers, resistors, switches, motors, generators, electric wires, and other various electrical devices. It can be widely used in resin molded products for equipment, and is particularly suitable as a material for piezoelectric components.

After applying treatments such as coating, impregnating, and casting depending on the intended use, it is cured by irradiation with ultraviolet rays, electron beams, etc.

As a light source for photocuring, an ultraviolet generator such as a high-pressure mercury lamp or a metal halide lamp is usually used, but generators such as electron beams, X-rays, and γ-rays can also be used.

Thus, according to the present invention, economical efficiency and workability are improved due to short curing time and omission of a drying process, as well as excellent water resistance and
It is possible to prevent deterioration of electrical characteristics due to moisture resistance.

Next, the present invention will be explained in more detail with reference to Examples. Note that parts in the examples represent parts by weight.

Example 1 30 parts of tricyclodecane dimethylol diacrylate,
70 parts of bifunctional bisphenol type epoxy acrylate (manufactured by Showa Kobunshi Co., Ltd., 5P-1509), 1-<4-
3 parts of isopropylphenyl)-2-hydroxy-2-methylzolo/4'-1-one (Darocur 1 manufactured by Merck & Co.)
116) to prepare a photocurable electrical insulating material, which is made into a film-like test piece with a film thickness of IWm.

For curing, the material was completely cured by repeated irradiation with a 2 kW high-pressure mercury lamp (2 kW high-pressure mercury lamp) 12000 L/6 (manufactured by Toshiba Electric Materials Corporation) having an intensity of 80 W/crn at a conveyor speed of 6 m/min at an irradiation distance of 10 crn. For comparison, various difunctional diluents were used in place of the above tricyclodecanemethylol diacrylate and cured in the same manner. Table 1 shows the results.

The results in Table 1 show that the electrical insulating material of the present invention is an excellent electrical insulating material with superior water absorption and water resistance, and less deterioration in volume resistivity compared to those using other difunctional diluents. It can be seen that it is.

Example 2 Tricyclodecane dimethylol diacrylate and bifunctional urethane acrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., Aroex M-1200, 200,000 to 300,000 cps/
50°C) in the ratio shown in Table 2, and this mixture 10
0 parts and 3 parts of Darokia 1116 (manufactured by Merck & Co., Ltd.) were blended to prepare an electrical insulating material. Next, a test was conducted in the same manner as in Example 1, and the performance was evaluated. The results are shown in Table 2.

As shown in Table 2, the photocurable electrical insulation material containing tricyclodecane dimethylol diacrylate has excellent water resistance.

Patent applicant: Zeon Corporation

Claims (1)

[Claims] 1. A photocurable electrical insulation material containing tricyclodecane dimethylols and a diester of α,β-unsaturated caldicic acid as a photocurable component.