JPS5846207B2 - Heat-resistant unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a heat-resistant unsaturated polyester resin composition, more specifically, it has excellent heat resistance and insulation properties, and is suitable for coil impregnation, casting, molding compound, right front use, etc. This invention relates to an unsaturated polyester resin composition.

Recently, there has been a strong demand for electrical equipment to be smaller, lighter, and more reliable.

As a result, it is desired more than ever to improve the heat resistance of insulating materials used in these electrical devices.

On the other hand, in order to improve the heat-resistant lifespan of electrical equipment, it is generally necessary to not only improve the heat resistance of the insulating material, for example, its electrical and mechanical properties after heating deterioration, but also to improve its thermal shock resistance during cooling and heating cycles. It is desirable that the insulating materials have excellent moisture resistance and moisture resistance, and it is also important that the various insulating materials have excellent mutual compatibility.

The present inventors have developed a dicyclopentadienyl monomaleate-based unsaturated polyester (abbreviated as D-based UP) that was previously invented in Japanese Patent No. 586518.

) resin has self-copolymerizability and has excellent heat resistance, electrical properties, adhesive strength, etc. However, it was later discovered that the cured product of this D-based UP was hard, brittle, and had poor crack resistance. It turns out there are drawbacks.

However, as a result of investigation, we were able to improve crack resistance by imparting flexibility to D-based UP without impairing its heat resistance by making it compatible with acrylonitrile-butadiene copolymer. .

As the acrylonitrile-butadiene copolymer, for example, Ube Industries' CTBNI 300X15.

1300X8, 1300X13, Idemitsu Petrochemical ■CN-
15 etc. can be used.

The ratio of its use can vary widely depending on the application, but from the viewpoint of curability, crack resistance, and physical properties of the cured product, D-based UP100
It can be used in a range of 20 to 200 parts by weight.

On the other hand, D-based UP refers to dicyclopentadienyl monomaleate obtained from dicyclopentadiene and maleic acid or hydroxylated dicyclopentadiene and maleic anhydride, and polyhydric alcohol, or polyhydric alcohol as necessary. It refers to unsaturated polyester obtained by reacting it with a basic acid, but also includes a resin solution obtained by dissolving it in a crosslinking monomer, if necessary.

These D-based UPs have superior compatibility with acrylonitrile-butadiene copolymer when compared with general unsaturated polyesters, but by using both together, the features of the UPs described above can be achieved. It is possible to impart the flexibility of polybutadiene resin without impairing heat resistance.

The acrylonitrile-butadiene copolymer is preferably used in an amount of 25 to 450 parts by weight, more preferably 60 to 250 parts by weight, based on 100 parts by weight of D-based UP.

D-based UP varnish (D-based UP and crosslinking monomer) 10
It is preferable to use 20 to 300 parts by weight of the acrylonitrile-butadiene copolymer with respect to 0 parts by weight, and 50 to 300 parts by weight.
It is more preferable to use 200 parts by weight.

In addition, the resin composition of the present invention can be used even when the resin alone is H type (
It can be used for impregnating, casting, and forming the right front of electrical equipment with a normal operating temperature of 180°C (40,000 hours) or more, but if necessary, it can also be used with inorganic brightening agents such as silica, alumina, and calcium carbonate, as well as glass, asbestos, and carbon. Fibrous photonic agents such as phenol fibers can also be used for compounds and molding.

On the other hand, since D-based UP is originally a self-copolymerizable resin, it can be made three-dimensional and hardened by using a radical polymerization catalyst as a hardening agent, especially without using a crosslinking monomer. However, in order to lower the viscosity, adjust flowability, hardenability, and other properties, a crosslinkable monomer can be used in combination.

This crosslinking monomer includes commonly used styrene,
Vinyltoluene, divinylbenzene, diallyl phthalate, various methacrylic acid esters, α-methylstyrene and other copolymerizable monomers can also be used.

Its usage ratio is 0 to 1 per 100 parts by weight of D-based UP.
The 00 weight portion is relatively balanced, but more can be added if lower viscosity is desired.

Examples of curing agents include acyl peroxides such as benzoyl peroxide and acetyl peroxide, hydroperoxides such as tertiary-butyl peroxide and cumene hydroperoxide, methyl ethyl ketone peroxide, ditertiary-butyl peroxide, dicumyl peroxide, etc. Oxyperoxides such as alkyl peroxides, tertiary-butyl perbenzoate, and tertiary-butyl peroxyacetate can be used.

The addition ratio of the curing agent is 0 to 100 parts by weight of D-based UP.
．． It can be used in a proportion of 2 to 3.0 parts by weight, preferably in a range of 0.5 to 2.0 parts by weight.

As the curing accelerator, commonly used metal salts such as naphthenic acid and cobalt octenoate, manganese, lead, iron, etc. can be used.
It is used in an amount of 0 to 2 parts by weight, preferably 0.2 to 1.0 parts by weight.

As the polymerization inhibitor, quinones and phenol compounds such as hydroquinone, benzoquinone, and catechol, which are used in general unsaturated polyester resins, can be used.

Example 1 300 g (2.0 mol) of hydroxylated dicyclopentadiene and 196 g of maleic anhydride in an 11-fish flask.
(2.0 mol) and 0.06 g of hydroquinone,
After reaction at 120℃ for 3 hours under nitrogen gas flow, acid value 226
Dicyclopentadienyl monomaleate was obtained.

Thereafter, 79.8 g (1.05 mol) of propylene glycol was added and reacted at 180 to 220°C for about 10 hours to obtain a viscous polyester (1) with an acid value of 18.5.

Styrene monomer io to 400g of this polyester (I)
og was added and mixed uniformly to obtain varnish (I).

Example 2 Using the same synthesis apparatus as in Example 1, 264 g (2.0 mol) of dicyclopenc diene and 232.9 g (2.0 mol) of maleic acid were synthesized.
,0 mol), 0.06 g of hydroquinone at 110-13
Dicyclopentadienyl monomaleate having an acid value of 226 was obtained in 4 hours at 0°C.

Then, neopentyl glycol 96.6.9 (1,0
5 mol) was added and reacted at 180 to 220°C for about 10 hours to obtain polyester (kawa) with an acid value of 20.5.

Diallyl phthalate 1509 was added to 350 g of this polyester (kawa) and mixed uniformly to obtain varnish (1).

Regarding the varnishes (1) and (If) obtained as above, the blending of the acrylonitrile (IJ) lubutadiene polymer was changed and typical characteristics were tested.

The results are shown in Table 1.

The heat-resistant temperature is 4, which was tested according to the IEEE57 method.
Estimated temperatures for 0,000 hours are shown, and the enameled wire used was a commercially available standard wire of type-H finished polyamideimide (upper layer) and type-H esterimide (lower layer).

From the results in Table 1, it can be seen that 10
It can be seen that crack resistance can be improved by using 20 to 200 parts by weight of the acrylonitrile-butadiene copolymer relative to 0 parts by weight.

In addition, acrylonitrile-butadiene copolymer is 200%
When the weight part is increased, the heat loss and crank resistance are slightly improved, but (1) the shear adhesive strength is significantly reduced;
(2) gelation time becomes slower and (3) volume resistivity gradually decreases.

From the above results, when the acrylonitrile-butadiene copolymer is used in an amount of 50 to 100 parts by weight per 100 parts by weight of varnish (I) or (II), the balance between mechanical properties, electrical properties, heat resistance, and crack resistance is achieved. You can see that it is removed.

Further, as is clear from Table 1, the heat resistance temperature for 40,000 hours is improved to more than iso° C. when acrylonitrile-butadiene copolymer is used in combination.

Claims (1)

[Scope of Claims] 1 (1) dicyclopentadienyl monomaleate-based unsaturated polyester, (2) acrylonitrile-butadiene copolymer, (3) a curing agent and, if necessary, (4) a curing accelerator. A heat-resistant unsaturated polyester resin composition comprising: 2. The heat-resistant unsaturated polyester resin composition according to claim 1, which contains a crosslinkable monomer. 3. The heat-resistant unsaturated polyester resin composition according to claim 1 or 2, which is reinforced with silica powder, aluminum powder, calcium carbonate, glass fiber, phenol fiber, carbon fiber, asbestos fiber, or the like.