JPS608355A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving light-weight BMC or SMC without lowering the electrical insulation, by compounding inorganic hollow particles washed with acetic acid. CONSTITUTION:Inorganic hollow particles washed with acetic acid is added to an unsaturated polyester resin composition as a part of the inorganic filler. The concentration of the acetic acid to be used for washing is about 0.5-5N. For example, 100pts.wt. of hollow particles are mixed with >=1pt.wt., practically 10-100pts.wt. of pure acetic acid, and stirred until the pH of the liquid layer becomes constant. The treated hollow particles are washed with water until the electrical conductivity of the washed waste water reaches <=30muOMEGA/cm, when the particles are dried and used as the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to an unsaturated polyester resin composition containing an inorganic filler, and more particularly to a lightweight electrical insulating material composition containing inorganic nitrogen particles.

[Prior art and its problems]

Unsaturated polyester resin, polymerizable monomer, curing catalyst,
A mixture consisting of a mold release agent, filler, reinforcing fibers, colorant, etc. is a so-called bulk molding compound (BM
It is known as C) and sheet molding compound (SMC), and is widely used as an electrical insulating material and a structural material because of its excellent electrical and mechanical properties, moldability, and economic efficiency.

In general, the specific gravity of 13Mc and SMC is about 1.8 to 2.2, and large molded parts using them have a problem in that they are stacked considerably and are very difficult to handle. B.M.
The reason for the high specific gravity of C and SMC is that their essential components are calcium carbonate, aluminum hydroxide, silica powder, mica powder, clay, calcium silicate, paricum sulfate, and other inorganic fillers and a large amount of glass fiber as reinforcing fiber. This is because it is included in

However, in order to obtain various physical properties of BMC and SMC,
These fillers and reinforcing fibers! It is extremely difficult to achieve weight reduction by significantly reducing the weight, and there is a problem in that the amount of resin increases relatively, resulting in a significant increase in cost and a significant loss of economic efficiency.

To date, attempts have been made to reduce the weight of BMC and SMC by reducing the amount of filler by 1 ton, foaming unsaturated polyester resin, and adding light aggregate.

However, reducing the amount of filler necessarily increases the amount of resin, which not only makes it impossible to maintain the physical properties of the molded product as described above, but also poses an economical problem.

Furthermore, when unsaturated polyester resin is foamed using various methods to reduce its weight, the mechanical strength of the molded product itself is significantly reduced, resulting in the problem that the molded product cannot withstand use unless the surface layer is reinforced with a different material.

Furthermore, so-called artificial lightweight aggregates obtained by artificially firing expanded tribute rock, expanded clay, expanded slate, fly ash, etc. as main raw materials, and so-called artificial lightweight aggregates manufactured using raw materials such as alumina, silica, glass, etc. An attempt has also been made to reduce the weight by incorporating a lightweight aggregate called micro hollow bodies (Japanese Patent Application Laid-open No. 53-18647). By blending these artificial lightweight aggregates, a significant weight reduction can be achieved, but since they all contain water-soluble alkaline components, if they are blended in large quantities, the electrical insulation resistance after water absorption will drop significantly, making them unsuitable for use as electrical insulating materials. There was a problem that it could not be used.

[Purpose of the invention]

The present inventors have made intensive studies to obtain an electrically insulating material composition that is improved from the above-mentioned drawbacks. It has been discovered that a lightweight electrical insulating material with good electrical insulation performance can be obtained by blending hollow particles, leading to the present invention.

[Summary of the invention]

That is, the present invention relates to an electrically insulating material composition characterized in that an unsaturated polyester resin composition containing an inorganic filler is blended with inorganic hollow particles in which a portion of the inorganic filler is acid-treated.

The unsaturated polyester resin used in the present invention is
Any resin that is generally used for BMC and SMC may be used, and is not particularly limited. -For example,
An acid component consisting of an α, β-unsaturated dibasic acid, an aliphatic saturated dibasic acid, an aromatic dibasic acid, or an alicyclic dibasic acid if necessary, and a polyhydric alcohol or alkylene oxide.
It is obtained by M condensation reaction.

Examples of α/β-unsaturated dibasic acids used in the production of unsaturated polyesters include maleic acid, hydrothermal maleic acid, fumaric acid, itaconic acid, citraconic acid, and α/β-unsaturated dibasic acids. Examples of the aliphatic saturated dibasic acid used in combination with a basic acid include adipic acid, cepatic acid, and the like.

Examples of aromatic saturated dibasic acids include phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid, and examples of alicyclic dibasic acids include tetraphthalic anhydride and endomethylenetetrahydrophthalic acid. .

In addition, polyhydric alcohols which are one of the components used in the production of unsaturated polyester include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1.3-butanediol, 1.4
-butanediol, 1,5-bentanediol, 16-
Glycols such as hexaneshionoheneobenterglyl, hydrogenated bisphenol A bisphenol A propylene oxide adduct; and triols such as glycerin and trimethylolpropane.
Examples of alkylene oxide include ethylene oxide,
Examples include propylene oxide.

As the inorganic filler used in the present invention, all those used in normal BMC and SMC, such as calcium carbonate, aluminum hydroxide, silica powder, mica powder, clay, barium sulfate, talc, and calcium silicate, can be used.

As the acid-treated inorganic hollow particles used in the present invention, silica microballoons (manufactured by Emerging Antoka Mink Co., Ltd.) are used.
, Shirasu Balloon (Shirasu Co., Ltd.), Fillite (Nippon Fillite), Ceramic Micro Balloon (Emerging and Coming Co., Ltd.), Perlite (Ube Industries), Q
-Cell (Philadelphia Quartz Co.), Glass Microballoon (Emerging & Cumming Co., Ltd.) 1fr: Can be obtained by washing with acetic acid.

The concentration of acetic acid is not limited to a certain degree, but an aqueous solution with an electric current of about 0.5 to 5 N is used, and an example of the treatment mode is as follows.

Put the hollow particles in a container, per 100 parts by weight of the hollow particles,
Add 1 part or more of acetic acid, in fact about 10 to 100 M of acetic acid, and stir. Lower layer (liquid layer) P,) i j
Stir Z until the point where P)I no longer changes.
continue.

When the PR becomes constant, the lower layer is removed, pure water is poured into the container, and the hollow particles are thoroughly washed with water. The amount of mold added to pure water is preferably 10 volumes or more per volume of hollow particles, and washing with water is repeated for 3 to 5 f cycles. The level of water washing is determined by the point at which the electrical conductivity of the washing wastewater becomes 30 μt)/ts or less, and when the electrical conductivity becomes less than this, water is removed to obtain hollow particles used in the present invention.

In addition to the above-mentioned unsaturated polyester resin, inorganic filler, and acid-treated inorganic hollow particles, the electrical bonding composition of the present invention includes styrene monomer, talolstyrene, vinyltoluene, diallyl phthalate, acrylic or methacrylic esters, vinyl acetate, One or more mixed polymerizable monomers such as triallylisocyanurate, penzoylno(-oxyl', t--7' tilperbenzoate,
Curing catalysts such as dicumyl chloride oxide, low shrinkage agents such as polystyrene, polymethyl methacrylate, polyvinyl acetate, styrene-vinyl acetate co-polymer, saturated polyesters consisting of propylene glycol and adipic acid or heptano(tinic acid), etc. BMC generally includes thermoplastic resins, metal stearates, mold release agents such as wax, inorganic and organic colorants, and reinforcing fibers such as glass fibers, asbestos fibers, and organic fibers.

All materials used for SMC can be used, and the amount used is determined by the intended electrical insulating material composition and the performance of the product (molded product), and is not particularly limited.

〔Effect of the invention〕

The electrical insulation performance according to the present invention has excellent electrical insulation performance while being lightweight.

[Embodiments of the invention]

Production of unsaturated polyester resin: 5.5 moles of maleic anhydride, 4.5 moles of isophthalic acid, and 10.3 moles of propylene glycol are used as reaction components, and an esterification reaction is carried out at 120 to 210°C in a gas atmosphere with N to give an acid value of 26. An unsaturated polyester resin was synthesized. Next, this resin was dissolved in styrene monomer to prepare a solution with a resin content of 70% by weight, while hydroquinone Y25'O
ppm was added and blended to prepare an unsaturated positive ester resin solution.

Production of polystyrene solution: 40 layers of polystyrene was dissolved in 60 layers of styrene monomer to prepare a low shrinkage resin solution.

Example 1 Microcell M (A-1) 1 manufactured by Nippon Philite Co., Ltd.
0000 weight 4r: 0.5N acetic acid aqueous solution 2A! So 5
After stirring for a while, the pH stabilized, so the lower layer was discarded and the washing operation was repeated using ion-exchanged water. Since the electrical conductivity of the washing waste liquid became 10 μTJ/cIIL, the washing operation was stopped, and after being separated, it was dehydrated under reduced pressure at 105° C. for 5 hours to obtain dry hollow particles.

An electrical insulating composition having the formulation shown in Table 1 was prepared using the obtained hollow particles, and the molding temperature was 155°C and the molding pressure was 50K.
f/cr1. JIS obtained under molding conditions of 3 minutes molding time
Using a test piece for measuring insulation resistance and a test piece for measuring shrinkage rate based on K-6911 as samples, the insulation resistance and specific gravity after boiling for 2 hours were measured, respectively. The results are shown in Table-1.

Comparative Examples 1 and 2 Hollow particles without acid treatment (Microcell M (A-1)
)) & Samples were prepared in the same manner as in the examples except for the ones used, and the insulation resistance and specific gravity after boiling for 2 hours were measured. The results are shown in Table-1.

Example 2 Acidophilic hollow particles (Microcell M (A) used in Example 1)
Samples were prepared in the same manner as in Example 1 except that -1')) was added in twice the amount of Example 1, and the insulation resistance and specific gravity after boiling for 2 hours were measured. The results are shown in Table-1.

Comparative Example 3 In an example in which no inorganic hollow particles were used, an electrical insulating material composition having the blending ratio shown in Table 1 was obtained.

A test piece for measurement was prepared using this composition 1 in the same manner as in the example, and the insulation resistance and specific gravity after boiling for 2 hours were measured. The results are shown in Table-1.

As is clear from the table, when no 1"-hollow particles are used (Comparative Example 3), the specific gravity is 1.85, whereas when 3% and 6% of 1"-hollow particles are mixed, the specific gravity is 1.59.
1.41, which is significantly smaller and lighter.

In addition, when comparing the presence and absence of acid treatment, when 3% and 6% of hollow particles without acid treatment were added, the insulation resistance decreased significantly, whereas when the hollow particles were mixed with acid treatment according to the present invention, the insulation resistance decreased significantly. Almost no decrease was observed in the insulation resistance of the electrical insulation composition, indicating that weight reduction was achieved while sufficient electrical insulation performance was maintained.

Below margin

Claims (1)

[Claims] In an unsaturated polyester resin composition containing an inorganic filler, a part of the inorganic filler and