JPS608354A - Light-weight insulating material composition - Google Patents

Abstract

PURPOSE:To provide a premix composition capable of giving a light-weight product without lowering the electrical characteristics, by compounding inorganic microballoons with specific organic fine powder. CONSTITUTION:A composition having an insulation resistance of >=10<10>OMEGA after boiling for 2hr and a specific gravity of <=1.5, and obtained by compounding an unsaturated polyester resin, a crosslinking agent, a shrinkage-controlling agent, a filler and reinforcing fibers, and containing 2-5wt% inorganic microballoons and 0-10wt% organic fine powder incompatible with the unsaturated polyester resin as a part of the above filler. The unsaturated polyester resin is preferably the one obtained by proceeding the esterification reaction to an acid value of about 30-20. The organic fine powder is e.g. hardened epoxy resin, hardened phenolic resin, etc.

Description

【発明の詳細な説明】 ［発明の属する技術分野］ 本発明は不飽和ポリエステル成形材料（以下ブリミック
ス成形材料と称す）に係シ、特に２時間煮沸後の電気絶
縁抵抗（試験法はＪＩＳＫ−６９１１に基づく。）が１
０１０〔０３以上であるような比重１．５以下の軽量電
気絶縁材料組成物に関する。Detailed Description of the Invention [Technical Field to which the Invention Pertains] The present invention relates to an unsaturated polyester molding material (hereinafter referred to as Brimix molding material), and in particular to electrical insulation resistance after boiling for 2 hours (test method is JISK-1). Based on 6911) is 1
The present invention relates to a lightweight electrical insulating material composition having a specific gravity of 1.5 or less, which is 010[03 or more].

［従来技術とその問題点］ 不飽和ポリエステル樹脂に充てん材、架橋剤、低収縮化
剤及び補強繊維を配合してなるブリミックス成形材料は
その優れた電気特性、成形性、難燃性等の特性のため電
気機器の絶縁材料並びに構造材料として広く使われてき
た。[Prior art and its problems] Brimix molding materials, which are made by blending unsaturated polyester resin with fillers, cross-linking agents, low-shrinkage agents, and reinforcing fibers, have excellent electrical properties, moldability, flame retardance, etc. Due to its properties, it has been widely used as an insulating material and structural material for electrical equipment.

一般にプリミックス成形材料の比重は１．８〜２．２程
度であり、これを使った大型成形部品はかなシの重量と
なシ取り扱いが大変困難であった０ブリミツクス成形材
料の比重を高くする原因はその必須成分である炭酸カル
シウム、水酸化マグネシウム、水酸化アルミニウム、硫
酸バリウム、クレー、マイカ粉等の無轡充てん材及び補
強材としてのガラス繊維等が多重に含まれているためで
ある。In general, the specific gravity of premix molding materials is around 1.8 to 2.2, and the specific gravity of premix molding materials, which are extremely difficult to handle and the weight of large molded parts using them, is high. This is because it contains multiple unfilled fillers such as essential components calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, clay, and mica powder, as well as glass fibers as reinforcing materials.

しかし、プリミックス成形材料の緒特性を得るためには
、これら充てん材及び補強材を大幅に減することは難か
しい。これまで、プリミックス成形材料の軽量化として
、以下の方法が試みられてきた。However, in order to obtain the properties of a premix molding material, it is difficult to significantly reduce the amount of these fillers and reinforcing materials. Up to now, the following methods have been attempted to reduce the weight of premix molding materials.

（１）成形材料中の樹脂分を増加させる方法。(1) A method of increasing the resin content in the molding material.

この方法は耐熱性、成形性、経済性に問題があった。This method had problems with heat resistance, moldability, and economic efficiency.

（２）発泡させる方法。(2) Foaming method.

この方法は機械的強度や耐コロナ性等の点で充分でなく
、電気絶縁材料として不向きであった。This method was insufficient in terms of mechanical strength and corona resistance, and was unsuitable as an electrical insulating material.

（３）軽量光てん材を配合する方法。(3) Method of blending lightweight optical fiber material.

しかして軽量光てん材を配合すると有効であることが一
般的に知られている。しかし、この軽量光てん材の一種
である無機微小中空体は含有する水溶性アルカリ成分の
ため多量には使用できない欠点がある。まだ有機微小中
空体は耐熱性、難燃性、耐コロナ性、経済性等の点から
不向きである。However, it is generally known that it is effective to include a lightweight optical fiber material. However, this inorganic micro hollow body, which is a type of lightweight optical fiber material, has the disadvantage that it cannot be used in large quantities because of the water-soluble alkali component it contains. Organic microhollow bodies are still unsuitable in terms of heat resistance, flame retardance, corona resistance, economic efficiency, etc.

また、無機光てん材に比して比重の小さい有機微粉末を
用いても大きな軽量効果は望めず、そのため大きな軽量
化を図るために多量に配合すると、耐熱性、難燃性、成
形性が著“しく低下する。In addition, even if organic fine powder is used, which has a lower specific gravity than inorganic photoresist materials, a large weight reduction effect cannot be expected. Therefore, if a large amount is added to achieve a large weight reduction, heat resistance, flame retardance, and moldability will deteriorate. Significantly decreased.

つまり、これまで試みられている軽量プリミックス成形
材料では電気特性が著しく低下し、電気絶縁材料として
は使用できなかった。In other words, the electrical properties of the lightweight premix molding materials that have been tried so far deteriorated significantly, and they could not be used as electrical insulating materials.

［発明の目的］ 本発明者らは前記の如き欠点を改良した軽量電気絶縁材
料組成物を得るべく鋭意検討した結果、従来のブリミッ
クス成形材料に、無機微小中空体を２％〜５チ及び、不
飽和ポリエステルに相溶しない有機微粉末をＯ％〜１０
チを配合することにより、２時間煮沸後の電気絶縁抵抗
が１０１０〔０３以上であり、比重が１．５以下である
軽量電気絶縁材料組成物を見出し、本発明に到った。[Object of the Invention] The present inventors have conducted intensive studies to obtain a lightweight electrical insulating material composition that improves the above-mentioned drawbacks, and have found that 2% to 5% of inorganic micro hollow bodies and , 0% to 10% of organic fine powder that is incompatible with unsaturated polyester
A lightweight electrical insulating material composition having an electrical insulation resistance of 1010[03] or more and a specific gravity of 1.5 or less after boiling for 2 hours was discovered by incorporating H, leading to the present invention.

即ち、本発明は２時間煮沸後の電気絶縁抵抗が１０１０
〔０３以上であり、比重が１．５以下である軽量電気絶
縁材料組成物を提供することを目的とする。That is, the present invention has an electrical insulation resistance of 1010 after boiling for 2 hours.
[An object of the present invention is to provide a lightweight electrical insulating material composition having a specific gravity of 0.03 or more and a specific gravity of 1.5 or less.

［発明の概要］ 以下本発明の詳細な説明すると、本発明は少なくとも不
飽和ポリエステル樹脂、架橋剤、低収縮化剤、充てん材
、無機微小中空体２チ〜５チ不飽和ポリエステルに相溶
しない有機微粉末（以後有機微粉末と略す。）０〜１０
重量％及び補強繊維を配合してなる軽量電気絶縁材料組
成物である。[Summary of the Invention] Hereinafter, the present invention will be described in detail.The present invention will be described in detail below. Organic fine powder (hereinafter abbreviated as organic fine powder) 0 to 10
% by weight and reinforcing fibers.

本発明に使用する不飽和ポリエステル樹脂は。The unsaturated polyester resin used in the present invention is:

多価アルコール成分とα、β−ジカルボン酸成分とを反
応組成とし、Ｎ２ガス雰囲気下１２０℃〜２１０℃でエ
ステル化反応させることによって容易に得られる。しか
してこのエステル化反応は酸化Ｉ〜加程度まで進めるこ
とがのぞましく、この反応に用いるジカルボン酸成分と
しては無水マレイン酸、フマル酸、イタコン酸、等の不
飽和ジカルボン酸、要スればフタル酸、イソフタル酸、
テレフタル酸、ヘキサヒドロ無水フタール酸、士ノ１り
酸、アジピン酸、無水ナジック、テトラ無水フタル酸等
の飽和ジカルボン酸等で一部を置換したものが挙げられ
る。一方、多価アルコール成分としてはネオペンチルグ
リコール、水添化ビスフェノールＡ、プロピレングリコ
ール、エチレンクリコール、シフロピレングリコール、
ジエチレングリコール、トリメチレングリコール、３−
メチルベンタンジオール、２−メチル−ブタンジオール
、４−シクロヘキサンジオール等から選ばれた１種もし
くは２種以上を用いることができる。It can be easily obtained by making a polyhydric alcohol component and an α,β-dicarboxylic acid component into a reaction composition and carrying out an esterification reaction at 120° C. to 210° C. in an N2 gas atmosphere. However, it is preferable that this esterification reaction be carried out to a degree of oxidation I or above, and the dicarboxylic acid component used in this reaction may include unsaturated dicarboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, etc. baphthalic acid, isophthalic acid,
Examples include those partially substituted with saturated dicarboxylic acids such as terephthalic acid, hexahydrophthalic anhydride, shinoric acid, adipic acid, nadic anhydride, and tetraphthalic anhydride. On the other hand, polyhydric alcohol components include neopentyl glycol, hydrogenated bisphenol A, propylene glycol, ethylene glycol, cyfropylene glycol,
Diethylene glycol, trimethylene glycol, 3-
One or more selected from methylbentanediol, 2-methyl-butanediol, 4-cyclohexanediol, etc. can be used.

本発明に用いられる架橋剤としては、スチレンビニルト
ルエン、ａ−メチルスチレン、ｔ−ブチルスチレン、ク
ロルスチレン等ノスチレン系単量体、フタル酸ジアリル
、酢酸ビニル、アクリル酸エステル類、メタクリル酸エ
ステル類等をあげることができる。Examples of the crosslinking agent used in the present invention include nostyrene monomers such as styrene vinyltoluene, a-methylstyrene, t-butylstyrene, and chlorostyrene, diallyl phthalate, vinyl acetate, acrylic esters, methacrylic esters, etc. can be given.

本発明に用いられる低収縮化剤は、スチレン。The low shrinkage agent used in the present invention is styrene.

エチレン、プロピレン、塩化ビニル、酢酸ビニル、メタ
クリル酸等の単独重合体や共重合体、飽和ポリエステル
等があげられる。Examples include homopolymers and copolymers of ethylene, propylene, vinyl chloride, vinyl acetate, methacrylic acid, and saturated polyesters.

更に本発明に用いられる充てん材としては、炭酸カルシ
ウム、水酸化マグネシウム、水酸化アルミニウム、硫酸
バリウム、クレー、マイカ粉等ノ無機充てん材が上げら
れる。Furthermore, examples of the filler used in the present invention include inorganic fillers such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, clay, and mica powder.

本発明に用いられる無機微小中空体としては、ガラスマ
イクロバルーン（エマージンアンドヵミンク社）、フィ
ライト（日本フィライト）、シリカバルーン（太平洋工
業建設工業）、シラスバルーン（王様工業）、マグライ
ト（三井田川タイル）、マイクロセル（日本フィライト
）、アルミナバブル（ツートン社）、ダイヤバルーン（
日本Ｍ　化学）、パーライト（三井金属）等が挙げられ
る。Inorganic micro hollow bodies used in the present invention include glass microballoons (Emerging and Caminck Co., Ltd.), phyllite (Nippon Phyllite), silica balloons (Taiheiyo Kogyo Kensetsu Kogyo), Shirasu balloons (Osama Kogyo), and Maglite (Miyidagawa). Tile), Microcell (Nippon Philite), Alumina Bubble (Two-Tone), Diamond Balloon (
(Japan M Chemical), pearlite (Mitsui Kinzoku), etc.

尚、本発明において無機微小中空体の配合割合を２〜５
重量％と限定したのは、２重量係未満の配合量では、単
独使用はもちろんのこと後述する有機微粉末１０重量％
との併用においても比重１．５以上となり、所望の軽量
化が出来ない。また無機微小中空体の配合割合が５チを
超えるものでは、２時間煮沸後の電気絶縁抵抗の大幅な
低下げかりでなく、その配合割合に比例した軽量効果が
得られないからである。In addition, in the present invention, the blending ratio of inorganic micro hollow bodies is 2 to 5.
The reason why the weight percentage is limited is that if the amount is less than 2% by weight, it can be used alone as well as 10% by weight of the organic fine powder described below.
Even when used in combination, the specific gravity becomes 1.5 or more, making it impossible to achieve the desired weight reduction. Moreover, if the blending ratio of inorganic micro hollow bodies exceeds 5, the electrical insulation resistance after 2 hours of boiling will not be significantly lowered, and the weight reduction effect proportional to the blending ratio will not be obtained.

本発明に用いられる有機微粉末としては、硬化エポキシ
樹脂、硬化ポリエステル樹脂、硬化フェノール樹脂、ポ
リアセタール、ポリエチレン、ポリプロピレン、等を原
料とする微粉末が挙げられる。尚、本発明において有機
微粉末の配合割合を０〜１０重量％と限定したのは、１
０重量％を超えるものでは成形性及び熱時硬度が極度に
低下し、さらには成形品の表面光沢を失うといっだ問題
が生じる。Examples of the organic fine powder used in the present invention include fine powders made from cured epoxy resins, cured polyester resins, cured phenol resins, polyacetals, polyethylene, polypropylene, and the like. In addition, in the present invention, the blending ratio of organic fine powder is limited to 0 to 10% by weight.
If the amount exceeds 0% by weight, the moldability and hardness when heated will be extremely reduced, and further problems will arise when the surface gloss of the molded product is lost.

また、ここで不飽和ポリエステル樹脂に相溶しない有機
微粉末と限定したのは、相溶する有機物をプリミックス
に配合するとその配合割合に応じて著しく増粘し、作業
性、成形性、成形品の機械的物性を著しく損うためであ
る。In addition, the organic fine powder that is incompatible with unsaturated polyester resin is limited here because if compatible organic substances are added to the premix, the viscosity will increase significantly depending on the blending ratio, resulting in poor workability, moldability, and molded products. This is because the mechanical properties of the material are significantly impaired.

本発明に用いられる補強繊維は、ブリミックス成形材料
の機械的特性、経済性を考慮して一般にガラス繊維が用
いられ、その他ビニロン繊維、アラミド繊維、ポリエチ
レン繊維、ポリプロピレン繊維等を併用することができ
る。As the reinforcing fiber used in the present invention, glass fiber is generally used in consideration of the mechanical properties and economic efficiency of the BRIMIX molding material, and other materials such as vinylon fiber, aramid fiber, polyethylene fiber, polypropylene fiber, etc. can also be used in combination. .

゛［発明の実施例］ 以下本発明を実施例に基すいて比較例と合わせて説明す
る。[Examples of the Invention] The present invention will be described below based on Examples and Comparative Examples.

実施例　１、 無水マイレン酸５．５モル、インフタール酸４．５モル
、プロピレングリコール１０．３モルを反応組成分とし
Ｎ２ガス雰囲気下１２０’Ｏ〜２１０”Ｏでエステル化
反応させ酸価がの不飽和ポリエステル樹脂を合成した。Example 1 5.5 moles of maleic anhydride, 4.5 moles of inphthalic acid, and 10.3 moles of propylene glycol were used as reaction components, and an esterification reaction was carried out at 120'O to 210"O in an N2 gas atmosphere to increase the acid value. An unsaturated polyester resin was synthesized.

次いでハイドロキノン２５０　ｐｐｒｎを加える一方ス
チレンモノマーを加え溶解し、樹脂分５０チの不飽和ポ
リエステル樹脂溶液を胴整した。前記の不飽和ポリエス
テル樹脂溶液、低収縮化剤、架橋剤、充てん材、微小中
空体、有機微粉末及び補強繊維を混合、混練し、パテ状
のブリミックス成形材料を製造した。組成を表−１に示
す。Next, 250 pprn of hydroquinone was added, while styrene monomer was added and dissolved to prepare an unsaturated polyester resin solution having a resin content of 50 t. The unsaturated polyester resin solution, low shrinkage agent, crosslinking agent, filler, micro hollow bodies, organic fine powder and reinforcing fibers were mixed and kneaded to produce a putty-like BRIMIX molding material. The composition is shown in Table-1.

上記によＩ）Ｓ’！整したプリミックス成形材料を原料
とし圧縮成形機を用い下記の成形条件でＪＩＳＫ−６９
１１に基６く絶縁抵抗測定用試験片及び成形収縮率測定
用試験片を成形した。According to the above I) S'! Using the prepared premix molding material as raw material and using a compression molding machine under the following molding conditions, JISK-69
A test piece for measuring insulation resistance and a test piece for measuring molding shrinkage rate were molded based on No. 11.

金型温度　１５０〜１６０℃ 成形圧力　５０〜５５　ｋｇ／ｃｄ 成形時間　１８０８ｅｃ 前記によって得られた試験片によって２時間煮沸後の絶
縁抵抗及び比重を測定した。尚、比重測定は成形収縮率
測定用円板より試験片を切シ出した。結果を表−１に示
す。Mold temperature: 150-160° C. Molding pressure: 50-55 kg/cd Molding time: 1808 ec The insulation resistance and specific gravity after boiling for 2 hours were measured using the test piece obtained above. For measuring specific gravity, a test piece was cut out from a disk for measuring mold shrinkage rate. The results are shown in Table-1.

実施例２，３．４及び５ 表−１に示した組成比によってブリミックス成形拐料を
製造し実施例１と同様の方法で成形及び測定した。結果
を組成比と合わせて表−１に示した０ 比較例１，２及び３ 表−１に示しだ組成比によって、ブリミックス成形材料
を製造し、実施例１と同様の方法で成形及び測定をした
。結果を組成比と合わせて表−１に示した。Examples 2, 3.4 and 5 Brimix molded materials were produced according to the composition ratios shown in Table 1, and molded and measured in the same manner as in Example 1. The results are shown in Table 1 along with the composition ratios. Comparative Examples 1, 2 and 3 Brimix molding materials were manufactured according to the composition ratios shown in Table 1, and molded and measured in the same manner as in Example 1. Did. The results are shown in Table 1 together with the composition ratio.

以下余白Below margin

Claims (1)

【特許請求の範囲】[Claims] 不飽和ポリエステル樹脂、架橋剤、低収縮化剤、充てん
材及び補強繊維を配合して成る不飽和ポリエステル樹脂
成形材料において、充てん材の一部として無機微小中空
体２〜５重量係及び不飽和ポリエステル樹脂に相溶しな
い有機微粉末０〜１０重量％を含み２時間煮沸後の絶縁
抵抗がｌ０ＩＯＣΩ〕以上であることを特徴とする比重
１．５以下の軽量電気絶縁材料組成物。In an unsaturated polyester resin molding material comprising an unsaturated polyester resin, a crosslinking agent, a low shrinkage agent, a filler and a reinforcing fiber, as part of the filler, an inorganic micro hollow body of 2 to 5 weight percent and an unsaturated polyester are used. A lightweight electrical insulating material composition having a specific gravity of 1.5 or less, which contains 0 to 10% by weight of an organic fine powder that is incompatible with a resin, and has an insulation resistance of 10 IOCΩ or more after boiling for 2 hours.