JP2560679B2 - Flame retardant electrical insulation composition - Google Patents
Flame retardant electrical insulation compositionInfo
- Publication number
- JP2560679B2 JP2560679B2 JP3094710A JP9471091A JP2560679B2 JP 2560679 B2 JP2560679 B2 JP 2560679B2 JP 3094710 A JP3094710 A JP 3094710A JP 9471091 A JP9471091 A JP 9471091A JP 2560679 B2 JP2560679 B2 JP 2560679B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- magnesium hydroxide
- flame
- polyolefin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は難燃性電気絶縁組成物、
特に難燃性ポリオレフィン電気絶縁組成物に関する。The present invention relates to a flame-retardant electrical insulating composition,
In particular it relates to flame retardant polyolefin electrical insulation compositions.
【０００２】[0002]
【従来の技術】難燃化剤をポリオレフィンに添加するこ
とにより、ポリオレフィン絶縁材料を難燃性とすること
が行われている。ポリエチレン等のポリオレフィンは、
絶縁体として絶縁抵抗、絶縁耐力、誘電率、耐水性、耐
湿性、耐溶剤性、耐薬品性等多くの点で優れているの
で、電線・ケーブルの絶縁被膜として広く用いられてい
るが、燃焼し易く、火源から電線・ケーブルを伝わって
火災が拡がることがしばしばあるため、難燃性にするこ
とが要求されている。特に、民生用電気機器、車両、船
舶、航空機、工場、高層ビル、トンネル等に使用する電
線・ケーブルでは難燃性を強く要求される。2. Description of the Related Art A polyolefin insulating material has been made flame-retardant by adding a flame retardant to the polyolefin. Polyolefin such as polyethylene is
It is widely used as an insulation coating for electric wires and cables because it is excellent as an insulator in terms of insulation resistance, dielectric strength, dielectric constant, water resistance, moisture resistance, solvent resistance, chemical resistance, etc. Since it is easy to do and a fire often spreads from the fire source through electric wires and cables, it is required to make it flame-retardant. In particular, electric wires and cables used for consumer electric devices, vehicles, ships, aircraft, factories, high-rise buildings, tunnels, etc. are strongly required to have flame retardancy.
【０００３】難燃性とするためにポリオレフィンに添加
する難燃化剤として、ハロゲン含有有機化合物が広く用
いられているが、火災時に有毒ガスや大量の煙を発生す
るため、最近では、このような欠点のない、水酸化アル
ミニウムや水酸化マグネシウム等の金属水酸化物を用い
た無機系難燃化剤が用いられるようになっている。[0003] Halogen-containing organic compounds are widely used as flame retardants added to polyolefins to make them flame-retardant. However, since they generate toxic gas and a large amount of smoke at the time of fire, it has recently been Inorganic flame retardants using metal hydroxides such as aluminum hydroxide and magnesium hydroxide, which have no such drawbacks, have come to be used.
【０００４】[0004]
【発明が解決しようとする課題】しかし、金属水酸化物
は、ポリオレフィン中に多量に添加しないと、最近の電
線ケーブル各種規格（例えばＩＥＥＥ規格３８３）で要
求される高度の難燃性を得ることができない。ところ
が、ポリオレフィンに金属水酸化物を多量に添加する
と、絶縁材料の成形加工に困難に生じ、絶縁体やシース
の引張特性等の機械的特性を著しく悪化させる。However, unless a large amount of metal hydroxide is added to the polyolefin, it is possible to obtain a high degree of flame retardance required by various standards for electric wires and cables (for example, IEEE standard 383). I can't. However, when a large amount of metal hydroxide is added to polyolefin, it is difficult to form the insulating material in the molding process, and mechanical properties such as tensile properties of the insulator and the sheath are significantly deteriorated.
【０００５】それ故、本発明の目的は、電線・ケーブル
等に用いる絶縁材料に要求される機械的特性を満足し、
かつすぐれた難燃性を有する電気絶縁組成物を実現する
ことである。Therefore, an object of the present invention is to satisfy the mechanical characteristics required for an insulating material used for electric wires and cables,
And to realize an electrical insulating composition having excellent flame retardancy.
【０００６】[0006]
【課題を解決するための手段】本発明では、電線・ケー
ブル等に用いる絶縁材料に要求される機械的特性を満足
し、かつすぐれた難燃性を有する電気絶縁組成物を実現
するため、エチレン酢酸ビニル共重合体を含むポリオレ
フィンから成る電気絶縁組成物に難燃化剤として、ポリ
オレフィン１００重量部に対し水酸化マグネシウムおよ
び焼成アルミン酸カルシウムを合計１００重量部以上、
しかも水酸化マグネシウムと焼成アルミン酸カルシウム
の重量比が９０：１０乃至５０：５０の範囲になるよう
に、添加する。According to the present invention, in order to realize an electrical insulating composition satisfying the mechanical properties required for an insulating material used for electric wires, cables, etc. and having excellent flame retardancy, ethylene is used. As a flame retardant for an electrically insulating composition made of a polyolefin containing a vinyl acetate copolymer, magnesium hydroxide and calcined calcium aluminate are added in a total amount of 100 parts by weight or more based on 100 parts by weight of the polyolefin.
Moreover, it is added so that the weight ratio of magnesium hydroxide and calcined calcium aluminate is in the range of 90:10 to 50:50.
【０００７】本発明の絶縁組成物を構成するポリオレフ
ィンは、エチレン酢酸ビニル共重合体を含む。エチレン
酢酸ビニル共重合体のほか、ポリエチレン、エチレンプ
ロピレン共重合体（他の重合成分を含んでもよい）、エ
チレンメチルアクリレート共重合体、エチレンエチルア
クリレート共重合体、エチレンブテン共重合体（他の重
合成分、例えばブタジエンを、含んでもよい）等を含ん
でもよい。３種以上のポリオレフィンを用いてもよい。
エチレン酢酸ビニル共重合体は、ポリオレフィン中少な
くとも１０重量％含まれることが好ましい。The polyolefin constituting the insulating composition of the present invention contains an ethylene vinyl acetate copolymer. In addition to ethylene vinyl acetate copolymer, polyethylene, ethylene propylene copolymer (may contain other polymerization components), ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butene copolymer (other polymerization Components, such as butadiene) may be included. You may use 3 or more types of polyolefins.
The ethylene vinyl acetate copolymer is preferably contained in the polyolefin in an amount of at least 10% by weight.
【０００８】水酸化マグネシウムは、凝集、強靱性、耐
水性等の点から、０．１乃至５μｍの範囲の平均粒子径
をもつものが好ましく、また脂肪酸、脂肪酸金属塩、シ
ランカプリング剤、チタネートカプリング剤等で表面処
理されることが好ましい。From the viewpoint of cohesion, toughness, water resistance, etc., magnesium hydroxide is preferably one having an average particle size in the range of 0.1 to 5 μm, and fatty acid, fatty acid metal salt, silane coupling agent, titanate coupling. It is preferable that the surface is treated with an agent or the like.
【０００９】焼成アルミン酸カルシウムは、アルミン酸
カルシウムを温度４００℃以上で焼成したもので、水酸
化マグネシウムと同様の表面処理がされていることが好
ましい。平均粒子径は０．１乃至５μｍの範囲が好まし
い。The calcined calcium aluminate is calcined calcium aluminate at a temperature of 400 ° C. or higher, and is preferably subjected to the same surface treatment as magnesium hydroxide. The average particle diameter is preferably in the range of 0.1 to 5 μm.
【００１０】水酸化マグネシウムと焼成アルミン酸カル
シウムは、ポリオレフィン１００重量部に対し合計１０
０重量部以上加えることが必要である。そうでないと、
充分な難燃性を得ることができない。しかし、多過ぎる
と機械的特性（強靱性、加工性を含む）を損なうので、
３００重量部以下とするのが好ましい。水酸化マグネシ
ウムと焼成アルミン酸カルシウムの重量比は、９０：１
０乃至５０：５０の範囲になるようにしないと、十分な
難燃性が得られない。The total amount of magnesium hydroxide and calcined calcium aluminate is 10 per 100 parts by weight of polyolefin.
It is necessary to add 0 part by weight or more. Otherwise,
It is not possible to obtain sufficient flame retardancy. However, if too much, the mechanical properties (including toughness and workability) are impaired, so
It is preferably 300 parts by weight or less. The weight ratio of magnesium hydroxide to calcined calcium aluminate is 90: 1.
Unless it is set within the range of 0 to 50:50, sufficient flame retardancy cannot be obtained.
【００１１】本発明の絶縁組成物は熱可塑性であり、成
形して用いられるが、そのまま成形してもよく、またポ
リオレフィンを架橋してもよい（部分架橋後成形または
成形後架橋）。架橋には、有機過酸化物の添加、電子線
照射、シラングラフト水架橋等のいずれを用いてもよ
い。有機過酸化物としては、ジクミルペルオキシド（di
cumyl peroxide) 、3-ビス（t-ブチルペルオキシイソプ
ロピル）ベンゼン等が好適である。The insulating composition of the present invention is thermoplastic and used by molding, but it may be molded as it is, or may be crosslinked with a polyolefin (partially crosslinked molding or postmolding crosslinking). For the crosslinking, any of addition of organic peroxide, electron beam irradiation, silane graft water crosslinking and the like may be used. As an organic peroxide, dicumyl peroxide (di
cumyl peroxide), 3-bis (t-butylperoxyisopropyl) benzene and the like are preferable.
【００１２】本発明の絶縁組成物は、ポリオレフィン１
００重量部に対し１重量部以上のホスファゼン化合物、
例えば、プロポキシホスファゼンオリゴマ、フェノキシ
ホスファゼンオリゴマ、アミノホスファゼンオリゴマ等
を含んでもよい。The insulating composition of the present invention comprises polyolefin 1
1 part by weight or more of phosphazene compound based on 00 parts by weight,
For example, it may include a propoxyphosphazene oligomer, a phenoxyphosphazene oligomer, an aminophosphazene oligomer and the like.
【００１３】本発明の絶縁組成物はさらに、架橋剤、架
橋助剤、酸化防止剤、軟化剤、滑剤、着色剤、カーボン
ブラック等を含んでもよい。The insulating composition of the present invention may further contain a crosslinking agent, a crosslinking aid, an antioxidant, a softening agent, a lubricant, a coloring agent, carbon black and the like.
【００１４】[0014]
【作用】本発明の難燃性電気絶縁組成物は、難燃化剤と
して水酸化マグネシウムとともに焼成アルミン酸カルシ
ウムを用いることにより、水酸化マグネシウムを機械的
特性が悪化するほど多量に添加しなくても、すぐれた難
燃性を得ることができる。焼成アルミン酸カルシウムの
共存による難燃性の向上の作用機構ははっきりしない
が、示差走査熱量計により求めた水酸化マグネシウムと
焼成アルミン酸カルシウムの混合物の吸熱ピークは、水
酸化マグネシウム単独の場合より約５０℃高温側にあ
り、これと関連があるように思われる。以下、実施例に
より本発明をさらに詳細に説明する。The flame-retardant electrical insulating composition of the present invention uses magnesium hydroxide as a flame retardant together with magnesium hydroxide to prevent addition of magnesium hydroxide in such a large amount that mechanical properties deteriorate. Also, excellent flame retardancy can be obtained. Although the mechanism of action for improving flame retardancy due to the coexistence of calcined calcium aluminate is not clear, the endothermic peak of the mixture of magnesium hydroxide and calcined calcium aluminate determined by a differential scanning calorimeter is about that of magnesium hydroxide alone. It is on the high temperature side of 50 ° C and seems to be related to this. Hereinafter, the present invention will be described in more detail with reference to Examples.
【００１５】[0015]
【実施例１〜４】表１に示す組成の絶縁組成物を調製し
た（単位は重量部) 。混練には１２インチロールを用い
た。エチレン酢酸ビニルコポリマーは酢酸ビニル成分２
５重量％を含みメルトインデックス（１９０℃）1.０の
もの、エチレンエチルアクリレートコポリマーはエチル
アクリレート成分２０重量％を含みメルトインデックス
（１９０℃）1.０のもの、エチレンプロピレンゴムはエ
チレン８０モル％とプロピレン２０モル％の共重合体
で、ムーニ粘度ＭＬ1+4 （１００℃）が４０、沃素価
（ＥＮＢ）２０のもの、エチレンブテンコポリマーはエ
チレン成分８０モル％、メルトインデックス（１９０
℃）3.０のものである。水酸化マグネシウムは平均粒子
径１μｍで、オレイン酸処理したもの、焼成アルミン酸
カルシウムは平均粒子径１μｍで、６００℃２４時間焼
成し、ステアリン酸処理したものである。Examples 1 to 4 Insulating compositions having the compositions shown in Table 1 were prepared (unit is parts by weight). A 12 inch roll was used for kneading. Ethylene vinyl acetate copolymer is a vinyl acetate component 2
5% by weight melt index (190 ° C) 1.0, ethylene-ethyl acrylate copolymer 20% by weight ethyl acrylate component melt index (190 ° C) 1.0, ethylene propylene rubber 80% ethylene And a propylene 20 mol% copolymer having a Mooney viscosity ML 1 + 4 (100 ° C.) of 40 and an iodine value (ENB) of 20. An ethylene butene copolymer has an ethylene component of 80 mol% and a melt index (190
C.) 3.0. Magnesium hydroxide has an average particle diameter of 1 μm and is treated with oleic acid, and calcined calcium aluminate has an average particle diameter of 1 μm and is calcined at 600 ° C. for 24 hours and treated with stearic acid.
【００１６】 [0016]
【００１７】各組成物を用いて下記のようにケーブルを
製作し、引張特性と難燃性を評価した。４０mm押出機
（Ｌ／Ｄは２２）を用いて、外径１．８mmの導体の外周
に紙セパレータ（厚さ１０μｍ）を縦添えしながら1.1
μｍの厚さに押出被覆した。実施例１，３，４について
は、押出被覆後圧力1.５ＭPaの水蒸気中で３分間加熱し
て、架橋を行った。引張特性と難燃性の評価は、次のよ
うに行った。 (1) 引張特性 ケーブルの伸線およびセパレータを取り除き、ＪＩＳダ
ンベル３００５に準拠して、引張速度５００mm／分で引
張試験を行った。 (2) 難燃性 ＵＬ４４に準拠した垂直燃焼試験を行い、燃焼時間が６
０秒以内のものを合格、６０秒を超えるものを不合格と
した。引張特性と難燃性を評価した結果を、組成ととも
に表１に示す。Cables were manufactured using the respective compositions as described below, and the tensile properties and flame retardancy were evaluated. Using a 40 mm extruder (L / D is 22), while vertically attaching a paper separator (thickness 10 μm) to the outer circumference of a conductor with an outer diameter of 1.8 mm, 1.1
It was extrusion coated to a thickness of μm. In Examples 1, 3 and 4, after extrusion coating, crosslinking was performed by heating for 3 minutes in steam having a pressure of 1.5 MPa. The tensile properties and flame retardancy were evaluated as follows. (1) Tensile property The wire drawing of the cable and the separator were removed, and a tensile test was carried out at a tensile speed of 500 mm / min in accordance with JIS dumbbell 3005. (2) Flame retardance A vertical combustion test based on UL44 was conducted and the combustion time was 6
Those within 0 seconds were passed and those over 60 seconds were rejected. The results of evaluation of tensile properties and flame retardancy are shown in Table 1 together with the composition.
【００１８】各組成物とも１２ＭPa以上の引張強さと、
４００％前後の伸びを示し、難燃性の試験結果は合格で
あった。Each composition has a tensile strength of 12 MPa or more,
It showed an elongation of around 400% and passed the flame retardancy test result.
【００１９】[0019]
【比較例１〜４】比較のため、表２に示す本発明外の組
成の絶縁組成物を調製した。調製方法、評価方法は実施
例１〜４と同じである。評価結果を、組成とともに表２
に示す。Comparative Examples 1 to 4 For comparison, insulating compositions having compositions other than the present invention shown in Table 2 were prepared. The preparation method and evaluation method are the same as in Examples 1 to 4. Table 2 shows the evaluation results together with the composition.
Shown in
【００２０】 [0020]
【００２１】表２から明らかなように、水酸化マグネシ
ウムと焼成アルミン酸カルシウムの合計を、ポリオレフ
ィン１００重量部に対し８０重量部にした比較例１は、
引張強さでは実施例１より若干優れるが、難燃性は不合
格である。充分な難燃性を得るためには、ポリオレフィ
ン１００重量部に対し合計８０重量部では不足なことを
示している。水酸化マグネシウム３０重量部に対し１０
０重量部の焼成アルミン酸カルシウムを用いた比較例２
は、難燃性が劣るだけでなく、引張強度も伸びも低下し
ている。この結果は、水酸化マグネシウムより多い焼成
アルミン酸カルシウムを用いると、機械的特性が悪くな
ることを示している。As is clear from Table 2, Comparative Example 1 in which the total amount of magnesium hydroxide and calcined calcium aluminate was 80 parts by weight with respect to 100 parts by weight of the polyolefin,
The tensile strength is slightly superior to that of Example 1, but the flame retardancy is unacceptable. In order to obtain sufficient flame retardancy, it is shown that 80 parts by weight in total is insufficient with respect to 100 parts by weight of polyolefin. 10 to 30 parts by weight of magnesium hydroxide
Comparative Example 2 with 0 part by weight of calcined calcium aluminate
Not only is inferior in flame retardancy, but also in tensile strength and elongation. The results show that using more calcined calcium aluminate than magnesium hydroxide results in poor mechanical properties.
【００２２】また、水酸化マグネシウム１００重量部に
対し１０重量部の焼成アルミン酸カルシウムを用いた比
較例３、および水酸化マグネシウムのみを用いた比較例
４（従来例に相当）は、難燃性が劣る。ポリオレフィン
１００重量部に対し難燃化剤を合計１００重量部以上含
んでいても、水酸化マグネシウムに対する焼成アルミン
酸カルシウムの重量比が９０：１０より小さくなると、
満足な難燃性が得られないことを示している。Further, Comparative Example 3 in which 10 parts by weight of calcined calcium aluminate was used per 100 parts by weight of magnesium hydroxide and Comparative Example 4 in which only magnesium hydroxide was used (corresponding to the conventional example) were flame retardant. Is inferior. Even if the flame retardant is contained in a total amount of 100 parts by weight or more based on 100 parts by weight of the polyolefin, if the weight ratio of the calcined calcium aluminate to the magnesium hydroxide is smaller than 90:10,
It shows that satisfactory flame retardancy cannot be obtained.
【００２３】[0023]
【発明の効果】本発明の難燃性電気絶縁組成物は、電線
・ケーブル等の絶縁体に要求される機械的特性を具え、
かつすぐれた難燃性を有する。The flame-retardant electrical insulation composition of the present invention has mechanical properties required for insulators such as electric wires and cables,
It also has excellent flame retardancy.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 3/44 Ｈ０１Ｂ 3/44 Ｍ // Ｈ０１Ｂ 7/34 7/34 Ｂ (56)参考文献 特開 昭63−39939（ＪＰ，Ａ) 特開 昭64−27111（ＪＰ，Ａ) 特開 昭63−286450（ＪＰ，Ａ) 特開 昭62−186411（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical display location H01B 3/44 H01B 3/44 M // H01B 7/34 7/34 B (56) References Kai 63-39939 (JP, A) JP 64-27111 (JP, A) JP 63-286450 (JP, A) JP 62-186411 (JP, A)
Claims (1)
レフィンから成る難燃性電気絶縁組成物において、 ポリオレフィン１００重量部に対し水酸化マグネシウム
および焼成アルミン酸カルシウムを合計１００〜３００
重量部含み、 前記水酸化マグネシウムと前記焼成アルミン酸カルシウ
ムの重量比が９０：１０乃至５０：５０の範囲にあるよ
うにしたことを特徴とする、難燃性電気絶縁組成物。1. A flame-retardant electrical insulating composition comprising a polyolefin containing an ethylene-vinyl acetate copolymer, wherein a total of 100 to 300 parts by weight of magnesium hydroxide and calcined calcium aluminate is added to 100 parts by weight of the polyolefin.
A flame-retardant electrical insulating composition, characterized in that the weight ratio of the magnesium hydroxide to the calcined calcium aluminate is in the range of 90:10 to 50:50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3094710A JP2560679B2 (en) | 1991-04-01 | 1991-04-01 | Flame retardant electrical insulation composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3094710A JP2560679B2 (en) | 1991-04-01 | 1991-04-01 | Flame retardant electrical insulation composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04304252A JPH04304252A (en) | 1992-10-27 |
| JP2560679B2 true JP2560679B2 (en) | 1996-12-04 |
Family
ID=14117716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3094710A Expired - Fee Related JP2560679B2 (en) | 1991-04-01 | 1991-04-01 | Flame retardant electrical insulation composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2560679B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6667358B1 (en) * | 1999-05-17 | 2003-12-23 | Dupont-Mitsui Polychemicals Co. | Flame retardant resin composition |
| JP4749524B2 (en) * | 1999-10-15 | 2011-08-17 | 三井・デュポンポリケミカル株式会社 | Flame retardant resin composition |
| CN113628782B (en) * | 2021-08-16 | 2023-04-07 | 贵州新曙光电缆有限公司 | Medium-voltage power flexible cable for wind power generation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0668928B2 (en) * | 1986-02-12 | 1994-08-31 | 日立電線株式会社 | Flame-retardant wire / cable |
| JPS6339939A (en) * | 1986-08-01 | 1988-02-20 | Hitachi Cable Ltd | Flame-retarding electrically insulating composition |
| JPS63286450A (en) * | 1987-05-20 | 1988-11-24 | Agency Of Ind Science & Technol | Non-halogenated flame-retardant composition for electrical insulation with improved radiation resistance |
| JPS6427111A (en) * | 1988-07-08 | 1989-01-30 | Hitachi Cable | Fire retardant insulated electric wire |
-
1991
- 1991-04-01 JP JP3094710A patent/JP2560679B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04304252A (en) | 1992-10-27 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |