JPH05339437A - Flame-resistant resin composition - Google Patents
Flame-resistant resin compositionInfo
- Publication number
- JPH05339437A JPH05339437A JP17941192A JP17941192A JPH05339437A JP H05339437 A JPH05339437 A JP H05339437A JP 17941192 A JP17941192 A JP 17941192A JP 17941192 A JP17941192 A JP 17941192A JP H05339437 A JPH05339437 A JP H05339437A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- resin composition
- weight
- resistant resin
- molecular weight
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐外傷性および耐摩耗
性に優れた難燃性樹脂組成物に関し、特に電線被覆材と
して有用な難燃性樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition having excellent external damage resistance and abrasion resistance, and particularly to a flame-retardant resin composition useful as a wire coating material.
【０００２】[0002]
【従来の技術】従来、ハロゲン含有組成物のように燃焼
時に有毒ガスを発生しないという利点を有する難燃性樹
脂組成物として、ポリオレフィンベースポリマーに難燃
性充填剤としての水和金属酸化物を適量配合してなる所
謂ノンハロゲン樹脂組成物が使用されている。しかしな
がら、該組成物を自己消火性を備える程度に難燃化する
には多量に水和金属酸化物を配合する必要があり、この
ような組成物は耐外傷性や耐摩耗性などの機械的強度が
脆く、例えば電線被覆材などの用途には不適切であると
いう問題があった。2. Description of the Related Art Conventionally, as a flame-retardant resin composition having an advantage that a toxic gas is not generated during combustion unlike a halogen-containing composition, a hydrated metal oxide as a flame-retardant filler is added to a polyolefin-based polymer. A so-called non-halogen resin composition prepared by mixing an appropriate amount is used. However, in order to make the composition flame-retardant to the extent that it has self-extinguishing properties, it is necessary to add a large amount of hydrated metal oxides, and such a composition has mechanical properties such as trauma resistance and abrasion resistance. There is a problem that the strength is brittle and it is unsuitable for applications such as electric wire coating materials.
【０００３】[0003]
【発明が解決しようとする課題】従って本発明は、優れ
た難燃性を有すると共に、耐外傷性や耐摩耗性などの機
械的強度にも優れた、電線被覆材などの用途に好適なノ
ンハロゲン難燃性樹脂組成物を提供することを課題とす
る。Therefore, the present invention is excellent in flame retardancy and is also excellent in mechanical strength such as external damage resistance and abrasion resistance, and is suitable for applications such as electric wire coating materials. An object is to provide a flame-retardant resin composition.
【０００４】[0004]
【課題を解決するための手段】本発明の難燃性樹脂組成
物は、密度が０．８５〜０．９３ｇ／cm3 のポリオレフ
ィンと、平均分子量が３０万以上でショアＤ硬度が５０
以上の超高分子量ポリエチレンとを、前者と後者との重
量比で９５〜６０：５〜４０の混合割合でブレンドした
ポリマー１００重量部に対し、水和金属酸化物を５０〜
３００重量部配合したことを特徴とするものである。The flame-retardant resin composition of the present invention comprises a polyolefin having a density of 0.85 to 0.93 g / cm 3 , an average molecular weight of 300,000 and a Shore D hardness of 50.
The above ultra high molecular weight polyethylene is blended with the former and the latter in a weight ratio of 95 to 60: 5 to 40 parts by weight of a polymer blended with 100 parts by weight of a hydrated metal oxide.
It is characterized by containing 300 parts by weight.
【０００５】[0005]
【発明の開示】本発明の、ポリオレフィンに所定量超高
分子量ポリエチレンを配合したベースポリマーであれ
ば、フィラー（水和金属酸化物）受容性に優れる上記密
度範囲のポリオレフィンの機械的強度が、高硬度であり
機械的強度にも優れる超高分子量ポリエチレンを分散さ
せることによって補強されるためか、難燃性向上のため
に水和金属酸化物を多量配合しても、当該難燃性樹脂組
成物の硬度が高レベルで維持できると共に耐外傷性や耐
摩耗性などの機械特性も高レベルで維持できることが判
明し、本発明を提案するに至った。DISCLOSURE OF THE INVENTION The base polymer of the present invention in which a predetermined amount of ultra-high molecular weight polyethylene is blended with the polyolefin has a high mechanical strength of the polyolefin in the above density range having excellent filler (hydrated metal oxide) receptivity. The flame-retardant resin composition may be reinforced by dispersing ultra-high-molecular-weight polyethylene that is hard and has excellent mechanical strength, or even if a large amount of hydrated metal oxide is added to improve flame retardancy. It was found that the hardness of can be maintained at a high level and mechanical properties such as external damage resistance and abrasion resistance can also be maintained at a high level, and the present invention has been proposed.
【０００６】本発明で使用される密度が０．８５〜０．
９３ｇ／cm3 のポリオレフィンとしては、ポリエチレ
ン、ポリプロピレン、ポリブテン、ポリ４−メチルペン
テン−１のようなα−オレフィン類、エチレン・プロピ
レン共重合体、エチレン・ブテン共重合体のようなα−
オレフィン同士の共重合体類、エチレン・酢酸ビニル共
重合体、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のようなα−オレフ
ィンと他種モノマーとの共重合体類などがあげられる。
就中、ポリエチレン等のポリα−オレフィン類、エチレ
ン・α−オレフィン共重合体類、エチレン・酢酸ビニル
共重合体、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等が好ましく使用
できる。The density used in the present invention is 0.85 to 0.
Examples of the 93 g / cm 3 polyolefin include α-olefins such as polyethylene, polypropylene, polybutene, and poly-4-methylpentene-1, α-olefins such as ethylene / propylene copolymers and ethylene / butene copolymers.
Copolymers of α-olefins with other monomers such as copolymers of olefins, ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, and ethylene / ethyl acrylate copolymers. Be done.
Among them, poly α-olefins such as polyethylene, ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer and the like can be preferably used. ..
【０００７】また超高分子量ポリエチレンとしては、平
均分子量が３０万以上のもの、好ましくは７０万以上の
もの、特に好ましくは１００万以上のものであって、そ
のショアＤ硬度が５０以上、好ましくは６０以上のもの
が好適に使用できる。The ultrahigh molecular weight polyethylene has an average molecular weight of 300,000 or more, preferably 700,000 or more, particularly preferably 1,000,000 or more, and has a Shore D hardness of 50 or more, preferably Those of 60 or more can be preferably used.
【０００８】当該ポリエチレンの平均分子量が３０万以
下であったりショアＤ硬度が５０以下であると、上記の
ポリオレフィンに当該ポリエチレンを配合しても得られ
る組成物の機械的強度をさほど向上させることができ
ず、本発明の目的を十分に達成できない。逆に平均分子
量が１００万以上、ショアＤ硬度が６０以上のものであ
れば、それ自身が優れた機械的特性を備えるポリエチレ
ンであり、上記のポリオレフィンに分散させると十分な
補強効果を発揮し、得られる樹脂組成物の硬度を高め耐
摩耗性や耐外傷性等の機械的特性を向上させ得る。When the polyethylene has an average molecular weight of 300,000 or less and a Shore D hardness of 50 or less, the mechanical strength of a composition obtained by blending the polyethylene with the above-mentioned polyolefin can be significantly improved. If not, the object of the present invention cannot be fully achieved. Conversely, if it has an average molecular weight of 1,000,000 or more and a Shore D hardness of 60 or more, it is a polyethylene having excellent mechanical properties by itself, and when it is dispersed in the above-mentioned polyolefin, it exerts a sufficient reinforcing effect, The hardness of the obtained resin composition can be increased and mechanical properties such as abrasion resistance and external damage resistance can be improved.
【０００９】該超高分子量ポリエチレンの具体例として
は、例えばリュブマーＬ４０００（三井石油化学株式会
社商品名；平均分子量１５０万、ショアＤ硬度６４）、
ハイゼックスミリオン１４５Ｍ（三井石油化学株式会社
商品名；平均分子量１００万、ショアＤ硬度６４）、ハ
イゼックスミリオン２４０Ｍ（三井石油化学株式会社商
品名；平均分子量３００万、ショアＤ硬度６６）等が挙
げられる。Specific examples of the ultra high molecular weight polyethylene include, for example, LUVMER L4000 (trade name of Mitsui Petrochemical Co., Ltd .; average molecular weight 1.5 million, Shore D hardness 64).
Hi-Zex Million 145M (trade name of Mitsui Petrochemical Co., Ltd .; average molecular weight 1,000,000, Shore D hardness 64), Hi-Zex Million 240M (trade name of Mitsui Petrochemical Co., Ltd .; average molecular weight 3,000,000, Shore D hardness 66) and the like can be mentioned.
【００１０】本発明においては、上記のポリオレフィン
と超高分子量ポリエチレンとを混合させてベースポリマ
ーを構成する。両者の混合割合は、ポリオレフィンと超
高分子量ポリエチレンとの重量比で、９５〜６０：５〜
４０、好ましくは９０〜６５：１０〜３５の範囲であ
る。超高分子量ポリエチレンの配合量が上記範囲より少
なすぎると耐外傷性改良効果が低くなるという傾向があ
り、逆に多すぎるとフィラー受容体としてのポリオレフ
ィンの割合が減るのでフィラー受容量も減り、その結果
難燃性が低下してしまうという傾向があるため好ましく
ない。In the present invention, the above-mentioned polyolefin is mixed with the ultrahigh molecular weight polyethylene to form the base polymer. The mixing ratio of both is 95 to 60: 5 in terms of the weight ratio of polyolefin and ultra high molecular weight polyethylene.
The range is 40, preferably 90 to 65:10 to 35. If the blending amount of the ultra high molecular weight polyethylene is less than the above range, the trauma resistance improving effect tends to be low, and conversely if the blending amount is too large, the proportion of the polyolefin as the filler acceptor decreases, so the filler accepting capacity also decreases. As a result, the flame retardancy tends to decrease, which is not preferable.
【００１１】本発明組成物に難燃性付与剤として混合さ
れる水和金属酸化物としては、例えば水酸化アルミニウ
ム、水酸化マグネシウム、ハンタイト（Ｍｇ3 Ｃａ（Ｃ
Ｏ3）4 ）とハイドロマグネサイトとの混合物等のハイ
ドロタルサイト類等があげられる。Examples of the hydrated metal oxide mixed in the composition of the present invention as a flame retardant imparting agent include, for example, aluminum hydroxide, magnesium hydroxide and huntite (Mg 3 Ca (C
Examples thereof include hydrotalcites such as a mixture of O 3 ) 4 ) and hydromagnesite.
【００１２】該水和金属酸化物の配合量は、上記ベース
ポリマー１００重量部当たり、５０〜３００重量部、好
ましくは７０〜２００重量部、特に好ましくは８０〜１
５０重量部である。その配合量が５０重量部未満では満
足できる難燃性が実現できず、３００重量部を越えると
本発明のベースポリマーを使用しても機械的強度が低下
する傾向が出るため望ましくない。The amount of the hydrated metal oxide compounded is 50 to 300 parts by weight, preferably 70 to 200 parts by weight, and particularly preferably 80 to 1 part by weight per 100 parts by weight of the base polymer.
It is 50 parts by weight. If the content is less than 50 parts by weight, satisfactory flame retardancy cannot be realized, and if it exceeds 300 parts by weight, mechanical strength tends to decrease even if the base polymer of the present invention is used, which is not desirable.
【００１３】本発明の難燃性樹脂組成物には、必要に応
じて種々の添加剤を配合してもよい。例えば、マレイン
酸変性のポリエチレン、ポリプロピレン、エチレンプロ
ピレンゴム等のポリマーブレンド相溶化剤、タルク、ク
レー、炭酸カルシウム、炭酸マグネシウム、シリカのよ
うな充填剤、カーボンブラック、酸化チタン、フタロシ
アニンブルー、ベンガラのような着色剤、ビンダードフ
ェノール類、芳香族アミン類のような老化防止剤、赤リ
ン、ホウ酸亜鉛、ヒドロキシ錫酸亜鉛、錫酸亜鉛、酸化
アンチモンのような難燃助剤、ステアリン酸、オレイン
酸、高級脂肪酸金属塩のような滑剤、加工助剤、チタネ
ート系やシラン系等のカップリング剤などを添加するこ
とができる。The flame-retardant resin composition of the present invention may contain various additives as required. For example, polymer blend compatibilizers such as maleic acid modified polyethylene, polypropylene, ethylene propylene rubber, talc, clay, fillers such as calcium carbonate, magnesium carbonate, silica, carbon black, titanium oxide, phthalocyanine blue, red iron oxide, etc. Colorants, Bindered phenols, Anti-aging agents such as aromatic amines, Red phosphorus, Zinc borate, Zinc hydroxystannate, Zinc stannate, Flame retardant aids such as antimony oxide, Stearic acid, Olein Lubricants such as acids and higher fatty acid metal salts, processing aids, titanate-based and silane-based coupling agents and the like can be added.
【００１４】さらに必要に応じて、ジクミルパーオキサ
イド、１，１−ビス（ｔ−ブチルパーオキシ）−３、
３，５−トリメチルシクロヘキサン等のパーオキサイ
ド、Ｐ−キノンジオキシム、Ｐ−Ｐ´−ジベンゾイル、
キノンジオキシム等のオキシム類、Ｎ−Ｎ´−メタフェ
ニレンジマレイミド、トリメチルプロパントリメタアク
リレート、ポリブタジエンオリゴマー、ジアリルフタレ
ート等の２官能性架橋助剤の１種または２種以上を少量
（例えば０．１〜３重量部）添加して熱処理してもよ
い。Further, if necessary, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,
Peroxides such as 3,5-trimethylcyclohexane, P-quinonedioxime, P-P'-dibenzoyl,
A small amount (for example, 0. (1 to 3 parts by weight) may be added for heat treatment.
【００１５】本発明の組成物は各種用途に適用可能であ
り、特に電線・ケーブルの絶縁体及び外部シース等の被
覆材料として極めて好適である。就中、自動車用電線、
ビル内配線ケーブル等に特に有用である。すなわち、本
発明組成物はハロゲンフリーであるので無公害であると
共に、機械的強度が優れているので外力への耐性が良好
でしかも薄肉化も可能である点で特に有利である。この
他に本発明組成物は、例えばパイプ、ホース、各種シー
ト、建材などにも好適に使用できる。The composition of the present invention can be applied to various uses, and is particularly suitable as a coating material for electric wire / cable insulators and outer sheaths. Above all, electric wires for automobiles,
It is especially useful for wiring cables in buildings. That is, since the composition of the present invention is halogen-free, it is non-polluting, and it is particularly advantageous in that it has excellent mechanical strength and thus has good resistance to external force and can be thinned. In addition to this, the composition of the present invention can be suitably used for pipes, hoses, various sheets, building materials, and the like.
【００１６】[0016]
【実施例】表１に示す配合で、７種類の本発明にかかる
難燃性樹脂組成物（実施例１〜７）の試料を作成した。
該試料は、各組成物を１３０℃のミキシングロールで混
練し、その後１７０℃×１０分の条件で加熱プレス成形
することにより形成した、厚さ１mmのシート状試料とし
た。また実施例品と比較のため、表１に示す配合で３種
類の難燃性樹脂組成物（比較例１〜３）からなるシート
状試料を前記と同様にして作成した。これらの試料の特
性を、以下の方法で評価した。その結果を表１に示す。[Examples] With the formulation shown in Table 1, seven types of samples of flame-retardant resin compositions according to the present invention (Examples 1 to 7) were prepared.
The sample was a sheet-like sample having a thickness of 1 mm, which was formed by kneading each composition with a mixing roll at 130 ° C. and then hot-press molding under the condition of 170 ° C. × 10 minutes. Further, for comparison with the example products, sheet-like samples composed of three types of flame-retardant resin compositions (Comparative Examples 1 to 3) with the formulations shown in Table 1 were prepared in the same manner as above. The characteristics of these samples were evaluated by the following methods. The results are shown in Table 1.
【００１７】抗張力、伸び試験 上記のシート状試料それぞれに対し、ＪＩＳ Ｋ６７２
３の引張り試験方法に準拠して抗張力及び伸び率を試験
した。なお、引張り強さは１．３Ｋｇ／mm2 以上を合格
とし、また伸び率は１５０％以上を合格とした。Tensile Strength and Elongation Test For each of the above sheet-like samples, JIS K672
Tensile strength and elongation were tested according to the tensile test method of No. 3. The tensile strength was 1.3 Kg / mm 2 or more, and the elongation was 150% or more.
【００１８】テーバ磨耗試験 上記のシート状試料それぞれに対し、ＡＳＴＭ−Ｄ１０
４４−５６『透明プラスチックの表面の耐摩耗性』測定
方法に準拠して、Ｈ−１８摩耗輪を用い１０００回実行
時の摩耗量をｍｇで示した。Taber Abrasion Test For each of the above sheet samples, ASTM-D10
44-56 "Abrasion resistance of the surface of transparent plastic" Based on the measuring method, the amount of abrasion after 1000 times of execution using an H-18 abrasion wheel is shown in mg.
【００１９】難燃性試験 上記のシート状試料それぞれに対し、ＪＩＳ Ｋ７２０
１（酸素指数法）に準拠して酸素指数を求め難燃性を評
価した。Flame Retardancy Test For each of the above sheet-like samples, JIS K720
Based on 1 (oxygen index method), the oxygen index was obtained and the flame retardancy was evaluated.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【発明の効果】以上説明した通りの本発明の難燃性樹脂
組成物によれば、所要の難燃性を十分備えていると共に
優れた対外傷性や耐摩耗性を備えており、各種用途に適
用した場合高耐久性とすることができる。また前記のよ
うな機械特性に優れているので、従来品に比べ薄肉成形
しても十分強度特性を満足させることができるので、例
えば電線被覆材として使用した場合、その電線外径を縮
小することが可能となる。さらにハロゲンフリーである
ので無公害である等、本発明は優れた効果を奏するもの
である。As described above, according to the flame-retardant resin composition of the present invention, the flame-retardant resin composition is sufficiently provided with required flame retardancy, and is excellent in external damage resistance and abrasion resistance. When applied to, it can be highly durable. In addition, since it has excellent mechanical properties as described above, it can satisfy the strength properties sufficiently even if it is formed thinner than conventional products.For example, when used as a wire covering material, the outer diameter of the wire should be reduced. Is possible. Furthermore, since the present invention is halogen-free, it is non-polluting, and the present invention has excellent effects.
Claims (1)
リオレフィンと、平均分子量が３０万以上でショアＤ硬
度が５０以上の超高分子量ポリエチレンとを、前者と後
者との重量比で９５〜６０：５〜４０の混合割合でブレ
ンドしたポリマー１００重量部に対し、水和金属酸化物
を５０〜３００重量部配合したことを特徴とする難燃性
樹脂組成物。1. A polyolefin having a density of 0.85 to 0.93 g / cm 3 and an ultra high molecular weight polyethylene having an average molecular weight of 300,000 or more and a Shore D hardness of 50 or more in a weight ratio of the former and the latter. A flame-retardant resin composition comprising 50 to 300 parts by weight of a hydrated metal oxide based on 100 parts by weight of a polymer blended at a mixing ratio of 95 to 60: 5 to 40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17941192A JPH05339437A (en) | 1992-06-12 | 1992-06-12 | Flame-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17941192A JPH05339437A (en) | 1992-06-12 | 1992-06-12 | Flame-resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05339437A true JPH05339437A (en) | 1993-12-21 |
Family
ID=16065400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17941192A Pending JPH05339437A (en) | 1992-06-12 | 1992-06-12 | Flame-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05339437A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999055776A1 (en) * | 1998-04-24 | 1999-11-04 | Chisso Corporation | Flame retardant polyolefin composition |
| JP2003510394A (en) * | 1999-09-17 | 2003-03-18 | エス・ア・ジェ・ウ・エム・ソシエテ・アノニム | Extrudable thermoplastic materials and fiber micromodules made from such materials |
| JP2012111001A (en) * | 2010-11-25 | 2012-06-14 | Nikon Corp | Work carrier and polishing device having work carrier |
| JP2012229343A (en) * | 2011-04-26 | 2012-11-22 | Mitsubishi Cable Ind Ltd | Resin composition and electric wire for automobile covered with the resin composition |
| JP2013035944A (en) * | 2011-08-08 | 2013-02-21 | Yazaki Energy System Corp | Crosslinked resin composition, wire and cable using the same |
| JP2014111889A (en) * | 2009-10-07 | 2014-06-19 | Sungyull Lee | Filler for artificial lawn, and artificial lawn containing the same |
-
1992
- 1992-06-12 JP JP17941192A patent/JPH05339437A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999055776A1 (en) * | 1998-04-24 | 1999-11-04 | Chisso Corporation | Flame retardant polyolefin composition |
| US6444736B1 (en) | 1998-04-24 | 2002-09-03 | Chisso Corporation | Flame retardant polyolefin composition |
| JP2003510394A (en) * | 1999-09-17 | 2003-03-18 | エス・ア・ジェ・ウ・エム・ソシエテ・アノニム | Extrudable thermoplastic materials and fiber micromodules made from such materials |
| JP2014111889A (en) * | 2009-10-07 | 2014-06-19 | Sungyull Lee | Filler for artificial lawn, and artificial lawn containing the same |
| JP2012111001A (en) * | 2010-11-25 | 2012-06-14 | Nikon Corp | Work carrier and polishing device having work carrier |
| JP2012229343A (en) * | 2011-04-26 | 2012-11-22 | Mitsubishi Cable Ind Ltd | Resin composition and electric wire for automobile covered with the resin composition |
| JP2013035944A (en) * | 2011-08-08 | 2013-02-21 | Yazaki Energy System Corp | Crosslinked resin composition, wire and cable using the same |
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