JPH05301996A - Flame-retardant resin composition - Google Patents

Flame-retardant resin composition

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Publication number
JPH05301996A
JPH05301996A JP13156692A JP13156692A JPH05301996A JP H05301996 A JPH05301996 A JP H05301996A JP 13156692 A JP13156692 A JP 13156692A JP 13156692 A JP13156692 A JP 13156692A JP H05301996 A JPH05301996 A JP H05301996A
Authority
JP
Japan
Prior art keywords
flame
resin composition
retardant resin
density
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.)
Granted
Application number
JP13156692A
Other languages
Japanese (ja)
Other versions
JP3210411B2 (en
Inventor
Kiyoshi Furukawa
清志 古川
Takanori Miyata
任規 宮田
Tadao Tachibana
忠男 橘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Cable Industries Ltd
Original Assignee
Mitsubishi Cable Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Priority to JP13156692A priority Critical patent/JP3210411B2/en
Publication of JPH05301996A publication Critical patent/JPH05301996A/en
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Publication of JP3210411B2 publication Critical patent/JP3210411B2/en
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Abstract

PURPOSE:To provide the subject flame-retardant non-halogen resin composition excellent in flame retardancy and mechanical strengths such as mar resistance and abrasion resistance and useful as a wire coating material, etc. CONSTITUTION:This invented flame-retardant resin composition is obtained by blending a polyolefin of 0.85 to 0.94g/cm<3> density with a high-density polyethylene of >=0.94g/cm<3> in a weight ratio of (95 to 65):(5 to 35), using the resultant mixture as the base polymer and blending 50 to 300 pts.wt. metallic oxide hydrate with 100 pts.wt. base polymer.

Description

【発明の詳細な説明】Detailed Description of the Invention

【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0.85〜0.94g/cm3 のポリオレフ
ィンと、密度が0.94g/cm3 以上の高密度ポリエチ
レンとを、前者と後者との重量比で95〜65:5〜3
5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 According to an aspect of the polyolefin having a density of 0.85~0.94g / cm 3, density and 0.94 g / cm 3 or more high-density polyethylene The weight ratio of the former to the latter is 95 to 65: 5 to 3
It is characterized in that 50 to 300 parts by weight of a hydrated metal oxide is blended with 100 parts by weight of a polymer blended at a mixing ratio of 5.

【0005】[0005]

【発明の開示】本発明の、ポリオレフィンに所定量高密
度ポリエチレンを配合したベースポリマーであれば、高
密度ポリエチレンが有する高結晶性が作用するためか、
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耐外傷性や耐摩耗性などの機械
特性が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 In the case of the base polymer of the present invention in which a predetermined amount of high density polyethylene is blended with polyolefin, the high crystallinity of high density polyethylene may act.
Even if a large amount of hydrated metal oxide is added to improve flame retardancy,
It has been found that mechanical properties such as external damage resistance and abrasion resistance of the flame-retardant resin composition can 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.
94g/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などが好ま
しく使用できる。
The density used in the present invention is 0.85 to 0.
Examples of the 94 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 can give. 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】また高密度ポリエチレンとしては、密度が
0.94g/cm3 以上のもの、好ましくは0.95g/
cm3 以上のものが使用でき、具体的にはユカロンEX4
0(三菱油化株式会社商品名;密度0.96g/c
m3 )、ハイゼックス5305(三井石油化学株式会社
商品名;密度0.954g/cm3 )、ショウレックスC
4502(昭和電工株式会社商品名;密度0.943g
/cm3 )、スタクレンE802(日本石油化学株式会社
商品名;密度0.967g/cm3 )、ニポロンハード6
200(東ソー株式会社商品名;密度0.957g/cm
3 )などを例示することができる。
The high-density polyethylene has a density of 0.94 g / cm 3 or more, preferably 0.95 g / cm 3.
cm 3 or more ones can be used, specifically Yukaron EX4
0 (trade name of Mitsubishi Petrochemical Co., Ltd .; density 0.96 g / c
m 3 ), Hi-Zex 5305 (trade name of Mitsui Petrochemical Co., Ltd .; density 0.954 g / cm 3 ), Shorex C
4502 (trade name of Showa Denko KK; Density 0.943 g
/ Cm 3 ), Staclen E802 (trade name of Nippon Petrochemicals Co. Ltd .; density 0.967 g / cm 3 ), Nipolon Hard 6
200 (trade name of Tosoh Corporation; density 0.957 g / cm
3 ) etc. can be illustrated.

【0008】本発明においては、上記のポリオレフィン
と高密度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、ポリオレフィンと高密度
ポリエチレンとの重量比で、95〜65:5〜35、好
ましくは90〜70:10〜30の範囲である。高密度
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
傷性や耐磨耗性の改良効果が低下するという傾向があ
り、逆に多すぎると非晶質部分が少なくなって難燃剤を
多量に混合できなくなり難燃性が低下するという傾向が
あるため好ましくない。
In the present invention, the above-mentioned polyolefin and high-density polyethylene are mixed to form a base polymer. The mixing ratio of both is 95 to 65: 5 to 35, preferably 90 to 70:10 to 30, as a weight ratio of polyolefin and high density polyethylene. If the amount of the high-density polyethylene is less than the above range, the effect of improving the trauma resistance and abrasion resistance tends to decrease, and conversely, if the amount is too large, the amorphous part decreases and the amount of flame retardant increases. It is not preferable because there is a tendency that mixing becomes impossible and flame retardancy decreases.

【0009】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
34 )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 with the composition of the present invention as a flame retardant imparting agent include aluminum hydroxide, magnesium hydroxide, huntite (Mg 3 Ca (C
Examples thereof include hydrotalcites such as a mixture of O 3 ) 4 ) and hydromagnesite.

【0010】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.

【0011】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.

【0012】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.

【0013】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.

【0014】[0014]

【実施例】表1に示す配合で、8種類の本発明にかかる
難燃性樹脂組成物(実施例1〜8)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 formulations shown in Table 1, eight kinds of flame-retardant resin compositions according to the present invention (Examples 1 to 8) 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.

【0015】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 was used.
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.

【0016】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-like 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.

【0017】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.

【0018】[0018]

【表1】 [Table 1]

【0019】[0019]

【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)

【特許請求の範囲】[Claims] 【請求項1】 密度が0.85〜0.94g/cm3 のポ
リオレフィンと、密度が0.94g/cm3 以上の高密度
ポリエチレンとを、前者と後者との重量比で95〜6
5:5〜35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。
A polyolefin as claimed in claim 1] density 0.85~0.94g / cm 3, density and 0.94 g / cm 3 or more high-density polyethylene, in a weight ratio of the former and the latter 95-6
Polymer 100 blended in a mixing ratio of 5: 5 to 35
A flame-retardant resin composition comprising 50 to 300 parts by weight of a hydrated metal oxide with respect to parts by weight.
JP13156692A 1992-04-24 1992-04-24 Flame retardant resin composition Expired - Lifetime JP3210411B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP13156692A JP3210411B2 (en) 1992-04-24 1992-04-24 Flame retardant resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP13156692A JP3210411B2 (en) 1992-04-24 1992-04-24 Flame retardant resin composition

Publications (2)

Publication Number Publication Date
JPH05301996A true JPH05301996A (en) 1993-11-16
JP3210411B2 JP3210411B2 (en) 2001-09-17

Family

ID=15061061

Family Applications (1)

Application Number Title Priority Date Filing Date
JP13156692A Expired - Lifetime JP3210411B2 (en) 1992-04-24 1992-04-24 Flame retardant resin composition

Country Status (1)

Country Link
JP (1) JP3210411B2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034162A (en) * 1997-03-31 2000-03-07 Sumitomo Wiring Systems, Ltd. Wear-resistant and flame-retardant resin composition, method of manufacturing resin composition, and insulated electric wire
US6190772B1 (en) 1998-07-14 2001-02-20 Sumitomo Wiring Systems, Ltd. Flame-retardant, wear-resistant resin composition, useful for electrical insulation
US6646205B2 (en) 2000-12-12 2003-11-11 Sumitomo Wiring Systems, Ltd. Electrical wire having a resin composition covering
CN101807451A (en) * 2010-04-14 2010-08-18 四川新蓉电缆有限责任公司 Cable fillers
JP2014518907A (en) * 2011-05-04 2014-08-07 ボレアリス エージー Polymer compositions for electrical devices
CN104403186A (en) * 2014-11-14 2015-03-11 宁波一舟塑胶有限公司 Composite synergistic flame-retardant smoke-suppression low-smoke halogen-free framework material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034162A (en) * 1997-03-31 2000-03-07 Sumitomo Wiring Systems, Ltd. Wear-resistant and flame-retardant resin composition, method of manufacturing resin composition, and insulated electric wire
US6190772B1 (en) 1998-07-14 2001-02-20 Sumitomo Wiring Systems, Ltd. Flame-retardant, wear-resistant resin composition, useful for electrical insulation
US6646205B2 (en) 2000-12-12 2003-11-11 Sumitomo Wiring Systems, Ltd. Electrical wire having a resin composition covering
US6756440B2 (en) 2000-12-12 2004-06-29 Sumitomo Wiring Systems, Ltd. Fire resistant resin composition and electrical wire having fire resistant covering
US6809140B2 (en) 2000-12-12 2004-10-26 Sumitomo Wiring Systems, Ltd. Fire resistant resin composition and electrical wire having fire resistant covering
CN101807451A (en) * 2010-04-14 2010-08-18 四川新蓉电缆有限责任公司 Cable fillers
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