JPS59160911A - Flame resistance, low smoke polyolefin resin coated wire - Google Patents
Flame resistance, low smoke polyolefin resin coated wireInfo
- Publication number
- JPS59160911A JPS59160911A JP3507383A JP3507383A JPS59160911A JP S59160911 A JPS59160911 A JP S59160911A JP 3507383 A JP3507383 A JP 3507383A JP 3507383 A JP3507383 A JP 3507383A JP S59160911 A JPS59160911 A JP S59160911A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- carbonate
- flame
- vinyl acetate
- smoke
- 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.)
- Pending
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- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、難燃性で煙の発生が少なく、かつ腐食性ガス
を発生しない難燃、低煙ポリオレフィン樹脂被覆電線に
関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a flame-retardant, low-smoke polyolefin resin-coated electric wire that is flame-retardant, generates little smoke, and does not generate corrosive gases.
近年、ビル用配線や機器内配線の難燃性に対する要求は
益々厳しくなっており、難燃性であることは言うまでも
なく、発煙性も少なく、その上人体及び機器に悪影響を
及ぼす有害なガスを発生しないことが求められている。In recent years, the requirements for flame retardancy for building wiring and equipment internal wiring have become increasingly strict, and it goes without saying that they must be flame retardant, emit less smoke, and, moreover, must be free of harmful gases that have an adverse effect on the human body and equipment. It is expected that this will not occur.
これらの要求を満たすには、ポリ塩化ビニル樹脂等のハ
ロゲンを分子構造に含む樹脂では、燃焼時に腐食性の有
害ガスを発生する為使用できない。又ポリオレフィン樹
脂等9ハロゲンを含まない樹脂では、一般的にハロゲン
化合物から成る難燃剤を添加して難燃化を計っており、
この場合も、燃焼時にハロゲンガスが発生する。そこで
ノ・ロゲンを使用しないいわゆる水和金属酸化物を添加
して難燃性を付与する方法が有効となり、水和金属酸化
物として水酸化アルミニウム、水酸化マグネシウム等を
使用することがよく知られている。To meet these requirements, resins containing halogen in their molecular structure, such as polyvinyl chloride resin, cannot be used because they generate corrosive and harmful gases when burned. In addition, for resins that do not contain 9 halogens, such as polyolefin resins, flame retardants consisting of halogen compounds are generally added to make them flame retardant.
In this case, halogen gas is also generated during combustion. Therefore, a method of imparting flame retardance by adding so-called hydrated metal oxides that do not use norogens has become effective, and it is well known that aluminum hydroxide, magnesium hydroxide, etc. are used as hydrated metal oxides. ing.
今、難燃性の評価方法の1つである酸素指数法U Is
−に−7201)によって、金属炭酸塩及び水和金属酸
化物を充填したポリオレフィン樹脂の酸素指数を測定し
、第1図に示した。第1図にお(1て、m は炭酸マグ
ネシウムの、(2)は水酸化マグネシウムの、(3)は
水酸化アルミニウムの、(4)はホウ酸亜鉛の充填剤量
に対する酸素指数の変化を示す。一般に難燃性を酸素指
数で表わす場合、水平難燃程度で酸素指数は22〜25
、垂直難燃て27〜30以上と言われている。今、垂直
難燃の難燃度である酸素指数30を達成するに必要な充
填剤量を第1図から求めると、100重量部以上の添加
が必要であることがわかる。Currently, the oxygen index method is one of the evaluation methods for flame retardancy.
The oxygen index of the polyolefin resin filled with metal carbonates and hydrated metal oxides was measured using the method (Ni-7201) and is shown in FIG. Figure 1 (1) shows the change in oxygen index with respect to the filler amount of m for magnesium carbonate, (2) for magnesium hydroxide, (3) for aluminum hydroxide, and (4) for zinc borate. Generally speaking, when flame retardancy is expressed as an oxygen index, the oxygen index is 22 to 25 at horizontal flame retardance level.
It is said that the vertical flame retardancy is 27-30 or higher. Now, when the amount of filler necessary to achieve an oxygen index of 30, which is the degree of flame retardance for vertical flame retardation, is determined from FIG. 1, it is found that 100 parts by weight or more is required to be added.
発煙性については、NBSスモークデンシティ−チャン
バーを用いて測定し、flaming での最大煙密
度(Dm)を第、2図に示した。第2図における符号は
第1図と同様の充填剤を示す。この図から、わかる様に
発煙量を少なくするには充填剤量を多くする必要がある
。所がポリエチレン等の結晶性ポリマーでは、100重
量部以上の充填剤を添加すれば、物性、加工性等が著し
く損われ成形できない。The smoke generation property was measured using an NBS smoke density chamber, and the maximum smoke density (Dm) at flaming is shown in Figure 2. The numbers in FIG. 2 indicate the same fillers as in FIG. As can be seen from this figure, it is necessary to increase the amount of filler in order to reduce the amount of smoke generated. However, in the case of crystalline polymers such as polyethylene, if 100 parts by weight or more of filler is added, the physical properties, processability, etc. will be significantly impaired and molding will not be possible.
その為、ペースポリマーとしては、これらの充填剤を多
量に添加しても物性、加工性等がある程度以上保持され
るものを使用しなければならない。Therefore, it is necessary to use a pace polymer that maintains its physical properties, processability, etc. to a certain extent even when a large amount of these fillers is added.
充填剤が多量に添加出来るポリマーとしては、EPゴム
等のゴム類、エチレン−酢酸ビニル共重合体、エチレン
−α−オレフィン共重合体等がある。これらのポリマー
の中でも酢酸ビニル含有量が50%以上であるエチレン
−酢酸ビニル共重合体は、200〜300重量部の高充
填でも成形可能であり、フィラー高充填ポリマーとして
適している。ベースポリマーとして、エチレン−酢酸ビ
ニル共重合体単独で使用することが好ましいが、要求さ
れる特性により、他のポリマー、例えばポリエチレン、
ポリプロピレン、エチレン−酢酸ビニル共重合体(酢酸
ビニル含有量5096未満)、エチレン−エチルアクリ
レート共重合体、エチレン−αオレフィン共重合体、E
Pゴム(EPDM)、ブチルゴム、ポリブタジェン、ポ
リウレタン等とブレンドして使用することも可能である
。Examples of polymers to which a large amount of filler can be added include rubbers such as EP rubber, ethylene-vinyl acetate copolymers, and ethylene-α-olefin copolymers. Among these polymers, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 50% or more can be molded even at a high filling of 200 to 300 parts by weight, and is suitable as a highly filled filler polymer. It is preferable to use ethylene-vinyl acetate copolymer alone as the base polymer, but depending on the required properties, other polymers such as polyethylene,
Polypropylene, ethylene-vinyl acetate copolymer (vinyl acetate content less than 5096), ethylene-ethyl acrylate copolymer, ethylene-α olefin copolymer, E
It is also possible to use it in a blend with P rubber (EPDM), butyl rubber, polybutadiene, polyurethane, etc.
この様にして、水和金属酸化物、金属炭酸塩等をハロゲ
ンを含まないポリマーに高充填して、腐食ガスを出さな
いで難燃化及び低煙化を計ることはすでによく知られる
ところである。所が機械的特性等の物性及び加工性の面
から見ると、充填する充填剤量は、出来るだけ少ない方
が好ましい。In this way, it is already well known that hydrated metal oxides, metal carbonates, etc. are highly loaded into halogen-free polymers to achieve flame retardancy and low smoke without emitting corrosive gases. . However, from the viewpoint of physical properties such as mechanical properties and processability, it is preferable that the amount of filler to be filled is as small as possible.
本発明は、この様な見地から、同一充填剤量あるいはよ
り少ない充填剤量で低煙、難燃化を計るべく検討したも
のである。From this perspective, the present invention was developed to achieve low smoke and flame retardancy with the same amount of filler or a smaller amount of filler.
本発明は、前述の水和金属酸化物あるいは金属炭酸塩に
ホウ酸亜鉛を添加することにより、低煙化と難燃化を同
時に計ることが出来ることを見い出され、この知見に基
いて為されたもので、その要旨とするところは酢酸ビニ
ル含有量が50重量%以上であるエチレン−酢酸ビニル
共重合体を主体とするポリオレフィン樹脂組成物に、充
填剤として水和金属酸化物あるいは金属炭酸塩とホウ酸
亜鉛とを両者あわせて100重量部以上とし、かつ、充
填剤中のホウ酸亜鉛の比率を0.25〜0.75 とし
て添加し放射線で架橋した組成物を絶縁又はシースとし
て用いたことを特徴とする放射線照射架橋低煙、難燃ポ
リオレフィン樹脂被覆電線にある。The present invention was made based on the discovery that low smoke and flame retardance can be achieved at the same time by adding zinc borate to the hydrated metal oxide or metal carbonate mentioned above. The gist of this is that a hydrated metal oxide or metal carbonate is added as a filler to a polyolefin resin composition mainly composed of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 50% by weight or more. and zinc borate in a total of 100 parts by weight or more, and the ratio of zinc borate in the filler was 0.25 to 0.75, and the composition was crosslinked with radiation and used as an insulation or sheath. It is a radiation-irradiated cross-linked, low-smoke, flame-retardant polyolefin resin coated electric wire.
〔発明の詳細な説明〕
本発明において、ポリオレフィン樹脂とは、酢酸ビニル
含有量が50重量%以上であるエチレン−酢酸ビニル共
重合体、単独あるいは、ポリエチレン、ポリプロピレン
、エチレン−酢酸ビニル共重合体、エチレン−エチルア
クリレート共重合体、エチレン−αオレフィン共重合体
、EPゴム、ブチルゴム、ポリブタジェン、ポリウレタ
ン等とのブレンド物を意味する。[Detailed Description of the Invention] In the present invention, the polyolefin resin refers to an ethylene-vinyl acetate copolymer having a vinyl acetate content of 50% by weight or more, alone, or polyethylene, polypropylene, ethylene-vinyl acetate copolymer, It means a blend with ethylene-ethyl acrylate copolymer, ethylene-α olefin copolymer, EP rubber, butyl rubber, polybutadiene, polyurethane, etc.
水和金属酸化物としては、水酸化アルミニウム、水酸化
マグネシウム、水酸化カルシウム、水酸化バリウムなど
が挙げられる。Examples of hydrated metal oxides include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like.
金属炭酸塩としては、炭酸マグネシウム、炭酸マグネシ
ウムカルシウム、炭酸カルシウム、炭酸亜鉛、炭酸バリ
ウムなどが挙げられる。Examples of metal carbonates include magnesium carbonate, calcium magnesium carbonate, calcium carbonate, zinc carbonate, and barium carbonate.
水和金属酸化物あるいは金属炭酸塩とホウ酸亜鉛の配合
量が合わせて100重量部以上である理由は、100重
量部以上添加しないと樹脂組成物の酸素指数が、垂直難
燃領域である30を越えないからである。一方、最大配
合量は、ポリオレフィン樹脂の種類によって異なる為、
−律に定められない。The reason why the combined amount of hydrated metal oxide or metal carbonate and zinc borate is 100 parts by weight or more is that if 100 parts by weight or more is not added, the oxygen index of the resin composition will be in the vertical flame retardant region of 30. This is because it does not exceed On the other hand, the maximum blending amount varies depending on the type of polyolefin resin, so
-Not prescribed by law.
例えば、酢酸ビニル含有量が50重量%を越えるエチレ
ン−酢酸ビニル共重合体単独の場合では、300重量部
程度までは配合することが出来る。For example, in the case of an ethylene-vinyl acetate copolymer alone having a vinyl acetate content exceeding 50% by weight, up to about 300 parts by weight can be blended.
本発明においては充填剤中のホウ酸亜鉛の重量比率が0
.25〜075のとき優れた低煙性と難燃性を示す。f
なわち、重量比率が025未満のときは発煙量低減の効
果が少なく、075を越えると酸素指数が30に満たな
くなる。In the present invention, the weight ratio of zinc borate in the filler is 0.
.. When it is 25 to 075, it exhibits excellent low smoke properties and flame retardancy. f
That is, when the weight ratio is less than 025, the effect of reducing the smoke amount is small, and when it exceeds 075, the oxygen index becomes less than 30.
本発明において、放射線架橋の効果は、低煙、難燃化を
計る為に多量に充填剤を添加することによる物性低下を
改善することにある。例えば、エチレン−酢酸ビニル共
重合体に水和金属酸化物を100重量部添加した場合の
抗張力は0.1 kg/mm 2と小さく、実用に耐え
ない。所が電子線を20Mrad照則することにより、
抗張力は0.6 kg/inm ”となり、通常の架硫
ゴム等と同等のレベルとなり、十分に実用できるもので
ある。In the present invention, the effect of radiation crosslinking is to improve the deterioration in physical properties caused by adding a large amount of filler to achieve low smoke and flame retardancy. For example, when 100 parts by weight of a hydrated metal oxide is added to an ethylene-vinyl acetate copolymer, the tensile strength is as small as 0.1 kg/mm 2 , which is not practical. By illuminating the electron beam at 20 Mrad,
The tensile strength is 0.6 kg/inm'', which is at the same level as ordinary cross-sulfurized rubber, and is sufficiently usable for practical use.
又、放射線架橋が最適である理由は、材料の成形温度に
よらず架橋することが出来る為である。Further, the reason why radiation crosslinking is optimal is that crosslinking can be performed regardless of the molding temperature of the material.
即ち、本発明のごとく充填剤を多量に添加する材料を有
機・ペルオキシドによる化学架橋で行なおうとする場合
、成形時のトルクが高くなり材料温度が200℃付近ま
で高くなり、有機ペルオキシドの分解温度(120〜1
80℃程度)を越えてしまい、成型機内で架橋が起こり
成形できない。That is, when attempting to chemically crosslink a material with a large amount of filler added as in the present invention using an organic peroxide, the torque during molding becomes high, the material temperature rises to around 200°C, and the decomposition temperature of the organic peroxide increases. (120~1
(approximately 80°C), crosslinking occurs in the molding machine, making molding impossible.
以下に本発明について具体例をもって説明する。The present invention will be explained below using specific examples.
第1表に示した配合で、絶縁外径2.4 mm、導体径
O8n1mの電線を作り電子線を20Mrad照射した
後、所定サイズに電線を並べNBSスモークチャンバー
による被覆層の発煙量(最大煙密度Dm )と酸素指第
1 表
1)エチレン−酢酸ビニル共重合体
、(酢酸ビニル含有量 60%)
2)水酸化アルミニウム
数を測定した。その結果をそれぞれ第3図、第4゜図に
示した。第3図から明らかな様に、ホウ酸亜鉛を添加す
るに従い、発煙量の低下がみられ充填剤をすべてホウ酸
亜鉛に置かえた場合には第44図から難燃性が満たされ
ない。第3図、第4図より、充填剤に占めるホウ酸亜鉛
比率が、0.25〜0.75が最適であることがわかる
。炭酸金属塩とホウ酸亜鉛の組合せについて、第2表に
示した配合で外径2.4mm、導体径0.8Mの電線を
作成し、電子線を20Mrad照射した後、発煙量及び
酸素指数を測定し、その結果をそれぞれ第5図、第6図
に示した。炭酸金属塩とホウ酸亜鉛の組合せでもやはり
、充填剤に占めるホウ酸亜鉛の比率が0.25〜075
の場合、難燃性、低煙性ともに優れていることがわかる
。Using the composition shown in Table 1, wires with an insulation outer diameter of 2.4 mm and a conductor diameter of O8n1m were made, and after being irradiated with an electron beam of 20 Mrad, the wires were arranged in a predetermined size and the amount of smoke emitted from the coating layer (maximum smoke) was measured using an NBS smoke chamber. Density Dm) and oxygen index Table 1 1) Ethylene-vinyl acetate copolymer, (vinyl acetate content 60%) 2) Aluminum hydroxide number were measured. The results are shown in Figures 3 and 4, respectively. As is clear from FIG. 3, as zinc borate is added, the amount of smoke generation decreases, and when all the filler is placed in zinc borate, the flame retardance is not satisfied as shown in FIG. 44. From FIG. 3 and FIG. 4, it can be seen that the optimal ratio of zinc borate to the filler is 0.25 to 0.75. Regarding the combination of metal carbonate and zinc borate, an electric wire with an outer diameter of 2.4 mm and a conductor diameter of 0.8 M was prepared using the composition shown in Table 2, and after irradiating it with an electron beam of 20 Mrad, the amount of smoke and oxygen index were measured. The results were shown in FIGS. 5 and 6, respectively. In the combination of metal carbonate and zinc borate, the ratio of zinc borate to the filler is 0.25 to 0.75.
In the case of , it can be seen that both flame retardancy and low smoke properties are excellent.
この様に本発明によって酸素指数が30以上という高難
燃性で、かつ、発煙性の少ない被覆電線が得られた。As described above, according to the present invention, a coated electric wire having high flame retardance with an oxygen index of 30 or more and low smoke generation was obtained.
第 2 表 1)エチレン−酢酸ビニル共重合体 (酢酸ビニル含有量 60%) 2)炭酸マグネシウムTable 2 1) Ethylene-vinyl acetate copolymer (Vinyl acetate content 60%) 2) Magnesium carbonate
第1図は、各種充填剤添加量と酸素指数の関係を示すグ
ラフである。
第2図は、各種充填剤添加量と発煙量の関係を示すグラ
フである。
第3図は、水和金属酸化物とホウ酸亜鉛の添加比率と発
煙量の関係を示すグラフである。
第4・図は、水和金属酸化物とホウ酸亜鉛の添加比率と
酸素指数の関係を示すグラフである。
第5図は、炭酸金属塩とホウ酸亜鉛の添加比率と発煙量
の関係を示すグラフである。
第6図は、炭酸金属塩とホウ酸亜鉛の添加比率と酸素指
数の関係を示すグラフである。
(1)は炭酸マグネシウム、(2)は水酸化マグネシウ
ム、(3)は水酸化アルミニウム、(4)はホウ酸亜鉛
である。
充i41量(更量含P)
!’yNt@/(ホ、)丙屹堂4凸すに級屓故イヒコ勿
)井5図FIG. 1 is a graph showing the relationship between the amount of various fillers added and the oxygen index. FIG. 2 is a graph showing the relationship between the amount of various fillers added and the amount of smoke generated. FIG. 3 is a graph showing the relationship between the addition ratio of hydrated metal oxide and zinc borate and the amount of smoke generated. Figure 4 is a graph showing the relationship between the addition ratio of hydrated metal oxide and zinc borate and the oxygen index. FIG. 5 is a graph showing the relationship between the addition ratio of metal carbonate and zinc borate and the amount of smoke generated. FIG. 6 is a graph showing the relationship between the addition ratio of metal carbonate and zinc borate and the oxygen index. (1) is magnesium carbonate, (2) is magnesium hydroxide, (3) is aluminum hydroxide, and (4) is zinc borate. Full i41 amount (additional amount included)! 'yNt@/(ho,) Heibado 4 convex suni class late Ihiko naru) well 5
Claims (3)
ン−酢酸ビニル共重合体を主体とするポリオレフィン樹
脂組成物に、充填剤として水利金属酸化物あるいは金属
炭酸塩とホウ酸亜鉛とを両者合せて100重量部以上添
加し、かつ充填剤中のホウ酸亜鉛の比率が025〜0.
75で、放射線照射により架橋した組成物を絶縁体又は
シースとして用いたことを特徴とする難燃、低煙ポリオ
レフィン樹脂被覆電線。(1) A polyolefin resin composition mainly composed of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 50% by weight or more is combined with a water-use metal oxide or metal carbonate and zinc borate as fillers. 100 parts by weight or more, and the ratio of zinc borate in the filler is 0.25-0.
75. A flame-retardant, low-smoke polyolefin resin-coated electric wire characterized in that a composition crosslinked by radiation irradiation is used as an insulator or a sheath.
マグネシウム、水酸化カルシウム、水酸化ノ<リウムか
ら成る群より選ばれたものであることを特徴とする特許
請求の範囲(1)項記載の難燃、低煙ポリオレフィン樹
脂被覆電線。(2) Claim (1) characterized in that the water use metal oxide is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and norium hydroxide. flame-retardant, low-smoke polyolefin resin-coated wire.
ムカルシウム、炭酸カルシウム、炭酸亜鉛、炭酸バリウ
ムから成る群より選ばれたものであることを特徴とする
特許請求の範囲第(1)項記載の難燃、低煙ポリオレフ
ィン樹脂被覆電線。(3) The flame retardant according to claim (1), wherein the metal carbonate is selected from the group consisting of magnesium carbonate, magnesium calcium carbonate, calcium carbonate, zinc carbonate, and barium carbonate. , low smoke polyolefin resin coated wire.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3507383A JPS59160911A (en) | 1983-03-03 | 1983-03-03 | Flame resistance, low smoke polyolefin resin coated wire |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3507383A JPS59160911A (en) | 1983-03-03 | 1983-03-03 | Flame resistance, low smoke polyolefin resin coated wire |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59160911A true JPS59160911A (en) | 1984-09-11 |
Family
ID=12431819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3507383A Pending JPS59160911A (en) | 1983-03-03 | 1983-03-03 | Flame resistance, low smoke polyolefin resin coated wire |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59160911A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0269567A (en) * | 1988-07-18 | 1990-03-08 | Gurit Essex Ag | Resin capable of forming flame-retardant, high-temperature-resistant polymeric resin by curing, and manufacture thereof |
-
1983
- 1983-03-03 JP JP3507383A patent/JPS59160911A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0269567A (en) * | 1988-07-18 | 1990-03-08 | Gurit Essex Ag | Resin capable of forming flame-retardant, high-temperature-resistant polymeric resin by curing, and manufacture thereof |
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