JPH024619B2 - - Google Patents
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- Publication number
- JPH024619B2 JPH024619B2 JP60067977A JP6797785A JPH024619B2 JP H024619 B2 JPH024619 B2 JP H024619B2 JP 60067977 A JP60067977 A JP 60067977A JP 6797785 A JP6797785 A JP 6797785A JP H024619 B2 JPH024619 B2 JP H024619B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- eea
- silica
- eva
- 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 - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- JJEPQBZQAGCZTH-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenoxy)ethoxy]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OCCOC1=C(Br)C(Br)=C(Br)C(Br)=C1Br JJEPQBZQAGCZTH-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔技術分野〕
本発明は樹脂組成物に関し、更に詳しくはエチ
レン−酢酸ビニル共重合体（以下EVAという）
並びにエチレン−エチルアクリレート共重合体
（以下EEAという）の少なくとも１種、及び直鎖
状ポリエチレン（以下LPEという）の樹脂成分
に、特定の二種類の化合物と特定の難燃剤とを配
合して成る組成物に関する。
〔従来技術〕
エチレン系重合体又はエチレン−エチルアクリ
レート共重合体（EEA）は優れた電気絶縁性を
有し、また放射線架橋、有機過酸化物架橋、シラ
ン化合物を用いるシラン架橋等各種の架橋手段を
適宜に採用して架橋出来、惹いては各種物性を改
善出来る利点があるため、従来から電気絶縁材料
を始め、各種の分野に巾広く使用されて来た。し
かしながら最近各種分野の技術レベルが向上し、
電気機器、車輌、自動車等の各分野に於いて絶縁
電線就中電子ワイヤーといわれる絶縁電線のより
高度の特性が要求されるようになり、耐油性、絶
縁電線製造時の加工性、難燃性、高温絶縁強度性
（Cut through property）等がより高度に要求さ
れるようになつて来た。
〔発明の目的並びにその概要〕
本発明者は従来からEVA又はEEA組成物につ
いて研究を続けて来たが、特に最近の技術レベル
の向上に応じた各種物性の特に優れたEVA又は
EEA組成物を開発すべく研究を続けて来た。そ
してこの研究に於いてEVA並びにEEAの少なく
とも１種の直鎖状ポリエチレン（以下LPEとい
う）とを特定量併用するときは、耐油性が、
EVA並びに（又は）EEAの特性をそのまま保持
したままで更に一段と向上することを見出した。
また更に研究を押し進める段階でEVA及びEEA
の少なくとも１種と、LPEとの併用組成に、特
にSb2O3と臭素系又は（及び）塩素系難燃剤とを
配合するときは、難燃性並びに耐加熱変形性がよ
り一段と優れるという新事実を見出した。
本発明者は引き続き上記特定配合物について研
究を続けた結果、この特定配合組成物に乾式シリ
カ、又はこれとZnO、焼成微粉末湿式シリカ、
Al2O3、硫酸バリウム、表面処理した炭酸カルシ
ウム並びにAl（OH）3の少なくとも１種を更に追
加配合するときは、上記特定配合組成の優れた各
特性即ち、耐油性、並びに耐加熱変形性が一段と
向上する上に、更に難燃性も著しく向上すること
を見出し、ここに本発明を完成するに至つた。即
ち本発明は、
(1) エチレン−酢酸ビニル共重合体又は（及び）
エチレン−エチルアクリレート共重合体100重
量部、直鎖状ポリエチレン５〜120重量部、臭
素系難燃剤又は（及び）塩素系難燃剤20〜80重
量部、Sb2O35〜50重量部及び乾式シリカ５〜
100重量部を含有して成る樹脂組成物、
(2) ZnO、焼成微粉末湿式シリカ、Al2O3、硫酸
バリウム、表面処理した炭酸カルシウム並びに
Al（OH）3の少なくとも１種、及び乾式シリカ
とを５〜100重量部含有して成る特許請求の範
囲第１項の樹脂組成物に係るものである。
〔発明の効果〕
本発明に於いてはEVA並びにEEAの少なくと
も１種とから成る樹脂配合物に、Sb2O3と臭素系
又は（及び）塩素系難燃剤とを含有させることに
より、得られる組成物就中この組成物を架橋する
ことにより、耐油性、耐加熱変形性並びに、難燃
性が著しく優れるという効果がある。そしてこれ
等の各特性を損なうことなく、更に乾式シリカ、
又はこれとZnO、焼成微粉末湿式シリカ、
Al2O3、硫酸バリウム、表面処理した炭酸カルシ
ウム並びにAl（OH）3の少なくとも１種とを配合
することにより、難燃性が極端に大きく向上する
という効果がある。
〔発明の構成〕
本発明の組成物は基本的には、EVA並びに
EEAの少なくとも１種100重量部、及びLPE5〜
120重量部好ましくは20〜80重量部を含有して成
るものである。
本発明に於いて使用されるEVAとしては、そ
の酢酸ビニル含量が20重量％以下好ましくは15重
量％以下のものであり、そのメルトインデツクス
（以下M.I.という）としても0.2〜５程度のものが
好ましい。EEAもエチルアクリレート含量が20
重量％以下、M.I.は0.2〜1.0が好ましい。これ等
EVA及びEEAは夫々単独で使用されても、また
併用されても良く、この併用の際の割合もEVA0
〜100重量％並びにEEA100〜０重量％の広い範
囲から適宜に選択されれば良い。またLPEとし
ては低密度のものが好ましく、たとえば密度0.91
〜0.93ｇ／cm3程度のものを好ましいものとして例
示出来る。他の好ましいものとしては炭素数が４
〜８程度のものを挙げることが出来る。その分子
量としてもかなり広い範囲のものが使用出来、通
常５万〜50万程度好ましくは８万〜20万程度のも
のを使用する。またLPE自体はその製法には何
等限定されず本発明の目的に合致するLPEが得
られるかぎり、各種の製法で製造されたものがい
ずれも使用出来る。
本発明に於いて使用されるシリカは乾式シリカ
であり、たとえば「アエロジルＲ−972」（デグサ
社、商品名）を代表例として例示出来る。
ZnOはフランス法、アメリカ法、湿式法のいず
れかの製法で作られものであり平均粒径通常1.0μ
以下のものである。
また焼成微粉末湿式シリカとは、常法により製
造した湿式シリカを高温通常800℃以上の高温で
熱処理することにより、表面シラノール基を減少
さや、水分移動を少なくし、且つ屈折率を大きく
したシリカであり、強熱減量2.0％以下、屈折率
1.448以上、平均粒径１〜4μのものである。この
シリカとしては塩野義製薬(株)のカープレツクス
CS5〜７がある。
硫酸バリウムは、特に沈降性の板状、柱状の粒
子形状で、純度が高く、平均粒径は数μ以下のも
のが望ましい。
表面処理した炭酸カルシウムとは特に押出加工
性、分散性を改良するためにシラン又はチタン等
の系統のカツプリング剤で表面処理されたもの
で、特に沈降性軽微性でビニル基等官能基を持ち
純度が高く平均粒径は数μ以下のものが望まし
い。Al2O3，Al（OH）3も純度が高いもので、粒径
は数μ以下が好適である。
本発明に於いては乾式シリカを或いはまたこの
乾式シリカの１部をZnO、焼成微粉末湿式シリ
カ、Al2O3、硫酸バリウム、表面処理した炭酸カ
ルシウム並びにAl（OH）3の少なくとも１種で置
き代えたものを、EVA並びにEEAの少なくとも
１種100重量部に対して10〜100重量部好ましくは
20〜50重量部使用する。また必要に応じ乾式シリ
カの一部を置換して使用されるZnO、焼成微粉末
湿式シリカ、Al2O3、硫酸バリウム、表面処理し
た炭酸カルシウム、並びにAl（OH）3の少なくと
も１種は乾式シリカの90重量％以下好ましくは50
〜80重量％程度置換される。
本発明に於いては、臭素系難燃剤としては従来
から用いられているものがいずれも有効に使用出
来、具体例としてはたとえばデカブロモジフエニ
ルオキサイド（例えば三井東圧フアイン(株)のプラ
ネロンDB−100）、ポリ（トリブロモ）スチレン
（日産フエロ有機化学(株)のパイロチエツク68PB）、
エチレングリコールビス（ペンタブロモフエニ
ル）エーテル（日産フエロ有機化学(株)のパイロチ
エツク77B）、塩素系難燃剤としてはビス（１，
２，５，６−ヘキサクロロジシクロペンテノ）シ
クロオクタン（Hooker chemicals and plastic
Co.のデクロランプラス25）を例示することが出
来る。これ等難燃剤はEVA並びにEEAの少なく
とも１種100重量部に対して20〜80重量部好まし
くは30〜50重量部の割合で使用される。
また本発明に於いてSb2O3はEVA並びにEEA
の少なくとも１種100重量部に対し５〜50重量部
好ましくは10〜30重量部配合される。
本発明組成物には更に必要に応じてその他の他
の通常の各種添加剤を添加することが出来る。こ
の際の他の添加剤としては、たとえばその他の難
燃剤、各種老化防止剤、無機充填剤等があり、ま
た架橋剤、架橋助剤等も使用出来することが出来
る。
〔実施例〕
以下に実施例を示して本発明をより具体的に説
明する。但し下記例に於いて部とあるは重量部を
意味するものとする。
実施例１〜７並びに比較例１〜２
第１表に示す配合割合で各成分を所定量配合充
分混練して組成物となした。この組成物について
常法に基づいて導体0.813mmφの軟銅単線、絶縁
は0.38mm厚の電線を製造し、30Mradの電子線量
で照射架橋した。各種物性を測定した。この結果
を第２表に示す。但し物性は夫々次の方法により
測定した。
〈耐油性〉
100℃のAGTM2号オイルの中に96時間浸漬後
室温に放置し、引張強さの残率が初期の50％以
上、伸びの残率が65％以上の時合格とする。
〈難燃性〉
UL Subject758に準じ、垂直にした電線に対
し、一定傾斜のバーナーから一定量の炎を15秒間
あてた後15秒間炎を取り除き、これを５回繰り返
す。電線が一定量以上燃え移らないか、もしくは
灰が滴下して下に敷いた綿に燃え移らなければ合
格とする。
〈加工性〉
コンパウンドを30mmφの押出機で銅線上に被覆
した時、押出した表面外観が滑らかであれば合格
とする。
〈加熱変形性〉
150℃の温度で電線上に250ｇの荷重を30分かけ
た時の変形率が40％以下であれば合格とする。
〈耐熱老化性〉
136℃で７日間、老化し、引張残率70％以上、
伸び残率65％以上、破壊電圧の残率50％以上であ
れば合格とする。
但し第１表中で重合体として使用した各種重合
体は夫々次のものを示す。
LPE−１：密度 0.920
M.I. 1.0
炭素数 ８
LPE−２：密度 0.925
M.I. 4.0
炭素数 ４
EVA−１：酢酸ビニル（以下EVという）含量
15wt％
M.I. 0.5
EVA−２：EV含量 10wt％
M.I. 1.0
EEA−１：エチルアクリレート（EVという）
含量 15wt％
M.I. 1.5
EEA−２：EV含量 15wt％
M.I. 0.5
又、Irganox1010はフエノール系酸化防止剤
で、テトラキス−〔メチレン−３−（3′，5′−ジ−
第３−ブチル−4′−ヒドロキシフエニル）プロピ
オネート〕メタンである。
実施例８〜10及び比較例３〜８
第３表に示す配合割合で各成分を用い、実施例
１と同様に処理して電線を製造した。また同様な
方法により各種物性を測定した。この結果を第４
表に示す。第４表中の合否判定は第２表に評価と
同じである。
但し第４表に於ける加工性は次の方法に依つ
た。
第２表の加工性の測定方法に於いて、各組成物
を0.5mm2撚線鋼線上に0.2mm厚で線速200m／minの
高速押出被覆した際の押出外観を肉眼で観測した
ものである。
[Technical Field] The present invention relates to a resin composition, and more specifically to an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA).
and at least one type of ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) and a resin component of linear polyethylene (hereinafter referred to as LPE), and two specific types of compounds and a specific flame retardant are blended. Regarding the composition. [Prior art] Ethylene polymers or ethylene-ethyl acrylate copolymers (EEA) have excellent electrical insulation properties, and can be used for various crosslinking methods such as radiation crosslinking, organic peroxide crosslinking, and silane crosslinking using silane compounds. It has been widely used in various fields including electrical insulation materials because it has the advantage of being able to crosslink by appropriately employing it and improve various physical properties. However, recently the technological level in various fields has improved,
In various fields such as electrical equipment, vehicles, and automobiles, insulated wires, especially electronic wires, are required to have more advanced characteristics, such as oil resistance, processability during insulated wire manufacturing, and flame retardancy. , high-temperature dielectric strength (cut through property), etc. have become more highly required. [Objective and summary of the invention] The present inventor has been researching EVA or EEA compositions for a long time, and has particularly developed EVA or EEA compositions with particularly excellent physical properties in accordance with recent technological advances.
We have continued our research to develop EEA compositions. In this research, when EVA and at least one kind of linear polyethylene (hereinafter referred to as LPE) of EEA were used together in a specific amount, the oil resistance was
It has been found that the characteristics of EVA and/or EEA can be further improved while maintaining the characteristics as they are.
In addition, EVA and EEA will be introduced at the stage of further research.
In particular, when Sb 2 O 3 and a brominated or (and) chlorinated flame retardant are combined in a combined composition with at least one of I found out the truth. As a result of continuing research on the above-mentioned specific compound, the present inventor found that this specific compound composition contained dry silica, ZnO in combination with it, calcined fine powder wet silica,
When at least one of Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and Al(OH) 3 is additionally blended, each of the excellent properties of the above-mentioned specific blend composition, such as oil resistance and heat deformation resistance, may be added. The present inventors have discovered that not only the flame retardance is further improved, but also the flame retardance is significantly improved, and the present invention has now been completed. That is, the present invention provides: (1) ethylene-vinyl acetate copolymer or (and)
100 parts by weight of ethylene-ethyl acrylate copolymer, 5 to 120 parts by weight of linear polyethylene, 20 to 80 parts by weight of brominated flame retardant or (and) chlorinated flame retardant, 5 to 50 parts by weight of Sb 2 O 3 and dry process Silica 5~
(2) ZnO, calcined finely powdered wet silica, Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and
The present invention relates to a resin composition according to claim 1, which contains 5 to 100 parts by weight of at least one Al(OH) 3 and dry silica. [Effects of the Invention] In the present invention, a flame retardant obtained by adding Sb 2 O 3 and a bromine-based or (and) chlorine-based flame retardant to a resin composition consisting of at least one of EVA and EEA. By crosslinking this composition, the composition has the effect of significantly improving oil resistance, heat deformation resistance, and flame retardancy. And without impairing each of these properties, dry silica,
Or this and ZnO, calcined fine powder wet silica,
By blending with at least one of Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and Al(OH) 3 , the flame retardance is extremely improved. [Structure of the Invention] The composition of the present invention basically comprises EVA and
100 parts by weight of at least one type of EEA, and LPE5~
It contains 120 parts by weight, preferably 20 to 80 parts by weight. The EVA used in the present invention has a vinyl acetate content of 20% by weight or less, preferably 15% by weight or less, and a melt index (hereinafter referred to as MI) of about 0.2 to 5. preferable. EEA also has an ethyl acrylate content of 20
The weight percent or less, MI is preferably 0.2 to 1.0. These etc.
EVA and EEA may be used alone or in combination, and the ratio when used in combination is EVA0.
It may be appropriately selected from a wide range of 100% to 100% by weight and 100% to 0% by weight EEA. In addition, it is preferable that the LPE has a low density, for example, a density of 0.91
~0.93 g/cm 3 can be exemplified as a preferable example. Another preferable example is a carbon number of 4.
I can list about 8 to 8. A fairly wide range of molecular weights can be used, and it is usually from 50,000 to 500,000, preferably from 80,000 to 200,000. Further, the LPE itself is not limited in any way to its production method, and any LPE produced by various production methods can be used as long as LPE that meets the purpose of the present invention can be obtained. The silica used in the present invention is a dry silica, such as "Aerosil R-972" (trade name, manufactured by Degussa) as a representative example. ZnO is manufactured using either the French method, the American method, or the wet method, and the average particle size is usually 1.0μ.
These are as follows. Calcined fine powder wet silica is silica produced by heat-treating wet silica produced by conventional methods at a high temperature, usually 800°C or higher, to reduce surface silanol groups, reduce water movement, and increase the refractive index. Ignition loss is 2.0% or less, refractive index
1.448 or more, with an average particle size of 1 to 4μ. This silica is Carplex manufactured by Shionogi & Co., Ltd.
There are CS5-7. Barium sulfate preferably has a sedimentary plate-like or columnar particle shape, has high purity, and has an average particle size of several microns or less. Surface-treated calcium carbonate is a type of calcium carbonate that has been surface-treated with a coupling agent such as silane or titanium to improve extrusion processability and dispersibility. It is desirable that the particle size is high and the average particle size is several microns or less. Al 2 O 3 and Al(OH) 3 are also highly pure and preferably have a particle size of several microns or less. In the present invention, the dry silica or a part of the dry silica is made of at least one of ZnO, calcined fine powder wet silica, Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and Al(OH) 3 . Preferably 10 to 100 parts by weight of the substituted material per 100 parts by weight of at least one of EVA and EEA.
Use 20-50 parts by weight. In addition, at least one of ZnO, calcined finely powdered wet silica, Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and Al(OH) 3 is used to replace a part of the dry silica if necessary. Less than 90% by weight of silica, preferably 50%
~80% by weight is replaced. In the present invention, any conventionally used brominated flame retardant can be effectively used, and specific examples include decabromodiphenyl oxide (for example, Planelon DB from Mitsui Toatsu Fine Co., Ltd.). -100), poly(tribromo)styrene (Pyrocheck 68PB from Nissan Ferro Organic Chemical Co., Ltd.),
Ethylene glycol bis(pentabromophenyl) ether (Pyrocheck 77B from Nissan Ferro Organic Chemical Co., Ltd.), bis(1,
2,5,6-hexachlorodicyclopenteno)cyclooctane (Hooker chemicals and plastic
An example of this is Dechloran Plus 25) from Co. These flame retardants are used in an amount of 20 to 80 parts by weight, preferably 30 to 50 parts by weight, per 100 parts by weight of at least one of EVA and EEA. In addition, in the present invention, Sb 2 O 3 is EVA and EEA.
5 to 50 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of at least one of the following. The composition of the present invention may further contain various other conventional additives, if necessary. Other additives in this case include, for example, other flame retardants, various anti-aging agents, inorganic fillers, etc., and crosslinking agents, crosslinking aids, etc. can also be used. [Example] The present invention will be described in more detail with reference to Examples below. However, in the following examples, "parts" means parts by weight. Examples 1 to 7 and Comparative Examples 1 to 2 Predetermined amounts of each component were mixed and sufficiently kneaded in the proportions shown in Table 1 to form compositions. A single annealed copper wire with a conductor of 0.813 mmφ and an electric wire of 0.38 mm in thickness was manufactured from this composition according to a conventional method, and cross-linked by irradiation with an electron beam dose of 30 Mrad. Various physical properties were measured. The results are shown in Table 2. However, the physical properties were measured by the following methods. <Oil resistance> After being immersed in AGTM No. 2 oil at 100℃ for 96 hours, it is left at room temperature, and it is considered to have passed if the residual tensile strength is 50% or more of the initial value and the residual elongation is 65% or more. <Flame retardant> According to UL Subject 758, apply a certain amount of flame from a burner at a certain angle to a vertical electric wire for 15 seconds, then remove the flame for 15 seconds, and repeat this 5 times. The test is passed if a certain amount of electric wire does not burn out, or if ash does not fall and spread to the underlying cotton. <Workability> When the compound is coated on copper wire using a 30mmφ extruder, if the extruded surface appearance is smooth, the product will pass. <Heating deformability> The wire is passed if the deformation rate is 40% or less when a load of 250g is applied to the wire for 30 minutes at a temperature of 150°C. <Heat aging resistance> Aging at 136℃ for 7 days, tensile retention of 70% or more,
If the residual elongation rate is 65% or more and the residual breakdown voltage is 50% or more, it will be passed. However, the various polymers used as polymers in Table 1 are shown below. LPE-1: Density 0.920 MI 1.0 Number of carbons 8 LPE-2: Density 0.925 MI 4.0 Number of carbons 4 EVA-1: Vinyl acetate (hereinafter referred to as EV) content 15wt% MI 0.5 EVA-2: EV content 10wt% MI 1.0 EEA- 1: Ethyl acrylate (referred to as EV) content 15wt% MI 1.5 EEA-2: EV content 15wt% MI 0.5 Irganox 1010 is a phenolic antioxidant, tetrakis-[methylene-3-(3',5'-di-
tert-butyl-4'-hydroxyphenyl)propionate]methane. Examples 8 to 10 and Comparative Examples 3 to 8 Electric wires were manufactured in the same manner as in Example 1 using each component in the mixing ratios shown in Table 3. Various physical properties were also measured using similar methods. This result is the fourth
Shown in the table. The pass/fail judgment in Table 4 is the same as the evaluation in Table 2. However, the workability in Table 4 was determined by the following method. In the processability measurement method shown in Table 2, each composition was coated on a 0.5 mm double- stranded steel wire by high-speed extrusion at a wire speed of 200 m/min at a thickness of 0.2 mm, and the extrusion appearance was observed with the naked eye. be.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
エチレン−エチルアクリレート共重合体100重量
部、直鎖状ポリエチレン５〜120重量部、臭素系
又は（及び）塩素系難燃剤20〜80重量部、
Sb2O35〜50重量部、及び乾式シリカ５〜100重量
部を含有して成る樹脂組成物。 ２ ZnO、焼成微粉末湿式シリカ、Al2O3、硫酸
バリウム、表面処理した炭酸カルシウム並びに
Al（OH）3の少なくとも１種、及び乾式シリカと
を５〜100重量部含有して成る特許請求の範囲第
１項の樹脂組成物。[Claims] 1. Ethylene-vinyl acetate copolymer or (and)
100 parts by weight of ethylene-ethyl acrylate copolymer, 5 to 120 parts by weight of linear polyethylene, 20 to 80 parts by weight of brominated or (and) chlorinated flame retardant,
A resin composition comprising 5 to 50 parts by weight of Sb 2 O 3 and 5 to 100 parts by weight of dry silica. 2 ZnO, calcined fine powder wet silica, Al 2 O 3 , barium sulfate, surface-treated calcium carbonate, and
The resin composition according to claim 1, comprising 5 to 100 parts by weight of at least one Al(OH) 3 and dry silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6797785A JPS61228049A (en) | 1985-03-30 | 1985-03-30 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6797785A JPS61228049A (en) | 1985-03-30 | 1985-03-30 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61228049A JPS61228049A (en) | 1986-10-11 |
| JPH024619B2 true JPH024619B2 (en) | 1990-01-29 |
Family
ID=13360554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6797785A Granted JPS61228049A (en) | 1985-03-30 | 1985-03-30 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61228049A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61228050A (en) * | 1985-03-30 | 1986-10-11 | Mitsubishi Cable Ind Ltd | Resin composition |
| JPH0649807B2 (en) * | 1985-05-17 | 1994-06-29 | 大日本インキ化学工業株式会社 | Flame-retardant resin composition |
| JPS63196655A (en) * | 1987-02-10 | 1988-08-15 | Yazaki Corp | Water-resistant, flame-retardant thermoplastic resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56116734A (en) * | 1980-02-19 | 1981-09-12 | Fujikura Ltd | Flame-retardant composition |
| JPS5851415A (en) * | 1981-09-22 | 1983-03-26 | 日立電線株式会社 | Flame resistant insulated wire |
| JPS61228050A (en) * | 1985-03-30 | 1986-10-11 | Mitsubishi Cable Ind Ltd | Resin composition |
-
1985
- 1985-03-30 JP JP6797785A patent/JPS61228049A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56116734A (en) * | 1980-02-19 | 1981-09-12 | Fujikura Ltd | Flame-retardant composition |
| JPS5851415A (en) * | 1981-09-22 | 1983-03-26 | 日立電線株式会社 | Flame resistant insulated wire |
| JPS61228050A (en) * | 1985-03-30 | 1986-10-11 | Mitsubishi Cable Ind Ltd | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61228049A (en) | 1986-10-11 |
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