JPH02105838A - Ethylene copolymer composition and ethylene copolymer molding - Google Patents
Ethylene copolymer composition and ethylene copolymer moldingInfo
- Publication number
- JPH02105838A JPH02105838A JP26002888A JP26002888A JPH02105838A JP H02105838 A JPH02105838 A JP H02105838A JP 26002888 A JP26002888 A JP 26002888A JP 26002888 A JP26002888 A JP 26002888A JP H02105838 A JPH02105838 A JP H02105838A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene copolymer
- stabilizer
- parts
- weight
- pts
- 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
Links
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000000465 moulding Methods 0.000 title 1
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 18
- 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 compound 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 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims description 10
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 230000005865 ionizing radiation Effects 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- RSJKGSCJYJTIGS-BJUDXGSMSA-N undecane Chemical group CCCCCCCCCC[11CH3] RSJKGSCJYJTIGS-BJUDXGSMSA-N 0.000 claims description 2
- -1 Sb2O3) Chemical compound 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 3
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical group C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 239000000454 talc Substances 0.000 abstract description 2
- 229910052623 talc Inorganic materials 0.000 abstract description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- QBMOKCWBZBOOTK-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Zr+4].[Sn+4] Chemical compound [O--].[O--].[O--].[O--].[Zr+4].[Sn+4] QBMOKCWBZBOOTK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 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 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 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
- 239000012778 molding material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は電気絶縁材料、電気部品成形材料として有用な
エチレン共重合体組成物に関する。更に詳しくは高耐熱
性でシリコーンゴムの代替が可能なエチレン共重合体組
成物及び該組成物を有機過酸化物又は電離放射線によっ
て架橋してなるエチレン共重合体成形品に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an ethylene copolymer composition useful as an electrical insulating material and a molding material for electrical parts. More specifically, the present invention relates to an ethylene copolymer composition that has high heat resistance and can be used as a substitute for silicone rubber, and to an ethylene copolymer molded article obtained by crosslinking the composition with an organic peroxide or ionizing radiation.
（従来の技術）
ポリエチレン、エチレン共重合体等のポリオレフィンに
ヒンダードフェノール系安定剤、硫黄系安定剤、亜鉛化
合物などを混合して耐熱性を向上させる試みは従来より
行なわれている。(Prior Art) Attempts have been made to improve heat resistance by mixing polyolefins such as polyethylene and ethylene copolymers with hindered phenol stabilizers, sulfur stabilizers, zinc compounds, and the like.
更にこれを電離放射線又は有機過酸化物によって架橋し
、架橋成形品にすることにより、本来９０℃程度の連続
使用耐熱温度でしかない架橋ポリオレフィンを１２０℃
〜１５０℃耐熱温度とすることができる。Furthermore, by crosslinking this with ionizing radiation or organic peroxide to make a crosslinked molded product, the crosslinked polyolefin, which originally has a continuous use temperature of about 90℃, can be heated to 120℃.
It can be made into the heat-resistant temperature of -150 degreeC.
最近では上記の安定剤の組み合わせを更に検討し、耐熱
性を向上させる試みがなされている０例えば特開昭６２
−２６５３３３号公報及び特開昭６２−２６５３３４号
公報にはベンズイミダゾール系化合物、ヒンダードフェ
ノール系化合物及び硫黄系化合物との３種類を組み合わ
せており、耐熱性を向上させている。Recently, combinations of the above-mentioned stabilizers have been further studied and attempts have been made to improve heat resistance.
JP-A-265333 and JP-A-62-265334 combine a benzimidazole compound, a hindered phenol compound, and a sulfur compound to improve heat resistance.
（本発明が解決しようとする課題）
従来の安定剤系は、比較的低充填である場合に充分な効
果を発揮できるが、成形性、ｌｌ！械物性。(Problems to be Solved by the Present Invention) Conventional stabilizer systems can exhibit sufficient effects when the loading is relatively low, but the moldability is poor! Mechanical properties.
電気特性などの特性向上のための充填剤、難燃化のため
の難燃剤を多量に充填した場合には、これらの充填物に
安定剤がある程度吸着されてしまい効果が逓減してしま
う欠点があった。そのために従来はその分を見込んでや
や多口に安定剤を使用していたが、その結果加硫阻害を
おこすことかあり、また経済的にも好ましくなかった。If a large amount of filler is used to improve properties such as electrical properties, or flame retardant is used to make flame retardant, the stabilizer will be adsorbed to some extent by these fillers, reducing the effectiveness. there were. For this reason, in the past, a relatively large amount of stabilizer was used to compensate for this, but as a result, vulcanization could be inhibited, and this was also economically unfavorable.
（課題を解決するための手段）
本発明者らは難燃剤や充填剤が多量に充填された場合に
も効果を以可なく発揮できる安定剤系を鋭意探索したと
ころ、全く窓外にも、ある構造を有する安定剤を使用す
ることによりこの課題が解決できることを見出し、本発
明に到った。(Means for Solving the Problems) The present inventors have earnestly searched for a stabilizer system that can be extremely effective even when filled with large amounts of flame retardants and fillers. The inventors have discovered that this problem can be solved by using a stabilizer having a certain structure, leading to the present invention.
すなわち本発明は
ビニルエステル及び／又は（メタ）アクリル酸エステル
から運ばれる１種又は２種以上の極性モノマーとエチレ
ンとの共重合体１００重量部に対し充填剤及び／又は難
燃剤が６０〜３００重量部混合され、更に２，４，８．
１０−テトラオキサスピロ［５，５）ウンデカン環を分
子中に有するヒンダードフェノール系安定剤０．１〜５
重量部及び２ ｆｌのイオウ原子を分子中に有する含硫
黄安定剤０１〜５重量部で安定化されてなるエチレン共
重合体組成物、
及び上記組成物を有機過酸化物又は電離放射線によって
架橋してなるエチレン共重合体成形品、を提供すること
にある。That is, in the present invention, the amount of filler and/or flame retardant is 60 to 300 parts by weight per 100 parts by weight of a copolymer of ethylene and one or more polar monomers carried from vinyl ester and/or (meth)acrylic acid ester. 2, 4, 8.
Hindered phenol stabilizer having 10-tetraoxaspiro[5,5)undecane ring in the molecule 0.1 to 5
an ethylene copolymer composition stabilized with 01 to 5 parts by weight of a sulfur-containing stabilizer having sulfur atoms in the molecule of 0.1 to 5 parts by weight, and crosslinking the above composition with an organic peroxide or ionizing radiation. An object of the present invention is to provide an ethylene copolymer molded product made of ethylene copolymer.
本発明で用いられる極性モノマーは酢酸ビニル。The polar monomer used in the present invention is vinyl acetate.
酪酸ビニルなどのビニルエステル及び／又は（メタ）ア
クリル酸メチル、（メタ）アクリル酸エチル、（メタ）
アクリル酸ブチル、などの（メタ）アクリル酸エステル
から選ばれる。Vinyl esters such as vinyl butyrate and/or methyl (meth)acrylate, ethyl (meth)acrylate, (meth)
Selected from (meth)acrylic esters such as butyl acrylate.
これらの極性上ツマ−の１種又は２種以上はエチレンと
公知の方法によって共重合され、エチレン共重合体とな
る。One or more of these polar polymers are copolymerized with ethylene by a known method to form an ethylene copolymer.
このとき極性モノマーの量はエチレン１００重量部に対
し５０重量部を越えると耐熱性が不充分であり好ましく
ない。エチレン共重合体とすると、羊なるポリエチレン
よりも安定剤の溶解度が高まるため高温での残存率が高
くなり、結果として高耐熱性が得られることは、周知の
事実である１本発明においても単なるポリエチレンでは
充分な耐熱性が得られず好ましくない。At this time, if the amount of the polar monomer exceeds 50 parts by weight per 100 parts by weight of ethylene, the heat resistance will be insufficient, which is not preferable. It is a well-known fact that when used as an ethylene copolymer, the solubility of the stabilizer is higher than that of polyethylene, which increases the residual rate at high temperatures, resulting in high heat resistance. Polyethylene is not preferred because it does not provide sufficient heat resistance.
本発明のエチレン共重合体は充填剤及び／又は難燃剤と
混合されて実用に供される。充填剤はエチレン共重合体
の成形性１機械物性、電気特性などの特性を向上させる
ため、又は増量剤として全体の価格を低下させるなどよ
り実用に適した性質に改善するために用いる。充填剤と
しては公知のものが使用でき、タルク、クレー、炭酸カ
ルシウム、ウオラストナイト、乾式シリカ、湿式シリカ
。The ethylene copolymer of the present invention is put into practical use after being mixed with a filler and/or a flame retardant. The filler is used to improve the properties of the ethylene copolymer, such as moldability, mechanical properties, and electrical properties, or as an extender to reduce the overall price and improve the properties to be more suitable for practical use. Known fillers can be used, including talc, clay, calcium carbonate, wollastonite, dry silica, and wet silica.
マイカ粉などから、必要に応じて選択される。Selected from mica powder, etc., depending on needs.
難燃剤はエチレン共重合体を難燃化するために用いられ
る。デカブロモジフェニルエーテル、ドデカプロモーＰ
−フェノキシジフヱニルエーテル。Flame retardants are used to make ethylene copolymers flame retardant. Decabromodiphenyl ether, dodecapromo P
-Phenoxydiphenyl ether.
パークロロペンタシクロデカンなどのハロゲン系難燃剤
、水酸ｆヒアルミニラム、水酸化マグネシウムなどの金
属水和物、三酸化アンチモン、三酸化モリブデン、酸化
亜鉛、ホウ酸亜鉛、ＷＩ化スズ酸化ジルコニウムなどの
金属酸化物から必要に応じて選択される。好ましくはハ
ロゲン系難燃剤金属水和物、金属酸化物の群からそれぞ
れ適当に組み合せて求められる難燃性の程度によって必
要とされる量を用いる。Halogenated flame retardants such as perchloropentacyclodecane, metal hydrates such as hyaluminum hydroxide, magnesium hydroxide, metals such as antimony trioxide, molybdenum trioxide, zinc oxide, zinc borate, and tin zirconium oxide Selected from oxides as required. Preferably, the halogenated flame retardants are used in appropriate combinations from the group of metal hydrates and metal oxides, respectively, and used in amounts required depending on the degree of flame retardancy required.
充填剤及び／又は難燃剤の使用量はエチレン共重合体１
００重量部に対して６０重量部以上３００重量部以下で
ある。６０重量部未満では、これら充填剤及び／又は難
燃剤の効果が充分でなく、３００重量部を越えると機械
物性が実用に耐えられない程弱くなる。The amount of filler and/or flame retardant used is 1 part of ethylene copolymer.
It is 60 parts by weight or more and 300 parts by weight or less relative to 00 parts by weight. If the amount is less than 60 parts by weight, the effect of these fillers and/or flame retardants will not be sufficient, and if it exceeds 300 parts by weight, the mechanical properties will be too weak for practical use.
エチレン共重合体と難燃剤及び／又は充填剤との組成物
を電気部品として使用する際に充分な耐熱性を得ること
ができるように該混合物に安定剤を使用する。Stabilizers are used in the mixture of ethylene copolymer and flame retardant and/or filler so that sufficient heat resistance can be obtained when the composition is used as an electrical component.
安定剤としては２，４，８．１０−テトラオキサスピロ
〔５、５〕ウンデカン環を分子中に有するヒンダードフ
ェノール系安定剤と２価のイオウ原子を分子中に有する
含硫黄安定剤との組み合せを用いる。この組み合せを用
いれば、充填剤や難燃剤が混合されていても、あたかも
それらが混合されていない場合と同様な耐熱性が得られ
る。As the stabilizer, a hindered phenol stabilizer having a 2,4,8.10-tetraoxaspiro[5,5]undecane ring in the molecule and a sulfur-containing stabilizer having a divalent sulfur atom in the molecule are used. Use combinations. By using this combination, even if fillers and flame retardants are mixed, the same heat resistance as if they were not mixed can be obtained.
上記ヒンダードフェノール系安定剤としては３゜９−ビ
ス［１，１−ジメチル−２・ （β−（３ｔ−ブチル−
４−ハイドロキシ−５−メチルフェニル）プロピオニル
オキシ）エチル］２，４，８゜１０−テトラオキサスピ
ロ［５，５）ウンデカン、３９−ビス〔１，トジメチル
−２１（３５−ジ−ｔ−ブチル−４−ハイドロキシフェ
ニル）プロピオニルオキシ）エチル）２，４，８．ｔ。The above-mentioned hindered phenol stabilizer is 3゜9-bis[1,1-dimethyl-2.(β-(3t-butyl-
4-Hydroxy-5-methylphenyl)propionyloxy)ethyl]2,4,8゜10-tetraoxaspiro[5,5)undecane, 39-bis[1,todimethyl-21(35-di-t-butyl- 4-hydroxyphenyl)propionyloxy)ethyl)2,4,8. t.
テトラオキサスピロ〔５、５〕ウンデカンなどがあげら
れ、エチレン共重合体１００重量部に対して０．１重量
部以上５重量部以下用いられる。０目１部未満では耐熱
性向上効果が充分でなく、５重量部を越えるとブルーム
する危険が高くなる。Examples include tetraoxaspiro[5,5]undecane, which is used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the ethylene copolymer. If it is less than 1 part by weight, the effect of improving heat resistance will not be sufficient, and if it exceeds 5 parts by weight, there is a high risk of blooming.
前記含硫黄安定剤には２価のイオウ原子はスルフィド結
合の形式又はチオール基の形式で分子中に組み込まれて
いる。中でもチオール基を有する安定剤が効果が高く好
ましい、スルフィド結合をフ
有する安定剤としてはジラウリル３．３−チオジプロピ
オネート、シミリスチル３．３−チオジプロピオネート
、ジステアリル３．３・チオジプロピオネート、ペンタ
エリスリトールテトラキス（３ラウリルチオプロピオネ
ート）、ビス〔２−メチル−４・（３−ラウリルチ第１
ロビオニルオキシ）−５−ｔ−ブチルフェニル〕スルフ
ィドなどがあげられる。In the sulfur-containing stabilizer, a divalent sulfur atom is incorporated into the molecule in the form of a sulfide bond or a thiol group. Among them, stabilizers having a thiol group are highly effective and preferred. Examples of stabilizers having a sulfide bond include dilauryl 3,3-thiodipropionate, similystyl 3,3-thiodipropionate, and distearyl 3,3-thiodipropionate. pionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis[2-methyl-4.(3-laurylthiopropionate)
Robionyloxy)-5-t-butylphenyl] sulfide and the like.
チオール基を有する安定剤としては２−メルカプトベン
ズイミダゾール、２−メルカプトメチルベンズイミダゾ
ールなどがあげられる。チオール基を有する安定剤は亜
鉛などの金属の塩として使用しても良い。Examples of the stabilizer having a thiol group include 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole. The stabilizer having a thiol group may be used as a salt of a metal such as zinc.
これら含硫黄安定剤はエチレン共重合体１００重量部に
対して０．１重量部以上５重量部以下用いられる。０．
１重量部未満では効果が充分でなく、５重量部を超える
とブルームする危険が高くなる。These sulfur-containing stabilizers are used in an amount of 0.1 parts by weight or more and 5 parts by weight or less per 100 parts by weight of the ethylene copolymer. 0.
If it is less than 1 part by weight, the effect is not sufficient, and if it exceeds 5 parts by weight, there is a high risk of blooming.
このようにして安定化されたエチレン共重合体組成物は
熱可塑性であり、公知の押出成形、射出成形によって所
望の形状に成形される。このままでは高温にさらされた
場合溶融してしまうので、架橋を行なう。The ethylene copolymer composition stabilized in this manner is thermoplastic and can be molded into a desired shape by known extrusion molding or injection molding. If left as is, it will melt if exposed to high temperatures, so crosslinking is performed.
架橋は有機過酸化物の熱分解により発生したラジカルを
利用した化学架橋法、荷電粒子、例えば電子の照射によ
って発生したラジカルを利用した照射架橋法などによっ
て行なわれる。具体的な方法は公知であり、その中から
適当な方法を選択すれば良い、詳しくは架橋設備ハンド
ブック（１９８３年大成社刊）に述べられている。Crosslinking is carried out by a chemical crosslinking method using radicals generated by thermal decomposition of an organic peroxide, or by an irradiation crosslinking method using radicals generated by irradiation with charged particles, such as electrons. Specific methods are publicly known, and an appropriate method may be selected from among them; details are described in Crosslinking Equipment Handbook (published by Taiseisha, 1983).
（実施例） 以下に実施例を示し、本発明の内容を詳述する。(Example) Examples are shown below to explain the content of the present invention in detail.
−膜内に実施は下記の方法によった。２１の加圧型ニー
グーに表−１に示すエチレン共重合体及び安定剤を表−
２に示す部数投入して１分間混練した０次に充填削、難
燃剤を投入して１０分間混練した。- The implementation in the membrane was carried out by the following method. The ethylene copolymer and stabilizer shown in Table 1 were added to the pressurized Ni-Goo of No. 21.
The number of parts shown in No. 2 was added and kneaded for 1 minute.
本発明の組成物は以上の操作で得られるが、成形品の一
例として架橋ポリオレフィン電線用絶縁体として評価す
るため更に以下の操作を行なった。Although the composition of the present invention was obtained by the above operations, the following operations were further performed in order to evaluate it as an example of a molded product as an insulator for a crosslinked polyolefin electric wire.
電子線架橋にて評価する場合はトリアリルイソシアヌレ
ートをエチレン共重合体組成物１００重量部に対し３重
量部更にニーダ−中に投入し、１分間混練した。化学架
橋にて評価する場合はトリアリルイソシアヌレートを３
重量部、２，５ジメチル−２，５・ジ−ｔ−ブチルパー
オキシヘキシンを４重量部投入して１分間混練した。When evaluating by electron beam crosslinking, 3 parts by weight of triallyl isocyanurate was added to 100 parts by weight of the ethylene copolymer composition into a kneader, and kneaded for 1 minute. When evaluating by chemical crosslinking, triallyl isocyanurate is
4 parts by weight of 2,5 dimethyl-2,5-di-t-butylperoxyhexine were added and kneaded for 1 minute.
この組成物を一軸ナイロン用押出機で０．８ｍｍ厚に銅
線上に被覆し、被覆線とした。This composition was coated onto a copper wire to a thickness of 0.8 mm using a uniaxial nylon extruder to obtain a coated wire.
電子線架橋は２０Ｍｒａｄの線葺を上記被覆線に照射す
ることによった。Electron beam crosslinking was carried out by irradiating the coated wire with a 20 Mrad wire.
化学架橋は２００℃の溶融塩中の滞留時間が２分になる
ように、加圧溶融塩加硫を行なった。引張強度は被覆の
みを約２５℃で５００ ｍ ｍ ／ ｍ ｉｎの速度で
評価し、耐熱性は被覆のみを１８０℃２４０時間熱老化
後の破断点伸び残率で示した。Chemical crosslinking was carried out by pressurized molten salt vulcanization such that the residence time in 200° C. molten salt was 2 minutes. The tensile strength was evaluated by evaluating only the coating at a rate of 500 mm/min at about 25°C, and the heat resistance was expressed by the residual elongation at break after heat aging the coating only at 180°C for 240 hours.
実施例に於ては、比較的充填剤及び／又は難燃剤を多量
に必要とする難燃ポリオレフィン絶縁体用に応用した例
を示して本発明の効果を明らかにした。In the examples, the effects of the present invention were clarified by showing an example in which the present invention was applied to a flame-retardant polyolefin insulator that requires a relatively large amount of filler and/or flame retardant.
実施例１．２，３．４と比較例１，２，３．６とは本発
明の安定剤を使用してそれぞれ充填物がある場合と、な
い場合の対比であるが、その差は高々１０％程度しかな
く、しかも両方高レベルの耐熱性を示している。Examples 1.2, 3.4 and Comparative Examples 1, 2, 3.6 are comparisons of cases in which the stabilizer of the present invention is used with and without packing, respectively, and the differences are at most It is only about 10%, and both exhibit a high level of heat resistance.
比較例４．５は本発明以外の安定剤を使用して、充填物
がある場合とない場合の対比であるが、充填剤がある場
合、耐熱性が大きく落ちてしまう不都合がある。Comparative Example 4.5 uses a stabilizer other than the present invention and compares cases with and without fillers, but the presence of fillers has the disadvantage that heat resistance is greatly reduced.
〈以下余白）
（発明の効果）
本発明によれば充填剤や難燃剤を適宜配合することによ
り所望の特性に調節されたポリオレフィン樹脂・組成物
に高い耐熱性を付与できる。それ故、その用途により必
要とされる特性の差故に多種多様な組成で配合されるポ
リオレフィン組成物に、−様に高い耐熱性を付与できる
など産業上有益である。(Hereinafter in the margins) (Effects of the Invention) According to the present invention, high heat resistance can be imparted to a polyolefin resin/composition whose properties are adjusted to desired properties by appropriately blending fillers and flame retardants. Therefore, it is industrially useful because it can impart high heat resistance to polyolefin compositions that are blended with a wide variety of compositions due to differences in properties required depending on their uses.
Claims (2)
ステルから選ばれる１種又は２種以上の極性モノマーと
エチレンとの共重合体１００重量部に対し充填剤及び／
又は難燃剤が６０〜３００重量部混合され、更に２，４
，８，１０−テトラオキサスピロ〔５、５〕ウンデカン
環を分子中に有するヒンダードフェノール系安定剤０．
１〜５重量部及び２価のイオウ原子を分子中に有する含
硫黄安定剤０．１〜５重量部で安定化されてなるエチレ
ン共重合体組成物。(1) A filler and/or
Or 60 to 300 parts by weight of flame retardant is mixed, and further 2,4 parts by weight.
, 8,10-tetraoxaspiro[5,5]undecane ring-containing hindered phenol stabilizer 0.
An ethylene copolymer composition stabilized with 1 to 5 parts by weight and 0.1 to 5 parts by weight of a sulfur-containing stabilizer having a divalent sulfur atom in the molecule.
て架橋してなるエチレン共重合体成形品。(2) An ethylene copolymer molded article obtained by crosslinking the above composition with an organic peroxide or ionizing radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63260028A JP2648877B2 (en) | 1988-10-14 | 1988-10-14 | Ethylene copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63260028A JP2648877B2 (en) | 1988-10-14 | 1988-10-14 | Ethylene copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02105838A true JPH02105838A (en) | 1990-04-18 |
| JP2648877B2 JP2648877B2 (en) | 1997-09-03 |
Family
ID=17342302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63260028A Expired - Fee Related JP2648877B2 (en) | 1988-10-14 | 1988-10-14 | Ethylene copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2648877B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0593102A (en) * | 1991-10-01 | 1993-04-16 | Tatsuta Electric Wire & Cable Co Ltd | Radiation-resistant elastomer composition |
| JP2008050019A (en) * | 2006-08-23 | 2008-03-06 | Rengo Co Ltd | Easily openable packaging bag |
| JP2008247424A (en) * | 2007-03-30 | 2008-10-16 | Tokyo Autom Mach Works Ltd | Packaging bag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925826A (en) * | 1982-08-04 | 1984-02-09 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| JPS6230139A (en) * | 1985-04-09 | 1987-02-09 | Sumitomo Chem Co Ltd | Prevention of yellowing of polyolefin resin with nitrogen oxide gas |
| JPS6263590A (en) * | 1985-09-13 | 1987-03-20 | Sumitomo Chem Co Ltd | Hydroxyphenylpropionic acid derivative and stabilizer for organic substance containing said derivative as active |
| JPS6356544A (en) * | 1986-08-27 | 1988-03-11 | Mitsubishi Cable Ind Ltd | Fire-retardant composition |
| JPH01163233A (en) * | 1987-12-18 | 1989-06-27 | Chisso Corp | Flame-retardant polyolefin composition |
-
1988
- 1988-10-14 JP JP63260028A patent/JP2648877B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925826A (en) * | 1982-08-04 | 1984-02-09 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| JPS6230139A (en) * | 1985-04-09 | 1987-02-09 | Sumitomo Chem Co Ltd | Prevention of yellowing of polyolefin resin with nitrogen oxide gas |
| JPS6263590A (en) * | 1985-09-13 | 1987-03-20 | Sumitomo Chem Co Ltd | Hydroxyphenylpropionic acid derivative and stabilizer for organic substance containing said derivative as active |
| JPS6356544A (en) * | 1986-08-27 | 1988-03-11 | Mitsubishi Cable Ind Ltd | Fire-retardant composition |
| JPH01163233A (en) * | 1987-12-18 | 1989-06-27 | Chisso Corp | Flame-retardant polyolefin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0593102A (en) * | 1991-10-01 | 1993-04-16 | Tatsuta Electric Wire & Cable Co Ltd | Radiation-resistant elastomer composition |
| JP2008050019A (en) * | 2006-08-23 | 2008-03-06 | Rengo Co Ltd | Easily openable packaging bag |
| JP2008247424A (en) * | 2007-03-30 | 2008-10-16 | Tokyo Autom Mach Works Ltd | Packaging bag |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2648877B2 (en) | 1997-09-03 |
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