JPH01101348A - Heat-resistant and flame-retardant composition - Google Patents
Heat-resistant and flame-retardant compositionInfo
- Publication number
- JPH01101348A JPH01101348A JP25934887A JP25934887A JPH01101348A JP H01101348 A JPH01101348 A JP H01101348A JP 25934887 A JP25934887 A JP 25934887A JP 25934887 A JP25934887 A JP 25934887A JP H01101348 A JPH01101348 A JP H01101348A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- propylene
- ethylene
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 26
- 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 title claims abstract description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011630 iodine Substances 0.000 claims abstract description 18
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 22
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 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 abstract description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 abstract description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 2
- 230000003449 preventive effect Effects 0.000 abstract 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 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 5
- -1 butyl-4-hydroxyphenyl Chemical group 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 1
- WJPZDRIJJYYRAH-UHFFFAOYSA-N [Zn].[Mo] Chemical class [Zn].[Mo] WJPZDRIJJYYRAH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical class [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- 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、特殊なエチレン−プロピレン−ジエン三元共
重合体をベースとする架橋性の耐熱性難燃性組成物に関
し、電線、就中、車両用電線のような耐熱絶縁電線の絶
縁被覆材などとして好適な組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a crosslinkable, heat-resistant, flame-retardant composition based on a special ethylene-propylene-diene terpolymer, which is suitable for use in electrical wires, in particular in vehicles. The present invention relates to a composition suitable as an insulation coating material for heat-resistant insulated wires such as utility wires.
従来の技術
従来、モーター用リード線や車両機関部の周辺部品用電
線などとして用いられている耐熱絶縁電線としては、ヨ
ウ素価が約１５以上のエチレン−プロピレン−ジエン三
元共重合体をベースとする難燃性絶＆ｉ＆ＩＩ成物を用
いて被覆されたものが知られている。Conventional technology Conventionally, heat-resistant insulated wires used as lead wires for motors and wires for peripheral parts of vehicle engines are based on ethylene-propylene-diene terpolymer with an iodine value of about 15 or more. Coatings using flame retardant I&II compositions are known.
ところで最近、上記耐熱絶縁ｉｔ標線類対して一層高度
の耐熱性の改善が要求されている０本発明者らはこの要
求に応え得る絶縁組成物を開発することを目的として、
また現用のヨウ素価が約１５以上のエチレン−プロピレ
ン−ジエン三元共重合体自体が左程耐熱性に優れている
とはいい難いので、該共重合体より耐熱性の優れている
ことが一般に知られているエチレン・プロピレン共重合
体を採用して開発研究を行ってきた。しかしながらエチ
レン・プロピレン共重合体は、難燃化することが困難で
あり、充分に難燃化しようとすると多量の難燃剤が必要
となって組成物の押出加工性や可撓性に悪影響がでる問
題がある。By the way, recently, there has been a demand for a higher degree of improvement in heat resistance for the above-mentioned heat-resistant insulation IT gauges.The present inventors aimed to develop an insulating composition that can meet this demand.
In addition, it is difficult to say that the currently used ethylene-propylene-diene terpolymer with an iodine value of about 15 or more has excellent heat resistance, so it is generally said that the copolymer has better heat resistance than the above copolymer. Development research has been conducted using a known ethylene-propylene copolymer. However, it is difficult to make ethylene-propylene copolymers flame retardant, and in order to make them sufficiently flame retardant, a large amount of flame retardant is required, which adversely affects the extrudability and flexibility of the composition. There's a problem.
解決を要すべき問題点
上記した理由から、エチレン−プロピレン共重合体組成
物と同等かまたはそれに近い耐熱性を有し、しかも従来
使用のエチレン−プロピレン−ジエン三元共重合体絶縁
組成物と同程度の難燃性を有する絶縁性の耐熱性難燃性
組成物の開発が焦眉となっている。Problems that need to be solved For the reasons mentioned above, it is necessary to use an insulating composition that has heat resistance equal to or close to that of an ethylene-propylene copolymer composition, and that is also comparable to the conventionally used ethylene-propylene-diene terpolymer insulating composition. There is an urgent need to develop an insulating, heat-resistant, flame-retardant composition that has the same degree of flame retardancy.
問題点を解決するための手段
上記した問題点を解決するための手段として、本発明は
ヨウ素価が１〜ｌＯのエチレン−プロピレン−ジエン三
元共重合体と該共重合体１００重量部に対し、２〜１５
重量部の老化防止剤、８〜１５０重砥部の難燃剤、１〜
５重量部の有機過酸化物架橋剤、および０．１〜５重量
部の多官能性架橋助剤とからなることを特徴とする耐熱
性難燃性組成物を提供しようとするものである。Means for Solving the Problems As a means for solving the above-mentioned problems, the present invention provides an ethylene-propylene-diene terpolymer having an iodine value of 1 to 1O, and a copolymer based on 100 parts by weight of the copolymer. , 2-15
Antioxidant, 8 to 150 parts by weight of flame retardant, 1 to 150 parts by weight of flame retardant,
It is an object of the present invention to provide a heat-resistant flame-retardant composition characterized by comprising 5 parts by weight of an organic peroxide crosslinking agent and 0.1 to 5 parts by weight of a polyfunctional crosslinking aid.
作用
本発明者らの引き続く開発研究から、ヘースとなる有機
高分子としてヨウ素価が１−１０のエチレン−プロピレ
ン−ジエン三元共重合体は、難燃化が容易であり、しか
も耐熱性にも優れていることがわかった。また該共重合
体に老化防止剤、難燃剤、有機過酸化物架橋剤、および
多官能性架橋助剤とを上記した特定量配合して得た本発
明の組成物は、通常の方法並びに条件で架橋することに
よりエチレン−プロピレン共重合体組成物の架橋体に匹
敵する耐熱性を有し、しかも実用上満足できる難燃性、
押出加工、および可撓性を兼備する架橋体となる。Effect The inventors' continued research and development revealed that ethylene-propylene-diene terpolymer with an iodine value of 1 to 10 is easy to make flame retardant and has excellent heat resistance as an organic polymer for forming haze. I found it to be excellent. Further, the composition of the present invention obtained by blending the above-mentioned specific amounts of an anti-aging agent, a flame retardant, an organic peroxide cross-linking agent, and a polyfunctional cross-linking auxiliary agent with the copolymer can be prepared by a conventional method and conditions. It has heat resistance comparable to a crosslinked product of an ethylene-propylene copolymer composition by crosslinking with
It becomes a crosslinked product that can be extruded and has flexibility.
発明の詳細な説明
本発明において用いられるエチレン−プロピレン−ジエ
ン三元共重合体は、ヨウ素価が１〜１０のものである。Detailed Description of the Invention The ethylene-propylene-diene terpolymer used in the present invention has an iodine value of 1 to 10.
このように、従来に比べてジエン成分の含有量が温かに
少ないものを用いることにより、本発明の目的が達成さ
れる。ヨウ素価が１未満のものでは得られる組成物の加
工性に乏しく、１０を超えるとその組成物の架橋体の耐
熱性が乏しい。エチレン−プロピレン−ジエン三元共重
合体におけるジエン成分としてはエチリデンノルボーネ
ン、ジシクロペンタジェン、１．４−ヘキサジエンなど
の環状又は鎖状の非共役ジエンなどがあげられるが、特
にジシクロペンタジェンの如く分岐のできやすいものが
好ましい。押出加工性の観点から、好ましく用いうるエ
チレン−プロピレン−ジエン三元共重合体はプロピレン
含量量が２５〜５０重量％で、粘度が５０以下（ムーニ
ー粘度；１００℃）であり、ヨウ素価が２〜６のもので
ある。In this way, the object of the present invention can be achieved by using a material with a lower diene component content than conventional ones. If the iodine value is less than 1, the resulting composition will have poor processability, and if it exceeds 10, the crosslinked product of the composition will have poor heat resistance. Examples of the diene component in the ethylene-propylene-diene terpolymer include cyclic or chain non-conjugated dienes such as ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene, but in particular dicyclopentadiene. It is preferable to use one that is easy to branch, such as. From the viewpoint of extrusion processability, the ethylene-propylene-diene terpolymer that can be preferably used has a propylene content of 25 to 50% by weight, a viscosity of 50 or less (Mooney viscosity; 100°C), and an iodine value of 2. ~6.
本発明に於いて老化防止剤としては、ゴムやプラスチッ
クなどに配合される公知のものが用いられる。配合量は
、エチレン−プロピレン−ジエン三元共重合体１００重
量部あたり、２〜１５重量部が適当であり、３〜１０重
量部が好ましい、その配合量が２重量部未満では得られ
る組成物の架橋体の耐熱性に乏しく、１５重量部を超え
るとブルーミングを起こし易い。As the anti-aging agent in the present invention, known anti-aging agents that are blended into rubbers, plastics and the like can be used. The appropriate amount is 2 to 15 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the ethylene-propylene-diene terpolymer.If the amount is less than 2 parts by weight, the composition obtained The crosslinked product has poor heat resistance, and if it exceeds 15 parts by weight, blooming tends to occur.
好ましく用いうる老化防止剤としては、２−メルカプト
ベンゾイミダゾールやその亜鉛塩等のイミダゾール類、
１，３．５− ）リス（３，５−ジ−ｔ−ブチル−４−
ヒドロキシベンジル）−５−）リアジン−２，４，６（
ＩＨ。Preferably used anti-aging agents include imidazoles such as 2-mercaptobenzimidazole and its zinc salt;
1,3.5- ) lis(3,5-di-t-butyl-4-
hydroxybenzyl)-5-) riazine-2,4,6(
IH.
３１１．５１１）−トリオン等のフェノール類、ビス〔
２−メチル−４−（３−ｎ−アルキル（ＣＩ２〜Ｃ１４
）チオプロピオニルオキシ）−５〜ｔ−ブチルフェニル
〕スルフィド、オクタデシル−３−（３，５−ジー多−
ブチルー４−ヒドロキシフヱニル）プロピオネート等の
ヒンダードフェノール類、１．２−ジヒドロ−２，２，
４−）リメチルニトノリンなどがあげられる。
、
本発明に於いて難燃剤としては、ゴムやプラスチックな
どの難燃剤として公知のものが用いられるが、下記の組
み合わせ組成のものが特に好ましい。311.511)-phenols such as trione, bis[
2-Methyl-4-(3-n-alkyl(CI2-C14
)thiopropionyloxy)-5-t-butylphenyl] sulfide, octadecyl-3-(3,5-di-poly-
Hindered phenols such as butyl-4-hydroxyphenyl) propionate, 1,2-dihydro-2,2,
4-) Limethylnitonoline and the like.
As the flame retardant in the present invention, those known as flame retardants for rubber, plastic, etc. can be used, but those having the following combination composition are particularly preferred.
すなわら、上記エチレン−プロピレン−ジエン三元共重
合体１００重量部に対して
＋ａｌ 含Ｂ「有機難燃剤５〜７０重量部（ｂｌ
５ｂｚＱｚ 、 １〜２０重量部（Ｃ１亜鉛化合
物 １〜３０重量部、および［ｄｌ 赤リン
１〜３０重量部の４成分からなるものである。In other words, 5 to 70 parts by weight of an organic flame retardant containing +al B to 100 parts by weight of the above ethylene-propylene-diene terpolymer (bl
5bzQz, 1 to 20 parts by weight (C1 zinc compound 1 to 30 parts by weight, and [dl red phosphorus
It consists of four components of 1 to 30 parts by weight.
（δ）成分としては、デカブロモジフェニルオキサイド
、テトラビスフェノールＡ−へキサブロモシクロデカン
、ビス（ブロモエチルエーテル）テトラブロモビスフェ
ノールＡ等が挙げられる。Examples of the component (δ) include decabromodiphenyl oxide, tetrabisphenol A-hexabromocyclodecane, bis(bromoethyl ether)tetrabromobisphenol A, and the like.
ｔｅｌ成分としては、亜鉛又は亜鉛元素を含む各種の有
機又は無機化合物が用いられる。たとえば３ＺｎＯ−２
８ｚＯｚ−３１１ｚＯ，２ＺｎＯ−３８ｇＯｔ−３！４
１１ｚＯ、等の硼酸鉛化合物類、ＺｎＯ−ＺｎＭｏＯ４
，ＣａＯ−ＺｎＭｏ０ａ、ＺｎＭｏ０ｓ−ＣａＳＯ４等
のモリブデン−亜鉛化合物等が挙げられる。特に好まし
くは、硼酸亜鉛、モリブデンの亜鉛化合物類である。As the tel component, zinc or various organic or inorganic compounds containing the zinc element are used. For example, 3ZnO-2
8zOz-311zO,2ZnO-38gOt-3!4
Lead borate compounds such as 11zO, ZnO-ZnMoO4
, CaO-ZnMo0a, ZnMo0s-CaSO4, and other molybdenum-zinc compounds. Particularly preferred are zinc borate and zinc compounds of molybdenum.
＋ｄ＋ｄｌとしては、従来市販されているものを広く使
用でき、たとえば赤リン分が８０重量％以上であって、
乾燥減量が０．８重量％以下且つ７４・メツシュ篩残分
が７％以下であるものが好ましい。As +d+dl, conventionally commercially available products can be widely used, for example, red phosphorus content is 80% by weight or more,
It is preferable that the loss on drying is 0.8% by weight or less and the 74.mesh sieve residue is 7% or less.
また、前記赤リンの表面がフェノール−ホルマリン樹脂
等の熱硬化性樹脂で被覆されたものも好ましい。その具
体例としては、ノーパレット＃１２０、ノーバレット＃
１２０ＵＦ［いずれも燐化学工業社型］等を挙げること
ができる。It is also preferable that the surface of the red phosphorus is coated with a thermosetting resin such as phenol-formalin resin. Specific examples include No Palette #120, No Pallet #
120UF [all manufactured by Rin Kagaku Kogyo Co., Ltd.], and the like.
ｆａｔ成分と（ｂｌ成分の組合わせのみでは両成分をか
なり多量に使用してもデ「燃性の向上効果が乏しく、ｆ
ａｔ成分と（ｂｌ成分の他に更にｔｃ＋ｃｌと（ｄｌ成
分とを上記した配合比で併用する事によって大幅な難燃
性の改善効果が得られる。特にｆｃｌ成分と（ｄ）成分
との使用量が略同じである場合に最も難燃化作用が大き
い。If only the fat component and (BL component) are combined, even if both components are used in fairly large amounts, the effect of improving flammability will be poor, and the f
A significant flame retardant improvement effect can be obtained by using together the at component, (bl component, tc + cl, and (dl) component in the above-mentioned blending ratio.In particular, the amount of the fcl component and (d) component used) The flame retardant effect is greatest when these are approximately the same.
難燃剤（ａｌ ｆｂｌ （ｃｌ ［ｄｌ成分は、その合
計量がエチレン−プロピレン−ジエン三元共重合体１０
０重量部あたり、８重量部〜１５０重量部の範囲で使用
される。８重量部より少ないと難燃性の向上作用かに乏
しく、１５０重量部より多いと組成物の機械特性、耐熱
性、加工性が低下する。したがって、難燃剤（ａ）’（
ｂｌ （ｃ） （ｄ）成分の合計量がエチレン−プロピ
レン−ジエン三元共重合体１００重量部あたり、好まし
くは２０重量部〜９０重量部、最も好ましくは３０重量
部〜６０ｆｔ量部である。Flame retardant (al fbl (cl [dl component is the total amount of ethylene-propylene-diene terpolymer copolymer 10
It is used in a range of 8 parts by weight to 150 parts by weight per 0 parts by weight. If it is less than 8 parts by weight, the effect of improving flame retardancy will be poor, and if it is more than 150 parts by weight, the mechanical properties, heat resistance, and processability of the composition will deteriorate. Therefore, flame retardant (a)'(
The total amount of components bl (c) and (d) is preferably 20 parts by weight to 90 parts by weight, most preferably 30 parts by weight to 60 parts by weight per 100 parts by weight of the ethylene-propylene-diene terpolymer.
本発明の組成物は、実用に際しては有機過酸化物架橋剤
と多官能性架橋助剤との作用により架橋される。有機過
酸化物架橋剤および多官能性架橋助剤については特に限
定はなく、ゴムやプラスチックなどを架橋するために通
常配合される公知のものが用いられる。In practical use, the composition of the present invention is crosslinked by the action of an organic peroxide crosslinking agent and a polyfunctional crosslinking aid. There are no particular limitations on the organic peroxide crosslinking agent and the polyfunctional crosslinking aid, and known ones that are commonly blended for crosslinking rubbers, plastics, etc. can be used.
好ましく用いうる有機過酸化物架橋剤としてはジクミル
パーオキサイド、１．３−ビス（ドブチルパーオキシイ
ソプロピル）ベンセン、１．１−ビス（１−ブチルパー
オキシ）−３，３・、５−トリメチルシクロヘキ ０、
サン、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキ
シ）バレレートなとがあげらる。Preferred organic peroxide crosslinking agents include dicumyl peroxide, 1.3-bis(dobutylperoxyisopropyl)benzene, 1.1-bis(1-butylperoxy)-3,3.,5- Trimethylcyclohex 0,
and n-butyl-4,4-bis(t-butylperoxy)valerate.
好ましく用いうる多官能性架橋助剤としては、トリアリ
ルイソシアヌレート、トリアリルシアヌレート、Ｎ、Ｎ
’−ｍ−フェニレンビスマレイミド、ｐ。As the polyfunctional crosslinking aid that can be preferably used, triallyl isocyanurate, triallyl cyanurate, N, N
'-m-phenylene bismaleimide, p.
ｐ−ジベンゾイルキノンジオキシム、ｐ−キノンジオキ
シムなどがあげられる。Examples include p-dibenzoylquinone dioxime and p-quinone dioxime.
有機過酸化物架橋剤の配合量はエチレン−プロピレン−
ジエン三元共重合体体１００量定部あたり、１〜５重量
部が適当であり、好ましくは２〜４重量部である。その
配合量が１重量部未満では得られる架橋体が架橋度にお
いて充分でなり、−方、５重狙部を超えると架橋体の耐
熱性が乏しくなる。The amount of organic peroxide crosslinking agent is ethylene-propylene-
The amount is suitably 1 to 5 parts by weight, preferably 2 to 4 parts by weight, per 100 parts by weight of the diene terpolymer. If the amount is less than 1 part by weight, the resulting crosslinked product will have a sufficient degree of crosslinking, while if it exceeds 5 parts by weight, the crosslinked product will have poor heat resistance.
多官能性架橋助剤の配合量はエチレン・プロピレン・ジ
エン三元共重合体１００重量部ｔ部あたり、０．１〜５
重屋部が適当であり、好ましくは０゜５〜３重ｕ部であ
る。その配合量が０．３重量部未満では架橋度に乏しく
、５重量部を超えると得られる架橋体が耐老化性に乏し
くなる。The blending amount of the polyfunctional crosslinking aid is 0.1 to 5 parts by weight per 100 parts by weight of the ethylene-propylene-diene terpolymer.
A double layer is suitable, preferably 0.5 to 3 layers. If the amount is less than 0.3 parts by weight, the degree of crosslinking will be poor, and if it exceeds 5 parts by weight, the resulting crosslinked product will have poor aging resistance.
本発明の組成物の架橋は、有機過酸化物架橋剤を分解さ
せる加熱処理方式がとられるが、その加熱処理は、たと
えば本発明組成物を用いた絶縁電線の製造の場合、導体
の上に本発明組成物を押出被覆し、高圧水蒸気架橋法、
ＬＣＭ、粒子流動床等の方法で架橋される。Crosslinking of the composition of the present invention takes a heat treatment method that decomposes the organic peroxide crosslinking agent. For example, in the case of manufacturing an insulated wire using the composition of the present invention, the heat treatment Extrusion coating of the composition of the present invention, high pressure steam crosslinking method,
Crosslinking is carried out by methods such as LCM and particle fluidized bed.
本発明の組成物には必要に応じ、ゴムやプラスチックな
どに通例配合されることのあるたとえばミストロンベー
パタルク、硫酸バリウム、焼成りレー、焼成シリカ、炭
酸カルシウム、酸化亜鉛等の充填剤、酸化チタン、カー
ボンブラック等の顔料、ステアリン酸、ステアリン酸ソ
ーダー等の滑剤、プロセス油等の加工助剤なとを通常量
配合してもよい、またポリエチレン、エチレン−酢酸ビ
ニル共重合体、エチレン−アクリル酸エチル共重合体、
塩素化ポリエチレン、アルファオレフィンエラストマー
、四フッ化エチレンープロピレン共重合体あるいはその
他の有機高分子を機械特性、耐油性、押出加工性を向上
させるため添加してよい、該有機高分子の配合量はエチ
レン・プロピレン・ジエン三元共重合体１００重量部に
対して１〜７０重量部程度、特に５〜５０ｉｌｉｆｆｉ
部程度が適当である。The composition of the present invention may contain fillers such as mistron vapor talc, barium sulfate, calcined ray, calcined silica, calcium carbonate, zinc oxide, etc., which are usually incorporated into rubbers and plastics, as necessary. Pigments such as titanium and carbon black, lubricants such as stearic acid and sodium stearate, and processing aids such as process oil may be added in normal amounts.Also, polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic ethyl acid copolymer,
Chlorinated polyethylene, alpha olefin elastomer, tetrafluoroethylene-propylene copolymer, or other organic polymer may be added to improve mechanical properties, oil resistance, and extrusion processability. About 1 to 70 parts by weight, especially 5 to 50 parts by weight per 100 parts by weight of the ethylene-propylene-diene terpolymer
Approximately 100% is appropriate.
発明の効果
本発明の組成物は加工性が良好であり、しかも所望の形
状に加工後は通常の加熱架橋方法で容易に架橋すること
ができる。また得られた架橋体は電気特性、可撓性に優
れ、エチレン−プロピレン共重合体ベース組成物の架橋
体に匹敵する耐熱性を有し、しかも従来使用のエチレン
−プロピレン−ジエン三元共重合体絶縁組成物と同程度
の難燃性を有する。したがって、本発明のＮ、ｌ酸物は
、電線、就中重両用電線等、耐熱性の要求される電線の
被覆材として頗る好適である。Effects of the Invention The composition of the present invention has good processability, and moreover, after being processed into a desired shape, it can be easily crosslinked by a normal heat crosslinking method. In addition, the obtained crosslinked product has excellent electrical properties and flexibility, and has heat resistance comparable to that of a crosslinked product based on an ethylene-propylene copolymer base composition. It has flame retardancy comparable to that of coalesced insulation compositions. Therefore, the N, L acid compound of the present invention is highly suitable as a coating material for electric wires that require heat resistance, such as electric wires, especially dual-purpose electric wires.
実施例
以下、実施例および比較例により本発明を一層詳細に説
明する。以下において、特に断らない限り、部、％は、
それぞれ重量部、重吋％を意味するものとする。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In the following, unless otherwise specified, parts and percentages are
They each mean parts by weight and % by weight.
実施例１
ヨウ素価が２のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２１２１、社製化学社！！り１００部と、亜鉛
華５部と、ステアリン酸１部と、カーボンブラック（ダ
イヤブラック■（）５部と、ミストロンベーパタルク３
０部と、デカブロモジフェニルオキサイド（臭素系難燃
剤グレートレークＤＥ−８３Ｒ、グレートレニク社製）
３０部と、５ｂｌＯｓ５部と、硼酸亜鉛５部と、赤リン
（ノーパレット１２０ｕＦ、Ｊｆｆｉ化学社製）５部と
、メルカプトベン
入内新興化学工業社製）３部と、１．２−ジヒドロ−２
、２．４− トリメチルキノリン（老防２２４、入内
新興化学工業社製）１部と、ナフテン系プロセス油（サ
ンセン４２４０、日本サンオイル社製） ５部と、ジク
ミルパーオキサイド（バークジ１１０１日零ｍＪＩ１１
）２．’を部と、Ｎ＋Ｎ’−ｍ−フェニレンビスマレイ
ミド（ＨＶＡ＃２、デュポン社製）１、５部とを２本ロ
ールで充分混練して混線組成物を得た。Example 1 100 parts of an ethylene-propylene-diene ternary copolymer (P2121, manufactured by Kagakusha!!) with an iodine value of 2, 5 parts of zinc white, 1 part of stearic acid, and carbon black (Diablack ■ () Part 5 and Mistron Bepa Taluk 3
0 parts and decabromodiphenyl oxide (brominated flame retardant Greatlake DE-83R, manufactured by Greatrenik)
30 parts, 5 parts of 5blOs, 5 parts of zinc borate, 5 parts of red phosphorus (no pallet 120 uF, manufactured by Jffi Chemical Co., Ltd.), 3 parts of mercaptoben (manufactured by Iriuchi Shinko Kagaku Kogyo Co., Ltd.), and 1,2-dihydro-2
, 1 part of 2.4-trimethylquinoline (Robo 224, manufactured by Iriuchisho Shinko Kagaku Kogyo Co., Ltd.), 5 parts of naphthenic process oil (Sansen 4240, manufactured by Nippon Sun Oil Co., Ltd.), and dicumyl peroxide (Bakuji 1101 Day Zero). mJI11
)2. ' and 1.5 parts of N+N'-m-phenylene bismaleimide (HVA #2, manufactured by DuPont) were sufficiently kneaded with two rolls to obtain a mixed wire composition.
実施例２
ヨウ素価が４のエチレン−プロピレン−ジエン三元共重
合体（Ｐ ２ ２ ６ ２、社製化学社製）を用いた他
は、実施例１に準じて混線組成物を得た。Example 2 A crosstalk composition was obtained according to Example 1, except that an ethylene-propylene-diene terpolymer (P 2 2 6 2, manufactured by Shasei Kagaku Co., Ltd.) having an iodine value of 4 was used.
実施例３
ヨウ素価が６のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２１６１，社製化学社製）を用いた他は、実施
例１に準じて混練組成物を得た。Example 3 A kneaded composition was obtained in accordance with Example 1, except that an ethylene-propylene-diene terpolymer (P2161, manufactured by Kagaku Kagaku Co., Ltd.) having an iodine value of 6 was used.
実施例４
ヨウ素価が４のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２２６２、社製化学社製）を用い、また硼酸亜
鉛に代わってＺｎＯ−ＺｎＭ。０４ケムガード９１１Ｂ
、日本シャウィンウィリアムスケミカル社製）５部を用
いた他は、実施例１に準じて混ｍ組成物を得た。Example 4 An ethylene-propylene-diene terpolymer (P2262, manufactured by Shasei Kagaku Co., Ltd.) having an iodine value of 4 was used, and ZnO-ZnM was used instead of zinc borate. 04 Chemguard 911B
A mixed composition was obtained according to Example 1, except that 5 parts of the compound (manufactured by Japan Shawin Williams Chemical Co., Ltd.) were used.
実施例５
ヨウ素価が４のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２２６２、社製化学社製）を用い、またＮ，Ｎ
’−トフエニレンビスマレイミドに代わってトリアリル
イソシアヌレート（日本化成社製）１．５部を用いた他
は、実施例１に準じて混練組成物を得た。Example 5 An ethylene-propylene-diene terpolymer (P2262, manufactured by Shasei Kagaku Co., Ltd.) with an iodine value of 4 was used, and N,N
A kneaded composition was obtained according to Example 1, except that 1.5 parts of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) was used in place of '-tophenylene bismaleimide.
実施例６
硼酸亜鉛１０部と、赤リン（ノーバレット１２０ｕＦ，
燐化学社製）１０部とを用いた他は、実施例２に準じて
混ｋ１１ｔＭｉ成物を得た。Example 6 10 parts of zinc borate and red phosphorus (Nobalet 120uF,
A mixed k11tMi composition was obtained in accordance with Example 2, except that 10 parts of (manufactured by Rin Kagaku Co., Ltd.) was used.
実施例７
ヨウ素価が４のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２２６２、社製化学社製）８０部と、エチレン
−酢酸ビニル共重合体（エバチー）Ｋ２ ０ １ ０、
三井石油化学社製）２０ｆｆｉｉｔ部とＮ，Ｎ’−ｍ・
−フェニレンビスマレイミド１部とを用いた他は、実施
例Ｘに阜して混練組成物を得た。Example 7 80 parts of an ethylene-propylene-diene ternary copolymer (P2262, manufactured by Shasei Kagaku Co., Ltd.) with an iodine value of 4, and an ethylene-vinyl acetate copolymer (Evacy) K2010,
Mitsui Petrochemical Co., Ltd.) 20ffiit part and N, N'-m・
- A kneaded composition was obtained in accordance with Example X, except that 1 part of phenylene bismaleimide was used.
実施例８
ヨウ素価が４のエチレン−プロピレン−ジエン三元共重
合体（Ｐ２２６２、住人化学社製）６０部と、アルファ
オレフィンエラストマー（タフマーＡ４０９０、三片石
油化学社製）４０部と、Ｎ、 Ｎ’ −ｍ−フェニレン
ビスマレイミド２部とを用いた他は、実施例Ｉに準じて
混練組成物を得た。Example 8 60 parts of an ethylene-propylene-diene terpolymer with an iodine value of 4 (P2262, manufactured by Sumima Kagaku Co., Ltd.), 40 parts of an alpha olefin elastomer (Tafmer A4090, manufactured by Mikata Petrochemical Co., Ltd.), N, A kneaded composition was obtained according to Example I, except that 2 parts of N'-m-phenylene bismaleimide was used.
実施例９
メルカプトベンツイミダゾール（ツクラックＭＢ、入内
新興化学工業社製）３部と、１．２−ジヒドロ−２，２
，４−）リメチルキノリン（老防２２４、入内新興化学
工業社製）１部とに代わって、１，３．５−トリス（３
，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−８
−トリアジン−２，４，６（ＩＨ，３１１，５１１）−
トリオン（ＭＡＲＫ Ａ０１８、アデカアーガス社製
）４部を用いた他は、実施例２に準じて混練組成°物を
得た。Example 9 3 parts of mercaptobenzimidazole (TSKURAK MB, manufactured by Irinai Shinko Kagaku Kogyo Co., Ltd.) and 1,2-dihydro-2,2
,4-)limethylquinoline (Robo 224, manufactured by Iriuchi Shinko Kagaku Kogyo Co., Ltd.) and 1 part of 1,3.5-tris(3
,5-di-t-butyl-4-hydroxybenzyl)-8
-Triazine-2,4,6(IH,311,511)-
A kneaded composition was obtained in accordance with Example 2, except that 4 parts of Trion (MARK A018, manufactured by Adeka Argus) was used.
実施例Ｉ０
１．２−ジヒドロ−２，２，４−トリメチルキノリンを
使用せず、かりＮ＋ Ｎ’−ｍ−２ヱニレンビスマレイ
ミドの使用７ｉ１を１部とした他は、実施例２に準じて
混練組成物を得た。Example I0 Same as Example 2 except that 1,2-dihydro-2,2,4-trimethylquinoline was not used and 1 part of 7i1 was used instead of N+N'-m-2enylene bismaleimide. A kneaded composition was obtained.
比較例！
硼酸亜鉛と赤リンとを共に使用しなかった他は実施例２
に準じて混練組成物を得た。Comparative example! Example 2 except that zinc borate and red phosphorus were not used together.
A kneaded composition was obtained according to .
比較例２
ヨウ素価がＯのエチレン−プロピレン−共重合体（ＥＰ
Ｏ２Ｐ、日本合成ゴム社製”）１００部を用いた他は、
実施例１に準じて混練組成物を得た。Comparative Example 2 Ethylene-propylene copolymer (EP
In addition to using 100 parts of O2P (manufactured by Japan Synthetic Rubber Co., Ltd.),
A kneaded composition was obtained according to Example 1.
比較例３
ヨウ素価が１９のエチレン−プロピレン−ジエン三元共
重合体（ＥＰ２１、日本合成ゴム社製）１００部を用い
た他は、実施例１に準じて混練組成物を得た。Comparative Example 3 A kneaded composition was obtained according to Example 1, except that 100 parts of an ethylene-propylene-diene ternary copolymer (EP21, manufactured by Japan Synthetic Rubber Co., Ltd.) having an iodine value of 19 was used.
評価試験
耐熱性：実施例、比較例の混練組成物を１７０’ｃで２
０分間プレス成形して得た厚さ約２龍の加硫シートを、
ＪＩＳに６３０１ ｒ加硫ゴ −ムの物理試験方法」
に準じて、２００℃のギアーオープン中で２日間老化さ
せ、得られた老化シートについてその伸び率を測定し、
伸びの絶対値が２００％以上の場合を○、この値未満の
場合を×として評価した。Evaluation test Heat resistance: The kneaded compositions of Examples and Comparative Examples were tested at 170'c for 2
A vulcanized sheet approximately 2 mm thick obtained by press molding for 0 minutes,
JIS 6301r ``Physical test method for vulcanized rubber''
According to the above, the aged sheet was aged for 2 days in a gear open at 200 ° C., and the elongation rate of the obtained aged sheet was measured.
The case where the absolute value of elongation was 200% or more was evaluated as ○, and the case where it was less than this value was evaluated as ×.
加工性：実施例、比較例の混練組成物をブラベンダープ
ラスチコーダーゴム用押出機（Ｌ／Ｄ ： １０）で約
２醜−径の紐状に押出しくダイの温度１００℃、シリン
ダ温度
８０℃、スクリュの回転数８０ｒｐｓ＋）、得られた紐
状物の外観が平滑な場合をＯ１外観に肌荒れ様の乱れが
ある場合を×として評価した。Processability: The kneaded compositions of Examples and Comparative Examples were extruded into a string shape with a diameter of about 2 mm using a Brabender Plasticorder rubber extruder (L/D: 10) at a die temperature of 100°C and a cylinder temperature of 80°C. , screw rotation speed 80 rps+), and the case where the appearance of the obtained string-like product was smooth was evaluated as O1, and the case where there was rough skin-like disturbance in the appearance was evaluated as ×.
難燃性：実施例、比較例の混練組成物を１７０℃で２０
分間プレス成形加硫して得た厚さ約３■ｌの加硫シート
を、ＪＩＳに７２０１ ｒ酸素指数法による高分子材料
の燃焼試験」に準じて酸素指数を測定評価した。Flame retardancy: The kneaded compositions of Examples and Comparative Examples were heated to 20°C at 170°C.
A vulcanized sheet having a thickness of about 3 liters obtained by press molding and vulcanization for minutes was evaluated by measuring the oxygen index according to JIS 7201 "Flammation test of polymeric materials by oxygen index method".
上記の試験結果を下表に示した。The above test results are shown in the table below.
特許出願人 三菱電線工業株式会社Patent applicant: Mitsubishi Cable Industries, Ltd.
Claims (1)
ン三元共重合体と該共重合体１００重量部に対し、２〜
１５重量部の老化防止剤、８〜１５０重量部の難燃剤、
１〜５重量部の有機過酸化物架橋剤、および０．１〜５
重量部の多官能性架橋助剤とからなることを特徴とする
耐熱性難燃性組成物。 ２、難燃剤がエチレン−プロピレン−ジエン三元共重合
体１００重量部に対して含Ｂｒ有機難燃剤５〜７０重量
部、Ｓｂ＿２Ｏ＿３１〜２０重量部、亜鉛化合物１〜３
０重量部、および赤リン１〜３０重量部とからなるもの
である特許請求の範囲第１項に記載の耐熱性難燃性組成
物。[Scope of Claims] 1. An ethylene-propylene-diene terpolymer having an iodine value of 1 to 10, and 2 to 100 parts by weight of the copolymer.
15 parts by weight of anti-aging agent, 8-150 parts by weight of flame retardant,
1 to 5 parts by weight of an organic peroxide crosslinking agent, and 0.1 to 5 parts by weight
1. A heat-resistant flame-retardant composition comprising: parts by weight of a polyfunctional crosslinking auxiliary agent. 2. The flame retardant is 5 to 70 parts by weight of a Br-containing organic flame retardant, 31 to 20 parts by weight of Sb_2O_, and 1 to 3 parts by weight of a zinc compound based on 100 parts by weight of the ethylene-propylene-diene terpolymer.
0 parts by weight, and 1 to 30 parts by weight of red phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62259348A JPH0813912B2 (en) | 1987-10-14 | 1987-10-14 | Heat resistant flame retardant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62259348A JPH0813912B2 (en) | 1987-10-14 | 1987-10-14 | Heat resistant flame retardant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01101348A true JPH01101348A (en) | 1989-04-19 |
| JPH0813912B2 JPH0813912B2 (en) | 1996-02-14 |
Family
ID=17332861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62259348A Expired - Lifetime JPH0813912B2 (en) | 1987-10-14 | 1987-10-14 | Heat resistant flame retardant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813912B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01101346A (en) * | 1987-10-14 | 1989-04-19 | Mitsubishi Cable Ind Ltd | Halogen-free flame-retardant and heat-resistant composition |
| JPWO2007094029A1 (en) * | 2006-02-10 | 2009-07-02 | 株式会社リッチェル | Pet toilet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57107503A (en) * | 1980-12-24 | 1982-07-05 | Hitachi Cable | Flame resistant electric insulating composition |
| JPS588738A (en) * | 1981-07-09 | 1983-01-18 | Tatsuta Electric Wire & Cable Co Ltd | Heat-resistant crosslinked polyolefin composition |
| JPS61240507A (en) * | 1985-04-17 | 1986-10-25 | 日立電線株式会社 | Flame resisting electric insulation composition |
| JPS63257114A (en) * | 1987-04-13 | 1988-10-25 | 三菱電線工業株式会社 | Heat resisting insulated cover material |
| JPS63291938A (en) * | 1987-05-25 | 1988-11-29 | Hitachi Cable Ltd | Flame-retardant electrical insulating composition |
| JPH01101346A (en) * | 1987-10-14 | 1989-04-19 | Mitsubishi Cable Ind Ltd | Halogen-free flame-retardant and heat-resistant composition |
-
1987
- 1987-10-14 JP JP62259348A patent/JPH0813912B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57107503A (en) * | 1980-12-24 | 1982-07-05 | Hitachi Cable | Flame resistant electric insulating composition |
| JPS588738A (en) * | 1981-07-09 | 1983-01-18 | Tatsuta Electric Wire & Cable Co Ltd | Heat-resistant crosslinked polyolefin composition |
| JPS61240507A (en) * | 1985-04-17 | 1986-10-25 | 日立電線株式会社 | Flame resisting electric insulation composition |
| JPS63257114A (en) * | 1987-04-13 | 1988-10-25 | 三菱電線工業株式会社 | Heat resisting insulated cover material |
| JPS63291938A (en) * | 1987-05-25 | 1988-11-29 | Hitachi Cable Ltd | Flame-retardant electrical insulating composition |
| JPH01101346A (en) * | 1987-10-14 | 1989-04-19 | Mitsubishi Cable Ind Ltd | Halogen-free flame-retardant and heat-resistant composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01101346A (en) * | 1987-10-14 | 1989-04-19 | Mitsubishi Cable Ind Ltd | Halogen-free flame-retardant and heat-resistant composition |
| JPWO2007094029A1 (en) * | 2006-02-10 | 2009-07-02 | 株式会社リッチェル | Pet toilet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813912B2 (en) | 1996-02-14 |
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