JPH02204909A - Wire covered by flame retardant urethane resin composition - Google Patents
Wire covered by flame retardant urethane resin compositionInfo
- Publication number
- JPH02204909A JPH02204909A JP2400189A JP2400189A JPH02204909A JP H02204909 A JPH02204909 A JP H02204909A JP 2400189 A JP2400189 A JP 2400189A JP 2400189 A JP2400189 A JP 2400189A JP H02204909 A JPH02204909 A JP H02204909A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- resin composition
- urethane resin
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 24
- 239000003063 flame retardant Substances 0.000 title claims abstract description 15
- 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 13
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- YMIUHIAWWDYGGU-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2,3,5,6-tetrabromo-4-(2,3,4,5,6-pentabromophenoxy)phenoxy]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC(C(=C1Br)Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br YMIUHIAWWDYGGU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005642 Oleic acid Substances 0.000 abstract description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- 239000004593 Epoxy Substances 0.000 abstract 3
- 150000002148 esters Chemical class 0.000 abstract 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 abstract 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 abstract 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 abstract 1
- 229960004232 linoleic acid Drugs 0.000 abstract 1
- 229960004488 linolenic acid Drugs 0.000 abstract 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 abstract 1
- -1 poly(ethylene adipate) Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- 239000004970 Chain extender Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は電線に関し、更に詳しくは、耐熱性、難燃性、
低温柔軟性が優れたウレタン樹脂組成物で被覆されてい
て、自動車の配線に用いるケーブル、ロボット用ケーブ
ル、弾性を生かしたカールコード等として有用な１！線
に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to electric wires, and more particularly, to electric wires with heat resistance, flame retardance,
It is coated with a urethane resin composition that has excellent low-temperature flexibility and is useful as cables used in automobile wiring, robot cables, curl cords that take advantage of its elasticity, etc. Regarding lines.
（従来の技術）
を線においては、導電性の金属芯線の周囲に被覆層が形
成される。この被覆層を構成する材料は電気絶縁性であ
って、通常は各種の樹脂組成物が使用されている。(Prior Art) In a wire, a coating layer is formed around a conductive metal core wire. The material constituting this coating layer is electrically insulating, and various resin compositions are usually used.
これらの樹脂組成物のうち、熱可塑性ウレタン樹脂とも
呼ばれるポリウレタンエラストマーはゴムとプラスチッ
クの両方の性質を備えていて、薄肉の被覆層を成形する
ことができ、また可撓性が良好で屈曲性に富むもので、
自動車の配線系統を構成する電線の被覆層材料として広
く用いられている。Among these resin compositions, polyurethane elastomer, also called thermoplastic urethane resin, has the properties of both rubber and plastic, and can be molded into a thin coating layer, and has good flexibility and flexibility. It is rich,
It is widely used as a coating layer material for electric wires that make up automotive wiring systems.
（発明が解決しようとする課題）
ところで、上記したポリウレタンエラストマーはその軟
化温度が１５０−１８０℃であり、高温下においては溶
融して比較的粘度の低い液状体になる性質を有している
。そのため、これを電線の被覆層材料として用いた場合
、その＠線の使用環境が何らかの理由で温度上昇したり
、また、過電流が流れて芯線の抵抗発熱により高温が発
生したりすると、流動化現象を起して被覆層の原形を保
持し得なくなるという問題が発生する。(Problems to be Solved by the Invention) By the way, the above-mentioned polyurethane elastomer has a softening temperature of 150 to 180°C, and has the property of melting at high temperatures to become a liquid with relatively low viscosity. Therefore, when this is used as a coating layer material for electric wires, if the temperature of the @ wire increases for some reason, or if an overcurrent flows and high temperatures occur due to resistance heat generation in the core wire, fluidization may occur. This causes a problem in that the original shape of the coating layer cannot be maintained.
一方、電線の被覆層材料には難燃性を備えることが求め
られている。ポリウレタンエラストマーを難燃化するた
めには、各種の難燃化剤を配合すればよい、しかしなが
ら、難燃化剤の配合は、いずれの場合にあっても、ポリ
ウレタンエラストマーが本来有する特性を損う結果を招
きやす（、また充分に高いレベルの難燃性が得られなか
ったり、更には、柔軟性が劣化して芯線に被覆加工する
ときの成形加工性を低下せしめるという不都合を招く。On the other hand, materials for coating layers of electric wires are required to have flame retardancy. In order to make polyurethane elastomer flame retardant, various flame retardants can be added. However, in any case, the addition of flame retardants impairs the inherent properties of polyurethane elastomer. This may lead to disadvantages such as not being able to obtain a sufficiently high level of flame retardancy, and furthermore, deteriorating flexibility and reducing moldability when coating the core wire.
本発明はポリウレタンエラスト−に関する上記したよう
な問題を解決して、耐熱性、難燃性、更には低温柔軟性
のいずれもが向上した難燃性ウレタン樹脂組成物で被覆
された電線の提供を目的とする。The present invention solves the above-mentioned problems regarding polyurethane elastomers, and provides an electric wire coated with a flame-retardant urethane resin composition that has improved heat resistance, flame retardancy, and low-temperature flexibility. purpose.
（課題を解決するための手段・作用）
上記した目的を達成するために、本発明においては、芯
線と該芯線を被覆する難燃性ウレタン樹脂組成物の被覆
層とから成る電線において、前記被覆層が、熱可塑性ウ
レタン樹脂１００重量部；ハロゲン含有リン酸エステル
１〜１５重量部；分子末端に位置しないエポキシ基を１
分子中に１個有する化合物０．１〜１５重量飢；テトラ
デカブロモジフェノキシベンゼン６〜１８重量部；三酸
化アンチモン５〜１６重量部；ならびに、多官能性モノ
マー１〜２０重量部から成る樹脂組成物の放射線照射に
よる架橋体であることを特徴とする難燃性ウレタン樹脂
組成物で被覆された電線が提供される。(Means and effects for solving the problem) In order to achieve the above-mentioned object, in the present invention, in an electric wire consisting of a core wire and a coating layer of a flame-retardant urethane resin composition that covers the core wire, the coating The layer contains 100 parts by weight of thermoplastic urethane resin; 1 to 15 parts by weight of halogen-containing phosphoric acid ester; 1 epoxy group not located at the end of the molecule.
A resin comprising 0.1 to 15 parts by weight of a compound having one compound in the molecule; 6 to 18 parts by weight of tetradecabromodiphenoxybenzene; 5 to 16 parts by weight of antimony trioxide; and 1 to 20 parts by weight of a polyfunctional monomer. An electric wire coated with a flame-retardant urethane resin composition is provided, which is a crosslinked product obtained by irradiating the composition.
本発明の電線は、芯線の被覆層に最大の特徴を有するも
のである。芯線の構成材料は従来から使用されている材
料であれば何であってもよく何ら限定されるものではな
い。The electric wire of the present invention has the greatest feature in the coating layer of the core wire. The constituent material of the core wire may be any conventionally used material and is not limited in any way.
さて、本発明にかかる被覆層は後述する樹脂組成物に放
射線を照射して架橋せしめた架橋体である。The coating layer according to the present invention is a crosslinked product obtained by irradiating a resin composition described below with radiation to crosslink it.
この樹脂組成物における第１の必須成分は、ベース樹脂
としての熱可塑性ウレタン樹脂である。The first essential component in this resin composition is a thermoplastic urethane resin as a base resin.
熱可塑性ウレタン樹脂としては、２官能ポリオール、例
えば、ポリ（エチレンアジペート）、ポリ（１，４−ブ
チルアジペート）、ポリ（１，６−ヘキサンアジペート
）、ポリーｅ−カプロラクタム、ポリ（ヘキサメチレン
カーボネート）等のポリエステルジオールまたはポリオ
キシテトラメチレングリコール等のポリエーテルジオー
ルと、鎖延長剤としてのグリコール、例えば、１．４−
ブチレングリコール、１．６−ヘキサンジオール、エチ
レングリコール等と、ジイソシアネート化合物、例えば
４．４°−ジフェニルメタンジイソシアネート、４．４
゛ジシクロヘキシルメタンジイソシアネート、イソホロ
ンジイソシアネート等とを反応させて、ポリオールとジ
イソシアネートとからなるソフトブロックと、グリコー
ルとジイソシアネートにより構成されるハードブロック
とにより組み立てて得られるポリマーである。Examples of the thermoplastic urethane resin include bifunctional polyols such as poly(ethylene adipate), poly(1,4-butyl adipate), poly(1,6-hexane adipate), poly e-caprolactam, and poly(hexamethylene carbonate). or polyether diols such as polyoxytetramethylene glycol and glycols as chain extenders, e.g.
Butylene glycol, 1.6-hexanediol, ethylene glycol, etc. and a diisocyanate compound, such as 4.4°-diphenylmethane diisocyanate, 4.4
It is a polymer obtained by reacting dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc., and assembling a soft block made of polyol and diisocyanate and a hard block made of glycol and diisocyanate.
第２の必須成分であるハロゲン含有リン酸エステルは難
燃化剤としての働きをし、例えば、トリスクロロエチル
ホスフェート、トリスジクロロプロピルホスフェート、
トリス（２，３−ジブロモプロピル）ホスフェートなど
をあげることができ、これらはそれぞれ１種または２種
以上を適宜に組合せて使用することができる。このハロ
ゲン含有リン酸エステルは、熱可塑性ウレタン樹脂１０
０重量部に対し１〜１５重量部配合される。ハロゲン含
有リン酸エステルのベース樹脂への配合量が１重量部未
満の場合は、得られた架橋体に充分な難燃性を付与する
ことができず、また１５重量部より多く配合されている
場合は、得られる架橋体の耐熱性、低温柔軟性が極端に
低下して不都合である。好ましい配合量は３〜１２１ｉ
量部である。The second essential component, halogen-containing phosphate ester, acts as a flame retardant, such as trischloroethyl phosphate, trisdichloropropyl phosphate,
Examples include tris(2,3-dibromopropyl) phosphate, and these can be used alone or in an appropriate combination of two or more. This halogen-containing phosphate ester is a thermoplastic urethane resin with 10%
It is blended in an amount of 1 to 15 parts by weight per 0 parts by weight. If the amount of halogen-containing phosphoric acid ester added to the base resin is less than 1 part by weight, sufficient flame retardancy cannot be imparted to the resulting crosslinked product, and if more than 15 parts by weight is added. In this case, the heat resistance and low-temperature flexibility of the resulting crosslinked product are extremely reduced, which is disadvantageous. The preferred blending amount is 3-121i
It is a quantity part.
第３の必須成分である分子末端に位置しないエポキシ基
を１分子中に１個有する化合物は、樹脂組成物を成形す
るときに、成形機内において、後述する熱可塑性ウレタ
ン樹脂のウレタン結合が崩壊して発生するアロファネー
ト結合等の架橋反応に起因して該熱可塑性ウレタン樹脂
の成形加工性が低下することを抑制する働きをする。あ
わせて、得られた架橋体の耐熱性の向上に寄与する。こ
のような化合物としては、例えば、エポキシ化オレイン
酸、エポキシ化リノール酸、エポキシ化すルイン酸の１
種または２種以上；エポキシ化大豆油、エポキシ化アマ
ニ油；オレイン酸、リノール酸、リルイン酸の各誘導体
、例えばこれらのエステル化合物をエポキシ化したもの
；アルキルグリシジルエーテルのようなエポキシ樹脂の
反応性希釈剤があげられる。A compound having one epoxy group in one molecule that is not located at the end of the molecule, which is the third essential component, will cause the urethane bonds of the thermoplastic urethane resin (described later) to collapse in the molding machine when molding the resin composition. It functions to suppress deterioration in the molding processability of the thermoplastic urethane resin due to crosslinking reactions such as allophanate bonds that occur in the process. In addition, it contributes to improving the heat resistance of the obtained crosslinked product. Examples of such compounds include epoxidized oleic acid, epoxidized linoleic acid, and epoxidized luic acid.
species or two or more; epoxidized soybean oil, epoxidized linseed oil; derivatives of oleic acid, linoleic acid, and lyluic acid, such as epoxidized ester compounds of these; reactivity of epoxy resins such as alkyl glycidyl ethers Examples include diluents.
これらの化合物は、それぞれ単独で配合してもよいし、
２種以上を適宜に組合せて配合してもよい。These compounds may be blended alone, or
Two or more types may be appropriately combined and blended.
この化合物は、熱可塑性ウレタン樹脂１００重量部に対
し０．１〜１５重量部配合される。この化合物のベース
樹脂への配合量が０．１重量部未満の場合は、樹脂組成
物の成形加工性の向上効果が少なく、また架橋体の耐熱
性を向上せしめることも少なくなる。また配合量が１５
重量部よりも多くなっても、上記した効果は飽和状態に
達するのみである。好ましい配合量は３〜１０重量部で
ある。This compound is blended in an amount of 0.1 to 15 parts by weight per 100 parts by weight of the thermoplastic urethane resin. If the amount of this compound added to the base resin is less than 0.1 parts by weight, the effect of improving the moldability of the resin composition will be small, and the heat resistance of the crosslinked product will not be improved much. Also, the blending amount is 15
Even if the amount exceeds 1 part by weight, the above-mentioned effects only reach a saturated state. The preferred amount is 3 to 10 parts by weight.
第４の必須成分であるテトラデカブロモジフェノキシベ
ンベンは、次式；
で示される化合物で、難燃化剤として機能する。The fourth essential component, tetradecabromodiphenoxybenben, is a compound represented by the following formula; and functions as a flame retardant.
この化合物は、熱可塑性ウレタン樹脂１００重量部に対
し、６〜２０重量部配合される。This compound is blended in an amount of 6 to 20 parts by weight per 100 parts by weight of the thermoplastic urethane resin.
配合量が６重量部未満の場合は得られた架橋体の難燃性
が不充分であり、また２０重量部より多い場合は架橋体
の耐熱性、低温柔軟性が著しく低下してしまうからであ
る。好ましい配合量は、ベース樹脂１００重量部に対し
、１０〜１６重量部である。If the amount is less than 6 parts by weight, the resulting crosslinked product will have insufficient flame retardancy, and if it is more than 20 parts by weight, the heat resistance and low temperature flexibility of the crosslinked product will be significantly reduced. be. The preferred blending amount is 10 to 16 parts by weight based on 100 parts by weight of the base resin.
第５の必須成分は三酸化アンチモンで、前記した難燃化
剤と一緒になって難燃性の向上に寄与する成分である。The fifth essential component is antimony trioxide, which, together with the above-mentioned flame retardant, contributes to improving flame retardancy.
三酸化アンチモンは、熱可塑性ウレタン樹脂１００重量
部に対し、５〜１６重量部配合される。配合量が５重量
部未満の場合は、得られた架橋体の難燃性が不充分であ
り、また１６重量部より多く配合しても難燃性付与効果
は飽和に達するのみであるからである。好ましい配合量
は、熱可塑性ウレタン樹脂１００重量部に対し、８〜！
６重量部である。Antimony trioxide is blended in an amount of 5 to 16 parts by weight based on 100 parts by weight of the thermoplastic urethane resin. If the amount is less than 5 parts by weight, the resulting crosslinked product will have insufficient flame retardancy, and even if more than 16 parts by weight is added, the flame retardant effect will only reach saturation. be. The preferred blending amount is 8 to 100 parts by weight of thermoplastic urethane resin!
6 parts by weight.
第６の必須成分は多官能性モノマーで、後述する放射線
架橋時における樹脂組成物の架橋助剤として機能する。The sixth essential component is a polyfunctional monomer, which functions as a crosslinking aid for the resin composition during radiation crosslinking, which will be described later.
用いる多官能性上ツマ−としては、３官能以上のものが
好ましく、例えば、トリメチロールプロパントリメタク
リレート、トリメチロールプロパントリアクリレート、
トリアリルシアヌレート、トリアクリルホルマールをあ
げることができる。これらはそれぞれ単独で用いてもよ
いし、２種以上を適宜に組合せて用いてもよい。The polyfunctional polymer used is preferably trifunctional or higher, such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
Examples include triallyl cyanurate and triaryl formal. Each of these may be used alone, or two or more types may be used in an appropriate combination.
多官能性モノマーは、熱可塑性ウレタン樹脂１００重量
部に対し、１〜２０重量部配合される。The polyfunctional monomer is blended in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic urethane resin.
配合量が１重量部未満の場合は、得られた架橋体の耐熱
性の低下を招き、また２０重量部を超える場合は架橋体
の低温柔軟性が著しく低下するからである。好ましい配
合量は、熱可塑性ウレタン樹脂１００重量部に対し、５
〜１６重量部である。If the amount is less than 1 part by weight, the heat resistance of the obtained crosslinked product will be reduced, and if it exceeds 20 parts by weight, the low temperature flexibility of the crosslinked product will be significantly reduced. The preferred blending amount is 5 parts by weight per 100 parts by weight of thermoplastic urethane resin.
~16 parts by weight.
本発明の電線は、上記した６つの必須成分を配合して樹
脂組成物を調製し、この樹脂組成物を用いて芯線に常法
の被覆加工を施して被覆層を形成し、ついでこの？Ｉ！
覆層に放射線を照射して前記樹脂組成物を架橋せしめる
ことにより製造することができる。For the electric wire of the present invention, a resin composition is prepared by blending the six essential components described above, and a core wire is coated with the resin composition in a conventional manner to form a coating layer. I!
It can be manufactured by irradiating the covering layer with radiation to crosslink the resin composition.
この放射線架橋時に、用いる放射線としては、電子線、
Ｔ線のような電離性放射線が好適である。During this radiation crosslinking, the radiation used is electron beam,
Ionizing radiation such as T-rays is preferred.
また、照射線量は１〜３０Ｍｒ ａ ｄであることが好
ましい、照射線量が１Ｍｒａｄより低い場合は架橋が充
分に進行せず、また３０Ｍｒａｄより高くても架橋効果
は飽和状態に達してしまうからである。より好ましくは
６〜２０Ｍｒａｄである。Further, the irradiation dose is preferably 1 to 30 Mrad, because if the irradiation dose is lower than 1 Mrad, crosslinking will not proceed sufficiently, and if it is higher than 30 Mrad, the crosslinking effect will reach a saturated state. . More preferably, it is 6 to 20 Mrad.
（発明の実施例）
実施例１〜６、比較例１〜６
第１表に示した各成分を表示の割合４１部）で配合して
得られた樹脂組成物を、外径が１．２ ｍのポリエチレ
ン樹脂被覆線の上に、外径が６．５−となるように押出
被覆した。ついでこれら樹脂組酸物の被覆層に、７５０
ＫｅＶの電子線を照射線量１２Ｍｒ ａ ｄで照射して
架橋せしめた。得られた各電線につき、下記仕様で耐熱
性、難燃性、低温柔軟性を測定した。(Examples of the Invention) Examples 1 to 6, Comparative Examples 1 to 6 A resin composition obtained by blending each component shown in Table 1 at the indicated ratio of 41 parts) was prepared with an outer diameter of 1.2 parts. The wire was extrusion coated onto a polyethylene resin-coated wire having an outer diameter of 6.5 mm. Then, a coating layer of these resin composite acids was coated with 750
Crosslinking was carried out by irradiation with a KeV electron beam at an irradiation dose of 12 Mr ad. The heat resistance, flame retardance, and low-temperature flexibility of each of the obtained electric wires were measured according to the following specifications.
耐熱性：電線を自己径のマンドレルに巻回し、２００°
Ｃの恒温槽内に３０分間放置
したのちこれを取り出して常温まで
冷却し、外観の溶融またはクランク
の発生の有無を観察した。Heat resistance: Wrap the wire around a mandrel of its own diameter, 200°
After being left in a constant temperature bath of C for 30 minutes, it was taken out and cooled to room temperature, and the appearance of melting or cracking was observed.
難燃性： ＵＬ６２ＶＷ−ＬｖＡ焼試験により合格、不
合格を判定。Flame retardancy: Pass or fail determined by UL62VW-LvA baking test.
低温柔軟性−一４５°Ｃの雰囲気に電線を１時間以上放
置したのち、この雰囲気中にお
いて、Ｒ＝２５ｍのマンドレルに電
線を巻回し、このときの被覆層のク
ラック発生の有無を観察。Low-temperature flexibility - After leaving the wire in an atmosphere of -45°C for more than 1 hour, the wire was wound around a mandrel with R = 25 m in this atmosphere, and the presence or absence of cracks in the coating layer was observed.
以上の結果を一括して第１表に示した。The above results are collectively shown in Table 1.
（以下余白）
（発明の効果）
以上の説明で明らかなように、本発明の電線は、その被
覆層を構成する樹脂組成物が耐熱性、難燃性、低温柔軟
性に優れているので、従来のポリウレタンエラストマー
被覆の電線に比べその工業的価値は大である。(The following is a blank space) (Effects of the Invention) As is clear from the above description, the electric wire of the present invention has excellent heat resistance, flame retardance, and low-temperature flexibility because the resin composition that constitutes the coating layer has excellent heat resistance, flame retardancy, and low-temperature flexibility. Its industrial value is greater than that of conventional polyurethane elastomer-coated wires.
Claims (1)
被覆層とから成る電線において、前記被覆層が、熱可塑
性ウレタン樹脂１００重量部；ハロゲン含有リン酸エス
テル１〜１５重量部；分子末端に位置しないエポキシ基
を１分子中に１個有する化合物０．１〜１５重量部；テ
トラデカブロモジフェノキシベンゼン６〜１８重量部；
三酸化アンチモン５〜１６重量部；ならびに、多官能性
モノマー１〜２０重量部から成る樹脂組成物の放射線照
射による架橋体であることを特徴とする難燃性ウレタン
樹脂組成物で被覆された電線。In an electric wire consisting of a core wire and a coating layer of a flame-retardant urethane resin composition covering the core wire, the coating layer comprises: 100 parts by weight of a thermoplastic urethane resin; 1 to 15 parts by weight of a halogen-containing phosphoric acid ester; 0.1 to 15 parts by weight of a compound having one unlocated epoxy group in one molecule; 6 to 18 parts by weight of tetradecabromodiphenoxybenzene;
An electric wire coated with a flame-retardant urethane resin composition, which is a crosslinked product obtained by irradiation of a resin composition comprising 5 to 16 parts by weight of antimony trioxide; and 1 to 20 parts by weight of a polyfunctional monomer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2400189A JPH02204909A (en) | 1989-02-03 | 1989-02-03 | Wire covered by flame retardant urethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2400189A JPH02204909A (en) | 1989-02-03 | 1989-02-03 | Wire covered by flame retardant urethane resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02204909A true JPH02204909A (en) | 1990-08-14 |
Family
ID=12126330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2400189A Pending JPH02204909A (en) | 1989-02-03 | 1989-02-03 | Wire covered by flame retardant urethane resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02204909A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1461383A1 (en) † | 2001-12-05 | 2004-09-29 | Isola Laminate Systems, Corp. | Thermosetting resin composition for high performance laminates |
-
1989
- 1989-02-03 JP JP2400189A patent/JPH02204909A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1461383A1 (en) † | 2001-12-05 | 2004-09-29 | Isola Laminate Systems, Corp. | Thermosetting resin composition for high performance laminates |
| EP1461383B2 (en) † | 2001-12-05 | 2012-06-06 | Isola Laminate Systems, Corp. | Thermosetting resin composition for high performance laminates |
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