JP2002525819A - Wire insulation - Google Patents
Wire insulationInfo
- Publication number
- JP2002525819A JP2002525819A JP2000571464A JP2000571464A JP2002525819A JP 2002525819 A JP2002525819 A JP 2002525819A JP 2000571464 A JP2000571464 A JP 2000571464A JP 2000571464 A JP2000571464 A JP 2000571464A JP 2002525819 A JP2002525819 A JP 2002525819A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- weight
- layers
- copolymer
- acrylate
- 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
- 238000009413 insulation Methods 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 51
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 239000002033 PVDF binder Substances 0.000 claims abstract description 30
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 30
- 229920000098 polyolefin Polymers 0.000 claims abstract description 29
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229920001897 terpolymer Polymers 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012212 insulator Substances 0.000 claims abstract description 17
- 230000005855 radiation Effects 0.000 claims abstract description 16
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 238000009472 formulation Methods 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 230000032798 delamination Effects 0.000 claims abstract description 7
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001733 carboxylic acid esters Chemical group 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 4
- 239000004020 conductor Substances 0.000 claims description 8
- 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 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 70
- 238000010894 electron beam technology Methods 0.000 description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 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 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 102100025367 Keratin, type II cytoskeletal 75 Human genes 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
Landscapes
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
- Laminated Bodies (AREA)
- Inorganic Insulating Materials (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Resistance Heating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Communication Cables (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Die Bonding (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
(57)【要約】 絶縁体を有する電線またはケーブルであって、該絶縁体が、(i)ポリオレフィン系配合物の少なくとも第一の層であって、該配合物のポリマー部分の少なくとも20重量%、好ましくは少なくとも40重量%、より好ましくは少なくとも60重量%、または特に好ましくは少なくとも80重量%が、カルボニル含有ポリマー(ホモポリマーまたはコポリマーまたはターポリマー)から成り、該ポリマーの少なくとも1種類の構成モノマーがカルボン酸エステル、好ましくはアクリレートまたはアセテート、特にアルキルアクリレート(好ましくは、メチルアクリレート、エチルアクリレート、プロピルアクリレート、またはブチルアクリレート)であり、コポリマーまたはターポリマーが使用される場合に該モノマーがコポリマーまたはターポリマーの少なくとも5重量%、好ましくは少なくとも9重量%、より好ましくは少なくとも15重量%を構成し、該コポリマーまたはターポリマーの残りの大部分が、オレフィンモノマー、好ましくはエチレンから誘導されるのが好ましい、ポリオレフィン系配合物の少なくとも第一の層;および、第一の層に接触する(ii)他の材料の配合物の少なくとも第二の層であって、該第二の層の少なくとも10重量%、より好ましくは少なくとも50重量%、特に好ましくは少なくとも90重量%、特に100重量%のポリビニリデンフルオライド(PVDF)、特に好ましくはVDFおよび部分または完全弗素化コモノマーに基づくコポリマー、最も好ましくはVDFとヘキサフルオロプロピレン(HFP)のコポリマーを含有する、他の材料の配合物の少なくとも第二の層を有して成り;23℃において1時間のアセトン浸漬試験中に該2層の離層を防止するか、またはASTM B1876-95の方法による該層間の剥離結合強度を少なくとも5Nに増加させ、好ましくは非架橋層間の結合強度と比較して、少なくとも50%、より好ましくは少なくとも100%、特に少なくとも500%または1000%で結合強度を増加させるのに充分であるように、該層(i)および(ii)を、相互に接触させながら、好ましくは放射線、より好ましくは電離線によって架橋反応に付されている;電線またはケーブル。 (57) [Summary] An electric wire or cable having an insulator, wherein the insulator is (i) at least a first layer of a polyolefin-based composition, at least 20% by weight of the polymer portion of the composition, preferably at least 40% by weight. %, More preferably at least 60% by weight, or particularly preferably at least 80% by weight, of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer), wherein at least one constituent monomer of said polymer is a carboxylic acid ester, preferably Is an acrylate or acetate, especially an alkyl acrylate (preferably, methyl acrylate, ethyl acrylate, propyl acrylate, or butyl acrylate), where a copolymer or terpolymer is used when the copolymer or terpolymer is used. Preferably, at least 5%, preferably at least 9%, more preferably at least 15% by weight of the polymer is comprised, and the remainder of the copolymer or terpolymer is preferably derived from olefin monomers, preferably ethylene. At least a first layer of a polyolefin-based formulation; and (ii) at least a second layer of a formulation of another material in contact with the first layer, wherein at least 10% by weight of the second layer. %, More preferably at least 50% by weight, particularly preferably at least 90% by weight, in particular 100% by weight, of polyvinylidene fluoride (PVDF), particularly preferably VDF and copolymers based on partially or fully fluorinated comonomers, most preferably VDF and Containing a copolymer of hexafluoropropylene (HFP), etc. Having at least a second layer of a formulation of the material; preventing delamination of the two layers during an acetone soak test at 23 ° C. for 1 hour, or delamination between the layers by the method of ASTM B1876-95 It is sufficient to increase the bond strength to at least 5N, preferably at least 50%, more preferably at least 100%, especially at least 500% or 1000%, as compared to the bond strength between the non-crosslinked layers. As such, the layers (i) and (ii) have been subjected to a crosslinking reaction, preferably in contact with one another, by radiation, more preferably by ionizing radiation; wires or cables.
Description
【0001】 (技術分野) 本発明は、ポリオレフィン系材料の層とポリビニリデンフルオライド系材料の
層との界面における強い結合が達成されている、電線またはケーブル(以下「電
線」と称する)用の絶縁体に関する。本発明は、電線の多層絶縁体に特に有効で
あり、そのような材料層の間の高性能結合を可能にし、その一方で、成形品また
は包装フィルムのような他の種類の物品の基準と異なる特殊な他の電線性能条件
の複雑な関係において許容されるバランスを維持する。TECHNICAL FIELD The present invention relates to an electric wire or cable (hereinafter referred to as “electric wire”) in which a strong bond is achieved at an interface between a layer of a polyolefin-based material and a layer of a polyvinylidene fluoride-based material. Related to insulators. The present invention is particularly useful for multilayer insulation of electrical wires, allowing for high performance bonding between such layers of material, while maintaining the standard for other types of articles such as moldings or packaging films. Maintain an acceptable balance in the complex relationship of different specific other wire performance conditions.
【0002】 (背景技術) 下記の略語が以下に使用される: PJ=一次ジャケット;プロラド=架橋促進剤;TMPTM=トリメチロールプ
ロパントリメタクリレ−ト;ASTM=American Society for Testing and Mat
erials;PVDF=ポリビニリデンフルオライド;VDF=ビニリデンフルオラ
イド;HFP=ヘキサフルオロプロピレン;HDPE=高密度ポリエチレン;E
EA=エチレン/エチルアクリレート;EMA=エチレン/メチルアクリレート;
EVA=エチレン/ビニルアセテート;EA=エチルアクリレート;MA=メチ
ルアクリレート;VA=ビニルアセテート。BACKGROUND OF THE INVENTION The following abbreviations are used for: PJ = primary jacket; prorad = crosslinking accelerator; TMPTM = trimethylolpropane trimethacrylate; ASTM = American Society for Testing and Mat
erials; PVDF = polyvinylidene fluoride; VDF = vinylidene fluoride; HFP = hexafluoropropylene; HDPE = high density polyethylene;
EA = ethylene / ethyl acrylate; EMA = ethylene / methyl acrylate;
EVA = ethylene / vinyl acetate; EA = ethyl acrylate; MA = methyl acrylate; VA = vinyl acetate.
【0003】 ポリオレフィン内層(コア)およびポリビニリデンフルオライド(PVDF)
外層(一次ジャケットまたはPJ)を有して成る二層電線絶縁体は、30年間に
わたって市販されており、複数社の製造会社から入手できる。これらの製品は全
て、内層(ポリオレフィン)と外層(PVDF)との間の非常に僅かな付着を有
し、従って、容易に分離することができる。構造物の強さを制限するこの結合の
不足から生じるいくつかの不都合を受け入れなければならなかった。例えば、機
械的応力、ある種の液体への暴露、鋭利物との接触、または衝撃に暴露された場
合に、外部絶縁層が亀裂を生じ、内層から剥がれる場合がある。絶縁体の耐摩耗
性および曲げ疲れ抵抗性、ならびに曲げた際のシワ(電線をシールするか、また
は電線をグロメットまたはコネクターに挿入するのを困難にする場合がある)に
対する抵抗性も、2つの容易に分離する絶縁層によって不利な影響を受ける。電
線における、ポリオレフィンおよびPVDFのような2つのそのような異なる種
類の材料の層を、商業的に許容されるコストおよび製造効率で結合させることは
不可能であると考えられていた。さらに、利用できる結合法は、電線の性能特性
に許容されない影響を与える場合がある。ポリオレフィンおよびPVDFを結合
させる従来の方法は、連結層材料を使用する方法である(例えば米国特許第55
89028号)が、これらはコストが高くなる場合が多く、電線に使用する場合
に、他の特性、例えば熱老化抵抗性を損なう場合あり、余分な層の形成によって
製造工程を複雑にする。それらは、得られる結合強度の点でも、有効性に限界が
ある。[0003] Polyolefin inner layer (core) and polyvinylidene fluoride (PVDF)
Double-layer wire insulation having an outer layer (primary jacket or PJ) has been commercially available for 30 years and is available from several manufacturers. All these products have very little adhesion between the inner layer (polyolefin) and the outer layer (PVDF) and can therefore be easily separated. Several inconveniences arising from this lack of bonding that limited the strength of the structure had to be accepted. For example, when exposed to mechanical stress, certain liquids, contact with sharps, or impact, the outer insulating layer may crack and peel from the inner layer. The abrasion resistance and bending fatigue resistance of the insulator, and the resistance to wrinkling when bent (which can make it difficult to seal the wires or insert the wires into grommets or connectors) are also two-fold. Disadvantageously affected by easily separating insulating layers. It was believed that it was not possible to combine layers of two such different types of materials, such as polyolefins and PVDF, in electrical wires at commercially acceptable costs and manufacturing efficiencies. Further, available coupling methods may have unacceptable effects on the performance characteristics of the wire. A conventional method of bonding polyolefin and PVDF is to use a tie layer material (eg, US Pat.
89028), however, these are often costly and can impair other properties, such as heat aging resistance, when used in electrical wires, and complicate the manufacturing process by forming extra layers. They also have limited effectiveness in terms of the bond strength obtained.
【0004】 (発明の開示) 本発明によれば、ポリオレフィン系コアおよびポリビニルデンフルオライド系
PJの異なる絶縁材料が、電線またはケーブルにおいて有意な付着レベルで結合
でき;この結合が、電線における前記の強さの問題を減少させるかまたは除去し
;予想に反して、亀裂生長抵抗性、コスト、または電線性能の総体的バランスに
許容されない影響を与えずに、この結合が得られる;ことが見い出された。DISCLOSURE OF THE INVENTION According to the present invention, different insulating materials of a polyolefin-based core and a polyvinyldenfluoride-based PJ can be bonded to a wire or cable at a significant adhesion level; It has been found that this bond is obtained without unacceptably affecting crack growth resistance, cost, or the overall balance of wire performance; Was.
【0005】 本発明の電線またはケーブル絶縁体において、意外なことに、ポリビニリデン
フルオライド系層に接触するポリオレフィン系層の選択された配合と、好ましく
は放射線、特に電離線の適用によって行われる架橋反応との組み合わせによって
、有意な結合強度が得られる。[0005] In the wire or cable insulation of the present invention, surprisingly, the selected formulation of the polyolefin-based layer in contact with the polyvinylidene fluoride-based layer and the crosslinking preferably effected by the application of radiation, especially ionizing radiation. Significant binding strength is obtained by combination with the reaction.
【0006】 従って、本発明は、 (i) ポリオレフィン系材料の少なくとも第一の層であって、該材料の少な
くとも20重量%、好ましくは少なくとも40重量%、より好ましくは少なくと
も60重量%、または少なくとも80重量%(全材料組成に基づく)の、非芳香
族主鎖を有するカルボニル含有ポリマー(ホモポリマーまたはコポリマーまたは
ターポリマー)を含んで成り、該ポリマーの少なくとも1種類の構成モノマーが
カルボン酸エステル、好ましくはアクリレートまたはアセテート、特にアルキル
アクリレート(好ましくは、メチルアクリレート、エチルアクリレート、プロピ
ルアクリレート、またはブチルアクリレート)であり、コポリマーまたはターポ
リマーが使用される場合に該モノマーがコポリマーまたはターポリマーの少なく
とも5重量%、好ましくは少なくとも9重量%、より好ましくは少なくとも15
重量%を構成し、該コポリマーまたはターポリマーの残りが、オレフィンモノマ
ー、好ましくはエチレンから誘導されるのが好ましい、ポリオレフィン系材料の
少なくとも第一の層;および、第一の層に接触する (ii) 少なくとも10重量%、より好ましくは少なくとも50重量%、ま
たは少なくとも90重量%のポリビニリデンフルオライド(PVDF)、特に好
ましくはVDFおよび部分または完全弗素化コモノマーに基づくコポリマー、最
も好ましくはVDFとヘキサフルオロプロピレン(HFP)のコポリマーを含有
する材料の少なくとも第二の層; を有して成り; 該層間の剥離結合強度を少なくとも5Nに増加させ、好ましくは非架橋層間の
結合強度と比較して、少なくとも50%、より好ましくは少なくとも100%、
特に少なくとも500%または1000%で結合強度を増加させるのに充分であ
るように、該層(i)および(ii)を、相互に接触させながら、好ましくは放
射線、より好ましくは電離線によって架橋反応に付されている; 絶縁体、を有する電線を提供する。Accordingly, the present invention relates to (i) at least a first layer of a polyolefin-based material, wherein at least 20%, preferably at least 40%, more preferably at least 60%, or at least 60% by weight of said material. 80% by weight (based on the total material composition) of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer) having a non-aromatic backbone, wherein at least one constituent monomer of the polymer is a carboxylic acid ester, Preferably, it is an acrylate or acetate, especially an alkyl acrylate (preferably methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate), and when a copolymer or terpolymer is used, the monomer is a copolymer or terpolymer. At least 5 wt%, preferably at least 9 wt%, more preferably at least 15
At least a first layer of a polyolefin-based material, preferably from an olefin monomer, preferably ethylene, comprising the remaining weight of the copolymer or terpolymer; and (ii) ) At least 10%, more preferably at least 50%, or at least 90% by weight of polyvinylidene fluoride (PVDF), particularly preferably VDF and a copolymer based on partially or fully fluorinated comonomers, most preferably VDF and hexafluoro At least a second layer of a material containing a copolymer of propylene (HFP); increasing the peel bond strength between said layers to at least 5N, preferably at least as compared to the bond strength between non-crosslinked layers. 50%, more preferably at least 100%,
The layers (i) and (ii) are brought into contact with one another, preferably by radiation, more preferably by ionizing radiation, such that at least 500% or 1000% is sufficient to increase the bond strength. An electric wire having an insulator.
【0007】 本発明の他の要旨によれば、 (i) ポリオレフィン系配合物の少なくとも第一の層であって、該配合物の
ポリマー部分の少なくとも20重量%、好ましくは少なくとも40重量%、より
好ましくは少なくとも60重量%、または特に好ましくは少なくとも80重量%
が、カルボニル含有ポリマー(ホモポリマーまたはコポリマーまたはターポリマ
ー)から成り、該ポリマーの少なくとも1種類の構成モノマーがカルボン酸エス
テル、好ましくはアクリレートまたはアセテート、特にアルキルアクリレート(
好ましくは、メチルアクリレート、エチルアクリレート、プロピルアクリレート
、またはブチルアクリレート)であり、コポリマーまたはターポリマーが使用さ
れる場合に該モノマーがコーまたはターポリマーの少なくとも5重量%、好まし
くは少なくとも9重量%、より好ましくは少なくとも15重量%を構成し、該コ
ポリマーまたはターポリマーの残りまたは残りの大部分が、オレフィンモノマー
、好ましくはエチレンから誘導されるのが好ましい、ポリオレフィン系配合物の
少なくとも第一の層;および、第一の層に接触する (ii) 他の材料の配合物の少なくとも第二の層であって、少なくとも10
重量%、より好ましくは少なくとも50重量%、特に好ましくは少なくとも90
重量%、特に100重量%のポリビニリデンフルオライド(PVDF)、特に好
ましくはVDFおよび部分または完全弗素化コモノマーに基づくコポリマー、最
も好ましくはVDFとヘキサフルオロプロピレン(HFP)のコポリマーを含有
する他の材料の配合物の少なくとも第二の層; を有して成り; 下記に説明するアセトン浸漬試験中に該2層の離層を防止するか、または下記
に説明するASTM B1876-95の方法による該層間の剥離結合強度を少なくとも5N
に増加させ、好ましくは非架橋層間の結合強度と比較して、少なくとも50%、
より好ましくは少なくとも100%、特に少なくとも500%または1000%
で結合強度を増加させるのに充分であるように、該層(i)および(ii)を、
相互に接触させながら、好ましくは放射線、より好ましくは電離線によって架橋
反応に付している; 絶縁体、を有する電線を提供する。In accordance with another aspect of the present invention, (i) at least a first layer of a polyolefin-based formulation, wherein the polymer portion of the formulation is at least 20% by weight, preferably at least 40% by weight, more Preferably at least 60% by weight, or particularly preferably at least 80% by weight
Consists of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer), wherein at least one constituent monomer of the polymer is a carboxylic acid ester, preferably an acrylate or acetate, especially an alkyl acrylate (
Preferably, methyl acrylate, ethyl acrylate, propyl acrylate, or butyl acrylate), wherein when a copolymer or terpolymer is used, the monomer is at least 5% by weight of the co or terpolymer, preferably at least 9% by weight, more At least a first layer of a polyolefin-based formulation, preferably comprising at least 15% by weight, wherein the rest or the majority of the remainder of the copolymer or terpolymer is preferably derived from olefin monomers, preferably ethylene; Contacting the first layer; (ii) at least a second layer of a blend of other materials, wherein at least 10
%, More preferably at least 50% by weight, particularly preferably at least 90% by weight.
% By weight, especially 100% by weight, of polyvinylidene fluoride (PVDF), particularly preferably other copolymers containing VDF and copolymers based on partially or fully fluorinated comonomers, most preferably copolymers of VDF and hexafluoropropylene (HFP) Preventing delamination of said two layers during an acetone soak test as described below, or said layer by the method of ASTM B1876-95 described below. Peel strength of at least 5N
And preferably at least 50% compared to the bond strength between the non-crosslinked layers,
More preferably at least 100%, especially at least 500% or 1000%
The layers (i) and (ii) are sufficient to increase the bond strength at
Providing a wire having a cross-linking reaction, preferably in contact with one another, by radiation, more preferably by ionizing radiation; an insulator.
【0008】 好ましくは、該2つの層の少なくとも1つにおけるポリマー材料の融点または
軟化点より高い温度において各層を相互に接触させ、従ってそれらの界面接触の
緊密性を最大にし、そうすることによって次の架橋反応における付着促進界面架
橋の形成を助長することができる。Preferably, the layers are brought into contact with each other at a temperature above the melting point or softening point of the polymer material in at least one of the two layers, thus maximizing the tightness of their interfacial contact, so that: Can promote the formation of adhesion-promoting interfacial cross-linking in the cross-linking reaction.
【0009】 ポリオレフィン系層(i)は、前記にそれについての条件を規定した配合物の
ポリマー部分の他に、既知の酸化防止剤、着色剤、充填剤、難燃剤等のような添
加剤として必要とされるものを含有して、必要とされる機械的、熱的、電気的特
性等を、ポリマーに付与することができる。[0009] The polyolefin-based layer (i) is used as an additive such as a known antioxidant, coloring agent, filler, flame retardant, etc., in addition to the polymer portion of the blend in which the conditions for the polyolefin are defined above. The required mechanical, thermal, electrical properties and the like can be imparted to the polymer, including those required.
【0010】 ポリビニリデンフルオライド系層(ii)も、既知の他の添加剤を含有して、
結合性の他に必要とされる特性を付与することができる。The polyvinylidene fluoride-based layer (ii) also contains other known additives,
The required properties can be imparted in addition to the binding property.
【0011】 本発明によって強い結合を得ることの利点は、以下のことを包含する: − 表面層、およびそれが(表面層)が基材に結合される場合の全体としての絶
縁体の、耐摩耗性; − 特に層の1つが損傷/貫通された場合の、増加した耐剥離性; − 熱が適用された場合の、2つの層の向上した耐ふくれ性; − 例えば、機械的応力または薬品、例えば溶剤への暴露による、2つの層間の
向上した離層/折りじわ/しわ抵抗性; − 適切な切断抵抗性およびノッチ生長抵抗性を維持しつつ、減少した電線曲げ
しわ発生および前記特性の向上を達成する(これは、強固に付着した層は一般に
、外層における切れ目またはノッチを内層にかなり容易に伝えると考えられる故
に、予想されないことであった)。The advantages of obtaining a strong bond according to the invention include the following: the resistance of the surface layer and of the insulator as a whole when it is bonded to the substrate; -Increased abrasion resistance, especially when one of the layers is damaged / penetrated;-improved bulging resistance of the two layers when heat is applied;-for example, mechanical stress or chemicals Improved delamination / crease / wrinkle resistance between the two layers, for example by exposure to solvents; reduced wire wrinkling and said properties while maintaining adequate cut and notch growth resistance (This was unexpected because a firmly adhered layer is generally considered to transmit cuts or notches in the outer layer to the inner layer quite easily).
【0012】 本明細書において記載される結合強度は、関心のある2つの材料の結合ストリ
ップ間の剥離強度として測定することができる。そのような試験に使用しうる一
般的な方法は、ASTM 1876-95である。この規格によれば、有意な結合は剥離力が
5Nを越える結合であり、強い結合は剥離力が10Nを越える結合である。電線
において加工された場合の、該層(i)および(ii)間の結合強度を測定する
従来の方法は、全長60mmの電線サンプルを、電線サンプルの長さの70%に相
当する深さで、23(+/−3)℃のアセトン(例えば、Fisher Scientific UK,
AR保証銘柄アセトン)に1時間入れる方法である。絶縁層の非常に僅かな結合
を有する電線は、ポリオレフィンコアの伸張に依存しない、電線の軸に沿ったP
VDF PJの伸張、および/またはPJのシワの発生を示し、それによって、
ところどころでコアから剥離する。それが生じた場合に、前記のPJの伸張は、
前記の試験の後に、サンプルのコアの切り口を1mmまたはそれ以上で越えて伸張
するPJ「チューブ」を与える。有意に結合した絶縁層を有する電線は、分離せ
ず、電線の軸に沿って、導体の切り口を越えて、コアおよびPJが両方とも伸張
し、および/または剥離せずにコアおよびPJ層の両方にシワを生じる。顕微鏡
によってシワの断面を検査することによって、そのようなコアおよびPJの両方
のシワの発生は、PJだけのシワの発生と区別することができる。[0012] The bond strength described herein can be measured as the peel strength between a bond strip of two materials of interest. A common method that can be used for such a test is ASTM 1876-95. According to this standard, a significant bond is a bond with a peel force of more than 5N, and a strong bond is a bond with a peel force of more than 10N. The conventional method of measuring the bond strength between the layers (i) and (ii) when processed in an electric wire is to conduct a wire sample having a total length of 60 mm at a depth corresponding to 70% of the length of the wire sample. Acetone at 23 (+/- 3) ° C (eg, Fisher Scientific UK,
It is a method of putting in AR guaranteed brand acetone) for 1 hour. Wires with very little bonding of the insulation layer have a P along the wire axis that is independent of the extension of the polyolefin core.
Indicating the expansion of the VDF PJ and / or the occurrence of wrinkles in the PJ,
Peeled from the core in some places. When that happens, the stretching of the PJ is
Following the test, a PJ "tube" is provided that extends 1 mm or more beyond the cut end of the sample core. Wires with a significantly bonded insulation layer do not separate, and along the wire axis, beyond the conductor cut, both the core and the PJ stretch and / or without delamination. Both produce wrinkles. By examining the cross-section of the wrinkles under a microscope, the occurrence of such core and PJ wrinkles can be distinguished from the occurrence of PJ-only wrinkles.
【0013】 電線を製造する方法は、前記の層(i)および(ii)の間の緊密な接触を生
じるどのような方法も包含する。そのような方法の例は、1つの材料を、他の二
層または多層押出品の予備形成層に被覆して、前記2種類の材料の1つまたは他
方をそれぞれ含有する絶縁層を形成する方法である。オレフィン系材料(i)が
電線における内層であるのが好ましく、PVDF系層(ii)が外層であるのが
好ましい。2種類の材料から作られる層を、同時押出、タンデム押出、多路押出
するか、または他の手段によってコーティングすることができる。チューブ引落
し押出のような既知の電線絶縁法を使用して1つまたはそれ以上の層を形成する
ことができるが、既知の加圧押出が、先に形成された下層に適用される第二絶縁
層および次の絶縁層の最適な付着に好ましい。[0013] The method of manufacturing the wire encompasses any method that produces intimate contact between the layers (i) and (ii). An example of such a method is a method of coating one material on a preformed layer of another two-layer or multi-layer extrudate to form an insulating layer containing one or the other of each of the two materials. It is. The olefin-based material (i) is preferably the inner layer of the electric wire, and the PVDF-based layer (ii) is preferably the outer layer. Layers made from the two materials can be co-extruded, tandem extruded, multi-pass extruded, or coated by other means. One or more layers can be formed using known wire insulation techniques, such as tube drawdown extrusion, but a known pressure extrusion is applied to the previously formed lower layer. Preferred for optimal deposition of the insulating layer and the next insulating layer.
【0014】 電線における絶縁体を、過酸化物のような化学試薬を使用しうる架橋反応に暴
露するが、該架橋反応は、好ましくは放射線、特に、ポリマー中にラジカル、従
って架橋、を形成させることができる電離線源からの放射線によって行うのが好
ましく、架橋のいくらかが、2つの材料の界面領域に形成されるのが好ましい。
少なくとも界面まで放射線が材料に透過するのが好ましいが、例えばイオンまた
はラジカル可動性が、放射線工程後に界面でまたは界面近くで分子反応を継続さ
せうる場合は、必ずしも必要ではない。放射線源は、例えば、放射性同位体、ま
たはX線源、あるいは非電離ラジカル発生源、例えば紫外線源であるが、好まし
くは電子ビーム、より好ましくは、2Mradより多い、好ましくは少なくとも5Mr
ad、より好ましくは少なくとも10Mrad、特に好ましくは少なくとも15Mradの
ビーム線量を材料に与える電子ビームが好ましい。[0014] The insulator in the wire is exposed to a cross-linking reaction which can use chemical reagents such as peroxides, which preferably form radiation, especially radicals, and thus cross-links, in the polymer. Preferably, the irradiation is effected by radiation from an ionizing source, and preferably some of the crosslinking is formed in the interface region of the two materials.
Preferably, the radiation penetrates the material at least up to the interface, but is not necessary if, for example, ionic or radical mobility allows the molecular reaction to continue at or near the interface after the radiation step. The radiation source is, for example, a radioisotope or X-ray source, or a non-ionizing radical generating source, for example an ultraviolet source, but is preferably an electron beam, more preferably more than 2 Mrad, preferably at least 5 Mr
An electron beam which gives a material a beam dose of ad, more preferably at least 10 Mrad, particularly preferably at least 15 Mrad is preferred.
【0015】 ある種の添加剤を使用することによって、界面結合強度を増加しうることが見
い出された。添加剤は、ポリオレフィン系材料および/またはPVDF系材料に
おける架橋促進剤(プロラド)を包含するのが好ましい。既知の架橋剤、好まし
くはメタクリレート/アクリレートに基づく架橋剤、特に好ましくはトリメチロ
ールプロパントリメタクリレート(TMPTM)タイプの架橋剤を、ポリオレフ
ィン材料および/またはPVDF系材料に使用することができる。It has been found that by using certain additives, the interfacial bond strength can be increased. The additive preferably includes a crosslinking accelerator (prorad) in the polyolefin-based material and / or the PVDF-based material. Known crosslinking agents, preferably those based on methacrylates / acrylates, particularly preferably those of the trimethylolpropane trimethacrylate (TMPTM) type, can be used for polyolefin materials and / or PVDF-based materials.
【0016】 実験結果 下記表に示す全ての結果は、既知の一般的なポリマー取扱法によって製造した
2つの材料のプレスプラックを試験することによって得た。プラックをプレスし
て、それらの面と面を結合させ、結合したアセンブリを指定のように照射した。
プラックにおける結合強度が比較的測定しやすい故に、これらの証明試験に電線
ではなくプラックを使用した。これらの実験の条件は以下の通りであった: プラック寸法: 150mmx150mmx0.85mm プレス温度: 200℃ プレス時間: 2分間の予熱、加圧下に1分間 プレス圧力: 300mmx300mmの金属板上で20〜40トン 冷却条件: 前記の圧力において、水冷300mmx300mm金属板の間に2分
間。Experimental Results All the results shown in the table below were obtained by testing press plaques of two materials made by known general polymer handling methods. The plaque was pressed to join the faces together and the combined assembly was irradiated as specified.
Plaques, rather than wires, were used in these certification tests because the bond strength at the plaques was relatively easy to measure. The conditions of these experiments were as follows: Plaque dimensions: 150 mm x 150 mm x 0.85 mm Press temperature: 200 ° C Press time: 2 minutes preheating, 1 minute under pressure Press pressure: 20-40 tons on 300 mm x 300 mm metal plate Cooling conditions: At the above pressure, between water cooled 300 mm x 300 mm metal plates for 2 minutes.
【0017】 適切なポリオレフィン材料とPVDF系材料の結合強度における、放射線量の影
響の例Examples of the effect of radiation dose on the bond strength between suitable polyolefin and PVDF-based materials
【表1】 [Table 1]
【0018】 電子ビーム架橋後の、適切なPVDF系材料への結合強度における、エチレンコ
ポリマー材料中のコモノマーのパーセンテージの影響の例Examples of the effect of the percentage of comonomer in an ethylene copolymer material on the bond strength to a suitable PVDF-based material after electron beam crosslinking
【表2】 [Table 2]
【0019】 電子ビーム架橋後の、適切なPVDF系材料との結合強度における、ポリオレフ
ィンポリマーブレンド中のコポリマーのパーセンテージの影響の例Examples of the effect of the percentage of copolymer in a polyolefin polymer blend on the bond strength with a suitable PVDF-based material after electron beam crosslinking
【表3】 [Table 3]
【0020】 電子ビーム架橋後の、適切なポリオレフィン系材料との結合強度における、PV
DF系材料タイプの影響の例[0020] PV after bonding with an appropriate polyolefin-based material after electron beam crosslinking
Example of influence of DF material type
【表4】 [Table 4]
【0021】 電子ビーム架橋後の、適切なPVDF系材料との結合強度における、オレフィン
材料中のプロラドの添加の影響の例Examples of the effect of the addition of prorad in olefin materials on bond strength with appropriate PVDF-based materials after electron beam crosslinking
【表5】 [Table 5]
【0022】 電線製造例 絶縁体が本発明の2つの結合したポリマー層から成る電線を、以下のように作
った: 絶縁体の内層(即ち、導線体により近い層)は、ポリオレフィン系材料であり
、主として(a)15重量%のEAを含有するEEAコポリマーおよび(b)H
DPEを、約8:2のコポリマー:HDPEの重量比で含んで成り、架橋促進剤
、安定剤、酸化防止剤、着色剤、および加工助剤を包含する一般的な他の添加剤
が、24重量%の合計レベルにおいて少ない割合で存在する。この層を金属導体
上に加圧押出した。 絶縁体の外層は、10重量%のHFPを含有するPVDF/HFPコポリマー
を主として含んで成り、このサンプルにおいて、架橋剤、ならびに着色剤、可塑
剤、安定剤、酸化防止剤、および加工助剤のような他の既知の添加剤を合計7.
5重量%の一般的な割合で含有する。この外層を、分離操作において、先に形成
された内層上に加圧押出した。次に、この被覆電線を電子ビームに通し、20Mr
adの放射線量に暴露した。Wire Making Examples Wires were made wherein the insulator consisted of two bonded polymer layers of the present invention as follows: The inner layer of the insulator (ie, the layer closer to the conductor) was a polyolefin-based material. , Mainly (a) an EEA copolymer containing 15% by weight of EA and (b) H
DPE comprises about 8: 2 copolymer: HDPE by weight, and other common additives including cross-linking accelerators, stabilizers, antioxidants, colorants, and processing aids comprise 24 parts by weight. It is present in small proportions at a total level of weight percent. This layer was pressure extruded onto a metal conductor. The outer layer of the insulator mainly comprises a PVDF / HFP copolymer containing 10% by weight of HFP, and in this sample, the crosslinker, and the colorants, plasticizers, stabilizers, antioxidants, and processing aids. Other known additives such as 7.
It is contained in a general proportion of 5% by weight. This outer layer was pressure extruded onto the previously formed inner layer in a separation operation. Next, the coated electric wire was passed through an electron beam,
Exposure to ad radiation dose.
【0023】 第二の例において電線を前記のように製造し、内層における架橋促進剤は4%
TMPTMであり、絶縁体の外層は10重量%のHFPを含有するPVDF/H
FPコポリマーだけから成った。次に、この被覆電線を電子ビームに通し、20
Mradの放射線量を受けた。この電線をアセトン浸漬試験にかけ、絶縁層が有意に
結合していることを確認した。In a second example, an electric wire was produced as described above, and the crosslinking accelerator in the inner layer was 4%
TMPTM, the outer layer of the insulator being PVDF / H containing 10% by weight of HFP
Consisted solely of the FP copolymer. Next, the coated electric wire was passed through an electron beam,
Received radiation dose of Mrad. This wire was subjected to an acetone immersion test, and it was confirmed that the insulating layer was significantly bonded.
【0024】 第三の例において、第二の例と同じ構造の電線を、内部絶縁層および外部絶縁
層のタンデム加圧押出によって製造した。次に、この被覆電線を電子ビームに通
し、20Mradの放射線量に暴露した。この電線をアセトン浸漬試験にかけ、絶縁
層が有意に結合していることを確認した。In a third example, an electric wire having the same structure as the second example was manufactured by tandem pressure extrusion of the inner insulating layer and the outer insulating layer. The coated wire was then passed through an electron beam and exposed to a radiation dose of 20 Mrad. This wire was subjected to an acetone immersion test, and it was confirmed that the insulating layer was significantly bonded.
【0025】 前記の第二の例のように製造した電線の向上した性能を、現在市販されている電
線と比較して示す。 過酷な取扱および最終使用環境に対する電線の強さの試験において、前記の構
造および製造法の電線(電線Aと称す)を、同じ寸法の市場の主流を占めている
市販のポリオレフィン/PVDF二層電線(電線Bと称す)と比較した。下記の
結果を得た。The improved performance of the wire manufactured as in the second example above is shown in comparison to currently marketed wires. In testing wire strength for harsh handling and end use environments, wires of the above construction and manufacturing method (referred to as wire A) were replaced by commercially available polyolefin / PVDF double-layer wires occupying the mainstream of the market with the same dimensions. (Referred to as electric wire B). The following results were obtained.
【0026】 掻取り摩耗抵抗性の向上の例 方法: 装置=従来型の電線掻取り摩耗試験機、電線寸法0.75mm2(導体
断面積)、ブレードタイプ:フラット、幅3.5mm、電線に垂直に保持、両側に
0.05mmの丸みある縁、適用荷重1.8kg、ストローク長さ10cm、55サ
イクル/分。Example of improvement of scraping abrasion resistance Method: Apparatus = conventional type wire scraping and abrasion tester, wire dimension 0.75 mm 2 (conductor cross section), blade type: flat, width 3.5 mm, wire Holds vertically, rounded edges with 0.05mm on both sides, applied load 1.8kg, stroke length 10cm, 55 cycles / min.
【表6】 [Table 6]
【表7】 [Table 7]
【0027】 冷間衝撃抵抗性の向上の例 方法: 電線寸法6mm2(導体の断面積)、衝撃重量800g、アンビルにお
ける落高275mm、7mmx2mmの寸法の電線に衝撃を与えるアンビル面積がそれ
ぞれの側45゜のテーパーで3.4mmに広がる、周囲温度5℃。絶縁体亀裂生長
の目視検査。Examples of Improvement of Cold Impact Resistance Method: Wire dimensions 6 mm 2 (conductor cross-sectional area), impact weight 800 g, drop on anvil 275 mm, area of anvil that impacts wires with dimensions of 7 mm × 2 mm Spread 3.4 mm with a 45 ° taper, ambient temperature 5 ° C. Visual inspection of insulator crack growth.
【表8】 [Table 8]
【0028】 耐溶剤性の向上の例 方法: 電線寸法:0.75mm2、電線の長さ:60mm、アセトン浸漬深さ:
電線の長さの75%、浸漬時間:1時間、温度:23℃。Example of Improvement in Solvent Resistance Method: Wire dimensions: 0.75 mm 2 , wire length: 60 mm, acetone immersion depth:
75% of the wire length, immersion time: 1 hour, temperature: 23 ° C.
【表9】 [Table 9]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) B32B 15/08 103 B32B 15/08 103Z 27/32 101 27/32 101 // B29K 27:12 B29K 27:12 33:00 33:00 105:22 105:22 B29L 31:34 B29L 31:34 Fターム(参考) 4F100 AB01C AK03A AK19B AK71A AL01A AL01B BA03 BA07 BA10A BA10C CA02 DD31 EH20 EH202 EH23 EH232 EJ05 EJ052 EJ53 EJ532 GB41 4F207 AA03E AA04E AA16 AA21E AB03 AD03 AD15 AG03 AH35 AP18 AR19 KA01 KB11 KB18 KB22 KB26 KJ05 KL58 KM03 KM15 KW33 KW50 5G309 RA04 RA09 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B32B 15/08 103 B32B 15/08 103Z 27/32 101 27/32 101 // B29K 27:12 B29K 27: 12 33:00 33:00 105: 22 105: 22 B29L 31:34 B29L 31:34 F term (reference) 4F100 AB01C AK03A AK19B AK71A AL01A AL01B BA03 BA07 BA10A BA10C CA02 DD31 EH20 EH202 EH23 EH232 EJ05 EJ052 EJ53 EJ532A41 GB41 AA04E AA16 AA21E AB03 AD03 AD15 AG03 AH35 AP18 AR19 KA01 KB11 KB18 KB22 KB26 KJ05 KL58 KM03 KM15 KW33 KW50 5G309 RA04 RA09
Claims (20)
0重量%(全材料組成に基づく)のカルボニル含有ポリマー(ホモポリマーまた
はコポリマーまたはターポリマー)を含んで成り、該ポリマーの少なくとも1種
類の構成モノマーがカルボン酸エステル、好ましくはアクリレートまたはアセテ
ート、特にアルキルアクリレート(例えば、メチルアクリレート、エチルアクリ
レート、プロピルアクリレート、またはブチルアクリレート)であり、コポリマ
ーまたはターポリマーが使用される場合に該モノマーがコポリマーまたはターポ
リマーの少なくとも5重量%を構成し、該コポリマーまたはターポリマーの残り
が、オレフィンモノマー、好ましくはエチレンから誘導されるのが好ましい、ポ
リオレフィン系材料の少なくとも第一の層;および、第一の層に接触する (ii) 全材料組成に基づいて少なくとも10重量%のポリビニリデンフル
オライド(PVDF)、またはVDFおよび部分または完全弗素化コモノマーに
基づくコポリマーを含有する材料の少なくとも第二の層; を有して成り; 該層(i)と(ii)との間の剥離結合強度を少なくとも5Nに増加させるの
に充分であるように、該層(i)および(ii)を、相互に接触させながら、架
橋反応に付されている; 電線またはケーブル。1. An electric wire or cable having an insulator, the insulator comprising: (i) at least a first layer of a polyolefin-based material,
0% by weight (based on the total material composition) of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer) in which at least one constituent monomer of the polymer is a carboxylic acid ester, preferably an acrylate or acetate, especially an alkyl An acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, or butyl acrylate), wherein when a copolymer or terpolymer is used, the monomer comprises at least 5% by weight of the copolymer or terpolymer; At least a first layer of a polyolefin-based material, the remainder of the polymer preferably being derived from an olefin monomer, preferably ethylene; and contacting the first layer (ii) based on the total material composition At least 10% by weight of polyvinylidene fluoride (PVDF), or at least a second layer of a material containing VDF and a copolymer based on partially or fully fluorinated comonomers. the layers (i) and (ii) have been subjected to a cross-linking reaction while contacting each other so as to be sufficient to increase the peel bond strength between ii) to at least 5N; cable.
ポリマー部分の少なくとも20重量%、好ましくは少なくとも40重量%、より
好ましくは少なくとも60重量%、または特に好ましくは少なくとも80重量%
が、カルボニル含有ポリマー(ホモポリマーまたはコポリマーまたはターポリマ
ー)から成り、該ポリマーの少なくとも1種類の構成モノマーがカルボン酸エス
テル、好ましくはアクリレートまたはアセテート、特にアルキルアクリレート(
好ましくは、メチルアクリレート、エチルアクリレート、プロピルアクリレート
、またはブチルアクリレート)であり、コポリマーまたはターポリマーが使用さ
れる場合に該モノマーがコポリマーまたはターポリマーの少なくとも5重量%、
好ましくは少なくとも9重量%、より好ましくは少なくとも15重量%を構成し
、該コポリマーまたはターポリマーの残りまたは残りの大部分が、オレフィンモ
ノマー、好ましくはエチレンから誘導されるのが好ましい、ポリオレフィン系配
合物の少なくとも第一の層;および、第一の層に接触する (ii) 他の材料配合物の少なくとも第二の層であって、該第二の層の少な
くとも10重量%、より好ましくは少なくとも50重量%、特に好ましくは少な
くとも90重量%、特別に100重量%のポリビニリデンフルオライド(PVD
F)、または特に好ましくはVDFおよび部分または完全弗素化コモノマーに基
づくコポリマー、最も好ましくはVDFとヘキサフルオロプロピレン(HFP)
のコポリマーを含有する、他の材料配合物の少なくとも第二の層; を有して成り; 23℃において1時間のアセトン浸漬試験中に該2層の離層を防止するか、ま
たはASTM B1876-95の方法による該層間の剥離結合強度を少なくとも5Nに増加
させ、好ましくは非架橋層間の結合強度と比較して、少なくとも50%、より好
ましくは少なくとも100%、特に少なくとも500%または1000%で結合
強度を増加させるのに充分であるように、該層(i)および(ii)を、相互に
接触させながら、好ましくは放射線、より好ましくは電離線によって架橋反応に
付されている; 電線またはケーブル。2. An electric wire or cable having an insulator, the insulator comprising: (i) at least a first layer of a polyolefin-based composition, wherein at least 20% by weight of a polymer portion of the composition; Preferably at least 40% by weight, more preferably at least 60% by weight, or particularly preferably at least 80% by weight
Consists of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer), wherein at least one constituent monomer of the polymer is a carboxylic acid ester, preferably an acrylate or acetate, especially an alkyl acrylate (
Preferably methyl acrylate, ethyl acrylate, propyl acrylate, or butyl acrylate), wherein when a copolymer or terpolymer is used, the monomer is at least 5% by weight of the copolymer or terpolymer;
A polyolefin-based formulation, preferably comprising at least 9% by weight, more preferably at least 15% by weight, wherein the remainder or the majority of the remainder of the copolymer or terpolymer is preferably derived from olefin monomers, preferably ethylene. And (ii) at least a second layer of another material formulation, wherein said second layer comprises at least 10% by weight of said second layer, more preferably at least 50% by weight of said second layer. % By weight, particularly preferably at least 90% by weight, especially 100% by weight of polyvinylidene fluoride (PVD
F), or particularly preferably a copolymer based on VDF and partially or fully fluorinated comonomers, most preferably VDF and hexafluoropropylene (HFP)
At least a second layer of another material formulation containing a copolymer of the following: preventing delamination of said two layers during an acetone soak test at 23 ° C. for 1 hour, or ASTM B1876- Increasing the peel bond strength between said layers by at least 95 by at least 5N, preferably at least 50%, more preferably at least 100%, especially at least 500% or 1000%, compared to the bond strength between non-crosslinked layers The layers (i) and (ii) have been subjected to a crosslinking reaction, preferably by radiation, more preferably by ionizing radiation, in contact with each other, so as to be sufficient to increase the strength; .
を防止するのに充分であるように、該層(i)および(ii)を、相互に接触さ
せながら、好ましくは放射線、より好ましくは電離線によって架橋反応に付され
ている請求項1に記載の電線またはケーブル。3. The layers (i) and (ii) are brought into contact with each other so as to be sufficient to prevent delamination of the two layers during an acetone soak test at 23 ° C. for 1 hour. The wire or cable according to claim 1, which is preferably subjected to a crosslinking reaction by radiation, more preferably by ionizing radiation.
50%、より好ましくは少なくとも100%、特に少なくとも500%または1
000%で結合強度を増加させる請求項1〜3のいずれかに記載の電線またはケ
ーブル。4. The crosslinking reaction is at least 50%, more preferably at least 100%, especially at least 500% or 1% as compared to the bond strength between the non-crosslinked layers.
The electric wire or cable according to any one of claims 1 to 3, wherein the bonding strength is increased by 000%.
材料の融点または軟化点より高い温度において、各層を相互に接触させる請求項
1〜4のいずれかに記載の電線またはケーブル。5. The wire or claim according to claim 1, wherein prior to crosslinking of the layers, the layers are brought into contact with each other at a temperature above the melting or softening point of the polymer material in at least one of the layers. cable.
ロプロピレン(HFP)のコポリマーを含んで成り、該コポリマーが、該層の材
料の大部分の重量%、好ましくは実質的に全てを構成する請求項1〜5のいずれ
かに記載の電線またはケーブル。6. The polyvinylidene fluoride-based layer comprises a copolymer of VDF and hexafluoropropylene (HFP), wherein the copolymer comprises a majority, preferably substantially all, of the material of the layer by weight. The electric wire or cable according to any one of claims 1 to 5, which constitutes.
量%、特に好ましくは9〜11重量%のヘキサフルオロプロピレン(HFP)含
有量の、VDFとヘキサフルオロプロピレン(HFP)のコポリマーを含んで成
る請求項1〜6のいずれかに記載の電線またはケーブル。7. A copolymer of VDF and hexafluoropropylene (HFP), wherein the polyvinylidene fluoride-based layer has a hexafluoropropylene (HFP) content of preferably 8 to 12% by weight, particularly preferably 9 to 11% by weight. The electric wire or cable according to any one of claims 1 to 6, comprising:
有ポリマーの混合物を含んで成る請求項1〜7のいずれかに記載の電線またはケ
ーブル。8. The electric wire or cable according to claim 1, wherein the polyolefin-based layer comprises a mixture of polyethylene and the carbonyl-containing polymer.
ルオライド系材料の外層を有して成る請求項1〜8のいずれかに記載の電線また
はケーブル。9. The electric wire or cable according to claim 1, comprising an inner layer of the polyolefin-based material and an outer layer of the polyvinylidene fluoride-based material.
またはケーブル。10. The wire or cable according to claim 9, wherein said outer layer is extruded under pressure into said inner layer.
請求項1〜10のいずれかに記載の電線またはケーブル。11. The wire or cable according to claim 1, wherein the crosslinking reaction is carried out by radiation, preferably by ionizing radiation.
して成る請求項1〜11のいずれかに記載の電線またはケーブル。12. An electric wire or cable according to claim 1, comprising alternating layers of the material constituting said layers (i) and (ii).
なくとも1種類の架橋促進剤を含有し、該架橋促進剤が、該層(i)の材料だけ
に添加されているのが好ましい請求項1〜12のいずれかに記載の電線またはケ
ーブル。13. The material of one or both of said layers (i) and (ii) contains at least one type of crosslinking accelerator, said crosslinking accelerator being added only to the material of said layer (i). The electric wire or cable according to any one of claims 1 to 12, which is preferably provided.
なくとも1種類の架橋促進剤を含有し、該架橋促進剤が、多官能性アクリレート
またはメタクリレートエステル、好ましくはトリメチロールプロパントリメタク
リレート(TMPTM)である請求項1〜13のいずれかに記載の電線またはケ
ーブル。14. The material of one or both of the layers (i) and (ii) contains at least one crosslinking accelerator, wherein the crosslinking accelerator is a polyfunctional acrylate or methacrylate ester, preferably The electric wire or cable according to any one of claims 1 to 13, which is trimethylolpropane trimethacrylate (TMPTM).
請求項14に記載の電線またはケーブル。15. The electric wire or cable according to claim 14, wherein the crosslinking accelerator is added only to the material of the layer (i).
好ましくは実質的にPVDFまたは該VDFコポリマーのみを含有する請求項1
〜15のいずれかに記載の電線またはケーブル。16. The polyvinylidene-based layer (ii) is substantially transparent,
2. The method of claim 1, wherein the composition comprises substantially only PVDF or the VDF copolymer.
16. The electric wire or cable according to any one of items 15 to 15.
工程、および該層を相互に接触させながら該架橋反応に付す工程、を含んで成る
請求項1〜16のいずれかに記載の電線またはケーブルの製造法。17. The method of claim 1, further comprising the step of providing said layers (i) and (ii) in contact with each other on a conductor, and subjecting said layers to said crosslinking reaction while contacting each other. A method for producing an electric wire or cable according to any one of the above.
も1つにおけるポリマー材料の融点または軟化点より高い温度において、各層を
相互に接触させる請求項17に記載の方法。18. The method of claim 17, wherein the layers are brought into contact with each other before (a) crosslinking the layers and (b) at a temperature above the melting or softening point of the polymer material in at least one of the layers. Method.
)を層(i)に加圧押出する請求項17または18に記載の方法。19. The layer (i) is extruded under pressure into a conductor and / or the layer (ii)
19. The method according to claim 17 or claim 18, wherein pressure is extruded into layer (i).
への導体の単一パスおいて、層(i)および(ii)を電線に同時押出するかま
たはタンデム押出する請求項17、18、または19に記載の方法。20. The method of claim 17, 18 or 18, wherein layers (i) and (ii) are co-extruded or tandem extruded into an electrical wire in a single pass of the conductor from the extrusion process unwind device to the extrusion process take-off device. 20. The method according to 19.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9820214.6A GB9820214D0 (en) | 1998-09-17 | 1998-09-17 | Bonding polymer interface |
GB9820214.6 | 1998-09-17 | ||
PCT/GB1999/003116 WO2000017889A1 (en) | 1998-09-17 | 1999-09-17 | Electrical wire insulation |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2002525819A true JP2002525819A (en) | 2002-08-13 |
Family
ID=10838985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000571464A Pending JP2002525819A (en) | 1998-09-17 | 1999-09-17 | Wire insulation |
Country Status (22)
Country | Link |
---|---|
EP (1) | EP1116243B1 (en) |
JP (1) | JP2002525819A (en) |
KR (1) | KR100638181B1 (en) |
CN (1) | CN1331160C (en) |
AT (1) | ATE321345T1 (en) |
AU (1) | AU766430B2 (en) |
BR (1) | BR9913843A (en) |
CA (1) | CA2340386C (en) |
CZ (1) | CZ299046B6 (en) |
DE (1) | DE69930532T2 (en) |
ES (1) | ES2260937T3 (en) |
GB (1) | GB9820214D0 (en) |
HU (1) | HU226699B1 (en) |
ID (1) | ID29877A (en) |
IL (2) | IL141338A0 (en) |
NO (1) | NO324458B1 (en) |
PL (1) | PL192515B1 (en) |
RO (1) | RO121928B1 (en) |
RU (1) | RU2231147C2 (en) |
TR (1) | TR200100761T2 (en) |
WO (1) | WO2000017889A1 (en) |
ZA (1) | ZA200101181B (en) |
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- 1998-09-17 GB GBGB9820214.6A patent/GB9820214D0/en not_active Ceased
-
1999
- 1999-09-17 ID IDW20010554A patent/ID29877A/en unknown
- 1999-09-17 EP EP99947633A patent/EP1116243B1/en not_active Expired - Lifetime
- 1999-09-17 RO ROA200100291A patent/RO121928B1/en unknown
- 1999-09-17 RU RU2001107973/09A patent/RU2231147C2/en not_active IP Right Cessation
- 1999-09-17 BR BR9913843-3A patent/BR9913843A/en not_active IP Right Cessation
- 1999-09-17 CZ CZ20010482A patent/CZ299046B6/en not_active IP Right Cessation
- 1999-09-17 AT AT99947633T patent/ATE321345T1/en not_active IP Right Cessation
- 1999-09-17 TR TR2001/00761T patent/TR200100761T2/en unknown
- 1999-09-17 CA CA002340386A patent/CA2340386C/en not_active Expired - Fee Related
- 1999-09-17 PL PL346214A patent/PL192515B1/en unknown
- 1999-09-17 KR KR1020017002898A patent/KR100638181B1/en active IP Right Grant
- 1999-09-17 WO PCT/GB1999/003116 patent/WO2000017889A1/en active IP Right Grant
- 1999-09-17 AU AU61019/99A patent/AU766430B2/en not_active Expired
- 1999-09-17 JP JP2000571464A patent/JP2002525819A/en active Pending
- 1999-09-17 IL IL14133899A patent/IL141338A0/en active IP Right Grant
- 1999-09-17 HU HU0103585A patent/HU226699B1/en unknown
- 1999-09-17 CN CNB998110302A patent/CN1331160C/en not_active Expired - Lifetime
- 1999-09-17 DE DE69930532T patent/DE69930532T2/en not_active Expired - Lifetime
- 1999-09-17 ES ES99947633T patent/ES2260937T3/en not_active Expired - Lifetime
-
2001
- 2001-02-08 IL IL141338A patent/IL141338A/en not_active IP Right Cessation
- 2001-02-12 ZA ZA200101181A patent/ZA200101181B/en unknown
- 2001-03-15 NO NO20011307A patent/NO324458B1/en not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002225204A (en) * | 2001-01-30 | 2002-08-14 | Reitekku:Kk | Modified fluororesin coated material and method for producing the same |
JP2005015793A (en) * | 2003-06-06 | 2005-01-20 | Arkema | Method for grafting fluoropolymer and multilayered structure containing obtained grafted polymer |
Also Published As
Publication number | Publication date |
---|---|
RO121928B1 (en) | 2008-07-30 |
CA2340386A1 (en) | 2000-03-30 |
NO20011307D0 (en) | 2001-03-15 |
EP1116243B1 (en) | 2006-03-22 |
EP1116243A1 (en) | 2001-07-18 |
BR9913843A (en) | 2001-08-14 |
CN1331160C (en) | 2007-08-08 |
CZ299046B6 (en) | 2008-04-09 |
HUP0103585A3 (en) | 2002-04-29 |
WO2000017889A1 (en) | 2000-03-30 |
NO20011307L (en) | 2001-03-15 |
HU226699B1 (en) | 2009-07-28 |
DE69930532T2 (en) | 2007-03-08 |
IL141338A (en) | 2006-12-31 |
PL192515B1 (en) | 2006-10-31 |
IL141338A0 (en) | 2002-03-10 |
PL346214A1 (en) | 2002-01-28 |
AU6101999A (en) | 2000-04-10 |
KR20010079751A (en) | 2001-08-22 |
ID29877A (en) | 2001-10-18 |
TR200100761T2 (en) | 2001-09-21 |
ES2260937T3 (en) | 2006-11-01 |
KR100638181B1 (en) | 2006-10-26 |
CN1318200A (en) | 2001-10-17 |
ZA200101181B (en) | 2002-05-13 |
DE69930532D1 (en) | 2006-05-11 |
NO324458B1 (en) | 2007-10-22 |
CZ2001482A3 (en) | 2001-07-11 |
CA2340386C (en) | 2009-04-14 |
GB9820214D0 (en) | 1998-11-11 |
HUP0103585A2 (en) | 2002-01-28 |
RU2231147C2 (en) | 2004-06-20 |
ATE321345T1 (en) | 2006-04-15 |
AU766430B2 (en) | 2003-10-16 |
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