JP2015160873A - Fluorine-containing elastomer composition and wire prepared using the same - Google Patents
Fluorine-containing elastomer composition and wire prepared using the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229920001971 elastomer Polymers 0.000 title claims abstract description 38
- 239000000806 elastomer Substances 0.000 title claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 22
- 239000011737 fluorine Substances 0.000 title claims abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 20
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 16
- 239000004945 silicone rubber Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000004711 α-olefin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000945 filler Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000012438 extruded product Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
Description
本発明は、含ふっ素エラストマ組成物及びそれを用いた電線に関し、特に、押出成形のための含ふっ素エラストマ組成物及びそれを用いた電線に関する。 The present invention relates to a fluorine-containing elastomer composition and an electric wire using the same, and more particularly to a fluorine-containing elastomer composition for extrusion molding and an electric wire using the same.
ふっ素樹脂、特に、テトラフルオロエチレン−プロピレン系共重合体に代表される、テトラフルオロエチレンと炭素数２〜４のα−オレフィンとの共重合体は、耐熱性、耐油性、耐薬品性、及び絶縁特性に優れている。このような性質は、電線の被覆材として求められている性質である。 Fluoropolymers, in particular, copolymers of tetrafluoroethylene and α-olefins having 2 to 4 carbon atoms, represented by tetrafluoroethylene-propylene copolymers, have heat resistance, oil resistance, chemical resistance, and Excellent insulation properties. Such a property is a property required as a coating material for electric wires.
特許文献１及び２では、テトラフルオロエチレンと炭素数２〜４のα−オレフィンとの共重合体に炭酸カルシウムを含む充填剤を配合することで、電線の被覆材に用いる材料の耐屈曲疲労性、耐熱変形性、機械的強度を向上させていることが記載されている。 In patent documents 1 and 2, the bending fatigue resistance of the material used for the coating | covering material of an electric wire is mix | blended with the filler containing a calcium carbonate in the copolymer of tetrafluoroethylene and a C2-C4 alpha olefin. It is described that heat resistance and mechanical strength are improved.
特許文献３及び４では、テトラフルオロエチレン−プロピレン共重合体を含む組成物に対して、オレフィン系樹脂又はビニル系樹脂にシリコーンがグラフト重合されたシリコーングラフト共重合体を添加することで、ダイスカスの発生を改善していることが記載されている。 In Patent Documents 3 and 4, by adding a silicone graft copolymer obtained by graft-polymerizing silicone to an olefin resin or vinyl resin to a composition containing a tetrafluoroethylene-propylene copolymer, It is described that the occurrence is improved.
特許文献５では、被覆層として内層と外層を設けた被覆電線において、内層側組成物中のポリマーブレンド（テトラフルオロエチレン−プロピレン共重合体／ポリビニリデンフルオライド）と、外層側組成物中のポリマーブレンド（テトラフルオロエチレン−プロピレン共重合体／エチレン−テトラフルオロエチレン共重合体）とで異なるものを用いており、外層側にダイスカスを効果的に抑制できる材料を用いて外観の向上を図っていることが記載されている。 In patent document 5, in the covered electric wire which provided the inner layer and the outer layer as a coating layer, the polymer blend (tetrafluoroethylene-propylene copolymer / polyvinylidene fluoride) in the inner layer side composition and the polymer in the outer layer side composition Different blends (tetrafluoroethylene-propylene copolymer / ethylene-tetrafluoroethylene copolymer) are used, and the appearance is improved by using a material that can effectively suppress die scum on the outer layer side. It is described.
しかしながら、特許文献１及び２の組成物では、充填剤の炭酸カルシウムに起因するダイスカスが発生しやすい。特許文献３及び４の組成物では、ダイスカス抑制のために用いるシリコーングラフト共重合体は高価であり、組成物は高価なものとなる。特許文献５の電線では、機械的強度、耐熱性等の必要とされる性能を満たしつつ外観を良好なものとするためには、被覆層を２層とする必要があり、この点についてさらなるコスト低減の余地がある。 However, in the compositions of Patent Documents 1 and 2, die scum caused by calcium carbonate as a filler is likely to occur. In the compositions of Patent Documents 3 and 4, the silicone graft copolymer used for suppressing die scum is expensive, and the composition becomes expensive. In the electric wire of Patent Document 5, in order to satisfy the required performance such as mechanical strength and heat resistance and to have a good appearance, it is necessary to have two coating layers, and this point is further costly. There is room for reduction.
そこで、本発明は、機械的強度、耐熱性に優れ、押出成形品の外観が良好で、かつ安価な含ふっ素エラストマ組成物及びそれを用いた電線を提供することを目的とする。 Therefore, an object of the present invention is to provide a fluorine-containing elastomer composition that is excellent in mechanical strength and heat resistance, has a good appearance of an extruded product, and is inexpensive, and an electric wire using the same.
上記目的を達成するために、本発明は、テトラフルオロエチレンと炭素数２〜４のα−オレフィンとの共重合体を含有する樹脂成分１００質量部に対して、シリカを５〜２０質量部、平均粒径が１．０〜４．０μｍの重質炭酸カルシウムを５〜５０質量部、及びシリコーンゴムを１〜２０質量部混和させたことを特徴とする含ふっ素エラストマ組成物を提供する。 In order to achieve the above object, the present invention provides 5 to 20 parts by mass of silica with respect to 100 parts by mass of a resin component containing a copolymer of tetrafluoroethylene and an α-olefin having 2 to 4 carbon atoms, Provided is a fluorine-containing elastomer composition comprising 5 to 50 parts by weight of heavy calcium carbonate having an average particle size of 1.0 to 4.0 μm and 1 to 20 parts by weight of silicone rubber.
前記シリコーンゴムは、ジメチルポリシロキサン、メチルビニルポリシロキサン、及びメチルフェニルポリシロキサンのうち１種類又は２種類以上を含むとよい。 The silicone rubber may include one or more of dimethylpolysiloxane, methylvinylpolysiloxane, and methylphenylpolysiloxane.
前記含ふっ素エラストマ組成物を用いて導体を被覆した含ふっ素エラストマ組成物を用いた電線であるとよい。 An electric wire using the fluorine-containing elastomer composition in which a conductor is coated with the fluorine-containing elastomer composition is preferable.
前記導体の直径は１．６±０．５ｍｍであり、前記被覆層の厚さが０．５ｍｍ以下であるとよい。 The diameter of the conductor is 1.6 ± 0.5 mm, and the thickness of the coating layer is preferably 0.5 mm or less.
本発明によれば、機械的強度、耐熱性に優れ、押出成形品の外観が良好で、かつ安価な含ふっ素エラストマ組成物及びそれを用いた電線を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in mechanical strength and heat resistance, the external appearance of an extrusion molded article is favorable, and an inexpensive fluorine-containing elastomer composition and an electric wire using the same can be provided.
以下、本発明の好適な実施形態を添付図面に基づいて詳述する。なお、本発明の実施形態は以下の記載に限定されるものではない。 DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, embodiment of this invention is not limited to the following description.
＜含ふっ素エラストマ組成物＞
本実施形態に係る含ふっ素エラストマ組成物（以下、エラストマ組成物）について説明する。本実施形態に係るエラストマ組成物は、テトラフルオロエチレン−α−オレフィン共重合体を含有する樹脂成分に対して、シリカと、炭酸カルシウムと、シリコーンゴムとを混和させたものである。なお、本発明の効果を奏する限りにおいて、樹脂成分には上記の共重合体の他の成分が含まれていてもよい。また、エラストマ組成物に架橋剤、架橋助剤、受酸剤、滑剤、他の無機充填剤、安定剤、酸化防止剤、可塑剤等の添加剤を適宜加えてもよい。
<Fluorine-containing elastomer composition>
The fluorine-containing elastomer composition (hereinafter referred to as an elastomer composition) according to this embodiment will be described. The elastomer composition according to this embodiment is obtained by mixing silica, calcium carbonate, and silicone rubber with a resin component containing a tetrafluoroethylene-α-olefin copolymer. In addition, as long as there exists an effect of this invention, the other component of said copolymer may be contained in the resin component. Moreover, you may add suitably additives, such as a crosslinking agent, a crosslinking adjuvant, an acid acceptor, a lubricant, another inorganic filler, a stabilizer, antioxidant, a plasticizer, to an elastomer composition.
テトラフルオロエチレン−α−オレフィン共重合体は、テトラフルオロエチレンと炭素数２〜４のα−オレフィンとを共重合して得られる。α−オレフィンとしては、エチレン、プロピレン、１−ブテン、及びイソブテンのうち、１種類又は２種類以上の組み合わせが含まれるが、プロピレンが好ましい。共重合体中の、テトラフルオロエチレンとα−オレフィンとの含有モル比は、９５：５〜３０：７０であることが好ましい。 The tetrafluoroethylene-α-olefin copolymer is obtained by copolymerizing tetrafluoroethylene and an α-olefin having 2 to 4 carbon atoms. The α-olefin includes one kind or a combination of two or more kinds of ethylene, propylene, 1-butene, and isobutene, and propylene is preferable. The content molar ratio of tetrafluoroethylene and α-olefin in the copolymer is preferably 95: 5 to 30:70.
また、この共重合体には、主成分のテトラフルオロエチレン及びα−オレフィンに加えて、これらと共重合可能な成分が含まれていてもよい。このような成分の例として、エチレン、イソブチレン、アクリル酸及びそのアルキルエステル、フッ化ビニル、フッ化ビニリデン、ヘキサフルオロプロペン、クロロエチルビニルエーテル、クロロトリフルオロエチレン、パーフルオロアルキルビニルエーテル等が挙げられる。このような、主成分以外の成分の含有量は、５０モル％以下であることが好ましく、さらに好ましくは３０％モル以下である。 In addition to the main components tetrafluoroethylene and α-olefin, the copolymer may contain components copolymerizable therewith. Examples of such components include ethylene, isobutylene, acrylic acid and alkyl esters thereof, vinyl fluoride, vinylidene fluoride, hexafluoropropene, chloroethyl vinyl ether, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and the like. The content of components other than the main component is preferably 50 mol% or less, more preferably 30% mol or less.
テトラフルオロエチレン−α−オレフィン共重合体は、数平均分子量が２万〜２０万とすることが好ましい。数平均分子量の調整方法は、単量体濃度、重合開始剤濃度、単量体量と重合開始剤量との比、重合温度、連鎖移動剤の使用等の共重合反応条件の操作により、重合の際に重合度を直接調整する方法がある。また、数平均分子量の調整は、共重合反応によって高分子量の共重合体を生成し、これを酸素存在下で加熱処理するなどして低分子化する方法によっても行うことができる。 The tetrafluoroethylene-α-olefin copolymer preferably has a number average molecular weight of 20,000 to 200,000. The method for adjusting the number average molecular weight is determined by the operation of the copolymerization reaction conditions such as the monomer concentration, the polymerization initiator concentration, the ratio of the monomer amount to the polymerization initiator amount, the polymerization temperature, and the use of a chain transfer agent. There is a method in which the degree of polymerization is directly adjusted. The number average molecular weight can also be adjusted by a method of reducing the molecular weight by, for example, producing a high molecular weight copolymer by a copolymerization reaction and subjecting it to heat treatment in the presence of oxygen.
シリカは、エラストマ組成物に含有させることにより、その引張強さを向上させる。シリカは、上記樹脂成分１００質量部に対して、５〜２０質量部混和される。シリカの混和量が５質量部未満であると、引張強さを向上させる効果が十分に得られず、２０質量部を超えると、エラストマ組成物の耐熱性が低下する。また、本実施形態で用いられるシリカは、乾式法で製造され、疎水性を有するように表面処理されたものである。このような表面処理がなされていないシリカを用いると、成形の際、エラストマ組成物の粘度（ムーニ粘度）が高くなり、押出性（成形性）が低下する。 Silica improves the tensile strength by being contained in the elastomer composition. Silica is mixed in an amount of 5 to 20 parts by mass with respect to 100 parts by mass of the resin component. If the mixing amount of silica is less than 5 parts by mass, the effect of improving the tensile strength cannot be sufficiently obtained, and if it exceeds 20 parts by mass, the heat resistance of the elastomer composition is lowered. Further, the silica used in the present embodiment is manufactured by a dry method and surface-treated so as to have hydrophobicity. When silica not subjected to such a surface treatment is used, the viscosity (Munii viscosity) of the elastomer composition increases during molding, and the extrudability (moldability) decreases.
炭酸カルシウムは、安価な充填剤で、エラストマ組成物中の含有量が多いほど、エラストマ組成物は低コストになる。本実施形態では、エラストマ組成物の耐熱性を確保するために、重質炭酸カルシウムが用いられる。炭酸カルシウムは、上記樹脂成分１００質量部に対して、５〜５０質量部混和される。炭酸カルシウムが５質量部未満であると、エラストマ組成物のコストを十分に低減できず、５０質量部を超えるとエラストマ組成物の耐熱性が低下する。なお、炭酸カルシウムの平均粒径は１．０〜４．０μｍである。炭酸カルシウムの平均粒径が１．０μｍ未満であるとエラストマ組成物の耐熱性が低下し、４．０μｍを超えるとエラストマ組成物の引張強さが不十分となる。 Calcium carbonate is an inexpensive filler, and the higher the content in the elastomer composition, the lower the cost of the elastomer composition. In this embodiment, heavy calcium carbonate is used to ensure the heat resistance of the elastomer composition. 5 to 50 parts by mass of calcium carbonate is mixed with 100 parts by mass of the resin component. If the calcium carbonate is less than 5 parts by mass, the cost of the elastomer composition cannot be sufficiently reduced, and if it exceeds 50 parts by mass, the heat resistance of the elastomer composition is lowered. In addition, the average particle diameter of calcium carbonate is 1.0-4.0 micrometers. When the average particle size of calcium carbonate is less than 1.0 μm, the heat resistance of the elastomer composition is lowered, and when it exceeds 4.0 μm, the tensile strength of the elastomer composition becomes insufficient.
シリコーンゴムは、ダイスにゴムコンパウンドが粘着して発生するダイスカスを抑制し、押出成形品の外観を良好にする。特に、本実施形態の場合、添加される炭酸カルシウムによってダイスカスが発生しやすくなっており、これを抑制するためにシリコーンゴムが加えられる。シリコーンゴムは、例えば、ジメチルポリシロキサン、メチルビニルポリシロキサン、メチルフェニルポリシロキサン等であり、これらのうち１種類又は２種類以上からなる。また、シリコーンゴムにシリカ等の充填剤が添加されたものでもよい。シリコーンゴムは、樹脂成分１００質量部に対して、１〜２０質量部混和される。シリコーンゴムが１質量部未満であると、ダイスカスの発生を抑制する効果が得にくく、２０質量部を超えると、エラストマ組成物の機械的強度（引張強さ）及び耐熱性が低下する。 Silicone rubber suppresses die scum generated when a rubber compound adheres to a die, and improves the appearance of an extruded product. In particular, in the case of this embodiment, die scum is easily generated by the added calcium carbonate, and silicone rubber is added to suppress this. Silicone rubber is, for example, dimethylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, and the like, and includes one or more of these. Moreover, what added fillers, such as a silica, to silicone rubber may be used. The silicone rubber is mixed in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. When the silicone rubber is less than 1 part by mass, it is difficult to obtain the effect of suppressing the occurrence of die scum, and when it exceeds 20 parts by mass, the mechanical strength (tensile strength) and heat resistance of the elastomer composition are lowered.
架橋剤、架橋助剤は樹脂成分を架橋するために加えられ、これにより成形品はゴム弾性を有するようになる。架橋剤としては、有機化酸化物、例えばα，α’−ジ（ターシャル−ブチルパーオキサイド）ジイソプロピルベンゼンが好ましい。架橋助剤は、架橋反応性を高めるために添加され、例えば、トリアリルイソシアヌレート、トリアリルシアヌレート、トリアリルトリメリテート、テトラアリルピロメリテート等のアリル型化合物が特に好ましい。 A cross-linking agent and a cross-linking aid are added to cross-link the resin component, whereby the molded article has rubber elasticity. The crosslinking agent is preferably an organic oxide such as α, α'-di (tertiary-butyl peroxide) diisopropylbenzene. The crosslinking aid is added to increase crosslinking reactivity, and for example, allyl compounds such as triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate and tetraallyl pyromellitate are particularly preferable.
受酸剤は、ポリマーの分解等により生じるハロゲン化水素（フッ化水素）を除去するために用いられ、酸化マグネシウムが好ましく用いられる。 The acid acceptor is used to remove hydrogen halide (hydrogen fluoride) generated by polymer decomposition or the like, and magnesium oxide is preferably used.
滑剤は、成形における材料の流動性及び離型性を向上させるために用いられ、ステアリン酸バリウム等が用いられる。 The lubricant is used to improve the fluidity and release properties of the material in molding, and barium stearate or the like is used.
＜含ふっ素エラストマ組成物を用いた電線＞
図１は、本発明の一実施形態に係る含ふっ素エラストマ組成物を用いた電線を模式的に示す断面図である。電線１は、導体２と、導体２の周囲を被覆する被覆層３とを有する。導体２は、金属線であり、本実施形態においては直径１．６±０．５ｍｍの錫めっき銅撚線であるが、これに限られない。被覆層３は、上で説明した含ふっ素エラストマ組成物からなる。本実施形態では、被覆層３の厚さは０．５ｍｍ以下であるが、これに限られない。
<Electric wire using fluorine-containing elastomer composition>
FIG. 1 is a cross-sectional view schematically showing an electric wire using a fluorine-containing elastomer composition according to an embodiment of the present invention. The electric wire 1 includes a conductor 2 and a coating layer 3 that covers the periphery of the conductor 2. The conductor 2 is a metal wire, which is a tin-plated copper stranded wire having a diameter of 1.6 ± 0.5 mm in the present embodiment, but is not limited thereto. The coating layer 3 is made of the fluorine-containing elastomer composition described above. In this embodiment, although the thickness of the coating layer 3 is 0.5 mm or less, it is not restricted to this.
＜実施例＞
以下、本発明の一実施形態に係る電線１ついて、実施例に基づいて説明する。まず、表１の実施例１〜６及び比較例１〜９の各欄に示す組成物を、ロールを用いて混練し、コンパウンドを作製した。
<Example>
Hereinafter, the electric wire 1 which concerns on one Embodiment of this invention is demonstrated based on an Example. First, the composition shown in each column of Examples 1 to 6 and Comparative Examples 1 to 9 in Table 1 was kneaded using a roll to prepare a compound.
これらのコンパウンドを用いて、ダイス１００℃、ヘッド８０℃、シリンダを上流側及び下流側ともに８０℃に設定した４０ｍｍ押出機（Ｌ／Ｄ＝２２）により、外径１．６ｍｍの錫めっき銅撚線（導体２）の外側を厚さ０．３ｍｍで押出被覆した。その後、１３ｋｇ／ｃｍ2のスチームにて３分間架橋を行った。 Using these compounds, a tin-plated copper twist with an outer diameter of 1.6 mm was made by a 40 mm extruder (L / D = 22) in which a die was set at 100 ° C., a head at 80 ° C., and a cylinder set at 80 ° C. on both the upstream and downstream sides. The outside of the wire (conductor 2) was extrusion coated with a thickness of 0.3 mm. Thereafter, crosslinking was carried out with 13 kg / cm 2 steam for 3 minutes.
このように製造した電線１の機械的強度（引張強さ、伸び）、耐熱性、ダイスカス発生の有無、コンパウンド価格を評価した。 The electrical strength 1 thus produced was evaluated for mechanical strength (tensile strength, elongation), heat resistance, presence / absence of die scum, and compound price.
機械的強度及び耐熱性は、ＪＩＳＣ３００５ ４．１６（２０００）に準拠して、電線１から導体２を引き抜いてチューブ形状として測定した。引張強さは１２ＭＰａ以上、伸びは２００％以上を合格とした。耐熱性は、２５０℃で４日間熱老化試験機に入れた後、取り出し、機械的強度（試験後）を測定し、これらの初期（試験前）の値と比較した。具体的には、引張強さ残率（％）＝（試験後の引張強さ／試験前の引張強さ）×１００、伸び残率（％）＝（試験後の伸び／試験前の伸び）×１００として、これらの数値がいずれも８０％以上であれば合格とした。 The mechanical strength and heat resistance were measured as a tube shape by drawing the conductor 2 from the electric wire 1 in accordance with JISC3005 4.16 (2000). The tensile strength was 12 MPa or more, and the elongation was 200% or more. The heat resistance was taken out at 250 ° C. for 4 days and then taken out, measured for mechanical strength (after test), and compared with these initial values (before test). Specifically, tensile strength residual rate (%) = (tensile strength after test / tensile strength before test) × 100, residual elongation rate (%) = (elongation after test / elongation before test) As x100, if any of these values was 80% or more, it was judged as acceptable.
ダイスカス発生の有無は目視によって確認し、コンパウンド価格は、同じの長さの電線を製造するためにかかるコンパウンドの材料費を比較した。 The presence or absence of die scum was confirmed by visual inspection, and the compound price was compared with the material cost of the compound to produce the same length of wire.
評価結果は表１の下欄に示した通りである。実施例１〜６は、機械的強度、耐熱性はいずれも合格、ダイスカスの発生はなく、コンパウンド価格は安いものであった。 The evaluation results are as shown in the lower column of Table 1. In Examples 1 to 6, the mechanical strength and heat resistance were both acceptable, no die scum was generated, and the compound price was low.
これに対し、比較例１は、充填剤としてシリカを単独で用いており、コンパウンド価格が高いものとなった。なお、比較例１では炭酸カルシウムを添加しておらず、シリコーンゴムを添加しなくてもダイスカスは発生しなかった。比較例２は、充填剤として炭酸カルシウムを単独で用いており、引張強さが不合格であった。 On the other hand, Comparative Example 1 uses silica alone as the filler, resulting in a high compound price. In Comparative Example 1, calcium carbonate was not added, and no die scum was generated even when silicone rubber was not added. In Comparative Example 2, calcium carbonate was used alone as a filler, and the tensile strength was unacceptable.
比較例３は、炭酸カルシウムの添加量が上で述べた範囲よりも少ないものであり、コンパウンド価格が高いものとなった。なお、比較例３では炭酸カルシウムを添加量が少量であるため、シリコーンゴムを添加しなくてもダイスカスは発生しなかった。比較例４は、炭酸カルシウムの添加量が上で述べた範囲よりも多いものであり、耐熱性が不合格であった。 In Comparative Example 3, the amount of calcium carbonate added was less than the range described above, and the compound price was high. In Comparative Example 3, since the amount of calcium carbonate added was small, no die scum was generated even if silicone rubber was not added. In Comparative Example 4, the amount of calcium carbonate added was larger than the range described above, and the heat resistance was unacceptable.
比較例５は、シリカの添加量が上で述べた範囲よりも多いものであり、耐熱性が不合格であった。 In Comparative Example 5, the amount of silica added was larger than the range described above, and the heat resistance was unacceptable.
比較例６は、炭酸カルシウムの平均粒径が上で述べた範囲よりも小さいものであり、耐熱性が不合格であった。比較例７は、炭酸カルシウムの平均粒径が上で述べた範囲よりも大きいものであり、引張強さが不合格であった。 In Comparative Example 6, the average particle diameter of the calcium carbonate was smaller than the range described above, and the heat resistance was unacceptable. In Comparative Example 7, the average particle size of the calcium carbonate was larger than the range described above, and the tensile strength was unacceptable.
比較例８は、シリコーンゴムの添加量が上で述べた範囲よりも少ないものであり、ダイスカスが発生した。比較例９は、シリコーンゴムの添加量が上で述べた範囲よりも多いものであり、引張強さ及び耐熱性が不合格であった。 In Comparative Example 8, the amount of silicone rubber added was less than the range described above, and dice was generated. In Comparative Example 9, the amount of silicone rubber added was larger than the range described above, and the tensile strength and heat resistance were unacceptable.
＜本実施形態の効果＞
以上の結果からわかるように、本実施形態に係る含ふっ素エラストマ組成物は、機械的強度、耐熱性に優れ、ダイスカス発生が抑制されるため、押出成形品の外観は良好であり、さらにコンパウンド価格が安価なものであることがわかる。そのため、この組成物を被覆層に用いた本実施形態の電線は、被覆層が１層であっても、機械的強度、耐熱性を満たしつつ、ダイスカスの発生が抑えられており、製造コストも安価になる。
<Effect of this embodiment>
As can be seen from the above results, the fluorine-containing elastomer composition according to the present embodiment is excellent in mechanical strength and heat resistance, suppresses the occurrence of die scum, and thus the appearance of the extruded product is good, and further, the compound price It can be seen that is cheap. Therefore, the electric wire of the present embodiment using this composition as a coating layer can suppress the occurrence of die scum while satisfying mechanical strength and heat resistance even when the coating layer is one layer, and the production cost is also low. It will be cheaper.
したがって、本実施形態によれば、機械的強度、耐熱性に優れ、押出成形品の外観が良好で、かつ安価な含ふっ素エラストマ組成物及びそれを用いた電線を提供することができる。 Therefore, according to this embodiment, it is possible to provide a fluorine-containing elastomer composition that is excellent in mechanical strength and heat resistance, has a good appearance of an extruded product, and is inexpensive, and an electric wire using the same.
１ 電線
２ 導体
３ 被覆層
1 Electric wire 2 Conductor 3 Coating layer
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| KR101732723B1 (en) * | 2015-09-08 | 2017-05-08 | 주식회사 경신전선 | Fluorosilicone elastomer composition, insulater prepared using the same, and electrical wire and cable thereof |
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