JP2005248068A - Flame-retardant polyethylene resin composition and flame-retardant insulated wire using the same - Google Patents
Flame-retardant polyethylene resin composition and flame-retardant insulated wire using the same Download PDFInfo
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本発明は、難燃性に優れると共に燃焼時にハロゲンのような有害なガスを発生することがなく、特に、家庭用引き込み電線、自動車用絶縁電線等の被覆材料として有用な難燃性ポリエチレン樹脂組成物、およびそれを導体上に被覆してなる難燃性絶縁電線に関する。 The present invention is excellent in flame retardancy and does not generate harmful gas such as halogen during combustion, and is particularly useful as a flame retardant polyethylene resin composition useful as a coating material for domestic lead-in wires, automotive insulated wires, etc. The present invention relates to an object and a flame-retardant insulated electric wire obtained by coating it on a conductor.
近年、環境等の問題から電線・ケーブルの被覆材料も、廃棄処分する際の焼却や埋め立て処理において、大気中や地中へ有害物質を排出しない材料への転換が進められており、難燃性絶縁電線の被覆材料においても従来のＰＶＣやハロゲン系難燃剤に代えて、燃焼時にハロゲンガスの発生しない、いわゆるハロゲンフリーの被覆材料が求められている。このようなハロゲンフリーの被覆材料としては、エチレン系単独重合体、エチレン系共重合体、エチレン・プロピレンゴム等を樹脂成分とし、これに水酸化マグネシウム、水酸化アルミニウム、水和珪酸アルミニウム等の金属水和物系難燃剤を配合したものが知られている。しかし、エチレン系重合体は本質的に難燃性を有していないので、これを高度に難燃化しようとした場合、金属水和物系難燃剤を多量に添加することが必要となり、その結果、被覆材料の硬度が増大し、引張り強度や伸びが低下し、また、柔軟性（可とう性）に乏しい絶縁電線となるなどの問題があった。 In recent years, due to environmental problems, wire and cable coating materials have also been converted to materials that do not emit harmful substances into the atmosphere or the ground in incineration and landfill treatment when disposed of. Also in the covering material of an insulated wire, what is called a halogen-free covering material which does not generate | occur | produce a halogen gas at the time of combustion is calculated | required instead of conventional PVC and a halogen-type flame retardant. As such halogen-free coating materials, ethylene homopolymers, ethylene copolymers, ethylene / propylene rubber, etc. are used as resin components, and metals such as magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, etc. A compound containing a hydrate-based flame retardant is known. However, since the ethylene polymer has essentially no flame retardancy, when trying to make it highly flame retardant, it is necessary to add a large amount of metal hydrate flame retardant. As a result, there was a problem that the hardness of the coating material was increased, the tensile strength and elongation were lowered, and the insulated wire had poor flexibility (flexibility).
上記のような問題を改善するため、樹脂組成としてエチレン系共重合体にスチレン系のエラストマーやアクリルゴムを混合して用いることによって、引張り強度や伸び等の機械的特性を向上させ、金属水和物とメラミンシアヌレート化合物によって難燃性を得ようとする提案が特許文献１に記載されている。これよれば、ＵＬ規格１５８１（電線、ケーブルおよびフレキシブルコードのための関連規格）に規定されている垂直燃焼試験のＶＷ−１規格に適合する難燃性が得られ、また、引張り強度、伸び等の機械特性を満足させることができるとされている。 In order to improve the above-mentioned problems, the mechanical properties such as tensile strength and elongation can be improved by using a mixture of ethylene copolymer and styrene elastomer or acrylic rubber as the resin composition. Patent Document 1 describes a proposal to obtain flame retardancy with a product and a melamine cyanurate compound. According to this, flame retardancy conforming to the VW-1 standard of the vertical combustion test specified in UL standard 1581 (related standard for electric wires, cables and flexible cords) can be obtained, and tensile strength, elongation, etc. It is said that the mechanical properties of can be satisfied.
しかし、ここに記載されている被覆組成物は、樹脂１００重量部に対して金属水和物系難燃剤１５０〜２８０重量部を配合してなるもので、このような金属水和物系難燃剤の多量の配合は、難燃性の向上には有効であるが、可とう性の低下や脆さの増大を招き、本発明が目的とする家庭用引き込み電線、自動車用絶縁電線等の被覆材料に要求されている種々の特性を満たすには不十分である。特に、家庭用引き込み電線や自動車用電線等においては、引張り強度や伸び等の可とう性の他に、電線を折り曲げた際に生じる白化現象や電線を束ねて使用した場合の電線どうしの融着といった問題も考慮する必要があり、これらの特性をすべて満足し得るものではなかった。
よって本発明が解決しようとする課題は、ハロゲンフリーであり、難燃性および可とう性に優れ、また電線を折り曲げた際の白化現象がなく、さらに電線を束ねて使用した場合に電線どうしの融着（ブロッキング）が生じない等の特性を有する難燃性被覆材料を提供すること、より具体的には、ＪＩＳ規格Ｃ３００５に規定されている６０度傾斜燃焼試験に合格する難燃性を有すると共に、引張り強度が１０．３ＭＰａ以上、伸びが３５０％以上で、自己径による曲げに対して白化せず、また９５℃×２時間の温度条件下でブロッキングを生じない難燃性被覆材料を提供すること、およびこの難燃性被覆材料を導体上に被覆した難燃性絶縁電線を提供することにある。 Therefore, the problem to be solved by the present invention is halogen-free, excellent in flame retardancy and flexibility, no whitening phenomenon when the electric wire is bent, and when the electric wires are bundled and used. Providing a flame retardant coating material having characteristics such as no occurrence of fusion (blocking), more specifically, having flame retardance that passes the 60-degree inclined combustion test defined in JIS standard C3005 In addition, it provides a flame-retardant coating material that has a tensile strength of 10.3 MPa or more, an elongation of 350% or more, does not whiten against bending due to its own diameter, and does not cause blocking under a temperature condition of 95 ° C. × 2 hours. It is another object of the present invention to provide a flame retardant insulated electric wire having a conductor coated with the flame retardant coating material.
前記解決しようとする課題は、請求項１に記載されるように、低密度ポリエチレン６０〜７７重量部、α‐オレフィン２０〜３０重量部および酸変性ポリエチレン３〜１０重量部からなるベース樹脂１００重量部に対し、シリコーン処理した水酸化マグネシウム８０〜１２０重量部を配合してなる難燃性ポリエチレン樹脂組成物とすることによって、解決される。 The problem to be solved is, as described in claim 1, 100 weight parts of base resin comprising 60 to 77 parts by weight of low density polyethylene, 20 to 30 parts by weight of α-olefin and 3 to 10 parts by weight of acid-modified polyethylene. This can be solved by preparing a flame retardant polyethylene resin composition comprising 80 to 120 parts by weight of magnesium hydroxide treated with silicone.
また請求項２に記載されるように、請求項１に記載の難燃性ポリエチレン樹脂組成物を、導体上に被覆してなる難燃性絶縁電線とすることによって、解決される。 Further, as described in claim 2, the problem is solved by making the flame-retardant polyethylene resin composition according to claim 1 into a flame-retardant insulated wire formed by coating a conductor.
本発明の難燃性ポリエチレン樹脂組成物を以上のような組成とすることによって、燃焼時にハロゲンガスのような有害物質を排出することがなく、ＪＩＳ規格Ｃ３００５に規定される６０度傾斜燃焼試験に合格する難燃性が得られ、また引張り強度が１０．３ＭＰａ以上、伸びが３５０％以上の機械的特性を有し、さらに自己径による曲げに対して白化せず（耐曲げ白化性）、９５℃×２時間の温度条件下で電線どうしがブロッキングを起こさない（耐ブロッキング性）等の優れた特性を得ることができる。そして、このような難燃性ポリエチレン樹脂組成物を導体上に被覆した難燃性絶縁電線は、特に家庭用引き込み電線や自動車用電線として好適な難燃性絶縁電線とすることができる。 By making the flame-retardant polyethylene resin composition of the present invention as described above, no harmful substances such as halogen gas are emitted during combustion, and the 60-degree inclined combustion test defined in JIS C3005 is used. Passing flame retardancy is obtained, it has mechanical properties such as a tensile strength of 10.3 MPa or more and an elongation of 350% or more, and it does not whiten against bending due to its own diameter (bending whitening resistance), 95 It is possible to obtain excellent characteristics such as that the electric wires do not cause blocking (blocking resistance) under a temperature condition of ° C x 2 hours. And the flame retardant insulated wire which coat | covered such a flame retardant polyethylene resin composition on the conductor can be used as a flame retardant insulated wire especially suitable as a domestic lead-in electric wire or an automobile electric wire.
以下に本発明を詳細に説明する。請求項１に記載の本発明は、低密度ポリエチレン６０〜７７重量部、α−オレフィン２０〜３０重量部、酸変性ポリエチレン３〜１０重量部からなるベース樹脂１００重量部に対し、シリコーン処理した水酸化マグネシウム８０〜１２０重量部を配合してなるものであり、このような組成の難燃性ポリエチレン樹脂組成物とすることによって、特に家庭用引き込み電線や自動車用電線等の被覆材料に要求される難燃性、機械特性、耐曲げ白化性、耐ブロッキング性等の特性を満足させることができる。 The present invention is described in detail below. The present invention according to claim 1 is a water treated with silicone with respect to 100 parts by weight of a base resin comprising 60 to 77 parts by weight of low density polyethylene, 20 to 30 parts by weight of α-olefin, and 3 to 10 parts by weight of acid-modified polyethylene. It is formed by blending 80 to 120 parts by weight of magnesium oxide, and is particularly required for coating materials such as domestic lead-in wires and automobile wires by using a flame-retardant polyethylene resin composition having such a composition. Properties such as flame retardancy, mechanical properties, bending whitening resistance, and blocking resistance can be satisfied.
前記本発明の難燃性ポリエチレン樹脂組成物に用いられるベース樹脂は、低密度ポリエチレンに、α−オレフィンおよび酸変性ポリエチレンを上記組成で配合してなるものである。ベース樹脂におけるα−オレフィンは、最終的に得られる被覆材料に好ましい引張り強度特性、および伸び特性を付与し耐曲げ白化性を向上させる。また酸変性ポリエチレンは、ベース樹脂相互間の相溶性を改善し、またベース樹脂中への水酸化マグネシウムの分散性を改善し、引張り強度、伸び等の特性を向上させることができる。 The base resin used in the flame retardant polyethylene resin composition of the present invention is obtained by blending α-olefin and acid-modified polyethylene with the above composition into low density polyethylene. The α-olefin in the base resin imparts preferable tensile strength characteristics and elongation characteristics to the finally obtained coating material and improves the bending whitening resistance. The acid-modified polyethylene can improve the compatibility between the base resins, improve the dispersibility of the magnesium hydroxide in the base resin, and improve the properties such as tensile strength and elongation.
前記ベース樹脂に用いることのできる低密度ポリエチレンは、その密度が０．９３ｇ／ｃｍ3以下のポリエチレンであるが、より好ましくは密度が０．９０ｇ／ｃｍ3以下の直鎖状低密度ポリエチレン、超低密度ポリエチレン等である。これらの低密度ポリエチレンは、ベース樹脂中に６０〜７７重量部の配合量で用いられる。配合量が６０重量部未満では伸びが低下し、また７７重量部を超えると曲げ白化が生じ易くなるので好ましくない。 The low density polyethylene that can be used for the base resin is a polyethylene having a density of 0.93 g / cm 3 or less, more preferably a linear low density polyethylene having a density of 0.90 g / cm 3 or less, Low density polyethylene. These low density polyethylenes are used in the base resin in an amount of 60 to 77 parts by weight. If the blending amount is less than 60 parts by weight, the elongation decreases, and if it exceeds 77 parts by weight, bending whitening tends to occur, such being undesirable.
また前記ベース樹脂に用いるα−オレフィンは、柔軟で結晶化度の低いオレフィンポリマーが好ましく、例えば、エチレン−ヘキセン共重合体（三井化学社のタフマー等）が使用される。このようなα−オレフィンを前記低密度ポリエチレンと組み合わせることによって、得られる被覆材料に好ましい伸びを与え、また、電線を折り曲げて使用した際に生じる白化現象を防止することができる。α−オレフィンは、ベース樹脂中に２０〜３０重量部の範囲の配合量で用いられ、配合量が２０重量部未満では良好な伸びおよび十分な耐曲げ白化性が得られず、３０重量部を超えると引張り強度が低下するほか、被覆材料に粘着性が生じ、電線を束ねて使用した場合に電線どうしが融着する、いわゆるブロッキングが生じるようになり好ましくない。 The α-olefin used in the base resin is preferably an olefin polymer that is flexible and has a low crystallinity. For example, an ethylene-hexene copolymer (such as Tuffmer from Mitsui Chemicals) is used. By combining such an α-olefin with the low-density polyethylene, it is possible to give a preferable elongation to the obtained coating material and to prevent the whitening phenomenon that occurs when the electric wire is bent and used. The α-olefin is used in the base resin in a blending amount in the range of 20 to 30 parts by weight. If the blending amount is less than 20 parts by weight, good elongation and sufficient bending whitening resistance cannot be obtained. Exceeding this is not preferable because the tensile strength is lowered, the coating material becomes sticky, and when the wires are bundled and used, so-called blocking occurs where the wires are fused.
さらに、前記ベース樹脂に用いることのできる酸変性ポリエチレンは、直鎖状低密度ポリエチレン、超低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体等のエチレン系共重合体を、マレイン酸、イタコン酸、フマル酸等の不飽和カルボン酸、或いはマレイン酸モノエステル、マレイン酸ジエステル、フマル酸ジエステル、無水マレイン酸、無水イタコン酸等の不飽和カルボン酸ジエステルで変性してなるものである。酸変性ポリエチレンは、ベース樹脂中に３〜１０重量部の範囲で配合量され、その配合量が３重量部未満では水酸化マグネシウムの分散性の改善効果が小さく、また１０重量部を超えると伸びの低下を引起して好ましくない。 Furthermore, the acid-modified polyethylene that can be used for the base resin is linear low density polyethylene, ultra-low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. An ethylene copolymer such as a polymer is added to an unsaturated carboxylic acid such as maleic acid, itaconic acid, or fumaric acid, or a maleic acid monoester, maleic acid diester, fumaric acid diester, maleic anhydride, itaconic anhydride, or the like. It is modified with a saturated carboxylic acid diester. The acid-modified polyethylene is blended in the base resin in the range of 3 to 10 parts by weight. If the blending amount is less than 3 parts by weight, the effect of improving the dispersibility of magnesium hydroxide is small. This is not preferable because it causes a decrease in.
前記酸変性ポリエチレンにおいて、不飽和カルボン酸等によるエチレン系共重合体の変性は、一般に良く知られた変性方法例えば、有機過酸化物やジクミル化合物などの触媒を用いる方法、電子線、β線、γ線などの高エネルギーの放射線を照射する方法などで製造することができる。具体的には、エチレン系共重合体に不飽和カルボン酸等および有機過酸化物等触媒の所定量を加え、溶融混練下でグラフト化反応を行なう方法、エチレン系共重合体、不飽和カルボン酸および有機過酸化物触媒等の所定量を適宜な有機溶媒に溶解し、溶液状態としてグラフト化反応を行なう方法、エチレン系共重合体を水中に分散し、これに不飽和カルボン酸等および有機化酸化物等触媒を供給しつつグラフト化反応を行なう方法などである。これらグラフト化反応法の中でも、実用性の点から溶融混練による方法が好ましい。なお、これら不飽和酸による変性において、不飽和酸の変性量は０．５〜７重量％程度である。 In the acid-modified polyethylene, the modification of the ethylene copolymer with an unsaturated carboxylic acid or the like is a generally well-known modification method such as a method using a catalyst such as an organic peroxide or a dicumyl compound, electron beam, β-ray, It can be manufactured by a method of irradiating high energy radiation such as γ rays. Specifically, a method of adding a predetermined amount of an unsaturated carboxylic acid or the like and a catalyst such as an organic peroxide to an ethylene copolymer and performing a grafting reaction under melt-kneading, an ethylene copolymer or an unsaturated carboxylic acid And a method in which a predetermined amount of an organic peroxide catalyst or the like is dissolved in an appropriate organic solvent and a grafting reaction is performed in a solution state, an ethylene copolymer is dispersed in water, and an unsaturated carboxylic acid, etc. For example, a grafting reaction may be performed while supplying a catalyst such as an oxide. Among these grafting reaction methods, a melt kneading method is preferable from the viewpoint of practicality. In addition, in modification | denaturation by these unsaturated acids, the modification | denaturation amount of an unsaturated acid is about 0.5 to 7 weight%.
本発明の難燃性ポリエチレン樹脂組成物においては、前記ベース樹脂と共にシリコーン処理水酸化マグネシが用いられる。水酸化マグネシウムは、高温に曝されると水を放出してその気化熱により自消性を発現する材料であるが、押出し加工性等からも好ましい。そして水酸化マグネシウムは、混練時の樹脂とのなじみ性を良好にするために表面処理が施される。特にシリコーンガムで処理したものが好ましく、このような処理が施された具体的な商品として、信越化学社製のＸ−２２−１８９４などが挙げられる。前記以外にも、ビニルトリメトキシシラン、ビニルトリエメトキシシラン、グリシドキシプロピルトリメトキシシラン、グリシドキシプロピルトリエトキシシラン、メタクリロキプロピルトリメトキシシランなど、一般に金属水和物の表面処理剤として公知の種々のシリコーン化合物が挙げられる。その被覆量としては、０．２〜５重量％程度とされる。また水酸化マグネシウムの粒径は、平均粒径で０．２〜３μｍ程度のものが好ましい。このような平均粒子径とすることによって、分散性がより良好なものとなり前記の効果が得られ易くなる。なお水酸化マグネシウムは、天然水酸化マグネシウム、合成水酸化マグネシウムのいずれも使用できる。 In the flame-retardant polyethylene resin composition of the present invention, silicone-treated magnesium hydroxide is used together with the base resin. Magnesium hydroxide is a material that releases water when exposed to high temperatures and exhibits self-extinguishing properties due to its heat of vaporization, but is also preferable from the viewpoint of extrusion processability. The magnesium hydroxide is subjected to a surface treatment in order to improve the compatibility with the resin during kneading. Particularly, those treated with silicone gum are preferred, and specific products subjected to such treatment include X-22-1894 manufactured by Shin-Etsu Chemical Co., Ltd. Besides the above, vinyl trimethoxysilane, vinyltriemethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, etc. are generally known as surface treatment agents for metal hydrates. And various silicone compounds. The coating amount is about 0.2 to 5% by weight. The average particle diameter of magnesium hydroxide is preferably about 0.2 to 3 μm. By setting it as such an average particle diameter, a dispersibility becomes more favorable and it becomes easy to acquire the said effect. As magnesium hydroxide, either natural magnesium hydroxide or synthetic magnesium hydroxide can be used.
本発明の難燃性ポリエチレン樹脂組成物は、前記ベース樹脂１００重量部に対し、前記シリコーン処理した水酸化マグネシウム８０〜１２０重量部を配合することによって得られる。その組成において、シリコーン処理水酸化マグネシウムの配合量が８０重量部未満では十分な難燃性が得られず、１２０重量部を超えると、難燃性においては満足な結果が得られるが、樹脂組成物自体の固さが増大し、引張り強度および伸び特性等が低下して可とう性に乏しい被覆材料となるなどの問題が生じる。 The flame-retardant polyethylene resin composition of the present invention can be obtained by blending 80 to 120 parts by weight of the magnesium treated magnesium hydroxide with 100 parts by weight of the base resin. In the composition, if the amount of the silicone-treated magnesium hydroxide is less than 80 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 120 parts by weight, satisfactory results can be obtained in flame retardancy. The problem is that the hardness of the object itself is increased, the tensile strength and elongation characteristics are lowered, and the coating material is poor in flexibility.
以上のようにして得られる本発明の難燃性ポリエチレン樹脂組成物は、ハロゲンフリーでかつ優れた難燃性を有し、また前記家庭用引き込み電線、自動車用電線等に要求されている可とう性、耐曲げ白化性、耐ブロッキングに優れるなどの特性を有している。すなわち、ＪＩＳ規格Ｃ３００５に規定される６０度傾斜燃焼試験に合格する難燃性が得られ、また引張り強度が１０．３ＭＰａ以上、伸びが３５０％以上の機械的特性を有し、さらに前記絶縁電線の自己径による曲げに対して白化しない耐曲げ白化性を有する。また９５℃×２時間の温度条件下で、電線どうしがブロッキングを起こさない耐ブロッキング性のものである。なお、本発明の難燃性ポリエチレン樹脂組成物には、必要に応じて各種の添加剤、例えば、紫外線吸収剤、酸化防止剤、老化防止剤、銅害防止剤、顔料、滑剤、相溶化剤等を、本発明の目的を損なわない範囲で適宜配合しても良く、また、場合により他の難燃助剤（赤燐、ポリ燐酸化合物、ヒドロキシ錫酸亜鉛等）などを併用してもよい。 The flame-retardant polyethylene resin composition of the present invention obtained as described above is halogen-free and has excellent flame retardancy, and is also required for the domestic lead-in wires, automobile wires and the like. It has properties such as excellent resistance, bending whitening resistance, and blocking resistance. That is, the flame retardancy that passes the 60-degree inclined combustion test specified in JIS standard C3005 is obtained, the tensile strength is 10.3 MPa or more, and the elongation is 350% or more. It has bending whitening resistance that does not whiten against bending due to its own diameter. Moreover, it is a thing with blocking resistance which does not raise | generate blocking between electric wires on the temperature conditions of 95 degreeC x 2 hours. In addition, the flame retardant polyethylene resin composition of the present invention includes various additives as necessary, for example, an ultraviolet absorber, an antioxidant, an antioxidant, a copper damage inhibitor, a pigment, a lubricant, and a compatibilizer. Etc. may be appropriately blended within the range not impairing the object of the present invention, and in some cases, other flame retardant aids (red phosphorus, polyphosphoric acid compound, hydroxy hydroxy stannate, etc.) may be used in combination. .
次に、前記難燃性ポリエチレン樹脂組成物を、電線の被覆材料として用いた場合の難燃性絶縁電線について述べる。請求項２に記載されるように、前記難燃性ポリエチレン樹脂組成物を導体上に被覆してなるもので、例えば３．１４〜３８ｍｍ２程度の銅導体上に、通常０．８〜１．２ｍｍ程度の厚さに押出し被覆される。このようにして得られた難燃性絶縁電線は、ＪＩＳ規格Ｃ３００５の６０度傾斜燃焼試験に合格する難燃性を有するものである。また、絶縁電線の自己径に対する耐曲げ白化性を有し、さらに９５℃×２時間の温度条件下で電線どうしがブロッキングを起こさない耐ブロッキング性にも合格する優れた特性のもので、特に家庭用引き込み電線、自動車用絶縁電線等として好ましく用いることができる。また前記難燃性絶縁電線は、電子線照射によって架橋してもよい。このような架橋被覆層を有する難燃性絶縁電線は、前述した特性の他に耐熱性や難燃性の向上効果も期待できる。電子線照射は、導体上に前記難燃性樹脂組成物を押出し被覆した後に行なう。このような電子線照射架橋は、通常照射線量１〜３０Ｍｒａｄ程度で行なえばよい。 Next, a flame-retardant insulated wire when the flame-retardant polyethylene resin composition is used as a coating material for the wire will be described. As described in claim 2, the flame-retardant polyethylene resin composition made of coated on a conductor, for example 3.14~38mm on about two copper conductor, typically 0.8 to 1. It is extrusion coated to a thickness of about 2 mm. The flame-retardant insulated wire thus obtained has flame retardancy that passes the JIS standard C3005 60 degree inclined combustion test. In addition, it has bending whitening resistance against the self-diameter of insulated wires, and also has excellent characteristics that pass blocking resistance that does not cause blocking between wires under a temperature condition of 95 ° C. × 2 hours. It can be preferably used as a lead-in electric wire, an insulated electric wire for automobiles and the like. The flame-retardant insulated wire may be cross-linked by electron beam irradiation. The flame-retardant insulated wire having such a crosslinked coating layer can be expected to have an effect of improving heat resistance and flame retardance in addition to the above-described characteristics. The electron beam irradiation is performed after the flame retardant resin composition is extrusion-coated on a conductor. Such electron beam irradiation cross-linking may be performed usually at an irradiation dose of about 1 to 30 Mrad.
以下に実施例並びに比較例を示し、本発明の効果を確認した。表１に記載の組成（数値は重量部で示した）で各成分を配合して各試料を作製した。各組成物を導体径３８ｍｍ２の銅導体上に押出し被覆して、外径２１ｍｍの絶縁電線とした。なお試料作製に用いた各配合成分は、（１）低密度ポリエチレン（宇部興産社のＢ０２８）、（２）α−オレフィン（三井化学社のタフマーＤＦ８０５）、（３）酸変性ポリエチレン（日本ポリオレフィン社のアドテックス６１００Ｍ）、（４）シリコーン処理水酸化マグネシウム（信越化学社のＸ−２２−１８９４）である。 Examples and comparative examples are shown below to confirm the effects of the present invention. Each sample was prepared by blending each component with the composition shown in Table 1 (values are shown in parts by weight). Each composition was extrusion-coated on a copper conductor having a conductor diameter of 38 mm 2 to obtain an insulated wire having an outer diameter of 21 mm. In addition, each compounding component used for sample preparation is (1) low density polyethylene (B028 of Ube Industries), (2) alpha-olefin (Tafmer DF805 of Mitsui Chemicals), (3) acid-modified polyethylene (Nippon Polyolefin Co., Ltd.) Adtex 6100M) and (4) silicone-treated magnesium hydroxide (X-22-1894, Shin-Etsu Chemical Co., Ltd.).
上記で得たそれぞれの試料について、（１）引張り強度および伸びについては、ＪＩＳ規格Ｃ３００５に従って測定、（２）耐曲げ白化性については、電線の自己径巻き付けによる白化の有無を、（３）難燃性についてはＪＩＳ規格Ｃ３００５の６０度傾斜燃焼試験により、評価実施試料数５本に対する合格数（合格数／５として記載）を、（４）耐ブロッキング性については、９５℃×２時間の温度条件下で電線どうしのブロッキングの有無を確認した。結果を表１に示した。 About each sample obtained above, (1) About tensile strength and elongation, it measured according to JIS standard C3005. (2) About bending whitening resistance, the presence or absence of whitening by the self-diameter winding of an electric wire was considered. Regarding the flame resistance, the number of samples to be evaluated (indicated as the number of samples to be evaluated / 5) by the 60-degree inclined combustion test of JIS standard C3005 (described as the number of samples to be evaluated / 5), and (4) the blocking resistance is a temperature of 95 ° C. × 2 hours. The presence or absence of blocking between the electric wires was confirmed under the conditions. The results are shown in Table 1.
表１に示した評価結果から明らかなとおり、実施例１〜４はいずれも本発明の要件を満たした組成の難燃性ポリエチレン樹脂組成物であり、これを用いた絶縁電線は、引張り強度、伸び、耐曲げ白化性、難燃性、耐ブロッキング性のいずれにおいても良好な結果を示した。これに対し、α−オレフィンの配合量が本発明の範囲を外れて少なかった比較例１は、柔軟性付与効果が小さく伸びおよび耐曲げ白化性に劣るものであった。またα−オレフィンの配合量が本発明の範囲を超えた比較例２では、伸びは大きいものの引張り強度が小さく、耐ブロッキング性にも劣るものであった。さらに、低密度ポリエチレンの配合量が本発明の範囲より少なく、かつ酸変性ポリエチレンの配合量が本発明範囲より多い比較例３は、伸びが小さく、反対に酸変性ポリエチレンの配合量が本発明の範囲より少ない比較例４は、分散性改善効果が小さく満足する引張り強度が得られなかった。さらに、シリコーン処理水酸化マグネシウムの配合量が本発明の範囲より少ない比較例５は、ＪＩＳ規格Ｃ３００５の６０度傾斜燃焼試験に５本の試料全てが合格せず、難燃性に問題がある。また比較例６は、シリコーン処理水酸化マグネシウムの配合量が本発明の範囲より多いため、引張り強度並びに伸びが小さく柔軟性に問題があった。 As is clear from the evaluation results shown in Table 1, Examples 1 to 4 are all flame retardant polyethylene resin compositions having a composition satisfying the requirements of the present invention, and the insulated wire using this has tensile strength, Good results were exhibited in all of elongation, bending whitening resistance, flame retardancy, and blocking resistance. On the other hand, Comparative Example 1 in which the blending amount of the α-olefin was less than the range of the present invention had a small flexibility imparting effect and was inferior in elongation and bending whitening resistance. In Comparative Example 2 in which the blending amount of the α-olefin exceeded the range of the present invention, the elongation was large but the tensile strength was small and the blocking resistance was poor. Further, Comparative Example 3 in which the blending amount of the low density polyethylene is less than the range of the present invention and the blending amount of the acid-modified polyethylene is larger than the range of the present invention is small in elongation, and conversely, the blending amount of the acid-modified polyethylene is In Comparative Example 4, which is less than the range, the effect of improving dispersibility is small, and a satisfactory tensile strength cannot be obtained. Furthermore, Comparative Example 5 in which the blending amount of the silicone-treated magnesium hydroxide is less than the range of the present invention has a problem in flame retardancy because all five samples do not pass the JIS standard C3005 60-degree inclined combustion test. In Comparative Example 6, the amount of the silicone-treated magnesium hydroxide was larger than the range of the present invention, so the tensile strength and elongation were small and there was a problem in flexibility.
以上のような本発明の絶縁電線は、前述の特性を有するので家庭用引き込み絶縁電線、自動車用絶縁電線等のみならず、種々の用途の難燃性絶縁電線として有用である。 Since the insulated wire of the present invention as described above has the above-mentioned characteristics, it is useful as a flame-retardant insulated wire for various applications as well as a housed insulated wire for automobiles, an insulated wire for automobiles, and the like.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007040275A1 (en) * | 2005-10-06 | 2007-04-12 | J-Power Systems Corporation | Water-treeing resistant insulating composition and water-treeing resistant electric wire/cable |
| EP2272907A2 (en) | 2009-07-08 | 2011-01-12 | Shin-Etsu Chemical Co., Ltd. | Wire or Cable |
| KR101240496B1 (en) | 2011-03-14 | 2013-03-11 | 신흥에스이씨주식회사 | Insulation films and methods of manufacturing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007040275A1 (en) * | 2005-10-06 | 2007-04-12 | J-Power Systems Corporation | Water-treeing resistant insulating composition and water-treeing resistant electric wire/cable |
| JP2007103247A (en) * | 2005-10-06 | 2007-04-19 | J-Power Systems Corp | Insulation composite and electric wire/cable |
| EP2272907A2 (en) | 2009-07-08 | 2011-01-12 | Shin-Etsu Chemical Co., Ltd. | Wire or Cable |
| US8729391B2 (en) | 2009-07-08 | 2014-05-20 | Shin-Etsu Chemical Co., Ltd. | Wire or cable |
| KR101240496B1 (en) | 2011-03-14 | 2013-03-11 | 신흥에스이씨주식회사 | Insulation films and methods of manufacturing the same |
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