JP5185329B2 - Wire covering material and electric wire using the covering material - Google Patents
Wire covering material and electric wire using the covering material Download PDFInfo
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Description
本発明は、電線におけるシース層、絶縁層等に用いられる電線用被覆材料に関し、詳しくは、外傷白化及び曲げ白化が極めて起こりにくく、しかも、優れた耐寒性、及び耐摩耗性を有する電線被覆材料及び該被覆材料を用いてなる電線に関する。 The present invention relates to a coating material for electric wires used for a sheath layer, an insulating layer, etc. in an electric wire, and more specifically, an electric wire coating material which is extremely unlikely to cause whitening and bending whitening, and has excellent cold resistance and wear resistance. And an electric wire using the coating material.
従来、電線・ケーブルにおけるシース層、絶縁層等に用いられる被覆材料において、難燃性が要求される場合、当該被覆材料析料にはポリ塩化ビニル（以下、ＰＶＣと称す）が使用されてきた。しかし、電線の廃棄焼却時にＰＶＣがダイオキンや塩化水素ガスなどの有毒ガスの発生原因となる疑いから、ＰＶＣの使用を制限し、環境負荷が少ないポリオレフィン系樹脂に金属水酸化物からなる難燃剤をブレンドしてなる難燃性ポリオレフィンが用いられるようになってきている。 Conventionally, polyvinyl chloride (hereinafter referred to as PVC) has been used as a coating material depositing material when flame resistance is required in coating materials used for sheath layers, insulating layers, and the like in electric wires and cables. . However, because PVC is suspected of causing toxic gases such as dioquine and hydrogen chloride gas during waste incineration of electric wires, the use of PVC is restricted, and flame retardants made of metal hydroxides are added to polyolefin resins with low environmental impact. Blended flame retardant polyolefins have been used.
上記金属水酸化物からなる難燃剤としては、水酸化アルミニウム、水酸化マグネシウム等が一般的である。しかし、ポリオレフィン系樹脂に金属水酸化物からなる難燃剤をブレンドしてなる被覆材料は、優れた難燃性を有するものの、特にシース層に用いた場合に、他の物体との擦れや引っ掻き傷、電線同士の擦れ（例えば、複数本の電線が撚り合わさった組物電線での電線間の位置ずれによる電線同士の擦れ）等による白化（以下、外傷白化とも称す）や屈曲した時の屈曲部での白化（以下、曲げ白化とも称す）を生じるという問題点を有している。 As the flame retardant composed of the metal hydroxide, aluminum hydroxide, magnesium hydroxide and the like are common. However, a coating material made by blending a flame retardant made of a metal hydroxide with a polyolefin resin has excellent flame retardancy, but particularly when used for a sheath layer, it is rubbed or scratched with other objects. , Whitening (hereinafter also referred to as trauma whitening) due to friction between wires (for example, friction between wires due to misalignment between wires in a braided wire in which multiple wires are twisted together), or a bent portion when bent Whitening (hereinafter also referred to as bending whitening) occurs.
外傷白化は、電線・ケーブル製造時のガイドロールとの接触や、電線・ケーブルの布設作業時等での他の物体との接触によって起こるが、シース層の表面のみで生じるので、電線の物性に大きく影響はしないが、電線の外観（見栄え）が損なわれるため、商品価値が低下してしまう。一方、曲げ白化は電線・ケーブルの布設作業等において電線を屈曲させた時に起こり、金属酸化物とベースレジンの界面剥離によるミクロクラックが原因と考えられるため、ミクロクラックがシース層の最底部まで侵行することによる、シース層の物性低下が懸念される。 Whitening of the wound occurs due to contact with the guide roll during the manufacture of the electric wire / cable and contact with other objects during the laying operation of the electric wire / cable, but it occurs only on the surface of the sheath layer. Although it does not greatly affect, the appearance (appearance) of the electric wire is impaired, so the commercial value is lowered. On the other hand, bending whitening occurs when an electric wire is bent in an electric wire / cable laying operation or the like, and is considered to be caused by microcracking due to interface peeling between the metal oxide and the base resin. There is a concern that the physical properties of the sheath layer may deteriorate due to the operation.
特許文献１には、上記シース層の白化を、アミノシラン系カップリング剤で表面処理した水酸化マグネシウムを用いることにより防止する提案がなされている。しかしながら、かかるアミノシラン系カップリング剤で表面処理した水酸化マグネシウムを用いても、シース層が強く擦られた場合に白化が起こり、また、シース層のベースレジン（ポリオレフィン樹脂）が比較的柔らかい場合には白化（外傷白化）が起こる。 Patent Document 1 proposes to prevent whitening of the sheath layer by using magnesium hydroxide surface-treated with an aminosilane coupling agent. However, even when magnesium hydroxide surface-treated with such an aminosilane coupling agent is used, whitening occurs when the sheath layer is rubbed strongly, and the sheath layer base resin (polyolefin resin) is relatively soft. Whitening (trauma whitening) occurs.
本発明は、上記事情に鑑み、外傷白化及び曲げ白化が極めて起こりにくい電線用被覆材料を提供することを第１の目的としている。また、外傷白化及び曲げ白化が極めて起こりにくく、しかも、優れた耐寒性及び耐摩耗性を有する電線用被覆材料を提供することを第２の目的としている。また、上記電線被覆材料からなるシース層及び／または絶縁層を有する電線を提供することを第３の目的としている。 In view of the above circumstances, a first object of the present invention is to provide a coating material for electric wires that hardly causes trauma whitening and bending whitening. Another object of the present invention is to provide a coating material for electric wires that is extremely unlikely to cause whitening and bending whitening, and that has excellent cold resistance and wear resistance. It is a third object of the present invention to provide an electric wire having a sheath layer and / or an insulating layer made of the above wire covering material.
本発明者等は、上記目的を達成すべく鋭意研究した結果、ポリオレフィン系樹脂からなるベース樹脂に、表面処理されていない水酸化マグネシウムとともに、酸無水物変性ポリオレフィン系樹脂をブレンドすると、白化が高いレベルで抑制され、しかも、耐寒性及び耐摩耗性等が向上した電線用被覆材料が得られることを知見し、該知見に基づき、本発明を完成させた。 As a result of diligent research to achieve the above object, the inventors of the present invention have high whitening when blended with a base resin composed of a polyolefin resin and an acid anhydride-modified polyolefin resin together with magnesium hydroxide that has not been surface-treated. It was found that a coating material for electric wires that is suppressed at a level and improved in cold resistance, wear resistance and the like can be obtained, and the present invention has been completed based on the knowledge.
すなわち、本発明は以下の特徴を有している。
（１）以下のＡ成分、Ｂ成分およびＣ成分を含み、「Ａ成分+Ｂ成分」が９０重量部あたりＤ成分が１０重量部以下であり、配合重量比が、Ａ成分：Ｂ成分＝９９：１〜６５：３５であり、（Ａ成分+Ｂ成分+Ｄ成分）：Ｃ成分＝１００：（５０〜１５０）である電線用被覆材料。
Ａ成分：ポリオレフィン系樹脂
Ｂ成分：α−オレフィン−酸無水物−二元共重合体、α−オレフィン−酸無水物−アクリル系化合物三元共重合体およびα−オレフィン−酸無水物−ビニルエステル系化合物三元共重合体の群から選ばれる少なくとも一種
Ｃ成分：表面処理がされていない水酸化マグネシウム
Ｄ成分：ポリイソブチレン
（２）Ｂ成分が、α−オレフィン−酸無水物−アクリル系化合物三元共重合体およびα−オレフィン−酸無水物−ビニルエステル系化合物三元共重合体の群から選ばれる少なくとも一種である上記（１）に記載の電線用被覆材料
（３）Ｂ成分おけるアクリル系化合物若しくはビニルエステル系化合物の含有量が０．１〜４０重量％である上記（２）に記載の電線用被覆材料。
（４）配合重量比が（Ａ成分+Ｂ成分）：Ｄ成分＝９９．５：０．５〜９０：１０である上記（１）から（３）のいずれか一項に記載の電線用被覆材料。
（５）上記（１）から（４）のいずれか一項に記載の電線用被覆材料からなるシース層および／または絶縁層を有する電線。
本発明における「電線用被覆材料」とは、シース材料および／または絶縁材料を含めた電線を被覆するための材料を意味する。
That is, the present invention has the following features.
(1) The following A component, B component and C component are included, “A component + B component” is 90 parts by weight, D component is 10 parts by weight or less, and the blending weight ratio is A component: B component = 99. : 1 to 65:35, (A component + B component + D component): C component = 100: (50 to 150).
Component A: Polyolefin resin Component B: α-olefin-acid anhydride-binary copolymer, α-olefin-acid anhydride-acrylic compound terpolymer and α-olefin-acid anhydride-vinyl ester At least one member selected from the group of terpolymers based on olefinic compounds C component: magnesium hydroxide not subjected to surface treatment D component: polyisobutylene (2) B component is an α-olefin-acid anhydride-acrylic compound The coating material for electric wires according to the above (1), which is at least one selected from the group consisting of a terpolymer and an α-olefin-acid anhydride-vinyl ester compound terpolymer, an acrylic resin in the component B The wire covering material according to (2) above, wherein the content of the compound or vinyl ester compound is 0.1 to 40% by weight.
(4) The coating weight for electric wires according to any one of (1) to (3) above, wherein the blending weight ratio is (component A + component B): component D = 99.5: 0.5 to 90:10 material.
(5) An electric wire having a sheath layer and / or an insulating layer made of the electric wire coating material according to any one of (1) to (4).
The “coating material for electric wire” in the present invention means a material for covering an electric wire including a sheath material and / or an insulating material.
本発明では、表面処理されていない水酸化マグネシウムと共に、酸無水物変性ポリオレフィン系樹脂を配合することにより、材料中での水酸化マグネシウムと樹脂間の接着性が向上し、外傷白化や曲げ白化が起こらず、しかも、優れた耐寒性及び耐摩耗性を有する電線・ケーブル用の被覆材料を得ることができる。 In the present invention, by adding an acid anhydride-modified polyolefin resin together with magnesium hydroxide that has not been surface-treated, the adhesion between magnesium hydroxide and the resin in the material is improved, and whitening and bending whitening can be achieved. It is possible to obtain a coating material for electric wires and cables which does not occur and has excellent cold resistance and wear resistance.
本発明の電線用被覆材料は、下記Ａ成分、Ｂ成分およびＣ成分を必須成分としている。
Ａ成分：ポリオレフィン樹脂
Ｂ成分：酸無水物変性ポリオレフィン系樹脂
Ｃ成分：表面処理されていない水酸化マグネシウム
The wire coating material of the present invention has the following components A, B and C as essential components.
Component A: Polyolefin resin Component B: Acid anhydride modified polyolefin resin Component C: Untreated surface magnesium hydroxide
本発明において、Ａ成分のポリオレフィン系樹脂は、主に電線用被覆材料に要求される基本物性（絶縁性、誘電率等の電気的性質、柔軟性、伸長性、引張強度等の機械的性質、耐薬品性等の化学的性質、加工性等）を担うベース成分であり、該ポリオレフィン系樹脂としては、通常、ポリエチレン系樹脂またはポリプロピレン系樹脂が使用される。該ポリエチレン系樹脂としては、エチレンの単独重合体、エチレンと他のビニル化合物との共重合体、またはこれらの混合物などが使用され、エチレンと他のビニル化合物との共重合体としては、エチレンと他のα−オレフインとの共重合体、エチレンと酢酸ビニル若しくはメチルアクリレート、若しくはエチルアクリレートとの共重合体などが好ましく、エチレンと他のα−オレフインとの共重合体におけるα−オレフインとしては、例えば、プロピレン、ブテン−１、ペンテン−１，４−メチル−１−ペンテン、へキセン−１、オクテン−１などが挙げられる。ポリプロピレン系樹脂としては、プロピレンの単独重合体、プロピレンと他のビニル化合物との共重合体、またはこれらの混合物などが使用され、プロピレンと他のビニル化合物との共重合体としては、プロピレンと他のα−オレフインとの共重合体が好ましく、当該α−オレフインとしては、例えば、ブテン−１、ペンテン−１、４−メチル−１−ペンテン、へキセン−１、オクテン−１などが挙げられる。これらのうち、特に好ましいものは、機械的特性と熱的性質の点から、ポリエチレン（ＰＥ）、エチレン−酢酸ビニル共重合体（ＥＶＡ）、エチレン−メチルアクリレート共重合体（ＥＭＡ）、エチレン−エチルアクリレート共重合体（ＥＥＡ）である。また、ポリエチレンは水酸化マグネシウムの受容性の点から、低密度ポリエチレン（ＬＤＰＥ）が好ましく、特に好ましくは、密度が０．８００〜０．９３０ｇ／ｃｍ３の範囲にあるものである。また、エチレン−酢酸ビニル共重合体は、酢酸ビニルの含有量が５〜４５重量％のものが好ましく、エチレン−メチルアクリレート共重合体はメチルアクリレートの含有量が５〜４５重量％のものが好ましく、エチレン−エチルアクリレート共重合体はエチルアクリレートの含有量が５〜４５重量％のものが好ましい。なお、上記密度はＪＩＳ Ｋ６９２２に規定の測定方法による。 In the present invention, the component A polyolefin-based resin mainly has basic physical properties (insulation properties, electrical properties such as dielectric constant, mechanical properties such as flexibility, extensibility, and tensile strength) required for the coating material for electric wires. Chemical properties such as chemical resistance, processability, etc.), and as the polyolefin resin, a polyethylene resin or a polypropylene resin is usually used. As the polyethylene resin, a homopolymer of ethylene, a copolymer of ethylene and another vinyl compound, or a mixture thereof is used. As a copolymer of ethylene and another vinyl compound, ethylene and Copolymers with other α-olefins, copolymers of ethylene and vinyl acetate or methyl acrylate, or ethyl acrylate, etc. are preferred, and α-olefins in copolymers of ethylene and other α-olefins include: Examples include propylene, butene-1, pentene-1,4-methyl-1-pentene, hexene-1, octene-1. As the polypropylene resin, a homopolymer of propylene, a copolymer of propylene and another vinyl compound, or a mixture thereof is used, and as a copolymer of propylene and another vinyl compound, propylene and other vinyl compounds are used. A copolymer with α-olefin is preferable. Examples of the α-olefin include butene-1, pentene-1, 4-methyl-1-pentene, hexene-1, and octene-1. Among these, particularly preferred are polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), and ethylene-ethyl in view of mechanical properties and thermal properties. An acrylate copolymer (EEA). The polyethylene is preferably low density polyethylene (LDPE) from the viewpoint of acceptability of magnesium hydroxide, and particularly preferably has a density in the range of 0.800 to 0.930 g / cm 3 . The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 5 to 45% by weight, and the ethylene-methyl acrylate copolymer preferably has a methyl acrylate content of 5 to 45% by weight. The ethylene-ethyl acrylate copolymer preferably has an ethyl acrylate content of 5 to 45% by weight. In addition, the said density is based on the measuring method prescribed | regulated to JISK6922.
Ｂ成分の酸無水物変性ポリオレフィン系樹脂は、分子内に少なくとも１個のビニル基を有する酸無水物を共重合成分として含有するポリオレフィン系樹脂であり、主として被覆材料の白化の原因となる水酸化マグネシウムと樹脂との界面剥離を防止する作用を有する。該酸無水物変性ポリオレフィン系樹脂としては、例えば、α−オレフイン−酸無水物二元共重合体、α−オレフイン−酸無水物−アクリル系化合物、若しくはビニルエステル系化合物三元共重合体などが挙げれ、これらは何れか一方または両者を併用してもよい。 The component B acid anhydride-modified polyolefin resin is a polyolefin resin containing an acid anhydride having at least one vinyl group in the molecule as a copolymerization component, and is mainly responsible for whitening of the coating material. It has the effect of preventing interface peeling between magnesium and resin. Examples of the acid anhydride-modified polyolefin resin include α-olefin-acid anhydride binary copolymer, α-olefin-acid anhydride-acrylic compound, or vinyl ester compound ternary copolymer. Any of these may be used, or both may be used in combination.
上記酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトランコン酸、無水グルタコン酸などが好ましく、特に好ましくは無水マレイン酸である。当該酸無水物が水酸化マグネシウムとの間に水素結合を形成して、水酸化マグネシウムと樹脂間に強い接着力が得られ、被覆材料中での水酸化マグネシウムと樹脂間の界面剥離が防止される。 As the acid anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaconic anhydride and the like are preferable, and maleic anhydride is particularly preferable. The acid anhydride forms a hydrogen bond between magnesium hydroxide and a strong adhesive force is obtained between the magnesium hydroxide and the resin, preventing interfacial delamination between the magnesium hydroxide and the resin in the coating material. The
上記α−オレフインとしてはエチレン、プロピレン、ブテン−１などが好ましく、特に好ましくはエチレンである。当該α−オレフインは当該Ｂ成分のＡ成分（ポリオレフィン系樹脂）への親和性を担う成分であり、かかる観点から、当該α−オレフインとしては、Ａ成分のポリオレフィン系樹脂の好適例として挙げたポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−メチルアクリレート共重合体、エチレン−エチルアクリレート共重合体に対して良好な親和性が得られるように、エチレンを用いるのが特に好ましい。 As the α-olefin, ethylene, propylene, butene-1, and the like are preferable, and ethylene is particularly preferable. The α-olefin is a component responsible for the affinity of the B component to the A component (polyolefin resin). From this viewpoint, as the α-olefin, polyethylene exemplified as a preferred example of the polyolefin resin of the A component It is particularly preferable to use ethylene so that good affinity can be obtained for the ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, and ethylene-ethyl acrylate copolymer.
上記アクリル系化合物としては、アクリル酸、メタクリル酸、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチルなどが好ましく、特に好ましくはアクリル酸エチルである。また、上記ビニルエステル系化合物としては、酢酸ビニルなどが好ましい。 As the acrylic compound, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and the like are preferable, and ethyl acrylate is particularly preferable. The vinyl ester compound is preferably vinyl acetate.
当該酸無水物変性ポリオレフィン系樹脂中の酸無水物の含有量は、例えば、α−オレフイン−酸無水物二元共重合体の場合、通常、０．０５〜１０重量％、好ましくは、０．１〜５．０重量％であり、α−オレフイン／酸無水物／アクリル系化合物若しくはビニルエステル系化合物三元共重合体の湯合、通常０．０５〜１０重量％、好ましくは、０．１〜５．０重量％である。当該樹脂の被覆材料中の樹脂成分と表面処理されていない水酸化マグネシウムとの配合比率にもよるが、酸無水物の含有量が上記範囲よりも少ない場合は十分な白化防止効果が得られにくく、多い場合は被覆材料の引張強度が低下する傾向を示す。 The content of the acid anhydride in the acid anhydride-modified polyolefin resin is, for example, 0.05 to 10% by weight in the case of an α-olefin-anhydride binary copolymer, preferably 0. 1 to 5.0% by weight, α-olefin / acid anhydride / acrylic compound or vinyl ester compound terpolymer, usually 0.05 to 10% by weight, preferably 0.1% -5.0 wt%. Although it depends on the blending ratio of the resin component in the coating material of the resin and magnesium hydroxide that has not been surface-treated, when the content of the acid anhydride is less than the above range, it is difficult to obtain a sufficient whitening prevention effect. When the amount is large, the tensile strength of the coating material tends to decrease.
本発明ではα−オレフイン−酸無水物−アクリル系化合物若しくはビニルエステル系化合物三元共重合体が白化防止の点で特に良好な結果を得ることができる。この理由としては、アクリル系化合物若しくはビニルエステル系化合物が共重合体の結晶化度を低下させ、かかる共重合体の結晶化度の低下により、成形収縮で発生する残留応力による水酸化マグネシウムと樹脂との界面の接着部の剥離が起こりにくくなり、また、共重合体の粘着力も向上して水酸化マグネシウムと樹脂間の接着力が向上し、白化防止効果が高まるためと考えられる。なお、上記三元共重合体におけるアクリル系化合物若しくはビニルエステル系化合物の含有量は、通常、０．１〜４０重量％、好ましくは、２〜３０重量％である。 In the present invention, an α-olefin-acid anhydride-acrylic compound or vinyl ester compound terpolymer can give particularly good results in terms of preventing whitening. The reason for this is that the acrylic compound or vinyl ester compound reduces the crystallinity of the copolymer, and magnesium hydroxide and resin due to residual stress generated by molding shrinkage due to the decrease in the crystallinity of the copolymer. It is considered that peeling of the adhesive portion at the interface with the resin becomes difficult to occur, and the adhesive strength of the copolymer is improved, the adhesive strength between the magnesium hydroxide and the resin is improved, and the whitening prevention effect is enhanced. In addition, content of the acryl-type compound or vinyl ester-type compound in the said ternary copolymer is 0.1 to 40 weight% normally, Preferably, it is 2 to 30 weight%.
当該酸無水物変性ポリオレフィン系樹脂の配合により、被覆材料の白化防止効果が得られるだけでなく、材料の耐摩耗性、耐寒性が大きく向上する。これは、水酸化マグネシウムと樹脂間に強い接着力が得られることによるものである。通常水酸化マグネシウム にはカップリング剤などの表面処理をして樹脂との相容性を向上させているが、本発明のように、ポリオレフィン系樹脂と酸無水物変性ポリオレフィン系樹脂とからなるベース樹脂、特にさらにポリイソブチレン含有させた場合には意外にも、水酸化マグネシウムに表面処理剤を使用すると耐外傷性、曲げ白化性が低下する傾向にある。 By blending the acid anhydride-modified polyolefin resin, not only the whitening prevention effect of the coating material can be obtained, but also the wear resistance and cold resistance of the material are greatly improved. This is because a strong adhesive force is obtained between the magnesium hydroxide and the resin. Usually, magnesium hydroxide is surface-treated with a coupling agent or the like to improve compatibility with the resin, but as in the present invention, a base comprising a polyolefin resin and an acid anhydride-modified polyolefin resin is used. Surprisingly, when a resin, particularly polyisobutylene is contained, if a surface treatment agent is used for magnesium hydroxide, the trauma resistance and bending whitening tend to be lowered.
Ｃ成分の表面処理されていない水酸化マグネシウムは、通常使用される合成品や天然品のいずれの水酸化マグネシウムでも良いが、被覆材料中での樹脂への接着性を向上させる点で、合成水酸化マグネシウムを用いることが好ましい。 合成品の水酸化マグネシウムとしては、比表面積（ＢＥＴ）で３〜７ｍ２／ｇ程度、結晶粒子径が０．５〜１．０μｍ程度、天然品の水酸化マグネシウムとしては、比表面積（ＢＥＴ）で３〜７ｍ２／ｇ程度、結晶粒子径が５〜１０μｍ程度のものを用いれば良い。 Magnesium hydroxide that is not surface-treated for component C may be any of the commonly used synthetic and natural magnesium hydroxides, but synthetic water is used in order to improve the adhesion to the resin in the coating material. It is preferable to use magnesium oxide. The synthetic magnesium hydroxide has a specific surface area (BET) of about 3 to 7 m 2 / g, the crystal particle diameter is about 0.5 to 1.0 μm, and the natural magnesium hydroxide has a specific surface area (BET). And about 3 to 7 m 2 / g and a crystal particle size of about 5 to 10 μm may be used.
後に詳しく説明するが、本発明では、水酸化マグネシウムと樹脂との接着界面にかかる衝撃力のより一層の緩和を目的に、Ａ成分及びＢ成分とは別に、さらに、Ｄ成分としてポリイソブチレンを配合してもよい。かかるＤ成分を配合しない態様、すなわち、被覆材料中のポリマー成分がＡ成分とＢ成分で構成される場合、これらＡ成分、Ｂ成分の配合重量比（Ａ成分：Ｂ成分）は、通常、９９：１〜５０：５０、好ましくは９７：３〜６５：３５である。かかる範囲を外れてＢ成分の量が多くなると（Ａ成分の量が少なくなると）、被覆材料の引張強度等の機械的強度および耐熱性が低下する傾向を示し、Ｂ成分の量が少なくなると（Ａ成分の量が多くなると）、白化防止効果が低下する傾向を示し、また、被覆材料の耐磨耗性及び耐寒性が低下する傾向を示す。 As will be described in detail later, in the present invention, in addition to the A component and the B component, polyisobutylene is further blended as the D component for the purpose of further reducing the impact force applied to the adhesive interface between the magnesium hydroxide and the resin. May be. In such an embodiment in which the component D is not blended, that is, when the polymer component in the coating material is composed of the component A and the component B, the blending weight ratio of these components A and B (component A: component B) is usually 99. : 1 to 50:50, preferably 97: 3 to 65:35. When the amount of the B component increases outside this range (when the amount of the A component decreases), the mechanical strength such as the tensile strength of the coating material and the heat resistance tend to decrease, and when the amount of the B component decreases ( When the amount of the component A increases, the whitening prevention effect tends to decrease, and the wear resistance and cold resistance of the coating material tend to decrease.
この種の被覆材料において、難燃剤に水酸化マグネシウムを用いる場合、十分な難燃性を得るには、概ね、材料中のポリマー成分１００重量部当たり水酸化マグネシウムを５０〜２００重量部程度配合するのが一般的であるが、本発明の被覆材料においても、Ｃ成分の表面処理されていない水酸化マグネシウムは、被覆材料中のポリマー成分１００重量部（すなわち、ポリイソブチレンを配合しない態様では、Ａ成分とＢ成分の合計配合量１００重量部、ポリイソブチレンを配合する態様では、Ａ成分とＢ成分とポリイソブチレンの合計配合量１００重量部）に対して、通常５０〜１５０重量部、好ましくは７０〜１３０重量部配合する。かかる範囲を外れてＣ成分の量が多くなると、被覆材料の柔軟性、伸長性、耐外傷白化性、耐曲げ白化性等が低下する傾向を示し、少なくなると、被覆材料の難燃性が低下する傾向を示す。 In this type of coating material, when using magnesium hydroxide as a flame retardant, about 50 to 200 parts by weight of magnesium hydroxide is generally blended per 100 parts by weight of the polymer component in the material in order to obtain sufficient flame retardancy. In the coating material of the present invention, the C component magnesium hydroxide that has not been surface-treated is 100 parts by weight of the polymer component in the coating material (that is, in the embodiment in which polyisobutylene is not blended), In the embodiment where the total blending amount of the component and the B component is 100 parts by weight and the polyisobutylene is blended, the total blending amount of the A component, the B component and the polyisobutylene is 100 parts by weight), usually 50 to 150 parts by weight, preferably 70 Add ~ 130 parts by weight. When the amount of the C component is increased outside this range, the flexibility, extensibility, damage whitening resistance, bending whitening resistance, etc. of the coating material tend to decrease, and when the amount decreases, the flame retardancy of the coating material decreases. Show a tendency to
本発明では、水酸化マグネシウムと樹脂との接着界面にかかる衝撃力のより一層の緩和を目的に、Ｄ成分：ポリイソブチレンを適量配合してもよく、当該Ｄ成分の配合により、被覆材料の外傷白化、曲げ白化がより高いレベルで防止される。なお、ここでの引張弾性率はＪＩＳ Ｋ ７１１３の測定方法で測定された値である。 In the present invention, an appropriate amount of D component: polyisobutylene may be blended for the purpose of further reducing the impact force applied to the adhesive interface between magnesium hydroxide and the resin. Whitening and bending whitening are prevented at a higher level. In addition, the tensile elasticity modulus here is the value measured by the measuring method of JISK7113.
当該Ｄ成分を配合する態様においては、被覆材料中におけるＡ成分とＢ成分の合計配合量に対するとＤ成分の配合比（（Ａ成分＋Ｂ成分）：ポリイソブチレン成分）は、通常、９９．５：０．５〜９０：１０（重量比）で、好ましくは９９：１〜９５：５とする。かかる範囲を外れて、ポリイソブチレン成分の配合量が多くなると、被覆材料の引張強さ等の機械的強度および耐熱性が低下する傾向を示し、少なくなるとポリイソブチレンの配合による効果が得られ難くなる。 In the aspect which mix | blends the said D component, the compounding ratio ((A component + B component): polyisobutylene component) of D component with respect to the total compounding quantity of A component and B component in a coating material is 99.5: 0.5 to 90:10 (weight ratio), preferably 99: 1 to 95: 5. If the blending amount of the polyisobutylene component increases outside this range, the mechanical strength such as the tensile strength of the coating material and the heat resistance tend to decrease, and if the blending amount decreases, the effect of blending the polyisobutylene becomes difficult to obtain. .
本発明の被覆材料には、この種の分野で使用されている公知のハロゲンを含まない補助資材を適量配合してもよい。かかる補助資材としては、安定剤、酸化防止剤、充填剤、着色剤、カーボンブラック、架橋剤、滑剤、加工性改良剤、帯電防止剤、難燃助剤等である。 The coating material of the present invention may contain an appropriate amount of a known halogen-free auxiliary material used in this type of field. Such auxiliary materials include stabilizers, antioxidants, fillers, colorants, carbon black, crosslinking agents, lubricants, processability improvers, antistatic agents, flame retardant aids, and the like.
本発明の被覆材料は、上記Ａ成分〜Ｃ成分を所望により上記各種補助配合材を加えて、バンバリーミキサー、加圧ニーダー、二軸押出機等の公知の混練装置で混練し、該混練物を射出成形、押出成形、回転成形、プレス成形等によつて所望の形態に成形することで製造される。 The coating material of the present invention is prepared by adding the above-mentioned various auxiliary compounding materials as desired, and kneading the kneaded product with a known kneading apparatus such as a Banbury mixer, a pressure kneader, or a twin-screw extruder. It is manufactured by molding into a desired form by injection molding, extrusion molding, rotational molding, press molding or the like.
本発明の電線用被覆材料は、外傷白化及び曲げ白化が高いレベルで防止され、しかも、優れた耐寒性及び耐摩耗性を有するもので、電線のシース層及び絶縁層の両方に使用できるが、白化防止の観点からは、シース層に特に好適である。 The coating material for electric wires of the present invention is capable of preventing whitening and bending whitening at a high level, and has excellent cold resistance and wear resistance, and can be used for both a sheath layer and an insulating layer of an electric wire. From the viewpoint of preventing whitening, it is particularly suitable for the sheath layer.
以下、実施例及び比較例により本発明を更に詳しく説明するが、本発明はかるる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by such an Example.
（実施例１〜３、比較例１〜４）表１の上欄に示す各成分をバンバリーミキサー（東洋精機製作所製）に一括投入し、２０分間混練した後、プレス成形により１６０℃で１０分間成形し、各実施例及び各比較例の試験シート及び試験片を作成し、それぞれについて以下の評価試験を行った。なお、各成分の配合量は重量部である。また、ＬＤＰＥ、およびエチレン−無水マレイン酸−アクリル酸エチル三元共重合体のＭＦＲ（メルトフローレート）はＪＩＳ Ｋ ６９９２による測定値である。ＬＤＰＥのＤ硬度はデュロメータ法に基づく値である。ポリイソブチレンの固有粘度は溶媒としてジイソブチレンを用いた測定値である。 (Examples 1 to 3, Comparative Examples 1 to 4) Each component shown in the upper column of Table 1 was put into a Banbury mixer (manufactured by Toyo Seiki Seisakusho), kneaded for 20 minutes, and then press molded at 160 ° C. for 10 minutes. It shape | molded, the test sheet and test piece of each Example and each comparative example were created, and the following evaluation tests were done about each. In addition, the compounding quantity of each component is a weight part. Further, MFR (melt flow rate) of LDPE and ethylene-maleic anhydride-ethyl acrylate terpolymer is a value measured according to JIS K6992. The D hardness of LDPE is a value based on the durometer method. The intrinsic viscosity of polyisobutylene is a measured value using diisobutylene as a solvent.
〔評価試験〕
・引張特性
厚さ１ｍｍの試験シートについて、引張強さ（ＭＰａ）と伸び（％）をＪＩＳＫ７１１３に従って測定。
・耐寒性
厚さ２ｍｍの試験シートについて、ＪＩＳ Ｃ ３００５に従って実施。試験温度は−５０℃で、亀裂無し（○）、亀裂あり（△）、破断（×）の３段階で評価。
・耐摩耗性
厚さ１ｍｍの試験シートについて、ＪＩＳ Ｋ ６９０２に準拠して，摩耗試験１０００回転後の重量減少量を測定。摩耗輪はテーバ社製Ｈ−１８を使用し、荷重は４．９Ｎとした。
・耐曲げ白化性
厚さ１ｍｍ、幅２０ｍｍ、長さ１００ｍｍの試験片を作製し、これを１８０度に２回折り曲げて目視により白化度を観察。白化せず（○）、部分的に白化（△）、全面的に白化（×）の３段階で評価。
・耐外傷白化性
耐磨耗試験実施後の試料の摩耗部の白化の度合いを、白化せず（○）、部分的に白化（△）、全面的に白化（×）の３段階で評価。
これらの試験結果が表１の下欄である。
〔Evaluation test〕
-Tensile property Measure tensile strength (MPa) and elongation (%) according to JISK7113 for a test sheet with a thickness of 1 mm.
・ Tested in accordance with JIS C 3005 for a test sheet having a cold resistance thickness of 2 mm. The test temperature was −50 ° C., and evaluation was made in three stages: no crack (◯), crack (Δ), and fracture (x).
・ Measures the weight loss after 1000 revolutions of the wear test for a 1 mm thick test sheet according to JIS K 6902. The wear wheel used was H-18 manufactured by Taber, and the load was 4.9N.
-Bending whitening resistance A test piece having a thickness of 1 mm, a width of 20 mm, and a length of 100 mm was prepared, bent twice at 180 degrees, and the degree of whitening was visually observed. Evaluation was made in three stages: no whitening (◯), partial whitening (Δ), and full whitening (×).
-Defect whitening resistance The degree of whitening of the worn portion of the sample after the wear resistance test was evaluated in three stages: no whitening (◯), partial whitening (△), and overall whitening (x).
These test results are in the lower column of Table 1.
表１から、実施例１〜３は曲げ白化、外傷白化が全く起こらず、しかも、優れた耐寒性及び耐摩耗性が得られることがわかる。 From Table 1, it can be seen that Examples 1 to 3 do not cause whitening or whitening of the wound at all, and obtain excellent cold resistance and wear resistance.
Claims (3)
「Ａ成分+Ｂ成分」が９０重量部あたり、任意成分としてＤ成分が１０重量部以下であり、
配合重量比が、Ａ成分：Ｂ成分＝９９：１〜６５：３５であり、
（Ａ成分+Ｂ成分+Ｄ成分）：Ｃ成分＝１００：（５０〜１５０）である電線用被覆材料。
Ａ成分：エチレン−酢酸ビニル共重合体
Ｂ成分：α−オレフィン−酸無水物−アクリル系化合物三元共重合体およびα−オレフィン−酸無水物−ビニルエステル系化合物三元共重合体の群から選ばれる少なくとも一種
Ｃ成分：表面処理がされていない水酸化マグネシウム
Ｄ成分：ポリイソブチレン
(Ｂ成分におけるアクリル系化合物若しくはビニルエステル系化合物の含有量は０．１〜４０重量％である) Including the following A component, B component and C component,
"A component + B component" per 90 parts by weight , D component as an optional component is 10 parts by weight or less,
The blending weight ratio is A component: B component = 99: 1 to 65:35,
(A component + B component + D component): C component = 100: The coating material for electric wires which is (50 to 150).
Component A: ethylene-vinyl acetate copolymer Component B: From the group of α -olefin-acid anhydride-acrylic compound ternary copolymer and α-olefin-acid anhydride-vinyl ester compound ternary copolymer At least one selected C component: magnesium hydroxide not subjected to surface treatment D component: polyisobutylene
(Content of acrylic compound or vinyl ester compound in component B is 0.1 to 40% by weight)
The electric wire which has the sheath layer and / or insulating layer which consist of the coating | coated material for electric wires of Claim 1 or 2 .
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| JPH02206632A (en) * | 1988-12-21 | 1990-08-16 | Nippon Petrochem Co Ltd | Flame-retardant polyolefin resin composition having improved surface haze properties |
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