JP6082741B2 - ノンハロゲン難燃性樹脂組成物及び当該樹脂組成物を有する絶縁電線・ケーブル - Google Patents
ノンハロゲン難燃性樹脂組成物及び当該樹脂組成物を有する絶縁電線・ケーブル Download PDFInfo
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- JP6082741B2 JP6082741B2 JP2014524767A JP2014524767A JP6082741B2 JP 6082741 B2 JP6082741 B2 JP 6082741B2 JP 2014524767 A JP2014524767 A JP 2014524767A JP 2014524767 A JP2014524767 A JP 2014524767A JP 6082741 B2 JP6082741 B2 JP 6082741B2
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- 239000001301 oxygen Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- 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
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- 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
- H01B3/448—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 other vinyl compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K3/20—Oxides; Hydroxides
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- Organic Insulating Materials (AREA)
Description
下記(a1)〜(a4)を(A)樹脂成分とし、
(a1)エチレン−酢酸ビニル共重合体:(A)樹脂成分全体に対して20〜80質量%、
(a2)エチレン−αオレフィン共重合体(ただし、エチレン−プロピレン共重合体を 除く。):(A)樹脂成分全体に対して5〜50質量%、
(a3)不飽和カルボン酸変性ポリオレフィン樹脂:(A)樹脂成分全体に対して5〜20質量%、
(a4)プロピレン系樹脂:(A)樹脂成分全体に対して5〜20質量%、
前記(A)樹脂成分の酢酸ビニル含有量を、前記(A)樹脂成分全体に対して10〜30質量%とし、
さらに、前記(A)樹脂成分100質量部に対して、
(b1)水酸化マグネシウム:120〜220質量部、
(b2)水酸化アルミニウム:20〜120質量部、
(b3)1,3,5−トリアジン誘導体化合物:30〜75質量部、
を含有することを特徴とする。
本発明に係るノンハロゲン難燃性樹脂組成物は、前記した本発明において、前記(b1 )水酸化マグネシウムと前記(b2)水酸化アルミニウムの配合比率が、水酸化アルミニ ウム/水酸化マグネシウム=30/170〜60/220であることを特徴とする。
(a1)エチレン−酢酸ビニル共重合体:
本発明の難燃性樹脂組成物に(a1)エチレン−酢酸ビニル共重合体(EVA)を含有させることにより、難燃性を向上することができる。
本発明の難燃性樹脂組成物に(a2)ポリエチレンやエチレン−αオレフィン共重合体を含有させることにより、機械的強度、伸び特性を向上することができる。
本発明の難燃性樹脂組成物に(a3)不飽和カルボン酸変性ポリオレフィン樹脂(不飽和カルボン酸で変性したポリオレフィン樹脂のこと。以下同じ。)を含有させることにより、機械的特性、耐磨耗性等を向上させることができる。不飽和カルボン酸変性ポリオレフィン樹脂における不飽和カルボン酸による変性量は、ポリオレフィン樹脂に対し、0.5〜15質量%のものを好ましく使用することができる。
本発明の難燃性樹脂組成物に(a4)プロピレン系樹脂を含有させることにより、耐熱性を向上させることができ、UL1581で規定されている、121℃で1時間後の加熱変形特性を満足することができることになる。
(b1)水酸化マグネシウム及び(b2)水酸化アルミニウム:
本発明では、使用できる金属水和物を(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムを併用するようにする。水酸化マグネシウムと水酸化アルミニウムを併用することにより、それぞれを単独で使用する場合と比較して難燃性が向上する。
本発明の難燃性樹脂組成物では、難燃剤である(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムに加えて、難燃助剤として、(b3)1,3,5−トリアジン誘導体化合物を併用する。本発明において1,3,5−トリアジン誘導体化合物は難燃助剤として作用し、金属水和物の水酸化マグネシウム及び水酸化アルミニウムと併用することにより、これらとの相乗効果を得られるため、(a1)エチレン−酢酸ビニル共重合体における酢酸ビニル含有量を比較的少なくすることができる。そして、エチレン−酢酸ビニル共重合体における酢酸ビニル含有量を比較的少なくすることにより、機械的特性、耐寒性及び絶縁特性の低下を抑え、優れた機械的特性、耐寒性、絶縁特性を維持することが可能となる。
本発明の難燃性樹脂組成物には、電線、ケーブル、コード、チューブ、電線部品、シート等の被覆材料において、一般的に使用されている各種の添加剤、例えば、酸化防止剤、金属不活性剤、難燃(助)剤((B)で挙げているものを除く。)、充填剤、滑剤等を任意成分として、本発明の目的を損なわない範囲で適宜配合することができる。なお、下記の任意成分は、1種を単独で使用してもよく、2種以上を組み合わせて使用するようにしてもよい。また、ここに挙げた以外の添加物や樹脂等を、本発明の目的を損なわない範囲で、添加するようにしてもよい。
表1及び表2に組成を示す各成分((A)樹脂成分、(B)難燃剤及び難燃助剤、(C)任意成分)を、バンバリーミキサーを用いて混合し、溶融混練した後、ペレット化して難燃性樹脂組成物(コンパウンド)を得た。
(a1)エチレン−酢酸ビニル共重合体:
(1)エチレン−酢酸ビニル共重合体(酢酸ビニル(VA)含有量 33質量%)(商品名:エバフレックスEV180、三井・デュポンポリケミカル(株)製)
(4)エチレン−1へキセン共重合体(商品名:カーネルKS240T、日本ポリエチレン(株)製)(密度 0.880g/cm3)
(5)マレイン酸変性ポリエチレン(商品名:アドテックスL6100M、日本ポリエチレン(株)製)
(6)エチレン−プロピレンブロック共重合体(商品名:ノバテックBC8A、日本ポリプロ(株)製)(エチレン含有量 15質量%)
(b1)水酸化マグネシウム:
(7)シランカップリング剤で表面処理された水酸化マグネシウム(商品名:キスマ5L、協和化学工業(株)製)
(8)無処理水酸化アルミニウム(商品名:ハイジライトH42M、昭和電工(株)製)
(9)メラミンシアヌレート(商品名:MC6000、日産化学工業(株)製)
(10)ヒンダードフェノール系酸化防止剤(商品名:イルガノックス1076、BASF社製)
得られた実施例1〜実施例5、参考例6、実施例7〜実施例17、比較例1〜比較例11の絶縁電線について、下記に示したUL1581に準拠した試験方法を用いて、「(1)引張試験」、「(2)垂直燃焼試験(VW−1)」、「(3)加熱変形試験」、「(4)低温巻き付け試験」、「(5)絶縁抵抗試験」及び「(6)電線融着性」の各試験を実施して、比較・評価した。結果を表1(実施例)及び表2(比較例)に示した。
絶縁電線から導体を抜き取った管状サンプルを準備し、標点距離25mm、引張速度500mm/分で、破断伸び(%)、破断強度(MPa)を測定した。破断強度が10.3MPa以上、破断伸びが150%以上を「○(合格)」とし、10.3MPa未満のものを「×」とした。なお、「○(合格)」のうち、特に、破断強度が12.0MPa以上、破断伸びが180%以上のものを「◎」とした。
絶縁電線サンプルを、たるみのない状態で垂直に張った状態のサンプル上部に指示旗、サンプル下部に綿を設置し、フードを外した状態で15秒の着火と60秒の離火を5回繰り返した。60秒以上のサンプルの燃焼、指示旗の燃焼及び綿の燃焼の全てが観察されなかったサンプルを「○(合格)」とし、それ以外を「×」とした。なお、「○(合格)」のうち、特に、着火1〜5回目のうち、全ての回が30秒以下の燃焼の場合を「◎」とした。
UL1581に基づき、絶縁電線サンプルの絶縁材料の加熱変形特性を測定した。250gfの負荷荷重を、50%以下を「○(合格)」とし、50%を超えるものを「×」とした。なお、「○(合格)」のうち、特に、25%以下のものは「◎」とした。
UL1581に基づき、絶縁電線サンプルを−10℃の環境下で4時間以上放置した後、同様に−10℃の環境下で冷却した、絶縁電線サンプル外径の2倍径を有する金属マンドレルに巻き付けた。巻き付け後に、絶縁材料にクラックが観察されなかったものを「○(合格)」とし、クラックが観察されたものを「×」とした。
50mの絶縁電線サンプルを20℃の水槽に24時間浸漬させ、絶縁抵抗値を測定した。測定電圧、荷電時間、測定時間はそれぞれ500V、10秒、50秒で行った。絶縁抵抗値が10MΩ・km以上であるものを「○(合格)」とし、10MΩ・km未満のものを「×」とした。なお、「○(合格)」のうち、特に、50MΩ・km以上のものを「◎」とした。
絶縁電線サンプルをボビンに巻き付け、60℃の環境下で24時間以上放置した。放置後、絶縁電線サンプル同士が融着せずにスムースに繰り出すことができたものを「○(合格)」とし、繰り出しが困難だったものを「×」とした。
Claims (5)
- 下記(a1)〜(a4)を(A)樹脂成分とし、
(a1)エチレン−酢酸ビニル共重合体:(A)樹脂成分全体に対して20〜80質量%、
(a2)エチレン−αオレフィン共重合体(ただし、エチレン−プロピレン共重合体を 除く。):(A)樹脂成分全体に対して5〜50質量%、
(a3)不飽和カルボン酸変性ポリオレフィン樹脂:(A)樹脂成分全体に対して5〜20質量%、
(a4)プロピレン系樹脂:(A)樹脂成分全体に対して5〜20質量%、
前記(A)樹脂成分の酢酸ビニル含有量を、前記(A)樹脂成分全体に対して10〜30質量%とし、
さらに、前記(A)樹脂成分100質量部に対して、
(b1)水酸化マグネシウム:120〜220質量部、
(b2)水酸化アルミニウム:20〜120質量部、
(b3)1,3,5−トリアジン誘導体化合物:30〜75質量部、
を含有することを特徴とするノンハロゲン難燃性樹脂組成物。 - 前記(b1)水酸化マグネシウムと前記(b2)水酸化アルミニウムの配合比率が、水 酸化アルミニウム/水酸化マグネシウム=30/170〜60/220であることを特徴 とする請求項1に記載のノンハロゲン難燃性樹脂組成物。
- 前記(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムの総和が、(A)樹脂成分100質量部に対して150〜280質量部であることを特徴とする請求項1また は請求項2に記載のノンハロゲン難燃性樹脂組成物。
- 前記(b3)1,3,5−トリアジン誘導体化合物が、メラミンシアヌレートであることを特徴とする請求項1ないし請求項3のいずれかに記載のノンハロゲン難燃性樹脂組成物。
- 前記請求項1ないし請求項4のいずれかに記載のノンハロゲン難燃性樹脂組成物が絶縁被覆材料として被覆されていることを特徴とする絶縁電線・ケーブル。
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