JP3827560B2 - Wire harness protective material and wire harness using the same - Google Patents

Description

【００３０】
二つめは、表１Ｂに示したもので、ＰＶＣ電線であって電線被覆材に老化防止剤が全く含有されていないものである。このＰＶＣ電線としては、表１Ｂに示したように、その電線被覆材がポリ塩化ビニル樹脂（重合度Ｐ＝１３００）１００重量部に対して可塑剤としてＤＩＮＰ（ジイソノニルフタレート）４０重量部、充填剤として炭酸カルシウム２０重量部、安定剤として亜鉛・カルシウム系のものが５重量部配合されたものを用いた。
【００３１】
【表１Ｂ】

【００３２】
三つめは、表１Ｃに示したもので、ＰＶＣ電線であって電線被覆材に老化防止剤が含有されているものである（単に「ＰＶＣ老防電線」ともいう）。このＰＶＣ老防電線としては、表１Ｃに示したように、その電線被覆材がポリ塩化ビニル樹脂（重合度Ｐ＝１３００）１００重量部に対して可塑剤としてＤＩＮＰ（ジイソノニルフタレート）４０重量部、充填剤として炭酸カルシウム２０重量部、安定剤として亜鉛・カルシウム系のものが５重量部のほか、老化防止剤が４．５重量部配合されたものを用いた。老化防止剤の配合量は、全体重量に対して、２．６５ｗｔ％（４．５÷１６９．５×１００＝２．６５ｗｔ％）と、その割合量は、ＰＶＣ老防電線に配合される老化防止剤の有機ポリマー（ＰＶＣとＤＩＮＰ）に対する含有率で表すと３．２１％（４．５÷１４０×１００＝３．２１％）となっている。
【００３３】
【表１Ｃ】

【００３４】
そしてこれら三種類の絶縁電線は、いずれも直径０．３２ｍｍの軟銅線を７本撚り合わせて外径約１．０ｍｍの銅撚線に形成した電気導体の周囲に表１Ａ〜表１Ｃに示したそれぞれの絶縁材料により被覆したものである。例えば、一つめのＨＦ電線は、表１Ａに示した樹脂組成物を２軸混練機で混合温度２５０℃で混合してペレタイザにてペレット状の組成物としたものを押し出し機を用いて０．３ｍｍ厚さに押し出し加工し、これを電線被覆層として７本の撚線からなる電気導体の周囲に形成したものである。その際の押し出し温度は、２５０℃である。また、二つめのＰＶＣ電線及び三つめのＰＶＣ老防電線は、表１Ｂ又は表１Ｃに示した樹脂組成物を２軸混練機で混合温度１８０℃で混合してペレタイザにてペレット状の組成物としたものを押し出し機を用いて０．３ｍｍ厚さに押し出し加工し、これを電線被覆層として７本の撚線からなる電気導体の周囲に形成したものである。その押し出し温度は、１８０℃である。
【００３５】
次に、本実施例に係るワイヤハーネス保護材が適用された各種電線束として以下の五種類のものを用意することとした。一つめは、表１ＡのＨＦ電線３０本からなるＨＦ単独電線束であり、あとの四つは、表１ＡのＨＦ電線と表１ＢのＰＶＣ電線又は表１ＣのＰＶＣ老防電線とからなる混在電線束である。各種電線束は、いずれも電線総数は３０本としているが、混在電線束については、混在比率（「ＰＶＣ電線又はＰＶＣ老防電線の本数：ＨＦ電線の本数」）をそれぞれ、「２５本：５本」、「２０本：１０本」、「１０本：２０本」および「５本：２５本」とした。
【００３６】
次に、各種実施例に供したワイヤハーネス保護材の組成及び試験結果について説明する。まず、表２〜表５は、ワイヤハーネス保護材としてのＰＶＣ粘着剤付きテープ、チューブ及びシートの組成及び試験結果を示したものであり、表２〜表３が銅害防止剤が含有されているものに相当し、表４〜表５が銅害防止剤及び老化防止剤が含有されているものに相当する。
【００３７】
【表２】

【００３８】
【表３】

【００３９】
【表４】

【００４０】
【表５】

【００４１】
各種組成について説明する。表２〜表５に示したＰＶＣ粘着剤付きテープ、チューブ及びシートは、いずれもポリ塩化ビニル（ＰＶＣ）樹脂（重合度Ｐ＝１３００）をベースポリマーとした基材を用いており、その基材としては、ＰＶＣ樹脂１００重量部に対して可塑剤としてＤＯＰ（ジオクチルフタレート）６０重量部、充填剤として炭酸カルシウム２０重量部、安定剤として亜鉛・カルシウム系のもの５重量部を配合したものを用い、表２〜表３に示したものにあっては、この配合物に、銅害防止剤が全く配合されていないもの（各従来品）、銅害防止剤が適当量配合されているもの（本実施例品１−１〜１−５及び２−１〜２−５）及び銅害防止剤が過剰に配合されているもの（比較例品１及び２）を用意し、表４〜表５に示したものにあっては、その配合物に、銅害防止剤及び老化防止剤が全く配合されていないもの（各従来品）、銅害防止剤及び老化防止剤が適当量配合されているもの（本実施例品３−１〜３−５及び４−１〜４−５）及び銅害防止剤が過剰に配合されているもの（比較例品３及び４）を用意した。尚、ＰＶＣチューブ、テープ及びシートの基材の老化防止剤の配合量は、上述したＨＦ電線の老化防止剤の割合量３％とほぼ同等となるように調整されている。ここでは有機ポリマー（ＰＶＣ及びＤＯＰ）に対する含有率を割合量として定義し、その割合量は、３．１２％（５÷１６０×１００＝３．１２％）に調整されている。
【００４２】
そして、表２及び表４に示したＰＶＣ粘着剤付きテープは、いずれも、上記基材の片側表面全体にスチレンブタジエンゴム（ＳＢＲ）やＮＲなどのゴム系材料による粘着剤を付与したものであり、その基材表面に付与される粘着剤としては、ＳＢＲ（スチレンブタジエンゴム）７０重量部に対してＮＲ（天然ゴム）３０重量部、亜鉛華２０重量部、ロジン系樹脂８０重量部を配合したものを用い、表２に示したものにあっては、この配合物に、銅害防止剤が全く配合されていないもの（従来品）、銅害防止剤を適当量配合したもの（本実施例品１−１〜１−５）、銅害防止剤を過剰に配合したもの（比較例品１）を用意し、表４に示したものにあっては、その配合物に、銅害防止剤及び老化防止剤が全く配合されていないもの（従来品）、銅害防止剤及び老化防止剤を適当量配合したもの（本実施例品３−１〜３−５）、銅害防止剤を過剰に配合したもの（比較例品３）を用意した。なお、粘着剤層の厚さは、０．０２ｍｍであり、基材と粘着剤層とのトータルの厚さは、０．１３ｍｍとなっている。尚、ＰＶＣチューブ、テープ及びシートの基材の老化防止剤の量は上述したＨＦ電線の老化防止剤の割合量３％とほぼ同等となるように調整されている。ここでは有機ポリマー（ＳＢＲ、ＮＲ及びロジン系樹脂）に対する含有率を割合量として定義し、その割合量は、３．３％（６÷１８０×１００＝３．３％）に調整されている。
【００４３】
すなわち、表４〜表５に示した銅害防止剤及び老化防止剤を含有させた粘着剤付きＰＶＣテープ、チューブ及びシートは、その基材及び該当する場合にはその粘着剤層に、それぞれ、表２〜表３に示した配合に更に老化防止剤を配合したものに相当している。
【００４４】
次に、上記のようにして作製された表２〜表５に示した従来品、各実施例品及び比較例品について試験及び評価を行った。まず、試験方法について説明する。試料としては、各表に示したＰＶＣ粘着剤付きテープ、チューブ及びシートを、それぞれ、上述した合計五種類のＨＦ単独電線束及び混在電線束の周りに巻き付けたものを用いた。試験は次のようにして行った。すなわち、これらの試料を１５０℃の恒温槽に９６時間放置し、その後、ＨＦ電線を取り出し、１０φマンドレル巻き付けにより、その被覆部分の亀裂の有無を確認した。
【００４５】
次に、試験結果について説明する。表２〜表５の試験結果は、いずれも銅害防止剤の配合量によってのみ区別し電線束の種類には言及していない。電線束の種類や混在比率の違いは試験結果に影響しなかったからである。結局、試験結果は、ＰＶＣ粘着剤付きテープ、チューブ及びシートは、従来品では外観は良好であったがＨＦ電線に亀裂が入り不良（×）と判定され、また、比較例品１〜４では電線には亀裂が生じなかったが、ＰＶＣ粘着剤付きテープ、チューブ及びシートがブルーミングを起こし不良（×）と判定された。そして本実施例品１−１〜１−５、２−１〜２−５、３−１〜３−５、４−１〜４−５はいずれも電線に亀裂が生じることはなく、外観も良好である（○）との判定が得られ、総合評価として良好である（○）との結果が得られた。
【００４６】
以上から、軟銅線を被覆する電線を束ねたＨＦ単独電線束又は混在電線束の周りに、銅害防止剤を適当量配合したＰＶＣ樹脂材料を主成分としたワイヤハーネス保護材（粘着剤付きテープ状物、チューブ状物及びシート状物）を巻き付ける等すれば、ＨＦ電線について良好な熱老化性能が得られることが判明した。これは、ＨＦ電線に含有されている銅害防止剤が消費されてもワイヤハーネス保護材に含有されている銅害防止剤が可塑剤にのってＨＦ電線へ拡散することにより、ＨＦ電線へ銅害防止剤が補給されるためであると考えられる。
【００４７】
また、ＨＦ電線に含有されている老化防止剤とほぼ同等の割合量の老化防止剤がワイヤハーネス保護材に含有されるようにしておけば、ＨＦ電線の老化防止剤が可塑剤の影響で抽出されることはない。これは、ワイヤハーネス保護材の老化防止剤の割合量をＨＦ電線の老化防止剤の割合量とほぼ同等にしたことで、ＨＦ電線に可塑剤が移行してきても（老化防止剤の）濃度勾配の関係でＨＦ電線の老化防止剤が抽出されないためであると考えられる。
【００４８】
表６〜表９は、ワイヤハーネス保護材としてのＨＦ粘着剤付きテープ、チューブ及びシートの組成及び試験結果を示したものであり、表６〜表７が銅害防止剤が含有されているものに相当し、表８〜表９が銅害防止剤及び老化防止剤が含有されているものに相当する。
【００４９】
【表６】

【００５０】
【表７】

【００５１】
【表８】

【００５２】
【表９】

【００５３】
各種組成について説明する。表６〜表９に示したＨＦ粘着剤付きテープ、チューブ及びシートは、いずれもポリオレフィン樹脂をベースポリマーとした基材を用いており、その基材としては、ポリオレフィン系樹脂１００重量部に対して臭素系の難燃剤を３重量部、さらに三酸化アンチモン１．５重量部配合したものを用い、表６〜表７に示したものにあっては、この配合物に、銅害防止剤が全く配合されていないもの（各従来品）、銅害防止剤が適当量配合されているもの（本実施例品５−１〜５−５及び６−１〜６−５）及び銅害防止剤が過剰に配合されているもの（比較品５及び６）を用意し、表８〜表９に示したものにあっては、その配合物に、銅害防止剤及び老化防止剤が全く配合されていないもの（各従来品）、銅害防止剤及び老化防止剤が適当量配合されているもの（本実施例品７−１〜７−５及び８−１〜８−５）及び銅害防止剤が過剰に配合されているもの（比較品７及び８）を用意した。尚、ＨＦチューブ、テープ及びシートの基材の老化防止剤の配合量は、上述したＨＦ電線の老化防止剤の割合量３％とほぼ同等となるように調整されている。ここでは有機ポリマー（ポリオレフィン）に対する含有率を割合量として定義し、その割合量は、３．５％（３．５÷１００×１００＝３．５％）に調整されている。
【００５４】
そして、表６及び表８に示したＨＦ粘着剤付きテープは、いずれも、ＰＶＣ系粘着剤付きテープの場合と同じ、すなわち、上記基材の片側表面全体にスチレンブタジエンゴム（ＳＢＲ）やＮＲなどのゴム系材料による粘着剤を付与したものであり、その基材表面に付与される粘着剤としては、ＳＢＲ（スチレンブタジエンゴム）７０重量部に対してＮＲ（天然ゴム）３０重量部、亜鉛華２０重量部、ロジン系樹脂８０重量部を配合したものを用い、表６に示したものにあっては、この配合物に、銅害防止剤が全く配合されていないもの（従来品）、銅害防止剤を適当量配合したもの（本実施例品５−１〜５−５）、銅害防止剤を過剰に配合したもの（比較例品５）を用意し、表８に示したものにあっては、その配合物に、銅害防止剤及び老化防止剤が全く配合されていないもの（従来品）、銅害防止剤及び老化防止剤を適当量配合したもの（本実施例品７−１〜７−５）、銅害防止剤を過剰に配合したもの（比較例品７）を用意した。なお、粘着剤層の厚さは、０．０２ｍｍであり、基材と粘着剤層とのトータルの厚さは、０．１３ｍｍとなっている。尚、ＨＦチューブ、テープ及びシートの老化防止剤の量は上述したＨＦ電線の老化防止剤の割合量３％とほぼ同等となるように調整されている。ここでは有機ポリマー（ＳＢＲ、ＮＲ及びロジン系樹脂）に対する含有率を割合量として定義し、その割合量は、３．３％（６÷１８０×１００＝３．３％）に調整されている。
【００５５】
すなわち、表８〜表９に示した銅害防止剤及び老化防止剤を含有させた粘着剤付きＨＦテープ、チューブ及びシートは、その基材及び該当する場合にはその粘着剤層に、それぞれ、表６〜表７に示した配合に更に老化防止剤を配合したものに相当している。
【００５６】
次に、上記のようにして作製された表６〜表９に示した従来品、各実施例品及び比較例品について試験及び評価を行った。まず、試験方法について説明する。試料としては、各表に示したＨＦ粘着剤付きテープ、チューブ及びシートを、それぞれ、上述した合計五種類のＨＦ単独電線束及び混在電線束の周りに巻き付けたものを用いた。試験は次のようにして行った。すなわち、これらの試料を１５０℃の恒温槽に９６時間放置し、その後、ＨＦ電線を取り出し、１０φマンドレル巻き付けにより、その被覆部分の亀裂の有無を確認した。
【００５７】
次に試験結果について説明する。表６〜表９の試験結果は、いずれも銅害防止剤の配合量によってのみ区別し電線束の種類には言及していない。電線束の種類や混在比率の違いは試験結果に影響しなかったからである。結局、試験結果は、ＨＦ粘着剤付きテープ、チューブ及びシートは、従来品では外観は良好であったがＨＦ電線に亀裂が入り不良（×）と判定され、また、比較例品５〜８では電線には亀裂が生じなかったが、ＨＦ粘着剤付きテープ、チューブ及びシートがブルーミングを起こし不良（×）と判定された。そして本実施例品５−１〜５−５、６−１〜６−５、７−１〜７−５、８−１〜８−５はいずれも電線に亀裂が生じることはなく、外観も良好である（○）との判定が得られ、総合評価として良好である（○）との結果が得られた。
【００５８】
以上から、軟銅線を被覆する電線を束ねたＨＦ単独電線束又は混在電線束の周りに、銅害防止剤を適当量配合した臭素系ポリオレフィン樹脂材料を主成分としたワイヤハーネス保護材（粘着剤付きテープ状物、チューブ状物及びシート状物）を巻き付ける等すれば、ＨＦ電線について良好な熱老化性能が得られることが判明した。空気中の水分や粘着剤等の影響による銅害をワイヤハーネス保護材によっても抑制できるためと考えられる。
【００５９】
また、ＨＦ電線に含有されている老化防止剤とほぼ同等の割合量の老化防止剤がワイヤハーネス保護材に含有されるようにしておけば、ＨＦ電線の老化防止剤がワイヤハーネス保護材へ移行することはない。老化防止剤の割合量をＨＦ電線の老化防止剤の割合量とほぼ同等にしたことで、濃度勾配が同等になると考えられるからである。
【００６０】
本発明は上記した実施の形態に何ら限定されるものではなく、本発明の趣旨を逸脱しない範囲で種々の改変が可能である。例えば、上記各種の実施例では、ワイヤーハーネス保護材としてＰＶＣ樹脂系のもの及びポリオレフィン系のものを示したが、その組成は各実施例のものに限定されるものではない。また、ポリオレフィン系のワイヤハーネス保護材については臭素系の難燃剤を少量配合したもの（低ハロゲン系のもの）を示したが、全くハロゲン元素が含まれないワイヤハーネス保護材であってもよい。
【００６１】
要するに本発明の趣旨は、ワイヤハーネス保護材としてのこれらの粘着剤付きテープ状物、チューブ状物又はシート状物について銅害防止剤を配合することによりＨＦ電線被覆材へ銅害防止剤を補給する又は補給しうる状態にしておくことにより、ＨＦ単独電線で使用される状態においても、ＰＶＣ電線と混在させて使用される状態においても、ＨＦ電線とワイヤハーネス保護材又はＰＶＣ電線との間の悪影響を回避し、ワイヤハーネスとしての電線品質の安定及び電線寿命の延長による恒久的使用を達成することにある。
【００６２】
【発明の効果】
本発明に係る請求項１に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物に銅害防止剤が含有されているものであるから、銅を含む電気導体を被覆する電線を束ねた電線束であって、ハロゲンフリー絶縁電線からなる電線束の銅害を抑制できるという効果がある。
【００６３】
請求項２に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物の基材が塩化ビニル樹脂材料からなるものであるから、ハロゲンフリー絶縁電線で銅害防止剤が消費されても、当該基材から当該ハロゲンフリー絶縁電線へ銅害防止剤を補給することができるという効果がある。
【００６４】
請求項３に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物の基材がハロゲンフリー樹脂材料からなるものであるから、空気中の水分や粘着剤等の影響による銅害を抑制することができるという効果がある。
【００６５】
請求項４に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物に含有される銅害防止剤の含有量を前記基材のベースポリマー１００重量部に対して０．００１重量部〜５重量部の範囲としたものであるから、熱老化性能の低下を阻止することができるという効果がある。
【００６６】
請求項５に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物に老化防止剤が含有されているものであるから、電線の劣化を防止することができるという効果がある。
【００６７】
請求項６に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物、チューブ状物又はシート状物に含有される老化防止剤の含有量を当該基材の老化防止剤の割合量が電線の老化防止剤の割合量とほぼ等しくなるようにしたものであるから、ハロゲンフリー絶縁電線から当該ワイヤハーネス保護材への老化防止剤の拡散が阻止されるという効果がある。
【００６８】
請求項７に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物の基材及び／又は粘着材に銅害防止剤が含有されているものであるから、銅を含む電気導体を被覆する電線を束ねた電線束であって、ハロゲンフリー樹脂材料により当該電気導体が被覆されたハロゲンフリー絶縁電線からなる電線束の銅害を抑制することができ、更に、当該基材及び／又は粘着材に含有される銅害防止剤の含有量をそれぞれ当該基材のベースポリマー１００重量部に対して０．００１重量部〜５重量部の範囲としたものであるから、熱老化性能の低下を阻止することができるという効果がある。
【００６９】
請求項８に記載のワイヤハーネス保護材は、その粘着剤付きテープ状物の基材及び／又は粘着材に老化防止剤が含有されているものであるから、電線の劣化を防止することができ、更に、当該基材及び／又は粘着材に含有される老化防止剤の含有量を当該基材の老化防止剤の割合量が電線の老化防止剤の割合量とほぼ等しくなるようにしたものであるから、ハロゲンフリー絶縁電線から当該ワイヤハーネス保護材への老化防止剤の拡散が阻止されるという効果がある。
【００７０】
請求項９に記載のワイヤハーネスは、銅を含む電気導体を被覆する電線を束ねた電線束であって、ハロゲンフリー樹脂材料により当該電気導体が被覆されたハロゲンフリー絶縁電線からなる電線束又はその一部を塩化ビニル樹脂材料により当該電気導体が被覆されたＰＶＣ絶縁電線に代えてなる電線束の周囲を請求項１から８に記載のワイヤハーネス保護材により被覆したものであるから、熱老化性能の低下を阻止することができ耐用年数が長くなるという効果がある。
【００７１】
請求項１０に記載のワイヤハーネスは、ハロゲンフリー樹脂材料からなる絶縁電線を束ねた電線束又はその一部を前記塩化ビニル樹脂材料からなる絶縁電線に代えて束ねた電線束の各電線の電線被覆材に銅害防止剤及び／又は老化防止剤を含有させたものであるから、ＰＶＣ老防電線からＨＦ電線へ銅害防止剤を補給することができるとともに、ＨＦ電線からＰＶＣ老防電線への老化防止剤の拡散が抑制されるという効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a wire harness protective material and a wire harness using the same, and more particularly, an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled and does not contain any halogen element or contain a halogen element. A wire bundle (also simply referred to as “HF single wire bundle”) consisting of a halogen-free insulated wire (simply referred to as “HF wire”) whose electrical conductor is coated with a polyolefin-based insulating resin material whose amount is at least lower than that of vinyl chloride resin, or Part of the wire is covered around a wire bundle (also simply called “mixed wire bundle”) instead of PVC insulated wire (also simply called “PVC wire”) covered with polyvinyl chloride (PVC) resin. Tape-like, tube-like or sheet-like wire harness protective material used as a HF and an HF single electric wire bundle or a mixed electric wire bundle About wire harness by covering the.
[0002]
[Prior art]
Wire harnesses used for wiring for automobiles and other vehicles are also referred to as assembled wires. Wires of appropriate specifications and thickness are selected, cut and bundled into a bundle of wires and wrapped in a tube or sheet. It is made by rolling and taping together, and various parts are attached to form a batch. In general, PVC wires are bundled with several copper wires and covered with a polyvinyl chloride (PVC) resin coating. As copper wires, annealed annealed copper and tin-plated annealed copper are used. A line is used. Moreover, as a tape, the PVC tape which provided the layer (adhesion layer) of the adhesive to the base material which consists of PVC resin, and a PVC tube and a PVC sheet are used widely as another exterior protection material. That is, PVC resin is generally used not only for electric wire insulation coating materials, but also for tape, tube, sheet and other electric wire protection materials and wire harness protection materials.
[0003]
However, for PVC wires that have been widely used as insulated wires, recently, alternatives have been studied as part of measures against environmental problems. For example, a large amount of inorganic filler as a flame retardant added to non-halogen polyolefins. Halogen-free electric wires have been proposed.
[0004]
Therefore, the inventors attach a PVC tube and a sheet to an HF single electric wire bundle, and attach a PVC tube and a sheet to a wire harness that binds both ends of the PVC tube and the sheet with an adhesive-attached PVC tape, or a mixed electric wire bundle. A wire harness in which both ends of a PVC tube and a sheet (also simply referred to as “PVC protective material”) were bound with a PVC tape with an adhesive was prepared, and the heat aging performance of each wire harness was examined. As a result, it was found that the heat aging performance of the wire harness of the mixed electric wire bundle is significantly inferior to the heat aging performance of the wire harness of the HF single electric wire bundle. The inventors have investigated the cause of the difference in the heat aging performance, and have come to think that it may be caused by the ionization of copper, the migration of plasticizer, and the like.
[0005]
First, copper ionization occurs when moisture in the air passes through the PVC protective material and enters the HF electric wire to ionize copper in the copper wire. This copper ion has a high oxidation potential and acts as a catalyst to break the chemical bond of the wire coating polymer, thereby causing the wire coating polymer to deteriorate. Copper ionization also occurs when the plasticizer blended in the PVC protective material diffuses into the HF electric wire and reacts with copper in the copper wire to promote copper ionization. This copper ion is also considered to be a catalyst that breaks the chemical bond of the wire coating polymer and degrades the wire coating polymer.
[0006]
Incidentally, the HF electric wire usually contains a predetermined amount of copper damage preventing agent in order to complex and stabilize copper ions generated by the influence of moisture in the air. Therefore, if copper ions are generated by reacting with the plasticizer as described above, a predetermined amount of copper damage inhibitor is insufficient.
[0007]
Furthermore, the copper damage prevention agent contained in the HF electric wire dissolves in the plasticizer transferred from the PVC protective material, and returns from the HF electric wire to the PVC protective material having a low concentration gradient (of the copper damage prevention agent). To go. Then, the copper damage preventing agent is consumed not only for stabilization of copper ions generated by the influence of air but also for stabilization of copper ions generated by the plasticizer, and from the HF electric wire on the plasticizer. Since it shifts to a protective material, it will decrease synergistically. For this reason, aging of the HF electric wire is promoted. In addition, the PVC protective material promotes aging because the plasticizer flows out.
[0008]
Furthermore, the HF electric wire contains a predetermined amount of an anti-aging agent. This anti-aging agent also dissolves when the plasticizer is transferred from the PVC protective material, and the PVC has a low concentration gradient from the HF electric wire. Reduced to return to protective material. For this reason, aging of the HF electric wire is promoted. In addition, the PVC protective material promotes aging because the plasticizer flows out.
[0009]
Furthermore, the inventors attach a tube and sheet (also referred to simply as “HF protective material”) using non-halogen polyethylene or polypropylene to the wire bundle, and use the non-halogen adhesive tape (HF protective material) to attach the tube. A heat aging test was also conducted for the wire harness in which sheets were bound. Also in this case, it was found that the heat aging performance of the wire harness composed of the mixed electric wire bundle is significantly inferior to the heat aging performance of the wire harness composed of the HF single electric wire bundle. The reason is considered that in the case of the mixed electric wire bundle, the same copper ionization and plasticizer migration as described above occur between the PVC electric wire and the HF electric wire.
[0010]
Therefore, the inventors repeated trial and error to utilize the migration of the plasticizer. If the copper protective agent is added to the PVC protective material at a higher concentration than the HF electric wire, the copper protective agent is plasticized. Since it dissolves in the agent, when the plasticizer migrates, the copper damage inhibitor can be spread on the plasticizer and diffused into the HF electric wire, leading to the idea that the consumption of copper damage inhibitor can be replenished. .
[0011]
In addition, the inventors of the anti-aging agent blended with the PVC protective material in the same proportion as the HF electric wire (ratio to the organic polymer), the anti-aging agent between adjacent protective materials and electric wires. Since the concentration gradients are equal, the inventors have come to the idea that even if the plasticizer is transferred, the anti-aging agent is not transferred and the decrease in the anti-aging agent of the HF electric wire can be suppressed.
[0012]
The problem to be solved by the present invention is that a wire harness in which a HF single electric wire bundle or a mixed electric wire bundle in which a part thereof is replaced with a PVC electric wire is used, is a tape with adhesive, a tube or a sheet as a protective material. Thermal aging performance by suppressing copper damage of HF electric wire and suppressing diffusion of anti-aging agent between HF electric wire and wire harness protective material or PVC electric wire when wire harness protective material is used An object of the present invention is to provide a wire harness protective material excellent in the above and a wire harness using the same. Thereby, it is going to achieve stabilization and permanent use of the electric wire quality of a wire harness.
[0013]
[Means for Solving the Problems]
In order to solve this problem, a wire harness protective material according to a first aspect of the present invention is an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled as described in claim 1, A wire bundle made of a halogen-free insulated wire in which the electric conductor is coated with a halogen-free resin material containing no element or having a halogen element content at least lower than that of the vinyl chloride resin, or a part of the wire bundle is made of the vinyl chloride resin material. Adhesive tape-like, tube-like, or sheet-like wire harness protective material used around a wire bundle in place of a PVC insulated wire coated with an electrical conductor, the adhesive-like tape-like material The gist is that the tube-shaped material and the sheet-shaped material contain a copper damage inhibitor.
[0014]
In the present invention, as the above-mentioned “copper wire”, tin-plated annealed copper wire is used in addition to annealed annealed copper. That is, any wire that covers an electrical conductor containing copper can be applied to the present invention. Moreover, as a base polymer used for the wire coating material of “halogen-free insulated wire”, olefin-based propylene polymer (homopolymer and propylene random or block copolymer), polyethylene (high density polyethylene, linear low density polyethylene, Low-density polyethylene, ultra-low-density polyethylene, etc.), polybutene polymer, ethylene copolymer (ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc.), olefin elastomer (polypropylene-ethylene / propylene copolymer) Etc.) or copolymers in which unsaturated double bonds in these copolymers are saturated by hydrogenation, and the like. These polymers can be used alone or as a mixture of two or more. A flame retardant containing no halogen such as metal hydrates such as magnesium hydroxide and aluminum hydroxide is added as a flame retardant. And copper damage prevention agent, anti-aging agent, a processing aid etc. may be added as needed, and also crosslinking may be given and heat resistance may be improved. In the present invention, it is desirable that a copper damage inhibitor and an antiaging agent are added. Low halogen compounds also conceptually include bromide-based flame retardants or those that impart flame retardancy using halogen-containing resins having a halogenation rate lower than that of PVC resins. In addition, in the case of “PVC insulated wires”, in order to give flexibility to PVC resin and improve the workability of the material, or to lower the material cost, the resin can be mixed well with water resistance and electrical insulation. An excellent plasticizer is also blended. An anti-aging agent may be further added thereto.
[0015]
According to the invention according to claim 1 having the above-described configuration, the adhesive tape-like material, tube-like material and sheet-like material contain a copper damage prevention agent. Even if the agent is consumed, the halogen-free insulated electric wire is supplemented with the copper damage preventing agent from the tape-like product with adhesive, tube-like product and sheet-like product. Thereby, copper damage is prevented beforehand.
[0016]
In this case, as described in claim 2, the base material of the tape-like product with pressure-sensitive adhesive, the tube-like material, and the sheet-like material can be made of a vinyl chloride resin material. As a “vinyl chloride resin material”, in order to give flexibility to PVC resin and improve the workability of the material, or to lower the material cost, it has good mixing with the resin, water resistance, electrical insulation, etc. It is also desirable to use an excellent plasticizer. This is because when the plasticizer is transferred from the tape-like product with pressure-sensitive adhesive, the tube-like material, and the sheet-like material, the copper damage preventing agent is replenished to the HF electric wire.
[0017]
Alternatively, as described in claim 3, the base material of the tape-like article with pressure-sensitive adhesive, the tube-like article and the sheet-like article contains no halogen element or the halogen element content is at least from vinyl chloride resin. Alternatively, those made of a low halogen-free resin material may be used. As the base polymer of the “halogen-free resin material”, the same polymer as the base polymer of the wire covering material of the halogen-free insulated wire can be used. A low halogen bromide-based flame retardant is added as a flame retardant. You may add the flame retardant which does not contain halogens, such as metal hydrates, such as magnesium hydroxide and aluminum hydroxide.
[0018]
And when described in claim 2 or 3, as described in claim 4, inclusion of the copper damage inhibitor contained in the tape-like product with adhesive, tube-like product or sheet-like product The amount may be in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the substrate. This is because there is no effect when the content of the copper damage inhibitor is less than 0.001 part by weight with respect to 100 parts by weight of the base polymer of the base material, and blooms when the content exceeds 5 parts by weight. The content of the copper damage inhibitor is more preferably in the range of 0.001 to 3 parts by weight. This is because when the amount exceeds 3 parts by weight, the workability to the product tends to be slightly deteriorated.
[0019]
In this case, as described in claim 5, it is desirable that an anti-aging agent is contained in the adhesive tape-like product, tube-like product, or sheet-like product. This is because the anti-aging agent in the wire covering material of the halogen-free insulated wire is prevented from diffusing into the wire harness protective material, and the deterioration of the heat aging performance of the halogen-free insulated wire is prevented.
[0020]
In this case, as described in claim 6, the content of the anti-aging agent contained in the adhesive tape-like product, tube-like product or sheet-like product is the proportion of the anti-aging agent in the base material. Is preferably substantially equal to the proportion of the anti-aging agent of the electric wire. Here, “amount of proportion of anti-aging agent for base material” means a proportion (%) of the anti-aging agent in the base material relative to the organic polymer, and “a proportion amount of anti-aging agent for electric wire” Refers to the ratio (%) of the antioxidant to the organic polymer. Thereby, the concentration gradient of the anti-aging agent disappears between the halogen-free insulated wire and the wire harness protective material, and the diffusion of the anti-aging agent is prevented.
[0021]
The wire harness protective material according to the second aspect of the present invention is an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled as described in claim 7 and does not contain any halogen element or halogen element. PVC insulation in which the electric conductor is covered with a vinyl chloride resin material or a part of a bundle of halogen-free insulated wires in which the electric conductor is covered with a halogen-free resin material whose content is at least lower than that of vinyl chloride resin It is a wire harness protective material used by coating around the wire bundle in place of the electric wire, and the adhesive tape-like material contains a copper damage inhibitor in the base material and / or the adhesive, The content of is set to a range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material.
[0022]
According to the wire harness protective material according to claim 7 having the above-mentioned configuration, since the copper damage prevention agent is contained in the adhesive tape and / or the adhesive, the halogen-free insulated wire prevents copper damage. Even if the agent is consumed, the halogen-free insulated electric wire is supplemented with the copper damage preventing agent from the adhesive tape. Thereby, copper damage is prevented beforehand. Moreover, the content of the copper damage inhibitor is in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material. This is because if the amount is less than 0.001 part by weight with respect to 100 parts by weight of the polymer, the effect is not obtained, and if it exceeds 5 parts by weight, the bloom occurs. The content of the copper damage inhibitor is more preferably in the range of 0.001 to 3 parts by weight. This is because when the amount exceeds 3 parts by weight, the workability to the product tends to be slightly deteriorated.
[0023]
In this case, as described in claim 8, the tape-like product with the pressure-sensitive adhesive contains an anti-aging agent in the base material and / or the pressure-sensitive adhesive, and each content is prevented from being anti-aging. It is preferable that the proportion amount of the agent is substantially equal to the proportion amount of the anti-aging agent of the electric wire. This is because the anti-aging agent in the wire covering material of the halogen-free insulated wire is prevented from diffusing into the wire harness protective material, and the deterioration of the heat aging performance of the halogen-free insulated wire is prevented.
[0024]
A wire harness according to a third aspect of the present invention is an electric wire bundle obtained by bundling electric wires covering an electric conductor containing copper, as described in claim 9, and contains no halogen element or contains a halogen element. A wire bundle made of a halogen-free insulated wire in which the electric conductor is coated with a halogen-free resin material whose amount is at least lower than that of vinyl chloride resin or a part thereof is replaced with a PVC insulated wire coated with the electric conductor with vinyl chloride resin. The gist of the present invention is that the wire bundle is covered with the wire harness protective material according to claim 1.
[0025]
According to the wire harness described in claim 9 having the above-described configuration, the wire harness protective material according to claim 1, that is, the pressure-sensitive adhesive, even if the copper damage preventing agent is consumed in the halogen-free insulated wire. A copper damage inhibitor is supplied to the halogen-free insulated wire from the attached tape-like material, tube-like material or sheet-like material. Thereby, copper damage is prevented beforehand. Furthermore, since the anti-aging agent is contained in the wire harness protective material, the anti-aging agent in the wire covering material of the halogen-free insulated wire is prevented from diffusing into the wire harness protective material, and the heat of the halogen-free insulated wire is prevented. A decline in aging performance is prevented. Due to these synergistic effects, the wire harness has stable electric wire quality and exhibits good durability over a long period of time.
[0026]
In this case, as described in claim 10, an electric wire bundle in which the insulated electric wires made of the halogen-free resin material are bundled or a part of the bundle is bundled instead of the insulated electric wire made of the vinyl chloride resin material. It is desirable that the wire covering material for each wire contains a copper damage inhibitor and / or an anti-aging agent. This is to prevent a decrease in the heat aging performance of the electric wire.
[0027]
In addition, it is desirable that the copper damage inhibitor and the anti-aging agent contained in each wire and wire harness protective material are the same. There are various types of copper damage prevention agents and anti-aging agents, but mutual replenishment of copper damage prevention agents between halogen-free insulated wires, PVC insulated wires and wire harness protectors by using the same type of each other. This is because the elution movement of the anti-aging agent and the anti-aging agent can be more effectively prevented.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
【Example】
Hereinafter, preferred embodiments of the present invention will be described in detail.
First, the following three types of insulating material-coated wires used for various wire bundles to which the wire harness protective material according to this example was applied were prepared. The first is shown in Table 1A, which is an HF electric wire that does not contain any halogen element in the electric wire covering material. As shown in Table 1A, the HF electric wire has a polyolefin-based polypropylene resin as a main component, and 80 parts by weight of magnesium hydroxide as a flame retardant with respect to 100 parts by weight of the polypropylene resin. A compound containing 3 parts by weight of an inhibitor (phenolic) and 1 part by weight of a copper damage inhibitor was used. The blending amount of the anti-aging agent is 1.63 wt% (3 ÷ 184 × 100 = 1.63 wt%) with respect to the total weight, and the proportion is the organic polymer of the anti-aging agent blended in the HF electric wire ( When expressed in terms of content relative to (polypropylene), it is 3% (3 ÷ 100 × 100 = 3%).
[0029]
[Table 1A]

[0030]
The second is shown in Table 1B, which is a PVC electric wire that does not contain any anti-aging agent in the wire covering material. As shown in Table 1B, this PVC electric wire is composed of 40 parts by weight of DINP (diisononyl phthalate) as a plasticizer with respect to 100 parts by weight of a polyvinyl chloride resin (polymerization degree P = 1300). As a stabilizer, 20 parts by weight of calcium carbonate and 5 parts by weight of a zinc / calcium stabilizer as a stabilizer were used.
[0031]
[Table 1B]

[0032]
The third one is shown in Table 1C, and is a PVC electric wire in which an anti-aging agent is contained in the wire covering material (also simply referred to as “PVC anti-aging wire”). As this PVC old electric wire, as shown in Table 1C, 40 parts by weight of DINP (diisononyl phthalate) as a plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin (polymerization degree P = 1300) As the filler, 20 parts by weight of calcium carbonate and 5 parts by weight of zinc / calcium stabilizer as a stabilizer and 4.5 parts by weight of an anti-aging agent were used. The blending amount of the anti-aging agent is 2.65 wt% (4.5 ÷ 169.5 × 100 = 2.65 wt%) with respect to the total weight, and the ratio amount is the aging blended in the PVC old electric wire. The content of the inhibitor relative to the organic polymer (PVC and DINP) is 3.21% (4.5 ÷ 140 × 100 = 3.21%).
[0033]
[Table 1C]

[0034]
These three types of insulated wires are shown in Tables 1A to 1C around the electric conductor formed by twisting seven 0.32 mm diameter soft copper wires into a copper stranded wire having an outer diameter of about 1.0 mm. Each is coated with an insulating material. For example, the first HF electric wire is prepared by mixing the resin composition shown in Table 1A with a twin-screw kneader at a mixing temperature of 250 ° C. and making it into a pellet-like composition with a pelletizer. Extruded to a thickness of 3 mm and formed as an electric wire covering layer around an electric conductor composed of seven stranded wires. The extrusion temperature at that time is 250 ° C. In addition, the second PVC electric wire and the third PVC old electric wire are prepared by mixing the resin composition shown in Table 1B or Table 1C with a biaxial kneader at a mixing temperature of 180 ° C. and pelletizing with a pelletizer. Was extruded to a thickness of 0.3 mm using an extruder, and this was formed as an electric wire covering layer around an electric conductor composed of seven stranded wires. The extrusion temperature is 180 ° C.
[0035]
Next, the following five types of wire bundles to which the wire harness protective material according to this example was applied were prepared. The first is a single HF wire bundle consisting of 30 HF wires in Table 1A, and the other four are mixed wires consisting of HF wires in Table 1A and PVC wires in Table 1B or PVC old wires in Table 1C. It is a bunch. Each of the various wire bundles has a total number of 30 wires, but for the mixed wire bundle, the mixing ratio (“number of PVC wires or PVC old wires: number of HF wires”) is “25: 5”, respectively. “Book”, “20: 10”, “10: 20” and “5: 25”.
[0036]
Next, the composition and test results of the wire harness protective material used in various examples will be described. First, Tables 2 to 5 show the compositions and test results of tapes with PVC adhesive as a wire harness protective material, tubes and sheets, and Tables 2 to 3 contain copper damage inhibitors. Tables 4 to 5 correspond to those containing copper damage inhibitors and anti-aging agents.
[0037]
[Table 2]

[0038]
[Table 3]

[0039]
[Table 4]

[0040]
[Table 5]

[0041]
Various compositions will be described. Each of the tapes, tubes and sheets with PVC adhesive shown in Tables 2 to 5 uses a base material made of a polyvinyl chloride (PVC) resin (polymerization degree P = 1300) as a base polymer. As a plasticizer with 60 parts by weight of DOP (dioctyl phthalate) as a plasticizer, 20 parts by weight of calcium carbonate as a filler, and 5 parts by weight of zinc / calcium as a stabilizer. In the compounds shown in Tables 2 to 3, this compound does not contain any copper damage inhibitor (each conventional product), and contains an appropriate amount of copper damage inhibitor ( Example products 1-1 to 1-5 and 2-1 to 2-5) and those containing an excessive amount of copper damage inhibitor (Comparative example products 1 and 2) were prepared, and Tables 4 to 5 were prepared. In what is shown in No harm prevention agent and anti-aging agent are blended (each conventional product), copper harm prevention agent and anti-aging agent are blended in appropriate amounts (Example products 3-1 to 3-5 and 4) -1 to 4-5) and those containing excessive copper damage inhibitors (Comparative Examples 3 and 4) were prepared. In addition, the compounding quantity of the anti-aging agent of the base material of a PVC tube, a tape, and a sheet | seat is adjusted so that it may become substantially equivalent to 3% of the ratio amount of anti-aging agent of the HF electric wire mentioned above. Here, the content ratio with respect to the organic polymer (PVC and DOP) is defined as a proportion amount, and the proportion amount is adjusted to 3.12% (5 ÷ 160 × 100 = 3.12%).
[0042]
And the tapes with PVC adhesive shown in Tables 2 and 4 are all obtained by applying an adhesive made of a rubber-based material such as styrene butadiene rubber (SBR) or NR to the entire surface of one side of the substrate. As the pressure-sensitive adhesive applied to the substrate surface, 30 parts by weight of NR (natural rubber), 20 parts by weight of zinc and 80 parts by weight of rosin resin are blended with 70 parts by weight of SBR (styrene butadiene rubber). In the case of those shown in Table 2, this compound contains no copper damage inhibitor (conventional product), and contains an appropriate amount of copper damage inhibitor (this example) Articles 1-1 to 1-5), and a compound containing an excessive amount of copper damage inhibitor (Comparative Example 1) are prepared. And no anti-aging agent (conventional product), copper Inhibitors and that the appropriate amount antioxidant (embodiment articles 3-1 to 3-5) were prepared that excessively blended copper inhibitor (Comparative Example product 3). The thickness of the pressure-sensitive adhesive layer is 0.02 mm, and the total thickness of the base material and the pressure-sensitive adhesive layer is 0.13 mm. In addition, the amount of the anti-aging agent for the PVC tube, the tape and the base material of the sheet is adjusted so as to be substantially equal to the above-described 3% proportion of the anti-aging agent for the HF electric wire. Here, the content ratio with respect to the organic polymer (SBR, NR, and rosin resin) is defined as a proportion amount, and the proportion amount is adjusted to 3.3% (6 ÷ 180 × 100 = 3.3%).
[0043]
That is, the adhesive-attached PVC tape, tube, and sheet containing the copper damage inhibitor and the anti-aging agent shown in Tables 4 to 5 are the base material and, if applicable, the adhesive layer, respectively. This corresponds to a combination of the compositions shown in Tables 2 and 3 with an antioxidant.
[0044]
Next, tests and evaluations were performed on the conventional products, the examples, and the comparative examples shown in Tables 2 to 5 manufactured as described above. First, the test method will be described. As a sample, the tape with the PVC adhesive shown in each table, a tube, and a sheet were wound around the total of five types of HF single electric wire bundle and mixed electric wire bundle, respectively. The test was conducted as follows. That is, these samples were left in a thermostatic bath at 150 ° C. for 96 hours, and then the HF electric wire was taken out and the presence or absence of cracks in the coated portion was confirmed by winding with a 10φ mandrel.
[0045]
Next, test results will be described. The test results in Tables 2 to 5 are all distinguished only by the blending amount of the copper damage inhibitor and do not mention the type of the wire bundle. This is because the difference in the type of wire bundle and the mixing ratio did not affect the test results. After all, the test results showed that the PVC adhesive tape, tube and sheet had a good appearance in the conventional product, but the HF electric wire was cracked and judged to be defective (x). In Comparative Examples 1 to 4, Although the electric wire did not crack, the PVC adhesive tape, tube, and sheet caused blooming and were judged to be defective (x). In addition, none of the examples 1-1 to 1-5, 2-1 to 2-5, 3-1 to 3-5, and 4-1 to 4-5 cause any cracks in the electric wire, and the appearance also The result of being good (◯) was obtained, and the result of being good (◯) as a comprehensive evaluation was obtained.
[0046]
From the above, wire harness protective material (tape with adhesive) mainly composed of PVC resin material containing an appropriate amount of copper damage prevention agent around HF single wire bundle or mixed wire bundle bundled with wires covering soft copper wire It has been found that a good heat aging performance can be obtained for the HF electric wire, for example, by wrapping a sheet, a tube and a sheet. This is because even if the copper damage inhibitor contained in the HF electric wire is consumed, the copper damage inhibitor contained in the wire harness protective material spreads on the plasticizer and spreads to the HF electric wire. It is thought that this is because copper damage prevention agents are replenished.
[0047]
In addition, if the anti-aging agent in the proportion equivalent to the anti-aging agent contained in the HF electric wire is contained in the wire harness protective material, the anti-aging agent of the HF electric wire is extracted by the influence of the plasticizer. It will never be done. This is because the proportion of the anti-aging agent in the wire harness protective material is almost the same as the proportion of the anti-aging agent in the HF electric wire, so that the concentration gradient (of the anti-aging agent) even if the plasticizer is transferred to the HF electric wire. This is probably because the anti-aging agent for HF electric wires is not extracted.
[0048]
Tables 6 to 9 show the compositions of HF adhesive tapes, tubes and sheets as wire harness protective materials, and test results, and Tables 6 to 7 contain copper damage inhibitors. Tables 8 to 9 correspond to those containing a copper damage inhibitor and an anti-aging agent.
[0049]
[Table 6]

[0050]
[Table 7]

[0051]
[Table 8]

[0052]
[Table 9]

[0053]
Various compositions will be described. The tapes, tubes, and sheets with HF pressure-sensitive adhesives shown in Tables 6 to 9 all use a base material having a polyolefin resin as a base polymer, and the base material is 100 parts by weight of the polyolefin resin. Using a compound containing 3 parts by weight of a brominated flame retardant, and further 1.5 parts by weight of antimony trioxide, the compounds shown in Tables 6 to 7 were completely free of copper damage prevention agents. What is not blended (each conventional product), what is blended with an appropriate amount of copper damage prevention agent (Example products 5-1 to 5-5 and 6-1 to 6-5) and copper damage prevention agent Prepared in excess (Comparative products 5 and 6), and in those shown in Tables 8 to 9, the compound was completely blended with copper damage inhibitor and anti-aging agent. None (each conventional product), copper damage inhibitor and anti-aging agent are blended in appropriate amounts It is those that have been prepared which (the embodiment product 7-1 to 7-5 and 8-1 to 8-5) and copper inhibitor is excessively blended (Comparative Product 7 and 8). In addition, the compounding quantity of the anti-aging agent of the base material of an HF tube, a tape, and a sheet | seat is adjusted so that it may become substantially equal to 3% of the ratio amount of anti-aging agent of the HF electric wire mentioned above. Here, the content with respect to the organic polymer (polyolefin) is defined as a proportion, and the proportion is adjusted to 3.5% (3.5 ÷ 100 × 100 = 3.5%).
[0054]
And the tapes with HF adhesive shown in Table 6 and Table 8 are all the same as the case of the tape with PVC adhesive, that is, styrene butadiene rubber (SBR), NR, etc. The pressure sensitive adhesive applied to the surface of the base material is 30 parts by weight of NR (natural rubber), 70 parts by weight of SBR (styrene butadiene rubber), and zinc white. 20 parts by weight and 80 parts by weight of rosin resin were used, and those shown in Table 6 contain no copper damage inhibitor (conventional product), copper Prepared with a suitable amount of harm prevention agent (Example products 5-1 to 5-5) and an excessive amount of copper harm prevention agent (Comparative Example product 5), and those shown in Table 8 In that case, the copper damage inhibitor and aging Stopper is not blended at all (conventional product), copper damage inhibitor and anti-aging agent are blended in appropriate amounts (Example products 7-1 to 7-5), and copper damage inhibitor is excessively blended. (Comparative Example Product 7) was prepared. The thickness of the pressure-sensitive adhesive layer is 0.02 mm, and the total thickness of the base material and the pressure-sensitive adhesive layer is 0.13 mm. The amount of the anti-aging agent for the HF tube, the tape and the sheet is adjusted so as to be approximately equal to the above-described 3% proportion of the anti-aging agent for the HF electric wire. Here, the content ratio with respect to the organic polymer (SBR, NR, and rosin resin) is defined as a proportion amount, and the proportion amount is adjusted to 3.3% (6 ÷ 180 × 100 = 3.3%).
[0055]
That is, the adhesive-attached HF tape, tube, and sheet containing the copper damage inhibitor and the anti-aging agent shown in Tables 8 to 9, respectively, the base material and, if applicable, the adhesive layer, This corresponds to the formulation shown in Tables 6 to 7 further blended with an antioxidant.
[0056]
Next, tests and evaluations were performed on the conventional products, the examples, and the comparative examples shown in Tables 6 to 9 manufactured as described above. First, the test method will be described. As samples, tapes with HF pressure-sensitive adhesive, tubes, and sheets shown in each table were respectively wound around the total of five types of HF single electric wire bundles and mixed electric wire bundles described above. The test was conducted as follows. That is, these samples were left in a thermostatic bath at 150 ° C. for 96 hours, and then the HF electric wire was taken out and the presence or absence of cracks in the coated portion was confirmed by winding with a 10φ mandrel.
[0057]
Next, test results will be described. The test results in Tables 6 to 9 are all distinguished only by the blending amount of the copper damage inhibitor and do not mention the type of the wire bundle. This is because the difference in the type of wire bundle and the mixing ratio did not affect the test results. After all, the test results showed that the HF pressure-sensitive adhesive tape, tube, and sheet had a good appearance in the conventional product, but the HF electric wire was cracked and determined to be defective (x). The wire did not crack, but the tape with HF adhesive, the tube, and the sheet caused blooming and were judged to be defective (x). And this example goods 5-1 to 5-5, 6-1 to 6-5, 7-1 to 7-5, and 8-1 to 8-5 are all not cracked in the electric wire, and the appearance is also The result of being good (◯) was obtained, and the result of being good (◯) as a comprehensive evaluation was obtained.
[0058]
From the above, a wire harness protective material (adhesive) mainly composed of a bromine-based polyolefin resin material containing an appropriate amount of a copper damage prevention agent around an HF single wire bundle or a mixed wire bundle bundled with an electric wire covering an annealed copper wire It has been found that a good heat aging performance can be obtained for the HF electric wire by winding a tape-like material, a tube-like material and a sheet-like material). It is considered that copper damage due to the influence of moisture in the air, adhesive, etc. can be suppressed by the wire harness protective material.
[0059]
In addition, if the anti-aging agent in the HF electric wire is contained in the wire harness protective material in an amount substantially equal to the anti-aging agent contained in the HF electric wire, the anti-aging agent of the HF electric wire is transferred to the wire harness protective material. Never do. This is because the concentration gradient is considered to be equivalent by making the proportion of the anti-aging agent substantially the same as the proportion of the anti-aging agent of the HF electric wire.
[0060]
The present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit of the present invention. For example, in the various examples described above, the PVC resin type and the polyolefin type are shown as the wire harness protective material, but the composition is not limited to those of the examples. Further, the polyolefin-based wire harness protective material is a material containing a small amount of bromine-based flame retardant (low halogen-based material), but may be a wire harness protective material that does not contain any halogen element.
[0061]
In short, the gist of the present invention is to replenish the HF electric wire covering material with a copper damage preventing agent by blending the copper damage preventing agent into the tape-like material, tube-like material or sheet-like material with adhesive as a wire harness protective material. In a state where it is used as a single HF wire or in a state where it is used in combination with a PVC wire, it can be used between a HF wire and a wire harness protective material or a PVC wire. The object is to avoid the adverse effects and achieve permanent use by stabilizing the quality of the wire as a wire harness and extending the life of the wire.
[0062]
【The invention's effect】
Since the wire harness protective material according to the first aspect of the present invention includes a copper damage preventive agent contained in the tape-like material, the tube-like material, or the sheet-like material with adhesive, the electricity containing copper An electric wire bundle in which electric wires covering a conductor are bundled, and there is an effect that copper damage of an electric wire bundle made of a halogen-free insulated electric wire can be suppressed.
[0063]
The wire harness protective material according to claim 2 is a tape-like material with a pressure-sensitive adhesive, a tube-like material, or a sheet-like material made of a vinyl chloride resin material. Even if the agent is consumed, there is an effect that the copper damage preventing agent can be replenished from the base material to the halogen-free insulated wire.
[0064]
Since the wire harness protective material according to claim 3 is made of a halogen-free resin material as the base material of the tape-like product, tube-like product or sheet-like product with adhesive, moisture in the air, adhesive, etc. There is an effect that it is possible to suppress copper damage due to the influence of the.
[0065]
The wire harness protective material according to claim 4, wherein the content of the copper damage inhibitor contained in the adhesive tape-like material, tube-like material or sheet-like material is 100 parts by weight of the base polymer of the base material. Therefore, there is an effect that the deterioration of the heat aging performance can be prevented.
[0066]
Since the wire harness protective material according to claim 5 contains an anti-aging agent in the adhesive tape-like material, tube-like material or sheet-like material, it can prevent the deterioration of the electric wire. There is an effect.
[0067]
The wire harness protective material according to claim 6 is characterized in that the content of the anti-aging agent contained in the tape-like product, the tube-like product or the sheet-like product with the adhesive is the proportion of the anti-aging agent of the substrate. Therefore, there is an effect that the diffusion of the anti-aging agent from the halogen-free insulated wire to the wire harness protective material is prevented.
[0068]
The wire harness protective material according to claim 7 covers an electric conductor containing copper because a copper damage preventive agent is contained in the base material and / or the adhesive material of the adhesive tape-like material. An electric wire bundle in which electric wires are bundled, and can suppress copper damage of an electric wire bundle made of a halogen-free insulated electric wire covered with the electric conductor with a halogen-free resin material, and further, the base material and / or the adhesive material Since the content of the copper damage inhibitor contained in each is in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material, the deterioration of heat aging performance is prevented. There is an effect that can be done.
[0069]
Since the wire harness protective material according to claim 8 contains an anti-aging agent in the base material and / or the adhesive material of the tape-like material with the adhesive, it can prevent the deterioration of the electric wire. Furthermore, the content of the anti-aging agent contained in the base material and / or the adhesive is such that the proportion of the anti-aging agent of the base material is substantially equal to the proportion of the anti-aging agent of the electric wire. Therefore, there is an effect that the diffusion of the anti-aging agent from the halogen-free insulated wire to the wire harness protective material is prevented.
[0070]
The wire harness according to claim 9 is an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, and is an electric wire bundle made of a halogen-free insulated electric wire covered with the electric conductor with a halogen-free resin material, or the wire bundle Heat aging performance since a part of a wire bundle that is partially replaced with a PVC insulated wire coated with the electrical conductor with a vinyl chloride resin material is coated with the wire harness protective material according to claim 1. It is possible to prevent the decrease in the service life and to prolong the service life.
[0071]
The wire harness according to claim 10 is an electric wire covering for each electric wire of an electric wire bundle in which insulated wires made of a halogen-free resin material are bundled or part of the bundle is bundled with the insulated wires made of the vinyl chloride resin material. Since the copper damage inhibitor and / or anti-aging agent is contained in the material, the copper damage preventive agent can be replenished from the PVC old wire to the HF wire, and from the HF wire to the PVC old wire. There is an effect that the diffusion of the anti-aging agent is suppressed.

Claims (10)

An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, and the electric conductor is covered with a halogen-free resin material that does not contain any halogen element or has a halogen element content that is at least lower than that of vinyl chloride resin. Tape or tube with adhesive used to coat a wire bundle made of halogen-free insulated wires or a part of the wire bundle in place of a PVC insulated wire coated with the electrical conductor with a vinyl chloride resin material Or it is a sheet-like wire harness protective material, Comprising: The copper-damage prevention agent contains in the said tape-like thing with adhesive, a tube-like thing, and a sheet-like thing, The wire harness protective material characterized by the above-mentioned. The wire harness protective material according to claim 1, wherein the base material of the tape-like material with adhesive, the tube-like material, and the sheet-like material is made of a vinyl chloride resin material. The adhesive tape-like, tube-like and sheet-like base materials are characterized by comprising no halogen element or a halogen-free resin material having a halogen element content at least lower than that of vinyl chloride resin. The wire harness protective material according to claim 1. The content of the copper damage inhibitor contained in the tape-like product, tube-like product or sheet-like product with pressure-sensitive adhesive is in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the substrate. The wire harness protective material according to claim 2 or 3, wherein The wire harness protective material according to claim 4, wherein the tape-like product with adhesive, tube-like product or sheet-like product contains an anti-aging agent. The proportion of the anti-aging agent contained in the tape-like article, tube-like article or sheet-like article with the pressure-sensitive adhesive is substantially equal to the proportion of the anti-aging agent of the electric wire. The wire harness protective material according to claim 5, which is configured as described above. An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, and the electric conductor is covered with a halogen-free resin material that does not contain any halogen element or has a halogen element content that is at least lower than that of vinyl chloride resin. A wire harness protective material used by covering a wire bundle made of a halogen-free insulated wire or a part of the wire bundle in place of the PVC insulated wire coated with the electric conductor with a vinyl chloride resin material, The adhesive tape-like product contains a copper damage inhibitor in the base material and / or the pressure sensitive adhesive, and each content is 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material. A wire harness protective material characterized by having a weight range. The tape-like product with the pressure-sensitive adhesive contains an anti-aging agent in the base material and / or the pressure-sensitive adhesive, and the content of the anti-aging agent in the base material is the proportion of the anti-aging agent in the wire. The wire harness protective material according to claim 7, wherein the wire harness protective material is substantially equal. An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, and the electric conductor is covered with a halogen-free resin material that does not contain any halogen element or has a halogen element content that is at least lower than that of vinyl chloride resin. The wire harness protective material according to any one of claims 1 to 8, wherein a wire bundle made of a halogen-free insulated wire or a part of the bundle is replaced with a PVC insulated wire covered with a vinyl chloride resin material. A wire harness characterized by being coated. The wire covering material of each wire of the wire bundle made of the halogen-free insulated wire or a part of the wire bundle obtained by replacing the PVC insulated wire with a part thereof contains a copper damage inhibitor and / or an anti-aging agent. The wire harness according to claim 9, wherein the wire harness is characterized.