JP4059971B2 - Glass run channel - Google Patents

Description

【００６３】
本発明において、全イソプレン単位に対する１，２−位および３，４−位で結合しているイソプレン単位含有量が４０％以上であるとき、耐傷付き性に優れた成形体を提供し得る熱可塑性エラストマーを得ることができる。
【００６４】
ブロック共重合体（ｃ）におけるスチレンまたはその誘導体の重合体ブロック（ｃ−１）の割合は、好ましくは５〜５０重量％、さらに好ましくは１０〜４５重量％の範囲である。すなわち、上記のイソプレン重合体ブロックまたはイソプレン・ブタジエン共重合体ブロック（ｃ−２）の割合は、好ましくは９５〜５０重量％、さらに好ましくは９０〜５５重量％の範囲である。
【００６５】
本発明においては、水素添加されたブロック共重合体（ｃ）が好ましい。水素添加されたブロック共重合体（ｃ）を用いると、耐候性と耐熱性により優れた成形体を提供し得る熱可塑性エラストマーが得られる。
本発明で用いられるブロック共重合体（ｃ）のメルトフローレート（ＭＦＲ；ＡＳＴＭ Ｄ １２３８、２３０℃、２．１６ｋｇ荷重、以下同じ）は、好ましくは０．０１〜３０ｇ／１０分、さらに好ましくは０．０１〜１０ｇ／１０分の範囲にある。メルトフローレートが上記のような範囲にあるブロック共重合体（ｃ）を用いると、耐傷付き性に優れた成形体を提供し得る熱可塑性エラストマーが得られる。
【００６６】
本発明で用いられるブロック共重合体（ｃ）のブロック形態としては、ブロック（ｃ−１）−ブロック（ｃ−２）−ブロック（ｃ−１）の形態が最も好ましいが、これに限られるものではない。
【００６７】
このようなブロック共重合体（ｃ）は、たとえば、以下のような方法により製造することができる。
(1) アルキルリチウム化合物を開始剤としてスチレンまたはその誘導体、イソプレンまたはイソプレン・ブタジエン混合物を逐次重合させる方法。
(2) スチレンまたはその誘導体、次いで、イソプレンまたはイソプレン・ブタジエン混合物を重合し、これをカップリング剤によりカップリングする方法。
(3) ジリチウム化合物を開始剤としてイソプレンまたはイソプレン・ブタジエン混合物、次いで、スチレンまたはその誘導体を逐次重合させる方法。
【００６８】
上記ブロック共重合体（ｃ）の製造方法の詳細は、たとえば特開平２−３００２５０号公報に記載されている。
また、上記のような方法により得られたブロック共重合体（ｃ）に水添処理を行なえば、水素添加されたブロック共重合体（ｃ）が得られる。水添されるブロックは、イソプレン重合体ブロックまたはイソプレン・ブタジエン共重合体ブロック（ｃ−２）である。
【００６９】
本発明においては、ブロック共重合体（ｃ）は、必要に応じて、上記の成分（ａ）、（ｂ）および（ｃ）の合計量１００重量部に対して、５〜６０重量部、好ましくは１０〜５０重量部、さらに好ましくは１０〜４０重量部の割合で用いられる。
【００７０】
ブロック共重合体（ｃ）を上記のような割合で用いると、特に耐摩耗性に優れた成形体を提供し得る熱可塑性エラストマーが得られる。
［高級脂肪酸アミド（ｄ）、シリコーンオイル（ｅ）、エステル（ｆ）およびフッ素系ポリマー（ｇ）］
本発明で用いられる高級脂肪酸アミド（ｄ）としては、具体的には、ラウリル酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベへミン酸アミド等の飽和脂肪酸アミド；
エルカ酸アミド、オレイン酸アミド、ブラシジン酸アミド、エライジン酸アミド等の不飽和脂肪酸アミド；
メチレンビスステアリン酸アミド、メチレンビスオレイン酸アミド、エチレンビスステアリン酸アミド、エチレンビスオレイン酸アミド等のビス脂肪酸アミドなどが挙げられる。これらの中では、エルカ酸アミド、オレイン酸アミド、エチレンビスオレイン酸アミドが好ましい。
【００７１】
本発明で用いられるシリコーンオイル（ｅ）としては、具体的には、ジメチルシリコーンオイル、フェニルメチルシリコーンオイル、フルオロシリコーンオイル、テトラメチルテトラフェニルトリシロキサン、変性シリコーン油などが挙げられる。これらの中では、ジメチルシリコーンオイル、フェニルメチルシリコーンオイルが好ましく用いられる。
【００７２】
このシリコーンオイル（ｅ）の動粘度［ＪＩＳ Ｋ ２２８３、２５℃］は、１０〜３０，０００ｃＳｔ、好ましくは５０〜１０，０００ｃＳｔ、さらに好ましくは１００〜５，０００ｃＳｔの範囲である。
【００７３】
本発明で用いられるエステル（ｆ）は、脂肪族アルコールと、ジカルボン酸あるいはモノカルボン酸とのエステルである。
このようなエステル（ｆ）としては、具体的には、セチルアルコールと酢酸とのエステル、セチルアルコールとプロピオン酸とのエステル、セチルアルコールと酪酸とのエステル、牛脂アルコールと酢酸とのエステル、牛脂アルコールとプロピオン酸とのエステル、牛脂アルコールと酪酸とのエステル、ステアリルアルコールと酢酸とのエステル、ステアリルアルコールとプロピオン酸とのエステル、ステアリルアルコールと酪酸とのエステル、ジステアリルアルコールとフタル酸とのエステル、グリセリンモノオレート、グリセリンモノステアレート、12- 水酸化ステアレート、グリセリントリステアレート、トリメチロールプロパントリステアレート、ペンタエリスリトールテトラステアレート、ブチルステアレート、イソブチルステアレート、ステアリン酸エステル、オレイン酸エステル、ベヘン酸エステル、カルシウムソープ含有エステル、イソトリデシルステアレート、セチルパルミテート、セチルステアレート、ステアリールステアレート、ベヘニルベヘネート、モンタン酸エチレングリコールエステル、モンタン酸グリセリンエステル、モンタン酸ペンタエリスリトールエステル、カルシウム含有モンタン酸エステルなどが挙げられる。これらの中では、ジステアリルアルコールとフタル酸とのエステル、グリセリンモノオレート、グリセリンモノステアレート、ステアリン酸エステル、モンタン酸グリセリンエステルが好ましい。特にジステアリルアルコールとフタル酸とのエステル、グリセリンモノステアレート、モンタン酸グリセリンエステルが好ましい。
【００７４】
本発明で用いられるフッ素系ポリマ−（ｇ）としては、具体的には、ポリテトラフルオロエチレン、ビニリデンフルオライド共重合物などが挙げられる。これらの中では、ポリテトラフルオロエチレンが好ましい。
【００７５】
本発明においては、上記の高級脂肪酸アミド（ｄ）、シリコーンオイル（ｅ）、エステル（ｆ）およびフッ素系ポリマー（ｇ）からなる群から選ばれる少なくとも１種の成分は、必要に応じて用いられ、ポリオレフィン（ａ）もしくはポリオレフィン組成物（ａ）’とオレフィン系熱可塑性エラストマー（ｂ）とブロック共重合体（ｃ）との合計量１００重量部に対して、０．０１〜１０重量部、好ましくは０．０５〜５重量部、さらに好ましくは０．１〜５重量部の割合で用いられる。上記ブロック共重合体（ｃ）は任意成分であるので、０重量部となる場合がある。
【００７６】
［液体ないし固体の潤滑油］
前記（３）の組成物で用いられる液体潤滑油としては、石油系潤滑油、合成潤滑油などが使用される。
【００７７】
石油系潤滑油としては、具体的には、流動パラフィン、スピンドル油、冷凍機油、ダイナモ油、タービン油、マシン油、シリンダー油などが使用される。
合成潤滑油としては、具体的には、合成炭化水素油、ポリグリコール油、ポリフェニルエーテル油、エステル油、リン酸エステル油、ポリクロロトリフルオロエチレン油、フルオロエステル油、塩素化ビフェニル油、シリコーン油などが使用される。
【００７８】
また、前記（３）の組成物で用いられる固体潤滑油としては、具体的には、黒鉛、二硫化モリブデンが主に使用されるが、他に窒化ホウ素、二硫化タングステン、酸化鉛、ガラス粉、金属石けんなども、使用することができる。固体潤滑油は、単独でも使用することができ、また、液体潤滑油と組み合わせて使用することができ、たとえば粉末、ゾル、ゲル、サスペンソイドなどの形態で超高分子量ポリオレフィンに配合することができる。
【００７９】
本発明で用いられる超高分子量ポリオレフィン組成物（Ｂ）には、必要に応じて、鉱物油系軟化剤、耐熱安定剤、帯電防止剤、耐候安定剤、老化防止剤、充填剤、着色剤、滑剤などの添加物を、本発明の目的を損なわない範囲で配合することができる。
【００８０】
上記（１）〜（３）の超高分子量ポリオレフィン組成物（Ｂ）は、上記熱可塑性エラストマー（Ａ）との共押出積層加工が行なえるため、本発明のガラスランチャンネルの製造に際し、フィルム（シート）成形工程を経ることなく、直接、熱可塑性エラストマー（Ａ）層と超高分子量ポリオレフィン組成物（Ｂ）層とを積層することができ、経済的である。
【００８１】
一方、超高分子量ポリオレフィン、たとえば上記（２）における１３５℃デカリン溶媒中で測定した極限粘度［η］が７〜４０ｄｌ／ｇの範囲内にある超高分子量ポリオレフィン（ａ−１）単独では、上記熱可塑性エラストマー（Ａ）との共押出積層加工を行なうことはできず、したがって、上記の熱可塑性エラストマー層と超高分子量ポリオレフィン層との積層に際しては、少なくとも一方を予めフィルム（シート）にしておく必要があり、上記超高分子量ポリオレフィン組成物（Ｂ）の場合と比較すると経済性に劣る。
【００８２】
本発明に係るガラスランチャンネルにおいて、水切り部３はガラスランチャンネル本体２と同一材質からなることが好ましい。
ガラスランチャンネル本体２が熱可塑性エラストマー（Ａ）からなっている場合には、水切り部３も同一材質で成形すれば、耐久性の点でも、滑性樹脂層９との接合強度の点でも十分に実用に耐える。
【００８３】
本発明に係るガラスランチャンネルにおいて用いることのできるシャークスキン（サメ肌）は、原料熱可塑性エラストマー（Ａ）の性状を適当に選ぶことにより、成形時に発現させ得る。
【００８４】
得られたシャークスキンの外観は、樹脂やエラストマーの押出成形時に見られることのあるメルトフラクチャーとは異なり、成形品の肌が周期的に荒れて微細な凹凸を生じている。
【００８５】
また、このシャークスキンの上に施された滑性樹脂層９表面にも、シャークスキンが現出していることが必要で、滑性樹脂層９の厚さは、通常３〜５０μｍとなるように積層する。また、本発明においては、必要に応じて、滑性樹脂層９の厚さをさらに厚くすることもできるし、また薄くすることもできる。
【００８６】
なお、水切り部３が窓ガラス１２と接触する部位は、窓ガラス１２の進入時と退出時とでは一般に異なるから、超高分子量ポリオレフィン組成物（Ｂ）による被覆および必要に応じて施されるシャークスキンの形成は、水切り部３の比較的広い範囲に施しておくことが好ましい。
【００８７】
また、図１に示す具体例では、ガラスランチャンネル本体２の内部には、窓ガラス端部と当接する部分１６があるが、この部分１６にも、熱可塑性エラストマー（Ａ）からなるガラスランチャンネル本体２表面に、超高分子量ポリオレフィン組成物（Ｂ）からなる滑性樹脂層９を設けることができる。
【００８８】
さらに、本発明においては、上記滑性樹脂層９の表面に起毛が存在していてもよい。上記起毛の加飾方法としては、（ａ）エメリーペーパーによるバフ掛けをして滑性樹脂層表面を起毛加飾する方法、（ｂ）針布ロール通しをして滑性樹脂層表面を起毛加飾する方法、（ｃ）ベルトサンダーもしくはドラムサンダーなどによるサンディングをして滑性樹脂層表面を起毛加飾する方法、（ｄ）特開昭６２−２７５，７３２号公報に記載されている熱微小体を衝突させて滑性樹脂層表面を起毛加飾する方法など、従来公知の起毛加飾方法が用いられる。
【００８９】
【発明の効果】
本発明によれば、接着剤の塗布工程、接着剤の硬化ないし焼付工程、およびその前後のエンボス加工工程をすべて省略することができ、その結果、工程数が少なくて済み、また、作業時間を短縮することができるため、経済性に優れたガラスランチャンネルを製造することができるとともに、耐久性、閉鎖時における窓ガラスとの緊密接触性、および開閉操作時における軽快摺動性に優れ、ねじったり折り曲げたりしても超高分子量ポリオレフィン組成物層に皺が生じないガラスランチャンネルを提供することができる。
【００９０】
以下、本発明を実施例により説明するが、本発明は、これら実施例に限定されるものではない。
【００９１】
【実施例１】
エチレン含有量７０モル％、ヨウ素価１２、ムーニー粘度ＭＬ₁₊₄ （１００℃）１２０のエチレン・プロピレン・5-エチリデン-2- ノルボルネン共重合体ゴム［以下、ＥＰＤＭと略す］８０重量部と、ＭＦＲ（ＡＳＴＭ Ｄ １２３８−６５Ｔ、２３０℃）１３ｇ／１０分、密度０．９１ｇ／ｃｍ³ のポリプロピレン［以下、ＰＰと略す］２０重量部とを、バンバリーミキサーを用いて、窒素雰囲気中、１８０℃で５分間混練した後、この混練物をロールに通してシート状にし、これをシートカッターで裁断して角ペレットを製造した。
【００９２】
次いで、この角ペレットと、1,3-ビス（ｔｅｒｔ- ブチルペルオキシイソプロピル）ベンゼン［以下、ペルオキシドと略す］０．３重量部と、ジビニルベンゼン［以下、ＤＶＢと略す］０．５重量部とをヘンシェルミキサーで攪拌混合した。
【００９３】
次いで、この混合物を、Ｌ／Ｄ＝４０、スクリュー径５０ｍｍの２軸押出機を用いて、窒素雰囲気中、２２０℃で押出して熱可塑性エラストマー（Ａ−１）を得た。
【００９４】
得られた熱可塑性エラストマー（Ａ−１）のゲル含量は、上記方法により求めたところ、８５重量％であった。
この熱可塑性エラストマー（Ａ−１）を２３０℃の温度で押出成形してガラスランチャンネル本体および水切り部を成形するとともに、その表面に、１３５℃デカリン溶媒中で測定した極限粘度［η］が２８ｄｌ／ｇの超高分子量ポリエチレン（ａ−１）２３重量％と、１３５℃デカリン中で測定した極限粘度［η］が０．７３ｄｌ／ｇの低分子量ポリエチレン（ａ−２）７７重量％とからなるポリエチレン組成物（ａ）’［１３５℃デカリン中で測定した極限粘度［η］：７．０ｄｌ／ｇ］７５重量部と熱可塑性エラストマー（Ａ−１）２５重量部を上述の２軸押出機で混練した超高分子量ポリエチレン組成物（Ｂ−１）を２５０℃で共押出積層してガラスランチャンネルを得た。
【００９５】
得られたガラスランチャンネルは、ほぼ台形状の形状をしており、図３において窓枠１３に固定されるガラスランチャンネル１の傾斜部と水平部との合計長さが１５００ｍｍ、垂直部の長さが９００ｍｍであり、図１において本体２の底部外幅が１５ｍｍ、側部外高が２０ｍｍ、水切り部３の長さが１０ｍｍであり、図１に示された断面形状にほぼ等しく、超高分子量ポリエチレン組成物層の厚みは平均３０μｍであった。
【００９６】
得られたガラスランチャンネルを試験窓枠に装着し、厚さ３．２ｍｍの窓ガラスを嵌装して耐久試験（窓ガラス上下繰返し試験）を行なった。その結果、このガラスランチャンネルは、５０，０００回の窓ガラス上下繰返し試験にも耐え、ガラスランチャンネルとしての機能を維持していた。
【００９７】
しかしながら、従来品のガラスランチャンネル（窓ガラス摺動部が軟質塩化ビニル樹脂層にナイロンフィルムを接着した積層構造になっている）は、２５，０００回で窓ガラス接触面において破壊を生じ、その結果、窓ガラスとの摩擦抵抗が著しく増大して使用に耐えられなくなった。
【００９８】
また、この実施例１で得られたガラスランチャンネルの直線部を長さ３０ｃｍに切り、中央から水切り部を外側にして１８０度折り曲げたが、超高分子量ポリエチレン組成物層（滑性樹脂層）に顕著な皺は見られなかった。
【００９９】
【実施例２】
実施例１において、ポリエチレン組成物（ａ）’６０重量部、熱可塑性エラストマー（Ａ−１）１５重量部、およびスチレン・イソプレン・スチレンブロック共重合体［スチレン含有量：２０重量％、イソプレン重合体部分における１，２−位および３，４−位で結合しているイソプレン単位含有量：５５％、メルトフローレート：２．５ｇ／１０分］（ｃ）２５重量部を上述の２軸押出機で混練した超高分子量ポリエチレン組成物（Ｂ−２）を用いた以外は、実施例１と同様に行なった。
【０１００】
得られたガラスランチャンネルを用いて、窓ガラス上下繰返し試験を実施例１と同様にして行なった結果、５０，０００回に耐えた。また、上述の折り曲げに対しても、超高分子量ポリエチレン組成物層に顕著な皺は見られなかった。
【０１０１】
【実施例３】
実施例１において、ＥＰＤＭおよびＰＰのほかに、ブチルゴム［エッソ社製、ＩＩＲ−０６５、不飽和度０．８モル％、以下、ＩＩＲと略す］１０重量部およびパラフィン系プロセスオイル［出光興産（株）製、商品名 ダイアナプロセスオイル］３０重量部を配合して熱可塑性エラストマー（Ａ−２）を製造した以外は、実施例１と同様に行なった。得られた熱可塑性エラストマー（Ａ−２）のゲル含量は、７０％であった。
【０１０２】
得られたガラスランチャンネルは、窓ガラス上下繰返し試験５０，０００回に耐えた。また、上述の折り曲げに対して、超高分子量ポリエチレン組成物層に顕著な皺は見られなかった。
【０１０３】
【実施例４】
実施例１において、ポリエチレン組成物（ａ）’７５重量部および熱可塑性エラストマー（Ａ−１）２５重量部の他に、エルカ酸アミド０．５重量部から超高分子量ポリエチレン組成物（Ｂ−３）を調製した以外は、実施例１と同様に行なった。
【０１０４】
得られたガラスランチャンネルは、窓ガラス上下繰返し試験５０，０００回に耐えた。また、上述の折り曲げに対しても、超高分子量ポリエチレン組成物層に顕著な皺は見られなかった。
【０１０５】
【比較例１】
実施例１において、超高分子量ポリエチレン組成物（Ｂ−１）の代わりに、ポリエチレン組成物（ａ）’を単独で用いた以外は、実施例１と同様に行なった。
【０１０６】
得られたガラスランチャンネルは、窓ガラス上下繰返し試験５０，０００回に耐えた。しかしながら、上述の折り曲げに対しては、超高分子量ポリエチレン組成物層の部分に皺が生じ白化が見られた。
【図面の簡単な説明】
【図１】図１は、本発明に係るガラスランチャンネルの断面図である。
【図２】図２は、図１に示すガラスランチャンネルの窓ガラスとの接触部の拡大断面図である。
【図３】図３は、ガラスランチャンネルの自動車ドアへの取付けを説明する図である。
【図４】図４は、窓ガラスの開放時におけるガラスランチャンネルの状態を示す断面図である。
【図５】図５は、窓ガラスの閉鎖時におけるガラスランチャンネルの状態を示す断面図である。
【符号の説明】
１ ・・・・・ガラスランチャンネル
１ａ ・・・底壁
１ｂ ・・・側壁
１ｃ ・・・溝部
２ ・・・・・ガラスランチャンネル本体
３ ・・・・・水切り部
４ ・・・・・窓ガラス接触部
７ ・・・・・熱可塑性エラストマーからなる基体層
８ ・・・・・微小凹凸の繰返し模様（必要に応じて施される）を有する基体層表面
９ ・・・・・超高分子量ポリオレフィン組成物からなる滑性樹脂層
１０ ・・・微小凹凸の繰り返し模様（必要に応じて施される）を有する滑性樹脂層表面[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a glass run channel, and more particularly, to a glass run channel provided with a window glass sliding portion constituted by a laminate made of a thermoplastic elastomer base layer and a slipping resin surface layer.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
In general, a window glass in a vehicle of an automobile needs to be opened and closed by raising and lowering for ventilation and ventilation or for talking with the outside of the vehicle. It is called a glass run channel between the window glass and the window frame in order to make it possible to perform a close (liquid-tight) sealing operation between the window glass and the window frame while facilitating the opening and closing operation of the window glass. A guide member is provided.
[0003]
The conventional glass run channel is formed of a soft synthetic resin such as a soft vinyl chloride resin or a vulcanized rubber such as an ethylene-propylene-diene copolymer rubber, and is extended from both ends of the bottom wall and the bottom wall. A glass run channel main body having a substantially U-shaped cross section and having a groove formed therein, and stretched so as to be close to each other toward the bottom wall from the vicinity of the tip of both side walls of the glass run channel main body. It consists of a tongue-shaped draining part.
[0004]
In the conventional glass run channel, the window glass sliding part has a nylon film or the like bonded to the surface to improve the separation from the drainage part of the window glass and to prevent the window glass from becoming dirty. In order to reduce the contact area with the window glass, embossing is performed before or after lamination of the nylon film or the like.
[0005]
In such a glass run channel, since there is no adhesion between the above-mentioned soft synthetic resin or vulcanized rubber and the surface material of nylons, the glass run channel main body is molded by using a soft synthetic resin or vulcanized rubber. It requires a process of applying an adhesive to the molded product and laminating a film such as nylon, and also requires embossing before or after this bonding. There is an inconvenience that it takes.
[0006]
In addition, since such a glass run channel has a lamination process with an adhesive, there is also a problem in durability, and there is a drawback that peeling between the surface film layer and the substrate is likely to occur due to aging and outdoor exposure. is there. Furthermore, the uneven pattern that can be formed by embossing is not yet satisfactory in the combination of fineness and uniformity, close contact between the window glass sliding part and the window glass at the time of closing, and at the time of opening There is still room for improvement in the light sliding property between the window glass sliding portion and the window glass.
[0007]
Therefore, the present inventors have intensively studied to solve the above-described problems of the glass run channel, and are composed of crystalline polyolefin and rubber as an elastomer constituting at least the sliding portion of the glass run channel. If a thermoplastic elastomer is selected and a specific ultra-high molecular weight polyolefin composition layer is laminated on the thermoplastic elastomer layer by heat-sealing, the manufacturing operation is easy, and durability and window glass when closed It was found that a glass run channel excellent in close contact with the glass and light sliding property with the window glass when opened could be obtained, and a new glass run channel was proposed. (JP-A-5-4522, JP-A-5-4308)
[0008]
However, this glass run channel has a high rigidity when an ultra high molecular weight polyolefin, for example, ultra high molecular weight polyethylene is used alone in the ultra high molecular weight polyolefin composition layer. When the glass run channel is twisted or bent, wrinkles are generated in the ultrahigh molecular weight polyolefin composition layer, which may impair the appearance of the product.
[0009]
As a result of repeated studies to improve this point, the present inventors have used an ultrahigh molecular weight polyolefin composition and an olefin-based thermoplastic elastomer as the ultrahigh molecular weight polyolefin composition. The inventors have found that a glass run channel having performance and capable of generating no wrinkles in the ultrahigh molecular weight polyolefin composition layer even when twisted or bent is obtained, and the present invention has been completed.
[0010]
OBJECT OF THE INVENTION
The present invention is intended to solve the problems associated with the prior art as described above, can be manufactured by simplifying the manufacturing process, durability, close contact with the window glass when closed, Another object of the present invention is to provide a glass run channel which is excellent in light slidability with a window glass at the time of opening and does not generate wrinkles in an ultrahigh molecular weight polyolefin composition layer even when twisted or bent.
[0011]
SUMMARY OF THE INVENTION
  The glass run channel according to the present invention is:
  A glass run channel body comprising a bottom wall and side walls extending from both ends of the bottom wall, having a substantially U-shaped cross section and having grooves formed therein, and the bottom wall from the vicinity of the ends of both side walls of the glass run channel body A glass run channel composed of a tongue-shaped drainer stretched so as to be close to each other toward the
  A window glass contact portion which is a surface in contact with the window glass of the draining portion,
  A thermoplastic elastomer (A) layer composed of crystalline polyolefin and rubber, an ultrahigh molecular weight polyolefin composition (B) layer, and
  The ultrahigh molecular weight polyolefin composition (B) layer is configured to come into contact with the window glass,
  The ultrahigh molecular weight polyolefin composition (B) is
  Ultra high molecular weight polyolefin (a-1) having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within a range of 7 to 40 dl / g, and an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 0. 0.1 to 5 dl / g of the polyolefin (a-2), and the ultrahigh molecular weight polyolefin (a-1) comprises the ultrahigh molecular weight polyolefin (a-1) and the polyolefin (a- 2) with respect to the total weight of 100% by weight and 15 to 40% by weight, andPolyolefin having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within a range of 3.5 to 8.3 dl / g(A) '10 to 90 parts by weight, and
  90 to 10 parts by weight of olefinic thermoplastic elastomer (b) comprising a crystalline olefinic resin and an olefinic rubber [component(A) 'And (b) is 100 parts by weight].
[0012]
As a preferable example of the thermoplastic elastomer (A) used in the present invention,
70 to 10 parts by weight of crystalline polypropylene (A-1),
30 to 90 parts by weight of rubber (A-2) made of ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber [the total amount of components (A-1) and (A-2) is 100 parts by weight And
And a thermoplastic elastomer in which the rubber (A-2) is crosslinked, which is obtained by dynamically heat-treating a mixture of the above in the presence of an organic peroxide.
[0013]
  MaThe ultra-high molecular weight polyolefin composition (B) preferably used in the present invention is
  Ultra high molecular weight polyolefin (a-1) having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within a range of 7 to 40 dl / g, and an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 0. 0.1 to 5 dl / g of the polyolefin (a-2), and the ultrahigh molecular weight polyolefin (a-1) comprises the ultrahigh molecular weight polyolefin (a-1) and the polyolefin (a- 2) and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g. The polyolefin composition (a) within 10 to 90 parts by weight,
  85 to 5 parts by weight of an olefinic thermoplastic elastomer (b) comprising a crystalline olefinic resin and an olefinic rubber, and
  A polymer block (c-1) of styrene or a derivative thereof and an isoprene polymer block and / or an isoprene-butadiene copolymer block, which are bonded at 1,2-position and 3,4-position with respect to all isoprene units. 5 to 60 parts by weight of a block copolymer (c) which may be hydrogenated with a polymer and / or copolymer block (c-2) having an isoprene unit content of 40% or more [ The total of components (a) ′, (b) and (c) is 100 parts by weight].
[0014]
Further, the ultrahigh molecular weight polyolefin composition (B) includes, in addition to the polyolefin (a) or the polyolefin composition (a) ', and the olefinic thermoplastic elastomer (b),
A polymer block (c-1) of styrene or a derivative thereof and an isoprene polymer block and / or an isoprene-butadiene copolymer block, which are bonded at 1,2-position and 3,4-position with respect to all isoprene units. A block copolymer (c) which may be hydrogenated and comprising a polymer and / or copolymer block (c-2) having an isoprene unit content of 40% or more, and / or
Contains at least one component selected from the group consisting of higher fatty acid amide (d), silicone oil (e), ester (f) of aliphatic alcohol and dicarboxylic acid or monocarboxylic acid, and fluorine-based polymer (g) You may do it.
[0015]
As a preferred example of the olefinic thermoplastic elastomer (b) constituting the ultrahigh molecular weight polyolefin composition (B),
70 to 10 parts by weight of crystalline polypropylene (A-1),
30 to 90 parts by weight of rubber (A-2) made of ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber [the total amount of components (A-1) and (A-2) is 100 parts by weight And
And a thermoplastic elastomer in which the rubber (A-2) is crosslinked, which is obtained by dynamically heat-treating a mixture of the above in the presence of an organic peroxide. In the present invention, the thermoplastic elastomer (A) and the olefinic thermoplastic elastomer (b) may be the same or different.
[0016]
The ultra high molecular weight polyolefin composition (B) may contain 1 to 20% by weight of a liquid or solid lubricating oil per ultra high molecular weight polyolefin composition (B).
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an example of the glass run channel according to the present invention will be specifically described with reference to the drawings.
[0018]
FIG. 1 is a cross-sectional view showing a cross-sectional structure of an example of a glass run channel according to the present invention.
In FIG. 1, 1 indicates the glass run channel of the present invention as a whole. The glass run channel 1 is composed of a bottom wall 1a and side walls 1b extending from both ends of the bottom wall 1a. The glass run channel 1 has a substantially U-shaped cross section (a U-shape), and a groove 1c is formed therein. A formed glass run channel body 2 is provided. Tongue-shaped draining portions 3 and 3 are stretched so as to be close to each other toward the bottom wall 1a from the vicinity of the ends of both side walls 1b and 1b of the glass run channel main body 2. 3 are configured such that the tips 5 and 5 are in a positional relationship that can be opened and closed. Moreover, the outer surface side of these draining parts 3 and 3 becomes the surface which contacts the window glass of vehicles, such as a motor vehicle, and comprises the window glass contact parts 4 and 4. FIG. Further, the glass run channel main body 2 is formed with mounting hooks 6 projecting so as to incline toward the tip end side of the side wall 1b on the outer sides of both side walls 1b and 1b.
[0019]
Although the main body 2 and the draining portion 3 are integrally formed of an elastomer, according to the present invention, at least the window glass contact portion 4 is made to have a base layer made of a specific thermoplastic elastomer (A) and a specific ultrahigh molecular weight. It is comprised with the slipping resin layer which consists of polyolefin compositions (B). As shown in FIG. 2 in which the window glass contact portion 4 is enlarged, the surface 8 of the base layer 7 is preferably provided with a repeating pattern of fine irregularities. On the surface 8 having such a sharkskin-like micro uneven pattern, the above-mentioned sliding resin layer 9 is laminated by heat fusion, and the outer surface 10 is provided with the same fine uneven pattern repeatedly. Preferably it is.
[0020]
FIGS. 3 to 5 are a perspective view and a sectional view of a window frame portion for explaining a method of mounting the glass run channel configured as described above to a window frame of an automobile.
As shown in FIGS. 3 to 5, a window glass 12 is attached to the door 11 of the automobile so that it can be opened and closed by moving up and down. On the other hand, the glass run channel 1 is fixed to the inner peripheral portion of the window frame 13 of the door 11.
[0021]
In order to fix the glass run channel 1 to the inner peripheral portion of the window frame 13, as shown in FIGS. 4 and 5, the window frame 13 has a substantially U-shaped cross section throughout (C-shaped). At the entrance portion of the concave portion 14 of the both side plate portions 14a that are formed and formed in the concave portion 14, a protruding portion 15 that protrudes inward is formed. Then, the glass run channel 1 is inserted into the recess 14 of the window frame 13 from the bottom wall side of the glass run channel body 2 so that the mounting hook 6 passes over the projection 15 of the window frame 13. Then, the mounting hook 6 is locked by the protrusion 15 and the glass run channel main body 2 is prevented from falling out of the recess 14 of the window frame 13. As a result, the glass run channel 1 is attached to the window frame 13. Can be fixed.
[0022]
As shown in FIG. 4, when the window glass 12 is lowered, the tips 5 and 5 of the draining portions 3 and 3 constituting the glass sliding portion of the glass run channel 1 are closed facing each other. In this state, it is possible to prevent dust and the like from entering the groove and soiling the surface of the window glass 12. On the other hand, as shown in FIG. 5, in the state where the window glass 12 is raised, the tips 5 and 5 of the draining portions 3 and 3 constituting the window glass sliding portion are inserted between the window glasses 12 therebetween. However, it is in contact with the surface of the window glass 12 so that a liquid-tight state is ensured.
[0023]
According to the present invention, the base layer 7 made of the thermoplastic elastomer (A) at least in the portion of the glass run channel 1 that comes into contact with the window glass, and the ultrahigh molecular weight polyolefin thermally fused to the surface of the base layer 7 A slipping resin layer 9 made of the composition (B) is provided.
[0024]
That is, the thermoplastic elastomer (A) used in the present invention can be thermoformed into an arbitrary shape and size, and has elasticity, flexibility, and flexibility required for the window slide portion of the glass run channel. It has excellent properties such as compressibility, and also has excellent properties such as durability, weather resistance, and water resistance. The thermoplastic elastomer (A) exhibits strong adhesiveness to the slipping resin layer 9 made of the ultrahigh molecular weight polyolefin composition (B) serving as the surface material layer, and is thermally bonded to the slipping resin layer 9. It is possible to form a laminated structure excellent in interlayer adhesive strength immediately after bonding and over time, and further in interlayer adhesive strength after a weather resistance test. Moreover, the thermoplastic elastomer (A) used as the base layer 7 in the present invention can be molded so as to exhibit a sharkskin-like molded appearance. This molding process and the ultrahigh molecular weight as the surface material layer Sharkskin-like micro uneven patterns are faithfully reproduced on the outer surface of the slippery resin layer 9 by combining the heat-seal process of the slippery resin layer 9 made of the polyolefin composition (B) and the base layer 7. You can also It is extremely difficult to copy the surface of such a sharkskin-like micro-concave pattern with a conventional adhesive coating method, and it has become possible only by a combination of the molding process and the thermal fusion process.
[0025]
According to the present invention, by adopting the above-described configuration, the adhesive application process, the adhesive curing or baking process, and the embossing process before or after it are all omitted, with a small number of processes and a small amount of labor. A glass run channel can be produced efficiently. In addition, by providing the slippery resin layer 9 made of the ultra-high molecular weight polyolefin composition (B) as a surface material layer, not only can the friction coefficient with the window glass be reduced, but also an uneven pattern by conventional embossing Compared to the above, it was possible to form a uniform shark-skin-like unevenness on the surface with a uniform pitch. Therefore, in the glass run channel according to the present invention, when the window glass is closed, close contact (liquid tight) with the window glass is possible, and when the window glass is opened, its sliding resistance is reduced, so that it is smooth and light. Open and close operation is possible.
[0026]
Thermoplastic elastomer (A)
The thermoplastic elastomer (A) used in the present invention is composed of crystalline polyolefin and rubber.
[0027]
Examples of the crystalline polyolefin used in the present invention include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms.
Specific examples of the crystalline polyolefin include the following (co) polymers.
(1) Ethylene homopolymer
(Manufacturing method may be either low pressure method or high pressure method)
(2) Copolymers of ethylene and other α-olefins up to 10 mol% or vinyl monomers such as vinyl acetate and ethyl acrylate
(3) Propylene homopolymer
(4) Random copolymers of propylene and other α-olefins up to 10 mol%
(5) Block copolymer of propylene and other α-olefin of 30 mol% or less
(6) 1-butene homopolymer
(7) Random copolymers of 1-butene and other α-olefins of 10 mol% or less
(8) 4-Methyl-1-pentene homopolymer
(9) Random copolymers of 4-methyl-1-pentene and other α-olefins of 20 mol% or less
Specific examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
[0028]
The rubber used in the present invention is not particularly limited, but olefin copolymer rubber is preferable.
The olefin copolymer rubber is an amorphous random elastic copolymer mainly composed of an α-olefin having 2 to 20 carbon atoms, and is an amorphous α composed of two or more α-olefins. -Olefin copolymer, α-olefin / non-conjugated diene copolymer composed of two or more kinds of α-olefin and non-conjugated diene.
[0029]
Specific examples of such olefin copolymer rubbers include the following rubbers.
(1) Ethylene / α-olefin copolymer rubber
[Ethylene / α-olefin (molar ratio) = about 90/10 to 50/50]
(2) Ethylene / α-olefin / non-conjugated diene copolymer rubber
[Ethylene / α-olefin (molar ratio) = about 90/10 to 50/50]
(3) Propylene / α-olefin copolymer rubber
[Propylene / α-olefin (molar ratio) = about 90/10 to 50/50]
(4) Butene / α-olefin copolymer rubber
[Butene / α-olefin (molar ratio) = about 90/10 to 50/50]
Specific examples of the α-olefin include α-olefins similar to the specific examples of the α-olefin constituting the crystalline polyolefin.
[0030]
Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.
[0031]
Mooney viscosity ML of these copolymer rubbers_{1 + 4} (100 ° C.) is preferably 10 to 250, particularly preferably 40 to 150. The iodine value when the non-conjugated diene is copolymerized is preferably 25 or less.
[0032]
In the thermoplastic elastomer, the olefin copolymer rubber can exist in all cross-linked states such as uncrosslinked, partially cross-linked, and overall cross-linked, but in the present invention, it exists in a cross-linked state. It is preferable that it exists in a partially crosslinked state.
[0033]
In addition to the above olefin copolymer rubber, other rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (IIR) are used as the rubber used in the present invention. And diene rubbers such as SEBS and polyisobutylene.
[0034]
In the thermoplastic elastomer (A) used in the present invention, the weight blending ratio of crystalline polyolefin and rubber (crystalline polyolefin / rubber) is usually 90/10 to 5/95, preferably 70/30 to 10/90. Range.
[0035]
When the olefin copolymer rubber and other rubber are used in combination as the rubber, the other rubber is preferably 40 parts by weight or less, preferably 100 parts by weight or less of the total amount of crystalline polyolefin and rubber. Is blended at a ratio of 5 to 20 parts by weight.
[0036]
The thermoplastic elastomer (A) preferably used in the present invention comprises crystalline polypropylene and ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber. These are present in a partially crosslinked state, and the weight blending ratio of crystalline polypropylene to rubber (crystalline polypropylene / rubber) is in the range of 70/30 to 10/90.
[0037]
The thermoplastic elastomer (A) may contain additives such as mineral oil softeners, heat stabilizers, antistatic agents, weathering stabilizers, anti-aging agents, fillers, colorants, and lubricants as necessary. , And can be blended as long as the object of the present invention is not impaired.
[0038]
As a more specific example of the thermoplastic elastomer (A) preferably used in the present invention,
70 to 10 parts by weight of crystalline polypropylene (A-1),
30 to 90 parts by weight of rubber (A-2) made of ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber [the total amount of components (A-1) and (A-2) is 100% by weight Part]
5 to 100 parts by weight of rubber (A-3) and / or mineral oil softener (A-4) other than this rubber (A-2)
And a thermoplastic elastomer in which the rubber (A-2) is crosslinked, which is obtained by dynamically heat-treating a mixture of the above in the presence of an organic peroxide.
[0039]
Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2, 5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Examples include carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.
[0040]
Among these, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert- Butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4- Bis (tert-butylperoxy) valerate is preferred, and 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.
[0041]
In the present invention, the organic peroxide is used in a proportion of 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on 100% by weight of the total amount of crystalline polyolefin and rubber.
[0042]
In the partial crosslinking treatment with the above organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane- Peroxy crosslinking aids such as N, N'-m-phenylene dimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate Polyfunctional methacrylate monomers such as, polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.
[0043]
By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has a good compatibility with the crystalline polyolefin and rubber, which are the main components of the cross-linked product, and has an action of solubilizing the organic peroxide. Therefore, a thermoplastic elastomer having a uniform crosslinking effect by heat treatment and a balance between fluidity and physical properties can be obtained.
[0044]
It is preferable to use the crosslinking aid or polyfunctional vinyl monomer as described above in a proportion of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the entire cross-linked product. When the blending ratio of the crosslinking aid or the polyfunctional vinyl monomer exceeds 2% by weight, the crosslinking reaction proceeds too quickly when the blending amount of the organic peroxide is large. On the other hand, when the amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as unreacted monomers in the thermoplastic elastomer, and the thermoplastic elastomer is heated during processing and molding. Changes in physical properties due to history may occur. Therefore, the crosslinking aid and the polyfunctional vinyl monomer should not be added in excess.
[0045]
The above “dynamic heat treatment” means kneading the above components in a molten state.
As the kneading device, a conventionally known kneading device, for example, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer, or the like is used. Among these, a non-open type kneading apparatus is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.
[0046]
The kneading is desirably performed at a temperature at which the half-life of the organic peroxide used is less than 1 minute. The kneading temperature is usually 150 to 280 ° C., preferably 170 to 240 ° C., and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The applied shear force is 100 sec as the shear rate.^-1Or more, preferably 500 to 10,000 sec^-1It is determined within the range.
[0047]
The thermoplastic elastomer (A) particularly preferably used in the present invention is partially crosslinked. This “partially crosslinked” means that the gel content measured by the following method is 20 to 98%. In the present invention, the gel content is preferably in the range of 40 to 98%.
[0048]
[Measurement method of gel content]
About 100 mg of a sample of thermoplastic elastomer is weighed and cut into 0.5 mm × 0.5 mm × 0.5 mm strips, and the resulting strips are then placed in 30 ml of cyclohexane in a sealed container at 23 ° C. Soak for 48 hours.
[0049]
Next, the sample is taken out on a filter paper and dried at room temperature until a constant weight is obtained for 72 hours or more.
A value obtained by subtracting the weight of the cyclohexane insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dry residue is defined as “corrected final weight (Y)”.
[0050]
On the other hand, the value obtained by subtracting the weight of the cyclohexane-soluble component (for example, softener) other than the polymer component and the weight of the cyclohexane-insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the sample is corrected. Initial weight (X) ”.
[0051]
Here, the gel content (cyclohexane insoluble matter) is determined by the following formula.
Gel content [wt%] = [corrected final weight (Y)] / [corrected initial weight (X)] × 100
Since the thermoplastic elastomer (A) used in the present invention is composed of crystalline polyolefin and rubber, it has excellent fluidity.
[0052]
The thermoplastic elastomer (A) as described above can be molded using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding or extrusion molding.
[0053]
Ultra-high molecular weight polyolefin composition (B)
Specific examples of the ultrahigh molecular weight polyolefin composition (B) used in the present invention include the following ultrahigh molecular weight polyolefin compositions.
[0054]
(1) a polyolefin (a) having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. in the range of 3.5 to 8.3 dl / g;
An olefin thermoplastic elastomer (b) comprising a crystalline olefin resin and an olefin rubber, and if necessary,
A polymer block (c-1) of styrene or a derivative thereof and an isoprene polymer block and / or an isoprene-butadiene copolymer block, which are bonded at 1,2-position and 3,4-position with respect to all isoprene units. A block copolymer (c) which may be hydrogenated and comprising a polymer and / or copolymer block (c-2) having an isoprene unit content of 40% or more, and / or
At least one component selected from the group consisting of higher fatty acid amide (d), silicone oil (e), ester (f) of aliphatic alcohol and dicarboxylic acid or monocarboxylic acid, and fluorine-based polymer (g);
A composition comprising:
[0055]
(2) Ultra high molecular weight polyolefin (a-1) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent of 7 to 40 dl / g, preferably 10 to 35 dl / g, and a 135 ° C. decalin solvent The intrinsic viscosity [η] measured in 0.1 to 5 dl / g, preferably consisting of low to high molecular weight polyolefin (a-2) in the range of 0.1 to 2 dl / g, The ultra high molecular weight polyolefin (a-1) is 15 to 40% by weight, preferably 18 to 35% by weight, based on 100% by weight of the total weight of the ultra high molecular weight polyolefin (a-1) and the polyolefin (a-2). And a polyolefin composition (a) ′ having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 3.5 to 8.3 dl / g,
An olefin thermoplastic elastomer (b) comprising a crystalline olefin resin and an olefin rubber, and if necessary,
The block copolymer (c), and / or
At least one component selected from the group consisting of higher fatty acid amide (d), silicone oil (e), ester (f) of aliphatic alcohol and dicarboxylic acid or monocarboxylic acid, and fluorine-based polymer (g);
A composition comprising:
[0056]
(3) A composition comprising the ultrahigh molecular weight polyolefin composition according to (1) or (2) above and 1 to 20% by weight of a liquid or solid lubricating oil per ultra high molecular weight polyolefin composition.
[0057]
[Polyolefin (a), ultrahigh molecular weight polyolefin (a-1) and polyolefin (a-2)]
The polyolefin (a) constituting the composition (1), the ultrahigh molecular weight polyolefin (a-1) and the polyolefin (a-2) constituting the composition (2) are, for example, ethylene, propylene, 1- Homopolymers or copolymers of α-olefins such as butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene Consists of. In the present invention, an ethylene homopolymer and a copolymer composed mainly of ethylene and composed of ethylene and another α-olefin are desirable.
[0058]
[Olefin-based thermoplastic elastomer (b)]
The said olefin type thermoplastic elastomer (b) can use the material similar to the olefin type thermoplastic elastomer (A) mentioned above. Components (b) and (A) may be exactly the same or different.
[0059]
[Block copolymer (c)]
The block copolymer (c) used in the present invention is a block (c-2) comprising a polymer block (c-1) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene-butadiene copolymer. And may be hydrogenated.
[0060]
The polymer component constituting the block (c-1) is styrene or a derivative thereof.
Specific examples of styrene derivatives include α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl- 4-Benzylstyrene, 4- (phenylbutyl) styrene and the like can be mentioned. As the polymer component constituting the block (c-1), styrene and α-methylstyrene are preferable.
[0061]
The polymer or copolymer constituting the block (c-2) is an isoprene polymer or an isoprene-butadiene copolymer, and is in the 1,2-position and 3,4-position with respect to the entire isoprene unit shown below. The content of the isoprene unit bonded at is 40% or more, preferably 45% or more.
[0062]
[Chemical 1]

[0063]
In the present invention, when the content of isoprene units bonded at 1,2-position and 3,4-position with respect to all isoprene units is 40% or more, thermoplasticity capable of providing a molded article having excellent scratch resistance. An elastomer can be obtained.
[0064]
The proportion of the polymer block (c-1) of styrene or a derivative thereof in the block copolymer (c) is preferably 5 to 50% by weight, more preferably 10 to 45% by weight. That is, the proportion of the isoprene polymer block or isoprene-butadiene copolymer block (c-2) is preferably in the range of 95 to 50% by weight, more preferably 90 to 55% by weight.
[0065]
In the present invention, a hydrogenated block copolymer (c) is preferred. When the hydrogenated block copolymer (c) is used, a thermoplastic elastomer capable of providing a molded article superior in weather resistance and heat resistance can be obtained.
The melt flow rate (MFR; ASTM D 1238, 230 ° C., 2.16 kg load, the same applies hereinafter) of the block copolymer (c) used in the present invention is preferably 0.01 to 30 g / 10 minutes, more preferably It exists in the range of 0.01-10 g / 10min. When the block copolymer (c) having a melt flow rate in the above range is used, a thermoplastic elastomer capable of providing a molded article having excellent scratch resistance can be obtained.
[0066]
As the block form of the block copolymer (c) used in the present invention, the form of block (c-1) -block (c-2) -block (c-1) is most preferable, but is not limited thereto. is not.
[0067]
Such a block copolymer (c) can be produced, for example, by the following method.
(1) A method of sequentially polymerizing styrene or a derivative thereof, isoprene or an isoprene-butadiene mixture using an alkyllithium compound as an initiator.
(2) A method of polymerizing styrene or a derivative thereof, then isoprene or an isoprene-butadiene mixture, and coupling this with a coupling agent.
(3) A method of sequentially polymerizing isoprene or an isoprene-butadiene mixture and then styrene or a derivative thereof using a dilithium compound as an initiator.
[0068]
Details of the method for producing the block copolymer (c) are described, for example, in JP-A-2-300250.
Moreover, if the block copolymer (c) obtained by the above methods is hydrogenated, the hydrogenated block copolymer (c) will be obtained. The hydrogenated block is an isoprene polymer block or an isoprene / butadiene copolymer block (c-2).
[0069]
In the present invention, the block copolymer (c) is preferably 5 to 60 parts by weight based on 100 parts by weight of the total amount of the components (a), (b) and (c), if necessary. Is used in a proportion of 10 to 50 parts by weight, more preferably 10 to 40 parts by weight.
[0070]
When the block copolymer (c) is used in the above ratio, a thermoplastic elastomer that can provide a molded article having particularly excellent wear resistance can be obtained.
[Higher fatty acid amide (d), silicone oil (e), ester (f) and fluorine-based polymer (g)]
Specific examples of the higher fatty acid amide (d) used in the present invention include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behemic acid amide;
Unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brassic acid amide, elaidic acid amide;
Examples thereof include bis fatty acid amides such as methylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis stearic acid amide, and ethylene bis oleic acid amide. Of these, erucic acid amide, oleic acid amide, and ethylenebisoleic acid amide are preferable.
[0071]
Specific examples of the silicone oil (e) used in the present invention include dimethyl silicone oil, phenylmethyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, and modified silicone oil. Of these, dimethyl silicone oil and phenylmethyl silicone oil are preferably used.
[0072]
The kinematic viscosity [JIS K 2283, 25 ° C.] of the silicone oil (e) is in the range of 10 to 30,000 cSt, preferably 50 to 10,000 cSt, more preferably 100 to 5,000 cSt.
[0073]
The ester (f) used in the present invention is an ester of an aliphatic alcohol and a dicarboxylic acid or a monocarboxylic acid.
Specific examples of such esters (f) include esters of cetyl alcohol and acetic acid, esters of cetyl alcohol and propionic acid, esters of cetyl alcohol and butyric acid, esters of beef tallow alcohol and acetic acid, tallow alcohol Ester of beryllic acid and propionic acid, ester of beef tallow alcohol and butyric acid, ester of stearyl alcohol and acetic acid, ester of stearyl alcohol and propionic acid, ester of stearyl alcohol and butyric acid, ester of distearyl alcohol and phthalic acid, Glycerol monooleate, glycerin monostearate, 12-hydroxystearate, glycerin tristearate, trimethylolpropane tristearate, pentaerythritol tetrastearate, butyl stearate, isobutyl stearate , Stearic acid ester, oleic acid ester, behenic acid ester, calcium soap-containing ester, isotridecyl stearate, cetyl palmitate, cetyl stearate, stearyl stearate, behenyl behenate, montanic acid ethylene glycol ester, Examples include glycerin montanate, pentaerythritol ester of montanate, and montanic acid ester containing calcium. Among these, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, stearic acid ester, and montanic acid glycerin ester are preferable. Particularly preferred are esters of distearyl alcohol and phthalic acid, glycerin monostearate, and glycerin montanate.
[0074]
Specific examples of the fluorine-based polymer (g) used in the present invention include polytetrafluoroethylene and vinylidene fluoride copolymer. Of these, polytetrafluoroethylene is preferred.
[0075]
In the present invention, at least one component selected from the group consisting of the above higher fatty acid amide (d), silicone oil (e), ester (f), and fluorine-based polymer (g) is used as necessary. , 0.01 to 10 parts by weight, preferably 100 parts by weight of the total amount of polyolefin (a) or polyolefin composition (a) ′, olefinic thermoplastic elastomer (b) and block copolymer (c), Is used in a proportion of 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight. Since the said block copolymer (c) is an arbitrary component, it may become 0 weight part.
[0076]
[Liquid or solid lubricant]
As the liquid lubricating oil used in the composition (3), petroleum-based lubricating oil, synthetic lubricating oil and the like are used.
[0077]
Specifically, liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, cylinder oil and the like are used as the petroleum-based lubricating oil.
Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil, silicone Oil is used.
[0078]
Specifically, as the solid lubricating oil used in the composition of (3), specifically, graphite and molybdenum disulfide are mainly used. In addition, boron nitride, tungsten disulfide, lead oxide, glass powder Metal soaps can also be used. The solid lubricating oil can be used alone or in combination with a liquid lubricating oil, and can be blended with the ultrahigh molecular weight polyolefin in the form of powder, sol, gel, suspension, etc.
[0079]
In the ultrahigh molecular weight polyolefin composition (B) used in the present invention, a mineral oil softener, a heat stabilizer, an antistatic agent, a weathering stabilizer, an antiaging agent, a filler, a colorant, Additives such as a lubricant can be blended within a range that does not impair the object of the present invention.
[0080]
Since the ultrahigh molecular weight polyolefin composition (B) of the above (1) to (3) can be co-extruded and laminated with the thermoplastic elastomer (A), the film ( Sheet) The thermoplastic elastomer (A) layer and the ultrahigh molecular weight polyolefin composition (B) layer can be directly laminated without going through the molding step, which is economical.
[0081]
On the other hand, an ultrahigh molecular weight polyolefin, for example, an ultrahigh molecular weight polyolefin (a-1) alone having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. in the above (2) in the range of 7 to 40 dl / g, Coextrusion laminating with the thermoplastic elastomer (A) cannot be performed. Therefore, at the time of laminating the thermoplastic elastomer layer and the ultrahigh molecular weight polyolefin layer, at least one of them is previously formed into a film (sheet). It is necessary and is inferior in economic efficiency as compared with the case of the ultra-high molecular weight polyolefin composition (B).
[0082]
In the glass run channel according to the present invention, the draining portion 3 is preferably made of the same material as the glass run channel body 2.
When the glass run channel main body 2 is made of a thermoplastic elastomer (A), it is sufficient in terms of durability and bonding strength with the sliding resin layer 9 if the draining portion 3 is also formed of the same material. Withstand practical use.
[0083]
The shark skin (shark skin) that can be used in the glass run channel according to the present invention can be expressed at the time of molding by appropriately selecting the properties of the raw thermoplastic elastomer (A).
[0084]
The appearance of the obtained shark skin is different from the melt fracture that may be seen during extrusion molding of resins and elastomers, and the skin of the molded product is periodically roughened to produce fine irregularities.
[0085]
Further, it is necessary that the sharkskin appears on the surface of the slippery resin layer 9 applied on the sharkskin, and the thickness of the slippery resin layer 9 is usually 3 to 50 μm. Laminate. In the present invention, the thickness of the slipping resin layer 9 can be further increased or decreased as necessary.
[0086]
In addition, since the site | part which the draining part 3 contacts with the window glass 12 generally differs at the time of the entrance and exit of the window glass 12, it is coated with the ultrahigh molecular weight polyolefin composition (B) and the shark applied as necessary The skin is preferably formed in a relatively wide range of the draining portion 3.
[0087]
In the specific example shown in FIG. 1, the glass run channel main body 2 has a portion 16 in contact with the end portion of the window glass. The portion 16 also has a glass run channel made of the thermoplastic elastomer (A). A slipping resin layer 9 made of the ultrahigh molecular weight polyolefin composition (B) can be provided on the surface of the main body 2.
[0088]
Furthermore, in the present invention, napping may exist on the surface of the sliding resin layer 9. As for the above-mentioned raising decoration method, (a) buffing with emery paper and raising the surface of the sliding resin layer, (b) passing through the needle cloth roll and raising the sliding resin layer surface. A method of decorating, (c) a method of sanding with a belt sander or a drum sander to decorate the surface of the slipping resin layer, and (d) a thermal micrometer described in JP-A-62-275732. Conventionally known brushed decoration methods such as a method of brushing the surface of the sliding resin layer by colliding the body are used.
[0089]
【The invention's effect】
According to the present invention, it is possible to omit the adhesive application process, the adhesive curing or baking process, and the embossing process before and after the process. As a result, the number of processes can be reduced, and the working time can be reduced. Because it can be shortened, it is possible to produce a glass run channel with excellent economy, durability, close contact with the window glass when closed, and light sliding performance during opening and closing operations. It is possible to provide a glass run channel that does not cause wrinkles in the ultrahigh molecular weight polyolefin composition layer even when bent or folded.
[0090]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[0091]
[Example 1]
Ethylene content 70mol%, iodine number 12, Mooney viscosity ML_{1 + 4} (100 ° C.) 120 ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [hereinafter abbreviated as EPDM] 80 parts by weight, MFR (ASTM D 1238-65T, 230 ° C.) 13 g / 10 min, density 0.91 g / cm^Three 20 parts by weight of polypropylene [hereinafter abbreviated as PP] was kneaded in a nitrogen atmosphere at 180 ° C. for 5 minutes using a Banbury mixer, and the kneaded product was passed through a roll to form a sheet, which was then used as a sheet cutter. The square pellets were manufactured by cutting.
[0092]
Next, this rectangular pellet, 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene [hereinafter abbreviated as peroxide], and 0.5 parts by weight of divinylbenzene [hereinafter abbreviated as DVB] The mixture was stirred and mixed with a Henschel mixer.
[0093]
Next, this mixture was extruded at 220 ° C. in a nitrogen atmosphere using a twin screw extruder having L / D = 40 and a screw diameter of 50 mm to obtain a thermoplastic elastomer (A-1).
[0094]
The gel content of the obtained thermoplastic elastomer (A-1) was 85% by weight as determined by the above method.
The thermoplastic elastomer (A-1) is extruded at a temperature of 230 ° C. to form a glass run channel main body and a draining portion, and the intrinsic viscosity [η] measured in a 135 ° C. decalin solvent is 28 dl on the surface. / G of ultra high molecular weight polyethylene (a-1) 23% by weight and low molecular weight polyethylene (a-2) 77% by weight having an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.73 dl / g. Polyethylene composition (a) ′ [Intrinsic viscosity [η] measured in decalin at 135 ° C .: 7.0 dl / g] 75 parts by weight and thermoplastic elastomer (A-1) 25 parts by weight using the above-mentioned twin screw extruder. The kneaded ultrahigh molecular weight polyethylene composition (B-1) was coextruded at 250 ° C. to obtain a glass run channel.
[0095]
The obtained glass run channel has a substantially trapezoidal shape. The total length of the inclined portion and the horizontal portion of the glass run channel 1 fixed to the window frame 13 in FIG. 1, the bottom outer width of the main body 2 is 15 mm, the side outer height is 20 mm, the length of the draining portion 3 is 10 mm, and is substantially equal to the cross-sectional shape shown in FIG. The average thickness of the molecular weight polyethylene composition layer was 30 μm.
[0096]
The obtained glass run channel was attached to a test window frame, and a window glass having a thickness of 3.2 mm was fitted thereto, and an endurance test (window glass up and down repeated test) was performed. As a result, this glass run channel withstood the 50,000 times window glass up-and-down repetition test and maintained its function as a glass run channel.
[0097]
However, the conventional glass run channel (the window glass sliding part has a laminated structure in which a nylon film is bonded to a soft vinyl chloride resin layer) is broken at the window glass contact surface after 25,000 times. As a result, the frictional resistance with the window glass increased significantly, making it unusable.
[0098]
In addition, the straight portion of the glass run channel obtained in Example 1 was cut into a length of 30 cm and bent 180 degrees from the center with the draining portion on the outside. The ultrahigh molecular weight polyethylene composition layer (sliding resin layer) There was no noticeable wrinkle.
[0099]
[Example 2]
In Example 1, 60 parts by weight of polyethylene composition (a), 15 parts by weight of thermoplastic elastomer (A-1), and styrene / isoprene / styrene block copolymer [styrene content: 20% by weight, isoprene polymer The content of isoprene units bonded at the 1,2- and 3,4-positions in the portion: 55%, melt flow rate: 2.5 g / 10 min] (c) 25 parts by weight of the above-described twin-screw extruder This was carried out in the same manner as in Example 1 except that the ultrahigh molecular weight polyethylene composition (B-2) kneaded in (1) was used.
[0100]
Using the obtained glass run channel, the window glass up / down repetition test was conducted in the same manner as in Example 1. As a result, it withstood 50,000 times. In addition, no remarkable wrinkle was observed in the ultrahigh molecular weight polyethylene composition layer even with respect to the above-described bending.
[0101]
[Example 3]
In Example 1, in addition to EPDM and PP, 10 parts by weight of butyl rubber [manufactured by Esso, IIR-065, unsaturation degree 0.8 mol%, hereinafter abbreviated as IIR] and paraffinic process oil [Idemitsu Kosan Co., Ltd. Product name Diana Process Oil] The same procedure as in Example 1 was conducted except that 30 parts by weight of the thermoplastic elastomer (A-2) was produced. The gel content of the obtained thermoplastic elastomer (A-2) was 70%.
[0102]
The resulting glass run channel withstood 50,000 repetitions of the window glass up / down repetition test. In addition, no remarkable wrinkles were observed in the ultrahigh molecular weight polyethylene composition layer with respect to the above-described bending.
[0103]
[Example 4]
In Example 1, in addition to 75 parts by weight of the polyethylene composition (a) and 25 parts by weight of the thermoplastic elastomer (A-1), 0.5 parts by weight of erucamide is added to the ultrahigh molecular weight polyethylene composition (B-3). ) Was carried out in the same manner as in Example 1, except that
[0104]
The resulting glass run channel withstood 50,000 repetitions of the window glass up / down repetition test. In addition, no remarkable wrinkle was observed in the ultrahigh molecular weight polyethylene composition layer even with respect to the above-described bending.
[0105]
[Comparative Example 1]
In Example 1, it carried out like Example 1 except having used polyethylene composition (a) 'independently instead of ultrahigh molecular weight polyethylene composition (B-1).
[0106]
The resulting glass run channel withstood 50,000 repetitions of the window glass up / down repetition test. However, with respect to the above-described bending, wrinkles occurred in the ultrahigh molecular weight polyethylene composition layer, and whitening was observed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a glass run channel according to the present invention.
2 is an enlarged cross-sectional view of a contact portion of the glass run channel shown in FIG. 1 with a window glass.
FIG. 3 is a view for explaining attachment of a glass run channel to an automobile door.
FIG. 4 is a cross-sectional view showing a state of a glass run channel when the window glass is opened.
FIG. 5 is a cross-sectional view showing a state of the glass run channel when the window glass is closed.
[Explanation of symbols]
1 ・ ・ ・ ・ ・ Glass run channel
1a ... bottom wall
1b: side wall
1c: Groove
2 ・ ・ ・ ・ ・ Glass run channel body
3 ...... Drainer
4 ... Window glass contact area
7 ・ ・ ・ ・ ・ Base layer made of thermoplastic elastomer
8... Base layer surface having a repetitive pattern of minute irregularities (applied as necessary)
9 ・ ・ ・ ・ ・ Sliding resin layer made of ultrahigh molecular weight polyolefin composition
10 ... Surface of the resin layer having a repetitive pattern of minute irregularities (applied as necessary)

Claims (5)

A glass run channel body comprising a bottom wall and side walls extending from both ends of the bottom wall, having a substantially U-shaped cross section and having grooves formed therein, and the bottom wall from the vicinity of the ends of both side walls of the glass run channel body A glass run channel composed of a tongue-shaped drainer stretched so as to be close to each other toward the
A window glass contact portion which is a surface in contact with the window glass of the draining portion,
A thermoplastic elastomer (A) layer composed of crystalline polyolefin and rubber, an ultrahigh molecular weight polyolefin composition (B) layer, and
The ultrahigh molecular weight polyolefin composition (B) layer is configured to come into contact with the window glass,
The ultrahigh molecular weight polyolefin composition (B) is
Ultra high molecular weight polyolefin (a-1) having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within a range of 7 to 40 dl / g, and an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 0. 0.1 to 5 dl / g of the polyolefin (a-2), and the ultrahigh molecular weight polyolefin (a-1) comprises the ultrahigh molecular weight polyolefin (a-1) and the polyolefin (a- 2) and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g. polyolefins located within (a) '10 to 90 parts by weight, and the olefin-based thermoplastic elastomer comprising a crystalline olefin resin and an olefin rubber (b) 90 to 10 parts by weight [the component (a)' and (b) Total glass run channel, characterized in that it consists of 100 parts by weight. The ultrahigh molecular weight polyolefin composition (B) is
Ultra high molecular weight polyolefin (a-1) having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within a range of 7 to 40 dl / g, and an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 0. 0.1 to 5 dl / g of the polyolefin (a-2), and the ultrahigh molecular weight polyolefin (a-1) comprises the ultrahigh molecular weight polyolefin (a-1) and the polyolefin (a- 2) and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g. The polyolefin composition (a) within 10 to 90 parts by weight,
85 to 5 parts by weight of an olefin thermoplastic elastomer (b) composed of a crystalline olefin resin and an olefin rubber, a polymer block (c-1) of styrene or a derivative thereof, an isoprene polymer block and / or isoprene A butadiene copolymer block in which the content of isoprene units bonded at 1,2-position and 3,4-position with respect to all isoprene units is 40% or more and / or copolymer block ( c-2) optionally hydrogenated block copolymer (c) 5 to 60 parts by weight [total of components (a) ′, (b) and (c) is 100 parts by weight] The glass run channel according to claim 1 . The ultra-high molecular weight polyolefin composition (B) further comprises a higher fatty acid amide (d), a silicone oil (e), an ester (f) of an aliphatic alcohol and a dicarboxylic acid or a monocarboxylic acid, and a fluorine-based polymer (g). at least one component selected from the group consisting of, the relative ultra high molecular weight polyolefin composition (B) 100 parts by weight, claim 1, characterized by containing from 0.01 to 10 parts by weight or 2. The glass run channel according to 2. The olefinic thermoplastic elastomer (b) constituting the ultrahigh molecular weight polyolefin composition (B) is:
70 to 10 parts by weight of crystalline polypropylene (A-1),
30 to 90 parts by weight of rubber (A-2) made of ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber [the total amount of components (A-1) and (A-2) is 100 parts by weight the to] from become mixture obtained by dynamic heat treatment in the presence of an organic peroxide, claim 1-3 in which the rubber (a-2) is characterized in that it is a thermoplastic elastomer which is crosslinked The glass run channel according to any one of the above. The ultra high molecular weight polyolefin composition (B) is ultra high molecular weight polyolefin composition (B) per 1 to 20% by weight of the claims 1-4, which is characterized by containing the liquid to solid lubricants The glass run channel according to any one of the above.

Images