JP2004155942A - Resin composition, manufacturing method therefor, molded article therewith, and automobile part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent properties including rigidity, heat resistance and thermal expansion resistance, and to provide a method for manufacturing the composition. <P>SOLUTION: This resin composition has an oxide compound (B) with a surface having a polar group and, partly, a hydrophobic group, dispersed in an olefin resin (A) having a polar group. This resin composition has excellent properties including rigidity, heat resistance and thermal expansion resistance, and is particularly useful for interior/exterior parts as well as for outer panels for vehicles. <P>COPYRIGHT: (C)2004,JPO

Description

【００３４】
本発明において、酸化化合物（Ｂ）の表面の表面の少なくとも一部に疎水基を導入する反応条件としては、所望の疎水基を酸化化合物（Ｂ）の表面に導入できる条件であれば特に制限されない。酸化化合物（Ｂ）に、所望の疎水基導入率が得られる量の上記した所望のシラン系化合物やカチオン系界面活性剤などの疎水基導入剤を添加し、適当な温度、圧力条件下で反応させればよい。尚、この際、反応速度を上げるために適当な酸触媒を添加してもよいし、分散安定性を向上させるため界面活性剤などを添加してもよい。さらに、上記反応は、無溶媒下であるいは溶媒中で行われてもよいが、好ましくは溶媒中で行われる。この際使用できる溶媒としては、後述するポリマーとの混練工程を考慮すると水が好ましいが、メチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール系溶媒、メチルエチルケトン等のケトン系溶媒、酢酸エチル等のエステル系溶媒などの極性有機溶媒、これら極性有機溶媒と水の混合溶媒、またはトルエンなどの非極性有機溶媒を用いてもよい。
【００３５】
本発明において、酸化化合物（Ｂ）の表面に極性基及び一部疎水基を導入する反応においては、その反応順序は、特に制限されず、酸化化合物（Ｂ）の表面に所望の極性基及び一部疎水基を導入できれば、特に制限されず、極性基および疎水基を同時に導入しても、極性基をまず導入した後、疎水基を導入しても、あるいは疎水基をまず導入した後、極性基を導入しても、いずれでもよい。なお、上述したように、酸化化合物（Ｂ）としてシリカ化合物を使用する場合には、シリカ化合物はその表面に多数のシラノール基（Ｓｉ−ＯＨ）、即ち、極性基（水酸基）を有しているため、極性基の導入のための処理を特に行なうことなく、そのまま疎水基の導入処理に使用してもよい。
【００３６】
本発明における酸化化合物（Ｂ）の形状は、特に限定されず、一般的な略球状だけでなく、直方体や板状、繊維のような直線形状、枝分かれした分岐形状なども用いることができる。
【００３７】
本発明における酸化化合物（Ｂ）の大きさもまた、特に限定されないが、ポリマーナノコンポジットとして目的とする性能を発現させるためには、少なくとも一辺がナノオーダーであることが必要である。ここで、「少なくとも一辺がナノオーダー」とは、酸化化合物（Ｂ）の形状が、略球状ならその直径、直方体や板状ならいずれかの少なくとも一辺が、または繊維のような直線形状や枝分かれした分岐形状ならその太さ断面の少なくとも短径が、ナノオーダーであることを意味する。ここでいう「ナノオーダー」の範囲は、特に限定されないが、物性の向上、分散のし易さ、入手の容易さ、コスト面などから、１〜２００ｎｍの範囲が好ましく、より好ましくは１〜１００ｎｍがよい。
【００３８】
本発明における酸化化合物（Ｂ）の樹脂組成物に対する配合量は、所望の均一分散性や所望の用途での要求特性（例えば、剛性、耐熱性及び耐熱膨張性などの）が得られるような量であれば特に制限されないが、重量分率で０．１〜６０質量％、より好ましくは１〜３０質量％が好ましい。０．１質量％未満では、酸化化合物（Ｂ）による配合効果が少なく、得られる樹脂組成物の剛性、耐熱性及び耐熱膨張性などの物性の向上がほとんど認められない。逆に、６０質量％を超えると、比重の増加が無視できなくなるばかりでなく、コスト面でも不利となり、オレフィン系樹脂（Ａ）の低コスト、低比重といった特長が損なわれる。また衝撃強度の低下も無視できないものとなる。一般に、ポリマーに充填材を大量に配合すると衝撃強度が減少するが、本発明の樹脂組成物はナノオーダーの充填材を用い、かつ充填材とポリマー間の相互作用が大きいため、衝撃強度の低下は実用上小さいが、６０質量％を超えるとこれが無視できなくなる。
【００３９】
本発明におけるオレフィン系樹脂（Ａ）とは、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ノルボルネン樹脂に代表される脂環式ポリオレフィン、およびこれらの共重合体、エチレン／プロピレンゴムに代表されるゴム成分との共重合体もしくはブレンド品などに、極性基を導入したものを指す。本発明においてはこれらオレフィン系樹脂の何れを用いてもよいが、コスト、汎用性、入手のし易さなどから、ポリプロピレン、ポリエチレン、若しくはポリプロピレンとポリエチレンの共重合体でかつ極性基を有するもの；またはポリプロピレン、ポリエチレン、若しくはポリプロピレンとポリエチレン共重合体のいずれか１種ををゴム変性したものでかつ極性基を有するものが特に好ましい。尚、本発明におけるオレフィン系樹脂（Ａ）に、非晶性のポリプロピレン、ポリメチルペンテン、脂環式ポリオレフィンなどの透明性の高いオレフィン系樹脂に極性基を導入したものを選択し、かつ酸化化合物（Ｂ）の長径を可視光波長である３８０ｎｍ以下とすることで、剛性、耐熱性、耐熱膨張性とともに、透明性にも優れた樹脂組成物を得ることができる。また、本発明において、オレフィン系樹脂（Ａ）は、単独で使用されてもあるいは２種以上の混合物の形態で使用されてもよい。
【００４０】
本発明におけるオレフィン系樹脂（Ａ）の有する極性基は、前述の充填材とポリマー間の相互作用向上のために必須のもので、前述した酸化化合物（Ｂ）の極性基と水素結合、イオン結合、共有結合などの化学的結合を生じ、相互作用を向上する。また、この相互作用により、分散性も相乗的に向上する。ここで、極性基とは、前述した酸化化合物（Ｂ）の極性基と化学的結合を生じるものであれば特に限定はされないが、相互作用の大きさ、樹脂組成物の物性のバランス、極性基の導入のし易さ、入手の容易さなどの理由から、無水ジカルボキシル基、カルボキシル基、カルボニル基、エポキシ基、アミノ基、アミド基、水酸基などが好ましく挙げられる。この際、オレフィン系樹脂（Ａ）の有する極性基は、単独で存在してもあるいは２種以上が共存してもいずれでもよい。ここで、無水ジカルボキシル基とは、隣接する２つのカルボキシル基が脱水縮合して無水化した基を指す。
【００４１】
オレフィン系樹脂に極性基を導入して本発明によるオレフィン系樹脂（Ａ）とする方法は特に限定されないが、例えば、所望の極性基を有する不飽和単量体を、重合開始剤などとともにオレフィン系樹脂に加え共重合させる方法が挙げられる。共重合の形態としてはランダム共重合、ブロック共重合、グラフト共重合などいずれでもよい。尚、極性基をホモポリマー中の全ての分子に導入してオレフィン系樹脂（Ａ）としてもよいし、もしくは極性基を導入したオレフィン系ポリマーを極性基を持たないホモポリマーにブレンドしオレフィン系樹脂（Ａ）としてもよい。後者の方法は、市販の極性基が予め導入されたオレフィン系ポリマーを、ブレンダーなどを用いてホモポリマーにブレンドすることで実現できるため、より簡便な方法といえ好ましい。この際、極性基は、後述する極性基濃度の範囲で存在することが好ましい。上記方法において、極性基を有する不飽和単量体の具体的な例としては、無水ジカルボキシル基を有するものとしては、無水マレイン酸、無水イタコン酸、及び無水メチルマレイン酸などが；カルボキシル基を有するものとしては、マレイン酸、イタコン酸、メチルマレイン酸、アクリル酸、メタクリル酸、クロトン酸、及びイソクロトン酸などが；カルボニル基を有するものとしては、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、及びメタクリル酸エチルなどが；エポキシ基を有するものとしては、アクリル酸グリシジル、及びメタクリル酸グリシジルなどが；アミノ基を有するものとしては、メタクリル酸アミノエチル、及びメタクリル酸ジエチルアミノエチルなどが；アミド基を有するものとしては、アクリルアミド、及びメタクリルアミドなどが；水酸基を有するものとしては、アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシプロピル、及びアリルアルコールなどが、それぞれ、挙げられる。
【００４２】
本発明において、極性基を導入したポリマー及び極性基を持たないポリマーの添加量は、特に制限されるものではないが、好ましくは、オレフィン系樹脂（Ａ）に含まれる極性基の濃度が、その極性基を含む不飽和単量体換算で、オレフィン系樹脂（Ａ）に対する重量分率として表わされる場合において、好ましくは０．００１〜１０質量％、より好ましくは０．００２〜５質量％の範囲となるような量であることが好ましい。ここで、「その極性基を含む不飽和単量体換算」とは、上述のように所望の極性基をこれを有する不飽和単量体を共重合させて導入すると仮定し、所望の極性基を導入するために用いたその不飽和単量体の分子量を用いて濃度を求めることを意味する。０．００１質量％未満では、上述した酸化化合物（Ｂ）の極性基との相互作用点が少なく、均一分散性も低下し、十分な物性が得られない。また、１０質量％を超えると、吸湿性が大きくなり、耐久性や寸法安定性といった物性に悪影響を及ぼすばかりでなく、ホモポリマーに比べ製造コストが高くなり、コスト的にも不利となる。
【００４３】
なお、本発明の樹脂組成物は、オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）を必須成分として、これら以外に、必要に応じて様々な添加剤、例えば帯電防止剤、酸化防止剤、熱安定剤、紫外線吸収剤、酸化防止剤、難燃剤、顔料、着色剤などを含んでもよい。
【００４４】
本発明の樹脂組成物の製造方法は、特に限定されず、公知の方法を単独であるいは組み合わせて使用できる。例えばオレフィン系樹脂（Ａ）を適当な溶剤に溶解し、これに酸化化合物（Ｂ）を加え十分撹拌した後、溶剤を除去する方法が使用できる。より均一分散性を向上するためには、下記の２つの製造方法のいずれかが好ましく使用される。
【００４５】
第一の方法は、オレフィン系樹脂（Ａ）を、酸化化合物（Ｂ）を溶媒（Ｓ）に均一分散した溶液（Ｃ）と、接触させながら混練した後、溶媒（Ｓ）を除去する製造方法である。したがって、本発明の第二は、極性基を有するオレフィン系樹脂（Ａ）を、表面に極性基および一部疎水基を有する酸化化合物（Ｂ）を溶媒（Ｓ）に均一分散した溶液（Ｃ）と、接触させながら混練した後、該溶媒（Ｓ）を除去することを含むことを特徴とする、樹脂組成物の製造方法である。本方法によると、酸化化合物（Ｂ）は、混練前に予め溶媒（Ｓ）に均一分散した状態であり、この状態を維持したままオレフィン系樹脂（Ａ）に混練されるため、生成する樹脂組成物でも良好な均一分散性が得られる。従来の技術の項で取り上げた層状クレイは溶媒に溶解しても、膨潤し層間距離が拡大はするものの、完全な剥離は困難であり、混練前の段階ではナノオーダーの充填材が凝集した状態に近いものである。このため、均一分散性の大小はその後の混練工程に大きく左右されることになる。これに対して、本発明の方法によると、このような問題が生じずに、酸化化合物（Ｂ）がオレフィン系樹脂（Ａ）中に均一に分散でき、これにより樹脂組成物に剛性、耐熱性及び耐熱膨張性などの物性が付与される。
【００４６】
ここで、オレフィン系樹脂（Ａ）と溶液（Ｃ）を接触する際の温度は、オレフィン系樹脂（Ａ）の溶融温度付近が好ましく、より好ましくはオレフィン系樹脂（Ａ）の溶融温度から２０℃低い温度（即ち、オレフィン系樹脂（Ａ）の溶融温度−２０℃）からオレフィン系樹脂（Ａ）の分解開始温度の範囲である。オレフィン系樹脂（Ａ）の溶融温度から２０℃低い温度（オレフィン系樹脂（Ａ）の溶融温度−２０℃）未満の温度で接触させると、オレフィン系樹脂（Ａ）と溶液（Ｃ）との混合が不十分になり、均一分散が十分行なわれない場合がある。尚、混練に用いる装置は特に限定されず、単軸や二軸の押出し機やオートクレーブを用いて行なえるが、均一分散性の面から二軸押出し機が特に好ましく、溶液（Ｃ）を加圧添加できるポンプと添加口、また溶媒（Ｓ）を除去できるベントを備えたものが特に好ましい。
【００４７】
上記第一の方法で用いられる溶媒（Ｓ）は、酸化化合物（Ｂ）を均一分散し得るものなら特に限定されず、単一溶媒でもあるいは混合溶媒でもよいが、８０質量％以上が水であることがより好ましい。水の存在量が８０質量％未満である場合、つまり水以外の溶媒（好ましくは有機溶媒）が２０質量％以上存在すると、混練設備の防爆対策や局所排気設備、溶媒回収設備が必要になり、また混練後の溶媒の除去にも多大な労力を伴うことになる。水以外の他の溶媒としては、メチルアルコール、エチルアルコール、イソプロピルアルコールなどのアルコール系溶媒、メチルエチルケトンなどのケトン系溶媒、酢酸エチルなどのエステル系溶媒といった極性有機溶媒が好ましく挙げられる。
【００４８】
上記第一の方法で用いられる溶液（Ｃ）に含まれる酸化化合物（Ｂ）の濃度は、重量分率で、１〜７０質量％、より好ましくは１０〜５０質量％の範囲が好ましい。この際、酸化化合物（Ｂ）の濃度が１質量％未満では、樹脂組成物に対する酸化化合物（Ｂ）の所望の配合量を得るために大量の溶液（Ｃ）が必要となり、混練時間や装置長の増大を招き、また混練後の脱気にも長時間を要するため、工数的にもコスト的にも好ましくない。また、７０質量％を超えると、溶媒（Ｓ）への酸化化合物（Ｂ）の均一分散がしづらくなり、また均一分散できたとしても再凝集し易くなる恐れがある。
【００４９】
次に、第二の方法としては、オレフィン系樹脂（Ａ）を、酸化化合物（Ｂ）を溶媒（Ｓ）に均一分散した溶液（Ｃ）および超臨界流体（Ｄ）と、接触させながら混練した後、溶媒（Ｓ）及び超臨界流体（Ｄ）を除去する製造方法があり、本方法は、第一の方法に超臨界流体（Ｄ）を加えた方法である。したがって、本発明の第三は、極性基を有するオレフィン系樹脂（Ａ）を、表面に極性基および一部疎水基を有する酸化化合物（Ｂ）を溶媒（Ｓ）に均一分散した溶液（Ｃ）および超臨界流体（Ｄ）と、接触させながら混練した後、該溶媒（Ｓ）と超臨界流体（Ｄ）とを除去することを含むことを特徴とする、樹脂組成物の製造方法である。なお、下記説明において、特記しない限り、溶媒（Ｓ）や溶媒（Ｃ）における酸化化合物（Ｂ）の濃度などは、上記第一の方法における説明と同様であるため、ここでは、説明を省略する。
【００５０】
上記第二の方法において、超臨界流体とは、物質ごとに特有の臨界圧力：Ｐｃおよび臨界温度：Ｔｃを越えた領域で存在する、気体や液体と異なる、もしくは双方の性質を併せ持つ分子集合体である。超臨界流体の特徴の一つとしては、高拡散性、高溶解性（高可塑性）が挙げられ、また両親媒性的な挙動を示すため、第一の方法に超臨界流体を加えることで、オレフィン系樹脂（Ａ）と酸化化合物（Ｂ）の相溶性がより向上し、酸化化合物（Ｂ）の均一分散性がさらに向上できるという利点がある。尚、理論的な詳細は未だ解明されていないが、本発明のように超臨界流体（Ｄ）と溶媒（Ｓ）を併せて用いることにより、エントレーナ効果が発現し、超臨界流体（Ｄ）を単独で用いた場合より酸化化合物（Ｂ）の均一分散性は向上する。また、超臨界流体は、特開平１１−１８１０８７号公報などに記載されているように溶媒の乾燥にも効果的であり、後工程なしで樹脂組成物中から溶媒（Ｓ）をほぼ完全に除去可能である点も特筆される。
【００５１】
第二の製造方法で用いられる超臨界流体（Ｄ）としては、特に制限されず、特開平１１−１８１０８７号公報などに記載される公知の超臨界流体が使用できる。具体的には、二酸化炭素、水、窒素、窒素酸化物、アンモニア、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ジメチルブタン、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサン、ジエチルエーテル、ベンゼン、トルエン、ハロゲン化炭化水素類等の超臨界流体が挙げられる。これらのうち、作業性や安全性、臨界温度：Ｔｃが樹脂の溶融温度や分解開始温度より低く、かつ混練後に脱気する際も作業環境にできるだけ優しく、低コストである点を考慮すると、超臨界二酸化炭素が最も好ましい。
【００５２】
また、本発明において、オレフィン系樹脂（Ａ）と、溶液（Ｃ）及び超臨界流体（Ｄ）とを接触する際の温度は、第一の製造方法と同様、オレフィン系樹脂（Ａ）の溶融温度付近が好ましく、より好ましくはオレフィン系樹脂（Ａ）の溶融温度から５０℃低い温度（即ち、オレフィン系樹脂（Ａ）の溶融温度−５０℃）からオレフィン系樹脂（Ａ）の分解開始温度の範囲である。但し、上述の通り、温度ｔは、臨界温度：Ｔｃ以上であることが必須である。この際、オレフィン系樹脂（Ａ）の溶融温度から５０℃低い温度（オレフィン系樹脂（Ａ）の溶融温度−５０℃）未満の温度で接触させると、オレフィン系樹脂（Ａ）と溶液（Ｃ）及び超臨界流体（Ｄ）との混合が不十分になり、均一分散が十分行なわれない場合がある。
【００５３】
上記第二の方法において、超臨界流体（Ｄ）の導入量は、オレフィン系樹脂（Ａ）と酸化化合物（Ｂ）の相溶性がより向上でき、酸化化合物（Ｂ）の均一分散性がさらに向上できるような量であれば特に制限されないが、好ましくは、オレフィン系樹脂（Ａ）に対して、１〜２０質量％の範囲である。この際、超臨界流体（Ｄ）の導入量が１質量％未満であると、均一分散性が不十分である場合があり、逆に、２０質量％を超えると、せん断応力が低下し均一分散性が低下する場合がある。なお、本発明において、溶液（Ｃ）及び超臨界流体（Ｄ）の添加順序は、特に限定されず、溶液（Ｃ）及び超臨界流体（Ｄ）を同時にオレフィン系樹脂（Ａ）に添加・混練しても、あるいは溶液（Ｃ）をまずオレフィン系樹脂（Ａ）に添加・混練した後、超臨界流体（Ｄ）をさらに添加・混練しても、あるいは超臨界流体（Ｄ）をまずオレフィン系樹脂（Ａ）に添加・混練した後、溶液（Ｃ）をさらに添加・混練しても、いずれでもよい。
【００５４】
第二の製造方法で用いる溶液（Ｃ）に含まれる酸化化合物（Ｂ）の濃度、溶媒（Ｓ）については第一の製造方法と同様である。但し、溶媒（Ｓ）については上述したエントレーナ効果の面から、２０質量％以下の範囲は変わらないが、メチルアルコール、エチルアルコール、イソプロピルアルコールなどのアルコール系溶媒、メチルエチルケトンなどのケトン系溶媒、酢酸エチルなどのエステル系溶媒といった極性有機溶媒を、第一の製造方法に比べ、積極的に用いることも効果的である。
【００５５】
第二の製造方法で用いる装置は特に制限されないが、第一の製造方法で示した溶液（Ｃ）の加圧添加口とベントを備えた二軸押出し機に、さらに超臨界流体（Ｄ）の加圧添加口を設けたものが好ましい。尚、溶液（Ｃ）と超臨界流体（Ｄ）の添加の順序については特に限定されず、装置のレイアウトや規模で決定すればよい。
【００５６】
本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合には透明性にも優れるため、これらの機能が要求される部材に好適であり、例えば、内装材では計器盤の透明カバーならびに外装材では窓ガラス（ウィンドウ）やヘッドランプ、サンルーフ及びコンビネーションランプカバー類などの、自動車や家電そして住宅に用いられる透明部材・備品に適している。特に、本発明の樹脂組成物は、軽量化と成形の自由度が要求される無機ガラス代替用途としての樹脂製ウィンドウ（特に、熱線付き樹脂製ウインドウ）；車両用内外装部品成形体及び車両用外板；樹脂製ワイパーシステム；樹脂製ドアミラーステイ；樹脂製ピラー；樹脂成形体；樹脂製ミラー；樹脂製ランプリフレクター；樹脂製エンジンルーム内カバー及びケース；樹脂製冷却装置部品；大気と連通した中空構造および／または密閉された中空構造を有する樹脂一体成形体；一の部品に異なる２種以上の機能が付与される一体成形部品；可動部と非可動部を有する成形体；ならびに炭化水素系燃料を収納する部品あるいは容器で、その効果を有効に発揮できる。
【００５７】
すなわち、請求項１６〜３５、３９〜４５は、本発明に係わる樹脂組成物の用途に関するものである。
【００５８】
以下、本発明に係わる樹脂組成物の用途について詳述する。
【００５９】
本発明の第四は、上記記載の本発明の樹脂組成物を用いた車両用内外装部品成形体及び車両用外板である。また、本発明の第五は、上記記載の本発明の樹脂組成物を用いた樹脂ウィンドウである。
【００６０】
本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合には透明性にも優れるため、樹脂ウィンドウ、さらには車両用の外装部品や車両用外板の用途に好適である。例えば、図１で示すような、ドアモール１、ドアミラーのフレーム枠２、ホイールキャップ３、スポイラー４、バンパー５、ウィンカーレンズ６、ピラーガーニッシュ７、リアフィニッシャー８、ヘッドランプカバー（図示せず）等の車両用外装部品成形体、図２ａ、図２ｂで示すような、フロントフェンダー２１、ドアパネル２２、ルーフパネル２３、フードパネル２４、トランクリッド２５、バックドアパネル（図示せず）等の車両用外板が挙げられる。また、例えば、図３で示すような、車両のフロントガラス（図示せず）、サイドガラス３１、リアガラス３２等に適用できる。前述したように本発明では、顔料などの着色剤を樹脂組成物に混練したり、着色フィルムをインサートしたり、塗装するなどして所望の色調の部品を得ることが可能である。また、車両用途以外でも剛性、耐熱性、耐熱膨張性などを求められる用途、例えば建築物や鉄道車両の内外装材、電気・電子製品の筐体などにも使用できる。
【００６１】
このような車両用部品や建築用内外装材などを含む各種部材の製造方法としては、射出成形、真空圧空成形、加熱圧縮成形、ブロー成形などを部品に合わせて適宜選択すればよい。一般的なガラス繊維強化樹脂は、せん断応力を繰り返し受けることによってガラス繊維が壊れるためにその物性が徐々に低下しリサイクル性も低いが、本発明の樹脂組成物は前述のようにナノオーダーの酸化化合物（Ｂ）を用いているため、せん断応力を受けにくく、物性の低下を抑えることができる。
【００６２】
本発明の第六は、本発明の樹脂組成物を含んで成ることを特徴とする樹脂製ワイパーシステム、樹脂製ドアミラーステイ、樹脂製ピラーである。本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合透明性にも優れるため、例えば樹脂製ワイパーシステム、樹脂製ドアミラーステイ、樹脂製ピラーなどのような視界の向上が要求される部品の用途に好適である。
【００６３】
従来のワイパーシステムは、黒色塗装仕上げの鋼鉄と黒色のゴムで構成され、低速作動時に視界が妨げられるという課題があった。また、従来のドアミラステーは、外板と同色もしくは黒色塗装仕上げの樹脂製であり、右左折時の視界が妨げられるという課題があった。また、従来のピラーは鋼鉄製であり、フロントピラー、センターピラーは通常走行時や右左折時、リアピラーは後方移動時や後方確認時に視界が妨げられるという課題があった。これらの部品に透明な樹脂材料を使用できれば視界は向上するが、高い剛性や耐熱性、加熱時／成形時の寸法安定性も要求されることから、従来の透明樹脂材料では実現が難しかった。これに対して、本発明の樹脂組成物は、高い剛性、耐熱性、耐熱膨張性を有し、前述のように非晶性ポリオレフィン系樹脂を用いた場合透明性にも優れるため、本発明の樹脂組成物を前述の部品に用いることで、これらの課題が解決可能となり、透明な上記部品が得られることが判明した。また、これらの部品の透明化は視界向上だけでなく、意匠性の向上にも寄与できると期待される。
【００６４】
一例として図４にワイパーシステムの模式図を示す。ワイパーシステムは、ワイパーアーム４１とワイパーブレード４２から構成され、ワイパーアーム固定用ナット穴４５を中心として半弧を描くように作動する。ワイパーブレード４２は、一般に弾性を有する支持部分４３と軟らかいゴム部分４４とから構成され、本発明のワイパーシステムにおいては、ワイパーアーム、ワイパーブレード、ワイパーブレード支持部分の少なくとも１つに本発明の樹脂組成物を透明材として用いたものである。なお、本発明のワイパーシステムにおいては、該ゴム部分として耐久性が高く比較的透明性の高いシリコンゴム等を用いることが好ましい。また、ワイパーブレードの支持部分として、本発明の樹脂組成物に適量のアクリルゴム成分を加えた樹脂組成物を用いて調製してもよい。ワイパーブレードの支持部分に適度な弾性を与えることができるからである。このような樹脂組成物としては、例えば、本発明の樹脂組成物１００質量部に対して、エチルアクリレートもしくはブチルアクリレートを主成分としたコポリマーのアクリルゴム（例えば、日本ゼオン（株）製、Ｎｉｐｏｌ ＡＲ３１、ＡＲ３２）を０．５〜３０質量部添加したものが挙げられる。
【００６５】
本発明のドアミラーステイや樹脂製ピラーとしては、本発明の樹脂組成物を透明材としてドアミラーステイやピラーに成形したものの他、本発明の樹脂組成物を他の樹脂と積層した多層積層体で構成してもよい。このような多層積層体は少なくとも本発明の樹脂組成物から成る層を一層以上含んでいればよく、好ましくは積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を設けたものである。多層積層体とすることで、本発明の樹脂組成物以外の他の付加機能を付加することができる。多層積層体を用いる場合の各層の厚さは、最終的な成形品の厚さと積層数から至適な厚さを選択することができる。このような多層積層体とする場合の他の樹脂としては、例えば、ポリエステル、ポリアミド、ポリカーボネートが代表的な例として挙げられる。なお、該多層積層体として、前記した積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を用いた本発明の熱可塑性樹脂積層体を使用することもできる。本発明の樹脂組成物や上記多層積層体を用いてワイパーシステム、ドアミラーステイや樹脂製ピラーを製造する方法は特に限定されない。また、ドアミラーステイやピラーを単独の部品としても成形する他、ドアミラーステイやピラーとして使用できるのであれば、例えば後記する一体成形体の製造方法等によって、ドアミラーステイとフロントピラーや各ピラーと樹脂ルーフパネルとの一体成形体とすることもできる。
【００６６】
本発明の第七は、透明部と不透明部を有する樹脂成形体であって、少なくとも透明部が上記樹脂組成物を含んで成ることを特徴とする樹脂成形体である。本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合透明性にも優れ、さらにオレフィン系樹脂は元来耐薬品性に優れた樹脂であるため、透明部と不透明部とを有し、これらを一体に成形した樹脂成形体の用途にも好適に使用できる。このような樹脂成形体を、自動車部品を例に説明する。
【００６７】
自動車には、各種ランプ類やカバー、ガラスなどの透明な部品と、外板や各種内装部品のような不透明な部品が混在している。これらの部品にはそれぞれ透明性、剛性、耐熱性、低線膨張率、耐薬品性など、異なる様々な特性が要求されるため、従来の樹脂材料ではこれら透明な部品と不透明な部品との一体化は難しかった。しかしながら、本発明の樹脂組成物は、射出成形、真空圧空成形などによって容易に成形できるため、本発明の樹脂組成物を透明材として使用して、高剛性、高耐熱性、低線膨張率、高耐薬品性を確保しつつ、透明な部分と不透明な部分とを一体成形させ、部品点数及び工程数の削減、部品重量を低下させることができる。また、透明部と不透明部の一体形成により、従来分割されていた外形線が一つの連続するラインで形成できるため、部品外観の向上が図れる。
【００６８】
より具体的には、透明性を必要とするヘッドランプはその周囲に存在するバンパ、フロントグリル、フェンダ、フードといった不透明の別の部品と接している。これらを一体成形すると部品点数の削減が可能となり、一体化された部品を組み付ければよいため、組み立て時の工程数も削減できる。特に、本発明の樹脂組成物は耐熱性に優れるため、ランプの熱源が近くて樹脂が溶融するなどの問題もない。従来のヘッドランプはポリカーボネート樹脂製でできているため耐光性が低く、太陽光に暴露されると黄変するため表層コーティングが必要であった。しかしながら、本発明の樹脂組成物を用いるとこのような問題も解決される。
【００６９】
このような樹脂組成物の製造方法としては特に制限させるものではない。例えば、透明性が必要とされる部品として自動車用ガラスがあり、この自動車用ガラスには、ドアに付属するサイドガラス、バックドアガラス、リアフェンダーとルーフに接着してあるリアクウォーターガラス、リアガラス等と呼称されている。サイドガラスやバックドアガラスは、ドアアウターとドアインナーとの間にガラスが配置される構造である。予めドアアウターとドアインナーとを用いて内部に中空部を形成させ、該中空部に本発明の樹脂組成物を流し込むことで、ドアアウター・ドアインナー・ガラスを一体に成形することができる。同様にして、ピラーガーニッシュとリアクウォーターガラスとを一体化することもできる。本発明の樹脂成形体を図５で示すが、上記ピラーガーニッシュとリアクウォーターガラスとを一体化した樹脂成形体に限らず、ランプ・フード・フェンダー一体樹脂成形体５１、ピラーガーニッシュ・ガラス一体樹脂成形体５２、ルーフ・フェンダ・ガラス一体樹脂成形体５３、バックドア・ガラス一体樹脂成形体５４、ドア・ガラス一体樹脂成形体５５等がある。なお、ドアロックやワイパーモーター等は後工程で部品の中空部に設置すればよい。
【００７０】
更に、自動車用内装材としてインストルメントパネルの場合には、従来から、計器類、その透明なカバー、クラスターリッドが別部品で作られている。しかしながら、本発明の樹脂組成物を用いて透明樹脂部と不透明樹脂部とを一体で成形すると、予めインストルメントパネル６１と計器類のカバー６２との一体化によってインストルメントパネルに数種の部品を集約させ、部品点数を削減しかつ軽量化を図ることができる。図６にこのようなインストルメントパネルの模式図を示す。
【００７１】
また、本発明の樹脂組成物の透明かつ高強度・高剛性の特徴を利用して、樹脂成形体の一部が透明部であり他の部分が不透明である、高強度・高剛性を保持した部材とすることもできる。例えば、ルーフの一部に本発明の樹脂組成物を用いると該部分を透明にすることができ、ガラス製サンルーフを設けなくとも透明なルーフとすることができる。なお、上記樹脂成形体において、不透明部は着色していてもよい。
【００７２】
本発明における透明部と不透明部とを有する樹脂成形体において、着色した不透明部の樹脂成形体を得るには、着色した原料樹脂を用いる方法、不透明部に塗装または印刷して着色する方法、または不透明樹脂として着色シートを使用する方法等がある。
【００７３】
着色した原料樹脂の調製方法としては、原料樹脂に予め顔料を分散させておく方法の他、原料樹脂ペレットと顔料ペレットを同時に溶融・混練させ、射出成形機を用いて金型内に射出して着色樹脂を得る方法がある。該着色樹脂を用いて本発明の樹脂成形体を製造するには、続いて金型を開き、または溶融樹脂通過経路を新たに作り、別のシリンダを用いて金型の空隙部に透明溶融樹脂を射出すればよい。これによって透明部と着色した不透明部とを有する樹脂成形体を製造することができる。なお、不透明樹脂を先に射出するか透明樹脂を先に射出するかはどちらでも良い。
【００７４】
塗装または印刷により着色した不透明部を形成するには、予め透明樹脂を溶融して目的の樹脂成形体を形成し、その後該樹脂成形体の表面または裏面から塗装または印刷を施して着色および不透明性を確保する方法である。溶融樹脂の賦形前に塗装または印刷を施し、その後に賦形することもできる。
【００７５】
不透明樹脂として着色シートを使用する場合には、予め着色された不透明シートを予備賦形しておき金型内に配置し、続いて溶融透明樹脂を金型内に注入し、樹脂を冷却固化させ、その後に金型より取り出せば、本発明の樹脂成形体を得ることができる。
【００７６】
また、上記方法によれば、例えばルーフ・フェンダ・ガラス一体樹脂成形体として、ガラス部が透明部であり、ルーフとフェンダとが不透明である樹脂成形体に限られず、ガラスの上部とルーフの一部が透明部であり、フェンダとガラスおよびルーフの残部が不透明の樹脂成形体とすることもできる。
【００７７】
更に、本発明の透明部と不透明部とが一体成形された樹脂成形体は、本発明の樹脂組成物と顔料とによって構成できるが、本発明の樹脂組成物と他の樹脂とを積層した多層積層体で構成することも可能である。このような多層積層体は少なくとも本発明の樹脂組成物から成る層を一層以上含んでいればよく、好ましくは積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を設けることができる。このように多層積層体とすることで本発明の樹脂組成物のみでは発現できないような付加機能をも付与することが可能となる。なお、多層を構成する他の樹脂の種類や各層の厚さは、樹脂成形体の用途に応じて適宜選択することができる。
【００７８】
本発明の第八は、本発明の樹脂組成物を含んで成ることを特徴とする熱線付き樹脂製ウィンドウ、樹脂製ミラー、樹脂製ランプリフレクター、樹脂製エンジンルーム内カバーおよびケース、樹脂製冷却装置部品である。
【００７９】
本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合透明性にも優れ、さらにオレフィン系樹脂は元来耐薬品性に優れた樹脂であるため、例えば樹脂製ウィンドウや樹脂製ミラー、ランプリフレクター、エンジンルーム内カバーおよびケース等の部品の用途に好適であり、部品点数、工程数、重量の低減が可能になる。更に本発明の樹脂組成物を透明材として用いることで、透明性が要求される部品の材料代替が可能になり、防曇性や視界の向上が図られる。
【００８０】
例えば、図７に示すリアウィンドウ７３、ドアウィンドウ７２、フロントウィンドウ７１などの樹脂製ウィンドウは、防曇機能を付与するため成形体の内部や表面に加熱可能な熱線ヒータを設けることがある。従来の透明樹脂材料を用いた場合には、熱線ヒータによる樹脂材料の耐熱性や熱膨張が課題となるが、本発明の樹脂組成物を用いるとこれらの問題がない。また、本発明の樹脂組成物は高い剛性を有するので、フロントウィンドウ７１、ドアウィンドウ７２、リヤウィンドウ７３等の大型部品に応用可能で軽量化することができる。なお、熱線ヒータの形成方法としては、例えばフィルム化された熱線部をインサート成形する方法や、室内側表面に熱線部を蒸着・塗布・印刷法等により形成する方法等が挙げられる。また、本発明の透明樹脂を用いて樹脂製サイドミラー７４（図７参照）を製造すると、従来のガラスや透明樹脂を用いた場合に比べ軽量化ができ、これに熱線ヒータを設ければ防曇機能を付与することも可能になる。図７に示したサイドミラー以外にも車室内のルームミラー等にも適用可能である。
【００８１】
また、図８に自動車ランプの横断面図を示す。車体側基体８１に固定されたアウタ部材８２の内部にリフレクター８３が配置され、該リフレクターにはバルブ８４と光軸調整器８５が連結し、該アウタ部材ははさらにアウタレンズ８６が嵌合されている。従来の樹脂材料を用いてリフレクターを構成すると、耐熱性・線膨張率・線膨張異方性に劣る場合があったが、本発明の樹脂組成物を用いるとこれらの問題が解決できる。特に、本発明の樹脂組成物は高い剛性を有するため軽量で高耐熱性が確保でき、かつ寸法安定性と表面平滑性に優れるランプリフレクターとでき、ヘッドランプ、フォグランプ、リアコンビランプ等のリフレクター、またはヘッドランプのサブリフレクター等に好適に使用できる。尚、反射部の形成方法としては、例えば該部材を製造する際に反射膜部をインサート成形する方法や、該部材を射出成形・プレス成形により成形後に、反射部に蒸着膜を形成させる方法等がある。
【００８２】
また、本発明の樹脂組成物を使用して、エンジンルーム内カバーおよびケースに応用することができる。エンジンルーム内を図９および図１０に示す。本発明の樹脂組成物は透明性、耐熱性、耐薬品性、剛性強度に優れるため、温度条件の厳しいエンジンルーム内において使用可能で、かつ軽量な部品とすることができる。このような部品として、例えばラジエーター９１、冷却液リザーブタンク９２、ウオシャータンクインレット９３、電気部品ハウジング９４、ブレーキオイルタンク９５、シリンダーヘッドカバー９６、エンジンボディー１０１、タイミングチェーン１０２、ガスケット１０３、フロントチェーンケース１０４などがある。しかも、本発明の樹脂組成物は透明であるため、上記ウオッシャータンクインレット、電気部品ハウジング、ブレーキオイルタンク、シリンダーヘッドカバー、タイミングベルトカバー等のタンクあるいはカバー内の視認性を向上させることができる。
【００８３】
本発明の樹脂組成物は、耐熱性、耐薬品性、剛性強度に優れたより軽量な部品とすることができることから、自動車エンジンルーム内で冷却水との接触下で使用される部品用途に好適に使用される。このような樹脂製冷却装置部品を図１１、１２に示す。例えば、図１１に示すウォーターパイプ１１１、Ｏ−リング１１２、ウォーターポンプハウジング１１３、ウォーターポンプインペラ１１４、ウォーターポンプ１１５、ウォーターポンププーリ１１６、図１２に示すウォーターパイプ１２１、サーモスタットハウジング１２２、サーモスタット１２３、ウォーターインレット１２４等のラジエータータンクのトップおよびベースなどのラジエータータンク部品、バルブなどの部品が挙げられる。該樹脂組成物を使用すると軽量化、耐薬品性向上、燃費向上が図られるため、その実用価値が高い。
【００８４】
なお、本発明の上記各部品は、本発明の樹脂組成物のみでも構成できるが、例えば本発明の樹脂組成物を他の樹脂材料と積層した多層積層体で構成することも可能である。このような多層積層体は少なくとも本発明の樹脂組成物から成る層を一層以上含んでいればよく、好ましくは積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を設けることができる。多層積層体とすることで本発明の樹脂組成物のみでは発現できないような付加機能をも付与することが可能となる。なお、各層を構成する他の樹脂の種類や各層の厚さなどは、使用目的に応じて適宜選択することができる。
【００８５】
本発明の第九は、上記樹脂組成物を含んで成る、大気と連通した中空構造および／あるいは密閉された中空構造を有することを特徴とする樹脂一体成形体である。上記のように、本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れ、また前述のように非晶性ポリオレフィン系樹脂を用いた場合透明性にも優れるため、例えば、ドアやルーフ、フード等のような中空構造を有する部品の用途に好適である。
【００８６】
自動車の外板および内外装部品は、鋼板と樹脂パネルより構成され、かつ部品内部に補機等を装着する中空構造を有している部品が多い。例えば、側面ドアおよびバックドアは、外側および内側を鋼板で中空構造を構成し、塗装を経て組み立て工程で内側鋼板に樹脂パネルを取り付け、中空構造内に各種補機等を取り付けている。また、ルーフ、フード、トランクリッド、バックドア等は、外板および補強レインホース等を鋼板で構成し、塗装後に内側に樹脂部品を取り付けている。これらの中空構造を有する部品は大型であり、剛性や寸法安定性も要求されるため、従来の樹脂材料では一体成形が難しかった。しかしながら、高剛性、低熱膨張率、低熱収縮率を有する本発明の樹脂組成物を使用すると一体成形が可能となり、これらの部品の部品点数、工程数、重量の低減が可能になる。
【００８７】
本発明の樹脂一体成形体は、本発明の樹脂組成物のみでも構成できるが、例えば本発明の樹脂組成物を他の樹脂材料と積層した多層積層体で構成することも可能である。このような多層積層体は少なくとも本発明の樹脂組成物から成る層を一層以上含んでいればよく、好ましくは積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を設けることができる。多層積層体とすることで本発明の樹脂組成物のみでは発現できないような付加機能をも付与することが可能となる。多層積層体を構成する他の樹脂の種類や各層の厚さなどは、使用目的に応じて適宜選択することができる。なお、該多層積層体として、前記した積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を用いた本発明の熱可塑性樹脂積層体を使用することもできる。
【００８８】
本発明の樹脂一体成形体は、最表面層に表皮材、意匠印刷層等の加飾層を設けることで意匠性、触感、質感を高め商品性を向上することができるため、一体成形体の最表層が加飾材で構成されることが好ましい。例えば、起毛シート、エンボス紋様シート、レーザー紋様シート、木目調シート等の表皮材を最表面層に設けた成形体は、ルーフ室内側、ピラーガーニッシュ類、インストルメントパネル等に用いることができる。前述の多層積層体を用いた場合には、意匠印刷層はその中間層に設けてもよく、表層を透明材とすることで光沢感、深み感を高めることができる。
【００８９】
本発明の中空構造を有する一体成形体において、中空構造は、気体、液体若しくは固体またはこれらの混合物が充填、封入されることが好ましい。断熱性能、遮音性能を向上させることができるからである。充填、封入される材料は、特に制限されず、公知の充填・封入材が使用できるが、例えば、透明性が要求される場合には、窒素、アルゴン、二酸化炭素、空気等の気体が好ましく、透明性が要求されない場合には、前述の気体の他、封入時の加熱で液状を示しかつ封入後の常温では固体状になるパラフイン、ワックス等が好ましい。上記封入材により、夏期には車室内から冷熱の逃げ、外気の高熱の侵入を、冬期には温熱の逃げ、外気の冷熱の侵入を抑制し快適な車室内環境を維持できる。また二重壁で内に中空部を有する構造により、外部からの騒音エネルギーを緩和、あるいは吸収し静粛な車室内環境を達成できる。また、フードに本発明の樹脂一体成形体を適用することでエンジンルームからの放射音、放射熱を低減できる。
【００９０】
本発明の中空構造を有する一体成形体の製造方法は、特に限定されず、公知の方法が適用できるが、例えば、一般的な真空圧空成形法、射出成形法、ブロー成形法、プレス成形法等を用いることができる、また、例えば、下記方法が好適に用いられる。
【００９１】
第一の方法としては、加圧流体導入経路を備えたホルダーに、２枚の本発明の樹脂組成物よりなる樹脂シートを固定し、公知の方法でホルダーをシールして２枚のシート間に密閉空間を形成する。各シートを荷重たわみ温度以上に加熱し、開放状態の金型に挿入した後に、軟化したシートの外周部を金型で押圧して溶着する。この際、外周部を溶着する前あるいは溶着しつつあるいは溶着した後に、好ましくは溶着する前あるいは溶着した後に、２枚のシート間の密閉空間に加圧流体を注入し、シートを拡張しつつ／または拡張後、金型を閉状態にして成形体が冷却するまで加圧流体圧を保持し、これにより中空構造を形成する。好ましくは、真空引き孔を設けた金型を用い、シート拡張時に真空吸引を併用して、金型面とシートとの密着性を高める。真空吸引を用いることによって、得られる一体成形体の転写性を向上できる。すなわち、本発明の第十は、本発明の樹脂組成物を含んでなる樹脂シート２枚を加熱し、これを開状態の金型に挿入し、シート外周部を押圧し、外周部を溶着する前あるいは溶着した後にシート間に加圧流体を注入し、シートを拡張しつつ／または拡張した後に、金型を閉状態にし、加圧流体圧を保持し中空構造を形成する、本発明の樹脂一体成形体の製造方法である。
【００９２】
第二の方法としては、閉状態の金型内に溶融した本発明の樹脂組成物を充填しつつあるいは充填した後、金型を後退して、キャビティ容積を拡大しつつ溶融樹脂内部に加圧流体を注入し中空構造を形成する方法である。すなわち、本発明の第十一は、閉状態の金型内に溶融した本発明の樹脂組成物を充填しつつ／または充填後、キャビティ容積を拡大しつつ加圧流体を溶融樹脂内に注入し中空構造を形成する、本発明の樹脂一体成形体の製造方法である。
【００９３】
第三の方法としては、金型片面のキャビティ面に本発明の樹脂組成物よりなる樹脂シートを１枚インサートし、背面に溶融樹脂を充填しつつ、あるいは充填後に金型を後退しキャビティ容積を拡大しつつ溶融樹脂内部に加圧流体を注入し中空構造を形成する方法、あるいは２枚の樹脂シートを用い金型両面のキャビティ面にシートをインサートし、シート間に溶融樹脂を充填しキャビティ容積を拡大し加圧流体を注入し中空構造を形成する方法である。すなわち、本発明の第十二は、開状態の金型キャビティ面に本発明の樹脂組成物を含んでなる樹脂シートを１枚もしくは２枚インサートし、金型を閉状態で２枚のシート間もしくは１枚のシート背面に溶融樹脂を充填しつつまたは充填した後、キャビティ容積を拡大しつつ加圧流体を溶融樹脂内に注入し中空構造を形成する、本発明の樹脂一体成形体の製造方法を提供するものである。
【００９４】
上記態様において、シートに充填される樹脂の種類は、本発明の樹脂組成物からなるシートと密着する樹脂であれば特に制限されないが、好ましくは、シートの樹脂組成物と接する樹脂種と同種の樹脂またはこれと溶解度パラメーター（ＳＰ値）が近いものが使用される。
【００９５】
本発明において、加圧流体しては、特に制限されず、樹脂シートの成分等を考慮して公知の加圧流体から選択される。例えば、空気、窒素ガス等の気体、水やシリコンオイル等の液体などが好ましく使用される。
【００９６】
本発明の中空構造を有する樹脂一体成形体の適用部品としては、図１３、１４に示すように、例えばフード１３１、ドア１３２、バックドア１３３、ルーフ１３４、フェンダー１３５、ウィンドウ１３６、トランクリッド１３７、センターコンソールボックス１４１、ピラーガーニッシュ１４２、インストルメントパネル１４３、ヘッドライニング等を挙げることができる。これらの部品はインナー／アウターおよび付帯する部品やレインホース等を同時にかつ一体で成形でき、部品数の低減および工程数を短縮することができる。更に中空部に気体、液体、固体あるいはこれらの混合物を封入することで付加的な機能を付与することができる。例えばフードではレインホースとの一体化や遮音・遮熱機能の付与が可能であり、ルーフではヘッドライニングとの一体化や断熱・遮音機能の付与が可能であり、ドアやフェンダーではインナー／アウターの一体化が可能である。
【００９７】
本発明の第十三は、本発明の樹脂組成物を含んで成る、異なる機能を有する２種類以上の部品を統合することを可能にし、ひとつの部品に異なる２種類以上の機能が付与される一体成形部品である。ここに異なる機能とは、例えば、インストルメントパネルのような表示機能、エアコンダクトなどのような通風機能、ルーフレール等の固定機能などをいう。本発明の樹脂組成物は、上述のように多彩な機能を有するため、種々の機能の確保が期待される部材に応用することができ、これらを一体成形することで異なる機能を有する二種類以上の部品を統合し、ひとつの部品に二種類以上の機能が付与された一体成形部品とすることができる。これによって大型部品の一体化、いわゆるモジュール化やインテグレーション（統合化）に好適であり、高品質を維持しながら部品点数、工程数、重量の低減が可能になる。
【００９８】
例えば、大型内装部品である図１５に示すインストルメントパネルは、現在、パネル部１５１とエアコンのエアダクトやケース１５２、クロスカービーム（ステアリングクロスメンバー）を別々に作り、これらを車の製造ラインで組み立てている。従来の樹脂材料でパネル部とエアコンのエアダクトやケースを一体成形しようとすると、大型かつ複雑な形状の部品のため成形収縮によるヒケや歪み、熱時の膨張などが課題となるが、本発明の樹脂組成物を用いることでこのような課題が解決可能となる。また、本発明の樹脂組成物は高い剛性を有するので、このような一体成形により部品全体を構造体とすることが可能で、従来スチールが使用されているクロスカービーム（ステアリングクロスメンバー）を廃することが可能である。また本発明の樹脂組成物を用いることでスチールでは後付けする必要があったブラケット等も一体成形可能となる。また一体成形時に金型内に表皮材等の加飾材を投入しインサート成形することにより、加飾材との一体成形も可能になる。同様の効果は例えばドアに適用した場合でも得られる。現在のドアインナーパネルはスチール製が主で、ここにサイドウィンドウ用のガイドレールやレギュレータ、ドアロック、スピーカ等の各種部品が製造ラインで組み付けられる。本発明の樹脂組成物を用いることでドアインナーパネル、ガイドレール、スピーカハウジング等を一体成形することができる。
【００９９】
図１６に本発明の一体成形部品の他の例を示す。図１６に示すように、大型外装部品であるルーフレール１６１を例にすると、前述した本発明の樹脂組成物製のルーフパネル１６２との一体成形が可能となる。ルーフレールは重量がかかり温度的にも厳しい環境で使用されるため、従来の樹脂材料では特に剛性と耐熱性が課題となっていた。しかしながら、本発明の樹脂組成物を用いるとこのような課題が解決可能となる。同様の効果は例えばスポイラーに適用した場合でも得られ、前述した本発明の樹脂組成物製のトランクリッドとの一体成形が可能である。
【０１００】
図１７に大型車体部品であるラジエーターコアを示す。現在フロントエンドモジュールとして樹脂製のラジエーターコアが世にでつつあるが、本発明の樹脂組成物を用いると、更に耐熱性、耐薬品性、剛性強度に優れたより軽量な部品とすることができ、ファンシュラウドやブラケット等も一体成形することができる。特に、本発明の樹脂組成物を用いると、ラジエーターのリザーバタンク、ヘッドランプカバー等の透明部を一体成形することができ、加えて、従来は別体であったバンパ補強材の一体化も可能となる。また、エンジンルーム内部品であるエアクリーナーやスロットルチャンバー等を例にすると、耐熱性と耐薬品性に優れ低線膨張の本発明の樹脂組成物を用いることで、これらを一体化することができる。従来からこのような一体化は試みられているが、エンジンルーム内は高温かつオイル等の薬品による厳しい環境であり、従来の樹脂材料ではこの対策が課題となっているが、本発明の樹脂組成物を用いるとこのような課題が解決可能となる。同様の効果はインテークマニホールドやシリンダヘッドカバーに適用した場合でも得られ、前述の部品とともに一体成形することも可能である。
【０１０１】
本発明の一体成形部品は、本発明の樹脂組成物のみでも構成できるが、本発明の樹脂組成物を他の樹脂材料と積層した多層積層体で構成することも可能である。このような多層積層体は少なくとも本発明の樹脂組成物から成る層を一層以上含んでいればよく、好ましくは積層体の最表面層と最下層、更に好ましくは中間層にも該樹脂組成物層を設けることができる。多層積層体とすることで本発明の樹脂組成物のみでは発現できないような付加機能をも付与することが可能となる。このような多層積層体として、上記熱可塑性樹脂積層体がある。
【０１０２】
本発明の樹脂組成物は、剛性、耐熱性、耐熱膨張性に優れるため、一体成形部品とした場合には、例えばスロットルチャンバーのような可動部と非可動部を有する部品の用途に好適である。したがって、本発明の第十四は、本発明の樹脂組成物を含んで成る可動部と非可動部を有する成形体である。
【０１０３】
自動車の吸排気系部品やエアコンユニット内には、可動部と非可動部を有する部品が多数用いられている。これらの部品は、主に空気などの気体の流れを制御するためのものであり、非可動部としての、気体を流路となる、即ち、流動気体を導入する筒状の部品（成形体）と、可動部としての、気体流動を制御する開閉可能な蓋から構成され、例えば、スロットルチャンバーやエアコンユニット内の各ドアが挙げられ、これらの部品では気密性が重要となる。また、特にエンジンルーム内の部品に適用する場合、耐熱性も要求されるため、この点も課題となった。しかし、低熱膨張率、低熱収縮率、高耐熱性を有する本発明の樹脂組成物を用いることで、これらの課題が解決可能となり、気密性に優れた部品とすることができる。更に本発明の樹脂組成物は高剛性なためこれらの部品の軽量化とそれによるレスポンスの向上が可能となる。
【０１０４】
本発明の可動部と非可動部を有する成形体は、例えば射出成形法を用いて可動部と非可動部を別々に成形した後、これらを組み立ててもよいが、例えば二色成形法等の方法で可動部と非可動部を一体成形することが好ましい。気密性がより向上し、また工程数や部品数の低減が可能になるためである。図１８に示すスロットルチャンバーを例に取ると、例えば次の方法で製造することができる。
【０１０５】
スロットルチャンバーは、非可動部である筒状のチャンバー部１８１と可動部である開閉バルブ１８２および開閉バルブシャフト１８３とを有する。まず、二色成形用金型内に、開閉バルブ用金属製シャフトをセットし、次に円筒状のチャンバーを射出成形し、続いて円盤状の開閉バルブを成形するためにスライドコアを後退して円盤状の開閉バルブを射出成形する。このとき金属製シャフトと円盤状の開閉バルブが一体化される。本発明によれば、可動部が気体流動を制御する開閉蓋であり非可動部は流動気体を導入する筒状成形品にも、好ましく応用することができる。
【０１０６】
本発明の樹脂組成物は、炭化水素系燃料の遮断性、ガスバリア性、耐薬品性に優れるため、炭化水素系燃料を収納する部品または容器、炭化水素系燃料を収納する部品または容器、例えば、燃料タンク等の炭化水素系燃料を収納する車両用の一連の燃料系部品、灯油容器等の家庭用品の用途に好適である。したがって、本発明の第十五は、本発明の樹脂組成物を含んで成る炭化水素系燃料を収納する部品あるいは容器である。
【０１０７】
図１９に、このような部品や容器である、自動車等の車両における樹脂製燃料タンクを示す。フィラーチューブ１９１を介して炭化水素系燃料であるガソリンが燃料タンク１９２に注入・貯蔵され、ついで当該ガソリンが燃料ポンプ１９３によりエンジン（図示せず；付号１９４としてのみ表示する）に圧送される形式の燃料系システムとなっている。燃料系部品において本発明の樹脂組成物が適用できる部品としては、燃料タンク１９２、フィラーキャップ１９５、ベントチューブ１９６、フューエルホース１９７、フューエルカットオフバルブ、デリバリーパイプ、エバポチューブ、リターンチューブ、フューエルセンダーモデュール等が挙げられる。燃料タンクはこれら車両の燃料系システム部品の中で最大規模の部品である。
【０１０８】
ここで、燃料タンクの樹脂化の現状と課題について詳述する。従来から、母材樹脂としてオレフィン系のＨＤＰＥ（高密度ポリエチレン）が使用され、その工法として吹き込み法で成形が行われてきた。これらの材料と工法には大きな変化はなかったが、タンクの層構造は大きく変化した。例えば、当初は単層型燃料タンクであったが、炭化水素の蒸散規制法の施行に伴い、炭化水素の透過低減のため燃料タンクの多層化が余儀なくされた。その結果、現在燃料タンクはＨＤＰＥ／ＰＡ（ポリアミド）またはＨＤＰＥ／ＥＶＯＨ（エチレン酢酸ビニル共重合体）の両端をＨＤＰＥで構成する３種５層からなる多層構造タンクが主流となっている。この場合の成形は、従来と同じ吹き込成形である。
【０１０９】
上記単層型燃料タンクにおいて、タンクより多くの炭化水素系燃料が透過するのは両者の相溶性が良いのが原因である。相溶の尺度である溶解度パラメータ（以下ＳＰ値）はＨＤＰＥが７．９、炭化水素系燃料が６〜８であり、両者は同じ領域にある。一方、多層タンクに用いるＰＡのＳＰ値は１３．６で、炭化水素系燃料とのＳＰ値の開きが大きい、換言すれば相溶性が悪い領域にある。これらより多層燃料タンクにおけるＰＡ材は炭化水素系燃料のタンク外への透過を阻止するバリアー層として設置されたものである。当該多層燃料タンクの創出により炭化水素の蒸散規制法を満たす技法が確立されたものの成形工程が煩雑となって大幅な価格上昇を招いた。上記問題に加えて、複数の樹脂の積層構造としたため、リサイクルの円滑性が失われ、リサイクル社会という時代の要請に応えがたい新たな課題を残した。
【０１１０】
これに対して、本発明の樹脂組成物中の酸化化合物（Ｂ）は極性基を残しているためＳＰ値が比較的高く、前述のＰＡやＥＶＯＨに相当する炭化水素系燃料の透過阻止の機能がある。従って、本発明の樹脂組成物を用いれば、単層型でも炭化水素の蒸散が少なく、製造コストの低減が図れ、かつリサイクル性に優れた車両用の燃料タンクを提供することができる。この際、本発明の樹脂組成物は、単層型または必要であれば多層型のいずれの場合であっても、従来と同様、吹き込成形によって車両用燃料タンクに成形することが使用できる。
【０１１１】
なお、車両用の燃料タンクに比べるとは効果はやや低いものの、本発明の樹脂組成物は、上記車両用の燃料タンク以外にも、灯油容器等の家庭用品に用いることもできる。これにより灯油の大気への蒸散が軽減され、地球環境の保全に寄与することができる。
【０１１２】
上記したように本発明では、更に、顔料等の着色剤を樹脂組成物に混練したり、着色層を挿入して所望の色調を有する部品を得ることも可能である。このため、上記記載の自動車以外でも美観、平滑性、透明感等の外観品質が要求され、かつ高剛性や表面の耐擦傷性を求められる用途、例えば建造物の外装材、内装材、鉄道車両の内装材等にも使用できる。
【０１１３】
このような車両用部品や建築用内装材などを含む各種部材の製造方法としては、上記で詳述したが、射出成形、真空圧空成形等を部品や用途に合わせて適宜選択すればよい。一般的なガラス繊維強化樹脂は、せん断応力を繰り返し受けることによってガラス繊維が壊れるためにその物性が徐々に低下しリサイクル性も低いが、本発明の樹脂組成物は上記表面改質シリカ組成物を用いているためせん断応力を受けにくく、物性の低下を抑えることができる。
【０１１４】
【実施例】
以下、本発明の実施例により具体的に説明する。本発明はこれによって限定されるものではない。なお、下記実施例において、特記しない限り、「部」は「質量部」を意味する。
【０１１５】
実施例１
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１１６】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部と、無水マレイン酸変性ポリオレフィン（日本ポリオレフィン（株）製：アドテックスＥＲ３２０Ｐ）２０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．０６質量％である。
【０１１７】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１１８】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例１とする。
【０１１９】
実施例２
オレフィン系樹脂（Ａ）には実施例１と同じものを用いた。酸化化合物（Ｂ）（溶液（Ｃ））としては、下記のものを使用した。
【０１２０】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、まず表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させ、次にアミノ基を有するシラン系化合物である３−アミノプロピルトリエトキシシラン（チッソ（株）製）を１／１０当量反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１２１】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例２とする。
【０１２２】
実施例３
酸化化合物（Ｂ）（溶液（Ｃ））には実施例１と同じものを用いた。オレフィン系樹脂（Ａ）としては、下記のものを使用した。
【０１２３】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部と、カルボニル基を有する変性ポリオレフィン（日本ポリオレフィン（株）製：レクスパールＲＢ）２０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．５質量％である。
【０１２４】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例３とする。
【０１２５】
実施例４
酸化化合物（Ｂ）（溶液（Ｃ））には実施例２と同じものを用いた。オレフィン系樹脂（Ａ）としては、下記のものを使用した。
【０１２６】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部と、エポキシ基を有する変性ポリオレフィン（日本ポリオレフィン（株）製：レクスパールＲＡ）２０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．４質量％である。
【０１２７】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例４とする。
【０１２８】
実施例５
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１２９】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ９００Ａ）にメタクリル酸アミノエチル（アルドリッチ製）と有機過酸化物であるブチルパーオキシベンゾエイトを加えよく混合したものを、二軸混練機で２００℃で混練し、アミノ基を有する変性ポリオレフィンを得た。この２０部とホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．０６質量％である。
【０１３０】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、まず表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させ、次に１／１０当量のエポキシ基を有するシラン系化合物である（３−グリシドキシプロピル）トリメトキシシラン（チッソ（株）製）を反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１３１】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例５とする。
【０１３２】
実施例６
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１３３】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ９００Ａ）にアクリルアミド（アルドリッチ製）と有機過酸化物であるブチルパーオキシベンゾエイトを加えよく混合したものを、二軸混練機で２００℃で混練し、アミド基を有する変性ポリオレフィンを得た。この２０部とホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．０６質量％である。
【０１３４】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、まず表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させ、次に１／２０当量のカルボキシル基を有するシラン系化合物である１，３−ビス（３−カルボキシプロピル）テトラメチルジシロキサン（チッソ（株）製）を反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１３５】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例６とする。
【０１３６】
実施例７
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１３７】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部と、水酸基を有する変性ポリオレフィン（三洋化成（株）製：ユーメックス１２０１Ｈ）２０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．１質量％である。
【０１３８】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させ、次に１／１０当量のアミド基を有するシラン系化合物であるビス（Ｎ−メチルベンズアミド）エトキシメチルシラン（チッソ（株）製）を反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１３９】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例７とする。
【０１４０】
実施例８
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１４１】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）８０部と、水酸基を有する変性ポリオレフィン（三洋化成（株）製：ユーメックス１２０１Ｈ）２０部をブレンダーにてよく混合しオレフィン系樹脂（Ａ）とした。尚、この時の極性基濃度は約０．１質量％である。
【０１４２】
酸化化合物（Ｂ）（溶液（Ｃ））：
水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）に、表面水酸基量（粒子表面にシラノール基が２個／ｎｍ^２と仮定し算出）に対して１／５０当量のトリメチルエトキシシラン（チッソ（株）製）を反応させ、次に１／１０当量のカルボニル基を有するシラン系化合物であるアセトキシプロピルトリメトキシシラン（チッソ（株）製）を反応させたものを溶液（Ｃ）とした。なおこのときシリカの疎水基導入率（Ｒ×Ｎ）は０．０６である。
【０１４３】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例８とする。
【０１４４】
実施例９
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））としては、実施例１と同じものを用いた。
【０１４５】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例９とする。
【０１４６】
実施例１０
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））としては、実施例２と同じものを用いた。
【０１４７】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて溶液（Ｃ）を添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を実施例１０とする。
【０１４８】
比較例１
オレフィン系樹脂（Ａ）及び酸化化合物（Ｂ）（溶液（Ｃ））として、下記のものを使用した。
【０１４９】
オレフィン系樹脂（Ａ）：ホモポリプロピレン（サンアロマー（株）製：ＰＭ８０２Ａ）を未処理のまま、比較用オレフィン系樹脂（Ａ）とした。
【０１５０】
酸化化合物（Ｂ）（溶液（Ｃ））：水分散のコロイダルシリカ（旭電化工業（株）製：アデライトＡＴ−４０、平均粒子径１５〜１８ｎｍ、シリカ濃度４０質量％、水溶媒）を未処理のまま比較用溶液（Ｃ）とした。よってこのときシリカの疎水基導入率（Ｒ×Ｎ）は０である。
【０１５１】
二軸混練機（（株）日本製鋼所製：ＴＥＸ３０ＸＳＳＴ改造機）を用いて、まず１０ｋｇ／ｈの混練速度で上記比較用オレフィン系樹脂（Ａ）を溶融混練し、シリンダ途中からプランジャポンプを用いて比較用溶液（Ｃ）を添加・混練し、続けて超臨界二酸化炭素を樹脂量の１０質量％程度となるようさらに添加・混練した。尚、溶液（Ｃ）の添加量は得られる樹脂組成物中の酸化化合物（Ｂ）の濃度が１０質量％になるよう調整した。得られた樹脂組成物を比較例１とする。
【０１５２】
実施例１１
上記実施例１〜１０および比較例１で得られた樹脂組成物を試験片に成形し、各試験片について以下の物性評価を行なった。評価結果を表１にまとめる。
【０１５３】
なお、本実施例における各種評価は以下の方法によった。
【０１５４】
（評価方法）
（１） 曲げ弾性率は、ＡＳＴＭ Ｄ７９０−１９９１に準拠して測定した。
【０１５５】
（２） 荷重たわみ温度は、ＡＳＴＭ Ｄ６４８−１９８８に準拠して測定した。
【０１５６】
【表１】

【０１５７】
表１から、実施例１〜１０の樹脂組成物は、比較例１のものに比べて、何れも剛性の大幅な向上と耐熱性の向上が認められることが分かる。また、比較例１の樹脂組成物は、実施例と、極性基及び疎水基を導入する処理を行わない以外は同様のシリカ化合物を酸化化合物（Ｂ）として用い、かつオレフィン系樹脂（Ａ）との混練法は、比較例１と実施例とでは同様であることを考慮すると、この結果は、本発明の樹脂組成物では均一分散性と相互作用が向上したことを示すものと考えられる。
【０１５８】
また、表１から、実施例１、２と実施例９、１０を比較すると、混練前の原料が同じであっても、超臨界流体を添加した方が、剛性及び耐熱性双方の物性向上の程度が大きく、均一分散性の向上に効果的であることが分かる。但し、超臨界流体を添加していない実施例９、１０でも、比較例１に対して十分な物性向上が認められることから、本発明の効果への寄与度は、製造方法より組成が大きいと考えられる。
【図面の簡単な説明】
【図１】図１は、本発明に係る樹脂組成物の車両用外装部品用途の一例を示す説明図である。
【図２】図２ａ、図２ｂは、本発明に係る樹脂組成物の車両用外板用途の一例を示す説明図である。
【図３】図３は、本発明に係る樹脂組成物の樹脂ウィンドウ用途の一例を示す説明図である。
【図４】図４は、本発明に係る樹脂製ワイパーシステの模式図である。
【図５】図５は、本発明に係る樹脂製ドアミラーステイの車両用外装部品用途の一例を示す説明図である。
【図６】図６は、本発明に係る透明樹脂部と不透明樹脂部とを一体で成形したインストルメントパネルを示す図である。
【図７】図７は、本発明に係る樹脂製ミラー、樹脂製ウィンドウを示す図である。
【図８】図８は、本発明の樹脂製ランプリフレクターを用いたヘッドランプ部を示す横断面図である。
【図９】図９は、本発明に係る樹脂組成物を用いたエンジンルーム内部品の一例を示す説明図である。
【図１０】図１０は、本発明に係る樹脂組成物を用いたエンジンルーム内部品の一例を示す説明図である。
【図１１】図１１は、本発明に係る樹脂組成物を用いた樹脂製冷却装置部品の一例を示す図である。
【図１２】図１２は、本発明に係る樹脂組成物を用いた樹脂製冷却装置部品の一例を示す図である。
【図１３】図１３は、本発明に係る樹脂組成物を用いた中空構造を有する樹脂一体成形体の一例を示す図である。
【図１４】図１４は、本発明に係る樹脂組成物を用いた中空構造を有する樹脂一体成形体の一例を示す図である。
【図１５】図１５は、本発明に係る樹脂組成物を用いた一体成形部品の一例を示す説明図である。
【図１６】図１６は、本発明に係る樹脂組成物を用いた一体成形部品の一例を示す説明図である。
【図１７】図１７は、本発明に係る樹脂組成物を用いた一体成形部品の一例を示す説明図である。
【図１８】図１８は、本発明に係る樹脂組成物を用いた可動部と非可動部を有する成形体の一例を示す図であり、図１８Ａは該成形体の横断面図、図１８Ｂは該成形体の上面図である。
【図１９】図１９は、本発明に係る樹脂組成物の車両用外装部品用途の一例を示す説明図である。
【符号の説明】
１…ドアモール、２…ドアミラーのフレーム枠、３…ホイールキャップ、
４…スポイラー、５…バンパー、６…ウィンカーレンズ、
７…ピラーガーニッシュ、８…リアフィニッシャー、
２１…フロントフェンダー、２２…ドアパネル、２３…ルーフパネル、
３１…サイドガラス、３２…リアガラス、４１…ワイパーアーム、
４２…ワイパーブレード、４３…弾性を有する支持部分、
４４…軟らかいゴム部分、４５…ワイパーアーム固定用ナット穴、
５１…ランプ・フード・フェンダー一体樹脂成形体、
５２…ピラーガーニッシュ・ガラス一体樹脂成形体、
５３…ルーフ・フェンダ・ガラス一体樹脂成形体、
５４…バックドア・ガラス一体樹脂成形体、
５５…ドア・ガラス一体樹脂成形体、
６１…インストルメントパネル、６２…計器類のカバー、
７１…フロントウィンドウ、７２…ドアウィンドウ、
７３…リヤウィンドウ、７４…樹脂製サイドミラー、
８１…車体側基体、８２…アウタ部材、８３…リフレクター、
８４…バルブ、８５…光軸調整器、８６…アウタレンズ、
９１…ラジエーター、９２…冷却液リザーブタンク、
９３…ウオシャータンクインレット、９４…電気部品ハウジング、
９５…ブレーキオイルタンク、９６…シリンダーヘッドカバー、
１０１…エンジンボディー、１０２…タイミングチェーン、
１０３…ガスケット、１０４…フロントチェーンケース、
１１１…ウォーターパイプ、１１２…Ｏ−リング、
１１３…ウォーターポンプハウジング、
１１４…ウォーターポンプインペラ、１１５…ウォーターポンプ、
１１６…ウォーターポンププーリ、１２１…ウォーターパイプ、
１２２…サーモスタットハウジング、１２３…サーモスタット、
１２４…ウォーターインレット、１３１…フード、１３２…ドア、
１３３…バックドア、１３４…ルーフ、１３５…フェンダー、
１３６…ウィンドウ、１３７…トランクリッド、
１４１…センターコンソールボックス、１４２…ピラーガーニッシュ、
１４３…インストルメントパネル、
１５１…パネル部、１５２…エアコンのエアダクトおよびケース、
１６１…ルーフレール、１６２…ルーフパネル、
１８１…チャンバー部、１８２…開閉バルブ、
１８３…開閉バルブシャフト、
１９１…フィラーチューブ、１９２…燃料タンク、１９３…燃料ポンプ、
１９４…エンジン、１９５…フィラーキャップ、１９６…ベントチューブ、
１９７…フューエルホース、１９８…空気室。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin composition having excellent physical properties such as rigidity, heat resistance and heat expansion property, a method for producing the same, and a molded article and an automobile part using the resin composition. The present invention relates to a resin composition useful as an exterior component or an outer panel and a method for producing the same, and a molded article and an automobile component using the resin composition.
[0002]
[Prior art]
As a method for improving physical properties such as rigidity, heat resistance, and thermal expansion resistance of a resin composition, a so-called polymer nanocomposite, which uses a nano-order level filler instead of a conventional reinforcing resin such as glass fiber or talc, has been developed. It is getting attention. Patent Literature 1 and Patent Literature 2 are examples of such a composite material.
[0003]
Of these, Patent Document 1 discloses a new material composition for a resin window and a technique for manufacturing the same. Specifically, in order to ensure the strength or rigidity and transparency of the resin window, a transparent non-woven resin is used. It is disclosed that a composite material of a transparent resin and silica fine particles is obtained by mixing inorganic silica fine particles during a process of polymerizing a crystalline organic polymer (for example, a transparent resin such as an acrylic resin). In the above Patent Document 1, for example, in Example 1, a polymerization reaction is carried out by mixing methyl methacrylate with benzoyl peroxide as a polymerization initiator, heating the mixture, and dropping silica fine particles dispersed in a methyl ethyl ketone solvent into the mixture. To obtain a resin composition.
[0004]
Patent Document 2 discloses that, in order to provide a composite material having excellent mechanical strength and toughness, a polyamide resin and a specific layered silicate are mutually bonded via an ionic bond, and these are uniformly formed. A composite material comprising a mixture is disclosed.More specifically, a layered clay represented by montmorillonite is used as a resin filler, and a polyamide monomer is impregnated between layers of the layered clay and then polymerized. And a composite material of the filler is obtained. In any case, by uniformly dispersing the nano-order filler at a high content, physical properties such as rigidity and heat resistance are improved without increasing the weight.
[0005]
In addition to these Patent Documents 1 and 2, the polyamide resin and the layered silicate are uniformly dispersed so as to have a specific reaction rate, and have excellent mechanical properties and heat resistance, and have excellent dyeability and whitening resistance. An improved polyamide composite material (for example, see Patent Document 3) or a polyolefin-based composite material having excellent mechanical strength and heat resistance in which a layered silicate is uniformly dispersed in a modified polyolefin without solvent (for example, see Patent Reference 4). These use a layered clay typified by montmorillonite as an inorganic filler, as in Patent Documents 1 and 2 described above, but instead of impregnating a monomer between layers, a polymer such as polyamide or polyolefin is used. This is a method of kneading with a layered clay and impregnating between layers to obtain a composite material of a polymer and a filler.
[0006]
In any of the above-mentioned polymer nanocomposites using a filler on the order of nanometers, improvement in the dispersibility of the fine filler is one of the major points in improving the physical properties. For this reason, in order to improve the dispersibility of the filler, as described in Patent Document 1 and Patent Document 2, a method in which the filler is added before the polymerization of the polymer, that is, at the stage of the monomer, and the polymer is sufficiently dispersed and then polymerized. Is being considered. However, this method is difficult to apply to olefin resins widely used as vehicle resins due to advantages such as low cost and low specific gravity. This is because catalysts used for polymerization of polypropylene or polyethylene, such as Ziegler-Natta catalysts and metallocene catalysts, are easily deactivated due to the presence of polar components. Therefore, the above-described method of adding a considerable amount of polar layered clay before polymerization is difficult to control the molecular weight and stereoregularity of the produced polymer, and requires a large amount of an expensive polymerization catalyst. Hard to say. In addition, a method of using a layered clay as a carrier and supporting a polymerization catalyst on the carrier has been studied, but it is hardly the best method for the same reason.
[0007]
On the other hand, as described above, the filler is kneaded with the polymer after polymerization as described in Patent Documents 3 and 4 in consideration of the case where it is difficult to add the filler before polymerization and the problem of cost. Various methods have been studied. When the matrix is a polar polymer such as polyamide, considerable dispersibility (delamination) can be obtained even by this method. However, olefin resins, which are non-polar polymers, can be improved significantly by modifying fillers and polymers, such as organic treatment of layered clay with alkylammonium salts and copolymerization of polyolefins with maleic acid. It is hard to say that sufficient dispersibility has been obtained.
[0008]
In consideration of such points, there has been studied a contrivance in a manufacturing method such as adding a solvent or a supercritical fluid to the molten resin at the time of kneading. An example of such a method is to mix and heat a thermoplastic resin, a clay (layered silicate) and a clay dispersant, melt the thermoplastic resin, and then knead it with a solvent such as water to form a thermoplastic resin. The method of dispersing the clay uniformly and finely in the resin (for example, see Patent Document 5) and the kneading of a thermoplastic resin and an inorganic filler (layered silicate) with a supercritical fluid allow the inorganic filler to be added to the thermoplastic resin. A method of uniformly dispersing (for example, see Patent Document 6) can be mentioned. By combining such a production method and the above-mentioned modification, the dispersibility (delamination property) of the layered clay is considerably improved even with an olefin resin which is a nonpolar polymer, but sufficient physical properties are still obtained. Hard to say.
[0009]
[Patent Document 1]
JP-A-11-343349
[Patent Document 2]
Japanese Patent No. 2519045
[Patent Document 3]
Japanese Patent Publication No. 7-47644
[Patent Document 4]
JP-A-10-30039
[Patent Document 5]
JP 2000-23997 A
[Patent Document 6]
JP 2000-53871 A
[0010]
[Problems to be solved by the invention]
As described above, one of the reasons why the improvement of the physical properties of the olefin-based nanocomposite is still insufficient is that most of the fillers studied so far are layered clays and their dispersion is insufficient. Layered clay becomes a nano-order filler only after complete delamination. Many studies on reforming and kneading methods have been devoted to this delamination, but a definitive method has not yet been established.
[0011]
The present invention has been made in view of such conventional problems, and has as its object to provide a resin composition having excellent physical properties such as rigidity, heat resistance, and thermal expansion resistance, and a method for producing the same.
[0012]
It is another object of the present invention to provide a resin composition having high rigidity and less occurrence of warpage or the like due to thermal deformation at a high temperature, and a method for producing the same. In particular, since organic resin materials have lower rigidity than metal materials such as steel and aluminum, they need to be thicker when applied to, for example, large parts such as car doors and vehicle body outer panels. Although the degree can be secured, the effect of weight reduction, which is a major aim of resinification, is diminished. It is therefore an object of the present invention to provide a resin composition having an excellent modulus of elasticity capable of improving rigidity and reducing weight without increasing the thickness of the resin material, and a method for producing the same.
[0013]
In addition, since the organic resin material releases residual stress during molding at a high temperature compared to the inorganic material and has a large thermal deformation, when applied to a large part such as a car body outer panel, for example, when the organic resin material is applied to a large part such as a car body outer plate, the heat generated by the steel material at the outer peripheral portion is reduced. Structural design to release the strain is required. If the structure that absorbs the elongation due to the thermal deformation is not sufficient, there arises a problem that a wavy surface is generated on the surface of the vehicle body outer plate or the vehicle body outer plate itself is broken. That is, an object of the present invention is to provide a resin composition capable of reducing the coefficient of thermal expansion of a resin material and a method for producing the same.
[0014]
Furthermore, the organic resin material has a lower hardness than steel, and when applied to a part exposed to the outside such as an outer plate of an automobile or interior materials or building materials touched by a human, the abrasion resistance of the resin surface due to foreign matter contact is improved. It is necessary. That is, an object of the present invention is to provide a resin composition which can be freely shaped in accordance with design specifications and which can be realized at low cost, and a method for producing the same, which has high rigidity, low thermal expansion, and scratch resistance. I do.
[0015]
Still another object is to provide a molded article and an automobile part using the resin composition.
[0016]
【The invention's effect】
The present invention disperses an oxidized compound (B) having a polar group and a partially hydrophobic group on the surface thereof in an olefin-based resin (A) having a polar group, whereby the oxidized compound (B) is converted to the olefin-based resin (A). The resin composition can be uniformly dispersed therein, thereby giving the resin composition obtained physical properties such as rigidity, heat resistance and thermal expansion resistance.
[0017]
The present invention relates to a vehicle interior / exterior component molded article using the above resin composition, a vehicle outer panel, a resin window, a resin wiper system, a resin door mirror stay, a resin pillar, a resin window with a heating wire, and a resin mirror. , Resin lamp reflectors, resin engine room covers and cases, engine room covers and cases, resin cooling device parts, using the above resin composition with excellent physical properties such as rigidity, heat resistance and thermal expansion resistance By doing so, it can be effectively used for vehicle applications that are large and have high demands on rigidity and impact resistance, and when an amorphous polyolefin resin is used as the olefin resin (A), it has excellent transparency. It can also be used effectively as a resin window that has a strong demand for securing a visual field.
[0018]
The resin composition of the present invention has been developed and studied by focusing on improving the affinity of an oxidized compound (B), particularly a silica compound, as an inorganic component to be added to the olefin resin (A). As a result, they found a method that can improve strength and heat resistance and reduce the coefficient of thermal expansion. If this material is used for industrial applications such as automobiles, home appliances, and houses, it is possible to reduce the weight of members and increase the degree of freedom in molding. For example, if it is used for the outer panel or exterior parts of an automobile, it can greatly contribute to reducing the weight of the vehicle and creating a new design.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, an embodiment of the present invention will be described in detail along with its operation.
[0020]
A first aspect of the present invention is that an olefin resin (A) having a polar group (hereinafter, also simply referred to as “olefin resin (A)”) has an oxidized resin having a polar group and a partially hydrophobic group on its surface. A resin composition in which compound (B) (hereinafter, also simply referred to as “oxidized compound (B)”) is dispersed.
[0021]
In the conventional technology section, it was stated that in polymer nanocomposite, improving dispersibility is one of the major points in improving physical properties, but at the same time, the interaction between the matrix polymer and the filler is also an important factor . That is, the greater the interaction between the polymer and the filler, the better the mechanical and thermal properties. The interaction also affects the dispersibility. If the interaction is weak, it is disadvantageous for uniform dispersion at the stage of compositing, and even if uniform dispersion can be achieved at the stage of composite, subsequent processing into the final product When heated and melted at the stage, there is a high possibility that the filler reagglomerates. Therefore, it is important to simultaneously improve the uniform dispersibility of the filler in the polymer and improve the interaction between the filler and the polymer. According to the present invention, it is possible to uniformly disperse the oxidized compound (B) as a filler in the olefin-based resin (A) which is a polymer, and the interaction between the oxidized compound (B) and the olefin-based resin (A). Can be improved, and therefore the mechanical properties and thermal properties such as rigidity, heat resistance, and thermal expansion resistance of the obtained resin compound can be improved.
[0022]
In the present invention, it is essential that the oxidized compound (B) has a polar group and a partial hydrophobic group on the surface. Examples of such an oxidized compound (B) include silica having a polar group on the surface, Titania, alumina, zirconia and the like, or a composite oxide compound in which the surface of titania is treated with alumina and a part of which is hydrophobized, for example, may be mentioned. In the present invention, any of these compounds may be used, but a silica compound is particularly preferred in terms of availability, cost, and surface treatment.
[0023]
In the present invention, the polar group on the surface of the oxidized compound (B) exists for the purpose of improving the interaction between the filler and the polymer, and the polar group on the olefin-based resin (A) side, which will be described later, has a hydrogen bond and an ion. By generating a chemical bond such as a bond or a covalent bond, these interactions are improved. This interaction also synergistically improves the uniform dispersibility of the oxidized compound (B) in the olefin resin (A). Here, examples of the polar group include a hydroxyl group, an amino group, a carboxyl group, an amide group, a carbonyl group, an imino group, an epoxy group, an ether group, and a sulfonic acid group. Among these polar groups, a hydroxyl group, an amino group, a carboxyl group, an amide group, a carbonyl group, and an epoxy group are preferred from the viewpoint of interaction with a polar group on the olefin resin (A) side described later. In the present invention, any one of these polar groups may be present alone or in combination on the surface of the oxidized compound (B).
[0024]
In the present invention, the method for introducing a polar group into the surface of the oxidized compound (B) and the treating agent used in the method are not particularly limited, and known methods and treating agents can be used. Many oxidized compounds usually have a hydroxyl group on the surface unless dehydration treatment or the like is performed at a high temperature. For example, a silica compound has many silanol groups (Si-OH) on the surface. Therefore, when a silica compound is used as the oxidized compound (B), even if it is used as it is without any particular treatment, it has a polar group (hydroxyl group) on its surface. Can be achieved. As a method of introducing a polar group other than a hydroxyl group, for example, taking a silica compound as an example, a method of reacting an alkoxysilane-based compound or a chlorosilane-based compound having a desired polar group with a silanol group on the surface, or a desired method. A method in which a cation having a polar group is adsorbed on the surface is exemplified. Among them, the former method is particularly preferable from the viewpoint of chemical and thermal stability. In the former method, an alkoxysilane-based compound or a chlorosilane-based compound having a desired polar group other than a hydroxyl group is not particularly limited, and a known compound can be used. Specific examples thereof include N- (2-aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane as those having an amino group. , 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, dimethylaminomethylethoxysilane and the like; those having a carboxyl group include 1,3-bis (3-carboxypropyl) tetramethyldisiloxane, carboxy Examples of ethylsilanetriol and the like having an amide group include bis (N-methylbenzamido) ethoxymethylsilane, bis [3- (triethoxysilyl) propyl] urea, and O- (methacryloxyethyl) -N- (tri Ethoxysilylpropyl) urethane, ureapropyl Examples of methoxysilane and the like having a carbonyl group include acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyltrimethoxysilane, 2- (carbomethoxy) ethylmethyldichlorosilane, (methacryloxymethyl) dimethylethoxysilane And those having an epoxy group include 5,6-epoxyhexyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, and the like, respectively.
[0025]
In the present invention, the reaction conditions for introducing a polar group to the surface of the oxidized compound (B) are not particularly limited as long as the desired polar group can be introduced to the surface of the oxidized compound (B). An appropriate amount of a polar group-introducing agent such as the above-described alkoxysilane-based compound or chlorosilane-based compound having a desired polar group may be added to the oxidized compound (B), and the reaction may be performed under appropriate temperature and pressure conditions. At this time, a suitable acid catalyst may be added to increase the reaction rate, or a surfactant or the like may be added to improve the dispersion stability. Further, the above reaction may be carried out without a solvent or in a solvent, but is preferably carried out in a solvent. As a solvent that can be used at this time, water is preferable in consideration of a kneading process with a polymer described later, but an alcohol solvent such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, a ketone solvent such as methyl ethyl ketone, and an ester solvent such as ethyl acetate are preferable. A polar organic solvent such as a solvent, a mixed solvent of these polar organic solvents and water, or a non-polar organic solvent such as toluene may be used.
[0026]
The hydrophobic group on the surface of the oxidized compound (B) in the present invention is not necessarily required from the viewpoint of improving the interaction between the filler and the polymer, unlike the above-mentioned polar group. In the present invention, it is essential that the compound (B) is present on at least a part of the surface of the oxidized compound (B) because it greatly contributes to improvement of the dispersibility of the compound (B). In the present invention, an olefin-based resin having a polar group is used, but the olefin-based resin still has a lower polarity than other polar polymers such as polyamide, and therefore, the introduction of a hydrophobic group to the surface of the oxidized compound (B). Is required. Here, the term "hydrophobic group" mainly refers to an alkyl group, but a group in which a polar group such as a hydroxyl group or an ether group is partially introduced at the terminal or in the middle of the alkyl group as a main chain may be used. . In this case, the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms and optionally having a branch can be used. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, There are a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group.
[0027]
The treating agent used to introduce a hydrophobic group on the surface of the oxidized compound (B) is not particularly limited. For example, when a silica compound is used as an example, an alkoxysilane-based compound or a chlorosilane-based compound having a desired hydrophobic group can be used on the surface. And a method in which a cationic surfactant having a desired hydrophobic group is adsorbed on the surface. The former is more preferable in terms of chemical and thermal stability. Specific examples of the alkoxysilane-based compound and the chlorosilane-based compound having a hydrophobic group include, for example, n-butyltrichlorosilane, n-butyltrimethoxysilane, n-decyltrichlorosilane, n-decyltriethoxysilane, dimethoxymethyl Chlorosilane, n-dodecyltrichlorosilane, n-dodecyltriethoxysilane, ethyltrichlorosilane, ethyltriethoxysilane, ethyltrimethoxysilane, n-heptyltrichlorosilane, n-hexadecyltrichlorosilane, n-hexadecyltrimethoxysilane, n-hexyltrichlorosilane, n-hexyltriethoxysilane, n-hexyltrimethoxysilane, methyltrichlorosilane, methyltriethoxysilane, n-octadecyltrichlorosilane, n-octadecyl Monosubstituted alkyl silane compounds such as triethoxysilane, n-octadecyltrimethoxysilane, n-propyltrichlorosilane, n-propyltriethoxysilane, and n-propyltrimethoxysilane; n-butylmethyldichlorosilane, Decylmethyldichlorosilane, di-n-butyldichlorosilane, diethyldichlorosilane, diethyldiethoxysilane, di-n-hexyldichlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldipropoxysilane, dimethylmethoxy Chlorosilane, di-n-octyldichlorosilane, docosylmethyldichlorosilane, dodecylmethyldichlorosilane, dodecylmethyldiethoxysilane, ethylmethyldichlorosilane, n-heptylmeth Disubstituted alkyl silane compounds such as rudichlorosilane, n-hexylmethyldichlorosilane, methylpentyldichlorosilane, n-octadecylmethoxydichlorosilane, n-octadecylmethyldichlorosilane, and propylmethyldichlorosilane; and n-decyldimethylchlorosilane , Ethyldimethylchlorosilane, n-octadecyldimethylchlorosilane, n-octadecyldimethylmethoxysilane, n-octyldimethylchlorosilane, n-propyldimethylchlorosilane, trimethylchlorosilane, trimethylethoxysilane, trimethylmethoxysilane, trimethyl-n-propoxysilane, and triethyl And trisubstituted alkyl silane compounds such as -n-propylchlorosilane.
[0028]
Examples of the cationic surfactant usable in the latter method include, for example, polyoxypropylene methyl diethyl ammonium chloride, N- (3-alkoxy-2-hydroxypropyl) trialkyl ammonium chloride, methyl bis (tallowamidoethyl) 2- Hydroxyethylammonium chloride, dimethyldialkylyloxyethylammonium chloride, and polydimethylmethylenepiperidinium chloride.
[0029]
In the present invention, the hydrophobicity of the surface of the oxidized compound (B) (the substitution rate of the surface polar group to the hydrophobic group), the length of the alkyl chain (the number of carbon atoms), the type of the polar group partially introduced into the alkyl chain, and the like are described. May be determined in consideration of the dispersibility in the solvent (S) described later together with the dispersibility in the olefin resin (A), and is not particularly limited, but is more preferably as follows.
[0030]
Taking a particularly preferred example of the silica compound as the oxidized compound (B), the product of the hydrophobization rate (R) of the silanol group and the total carbon number (N) of the alkyl group (R × N: In the present specification, “R × N: Hydrophobic group is preferably introduced to the surface of the oxidized compound (B), so that the hydrophobic group introduction rate is preferably 0.01 to 8, more preferably 0.05 to 2. The introduction ratio (R × N) is preferably 0.01 to 8, more preferably 0.05 to 2. Thereby, the silanol group of the silica compound is hydrophobized by the alkyl group, whereby the affinity with the olefin resin (A) is improved, and the uniform dispersibility in the resin (A) is improved.
[0031]
Here, the hydrophobization rate (R) of the silanol group is a ratio of hydrogen atoms contained in the silanol group on the surface of the silica compound substituted with the alkyl group, and is a number exceeding 0 and 1 or less. When a polar group other than a silanol group is introduced as described above, the surface state before introducing a polar group other than a silanol group is considered as a reference. The total carbon number (N) of the alkyl group is the total number of carbon atoms of the alkyl group added by directly substituting the hydrogen atoms of the silanol group.
[0032]
For example, the structure of the surface of a silica compound is schematically shown in the following formula, and when this is modified with dimethyldichlorosilane to obtain a modified silica composition shown in the following right formula, the hydrophobization rate of silanol is obtained. Since (R) modifies two of the four silanol groups, the hydrophobization rate (R) is 2/4 = 0.5, and four methyl groups are added. The total number of carbon atoms (N) of the alkyl group is 4, and the hydrophobic group introduction rate (R × N) is 2 from this.
[0033]
Embedded image

[0034]
In the present invention, the reaction conditions for introducing a hydrophobic group into at least a part of the surface of the oxide compound (B) are not particularly limited as long as the desired hydrophobic group can be introduced on the surface of the oxide compound (B). . To the oxidized compound (B), a hydrophobic group-introducing agent such as the above-mentioned desired silane compound or cationic surfactant is added in such an amount that a desired hydrophobic group-introducing ratio is obtained, and the reaction is carried out under appropriate temperature and pressure conditions. You can do it. At this time, a suitable acid catalyst may be added to increase the reaction rate, or a surfactant or the like may be added to improve the dispersion stability. Further, the above reaction may be carried out without a solvent or in a solvent, but is preferably carried out in a solvent. As a solvent that can be used at this time, water is preferable in consideration of a kneading process with a polymer described later, but an alcohol solvent such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, a ketone solvent such as methyl ethyl ketone, and an ester solvent such as ethyl acetate are preferable. A polar organic solvent such as a solvent, a mixed solvent of these polar organic solvents and water, or a non-polar organic solvent such as toluene may be used.
[0035]
In the present invention, in the reaction for introducing a polar group and a partial hydrophobic group to the surface of the oxidized compound (B), the order of the reaction is not particularly limited, and the desired polar group and one-sided hydrophobic group may be added to the surface of the oxidized compound (B). There is no particular limitation, as long as the polar group can be introduced.If the polar group and the hydrophobic group are introduced simultaneously, the polar group is introduced first, then the hydrophobic group is introduced, or the hydrophobic group is introduced first, A group may be introduced or any of them may be introduced. As described above, when a silica compound is used as the oxide compound (B), the silica compound has a large number of silanol groups (Si-OH), that is, polar groups (hydroxyl groups) on its surface. Therefore, the process for introducing a polar group may be directly used for the process for introducing a hydrophobic group without performing a process for introducing a polar group.
[0036]
The shape of the oxidized compound (B) in the present invention is not particularly limited, and may be not only a general substantially spherical shape but also a linear shape such as a rectangular parallelepiped, a plate, a fiber, or a branched shape.
[0037]
The size of the oxidized compound (B) in the present invention is also not particularly limited, but it is necessary that at least one side has a nano-order in order to exhibit the desired performance as a polymer nanocomposite. Here, “at least one side is nano-order” means that the shape of the oxide compound (B) is substantially spherical, its diameter is at least one side in the case of a rectangular parallelepiped or a plate, or a linear shape such as fiber or branched. In the case of a branched shape, it means that at least the minor axis of the cross section of the thickness is on the order of nanometers. The range of the “nano order” here is not particularly limited, but is preferably in the range of 1 to 200 nm, more preferably 1 to 100 nm, from the viewpoint of improvement in physical properties, ease of dispersion, availability, cost, and the like. Is good.
[0038]
The compounding amount of the oxidized compound (B) in the present invention with respect to the resin composition is such that the desired uniform dispersibility and the required characteristics (eg, rigidity, heat resistance and heat expansion resistance) for the desired application can be obtained. The amount is not particularly limited as long as it is 0.1% to 60% by mass, more preferably 1% to 30% by mass. If it is less than 0.1% by mass, the compounding effect of the oxidized compound (B) is small, and almost no improvement in physical properties such as rigidity, heat resistance and heat expansion of the obtained resin composition is recognized. On the other hand, if it exceeds 60% by mass, not only the increase in specific gravity cannot be ignored, but also the cost is disadvantageous, and the features of the olefin resin (A) such as low cost and low specific gravity are impaired. In addition, a decrease in impact strength cannot be ignored. In general, when a filler is added to a polymer in a large amount, the impact strength is reduced. However, the resin composition of the present invention uses a nano-order filler and has a large interaction between the filler and the polymer. Is practically small, but when it exceeds 60% by mass, it cannot be ignored.
[0039]
The olefin resin (A) in the present invention refers to an alicyclic polyolefin represented by polyethylene, polypropylene, polymethylpentene, norbornene resin, a copolymer thereof, and a rubber component represented by ethylene / propylene rubber. It refers to a copolymer or blend product into which a polar group has been introduced. In the present invention, any of these olefin-based resins may be used, but from the viewpoint of cost, versatility, availability, and the like, polypropylene, polyethylene, or a copolymer of polypropylene and polyethylene and having a polar group; Alternatively, one obtained by rubber-modifying one of polypropylene, polyethylene, or polypropylene and polyethylene copolymer and having a polar group is particularly preferable. The olefin resin (A) in the present invention is selected from those obtained by introducing a polar group into a highly transparent olefin resin such as amorphous polypropylene, polymethylpentene, or alicyclic polyolefin, and an oxidized compound. By setting the major axis of (B) to 380 nm or less, which is a visible light wavelength, a resin composition having excellent rigidity, heat resistance, heat expansion resistance, and transparency can be obtained. In the present invention, the olefin resin (A) may be used alone or in the form of a mixture of two or more.
[0040]
The polar group of the olefin-based resin (A) in the present invention is essential for improving the interaction between the filler and the polymer, and the polar group of the oxidized compound (B) and hydrogen bond and ionic bond. A chemical bond such as a covalent bond is generated, and the interaction is improved. In addition, this interaction also synergistically improves the dispersibility. Here, the polar group is not particularly limited as long as it forms a chemical bond with the above-mentioned polar group of the oxidized compound (B), but the magnitude of the interaction, the balance of the physical properties of the resin composition, the polar group Preferred are a dicarboxylic acid anhydride group, a carboxyl group, a carbonyl group, an epoxy group, an amino group, an amide group, a hydroxyl group, and the like, because of the ease of introduction and availability. At this time, the polar group of the olefin-based resin (A) may be present alone or in combination of two or more. Here, the anhydrous dicarboxyl group refers to a group in which two adjacent carboxyl groups are dehydrated and condensed to make them anhydrous.
[0041]
The method for introducing a polar group into the olefin resin to obtain the olefin resin (A) according to the present invention is not particularly limited. For example, an unsaturated monomer having a desired polar group may be converted into an olefin resin together with a polymerization initiator and the like. A method of copolymerizing in addition to the resin may be used. The form of copolymerization may be any of random copolymerization, block copolymerization, and graft copolymerization. The olefin resin (A) may be obtained by introducing a polar group into all the molecules in the homopolymer, or an olefin resin having a polar group introduced therein may be blended with a homopolymer having no polar group. (A) may be used. The latter method is preferable because it can be realized by blending a commercially available olefin polymer into which a polar group has been introduced in advance with a homopolymer using a blender or the like. At this time, the polar group is preferably present in the range of the concentration of the polar group described below. In the above method, specific examples of the unsaturated monomer having a polar group include those having a dicarboxyl anhydride, such as maleic anhydride, itaconic anhydride, and methylmaleic anhydride; As those having maleic acid, itaconic acid, methylmaleic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and the like; those having a carbonyl group include methyl acrylate, ethyl acrylate, methyl methacrylate, And those having an epoxy group include glycidyl acrylate and glycidyl methacrylate; those having an amino group include aminoethyl methacrylate and diethylaminoethyl methacrylate; Acrylamide And the like methacrylamide; is as having a hydroxyl group, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and allyl alcohol, respectively, thereof.
[0042]
In the present invention, the addition amount of the polymer having a polar group and the polymer having no polar group is not particularly limited, but preferably, the concentration of the polar group contained in the olefin-based resin (A) is When expressed as a weight fraction with respect to the olefin-based resin (A) in terms of an unsaturated monomer containing a polar group, the range is preferably from 0.001 to 10% by mass, more preferably from 0.002 to 5% by mass. Preferably, the amount is such that Here, "in terms of the unsaturated monomer containing the polar group" means that the desired polar group is introduced by copolymerizing the unsaturated monomer having the same with the desired polar group, as described above. Means that the concentration is determined using the molecular weight of the unsaturated monomer used to introduce When the content is less than 0.001% by mass, the interaction point with the polar group of the oxidized compound (B) is small, the uniform dispersibility is reduced, and sufficient physical properties cannot be obtained. On the other hand, if it exceeds 10% by mass, not only the hygroscopicity becomes large, which adversely affects physical properties such as durability and dimensional stability, but also the production cost becomes higher than that of a homopolymer, which is disadvantageous in cost.
[0043]
The resin composition of the present invention contains an olefin-based resin (A) and an oxidized compound (B) as essential components, and, if necessary, various additives such as an antistatic agent, an antioxidant, It may contain stabilizers, ultraviolet absorbers, antioxidants, flame retardants, pigments, colorants and the like.
[0044]
The method for producing the resin composition of the present invention is not particularly limited, and known methods can be used alone or in combination. For example, a method in which the olefin resin (A) is dissolved in an appropriate solvent, the oxidized compound (B) is added thereto, the mixture is sufficiently stirred, and then the solvent is removed can be used. In order to further improve the uniform dispersibility, one of the following two production methods is preferably used.
[0045]
The first method is a production method in which an olefin resin (A) is kneaded with a solution (C) in which an oxidized compound (B) is uniformly dispersed in a solvent (S) while being in contact with the solution, and then the solvent (S) is removed. It is. Accordingly, a second aspect of the present invention is a solution (C) in which an olefin resin (A) having a polar group is uniformly dispersed in a solvent (S) with an oxidized compound (B) having a polar group and a partial hydrophobic group on the surface. And removing the solvent (S) after kneading while contacting the resin composition with the resin composition. According to this method, the oxidized compound (B) is in a state of being uniformly dispersed in the solvent (S) before kneading, and is kneaded with the olefin-based resin (A) while maintaining this state. Good uniform dispersibility can be obtained even with a material. Even if the layered clay taken up in the section on conventional technology dissolves in a solvent, it swells and the interlayer distance increases, but it is difficult to completely remove it.Before kneading, a nano-order filler aggregates. It is close to. For this reason, the magnitude of the uniform dispersibility greatly depends on the subsequent kneading step. On the other hand, according to the method of the present invention, the oxide compound (B) can be uniformly dispersed in the olefin-based resin (A) without such a problem, whereby the resin composition has rigidity and heat resistance. And physical properties such as thermal expansion resistance.
[0046]
Here, the temperature at which the olefin resin (A) is brought into contact with the solution (C) is preferably around the melting temperature of the olefin resin (A), more preferably 20 ° C. from the melting temperature of the olefin resin (A). The temperature ranges from a low temperature (that is, the melting temperature of the olefin resin (A) −20 ° C.) to the decomposition start temperature of the olefin resin (A). When contact is made at a temperature lower than the melting temperature of the olefin-based resin (A) by 20 ° C. (the melting temperature of the olefin-based resin (A) −20 ° C.), the mixing of the olefin-based resin (A) and the solution (C) May be insufficient, and uniform dispersion may not be sufficiently performed. The apparatus used for kneading is not particularly limited, and can be performed using a single-screw or twin-screw extruder or an autoclave. However, a twin-screw extruder is particularly preferable in terms of uniform dispersibility, and the solution (C) is pressurized. It is particularly preferable to provide a pump capable of addition, an addition port, and a vent capable of removing the solvent (S).
[0047]
The solvent (S) used in the first method is not particularly limited as long as it can uniformly disperse the oxidized compound (B). A single solvent or a mixed solvent may be used, but 80% by mass or more is water. Is more preferable. When the amount of water is less than 80% by mass, that is, when a solvent other than water (preferably an organic solvent) is present in an amount of 20% by mass or more, explosion-proof measures for kneading equipment, local exhaust equipment, and solvent recovery equipment are required. Also, removal of the solvent after kneading requires a great deal of labor. Preferred examples of the solvent other than water include polar organic solvents such as alcohol solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ketone solvents such as methyl ethyl ketone, and ester solvents such as ethyl acetate.
[0048]
The concentration of the oxidized compound (B) contained in the solution (C) used in the first method is preferably in a range of 1 to 70% by mass, more preferably 10 to 50% by mass in terms of weight fraction. At this time, when the concentration of the oxidized compound (B) is less than 1% by mass, a large amount of the solution (C) is required to obtain a desired blending amount of the oxidized compound (B) with respect to the resin composition. And it takes a long time to deaerate after kneading, which is not preferable in terms of man-hour and cost. On the other hand, when the content exceeds 70% by mass, it is difficult to uniformly disperse the oxidized compound (B) in the solvent (S).
[0049]
Next, as a second method, the olefin resin (A) was kneaded while being in contact with a solution (C) in which the oxidized compound (B) was uniformly dispersed in the solvent (S) and a supercritical fluid (D). Thereafter, there is a production method for removing the solvent (S) and the supercritical fluid (D), and this method is a method in which the supercritical fluid (D) is added to the first method. Therefore, the third aspect of the present invention is a solution (C) in which an olefin resin (A) having a polar group is uniformly dispersed in a solvent (S) with an oxidized compound (B) having a polar group and a partially hydrophobic group on the surface. And kneading while making contact with the supercritical fluid (D), followed by removing the solvent (S) and the supercritical fluid (D), thereby producing a resin composition. In the following description, unless otherwise specified, the concentration of the oxidized compound (B) in the solvent (S) or the solvent (C) is the same as the description in the first method, and the description is omitted here. .
[0050]
In the above-mentioned second method, the supercritical fluid is a molecular assembly which exists in a region exceeding a critical pressure: Pc and a critical temperature: Tc peculiar to each substance, is different from a gas or a liquid, or has both properties. It is. One of the features of supercritical fluids is high diffusivity, high solubility (high plasticity), and it exhibits amphipathic behavior, so by adding a supercritical fluid to the first method, There is an advantage that the compatibility between the olefin resin (A) and the oxide compound (B) is further improved, and the uniform dispersibility of the oxide compound (B) can be further improved. Although the theoretical details have not been elucidated yet, by using the supercritical fluid (D) and the solvent (S) together as in the present invention, an entrainer effect is exhibited, and the supercritical fluid (D) is produced. The uniform dispersibility of the oxidized compound (B) is improved as compared with the case where the compound is used alone. Further, the supercritical fluid is also effective for drying the solvent as described in JP-A-11-181087 and the like, and the solvent (S) is almost completely removed from the resin composition without a post-process. It is noteworthy that it is possible.
[0051]
The supercritical fluid (D) used in the second production method is not particularly limited, and a known supercritical fluid described in Japanese Patent Application Laid-Open No. H11-18087 can be used. Specifically, carbon dioxide, water, nitrogen, nitrogen oxides, ammonia, methane, ethane, propane, butane, pentane, hexane, dimethylbutane, methanol, ethanol, propanol, butanol, cyclohexane, diethyl ether, benzene, toluene, Supercritical fluids such as halogenated hydrocarbons are included. Among them, workability, safety and critical temperature: Tc is lower than the melting temperature and decomposition start temperature of the resin, and the degassing after kneading is as friendly to the working environment as possible and the cost is low. Supercritical carbon dioxide is most preferred.
[0052]
In the present invention, the temperature at which the olefin-based resin (A) is brought into contact with the solution (C) and the supercritical fluid (D) is the same as in the first production method. The temperature is preferably around the temperature, and more preferably, the temperature at which the olefin resin (A) starts to decompose at a temperature 50 ° C. lower than the melting temperature of the olefin resin (A) (ie, the melting temperature of the olefin resin (A) −50 ° C.). Range. However, as described above, the temperature t must be equal to or higher than the critical temperature: Tc. At this time, if the contact is made at a temperature lower than the melting temperature of the olefin resin (A) by 50 ° C. (the melting temperature of the olefin resin (A) −50 ° C.), the olefin resin (A) and the solution (C) In some cases, mixing with the supercritical fluid (D) becomes insufficient, and uniform dispersion may not be sufficiently performed.
[0053]
In the second method, the amount of the supercritical fluid (D) introduced can further improve the compatibility between the olefin resin (A) and the oxide compound (B), and further improve the uniform dispersibility of the oxide compound (B). The amount is not particularly limited as long as it is possible, but is preferably in the range of 1 to 20% by mass based on the olefin resin (A). At this time, if the introduction amount of the supercritical fluid (D) is less than 1% by mass, the uniform dispersibility may be insufficient. On the other hand, if it exceeds 20% by mass, the shear stress is reduced and the uniform dispersion is reduced. Performance may be reduced. In the present invention, the order of adding the solution (C) and the supercritical fluid (D) is not particularly limited, and the solution (C) and the supercritical fluid (D) are simultaneously added to the olefin resin (A) and kneaded. Alternatively, the solution (C) is first added and kneaded to the olefin resin (A), and then the supercritical fluid (D) is further added and kneaded, or the supercritical fluid (D) is first added to the olefin resin. After adding and kneading to the resin (A), the solution (C) may be further added and kneaded, or both may be used.
[0054]
The concentration of the oxidized compound (B) and the solvent (S) contained in the solution (C) used in the second production method are the same as in the first production method. However, the solvent (S) does not change in the range of 20% by mass or less from the viewpoint of the above-mentioned entrainer effect, but alcohol solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, ketone solvents such as methyl ethyl ketone, and ethyl acetate. It is also effective to positively use a polar organic solvent such as an ester-based solvent as compared with the first production method.
[0055]
Although the apparatus used in the second production method is not particularly limited, the supercritical fluid (D) is further added to a twin-screw extruder having a pressure addition port and a vent of the solution (C) shown in the first production method. Those provided with a pressure addition port are preferred. The order of adding the solution (C) and the supercritical fluid (D) is not particularly limited, and may be determined according to the layout and scale of the device.
[0056]
The resin composition of the present invention is excellent in rigidity, heat resistance, and thermal expansion resistance, and is also excellent in transparency when an amorphous polyolefin-based resin is used as described above, so these functions are required. Suitable for members, for example, transparent members and equipment used for automobiles, home appliances, and houses, such as transparent covers for instrument panels for interior materials and windowpanes (windows), headlamps, sunroofs, and combination lamp covers for exterior materials. Suitable for. In particular, the resin composition of the present invention is a resin window (particularly, a resin window with a hot wire) as a substitute for inorganic glass which is required to be lightweight and has a high degree of freedom in molding; Outer plate; Resin wiper system; Resin door mirror stay; Resin pillar; Resin molded body; Resin mirror; Resin lamp reflector; Resin engine room cover and case; Resin cooling device parts; Hollow communicating with atmosphere Resin integral molded body having a structure and / or a closed hollow structure; an integral molded part in which one part is provided with two or more different functions; a molded body having a movable part and a non-movable part; and a hydrocarbon-based fuel The effect can be effectively exerted with a part or a container for storing.
[0057]
That is, claims 16 to 35 and 39 to 45 relate to uses of the resin composition according to the present invention.
[0058]
Hereinafter, the use of the resin composition according to the present invention will be described in detail.
[0059]
A fourth aspect of the present invention is a vehicle interior / exterior component molded article and a vehicle outer panel using the above-described resin composition of the present invention. A fifth aspect of the present invention is a resin window using the above-described resin composition of the present invention.
[0060]
The resin composition of the present invention has excellent rigidity, heat resistance, and thermal expansion resistance, and also has excellent transparency when an amorphous polyolefin-based resin is used as described above. It is suitable for use as an exterior component or a vehicle outer panel. For example, as shown in FIG. 1, a door molding 1, a frame frame 2 of a door mirror, a wheel cap 3, a spoiler 4, a bumper 5, a blinker lens 6, a pillar garnish 7, a rear finisher 8, a head lamp cover (not shown), and the like. As shown in FIGS. 2A and 2B, a vehicle exterior panel such as a front fender 21, a door panel 22, a roof panel 23, a hood panel 24, a trunk lid 25, a back door panel (not shown), and the like. No. Further, for example, as shown in FIG. 3, the present invention can be applied to a windshield (not shown) of a vehicle, a side glass 31, a rear glass 32, and the like. As described above, in the present invention, a component having a desired color tone can be obtained by kneading a colorant such as a pigment into the resin composition, inserting a colored film, or painting. Further, it can be used for applications requiring rigidity, heat resistance, thermal expansion resistance, etc., other than vehicle applications, such as interior and exterior materials of buildings and railway vehicles, and housings of electric and electronic products.
[0061]
As a method for manufacturing various members including such vehicle parts and architectural interior / exterior materials, injection molding, vacuum pressure molding, heat compression molding, blow molding, or the like may be appropriately selected according to the parts. The general glass fiber reinforced resin is gradually deteriorated in physical properties and the recyclability is low because the glass fiber is broken by repeatedly receiving the shear stress, but the resin composition of the present invention has a nano-order oxidation as described above. Since the compound (B) is used, it is difficult to receive a shear stress, and a decrease in physical properties can be suppressed.
[0062]
A sixth aspect of the present invention is a resin wiper system, a resin door mirror stay, and a resin pillar characterized by comprising the resin composition of the present invention. The resin composition of the present invention is excellent in rigidity, heat resistance and thermal expansion resistance, and also excellent in transparency when an amorphous polyolefin resin is used as described above. For example, a resin wiper system, a resin door mirror It is suitable for the use of components such as stays, resin pillars and the like that require improvement in visibility.
[0063]
The conventional wiper system is composed of black painted steel and black rubber, and has a problem that visibility is obstructed during low-speed operation. Further, the conventional door mirror stays are made of resin of the same color or black paint finish as the outer plate, and there is a problem that visibility when turning right or left is obstructed. In addition, the conventional pillars are made of steel, and there is a problem that the front pillar and the center pillar obstruct visibility when the vehicle travels normally or turns left and right, and the rear pillar obstructs the view when moving backward or confirming backward. The visibility can be improved if a transparent resin material can be used for these components. However, since high rigidity, heat resistance, and dimensional stability during heating / forming are required, it has been difficult to realize the conventional transparent resin material. On the other hand, the resin composition of the present invention has high rigidity, heat resistance, and thermal expansion resistance, and also has excellent transparency when the amorphous polyolefin-based resin is used as described above. It has been found that these problems can be solved by using the resin composition for the above-mentioned parts, and the above-mentioned transparent parts can be obtained. Further, it is expected that the transparency of these parts can contribute not only to the improvement of the visibility but also to the improvement of the design.
[0064]
As an example, FIG. 4 shows a schematic diagram of a wiper system. The wiper system includes a wiper arm 41 and a wiper blade 42, and operates so as to draw a semi-arc about the wiper arm fixing nut hole 45. The wiper blade 42 is generally composed of a support portion 43 having elasticity and a soft rubber portion 44. In the wiper system of the present invention, at least one of the wiper arm, the wiper blade and the wiper blade support portion has the resin composition of the present invention. An object is used as a transparent material. In the wiper system of the present invention, it is preferable to use silicone rubber or the like having high durability and relatively high transparency as the rubber portion. Alternatively, the support portion of the wiper blade may be prepared using a resin composition obtained by adding an appropriate amount of an acrylic rubber component to the resin composition of the present invention. This is because appropriate elasticity can be given to the support portion of the wiper blade. As such a resin composition, for example, an acrylic rubber of a copolymer containing ethyl acrylate or butyl acrylate as a main component (for example, Nipol AR31 manufactured by Zeon Corporation, based on 100 parts by mass of the resin composition of the present invention) , AR32) in an amount of 0.5 to 30 parts by mass.
[0065]
As the door mirror stay or the resin pillar of the present invention, besides the door mirror stay or the pillar formed of the resin composition of the present invention as a transparent material, the resin composition of the present invention is constituted by a multilayer laminate in which the resin composition of the present invention is laminated with another resin. May be. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Is provided. By forming a multilayer laminate, additional functions other than the resin composition of the present invention can be added. When a multilayer laminate is used, an optimal thickness can be selected from the thickness of the final molded article and the number of layers, as the thickness of each layer. Examples of other resins in the case of forming such a multilayer laminate include, for example, polyester, polyamide, and polycarbonate. In addition, as the multilayer laminate, the thermoplastic resin laminate of the present invention using the resin composition layer also for the outermost layer and the lowermost layer of the above-mentioned laminate, and more preferably also for the intermediate layer, can be used. A method for producing a wiper system, a door mirror stay, or a resin pillar using the resin composition of the present invention or the multilayer laminate described above is not particularly limited. In addition to molding the door mirror stays and pillars as a single component, if the door mirror stays and pillars can be used, for example, by a method of manufacturing an integrally molded body described later, the door mirror stays and the front pillars, or each pillar and the resin roof can be used. It is also possible to form an integrally molded body with the panel.
[0066]
A seventh aspect of the present invention is a resin molded article having a transparent part and an opaque part, wherein at least the transparent part contains the resin composition. The resin composition of the present invention has excellent rigidity, heat resistance, and thermal expansion resistance, and also has excellent transparency when an amorphous polyolefin resin is used as described above, and the olefin resin is originally chemically resistant. Since it is an excellent resin, it has a transparent part and an opaque part, and can be suitably used for a resin molded article obtained by integrally molding these parts. Such a resin molded article will be described by taking an automobile part as an example.
[0067]
Automobiles include a mixture of transparent parts such as various lamps, covers, and glass, and opaque parts such as outer panels and various interior parts. Each of these components requires different characteristics such as transparency, rigidity, heat resistance, low coefficient of linear expansion, and chemical resistance, so conventional resin materials combine these transparent and opaque components. Conversion was difficult. However, since the resin composition of the present invention can be easily molded by injection molding, vacuum pressure molding, etc., using the resin composition of the present invention as a transparent material, high rigidity, high heat resistance, low linear expansion coefficient, A transparent part and an opaque part are integrally molded while ensuring high chemical resistance, so that the number of parts and the number of steps can be reduced, and the weight of parts can be reduced. In addition, since the transparent portion and the opaque portion are integrally formed, the outline that has been conventionally divided can be formed by one continuous line, so that the appearance of the component can be improved.
[0068]
More specifically, a headlamp that requires transparency contacts another opaque component, such as a bumper, a front grill, a fender, and a hood, that surround the headlamp. When these are integrally molded, the number of parts can be reduced, and the number of steps at the time of assembling can be reduced because the integrated parts may be assembled. In particular, since the resin composition of the present invention is excellent in heat resistance, there is no problem that the heat source of the lamp is close and the resin is melted. The conventional headlamp is made of polycarbonate resin and therefore has low light resistance, and turns yellow when exposed to sunlight, so a surface layer coating was required. However, such a problem is solved by using the resin composition of the present invention.
[0069]
The method for producing such a resin composition is not particularly limited. For example, there is an automotive glass as a component that requires transparency, such as a side glass attached to a door, a back door glass, a rear quarter glass adhered to a rear fender and a roof, a rear glass, and the like. It is called. The side glass and the back door glass have a structure in which glass is disposed between a door outer and a door inner. By forming a hollow portion inside using a door outer and a door inner in advance and pouring the resin composition of the present invention into the hollow portion, the door outer, the door inner, and the glass can be integrally formed. Similarly, the pillar garnish and the rear quarter glass can be integrated. The resin molded product of the present invention is shown in FIG. 5, but is not limited to the resin molded product in which the pillar garnish and the rear quarter glass are integrated, but also a resin molded product 51 integrated with a lamp, a hood and a fender, and a resin molded product integrated with a pillar garnish glass. Body 52, a roof / fender / glass integrated resin molded body 53, a back door / glass integrated resin molded body 54, a door / glass integrated resin molded body 55, and the like. Note that a door lock, a wiper motor, and the like may be installed in a hollow portion of a component in a later process.
[0070]
Further, in the case of an instrument panel as an interior material for a vehicle, instruments, a transparent cover thereof, and a cluster lid are conventionally made of separate parts. However, when the transparent resin portion and the opaque resin portion are integrally formed using the resin composition of the present invention, several types of parts are formed in the instrument panel by integrating the instrument panel 61 and the instrument cover 62 in advance. By consolidating, the number of parts can be reduced and the weight can be reduced. FIG. 6 shows a schematic diagram of such an instrument panel.
[0071]
In addition, utilizing the characteristics of the transparent and high strength and high rigidity of the resin composition of the present invention, a part of the resin molded body is a transparent part and the other part is opaque, and has maintained high strength and high rigidity. It can also be a member. For example, when the resin composition of the present invention is used for a part of a roof, the part can be made transparent, and a transparent roof can be obtained without providing a glass sunroof. In the resin molded body, the opaque portion may be colored.
[0072]
In the resin molded article having a transparent part and an opaque part in the present invention, in order to obtain a resin molded article of a colored opaque part, a method using a colored raw material resin, a method of painting or printing on the opaque part, or a method of coloring There is a method using a colored sheet as the opaque resin.
[0073]
As a method for preparing a colored raw resin, in addition to a method in which a pigment is dispersed in the raw resin in advance, a raw resin pellet and a pigment pellet are simultaneously melted and kneaded, and are injected into a mold using an injection molding machine. There is a method of obtaining a colored resin. In order to manufacture the resin molded article of the present invention using the colored resin, subsequently, the mold is opened, or a new molten resin passage is newly formed, and the transparent molten resin is formed in the cavity of the mold using another cylinder. Should be injected. Thereby, a resin molded body having a transparent portion and a colored opaque portion can be manufactured. Either the opaque resin may be injected first or the transparent resin may be injected first.
[0074]
In order to form a colored opaque portion by painting or printing, a transparent resin is melted in advance to form a desired resin molded body, and thereafter, painting or printing is performed from the front or back surface of the resin molded body to give a colored and opaque portion. How to ensure. Painting or printing can be performed before shaping the molten resin, and shaping can be performed thereafter.
[0075]
When a colored sheet is used as the opaque resin, a pre-colored opaque sheet is preliminarily shaped and placed in a mold, and then a molten transparent resin is injected into the mold, and the resin is cooled and solidified. After that, if it is taken out from the mold, the resin molded product of the present invention can be obtained.
[0076]
Further, according to the above-described method, for example, the roof / fender / glass integrated resin molded body is not limited to a resin molded body in which the glass part is a transparent part and the roof and the fender are opaque. The portion may be a transparent portion, and the fender, glass, and the rest of the roof may be an opaque resin molded body.
[0077]
Further, the resin molded body of the present invention in which the transparent part and the opaque part are integrally molded can be constituted by the resin composition of the present invention and the pigment, and a multilayer obtained by laminating the resin composition of the present invention and another resin. It is also possible to form a laminate. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Can be provided. By thus forming a multilayer laminate, it is possible to provide an additional function that cannot be exhibited only by the resin composition of the present invention. In addition, the kind of other resin which comprises a multilayer and the thickness of each layer can be suitably selected according to the use of a resin molded object.
[0078]
An eighth aspect of the present invention is a resin window with a hot wire, a resin mirror, a resin lamp reflector, a resin engine room cover and case, and a resin cooling device, comprising the resin composition of the present invention. Parts.
[0079]
The resin composition of the present invention has excellent rigidity, heat resistance, and thermal expansion resistance, and also has excellent transparency when an amorphous polyolefin resin is used as described above, and the olefin resin is originally chemically resistant. This resin is suitable for use in parts such as a resin window, a resin mirror, a lamp reflector, a cover and a case in an engine room, and the number of parts, the number of steps, and the weight can be reduced. Further, by using the resin composition of the present invention as a transparent material, it becomes possible to substitute materials for parts requiring transparency, and to improve anti-fog properties and visibility.
[0080]
For example, the resin window such as the rear window 73, the door window 72, and the front window 71 shown in FIG. 7 may be provided with a heat wire heater that can be heated inside or on the surface of the molded body to provide an anti-fog function. When a conventional transparent resin material is used, heat resistance and thermal expansion of the resin material by a hot-wire heater become problems. However, when the resin composition of the present invention is used, these problems do not occur. Further, since the resin composition of the present invention has high rigidity, it can be applied to large components such as the front window 71, the door window 72, and the rear window 73, and can be reduced in weight. Examples of the method of forming the hot-wire heater include a method of insert-molding a hot-wire portion formed into a film, and a method of forming a hot-wire portion on the indoor side surface by vapor deposition, coating, printing, or the like. Also, when the resin side mirror 74 (see FIG. 7) is manufactured using the transparent resin of the present invention, the weight can be reduced as compared with the case where the conventional glass or transparent resin is used. It is also possible to provide a fogging function. In addition to the side mirror shown in FIG.
[0081]
FIG. 8 is a cross-sectional view of an automobile lamp. A reflector 83 is disposed inside an outer member 82 fixed to the vehicle body-side base body 81, and a bulb 84 and an optical axis adjuster 85 are connected to the reflector 83. The outer member is further fitted with an outer lens 86. . When a reflector is formed using a conventional resin material, the heat resistance, the coefficient of linear expansion, and the anisotropy of linear expansion were sometimes inferior. However, these problems can be solved by using the resin composition of the present invention. In particular, since the resin composition of the present invention has high rigidity, it can secure light weight and high heat resistance, and can be a lamp reflector excellent in dimensional stability and surface smoothness, and can be used as a reflector such as a head lamp, a fog lamp, or a rear combination lamp, or It can be suitably used for a sub-reflector of a headlamp. As a method of forming the reflecting portion, for example, a method of insert-molding the reflecting film portion when manufacturing the member, a method of forming a vapor-deposited film on the reflecting portion after molding the member by injection molding or press molding, and the like. There is.
[0082]
Further, the resin composition of the present invention can be applied to a cover and a case in an engine room. 9 and 10 show the inside of the engine room. Since the resin composition of the present invention is excellent in transparency, heat resistance, chemical resistance, and rigidity, it can be used in an engine room where temperature conditions are severe and can be a lightweight component. Such components include, for example, a radiator 91, a coolant reserve tank 92, a washer tank inlet 93, an electrical component housing 94, a brake oil tank 95, a cylinder head cover 96, an engine body 101, a timing chain 102, a gasket 103, and a front chain case. 104 and the like. Moreover, since the resin composition of the present invention is transparent, visibility in a tank or cover such as the above-mentioned washer tank inlet, electric component housing, brake oil tank, cylinder head cover, timing belt cover and the like can be improved.
[0083]
Since the resin composition of the present invention can be a lighter component having excellent heat resistance, chemical resistance, and rigidity, it is suitable for use in components used under contact with cooling water in an automobile engine room. used. Such resin cooling device parts are shown in FIGS. For example, a water pipe 111, an O-ring 112, a water pump housing 113, a water pump impeller 114, a water pump 115, a water pump pulley 116 shown in FIG. 11, a water pipe 121, a thermostat housing 122, a thermostat 123, and water shown in FIG. Radiator tank parts such as the top and base of the radiator tank such as the inlet 124, and parts such as valves. When the resin composition is used, weight reduction, improvement in chemical resistance, and improvement in fuel efficiency are achieved, so that its practical value is high.
[0084]
The components of the present invention can be composed of the resin composition of the present invention alone, but can also be composed of, for example, a multilayer laminate in which the resin composition of the present invention is laminated with another resin material. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Can be provided. By forming a multilayer laminate, it is possible to provide additional functions that cannot be exhibited only by the resin composition of the present invention. In addition, the kind of other resin which comprises each layer, the thickness of each layer, etc. can be suitably selected according to the purpose of use.
[0085]
A ninth aspect of the present invention is an integrated resin article having the above-mentioned resin composition and having a hollow structure communicating with the atmosphere and / or a closed hollow structure. As described above, the resin composition of the present invention has excellent rigidity, heat resistance, and thermal expansion resistance, and also has excellent transparency when an amorphous polyolefin-based resin is used as described above. It is suitable for use in parts having a hollow structure such as a roof and a hood.
[0086]
2. Description of the Related Art Outer and inner and outer parts of an automobile are often composed of a steel plate and a resin panel and have a hollow structure in which accessories and the like are mounted inside the part. For example, the side door and the back door have a hollow structure formed of a steel plate on the outside and the inside, and a resin panel is attached to the inside steel plate in an assembling process after painting, and various accessories and the like are attached in the hollow structure. The roof, hood, trunk lid, back door, and the like have outer plates and reinforcing rain hoses made of steel plates, and resin parts are attached inside after painting. These parts having a hollow structure are large in size, and are required to have rigidity and dimensional stability, so that it has been difficult to integrally mold with a conventional resin material. However, when the resin composition of the present invention having high rigidity, low coefficient of thermal expansion, and low coefficient of thermal shrinkage is used, integral molding becomes possible, and the number of these components, the number of steps, and the weight can be reduced.
[0087]
The resin integrated molded article of the present invention can be composed of only the resin composition of the present invention, but can also be composed of, for example, a multilayer laminate in which the resin composition of the present invention is laminated with another resin material. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Can be provided. By forming a multilayer laminate, it is possible to provide additional functions that cannot be exhibited only by the resin composition of the present invention. The type of other resin constituting the multilayer laminate, the thickness of each layer, and the like can be appropriately selected according to the purpose of use. In addition, as the multilayer laminate, the thermoplastic resin laminate of the present invention using the resin composition layer also for the outermost layer and the lowermost layer of the above-mentioned laminate, and more preferably also for the intermediate layer, can be used.
[0088]
The resin-integrated molded article of the present invention can improve the design, touch, and texture by providing a decorative layer such as a skin material and a design printing layer on the outermost surface layer, and can improve the product quality. It is preferable that the outermost layer is made of a decorative material. For example, a molded article provided with a skin material such as a brushed sheet, an embossed pattern sheet, a laser pattern sheet, and a woodgrain sheet on the outermost surface layer can be used for a roof indoor side, pillar garnishes, instrument panels, and the like. When the above-mentioned multilayer laminate is used, the design printing layer may be provided in the intermediate layer, and the glossiness and depth can be enhanced by using a transparent material for the surface layer.
[0089]
In the integrally formed article having a hollow structure of the present invention, the hollow structure is preferably filled and sealed with a gas, a liquid, a solid, or a mixture thereof. This is because heat insulation performance and sound insulation performance can be improved. The material to be filled and sealed is not particularly limited, and a known filling and sealing material can be used.For example, when transparency is required, a gas such as nitrogen, argon, carbon dioxide, or air is preferable. When transparency is not required, it is preferable to use, in addition to the above-mentioned gases, paraffin, wax, and the like, which are liquid when heated at the time of encapsulation and become solid at room temperature after encapsulation. With the above-mentioned encapsulant, it is possible to maintain a comfortable vehicle interior environment by suppressing the escape of cold heat and the invasion of high heat of the outside air from the vehicle compartment in the summer, and the escape of heat and the invasion of the cold heat of the outside air in the winter. In addition, the double-walled structure having a hollow portion inside can reduce or absorb external noise energy to achieve a quiet vehicle interior environment. Further, by applying the resin-integrated molded body of the present invention to a hood, sound radiation and heat radiation from an engine room can be reduced.
[0090]
The method for producing the integrally molded article having a hollow structure of the present invention is not particularly limited, and known methods can be applied. Examples thereof include a general vacuum pressure molding method, an injection molding method, a blow molding method, and a press molding method. Can be used. For example, the following method is preferably used.
[0091]
As a first method, two resin sheets made of the resin composition of the present invention are fixed to a holder provided with a pressurized fluid introduction path, and the holder is sealed by a known method to form a space between the two sheets. Form a closed space. After each sheet is heated to a temperature equal to or higher than the deflection temperature under load and inserted into a mold in an open state, the outer peripheral portion of the softened sheet is pressed and welded with the mold. At this time, a pressurized fluid is injected into the sealed space between the two sheets before or during or after the outer peripheral portion is welded or after the welding, preferably before or after the welding, and the sheet is expanded / Alternatively, after expansion, the mold is closed and the pressurized fluid pressure is maintained until the molded body cools, thereby forming a hollow structure. Preferably, a mold provided with a vacuum evacuation hole is used, and vacuum suction is also used at the time of sheet expansion to enhance the adhesion between the mold surface and the sheet. By using vacuum suction, the transferability of the obtained integrally molded body can be improved. That is, the tenth aspect of the present invention is to heat two resin sheets containing the resin composition of the present invention, insert this into an open mold, press the sheet outer peripheral portion, and weld the outer peripheral portion. A resin according to the present invention, in which a pressurized fluid is injected between the sheets before or after welding, and after the sheet is expanded and / or expanded, the mold is closed and the pressurized fluid pressure is maintained to form a hollow structure. This is a method for producing an integrally molded article.
[0092]
As a second method, while filling or after filling the molten resin composition of the present invention in a mold in a closed state, the mold is retracted and pressurized inside the molten resin while expanding the cavity volume. This is a method of forming a hollow structure by injecting a fluid. That is, in the eleventh aspect of the present invention, while filling the molten resin composition of the present invention in a closed mold, and / or after filling, the pressurized fluid is injected into the molten resin while expanding the cavity volume. It is a manufacturing method of the resin integral molding of the present invention which forms a hollow structure.
[0093]
As a third method, a single resin sheet made of the resin composition of the present invention is inserted into the cavity surface of one side of the mold, and the cavity is filled by filling the molten resin on the back surface or withdrawing the mold after filling to reduce the cavity volume. A method of forming a hollow structure by injecting a pressurized fluid into the molten resin while expanding, or inserting two sheets of resin into the cavity surfaces on both sides of the mold, filling the molten resin between the sheets, and filling the cavity volume And a pressurized fluid is injected to form a hollow structure. That is, the twelfth aspect of the present invention is that one or two resin sheets containing the resin composition of the present invention are inserted into the mold cavity surface in the open state, and the mold is closed to remove the two sheets. Alternatively, a method of manufacturing a resin-integrated molded article according to the present invention, in which a back surface of one sheet is filled with a molten resin or, after filling, a cavity is formed by injecting a pressurized fluid into the molten resin while expanding the cavity volume. Is provided.
[0094]
In the above embodiment, the type of the resin to be filled in the sheet is not particularly limited as long as the resin is in close contact with the sheet made of the resin composition of the present invention, but is preferably the same type as the resin type in contact with the resin composition of the sheet. A resin or a resin having a solubility parameter (SP value) close to the resin is used.
[0095]
In the present invention, the pressurized fluid is not particularly limited, and is selected from known pressurized fluids in consideration of the components of the resin sheet and the like. For example, air, a gas such as nitrogen gas, or a liquid such as water or silicone oil is preferably used.
[0096]
As shown in FIGS. 13 and 14, as an application part of the resin-integrated molded body having a hollow structure of the present invention, for example, a hood 131, a door 132, a back door 133, a roof 134, a fender 135, a window 136, a trunk lid 137, The center console box 141, the pillar garnish 142, the instrument panel 143, the head lining, and the like can be given. These components can simultaneously and integrally form the inner / outer and accessory components, the rain hose, and the like, and can reduce the number of components and the number of steps. Further, an additional function can be provided by enclosing a gas, a liquid, a solid, or a mixture thereof in the hollow portion. For example, the hood can be integrated with a rain hose and can provide sound insulation and heat insulation functions, the roof can be integrated with a head lining and the insulation and sound insulation functions can be provided, and doors and fenders can have inner / outer parts. Integration is possible.
[0097]
A thirteenth aspect of the present invention makes it possible to integrate two or more kinds of parts having different functions, each of which comprises the resin composition of the present invention, and one part is provided with two or more different kinds of functions. It is an integrally molded part. Here, the different functions include, for example, a display function such as an instrument panel, a ventilation function such as an air conditioner duct, and a fixing function such as a roof rail. Since the resin composition of the present invention has various functions as described above, it can be applied to members expected to secure various functions, and two or more types having different functions by integrally molding these. Can be integrated to form an integrally molded part in which two or more functions are added to one part. This is suitable for integration of large parts, so-called modularization and integration (integration), and it is possible to reduce the number of parts, the number of steps, and the weight while maintaining high quality.
[0098]
For example, the instrument panel shown in FIG. 15, which is a large interior component, currently has a panel part 151, an air duct for an air conditioner, a case 152, and a cross car beam (steering cross member) that are separately manufactured and assembled on a car production line. ing. If it is attempted to integrally mold the panel part and the air duct or case of the air conditioner with a conventional resin material, sinks and distortions due to molding shrinkage due to molding and shrinkage due to large and complex shaped parts, expansion due to heat, etc. will be issues. Such a problem can be solved by using a resin composition. In addition, since the resin composition of the present invention has high rigidity, it is possible to form the entire part into a structure by such integral molding, and to eliminate a cross car beam (steering cross member) conventionally using steel. It is possible to do. Further, by using the resin composition of the present invention, it is possible to integrally mold a bracket or the like which had to be retrofitted with steel. In addition, when a decorating material such as a skin material is put into a mold during insert molding and insert molding is performed, integral molding with the decorating material can be performed. A similar effect can be obtained, for example, when applied to a door. At present, door inner panels are mainly made of steel, and various parts such as side window guide rails, regulators, door locks, and speakers are assembled on a production line. By using the resin composition of the present invention, a door inner panel, a guide rail, a speaker housing and the like can be integrally formed.
[0099]
FIG. 16 shows another example of the integrally molded part of the present invention. As shown in FIG. 16, when the roof rail 161 which is a large exterior component is taken as an example, it can be integrally formed with the roof panel 162 made of the resin composition of the present invention described above. Since the roof rail is heavy and used in an environment that is severe in terms of temperature, rigidity and heat resistance have been particularly issues with conventional resin materials. However, such problems can be solved by using the resin composition of the present invention. Similar effects can be obtained, for example, when applied to a spoiler, and can be integrally formed with the above-described trunk lid made of the resin composition of the present invention.
[0100]
FIG. 17 shows a radiator core which is a large body part. At present, resin-made radiator cores are becoming popular as front-end modules.However, when the resin composition of the present invention is used, it is possible to further reduce heat resistance, chemical resistance, rigidity, and to make lighter parts, Shrouds, brackets and the like can also be integrally formed. In particular, when the resin composition of the present invention is used, a transparent portion such as a radiator reservoir tank or a headlamp cover can be integrally formed, and in addition, a bumper reinforcing material which has been conventionally a separate body can be integrated. It becomes. Further, when an air cleaner, a throttle chamber, and the like, which are components in an engine room, are taken as an example, by using the resin composition of the present invention having excellent heat resistance and chemical resistance and low linear expansion, these components can be integrated. . Conventionally, such integration has been attempted, but the engine room is in a severe environment with high temperature and chemicals such as oil, and this countermeasure has been a problem with conventional resin materials. The use of an object can solve such a problem. The same effect can be obtained even when applied to an intake manifold or a cylinder head cover, and it can be integrally formed with the above-mentioned parts.
[0101]
The integrally molded part of the present invention can be constituted only by the resin composition of the present invention, but can also be constituted by a multilayer laminate in which the resin composition of the present invention is laminated with another resin material. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Can be provided. By forming a multilayer laminate, it is possible to provide additional functions that cannot be exhibited only by the resin composition of the present invention. As such a multilayer laminate, there is the above-mentioned thermoplastic resin laminate.
[0102]
Since the resin composition of the present invention is excellent in rigidity, heat resistance, and thermal expansion resistance, when formed into an integrally molded part, it is suitable for use as a part having a movable part and a non-movable part such as a throttle chamber. . Therefore, a fourteenth aspect of the present invention is a molded article having a movable part and a non-movable part comprising the resin composition of the present invention.
[0103]
2. Description of the Related Art Many components having a movable part and a non-movable part are used in intake and exhaust system parts of automobiles and air conditioner units. These parts are mainly for controlling the flow of gas such as air, and serve as non-movable parts, which serve as flow paths for gas, that is, cylindrical parts (formed bodies) for introducing flowing gas. And a movable part, which can be opened and closed, for controlling gas flow, such as a throttle chamber and each door in an air conditioner unit. Airtightness is important for these parts. In particular, when applied to parts in an engine room, heat resistance is also required. However, by using the resin composition of the present invention having a low coefficient of thermal expansion, a low coefficient of thermal shrinkage, and high heat resistance, these problems can be solved, and a component having excellent airtightness can be obtained. Furthermore, since the resin composition of the present invention has high rigidity, it is possible to reduce the weight of these components and thereby improve the response.
[0104]
The molded body having the movable portion and the non-movable portion of the present invention may be assembled separately after molding the movable portion and the non-movable portion separately using, for example, an injection molding method. It is preferable that the movable part and the non-movable part are integrally formed by a method. This is because the airtightness is further improved, and the number of steps and the number of parts can be reduced. Taking the throttle chamber shown in FIG. 18 as an example, it can be manufactured, for example, by the following method.
[0105]
The throttle chamber has a cylindrical chamber portion 181 which is a non-movable portion, and an opening / closing valve 182 and an opening / closing valve shaft 183 which are movable portions. First, a metal shaft for an on-off valve is set in a two-color molding die, then a cylindrical chamber is injection-molded, and then the slide core is retracted to form a disc-shaped on-off valve. Injection molding of a disk-shaped open / close valve. At this time, the metal shaft and the disc-shaped on-off valve are integrated. According to the present invention, the movable portion is an opening / closing lid for controlling gas flow, and the non-movable portion can be preferably applied to a cylindrical molded product into which flowing gas is introduced.
[0106]
The resin composition of the present invention is a component or a container for storing a hydrocarbon-based fuel, a component or a container for storing a hydrocarbon-based fuel, for example, because the hydrocarbon-based fuel has excellent barrier properties, gas barrier properties, and chemical resistance. It is suitable for use in a series of fuel system parts for vehicles that store hydrocarbon fuel such as a fuel tank, and household goods such as kerosene containers. Accordingly, a fifteenth aspect of the present invention is a component or container for storing a hydrocarbon-based fuel containing the resin composition of the present invention.
[0107]
FIG. 19 shows a resin fuel tank for a vehicle such as an automobile, which is such a component or container. Gasoline, which is a hydrocarbon-based fuel, is injected and stored in a fuel tank 192 via a filler tube 191, and then the gasoline is pumped by a fuel pump 193 to an engine (not shown; indicated only as reference numeral 194). Fuel system. The fuel tank 192, the filler cap 195, the vent tube 196, the fuel hose 197, the fuel cutoff valve, the delivery pipe, the evaporative tube, the return tube, and the fuel sender module as components to which the resin composition of the present invention can be applied in the fuel system component. And the like. The fuel tank is the largest component of these vehicles' fuel system components.
[0108]
Here, the current state and issues of resinification of the fuel tank will be described in detail. Hitherto, olefin-based HDPE (high-density polyethylene) has been used as a base resin, and molding has been performed by a blowing method. Although there were no significant changes in these materials and construction methods, the layer structure of the tank changed significantly. For example, the fuel tank was initially a single-layer fuel tank, but with the enforcement of the Regulation on Evaporation of Hydrocarbons, the fuel tanks had to be multi-layered to reduce hydrocarbon permeation. As a result, at present, the mainstream of the fuel tank is a multi-layer tank composed of three types and five layers in which both ends of HDPE / PA (polyamide) or HDPE / EVOH (ethylene-vinyl acetate copolymer) are made of HDPE. The molding in this case is the same as the conventional blow molding.
[0109]
In the single-layer fuel tank, the permeation of more hydrocarbon-based fuel than the tank is due to the good compatibility between the two. The solubility parameter (hereinafter referred to as SP value), which is a measure of compatibility, is 7.9 for HDPE and 6 to 8 for hydrocarbon-based fuel, and both are in the same region. On the other hand, the SP value of PA used for the multi-layer tank is 13.6, which is in a region where the SP value is greatly different from that of the hydrocarbon-based fuel, in other words, the compatibility is poor. From these, the PA material in the multilayer fuel tank is provided as a barrier layer for preventing the permeation of the hydrocarbon-based fuel to the outside of the tank. The creation of the multi-layer fuel tank has established a technique that satisfies the regulation on the regulation of evaporation of hydrocarbons, but the molding process has become complicated and has led to a significant increase in price. In addition to the above problems, the laminated structure of a plurality of resins has led to a loss of smoothness in recycling, leaving a new problem that cannot be met in the age of a recycling society.
[0110]
On the other hand, the oxidized compound (B) in the resin composition of the present invention has a relatively high SP value due to the presence of the polar group, and has a function of preventing the permeation of the hydrocarbon-based fuel corresponding to the aforementioned PA or EVOH. There is. Therefore, the use of the resin composition of the present invention can provide a fuel tank for a vehicle which has a small amount of hydrocarbon transpiration even in a single-layer type, reduces production costs, and is excellent in recyclability. In this case, the resin composition of the present invention can be used for molding into a fuel tank for a vehicle by blow molding as in the conventional case, whether it is a single layer type or a multilayer type if necessary.
[0111]
Although the effect is slightly lower than that of a fuel tank for a vehicle, the resin composition of the present invention can be used for household goods such as a kerosene container in addition to the fuel tank for a vehicle. This reduces the evaporation of kerosene into the atmosphere, which can contribute to the preservation of the global environment.
[0112]
As described above, in the present invention, it is also possible to obtain a component having a desired color tone by kneading a colorant such as a pigment into the resin composition or inserting a colored layer. For this reason, in addition to the automobiles described above, applications requiring appearance quality such as aesthetics, smoothness, and transparency, and requiring high rigidity and surface scratch resistance, for example, exterior materials for buildings, interior materials, and railway vehicles It can also be used for interior materials.
[0113]
The method of manufacturing various members including such vehicle parts and building interior materials has been described in detail above, but injection molding, vacuum pressurized air molding and the like may be appropriately selected according to the parts and applications. General glass fiber reinforced resin, the glass fiber is broken by repeatedly receiving shear stress, the physical properties of which gradually decrease and the recyclability is low, but the resin composition of the present invention is obtained by using the above surface-modified silica composition. Since it is used, it is hardly subjected to shear stress, and a decrease in physical properties can be suppressed.
[0114]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples. The present invention is not limited by this. In the following examples, “parts” means “parts by mass” unless otherwise specified.
[0115]
Example 1
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0116]
Olefin resin (A): 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) and 20 parts of maleic anhydride-modified polyolefin (manufactured by Nippon Polyolefin Co., Ltd .: Adtex ER320P) are mixed well in a blender to obtain an olefin resin. Resin (A) was used. The concentration of the polar group at this time is about 0.06% by mass.
[0117]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (made by Asahi Denka Kogyo Co., Ltd .: Adelite AT-40, average particle diameter 15 to 18 nm, silica concentration 40% by mass, aqueous solvent) Hydroxyl group content (2 silanol groups on the particle surface / nm ² A solution (C) was prepared by reacting 1/50 equivalent of trimethylethoxysilane (manufactured by Chisso Corporation) with respect to the above (calculated assuming that :). At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0118]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 1.
[0119]
Example 2
The same olefin resin (A) as in Example 1 was used. The following compounds were used as the oxidized compound (B) (solution (C)).
[0120]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (Adelite AT-40 manufactured by Asahi Denka Kogyo KK, average particle diameter 15 to 18 nm, silica concentration 40 mass%, aqueous solvent) Surface hydroxyl group content (2 silanol groups on the particle surface / nm ² 1/50 equivalents of trimethylethoxysilane (manufactured by Chisso Corporation), and then 3-aminopropyltriethoxysilane (Chisso Corporation) which is a silane compound having an amino group. Was reacted at 1/10 equivalent to obtain a solution (C). At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0121]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 2.
[0122]
Example 3
The same oxide compound (B) (solution (C)) as in Example 1 was used. The following were used as the olefin-based resin (A).
[0123]
Olefin resin (A): 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) and 20 parts of a modified polyolefin having a carbonyl group (manufactured by Nippon Polyolefin Co., Ltd .: Lexpearl RB) are mixed well in a blender to obtain an olefin. The resin (A) was used. The concentration of the polar group at this time is about 0.5% by mass.
[0124]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 3.
[0125]
Example 4
The same oxide compound (B) (solution (C)) as in Example 2 was used. The following were used as the olefin-based resin (A).
[0126]
Olefinic resin (A): 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) and 20 parts of a modified polyolefin having an epoxy group (manufactured by Nippon Polyolefin Co., Ltd .: Lexpearl RA) are mixed well in a blender to obtain an olefin. The resin (A) was used. The concentration of the polar group at this time is about 0.4% by mass.
[0127]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 4.
[0128]
Example 5
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0129]
Olefin-based resin (A): Homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM900A), mixed with aminoethyl methacrylate (manufactured by Aldrich) and butyl peroxybenzoate as an organic peroxide, and mixed well. The mixture was kneaded at 200 ° C. with a machine to obtain a modified polyolefin having an amino group. 20 parts of this and 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) were mixed well in a blender to obtain an olefin resin (A). The concentration of the polar group at this time is about 0.06% by mass.
[0130]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (Adelite AT-40 manufactured by Asahi Denka Kogyo KK, average particle diameter 15 to 18 nm, silica concentration 40 mass%, aqueous solvent) Surface hydroxyl group content (2 silanol groups on the particle surface / nm ² 1/50 equivalent of trimethylethoxysilane (manufactured by Chisso Corp.), and then 1/10 equivalent of a silane compound having an epoxy group (3-glycidoxypropyl). ) Trimethoxysilane (manufactured by Chisso Corporation) was reacted to obtain a solution (C). At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0131]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 5.
[0132]
Example 6
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0133]
Olefin-based resin (A): homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM900A), acrylamide (manufactured by Aldrich) and butyl peroxybenzoate as an organic peroxide are mixed well, and the mixture is mixed well by a twin-screw kneader. Kneaded at ℃ to obtain a modified polyolefin having an amide group. 20 parts of this and 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) were mixed well in a blender to obtain an olefin resin (A). The concentration of the polar group at this time is about 0.06% by mass.
[0134]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (Adelite AT-40 manufactured by Asahi Denka Kogyo KK, average particle diameter 15 to 18 nm, silica concentration 40 mass%, aqueous solvent) Surface hydroxyl group content (2 silanol groups on the particle surface / nm ² 1/50 equivalents of trimethylethoxysilane (manufactured by Chisso Corp.), and 1/20 equivalents of 1,3-bis (3 (Carboxypropyl) tetramethyldisiloxane (manufactured by Chisso Corporation) was reacted to obtain a solution (C). At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0135]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 6.
[0136]
Example 7
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0137]
Olefin-based resin (A): 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) and 20 parts of a modified polyolefin having a hydroxyl group (manufactured by Sanyo Chemical Co., Ltd .: Umex 1201H) are mixed well in a blender to obtain an olefin-based resin. (A). The concentration of the polar group at this time is about 0.1% by mass.
[0138]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (made by Asahi Denka Kogyo Co., Ltd .: Adelite AT-40, average particle diameter 15 to 18 nm, silica concentration 40% by mass, aqueous solvent) Hydroxyl group content (2 silanol groups on the particle surface / nm ² 1/50 equivalent of trimethylethoxysilane (manufactured by Chisso Corp.), and then bis (N-methylbenzamide) which is a silane compound having an amide group of 1/10 equivalent A solution reacted with ethoxymethylsilane (manufactured by Chisso Corporation) was used as a solution (C). At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0139]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 7.
[0140]
Example 8
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0141]
Olefin-based resin (A): 80 parts of homopolypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) and 20 parts of a modified polyolefin having a hydroxyl group (manufactured by Sanyo Chemical Co., Ltd .: Umex 1201H) are mixed well in a blender to obtain an olefin-based resin. (A). The concentration of the polar group at this time is about 0.1% by mass.
[0142]
Oxidized compound (B) (solution (C)):
Water-dispersed colloidal silica (made by Asahi Denka Kogyo Co., Ltd .: Adelite AT-40, average particle size 15 to 18 nm, silica concentration 40% by mass, aqueous solvent) is added to the surface hydroxyl group amount (two silanol groups on the particle surface / nm ² 1/50 equivalent of trimethylethoxysilane (manufactured by Chisso Corporation), and then 1/10 equivalent of acetoxypropyltrimethoxysilane (a nitrogen-containing compound) having a carbonyl group. The solution (C) was reacted. At this time, the hydrophobic group introduction ratio (R × N) of the silica was 0.06.
[0143]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 8.
[0144]
Example 9
The same olefin resin (A) and oxidized compound (B) (solution (C)) as in Example 1 were used.
[0145]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 9.
[0146]
Example 10
The same olefin resin (A) and oxidized compound (B) (solution (C)) as in Example 2 were used.
[0147]
First, the olefin resin (A) is melt-kneaded at a kneading speed of 10 kg / h using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and the solution is mixed from the middle of the cylinder using a plunger pump. (C) was added and kneaded. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Example 10.
[0148]
Comparative Example 1
The following were used as the olefin resin (A) and the oxidized compound (B) (solution (C)).
[0149]
Olefin-based resin (A): A homo-polypropylene (manufactured by Sun Allomer Co., Ltd .: PM802A) was used as a comparative olefin-based resin (A) without treatment.
[0150]
Oxidized compound (B) (solution (C)): water-dispersed colloidal silica (manufactured by Asahi Denka Kogyo KK: Adelite AT-40, average particle diameter 15 to 18 nm, silica concentration 40% by mass, aqueous solvent) is untreated This was used as a comparative solution (C) as it was. Therefore, at this time, the hydrophobic group introduction rate (R × N) of the silica is 0.
[0151]
First, the comparative olefin-based resin (A) was melt-kneaded at a kneading speed of 10 kg / h by using a twin-screw kneader (manufactured by Nippon Steel Works: TEX30XSST modified machine), and a plunger pump was used in the middle of the cylinder. The comparative solution (C) was added and kneaded, and then supercritical carbon dioxide was further added and kneaded so as to be about 10% by mass of the resin amount. The addition amount of the solution (C) was adjusted so that the concentration of the oxidized compound (B) in the obtained resin composition was 10% by mass. The obtained resin composition is referred to as Comparative Example 1.
[0152]
Example 11
The resin compositions obtained in Examples 1 to 10 and Comparative Example 1 were molded into test pieces, and the following physical properties were evaluated for each test piece. Table 1 summarizes the evaluation results.
[0153]
In addition, various evaluations in this example were based on the following methods.
[0154]
(Evaluation method)
(1) The flexural modulus was measured according to ASTM D790-1991.
[0155]
(2) The deflection temperature under load was measured according to ASTM D648-1988.
[0156]
[Table 1]

[0157]
From Table 1, it can be seen that all of the resin compositions of Examples 1 to 10 show a significant improvement in rigidity and an improvement in heat resistance as compared with those of Comparative Example 1. Further, the resin composition of Comparative Example 1 used the same silica compound as the oxide compound (B) except that the treatment for introducing a polar group and a hydrophobic group was not performed, and the olefin resin (A) Considering that the kneading method is the same in Comparative Example 1 and Example, it is considered that this result indicates that the resin composition of the present invention has improved uniform dispersibility and interaction.
[0158]
In addition, from Table 1, when Examples 1 and 2 are compared with Examples 9 and 10, even if the raw materials before kneading are the same, adding the supercritical fluid improves the physical properties of both rigidity and heat resistance. It can be seen that the degree is large and it is effective for improving the uniform dispersibility. However, even in Examples 9 and 10 in which the supercritical fluid was not added, since the physical properties were sufficiently improved with respect to Comparative Example 1, the contribution to the effect of the present invention was that the composition was larger than that of the production method. Conceivable.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing an example of an application of a resin composition according to the present invention to exterior parts for vehicles.
FIGS. 2a and 2b are explanatory views showing an example of a vehicle outer panel application of the resin composition according to the present invention.
FIG. 3 is an explanatory view showing an example of a resin window application of the resin composition according to the present invention.
FIG. 4 is a schematic view of a resin wiper system according to the present invention.
FIG. 5 is an explanatory view showing an example of a vehicle exterior component application of the resin door mirror stay according to the present invention.
FIG. 6 is a view showing an instrument panel obtained by integrally molding a transparent resin portion and an opaque resin portion according to the present invention.
FIG. 7 is a view showing a resin mirror and a resin window according to the present invention.
FIG. 8 is a cross-sectional view showing a headlamp section using the resin lamp reflector of the present invention.
FIG. 9 is an explanatory view showing an example of a component in an engine room using the resin composition according to the present invention.
FIG. 10 is an explanatory view showing an example of a part in an engine room using the resin composition according to the present invention.
FIG. 11 is a view showing an example of a resin cooling device component using the resin composition according to the present invention.
FIG. 12 is a view showing an example of a resin cooling device component using the resin composition according to the present invention.
FIG. 13 is a view showing an example of an integrally molded resin having a hollow structure using the resin composition according to the present invention.
FIG. 14 is a view showing an example of a resin integrated molded article having a hollow structure using the resin composition according to the present invention.
FIG. 15 is an explanatory view showing an example of an integrally molded part using the resin composition according to the present invention.
FIG. 16 is an explanatory view showing an example of an integrally molded part using the resin composition according to the present invention.
FIG. 17 is an explanatory view showing an example of an integrally molded part using the resin composition according to the present invention.
FIG. 18 is a view showing an example of a molded article having a movable part and a non-movable part using the resin composition according to the present invention, FIG. 18A is a cross-sectional view of the molded article, and FIG. It is a top view of this molded object.
FIG. 19 is an explanatory view showing an example of the application of the resin composition according to the present invention to a vehicle exterior component.
[Explanation of symbols]
1 ... door molding, 2 ... frame frame of door mirror, 3 ... wheel cap,
4 spoiler, 5 bumper, 6 blinker lens,
7 ... pillar garnish, 8 ... rear finisher,
21: front fender, 22: door panel, 23: roof panel,
31 ... side glass, 32 ... rear glass, 41 ... wiper arm,
42: a wiper blade; 43: a support portion having elasticity;
44: soft rubber part, 45: nut hole for fixing the wiper arm,
51 ... lamp, hood, fender integrated resin molded body,
52: pillar garnish, glass-integrated resin molded body,
53: Roof, fender, glass-integrated resin molding,
54: Backdoor / glass integrated resin molding,
55: Door / glass integrated resin molded body,
61: instrument panel, 62: instrument cover,
71: front window, 72: door window,
73 ... rear window, 74 ... resin side mirror,
81: body side body, 82: outer member, 83: reflector,
84: bulb, 85: optical axis adjuster, 86: outer lens,
91: radiator, 92: coolant reserve tank,
93 ... Washer tank inlet, 94 ... Electrical component housing,
95: brake oil tank, 96: cylinder head cover,
101: engine body, 102: timing chain,
103 ... gasket, 104 ... front chain case,
111: water pipe, 112: O-ring,
113 ... water pump housing,
114 ... water pump impeller, 115 ... water pump,
116: water pump pulley, 121: water pipe,
122: thermostat housing, 123: thermostat,
124 ... water inlet, 131 ... hood, 132 ... door,
133: back door, 134: roof, 135: fender,
136: window, 137: trunk lid,
141: center console box, 142: pillar garnish,
143 ... instrument panel,
151 ... panel part, 152 ... air duct and case of air conditioner,
161: roof rail, 162: roof panel,
181: chamber part, 182: open / close valve,
183: open / close valve shaft,
191, filler tube, 192, fuel tank, 193, fuel pump,
194: engine, 195: filler cap, 196: vent tube,
197: Fuel hose, 198 ... Air chamber.

Claims (45)

A resin composition characterized by dispersing an oxidized compound (B) having a polar group and a partially hydrophobic group on its surface in an olefin resin (A) having a polar group. The resin composition according to claim 1, wherein the polar group of the oxidized compound (B) is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an amide group, a carbonyl group, and an epoxy group. The resin composition according to claim 1, wherein the oxidized compound (B) is a silica compound. The silica compound is selected such that the product (R × N) of the hydrophobicity of the silanol group (R) and the total carbon number of the alkyl group (N) is 0.01 to 8 for the hydrophobic group on the surface of the silica compound. The resin composition according to claim 3, which is introduced on a surface of the resin composition. The resin composition according to any one of claims 1 to 4, wherein at least one side of the oxidized compound (B) has a range of 1 to 200 nm. The resin composition according to any one of claims 1 to 5, wherein the oxidized compound (B) is contained in the resin composition in an amount of 0.1 to 60% by mass. The polar group of the olefin resin (A) is at least one selected from the group consisting of a dicarboxylic anhydride group, a carboxyl group, a carbonyl group, an epoxy group, an amino group, an amide group and a hydroxyl group. 7. The resin composition according to any one of the above items 6. The polar group of the olefin-based resin (A) is present at a ratio of 0.001 to 10% by mass relative to the olefin-based resin (A) in terms of an unsaturated monomer containing the polar group. The resin composition according to any one of claims 1 to 7. 9. The olefin resin (A) according to claim 1, wherein the olefin resin (A) is any one of polypropylene, polyethylene, and a copolymer of polypropylene and polyethylene, and has a polar group. 10. Resin composition. 9. The resin according to claim 1, wherein the olefin-based resin (A) is obtained by rubber-modifying any one of polypropylene, polyethylene, and a copolymer of polypropylene and polyethylene and has a polar group. The resin composition according to claim 1. After kneading the olefin-based resin (A) having a polar group with a solution (C) in which an oxidized compound (B) having a polar group and a partially hydrophobic group on the surface is uniformly dispersed in a solvent (S), A method for producing a resin composition, comprising removing the solvent (S). A solution (C) in which an olefin resin (A) having a polar group is uniformly dispersed in a solvent (S) with an oxidizing compound (B) having a polar group and a partially hydrophobic group on the surface, and a supercritical fluid (D); A method for producing a resin composition, comprising removing the solvent (S) and the supercritical fluid (D) after kneading while contacting. The method for producing a resin composition according to claim 11, wherein the concentration of the oxidized compound (B) in the solution (C) is 1 to 70% by mass. 14. The method for producing a resin composition according to claim 12, wherein the supercritical fluid (D) is supercritical carbon dioxide. The method for producing a resin composition according to any one of claims 11 to 14, wherein 80% by mass or more of the solvent (S) is water. A vehicle interior / exterior part molded article or a vehicle outer panel, comprising the resin composition according to claim 1. A resin window comprising the resin composition according to claim 1. A resin wiper system comprising the resin composition according to claim 1. A resin door mirror stay comprising the resin composition according to claim 1. A resin pillar comprising the resin composition according to claim 1. A resin molded article having a transparent part and an opaque part, wherein at least the transparent part comprises the resin composition according to any one of claims 1 to 10. 22. The resin molded product according to claim 21, wherein the transparent portion and the opaque portion are integrally formed. The resin molded product according to claim 21 or 22, wherein the opaque portion of the resin molded product is formed by being colored with a pigment dispersed in a resin. The resin molding according to claim 21 or 22, wherein the opaque portion of the resin molding is painted or printed before or after molding. The resin molded product according to claim 11, wherein the opaque portion of the resin molded product is formed using a colored sheet. A resin window with a heating wire, comprising the resin composition according to claim 1. A resin mirror comprising the resin composition according to claim 1. A resin lamp reflector comprising the resin composition according to claim 1. A resin engine room cover and case, comprising the resin composition according to claim 1. 30. The cover and case according to claim 29, wherein the cover and the case are transparent. A resin cooling device part comprising the resin composition according to claim 1. A resin integrated molded article comprising the resin composition according to any one of claims 1 to 10, having a hollow structure communicating with the atmosphere and / or a closed hollow structure. 33. The resin molded article according to claim 32, wherein the hollow structure is filled and sealed with a gas, a liquid, a solid, or a mixture thereof. 34. The resin integrated molded article according to claim 32, wherein the outermost layer of the integrated molded article is made of a decorative material. 35. The resin integrated molded product according to claim 32, wherein the resin integrated molded product is an outer plate or an interior / exterior component of an automobile. A resin sheet comprising the resin composition according to any one of claims 1 to 10, wherein the resin sheet is heated, inserted into a mold in an open state, the outer periphery of the sheet is pressed, and the outer periphery is welded. Before or after welding, injecting a pressurized fluid between the sheets, expanding and / or expanding the sheet, closing the mold, holding the pressurized fluid pressure and forming a hollow structure, A method for producing the resin-integrated molded product according to any one of claims 32 to 35. A pressurized fluid is injected into the molten resin while filling or after filling the resin composition according to any one of claims 1 to 10 which has been melted into a mold in a closed state. The method for producing an integrally molded resin article according to any one of claims 32 to 35, comprising a step of forming a hollow structure. One or two resin sheets comprising the resin composition according to any one of claims 1 to 10 are inserted into the mold cavity surface in an open state, and the mold is closed between two sheets. 36. The method according to claim 32, further comprising the step of injecting a pressurized fluid into the molten resin while filling or after filling the back surface of one sheet with the molten resin and expanding the cavity volume to form a hollow structure. The method for producing a resin-integrated molded product according to claim 1. An integrated unit comprising two or more components having different functions, comprising the resin composition according to any one of claims 1 to 10, wherein one or more components are provided with the two or more different functions. Molded parts. A molded article having a movable part and a non-movable part, comprising the resin composition according to claim 1. 41. The molded article according to claim 40, wherein the movable part and the non-movable part are integrally obtained by two-color molding. 42. The molded article according to claim 40, wherein the movable part is an opening / closing lid for controlling gas flow, and the non-movable part is a cylindrical molded product for introducing a flowing gas. A part or container for storing a hydrocarbon-based fuel comprising the resin composition according to claim 1. 44. The component or container for storing a hydrocarbon-based fuel according to claim 43, which is a series of fuel-based components for a vehicle. The component or container for storing a hydrocarbon-based fuel according to claim 43 or 44, which is a fuel tank for a vehicle.

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