JP2004285192A - Composition, resin composition, method for producing the composition, method for producing the resin composition, and molded form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition excellent in mechanical strength including rigidity and impact resistance, surface hardness and thermal stability, thus suitably usable as a practical organic glass or the like, and to provide a composition as an intermediate for making the resin composition. <P>SOLUTION: The resin composition is obtained by the following process: An oxide bearing on the surface chlorinated aliphatic hydrocarbon groups is dispersed in a chlorinated hydrocarbon solvent to prepare a 1st solution, subsequently 2,2-bis(4-hydroxyphenyl)propane is dissolved in a specified organic solvent to prepared a 2nd solution, the 1st and 2nd solutions are then mixed together to prepare a mixed solution, an organic base catalyst is put into the mixed solution to cause a dehydrochlorination reaction followed by mixing phosgene into the system to carry out a polymerization, thus affording the objective resin composition where a polycarbonate is chemically bound via the aliphatic hydrocarbon groups to the oxide. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００３１】
また、前記酸化化合物の表面に前記塩素化脂肪族炭化水素基を付加する際に用いる前記化合物としては、前記塩素化脂肪族炭化水素基を含むシラン化合物を用いることが好ましい。すなわち、前記酸化化合物に対して、前記シラン化合物を用いたシランカップリング処理を施すことによって、前記酸化化合物の表面に前記塩素化脂肪族炭化水素基を形成することが好ましい。これによって、上述した付加操作を簡易に行うことができる。
【００３２】
特に、酸化化合物としてシリカ微粒子を用いる場合は、前記シラン化合物としてアルコキシシランを用いることができ、このアルコキシシランのアルコキシ基を加水分解を経てシラノール基に変換した後、上述した表面処理を行うことが好ましい。この場合は、前記シラノール基がシリカ微粒子表面の水酸基と脱水縮合反応により強固に結合し、安定な塩素化脂肪族炭化水素基を含むシリカ微粒子を得ることができる。
【００３３】
なお、前記シラン化合物として３−クロロプロピルトリメトキシシランを用いた場合の、前記脱水縮合反応における反応式を以下に示す。
【００３４】
【化２】

【００３５】
【化３】

【００３６】
本発明の樹脂組成物は、上述のようにして得た組成物に対してホスゲン法における溶液重合法を施すことによって作製する。具体的には、前述した混合溶液中に必要に応じて追加のビスフェノールＡ及びホスゲンを投入し、さらにトリエチルアミン、ピリジン及びジメチルアニリンなどの有機塩基触媒を投入して、縮重合を生じさせ、上述したようなポリカーボネートが脂肪族炭化水素基を介して酸化化合物と化学的に結合してなる樹脂組成物を得る。
【００３７】
このようにして得た樹脂組成物は、ポリカーボネート単独の場合に比べて透明性、強度、弾性率などの向上が見られ、線膨脹率の低減が見られた。前記酸化化合物の補強効果によるものであり、アスペクト比（長さ／太さ）の大きい方が有効で、補強効果や線膨脹率低減効果が大きい。
【００３８】
なお、以下においては、ビスフェノールＡとプロピレンを介して化学的に結合したシリカ微粒子を含む組成物に対して、上述した溶液重合法を施した場合の反応式を示す。
【００３９】
【化４】

【００４０】
図１は、上記反応式を経て得られた樹脂組成物の構造を概念的に示すモデル図である。図１から明らかなように、前記樹脂組成物は、シリカ微粒子の周囲にポリカーボネートが分子鎖を拡張して結合したような構成を呈することが想定される。
【００４１】
なお、ポリカーボネイトの合成方法として、上述したホスゲン法の他にエステル交換反応による方法があるが、これは、一般に分子量が大きくならず、そのため強度、弾性率が低く、自動車部品などの要求仕様を満足できない。
【００４２】
（成形体及び部品）
本発明の樹脂組成物は、透明性や衝撃強度を犠牲にすることなく剛性の向上を実現し、また熱膨張率が低く、高温時にソリなどを抑制し得るという特性を兼ね備えているため、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並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。
【００４３】
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、熱線付き樹脂製ウィンドウ）；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；樹脂製ビラー；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及び／又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などの用途において、その効果を有効に発揮できる。
以下、本発明の樹脂塑性物の用途について詳述する。
【００４４】
＜車両用内外装部品成形体及び車両用外板＞
本発明に係る樹脂組成物用途の一つとしては、車両用内外装部品成形体及び車両用外板を挙げることができる。本発明の樹脂組成物は、透明性、耐衝撃性、剛性に優れ、さらに高耐熱性であり、熱膨張率が低く、熱時／成形時の寸法安定性にも優れるため、車両用の内外装部品成形体や車両用外板の用途に好適である。
【００４５】
図２及び図３（ａ）は、セダン系自動車のリアサイドからの外観斜視図であり、図３（ｂ）は、前記セダン系自動車の平面図である。車両用の内外装部品成形体としては、図２に示すような、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、スボイラー４、バンパー５、ウインカーレンズ６、ビラーガーニツシュ７、リアフイニツシヤー８、ヘッドランプカバー（図示せず）等を例示することができる。車両用外板としては、図３（ａ）や図３（ｂ）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）等を例示することができる。
【００４６】
＜樹脂製ワイパーシステム、樹脂製ドアミラーステイ及び樹脂製ピラー＞
本発明の樹脂組成物の用途の一つとして、樹脂製ワイパーシステム、樹脂製ドアミラーステイ及び樹脂製ピラーを挙げることができる。上述したように、本発明の樹脂組成物は、透明性、耐衝撃性、剛性に優れ、さらに高耐熱性であり、熱膨張率が低く、熱時／成形時の寸法安定性にも優れるため、ワイパーシステム等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。
【００４７】
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、従来のドアミラーステイは、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、従来のビラーは鋼鉄製であり、フロントビラー、センタービラーは通常走行時や右左折時、リアビ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。
【００４８】
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、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、透明性に優れ、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上記したような透明材として用いることで、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。
【００４９】
本発明のワイパーシステムの一実施態様を、図４に模式的に示す。図４に示されるように、ワイパーシステム３０は、ワイパーアーム３１とワイパーブレード３２から構成され、ワイパーアーム固定用ナット穴３３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３２は、弾性を有する支持部品と軟らかいゴム部品とから構成されている。
【００５０】
本発明のワイパーシステムにおいては、ワイパーアーム３１とワイパーブレード３２の支持部品の少なくとも一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けるワイパーブレード３２のゴム部品については、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のが好ましい。また、ワイパーブレード３２の支持部品は、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−ゴム混合組成物を用いて調製してもよい。これによって、ワイパーブレードの支持部品に適度な弾性を与えることができるからである。
【００５１】
このような樹脂−ゴム混合組成物としては、例えば、本発明の樹脂組成物１００質量部に対して、アクリルゴム成分（アクリル酸エチル、アクリル酸プチルやその共重合体等で、例えば日本ゼオン株式会社製Ｎｉｐｏｌ ＡＲ３１がある）を１〜３０質量部添加したものがある。
【００５２】
ドアミラーステー及びビラーに対しては、本発明の樹脂組成物のみを透明材として用いてもよいが、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（１層以上）にも前記樹脂組成物から成る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。
【００５３】
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材料としては、ポリカーボネート、ポリスチレン、スチレン／メチルメタアクリレート共重合体等がある。
【００５４】
また、製造方法や構成は特に限定されず、それぞれ単独の部品としてもよいし、例えば、ドアミラーステー及びフロントビラー、あるいは各ビラー及び樹脂ルーフパネルを、後述する一体成形体の製造方法等によって一体化してもよい。
【００５５】
＜樹脂成形体＞
本発明に係る樹脂組成物の用途の一つとしては、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本発明の樹脂組成物を含んで成ることを特徴とする。本発明の樹脂組成物は、高剛性、高耐熱性であり、熱時／成形時の寸法安定性、耐薬品性、透明性、耐衝撃性にも優れるため、透明部と不透明部を併せもつ部品の用途に好適である。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本発明の樹脂組成物を含んで成る樹脂成形体を適用してなる例として、自動車部品を例に説明する。
【００５６】
自動車には、例えば、各種ランプ類やカバー、ガラスのような透明な部品と、例えば、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、低成形収縮率、耐薬品性等、異なる様々な特性が要求されるため、従来、樹脂材料ではこれら透明な部品と不透明な部品の一体化は難しかった。
【００５７】
これに対して、高剛性、高耐熱性、低線膨張率、低成形収縮率、高耐薬品性という特徴を有する本発明の樹脂組成物を少なくとも透明材として使用することで、これらの課題が解決可能になる。さらに、透明な部品と不透明な部品を一体成形することにより部品点数及び工程数の削減、部品重量の低下が可能になる。また、数種の部品を一体で形成できるため、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ことから、部品外観の向上が図れる。
【００５８】
例えば、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、フードといった別々の（透明又は不透明な）部品と接している。これら透明部・不透明部を一体成形することにより部品点数の削減が可能である。さらに、従来は個々の部品を一つずつ組みつけていたが、一体化された部品一つ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。
【００５９】
また、本発明の樹脂組成物は、高い耐熱性を有するため、ランプの熱源が近くても樹脂が溶けてしまうなどの問題も発生しない。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おり、耐光性が低く、太陽光に暴露されると黄変するため、表層にコーティングしなければならなかったが、本発明の材料（樹脂組成物）を用いることにより、このような課題も解決される。
【００６０】
また、例えば、透明性を必要とする自動車用ガラスには、ドアに付属するサイドガラスとバックドアガラス、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とリアガラス等がある。本発明の樹脂組成物を少なくとも透明部に用いることにより、これらとガラスとの一体成形部品を得ることができる。例えば、サイドガラスとバックドアガラスとは、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ているが、本発明の材料（樹脂組成物）を用いて内部に中空部を形成することにより、ドアアウター・ドアインナー・ガラスを一体型でかつ同時に成形することができ、部品点数を削減することができる。
【００６１】
さらには、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、前記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・ガラスを一体的に成形することができる。なお、ドアロック、ワイパーモーター等は後工程で部品の中空部に設置する。同様にして、ビラーガーニツ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。
【００６２】
また、例えば、本発明の材料（樹脂組成物）が持つ透明かつ高強度・高剛性の特徴を利用して、構造用部品の部分的な透明化にも適用できる。例えば、ルーフの一部に本発明の樹脂組成物を用いると前記部分を透明にすることができる。したがって、ガラス製サンルーフを設けなくとも透明なルーフを得ることができる。このように、本発明の樹脂組成物を使用することによって、樹脂成形体の一部が透明部であり他の部分が不透明部である、高強度・高剛性を保持した構造用部品を形成することもできる。なお、不透明部は着色していてもよい。
【００６３】
図５は、ワゴン車のリアサイドからの外観斜視図である。図５に示すワゴン車は、透明部と不透明部とを有する樹脂成形体である、ランプフード・フェンダー一体樹脂成形体４１、ビラーガーニツシュ・ガラス一体樹脂成形体４２、ルーフフェンダ・ガラス一体樹脂成形体４３、バックドア・ガラス一体樹脂成形体４４及びドア・ガラス一体樹脂成形体４５等を有している。本発明の樹脂組成物は、これらの樹脂成形体の透明部に適用することができる。例えば、ランプフード・フェンダー一体樹脂成形体４１のランプフードなどに適用することができる。このように本発明の樹脂組成物を用いれば、部品点数を削減することができ、部品取り付けの工程数を削減することができる。
【００６４】
図６は、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及び計器類のカバーを示す模式図である。前記透明樹脂部に対して本発明の樹脂組成物を適用するようにすれば、前記透明樹脂部と前記不透明樹脂部とを一体的に成形できるため、予めインストルメントパネル５１と計器類のカバー５２とを同時に（一体的に）成形しておき、インストルメントパネル５１に数種の部品を集約することで、部品点数を削減し、かつ軽量化を図ることができる。
【００６５】
なお、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、不透明部に塗装又は印刷して着色する方法、又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。
【００６６】
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ベ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。前記着色樹脂を用いて前記樹脂成形体を製造するには、前記着色樹脂を含む前記金型を開き、又は溶融樹脂通過経路を新たに作製して、別のシリンダを用い、前記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。
【００６７】
塗装又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、その後前記樹脂成形体の表面あるいは裏面から塗装あるいは印刷を施して、着色及び不透明性を確保する。溶融樹脂の賦形前に塗装又は印刷を施し、その後に賦形することもできる。
【００６８】
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、次いで、金型内に配置する。次いで、溶融透明樹脂を前記金型内に注入し、冷却固化した後に前記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。
【００６９】
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とが透明部であり、フェンダとガラス及びルーフの残部とが不透明の樹脂成形体とすることもできる。
【００７０】
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のみ（一部、顔料等により着色する場合を含む）によって構成できるが、例えば、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前記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。
【００７１】
＜樹脂ウインドウ、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及びケース、樹脂製冷却装置部品＞
本発明に係る樹脂組成物の用途の一つとしては、前記樹脂組成物を含んで成ることを特徴とする樹脂製ウィンドウ、特に好ましくは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及びケース、樹脂製冷却装置部品である。
【００７２】
本発明の樹脂組成物は、高剛性、高耐熱性であり、熱時／成形時の寸法安定性、耐薬品性、透明性にも優れるため、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及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。
【００７３】
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説明図であって、これらの車両用部品の位置を解説したセダン系自動車の平面図である。例えば、図７に示すように、リアウィンドウ６３、ドアウィンドウ（サイドウィンドウ）６２、フロントウィンドウ６１などの樹脂製ウィンドウは、防曇機能を付与するため、成形体の内部あるいは表面に加熱可能な熱線ヒータを設けることがある。このような場合では、ウィンドウは、風雨を防ぐための部品として、図７のように車両の前面と後面そして側面のドアに設置されるが、その使用面積は３〜４ｍ^２と大きく、また、従来の無機ガラスの場合では、重量が３０〜３５ｋｇと重いため、本発明の樹脂組成物を使用することにより、軽量化が期待できる。
【００７４】
また、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は加熱時／成形時の寸法安定性に優れるため、本発明の樹脂組成物を用いるとこれらの問題がない。さらに、本発明の樹脂組成物は高い剛性を有するので、図７におけるようなフロントウィンドウ６１、ドアウィンドウ６２、リヤウィンドウ６３等の大型部品に応用可能で軽量化することができる。
【００７５】
なお、熱線ヒータの形成方法としては、特に制限されず、公知の方法が使用できる。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、ドアウィンドウ、リヤウィンドウ等の大型部品にも適用可能で、軽量化が可能となる。
【００７６】
また、本発明の透明樹脂を用いて樹脂製サイドミラー６４（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。
【００７７】
上記したように、本発明の樹脂組成物は、透明性や衝撃強度を犠牲にすることなく剛性の向上を実現し、また熱膨張率が低く、高温時にソリなどを抑制し得るという特性を兼ね備えているために、安全性と機能面で解決すべき課題があるためまだ本格的な採用までには至っていなかったウィンドウやミラーなどの様々な用途にも適用することができる。これにより、従来要望の高かった車両の軽量化及びデザインの自由度の拡大が達成できる。
【００７８】
また、近年、ワンボックス型のＲＶ車の普及が目覚しくウィンドウの占める割合が増大してきており、軽量化と乗員の視認性と快適性向上から、ウィンドウの樹脂化に対する要求は益々強くなってきている。本発明の樹脂組成物により成形される透明樹脂製ガラスは、これら自動車用ウィンドウに要求される機能を備えており、車両の軽量化と快適性向上に貢献できるものである。なお、上記記載の樹脂ウィンドウ以外でも美観、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。
【００７９】
また、図８に自動車ランプの横断面図を示す。図８に示すように、車体側基体７１に固定されたアウタ部材７２の内部にリフレクター７３が配置され、リフレクター７３にはバルブ７４と光軸調整器７５が連結され、アウタ部材７２は、さらにアウタレンズ７６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７３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ことで、これらの課題が解決できる。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することができ、ヘッドランプ、フオグランプ、リアコンビランプ等のリフレクター、又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。
【００８０】
なお、反射部の形成方法としては、例えば、前記部材を製造する際に反射膜をインサート成形する方法や、前記部材を射出成形・プレス成形により成形した後に、前記反射部に蒸着膜を形成させる方法等がある。
【００８１】
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及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及び図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は、例えば、ラジエーター８１、冷却液リザーブタンク８２、ウォシヤータンクインレット８３、電気部品ハウジング８４、ブレーキオイルタンク８５、シリンダーヘッドカバー８６、エンジンボディー９１、タイミングチェーン９２、ガスケット９３、フロントチェーンケース９４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、上記ウォッシヤ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。
【００８２】
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に示すウォータパイプ１０１、０−リング１０２、ウォータポンプハウジング１０３、ウォータポンプインペラ（羽車）１０４、ウォータポンプ１０５、ウォータポンププーリ１０６、図１２に示すウォータパイプ１１１、サーモスタットハウジング１１２、サーモスタット１１３、ウォータインレット１１４等のラジェタータンクのトップ及びベースなどのラジェタータンク部品、冷却液リザーブタンク、バルブなどの部品が挙げられる。前記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。
【００８３】
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前記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。
【００８４】
＜中空構造及び／又は密閉された中空構造を有する樹脂一体成形体＞
本発明に係る樹脂組成物の用途の一つとして、前記樹脂組成物を含んで成る、大気と連通した中空構造及び／又は密閉された中空構造を有する樹脂一体成形体を例示することができる。上記のように、本発明の樹脂組成物は、高剛性、高耐熱性であり、加熱時／成形時の寸法安定性にも優れるため、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。本発明の樹脂一体成形体としては、自動車の外板及び内外装部品が好ましく挙げられる。
【００８５】
この際、自動車の外板及び内外装部品は、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、側面ドア及びバックドアは、外側及び内側を中空構造を有する銅板で構成し、塗装を経て組み立て工程で内側銅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、外板及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。
【００８６】
上述した樹脂一体成形体は、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前記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。
【００８７】
前記樹脂一体成形体は、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。
【００８８】
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、又はこれらの２種以上からなる混合物が充填、封入されることが好ましい。これによって、前記一体成形品の断熱性能、遮音性能を向上させることができるからである。
【００８９】
具体的な充填・封入材料としては、特に制限されず、公知の充填・封入材が使用できる。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ィン、ワックス等が好ましい。
【００９０】
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抑制することができ、冬期には温熱の逃げ、外気の冷熱の侵入を抑制して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。
【００９１】
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、下記第一から第三の方法が好適に用いられる。
【００９２】
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する間、又は溶着した後に、好ましくは溶着する前又は溶着した後に、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／又は拡張後、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。
【００９３】
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、前記樹脂一体成形体の代表的な１つの製造方法としては、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／又は拡張した後に、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。
【００９４】
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、前記金型を後退して、キヤ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、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／又は充填後、キヤ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て、中空構造を形成するものである。
【００９５】
第三の方法としては、金型片面のキヤ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ヤ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ヤ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ヤ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、開状態の金型キヤ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、金型を閉状態で前記１枚のシートの背面あるいは前記２枚のシート間に溶融樹脂を充填しつつ又は充填した後、キヤ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ものである。
【００９６】
上記態様において、シート間あるいはシートの背面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、前記シートを構成する本発明の樹脂組成物と接する樹脂と同種の樹脂、又は本発明の樹脂組成物とＳＰ値が近いものが使用される。このような充填樹脂としては、ポリカーボネート樹脂、スチレン系樹脂、ポリ−４−メチルペンテン−１、熱可塑性ポリウレタン樹脂等が挙げられ、特にポリカーボネート樹脂を使用することが好ましい。
【００９７】
前記ポリカーボネート樹脂は、ビスフェノールＡに代表される二価のフェノール系化合物から誘導される重合体で、ホスゲン法、エステル交換法、あるいは固相重合法のいずれにより製造されたものでもよい。更に、従来からあるポリカーボネート樹脂の他にエステル交換法で重合したポリカーボネート樹脂でもよい。
【００９８】
また、上述した加圧流体の種類についても特に制限されず、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することができる。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。
【００９９】
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１２１、ドア１２２、バックドア１２３、ルーフ１２４、フェンダー１２５、ウィンドウ１２６、トランクリッド１２７、センターコンソールボックス１３１、ビラーガーニツシュ１３２、インストルメントパネル１３３、ヘッドライニング（図示せず）等を挙げることができる。これらの部品はインナー／アウター及び付帯する部品やレインホース等を同時かつ一体的に成形することができ、部品数の低減及び工程数を短縮することができる。
【０１００】
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、断熱性能、遮音性能等の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。
【０１０１】
＜２種類上の機能を有する一体成形部品＞
本発明に係る樹脂組成物の用途の一つとしては、前記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、単一の部品に異なる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。
【０１０２】
本発明の樹脂組成物は、高剛性、高耐熱性であり、加熱時／成形時の寸法安定性、耐薬品性等の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、単一の部品に２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。
【０１０３】
例えば、大型内装部品であるインストルメントパネルは、現在、パネル部とエアコンのエアダクトやケース、クロスカービーム（ステアリングクロスメンバー）などとを別々に作り、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とを一体成形しようとすると、得られる成形部品は大型化し、かつ複雑な形状を有するようになるため、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。
【０１０４】
また、本発明の樹脂組成物は上記したように高耐熱性を有し、加熱時／成形時の寸法安定性に優れているので、本発明の樹脂組成物を含んで成る一体成形部品であるインストルメントパネルは、図１５に示すように、パネル部１４１とエアコンのエアダクトやケース１４２を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。
【０１０５】
さらに、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部品とすることができる。
【０１０６】
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１５１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１５２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、また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（耐寒性を含む）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ことで、このような課題が解決可能となる。同様の効果は、例えば、スボ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。
【０１０７】
また、図１７に示すように、大型車体部品であるラジエタコアを例にすると、現在フロントエンドモジュールとして樹脂製のラジエタコアが世に出つつあるが、本発明の樹脂組成物を用いることで更に耐熱性、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、又はファンシュラウドやブラケット等も一体成形可能となる。また、本発明では、樹脂組成物を透明材として用いることも可能であり、このような場合には、例えば、ラジェタのリザーバタンク、ヘッドランプカバー等の透明部材を含めて一体成形することも可能である。さらに、従来は別体であったバンパ補強材をも含めて一体成形することも可能となる。
【０１０８】
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ヤンバー等を例にすると、耐熱性と耐薬品性に優れ、低熱線膨張の本発明の樹脂組成物を用いることで、これらの一体成形が可能となる。従来より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になるが、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。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。
【０１０９】
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前記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
【０１１０】
＜可動部と非可動部とを有する成形体＞
本発明の樹脂組成物は、高剛性、高耐熱性であり、加熱時／成形時の寸法安定性にも優れるため、例えば、スロットルチヤ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、本発明に係る樹脂組成物の用途の一つとして、本発明の樹脂組成物を含んで成る可動部と非可動部とを有する成形体を例示することができる。
【０１１１】
自動車の吸排気系部品やエアコンユニット内には、可動部と非可動部と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、非可動部として気体の流路となる、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、スロットルチヤ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。
【０１１２】
従来の樹脂材料を用いてこれらの部品の筒状部分と蓋部分を成形しようとすると、成形収縮率や熱膨張率が大きいため、寸法精度が上げられず、開閉部分の気密性が課居であった。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。しかしながら、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。また、本発明の樹脂組成物は高剛性であるため、これらの樹脂組成物を用いることにより、部品の軽量化とそれによるレスボンスの向上が可能となる。
【０１１３】
本発明の可動部と非可動部を有する成形体の製造方法は、特に制限されず公知の方法が使用できる。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、これらを組み立てる方法を使用してもよいが、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。これによって、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ヤンバーを例に取ると、例えば、下記方法で製造可能である。
【０１１４】
スロットルチヤンバーは、非可動部である筒状のチャンバー部１７１と、可動部である開閉バルブ１７２及び開閉バルブシャフト１７３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、次いで、円筒状のチヤンバーを射出成形し、次いで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させ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とが一体化される。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が流動気体を導入する筒状成形品である場合にも、好ましく応用することができる。
【０１１５】
＜炭化水素系燃料収納用の部品又は容器＞
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又は容器、炭化水素系燃料を収納する部品又は容器、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、本発明に係る樹脂組成物の用途の一つとして、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を例示することができる。
【０１１６】
図１９に、前述した炭化水素系燃料の収納容器の一例として、自動車等の車両における樹脂製燃料タンクを示す。フイラーチューブ１８１を介して炭化水素系燃料であるガソリンが燃料タンク１８２に注入・貯蔵され、次いで、前記ガソリンが燃料ポンプ１８３によりエンジン（図示せず；符号１８４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。
【０１１７】
図１９に示す樹脂製燃料タンクにおいて、本発明の樹脂組成物が適用できる部品としては、燃料タンク本体１８２、フイラーキャップ１８５、ペントチューブ１８６、フューエルホース１８７、フューエルカットオフバルブ（図示せず）、デリバリーパイプ（図示せず）、エバポチューブ（図示せず）、リターンチューブ（図示せず）、フューエルセンダーモデュール（図示せず）等が挙げられる。
【０１１８】
燃料タンク本体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。近年においては、燃料タンク本体を樹脂化する試みがなされ、部品形状の自由度増の効果により、金属製の燃料タンク本体に比較して、貯蔵燃料量が約１０リットルほど増大させることができ、重量を２５％程度軽減することができた。このような利点から燃料タンクの樹脂化への期待が一層高まっている。
【０１１９】
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イン系の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）又は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。
【０１２０】
単層型燃料タンクにおいて、このタンクから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。
【０１２１】
前記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。
【０１２２】
これに対して、本発明の樹脂組成物中の表面改質したシリカ化合物は、シラノール基を残しているためＳＰ値は１１を超え、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。また、本発明の樹脂組成物の主たる成分は、アクリル等の極性基を有するＳＰ値が１１以上の樹脂が主体であり、炭化水素系燃料としてのガソリンとは馴染みにくい、換言すれば相溶性が悪い材料構成となっているため、燃料タンクとしてより望ましい材料である。
【０１２３】
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法規制を満たす車両用の燃料タンクを提供することができる。これにより課題である製造コストの低減が図れ、かつリサイクルの社会的要請に応えることできるようになる。この際、本発明の樹脂組成物は、単層型又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。
【０１２４】
なお、車両用の燃料タンクに比べると効果はやや低いものの、本発明の樹脂組成物は、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。
【０１２５】
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。
【０１２６】
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、上記で詳述したような、射出成形及び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、上記表面改質したシリカ化合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。
【０１２７】
【実施例】
以下、本発明を実施例に基づいて詳細に説明する。なお、以下に示す各実施例及び各比較例において、全光線透過率、透過電子顕微鏡での分散状態、曲げ強度、曲げ弾性率、及び線膨張係数は、下記装置を用いて評価した。
・全光線透過率：ヘイズメーター（村上色彩研究所製ＨＭ−６５）で測定
・透過電子顕微鏡での分散状態：日立製作所製Ｈ−８００を用いて８００００倍で観察し、黒色がシリカ微粒子で白色が樹脂として分散状態を観察
・曲げ強度、弾性率：オートグラフ島津製作所製 ＤＣＳ−１０Ｔ）で測定
・ 線膨脹係数の測定：熱機械測定装置（セイコー電子工業製ＴＭＡ１２０Ｃ）で測定
【０１２８】
（実施例１）
メチレンクロライド溶液２５０ｍｌに、ビスフェノールＡ２２８ｇ、および酸化による着色防止剤としての、ハイドロサルファイド（ヒドロ亜硫酸ナトリウム）０．２５ｇを溶解した。次いで、このようにして得た溶液に、シリカ微粒子（アエロジル２００：日本アエロジル製）に対して３−クロロプロピルトリメトキシシランを用いた表面処理を行い、表面に塩素化プロピル基を付加させて得た酸化化合物５３ｇを分散混合させて得たメチレンクロライド溶液７５０ｍｌを加えた。次いで、脱塩酸反応の触媒として１％トリエチルアミンのメチレンクロライド溶液１５ｍｌを添加して約１時間攪拌し、シリカ表面の塩素化プロピル基にビスフェノールＡを共有結合させた。
【０１２９】
次いで、上述した混合溶液中にホスゲンを２ｇ／ｍｉｎの速度で約５０分間かけて吹き込みながら攪拌した。次いで、前記混合溶液中に脱塩酸反応触媒として１％トリエチルアミンのメチレンクロライド溶液１５ｍｌを加え、約１時間攪拌させることによって、ビスフェノールＡとホスゲンとを縮重合し、シリカを共有結合したポリカーボネイト樹脂の溶液を得た。
【０１３０】
次いで、前記溶液をリン酸で中和した後水洗し、メタノール中に滴下させた後重合組成物を沈殿させ、濾過及び乾燥して、白色粉末状の樹脂組成物を得た。このようにして得た樹脂組成物は、乾燥及び粉砕した後熱プレス成形し、シート状の成形品とした。この成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１３１】
（実施例２）
メチレンクロライド溶液２５０ｍｌに、ビスフェノールＡ２２８ｇ、および酸化による着色防止剤としての、ハイドロサルファイド（ヒドロ亜硫酸ナトリウム）０．２５ｇを溶解した。次いで、このようにして得た溶液に、水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）を、予め蒸発乾燥して粉末としたものに対して、実施例１同様の表面処理を行い、表面に塩素化プロピル基を付加させて得た酸化化合物５３ｇを分散混合させて得たメチレンクロライド溶液７５０ｍｌを加えた。次いで、脱塩酸反応の触媒として１％トリエチルアミンのメチレンクロライド溶液１５ｍｌを添加して約１時間攪拌し、シリカ表面の塩素化プロピル基にビスフェノールＡを共有結合させた。
【０１３２】
次いで、上述した混合溶液中に、実施例１と同様にしてホスゲンを添加して重合し、目的とする白色粉末状の樹脂組成物を得た。次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１３３】
（実施例３）
水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）に代えて、水溶性の鎖状コロイダルシリカ（スノーテックスＯＵＰ：日産化学製）を用いた以外は、実施例２と同様にして表面に塩素化プロピル基を有するシリカ微粒子を得、実施例２と同様のホスゲン法を用いた重合過程を経ることにより目的とする白色粉末状の樹脂組成物を得た。
【０１３４】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１３５】
（実施例４）
水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）に代えて、水溶性のパールネックレス状コロイダルシリカ（スノーテックスＰＳ−ＳＯ：日産化学製）を用いた以外は、実施例２と同様にして表面に塩素化プロピル基を有するシリカ微粒子を得、実施例２と同様のホスゲン法を用いた重合過程を経ることにより目的とする白色粉末状の樹脂組成物を得た。
【０１３６】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１３７】
（実施例５）
塩素化プロピル基を表面に有するシリカ微粒子を得る際に、メチレンクロライド溶液に代えてクロルベンゼン溶液を用い、実施例１と同様の条件で前記シリカ微粒子を得、実施例１と同様の条件で重合を実施して目的とする白色粉末状の樹脂組成物を得た。
【０１３８】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１３９】
（実施例６）
塩素化プロピル基を表面に有するシリカ微粒子を得る際に、メチレンクロライド溶液に代えてクロルホルム溶液を用い、実施例１と同様の条件で前記シリカ微粒子を得、実施例１と同様の条件で重合を実施して目的とする白色粉末状の樹脂組成物を得た。
【０１４０】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１４１】
（実施例７）
塩素化プロピル基を表面に有するシリカ微粒子を得る際に、メチレンクロライド溶液に代えて１，２ジクロロエタン溶液を用い、実施例１と同様の条件で前記シリカ微粒子を得、実施例１と同様の条件で重合を実施して目的とする白色粉末状の樹脂組成物を得た。
【０１４２】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性があり、強度、弾性率の向上と熱膨脹率の低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表１に示す。
【０１４３】
【表１】

【０１４４】
（比較例１）
ポリカーボネート樹脂（ユーピロンＳ２０００三菱エンプラ製）１２０ｇをメチレンクロライド溶液２４０ｇに溶解し、次いで、前記溶液中に、シリカ微粒子（アエロジル２００：日本アエロジル製）をメチル基で表面処理をしたシリカ３０ｇを分散混合させて、ポリカーボネイト樹脂／シリカ混合溶液を調整した。この混合溶液をメタノールに滴下させて樹脂組成物を沈殿させ、濾過し、乾燥した後、白色状の粉末とした。
【０１４５】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性が不足し、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１４６】
（比較例２）
ポリカーボネート樹脂（ユーピロンＳ２０００三菱エンプラ製）１２０ｇをメチレンクロライド溶液２４０ｇに溶解し、次いで、前記溶液中に、水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）を、予め蒸発乾燥し、粉末とし、この粉末を（アエロジル２００：日本アエロジル製）をメチル基で表面処理をして得たシリカ微粒子３０ｇを分散混合させて、ポリカーボネイト樹脂／シリカ混合溶液を調整した。この混合溶液をメタノールに滴下させて樹脂組成物を沈殿させ、濾過し、乾燥した後、白色状の粉末とした。
【０１４７】
次いで、前記樹脂組成物を実施例１同様に加工してシート状の成形品を得、各種の測定に供した。得られた成形品は、透明性が不足し、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１４８】
（比較例３）
前記水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）に代えて、鎖状コロイダルシリカ（スノーテックスＯＵＰ：日産化学製）を用いた以外は、比較例２と同様にして樹脂組成物を得、比較例２と同様にしてシート状成形品を得た。得られた成形品は、透明性が不足し、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１４９】
（比較例４）
前記水溶性の球状コロイダルシリカ（スノーテックスＳＴ−Ｏ：日産化学製）に代えて、鎖状コロイダルシリカ（スノーテックスＯＵＰ：日産化学製）を用いた以外は、比較例２と同様にして樹脂組成物を得、比較例２と同様にしてシート状成形品を得た。得られた成形品は、透明性が不足し、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１５０】
（比較例５）
メチル基で表面処理をしたシリカ（アエロジルＲ９７４：日本アエロジル製）粉末２０ｇをポリカーボネイト樹脂（ユーピロンＳ２０００三菱エンプラ製）８０ｇに、小型ニーダーで溶融混合し、得られた組成物を、粉砕し、熱プレス成形により、シート状の成形品を得た。得られた成形品は、透明性が極めて悪く、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１５１】
（比較例６）
水溶性の球状コロイダルシリカ（スノーテックスＳＴ−０：日産化学製）を予め蒸発乾燥して粉末とし、この粉末をメチル基で表面処理をしたシリカ粉末２０ｇをポリカーボネイト樹脂（ユーピロンＳ２０００三菱エンプラ製）８０ｇに、小型ニーダーで溶融混合し、得られた組成物を、粉砕し、熱プレス成形により、シート状の成形品を得た。得られた成形品は、透明性が極めて悪く、強度、弾性率の僅かな向上と熱膨脹率の僅かな低下が見られた。また、透過電子顕微鏡によってシリカの配合割合を調べたところ、２０ｗｔ％であった。各測定値を表２に示す。
【０１５２】
なお、表２には、上述したシリカ微粒子を有しないポリカーボネート樹脂単体の諸特性を併記した。
【０１５３】
【表２】

【０１５４】
以上、本発明を発明の実施の形態に即して詳細に説明したが、本発明は上記内容に限定されるものではなく、本発明の範疇を逸脱しない限りにおいてあらゆる変形や変更が可能である。
【０１５５】
【発明の効果】
以上説明したように、本発明によれば、剛性や耐衝撃性などの機械的強度、並びに表面高度及び熱的安定性に優れ、実用的な有機ガラスなどとして好適に使用することのできる樹脂組成物、及びこの樹脂組成物を作製するための中間体としての組成物を提供することができる。また、前記樹脂組成物の製造方法及び前記組成物の製造方法、さらには、前記樹脂組成物を利用した種々の成形体及び部品、並びにこれら成形体及び部品の製造方法を提供することができる。
【図面の簡単な説明】
【図１】本発明の樹脂組成物の一例における構造を概念的に示すモデル図である。
【図２】本発明に係る樹脂組成物の車両用外装部品用途の一例として、ドアモール、ドアミラーのフレーム枠、ホイールキャップ、スボイラー、バンパー、ウインカーレンズ及びビラーガーニツシュを示す説明図であって、これらの車両用外装部品の位置を解説したセダン系自動車のリアサイドからの外観斜視図である。
【図３】本発明に係る樹脂組成物の車両用外板用途の一例として、フロントフェンダー、ドアパネル、ルーフパネル、フロントパネル及びリアパネルを示す説明図であって、図３（ａ）は、これらの車両用外板の位置を解説したセダン系自動車のリアサイドからの斜視図であり、図３（ｂ）は、セダン系自動車の平面図である。
【図４】本発明に係る樹脂製ワイパーシステムの模式図である。
【図５】本発明に係る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本発明の樹脂組成物を含んで成る樹脂成形体の車両用外装部品用途の一例として、ランプ・フード・フェンダーー体樹脂成形体、ビラーガーニツシュ・ガラスー体樹脂成形体、ルーフ・フェンダ・ガラスー体樹脂成形体、バックドア・ガラスー体樹脂成形体及びドア・ガラスー体樹脂成形体を示す説明図であって、これらの車両用外装部品の位置を解説したワゴン車のリアサイドからの外観斜視図である。
【図６】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及び計器類のカバーを示す模式図である。
【図７】本発明に係る樹脂製ミラー、樹脂製ウィンドウを示す説明図であって、これらの車両用部品の位置を解説したセダン系自動車の平面図である。
【図８】本発明の樹脂製ランプリフレクターを示す横断面図である。
【図９】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として、ラジエーター、冷却液リザーブタンク、ウォシヤ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及びシリンダーヘッドカバーを示す説明図であって、自動車のフードパネルを取り外した状態でのエンジンルーム内の概略斜視図である。
【図１０】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として、エンジンボディー、タイミングチェーン、ガスケット及びフロントチェーンケースを示す説明図であって、これらの各部品構成がわかるようにした分解斜視図である。
【図１１】本発明に係る樹脂組成物を用いてなる樹脂製冷却装置部品の一例として、ウォータパイプ、Ｏ−リング、ウォータポンプハウジング、ウォータポンプインペラ（羽車）、ウォータポンプ及びウォータポンププーリを示すセ説明図であって、これらの各部品構成がわかるようにした分解斜視図である。
【図１２】本発明に係る樹脂組成物を用いてなる樹脂製冷却装置部品の他の一例として、ウォータパイプ、サーモスタットハウジング、サーモスタット、及びウォータインレットを示す図であって、これらの各部品構成がわかるようにした分解斜視図である。
【図１３】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として、フード、ドア、バックドア、ルーフ、フェンダー、ウィンドウ及びトランクリッドを示す説明図であって、図１３（ａ）は、これらの位置を示すためのセダン系自動車のドアを開いた状態でのリアサイドからの外観斜視図であり、図１３（ｂ）は、ワンボックスカーのリアサイドからの外観斜視図である。
【図１４】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他の一例として、センターコンソールボックス、ビラーガーニツシュ及びインストルメントパネルを示す説明図であって、図１４（ａ）は、センターコンソールボックス位置を示す自動車の車室内の前席の斜視図であり、図１４（ｂ）は、ビラーガーニツシュ及びインストルメントパネル位置を示す自動車の車室内斜視図である。
【図１５】本発明に係る樹脂組成物を用いた、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の一例として、インストルメントパネル部とエアコンのエアダクトやケースとの一体成形部品を示す説明図である。
【図１６】本発明に係る樹脂組成物を用いた一体成形部品の他の一例として、ルーフレールとルーフパネルとの一体成形部品を示す説明図であって、自動車のルーフ部分の外観斜視図である。
【図１７】本発明に係る樹脂組成物を用いた、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の他の一例として、ラジエタコアの一体成形部品を示す説明図である。
【図１８】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として、チヤンバーの可動部である開閉バルブと、非可動部である開閉バルブ及び開閉バルブシャフトを有する成形体を示す図であって、図１８（ａ）は、これらチヤンバー部、開閉バルブ及び開閉バルブシャフトを有する成形体の横断面図であり、図１８（ｂ）は、図１８（ａ）のＡ−Ａ線に沿って切断し上部から見た前記チヤンバー部の断面図である。
【図１９】本発明に係る樹脂組成物の車両用外装部品用途の一例として、燃料タンク及びその周辺の燃料系部品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 スボイラー
５ バンパー
６ ウインカーレンズ
７ ビラーガーニツシュ
８ リアフイニツシヤー
２１ フロントフェンダー
２２ ドアパネル
２３ ルーフパネル
２４ フードパネル
２５ トランクリッド
３０ ワイパーシステム
３１ ワイパーアーム
３２ ワイパープレード
３３ ワイパーアーム固定用ナット穴
４１ ランプフード・フェンダー一体樹脂成形体
４２ ビラーガーニツシュ・ガラス一体樹脂成形体
４３ ルーフフェンダ・ガラス一体樹脂成形体
４４ バックドア・ガラス一体樹脂成形体
４５ ドア・ガラス一体樹脂成形体
５１ インストルメントパネル
５２ 計器類のカバー
６１ フロントウィンドウ
６３ リアウィンドウ
７１ 車体側基体
７３ リフレクター
７５ 光軸調整器
８１ ラジエーター
６２ ドアウィンドウ
６４ サイドミラー
７２ アウタ部材
７４ バルブ
７５ アウタレンズ
８２ 冷却液リザーブタンク
８３ ウォシヤータンクインレット
８４ 電気部品ハウジング
８６ シリンダーヘッドカバー
９２ タイミングチェーン
９４ フロントチェーンケース
８５ ブレーキオイルタンク
９１ エンジンボディー
９３ ガスケット
１０１ ウォータパイプ
１０２ Ｏ−リング
１０３ ウォータポンプハウジング
１０４ ウォータポンプインペラ（羽車）
１０５ ウォータポンプ
１０６ ウォータポンププーリ
１１１ ウォータパイプ
１１２ サーモスタットハウジング
１１３ サーモスタット
１１４ ウォータインレット
１２１ フード
１２２ ドア
１２３ バックドア
１２４ ルーフ
１２５ フェンダー
１２６ ウィンドウ
１２７ トランクリッド
１３１ センターコンソールボックス
１３２ ビラーガーニツシュ
１３３ インストルメントパネル
１４１ パネル部
１４２ エアコンのエアダクトやケース
１５１ ルーフレール
１５２ ルーフパネル
１７１ …チヤンバー部
１７２ 開閉バルブ
１７３ 開閉バルブシャフト
１８１ フイラーチューブ
１８２ 燃料タンク
１８３ 燃料ポンプ
１８５ フイラーキャップ
１８６ …ペントチューブ
１８７ フユーエルホース
１８８ 空気室[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a resin composition having high rigidity and strength, and high surface height and thermal stability, which can be suitably used as a practical organic glass, and an intermediate for producing the resin composition. It relates to the composition as a body. The present invention also relates to a method for producing the resin composition and a method for producing the composition. Furthermore, the present invention relates to various molded articles and parts using the resin composition, and a method for producing these molded articles and parts.
[0002]
[Prior art]
Automotive glazings occupy a large portion of the outer shape and are important driving and cosmetic components. With the advent of various types of bent glass, the degree of freedom of the shape of the window glass has been increased, and the area used has also been increased. For this reason, weight reduction and safety are required for the window glass. In addition, recent headlamps have many new shapes, and demands for shape flexibility, optical performance, and the like are increasing.
[0003]
Conventionally, inorganic glass has been used for the above-mentioned applications such as window glass. In recent years, attempts have been made to use resin glass instead of the inorganic glass. However, resin-made glass has a smaller elastic modulus than inorganic glass, and thus has been difficult to apply to large window glass parts and the like.
[0004]
On the other hand, in order to improve the mechanical strength and the like of the resin composition, a filler such as glass fiber is generally blended as a reinforcing material. However, such a fibrous filler has a diameter of about 10 μm and a length of about 200 μm, so that visible light is not transmitted, but is reflected and becomes opaque. Therefore, such a filler-reinforced resin composition cannot be applied to the window glass of automobiles as the above-mentioned resin glass.
[0005]
In addition, resin glass has a lower surface hardness than inorganic glass, and is liable to be scratched by a wiper or the like, and from this point, application to window glass parts and the like is difficult. In view of this problem, attempts have been made to apply a coupling treatment to the surface of the resin composition constituting the resin glass and to cure the surface, but even in this case, the surface hardness is such that it can withstand long-term friction. Cannot be realized, and the above-mentioned problem of abrasion has not been solved.
[0006]
Further, in order to compensate for the above-mentioned drawbacks such as mechanical strength and surface height of resin glass, attempts have been made to produce window glass parts by laminating resin glass and inorganic glass. Due to such factors, interfacial peeling is caused particularly in summer or the like, so that it has not been put to practical use.
[0007]
In JP-A-11-343349 and the like, attempts have been made to improve the mechanical strength such as heat resistance and impact resistance of a target resin composition by blending silica fine particles in a process of synthesizing an acrylic resin. However, because the mechanical strength of the acrylic resin itself is not sufficient, the intended mechanical strength cannot be realized. Further, in the examples of the above publication, it is disclosed that a polycarbonate resin is dissolved in a methylene chloride solvent and silica fine particles are mixed therein, but in order to obtain a desired mechanical strength, silica is comparatively used. If it is blended in a large amount, it becomes difficult to uniformly mix and disperse, and as a result, it is impossible to achieve the intended improvement in mechanical strength, and further, the transparency has been deteriorated due to the influence of aggregated silica. .
[0008]
[Problems to be solved by the invention]
The present invention provides a resin composition which is excellent in mechanical strength such as rigidity and impact resistance, and excellent in surface height and thermal stability, and which can be suitably used as a practical organic glass, and the like. It is intended to provide a composition as an intermediate for making. Further, the present invention provides a method for producing the resin composition, a method for producing the composition, and various molded articles and parts using the resin composition, and methods for producing these molded articles and parts. With the goal.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides:
The present invention relates to a composition, characterized in that 2,2-bis (4-hydroxyphenyl) propane is chemically bonded to an oxidized compound via an aliphatic hydrocarbon group.
[0010]
Also, the present invention
The present invention relates to a resin composition characterized in that polycarbonate is chemically bonded to an oxidized compound via an aliphatic hydrocarbon group.
[0011]
The present inventors have conducted intensive studies to achieve the above object. As a result, as a base material of the intended resin composition, a polycarbonate resin having an inherently high mechanical strength and thermal stability is used, and various modifications and improvements are made to this, thereby making the conventional inorganic resin. Attempts were made to achieve mechanical strength, surface height and thermal stability that could replace glass.
[0012]
In order to improve the strength, rigidity and the like of the polycarbonate resin, the improvement is performed in consideration of the molecular structure of the polycarbonate as a constituent element. Generally, if the crystallinity of the polycarbonate resin is improved, the strength and the like are improved, but the transparency and the like are deteriorated. Therefore, an attempt was made to achieve the above object by making various changes not to the polycarbonate resin serving as the base material but to the filler contained therein.
[0013]
Various reports have been made on the types and sizes of fillers, and when a fiber-based filler is blended as described above, the transparency deteriorates when the major axis is longer than the visible light range. Or On the other hand, when a filler such as silica is blended in a large amount, not only the desired mechanical strength cannot be realized due to the aggregation effect, but also the transparency is deteriorated. Therefore, the present inventors examined the presence state of the above-described filler in the polycarbonate resin as a base material, and studied a method of blending the filler into the polycarbonate resin.
[0014]
As a result, according to the present invention, by chemically bonding an oxidizing compound filler such as silica to a polycarbonate via an aliphatic hydrocarbon group, the oxidizing compound filler can be strongly bonded to the polycarbonate. I found what I can do. Further, the present inventors have found that the oxidized compound filler is directly bonded to the polycarbonate, so that the oxidized compound filler is uniformly dispersed without agglomeration in the finally obtained resin composition.
[0015]
Therefore, according to the present invention, only by blending a relatively small amount of an oxidizing compound filler, sufficient mechanical strength and surface height, furthermore, thermal stability can be obtained in combination with the inherent properties of the polycarbonate resin. Can be realized. Also, when a relatively large amount of oxidized compound filler is blended to further improve the mechanical strength, etc., it will be dispersed uniformly without agglomeration in the resin, so it will maintain sufficiently high transparency In this state, the intended mechanical strength can be realized.
[0016]
In the present invention, the “resin composition” means an original resin composition that can be used as a resin glass or the like, and the “composition” is defined as defined in claim 1. Before the polymerization of 2,2-bis (4-hydroxyphenyl) propane, 2,5-bis (4-hydroxyphenyl) propane is bonded to the oxidized compound via an aliphatic hydrocarbon group. It means a quantitative composition. Therefore, in the present invention, the above-mentioned resin composition is obtained by first preparing the above-mentioned composition and then going through a polymerization process.
[0017]
The details and other features of the present invention, a method for manufacturing a resin plastic material, a molded body, a part, and a method for manufacturing these will be described in the following embodiments of the invention.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
(Composition and resin composition)
In the composition of the present invention, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “bisphenol A”) is chemically bonded to an oxidized compound via an aliphatic hydrocarbon group. It is necessary to be. Although the kind of the aliphatic hydrocarbon group is not particularly limited, the oxidized compound and the oxidized compound are more robust through the availability and covalent bond of the aliphatic hydrocarbon which is a raw material of the aliphatic hydrocarbon group. For the reason that a chemical bond can be easily formed, alkylene (—CH ₂ (CH ₂ ) NCH ₂ -, N = 1 to 3). In particular, propylene (n = 1) is preferred among the above-mentioned alkylenes because the raw materials used in the production process are inexpensive and easily available.
[0019]
The shape of the oxidized compound is not particularly limited, and may be not only a general particle shape, a spherical shape, and a substantially spherical shape, but also a chain shape, a rectangular parallelepiped or a plate shape, a linear shape such as a fiber, a branched shape and the like. However, it is preferably spherical, pearl necklace-shaped or chain-shaped.
[0020]
The size of the oxidized compound is not particularly limited as long as it can be uniformly dispersed in polycarbonate in bisphenol A or the finally obtained resin. In order to obtain a composition or resin composition having high strength, low thermal expansion coefficient and high transparency, it is desirable to use an oxide compound as small as possible. More preferably, the oxide compound has an average primary particle size of 380 nm or less, particularly preferably 1 nm to 200 nm, in the visible light wavelength region (380 to 770 nm) or less. Thereby, the transparency of the composition and the resin composition in the visible light wavelength region can be sufficiently ensured.
[0021]
In addition, the above-mentioned "average primary particle diameter" refers to the average value of the length of the longest part of the oxide compound in the linear distance.
[0022]
The type of the oxide compound is not particularly limited, but silica, titania, alumina, zirconia and the like can be preferably used. Silica is particularly preferred because it is particularly inexpensive, easily available, and can be strongly bonded to bisphenol A by a covalent bond via the aliphatic hydrocarbon group.
[0023]
As the silica, it is preferable to use a silica fine particle obtained by a dry process, the surface of which is previously treated with a chlorinated aliphatic hydrocarbon group, but colloidal silica can also be used. Silica fine particles produced by a dry method are produced by flame hydrolysis using silicon tetrachloride, hydrogen and oxygen as raw materials. Colloidal silica is grown in liquid using sodium silicate (water glass) as a raw material.
[0024]
As described in detail below, by subjecting the composition obtained as described above to a solution polymerization method using the phosgene method, the polycarbonate is chemically bonded to the oxidized compound via an aliphatic hydrocarbon group. Thus, a resin composition of the present invention is obtained. Therefore, the types of aliphatic hydrocarbon groups and the types, shapes, and sizes of the oxidized compounds that can be suitably used in the above-described composition can be applied to the above-described resin composition as it is.
[0025]
The polycarbonate in the resin composition is preferably an aromatic polycarbonate. Since the aromatic polycarbonate has a phenyl group, the movement of the main chain is suppressed, and as a result, it exhibits high heat resistance and also exhibits high impact resistance due to the three-dimensional structure of the main chain.
[0026]
(Method for producing composition and method for producing resin composition)
The composition of the present invention is prepared as follows. First, the oxidized compound is reacted with a predetermined compound to add a chlorinated aliphatic hydrocarbon group to the surface of the oxidized compound. The chlorinated aliphatic hydrocarbon group is determined according to the type of the aliphatic hydrocarbon group to be bonded to the oxidized compound, and when the aliphatic hydrocarbon group is an alkylene, it is a chlorinated alkyl group, The preferred propylene is chlorinated propyl.
[0027]
Next, the oxidized compound subjected to the surface treatment as described above is dispersed and mixed in a chlorinated hydrocarbon solvent to prepare a first solution. In addition, as said chlorinated hydrocarbon solvent, methylene chloride, 1,2-dichloroethane, chloroform, and chlorobenzene can be exemplified.
[0028]
Next, bisphenol A is dissolved and mixed in a predetermined organic solvent to prepare a second solution. Next, a mixed solution of the first solution and the second solution is prepared, and an organic base catalyst such as triethylamine, pyridine and dimethylaniline is charged into the mixed solution to perform a dehydrochlorination reaction. As a result, it is possible to obtain the composition of the present invention in which bisphenol A is chemically bonded to the oxidized compound via an aliphatic hydrocarbon group. The chlorinated hydrocarbon solvent as described above can be used as the organic solvent.
[0029]
Further, the following shows a reaction formula in the case where silica fine particles are used as the oxidizing compound and propylene is used as the aliphatic hydrocarbon group.
[0030]
Embedded image

[0031]
Further, as the compound used for adding the chlorinated aliphatic hydrocarbon group to the surface of the oxidized compound, it is preferable to use a silane compound containing the chlorinated aliphatic hydrocarbon group. That is, the chlorinated aliphatic hydrocarbon group is preferably formed on the surface of the oxidized compound by subjecting the oxidized compound to a silane coupling treatment using the silane compound. Thus, the above-described additional operation can be easily performed.
[0032]
In particular, when silica fine particles are used as the oxidizing compound, alkoxysilane can be used as the silane compound.After converting the alkoxy group of the alkoxysilane into a silanol group through hydrolysis, the above-described surface treatment can be performed. preferable. In this case, the silanol groups are firmly bonded to the hydroxyl groups on the surfaces of the silica fine particles by a dehydration condensation reaction, whereby stable silica fine particles containing a chlorinated aliphatic hydrocarbon group can be obtained.
[0033]
The reaction formula in the dehydration condensation reaction when 3-chloropropyltrimethoxysilane is used as the silane compound is shown below.
[0034]
Embedded image

[0035]
Embedded image

[0036]
The resin composition of the present invention is prepared by subjecting the composition obtained as described above to a solution polymerization method in the phosgene method. Specifically, if necessary, additional bisphenol A and phosgene are charged into the above-mentioned mixed solution, and further, an organic base catalyst such as triethylamine, pyridine and dimethylaniline is charged to cause condensation polymerization, and A resin composition comprising such a polycarbonate chemically bonded to an oxidized compound via an aliphatic hydrocarbon group is obtained.
[0037]
In the resin composition thus obtained, the transparency, strength, elastic modulus, and the like were improved as compared with the case of using polycarbonate alone, and the linear expansion coefficient was reduced. This is due to the reinforcing effect of the oxide compound, and the larger the aspect ratio (length / thickness) is, the more effective the reinforcing effect and the effect of reducing the linear expansion coefficient are.
[0038]
In the following, a reaction formula in the case where the above-described solution polymerization method is applied to a composition containing silica fine particles chemically bonded via bisphenol A and propylene is shown.
[0039]
Embedded image

[0040]
FIG. 1 is a model diagram conceptually showing the structure of the resin composition obtained through the above reaction formula. As apparent from FIG. 1, it is assumed that the resin composition has a structure in which polycarbonate is bonded to the periphery of the silica fine particles by expanding the molecular chain.
[0041]
As a method for synthesizing polycarbonate, there is a transesterification method in addition to the above-described phosgene method. However, this method generally does not increase the molecular weight, and therefore has low strength and elastic modulus, and satisfies the required specifications of automobile parts and the like. Can not.
[0042]
(Molds and parts)
The resin composition of the present invention realizes improvement of rigidity without sacrificing transparency and impact strength, and has a low coefficient of thermal expansion, and also has a property of suppressing warpage at a high temperature. For example, it is suitable for automobiles, home appliances and houses, such as transparent covers for instrument panels for interior materials and window glasses (windows), headlamps, sunroofs and combination lamp covers for interior materials. Suitable for the transparent members and equipment used.
[0043]
In particular, the resin composition of the present invention is a resin window (particularly, a resin window with a hot wire) as an alternative to inorganic glass which is required to be lightweight and has a high degree of freedom in molding; Resin wiper system; Resin door mirror stay; Resin biller; Resin molded body; Resin mirror; Resin lamp reflector; Resin engine room cover and case; Resin cooling device parts; Hollow communicating with atmosphere Resin-integrated molded article having a structure and / or a closed hollow structure; an integrally molded part in which one part is provided with two or more different functions; a molded article having a movable part and a non-movable part; and a hydrocarbon-based fuel The effect can be effectively exerted in applications such as a part or a container for storing a container.
Hereinafter, the use of the resin plastic material of the present invention will be described in detail.
[0044]
<Vehicle interior / exterior part molded product and vehicle outer panel>
As one of the uses of the resin composition according to the present invention, a molded article for interior and exterior parts for a vehicle and an outer panel for a vehicle can be given. The resin composition of the present invention is excellent in transparency, impact resistance, rigidity, high heat resistance, low coefficient of thermal expansion, and excellent in dimensional stability during heating / molding. It is suitable for use as an exterior part molded product or a vehicle outer panel.
[0045]
2 and 3A are external perspective views of the sedan vehicle from the rear side, and FIG. 3B is a plan view of the sedan vehicle. As the interior / exterior component molding for a vehicle, as shown in FIG. And a headlamp cover (not shown). As the vehicle outer panel, as shown in FIGS. 3A and 3B, 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), etc. Can be exemplified.
[0046]
<Resin wiper system, Resin door mirror stay and Resin pillar>
One of the uses of the resin composition of the present invention includes a resin wiper system, a resin door mirror stay, and a resin pillar. As described above, the resin composition of the present invention has excellent transparency, impact resistance, rigidity, high heat resistance, low coefficient of thermal expansion, and excellent dimensional stability during heat / molding. , Such as a wiper system, etc., which are required to improve visibility.
[0047]
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. In addition, the conventional door mirror stay is made of a resin having the same color or black paint finish as the outer plate, and has a problem that visibility when turning right or left is obstructed. Further, the conventional biller is made of steel, and the front biller and the center biller have a problem that visibility is obstructed when the vehicle is traveling normally or turning left and right, and the rear biller is blocked when moving backward or confirming backward.
[0048]
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 heat / molding are required, it has been difficult to realize the conventional transparent resin material. On the other hand, by using the resin composition of the present invention having excellent transparency, high rigidity, a low coefficient of thermal expansion, and a low coefficient of thermal shrinkage as a transparent material as described above, these problems can be solved, and transparent The above parts are obtained. Transparency of these parts is expected to contribute not only to the visibility but also to the design.
[0049]
One embodiment of the wiper system of the present invention is schematically shown in FIG. As shown in FIG. 4, the wiper system 30 includes a wiper arm 31 and a wiper blade 32, and operates so as to draw a semi-arc around the wiper arm fixing nut hole 33. The wiper blade 32 is composed of an elastic supporting component and a soft rubber component.
[0050]
In the wiper system of the present invention, at least one of the support parts of the wiper arm 31 and the wiper blade 32 uses the resin composition of the present invention as a transparent material. It is preferable that the rubber component of the wiper blade 32 in the wiper system of the present invention be made of silicon rubber or the like having high durability and relatively high transparency. Further, the support component of the wiper blade 32 may be prepared using a resin-rubber mixed composition obtained by adding an appropriate amount of an acrylic rubber component to the resin composition of the present invention. Thereby, a suitable elasticity can be given to the support component of the wiper blade.
[0051]
As such a resin-rubber mixed composition, for example, an acrylic rubber component (ethyl acrylate, butyl acrylate or a copolymer thereof, for example, Nippon Zeon Co., Ltd., based on 100 parts by mass of the resin composition of the present invention) 1-30 parts by mass of Nipol AR31 manufactured by Nissan Co., Ltd.).
[0052]
For the door mirror stay and the biller, only the resin composition of the present invention may be used as a transparent material.For example, the resin composition of the present invention may be formed of a multilayer laminate in which another resin material is laminated. It is possible. Such a multilayer laminate only needs to include at least one layer composed of the resin composition of the present invention. Preferably, the multilayer laminate has an outermost layer and a lowermost layer, more preferably an intermediate layer (one or more layers). A layer made of the resin composition can also 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.
[0053]
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. Other resin materials for such a multilayer laminate include polycarbonate, polystyrene, styrene / methyl methacrylate copolymer, and the like.
[0054]
Further, the manufacturing method and configuration are not particularly limited, and each may be a single part. For example, a door mirror stay and a front biller, or each biller and a resin roof panel may be integrated by a manufacturing method of an integrally molded body described later. May be.
[0055]
<Resin molded body>
One application of the resin composition according to the present invention is a resin molded article having a transparent portion and an opaque portion, wherein at least the transparent portion contains the resin composition of the present invention. Since the resin composition of the present invention has high rigidity and high heat resistance, and also has excellent dimensional stability during heating / molding, chemical resistance, transparency, and impact resistance, it has both a transparent portion and an opaque portion. Suitable for use in parts. Automobile parts will be described as an example of a resin molded body having a transparent portion and an opaque portion, wherein at least the transparent portion is a resin molded body containing the resin composition of the present invention.
[0056]
Automobiles include, for example, transparent components such as various lamps, covers, and glass, and opaque components such as outer panels and various interior components. Each of these parts requires different characteristics such as transparency, rigidity, heat resistance, low coefficient of linear expansion, low molding shrinkage, and chemical resistance. It was difficult to integrate various parts.
[0057]
In contrast, the use of the resin composition of the present invention, which has the characteristics of high rigidity, high heat resistance, low coefficient of linear expansion, low molding shrinkage, and high chemical resistance, at least as a transparent material solves these problems. Can be resolved. Furthermore, by integrally molding the transparent component and the opaque component, the number of components and the number of steps can be reduced, and the weight of the component can be reduced. In addition, since several types of components can be integrally formed, a conventionally divided outer shape can be formed by one continuous line, so that the appearance of the components can be improved.
[0058]
For example, headlamps that require transparency are in contact with separate (transparent or opaque) components such as bumpers, front grilles, fenders, and hoods that surround the headlamp. The number of parts can be reduced by integrally molding the transparent portion and the opaque portion. Further, in the past, individual components were assembled one by one. However, since only one integrated component may be assembled, the number of steps during assembly can be reduced.
[0059]
Further, since the resin composition of the present invention has high heat resistance, there is no problem that the resin is melted even when the heat source of the lamp is near. Conventional headlamps are made of polycarbonate resin, have low light fastness, and turn yellow when exposed to sunlight, so they had to be coated on the surface layer. ) Can also solve such a problem.
[0060]
In addition, for example, automotive glass requiring transparency includes a side glass and a back door glass attached to a door, a rear quarter glass and a rear glass adhered to a rear fender and a roof, and the like. By using the resin composition of the present invention for at least the transparent portion, an integrally molded part of these and glass can be obtained. For example, the side glass and the back door glass have a glass disposed between a door outer and a door inner. However, by forming a hollow portion inside using the material (resin composition) of the present invention, a door is formed. The outer door inner glass can be formed integrally and simultaneously, thereby reducing the number of parts.
[0061]
Furthermore, 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 are integrally formed. Can be. The door lock, wiper motor, etc. will be installed in the hollow part of the component in a later process. Similarly, the biller garnish and the rear water glass can be integrated.
[0062]
Further, for example, it can be applied to partial transparency of structural parts by utilizing the transparent, high strength, and high rigidity characteristics of the material (resin composition) of the present invention. For example, when the resin composition of the present invention is used for a part of a roof, the part can be made transparent. Therefore, a transparent roof can be obtained without providing a glass sunroof. As described above, by using the resin composition of the present invention, a structural part having high strength and high rigidity, in which a part of the resin molded body is a transparent part and the other part is an opaque part, is formed. You can also. Note that the opaque portion may be colored.
[0063]
FIG. 5 is an external perspective view of the wagon vehicle from the rear side. The wagon car shown in FIG. 5 is a resin molded body having a transparent part and an opaque part, a lamp hood / fender integrated resin molded body 41, a biller garnish / glass integrated resin molded body 42, and a roof fender / glass integrated resin. It has a molded body 43, a backdoor / glass integrated resin molded body 44, a door / glass integrated resin molded body 45, and the like. The resin composition of the present invention can be applied to transparent portions of these resin molded articles. For example, the present invention can be applied to a lamp hood of a lamp hood / fender integrated resin molded body 41. As described above, by using the resin composition of the present invention, the number of parts can be reduced, and the number of steps for mounting parts can be reduced.
[0064]
FIG. 6 is a schematic view showing an instrument panel and a cover of an instrument in which a transparent resin portion and an opaque resin portion are integrally formed. If the resin composition of the present invention is applied to the transparent resin portion, the transparent resin portion and the opaque resin portion can be integrally formed, so that the instrument panel 51 and the instrument cover 52 are previously formed. By simultaneously molding (integrally) the above and integrating several types of components into the instrument panel 51, the number of components can be reduced and the weight can be reduced.
[0065]
Note that, in a resin molded body having a transparent portion and an opaque portion, in order to obtain a colored opaque resin molded body, a method using a colored raw resin, a method of painting or printing on the opaque portion, or a method of coloring the opaque portion, or There is a method using a colored sheet as the resin.
[0066]
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 beret 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. To produce the resin molded body using the colored resin, open the mold containing the colored resin, or newly create a molten resin passage, using another cylinder, the cavity of the mold What is necessary is just to inject a transparent molten resin into a part. 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.
[0067]
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 then painted or printed from the front or back surface of the resin molded body, thereby coloring and opaque. Secure Painting or printing can be performed before shaping the molten resin, and shaping can be performed thereafter.
[0068]
When a colored sheet is used as the opaque resin, a pre-colored opaque sheet is pre-shaped and then placed in a mold. Next, the molten transparent resin is poured into the mold, cooled and solidified, and then taken out of the mold to obtain the resin molded product of the present invention.
[0069]
Further, according to the above method, for example, as a roof fender-glass integrated resin molded body, the glass part 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. Is a transparent portion, and the fender, glass, and the rest of the roof can be an opaque resin molded body.
[0070]
Furthermore, the resin molded article of the present invention in which the transparent portion and the opaque portion are integrally molded can be constituted only by the resin composition of the present invention (including a case where the resin composition is partially colored with a pigment or the like). It is also possible to constitute a multilayer laminate in which the above resin composition and another resin are laminated. Such a multilayer laminate may include at least one layer composed of the resin composition of the present invention, preferably the outermost surface 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.
[0071]
<Resin window, resin mirror, resin lamp reflector, resin engine room cover and case, resin cooling device parts>
As one of the uses of the resin composition according to the present invention, a resin window characterized by comprising the resin composition, particularly preferably a resin window with a hot wire, a resin mirror, a resin lamp reflector, These are the resin engine room cover and case, and the resin cooling device parts.
[0072]
The resin composition of the present invention has high rigidity and high heat resistance, and is excellent in dimensional stability during heating / molding, chemical resistance, and transparency. Therefore, for example, a resin window, a resin mirror, a lamp reflector, It is suitable for the use of parts such as an engine room cover and a case, 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.
[0073]
FIG. 7 is an explanatory view showing the resin mirror and the resin window according to the present invention, and is a plan view of a sedan-type automobile illustrating the positions of these vehicle components. For example, as shown in FIG. 7, resin windows such as a rear window 63, a door window (side window) 62, and a front window 61 are provided with a heat ray that can be heated inside or on the surface of the molded body in order to provide an anti-fog function. A heater may be provided. In such a case, the windows are installed on the front, rear, and side doors of the vehicle as shown in FIG. 7 as components for preventing wind and rain, but the used area is 3 to 4 m. ² In the case of the conventional inorganic glass, the weight is as heavy as 30 to 35 kg, so that the use of the resin composition of the present invention can be expected to reduce the weight.
[0074]
In addition, when a conventional transparent resin material is used, heat resistance and thermal expansion of the resin material due to a hot-wire heater are problems. However, the resin composition of the present invention has excellent dimensional stability during heating / molding. The use of the resin composition of the present invention eliminates these problems. Further, since the resin composition of the present invention has high rigidity, it can be applied to large parts such as the front window 61, the door window 62, and the rear window 63 as shown in FIG.
[0075]
The method of forming the hot wire heater is not particularly limited, and a known method can be used. For example, a method of insert molding a hot wire portion formed into a film, a method of forming a hot wire portion on the indoor side surface by a vapor deposition, application, printing method, or the like can be used. Further, since the resin composition of the present invention has high rigidity, it can be applied to large components such as a front window, a door window, and a rear window, and can be reduced in weight.
[0076]
In addition, when the resin side mirror 64 (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. 7, the present invention can be applied to a room mirror or the like in a vehicle interior.
[0077]
As described above, the resin composition of the present invention realizes improvement in rigidity without sacrificing transparency and impact strength, has a low coefficient of thermal expansion, and has characteristics of suppressing warpage and the like at high temperatures. Therefore, it can be applied to various uses such as windows and mirrors, which have not been fully adopted yet because there are issues to be solved in terms of safety and function. As a result, it is possible to achieve a reduction in the weight of the vehicle and an increase in the degree of freedom in design, which have been demanded in the past.
[0078]
In recent years, the use of one-box type RVs has been remarkably widespread, and the proportion of windows has been increasing, and the demand for resin windows has been increasing in order to reduce weight and improve occupant visibility and comfort. . The transparent resin glass formed from the resin composition of the present invention has the functions required for these automotive windows, and can contribute to weight reduction and improved comfort of the vehicle. In addition to the resin windows 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 railways It can also be used as interior materials for vehicles.
[0079]
FIG. 8 is a cross-sectional view of an automobile lamp. As shown in FIG. 8, a reflector 73 is disposed inside an outer member 72 fixed to the vehicle body-side base 71, a bulb 74 and an optical axis adjuster 75 are connected to the reflector 73, and the outer member 72 further includes an outer lens. 76 are fitted. When the reflector 73 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 high heat resistance at light weight, and can be a lamp reflector having excellent dimensional stability and surface smoothness, such as a head lamp, a fog lamp, and a rear combination lamp. It can be suitably used for a reflector or a sub-reflector of a headlamp.
[0080]
In addition, as a method of forming the reflection portion, for example, a method of insert-molding a reflection film when manufacturing the member, or forming the member by injection molding / press molding, and then forming a vapor deposition film on the reflection portion. There are methods.
[0081]
Further, the resin composition of the present invention can be applied to an engine room cover and a case. 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, radiator 81, coolant reserve tank 82, washer tank inlet 83, electrical component housing 84, brake oil tank 85, cylinder head cover 86, engine body 91, timing chain 92, gasket 93, front There is a chain case 94 and the like. In addition, since the resin composition of the present invention is transparent, visibility in the 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.
[0082]
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 101, a 0-ring 102, a water pump housing 103, a water pump impeller (impeller) 104, a water pump 105, a water pump pulley 106 shown in FIG. 11, a water pipe 111 shown in FIG. 12, a thermostat housing 112, Examples include radiator tank components such as the top and base of the radiator tank such as the thermostat 113 and the water inlet 114, and components such as a coolant reserve tank and a valve. 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.
[0083]
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 surface 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.
[0084]
<Integrated resin molded body having a hollow structure and / or a closed hollow structure>
As one of the uses of the resin composition according to the present invention, a resin integrated molded article having the hollow structure communicating with the atmosphere and / or having a sealed hollow structure, which includes the resin composition, can be exemplified. As described above, the resin composition of the present invention has high rigidity and high heat resistance, and also has excellent dimensional stability at the time of heating / forming, and thus has a hollow structure such as a door, a roof, and a hood. It is suitable for the use of parts having. Preferred examples of the resin-integrated molded article of the present invention include outer plates and interior / exterior parts of automobiles.
[0085]
At this time, the outer plate and the interior / exterior parts of the 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 parts. For example, the side door and the back door are formed of a copper plate having a hollow structure on the outside and the inside, and a resin panel is attached to the inside copper plate in an assembling process after painting, and various auxiliary machines 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.
[0086]
Although the above-mentioned resin integrated molded article can be constituted only by the resin composition of the present invention, for example, it can 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 surface 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.
[0087]
The resin-integrated molded product, the outermost surface layer, a decorative material such as a design printing layer and the like, by providing a decorative layer, such as design, tactile feel, texture can be enhanced to improve the product quality, the outermost layer of the integrated molded product Is preferably 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.
[0088]
In the integrally molded 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 of two or more of these. Thereby, the heat insulation performance and the sound insulation performance of the integrally molded article can be improved.
[0089]
The specific filling / sealing material is not particularly limited, and a known filling / sealing material can be used. For example, when transparency is required, nitrogen, argon, carbon dioxide, a gas such as air is preferable, and when transparency is not required, in addition to the above-mentioned gases, a liquid is shown by heating at the time of sealing and Paraffin, wax, etc., which become solid at room temperature after encapsulation, are preferred.
[0090]
With the above-mentioned encapsulant, it is possible to suppress the escape of cold heat from the passenger compartment and the invasion of high heat from the outside air in the summer, and to escape the warmth in the winter and suppress the invasion of cold heat from the outside air to maintain a comfortable interior environment. it can. 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.
[0091]
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. And, for example, the following first to third methods are suitably used.
[0092]
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, before or during welding of the outer peripheral portion, or after welding, preferably before or after welding, a pressurized fluid is injected into a closed space between the two sheets to expand the sheets. After the expansion, the mold is closed and the pressurized fluid pressure is maintained until the compact cools, thereby forming a hollow structure.
[0093]
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, as one typical production method of the resin integrated molded body, two resin sheets containing the resin composition of the present invention are heated and inserted into a mold in an open state. Before or after welding the outer peripheral portion, a pressurized fluid is injected between the sheets, and while the sheet is expanded and / or expanded, the mold is closed, and the pressurized fluid pressure is maintained and the hollow Form the structure.
[0094]
As a second method, while filling or after filling the molten resin composition of the present invention into a mold in a closed state, the mold is retracted to add the inside of the molten resin while expanding the cavity volume. This is a method of forming a hollow structure by injecting a pressurized fluid. That is, while filling the molten resin composition of the present invention in a closed mold, and / or after filling, pressurized fluid is injected into the molten resin while expanding the cavity volume to form a hollow structure. It is.
[0095]
As a third method, one resin sheet made of the resin composition of the present invention is inserted into the mold surface on one side of the mold, and the mold is retracted while filling the back surface with the molten resin, or after filling, to reduce the cavity volume. A method of forming a hollow structure by injecting a pressurized fluid into the interior of the molten resin while expanding, or using two resin sheets, inserting the sheets into the cavities on both sides of the mold and filling the molten resin between the sheets to achieve a cavity volume And a pressurized fluid is injected to form a hollow structure. That is, 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 back of the one sheet or the two sheets is inserted with the mold closed. During or after filling with the molten resin, a pressurized fluid is injected into the molten resin while increasing the cavity volume to form a hollow structure.
[0096]
In the above embodiment, the type of the resin to be filled between the sheets or on the back surface of 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. The same kind of resin as the resin in contact with the resin composition described above, or a resin having an SP value close to that of the resin composition of the present invention is used. Examples of such a filling resin include a polycarbonate resin, a styrene-based resin, poly-4-methylpentene-1, a thermoplastic polyurethane resin and the like, and it is particularly preferable to use a polycarbonate resin.
[0097]
The polycarbonate resin is a polymer derived from a dihydric phenolic compound represented by bisphenol A, and may be produced by any of a phosgene method, a transesterification method, or a solid phase polymerization method. Further, in addition to a conventional polycarbonate resin, a polycarbonate resin polymerized by a transesterification method may be used.
[0098]
The type of the pressurized fluid described above is not particularly limited, and can be 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.
[0099]
As shown in FIGS. 13 and 14, applicable parts of the resin integrated molded article having a hollow structure of the present invention include, for example, a hood 121, a door 122, a back door 123, a roof 124, a fender 125, a window 126, and a trunk lid 127. , Center console box 131, biller garnish 132, instrument panel 133, head lining (not shown), and the like. These components can simultaneously and integrally form the inner / outer and accompanying components, a rain hose, and the like, and can reduce the number of components and the number of steps.
[0100]
Further, by enclosing a gas, a liquid, a solid, or a mixture thereof in the hollow portion, additional functions such as heat insulation performance and sound insulation performance can be provided. 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 headlining and can have heat insulation and sound insulation functions, and the doors and fenders can have inner / outer parts. Can be integrated.
[0101]
<Integrally molded parts with two types of functions>
One of the uses of the resin composition according to the present invention is to make it possible to integrate two or more types of parts having different functions, comprising the resin composition, and to form two or more different types into a single part. It is an integrally molded part provided with the function of 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.
[0102]
The resin composition of the present invention has high rigidity and high heat resistance, and has various functions such as dimensional stability during heating / molding and chemical resistance. They can be applied, and by integrally molding them, two or more types of components having different functions can be integrated to form an integrally molded component in which two or more types of functions are given to a single component. 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.
[0103]
For example, in the case of instrument panels, which are large interior parts, panel panels, air ducts and cases for air conditioners, cross car beams (steering cross members), and the like are separately manufactured, and these are assembled on a car production line. If an attempt is made to integrally mold the panel and the air duct or case of the air conditioner with a conventional resin material, the resulting molded part becomes large and has a complicated shape. Swelling and the like are problems, but such problems can be solved by using the resin composition of the present invention.
[0104]
Further, since the resin composition of the present invention has high heat resistance as described above and is excellent in dimensional stability during heating / forming, it is an integrally molded part containing the resin composition of the present invention. As shown in FIG. 15, the instrument panel can be formed by integrally molding the panel portion 141 and the air duct and case 142 of the air conditioner into a whole structure. Cross members) can be eliminated.
[0105]
Furthermore, by using the resin composition of the present invention, it is possible to integrally mold a bracket or the like that 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. The same 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, the door inner panel, the guide rail, the speaker housing, and the like can be formed as an integrally molded part.
[0106]
FIG. 16 shows another example of the integrally molded part of the present invention. As shown in FIG. 16, when the roof rail 151 which is a large exterior component is taken as an example, it can be integrally formed with the above-described roof panel 152 made of the resin composition of the present invention. Since the roof rail is heavy and is used in an environment that is severe also in terms of temperature, the conventional resin materials have been particularly problematic in rigidity and heat resistance (including cold resistance). However, such problems can be solved by using the resin composition of the present invention. The same effect can be obtained, for example, when applied to a boiler, and can be integrally formed with the above-described trunk lid made of the resin composition of the present invention.
[0107]
Further, as shown in FIG. 17, taking a radiator core as a large body part as an example, a resin radiator core is currently appearing as a front-end module. Lighter parts having excellent chemical resistance and rigidity can be obtained, or a fan shroud, a bracket, and the like can be integrally formed. Further, in the present invention, it is also possible to use the resin composition as a transparent material, and in such a case, for example, it is also possible to integrally mold including a transparent member such as a radiator reservoir tank and a headlamp cover. It is. Further, it is also possible to integrally mold including a bumper reinforcing material which is conventionally a separate body.
[0108]
In the case of an air cleaner or a throttle chamber, which is a component in an engine room, the resin composition of the present invention, which has excellent heat resistance and chemical resistance and low thermal expansion, can be integrally molded. It becomes. Conventionally, such integration has been attempted, but the engine room is in a severe environment due to high temperature and chemicals such as oil, and this measure is a problem with conventional resin materials. Such a problem can be solved by using it. Similar effects can be obtained when applied to an intake manifold or a cylinder head cover, and can be integrally formed with the above-mentioned parts.
[0109]
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 surface layer and the lowermost layer of the laminate, and more preferably the intermediate layer also has the resin composition layer. Can be provided. By using a multilayer laminate, it is possible to provide additional functions that cannot be exhibited only with the resin composition of the present invention.
[0110]
<Mold having movable part and non-movable part>
Since the resin composition of the present invention has high rigidity and high heat resistance and excellent dimensional stability during heating / forming, it is used for parts having a movable part and a non-movable part such as a throttle chamber. It is suitable for. Therefore, as one of the uses of the resin composition according to the present invention, a molded article having a movable portion and a non-movable portion containing the resin composition of the present invention can be exemplified.
[0111]
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 an automobile and an air conditioner unit. These components are mainly for controlling the flow of gas such as air, and serve as gas passages as non-movable parts, that is, cylindrical components (molded bodies) for introducing flowing gas, The movable portion is constituted by a lid that can be opened and closed to control the gas flow, and includes, for example, a throttle chamber and each door in an air conditioner unit. Airtightness is important for these components.
[0112]
When attempting to mold the cylindrical part and lid part of these parts using conventional resin materials, the molding shrinkage and thermal expansion rates are large, so the dimensional accuracy cannot be improved, and the airtightness of the opening and closing parts is limited. there were. 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. Further, since the resin composition of the present invention has high rigidity, the use of these resin compositions makes it possible to reduce the weight of parts and thereby improve the responsivity.
[0113]
The method for producing a molded article having a movable part and a non-movable part of the present invention is not particularly limited, and a known method can be used. The molded body having a movable portion and a non-movable portion of the present invention, for example, after separately molding the movable portion and the non-movable portion using an injection molding method, a method of assembling these may be used, for example, It is preferable that the movable portion and the non-movable portion are integrally formed by a method such as a two-color molding method. Thereby, 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 by the following method, for example.
[0114]
The throttle chamber has a cylindrical chamber portion 171 that is a non-movable portion, and an opening / closing valve 172 and an opening / closing valve shaft 173 that are movable portions. First, a metal shaft for an opening / closing 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 disk-shaped opening / closing valve. Injection molding of an open / close valve. At this time, the metal shaft and the disc-shaped on-off valve are integrated. According to the present invention, the present invention can be preferably applied to a case where the movable portion is an opening / closing lid for controlling gas flow and the non-movable portion is a cylindrical molded product for introducing a flowing gas.
[0115]
<Parts or container for storing hydrocarbon fuel>
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. Therefore, as one of the uses of the resin composition according to the present invention, a part or container for storing a hydrocarbon-based fuel containing the resin composition of the present invention can be exemplified.
[0116]
FIG. 19 shows a resin fuel tank in a vehicle such as an automobile as an example of the storage container for the hydrocarbon-based fuel described above. Gasoline, which is a hydrocarbon fuel, is injected and stored in a fuel tank 182 via a filler tube 181, and then the gasoline is pumped by a fuel pump 183 to an engine (not shown; indicated only as 184). Fuel system.
[0117]
In the resin fuel tank shown in FIG. 19, the parts to which the resin composition of the present invention can be applied include a fuel tank main body 182, a filler cap 185, a pent tube 186, a fuel hose 187, a fuel cut-off valve (not shown), A delivery pipe (not shown), an evaporative tube (not shown), a return tube (not shown), a fuel sender module (not shown), and the like can be given.
[0118]
The fuel tank body is the largest component of the fuel system components of these vehicles. In recent years, attempts have been made to convert the fuel tank body to resin, and due to the effect of increasing the degree of freedom in the shape of parts, the amount of stored fuel can be increased by about 10 liters as compared with a metal fuel tank body. The weight could be reduced by about 25%. Due to these advantages, expectations for resinification of fuel tanks are increasing.
[0119]
Here, the current state and issues of resinification of the fuel tank will be described in detail. Conventionally, 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 layers 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.
[0120]
In a single-layer fuel tank, the permeation of a large amount of hydrocarbon-based fuel from this 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 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.
[0121]
The creation of the multi-layer fuel tank has established a technique that satisfies the regulations on the regulation of evaporation of hydrocarbons. However, the molding process has become complicated, resulting in a significant increase in price. In addition to the above-mentioned problems, the laminated structure of a plurality of resins loses the smoothness of recycling, leaving a new problem that cannot be met in the age of a recycling society.
[0122]
On the other hand, the surface-modified silica compound in the resin composition of the present invention has a SP value of more than 11 due to the remaining silanol groups, and prevents the permeation of the above-mentioned hydrocarbon fuel corresponding to PA or EVOH. Function. The main component of the resin composition of the present invention is mainly composed of a resin having a polar group such as acryl and having an SP value of 11 or more, and is not easily compatible with gasoline as a hydrocarbon-based fuel, in other words, the compatibility is poor. Due to the poor material composition, it is a more desirable material for a fuel tank.
[0123]
Therefore, by using the resin composition of the present invention, it is possible to provide a fuel tank for a vehicle which satisfies the regulations on the evaporation of hydrocarbons even in a single-layer type. As a result, it is possible to reduce the production cost, which is a problem, and to meet social demands for recycling. In this case, the resin composition of the present invention can be used to form 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.
[0124]
Although the effect is slightly lower than that of a fuel tank for vehicles, the resin composition of the present invention can also be used for household products such as kerosene containers. This reduces the evaporation of kerosene into the atmosphere, which can contribute to the preservation of the global environment.
[0125]
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 scratch resistance of the surface, such as exterior materials for buildings, interior materials, and railways It can also be used as interior materials for vehicles.
[0126]
As a method for manufacturing various members including such vehicle parts and building interior materials, injection molding, vacuum pressure molding, and the like, as described in detail above, may be appropriately selected according to the parts and applications. General glass fiber reinforced resin, the physical properties of the glass fiber is gradually reduced due to breakage of the glass fiber by repeatedly receiving shear stress, the recyclability is also low, the resin composition of the present invention, the surface-modified silica Since a compound is used, it is hardly subjected to shear stress, and a decrease in physical properties can be suppressed.
[0127]
【Example】
Hereinafter, the present invention will be described in detail based on examples. In each of the following examples and comparative examples, the total light transmittance, the dispersion state under a transmission electron microscope, the bending strength, the bending elastic modulus, and the coefficient of linear expansion were evaluated using the following apparatus.
・ Total light transmittance: Measured with a haze meter (HM-65 manufactured by Murakami Color Research Laboratory)
-Dispersion state by transmission electron microscope: Observed at 80,000 times using H-800 manufactured by Hitachi, Ltd., and observed dispersion state as black silica particles and white resin.
・ Bending strength and elastic modulus: Measured with Autograph Shimadzu DCS-10T)
-Measurement of linear expansion coefficient: Measured with a thermomechanical measuring device (TMA120C manufactured by Seiko Denshi Kogyo)
[0128]
(Example 1)
In 250 ml of a methylene chloride solution, 228 g of bisphenol A and 0.25 g of hydrosulfide (sodium hydrosulfite) as a coloring inhibitor due to oxidation were dissolved. Subsequently, the solution thus obtained is subjected to a surface treatment using 3-chloropropyltrimethoxysilane with respect to silica fine particles (Aerosil 200: manufactured by Nippon Aerosil Co., Ltd.) to add a chlorinated propyl group to the surface. 750 ml of a methylene chloride solution obtained by dispersing and mixing 53 g of the oxidized compound was added. Next, 15 ml of a 1% triethylamine in methylene chloride solution was added as a catalyst for the dehydrochlorination reaction, and the mixture was stirred for about 1 hour, whereby bisphenol A was covalently bonded to the chlorinated propyl group on the silica surface.
[0129]
Then, the mixture was stirred while phosgene was blown into the above mixed solution at a rate of 2 g / min for about 50 minutes. Next, 15 ml of a 1% triethylamine methylene chloride solution as a catalyst for the dehydrochlorination reaction was added to the mixed solution, and the mixture was stirred for about 1 hour to polycondensate bisphenol A and phosgene, and a solution of a polycarbonate resin having silica covalently bonded thereto. Got.
[0130]
Next, the solution was neutralized with phosphoric acid, washed with water, dropped into methanol, and the polymer composition was precipitated, filtered and dried to obtain a white powdery resin composition. The resin composition thus obtained was dried and pulverized and then subjected to hot press molding to obtain a sheet-like molded product. This molded article was transparent, and improved strength and elastic modulus and reduced thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0131]
(Example 2)
In 250 ml of a methylene chloride solution, 228 g of bisphenol A and 0.25 g of hydrosulfide (sodium hydrosulfite) as a coloring inhibitor due to oxidation were dissolved. Next, a water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical Industries, Ltd.) was evaporated and dried in advance into a powder in the solution thus obtained, and the same surface treatment as in Example 1 was performed. Was performed, and 750 ml of a methylene chloride solution obtained by dispersing and mixing 53 g of an oxidized compound obtained by adding a chlorinated propyl group to the surface was added. Next, 15 ml of a 1% triethylamine in methylene chloride solution was added as a catalyst for the dehydrochlorination reaction, and the mixture was stirred for about 1 hour, whereby bisphenol A was covalently bonded to the chlorinated propyl group on the silica surface.
[0132]
Next, phosgene was added to the above-mentioned mixed solution in the same manner as in Example 1 to carry out polymerization to obtain a target white powdery resin composition. Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0133]
(Example 3)
In the same manner as in Example 2 except that a water-soluble linear colloidal silica (Snowtex OUP: manufactured by Nissan Chemical) was used instead of the water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical). Silica fine particles having a chlorinated propyl group on the surface were obtained and subjected to a polymerization process using the same phosgene method as in Example 2 to obtain a target white powdery resin composition.
[0134]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0135]
(Example 4)
Example 2 was repeated except that a water-soluble pearl necklace-shaped colloidal silica (Snowtex PS-SO: manufactured by Nissan Chemical) was used instead of the water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical). In the same manner, silica fine particles having a chlorinated propyl group on the surface were obtained, and the desired white powdery resin composition was obtained through a polymerization process using the same phosgene method as in Example 2.
[0136]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0137]
(Example 5)
When obtaining silica fine particles having a chlorinated propyl group on the surface, a chlorobenzene solution was used instead of the methylene chloride solution, and the silica fine particles were obtained under the same conditions as in Example 1 and polymerized under the same conditions as in Example 1. Was carried out to obtain a target white powdery resin composition.
[0138]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0139]
(Example 6)
When obtaining silica fine particles having a chlorinated propyl group on the surface, using a chloroform solution instead of a methylene chloride solution, the silica fine particles were obtained under the same conditions as in Example 1, and polymerization was performed under the same conditions as in Example 1. By carrying out, the desired white powdery resin composition was obtained.
[0140]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0141]
(Example 7)
When obtaining silica fine particles having a chlorinated propyl group on the surface, a 1,2-dichloroethane solution was used instead of the methylene chloride solution, and the silica fine particles were obtained under the same conditions as in Example 1. To obtain a target white powdery resin composition.
[0142]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded article was transparent, and improved strength and elastic modulus and decreased thermal expansion coefficient were observed. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 1 shows the measured values.
[0143]
[Table 1]

[0144]
(Comparative Example 1)
120 g of a polycarbonate resin (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics) is dissolved in 240 g of a methylene chloride solution, and 30 g of silica whose surface is treated with methyl groups of fine silica particles (Aerosil 200: manufactured by Nippon Aerosil) are dispersed and mixed in the solution. Thus, a polycarbonate resin / silica mixed solution was prepared. This mixed solution was dropped into methanol to precipitate a resin composition, which was filtered, dried, and then turned into a white powder.
[0145]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded product was insufficient in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0146]
(Comparative Example 2)
120 g of a polycarbonate resin (Iupilon S2000, manufactured by Mitsubishi Engineering Plastics) was dissolved in 240 g of a methylene chloride solution, and then water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical) was previously evaporated and dried in the solution. A powder was prepared, and 30 g of silica fine particles obtained by subjecting this powder (Aerosil 200: manufactured by Nippon Aerosil) to a surface treatment with a methyl group was dispersed and mixed to prepare a polycarbonate resin / silica mixed solution. This mixed solution was dropped into methanol to precipitate a resin composition, which was filtered, dried, and then turned into a white powder.
[0147]
Next, the resin composition was processed in the same manner as in Example 1 to obtain a sheet-like molded product, which was subjected to various measurements. The obtained molded product was insufficient in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0148]
(Comparative Example 3)
Resin composition in the same manner as in Comparative Example 2 except that a chain colloidal silica (Snowtex OUP: manufactured by Nissan Chemical) was used instead of the water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical). And a sheet-like molded product was obtained in the same manner as in Comparative Example 2. The obtained molded product was insufficient in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0149]
(Comparative Example 4)
Resin composition in the same manner as in Comparative Example 2 except that a chain colloidal silica (Snowtex OUP: manufactured by Nissan Chemical) was used instead of the water-soluble spherical colloidal silica (Snowtex ST-O: manufactured by Nissan Chemical). And a sheet-like molded product was obtained in the same manner as in Comparative Example 2. The obtained molded product was insufficient in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0150]
(Comparative Example 5)
20 g of silica (Aerosil R974: Nippon Aerosil) powder surface-treated with a methyl group is melt-mixed with 80 g of polycarbonate resin (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics) using a small kneader, and the obtained composition is pulverized and hot-pressed. By molding, a sheet-like molded product was obtained. The resulting molded article was extremely poor in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0151]
(Comparative Example 6)
Water-soluble spherical colloidal silica (Snowtex ST-0: manufactured by Nissan Chemical Industries, Ltd.) was previously evaporated to dryness to obtain a powder, and 20 g of a silica powder obtained by surface-treating this powder with a methyl group was used to obtain 80 g of a polycarbonate resin (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics). Then, the resulting composition was melt-mixed with a small kneader, and the obtained composition was pulverized and hot-pressed to obtain a sheet-like molded product. The resulting molded article was extremely poor in transparency, and showed a slight improvement in strength and elastic modulus and a slight decrease in coefficient of thermal expansion. Further, when the blending ratio of silica was examined by a transmission electron microscope, it was 20 wt%. Table 2 shows the measured values.
[0152]
Table 2 also shows various properties of the polycarbonate resin alone having no silica fine particles.
[0153]
[Table 2]

[0154]
As described above, the present invention has been described in detail with reference to the embodiments of the present invention. However, the present invention is not limited to the above description, and various modifications and changes are possible without departing from the scope of the present invention. .
[0155]
【The invention's effect】
As described above, according to the present invention, a resin composition which is excellent in mechanical strength such as rigidity and impact resistance, and excellent in surface height and thermal stability, and can be suitably used as a practical organic glass or the like And a composition as an intermediate for producing the resin composition. In addition, it is possible to provide a method for producing the resin composition, a method for producing the composition, and various molded articles and parts using the resin composition, and methods for producing these molded articles and parts.
[Brief description of the drawings]
FIG. 1 is a model diagram conceptually showing the structure of an example of the resin composition of the present invention.
FIG. 2 is an explanatory view showing door molding, a frame frame of a door mirror, a wheel cap, a boiler, a bumper, a turn signal lens, and a biller garnish as an example of a vehicle exterior component application of the resin composition according to the present invention, FIG. 3 is an external perspective view of the sedan-type vehicle from the rear side, illustrating the positions of these vehicle exterior parts.
FIG. 3 is an explanatory view showing a front fender, a door panel, a roof panel, a front panel, and a rear panel as an example of a vehicle outer panel application of the resin composition according to the present invention, and FIG. FIG. 3B is a perspective view from the rear side of the sedan-based vehicle illustrating the position of the vehicle outer panel, and FIG. 3B is a plan view of the sedan-based vehicle.
FIG. 4 is a schematic view of a resin wiper system according to the present invention.
FIG. 5 is a diagram showing an example of a resin molded product having a transparent portion and an opaque portion according to the present invention, wherein at least the transparent portion contains the resin composition of the present invention; Explanatory drawing showing a hood / fender body resin molded article, a biller garnish, a vitreous body resin molded article, a roof / fender / glassy body resin molded article, a back door / a glass / body resin molded article, and a door / glass / body resin molded article. FIG. 2 is an external perspective view of a wagon vehicle from the rear side, illustrating the positions of these vehicle exterior parts.
FIG. 6 is a schematic diagram showing an instrument panel and a cover of an instrument in which a transparent resin portion and an opaque resin portion according to the present invention are integrally formed.
FIG. 7 is an explanatory view showing a resin mirror and a resin window according to the present invention, and is a plan view of a sedan-based automobile illustrating the positions of these vehicle components.
FIG. 8 is a cross-sectional view showing a resin lamp reflector of the present invention.
FIG. 9 is an explanatory view showing a radiator, a coolant reserve tank, a washer tank inlet, an electric component housing, a brake oil tank, and a cylinder head cover as examples of parts in an engine room using the resin composition according to the present invention. FIG. 3 is a schematic perspective view of the interior of an engine room with a hood panel of the automobile removed.
FIG. 10 is an explanatory view showing an engine body, a timing chain, a gasket, and a front chain case as an example of parts in an engine room using the resin composition according to the present invention. FIG.
FIG. 11 shows an example of a resin cooling device part using the resin composition according to the present invention, a water pipe, an O-ring, a water pump housing, a water pump impeller (impeller), a water pump, and a water pump pulley. FIG. 2 is an exploded perspective view showing the respective components, so that the configuration of each of these components can be understood.
FIG. 12 is a view showing a water pipe, a thermostat housing, a thermostat, and a water inlet as another example of a resin cooling device part using the resin composition according to the present invention, and these respective component configurations are shown. FIG. 3 is an exploded perspective view for easy understanding.
FIG. 13 is an explanatory view showing a hood, a door, a back door, a roof, a fender, a window, and a trunk lid as an example of an integrally molded resin having a hollow structure, using the resin composition according to the present invention; FIG. 13 (a) is a perspective view from the rear side of the sedan vehicle with the door open to show these positions, and FIG. 13 (b) is a perspective view from the rear side of the one-box car. FIG.
FIG. 14 is an explanatory diagram showing a center console box, a biller garnish, and an instrument panel as another example of a resin integrated molded article having a hollow structure using the resin composition according to the present invention. 14 (a) is a perspective view of a front seat in a vehicle cabin showing a center console box position, and FIG. 14 (b) is a vehicle cabin perspective view showing a biller garnish and an instrument panel position. is there.
FIG. 15 shows an example of an integrally molded part using a resin composition according to the present invention, in which two or more different functions are imparted to one part, as an integral molding of an instrument panel and an air duct or a case of an air conditioner. It is explanatory drawing which shows a component.
FIG. 16 is an explanatory view showing an integrally molded part of a roof rail and a roof panel as another example of an integrally molded part using the resin composition according to the present invention, and is an external perspective view of a roof portion of an automobile. .
FIG. 17 is an explanatory view showing an integrally molded part of a radiator core as another example of an integrally molded part using a resin composition according to the present invention, in which two or more different functions are imparted to one part.
FIG. 18 shows an example of a molded article having a movable part and a non-movable part using the resin composition according to the present invention, which is an open / close valve that is a movable part of a chamber, and an open / close valve and an open / close valve shaft that are non-movable parts. FIG. 18 (a) is a cross-sectional view of a formed body having the chamber portion, the opening / closing valve, and the opening / closing valve shaft, and FIG. 18 (b) is a view showing FIG. 18 (a). FIG. 3 is a cross-sectional view of the chamber section taken along a line AA of FIG.
FIG. 19 is an explanatory view showing a fuel tank and fuel-related parts around the fuel tank as an example of a vehicle exterior part application of the resin composition according to the present invention.
[Explanation of symbols]
1 door mall
2 Door mirror frame
3 Wheel cap
4 Boiler
5 bumper
6 turn signal lens
7 Biller Garnish
8 Rear Finisher
21 Front fender
22 Door panel
23 Roof panel
24 Food Panel
25 Trunk lid
30 Wiper system
31 Wiper arm
32 wiper blade
33 Nut hole for fixing wiper arm
41 Lamp hood / fender integrated resin molding
42 Resin molded body with glass garnish and glass
43 Roof fender / glass integrated resin molded product
44 Backdoor / Glass integrated resin molding
45 Door / glass integrated resin molding
51 Instrument panel
52 Instrument cover
61 Front window
63 Rear window
71 Body side body
73 reflector
75 Optical axis adjuster
81 radiator
62 Door window
64 side mirror
72 Outer member
74 valve
75 Outer lens
82 Coolant reserve tank
83 Washer tank inlet
84 electrical component housing
86 cylinder head cover
92 Timing Chain
94 Front chain case
85 Brake oil tank
91 engine body
93 gasket
101 water pipe
102 O-ring
103 Water pump housing
104 Water pump impeller (impeller)
105 Water pump
106 Water pump pulley
111 water pipe
112 thermostat housing
113 Thermostat
114 Water Inlet
121 Food
122 door
123 backdoor
124 roof
125 fender
126 windows
127 trunk lid
131 Center console box
132 Biller Garnish
133 Instrument panel
141 Panel
142 Air duct and case of air conditioner
151 roof rail
152 Roof panel
171… Chamber section
172 Open / close valve
173 Open / close valve shaft
181 Filler tube
182 fuel tank
183 fuel pump
185 Filler cap
186… Pent tube
187 Fuel Horse
188 air chamber

Claims (62)

A composition, characterized in that 2,2-bis (4-hydroxyphenyl) propane is chemically bonded to an oxidized compound via an aliphatic hydrocarbon group. The composition according to claim 1, wherein the aliphatic hydrocarbon group is an alkylene. The composition of claim 2, wherein the alkylene is propylene. The composition according to any one of claims 1 to 3, wherein the oxidized compound has a spherical shape, a pearl necklace shape, or a chain shape. The composition according to any one of claims 1 to 4, wherein the oxide compound has an average primary particle diameter of 380 nm or less in visible light wavelength. The composition according to claim 5, wherein the average primary particle diameter of the oxidized compound is 1 nm to 200 nm. The composition according to any one of claims 1 to 6, wherein the oxidized compound is silica fine particles. A resin composition, characterized in that polycarbonate is chemically bonded to an oxidized compound via an aliphatic hydrocarbon group. The resin composition according to claim 8, wherein the aliphatic hydrocarbon group is an alkylene. The resin composition according to claim 9, wherein the alkylene is propylene. The resin composition according to any one of claims 8 to 10, wherein the oxide compound has a spherical shape, a pearl necklace shape, or a chain shape. The resin composition according to any one of claims 8 to 11, wherein the oxide compound has an average primary particle diameter of 380 nm or less in visible light wavelength. The resin composition according to claim 12, wherein the average primary particle diameter of the oxidized compound is 1 nm to 200 nm. The resin composition according to any one of claims 8 to 13, wherein the oxidized compound is silica fine particles. The resin composition according to any one of claims 8 to 14, wherein the polycarbonate is an aromatic polycarbonate. A step of adding a chlorinated aliphatic hydrocarbon group to the surface of the oxidized compound,
Preparing a first solution by dispersing and mixing the oxidized compound having the chlorinated aliphatic hydrocarbon group in a chlorinated hydrocarbon solvent,
Dissolving and mixing 2,2-bis (4-hydroxyphenyl) propane in a predetermined organic solvent to prepare a second solution;
Mixing the first solution and the second solution to form a mixed solution, and introducing an organic base catalyst into the mixed solution to cause a dehydrochlorination reaction;
The method for producing a composition according to any one of claims 1 to 7, comprising: The method for producing a composition according to claim 16, wherein the addition of the chlorinated aliphatic hydrocarbon group is performed by a coupling treatment using a silane compound containing the chlorinated aliphatic hydrocarbon group. . 18. The method according to claim 16, wherein the organic solvent dissolving the 2,2-bis (4-hydroxyphenyl) propane is a chlorinated hydrocarbon. The composition according to any one of claims 16 to 18, wherein the chlorinated hydrocarbon is at least one selected from the group consisting of methylene chloride, 1.2-dichloroethane, chloroform, and chlorobenzene. Production method. The method for producing a composition according to any one of claims 16 to 19, wherein the chlorinated aliphatic hydrocarbon group is a chlorinated alkyl group. The method according to claim 20, wherein the chlorinated alkyl group is a chlorinated propyl group. A step of adding a chlorinated aliphatic hydrocarbon group to the surface of the oxidized compound,
Preparing a first solution by dispersing and mixing the oxidized compound having the chlorinated aliphatic hydrocarbon group in a chlorinated hydrocarbon solvent,
Dissolving and mixing 2,2-bis (4-hydroxyphenyl) propane in a predetermined organic solvent to prepare a second solution;
Mixing the first solution and the second solution to form a mixed solution, and introducing an organic base catalyst into the mixed solution to cause a dehydrochlorination reaction;
Mixing phosgene in the mixed solution and polymerizing,
The method for producing a resin composition according to any one of claims 8 to 15, comprising: The production of the resin composition according to claim 22, wherein the addition of the chlorinated aliphatic hydrocarbon group is performed by a coupling treatment using a silane compound containing the chlorinated aliphatic hydrocarbon group. Method. 24. The method according to claim 22, wherein the organic solvent dissolving the 2,2-bis (4-hydroxyphenyl) propane is a chlorinated hydrocarbon. The resin composition according to any one of claims 22 to 24, wherein the chlorinated hydrocarbon is at least one selected from the group consisting of methylene chloride, 1.2-dichloroethane, chloroform, and chlorobenzene. Manufacturing method. The method according to any one of claims 22 to 25, wherein the chlorinated aliphatic hydrocarbon group is a chlorinated alkyl group. The method according to claim 26, wherein the chlorinated alkyl group is a chlorinated propyl group. A molded article for interior and exterior parts for vehicles, comprising the resin composition according to any one of claims 8 to 15. A vehicle outer panel comprising the resin composition according to any one of claims 8 to 15. A resin wiper system comprising the resin composition according to any one of claims 8 to 15. A resin door mirror stay, comprising the resin composition according to claim 8. A resin-made biller comprising the resin composition according to claim 8. A resin molded product having a transparent part and an opaque part, characterized in that at least the transparent part contains the resin composition according to any one of claims 8 to 15. The resin molded body according to claim 33, wherein the transparent part and the opaque part are integrally molded. 35. The resin molded product according to claim 33, wherein the opaque portion is formed by coloring with a pigment dispersed in a resin. The resin opaque part according to claim 33 or 34, wherein the opaque part of the resin molded part is formed by painting or printing before or after molding. 35. The resin molded product according to claim 33, wherein the opaque portion of the resin molded component is formed using a colored sheet. A resin window with a hot wire, comprising the resin composition according to claim 8. A resin mirror, comprising the resin composition according to claim 8. A resin lamp reflector comprising the resin composition according to claim 8. A resin engine room interior cover comprising the resin composition according to any one of claims 8 to 15. The resin engine room interior cover according to claim 39, wherein a portion including the resin composition is transparent. A resin engine room inner case, comprising the resin composition according to any one of claims 8 to 15. The resin engine room inner case according to claim 43, wherein the portion made of the resin composition is transparent. A resin cooling device part comprising the resin composition according to claim 8. A resin integrated molded article comprising the resin composition according to any one of claims 8 to 15 and having a hollow structure communicating with the atmosphere and / or a closed hollow structure. 47. The resin molded article according to claim 46, wherein the hollow structure is filled and sealed with a gas, a liquid, a solid, or a mixture of at least two of them. 48. The resin-integrated molded product according to claim 46, wherein the outermost layer is formed of a decorative material. 49. An outer panel of an automobile, comprising the resin-integrated molded product according to any one of claims 46 to 48. An interior / exterior component comprising the resin integral molded product according to any one of claims 46 to 48. 16. Heating two resin sheets containing the resin composition according to any one of claims 8 to 15, inserting the resin sheet into a mold in an open state, pressing the sheet outer peripheral portion, and welding the outer peripheral portion. Before or after welding, a pressurized fluid is injected between the sheets, and during or after expansion of the sheet, the mold is closed, and the pressurized fluid pressure is maintained to form a hollow structure. The method for producing a resin-integrated molded product according to any one of claims 46 to 48, characterized in that: Melting the pressurized fluid while expanding the cavity volume of the mold during or after melting and filling the resin composition according to any one of claims 8 to 15 into the mold in a closed state. The method for producing a resin-integrated molded product according to any one of claims 46 to 48, wherein the hollow structure is formed by injecting the resin into a resin. One or two resin sheets containing the resin composition according to any one of claims 8 to 15 are inserted into the mold cavity surface in the open state, the mold is closed, and the mold is closed. 49. The hollow structure is formed by injecting a pressurized fluid into the molten resin while expanding the cavity capacity of the mold during or after filling the back surface with the molten resin. The method for producing a resin integrated molded article according to any one of the above. A resin component according to any one of claims 8 to 15, wherein two or more types of components having different functions are integrated, and a single component is provided with at least these two or more types of functions. To be an integrally molded part. A molded article comprising the resin composition according to any one of claims 8 to 15 and having a movable portion and a non-movable portion. The molded article according to claim 55, wherein the movable section and the non-movable section are integrally formed by two-color molding. 57. The molded article according to claim 55, 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 component containing a hydrocarbon-based fuel, comprising the resin composition according to claim 8. 59. The hydrocarbon fuel storage component of claim 58, comprising a series of fuel components for a vehicle. A container for storing a hydrocarbon-based fuel, comprising the resin composition according to claim 8. 61. The hydrocarbon fuel storage component according to claim 60, comprising a fuel tank for a vehicle. 62. The hydrocarbon-based fuel storage component according to claim 61, wherein the vehicle fuel tank is formed by a blow molding method.

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