JP2004025824A - Recycled foamed laminated sheet for automobile upholsteries using resin and recycling method of automobile upholstery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recycling method of an automobile upholstery enabling a material recycling by which a waste material can be recycled for fabricating an automobile upholsteries and obtain a foamed laminated sheet for automobile upholsteries or the automobile upholstery which holds the properties such as a light weight, heat insulation, molding processability and heat resistance required for the automobile upholstery. <P>SOLUTION: The automobile upholstery comprises the foamed laminated sheet formed by laminating a non-foaming layer on the both sides of a foamed layer whose base resin is a modified polyphenylene ether resin, a skin material laminated on one side of the sheet and an abnormal-note preventing material properly laminated on the other side of the sheet. The skin material and the abnormal-note preventing material are substantially separated and removed from both of the trimmings and waste materials of the automobile upholstery. The reclaimed resin is obtained by extrusion-molding and pelletizing the resin composition derived from the foamed laminated sheet. The resin is used for fabricating at least one side of the non-foamed layers of the foamed laminated sheet. <P>COPYRIGHT: (C)2004,JPO

Description

【０１１５】
【表２】

【０１１６】
〔樹脂の種類〕
変性ＰＰＥ　　　：変性ポリフェニレンエーテル
ＰＳ　　　　　　：ポリスチレン
ＳＭＡＡ共重合体：スチレン−メタアクリル酸共重合体
ＨＩＰＳ　　　　：ハイインパクトポリスチレン
ＳＢＳ　　　　　：ポリスチレン−ポリブタジエンブロック共重合体
ＳＥＰＳ　　　　：ポリスチレン−水素添加ポリブタジエンブロック共重合体
酸変性ＳＥＢＳ　：ポリスチレン−酸変性水素添加ポリブタジエンブロック共重合体
【０１１７】
また、実施例および比較例で行った評価方法を以下に示す。
〔発泡層および成形体の厚さ〕
１次発泡シート、成形体の幅方向に２０ヶ所の厚さを測定し、その測定値の平均値を算出した。
【０１１８】
〔発泡倍率〕
１次発泡シートの密度ｄｆをＪＩＳＫ７２２２に準じて測定し、耐熱性樹脂の密度ｄｐをＪＩＳＫ７１１２に準じて測定し、次式より求めた。
発泡倍率＝ｄｐ／ｄｆ
【０１１９】
〔独立気泡率〕
ＡＳＴＭＤ−２８５９に準じて評価して求めた（マルチピクノメーター（ベックマン社製）を使用）。
【０１２０】
〔セル径〕
発泡層の断面を光学顕微鏡で観察し、２０個のセル径を測定し、その測定値の平均値を算出した。
【０１２１】
〔目付〕
１次発泡シートの押出し方向に５ヶ所より、１０ｃｍ×１０ｃｍの大きさの試験片を切り出し、それらの重量を測定したのち、平均値を算出した。
【０１２２】
〔ビカット軟化温度〕
ＪＩＳ　Ｋ　７２０６に準じて測定した。
【０１２３】
〔ＩＺＯＤ衝撃値〕
ＪＩＳ　Ｋ　６９１１，５．２１に準じ、２号試験片を使用し、ノッチ有りで測定した。
【０１２４】
〔実装耐熱性試験〕
図５に示すような自動車天井材２２（幅９３０ｍｍ×長さ１４２４ｍｍ）を自動車天井部（カットボディ）に装着し、サンバイザー、ルームミラー、ルームランプ、ガニッシュ、ピラーを介して実車と同等となるように固定した。なお、図中２４はアシストグリップ取付穴、２６はサンバイザー取付穴、２８はサンバイザー留め取付孔、３０はルームミラー取付穴、３２は室内灯取付穴である。また、フロント部分に測定点を６点、成形体の中心線と対称に１２０ｍｍ間隔で刻印した（図５中ａ〜ｆ）。フロント部の測定点付近に標線を設け垂直方向の距離を測定した。次に、８０±１℃に設定した恒温室に、天井材を取付けた自動車天井部を２４時間投入した後、成形体フロント部に刻印された測定点の、垂直方向寸法変化量の絶対値を測定した。
判定の基準としては自動車内装材としての実用性を考慮して、以下の基準を用いた。
○・・・フロント部の変形量の絶対値が２ｍｍ以内
×・・・フロント部の変形量の絶対値が２ｍｍ以上
【０１２５】
〔落球衝撃試験〕
自動車天井材の一般部から３００ｍｍ×３００ｍｍのサンプルを切り出し、０℃恒温層中に室外側を上にして２時間以上放置の後、２ｍの高さから、４５ｇ（２２φ）の鉄球を自然落下させ、室外側非発泡層の割れの有無を観察した。
判定の基準としては自動車内装材としての実用性を考慮して、以下の基準を用いた。
○・・・非発泡層の割れ無し
×・・・非発泡層の割れ有り
【０１２６】
実施例１
〔再生に利用される自動車天井材の製造方法〕
ＰＰＥ系樹脂成分４０重量％，ＰＳ系樹脂成分６０重量％となるように変性ＰＰＥ系樹脂（Ａ）５７．１部とＰＳ系樹脂（Ｂ）４２．９部とを混合した混合樹脂（ビカット軟化温度１４５℃）１００部に対してｉｓｏ−ブタンを主成分とする発泡剤（ｉｓｏ−ブタン／ｎ−ブタン＝８５／１５）３．４部およびタルク０．３２部を押出機により混練した。この混練樹脂をサーキュラーダイスより樹脂温２００℃で押出し、８ｍ／分の速さの引き取りロールを介して巻取りロールにロール状に巻取り、一次厚み２．４ｍｍ、一次発泡倍率１２倍、独立気泡率９０％、セル径０．１９ｍｍ、目付け１８０ｇ／ｍ^２の発泡シートを得た。
【０１２７】
次いで、この発泡シートをロールより８ｍ／分の速さで繰り出しながら、ＳＭＡＡ共重合体樹脂（Ｃ）５０部とＨＩＰＳ樹脂（Ｄ）５０部の混合樹脂（ビカット軟化温度１１５℃）を樹脂温度が２４５℃となるように押出機で溶融・混練し、Ｔダイを用いてフィルム状に押出し、更に、異音防止材（Ｋ１）を供給し、溶融状態でフィルム状の非発泡層を、まず異音防止材（Ｋ１）を接触させた後、溶融状態でフィルム状の非発泡層を発泡層と異音防止材で挟み込む形で積層し、発泡シートの片面（室外側）に厚さ１５０μｍの耐熱性の改善されたＰＳ系樹脂非発泡層を形成した。
【０１２８】
更に、この耐熱性の改善されたＰＳ系樹脂非発泡層を形成したシートをロールから８ｍ／分の速さで繰り出しながら、ＰＰＥ系樹脂成分２０重量％、ＰＳ系樹脂成分８０重量％となるように変性ＰＰＥ系樹脂（Ａ）２８．６部、ＰＳ系樹脂（Ｂ）７１．４部を混合した混合樹脂（ビカット軟化温度１２５℃）を樹脂温度が２６５℃となるように押出機で溶融・混練しＴダイを用いてフィルム状に押出し、発泡積層シートの他方の面（室内側）に厚さ１２０μｍの変性ＰＰＥ系樹脂非発泡層を形成し、非発泡層を両面に積層した発泡積層シート（Ｉ）を得た。
【０１２９】
得られた発泡積層シート（Ｉ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１３０】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、変性ＰＰＥ系樹脂非発泡層が車内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１３１】
〔自動車天井材の端材の再利用〕
上記自動車天井材の成形加工時に発生したトリミング屑を回収した。回収されたトリミング屑を、粉砕機により５ｍｍサイズのチップ状に粉砕し、篩および比重分離により不織布層（表皮材、異音防止材）を分離、除去した。得られた基材粉砕分離品にＳＢＳ（Ｅ）を５部添加し、さらに自動車天井材用ＰＰ架橋発泡シートを５部添加して２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、押出機先端に取り付けた１００メッシュのスクリーンを通過させた後、孔状のダイスより樹脂を押出した。なお、溶融・混練時にはベント孔より発生するガス成分を回収した。このようにして再生樹脂（ａ）を採取した。
【０１３２】
室内側非発泡層の構成樹脂に再生樹脂（ａ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ａ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（ＩＩ）を得た。
【０１３３】
得られた発泡積層シート（ＩＩ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１３４】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１３５】
得られた自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、得られた自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１３６】
実施例２
基材粉砕分離品にＳＢＳ（Ｅ）を１０部添加する以外は実施例１と同様にして、再生樹脂（ｂ）を採取した。室内側非発泡層の構成樹脂に再生樹脂（ｂ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｂ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１の自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（ＩＩＩ）を得た。
【０１３７】
得られた発泡積層シート（ＩＩＩ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。
【０１３８】
その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１３９】
得られた自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、得られた自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１４０】
実施例３
基材粉砕分離品にＳＥＰＳ（Ｆ）を５部添加する以外は実施例１と同様にして、再生樹脂（ｃ）を採取した。
【０１４１】
室内側非発泡層の構成樹脂に再生樹脂（ｃ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｃ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１の自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（ＩＶ）を得た。
【０１４２】
得られた発泡積層シート（ＩＶ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１４３】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１４４】
得られた自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、得られた自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１４５】
実施例４
基材粉砕分離品に酸変性ＳＥＢＳ（Ｇ）を５部添加する以外は実施例１と同様にして、再生樹脂（ｄ）を採取した。室内側非発泡層の構成樹脂に再生樹脂（ｄ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｄ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１の自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（Ｖ）を得た。
【０１４６】
得られた発泡積層シート（Ｖ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１４７】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１４８】
得られた自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、得られた自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１４９】
比較例１
上記実施例１〜４において、再生樹脂の製造用に使用された自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、この自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１５０】
比較例２
実施例１で得られた基材粉砕分離品に自動車天井材用ＰＰ架橋発泡シートを５部添加して２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、押出機先端に取り付けた１００メッシュのスクリーンを通過させた後、孔状のダイスより樹脂を押出した。なお、溶融・混練時にはベント孔より発生するガス成分を回収した。このようにして再生樹脂（ｅ）を採取した。
【０１５１】
室内側非発泡層の構成樹脂に再生樹脂（ｅ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｅ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１の自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（ＶＩ）を得た。
【０１５２】
得られた発泡積層シート（ＶＩ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１５３】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１５４】
得られた自動車天井材の一般部を切り出し、０℃で室外側より落球衝撃試験を実施した。また、得られた自動車天井材をカットボディに装着し、８０℃の耐熱試験を実施した。得られた結果を表４に示す。また、室内側および室外側非発泡層の構成樹脂の物性を表３に示す。
【０１５５】
表３および表４より再生樹脂を非発泡層の構成樹脂に使用した自動車天井材は、相溶化剤である熱可塑性エラストマーを添加することによって、再生樹脂を構成樹脂に使用しない自動車天井材と同様に実用上遜色の無い特性を有しており、再生樹脂を構成樹脂に使用することが可能であることがわかる。
【０１５６】
【表３】

【０１５７】
【表４】

【０１５８】
実施例５
〔再生に利用される自動車天井材の製造方法〕
ＰＰＥ系樹脂成分４０重量％，ＰＳ系樹脂成分６０重量％となるように変性ＰＰＥ系樹脂（Ａ）５７．１部とＰＳ系樹脂（Ｂ）４２．９部とを混合した混合樹脂（ビカット軟化温度１４５℃）１００部に対してｉｓｏ−ブタンを主成分とする発泡剤（ｉｓｏ−ブタン／ｎ−ブタン＝８５／１５）３．４部およびタルク０．３２部を押出機により混練した。この混練樹脂をサーキュラーダイスより樹脂温２００℃で押出し、８ｍ／分の速さの引き取りロールを介して巻取りロールにロール状に巻取り、一次厚み２．４ｍｍ、一次発泡倍率１２倍、独立気泡率９０％、セル径０．１９ｍｍ、目付け１８０ｇ／ｍ^２の発泡シートを得た。
【０１５９】
次いで、上記発泡シートをロールより８ｍ／分の速さで繰り出しながら、ＳＭＡＡ共重合体樹脂（Ｃ）５０部とＨＩＰＳ樹脂（Ｄ）５０部の混合樹脂（ビカット軟化温度１１５℃）を樹脂温度が２４５℃となるように押出機で溶融・混練し、Ｔダイを用いてフィルム状に押出し、溶融状態でフィルム状の非発泡層を発泡シート表面に接触させ、発泡シートの片面（室外側）に厚さ１５０μｍの耐熱性の改善されたＰＳ系樹脂非発泡層を形成した。
【０１６０】
更に、この耐熱性の改善されたＰＳ系樹脂非発泡層を形成したシートをロールから８ｍ／分の速さで繰り出しながら、ＰＰＥ系樹脂成分２０重量％、ＰＳ系樹脂成分８０重量％となるように変性ＰＰＥ系樹脂（Ａ）２８．６部、ＰＳ系樹脂（Ｂ）７１．４部を混合した混合樹脂（ビカット軟化温度１２５℃）を樹脂温度が２６５℃となるように押出機で溶融・混練し、Ｔダイを用いてフィルム状に押出した溶融状態でフィルム状の非発泡層を、発泡積層シートの他方の面（室内側）に接触させ、厚さ１２０μｍの変性ＰＰＥ系樹脂非発泡層を形成し、非発泡層を両面に積層した発泡積層シート（ＶＩＩ）を得た。
【０１６１】
得られた発泡積層シート（ＶＩＩ）の室外側非発泡層上に、片側表面にホットメルト接着剤が点在した異音防止材（Ｋ２）を、点在したホットメルト接着剤が室外側非発泡層に接触するように配して１２０℃の熱ロールにて熱圧着した。
【０１６２】
さらに、発泡積層シート（Ａ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１６３】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、変性ＰＰＥ系樹脂非発泡層が車内側になるように金型に配置し、金型クリアランス４．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１６４】
上記構成の自動車天井材を粉砕機により５ｍｍサイズのチップ状に粉砕し、エタノールが入ったタンクの中に粉砕チップを投入した。３０分放置後、表皮材および異音防止材と発泡積層体が完全に分離していることが確認された。また、表皮材および異音防止材が沈殿し、発泡積層体が浮遊していることが確認された。浮遊している発泡積層体を１０メッシュの網ですくい上げ回収した。回収された発泡積層体を８０℃のオーブン中に１時間放置し、発泡積層体表面に付着したエタノールを取り除いた後、ＳＢＳを５部添加し、さらに自動車天井材用ＰＰ架橋発泡シートを５部添加して２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、孔状のダイスより樹脂を押出した。なお、溶融・混練時にはベント孔より発生するガス成分を回収した。このようにして溶剤の含まない再生樹脂（ｆ）を採取した。
【０１６５】
室内側非発泡層の構成樹脂に再生樹脂（ｆ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｆ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１と同様にして自動車内装材用発泡積層シート（ＶＩＩＩ）を得た。
【０１６６】
得られた発泡積層シート（ＶＩＩＩ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ１）を介して仮止めした。
【０１６７】
この１次発泡積層シートのホットメルトフィルム（Ｍ１）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１６８】
実施例６
ホットメルトフィルム（Ｍ２）を使用したこと以外は、実施例５と同様にして自動車天井材を得た。
【０１６９】
上記構成の自動車天井材のトリミング屑を粉砕機により５ｍｍサイズのチップ状に粉砕し、エタノールが入ったタンクの中に粉砕チップを投入した。３０分放置後、表皮材および異音防止材と発泡積層体が完全に分離していることが確認された。また、表皮材および異音防止材が沈殿し、発泡積層体が浮遊していることが確認された。浮遊している発泡積層体を１０メッシュの網ですくい上げ回収した。回収された発泡積層体を８０℃のオーブン中に１時間放置し、発泡積層体表面に付着したエタノールを取り除いた後、ＳＢＳを５部添加し、さらに自動車天井材用ＰＰ架橋発泡シートを５部添加して２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、孔状のダイスより樹脂を押出した。なお、溶融・混練時にはベント孔より発生するガス成分を回収した。このようにして溶剤の含まない再生樹脂（ｇ）を採取した。
【０１７０】
室内側非発泡層の構成樹脂に再生樹脂（ｇ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｇ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１における自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（ＩＸ）を得た。
【０１７１】
得られた発泡積層シート（ＩＸ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ２）を介して仮止めした。
【０１７２】
この１次発泡積層シートのホットメルトフィルム（Ｍ２）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１７３】
実施例７
ホットメルトフィルム（Ｍ３）を使用したこと以外は、実施例５と同様にして自動車天井材を得た。
【０１７４】
上記構成の自動車天井材のトリミング屑を粉砕機により５ｍｍサイズのチップ状に粉砕し、エタノールが入ったタンクの中に粉砕チップを投入した。３０分放置後、表皮材および異音防止材と発泡積層体が完全に分離していることが確認された。また、表皮材および異音防止材が沈殿し、発泡積層体が浮遊していることが確認された。浮遊している発泡積層体を１０メッシュの網ですくい上げ回収した。回収された発泡積層体を８０℃のオーブン中に１時間放置し、発泡積層体表面に付着したエタノールを取り除いた後、ＳＢＳを５部添加し、さらに自動車天井材用ＰＰ架橋発泡シートを５部添加して２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、孔状のダイスより樹脂を押出した。なお、溶融・混練時にはベント孔より発生するガス成分を回収した。このようにして溶剤の含まない再生樹脂（ｈ）を採取した。
【０１７５】
室内側非発泡層の構成樹脂に再生樹脂（ｈ）を使用し、室外側非発泡層の構成樹脂に再生樹脂（ｈ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部を使用した以外は、実施例１における自動車内装材用発泡積層シートの製造方法と同様にして自動車内装材用発泡積層シート（Ｘ）を得た。
【０１７６】
得られた発泡積層シート（Ｘ）の室内側非発泡層上に、表皮材（Ｌ）をホットメルトフィルム（Ｍ３）を介して仮止めした。
【０１７７】
この１次発泡積層シートのホットメルトフィルム（Ｍ３）面に表皮材（Ｌ）を仮止めした表皮材を有する１次発泡積層シートの四方をクランプしてオーブンに入れ、発泡積層シート表面温度が１４５℃となるように６０秒加熱した。その後、表皮材（Ｌ）が室内側になるように金型に配置し、金型クリアランス５．０ｍｍでプラグ成形を行い、トリミング、パンチング加工を施し、良好な自動車天井材を得た。
【０１７８】
比較例３
実施例５と同様の構成からなる自動車天井材のトリミング屑を用いて、粉砕機により５ｍｍサイズのチップ状に粉砕し、粉砕屑を２７０℃に加熱された２軸押出機を用いて、溶融・混練した後、孔状のダイスより樹脂を押出し再生樹脂（ｉ）を得た。
【０１７９】
再生樹脂（ｉ）７０部、ＨＩＰＳ樹脂（Ｄ）３０部の混合樹脂を２７０℃に加熱された単軸押出機で溶融・混練し、Ｔダイを用いてフィルム状に押出したところ、縞模様の厚みムラの多いフイルムが得られた。厚み調整すると部分的に裂けが発生し均一なフイルムを採取することはできなかった。
【０１８０】
以上の結果から、表皮材、異音防止材と発泡積層体をホットメルト接着剤を介して積層一体化して製造された自動車内装材は、有機溶剤中に積層構造の廃材を浸すことで不織布表皮材、不織布異音防止材から溶剤が進入し、ホットメルト接着剤が溶解されて容易に表皮材、異音防止材と発泡積層体に分離すること、更に、分離した表皮材と発泡積層体には大きな密度差があり、溶剤中で浮遊物と沈殿物に分かれるので樹脂成分（発泡積層体）を容易に回収することができることが分かる。このことから溶剤を用いて発泡積層体を溶解したのち蒸留によって分離回収する方法に比べ、非常に簡便に分離回収が出来る。
【０１８１】
【発明の効果】
本発明の方法によれば、自動車内装材の端材や廃材から簡便な操作で樹脂成分を回収することができ、自動車内装材に要求される品質を損なうことなく、自動車内装材の製造に再利用することができる。本発明はリサイクル樹脂を製品に戻す方策を提示するものであり、最近の環境負荷の抑制に向けた市場ニ−ズに工業レベルで対応できるものである。
【図面の簡単な説明】
【図１】本発明に係る再生に利用される自動車内装材の一実施態様を示す部分断面説明図である。
【図２】本発明に係る再生に利用される自動車内装材の他の一実施態様を示す部分断面説明図である。
【図３】本発明に係る再生樹脂を使用した自動車内装材用発泡積層シートの一実施態様を示す部分断面説明図である。
【図４】本発明に係る再生樹脂を使用した自動車内装材用発泡積層シートの他の一実施態様を示す部分断面説明図である。
【図５】本発明に係るトリミング加工を施した自動車天井材の一例を示す平面説明図である。
【符号の説明】
１　発泡層
３　室内側非発泡層
５　室外側非発泡層
７　接着剤層
９　表皮材用不織布層
１１　異音防止用不織布層
１０　発泡層
１２　室内側非発泡層
１４　室外側非発泡層
１６　接着剤層
１８　表皮材用不織布層
２０　異音防止用不織布層
２２　自動車天井材
２４　アシストグリップ取付け穴
２６　サンバイザー取付け穴
２８　サンバイザー留め取付け穴
３０　ルームミラー取付け穴
３２　室内灯取付け穴[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a foamed laminated sheet for an automobile interior material using a recycled resin and a method for reusing an automobile interior material. More specifically, foam laminate for automotive interior materials (especially for automotive ceiling materials) that reuses resin recycled from offcuts or waste materials of automotive interior materials and maintains quality that can withstand use at high temperatures The present invention relates to a method for reusing seats and automobile interior materials.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, as an automobile ceiling material, a material obtained by laminating a skin material in consideration of a design surface on a foam laminate has been widely used. Further, an abnormal noise preventing material may be provided on the surface of the foam laminate opposite to the skin material. An automobile ceiling material using such a foam laminate has features of being lightweight, having high heat insulating properties, and being excellent in moldability.
[0003]
Examples of the foamed laminate include a foamed layer made of a styrene-maleic anhydride copolymer resin, and a non-foamed layer made of a styrene-maleic anhydride copolymer resin (heat-resistant PS resin) laminated on both sides of the foamed layer. A non-foamed layer of a modified PPE-based resin laminated on both sides of a foamed layer of a modified polyphenylene ether-based resin (hereinafter also referred to as a modified PPE-based resin) having excellent properties is widely used. As a skin material, a polyethylene terephthalate-based nonwoven fabric is widely used, and is bonded to a foam laminate with a hot melt adhesive or the like.
[0004]
In the molding of automobile ceiling materials, a large amount of waste is generated due to a large amount of trimming loss and molding defects. For example, in the production process of the molded ceiling, about 25% of the waste is usually generated with respect to the raw material, even if the material is only scraps.
[0005]
At present, these generated wastes are incinerated, but there is an increasing demand for material recycling from the viewpoint of environmental conservation and effective use of resources.
[0006]
In the material recycling of automobile ceiling materials, it is basically essential to separate the base resin of the foam laminate from other materials such as the skin, and it is considered that recycling can be easily realized if completely separated. The conventional separation technique involves finely pulverizing offcuts and waste materials and then separating the materials into individual materials. In a dry method, a wind separator is generally used.
[0007]
Although attempts have been made to produce a foamed sheet by mixing a raw material of a foamed sheet obtained by crushing and separating an interior material for a vehicle including a foamed sheet and a nonwoven fabric skin material into raw materials (for example, see Patent Document 1). ), The skin material component remaining on the foam sheet component may have an adverse effect on foaming, and a foam sheet of stable quality may not be obtained.
[0008]
On the other hand, polyester fiber or polyolefin resin is widely used in the base material (skin material, noise control material, hot melt adhesive, etc.) for automobile ceiling materials. Polyester fiber or polyolefin-based resin may be mixed in from other automobile parts. Therefore, when recycling the above-mentioned automotive ceiling material made of the PS-based or modified PPE-based foam laminate, polyester-based fiber or polyolefin-based resin is used. Separation of the resin is required.
[0009]
However, in the separation of polyester fiber or polyolefin resin, there is a limit to the separation by the wind separation method using the specific gravity difference of the constituent layers as used for the separation of the skin material, and the polyester fiber or polyolefin resin is limited. It is desired to establish a technology that makes good use of recycled resin containing resin.
[0010]
[Patent Document 1]
JP-A-11-156854
[0011]
[Problems to be solved by the invention]
An object of the present invention is to provide a method of reusing an automobile interior material that enables material recycling while maintaining practical properties as an automobile interior material such as lightness, heat insulation, molding processability, and heat resistance. I do.
[0012]
Another object of the present invention is to provide a foamed laminated sheet for automobile interiors that uses a recycled resin and maintains the characteristics required for automobile interior materials.
[0013]
[Means for Solving the Problems]
The present inventors have developed a foam laminated sheet for an automobile interior using a material recycled resin while retaining practical properties required as an automobile interior material such as light weight, moldability, heat resistance, rigidity, and impact resistance. In order to provide the following, the structure of the base material was intensively studied. As a result, the resin (hereinafter referred to as “recycled resin”) is obtained by substantially separating and removing abnormal noise preventive materials, skin materials, and the like contained therein from waste materials of automobile interior materials or scrap materials generated in the production of automobile interior materials and automobiles. , Regenerated resin) is used for at least one non-foamed layer of a foamed laminated sheet comprising a foamed layer having a heat-resistant resin, especially a modified polyphenylene ether-based resin as a base resin, and a non-foamed layer laminated on both surfaces thereof. By doing so, it has been found that waste or scrap wood of automobile interior materials can be reused in the production of automobile interior materials while maintaining the characteristics required for automobile interior materials.
[0014]
During the regeneration of the resin, it is necessary to substantially separate and remove the polyester fibers derived from the noise control material, the skin material, and the like contained in the offcuts and waste materials of the automobile interior materials. Modified PPE-based resin, heat-resistant polystyrene-based resin (hereinafter also referred to as heat-resistant PS-based resin) or polystyrene-based resin (hereinafter also referred to as PS-based resin), which are base resins for foamed and non-foamed layers in automotive interior materials. It is known that compatibility with polyester-based fibers (resin) is not good. When the resin is regenerated in a state containing a large amount of polyester-based fibers, phase separation occurs, and the obtained resin has brittle physical properties. It may be inferior in impact, and may be unsuitable as a material for automobile interior materials.
[0015]
Furthermore, it is necessary to use a resin regenerated from scraps or waste materials of automobile interior materials for at least one non-foamed layer of a foamed layer using a modified polyphenylene ether-based resin as a base resin. The non-foamed layer is easier to adjust the physical properties than the foamed layer, and even if the heat resistance is reduced by blending the recycled resin with another resin to adjust the physical properties, the reuse of automobile interior materials is high. Since it is made of a heat-resistant foamed layer, the non-foamed layer obtained by using the recycled resin can still maintain satisfactory heat resistance.
[0016]
The base resin of the foam layer of the automobile interior material used for recycling is preferably a modified polyphenylene ether-based resin. Further, the base resin of the foam layer of the foam laminated sheet manufactured using the recycled resin is also a modified polyphenylene. It is preferably an ether-based resin.
[0017]
The resin component obtained by substantially separating and removing the noise preventing material and the skin material from the waste material or the scrap material of the automobile interior material is regenerated into a pellet by extrusion molding. The regeneration is preferably carried out by substantially separating the noise-preventing material and the skin material from the waste material or offcuts of the automobile interior material, and removing the resin component from which the polyester fiber component has been removed to 3% by weight or less. It is performed by extruding using a screw extruder or extruding at a temperature of 270 ° C. or more using a single screw extruder. When a recycled resin containing a small amount of fiber component in the resin is used for the non-foamed layer, the fiber component having a fiber length of 1 mm or more becomes a nucleus to generate fish eyes, etc., resulting in poor appearance and non-foamed layer. May be heterogeneous, but may be extruded using a twin-screw extruder, or extruded using a single-screw extruder at a temperature higher than the melting temperature of the polyester fiber (270 ° C or higher). By doing so, the polyester fibers in the regenerated resin are melted and refined, the fiber length of the fiber component becomes 1 mm or less, and generation of fish eyes and the like can be suppressed. It is preferable that the fiber component content of the non-foamed layer containing the recycled resin is 0.1 to 3% by weight, and the fiber length of the fiber component is 1 mm or less.
[0018]
Polyolefin-based resins such as hot melt adhesive layers contained in offcuts and waste materials of automobile interior materials and skin layers such as olefin-based thermoplastic elastomer skin (TPO skin) and polyethylene-based foam cushioning layers during resin regeneration In addition, it is desirable to minimize mixing of recycled materials such as polyolefin resin which may be mixed in from other automobile members when scraps or waste materials of the vehicle interior material are collected. It is known that the compatibility of a modified PPE resin, a heat-resistant PS resin, and a PS resin and a polyolefin resin, which are base resins of a foamed layer and a non-foamed layer in an automobile interior material, is poor. If the resin is regenerated with a large amount contained, phase separation occurs and the resulting resin becomes brittle and inferior in impact resistance, and may not be suitable as a material for automotive interior materials. Preferably, the content of the polyolefin-based resin contained in the regenerated resin is suppressed to 10% by weight or less. However, it is not easy to completely remove the polyolefin-based resin contained in the offcuts and waste materials of automobile interior materials.
[0019]
Therefore, the present inventors further conducted various studies on the addition of a modified PPE-based resin, a heat-resistant PS-based resin, and a compatibilizer expected to have an effect of improving the compatibility between the PS-based resin and the polyolefin-based resin. It has been found that by adding a small amount of a thermoplastic elastomer, particularly a styrene-based thermoplastic elastomer (for example, a styrene-butadiene-based thermoplastic elastomer), to a regenerated resin, the impact resistance of the obtained regenerated resin is significantly improved. Since the regenerated resin contains a high heat-resistant resin derived from the foamed layer, even if the heat resistance is reduced by the addition of the thermoplastic elastomer, the non-foamed layer formed of the regenerated resin is used for the automobile interior used for the regeneration. The same heat resistance as the non-foamed layer of the material can be maintained.
[0020]
If the foam laminate sheet and the covering material such as skin material and noise control material are bonded by hot-melt adhesive, they can be easily separated by immersing the offcuts or waste material of the car interior material in an organic solvent. can do. However, when the covering material is laminated on the foam laminated sheet without using an adhesive, such a wet method cannot be applied. Then, the present inventors have further studied and found that in the case of a foamed laminated sheet composed of a foamed layer and a non-foamed layer laminated on both surfaces thereof, when an impact force is applied to the automobile interior material, the impact force is reduced to the non-foamed layer ( To concentrate on the skin layer), it has been found that the peeling of the skin material and the pulverization of the foam laminate can be efficiently performed by impact pulverization. Therefore, by crushing offcuts or waste materials of automobile interior materials and separating the crushed material by a sieve and / or specific gravity separation, the skin material and the noise prevention material can be substantially separated from the offcuts or waste materials of automobile interior materials. Can be separated and removed.
[0021]
The present invention has been completed based on the above findings. That is, the present invention
1) A foamed laminated sheet comprising a foamed layer having a modified polyphenylene ether-based resin as a base resin and a non-foamed layer laminated on both sides thereof, wherein at least one of the non-foamed layers comprises a modified polyphenylene ether-based resin Foamed laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foamed layer having a base resin as the base resin, a skin material laminated on one surface thereof, and an abnormal noise preventive material appropriately laminated on the other surface A recycled resin obtained by substantially separating and removing a skin material and an abnormal noise preventive material from scraps or waste materials of automobile interior materials composed of a polyolefin resin and a styrene-based heat. A foamed laminated sheet for automotive interior materials, characterized by containing a plastic resin elastomer,
2) The foam laminated sheet for automobile interior materials according to 1), wherein the content of the recycled resin contained in the constituent resin of the non-foamed layer is 50% by weight or more.
3) The foamed laminated sheet for automotive interior materials according to 1) or 2), wherein the recycled resin contains 0.1 to 10% by weight of a polyolefin resin.
4) The foamed laminated sheet for automobile interior materials according to any one of 1) to 3), wherein the content of the styrene-based thermoplastic elastomer contained in the recycled resin is 1 to 20% by weight.
5) The foamed laminated sheet for an automotive interior material according to any one of 1) to 4), wherein the styrene-based thermoplastic elastomer contained in the recycled resin is a styrene-butadiene-based thermoplastic elastomer (SBS).
6) A foamed laminated sheet comprising a foamed layer having a modified polyphenylene ether-based resin as a base resin and a non-foamed layer laminated on both surfaces thereof, wherein at least one of the non-foamed layers comprises a modified polyphenylene ether-based resin Foamed laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foamed layer having a base resin as the base resin, a skin material laminated on one surface thereof, and an abnormal noise preventive material appropriately laminated on the other surface A recycled resin obtained by regenerating after substantially separating and removing the skin material and the noise preventing material from the offcuts or waste material of the automobile interior material comprising the recycled resin, wherein the non-foamed layer containing the recycled resin is based on the layer. A foamed laminated sheet for an automobile interior material, comprising 0.1 to 3% by weight of a polyester fiber and having a fiber length of 1 mm or less.
7) The vehicle according to any one of 1) to 6), wherein the Vicat softening temperature of the base resin constituting the foamed layer is higher than the Vicat softening temperature of the base resin constituting the non-foamed layer laminated on both surfaces thereof. Foam laminated sheet for interior material,
8) The foamed laminated sheet for automobile interior materials according to any one of 1) to 7), wherein the modified polyphenylene ether-based resin of the foamed layer comprises 35 to 75% by weight of a phenylene ether component and 65 to 25% by weight of a styrene-based component. ,
9) A foamed laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foamed layer using a modified polyphenylene ether-based resin as a base resin, a skin material laminated on one surface thereof, and an appropriate material on the other surface A method for reusing an automobile interior material comprising a laminated noise-preventing material, wherein in the production of a foamed laminated sheet having the same structure as described above, a skin material and a noise-prevention material are obtained from scraps or waste material of the automobile interior material. A method for recycling automobile interior materials, comprising forming at least one non-foamed layer of a foamed laminated sheet from a resin containing a regenerated resin obtained by regenerating after substantially separating and removing the resin.
10) The method for reusing an automobile interior material according to 9), wherein the content of the recycled resin contained in the constituent resin of the non-foamed layer is 50% by weight or more.
11) After pulverizing offcuts or waste materials of automobile interior materials, sieve and / or specific gravity separation substantially separates and removes a skin material and a noise prevention material from offcut materials or waste materials of automobile interior materials. ) Method for reusing automotive interior materials
12) The method according to the above item 9) or 10), wherein the scrap material or the waste material of the automobile interior material is impregnated in an organic solvent, and the skin material and the noise preventing material are substantially separated and removed from the scrap material or the waste material of the automobile interior material. How to reuse automotive interior materials,
13) An organic solvent used for substantially separating and removing a skin material and an abnormal noise prevention material contained in offcuts or waste materials of automobile interior materials is alcohols 9), 10) or 12) A method for reusing automobile interior materials according to the item,
14) The organic solvent used for substantially separating and removing the skin material and the noise preventing material contained in the offcuts or waste material of the automobile interior material is an aliphatic hydrocarbon 9), 10) or 12) the method for reusing automobile interior materials according to the above,
15) The automobile interior according to any one of 9) to 14), wherein the recycled resin is a resin that is recycled by extruding a foamed laminated sheet portion recovered from scraps or waste materials at a temperature of 270 ° C. or more. How to reuse materials,
16) The method for reusing an automotive interior material according to any one of 9) to 15), wherein the recycled resin contains 0.1 to 10% by weight of a polyolefin resin.
17) The method for reusing an automobile interior material according to any one of 9) to 16), wherein the recycled resin contains 1 to 20% by weight of a styrene-based thermoplastic elastomer based on the total amount.
18) The method for reusing an automotive interior material according to any one of 9) to 17), wherein the styrene-based thermoplastic elastomer contained in the recycled resin is a styrene-butadiene-based thermoplastic elastomer (SBS).
19) The automobile according to any one of 9) to 18), wherein the Vicat softening temperature of the base resin constituting the foamed layer is higher than the Vicat softening temperature of the base resin constituting the non-foamed layer laminated on both surfaces thereof. How to reuse interior materials,
20) The method for reusing an automobile interior material according to any one of 9) to 19), wherein the thermoplastic resin constituting the non-foamed layer is a modified polyphenylene ether-based resin.
21) The method for reusing an automobile interior material according to any one of 9) to 20), wherein the thermoplastic resin constituting the non-foamed layer is made of a polystyrene resin having improved heat resistance.
22) The method for reusing an automotive interior material according to any one of 9) to 21), wherein the modified polyphenylene ether-based resin of the foamed layer comprises 35 to 75% by weight of a phenylene ether component and 65 to 25% by weight of a styrene-based component. , Concerning.
[0022]
According to the method of the present invention, a foamed laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foamed layer having a modified polyphenylene ether-based resin as a base resin, and a skin material laminated on one surface thereof The resin component recovered from the scraps or waste materials of the automobile interior material composed of the noise preventing material appropriately laminated on the other surface can be repeatedly used in the production of the automobile interior material.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a foamed laminated sheet for an automobile interior material using a recycled resin (recycled resin) and a method for producing an automobile interior material.
[0024]
First, an automobile interior material used for recycling will be described in detail with reference to the drawings.
[0025]
As shown in FIG. 1, an automobile interior material used for recycling includes a non-foamed layer (chamber) having a thermoplastic resin as a base resin on both sides of a foamed layer (1) having a modified polyphenylene ether-based resin as a base resin. An inner non-foamed layer (3) and an outdoor non-foamed layer (5) are formed, and a non-woven fabric layer for a skin material is formed on the surface of the indoor non-foamed layer (3) via an adhesive layer (7). 9) is laminated, and a nonwoven fabric layer (11) for preventing abnormal noise is laminated on the surface of the outdoor non-foamed layer (5) by an anchor effect without substantially interposing an adhesive layer.
[0026]
As another mode of the automobile interior material used for recycling, as shown in FIG. 2, a thermoplastic resin is used as a base resin on both sides of a foam layer (1) using a heat-resistant resin as a base resin. A non-foamed layer (an indoor non-foamed layer (3) and an outdoor non-foamed layer (5)) is formed, and a skin material is provided on the surface of the indoor non-foamed layer (3) via an adhesive layer (7). And a nonwoven fabric layer (11) for preventing noise is laminated on the surface of the outdoor non-foamed layer (5) via an adhesive layer (7).
[0027]
The present invention can be applied to an automobile interior material in which a nonwoven fabric layer for preventing abnormal noise is not provided in some cases.
[0028]
The base resin constituting the foamed layer (1) may be a polystyrene or a blend of a heat-resistant polystyrene resin and polyphenylene ether (PPE), or a styrene-phenylene ether copolymer such as a styrene graft polymer on PPE. It is a polyphenylene ether-based resin (modified PPE-based resin). These resins are suitable for automobile interior materials according to the present invention because they can withstand indoor and outdoor temperature environments and have little deformation due to temperature.
[0029]
Examples of the PPE used in the modified PPE resin include poly (2,6-dimethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-4-ether), and poly (2,6 -Diethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2-methyl-6-n-propylphenylene-1,4-ether), poly (2 -Methyl-6-n-butylphenylene-1,4-ether), poly (2-methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene-1,4-ether) Ether), poly (2-ethyl-6-chlorophenylene-1,4-ether) and the like, and these are used alone or in combination of two or more.
[0030]
Among the modified PPE resins, a polystyrene resin forming a mixed resin with the PPE resin is styrene or a derivative thereof, for example, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethyl. It is a resin containing styrene or the like as a main component (60% by weight or more, preferably 70% by weight or more). Therefore, the polystyrene-based resin is not limited to a homopolymer composed only of styrene or a styrene derivative, and may be a copolymer produced by copolymerizing with another monomer. Other monomers copolymerizable with styrene or its derivatives include, for example, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or maleic anhydride, itaconic acid, Examples include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, and these may be used alone or in combination of two or more. Specific examples of the PS resin mixed with the PPE resin include, for example, polystyrene, styrene-α-methylstyrene copolymer, high-impact polystyrene (styrene-butadiene copolymer, styrene-acrylonitrile-butadiene copolymer) And copolymers of styrene and a carboxyl group-containing monomer, such as styrene-maleic anhydride copolymer and styrene-itaconic acid copolymer.
[0031]
Specific examples of the styrene monomer to be copolymerized with, preferably graft-polymerized with, phenylene ether or PPE resin include, for example, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-Methylstyrene, ethylstyrene and the like. These can be used alone or in combination of two or more. Of these, styrene is preferred in terms of versatility and cost.
[0032]
The modified PPE resin used as the base resin of the foamed layer is preferably 35 to 75% by weight of a phenylene ether component, 65 to 25% by weight of a styrene component, more preferably 35 to 60% by weight of a phenylene ether component, and styrene. Component 65 to 40% by weight, particularly preferably 38 to 58% by weight of phenylene ether component and 62 to 42% by weight of styrene component. If the mixing ratio of the PPE-based resin is small, the heat resistance tends to be inferior. If the mixing ratio of the PPE-based resin is large, the viscosity during heating and flowing tends to increase, and foam molding tends to be difficult.
[0033]
The primary foamed layer forming the foamed layer (1) has a layer thickness of 1 to 5 mm, further 1.5 to 3.5 mm, a foaming ratio of 3 to 20 times, further 5 to 15 times, and a cell diameter. Is 0. 05 to 0. It is preferably 9 mm, more preferably 0.1 to 0.7 mm, and the closed cell ratio is 70% or more, and further preferably 80% or more. When the thickness of the primary foamed layer is less than 1 mm, the strength and the heat insulating property are poor, and it may not be suitable as a foamed laminated sheet for automotive interior materials. On the other hand, if it exceeds 5 mm, heat is difficult to be transmitted to the center in the thickness direction of the foamed layer (1) at the time of molding heating, so that sufficient heating cannot be performed and moldability may be deteriorated. In addition, if the heating time is increased to perform sufficient heating, cells on the surface of the foamed layer may be broken, which may make it difficult to obtain an acceptable product. When the primary expansion ratio is less than 3 times, flexibility is poor, breakage due to bending or the like is likely to occur, and the effect of weight reduction is small. If the primary expansion ratio exceeds 20 times, the strength tends to decrease, and the moldability tends to decrease due to difficulty in heating to the center. Further, when the cell diameter is 0.05 mm or less, it is difficult to obtain sufficient strength, and when the cell diameter is 0.9 mm or more, the heat insulating property tends to be poor. When the closed cell ratio is 70% or less, heat insulation and rigidity are poor, and it is difficult to obtain a desired secondary expansion ratio by molding and heating, and the moldability tends to be poor.
[0034]
The amount of the remaining volatile components in the primary foam layer forming the foam layer (1) is preferably 1 to 5% by weight, more preferably 2 to 4% by weight based on the total weight of the foam layer. If the residual volatile component is less than 1% by weight, the secondary expansion ratio becomes too low, and good molding may not be achieved. On the other hand, when the residual volatile component exceeds 5% by weight, an air pocket may be generated between the non-foamed layer and the dimensional stability over time. The amount of the remaining volatile component may be measured by gas chromatography, but usually, the foamed layer sample is heated in a temperature range not lower than the temperature at which the modified PPE-based resin starts to soften and lower than the decomposition temperature to remove the volatile component. It is volatilized sufficiently and measured by the weight difference before and after heating.
[0035]
The base resin of the foamed layer (1) used in the present invention may contain a cell nucleus modifier, an impact resistance improver, a lubricant, an antioxidant, an antistatic agent, a pigment, a stabilizer, an odor, if necessary. You may add a reducing agent etc.
[0036]
Non-foamed layers (3) and (5) are laminated on both sides of the foamed layer (1) of the present invention, which are used to control deformation when the temperature in the vehicle interior changes and to stabilize the shape of the molded body during molding. This is because the movement of the foamed layer needs to be controlled by the non-foamed layer inside and outside the room for the purpose of achieving the above.
[0037]
The base resin of the non-foamed layers (3) and (5) preferably has a lower softening temperature than the base resin of the foamed layer (1). Furthermore, it is preferable that the Vicat softening temperature is lower than the base resin of the foamed layer (1) by 10 ° C. or more. This is because when the softening temperature of the base resin of the non-foamed layers (3) and (5) is higher than or equal to the softening temperature of the base resin of the foamed layer (1), the non-foamed layers (3) and (5) If the base resin is heated to a high temperature until the base resin melts and softens and penetrates into the nonwoven fabric layer, the problem that the cells forming the foamed layer (1) are broken may occur.
[0038]
As the thermoplastic resin used for the non-foamed layers (3) and (5), a modified PPE-based resin and a heat-resistant PS-based resin are preferable from the viewpoint of adhesion to the foamed layer (1) made of the modified PPE-based resin. These are used alone or in combination of two or more.
[0039]
For the non-foamed layer (3), a modified PPE resin is particularly preferably used. The modified PPE-based resin is obtained by modifying the PPE-based resin by polymerization or mixing with a monomer mainly composed of a styrene-based compound or a polymer thereof as in the case of the foamed layer (1) described above. For example, a mixed resin of a PPE-based resin and a PS-based resin, a PPE-styrene copolymer obtained by polymerizing a styrene-based monomer on a PPE-based resin, and a mixture of the copolymer and a PS-based resin or a PPE-based resin And a mixture of the copolymer, a PPE-based resin, and a PS-based resin. Among these, a mixed resin of a PPE-based resin and a PS-based resin is preferred from the viewpoint of easy production.
[0040]
Specific examples and preferred examples of these PPE-based resins, PS-based resins and styrene-based monomers, specific examples of monomers polymerizable with PS-based resins and styrene monomers, reasons for using them, and the like, This is the same as the case described for the foam layer (1). However, as a preferred specific example of the PS resin, a rubber-modified polystyrene resin represented by HIPS is added because the non-foamed layers (3) and (5) have a large effect of improving the impact resistance.
[0041]
When a modified PPE resin is used as the base resin used for the non-foamed layer (3) on the indoor side, a resin having a Vicat softening temperature equal to or higher than the heat resistance evaluation temperature in consideration of the temperature rise in the automobile interior is preferable. The reason for this is that if the indoor-side non-foamed layer (3) softens at the heat-resistant evaluation temperature, it cannot function to control the cell movement of the foamed layer (1).
[0042]
When a polystyrene-based resin (heat-resistant PS-based resin) having improved heat resistance is used as the base resin of the outdoor non-foamed layer (5), the heat resistance is the same as that of the indoor non-foamed layer (3). Those having a Vicat softening temperature equal to or higher than the evaluation temperature and having a Vicat softening temperature lower by 10 ° C. or more than the base resin of the foamed layer are preferable.
[0043]
The heat-resistant PS-based resin used as the base resin of the non-foamed layer (5) is a copolymer of styrene or a derivative thereof and another monomer, and has an improved heat resistance capable of polymerizing with styrene or a derivative thereof. Examples of the monomer having an effect include, for example, maleic acid, fumaric acid, acrylic acid, methacrylic acid, unsaturated carboxylic acids such as itaconic acid or derivatives thereof and acid anhydrides thereof, acrylonitrile, nitrile compounds such as methacrylonitrile or And derivatives thereof. These may be used alone or in combination of two or more. The monomer copolymerizable with styrene or a derivative thereof having an effect of improving heat resistance is used in an amount of usually 40% by weight or less, preferably 30% by weight or less.
[0044]
In addition, when polymerizing styrene or a styrene derivative, the heat-resistant PS-based resin is obtained by adding a synthetic rubber or rubber latex and polymerizing the same with maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, or the like. It may be a copolymer with a saturated carboxylic acid or a derivative thereof and an acid anhydride thereof, or a nitrile compound such as acrylonitrile or methacrylonitrile.
[0045]
Among these, a styrene-maleic anhydride copolymer, a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, and an acrylonitrile-butadiene-styrene copolymer have the heat resistance improving effect, It is preferable from the viewpoint of performance and cost.
[0046]
The heat-resistant PS resin may be used alone or in combination of two or more. The heat-resistant PS-based resin may be used by blending with another thermoplastic resin. Examples of the blended thermoplastic resin include polystyrene, HIPS, and polycarbonate. Among these, HIPS is preferred from the viewpoints of versatility, uniform dispersion, high effect of improving the impact resistance of the non-foamed layer, cost, and the like. Known HIPS can be used, and the content of the rubber component is usually 1 to 15% by weight.
[0047]
Next, in the automobile interior material used for recycling, the thickness of the non-foamed layers (3) and (5) laminated on the foamed layer (1) is preferably 50 to 300 μm, more preferably 75 to 200 μm. When the thickness of the non-foamed layers (3) and (5) is less than 50 μm, the strength, rigidity, heat resistance and the like are inferior. When the thickness is more than 300 μm, the moldability of the laminated sheet tends to be inferior.
[0048]
When forming the non-foamed layers (3) and (5), if necessary, an impact resistance improving agent, a filler, a lubricant, an antioxidant, an antistatic agent, a pigment, a stabilizer, an odor reducing agent, and the like are used. You may add individually or in combination of 2 or more types.
[0049]
The impact resistance improver is prepared by laminating the non-foamed layers (3) and (5) on the foamed layer (1) and performing a secondary foaming to form a laminated sheet as an automobile interior material. This is effective for preventing cracks in the non-foamed layers (3) and (5) when transporting the molded article. Any impact modifier may be used without particular limitation as long as the effect is exhibited by mixing with the base resin. The impact modifier may be a component capable of exhibiting the impact modifying effect introduced into the thermoplastic resin by modification by polymerization. For example, a mixture containing an impact modifying component such as HIPS may be mixed. When used for a non-foamed layer, impact resistance can be imparted to the non-foamed layers (3) and (5).
[0050]
As shown in FIGS. 1 and 2, the automobile interior material used for the reproduction may have a nonwoven fabric layer (11) for preventing abnormal noise on the surface of the outdoor non-foamed layer (5). The nonwoven fabric layer (11) for preventing abnormal noise is generated when the vehicle is mounted on an automobile, when the interior of the vehicle is rapidly cooled by a cooler or the like, or when traveling on uneven road surfaces or traveling on a sharp curve. Effective for preventing abnormal noise.
[0051]
As the nonwoven fabric layer (11) for preventing abnormal noise, any kind of cloth can be used as long as the raw fibers are bonded with an adhesive, a molten fiber, or a mechanical method. The type of the raw material fiber is not particularly limited, and any of synthetic fibers, semi-synthetic fibers, and natural fibers can be used. Specifically, synthetic fibers such as polyester, polypropylene, polyamide (nylon), and polyacrylonitrile, and natural fibers such as wool, cotton, and cellulose can be used. Among them, polyester fibers are preferable, and heat resistance is particularly high. Polyethylene terephthalate fibers are preferred.
[0052]
These fibers can be used alone or in combination of two or more. Depending on the method of manufacturing and processing the non-woven fabric, a bonding binder bonding cloth, a needle punch cloth, a spun-pound cloth, a spray fiber cloth, a stitch bond cloth, or the like can be used, and any of the non-woven cloths can be used.
[0053]
The nonwoven fabric layer (11) for preventing abnormal noise is 10 to 50 g / m2 in consideration of quality and cost. ² And preferably 20 to 40 g / m2. ² Preferably. 10g / m ² In the following basis weight, the surface of the outdoor non-foamed layer (5) may be partially exposed at the portion where the non-woven fabric layer (11) for preventing abnormal noise is provided, and an effective noise preventing effect may not be exhibited. On the other hand, 50 g / m ² With the above basis weight, heat distortion may occur in the interior material or the cost may increase unnecessarily due to molding distortion of the nonwoven fabric layer (11) for preventing abnormal noise.
[0054]
Examples of the method of providing the nonwoven fabric layer (11) for preventing abnormal noise on the base material for automobile interior materials include a method of laminating the nonwoven fabric layer (5) through the adhesive layer (7) on the outdoor non-foamed layer. The base resin of (5) is melted, and the melted base resin of the outdoor non-foamed layer (5) is pressure-bonded with the foamed layer (1) and the nonwoven fabric layer (11) for noise prevention, and substantially adhered. A method of laminating without using an agent layer is preferable, and a method of laminating substantially without using an adhesive layer is particularly preferable. The reason is that the base resin of the outdoor non-foamed layer (5) permeates moderately into the nonwoven fabric layer (11) for preventing abnormal noise, and good adhesiveness is obtained by an anchor effect. Long-term use, stable adhesiveness without falling off even in use in harsh environments can be obtained, and the core layer, non-foamed layer, and non-woven fabric layer are laminated at the same time in one process, which makes the work complicated. And that it is possible to suppress an increase in manufacturing cost because an adhesive layer is not substantially used.
[0055]
Furthermore, the adhesive surface of the foam layer (1) with the outdoor non-foam layer (5) is not easily damaged by the base resin of the molten outdoor non-foam layer (5). ) And the nonwoven fabric layer (11) for preventing abnormal noise are obtained, so that the melted base resin of the non-foamed outside layer (5) is removed by the nonwoven fabric layer (11) for preventing abnormal noise. After the contact, the foamed layer (1) is brought into contact with the melted base resin of the outdoor non-foamed layer (5) from the opposite surface of the nonwoven fabric layer (11) for noise prevention, and then pressure-bonded and integrated. preferable.
[0056]
As shown in FIGS. 1 and 2, a car interior material used for recycling has a nonwoven fabric layer (9) for a skin material laminated on the surface of an indoor non-foamed layer (3) via an adhesive layer (7). Have been.
[0057]
As the non-woven fabric layer (9) for the skin material, any type of fabric can be used as long as the raw fibers are bonded with an adhesive, a molten fiber, or a mechanical method. The type of the raw material fiber is not particularly limited, and any of synthetic fibers, semi-synthetic fibers, and natural fibers can be used. Specifically, synthetic fibers such as polyester, polypropylene, polyamide (nylon), and polyacrylonitrile, and natural fibers such as wool, cotton, and cellulose can be used. Among them, polyester fibers are preferable, and heat resistance is particularly high. Polyethylene terephthalate fibers are preferred.
[0058]
Although a woven fabric of the above fibers can be used as the skin material, a nonwoven fabric is preferred from the viewpoint of moldability. Examples of the type of nonwoven fabric include a bonding binder adhesive fabric, a needle punch fabric, a spun pond fabric, a spray fiber fabric, a stitch bond fabric, and the like, depending on the manufacturing process, and any of the nonwoven fabrics can be used.
[0059]
As a method of bonding the nonwoven fabric layer (9) for the skin material to the automobile interior material, a method of bonding the skin material to which the adhesive layer (7) has been previously bonded to the base material for the automobile interior material by using a heat roll, A method in which a skin material is temporarily fixed to a base material for an automobile interior material to which an adhesive layer (7) has been previously bonded, and molding and bonding are simultaneously performed during heat molding. A) a method of fusing the base resin of the room-side non-foamed layer (3) between the foamed layer (1) and the nonwoven fabric layer (9) for the skin material, and pressing the melted base resin. The base resin of the indoor non-foamed layer (12) is melted during the production of the base material for automobile interior materials, and the melted base resin of the indoor non-foamed layer (3) is combined with the foamed layer (1) and the skin material. The method of sandwiching and press-fitting between nonwoven fabric layers (9) for use is advantageous in terms of cost since an adhesive layer is not substantially used, and is more preferable.
[0060]
Next, considering the quality and cost, the nonwoven fabric layer (9) for the skin material is 100 to 300 g / m2. ² It is preferable to have a basis weight of 140 to 200 g / m ² It is preferable to have a basis weight of 100g / m ² With the following basis weight, a sufficient feeling as an interior material may not be obtained. On the other hand, 300 g / m ² In the above basis weight, the molding distortion of the skin material may affect the thermal deformation.
[0061]
The adhesive layer (7) has a function of bonding the indoor non-foamed layer (3) and the nonwoven fabric layer (9) for the skin material by at least a chemical bond such as an intermolecular force, a hydrogen bond, and a covalent bond. Things are used.
[0062]
Specific examples of the adhesive layer (7) include thermoplastic adhesives such as vinyl acetate, cellulose, acrylic, polyamide, and polyvinyl acetate, urethane, melamine, phenol, epoxy, polyester, and the like. Thermosetting adhesives such as acrylics, rubber adhesives such as chloroprene rubber, nitrile rubber, silicone rubber, natural adhesives such as starch, protein, and natural rubber, and hot melt adhesives . Among these, a hot melt adhesive (hot melt film) is preferable in practical characteristics.
[0063]
Specific examples of the hot melt adhesive include polyolefin, modified polyolefin, polyurethane, ethylene-vinyl acetate copolymer resin, polyamide, polyester, thermoplastic rubber, styrene-butadiene copolymer, and styrene-isoprene. Those containing a resin such as a copolymer system as a component are exemplified. Among these, a modified polyolefin-based hot melt adhesive and an ethylene-vinyl acetate copolymer-based hot melt adhesive are particularly preferred from the viewpoints of heat resistance, adhesiveness, cost, and the like. The ethylene-vinyl acetate copolymer resin-based hot melt adhesive is soluble in aliphatic hydrocarbons such as n-hexane and hexane when the ethylene component is large, and in alcohols such as methanol and ethanol when the vinyl acetate component is large. It has the property of being.
[0064]
The hot melt adhesive (hot melt film) may contain a tackifier resin for the purpose of improving tackiness and wettability. Examples of the tackifier resin include rosin resin and rosin derivative resin, terpene resin and modified terpene resin, aliphatic petroleum resin, aromatic petroleum resin, and alicyclic hydrogenated petroleum resin. Of these, rosin resins, rosin derivative resins, and alicyclic hydrogenated petroleum resins are preferable because of their excellent adhesiveness and compatibility with the base polymer. The rosin resin and the rosin derivative resin are soluble in alcohols and terpene oils, and the alicyclic hydrogenated petroleum resin is soluble in aliphatic hydrocarbons.
[0065]
Next, an example of an automotive interior material foamed laminated sheet using a recycled resin (recycled resin) will be described in detail with reference to the drawings.
[0066]
FIG. 3 shows a configuration of a foam laminated sheet for an automobile interior material using a recycled resin (recycled resin) according to one embodiment of the present invention, and a foamed layer (10) using a heat-resistant resin as a base resin. Non-foamed layers (indoor-side non-foamed layer (12) and outdoor-side non-foamed layer (14)) containing resin (recycled resin) recycled from scrap materials or waste materials of automobile interior materials in constituent resin on both surfaces of The nonwoven fabric layer (18) for the skin material is laminated on the surface of the non-foamed layer (12) on the indoor side via the adhesive layer (16), and is substantially formed on the surface of the non-foamed layer (14) on the outdoor side. A nonwoven fabric layer (20) for preventing abnormal noise is laminated by an anchor effect without interposing an adhesive layer.
[0067]
FIG. 4 shows a configuration of a foam laminated sheet for an automobile interior material using a recycled resin (recycled resin) according to another embodiment of the present invention, wherein a foamed layer (a heat-resistant resin as a base resin) is used. 10) Non-foamed layers (indoor-side non-foamed layer (12) and outdoor-side non-foamed layer (14)) containing resin (recycled resin) recycled from scraps or waste materials of automobile interior materials in the constituent resin on both surfaces of ), A nonwoven fabric layer (18) for a skin material is laminated on the surface of the indoor-side non-foaming layer (12) via an adhesive layer (16), and the surface of the outdoor-side non-foaming layer (14) A nonwoven fabric layer (20) for noise prevention is laminated via an adhesive layer (16).
[0068]
In the present invention, when a recycled resin is used for the non-foamed layers (12) and (14), it can be used for both or one of the non-foamed layers. When only one of the recycled resins is used, it is preferably used for the outdoor non-foamed layer (14).
[0069]
In the present invention, a foamed laminated sheet for an automobile interior material using a recycled resin as a non-foamed layer as described above is referred to as a foamed laminated sheet for an automobile interior material using a recycled resin.
[0070]
The detailed description of the foam layer (10), the adhesive layer (16), the non-woven fabric layer (18) for the skin material, and the non-woven fabric layer (20) for preventing abnormal noise will be described in detail in the automobile interior materials used for the regeneration. These are the same as those described in the sections of the foam layer (1), the adhesive layer (7), the nonwoven fabric layer (9) for the skin material, and the nonwoven fabric layer (11) for preventing abnormal noise.
[0071]
As shown in FIGS. 3 and 4, the foamed laminated sheet for automobile interior material using recycled resin has non-foamed layers (12) and (14) laminated on both sides of a foamed layer (10).
[0072]
The resin constituting at least one of the non-foamed layers (12) and (14) includes a recycled resin recycled from offcuts or waste materials of automobile interior materials. The content of the recycled resin in the resin constituting the non-foamed layer is preferably 50 to 100% by weight.
[0073]
As the thermoplastic resin additionally used as the recycled resin used as the constituent resin of the non-foamed layers (12) and (14), HIPS resin, heat-resistant PS resin, modified PPE resin, and other thermoplastic resins are used. And these may be used alone or in combination of two or more. Among these, modified PPE-based resins, heat-resistant PS-based resins, and HIPS-based resins are preferably used from the viewpoint of ease of recycling.
[0074]
The base resin of the non-foamed layers (12) and (14) preferably has a lower softening temperature than the base resin of the foamed layer (10). Furthermore, it is preferable that the Vicat softening temperature is lower by 10 ° C. or more than the base resin of the foamed layer (10). This is because if the softening temperature of the base resin of the non-foamed layers (12) and (14) is higher than or equal to the softening temperature of the base resin of the foamed layer (10), the non-foamed layers (12) and ( If the base resin is heated to a high temperature until the base resin melts and softens and penetrates into the nonwoven fabric layer, the problem that the cells forming the foamed layer (10) may be broken may occur. Therefore, in order to adjust the Vicat softening temperature of the base resin of the non-foamed layers (12) and (14), it is preferable to mix an appropriate amount of the thermoplastic resin with the regenerated resin.
[0075]
The rigidity of the indoor non-foamed layer (12) is preferably equal to or higher than the rigidity of the outdoor non-foamed layer (14). This is because the outdoor-side non-foamed layer (12) has a function of suppressing the movement of the cells of the laminated foamed layer (10) and the movement of the abnormal noise prevention material (20), while The foam layer (12) has a function of suppressing the cell movement of the laminated foam layer (10), and at the same time, suppressing the movement of the skin material (18) which is more rigid than the abnormal noise preventing material (20). It depends. For this reason, in order to adjust the rigidity of the non-foamed layers (12) and (14), it is preferable to mix an appropriate amount of the thermoplastic resin with the recycled resin.
[0076]
Further, it is preferable that the impact resistance of the outdoor non-foamed layer (14) is equal to or higher than the impact resistance of the indoor non-foamed layer (12). This is because the skin material (18) laminated on the indoor-side non-foamed layer (12) acts as a cushion material and can be expected to reduce external impact, whereas the outdoor-side non-foamed layer (12) This is because the noise preventing material (20) laminated on 14) cannot be expected to function as a cushioning material due to its small thickness. For this reason, in order to adjust the impact resistance of the non-foamed layers (12) and (14), it is preferable to mix an appropriate amount of the thermoplastic resin with the recycled resin.
[0077]
Further, when forming the non-foamed layers (12) and (14), a filler, a lubricant, an antioxidant, an antistatic agent, a pigment, a stabilizer, an odor reducing agent, etc. may be added to the base resin as required. May be added alone or in combination of two or more.
[0078]
In the automotive interior material of the present invention obtained using a recycled resin, the thickness of the non-foamed layers (12) and (14) laminated on the foamed layer (10) is preferably 50 to 300 μm, more preferably 75 to 200 μm. . When the thickness of the non-foamed layers (12) and (14) is less than 50 μm, the strength, rigidity, heat resistance and the like are inferior. When the thickness is more than 300 μm, the moldability of the laminated sheet tends to be inferior.
[0079]
At least one of the non-foamed layers (12) and (14) contains, as a base resin, a recycled resin recycled from scraps or waste materials of automobile interior materials used for the above-mentioned recycling.
[0080]
Here, the offcuts or waste material of the automobile interior material used for the regeneration refers to all the offcut material and waste material generated in each process related to the production of the automobile interior material, and specific examples thereof include a foam sheet. Edge cut when adjusting the product width in the manufacturing process, edge cut when adjusting the product width or product length in the foam laminated sheet manufacturing process, cut when trimming and punching in the molding process Edge or waste material, defective products generated in each process, and the like. In addition, the offcuts and waste materials generated when manufacturing the automobile interior materials include the offcut materials and waste materials generated when manufacturing the automobile interior materials using the recycled resin.
[0081]
Recycled resin is used for manufacturing automotive interior materials and hot melt adhesive layers, skin layers (TPO skin, polyethylene foam cushioning layers) contained in offcuts and waste materials generated during the production of automotive interior materials, and automotive interior materials The content of the polyolefin-based resin derived from the polyolefin-based resin base material and the like that may be mixed in during the collection of the offcuts or waste materials generated during the process is suppressed to 10% by weight or less, and It is preferable that a thermoplastic elastomer, particularly a styrene-based thermoplastic elastomer, is blended therein.
[0082]
When the content of the polyolefin resin contained in the regenerated resin is 10% by weight or more, the effect of improving the compatibility of the thermoplastic elastomer, particularly the styrene-based thermoplastic elastomer, may not be effectively exhibited. When the content of the polyolefin-based resin contained in the recycled resin is 10% by weight or more, for example, an appropriate amount of offcuts not containing the polyolefin-based resin generated in a foam sheet manufacturing process or the like is mixed with the recycled resin. Thereby, the content of the polyolefin-based resin can be adjusted to 10% or less.
[0083]
Examples of the thermoplastic elastomer blended in the recycled resin include a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a PVC-based thermoplastic elastomer, and a urethane-based thermoplastic elastomer. Among them, a styrene-based thermoplastic elastomer is preferable because of good compatibility with the styrene-based resin and the PPE-based resin.
[0084]
Examples of the styrene-based thermoplastic elastomer include, for example, SBS using polybutadiene as a soft segment, SIS using polyisoprene, SEBS using hydrogenated polybutadiene, SEPS using hydrogenated polyisoprene, Acid-modified SEBS using hydrogenated polybutadiene modified with maleic anhydride or the like can be used. Among them, styrene-butadiene-based thermoplastic elastomer (SBS) is particularly preferred from the viewpoint of cost and compatibility improving effect.
[0085]
The amount of the styrene-based thermoplastic elastomer to be blended in the recycled resin is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, based on the total of the recycled resin and the elastomer. When the amount is less than 1% by weight, the effect of improving the compatibility is not exhibited, and the improvement of the impact resistance may not be exhibited. On the other hand, if the amount is more than 20% by weight, the rigidity of the non-foamed layer is weakened, and the bending stiffness of the molded product may be deteriorated. May increase.
[0086]
Next, a method of regenerating resin from scrap materials and waste materials of automobile interior materials will be described.
[0087]
The offcuts and waste materials of the automobile interior materials are regenerated after the abnormal noise preventing material and the skin material contained in the offcuts and waste materials are substantially separated and removed.
[0088]
Here, "to substantially separate and remove the noise preventing material and the skin material" means that when the recycled resin is used as a non-foamed layer, polyester fibers derived from the skin material and the noise preventing material are brought to a level at which there is no practical problem. Means to remove the fibers. Preferably, the content of fibers such as polyester fibers in the recycled resin is suppressed to 3% by weight or less.
[0089]
Methods for substantially separating and removing the skin materials (18) and (20) include a wet separation method using an organic solvent and a dry separation method. As a separation method using a dry separation method, it is preferable to pulverize an automobile interior material, in particular, after impact pulverization, and to separate a fiber portion with a sieve, or to separate a fiber portion with a specific gravity separator after impact pulverization. In order to increase the separation accuracy, it is also possible to reduce the diameter of the screen of the impact crusher after passing through the crushed sieve after impact crushing. Similarly, after the impact pulverization, it is also possible to separate the specific gravity-separated product again by reducing the diameter of the screen of the impact pulverizer. After the impact pulverization, it is also possible to reduce the screen diameter of the impact pulverizer of the pass product of the sieve again and to separate the specific gravity after the pulverization.
[0090]
The separation method of the nonwoven fabric layer using the wet separation method is applied to an automobile interior material in which an anti-noise material is not laminated, an automobile in which an anti-noise material is laminated to a base material via a hot melt adhesive in addition to a skin material. The nonwoven fabric layer can be separated and removed by using an organic solvent which is particularly effective for the interior material and can dissolve or decompose the adhesive layer such as a hot melt adhesive.
[0091]
This is because, when an automobile interior material is immersed in an organic solvent that can dissolve or decompose the adhesive layer, the organic solvent penetrates into the nonwoven fabric layer, and the adhesive layer is dissolved or decomposed. Separate into the removed foam laminate and nonwoven layer. Since the foamed laminate from which the nonwoven fabric layer has been removed floats and the nonwoven fabric layer precipitates in the solvent, separation and recovery can be performed by utilizing the difference in buoyancy between the two. In this case, the foamed layer is preferably a closed-cell foamed layer in which the organic solvent does not penetrate into the foam even when immersed in the organic solvent for a long time. Here, the closed cell foam layer means a layer having a closed cell ratio of 70% or more. As a skin material and a noise prevention material, a high-density nonwoven fabric of polyethylene terephthalate is preferable in that separation by buoyancy can be performed efficiently.
[0092]
As the organic solvent, those having the property of dissolving or decomposing the adhesive layer (16) and not dissolving the foam laminate, the noise control material and the skin material are preferably used. Is selected according to the type. For example, when a hot-melt film containing a rosin resin or a rosin derivative resin as a tackifier resin or a hot-melt film based on an ethylene-vinyl acetate copolymer resin having a large amount of ethylene component is used as an adhesive layer, And organic solvents such as methanol, ethanol, isopropanol, butanol, isobutanol, 2-methyl-1-propanol and 2-methyl-2-propanol. ₁ ~ C ₄ Some lower aliphatic alcohols are used. When using a hot melt film having a vinyl acetate component-rich ethylene-vinyl acetate copolymer resin as a base resin as an adhesive layer, or using a hot melt film containing an alicyclic hydrogenated petroleum resin as an adhesive layer When used, pentane, isopentane, neopentane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, nonane, cyclopentane, cyclohexane, methyl- C such as cyclopentane, cycloheptane and cyclooctane ₅ ~ C ₉ Degrees of aliphatic hydrocarbons are used. As the alcohols, C, such as methanol, ethanol, propanol, and isopropanol, are used in consideration of safety, cost, boiling point, and the like. ₁ ~ C ₃ Lower aliphatic alcohols are preferable, and among them, C ₁ ~ C ₃ Particularly preferred are lower saturated aliphatic alcohols. Aliphatic hydrocarbons include C, such as pentane, isopentane, hexane, cyclopentane and cyclohexane. ₅ ~ C ₆ Of aliphatic hydrocarbons are preferred, and ₅ ~ C ₆ Particular degrees of saturated aliphatic hydrocarbons are particularly preferred. These organic solvents may be used alone or in combination of two or more. Further, the hot melt film may be used by mixing with water as long as the property of dissolving or decomposing the hot melt film is not impaired.
[0093]
Furthermore, when the resin constituting the foam laminate is a PS-based resin, when limonene manufactured from citrus is used as a solvent, the foam laminate is slightly dissolved, but is efficiently separated without adversely affecting the environment.・ Can be collected.
[0094]
As a separation method using an organic solvent, for example, a waste material of an automobile interior material is pulverized to an appropriate size by a pulverizer, and is put into a tank containing an organic solvent. By immersing in a solvent for 10 to 30 minutes, the hot melt film is dissolved or decomposed, and the nonwoven fabric layer and the foam laminate are separated. By using a closed cell foam laminate that is difficult for organic solvent to penetrate and a nonwoven fabric skin material that easily penetrates the organic solvent, the skin material precipitates and the foam laminate floats in the organic solvent due to the density. It can be easily separated and collected. The organic solvent adhering to the surface of the separated and collected foam laminate waste is removed by a dryer, dry air, or the like. By using inexpensive, low-boiling alcohols or inexpensive, low-boiling aliphatic hydrocarbons as solvents, the foamed laminate and foam material can be selectively dissolved and dissolved without dissolving the foamed laminate and skin material. After the body and the skin material are collected, the attached organic solvent can be easily removed, so that the solvent can be reused without fear of deterioration in physical properties due to the solvent.
[0095]
The recovered foamed laminate (recovered resin component) is preferably added and mixed with a predetermined amount of a thermoplastic elastomer, particularly a styrene-based thermoplastic elastomer, and then melted and kneaded using an extruder, and extruded from a die into resin pellets. Will be played as
[0096]
In the production of a recycled resin, generally known single-screw extruders and twin-screw extruders are used. Among them, a twin-screw extruder is particularly preferable. The reason for this is that the fibers contained in the recovered resin component are incompletely separated due to incomplete separation, and the fibers such as the polyester fiber derived from the skin material and the skin material remaining to a small amount are cut to a fiber length of 1 mm or less. In this case, generation of fish eyes can be suppressed.
[0097]
Extrusion conditions in the production of the recycled resin include, for example, a temperature (for example, 200 to 250 ° C.) at which fibers such as polyester fibers remaining due to incomplete separation and remaining in the resin component recovered by the pulverization method do not melt. Extrusion may be carried out by inserting a screen mesh into the die of the extruder to remove fibers having a fiber length of 1 mm or more in the resin, or at a temperature higher than the temperature at which fibers such as polyester fibers melt (polyester fibers). Extrusion at 270 ° C. or more in the case of a system fiber) may be performed to melt and refine the resin, so that the fiber having a fiber length of 1 mm or more does not exist in the regenerated resin.
[0098]
In particular, when a recycled resin is produced using a single-screw extruder, it is preferable to extrude at a temperature at which fibers such as polyester fibers dissolve or higher (270 ° C. or higher for polyester fibers). This is because, in a single-screw extruder, the effect of cutting incompletely separated fibers contained in the recovered resin component and a small amount of remaining fibers is not sufficient. This is because it is necessary to prevent a fiber having a fiber length of 1 mm or more from being present in the resin.
[0099]
Next, a method for manufacturing an automobile interior material will be described. The foamed layers (1) and (10) used in the present invention are prepared by, for example, melting and kneading a modified polyphenylene ether-based resin to which various additives have been added at 150 ° C. to 300 ° C. with an extruder. Under a high temperature and a high pressure of 3 to 30 MPa, 1 to 15 parts by weight of a foaming agent is press-fitted to 100 parts by weight of a resin, and adjusted to an optimum foaming temperature (150 to 300 ° C.). (Usually in the atmosphere), and then brought into contact with a mandrel or the like, formed into a sheet while being taken up at a speed of, for example, 0.5 to 40 m / min, cut, and wound. .
[0100]
Examples of the foaming agent used when producing the foamed layers (1) and (10) include hydrocarbon-based foaming agents such as butane, propane, and pentane. These may be used alone or in combination of two or more.
[0101]
As a method of laminating the non-foamed layers (3), (5), (12) and (14) on the foamed layers (1) and (10), the foamed layer (1) supplied and foamed in advance is supplied. The non-foamed layers (3), (5), (12) and (14) in the form of a film are brought into contact with the upper or lower surface of (10) in a molten state supplied from an extruder, laminated in layers, and pressed by a cooling roller or the like. Is preferred.
[0102]
As a method of forming an automotive interior material from the obtained foamed laminated sheet, the foamed laminated sheet is clamped and guided to the center of a heating furnace having heaters above and below, and heated to a temperature suitable for molding, for example, 120 to 200 ° C. After secondary foaming, the mold with temperature control is molded so that the surface provided with the anti-noise material is placed outside the vehicle and the surface provided with the skin material is placed inside the vehicle. Is done.
[0103]
Examples of molding methods include plug molding, free drawing molding, plug and ridge molding, ridge molding, matched molding, straight molding, drape molding, reverse draw molding, air slip molding, plug assist molding, and plug assist reverse draw. Examples of the method include molding.
[0104]
When the foamed laminated sheet is heated and subjected to secondary foaming, the foamed laminated sheet is usually foamed 1.2 to 4 times, and more preferably 1.5 to 3 times. preferable.
[0105]
In addition, the recycled resin of the present invention can be used as a raw material of an extruded product such as a resin film, a resin sheet, and a foam sheet.
[0106]
The film or sheet can be directly extruded, calendered or pressed from a separated and recovered product in which the skin material and noise control material are substantially separated and removed from the scraps or waste materials of automotive interior materials, but the quality is stable. It is preferable to extrude the reclaimed resin in the form of pellets.
[0107]
In the production of the recycled resin, a polystyrene-based resin or a modified polyphenylene ether-based resin may be added to the separated and recovered product and extruded into a pellet.
[0108]
It is also possible to produce a molded film or sheet by extruding a recycled resin pellet consisting of a separated and recovered product alone.However, in view of the physical properties of the molded product, a polystyrene-based recycled resin pellet consisting of a separated and recovered product alone is used. After blending the resin or modified polyphenylene ether-based resin, extrusion is used to produce a film or sheet, or a film or sheet is produced using pellets obtained by adding a polystyrene-based resin or modified polyphenylene ether-based resin to a separated and recovered product. preferable.
[0109]
Further, in order to make the resin composition for extrusion molding of the present invention a higher-performance one, a phenolic antioxidant, an antioxidant such as a thioether antioxidant, a phosphorus stabilizer, a heat stabilizer such as a phosphorus stabilizer, And the like are used alone or in combination of two or more. Further, if necessary, inorganic fillers, stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity imparting agents Ordinary additives such as a dispersant, a compatibilizer, and an antibacterial agent can be added to the resin composition.
[0110]
The extruded product is specifically used as an interior material of an automobile, a door panel, a door trim, a front panel, a part of an automobile ceiling material, for example, as a non-foamed layer of an automobile ceiling material, or a trunk of an automobile. Can be used for
[0111]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, “parts” indicates “parts by weight”.
[0112]
In the examples, the heat resistance evaluation temperature was set to 80 ° C., but this was selected as one criterion for evaluating the invention, and the heat resistance evaluation temperature actually applied differs depending on each automobile manufacturer. It is.
[0113]
Table 1 shows the resins used in the examples and comparative examples, and Table 2 shows the skin material, the noise preventing material, and the adhesive.
[0114]
[Table 1]

[0115]
[Table 2]

[0116]
[Type of resin]
Modified PPE: Modified polyphenylene ether
PS: polystyrene
SMAA copolymer: Styrene-methacrylic acid copolymer
HIPS: High impact polystyrene
SBS: polystyrene-polybutadiene block copolymer
SEPS: polystyrene-hydrogenated polybutadiene block copolymer
Acid-modified SEBS: polystyrene-acid-modified hydrogenated polybutadiene block copolymer
[0117]
The evaluation methods performed in the examples and comparative examples are described below.
(Thickness of foam layer and molded body)
The thickness of the primary foam sheet and the molded body at 20 locations in the width direction was measured, and the average of the measured values was calculated.
[0118]
(Expansion ratio)
The density df of the primary foam sheet was measured according to JIS K7222, and the density dp of the heat-resistant resin was measured according to JIS K7112, and was determined by the following equation.
Expansion ratio = dp / df
[0119]
(Closed cell rate)
It was evaluated and determined according to ASTM D-2859 (using a multi-pycnometer (manufactured by Beckman)).
[0120]
[Cell diameter]
The cross section of the foamed layer was observed with an optical microscope, the diameter of 20 cells was measured, and the average of the measured values was calculated.
[0121]
(Weight)
Test pieces having a size of 10 cm × 10 cm were cut out from five places in the extrusion direction of the primary foam sheet, their weights were measured, and the average value was calculated.
[0122]
(Vicat softening temperature)
It measured according to JISK7206.
[0123]
[IZOD impact value]
According to JIS K 6911, 5.21, a No. 2 test piece was used and measured with a notch.
[0124]
(Mounting heat resistance test)
An automobile ceiling member 22 (width 930 mm × length 1424 mm) as shown in FIG. 5 is mounted on an automobile ceiling (cut body), and becomes equivalent to an actual vehicle via a sun visor, a room mirror, a room lamp, a ganish, and a pillar. So fixed. In the drawing, 24 is an assist grip mounting hole, 26 is a sun visor mounting hole, 28 is a sun visor fixing mounting hole, 30 is a rearview mirror mounting hole, and 32 is an interior light mounting hole. Also, six measurement points were stamped on the front part at intervals of 120 mm symmetrically with the center line of the molded body (a to f in FIG. 5). A marking line was provided near the measurement point in the front part, and the vertical distance was measured. Next, after placing the automobile ceiling with the ceiling material in a constant temperature chamber set at 80 ± 1 ° C. for 24 hours, the absolute value of the vertical dimensional change of the measurement point stamped on the front of the molded body was measured. It was measured.
The following criterion was used as a criterion for the judgment in consideration of practicality as an interior material of an automobile.
○ ・ ・ ・ The absolute value of the deformation of the front part is within 2mm
×: Absolute value of deformation of front part is 2 mm or more
[0125]
(Falling ball impact test)
Cut out a 300mm x 300mm sample from the general part of the car ceiling material, leave it in the constant temperature layer at 0 ° C with the outdoor side facing up for 2 hours or more, and then naturally drop a 45g (22φ) iron ball from a height of 2m Then, the presence or absence of cracks in the outdoor non-foamed layer was observed.
The following criterion was used as a criterion for the judgment in consideration of practicality as an interior material of an automobile.
○ ・ ・ ・ No crack of non-foamed layer
×: Cracking of non-foamed layer
[0126]
Example 1
[Method of manufacturing automobile ceiling materials used for recycling]
A mixed resin obtained by mixing 57.1 parts of the modified PPE resin (A) and 42.9 parts of the PS resin (B) so as to be 40% by weight of the PPE resin component and 60% by weight of the PS resin component (Vicat softening). 3.4 parts of a foaming agent containing iso-butane as a main component (iso-butane / n-butane = 85/15) and 0.32 part of talc were kneaded with 100 parts of an extruder. The kneaded resin is extruded from a circular die at a resin temperature of 200 ° C., wound up on a take-up roll via a take-up roll at a speed of 8 m / min, a primary thickness of 2.4 mm, a primary expansion ratio of 12 times, and closed cells. 90%, cell diameter 0.19mm, basis weight 180g / m ² Was obtained.
[0127]
Next, while the foamed sheet is being unwound from the roll at a speed of 8 m / min, the mixed resin (Vicat softening temperature 115 ° C.) of 50 parts of the SMAA copolymer resin (C) and 50 parts of the HIPS resin (D) has a resin temperature of 50 ° C. The mixture is melted and kneaded with an extruder at 245 ° C., extruded into a film using a T-die, and further supplied with an anti-sound material (K1). After contacting the sound-preventing material (K1), a film-like non-foaming layer is laminated in a molten state by sandwiching the non-foaming layer between the foaming layer and the abnormal sound-preventing material, and heat-resistant with a thickness of 150 μm on one side (outdoor side) of the foam sheet A PS resin non-foamed layer having improved properties was formed.
[0128]
Furthermore, the sheet on which the PS resin non-foamed layer having improved heat resistance is formed is fed out from a roll at a speed of 8 m / min, so that the PPE resin component becomes 20% by weight and the PS resin component becomes 80% by weight. A mixed resin (Vicat softening temperature 125 ° C.) obtained by mixing 28.6 parts of a modified PPE resin (A) and 71.4 parts of a PS resin (B) was melted with an extruder so that the resin temperature became 265 ° C. Kneaded, extruded into a film using a T-die, formed a non-foamed layer of a modified PPE resin having a thickness of 120 μm on the other surface (inside of the room) of the foamed laminated sheet, and laminated a non-foamed layer on both sides. (I) was obtained.
[0129]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (I).
[0130]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the modified PPE-based resin non-foamed layer was placed in a mold so as to be on the inside of the vehicle, plug-molded with a mold clearance of 5.0 mm, trimmed and punched, and a good automobile ceiling material was obtained.
[0131]
[Reuse of offcuts from automobile ceiling materials]
Trimming waste generated during the molding of the automobile ceiling material was collected. The collected trimming waste was pulverized into chips having a size of 5 mm by a pulverizer, and a nonwoven fabric layer (skin material and noise preventing material) was separated and removed by a sieve and specific gravity separation. 5 parts of SBS (E) is added to the obtained crushed and separated base material, and 5 parts of a PP crosslinked foam sheet for automobile ceiling materials are added, and the mixture is melted using a twin-screw extruder heated to 270 ° C. After kneading, the mixture was passed through a 100-mesh screen attached to the tip of the extruder, and then the resin was extruded from a hole-shaped die. In addition, at the time of melting and kneading, gas components generated from the vent holes were collected. Thus, the recycled resin (a) was collected.
[0132]
Interior of an automobile except that recycled resin (a) is used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (a) and 30 parts of the HIPS resin (D) are used as the constituent resin of the outdoor non-foamed layer In the same manner as in the method for producing a foam laminated sheet for a material, a foam laminated sheet (II) for an automobile interior material was obtained.
[0133]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (II).
[0134]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0135]
A general part of the obtained automobile ceiling material was cut out, and a falling ball impact test was performed at 0 ° C. from the outdoor side. Further, the obtained automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0136]
Example 2
A recycled resin (b) was collected in the same manner as in Example 1 except that 10 parts of SBS (E) was added to the crushed and separated base material. Example 1 Except that the recycled resin (b) was used as the constituent resin of the indoor-side non-foamed layer, and 70 parts of the recycled resin (b) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor-side non-foamed layer. A foam laminated sheet (III) for an automobile interior material was obtained in the same manner as in the method for producing a foam laminated sheet for an automobile interior material of 1.
[0137]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (III). The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds.
[0138]
Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0139]
A general part of the obtained automobile ceiling material was cut out, and a falling ball impact test was performed at 0 ° C. from the outdoor side. Further, the obtained automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0140]
Example 3
A recycled resin (c) was collected in the same manner as in Example 1 except that 5 parts of SEPS (F) was added to the pulverized and separated base material.
[0141]
Example 2 Except that the recycled resin (c) was used as the constituent resin of the indoor-side non-foamed layer, and 70 parts of the recycled resin (c) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor-side non-foamed layer. A foam laminated sheet (IV) for an automobile interior material was obtained in the same manner as in the method for producing a foam laminated sheet for an automobile interior material of 1.
[0142]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (IV).
[0143]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0144]
A general part of the obtained automobile ceiling material was cut out, and a falling ball impact test was performed at 0 ° C. from the outdoor side. Further, the obtained automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0145]
Example 4
The recycled resin (d) was collected in the same manner as in Example 1 except that 5 parts of the acid-modified SEBS (G) was added to the pulverized and separated base material. Example 1 except that the recycled resin (d) was used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (d) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor non-foamed layer. A foam laminated sheet (V) for an automobile interior material was obtained in the same manner as in the method for producing a foam laminated sheet for an automobile interior material of 1.
[0146]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (V).
[0147]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0148]
A general part of the obtained automobile ceiling material was cut out, and a falling ball impact test was performed at 0 ° C. from the outdoor side. Further, the obtained automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0149]
Comparative Example 1
In the above Examples 1 to 4, a general part of the automobile ceiling material used for the production of the recycled resin was cut out, and a falling ball impact test was performed at 0 ° C from the outdoor side. Further, this automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0150]
Comparative Example 2
After adding 5 parts of PP crosslinked foam sheet for automobile ceiling material to the crushed and separated base material obtained in Example 1, using a twin-screw extruder heated to 270 ° C. and melting and kneading, the extruder tip After passing through a 100-mesh screen attached to the resin, the resin was extruded from a hole-shaped die. In addition, at the time of melting and kneading, gas components generated from the vent holes were collected. Thus, the regenerated resin (e) was collected.
[0151]
Example 1 except that the recycled resin (e) was used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (e) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor non-foamed layer. A foam laminated sheet (VI) for automobile interior materials was obtained in the same manner as in the method for producing a foam laminated sheet for automobile interior materials of 1.
[0152]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (VI).
[0153]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0154]
A general part of the obtained automobile ceiling material was cut out, and a falling ball impact test was performed at 0 ° C. from the outdoor side. Further, the obtained automobile ceiling material was mounted on a cut body, and a heat resistance test at 80 ° C. was performed. Table 4 shows the obtained results. Table 3 shows the physical properties of the constituent resins of the non-foamed layer on the indoor side and the outdoor side.
[0155]
According to Tables 3 and 4, the automobile ceiling material using the recycled resin as the constituent resin of the non-foamed layer is similar to the automobile ceiling material not using the recycled resin as the constituent resin by adding a thermoplastic elastomer as a compatibilizer. It shows that the recycled resin can be used as a constituent resin.
[0156]
[Table 3]

[0157]
[Table 4]

[0158]
Example 5
[Method of manufacturing automobile ceiling materials used for recycling]
A mixed resin obtained by mixing 57.1 parts of the modified PPE resin (A) and 42.9 parts of the PS resin (B) so as to be 40% by weight of the PPE resin component and 60% by weight of the PS resin component (Vicat softening). 3.4 parts of a foaming agent containing iso-butane as a main component (iso-butane / n-butane = 85/15) and 0.32 part of talc were kneaded with 100 parts of an extruder. The kneaded resin is extruded from a circular die at a resin temperature of 200 ° C., wound up on a take-up roll via a take-up roll at a speed of 8 m / min, a primary thickness of 2.4 mm, a primary expansion ratio of 12 times, and closed cells. 90%, cell diameter 0.19mm, basis weight 180g / m ² Was obtained.
[0159]
Next, while the foamed sheet is being unwound from the roll at a speed of 8 m / min, the mixed resin (Vicat softening temperature 115 ° C.) of 50 parts of the SMAA copolymer resin (C) and 50 parts of the HIPS resin (D) is heated to a resin temperature. The mixture is melted and kneaded with an extruder at 245 ° C., extruded into a film using a T-die, and a non-foamed layer in a film state is brought into contact with the surface of the foam sheet in a molten state. A PS resin non-foamed layer having a thickness of 150 μm and improved heat resistance was formed.
[0160]
Furthermore, the sheet on which the PS resin non-foamed layer having improved heat resistance is formed is fed out from a roll at a speed of 8 m / min, so that the PPE resin component becomes 20% by weight and the PS resin component becomes 80% by weight. A mixed resin (Vicat softening temperature 125 ° C.) obtained by mixing 28.6 parts of a modified PPE resin (A) and 71.4 parts of a PS resin (B) was melted with an extruder so that the resin temperature became 265 ° C. A film-like non-foamed layer is brought into contact with the other surface (inside of the room) of the foamed laminated sheet in a molten state after being kneaded and extruded into a film by using a T-die, and a modified PPE resin non-foamed layer having a thickness of 120 μm is formed. Was formed, and a foam laminated sheet (VII) in which a non-foamed layer was laminated on both sides was obtained.
[0161]
On the outdoor non-foamed layer of the obtained foamed laminated sheet (VII), an abnormal noise preventive material (K2) having a hot melt adhesive scattered on one surface, and an outdoor hot non-foamed adhesive having a hot melt adhesive scattered on one surface. The layers were arranged so as to be in contact with the layers, and thermocompression-bonded with a 120 ° C. heat roll.
[0162]
Further, the skin material (L) was temporarily fixed on the non-foamed layer on the indoor side of the foam laminated sheet (A) via the hot melt film (M1).
[0163]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the modified PPE-based resin non-foamed layer was placed in a mold so as to be on the inside of the vehicle, plug-molded with a mold clearance of 4.0 mm, trimmed and punched, and a good automobile ceiling material was obtained.
[0164]
The automobile ceiling material having the above configuration was pulverized into chips having a size of 5 mm by a pulverizer, and the pulverized chips were put into a tank containing ethanol. After standing for 30 minutes, it was confirmed that the skin material, the abnormal noise preventing material, and the foam laminate were completely separated. In addition, it was confirmed that the skin material and the noise preventing material precipitated, and the foam laminate was floating. The floating foam laminate was scooped up with a 10-mesh net and collected. The collected foam laminate was left in an oven at 80 ° C. for 1 hour to remove ethanol adhering to the foam laminate surface, 5 parts of SBS was added, and 5 parts of a PP crosslinked foam sheet for automobile ceiling materials were further added. The mixture was melted and kneaded using a twin-screw extruder heated to 270 ° C., and then the resin was extruded from a hole-shaped die. In addition, at the time of melting and kneading, gas components generated from the vent holes were collected. Thus, a recycled resin (f) containing no solvent was collected.
[0165]
Example 1 Except that the recycled resin (f) was used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (f) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor non-foamed layer. In the same manner as in Example 1, a foam laminated sheet (VIII) for an automobile interior material was obtained.
[0166]
The skin material (L) was temporarily fixed via a hot melt film (M1) on the indoor non-foamed layer of the obtained foamed laminated sheet (VIII).
[0167]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M1) of the primary foam laminated sheet is clamped in four sides and placed in an oven, and the foam laminated sheet surface temperature is set to 145. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0168]
Example 6
An automobile ceiling material was obtained in the same manner as in Example 5, except that a hot melt film (M2) was used.
[0169]
The trimming waste of the automobile ceiling material having the above configuration was pulverized into chips having a size of 5 mm by a pulverizer, and the pulverized chips were put into a tank containing ethanol. After standing for 30 minutes, it was confirmed that the skin material, the abnormal noise preventing material, and the foam laminate were completely separated. In addition, it was confirmed that the skin material and the noise preventing material precipitated, and the foam laminate was floating. The floating foam laminate was scooped up with a 10-mesh net and collected. The collected foam laminate was left in an oven at 80 ° C. for 1 hour to remove ethanol adhering to the foam laminate surface, 5 parts of SBS was added, and 5 parts of a PP crosslinked foam sheet for automobile ceiling materials were further added. The mixture was melted and kneaded using a twin-screw extruder heated to 270 ° C., and then the resin was extruded from a hole-shaped die. In addition, at the time of melting and kneading, gas components generated from the vent holes were collected. Thus, a recycled resin (g) containing no solvent was collected.
[0170]
Example 1 Except that the recycled resin (g) was used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (g) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor non-foamed layer. A foam laminated sheet (IX) for automobile interior materials was obtained in the same manner as in the method for producing a foam laminated sheet for automobile interior materials in 1.
[0171]
The skin material (L) was temporarily fixed via a hot melt film (M2) on the indoor non-foamed layer of the obtained foamed laminated sheet (IX).
[0172]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M2) of the primary foam laminated sheet is clamped on all sides of the primary foam laminated sheet and placed in an oven. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0173]
Example 7
An automobile ceiling material was obtained in the same manner as in Example 5, except that a hot melt film (M3) was used.
[0174]
The trimming waste of the automobile ceiling material having the above configuration was pulverized into chips having a size of 5 mm by a pulverizer, and the pulverized chips were put into a tank containing ethanol. After standing for 30 minutes, it was confirmed that the skin material, the abnormal noise preventing material, and the foam laminate were completely separated. In addition, it was confirmed that the skin material and the noise preventing material precipitated, and the foam laminate was floating. The floating foam laminate was scooped up with a 10-mesh net and collected. The collected foam laminate was left in an oven at 80 ° C. for 1 hour to remove ethanol adhering to the foam laminate surface, 5 parts of SBS was added, and 5 parts of a PP crosslinked foam sheet for automobile ceiling materials were further added. The mixture was melted and kneaded using a twin-screw extruder heated to 270 ° C., and then the resin was extruded from a hole-shaped die. In addition, at the time of melting and kneading, gas components generated from the vent holes were collected. Thus, a recycled resin (h) containing no solvent was collected.
[0175]
Example 1 Except that the recycled resin (h) was used as the constituent resin of the indoor non-foamed layer, and 70 parts of the recycled resin (h) and 30 parts of the HIPS resin (D) were used as the constituent resin of the outdoor non-foamed layer. A foam laminated sheet (X) for an automobile interior material was obtained in the same manner as in the method for producing a foam laminated sheet for an automobile interior material in Example 1.
[0176]
The skin material (L) was temporarily fixed via a hot melt film (M3) on the indoor non-foamed layer of the obtained foamed laminated sheet (X).
[0177]
The primary foam laminated sheet having the skin material (L) temporarily fixed on the surface of the hot melt film (M3) of the primary foam laminated sheet is clamped on all sides and placed in an oven. C. for 60 seconds. Thereafter, the skin material (L) was placed in a mold so as to be on the indoor side, plug molding was performed with a mold clearance of 5.0 mm, trimming and punching were performed, and a good automobile ceiling material was obtained.
[0178]
Comparative Example 3
Using the trimming waste of the automobile ceiling material having the same configuration as that of the fifth embodiment, it is pulverized into a chip having a size of 5 mm by a pulverizer, and the pulverized waste is melted by using a twin-screw extruder heated to 270 ° C. After kneading, the resin was extruded from a hole-shaped die to obtain a regenerated resin (i).
[0179]
A mixed resin of 70 parts of the recycled resin (i) and 30 parts of the HIPS resin (D) was melted and kneaded by a single screw extruder heated to 270 ° C., and extruded into a film using a T-die. A film having a large thickness unevenness was obtained. When the thickness was adjusted, the film was partially torn and a uniform film could not be obtained.
[0180]
From the above results, the automotive interior material manufactured by laminating and integrating the skin material, the noise control material and the foam laminate through the hot melt adhesive, the nonwoven fabric skin is obtained by immersing the waste material of the laminated structure in the organic solvent. The solvent enters from the material and nonwoven noise preventive material, and the hot melt adhesive is dissolved and easily separated into the skin material, the abnormal noise preventive material and the foam laminate, and further to the separated skin material and foam laminate. Has a large density difference, and is separated into a suspended matter and a precipitate in the solvent, so that the resin component (foamed laminate) can be easily recovered. From this, separation and recovery can be performed very easily as compared with a method in which the foamed laminate is dissolved using a solvent and then separated and recovered by distillation.
[0181]
【The invention's effect】
According to the method of the present invention, a resin component can be recovered from scrap materials and waste materials of automobile interior materials by a simple operation, and can be reused in the production of automobile interior materials without deteriorating the quality required for automobile interior materials. Can be used. The present invention proposes a method of returning recycled resin to a product, and can respond to recent market needs for controlling environmental loads at an industrial level.
[Brief description of the drawings]
FIG. 1 is a partially sectional explanatory view showing one embodiment of an automobile interior material used for recycling according to the present invention.
FIG. 2 is a partial cross-sectional explanatory view showing another embodiment of an automobile interior material used for recycling according to the present invention.
FIG. 3 is a partial cross-sectional explanatory view showing one embodiment of a foamed laminated sheet for an automobile interior material using a recycled resin according to the present invention.
FIG. 4 is a partially sectional explanatory view showing another embodiment of the foamed laminated sheet for an automobile interior material using the recycled resin according to the present invention.
FIG. 5 is an explanatory plan view showing an example of a trimmed automobile ceiling material according to the present invention.
[Explanation of symbols]
1 foam layer
3 Indoor non-foaming layer
5 Outdoor non-foaming layer
7 Adhesive layer
9 Non-woven fabric layer for skin material
11 Non-woven fabric layer for noise prevention
10 Foam layer
12 Indoor non-foaming layer
14 Outdoor non-foaming layer
16 Adhesive layer
18 Non-woven fabric layer for skin material
20 Non-woven fabric layer for noise prevention
22 Automotive ceiling materials
24 Assist grip mounting hole
26 Sun visor mounting hole
28 Sun visor mounting holes
30 Room mirror mounting hole
32 Interior light mounting hole

Claims (22)

A foamed laminated sheet comprising a foamed layer having a modified polyphenylene ether-based resin as a base resin and a non-foamed layer laminated on both surfaces thereof, wherein at least one of the non-foamed layers comprises a modified polyphenylene ether-based resin. A foam laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foam layer as a material resin, a skin material laminated on one surface thereof, and an abnormal noise prevention material laminated appropriately on the other surface A recycled resin obtained by substantially separating and removing a skin material and a noise preventing material from scraps or waste materials of automobile interior materials and then regenerating the resin, and in the recycled resin, a polyolefin resin and a styrene thermoplastic resin are contained. A foam laminated sheet for an automobile interior material, comprising an elastomer. The foamed laminated sheet for an automobile interior material according to claim 1, wherein the content of the recycled resin contained in the constituent resin of the non-foamed layer is 50% by weight or more. The foamed laminated sheet for an automobile interior material according to claim 1 or 2, wherein the recycled resin contains 0.1 to 10% by weight of a polyolefin resin. The foamed laminated sheet for an automobile interior material according to any one of claims 1 to 3, wherein the content of the styrene-based thermoplastic elastomer contained in the recycled resin is 1 to 20% by weight. The foamed laminated sheet for an automobile interior material according to any one of claims 1 to 4, wherein the styrene-based thermoplastic elastomer contained in the recycled resin is a styrene-butadiene-based thermoplastic elastomer (SBS). A foamed laminated sheet comprising a foamed layer having a modified polyphenylene ether-based resin as a base resin and a non-foamed layer laminated on both surfaces thereof, wherein at least one of the non-foamed layers comprises a modified polyphenylene ether-based resin. A foam laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foam layer as a material resin, a skin material laminated on one surface thereof, and an abnormal noise prevention material laminated appropriately on the other surface A recycled resin obtained by substantially separating and removing a skin material and a noise preventing material from scraps or waste materials of an automobile interior material and then regenerating the resin, wherein the non-foamed layer containing the recycled resin is made of polyester with respect to the layer. A foam laminated sheet for automobile interior materials, comprising 0.1 to 3% by weight of a system fiber and a fiber length of 1 mm or less. The Vicat softening temperature of the base resin constituting the foamed layer is higher than the Vicat softening temperature of the base resin constituting the non-foamed layer laminated on both surfaces thereof, for an automotive interior material according to any one of claims 1 to 6. Foam laminated sheet. The foamed laminated sheet for an automobile interior material according to any one of claims 1 to 7, wherein the modified polyphenylene ether-based resin of the foamed layer comprises 35 to 75% by weight of a phenylene ether component and 65 to 25% by weight of a styrene-based component. A foamed laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on both sides of a foamed layer having a modified polyphenylene ether-based resin as a base resin, and a skin material laminated on one surface thereof and appropriately laminated on the other surface A method of reusing an automobile interior material made of a noise-preventing material, wherein in the production of a foamed laminated sheet having the same structure as described above, the skin material and the noise-preventing material are substantially formed from scraps or waste material of the automobile interior material. A method for reusing an automobile interior material, wherein at least one non-foamed layer of a foamed laminated sheet is formed from a resin containing a regenerated resin obtained by regenerating after being separated and removed. The method according to claim 9, wherein the content of the recycled resin contained in the constituent resin of the non-foamed layer is 50% by weight or more. 11. The surface material and the noise preventive material are substantially separated and removed from the scraps or waste materials of the automobile interior material by sieving and / or specific gravity separation after grinding the scrap materials or waste materials of the automobile interior material. How to reuse automotive interior materials. The automobile interior material according to claim 9 or 10, wherein the scrap material or the waste material of the automobile interior material is impregnated in an organic solvent, and the skin material and the noise prevention material are substantially separated and removed from the scrap material or the waste material of the automobile interior material. Reuse method. 13. The organic solvent used for substantially separating and removing the skin material and the noise preventing material contained in the offcuts or waste material of the automobile interior material is an alcohol. How to reuse automotive interior materials. 11. The organic solvent used for substantially separating and removing the skin material and the noise preventing material contained in the offcuts or waste material of the automobile interior material is an aliphatic hydrocarbon. Or a method for reusing automobile interior materials according to item 12. The automobile interior material according to any one of claims 9 to 14, wherein the regenerated resin is a resin regenerated by extruding a foamed laminated sheet portion recovered from scraps or waste materials at a temperature of 270 ° C or higher. How to Use. The method according to any one of claims 9 to 15, wherein the recycled resin contains 0.1 to 10% by weight of a polyolefin resin. The method for reusing an automobile interior material according to any one of claims 9 to 16, wherein the recycled resin contains a styrene-based thermoplastic elastomer in an amount of 1 to 20% by weight based on the total amount. The method according to any one of claims 9 to 17, wherein the styrene-based thermoplastic elastomer contained in the recycled resin is a styrene-butadiene-based thermoplastic elastomer (SBS). The automotive interior material according to any one of claims 9 to 18, wherein the Vicat softening temperature of the base resin constituting the foamed layer is higher than the Vicat softening temperature of the base resin constituting the non-foamed layer laminated on both surfaces thereof. Reuse method. 20. The method according to claim 9, wherein the thermoplastic resin constituting the non-foamed layer comprises a modified polyphenylene ether-based resin. 21. The method according to any one of claims 9 to 20, wherein the thermoplastic resin constituting the non-foamed layer comprises a polystyrene resin having improved heat resistance. 22. The method according to claim 9, wherein the modified polyphenylene ether-based resin of the foamed layer comprises 35 to 75% by weight of a phenylene ether component and 65 to 25% by weight of a styrene-based component.

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