JP4032912B2 - Method of recovering thermoplastic resin from waste optical disc, thermoplastic resin composition including recovered thermoplastic resin, and thermoplastic resin molded article - Google Patents

Description

（（Ｉ）式中、Ｒ¹、Ｒ²及びＲ³は、それぞれ相互に独立して選ばれる炭素数１〜８のアルキル基、又はアルキル置換されていても良い炭素数６〜２０のアリール基を表し、ｎは０又は１である。）
【００６２】
【化２】

（（II）式中、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、それぞれ相互に独立して選ばれるアリール基又はアルカリール基を表し、Ｘはアリーレン基を表し、ｊ、ｋ、ｌ、及びｍは、それぞれ相互に独立して０又は１である。Ｎは１〜５の整数であるが、リン酸エステル化合物の混合物の場合は、Ｎは平均値（１≦Ｎ≦５）を表す。）
【００６３】
前記一般式（Ｉ）で表されるリン酸エステル化合物の具体例としては、ビス−（フェニル）−メチルホスフェート、ビス−（エチル）−フェニルホスフェート、ビス−（エチル）−２，６−ジメチルフェニルホスフェート、ビス−（フェニル）−エチルホスフェート、ビス−（フェニル）−ブチルホスフェート、ビス−（ネオペンチル）−フェニルホスフェート、ビス−（４−メチルフェニル）−２−エチルヘキシルホスフェート、ビス−（２−エチルヘキシル）−フェニルホスフェート、ビス−（フェニル）−２−エチルヘキシルホスフェート、ビス−（フェニル）−オクチルホスフェート、ビス−（オクチル）フェニルホスフェート、ビス−（３，５，５−トリメチルヘキシル）フェニルホスフェート、ビス−（２，５，５−トリメチルヘキシル）−４−メチルフェニルホスフェート、ビス−（フェニル）−イソデシルホスフェート、ビス−（ドデシル）−４−メチルフェニルホスフェート、ビス−（ドデシル）フェニルホスフェート、トリス−（フェニル）ホスフェート、トリス−（２−メチルフェニル）ホスフェート、トリス−（４−メチルフェニル）ホスフェート、ビス−（２−メチルフェニル）フェニルホスフェート、ビス−（４−メチルフェニルフェニル）フェニルホスフェート、ビス−（フェニル）−２−メチルフェニルホスフェート、ビス−（フェニル）−４−メチルフェニルホスフェート、トリス−（イソプロピルフェニル）ホスフェート、ビス−（イソプロピルフェニル）フェニルホスフェート、ビス−（フェニル）−イソプロピルフェニルホスフェート、トリス−（ノニルフェニル）ホスフェート、トリス−（２，６−ジメチルフェニル）ホスフェート、ビス−（２，６−ジメチルフェニル）フェニルホスフェート、ビス−（２，６−ジメチルフェニル）−２，６−ジメチルフェニルホスフェート、ビス−（２，６−ジメチルフェニル）−４−ｔ−ブチルフェニルホスフェート、ビス−（２，６−ジメチルフェニル）−４−メチルフェニルホスフェート、ビス−（２，６−ジメチルフェニル）−３−メチルフェニルホスフェート、ビス−（２，６−ジメチルフェニル）−４−イソプロピルフェニルホスフェート、ビス−（２，６−ジメチルフェニル）−２−イソプロピルフェニルホスフェートが挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。
【００６４】
また、前記一般式（II）で表される縮合リン酸エステル化合物も１種を単独で用いても良く、２種以上を混合して用いても良い。従って、前記一般式（II）において、Ｎの値は、必ずしも整数である必要はなく、混合物の場合は、縮合リン酸エステル化合物の混合物中の平均値を表す。前記一般式（II）において、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は好ましくはクレジル基、フェニル基、キシレニル基、プロピルフェニル基、ブチルフェニル基であり、Ｘのアリーレン基は、例えばレゾルシノール、ハイドロキノン、ビスフェノールＡ及びこれらの塩素化物及び臭素化物などのジヒドロキシ化合物から誘導される基であっても良いし、フェニレン基等であっても良い。
【００６５】
リン系難燃剤としては、上記リン酸エステル化合物と縮合リン酸エステルとを併用しても良い。
【００６６】
本発明で使用される臭素系難燃剤としては、臭素化エポキシ重合体から選ばれる少なくとも１種の難燃剤が挙げられる。臭素化エポキシ重合体とは、臭素化ビスフェノール化合物とエピクロロヒドリン、又は臭素化ビスフェノール化合物ジグリシジルエーテルの付加重合体をいう。ここで、臭素化ビスフェノール化合物としてはテトラブロモビスフェノールＡ、ジブロモビスフェノールＡ、テトラブロモビスフェノールＦ、テトラブロモビスフェノールＳ等が挙げられる。臭素化エポキシ重合体の分子量は、重合度（臭素化ビスフェノール化合物・２−ヒドロキシプロパン単位の繰返数）に応じて数百から数万までのものがある。臭素化エポキシ重合体の分子末端は、エポキシ基のままであってもアリール基やアルキル基で変性されていても良く、更に、これらのアリール基やアルキル基は臭素で置換されていても良い。アリール基としてはフェニル基、キシリル基、トリブロモフェニル基等が挙げられ、アルキル基としては、メチル基、エチル基、トリブロモネオペンチル基等が挙げられる。
【００６７】
臭素化エポキシ重合体の具体的な例としては、テトラブロモビスフェノールＡ・エポキシ重合体及びトリブロモフェノール変性テトラブロモビスフェノールＡ・エポキシ重合体等が挙げられる。
【００６８】
このような難燃剤（Ｃ）の配合量が前述の樹脂成分１００重量部に対して３０重量部を超えると得られる成形品の耐熱性や機械特性が低下するので、難燃剤（Ｃ）は、前記樹脂成分１００重量部に対して３０重量部以下、特に５〜２５重量部とするのが好ましい。
【００６９】
本発明で添加するドリップ防止剤（Ｄ）としては、樹脂中にフッ素原子を有する樹脂が挙げられ、具体的にはポリモノフルオロエチレン、ポリジフルオロエチレン、ポリトリフルオロエチレン、ポリテトラフルオロエチレン、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体などを挙げることができ、これらは１種を単独で、或いは２種以上を組み合わせて用いることができるが、これらの中で特にポリテトラフルオロエチレンが好ましい。このようなフッ素系樹脂の製造方法には特に制限はなく、乳化重合、懸濁重合、塊状重合、溶液重合などの通常公知の方法を採用することができるが、燃焼時の耐ドリッピング性の観点から乳化重合で製造されたフッ素系樹脂が好ましい。
【００７０】
フッ素系樹脂は、燃焼時の溶融滴下性の改善のための成分であり、前記難燃剤（Ｃ）の配合によりフッ素系樹脂を配合しない場合であっても十分な難燃性を得ることができるが、フッ素系樹脂を配合することにより、ＵＬ９４燃焼ランクにおいてＶ−０をも達成することが可能となる。ただし、フッ素系樹脂の配合量が多過ぎると樹脂の機械的強度及び加工流動性が低下することから、フッ素系樹脂を配合する場合、その配合量は前記樹脂成分１００重量部に対して１重量部以下、特に０．０１〜１重量部とするのが好ましい。フッ素系樹脂の配合量が前記樹脂成分１００重量部に対して、０重量部の場合はＵＬ９４燃焼ランクにおいてＶ−２を目的とした場合であり、０．０１重量部以上の添加の場合によりドリップ防止効果が発揮できＶ−０を達成できる。
【００７１】
本発明の熱可塑性樹脂組成物は、更に、前記樹脂成分１００重量部に対して、カーボン繊維、金属繊維等の無機充填剤（Ｅ）の１種又は２種以上を５〜６０重量部含有していても良い。
【００７２】
このカーボン繊維としては、繊維径が４〜２０μｍで繊維長が３〜２０ｍｍであるものが好ましい。カーボン繊維の繊維径が４μｍ未満では、カーボン繊維の製造が困難で高価となり、また、２０μｍを超えると少量配合で十分な導電性、電磁波遮蔽効果を得ることができない。カーボン繊維の繊維長が３ｍｍ未満では少量配合で十分な導電性、電磁波遮蔽効果を得ることができず、２０ｍｍを超えると樹脂溶融時の流動性が低下し、混練押出が難しくなる傾向になる。なお、カーボン繊維の形態としては特に制限はなく、ＰＡＮ系、ピッチ系のいずれでも良い。カーボン繊維の好ましい配合量は、前記樹脂成分１００重量部に対して５〜４０重量部である。この配合量が５重量部未満であると、十分な導電性、電磁波遮蔽効果が得られず、４０重量部を超えると外観が悪くなるのみならず、生産時に混練押出機等を用いた場合、混練機内で過剰な剪断発熱を起こし、ポリマーが分解して生産不可能となる。
【００７３】
金属繊維としてはステンレス繊維が好ましく、繊維径が５〜６０μｍ、繊維長が２〜１０ｍｍであるものが好ましい。ステンレス繊維の繊維径が５μｍ未満であるとステンレス繊維の製造が難しくなり、６０μｍを超えると少量での高い導電性、電磁波遮蔽効果が得にくい傾向にある。また、繊維長が２ｍｍ未満であると少量での高い導電性、電磁波遮蔽効果が得にくく、１０ｍｍを超えると樹脂溶融時の流動性が低下し、混練押出が難しくなる傾向にある。ステンレス繊維の好ましい配合量は、前記樹脂成分１００重量部に対して５〜４０重量部である。この配合量が５重量部未満であると十分な導電性、電磁波遮蔽効果が得られず、４０重量部を超えると外観が悪くなるのみならず、生産時に混練押出機等を用いた場合、混練機内で過剰な剪断発熱を起こし、ポリマーが分解して生産不可能となる。
【００７４】
なお、カーボン繊維とステンレス繊維とを併用配合する場合、その配合割合は、重量比でカーボン繊維：ステンレス繊維＝１：０．５〜３とするのが導電性及び電磁波遮蔽効果の面で好ましく、また、カーボン繊維とステンレス繊維の合計の配合量は樹脂成分１００重量部に対して５〜６０重量部、特に５〜４０重量部であることが好ましい。
【００７５】
また、本発明の熱可塑性樹脂組成物には、本発明の趣旨を妨げない範囲で、公知の酸化防止剤、紫外線吸収剤、滑剤、可塑剤、離型剤、帯電防止剤、着色剤（顔料、染料など）、フィラー、アンチモン化合物などの難燃助剤、抗菌剤、防カビ剤、シリコーンオイル、カップリング剤などの各種の添加剤を含んでいても良い。また、リン系難燃剤や臭素系以外の難燃剤やカーボン繊維やステンレス繊維以外の導電性物質を含有していても良い。
【００７６】
これらの配合成分を混合して本発明の熱可塑性樹脂組成物を製造する方法としては特に制限はないが、例えば、押出機、バンバリーミキサー等を用いた溶融混練法が好ましい。
【００７７】
このようにして得られる本発明の熱可塑性樹脂組成物は、射出成形、シート押出、真空成形、圧空成形、異形押出成形、発泡成形、ブロー成形などによって、各種成形品に成形することができる。
【００７８】
本発明の熱可塑性樹脂組成物を成形して得られる本発明の熱可塑性樹脂成形品は、熱可塑性樹脂組成物の配合組成を調整することにより、車両用部品や一般機材の用途をはじめ、例えば、難燃剤（Ｃ）及びドリップ防止剤（Ｄ）を配合することによる高度な難燃性によりＯＡ機器への用途が可能であり、更に、前記無機充填剤（Ｅ）を配合して導電性を付与することにより電磁波障害（ＥＭＩ）が問題となる可能性のある電気電子機器及び電子機器部品のハウジング等、特に、コンピュータ、プリンタ、コピー機等のＯＡ機器、更にモバイルコンピュータをはじめとする携帯情報機器のハウジング等に好適に使用することができる。
【００７９】
【実施例】
以下に、合成例、実施例、比較例及び参考例を挙げて本発明をより具体的に説明するが、本発明は、その要旨を超えない限り、以下の実施例に何ら制限されるものではない。
【００８０】
なお、以下において、粘度平均分子量（Ｍｖ）は下記の方法で測定した。
［粘度平均分子量（Ｍｖ）の測定方法］
試料を塩化メチレンを溶媒とする溶液として、ウェベローデ粘度計を用いて測定し、下記ｓｃｈｎｅｌｌの粘度式を用いて求めた。
〔η〕＝１．２３×１０^−４×Ｍｖ^０．８３
（式中、ηは固有粘度を示す。）
【００８１】
［廃ＣＤからのポリカーボネート樹脂の回収］
実施例１〜３、比較例１２〜１５
市場から回収された廃ＣＤを円盤の状態で１００枚、互いに数ｍｍの間隔をあけて、表１に示す組成及びｐＨの酸溶液３０Ｌに３０℃で表１に示す時間浸漬した。その後、廃ＣＤを酸溶液から取り出し水洗した後８０℃で風乾した。
【００８２】
その結果、実施例１〜３及び比較例１２，１３ではアルミニウム反射膜、保護膜、印刷膜等の被膜をすべて溶解ないし剥離除去することができ、不純物を含まないポリカーボネート樹脂を回収することができた。ただし、実施例１〜３では１０分の浸漬処理で完全に被膜を剥離除去できたが、比較例１２，１３では、処理に４５分を要した。また、比較例１４，１５では６０分の処理でも十分に被膜を除去し得なかった。
【００８３】
【表１】

【００８４】
なお、回収されたポリカーボネート樹脂が回収前のポリカーボネート樹脂と物性面で差異がないことを調べるために、回収前の廃ＣＤの基板の成形材料であるポリカーボネート樹脂と、回収されたポリカーボネート樹脂の粘度平均分子量を調べたところ、成形前のポリカーボネート樹脂の粘度平均分子量は１．４５×１０^４であった。
【００８５】
一方、各例で回収されたポリカーボネート樹脂の粘度平均分子量測定結果は、表２に示す通りであり、成形前のポリカーボネート樹脂に対して分子量低下は起こっておらず、使用前と同等の物性のポリカーボネート樹脂を回収することができたことがわかる。
【００８６】
比較例１
処理液として水酸化ナトリウム８重量％、グルコン酸ソーダ１．８重量％、アルキルアミンオキサイド０．２重量％を含むアルカリ溶液（ｐＨ１４）を用いたこと以外は、実施例１と同様にして剥離処理を行った。６０分間浸漬後、廃ＣＤを処理液から取り出し水洗したところ、アルミニウム反射膜、保護膜、印刷膜等の被膜は十分に剥離、除去されておらず、不純物を含まないポリカーボネート樹脂を回収することはできなかった。
【００８７】
比較例２
処理温度を９０℃としたこと以外は、比較例１と同様にして剥離処理を行った。６０分間浸漬後、廃ＣＤを処理液から取り出し水洗したところ、アルミニウム反射膜、保護膜、印刷膜等の被膜はすべて溶解、ないし剥離して除去されており、不純物を含まないポリカーボネート樹脂を回収することができた。
【００８８】
しかし、回収されたポリカーボネート樹脂の粘度平均分子量を測定したところ、表２に示すように、分子量の低下が認められた。
【００８９】
比較例３
廃ＣＤ１００枚を約２〜１０ｍｍに破砕してからアルカリ溶液で処理したこと以外は、比較例１と同様にして剥離処理を行った。６０分間浸漬後、廃ＣＤの破片を処理液から取り出し水洗したところ、アルミニウム反射膜、保護膜、印刷膜等の被膜は剥離、除去されておらず、不純物を含まないポリカーボネート樹脂を回収することはできなかった。
【００９０】
【表２】

【００９１】
［熱可塑性樹脂組成物及び熱可塑性樹脂成形品の製造］
以下において、「部」は「重量部」を示す。
【００９２】
合成例１：ゴム含有グラフト共重合体（ａ−１−１）の製造
以下の配合にて、乳化重合法によりＡＢＳ共重合体を合成した。
〔配合〕
スチレン（ＳＴ） ３５部
クリロニトリル（ＡＮ） １５部
ポリブタジエン・ラテックス ５０部（固形分として）
不均化ロジン酸カリウム １部
水酸化カリウム ０．０３部
ターシャリードデシルメルカプタン（ｔ−ＤＭ） ０．１部
クメンハイドロパーオキサイド ０．３部
硫酸第一鉄 ０．００７部
ピロリン酸ナトリウム ０．１部
結晶ブドウ糖 ０．３部
蒸留水 １９０部
【００９３】
オートクレーブに蒸留水、不均化ロジン酸カリウム、水酸化カリウム及びポリブタジエン・ラテックスを仕込み、６０℃に加熱後、硫酸第一鉄、ピロリン酸ナトリウム、結晶ブドウ糖を添加し、６０℃に保持したままＳＴ、ＡＮ、ｔ−ＤＭ及びクメンハイドロパーオキサイドを２時間かけて連続添加し、その後７０℃に昇温して１時間保って反応を完結した。かかる反応によって得たＡＢＳラテックスに酸化防止剤を添加し、その後硫酸により凝固させ、十分水洗後、乾燥してＡＢＳグラフト共重合体（ａ−１−１）を得た。
【００９４】
合成例２：ゴム含有グラフト共重合体（ａ−１−２）の製造
エチレン−プロピレン−非共役ジエン共重合体ゴムラテックス（エチレン：プロピレン：非共役ジエン（５−エチレン−２−ノルボルネン） ５０部（固形分として）の存在下、ＡＮ１５部、ＳＴ３５部を反応させたこと以外は、合成例１と同様にしてＡＥＳグラフト共重合体（ａ−１−２）を得た。
【００９５】
合成例３：ゴム含有グラフト共重合体（ａ−１−３）の製造
ポリブチルアクリレート ５０部（固形分として）の存在下、ＡＮ１５部、ＳＴ３５部を反応させたこと以外は、合成例１と同様にしてＡＳＡグラフト共重合体（ａ−１−３）を得た。
【００９６】
合成例４：硬質共重合体（ａ−２−１）の製造
窒素置換した反応器に水１２０部、アルキルベンゼンスルホン酸ソーダ０．００２部、ポリビニルアルコール０．５部、アゾイソブチルニトリル０．３部、ｔ−ＤＭ０．５部と、ＡＮ３５部、ＳＴ６５部からなるモノマー混合物を使用し、ＳＴの一部を逐次添加しながら開始温度６０℃から５時間昇温加熱後、１２０℃に到達させた。更に、１２０℃で４時間反応した後、重合物を取り出し、硬質共重合体（ａ−２−１）を得た。
【００９７】
合成例５：硬質共重合体（ａ−２−２）の製造
ＡＮ２５部、ＳＴ２０部、α−メチルスチレン３５部、Ｎ−フェニルマレイミド２０部からなるモノマー混合物を使用し、スチレン、α−メチルスチレン、Ｎ−フェニルマレイミドの一部を逐次添加したこと以外は合成例４と同様にして重合を行って、硬質共重合体（ａ−２−２）を得た。
【００９８】
ポリカーボネート樹脂（ｂ−１）としては、以下のものを用いた。
ポリカーボネート樹脂（ｂ−１−１）：三菱エンジニアリングプラスチック（株）製ポリカーボネート樹脂「Ｈ−４０００」（粘度平均分子量（Ｍｖ）：１５，０００）
ポリカーボネート樹脂（ｂ−１−２）：三菱エンジニアリングプラスチック（株）製ポリカーボネート樹脂「Ｓ−３０００」（粘度平均分子量（Ｍｖ）：２１，０００）
ポリカーボネート樹脂（ｂ−１−３）：三菱エンジニアリングプラスチック（株）製ポリカーボネート樹脂「Ｅ−２０００」（粘度平均分子量（Ｍｖ）：３１，０００）
【００９９】
回収ポリカーボネート樹脂（ｂ−２）としては、以下のものを用いた。
【０１００】
回収ポリカーボネート樹脂（ｂ−２−１）：廃ＣＤを実施例１で用いた酸溶液に５分間浸漬して被膜を除去したものを水洗、乾燥して破砕したもの。この廃ＣＤに使用されている原料ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）は１５，０００であり、回収ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）も１５，０００であった。
【０１０１】
ポリカーボネート樹脂（ｂ−２−２）：廃ＭＤを実施例２で用いた酸溶液に５分間浸漬して被膜を除去したものを水洗、乾燥して破砕したもの。この廃ＭＤに使用されている原料ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）は１５，０００であり、回収ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）も１４，９００であった。
【０１０２】
ポリカーボネート樹脂（ｂ−２−３）：廃ＣＤを比較例１４で用いた酸溶液に９０分間浸漬したもので金属被膜や塗料を十分に剥離することはできなかったものを、水洗、乾燥して破砕したもの。この廃ＣＤに使用されている原料ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）は１５，０００であり、回収ポリカーボネート樹脂の粘度平均分子量（Ｍｖ）は１３，５００であった。
【０１０３】
ポリカーボネート樹脂（ｂ−２−４）：廃ＣＤの金属被膜や塗装を除去せずにそのまま破砕したもの。
【０１０４】
ポリカーボネート樹脂（ｂ−２−５）：廃ＭＤの金属被膜や塗装を除去せずにそのまま破砕したもの。
【０１０５】
難燃剤（Ｃ）としては、以下のものを用いた。
難燃剤（ｃ−１）：旭電化工業製リン酸エステル系難燃剤「ＦＰ−５００」
難燃剤（ｃ−２）：大日本インキ社製臭素系難燃剤「ＥＣ−２０」
【０１０６】
ドリップ防止剤（Ｄ）としては、以下のものを用いた。
ドリップ防止剤（ｄ）：デュポン社製ポリテトラフルオロエチレン「テフロン（登録商標）６−Ｊ」
【０１０７】
無機充填剤（Ｅ）としては、以下のものを用いた。
無機充填剤（ｅ−１）：東邦レーヨン社製カーボン繊維「ベスファイト」（平均繊維径＝７μｍ、平均繊維長＝６ｍｍ）
無機充填剤（ｅ−２）：ベカルト社製ステンレス繊維「ベキシールド」（平均繊維径＝８μｍ、平均繊維長＝６ｍｍ）
【０１０８】
実施例８〜１５、比較例４〜１１、参考例１〜４
表３，４に示す配合割合で、更に、滑剤、酸化防止剤等の添加剤と共に混合した後、２２０〜２４０℃で２軸押出機（日本製鋼所製「ＴＥＸ−４４」）にて溶融混合し、ペレット化した。この樹脂ペレットを２オンス射出成形機（東芝（株）製）にて２２０〜２６０℃にて成形し、必要なテストピースを作成し、各種物性を下記の方法で測定し、結果を表３，４に示した。
【０１０９】
なお、参考例１〜４は、回収ポリカーボネート樹脂を用いず、新品のポリカーボネート樹脂のみを使用した例である。
〔メルトフローレート（ｇ／１０ｍｉｎ）〕 ＪＩＳ Ｋ７２１０（表３では２３０℃，表４では２２０℃／９８Ｎ）
〔アイゾット衝撃強度（Ｊ／ｍ）〕 ＡＳＴＭ Ｄ２５６（常温）
〔曲げ弾性率（ＭＰａ）〕 ６．４ｍｍ厚み（ＡＳＴＭ Ｄ７９０）
〔熱変形温度（℃）〕 ＡＳＴＭ Ｄ６４８
〔燃焼性〕 ２ｍｍ厚みの試験片に対してＵＬ９４に準じた燃焼試験を行い、燃焼性を調べた。
〔表面外観〕 目視により成形品表面を観察し、異物が無く、外観が良好なものは○、異物があり外観が悪いものは×と判定した。
【０１１０】
【表３】

【０１１１】
【表４】

【０１１２】
表３、表４より、次のことが明らかである。
【０１１３】
本発明の実施例８〜１１では、比較例４〜７に比べて表面外観、アイゾット衝撃強度が優れていることが分かる。また、実施例８は、参考例１と比較可能であり、また、実施例１０は、参考例２と比較可能であり、実施例８及び１０は参考例１，２と同等の特性を示しており、実用に十分耐えることが予想される。
【０１１４】
難燃剤やドリップ防止剤を添加した実施例１２，１３と比較例８，９について、燃焼性への効果は認められるが、表面外観、アイゾット衝撃強度については、実施例１２，１３の方がはるかに優れていることが分かる。また、実施例１２は、参考例３と同等の特性を示しており、十分実用に耐えることが予想される。
【０１１５】
さらに実施例１４，１５と比較例１０，１１は、無機充填剤であるカーボン繊維やステンレス繊維を配合した樹脂組成物であり、電磁波遮蔽効果について、一辺１５０ｍｍ、厚み３ｍｍの正方形の試験片を作成して、（株）アドバンテスト製のＴＲ−１７３０１ＡとＲ３３６１Ａを併用して磁界波（周波数３００ＭＨｚ)を測定したところ、実施例１４，１５と比較例１０，１１及び参考例４の電磁波遮蔽効果は、５０〜５５（ｄＢ）の範囲にあり、いずれも電磁波遮蔽効果が認められた。また、燃焼性への効果も認められた。しかし、表面外観、アイゾット衝撃強度の特性は、比較例１０，１１よりも実施例１４，１５の方がはるかに優れている。また、実施例１４は参考例４と同等の特性を示しており、十分実用に耐えることが予想される。
【０１１６】
以上のように、実施例では、比較例の粉砕品を使用したものに比べて、耐衝撃強度及び外観が優れている。また、参考例に示したように実施例の特性は、回収ポリカーボネート樹脂を再利用していないものと匹敵する特性を有していることが明らかである。
【０１１７】
【発明の効果】
以上詳述した通り、本発明の廃光学式ディスクからの熱可塑性樹脂の回収方法によれば、光学式ディスクの廃棄物から、熱可塑性樹脂基板上の金属反射膜等の被膜のみを容易かつ効率的に除去して、基板の構成材料である熱可塑性樹脂を、その物性を低下させることなく、そのまま再利用可能な物性を維持して高い回収率で回収することができる。
【０１１８】
また、本発明の熱可塑性樹脂組成物及び熱可塑性樹脂成形品によれば、このようにして回収した熱可塑性樹脂を用いて表面外観及び耐衝撃性等に優れた熱可塑性樹脂成形品を提供することができる。
【０１１９】
本発明によれば、近年益々その需要が増加し、不良品、検査用サンプル、回収品等の発生量も益々増加することが見込まれる光学式ディスクの廃棄物から熱可塑性樹脂を容易かつ効率的に、しかも安価に回収してこれを再利用することが可能となり、廃棄物の減量及び環境の維持、資源の有効利用等の面において、本発明の工業的有用性は極めて高い。[0001]
BACKGROUND OF THE INVENTION
  The present invention treats the waste of an optical disk, particularly a compact disk (hereinafter sometimes simply referred to as “CD”) formed by forming an aluminum reflective film on a thermoplastic resin substrate such as polycarbonate resin. The present invention relates to a method for recovering a quality thermoplastic resin, a thermoplastic resin composition excellent in surface appearance and impact resistance, and a thermoplastic resin molded article using the thermoplastic resin recovered by this method.
[0002]
[Prior art]
  Optical discs such as CDs and laser discs that serve as optical information recording media can reproduce sound and images by detecting minute irregularities provided on the disc substrate with laser light, and information recording provided on the substrate surface Various systems are provided, such as those for recording / reproducing information by layer, and those for erasing or overwriting the recorded information.
[0003]
  Optical discs such as CDs are generally provided with a metallic reflective film such as aluminum on a thermoplastic resin substrate via a magneto-optical layer or a dielectric layer as required, and then a protective coating is applied thereon. In addition, it is manufactured with necessary printing. Transparent resins such as polycarbonate resin, polymethyl methacrylate resin, and amorphous cyclic polyolefin resin are used as the thermoplastic resin that constitutes the substrate. Among them, polycarbonate resin is used in most CDs, and it is produced on a large scale. Has been done.
[0004]
  While CD is industrially mass-produced, it requires extremely high storage capacity and extremely high quality, so it must be a defective product even if it has minute defects. In addition, in order to maintain high quality, a large amount of inspection samples are extracted from various parts of the production process. Furthermore, since there are many used items, used items, collected items, etc. returned from the market etc., the disposal of these large quantities of waste products is a problem.
[0005]
  Conventionally, waste optical discs are collected by CD manufacturers or polycarbonate resin manufacturers, and are either crushed and landfilled or disposed of by incineration. However, incineration requires a special structure for incineration. Also, landfilling has a problem of environmental pollution.
[0006]
  Therefore, proposals have been made to remove coatings such as a reflective layer and a protective coating layer formed on the optical disc from the resin substrate, and to recover and reuse the resin.
[0007]
  For example, as a method of recovering polycarbonate resin from CD waste, there is a method of mechanically scraping the coating on the surface by a wire brush method or a sand blast method. Not only is it mixed, but part of the polycarbonate is also scraped off, so the recovery rate is poor. For the purpose of increasing the recording capacity, a CD in which a thin resin substrate is bonded with the recording layer inside is provided. In such a bonded CD, since the recording layer is on the inside, the coating is ground. There is also a problem that cannot be done.
[0008]
  Japanese Patent Application Laid-Open No. 9-316316 describes a method of pulverizing and using an optical disc as it is, but in this method, aluminum powder and a coating film are mixed, so that it can be obtained using recovered resin. The thermoplastic resin molded article has a drawback that the impact resistance is remarkably lowered and its use is limited.
[0009]
  Japanese Patent Laid-Open Nos. 5-200379, 6-223416, and 4-360035 disclose a method in which waste CD is pulverized or crushed to a specific size and then chemically treated with an alkaline aqueous solution. Proposed. In these methods, the coating is removed from the resin substrate by making the CD fine so that the metal portions of the information recording layer and the reflective layer are easily dissolved in an alkaline aqueous solution. However, in these methods, first, it is necessary to pulverize or crush the waste CD to a specific size, which requires equipment for pulverization and crushing, which is not only economical but also poor in efficiency. In addition, deterioration of the conventional environment due to generation of dust during pulverization and crushing may be a problem. In particular, the method described in Japanese Patent Application Laid-Open No. 4-360035 discloses that after pulverizing or crushing a CD to a specific size, it is brought into contact with a strongly alkaline aqueous solution containing caustic alkali heated to a high temperature of 75 to 100 ° C. Although the polycarbonate is weak against alkali, the polycarbonate resin obtained by peeling off the coating on the surface is reduced in molecular weight and physical properties due to high-temperature alkali. The molded product obtained by molding again has a disadvantage that it is inferior in quality.
[0010]
  Japanese Patent Application Laid-Open No. 5-345321 proposes a method for removing a film by immersing a CD in hot water for a long time. In the case of a polycarbonate resin substrate, there is a drawback that molecular weight is decreased and whitening is likely to occur, which is not a preferable method for reusing the recovered resin.
[0011]
[Patent Document 1]
          JP-A-9-316316
[Patent Document 2]
          Japanese Patent Laid-Open No. 5-200379
[Patent Document 3]
          JP-A-6-223416
[Patent Document 4]
          JP-A-4-360035
[Patent Document 5]
          JP-A-5-345321
[0012]
[Problems to be solved by the invention]
  As described above, conventionally, from the waste of the optical disk, only the coating such as the metal reflective film on the thermoplastic resin substrate is easily and efficiently removed, and the thermoplastic resin which is the constituent material of the substrate is removed. No method has been proposed for recovering at a high recovery rate while maintaining the physical properties that can be reused as they are without deteriorating their physical properties, and in any method, the recovery rate, processing efficiency, economic efficiency, workability, Or, it has a defect in any of the physical properties of the recovered thermoplastic resin.
[0013]
  The present invention solves the above-described conventional problems, and easily and efficiently removes only a coating film such as a metal reflective film on a thermoplastic resin substrate from the waste of an optical disk, thereby providing a thermal material that is a constituent material of the substrate. It is an object of the present invention to provide a method for recovering a thermoplastic resin from a waste optical disc that can recover the plastic resin at a high recovery rate while maintaining the physical properties that can be reused as it is without deteriorating its physical properties. To do.
[0014]
  Another object of the present invention is to provide a thermoplastic resin molded article excellent in surface appearance and impact resistance using the recovered thermoplastic resin.
[0015]
[Means for Solving the Problems]
  The method for recovering a thermoplastic resin from a waste optical disc according to the present invention includes a method for recovering a thermoplastic resin from a waste of an optical disc in which a coating including a metal reflection film is formed on a thermoplastic resin substrate. The disc is brought into contact with an acid solution to dissolve or peel off the coating, and then washed with water and dried.A method, wherein the acid solution is an aqueous solution comprising an inorganic acid, an organic acid, a halogen compound, and a penetrantIt is characterized by that.
[0016]
  In the present invention, since an acid solution is used, it can be recovered while maintaining the initial physical properties without adversely affecting the physical properties of a thermoplastic resin such as a polycarbonate resin, and can be easily remolded and reused. Is possible.
[0017]
  The present invention is particularly effective for recovering a polycarbonate resin as a thermoplastic resin, and the acid solution is preferably an acid solution having a pH of 3 or less, particularly an aqueous solution containing an inorganic acid, an organic acid, a halogen compound and a penetrant. In this case, the inorganic acid includes one or more selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and the organic acid includes citric acid, sulfamic acid, oxalic acid, glycolic acid, acetic acid and formic acid. 1 type or 2 or more types selected from the group which consists of are mentioned, As a halogen compound, 1 type or 2 or more types chosen from the group which consists of sodium halide, potassium halide, ammonium halide, and hydrohalic acid are mentioned. Examples of the penetrant include one or more selected from the group consisting of polyoxyalkylene alkyl ethers, alkylbenzene sulfonates and naphthalene sulfonates.
[0018]
  The concentration of the inorganic acid in the acid solution is preferably 10 to 80% by weight, the concentration of the organic acid is preferably 1 to 20% by weight, and the concentration of the halogen compound is 1 to 30% by weight. Preferably, the concentration of the penetrant is 0.1 to 5% by weight.
[0019]
  In the present invention, it is preferable that the optical disc is directly contacted with the acid solution without crushing, and in this case, facilities for crushing and crushing are not required, and economical efficiency, workability, and processing efficiency are eliminated. Will improve. In addition, when crushing is performed, crushing films such as reflective films, protective films, and printed films on the substrate, especially the printed films, are present as highly viscous foreign substances in the acid solution, and workability during processing is increased. However, if the film is not crushed, these films can be dissolved or peeled and removed with excellent handleability, and the subsequent recovery of the thermoplastic resin is facilitated.
[0020]
  According to the method for recovering a thermoplastic resin from the waste optical disc of the present invention, it can be easily recovered without impairing the physical properties of the thermoplastic resin constituting the substrate. Molecular weight M of thermoplastic resin as molding material for waste CD substrate₀In contrast, the molecular weight M of the recovered thermoplastic resin_XIs M₀× 1 to M₀× 0.95, almost no decrease in molecular weight, and having substantially the same physical properties can be obtained.
[0021]
  The thermoplastic resin composition of the present invention is a thermoplastic resin recovered by such a method of recovering a thermoplastic resin from the waste optical disc of the present invention (hereinafter sometimes referred to as “recovered thermoplastic resin”). In particular, it preferably contains a rubber-reinforced styrene-based resin and a recovered polycarbonate resin as a recovered thermoplastic resin, and particularly preferably a thermoplastic resin composition having the following composition.
[0022]
  (A) A rubber-containing graft obtained by graft polymerization of one or more vinyl monomers selected from an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubber-like polymer ( (Co) polymer (a-1) 5 to 100% by weight and one or more monomers selected from aromatic vinyl monomers and vinyl cyanide monomers. ) 10 to 70 parts by weight of a rubber-reinforced styrene resin containing 95 to 0% by weight of the polymer (a-2);
  (B) Polycarbonate containing 0 to 99% by weight of polycarbonate resin (b-1) having a number average molecular weight of 18,000 to 40,000 by solution viscosity method and 100 to 1% by weight of the recovered polycarbonate resin (b-2) 90 to 30 parts by weight of resin
(However, the total of (A) rubber-reinforced styrene resin and (B) polycarbonate resin is 100 parts by weight) thermoplastic resin composition (in addition, “(co) polymer” means “polymer and / or Copolymer ").
[0023]
  The thermoplastic resin composition further comprises (C) a flame retardant of 0 to 30 parts by weight or less and (D) a drip with respect to a total of 100 parts by weight of (A) a rubber-reinforced styrene resin and (B) a polycarbonate resin. 1 part by weight or less of the inhibitor and / or (E) 5 to 60 parts by weight of an inorganic filler may be included.
[0024]
  With such a thermoplastic resin composition, it is possible to provide a high-performance and high-quality thermoplastic resin molded article having excellent surface appearance and impact resistance, and recovering the thermoplastic resin from the waste optical disc. It can be reused for a wide range of purposes.
[0025]
  The thermoplastic resin molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention, and has excellent surface appearance and impact resistance, and further has high flame retardancy and electromagnetic wave shielding effect. Such excellent functionality can also be imparted, and it can be suitably used for housings for OA equipment, electrical and electronic equipment, electronic equipment parts, etc., as well as applications for vehicle parts and general equipment.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described in detail.
[0027]
  First, a method for recovering the thermoplastic resin from the waste optical disc of the present invention will be described.
[0028]
  There is no particular limitation on the waste such as an optical disc (hereinafter, sometimes referred to as “waste optical disc” or “waste CD”) to be processed by the recovery method of the present invention, and on a substrate made of a thermoplastic resin. At least one surface of the film is formed with a metal reflective film made of a vapor deposition film such as aluminum, or a layer in which these are laminated, a protective coating film, a printed film, and in some cases, a film such as a dielectric layer or a magneto-optical layer. An information recording film layer, a reflective film layer, and the like are formed, and examples include commercially available music CDs, game CDs, MDs, MOs, and DVDs. This waste CD may be a laminate of two substrates with such a coating inside. The thermoplastic resin constituting the substrate is not particularly limited, and examples thereof include transparent resins such as polycarbonate resin, polymethyl methacrylate resin, and amorphous cyclic polyolefin resin, but the present invention is most widely used particularly as a substrate for CD and the like. The present invention is very effectively applied to waste CD using a polycarbonate resin substrate.
[0029]
  In the present invention, such a waste CD is preferably treated with an acid solution as it is without being crushed to remove the reflective film and the protective coating film, but may be already crushed or crushed. You may do it. However, for the reasons described above, in the present invention, it is preferable to treat the waste CD as it is without crushing the waste CD.
[0030]
  When the pH of the acid solution to be used is high, the treatment time required for removing the coating becomes long. Therefore, the pH is preferably 3.5 or less, particularly 3 or less, and particularly preferably 1 or less. Although the treatment time varies depending on the composition of the acid solution, the treatment time may be about 5 minutes if the acid solution is pH 1 or less, and the treatment time is about 20 to 30 minutes if the acid solution is pH 3 or less. . In the case of an acid solution exceeding pH 3, a longer treatment time is required.
[0031]
  This acid solution,NothingAqueous solutions containing organic acids, organic acids, halogenated compounds and penetrantsAndExamples of the inorganic acid used in the acid solution include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and examples of the organic acid include citric acid, sulfamic acid, oxalic acid, glycolic acid, acetic acid, formic acid, and halogen compounds. Examples thereof include sodium halides such as chlorine, iodine and fluorine, potassium halides, ammonium halides, hydrohalic acids, etc., and penetrants include polyoxyalkylene alkyl ethers, alkylbenzene sulfonates, naphthalene sulfates. Examples include phonates. One of these inorganic acids, organic acids, halogenated compounds, and penetrants can be used alone or in admixture of two or more.
[0032]
  Acid solutions include inorganic acids, organic acids, halogen compounds and permeationAgentBy including all, the film can be removed very easily and in a short time, which is preferable.
[0033]
  In addition, when using a hydrohalic acid as a halogen compound, it can combine with an inorganic acid.
[0034]
  That is, the inorganic acid has an action of removing a metallic reflective film such as aluminum and a printed film, and the organic acid has an action of promoting the removal of a metallic reflective film such as aluminum. For this reason, the metal reflective film such as aluminum and the printed film can be efficiently removed by using the inorganic acid and the organic acid in combination. In addition, the incorporation of a halogen compound makes it possible to easily penetrate an inorganic acid, an organic acid or the like into a metal reflective film layer such as aluminum, and has the effect of promoting the removal of the metal reflective film such as aluminum and the removal of the printed film. Is done. Further, the penetrating agent also has the effect of promoting the penetration of inorganic acid, organic acid, etc. into the aluminum reflective film layer, and a remarkably good processing efficiency can be obtained by these synergistic effects.
[0035]
  In this case, the preferable content of each component in the acid solution is as follows.
    Inorganic acid: 10 to 80% by weight
    Organic acid: 1 to 20% by weight
    Halogen compound: 1 to 30% by weight
    Penetration agent: 0.1 to 5% by weight
[0036]
  If the content of the inorganic acid, organic acid, halogen compound, and penetrant is not within the above range, the reflective film and the protective coating may not be easily and efficiently removed. A particularly preferable composition range is 20 to 60% by weight of an inorganic acid, 1 to 10% by weight of an organic acid, 5 to 20% by weight of a halogen compound, and 0.1 to 2% by weight of a penetrant.
[0037]
  In addition, the total content of inorganic acid, organic acid, halogenated compound and penetrant in the acid solution is 15 to 80% by weight, particularly 20 to 60% by weight, from the viewpoint of handleability and treatment efficiency as an aqueous solution. It is preferable.
[0038]
  The treatment temperature with this acid solution is preferably 10 to 50 ° C, particularly preferably 25 to 35 ° C. When the processing temperature is too low, the processing time is long and not efficient, and when the processing temperature is too high, handling becomes difficult and heating is required, which is not economical.
[0039]
  The treatment time with the acid solution varies depending on the composition and temperature of the acid solution, but is preferably 5 to 60 minutes. If the treatment time is less than 5 minutes, peeling of the coating film on the surface becomes insufficient, resulting in deterioration of the surface appearance and impact resistance of the thermoplastic resin molded product obtained by reusing it, and exceeding 60 minutes. When a long time is required, the molecular weight of the recovered thermoplastic resin may be lowered, and the impact resistance of the obtained thermoplastic resin molded product may be lowered.
[0040]
  In the present invention, the waste CD can be easily dissolved or peeled and removed by simply immersing the waste CD in such an acid solution for a predetermined time. Therefore, the substrate-like thermoplastic resin can be recovered simply by washing and drying the waste CD after being immersed in the acid solution. The washing temperature may be 1 to 99 ° C. as long as the water maintains a liquid at normal pressure. Moreover, it is preferable to perform drying by 30-120 degreeC air drying. In addition, a vibration may be added to waste CD at the time of immersion, or a physical effect | action by an ultrasonic wave etc. may be added.
[0041]
  Thus, the recovered thermoplastic resin has almost no problem of deterioration in physical properties with respect to the thermoplastic resin constituting the waste CD substrate before recovery. For example, the thermoplastic resin of the molding material of the waste CD substrate Molecular weight M₀In contrast, the molecular weight M of the recovered thermoplastic resin_XIs M₀× 1 to M₀× 0.95, almost no decrease in molecular weight, and having substantially the same physical properties can be obtained.
[0042]
  Next, the thermoplastic resin composition and thermoplastic resin molded article of the present invention containing the recovered thermoplastic resin recovered in this way will be described.
[0043]
  The thermoplastic resin composition of the present invention is preferably
  (A) A rubber-containing graft obtained by graft polymerization of one or more vinyl monomers selected from an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubber-like polymer ( (Co) polymer (a-1) 5 to 100% by weight and one or more monomers selected from aromatic vinyl monomers and vinyl cyanide monomers. ) 10 to 70 parts by weight of a rubber-reinforced styrene resin containing 95 to 0% by weight of the polymer (a-2);
  (B) Polycarbonate containing 0 to 99% by weight of polycarbonate resin (b-1) having a number average molecular weight of 18,000 to 40,000 by solution viscosity method and 100 to 1% by weight of the recovered polycarbonate resin (b-2) 90 to 30 parts by weight of resin
(However, the total of (A) rubber-reinforced styrene resin and (B) polycarbonate resin is 100 parts by weight).
[0044]
  Of the rubber-reinforced styrene-based resin (A) component, the rubber-like polymer in the rubber-containing graft (co) polymer (a-1) includes a vinyl monomer copolymerizable with polybutadiene and butadiene. Conjugated diene polymers such as copolymers, acrylic ester polymers, acrylic ester polymers such as copolymers of vinyl monomers copolymerizable with acrylic esters, ethylene-propylene or butene Preferably, a propylene-nonconjugated diene copolymer, a polyorganosiloxane polymer, and the like are used. Here, as the acrylic ester of the acrylic ester polymer, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, 2-ethylhexyl Examples of the diene contained in the ethylene-propylene-nonconjugated diene copolymer include dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,5, and the like. -Cyclooctadiene, 6-methyl-1,5-heptadiene, 11-ethyl-1,11-tridecadiene, 5-methylene-2-norbornene and the like. As the rubbery polymer, one of these can be used alone or as a composite rubber of two or more.
[0045]
  Examples of the vinyl monomer to be graft-polymerized to such a rubbery polymer include an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth) acrylic ester used as necessary. , Other monomers capable of graft polymerization, such as maleimide compounds and unsaturated carboxylic acids. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, bromostyrene, and the like, and styrene and α-methylstyrene are particularly preferable. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. Examples of other monomers include (meth) acrylic acid esters such as methacrylic acid esters or acrylic acid esters such as methyl methacrylate and methyl acrylate, and maleimide compounds include N-phenylmaleimide and N-cyclohexyl. Maleimide and the like can be mentioned, and examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid and fumaric acid. These can be used individually by 1 type or in mixture of 2 or more types, respectively.
[0046]
  In the graft (co) polymer, the ratio of these monomer components is, by weight, aromatic vinyl monomer: vinyl cyanide monomer: other monomer = 95-60: 5 40: 0 to 50 is preferable.
[0047]
  A preferable content of the rubbery polymer in the rubber-containing graft (co) polymer (a-1) is 40 to 70% by weight. If this content is less than 40% by weight, the impact resistance of the resulting molded product will be inferior, and if it exceeds 70% by weight, the graft ratio will be lowered, so that the impact resistance will be inferior.
[0048]
  Of the rubber-reinforced styrene resin (A) component used in the present invention, the hard (co) polymer (a-2) is further required to have an aromatic vinyl monomer and a vinyl cyanide monomer. A polymer or a copolymer obtained by polymerizing or copolymerizing one or more of other copolymerizable unsaturated monomers used depending on the condition, and comprising an aromatic vinyl monomer and a vinyl cyanide monomer. The monomer and other copolymerizable unsaturated monomers used as necessary are the same as those exemplified as the monomer to be grafted to the rubber-containing graft (co) polymer (a-1). Monomers are used.
[0049]
  In the hard (co) polymer (a-2), the ratio of these monomer components is as follows: aromatic vinyl monomer: vinyl cyanide monomer: other monomer = 80-60: It is preferable to set it as 20-40: 0-60.
[0050]
  Further, the weight average molecular weight of the hard (co) polymer (a-2) is preferably 80,000 to 200,000. When the molecular weight is less than 80,000, the impact resistance is inferior, and when it exceeds 200,000, the molding is performed. Workability deteriorates.
[0051]
  The rubber-reinforced styrene resin (A) according to the present invention is composed of a rubber-containing graft (co) polymer (a-1) and a hard (co) polymer (a-2). These ratios are set to 100% by weight in total of 5 to 100% by weight of the rubber-containing graft (co) polymer (a-1) and 95 to 0% by weight of the hard (co) polymer (a-2). If the amount of the hard (co) polymer (a-2) is large and the amount of the rubber-containing graft (co) polymer (a-1) is small, the resulting molded article has poor impact resistance.
[0052]
  Among the polycarbonate resin (B) components used in the present invention, a polycarbonate resin (b-) having a number average molecular weight (hereinafter sometimes referred to as “viscosity average molecular weight”) by a solution viscosity method of 18,000 to 40,000. 1) can be produced by reaction of one or more bisphenols with phosgene or a carbonic acid diester. Specific examples of bisphenols include hydroquinone, 4,4-dihydroxyphenyl, bis- (4-hydroxyphenyl) -alkane, bis- (4-hydroxyphenyl) -cycloalkane, bis- (4-hydroxyphenyl) -sulfide Bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -ketone, bis- (4-hydroxyphenyl) -sulfone, or their alkyl-substituted, aryl-substituted, halogen-substituted, etc. These may be used alone or in combination of two or more.
[0053]
  As the polycarbonate resin (b-1), 2,2-bis- (4-hydroxyphenyl) propane, a bisphenol A-based polycarbonate resin using bisphenol A as a raw material is preferable because it can be easily obtained on the market.
[0054]
  Among the polycarbonate resin (B) components used in the present invention, the polycarbonate resin (b-2) is a recovered polycarbonate resin recovered by the method for recovering a thermoplastic resin from the waste optical disc of the present invention described above. .
[0055]
  The waste optical disc for recovering the recovered polycarbonate resin (b-2) is not particularly limited, and may be any of commercially available music CDs, game CDs, MD, MO, DVD, etc. All that uses is used as a base material. The recovered polycarbonate resin (b-2) may be used after being pulverized after the film is peeled off with an acid solution as in the examples described later, or may be used after being pulverized before the peeling process.
[0056]
  The polycarbonate resin (B) component used in the present invention is composed of 0 to 99% by weight of a polycarbonate resin (b-1) having a viscosity average molecular weight of 18,000 to 40,000 and 100 to 1% by weight of the recovered polycarbonate resin (b-2). %, And the range of the viscosity average molecular weight of the polycarbonate resin (B) obtained by mixing the recovered polycarbonate resin (b-2) with the polycarbonate resin (b-1) as necessary is 12,000-30, 000 is desirable. If the viscosity average molecular weight is less than 12,000, the impact strength of the obtained thermoplastic resin molded article is low, and if it exceeds 30,000, the fluidity of the thermoplastic resin composition tends to deteriorate, so this viscosity average molecular weight range. The recovered polycarbonate resin (b-2) is blended with a polycarbonate resin (b-1) having a large viscosity average molecular weight.
[0057]
  In the thermoplastic resin composition of the present invention, 10 to 70 parts by weight of the rubber-reinforced styrenic resin (A) and 90 to 30 parts by weight of the polycarbonate resin (B) are blended as the resin component in a total of 100 parts by weight. However, it is particularly preferable to blend them so that the total rubber content in the resin component is 3 to 20% by weight. If the total rubber content is less than 3% by weight, the resulting molded thermoplastic resin product is inferior in impact resistance. If the total rubber content exceeds 20% by weight, the thermoplastic resin composition has poor fluidity. Become.
[0058]
  Furthermore, the thermoplastic resin composition of the present invention may contain 30 parts by weight or less of the flame retardant (C) and 1 part by weight or less of the anti-drip agent (D) with respect to 100 parts by weight of the resin component. good.
[0059]
  As the flame retardant (C), a flame retardant selected from a phosphorus-based flame retardant and a bromine-based flame retardant can be used alone or in admixture of two or more.
[0060]
  Examples of the phosphorus-based flame retardant used in the present invention include red phosphorus and phosphorus compounds. Examples of the phosphorus compound include phosphine, phosphine oxide, bisphosphine, phosphonium salt, phosphinate, phosphate ester, and phosphite ester. Etc. Of these, phosphate ester-based flame retardants are preferred in that there is no problem of mold contamination or generation of corrosive gas during molding. Examples of the phosphate ester flame retardant include a phosphate ester compound represented by the following general formula (I) and a condensed phosphate ester compound represented by the following general formula (II).
[0061]
[Chemical 1]

((I) where R¹, R²And R^ThreeRepresents an alkyl group having 1 to 8 carbon atoms which is independently selected from each other, or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted, and n is 0 or 1. )
[0062]
[Chemical formula 2]

((II) where R^Four, R^Five, R⁶And R⁷Represents an aryl group or an alkaryl group independently selected from each other, X represents an arylene group, and j, k, l, and m are each independently 0 or 1. N is an integer of 1 to 5, but in the case of a mixture of phosphate ester compounds, N represents an average value (1 ≦ N ≦ 5). )
[0063]
  Specific examples of the phosphoric acid ester compound represented by the general formula (I) include bis- (phenyl) -methyl phosphate, bis- (ethyl) -phenyl phosphate, bis- (ethyl) -2,6-dimethylphenyl. Phosphate, bis- (phenyl) -ethyl phosphate, bis- (phenyl) -butyl phosphate, bis- (neopentyl) -phenyl phosphate, bis- (4-methylphenyl) -2-ethylhexyl phosphate, bis- (2-ethylhexyl) -Phenyl phosphate, bis- (phenyl) -2-ethylhexyl phosphate, bis- (phenyl) -octyl phosphate, bis- (octyl) phenyl phosphate, bis- (3,5,5-trimethylhexyl) phenyl phosphate, bis- ( 2,5,5-trimethyl Xyl) -4-methylphenyl phosphate, bis- (phenyl) -isodecyl phosphate, bis- (dodecyl) -4-methylphenyl phosphate, bis- (dodecyl) phenyl phosphate, tris- (phenyl) phosphate, tris- (2 -Methylphenyl) phosphate, tris- (4-methylphenyl) phosphate, bis- (2-methylphenyl) phenyl phosphate, bis- (4-methylphenylphenyl) phenyl phosphate, bis- (phenyl) -2-methylphenyl phosphate Bis- (phenyl) -4-methylphenyl phosphate, tris- (isopropylphenyl) phosphate, bis- (isopropylphenyl) phenyl phosphate, bis- (phenyl) -isopropylphenyl phosphate, Lis- (nonylphenyl) phosphate, tris- (2,6-dimethylphenyl) phosphate, bis- (2,6-dimethylphenyl) phenyl phosphate, bis- (2,6-dimethylphenyl) -2,6-dimethylphenyl Phosphate, bis- (2,6-dimethylphenyl) -4-t-butylphenyl phosphate, bis- (2,6-dimethylphenyl) -4-methylphenyl phosphate, bis- (2,6-dimethylphenyl) -3 -Methylphenyl phosphate, bis- (2,6-dimethylphenyl) -4-isopropylphenyl phosphate, bis- (2,6-dimethylphenyl) -2-isopropylphenyl phosphate, and these are used alone. Or two or more of them may be used in combination.
[0064]
  Moreover, the condensed phosphate ester compound represented by the general formula (II) may be used alone or in combination of two or more. Therefore, in the said general formula (II), the value of N does not necessarily need to be an integer, and in the case of a mixture, it represents the average value in the mixture of a condensed phosphate ester compound. In the general formula (II), R^Four, R^Five, R⁶And R⁷Is preferably cresyl group, phenyl group, xylenyl group, propylphenyl group, butylphenyl group, and the arylene group of X is derived from dihydroxy compounds such as resorcinol, hydroquinone, bisphenol A and their chlorinated and brominated compounds. Or a phenylene group or the like.
[0065]
  As the phosphoric flame retardant, the above phosphoric acid ester compound and the condensed phosphoric acid ester may be used in combination.
[0066]
  The brominated flame retardant used in the present invention includes at least one flame retardant selected from brominated epoxy polymers. The brominated epoxy polymer refers to an addition polymer of a brominated bisphenol compound and epichlorohydrin or a brominated bisphenol compound diglycidyl ether. Here, examples of the brominated bisphenol compound include tetrabromobisphenol A, dibromobisphenol A, tetrabromobisphenol F, and tetrabromobisphenol S. The molecular weight of the brominated epoxy polymer ranges from several hundred to several tens of thousands depending on the degree of polymerization (the number of repetitions of brominated bisphenol compound and 2-hydroxypropane unit). The molecular end of the brominated epoxy polymer may be an epoxy group or may be modified with an aryl group or an alkyl group, and these aryl group or alkyl group may be substituted with bromine. Examples of the aryl group include a phenyl group, a xylyl group, and a tribromophenyl group. Examples of the alkyl group include a methyl group, an ethyl group, and a tribromoneopentyl group.
[0067]
  Specific examples of the brominated epoxy polymer include tetrabromobisphenol A / epoxy polymer and tribromophenol-modified tetrabromobisphenol A / epoxy polymer.
[0068]
  When the blending amount of such a flame retardant (C) exceeds 30 parts by weight with respect to 100 parts by weight of the resin component described above, the heat resistance and mechanical properties of the obtained molded product are deteriorated. It is preferably 30 parts by weight or less, particularly 5 to 25 parts by weight based on 100 parts by weight of the resin component.
[0069]
  Examples of the anti-drip agent (D) added in the present invention include resins having a fluorine atom in the resin. Specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetra Fluoroethylene / hexafluoropropylene copolymers can be mentioned, and these can be used alone or in combination of two or more. Among these, polytetrafluoroethylene is particularly preferred. There are no particular restrictions on the method for producing such a fluororesin, and generally known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization can be employed. From the viewpoint, a fluororesin produced by emulsion polymerization is preferred.
[0070]
  The fluororesin is a component for improving the melt dripping property at the time of combustion, and sufficient flame retardancy can be obtained even when the fluororesin is not blended by blending the flame retardant (C). However, it becomes possible to achieve V-0 in the UL94 combustion rank by blending the fluororesin. However, since the mechanical strength and processing fluidity of the resin decrease when the amount of the fluorine resin is too large, when the fluorine resin is compounded, the compounding amount is 1 weight with respect to 100 parts by weight of the resin component. Part or less, particularly 0.01 to 1 part by weight. When the blending amount of the fluororesin is 0 part by weight with respect to 100 parts by weight of the resin component, it is a case where V-2 is aimed at the UL94 combustion rank. The prevention effect can be exhibited and V-0 can be achieved.
[0071]
  The thermoplastic resin composition of the present invention further contains 5 to 60 parts by weight of one or more inorganic fillers (E) such as carbon fiber and metal fiber with respect to 100 parts by weight of the resin component. May be.
[0072]
  As this carbon fiber, what has a fiber diameter of 4-20 micrometers and a fiber length of 3-20 mm is preferable. If the fiber diameter of the carbon fiber is less than 4 μm, it is difficult and expensive to produce the carbon fiber, and if it exceeds 20 μm, sufficient conductivity and electromagnetic wave shielding effect cannot be obtained with a small amount. If the fiber length of the carbon fiber is less than 3 mm, sufficient conductivity and electromagnetic wave shielding effect cannot be obtained with a small amount, and if it exceeds 20 mm, the fluidity at the time of melting the resin is lowered, and kneading extrusion tends to be difficult. In addition, there is no restriction | limiting in particular as a form of carbon fiber, Any of a PAN system and a pitch system may be sufficient. A preferable blending amount of the carbon fiber is 5 to 40 parts by weight with respect to 100 parts by weight of the resin component. When the blending amount is less than 5 parts by weight, sufficient conductivity and electromagnetic wave shielding effect cannot be obtained, and when it exceeds 40 parts by weight, not only the appearance is deteriorated, but also when a kneading extruder or the like is used during production, Excessive shearing heat is generated in the kneader, so that the polymer is decomposed and cannot be produced.
[0073]
  The metal fiber is preferably a stainless fiber, and preferably has a fiber diameter of 5 to 60 μm and a fiber length of 2 to 10 mm. When the fiber diameter of the stainless steel fiber is less than 5 μm, it is difficult to produce the stainless steel fiber. When the fiber diameter exceeds 60 μm, high conductivity and electromagnetic wave shielding effect in a small amount tend to be difficult to obtain. Further, if the fiber length is less than 2 mm, high conductivity and electromagnetic wave shielding effect in a small amount are difficult to obtain, and if it exceeds 10 mm, the fluidity at the time of melting the resin tends to be lowered and kneading extrusion tends to be difficult. A preferable blending amount of the stainless fiber is 5 to 40 parts by weight with respect to 100 parts by weight of the resin component. When the blending amount is less than 5 parts by weight, sufficient conductivity and electromagnetic wave shielding effect cannot be obtained, and when it exceeds 40 parts by weight, not only the appearance is deteriorated, but also when a kneading extruder or the like is used during production, Excessive shearing heat is generated in the machine, and the polymer decomposes and cannot be produced.
[0074]
  In addition, when the carbon fiber and the stainless fiber are used in combination, the mixing ratio is preferably carbon fiber: stainless fiber = 1: 0.5 to 3 in terms of weight ratio in terms of conductivity and electromagnetic shielding effect, Moreover, it is preferable that the total compounding quantity of a carbon fiber and a stainless fiber is 5-60 weight part with respect to 100 weight part of resin components, especially 5-40 weight part.
[0075]
  In addition, the thermoplastic resin composition of the present invention includes known antioxidants, ultraviolet absorbers, lubricants, plasticizers, mold release agents, antistatic agents, colorants (pigments) as long as they do not interfere with the spirit of the present invention. And other additives such as flame retardant aids such as fillers and antimony compounds, antibacterial agents, antifungal agents, silicone oils, and coupling agents. Further, it may contain a phosphorus-based flame retardant, a flame retardant other than bromine, or a conductive material other than carbon fiber or stainless fiber.
[0076]
  Although there is no restriction | limiting in particular as a method of mixing these compounding components and manufacturing the thermoplastic resin composition of this invention, For example, the melt-kneading method using an extruder, a Banbury mixer, etc. is preferable.
[0077]
  The thermoplastic resin composition of the present invention thus obtained can be molded into various molded products by injection molding, sheet extrusion, vacuum molding, pressure molding, profile extrusion molding, foam molding, blow molding and the like.
[0078]
  The thermoplastic resin molded article of the present invention obtained by molding the thermoplastic resin composition of the present invention can be used for vehicle parts and general equipment by adjusting the composition of the thermoplastic resin composition, for example, The flame retardant (C) and the anti-drip agent (D) can be used for OA equipment due to the high flame retardancy, and further, the inorganic filler (E) can be blended to provide conductivity. This may cause problems with electromagnetic interference (EMI), such as electrical and electronic equipment and housing of electronic equipment parts, especially OA equipment such as computers, printers, copiers, and mobile information including mobile computers. It can be suitably used for a housing of an apparatus.
[0079]
【Example】
  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, comparative examples, and reference examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Absent.
[0080]
  In the following, the viscosity average molecular weight (Mv) was measured by the following method.
[Measurement Method of Viscosity Average Molecular Weight (Mv)]
  The sample was measured as a solution using methylene chloride as a solvent, using a Webellode viscometer, and determined using the following Schnell viscosity equation.
      [Η] = 1.23 × 10^-4× Mv^0.83
      (In the formula, η indicates the intrinsic viscosity.)
[0081]
[Recovery of polycarbonate resin from waste CD]
  Example 13, Comparative Examples 12-15
  100 waste CDs collected from the market were immersed in 30 L of an acid solution having the composition and pH shown in Table 1 at 30 ° C. for 30 hours at a distance of several mm from each other in a disk shape. Thereafter, the waste CD was taken out from the acid solution, washed with water, and then air-dried at 80 ° C.
[0082]
  As a result, Examples 1 to3 and Comparative Examples 12 and 13Then, all the coatings such as the aluminum reflecting film, the protective film and the printing film could be dissolved or peeled off, and the polycarbonate resin containing no impurities could be recovered. However, in Examples 1 to 3, the film could be completely peeled and removed by the immersion treatment for 10 minutes.Comparative Examples 12 and 13Then, it took 45 minutes to process. Also,Comparative Examples 14 and 15Then, the film could not be removed sufficiently even after the treatment for 60 minutes.
[0083]
[Table 1]

[0084]
  In order to check that the recovered polycarbonate resin has no difference in physical properties from the polycarbonate resin before recovery, the viscosity average of the polycarbonate resin that is the molding material of the waste CD substrate before recovery and the recovered polycarbonate resin When the molecular weight was examined, the viscosity average molecular weight of the polycarbonate resin before molding was 1.45 × 10.⁴Met.
[0085]
  On the other hand, the viscosity average molecular weight measurement results of the polycarbonate resin recovered in each example are as shown in Table 2, and the molecular weight does not decrease with respect to the polycarbonate resin before molding, and the polycarbonate has the same physical properties as before use. It can be seen that the resin could be recovered.
[0086]
  Comparative Example 1
  Exfoliation treatment was carried out in the same manner as in Example 1 except that an alkaline solution (pH 14) containing 8% by weight of sodium hydroxide, 1.8% by weight of sodium gluconate and 0.2% by weight of alkylamine oxide was used as the treatment liquid. Went. After soaking for 60 minutes, the waste CD is taken out of the processing solution and washed with water. The aluminum reflective film, protective film, printed film, etc. are not sufficiently peeled off and removed, and it is possible to collect polycarbonate resin that does not contain impurities. could not.
[0087]
  Comparative Example 2
  Exfoliation treatment was performed in the same manner as Comparative Example 1 except that the treatment temperature was 90 ° C. After soaking for 60 minutes, the waste CD is taken out of the processing solution and washed with water. As a result, all the coatings such as the aluminum reflective film, protective film, and printed film are dissolved or removed, and the polycarbonate resin containing no impurities is recovered. I was able to.
[0088]
  However, when the viscosity average molecular weight of the recovered polycarbonate resin was measured, as shown in Table 2, a decrease in molecular weight was observed.
[0089]
  Comparative Example 3
  Exfoliation treatment was performed in the same manner as in Comparative Example 1 except that 100 waste CDs were crushed to about 2 to 10 mm and then treated with an alkaline solution. After soaking for 60 minutes, the waste CD fragments are removed from the treatment liquid and washed with water. The aluminum reflective film, protective film, printed film, etc. are not peeled off and removed, and it is possible to collect polycarbonate resin that does not contain impurities. could not.
[0090]
[Table 2]

[0091]
[Production of thermoplastic resin composition and thermoplastic resin molded article]
  In the following, “part” means “part by weight”.
[0092]
  Synthesis Example 1: Production of rubber-containing graft copolymer (a-1-1)
  An ABS copolymer was synthesized by the emulsion polymerization method with the following composition.
[Combination]
    Styrene (ST) 35 parts
    15 parts of acrylonitrile (AN)
    50 parts of polybutadiene latex (as solids)
    Disproportionated potassium rosinate 1 part
    Potassium hydroxide 0.03 parts
    Terrierid decyl mercaptan (t-DM) 0.1 part
    Cumene hydroperoxide 0.3 parts
    Ferrous sulfate 0.007 parts
    Sodium pyrophosphate 0.1 part
    0.3 parts of crystalline glucose
    190 parts distilled water
[0093]
  Charge the autoclave with distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutadiene latex, heat to 60 ° C, add ferrous sulfate, sodium pyrophosphate, and crystalline glucose, and keep it at 60 ° C. AN, t-DM and cumene hydroperoxide were continuously added over 2 hours, and then the temperature was raised to 70 ° C. and maintained for 1 hour to complete the reaction. An antioxidant was added to the ABS latex obtained by this reaction, then coagulated with sulfuric acid, sufficiently washed with water, and dried to obtain an ABS graft copolymer (a-1-1).
[0094]
  Synthesis Example 2: Production of rubber-containing graft copolymer (a-1-2)
  Reaction of 15 parts of AN and 35 parts of ST in the presence of 50 parts (as solids) of ethylene-propylene-nonconjugated diene copolymer rubber latex (ethylene: propylene: nonconjugated diene (5-ethylene-2-norbornene)) Except for this, an AES graft copolymer (a-1-2) was obtained in the same manner as in Synthesis Example 1.
[0095]
  Synthesis Example 3: Production of rubber-containing graft copolymer (a-1-3)
  An ASA graft copolymer (a-1-3) was obtained in the same manner as in Synthesis Example 1, except that 15 parts of AN and 35 parts of ST were reacted in the presence of 50 parts of polybutyl acrylate (as a solid content).
[0096]
  Synthesis Example 4: Production of hard copolymer (a-2-1)
  Monomer consisting of 120 parts water, 0.002 part sodium alkylbenzene sulfonate, 0.5 part polyvinyl alcohol, 0.3 part azoisobutylnitrile, 0.5 part t-DM, 35 parts AN, and 65 parts ST in a nitrogen-substituted reactor. Using the mixture, heating was started at a starting temperature of 60 ° C. for 5 hours and then reached 120 ° C. while adding a portion of ST sequentially. Furthermore, after reacting at 120 ° C. for 4 hours, the polymer was taken out to obtain a hard copolymer (a-2-1).
[0097]
  Synthesis Example 5: Production of hard copolymer (a-2-2)
  Example of synthesis except that a monomer mixture consisting of 25 parts of AN, 20 parts of ST, 35 parts of α-methylstyrene and 20 parts of N-phenylmaleimide was used, and a part of styrene, α-methylstyrene and N-phenylmaleimide was sequentially added. Polymerization was conducted in the same manner as in Example 4 to obtain a hard copolymer (a-2-2).
[0098]
  The following were used as the polycarbonate resin (b-1).
  Polycarbonate resin (b-1-1): Polycarbonate resin “H-4000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (viscosity average molecular weight (Mv): 15,000)
  Polycarbonate resin (b-1-2): Polycarbonate resin “S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (viscosity average molecular weight (Mv): 21,000)
  Polycarbonate resin (b-1-3): Polycarbonate resin “E-2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (viscosity average molecular weight (Mv): 31,000)
[0099]
  As the recovered polycarbonate resin (b-2), the following was used.
[0100]
  Recovered polycarbonate resin (b-2-1): Waste CD was immersed in the acid solution used in Example 1 for 5 minutes to remove the coating, washed with water, dried and crushed. The viscosity average molecular weight (Mv) of the raw material polycarbonate resin used for this waste CD was 15,000, and the viscosity average molecular weight (Mv) of the recovered polycarbonate resin was also 15,000.
[0101]
  Polycarbonate resin (b-2-2): Waste MD was immersed in the acid solution used in Example 5 for 5 minutes to remove the coating, washed with water, dried and crushed. The raw material polycarbonate resin used for the waste MD had a viscosity average molecular weight (Mv) of 15,000, and the recovered polycarbonate resin also had a viscosity average molecular weight (Mv) of 14,900.
[0102]
  Polycarbonate resin (b-2-3): Waste CDComparative Example 14What was dipped in the acid solution used in 90 minutes and was not able to sufficiently peel off the metal film or paint, washed with water, dried and crushed. The viscosity average molecular weight (Mv) of the raw material polycarbonate resin used for the waste CD was 15,000, and the viscosity average molecular weight (Mv) of the recovered polycarbonate resin was 13,500.
[0103]
  Polycarbonate resin (b-2-4): A product obtained by crushing a waste CD without removing the metal coating or coating.
[0104]
  Polycarbonate resin (b-2-5): A crushed as it is without removing the metal coating or coating of waste MD.
[0105]
  The following were used as the flame retardant (C).
  Flame retardant (c-1): Phosphoric ester flame retardant “FP-500” manufactured by Asahi Denka Kogyo
  Flame retardant (c-2): Bromine flame retardant “EC-20” manufactured by Dainippon Ink
[0106]
  As the anti-drip agent (D), the following were used.
  Anti-drip agent (d): Polytetrafluoroethylene “Teflon (registered trademark) 6-J” manufactured by DuPont
[0107]
  The following were used as the inorganic filler (E).
  Inorganic filler (e-1): Carbon fiber “Besphite” manufactured by Toho Rayon Co., Ltd. (average fiber diameter = 7 μm, average fiber length = 6 mm)
  Inorganic filler (e-2): stainless steel fiber “Bekishield” manufactured by Bekaert (average fiber diameter = 8 μm, average fiber length = 6 mm)
[0108]
  Examples 8-15, Comparative Examples 4-11, Reference Examples 1-4
  After mixing with additives such as lubricants and antioxidants at the blending ratios shown in Tables 3 and 4, melt mixing at 220 to 240 ° C. with a twin screw extruder (“TEX-44” manufactured by Nippon Steel) And pelletized. This resin pellet was molded at 220 to 260 ° C. with a 2 ounce injection molding machine (manufactured by Toshiba Corporation), necessary test pieces were prepared, and various physical properties were measured by the following methods. This is shown in FIG.
[0109]
  Reference Examples 1 to 4 are examples in which only the new polycarbonate resin is used without using the recovered polycarbonate resin.
[Melt flow rate (g / 10 min)] JIS K7210 (230 ° C in Table 3, 220 ° C / 98N in Table 4)
[Izod impact strength (J / m)] ASTM D256 (room temperature)
[Flexural modulus (MPa)] 6.4 mm thickness (ASTM D790)
[Heat deformation temperature (° C)] ASTM D648
[Flammability] A 2 mm-thickness test piece was subjected to a combustion test according to UL94 to examine the flammability.
[Surface Appearance] The surface of the molded product was visually observed, and it was determined that there was no foreign matter and the appearance was good, and that the appearance was bad and the appearance was bad was ×.
[0110]
[Table 3]

[0111]
[Table 4]

[0112]
  From Tables 3 and 4, the following is clear.
[0113]
  In Examples 8-11 of this invention, it turns out that surface appearance and Izod impact strength are excellent compared with Comparative Examples 4-7. In addition, Example 8 can be compared with Reference Example 1, Example 10 can be compared with Reference Example 2, and Examples 8 and 10 show the same characteristics as Reference Examples 1 and 2. Therefore, it is expected to withstand practical use.
[0114]
  Although Examples 12 and 13 and Comparative Examples 8 and 9 to which flame retardants and anti-drip agents were added had an effect on combustibility, Examples 12 and 13 were far more excellent in terms of surface appearance and Izod impact strength. It turns out that it is excellent in. In addition, Example 12 shows the same characteristics as Reference Example 3, and is expected to be sufficiently practical.
[0115]
  Further, Examples 14 and 15 and Comparative Examples 10 and 11 are resin compositions in which carbon fibers or stainless fibers as inorganic fillers are blended, and a square test piece having a side of 150 mm and a thickness of 3 mm is created for the electromagnetic wave shielding effect. Then, when the magnetic wave (frequency 300 MHz) was measured in combination with TR-17301A and R3361A manufactured by Advantest Co., Ltd., the electromagnetic wave shielding effects of Examples 14 and 15, Comparative Examples 10 and 11 and Reference Example 4 were It was in the range of 50 to 55 (dB), and the electromagnetic wave shielding effect was recognized in all. Moreover, the effect on combustibility was recognized. However, Examples 14 and 15 are far superior to Comparative Examples 10 and 11 in terms of surface appearance and Izod impact strength characteristics. In addition, Example 14 shows the same characteristics as Reference Example 4, and is expected to be sufficiently practical.
[0116]
  As mentioned above, in an Example, compared with what uses the ground product of a comparative example, impact strength strength and appearance are excellent. Further, as shown in the reference example, it is apparent that the characteristics of the examples have characteristics comparable to those in which the recovered polycarbonate resin is not reused.
[0117]
【The invention's effect】
  As described above in detail, according to the method for recovering a thermoplastic resin from a waste optical disc of the present invention, only a coating such as a metal reflective film on a thermoplastic resin substrate can be easily and efficiently removed from the waste of the optical disc. The thermoplastic resin, which is a constituent material of the substrate, can be recovered at a high recovery rate while maintaining the reusable physical properties without reducing the physical properties.
[0118]
  Moreover, according to the thermoplastic resin composition and the thermoplastic resin molded article of the present invention, a thermoplastic resin molded article having excellent surface appearance and impact resistance is provided using the recovered thermoplastic resin. be able to.
[0119]
  According to the present invention, the demand for thermoplastic resin is easily and efficiently increased from the waste of optical disks, which are expected to increase in demand in recent years, and the amount of defective products, test samples, recovered products, etc. is expected to increase. Moreover, it can be recovered at low cost and reused, and the industrial utility of the present invention is extremely high in terms of waste reduction, environmental maintenance, effective use of resources, and the like.

Claims (14)

In a method for recovering thermoplastic resin from waste optical discs in which a coating including a metal reflective film is formed on a thermoplastic resin substrate,
The optical disc is brought into contact with an acid solution, the film is dissolved or peeled off, washed with water, and dried .
A method for recovering a thermoplastic resin from a waste optical disc , wherein the acid solution is an aqueous solution containing an inorganic acid, an organic acid, a halogen compound, and a penetrant .   2. The method for recovering a thermoplastic resin from a waste optical disc according to claim 1, wherein the thermoplastic resin is a polycarbonate resin.   The method for recovering a thermoplastic resin from a waste optical disc according to claim 1 or 2, wherein the acid solution has a pH of 3 or less. The inorganic acid of the acid solution is one or more selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and the organic acid consists of citric acid, sulfamic acid, oxalic acid, glycolic acid, acetic acid and formic acid. One or more selected from the group, the halogen compound is one or more selected from the group consisting of sodium halide, potassium halide, ammonium halide and hydrohalic acid, and the penetrant is The waste optical system according to any one of claims 1 to 3, wherein the optical system is one or more selected from the group consisting of polyoxyalkylene alkyl ethers, alkylbenzene sulfonates and naphthalene sulfonates. Recovery method of thermoplastic resin from disk. The acid solution has an inorganic acid concentration of 10 to 80% by weight, an organic acid concentration of 1 to 20% by weight, a halogen compound concentration of 1 to 30% by weight, and a penetrant concentration of 0. The method for recovering a thermoplastic resin from a waste optical disc according to any one of claims 1 to 4, wherein the content is 1 to 5% by weight. The method for recovering a thermoplastic resin from a waste optical disk according to any one of claims 1 to 5 , wherein the optical disk is brought into contact with the acid solution without being crushed. The molecular weight M _{X of} the recovered thermoplastic resin is M ₀ × 1 to M ₀ × 0.95 with respect to the molecular weight M ₀ of the thermoplastic resin of the molding material of the substrate of the optical disk. A method for recovering a thermoplastic resin from a waste optical disc according to any one of claims 1 to 6 . A thermoplastic resin composition comprising a thermoplastic resin recovered by the method for recovering a thermoplastic resin from a waste optical disc according to any one of claims 1 to 7 . 9. The thermoplastic resin composition according to claim 8, wherein the thermoplastic resin composition is recovered by a method for recovering a thermoplastic resin from a rubber-reinforced styrene resin and a waste optical disk according to any one of claims 1 to 7. A thermoplastic resin composition comprising a polycarbonate resin. In claim 9 ,
(A) A rubber-containing graft obtained by graft polymerization of one or more vinyl monomers selected from an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubber-like polymer ( 10) to 70 parts by weight of a rubber-reinforced styrene resin containing a (co) polymer (a-1);
(B) 90 to 30 parts by weight of polycarbonate resin containing the recovered polycarbonate resin (b-2) (however, (A) 100 parts by weight in total of rubber-reinforced styrene resin and (B) polycarbonate resin) A thermoplastic resin composition characterized by the above. In claim 10 ,
(A) A rubber-containing graft obtained by graft polymerization of one or more vinyl monomers selected from an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubber-like polymer ( Co) polymer (a-1) 5% by weight or more and a hard (co) polymerized from one or more monomers selected from aromatic vinyl monomers and vinyl cyanide monomers 10 to 70 parts by weight of a rubber-reinforced styrene resin containing 95% by weight or less of the polymer (a-2);
(B) Polycarbonate resin 90 containing 99% by weight or less of polycarbonate resin (b-1) having a number average molecular weight of 18,000 to 40,000 by solution viscosity method and 1% by weight or more of the recovered polycarbonate resin (b-2) -30 parts by weight (however, the total of (A) rubber-reinforced styrene resin and (B) polycarbonate resin is 100 parts by weight). In Claim 10 or 11 , (C) 30 parts by weight or less of flame retardant and (D) 1 part by weight of anti-drip agent for 100 parts by weight of the total of (A) rubber-reinforced styrene resin and (B) polycarbonate resin The thermoplastic resin composition characterized by including the following. In any one of claims 10 to 12, (A) 100 parts by weight of the total of the rubber-reinforced styrene resin and (B) a polycarbonate resin, comprising (E) an inorganic filler 5 to 60 parts by weight A thermoplastic resin composition characterized by the above. A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to any one of claims 8 to 13 .