JP4456253B2 - Synthetic fiber treatment agent for carbon fiber production and method for treating synthetic fiber for carbon fiber production - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は炭素繊維製造用合成繊維処理剤（以下、単に処理剤という）及び炭素繊維製造用合成繊維の処理方法（以下、単に処理方法という）に関する。ピッチ繊維やアクリル繊維から炭素繊維を製造する場合、高品質の炭素繊維を低コストで製造するため、耐炎化工程において、耐炎化繊維相互の融着防止を図ることが要求されると同時に、糸切れの発生防止を図ることが要求される。本発明はかかる要求に応える処理剤及び処理方法に関する。
【０００２】
【従来の技術】
従来、上記のような処理剤として、各種の変性ポリオルガノシロキサンを含有するものが使用されている。これには、１）ポリオキシアルキレン変性ポリオルガノシロキサンやエポキシ変性ポリオルガノシロキサンを含有する処理剤（特開昭５２−１４８２２７）、２）アミノ変性ポリオルガノシロキサンを含有する処理剤（特公昭６４−５０８、特公昭５２−２４１３６、特開昭６０−９９０１１、特開平２−９１２２４、特開平６−２２０７２３、特開平８−２０９５４３）等がある。ところが、かかる従来の処理剤には、耐炎化工程において、耐炎化繊維相互の融着防止と糸切れの発生防止とを同時に且つ充分に図ることができないという問題がある。
【０００３】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、耐炎化工程において、耐炎化繊維相互の融着防止と糸切れの発生防止とを同時に且つ充分に図ることができる処理剤及び処理方法を提供する処にある。
【０００４】
【課題を解決するための手段】
しかして本発明者らは、上記の課題を解決するべく研究した結果、特定のアミノ変性ポリオルガノシロキサンと特定の多環芳香族化合物とを合計で所定量以上且つ双方を所定割合で含有して成る処理剤が正しく好適であり、またかかる処理剤を炭素繊維製造用合成繊維に所定量付着させる処理方法が正しく好適であることを見出した。
【０００５】
すなわち本発明は、下記の式１で示されるアミノ変性ポリオルガノシロキサンと下記の式２で示される多環芳香族化合物とを合計で５５重量％以上含有し且つ該アミノ変性ポリオルガノシロキサン／該多環芳香族化合物＝９５／５〜６０／４０（重量比）の割合で含有して成ることを特徴とする処理剤に係る。
【０００６】
【式１】
Ｔn−Ｂ−Ｏ−Ｙ−ＯＨ
【０００７】
式１、式２において、
Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7：メチル基
Ａ1，Ａ2：メチル基
Ｘ：３−アミノプロピル基又はＮ−（２−アミノエチル）−３−アミノプロピル基
ｐ：１〜１０００の整数
ｑ：１〜５０の整数
ｎ：１〜５の整数
Ｂ：フェノールから水酸基と芳香環に直結する１〜３個の水素とを除いた残基又は置換基として炭素数１〜３のアルキル基を有するアルキルフェノールから水酸基と芳香環に直結する１〜３個の水素とを除いた残基
Ｔ：ベンジル基
Ｙ：オキシエチレン単位のみ又はオキシエチレン単位とオキシプロピレン単位の双方からなるオキシアルキレン単位の数が１〜３０の（ポリ）オキシアルキレングリコールから全ての水酸基を除いた残基
【０００８】
また本発明は、前記のような本発明に係る処理剤を、炭素繊維製造用合成繊維に対し０．２〜１．５重量％となるよう付着させることを特徴とする処理方法に係る。
【０００９】
式１で示されるアミノ変性ポリオルガノシロキサンは、アミノ変性基を主鎖の側鎖にのみ有するアミノ変性ポリオルガノシロキサンである。かかるアミノ変性ポリオルガノシロキサンは、主鎖を構成する２価のオルガノシロキサン単位と、末端を構成する１価のオルガノシロキサン単位及び１価のオルガノシリル単位とで構成されている。主鎖を構成する２価のオルガノシロキサン単位には、式１中のｐで括られた２価のオルガノシロキサン単位とｑで括られた２価のオルガノシロキサン単位とがあり、ｑで括られた２価のオルガノシロキサン単位はアミノ変性基を有する。上記のような２価のオルガノシロキサン単位の結合位置はそれらが主鎖を構成する限りにおいて特に制限されない。
【００１０】
式１で示されるアミノ変性ポリオルガノシロキサンにおいて、主鎖を構成するｐで括られた２価のオルガノシロキサン単位のＲ3，Ｒ4はメチル基である。またｐで括られた２価のオルガノシロキサン単位の数は、１〜１０００とするが、５０〜５００とするのが好ましい。
【００１１】
式１で示されるアミノ変性ポリオルガノシロキサンにおいて、主鎖を構成するｑで括られた２価のオルガノシロキサン単位のＸは、アミノ変性基であり、３−アミノプロピル基又はＮ−（２−アミノエチル）−３−アミノプロピル基である。またｑで括られた２価のオルガノシロキサン単位のＲ5は、Ｒ3，Ｒ4と同様、メチル基である。かかるｑで括られた２価のオルガノシロキサン単位の数は、１〜５０とするが、１〜２０とするのが好ましい。
【００１２】
式１で示されるアミノ変性ポリオルガノシロキサンにおいて、主鎖の末端を構成する１価のオルガノシロキサン単位のＲ1，Ｒ2は、Ｒ3，Ｒ4と同様、メチル基であり、また主鎖の末端を構成する１価のオルガノシロキサン単位のＡ1もメチル基である。
【００１３】
式１で示されるアミノ変性ポリオルガノシロキサンにおいて、主鎖の末端を構成する１価のオルガノシリル単位のＲ6，Ｒ7は、Ｒ3，Ｒ4と同様、メチル基であり、また主鎖の末端を構成する１価のオルガノシリル単位のＡ2もメチル基である。
【００１４】
式１で示されるアミノ変性ポリオルガノシロキサンは、公知の方法で合成できる。これには例えば、１）環状ジオルガノポリシロキサンを、アルカリ触媒の存在下に、α、ω−ジヒドロキシアミノ変性ポリオルガノシロキサンと反応させる方法、２）ハイドロジェンポリオルガノシロキサンを、クロル白金酸触媒の存在下に、アリールアミン化合物と反応させる方法等が挙げられる。
【００１５】
式２で示される多環芳香族化合物において、式２中のＢは、フェノールから水酸基と芳香環に直結する１〜３個の水素とを除いた残基、又は置換基として炭素数１〜３のアルキル基を有するアルキルフェノールから水酸基と芳香環に直結する１〜３個の水素を除いた残基である。また式２中のＴは、ベンジル基である。かかるＴの数ｎは、１〜３である。更に式２中のＹは、１）１〜３０個のオキシエチレン単位を有する（ポリ）オキシエチレングリコールから全ての水酸基を除いた残基、又は２）合計で２〜３０個のオキシエチレン単位とオキシプロピレン単位との双方を有する（ポリ）オキシエチレン（ポリ）オキシプロピレングリコールから全ての水酸基を除いた残基である。
【００１６】
以上説明した式２で示される多環芳香族化合物としては、α−（トリベンジルフェニル）−ω−ヒドロキシ−ポリオキシエチレン（オキシエチレン単位の数１、以下ｖ＝１という）、α−（ジベンジルフェニル）−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝５）、α−（ジベンジルフェニル）−ω−ヒドロキシ−ポリオキシエチレンポリオキシプロピレン（ｖ＝１０、ｗ＝２）、α−（ジベンジルメチルフェニル）−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝１０）、α−（モノベンジルオルソメチルフェニル）−ω−ヒドロキシ−オキシエチレン（ｖ＝１）等が挙げられる。
【００１７】
式２で示される多環芳香族化合物は、公知の方法で合成できる。例えば、芳香環に直結する１個の水酸基を有する芳香族化合物に、ルイス酸触媒の存在下で、ベンジルクロライドを反応させて、該芳香環に直結する水素をベンジル基で置換した後、更に水酸化カリウム触媒の存在下でアルキレンオキサイドを付加重合させる方法が挙げられる。
【００１８】
本発明に係る処理剤は、以上説明したアミノ変性ポリオルガノシロキサンと多環芳香族化合物とを合計で５５重量％以上、好ましくは６０重量％以上含有し、且つ該アミノ変性ポリオルガノシロキサン／該多環芳香族化合物＝９５／５〜６０／４０（重量比）の割合、好ましくは９０／１０〜７５／２５（重量比）の割合で含有して成るものである。
【００１９】
本発明に係る処理剤は、以上説明したように、アミノ変性ポリオルガノシロキサンと多環芳香族化合物とを合計で所定量以上且つ双方を所定割合で含有するものであるが、更に有機カルボン酸のアミン塩を含有することができる。かかる有機カルボン酸のアミン塩を構成することとなる有機カルボン酸としては、１）酢酸、プロピオン酸、カプロン酸、ラウリン酸、２−エチルヘキサン酸、イソステアリン酸、オレイン酸、エルカ酸等の炭素数２〜３０の脂肪族モノカルボン酸、２）マロン酸、アジピン酸、イタコン酸、セバシン酸、ペンタデセニルコハク酸等の炭素数３〜３０の脂肪族ジカルボン酸、３）安息香酸、フタル酸、トリメリット酸等の炭素数７〜３０の芳香族カルボン酸、４）乳酸、酒石酸、リシノール酸、１２−ヒドロキシステアリン酸等の炭素数３〜３０の脂肪族ヒドロキシカルボン酸、５）チオジプロピオン酸等の炭素数３〜３０の含硫黄脂肪族カルボン酸等が挙げられる。なかでも炭素数２〜２２の脂肪族モノカルボン酸、炭素数２〜２２の脂肪族ヒドロキシカルボン酸が好ましく、酢酸、プロピオン酸、カプロン酸、ラウリン酸、オレイン酸等の炭素数２〜１８の脂肪族モノカルボン酸が特に好ましい。
【００２０】
また有機カルボン酸のアミン塩を構成することとなるアミン化合物としては、１）メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、ブチルアミン、ジブチルアミン、トリブチルアミン、オクチルアミン等の脂肪族アミン、２）モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、イソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ブチルジエタノールアミン、オクチルジエタノールアミン、ラウリルジエタノールアミン等のアルカノールアミン、３）α−ラウリルアミノ−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝６）、α−ステアリルアミノ−ω−ヒドロキシ−ポリオキシプロピレン（ｗ＝６）、α−オレイルアミノ−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝１５）等の脂肪族アミンのポリオキシアルキレン付加物、４）アニリン、ピリジン、モルホリン、ピペラジン、これらの誘導体等の芳香族アミン又は複素環アミン等が挙げられる。なかでもアルカノールアミン、脂肪族アミンのポリオキシアルキレン付加物が好ましい。以上説明した有機カルボン酸のアミン塩の含有量は、処理剤中、０．５〜２０重量％とするが、１〜１５重量％とするのが好ましい。
【００２１】
本発明に係る処理剤は、それが以上説明したような有機カルボン酸のアミン塩を含有するものの場合、更にポリオキシアルキレン変性ポリオルガノシロキサンを含有することができる。かかるポリオキシアルキレン変性ポリオルガノシロキサンとしては、主鎖の側鎖にポリオキシアルキレン変性基を有するものや主鎖の末端にポリオキシアルキレン変性基を有するもの等、各種が挙げられるが、主鎖の側鎖にポリオキシアルキレン変性基を有する数平均分子量１０００〜３００００のポリオキシアルキレン変性ポリオルガノシロキサンが好ましい。またポリオキシアルキレン変性ポリオルガノシロキサンのポリオキシアルキレン変性基としては、１）ポリオキシエチレン変性基、２）ポリオキシエチレン／ポリオキシプロピレン変性基が挙げられるが、なかでもポリオキシエチレン変性基が好ましく、数平均分子量２０００〜１５０００のポリオキシエチレン変性ポリオルガノシロキサンがより好ましい。以上説明したポリオキシアルキレン変性ポリオルガノシロキサンの含有量は、処理剤中、３〜２５重量％とするが、５〜２０重量％とするのが好ましい。
【００２２】
以上、本発明に係る処理剤について説明したが、該処理剤が式１で示されるアミノ変性ポリオルガノシロキサンと、式２で示される多環芳香族化合物と、前記した有機カルボン酸のアミン塩と、前記したポリオキシアルキレン変性ポリオルガノシロキサンとで構成される場合、該アミノ変性ポリオルガノシロキサンを６０〜８５重量％、該多環芳香族化合物を１０〜２５重量％、該有機カルボン酸のアミン塩を１〜１５重量％及び該ポリオキシアルキレン変性ポリオルガノシロキサンを５〜２０重量％（合計１００重量％）で含有するものが最も好ましい。
【００２３】
本発明に係る処理方法では、以上説明したような本発明に係る処理剤を炭素繊維製造用合成繊維に対し０．２〜１．５重量％、好ましくは０．３〜１．２重量％となるよう付着させる。
【００２４】
本発明に係る処理方法において、処理剤の付着方法としては、浸漬給油法、ローラー給油法、計量ポンプを用いたガイド給油法、スプレー給油法等の公知の方法が挙げられるが、浸漬給油法、ローラー給油法、計量ポンプを用いたガイド給油法が好ましい。
【００２５】
本発明に係る処理剤を炭素繊維製造用合成繊維に付着させるに当たり、該処理剤はその水性液、通常は水性エマルジョンとして用いるのが好ましい。処理剤の炭素繊維製造用合成繊維への付着に際しては、合目的的に他の成分、例えば、抗酸化剤、防腐剤、防錆剤等を併用することができるが、その使用量は可及的に少量とするのが好ましい。
【００２６】
本発明に係る処理剤及び処理方法は炭素繊維製造用のピッチ繊維或はアクリル繊維に適用できるが、アクリル繊維に適用する場合により効果が高い。
【００２７】
【発明の実施の形態】
本発明に係る処理剤及び処理方法の実施形態としては、次の１）〜１２）が挙げられる。
１）下記のアミノ変性ポリオルガノシロキサン（Ｍ−１）７７重量％、及び下記の多環芳香族化合物（Ｎ−１）２３重量％（合計１００重量％）から成る処理剤（Ｔ−１）。そしてこの処理剤（Ｔ−１）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１）として０．６重量％となるよう付着させる処理方法。
アミノ変性ポリオルガノシロキサン（Ｍ−１）：式１中のＲ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7，Ａ1，Ａ2がメチル基、ＸがＮ−（２−アミノエチル）−３−アミノプロピル基、ｐが６０、ｑが１である場合のアミノ変性ポリオルガノシロキサン。
多環芳香族化合物（Ｎ−１）：式２中のＴがベンジル基、ｎが３、Ｂがフェノールから水酸基と３個の水素とを除いた残基、Ｙがポリオキシエチレン（ｖ＝５）グリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
【００２８】
２）下記のアミノ変性ポリオルガノシロキサン（Ｍ−２）８５重量％、及び下記の多環芳香族化合物（Ｎ−２）１５重量％（合計１００重量％）から成る処理剤（Ｔ−２）。そしてこの処理剤（Ｔ−２）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−２）として０．８重量％となるよう付着させる処理方法。
アミノ変性ポリオルガノシロキサン（Ｍ−２）：式１中のＲ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7，Ａ1，Ａ2がメチル基、ＸがＮ−（２−アミノエチル）−３−アミノプロピル基、ｐが３２０、ｑが６である場合のアミノ変性ポリオルガノシロキサン。
多環芳香族化合物（Ｎ−２）：式２中のＴがベンジル基、ｎが２、Ｂがフェノールから水酸基と２個の水素を除いた残基、Ｙがポリオキシエチレン（ｖ＝１５）グリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
【００２９】
３）下記のアミノ変性ポリオルガノシロキサン（Ｍ−３）８９重量％、下記の多環芳香族化合物（Ｎ−３）８重量％、及び下記の多環芳香族化合物（Ｎ−５）３重量％（合計１００重量％）から成る処理剤（Ｔ−３）。そしてこの処理剤（Ｔ−３）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−３）として１．０重量％となるよう付着させる処理方法。
アミノ変性ポリオルガノシロキサン（Ｍ−３）：式１中のＲ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7，Ａ1，Ａ2がメチル基、Ｘが３−アミノプロピル基、ｐが６０、ｑが１である場合のアミノ変性ポリオルガノシロキサン。
多環芳香族化合物（Ｎ−３）：式２中のＴがベンジル基、ｎが２、Ｂがフェノールから水酸基と２個の水素とを除いた残基、Ｙがポリオキシエチレン（ｖ＝１０）ポリオキシプロピレン（ｗ＝２）グリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
多環芳香族化合物（Ｎ−５）：式２中のＴがベンジル基、ｎが３、Ｂがフェノールから水酸基と３個の水素とを除いた残基、Ｙがエチレングリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
【００３０】
４）下記のアミノ変性ポリオルガノシロキサン（Ｍ−４）８０重量％、及び下記の多環芳香族化合物（Ｎ−４）２０重量％（合計１００重量％）から成る処理剤（Ｔ−４）。そしてこの処理剤（Ｔ−４）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−４）として１．２重量％となるよう付着させる処理方法。
アミノ変性ポリオルガノシロキサン（Ｍ−４）：式１中のＲ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7，Ａ1，Ａ2がメチル基、Ｘが３−アミノプロピル基、ｐが４５０、ｑが１５である場合のアミノ変性ポリオルガノシロキサン。
多環芳香族化合物（Ｎ−４）：式２中のＴがベンジル基、ｎが２、Ｂがメチルフェノールから水酸基と芳香環に直結する２個の水素とを除いた残基、Ｙがポリオキシエチレン（ｖ＝１０）グリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
【００３１】
５）前記のアミノ変性ポリオルガノシロキサン（Ｍ−１）７８重量％、前記の多環芳香族化合物（Ｎ−１）２０重量％、及び下記の有機カルボン酸のアミン塩（Ｆ−１）２重量％（合計１００重量％）から成る処理剤（Ｔ−８）。そしてこの処理剤（Ｔ−８）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−８）として０．６重量％となるよう付着させる処理方法。
有機カルボン酸のアミン塩（Ｆ−１）：酢酸のα−ラウリルアミノ−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝６）塩
【００３２】
６）前記のアミノ変性ポリオルガノシロキサン（Ｍ−２）８０重量％、前記の多環芳香族化合物（Ｎ−２）１４重量％、及び下記の有機カルボン酸のアミン塩（Ｆ−２）６重量％（合計１００重量％）から成る処理剤（Ｔ−９）。そしてこの処理剤（Ｔ−９）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−９）として０．８重量％となるよう付着させる処理方法。
有機カルボン酸のアミン塩（Ｆ−２）：プロピオン酸のα−ステアリルアミノ−ω−ヒドロキシ−ポリオキシプロピレン（ｗ＝６）塩
【００３３】
７）前記のアミノ変性ポリオルガノシロキサン（Ｍ−３）８１重量％、前記の多環芳香族化合物（Ｎ−３）８重量％、前記の多環芳香族化合物（Ｎ−５）３重量％及び下記の有機カルボン酸のアミン塩（Ｆ−３）８重量％（合計１００重量％）から成る処理剤（Ｔ−１０）。そしてこの処理剤（Ｔ−１０）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１０）として０．８重量％となるよう付着させる処理方法。
有機カルボン酸のアミン塩（Ｆ−３）：ラウリン酸のジエタノールアミン塩
【００３４】
８）前記のアミノ変性ポリオルガノシロキサン（Ｍ−４）７２重量％、前記の多環芳香族化合物（Ｎ−４）１８重量％、及び下記の有機カルボン酸のアミン塩（Ｆ−４）１０重量％（合計１００重量％）から成る処理剤（Ｔ−１１）。そしてこの処理剤（Ｔ−１１）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１１）として１．０重量％となるよう付着させる処理方法。
有機カルボン酸のアミン塩（Ｆ−４）：ステアリン酸のモノエタノールアミン塩
【００３５】
９）前記のアミノ変性ポリオルガノシロキサン（Ｍ−１）６５重量％、前記の多環芳香族化合物（Ｎ−２）１９重量％、前記の有機カルボン酸のアミン塩（Ｆ−１）１０重量％、及び下記のポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−１）６重量％（合計１００重量％）から成る処理剤（Ｔ−１５）。そしてこの処理剤（Ｔ−１５）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１５）として０．６重量％となるよう付着させる処理方法。
ポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−１）：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量３０００のポリオキシエチレン変性ポリジメチルシロキサン
【００３６】
１０）前記のアミノ変性ポリオルガノシロキサン（Ｍ−２）７１重量％、前記の多環芳香族化合物（Ｎ−３）１２重量％、前記の有機カルボン酸のアミン塩（Ｆ−２）８重量％、及び下記のポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−２）９重量％（合計１００重量％）から成る処理剤（Ｔ−１６）。そしてこの処理剤（Ｔ−１６）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１６）として０．８重量％となるよう付着させる処理方法。
ポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−２）：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量１５０００のポリオキシエチレン変性ポリジメチルシロキサン
【００３７】
１１）前記のアミノ変性ポリオルガノシロキサン（Ｍ−３）７６重量％、前記の多環芳香族化合物（Ｎ−１）６重量％、前記の多環芳香族化合物（Ｎ−５）３重量％、前記の有機カルボン酸のアミン塩（Ｆ−３）３重量％、及び下記のポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−３）１２重量％（合計１００重量％）から成る処理剤（Ｔ−１７）。そしてこの処理剤（Ｔ−１７）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１７）として１．０重量％となるよう付着させる処理方法。
ポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−３）：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量２５０００のポリオキシエチレン変性ポリジメチルシロキサン
【００３８】
１２）前記のアミノ変性ポリオルガノシロキサン（Ｍ−４）７２重量％、前記の多環芳香族化合物（Ｎ−４）１２重量％、下記の多環芳香族化合物（Ｎ−６）１重量％、前記の有機カルボン酸のアミン塩（Ｆ−４）６重量％、及び前記のポリオキシエチレン変性ポリオルガノシロキサン（Ｓ−１）９重量％（合計１００重量％）から成る処理剤（Ｔ−１８）。そしてこの処理剤（Ｔ−１８）を水性エマルジョンとなし、炭素繊維製造用アクリルフィラメントに、処理剤（Ｔ−１８）として０．８重量％となるよう付着させる処理方法。
多環芳香族化合物（Ｎ−６）：式２中のＴがベンジル基、ｎが１、Ｂがフェノールから水酸基と１個の水素とを除いた残基、Ｙがエチレングリコールから全ての水酸基を除いた残基である場合の多環芳香族化合物
【００３９】
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り、部は重量部、％は重量％である。
【００４０】
【実施例】
試験区分１（処理剤の調製）
・実施例１｛処理剤（Ｔ−１）の調製｝
表１に記載のアミノ変性ポリオルガノシロキサン（Ｍ−１）７７部と、表２に記載の多環芳香族化合物（Ｎ−１）２３部とを混合して、実施例１の処理剤（Ｔ−１）を調製した。
【００４１】
・実施例２〜４、８〜１８、参考例５〜７及び比較例１〜３｛処理剤（Ｔ−２）〜（Ｔ−１８）及び（Ｒ−１）〜（Ｒ−３）の調製｝
表１に記載のアミノ変性ポリオルガノシロキサン、表２に記載の多環芳香族化合物等を用い、実施例１の処理剤（Ｔ−１）と同様にして、実施例２〜４、８〜１８、参考例５〜７の処理剤（Ｔ−２）〜（Ｔ−１８）及び比較例１〜３の処理剤（Ｒ−１）〜（Ｒ−３）を調製した。以上の各例で調製した処理剤の内容を表３にまとめて示した。
【００４２】
【表１】
表１において、
Ｓ−１：メチル基
Ｓ−２：水酸基
Ｓ−３：γ−トリフロロプロピル基
Ｓ−４：フェニル基
Ｓ−５：メチルオキシ基
Ｘ−１：Ｎ−（２−アミノエチル）−３−アミノプロピル基
Ｘ−２：３−アミノプロピル基
【００４４】
【表２】
表２において、
Ｅ−１：フェノールから水酸基と３個の水素を除いた残基
Ｅ−２：フェノールから水酸基と２個の水素を除いた残基
Ｅ−３：メチルフェノールから水酸基と芳香環に直結する２個の水素を除いた残基
Ｅ−４：フェノールから水酸基と１個の水素を除いた残基
Ｅ−５：フェニルフェノールから水酸基と２個の水素を除いた残基
Ｅ−６：ナフトールから水酸基と１個の水素を除いた残基
【００４６】
【表３】
表３において、
Ｆ−１：酢酸のα−ラウリルアミノ−ω−ヒドロキシ−ポリオキシエチレン（ｖ＝６）塩
Ｆ−２：プロピオン酸のα−ステアリルアミノ−ω−ヒドロキシ−ポリオキシプロピレン（ｗ＝６）塩
Ｆ−３：ラウリン酸のジエタノールアミン塩
Ｆ−４：ステアリン酸のモノエタノールアミン塩
Ｆ−５：マロン酸のモルホリン塩
Ｆ−６：フタル酸のジエタノールアミン塩
Ｆ−７：乳酸のトリエチルアミン塩
Ｓ−１：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量３０００のポリオキシエチレン変性ポリジメチルシロキサン
Ｓ−２：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量１５０００のポリオキシエチレン変性ポリジメチルシロキサン
Ｓ−３：主鎖の側鎖にポリオキシエチレン変性基を有する数平均分子量２５０００のポリオキシエチレン変性ポリジメチルシロキサン
Ｚ−１：数平均分子量２００００のフェニル変性ポリジメチルシロキサン
Ｚ−２：数平均分子量３００００のエポキシ変性ポリジメチルシロキサン
【００４８】
試験区分２（炭素繊維製造用アクリルフィラメントへの処理剤の付着、炭素繊維の製造及び評価）
・実施例１９〜２２、２６〜３６、参考例２３〜２５及び比較例４〜６（炭素繊維製造用アクリルフィラメントへの処理剤の付着）
試験区分１で調製した各例の処理剤３０部にそれぞれ水７０部を加え、ホモジナイザーを用いて水性エマルジョンとした。この水性エマルジョンを常法により製造したアクリルフィラメント｛１７８００デジテックス（１６０００デニール／１２０００フィラメント）｝に浸漬給油法にて付着した（実施例１９〜２２、２６〜３６、参考例２３〜２５及び比較例４〜６）。
【００４９】
・炭素繊維の製造
上記のように処理剤の水性エマルジョンを付着した各例のアクリルフィラメントを、乾熱ローラーを用い、１１５℃で４秒間乾燥して、プレカーサートウとした。このプレカーサートウを２４０℃の強制循環式オーブン中で６０分間耐炎化処理して耐炎化繊維とし、次いでこの耐炎化繊維を窒素雰囲気中にて３００〜１８００℃の温度勾配を持つ焼成炉で５０分間焼成して炭素繊維とした。
【００５０】
・処理剤の付着量の測定
ＪＩＳ−Ｌ１０７３（合成繊維フィラメント糸試験方法）に準拠し、抽出溶剤としてノルマルヘキサン／エタノール＝７０／３０（容量比）の混合溶剤を用いて、前記プレカーサートウへの処理剤の付着量を測定した。結果を表４にまとめて示した。
【００５１】
・融着防止性の評価
前記耐炎化繊維について任意の１０箇所から２cm長の短繊維１０片を切り出し、試料片とした。この試料片を白紙上で軽く振盪して、その融着状態を肉眼観察した。同様の試験を５回行ない、下記の基準で融着防止性を評価した。
◎：融着なし
○：融着ごく僅かあり
△：融着ややあり
×：融着大
【００５２】
・前記耐炎化工程での糸切れの発生防止性の評価
前記耐炎化繊維５０kgを製造した際の糸切れの状態を観察した。同様の試験を５回行ない、次の基準で評価した。結果を表４にまとめて示した。
◎：糸切れはなく、工程通過性に全く問題なし
○：糸切れはごく僅かあるが、工程通過性に殆ど問題なし
△：糸切れが明らかにあり、工程通過性に問題あり
×：糸切れが著しく、工程通過性に著しく問題あり
【００５３】
【表４】
表４において、
評価１：融着防止性
評価２：耐炎化工程での糸切れの発生防止性
付着量：アクリルフィラメントに対する処理剤の付着量（％）
【００５５】
【発明の効果】
既に明らかなように、以上説明した本発明には、炭素繊維の製造において、耐炎化工程での耐炎化繊維相互の融着防止と耐炎化工程での糸切れの発生防止とを同時に且つ充分に図ることができるという効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a synthetic fiber treating agent for producing carbon fibers (hereinafter simply referred to as a treating agent) and a method for treating synthetic fibers for producing carbon fibers (hereinafter simply referred to as a treating method). When producing carbon fiber from pitch fiber or acrylic fiber, high-quality carbon fiber is produced at low cost, and in the flameproofing process, it is required to prevent fusion between the flameproofed fibers. It is required to prevent cutting. The present invention relates to a treatment agent and a treatment method that meet such a demand.
[0002]
[Prior art]
Conventionally, those containing various modified polyorganosiloxanes have been used as the treatment agents as described above. This includes 1) a treating agent containing polyoxyalkylene-modified polyorganosiloxane and epoxy-modified polyorganosiloxane (Japanese Patent Laid-Open No. 52-148227), and 2) a treating agent containing amino-modified polyorganosiloxane (Japanese Examined Patent Publication 64-64). 508, JP-B-52-24136, JP-A-60-99011, JP-A-2-91224, JP-A-6-220723, JP-A-8-209543) and the like. However, such a conventional treatment agent has a problem that it is impossible to simultaneously and sufficiently prevent the fusion between the flame-resistant fibers and the occurrence of yarn breakage in the flame resistance step.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a treating agent and a treating method capable of simultaneously and sufficiently preventing the fusion between the flame-resistant fibers and the occurrence of yarn breakage in the flame-proofing step. .
[0004]
[Means for Solving the Problems]
As a result, the present inventors have studied to solve the above problems, and as a result, the specific amino-modified polyorganosiloxane and the specific polycyclic aromatic compound are contained in a predetermined amount or more in a predetermined ratio in total. It has been found that a treatment method comprising the above treatment agent is correctly suitable, and that a treatment method in which a predetermined amount of such treatment agent is attached to a synthetic fiber for carbon fiber production is correctly suitable.
[0005]
That is, the present invention contains a total of 55 wt% or more of the amino-modified polyorganosiloxane represented by the following formula 1 and the polycyclic aromatic compound represented by the following formula 2 and It is related with the processing agent characterized by including in the ratio of a ring aromatic compound = 95 / 5-60 / 40 (weight ratio).
[0006]
[Formula 1]
T n -B-O-Y-OH
[0007]
In Equation 1 and Equation 2,
R 1 , R 2 , R Three , R Four , R Five , R 6 , R 7 : Methyl group
A 1 , A 2 : Methyl group
X: 3-aminopropyl group or N- (2-aminoethyl) -3-aminopropyl group
p: an integer from 1 to 1000
q: an integer from 1 to 50
n: an integer from 1 to 5
B: 1-3 groups directly bonded to a hydroxyl group and an aromatic ring from an alkylphenol having an alkyl group having 1 to 3 carbon atoms as a residue or substituent obtained by removing from the phenol a hydroxyl group and 1 to 3 hydrogen atoms directly bonded to the aromatic ring Residues excluding hydrogen
T: benzyl group
Y: Residue obtained by removing all hydroxyl groups from (poly) oxyalkylene glycol having 1 to 30 oxyalkylene units consisting of only oxyethylene units or both oxyethylene units and oxypropylene units
[0008]
Moreover, this invention concerns on the processing method characterized by making the processing agent concerning the above inventions adhere to 0.2 to 1.5 weight% with respect to the synthetic fiber for carbon fiber manufacture.
[0009]
The amino-modified polyorganosiloxane represented by Formula 1 is an amino-modified polyorganosiloxane having an amino-modified group only in the side chain of the main chain. Such an amino-modified polyorganosiloxane is composed of a divalent organosiloxane unit constituting the main chain, a monovalent organosiloxane unit and a monovalent organosilyl unit constituting the terminal. The divalent organosiloxane unit constituting the main chain includes a divalent organosiloxane unit enclosed by p in formula 1 and a divalent organosiloxane unit enclosed by q, and enclosed by q. The divalent organosiloxane unit has an amino-modified group. The bonding positions of the above divalent organosiloxane units are not particularly limited as long as they constitute the main chain.
[0010]
In the amino-modified polyorganosiloxane represented by the formula 1, R of divalent organosiloxane units bounded by p constituting the main chain. Three , R Four Is a methyl group. The number of divalent organosiloxane units enclosed by p is 1-1000, but is preferably 50-500.
[0011]
In the amino-modified polyorganosiloxane represented by the formula 1, X in the divalent organosiloxane unit enclosed by q constituting the main chain is an amino-modified group, and is a 3-aminopropyl group or N- (2-amino Ethyl) -3-aminopropyl group. R of the divalent organosiloxane unit enclosed by q Five Is R Three , R Four As well as a methyl group. The number of divalent organosiloxane units enclosed by q is 1 to 50, preferably 1 to 20.
[0012]
In the amino-modified polyorganosiloxane represented by Formula 1, R of the monovalent organosiloxane unit constituting the terminal of the main chain 1 , R 2 Is R Three , R Four As in A, a monovalent organosiloxane unit A which is a methyl group and constitutes the end of the main chain 1 Is also a methyl group.
[0013]
In the amino-modified polyorganosiloxane represented by Formula 1, R of the monovalent organosilyl unit constituting the terminal of the main chain 6 , R 7 Is R Three , R Four As in A, a monovalent organosilyl unit A which is a methyl group and constitutes the end of the main chain 2 Is also a methyl group.
[0014]
The amino-modified polyorganosiloxane represented by Formula 1 can be synthesized by a known method. This includes, for example, 1) a method of reacting a cyclic diorganopolysiloxane with an α, ω-dihydroxyamino-modified polyorganosiloxane in the presence of an alkali catalyst, and 2) a hydrogen polyorganosiloxane of a chloroplatinic acid catalyst. Examples thereof include a method of reacting with an arylamine compound in the presence.
[0015]
In the polycyclic aromatic compound represented by the formula 2, B in the formula 2 is a residue obtained by removing from a phenol a hydroxyl group and 1 to 3 hydrogen atoms directly bonded to the aromatic ring, or a substituent having 1 to 3 carbon atoms. This is a residue obtained by removing 1 to 3 hydrogen atoms directly bonded to a hydroxyl group and an aromatic ring from an alkylphenol having an alkyl group. T in Formula 2 is a benzyl group. The number n of T is 1 to 3. Further, Y in Formula 2 is 1) a residue obtained by removing all hydroxyl groups from (poly) oxyethylene glycol having 1 to 30 oxyethylene units, or 2) 2 to 30 oxyethylene units in total. It is a residue obtained by removing all hydroxyl groups from (poly) oxyethylene (poly) oxypropylene glycol having both oxypropylene units.
[0016]
Examples of the polycyclic aromatic compound represented by the formula 2 described above include α- (tribenzylphenyl) -ω-hydroxy-polyoxyethylene (number of oxyethylene units, hereinafter referred to as v = 1), α- (di Benzylphenyl) -ω-hydroxy-polyoxyethylene (v = 5), α- (dibenzylphenyl) -ω-hydroxy-polyoxyethylene polyoxypropylene (v = 10, w = 2), α- (dibenzyl Methylphenyl) -ω-hydroxy-polyoxyethylene (v = 10), α- (monobenzylorthomethylphenyl) -ω-hydroxy-oxyethylene (v = 1) and the like.
[0017]
The polycyclic aromatic compound represented by Formula 2 can be synthesized by a known method. For example, an aromatic compound having one hydroxyl group directly bonded to an aromatic ring is reacted with benzyl chloride in the presence of a Lewis acid catalyst to replace hydrogen directly bonded to the aromatic ring with a benzyl group, and then water. Examples include a method of addition polymerization of alkylene oxide in the presence of a potassium oxide catalyst.
[0018]
The treating agent according to the present invention contains the amino-modified polyorganosiloxane and the polycyclic aromatic compound described above in a total of 55% by weight or more, preferably 60% by weight or more, and the amino-modified polyorganosiloxane / the many The ring aromatic compound is contained in a ratio of 95/5 to 60/40 (weight ratio), preferably 90/10 to 75/25 (weight ratio).
[0019]
As described above, the treatment agent according to the present invention contains a total amount of the amino-modified polyorganosiloxane and the polycyclic aromatic compound in a predetermined amount and both in a predetermined ratio. An amine salt can be contained. Examples of the organic carboxylic acid that constitutes the amine salt of such organic carboxylic acid include 1) carbon number of acetic acid, propionic acid, caproic acid, lauric acid, 2-ethylhexanoic acid, isostearic acid, oleic acid, erucic acid, and the like. 2-30 aliphatic monocarboxylic acids, 2) malonic acid, adipic acid, itaconic acid, sebacic acid, pentadecenyl succinic acid and other C3-C30 aliphatic dicarboxylic acids, 3) benzoic acid, phthalic acid , Aromatic carboxylic acids having 7 to 30 carbon atoms such as trimellitic acid, 4) aliphatic hydroxycarboxylic acids having 3 to 30 carbon atoms such as lactic acid, tartaric acid, ricinoleic acid, 12-hydroxystearic acid, and 5) thiodipropion Examples thereof include sulfur-containing aliphatic carboxylic acids having 3 to 30 carbon atoms such as acids. Among these, aliphatic monocarboxylic acids having 2 to 22 carbon atoms and aliphatic hydroxycarboxylic acids having 2 to 22 carbon atoms are preferable, and fatty acids having 2 to 18 carbon atoms such as acetic acid, propionic acid, caproic acid, lauric acid, and oleic acid. Group monocarboxylic acids are particularly preferred.
[0020]
Examples of amine compounds that constitute the amine salts of organic carboxylic acids include 1) aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, octylamine, 2) Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, butyldiethanolamine, octyldiethanolamine, lauryldiethanolamine, 3) α-laurylamino-ω-hydroxy-polyoxyethylene (V = 6), α-stearylamino-ω-hydroxy-polyoxypropylene (w = 6), α-oleylamino-ω-hydro Sheet - Polyoxyethylene (v = 15) aliphatic polyoxyalkylene adducts of amines such as, 4), pyridine, morpholine, piperazine, aromatic amines or heterocyclic amines such as derivatives thereof. Of these, alkanolamines and polyoxyalkylene adducts of aliphatic amines are preferred. The content of the amine salt of the organic carboxylic acid described above is 0.5 to 20% by weight in the treating agent, but preferably 1 to 15% by weight.
[0021]
When the treating agent according to the present invention contains an amine salt of an organic carboxylic acid as described above, it can further contain a polyoxyalkylene-modified polyorganosiloxane. Examples of the polyoxyalkylene-modified polyorganosiloxane include various types such as those having a polyoxyalkylene-modified group at the side chain of the main chain and those having a polyoxyalkylene-modified group at the end of the main chain. A polyoxyalkylene-modified polyorganosiloxane having a number-average molecular weight of 1000 to 30000 having a polyoxyalkylene-modified group in the side chain is preferred. Examples of the polyoxyalkylene-modified group of the polyoxyalkylene-modified polyorganosiloxane include 1) a polyoxyethylene-modified group, and 2) a polyoxyethylene / polyoxypropylene-modified group. Among them, a polyoxyethylene-modified group is preferable. Polyoxyethylene-modified polyorganosiloxane having a number average molecular weight of 2000 to 15000 is more preferable. The content of the polyoxyalkylene-modified polyorganosiloxane described above is 3 to 25% by weight in the treating agent, but is preferably 5 to 20% by weight.
[0022]
The treatment agent according to the present invention has been described above. The treatment agent is an amino-modified polyorganosiloxane represented by Formula 1, a polycyclic aromatic compound represented by Formula 2, and an amine salt of the organic carboxylic acid described above. When the polyoxyalkylene-modified polyorganosiloxane is used, the amino-modified polyorganosiloxane is 60 to 85% by weight, the polycyclic aromatic compound is 10 to 25% by weight, and the amine salt of the organic carboxylic acid. 1 to 15% by weight and those containing 5 to 20% by weight (100% by weight in total) of the polyoxyalkylene-modified polyorganosiloxane are most preferable.
[0023]
In the treatment method according to the present invention, the treatment agent according to the present invention as described above is 0.2 to 1.5% by weight, preferably 0.3 to 1.2% by weight, based on the synthetic fiber for carbon fiber production. Adhere to become.
[0024]
In the treatment method according to the present invention, examples of the method for attaching the treatment agent include known methods such as an immersion oil supply method, a roller oil supply method, a guide oil supply method using a metering pump, and a spray oil supply method. A roller oiling method and a guide oiling method using a metering pump are preferred.
[0025]
In attaching the treatment agent according to the present invention to the synthetic fiber for carbon fiber production, the treatment agent is preferably used as an aqueous liquid, usually an aqueous emulsion. When adhering the treatment agent to the synthetic fiber for carbon fiber production, other components such as antioxidants, preservatives, rust inhibitors, etc. can be used in combination for the purpose, but the amount used is as much as possible. It is preferable to use a small amount.
[0026]
The treatment agent and treatment method according to the present invention can be applied to pitch fibers or acrylic fibers for producing carbon fibers, but the effect is higher when applied to acrylic fibers.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the treatment agent and the treatment method according to the present invention include the following 1) to 12).
1) A treating agent (T-1) comprising 77% by weight of the following amino-modified polyorganosiloxane (M-1) and 23% by weight (total 100% by weight) of the following polycyclic aromatic compound (N-1). And the processing method which makes this processing agent (T-1) into an aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.6 weight% as a processing agent (T-1).
Amino-modified polyorganosiloxane (M-1): R in formula 1 1 , R 2 , R Three , R Four , R Five , R 6 , R 7 , A 1 , A 2 Is a methyl group, X is an N- (2-aminoethyl) -3-aminopropyl group, p is 60, and q is 1.
Polycyclic aromatic compound (N-1): T in formula 2 is a benzyl group, n is 3, B is a residue obtained by removing a hydroxyl group and three hydrogens from phenol, Y is polyoxyethylene (v = 5) ) Polycyclic aromatic compounds in the case of residues obtained by removing all hydroxyl groups from glycol
[0028]
2) A treating agent (T-2) comprising 85% by weight of the following amino-modified polyorganosiloxane (M-2) and 15% by weight (100% by weight in total) of the following polycyclic aromatic compound (N-2). And the processing method which makes this processing agent (T-2) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.8 weight% as a processing agent (T-2).
Amino-modified polyorganosiloxane (M-2): R in formula 1 1 , R 2 , R Three , R Four , R Five , R 6 , R 7 , A 1 , A 2 Is a methyl group, X is an N- (2-aminoethyl) -3-aminopropyl group, p is 320, and q is 6, an amino-modified polyorganosiloxane.
Polycyclic aromatic compound (N-2): T in formula 2 is benzyl group, n is 2, B is a residue obtained by removing hydroxyl and 2 hydrogen from phenol, Y is polyoxyethylene (v = 15) Polycyclic aromatic compounds in the case of residues obtained by removing all hydroxyl groups from glycol
[0029]
3) 89% by weight of the following amino-modified polyorganosiloxane (M-3), 8% by weight of the following polycyclic aromatic compound (N-3), and 3% by weight of the following polycyclic aromatic compound (N-5) A processing agent (T-3) comprising (total 100% by weight). And the processing method which makes this processing agent (T-3) into an aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 1.0 weight% as a processing agent (T-3).
Amino-modified polyorganosiloxane (M-3): R in formula 1 1 , R 2 , R Three , R Four , R Five , R 6 , R 7 , A 1 , A 2 Is an amino-modified polyorganosiloxane in which X is a methyl group, X is a 3-aminopropyl group, p is 60, and q is 1.
Polycyclic aromatic compound (N-3): T in formula 2 is benzyl group, n is 2, B is a residue obtained by removing hydroxyl and two hydrogen from phenol, Y is polyoxyethylene (v = 10) ) Polycyclic aromatic compound in the case of a residue obtained by removing all hydroxyl groups from polyoxypropylene (w = 2) glycol
Polycyclic aromatic compound (N-5): T in formula 2 is benzyl group, n is 3, B is a residue obtained by removing hydroxyl and 3 hydrogen from phenol, Y is all hydroxyl groups from ethylene glycol Polycyclic aromatic compounds when the residue is excluded
[0030]
4) A treating agent (T-4) comprising 80% by weight of the following amino-modified polyorganosiloxane (M-4) and 20% by weight (100% in total) of the following polycyclic aromatic compound (N-4). And the processing method which makes this processing agent (T-4) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 1.2 weight% as a processing agent (T-4).
Amino-modified polyorganosiloxane (M-4): R in formula 1 1 , R 2 , R Three , R Four , R Five , R 6 , R 7 , A 1 , A 2 Is an amino-modified polyorganosiloxane in which X is a methyl group, X is a 3-aminopropyl group, p is 450, and q is 15.
Polycyclic aromatic compound (N-4): in formula 2, T is a benzyl group, n is 2, B is a residue obtained by removing methyl hydrogen from hydroxyl group and two hydrogen atoms directly connected to the aromatic ring, Y is poly Polycyclic aromatic compound in the case of a residue obtained by removing all hydroxyl groups from oxyethylene (v = 10) glycol
[0031]
5) The above-mentioned amino-modified polyorganosiloxane (M-1) 78% by weight, the above polycyclic aromatic compound (N-1) 20% by weight, and the following organic carboxylic acid amine salt (F-1) 2% % (Total of 100% by weight) treatment agent (T-8). And the processing method which makes this processing agent (T-8) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.6 weight% as a processing agent (T-8).
Amine salt of organic carboxylic acid (F-1): α-laurylamino-ω-hydroxy-polyoxyethylene (v = 6) salt of acetic acid
[0032]
6) 80% by weight of the above-mentioned amino-modified polyorganosiloxane (M-2), 14% by weight of the above polycyclic aromatic compound (N-2), and 6% by weight of the following organic carboxylic acid amine salt (F-2) % (Total of 100% by weight) (T-9). And the processing method which makes this processing agent (T-9) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.8 weight% as a processing agent (T-9).
Amine salt of organic carboxylic acid (F-2): α-stearylamino-ω-hydroxy-polyoxypropylene (w = 6) salt of propionic acid
[0033]
7) 81 wt% of the amino-modified polyorganosiloxane (M-3), 8 wt% of the polycyclic aromatic compound (N-3), 3 wt% of the polycyclic aromatic compound (N-5) and The processing agent (T-10) which consists of 8 weight% (total 100 weight%) of the amine salt (F-3) of the following organic carboxylic acid. And the processing method which makes this processing agent (T-10) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.8 weight% as a processing agent (T-10).
Amine salt of organic carboxylic acid (F-3): Diethanolamine salt of lauric acid
[0034]
8) 72% by weight of the amino-modified polyorganosiloxane (M-4), 18% by weight of the polycyclic aromatic compound (N-4), and 10% by weight of an amine salt (F-4) of the following organic carboxylic acid % (Total of 100% by weight) treatment agent (T-11). And the processing method which makes this processing agent (T-11) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 1.0 weight% as a processing agent (T-11).
Amine salt of organic carboxylic acid (F-4): monoethanolamine salt of stearic acid
[0035]
9) 65% by weight of the amino-modified polyorganosiloxane (M-1), 19% by weight of the polycyclic aromatic compound (N-2), 10% by weight of the amine salt of the organic carboxylic acid (F-1) And a treating agent (T-15) comprising 6% by weight (100% by weight in total) of the following polyoxyethylene-modified polyorganosiloxane (S-1). And the processing method which makes this processing agent (T-15) into an aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.6 weight% as a processing agent (T-15).
Polyoxyethylene-modified polyorganosiloxane (S-1): polyoxyethylene-modified polydimethylsiloxane having a number-average molecular weight of 3000 having a polyoxyethylene-modified group in the side chain of the main chain
[0036]
10) 71% by weight of the amino-modified polyorganosiloxane (M-2), 12% by weight of the polycyclic aromatic compound (N-3), 8% by weight of the amine salt of the organic carboxylic acid (F-2) And a treating agent (T-16) comprising 9% by weight (100% by weight in total) of the following polyoxyethylene-modified polyorganosiloxane (S-2). And the processing method which makes this processing agent (T-16) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.8 weight% as a processing agent (T-16).
Polyoxyethylene-modified polyorganosiloxane (S-2): polyoxyethylene-modified polydimethylsiloxane having a number-average molecular weight of 15,000 having a polyoxyethylene-modified group in the side chain of the main chain
[0037]
11) 76% by weight of the amino-modified polyorganosiloxane (M-3), 6% by weight of the polycyclic aromatic compound (N-1), 3% by weight of the polycyclic aromatic compound (N-5), Treatment agent (T-17) comprising 3% by weight of the above-mentioned amine salt of organic carboxylic acid (F-3) and 12% by weight of polyoxyethylene-modified polyorganosiloxane (S-3) (100% in total) . And the processing method which makes this processing agent (T-17) an aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 1.0 weight% as a processing agent (T-17).
Polyoxyethylene-modified polyorganosiloxane (S-3): polyoxyethylene-modified polydimethylsiloxane having a number average molecular weight of 25,000 having a polyoxyethylene-modified group in the side chain of the main chain
[0038]
12) 72 wt% of the amino-modified polyorganosiloxane (M-4), 12 wt% of the polycyclic aromatic compound (N-4), 1 wt% of the following polycyclic aromatic compound (N-6), A treating agent (T-18) comprising 6% by weight of the above-described amine salt of organic carboxylic acid (F-4) and 9% by weight (100% in total) of the polyoxyethylene-modified polyorganosiloxane (S-1). . And the processing method which makes this processing agent (T-18) into aqueous emulsion, and adheres it to the acrylic filament for carbon fiber manufacture so that it may become 0.8 weight% as a processing agent (T-18).
Polycyclic aromatic compound (N-6): T in formula 2 is benzyl group, n is 1, B is a residue obtained by removing hydroxyl and one hydrogen from phenol, Y is all hydroxyl groups from ethylene glycol Polycyclic aromatic compounds when the residue is excluded
[0039]
Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated, parts are parts by weight and% is% by weight.
[0040]
【Example】
Test Category 1 (Preparation of treatment agent)
Example 1 {Preparation of treating agent (T-1)}
77 parts of the amino-modified polyorganosiloxane (M-1) shown in Table 1 and 23 parts of the polycyclic aromatic compound (N-1) shown in Table 2 were mixed to prepare the treating agent (T -1) was prepared.
[0041]
Examples 2 to 4, 8 to 18, Reference Examples 5 to 7 and Comparative Examples 1 to 3 {Preparation of treating agents (T-2) to (T-18) and (R-1) to (R-3) }
Examples 2-4 and 8-18 were carried out in the same manner as the treating agent (T-1) of Example 1 using the amino-modified polyorganosiloxane shown in Table 1 and the polycyclic aromatic compound shown in Table 2. The treatment agents (T-2) to (T-18) of Reference Examples 5 to 7 and the treatment agents (R-1) to (R-3) of Comparative Examples 1 to 3 were prepared. Table 3 summarizes the contents of the treatment agents prepared in the above examples.
[0042]
[Table 1]
In Table 1,
S-1: Methyl group
S-2: Hydroxyl group
S-3: γ-trifluoropropyl group
S-4: Phenyl group
S-5: Methyloxy group
X-1: N- (2-aminoethyl) -3-aminopropyl group
X-2: 3-aminopropyl group
[0044]
[Table 2]
In Table 2,
E-1: Residue obtained by removing a hydroxyl group and three hydrogens from phenol
E-2: Residue obtained by removing a hydroxyl group and two hydrogens from phenol
E-3: Residue obtained by removing two hydrogen atoms directly connected to a hydroxyl group and an aromatic ring from methylphenol
E-4: Residue obtained by removing a hydroxyl group and one hydrogen from phenol
E-5: Residue obtained by removing a hydroxyl group and two hydrogens from phenylphenol
E-6: Residue obtained by removing a hydroxyl group and one hydrogen from naphthol
[0046]
[Table 3]
In Table 3,
F-1: α-Laurylamino-ω-hydroxy-polyoxyethylene (v = 6) salt of acetic acid
F-2: α-stearylamino-ω-hydroxy-polyoxypropylene (w = 6) salt of propionic acid
F-3: Diethanolamine salt of lauric acid
F-4: monoethanolamine salt of stearic acid
F-5: morpholine salt of malonic acid
F-6: Diethanolamine salt of phthalic acid
F-7: Triethylamine salt of lactic acid
S-1: Polyoxyethylene-modified polydimethylsiloxane having a number average molecular weight of 3000 having a polyoxyethylene-modified group in the side chain of the main chain
S-2: Polyoxyethylene-modified polydimethylsiloxane having a number average molecular weight of 15,000 having a polyoxyethylene-modified group in the side chain of the main chain
S-3: Polyoxyethylene-modified polydimethylsiloxane having a number average molecular weight of 25,000 having a polyoxyethylene-modified group in the side chain of the main chain
Z-1: Phenyl-modified polydimethylsiloxane having a number average molecular weight of 20000
Z-2: Epoxy-modified polydimethylsiloxane having a number average molecular weight of 30,000
[0048]
Test Category 2 (Attachment of treatment agent to acrylic filament for carbon fiber production, production and evaluation of carbon fiber)
Examples 19 to 22, 26 to 36, Reference Examples 23 to 25, and Comparative Examples 4 to 6 (Attachment of treatment agent to acrylic filament for carbon fiber production)
70 parts of water was added to 30 parts of the treating agent of each example prepared in Test Category 1, and an aqueous emulsion was prepared using a homogenizer. This aqueous emulsion was adhered to an acrylic filament {17800 digitex (16000 denier / 12000 filament)} produced by a conventional method by an immersion oiling method (Examples 19 to 22, 26 to 36, Reference Examples 23 to 25 and Comparative Examples). 4-6).
[0049]
・ Manufacture of carbon fiber
The acrylic filament of each example to which the aqueous emulsion of the treatment agent was attached as described above was dried at 115 ° C. for 4 seconds using a dry heat roller to obtain a precursor tow. The precursor tow was flame-treated in a forced circulation oven at 240 ° C. for 60 minutes to form flame-resistant fibers, and then the flame-resistant fibers were placed in a firing atmosphere having a temperature gradient of 300 to 1800 ° C. in a nitrogen atmosphere for 50 minutes. Firing was made into carbon fiber.
[0050]
・ Measurement of treatment agent adhesion
Based on JIS-L1073 (synthetic fiber filament yarn test method), using a mixed solvent of normal hexane / ethanol = 70/30 (volume ratio) as an extraction solvent, the adhesion amount of the treatment agent to the precursor tow was measured. . The results are summarized in Table 4.
[0051]
・ Evaluation of adhesion prevention
Ten pieces of 2 cm long short fibers were cut out from any 10 locations of the flameproofed fibers, and used as sample pieces. The sample piece was shaken lightly on white paper, and the fused state was visually observed. The same test was performed 5 times, and the anti-fusing property was evaluated according to the following criteria.
A: No fusion
○: Very little fusion
Δ: Slightly fused
×: Large fusion
[0052]
・ Evaluation of yarn breakage prevention in the flameproofing process
The state of yarn breakage when 50 kg of the flameproof fiber was produced was observed. The same test was conducted 5 times and evaluated according to the following criteria. The results are summarized in Table 4.
◎: No thread breakage, no problem with process passage
○: Yarn breakage is negligible, but there is almost no problem in process passage
△: Clear thread breakage and problem in process passage
×: Yarn breakage is significant and there is a significant problem in process passability
[0053]
[Table 4]
In Table 4,
Evaluation 1: Anti-fusing property
Evaluation 2: Prevention of yarn breakage in the flameproofing process
Adhesion amount: Adhesion amount of treatment agent to acrylic filament (%)
[0055]
【The invention's effect】
As is clear from the above, the present invention described above, in the production of carbon fiber, simultaneously and sufficiently prevents the fusion between the flame-resistant fibers in the flame-proofing process and the occurrence of yarn breakage in the flame-proofing process. There is an effect that it can be planned.
Claims (8)
【式１】
Ｔn−Ｂ−Ｏ−Ｙ−ＯＨ
（式１、式２において、
Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7：メチル基
Ａ1，Ａ2：メチル基
Ｘ：３−アミノプロピル基又はＮ−（２−アミノエチル）−３−アミノプロピル基
ｐ：１〜１０００の整数
ｑ：１〜５０の整数
ｎ：１〜５の整数
Ｂ：フェノールから水酸基と芳香環に直結する１〜３個の水素とを除いた残基又は置換基として炭素数１〜３のアルキル基を有するアルキルフェノールから水酸基と芳香環に直結する１〜３個の水素とを除いた残基
Ｔ：ベンジル基
Ｙ：オキシエチレン単位のみ又はオキシエチレン単位とオキシプロピレン単位の双方からなるオキシアルキレン単位の数が１〜３０の（ポリ）オキシアルキレングリコールから全ての水酸基を除いた残基） A total of 55% by weight or more of the amino-modified polyorganosiloxane represented by the following formula 1 and the polycyclic aromatic compound represented by the following formula 2 and the amino-modified polyorganosiloxane / the polycyclic aromatic compound = A synthetic fiber treatment agent for producing carbon fiber, comprising 95/5 to 60/40 (weight ratio).
[Formula 1]
T n —B—O—Y—OH
(In Formula 1 and Formula 2,
R 1, R 2, R 3 , R 4, R 5, R 6, R 7: methyl group A 1, A 2: Methyl group X: 3- aminopropyl group or N-(2-aminoethyl) -3- aminopropyl group p: 1 to 1000 integer q: 1 to 50 integer n: 1 to 5 integer B: residual excluding a 1-3 hydrogen directly connected to phenol or et water group and Kaoru incense ring residue group or excluding the 1-3 hydrogen directly connected to alkyl phenol or et water group and fang incense ring having an alkyl group of carbon number 1-3 as a location substituent T: benzyl group Y: polyoxyethylene A residue obtained by removing all hydroxyl groups from (poly) oxyalkylene glycol having 1 to 30 oxyalkylene units consisting of only units or oxyethylene units and oxypropylene units )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111499871A (en) * | 2020-03-17 | 2020-08-07 | 北京化工大学 | A kind of aromatic carboxylic acid polysiloxane ammonium salt system and preparation method thereof |
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| JP4624601B2 (en) * | 2001-06-14 | 2011-02-02 | 竹本油脂株式会社 | Synthetic fiber treatment agent for carbon fiber production and method for treating synthetic fiber for carbon fiber production |
| JP4699821B2 (en) * | 2005-06-03 | 2011-06-15 | 松本油脂製薬株式会社 | Acrylic fiber oil for carbon fiber production |
| WO2012000189A1 (en) * | 2010-06-30 | 2012-01-05 | Dow Global Technologies Llc | Branched secondary alcohol alkoxylate surfactants for textile processing |
| JP6167735B2 (en) * | 2013-08-01 | 2017-07-26 | 三菱ケミカル株式会社 | Oil agent composition for carbon fiber precursor acrylic fiber, oil agent composition dispersion for carbon fiber precursor acrylic fiber, and method for producing carbon fiber precursor acrylic fiber bundle |
| JP6535149B2 (en) | 2017-03-09 | 2019-06-26 | 松本油脂製薬株式会社 | Acrylic fiber treatment agent and use thereof |
| WO2024057740A1 (en) | 2022-09-13 | 2024-03-21 | 松本油脂製薬株式会社 | Treatment agent for acrylic fibers and use of same |
| JP7448735B1 (en) | 2022-09-13 | 2024-03-12 | 松本油脂製薬株式会社 | Treatment agents for acrylic fibers and their uses |
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| JPS60104578A (en) * | 1983-11-05 | 1985-06-08 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
| JPH0686707B2 (en) * | 1984-09-14 | 1994-11-02 | 竹本油脂株式会社 | Method for preventing fusion of precursor fiber in production of carbon fiber |
| JPS63315613A (en) * | 1987-06-18 | 1988-12-23 | Toa Nenryo Kogyo Kk | Production of carbon and graphite fiber |
| JPH0657888B2 (en) * | 1988-02-24 | 1994-08-03 | 竹本油脂株式会社 | Oil agent for carbon fiber production |
| JPH0533263A (en) * | 1990-11-30 | 1993-02-09 | Petoca:Kk | Reinforcing fiber for carbon-carbon composite material and method for manufacturing composite material |
| JP3949777B2 (en) * | 1997-06-20 | 2007-07-25 | 三菱レイヨン株式会社 | Carbon fiber precursor acrylic fiber |
| JP3945549B2 (en) * | 1997-06-20 | 2007-07-18 | 信越化学工業株式会社 | Oil for carbon fiber precursor |
| JP4229413B2 (en) * | 1999-10-20 | 2009-02-25 | 竹本油脂株式会社 | Synthetic fiber treatment agent for carbon fiber production and method for treating synthetic fiber for carbon fiber production |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499871A (en) * | 2020-03-17 | 2020-08-07 | 北京化工大学 | A kind of aromatic carboxylic acid polysiloxane ammonium salt system and preparation method thereof |
| CN111499871B (en) * | 2020-03-17 | 2022-04-12 | 北京化工大学 | Aromatic carboxylic acid polysiloxane ammonium salt system and preparation method thereof |
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