JP4561020B2 - Bundling agent for glass fiber containing cationic surfactant - Google Patents

Description

【化４】

［式中、Ｒ¹及びＲ²は同一でも異なっていてもよく、それぞれ炭素数１〜１２のアルキレン基、ｎは０〜１０の整数、ｍは１〜１０の整数を示す。］
【０００９】
本発明のガラス繊維用集束剤においては、第１の脂肪酸及び第２の脂肪酸が、同一又は異なる炭素数６〜３２の飽和脂肪酸であり、Ｒ¹及びＲ²がエチレン基であることが好ましい。また、カルボニル基含有架橋剤が、尿素であることが好ましい。
【００１０】
本発明のガラス繊維用集束剤においては、また、油剤１００重量部に対する第１のカチオン界面活性剤の重量が１０〜５０重量部であることが好ましく、第１のカチオン界面活性剤１００重量部に対する第２のカチオン界面活性剤の重量が５〜５０重量部であることが好ましく、更に、澱粉が、残存粒子率３０〜７０重量％の澱粉であることが好ましい。
【００１１】
本発明のガラス繊維束は、上記本発明のガラス繊維用集束剤により、ガラス繊維フィラメントが複数本集束されてなることを特徴とするものであり、かかるガラス繊維束においては、ガラス繊維フィラメント１００重量部に対するガラス繊維用集束剤の不揮発成分重量が、０．５〜１．５重量部であることが好ましい。
なお、本発明において不揮発成分とは、ガラス繊維用集束剤をガラス繊維フィラメントに塗布して１１０℃に加熱した場合に揮発しない成分をいい、不揮発成分重量とはその成分の重量をいう。
【００１２】
本発明のガラス繊維織物の製造方法は、ガラス繊維束を経糸及び緯糸としてエアジェット織機により製織するガラス繊維織物の製造方法であって、経糸及び緯糸のうち少なくとも緯糸は、上記本発明のガラス繊維束であることを特徴とするものである。
【００１３】
【発明の実施の形態】
上述のように、本発明のガラス繊維用集束剤は、澱粉、油剤、界面活性剤及び水を必須成分として含有するが、本発明においては、界面活性剤の少なくとも一部に以下の特定のカチオン界面活性剤（ａ）及び（ｂ）を組み合わせて用いたことが大きな特徴である。
（ａ）第１の脂肪酸と上記一般式（１）で表される第１のアミン化合物とを反応させてなる第１のカチオン界面活性剤（以下、単に「第１のカチオン界面活性剤」という。）。
（ｂ）第２の脂肪酸と上記一般式（２）で表される第２のアミン化合物との反応生成物をカルボニル基含有架橋剤と反応させてなる第２のカチオン界面活性剤（以下、単に「第２のカチオン界面活性剤」という。）。
【００１４】
従来より、第２のカチオン界面活性剤に対応する界面活性剤を含むガラス繊維用集束剤は知られており（例えば、上記特開昭４９−１００３９１号公報）、かかる界面活性剤は、それを含むガラス繊維用集束剤が塗布されたガラス繊維束の集束性、柔軟性及び潤滑性を向上させることが可能であるとされているが（同公報）、本発明者らは、第２のカチオン界面活性剤を第１のカチオン界面活性剤と組み合わせることにより、それらを含むガラス繊維用集束剤が塗布されたガラス繊維束が高速で衝撃を受けた場合であっても、ガラス繊維フィラメント表面が効果的に保護され毛羽の発生が防止されるという全く新規な知見を得、かかる知見に基づき本発明を想到するに至ったものである。
【００１５】
以下、本発明のガラス繊維用集束剤の必須成分である、澱粉、油剤、界面活性剤及び水のそれぞれについて詳述する。先ず、澱粉について説明する。
【００１６】
本発明において用いられる澱粉としては、コーン澱粉（コーンスターチ）、タピオカ澱粉、小麦澱粉、甘藷澱粉、馬鈴薯澱粉、ハイアミロースコーン澱粉、サゴ澱粉、米澱粉等が挙げられる。また、馬鈴薯澱粉のアミロース抽出物や、酵素により合成された特殊な澱粉も使用することができる。これらの澱粉は、エーテル化、エステル化、グラフト化、架橋等の加工が施されたものであってもよい。
【００１７】
エーテル化された澱粉としては、カルボキシメチルエーテル化澱粉、ヒドロキシアルキルエーテル化澱粉、アルキルエーテル化澱粉、ベンジルエーテル化澱粉、カチオンエーテル化澱粉等が挙げられる。また、エステル化された澱粉としては、酢酸エステル化澱粉、燐酸エステル化澱粉、硫酸エステル化澱粉、硝酸エステル化澱粉、キサントゲン酸エステル化澱粉等が挙げられる。このエーテル化及びエステル化のいずれにおいても、澱粉の置換度には特に制限はない。
【００１８】
グラフト化された澱粉としては、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリルアミド、スチレン、マレイン酸等の不飽和二重結合を有するモノマーの少なくとも１種を澱粉にグラフト重合させたものが例示可能である。
【００１９】
澱粉としては、更に、未加工の澱粉に対して架橋を導入したもの、又は上記のエーテル化、エステル化、グラフト化が施された澱粉に対して架橋を導入したものを挙げることができる。架橋を導入する場合においては、澱粉中の水酸基と反応性の官能基を２以上有する化合物や、澱粉中の水酸基との反応により水酸基反応性の官能基を新たに生じるような化合物が架橋剤として用いられる。このような架橋剤としては、エピクロルヒドリン、ホルムアルデヒド、ジエポキシド化合物、ジアルデヒド化合物等を挙げることができる。
【００２０】
本発明において用いられる澱粉におけるアミロース成分の量及びアミロペクチン成分の量は任意である。アミロース成分が５０重量％未満の通常型澱粉（典型的にはアミロース成分を約３０重量％、アミロペクチン成分を約７０重量％含む）、及び、アミロース成分を５０重量％以上含むハイアミロース型澱粉（典型的にはアミロース成分を約７０重量％、アミロペクチン成分を約３０重量％含む）のいずれもが使用可能である。通常型澱粉を含有する集束剤は接着性に優れ、ハイアミロース型澱粉を含有する澱粉は皮膜形成性に優れると一般的に言われている。本発明においては、用いる澱粉の少なくとも一部は、ハイアミロース型澱粉であることが好ましく、通常型澱粉とハイアミロース型澱粉を組み合わせて使用することがより好ましい。澱粉の重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として４０〜８０重量％が好ましく、４５〜７５重量％がより好ましい。
【００２１】
本発明においては、また、残存粒子率３０〜７０重量％の澱粉を用いることが好ましい。ここで、澱粉の残存粒子率とは以下の方法により求められる比率をいう。すなわち、澱粉を水に分散させた後、９５℃に加熱して糊化させ糊液（澱粉比率は無水換算で、糊液全重量を基準として５重量％）を得、これを遠心分離（５０００ｒｐｍ、１０分）して上澄み液を採取し、それを１１０℃にて３０分乾燥させ固形分率（重量％）を測定する。残存粒子率（重量％）は、この固形分率（重量％）を用い以下の式（Ｉ）により算出する。
【数１】

【００２２】
残存粒子率が上記重量％である場合は、本発明のガラス繊維用集束剤でガラス繊維フィラメントを複数本集束してガラス繊維束を作製する場合において、ガラス繊維フィラメントを集束する接着強度が上昇する傾向にある。かかる残留粒子率は、４０〜６５重量％であることが更に好ましい。なお、澱粉を複数種組み合わせて用いる場合は、残留粒子率は平均値を用いる。
【００２３】
次に、本発明のガラス繊維用集束剤における油剤について説明する。本発明において用いることのできる油剤としては、変性シリコーンオイル、牛脂油等の動物油及びこの水素添加物；ゴマ油、ナタネ油、パーム油等の植物油及びこの水素添加物；高級飽和脂肪酸と高級飽和アルコールの縮合物（ラウリルステアレート等のステアリン酸エステル等）；パラフィンワックス等が例示できる。ガラス繊維用集束剤における油剤は、ガラス繊維束に滑りを与え、機械上での摩擦を減少させガラス繊維を保護する機能を有する。油剤の重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として５〜３０重量％が好ましく、１０〜２５重量％がより好ましい。
【００２４】
次に、本発明における界面活性剤について説明する。本発明においては、界面活性剤として第１のカチオン界面活性剤及び第２のカチオン界面活性剤を必須成分として含有する。
【００２５】
第１のカチオン界面活性剤は、第１の脂肪酸と下記一般式（１）で表される第１のアミン化合物とを反応させてなるものである。
【化５】

【００２６】
上記式中、Ｒ¹は炭素数１〜１２のアルキレン基、ｎは０〜１０の整数を示し、一般式（１）で表される第１のアミン化合物の具体例としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミンが挙げられる。本発明においては、Ｒ¹は炭素数２〜１０のアルキレン基がより好ましく、炭素数２〜６のアルキレン基が更に好ましく、エチレン基が特に好ましい。ｎは１〜８がより好ましく、１〜６が更に好ましく、３が特に好ましい。したがって、第１のアミン化合物としては、テトラエチレンペンタミンが好ましい。
【００２７】
一方、上記第１のアミン化合物と反応させる第１の脂肪酸としては、飽和又は不飽和脂肪酸が挙げられ、本発明においては、炭素数６〜３２の飽和脂肪酸を用いることが好ましい。第１の脂肪酸としては、炭素数１２〜３０の飽和脂肪酸がより好ましく、炭素数１２〜２２の飽和脂肪酸が更に好ましく、ステアリン酸が特に好ましい。
【００２８】
第１の脂肪酸と一般式（１）で表される第１のアミン化合物とを反応させることにより第１のカチオン界面活性剤が得られるが、かかる界面活性剤はアミド化合物であり、第１の脂肪酸をＲ¹¹−ＣＯＯＨ（Ｒ¹¹は飽和又は不飽和炭化水素基）とした場合に、例えば、下記一般式（３）や（４）で表すことができる（式中のＲ¹及びｎは上記と同義）。
【化６】

【化７】

【００２９】
なお、第１の脂肪酸と第１のアミン化合物からアミド化合物を得る場合においては、公知の反応条件及び反応触媒を採用することができ、第１の脂肪酸及び第１のアミン化合物のそれぞれは、１種又は２種以上を組み合わせて用いることができる。また、得られるアミド化合物（第１のカチオン界面活性剤）は、単一化合物からなるものであっても、反応で得られる複数の化合物の混合物であってもよい。なお、本発明における第１のカチオン界面活性剤は、酢酸等の弱酸でｐＨを調整させたものであってもよい。
【００３０】
本発明においては、第１のカチオン界面活性剤として、テトラエチレンペンタミンとステアリン酸の反応生成物（縮合物）に酢酸を加えｐＨを４．５〜５．５に調整したカチオン界面活性剤（以下、該カチオン界面活性剤における固形分を「ＴＥＰＡ／ＳＡ」と記す。）を用いることが好ましい。ＴＥＰＡ／ＳＡにおけるテトラエチレンペンタミンとステアリン酸の反応比率はモル比として、前者／後者＝１／１〜１／２が好ましい。
【００３１】
第２のカチオン界面活性剤は、第２の脂肪酸と下記一般式（２）で表される第２のアミン化合物との反応生成物をカルボニル基含有架橋剤と反応させてなるものである。
【化８】

【００３２】
上記式中、Ｒ²は炭素数１〜１２のアルキレン基、ｍは１〜１０の整数を示す。本発明においては、Ｒ²は炭素数２〜１０のアルキレン基がより好ましく、炭素数２〜６のアルキレン基が更に好ましく、エチレン基が特に好ましい。ｍは１〜８がより好ましく、１〜４が更に好ましく、１が特に好ましい。したがって、第１のアミン化合物としては、アミノエチルエタノールアミンが好ましい。
【００３３】
一方、上記第２のアミン化合物と反応させる第２の脂肪酸としては、飽和又は不飽和脂肪酸が挙げられ、本発明においては、炭素数６〜３２の飽和脂肪酸を用いることが好ましい。第２の脂肪酸としては、炭素数１２〜３０の飽和脂肪酸がより好ましく、炭素数１２〜２２の飽和脂肪酸が更に好ましく、ステアリン酸が特に好ましい。
【００３４】
また、カルボニル基含有架橋剤とは、第２の脂肪酸と第２のアミン化合物との反応生成物を、複数結合せしめる化合物であってカルボニル基を有する化合物を意味する。当該カルボニル基含有架橋剤による結合は、反応生成物中の第２のアミン化合物に由来するアミノ基の部分で生じることが好ましい。そして、本発明におけるカルボニル基含有架橋剤としては、尿素が特に好ましい。
【００３５】
第２の脂肪酸と一般式（２）で表される第２のアミン化合物との反応生成物は、第２の脂肪酸をＲ¹²−ＣＯＯＨ（Ｒ¹²は飽和又は不飽和炭化水素基）とした場合に、例えば、下記一般式（５）、（６）及び（７）で表すことができる（式中のＲ²及びｍは上記と同義）。
【化９】

【化１０】

【化１１】

【００３６】
なお、第２の脂肪酸と第２のアミン化合物から反応生成物を得る場合においては、公知のアミド化及び／又はエステル化反応条件及び反応触媒を採用することができ、第２の脂肪酸及び第２のアミン化合物のそれぞれは、１種又は２種以上を組み合わせて用いることができる。また、得られる反応生成物は、単一化合物からなるものであっても、反応で得られる複数の化合物の混合物であってもよい。
【００３７】
上記反応生成物とカルボニル基含有架橋剤と反応させることにより第２のカチオン界面活性剤が得られるが、カルボニル基含有架橋剤が尿素である場合は、得られる第２のカチオン界面活性剤は、例えば、下記一般式（８）の化学構造を有している。
【化１２】

【００３８】
上記式中、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴は同一でも異なってもよく、それぞれ、水素原子又はＲ¹²ＣＯ−基を示し、ｍ１、ｍ２、ｍ３及びｍ４はそれぞれ０以上の整数である。但し、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴の全てが同時に水素原子であってはならず、ｍ１＋ｍ２＋１＝ｍ、ｍ３＋ｍ４＋１＝ｍである。なお、Ｒ¹²及びｍは上記と同義である。
【００３９】
本発明において、第２のカチオン界面活性剤は、酢酸等の弱酸でｐＨを調整させたものであってもよく、例えば、上記一般式（８）のカチオン界面活性剤を酢酸でｐＨ調整した場合は、下記一般式（８ａ）で表されるカチオン界面活性剤が得られる。
【化１３】

【００４０】
本発明においては、第２のカチオン界面活性剤として、アミノエチルエタノールアミンとステアリン酸との反応生成物を尿素と反応させたカチオン界面活性剤、又は、これを更に酢酸でｐＨ調整（中和）して得られるカチオン界面活性剤を用いることが特に好ましい。この場合において、前者のカチオン界面活性剤は、例えば下記一般式（９）で表すことができ、後者のカチオン界面活性剤は、例えば下記一般式（１０）で表すことができる。
【化１４】

【化１５】

【００４１】
上記式中、Ｘ¹¹、Ｘ¹²、Ｘ¹³及びＸ¹⁴は同一でも異なってもよく、それぞれ、水素原子又はＣ₁₇Ｈ₃₅ＣＯ−基を示す。但し、Ｘ¹¹、Ｘ¹²、Ｘ¹³及びＸ¹⁴の全てが同時に水素原子であってはならない。
【００４２】
本発明における第１のカチオン界面活性剤は、上記油剤を乳化させると共に本発明のガラス繊維用集束剤で集束されたガラス繊維束を柔軟にする働きを有していると考えられる。また、第２のカチオン界面活性剤は、分子中央部分に親水基であるカルボニル基を有するため、乳化された上記油剤をガラス繊維束の内部に浸透させる働きを有していると考えられる。そして、かかる働きがあいまって、ガラス繊維束が高速で衝撃を受けた場合であっても、ガラス繊維フィラメント表面が効果的に保護され毛羽の発生が防止されるという本発明の効果が得られるものと推測される。
【００４３】
本発明における第１のカチオン界面活性剤の重量は、油剤１００重量部に対して１０〜５０重量部であることが好ましく、２０〜４０重量部であることがより好ましい。第１のカチオン界面活性剤の重量が上記範囲内である場合は、油剤の乳化及びガラス繊維束の柔軟化が特に良好に行われるようになり、ガラス繊維束の毛羽の発生が特に効率的に防止される。また、第１のカチオン界面活性剤１００重量部に対する第２のカチオン界面活性剤の重量は、５〜５０重量部であることが好ましく、１０〜３０重量部であることがより好ましい。第２のカチオン界面活性剤の重量が上記範囲内である場合は、乳化された油剤をガラス繊維束の内部に浸透させる働きが良好となり、ガラス繊維束の毛羽の発生が特に効率的に防止される。なお、第１のカチオン界面活性剤の重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として０．５〜１５重量％が好ましく、１〜１０重量％がより好ましい。そして、第２のカチオン界面活性剤の重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として０．０２５〜７．５重量％が好ましく、０．０５〜５重量％がより好ましい。
【００４４】
本発明のガラス繊維用集束剤は、第１のカチオン界面活性剤及び第２のカチオン界面活性剤以外の界面活性剤を含有していてもよい。かかる界面活性剤としては、カルボキシベタイン等の両性界面活性剤、ポリオキシエチレンポリアルキルエーテル等のノニオン性界面活性剤等が挙げられる。第１のカチオン界面活性剤及び第２のカチオン界面活性剤以外の界面活性剤を用いる場合は、その重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として０．５〜５重量％が好ましい。
【００４５】
本発明のガラス繊維用集束剤は、上述した澱粉、油剤及び界面活性剤の他に、水を必須成分とする。水は上述した成分を溶解又は分散可能であればよく、例えば、イオン交換水、蒸留水が好適に用いられる。水の重量はガラス繊維用集束剤全重量を基準として８０〜９８重量％であることが好ましく、９０〜９７重量％であることがより好ましい。
【００４６】
本発明のガラス繊維用集束剤は、上記必須成分の他、更に、防腐剤、帯電防止剤等を含有するものであってもよい。また、メタノール、エタノール、イソプロパノール等のアルコールやその他有機溶剤を少量含有していてもよい。
【００４７】
本発明において用いることのできる防腐剤は、黴や細菌等により分解を受けやすい澱粉等の成分を保護できるものであればよく、その種類は特に制限されない。好適な防腐剤としては、ホルムアルデヒドを挙げることができる。防腐剤の重量は、澱粉１００重量部に対して０．３〜２重量部であることが好ましく、０．３〜１重量部であることがより好ましい。
【００４８】
本発明において用いることのできる帯電防止剤としては、硝酸リチウム、塩化リチウム等の無機塩や４級アンモニウム塩等が挙げられ、かかる帯電防止剤の重量は、ガラス繊維用集束剤の不揮発成分の全重量を基準として０．０１〜１．０重量％であることが好ましい。
【００４９】
本発明のガラス繊維用集束剤は以下に述べるような製造方法により効率的に製造することができる。すなわち、澱粉を水に分散させた後、９０〜９８℃に加熱し糊化させて８０℃以下に冷却し、これに、第１のカチオン界面活性剤及び第２のカチオン界面活性剤を含む界面活性剤、油剤の水溶液（又は水分散物）をそれぞれ単独で、若しくは混合した状態で添加し、必要に応じて更に水で希釈する。
上記必須成分以外の防腐剤、帯電防止剤等を添加する場合も、これらを単独又は水溶液（又は水分散物）として、糊化した澱粉溶液に加えればよい。
【００５０】
次に、本発明のガラス繊維束について説明する。本発明のガラス繊維束は、上述のガラス繊維用集束剤によりガラス繊維フィラメントが複数本集束されてなるものである。すなわち、本発明のガラス繊維束は、複数本のガラス繊維フィラメントと本発明のガラス繊維用集束剤とから構成されており、ガラス繊維用集束剤は複数のガラス繊維フィラメント間に存在し、ガラス繊維フィラメントを束ねる接着剤（バインダ）として機能している。また、ガラス繊維用集束剤はガラス繊維フィラメントの外周を連続又は不連続膜として被覆し、ガラス繊維を保護する機能も有している。なお、本発明において、ガラス繊維束に存在するガラス繊維用集束剤は、該集束剤の不揮発成分であることが好ましい。
【００５１】
ガラス繊維用集束剤は、ガラス繊維束の使用時にガラス繊維フィラメントを束状に保っておくだけの強度を有していればよく、ガラス繊維束内に一様に分布している必要はない。すなわち、ガラス繊維フィラメント同士の接着性の観点からは、ガラス繊維用集束剤はガラス繊維束の外縁部から中心部へ向けて略均一の濃度で分布していることが好ましいが、例えば、外縁部の濃度が高く中心部の濃度が低い場合であってもガラス繊維フィラメントを保持可能であり実用上問題とならないため、かかる構成のガラス繊維束も本発明において採用可能である。
【００５２】
本発明のガラス繊維束に用いられるガラス繊維フィラメントのフィラメント径は３〜２３μｍが好ましく、ガラス繊維束はかかるガラス繊維フィラメントが５０〜１２００本集束されてなるものであることが好ましい。ガラス繊維フィラメントのガラス組成としては、例えば、Ｅガラス、Ｓガラス、Ｃガラス等が挙げられる。本発明において、ガラス繊維フィラメント１００重量部に対するガラス繊維用集束剤の不揮発成分重量は、０．５〜１．５重量部であることが好ましく、０．７〜１．２重量部がより好ましい。また、本発明のガラス繊維束の態様としては、ガラス繊維ヤーン、ガラス繊維ロービング及びガラス繊維チョップドストランドが挙げられる。
【００５３】
本発明のガラス繊維束は、例えば、白金ノズル（ブッシング）から引き出されたガラス繊維フィラメントにローラー型アプリケーターやベルト型アプリケーター等を用いてガラス繊維用集束剤を塗布し、これを集束機で集束することによってガラス繊維フィラメントを束ね、次いで、これを室温〜１５０℃で乾燥し、水等の揮発成分を除去することにより製造することができる。なお、適宜、加撚を施してもよい。
【００５４】
次に、本発明のガラス繊維織物の製造方法について説明する。本発明のガラス繊維織物の製造方法は、ガラス繊維束を経糸及び緯糸としてエアジェット織機により製織するガラス繊維織物の製造方法であって、前記経糸及び緯糸のうち少なくとも緯糸は、上述した本発明のガラス繊維束であることを特徴とするものである。
【００５５】
本発明のガラス繊維織物の製造方法においては、巻取りチューブ（外径：１５〜４０ｃｍ、長さ：１０〜６０ｃｍ程度）の周囲に１０〜２００ｋｍ程度巻き付けて巻糸体としたガラス繊維束を用い、かかる巻糸体からガラス繊維束を解舒して製織に供することが製造工程上好ましい。なお、本発明のガラス繊維束を経糸として用いる場合は、製織に先立って経糸に二次サイズ剤を塗布してもよい。
【００５６】
本発明のガラス繊維織物の製造方法においては、また、５〜５００ＴＥＸ（好ましくは２２〜６８ＴＥＸ）のガラス繊維束を経糸及び緯糸として用い、織り密度が、経方向で１６〜６４本／２５ｍｍ、緯方向で１５〜６０本／２５ｍｍになるように製織することが好ましい。
【００５７】
エアジェット織機におけるエアノズル周辺の要部模式図は図１（ａ）及び（ｂ）に示されており、同図に示されるように、飛走する緯糸（ガラス繊維束）はバルーンブレーカと高速で接触するが、本発明のガラス繊維織物の製造方法によれば、緯糸として本発明のガラス繊維用集束剤で集束したガラス繊維束を用いるため、バルーンブレーカと緯糸との衝突によってもガラス繊維束表面に毛羽が生じ難く、このために製織を効率的に行うことができ、得られるガラス繊維織物の製品品質を向上させることも可能になる。
【００５８】
【実施例】
以下、本発明の好適な実施例についてさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００５９】
［ガラス繊維用集束剤の製造］
（実施例１）
エーテル化ハイアミロースコーンスターチ２．０ｋｇ及びエピクロルヒドリンで架橋した架橋コーンスターチ２．０ｋｇに７０ｋｇの水を加え分散させた。次いで、これを加熱昇温し９５℃で３０分間糊化した後、６５℃まで冷却した（得られた液をＡ液とする）。
【００６０】
一方、ステアリン酸とアミノエチルエタノールアミンをモル比１：１で脱水しながら１８０℃で反応させて得られた生成物２モルに、尿素１モルを加え１８０℃で反応（架橋）させることにより得られた第２のカチオン界面活性剤（以下「界面活性剤Ａ」という。）６０ｇ、加熱溶解させた牛脂油０．６ｋｇ、パーム油０．４ｋｇ、及びポリオキシエチレンポリプロピレンエーテル界面活性剤（ＨＬＢ＝１１）０．１ｋｇに熱湯を加えながらミキサーで攪拌した。攪拌を５分間継続した後に熱湯で希釈して、総重量を５ｋｇとした（得られた液をＢ液とする）。
【００６１】
また、第１のカチオン界面活性剤であるＴＥＰＡ／ＳＡ（テトラエチレンペンタミンとステアリン酸とのモル比：前者／後者＝１／２）３００ｇに熱湯を加えて総重量を２ｋｇとした（得られた液をＣ液とする）。更に、ホルマリン液（ホルムアルデヒド３０重量％水溶液）１００ｇを水で１０倍に希釈した（得られた液をＤ液とする）。
【００６２】
次いで、６５℃のＡ液に、Ｂ液、Ｃ液及びＤ液を順次全量添加した後、総重量が１００ｋｇになるように湯を加えてガラス繊維用集束剤を得、６０℃で保温した。なお、エーテル化ハイアミロースコーンスターチの残留粒子率は５０重量％であり、架橋コーンスターチの残留粒子率は８０重量％であり、澱粉の残留粒子率は平均で６５重量％であった。
【００６３】
（実施例２）
エーテル化ハイアミロースコーンスターチの重量を１．０ｋｇとし、エピクロルヒドリンで架橋した架橋コーンスターチ２．０ｋｇに代えて、エーテル化コーンスターチ３．０ｋｇを用いた他は実施例１と同様にして、ガラス繊維用集束剤を得、６０℃で保温した。なお、エーテル化ハイアミロースコーンスターチの残留粒子率は５０重量％であり、エーテル化コーンスターチの残留粒子率は５重量％であり、澱粉の残留粒子率は平均で１６重量％であった。
【００６４】
（比較例１）
エーテル化ハイアミロースコーンスターチ１．０ｋｇ及びエーテル化コーンスターチ３．０ｋｇに７０ｋｇの水を加え分散させた。次いで、これを加熱昇温し９５℃で３０分間糊化した後、６５℃まで冷却した（得られた液をＡ１液とする）。
【００６５】
一方、加熱溶解させた牛脂油０．６ｋｇ、パーム油０．４ｋｇ、ポリオキシエチレンポリプロピレンエーテル界面活性剤（ＨＬＢ＝１１）０．１ｋｇに熱湯を加えながらミキサーで攪拌した。攪拌を５分間継続した後に熱湯で希釈して、総重量を５ｋｇとした（得られた液をＢ１液とする）。
【００６６】
また、第１のカチオン界面活性剤であるＴＥＰＡ／ＳＡ（テトラエチレンペンタミンとステアリン酸とのモル比：前者／後者＝１／２）３００ｇに熱湯を加えて総重量を２ｋｇとした（得られた液をＣ１液とする）。更に、ホルマリン液（ホルムアルデヒド３０重量％水溶液）１００ｇを水で１０倍に希釈した（得られた液をＤ１液とする）。
【００６７】
次いで、６５℃のＡ１液に、Ｂ１液、Ｃ１液及びＤ１液を順次全量添加した後、総重量が１００ｋｇになるように湯を加えてガラス繊維用集束剤を得、６０℃で保温した。なお、エーテル化ハイアミロースコーンスターチの残留粒子率は５０重量％であり、エーテル化コーンスターチの残留粒子率は５重量％であり、澱粉の残留粒子率は平均で１６重量％であった。
【００６８】
（比較例２）
エーテル化ハイアミロースコーンスターチ１．０ｋｇ及びエーテル化コーンスターチ３．０ｋｇに７０ｋｇの水を加え分散させた。次いで、これを加熱昇温し９５℃で３０分間糊化した後、６５℃まで冷却した（得られた液をＡ２液とする）。
【００６９】
一方、界面活性剤Ａ６０ｇ、加熱溶解させた牛脂油０．６ｋｇ、パーム油０．４ｋｇ及びポリオキシエチレンポリプロピレンエーテル界面活性剤（ＨＬＢ＝１１）０．１ｋｇに熱湯を加えながらミキサーで攪拌した。攪拌を５分間継続した後に熱湯で希釈して、総重量を５ｋｇとした（得られた液をＢ２液とする）。また、ホルマリン液（ホルムアルデヒド３０重量％水溶液）１００ｇを水で１０倍に希釈した（得られた液をＤ２液とする）。
【００７０】
次いで、６５℃のＡ２液に、Ｂ２液及びＤ２液を順次全量添加した後、総重量が１００ｋｇになるように湯を加えてガラス繊維用集束剤を得、６０℃で保温した。なお、エーテル化ハイアミロースコーンスターチの残留粒子率は５０重量％であり、エーテル化コーンスターチの残留粒子率は５重量％であり、澱粉の残留粒子率は平均で１６重量％であった。
【００７１】
［ガラス繊維束の製造］
（実施例３〜４及び比較例３〜４）
ロールコーターを用いて、Ｅガラスのガラス繊維フィラメント（フィラメント径９μｍ）に、実施例１〜２及び比較例１〜２で得られたガラス繊維用集束剤それぞれを塗布し４００本集束して、１２０℃で２５時間乾燥させガラス繊維束を得た。なお、得られたガラス繊維束におけるガラス繊維用集束剤（不揮発成分）の付着量は、ガラス繊維フィラメント１００重量部に対して、１．０重量部であった。なお、実施例１〜２及び比較例１〜２で得られたガラス繊維用集束剤を用いたものが、それぞれ実施例３〜４及び比較例３〜４に該当する。
【００７２】
［ガラス繊維織物の製造］
（実施例５〜６及び比較例５〜６）
実施例３〜４及び比較例３〜４で得られたガラス繊維束に以下の表１に示す組成のサイズ剤を塗布した後、揮発成分を除去させた（ガラス繊維束１００重量部に対するサイズ剤の被覆量は不揮発成分として１重量部）。このガラス繊維束を経糸として用い、実施例３〜４及び比較例３〜４で得られたガラス繊維束を緯糸として用い、バルーンブレーカを備えた高速エアージェット織機（津田駒工業社製、ＺＡ）にて製織を行い、ＩＰＣスペック７６２８タイプのガラス繊維織物を得た。なお、製織中にバルーンブレーカと接触した緯糸の飛走速度は３２５０ｍ／分であった。また、実施例１〜２及び比較例１〜２のガラス繊維用集束剤が塗布された経糸に対して、それぞれ実施例１〜２及び比較例１〜２のガラス繊維用集束剤が塗布された緯糸を用いた。そして、実施例１〜２及び比較例１〜２のガラス繊維用集束剤塗布された経糸及び緯糸を用いたものが、それぞれ実施例５〜６及び比較例５〜６に該当する。
【００７３】
【表１】

【００７４】
［毛羽の評価］
実施例５〜６及び比較例５〜６の方法でガラス繊維織物を１００ｍ作製し、織長５０ｃｍあたりに発生した毛羽による突起物発生数を測定し、以下の表２に示す基準で評価した。
【００７５】
【表２】

【００７６】
毛羽の評価結果を、以下の表３に示す。なお、結果は塗布されたガラス繊維用集束剤の種類に基づいて示し（実施例１〜２及び比較例１〜２と記載）、ガラス繊維用集束剤の含有成分のうち不揮発成分の重量％、油剤１００重量部に対する第１のカチオン界面活性剤の重量、第１のカチオン界面活性剤１００重量部に対する第２のカチオン界面活性剤の重量、及び澱粉の残留粒子率も併記した。
【００７７】
【表３】

【００７８】
【発明の効果】
以上説明したように、本発明によれば、エアジェット織機による製織時における摩擦や衝撃による毛羽の発生を効果的に防止することが可能なガラス繊維集束剤を提供することが可能になる。また、かかるガラス繊維集束剤で集束されてなるガラス繊維束、及び、かかるガラス繊維束を用いたガラス繊維織物の製造方法を提供することが可能になる。
【図面の簡単な説明】
【図１】エアジェット織機におけるエアノズル周辺の要部模式図であり、（ａ）は斜視図、（ｂ）は上面図である。
【符号の説明】
１…ガラス繊維巻糸体、２…バルーンブレーカ、３…エアノズル、４…おさ、１０…ガラス繊維束。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glass fiber sizing agent, a glass fiber bundle that is bundled with the glass fiber sizing agent, and a method for producing a glass fiber fabric using the glass fiber bundle.
[0002]
[Prior art]
The glass fiber fabric is manufactured by weaving with various weaving machines using a glass fiber bundle formed by bundling glass fiber filaments with a bundling agent as warp and weft.
And as a weaving machine for glass fiber fabrics, it is common to use an air jet weaving machine in which wefts fly with air jetted from an air nozzle.
[0003]
FIG. 1 is a schematic view of a main part around an air nozzle in such an air jet loom, and FIGS. 1 (a) and 1 (b) show a perspective view and a top view, respectively. In the air jet loom shown in the figure, a glass fiber bundle 10 which is a weft is unwound from a glass fiber wound body 1 in which the fiber bundle is wound in a truncated cone shape by air jetted from an air nozzle 3. Then, while the position is held by the sheath 4, it flies so as to intersect with a warp (not shown) orthogonal to the glass fiber bundle 10, and a glass fiber fabric is formed. Between the glass fiber wound body 1 and the air nozzle 3, a balloon breaker 2 that is a flare-shaped cylinder is disposed, and when the flying glass fiber bundle 10 contacts the inner surface of the balloon breaker 2, the glass fiber The flying of the glass fiber bundle 10 which has been unwound from the wound body 1 and caused a large swell is stabilized.
[0004]
By the way, since the flight of the glass fiber bundle 10 in the air jet loom is very high speed, the glass fiber bundle 10 receives a large impact when the glass fiber bundle 10 comes into contact with the balloon breaker 2. Conventionally, there has been a problem that fluff is generated in the bundle 10 to cause poor weaving or defective products.
[0005]
Since it is impossible to remove the balloon breaker 2 in the manufacturing process of the glass fiber fabric, in order to solve the above problem, even if the balloon breaker 2 is brought into contact with the balloon breaker 2 at a high speed, a glass fiber bundle that does not generate fluff Therefore, it is essential to improve the performance of the glass fiber sizing agent. However, it has been impossible to prevent fuzz with existing sizing agents for glass fibers (for example, the sizing agent disclosed in JP-A No. 49-1000039).
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of such problems of the prior art, and provides a glass fiber sizing agent capable of effectively preventing the generation of fluff due to friction and impact during weaving with an air jet loom. For the purpose. Another object of the present invention is to provide a glass fiber bundle that is bundled with such a glass fiber sizing agent, and a method for producing a glass fiber fabric using the glass fiber bundle.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have added a cationic surfactant having a specific structure as a surfactant to a water-based glass fiber sizing agent containing starch as a film-forming agent. The inventors have found that the above object can be achieved by using two types in combination, and completed the present invention.
[0008]
That is, the glass fiber sizing agent of the present invention is a glass fiber sizing agent containing starch, an oil agent, a surfactant, and water, and the surfactant comprises the first fatty acid and the following general formula ( Reaction between the first cationic surfactant obtained by reacting the first amine compound represented by 1) and the second fatty acid and the second amine compound represented by the following general formula (2) And a second cationic surfactant obtained by reacting the product with a carbonyl group-containing crosslinking agent.
[Chemical 3]

[Formula 4]

[Wherein R ¹ And R ² May be the same or different and each represents an alkylene group having 1 to 12 carbon atoms, n is an integer of 0 to 10, and m is an integer of 1 to 10. ]
[0009]
In the sizing agent for glass fibers of the present invention, the first fatty acid and the second fatty acid are the same or different saturated fatty acids having 6 to 32 carbon atoms, R ¹ And R ² Is preferably an ethylene group. The carbonyl group-containing crosslinking agent is preferably urea.
[0010]
In the sizing agent for glass fibers of the present invention, the weight of the first cationic surfactant with respect to 100 parts by weight of the oil is preferably 10 to 50 parts by weight, and with respect to 100 parts by weight of the first cationic surfactant. The weight of the second cationic surfactant is preferably 5 to 50 parts by weight, and the starch is preferably starch having a residual particle ratio of 30 to 70% by weight.
[0011]
The glass fiber bundle of the present invention is characterized in that a plurality of glass fiber filaments are bundled by the glass fiber sizing agent of the present invention. In such a glass fiber bundle, the weight of the glass fiber filament is 100 weight. It is preferable that the non-volatile component weight of the glass fiber sizing agent with respect to parts is 0.5 to 1.5 parts by weight.
In the present invention, the nonvolatile component refers to a component that does not volatilize when a glass fiber sizing agent is applied to a glass fiber filament and heated to 110 ° C., and the nonvolatile component weight refers to the weight of the component.
[0012]
The method for producing a glass fiber fabric of the present invention is a method for producing a glass fiber fabric in which a glass fiber bundle is used as a warp and a weft by an air jet loom, and at least the weft and the weft are the glass fibers of the present invention. It is characterized by being a bundle.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the glass fiber sizing agent of the present invention contains starch, an oil agent, a surfactant and water as essential components. In the present invention, at least a part of the surfactant includes the following specific cations. A great feature is that the surfactants (a) and (b) are used in combination.
(A) a first cationic surfactant obtained by reacting the first fatty acid and the first amine compound represented by the general formula (1) (hereinafter simply referred to as “first cationic surfactant”) .)
(B) a second cationic surfactant obtained by reacting a reaction product of the second fatty acid and the second amine compound represented by the above general formula (2) with a carbonyl group-containing crosslinking agent (hereinafter simply referred to as “a second cationic surfactant”). Referred to as "second cationic surfactant").
[0014]
Conventionally, a glass fiber sizing agent containing a surfactant corresponding to the second cationic surfactant has been known (for example, the above-mentioned JP-A No. 49-1000039). Although it is said that it is possible to improve the bundling property, flexibility and lubricity of the glass fiber bundle to which the glass fiber bundling agent is applied (the same publication), the present inventors have described the second cation. By combining the surfactant with the first cationic surfactant, the surface of the glass fiber filament is effective even when the glass fiber bundle coated with the glass fiber sizing agent containing them is subjected to impact at high speed. The present inventors have obtained a completely new finding that it is protected and the generation of fluff is prevented, and the present invention has been conceived based on this finding.
[0015]
Hereinafter, each of starch, oil agent, surfactant and water, which are essential components of the sizing agent for glass fibers of the present invention, will be described in detail. First, starch will be described.
[0016]
Examples of the starch used in the present invention include corn starch (corn starch), tapioca starch, wheat starch, sweet potato starch, potato starch, high amylose corn starch, sago starch, and rice starch. Moreover, the amylose extract of a potato starch and the special starch synthesize | combined with the enzyme can also be used. These starches may be subjected to processing such as etherification, esterification, grafting, and crosslinking.
[0017]
Examples of the etherified starch include carboxymethyl etherified starch, hydroxyalkyl etherified starch, alkyl etherified starch, benzyl etherified starch, and cationic etherified starch. Examples of the esterified starch include acetate esterified starch, phosphate esterified starch, sulfate esterified starch, nitrate esterified starch, and xanthate esterified starch. In both the etherification and esterification, there is no particular limitation on the degree of starch substitution.
[0018]
Grafted starch is a graft polymerized with at least one monomer having an unsaturated double bond such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, styrene, maleic acid, etc. Can be exemplified.
[0019]
Examples of the starch further include those obtained by introducing cross-linking to raw starch, and those obtained by introducing cross-linking to the above-mentioned starch that has been etherified, esterified or grafted. In the case of introducing cross-linking, a compound having two or more functional groups reactive with hydroxyl groups in starch or a compound that newly generates a hydroxyl-functional functional group by reaction with hydroxyl groups in starch is used as a crosslinking agent. Used. Examples of such a crosslinking agent include epichlorohydrin, formaldehyde, diepoxide compounds, dialdehyde compounds, and the like.
[0020]
The amount of the amylose component and the amount of the amylopectin component in the starch used in the present invention are arbitrary. Regular starch having an amylose component of less than 50% by weight (typically containing about 30% by weight of amylose component and about 70% by weight of amylopectin component), and high amylose type starch containing typically 50% by weight or more of amylose component (typically In particular, any one of about 70% by weight of the amylose component and about 30% by weight of the amylopectin component can be used. It is generally said that the sizing agent containing normal type starch is excellent in adhesiveness, and the starch containing high amylose type starch is excellent in film-forming property. In the present invention, at least a part of the starch used is preferably a high amylose type starch, and more preferably a combination of normal type starch and high amylose type starch. The weight of the starch is preferably 40 to 80% by weight, more preferably 45 to 75% by weight, based on the total weight of the nonvolatile components of the glass fiber sizing agent.
[0021]
In the present invention, it is preferable to use starch having a residual particle ratio of 30 to 70% by weight. Here, the residual particle ratio of starch means a ratio determined by the following method. That is, after starch is dispersed in water, it is gelatinized by heating to 95 ° C. to obtain a paste liquid (the starch ratio is 5% by weight based on the total weight of the paste liquid in terms of anhydrous), and this is centrifuged (5000 rpm 10 minutes), the supernatant is collected, dried at 110 ° C. for 30 minutes, and the solid content rate (% by weight) is measured. The residual particle ratio (% by weight) is calculated by the following formula (I) using this solid content ratio (% by weight).
[Expression 1]

[0022]
When the residual particle ratio is the above-mentioned weight%, when a glass fiber bundle is produced by bundling a plurality of glass fiber filaments with the glass fiber bundling agent of the present invention, the adhesive strength for bundling the glass fiber filaments increases. There is a tendency. The residual particle ratio is more preferably 40 to 65% by weight. In addition, when using combining multiple types of starch, a residual particle rate uses an average value.
[0023]
Next, the oil agent in the sizing agent for glass fibers of the present invention will be described. Oils that can be used in the present invention include animal oils such as modified silicone oil and beef tallow oil and hydrogenated products thereof; vegetable oils such as sesame oil, rapeseed oil and palm oil and hydrogenated products thereof; higher saturated fatty acids and higher saturated alcohols. Examples include condensates (stearic acid esters such as lauryl stearate); paraffin wax and the like. The oil agent in the sizing agent for glass fibers has a function of giving a slip to the glass fiber bundle, reducing friction on the machine, and protecting the glass fibers. The weight of the oil agent is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, based on the total weight of the nonvolatile components of the glass fiber sizing agent.
[0024]
Next, the surfactant in the present invention will be described. In the present invention, the surfactant contains the first cationic surfactant and the second cationic surfactant as essential components.
[0025]
The first cationic surfactant is obtained by reacting the first fatty acid and the first amine compound represented by the following general formula (1).
[Chemical formula 5]

[0026]
In the above formula, R ¹ Represents an alkylene group having 1 to 12 carbon atoms, n represents an integer of 0 to 10, and specific examples of the first amine compound represented by the general formula (1) include diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. , Pentaethylenehexamine, and hexaethyleneheptamine. In the present invention, R ¹ Is more preferably an alkylene group having 2 to 10 carbon atoms, still more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an ethylene group. As for n, 1-8 are more preferable, 1-6 are still more preferable, and 3 is especially preferable. Therefore, tetraethylenepentamine is preferable as the first amine compound.
[0027]
On the other hand, examples of the first fatty acid to be reacted with the first amine compound include saturated or unsaturated fatty acids. In the present invention, it is preferable to use a saturated fatty acid having 6 to 32 carbon atoms. As the first fatty acid, a saturated fatty acid having 12 to 30 carbon atoms is more preferable, a saturated fatty acid having 12 to 22 carbon atoms is further preferable, and stearic acid is particularly preferable.
[0028]
The first cationic surfactant is obtained by reacting the first fatty acid and the first amine compound represented by the general formula (1), and the surfactant is an amide compound, Fatty acid R ¹¹ -COOH (R ¹¹ Is a saturated or unsaturated hydrocarbon group), for example, it can be represented by the following general formula (3) or (4) (R in the formula: ¹ And n are as defined above.
[Chemical 6]

[Chemical 7]

[0029]
In the case of obtaining an amide compound from the first fatty acid and the first amine compound, known reaction conditions and reaction catalysts can be employed, and each of the first fatty acid and the first amine compound is 1 Species or a combination of two or more can be used. Further, the amide compound (first cationic surfactant) obtained may be a single compound or a mixture of a plurality of compounds obtained by the reaction. In addition, the 1st cationic surfactant in this invention may adjust pH with weak acids, such as an acetic acid.
[0030]
In the present invention, as the first cationic surfactant, a cationic surfactant in which acetic acid is added to the reaction product (condensate) of tetraethylenepentamine and stearic acid to adjust the pH to 4.5 to 5.5 ( Hereinafter, the solid content in the cationic surfactant is preferably referred to as “TEPA / SA”. The molar ratio of tetraethylenepentamine and stearic acid in TEPA / SA is preferably the former / the latter = 1/1 to 1/2.
[0031]
The second cationic surfactant is obtained by reacting a reaction product of the second fatty acid and the second amine compound represented by the following general formula (2) with a carbonyl group-containing crosslinking agent.
[Chemical 8]

[0032]
In the above formula, R ² Represents an alkylene group having 1 to 12 carbon atoms, and m represents an integer of 1 to 10. In the present invention, R ² Is more preferably an alkylene group having 2 to 10 carbon atoms, still more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an ethylene group. As for m, 1-8 are more preferable, 1-4 are still more preferable, and 1 is especially preferable. Accordingly, aminoethylethanolamine is preferred as the first amine compound.
[0033]
On the other hand, examples of the second fatty acid to be reacted with the second amine compound include saturated or unsaturated fatty acids. In the present invention, it is preferable to use a saturated fatty acid having 6 to 32 carbon atoms. As the second fatty acid, a saturated fatty acid having 12 to 30 carbon atoms is more preferable, a saturated fatty acid having 12 to 22 carbon atoms is further preferable, and stearic acid is particularly preferable.
[0034]
The carbonyl group-containing crosslinking agent means a compound having a carbonyl group, which is a compound that bonds a plurality of reaction products of the second fatty acid and the second amine compound. The binding by the carbonyl group-containing crosslinking agent preferably occurs at the amino group portion derived from the second amine compound in the reaction product. And as a carbonyl group containing crosslinking agent in this invention, urea is especially preferable.
[0035]
The reaction product of the second fatty acid and the second amine compound represented by the general formula (2) is obtained by converting the second fatty acid to R ¹² -COOH (R ¹² Can be represented by, for example, the following general formulas (5), (6) and (7) (R in the formula) ² And m are as defined above.
[Chemical 9]

[Chemical Formula 10]

Embedded image

[0036]
In the case of obtaining a reaction product from the second fatty acid and the second amine compound, known amidation and / or esterification reaction conditions and reaction catalysts can be adopted, and the second fatty acid and the second fatty acid can be used. Each of these amine compounds can be used alone or in combination of two or more. Moreover, the reaction product obtained may be a single compound or a mixture of a plurality of compounds obtained by the reaction.
[0037]
A second cationic surfactant is obtained by reacting the reaction product with a carbonyl group-containing crosslinking agent. When the carbonyl group-containing crosslinking agent is urea, the obtained second cationic surfactant is: For example, it has a chemical structure of the following general formula (8).
Embedded image

[0038]
In the above formula, X ¹ , X ² , X ^Three And X ^Four May be the same or different and each represents a hydrogen atom or R ¹² CO— group is shown, and m1, m2, m3 and m4 are each an integer of 0 or more. However, X ¹ , X ² , X ^Three And X ^Four Must not be hydrogen atoms at the same time, and m1 + m2 + 1 = m and m3 + m4 + 1 = m. R ¹² And m are as defined above.
[0039]
In the present invention, the second cationic surfactant may have a pH adjusted with a weak acid such as acetic acid. For example, when the pH of the cationic surfactant of the general formula (8) is adjusted with acetic acid, Gives a cationic surfactant represented by the following general formula (8a).
Embedded image

[0040]
In the present invention, as the second cationic surfactant, a cationic surfactant obtained by reacting a reaction product of aminoethylethanolamine and stearic acid with urea, or pH adjustment (neutralization) with acetic acid. It is particularly preferable to use a cationic surfactant obtained as described above. In this case, the former cationic surfactant can be represented by, for example, the following general formula (9), and the latter cationic surfactant can be represented, for example, by the following general formula (10).
Embedded image

Embedded image

[0041]
In the above formula, X ¹¹ , X ¹² , X ¹³ And X ¹⁴ May be the same or different and each represents a hydrogen atom or C ₁₇ H ₃₅ CO-group is shown. However, X ¹¹ , X ¹² , X ¹³ And X ¹⁴ Must not be hydrogen atoms at the same time.
[0042]
The first cationic surfactant in the present invention is considered to have a function of emulsifying the oil agent and softening the glass fiber bundle focused with the glass fiber sizing agent of the present invention. Moreover, since the 2nd cationic surfactant has a carbonyl group which is a hydrophilic group in the center part of a molecule | numerator, it is thought that it has the function to permeate | transmit the emulsified said oil agent inside a glass fiber bundle. And even if this function is combined, even when the glass fiber bundle is impacted at high speed, the effect of the present invention is obtained that the surface of the glass fiber filament is effectively protected and the generation of fluff is prevented. It is guessed.
[0043]
The weight of the first cationic surfactant in the present invention is preferably 10 to 50 parts by weight and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the oil. When the weight of the first cationic surfactant is within the above range, emulsification of the oil agent and softening of the glass fiber bundle are performed particularly well, and generation of fluff of the glass fiber bundle is particularly efficiently performed. Is prevented. Further, the weight of the second cationic surfactant with respect to 100 parts by weight of the first cationic surfactant is preferably 5 to 50 parts by weight, and more preferably 10 to 30 parts by weight. When the weight of the second cationic surfactant is within the above range, the function of allowing the emulsified oil agent to penetrate into the inside of the glass fiber bundle is improved, and generation of fluff in the glass fiber bundle is particularly effectively prevented. The The weight of the first cationic surfactant is preferably 0.5 to 15% by weight and more preferably 1 to 10% by weight based on the total weight of the nonvolatile components of the glass fiber sizing agent. The weight of the second cationic surfactant is preferably 0.025 to 7.5% by weight, more preferably 0.05 to 5% by weight based on the total weight of the nonvolatile components of the glass fiber sizing agent.
[0044]
The sizing agent for glass fibers of the present invention may contain a surfactant other than the first cationic surfactant and the second cationic surfactant. Examples of such surfactants include amphoteric surfactants such as carboxybetaine and nonionic surfactants such as polyoxyethylene polyalkyl ether. When a surfactant other than the first cationic surfactant and the second cationic surfactant is used, the weight is 0.5 to 5% by weight based on the total weight of the nonvolatile components of the glass fiber sizing agent. Is preferred.
[0045]
The sizing agent for glass fibers of the present invention contains water as an essential component in addition to the above-described starch, oil agent and surfactant. Water may be used as long as it can dissolve or disperse the above-described components. For example, ion-exchanged water or distilled water is preferably used. The weight of water is preferably 80 to 98% by weight, more preferably 90 to 97% by weight, based on the total weight of the sizing agent for glass fibers.
[0046]
The sizing agent for glass fibers of the present invention may contain a preservative, an antistatic agent and the like in addition to the above essential components. Moreover, alcohol, such as methanol, ethanol, and isopropanol, and other organic solvents may be contained in a small amount.
[0047]
The preservative that can be used in the present invention is not particularly limited as long as it can protect components such as starch that are susceptible to decomposition by sputum and bacteria. A suitable preservative is formaldehyde. The weight of the preservative is preferably 0.3 to 2 parts by weight and more preferably 0.3 to 1 part by weight with respect to 100 parts by weight of starch.
[0048]
Examples of the antistatic agent that can be used in the present invention include inorganic salts such as lithium nitrate and lithium chloride, quaternary ammonium salts, and the like. The weight of the antistatic agent is the total of the non-volatile components of the sizing agent for glass fibers. It is preferably 0.01 to 1.0% by weight based on the weight.
[0049]
The sizing agent for glass fibers of the present invention can be efficiently produced by a production method as described below. That is, after the starch is dispersed in water, it is heated to 90 to 98 ° C. to be gelatinized and cooled to 80 ° C. or less, and this includes an interface containing the first cationic surfactant and the second cationic surfactant. The aqueous solution (or aqueous dispersion) of the activator and oil agent is added alone or in a mixed state, and further diluted with water as necessary.
When adding preservatives, antistatic agents and the like other than the above essential components, these may be added alone or as an aqueous solution (or aqueous dispersion) to the gelatinized starch solution.
[0050]
Next, the glass fiber bundle of the present invention will be described. The glass fiber bundle of the present invention is formed by bundling a plurality of glass fiber filaments with the above-mentioned bundling agent for glass fibers. That is, the glass fiber bundle of the present invention is composed of a plurality of glass fiber filaments and the glass fiber sizing agent of the present invention, and the glass fiber sizing agent is present between the plurality of glass fiber filaments. It functions as an adhesive (binder) for bundling filaments. The sizing agent for glass fibers also has a function of protecting the glass fibers by coating the outer periphery of the glass fiber filaments as a continuous or discontinuous film. In the present invention, the glass fiber sizing agent present in the glass fiber bundle is preferably a non-volatile component of the sizing agent.
[0051]
The sizing agent for glass fibers only needs to have a strength sufficient to keep the glass fiber filaments in a bundle shape when the glass fiber bundle is used, and does not need to be uniformly distributed in the glass fiber bundle. That is, from the viewpoint of adhesiveness between glass fiber filaments, the glass fiber sizing agent is preferably distributed at a substantially uniform concentration from the outer edge of the glass fiber bundle toward the center. The glass fiber bundle can be held in the present invention even when the concentration is high and the concentration at the center is low, and this is not a problem in practical use.
[0052]
The glass fiber filament used in the glass fiber bundle of the present invention preferably has a filament diameter of 3 to 23 μm, and the glass fiber bundle is preferably formed by bundling 50 to 1200 glass fiber filaments. Examples of the glass composition of the glass fiber filament include E glass, S glass, and C glass. In this invention, it is preferable that the non-volatile component weight of the sizing agent for glass fibers with respect to 100 weight part of glass fiber filaments is 0.5-1.5 weight part, and 0.7-1.2 weight part is more preferable. Moreover, as an aspect of the glass fiber bundle of this invention, a glass fiber yarn, a glass fiber roving, and a glass fiber chopped strand are mentioned.
[0053]
In the glass fiber bundle of the present invention, for example, a glass fiber sizing agent is applied to a glass fiber filament drawn from a platinum nozzle (bushing) using a roller-type applicator, a belt-type applicator, or the like, and the resulting glass fiber bundle is focused by a sizing machine. Thus, the glass fiber filaments can be bundled and then dried at room temperature to 150 ° C. to remove volatile components such as water. In addition, you may give twist suitably.
[0054]
Next, the manufacturing method of the glass fiber fabric of this invention is demonstrated. The method for producing a glass fiber fabric of the present invention is a method for producing a glass fiber fabric in which a glass fiber bundle is woven by an air jet loom as warp yarns and weft yarns, and at least of the warp yarns and weft yarns, It is a glass fiber bundle.
[0055]
In the manufacturing method of the glass fiber fabric of this invention, the glass fiber bundle used as the wound body by winding about 10-200 km around the winding tube (outer diameter: 15-40 cm, length: about 10-60 cm) is used. In view of the production process, it is preferable to unwind the glass fiber bundle from the wound body and use it for weaving. In addition, when using the glass fiber bundle of this invention as a warp, you may apply | coat a secondary sizing agent to a warp prior to weaving.
[0056]
In the method for producing a glass fiber fabric of the present invention, a glass fiber bundle of 5 to 500 TEX (preferably 22 to 68 TEX) is used as warp and weft, and the weave density is 16 to 64/25 mm in the warp direction. It is preferable to weave so that it is 15-60 pieces / 25 mm in the direction.
[0057]
The schematic diagram of the main part around the air nozzle in the air jet loom is shown in FIGS. 1 (a) and 1 (b). As shown in the figure, the flying weft (glass fiber bundle) is at high speed with the balloon breaker. However, according to the method for producing a glass fiber fabric of the present invention, since the glass fiber bundle bundled with the glass fiber sizing agent of the present invention is used as the weft, the surface of the glass fiber bundle is also affected by the collision between the balloon breaker and the weft. Therefore, weaving can be performed efficiently and the product quality of the resulting glass fiber fabric can be improved.
[0058]
【Example】
EXAMPLES Hereinafter, although the preferable Example of this invention is described in detail, this invention is not limited to these Examples.
[0059]
[Manufacture of sizing agent for glass fiber]
Example 1
70 kg of water was added and dispersed in 2.0 kg of etherified high amylose corn starch and 2.0 kg of crosslinked corn starch crosslinked with epichlorohydrin. Subsequently, this was heated and heated, gelatinized at 95 ° C. for 30 minutes, and then cooled to 65 ° C. (the obtained liquid was designated as A liquid).
[0060]
On the other hand, stearic acid and aminoethylethanolamine were obtained by reacting at 180 ° C. with 1 mol of urea added to 2 mol of the product obtained by reacting at 180 ° C. while dehydrating at a molar ratio of 1: 1. 60 g of the obtained second cationic surfactant (hereinafter referred to as “surfactant A”), 0.6 kg of beef tallow oil dissolved by heating, 0.4 kg of palm oil, and polyoxyethylene polypropylene ether surfactant (HLB = 11) The mixture was stirred with a mixer while adding hot water to 0.1 kg. Stirring was continued for 5 minutes and then diluted with hot water to a total weight of 5 kg (the obtained liquid was designated as B liquid).
[0061]
Moreover, hot water was added to 300 g of the first cationic surfactant TEPA / SA (molar ratio of tetraethylenepentamine and stearic acid: former / latter = 1/2) to a total weight of 2 kg (obtained). The solution is referred to as solution C). Furthermore, 100 g of formalin solution (formaldehyde 30% by weight aqueous solution) was diluted 10 times with water (the obtained solution is designated as solution D).
[0062]
Next, all of B liquid, C liquid and D liquid were sequentially added to A liquid at 65 ° C., and hot water was added so that the total weight was 100 kg to obtain a glass fiber sizing agent, which was kept at 60 ° C. The residual particle ratio of etherified high amylose corn starch was 50% by weight, the residual particle ratio of crosslinked corn starch was 80% by weight, and the residual particle ratio of starch was 65% by weight on average.
[0063]
(Example 2)
Glass fiber bundling agent in the same manner as in Example 1 except that the weight of etherified high amylose corn starch was 1.0 kg, and 2.0 kg of etherified corn starch was used instead of 2.0 kg of crosslinked corn starch crosslinked with epichlorohydrin. And kept at 60 ° C. The residual particle ratio of etherified high amylose corn starch was 50% by weight, the residual particle ratio of etherified corn starch was 5% by weight, and the residual particle ratio of starch was 16% by weight on average.
[0064]
(Comparative Example 1)
70 kg of water was added and dispersed in 1.0 kg of etherified high amylose corn starch and 3.0 kg of etherified corn starch. Subsequently, this was heated and heated, gelatinized at 95 ° C. for 30 minutes, and then cooled to 65 ° C. (the obtained liquid was designated as A1 liquid).
[0065]
On the other hand, 0.6 kg of beef tallow oil, 0.4 kg of palm oil and 0.1 kg of polyoxyethylene polypropylene ether surfactant (HLB = 11) dissolved with heating were stirred with a mixer while adding hot water. Stirring was continued for 5 minutes and then diluted with hot water to a total weight of 5 kg (the obtained liquid was designated as B1 liquid).
[0066]
Moreover, hot water was added to 300 g of the first cationic surfactant TEPA / SA (molar ratio of tetraethylenepentamine and stearic acid: former / latter = 1/2) to a total weight of 2 kg (obtained). The solution is referred to as solution C1). Furthermore, 100 g of formalin solution (formaldehyde 30% by weight aqueous solution) was diluted 10 times with water (the obtained solution is designated as D1 solution).
[0067]
Next, all the B1 liquid, C1 liquid and D1 liquid were sequentially added to the A1 liquid at 65 ° C., and then hot water was added so that the total weight became 100 kg to obtain a glass fiber sizing agent, which was kept at 60 ° C. The residual particle ratio of etherified high amylose corn starch was 50% by weight, the residual particle ratio of etherified corn starch was 5% by weight, and the residual particle ratio of starch was 16% by weight on average.
[0068]
(Comparative Example 2)
70 kg of water was added and dispersed in 1.0 kg of etherified high amylose corn starch and 3.0 kg of etherified corn starch. Subsequently, this was heated and heated, gelatinized at 95 ° C. for 30 minutes, and then cooled to 65 ° C. (the obtained liquid was designated as A2 liquid).
[0069]
On the other hand, 60 g of surfactant A, 0.6 kg of beef tallow oil dissolved with heating, 0.4 kg of palm oil, and 0.1 kg of polyoxyethylene polypropylene ether surfactant (HLB = 11) were stirred with a mixer while adding hot water. Stirring was continued for 5 minutes and then diluted with hot water to a total weight of 5 kg (the obtained liquid was designated as B2 liquid). In addition, 100 g of formalin solution (formaldehyde 30% by weight aqueous solution) was diluted 10 times with water (the obtained solution is referred to as D2 solution).
[0070]
Subsequently, after adding all the B2 liquid and D2 liquid sequentially to 65 degreeC A2 liquid, hot water was added so that a total weight might be set to 100 kg, the glass fiber sizing agent was obtained, and it heat-retained at 60 degreeC. The residual particle ratio of etherified high amylose corn starch was 50% by weight, the residual particle ratio of etherified corn starch was 5% by weight, and the residual particle ratio of starch was 16% by weight on average.
[0071]
[Manufacture of glass fiber bundles]
(Examples 3-4 and Comparative Examples 3-4)
Using a roll coater, each of the glass fiber sizing agents obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was applied to glass fiber filaments of E glass (filament diameter 9 μm). The glass fiber bundle was obtained by drying at 25 ° C. for 25 hours. In addition, the adhesion amount of the glass fiber sizing agent (nonvolatile component) in the obtained glass fiber bundle was 1.0 part by weight with respect to 100 parts by weight of the glass fiber filament. In addition, the thing using the sizing agent for glass fibers obtained in Examples 1-2 and Comparative Examples 1-2 corresponds to Examples 3-4 and Comparative Examples 3-4, respectively.
[0072]
[Manufacture of glass fiber fabrics]
(Examples 5-6 and Comparative Examples 5-6)
After applying the sizing agent having the composition shown in Table 1 below to the glass fiber bundles obtained in Examples 3 to 4 and Comparative Examples 3 to 4, volatile components were removed (sizing agent for 100 parts by weight of the glass fiber bundle). The coating amount is 1 part by weight as a non-volatile component). Using this glass fiber bundle as a warp, using the glass fiber bundle obtained in Examples 3 to 4 and Comparative Examples 3 to 4 as a weft, a high-speed air jet loom equipped with a balloon breaker (manufactured by Tsuda Koma Kogyo Co., Ltd., ZA) Weaving was performed to obtain a glass fiber fabric of IPC spec 7628 type. In addition, the flying speed of the weft that contacted the balloon breaker during weaving was 3250 m / min. Further, the glass fiber sizing agent of Examples 1-2 and Comparative Examples 1-2 was applied to the warp yarns applied with the glass fiber sizing agent of Examples 1-2 and Comparative Examples 1-2, respectively. Weft was used. And the thing using the warp and the weft with which the sizing agent for glass fibers of Examples 1-2 and Comparative Examples 1-2 was applied corresponds to Examples 5-6 and Comparative Examples 5-6, respectively.
[0073]
[Table 1]

[0074]
[Evaluation of fluff]
100 m of glass fiber fabric was prepared by the methods of Examples 5 to 6 and Comparative Examples 5 to 6, and the number of protrusions generated by fluff generated per 50 cm woven length was measured and evaluated according to the criteria shown in Table 2 below.
[0075]
[Table 2]

[0076]
The evaluation results of the fluff are shown in Table 3 below. In addition, a result is shown based on the kind of apply | coated sizing agent for glass fiber (it describes as Examples 1-2 and Comparative Examples 1-2), the weight% of a non-volatile component among the containing components of the sizing agent for glass fibers, The weight of the first cationic surfactant with respect to 100 parts by weight of the oil agent, the weight of the second cationic surfactant with respect to 100 parts by weight of the first cationic surfactant, and the residual particle ratio of starch were also shown.
[0077]
[Table 3]

[0078]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a glass fiber sizing agent that can effectively prevent generation of fluff due to friction or impact during weaving by an air jet loom. In addition, it is possible to provide a glass fiber bundle that is bundled with such a glass fiber sizing agent, and a method for producing a glass fiber fabric using such a glass fiber bundle.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of a main part around an air nozzle in an air jet loom, where (a) is a perspective view and (b) is a top view.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Glass fiber wound body, 2 ... Balloon breaker, 3 ... Air nozzle, 4 ... Length, 10 ... Glass fiber bundle.

Claims (9)

A glass fiber sizing agent comprising starch, an oil agent, a surfactant, and water,
The surfactant includes a first cationic surfactant obtained by reacting a first fatty acid and a first amine compound represented by the following general formula (1), and a second fatty acid and the following general formula. A glass fiber sizing agent comprising: a second cationic surfactant obtained by reacting a reaction product of the second amine compound represented by (2) with a carbonyl group-containing crosslinking agent.

[In formula, R < ¹ > and R < ² > may be same or different, respectively, C1-C12 alkylene group, n is an integer of 0-10, m shows the integer of 1-10. ] The glass according to claim 1, wherein the first fatty acid and the second fatty acid are the same or different saturated fatty acids having 6 to 32 carbon atoms, and the R ¹ and the R ² are ethylene groups. Fiber sizing agent. The sizing agent for glass fibers according to claim 1 or 2, wherein the carbonyl group-containing crosslinking agent is urea. The sizing agent for glass fibers according to any one of claims 1 to 3, wherein the weight of the first cationic surfactant with respect to 100 parts by weight of the oil is 10 to 50 parts by weight. 5. The glass according to claim 1, wherein the weight of the second cationic surfactant is 5 to 50 parts by weight with respect to 100 parts by weight of the first cationic surfactant. Fiber sizing agent. The sizing agent for glass fibers according to any one of claims 1 to 5, wherein the starch is a starch having a residual particle ratio of 30 to 70% by weight. A glass fiber bundle formed by bundling a plurality of glass fiber filaments with the glass fiber bundling agent according to any one of claims 1 to 6. The glass fiber bundle according to claim 7, wherein a non-volatile component weight of the glass fiber sizing agent with respect to 100 parts by weight of the glass fiber filament is 0.5 to 1.5 parts by weight. A method for producing a glass fiber fabric, in which a glass fiber bundle is woven by an air jet loom as warp and weft,
The method according to claim 7, wherein at least one of the warp and the weft is a glass fiber bundle according to claim 7 or 8.

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