TW201821673A - 碳纖維前驅體用油劑及碳纖維前驅體 - Google Patents
碳纖維前驅體用油劑及碳纖維前驅體 Download PDFInfo
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Abstract
本發明提供一種碳纖維前驅體用油劑及附著有該碳纖維前驅體用油劑之碳纖維前驅體,其可對碳纖維前驅體賦予優異之抗靜電性與集束性,結果可提高製造碳纖維前驅體時之步驟通過性,又,可抑制碳纖維前驅體之製造機械等生銹。
作為碳纖維前驅體用油劑,本發明使用含有基底成分、包含特定之含氮化合物之陽離子界面活性劑及非離子界面活性劑而成者。
Description
本發明係關於一種碳纖維前驅體用油劑及碳纖維前驅體,進而詳細而言關於一種可對碳纖維前驅體賦予優異之抗靜電性與集束性,並且可抑制碳纖維前驅體之製造機械等生銹之碳纖維前驅體用油劑及附著有該碳纖維前驅體用油劑之碳纖維前驅體。
習知以來,作為碳纖維前驅體用油劑,提出有含有酯化合物及含氮界面活性劑者(例如參照專利文獻1),含有改質矽酮、多元酸及源自其之鹽者(例如參照專利文獻2),含有改質矽酮及鹼性化合物者(例如參照專利文獻3),含有酯化合物及水溶性醯胺系化合物者(例如參照專利文獻4),含有胺基改質矽酮、非離子界面活性劑及抗靜電劑者(例如參照專利文獻5)等。然而,該等習知之碳纖維前驅體用油劑均存在對碳纖維前驅體所賦予之抗靜電性與集束性不充分且碳纖維前驅體之製造機械等容易生銹之問題。
[專利文獻1]日本專利特開昭58-214581號公報
[專利文獻2]日本專利特開平10-102380號公報
[專利文獻3]日本專利特開平2-91226號公報
[專利文獻4]日本專利特開2010-024582號公報
[專利文獻5]日本專利特開2015-221957號公報
本發明所欲解決之問題在於提供一種碳纖維前驅體用油劑及附著有該碳纖維前驅體用油劑之碳纖維前驅體,其可對碳纖維前驅體賦予抗靜電性與集束性,結果可提高製造碳纖維前驅體時之步驟通過性,又,可抑制碳纖維前驅體之製造機械等生銹。
本發明者等人為了解決上述問題而進行研究,結果發現含有基底成分、非離子界面活性劑及特定之陽離子界面活性劑而成之碳纖維前驅體用油劑正好適合。
即,本發明係關於一種碳纖維前驅體用油劑,其含有基底成分、陽離子界面活性劑及非離子界面活性劑而成,其特徵在於陽離子界面活性劑為下述化1所表示之化合物。又,本發明係關於一種附著有該碳纖維前驅體用油劑之碳纖維前驅體。
於化1中,R1:碳數6~18之脂肪族烴基
R2:羥乙基、羥丙基或碳數1~7之烷基
R3:碳數1~4之烷基
Y-:甲基硫酸基、乙基硫酸基或下述化2所表示之有機基
於化2中,R4、R5:碳數1~4之烷基或氫原子
首先,對本發明之碳纖維前驅體用油劑(以下稱為本發明之油劑)進行說明。本發明之油劑係含有基底成分、非離子界面活性劑及特定之陽離子界面活性劑而成者。
作為供於本發明之油劑之基底成分並無特別限制,較佳為選自於25℃下為液狀之環氧改質矽酮、於25℃下為液狀之胺基改質矽酮及於25℃下為液狀之醯胺改質矽酮中之至少一者。該等可使用市售品,作為於25℃下為液狀之環氧改質矽酮,可列舉東麗道康寧公司製造之商品名SF-8413(25℃之黏度:17000mm2/s,環氧當量:3800g/mol)、東麗道康寧公司製造之商品名BY16-876(25℃之黏度:2400mm2/s,環氧當量:2800g/mol)、信越化學工業公司製造之商品名:X-22-343(25℃之黏度:25mm2/s,環氧當量:620g/mol)等。又,作為於25℃下為液狀之胺基改質矽酮,可列舉信越化學工業公司製造之商品名KF-880(25℃之黏度:650mm2/s,胺當量:1800g/mol)、信越化學工業公司製造之商品名KF-8012(25℃之黏度:90mm2/s,胺當量:2200g/mol)、信越化學工業公司製造之商品名KF-8008(25℃之黏度:450mm2/s,胺當量:5700g/mol)、信越化學工業公司製造之商品名KF-8005(25℃之黏度:1200 mm2/s,胺當量:11000g/mol)、信越化學工業公司製造之商品名KF-860(25℃之黏度:250mm2/s,胺當量:7600g/mol)、信越化學工業公司製造之商品名KF-393(25℃之黏度:70mm2/s,胺當量:350g/mol)、東麗道康寧公司製造之商品名FZ-3505(25℃之黏度:90mm2/s,胺當量:4000g/mol)、東麗道康寧公司製造之商品名BY16-872(25℃之黏度:20000mm2/s,胺當量:1800g/mol)、邁圖高新材料日本有限公司製造之商品名TSF4702(25℃之黏度:500mm2/s,胺當量:1600g/mol)、邁圖高新材料日本有限公司製造之商品名TSF4706(25℃之黏度:50mm2/s,胺當量:1600g/mol)等。進而,作為於25℃下為液狀之醯胺改質矽酮,可列舉信越化學工業公司製造之商品名KF-3935(25℃之黏度:25mm2/s)等。其中,更佳為於25℃下為液狀之胺基改質矽酮。該等可單獨使用,又亦可併用兩種以上。
於供於本發明之油劑之基底成分中,於25℃下為液狀係指25℃之黏度為270000mm2/s以下之物質。
供於本發明之油劑之陽離子界面活性劑係上述化1所表示之化合物。於化1中,R1為己基、庚基、辛基、癸基、癸烯基、十一烷基、十一碳烯基、十二烷基、十二碳烯基、十三烷基、十三碳烯基、十四烷基、十四碳烯基、十五烷基、十五碳烯基、十六烷基、十六碳烯基、十七烷基、十七碳烯基、十八烷基、十八碳烯基等碳數6~18之脂肪族烴基。R2為羥乙基、羥丙基或碳數1~7之烷基,具體而言,作為羥乙基,可列舉1-羥乙基、2-羥乙基等,作為羥丙基,可列舉1-羥丙基、2-羥丙基、3-羥丙基等,作為碳數1~7之烷基,可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基等。R3為甲基、乙基、丙基、丁基等碳數1~4之烷基。Y-為甲基 硫酸基、乙基硫酸基或上述化2所表示之有機基。於化2中R4及R5為甲基、乙基、丙基、丁基等碳數1~4之烷基或氫原子。其中,作為陽離子界面活性劑,較佳為選自化1中之Y-為甲基硫酸基之情形之化1所表示之化合物及化1中之Y-為乙基硫酸基之情形之化1所表示之化合物中之至少一者。該等可單獨使用,又,亦可併用兩種以上。
化2所表示之化合物之合成方法並無特別限制,例如可列舉藉由N-2-羥乙基胺乙基胺與特定碳數之脂肪酸之醯胺化反應及脫水環化反應生成咪唑啉化合物後,使該咪唑啉化合物與作為四級化劑之二甲基硫酸或二乙基硫酸反應之方法或與磷酸烷基酯反應之方法等。
作為供於本發明之油劑之非離子界面活性劑,其種類並無特別限制,可列舉(1)甲醇、乙醇、丙醇、丁醇、戊醇、己醇、辛醇、壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、十七烷醇、十八烷醇、十九烷醇、二十烷醇、二十一烷醇、二十二烷醇、二十三烷醇、二十四烷醇、二十五烷醇、二十六烷醇、二十七烷醇、二十八烷醇、二十九烷醇、三十烷醇等直鏈烷基醇,(2)異丙醇、異丁醇、異己醇、2-乙基己醇、異壬醇、異癸醇、異十三烷醇、異十四烷醇、異三十烷醇、異十六烷醇、異十七烷醇、異十八烷醇、異十九烷醇、異二十烷醇、異二十一烷醇、異二十二烷醇、異二十三烷醇、異二十四烷醇、異二十五烷醇、異二十六烷醇、異二十七烷醇、異二十八烷醇、異二十九烷醇、異十五烷醇等支鏈烷基醇,(3)十四碳烯醇、十六碳烯醇、十七碳烯醇、十八碳烯醇、十九碳烯醇等直鏈烯基醇,(4)異十六碳烯醇、異十八 碳烯醇等支鏈烯基醇,(5)環戊醇、環己醇等環狀烷基醇,(6)辛酸、壬酸、癸酸、十一酸、十二酸、十三酸、十四酸、十五酸、十六酸、十七酸、十八酸、十九酸、二十酸、二十一酸、二十二酸等直鏈烷基羧酸,(7)2-乙基己酸、異十二酸、異十三酸、異十四酸、異十六酸、異十八酸等支鏈烷基羧酸,(8)十八碳烯酸、十八碳二烯酸、十八碳三烯酸等直鏈烯基羧酸,(9)苯酚、苄醇、單苯乙烯化苯酚、二苯乙烯化苯酚、三苯乙烯化苯酚等芳香族醇,(10)苯甲酸等芳香族羧酸等使以上(1)~(10)之醇類或羧酸類加成環氧乙烷及/或環氧丙烷而成者。其中,作為非離子界面活性劑,較佳為相對於丁醇、戊醇、己醇、辛醇、壬醇、癸醇、十一醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、十七烷醇、十八烷醇、十九烷醇、二十醇、異丁醇、異己醇、2-乙基己醇、異壬醇、異癸醇、異十三烷醇、異十四烷醇、十四烯醇、十六烯醇、十七烯醇、十八烯醇、十九烯醇等直鏈烯醇、苯酚、苄醇、單苯乙烯化苯酚、二苯乙烯化苯酚、三苯乙烯化苯酚等芳香族醇等碳數4~40之有機醇1莫耳以1~50莫耳之比例使環氧乙烷進行加成反應而成者。該等非離子界面活性劑可單獨使用,又,亦可併用兩種以上。
於本發明之油劑中,基底成分、陽離子界面活性劑及非離子界面活性劑之比例並無特別限制,較佳為以基底成分、陽離子界面活性劑及非離子界面活性劑之含有比例之合計成為100質量%之方式含有50~95質量%比例之基底成分、0.01~30質量%比例之陽離子界面活性劑及3~45質量%比例之非離子界面活性劑而成者。
本發明之油劑較佳為進而含有有機多元酸鹽者。作為 有機多元酸鹽,可列舉丁二酸鹽、烯基琥珀酸鹽、2-羥基丁二酸鹽、2-羥基丙烷-1,2,3-三羧酸鹽、戊烷-1,5-二羧酸鹽、己二酸鹽、丙二酸鹽、酒石酸鹽、鄰苯二甲酸鹽、順丁烯二酸鹽、反丁烯二酸鹽、偏苯三甲酸鹽、均苯四甲酸鹽等,其中,較佳為丁二酸鉀鹽、烯基琥珀酸二鉀鹽、琥珀酸之二乙醇胺鹽、檸檬酸二鈉鹽、鄰苯二甲酸之二乙醇胺鹽等有機多元酸鹽之鹼金屬鹽或胺鹽。
於本發明之油劑進而含有有機多元酸鹽之情形時,較佳為以基底成分、陽離子界面活性劑、非離子界面活性劑及有機多元酸鹽之含有比例之合計成為100質量%之方式含有50~95質量%比例之基底成分、0.01~30質量%比例之陽離子界面活性劑、3~45質量%比例之非離子界面活性劑及15質量%以下比例之有機多元酸鹽而成者。
其次,對本發明之碳纖維前驅體(以下稱為本發明之前驅體)進行說明。本發明之前驅體為附著有本發明之油劑之碳纖維前驅體。
使本發明之油劑附著於碳纖維前驅體上之比例並無特別限制,較佳為以相對於碳纖維前驅體成為0.2~1.5質量%之方式附著本發明之油劑,更佳為以成為0.3~1.2質量%之方式附著。作為本發明之油劑之附著方法可應用公知之方法,此處例如可列舉浸漬供油法、輥式供油法、使用計量泵之導引供油法等。
根據本發明,可對碳纖維前驅體賦予優異之抗靜電性與集束性,結果可提高製造碳纖維前驅體時之步驟通過性,又,可抑制碳纖維前驅體之製造機械等生銹。
以下,為了使本發明之構成及效果更具體而列舉實施例等,但本發明不限定於該等實施例。再者,於以下之實施例及比較例中,份意指質量份,又,%意指質量%。
準備下述基底成分。
A-1:25℃之動黏度為650mm2/s、胺當量為1800g/mol之胺基改質聚有機矽氧烷(信越化學工業公司製造之商品名KF-880)
A-2:25℃之動黏度為90mm2/s、胺當量為2200g/mol之胺基改質聚有機矽氧烷(信越化學工業公司製造之商品名KF-8012)
A-3:25℃之動黏度為450mm2/s、胺當量為5700g/mol之胺基改質聚有機矽氧烷(信越化學工業公司製造之商品名KF-8008)
A-4:25℃之動黏度為250mm2/s、胺當量為7600g/mol之胺基改質聚有機矽氧烷(信越化學工業公司製造之商品名KF-860)
A-5:25℃之動黏度為17000mm2/s、環氧當量:3800g/mol之環氧改質聚有機矽氧烷(東麗道康寧公司製造之商品名SF-8413)
將十八碳烯酸282g(1莫耳)及N-2-羥乙基胺基乙基胺104g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生 成之水一面進行8小時反應,而獲得1-(2-羥乙基)-2-十七碳烯基-2-咪唑啉350g。將所獲得之1-(2-羥乙基)-2-十七碳烯基-2-咪唑啉175g(0.5莫耳)加溫至70~90℃,一面攪拌一面於該溫度下緩慢地滴加二乙基硫酸77g(0.5莫耳)進行四級化反應。滴加結束後,於相同溫度下進行2小時熟成,然後獲得反應物252g。對所獲得之反應物進行分析,結果為1-(2-羥乙基)-1-乙基-2-十七碳烯基-2-咪唑啉鎓乙基硫酸鹽。將其設為陽離子界面活性劑B-1。
將辛酸144g(1莫耳)及N-丙基胺乙基胺102g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-丙基-2-庚基-2-咪唑啉210g。將所獲得之1-丙基-2-庚基-2-咪唑啉105g(0.5莫耳)加溫至70~90℃並熔融後,一面攪拌一面於該溫度下緩慢地滴加二甲基硫酸63g(0.5莫耳)進行四級化反應。滴加結束後,於相同溫度下進行2小時熟成,然後獲得反應物168g。對所獲得之反應物進行分析,結果為1-丙基-1-甲基-2-庚基-2-咪唑啉鎓甲基硫酸鹽。將其設為陽離子界面活性劑B-2。
將十二酸200g(1莫耳)及N-3-羥丙基胺乙基胺118g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-(3-羥丙基)-2-十一烷基-2-咪唑啉282g。將所獲得之1-(3-羥丙基)-2-十一烷基-2-咪唑啉141g(0.5莫 耳)加溫至70~90℃並熔融後,一面攪拌一面於該溫度下緩慢地滴加二乙基硫酸77g(0.5莫耳)進行四級化反應。滴加結束後,於相同溫度下進行2小時熟成,然後獲得反應物218g。對所獲得之反應物進行分析,結果為1-(3-羥丙基)-1-乙基-2-十一烷基-2-咪唑啉鎓乙基硫酸鹽。將其設為陽離子界面活性劑B-3。
將十八酸284g(1莫耳)及N-2-羥乙基胺乙基胺104g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-(2-羥乙基)-2-十七烷基-2-咪唑啉352g。將所獲得之1-(2-羥乙基)-2-十七烷基-2-咪唑啉176g(0.5莫耳)加溫至70~90℃,一面攪拌一面於該溫度下緩慢地滴加二乙基硫酸77g(0.5莫耳)進行四級化反應。滴加結束後,於相同溫度下進行2小時熟成,然後獲得反應物253g。對所獲得之反應物進行分析,結果為1-(2-羥乙基)-1-乙基-2-十七烷基-2-咪唑啉鎓乙基硫酸鹽。將其設為陽離子界面活性劑B-4。
將十二酸200g(1莫耳)及N-2-羥乙基胺乙基胺104g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-(2-羥乙基)-十一烷基-2-咪唑啉268g。於氮氣環境下一面攪拌所獲得之1-(2-羥乙基)-十一烷基-2-咪唑啉134g(0.5莫耳)一面加溫至80℃,歷時10分鐘滴加磷酸三甲酯70g(0.5莫耳),將反應溫度維持於80~85℃使其進行反應。進而, 於相同溫度下進行3小時熟成而獲得反應物204g。對所獲得之反應物進行分析,結果為1-(2-羥乙基)-十一烷基-2-咪唑啉四級化物。將其設為陽離子界面活性劑B-5。
將十九碳烯酸296g(1莫耳)及N-丙基胺乙基胺102g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-丙基-2-十八碳烯基-2-咪唑啉362g。於氮氣環境下一面攪拌所獲得之1-丙基-2-十八碳烯基-2-咪唑啉181g(0.5莫耳)一面加溫至80℃,歷時10分鐘滴加磷酸三乙酯91g(0.5莫耳),將反應溫度維持於80~85℃使其進行反應。進而,於相同溫度下進行3小時熟成而獲得反應物272g。對所獲得之反應物進行分析,結果為1-丙基-2-十八碳烯基-2-咪唑啉四級化物。將其設為陽離子界面活性劑B-6。
將壬酸158g(1莫耳)及N-2-羥乙基胺乙基胺104g(1莫耳)加入燒瓶中並保持於180℃,一面藉由氮氣氣流蒸餾去除所生成之水一面進行8小時反應,而獲得1-(2-羥乙基)-辛基-2-咪唑啉226g。於氮氣環境下一面攪拌所獲得之1-(2-羥乙基)-辛基-2-咪唑啉113g(0.5莫耳)一面加溫至80℃,歷時10分鐘滴加磷酸三乙酯91g(0.5莫耳),將反應溫度維持於80~85℃使其進行反應。進而,於相同溫度下進行3小時熟成而獲得反應物204g。對所獲得之反應物進行分析,結果為1-(2-羥乙基)-辛基-2-咪唑啉四級化物。將其設為陽 離子界面活性劑B-7。
將以上所合成之陽離子界面活性劑之內容彙總示於表1。
‧rB-1~rB-3準備如下者。
rB-1:藉由二乙基硫酸使二伸乙基三胺與二十二酸反應所獲得之醯胺化合物陽離子化而成之水溶性醯胺系化合物
rB-2:二烷基乙基甲基銨乙基硫酸鹽(Lion Akzo公司製造之商品名Alucard 2HT-50ES)
rB-3:十二烷基三甲基氯化銨(花王公司製造之商品名Quartamin 24P)
C-1之合成:將1-十二烷醇186g(1.0莫耳)及氫氧化鉀1g加入高壓釜中並利用氮氣沖洗後,加溫至120℃,添加環氧乙烷308g(7莫耳)進行反應。進行1小時之熟成反應後,藉由吸附材處理去除觸媒而獲得反應物。對所獲得之反應物進行分析,結果為1分子中包含1個1-十二烷醇基與合計7個氧化乙烯單位之化合物。將其設為非離子界面活性劑C-1。
藉由與C-1相同之方式合成或準備如下非離子界面活性劑。
C-2:聚氧乙烯(n=5)辛基醚
C-3:聚氧乙烯(n=40)二十二烷基醚
C-4:聚氧乙烯烷基醚(日本觸媒公司製造之商品名Softanol 50)
C-5:聚氧乙烯(n=40)十八烷基醚
C-6:聚氧乙烯(n=10)壬基苯基醚
rC-1:β-十八烷基硫代丙酸十八碳烯酯
rC-2:氧化二辛基十八碳烯胺
rC-3:聚乙二十六酸酯(n=8)
rC-4:聚氧乙烯(n=30)氫化蓖麻油醚
rC-5:偏苯三甲酸三異癸酯
準備下述有機多元酸鹽。
D-1:鄰苯二甲酸二乙醇胺鹽
D-2:十二碳烯基琥珀酸二鉀鹽
D-3:十二碳烯基琥珀酸鈣鹽
rD-1:十八酸鉀鹽
準備下述其他化合物。
rX-1:乙酸銨鹽
rX-2:氫氧化銨鹽
將試驗劃分1~5中合成或準備之基底成分A-1 140g、陽離子界面活性劑B-1 30g、非離子界面活性劑C-1 20g、有機多元酸鹽D-1 10g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例1之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 110g、陽離子界面活性劑B-2 20g、非離子界面活性劑C-2 50g、有機多元酸鹽D-2 20g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例2之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-3 170g、陽離子界面活性劑B-2 8g、非離子界面活性劑C-3 20g、有機多元酸鹽D-1 2g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例3之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-4 190g、陽離子界面活性劑B-3 6g、非離子界面活性劑C-4 6g、有機多元酸鹽D-2 1g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例4之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 120g、陽離子界面活性劑B-4 14g、非離子界面活性劑C-5 60g、有機多元酸鹽D-2 6g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例5之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-1 150g、陽離子界面活性劑B-3 40g、非離子界面活性劑C-6 26g、有機多元酸鹽D-2 4g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例6之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-3 160g、陽離子界面活性劑B-1 20g、非離子界面活性劑C-4 10g、有機多元酸鹽D-2 10g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為 50%之方式緩慢地添加離子交換水,藉此製備實施例7之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-3 60g、陽離子界面活性劑B-2 10g、非離子界面活性劑C-3 120g、有機多元酸鹽D-3 10g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例8之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-1 50g、陽離子界面活性劑B-1 40g、非離子界面活性劑C-2 90g、有機多元酸鹽D-3 20g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例9之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 176g、陽離子界面活性劑B-3 8g、非離子界面活性劑C-1 6g、C-4 10g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例10之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 130g、陽離子界面活性劑B-2 20g、非離子界面活性劑C-3 50g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例11之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-1 40g、陽離子界面活性劑B-4 20g、非離子界面活性劑C-5 140g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例12之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-5 104g、陽離子界面活性劑B-5 16g、非離子界面活性劑C-2 80g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例13之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-5 170g、陽離子界面活性劑B-6 4g、非離子界面活性劑C-3 26g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例14之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-5 130g、陽離子界面活性劑B-7 10g、非離子界面活性劑C-2 60g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備實施例15之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-1 176g、非離子界面活性劑C-4 24g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例1之油劑之50%水性液。
藉由與實施例1相同之方式將非離子界面活性劑C-6 30g、rC-1 120g、rC-2 20g、rC-3 20g、rC-4 10g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例2之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 120g、A-5 46g、非離子界面活性劑C-4 30g、rX-1 4g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例3之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 199.4g、rX-2 0.6g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例4之油劑之50%水性液。
藉由與實施例1相同之方式將非離子界面活性劑C-1 160g、有機多元酸鹽D-1 40g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例5之油劑之50%水性液。
藉由與實施例1相同之方式將陽離子界面活性劑rB-1 30g、非離子界面活性劑C-1 80g、rC-5 90g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例6之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-2 140g、非離子界面活性劑C-4 40g、有機多元酸鹽rD-1 20g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例7之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-4 172g、陽離子界面活性劑rB-2 4g、非離子界面活性劑C-1 24g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例8之油劑之50%水性液。
藉由與實施例1相同之方式將基底成分A-4 172g、陽離子界面活性劑rB-3 4g、非離子界面活性劑C-1 24g加入燒杯中並充分混合,一面繼續攪拌一面以固形份濃度成為50%之方式緩慢地添加離子交換水,藉此製備比較例9之油劑之50%水性液。
將以上所製備之各例之碳纖維前驅體用油劑之內容彙總示於表2。
利用輥式供油法使試驗劃分6中製備之各例之油劑之50%水性液作為碳纖維前驅體用油劑,以成為0.5±0.1%之方式附著於丙烯酸系長線(75丹尼/40絲)上後,使用乾燥輥,於115℃下乾燥4秒鐘而 獲得試樣線A。將該試樣線A用於下述電阻值及產電之評價。又,利用浸漬法使試驗劃分6中製備之各例之油劑之50%水性液作為碳纖維前驅體用油劑,以成為0.5±0.1%之方式附著於丙烯酸系長線(16000丹尼/12000絲)上後,使用乾燥輥於115℃下乾燥4秒鐘而獲得試樣線B。將該試樣線B用於下述集束性之評價。
將上述試樣線A於20×65%RH之環境下放置24小時,於該條件下將評價資料10g放入電阻測定用盒(40ml容量)中,使用東亞電波工業公司製造之商品名SM-5E型絕緣計測定電阻(logΩ),並利用以下基準對電阻值進行評價。
◎:未滿9
○:9~未滿10
×:10~未滿11
××:11以上
將上述試樣線A於20×65%RH之環境下放置24小時,於該條件下以初始張力20g、線速100m/min使其與鍍鉻緞光加工面加工針進行接觸移行,利用集電式電位測定器(春日電機公司製造)測定接觸後之產電,並利用以下基準對所產生之電氣進行評價。
5:未滿50伏特
4:50伏特以上~未滿100伏特
3:100伏特以上~未滿300伏特
2:300伏特以上~未滿500伏特
1:500伏特以上
於製造上述試樣線B 50kg時,目視觀察通過各步驟時及捲取時之碳纖維前驅體纖維之集束狀態。實施5次同樣之試驗,並利用以下基準對集束性進行評價。
◎:集束性非常良好,步驟通過性完全沒有問題。
○:集束性良好,步驟通過性沒有問題。
×:集束性不足,步驟通過性稍有問題。
××:集束性不良,步驟通過性有極大問題。
於試驗劃分6中所製備之各例之碳纖維前驅體用油劑之50%水性液中,進而添加離子交換水而使固形份濃度成為2%,將洗淨之金屬導輥浸漬於該水溶液中後,於20℃×100%RH下放置24小時,目視觀察各金屬導輥之生銹狀態,並利用以下基準對銹進行評價。
○:未確認到生銹。
×:確認到生銹。
將以上所評價之各例之碳纖維前驅體用油劑之結果彙總示於表3。
根據與表2對應之表3之結果可明確,根據本發明,可對碳纖維前驅體賦予優異之抗靜電性與集束性,結果可提高製造碳纖維前驅體時之步驟通過性,又,可抑制碳纖維前驅體之製造機 械等生銹。
Claims (9)
- 一種碳纖維前驅體用油劑,其係含有基底成分、陽離子界面活性劑及非離子界面活性劑而成者,其特徵在於,陽離子界面活性劑為下述化1所表示之化合物,
- 如請求項1之碳纖維前驅體用油劑,其中,陽離子界面活性劑為選自化1中之Y -為甲基硫酸基之情形下之化1所表示之化合物及化1中之Y -為乙基硫酸基之情形下之化1所表示之化合物中之至少一者。
- 如請求項1或2之碳纖維前驅體用油劑,其中,基底成分為選自於25℃下為液狀之環氧改質矽酮、於25℃下為液狀之胺基改質 矽酮及於25℃下為液狀之醯胺改質矽酮中之至少一者。
- 如請求項1或2之碳纖維前驅體用油劑,其中,基底成分為於25℃下為液狀之胺基改質矽酮。
- 如請求項1或2之碳纖維前驅體用油劑,其中,非離子界面活性劑為以相對於碳數4~40之有機醇1莫耳為1~50莫耳之比例使環氧乙烷進行加成反應而成之化合物。
- 如請求項1或2之碳纖維前驅體用油劑,其係以基底成分、陽離子界面活性劑及非離子界面活性劑之含有比例之合計成為100質量%的方式含有50~95質量%比例之基底成分、0.01~30質量%比例之陽離子界面活性劑及3~45質量%比例之非離子界面活性劑而成。
- 如請求項6之碳纖維前驅體用油劑,其係進而含有有機多元酸鹽,以基底成分、陽離子界面活性劑、非離子界面活性劑及有機多元酸鹽之含有比例之合計成為100質量%的方式含有50~95質量%比例之基底成分、0.01~30質量%比例之陽離子界面活性劑、3~45質量%比例之非離子界面活性劑及15質量%以下比例之有機多元酸鹽而成。
- 如請求項7之碳纖維前驅體用油劑,其中,有機多元酸鹽為有機多元酸之鹼金屬鹽或胺鹽。
- 一種碳纖維前驅體,其附著有請求項1至8中任一項之碳纖維前驅體用油劑。
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JPS61108767A (ja) | 1984-10-31 | 1986-05-27 | 竹本油脂株式会社 | 合成繊維用帯電防止剤 |
JPS6392781A (ja) * | 1986-10-03 | 1988-04-23 | 竹本油脂株式会社 | 綿紡績用油剤 |
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JP5277005B2 (ja) | 2009-01-30 | 2013-08-28 | 松本油脂製薬株式会社 | 炭素繊維製造用アクリル繊維油剤およびそれを用いた炭素繊維の製造方法 |
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US10072359B2 (en) * | 2011-06-06 | 2018-09-11 | Mitsubishi Chemical Corporation | Oil agent for carbon fiber precursor acrylic fiber, oil composition for carbon fiber precursor acrylic fiber, processed-oil solution for carbon-fiber precursor acrylic fiber, and method for producing carbon-fiber precursor acrylic fiber bundle, and carbon-fiber bundle using carbon-fiber precursor acrylic fiber bundle |
JP5990749B2 (ja) * | 2012-03-16 | 2016-09-14 | 出光興産株式会社 | 潤滑油組成物、該潤滑油組成物を用いた摺動機構 |
JP5213288B1 (ja) * | 2012-11-26 | 2013-06-19 | 竹本油脂株式会社 | 合成繊維の処理方法、合成繊維、合成繊維の精紡方法及び紡績糸 |
JP6190673B2 (ja) * | 2013-09-06 | 2017-08-30 | 松本油脂製薬株式会社 | 炭素繊維製造用アクリル繊維処理剤及びその用途 |
WO2016024451A1 (ja) | 2014-08-12 | 2016-02-18 | 松本油脂製薬株式会社 | アクリル繊維処理剤及びその用途 |
JP2015221957A (ja) | 2015-06-30 | 2015-12-10 | 三菱レイヨン株式会社 | 炭素繊維前駆体アクリル繊維束とその製造方法 |
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CN109563680B (zh) | 2020-09-11 |
TWI712719B (zh) | 2020-12-11 |
TWI712720B (zh) | 2020-12-11 |
CN109563680A (zh) | 2019-04-02 |
WO2018100788A1 (ja) | 2018-06-07 |
TW201821672A (zh) | 2018-06-16 |
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