TWI490393B - 光亮劑之水溶液 - Google Patents
光亮劑之水溶液 Download PDFInfo
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Description
本發明係關於二苯乙烯光亮劑與聚乙烯醇之儲存穩定性水溶液,其可直接為造紙者所使用。
眾所周知,塗覆紙之白度及由此之吸引性可藉由將光亮劑添加至塗覆漿中而得到改良。為滿足對更高白度之塗覆紙的需求,需要更有效之光亮劑。
WO 96/00221揭示用於紙、織物及清潔劑之衍生自胺基酸之四磺化二苯乙烯增亮劑。聚乙烯醇係包括於添加劑一列中,據說該等添加劑在塗覆於紙表面時增強增亮劑之效能。
WO 98/42685揭示藉由使用某些胺基酸、放棄WO 96/00221之化合物而製得之六磺化二苯乙烯增亮劑。亦描述一種藉由使用增亮劑作為著色塗覆組合物之部分以用於紙表面之螢光增白的方法,該組合物亦包含作為水溶性輔助黏合劑或保護膠體之聚乙烯醇。
EP 1355004描述並非衍生自胺基酸之某些二苯乙烯增亮劑用於使含水塗覆漿增亮的用途,該等水性塗覆漿包含至少一種乳膠黏合劑及至少一種與其不同之合成輔助黏合劑。聚乙烯醇係作為較佳合成輔助黏合劑而列出。
日本未審查專利公開案62-106965揭示衍生自胺基酸之某些六磺化二苯乙烯增亮劑。據稱該等增亮劑對於紙之螢光增白十分有效,且可作為漿料溶液或著色塗覆組合物之部分塗覆至紙表面。聚乙烯醇係作為漿料溶液之可能組份而提及。
即使自先前技術已知聚乙烯醇在其他化合物中可增強增亮效能,直至現在,當欲使用該醇時,造紙者亦必須將其獨立地添加至塗覆漿中。因此,簡化製備經增亮之塗覆紙之方法的需要仍然存在。
現已驚奇地發現,有可能製造基本上由二苯乙烯光亮劑及聚乙烯醇組成之儲存穩定性溶液,其可直接為造紙者所使用,此係因為可將其以水稀釋且/或直接量入塗覆組合物中以提供白度特別高之塗覆紙。
因此,本發明提供光亮劑之水溶液,其基本上由以下物質組成:(a)至少一種式(1)之光亮劑:
其中:M為氫、鹼金屬原子、銨或衍生自胺之陽離子,較佳為氫或鈉,最佳為鈉,n為1或2,且X為天然或非天然胺基酸,自其已移除胺基之一氫原子;(b)具有大於75%之水解度及2-40 mPa.s之布絡克菲爾德(Brookfield)黏度(在20℃下,4% w/w水溶液)之聚乙烯醇;及(c)水。
在n為1之光亮劑中,SO3
M基團較佳係位於苯環之4位。
在n為2之光亮劑中,SO3
M基團較佳係位於苯環之2位、5位。
可自其衍生X之胺基酸的實例為丙胺酸、2-胺基丁酸、天冬醯胺酸、天冬胺酸、S-羧甲基半胱胺酸、磺基丙胺酸、半胱胺酸、麩胺酸、麩醯胺酸、甘胺酸、亞胺二乙酸、異白胺酸、白胺酸、甲硫胺酸、N-甲基牛磺酸、正白胺酸、正纈胺酸、苯丙胺酸、2-苯基甘胺酸、哌啶甲酸、脯胺酸、肌胺酸、絲胺酸、牛磺酸、酥胺酸及纈胺酸。當胺基酸含有對掌性中心時,可使用光學異構體或外消旋混合物。
較佳之胺基酸為天冬胺酸、麩胺酸及亞胺二乙酸。
該等水溶液可含有高達10重量%之鹽,通常為作為來自光亮劑製造之副產物而形成的氯化鈉。
該等水溶液亦可含有一或多種防凍劑、殺生物劑、錯合劑或其他添加劑以及在光亮劑製備期間所形成之有機副產物。
該聚乙烯醇較佳具有大於或等於80%之水解度及2-20 mPa.s之布絡克菲爾德黏度。
較佳地,聚乙烯醇對光亮劑之重量比位於0.01:1至1.5:1之範圍內。最佳地,該比率位於0.03:1至1:1之範圍內。
溶液之水含量適宜為至少使得該溶液仍為可攪拌且較佳為可易於澆注的量;在濃溶液中,光亮劑之濃度有利地為位於以溶液重量計6至60%、較佳10至50%之範圍內。
該等水溶液之pH較佳為中性至明顯鹼性,詳言之位於pH 7至pH 10之範圍內。若有必要,則可藉由添加M-相應鹼(例如鹼金屬氫氧化物或碳酸鹽、氨或胺)來調節pH。
本發明之光亮劑溶液為儲存穩定性的,且因為可將其以水稀釋且/或直接量入塗覆組合物中,因此可將其直接使用。因此,本發明之另一目標為將增亮劑溶液添加至塗覆組合物中以獲得經塗覆及光學增亮之紙。
因此,本發明亦提供一種用於製造至少在塗覆中得以光學增亮之塗覆紙的方法,其中如上述之塗覆組合物係於薄片成形後而塗覆至紙上。
該等塗覆組合物實質上為含水組合物,其含有至少一種黏合劑及白色顏料,後者詳言之為乳白色顏料,且可額外地含有諸如分散劑及消泡劑之另外添加劑。
儘管有可能製造不含白色顏料之塗覆組合物,但是用於印刷之最佳白色基質係使用含有以重量計10-70%之白色顏料的不透明塗覆組合物來製得。此等白色顏料通常為無機顏料,例如矽酸鋁(高嶺土,另外稱作瓷土)、碳酸鈣(白堊)、二氧化鈦、氫氧化鋁、碳酸鋇、硫酸鋇或硫酸鈣(石膏)。
該等黏合劑可為在造紙工業中普遍用於製造塗覆組合物之彼等者中的任一者且可由單一黏合劑或由主要黏合劑與次要黏合劑之混合物組成。該單獨或主要黏合劑較佳為合成乳膠,通常為苯乙烯-丁二烯、乙酸乙烯酯、苯乙烯丙烯酸、乙烯丙烯酸或乙烯乙酸乙烯酯聚合物。該次要黏合劑可例如為澱粉、羧甲基纖維素、酪蛋白、大豆聚合物或聚乙烯醇。
該單獨或主要黏合劑係以通常位於以白色顏料重量計5-25%範圍內之量來使用。該次要黏合劑係以通常位於以白色顏料重量計0.1-10%範圍內之量來使用。
式(1)之光亮劑係以通常位於以白色顏料重量計0.01-1%範圍內、較佳位於以白色顏料重量計0.05-0.5%範圍內之量來使用。
以下實例將對本發明進行更詳細的解釋。若非另外指明,否則"%"及"份"係以重量計;黏度係使用布絡克菲爾德黏度計在20℃下針對4%水溶液而測得。
藉由將13.1份(0.01 mol)式(4)之光亮劑、6.3份具有98.5%之水解度及2.75 mPa.s之布絡克菲爾德黏度的聚乙烯醇及80.6份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液1a。將溶液之pH以氫氧化鈉調至9.0。
藉由將15.1份(0.01 mol)式(5)之光亮劑、6.3份具有98.5%之水解度及2.75 mPa.s之布絡克菲爾德黏度的聚乙烯醇及78.6份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液1b。將溶液之pH以氫氧化鈉調至9.0。
藉由將15.1份(0.01 mol)式(5)之光亮劑及84.9份水攪拌在一起來製成光亮劑溶液1c。將溶液之pH以氫氧化鈉調至9.0。
藉由將12.2份(0.01 mol)式(6)之光亮劑、6.3份具有98.5%之水解度及2.75 mPa.s之布絡克菲爾德黏度的聚乙烯醇及81.5份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液1d。將溶液之pH以氫氧化鈉調至9.0。
藉由將13.1份(0.01 mol)式(4)之光亮劑、6.3份具有85%之水解度及3.7 mPa.s之布絡克菲爾德黏度的聚乙烯醇及80.6份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液2a。將溶液之pH以氫氧化鈉調至9.0。
藉由將15.1份(0.01 mol)式(5)之光亮劑、6.3份具有85%之水解度及3.7 mPa.s之布絡克菲爾德黏度的聚乙烯醇及78.6份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液2b。將溶液之pH以氫氧化鈉調至9.0。
藉由將15.1份(0.01 mol)式(5)之光亮劑及84.9份水攪拌在一起來製成光亮劑溶液2c。將溶液之pH以氫氧化鈉調至9.0。
藉由將12.2份(0.01 mol)式(6)之光亮劑、6.3份具有85%之水解度及3.7 mPa.s之布絡克菲爾德黏度的聚乙烯醇及81.5份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液2d。將溶液之pH以氫氧化鈉調至9.0。
藉由將18.9份(0.0125 mol)式(5)之光亮劑、1.2份具有85%之水解度及3.7 mPa.s之布絡克菲爾德黏度的聚乙烯醇及79.9份水攪拌在一起,同時加熱至90-95℃,直至獲得在冷卻至室溫之後保持穩定之澄清溶液,從而製成光亮劑溶液3a。將溶液之pH以氫氧化鈉調至9.0。
藉由將18.9份(0.0125 mol)式(5)之光亮劑及81.1份水攪拌在一起來製成光亮劑溶液3b。將溶液之pH以氫氧化鈉調至9.0。
製備塗覆組合物,其含有500份白堊(以商標名Hydrocarb 90自OMYA購得)、500份黏土(以商標名Kaolin SPS自IMERYS購得)、470份水、6份分散劑(聚丙烯酸之鈉鹽,以商標名Polysalz S自BASF購得)、200份乳膠(丙烯酸酯共聚物,以商標名Acronal S320D自BASF購得)及50份之羧甲基纖維素(以商標名Finnfix 5.0自Noviant購得)於水中之10%溶液。藉由添加水,將固體含量調節至60%,且以氫氧化鈉將pH調至8-9。
向經攪拌之塗覆組合物中以0.5至4.0%之濃度範圍分別添加如製備實例1A、1B、1C及1D中所描述而製得的溶液1a、1b、1c及1d。接著使用在桿體上具有標準速度設定及標準負載之自動線繞桿式塗覆器,將經增亮之塗覆組合物塗覆至市售75 gsm中性上膠白紙基薄片。接著在熱氣流中將該塗覆紙乾燥5分鐘。使乾燥紙處於正常狀態,接著在經校正之Elrepho光譜光度計上量測CIE白度。
分別使用如製備實例2A、2B、2C及2D中所描述而製得之溶液2a、2b、2c及2d重複應用實例1。
製備塗覆組合物,其含有500份白要(以商標名Hydrocarb 90自OMYA購得)、500份黏土(以商標名Kaolin SPS自IMERYS購得)、370份水、6份分散劑(聚丙烯酸之鈉鹽,以商標名Polysalz S自BASF購得)、200份乳膠(丙烯酸酯共聚物,以商標名Acronal S320D自BASF購得)及400份之陰離子馬鈴薯澱粉(來自AVEBE B.A.之帕凡曼施(Perfectamyl)A4692)於水中之20%溶液。藉由添加水,將固體含量調節至60%,且以氫氧化鈉將pH調至8-9。
向經攪拌之塗覆組合物中以0.5至4.0%之濃度範圍分別添加如製備實例3A及3B中所描述而製得的溶液3a及3b。接著使用在桿體上具有標準速度設定及標準負載之自動線繞桿式塗覆器,將經增亮之塗覆組合物塗覆至市售75 gsm中性上膠白紙基薄片。接著在熱氣流中將該塗覆紙乾燥5分鐘。使乾燥紙處於正常狀態,接著在經校正之Elrepho光譜光度計上量測CIE白度。
本發明之結果清楚顯示含有聚乙烯醇之本發明溶液在白度上具有令人驚奇的優越性。
Claims (9)
- 一種塗覆組合物,其包含水性光亮劑溶液,該光亮劑溶液基本上由以下所組成:(a)至少一種式(1)之光亮劑:
- 如請求項1之塗覆組合物,其中:M為氫或鈉,n為2,其中該聚乙烯醇具有大於或等於80%之水解度及2-20mPa.s之布絡克菲爾德黏度。
- 如請求項1之塗覆組合物,其中該光亮劑溶液另包含高達10重量%之鹽,其中該鹽為來自光亮劑製造之副產物。
- 如請求項1之塗覆組合物,其中該光亮劑溶液另包含一或多種防凍劑、殺生物劑或錯合劑。
- 如請求項1之塗覆組合物,其中該光亮劑溶液另包含一或多種在光亮劑製備期間所形成之有機副產物。
- 如請求項1之塗覆組合物,其包含0.5至4.0%之溶液。
- 一種經如請求項1之塗覆組合物塗覆之紙。
- 一種製造塗覆紙之方法,其包含在薄片成形之後,將包含溶液之塗覆組合物塗覆於紙上,其中該溶液包含水性光亮劑溶液,該光亮劑溶液基本上由以下所組成: (a)至少一種式(1)之光亮劑:
- 如請求項8之方法,其中該式(1)之光亮劑係以一或多種白色顏料之0.05至0.5重量%之量來使用於該塗覆組合物中。
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EP20050007691 EP1712677A1 (en) | 2005-04-08 | 2005-04-08 | Aqueous solutions of optical brighteners |
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EP (2) | EP1712677A1 (zh) |
JP (1) | JP4728391B2 (zh) |
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CN (1) | CN101155962B (zh) |
AR (1) | AR056305A1 (zh) |
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ES (1) | ES2347074T3 (zh) |
HK (1) | HK1121789A1 (zh) |
IL (1) | IL186384A (zh) |
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CN104312202A (zh) * | 2014-09-29 | 2015-01-28 | 浙江亿得化工有限公司 | 低碱或无碱型活性深红染料及其制备方法 |
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- 2006-04-06 AR ARP060101356 patent/AR056305A1/es not_active Application Discontinuation
- 2006-04-06 TW TW095112145A patent/TWI490393B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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DE602006015789D1 (de) | 2010-09-09 |
BRPI0609733B1 (pt) | 2018-06-19 |
EP1869252A2 (en) | 2007-12-26 |
IL186384A0 (en) | 2008-01-20 |
KR20080004482A (ko) | 2008-01-09 |
US20090081475A1 (en) | 2009-03-26 |
WO2006108785A2 (en) | 2006-10-19 |
CA2600299C (en) | 2015-06-02 |
CA2600299A1 (en) | 2006-10-19 |
RU2007141414A (ru) | 2009-05-20 |
NO20075021L (no) | 2008-01-08 |
JP2008534762A (ja) | 2008-08-28 |
RU2375511C2 (ru) | 2009-12-10 |
HK1121789A1 (en) | 2009-04-30 |
IL186384A (en) | 2011-12-29 |
JP4728391B2 (ja) | 2011-07-20 |
ES2347074T3 (es) | 2010-10-25 |
AU2006233879A1 (en) | 2006-10-19 |
BRPI0609733A2 (pt) | 2010-04-27 |
KR101329924B1 (ko) | 2013-11-14 |
EP1869252B1 (en) | 2010-07-28 |
US20140374042A1 (en) | 2014-12-25 |
CN101155962A (zh) | 2008-04-02 |
EP1712677A1 (en) | 2006-10-18 |
CN101155962B (zh) | 2012-09-05 |
WO2006108785A3 (en) | 2007-05-10 |
PT1869252E (pt) | 2010-09-07 |
ATE475746T1 (de) | 2010-08-15 |
US8859679B2 (en) | 2014-10-14 |
TW200710309A (en) | 2007-03-16 |
ZA200707652B (en) | 2009-10-28 |
AR056305A1 (es) | 2007-10-03 |
AU2006233879B2 (en) | 2011-04-28 |
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