TWI399370B - 光學增亮劑之儲存穩定溶液 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/68—Triazinylamino stilbenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2582—Coating or impregnation contains an optical bleach or brightener or functions as an optical bleach or brightener [e.g., it masks fabric yellowing, etc.]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Liquid Crystal Substances (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明係關於基於二胺基芪衍生物之光學增亮劑之儲存穩定溶液,其無需額外之增溶添加劑。
吾人已熟知可藉由添加光學增亮劑(OBA)以改良紙張、板材、紡織品及不織布產品之白度及附隨之吸引力。紙張及板材工業中最重要之光學增亮劑為4,4'-二胺基芪-2,2'-二磺酸之經苯胺基取代之雙三嗪基衍生物。該苯胺基取代基可含有額外磺酸基團,其提供更佳之水溶性。光學增亮劑(其中該苯胺基取代基不含磺酸基)對於纖維素纖維具有尤其高之親和力,且尤其適於在造紙方法之濕端使用。為了便於操作及計量,紙張與板材工業需要以液體形式(較佳為濃縮水溶液之形式)提供光學增亮劑。此外,該液體形式必須在廣泛溫度範圍內(通常為4至50℃)之長期儲存中保持穩定。從前,添加至多30重量%之諸如尿素或乙二醇之增溶助劑以提供儲存穩定性。該等增溶劑對於纖維素不具有親和力,但會污染造紙廠之流出物。因此需要4,4'-二胺基芪-2,2'-二磺酸之經苯胺基取代之雙三嗪基衍生物,其可在不添加增溶助劑之情況下形成穩定、濃縮水溶液。
GB 1,243,276對含有至少一個(較佳兩個)丙醯胺基之4,4'-二胺基芪-2,2'-二磺酸之雙三嗪基衍生物請求專利,並對其作為紙張增亮劑之用途申請專利。該案揭示式(A)化合物之製備及應用。
將該化合物作為固體分離,並在將其應用於纖維素纖維之水性懸浮液前以0.1%之濃度溶解於水中。
GB 1,247,765中亦描述了化合物(A)。
根據EP 376,893 A2,化合物(A)亦為洗衣液組合物之較佳組分。其發明者聲明:"本發明之光學增亮劑以粉末形式或作為水溶液而使用。該等溶液具有18至75重量%活性物質之含量,且較佳亦含有增溶物質。"
在GB 1,243,276、GB 1,247,765或EP 376,893 A2中未提供對於除鈉以外使用其他抗衡離子之優勢的建議。
WO 02/055646試圖藉由提供兩種或兩種以上雙(三嗪胺基)芪衍生物,以解決形成雙磺酸化光學增亮劑之穩定、濃縮水溶液之問題。實例1描述穩定水溶液之製備,其含有等莫耳化合物(B)及(C)(各為混合鈉鹽/三乙醇銨鹽之形式)混合物形式之0.2844 mol/kg光學增亮劑。
然而,儲存穩定性亦依賴於添加劑-參見WO 02/055646第10頁之(F1)-其較佳以溶液之0.2至3重量%之濃度使用。較佳添加劑(F1)為三級烷基醇胺,尤其較佳為三異丙醇胺。
WO 2005/028749 A1揭示了包含烷基醇胺及雙(三嗪胺基)芪衍生物之光學增亮劑組合物。較佳烷基醇胺為2-胺基-2-甲基-1-丙醇、1-胺基-2-丙醇或2-胺基-2-甲基-1-丙醇與2-(N-甲胺基)-2-甲基-1-丙醇之混合物。
日本未審查專利公開案62-273266對包含雙(三嗪胺基)芪衍生物之四級銨鹽之光學增亮劑組合物請求專利。該較佳四級銨離子為三甲基-β-羥乙銨離子。
EP-A-884 312揭示式(D)之雙(三嗪胺基)芪衍生物之水合物
其中M及M1分別代表氫、鹼土金屬或銨。主張該水合物可實現使用少量調配物助劑生成穩定液體懸浮液。
然而造紙者為了便於(例如)操作及計量,較佳使用溶液形式之光學增亮劑。因此仍需要提供無增溶助劑之二磺酸
化光學增亮劑之穩定、濃縮水溶液。
現令人驚奇地發現,4,4'-二胺基芪-2,2'-二磺酸之經苯胺基取代之雙三嗪基衍生物之一特定鹽形式可在不添加增溶助劑之情況下形成穩定濃縮溶液。
因此本發明提供式(1)之化合物
其中R為氫或甲基,R1為氫、具有1至4個碳原子之烷基、含有2至4個碳原子之β-羥基烷基、含有3或4個碳原子之β-烷氧基烷基或CH2CH2CONH2,R2為氫或甲基,M+為Li+、Na+或K+,及n小於或等於1.5。
如下化合物為較佳,其中R為氫或甲基,R1為氫、甲基、含有2或3個碳原子之β-羥基烷基,R2為氫或甲基,
M+為Na+,及n小於或等於1.5。
如下化合物為更佳,其中R為氫R1為氫、甲基或含有2個碳原子之β-羥基烷基,R2為氫M+為Na+,及n小於或等於1.5。
如下化合物為尤其較佳,其中R為氫R1為-CH2CH2OH,R2為氫M+為Na+,及n小於或等於1.2。
本發明亦提供一種用於製備以上化合物之方法,該方法之特徵在於藉由使用2-二甲胺基乙醇及無機酸(例如HCl或H2SO4)進行處理或藉由使用陽離子離子交換樹脂及2-二甲胺基乙醇進行連續處理,將水溶液形式之式(2)化合物
轉化為混合鹽形式(1),其中至少25%與磺酸鹽基團相關
聯之M+離子由(CH3)2NH+CH2CH2OH離子置換。隨後視情況將該式(1)化合物分離,並可進一步藉由薄膜過濾將其與過量之鹽及烷醇胺分離。
該較佳薄膜過濾方法為使用例如聚碸、聚偏二氟乙烯、乙酸纖維素酯或薄膜之超濾方法。
本發明進一步提供式(1)之一或多種化合物之水溶液,其可視情況含有一或多種載體、防凍劑、消泡劑、助溶劑、防腐劑、錯合劑等,及製備該光學增亮劑期間所形成之有機副產物。
已知載劑對有色塗層增亮劑組合物提供改良之增白特性,且可為(例如)聚乙二醇、聚乙烯醇或羧甲基纖維素。
防凍劑可為例如尿素、二甘醇或三乙二醇。
助溶劑可為例如尿素、三乙醇胺、三異丙醇胺或2-二甲胺基乙醇。
式(1)化合物及其溶液適合作為光學增亮劑用於增白紡織品、紙張、板材及不織布。其尤其有用於紙張及板材之增白,並適於應用於紙漿水性懸浮液或紙張表面,尤其在一有色塗層組合物中。其特徵在於高儲存穩定性、高產量及易用性。其亦與纖維素物件(尤其紙張及板材)生產中習知使用之其他添加劑高度相容。
本發明又關於一種用於紙張增白之方法,其包含如下主要步驟:提供一紙漿懸浮液,添加以乾燥纖維計0.01至2重量%之包含至少一式(1)化
合物的水溶液,由該紙漿懸浮液製造一紙張,擠壓並乾燥該紙張。
本發明尚關於一種用於紙張增白之方法,其包含如下主要步驟:藉由將白堊或其他白色顏料、一或多種分散劑、一原生乳膠黏合劑與視情況之第二黏合劑及視情況之其他添加劑共同混合,製備一水性塗層組合物,添加以乾燥顏料計0.01至3重量%之包含至少一式(1)化合物的水溶液,將該塗層組合物塗覆至一紙張,乾燥該經塗覆之紙張。
以下實例將更詳細說明本發明。若未另外指出,則"份"表示"重量份"且"%"表示"重量%"。使用由GE Infrastructure Water & Process Technologies所提供之G系列薄膜超濾薄膜元件進行薄膜過濾。
在60℃下,將291份之式(3)胺
添加至7750份水中之824份式(4)化合物之經攪拌懸浮液
將該混合物加熱至回流並保持4小時,同時藉由添加30%水溶液形式之氫氧化鈉將pH值控制為8.5-9.0。添加44份氯化鈉,並在回流溫度下將該化合物再攪拌10分鐘。隨後在攪拌停止前將該混合物冷卻至90℃。靜置10分鐘後,將含有式(A)化合物之下層油相(1990份)與該含鹽之含水相分離,並在80℃下於攪拌同時將其添加至1570份冷水中。隨後在50℃下用350份冷水中197份2-二甲胺基乙醇之溶液及197份37%水性氫氯酸處理由此形成之溶液。將該混合物在50℃下攪拌10分鐘,隨後冷卻至20℃。靜置1小時後,將下層油相分離,並用水稀釋至5000份。在藉由蒸餾移除水之前,藉由水溶液之薄膜過濾移除過量氯化鈉及烷基醇胺,以產生含有28%式(5)化合物之3520份水溶液。
在有或無晶種存在之情況下,將由此形成之水溶液在4℃下穩定儲存至少兩週。
繼續實例1,直至首次將油(1990份)與含鹽之含水相分離。隨後將油倒入2700份水中之309份氯化膽鹼之經攪拌溶液。在藉由蒸餾移除水之前,藉由該水溶液之薄膜過濾移除過量鹽,以產生含有28%式(6)化合物之3520份水溶液。
在有晶種存在之情況下,使由此形成之水溶液在4℃下4天之儲存內沉澱。
繼續實例1,直至用水(1570份)將來自第一次相分離之油(1990份)稀釋。隨後在50℃下用350份冷水中之196份2-胺基-2-甲基-1-丙醇之溶液及197份37%水性氫氯酸處理由此形成之溶液。將混合物在50℃下攪拌10分鐘,隨後冷卻至20℃。靜置1小時後,將下層油相分離,並用水稀釋至5000份。在藉由蒸餾移除水之前,藉由該水溶液之薄膜過濾移除過量氯化鈉及烷基醇胺,以產生含有28%式(7)化合
物之3520份水溶液。
在有晶種存在之情況下,使由此形成之水溶液在4℃下4天之儲存內沉澱。
繼續實例1,直至用水(1570份)將來自第一次相分離之油(1990份)稀釋。隨後在50℃下用350份冷水中之135份乙醇胺之溶液及197份37%水性氫氯酸處理由此形成之溶液。將該混合物在50℃下攪拌10分鐘,隨後冷卻至20℃。靜置1小時後,將下層油相分離,並用水稀釋至5000份。在藉由蒸餾移除水之前,藉由該水溶液之薄膜過濾移除過量氯化鈉及烷基醇胺,以產生含有27%式(8)化合物之3520份水溶液。
在有晶種存在之情況下,使由此形成之水溶液在4℃下1天之儲存內沉澱。
繼續實例1,直至用水(1570份)將來自第一次相分離之油(1990份)稀釋。在藉由蒸餾移除水之前,在50℃下藉由該水溶液之薄膜過濾移除過量氯化鈉,以產生含有26%式(A)化合物之3520份水溶液。
藉由冷卻至室溫使由此形成之水溶液沉澱。
繼續實例1,直至首先將油(1990份)與含鹽之含水相分離。在80℃下於攪拌同時將該油添加至1582份冷水中之171份37%水性氫氯酸及150份2-二甲胺基乙醇溶液。將該混合物攪拌10分鐘並冷卻至20℃。靜置1小時後,將下層油相分離,並用水稀釋至5000份。藉由薄膜過濾處理該水溶液以移除過量氯化鈉,隨後藉由蒸餾將其濃縮。另外添加7份2-二甲胺基乙醇作為助溶劑。調整強度以獲得3520份含有28%式(9)化合物及0.2% 2-二甲胺基乙醇之水溶液。
在有或無晶種存在之情況下,將由此形成之溶液在4℃下穩定儲存至少兩週。
將製備實例1之產物,以乾燥纖維計之0.2至2重量%濃度範圍,添加至漂白雲杉亞硫酸纖維素與漂白山毛櫸亞硫酸纖維素(打漿至20 SR之Schopper Riegler濕度)之50:50混合物之200份2.5%水性懸浮液中。將懸浮液攪拌5分鐘,接著稀釋至1000份。隨後藉由使該懸浮經一金屬絲網並條(drawing)而製得紙張。經壓縮及乾燥後,在一Minolta CM-700d分光光度計上量測該紙張白度。
該表之結果清楚地說明由本發明化合物所提供之優異增白效果。
製得含有500份白堊(以Hydrocarb 90之商標購自OMYA)、500份黏土(以Kaolin SPS之商標購自IMERYS)、470份水、6份分散劑(一種聚丙烯酸鈉鹽,以Polysalz S之商標購自BASF)、200份乳膠(一種丙烯酸酯共聚物,可以Acronal S320D之商標購自BASF)、水中40份10%聚乙烯醇溶液(可以Mowiol 4-98之商標購自Kuraray)及水中50份10%羧甲基纖維素溶液(可以Finnfix 5.0之商標購自Noviant),之塗層組合物。藉由添加水將該等固體含量調整為60%,並使用氫氧化鈉將pH值調整為8-9。
將製備實例1之產物以0.5、1.0及1.5%之濃度添加至經攪拌之塗層組合物。隨後使用一自動線繞棒敷帖器,以一標準速度設置及一標準棒上負載,將該增亮塗層組合物塗覆於一市售75 gsm中等尺寸白紙基板。隨後將該經塗覆紙張在一熱氣流中乾燥5分鐘。允許調節該經乾燥紙張,隨後在一經校準Elrepho分光光度計上量測CIE白度。
該表之結果清楚地說明由本發明化合物所提供之優異增白效果。
Claims (14)
- 一種式(1)之化合物,
- 如請求項1之化合物,其中R為氫或甲基,R1為氫、甲基、含有2或3個碳原子之β-羥基烷基,R2為氫或甲基,M+為Na+,及n小於或等於1.5且大於0。
- 如請求項1之化合物,其中R為氫, R1為氫、甲基或含有2個碳原子之β-羥基烷基,R2為氫,M+為Na+,及n小於或等於1.5且大於0。
- 如請求項1之化合物,其中R為氫,R1為-CH2CH2OH,R2為氫,M+為Na+,及n小於或等於1.2且大於0。
- 一種水溶液,其含有20至40重量%之至少一種如請求項1至4中任一項之式(1)化合物作為活性物質。
- 如請求項5之水溶液,其中該活性物質之濃度為25至35重量%。
- 如請求項5或6之水溶液,其另外含有一或多種載劑、防凍劑、消泡劑、助溶劑、防腐劑、錯合劑及製備該光學增亮劑期間所形成之有機副產物。
- 一種製備如請求項1至4中任一項之式(1)化合物之方法,其中藉由使用2-二甲胺基乙醇及無機酸進行處理或藉由使用陽離子離子交換樹脂及2-二甲胺基乙醇進行連續處理,將水溶液形式之式(2)化合物
- 如請求項8之方法,其中將該式(1)化合物分離,並進一步藉由薄膜過濾使其與過量鹽及烷基醇胺分離。
- 一種製備如請求項7之溶液之方法,其中將額外組份添加至由製備該式(1)化合物所得之水溶液中。
- 一種如請求項1至4中任一項之式(1)化合物之用途,或如請求項5至7中任一項之水溶液之用途,其係用於紡織品、紙張、板材及不織布之光學增亮。
- 如請求項11之用途,其係用於水性紙漿懸浮液。
- 一種用於紙張增白之方法,其包含如下主要步驟提供一紙漿懸浮液,添加以乾燥纖維計0.01至2重量%之如請求項5至7中任一項之水溶液,由該紙漿懸浮液製造一紙張,擠壓並乾燥該紙張。
- 一種用於紙張增白之方法,其包含如下主要步驟藉由將白堊或其他白色顏料、一或多種分散劑、一原生乳膠黏合劑與視情況之第二黏合劑及視情況之其他添加劑共同混合,製備一水性塗層組合物, 添加以乾燥顏料計0.01至3重量%之如請求項5至7中任一項之水溶液,將該塗層組合物塗覆至一紙張,乾燥該經塗覆之紙張。
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US3956283A (en) * | 1973-05-22 | 1976-05-11 | Sandoz Ltd. | Bis-(triazinylamino)-stillene derivatives |
WO2003044275A1 (en) * | 2001-11-21 | 2003-05-30 | Clariant International Ltd | Improvements relating to optical brighteners |
WO2005049682A1 (en) * | 2003-11-18 | 2005-06-02 | Ciba Specialty Chemicals Holding Inc. | Fluorescent whiteninig pigments |
Also Published As
Publication number | Publication date |
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RU2437874C2 (ru) | 2011-12-27 |
AR057724A1 (es) | 2007-12-12 |
CA2610518A1 (en) | 2007-02-15 |
CN101253161A (zh) | 2008-08-27 |
AU2006278119A1 (en) | 2007-02-15 |
PT1912955E (pt) | 2014-02-24 |
EP1752453A1 (en) | 2007-02-14 |
ES2446067T3 (es) | 2014-03-06 |
BRPI0614473B1 (pt) | 2018-07-31 |
NO20076018L (no) | 2008-05-02 |
CN101253161B (zh) | 2012-09-05 |
WO2007017336A1 (en) | 2007-02-15 |
CA2610518C (en) | 2013-09-10 |
ZA200710411B (en) | 2009-08-26 |
TW200712055A (en) | 2007-04-01 |
BRPI0614473A2 (pt) | 2011-03-29 |
JP2009503212A (ja) | 2009-01-29 |
US20100159763A1 (en) | 2010-06-24 |
IL189147A0 (en) | 2008-08-07 |
EP1912955A1 (en) | 2008-04-23 |
KR101365333B1 (ko) | 2014-02-19 |
EP1912955B1 (en) | 2013-12-11 |
RU2008108079A (ru) | 2009-09-10 |
KR20080032140A (ko) | 2008-04-14 |
AU2006278119B2 (en) | 2012-04-05 |
US8221588B2 (en) | 2012-07-17 |
JP5437632B2 (ja) | 2014-03-12 |
HK1124047A1 (en) | 2009-07-03 |
IL189147A (en) | 2012-03-29 |
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