TWI507490B - 高品質噴墨印刷用的光學增亮組成物 - Google Patents
高品質噴墨印刷用的光學增亮組成物 Download PDFInfo
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Description
本發明係關於包含二胺基菧之衍生物、黏合劑和二價金屬鹽之適用於高品質噴墨印刷的基材光學增亮之液態組成物。
噴墨印刷在近年來成為在紙片上記錄資料和影像之非常重要的方式。多彩影像的低成本、易製造及相當高速率為此技術的一些優點。但是噴墨印刷對於基材有一些重大要求以符合短乾燥時間、高印密度和清晰度,及降低色至色的滲色(color-to-color bleed)之要求。此外,此基材應具有高亮度。普通紙(例如)吸收噴墨印刷中使用的水性陰離子染料或顏料的能力欠佳;墨留在紙面上的時間長,此造成墨發生擴散且導致印跡清晰度低。達到短乾燥時間並提供高印密度和清晰度的一個方法係使用特別之經矽石塗覆的紙。但是,此紙的製造成本高。
US 6,207,258提供此問題的部分解決方式,其揭示著色的噴墨印刷品質可藉由使用含有二價金屬鹽的水性上膠介質處理基材表面而改良。氯化鈣和氯化鎂為較佳的二價金屬鹽。此上膠介質亦可含有用於處理未經塗覆的紙中所使用之其他慣用的紙添加劑。慣用的紙添加劑含括光學增亮劑(OBA),已知其可明顯改良紙的白度並藉此改良噴墨印跡和背景之間的對比。US 6,207,258未提出使用本發明之光學增亮劑的例子。
WO 2007/044228主張包括烯基丁二酸酐上膠劑和/或烷基酮烯二聚體上膠劑並添加金屬鹽之組成物,其並未提到使用本發明之光學增亮劑。
WO 2008/048265主張一種用以印刷之記錄薄片,其包含自木質纖維素纖維形成的基材,該基材的至少一個表面經水溶性二價金屬鹽處理。此記錄薄片具有增進的影像乾燥時間。光學增亮劑含括於包含氯化鈣和一或多種澱粉之較佳表面處理的任意組份列表中。其並未提出使用本發明之光學增亮劑的例子。
WO 2007/053681描述一種上膠組成物,其當施用至噴墨基材時,改良印密度、色至色的滲色、印跡清晰度和/或影像乾燥時間。此上膠組成物包含至少一種顏料(以沉澱或研磨的碳酸鈣為佳)、至少一種黏合劑,它的一個例子係包括澱粉和聚乙烯醇、至少一種含氮的有機物種(以氯化二烯丙基二甲基銨(DADMAC)的聚合物或共聚物為佳)和至少一種無機鹽之多組份系統。此上膠組成物亦可含有至少一種光學增亮劑,其例子為Clariant的Leucophor BCW和Leucophor FTS。
只有在可相容的水溶性光學增亮劑可資利用時,才能完全展現在試圖用於著色的噴墨印刷之基材中使用二價金屬鹽(如氯化鈣)的優點。但已熟知水溶性光學增亮劑有在高鈣濃度中沉澱的傾向(請參考,例如Taylor & Francis於1998年發行,著者為Werner Kss和Horst Behrens的Tracing Technique in Geohydrology,第50頁)。
據此,對於與含有二價金屬鹽的上膠組成物具良好相容性之水溶性光學增亮劑有需求存在。
現已發現式(1)的光學增亮劑與含有二價金屬鹽的上膠組成物具有令人訝異的良好相容性。
因此,本發明提出一種用於基材(以紙為佳)之光學增亮之上膠組成物,其特別適用於著色的噴墨印刷,該上膠組成物包含
(a)至少一種黏合劑,
(b)至少一種二價金屬鹽,該至少一種二價金屬鹽選自氯化鈣、氯化鎂、溴化鈣、溴化鎂、碘化鈣、碘化鎂、硝酸鈣、硝酸鎂、甲酸鈣、甲酸鎂、乙酸鈣、乙酸鎂、硫酸鈣、硫酸鎂、硫代硫酸鈣、或硫代硫酸鎂、或該等化合物之混合物,
(c)水,和
(d)至少一種式(1)的光學增亮劑
[M+
]n
[X+
]6-n
其中M和X 相同或不同且彼此獨立地選自氫、鹼金屬陽離子、銨、經C1-C4直鏈或支鏈烷基單-、二-或三取代的銨、經C1-C4直鏈或支鏈羥烷基單-、二-或三取代的銨、或該等化合物之混合物,和n 是在0至6的範圍內。
較佳的式(1)化合物中,M和X 相同或不同且彼此獨立地選自鹼金屬陽離子和三取代的C1-C4直鏈或支鏈羥烷基、或該等化合物之混合物,和n 是在0至6的範圍內。
更佳的式(1)化合物中M和X 相同或不同且彼此獨立地選自Li、Na、K和三取代的C1-C3直鏈或支鏈羥烷基、或該等化合物之混合物,和n 是在0至6的範圍內。
特別佳的式(1)化合物中M和X 相同或不同且彼此獨立地選自Na、K和三乙醇胺,或該等化合物之混合物,和n 是在0至6的範圍內。
該上膠組成物中的光學增亮劑濃度可介於0.2和30克/升之間,以介於1和15克/升之間為佳,介於2和12克/升之間最佳。
此黏合劑典型地是經酵素或化學方式改質的澱粉,如,經氧化的澱粉、羥乙基化的澱粉或乙醯化的澱粉。取決於實施的特別體系,此澱粉亦可為天然澱粉、陰離子性澱粉、陽離子性澱粉、或兩性。此澱粉來源可為任何者,澱粉來源的例子包括玉米、麥、洋芋、米、木薯和西谷(sago)。也可以使用一或多種次要黏合劑(如,聚乙烯醇)。
該上膠組成物中之黏合劑濃度可介於1和30重量%之間,以介於2和20重量%之間為佳,介於5和15重量%之間更佳。
較佳的二價金屬鹽選自氯化鈣、氯化鎂、溴化鈣、溴化鎂、硫酸鈣、硫酸鎂、硫代硫酸鈣、或硫代硫酸鈣鎂、或該等化合物之混合物。
更佳的二價金屬鹽係選自氯化鈣或氯化鎂或該等化合物之混合物。
該上膠組成物中的二價金屬鹽濃度可介於1和100克/升之間,介於2和75克/升之間較佳,介於5和50克/升之間最佳。
當二價金屬鹽係鈣鹽和鎂鹽之混合物時,鈣鹽的量可在0.1至99.9%的範圍內。
該上膠組成物的pH值典型地在5-13的範圍內,以6-11為佳。
除了一或多種黏合劑、一或多種二價金屬鹽、一或多種光學增亮劑和水以外,該上膠組成物還可含有製備光學增亮劑期間內形成的副產物及其他慣用的紙添加劑。此添加劑的例子係載體、消沫劑、蠟乳液、染料、無機鹽、助溶劑、防腐劑、錯合劑、表面上膠劑、交聯劑、顏料、或特殊樹脂..等。
本發明的另一方面,光學增亮劑可以事先與聚乙烯醇混合,以促進上膠組成物中之光學增亮劑的效能。此聚乙烯醇可具有任何水解程度,包括60至99%。該光學增亮劑/聚乙烯醇混合物可含有任何量的光學增亮劑和聚乙烯醇。製造光學增亮劑/聚乙烯醇混合物的例子可見於WO 2008/017623。
該光學增亮劑/聚乙烯醇混合物可為水性混合物。
該光學增亮劑/聚乙烯醇混合物可含有任何量的光學增亮劑,包括10至50重量%的至少一種光學增亮劑。此外,此光學增亮劑/聚乙烯醇混合物可含有任何量的聚乙烯醇,包括0.1至10重量%的聚乙烯醇。
該上膠組成物可藉此技術領域已知的任何表面處理方法施用至紙基材表面。施用方法的例子包括施膠加壓施用、砑光上膠施用、槽法上膠、塗覆施用和噴灑施用。(請參考,例如,Handbook for Pulp & Paper Technologists,G. A. Smook,2nd
Edition Angus Wilde Publications,1992,p.283-286和US 2007/0277950)。較佳施用法係施膠加壓,如,膠泥施膠加壓或桿計量施膠加壓。預先形成的紙片通過上膠組成物滿溢的雙輥壓區(two-roll nip)。此紙吸收一些組成物,餘者留在壓區中。
紙基材含有纖維素纖維的網,其中的纖維素纖維可為合成者或源自於任何纖維質植物,包括木質和非木質來源。較佳地,此纖維素纖維源自於硬木和/或軟木。此纖維可為原始纖維或再生纖維,或原始和再生纖維的任何組合。
紙基材中所含的纖維素纖維可藉如,分別於Handbook for Pulp & Paper Technologists,G. A. Smook,2nd
Edition Angus Wilde Publications,1992中的第13和15章,所描述的物理和/或化學方法改質。纖維素纖維之化學改質的一個例子係添加光學增亮劑,此如EP 884,312、EP 899,373、WO 02/055646、WO 2006/061399、WO 2007/017336、WO 2007/143182、US 2006-0185808和US 2007-0193707中所述者。
該上膠組成物係藉由在介於20℃和90℃之間的溫度將光學增亮劑(或光學增亮劑/聚乙烯醇混合物)和二價金屬鹽加至預先形成的黏合劑水溶液而製備。較佳地,在介於50℃和70℃之間的溫度,該二價金屬鹽於光學增亮劑(或光學增亮劑/聚乙烯醇混合物)之前添加。
含有本發明上膠組成物的紙基材可以具有任何ISO亮度,包括ISO亮度至少80,至少90和至少95。
本發明的紙基材可以具有任何CIE白度,包括至少130,至少146,至少150,和至少156。相較於慣用之含有相似量光學增亮劑的上膠組成物,此上膠組成物有增進薄片之CIE白度的趨勢。
相較於慣用之含有類似量光學增亮劑的上膠組成物,本發明之上膠組成物之使得已施用彼之薄片綠化的趨勢減低。綠化係與薄片的飽和度有關的現象,其使得薄片的白度不會提高,即使提高光學增亮劑的量時亦然。綠化趨勢藉a*-b*圖線測定,a*和b*為CIE Lab系統中的色座標。據此,本發明之上膠組成物提供使用者在二價金屬離子存在時,有效提高在紙上之光學增亮劑濃度的能力且未達飽和,且同時維持或增進紙的CIE白度和ISO亮度。
本發明之紙基材展現適用於噴墨印刷的增進性質,此基材亦可用於多用途和雷射噴墨印刷。這些應用可包括須要定度尺寸紙基材及紙卷基材者。
本發明之紙基材可含有影像。此影像可以任何物質(包括染料、顏料和調色劑)形成於基材料上。
一旦在基材上形成影像,印刷密度可為任何光學印刷密度,包括光學印刷密度至少1.0,至少1.2,至少1.4,至少1.6。測定光學印刷密度的方法可見於EP 1775141。
式(1)中M=Na且n=6的化合物之製備已於之前述於WO 02/060883和WO 02/077106。未曾提出M≠X且n<6的式(1)化合物之製備例。
式(1)化合物係藉三聚鹵化氰(cyanuric halide)與下列物質之逐步反應製得
(a)如下式的胺
其為自由酸、部分-或全鹽形式,
(b)如下式的二胺
其為自由酸、部分-或全鹽形式,及
(c)如下式的二異丙醇胺。
可使用的三聚鹵化氰為氟化物、氯化物或溴化物。以三聚氯化氰為佳。
各反應可在水性介質中進行,此三聚鹵化氰懸浮於水中,或懸浮於含水/有機介質中,此三聚鹵化氰溶解於溶劑(如,丙酮)中。每種胺可以未經稀釋地引入,或以水溶液或懸浮液形式引入。此胺可以任何順序反應,但以先將芳族胺反應為佳。各種胺可以化學計量比或過量反應。基本上,此芳族胺以化學計量比或略為過量反應;二異丙醇胺通常以超過化學計量比5-30%使用。
用於三聚鹵化氰的第一個鹵素之取代反應,於0至20℃的溫度範圍內,且在酸性至中性pH條件(以在2至7的pH範圍內為佳)下操作較佳。用於三聚鹵化氰的第二個鹵素之取代反應,於20至60℃的溫度範圍內,且在弱酸性至弱鹼性條件(以在4至8的pH範圍內為佳)下操作較佳。用於三聚鹵化氰的第三個鹵素之取代反應,於60至102℃的溫度範圍內,且在弱酸性至鹼性條件(以在7至10的pH範圍內為佳)下操作較佳。
通常藉由添加適當的鹼來控制各反應的pH,鹼之選擇通常取決於所欲的產物組成。較佳的鹼是,例如,鹼金屬(如,鋰、鈉或鉀)氫氧化物、碳酸鹽或碳酸氫鹽,或脂族三級胺(如,三乙醇胺或三異丙醇胺)。當使用二或更多種不同的鹼之組合時,這些鹼可以任何順序添加,或同時添加。
須使用酸調整反應pH時,可以使用的酸的例子包括氫氯酸、硫酸、甲酸和醋酸。
含有一或多種通式(1)之水溶液可藉膜過濾或藉沉澱及之後使用適當的鹼之溶液的程序而任意地經去鹽化。
較佳的膜過濾法係使用如,聚碸、聚偏氟乙烯、纖維素乙酸酯或薄膜,之超過濾法。
下列實例以更詳細的方式說明本發明。若未明示,則“份”代表“重量份”而“%”代表“重量%”。
階段1:31.4份的苯胺-2,5-二磺酸單鈉鹽加至150份水中並藉約25℃之pH值約8-9之約30%的氫氧化鈉溶液之助溶解。所得溶液以約30分鐘添加至分散於30份水、70份冰和0.1份抗發泡劑的18.8份三聚氯化氰中。使用冰/水浴及有須要時,在反應混合物中添加冰,使溫度維持低於5℃。使用約20%碳酸鈉溶液使pH維持於約4-5。添加終了之後,使用約20%碳酸鈉溶液使pH提高至約6,並於約0-5℃持續攪拌直到反應完全(3-4小時)。
階段2:8.8份的碳酸氫鈉加至反應混合物中。把藉由在氮氣下,藉約45-50℃之pH值約8-9之約30%氫氧化鈉溶液之助,將18.5份4,4’-二胺基菧-2,2’-二磺酸溶解於80份水中而得的水溶液滴入反應混合物中。所得混合物於約45-50℃加熱直到反應完全(3-4小時)。
階段3:然後,添加17.7份的二異丙醇胺且溫度逐漸提高至約85-90℃並於使用約30%氫氧化鈉溶液使pH維持於約8-9的同時,維持於此溫度直到反應完全(2-3小時)。然後,將溫度降至50℃且反應混合物經過濾並冷卻至室溫。溶液調整至可提供式(1)中M=X=Na且n=6的化合物之水溶液之濃度(0.125莫耳/公斤,17.8%)。
依照與實例1相同的程序,差別僅在於使用約30%的氫氧化鉀溶液代替階段3中之約30%的氫氧化鈉溶液,得到式(1)中M=Na,X=K且的化合物之水溶液(0.125莫耳/公斤,約18.0%)。
依照與實例1相同的程序,差別僅在於使用10份碳酸氫鉀代替階段2中的8.8份碳酸氫鈉及使用約30%的氫氧化鉀溶液代替階段2和3中之約30%的氫氧化鈉溶液,得到式(1)中M=Na,X=K且的化合物之水溶液(0.125莫耳/公斤,約18.3%)。
依照與實例1相同的程序,差別僅在於使用約30%的氫氧化鉀溶液代替階段1、2和3中之約30%的氫氧化鈉溶液,使用約20%的碳酸鉀溶液代替階段1中之約20%的碳酸鈉溶液,及使用10份碳酸氫鉀代替階段2中的8.8份碳酸氫鈉,得到式(1)中M=Na,X=K且的化合物之水溶液(0.125莫耳/公斤,約18.8%)。
依照與實例1相同的程序,差別僅在於使用約10%的氫氧化鋰溶液代替階段3中之約30%的氫氧化鈉溶液,得到式(1)中M=Na,X=Li且的化合物之水溶液(0.125莫耳/公斤,約17.7%)。
依照與實例1相同的程序,差別僅在於使用3.7份碳酸鋰代替階段2中使用的8.8份碳酸氫鈉及使用約10%氫氧化鋰溶液代替階段2和3中的約30%氫氧化鈉溶液,得到式(1)中M=Na,X=Li且的化合物之水溶液(0.125莫耳/公斤,約17.3%)。
實例1中得到的式(1)化合物之濃縮液以濃鹽酸沈澱然後過濾而分離出式(1)中M=H的化合物。然後,將此壓餅溶解於7當量三乙醇胺之水溶液中,以得到式(1)中M=Na,X=三乙醇銨且的化合物之水溶液(0.125莫耳/公斤,約24.2%)。
藉攪拌下列者同時加熱至90-95℃,直到得到冷卻至室溫之後仍維持安定的透明溶液,而製造光學增亮溶液8
- 根據實例4製備之含有式(1)中M=Na,X=K且的化合物之水溶液,
- 聚乙烯醇,其水解度為85%且Brookfield黏度為3.4-4.0mPa.s和
- 水。
選擇各組份的份數以使得最後的水溶液8所含之根據實例4製備之式(1)中M=Na,X=K且的化合物的濃度為0.125莫耳/公斤並含有2.5%水解度為85%且Brookfield黏度為3.4-4.0mPa.s的聚乙烯醇。溶液8的pH在8-9的範圍內。
藉由將根據實例1至8製備的式(1)化合物之水溶液以0至50克/升(0至約12.5克/升光學增亮劑)的濃度範圍加至氯化鈣(35克/升)和陰離子性澱粉(50克/升)(Penford Starch 260)於60℃攪拌的水溶液中而製得上膠組成物。使此上膠溶液冷卻,然後倒在實驗室施膠加壓機的移動輥之間並施用至市售75克/平方米AKD(烷基烯酮二聚物)上膠的漂白紙基材片上。此經處理的紙在平板乾燥機(flat bed drier)中於70℃乾燥5分鐘。使此經乾燥的紙適應環境,然後在經校正的Auto Elrepho光譜儀上測定CIE白度。其結果示於表1。
藉由將US 2005/0124755 A1第8頁的表中所揭示的六磺酸基化合物之水溶液以由0至50克/升(0至約12.5克/升的光學增亮劑)的濃度範圍加至氯化鈉(35克/升)和陰離子性澱粉(50克/升)(Penford Starch 260)於60℃攪拌的水溶液中而製得上膠組成物。使此上膠溶液冷卻,然後倒在實驗室施膠加壓機的移動輥之間並施用至市售75克/平方米AKD(烷基烯酮二聚物)上膠的漂白紙基材片上。此經處理的紙在平板乾燥機中於70℃乾燥5分鐘。使此經乾燥的紙適應環境,然後在經校正的Auto Elrepho光譜儀上測定CIE白度。其結果示於表1。
表1中的結果清楚證實本發明之組成物提供極佳的白化效果。
印刷性評估係以使用下拉輥將黑色顏料墨液施用至紙並使其乾燥的方式進行。光學密度係使用Ihara Optical Densitometer R710測定。其結果示於表2。
光學密度=log10
1/R,其中R=反射值
表2中的結果顯示本發明之組成物對於墨印密度沒有負面影響。
Claims (11)
- 一種用於噴墨印刷用的基材之光學增亮之上膠組成物,其包含:(a)至少一種黏合劑,(b)至少一種二價金屬鹽,該至少一種二價金屬鹽選自氯化鈣、氯化鎂、溴化鈣、溴化鎂、碘化鈣、碘化鎂、硝酸鈣、硝酸鎂、甲酸鈣、甲酸鎂、乙酸鈣、乙酸鎂、硫酸鈣、硫酸鎂、硫代硫酸鈣、或硫代硫酸鎂、或該等化合物之混合物,(c)水,和(d)至少一種式(1)的光學增亮劑
- 如申請專利範圍第1項之組成物,其中M和X 相同或不同且彼此獨立地選自Na、K和三乙醇胺、或該等化合物之混合物,和n 是在0至6的範圍內。
- 如申請專利範圍第1項之組成物,其中該二價金屬鹽係氯化鈣或氯化鎂或該等化合物之混合物。
- 如申請專利範圍第1項之組成物,其中該上膠組成物中的二價金屬鹽濃度介於5和50克/升之間。
- 如申請專利範圍第1項之組成物,其中該上膠組成物中的光學增亮劑濃度介於2和12克/升之間。
- 如申請專利範圍第1項之組成物,其中該上膠組成物另含有製備光學增亮劑期間內形成的副產物及其他慣用的紙添加劑,該添加劑係載體、消沫劑、蠟乳液、染料、無機鹽、助溶劑、防腐劑、錯合劑、表面上膠劑、交聯劑、顏料、或特殊樹脂。
- 如申請專利範圍第1項之組成物,其中該上膠組成物另含有聚乙烯醇。
- 一種製造如申請專利範圍第1至7項中任一項之上膠組成物之方法,其中在介於20℃和90℃之間的溫度將該光學增亮劑溶液和該二價金屬鹽加至預先形成的黏合劑水溶液。
- 一種紙基材,包含:纖維素纖維網;和如申請專利範圍第1至7項中任一項之上膠組成物。
- 一種經增亮的紙之製法,其特徵在於該紙的表面以申請專利範圍第1至7項中任一項之上膠組成物處理。
- 一種在紙基材上提供影像的方法,包含以墨、顏料或調色劑(toner)在包含纖維素纖維網和申請專利範圍第1至7項中任一項之上膠組成物的紙基材上印刷影像。
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- 2009-11-20 JP JP2011537879A patent/JP2012509796A/ja active Pending
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2011
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2013
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2015
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Also Published As
Publication number | Publication date |
---|---|
CA2744839C (en) | 2016-10-11 |
KR20110087340A (ko) | 2011-08-02 |
JP2012509796A (ja) | 2012-04-26 |
WO2010060570A1 (en) | 2010-06-03 |
TW201035261A (en) | 2010-10-01 |
IL213182A (en) | 2016-07-31 |
JP2017165106A (ja) | 2017-09-21 |
IL213182A0 (en) | 2011-07-31 |
RU2519372C2 (ru) | 2014-06-10 |
AR073426A1 (es) | 2010-11-03 |
RU2011126195A (ru) | 2013-01-10 |
ZA201102775B (en) | 2012-01-25 |
US20150345082A1 (en) | 2015-12-03 |
US20190358984A1 (en) | 2019-11-28 |
BRPI0921223A2 (pt) | 2016-02-23 |
CN102224294A (zh) | 2011-10-19 |
BRPI0921223A8 (pt) | 2019-02-05 |
BRPI0921223B1 (pt) | 2019-04-30 |
EP2370633B1 (en) | 2014-03-26 |
PL2370633T3 (pl) | 2014-08-29 |
US20130244147A1 (en) | 2013-09-19 |
US20100129553A1 (en) | 2010-05-27 |
JP2015147421A (ja) | 2015-08-20 |
KR101747669B1 (ko) | 2017-06-27 |
EP2370633A1 (en) | 2011-10-05 |
CN102224294B (zh) | 2013-12-25 |
AU2009319368A1 (en) | 2010-06-03 |
CA2744839A1 (en) | 2010-06-03 |
JP6457585B2 (ja) | 2019-01-23 |
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