CN104231243B - 胭脂红着色剂 - Google Patents
胭脂红着色剂 Download PDFInfo
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- CN104231243B CN104231243B CN201410245863.5A CN201410245863A CN104231243B CN 104231243 B CN104231243 B CN 104231243B CN 201410245863 A CN201410245863 A CN 201410245863A CN 104231243 B CN104231243 B CN 104231243B
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- Prior art keywords
- acid
- carmine
- polymer
- polyester
- modified
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Abstract
本公开提供了一种经改性的胭脂红,其可包含诸如聚酯的聚合物或诸如多羧酸的缀合分子。
Description
技术领域
生物基着色剂包含天然来源的着色部分胭脂红。胭脂红基着色剂可用于制备有色聚合物,如聚酯聚合物,从而制得例如红色聚酯聚合物。
背景技术
聚合物通常与着色剂混合,以产生一系列已知的有色塑料、材料等。然而,与聚合物一起使用着色剂存在缺点。例如,颜料可能难以分散于溶剂中,且分散体或悬浮体随后必须可引入聚合反应中,或者必须可分别与聚合物混合并与聚合物反应。染料尽管可溶,但也具有缺点,如差的热稳定性和差的耐光性。
随着对环境和健康的增加的关注,对发现石油基试剂的合适的试剂替代品和与聚合物合成和使用相关的某些着色剂存在兴趣和/或需要。那么,希望提供可生物再生的试剂,如着色剂,其对环境和健康具有降低的不利影响,并具有改进的热稳定性和时间稳定性和耐光性。
发明内容
本公开提供了一种包含经改性的胭脂红的红色/橙色/紫色着色剂(取决于pH),其具有将聚合物着色的用途而无需额外的着色步骤,所述聚合物可用于油墨、塑料、油漆、挤出产品、注塑产品、布料、绳索、调色剂、容器、屏幕、数据存储设备等中。经改性的胭脂红可结合至化合物、聚合物等。
具体实施方式
本公开提供了一种新型生物基着色剂。所述着色剂由天然来源的着色分子部分胭脂红(其也称为绯红色淀、胭脂虫红、天然红4、C.I.75470或E120)组成。天然亮红色颜料为胭脂红酸的铝盐,其由一些介壳虫(如胭脂虫和波兰胭脂虫)产生。
胭脂红(或胭脂虫红)获自雌性昆虫、胭脂虫或雌性胭脂虫,或那些物种的卵。干燥雌性昆虫的壳,然后胭脂红酸在溶剂中提取,并从不可溶材料中分离。澄清溶液随后用含铝化合物(如明矾)或用另一沉淀剂处理,然后与含铝化合物组合以形成胭脂红。胭脂红在酸性介质中(pH3)为橙色,在接近中性的介质中为红色(pH5.5),在约pH7下为紫色。
胭脂红为抵抗随时间的降解的少数天然水溶性着色剂之一。胭脂红为光稳定和热稳定的,并且抗氧化。胭脂红酸为7-α-D-吡喃葡萄糖基-9,10-二氢-3,5,6,8-四羟基-1-甲基-9,10-二氧蒽甲酸。
胭脂红(或胭脂红酸)作为多元醇试剂包括于聚合反应(如聚酯缩聚反应混合物)中,以形成红色聚酯聚合物,所述红色聚酯聚合物可模制、熔融、纺织等成为感兴趣的所需形式。在聚酯反应的情况中,胭脂红可为聚合物主链的一体部分,或者可共价附接至聚合物链上的合适的反应性位点,从而保持红色。可使用具有可与胭脂红反应的合适位点的任何聚合物。
除非另外指出,否则与可通过本领域已知的方法确定的已知度量相关的在说明书和权利要求书中所用的表示量和条件等的所有数字在所有情况下均理解为由术语“约”修饰。“约”意在表示与所述值的变化不超过10%。本文也使用术语“等同”、“类似”、“基本上”、“大体上”、“大约”和“匹配”或它们的语法变型,这些术语具有通常可接受的定义或者至少理解为具有与“约”相同的含义。
如本文所用,“生物基”意指全部或显著部分(例如产品的至少约50重量%,至少约60重量%,至少约70重量%,至少约80重量%,至少90重量%)由生物产品(包括植物、动物和海洋材料)组成的产品。通常,生物基材料为可生物降解的,即大体上或完全可生物降解,大体上意指材料的大于50%,大于60%,大于70%或更多在大约数天、数周、一年或更长,但通常不超过五年内通过生物或环境方式(如细菌、动物、植物等对材料的作用)从初始分子降解成另一形式。
“多元酸”为形成用于调色剂的聚酯聚合物的单体,其包含至少两个反应性酸性基团(如羧酸基团),至少三个酸性基团或更多。二元酸、三元酸等由多元酸体现。因此,二羧酸、三羧酸、“多羧酸”为多元酸的例子,并包含具有两个、三个或更多个反应性羧酸基团或部分的分子。
“多元醇”为形成用于调色剂的聚酯聚合物的单体,其包含至少两个反应性羟基(如醇),至少三个羟基或更多。因此,二醇或二元醇、三醇或三元醇等由多元醇涵盖。
为了本文的目的,聚合物被称为包含用于形成或生成所述聚合物的反应物,尽管一旦引入聚合物中,该反应物可能不再包含相同的分子式。因此,例如,聚酯聚合物通常通过使醇与酸反应而形成。该反应通常涉及在缩合反应中失去水分子。尽管如此,为了本公开的目的,尽管两个邻近的醇和酸反应物共同失去水分子,但所述聚酯被称为包含醇和酸反应物。因此,如果异山梨醇分子与壬二酸反应而形成聚酯,所述聚酯被称为包含壬二酸和异山梨醇。
“胭脂红”为胭脂红酸的铝盐的任意形式(其在大于约4且小于约6.5的略微酸性的pH下包含红色),或者为胭脂红酸的改性形式(其在该pH范围内具有红色)。胭脂红的改性形式或“改性胭脂红”的例子为胭脂红和缀合分子的缀合物,所述缀合分子如羧酸或多羧酸,如琥珀酸、草酸、丙二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、马来酸、富马酸、戊烯二酸、创伤酸、粘康酸、柠檬酸、异柠檬酸、乌头酸、均苯三甲酸、苯六甲酸等。根据设计选择,单个或多个缀合分子可以以各种比例与胭脂红部分混合,如单个胭脂红部分结合至单个缀合部分,胭脂红部分与缀合部分的比例为2:1至约100:1或更大,至1:2至约1:100或更大。而且,根据设计选择,多个分子可以以各种比例与多个胭脂红部分混合,从而形成聚集体或网络。改性胭脂红的其他形式包括聚合物。因此,例如,胭脂红可在酯缩聚反应过程中作为聚合物的单体引入,以产生具有红色的聚酯聚合物,从而获得例如红色/洋红色聚合物。根据设计选择,各种量的胭脂红可在酯化反应中作为多元醇引入。或者,缀合分子包括聚合物,所述聚合物与胭脂红混合,以允许胭脂红加成反应至聚合物。因此,一个或多个胭脂红部分可构成聚合物的一个或多个侧基。根据设计选择,各种数目和量的胭脂红可添加至聚合物。根据设计选择,改性胭脂红可含有胭脂红与缀合分子或单体(基本上任何非胭脂红分子)的任何相对摩尔组合。因此,根据设计选择,胭脂红与非胭脂红分子的比例可为约0.01摩尔%至约99.99摩尔%,至约99.99摩尔%至约0.01摩尔%,以及那些极值之间的所有比例。
包含多元醇单体或组分或者包含对羟基反应性的侧基的任何聚合物可用于与胭脂红反应。本公开将示例聚酯聚合物。
聚酯树脂可例如在酯化反应中合成获得,所述酯化反应涉及包含多元酸的试剂和包含多元醇的另一试剂。在实施方案中,醇试剂包含三个或更多个羟基,在实施例中,包含四个或更多个羟基,或更多。在实施方案中,多元酸包含三个或更多个羧酸基团,在实施例中,包含四个或更多个羧酸基团,或更多。包含三个或更多个官能团的试剂实现、促进或实现且促进聚合物支化和交联。
可用于产生无定形聚酯树脂的多元醇的例子包括1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、戊二醇、己二醇、2,2-二甲基丙二醇、2,2,3-三甲基己二醇、庚二醇、十二烷二醇、1,4-环己烷二甲醇、1,3-环己烷二甲醇、二甲苯二甲醇、环己二醇、二乙二醇、双(2-羟乙基)氧化物、二丙二醇、二丁二醇和它们的组合。多元醇的量可变化,并可以以例如树脂的约40至约60摩尔%,树脂的约42至约55摩尔%,树脂的约45至约53摩尔%的量存在。
可用于产生无定形树脂的多元酸或聚酯的例子包括对苯二甲酸、邻苯二甲酸、间苯二甲酸、富马酸、偏苯三甲酸、富马酸二乙酯、衣康酸二甲酯、顺式-1,4-二乙酰氧基-2-丁烯、富马酸二甲酯、马来酸二乙酯、马来酸、琥珀酸、衣康酸、琥珀酸、环己酸、琥珀酸酐、十二烷基琥珀酸、十二烷基琥珀酸酐、戊二酸、戊二酸酐、己二酸、庚二酸、辛二酸、壬二酸、十二烷二酸、萘二甲酸二甲酯、对苯二甲酸二甲酯、对苯二甲酸二乙酯、间苯二甲酸二甲酯、间苯二甲酸二乙酯、邻苯二甲酸二甲酯、邻苯二甲酸酐、邻苯二甲酸二乙酯、琥珀酸二甲酯、萘二甲酸、二聚体二酸、富马酸二甲酯、马来酸二甲酯、戊二酸二甲酯、己二酸二甲酯、十二烷基琥珀酸二甲酯和它们的组合。
对于形成结晶聚酯树脂,合适的多元醇包括具有约2至约36个碳原子的脂族多元醇,如1,2-乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、2,2-二甲基丙-1,3-二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇等;碱性磺基-脂族二醇,如2-磺基-1,2-乙二醇钠、2-磺基-1,2-乙二醇锂、2-磺基-1,2-乙二醇钾、2-磺基-1,3-丙二醇钠、2-磺基-1,3-丙二醇锂、2-磺基-1,3-丙二醇钾,它们的混合物等,包括它们的结构异构体。
用于制备结晶树脂的多元酸或聚酯试剂的例子包括草酸、琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、富马酸、富马酸二甲酯、衣康酸二甲酯、顺式-1,4-二乙酰氧基-2-丁烯、富马酸二乙酯、马来酸二乙酯、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘-2,6-二甲酸、萘-2,7-二甲酸、环己烷二甲酸、丙二酸、中康酸、它们的聚酯或酸酐;碱性磺基-有机多元酸,如以下的钠盐、锂盐或钾盐:二甲基-5-磺基-间苯二甲酸酯、二烷基-5-磺基-间苯二甲酸酯-4-磺基-1,8-萘二甲酸酐、4-磺基-邻苯二甲酸、二甲基-4-磺基-邻苯二甲酸酯、二烷基-4-磺基-邻苯二甲酸酯、4-磺苯基-3,5-二羰基甲氧基苯、6-磺基-2-萘基-3,5-二羰基甲氧基苯、磺基-对苯二甲酸、二甲基-磺基-对苯二甲酸酯、5-磺基-间苯二甲酸、二烷基-磺基-对苯二甲酸酯、磺基-对羟基苯甲酸、N,N-双(2-羟乙基)-2-氨基乙烷磺酸酯,或它们的混合物。多元酸可选择为例如在实施例中约40至约60摩尔%,约42至约52摩尔%,约45至约50摩尔%的量。任选地,可选择树脂的约0.1至约10摩尔%的量的第二多元酸。
在实施例中,在酯化反应中的多元醇试剂的一部分可根据设计选择包含不同的量的胭脂红,所述胭脂红以不同的量(以包括于酯化反应中的胭脂红和任选的另一多元醇的量计)构成聚酯聚合物的主链。
聚酯聚合物是已知的,如果聚合物包含可与羟基反应的基团(如酸基团,如羧酸基团),则该聚合物可用作缀合分子,并可与胭脂红结合,其中胭脂红共价键合至可与羟基反应的基团。可将不同的量的胭脂红掺入加成反应中,以赋予聚合物红色。
可在聚酯反应中使用的缩合催化剂包括四烷基钛酸酯;二烷基锡氧化物,如二丁基锡氧化物;四烷基锡,如二丁基锡二月桂酸酯;二丁基锡二乙酸酯;二烷基锡氧化物氢氧化物,如丁基锡氧化物氢氧化物;铝烷氧化物;烷基锌;二烷基锌;氧化锌;氧化亚锡;氯化亚锡或它们的组合。在实施例中,这种催化剂可包括宾夕法尼亚州费城的阿科玛公司(ArkemaInc.,Philadelphia,PA)的丁基锡酸(Fascat)和二丁基锡氧化物(Fascat)。
这种催化剂可以以例如约0.01摩尔%至约5摩尔%的量(以反应混合物中的起始多元酸、多元醇或聚酯试剂的量计)使用。
聚合物可为交联的。可交联聚合物可包含例如一个或多个可交联基团(如C=C键),或侧基(pendant group)或侧基(side group)(如羧酸基团)。聚合物可例如通过使用引发剂的自由基聚合而交联。
合适的引发剂包括过氧化物,如有机过氧化物或偶氮化合物。所用的引发剂的量与交联程度成比例,因此与聚合物的凝胶含量成比例。所用的引发剂的量可为例如聚合物的约0.01至约10重量%,约0.1至约5重量%。在交联中,希望消耗基本上全部的引发剂。交联可在高温下进行,因此反应可为迅速的。
可将包含至少三个官能团的一种或多种试剂引入聚合物中或引入分支中,以能够支化、进一步支化和/或交联。例如,在聚酯的情况中,这种多官能单体包括1,2,4-苯-三甲酸、1,2,4-环己烷三甲酸、2,5,7-萘三甲酸、1,2,4-萘三甲酸、1,2,5-己烷三甲酸、1,3-二羧基-2-甲基-2-亚甲基-羧基丙烷、四(亚甲基-羧基)甲烷和1,2,7,8-辛烷四甲酸、它们的酸酐、它们的低级烷基酯等。支化剂可以以约0.01至约10摩尔%,约0.05至约8摩尔%,约0.1至约5摩尔%的量使用。
通常,如本领域已知,多元酸和多元醇试剂任选地与催化剂混合,并在高温(如约180℃或更高,约190℃或更高,约200℃或更高等)下温育(其可绝氧进行),以使酯化能够发生直至平衡,这通常产生水或醇(如甲醇),所述水或醇源于在酯化反应中形成酯键。反应可在真空下进行以促进聚合。产物可通过实施已知方法进行收集,并可再次通过实施已知方法进行干燥以产生颗粒。
因此,胭脂红包含于多元酸/聚酯和多元醇的反应混合物中,并包括任何其他试剂,如催化剂。然后在促进缩合反应发生的条件下温育所述混合物。或者,胭脂红与聚合物混合以使一个或多个胭脂红残基能够加成于聚合物上或加成至聚合物。
胭脂红的多个羟基可实现经改性的胭脂红分子和包含多个胭脂红分子的聚集分子的形成。这种聚集体或经改性的胭脂红分子可用作将胭脂红残基引入分子或组合物中或引入分子或组合物上的试剂。经改性的胭脂红和聚集体为稳定的,并可通过缀合至一个或多个胭脂红部分的分子而具有提高的与其他材料的相容性。经改性的胭脂红和较小的聚集体可为水溶性的,而较大的聚集体可在溶液中形成网络或颗粒。
因此,与羟基反应的分子可用作缀合分子,以形成经改性的胭脂红分子或胭脂红聚集体。缀合分子的例子包括酸、胺等。在实施例中,所述试剂可包含多个可与羟基反应的基团。在实施例中,所述试剂可为获自生物源的试剂,或者为可生物降解的。合适的试剂的例子包括羧酸、二酸等,如氨基酸、乙酸、草酸、苯甲酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、柠檬酸、异柠檬酸、乌头酸、苯六甲酸等。在实施例中,缀合至一个或多个胭脂红部分的分子包括聚合物,如聚酯。通常,反应仅需要将胭脂红和缀合试剂悬浮并混合于合适的缓冲液中,并允许加成反应发生。
感兴趣的红色聚合物可在这种聚合物的任何已知用途中使用,而无需添加红色着色剂以获得最终产品。因此,可使用感兴趣的着色剂制备塑料材料,如片材、容器、线、纱、材料、泡沫、密封件、垫片、耐用塑料、粘合剂、涂料,包括挤出产品(如管、棒和圆柱体)以及注塑产品(如玩具、数据存储设备等),以获得它们的红色形式。
除非另外指出,否则份数和百分数以重量计。
实例1胭脂红聚酯的合成
在250ml圆底烧瓶(RBF)中装入壬二酸(AA,44.7mmol,0.07当量,8.41g)、胭脂红(6.38mmol,0.01当量,3.14g)、琥珀酸(SA,287mmol,0.45当量,33.9g)、异山梨醇(IS,300mmol,0.47当量,43.8g)和丁基(羟基)氧化锡(butyl(hydroxyl)stannanone)催化剂(6.38mmol,0.01当量,1.333g)。烧瓶安装有顶置式搅拌器、加热套、氮气管线、冷凝器和Dean-Stark分水器。聚合在起始于200℃(4小时)至215℃(3小时)的温度范围内进行。水在缩聚过程中形成,并在分水器中收集。当软化点(Ts)达到59.1℃时,从烧瓶中放出聚合物。树脂的Ts通过由FP80中央处理器和FP83滴落池(Dropping Cell)组成的Mettler FP800热分析系统测定。温度程控为以1℃/min增加,直至达到目标Ts。
实例2胭脂红聚酯的合成
在250ml RBF中装入AA(38.3mmol,0.06当量,7.21g)、胭脂红(5.11mmol,0.008当量,2.51g)、SA(295mmol,0.462当量,34.8g)、IS(300mmol,0.47当量,43.8g)和丁基(羟基)氧化锡催化剂(6.38mmol,0.01当量,1.333g)。烧瓶安装有顶置式搅拌器、加热套、氮气管线、冷凝器和Dean-Stark分水器。聚合在起始于205℃(8小时)至215℃(3小时)的温度范围内进行。水在缩聚过程中形成,并在分水器中收集。当Ts达到65.5℃时,从烧瓶中放出聚合物。
实例3胭脂红聚酯的合成
在250ml RBF中装入1,9-壬二醇(400mmol,0.40当量,64.1g)、胭脂红(5.0mmol,0.005当量,2.46g)、SA(495mmol,0.495当量,58.5g)、IS(100mmol,0.10当量,14.61g)和丁基(羟基)氧化锡催化剂(6.20mmol,0.0062当量,1.295g)。烧瓶安装有顶置式搅拌器、加热套、氮气管线、冷凝器和Dean-Stark分水器。聚合在起始于205℃(4小时)至215℃(15小时)的温度范围内进行。水在缩聚过程中形成,并在分水器中收集。当软化点(Ts)达到53.9℃时,从烧瓶中放出聚合物。
实例4胭脂红聚酯的合成
在250ml RBF中装入1,9-壬二醇(278mmol,0.37当量,44.5g)、胭脂红(1.50mmol,0.002当量,0.739g)、SA(375mmol,0.50当量,44.3g)、IS(IS,96mmol,0.128当量,14.03g)和丁基(羟基)氧化锡催化剂(3.75mmol,0.005当量,0.783g)。烧瓶安装有顶置式搅拌器、加热套、氮气管线、冷凝器和Dean-Stark分水器。聚合在起始于210℃(12小时)至215-220℃(10小时)的温度范围内进行。水在缩聚过程中形成,并在分水器中收集。聚合物从烧瓶中放出。
实例5胭脂红聚合物的表征
如下表1显示了胭脂红基聚合物的分析数据。为了比较,也在表中显示由SA(0.415当量)、IS(0.488当量)和AA(0.098当量)制得的对照生物聚合物,以及对照低分子量无定形聚酯树脂和对照高分子量树脂的类似数据。实例1-4的含胭脂红的聚合物的形态/结构通过在聚合物中包含1,9-壬二醇(结晶)或壬二酸(1,9-壬二酸,无定形)而进行控制。实例3和4的聚合物基于熔点显示结晶性质。
表1
如本领域已知的那样,将实例1-4的四个含胭脂红的聚合物作为膜施用至加热的凹版印刷板上,并作为印刷物施用至Xerox Digital Color Elite纸基材上。然后,使用GretagMacbethSpectrolino光谱仪测量印刷样品的光谱特性,CIE L*a*b*与Pantone原色进行比较。聚合物的a*b*值显示红/洋红着色有淡黄色。
实例6胭脂红缀合物的制备
在100ml RBF中装入胭脂红(5摩尔,0.5当量,2.462g)和SA(50mmol,5当量,5.90g)。烧瓶安装有顶置式搅拌器、加热套、氮气管线、冷凝器和Dean-Stark分水器。聚合在起始于178℃的温度范围内进行3小时。水在缩聚过程中形成,并在分水器中收集。所得材料可用作进一步缩聚的大分子单体。将琥珀酸加成至侧羟基在胭脂红分子上提供了更长的侧链,以有助于提供一定的柔性,即柔性间隔基。
Claims (8)
1.一种经改性的胭脂红,其包含聚合物,其中胭脂红部分构成聚合物的侧基。
2.根据权利要求1所述的经改性的胭脂红,其中所述聚合物包括聚酯。
3.根据权利要求1所述的经改性的胭脂红,其包含一种或多种缀合分子。
4.根据权利要求3所述的经改性的胭脂红,其中所述缀合分子包括羧酸或多羧酸。
5.根据权利要求4所述的经改性的胭脂红,其中所述多羧酸包括琥珀酸或壬二酸。
6.根据权利要求2所述的经改性的胭脂红,其中所述聚酯包括琥珀酸、壬二酸和异山梨醇中的一种或多种。
7.一种包含胭脂红部分的聚酯聚合物,其中胭脂红部分构成聚合物的侧基。
8.根据权利要求7所述的聚酯聚合物,其包含琥珀酸、壬二酸或异山梨醇。
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US13/920,164 US10184024B2 (en) | 2013-06-18 | 2013-06-18 | Carmine colorants |
US13/920164 | 2013-06-18 |
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JP (1) | JP2015004061A (zh) |
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CN (1) | CN104231243B (zh) |
CA (1) | CA2852325C (zh) |
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FR3025797B1 (fr) * | 2014-09-12 | 2018-03-02 | Arkema France | Resines polyesters hydroxyles ou carboxyles biosourcees. |
FR3025798B1 (fr) | 2014-09-12 | 2016-09-16 | Arkema France | Procede specifique de preparation de polyesters biosources. |
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CN1649931A (zh) * | 2002-04-30 | 2005-08-03 | 巴斯福股份公司 | 制备高官能度超支化聚酯的方法 |
CN102419522A (zh) * | 2010-09-24 | 2012-04-18 | 富士施乐株式会社 | 黄色色调剂、显影剂、色调剂盒、处理盒、设备和方法 |
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US3278486A (en) * | 1959-02-17 | 1966-10-11 | Scripto Inc | Colored polymeric materials |
JPS5933620B2 (ja) * | 1976-06-01 | 1984-08-16 | ポ−ラ化成工業株式会社 | 顔料の製造法 |
US4636261A (en) * | 1984-10-24 | 1987-01-13 | Heinze Richard F | Dry lake system |
US4804719A (en) * | 1988-02-05 | 1989-02-14 | Eastman Kodak Company | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
US5147673A (en) * | 1989-08-16 | 1992-09-15 | Jose Schul | Colorant based on carminic acid, method of preparation, and method of coloring a foodstuff |
US6818730B2 (en) * | 2002-04-26 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Process to produce polyesters which incorporate isosorbide |
RU2243981C1 (ru) * | 2003-09-03 | 2005-01-10 | Открытое акционерное общество "Лианозовский молочный комбинат" | Комплексное соединение карминовой кислоты, способ его получения, пищевой продукт и напиток, содержащие комплексное соединение карминовой кислоты |
US20060089421A1 (en) * | 2004-10-25 | 2006-04-27 | Sundar Vasudevan | Polymeric colorants having pigment and dye components and corresponding ink compositions |
US8163459B2 (en) * | 2010-03-01 | 2012-04-24 | Xerox Corporation | Bio-based amorphous polyester resins for emulsion aggregation toners |
JP2012073304A (ja) * | 2010-09-28 | 2012-04-12 | Tomoegawa Paper Co Ltd | 電子写真用トナー |
WO2013003616A1 (en) * | 2011-06-30 | 2013-01-03 | E. & J. Gallo Winery | Natural crystalline colorant and process for production |
JP6128579B2 (ja) * | 2011-09-27 | 2017-05-17 | 国立研究開発法人産業技術総合研究所 | ポリエステル樹脂の製造方法 |
US9181389B2 (en) * | 2013-05-20 | 2015-11-10 | Xerox Corporation | Alizarin-based polymer colorants |
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CN1649931A (zh) * | 2002-04-30 | 2005-08-03 | 巴斯福股份公司 | 制备高官能度超支化聚酯的方法 |
CN102419522A (zh) * | 2010-09-24 | 2012-04-18 | 富士施乐株式会社 | 黄色色调剂、显影剂、色调剂盒、处理盒、设备和方法 |
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RU2014124524A (ru) | 2015-12-27 |
KR20140147013A (ko) | 2014-12-29 |
US10184024B2 (en) | 2019-01-22 |
JP2015004061A (ja) | 2015-01-08 |
RU2664931C2 (ru) | 2018-08-23 |
CN104231243A (zh) | 2014-12-24 |
DE102014210818A1 (de) | 2014-12-18 |
US20140371419A1 (en) | 2014-12-18 |
CA2852325C (en) | 2018-08-28 |
CA2852325A1 (en) | 2014-12-18 |
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