CN102015843B - 通过喷雾干燥得到的聚合物包封着色剂 - Google Patents
通过喷雾干燥得到的聚合物包封着色剂 Download PDFInfo
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- CN102015843B CN102015843B CN200980116647.8A CN200980116647A CN102015843B CN 102015843 B CN102015843 B CN 102015843B CN 200980116647 A CN200980116647 A CN 200980116647A CN 102015843 B CN102015843 B CN 102015843B
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Classifications
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Abstract
本发明涉及一种制备聚合物粒子的方法,该聚合物粒子包含有效量的至少一种着色剂、聚合物基质和分布在聚合物基质内的第二粒子。该方法包括下列步骤:A)制备由单体共混物在水相中形成的聚合物乳液并在水相中形成第二粒子;B)向水相中添加有效着色量的至少一种着色剂;C)将着色剂分散或溶解在水相中;和D)使乳液在喷雾干燥装置中脱水。
Description
本发明涉及一种改进的制备聚合物粒子的方法,该聚合物粒子包含有效量的至少一种着色剂,如颜料、染料或色淀。
WO 2005/123009和WO 123796公开了一种制备聚合物粒子的方法,所述聚合物粒子在其聚合物结构内含有至少一种着色剂。这些有色包封的聚合物从油包水型乳液获得。该方法使用大量的烃溶剂和稳定剂。在随后的工序中不得不将烃溶剂从乳液中除去。
本发明的一个目的是提供一种技术上更可行且更方便的方法,该方法用于制备个人护理和/或化妆品组合物。这些组合物包含含包埋(entraped)或包封的着色剂的聚合物粒子,并且当经受不同环境时在更长的时段内保持该着色剂。当着色剂特别是水溶性染料(在这种情况下通常难以永久保持该染料)时,这尤其重要。在化妆品组合物中,如果不永久保持染料,这可损害化妆品在长期使用后的视觉效果。
令人吃惊地发现,喷雾干燥不含烃溶剂的水乳液是一种制备在其聚合物结构内含有至少一种着色剂的聚合物粒子的替代方法。
本发明涉及一种改进的制备聚合物粒子的方法,该聚合物粒子包含有效量的至少一种着色剂、聚合物基质和分散在聚合物基质内的第二粒子,
其中聚合物基质由单体共混物形成,该单体共混物包含为烯属不饱和离子单体的第一单体,和为烯属不饱和疏水性单体的第二单体,并且所述第二单体能形成玻璃化转变温度超过50℃的均聚物,
其中第二粒子包含由烯属不饱和疏水性单体和任选其它单体形成的疏水性聚合物,该烯属不饱和疏水性单体能够形成玻璃化转变温度超过50℃的聚合物,和其中疏水性聚合物与聚合物基质不同,
该方法主要由以下步骤组成:
A)制备由包含第一和第二单体的单体共混物在水相中形成的聚合物乳液,在所述水相中形成第二粒子或将第二粒子与所述水相结合;
B)向所述水相中添加有效着色量的至少一种着色剂;
C)将所述着色剂分散和均化所述水相;和
D)使乳液在喷雾干燥装置中脱水。
本发明另外涉及一种制备个人护理或化妆品组合物的方法,该方法包括将可通过上述方法获得的聚合物粒子进一步加工成个人护理或化妆品组合物。
根据本发明的微粒着色剂共混物具有增强的视觉性能,如更自然的皮肤状外观。此外,基质聚合物在严格配制条件或处理下不破碎,因此在储存和使用期间保持所需的美学效应。
优选用于形成基质聚合物的第一单体以形成抗衡离子的挥发性组分的盐形式存在。在脱水步骤D)期间,盐的挥发性组分蒸发。这意味着蒸发了至少一部分抗衡离子组分。例如,当由单体单元的铵盐形成聚合物基质时,挥发性组分氨将在脱水步骤中蒸发。在蒸馏阶段,基质聚合物于是将转化成其游离酸形式。
用于本发明的粒子包含着色剂。着色剂可选自颜料、染料或色淀。在制备粒子的过程中,特别希望将着色剂溶解或分散在水相中以使它能遍及基质聚合物分布。
如上所述聚合物微粒呈现改进的抗破碎性以及改进的视觉性能。此外,即使在长期使用下聚合物基质也不会导致包埋的着色剂释放。特别希望提供其中着色剂遍及基质聚合物分布和其中基质聚合物对于着色剂不可渗透的粒子。
如果使基质聚合物交联,聚合物基质的刚性能够被进一步增强。这可以通过在本方法中包括交联步骤进行。这可通过在聚合物中包含自交联基团来实现,例如带有羟甲基官能团的单体重复单元。优选通过在水相聚合物中包含交联剂来实现交联。合适的交联剂是与聚合物链上的官能团反应的化合物。例如,当聚合物链含有阴离子基团时,合适的交联剂包括氮丙啶、双环氧化合物、碳二酰胺(carbodiamide)、硅烷或多价金属,例如铝、锌或锆。特别优选的交联剂是碳酸铵锆或氧化锌。另一类特别优选的交联剂包括在聚合物链之间形成共价键的化合物,例如硅烷或双环氧化合物。理想的是,交联过程发生在脱水步骤中。
已发现由能够形成玻璃化转变温度超过50℃,优选大于60或80℃的均聚物的疏水性单体的特殊组合形成的聚合物在对着色剂以及其它活性物不可渗透性方面,显示出相当大的性能改进。疏水性单体是指在水中的溶解度小于5g/100ml水的单体。
聚合物的玻璃化转变温度(Tg)在Kirk-Othmer,Encyclopedia ofChemical Technology,第19卷,第四版,第891页中定义为这样的温度:在该温度以下(1)整个分子的过渡运动和(2)链的40-50个碳原子片段的卷曲和展开都是冻结的。因此,在其Tg以下,聚合物不能显示出流动或橡胶弹性。可使用差示扫描量热法(DSC)测定聚合物的Tg。
通常粒子的平均粒度直径小于约100μm(微米)。优选平均粒度直径在约1-60μm范围内,例如1-40μm,尤其是1-30μm。通过Sympatec HELOS粒度分析仪根据手册中记载的标准步骤,测定平均粒度。
用于制备基质聚合物的单体共混物可含有至少50重量%的疏水性单体,其余由离子单体组成。根据优选实施方案,疏水性单体的存在量为至少60重量%。优选的组成中含有65-90重量%的疏水性聚合物,例如70或75%。
疏水性单体的特定实例包括苯乙烯、(甲基)丙烯酸C1-C4烷基酯如甲基丙烯酸甲酯、丙烯酸甲酯、(甲基)丙烯酸乙酯或(甲基)丙烯酸正丁酯或叔丁酯、甲基丙烯酸苯酯、(甲基)丙烯酸C5-C12环烷基酯如甲基丙烯酸环己酯或甲基丙烯酸异冰片酯。
根据优选的实施方案,Tg应高于60℃或高于80℃。
离子单体可含有阴离子或阳离子基团,或者可为潜在的离子型的,例如酸酐的形式。优选离子单体是烯属不饱和阴离子或潜在的阴离子单体。合适的阴离子或潜在的阴离子单体包括丙烯酸、甲基丙烯酸、乙基丙烯酸、富马酸、马来酸、马来酸酐、衣康酸、衣康酸酐、巴豆酸、乙烯基乙酸、(甲代)烯丙基磺酸、乙烯基磺酸和2-丙烯酰胺基-2-甲基丙烷磺酸。优选的阴离子单体是羧酸或酸酐,如(甲基)丙烯酸。
当离子单体是阴离子型的,例如羧酸或酸酐时,挥发性抗衡离子可以是氨或挥发性胺组分。挥发性胺组分是可在低温至中等温度,例如至多200℃的温度下蒸发的液体。优选,可在减压下在低于100℃的温度下蒸发该挥发性胺。可以游离酸的形式产生聚合物,然后用氢氧化铵或挥发性胺的水溶液中和,该挥发性胺例如乙醇胺、甲醇胺、1-丙醇胺、2-丙醇胺、二甲醇胺或二乙醇胺。或者,可通过使阴离子单体的铵或挥发性胺盐与疏水性单体共聚合来制备该聚合物。
可通过任何合适的聚合方法制备基质聚合物。例如可通过水乳液聚合制备该聚合物,如EP-A-697423或美国专利说明书No.5,070,136所述的方法。然后可通过添加氢氧化铵或挥发性胺的水溶液来中和该聚合物。
在典型的聚合方法中,使疏水性单体和阴离子单体的共混物乳化到含有合适量乳化剂的水相中。乳化剂可为任何市场上可买到的、适于形成水乳液的乳化剂。这些乳化剂往往在水相中比在水不混溶的单体相中更加易溶,因而往往显示出高亲水亲油平衡(HLB)。可通过已知的乳化技术进行单体的乳化,已知的乳化技术包括使单体/水相经受剧烈搅拌或剪切,或者将单体/水相通过筛网或网孔。然后可通过使用合适的引发剂体系,例如UV引发剂或热引发剂来进行聚合。合适的引发聚合的技术将提高单体的水乳液的温度至高于70或80℃,然后添加50-1000ppm过硫酸铵,以单体重量计。
基质聚合物具有至多200,000的分子量(使用标准工业参数,通过GPC测定)。优选地,聚合物具有低于50,000的分子量,例如2,000-20,000。根据一个优选的实施方案,基质聚合物的最优分子量为约6,000-12,000。
特别优选的基质聚合物是苯乙烯与丙烯酸铵的共聚物。更优选地,当该方法采用交联剂时,使用此聚合物,交联剂尤其是碳酸铵锆或氧化锌。
在该方法的可选择变型中,离子单体可为阳离子或潜在的阳离子型的,例如烯属不饱和胺。在本发明的这个形式中,挥发性抗衡离子组分为挥发性酸组分。可以与前述阴离子基质聚合物类似的方式形成基质聚合物,所不同的是用阳离子或潜在的阳离子单体代替阴离子单体。如果以游离胺和疏水性单体的共聚物形式制得聚合物,则通过包括合适的挥发性酸例如乙酸或甲酸将其中和。优选通过挥发性羧酸中和聚合物。
合适的阳离子或潜在的阳离子单体包括(甲基)丙烯酸二烷基氨基烷基酯、二烷基氨基烷基(甲基)丙烯酰胺或烯丙胺及其它烯属不饱和胺及它们的酸加成盐。合适的(甲基)丙烯酸二烷基氨基烷基酯包括丙烯酸二甲基氨基甲酯、甲基丙烯酸二甲基氨基甲酯、丙烯酸2-二甲基氨基乙酯、甲基丙烯酸二甲基氨基乙酯、丙烯酸二乙基氨基乙酯、甲基丙烯酸二乙基氨基乙酯、丙烯酸二甲基氨基丙酯、甲基丙烯酸二甲基氨基丙酯、丙烯酸二乙基氨基丙酯、甲基丙烯酸二乙基氨基丙酯、丙烯酸二甲基氨基丁酯、甲基丙烯酸二甲基氨基丁酯、丙烯酸二乙基氨基丁酯和甲基丙烯酸二乙基氨基丁酯。典型的二烷基氨基烷基(甲基)丙烯酰胺包括二甲基氨基甲基丙烯酰胺、二甲基氨基甲基甲基丙烯酰胺、二甲基氨基乙基丙烯酰胺、二甲基氨基乙基甲基丙烯酰胺、二乙基氨基乙基丙烯酰胺、二乙基氨基乙基甲基丙烯酰胺、二甲基氨基丙基丙烯酰胺、二甲基氨基丙基甲基丙烯酰胺、二乙基氨基丙基丙烯酰胺、二乙基氨基丙基甲基丙烯酰胺、二甲基氨基丁基丙烯酰胺、二甲基氨基丁基甲基丙烯酰胺、二乙基氨基丁基丙烯酰胺和二乙基氨基丁基甲基丙烯酰胺。典型的烯丙胺包括二烯丙基胺和三烯丙基胺。
第二粒子包含已经由烯属不饱和疏水性单体和任选的其它单体形成的疏水性聚合物,该烯属不饱和疏水性单体能够形成玻璃化转变温度超过50℃的均聚物,该疏水性聚合物与基质聚合物不同。烯属不饱和疏水性单体可以是以上关于用于形成基质聚合物的第二单体所定义的任何单体。优选,疏水性单体与用于形成基质聚合物的第二单体相同。所述疏水性单体的特定实例包括苯乙烯、(甲基)丙烯酸甲酯、甲基丙烯酸叔丁酯、甲基丙烯酸苯酯、甲基丙烯酸环己酯和甲基丙烯酸异冰片酯。优选疏水性单体是苯乙烯。
疏水性单体可以是单独聚合的,或者可任选地与一种或多种以上定义的其它疏水性单体聚合。可包括其它单体,它们不是能够形成玻璃化转变温度超过50℃的均聚物的疏水性单体,其它单体例如是疏水性单体,例如丙烯酸或甲基丙烯酸的较长链烷基酯,如丙烯酸2-乙基己酯或丙烯酸硬脂酯。如果包括这类单体,那么它们的存在量应该不超过20重量%,基于用于第二粒子的单体的重量。优选,这些单体的存在量小于10重量%,更优选小于5重量%。
或者,其它单体可为亲水性单体。亲水性单体可为非离子型的,例如丙烯酰胺,或它可为离子型的,例如关于用于形成基质聚合物的第一单体所定义的。这类单体往往以较小比例使用,从而聚合物是疏水性的。当包括这类单体时,它们的存在量应该不超过20重量%,基于用于第二粒子的单体重量。优选,这些单体的存在量小于10重量%,更优选小于5重量%。
特别优选第二粒子包含已完全由一种或多种烯属不饱和疏水性单体形成的疏水性聚合物,所述疏水性单体能够形成玻璃化转变温度超过50℃的均聚物。特别合适的疏水性聚合物是苯乙烯和甲基丙烯酸甲酯的共聚物或苯乙烯的均聚物。苯乙烯与甲基丙烯酸甲酯的聚合物通常包含至少40重量%的苯乙烯和至多60重量%的甲基丙烯酸甲酯。优选,共聚物具有50∶50-95∶5,更优选60∶40-80∶20,特别优选70∶30-75∶25的苯乙烯与甲基丙烯酸甲酯的重量比。
第二粒子具有小于1μm,特别是小于750nm的平均粒度。优选第二粒子具有50-500nm范围的平均粒度。可通过任何常规手段制备第二粒子,如水乳液聚合。优选,该粒子可通过现有技术中记录的任何典型的微乳液聚合方法,例如如EP-A-531005或EP-A-449450中所述的方法,通过含水微乳液聚合制备。
可通过形成包含连续水相(20-80重量%)、包含单体的分散油相(10-30重量%)和表面活性剂和/或稳定剂(10-70重量%)的微乳液来制备第二粒子。通常,表面活性剂和/或稳定剂主要存在于水相中。优选的表面活性剂和/或稳定剂是用于形成聚合物基质的聚合物水溶液。特别优选的表面活性剂/稳定剂是丙烯酸铵与苯乙烯的共聚物,如以上关于基质聚合物所定义的。
可通过合适的引发体系,例如UV引发剂或热引发剂来引起微乳液中单体的聚合。合适的引发聚合的技术例如有提高单体的水乳液的温度至高于70或80℃,然后添加50-1000ppm的过硫酸铵或偶氮化合物如偶氮二异丁腈,以单体的重量计。或者,可使用过氧化物,例如室温固化过氧化物,或光引发剂。可优选在约室温下例如用光引发剂进行聚合。
第二粒子包含具有高达2,000,000分子量(使用标准工业参数,通过GPC测定)的聚合物。优选聚合物具有低于500,000的分子量,例如5,000-300,000。聚合物第二粒子的最优分子量为100,000-200,000。
优选第二粒子具有核壳构造,其中核包含被聚合壳包围的疏水性聚合物。更优选第二粒子包含含疏水性聚合物的核和含基质聚合物的壳。特别优选在疏水性聚合物核周围并且在聚合的过程中形成基质聚合物壳。
根据本发明方法的粒子包含着色剂。它们可另外包含其它活性成分,例如UV吸收剂、UV反射剂、阻燃剂或活性染料示踪材料。
粒子包埋一种或多种着色剂,例如为染料、颜料或色淀。合适的着色剂包括被CTFA和FDA批准用于化妆品中的任何有机或无机颜料或着色剂,如色淀、铁氧化物、二氧化钛、铁硫化物或其它常规用于化妆品配方的颜料。
合适的颜料的实例包括无机颜料如碳黑、D&C Red 7、钙色淀、D&CRed 30、滑石色淀、D&C Red 6、钡色淀、黄褐色氧化铁、黄色氧化铁、褐色氧化铁、滑石、高岭土、云母、云母钛、红色氧化铁、硅酸镁和氧化钛;和有机颜料如Red No.202、Red No.204、Red No.205、Red No.206、Red No.219、Red No.228、Red No.404、Yellow No.205、Yellow No.401、Orange No.401和Blue No.404。翁染料的实例为Red No.226、Blue No.204和Blue No.201。色淀染料的实例包括各种用铝、钙或钡色淀的酸性染料。
在一个实施方案中,着色剂是水溶性染料的水溶液。这类染料可包括FD&C Blue No.11、FD&C Blue No.12、FD&C Green No.13、FD&C RedNo.13、FD&C Red No.140、FD&C Yellow No.15、FD&C Yellow No.16、D&C Blue No.14、D&C Blue No.19;D&C Green No.15、D&C Green No.16、D&C Green No.18、D&C Orange No.14、D&C Orange No.15、D&COrange No.110、D&C Orange No.111、D&C Orange No.117、FD&C RedNo.14、D&C Red No.16、D&C Red No.17、D&C Red No.18、D&C RedNo.19、D&C Red No.117、D&C Red No.119、D&C Red No.121、D&CRed No.122、D&C Red No.127、D&C Red No.128、D&C Red No.130、D&C Red No.131、D&C Red No.134、D&C Red No.139、FD&C Red No.140、D&C Violet No.12、D&C Yellow No.17、Ext.D&C Yellow No.17、D&C Yellow No.18、D&C Yellow No.111、D&C Brown No.11、Ext.D&CViolet No.12、D&C Blue No.16和D&C Yellow No.110。
上述染料是众所周知的、市场上可买到的材料,它们的化学结构例如描述在21C.F.R.Part 74(1988年4月1日修订)和the Cosmetics,Toiletryand Fragrances Association,Inc.出版的the CTFA Cosmetic IngredientHandbook 1988中。
证实的染料可以是水溶性的,或优选其色淀。色淀是通过将可溶性染料沉淀在反应层或吸收层上而制备的有机颜料,其是含颜料组合物的主要部分。大多数色淀源自铝、钡或钙。这些不溶性颜料主要用在化妆品中,其是粉末或者是液体,当希望临时着色时,并不染污皮肤,而油溶性染料往往染污皮肤。色淀与无机色料如氧化铁、氧化锌和二氧化钛一起用于这些产品中。
着色剂还可以是潜在的着色剂物质,例如成色剂,其暴露于合适的触发机制例如热或辐照时显现出颜色。可将这种包埋的成色剂涂布到合适的基底上或结合到合适的基底中,然后处理它以显现颜色。即使成色剂被包埋在聚合物粒子内,它仍可被活化。
下表列出了被批准用于食品、药物和/或化妆品的目前可用的颜料和着色剂。本文使用的所选着色剂优选选自下列例举项。
表1-被证实可用于食品、药物、化妆品的染料(FDC颜色)
FD&C Blue No.1 | FD&C Green No.3 | FD&C Red No.4 |
FD&C Red No.40 | FD&C Yellow No.5 | FD&C Yellow No.6 |
表2-被证实可用于局部施涂的药物和化妆品的染料
Ext.DC Violet#2 | Ext.D&C Yellow No.7 | Ext.D&C Violet No.2 |
D&C Brown No.1 | FD&C Red No.4 | D&C Red No.17 |
D&C Red No.31 | D&C Red No.34 | D&C red No.39 |
D&C Violet No.2 | D&C Blue No.4 | D&C Green No.6 |
D&C Green No.8 | D&C Yellow No.7 | D&C Yellow No.8 |
D&C Yellow No.11 | D&C Orange No.4 | D&C Orange No.10 |
D&C Orange No.11 |
表3-被证实仅可用于药物和食品的染料
D&C Blue No.4 | D&C Brown No.1 | D&C green No.5 |
D&C Green No.6 | D&C Green No.8 | D&C Orange No.4 |
D&C Orange No.5 | D&C Orange No.10 | D&C Orange No.11 |
D&C Red No.6 | D&C Red No.7 | D&C Red No.17 |
D&C Red No.21 | D&C Red No.22 | D&C Red No.27 |
D&C Red No.28 | D&C Red No.30 | D&C Red No.31 |
D&C Red No.33 | D&C Red No.34 | D&C Red No.36 |
D&C Violet No.2 | D&C Yellow No.7 | D&C Yellow No.8 |
D&C Yellow No.10 | D&C Yellow No.11 |
一些着色添加剂不需要证明并且被永久列为化妆品用途,包括铝粉、胭脂树橙、氯氧化铋、青铜粉、焦糖、胭脂红、β-胡萝卜素、氢氧化铬绿、氧化铬绿铜(金属粉末)、二羟丙酮、EDTA二钠-铜、亚铁氰化铁铵、亚铁氰化铁、鸟嘌呤(珠光粉)、愈创烯(甘菊环)、铁氧化物、发光硫化锌、锰紫、云母、叶蜡石、银(用于使指甲上光剂着色)、二氧化钛、群青(蓝、绿、粉红、红&紫)和氧化锌。
随后的脱水步骤可通过任何方便的手段实现。通常,这需要高温,例如150℃或更高的温度。虽然可使用高得多的温度例如高达250℃,但通常优选使用低于220℃的温度。可通过WO 97/34945中所述的喷雾干燥法实现脱水。
脱水步骤从基质聚合物的水溶液中除去水以及挥发性抗衡离子组分,得到在水中不溶和不溶胀的干聚合物基质,其中含有遍及聚合物基质分布的着色剂。
通过喷雾干燥法获得聚合物粒子,其中至少90重量%的粒子尺寸小于250μm,优选100μm。根据优选的实施方案,至少90%微粒的粒度小于50μm。优选包封的着色剂微球的平均直径尺寸为0.1-50μm,例如1-40μm和尤其是1-30μm。
优选的微粒至少90%的尺寸范围为50-250μm。
通过使用常规喷雾干燥器使如上所述水乳液经受常规喷雾干燥条件,通过合适选择喷雾干燥孔、泵送通过孔的速率、干燥(温度和干燥器)速率喷雾干燥材料的尺寸,以已知的方式控制粒度,可生产所需粒度的微粒。
优选包封的着色剂微球的平均直径为0.1-60μm,例如1-40μm,尤其是1-30μm。
根据预定用途,优选的平均直径将改变。例如,液体的面部化妆品配方包含至少两种包封的着色剂并且优选的粒度为10-30μm。另外的实施方案可以是唇膏配方,其包含至少两种包封的着色剂,着色剂的优选粒度为1-10μm。
在应用时,施涂个人护理或化妆品配方组合物产生所需的效果,所述组合物包含通过本发明方法获得的(微)包封着色剂。值得注意地,含有至少两种具有独特且不同的颜色的微包封着色剂的共混物,特别是超过一种原色的共混物的组合物是产生自然、肤色质地效果的有效方法。原色意思是指红色、黄色和蓝色。该包封着色剂的另外有利特征是消除非包封着色剂常常遇到的碾磨或研磨。
个人护理或化妆品组合物以组合物的总重计包含0.1-70重量%,例如1-50重量%,尤其是5-35重量%的至少1种,优选2种通过本发明方法获得的包封着色剂,以及化妆品可用的载体或助剂。尽管水是化妆品可接受的,并且大多数情况下会存在水,术语“化妆品可用的载体或助剂”用来指至少一种除水以外的通常用于个人护理或化妆品组合物的物质。
可将个人护理或化妆品制剂配制为油包水型或水包油型乳液,配制为离子或非离子两亲性脂质的有泡分散体,配制为凝胶,或配制为固体条状物。优选化妆品制剂为液体形式。
作为油包水型或水包油型乳液,个人护理或化妆品制剂优选含有5-50%的油相,5-20%的乳化剂和30-90%的水。油相可含有任何适用于化妆品配方的油,例如一种或多种烃油、蜡、天然油、硅油、脂肪酸酯或脂肪醇。
化妆品液体可包括较少量,例如至多10重量%的一元醇或多元醇如乙醇、异丙醇、丙二醇、己二醇、丙三醇或山梨醇。
化妆品配方可包含在多种化妆品制剂中。尤其是下列制剂,例如考虑:
-皮肤护理制剂,例如皮肤乳液,多重乳液或美肤油和爽身粉;
-化妆品个人护理制剂,例如以唇膏、润唇膏、眼影膏、液体化妆品、日霜或粉形式的面部化妆品,面部乳液,霜和粉(疏松或压制的);和
-防晒制剂,如晒黑乳液、霜和油,防晒乳和预晒剂。
下列实施例说明本发明,但不限制其范围:
实施例
粒度分析
使用装有Quixcel分散体系的Sympatec HELOS粒度分析仪测定聚合物粒子的平均粒度。设备购自Sympatec GmbH。
实施例1
1.1制备微乳液聚合物
向装有机械搅拌器、冷凝器、氮气进口、温度探针和供料口的1升树脂罐中放入154.85g水和483.9g低分子量苯乙烯丙烯酸共聚物(65/35重量%单体比,分子量6000)的铵盐的32%溶液。将内容物加热到85℃并用氮气脱气30分钟。通过混合245.0g苯乙烯与105.0g甲基丙烯酸甲酯制备单体相。通过将1.97g过硫酸铵溶解在63.7g水中制备引发剂供料。当反应器达到温度并脱气时,向反应器中添加0.66g过硫酸铵。在2分钟后,开始单体和引发剂供料,分别适当地为3和4小时的供料。在整个供料期间保持反应器内容物在85℃。完成供料后,将反应器内容物在85℃小保持另外1小时,然后将其冷却到25℃。所形成的含水产物是pH 8.3的微乳液聚合物,并且Brookfield RVT粘度为700cPs。该46%聚合物微乳液含有32重量%的苯乙烯-甲基丙烯酸甲酯共聚物(70/30重量%单体比,分子量200,000)微乳液,该微乳液被14重量%的苯乙烯-丙烯酸(65/35重量%单体比,分子量6000)稳定化。苯乙烯-甲基丙烯酸甲酯共聚物的分散胶乳聚合物的平均粒度为195nm。
1.2该实施例说明含有10重量%黄色颜料的黄色聚合物粒子的制备。
通过用100.0g去离子水稀释155.4g根据实施例1.1制备的46%聚合物微乳液,接着添加1.0g消泡剂Burst 5470(购自Ciba)制备含水供料。将稀释的混合物放在顶部匀浆器(Silverson L4R)下,然后在高剪切混合下添加10.0g Yellow#5Al色淀粉末(购自Kingfisher)和20.0g氧化锌(购自NorkemChemicals)。使所形成的着色的混合物均匀化总计15分钟的时间以在含水微乳液聚合物中形成均匀平滑的颜料分散体。
使用实验室喷雾干燥器(Buchi B191型)以3ml/min的供料速度,在180℃的进口温度下将该分散体喷雾干燥。最终产物是自由流动的黄色微珠,其具有25μm的平均粒度直径。基质聚合物是氧化锌交联的苯乙烯-丙烯酸共聚物,其中大约200纳米尺寸的苯乙烯-甲基丙烯酸甲酯的第二聚合物粒子遍及基质分布。
实施例2
用和实施例1描述的相同方法制备红色微珠,不同的是使用20.0g Red#36颜料(购自Ciba)代替Yellow#5Al色淀粉末。
实施例3
用和实施例1描述的相同方法制备蓝色微珠,不同的是使用20.0g BlueAl色淀(购自Kingfisher)代替Yellow#5Al色淀粉末。
实施例4
该实施例证明了该方法在中间工厂规模喷雾干燥器上的实用性。
通过将309.2kg具有与实施例1所述相同组成的46%的聚合物微乳液与129.2kg水和2.0kg Burst 5470消泡剂混合,制备稀释的聚合物溶液。向该稀释的聚合物溶液中添加19.9kg FDC yellow 5Al色淀和39.7kg氧化锌。将所形成的混合物放置在高剪切混合器(Drais溶解器)下并混合30分钟以形成黄色的水分散体。装有2个双物质喷嘴的中间工厂喷雾干燥器DT3用于干燥所述黄色的分散体。在5巴空气压力和110℃出口温度下,以200kg/h的速率,泵送水分散体。喷雾干燥含水的供料以获得黄色的粉末产品,其具有20μm的平均微珠粒度,通过卡尔费希尔(Karl Fischer)法测量的含水量为2.3%。
Claims (10)
1.一种制备聚合物粒子的方法,该聚合物粒子包含有效量的至少一种着色剂、聚合物基质和分布在聚合物基质内的第二粒子,
其中聚合物基质由单体共混物形成,该单体共混物包含为烯属不饱和离子单体的第一单体,和为烯属不饱和疏水性单体的第二单体,并且所述第二单体能形成玻璃化转变温度超过50℃的均聚物,
其中第二粒子包含由烯属不饱和疏水性单体和任选其它单体形成的疏水性聚合物,所述烯属不饱和疏水性单体能够形成玻璃化转变温度超过50℃的聚合物,其中所述疏水性聚合物与所述聚合物基质不同,
该方法主要由以下步骤组成:
A)制备由包含所述第一和第二单体的单体共混物在水相中形成的聚合物乳液,在所述水相中形成第二粒子或将第二粒子与所述水相结合;
B)向所述水相中添加有效着色量的至少一种着色剂;
c)将所述着色剂分散或溶解在所述水相中;和
D)使乳液在喷雾干燥装置中脱水。
2.根据权利要求1的方法,其中聚合物基质由分子量为2,000-20,000的低分子量苯乙烯丙烯酸共聚物的铵盐形成。
3.根据权利要求1的方法,其中第二粒子由苯乙烯-甲基丙烯酸甲酯共聚物形成。
4.根据权利要求1的方法,其包括分散着色剂,所述着色剂选自至少一种选自颜料、染料或色淀的着色剂。
5.根据权利要求1的方法,其主要由以下步骤组成:
A)制备分子量为2,000-20,000的低分子量苯乙烯丙烯酸共聚物的铵盐的乳液,在水相中从苯乙烯-甲基丙烯酸甲酯共聚物形成第二粒子;
B)向水相中添加有效着色量的至少一种着色剂;
c)将着色剂分散或溶解在水相中;和
D)使乳液在喷雾干燥装置中脱水。
6.根据权利要求1的方法,其中聚合物粒子具有小于100μm的平均粒度。
7.根据权利要求1的方法,其中聚合物粒子具有小于50μm的平均粒度。
8.根据权利要求1的方法,其中第二粒子具有小于750nm的平均粒度。
9.根据权利要求1的方法,其中将两种不同的着色剂分散在水相中。
10.一种制备个人护理或化妆品组合物的方法,该方法包括将通过根据权利要求1-9中任一项的方法获得的聚合物粒子进一步加工成个人护理或化妆品组合物。
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US9349604B2 (en) * | 2013-10-20 | 2016-05-24 | Tokyo Electron Limited | Use of topography to direct assembly of block copolymers in grapho-epitaxial applications |
US9793137B2 (en) | 2013-10-20 | 2017-10-17 | Tokyo Electron Limited | Use of grapho-epitaxial directed self-assembly applications to precisely cut logic lines |
US9947597B2 (en) | 2016-03-31 | 2018-04-17 | Tokyo Electron Limited | Defectivity metrology during DSA patterning |
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