CN119072297A - 微胶囊和方法 - Google Patents
微胶囊和方法 Download PDFInfo
- Publication number
- CN119072297A CN119072297A CN202380035941.6A CN202380035941A CN119072297A CN 119072297 A CN119072297 A CN 119072297A CN 202380035941 A CN202380035941 A CN 202380035941A CN 119072297 A CN119072297 A CN 119072297A
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- CN
- China
- Prior art keywords
- polyquaternium
- microcapsule
- gum
- microcapsules
- protein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
本发明涉及一种微胶囊,其中所述微胶囊具有核心和壳;所述核心包含选自香料的核心材料;所述壳包含植物蛋白和多糖,其中所述多糖选自:果胶、天然或化学修饰纤维素、黄原胶、魔芋胶、木葡聚糖、瓜尔胶、他拉胶、刺槐豆胶、菊粉、凝胶多糖胶、定优胶、藻酸盐、结冷胶和角叉菜胶;本发明还涉及产生本发明微胶囊的方法,其中所述方法不涉及化学共价交联。
Description
技术领域
本发明涉及微胶囊及产生所述微胶囊的方法。
背景技术
微胶囊用于各种应用中以将活性材料递送至基材。已知微胶囊提供各种益处,例如延迟活性物质的释放或保护活性物质不受各种组合物中的其它成分的影响。常规微胶囊通常具有由合成聚合物如三聚氰胺甲醛聚合物或聚丙烯酸酯聚合物形成的微胶囊壁。
WO 2020/131879A1公开了在壳中具有共价交联的多异氰酸酯的豌豆蛋白微胶囊。
仍然需要改进的微胶囊,特别是需要改进的用微胶囊处理的表面的感觉。
发明内容
已经发现用本发明的微胶囊处理的表面对消费者具有改善的感觉。
因此,在本发明的第一方面,提供了一种微胶囊,其中所述微胶囊具有核心和壳;所述核心包含选自香料的核心材料;所述壳包含植物蛋白和多糖,其中所述多糖选自:果胶、天然或化学改性纤维素、黄原胶、魔芋胶、木葡聚糖、瓜尔胶、塔拉胶、刺槐豆胶、菊粉、凝胶多糖胶、定优胶、藻酸盐、结冷胶和角叉菜胶。
优选地,微胶囊是可生物降解的。
优选地,微胶囊包封可生物降解的香料。
优选地,微胶囊的壳中使用的蛋白质选自豌豆蛋白。
优选地,微胶囊的壳中使用的多糖选自藻酸盐、结冷胶、角叉菜胶,更优选地,多糖是藻酸盐。
优选地,微胶囊包含1至80重量%,优选2至70重量%的壳材料。
优选地,微胶囊还包含附着于所述微胶囊的壳的沉积助剂。
在第二方面,本发明提供了制备根据本发明第一方面的微胶囊的方法,其中该方法不涉及化学共价交联。
优选地,该方法选自离子交联、带电聚合物交联或氢键键合,更优选地离子交联。
具体实施方式
通过阅读以下详细描述和所附权利要求,这些和其它方面、特征和优点对于本领域技术人员将变得显而易见。为了避免疑问,本发明的一个方面的任何特征可用于本发明的任何其它方面。词语“包含”旨在表示“包括”,但不一定是“由…组成”或“由…构成”。换句话说,所列出的步骤或选项不需要是穷举的。
应注意,以下描述中给出的实例旨在阐明本发明,而不旨在将本发明限于这些实例本身。类似地,除非另有说明,所有百分比均为重量/重量百分比。除了在操作实施例和对比例中,或另外明确指出的地方,本说明书中表示材料的量或反应条件、材料的物理性质和/或用途的所有数字应理解为由词语“约”修饰。以“从x到y”的形式表示的数值范围应理解为包括x和y。当对于特定特征以“从x到y”的格式描述多个优选范围时,应理解也涵盖组合不同端点的所有范围。
微胶囊组合物在本文中应理解为是指包含加入到进一步组合物中的微胶囊的组合物。微胶囊组合物可以仅包含微胶囊或可以是包含微胶囊的浆料的形式。
微胶囊在本文中应理解为意指微胶囊(壁和核心),即不含溶剂或浆料。
微胶囊可以简单地作为微胶囊提供,但优选以在浆料中包含微胶囊的微胶囊组合物提供。微胶囊包含微胶囊核心和包封核心的微胶囊壁,所述微胶囊核心包含选自香料和/或有益剂的核心材料。微胶囊壁包含壁聚合物及任选但优选地交联剂。通常,微胶囊包含10重量%至98重量%的核心材料,1重量%至40重量%的包含蛋白质和多糖的壳材料,以及任选地0.2重量%至6重量%的交联剂。
微胶囊可通过任何合适的方法制备,包括本文所述的那些示例性方法。
如本文所用,术语“香料”和“芳香剂”可互换使用以指代相同材料。
生物降解性
其中本文所用的材料被称为可生物降解的,意指它们满足如OECD中定义的生物降解性的要求。具体地,根据OECD标准301F测试材料的生物降解性。
微胶囊
微胶囊可被认为是包封活性物质的胶囊。本文所用的微胶囊具有选自香料和/或有益剂的核心材料,以及包含蛋白质和多糖的壳。
微胶囊壳材料
微胶囊壳包含植物蛋白和多糖聚合物。可通过各种方法处理蛋白质和多糖以提供衍生物,包括但不限于水解、缩合、功能化如乙氧基化、交联等。微胶囊壁材料优选在水性溶液中。微胶囊壳优选包含按微胶囊壳的重量计20重量%至100重量%,更优选30重量%至98重量%,更优选35重量%至95重量%,并且最优选65重量%至90重量%的蛋白质和多糖。
如本领域中常规的,“多肽”或“蛋白质”是由在链中键合在一起形成蛋白质分子的部分(或全部)的氨基酸残基组成的线性有机聚合物。本文所用的“多肽”或“蛋白质”是指天然多肽、,多肽衍生物和/或修饰的多肽。多肽可以表现出1,000Da至40,000,000Da,优选大于10,000Da,更优选100,000Da,最优选大于1,000,000Da并且优选小于3,000,000Da的平均分子量。
适用于本发明的蛋白质包括植物蛋白。
合适的优选蛋白质包括选自鹰嘴豆、豌豆蛋白、马铃薯蛋白、糙米蛋白、白米蛋白、小麦蛋白、大麦蛋白、南瓜籽蛋白、燕麦蛋白、杏仁蛋白及其组合的蛋白质。这包括上述蛋白质的衍生物。
优选的蛋白质种类是植物蛋白。植物蛋白是在各种植物组织中积累的蛋白质。优选的植物蛋白可分为两类:种子或谷物蛋白和植物的蛋白。种子/谷物蛋白是在种子/谷物发育的后期在种子/谷物中积累至高水平的一组蛋白质,而植物的蛋白是在营养组织如叶、茎和(取决于植物物种)块茎中积累的蛋白质。
种子/谷物/豆类贮存蛋白的优选实例是来自以下的蛋白质:大豆、羽扇豆、豌豆、鹰嘴豆、苜蓿、蚕豆、兵豆和扁豆;来自油料种子植物如油菜、棉籽和向日葵;来自谷物如小麦、玉米、大麦、麦芽、燕麦、黑麦和水稻(例如,糙米蛋白),或其组合。
植物蛋白的优选实例是蛋白质形式:马铃薯或甘薯块茎。
术语植物蛋白旨在包括植物蛋白质分离物、植物蛋白质浓缩物或其组合。植物蛋白质分离物和浓缩物通常理解为由几种蛋白质组成。例如,豌豆蛋白分离物和浓缩物可以包括豆球蛋白、豌豆球蛋白和convicilin蛋白。类似地,糙米蛋白分离物可以包括白蛋白、球蛋白和谷蛋白。术语“植物蛋白”还旨在包括部分或完全修饰或变性的植物贮藏蛋白。单独的多肽(例如,豆球蛋白、豌豆球蛋白、convicilin、白蛋白、球蛋白或谷蛋白)也可用于制备本发明的微胶囊。
天然蛋白质可能是优选的。然而,该方法可包括通过pH调节、加热或向水包油乳液中加入离液剂或在加入水包油乳液之前向蛋白质中加入离液剂使蛋白质变性的步骤。
变性是其中通过应用变性条件使蛋白质(多肽)失去以其天然状态存在的四级结构、三级结构和二级结构的过程。在变性过程中,蛋白质通过解折叠改变其构象结构,从而使胺和羟基可用于交联以形成微胶囊壁。蛋白质变性的示例性条件包括但不限于辐射、暴露于热或冷、用酸或碱改变pH、暴露于变性剂如洗涤剂、无机盐、有机溶剂(例如,醇、乙酸乙酯和氯仿)、脲或其它离液剂,或机械应力(包括剪切)。示例性离液剂为胍盐(例如,盐酸胍和碳酸胍)、尿素、聚山梨醇酯、苯甲酸钠、香草醛、邻甲酚、苯酚、丙醇、甲酰胺、乙醇、果糖、硫酸铵、氯化铵、硝酸铵、磷酸铵、硫酸钾、氯化钾、碘化钾、硝酸钾、磷酸钾、硫酸钠、氯化钠、溴化钠、硝酸钠、磷酸钠、硫氰酸胍、木糖、甘油、苯甲醇、乙酸乙酯、Triton X-100、醋酸乙酯、鲸蜡基三甲基卤化铵、丙酮、十二烷基硫酸钠(SDS)、氢氯酸、硫酸、聚乙二醇、戊二醛及其组合。
可以使用任何量的离液剂。可能优选的是用离液剂使蛋白质变性,使得微胶囊制备中使用的20重量%至100重量%,优选40重量%至100重量%,更优选60重量%至100重量%,最优选90重量%至100重量%的蛋白质变性。
微胶囊中使用的蛋白质也可以被衍生化或修饰(例如,衍生化或化学修饰)。例如,可通过共价连接糖、脂质、辅因子、肽或其它化学基团(包括磷酸根、乙酸根、甲基和其它天然或非天然分子)来修饰蛋白质。
最优选的植物蛋白是豌豆蛋白。
多糖是包含多个单糖单元的一类碳水化合物。本文所用的“多糖”是指天然多糖、多糖衍生物和/或改性多糖。
所用的多糖选自果胶(例如各种来源如柑橘、甜菜或苹果)、纤维素(天然或化学修饰的,如羟乙基纤维素)、黄原胶、魔芋胶、木葡聚糖、瓜尔胶、塔拉胶、刺槐豆胶、菊粉、凝胶多糖胶、定优胶、藻酸盐、结冷胶和角叉菜胶。
特别优选的多糖包括:藻酸盐、结冷胶和角叉菜胶。
微胶囊中使用的多糖也可以被衍生化或修饰(例如,衍生化或化学修饰)。例如,可通过共价连接糖、脂质、辅因子、肽或其它化学基团(包括磷酸根、乙酸根、甲基和其它天然或非天然分子)来修饰蛋白质。合适的多糖衍生物的实例包括:羟乙酸淀粉、羧甲基淀粉、羟烷基纤维素和交联改性纤维素。
微胶囊优选包含按微胶囊的重量计0.1重量%至90重量%的微胶囊壳,优选1重量%至80重量%,更优选2重量%至70重量%的微胶囊壳。优选地,壳材料的该含量仅由按微胶囊重量计的蛋白质和多糖的含量计算。
本文所述的微胶囊壁聚合物优选是交联的,然而制备微胶囊的方法不涉及化学共价交联。
优选地,该方法选自离子交联、带电聚合物交联或氢键键合,更优选离子交联。
合适的交联方法包括:离子交联、带电聚合物交联或氢键键合,以及微胶囊壁聚合物结构内的内部交联(包括凝聚层的形成)。优选地,该方法涉及离子交联,例如盐桥交联。当使用交联剂如离子交联剂时,交联剂优选以微胶囊重量的0.1重量%-10重量%的水平存在。
适用于本发明的交联剂是离子交联剂。离子交联剂是能够与蛋白质或多糖聚合物的官能团形成盐桥的多价离子。合适的离子交联剂包括钙、铜、铝、镁、锶、钡、锌、锡、有机阳离子、聚(氨基酸)、聚(乙烯亚胺)、聚(乙烯基胺)、聚(烯丙基胺)和多糖,且多价阴离子选自二羧酸、硫酸根离子、碳酸根离子、聚(丙烯酸)、聚(甲基丙烯酸)、丙烯酸或甲基丙烯酸的共聚物、磺化的聚(苯乙烯)和具有羧酸基团的聚(苯乙烯)及其混合物。特别优选的是钙盐、镁盐、钠盐、钾盐、锶盐、钡盐、锌盐。
内部交联是微胶囊壁聚合物之间的交联,而不使用交联剂。内部交联可以是与相同的聚合物(即,具有正电荷和负电荷两者的聚合物)交联或在形成微胶囊壁的两种不同聚合物之间交联。当使用两种具有相反电荷的不同聚合物时,这被称为通过凝聚形成的凝聚层。
优选地,凝聚层在具有一种电荷的第一蛋白质或多糖和具有相反电荷的第二蛋白质或多糖之间形成。具有正电荷的聚合物和具有负电荷的聚合物之间的比率优选为10/0.1至0.1/10,更优选为10/1至1/10,最优选为6/1至1/6。
具有正电荷的蛋白质的实例可以是明胶蛋白,且具有负电荷的蛋白质或多糖可以选自阿拉伯树胶、黄原胶、藻酸盐、果胶酸盐、角叉菜胶、聚丙烯酸和甲基丙烯酸、黄原胶和植物胶和/或其混合物。
内部交联的,即在微胶囊壁聚合物内的正和负单体之间具有静电相互作用的微胶囊可以使用如上所述的盐桥进一步交联或“硬化”。
微胶囊可以任选地包含进一步的交联剂。进一步的交联剂可以选自转谷氨酰胺酶、过氧化物酶、次生植物物质(选自多酚,特别是单宁、没食子酸、阿魏酸、橙皮苷、肉桂醛、香草醛、香芹酚)以及两种或更多种前述交联剂的混合物。
微胶囊核心材料
核心材料选自香料。
核心也可称为内相。微胶囊的核心包含活性材料并且任选地还包含如上所述的溶剂和/或交联剂。核心优选是非水性的。
微胶囊将香料包封在核心中(即核心材料全部或部分是香料)。优选地,香料是可生物降解的,其中根据OECD标准301F测试香料的生物降解性。
内部非水相可优选包含20-80重量%,优选25-75重量%,甚至更优选33-50重量%的待包封活性物质,和优选0.1-5重量%,优选0.15-3.5重量%,甚至更优选0.5-2.5重量%的交联剂和其余的组合物溶剂。
有益剂可溶解在溶剂中。合适的溶剂的实例包括植物油、甘油酯、脂肪酸和支链醇的酯、烃等。具体实例包括:邻苯二甲酸二乙酯、肉豆蔻酸异丙酯、(松香树脂,可得自Eastman)、苯甲酸苄酯、柠檬酸乙酯、柠檬烯或其它萜烯、三醋精或异链烷烃,优选地苯甲酸苄酯、柠檬烯或其它萜烯、异链烷烃或其组合。优选地,如果存在,溶剂为活性材料的0至30重量%,更优选活性材料的0至20重量%,最优选活性材料的0至10重量%。
最优选地微胶囊核心材料包含香料。香料组分是本领域公知的。有用的香料组分可包括天然和合成来源的材料。它们包括单一化合物和混合物。此类组分的具体实例可见于当前文献中,例如Fenaroli's Handbook of Flavor Ingredients,1975,CRC Press;Synthetic Food Adjuncts,1947,M.B.Jacobs,Van Nostrand编辑;或Perfume and FlavorChemicals by S.Arctander 1969,Montclair,N.J.(USA)。这些物质是加香、调味和/或加香消费品领域的技术人员所熟知的。
特别优选的香料组分是释香香料组分和直接(substantive)香料组分。释香香料组分由小于250℃的沸点和大于2.5的LogP定义。优选地包封的香料组合物包含至少20重量%的释香香料成分,更优选至少30重量%,最优选至少40重量%的释香香料成分。直接香料组分由大于250℃的沸点和大于2.5的LogP定义。优选地包封的香料组合物包含至少10重量%的直接香料成分,更优选至少20重量%,最优选至少30重量%的直接香料成分。在标准压力(760mmHg)下测量沸点。优选地香料组合物将包含释香和直接香料组分的混合物。香料组合物可包含其它香料组分。
多种香料组分存在于微胶囊中是常见的。在用于本发明的组合物中,设想在微胶囊中存在三种或更多种不同的香料组分,优选四种或更多种不同的香料组分,更优选五种或更多种不同的香料组分,最优选六种或更多种不同的香料组分。可应用最多300种香料组分。
优选地,包封的活性物质的量为微胶囊重量的5重量%至95重量%,优选10重量%至90重量%,更优选15重量%至85重量%,并且最优选20重量%至80重量%。
沉积助剂
优选地,微胶囊还包含一种或多种附着于微胶囊壳的沉积助剂。
如果使用,则优选地沉积助剂选自三甲基铵、甲基丙烯酰胺丙基三甲基铵、丙烯酰胺丙基三甲基铵、丙烯酰胺、丙烯酸、二甲基铵、木糖(xlylose)、半乳糖、羟丙基化葡萄糖、壳聚糖、羟乙基化葡萄糖、羟甲基化葡萄糖、乙烯基胺、乙烯亚胺、功能化支化聚乙烯亚胺、乙烯基甲酰胺、乙烯基吡咯烷酮、己内酯、邻苯二酚、乙烯基醇、脱乙酰壳多糖、聚季铵盐-4、聚季铵盐-5、聚季铵盐-6、聚季铵盐-7、聚季铵盐-10、聚季铵盐-11、聚季铵盐-16、聚季铵盐-22、聚季铵盐-24、聚季铵盐-28、聚季铵盐-37、聚季铵盐-39、聚季铵盐-44、聚季铵盐-46、聚季铵盐-47、聚季铵盐-53、聚季铵盐-55、聚季铵盐-67、聚季铵盐-68、聚季铵盐-69、聚季铵盐-73、聚季铵盐-74、聚季铵盐-77、聚季铵盐-78、聚季铵盐-79、聚季铵盐-80、聚季铵盐-81、聚季铵盐-82、聚季铵盐-86、聚季铵盐-88、聚季铵盐-101、聚季铵盐-79水解角蛋白、聚乙烯基胺、聚乙烯亚胺、乙烯基胺和乙烯基甲酰胺的共聚物、丙烯酰胺与3-甲基丙烯酰基氨基丙基三甲基铵的共聚物、3-丙烯酰胺丙基三甲基铵聚合物或其共聚物、二烯丙基二甲基氯化铵聚合物及其共聚物、具有由羟丙基三甲基铵功能化的糖单元的多糖、乙基三甲基氯化铵甲基丙烯酸盐和水解小麦蛋白共聚物、烷基-甲基铵羟丙基水解蛋白及其组合。
更优选地,使用的任何沉积助剂根据OECD标准301F是可生物降解的。
微胶囊组合物
如本文所用,术语“微胶囊”是指优选具有0.1至1000微米,优选0.1至300微米,更优选1至200微米,例如20至200微米的中位粒径d(50)的胶囊。
中位粒径d(50)通过激光衍射分析测定,例如通过使用来自Malvern的Horiba LA940或Mastersizer 3000采用“米氏散射理论”评估。中位值定义为其中群体的一半位于该点之上,且一半位于该点之下的值。对于粒度分布,中位值称为“d(50)”或“D50”。
微胶囊可带正电或带负电,其ζ电位优选为-200mV至+200mV,更优选25mV至200mV,最优选40mV至100mV。优选地,微胶囊是带正电的。ζ电位是微胶囊中电动电势的量度。从理论观点来看,ζ电位是水相(即分散介质)和附着于微胶囊表面的水固定层之间的电位差。ζ电位可以使用理论模型和实验确定的电泳迁移率或动态电泳迁移率来计算。ζ电位常规地通过诸如微电泳,或电泳光散射,或电声现象的方法测量。关于ζ电位测量的更详细讨论,参见Dukhin和Goetz,“Ultrasound for characterizing colloids”,Elsevier,2002。
本发明的微胶囊组合物可以是含有溶剂,优选水的浆料。微胶囊优选以微胶囊组合物重量的0.1重量%至80重量%,更优选1重量%至65重量%,最优选5重量%至45重量%存在于浆料中。浆料可以包含增稠或悬浮剂,例如黄原胶、羧甲基纤维素(CMC)、微晶纤维素(MCC)或瓜尔胶。
或者,本发明的微胶囊组合物也可干燥成固体形式,例如喷雾干燥、热干燥和带式干燥。
微胶囊组合物可以通过用水洗涤胶囊浆料直到达到中性pH(6至8的pH)来纯化。为了本发明的目的,可以使用任何常规方法洗涤胶囊悬浮液,包括使用分液漏斗、滤纸、离心等。胶囊悬浮液可以洗涤一次、两次、三次、四次、五次、六次或更多次,直到达到中性pH,例如pH 6-8和6.5-7.5。纯化的胶囊的pH可以使用任何常规方法测定,包括但不限于pH试纸、pH指示剂或pH计。在本发明的某些实施方案中,胶囊的纯化包括在用水洗涤胶囊悬浮液的步骤之前向胶囊悬浮液中加入盐的附加步骤。在本发明的该步骤中使用的示例性盐包括但不限于氯化钠、氯化钾或亚硫酸氢盐。
微胶囊的制备
当制备微胶囊时,聚合物可以在溶剂中提供。用于制备微胶囊壁的合适溶剂包括水或水与至少一种水混溶性有机溶剂的混合物。合适的有机溶剂包括甘油、1,2-丙二醇、1,3-丙二醇、乙二醇、二甘醇、三甘醇和其它类似物。优选地,溶剂是水。
还可以存在稳定剂。稳定剂可选自丙烯酸类共聚物(优选地具有磺酸盐基团)、丙烯酰胺和丙烯酸的共聚物、丙烯酸烷基酯和N-乙烯基吡咯烷酮的共聚物,例如K15、K30或K90(BASF);聚羧酸钠、聚苯乙烯磺酸钠、乙烯基和甲基乙烯基醚-马来酐共聚物以及乙烯、异丁烯或苯乙烯-马来酸酐共聚物、微晶纤维素(其可以例如以名称商购获得)、迪优坦胶(diutan gum)、黄原胶或羧甲基纤维素。
微胶囊的交联优选涉及催化剂。催化剂可以存在于微胶囊核心活性材料中或单独加入到水包油乳液或分散液中。用于形成根据本发明的微胶囊的优选催化剂是二氮杂双环[2.2.2]辛烷(DABCO),也称为三亚乙基二胺(TEDA)。还合适的是基于铋或锡的催化剂、转谷氨酰胺酶、过氧化物酶、选自多酚(特别是单宁)、没食子酸、阿魏酸、橙皮苷、肉桂醛、香草醛、香芹酚及其混合物的次生植物化合物。
可选地或另外地,微胶囊的形成可通过加热水包油乳液或分散液来催化。例如,加热至60℃至90℃范围内的温度范围。
可以实施各种合适的生产方法来产生适用于本发明的微胶囊。
一种合适的方法是界面聚合。界面聚合的实例包括以下步骤:
(i)提供包括至少一种第一交联剂的微胶囊核心材料,其中交联剂基本上与核心材料一起溶解。这是油相。非水性溶剂可以任选地存在;
(ii)提供包含至少一种蛋白质和至少一种多糖的微胶囊壁材料。这是水相。水性溶剂可以任选地存在;
(iii)用微胶囊壁材料乳化或分散微胶囊核心材料。优选比率为70:30至60:40,优选地30:70-60:40的范围内。任选地,可以使用乳化剂。乳化可以通过使用高速混合来实现。在该阶段完成后,存在水包油乳液或分散液,其中具有待包封的活性物质的内相以液滴形式精细乳化或分散在外壁材料相中;
(iv)任选地通过添加至少一种催化剂进行第一交联以获得微胶囊浆料,任选地添加进一步的蛋白质和/或多糖聚合物;
(v)固化微胶囊浆料,优选在至少60℃的温度下,优选至少30分钟,然后冷却;
(vi)任选地干燥,使用诸如喷雾干燥、过滤或冷冻干燥的方法。
可选方法包括3D打印微胶囊。微胶囊壳和微胶囊核心都可以使用印刷系统打印。参见WO 2016172699A1。打印步骤通常包括以逐层方式沉积活性材料和微胶囊壳材料,优选通过单独的打印头。
使用
织物护理可以通过各种参数来定义,特别是织物手感、柔软性和回弹性。这些是随着织物损坏时降低的量度。换句话说,织物护理可以被认为是织物的防止损坏或维护。织物手感定义为当消费者触摸织物时评价的织物的估计质量。织物手感的重要组成部分包括纺织品样品的光滑度、可压缩性和弹性。本文所述的组合物还可为用组合物处理的织物提供改善的软化和/或回弹性。回弹性是纤维在折叠、折皱或变形后回弹到其自然位置的能力。织物手感、回弹性或软化的改善可以使用感官评价来测量。或者,可以使用机器测量。用于测量相对手感值、回弹性或柔软度的合适机器是由Nu Cybertek,Inc.提供的织物手感的改善可以使用AATCC TM202-2012(2020),Relative HandValue of Textiles:Instrumental Method测量。
实施例
实施例1
微胶囊的制备
以下微胶囊用于评估本文所述的组合物的效果:
·微胶囊A-三聚氰胺甲醛微胶囊
·微胶囊B-豌豆蛋白质且具有多异氰酸酯交联(聚[(苯基异氰酸酯-共-甲醛])
·微胶囊1-豌豆蛋白和海藻酸钠混合且具有盐交联
在所有微胶囊中使用相同型号的芳香组合物。
通过将福尔马林分散在水中并调节pH至9来制备微胶囊A。加入三聚氰胺和0.28g氯化钠。将混合物加热至约65℃持续一小时。加入另外的水并将溶液加热至约75℃。将pH调节至4。然后在均质化下加入芳香剂。继续加热和搅拌3小时。然后将混合物冷却并将pH调节至7。
表1:微胶囊A组合物
微胶囊B如下制备:首先通过混合23.2g模型芳香剂和4.8g辛酸/癸酸甘油三酯,0.38g苯甲酸苄酯和0.38g芳族多异氰酸酯制备油相。在单独的烧杯中,通过在170g水中混合1.182g豌豆蛋白分离物获得水溶液。然后使用ultra turrax混合器以5000转/分钟(RPM)的剪切速率将油相乳化到水相中以形成水包油乳液。然后将水包油乳液在55℃下固化2小时。
表2:微胶囊B组合物
微胶囊B是如WO2020/131879A1中所述的共价交联的多异氰酸酯微胶囊。
微胶囊1(根据本发明)如下制备:在去矿物质水中制备豌豆蛋白溶液,并使用几滴碳酸钠溶液将pH调节至pH 9。将其加热至85℃并在龙卷风混合器上以300RPM混合2小时。2小时后,用几滴2M HCl溶液将pH降至pH 7,且加入1.5g藻酸钠。
将其在300RPM下进一步混合90分钟直至均质化,然后放置过夜以冷却。冷却后次日,加入22.5g芳香油并在300RPM下混合1小时。然后将预聚物混合物在不同浓度下加入到含有吐温80、氯化钙和去离子水的80ml溶液中。将溶液均质化以产生悬浮液。
表2:微胶囊1组合物
织物调理剂的制备
表4:织物调理剂组合物
织物软化活性物质1-二烷氧基乙基羟乙基甲基铵甲基硫酸盐
通过在约65℃下熔融织物软化活性物质来制备织物调理剂。将水加热至约40℃。在搅拌下加入微量物质和织物软化活性物质。然后将水稍微冷却。组合物然后冷却至室温。然后将香料微胶囊加入到组合物中。2重量%是基于微胶囊的重量。
洗涤方法
洗涤在涤垢仪(terg-o-tometer)罐中进行。将0.5ml的测试织物调理剂组合物和1L的水加入到tergo罐中,随后加入40g针织棉布。测试监测物在液体中漂洗10分钟并旋转30秒。然后将织物在环境条件下悬挂干燥。
分析
使用Phabrometer通过NUCybertek*评价织物的性能。
从测试织物上切出11.3cm圆盘。使用Phabrometer并根据AATCC标准TM202进行织物测量。
对每种织物进行10次重复测量,并将结果平均。
表5:结果
微胶囊类型 | 相对手感值 |
微胶囊A | 1.4682 |
微胶囊B | 1.5633 |
微胶囊1 | 1.9391 |
较高的分数表示改善的相对手感值。与常规三聚氰胺甲醛微胶囊以及如WO2020/131879A1中所描述的共价交联的多异氰酸酯微胶囊相比,根据本发明的微胶囊提供了改善的相对手感值。
实施例2
如实施例1制备微胶囊B和1。
织物调理剂的制备
表6:织物调理剂组合物
织物软化活性物质1-二烷氧基乙基羟乙基甲基铵甲基硫酸盐
通过在约65℃下熔融织物软化活性物质来制备织物调理剂。将水加热至约40℃。在搅拌下加入微量物质和织物软化活性物质。然后将水稍微冷却。组合物然后冷却至室温。然后将香料微胶囊加入到组合物中。重量%是基于微胶囊的重量。
洗涤方法
洗涤在涤垢仪罐中进行。将0.5ml的测试织物调理剂组合物和1L的水加入到tergo罐中,随后加入40g针织棉布。测试监测物在液体中漂洗10分钟并旋转30秒。然后将织物在环境条件下悬挂干燥。
分析
使用Phabrometer通过NUCybertek*评价织物的性能。从测试织物上切出11.3cm圆盘。使用Phabrometer并根据AATCC标准TM202进行织物测量。
对每种织物进行10次重复测量,并将结果平均。
表7:结果
微胶囊类型 | 悬垂 | 回弹性 |
微胶囊B | 20.85 | 60.58 |
微胶囊1 | 18.68 | 56.96 |
较低的数值表示改进的织物性能。用包含具有离子交联剂的微胶囊的产品处理的织物具有更好的织物形状和悬垂性。
实施例3
根据以下示例性方法制备进一步的微胶囊,与所指出的一般方法具有任何微小偏差:-
一般方法
在去矿物质水中制备豌豆蛋白溶液,并使用几滴碳酸钠溶液将pH调节至pH 9。将其加热至85℃并在龙卷风混合器上以300RPM混合2小时。2小时后,用几滴2M HCl溶液将pH降至pH 7,并加入1g多糖。
将其在300RPM下进一步混合90分钟直至均匀,然后放置过夜以冷却。冷却后第二天,加入15g芳香油并在300RPM下混合1小时。然后将预聚物混合物在不同浓度下加入到含有吐温80、氯化钙和去离子水的40ml溶液中。将溶液均质化以产生悬浮液。
将微胶囊2分散在80g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表8:微胶囊2组合物
将微胶囊3分散在80g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85C,2小时
表9:微胶囊3组合物
将微胶囊4分散在80g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表10:微胶囊4组合物
将微胶囊5分散在80g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表11:微胶囊5组合物
将微胶囊6分散在80g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表12:微胶囊6组合物
将微胶囊7分散在300g含有1%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表13:微胶囊7组合物
将微胶囊8分散在300g含有1.5%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表14:微胶囊8组合物
将微胶囊9分散在300g含有1.5%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85℃,2小时
表15:微胶囊9组合物
将微胶囊10分散在300g含有1%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85C,2小时
表16:微胶囊10组合物
将微胶囊11分散在150g含有2%乳化剂(吐温80)和2%CaCl2.2H2O的去矿物质水中。
均质化速率20000RPM,加热温度85C,2小时
表17:微胶囊11组合物
Claims (9)
1.一种微胶囊,其中所述微胶囊具有核心和壳;所述核心包含选自香料的核心材料;所述壳包含植物蛋白和多糖,其中所述多糖选自:果胶、天然或化学改性纤维素、黄原胶、魔芋胶、木葡聚糖、瓜尔胶、塔拉胶、刺槐豆胶、菊粉、凝胶多糖胶、定优胶、藻酸盐、结冷胶和角叉菜胶。
2.根据权利要求1所述的微胶囊,其中所述微胶囊是可生物降解的。
3.根据权利要求1或权利要求2所述的微胶囊,其中所述微胶囊包封可生物降解的香料。
4.根据前述权利要求中任一项所述的微胶囊,其中所述蛋白是豌豆蛋白。
5.根据前述权利要求中任一项所述的微胶囊,其中所述多糖选自:藻酸盐、结冷胶、角叉菜胶,更优选地所述多糖是藻酸盐。
6.根据前述权利要求中任一项所述的微胶囊,其中所述微胶囊包含1重量%至80重量%,优选地2重量%至70重量%的壳材料。
7.根据前述权利要求中任一项所述的微胶囊,其中所述微胶囊还包含附着于所述微胶囊的壳的沉积助剂,优选地所述沉积助剂选自三甲基铵、甲基丙烯酰胺丙基三甲基铵、丙烯酰胺丙基三甲基铵、丙烯酰胺、丙烯酸、二甲基铵、木糖、半乳糖、羟丙基化葡萄糖、壳聚糖、羟乙基化葡萄糖、羟甲基化葡萄糖、乙烯基胺、乙烯亚胺、功能化支化聚乙烯亚胺、乙烯基甲酰胺、乙烯基吡咯烷酮、己内酯、邻苯二酚、乙烯基醇、脱乙酰壳多糖、聚季铵盐-4、聚季铵盐-5、聚季铵盐-6、聚季铵盐-7、聚季铵盐-10、聚季铵盐-11、聚季铵盐-16、聚季铵盐-22、聚季铵盐-24、聚季铵盐-28、聚季铵盐-37、聚季铵盐-39、聚季铵盐-44、聚季铵盐-46、聚季铵盐-47、聚季铵盐-53、聚季铵盐-55、聚季铵盐-67、聚季铵盐-68、聚季铵盐-69、聚季铵盐-73、聚季铵盐-74、聚季铵盐-77、聚季铵盐-78、聚季铵盐-79、聚季铵盐-80、聚季铵盐-81、聚季铵盐-82、聚季铵盐-86、聚季铵盐-88、聚季铵盐-101、聚季铵盐-79水解角蛋白、聚乙烯基胺、聚乙烯亚胺、乙烯基胺和乙烯基甲酰胺的共聚物、丙烯酰胺与3-甲基丙烯酰基氨基丙基三甲基铵的共聚物、3-丙烯酰胺丙基三甲基铵聚合物或其共聚物、二烯丙基二甲基氯化铵聚合物及其共聚物、具有由羟丙基三甲基铵功能化的糖单元的多糖、乙基三甲基氯化铵甲基丙烯酸盐和水解小麦蛋白共聚物、烷基-甲基铵羟丙基水解蛋白及其组合。
8.一种制备根据权利要求1-7中任一项所述的微胶囊的方法,其中所述方法不涉及化学共价交联,优选地所述方法选自离子交联、带电聚合物交联或氢键键合,更优选地离子交联。
9.根据权利要求9所述的制备微胶囊的方法,其中所述方法选自离子交联、带电聚合物交联或氢键键合,优选地离子交联。
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