CN1678694B - 用于化妆和个人护理配方的具有至少一层SiOx涂层的彩色光泽颜料 - Google Patents
用于化妆和个人护理配方的具有至少一层SiOx涂层的彩色光泽颜料 Download PDFInfo
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- CN1678694B CN1678694B CN038204231A CN03820423A CN1678694B CN 1678694 B CN1678694 B CN 1678694B CN 038204231 A CN038204231 A CN 038204231A CN 03820423 A CN03820423 A CN 03820423A CN 1678694 B CN1678694 B CN 1678694B
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- Prior art keywords
- sio
- acid
- siox
- oil
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Classifications
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- C01P2006/00—Physical properties of inorganic compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
本发明涉及化妆和个人护理制剂或配方,包含基于化妆制剂或配方的总重量计:(a)0.0001-90重量%的光泽颜料,该光泽颜料含有:(a1)由基本透明或金属反射材料组成的芯,和(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,和(b)10-99.9999%的(化妆)适宜的载体材料。
Description
本发明涉及化妆和个人护理制剂或配方,包含基于化妆制剂或配方的总重量计:
(a)0.0001-90重量%的光泽颜料,该光泽颜料含有:
(a1)由基本透明或金属反射材料组成的芯,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,和
(b)10-99.9999%的(化妆)适宜载体材料。
化妆组合物,例如游离粉末、压实粉末、粉底、胭脂、眼影和唇膏,在其应用到皮肤的至少一部分(包括嘴唇)上以及表面体生长之前和/或之后,可以包含适宜的载体和各种着色剂以赋予该组合物以一定的颜色。
较严格范围的着色剂,例如颜料,例如色淀,无机颜料和珠光颜料,目前用于形成颜色。色淀使得有可能获得生动的颜色,但是通常对光、温度和pH不稳定。在使用之后,通过排出着色剂,一些还以不可见的方式污染皮肤。相比之下,元机颜料例如元机氧化物是非常稳定的,但是得到相当灰暗和苍白的颜色。珠光颜料不能提供具有虹彩效果的强烈颜色。但是,珠光颜料使得有可能获得一般具有较弱色彩效果的各种颜色,例如该色彩效果主要在仅仅一个给定的对应于光谱反射的角度上才可见。例如,专利WO-A-96/03962公开了乳液形式的化妆组合物,其包含硅油;小片型的“干扰性”颜料,由载体例如云母组成,该载体被给定的氧化钛层涂覆到给定的厚度;和基于氧化铁的颜料。由于在该组合物中存在干扰性颜料,所以该组合物得到与给定角度一致的色调,不会产生角色差效果。
本发明的一个目的是提供一种能克服至少一种上述缺点的化妆组合物。本发明的另一个目的是提供一种显示至少一种以下效果的化妆组合物:例如美学、角色差和体积效果。这些效果可以通过使用例如选自粉底、眼影、胭脂、唇膏、唇彩、唇油、睫毛油和眼线的组合物获得。
因此,本发明涉及化妆和个人护理制剂或配方,包含:
(a)0.0001-90重量%的光泽颜料,该光泽颜料含有:
(a1)由基本透明或金属反射材料组成的芯,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,和
(b)10-99.9999%的(化妆)适宜载体材料,基于化妆制剂或配方的总重量计。
根据本发明的制剂特别是适合于化妆嘴唇或皮肤和适合于头发或指甲染色的制剂或配方。
化妆制剂是例如唇膏、胭脂、粉底、指甲油和洗发水。
光泽颜料可以单独使用或以混合物形式使用。另外,光泽颜料可以与其它颜料和/或着色剂一起使用。
根据本发明的化妆制剂和配方优选含有0.005-50重量%的光泽颜料,基于制剂的总重量计。
适用于本发明化妆制剂和配方的载体材料包括在这些组合物中常用的材料。
根据本发明的化妆制剂和配方可以是例如棒、软膏、乳油、乳液、悬浮液、分散液、粉末或溶液的形式。它们例如是唇膏、睫毛油制剂、胭脂、眼影、粉底、眼线、粉末或指甲油。
如果制剂是棒的形式,例如唇膏、眼影、胭脂或粉底,则这些制剂包含相当部分的脂肪组分,这些组分包含一种或多种蜡,例如地蜡、羊毛脂、羊毛醇、氢化羊毛脂、乙酰化羊毛脂、羊毛脂蜡、蜂蜡、小烛树蜡、微晶蜡、巴西棕榈蜡、十六醇、硬脂醇、可可油、羊毛脂肪酸、凡士林、矿脂,单-、二-或三甘油酯,或它们在25℃下呈固态的脂肪酯,硅蜡,例如甲基十八烷-氧基聚硅氧烷和聚(二甲基硅氧基)硬脂氧基硅氧烷,硬脂酸单乙醇胺,松香(colophane)及其衍生物,例如松香二醇酯和松香甘油酯,在25℃下呈固体的氢化油,糖甘油酯,和钙、镁、锆和铝的油酸盐、肉豆蔻酸盐、羊毛脂酸盐、硬脂酸盐和二羟基硬脂酸盐。
脂肪组分还可以包含至少一种蜡和至少一种油的混合物,在这种情况下例如以下油是合适的:石蜡油,purcelline油,过氢角鲨烯,甜杏仁油、鳄梨油,海棠果素油,蓖麻油,芝麻油,霍霍巴油,沸点为约310-410℃的矿物油,硅油,例如二甲基聚硅氧烷,亚油醇,亚麻醇,油醇,谷粒油,例如麦芽油,羊毛脂酸异丙酯,棕榈酸异丙酯,肉豆蔻酸异丙酯,肉豆蔻酸丁酯,肉豆蔻酸十六烷基酯,硬脂酸十六烷基酯,硬脂酸丁酯,油酸癸基酯,乙酰基甘油三酯,醇和多元醇例如乙二醇和甘油的辛酸酯和癸酸酯,醇和多元醇,例如十六醇、异硬脂醇的蓖麻酸酯,羊毛脂酸异十六烷基酯,己二酸异丙酯,月桂酸己酯和辛基十二醇。
在棒形式的这种制剂中的脂肪组分可以通常最高达到制剂总重量的99.91重量%。
根据本发明的化妆制剂和配方可以另外含有其它组分,例如二醇,聚乙二醇,聚丙二醇,单链烷醇酰胺,未着色的聚合、元机或有机的填料,防腐剂,UV过滤剂或其它在化妆中常用的助剂和添加剂,例如天然或合成的或部分合成的二-或三-甘油酯,矿物油,硅油,蜡,脂肪醇,Guerbet醇或其酯,亲油性官能化妆活性成分,包括防晒剂,或这些物质的混合物。
适合于皮肤化妆的亲油性官能化妆活性成分、活性成分组合物或活性成分提取物是可用于真皮或局部施用的组分或组分混合物。例如可以提及以下成分:
-在皮肤表面和头发上具有清洁作用的活性成分:这些包括所有用于清洁皮肤的物质,例如油、皂、合成洗涤剂和固体物质;
-具有除味和防汗作用的的活性成分:它们包括基于铝盐或锌盐的防汗剂,含有杀菌或抑菌除味物质的除味剂,例如三氯羟基二苯醚、六氯二苯酚甲烷,醇和阳离子物质,例如季铵盐,和吸味剂,例如Grillocin(蓖麻酸锌和各种添加剂的组合)或柠檬酸三乙酯(任选与抗氧化剂组合,例如丁基羟基甲苯)或离子交换树脂;
-用于防晒的活性成分(UV过滤剂):合适的活性成分是能吸收来自日光的UV辐射并将其转化成热的过滤剂物质(防晒制品);根据所需的作用,以下光防护剂是优选的:能在约280-315nm范围内选择性吸收能引起晒伤的高能UV辐射并在长波范围内例如315-400nm范围(UV-A范围)内传输的光防护剂(UV-B吸收剂),以及仅仅能吸收315-400nm的UV-A范围内的较长波辐射的光防护剂(UV-A吸收剂);合适的光防护剂是例如有机UV吸收剂,选自对氨基苯甲酸衍生物,水杨酸衍生物,二苯甲酮衍生物,二苯甲酰基甲烷衍生物,二苯基丙烯酸酯衍生物,苯并呋喃衍生物,含有一个或多个有机硅基团的聚合物UV吸收剂,肉桂酸衍生物,樟脑衍生物,三苯胺基-s-三嗪衍生物,苯基苯并咪唑磺酸及其盐,邻氨基苯甲酸基酯,苯并***衍生物,和/或选自氧化铝-或二氧化硅一涂覆的TiO2、氧化锌和云母的无机微颜料;其中合适的UV过滤剂物质列在下面:
-防昆虫的活性成分(驱虫剂)是要防止昆虫接触皮肤和在皮肤上存活的试剂:它们驱除昆虫并且蒸发缓慢;最常用的驱虫剂是二乙基甲苯甲酰胺(DEET);其它常用驱虫剂见“Pflegekosmetik”(W.Raab和U.Kindl,Gustav-Fischer-Verlag Stuttgart/纽约,1991)第61页;
-用于防止化学和机械影响的活性成分:这些包括所有能在皮肤和外部有害物质之间形成屏障的物质,例如石蜡油,硅油,植物油,PCL产品和用于防止水溶液的羊毛脂,成膜剂,例如藻酸钠,藻酸三乙醇胺,聚丙烯酸酯,聚乙烯醇或用于防止有机溶剂影响的纤维素醚,或基于矿物油、植物油或硅油的物质,作为用于防止对皮肤的严重机械应力的“润滑剂”;
-保湿物质:以下物质例如用作湿度控制剂(保湿剂):乳酸钠,脲,醇,山梨醇,甘油,丙二醇,胶原,弹性蛋白和透明质酸;
-具有角质塑化作用的活性成分:过氧化苯甲酰,视黄酸,胶态硫和视黄醇;
-抗微生物剂,例如三氯羟基二苯醚或季铵化合物;
-皮肤用的油基或油溶性维生素或维生素衍生物:例如维生素A(游离酸或其衍生物形式的视黄醇),泛醇,泛酸,叶酸,以及它们的组合物,维生素E(生育酚),维生素F;必需脂肪酸;或烟酰胺(烟酸酰胺);
-基于维生素的胎盘提取物:活性成分组合物,特别含有维生素A、C、E、B1、B2、B6、B12、叶酸和生物素,氨基酸和酶,以及痕量元素镁、硅、磷、钙、锰、铁或铜的化合物;
-皮肤修复复合物:可从钝化的和分解的双叉杆菌族的细菌簇获得;
-植物和植物提取物:例如山金车花、芦荟、须地衣、常春藤、大荀麻、人参、指甲花、挪威甘菊、万寿菊、迷迭香、鼠尾草、马尾或百里香;
-动物提取物:例如王浆、蜂胶、蛋白质或胸腺提取物;
-皮肤用化妆油:非离子甘油酯,例如Miglyol 812,杏仁油,鳄梨油,巴西棕榈油,棉子油,琉璃苣油,蓟油,花生油,γ-谷维素,玫瑰籽油,***油,榛子油,黑醋梨子油,霍霍巴油,樱桃核油,鲑鱼油,亚麻子油,玉米子油,澳大利亚坚果核油,杏仁油,夜来香油,貂油,橄榄油,核桃核油,桃仁油,乳香黄连木油,菜子油,稻籽(rice-seed)油,蓖麻油,红花油,芝麻油,豆油,葵花子油,茶树油,葡萄子油或麦芽油。
棒形式的制剂优选是无水的,但是可以在某些情况下含有一定量的水,但是,水的量通常不超过40重量%,基于化妆制剂的总重量计。
如果根据本发明的化妆制剂和配方是半固体产品的形式,也就是软膏或乳油的形式,则它们可以相似地是无水的或含水的。这些制剂和配方是例如睫毛油、眼线剂、粉底、胭脂、眼影或用于处理眼圈的组合物。
另一方面,如果这些软膏或乳油是含水的,则它们特别是油包水型或水包油型乳液,除了颜料之外还含有1-98.8重量%的脂肪相,1-98.8重量%的水相和0.2-30重量%的乳化剂。
这些软膏和乳油可以还包含其它常规添加剂,例如香料、抗氧化剂、防腐剂、凝胶形成剂、UV过滤剂、着色剂、颜料、珠光剂、非着色的聚合物以及无机或有机填料。
如果这些制剂是粉末的形式,则它们基本上包含矿物或无机或有机填料,例如滑石、高岭土、淀粉、聚乙烯粉末或聚酰胺粉末,以及助剂例如粘合剂、着色剂等。
这些制剂可以相似地含有各种化妆品中常用的助剂,例如香料、抗氧化剂、防腐剂等。
如果根据本发明的化妆制剂和配方是指甲油,则它们基本上由硝基纤维素和在溶剂体系中的溶液形式的天然或合成聚合物组成,该溶液可以含有其它助剂,例如珠光剂。在此实施方案中,着色聚合物以约0.1-5重量%的量存在。
根据本发明的化妆制剂和配方还用于头发染色,在这种情况下它们是以洗发水、发乳或凝胶的形式使用,由在化妆品工业中常用的基础物质和本发明的颜料组成。
用于头发染色的组合物可以还含有任何已知用于这种制剂的活性成分、添加剂或助剂。
适用于这些配方的助剂通常是染发领域中常用的,例如表面活性剂、溶剂、碱、酸、香料、聚合物助剂、增稠剂和光稳定剂。
用于头发染色的组合物在许多情况下含有至少一种表面活性剂。
合适的表面活性剂是阴离子、两性离子、两性、非离子和阳离子表面活性剂。但是,在许多情况下,已经证明有利的是选择阴离子、两性离子和非离子表面活性剂。
适用于头发染色组合物的阴离子表面活性剂包括适用于人体的所有阴离子表面活性物质。这些物质的特征在于具有赋予水溶性的阴离子基团,例如羧酸根、硫酸根、磺酸根或磷酸根,和具有约10-22个碳原子亲油性烷基。另外,二醇或聚二醇醚基团、酯、醚和酰胺基团以及羟基可以存在于分子中。以下是适宜的阴离子表面活性剂的例子,各自是钠、钾或铵盐或在链烷醇基团中具有2或3个碳原子的单、二或三链烷醇铵盐的形式:
-具有10-22个碳原子的直链脂肪酸(皂),
-式R-O-(CH2-CH2-O)x-CH2-COOH的醚羧酸,其中R是具有10-22个碳原子的直链烷基,x=0或1-16,
-在酰基中具有10-18个碳原子的酰基肌氨酸,
-在酰基中具有10-18个碳原子的酰基氨基乙磺酸盐,
-在酰基中具有10-18个碳原子的酰基异硫代硫酸盐,
-在烷基中具有8-18个碳原子的磺基琥珀酸单和二烷基酯,和在烷基中具有8-18个碳原子并具有1-6个氧乙基的磺基琥珀酸单烷基聚氧乙基酯,
-具有12-18个碳原子的直链烷磺酸盐,
-具有12-18个碳原子的直链α-烯烃磺酸盐,
-具有12-18个碳原子的脂肪酸的α-磺基脂肪酸甲基酯,
-烷基硫酸盐和具有式R’-O-(CH2-CH2-O)x,-SO3H的烷基聚二醇醚硫酸盐,其中R’优选是具有10-18个碳原子的直链烷基,x’=0或1-12,
-表面活性羟基磺酸盐的混合物,根据DE-A-3 725 030,特别是第3页40-55行,
-硫酸盐化羟基烷基聚乙烯和/或羟基亚烷基丙二醇醚,根据DE-A-3 723 354,特别是第4页42-62行,
-具有12-24个碳原子和1-6个双键的不饱和脂肪酸的磺酸盐,根据DE-A-3 926 344,特别是第2页36-54行,
-酒石酸和柠檬酸与醇的酯,它是约2-15个分子的环氧乙烷和/或环氧丙烷与具有8-22个碳原子的脂肪醇的加成产物,或
-WO 00/10518中描述的阴离子表面活性剂,特别是第45页第11行到第48页第3行。
优选的阴离子表面活性剂是烷基硫酸盐,烷基聚二醇醚硫酸盐和在烷基中具有10-18个碳原子和在分子中具有至多12个二醇醚基团的醚羧酸,以及特别是饱和的和尤其不饱和C8-C22羧酸的盐,例如油酸、硬脂酸、异硬脂酸和棕榈酸。
在分子中带有至少一个季铵基团和至少一个-COO(-)或-SO3 (-)基团的表面活性化合物称为两性离子表面活性剂。特别合适的两性离子表面活性剂是所谓的甜菜碱,例如N-烷基-N,N-二甲基氨基乙酸铵,例如椰油烷基二甲基氨基乙酸铵,N-酰基氨基丙基-N,N-二甲基氨基乙酸铵,例如椰油酰基氨基丙基二甲基氨基乙酸铵,和在烷基或酰基中具有8-18个碳原子的2-烷基-3-羧甲基-3-羟基乙基咪唑啉,以及椰油酰基氨乙基羟乙基羧甲基氨基乙酸盐。优选的两性离子表面活性剂是脂肪酸酰胺衍生物,CTFA命名为椰油酰氨基丙基甜菜碱。
两性表面活性剂是指这样的表面活性化合物,它除了C8-C18烷基或C8-C18酰基之外,还在分子中含有至少一个游离氨基和至少一个-COOH基团或-SO3H基团,并能形成内盐。
合适的两性表面活性剂的例子包括N-烷基氨基乙酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基氨基丙基-氨基乙酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基氨基乙酸,各自在烷基中具有约8-18个碳原子。特别优选的两性表面活性剂是N-椰油烷基-氨基丙酸盐、椰油酰基氨基乙基氨基丙酸盐和C12-C18酰基肌氨酸。
非离子表面活性剂描述在WO 00/10519中,特别是第45页第11行到第50页第12行。
非离子表面活性剂含有亲水基团,例如多元醇基团、聚亚烷基二醇醚基团或多元醇基团和聚二醇醚基团的组合。这些化合物是例如:
-2-30摩尔环氧乙烷和/或0-5摩尔环氧丙烷与具有8-22个碳原子的直链脂肪醇、与具有12-22个碳原子的脂肪酸和与在烷基中具有8-15个碳原子的烷基酚形成的加成产物,
-1-30摩尔环氧乙烷与甘油的加成产物的C12-C22脂肪酸单和二酯,
-C8-C22烷基单和低聚苷及其乙氧基化类似物,
-5-60摩尔环氧乙烷与蓖麻油和氢化蓖麻油的加成产物,
-环氧乙烷与脱水山梨醇脂肪酸酯的加成产物,
-环氧乙烷与脂肪酸链烷醇酰胺的加成产物。
可以用于本发明制剂(组合物)中的阳离子表面活性剂的例子特别是季铵化合物。优选卤化铵,例如烷基三甲基氯化铵,二烷基二甲基氯化铵和三烷基甲基氯化铵,例如十六烷基三甲基氯化铵,硬脂基三甲基氯化铵,二硬脂基二甲基氯化铵,月桂基二甲基氯化铵,月桂基二甲基苄基氯化铵和三(十六烷基)甲基氯化铵。可以根据本发明使用的其它阳离子表面活性剂是季铵化蛋白质水解物。
根据本发明也合适的是阳离子硅油,例如工业产品Q2-7224(生产者:Dow Corning;稳定化的三甲基甲硅烷基氨基封端的二甲基聚硅氧烷),Dow Corning 929乳液(包含羟基氨基改性的硅氧烷,也称为氨基封端的二甲基聚硅氧烷),SM-2059(生产者:GeneralElectric),SLM-55067(生产者:Wacker)和Abil-Quat 3270和3272(生产者:Th.Goldschmidt;二季化聚二甲基硅氧烷,quaternium-80)或WO00/12507中描述的硅氧烷,特别是第45页第9行到第55页第2行。烷基酰氨基胺、特别是脂肪酸酰氨基胺,例如以商品名Tego Amid18获得的硬脂基酰氨基丙基二甲基胺的特点不仅在于良好的调节作用,而且特别在于良好的生物可降解性。
可以用作阳离子表面活性剂的季化糖衍生物的例子是商品Gluquat100,根据CTFA命名为“月桂基甲基葡糖醚-10羟丙基二甲基氯化铵”。
用作表面活性剂的含有烷基的化合物可以是单一的物质,但是在这些物质的制备中通常优选使用植物或动物来源的天然原料,结果是获得的物质混合物根据使用的特定原料具有不同的烷基链长度。
作为环氧乙烷和/或环氧丙烷与脂肪醇的加成产物或这些加成产物的衍生物的表面活性剂可以是具有“正常”同系物分布的产品或具有受限同系物分布的产品。“正常”同系物分布理解为指在使用碱金属、碱金属氢氧化物或碱金属醇盐作为催化剂的脂肪醇与氧化烯的反应中获得的同系物混合物。另一方面,受限同系物分布是在例如水滑石、醚羧酸的碱金属盐、碱金属氧化物、氢氧化物或醇盐作为催化剂使用时获得的。具有受限同系物分布的产品是优选使用的。
其它优选的根据本发明配方的活性成分、助剂和添加剂列在下面:
-非离子聚合物,例如乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物,聚乙烯基吡咯烷酮和乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物和聚硅氧烷,
-阳离子聚合物,例如季铵纤维素醚,具有季化基团的聚硅氧烷,二甲基二烯丙基氯化铵聚合物,二甲基二烯丙基氯化铵和丙烯酸的共聚物,以商品名Merquat280获得,其在头发着色中的用途描述在例如DE-A-4 421 031中,特别是第2页第20-49行,或EP-A-953 334,特别是第27页第17行到第30页第11行,丙烯酰胺/二甲基二烯丙基氯化铵共聚物,二乙基硫酸盐季化的甲基丙烯酸二甲基氨基乙基酯/乙烯基吡咯烷酮共聚物,乙烯基吡咯烷酮/甲基氯化咪唑鎓共聚物,
-季化聚乙烯醇,
-两性离子和两性聚合物,例如丙烯酰胺基丙基三甲基氯化铵/丙烯酸酯共聚物和辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙基酯/甲基丙烯酸2-羟丙基酯共聚物,
-阴离子聚合物,例如聚丙烯酸,交联聚丙烯酸,乙酸乙烯酯/巴豆酸共聚物,乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物,乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物,甲基乙烯基醚/马来酸酐共聚物和丙烯酸/丙烯酸乙酯/N-叔丁基丙烯酰胺三元共聚物,
-增稠剂,例如琼脂、瓜尔胶,藻酸盐,黄原胶,***胶,刺梧桐树胶,刺槐豆粉,亚麻子胶,葡聚糖,纤维素衍生物,例如甲基纤维素,羟烷基纤维素和羧甲基纤维素,淀粉级分和衍生物,例如直链淀粉,支链淀粉和糊精,粘土,例如膨润土或完全合成的水胶体,例如聚乙烯醇,或Salcare类例如Salcare SC80(硬脂基醚-10烯丙基醚/丙烯酸酯共聚物)、Salcare SC81(丙烯酸酯共聚物)、Salcare SC91和Salcare AST(丙烯酸钠共聚物/PPG-1十三烷醇聚醚-6),
-结构化剂,例如葡萄糖和马来酸,
-头发调理化合物,例如磷脂,例如大豆卵磷脂,蛋卵磷脂,和脑磷脂,硅油,以及调理化合物,例如描述在DE-A-19 729 080中,特别是第2页第20-49行,EP-A-834 303,特别是第2页第18行到第3页第2行,或EP-A-312 343,特别是第2页第59行到第3页第11行,
-蛋白质水解物,特别是弹性蛋白、胶原、角蛋白、牛奶蛋白、大豆蛋白和小麦蛋白水解物,它们与脂肪酸的缩合产物以及季化蛋白质水解物,
-香料油,二甲基异山梨醇和环糊精,
-增溶剂,例如乙醇、异丙醇、乙二醇、丙二醇、甘油和二甘醇,
-抗皮屑活性成分,例如梨酮、油胺和吡啶硫酮锌,
-其它用于调节pH值的物质,
-活性成分例如泛醇、泛酸、尿囊素、吡咯烷酮羧酸及其盐,植物提取物和维生素,
-胆固醇,
-光稳定剂和UV吸收剂,例如描述在EP-A-819 422中,特别是第4页34-37行,
-稠度调节剂,例如糖酯、多元醇酯或多元醇烷基醚,
-脂肪和蜡,例如鲸蜡、蜂蜡、褐煤蜡、石蜡、脂肪醇和脂肪酸酯,
-脂肪链烷醇酰胺,
-聚乙二醇和聚丙二醇,分子量为150-50000,例如描述在EP-A-801942中,特别是第3页44-55行,
-络合剂,例如EDTA、NTA和膦酸,
-膨胀和穿透物质,例如多元醇和多元醇醚,详细地描述在例如EP-A-962 219中,特别是第27页18-38行,例如甘油、丙二醇、丙二醇单***、丁二醇、苄醇、碳酸盐、碳酸氢盐、胍、脲以及伯、仲和叔磷酸盐,咪唑、单宁、吡咯,
-不透明剂,例如胶乳,
-珠光剂,例如乙二醇单和二硬脂酸酯,
-推进剂,例如丙烷-丁烷混合物,N2O,二甲基醚,CO2和空气,以及
-抗氧化剂,
-多元醇或多元醇醚,描述在EP-A-962 219中,特别是第27页14-38行,
-增稠聚合物,描述在EP-A-970 684中,特别是第48页16行到第51页第4行,
-含糖的聚合物,描述在EP-A-970 687中,特别是第28页17行到第29页第23行,
-季铵盐,描述在WO00/10517中,特别是第44页16行到第46页第23行。
UV吸收剂的使用可以有效地保护天然和染色的头发免受日光射线的损害和提高染色头发的洗涤牢固性。
在用于头发染色的组合物中优选的UV吸收剂是:
-阳离子苯并***UV吸收剂,例如描述在WO 01/36396中,特别是第1页第20行到第2页第24行,并优选在第3-5页和第26-37页,或
-阳离子苯并***UV吸收剂与抗氧化剂的组合,描述在WO01/36396中,特别是第11页第14行到第18页,或
-UV吸收剂与抗氧化剂的组合,描述在美国专利5 922 310中,特别是第2栏第1-3行,
-UV吸收剂与抗氧化剂的组合,描述在美国专利4 786 493中,特别是第1栏42行到第2栏第7行,并优选在第3栏第43行到第5栏第20行,或
-UV吸收剂的组合,描述在美国专利5 830 441中,特别是第4栏53-56行,或
-UV吸收剂的组合,描述在WO 01/36396中,特别是第11页第9-13行,或
-三嗪衍生物,提供有效的UV保护作用,描述在WO 98/22447中,特别是第1页第23行到第2页第4行,并优选在第2页第11行到第3页第15行,且最优选在第6-7页和第12-16页,或
-WO 98/22447中描述的化妆配方与一种或多种在下列专利中描述的其它UV过滤剂的组合:
(缩写T:表格,R:行,Comp:化合物,Ex:专利实施例的化合物,p=页;pp=页)
EP 895776 R 48-58,p3;R25+33,p5中的化合物 |
WO 9220690 实施例3-6中的聚合物 |
EP 1000950 Table1,pp18-21中的化合物 |
EP 1060734 T1-3,pp11-14 |
EP 1059082 Ex1; 1,pp9-11 |
EP 1008586 Ex1-3,pp 13-15 |
EP 1005855 T3,p13 |
EP 1129695 Ex1-7,pp13-14 |
EP 967200 Ex2;T3-5,pp17-20 |
EP 945125 T3a+b,pp14-15 |
EP 924246 T2,p9 |
EP 911020 T2,p11-12 |
EP 916335 T2-4,pp19-41 |
EP 852137 T2,pp41-46 |
EP 858318 T1,p6 |
EP 826361 T1,pp5-6 |
EP 503338 T1,pp9-10 |
WO 9301164 T1+2,pp13-22 |
EP 823418 Ex1-4,pp7-8 |
WO 9714680 Ex1-3,p10 |
EP 1027883 Comp Vll,p3 |
EP 832641 Ex 5+6p7;t2,p8 |
US 5338539 Ex1-9,pp3+4 |
EP 517103 Ex3,4,9,10pp6-7 |
EP 1123934 T3,p10 |
EP 1027883 CompI-VI,p3 |
EP 969004 Ex5,T1,pp6-8 |
US 5801244 Ex1-5,pp6-7 |
EP 832642 Ex22,T3pp,10-15;T4,p16 |
US 5346691(EP 570838) Ex40,p7;T5,p8 |
EP 517104 Ex1,T1,pp4-5; Ex8,T2,pp6-8 |
WO 200149686 Ex1-5,pp16-21 |
EP 944624 Ex1+2,pp13-15 |
EP 933376 Ex1-15,pp10-21 |
EP 863145 Ex1-11,pp12-18 |
EP 780382 Ex1-11,pp5-7 |
EP 626950 所有实施例 |
EP 1081140 Ex1-9,pp11-16 |
WO 9217461 Ex1-22,pp10-20 |
WO 0168047 pp85-96中的表 |
EP 613893 Ex1-5+15,T1,pp6-8 |
EP 1064922 Comp1-34,pp6-14 |
EP 1028120 Ex1-5,pp5-13 |
EP 1008593 Ex1-8,pp4-5 |
EP 669323 Ex1-3,p5 |
EP 1108712 4,5-二吗啉代-3-羟基哒嗪 |
JP 2000319629 CAS Regno.80142-49-0,137215-83-9,307947-82-6 |
EP 420707B1 Ex3,p13(80142-49-0) |
US 5635343 所有实施例 |
EP 1167358 所有实施例 |
当UV吸收剂与抗氧化剂组合时,可以观察到协同效应。可以使用的抗氧化剂的例子列在WO 01/36396(11-18页)、美国专利5 922 310和美国专利4 786 493中。
合适的化妆制剂可以通常含有0.05-40重量%,优选0.1-20重量%的一种或多种UV吸收剂,基于组合物的总重量计。
在本发明的另一个实施方案中,UV吸收剂被微细化,例如通过下述方法进行:
-用硬研磨介质进行湿研磨,例如在水或合适的有机溶剂中的硅酸锆和保护性表面活性剂或保护性聚合物;
-从合适的溶剂喷雾干燥,例如水悬浮液或含有有机溶剂的悬浮液,或在水、乙醇、二氯乙烷、甲苯或N-甲基吡咯烷酮中的真溶液等;
-通过超临界流体(例如二氧化碳)RESS方法(超临界溶液的快速膨胀)进行膨胀,其中UV过滤剂被溶解,或流体二氧化碳与一种或多种UV过滤剂在合适有机溶剂中的溶液一起膨胀;
-用合适的溶剂再沉淀,包括超临界流体(GASR方法=气体反溶剂重结晶/PCA方法=用压缩反溶剂进行沉淀)。
用于制备微细化有机UV吸收剂的研磨设备可以使用例如喷射磨、球磨、振动磨或锤磨,优选高速混合磨。研磨优选用研磨助剂进行,例如烷基化乙烯基吡咯烷酮聚合物,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,酰基谷氨酸盐,烷基聚葡萄糖苷,鲸蜡硬脂醇聚醚-25或磷脂。
如此获得的微细化UV吸收剂通常具有0.02-2微米的平均粒度,优选0.05-1.5微米,更特别是0.1-1.0微米。
UV吸收剂也可以以粉末形式干态使用。为此,UV吸收剂进行公知的研磨方法,例如真空雾化、逆流喷雾干燥等。这些粉末具有0.1-2微米的粒度。为了避免出现聚集,UV吸收剂可以在粉末化工艺之前用表面活性化合物涂覆,例如用阴离子、非离子或两性表面活性剂,例如磷脂或公知的聚合物,例如PVP,或丙烯酸酯。
根据本发明的制剂还可以含有抗微生物剂。在配方中使用的优选的抗微生物防腐剂和抗微生物活性剂(在大多数情况下使用抗微生物物质的INCI名称):甲醛和低聚甲醛,羟基联苯及其盐,例如邻苯基苯酚,双(2-巯基吡啶氧化)锌(zinc pyrithion),氯丁醇,羟基苯甲酸及其盐和酯,例如对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯,二溴六脒及其盐,包括异硫代硫酸盐(4,4’-六亚甲基二氧基-二(3-溴苯并脒)和4,4’-六亚甲基二氧基-二(3-溴苯并脒鎓-2-羟基乙磺酸盐),汞,(乙酰-O)苯基(特别是苯基乙酸汞)和汞盐(2-),(原硼酸盐(3-)-O)苯基,dihydrogene(特别是苯基硼酸汞),1,3-二(2-乙基己基)-六氢-5-甲基-5-嘧啶(Hexetidin),5-溴-5-硝基-1,3-二噁烷,2-溴-2-硝基-1,3-丙二醇,2,4-二氯苄基醇,3,4,4’-三氯-N-碳酰苯胺(Trichlorcarban),对氯间甲酚,2,4,4’-三氯-2-羟基二苯基醚(三氯羟基二苯醚),4,4’-二氯-2-羟基二苯基醚,4-氯-3,5-二甲基苯酚(Chloroxylenol),咪唑烷基脲,聚(六亚甲基双胍)盐酸盐,2-苯氧基乙醇(苯氧基乙醇),六亚甲基四胺(Methenamine),1-(3-氯烯丙基)-3,5,7-三氮杂-1-氮鎓金刚烷氯化物(Quaternium 15),1-(4-氯苯氧基)-1-(1-咪唑基)3,3-二甲基-2-丁酮(Climbazole),1,3-二(羟基甲基)-5,5-二甲基-2,4-咪唑烷二酮(DMDM乙内酰脲),苄基醇,1,2-二溴-2,4-二氰基丁烷,2,2’-亚甲基-二(6-溴-4-氯苯酚)(溴氯苯),甲基氯代异噻唑酮,甲基异噻唑酮,辛基异噻唑酮,苄基异噻唑酮,2-苄基-4-氯苯酚(氯苯酚),氯代乙酰胺,洗必太,乙酸洗必太,葡糖酸洗必太,洗必太盐酸盐,1-苯氧基-丙-2-醇(苯氧基异丙醇),4,4-二甲基-1,3-噁唑烷(二甲基噁唑烷),二偶氮烷基脲,4,4’-六亚甲基二氧基二苄脒和4,4’-六亚甲基二氧基二(苄脒鎓-2-羟基乙磺酸盐),戊二醛(1,5-戊二醛),7-乙基二环噁唑烷,3-(4-氯苯氧基)-1,2-丙二醇(chlorophenesin),苯基甲氧基甲醇和((苯基甲氧基)甲氧基)-甲醇(benzylhemiformal),N-烷基(C12-C22)三甲基溴化铵和氯化铵(十六烷基三甲基溴化铵,十六烷基三甲基氯化铵),苄基-二甲基-(4-(2-(4-(1,1,3,3-四甲基丁基)-苯氧基)-乙氧基)-乙基)-氯化铵(苄索氯铵),烷基(C8-C18)-二甲基苄基氯化铵、溴化铵和糖精盐(苯扎氯铵,苯扎溴铵,苯扎糖精铵),苯甲酸及其盐和酯,丙酸及其盐,水杨酸及其盐,山梨酸及其盐,碘酸钠,无机亚硫酸盐和亚硫酸氢盐,例如亚硫酸钠,脱氢乙酸,甲酸,(1-乙基)2-巯基苯甲酸汞盐(2-)-O,S-,hydrogene(硫柳汞或Thiomerosal),10-十一碳烯酸及其盐,吡啶酮氨基乙醇盐(吡啶酮乙醇胺盐),羟基甲基氨基乙酸钠(羟基甲基氨基乙酸钠),3-碘-2-丙炔基丁基氨基甲酸酯,10-十一碳烯酸,和硫。
也可以使用与天然抗微生物剂的组合或具有抗微生物活性的化学改性的天然物质,例如脱乙酰壳多糖以及脱乙酰壳多糖衍生物,法呢醇,植物提取物例如丁子香油、蓝柏油等。
下面给出洗发水/浴液配方的典型配方例子,它们能提供当从包装不同角度观察和在皮肤及头发上时具有光泽效果和从亮到暗/从暗到亮色彩或颜色之间变化的头发和/或身体清洁产品:
1)适量至100%;2)按照需要
下面给出头发凝胶配方的典型配方例子,它们能提供头发造型/固定产品,当从头发上和包装中不同角度观察时具有光泽效果和色彩从亮到暗/从暗到亮或颜色之间的变化:
1)适量至100%;2)按照需要
根据本发明的化妆和个人护理制剂和配方也可以以洗剂、乳剂、烛剂或皂的形式使用,它们由在化妆工业中常用的基础物质和本发明的颜料组成。
下面给出洗剂/乳剂的典型配方例子,它们能提供在包装中和皮肤上具有皮肤保湿、调理、舒缓效果以及发光效果和色彩从亮到暗/从暗到亮或颜色之间变化的效果:
1)适量至100%
下面给出烛剂的典型配方例子,它们能提供当从不同角度、有光或无光时的发光效果和色彩从亮到暗/从暗到亮或颜色之间变化的效果:
1)适量至100%
下面给出皂的典型配方例子,它们能提供清洁作用和当从在皂条上、手、面部和身体上以及在包装中不同角度观察时的发光效果和色彩从亮到暗/从暗到亮或颜色之间变化的效果:
1)适量至100%
本发明的化妆和个人护理制剂和配方按照常规方式制备,例如通过将各组分一起混合或搅拌,任选在加热下进行以使混合物熔化。
光泽颜料通常包含:
(a1)由基本透明或金属反射材料组成的芯,和
(a2)至少一层由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比是平均0.03-0.95。
这些着色的光泽颜料及其制备描述在EP-A-0 803 549中,将其引入本文供参考。
光泽颜料的平面-平行结构的颗粒(薄片)通常具有1微米至5毫米的长度、1微米至2毫米的宽度和20纳米至2微米的厚度,长度与厚度之比是至少2∶1,该颗粒具有两个基本平行的表面,其间的距离是芯的最短轴。
薄片不是均匀形状的。但是,为了简洁,在下面将称薄片具有“直径”。薄片具有高度平面平行性和在±10%范围内的确定厚度,特别是在±5%范围内的平均厚度。目前优选的是薄片的直径在约1-60微米的优选范围内,更优选约5-40微米。因此,本发明的薄片的纵横比优选约2.5-625,更优选约50-250。
术语“氧化硅层,其中氧与硅的摩尔比平均是0.03-0.95,即0.03≤x≤0.95的SiOx”表示在氧化硅层的平均值下氧与硅的摩尔比是0.03-0.95。氧化硅层的组成可以通过ESCA(化学分析用电子能谱法)测定。
因此,术语“0.95<z≤2.0的SiOz”表示在氧化硅层的平均值下氧与硅的摩尔比是0.95-2.0。氧化硅层的组成可以通过ESCA(化学分析用电子能谱法)测定。
根据本发明,术语“铝”包括铝和铝的合金。铝的合金例如描述在G.Wassermann,Ullmannsder IndustriellenChemie,4,Auflage,Verlag Chemie,Weinheim,Band 7,S.281-292。特别合适的是对腐蚀稳定的铝合金,描述在WO00/12634的第10-12页,除了铝之外,还包括小于20重量%、优选小于10重量%的硅、镁、锰、铜、锌、镍、钒、铅、锑、锡、镉、铋、钛、铬和/或铁。
光泽颜料优选具有以下层结构:
(a3)SiOz,特别是SiO2,
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,优选0.03-0.24,
(a1)由基本透明或金属反射材料组成的芯,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,优选0.03-0.24,
(a3)SiOz,特别是SiO2,
或者
(a4)由任何固体材料组成的涂层,其组成与涂层(a3)不同,
(a3)SiOz,特别是SiO2,
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,优选0.03-0.24,
(a1)由基本透明或金属反射材料组成的芯,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,优选0.03-0.24,
(a3)SiOz,特别是SiO2,
(a4)由任何固体材料组成的涂层,其组成与涂层(a3)不同,
其中0.95<z≤2.0,特别是1.4≤z≤2.0。
如果芯由金属反射材料组成,则该材料优选选自Ag、Al、Au、Cu、Cr、Ge、Mo、Ni、Si、Ti、Zn、它们的合金、石墨、Fe2O3和MoS2。特别优选Al。
如果芯由透明材料组成,则该材料优选选自云母、SiOz,特别是SiO2和SiOz/TiO2混合物。特别优选SiOz,其中0.95<z≤2.0,特别是1.4≤z≤2.0。
涂层(a4)的材料有利地是金属氧化物,例如TiO2、ZrO2、SiO、SiO2、SnO2、GeO2、ZnO、Al2O3、V2O5、Fe2O3、Cr2O3、PbTiO3或CuO,或它们的混合物。
涂层(a4)的材料优选是具有“高”折射指数的介电材料,也就是说,折射指数大于约1.65,优选大于约2.0,最优选大于约2.2,这适用于硅/氧化硅基材的整个表面。这种介电材料的例子是硫化锌(ZnS)、氧化锌(ZnO)、氧化锆(ZrO2)、二氧化钛(TiO2)、碳、氧化铟(In2O3)、氧化铟锡(ITO)、五氧化二钽(Ta2O5)、氧化铬(Cr2O3)、氧化铈(CeO2)、氧化钇(Y2O3)、氧化铕(Eu2O3),氧化铁,例如铁(II)/铁(III)氧化物(Fe3O4)和铁(III)氧化物(Fe2O3),氮化铪(HfN),碳化铪(HfC),氧化铪(HfO2),氧化镧(La2O3),氧化镁(MgO),氧化铌(Nd2O3),氧化镤(Pr6O11),氧化钐(Sm2O3),三氧化锑(Sb2O3),一氧化硅(SiO),三氧化硒(Se2O3),氧化锡(SnO2),三氧化钨(WO3)或它们的组合物。介电材料优选是金属氧化物,金属氧化物可以是一种氧化物或多种氧化物的混合物,其具有或不具有吸收性能,例如TiO2、ZrO2、Fe2O3、Fe3O4、Cr2O3或ZnO,其中特别优选TiO2和ZrO2。
通过在涂层(a4)之上、特别在TiO2层之上施用具有低折射指数的金属氧化物,例如SiO2、Al2O3、A1OOH、B2O3或它们的混合物,优选SiO2,可以获得颜色更强烈和更透明的颜料(WO93/08237)。
为了起到对于气候和光的稳定作用,可以按照本身公知的方式使用额外的涂层。
金属氧化物层优选通过湿化学方法施加,在本文中可以使用为了制备珠光颜料而开发的湿化学涂覆方法;这种技术例如描述在DE-A-1467 468、DE-A-19 59 988、DE-A-20 09 566、DE-A-22 14 545、DE-A-22 15 191、DE-A-22 44 298、DE-A-23 13 331、DE-A-25 22 572、DE-A-3137 808、DE-A-31 37 809、DE-A-31 51 343、DE-A-31 51 354、DE-A-31 51 355、DE-A-32 11 602和DE-A-32 35 017、DE 195 99 88、WO93/08237和WO 98/53001中,或在其它专利文件和出版物中。
为了涂覆,将基材颗粒悬浮在水中,并在适合于水解并选择使得金属氧化物和/或金属氧化物水合物直接沉淀到颗粒上而不会发生二次沉淀的pH下加入一种或多种可水解的金属盐。该pH通常通过同时计量加入碱或强碱来保持恒定。颜料然后被分离出来,洗涤和干燥,并在需要时进行煅烧,煅烧温度可以根据具体的涂层最优化。在需要时,可以在涂覆各涂层之后分离出颜料,干燥,和在需要时在再悬浮以通过沉淀涂覆其它层之前进行煅烧(参见US-A-6 132 873)。
在优选的实施方案中,光泽颜料具有以下层结构:SiOx/SiOz/SiOx,SiOz/SiOx/SiOz/SiOx/SiOz,特别是SiO2/SiOx/SiOz/SiOx/SiO2,SiOx/Al/SiOx,SiOz/SiOx/Al/SiOx/SiOz,特别是SiO2/SiOx/Al/SiOx/SiO2,TiO2/SiOz/SiOx/SiOz/SiOx/SiOz/TiO2,特别是TiO2/SiO2/SiOx/SiOz/SiOx/SiO2/TiO2或TiO2/SiOz/SiOx/Al/SiOx/SiOz/TiO2,特别是TiO2/SiO2/SiOx/Al/SiOx/SiO2/TiO2,其中x是0.03-0.95,0.95<z≤2.0,特别是1.4<z≤2.0。
含有以下层结构的光泽颜料是新颖的并且构成本发明的另一方面:
(a1)由SiOz组成的芯,其中0.95<z≤2.0,特别是1.4≤z≤2.0,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,特别是
光泽颜料具有以下层结构:
(a3)任选的SiO2涂层,
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,
(a1)由SiOz组成的芯,其中0.95<z≤2.0,特别是1.4≤z≤2.0,和
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,和
(a3)任选的SiO2涂层。
在本发明的这一方面,特别优选的光泽颜料具有以下层结构:
SiOx/SiOz/SiOx,SiOz/SiOx/SiOz/SiOx/SiOz,特别是SiO2/SiOx/SiOz/SiOx/SiO2,TiO2/SiOz/SiOx/SiOz/SiOx/SiOz/TiO2,特别是TiO2/SiO2/SiOx/SiOz/SiOx/SiO2/TiO2,其中z是0.95-2.0,特别是1.40-2.00,x是0.03-0.95,特别是0.05-0.50。
光泽颜料通常具有2微米至5毫米的长度、2微米至2毫米的宽度和20纳米至1.5微米的厚度,长度与厚度之比是至少2∶1,具有SiOz芯的颗粒具有两个基本平行的表面,其间的距离是芯的最短轴,和具有涂覆在这些平行面上的SiOx层和任选的其它层。其它层可以涂覆在平行面或整个表面上。
芯是具有1-50微米平均直径和20-500nm厚度的小片。
SiOx层的厚度通常是5-200nm,优选5-100nm。
SiOz层的厚度通常是1-200nm,优选2-100nm。
TiO2层的厚度通常是1-200nm,优选10-150nm。
另外,本发明还涉及光泽颜料,包含:
(a1)由金属反射材料组成的芯,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.24,特别是光泽颜料具有以下层结构:
(a3)任选的SiOz涂层,其中0.95<z≤2.0,特别是1.4≤z≤2.0,
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比是平均0.03-0.24,
(a1)由金属反射材料,特别是铝组成的芯,和
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比是平均0.03-0.24,和
(a3)任选的SiOz涂层,其中0.95<z≤2.0,特别是1.4≤z≤2.0,
这是新颖的,并构成本发明的另一方面。
在本发明的此方面中,特别优选的光泽颜料具有以下层结构:
SiOx1/Al/SiOx1,SiOz/SiOx1/Al/SiOx1/SiOz,特别是SiO2/SiOx1/Al/SiOx1/SiO2,和TiO2/SiOz/SiOx1/Al/SiOx1/SiOz/TiO2,特别是TiO2/SiO2/SiOx1/Al/SiOx1/SiO2/TiO2,其中x1是0.03-0.24,0.95<z≤2.0,优选1.4≤z≤2.0。
另外,本发明涉及具有以下层结构的光泽颜料:
(a3)SiOz涂层,其中0.95<z≤1.95,特别是1.4≤z≤1.80,
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比是平均0.03-0.95,
(a1)由金属反射材料,特别是铝组成的芯,和
(a2)基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比是平均0.03-0.95,和
(a3)SiOz涂层,其中0.95<z≤1.95,特别是1.40≤z≤1.80。
在本发明的此方面,特别优选的光泽颜料具有以下层结构:
SiOz1/SiOx/Al/SiOx/SiOz1,或TiO2/SiOz1/SiOx/Al/SiOx/SiOz1/TiO2,其中0.95<z1≤1.95,优选1.4≤z1≤1.8,x1是0.03-0.95,z1优选是≥1.0且≤1.8。
芯是具有1-50微米平均直径的小片,优选由铝组成。芯的厚度取决于所用的金属,在铝的情况下是20-100nm,特别是40-60nm。
SiOx层的厚度通常是5-200nm,优选5-100nm。
SiOz层的厚度通常是1-200nm,优选2-100nm。
TiO2层的厚度通常是1-200nm,优选10-150nm。
SiOx、SiOz、SiO2和TiO2层以相对于Al芯的镜面对称方式排列,或SiOz优选具有相同的层厚度。在本发明的另一个实施方案中,基材层可以在两面都被具有不同层厚度的金属氧化物包围。
为了对气候和光起稳定作用的目的,可以按照本身已知的方式使用额外的涂层。
例如,SiO2保护层可以涂在二氧化钛层的上面,可以使用以下方法:将苏打水玻璃溶液计量加入正被涂覆的材料悬浮液中,该悬浮液已经被加热到约50-100℃,特别是70-80℃。通过同时添加10%盐酸,使得pH保持在4-10,优选6.5-8.5。在加入水玻璃溶液之后,搅拌进行30分钟。
通过在化妆品中使用本发明的光泽颜料,可以获得颜色根据视角变化的化妆品(“转向效果(flop effect)”)。特别是,仅仅由硅和氧组成的不含TiO2涂层的光泽颜料由于不含重金属,特别适用于化妆应用。
通过包括以下步骤的方法获得SiOx/SiOy薄片,其中0.95<y≤1.8,优选1.0≤y≤1.5:
a)将分离剂气相沉积到(可移动的)载体上,得到分离剂层,
b)将SiOx层气相沉积到分离剂层上(0.03<x≤0.95),
c)将SiOy层(0.95<y≤1.8)气相沉积到步骤b)中得到的SiOx层上,
d)将SiOx层(0.03<x≤0.95)气相沉积到步骤c)中得到的SiOy层上,
e)将分离剂层溶解在溶剂中,
f)从溶剂中分离出光泽颜料,
步骤c)中的SiOy层是从装有含有Si和SiO2、SiOy或其混合物的进料的蒸发器中气相沉积的,和
SiOx层是从装有Si的蒸发器中气相沉积的。
上述方法使得与天然云母功能颜料以及在湿方法中生产的功能颜料相比,该光泽颜料具有高度的平面平行性和±10%范围内的确定厚度,优选在±5%范围内的平均厚度。
冷凝到载体上的分离剂可以是清漆、聚合物,例如US-B-6 398 999中描述的热塑性聚合物,溶于有机溶剂或水和可真空蒸发的有机物质,例如蒽,蒽醌,乙酰氨基苯酚,乙酰基水杨酸,樟脑酸酐,苯并咪唑,苯-1,2,4-三甲酸,联苯-2,2-二甲酸,二(4-羟基苯基)砜,二羟基蒽醌,乙内酰脲,3-羟基苯甲酸,8-羟基喹啉-5-磺酸一水合物,4-羟基香豆素,7-羟基香豆素,3-羟基萘-2-甲酸,间苯二甲酸,4,4-亚甲基-二-3-羟基萘-2-甲酸,萘-1,8-二甲酸酐,邻苯二甲酰胺及其钾盐,酚酞,吩噻嗪,糖精及其盐,四苯基甲烷,苯并[9,10]菲,三苯基甲醇,或至少两种这些物质的混合物。分离剂优选是可溶于水和可真空蒸发的元机盐(参见例如DE 198 44 357),例如氯化钠,氯化钾,氯化锂,氟化钠,氟化钾,氟化锂,氟化钙,氟化铝钠和四硼酸二钠。
SiOy层是通过将细硅和石英(SiO2)粉末的优选化学计量混合物在蒸发器中在高真空下加热到超过1300℃来获得,例如描述在DE4342574 C1和US 6 202 591中。反应产物是一氧化硅气体,其在真空下直接定向在通过的载体上,作为SiO冷凝下来。也可以使用非化学计量的混合物。蒸发器装有的进料含有Si和SiO2的混合物、SiOy或它们的混合物,彼此反应的物质(Si和SiO2)的粒度有利地是小于0.3mm。Si与SiO2的重量比有利地是0.15∶1到0.75∶1(重量份);优选存在化学计量的混合物。在蒸发器中存在的SiOy直接蒸发。Si与SiO2在超过1300℃的温度下反应形成一氧化硅蒸气。
根据本发明,步骤e)在高于步骤a)-d)的压力和低于大气压的压力下进行。
(可移动的)载体优选包括一种或多种连续的金属带,具有或不具有聚合物涂层,或一种或多种聚酰亚胺或聚对苯二甲酸乙二酯带。(可移动的)载体还可包括一种或多种盘、圆柱或其它旋转对称的物体,它们围绕轴旋转。
光泽颜料优选通过洗出和随后过滤、沉淀、离心、滗析或蒸发而从分离剂的溶液中分离出来。此外,在洗出溶剂中所含的溶解的分离剂之后,光泽颜料可以与溶剂一起冷冻,并随后进行冷冻干燥工艺,此时由于低于三相点的升华而分离出溶剂,并且干燥产物以单独的平面平行结构保留下来。
从蒸发的SiO开始冷凝在可移动载体上的一氧化硅对应于式SiOy,其中0.95<y≤1.8,优选1.1≤y≤1.5,小于1的y值是通过在蒸发器材料中的过量硅获得的。除了在超高真空下之外,在数个10-2Pa的工业真空中蒸发的SiO总是作为SiOy冷凝,其中1≤y≤1.8,特别是1.1≤y≤1.5,这是因为高真空设备总是由于从表面释放的气体而含有痕量的水蒸气,它与易于反应的SiO在蒸发温度下反应。SiOy层可以通过氧化热处理转变成SiOy+a层,其中0.05≤a≤1.05。
如果在数个10-2Pa的工业真空中蒸发,Si被蒸发而不是SiO,获得的氧化硅具有小于等摩尔氧的含量,即SiOx,其中0.03≤x≤0.95,特别是0.05≤x≤0.50,更特别是0.10≤x≤0.30,其具有特别高的氧化稳定性以及高折射指数,即使在薄层中也是如此。在氧气存在下在150-500℃、优选175-300℃下加热出乎意料地得到非常薄的,例如约20nm厚的表面二氧化硅层,这表示一种生产具有层顺序SiO2/SiOx/SiOz/SiOx/SiO2的结构的非常方便的方法,其中0.95<z≤2.0,特别是1.40≤z≤2.0。如果希望获得较厚的二氧化硅层,则可以方便地通过例如上述SiOy的蒸气沉积和氧化热处理来制备。
详细地说,盐例如NaCl在SiOx和SiOy层之后被连续地蒸气沉积在载体上,该载体可以是连续的金属带,经过在小于0.5Pa真空下的蒸发器,盐的蒸气沉积厚度是约20-100nm,优选30-60nm。在其进一步的过程中,闭合形成环的带形载体经过具有公知结构模式的动态真空封闭室(参见US 6 270 840)进入1-5×104Pa压力、优选600-109Pa压力和特别是103-5×103Pa压力的区域,在那里浸入溶解浴中。溶剂的温度,在盐的情况下是水的温度,应该选择使得其蒸气压在所规定的压力范围内。在机械协助下,分离剂层快速地溶解,产物层破裂成薄片,然后以悬浮液的形式存在于溶剂中。在其进一步的过程中,带被干燥,不含任何与其粘附的污染物。它经过第二组动态真空封闭室返回蒸发室,在那里重复进行用分离剂和产物层涂覆的工艺。
在这两种情况下存在的、包含产物结构和溶剂以及溶解在其中的分离剂的悬浮液然后在另一个操作中按照公知的技术分离。为此,产物结构首先在液体中浓缩,用新鲜溶剂洗涤几次以便洗出溶解的分离剂。产物是仍然湿的固体形式,然后通过过滤、沉淀、离心、滗析或蒸发分离。
在干燥之后,产物、即SiOy层可以进行氧化热处理。公知的方法可以用于此目的。空气或一些其它含氧气体通过平面平行结构,其可以是松散材料的形式或流化床的形式,在超过200℃、优选超过400℃和特别是500-1000℃的温度下进行几小时。产物然后通过研磨或空气筛分达到所希望的粒度,并输送用于其他用途。
在大气压下洗出之后对平面平行结构的分离可以在温和条件下通过冷冻悬浮液进行,该悬浮液已经被浓缩到固含量为约50%,按照公知的方式在约-10℃和50Pa压力下进行冷冻干燥。干燥物质作为产物留下,其可以通过涂覆或化学转化进行进一步加工的步骤。
代替使用连续带,可以通过在具有旋转体的设备中进行分离剂和SiO的蒸气沉积、溶解和干燥载体步骤来生产产品,参见DE-A-199 52032。旋转体可以是一个或多个盘、圆柱或任何其它旋转对称物体。
上述方法使得可以生产具有高生产率、良好稳定性能且以具有良好色饱和度和遮盖力的色调为特征的光泽颜料。
根据本发明方法生产的光泽颜料具有高度的色纯度和光泽,并且是高度剪切稳定的。从载体中溶解出来的颜料小片具有相对于彼此基本相同的和可重现的光学性能,例如从特定角度观察时相同的色调,这是因为各层的厚度可以得到控制。
具有TiO2的任选涂层可以得到更强烈的颜色,优选通过湿化学方法沉淀涂覆。
二氧化钛层可以例如与DE-A-195 01 307描述的方法类似地获得,其中通过控制水解一种或多种钛酸酯来生产二氧化钛层,在适宜时在有机溶剂和碱性催化剂存在下通过溶胶-凝胶方法进行。合适的碱性催化剂是例如胺,例如三乙胺、乙二胺、三丁胺、二甲基乙醇胺和甲氧基丙胺。
有机溶剂是水混溶性有机溶剂,例如C1-4醇,特别是异丙醇。
合适的钛酸酯选自钛的烷基和芳基醇盐、羧酸盐和羧基-或烷基-或芳基-取代的烷基醇盐或羧酸盐。钛酸四异丙酯的使用是优选的。另外,可以使用钛的乙酰丙酮酸盐和乙酰乙酰丙酮酸盐,例如乙酰丙酮酸钛。
根据本发明的一个实施方案,US-A-3 553 001中描述的方法用于涂覆二氧化钛层。
钛盐水溶液被缓慢加入被涂覆的材料的悬浮液中,该悬浮液已经被加热到约50-100℃,特别是70-80℃,并且基本恒定的约为0.5-5、特别是约1.2-2.5的pH值通过同时计量添加碱例如氨水溶液或碱金属氢氧化物水溶液来保持。一旦达到所需层厚度的沉淀TiO2,马上停止添加钛盐溶液和碱。
该方法也称为滴定方法,特征在于避免了过量的钛盐。这通过在单位时间内仅仅加入水解所需的量来实现,该量对于用水合的TiO2均匀涂覆是必须的,并且该量在单位时间内可以被正在被涂覆的颗粒表面所吸收。一般,锐钛矿形式的TiO2在初始颜料的表面上形成。但是,通过加入少量的SnO2,可以强制形成金红石结构。例如,如WO 93/08237所述,二氧化锡可以在二氧化钛沉积之前沉积,锐钛矿形式的TiO2可以通过在800-900℃煅烧被转化成金红石形式的TiO2。
在合适时,SiO2保护层可以涂覆在二氧化钛层之上,可以使用以下方法:将苏打水玻璃溶液计量加入正被涂覆的材料悬浮液中,该悬浮液已经被加热到约50-100℃,特别是70-80℃。通过同时添加10%盐酸,使得pH保持在4-10,优选6.5-8.5。在加入水玻璃溶液之后,搅拌进行30分钟。
通过在TiO2层之上涂覆具有低折射指数的金属氧化物,例如SiO2、Al2O3、AlOOH、B2O3或它们的混合物,优选SiO2,并在后一层上再涂覆另一层TiO2,可以获得颜色更强烈和更透明的颜料。
还可以将最终的颜料进行随后的涂覆或随后的处理,进一步增加对光、气候和化学品的稳定性或促进颜料可加工性,特别是将其引入各种介质中。例如,在DE-A-22 15 191、DE-A-31 51 354、DE-A-32 35017或DE-A-33 34 598中描述的方法适合作为随后的处理或随后的涂覆。
根据本发明的光泽颜料颗粒可以在适宜时被引入聚合物中,例如通过在许多调色剂颗粒应用中本身公知的乳液聚合方式获得,或通过引入到热塑性塑料或聚合物分散液或溶液中获得。
根据本发明的光泽颜料可以用于所有常规目的,例如用于在物体、表面涂层(包括功能修饰,包括用于汽车部件的那些)和印刷油墨中的着色聚合物,和例如用于化妆品。这些应用从参考文献中已经知道,例如“Industrial Organic Pigments”(W.Herbst andK.Hunger,VCH Verlagsgesellschaft mbH,Weinheim/纽约,第2版,完全修改版,1997)。
根据本发明的光泽颜料(功能颜料)显示角色差性能(“色移动”,即根据入射光和视角产生不同颜色)和导致明亮的、高度饱和(鲜艳)的颜色。它们因此非常适合于与常规的透明颜料组合,例如有机颜料,例如二酮基吡咯并吡咯,喹吖啶、二噁嗪,苝,异吲哚酮等,透明颜料可以具有与功能颜料相似的颜色。但是,与例如EP 388 932或EP 402943相似,当透明颜料和功能颜料的颜色互补时,获得特别有趣的组合效果。
根据本发明的光泽颜料可以用于着色高分子量有机材料,获得优异的结果。
可以使用本发明的光泽颜料或颜料组合物着色的高分子量有机材料可以是天然或合成来源的。高分子量有机材料通常具有约103-108g/mol或更高的分子量。它们可以例如是天然树脂,干燥油,橡胶或酪蛋白,或由其衍生的天然物质,例如氯化橡胶、油改性的醇酸树脂,粘胶纤维,纤维素醚或酯,例如乙基纤维素、乙酸纤维素、丙酸纤维素、乙酰丁酸纤维素或硝基纤维素,但是特别是全部合成的有机聚合物(热固性热塑性和热塑性塑料),通过聚合、缩聚或加聚获得。从聚合树脂的种类来说,特别可以提到聚烯烃,例如聚乙烯、聚丙烯或聚异丁烯,以及取代的聚烯烃,例如氯乙烯、乙酸乙烯酯、苯乙烯、丙烯腈、丙烯酸酯、甲基丙烯酸酯或丁二烯的聚合产物,以及所述单体的共聚产物,例如特别是ABS或EVA。
从加聚树脂和缩聚树脂系列来说,可以提到例如甲醛和酚类的缩聚产物,所谓的酚醛塑料,以及甲醛与脲、硫脲或蜜胺的缩合产物,所谓的氨基塑料,和用作表面涂料树脂的聚酯,其是饱和的,例如醇酸树脂,或是不饱和的,例如马来酸酯树脂;以及线性聚酯和聚酰胺、聚氨酯或聚硅氧烷。
所述高分子量化合物可以以塑性物质或熔体的形式单独存在或作为混合物存在。它们还可以以单体的形式或溶解形式的聚合状态存在,作为成膜剂或粘合剂,用于表面涂料或印刷油墨,例如沸腾亚麻子油、硝基纤维素、醇酸树脂、蜜胺树脂和脲醛树脂或丙烯酸树脂。
根据预期目的,已经证明有利的是使用根据本发明的光泽颜料或光泽颜料组合物作为调色剂或是制剂的形式。根据调节方法或预期应用,可以有利地在调节工艺之前或之后向功能颜料中加入一定量的纹理改进剂,前提是它对功能颜料用于着色高分子量有机材料、特别是聚乙烯没有不良影响。合适的试剂特别是含有至少18个碳原子的脂肪酸,例如硬脂酸或山萮酸,或酰胺或其金属盐,特别是镁盐,以及增塑剂、蜡、树脂酸例如松香酸,松香皂,烷基酚;或脂肪醇,例如硬脂醇;或含有8-22个碳原子的1,2-二羟基化合物,例如1,2-十二烷二醇,以及改性的松香马来酸酯树脂或富马酸松香树脂。质地改进剂的添加量优选是0.1-30重量%,特别是2-15重量%,基于最终产物计。
根据本发明的光泽颜料可以以任何着色有效量加入正在被染色的高分子量有机材料中。含有高分子量有机材料和基于高分子量有机材料计0.01-80重量%、优选0.1-30重量%本发明功能颜料的着色组合物是有利的。通常在实践中可以使用1-20重量%、特别是约10重量%的浓度。高浓度、例如高于30重量%通常是浓缩物的形式(“母料”),可以用作用于生产具有较低颜料含量的着色材料的着色剂,在常规配方中本发明的颜料具有特别低的粘度,使得它们仍然能良好地加工。
为了着色有机材料,本发明的功能颜料可以单独使用。但是,为了实现不同的色调或颜色效果,除了本发明的功能颜料之外,也可以向高分子量有机物质中加入任何所需量的其它赋予颜色的成分,例如白色、彩色、黑色或功能颜料。当着色的颜料与本发明功能颜料混合使用时,总量优选是0.1-10重量%,基于高分子量有机材料计。特别高的角色差是通过本发明功能颜料与其它颜色(特别是互补颜色)的彩色颜料的优选组合来提供的,其中使用功能颜料获得的着色和使用彩色颜料获得的着色在10°测量角下在色调上的差别(ΔH*)是20-340,特别是150-210。
优选,本发明的光泽颜料与透明彩色颜料组合,透明彩色颜料可以与本发明的功能颜料存在于相同的介质中,或存在于相邻的介质中。其中功能颜料与彩色颜料有利地存在于相邻介质中的排列的例子是多层功能表面涂层。
用本发明颜料着色高分子量有机物质的操作例如通过将这种颜料(在合适时以母料的形式)与基材用辊炼机或混合或研磨设备进行混合来进行。着色的材料然后使用本身公知的方法,例如压延、压缩模塑、挤出、涂覆、灌塑或注塑形成所需的最终形式。任何在塑料工业中常用的添加剂例如增塑剂、填料或稳定剂可以按照常规用量在引入颜料之前或之后加入聚合物中。特别是,为了生产非硬质的成型产品或降低它们的脆性,希望在成型之前向高分子量化合物中加入增塑剂,例如磷酸、邻苯二甲酸或癸二酸的酯。
为了着色表面涂料和印刷油墨,高分子量有机材料和本发明的光泽颜料在合适时与常规添加剂例如填料、其它颜料、干燥剂或增塑剂一起细分散或溶解在相同的有机溶剂或溶剂混合物中,各组分可以单独溶解或分散或者许多组分一起溶解或分散,和仅仅在这之后将全部组分放在一起。
本发明功能颜料在正在被着色的高分子量有机材料中的分散以及本发明颜料组合物的加工优选在仅仅出现较弱剪切力的条件下进行,使得功能颜料不会分成更小的级分。
例如在塑料、表面涂料或印刷油墨,特别是在表面涂料或印刷油墨,更特别是在表面涂料中获得的着色的优点是具有优异的性能,特别是极高的饱和度、出色的牢固性能和高的角色差。
当正在被着色的高分子量有机材料是表面涂料时,它特别是专业表面涂料,尤其是汽车修饰涂料。
以下实施例仅仅用于说明的目的,不能理解为以任何方式限制本发明的范围。除非另有说明,百分比和份数都以重量计。
实施例1
将约50nm的NaCl层在真空室中在低于约10-2Pa的压力下蒸气沉积在金属载体上。然后,在相同的压力下,以下材料依次进行蒸气沉积:Si(高于1850℃)、SiO(1350-1550℃)和Si(高于1850℃),从而在金属带上得到具有以下层结构的膜:SiOx/SiO/SiOx。
然后将分离剂溶解在水中,此时薄片从基材中分离出来。在大气压下,所得的悬浮液进行过滤浓缩,用去离子水洗涤数次以除去存在的Na+和Cl-离子。然后进行干燥,任选地在200℃在烘箱中将松散材料形式的平面平行SiOx结构体加热2小时,在烘箱中通过被加热到200℃的空气。在加热小片时,在表面上、在SiOx层上形成约20nm厚的SiO2层。在冷却之后,进行研磨和通过空气筛分分级。
根据上述方法,获得下表中表示的产品:
当视角变化时,根据实施例1获得的颜料显示颜色变化。
在镜面状钢带上升华的颜料具有SiOx(45nm)/SiOy(280nm)/SiOx(45nm)的层序列,其中x是0.3,y是0.95-1.2,下表显示L/C/h值(标准明度D65;CIE 31颜色坐标)对视角的依赖性。
视角(°) | L | C | H |
10 | 69 | 59.3 | 343 |
20 | 71.8 | 50.5 | 351 |
30 | 76.6 | 38.5 | 13 |
40 | 81 | 32.8 | 55.6 |
50 | 83.6 | 42.9 | 89.1 |
60 | 85.2 | 45 | 102.7 |
实施例2
唇膏基料具有以下组成:
将物质8-10一起混合,将物质13和14分散在所得的混合物中。所得的糊料然后通过三辊设备数次。同时,物质1-6进行熔化、一起搅拌,直到均匀,然后搅拌加入物质7、11和12。两种混合物然后一起趁热混合,直到实现均匀的分布。热物质然后倒入唇膏模具中,使其冷却。获得的唇膏具有出色光稳定性的强烈色彩和非常好的光泽,没有显示色料扩散。
实施例3
指甲油
指甲油具有例如以下配方[%]:
乙酸甲酯 | 8.0 |
乙酸乙酯 | 8.0 |
乙酸丙酯 | 12.0 |
乙酸丁酯 | 25.0 |
聚酯树脂 | 7.5 |
硝基纤维素/异丙醇 | 21.0 |
甲苯磺酰胺环氧树脂 | 9.0 |
樟脑 | 1.5 |
邻苯二甲酸二丁酯 | 5.0 |
司拉氯铵水辉石 | 1.0 |
二氧化钛 | 0.6 |
根据实施例1a的颜料 | 1.2 |
氧氯化铋 | 0.2 |
实施例4
唇膏具有以下组成:
将相A的组分进行组合,在90-105℃加热,混合直到均匀。相B的组分然后在搅拌的同时加入直到均匀。在唇膏倒入模具时温度保持在70℃以上。
实施例5
无滑石的疏松面部用粉末具有以下组成:
所有组分在共混机中组合并混合良好。
实施例7
水包油型面部用粉底具有以下组成:
相 | 组分 | 商品名 | 份数 |
A | 去离子水 | 水 | 60.24 |
A | 10%KOH溶液 | 10%KOH溶液 | 1.30 |
A | PEG-12聚二甲基硅氧烷 | DC 193表面活性剂<sup>10)</sup> | 0.10 |
A | 根据实施例1a、1b、1c、1d或1e的颜料 | 5.00 | |
A | 滑石 | Talc<sup>11)</sup> | 0.72 |
B | 1,3-丁二醇 | Jeechem BUGL<sup>12)</sup> | 4.00 |
C | 1,3-丁二醇 | Jeechem BUGL<sup>12)</sup> | 2.00 |
C | Veegum Plus<sup>13)</sup> | 0.12 | |
C | 对羟基苯甲酸甲酯 | Nipagin M<sup>5)</sup> | 0.02 |
D | 对羟基苯甲酸丙酯 | Nipasol M<sup>5)</sup> | 0.10 |
D | 二-PPG-3肉豆蔻基醚己二酸酯 | Cromollient DP3-A<sup>14)</sup> | 14.00 |
D | 马来酸二乙基己基酯 | Pelemol DOM<sup>15)</sup> | 4.00 |
D | 硬脂基醚-10 | Lipocol S-10<sup>1)</sup> | 2.00 |
将相A的组分进行组合,开始加热到80℃。加入相B和C的组分,均化1小时。在另一个烧瓶中组合相D的组分并加热到80℃。在相D中的所有组分均匀之后,将其缓慢加入主要混合物中,同时继续均化。在完成添加相D时,将配方在80℃均化15分钟,然后冷却到50℃,并加入相E。
实施例8
粉末眼影具有以下组成:
所有组分组合并良好地混合,加热到100℃,和在2000psi下压制。
实施例9
指甲油具有以下组成:
相A的组分进行组合,混合直到均匀。相B的组分在另一个容器中组合,混合直到均匀。在搅拌下将相B加入相A,直到均匀。
实施例10
唇彩具有以下组成:
相 | 组分 | 商品名 | 份数 |
A | 根据实施例1a、1b、1c、1d或1e的颜料 | 5.15 | |
B | C<sub>24-30</sub>醇 | Performacol 425<sup>20)</sup> | 1.75 |
B | 巴西棕榈蜡 | 巴西棕榈蜡<sup>3)</sup> | 1.70 |
B | 微晶蜡 | 微晶蜡1275<sup>21)</sup> | 4.00 |
B | 三异硬脂基聚甘油-3二聚体二亚油酸酯 | Schercemol PTID<sup>2)</sup> | 43.30 |
B | 柠檬酸三异硬脂基酯 | Schercemol TISC<sup>2)</sup> | 38.40 |
B | PE/PVA共聚物大豆甘油酯 | Enviropur 301<sup>22)</sup> | 5.00 |
B | 对羟基苯甲酸甲酯 | 对羟基苯甲酸甲酯<sup>23)</sup> | 0.20 |
B | 对羟基苯甲酸丙酯 | 对羟基苯甲酸丙酯<sup>23)</sup> | 0.10 |
B | 生育酚 | 生育酚<sup>24)</sup> | 0.10 |
C | 食用香料 | 食用香料<sup>25)</sup> | 0.30 |
100.00 |
将相B的组分进行组合,在85-87℃加热,混合直到均匀。相A的组分然后在搅拌下加入,直到均匀。温度降低到70-72℃,加入相C的组分。
实施例11
压粉具有以下组成:
对相A的组分进行混合,在混合下缓慢加入相B的组分。
实施例12
乳油至粉末胭脂具有以下组成:
将相A的组分在均化器中混合,并加热到70-75℃。将相B的组分进行组合并混合直到均匀。将相B加入相A中,温度保持在70-75℃,同时混合30分钟。将该混合物倒入容器中。
实施例13
防水睫毛油具有以下组成:
将相A和相B的组分各自混合,并加热到85℃。保持温度,将相B加入相A中,将该混合物均化直到均匀。将相C的组分加入相A和B的混合物中,混合直到均匀。继续混合,并加入相D的组分。
供应商:
1)Lipo Chemicals,Inc.;2)Scher Chemicals,Inc.;3)Ross Wax;4)Rita;5)Clariant AG;6)Ciba SC;7)Brooks Industries,Inc.;8)Presperse,Inc.;9)International Speclalty Products(ISP);10)Dow Corning;11)Whittaker,Clark and Daniels,Inc;12)Jeen International,13)R.T.Vanderbilt Co.,Inc.;14)Croda International;15)Phoenlx Chemical Inc.,16)Mclntyre Group Ltd.;16)Witco Corp.;17)Whittaker,Clark&Daniels;18)Engelhard Corp.;19)Telechemlsche,Inc.;20)New Phase Technology;21)Strahl and Pitsch Inc.;22)React Inc;23)Protameen Chemicals;24)Roche Vltamins;25)Atlanta Fragrance;26)Warner Jenkinson Cosmetic Colors;27)BASF AG;28)CP Kelco;29)Cognis AG.
Claims (4)
1.化妆和个人护理制剂,包含基于化妆制剂或配方的总重量计:
(a)0.0001-90重量%的光泽颜料,该光泽颜料含有:
(a1)由透明材料组成的芯,其中所述透明材料选自云母、SiOz和SiOz/TiO2混合物,其中0.95<z≤2.0,和
(a2)至少一层基本由一种或多种氧化硅组成的涂层,其中氧与硅的摩尔比平均是0.03-0.95,和
(b)10-99.9999%的化妆适宜的载体材料。
2.权利要求1的制剂,其中光泽颜料具有以下层结构:SiO2/SiOx/SiOz/SiOx/SiO2或TiO2/SiO2/SiOx/SiOz/SiOx/SiO2/TiO2,其中x是0.03-0.90,0.95<z≤2.0。
3.权利要求2的制剂,其中x是0.05-0.5。
4.权利要求2的制剂,其中1.4≤z≤2.0。
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EP03405024 | 2003-01-22 | ||
PCT/EP2003/009269 WO2004020530A1 (en) | 2002-08-30 | 2003-08-21 | Coloured gloss pigments having at least one coating of siox, with x=0.03 to 0.95 for use in cosmetic and personal care formulations |
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2003
- 2003-08-21 EP EP03747920A patent/EP1532211A1/en not_active Withdrawn
- 2003-08-21 WO PCT/EP2003/009269 patent/WO2004020530A1/en active Application Filing
- 2003-08-21 AU AU2003267003A patent/AU2003267003A1/en not_active Abandoned
- 2003-08-21 US US10/524,457 patent/US20060165620A1/en not_active Abandoned
- 2003-08-21 MX MXPA05002191A patent/MXPA05002191A/es active IP Right Grant
- 2003-08-21 BR BR0313832-1A patent/BR0313832A/pt not_active IP Right Cessation
- 2003-08-21 JP JP2004532103A patent/JP4478021B2/ja not_active Expired - Lifetime
- 2003-08-21 CN CN038204231A patent/CN1678694B/zh not_active Expired - Fee Related
- 2003-08-21 KR KR1020057003460A patent/KR20050057036A/ko active IP Right Grant
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WO2002010290A1 (en) * | 2000-07-27 | 2002-02-07 | Flex Products, Inc. | Composite reflective flake based pigments, method for their preparation and colorant comprising them |
Also Published As
Publication number | Publication date |
---|---|
AU2003267003A1 (en) | 2004-03-19 |
JP2005536562A (ja) | 2005-12-02 |
MXPA05002191A (es) | 2005-06-08 |
JP4478021B2 (ja) | 2010-06-09 |
WO2004020530A1 (en) | 2004-03-11 |
BR0313832A (pt) | 2005-07-05 |
KR20050057036A (ko) | 2005-06-16 |
EP1532211A1 (en) | 2005-05-25 |
US20060165620A1 (en) | 2006-07-27 |
CN1678694A (zh) | 2005-10-05 |
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