CN102639649B - 表面改性的颜料 - Google Patents
表面改性的颜料 Download PDFInfo
- Publication number
- CN102639649B CN102639649B CN200980161297.7A CN200980161297A CN102639649B CN 102639649 B CN102639649 B CN 102639649B CN 200980161297 A CN200980161297 A CN 200980161297A CN 102639649 B CN102639649 B CN 102639649B
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- CN
- China
- Prior art keywords
- composition
- quaternary ammonium
- pigments
- granules
- polyquaternary amine
- 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.)
- Expired - Fee Related
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- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/021—Calcium carbonates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- C09C1/04—Compounds of zinc
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
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- C—CHEMISTRY; METALLURGY
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
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- C09C1/3676—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/402—Satin white, modifications thereof, e.g. carbonated or silicated; Calcium sulfoaluminates; Mixtures thereof, e.g. with calcium carbonate or kaolin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
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- C—CHEMISTRY; METALLURGY
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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Landscapes
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- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dermatology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Cosmetics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
一种组合物,其包含用阳离子材料和三异硬脂酸异丙氧钛盐涂布的颜料颗粒。该颜料颗粒可包括在用于在表面比如皮肤上沉积的清洁组合物中。
Description
发明背景
需要以消费者可感觉其皮肤容光焕发、光滑和/或有光泽这样的方式增大皮肤光亮度。这些特性经消费者评定得到评价。皮肤光亮度也与皮肤光泽测量有关。尽管可通过使用沉积可增加光泽的颜料的驻留产品(leave on product)赋予皮肤光亮度,期望能够通过使用包括颜料的清洁组合物增大光泽。
对于使用清洁组合物的问题是组合物通过自皮肤清除油脂和污垢实施其清洁功能。为了有效,颜料需要改性以粘附于皮肤以避免经清洁组合物洗掉。
期望产生可自清洁组合物传递的可粘附于皮肤的颜料。
发明概述
组合物,其包含用阳离子材料和三异硬脂酸异丙氧钛盐涂布的颜料颗粒。以及增大基底上光泽的方法,其包含对基底施用组合物。
详细描述
如自始至终所使用的那样,范围用作描述处于所述范围内的每个和全部数值的缩略法。处于范围内的任何数值可选择作为所述范围的端点。另外,本文所引用的所有参考文献据此通过引用以其全部结合。在本公开和所引用参考文献的定义中如果发生冲突,本公开为准。
除非另外详细说明,本处和说明书的别处表示的所有百分数和量应理解为指%(重量)。所给予的量为基于材料的有效重量。
本发明涉及用阳离子材料和三异硬脂酸异丙氧钛盐(isopropyltitanium triisostearate)涂布的颜料颗粒。
颜料颗粒可为赋予光泽的任何颗粒。颜料颗粒的实例包括(但不限于)云母/二氧化钛、云母/氧化铁、云母、二氧化钛、氧化锌、氧化铁、氧化铬、硅石、滑石、高岭土及其组合。在一个实施方案中,颜料颗粒为云母/二氧化钛。可选择粒度为提供可测量的光泽的任何大小。颗粒的粒度为在用阳离子材料或任何其它涂料涂布之前的大小。在一个实施方案中,粒度为1-1000微米。在其它的实施方案中,粒度为至少10、20、30、40、50、60、60、80、90、100或150微米。在其它的实施方案中,粒度至高达100、150、250、300、350、400、450、500、600、700、800、900或1000微米。任何前述最小量可与任何最大量组合形成范围。在一个实施方案中,粒度为50-100微米。
阳离子材料可为具有阳离子电荷的任何材料。在一些实施方案中,阳离子材料为选自INCI季铵(Quaternium)系列的阳离子材料。在一些实施方案中,阳离子材料为阳离子聚合物。在某些实施方案中,阳离子材料选自INCI聚季铵(Polyquaternium)系列。聚季铵和季铵系列材料的实例包括(但不限于)聚季铵-1、聚季铵-2、聚季铵-4、聚季铵-5、聚季铵-6、聚季铵-7、聚季铵-8、聚季铵-9、聚季铵-10、聚季铵-11、聚季铵-12、聚季铵-13、聚季铵-14、聚季铵-15、聚季铵-16、聚季铵-17、聚季铵-18、聚季铵-19、聚季铵-20、聚季铵-22、聚季铵-24、聚季铵-27、聚季铵-28、聚季铵-29、聚季铵-30、聚季铵-31、聚季铵-32、聚季铵-33、聚季铵-34、聚季铵-35、聚季铵-36、聚季铵-37、聚季铵-39、聚季铵-42、聚季铵-43、聚季铵-44、聚季铵-45、聚季铵-46、聚季铵-47、聚季铵-48、聚季铵-49、聚季铵-50、聚季铵-51、聚季铵-52、聚季铵-53、聚季铵-54、聚季铵-55、聚季铵-56、聚季铵-57、聚季铵-58、聚季铵-59、聚季铵-60、聚季铵-61、聚季铵-62、聚季铵-63、聚季铵-64、聚季铵-65、聚季铵-66、聚季铵-67、聚季铵-68、聚季铵-69、聚季铵-70、聚季铵-71、聚季铵-72、聚季铵-73、聚季铵-74、聚季铵-75、聚季铵-76、聚季铵-77、聚季铵-78、聚季铵-79、聚季铵-80、聚季铵-81、聚季铵-82、聚季铵-83、聚季铵-84、聚季铵-85、聚季铵-86、聚季铵-87、聚季铵-88、聚季铵-90、聚季铵-93、聚季铵-94、聚季铵-4/羟丙基淀粉共聚物、季铵-8、季铵-14、季铵-15、季铵-16、季铵-18、季铵-18膨润土、季铵-18/苄烷铵膨润土、季铵-18锂蒙脱石、季铵-18甲基硫酸盐、季铵-22、季铵-24、季铵-26、季铵-27、季铵-30、季铵-33、季铵-43、季铵-45、季铵-51、季铵-52、季铵-53、季铵-56、季铵-60、季铵-61、季铵-63、季铵-70、季铵-71、季铵-72、季铵-73、季铵-75、季铵-76水解胶原、季铵-77、季铵-78、季铵-79水解胶原、季铵-79水解角蛋白、季铵-79水解乳蛋白、季铵-79水解蚕丝、季铵-79水解大豆蛋白、季铵-79水解小麦蛋白、季铵-80、季铵-81、季铵-82、季铵-83、季铵-84、季铵-85、季铵-86、季铵-87、季铵-88、季铵-89、季铵-90、季铵-90膨润土、季铵-91、季铵-92、季铵-93、有机硅季铵-1、有机硅季铵-2、有机硅季铵-2泛醇琥珀酸酯、有机硅季铵-3、有机硅季铵-4、有机硅季铵-5、有机硅季铵-6、有机硅季铵-7、有机硅季铵-8、有机硅季铵-9、有机硅季铵-10、有机硅季铵-11、有机硅季铵-12、有机硅季铵-15、有机硅季铵-16、有机硅季铵-16/环氧丙氧基聚二甲基硅氧烷交联聚合物、有机硅季铵-17、有机硅季铵-18、有机硅季铵-19、有机硅季铵-20、有机硅季铵-21、有机硅季铵-22、有机硅季铵-24、PEG-2椰油酰基季铵-4、PEG-15椰油酰基季铵-4、PEG-2油烯基季铵-4、PEG-15油烯基季铵-4、PEG-2硬脂基季铵-4、PEG-15硬脂基季铵-4、聚二甲基氨基丙基甲基丙烯酰胺甲基氯化季铵。
在一个实施方案中,阳离子材料为聚季铵-67,其为与三甲基铵取代的环氧化物和十二烷基二甲基铵(二甲基十二烷基)取代的环氧化物反应的羟乙基纤维素的聚合季铵盐的通用INCI名称。聚季铵-67可以SoftCAT商品名得自Dow Chemical Company的Amerchol子公司。在一个实施方案中,聚季铵-67为SoftCAT SK-MH。
在其它的实施方案中,阳离子材料为阳离子聚合物。在本申请中,表达方式“阳离子聚合物”表明含有阳离子基团或其可电离为阳离子基团的基团的聚合物。在某些实施方案中,阳离子聚合物选自含有包含伯、仲、叔和/或季胺基团的单元的那些聚合物,这些胺基团可形成聚合物链的部分或者可由侧链取代基携带。在某些实施方案中,阳离子聚合物具有在约103-3x106之间的分子质量。在某些实施方案中,所使用的阳离子聚合物为含有至少10%(重量)包含胺基团或季铵基团的单元的那些,其季铵化值,表示为每克聚合物的阳离子当量,为例如至少等于0.05阳离子meq/g(meq:毫当量)。当阳离子聚合物带有由侧链取代基携带的胺或季铵基团时,聚合物链为例如丙烯酸、乙烯基、硅化、氟化或糖链。在某些实施方案中,阳离子聚合物选自季铵化蛋白、季铵化聚硅氧烷、聚胺型聚合物、聚氨基酰胺和季聚铵。
季铵化蛋白特别地为在链末端带有季铵基团或向其接枝季铵基团的化学改性多肽。在这些蛋白中,尤其可提及:
带有三乙基铵基团的胶原水解产物比如在名称QUAT-PRO ETM下由公司Maybrook销售和在CTFA字典称为“三乙基铵水解胶原乙基硫酸盐”的产品,
带有三甲基铵或硬脂基三甲基氯化铵基团的胶原水解产物,在名称QUAT-PRO STM下由公司Maybrook销售和在CTFA字典称为“硬脂基三甲基铵水解胶原蛋白”;
带有三甲基苄基铵基团的动物蛋白水解产物比如在名称CROTEIN BTATM下由公司Croda销售和在CTFA字典称为“苄基三甲基铵水解动物蛋白”的产品;
在多肽链上带有包含至少一个具有1-18个碳原子的烷基的季铵基团的蛋白水解产物。
在这些蛋白水解产物当中,尤其可提及:
CROQUAT LTM,其肽链具有平均分子量为约2500并且其季铵基团包含C12烷基;
CROQUAT MTM,其肽链具有平均分子量为约2500并且其季铵基团包含C10-C18烷基;
CROQUAT STM,其多肽链具有平均分子量为约2700并且其季铵基团包含C18烷基;
CROTEIN QTM,其多肽链具有平均分子量为12000等级并且其季铵基团包含至少一个具有1-18个碳原子的烷基。这些不同产品由公司Croda销售。
其它季铵化蛋白为对应于下式的那些蛋白:
X-为有机或无机酸的阴离子,其中A表示衍生于胶原蛋白水解产物的蛋白残基,R5表示包含至高达30个碳原子的亲脂性基团,R6表示具有1-6个碳原子的亚烷基,这些蛋白具有在1500-10000之间,优选地为2000-5000之间的分子量。可提及例如由公司Inolex在名称LEXEIN QX 3000TM下销售,在CTFA字典称为“椰油基-三甲基铵胶原水解产物”的产品。
在季铵化蛋白当中,也可提及季铵化植物蛋白,比如小麦、玉米或大豆蛋白;象季铵化小麦蛋白,可提及由公司CRODA在名称HYDROTRITICUM WQ或QMTM下销售,在CTFA字典称为“椰油基二甲基铵水解小麦蛋白”,HYDROTRITICUM QLTM,在CTFA字典称为“月桂基二甲基铵水解小麦蛋白”,或者在名称HYDROTRITICUMQSTM下在CTFA字典称为“硬脂基二甲基铵水解小麦蛋白”的那些小麦蛋白。
另一个家族的阳离子聚合物为硅化阳离子聚合物。在这些聚合物当中,可提及:
(a)在CTFA字典称为“氨端聚二甲基硅氧烷”并对应于下式的季铵化聚硅氧烷:
其中x’和y’为依分子量而定的整数,分子量通常在5000-10000之间;
(b)对应于下式的硅化阳离子聚合物
其中
G为氢原子或苯基或OH基团或C1-C8烷基,优选地为甲基,a表示0或1-3的整数,并且优选地为0,
b表示0或1并且优选地为1,
总数(n+m)为1-2000的整数并且优选地为50-150,n可能表示0-1999并且优选地为49-149的数目,并且m可能表示1-2000并且优选地为1-10的整数;
R’为式CqH2qL的一价基团,其中q为2-8的数目和L选自:
NR”--CH2--CH2--N(R”)2
N(R”)2
⊕N(R40)3A
⊕N(R”)H2A
NR”CH2--CH2--⊕NR”H2A
NR”CH2--CH2--⊕NR”H2A,其中R”可表示氢、苯基、苄基、一价饱和烃基团并且优选地为具有1-20个碳原子的烷基,和A表示卤离子比如氟离子、氯离子、溴离子或碘离子。
进入该定义内的特别有用产物为称为“三甲基甲硅烷基氨端聚二甲基硅氧烷”、对应于下式的聚合物:
其中n和m具有以上(式III)所给出的含义。这样的聚合物在专利申请EP-A-95238中得到描述。
(c)对应于下式的硅化阳离子聚合物:
其中
R7表示具有1-18个碳原子的一价烃基团并且特别地为烷基或链烯基和优选地为甲基;
R8表示二价烃基团,优选地为C1-C18亚烷基或C1-C18并优选C1-C8二价亚烷氧基;
Q-为卤离子,优选地为氯离子;
r表示2-20并优选2-8的平均统计值;
s表示20-200并优选20-50的平均统计值;
这样的聚合物在美国专利号4185087中更具体地描述。进入该类型的一种聚合物为由公司Union Carbide在名称UCAR SILICONEALE 56TM下销售的聚合物。
当这些硅化聚合物得到使用时,特别有利的实施方案是其与阳离子表面活性剂、任选非离子型表面活性剂同时使用。这可用于例如符合本发明的组合物,在名称EMULSION CATIONIQUE DC 929TM下由公司DOW CORNING销售的商用产品,其除了氨端聚二甲基硅氧烷外,包含对应于下式的阳离子表面活性剂:
其中R9表示具有14-22个碳原子的链烯基和/或烷基基团的混合物,源于牛油脂肪酸,和下式的非离子型表面活性剂:
C9H19-C6H4-(OC2H4)10-OH
已知名称为NONOXYNOL 10TM。
可用于本发明该实施方案的另一种组合物为含有在名称DOWCORNING Q2 7224TM下由公司Dow Corning所销售产品的组合物,其组合地包含式(IV)的三甲基甲硅烷基氨端聚二甲基硅氧烷、也称为辛苯聚醇-40的下式非离子型表面活性剂
其中n=6也称为异月桂醇聚醚-6的下式另一种非离子型表面活性剂和乙二醇
可根据本发明使用的聚胺、聚氨基酰胺和季聚铵型聚合物特别在法国专利号8207996或8404475中得到描述。在这些聚合物当中,可提及:
(1)季铵化或非季铵化乙烯基吡咯烷酮-二烷基氨基烷基丙烯酸酯或甲基丙烯酸酯共聚物,比如在名称GAFQUATTM下由公司GAPCORPORATION销售的产品,比如GAFQUAT 734TM或755TM或者称为COPOLYMERE 937TM的产品。这些聚合物在法国专利2077143和2393573中得到详细描述。
(2)包含季铵基团在法国专利1492597中描述的纤维素醚衍生物,并且特别是在名称“JR”(JR 400TM,JR 125TM,JR 30MTM)或“LR”(LR400TM,LR 30MTM)下由公司Union Carbide Corporation销售的聚合物。这些聚合物在CTFA字典中也定义为已经与三甲基铵基团取代的环氧化物反应的羟乙基纤维素的季铵盐。
(3)阳离子纤维素衍生物,比如用水溶性季铵单体接枝的纤维素共聚物或纤维素衍生物,并且其在美国专利号4131576中得到更详细描述,比如用甲基丙烯酰乙基三甲基铵、甲基丙烯酰胺基丙基三甲基铵或二甲基二烯丙基铵的盐接枝的羟基烷基纤维素如羟甲基、羟乙基或羟丙基纤维素。相应于该定义的商用产品更特别地为在名称CELQUAT L 200TM和CELQUAT H 100TM下由公司National Starch销售的产品。
(4)更特别地在美国专利号3589578和4031307中描述的阳离子多糖和更特别地在名称JAGUAR C.13STM下由公司Meyhall销售的产品。
(5)由哌嗪基单元和用氧、硫或氮原子或用芳环或杂环任选地中断的直链或支链二价亚烷基或羟基亚烷基组成的聚合物以及这些聚合物的氧化和/或季铵化产物。这样的聚合物在法国专利2162025和2280361中得到描述。
(6)特别地通过酸性化合物与聚胺的缩聚反应制备的水溶性聚氨基聚酰胺。这些聚氨基酰胺可由表卤代醇、双环氧化物、双酐、不饱和酐、双-不饱和衍生物、双-卤代醇、双-吖丁啶鎓(bis-azetidinium)、双-卤代酰基二胺、双-烷基卤化物交联,或者由对双-卤代醇、双-吖丁啶鎓、双-卤代酰基二胺、双-烷基卤化物、表卤代醇、双环氧化物或双-不饱和衍生物有反应活性的双官能化合物的反应生成的低聚物交联;交联剂尤其以0.025-0.35摩尔/聚氨基聚酰胺的胺基团范围内的比例使用。这些聚氨基聚酰胺可烷基化或者设想它们包含一个或更多个季铵化叔胺官能团。这样的聚合物特别地在法国专利2252840和2368508中得到描述。
(7)由聚亚烷基聚胺与聚羧酸的缩合反应随后使用双功能试剂烷基化生成的聚氨基聚酰胺衍生物。可提及例如己二酸-二烷基氨基羟基烷基二亚烷基三胺聚合物,其中烷基包含1-4个碳原子并且优选表示甲基、乙基或丙基。这样的聚合物在法国专利1583363中得到描述。在这些衍生物当中,可更特别地提及在名称CARTARETINE F、F4或F8 TM下由公司Sandoz销售的己二酸/二甲基氨基羟基丙基/二亚乙基三胺聚合物。
(8)通过包含两个伯胺基团和至少一个仲胺基团的聚亚烷基聚胺与选自二甘醇酸和具有3-8个碳原子的饱和脂肪族二羧酸的二羧酸反应得到的聚合物。聚亚烷基聚胺与二羧酸的摩尔比在0.8∶1-1.4∶1之间,所生成的聚氨基聚酰胺与表氯醇反应,表氯醇与聚氨基聚酰胺的仲胺基团的摩尔比在0.5∶1-1.8∶1之间。这样的聚合物特别地在美国专利号3227615和2961347中得到描述。
该类型的聚合物特别地在名称HERCOSETT 57TM下由公司Hercules Incorporated,或者在名称PD 170TM或DELSETTE 101TM下由公司Hercules销售,在己二酸/环氧丙基/二亚乙基三胺共聚物的情况下。
(9)具有分子量为20000-3000000的环聚物,比如包含对应于下式(VI)或(VI’)的链单元作为主要成分的均聚物
k和t等于0或1,和总数k+t-1,R12表示氢或甲基,R10和R11相互独立地表示具有1-22个碳原子的烷基、其中烷基优选地具有1-5个碳原子的羟基烷基、低级氨基烷基,并且其中R10和R11可与它们所连接的氮原子一起表示杂环基团比如哌啶基或吗啉基,以及包含式(VI)或(VI’)单元和源于丙烯酰胺或双丙酮丙烯酰胺的单元的共聚物,Y为阴离子比如溴离子、氯离子、乙酸根、硼酸根、枸橼酸根、酒石酸根、硫酸氢根、亚硫酸氢根、硫酸根和磷酸根。在以上所定义的聚合物当中,更特别地可提及在名称MERQUAT 100TM下具有分子量为少于100000的二甲基二烯丙基氯化铵均聚物,和具有分子量为大于500000并在名称MERQUAT 550TM下由公司Merck销售的二甲基二烯丙基氯化铵与丙烯酰胺共聚物。这些聚合物更特别地在法国专利2080759及其附加号2190406的证书中得到描述。
(10)含有对应于下式的重复单元的季聚铵聚合物:
其中R13与R14、R15与R16为相同或不同的,表示含有1-20个碳原子的脂肪族、脂环族或芳基脂肪族基团或低级羟基烷基脂肪族基团,或者R13与R14和R15与R16一起或单独地与它们所连接的氮原子构成任选地含有除氮以外第二个杂原子的杂环,或者R13、R14、R15和R16表示用腈、酯、酰基或酰胺基团或以下基团取代的线形或分支的C2-C6烷基
或
其中R17为亚烷基和D为季铵基。
A2和B2表示含有2-20个碳原子的聚亚甲基,其可为线形或分支的、饱和或不饱和的并且其可含有结合于主链或插入到主链中的一个或更多个芳环或者一个或更多个氧或硫原子或者SO、SO2、二硫化物、氨基、烷基氨基、羟基、季铵、脲基、酰胺或酯基团和
Xe 1表示衍生于无机或有机酸的阴离子。
A2和R13和R15可与它们所连接的两个氮原子形成哌嗪环,另外,如果A2表示饱和或不饱和的、线形或分支的亚烷基或羟基亚烷基,B2也可表示以下基团:
-(CH2)n-CO-D-OC-(CH2)n-
其中D表示:
a)下式的二醇残基:O--Z--O--
其中Z表示线形或分支的烃基团或对应于下式的基团:
或
其中x和y表示1-4的整数,代表确定和独特的聚合度,或者为1-4的任何数目,代表平均聚合度;
b)双-仲二胺残基比如哌嗪衍生物,
c)下式的双-伯二胺残基:--NH-Y-NH--,其中Y表示线形或分支的烃基团或者二价基团
d)下式的次脲基基团:--NH-CO-NH--;
X为阴离子比如氯离子或溴离子。
这些聚合物具有的分子质量通常在1000-100000之间。该类型的聚合物特别地在法国专利2320330、2270846、2316271、2336434和2413907和美国专利号2273780、2375853、2388614、2454547、3206462、2261002、2271378、3874870、4001432、3929990、3966904、4005193、4025617、4025627、4025653、4026945和4027020中得到描述。
(11)下式单元组成的季聚铵聚合物:
其中R18、R19、R20和R21,其为相同或不同的,表示氢原子或者甲基、乙基、丙基、β-羟基乙基、β-羟基丙基或--CH2CH2(OCH2CH2)pOH基团,其中p等于0或1-6之间的整数,条件是R18、R19、R20和R21不同时表示氢原子,x和y,其为相同或不同的,为1-6之间的整数;
m等于0或1-34之间的整数,
X表示卤素原子,
A表示二卤化基团的残基并且优选表示--CH2-CH2-O-CH2-CH2--。这样的化合物在欧洲专利申请122 324中得到更详细描述。
(12)衍生于丙烯酸或甲基丙烯酸、包含以下单元的均聚物或共聚物:
或
其中R24表示H或CH3。A1为1-6个碳原子的线形或分支的烷基或1-4个碳原子的羟基烷基,R25、R26、R27,其为相同或不同的,表示具有1-18个碳原子的烷基或苄基,R22和R23表示氢或具有1-6个碳原子的烷基。X2 表示甲基硫酸根阴离子或卤化物比如氯离子或溴离子。可得到使用的共聚单体(一或多种)属于包含以下的家族:丙烯酰胺、甲基丙烯酰胺、双丙酮丙烯酰胺、氮由低级烷基取代的丙烯酰胺和甲基丙烯酰胺、丙烯酸或甲基丙烯酸的烷基酯、乙烯基吡咯烷酮和乙烯基酯。
13)季乙烯基吡咯烷酮和乙烯基咪唑聚合物比如在名称LUVIQUAT FC 905TM、FC 550TM和FC 370°下由公司BASF销售的产品。
其根据本发明使用的其它阳离子聚合物为聚亚烷基亚胺特别是聚亚乙基亚胺、含有乙烯基吡啶或乙烯基吡啶鎓单元的聚合物、聚胺与表氯醇的缩合物、季聚次脲基和壳多糖衍生物。
在其可用于本发明组合物的阳离子聚合物当中,尤其可提及以下聚合物:
在名称MIRAPOL AD 1TM下由公司Miranol销售的包含下式单元的聚合物:
在名称MIRAPOL AZ1TM下由公司Miranol销售的包含下式单元的聚合物:
在名称POLYMAPTACTM下由公司Texaco Chemicals销售的聚(甲基丙烯酰胺基丙基三甲基氯化铵);
在法国专利号2270846中得到描述的紫罗烯型季铵化聚合物,并且更特别地为包含以下单元的那些聚合物
在名称MERQUAT 100TM和MERQUAT 550TM下由公司Merck销售的二甲基二烯丙基铵环聚物;
季乙烯基吡咯烷酮和乙烯基咪唑聚合物,比如在名称LUVIQUATFC 905TM、FC 550TM和FC 370TM下由公司BASF销售的那些聚合物
季铵化或非季铵化乙烯基吡咯烷酮/二烷基氨基烷基丙烯酸酯或甲基丙烯酸酯共聚物,比如在名称COPOLYMERE 937TM、GAFQUAT734TM或755TM下由公司GAF销售的产品;
季纤维素醚聚合物比如在名称“JR”比如JR 125TM、JR 400TM、JR30-M TM和LR比如LR 400TM和LR 30TM下由公司Union CarbideCorporation销售的那些聚合物;
阳离子纤维素衍生物比如在名称CELQUAT L 200TM和CELQUAT H 100TM下由公司National Starch销售的产品;
在美国专利号4157388中所描述类型的季铵聚合物,并且更特别地为在名称MIRAPOL A 15TM下由公司Miranol销售的包含下式单元的聚合物:
在名称ONAMER MTM下由公司Onyx Internationale销售的聚(二甲基丁烯基氯化铵)-α,ω-双(氯化三乙醇铵);
具有硅化骨架的含胺聚合物,比如由Dow Corning销售的阳离子乳液DC929TM中含有的氨端聚二甲基硅氧烷。
在一个实施方案中,阳离子材料基于颜料颗粒总重量的量为0.1-10重量%。在其它的实施方案中,阳离子材料的量为至少0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.5、2、2.5、3、3.5、4、4.5或5重量%。在其它的实施方案中,阳离子材料的量为少于1、1.5、2、2.5、3、3.5、4、4.5、5、6、7、8、9或10重量%。任何前述最小量可与任何最大量组合形成范围。在另一个实施方案中,颜料颗粒具有的粒度为50-100微米,并且在这些颗粒上阳离子材料的量可为任何的前述量。
颜料颗粒也包括三异硬脂酸异丙氧钛盐(ITT)。三异硬脂酸异丙氧钛盐可在阳离子材料施用到颜料颗粒之前或之后加入到颜料颗粒。在一个实施方案中,ITT基于颜料颗粒总重量的量为0.1-5重量%。在其它的实施方案中,ITT的量为至少0.1、0.5、1、1.5、2、2.5、3、3.5、4或4.5重量%。在其它的实施方案中,ITT的量为少于1、2、3、4或5重量%。任何前述最小量可与任何最大量组合形成范围。在另一个实施方案中,颜料颗粒具有的粒度为50-100微米,并且在这些颗粒上的ITT量可为任何的前述量。
在一个实施方案中,颜料颗粒被预涂布。所谓预涂布,意指在将颜料颗粒加入到含有除它本身的材料的组合物之前,预先用阳离子材料和三异硬脂酸异丙氧钛盐涂布颜料颗粒。
具有阳离子材料的颗粒,其包括在阳离子材料施用之后加入的ITT,可使用以下程序制造。
(i)将阳离子材料在混合下加入到容器中的水中,容器中存在足够量的水以在加热下溶解阳离子材料。
(ii)将阳离子材料/水加热和混合,直到阳离子材料溶解。
(iii)将颜料混合到该混合物中。
(iv)将材料在105℃下干燥,直到充分干燥(约3小时)。
(v)将材料冷却并轻轻切碎。
(vi)筛分(例如用10号筛)材料,以除去结块。
(vii)以1∶2比率将三异硬脂酸异丙氧钛盐溶于ISOPAR C溶剂中。
(viii)在搅拌器中于混合下将溶液加入到在步骤(ix)中得到的粉末中。
(ix)溶液在85℃下干燥1小时。
(x)将材料冷却并轻轻切碎。
具有阳离子材料的颗粒,其包括在阳离子材料施用之前加入的ITT,可使用以下程序制造。
(i)以1∶2比率将三异硬脂酸异丙氧钛盐溶于ISOPAR C溶剂中。
(ii)在搅拌器中于混合下将溶液加入到颜料颗粒中。
(iii)溶液在85℃下干燥1小时。
(iv)将材料冷却并轻轻切碎。
(v)将阳离子材料在混合下加入到容器中的水中,容器中存在足够量的水以在加热下溶解阳离子材料。
(vi)将阳离子材料/水加热和混合,直到阳离子材料溶解。
(vii)将来自步骤(iv)的颜料混合到该混合物中。
(viii)将混合物在105℃下干燥,直到充分干燥(约3小时)。
(ix)将材料冷却并轻轻切碎。
(x)筛分(例如用40号筛)材料,以除去结块。
颜料颗粒可包括在清洁组合物比如体用洗剂、沐浴凝胶、洗手液或条皂中。颗粒在清洁系统中的量可为通常用于颗粒的任何量。在某些实施方案中,所述量为组合物的0.01-20重量%、0.1-10重量%或0.15-2重量%。在其它的实施方案中,所述量为至少0.1、0.15、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.2、1.2、1.3、1.4、1.5或2重量%至高达20重量%。颗粒可通过用于加入颜料的任何标准加入程序加入到清洁组合物中。
多种阴离子型表面活性剂可用于清洁组合物中,包括例如长链烷基(C6-C22)材料比如长链烷基硫酸盐、长链烷基磺酸盐、长链烷基磷酸盐、长链烷基醚硫酸盐、长链烷基α烯烃磺酸盐、长链烷基牛磺酸盐、长链烷基羟乙基磺酸盐(SCI)、长链烷基甘油醚磺酸盐(AGES)、磺基琥珀酸盐、Stepan-MildTM PCL 2-磺基月桂酸甲酯钠和2-磺基月桂酸二钠和磺基乙酸月桂酯钠共混物等。这些阴离子型表面活性剂可被烷氧基化例如乙氧基化,虽然烷氧基化不必需。这些表面活性剂作为其含有钠、钾、烷基和铵或链烷醇胺的盐形式通常为高水溶性的,并可提供高发泡清洁能力。可使用其它的同等的阴离子型表面活性剂。在一个实施方案中,阴离子型表面活性剂包含月桂醇聚醚硫酸钠、烷醇聚醚硫酸钠及其组合。阴离子型表面活性剂可以任何要求的量包括在内。在一个实施方案中,阴离子型表面活性剂以0-约15%(重量)的量存在于组合物中。在一个实施方案中,阴离子型表面活性剂以约6-约8%(重量)的量存在。
两性表面活性剂也可包括在组合物中。这些表面活性剂通常其特征在于高表面活性剂活性、泡沫形成和温和性的组合。两性表面活性剂包括(但不限于)脂肪族仲胺和叔胺的衍生物,其中脂肪族基团可为直链或分支的,并且其中脂肪族取代基中的一个含有约8-约18个碳原子,一个含有阴离子水增溶基团例如羧基、磺酸根、硫酸根、磷酸根或膦酸根。这样的化合物的实例包括3-十二烷基氨基丙酸钠、3-十二烷基氨基丙磺酸钠、N-烷基牛磺酸和N-高级烷基天门冬氨酸。可使用其它的同等的两性表面活性剂。两性表面活性剂的实例包括(但不限于)一定范围的甜菜碱,包括例如高级烷基甜菜碱,比如椰油基二甲基羧甲基甜菜碱、十二烷基二甲基羧甲基甜菜碱、十二烷基二甲基α-羧乙基甜菜碱、十六烷基二甲基羧甲基甜菜碱、十二烷基双-(2-羟基乙基)羧甲基甜菜碱、十八烷基双-(2-羟基丙基)羧甲基甜菜碱、油烯基二甲基γ-羧丙基甜菜碱和十二烷基双-(2-羟基丙基)α-羧乙基甜菜碱;磺基甜菜碱比如椰油基二甲基磺基丙基甜菜碱、十八烷基二甲基磺基丙基甜菜碱、酰胺甜菜碱、酰胺磺基甜菜碱等。具有长链烷基特别是椰油基的甜菜碱,可作为包括酰胺基的那些甜菜碱特别有用,比如椰油酰胺基丙基和椰油酰胺基乙基甜菜碱。两性表面活性剂可以任何要求的量包括在内。在一个实施方案中,两性表面活性剂以0-约15%(重量)的量存在于组合物中。在一个实施方案中,两性表面活性剂以约4-约6%(重量)的量存在于组合物中。
非离子型表面活性剂包括(但不限于)聚山梨醇酯20、具有C8-C22烷基的长链烷基葡糖苷;椰子油脂肪酸单乙醇酰胺比如椰油酰胺MEA;椰子油脂肪酸二乙醇酰胺、脂肪醇乙氧基化物(烷基聚乙二醇);烷基酚聚乙二醇;烷基硫醇聚乙二醇;脂肪胺乙氧基化物(烷基氨基聚乙二醇);脂肪酸乙氧基化物(酰基聚乙二醇);聚丙二醇乙氧基化物(例如可自BASF市售得到的PLURONICTM嵌段共聚物);脂肪酸烷醇酰胺,(脂肪酸酰胺聚乙二醇);N-烷基-、N-烷氧基多羟基脂肪酸酰胺;蔗糖酯、山梨醇酯、聚乙二醇醚;及其组合。非离子型表面活性剂可以任何要求的量包括在内。在一个实施方案中,非离子型表面活性剂以0-约3%(重量)的量存在于组合物中。在一个实施方案中,非离子型表面活性剂以约0.5-约1.5%(重量)的量存在于组合物中。
阳离子型表面活性剂也可包括在组合物中。阳离子型表面活性剂的实例包括(但不限于)任何季铵或聚季铵化合物。阳离子型表面活性剂可以任何要求的水平包括在内。在一个实施方案中,阳离子型表面活性剂以0-约2%(重量)的量存在于组合物中。在一个实施方案中,阳离子型表面活性剂以约0.1-约0.3%(重量)的量存在于组合物中。
许多另外的表面活性剂在McCUTCHEON′S DETERGENTS ANDEMULSIFIERS(McCUTCHEON的去污剂和乳化剂,1989)和本领域普通技术人员公知的其它参考资料中得到描述。
另外,悬浮剂可包括在内以构成表面活性剂,助于悬浮颗粒。悬浮剂为增大组合物悬浮材料的能力的任何材料。悬浮剂的实例包括(但不限于)合成构成剂(structuring agent)、聚合物树胶、多糖、果胶、藻酸盐、阿拉伯半乳聚糖、角叉菜、胞外多糖胶、黄原胶、瓜耳胶、鼠李聚糖(rhamsan)胶、红藻胶及其它天然树胶。合成构成剂在一个实施方案中为聚丙烯酸酯。用于形成固体颗粒稳定混悬液的一种丙烯酸酯水溶液由Lubrizol作为CARBOPOLTM树脂制造,也称为CARBOMERTM,其为亲水性高分子量、交联丙烯酸聚合物。在一个实施方案中,聚合物为CARBOPOLTM Aqua SF-1。可使用的其它聚合物包括(但不限于)CARBOPOLTM Aqua 30、具有分子量为约4000000的CARBOPOLTM 940和具有分子量为约3000000的CARBOPOLTM934。
悬浮剂可单独或组合使用。悬浮剂的量可为提供所要求水平的悬浮能力的任何量。在一个实施方案中,悬浮剂以组合物的约0.01-约15%(重量)的量存在。在其它的实施方案中,悬浮剂的量为约1%-约10%。
清洁组合物可含有油和/或矿脂。可使用的油类可为任何植物油,比如向日葵、大豆、蓖麻等。
颜料颗粒也可包括在口腔护理组合物中,用于将颜料颗粒传递至口腔中的表面,比如牙齿。
颜料颗粒也可包括在家庭护理组合物比如硬表面清洗剂、洗碗组合物、织物柔软剂或洗衣去污剂中。
组合物可用于增大基底上光泽的方法。组合物被施用于基底。所使用的颗粒为可提供光泽的颗粒。在施用之后,组合物可被遗留一定时间段然后除去。时间段可为任何所要求的时间段比如5、10、15、20、30、45或60秒或者1、2、3、4、5、10、15、30、60分钟或者任何时间长度。
该施用可来自清洁组合物,其中组合物被施用于皮肤以清洗皮肤。在皮肤上施用组合物和使组合物起泡之后,组合物可于皮肤上遗留一定时间段,之后冲洗泡沫,并且干燥皮肤。
Claims (15)
1.组合物,其包含用阳离子聚合物和三异硬脂酸异丙氧钛盐预涂布的颜料颗粒,其中阳离子聚合物基于颜料颗粒总重量的量为0.1-10重量%,三异硬脂酸异丙氧钛盐基于颜料颗粒总重量的量为0.1-5重量%。
2.权利要求1的组合物,其中颗粒为选自云母/二氧化钛、云母/氧化铁、云母、二氧化钛、氧化锌、氧化铁、氧化铬、硅石、滑石和高岭土的至少一种材料。
3.权利要求1的组合物,其中颗粒为云母/二氧化钛。
4.权利要求1的组合物,其进一步包含表面活性剂。
5.权利要求4的组合物,其中颜料颗粒为云母/二氧化钛。
6.权利要求4的组合物,其中组合物为体用洗剂。
7.权利要求4的组合物,其进一步包含选自油和矿脂的至少一种材料。
8.增大表面上光泽的方法,其包含向表面施用权利要求1的组合物。
9.权利要求8的方法,其进一步包含自表面清洗组合物。
10.权利要求8的方法,其中颜料颗粒为云母/二氧化钛。
11.权利要求8的方法,其中组合物进一步包含表面活性剂。
12.权利要求11的方法,其中组合物进一步包含选自油和矿脂的至少一种材料。
13.权利要求11的方法,其中颜料颗粒为云母/二氧化钛。
14.权利要求1的组合物,其中颜料颗粒首先用阳离子聚合物涂布,然后用三异硬脂酸异丙氧钛盐涂布。
15.权利要求1的组合物,其中颜料颗粒首先用三异硬脂酸异丙氧钛盐涂布,然后用阳离子聚合物涂布。
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CN118126541B (zh) * | 2024-04-30 | 2024-08-02 | 成都先进金属材料产业技术研究院股份有限公司 | 一种改善钛白粉着色底相scx值的方法 |
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