CN1723250A - 基于涂覆有SiOz(0.70≤z≤2.0)的铝的薄片形式的颜料 - Google Patents
基于涂覆有SiOz(0.70≤z≤2.0)的铝的薄片形式的颜料 Download PDFInfo
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- CN1723250A CN1723250A CN200380105546.3A CN200380105546A CN1723250A CN 1723250 A CN1723250 A CN 1723250A CN 200380105546 A CN200380105546 A CN 200380105546A CN 1723250 A CN1723250 A CN 1723250A
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- Prior art keywords
- layer
- sio
- pigment
- deck
- aluminum slice
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- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 44
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
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- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 235000011912 vitamin B7 Nutrition 0.000 description 1
- 239000011735 vitamin B7 Substances 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
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Abstract
本发明涉及一种铝薄片,它包括(A1)一层由SiOz组成的层,(B)在(A1)层上,一层由铝组成的层以及(A2)在(B)层上,一层由SiOz组成的层,其中,0.70≤z≤2.0,本发明涉及一种用于制造所述铝薄片的方法以及所述铝薄片在涂料、静电涂覆、在喷墨印刷、化妆品、涂层、油墨、塑性材料、在用于陶瓷和玻璃的釉料、在安全印刷以及在干涉颜料制造中的用途。
Description
本发明涉及一种铝薄片,它包括
(A1)一层由SiOz组成的层,
(B)在(A1)层上,一层由铝组成的层以及
(A2)在(B)层上,一层由SiOz组成的层,
其中,0.70≤z≤2.0,本发明涉及一种用于制造所述铝薄片的方法以及所述铝薄片在涂料、静电涂覆、在喷墨印刷、化妆品、涂层、油墨(printing ink)、塑性材料、在用于陶瓷和玻璃的釉料、在安全印刷(security printing)以及在干涉颜料(interference pigment)制造中的用途。
通过PVD(物理汽相沉积)方式汽相沉积SiO或SiO2保护层的铝薄片是已知的。
WO00/69975公开了一种铝薄片,其包括:
(a)一层绝缘材料(dielectric material),例如一氧化硅或二氧化硅,
(b)一层金属,例如铝,
一层绝缘材料,例如一氧化硅或二氧化硅。
(c)绝缘层的厚度使得金属的光学性能不受到显著影响,即所述厚度在10-20nm的范围内。
US-A-6,013,370公开了一种铝薄片,其包括:
(a)一层绝缘材料,例如二氧化硅,
(b)一层金属,例如铝,
(c)一层绝缘材料,例如二氧化硅。绝缘层的厚度使得金属的光学性能不受到显著影响,即所述厚度在50-200nm的范围内。
在WO00/24946的实施例2中,公开了涂覆有SiO的铝薄片的制造。根据其说明书,SiO保护层的厚度为15nm或者更少。
令人惊讶的是,现在发现如果所述SiOz层的层厚在200-350nm的范围内,优选在250-300nm的范围内时,可获得同现有技术中公知的铝薄片相比,具有更明亮的外观和更大的亮度的金属薄片,其中0.70≤z≤2.0,优选1.4≤z≤2.0。
因此,本发明涉及一种铝薄片,其包括:
(A1)一层由SiOz组成的层,
(B)在(A1)层上,一层由铝组成的层以及
(A2)在(B)层上,一层由SiOz组成的层,
其中,0.70≤z≤2.0,优选1.4≤z≤2.0,本发明涉及一种用于制造所述铝薄片的方法以及所述铝薄片在涂料、静电涂覆、在喷墨印刷、化妆品、涂层、油墨、塑性材料、在用于陶瓷和玻璃的釉料、在安全印刷以及在随角异色效应颜料(effect pigment)制造中的用途。
在一种优选实施方案中,本发明涉及一种铝薄片,其包括:
(D1)一层由SiO2组成的层,
(B)在层(D1)上,一层由铝组成的层,以及
(D2)在层(B)上,一层SiO2组成的层。
SiOz或SiO2层的层厚为200-350nm,优选为250-300nm。
由铝组成的(B)层的层厚通常为10-100nm,优选为30-50nm。
术语“SiOz,0.70≤z≤2.0”意思为氧化硅层中氧对硅摩尔比率的平均值为0.70-2.0。通过ESCA(化学分析用电子能谱法)可确定氧化硅层的成分。
术语“SiOy,0.70≤y≤1.95”意思为氧化硅层中氧对硅摩尔比率的平均值为0.70-1.95。通过ESCA(化学分析用电子能谱法)可确定氧化硅层的成分。
根据本发明,术语“铝”包括铝和铝的合金。例如在G.Wassermann,在Ullmanns Enzyklopdieder industriellen Chemie,4.Auflage,Verlag Chemie,Weinheim,Band7,S.281-292中描述了铝的合金。特别适宜的是WO00/12634 10-12页中公开的耐蚀铝合金,除铝硅合金之外,其还包括以重量计,低于20%、优选以重量计,低于10%的镁、锰、铜、锌、镍、钒、铅、锑、锡、镉、铋、钛、铬和/或铁。
所述铝薄片具有一个铝核,所述铝核具有两个大体平行的表面,所述平面之间的距离为核的最短轴,用氧化硅涂覆所述平行表面,但不涂覆侧面。此外,涂覆有氧化硅层的铝薄片的长度为2μm-5mm,宽度为2μm-2mm,厚度为410-800nm,且长度和厚度的比率至少为2∶1。优选铝薄片具有1-60μm的长度和宽度,优选为2-40μm,最优选为5-20μm。长度与厚度的比率为大约2∶1至大约150∶1,长度和宽度的比率为3∶1至1∶1。
氧化硅/铝薄片形状不均匀。不过,为了简洁,将提到薄片具有“直径”。所述氧化硅/铝薄片具有很高的平面平行度,并具有在平均厚度±10%范围内,特别在±5%范围内的规定厚度。所述氧化硅/铝薄片具有410-800nm,特别为530-650nm的厚度。目前优选所述薄片的直径在大约2-40μm的优选范围内,更优选的范围为大约5-20μm。这样,本发明薄片的纵横比在大约8-40的优选范围内。
为提高对气候作用的稳定性和耐光性,在高于200℃的温度,优选高于400℃并低于600℃的温度下,用空气或者其它含氧气体氧化0.70≤y≤1.8的SiOy,或将之转化为SiO2层。例如,在含氧气氛下,通过在500-600℃下加热几小时,可将涂覆有SiOy(y=1)的铝薄片转化为涂覆有SiOz(z=1.40-2.00)的铝薄片。在所述方法中,如果未将全部SiOy转化为SiO2,则SiO2层在SiOy层的表面上形成,y值朝着铝层逐渐降低。
本发明的另一优选实施方案涉及一种铝薄片,其包括:
(C1)一层由SiO2组成的层,
(A1)在层(C1)上,一层由SiOy组成的层,
(B)在层(A1)上,一层由铝组成的层,
(A2)在层(B)上,一层由SiOy组成的层,以及
(C2)在层(A2)上,一层由SiO2组成的层,
其中,0.70≤y<1.95,优选1.0≤y≤1.8,最优选1.4≤ y≤1.8。
由铝组成的层(B)的层厚通常为10-100nm,优选为30-50nm。
当铝薄片为终产物时,由SiOz组成的层(A1)和(A2)的层厚,由SiO2组成的层(D1)和(D2)的层厚,由SiOy组成的层(A1)和由SiO2组成的层(C1)的层厚,以及由SiOy组成的层(A2)和由SiO2组成的层(C2)的层厚为200-350nm,优选为250-300nm,当铝薄片为用于干涉颜料的中间产物时,所述厚度为200-500nm。当铝薄片为终产物时,特别优选y大约为1的SiOy具有大约250±10nm的厚度,SiO2具有大约300±10nm的厚度。
可将根据本发明的铝薄片用在公知铝薄片的常规应用中。可提及的实例为在涂料、静电涂覆、在喷墨印刷、化妆品、涂层、油墨、塑性材料、在用于陶瓷和玻璃的釉料、在安全印刷中使用根据本发明的铝薄片。
将制成的铝薄片进行后涂覆或者后处理也是可能的,其进一步增加了对光、气候作用和化学药品的稳定性,或者使颜料的处理,特别是掺入多种介质变得容易。例如在EP-A-477433,EP-A-826745或者EP-A-1084198中公开的方法适宜作为后处理或者后涂覆。
通过进一步涂覆层,可将所述铝薄片进一步转化成干涉颜料。例如在下面的专利:EP-A-571836,EP-A-708154,EP-A-768343,EP-A-1025168以及WO00/34395中公开了这种颜料的基本结构。
为了能够在含水组合物中使用所述铝薄片(薄片形式的铝),保护这些颜料使之抵抗由于水带来的腐蚀是必要的。根据R.Besold,Aluminiumpigments für wssrige Beschichtungen-Widerspruch oder Wirklichkeit?,Farbe+Lack97(1991)311-314,公知许多用来稳定铝颜料的工艺规程,其可被分成两类:
-在颜料表面吸附腐蚀抑制剂
-磷酸酯:DE-A3020073,EP-A-170474,EP-A-133644,US-A-4,565,716,US-A-4,808,231,
-磷酸盐和亚磷酸盐:US-A-4,565,716,US-A-4,808,231,EP-A-240367,
-钒酸盐:EP-A-305560,EP-A-104075,
-铬酸盐:US-A-2,904523,US-A-4,693,754,EP-A-259592,
-二聚酸:DE-A3002175,以及
-用连续无机保护层包覆颜料:
-SiO2:US-A-2,885,366,US-A-3,954,496,
-Fe2O3:DE-A-3003352,
-TiO2:DE-A-3813335,
或者用有机保护层:
-DE-A-3630356,DE-A-3147177,EP-A-477433,特别是用磷酸改性的树脂:EP-A-170474,CA-A-1,273,733,AT-A-372696,DE-A-3807588,EP-A-319971。
在一种特别优选的实施方案中,以氧化硅/金属基底为基础的干涉颜料还包括一绝缘材料层,其具有“高”折射率,即折射率大于大约1.65,优选大于大约2.0,最优选大于大约2.2,将所述绝缘材料施加在氧化硅/金属基底的整个表面上。这样一种绝缘材料的实例为硫化锌(ZnS),氧化锌(ZnO),氧化锆(ZrO2),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(CeO),氧化钇(Y2O3),氧化铕(Eu2O3),氧化铁例如氧化铁(II)/铁(III)(Fe3O4)以及氧化铁(III)(Fe2O3),氮化铪(HfN),碳化铪(HfC),氧化铪(HfO2),氧化镧(La2O3),氧化镁(MgO),氧化钕(Nd2O3),氧化镨(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),或者其组合。所述绝缘材料优选为金属氧化物,所述金属氧化物可能为具有或不具有吸收性能的单一氧化物或者氧化物的混合物,例如为TiO2,ZrO2,Fe2O3,Fe3O4,Cr2O3,钛铁矿,氧化铁水合物,钛的低价氧化物,或者ZnO,特别优选TiO2。通过在TiO2层的上部施加低折射率的金属氧化物来获得颜色更浓郁的颜料是可能的。可被使用的适宜的低折射率绝缘材料的非限制性实例包括二氧化硅(SiO2),氧化铝(Al2O3),以及金属氟化物例如氟化镁(MgF2),氟化铝(AlF3),氟化铈(CeF3),氟化镧(LaF3),氟化铝钠(例如Na3AlF6或者Na5Al3F14),氟化钕(NdF3),氟化钐(SmF3),氟化钡(BaF2),氟化钙(CaF2),氟化锂(LiF)及其组合,或者任意其它折射率为大约1.65或者更低的低折射率材料。例如可将有机单体或者聚合物用作低折射率材料,其包括二烯或者烯烃如丙烯酸酯(例如甲基丙烯酸酯),全氟链烯聚合物,聚四氟乙烯(TEFLON),氟化乙丙烯(FEP)聚合物,聚对苯二甲撑,对二甲苯,其组合及类似物。此外,前述材料包括经蒸发、冷凝及交联的透明的丙烯酸酯层,其可通过在US专利No.5,877,895或EP-A733,919中公开的方法沉积,在此参考引用其所公开的内容。优选SiO2、Al2O3、AlOOH、B2O3或其混合物。最优选SiO2。
可通过CVD(化学汽相沉积)或者通过湿法化学涂覆来施加所述金属氧化层。在有水蒸气存在(相对低分子量的金属氧化物例如四氧化三铁)或者在有氧、以及适合条件下有水蒸气存在时(例如氧化镍和氧化钴),可通过金属羰基化合物的分解来获得所述金属氧化物层。特别通过金属羰基化合物(例如五羰基铁、六羟基化铬;EP-A-45851)的氧化气相分解方式、通过金属醇化物(例如四正和异丙醇钛和锆;DE-A-4140900)或者金属卤化物(例如四氯化钛;EP-A-338428)的水解气相分解的方式、通过有机锡化合物(特别是烷基锡化合物例如四丁基锡和四甲基锡;DE-A-4403678)的氧化分解的方式、或者通过在EP-A-668329中公开的有机硅化合物(特别是二-叔-丁氧基乙酰氧硅烷)的气相水解的方式来施加所述金属氧化物层。在流化床反应器中进行涂覆操作是可能的(EP-A-045851和EP-A-106235)。
可按照在DE-A-4236332、EP-A-678561以及EP-A-826745中公开的钝化法,通过金属氧化物-卤化物(例如CrO2Cl2、VOCl3),特别是三卤氧化磷(例如POCl3)、磷酸和亚磷酸酯(例如二-和三-甲基和二-和三-乙基亚磷酸酯)和含氨基的有机硅化合物(3-氨基丙基-三乙氧基和-三甲氧基硅烷)的水解或者氧化气相分解来施加含磷酸盐、铬酸盐和/或钒酸盐以及还含磷酸盐和SiO2的金属氧化物层。
优选通过湿法化学方法、通过沉积来施加金属锆、钛、铁和锌的氧化物层、这些金属的氧化物水合物、铁钛矿、钛的低价氧化物或其混合物。在适当情况下,将所述金属氧化物还原是可能的。在湿法化学涂覆的情况下,可使用被研究用于制造珠光颜料的湿法化学涂覆方法,所述方法被描述于,例如DE-A-1467468、DE-A-1959988、DE-A-2009566、DE-A-2214545、DE-A-22215191、DE-A-2244298、DE-A-2313331、DE-A-2522572、DE-A-3137808、 DE-A-3137809、DE-A-3151343、DE-A-3151354、DE-A-3151355、DE-A-3211602和DE-A-3235017、DE1959988、WO93/08237、WO98/53001以及WO03/6558中。
优选的高折射率金属氧化物为TiO2和/或氧化铁、优选的低折射率金属氧化物为SiO2。可将TiO2层进行金红石或者锐钛型(anastase)改性,优选金红石改性。也可通过公知的方式,例如在EP-A-735,114、DE-A-3433657、DE-A-4125134、EP-A-332071、EP-A-707,050或者如WO93/19131中所描述的那样,用氨气、氢气、烃蒸气或其混合物、或金属粉末将TiO2层还原。
为了涂覆,将基底颗粒悬浮在水中,在适宜水解的pH值,添加一种或多种水解性金属盐,选择pH从而使得金属氧化物或金属氧化物水合物直接沉积在颗粒上而不发生副沉积。一般可通过同时计量供给碱使pH保持恒定。然后将颜料分离、清洗、干燥并在适宜的情况下焙烧。优化有关涂覆的焙烧温度是可能的。如果期望,在施加各个涂层之后,可将颜料分离、干燥并在适宜的情况下焙烧,然后再将其重新悬浮以用于进一步沉积层。
例如可以用与DE-A-19501307相似的方法,通过控制一种或多种金属酸性酯的水解来制备金属氧化物层,适宜时在有机溶剂和碱性催化剂存在的条件下,通过溶胶-凝胶方法来获得金属氧化物层。适宜的碱性催化剂例如为胺类如三乙胺、乙二胺、三丁基胺、二甲基乙醇胺以及甲氧基丙基胺。所述有机溶剂为一种水溶性有机溶剂如C1-4醇、特别是异丙醇。
适宜的金属酸性酯选自钒、钛、锆、硅、铝和硼的烷基和芳基醇化物、羧化物,以及被羧基、或者烷基、或者芳基所取代的烷基醇化物或羧化物。优选使用铝酸三异丙基酯、钛酸四异丙基酯、锆酸四异丙基酯、原硅酸四乙基酯以及硼酸三乙基酯。此外,也可使用上述金属的乙酰基丙酮化物和乙酰乙酰基丙酮化物。这种类型的金属酸性酯的优选实例为乙酰基丙酮锆、乙酰基丙酮铝、乙酰基丙酮钛以及二异丁基油烯基乙酰乙酰基铝酸酯或者二异丙基油烯基乙酰乙酰基丙酮酸酯以及金属酸性酯的混合物,例如Dynasil(Hüls),一种铝/硅金属酸性酯的混合物。
作为一种具有高折射率的金属氧化物,优选使用二氧化钛,根据本发明的一种实施方案,使用US-B-3553001中公开的方法来施加二氧化钛层。
将一种水溶性钛盐溶液缓慢地添加到被涂覆材料的悬浮液中,将所述悬浮液加热到大约50-100℃,特别是70-80℃,通过同时计量供给碱例如氨水溶液或碱金属氢氧化物溶液以使pH维持在大体为约0.5-5的恒定值,特别为约1.2-2.5的恒定值。一旦达到了期望层厚的TiO2沉积物,就可停止添加钛盐溶液和碱。
这种也被称作滴定法的方法以可以避免过量的钛盐而著名。它可通过以下方法达成,即每单位时间,对于水解反应,仅仅进料为了均匀涂覆水合TiO2所必需的原料量,且每单位时间形成的水合TiO2数量可被被涂覆颗粒的可用表面所吸收。原则上,锐钛矿形式的TiO2在初始颜料的表面上形成。但是,通过添加少量的SnO2,使得形成金红石型结构是可能的。
TiO2层的厚度通常为5-100nm,特别为10-25nm。
任选通过常规的工艺规程来将TiO2层还原:US-B-4,948,631(NH3,750-850℃),WO93/19131(H2>900℃)或者DE-A-19843014(固体还原剂,例如硅,>600℃)。
在适宜时,可在二氧化钛层的上面施加SiO2(保护)层,为此可使用下面的方法:将苏打水玻璃溶液计量供给到被涂覆材料的悬浮液中,将所述悬浮液加热到大约50-100℃,特别是70-80℃。通过同时添加10%的盐酸将pH维持在4-10,优选维持在6.5-8.5。在添加水玻璃溶液之后,搅拌30分钟。
优选通过将涂覆有SiO2或SiOy的铝薄片悬浮在水中并用一种具有高折射率的金属氧化物水合物、并在适宜时用一种低折射率的金属氧化物水合物进行涂覆来获得干扰色颜料,所述涂覆通过常规的方法、即通过相应的水溶性金属化合物的添加和水解来进行,通过同时添加酸或碱来建立沉积所述金属氧化物水合物所需要的pH值并保持恒定,随后,从水悬浮液中分离涂覆有载体的材料、干燥并在适宜时煅烧(参见例如DE1959988、DE2215191、DE2244298、DE2313331、DE2522572、DE3137808、DE3137809、DE3151343、DE3151355、DE3211602、DE3235017、WO93/08237以及WO98/53011)。
在涂覆有SiOz的金属基底上,例如可通过如在US-B-6,524,381中公开的等离子体辅助真空法(使用振动运输机、旋转鼓式涂布器、振荡鼓式涂布器以及自由下落室)来沉积金刚石型碳和无定形碳从而替代具有US-B-6,524,381中高折射率材料的金属氧化物层。
因此,本发明还涉及基于硅氧化物/铝基底的平面平行结构(颜料),在所述基底表面上具有厚度为5-150nm,特别为20-70nm,更特别为30-70nm的碳层,特别是金刚石型碳层。
在所述方法中,例如在US-B-6,015,597中,通过等离子体沉积将金刚石型网状(DLN)涂层沉积在来自含碳气体例如乙炔、甲烷、丁二烯及其混合物、任选的Ar以及任选的含有另外成分的气体颗粒上。在减压(相对于大气压)和受控环境中进行沉积。通过向一种含碳气体施加电场来在一反应室中形成一种富碳等离子体。将被涂覆的颗粒容纳在反应器的器皿或容器中,并在接近等离子体时被激发。等离子体中的物种在颗粒表面上反应形成共价键,从而导致在颗粒的表面上形成DLN。
术语“金刚石型网状物”(DLN)是指一种包括碳和任选包括一种或多种其它成分的无定形膜或者涂层,所述成分选自氢、氮、氧、氟、硅、硫、钛以及铜。金刚石型网状物包括大约30-100原子百分比的碳,其余为任选的其它成分。
例如可通过EP-A-1034320中公开的方法和装置来用金刚石型碳层或者金刚石型网状物涂覆涂覆有SiOz的薄片,其包括:
提供一种电容耦合反应器系统,它包括在抽空的反应室中的两个电极,
在接近其中一个电极处放置大量颗粒;
抽空所述反应室;
使高频能量作用在接近颗粒的那个电极上,并使另一电极接地,
将一含碳源,例如烃气体如乙炔、甲烷、丁二烯及其混合物引入到反应室中,从而在接近大量颗粒的地方形成包括反应物种的等离子体,
进一步在接地电极的周围形成离子云,
以这样一种方式激发所述薄片,即要使其表面暴露给等离子体中的反应物种,同时使得所述颗粒大体上保持在所述离子云内。
所述金刚石型网状物可由碳组成,适宜地可包括一种或多种由氢、氮、氧、氟、硅、硫、钛或铜组成的成分。
因此,本发明也涉及一种基于本发明铝薄片的颜料,其在层(A1)和(A2)上,或者在层(C1)和(C2)上,优选在所述铝薄片的整个表面上,包括一层由绝缘材料层组成的层(E),所述绝缘材料具有“高”折射率,特别为TiO2或者为碳,优选为金刚石型碳,以及
涉及一种基于本发明铝薄片的颜料,其在层(D1)和(D2)上,优选在所述铝薄片的整个表面上,包括一层由绝缘材料层组成的层(E),所述绝缘材料具有“高”折射率,特别为TiO2或者为碳,优选为金刚石型碳。
所述碳层的厚度通常为5-150nm,优选为30-70nm。
此外,如在EP-A-0982376中所述,可用掺氮碳层涂覆涂覆有SiOz的铝薄片。在EP-A-0982376中公开的方法包括下述步骤:
(a)使涂覆有氧化硅的铝薄片在液体中悬浮,
(b)适宜时添加一种表面改性和/或一种聚合催化剂,
(c)在步骤(b)之前或之后,添加一种或多种包括氮和碳原子的聚合物,或者一种或多种能够形成这种聚合物的单体,
(d)在所述薄片的表面上形成一种聚合物涂层,
(e)分离所述被涂覆的薄片以及
(f)在气体气氛下,将被涂覆的薄片加热到100-600℃的温度。
所述聚合物可以为聚吡咯、聚酰胺、聚苯胺、聚氨酯、丁腈橡胶或者一种密胺甲醛树脂,优选聚丙烯腈,或者所述单体为吡咯衍生物,一种丙烯腈、甲基丙烯腈、巴豆腈、丙烯酰胺、甲基丙烯酰胺或者丁烯酰胺,优选为一种丙烯腈、甲基丙烯腈或者巴豆腈,最优选为丙烯腈。
优选地,在步骤(f)中,先在含氧气氛中,将所述薄片加热到100℃-300℃,然后在惰性气氛中,将之加热到200℃-600℃。
因此,本发明涉及基于本发明铝薄片的颜料,在涂覆有氧化硅的铝薄片的整个表面上,其包括一层(F),其包含按重量计50-95%的碳,按重量计5-25%的氮,按重量计0-25%的氢、氧和/或硫元素,按重量计的百分比数据与层(F)的总重量有关。
所述掺氮碳层的厚度通常为10-150nm,优选为30-70nm。
本发明还涉及基于本发明的铝薄片颜料在涂料、纺织品(参见例如PCT/EP03/11188)、喷墨印刷(参见例如PCT/EP03/50690)、化妆品(参见例如PCT/EP03/09269)、油墨、塑性材料、涂层,特别是在汽车精饰、在用于陶瓷和玻璃的釉料、以及在安全印刷中的用途。
如果通过PVD来施加铝核上的层,那些层将仅在所述核的平行表面上出现,而不在侧面上出现。如果通过湿法化学沉积来进一步施加层,它们将覆盖所述薄片的整个表面。
可通过包括下述步骤的方法(US-B-6,270,840、WO00/18978、WO02/090613、WO03/90613)来基本上获得涂覆有SiOy的铝薄片:
a)在一种载体上蒸气沉积一种分离剂以产生分离剂层,
b)在所述分离剂层上蒸气沉积一SiOy层,
c)在所述SiOy层上蒸气沉积一Al层,
d)在所述Al层上蒸气沉积一SiOy层,
e)将所述分离剂层溶解在一溶剂中以及
f)将所述涂覆有SiOy的铝薄片从溶剂中分离,其中0.70≤y≤1.95,优选1.0≤y≤1.80,最优选1.10≤y≤1.80。
优选由一氧化硅蒸气形成所述氧化硅层(SiOy),所述蒸气通过在一蒸发器中,在高于1300℃温度下,通过Si和SiO2混合物的反应制得。优选在高于1300℃的温度下,通过蒸发以重量计含硅量高达20%的一氧化硅来形成0.70≤y≤0.99的SiOy层。
上述方法使得到的涂覆有氧化硅的铝薄片具有很高的平面平行度,并具有在平均厚度±10%范围内,特别在±5%范围内的规定厚度,且具有低反射。
在高真空下,优选通过将蒸发器中的细粒硅和石英(SiO2)粉末的化学计量混合物加热到高于1300℃来获得SiOy层,所述蒸发器例如已在DE4342574C1和US-A-6202591中公开。反应产物为一氧化硅气体,在真空下,其被直接导向传递载体上,并在那里冷凝为SiO。也可使用非化学计量的混合物。所述蒸发器包括一料炉,所述料炉包括Si和SiO2的混合物、SiOy或其混合物,彼此(Si和SiO2)反应的物质颗粒大小有利地小于0.3mm。Si与SiO2的重量比有利地在0.15∶1-0.75∶1之间(重量份);优选提供化学计量的混合物。蒸发器中的SiOy直接蒸发。Si和SiO2在高于1300℃的温度下反应形成一氧化硅蒸气。在载体上冷凝的分离剂可为一种光漆,一种在US-B-6398999中公开的热塑性聚合物如丙烯酸类聚合物或苯乙烯聚合物或其混合物,一种可溶于有机溶剂或水且在真空中可蒸发的有机物质如蒽、蒽醌、乙酰胺基酚、乙酰水杨酸、樟脑酸酐、苯并咪唑、苯-1,2,4三羧酸、联苯-2,2-二羧酸、二(4-羟苯基)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-羧酸、间苯二酸、4,4-亚甲基双-3-羟基萘-2-羧酸、萘-1,8-二羧-酸酐、酞酰亚胺及其钾盐、酚酞、吩噻嗪、糖精及其盐、四苯基甲烷、三苯撑、三苯基甲醇或这些物质中至少两种的混合物。优选所述分离剂为可溶于水且可在真空中蒸发的无机盐(参见例如DE19844357)如氯化钠、氯化钾、氯化锂、氟化钠、氟化钾、氟化锂、氟化钙、氟化铝钠以及四硼酸二钠。
通常在高于步骤a)和b)且低于大气压力的压力下进行步骤e)。
优选(可移动的)载体包括一个或多个具有或不具有聚合物涂层的连续金属带,或者一个或多个聚酰亚胺或聚对苯二甲酸乙二醇酯带。所述可移动的载体还可包括一个或多个圆盘、圆筒或其它旋转对称体,所述对称体围绕一轴旋转。
优选通过洗净,接着通过过滤、沉淀、离心作用、滗析和蒸发来将涂覆有SiOy的铝薄片从所述分离剂的溶剂中分离。此外,在洗净含在溶剂中的、溶解的分离剂之后,可使涂覆有SiOy的铝薄片同所述溶剂一起冷冻,随后进行冷冻干燥处理,其间作为低于三相点的升华作用的结果,所述溶剂被分离,所述干燥薄片以单独的平面平行结构形式留下来。
所述冷凝的硅的低价氧化物符合分子式SiOy,0.95≤y≤1.8,优选大约1.0≤y≤1.5,通过在蒸发器中的材料里含有过量的硅来获得低于1的y值。除了在超高真空下之外,在10-2Pa级的工业真空中,被蒸发的SiO总是冷凝为SiOy,1≤y≤1.8,特别地1.1≤y≤1.5,这是因为高真空装置总是包括痕量水蒸气,这是气体从表面排放的结果,所述水蒸气在蒸发温度下同易反应的SiO反应。
详细地,把一种盐例如NaCl,接着是硅的低价氧化物(SiOy)、Al和SiOy各层相继蒸发沉积在一种载体上,其可以为一种连续的金属带,所述各种物质可在<0.5Pa的真空下经由所述蒸发器通过。所述盐的蒸发沉积厚度大约为20-100nm,优选为30-60nm,SiO的厚度取决于产物的预定用途,为200-500nm,铝的厚度为10-100nm。此外,闭合形成一环线的带式载体运行通过公知结构的动态真空密封室(参照US6270840)的1-5×104Pa,优选600-109Pa,特别地103-5×103Ta压力区域,在所述区域,所述载体浸在分开热浴中。选择所述溶剂的温度从而使得其蒸气压在所述压力范围内。用机械辅助手段,将分离剂层快速溶解,并使产物层分裂为薄片,然后所述薄片在溶剂中以悬浮物形式存在。此外,将所述带干燥并使之摆脱任何仍黏附在它上面的污染物。所述带通过第二组动态真空密封室,返回到蒸发室,在其中重复用分离剂和产物层涂覆的过程。
然后根据公知技术,在进一步操作中,将在两种情况下获得的悬浮液分离,所述悬浮液包括产品组织和具有分离剂溶解在其中的溶剂。为此,首先在液体中将所述产品组织浓缩并用新鲜溶剂清洗几次以洗掉所述溶解的分离剂。然后通过过滤、沉淀、离心作用、滗析或蒸发将仍然很湿的、固体形式的产物分离并将之干燥。
在大气压下洗净之后,在温和条件下,通过冷冻所述悬浮液可进行平面平行组织的分离,所述悬浮液已被浓缩为固体含量大约为50%,并以公知方式在大约-10℃和50Pa压力下,将之冷冻干燥。所述干燥物质作为产物留下来,可通过涂覆或化学转化对其进行进一步加工步骤。
通过进行分离剂和SiOy,Al和SiOy的蒸发沉积步骤、分离步骤、以及根据DE-A-19952032干燥载体的步骤,代替使用连续带,可能生产应用旋转体的产品。所述旋转体可以为一个或多个圆盘、一个圆筒或者任意其它的旋转对称体。
然后将所述薄片进行氧化加热处理。例如,在高于200℃的温度,优选高于400℃的温度,特别地在400-600℃的温度,将空气或者一些其它含氧气体通过所述薄片,其以松散料形式存在或位于流化床中。
将膜的碎片粉碎为颜料大小可以这样来实施,例如在液体介质中,或者在具有旋转分级器的空气喷射碾磨机中干燥所述碎片之后,通过超声波或者使用高速搅拌的机械方式来实施。取决于是否在液体介质中或者在干燥状态下进行颜料粉碎,可在粉碎工序过程中或在粉碎工序后,通过上述方法中的一种进行铝颜料的游离金属表面的钝化。
将铝薄片或者颜料进行后涂覆或者后处理也是可能的,所述后处理进一步增加了对光、气候作用和化学物质的稳定性,或使处理的颜料容易操作,特别是容易并入到多种介质中。例如在EP-A-1084198、EP-A-826745、DE-A-2215191、DE-A-3151354、DE-A-3235017或者DE-A-3334598公开的方法适宜用作后处理或者后涂覆。
适宜时,可使用下面的方法来施加一层SiO2保护层:将苏打水玻璃溶液计量供给到被涂覆材料的悬浮液中,所述悬浮液已被加热到大约50-100℃,特别是70-80℃。通过同时添加10%的盐酸将pH维持在4-10,优选维持在6.5-8.5。在添加水玻璃溶液之后,搅拌30分钟。
根据本发明的颜料以具有很均匀的厚度而著名,作为厚度均匀的结果,可获得很高的色纯度和色强度。金属或非金属的、无机薄片形颗粒或者颜料为随角异色效应颜料(特别是金属随角异色效应颜料或者干涉颜料),即,除了给应用介质以颜色之外,所述颜料还给予额外的性能例如随角异色(移动)、使有光泽(不是表面光泽)或者纹理。在金属随角异色效应颜料(铝薄片)上,在定向颜料颗粒上发生大体上定向的反射。在干涉颜料(颜料)的情况下,给色效应是由于在很薄的高折射层中光的干涉现象造成的。
可将根据本发明的颜料用于所有常规用途,例如用于物质、涂层(包括效果精饰、其包括用于汽车部件的效果精饰)以及油墨(包括胶印、凹版印刷、烫金和橡皮版印刷)中对聚合物的染色,还用于例如化妆品、喷墨印刷、纺织品染色、用于陶瓷和玻璃的釉料以及纸和塑料的激光印记。由参考书已知这些应用,例如“IndustrielleOrganische Pigmente”(W.Herbst and K.Hunger,VCHVerlagsgesellschaft mbH,Weinheim/New York,2nd,completelyrevised edition,1995).
当根据本发明的颜料为干涉颜料(随角异色效应颜料)时,它们是角色差的,并导致明亮的、高饱和(有光泽的)的颜色。因此,它们特别适宜同传统透明颜料例如有机颜料如二酮基吡咯并吡咯、喹吖啶酮、二噁嗪、苝、异吲哚啉-1-酮等结合使用。透明颜料具有与随角异色效应颜料相似的颜色是可能的。特别地,当透明颜料和随角异色效应颜料的颜色互补时,例如和EP-A-388932或EP-A-402943类似,可获得有趣的联合效果。
根据本发明的颜料用于使高分子量的有机材料染色时,具有极好的效果。
可使用根据本发明的颜料或颜料组合物进行染色的高分子量的有机材料可为天然或者合成物质。高分子量有机材料通常具有大约103-108g/mol或者更大的分子量。它们可以是例如天然树脂、干性油、橡胶或酪蛋白、或者由其衍生的天然物质如氯化橡胶、油改性的醇酸树脂、粘胶、纤维素醚或酯如乙基纤维素、醋酸纤维素、丙酸纤维素、乙酰丁酸纤维素或硝化纤维,但是特别为通过聚合、缩聚或者加聚作用获得的全合成有机聚合物(热固塑料和热塑性塑料)。根据聚合树脂的分类,特别可提及的为聚烯烃类如聚乙烯、聚丙烯、聚异丁烯以及取代的聚烯烃如氯乙烯、醋酸乙烯酯、苯乙烯、丙烯腈、丙烯酸酯、甲基丙烯酸酯或者丁二烯的聚合产物,也可为所述单体的共聚产物如特别为ABS或EVA。
在所述一系列加聚树脂和缩聚树脂中,可提及的为例如酚类与甲醛的缩合物,即所谓的酚醛塑料;带有尿素、硫脲或三聚氰胺与甲醛的缩合物,即所谓的氨基塑料;用作表面涂覆树脂的聚酯,可以是饱和的如醇酸树脂,也可以是不饱和的如顺丁烯二酸树脂;以及线性的聚酯、聚酰胺、聚氨基甲酸酯或者硅树脂。
所述高分子量的化合物可以塑料或熔融物的形式单独或在混合物中存在。它们也可作为成膜剂或者用于涂层或油墨的粘合剂,以其单体或以聚合状态并以溶解的形式存在,例如为熟亚麻仁油、硝化纤维、醇酸树脂、三聚氰胺树脂、脲甲醛树脂或者丙烯酸树脂。
取决于预定目的,已证明将根据本发明的(随角异色效应)颜料或者(随角异色效应)颜料组合物用作有机调色剂或以制品的形式使用是有利的。假设将随角异色效应颜料用于使高分子量有机材料,特别是聚乙烯染色没有不利效果的话,则取决于调节方法和预定用途,在调节过程之前或之后,将一定量的织物改性剂添加到随角异色效应颜料中是有利的。特别地,适宜的试剂为含有至少18个碳原子的脂肪酸,例如硬脂酸或山萮酸,或者上述酸的酰胺或其金属盐特别是镁盐,也可是增塑剂、蜡、树脂酸如松香酸、松香皂、烷基酚或脂族醇如十八醇,或者含有8-22个碳原子的脂肪族1,2-二羟基化合物如1,2-十二烷二醇,以及改性的松香顺丁烯二酸树脂或者富马酸松香树脂。优选添加以终产物重量计0.1-30%的织物改性剂,特别为以终产物重量计的2-15%。
可以任意具有染色效果的量将根据本发明的(随角异色效应)颜料添加到被染色的高分子量的有机材料中。包括高分子量有机材料和以重量计,为所述高分子量有机材料的0.01-80%、优选0.1-30%根据本发明颜料的颜料组合物是有利的。实际上,经常使用以重量计1-20%,特别为以重量计大约10%的浓度。
高浓度例如以重量计高于30%的浓度通常为浓缩物(母料)的形式,可将所述浓缩物用作制备具有相对较低颜料含量的颜料材料的染色剂,在常规配方中,所述根据本发明的颜料具有超低的粘度,从而使之仍可很好地加工。
为使有机材料染色,可单独使用根据本发明的随角异色效应颜料。然而,为了达到不同的色度和色彩效果,除了根据本发明的随角异色效应颜料之外,向高分子量的有机物质中添加任意期望量的其它染色成分如白色、彩色、黑色或者效应颜料是可能的。当彩色颜料同根据本发明的随角异色效应颜料混合使用时,优选以重量计,总量为高分子量有机材料的0.1-10%。特别地,优选通过将根据本发明的随角异色效应颜料同另一种颜色的彩色颜料,特别是一种互补色彩色颜料结合使用,可提供高角色差,在10°测量角时,使用随角异色效应颜料的色泽和使用所述彩色颜料的色泽具有20-340,特别是150-210的色度差(ΔH*)。
优选将根据本发明的随角异色效应颜料同透明彩色颜料结合使用,所述透明彩色颜料存在于与根据本发明的随角异色效应颜料相同的介质中,或者存在于邻近介质中是可能的。一种随角异色效应颜料和彩色颜料有利地存在于邻近介质中的方案实例为一种多层随角异色效应涂覆物。
例如通过使用辊式破碎机或者混合或碾磨装置来使这样一种颜料,适宜时以母料的形式,同基底混合,从而用根据本发明的颜料使高分子量有机物质染色。然后使用本身已知的方法例如轧光、压力成型、挤压、涂覆、浇注、注塑成型使染色后的材料达到期望的最终形态。在加入所述颜料之前或之后,可将任何塑料工业中常规的添加剂例如增塑剂、填充剂或者稳定剂以常规量添加到所述聚合物中。特别地,为了制备柔性形态的工件,或者为了降低它们的脆度,在成形之前,期望将增塑剂例如磷酸、酞酸或癸二酸的酯类添加到高分子量化合物中。
为了使涂层和油墨染色,将高分子量有机材料和根据本发明的随角异色效应颜料,适宜时同常规添加剂一起很好地分散或溶解在相同的有机溶剂或溶剂混合物中,所述常规添加剂例如为填充剂、其它颜料、干燥剂或增塑剂。将每一种成分分开溶解或分散,或者将一些成分一起溶解或分散,并仅在此之后才有可能使所有成分混合在一起。
优选在这样一种条件下将根据本发明的随角异色效应颜料分散在将被染色的高分子量有机材料中,并加工根据本发明的颜料组合物,在所述条件下,仅产生相对弱的剪切力从而使得随角异色效应颜料不会破碎成更小的部分。
所述塑料包括以重量计0.1-50%,特别地以重量计0.5-7%的本发明颜料。在涂层部分,使用的本发明颜料以重量计为0.1-10%。在粘合剂体系的染色中,例如用于凹雕、胶印或网目印刷的涂料和油墨,在所述油墨中添加以重量计0.1-50%,优选以重量计5-30%,特别地以重量计8-15%的所述颜料。
例如在塑料、涂层或者油墨中,特别地在涂层或油墨中,更特别地在涂层中获得的色彩以极好的性能、特别地以超高饱和度、突出的不褪色性能和高角色差而著名。
当所述被染色的高分子量材料是一涂层时,具体地可以是一种专业涂层,非常具体地为一种汽车精饰涂层。
根据本发明的随角异色效应颜料也适于给嘴唇或者皮肤化妆,并适于给头发和指甲染色。
因此,本发明还涉及化妆品制品或配方,所述制品或配方包括以重量计,基于化妆品制品或配方总重量0.0001-90%的颜料,特别是根据本发明的随角异色效应颜料和10-99.9999%的化妆品的适宜载体材料。
这样的化妆品制品或配方例如为口红、胭脂、粉底、指甲油和洗发剂。
可单独或以混合物的形式使用所述颜料。此外,将根据本发明的颜料同其它颜料和/或染色剂一起使用,例如如前所述或如在化妆品制备中公知的那样结合使用是可能的。
优选根据本发明的化妆品制品和配方包含以重量计,基于制品总重量0.005-50%的根据本发明的颜料。
根据本发明,化妆品制品和配方的适宜载体材料包括用于这种组合物的常规材料。
根据本发明的化妆品制品和配方可为例如棍、软膏、霜、乳液、悬浮液、分散体系、粉末或溶液的形式。它们例如为口红、睫毛油制品、胭脂、眼影、粉底、眼线膏、脂粉或指甲油。
如果所述制品为棍形,例如为口红,眼影、胭脂或粉底,所述制品大部分由脂肪类成分组成,其由一种或多种蜡例如地蜡、羊毛脂、羊毛脂醇、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、鲸蜡醇、十八醇、可可脂、羊毛脂脂肪酸、石油冻、石油膏、单、二或三-甘油酯或其脂肪酸酯,后者在25℃为固体、硅酮蜡如甲基正十八烷-羟基聚硅氧烷和聚(二甲基硅氧基)-硬脂氧基硅氧烷、硬脂酸单乙醇胺、松香(colophane)及其衍生物例如乙二醇松香酯、甘油松香酯和氢化油,后者在25℃为固体、糖类甘油酯和钙、镁、锆和铝的油酸盐、十四酸盐、亚油酸盐、硬脂酸盐和二羟基硬脂酸盐组成。
所述脂肪成分还可以由至少一种蜡和至少一种油的混合物组成,在这种情况下,例如下述油是适宜的:石蜡油、purcelline油、全氢化角鲨烯、甜杏仁油、鳄梨油、美珊瑚属油、蓖麻油、芝麻油、希蒙德木油、沸点大约为310-410℃的矿物油、硅油例如二甲聚硅氧烷、亚油烯基醇、亚麻醇、油醇、谷类杂醇油例如麦胚油、亚油酸异丙基酯、棕榈酸异丙酯、肉豆蔻酸异丙酯、肉豆蔻酸丁酯、鲸蜡醇肉豆蔻酸酯、硬脂酸十六基酯、硬脂酸丁酯、油酸癸基酯、乙酰甘油酯、醇类和多元醇类的辛酸酯和癸酸酯,例如乙二醇和甘油的辛酸酯和癸酸酯、醇类和多元醇类的蓖麻醇酸酯例如鲸蜡醇、异十八醇的蓖麻醇酸酯、亚油酸异鲸蜡基酯、己二酸异丙基酯、月桂酸己基酯以及辛基十二烷醇。
棍形制品的脂肪成分以重量计,通常可高达所述制品总重量的99.91%。
根据本发明的化妆品制品和配方还可包括其它成分例如乙二醇、聚丙二醇、单链烷醇酰胺、未染色的聚合、无机或有机填充物、防腐剂、紫外线滤光剂或其它助剂,以及在化妆品中的常规添加剂例如天然或合成的,或者部分合成的二或三-甘油酯、矿物油、硅油、蜡、脂肪族醇、盖尔贝醇或其酯,亲油性功能的化妆品有效成份包括防晒滤光剂、或者这些物质的混合物。
亲油性功能化妆品的有效成份适宜用作护肤品;有效成份组合物或有效成份的提取物是一种经许可用于皮肤或者局部施用的成分或成分混合物。下面将通过实施例提到:
-在皮肤表面和头发上具有清洗作用的有效成分;这包括所有用于清洗皮肤的物质例如油、肥皂、合成洗涤剂和固态物质。
-具有去臭和止汗作用的有效成分:它们包括基于铝盐或锌盐的止汗剂、包括杀菌或抑菌的去臭物质的除臭剂,例如三氯苯氧氯酚、六氯酚、醇类和阳离子物质例如季铵盐、以及气味吸收剂例如Grillocin(蓖麻醇酸酯锌和多种添加剂的组合物)或者柠檬酸三乙酯(任选与一种抗氧化剂结合使用,例如丁基羟基甲苯)或者离子交换树脂;
-提供抗阳光的有效成分(紫外线滤光剂):所述滤光物质(防晒剂)为适宜的有效成分,其能吸收来自阳光的UV辐射并将之转化为热量;取决于预定的作用,优选下述光保护剂:选择性吸收太阳暴晒导致的、在大约280-315nm范围内的高能量UV辐射(UV-B吸收剂)且发射更长的波长例如315-400nm(UV-A范围)的光保护剂,以及仅吸收更长波长UV-A范围辐射的光保护剂(UV-A吸收剂),所述UV-A范围为315-400nm;适宜的光保护剂例如为来自对氨基苯甲酸衍生物、水杨酸衍生物、二苯甲酮衍生物、二苯甲酰甲烷衍生物、二苯基丙烯酸酯衍生物、苯并呋喃衍生物的有机UV吸收剂;包括一种或多种有机硅基团的聚合物UV吸收剂、肉桂酸衍生物、樟脑衍生物、三苯氨基-S-三嗪衍生物、苯基苯并咪唑磺酸及其盐、氨茴酸甲酯、苯并三唑衍生物、和/或选自涂覆有氧化铝或二氧化硅的TiO2、氧化锌或云母的无机微米颜料;
-抗虫(驱虫剂)的有效成分为那些用来阻止昆虫接触皮肤并在皮肤上有效的试剂;它们将昆虫驱走并缓慢蒸发;最常使用的驱虫剂为二乙基甲苯酰胺(DEET);也可找到其它常规的驱虫剂例如参看“Pflegekosmetik”
(W.Raab and U.Kindl,Gustav-Fischer-Verlag Stuttgart/NewYork,1991)第161页;
-用于保护抵抗化学和机械影响的有效成分:其包括所有在皮肤和外部有害物质之间形成阻挡层的物质,例如石蜡油、硅油、植物油、PCL产品和用于保护抵抗水溶液的羊毛脂,成膜剂例如海藻酸钠、三乙醇胺藻朊酸盐、聚丙烯酸脂、聚乙烯醇或纤维素,用于保护抵抗有机溶剂作用的醚类,或者基于矿物油、植物油或硅油作为“润滑剂”用于保护抵抗皮肤上严重机械应力的物质;
-润湿剂:例如将下述物质用作湿度控制剂(润湿剂):乳酸钠、尿素、醇类、山梨糖醇、甘油、丙二醇、胶原、弹性蛋白和透明质酸;
-具有塑性角质效应的有效成分:过氧化苯甲酰、维生素A酸、胶态硫和间苯二酚;
-杀菌剂,例如三氯苯氧氯酚或者季铵化合物;
-可施加在皮肤上的油性或油溶性维生素或者维生素衍生物:例如维生素A(游离酸形式的视黄醇或其衍生物)、泛酰醇、泛酸、叶酸及其组合物、维生素E(生育酚)、维生素F、必需脂肪酸、或尼克酰胺(烟酰胺);
-维生素基的胎盘提取物:有效成分组成特别包括维生素A、C、E、B1、B2、B6、B12叶酸和维生素H、氨基酸、酶类、以及痕量元素镁、硅、磷、钙、锰、铁或铜的化合物;
-修复皮肤的络合剂:可从失去活性和蜕变的双岐杆菌培养液中获得;
-植物和植物提取物:例如山金车酊、芦荟、须松罗、常春藤、小荨麻、人参、指甲花、春黄菊、万寿菊、迷迭香、圣人、木贼、百里香;
-动物提取物:例如王浆、蜂胶、蛋白质、胸腺提取物;
-可施加在皮肤上的化妆油:Miglyol 812型中性油、苦杏仁油、鳄梨油、巴巴苏油、棉子油、琉璃苣籽油、蓟油、花生油、伽马-谷维素、玫瑰果仁油、大麻籽油、榛子油、黑醋栗植物油、希蒙德木油、樱桃核油、鲑鱼油、亚麻子油、玉米胚油、昆士兰果油、杏仁油、月见草油、貂油、橄榄油、美洲山核桃胡桃油、桃仁油、乳香黄连木油、菜油、水稻胚油、蓖麻油、红花油、芝麻油、豆油、向日葵油、茶树油、葡萄子油、麦胚油。
棍状形式的制品优选为无水的,但在某些情况下,可包含一定量的水,但是以重量计,通常不超过化妆制品总重量的40%。
如果根据本发明的化妆制品或配方为半固体产品,也就是说为软膏或面霜的形式,它们同样可以是无水或含水的。这种制品和配方例如为睫毛油、眼影膏、粉底、胭脂、眼影膏或者用于处理眼下部环形部分的组合物。
另一方面,如果软膏或者面霜是含水的,特别地,它们为油包水型或水包油型的水乳液,除了所述颜料,以重量计,它们包括1-98.8%的脂肪相,1-98.8%的水相以及0.2-30%的乳化剂。
这种软膏和面霜还可包括常规添加剂,例如香料、抗氧化剂、防腐剂、凝胶形成剂、紫外线滤光剂、染色剂、颜料、珠光剂、非彩色聚合物、以及无机或有机填充剂。
如果制品为粉末形式,它们大体上由矿物、或无机或有机填充剂组成,例如滑石、高岭土、淀粉、聚乙烯粉末、聚酰胺粉末以及助剂例如粘合剂、染色剂等等。
这些制品同样也可包括多种在化妆品中使用的常规助剂,例如香料、抗氧化剂、防腐剂等等。
如果根据本发明的制品和配方为指甲油,它们大体上由硝化纤维和以溶剂体系中溶液形式存在的天然聚合物或合成聚合物组成,所述溶液包括其它助剂例如珠光剂是可能的。
在那种实施方案中,以重量计,所述彩色聚合物以大约0.1-5%的量存在。
根据本发明的制品和配方也可用于头发着色,在所述情况下,它们以洗发剂、膏状物或凝胶的形式使用,其由化妆品工业通常使用的基本物质和根据本发明的颜料组成。
可以常规方式制备根据本发明的制品和配方,例如将所述成分混合或搅拌在一起,任选地可加热从而使得所述混合物融解。
下面说明本发明的实施例不限制本发明的范围。除非标明,百分比和等分各为重量百分比和重量等分。
实施例
实施例1
在真空室中,在低于大约10-2Pa的压力下,将大约50nm的NaCl层蒸气沉积在金属载体上。在相同的压力下,然后将下述物质连续蒸气沉积:SiO、Al和SiO,从而在金属带上制备具有下述层结构的膜:
SiO(270nm)/Al(40nm)/SiO(270nm)。
然后将分离剂溶解在水中,于是薄片从基底分离。在大气压下,将所得悬浮液通过过滤浓缩,为了去除存在的Na+和Cl-离子并用去离子水清洗几次。在干燥之后,获得呈现金属光泽、同现有铝薄片相比,具有更明亮外观和更大亮度的、涂覆有SiO的铝薄片。
为了增加耐气候性和耐光性,可在炉中将松散料形式的颜料在200℃下加热2小时,其中加热到200℃的空气通过所述炉。
Claims (10)
1.一种铝薄片,包括:
(A1)一层由SiOz组成的层,
(B)在(A1)层上,一层由铝组成的层以及
(A2)在(B)层上,一层由SiOz组成的层,
其中,0.70≤z≤2.0。
2.根据权利要求1的铝薄片,包括:
(C1)一层由SiO2组成的层,
(A1)在层(C1)上,一层由SiOy组成的层,
(B)在层(A1)上,一层由铝组成的层,
(A2)在层(B)上,一层由SiOy组成的层,以及
(C2)在层(A2)上,一层由SiO2组成的层,
其中,0.95≤y≤2.0。
3.一种铝薄片,包括:
(D1)一层由SiO2组成的层,
(B)在层(D1)上,一层由铝组成的层,以及
(D2)在层(B)上,一层由SiO2组成的层,其中所述SiO2层的层厚为200-500nm,特别为200-350nm。
4.根据权利要求1-3中任一的铝薄片,其中所述由铝组成的层(B)的层厚为10-100nm,优选为30-50nm。
5.根据权利要求1或2的铝薄片,其中由SiOz组成的层(A1)和(A2)的层厚、由SiO2组成的层(D1)和(D2)的层厚、由SiOy组成的层(A1)和由SiO2组成的层(C1)的层厚,以及由SiOy组成的层(A2)和由SiO2组成的层(C2)的层厚为200-350nm,优选为250-300nm。
6.根据权利要求1,2,3,4和5中任一的基于所述铝薄片的颜料,在层(A1)和(A2)上、或在层(C1)和(C2)上、或在层(D1)和(D2)上、或在所述铝薄片的整个表面上,包括一层由绝缘材料组成的层(E),该绝缘材料具有“高”折射率,特别为TiO2或者为碳,优选为金刚石型碳。
7.根据权利要求1,2,3,4和5中任一的基于所述铝薄片的颜料,在所述铝薄片的整个表面上,包括一(F)层,其由以重量计50-95%的碳,以重量计5-25%的氮,以重量计0-25%的氢、氧和/或硫元素组成,以重量计的百分比数值基于(F)层的总重量。
8.根据权利要求6或7中任一的颜料,其中层(E)或(F)的层厚为10-150nm,优选为30-70nm。
9.根据权利要求1-5中任一的铝薄片在涂料、静电涂覆、在喷墨印刷、化妆品、涂层、油墨、塑性材料、在用于陶瓷和玻璃的釉料、在安全印刷中的用途,或者根据权利要求6,7或8的颜料在涂料、喷墨印刷、化妆品、涂层、油墨、塑性材料、在用于陶瓷和玻璃的釉料以及在安全印刷中的用途。
10.一种组合物,包括根据权利要求1-5中任一的铝薄片或者包括根据权利要求6,7或8的颜料。
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CH20022089/02 | 2002-12-10 |
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CN200380105546.3A Pending CN1723250A (zh) | 2002-12-10 | 2003-12-01 | 基于涂覆有SiOz(0.70≤z≤2.0)的铝的薄片形式的颜料 |
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US (1) | US20060034787A1 (zh) |
EP (1) | EP1570007A2 (zh) |
JP (1) | JP2006509088A (zh) |
KR (1) | KR20050085428A (zh) |
CN (1) | CN1723250A (zh) |
AU (1) | AU2003300248A1 (zh) |
CA (1) | CA2507555A1 (zh) |
MX (1) | MXPA05006198A (zh) |
RU (1) | RU2005121668A (zh) |
WO (1) | WO2004052999A2 (zh) |
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- 2003-12-01 CN CN200380105546.3A patent/CN1723250A/zh active Pending
- 2003-12-01 RU RU2005121668/15A patent/RU2005121668A/ru not_active Application Discontinuation
- 2003-12-01 KR KR1020057010335A patent/KR20050085428A/ko not_active Application Discontinuation
- 2003-12-01 MX MXPA05006198A patent/MXPA05006198A/es unknown
- 2003-12-01 WO PCT/EP2003/050914 patent/WO2004052999A2/en active Application Filing
- 2003-12-01 US US10/537,724 patent/US20060034787A1/en not_active Abandoned
- 2003-12-01 AU AU2003300248A patent/AU2003300248A1/en not_active Abandoned
- 2003-12-01 JP JP2004558100A patent/JP2006509088A/ja not_active Withdrawn
- 2003-12-01 CA CA002507555A patent/CA2507555A1/en not_active Abandoned
- 2003-12-01 EP EP03799525A patent/EP1570007A2/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101535419B (zh) * | 2006-08-28 | 2012-11-14 | 韩国化学研究院 | 具有大纵横比的珠光颜料及其制备方法 |
CN113544219A (zh) * | 2019-03-05 | 2021-10-22 | 东洋铝株式会社 | 黑色铝颜料及其制造方法 |
CN115160831A (zh) * | 2022-06-22 | 2022-10-11 | 合肥旭阳铝颜料有限公司 | 一种具有镜面效果的水性铝颜料及其制备方法和应用 |
CN115160831B (zh) * | 2022-06-22 | 2023-11-28 | 合肥旭阳铝颜料有限公司 | 一种具有镜面效果的水性铝颜料及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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KR20050085428A (ko) | 2005-08-29 |
US20060034787A1 (en) | 2006-02-16 |
WO2004052999A2 (en) | 2004-06-24 |
JP2006509088A (ja) | 2006-03-16 |
WO2004052999A3 (en) | 2004-07-29 |
RU2005121668A (ru) | 2006-02-10 |
EP1570007A2 (en) | 2005-09-07 |
MXPA05006198A (es) | 2005-08-19 |
CA2507555A1 (en) | 2004-06-24 |
AU2003300248A1 (en) | 2004-06-30 |
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