CN101410462B - 具有金色调的光辉性颜料以及含有该颜料的化妆料、涂料、油墨和树脂组合物 - Google Patents
具有金色调的光辉性颜料以及含有该颜料的化妆料、涂料、油墨和树脂组合物 Download PDFInfo
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- CN101410462B CN101410462B CN2007800115910A CN200780011591A CN101410462B CN 101410462 B CN101410462 B CN 101410462B CN 2007800115910 A CN2007800115910 A CN 2007800115910A CN 200780011591 A CN200780011591 A CN 200780011591A CN 101410462 B CN101410462 B CN 101410462B
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- overlay film
- yellow
- pigment
- nickel
- photoluminescent pigment
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 69
- 239000010931 gold Substances 0.000 title claims abstract description 69
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- 239000000463 material Substances 0.000 claims abstract description 128
- 239000011521 glass Substances 0.000 claims abstract description 101
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 43
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
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- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229940043774 zirconium oxide Drugs 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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Abstract
本发明提供一种具有金色调的光辉性颜料,其包含鳞片状玻璃基材(10)、含有选自银、镍和镍系合金中的至少1种金属材料的基底覆膜(20)、含有金的金覆膜(30)以及含有黄色色素和母材的黄色覆膜(40)。上述基底覆膜(20)、上述金覆膜(30)和上述黄色覆膜(40)分别形成层以包覆上述鳞片状玻璃基材(10),且上述基底覆膜(20)、上述金覆膜(30)和上述黄色覆膜(40)中,上述基底覆膜(20)被配置在最内侧。
Description
技术领域
本发明涉及具有金色调的光辉性颜料、进一步涉及含有该颜料的化妆料、涂料、油墨和树脂组合物等。
背景技术
一直以来,作为光辉性颜料,已知鳞片状的铝粒子、石墨片粒子、鳞片状玻璃粒子、用银包覆的鳞片状玻璃粒子、用二氧化钛或氧化铁等金属氧化物包覆的云母片粒子等。
这些光辉性颜料的表面具有反射光并闪闪地发光的特性,因而作为涂料、油墨、树脂组合物或化妆料等材料使用。在通过涂布涂料而获得的涂饰面、使用了油墨的印刷面、或使用树脂组合物成形得到的树脂成形物的表面上,这些光辉性颜料与这些面质地的色调互相结合、赋予其富有变化且美妆性优异的独特外观。
另外,作为具有金属光泽的光辉性颜料,已知有如下物质。
(1)铝粉体或者将在箔状树脂上包覆有金属的物质进行粉碎加工而获得的粉体
(2)在云母粉体上进行了金属包覆的物质
这些光辉性颜料由于具有金属光泽,因此能够赋予使用对象很强的光辉感,从而可以赋予使用对象设计性特别优异的外观。
因此,光辉性颜料可分别与汽车、摩托车、OA机器、手机、家庭电子制品等涂饰中所使用的涂料、各种印刷物或笔记用具类等的油墨、或化妆料混合而加以利用,因此被用于广泛的用途中。
其中,具有金色调的光辉性颜料由于呈现富于高级感的色彩,因此优选地被用于这些各种用途中。
作为具有金色调的光辉性颜料,例如METASHINE(注册商标)GG已经由本申请人上市。该光辉性颜料中,薄片状玻璃基材用银包覆、进而用金包覆。还提出了含有用金属包覆的薄片状玻璃基材的化妆料(例如参照日本特开2002-138010号公报)。
还公开了云母等基材被金属氧化物包覆的金属颜料(例如参照日本特开平9-12919号公报)。该金属颜料中,基材被掺杂有碳的二氧化钛层和氧化铁(III)层依次包覆。
还公开了玻璃薄片被二氧化钛覆膜和氧化铁覆膜依次包覆的化妆品用珍珠光泽颜料(例如参照日本特开2004-352725号公报)。另外,还公开了鳞片状玻璃粉体被金属覆膜层包覆、金属覆膜层被含有无机或有机颜料的二氧化硅类被膜包覆的着色光辉性颜料(例如参照WO2005/071019号)。
以往,对于具有金覆膜的光辉性颜料,为了获得纯金般的色调,需要使金覆膜的厚度达到10nm~20nm以上。因此,具有金色调的光辉性颜料不得不变得昂贵,由于成本方面的原因,其用途有受限的倾向。
另外,对于具有氧化物覆膜的光辉性颜料,即使欲获得纯金般的色调,也有由于观察角度而无法成为所期望色调的问题。
发明内容
本发明提供一种光辉性颜料、以及含有该颜料的化妆料、涂料、油墨或树脂组合物等,其中,即使金覆膜的厚度薄于以往金覆膜的厚度,也可以获得纯金般的色调。
本发明具有金色调的光辉性颜料的特征在于,包含:鳞片状玻璃基材、含有选自银、镍和镍系合金中的至少1种金属材料的基底覆膜、含有金的金覆膜以及含有黄色色素和母材的黄色覆膜,其中,上述基底覆膜、上述金覆膜和上述黄色覆膜分别形成层以包覆上述鳞片状玻璃基材,且上述基底覆膜、上述金覆膜和上述黄色覆膜中,上述基底覆膜被配置在最内侧。
本发明的化妆料含有本发明的具有金色调的光辉性颜料。
本发明的涂料含有本发明的具有金色调的光辉性颜料。
本发明的油墨含有本发明的具有金色调的光辉性颜料。
本发明的树脂组合物含有本发明的具有金色调的光辉性颜料。
附图说明
图1为本发明具有金色调的光辉性颜料的一个例子的截面示意图。
图2为本发明具有金色调的光辉性颜料另一个例子的截面示意图。
图3为说明色调的测定方法的概念图。
图4为说明动态指数的测定方法的概念图。
具体实施方式
如图1所示,本发明具有金色调的光辉性颜料(以下有时也仅称作“光辉性颜料”)的一个例子中,其包含鳞片状玻璃基材10、基底覆膜20、金覆膜30和黄色覆膜40。鳞片状玻璃基材10由基底覆膜20、金覆膜30以及黄色覆膜40依次包覆。另外,如图2所示,本发明光辉性颜料的另一个例子中,鳞片状玻璃基材10由基底覆膜20、黄色覆膜40以及金覆膜30依次包覆。
(用途)
本发明光辉性颜料的安全性高、稳定,且由于具有金色调,因此可被添加而用于各种用途,例如化妆料、油墨、涂料或树脂组合物等中。
作为上述化妆料,可列举出面部化妆料、彩妆化妆料、毛发化妆料等。本实施方式的光辉性颜料特别适宜用于底霜、粉等粉底,眼影,指甲油,眼线,睫毛膏,口红以及香粉(lame powder)等彩妆化妆料中。化妆料的形态并无特别限定,可列举出粉末状、饼状、笔状、棒状、软膏状、液体状、乳液状以及膏状等。
作为使用了上述油墨的印刷对象,可列举出包装箱、包装纸、壁纸、织物、化妆版、纺织品、各种薄膜以及标签等。
作为上述涂料可应用的领域,可列举出汽车、摩托车和自行车等外部装饰、建材、瓦、家具、家庭用品、容器、办公用品以及运动用品等。
作为使用上述树脂组合物进行成形的成形体,可列举出化妆料用容器、食品容器、墙壁装饰材料、地板材料、家电制品的框体、服饰用品、文具、玩具、浴槽、洗浴用品、鞋类、运动用品以及洗手间用品等。
本实施方式的光辉性颜料除了上述用途以外,还可以作为水彩绘具、油画绘具、合成皮革、织物印花、纽扣、漆器、陶瓷器颜料等的材料使用。
(鳞片状玻璃基材)
鳞片状玻璃基材10的形状随使用用途的不同而不同,并无特别限定。一般优选平均粒径为1μm~500μm、平均厚度为0.3μm~10μm。如果平均粒径过大,则光辉性颜料在配合于涂料或树脂组合物等中时,有鳞片状玻璃基材10破碎的危险。另一方面,如果平均粒径过小,则在涂膜或树脂成形物等中,光辉性颜料(粒子)的主平面朝向任意的方向,且各个粒子发出的反射光变弱。因此,有损光辉感。如果平均粒径为1μm~500μm,则可以抑制光辉性颜料在配合过程中破碎、且可提高光辉感。
本发明光辉性颜料的一个例子,例如在用于化妆料时,鳞片状玻璃基材10的平均粒径可以根据化妆料的种类等进行适当选择,通常优选为20μm~500μm、更优选为20μm~250μm。如果平均粒径为20μm~500μm,则各粒子的光辉强、能实现具有更加闪亮的粒子感的化妆料。
鳞片状玻璃基材10的平均厚度优选为0.5μm~7μm、更优选为0.5~3μm。如果平均厚度为0.5μm~7μm,则含有本发明光辉性颜料的化妆料在构成肌肤、指甲、嘴唇等角质的角蛋白表面上的伸展性和使用感良好,因此优选。
作为本发明光辉性颜料的一个例子,例如在用于油墨时,鳞片状玻璃基材10的平均粒径优选为1μm~40μm、更优选为15~30μm。例如,在利用凹版印刷等方法印刷油墨时,如果光辉性颜料的平均粒径为1μm~40μm,则印刷版起雾(plate fogging)等的印刷适应性变得良好。其中,印刷版起雾是指在印刷时刮刀片无法将版上的油墨充分地刮掉,该油墨被转印到被印刷体上,从而引起印刷物污染的现象。
鳞片状玻璃基材10的平均厚度优选为0.3μm~3μm。如果平均粒径为0.3μm~3μm,则印刷的表面加工性变得良好。
对鳞片状玻璃基材10的制造方法并无特别限定,但例如优选吹塑法。吹塑法中,首先将原料碎玻璃熔融。将熔融的玻璃从圆形缝隙中连续地排出,同时从设置在圆形夹缝内侧的吹嘴吹入空气等气体。由此,在熔融的玻璃膨胀的同时对其进行拉伸,使成为球状。将该球状的玻璃粉碎,即可获得鳞片状玻璃基材10。
通过上述吹塑法制造的鳞片状玻璃基材10具有平滑的表面,因此良好地反射光。将使用了上述鳞片状玻璃基材10的光辉性颜料的一个例子配合到涂料或树脂组合物等中,由于能够获得光辉感高的涂饰面或树脂成形体等,因此优选。作为这样的鳞片状玻璃基材10的市售品,例如可列举出日本板硝子株式会社制的MICROGLAS(注册商标)、GLASFLAKE(注册商标)系列(RCF-160、REF-160、RCF-015、REF-015)。
(基底覆膜)
基底覆膜20含有选自银、镍和镍系合金中的至少1种金属材料作为主成分。基底覆膜20含有银单体时,基底覆膜20可以实质上由银构成。基底覆膜20含有镍单体时,基底覆膜20可以实质上由镍构成。
将本发明光辉性颜料的总质量设定为100质量%时,选自银、镍和镍系合金中的至少1种金属材料优选含有10质量%以上、进一步优选含有15质量%以上、更加优选含有20~25质量%。
作为镍系合金,例如优选镍-磷合金、镍-钨-磷合金、镍-铁-钨-磷合金、镍-钴合金、镍-钴-磷合金、镍-钯-磷合金、镍-锡-磷合金或镍-铜-磷合金。由于镍系合金的耐水性和耐腐蚀性高于镍单体,因此当基底覆膜20含有镍系合金时,含有本发明光辉性颜料的油墨或涂料等的耐水性和耐腐蚀性提高。但是,从确保高光辉感的观点出发,镍系合金中的镍含量优选为60原子%以上、更优选为70原子%以上。
本发明光辉性颜料中由于用上述基底覆膜20包覆鳞片状玻璃基材10,因此反射光量增大、光辉性颜料的光辉感提高。
用基底覆膜20包覆鳞片状玻璃基材10的方法并无特别限定,可以使用公知的覆膜形成方法。
作为在表面上形成有银覆膜并呈现光辉感的鳞片状玻璃基材的市售品,具体地可列举出日本板硝子株式会社制的MICROGLAS(注册商标)、METASHINE(注册商标)PS系列(MC2080PS、MC5480PS、MC5230PS、MC5150PS、MC5090PS、MC5030PS、ME2040PS、ME2025PS)等。
作为呈现出与上述形成有银覆膜的鳞片状玻璃基材同样的光辉感、而表面形成有镍-磷合金覆膜的鳞片状玻璃基材的市售品,例如可列举出日本板硝子株式会社制的MICROGLAS(注册商标)、METASHINE(注册商标)NS系列(MC5048NS、MC5230NS、MC5150NS、MC5090NS、MC5030NS)等。
当基底覆膜20由含有银的含银基底覆膜构成时,其膜厚优选为20~100nm。含银基底覆膜的膜厚为20~100nm时,可以充分地获得设置含银基底覆膜所产生的反射光量的增大效果、且可以抑制设置基底覆膜所造成的成本增加。
基底覆膜20由含有镍或镍系合金的含镍基底覆膜构成时,其膜厚优选为40~200nm。含镍基底覆膜的膜厚为40~200nm时,可以充分地获得设置含镍基底覆膜所产生的反射光量的增大效果、且可以抑制设置基底覆膜所造成的成本增加。
基底覆膜20如图1和图2的例子所示,并非限定于由单层构成的覆膜。例如可以为由含镍膜和含银膜构成的2层结构。
(金覆膜)
金覆膜30可以含有金,但也可以实质上由金构成。金覆膜的形成方法并无特别限定。金覆膜的形成方法例如可列举出溅射法、CVD法、非电解镀层法等方法,但其中,从容易均匀成膜的观点出发,优选非电解镀层法。
金覆膜30的膜厚优选为0.5~5nm、更优选为1~3nm、进一步优选为1~2nm。金覆膜30的膜厚越薄,则金覆膜30对可见光的透过性变得越高。透过金覆膜30的光在基底覆膜20处反射,在基底覆膜20处经反射的光在界面处发生折射和/或散射等,从而增大光辉性颜料的光辉感。但是,如果金覆膜30的膜厚过薄,则会有损光辉性颜料的金色调。如果金覆膜的膜厚为0.5nm~5nm,则由基底覆膜20反射产生的光量的增大效果与金覆膜30的色调、进而与黄色覆膜的色调相辅相成,因此可以提供具有良好金色调的光辉性颜料。另外,由于上述膜厚薄于构成以往光辉性颜料的金覆膜的膜厚,因此本发明中可以大幅度地降低光辉性颜料的成本。
(黄色覆膜)
黄色覆膜40含有母材和保持在母材中的黄色色素。另外,黄色覆膜40还需要能透过可见光。透过黄色覆膜的可见光到达基底覆膜或金覆膜后发生反射。通过该反射,表现出光辉性颜料的高光辉性。
作为可见光能够透过的母材材料,例如可列举出选自氢氧化铝、氢氧化锆、氢氧化钙、水合氧化铝、水合氧化锆、水合氧化钙、二氧化硅和水滑石中的至少1种材料。
其中,优选选自氢氧化铝、水合氧化铝、氢氧化锆以及水合氧化锆中的至少1种材料。这些材料作为使后述水溶性黄色色素对Al和/或Zr发生色淀化的材料是适宜的。另外,由于透明性非常高,因此适宜作为包覆鳞片状玻璃基材的材料。
黄色色素例如可列举出以下的水溶性色素和非水溶性色素。
<水溶性色素>
作为水溶性色素优选的具体例子,例如可列举出由色指数通用名称(C.I.G.N)规定的酸性黄23(日本的法定色素名称中为黄色4号,对以下括号内的色素名同样)、食品黄3(黄色5号)、酸性黄73(黄色202号(1)、黄色202号(2))、酸性黄3(黄色203号)、酸性黄40(黄色402号)、酸性黄1(黄色403号)、酸性黄36(黄色406号)、酸性黄11(黄色407号)等黄色的酸性色素。
<非水溶性色素>
作为非水溶性色素优选的具体例子,例如可列举出由上述C.I.G.N规定的酸性黄73(黄色201号)、溶剂黄33(黄色204号)、颜料黄12(黄色205号)、颜料黄1(黄色401号)、溶剂黄5(黄色404号)、溶剂黄6(黄色405号)、颜料黄110、颜料黄139、颜料黄150、颜料黄154等黄色颜料。
对于含有黄色色素的黄色覆膜的形成方法并无特别限定,可以使用公知的方法形成。以下说明几个黄色覆膜的形成方法的例子。
<含有水溶性色素的黄色覆膜的形成方法>
在含有上述水溶性色素的黄色覆膜的形成方法的一个例子中,首先例如用氢氧化铝或氢氧化锆等氢氧化物等将包覆对象物包覆以形成母材。接着,在母材中使水溶性色素浸透,然后将水溶性色素色淀化。水溶性色素在母材中的浸透,例如通过用水将被母材包覆的鳞片状玻璃基材浆料化、并向该浆料中添加水溶性色素而进行。通过加热添加有水溶性色素的浆料而使水溶性色素色淀化,该方法的详细内容例如公开在DE2429762、US4084983、日本特开2002-188023号公报、日本特开2002-194247号公报等中。
根据上述文献,氢氧化铝例如可以通过使酸性铝化合物与适当的碱反应而获得。另外,氢氧化铝还可以通过使碱性铝化合物与适当的酸反应而获得。可以在通过将含有鳞片状玻璃基材的包覆对象物添加于水中而获得的悬浊液中进行这些反应的任何一个,氢氧化铝析出到鳞片状玻璃基材的表面,从而形成由氢氧化铝构成的母材。
作为酸性铝化合物,水溶性矿物酸的铝盐例如可列举出氯化铝、硫酸铝、硝酸铝、磷酸铝等。作为碱性的铝化合物,可列举出铝酸钠等铝酸碱金属盐等。作为适当的碱,例如可列举出氢氧化钠水溶液或氢氧化铵水溶液等。作为适当的酸,例如可列举出盐酸、硫酸或硝酸等。
所用碱或酸的量只要是能够使充分量的氢氧化铝在鳞状片玻璃基材的表面上析出的量即可。上述反应中的上述悬浊液的pH恒定地维持在3~9的范围内,悬浊液的温度维持在30~100℃、优选维持在40~75℃的范围内。将维持了pH和温度的悬浊液搅拌5分钟~4小时、优选30分钟~2小时。
作为锆源优选的具体例子,只要是锆盐类则无特别限定,例如可列举出二氯氧化锆(zirconium oxochloride)、硫酸氧锆(zirconium oxosulfate)、硝酸氧锆(zirconium oxonitrate)、醋酸氧锆(zirconium oxoacetate)、锆醇盐(zirconium alkoxide)等锆化合物。锆源更优选为水溶性的锆化合物,也可以为含有通过水解锆化合物而获得的固体状氢氧化锆的浆料溶液。上述浆料溶液例如可列举出使用氢氧化铵等将氧代硝酸锆的水溶液水解而获得的水溶性不足的氢氧化锆的浆料溶液。
接着,以母材的材料为水滑石的情况为例,说明母材的形成方法。
水滑石为采用2价~3价金属复合氢氧化物形态的层状晶体化合物,并具有阴离子交换性。
含有水溶性黄色染料(酸性色素)的水滑石化合物覆膜的组成可由下述通式(氧化物表示)表示。
M1 1-x·M2 x(OH)2·X2/n·mH2O
其中,式中,x表示0.10≤x≤0.75范围的数值、X表示1价或2价的酸性色素、n表示1或2的原子价、m表示0≤m≤30范围的数值。M1为选自Mg、Mn、Fe、Co、Ni、Cu和Zn中的至少1种的2价金属,M2为选自Al、Cr、Mn、Fe、Co和Ga中的至少1种的3价金属。
含有黄色染料(酸性色素)的水滑石化合物覆膜例如如下形成。
调整在水中添加M1的盐和M2的盐、包覆对象物和酸性色素而获得的悬浊液。作为包覆对象物,可列举出由基底覆膜包覆的鳞片状玻璃基体或由基底覆膜和金覆膜包覆的鳞片状玻璃基体。该混悬液例如用碱进行中和。如此在用水滑石将包覆对象物包覆的同时,将酸性色素***该水滑石母材中。该方法的详细内容例如公开于日本特开2001-234090号公报、日本特开2003-213156号公报。
作为M1的盐,例如可列举出M1的氯化物、硫酸盐、硝酸盐等水溶性盐类。作为M2的盐,可列举出M2的氯化物、硫酸盐、硝酸盐等水溶性盐类。作为上述碱,可列举出氢氧化钠、氢氧化钾、氢氧化铵等。
上述含有水溶性色素的黄色覆膜的厚度优选为10nm~100nm。黄色覆膜的厚度为10nm~100nm时,由于能够含有合适量的黄色色素,因此光辉性颜料可获得适宜的色调和光辉感。
黄色覆膜中的黄色色素的含量,将光辉性颜料总质量设定为100质量%时,优选为0.1~10质量%、更优选为0.5~5质量%、进一步优选为1~3质量%。
<含有非水溶性色素的黄色覆膜的形成方法>
在含有非水溶性色素的黄色覆膜的形成方法的一个例子中,首先在含有能够水解、缩聚的有机金属化合物和非水溶性色素的涂布溶液中分散包覆对象。包覆对象为由基底覆膜和金覆膜依次包覆的鳞片状玻璃基材或为由基底覆膜包覆的鳞片状玻璃基材。然后,通过对其持续搅拌1~15小时,使有机金属化合物水解、缩聚。由此,可以在鳞片状玻璃基材的表面上形成含有非水溶性色素的覆膜。涂布溶液中的由基底覆膜和金覆膜依次包覆的鳞片状玻璃基材的添加量,将光辉性颜料总质量设定为100质量%时,优选确定为1~30质量%。金覆膜的质量由于少至可以忽略的程度,因此对于涂布溶液中的由基底覆膜包覆的鳞片状玻璃基材的添加量,将光辉性颜料总质量设定为100质量%时,优选确定为1~30质量%。
接着,将被黄色覆膜包覆的鳞片状玻璃基材过滤、水洗、干燥。用于干燥的热处理优选在室温~200℃下进行1~5小时。
作为有机金属化合物优选的具体例子,可列举出有机硅化合物、有机钛化合物、有机锆化合物或有机铝化合物等,但其中,从可见光的透过性高的角度出发,优选有机硅化合物。有机金属化合物含有有机硅化合物时,形成作为母材的二氧化硅类被膜。该方法的详细内容例如公开在日本特开平5-171055、日本特开平7-133211、日本特开2006-176742等中。
黄色覆膜的厚度并无特别限定,从确保良好的色调、确实地保持非水溶性色素、确保覆膜的高表面平滑性以及降低成本的观点出发,优选为10nm~500nm。
二氧化硅类覆膜可以含有二氧化硅(SiO2)作为主成分,也可以实质上仅由二氧化硅构成。二氧化硅覆膜为了调整覆膜的折射率、提高耐碱性,也可以含有二氧化钛或二氧化锆等。
作为涂布溶液中所含的可水解、缩聚的有机硅化合物优选的具体例子,可列举出四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷等四烷氧基硅烷,或甲基三甲氧基硅烷、甲基三乙氧基硅烷、甲基三丙氧基硅烷、甲基三丁氧基硅烷等甲基三烷氧基硅烷。
其中,分子量较小的化合物、例如具有碳原子数为3以下的烷氧基的四烷氧基硅烷由于易于形成致密的覆膜,因此优选。另外,更优选为四烷氧基硅烷的聚合物、且平均聚合度为5以下的化合物。
涂布溶液例如优选含有0.5~20质量%的有机硅化合物、0.01~5质量%的非水溶性色素。涂布溶液除了这些以外,还含有用于水解的水和醇类溶剂。
涂布溶液中水的含量优选为0.1~20质量%。
作为醇类溶剂,例如优选甲醇、乙醇、1-丙醇、2-丙醇、丁醇、戊醇等。进一步优选碳原子数为3以下的链式饱和1元醇,因为其常温下的蒸发速度快。作为碳原子数为3以下的链式饱和1元醇,可列举出甲醇、乙醇、1-丙醇、2-丙醇等。涂布溶液中的上述醇类溶剂的含量例如优选为50~98质量%。
涂布溶液可以含有催化剂。作为催化剂,从促进有机硅化合物的水解、缩聚,且可对各粒子(由基底覆膜和金覆膜依次包覆的鳞片状玻璃基材或由基底覆膜依次包覆的鳞片状玻璃基材)形成良好黄色覆膜的观点出发,优选氢氧化铵、氢氧化钠等碱催化剂。涂布溶液中催化剂的含量优选为0.1~10质量%。
涂布溶液的pH适宜为9~13。
非水溶性色素的平均粒径并无特别限定,优选为10nm~500nm。如果平均粒径过小,则黄色颜料的耐久性极度变差。另一方面,如果平均粒径过大,则黄色颜料所导致的反射光的遮挡增大,光辉感降低、色泽也变差。
非水溶性色素的含量,将本发明光辉性颜料的总质量设定为100质量%时,优选为2.0质量%以下、更优选为小于1.0质量%、进一步优选为0.01~0.8质量%。
以下举出实施例和比较例详细地说明本发明的一个例子。
各种平均粒径使用激光衍射式粒度计来测定。
鳞片状玻璃基材的平均厚度通过测定100粒鳞片状玻璃基材的厚度,并取其平均来求得。各鳞片状玻璃基材的厚度通过使用干涉显微镜来测定直接光(未受到相位物体的影响的光)与透过鳞片状玻璃基材的光的光路差而求得。
各覆膜的厚度使用二次离子质量分析(SIMS:二次离子质谱仪)来测定。具体地,基于从光辉性颜料的表面到鳞片状玻璃基材的表面的成分分布来决定。
[实施例1]
实施例1的光辉性颜料如图1的例子所示,鳞片状玻璃基材具有由基底覆膜(银覆膜)、金覆膜和黄色覆膜依次包覆的结构。构成黄色覆膜的母材由二氧化硅构成。实施例1的光辉性颜料如下制备。
(由银覆膜包覆的鳞片状玻璃基材)
首先,作为由银覆膜包覆的鳞片状玻璃基材,准备日本板硝子株式会社制的MC2080PS。该鳞片状玻璃基材具有通过非电解镀层法、用银覆膜(厚度为20~100nm)包覆的结构。
(金覆膜的形成)
金覆膜如下所示通过非电解镀层法形成。首先,在纯水300mL中添加作为还原剂的L-抗坏血酸钠6g、作为pH调节剂的磷酸氢二钠3g,对它们进行搅拌的同时加热至60℃。向所得的溶解液中添加作为金原料的亚硫酸金钠水溶液(浓度为50g/L)13g,获得镀金液。
接着,向镀金液中添加由银覆膜包覆的鳞片状玻璃基材(日本板硝子株式会社制、MC2080PS)30g。然后搅拌20~30分钟,通过非电解镀层反应,在银覆膜上形成平均厚度为1.4nm的金覆膜。
接着,重复数次过滤和水洗后,通过在180℃下对由银覆膜和金覆膜包覆的鳞片状玻璃基材进行2小时的加热处理,使其干燥。由银覆膜和金覆膜包覆的鳞片状玻璃基材的平均粒径为80μm、平均厚度为1.3μm、呈现出带有浅黄色的金属光泽。
(分散有黄色颜料的二氧化硅覆膜的形成)
接着,如下通过溶胶-凝胶法在金覆膜上形成作为黄色覆膜的分散有非水溶性黄色颜料的二氧化硅覆膜。
将四乙氧基硅烷15mL、异丙醇(IPA)300mL和纯水60mL混合。向所得的混合液中添加2.0g含有10质量的%C.I.G.N所表示的颜料黄110的微粒(黄色颜料、平均粒径为约100nm)的溶液,进行混合,获得二氧化硅覆膜形成溶液。
向该二氧化硅覆膜形成溶液中添加30g由银覆膜和金覆膜包覆的鳞片状玻璃基材,用搅拌机对它们进行搅拌混合。然后,向二氧化硅覆膜形成溶液中添加14mL氢氧化铝溶液(浓度为25质量%),然后搅拌二氧化硅覆膜形成溶液2~3小时,使其发生脱水缩合反应。由此,可以在二氧化硅覆膜形成溶液中,在鳞片状玻璃基材的表面上均匀地析出分散有黄色颜料的二氧化硅覆膜。
接着,在过滤后,通过在180℃下对由银覆膜、金覆膜和二氧化硅覆膜包覆的鳞片状玻璃基材进行2小时的加热处理,使其干燥。如此,获得具有分散有黄色颜料的二氧化硅覆膜(膜厚为100nm)的光辉性颜料。该光辉性颜料呈现出纯金的色调。
[实施例2]
实施例2的光辉性颜料如图2的例子所示,鳞片状玻璃基材具有由基底覆膜(银覆膜)、黄色覆膜和金覆膜依次包覆的结构。对于由银覆膜包覆的鳞片状玻璃基材,与实施例1同样地使用MC2080PS。分散有黄色颜料的二氧化硅覆膜和金覆膜的形成方法等与实施例1中的方法同样。
[实施例3]
实施例3的光辉性颜料如图1的例子所示,鳞片状玻璃基材具有由基底覆膜(银覆膜)、金覆膜和黄色覆膜依次包覆的结构。实施例3的光辉性颜料除了使用水溶性的黄色染料作为黄色覆膜所含的黄色色素、使用氢氧化铝作为构成黄色覆膜的母材材料以外,与实施例1的光辉性颜料同样。
首先,与实施例1同样,作为由银覆膜包覆的鳞片状玻璃基材,使用日本板硝子株式会社制的MC2080PS,通过非电解镀层反应,在银覆膜上形成平均厚度为1.4nm的金覆膜。接着,重复数次过滤和水洗后,通过在180℃下对由银覆膜和金覆膜包覆的鳞片状玻璃基材进行2小时的加热处理,使其干燥。由银覆膜和金覆膜包覆状态的鳞片状玻璃基材的平均粒径为80μm、平均厚度为1.3μm、呈现出带有浅黄色的金属光泽。
接着,制备10质量%的硝酸铝(III)9水合物[Al(NO3)3·9H2O]水溶液。另一方面,将由银覆膜和金覆膜包覆的鳞片状玻璃基材约30g添加到精制水0.3L中获得悬浊液,用水浴将所得的悬浊液的温度保持在75℃,使用稀硝酸将悬浊液的pH调整至6。接着,用10分钟的时间缓慢地添加上述硝酸铝(III)9水合物水溶液20g和氢氧化钠水溶液(10质量%)8g。添加了这些水溶液后,继续将悬浊液的温度保持在75℃、将pH维持在6,同时继续搅拌悬浊液30分钟。之后用滤纸过滤悬浊液,将所得的过滤固态物水洗,获得依次形成有银覆膜、金覆膜和氢氧化铝覆膜的鳞片状玻璃基材。
接着,将形成有银覆膜、金覆膜和氢氧化铝覆膜的鳞片状玻璃基材约30g添加到0.3L精制水中。用水浴将所得的悬浊液的温度保持在70℃,同时向该悬浊液中添加含有10质量%的酸性黄23(黄色4号)的溶液14g。添加了该溶液后,将悬浊液的温度保持在70℃、将pH维持在6,同时继续搅拌悬浊液15分钟。之后用滤纸过滤悬浊液,将所得的过滤固态物干燥,接着在120℃下对该过滤固态物进行加热处理2小时。如此,获得具有分散有黄色染料的氢氧化铝(母材、膜厚为30nm)的光辉性颜料。该光辉性颜料呈现出纯金的色调。
[实施例4]
实施例4的光辉性颜料如图1的例子所示,鳞片状玻璃基材具有由基底覆膜(镍-磷合金覆膜、镍原子%为85)、金覆膜和黄色覆膜依次包覆的结构。实施例4的光辉性颜料中,基底覆膜为镍-磷合金覆膜,黄色覆膜中所含的黄色色素为非水溶性的黄色颜料,构成黄色覆膜的母材材料为二氧化硅。除上述内容以外,实施例4的光辉性颜料与实施例1的光辉性颜料相同。
首先,作为由镍-磷合金覆膜包覆的鳞片状玻璃基材,准备日本板硝子株式会社制的MC5150NS(平均粒径为150μm、平均厚度为5.0μm)。日本板硝子株式会社制的MC5150NS为在鳞片状玻璃基材上通过非电解镀层法形成有镍-磷合金覆膜(厚度为约150nm)的材料。
(金覆膜的形成)
金覆膜如下所示通过非电解镀层法形成。首先,在纯水300mL中添加作为还原剂的L-抗坏血酸钠3g、作为pH调节剂的磷酸氢二钠1.5g,在对其搅拌的同时加热至60℃,使之溶解。向所得的溶解液中添加作为金原料的亚硫酸金钠水溶液(浓度为50g/L)6.5g,获得镀金液。
接着,向镀金液中添加由镍-磷合金覆膜包覆的鳞片状玻璃基材(日本板硝子株式会社制、MC5150NS)30g。在搅拌20~30分钟的同时,通过非电解镀层反应,在镍-磷合金覆膜上形成平均厚度为2.8nm的金覆膜。
接着,重复数次过滤和水洗后,通过在180℃下对由镍-磷合金覆膜和金覆膜包覆的鳞片状玻璃基材金覆膜进行2小时的加热处理,使其干燥。由镍-磷合金覆膜和金覆膜包覆的鳞片状玻璃基材的平均粒径为150μm、平均厚度为5μm、呈现出带有浅黄色的金属光泽。
(分散有黄色颜料的二氧化硅覆膜的形成)
接着,如下所示通过溶胶-凝胶法在金覆膜上形成作为黄色覆膜的分散有非水溶性黄色颜料的二氧化硅覆膜。
将四乙氧基硅烷3.8mL、异丙醇(IPA)300mL和纯水12mL混合。向所得的混合液中添加0.5g含有10质量%的C.I.G.N所表示的颜料黄110的微粒(黄色颜料、平均粒径为约100nm)的溶液,进行混合,获得二氧化硅覆膜形成溶液。
向该二氧化硅覆膜形成溶液中添加30g由镍-磷合金覆膜和金覆膜包覆的鳞片状玻璃基材,用搅拌机进行搅拌混合。然后,向二氧化硅覆膜形成溶液中添加3.5mL氢氧化铝溶液(浓度为25%),然后通过搅拌二氧化硅覆膜形成溶液2~3小时,使其发生脱水缩合反应。由此,能够在二氧化硅覆膜形成溶液中,在金覆膜上均匀地析出分散有黄色颜料的二氧化硅覆膜。
接着,重复数次过滤和水洗后,通过在180℃下对由镍-磷合金覆膜、金覆膜和二氧化硅覆膜包覆的鳞片状玻璃基材进行2小时的加热处理,使其干燥。如此,获得具有分散有黄色颜料的二氧化硅覆膜(膜厚为100nm)的光辉性颜料。该光辉性颜料呈现出纯金的色调。
[实施例5]
实施例5的光辉性颜料如图1的例子所示,鳞片状玻璃基材具有由基底覆膜(银覆膜)、金覆膜和黄色覆膜依次包覆的结构。实施例5的光辉性颜料除了使用水溶性的黄色染料作为黄色覆膜所含的黄色色素、使用水滑石作为构成黄色覆膜的母材材料以外,与实施例1的光辉性颜料相同。
首先,与实施例1同样,作为由银覆膜包覆的鳞片状玻璃基材使用日本板硝子株式会社制的MC2080PS,通过非电解镀层反应,在银覆膜上形成平均厚度为1.4nm的金覆膜。接着,重复数次过滤和水洗后,通过在180℃下对由银覆膜和金覆膜包覆的鳞片状玻璃基材进行2小时的加热处理,使其干燥。成为由银覆膜和金覆膜包覆状态的鳞片状玻璃基材的平均粒径为80μm、平均厚度为1.3μm,并呈现出带有浅黄色的金属光泽。
接着,制备在精制水50ml中溶解有3g氯化铝6水合物和5g氯化镁6水合物的调整液。另一方面,将由银覆膜和金覆膜包覆的鳞片状玻璃基材约30g、含酸性黄23的水溶液(10质量%)13.5g和含食品黄3的水溶液(10质量%)0.5g添加于精制水0.3L中,获得悬浊液,用水浴将所得的悬浊液的温度保持在75℃,用10分钟的时间向悬浊液中滴加上述调整液总量。上述调整液的滴加中,使用10质量%的氢氧化钠水溶液将悬浊液的pH维持在6。继续将pH维持在6,同时在90℃下搅拌悬浊液30分钟。
之后,用滤纸过滤悬浊液,将所得的过滤固态物干燥,接着在120℃下对过滤固态物进行2小时的加热处理。由此,获得具有含有黄色染料的水滑石(母材、膜厚为30nm)的光辉性颜料。该光辉性颜料呈现出带红色的纯金的色调。
[比较例1]
比较例1的光辉性颜料的鳞片状玻璃基材具有由银覆膜和分散有黄色颜料的二氧化硅覆膜依次包覆的结构。比较例1的光辉性颜料除了没有金被膜以及二氧化硅覆膜形成溶液中的黄色颜料的含量不同以外,与实施例1的光辉性颜料相同。作为由银覆膜包覆的鳞片状玻璃基材,与实施例1同样地使用MC2080PS。二氧化硅覆膜形成溶液如下进行调整。分散有黄色颜料的二氧化硅覆膜按照与实施例1的覆膜同样的步骤形成。
将四乙氧基硅烷15mL、异丙醇(IPA)300mL和纯水60mL混合。向所得的混合液中添加6.0g含有10质量%的C.I.G.N所表示的颜料黄110的微粒(黄色颜料、平均粒径为约100nm)的溶液,进行混合,获得二氧化硅覆膜形成溶液。
[比较例2]
比较例2的光辉性颜料为日本特开2004-352725号公报中所记载的光辉性颜料,鳞片状玻璃基材具有被二氧化钛覆膜和氧化铁覆膜依次包覆的结构。
(二氧化钛覆膜的形成方法)
将由C玻璃构成的鳞片状玻璃基材(日本板硝子株式会社制、MC2080FF、平均粒径为80μm)30g分散于333mL的蒸馏水中。将该分散液加热至75℃,使用稀盐酸将分散液的pH调节至1.6。接着,向分散液中缓慢添加18质量%的氯化锡(II)溶液7mL,之后以100mL/小时的速度添加四氯化钛40质量%的水溶液。在添加四氯化钛水溶液的过程中,添加氢氧化钠的稀释水溶液,将分散液的pH保持在1.6。通过添加四氯化钛水溶液,在鳞片状玻璃基材的表面上可观察到由干涉而产生的金色,继续添加四氯化钛水溶液直至观察到所期望的金色。接着,从分散液中过滤已成为浆料状的鳞片状玻璃基材,用蒸馏水洗涤经过滤的鳞片状玻璃基材,获得被二氧化钛覆膜包覆的鳞片状玻璃基材。
(氧化铁覆膜的形成方法)
接着,将被二氧化钛覆膜包覆的鳞片状玻璃基材分散于300mL的蒸馏水中。将该分散液加热至76℃,用稀盐酸将分散液的pH调节至3.2。接着,向分散液中以0.2mL/小时的速度添加10质量%的氯化铁(III)水溶液。在添加上述氯化铁(III)水溶液的过程中,添加氢氧化钠的稀释水溶液,将分散液的pH保持在3.2。继续添加上述氯化铁(III)水溶液直至观察到所期望的金色。接着,从分散液中过滤已成为浆料状的鳞片状玻璃基材,用蒸馏水洗涤过滤固态物。之后,在600℃下烧成过滤固态物,从而在二氧化钛覆膜上形成Fe2O3覆膜。如此,获得鳞片状玻璃基材由二氧化钛覆膜和氧化铁覆膜依次包覆的光辉性颜料。
[标准例]
标准例的鳞片状玻璃基材为由银覆膜和金覆膜(平均厚度为10nm)依次包覆的材料。金覆膜的形成使用以下的非电解镀金液来进行。
首先,在纯水300mL中添加作为还原剂的L-抗坏血酸钠14g和作为pH调节剂的磷酸氢二钠7g,在搅拌的同时将之加热至60℃,使之溶解。向所得的溶解液中添加作为金原料的亚硫酸金钠水溶液(浓度为50g/L)91g,获得镀金液。除此以外,与实施例1同样操作,在银覆膜上形成平均厚度为10nm的金覆膜。
[评价用试样的制备]
向由30质量%丙烯酸树脂和70质量%有机溶剂构成的透明涂料(日本Paint株式会社制)中分别以10质量%的比例配合实施例、比较例和标准例的光辉性颜料,用混炼机进行混合。如此,制备各涂料,并将各涂料涂布在市售的黑白遮蔽纸上以使得涂膜的厚度为9mil(9/1000×25.4mm),然后将涂膜自然干燥。以干燥后的涂膜分别为评价用试样。
对各评价用试样进行以下项目的评价。
(1)遮蔽性能
(2)金属光泽度
(3)反射色调的角度依赖性
(1)遮蔽性能
对涂布在黑白遮蔽纸上的涂膜,用色度计(Konica Minolta Sensing株式会社制、CR-400)测定其亮度。其中,用色度图L*a*b*测定亮度(L*)。使用C光源作为此时的观察光源。由测定的白色部的亮度L*(白)和黑色部的亮度L*(黑),计算亮度差(△L*=L*(白)-L*(黑))并示于表1中。△L*越小,则表示遮蔽性能越优异。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 标准例 | |
L*(白) | 81.5 | 80.2 | 82.1 | 62.3 | 81.8 | 84.1 | 84.8 | 79.8 |
L*(黑) | 80.7 | 79.7 | 81.3 | 61.6 | 81.0 | 83.1 | 67.0 | 79.2 |
△L* | 0.8 | 0.5 | 0.8 | 0.7 | 0.8 | 0.8 | 17.8 | 0.6 |
如表1所示,任一个实施例中,△L*均小、遮蔽性能优异,具有与标准例同等的遮蔽性能。另一方面,比较例2的△L*大、遮蔽性能差于标准例。
(2)金属光泽度
涂布在黑白遮蔽纸上的涂膜的金属光泽度用光度计(株式会社村上色彩研究所制、GM-O26PR)进行测定。其中,观察光源使用D65光源。相对于涂膜面以偏离垂直方向60°或20°的角度入射光,分别测定正反射的光的光量。用测得的光量值,根据ISO2813计算光泽度并示于表2。该值越高,则表明光泽度越高。
表2
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 标准例 | |
光泽度(60°) | 74.3 | 78.3 | 73.3 | 68.5 | 77.7 | 59.6 | 51.6 | 80.3 |
光泽度(20°) | 24.6 | 26.4 | 24.2 | 20.3 | 26.5 | 18.9 | 14.6 | 27.3 |
如表2所示,任一个实施例中的金属光泽度均为接近标准例的金属光泽度的值。另一方面,比较例1和2的金属光泽度均小于标准例的金属光泽度。
(3)反射色调的角度依赖性
如图3所示,在相对于涂膜5的表面能够以45°的角度入射光的位置上配置观察光源6。观察光源6使用D65光源。由观察光源6射出光,利用检测器7测定反射光的色调。
另外,检测器7配置在能够接受从入射光的正反射方向(即相对于涂膜5的表面为45°的方向)向观察光源侧偏离15°方向的反射光(将该反射光的色调称作“高亮色调”)的位置上。其理由如下所述。
在光辉性颜料和涂膜面上,正反射的反射光的光量过大。因此,难以分辨光辉性颜料的发色。如果从偏离正反射方向15°的角度观测,则可消除在涂膜面上的正反射的影响、从而易于测定由光辉性颜料的反射所产生的色调。
另外,如图3所示,利用检测器7测定从正反射方向向观察光源侧偏离75°方向的反射光的色调(阴影色调)。如果从偏离正反射方向75°的角度观测,则可消除正反射所产生的影响、可以测定光辉性颜料本身的色调。
高亮色调和阴影色调使用多角度分光测色计(株式会社COLORTECHNO SYSTEM制)进行测定。其中,用色度图L*a*b*测定L*、a*和b*。测定结果示于表3(高亮色调)和表4(阴影色调)中。
表3
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 标准例 | |
L* | 135.1 | 134.4 | 135.3 | 123.9 | 136.0 | 137.7 | 114.9 | 133.6 |
a* | 2.5 | 2.3 | 2.7 | 1.8 | 5.7 | 2.8 | 0.5 | 2.6 |
b* | 38.9 | 37.4 | 38.4 | 34.7 | 36.7 | 38.6 | 51.1 | 39.5 |
从表3可知,任一个实施例均得到了近似于标准例的高亮色调。另一方面,比较例2得到了与标准例不同的色调。
表4
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 标准例 | |
L* | 33.5 | 30.8 | 32.5 | 30.2 | 33.2 | 39.7 | 63.2 | 30.2 |
a* | 1.3 | 1.5 | 1.6 | 1.8 | 4.2 | 0.14 | 4.7 | 1.8 |
b* | 12.9 | 12.3 | 12.7 | 10.5 | 10.6 | 20.4 | 20.2 | 11.6 |
从如表4可知,任一个实施例均得到了近似于标准例的阴影色调。另一方面,比较例均得到了与标准例不同的色调,特别是比较例2中的相差程度较大。
观察角度所引起的亮度变化通过由下述数学式1定义的动态指数表示。
[数学式1]FI=2.69×(L* 15°-L* 110°)1.11/(L* 45°)0.86
这里,L* 15°、L* 110°、L* 45°为在相对于正反射的方向分别向观察光源侧倾斜15°、110°、45°的位置上测定的亮度。各亮度用色度图L*a*b*测定(参照图4)。
动态指数为将高亮色调和阴影色调的亮度变化数值化的结果,数值如果越大,则亮度变化的程度越大。另外,如果FI与标准例的值相同或相近,则可以评价为具有纯金般的色调。
上述动态指数也使用多角度分光测色计测定,其结果示于表5。观察光源使用D65光源。
表5
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 标准例 | |
FI(白) | 21.0 | 21.6 | 22.1 | 20.7 | 22.1 | 15.7 | 6.7 | 22.1 |
FI(黑) | 22.1 | 22.3 | 22.5 | 21.0 | 22.8 | 17.4 | 26.7 | 23.8 |
如表5所示,无论基底的颜色为白色还是黑色,实施例的动态指数值均接近于标准例的动态指数值。另一方面,比较例的动态指数均为偏离标准例的动态指数值。
如上所述,实施例的光辉性颜料中,尽管金覆膜的膜厚为标准例的金覆膜膜厚的一半以下,也具有与标准例同样的金色色调。因此,实施例的光辉性颜料与标准例的光辉性颜料相比,在成本方面上具有优点。
如上所示,本发明能够提供一种光辉性颜料、以及含有该颜料的化妆料、涂料、油墨和树脂组合物等,由于其具有将含有选自银、镍和镍系合金中的至少1种金属材料的基底覆膜作为其它覆膜的基底,并进一步具有黄色覆膜,因此即使金覆膜的厚度薄于以往金覆膜的厚度,也可获得纯金般的色调。
本发明光辉性颜料即使金覆膜的厚度薄于以往金覆膜的厚度,也会呈现纯金般色调。因此,本发明光辉性颜料可以在广泛的领域中使用,因此是有用的。
Claims (14)
1.一种具有金色调的光辉性颜料,其特征在于,其包含:鳞片状玻璃基材、含有选自银、镍和镍系合金中的至少1种金属材料的基底覆膜、含有金的金覆膜、以及含有黄色色素和母材的黄色覆膜,其中,所述基底覆膜、所述金覆膜和所述黄色覆膜分别形成层以包覆所述鳞片状玻璃基材,且所述基底覆膜、所述金覆膜和所述黄色覆膜中,所述基底覆膜被配置在最内侧。
2.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述金覆膜的膜厚为0.5~5nm。
3.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述基底覆膜为含有银的含银基底覆膜,且所述含银基底覆膜的膜厚为20~100nm。
4.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述基底覆膜为含有镍或镍系合金的含镍基底覆膜,且所述含镍基底覆膜的膜厚为40~200nm。
5.根据权利要求1所述的光辉性颜料,其中,所述镍系合金为镍-磷合金、镍-钨-磷合金、镍-铁-钨-磷合金、镍-钴合金、镍-钴-磷合金、镍-钯-磷合金、镍-锡-磷合金或镍-铜-磷合金。
6.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述黄色色素为水溶性色素,且所述母材含有选自氢氧化铝、氢氧化锆、氢氧化钙、水合氧化铝、水合氧化锆、水合氧化钙以及水滑石中的至少1种材料。
7.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述黄色色素为非水溶性色素,且所述母材含有二氧化硅。
8.根据权利要求6所述的具有金色调的光辉性颜料,其中,所述水溶性色素为选自由色指数通用名称规定的酸性黄23、食品黄3、酸性黄73、酸性黄3、酸性黄40、酸性黄1、酸性黄36以及酸性黄11中的至少1种。
9.根据权利要求7所述的具有金色调的光辉性颜料,其中,所述非水溶性色素为选自由色指数通用名称规定的酸性黄73、溶剂黄33、颜料黄12、颜料黄1、溶剂黄5、溶剂黄6、颜料黄110、颜料黄139、颜料黄150和颜料黄154中的至少1种。
10.根据权利要求1所述的具有金色调的光辉性颜料,其中,所述鳞片状玻璃基材的平均粒径为1μm~500μm、平均厚度为0.3μm~10μm。
11.一种化妆料,其特征在于,其含有权利要求1~10任一项所述的具有金色调的光辉性颜料。
12.一种涂料,其特征在于,其含有权利要求1~10任一项所述的具有金色调的光辉性颜料。
13.一种油墨,其特征在于,其含有权利要求1~10任一项所述的具有金色调的光辉性颜料。
14.一种树脂组合物,其特征在于,其含有权利要求1~10任一项所述的具有金色调的光辉性颜料。
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PCT/JP2007/056500 WO2007116769A1 (ja) | 2006-03-27 | 2007-03-27 | 金色調を有する光輝性顔料、これを含有する化粧料、塗料、インク、または樹脂組成物 |
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US (1) | US20090069447A1 (zh) |
EP (1) | EP2011836B1 (zh) |
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KR (1) | KR20080104140A (zh) |
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JP5026728B2 (ja) * | 2006-04-03 | 2012-09-19 | 花王株式会社 | メイクアップ化粧料 |
DE102009058243A1 (de) * | 2009-12-14 | 2011-06-16 | Giesecke & Devrient Gmbh | Dünnschichtelement mit Mehrschichtstruktur |
CN102391687B (zh) * | 2011-09-05 | 2013-08-28 | 福州坤彩精化有限公司 | 金属银涂布的玻璃基效果颜料及其制备方法 |
EP2873752B1 (en) | 2012-07-13 | 2020-05-20 | Toyo Kohan Co., Ltd. | Electroless gold plating method and gold-plate-coated material |
AU2014369110B2 (en) * | 2013-12-20 | 2018-05-10 | Philip Morris Products, S.A. | Wax encapsulated flavour delivery system for tobacco |
WO2016012074A1 (en) * | 2014-07-25 | 2016-01-28 | Merck Patent Gmbh | Colored effect pigments |
CA2988904C (en) * | 2016-12-21 | 2020-05-05 | Viavi Solutions Inc. | Hybrid colored metallic pigment |
CA2988898C (en) * | 2016-12-21 | 2021-05-11 | Viavi Solutions Inc. | Particles having a vapor deposited colorant |
DE102016226166A1 (de) * | 2016-12-23 | 2018-06-28 | Krones Ag | Verfahren und Direktdruckmaschine zur Bedruckung von Behältern aus unterschiedlichen Materialtypen im Direktdruck |
WO2018186076A1 (ja) * | 2017-04-06 | 2018-10-11 | 日本板硝子株式会社 | 紫外線遮蔽材、並びに、それを配合した組成物及び塗装体 |
JP6395987B1 (ja) * | 2017-04-06 | 2018-09-26 | 日本板硝子株式会社 | 紫外線遮蔽材、並びに、それを配合した組成物及び塗装体 |
CN111923512A (zh) * | 2020-08-06 | 2020-11-13 | 贵州金马包装材料有限公司 | 一种金色复合铝箔卡纸 |
CN116685645A (zh) * | 2021-02-18 | 2023-09-01 | Dic株式会社 | 颜料、化妆品、油墨、涂料、调色剂和成形物 |
JP7113412B1 (ja) * | 2022-04-06 | 2022-08-05 | 東洋インキScホールディングス株式会社 | 保護膜、保護膜を有する筐体およびそれを用いてなる電子機器 |
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EP2011836B1 (en) | 2013-03-06 |
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US20090069447A1 (en) | 2009-03-12 |
WO2007116769A1 (ja) | 2007-10-18 |
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