CN102209695B - 混凝土着色组合物及方法 - Google Patents
混凝土着色组合物及方法 Download PDFInfo
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- CN102209695B CN102209695B CN200980144642.6A CN200980144642A CN102209695B CN 102209695 B CN102209695 B CN 102209695B CN 200980144642 A CN200980144642 A CN 200980144642A CN 102209695 B CN102209695 B CN 102209695B
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- INRGAWUQFOBNKL-UHFFFAOYSA-N {4-[(Vinyloxy)methyl]cyclohexyl}methanol Chemical compound OCC1CCC(COC=C)CC1 INRGAWUQFOBNKL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/71—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being an organic material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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Abstract
本发明提供了适于为水泥质或矿物基材的表面提供颜色的酸性组合物和方法。具体地,本发明涉及适于处理水泥质或矿物基材的表面的酸性组合物和方法,它们具有利用低腐蚀性酸基溶液的优点。这种酸性组合物中包含含有弱碱以及与其处于平衡状态的共轭酸的物质。这种物质的存在缓和了酸的腐蚀行为,同时仍允许发生优异的着色作用。
Description
优先权
本非临时专利申请是于2008年11月7日递交的标题为“CONCRETECOLORING COMPOSITIONS AND METHODS”的美国专利申请序列号12/291,316的部分继续申请,专利申请12/291,316的全部内容通过引用插入本文。
技术领域
本发明一般性地涉及适于为水泥质或矿物基材的表面提供颜色的组合物和方法。
背景技术
水泥基组合物在建筑材料(例如水泥壁板和装饰产品(trimproduct),如纤维水泥产品)、瓷砖铺设、墙壁以及池灰泥、拉毛灰泥、自流平复合物、屋顶瓦片和水泥修补中具有广泛应用。混凝土及类似材料由碱土金属通常通过如下生产:将波特兰水泥与沙子、砂砾和水进行混合。水泥与水反应从而生成金属碳酸盐(诸如碳酸钙)等。混合物中的碳酸钙不溶于水,但容易与大多数酸进行反应。
一段时间以来一直需要生产有色混凝土,以改善混凝土或水泥基组合物的装饰外观。例如,美国专利3,930,740公开了一种用于在添加了颜料的新混凝土中印上非重复石头图案的工具。美国专利5,735,094公开了一种用于涂覆由液体灰泥组成的装饰涂层的方法,所述液体灰泥包含有色颜料。将染料和颜料加入水泥材料中也可广泛用于上述所有材料中。
现有技术已知若干种为混凝土表面提供颜色或装饰的方法。这些包括:吹扫部分固化的混凝土从而生成帚状表面;或者添加着色剂使其与混凝土共混物混合。然而,此后需要彻底清洁涂覆设备,这非常费力费钱。这种方法成本很高并且效率很低,这是因为着色剂昂贵,其与混凝土充分混合但仅仅在可见的表面需要它们。已知更精细的表面处理,其包括:将尺寸和颜色不同的石子通过水泥或树脂包埋在混合物区域中。
本领域已知使混凝土着色或染色的最常用方法之一包括:用含有金属盐的酸性溶液洗涤混凝土表面。这种接触有助于使表面显现颜色。在涂覆酸性染色溶液并且使颜色显现之后,一般将中和剂涂覆到被染色的混凝土上,然后涂覆透明的聚合物密封保护涂层。这种透明的顶涂层(top coat)有助于进一步实现颜色的显现。
本领域中使混凝土着色的第二种常用方法包括:用酸性溶液洗涤混凝土表面从而粗糙化或刻蚀表面;采用常见的碳酸氢钠(baking soda)和水的混合物中和并冲洗掉刻蚀溶液;用聚合物基染料或漆料使表面着色;用透明涂层整理表面。
其他已知方法包括:用诸如盐酸的矿物酸刻蚀或者用金刚石研磨混凝土表面,然后涂覆水泥质覆盖层。这种方法在Bob Harris′Guide toConcrete Overlays & Toppings(Decorative Concrete Institute 251 Villa RosaRoad Temple,GA 30179)中有所描述。在水泥质覆盖层已经适当固化后,它可以被含有金属盐的酸性溶液染色。这些使用含金属盐的酸性溶液的染色技术是想要的,因为它们为混凝土提供非常持久快捷的着色。通常,这些方法使用高腐蚀性的酸性溶液,这使操作很危险。用于使混凝土染色的一些其他想要的技术在Bob Harris′Guide to Stained Concrete Interior Floors(Decorative Concrete Institute 251 Villa Rosa Road Temple,GA 30179)中有所描述。
发明内容
本发明人已经发现,向含有适当金属盐的酸基着色组合物中掺入弱碱可以缓和所述酸的腐蚀特性,同时仍允许进行有效着色。在具有代表性的实施方式中,碱在水性介质中与共轭酸平衡,从而缓和所述酸的腐蚀特性。向酸性着色组合物中掺入弱碱会获得一种更安全、有效的使水泥基材染色的方法。尽管组合物可由单独的成分(包括所需酸和弱碱)得到,但是该组合物更容易由处理简单安全的成分诸如质子化形式的弱碱的盐制造。当这样的盐溶解在水性介质中时,酸性和碱性特性于是就地形成。例如,质子化弱碱的盐的代表性实施方式是脲单盐酸盐,其是可商购的稳定固体。当溶解在水中时,得到还包含由脲衍生得到的处于平衡的水性物质的酸性溶液。
与此相反,传统的混凝土酸染料用诸如盐酸的酸以使混凝土中的碳酸钙和氧化钙分解并促进与金属盐的离子交换,但这在没有有效量的任何弱碱或其共轭物的存在下进行。尽管单独的酸和金属盐确实也使材料的表面着色,但是在没有碱的缓和效应的情况下单独使用酸和金属盐往往会产生过量的氯化氢烟雾。此外,传统的盐酸溶液具有非常强的腐蚀性,因而制备、操作和使用都很危险。
将酸与弱碱组合的额外优点在于,在染色过程中,经染色的混凝土自中和。这节省了在冲洗之前进行中和的需要,但是如果需要中和步骤仍可进行。与此相反,通常,传统的酸染色剂在施用后必需被冲洗掉以除去过量的盐沉淀。在冲洗之前,使用盐酸的传统酸染色剂必需被中和,否则冲洗的流出物会污染相邻的混凝土。所使用的常见中和剂是氨或氢氧化钠,或者碳酸氢钠溶液。
本发明的组合物也可用在Bob Harris′Guide to Stained Concrete InteriorFloors(Decorative Concrete Institute 251 Villa Rosa Road Temple,GA 30179中所描述的任意染色方法中。
一方面,本发明涉及一种方法,所述方法包括将组合物涂覆到水泥质或矿物基材的表面上的步骤,所述组合物包含:(i)酸,其具有小于6的pKa;(ii)弱碱,其中所述弱碱的共轭酸的pKa小于7但大于所述酸的pKa;和(iii)一种或多种金属盐,所述金属盐能够在所述组合物被涂覆到水泥质或矿物基材上时提供颜色。该处理可被用于改变表面的颜色。处理后,可选将保护顶涂层涂覆到经处理表面。这样的顶涂层不仅有助于保护表面,而且它们可以有助于进一步显现表面的颜色。这种方法特别可用于处理纤维水泥建筑产品。另一方面,本发明涉及根据所述方法制备的经染色的基材,包括但不限于纤维水泥建筑产品。
另一方面,本发明涉及一种方法,所述方法包括将组合物涂覆到纤维水泥基材的表面的至少一部分上的步骤,和涂覆保护涂层以覆盖所述纤维水泥表面的步骤,所述组合物包含如下的反应混合物:(i)酸,其具有小于6的pKa;(ii)弱碱,其中所述弱碱的共轭酸的pKa小于7但大于所述酸的pKa;和(iii)一种或多种金属盐,所述金属盐能够在所述组合物被涂覆到纤维水泥基材上时提供颜色。
另一方面,本发明涉及一种方法,所述方法包括如下步骤:(a)将质子化碱的盐掺入水性液体载剂中,所述质子化碱具有小于约7的pKa;(b)将过渡金属的盐掺入所述水性液体载体;和(c)使所得组合物与水泥质表面接触。
另一方面,本发明涉及一种体系,其包含(a)水泥质表面;和(b)与所述表面接触的水性组合物,其中所述组合物包含(i)含有处于平衡状态的弱碱与所述弱碱的共轭酸的水性物质,所述弱碱的所述共轭酸具有小于约7的pKa;和(ii)含有过渡金属离子和相应阴离子的水性物质,其中相应于所述过渡金属离子和所述阴离子的盐是路易斯(Lewis)酸。
另一方面,本发明涉及一种方法,其包括将酸性组合物涂覆到纤维水泥基材的表面的至少一部分上的步骤,和涂覆辐射固化保护涂层以覆盖所述纤维水泥表面的步骤,所述酸性组合物包含如下的反应混合物:(i)酸,其具有小于6的pKa;和(ii)一种或多种金属盐,所述金属盐能够在所述组合物被涂覆到纤维水泥基材上时提供颜色。
发明详述
本发明涉及组合物(例如溶液和分散液)以及使用这些组合物为水泥质或矿物基材提供颜色的方法。优选地,组合物是水性的,但可选包含一种或多种其他液体载剂。本文中使用的“水泥质基材”意在包括传统的水泥基材以及任何包含水泥和其他成分的复合物。水泥通常是在水性介质的存在下固化的无机粘接剂。水泥的实例包括波特兰水泥、非波特兰水泥以及由这些得到的共混物。波特兰水泥及其共混物的实例包括高炉水泥、粉煤灰水泥、火山灰水泥、硅灰水泥、砌筑水泥、膨胀水泥、彩色水泥等。非波特兰水泥包括煅石膏、火山灰石灰水泥、石灰渣水泥、多硫化水泥(supersulfated cement)、铝酸钙水泥、硫铝酸钙水泥、天然水泥和地聚水泥(geopolymer cement)。根据一种分类,水泥可以是水硬化的或非水硬化的。水泥被用于生产混凝土、灰泥、瓷砖、建筑材料,诸如壁板产品、砖、合成石路(synthetic stones road)、人行道、家具、容器、流体管道等。因此,水泥质材料包括被称为纤维水泥(fibercement)的复合物。纤维水泥是一种广泛用于生产建筑材料、特别是壁板(用于覆盖商用结构、住宅、农用结构或其他结构的外表面)的复合物。纤维水泥通常是包含水泥粘接剂和一种或多种有机或无机纤维的复合物。纤维素纤维常用在纤维水泥中。纤维水泥还可以包含一种或多种常被添加到水泥产品中的其他成分,包括沙子、蛭石,珍珠岩,粘土等。
因此,“水泥质基材”具体包括纤维水泥建筑产品,例如若干种优选的纤维水泥壁板产品可得自Mission Vieio,CA的James Hardie BuildingProducts Inc.,包括以HARDIEHOMETM壁板、HARDIP ANELTM垂直壁板、HARDIPLANKTM搭接壁板、HARDIESOFFITTM面板、HARDITRIMTM板和HARDISHINGLETM壁板销售的那些产品。其他适当的纤维水泥壁板基材包括,得自德国Iserlohn的Knauf USG Systems GmbH & Co.KG的AQU AP ANELTM水泥板产品;得自Cemplank of Mission Viejo,CA的CEMPLANKTM,CEMPANELTM和CEMTRIMTM水泥板产品;得自CertainTeed Corporation of Valley Forge,PA的WEATHERBOARDSTM水泥板产品;得自MaxiTile Inc.of Carson,CA的MAXITILETM,MAXISHAKETM和MAXISLATETM水泥板产品;得自Nichiha U.S.A.,Inc.of Norcross,GA的BRESTONETM,CINDERSTONETM,LEDGESTONETM,NEWPORT BRICKTM,SIERRA PREMIUMTM和VINTAGE BRICKTM水泥板产品;得自中国张家港Evernice Building Materials Co.,Ltd.的EVERNICETM水泥板产品以及得自印度Everest Industries Ltd.的EBOARDTM水泥板产品。
组合物优选是酸性的,并且包含处于平衡状态的弱碱与共轭酸的水性物质和一种或多种金属盐的一种或多种水性物质。在一些实施方式中,这样的金属盐可以是Lewis酸。本文中使用的“弱碱”是指,其共轭酸具有小于约7、优选在约-1至约7的范围内、更优选在约-1至约5的范围内、最优选在约-1至约3的范围内的pKa的碱。理想地,组合物是酸性的,并且可以包含对应于具有小于6pKa的酸的水性物质,对应于其共轭酸的pKa小于7但大于所述酸的pKa的弱碱的水性物质,和一种或多种水溶性金属盐。在各种实施方式中,组合物中的水溶性金属盐可以包括过渡元素的盐。在一些实施方式中,弱碱当被施用到水泥材料中使可以分解,结果分解产物也是碱。例如,并不希望受缚于任何理论,我们相信,水性脲物质可以分解从而形成含有氨的产品。
碱的强度通过其共轭酸的pKa来定义。碱的共轭酸的pKa越高,该碱越强。例如,乙酸盐是其共轭酸(乙酸)具有4.75pKa的弱碱。乳酸盐是其共轭酸(乳酸)具有3.86pKa的弱碱。根据这个定义,乙酸盐被认为是比乳酸盐更强的碱。某些实施方式包括如下弱碱,该弱碱当被施用到基材上时能够分解成在25℃下具有大于0.01psi蒸气压的一种或多种组分。例如,并不希望受缚于任何理论,我们相信水性脲物质可以分解成氨、二氧化碳以及水。在一些实施方式中,水性酸是卤化氢,诸如HCl。在另一些实施方式中,弱碱优选包含水性脲物质。
可用在本发明中的弱碱包括:
(1)下式的被取代脲类
R1R2-N-C(O)-N-R3R4
其中R1、R2、R3和R4是C1-C10碳原子或氢,这种被取代的脲类包括例如脲、四甲基脲、乙酰脲、咪唑烷酮、或被取代的咪唑烷酮类、嘧啶酮、嘧啶二酮等;
(2)酰胺类,诸如甲酰胺和二甲基甲酰胺;或乙酰胺类,诸如二甲基乙酰胺、己内酰胺;和吡咯烷酮;
(3)碳酸的酯,诸如碳酸的烷基酯和芳基酯,例如碳酸二甲基酯、碳酸亚丙基酯、乙二醇双(甲基碳酸酯)、碳酸乙基·M-甲苯基酯;
(4)氨基甲酸酯,诸如氨基甲酸烷基酯和芳基酯,例如乙基氨基甲酸乙基酯、噁唑烷酮和噁唑烷二酮;和
(5)氨基酸,诸如甘氨酸、丙氨酸、亮氨酸、缬氨酸、苯丙氨酸、天冬氨酸、谷氨酸、半胱氨酸、赖氨酸和组氨酸。
弱碱的其他实例包括烷醇胺,包括三乙醇胺、二乙醇胺、一乙醇胺,和下式(HO-[(R)O]x-R)y-NH3-y的烷氧基化胺,其中每个R独立地是C2至C8烷基,X可以从1变化至100,y可以从1变化至3;具有含氮杂环基团(包括但不限于吡啶、嘧啶、咪唑、四唑、吡嗪、喹啉、异喹啉、吲哚、异吲哚、苯并咪唑、嘌呤、吡咯、异吡咯、喹唑啉、哒嗪、吡嗪、噌啉、二氮杂萘、喹喔啉、黄嘌呤、次黄嘌呤和蝶呤)的聚合物;丙烯酰胺和环状酰胺(诸如己内酰胺)的聚合物和共聚物;吡咯烷酮、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮的共聚物、甲基丙烯酰胺、聚甲基丙烯酰胺、甲基丙烯酰胺的共聚物;氨;胍;羟基脲;氨基脲(semicarbazide);一、二或三(烷基或芳基)脲;以及在二(烷基或芳基)脲中的烷基或芳基可以在相同的或不同的氮原子上的情况下,O-甲基羟基胺(甲氧基胺);苯胺和肼。优选的碱是含氮碱。优选的是被取代的脲。最优选的是尿素。
在优选的实施方式中,所用弱碱的量可通过酸当量的化学计量平衡确定。酸的摩尔当量可由每摩尔酸中可以在低于pH 9.0的pH值下被离子化的质子总数来确定。例如,(i)盐酸中每摩尔盐酸具有1个可离子化的质子,(ii)硫酸中每摩尔硫酸具有两个可离子化的质子;(iii)磷酸中每摩尔磷酸仅具有两个可离子化的质子和一个可以在高于9.0的pH值下被离子化的质子。优选的组合物包含,相对于酸的总摩尔当量,至少5%、更优选至少10%、更优选至少50%摩尔当量的弱碱。优选的组合物包含,相对于酸的总摩尔当量,小于200%、更优选小于175%、更优选小于150%摩尔当量的弱碱。
在一些实施方式中,酸的当量可以来自多种来源。例如,如果溶液得自第一酸源和金属盐(其也是Lewis酸),那么第一酸源和金属盐都为组合物提供酸当量。这样的本发明的着色组合物的说明性实例可以由如下成分得到,所述成分包括脲单盐酸盐,这可被视为第一酸源;和着色盐,其是Lewis酸,诸如FeCl2。我们认为,脲单盐酸盐中每摩尔添加的脲单盐酸盐提供1摩尔氢离子和1摩尔氯离子,氯化亚铁中每摩尔添加的氯化亚铁添加2摩尔氢离子和2摩尔氯离子。因此,这两种成分当溶解在水中时都提供对应于水性HCl的酸当量。
可用在本发明中的酸可以包括羧酸,诸如乙酸、马来酸、柠檬酸、甲酸和苯甲酸;磷酸、膦酸诸如乙基膦酸;多磷酸(polyphosphoric acids)(诸如焦磷酸和六偏磷酸);硫酸、磺酸(诸如苄基磺酸);硝酸和亚硝酸;卤化氢(诸如氟化氢、氯化氢、溴化氢和碘化氢)。优选的是磷酸和多磷酸、硝酸或亚硝酸和氯化氢。更优选的是磷酸、焦磷酸和氯化氢。最优选的是氯化氢。
优选的组合物包含足量的酸,使得所得组合物的pH小于约6、优选小于约4、更优选小于约2、最优选小于约1。在这样的组合物中,pH优选大于约-2,更优选大于约-1。在一些代表性的组合物中,这相当于组合物包含,基于所述组合物的总重量,至少0.25重量%、更优选至少0.5重量%、最优选至少1重量%的酸。优选的组合物包含,基于所述组合物的总重量,小于20重量%、更优选小于15重量%、最优选小于10重量%的酸。适当的酸优选具有小于6、更优选小于5、最优选小于3、最好小于1的pKa。
在一些实施方式中,所需要的酸可以直接添加到组合物以提供所需要的酸性pH特性。或者也可以使用可以原位形成酸性物质的非酸性成分,诸如质子化碱的盐。
优选的组合物包含金属离子,它们通常以可水溶的或可酸溶的金属盐形式引入。可用在本发明的各种组合物中的金属盐可以包括钛、钒、铬、锰、铁、钴、镍、铜、铝、镁或钡的氯化物、硫酸盐、硝酸盐、亚硝酸盐、磷酸盐或膦酸盐。适当的金属盐的具体实例包括但不限于VCl3,Cr(CH3CO2)3,Cr(CH3CO2)2,CrCl3,CrCl2,Cr2(SO4)3,Cr(SO4),Cr(NO3)3,CrPO4,MnCl2,Mn2(PO4)3,MnSO4,Mn(NO3)2,MnCO3,FeCl2,FeCl3,FeSO4,Fe2(SO4)3,FePO4,Fe(H2NSO3)2,Fe(NOs)3,Fe(C2O4),CoCl2,CoCl3,CoSO4,Co(NO3)2,CuCl,CBrI2,CuCl2,Cu(CH3CO2)2,Cu(HCO2)2,Cu(C2O4),CuCO3,CuSO4,Cu(NO3)2,NiCl2,和NiCl3。优选的金属盐包括Fe,Cr,Mn,Cu,和Co的盐。
金属盐的衡量单位是基于全部组合物重量的金属离子的重量百分比。例如,如果将10克无水氯化亚铁(FeCl2)添加到90克水中,那么所得组合物包含4.41%的铁(Fe(II))离子。适当的组合物可以包含一种以上类型的金属离子,诸如铁离子和铜离子。优选的组合物包含,基于全部组合物的重量,至少0.1重量%、更优选至少0.2重量%、最优选至少0.5重量%的金属离子总量。优选的组合物包含,基于全部组合物的重量,小于25重量%、更优选小于20重量%、最优选小于15重量%的金属离子总量。
本发明的组合物可以进一步包含一种或多种可选添加剂。一种可选添加剂是金属离子络合剂,它们有助于与基材的反应和/或调节组合物成分的溶解性。络合剂的实例包括EDTA、氨基膦酸盐(诸如以商品名DequestTM销售的那些);磷酸盐和多磷酸盐。其他可选添加剂包括表面活性剂、消泡剂、分散剂或有机溶剂(包括能够改善组合物的润湿性的那些添加剂)。还可以使用这些可选添加剂的混合物。
本发明着色组合物的水性实施方式除了水以外还可以包含一种或多种可选溶剂。适当的可选溶剂包括:可与水混溶的溶剂,诸如甲醇、乙醇、异丙醇、正丙醇、丙酮、乙二醇烷基醚、丙二醇烷基醚和二丙酮醇;以及与水不可混溶的溶剂,诸如乙酸烷基酯、乙酸丁酯、甲基异戊基甲酮、乙酸戊酯、二异丁基甲酮、二甲苯、甲苯、丁醇和石油醚。适当的可选消泡剂包括:硅酮、石油、矿物油、天然油或聚合消泡剂,以及这些消泡剂的混合物。如果使用,消泡剂的量,基于全部组合物的重量,优选介于0.005重量%和5重量%之间,更优选介于0.01重量%和4重量%之间,更优选介于0.05重量%和3重量%之间。
典型的表面活性剂可以包括阴离子表面活性剂和非离子表面活性剂。如果使用,表面活性剂的量,基于全部组合物的重量,优选介于0.05重量%和5重量%之间,更优选介于0.1重量%和4重量%之间,更优选介于0.2重量%和3重量%之间。适当的阴离子表面活性剂包括例如高级脂肪醇的硫酸盐,诸如十二烷基硫酸钠;烷基芳基磺酸盐,诸如异丙基苯磺酸钠或钾或者异丙基萘磺酸钠或钾;高级烷基磺基琥珀酸碱金属盐,诸如辛基磺基琥珀酸钠;N-甲基-N-棕榈酰月桂酸钠;油基羟乙基磺酸钠(sodiumoleyl isothionate);烷基芳基多乙氧基乙醇硫酸、磺酸或磷酸的碱金属盐和铵盐,诸如具有1至50个氧乙烯单元的四辛基苯氧基多乙氧基乙基硫酸钠;烷基多乙氧基乙基硫酸、磺酸和磷酸的碱金属盐和铵盐;芳基多乙氧基乙醇硫酸、磺酸和磷酸的碱金属盐和铵盐。
合适的非离子表面活性剂包括具有约7至18个碳原子的烷基和约6至约60个氧乙烯单元的烷基苯氧基多乙氧基乙醇,诸如庚基苯氧基多乙氧基乙醇、甲基辛基苯氧基多乙氧基乙醇;亚甲基联接的烷基苯酚的多乙氧基乙醇衍生物;含硫试剂,诸如将约6至60摩尔的氧化乙烷与壬基硫醇、十二烷基硫醇缩合或者与烷基硫代苯酚缩合制成的那些,其中所述烷基包含6至16个碳原子;长链羧酸的氧化乙烯衍生物,所述羧酸诸如为月桂酸、肉豆蔻酸、棕榈酸、油酸和在每分子含有6至60个氧乙烯单元的妥尔酸中找到的那些酸的混合物;长链醇的类似氧化乙烯的缩合物,所述长链醇诸如为辛醇、癸醇、月桂醇或鲸蜡醇;被醚化或被酯化的具有疏水烃链的多羟基化合物的氧化乙烯衍生物,诸如含有6至60个氧乙烯单元的山梨聚糖单硬脂酸酯;氧化乙烯片段与一个或多个疏水的氧化丙烯片段组合的嵌段共聚物。
典型的分散剂可以包括烯属不饱和羧酸的聚合物和共聚物,所述烯属不饱和羧酸诸如为(甲基)丙烯酸、富马酸、衣康酸、马来酸、马来酸酐,以及富马酸的单酯;含磷酸单体,诸如(甲基)丙烯酸磷酰基乙酯(phosphoethyl(meth)acrylate)和烯丙基膦酸;和含硫酸单体,诸如2-丙烯酰氨基-2-甲基-1-丙磺酸、(甲基)丙烯酸磺基乙酯和乙烯基硫酸。这包括以商品名TamolTM销售的分散剂。还可以使用柠檬酸、草酸、磷酸、焦磷酸和多磷酸。
本发明还提供了一种对水泥质或矿物基材的表面进行染色的方法,所述方法包括:将本文所述组合物中的任意一种涂覆到水泥质或矿物基材的表面上。所述方法可以以单次操作方式进行,其包括:
用过量的染色组合物(例如溶液或分散液)完全润湿所述表面;
允许组合物与基材反应并显现颜色;
允许所述染色剂就地干燥;
可选将酸中和组合物(例如溶液或分散液)施用到被染色的水泥或矿物表面。
中和组合物(例如溶液或分散液)可以包括弱碱的水性混合物(优选溶液),所述弱碱诸如为碳酸盐和碳酸氢盐,例如碳酸(氢)钠、钾、锂、铈、铵;或者为磷酸盐,诸如磷酸二钠、二钾、二锂、二铈或二铵;或者为有机碱源,诸如烷基胺和烷醇胺。
优选的中和溶液优选包含基于所述酸染色组合物中的全部酸当量至少10%摩尔当量的弱碱,诸如碳酸氢钠,更优选包含基于所述酸染色组合物中的全部酸当量至少50%摩尔当量的弱碱,最优选包含基于所述酸染色组合物中的全部酸当量至少100%摩尔当量的弱碱。
本发明的实践可以进一步包括:向先前被染色的水泥质或矿物基材上至少部分涂覆透明的保护涂层。所述保护涂层可以直接涂覆到基材上。或者,一个或多个中间层可以置于基材和保护涂层之间。通常,保护涂层(特别是基本上透明的那些涂层)的应用增强了并且进一步实现了被染色基材的颜色显现。
可以使用各种保护涂层。在某些情况下,可能需要将蜡状透明涂层涂覆到先前被染色的基材(例如混凝土、水泥质或矿物基材)上。可用在本发明中的典型蜡包括:天然植物蜡或蜂蜡,石蜡,巴西棕榈蜡和被诸如聚乙烯、聚丙烯或聚四氟乙烯的有机聚合物改性的上述天然蜡。
也可以使用聚合物保护涂层。可用在本发明中以形成保护涂层的典型聚合物包括,丙烯酸类树脂、苯乙烯-丙烯酸、聚氨酯、聚酯、醇酸树脂、环氧-酯、硅酮和环氧-酰胺。特别有利的是利用在涂覆在被染色的混凝土上后会交联的聚合物化学品。适当的交联聚合物的实例可以是如下的那些:利用可空气固化的干性油官能团、环氧-酰胺反应、硅氧烷缩合、酰肼-羰基反应、氮丙啶-酸反应、异氰酸酯-羟基反应、或碳二酰亚胺-酸反应的交联聚合物。还适当的是可辐射固化(例如可UV固化、可可见光固化或可电子束固化)涂层。优选的是那些提供高度耐磨性的化学品。对于消费者或野外-涂覆应用(field-applied application)而言,最优选的是空气干燥的环氧-酯、双组分环氧酰胺、可空气固化的醇酸树脂和氮丙啶交联的聚氨酯。对于工厂-涂覆应用(例如当制造染色的纤维水泥基材时)而言,优选使用双组分交联技术(例如异氰酸酯、三聚氰胺、不饱和或环氧交联)、粉末涂层、层压板、水性热塑性涂层体系(例如乳胶,更优选耐压碎乳胶,如在美国专利申请号11/560,329中描述的那些)、氟聚合物、热固化或辐射固化涂层(紫外线(UV)固化、可见光固化、近红外(NIR)固化或电子束固化)等。优选的工厂涂覆整理层是可辐射固化的水性涂层或100%固体涂层。
适当的可辐射固化保护涂层组合物可以包含烯属低聚物或聚合物,它们可以是无水的或水性的。适当的烯属低聚物或聚合材料的一个实例是(甲基)丙烯酸酯材料。本文使用的“(甲基)丙烯酸酯材料”意在包括甲基丙烯酸酯材料和丙烯酸酯材料。适当的烯属低聚物或聚合物包括聚氨酯类、环氧类、丙烯酸类、聚酯类、三聚氰胺类、胺类及其混合物。适当的聚氨酯类包括来自SARTOMER的CN 929,CN 963,CN 980,CN 981,CN 982,CN983,CN 9001;来自BAYER Material Sciences的Bayhydrol 2348,2282,和2317。适当的环氧类包括来自SARTOMER的CN 104,CN 120,CN 121和CN 151。适当的丙烯酸类包括来自SARTOMER的CN 816。适当的聚酯包括来自SARTOMER的CN2200,CN2257,CN2258,CN2259,和CN2260。适当的三聚氰胺类包括来自SARTOMER的CN 9890。适当的胺包括来自SARTOMER的CN 501,CN 550,CN 551,和CN 2100。
可辐射固化涂料组合物可以包含可交联稀释剂。可交联稀释剂通常包括烯属单体材料,以与不饱和低聚物或聚合物交联且降低涂料的粘度,从而可以使用标准涂装技术和设备。合适的烯属单体材料的一个实例是(甲基)丙烯酸酯单体材料。可以使用的适当(甲基)丙烯酸酯单体具有至少一个(甲基)丙烯酸酯官能团,例如丙烯酸酯和甲基丙烯酸酯化合物及其官能衍生物。(甲基)丙烯酸酯单体材料的实例包括,通常具有在约50至约750范围内分子量的单官能、二官能、三官能、四官能和五官能(甲基)丙烯酸酯材料。一些这样的材料在P.K.T.Oldring″Chemistry & Technology of UV &EB Formulation for Coatings,Inks & Paints″,Volume II,1991,SITATechnology中有所描述。当使用(甲基)丙烯酸酯单体材料时,其优选占涂料组合物的约10至70wt%,更优选占涂料组合物的约20至60wt%。
适当的(甲基)丙烯酸酯单体材料可以包括一种或多种不同的(甲基)丙烯酸酯单体,每种单体具有一个或多个(甲基)丙烯酸酯基团。(甲基)丙烯酸单体的(甲基)丙烯酸酯官能团被键合到各种核心结构基团上,所述核心结构基团可以基于各种有机结构,包括三丙二醇、异冰片醇、异癸醇、苯氧基乙基醇、三羟乙基异氰尿酸酯、三羟甲基丙烷乙氧化物、己二醇、乙氧化的和丙氧化的新戊二醇、氧乙基化的苯酚、聚乙二醇、双酚乙氧化物、新戊二醇丙氧化物、三羟甲基丙烷、丙氧基化的丙三醇、季戊四醇、四氢糠醇、β-羧基乙醇、上述的被取代衍生物、上述的组合等。
(甲基)丙烯酸酯单体材料的一个目的是降低含有烯属低聚物或聚合物的涂料组合物的粘度。此外,(甲基)丙烯酸酯单体可以为涂料组合物提供或增强所希望特性,诸如耐化学性和硬度。我们认为,在单体的各个取代基上存在若干个(甲基)丙烯酸酯基团会导致固化组合物中的每个单体和树脂分子之间的多重相互作用。这些多重相互作用可以导致增强的耐化学性、耐磨性和/或硬度。
适当(甲基)丙烯酸酯单体的实例包括(甲基)丙烯酸异冰片酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸苯氧基乙酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷乙氧化物三(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、二三羟甲基丙烷四(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸β-羧基乙酯、双酚A乙氧化物二(甲基)丙烯酸酯、和乙氧化的和丙氧化的新戊二醇二(甲基)丙烯酸酯。
可被用作可交联稀释剂的适当烯属单体材料的另一实例是烯丙基醚单体材料。适当的烯丙基醚单体材料包括一种或多种不同的烯丙基醚单体,每种单体具有一个或多个烯丙基醚基团。烯丙基醚单体的烯丙基醚官能团被键合到基于各种多元醇的核心结构基团上。适当的多元醇包括新戊二醇、三羟甲基丙烷、乙二醇、丙二醇、丁二醇、二乙二醇、三亚甲基二醇、三乙二醇、三羟甲基乙烷、季戊四醇、丙三醇、二丙三醇、1,4-丁二醇、1,6-己二醇、1,4-环己烷二甲醇等。
适当的烯丙基醚单体的实例包括羟乙基烯丙基醚、羟丙基烯丙基醚、三羟甲基丙烷单烯丙基醚、三羟甲基丙烷二烯丙基醚、三羟甲基乙烷单烯丙基醚、三羟甲基乙烷二烯丙基醚、丙三醇单烯丙基醚、丙三醇二烯丙基醚、季戊四醇单烯丙基醚、季戊四醇二烯丙基醚、季戊四醇三烯丙基醚、1,2,6-己二醇单烯丙基醚、1,2,6-己二醇二烯丙基醚等。这些化合物的丙氧化形式和乙氧化形式也是合适的。
适当烯属单体材料的另一个实例是乙烯基醚单体材料。乙烯基醚单体材料包括一种或多种不同的乙烯基醚单体,每种单体具有一个或多个乙烯基醚基团。适当的乙烯基醚单体的实例包括4-羟丁基乙烯基醚、1,4-环己烷二甲醇单乙烯基醚、1,4-环己烷二甲醇二乙烯基醚、乙二醇单乙烯基醚、乙二醇二乙烯基醚、二乙二醇单乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚等。这些化合物的丙氧化形式和乙氧化形式也是合适的。
可交联稀释剂可以包括(甲基)丙烯酸酯、烯丙基醚和乙烯基醚单体材料的混合物。此外,可以通过添加其他烯属单体材料来补充可交联稀释剂。这样的单体材料包括诸如乙烯基醚马来酸酯单体等的官能材料。
本发明的一些优选涂料组合物、特别是具有(甲基)丙烯酸酯官能团的那些可通过UV或可见光固化。这些涂料组合物通常包括光引发剂,从而当曝光时引起固化反应。光引发剂通常响应于特定波长范围的光线产生自由基,以引发使树脂和(甲基)丙烯酸酯单体材料的丙烯酸酯双键交联的自由基反应,从而使涂层固化。
其中,适于用在本发明与具有(甲基)丙烯酸酯或烯丙基醚官能团的树脂一起使用的光引发剂是α-裂解型光引发剂和夺氢型光引发剂。光引发剂优选占涂料组合物的约0.5至15wt%。光引发剂可以包含协助光化学引发反应的其他试剂,诸如助引发剂或光引发剂协同剂。
本发明中适当的裂解型光引发剂包括α.,α.-二乙氧基苯乙酮(DEAP);二甲氧基苯基苯乙酮(Irgacure 651);羟基环己基苯基甲酮(Irgacure 184);2-羟基-2-甲基-1-苯基丙-1-酮(Darocur 1173);Irgacure 1700,和Darocur 4265,所有这些得自Ciba Corporation,Ardsley,N.Y。Irgacure 1700是双-(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基苯基氧化膦和2-羟基-2-甲基-1-苯基丙-1-酮的25∶75共混物。Darocur 4265是2-羟基-2-甲基-1-苯基丙-1酮和2,4,6-三甲基苯甲酰基二苯基氧化膦(TPO)的50∶50共混物。BASF Corporation的LucirinTPO光引发剂(2,4,6-三甲基苯甲酰基-二苯基氧化膦)和Sartomer的KIP 100光引发剂(70%的低聚[2-羟基-2-甲基-[4-(1-甲基乙烯基)苯基]丙-1-酮]和30%的2-羟基-2-甲基-1-苯基丙-1-酮的混合物)也是合适的。
适当的夺氢型光引发剂包括二苯甲酮、被取代的二苯甲酮(例如Fratelli-Lamberti的Escacure TZT)和其他二芳基甲酮,诸如氧杂蒽酮、硫杂蒽酮、米蚩酮、苯偶酰、醌类以及上述所有的被取代衍生物。
Irgacure 500是比例为1∶1的Irgacure 184和二苯甲酮的混合物,其是α-裂解型光引发剂和夺氢型光引发剂的混合物的良好实例。光引发剂的其他混合物也可以用在涂料组合物中。优选的光引发剂包括Darocur 1173,KIP 100,二苯甲酮和Irgacure 184。樟脑醌是适用于采用可见光固化涂料组合物的光引发剂的一个实例。本发明的涂料组合物还可以包含助引发剂或光引发剂协同剂。助引发剂可以是(1)叔脂族胺,如甲基二乙醇胺和三乙醇胺;(2)芳族胺,如戊基对二甲基氨基苯甲酸酯、2-正丁氧基乙基-4-(二甲基氨基)苯甲酸酯、2-(二甲基氨基)乙基苯甲酸酯、乙基-4-(二甲基氨基)苯甲酸酯、和2-乙基己基-4-(二甲基氨基)苯甲酸酯;(3)(甲基)丙烯酸酯化胺,如Ebecryl 7100和Uvecryl P 104和P 115,所有都得自UCBRadCure Specialties;(4)氨基官能的丙烯酸酯或甲基丙烯酸酯树脂或低聚物共混物,诸如Ebecryl 3600或Ebecryl 3703,这二者都得自UCBRadCure Specialties。也可以使用以上四类胺的组合。
具有乙烯基醚官能团的涂料组合物可以采用阳离子生成光引发剂通过UV或可见光固化。适当的阳离子生成光引发剂的实例包括超强酸生成光引发剂,诸如三芳基锍盐。一种可用的三芳基锍盐是三苯基六氟磷酸锍Ph3S+PF6.-(可以UV16990得自Union Carbide)。
可以通过UV或可见光固化的一些涂料组合物也可以采用电子束固化。利用电子束固化涂料组合物的技术和设备是本领域已知的,并且通常不需要光引发剂。
可固化涂料组合物还可以包含被称为性能增强添加剂的成分组中的一种。涂料组合物可以包含一种以上的性能增强添加剂。可用在可固化涂料组合物中的典型性能增强添加剂包括表面活性试剂、颜料、固化指示剂、填料、UV吸收剂、受阻胺光稳定剂(HALS)和荧光增白剂。
可固化涂料组合物可以包含表面活性试剂,这种表面活性试剂会改进可固化涂料组合物与基材的相互作用,具体地该试剂可以改进组合物润湿基材的能力。表面活性试剂也可以具有其他性质。例如,表面活性试剂还可以包括流平剂、消泡剂或流动剂等。表面活性试剂影响可固化涂料组合物的品质,包括涂料组合物的处理,涂料组合物在基材的表面上的铺展,以及涂料组合物与基材的结合情况。表面活性试剂优选可以占可固化涂料组合物的约0.1至3重量%。示例性的表面活性试剂包括聚二甲基硅氧烷表面活性剂(例如Silwet L-7602,Silwet L-7622;OSI Specialties或Byk 306,Byk-Chemie)和氟化的表面活性试剂(例如Fluorad FC-430;3MCompany)。表面活性试剂可以包括消泡剂。合适的消泡剂包括聚硅氧烷消泡剂,诸如甲基烷基聚硅氧烷,如Byk 077或Byk 500(Byk-Chemie);聚合物消泡剂(例如Byk 051;Byk-Chemie)。
对于一些应用,需要涂层是至少部分透明的、着色的、染色的,并且/或者具有其他可见特性。提供这样性质的试剂也可以包含在本发明中。组合物还可以包含光泽控制添加剂或荧光增白剂,诸如来自Ciba-Geigy的Uvitex OB。
在某些情况下,有利的是保护涂料组合物中包含填料或惰性成分。填料和惰性成分包括例如粘土、玻璃珠、碳酸钙、滑石、硅石、有机填料等。填料使组合物增量、降低组合物的成本、改变组合物的外观或者为组合物提供在固化前后所需要的特定。适当的填料是本领域技术人员已知的或者可以利用标准方法测定。填料或惰性成分如果存在优选占涂料组合物的至多40重量%,更优选占0.5至40wt%。
保护涂料组合物还可以包含其他成分,诸如那些会改进可固化涂料组合物在被储存、加工或应用时以及在其他或随后阶段时的性质的成分。可以根据需要将蜡、平光剂、划痕和磨损添加剂以及其他类似的性能增强添加剂以有效提升固化涂层和涂料组合物性能的量用在本发明中。涂层的所需性能特征包括耐化学性、耐磨性、硬度、光泽、反射率、外观,或者这些特性的组合,以及其他类似特性。
各种其他可选添加剂也可用于保护涂料组合物,这对本领域普通技术人员来说是已知的,包括在Koleske等人的Paint and Coatings Industry,April 2003,pages 12-86中描述的那些。例如,最终面涂层组合物可以包含一种或多种性能或性质增强添加剂,诸如着色剂、染料、增稠剂、热稳定剂、流平剂、防缩孔剂、固化指示剂、增塑剂、沉降抑制剂、紫外光吸收剂等。而且,对于利用工厂涂布设备(例如帘涂机)的应用而言,组合物可以包含为所选用的设备和装置所设计的添加剂。上述添加剂通常利用本领域普通技术人员所熟知的标准方法根据具体场地进行选择。
可以通过本领域普通技术人员已知的任何常规方法涂覆着色组合物,例如通过辊涂、喷涂、喷墨沉积或者将组合物刷涂到基材(例如混凝土基材)上。在工厂应用的装置中,适当的方法还包括帘涂,以及将涂层涂覆到移动基材上的其他方法。通常,涂覆方法将影响最终结果。例如,喷涂在染色剂上将形成更自然的外观;而刷涂将产生更均匀的结果。使用多层含有不同染色剂的涂层会形成更多样的颜色。如果需要,可以喷刷图案,或者甚至在基材顶部预沉积“抗蚀剂”,从而使随后涂覆的染色剂以不同方式对施用了抗蚀剂的区域进行染色。在一个实施方式中,抗蚀剂是疏水材料,这会防止被涂覆的染色剂润湿混凝土表面。适当的疏水材料包括例如,蜡(例如石蜡)、油(例如矿物油)或挥发性疏水溶剂(例如芳族150)。优选的抗蚀材料使被涂覆的染色剂在混凝土的表面上“成珠”(bead up)。这种抗蚀剂可以以任何期望的设计涂覆。在另一实施方式中,挥发性抗蚀剂以所需图案被涂覆到混凝土上,染色剂被涂覆到混凝土上并干燥,使挥发性疏水抗蚀剂蒸发,从而使经抗蚀剂处理的区域可染色,随后对先前经抗蚀剂处理的区域进行染色剂涂覆。在另一实施方式中,挥发性疏水抗蚀剂以所需图案被涂覆到混凝土上,染色剂被涂覆到混凝土上并干燥,使挥发性疏水抗蚀剂蒸发,从而使经抗蚀剂处理的区域可染色,以与先前图案不同的所需图案对混凝土施用挥发性疏水抗蚀剂的第二涂覆,随后对混凝土进行染色剂涂覆。上述涂覆方法可以重复若干次,从而在混凝土上形成复杂设计。
实施例
如下是染色组合物的非限制性实例,它们用于进一步阐述本发明的优点。
实施例1
该实施例和以下实施例描述了着色组合物,在该组合物中,酸性由易于处理的成分就地生成。脲单盐酸盐是稳定的固体,其是质子化脲的盐酸盐。并不希望受缚于任何理论,该化合物当被溶解在水中时被认为解离成氢离子、水性脲物质和氯离子,所述水性脲物质被认为至少包含与共轭酸平衡的脲。当组合物与水泥质基材反应时,至少部分水性脲物质被认为分解成包含氨和碳酸的产物。碳酸接着分解成水和CO2。氨是比尿素更强的碱,较强碱的形成可能有助于组合物的自中和。尿素的降解有可能还可以释放额外的酸性物质,以提高组合物的刻蚀性能。示意性地,具有类似分解特性的脲或碱可被视为组合物的屏蔽和可控释放酸势(acidpotential),因而使酸使用安全,然而仍旧有效。FeCl2不仅是提供着色作用的盐,还是Lewis酸。在水性溶液中,1摩尔这种盐解离产生约2摩尔的氢离子。
材料 | 重量(lb) | 体积(加仑) |
水 | 54.75 | 6.57 |
脲单盐酸盐 | 9 | 0.89 |
32%FeCl2溶液 | 37.5 | 3.51 |
硅氧烷消泡剂* | 0.1 | 0.011 |
总量 | 101.35 | 10.98 |
*可商购的消泡聚合物和聚硅氧烷的专有产品
这个实例得到“浅黄褐色”或棕褐色的染色材料。
实施例2
材料 | 重量(lb) | 体积(加仑) |
水 | 48.26 | 5.79 |
脲单盐酸盐 | 9 | 0.89 |
CuCl2·2H2O | 15.3 | 0.72 |
水 | 18 | 2.16 |
32%FeCl2溶液 | 9 | 0.84 |
硅氧烷消泡剂* | 0.1 | 0.012 |
总量 | 99.66 | 10.41 |
*可商购的消泡聚合物和聚硅氧烷的专有产品
这个实例得到橄榄色或绿色的染色材料。
实施例3
材料 | 重量(lb) | 体积(加仑) |
水 | 19.89 | 2.38 |
脲单盐酸盐 | 9.89 | 0.98 |
硅氧烷消泡剂* | 0.1 | 0.011 |
FeCl2溶液,40% | 31.25 | 2.67 |
MnCl2·4H2O | 21.43 | 1.27 |
脲单盐酸盐 | 1.75 | 0.17 |
水 | 15.78 | 1.89 |
总量 | 100.09 | 9.37 |
*可商购的消泡聚合物和聚硅氧烷的专有产品
这个实例得到“咖啡”色或棕色的染色材料。
实施例4
将实施例1的“浅黄褐色”染色材料涂覆到水泥纤维板基材上,并干燥。浅黄褐色颜色显现。在颜色更充分的显现后,涂覆下述顶涂层。
实施例4a-可电子束固化的顶涂层
在由实施例4得到的经染色的板材上顶涂可电子束固化的涂层,所述涂层包含132.5份CN991(Sartomer)和56.8份己二醇二丙烯酸酯(Sartomer)。该涂层通过AEB(Wilmington,MA)供应的电子束在150kV、50英尺/分钟线速度、500ppm氧含量和光束设置10下固化。所得涂层是硬质的耐久保护顶涂层。
实施例4b-可紫外线固化的顶涂层
在由实施例4得到的经染色的板材上顶涂可紫外线固化的涂层,所述涂层包含132.5份CN991(Sartomer)、56.8份己二醇二丙烯酸酯(Sartomer)和10份KIP 100(Sartomer)。该涂层通过两盏300瓦/英寸中压汞灯在60英尺每分钟的线速度下固化。
所得涂层是硬质的耐久保护顶涂层。
实施例4c-热塑性顶涂层
在由实施例4得到的经染色的板材上顶涂水基乳胶/含氟聚合物共混物涂层,所述涂层包含159.1份XK-90(DSM,Elgin,IL)、143.19份Lumiflon4300(Asahi Glass Company)和25份水。该涂层在300℉(149℃)烘箱中干燥,直到实现200℉(93.3℃)的板表面温度。
所得涂层是硬质的耐久保护顶涂层。
实施例4d-可紫外线固化的顶涂层
在由实施例4得到的经染色的板材上顶涂水基紫外线固化涂层,所述涂层由100份Bayhydrol UV LS 2317和1.5份Irgacure 500(Ciba)组成。该涂层要么首先空气干燥直到“表干”要么首先在300℉(149℃)热空气烘箱中干燥至约160至180℉(71至82℃)的BST(板表面温度),然后通过两盏300瓦/英寸中压汞灯在60英尺每分钟的线速度下固化。
所得涂层预期为硬质的耐久保护涂层。
实施例5
将实施例3的“咖啡色”染色材料涂覆到水泥纤维板基材上,并干燥。
实施例5a-可电子束固化的顶涂层
在由实施例5得到的经染色的板材上顶涂可电子束固化的涂层,所述涂层包含132.5份CN991(Sartomer)和56.8份己二醇二丙烯酸酯(Sartomer)。该涂层通过AEB(Wilmington,MA)供应的电子束在150kV、50英尺/分钟线速度、500ppm氧含量和光束设置10下固化。
所得涂层是硬质的耐久保护顶涂层。
实施例5b-可紫外线固化的顶涂层
在由实施例5得到的经染色的板材上顶涂可紫外线固化的涂层,所述涂层包含132.5份CN991(Sartomer)、56.8份己二醇二丙烯酸酯(Sartomer)和10份KIP 100(Sartomer)。该涂层通过两盏300瓦/英寸中压汞灯在60英尺每分钟的线速度下固化。
所得涂层是硬质的耐久保护顶涂层。
实施例5c-热塑性顶涂层
在由实施例5得到的经染色的板材上顶涂水基乳胶/含氟聚合物共混物涂层,所述涂层包含159.1份XK-90(DSM,Elgin,IL)、143.19份Lumiflon4300(Asahi Glass Company)和25份水。该涂层在300℉(149℃)烘箱中干燥,直到实现200℉(93.3℃)的板表面温度。
所得涂层是硬质的耐久保护顶涂层。
实施例5d-可紫外线固化的顶涂层
在由实施例5得到的经染色的板材上顶涂水基紫外线固化涂层,所述涂层由100份Bayhydrol UV LS 2317和1.5份Irgacure 500(Ciba)组成。该涂层要么首先空气干燥直到“表干”要么首先在300℉(149℃)热空气烘箱中干燥至约160至180℉(71至82℃)的BST(板表面温度),然后通过两盏300瓦/英寸中压汞灯在60英尺每分钟的线速度下固化。
所得涂层预期为硬质的耐久保护涂层。
这些实施方式或实例应当被认为是非限制性的,它们仅仅表示本发明组合物和方法的几种可能性。尽管本发明的原理结合具体实施方式进行描述,但是应当清楚地认识到:仅通过实施例进行描述,这些描述并不限制本发明的范围。同样,可以在其它并未脱离本发明的精神或本质的具体形式来具体表明本发明,因此应当参照所附权利要求而非前述说明来表示本发明的范围。
Claims (11)
1.一种使纤维水泥基材着色的方法,所述方法包括如下步骤:
a)提供组合物,所述组合物包含如下组分的反应混合物:(i)酸,其具有小于6的pKa;(ii)弱碱,其中所述弱碱的共轭酸的pKa小于7但大于所述酸的pKa;和(iii)一种或多种金属盐,所述金属盐在所述组合物被涂覆到所述纤维水泥基材的表面上时会为所述纤维水泥基材的表面提供颜色;
b)将所述组合物涂覆到所述纤维水泥基材的至少部分表面上,
c)使所述组合物与所述基材的表面发生反应并显现颜色;和
d)涂覆保护涂层以覆盖所述纤维水泥基材的表面。
2.如权利要求1的方法,其中,所述保护涂层由包括至少一种可辐射固化组分的成分衍生得到,并且其中步骤(d)还包括利用辐射固化所述保护涂层。
3.如前述权利要求中任意一项所述的方法,其中,所述酸具有小于1的pKa。
4.如前述权利要求1或2所述的方法,其中,所述组合物还包含金属离子络合剂。
5.如前述权利要求1或2所述的方法,其中,所述步骤b)包括,用过量的所述组合物至少部分润湿所述纤维水泥基材的表面,并且所述方法还包括如下步骤:
干燥所述基材表面。
6.如权利要求5所述的方法,还包括中和所述着色表面的步骤。
7.如前述权利要求1或2所述的方法,还包括如下步骤:在所述着色表面的至少一部分上涂覆至少部分透明的保护涂层。
8.如前述权利要求1或2所述的方法,还包括如下步骤:在步骤b)之前对所述纤维水泥基材的表面应用疏水性抗蚀剂。
9.如前述权利要求1或2所述的方法,其中,所述弱碱在涂覆到所述基材上时分解成一种或多种组分,这些组分包括另一种碱。
10.如前述权利要求1或2所述的方法,其中,所述弱碱在涂覆到所述基材上时分解成一种或多种组分,这些组分在25℃下的蒸汽压大于0.01psi。
11.一种使纤维水泥基材的表面着色的方法,包括如下步骤:
a)将酸性组合物涂覆到所述纤维水泥基材的至少部分表面上,所述酸性组合物包含如下组分的反应混合物:(i)酸,其具有小于6的pKa;和(ii)一种或多种金属盐,所述金属盐在所述酸性组合物被涂覆到所述纤维水泥基材的表面上并且与所述纤维水泥基材的表面反应时提供颜色;
b)使所述酸性组合物与所述基材的表面反应并显现颜色;和
c)涂覆辐射固化的保护涂层,以覆盖所述纤维水泥表面。
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US12/291,316 | 2008-11-07 | ||
US12/291,316 US8092555B2 (en) | 2007-05-10 | 2008-11-07 | Concrete coloring compositions and methods |
PCT/US2009/005984 WO2010053552A1 (en) | 2008-11-07 | 2009-11-05 | Concrete coloring compositions and methods |
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EP2365946B1 (en) | 2018-07-04 |
AU2009311647A1 (en) | 2010-05-14 |
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US20120247372A1 (en) | 2012-10-04 |
EP2365946A4 (en) | 2015-04-15 |
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