CN112424246B - 耐污涂料组合物 - Google Patents
耐污涂料组合物 Download PDFInfo
- Publication number
- CN112424246B CN112424246B CN201980047407.0A CN201980047407A CN112424246B CN 112424246 B CN112424246 B CN 112424246B CN 201980047407 A CN201980047407 A CN 201980047407A CN 112424246 B CN112424246 B CN 112424246B
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- coating composition
- substrate
- resin particles
- urethane acrylate
- matting agent
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 90
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 69
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000006224 matting agent Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
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- 238000002360 preparation method Methods 0.000 abstract description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
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- 239000000523 sample Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
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- 238000010998 test method Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
一种涂料组合物，其由(i)氨酯丙烯酸酯树脂颗粒；(ii)丙烯酸树脂颗粒的混合物的水性分散体；以及(iii)消光剂制备。一种赋予基材耐污性的方法，其包括将涂料组合物施涂到该基材的至少一部分上。
Description
技术领域
本发明涉及耐污涂料组合物以及由其制备的低光泽度涂料。
背景技术
在水性建筑油漆以及其它涂料组合物中，可以通过配制在干燥时产生光滑、有光泽表面的组合物来实现耐污性。耐污性是指耐污迹，难以被污渍润湿，难以被污渍粘附和/或在不损害涂层的情况下易于去除污渍(即可洗性)。常规高光油漆或半光油漆耐污渍和/或可洗涤。
发明内容
本发明包含一种涂料组合物，其包括氨酯丙烯酸酯树脂颗粒和丙烯酸树脂颗粒的混合物的水性分散体(其中氨酯丙烯酸酯树脂颗粒和丙烯酸树脂颗粒彼此不同)以及消光剂。
具体实施方式
为了以下详细描述的目的，应当理解，本发明可以采取各种替代性变化和步骤顺序，除非明确地相反指定。还应理解，以下说明书中描述的具体组合物、涂覆的基材、多层涂层和方法仅是本发明的示例性实施例。此外，除了在任何操作示例中，或者在另外指明的情况下，在说明书和权利要求中使用的表示例如成分的数量的所有数字应被理解为在所有情况下由术语“约”修饰。因此，除非有相反的指示，否则在下面的说明书和所附权利要求中阐述的数值参数是近似值，其可以根据本发明要获得的期望的特性而变化。至少，并不是试图将等同原则的应用限制到权利要求的范围，每个数值参数至少应该根据所记录的有效数字的数量并通过应用普通的舍入技术来解释。
尽管阐述本发明的广泛范围的数值范围和参数是近似值，但是在具体示例中阐述的数值被尽可能精确地记录。然而，任何数值都固有地含有某些由于各自测试测量中的标准偏差所必然导致的误差。
此外，应当理解，本文所述的任何数值范围旨在包含其中归入的所有子范围。例如，“1至10”的范围旨在包含所述最小值1和所述最大值10之间(并包含此二值)的所有子范围，即具有大于等于1的最小值和小于等于10的最大值。
在本申请中，除非另外具体说明，否则单数的使用包含复数并且复数涵盖单数。此外，在本申请中，除非另外具体说明，否则“或”的使用意指“和/或”，即使“和/或”可以明确地用于某些情况。
如上所述，本发明的某些实施例涉及水性分散体。如本文所用，术语“分散体”是指两相体系，其中一相包含细分散的颗粒(例如直径小于500nm，分布在整个第二相(其为连续相)。本发明的分散体通常为“水包有机相”乳液，其中水性介质提供了分散体的连续相，其中颗粒作为有机相悬浮在其中。
如本文所用，术语“水性”、“水相”、“水性介质”等是指仅由水组成或主要包括水(例如至少50重量％的水)与另一种材料(例如，惰性有机溶剂)的组合的介质。在某些实施例中，存在于本发明的水性分散体中的有机溶剂的量小于20重量％，例如小于10重量％，或在一些情况下小于5重量％，或在其它情况下小于2重量％，其中重量百分比基于分散体的总重量计。合适的有机溶剂的非限制性示例为丙二醇单丁醚、乙二醇单己基醚、乙二醇单丁醚、正丁醇、苯甲醇和石油醚。
与“树脂”互换使用的术语“聚合物”意指涵盖低聚物，并且包含但不限于均聚物和共聚物。“预聚物”是指作为中间阶段产生的聚合物，其在聚合完成之前进一步反应。
具有改善的耐污性的本发明的涂料组合物包括氨酯丙烯酸酯树脂颗粒(i)和丙烯酸树脂颗粒(ii)的水性分散体与消光剂(iii)的混合物。“混合物”是指组分(i)、(ii)、(iii)彼此不反应，而是保持为不同的颗粒。虽然不限于此，但本发明的涂料组合物可用作建筑油漆，诸如用于涂覆表面诸如内墙等的内部油漆。
水性分散体包含氨酯丙烯酸酯树脂颗粒(i)，其作为通过聚合树脂反应混合物获得的反应产物的水性分散体产生，该树脂反应混合物包含：(A)含羧基的聚氨酯预聚物，其包含通过使以下的混合物反应获得的反应产物：(a)多元醇；(b)含有至少一个丙烯酸官能团和至少一个活性氢基团的可聚合的烯键式不饱和单体；(c)多异氰酸酯；(d)链终止胺，以及(e)扩链胺；(B)可聚合的烯键式不饱和单体；以及(C)中和胺。氨酯丙烯酸酯树脂颗粒的分散体可通过以下制备：形成含羧基、异氰酸酯封端的聚氨酯预聚物，向该预聚物中加入多烯键式不饱和单体以得到预聚物/单体混合物，将该预聚物/单体混合物与中和剂(例如中和胺)、链终止剂和扩链剂一起分散在水中，并使烯键式不饱和单体聚合。
产生聚氨酯预聚物的反应混合物(A)中的合适的多元醇(a)包含数均分子量(MN)(如通过凝胶渗透色谱法使用聚苯乙烯标准物测定的)在300-7000范围内的那些，特别是二醇和三醇及其混合物，但更高官能度的多元醇也可例如作为与二醇混合的次要组分使用。多元醇可为在常规聚氨酯制剂中使用的任何化学类别的聚合物多元醇的成员。具体而言，多元醇可为聚酯、聚酯酰胺、聚醚、聚硫醚、聚碳酸酯、聚缩醛、聚烯烃或聚硅氧烷。
可以使用的聚酯多元醇包含但不限于多元醇诸如乙二醇、丙二醇、二乙二醇、新戊二醇、1,4-丁二醇、呋喃二甲醇、环己烷二甲醇、甘油、三羟甲基丙烷或季戊四醇或其混合物与多元羧酸，特别是二羧酸或其成酯衍生物，例如琥珀酸、戊二酸和己二酸或其甲酯、邻苯二甲酸酐或对苯二甲酸二甲酯的羟基封端的反应产物。也可使用通过内酯(例如己内酯)与多元醇的连接获得的聚酯。
聚酯酰胺可通过在聚酯化混合物中包含氨基醇(诸如乙醇胺)来获得。可使用的聚醚多元醇包含通过环状氧化物(例如环氧乙烷、环氧丙烷或四氢呋喃)的聚合或通过将一种或多种这样的氧化物添加到多官能引发剂(例如水、乙二醇、丙二醇、二乙二醇、环己烷二甲醇、甘油、三羟甲基丙烷、季戊四醇或双酚A)中而获得的产物。特别有用的聚醚包含聚氧化丙烯二醇和三醇、聚(氧化乙烯-氧化丙烯)二醇和三醇，其通过将氧化乙烯和氧化丙烯同时或依次加入到合适的引发剂中而获得，以及聚四亚甲基醚二醇，其通过四氢呋喃的聚合而获得。
可使用的聚硫醚多元醇包含通过硫二甘醇单独或与其它二醇、二羧酸、甲醛、氨基醇或氨基羧酸缩合获得的产物。
可使用的聚碳酸酯多元醇包含通过使二醇(诸如1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二甘醇或四甘醇)与碳酸二芳基酯(例如碳酸二苯酯)或与光气反应获得的产物。
可使用的聚缩醛多元醇包含通过二醇(例如二甘醇、三甘醇或己二醇)与甲醛反应制备的那些。合适的聚缩醛也可通过聚合环状缩醛来制备。
合适的聚烯烃多元醇包含羟基封端的丁二烯均聚物和共聚物。
反应混合物(A)的多元醇(a)可进一步包含含有酸基团的单体，诸如含羧基的二醇和三醇，其可使聚氨酯预聚物具有水分散性。合适的含羧基的二醇包含，例如，式R1C(CH2OH)2COOH的二羟基链烷酸，其中R1为氢或C1-C10烷基，诸如2,2-二羟甲基丙酸(DMPA)。如果需要，含羧基的二醇或三醇可在并入预聚物中之前通过与二羧酸反应并入聚酯中。有用的含酸基团的化合物包含氨基羧酸，例如赖氨酸、胱氨酸和3,5-二氨基苯甲酸。
包含在反应混合物(A)中的含有至少一个丙烯酸官能团和至少一个活性氢基团的可聚合的烯键式不饱和单体(b)包含烯键式不饱和基团，诸如丙烯酸酯、甲基丙烯酸酯。丙烯酸酯和甲基丙烯酸酯官能团可由式CH2＝C(R2)-C(O)O-表示，其中R2为氢或甲基。组分(b)中包含的其它单体可包含氨基甲酸烯丙酯和碳酸烯丙酯。氨基甲酸烯丙酯和碳酸烯丙酯可分别由式CH2＝CH-CH2-NH-C(O)O-和CH2＝CH-CH2-O-(C)O-表示。例如，在制备聚氨酯预聚物中使用的具有丙烯酸官能团和活性氢基团的烯键式不饱和单体可包括(甲基)丙烯酸羟烷基酯。合适的(甲基)丙烯酸羟烷基酯包含在烷基中具有1至18个碳原子的那些，该烷基是取代的或未取代的。此类材料的具体非限制性示例包含(甲基)丙烯酸2-羟乙酯(HEMA)、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸2-羟丁酯、己-1,6-二醇单(甲基)丙烯酸酯、(甲基)丙烯酸4-羟丁酯及其混合物。如本文所用，术语“(甲基)丙烯酸酯”意在包含丙烯酸酯和甲基丙烯酸酯两者。
用于产生聚氨酯预聚物的反应混合物(A)中的多异氰酸酯(c)可为脂族或芳族的或其混合物。可使用二异氰酸酯，尽管可使用更高级的多异氰酸酯，诸如二异氰酸酯的异氰脲酸酯，诸如二苯基甲烷二异氰酸酯(MDI)(包含其2,4'、2,2'和4,4'异构体、其均聚物和混合物、二苯基甲烷二异氰酸酯(MDI)的混合物及其低聚物，以及如本文所述的多异氰酸酯与含有异氰酸酯反应性氢原子的组分形成聚合的多异氰酸酯(预聚物)的反应产物)、甲苯二异氰酸酯(TDI)(包含其任何合适的异构体混合物中的2,4TDI和2,6TDI、六亚甲基二异氰酸酯(HMDI或HDI)、异佛尔酮二异氰酸酯(IPDI)、亚丁基二异氰酸酯、三甲基六亚甲基二异氰酸酯)、二(异氰酸根合环己基)甲烷(包含4,4'-二异氰酸根合二环己基甲烷(H12MDI)、异氰酸根合甲基-1,8-辛烷二异氰酸酯、四甲基二甲苯二异氰酸酯(TMXDI)、1,5-萘二异氰酸酯(NDI)、对亚苯基二异氰酸酯(PPDI)、1,4-环己烷二异氰酸酯(CD)、联甲苯胺二异氰酸酯(TODD)、这些多异氰酸酯的任何合适的混合物，以及这些多异氰酸酯中的一种或多种与MDI型多异氰酸酯的任何合适的混合物)。
合适的链终止胺(d)包含C1-C6烷基胺(诸如丁胺、二乙胺、二异丙胺和二丁胺)和C1-C6羟基胺(诸如乙醇胺、二乙醇胺和二异丙醇胺)。合适的扩链胺(e)可包含乙二胺、二亚乙基三胺、三亚乙基四胺、丙二胺、丁二胺、六亚甲基二胺、环己二胺、哌嗪、2-甲基哌嗪、苯二胺、甲苯二胺、三(2-氨基乙基)胺、4,4'-亚甲基双(2-氯苯胺)、3,3'-二氯-4,4'-二苯基二胺、2,6-二氨基吡啶、4,4'-二氨基二苯基甲烷、异佛尔酮二胺，以及二亚乙基三胺与丙烯酸酯或其水解产物的加合物，特别是C2-C10烷基胺(诸如二甲基乙二胺(DMEA))。所用的扩链剂的量应该大约等于预聚物中的游离异氰酸酯基团，并且扩链剂中的活性氢与预聚物中的异氰酸酯基团的比例可在(0.7至1.3):1的范围内。
水分散性聚氨酯预聚物可以常规方式通过使化学计量过量的多异氰酸酯与多元醇在基本上无水的条件下在30℃至130℃之间的温度下反应直至异氰酸酯基团和活性氢(羟基)基团之间的反应基本上完成来制备。多异氰酸酯和含活性氢的组分以这样的比例适当地反应，使得异氰酸酯基团的数目与活性氢基团的数目的比例在1.1:1至6:1的范围内，诸如在1.5:1至3:1的范围内。
合适的助剂和/或添加剂可包含在反应混合物(A)中，诸如自由基聚合抑制剂和/或抗氧化剂(抗黄化添加剂)，诸如3-甲基-2-丁烯醇、有机焦碳酸酯和亚磷酸三苯酯。
包含在树脂反应混合物中的合适的可聚合的烯键式不饱和单体(B)包含烯键式不饱和烃、酯和醚，诸如丙烯酸和甲基丙烯酸的酯，以及乙烯醇和苯乙烯的酯。具体示例包含丁二烯、异戊二烯、苯乙烯、取代的苯乙烯、丙烯酸、甲基丙烯酸和马来酸的低级烷基(C1-C6)酯(诸如甲基丙烯酸丁酯(BMA)、乙酸乙烯酯和丁酸乙烯酯)、丙烯腈、乙烯基甲基醚、丙基醚和丁基醚、氯乙烯、偏二氯乙烯等。其它合适的多烯键式不饱和单体包含甲基丙烯酸烯丙酯、C1-C6二醇的二丙烯酸酯(诸如二丙烯酸丁二醇酯和二丙烯酸己二醇酯)、二乙烯基苯、二乙烯基醚、二乙烯基硫醚、三羟甲基丙烷三丙烯酸酯等。
包含中和胺(C)以中和羧基的酸官能度，并将中和胺(C)加入到树脂反应中以使反应产物水可分散，即基本上中和羧基官能度的量，如本领域所熟知的。适当地，以每当量羧基官能度65％至100％胺当量添加胺。可用于实施本发明的叔胺是相对挥发性的，使其在固化时从涂层中蒸发。示例将包含式N(R3)(R4)(R5)的胺，其中R3、R4和R5独立地为C1–C4烷基和羟烷基。这种叔胺的示例为三乙胺、二甲基乙醇胺、甲基二乙醇胺和甲基二乙胺。可使用本领域所熟知的技术将预聚物/单体混合物分散在水中。可在搅拌下将混合物添加到水中，或可选地，可将水搅拌到混合物中。
通过向其中添加自由基引发剂来使所述树脂反应混合物进行自由基引发的聚合。合适的自由基引发剂包含所谓的氧化还原引发剂，其由至少一种有机还原剂和至少一种过氧化物和/或氢过氧化物(例如，叔丁基氢过氧化物)与硫化合物(例如，羟基甲亚磺酸的钠盐、亚硫酸钠、亚硫酸氢钠、硫代硫酸钠或丙酮亚硫酸氢盐加合物)，或过氧化氢与抗坏血酸组成。或者，树脂反应混合物的自由基聚合可通过在升高的温度下加入聚合引发剂进行，该升高的温度即足以以维持聚合反应的速率释放自由基并完成预聚物的扩链的温度，因为扩链反应在向水分散体中加入扩链剂后开始进行。合适的温度范围为50℃至90℃。合适的热自由基引发剂包含但不限于过氧化物化合物、偶氮化合物、过硫酸盐化合物及其混合物。
应当理解，烯键式不饱和单体(B)和胺组分(C)的添加顺序可以变化。可在一个或多个阶段中将引发剂组合物添加到树脂反应混合物中以实现并继续聚合。
丙烯酸树脂颗粒(ii)的水性分散体包含烯键式不饱和单体的反应产物，其可包含多烯键式不饱和单体。
合适的仅具有一个不饱和位点的烯键式不饱和单体，即单烯键式不饱和单体包含但不限于苯乙烯、α-对甲基苯乙烯、乙烯基甲苯、4-甲基苯乙烯、叔丁基苯乙烯、2-氯苯乙烯、乙烯基吡啶、乙烯基吡咯烷酮、巴豆酸甲酯、巴豆酸钠、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸异丁酯、甲基丙烯酸正戊酯、甲基丙烯酸异戊酯、甲基丙烯酸正己酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸正辛酯、甲基丙烯酸甲基烯丙酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸烯丙酯、甲基丙烯酸环己酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、甲基丙烯酸N,N-二甲基氨基乙酯、甲基丙烯酸N,N-二乙基氨基乙酯、甲基丙烯酸叔丁基氨基乙酯、甲基丙烯酸2-磺基乙酯、甲基丙烯酸三氟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸2-正丁氧基乙酯、甲基丙烯酸2-氯乙酯、甲基丙烯酸2-乙基丁酯、甲基丙烯酸肉桂酯、甲基丙烯酸环戊酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸糠酯、甲基丙烯酸六氟异丙基酯、甲基丙烯酸3-甲氧基丁基酯、甲基丙烯酸2-甲氧基丁酯、甲基丙烯酸2-硝基-2-甲基丙酯、甲基丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯基乙酯、甲基丙烯酸炔丙酯、甲基丙烯酸四氢糠酯、甲基丙烯酸四氢吡喃酯、甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N-乙基甲基丙烯酰胺、N,N-二乙基甲基丙烯酰胺、N,N-二甲基甲基甲基丙烯酰胺、N-苯基甲基丙烯酰胺、丙烯酰胺、N,N-二乙基丙烯酰胺、N-乙基丙烯酰胺、甲基2-氰基丙烯酸酯、甲基α-氯丙烯酸酯、甲基丙烯醛、丙烯醛、甲基丙烯腈和丙烯腈。
可用于丙烯酸树脂颗粒(ii)的多烯键式不饱和单体的具体非限制性示例包含但不限于二丙烯酸酯，诸如1,6-己二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、二甘醇二丙烯酸酯、四甘醇二丙烯酸酯、三丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、聚(丁二醇)二丙烯酸酯、四甘醇二甲基丙烯酸酯、1,3-丁二醇二丙烯酸酯、三甘醇二丙烯酸酯、三异丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯和/或双酚A二甲基丙烯酸酯；三丙烯酸酯，诸如三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇单羟基三丙烯酸酯和/或三羟甲基丙烷三乙氧基三丙烯酸酯；四丙烯酸酯，诸如季戊四醇四丙烯酸酯和/或二-三羟甲基丙烷四丙烯酸酯；和/或五丙烯酸酯，诸如二季戊四醇(单羟基)五丙烯酸酯。
丙烯酸类聚合物可以经由水性乳液聚合技术或经由具有能够成盐的基团(诸如酸或胺基)的有机溶液聚合技术来制备。在用碱或酸中和这些基团时，可以将聚合物分散到水性介质中。
本发明的消光剂(iii)包含无机和/或有机消光剂。合适的无机消光剂包含二氧化硅、硅酸铝和/或碳酸钙，其粒度小于100微米，诸如小于10微米。合适的有机消光剂包含蜡、热塑性聚合物和/或热固性聚合物，其中有机消光剂不同于氨酯丙烯酸酯树脂颗粒(i)和丙烯酸树脂颗粒(ii)。消光剂应当能够赋予涂料低光泽度，其中低光泽度定义为MasterPainters Institute(MPI)的1至3的光泽度水平(分别为无光饰面、天鹅绒样饰面和蛋壳状饰面)，其60°光泽度低于20个单位，而85°光泽度低于35个单位。
已经发现，当氨酯丙烯酸酯树脂颗粒的z-平均粒度小于丙烯酸颗粒的z-平均粒度时，可以改善耐污性。相反，当丙烯酸树脂颗粒的z-平均粒度小于氨酯丙烯酸酯树脂颗粒时，不能改善耐污性。z-平均粒度可使用本领域熟知的动态光散射技术和仪器测量。将样品稀释并分散在适当溶剂中以进行光散射。测量仪器，诸如Malvern Zetasizer Nano ZS，评估样品的光强度图案的变化，并计算平均粒径和分布。例如，丙烯酸树脂颗粒的z-平均粒度可以比氨酯丙烯酸酯树脂颗粒大至少10％，诸如至少20％或30％或40％或50％或60％。例如，丙烯酸树脂的粒度可在120nm至150nm的范围内，而氨酯丙烯酸酯树脂的粒度可在55nm至140nm的范围内。不希望受任何特定理论限制，在一方面，较小的氨酯丙烯酸酯树脂颗粒可填充较大的丙烯酸树脂颗粒之间的间隙，从而形成更耐污渍渗透的紧密填充的漆膜。此外，氨酯丙烯酸酯树脂颗粒可能自分层到漆膜的表面，从而在表面上形成耐污渍渗透的富含树脂的区域。氨酯丙烯酸酯颗粒和丙烯酸树脂颗粒各自的z-平均粒度可经由聚合条件和/或单体组分浓度来选择，如本领域所熟知的。例如，可通过改变包含在胺组分(c)中的叔胺的相对量来调节氨酯丙烯酸酯颗粒的z-平均粒度。特别地，较高量的中和胺导致较小的氨酯丙烯酸酯颗粒。水分散性聚氨酯聚合物含有水相容性链段和水不相容链段。不受任何特定理论的限制，据信，当将水分散性聚氨酯聚合物添加到水中时，聚合物链自身排列形成微粒，其中水相容性链段位于微粒的表面，而水不相容链段在微粒内部。具有相对较多的水相容性链段和相对较少的水不相容链段的聚合物将形成具有相对较高表面积和相对较低内部体积的微粒，从而产生较小尺寸的微粒。聚氨酯聚合物中更大量的酸和更大量的中和胺导致更多的与水相容性聚合物链段和更少的水不相容聚合物链段，从而导致更小的微粒。在通过聚合可聚合的烯键式不饱和单体(B)完成微粒结构之前，聚氨酯聚合物中50％至100％的酸可用中和胺(C)中和。
氨酯丙烯酸酯树脂颗粒可包括30重量％至90重量％，诸如50重量％至80重量％的聚氨酯预聚物(A)，以及10重量％至70重量％，诸如20重量％至50重量％的由可聚合烯键式不饱和单体(B)形成的聚合物。聚氨酯预聚物(A)可包括30重量％至90重量％，诸如40重量％至60重量％的多元醇(a)；0.3重量％至8重量％，诸如0.5重量％至3重量％的含有至少一个羟基的可聚合的烯键式不饱和单体(b)；20重量％至60重量％，诸如30重量％至50重量％的多异氰酸酯(c)；0.2重量％至6重量％，诸如0.4重量％至3重量％的链终止胺(d)；0.5重量％至6重量％，诸如2重量％至4重量％的扩链胺(e)。聚氨酯预聚物(a)的数均分子量(MN，通过凝胶渗透色谱法测定)可在1800-25000，诸如5000-10000的范围内，并且酸当量重量可以为800至3000，诸如1000至2000(通过用标准碱溶液滴定测定)。
同样地，可通过改变表面活性剂类型和/或浓度和/或使用种子胶乳来调节丙烯酸树脂颗粒的z-粒度。表面活性剂类型和浓度可以决定在乳液聚合过程中形成的胶束的数目和尺寸，这进而决定所得丙烯酸胶乳的粒度。表面活性剂在胶束内的成核和生长过程中稳定聚合物颗粒。为了更好地控制粒度并产生较窄的粒度分布，可以使用种子胶乳作为聚合的成核点。当加入单体和表面活性剂以生长胶乳颗粒时，颗粒的数量保持恒定。
本发明的涂料组合物可通过将氨酯丙烯酸酯树脂颗粒的水性分散体、丙烯酸树脂颗粒的水性分散体和消光剂以任何顺序混合在一起来制备。消光剂可在其制备过程(诸如在研磨阶段)中掺入到丙烯酸树脂颗粒的水性分散体中。基于总树脂固体，本发明的涂料组合物可包含至少5重量％且至多50重量％，包含其间的所有量的氨酯丙烯酸酯树脂。例如，氨酯丙烯酸酯树脂可占涂料组合物中的总树脂固体的10-35重量％，包含其间的所有量。基于总树脂固体，本发明的涂料组合物可包含至少50重量％且至多95重量％，包含其间的所有量的丙烯酸。例如，丙烯酸可占涂料组合物中总树脂固体的65-90重量％，包含其间的所有量。基于总固体，消光剂可以5-50重量％(包含其间的所有量)的量存在于涂料组合物中，余量的固体归因于制剂的其它组分，诸如颜料、树脂、流变改性剂、润湿剂、消泡剂、聚结剂和灭微生物剂。
除了上述抗氧化剂、催化剂和引发剂，诸如灭微生物剂、生物抑制剂、增强剂、触变剂、促进剂、表面活性剂、聚结剂、增塑剂、增量剂、稳定剂、腐蚀抑制剂、稀释剂、受阻胺光稳定剂和UV光吸收剂之外，本发明的涂料组合物可配制成还包含多种任选的成分和/或添加剂。取决于此类其他组分(特别是聚结剂和/或增塑剂)的挥发性有机化合物(VOC)，本发明的涂料组合物可含有极少或不含VOC，诸如低于50g/L或低于25g/L或低于5g/L或不含VOC。
本发明还涉及一种用本文所述的耐污涂料组合物涂覆基材的方法。该方法包含将涂料组合物涂覆在至少一部分基材上。涂料组合物可以以液体形式施涂并干燥，诸如在-10℃至50℃范围内的环境温度条件下。
涂料组合物的配制涉及以正确比例选择和混合合适的涂料成分以提供具有特定加工和处理性能的油漆以及具有所需性能的最终干漆膜的过程。水性涂料组合物可通过常规施涂方法施涂，诸如例如刷涂、辊涂和喷涂方法，诸如例如空气雾化喷涂、空气辅助喷涂、无空气喷涂、高容量低压力喷涂和空气辅助的无空气喷涂。合适的基材包含但不限于例如，混凝土、水泥板、MDF(中密度纤维板)和刨花板、石膏板、木材、石头、金属、塑料、墙纸和纺织品等，其可通过水性或溶剂性底漆预先涂底漆。当将其涂覆到基材上并干燥以在其上形成涂层时，发现含有氨酯丙烯酸酯树脂和丙烯酸树脂以及消光剂的干燥涂层在低光泽度水平下具有耐污性。耐污性可如下文示例中所述测定。
说明本发明的是以下示例，这些示例不应被认为是将本发明限制于其细节。除非另外指明，否则示例以及整个说明书中的所有份数和百分比均按重量计。
示例
在示例中使用以下基础制剂和测试方法。
I.基础制剂
根据表1中的基础制剂(无VOC)，用不同的树脂共混物制备涂料组合物，保持总树脂固体重量恒定。使用高速Cowles分散器以足以在叶片与油漆相遇处产生涡流的速度混合研磨成分。在加入消光剂后，重新开始研磨过程20分钟，然后使用常规实验室混合器加入稀释成分，并在最后一次添加后混合30分钟。
表1.基础制剂。
1硅酸镁流变改性剂，可获自The Carey Company(Addison,IL)。
2羟乙基纤维素流变改性剂，可获自SETylose USA(Plaquemine,LA)。
3矿物油消泡剂，可获自Ashland(Columbus,OH)。
4分散剂，可获自The Dow Chemical Company(Midland,MI)。
5非离子表面活性剂，可获自Evonik Industries AG(Essen,Germany)。
6硅酸铝消光剂，可获自The Cary Company(Addison,IL)。
7疏水改性的环氧乙烷尿烷流变改性剂，可获自The Dow Chemical Company。
8金红石型二氧化钛浆液，可获自Tronox Limited(Stamford,CT)。
9聚结剂(无VOC)，可获自The Eastman Chemical Company(Kingsport,TN)。
10灭微生物剂，可获自Thor Specialties,Inc.(Shelton,CT)。
II.耐污性测试方法
耐污性测试方法是ASTMD 4828的更具有挑战性的改进版本，旨在使用更少的擦洗循环来去除污渍。通过使用7密耳的马蹄形刮涂棒将基础制剂刮涂到黑色Leneta磨砂板(Form P121-10N)上来制备薄膜。在施涂污渍之前，将薄膜在环境条件下干燥7天。通过用以下流体饱和的一英寸滤纸条将以下污渍施涂到漆膜上：红酒、葡萄汁、咖啡浓缩物和热咖啡(70℃)。将以下污渍直接施涂于漆膜：芥末、红色唇膏、绿色蜡笔、石墨粉和Leneta染色介质ST-1。30分钟之后，将唇膏和Leneta介质擦掉，并将漆膜漂洗并放置在可洗性机器(GardnerAbrasion Tester)中。将含有10g水和6g SOFT(清洁剂，Henkel Corporation)的湿纤维素海绵放置在1000g支架中，并将板擦洗6个循环。将板冲洗并干燥至少2小时之后，将9种污渍中的每一种以0(无污渍去除)至10(污渍完全去除)的整数等级评级。
III.光泽度测试方法
低光泽度在本文中定义为Master Painters Institute(MPI)的1至3的光泽度水平(分别为无光饰面、天鹅绒样饰面和蛋壳状饰面)，其60°光泽度低于20个单位，而85°光泽度低于35个单位。光泽度使用BYK Gardner的micro-TRI-光泽度计根据ASTMD 523测量。
示例1-11：聚氨酯丙烯酸酯(PUA)的合成
示例1(PUA1)
在配备有电子温度探头、机械搅拌器、冷凝器和加热套的四颈圆底烧瓶中制备聚氨酯丙烯酸酯树脂。使用以下组分：
表2
11聚酯多元醇，可获自Chemtura Corporation Middlebury(CT)。
12抗氧化剂/自由基清除剂，可获自Oxiris(Barcelona,Spain)。
13灭微生物剂，可获自Lonza(Allendale,NJ)。
将进料A在烧瓶中在90℃下搅拌三十分钟。加入进料B，并将混合物调节至50℃。在20分钟内加入进料C。使用进料D冲洗用于进料C的加料漏斗。将反应混合物在90℃下保持三小时。
在氮气气氛下，在单独的四颈烧瓶中将进料E加热至85℃。在15分钟内，将1085g进料A、B、C和D的反应产物加入到进料E中。将混合物冷却至28℃，建立氮气气氛并保持在烧瓶中，以进行其余的反应。将进料F、G和H加入反应烧瓶中，然后加入进料I三十分钟。温度放热升高至39℃。在布氏粘度计DV-II+Pro上使用#2转子以60RPM在25℃下测量布氏粘度。通过将初始样品重量与暴露于110℃1小时后的样品重量进行比较来测量非挥发物含量。最终分散体的布氏粘度为170厘泊，pH为7.61，以及非挥发物含量为28.9％。基于固体的单体含量记录在表3中。
示例2-11(PUA2-PUA11)
使用表3中记录的单体含量，使用聚酯多元醇(FOMREZ 55-112)或聚醚多元醇(POLYTHF 1000)，在示例2-11中重复示例1。以与示例1中相同的相对于单体的量加入进料H和I中的引发剂。在示例2-7和11中，将示例1的进料E中的EDA和DEA用己二酸二酰肼(ADH)代替。聚氨酯和丙烯酸类聚合物的组分的百分比记录为总固体聚氨酯丙烯酸酯聚合物的重量百分比。中和胺TEA和DMEA的百分比记录为最终聚氨酯丙烯酸酯树脂在水中的分散体的重量百分比。在如下所述的所有示例中，具有表3中的组成的聚氨酯丙烯酸酯树脂用于制备基础制剂，将其以总树脂固体的10％至33％与基础丙烯酸胶乳RHOPLEXTMSG-30共混。
表3.聚氨酯丙烯酸酯组合物(PUA1-PUA11)。
14聚醚多元醇，可获自BASF Corporation(Florham Park,NJ)。
示例12-16
在表4中记录的示例12-16中，使用对照树脂(仅基础丙烯酸胶乳，对比例12)和PUA1与基础丙烯酸的共混物(示例13和14)制备基础制剂。从对比例15和16中排除消光剂。当存在消光剂时，含有PUA/基础丙烯酸共混物的基础制剂(示例13和14)的光泽度水平与100％基础丙烯酸对照(对比例12)相当。
表4.有和无消光剂的基础制剂。
示例17-23
在表5中记录的示例17-23中，使用对照树脂(仅基础丙烯酸胶乳，对比例17)和33％PUA和67％基础丙烯酸的共混物(在示例18-23中使用示例2-7的聚氨酯丙烯酸酯树脂(PUA2-PUA7))制备基础制剂。与仅包含基础丙烯酸对照树脂的基础制剂(对比例17)相比，在包含含有PUA18-PUA23的树脂共混物的基础制剂(示例18-23)中，耐污性提高了高达51％。
表5.含有33％PUA/67％基础丙烯酸共混物的制剂。
示例24-26
在表6中记录的示例24-26中，使用示例2的聚氨酯丙烯酸酯树脂(PUA2)与基础丙烯酸胶乳以不同的共混比制备基础制剂。当PUA的量从基础制剂中的树脂共混物固体的10％增加至30％时，耐污性提高。
表6.PUA的阶梯共混。
示例27-30
在表7中记录的示例27-30中，使用示例8-11的聚氨酯丙烯酸酯树脂(PUA8-PUA11)以30％PUA/70％基础丙烯酸胶乳的比例制备基础制剂。通过改变如表3所示的中和叔胺(DMEA)的量实现表6中记录的PUA8-11的粒度。使用Malvern Instruments的Zetasizer测量z-平均粒度。用减小粒度(比对比例31中所示的基础丙烯酸树脂小)的PUA树脂颗粒(示例27-29)可提高耐污性。当PUA树脂颗粒大于基础丙烯酸时，耐污性没有提高(对比例30)。
表7.各种PUA粒度。
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对比例31-35
在表8中记录的对比例31-35中，使用对照(仅基础丙烯酸胶乳，对比例31)和30％对比丙烯酸A-D与70％基础丙烯酸的共混物制备基础制剂。对比丙烯酸树脂使用本领域熟知的乳液聚合方法合成，并且在组成上类似于基础丙烯酸树脂。在对比丙烯酸树脂的各种粒度下，在基础制剂中使用30％对比丙烯酸/70％基础丙烯酸共混物，观察到的耐污性的提高可忽略不计。这表明PUA与基础丙烯酸共混过程中，某种程度的树脂不相容性会导致对耐污性提高产生粒度效应。
表8.对比丙烯酸树脂共混物。
示例36-39
在示例36和37中，使用PUA1制备基础制剂，并以10％和20％与基础丙烯酸胶乳共混。在对比例38和39中，示例36和37的PUA1用聚氨酯树脂(PUR，NeoRez R-2180，可获自DSMCoating Resins,LLC,The Netherlands)代替。
与包含10％和20％PUR树脂共混物的基础制剂相比，对于包含10％和20％PUA1树脂共混物的基础制剂观察到更大的耐污性。
表9.对比聚氨酯树脂共混物。
| 示例36 | 示例37 | 对比例38 | 对比例39 | |
| 污渍 | 10％PUA 1 | 20％PUA 1 | 10％PUR | 20％PUR |
| 酒 | 3 | 5 | 3 | 4 |
| 葡萄汁 | 5 | 7 | 4 | 6 |
| 咖啡浓缩物 | 7 | 8 | 6 | 7 |
| 热咖啡 | 6 | 7 | 5 | 6 |
| 芥末 | 2 | 3 | 2 | 0 |
| 唇膏 | 5 | 8 | 3 | 5 |
| 绿色蜡笔 | 9 | 9 | 9 | 7 |
| 石墨 | 10 | 10 | 7 | 7 |
| Leneta油 | 9 | 9 | 7 | 5 |
| 总计 | 56 | 66 | 46 | 47 |
鉴于上述描述和示例，本发明因此尤其涉及以下条款和权利要求的主题，但不限于此。
条款1：一种涂料组合物，其包括(i)氨酯丙烯酸酯树脂颗粒和(ii)丙烯酸树脂颗粒的混合物的水性分散体，以及(iii)消光剂，其中所述(i)氨酯丙烯酸酯树脂颗粒和(ii)丙烯酸树脂颗粒彼此不同。
条款2：根据条款1所述的涂料组合物，其中所述氨酯丙烯酸酯树脂包括脲基。
条款3：根据条款1所述的涂料组合物，其中基于总树脂固体，所述涂料组合物包括5-50重量％的氨酯丙烯酸酯树脂。
条款4：根据条款3所述的涂料组合物，其中基于总树脂固体，所述涂料组合物包括10-35重量％的氨酯丙烯酸酯树脂。
条款5：根据条款1所述的涂料组合物，其中所述消光剂包括无机消光剂。
条款6：根据条款5所述的涂料组合物，其中所述无机消光剂包括二氧化硅、硅酸铝和/或碳酸钙。
条款7：根据条款1所述的涂料组合物，其中所述消光剂包括有机消光剂。
条款8：根据条款7所述的涂料组合物，其中所述有机消光剂包括蜡、热塑性聚合物和/或热固性聚合物，其中所述有机消光剂不同于所述氨酯丙烯酸酯树脂颗粒(a)和所述丙烯酸树脂颗粒(b)。
条款9：根据条款1所述的涂料组合物，其中基于总固体，所述消光剂以5重量％至50重量％的量存在。
条款10：根据条款1所述的涂料组合物，其中将所述涂料组合物施涂到基材上并在干燥后作为涂层时，其具有不超过20个单位的60°光泽度水平。
条款11：根据条款10所述的涂料组合物，其中当将所述涂料组合物施涂到基材上并在干燥后作为涂层时，其具有不超过35单位的85°光泽度水平。
条款12：根据条款1-11中任一项所述的涂料组合物，其中所述丙烯酸树脂颗粒的z-平均粒度比所述氨酯丙烯酸酯树脂颗粒大至少10％。
条款13：根据条款1-12中任一项所述的涂料组合物，其中当将所述涂料组合物施涂到基材并干燥以形成涂层时，与不包含所述氨酯丙烯酸酯树脂颗粒的相同涂料组合物相比，所述涂料表现出提高的耐污性。
条款14：根据条款1-13中任一项所述的涂料组合物，其中所述氨酯丙烯酸酯树脂颗粒的z-平均粒度比所述丙烯酸树脂颗粒小至少50％。
条款15：根据条款1-14中任一项所述的涂料组合物，其中所述组合物的VOC小于50g/L。
条款16：根据条款1-15中任一项所述的涂料组合物，其中所述氨酯丙烯酸酯树脂颗粒和所述丙烯酸树脂颗粒彼此不相容。
条款17：一种赋予具有低光泽度的基材耐污性的方法，其包括将根据条款1-15中任一项所述的涂料组合物施涂到所述基材的至少一部分上。
条款18：根据条款17所述的方法，其还包括在环境温度下干燥所述涂料组合物以形成涂层。
条款19：一种基材，其至少部分涂覆有根据条款1-16任一项所述的涂料组合物。
条款20：根据条款19所述的基材，其中所述基材的涂覆部分为至少部分非金属的。
条款21：根据条款19所述的基材，其中所述基材的涂覆部分是非金属的。
条款22：根据条款19-21中任一项所述的基材，其中所述基材为建筑组件。
尽管以上出于说明目的描述了本发明的特定方面，但是对于本领域技术人员来说显而易见的是，在不脱离所附权利要求中定义的本发明的前提下，可以对本发明的细节进行多种变化。
Claims (21)
1.一种涂料组合物，其包括以下的混合物：
(i)氨酯丙烯酸酯树脂颗粒和(ii)丙烯酸树脂颗粒的混合物的水性分散体，其中所述(i)氨酯丙烯酸酯树脂颗粒与所述(ii)丙烯酸树脂颗粒彼此不同；以及
(iii)消光剂，
其中所述丙烯酸树脂颗粒的z-平均粒度比所述氨酯丙烯酸酯树脂颗粒大至少10％。
2.根据权利要求1所述的涂料组合物，其中所述氨酯丙烯酸酯树脂包括脲基。
3.根据权利要求1所述的涂料组合物，其中基于总树脂固体，所述涂料组合物包括5-50重量％的氨酯丙烯酸酯树脂。
4.根据权利要求3所述的涂料组合物，其中基于总树脂固体，所述涂料组合物包括10-35重量％的氨酯丙烯酸酯树脂。
5.根据权利要求1所述的涂料组合物，其中所述消光剂包括无机消光剂。
6.根据权利要求5所述的涂料组合物，其中所述无机消光剂包括二氧化硅、硅酸铝和/或碳酸钙。
7.根据权利要求1所述的涂料组合物，其中所述消光剂包括有机消光剂。
8.根据权利要求7所述的涂料组合物，其中所述有机消光剂包括蜡、热塑性聚合物和/或热固性聚合物，其中所述有机消光剂不同于所述氨酯丙烯酸酯树脂颗粒(a)和所述丙烯酸树脂颗粒(b)。
9.根据权利要求1所述的涂料组合物，其中基于总固体，所述消光剂以5重量％至50重量％的量存在。
10.根据权利要求1所述的涂料组合物，其中当将所述涂料组合物施涂到基材上并干燥作为涂层时，其具有不超过20个单位的60°光泽度水平。
11.根据权利要求10所述的涂料组合物，其中当将所述涂料组合物施涂到基材上并干燥作为涂层时，其具有不超过35个单位的85°光泽度水平。
12.根据权利要求1所述的涂料组合物，其中当将所述涂料组合物施涂到基材并干燥以形成涂层时，与不包含所述氨酯丙烯酸酯树脂颗粒的相同涂料组合物相比，所述涂料表现出提高的耐污性。
13.根据权利要求1所述的涂料组合物，其中所述氨酯丙烯酸酯树脂颗粒的z-平均粒度比所述丙烯酸树脂颗粒小至少50％。
14.根据权利要求1所述的涂料组合物，其中所述组合物的VOC小于50g/L。
15.一种赋予具有低光泽度的基材耐污性的方法，其包括将根据权利要求1所述的涂料组合物施涂到所述基材的至少一部分上。
16.根据权利要求15所述的方法，其还包括在环境温度下干燥所述涂料组合物以形成涂层。
17.一种赋予具有低光泽度的基材耐污性的方法，其包括将根据权利要求10所述的涂料组合物施涂到所述基材的至少一部分上。
18.一种基材，其至少部分涂覆有根据权利要求1所述的涂料组合物。
19.根据权利要求18所述的基材，其中所述基材的涂覆部分为至少部分非金属的。
20.根据权利要求18所述的基材，其中所述基材的涂覆部分为非金属的。
21.根据权利要求18所述的基材，其中所述基材为建筑组件。
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| US11193039B2 (en) | 2021-12-07 |
| CN112424246A (zh) | 2021-02-26 |
| WO2020016766A1 (en) | 2020-01-23 |
| EP3824006A1 (en) | 2021-05-26 |
| AU2019307870A1 (en) | 2021-02-18 |
| MX2021000464A (es) | 2021-04-19 |
| US20200017709A1 (en) | 2020-01-16 |
| CA3106496A1 (en) | 2020-01-23 |
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