CN114402040A - 疏水改性颜料组合物 - Google Patents

疏水改性颜料组合物 Download PDF

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CN114402040A
CN114402040A CN202080063861.8A CN202080063861A CN114402040A CN 114402040 A CN114402040 A CN 114402040A CN 202080063861 A CN202080063861 A CN 202080063861A CN 114402040 A CN114402040 A CN 114402040A
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salt
pigment particles
range
auxiliary
structural units
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D·G·巴顿
J·C·勃林
J·F·卡列哈斯
A·查克拉瓦蒂
A·卡茨
M·K·米什拉
C·J·拉德克
A·K·范戴克
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University of California
Dow Global Technologies LLC
Rohm and Haas Co
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University of California
Dow Global Technologies LLC
Rohm and Haas Co
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Abstract

本发明为一种组合物，其包含涂有有机硅烷聚合物的金属氧化物颜料颗粒的水性分散液，所述有机硅烷聚合物包含烷基三羟基硅烷或其盐、二烷基二羟基硅烷或其盐以及辅助烷基硅烷三醇的结构单元。本发明的所述组合物为颜料颗粒提供疏水性，由此赋予防水性，并且允许水中的颜料的高负载量而无粘度增加。所述分散液还适用于在由涂料产生的涂层中提供抗污渍性和抗腐蚀性。

Description

疏水改性颜料组合物
相关申请的交叉引用
本申请要求2019年10月2日提交的第62/909,344号美国临时申请的优先权，所述申请以全文引用的方式并入本文中。
背景技术
本发明涉及一种包含疏水改性颜料颗粒的组合物。
水性涂料调配物的性能部分地受用于使涂料不透明的无机颜料的表面化学物质的影响。颜料如广泛使用的TiO2在其天然状态下倾向于为亲水性的，并且因此作为颜料-结合剂界面处的水、离子和水溶性着色剂渗透的屏障不是特别有效。由于此原因，改性无机颜料颗粒的表面以提供具有改进的抗污渍性和抗腐蚀性的涂层是有利的。
颜料颗粒在涂料调配物中的分散稳定性影响最终薄膜的遮盖效率。颜料聚集体比独立的初级颗粒提供更少的遮盖力；因此，进一步有利的是，改性颜料颗粒的表面以使薄膜中的颜料聚集最小化，由此减少调配物中所需的颜料的量。
所属领域已知用疏水基团改性颜料颗粒的表面。举例来说，US 2017/0022384 A1公开了用聚硅氧烷或甲硅烷基改性的无机颜料颗粒的水性分散液。理论上，预期疏水改性的颜料颗粒会改进屏障特性，由此改进遮盖力。然而，在实践中，因为疏水改性的颜料颗粒的润湿性较差并且疏水改性的颜料颗粒的水性分散液的稳定性较差，所以调配物设计师仍然难以将疏水改性的颜料颗粒分散于水中。分散剂(分散剂与表面活性剂)的使用可以部分解决这些问题，但分散剂本身存在问题，包括限制形成薄膜、提高水敏感性、提高对离子和极性化合物的渗透性、破坏对某些衬底的粘附性，以及促进非成薄膜添加剂如表面活性剂、消泡剂、聚结剂和分散剂向涂层表面的渗出(冒出)。
因此，有利的是，将疏水改性的颜料的水性分散液的颜料体积浓度增加到超过37体积％而不伴随粘度增加，并且进一步有利的是，能够将颜料分散于水中同时基本减少或甚至消除辅助分散剂的使用。
发明内容
本发明通过提供一种组合物解决了所属领域的需要，所述组合物包含涂有有机硅烷聚合物的金属氧化物颜料颗粒的水性分散液，所述有机硅烷聚合物包含以下结构单元：a)烷基三羟基硅烷或其盐，浓度范围为50到98.9摩尔百分比；b)二烷基二羟基硅烷或其盐，浓度范围为1到49.9摩尔百分比；以及c)辅助烷基硅烷三醇，浓度范围为0.1到4摩尔百分比；其中所有浓度均基于烷基三羟基硅烷单体、二烷基二羟基硅烷单体和辅助烷基硅烷三醇的总结构单元；其中所述辅助烷基硅烷三醇为3-氨基丙基硅烷三醇或其盐或3,3,3-三氟丙基硅烷三醇或其盐；并且其中所述水性分散液的pH范围为7.5到12。本发明提供在高固体含量下在可接受的低粘度下疏水改性的颜料颗粒的水性分散液。此类分散液形成明显耐水性且展现额外益处(如抗腐蚀性和抗污渍性)的涂层。
具体实施方式
本发明是一种组合物，其包含涂有有机硅烷聚合物的金属氧化物颜料颗粒的水性分散液，所述有机硅烷聚合物包含以下结构单元：a)烷基三羟基硅烷或其盐，浓度范围为50到98.9摩尔百分比；b)二烷基二羟基硅烷或其盐，浓度范围为1到49.9摩尔百分比；以及c)辅助烷基硅烷三醇，浓度范围为0.1到4摩尔百分比；其中所有浓度均基于烷基三羟基硅烷单体、二烷基二羟基硅烷单体和辅助烷基硅烷三醇的总结构单元；其中所述辅助烷基硅烷三醇为3-氨基丙基硅烷三醇或其盐或3,3,3-三氟丙基硅烷三醇或其盐；并且其中所述水性分散液的pH范围为7.5到12。
如本文所用，烷基三羟基硅烷的结构单元是指以下片段：
Figure BDA0003542410610000021
其中R为烷基，优选C1-C18烷基，更优选C1-C4烷基并且最优选甲基；并且每个R1独立地为H，与颜料颗粒键结的键；M或其它Si原子；其中M为碱金属或铵抗衡离子，优选锂、钠或钾抗衡离子；并且虚线表示氧原子与颜料颗粒的连接点。
如本文所使用，二烷基三羟基硅烷的结构单元是指以下片段：
Figure BDA0003542410610000031
其中每个R独立地为烷基，优选C1-C18烷基，更优选C1-C4烷基并且最优选甲基；并且每个R1独立地为H，与颜料颗粒键结的键；M或其它Si原子；其中M为碱金属或铵抗衡离子，优选锂、钠或钾抗衡离子；并且虚线表示氧原子与颜料颗粒的连接点。
优选地，有机硅烷聚合物包含60，更优选65，并且最优选68摩尔百分比到优选90，更优选到85，并且最优选到80摩尔百分比的烷基三羟基硅烷或其盐的结构单元。有机硅烷聚合物进一步优选地包含10、更优选地15并且最优选地20摩尔百分比到40、并且更优选到30摩尔百分比的二烷基二羟基硅烷或其盐的结构单元；和0.2、更优选地0.5摩尔百分比到3.5、更优选到3.2摩尔百分比的辅助烷基硅烷三醇的结构单元。优选至少90重量％，更优选至少95重量％的有机硅烷聚合物包含烷基三羟基硅烷和二烷基二羟基硅烷的结构单元。在本发明的一个实施例中，100重量％有机硅烷聚合物包含烷基三羟基硅烷或其盐、二烷基二羟基硅烷或其盐和辅助烷基硅烷三醇的结构单元。
疏水改性的金属氧化物颜料颗粒的水性分散液可通过以下来制备：a)使金属氧化物颜料颗粒或金属氧化物颜料颗粒的水性分散液与碱接触以形成碱化金属氧化物颜料颗粒或碱化金属氧化物颗粒的水性分散液，然后b)在存在水的情况下和在7.5、优选8.5、更优选9并且最优选9.2到12，优选到11、更优选到10并且最优选到9.8的pH范围下使碱化金属氧化物颗粒与有机硅烷接触以形成疏水改性的颜料颗粒的水性分散液。在此方面中，在第一步中，优选使金属氧化物颜料颗粒的水性分散液与碱接触以形成碱化金属氧化物颗粒的水性分散液。烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇在与碱化颜料颗粒的水性分散液接触之前都有利地转化成其在水性溶液中的对应盐。优选地，烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇，更优选甲基三羟基硅烷、二甲基二羟基硅烷和辅助烷基硅烷三醇与颜料颗粒以调节到≥12的pH的水性混合物形式接触。在另一实施例中，颜料颗粒可与有机硅烷接触而无需碱预处理。
最优选的烷基三羟基硅烷、甲基三羟基硅烷可以商购获得或通过在≥12pH下的聚甲基氢硅氧烷(PMHS)的含水碱金属氢氧化物水解来原位制备。已经发现，对于储存特别有利的是，将甲基三羟基硅烷的水溶液保持在高pH下直到与颜料颗粒接触以使甲基三羟基硅烷的自缩合最小化。最优选的二烷基二羟基硅烷、二甲基二羟基硅烷有利地通过用强碱如KOH水解二甲氧基二甲基硅烷来制备。
进一步有利的是，在有机硅烷添加步骤期间，通过将强酸分别和伴随地添加到颜料颗粒或碱性颜料颗粒中以将pH保持在9到10、更优选9.2到9.8范围内。
如本文所使用，金属氧化物颗粒包括金属氧化物和类金属氧化物颗粒，其实例包括钛、铝、硅、铁、钙、镁、锆或锌及其混合物的氧化物和碳酸盐。优选的颜料颗粒的实例包括CaCO3、Al2O3、SiO2和TiO2颜料颗粒。TiO2颜料颗粒包括金红石和锐钛矿TiO2以及用各种金属氧化物和氢氧化物包括氧化铝、二氧化硅和氧化锆处理的TiO2表面。
金属氧化物颜料颗粒的平均粒度优选为10nm、更优选20nm、更优选50nm、更优选100nm、更优选200nm并且最优选240nm到优选5μm、更优选到1μm、更优选到500nm、更优选到400nm并且最优选到300nm。金属氧化物颜料颗粒的平均粒度由通过使用MalvernZetasizer纳米粒度分析仪的动态光散射测定的平均粒度限定。
碱被用来预处理颜料颗粒，其中期望预处理的颗粒包括胺，如三甲胺、三乙胺、二甲胺、二乙胺、2-氨基-2-甲基-1-丙醇、哌啶和哌嗪；氨基酸，如精氨酸、组氨酸和赖氨酸；亚氨基烷基二胺，如胍；嘌呤，如腺嘌呤；嘧啶，如胞嘧啶；氢氧化铵；氢氧化季四-C1-C12烷基铵，如氢氧化四甲基铵、氢氧化四乙基铵和氢氧化四丁基铵；以及碱金属氢氧化物，如LiOH、NaOH和KOH。相对于颜料颗粒的碱反应性位点，碱优选以化学计量方式或化学计量过量方式使用。这类反应性位点包括酸性OH基团和路易斯酸金属阳离子，如AlIII、TiIV、ZrIV、ZnIV、CaII及MgII。
烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇(优选地这些有机硅烷的盐)有利地以足以将颜料颗粒转化成疏水改性的颜料颗粒的量添加到颜料颗粒中。术语“疏水改性的”是指相对于未改性的干颜料颗粒，如使用DVS Advantage ET分析仪(表面测量系统(Surface Measurement Systems))所测量，在90％相对湿度下，改性颜料颗粒具有<25重量％水吸收量。
有机硅烷结合于颜料颗粒以形成包含烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇或其盐的结构单元的疏水性有机硅烷聚合物涂层。优选地，对于粒度在250nm到350nm范围内的颜料颗粒，有机硅烷聚合物中的wt.％Si并且由烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇相对于颜料颗粒的添加产生，优选地在0.1wt.％、更优选地0.5wt.％，并且最优选地1wt.％到优选地4wt.％，并且更优选到3wt.％范围内。或者，有机硅烷聚合物中的和由将烷基三羟基硅烷、二烷基二羟基硅烷和烷基硅烷三醇添加到碱化颜料颗粒中而产生的Si原子浓度优选在4、更优选10并且最优选20个Si原子/nm2的外部颜料表面积到优选120、更优选到100、更优选到80并且最优选到60个Si原子/nm2外部颜料表面积范围内。如本文所使用，外部颜料表面积是指如通过如使用Malvern Zetasizer纳米粒度分析仪进行的动态光散射所测量的具有与颜料颗粒直径相同的直径的球体的几何外表面积。通过消化随后通过电感耦合等离子体-原子发射光谱法(ICP-AES)进行的Si分析来测定掺入颜料颗粒上的烷基三羟基硅烷、二烷基二羟基硅烷和辅助烷基硅烷三醇的程度。
出人意料地发现，与具有相同浓度的分散剂的未改性颜料浆料相比，具有少量或无添加分散剂(其可为分散剂或表面活性剂)的自分散疏水改性的颜料颗粒的水性分散液可以在0.37到0.5(对应于对于Ti-Pure R706 TiO2的约70到80wt.％固体)的体积固体分数下制备，而浆料粘度无任何显著增加。因此，对于包含疏水改性的颜料颗粒的70重量％固体(0.37体积固体分数)水性浆料，在没有辅助分散剂的情况下，在0.1s-1剪切速率下的剪切应力优选不大于0.03Pa。
对于相同的浆料，在没有辅助分散剂的情况下，在0.1s-1剪切速率下的粘度优选不大于0.4Pa·s，并且在100s-1剪切速率下的粘度优选不大于0.03Pa·s。这些粘度比水的粘度高约35到450倍，并且为易于倾倒的液体状浆料。已发现少量分散剂的存在可进一步改进剪切应力和粘度，但即使在不存在分散剂的情况下，流变学特性也是完全可接受的。
对于包含疏水改性的颜料颗粒的75重量％固体(0.43体积固体分数)水性浆料，在0.1s-1剪切速率下的剪切应力优选不大于0.22Pa。对于相同的浆料，在不存在辅助分散剂的情况下，在0.1s-1剪切速率下的粘度优选不大于2.2Pa·s，并且在100s-1剪切速率下的粘度优选不大于0.035Pa·s。在相对于表面活性剂(如TRITONTM X-100表面活性剂(陶氏化学公司或其附属公司的商标))的颜料质量少到0.08wt.％的存在下，已观察到在0.1s-1的剪切速率下，剪切应力显著降低到0.06Pa。此外，在存在少量表面活性剂的情况下，粘度基本上在0.1s-1的剪切速率下降低至0.6Pa·s，并且在100s-1的剪切速率下大于0.035Pa·s。这些粘度比水的粘度高约40到2500倍，并且同样为易于倾倒的液体状浆料。
对于包含疏水改性的颜料颗粒的80重量％固体(0.50体积固体分数)水性浆料，在0.1s-1剪切速率下的剪切应力优选不大于2.2Pa。对于相同的浆料，在0.1s-1剪切速率下的粘度优选不大于22Pa·s，并且在100s-1剪切速率下的粘度优选不大于0.2Pa·s。在存在少量分散剂的情况下，在0.1s-1的剪切速率下，粘度和剪切应力分别不大于20Pa·s和2Pa。这些粘度比水的粘度高约225到25,000倍。
已发现疏水改性的颜料颗粒的水性分散液可以在没有辅助分散剂的情况下实现，如US 2017/0022384 A1的教示中所要求。因此，在本发明的另一方面中，本发明的组合物包含基本上不存在分散剂，即以颜料的重量计的小于0.09，优选小于0.05、更优选小于0.01并且最优选0重量％的分散剂。基本上不存在分散剂在涂层调配物中是特别有利的，因为分散剂，特别是阴离子聚合物分散剂，限制形成薄膜、促进腐蚀并增加了涂层的水敏感性并促进非固体(例如盐与聚电解质)不希望地渗出到涂层表面上。
疏水改性的颜料颗粒的水性分散液的制备优选在不存在有机溶剂的情况下进行。(尽管在过程中原则上可以产生少量的C1-C4醇，但这些副产物不构成有机溶剂。)因此，本发明的方法优于先前描述的需要使用有机溶剂的颜料改性方法。
本发明的组合物适用于涂层调配物，其包括胶乳并且优选一种或多种另外的材料包括消泡剂、表面活性剂、增稠剂、增量剂、聚结剂、杀生物剂和着色剂。所述组合物提供的涂料组合物与未疏水改性的颜料颗粒相比具有改善的耐水性，以及耐污性或抗腐蚀性或两者，如以下实施例所证明的。
实例
颜料颗粒胺官能化的计算
如《ACS催化(ACS Catalysis)》2014,302-310中所描述，通过酸碱反滴定(acid-base back titration)测定胺官能化的程度。
中间体实例1-由聚甲基氢硅氧烷制备甲基三羟基硅烷
向3颈塑料旋转瓶中添加4M KOH溶液(244mL)。将溶液用N2吹扫15min，然后将聚甲基氢硅氧烷(PMHS，来自奥德里奇(Aldrich)目录号176206，Mn＝1700-3200g/mol，CAS号63148-57-2，36mL)在25s内添加，然后进一步脱气。将得到的脱气溶液在N2下以600rpm搅拌6h。FTIR光谱分析证实所有PMHS均转化为甲基三羟基硅烷(MTHS)。将溶液储存在紧密封盖的容器中以防止暴露于大气中的二氧化碳。水中MTHS的浓度为0.234g/mL。
中间体实例2-制备二甲基二羟基硅烷单钾盐
将盖有橡胶隔膜的特氟龙(Teflon)圆底烧瓶置于冰浴中并用N2吹扫10min。然后通过针和注射器通过隔膜将二甲基二甲氧基硅烷(11.6mL，95％v/v，密度＝0.88g/mL)添加到烧瓶中。在搅拌下将4M KOH溶液(20.2mL，0.08摩尔KOH)以20μL/5s的速率添加到烧瓶中2min，然后以2.5mL/min的速率添加剩余的添加物。在添加完KOH后，将溶液再搅拌10min，然后在60℃下旋转蒸发去除水和释放的甲醇30min，然后在70℃下进行15min。获得产物(10.20g)并通过1H和29Si NMR光谱法识别为二甲基二羟基硅烷的单钾盐(K-DMDS)。
中间体实例3-制备甲基三羟基硅烷:二甲基二羟基硅烷:3-氨基丙基硅烷三醇的74:25:1混合物
将如中间体实例2中所制备的K-DMDS水溶液(0.20g溶解于0.61mL水中)、如中间体实例1中所制备的MTHS溶液的一部分(1.81mL)和氨基丙基硅烷三醇(APST，0.033mL(23.5％水溶液))混合以形成MTHS:K-DMDS:APST的74:25:1摩尔:摩尔:摩尔混合物。将混合物涡旋以得到透明溶液(2.6mL)，其进一步用于颜料的疏水改性。所得混合物的pH为约14。
中间体实例4-制备丙烯酸粘合剂
向装备有冷凝器、搅拌器和热电偶的4颈反应烧瓶中添加去离子水(700g)。在N2下将烧瓶的内容物加热到88℃。在第二容器中，通过混合去离子水(500g)、月桂基硫酸钠溶液(SLS，24.4g，28％活性于水中)、丙烯酸丁酯(492g)、甲基丙烯酸甲酯(502g)、甲基丙烯酸(10.0g)和正十二烷基硫醇(2.5g)制备单体乳液(ME-1)。将SLS(7.0g，28％活性于水中)和碳酸钠溶液(35g，14.3％活性于水中)添加到烧瓶中，接着添加去离子水冲洗(40g)。然后将ME-1(40.7g)的一部分添加到烧瓶中，接着添加过硫酸铵(APS，4.0g溶解于30g去离子水中)，接着添加去离子水冲洗(35g)。在观察到小放热之后，同时添加APS(1.0g溶解于60g去离子水中)溶液，接着去离子水冲洗(35g)，同时维持87℃的反应器温度超过120min来计量ME-1的剩余部分。在进料完成之后，将反应烧瓶维持在87℃下持续额外1h。然后添加氧化还原对以减少任何残余单体并且然后冷却批料并且添加氢氧化铵(28％活性)以将pH调节到8.5。所得分散液具有40.2重量％的固体含量和98nm的z平均粒子直径。
实例1-用甲基三羟基硅烷:二甲基二羟基硅烷:3-氨基丙基硅烷三醇的74:25:1混合物对TEA-改性的TiO2的疏水性改性
A.用三乙胺进行TiO2的预处理
将Ti-R706 TiO2粉末(250g)、水(500mL)、TAMOLTM 1124分散剂(2.5mL，陶氏化学公司或其附属公司的商标)和三乙胺(TEA，2.5mL)添加到1-在圆底烧瓶中以形成浆料，将其用机动顶置式混合器以1950rpm搅拌20h。通过将浆料以四等份转移到离心容器中，并以14,000rpm离心3min来去除过量胺。用刮铲将离心后收集的固体块碎成小块，随后向四个部分中的每一个中添加水(250mL)。使各样品经历涡流混合5min，随后超声波处理5min。再次在14,000rpm下将样品离心3min，产生固体含量为83.8wt.％TiO2的湿糊状物。对于每一样品重复整个水洗过程四次，以产生具有83.8wt.％固体的不含任何胺或氨气味的浆料。通过大量水洗步骤的未回收的胺被认为与颗粒表面结合；所得颗粒为胺官能化的TiO2颗粒。
如《ACS催化》2014,4,302中所述，通过使用0.01M HCl和0.01M NaOH进行酸碱反滴定测量TiO2颗粒的胺官能化程度。发现在TEA处理的TiO2颗粒(TEA-R706)的表面上可获得34μmol/g碱性位点，其对应于2个TEA分子的结合胺的表面覆盖度/nm2总颜料表面积。
进行毛细管上升测试以评估TEA-R706的疏水性。毛细管上升测试如下进行：使用在水性HEPES缓冲液中调节至pH 8的2.5mM溴百里酚染料溶液。用棉花将一端封闭的1.5-mm直径的毛细管用干燥的颜料粉末填充至4cm的高度。然后，将毛细管浸入染料溶液中4h并用尺子测量染料的上升。随后使用Washburn等式由染料上升的高度计算接触角。TEA-R706显示出3.2cm的溴百里酚蓝染料的毛细管上升，表明其不是疏水性材料。
B.用甲基三羟基硅烷、二甲基二羟基硅烷和3-氨基丙基硅烷三醇的74:25:1混合物对TEA-R706进行疏水性改性
将TEA-R706湿糊状物(13.6g)，TAMOLTM 1124分散剂(68μL)、两个10-mm ZrO2珠粒和水(0.2mL)置于塑料容器中并与Flacktek高速混合器在1700rpm下混合2min以形成浆料。将额外水(0.845mL)添加到浆料中并且在不存在ZrO2珠粒的情况下在3500rpm下进行进一步高剪切混合持续3min以形成颜料固体含量为77.5wt.％的浆料。
将MTHS、K-DMDS和APST(2.6mL)的水性混合物添加到浆料中，同时添加2.0M HCl(3.2mL)，以将浆料的pH调节到9.5。将浆料以3500rpm混合持续3min，然后添加水(2.5mL)，然后涡旋4h。然后将浆料用水(200mL)洗涤并以14000rpm离心5min。用刮铲将离心后收集的固体块破碎并用水(200mL)洗涤，然后再次离心。此程序再重复两次，并且获得TiO2固体含量为80wt.％的湿糊状物的所得产物。
将产物干燥24小时并证实其疏水性如下：将干燥的粉末(100mg)置于装有去离子水(200mL)的烧杯中并观察2h以获得沉降的证据。2h后，粉末完全可漂浮在水上，并且没有观察到粉末的沉降，这提供了疏水性的强有力证据。毛细管上升测试证实了材料的疏水性：在观察到在pH 8.7的疏水性材料的高剪切应力测试之前和之后，在pH 8下没有溴百里酚染料水溶液的上升。
实例2-用甲基三羟基硅烷:二甲基二羟基硅烷:3-氨基丙基硅烷三醇的72:25:3混合物对TEA-改性的TiO2进行疏水性改性
程序基本上如实例1中所描述来进行，不同之处在于MTHS、K-DMDS和APST的掺合物通过合并K-DMDS(0.20g溶解于0.61mL水中)的水溶液、如中间体实例1中所制备的MTHS溶液(1.76mL)的一部分和氨基丙基硅烷三醇(APST，0.10mL(23.5％水溶液))掺合以形成MTHS:K-DMDS:APST的72:25:3摩尔:摩尔:摩尔混合物来制备。如上文所描述确认所得改性TiO2的疏水性。
腐蚀研究
通过合并中间体实例2的丙烯酸粘合剂(12.79g，40.2重量百分比固体)；稀盐水溶液(120mg NaCl溶解于1.77g去离子水中)；实例1或2疏水改性的颜料(4.64g，75wt.％颜料)；NaCl(0.12g)；RHOPLEXTM 2020E增稠剂(0.6g，陶氏化学公司或其附属公司的商标)；以及NaNO2(0.2g，10％水溶液)来制备涂料调配物。
使用3密耳棒施料器(BYK-加德纳)将涂料涂层施加到17.8cm×10.15cm软钢衬底(美国信赖金属铝公司(Reliance metal and Aluminium Co,USA))，且在环境条件下干燥72h。随后，将干燥的涂层在连续氧气流动下浸没到腐蚀溶液(0.1M HCl+0.1M NaCl)中持续1h。将经涂布衬底从腐蚀溶液去除且在环境条件下干燥12h。将衬底浸没于腐蚀溶液(1h)中接着在环境条件下干燥(12h)的循环重复9次循环。使用丙酮和棉花去除小部分的涂层，并且通过计数存在于软钢衬底上的腐蚀点的数目以及沿着划线扩散的腐蚀来观察底层腐蚀的程度。
尽管对于经TEA处理的R706 TiO2颗粒观察到沿划线的完全底涂层腐蚀和腐蚀扩散，并且对于未改性的R706 TiO2(天然R706)观察到几乎完全腐蚀，但对于使用实例1疏水改性的TiO2制备的涂料调配物，仅观察到2.6腐蚀点/cm2，并且对于使用实例2疏水改性的TiO2制备的涂料调配物，仅观察到1.5腐蚀点/cm2；然而，对于来自实例1的涂料调配物，沿划线扩散的腐蚀不太明显。表1使腐蚀等级数与观察到的腐蚀点相关联，且表2使腐蚀等级与对于使用天然R706制备的涂料和来自实例1和实例2的疏水改性TiO2观察到的腐蚀相关联。
表1-腐蚀等级
等级 腐蚀点/cm<sup>2</sup>
0 完全腐蚀
1 >15-40
2 >7.5-15
3 >3-7.5
4 >0.75-3
5 0-0.75
表2-使用未改性的TiO2对改性的TiO2的涂料的腐蚀
实例 等级
天然R706 0
1 4
2 4
当使用含有疏水改性的TiO2的涂料时，结果显示抗腐蚀性的显著改进。
实例3-用甲基三羟基硅烷:二甲基二羟基硅烷:3,3,3-三氟丙基硅烷三醇的74:25:1混合物对TiO2的疏水性改性
步骤基本上如实例1中所描述进行，不同之处在于MTHS、K-DMDS和3,3,3-三氟丙基硅烷三醇(TFPST)的掺合物通过合并K-DMDS(0.20g溶解于0.61mL水中)的水溶液、如中间体实例1中所制备的MTHS溶液(1.81mL)的一部分和三甲氧基(3,3,3-三氟丙基)硅烷(TMTFS，12μL)掺合以形成MTHS:K-DMDS:FEST的72:25:3摩尔:摩尔:摩尔混合物来制备。(通过ATR-FTIR光谱法确认TMTFS对FEST的完全水解。)如上文所描述确认所得改性TiO2的疏水性。
通过将丙烯酸粘合剂(12.79g，40.2重量百分比固体)；去离子水(1.97g)；实例1或实例3疏水改性的颜料(4.64g，75wt.％颜料)；和RHOPLEXTM 2020E增稠剂(0.6g)合并来制备涂料调配物。将涂料施用到丙烯酸衬底并且在污渍测试之前干燥48h。选择茶、咖啡、红酒和蕃茄酱用于污点测试。污点测试程序是这样进行的，首先将1cm×1cm的纸巾与染色材料一起浸泡15min，然后将浸泡过的毛巾放在涂层表面上2h，从而将染色材料施用在经涂布表面上。去除毛巾且将污渍用水冲洗，接着用棉和1％清洁剂溶液进行轻微擦洗。表3说明洗涤后残余污点的污点等级数与污点定性外观之间的相关性。
表3-去污等级
等级 定性的去污性能
0 无去污，极强可见痕迹
1 去污效果极差、强可见痕迹
2 去污效果差，可见痕迹
3 去污效果良好，痕迹轻
4 去污效果极好，极少痕迹
5 去污效果极佳，无可见痕迹
表4说明各种涂料的污点等级结果：具有未改性的TiO2的涂料(天然R-706)；具有如实例1中所描述改性的TiO2的涂料(实例1TiO2)；以及具有如实例3中所描述改性的TiO2的涂料(实例3TiO2)。
表4-具有改性和未改性TiO2的涂料的污点等级
污点 天然R-706 实例1TiO<sub>2</sub> 实例3TiO<sub>2</sub>
茶 1 5 5
咖啡 1 3 4
红酒 1 5 3
番茄酱 3 5 5
结果显示，与含有未改性的TiO2的涂料相比，具有疏水改性的TiO2的涂料展现出对污点的优良抗性。

Claims (8)

1.一种组合物，其包含涂有有机硅烷聚合物的金属氧化物颜料颗粒的水性分散液，所述有机硅烷聚合物包含以下结构单元：a)烷基三羟基硅烷或其盐，浓度范围为50到98.9摩尔百分比；b)二烷基二羟基硅烷或其盐，浓度范围为1到49.9摩尔百分比；以及c)辅助烷基硅烷三醇，浓度范围为0.1到4摩尔百分比；其中所有浓度均基于烷基三羟基硅烷单体、二烷基二羟基硅烷单体和所述辅助烷基硅烷三醇的总结构单元；其中所述辅助烷基硅烷三醇为3-氨基丙基硅烷三醇或其盐或3,3,3-三氟丙基硅烷三醇或其盐；并且其中所述水性分散液的pH范围为7.5到12。
2.根据权利要求1所述的组合物，其中所述金属氧化物颜料颗粒为CaCO3、Al2O3、SiO2或TiO2颜料颗粒或其组合；其中所述烷基三羟基硅烷或其盐的结构单元的浓度在60到90摩尔百分比范围内；所述二烷基二羟基硅烷或其盐的结构单元的浓度在10到40摩尔百分比范围内；并且所述辅助烷基硅烷三醇或其盐的结构单元的浓度在0.2到3.5摩尔百分比范围内。
3.根据权利要求2所述的组合物，其中所述金属氧化物颜料颗粒为TiO2颜料颗粒；其中所述烷基三羟基硅烷或其盐的结构单元的浓度在65到85摩尔百分比范围内；所述二烷基二羟基硅烷或其盐的结构单元的浓度在15到30摩尔百分比范围内；并且所述辅助烷基硅烷三醇或其盐的结构单元的浓度在0.5到3.2摩尔百分比范围内。
4.根据权利要求1到3中任一项所述的组合物，其中所述辅助烷基硅烷三醇为3-氨基丙基硅烷三醇；所述烷基三羟基硅烷为甲基三羟基硅烷；并且所述二烷基二羟基硅烷为二甲基二羟基硅烷。
5.根据权利要求1到3中任一项所述的组合物，其中所述辅助烷基硅烷三醇为3,3,3-三氟丙基硅烷三醇；所述烷基三羟基硅烷为甲基三羟基硅烷；并且所述二烷基二羟基硅烷为二甲基二羟基硅烷。
6.根据权利要求3所述的组合物，其包含以所述TiO2颗粒的重量计的小于0.09重量％的分散剂。
7.根据权利要求6所述的组合物，其包含以所述TiO2颗粒的重量计的小于0.01重量％的分散剂。
8.根据权利要求1所述的组合物，其进一步包括乳胶、增稠剂和一种或多种选自由以下组成的组的材料：消泡剂、表面活性剂、增量剂、聚结剂、杀生物剂和着色剂。
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