CN103910853A - 硅氧烷-氨基甲酸酯基污损脱附涂料 - Google Patents

硅氧烷-氨基甲酸酯基污损脱附涂料 Download PDF

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CN103910853A
CN103910853A CN201210599271.4A CN201210599271A CN103910853A CN 103910853 A CN103910853 A CN 103910853A CN 201210599271 A CN201210599271 A CN 201210599271A CN 103910853 A CN103910853 A CN 103910853A
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isocyanate group
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organic compound
polysiloxane polymer
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CN103910853B (zh
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P·J·鲍帕
李艳香
陈红宇
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Dow Global Technologies LLC
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Priority to EP15163590.1A priority patent/EP2927255A1/en
Priority to EP13197662.3A priority patent/EP2749583B1/en
Priority to US14/132,119 priority patent/US9145500B2/en
Priority to BR102013032886A priority patent/BR102013032886B8/pt
Priority to KR1020130160349A priority patent/KR102104265B1/ko
Priority to JP2013264148A priority patent/JP6235329B2/ja
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Abstract

本发明提供了一种能形成聚氨酯-聚硅氧烷网络的双组分可湿固化涂料组合物。该涂料组合物适用于海洋防污损涂料中，其提供了一种双组分可湿固化组合物，包括：(a)第一组分，其包括至少一种多官能多元醇；(b)第二组分，其包括：(i)至少一种具有至少两个异氰酸酯基或巯基官能团的聚硅氧烷聚合物和(ii)至少一种异氰酸酯基官能化的有机化合物；和(c)溶剂。还提供了使用所述固化组合物涂敷基底的方法以及由该涂敷的基底制备的制品。

Description

硅氧烷-氨基甲酸酯基污损脱附涂料
本发明涉及一种能形成聚氨酯-聚硅氧烷网络的双组分可湿固化的涂料组合物。该涂料组合物适用于海洋防污损涂料。
在海洋环境中到处都会发生生物污损，这对于海洋物体，例如船舶，是一个巨大的问题。一种限制污损微生物堆积的方法是使用基于硅酮弹性体的自清洁污损脱附涂料。基于聚二甲基硅氧烷(PDMS)的硅酮污损脱附涂料具有橡胶的弹性，低表面能和光滑的表面；这使得在流体动力阻力产生的切变应力下海洋微生物易于从涂料表面分离。但是，PDMS是柔软、易磨损，需要频繁的重新施用；因此，需要花费时间和金钱来维持。
一种有效改善基于PDMS的硅酮涂料的机械性能的方法是将PDMS与具有更好机械性能的其他聚合物混合，例如聚氨酯(PU)。聚硅氧烷和聚氨酯具有十分不同，但是却非常有用的物理和机械性能，这使得它们具有广泛的用途。在污损脱附涂料中当与聚二甲基硅氧烷组合时，聚氨酯由于机械强度、弹性、阻粘性、耐磨性显得十分突出。但是聚硅氧烷和聚氨酯的均一物理混合是难以达到的，这归因于这些树脂不相容的性质以及在初始混合后它们明显的相分离倾向。
美国专利US8,299,200(要求国际专利公布WO2009/025924的优先权)公开了一种使包括多异氰酸酯、多元醇和具有可以和多异氰酸酯反应的官能团的聚硅氧烷的混合物反应制备得到的聚硅氧烷改性聚氨酯涂料。可以和多异氰酸酯反应的官能团仅连接于聚硅氧烷链的一端。理论上来说，仅仅在一端连接的聚硅氧烷的涂料能得到高流动性的表面并且可以使污损生物更易脱附。但是，这样的硅氧烷是昂贵的，并且由该体系制得的涂料没有显示出在海洋环境中涂料所需求的性能参数。美国专利US5,820,491公开了一种双组分氨基甲酸酯面漆，包括多元醇组分、异氰酸酯组分和羟基官能化的聚醚改性聚硅氧烷共聚物组分。由该体系制得的涂料没有显示出在海洋环境中涂料所需要的性能参数。所需要的是替代性的、便宜的、简单的和均一的涂料组合物，其混合了PMDS和PU两者的性能，并且达到或超出海洋环境中涂料所需要的性能参数。
本发明提供了一种双组分可湿固化组合物，包括：(a)第一组分，其包括至少一种多官能多元醇；(b)第二组分，其包括：(i)至少一种具有至少两个异氰酸酯基官能团的聚硅氧烷聚合物和(ii)至少一种异氰酸酯基官能化的有机化合物；和(c)溶剂。本发明还提供了一种涂敷基底的方法，包括：(a)形成一种双组分可湿固化组合物，包括：(i)第一组分，其包括至少一种多官能多元醇；(ii)第二组分，其包括：(A)至少一种具有至少两个异氰酸酯基官能团的聚硅氧烷聚合物和(B)至少一种异氰酸酯基官能化的有机化合物；和(iii)溶剂；(b)任选的混入一种或多种颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或它们的组合；(c)将步骤(a)和(b)的组合物施用至基底并固化该组合物。
本发明还提供了一种双组分可湿固化组合物，包括：(a)第一组分，其包括：(i)至少一种多官能多元醇和(ii)至少一种具有至少两个巯基官能团的聚硅氧烷聚合物；(b)第二组分，其包括至少一种异氰酸酯基官能化的有机化合物；和(c)溶剂。本发明还提供了一种涂敷基底的方法，包括：(a)形成一种双组分可湿固化组合物，所述组合物包括：(i)第一组分，其包括：(A)至少一种多官能多元醇和(B)至少一种具有至少两个巯基官能团的聚硅氧烷聚合物；(ii)第二组分，其包括至少一种异氰酸酯基官能化的有机化合物；和(iii)溶剂；(b)任选的混入一种或多种颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或它们的组合；(c)将步骤(a)和(b)的组合物施用至基底并固化该组合物。
术语“多元醇”指的是包括多个羟基基团的醇分子。术语“多官能多元醇”指的是具有多于一个可交联反应位点的多元醇。术语“聚氨醋”指的是其中聚合物单元通过氨基甲酸酯连接，即-O-CO-NH-，和/或一个或多个脲连接，即-NH-CO-NH-，连接的树脂。术语“异氰酸酯基”指的是具有-N＝C＝O结构式的官能团。术语“巯基”指的是具有-SH结构式的官能团，也被称作硫醇基团。
本发明的聚硅氧烷聚合物具有如下结构式：
其中每个R1、R2、R3、R4、R5、R6、R7、R8、R9或R10各自独立的选自取代或未取代的C1至C60烃基，前提是(i)至少一个R1至R10基团为异氰酸酯基官能团或巯基基团所取代和(ii)聚硅氧烷聚合物具有至少两个异氰酸酯基或巯基官能团。优选的，至少一个R1至R10基团为异氰酸酯基官能团所取代和聚硅氧烷聚合物具有至少两个异氰酸酯基官能团。每个m和n各自独立的是0至更大的整数，前提是m+n≥1。优选的，异氰酸酯基官能化的聚硅氧烷具有4,000至15,000的数均分子量，更优选6,000至10,000。数均分子量是使用混合D柱和聚苯乙烯标准通过GPC Viscotek VE2001测定的。合适的异氰酸酯基官能化的聚硅氧烷的例子包括但不限于来自Siltech Corp.的和D-100材料，其是由如下结构式所示的线性双官能聚硅氧烷：
其中，a≥1和来自Siltech Corp.的由如下结构式所示的多官能聚硅氧烷：
其中
其中，a≥1和b＞1。
本发明的聚硅氧烷聚合物占可固化组合物固体总重量(即不包括可固化组合物中所使用的溶剂)的2-40wt％。优选聚硅氧烷聚合物占可固化组合物固体总重量的5-30wt％和更优选占可固化组合物固体总重量的10-25wt％。
本发明的多官能多元醇可选自丙烯酸类多元醇(acrylic polyol)、天然油多元醇、聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇和它们的混合物。优选丙烯酸类多元醇。合适的丙烯酸类多元醇包括Tg为0-45℃、优选10-40℃、最优选20-35℃和数均分子量(Mn)为2,000-25,000g/mol、优选3,000-15,000g/mol、最优选4,000-8,000g/mol的丙烯酸类聚合物。可购买的合适的丙烯酸类多元醇的例子包括来自陶氏化学公司(TheDowChemical Company)的ParaloidTMAU-750，来自陶氏化学公司的ParaloidTM AU-830，来自拜尔材料科学公司(Bayer Material ScienceAG)的和来自BASF Corporation的本发明的多官能多元醇占可固化组合物总重量的35-60wt％。优选多官能多元醇占可固化组合物总重量的40-55wt％和最优选占可固化组合物总重量的40-50wt％。丙烯酸类聚合物的玻璃化转变温度(即“Tg”)是使用来自TA instruments的DSC ModelQ100V9.8Build296以标准电池FC测量的。
合适的天然油多元醇(NOPs)包括未改性的NOPs，举例来说，例如，天然种子油二元醇单体；和改性的NOPs，举例来说，例如，可购买的来自陶氏化学公司的Gen 1 NOP DWD2080，其是经过重构的NOP分子，其中饱和单体、单羟基、双羟基和三羟基甲基酯的重量比为大约32％、38％、28％和2％。另一个例子，可购买的Gen4NOP是由UnoxolTM二醇和分离自种子油单体的种子油二醇单体之间的反应得到的。UnoxolTM二醇是顺式、反式-1，3-和顺式、反式-1，4-环己烷二甲醇的混合物，可购自陶氏化学公司。Gen4NOP具有如下结构，羟基当量为170g/mol。
得自天然油的多元醇是基于或得自可再生的原料资源，例如天然和/或基因改性植物蔬菜种子油和/或动物来源的脂肪。所述油和/或脂肪通常包括甘油三酯，即脂肪酸与甘油连接在一起。优选的是甘油三酯中具有至少大约70％为不饱和脂肪酸的蔬菜油。天然产物可含有至少大约85wt％的不饱和脂肪酸。优选的蔬菜油的例子包括但不限于，例如，来自以下的蔬菜油：蓖麻、大豆、橄榄、花生、油菜籽、玉米、芝麻、棉花、菜籽(canola)、红花、亚麻籽、棕榈树、葡萄籽、黑色籽草(black caraway)、南瓜籽、琉璃苣籽、树木胚芽(wood germ)、杏仁、阿月浑子、杏仁、澳大利亚坚果、鳄梨、沙棘(sea buckthorn)、大麻、榛实、夜来香、野玫瑰、蓟、胡桃、向日葵、麻疯籽油(jatropha seed oils)、或其组合。
另外，也可以使用来自生物体例如海藻的油。动物产品的例子包括猪油、牛油、鱼油及其混合物。也可以使用植物和动物基油/脂肪的组合。
NOP的平均羟基官能度为1至10；优选2至6。NOP可具有100至3,000的数均分子量；优选300至2,000；更优选350至1,500。
合适的异氰酸酯基官能化的有机化合物包括脂族或环脂族多异氰酸酯，例如六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、亚甲基二(对-环己基异氰酸酯)(H12MDI)、间-四甲基二甲苯基二异氰酸酯(m-TMXDI)、环己基二异氰酸酯(CHDI)、1，3-双(异氰酸甲酯基)环己烷和1，4-双(异氰酸甲酯基)环己烷；二异氰酸酯的三聚体，例如来自拜尔材料科学公司以N-3390商标销售的六亚甲基二异氰酸酯(HDI)的三聚体，，来自Perstorp Polyols，Inc.以商标销售的异佛尔酮二异氰酸酯(IPDI)的三聚体，，和它们的混合物。优选的异氰酸酯基官能化的有机化合物是六亚甲基二异氰酸酯(HDI)和异佛尔酮二异氰酸酯(IPDI)的三聚体；以及最优选六亚甲基二异氰酸酯(HDI)的三聚体。本发明的异氰酸酯基官能化的有机化合物占可固化组合物总重量的8-30wt％。优选异氰酸酯基官能化的有机化合物占可固化组合物总重量的10-30wt％和最优选占可固化组合物总重量的15-25wt％。
合适的氨基甲酸酯基溶剂包括芳香烃，例如二甲苯、甲苯；酮，例如甲基异丁基酮或丙酮，酯，例如醋酸丁酯或醋酸己酯；多元醇醚酯，例如丙二醇单甲基醚醋酸酯；酯，例如丙酸丙酯或丙酸丁酯，和其混合物。溶剂占可固化组合物总重量的10-60wt％。优选溶剂占可固化组合物总重量的15-50wt％和最优选占可固化组合物总重量的20-40wt％。
所述可固化组合物适用作涂料，和其可包括在此类型组合物中通常含有的各种添加剂。其他的添加剂的例子包括但不限于，颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或包括一种或多种前述添加剂的组合。
合适的增黏剂包括硅烷增黏剂，例如3-环氧丙氧丙基三甲氧基硅烷，其可以增加污损脱附外涂料的湿粘性而不需要中间涂层或粘结层。优选的，硅烷增黏剂占固化组合物总重量的0.5-3wt％，更优选占可固化组合物总重量的1-3wt％，以及最优选占可固化组合物总重量的1.5-3wt％。
本发明的可固化涂料组合物可以是无着色的透明清晰涂料，或者用于底漆、底漆腻子(basecoat)、面漆应用的着色体系。所述颜料可以是任何有机或无机颜料。对于特定的应用，可能需要数种不同的颜料以达到所期望的颜色。合适的颜料包括但不限于，二氧化钛，重晶石，粘土，碳酸钙，氧化铁红，CI颜料黄42，CI颜料蓝15、15:1、15:2、15:3、15:4(酞菁铜)，CI颜料红49:1，CI颜料红57:1和炭黑。
可以使用现有技术中已知的技术将得到的涂料组合物施加到基底上，例如喷涂、刮涂、辊涂。该涂层的额定干膜厚度(DFT)大于或等于2密耳，优选大于2.5密耳和更优选大于3密耳。可涂敷的基底包括但不限于塑料，木材，金属例如铝、钢或镀锌钢板，镀锡钢，混凝土，玻璃，复合材料，氨酯弹性体，上底漆的(着色的)基底等。涂层可在室温或升高的温度下、在强风型干燥箱或其他类型热源中进行固化。
下述实施例是对本发明的解释。
实验方法：
实施例中所用到的原料如下所述。
原料
测试步骤：
模拟藤壶拉脱强度(Pseudo-barnacle pull off strength)测试
根据如文献(Kohl JG&SingerIL，Pull-off behavior ofepoxy bonded to siliconeduplex coatings，Progress in Organic Coatings，1999，36：15-20)中所描述的修正的步骤使用商标名为InstronTM Model1122的Instron机器进行该测试。使用十毫米半径的铝质圆柱，并使用环氧粘合剂(来自Henkel LoctiteAmericas，www.loctite.com)将铝质圆柱粘结于被涂敷的面板上。在大约1小时的固化后除去多余的环氧。在室温下使环氧粘合剂至少硬化三天。使用Instron机器将圆柱拉脱直至圆柱从涂料表面分离。对于每个测试，使用至少两个、优选三个重复的样品，记录拉脱强度(以Mpa为单位测量)的平均值。模拟藤壶拉脱强度的阈值是0.6Mpa。
接触角测试
使用来自AST Products，Inc.的VCA Optima接触角测量仪测试涂料的水接触角。将0.5-1μl的水滴置于涂料表面。在平衡时间后测量接触角。更高的接触角意味着涂料表面是疏水的。对于污损脱附涂料而言，接触角必须≥100°。
抗冲强度
根据ASTM D2794使用Gardner抗冲测试仪测量涂料的抗冲强度。该测试需要将重物掉落至停留在涂料表面的压头上。所述重物从一个已知的高度掉落，压头在被涂敷的面板上形成凹陷。在凹陷处或其周围观察涂料的破裂或分层。以英寸-磅(in-lb)为单位记录产生破裂/分层的力。没有导致涂料不合格的最大的力为160in-lbs。测试是通过直接冲击涂料，涂料朝上进行的。抗冲强度的阈值为80in-lbs。
交叉线附着力
根据ASTM D3359测量交叉线附着力。4B或5B的等级被认为是可以接受的附着力水平。
附着力-热水浸渍
将固化的面板浸渍于热水(80℃)中5天。完成后将面板移出热水浴，干燥并冷却至实验室环境温度。视觉观察涂料在源自交叉线附着力测试的刻线区域的分层、涨裂和起泡等情况。如果没有观察到损伤，该面漆被评价为附着力合格。
涂敷应用&固化
使用钢丝缠绕刮棒或者8线湿膜涂布机将涂料涂敷至4英寸×12英寸的铬酸铝预处理和磷酸钢预处理(steel phosphate pre-treated panel)的面板上。通过使用不起毛布和IPA擦拭进行预清洁从而除去油，然后在加压空气或氮气下干燥。测试前，涂敷的基板在大约50％湿度(RH)和实验室环境温度(～24℃)下固化至少7天。
配方：
实施例1-29 & 对比例1-3
涂料配方是在FlackTek speedMixwerTM(Medel DAC150FV-K，FlackTek，Inc.)双不对称离心机中制备的。配方按如下步骤制备：
1、除了其他在配方表格中特别提及的溶剂，将等重量份的MIBK，丙酸正丁酯和丙酸正丙酯制成溶剂混合物
2、使用上述溶剂混合物和1％DBTDL制备成1％的催化剂溶液
3、将多元醇、溶剂、催化剂溶液和增黏剂(如果配方中含有的话)加至SpeedMixer杯中
4、以～3000rpm的转速混合所述混合物30秒
5、将异氰酸酯基官能化组分加至SpeedMixer杯中
6、以～3000rpm的转速混合所述混合物30秒
7、涂敷基板并按照上面所述的进行固化
实施例1-6测试结果
这些结果表明不同玻璃化转变温度的丙烯酸类多元醇得到了具有如抗冲强度结果表示的优良的韧性和脱附性能的涂料。这也表明不同程度的PDMS聚合物上的异氰酸酯基的官能度(Silmer C-50是三官能度的，而Silmer Di-100是双官能度的)得到了相同的结果。这些实施例中异氰酸酯基官能化的PDMS的含量是基于配方中固体总量的10％。
实施例7-12测试结果
这些结果表明不同程度的异氰酸酯基官能化的PDMS提供了有韧性的涂料(抗冲强度)和良好的脱附性能。基于配方中总的固体量，在这些配方中异氰酸酯基官能化的PDMS的含量为5-20％。这也特别表明可以使用不同重均分子量的异氰酸酯基官能化的PDMS：Silmer NCO Di-50(MW4300g/mol)和SilmerNCO Di-100(MW8000g/mol)。
实施例13-15测试结果
这些结果进一步扩展表明不同程度的异氰酸酯基官能化的PDMS提供了有韧性的涂料(抗冲强度)和良好的脱附性能。基于配方中总的固体量，在这些配方中异氰酸酯基官能化的PDMS的含量为20-30％。
实施例16和17测试结果
这些数据证实了之前在配方中含20％和25％的异氰酸酯基官能化的PDMS的数据，使用新的大量的丙烯酸类多元醇A，标记的丙烯酸类多元醇D(略微高的羟基当量)仍然表现出优良的韧性(抗冲强度)和脱附性能。
实施例18和19测试结果
这些数据证实了也可以使用除丙烯酸类多元醇外的其他多元醇。但是，优选丙烯酸类多元醇。
实施例20-25测试结果
实施例 外涂层间隔 模拟藤壶 交叉线 热水
附着力 附着力 粘附力
小时 MPa
20 24 0.32 5B 通过
21 48 0.29 5B 通过
22 72 0.23 5B 通过
23 96 0.31 5B 通过
24 168 0.2 5B 未通过
25 168 0.23 5B 未通过
实施例20-25表明粘结层或中间涂层不需要达到可接受的污损脱附性能和与底涂层的附着力。实施例20-25是按照上面所述的制备的，并施用至使用商业化海洋环氧底漆(Interguard264，由International Paint生产)涂过底漆的处理过的金属面板，所述海洋环氧底漆是按照厂家推荐的方法使用的。底漆被施用至基板然后各自按照24、48、72、96和168小时(实施例20-25-实施例24&25在168小时后施用不同程度的硅酮)、按照上面所描述的进行固化。
这些实施例表明在底涂层和污损脱附顶涂层之间不使用粘结层或中间涂层也能达到优良的脱附性能。这些结果还表明在施用顶涂层至底涂层之间24-144小时、优选24-120小时、更优选48-96小时的优选的外涂层窗，具有如热水附着力测试所证明的优良的附着力。
实施例26-29测试结果
实施例 外涂层间隔 模拟藤壶 交叉线 热水
附着力 附着力 粘附力
小时 MPa
26 24 0.32 5B 通过
27 48 0.24 5B 通过
28 72 0.26 5B 通过
29 96 0.25 5B 通过
实施例26-29表明可以使用硅烷增黏剂进一步增强污损脱附顶涂层的湿附着力，而不需要中间涂层或粘结层。
实施例24-27是按照上面所述的制备的，并将其施加到使用商业化海洋环氧底漆(Interguard264，由International Paint生产)涂过底漆的处理过的金属面板，所述海洋环氧底漆是按照厂家推荐的方法使用。将底漆施加到基板然后各自固化24、48、72或96小时(实施例24-27)。底漆的额定干膜厚度(DFT)为4-4.5密耳。施加面漆使其DFT大于2.5密耳然后按照上面上述的进行固化。
这些实施例表明在当在面漆配方中加入硅烷增黏剂时，底涂层和具有如热水附着力测试所证明的优良的附着力的污损脱附顶涂层之间不使用粘结层或中间涂层就能得到优良的脱附性能。视觉上观察在热水附着力测试后实施例26-29较实施例20-23更好。硅烷增黏剂的量为0.5-3wt％，优选1-3wt％，更优选1.5-3wt％。
对比例
下面的对比例是2K氨基甲酸酯体系。但是它们在性能和固化的涂料组合物方面与本发明不同。
比较例26-29测试结果
比较例 接触角 模拟藤壶附着力 交叉线附着力 热水粘附力
MPa
1 91° 0.06 5B 未通过
2 74° 0.13 5B 未通过
3 50° 0.01 5B 未通过
没有一个接触角满足显示出≥100°水接触角的污损脱附涂料的阈值。归因于可以轻易从表面擦去的严重模糊掉的硅氧烷成分，每个对比例的涂料质量都十分低劣。虽然模拟藤壶附着力满足要求，但是在浸渍后没有一个涂料通过热水附着力测试，所有的涂料都从表面严重分层和破裂。这些对比例表明本发明相比其他2K氨基甲酸酯污损脱附技术具有性能优势，本发明不需要中间涂层或粘结层就实现的更好的附着力和更好的涂料质量高度。

Claims (18)

1.一种双组分可湿固化组合物，其包括：
(a)第一组分，其包括至少一种多官能多元醇；
(b)第二组分，其包括：(i)至少一种具有至少两个异氰酸酯基官能团的聚硅氧烷聚合物和(ii)至少一种异氰酸酯基官能化的有机化合物；和
(c)溶剂。
2.如权利要求1所述的组合物，其特征在于，所述聚硅氧烷聚合物具有4,000至15,000的数均分子量。
3.如权利要求1所述的组合物，其特征在于，基于可固化组合物总的固体重量，其中聚硅氧烷聚合物为2-40wt％。
4.如权利要求1所述的组合物，其特征在于，所述聚硅氧烷聚合物是：
(i)具有如下结构式的双官能聚硅氧烷：
其中a≥1；或
(ii)具有如下结构式的多官能聚硅氧烷：
其中
其中a≥1和b＞1。
5.如权利要求1所述的组合物，其特征在于，所述多官能多元醇选自丙烯酸类多元醇、天然油多元醇、聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇及其混合物。
6.如权利要求1所述的组合物，其特征在于，所述多官能多元醇是Tg为0℃-45℃和数均分子量为2,000g/mol至25,000g/mol的丙烯酸类聚合物。
7.如权利要求1所述的组合物，其特征在于，所述多官能多元醇占所述可固化组合物总重量的35-60wt％。
8.如权利要求1所述的组合物，其特征在于，所述异氰酸酯基官能化的有机化合物选自六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、亚甲基二(对-环己基异氰酸酯)(H12MDI)、间-四甲基二甲苯基二异氰酸酯(m-TMXDI)、环己基二异氰酸酯(CHDI)、1，3-双(异氰酸甲酯基)环己烷、1，4-双(异氰酸甲酯基)环己烷、二异氰酸酯的三聚体及其混合物。
9.如权利要求1所述的组合物，其特征在于，所述异氰酸酯基官能化的有机化合物占所述可固化组合物总重量的8-30wt％。
10.如权利要求1所述的组合物，其进一步包括一种或多种颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或它们的组合。
11.如权利要求所述10的组合物，其特征在于，所述增黏剂是3-环氧丙氧丙基三甲氧基硅烷。
12.如权利要求4所述的组合物，其中：
(a)基于所述可固化组合物总的固体重量，聚硅氧烷聚合物占2-40wt％，并且其具有4,000至15,000的数均分子量；
(b)多官能多元醇占所述可固化组合物总重量的35-60wt％，并且其是Tg为0℃-45℃和数均分子量为2,000g/mol至25,000g/mol的丙烯酸类聚合物；和
(c)异氰酸酯基官能化的有机化合物占可所述固化组合物总重量的8-30wt％，并且其选自六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、亚甲基二(对-环己基异氰酸酯)(H12MDI)、间-四甲基二甲苯基二异氰酸酯(m-TMXDI)、环己基二异氰酸酯(CHDI)、1，3-双(异氰酸甲酯基)环己烷、1，4-双(异氰酸甲酯基)环己烷、二异氰酸酯的三聚体及其混合物。
13.一种涂敷基底的方法，包括：
(a)形成一种双组分可湿固化的组合物，包括：
(i)第一组分，其包括至少一种多官能多元醇；
(i)第二组分，其包括：(A)至少一种具有至少两个异氰酸酯基官能团的聚硅氧烷聚合物和(B)至少一种异氰酸酯基官能化的有机化合物；和
(ii)溶剂；
(b)任选的混入一种或多种颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或它们的组合；
(c)将步骤(a)和(b)的组合物施用至基底并固化该组合物。
14.由权利要求13的方法得到的涂敷制品。
15.如权利要求14的涂敷制品，其涂层具有大于或等于2密耳的额定干膜厚度(DFT)。
16.一种双组分可湿固化的组合物，包括：
(a)第一组分，其包括：(i)至少一种多官能多元醇和(ii)至少一种具有至少两个巯基官能团的聚硅氧烷聚合物；
(b)第二组分，其包括至少一种异氰酸酯基官能化的有机化合物；和
(c)溶剂。
17.一种涂敷基底的方法，包括：
(a)形成一种双组分可湿固化的组合物，包括：
(i)第一组分，其包括：(A)至少一种多官能多元醇和(B)至少一种具有至少两个巯基官能团的聚硅氧烷聚合物；
(ii)第二组分，其包括至少一种异氰酸酯基官能化的有机化合物；和
(iii)溶剂；
(b)任选的混入一种或多种颜料、染料、光泽度降低剂、固化催化剂、流平剂、脱气剂、增黏剂、分散助剂、阻燃剂、热稳定剂、光稳定剂、抗氧化剂、增塑剂、抗静电剂、紫外(UV)吸收剂、润滑剂或它们的组合；
(c)将步骤(a)和(b)的组合物施用至基底并固化该组合物。
18.由权利要求17的方法得到的涂敷制品。
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CN109153767B (zh) * 2016-05-24 2021-09-24 巴斯夫涂料有限公司 涂覆剂和由其制备的具有改进抗污性和清洁性的涂层及其用途
US11597794B2 (en) 2016-05-24 2023-03-07 Basf Coatings Gmbh Coating compositions and coatings produced therefrom with improved soiling resistance and (self-)cleaning properties and use thereof
CN110511671A (zh) * 2019-08-07 2019-11-29 安徽海德化工科技有限公司 一种用于石油蒸馏塔抗开裂耐热涂料
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BR102013032886A2 (pt) 2019-10-15
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US20150307745A1 (en) 2015-10-29
US20140186621A1 (en) 2014-07-03
US9145500B2 (en) 2015-09-29
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