CN104140724B - 多层涂层体系、涂覆方法和经其涂覆的基底 - Google Patents
多层涂层体系、涂覆方法和经其涂覆的基底 Download PDFInfo
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- CN104140724B CN104140724B CN201410353120.XA CN201410353120A CN104140724B CN 104140724 B CN104140724 B CN 104140724B CN 201410353120 A CN201410353120 A CN 201410353120A CN 104140724 B CN104140724 B CN 104140724B
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract
本发明提供了一种多层涂层体系,其包括第一涂料组合物和第二涂料组合物,其中所述第一涂料组合物包含玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a);而第二涂料组合物包含三官能度聚酯丙烯酸酯、六官能度聚氨酯丙烯酸酯和九官能度聚氨酯丙烯酸酯。本发明还提供用所述多层涂层体系涂覆基底的方法以及经所述多层涂层体系涂覆的基底。
Description
技术领域
本发明涉及一种具有高光泽度多层涂层体系,具体而言涉及包含高玻璃化转变温度的丙烯酸树脂的第一涂料组合物和具有三种不同官能度的树脂组合的第二涂料组合物的多层涂层体系。本发明还涉及用所述多层涂层体系涂覆基底的方法以及经所述多层涂层体系涂覆的基底。
背景技术
紫外光(UV)固化是一种先进的材料表面处理技术,它利用UV引发具有化学活性的液态材料快速聚合交联,瞬间固化成膜。有“5E”特点的UV固化技术,以高效、经济、节能、环境友好、适用性广为标志,已经成为21世纪的绿色工业新技术。该技术被广泛应用于涂料、油墨、交联剂、结构材料的快速固化,尤其适用于电子消费产品的表面涂层。
目前电子产品尤其是手机的外壳通常采用底漆加UV面漆的体系来涂覆。底漆采用1K体系,涂料可使用的时间长,漆膜一次烘烤成膜后,后期基本不需要加烤,节省能源。UV面漆具有固化速度快,节省能源,生产效率高,固化产性能好,适合于高速自动化生产等突出优点。然而,目前存在的双涂层体系在经历水煮、温湿循环、QUV等测试后,很难完全克服漆膜起泡的问题。这影响了手机的质感和外观。因此,在本领域对能够克服底漆+UV涂层起泡并具有高光泽度的涂层体系存在需求。
发明内容
本发明提供了一种多层涂层体系,其包括第一涂料组合物和第二涂料组合物,其中所述第一涂料组合物包含玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a);而第二涂料组合物包含三官能度聚酯丙烯酸酯、六官能度聚氨酯丙烯酸酯和九官能度聚氨酯丙烯酸酯。
本发明还提供了在基底上形成所述多层涂层体系的方法,包括:(1)将第一涂料组合物施用于所述基底的至少一部分上,形成底漆,和(2)将第二涂料组合物施用于所述底漆的至少一部分上,形成清漆。
本发明还提供经一种经涂覆的基底,包括基底和沉积在至少一部分所述基底上的上述多层涂层体系。
具体实施方式
除了实施例中的或另外明确说明的,应当认为说明书和权利要求书中使用的所有代表成分的数量、反应条件等的数值在所有情况下均可按照术语“约”进行变化。因此,除非有相反的说明,否则以下的说明书和权利要求书中所列出的数值参数均为近似值,可以按照本发明想要获得的性能而变化。起码,而不是为了限制相当于权利要求范围的这一原则的实施,每个数值参数至少应当按照有效数字来解释并运用普通的舍入法。
尽管列出本发明宽范围的数值范围和参数是近似值,但具体实施例中列出的数值记录得尽可能准确。但是,任何一个数值本来就具有一定的误差。该误差是其相应的测量方法中得出的标准偏差的必然结果。
在一个实施方式中,提供了一种多层涂层体系,其包括第一涂料组合物和第二涂料组合物,其中所述第一涂料组合物包含玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a);而第二涂料组合物包含三官能度聚酯丙烯酸酯、六官能度聚氨酯丙烯酸酯和九官能度聚氨酯丙烯酸酯。
第一涂料组合物通常作为底漆涂布于至少部分基底上。
在所述第一涂料组合物中,所述丙烯酸树脂(a)的玻璃化转变温度优选在约75-90℃的范围内。所述丙烯酸树脂的重均分子量通常在10000至150000的范围内,优选为30000至120000,更优选为30000-80000。适用的丙烯酸树脂可为均聚物或共聚物,其可由选自下述的一种或多种单体聚合而成:丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸β-羟基乙基酯、丙烯酸异辛酯、丙烯酸异冰片酯,丙烯酸月桂酯、丙烯酸羟基丁酯、丙烯酸-2-羟基丙酯、丙烯酸十八醇酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸β-羟基乙基酯、苯乙烯、甲基丙烯酸异辛酯、甲基丙稀酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基丙酯和甲基丙烯酸十八醇酯。
通常,所述丙烯酸树脂(a)以基于第一涂料组合物的重量计约10-50wt%的量存在于该第一涂料组合物中。当该丙烯酸树脂的量低于10wt%时,由该第一涂料组合物形成的涂层的漆膜较软,附着较好,涂覆第二涂层后,漆膜的附着性虽然较好,但是水煮后起泡严重。当该量高于50wt%时,漆膜的耐水煮性能提高但是附着性会变差。当该丙烯酸树脂的含量位于该含量范围之内时,可实现优异的附着性和耐水煮平衡。
很多商业可得的此类丙烯酸树脂可用于本发明中。例如,可用于本发明的此类丙烯酸树脂的实例包括但不限于:来自DSM的NEOCRYLB-805、来自三菱丽阳的DIANALMB-2952和LR-7666、来自DIC的ACRYDICSHA-288A、来自加合的A-33R,以及它们的任意组合。
所述第一涂料组合物还可包含一种玻璃化转变温度在30-65℃范围内的丙烯酸树脂(b)。
所述丙烯酸树脂(b)的玻璃化转变温度优选在约50-65℃的范围内。所述丙烯酸树脂的重均分子量通常在10000至150000的范围内,优选为30000至120000,更优选为30000-80000。适用的丙烯酸树脂可为均聚物或共聚物,其可由选自下述的一种或多种单体聚合而成:丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸β-羟基乙基酯、丙烯酸异辛酯、丙烯酸异冰片酯,丙烯酸月桂酯、丙烯酸羟基丁酯、丙烯酸-2-羟基丙酯、丙烯酸十八醇酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸β-羟基乙基酯、苯乙烯、甲基丙烯酸异辛酯、甲基丙稀酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基丙酯和甲基丙烯酸十八醇酯。
所述丙烯酸树脂(b)可以以基于第一涂料组合物的重量计约5-25wt%的量存在于该第一涂料组合物中。当该丙烯酸树脂的量低于5wt%时,漆膜的附着性变差。当该量高于25wt%时,漆膜的附着性提高但水煮后起泡严重。
很多商业可得的此类丙烯酸树脂可用于本发明中。例如,可用于本发明的此类丙烯酸树脂的实例包括但不限于:来自罗门哈斯的PARALOIDB44、来自日立化成的AD70、来自DIC的SHA-288,以及它们的任意组合。
在一个优选的实施方式中,所述第一涂料组合物可包含按该第一涂料组合物的重量计约10-50wt%的丙烯酸树脂(a)和约5-25wt%的丙烯酸树脂(b)。所形成的涂层可具有优良的附着性、耐水煮性。
根据本发明的多层涂层体系的第一涂料组合物还可包含有机溶剂和一种或多种本发明所属技术领域常用的其他添加剂。
对所用的溶剂并没有特别限制,可为本领域技术人员已知的任何有机溶剂,其包括但不限于脂族或芳族烃,如Solvesso100TM、甲苯或二甲苯,醇类,如丁醇或异丙醇,酯类,如乙酸乙酯、乙酸丁酯或醋酸异丁酯,酮类,如丙酮、甲基异丁基酮或丁酮,酶、醚醇或醚酯,如3-乙氧基丙酸乙酯,或上述的任意混合物。优选醋酸乙酯和/或丁酮。所述溶剂的用量通常占所述第一涂料组合物的0-50wt%。
所述一种或多种其他添加剂包括但不限于分散剂、流平剂、抗氧化剂、消泡剂、流变助剂等。这些添加剂的类型是本领域技术人员熟知的,而且其用量是本领域技术人员根据实际需求容易确定的。
在某些实施方式中,所述第一涂层组合物包含纤维素酯添加剂,诸如醋酸纤维素(CA)、醋酸丙酸纤维素(CAP)和/或醋酸丁酸纤维素(CAB)。此类添加剂可通过改进第一涂料组合物的流动和流平以及改进金属小片的取向(如果这样的金属小片存在于该第一涂料组合物中以提供“金属化”感官)来改进底漆加清漆涂料体系的外观。另外,这样的添加剂可通过促进第一涂料组合物的快速干燥和早期固化发展从而有助于减少与后续施加的第二涂料组合物(UV固化组合物)的混合。通常,所述纤维素酯可以足以赋予所需涂料特性的量存在。例如。所述纤维素酯可以占第一涂料组合物重量的约0-20wt%。
所述第二涂层组合物是UV可固化的涂料组合物,其通常作为清漆层涂覆于第一涂料组合物上。
在本发明所述的第二涂料组合物中,所述三官能度聚酯丙烯酸酯是羟基聚酯与丙烯酸的反应产物。优选地,适用的三官能度聚酯丙烯酸在室温下通常具有约5000-12000mPa的粘度,且其玻璃化转变温度高于约250℃。在低官能UV固化低聚物中,所述三官能度聚酯丙烯酸酯具有优良的柔韧性和防水性。
通常,所述三官能度聚酯丙烯酸酯以基于第二涂料组合物的重量计约5-25wt%的量存在于该第二涂料组合物中。当该三官能度聚酯丙烯酸酯的量低于5wt%时,漆膜的耐水煮性能增强,但其附着性会变差,使得漆膜容易发脆。当该量高于25wt%时,所得漆膜的耐水煮测试变差,起泡严重。
很多商业可得的三官能度聚酯丙烯酸酯可用于本发明中。例如,可用于本发明的所述三官能度聚酯丙烯酸酯的实例包括但不限于下述:来自长兴的6130B-80、EM2382和6151;来自阿克玛的CN989;来自湛新的EB8405;来自东亚合成的M-7100;来自TOA-DICZHANGJIAGANGCHEMICAL的M-8060;以及它们的任意组合。
在本发明所述的第二涂料组合物中,所述六官能度聚氨酯丙烯酸酯是季戊四醇三丙烯酸酯(PETA)、脂肪族二异氰酸酯和羟基多元醇的缩聚产物。优选地,所述六官能度聚氨酯丙烯酸酯具有PETA-二异氰酸酯-骨架-二异氰酸酯-PETA的通式结构。所述六官能度聚氨酯丙烯酸酯具有耐磨性好、表面硬度高、固化速度快等优势。所述六官能度聚氨酯丙烯酸酯通常也具有优良的附着性、柔韧性、流平性和耐水性,但是其具有黄变和咬底的缺陷。
通常,所述六官能度聚氨酯丙烯酸酯以基于第二涂料组合物的重量计约5-25wt%的量存在于该第二涂料组合物中。当该六官能度聚氨酯丙烯酸酯的量低于5wt%时,漆膜的附着性变差,涂层变脆。当该量高于25wt%时,所得涂层的附着性提高,但是容易引起涂层咬底,从而影响涂层外观,此外涂层黄变增加。
很多商业可得的六官能度聚氨酯丙烯酸酯可用于本发明中。例如,可用于本发明的所述六官能度聚氨酯丙烯酸酯的实例包括但不限于下述:来自立大的U-0606、来自长兴的DR-U123、来自QUALIPOLYCHEMICALCORP的GU6300Y,以及它们的任意组合。
在本发明所述的第二涂料组合物中,所述九官能度聚氨酯丙烯酸酯是多异氰酸酯和羟基丙烯酸酯的反应产物。在高官能UV固化低聚物中,所述九官能聚氨酯丙烯酸酯具有优良的柔韧性。此外,该树脂还具有出色的防水性和耐化学品性。
通常,所述九官能度聚氨酯丙烯酸酯以基于第二涂料组合物的重量计约5-50wt%的量存在于该第二涂料组合物中。当该九官能度聚氨酯丙烯酸酯的量低于5wt%时,漆膜的柔韧性增强但耐水煮性差。当该量高于50wt%时,漆膜的耐水煮性性提高,但是涂层变脆,而且附着性变差。
很多商业可得的九官能度聚氨酯丙烯酸酯可用于本发明中。例如,可用于本发明的所述九官能度聚氨酯丙烯酸酯的实例包括但不限于下述:来自三井的RA1353、RA4800M;来自根上的UN-3320HS;来自长兴的DR-U076、6195-100和6197;来自美源的SC2152;来自立骅的U-0930;来自湛新的EB1290N;来自阿克玛的CN9010;来自的GUANGZHOUWUXMATERIALCO的W4905,以及它们的任意组合。
在一个实施方式中,本发明的多层涂层体系中的第二涂料组合物还包含基于该第二涂料组合物的重量计约5-25wt%的稀释单体。所用的稀释单体优选为双官能的丙烯酸酯类单体。当第二涂料组合物中存在的稀释单体的含量太低时,则组合物的粘度太大,导致操作性变差,存在流平性不良等缺陷。当第二涂料组合物中存在的稀释单体的含量太高时,容易引起涂层咬底从而影响涂层外观。
可用于本发明中的稀释单体包括但不限于:二丙烯酸二丙醇酯、二丙烯酸三丙二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸二乙二醇酯、二丙烯酸聚乙二醇(400)酯、二丙烯酸聚乙二醇(600)酯、二甲基丙烯酸二乙二醇酯、二丙烯酸乙氧基化双酚酯、二甲基丙烯酸乙氧基化双酚酯、二丙烯酸三环癸烷二甲醇酯、二丙烯酸丙氧化(2)新戊二醇酯,以及它们的任意组合。
在一个实施方式中,本发明多层涂层体系中的第二涂料组合物还包含基于该第二涂料组合物的重量计约1-9wt%的光引发剂。对所使用的光引发剂并没有特别限定,只要其能够经光照射后发生裂解而产生自由基,从而引发光聚合反应。可用的光引发剂包括但不限于苯偶姻衍生物、苯偶酰缩酮衍生物、二烷氧基苯乙酮、α-羟烷基苯酮、α-胺烷基苯酮、酰基膦氢化物、酯化肟酮化合物、芳基过氧酯化合物、卤代甲基芳酮、有机含硫化合物、苯甲酰甲酸酯等。根据需要,可以选择两种或超过两种的光引发剂。
除上述组分外,根据本发明的多层涂层体系的第二涂料组合物还可包含有机溶剂和一种或多种本发明所属技术领域常用的其他添加剂。
对所用的溶剂并没有特别限制,可为本领域技术人员已知的任何有机溶剂,其包括但不限于脂族或芳族烃,如Solvesso100TM、甲苯或二甲苯,醇类,如丁醇或异丙醇,酯类,如乙酸乙酯、乙酸丁酯或醋酸异丁酯,酮类,如丙酮、甲基异丁基酮或丁酮,酶、醚醇或醚酯,如3-乙氧基丙酸乙酯,或上述的任意混合物。优选醋酸异丁酯和/或丁酮。所述溶剂的用量通常占所述第二涂料组合物的0-50wt%。
所述一种或多种其他添加剂包括但不限于分散剂、流平剂、抗氧化剂、消泡剂、流变助剂等。这些添加剂的类型是本领域技术人员熟知的,而且其用量是本领域技术人员根据实际需求容易确定的。
在一个实施方式中,本发明还提供了将所述多层涂层体系施用于基底的方法,其包括将第一涂料组合物作为底漆施用于所述基底的至少一部分,以及将第二涂料组合物作为清漆施用于所述第一涂料组合物的至少一部分上。
典型地,使用本领域已知的技术将第一涂料组合物施用于基底的至少一部分。例如,可使用喷涂、辊涂、淋涂、浸泡/浸渍、刷涂或流涂方法中的一种或多种将第一涂料组合物施用于基底的至少一部分。可以使用本领域已知的任何合适的方法使第一涂料组合物固化。优选地,通过在60-80℃烘烤约10-30min,使溶剂挥发,从而实现固化。底漆的膜厚通常在5-20μm的范围内。
然后,可以使用上述任何方法将第二涂料组合物施加于底漆上并使其固化。优选地,固化通过下述步骤实现:在45-60℃烘烤约5-10min,使溶剂挥发,然后在UV能量为400-1600mj/cm2,光强在80-250mw/cm的照射强度下进行UV辐照。面漆的膜厚通常在15-30μm的范围内。
本发明的多层涂层体系可涂覆于任何基底。所述基底可包括但不限于瓷砖、木材、皮革、石材、玻璃、合金、纸张、塑料、纤维、棉织品等,优选为金属或塑料。所述塑料基底,尤其指电子产品诸如移动电话、个人数码助手、智能手机、个人计算机等的基底,例如可为聚丙烯(PC)、丙烯腈-丁二烯-苯乙烯(ABS)树脂、玻璃纤维(GF)或其任意组合。
实施例
提供下述实施例进一步阐述本发明,但不应认为其将本发明限制在实施例所述的细节。除另外说明之外,下述实施例以及通篇说明书中所有的份数和百分数均以重量计。
实施例
第一涂料组合物的制备
使用表1中所列的组分和量制备本发明多层涂层体系中的第一涂料组合物。
表1.第一涂料组合物的配制
*基于第一涂料组合物的总重量(g):
1DSMNEORESINSNEOCRYLB-805,Tg90℃;
2PARALOIDB44ACRYLICRESIN,Tg40℃;
3DIANALMB-2952,Tg84℃;
4BYK-323,有机硅流平剂,供应商BYK;
5CAB381-2,供应商伊士曼。
第二涂料组合物的制备
使用表2中所列的组分和量制备本发明多层涂层体系中的第二涂料组合物。
表2.第二涂料组合物的配制
*基于第二涂料组合物的总重量(g):
1M-8060,供应商TOA-DICZHANGJIAGANGCHEMICAL;
2EB130,供应商Allnex;
3W4905,供应商GUANGZHOUWUXMATERIALSCIENCECO;
4GU6300Y,供应商QUALIPOLYCHEMICALCORP;
5BYK-3550和BYK-333(重量比为3:1),供应商BYK;
6DBC184,供应商台湾双键;MBF,供应商Ciba,两种光引发剂重量比为1:1;
7丁酮、醋酸异丁酯。
涂层制备过程
将上述表1中所示的第一涂料组合物实施例1-5(底漆)加入稀释剂(按一定比例混合的醋酸乙酯/异丙醇/乙二醇丁醚)稀释,使得稀释后的涂料组合物粘度为8-10s。然后将经稀释的涂料组合物采用喷涂方法涂覆于基底(PC、PC+ABS、ABS或PC+GF),并在60-80℃烘烤10-30min,以去除溶剂,并形成底漆。将表2中所述的第二涂料组合物实施例6-10(清漆)加入稀释剂(按一定比例混合的醋酸乙酯/异丙醇/乙二醇丁醚)稀释,使得稀释后的涂料组合物粘度为7.5-10s。然后将经稀释的各涂料组合物采用喷涂方法分别涂覆于底漆上,并在45-60℃烘烤5-10min,以去除溶剂。然后通过UV光照射(UV能量400-1600mJ/cm2,光强80-250mw/cm),使光引发剂裂解产生活性自由基,从而引发单体和树脂聚合,形成三维立体交联网络而成膜。由此制得本发明的双涂层实施例11-15。
然后对涂覆有本发明的双涂层体系11-15的基底进行如下性能测试。结果示于下表3中。
1.涂膜与基底的附着力测试
用NT刀在试样表面划6x6道(25个1mm2方格,划线应深及基底),保持测试表面尽可能平整(保持刀刃锋利)。若试样太小没有足够的空间划格,则划45度交叉格。将Nichiban胶带(No.405)、Scotch胶带(No.610)或同类型其它胶带(18mm宽,胶带粘性应当大于等于5.3N/18mm宽)粘贴至试样表面,并用橡皮将胶带压实,使胶带与测试表面充分接触,静置3分钟。沿90度方向迅速撕下胶带,目测检验测试表面,参照ISO标准评级。
ISO标准评级
0级:5B
切口的边缘完全光滑,格子边缘没有任何剥离。
1级:4B
在切口相交处有小片剥离,划格区内实际破损小于等于5%。
2级:3B
切口的边缘或相交处有剥离,其面积在5%-15%。
3级:2B
沿切口边缘有部分剥离或整大片剥离,或部分格子被整片剥离,剥离的面积在15%-35%。
4级:1B
切口边缘大于剥离或一些方格部分或全部剥落,其面积在35%-65%。
5级:0B
在划线边缘及交叉处有成片的油漆脱落,且脱落总面漆大于65%。
通常,当该涂层体系用于手机外壳应用时,要求测试结果在4B或4B以上。
2.UV照射测试
单循环:4小时UV照射(UV-A,340nm,0.63W/m2/nm,60℃)+4小时湿度储存(50℃),总共12个循环(4天)。试样表面的一半用铝箔覆盖(留待与试验后部位比较)。
UV照射之后,检查试样表面涂层的颜色、光泽和表面粗糙度变化。通过X-rite色差仪测试ΔE值来显示颜色变化(深色ΔE≤0.7,浅色ΔE≤1)。在进行UV测试前,需测试的测试板先用色差仪打色差,得到L1、a1和b1值。UV照射后,再次将测试板用色差仪打色差,得到L2、a2、b2值。按照下式计算ΔE:
目测观察试样表面是否存在气泡、裂痕等。之后,在涂层表面贴上405胶带(用手指压实)并将胶带与涂层表面成90度角快速剥离。检查胶带剥离时表面涂层是否脱落。
3.化妆品测试
将下述化妆品各取10g放入量杯中混合均匀(一次配样仅能使用一次,不允许隔天使用):大宝美容日霜/妮维雅男士须后润肤露、大宝清爽保湿防晒露/凡士林倍护润手霜、大宝SOD蛋白霜/强生婴儿保湿润肤露、强生婴儿润肤油、水宝宝运动防晒SPF30(CoppertonesportsunscreenSPF30)和水宝宝运动防晒SPF50(oppertoneultraguardsunscreenSPF50)。用一支牙刷将以上混合物均匀涂抹到试样表面。将涂有化妆品的试样放入环境测试炉中,在温度70℃、湿度85%分别进行48小时和72小时的测试。另外,将涂有上述化妆品混合物的试样于常温放置4小时。
上述测试完成后,检查试样表面涂层的颜色、光泽和表面粗糙度变化。目测观察试样表面是否存在气泡、裂痕等。之后,在涂层表面贴上405胶带(用手指压实)并将胶带与涂层表面成90度角快速剥离。检查胶带剥离时表面涂层是否脱落。
4.温湿循环测试
使测试试样经历下述循环:从温度21℃湿度、60%RH,经过3h转变到-40℃,在此条件下持续2h;然后从-40℃温度经过6h转变到温度85℃、湿度50%RH,在此条件下持续2h;然后转变到温度21℃、湿度60%RH,一个循环结束。一共持续循环5次。
上述测试完成后,目测观察试样表面涂层是否存在明显的色差。目测观察试样表面是否存在气泡、裂痕和变形。之后,在涂层表面贴上405胶带(用手指压实)并将胶带与涂层表面成90度角快速剥离。检查胶带剥离时表面涂层是否脱落。
5.水煮测试
在进行该测试之前,对试样遵照外观检验规范检查,观察外观是否出现麻点针孔等不良缺陷。利用蒸馏水进行该测试。在水温达到80℃后,将试样置于蒸馏水中,并保持30分钟。在测试过程中,试样不能叠层放置。测试完成后2小时以上,将试样于常温(25℃)下放置。
目测观察涂层表面是否存在腐蚀、裂开、气泡、擦掉等现象。之后,在涂层表面贴上405胶带(用手指压实)并将胶带与涂层表面成90度角快速剥离。检查胶带剥离时表面涂层是否脱落。
6.翻滚耐磨测试
将测试样品(烤漆后产品)配成整机,放入震动耐磨仪(R180/530TE30,德国Rosler)中,按照测试标准程序进行测试。测试完成后,测量涂层表面的漆膜剥落面积。
表3.各项性能测试结果
尽管已解释和描述了本发明的特定方面,对本领域技术人员来说很明显的是可做出多种其它改变和修饰而不会背离本发明的精神和范围。因此所附权利要求意图涵盖落入本发明范围内的所有这些改变和修饰。
Claims (9)
1.一种多层涂层体系,其包括第一涂料组合物和第二涂料组合物,其中所述第一涂料组合物包含按该第一涂料组合物的重量计为10-50wt%且玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a)和按该第一涂料组合物的重量计为5-25wt%且玻璃化转变温度(Tg)在30-65℃范围内的丙烯酸树脂(b);而第二涂料组合物包含按该第二涂料组合物的重量计5-25wt%的三官能度聚酯丙烯酸酯、5-25wt%的六官能度聚氨酯丙烯酸酯和5-50wt%的九官能度聚氨酯丙烯酸酯。
2.如权利要求1所述的多层涂层体系,其中所述丙烯酸树脂(a)具有75-90℃的Tg。
3.如权利要求1所述的多层涂层体系,其中所述三官能度聚酯丙烯酸酯是羟基聚酯与丙烯酸的反应产物。
4.如权利要求1所述的多层涂层体系,其中所述六官能度聚氨酯丙烯酸酯是季戊四醇三丙烯酸酯、脂肪族二异氰酸酯和羟基多元醇的缩聚产物。
5.如权利要求1所述的多层涂层体系,其中所述九官能度聚氨酯丙烯酸酯是多异氰酸酯和羟基丙烯酸酯的反应产物。
6.一种在基底上形成多层涂层体系的方法,包括:
(1)将第一涂料组合物施用于所述基底的至少一部分上,形成底漆,和
(2)将第二涂料组合物施用于所述底漆的至少一部分上,形成清漆,
其中所述第一涂料组合物包含按该第一涂料组合物的重量计为10-50wt%且玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a)和按该第一涂料组合物的重量计为5-25wt%且玻璃化转变温度(Tg)在30-65℃范围内的丙烯酸树脂(b);而第二涂料组合物包含按该第二涂料组合物的重量计5-25wt%的三官能度聚酯丙烯酸酯、5-25wt%的六官能度聚氨酯丙烯酸酯和5-50wt%的九官能度聚氨酯丙烯酸酯。
7.一种经涂覆的基底,包括:
(1)基底;和
(2)沉积在所述基底的至少一部分上的多层涂层体系,
其中所述多层涂层体系包括第一涂料组合物和第二涂料组合物,其中所述第一涂料组合物包含按该第一涂料组合物的重量计为10-50wt%且玻璃化转变温度(Tg)为至少70℃的丙烯酸树脂(a)和按该第一涂料组合物的重量计为5-25wt%且玻璃化转变温度(Tg)在30-65℃范围内的丙烯酸树脂(b);而第二涂料组合物包含按该第二涂料组合物的重量计5-25wt%的三官能度聚酯丙烯酸酯、5-25wt%的六官能度聚氨酯丙烯酸酯和5-50wt%的九官能度聚氨酯丙烯酸酯。
8.如权利要求7所述的经涂覆基底,其中所述基底包括由下述物质形成的塑料基底:聚丙烯、丙烯腈-丁二烯-苯乙烯共聚物、玻璃纤维及其任意组合。
9.如权利要求7所述的经涂覆基底,其中所述基底为用于移动电话、个人数码助手、智能手机和个人计算机的基底。
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CN201410353120.XA CN104140724B (zh) | 2014-07-23 | 2014-07-23 | 多层涂层体系、涂覆方法和经其涂覆的基底 |
HK15104472.2A HK1203995A1 (zh) | 2014-07-23 | 2015-05-12 | 多層塗層體系、塗覆方法和經其塗覆的基底 |
AU2015292062A AU2015292062B2 (en) | 2014-07-23 | 2015-07-22 | Multi-layer coating system, coating method, and coated substrate therewith |
KR1020177005017A KR101977515B1 (ko) | 2014-07-23 | 2015-07-22 | 다층 코팅 시스템, 코팅 방법, 및 다층 코팅 시스템으로 코팅된 기재 |
EP15825304.7A EP3172284A4 (en) | 2014-07-23 | 2015-07-22 | Multi-layer coating system, coating method, and coated substrate therewith |
PCT/CN2015/084778 WO2016011944A1 (en) | 2014-07-23 | 2015-07-22 | Multi-layer coating system, coating method, and coated substrate therewith |
BR112017001335A BR112017001335A2 (pt) | 2014-07-23 | 2015-07-22 | sistema de revestimento de múltiplas camadas, método para formar um sistema de revestimento de múltiplas camadas e substrato revestido |
MX2017001053A MX2017001053A (es) | 2014-07-23 | 2015-07-22 | Sistema de revestimiento multicapas, método de revestimiento y sustrato de revestimiento del mismo. |
RU2017105801A RU2655125C1 (ru) | 2014-07-23 | 2015-07-22 | Система многослойного покрытия, способ нанесения покрытия и подложка с покрытием, нанесенным при ее использовании |
US15/328,098 US20170247568A1 (en) | 2014-07-23 | 2015-07-22 | Multi-Layer Coating System, Coating Method, and Coated Substrate Therewith |
CA2955863A CA2955863C (en) | 2014-07-23 | 2015-07-22 | Multi-layer coating system, coating method, and coated substrate therewith |
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CN104140724B (zh) * | 2014-07-23 | 2016-06-08 | Ppg涂料(天津)有限公司 | 多层涂层体系、涂覆方法和经其涂覆的基底 |
CN106634103A (zh) * | 2016-12-30 | 2017-05-10 | Ppg涂料(天津)有限公司 | 防眩光uv固化涂料组合物、涂覆方法和经其涂覆的基底 |
CN106700879B (zh) * | 2016-12-30 | 2019-08-27 | Ppg涂料(天津)有限公司 | 多层涂层体系、涂覆方法和经其涂覆的基底 |
KR102429958B1 (ko) * | 2017-06-21 | 2022-08-09 | 현대자동차주식회사 | 차량의 전파투과 커버용 자외선 경화형 프라이머 |
WO2019105452A1 (zh) * | 2017-11-30 | 2019-06-06 | Ppg涂料(天津)有限公司 | 水性柔软触感涂料组合物和由其形成的耐磨涂层 |
CN108977039A (zh) * | 2018-08-07 | 2018-12-11 | 太仓佩琦涂料有限公司 | 双重固化uv清漆 |
CN109880411A (zh) * | 2018-12-21 | 2019-06-14 | 宁波激智科技股份有限公司 | 一种硬化层涂布液及一种硬化膜 |
CN111961435B (zh) * | 2020-08-25 | 2022-05-13 | Oppo(重庆)智能科技有限公司 | 转印胶及其制备方法、壳体组件及其加工方法、电子设备 |
WO2022182338A1 (en) * | 2021-02-24 | 2022-09-01 | Hewlett-Packard Development Company, L.P. | Covers for electronic devices |
CN112986135A (zh) * | 2021-02-24 | 2021-06-18 | 富思特新材料科技发展股份有限公司 | 一种底漆抗脱落性的测试方法 |
CN113185646A (zh) * | 2021-06-12 | 2021-07-30 | 湖南创瑾科技有限公司 | 导电3d打印材料及其制备方法 |
CN114350246A (zh) * | 2021-12-23 | 2022-04-15 | 广东立邦长润发科技材料有限公司 | 一种用于spc地板的多功能面漆 |
CN116063919B (zh) * | 2022-11-24 | 2024-01-30 | 长沙广欣新材料科技有限公司 | 一种用于三聚氰胺板材uv覆膜上光的附着力树脂 |
CN116426181B (zh) * | 2023-04-28 | 2024-03-08 | 优美特(北京)环境材料科技股份公司 | 水性涂料组合物及由其形成的漆膜 |
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WO2016011944A1 (en) | 2016-01-28 |
CA2955863A1 (en) | 2016-01-28 |
HK1203995A1 (zh) | 2015-11-06 |
BR112017001335A2 (pt) | 2018-03-13 |
AU2015292062A1 (en) | 2017-03-09 |
EP3172284A4 (en) | 2018-02-21 |
CN104140724A (zh) | 2014-11-12 |
MX2017001053A (es) | 2017-07-14 |
CA2955863C (en) | 2018-07-10 |
AU2015292062B2 (en) | 2018-02-22 |
KR101977515B1 (ko) | 2019-05-10 |
EP3172284A1 (en) | 2017-05-31 |
KR20170062445A (ko) | 2017-06-07 |
RU2655125C1 (ru) | 2018-05-23 |
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