CN115003763A - 涂布木材的方法 - Google Patents
涂布木材的方法 Download PDFInfo
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- CN115003763A CN115003763A CN202180011064.XA CN202180011064A CN115003763A CN 115003763 A CN115003763 A CN 115003763A CN 202180011064 A CN202180011064 A CN 202180011064A CN 115003763 A CN115003763 A CN 115003763A
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- monomer
- monomers
- anionic polymer
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Abstract
本发明涉及一种用至少两种水基涂料组合物涂布木材的方法,该方法包括:a)施用包含至少一种Hansch参数≤1.6的阴离子聚合物A的涂料组合物A,并干燥所述水性涂料组合物A或允许其干燥,和b)施用含有至少一种Hansch参数≥1.7的阴离子聚合物B和颜料的涂料组合物B,并干燥所述水性涂料组合物B或允许其干燥,条件是阴离子聚合物B和阴离子聚合物A的Hansch参数相差至少0.5。本发明还涉及相应涂布的木材,以及涂料组合物A作为涂布木材的底涂层的用途,所述涂料组合物A包含Hansch参数≤1.6的水性阴离子聚合物A。
Description
本发明提供了一种通过施用水性聚合物分散体用至少两种水基涂料组合物涂布木材的方法。
用不透明或半不透明的涂料涂装木材,通常会显示出涂层的变色,因为木材成分主要集中在木节中。许多木材类型--例如松木--含有树脂酸、二苯基乙烯、木脂素或单宁等物质。这些成分通常被称为提取物,是天然存在的物质,尤其集中在木节中。根据水溶性提取物的性质,它们通过水分从木材中提取出来,并通过涂层迁移到涂层-空气界面,在那里发色成分集中,并可以色斑(stain)的形式导致变色。这就是所谓的提取物渗色。木节,尤其是许多软木树种的木节,含有大量和高浓度的这些提取物,因此,涂在这些木节上的涂料有很强的变色倾向。这被称为木节渗色。较便宜的木材,如松木,通常含有大量这些木节,因此有很大的倾向显示渗色和着色。
木材通常用底漆(防污(stain blocking)涂料组合物)处理,以密封木材,提高后续面漆的附着力,并抑制发色成分的迁移。鉴于水基涂料的性质,着色剂经常从基材渗入和/或通过涂层,导致涂层表面变色。
US 3,847,857教导了一种基于阳离子水基分散体的底漆涂层。其基本概念是,大部分阴离子着色剂不被聚合物中的阳离子官能团溶解,并被截留在底漆膜中。阳离子聚合物是甲基丙烯酸二甲氨基乙酯、甲基丙烯酸甲酯和二甲基丙烯酸乙二醇酯的共聚物。
WO 2009/007232教导了一种基于阳离子甲基丙烯酸酯低聚物分散体和丙烯酸酯在该低聚物存在下乳液聚合产物的阳离子涂料组合物。该低聚物和聚合物都显示出对单宁渗色和对尼古丁或标记物的防止特性。
这两种教导都是关于阳离子涂料组合,其有严重缺点。阳离子涂料组合物在生产和应用中都会产生问题。制造商在他们的工厂生产不同的涂料组合物。由于所有涂料组合物的大部分是阴离子的,改用阳离子配方会导致结块和强杂质。
美国专利申请2010/0124614公开了一种防污阴离子水性涂料组合物,该组合物包括烯键式不饱和非离子单体与小于1.5%的(甲基)丙烯酸磷酸乙酯和小于3%的甲基丙烯酸共聚的共聚物。即使解决了单宁渗色问题,在像松木这样少单宁的木材上仍然表现出木节渗色。
EP 1149875教导了一种基于苯乙烯、丙烯酸酯和强酸单体甲基丙烯酸磷酸乙酯作为水性防污组合物中粘合剂的共聚物的水性乳液。这种施用在塑料、木材或金属等不同基材上的涂层,通过疏水聚合物中的甲基丙烯酸磷酸乙酯基团络合色斑,防止标记笔或单宁等色斑从木质基材迁移到涂层顶部。
因此,本发明的一个目的是提供一种不透明涂层系统,该涂层系统可容忍制造过程中的杂质,并且显示出高的水稳定性和低的弄脏倾向或提升的耐着色性。
此外,本发明的一个目的是提供一种基于聚丙烯酸酯或聚乙酸乙烯酯的透明底涂层--下文称为底漆--其防止松木木节上的白色面漆变黄。特别是该系统可以防止少单宁的木材(尤其是松木)的木节变色。
此外,本发明的一个目的是提供一种处理木材(特别是松木)以防止着色的方法。
该目的通过用至少两种水基涂料组合物涂布木材的方法来实现,该方法包括:
a)施用包含至少一种Hansch参数≤1.6的阴离子聚合物A的涂料组合物A,并干燥所述水性涂料组合物A或允许其干燥,
b)施用含有至少一种Hansch参数≥1.7的阴离子聚合物B和颜料的涂料组合物B,并干燥所述水性涂料组合物B或允许其干燥,
条件是阴离子聚合物B和阴离子聚合物A的Hansch参数相差至少0.5。
本发明的另一个目的是根据本发明方法涂布的木材。
本发明的另一个目的是涂料组合物A作为涂布木材的底涂层的用途,所述涂料组合物A包含Hansch参数≤1.6的水性阴离子聚合物A。
本发明的另一个目的是一种防污方法,包括应用根据本发明的方法步骤。
此处使用的术语“色斑渗色”是指从木质基材中产生的物质迁移到涂层中,导致可见的变化。
聚合物A至少由单体A1和A2形成。“Hansch参数≤1.6的聚合物A”是指在此选择单体A1和A2以及任选的另外的单体的性质和量,使得聚合物A的Hansch参数≤1.6。
聚合物B至少由单体B1和B2形成。“Hansch参数≥1.7的聚合物B”是指在此选择单体B1和B2以及任选的另外的单体的性质和量,使得聚合物B的Hansch参数≥1.7。
聚合物A的一个基本特征是其Hansch参数≤1.6,有利地在0.4-1.2的范围内,特别有利地在0.6-1.2的范围内。
聚合物B的一个基本特征是其Hansch参数≥1.7,有利地在1.8-4.0的范围内,特别有利地在2.0-4.0的范围内。
根据本发明,阴离子聚合物B和阴离子聚合物A的Hansch参数相差至少0.5,有利地至少1.0,特别有利地至少1.5。
Hansch参数通常是单体M和由其形成的聚合物P的疏水性的度量。
计算Hansch参数的理论考虑来自:Hansch,Fujita,J.Amer.Chem.Soc.,1964,86,第1616-1626页;H.Kubinyi,Methods and Principles of Medicinal Chemistry,第1卷,R.Mannhold et al.,出版社:VCH,Weinheim(1993);C.Hansch和A.Leo,SubstituentConstants for Correlation Analysis,于Chemistry and Biology,Wiley,New York(1979);和C.Hansch,P.Maloney,T.Fujita和R.Muir,Nature,1962,194,第178-180页。
在本文中,单体的Hansch参数通常使用“KOWWIN v1.68”(2010年9月)软件计算,该软件由美国环境保护署(EPA)向公众提供,作为“Estimation Programs InterfaceSuiteTMforWindows,v4.11”[2012],美国环境保护署,华盛顿特区,美国。该程序确定了本文中使用的单体A1和A2以及单体B1和B2的Hansch参数。由于所使用的聚合物1和2或它们的水性聚合物的pH值有利地在中性至微碱性范围内,假定含有酸基团的单体完全去质子化,因此在每种情况下都用指定的盐进行计算。
由单体M形成的聚合物P的Hansch参数通常由以下通式计算:
HPP=x1·HPM1+x2·HPM2+....xn·HPMn
其中,
HPP:计算的由单体M1,M2…Mn形成的聚合物P的Hansch参数
x1,x2,xn:掺入聚合物P的单体M1,M2…Mn的重量比例,以百分比计,其中x1+x2+....xn=1
HPM1,HPM2,HPMn:对各单体M1,M2…Mn计算的各Hansch参数。
例如,由15重量%的丙烯酸铵和85重量%的苯乙烯形成的聚合物,其Hansch参数如下计算:
HPP=x丙烯酸盐·HP丙烯酸盐+x苯乙烯·HP苯乙烯
HPP=0.15·(-2.43)+0.85·2.89=2.09
当以不同单体组成逐步聚合形成聚合物A时,则不同的聚合物被视为一种单体组成计算Hansch参数。
使用该计算方案,根据美国专利申请2010/0124614的发明的实施例的Hansch参数为3.25,比较例的Hansch参数为3.21。对于EP 1149875,最非极性聚合物(实施例2)的Hansch参数为3.1,最极性聚合物(实施例3)的Hansch参数为1.7。
US 5,527,619的聚合物Hansch参数计算值为1.6。
涂料组合物A
根据本发明,涂料组合物A包含至少一种Hansch参数≤1.6的阴离子聚合物A。优选地,阴离子聚合物A是通过包含烯键式不饱和单体A的混合物进行自由基水性乳液聚合而得的。
有用的单体A1包括酸官能化单体,优选所有α,β-单烯键式不饱和C3-至C6-、优选C3-或C4-单羧酸或二羧酸。本发明同样应包括上述羧酸的完全或部分中和的水溶性盐,特别是碱金属盐或铵盐。实例包括丙烯酸、甲基丙烯酸、乙基丙烯酸、衣康酸、烯丙基乙酸、巴豆酸、乙烯基乙酸、富马酸、马来酸、2-甲基马来酸,但也包括烯键式不饱和二羧酸的单酯,例如C1-C8醇的马来酸单烷基酯,以及上述酸的铵盐、钠盐或钾盐。单体A1优选选自丙烯酸、甲基丙烯酸、巴豆酸、富马酸、马来酸、马来酸酐、2-甲基马来酸和衣康酸。然而,根据本发明,丙烯酸和/或甲基丙烯酸特别有利地用作单体A1。
有用的单体A2包括所有非离子型烯键式不饱和单体,并可与之共聚。有用的单体A2的实例包括乙烯基芳香族化合物如苯乙烯,α-甲基苯乙烯,邻氯苯乙烯或乙烯基甲苯,氯乙烯或偏二氯乙烯等乙烯基卤化物,由乙烯醇和由具有1至18个碳原子、优选2至12个碳原子的单羧酸衍生的酯,例如乙酸乙烯酯,丙酸乙烯酯,正丁酸乙烯醇酯,月桂酸乙烯酯和硬脂酸乙烯酯,C1-至C12-烷基乙烯基醚,如甲基乙烯基醚,乙基乙烯基醚,正丙基乙烯基醚,正丁基乙烯基醚,正戊基乙烯基醚,正己基乙烯基醚,由优选具有3至6个碳原子的α,β-单烯键式不饱和的单羧酸和二羧酸(具体实例为丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸)与一般具有1至12个、优选1至8个、特别是1至4个碳原子的烷醇衍生的酯,具体实例为丙烯酸和甲基丙烯酸的甲基、乙基、正丁基、异丁基、戊基、己基、庚基、辛基、壬基、癸基和2-乙基己基酯,富马酸和马来酸的二甲基或二正丁基酯,α,β-单烯键式不饱和羧酸的腈,例如丙烯腈、甲基丙烯腈、富马酸腈、马来腈,以及C4-8共轭二烯,如1,3-丁二烯(丁二烯)和异戊二烯。一种有用的单体也是乙烯。上述单体占所有单体A2总量的比例一般≥60重量%,优选≥80重量%,特别优选≥95重量%,从而构成主要单体A2。优选地,根据本发明,聚合物A包括作为主要单体A2的以下物质,即丙烯酸或甲基丙烯酸与C1-C12醇的酯,特别是丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯或甲基丙烯酸甲酯,乙烯基芳香族化合物,特别是苯乙烯或α-甲基苯乙烯,α,β-单烯键式不饱和羧酸的腈,特别是丙烯腈,和/或共聚形式的C2-C12单羧酸的乙烯基酯。
其他有用的单体A2在较小程度上是那些烯键式不饱和单体,其包含至少一个磺基和/或其相应阴离子或至少一个氨基、酰胺基、脲基或N-杂环基和/或其氮质子化或烷基化的铵衍生物。实例包括丙烯酰胺和甲基丙烯酰胺;以及乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸、苯乙烯磺酸及其水溶性盐,以及N-乙烯基吡咯烷酮、2-乙烯基吡啶、4-乙烯基吡啶、2-乙烯基咪唑、2-(N,N-二甲氨基)丙烯酸乙酯、2-(N,N-二甲氨基)甲基丙烯酸乙酯、2-(N,N-二乙氨基)丙烯酸乙酯、2-(N,N-二乙氨基)甲基丙烯酸乙酯、2-(N-叔丁基氨基)甲基丙烯酸乙酯、N-(3-N′,N′-二甲氨基丙基)甲基丙烯酰胺,和甲基丙烯酸2-(1-咪唑啉-2-酮)乙酯。上述单体A2的用量一般为≤10重量%,优选≤5重量%,特别是≤1重量%,每种情况下基于单体A2的总量计。
根据本发明可使用的其他单体A2是官能化的烯键式不饱和化合物,选自丙烯酸乙酰乙酰氧基乙酯、丙烯酸乙酰乙酰氧基丙酯、丙烯酸乙酰乙酰氧基丁酯、甲基丙烯酸乙酰乙酰氧基乙酯、甲基丙烯酸乙酰乙酰氧基丙酯、甲基丙烯酸乙酰乙酰氧基丁酯、双丙酮丙烯酰胺和双丙酮甲基丙烯酰胺。上述单体A2的用量一般为≤15重量%,优选≤8重量%,特别是≤3重量%,每种情况下基于单体A2的总量计。
通常提高由聚合物基质形成的膜的完整性的单体A2一般具有至少一个环氧基、至少一个羰基或至少两个非共轭的烯键式不饱和双键。这些单体的实例是具有两个乙烯基部分的单体,具有两个亚乙烯基部分的单体,以及具有两个烯基部分的单体。这里特别有利的单体是二元醇与α,β-单烯键式不饱和单羧酸的二酯,其中优先考虑丙烯酸和甲基丙烯酸。具有两个非共轭的烯键式不饱和双键的这类单体的实例是亚烷基二醇二丙烯酸酯和亚烷基二醇二甲基丙烯酸酯,例如乙二醇二丙烯酸酯、1,2-丙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯和乙二醇二甲基丙烯酸酯、1,2-丙二醇二甲基丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯,以及二乙烯基苯、甲基丙烯酸乙烯酯、丙烯酸乙烯酯、甲基丙烯酸烯丙酯、丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、亚甲基双丙烯酰胺、丙烯酸环戊二烯酯、三烯丙基氰尿酸酯和三烯丙基异氰尿酸酯。上述单体A2的用量一般为≤5重量%,优选≤3重量%,特别优选≤1.5重量%,每种情况下基于单体A2的总量计。
然而,优选使用的单体A2选自乙酸乙烯酯、乙烯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸正丁酯、甲基丙烯酸正丁酯和/或丙烯酸2-乙基己酯。
因此,有利的是,所述至少一种聚合物A以共聚形式包括作为单体A1的丙烯酸和/或甲基丙烯酸,以及作为单体A2的乙酸乙烯酯、乙烯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸正丁酯、甲基丙烯酸正丁酯和/或丙烯酸2-乙基己酯。
优选地,阴离子聚合物A通过包含烯键式不饱和单体A的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.1至≤5重量%的至少一种酸官能化单体作为单体A1,基于单体A的总量计,优选丙烯酸和/或甲基丙烯酸,以及
-95至99.9重量%的至少一种非离子单体作为单体A2,基于单体A的总量计,优选至少60重量%的单体A2选自乙酸乙烯酯、乙烯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸正丁酯、甲基丙烯酸正丁酯和丙烯酸2-乙基己酯,且至多40重量%的单体A2为其它单体A2。
根据一个优选的实施方案,阴离子聚合物A通过包含烯键式不饱和单体A的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.1至≤5重量%的单体A1,基于单体A的总量计,所述单体A1是丙烯酸和/或甲基丙烯酸,以及
-95至99.9重量%的至少一种非离子单体作为单体A2,基于单体A的总量计,而至少60重量%的单体A2选自丙烯酸乙酯、丙烯酸甲酯和甲基丙烯酸甲酯,特别优选丙烯酸乙酯,且至多40重量%的单体A2是其它单体A2。
根据另一优选的实施方案,阴离子聚合物A通过包含烯键式不饱和单体A的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.1至≤5重量%的单体A1,基于单体A的总量计,所述单体A1是丙烯酸和/或甲基丙烯酸,以及
-95至99.1重量%的至少一种非离子单体作为单体A2,基于单体A的总量计,而至少60重量%的单体A2选自乙酸乙烯酯和乙烯,且至多40重量%的单体A2为其它单体A2。
在水性介质中烯键式不饱和化合物(单体)进行自由基引发的乳液聚合已经被广泛描述,因此对本领域技术人员来说是众所周知的[关于这方面,参见《聚合物科学与工程百科全书》(Encyclopedia of Polymer Science and Engineering),第8卷,第659页以下的Emulsionspolymerisation[乳液聚合](1987);D.C.Blackley,《高聚物胶乳》(HighPolymer Latices),第1卷,第35页以下(1966);H.Warson,《合成树脂乳液的应用》(TheApplications of Synthetic Resin Emulsions),第5章,第246页以下(1972);D.Diederich,Chemie in unserer Zeit 24,第135至142页(1990);《乳液聚合》(EmulsionPolymerisation),Interscience Publishers,New York(1965);DE-A-4003 422和Dispersionen synthetischer Hochpolymerer[合成高聚物的分散体],F.Springer-Verlag,Berlin(1969)]。自由基引发的水性乳液聚合通常是通过将单体(通常同时包含如乳化剂和/或保护胶体等分散助剂)分散在水性介质中,并使用至少一种水溶性自由基聚合引发剂使其聚合来实现。经常使用本领域技术人员同样已知的化学和/或物理方法来减少所获得的水性聚合物分散体中未转化单体的残留含量[参见例如EP-A 771328、DE-A 19624299、DE-A 19621027、DE-A19741184、DE-A 19741187、DE-A 19805122、DE-A19828183、DE-A19839199、DE-A 19840586和19847115],通过稀释或浓缩将聚合物固含量调节到所需的值,或者向水性聚合物分散体中添加其他常规添加物,例如泡沫调节添加剂或粘度调节添加剂。
阴离子聚合物A的制备可能是一个多阶段聚合过程,即对两种或多种不同的单体混合物进行两个或多个阶段的连续聚合。这是本领域技术人员原则上已知的。因此,对于根据EP-A574803的发明EP-A中实施例1至10的所有实施例,或EP-A1732962的所有实施例,公开了合适的制备方法。因此,所述至少一种聚合物A可以纯形式(本体)或溶解在适当的溶剂中或分散在适当的液体介质中。
聚合后获得的水性聚合物分散体A包括重均粒径在≥10且≤800nm的范围内、有利地在≥20且≤400nm的范围内、特别是在≥30且≤150nm的范围内的聚合物颗粒。
涂料组合物B
根据本发明,涂料组合物B包含至少一种Hansch参数≥1.7的阴离子聚合物B。优选地,阴离子聚合物B是通过包含烯键式不饱和单体B的混合物进行自由基水性乳液聚合得到的。
这里,单体B1对应于单体A1,单体B2对应于单体A2(如上所述),除了选择这些单体的性质和量以使由此获得的聚合物B具有≥1.7的Hansch参数之外。
所用的单体B1优选为丙烯酸和/或甲基丙烯酸,所用的单体B2优选为苯乙烯、α-甲基苯乙烯、甲基丙烯酸甲酯、丙烯酸正丁酯和/或丙烯酸2-乙基己酯。
在聚合物B的制备中,根据本发明,单体B1的总量≤5重量%,优选≤3重量%,特别优选≤0.5重量%,单体B2的总量相应地≥95重量%,优选≥97重量%,特别优选≥99.5重量%。
优选地,阴离子聚合物B通过包含烯键式不饱和单体B的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.5至≤5重量%的至少一种酸官能化单体作为单体B1,基于单体B的总量计,优选丙烯酸和/或甲基丙烯酸
-95至99.5重量%的至少一种非离子单体作为单体B2,基于单体B的总量计,优选至少60%的单体B2选自苯乙烯和C4-C10-烷基丙烯酸酯,优选选自苯乙烯、α-甲基苯乙烯、甲基丙烯酸甲酯、丙烯酸正丁酯和丙烯酸2-乙基己酯,且至多40重量%的单体B2为其它单体B2。
根据一个优选的实施方案,阴离子聚合物B通过包含烯键式不饱和单体B的混合物进行自由基水性乳液聚合得到,其中所述单体混合物包括:
-0.5至≤5重量%的单体B1,基于单体B的总量计,所述单体B1为丙烯酸和/或甲基丙烯酸,以及
-95至99.5重量%的至少一种非离子单体作为单体B2,基于单体B的总量计,而至少60重量%的单体B2由苯乙烯和至少一种C4-C10-烷基丙烯酸酯组成,优选所述C4-C10-烷基丙烯酸酯选自丙烯酸正丁酯、甲基丙烯酸正丁酯和丙烯酸2-乙基己酯,且至多40重量%的单体B2是其它单体B2。
根据另一优选的实施方案,阴离子聚合物B是通过包含烯键式不饱和单体B的混合物进行自由基水性乳液聚合得到的,其中所述单体混合物包括:
-0.1至≤5重量%的单体B1,基于单体B的总量计,所述单体B1为丙烯酸和/或甲基丙烯酸,以及
-95至99.1重量%的至少一种非离子单体作为单体B2,基于单体B的总量计,而至少60重量%的单体B2由甲基丙烯酸甲酯和至少一种C4-C10-烷基丙烯酸酯组成,优选所述C4-C10-烷基丙烯酸酯选自丙烯酸正丁酯、甲基丙烯酸正丁酯和丙烯酸2-乙基己酯,并且至多40重量%的单体B2是其它单体B2。
所述至少一种阴离子聚合物B的制备原则上是本领域技术人员已知的,并且与上述阴离子聚合物A的制备类似。
聚合后获得的水性聚合物分散体B包括重均粒径在≥10nm且≤800nm的范围内、有利地在≥20nm且≤400nm的范围内、特别是在≥30nm且≤150nm的范围内的聚合物颗粒。
本发明的水基涂料组合物B包含至少一种阴离子聚合物和颜料。所用的颜料原则上可以是本领域技术人员熟悉的任何白色或彩色颜料。根据CDChemie Lexikon-Version 1.0,Stuttgart/New York:Georg Thieme Verlag 1995参考DIN 55943,颜料应理解为指几乎不溶于应用介质的颗粒状无机或有机、有色或无色的染色剂。
由于其高折射率(金红石型:2.70,锐钛矿型:2.55)和良好的遮盖性,应提及各种二氧化钛同质异形体作为最重要的白色颜料。另外,氧化锌和硫化锌也可用作白色颜料。这些白色颜料可以表面涂布或未涂布的形式使用。另外,也可使用有机白色颜料,例如富含苯乙烯和羧基并具有约300至400nm粒径的非成膜中空聚合物颗粒(称为不透明颗粒)。
除了白色颜料外,可以使用本领域技术人员熟悉的各种不同颜色的颜料来完成染色,例如,价格稍低的无机铁氧化物或硫化物、镉氧化物或硫化物、铬氧化物或硫化物和铅氧化物或硫化物、钼酸铅、钴蓝或炭黑,以及价格稍高的有机颜料,例如酞菁、偶氮颜料、喹吖啶酮、苝或咔唑。然而,根据本发明,优选使用二氧化钛,特别是金红石形式的二氧化钛作为至少一种颜料。
优选的是二氧化钛、碳酸钙、粘土、滑石,最优选的是二氧化钛。
涂层一旦施用,可在环境温度下自然干燥,更优选在10-80℃范围内的温度下,最优选在25-60℃之间。
根据本发明,用至少两种水基涂料组合物涂布木材的方法包括施用和干燥涂料组合物A以及施用和干燥涂料组合物B。涂料组合物A可以作为一层、两层或多层施用,优选作为一层。此外,可以将涂料组合物B作为一层、两层或更多层施用,优选作为一层。
在优选的实施方案中,阴离子聚合物A是通过单体混合物进行自由基水性乳液聚合得到的,所述单体混合物包括基于单体A总量的0.1至≤5重量%的丙烯酸和基于单体A总量的95至99.1重量%的至少一种非离子单体A2,而至少60重量%的单体A2选自乙酸乙烯酯和丙烯酸乙酯;
阴离子聚合物B是通过单体混合物进行自由基水性乳液聚合得到的,所述单体混合物包括基于单体B总量的0.5至≤5重量%的丙烯酸和/或甲基丙烯酸和基于单体B总量的95至99.5重量%的至少一种非离子单体B2,而至少60重量%的单体B2是苯乙烯。
涂料组合物A和/或B可施用于各种木材和木材复合材料,如单板。软木和硬木都可以应用,更特殊的种类有松木、云杉木、榉木、橡木、胡桃木、樱桃木、桉木和梣木。优选富含树脂化合物的种类,最优选的是松木。
可通过任何常规方法施用到基材上,包括刷涂、浸渍、流涂、喷涂、辊涂和垫涂。
在本发明方法中使用的涂料组合物A和/或B还可以包括本领域技术人员在性质和量方面熟悉的其他常规助剂,例如填料、可溶性染料、光学增白剂、保持剂、润湿剂、成膜助剂、消泡剂、防腐剂、杀菌剂、粘液控制剂、增塑剂、抗粘连剂、缓冲物质、疏水剂等。
所用的填料基本上是无机材料,与颜料相比具有较低的折射率(根据DIN 55943和DIN 55945,白色填料的折射率值<1.7)。粉状填料通常是天然存在的矿物,例如方解石、白垩、白云石、高岭土、滑石、云母、硅藻土、重晶石、石英或滑石/绿泥石组合,但也有合成的无机化合物,例如沉淀碳酸钙、煅烧高岭土或硫酸钡和气相二氧化硅。所用的填料优选为结晶方解石或无定形白垩形式的碳酸钙。
任选地,涂料组合物A和/或B还可以包括至少一种优选用作成膜助剂的有机溶剂。为此,有用的实例包括芳香烃,如溶剂石脑油、苯、甲苯、二甲苯,或例如作为100、150或200出售的芳香烃混合物,氯苯,酯类如乙酸乙酯、乙酸丁酯、乙二醇一甲醚乙酸酯、乙二醇乙酸酯、甲氧基丙基乙酸酯、2,2,4-三甲基戊烷-1,3-二醇单异丁酸酯(来自Eastman的)、二丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单甲醚乙酸酯,醚类如丁二醇、四氢呋喃、二噁烷、乙二醇醚、二乙二醇单乙醚、二乙二醇单甲醚、二乙二醇单正丁基醚、二乙二醇单正己基醚、二乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二正丁基醚、二乙二醇二正己基醚、乙二醇二-2-乙基己基醚、乙二醇二正丁基醚、乙二醇二正己基醚、乙二醇二正丙基醚、二丙二醇二甲醚、二丙二醇单甲醚、二丙二醇单正丁基醚、二丙二醇单正丙基醚、二丙二醇单叔丁基醚、二丙二醇二叔丁基醚、丙二醇单乙醚、丙二醇单甲醚、丙二醇单正丙基醚、丙二醇单苯醚、丙二醇单叔丁基醚、丙二醇二苯醚、丙二醇单正丁基醚、三丙二醇单甲醚和聚烯丙基缩水甘油醚,酮类如丙酮、甲乙酮,卤代有机溶剂如二氯甲烷或三氯单氟乙烷或其他有机溶剂,例如苯甲醇、邻苯二甲酸二丁酯、丙二醇、磷酸三(丁氧基乙基)酯。
成膜助剂的使用特别是为了降低乳液聚合物的最低成膜温度,从而有助于良好的成膜。
涂料组合物A可以含有颜料。优选其不含颜料。
根据本发明施用的涂料组合物B通常具有≥0%且≤60%、有利地≥5%且≤40%、特别有利地≥10%且≤30%的颜料体积浓度。颜料体积浓度(PVC)在这里被理解为颜料和填料的体积乘以100,除以粘合剂聚合物的体积加上颜料和填料的体积。
特别重要的是,本发明还包括涂料组合物,特别是用于特定使用领域的涂料制剂,尤其是,
包含以下物质的覆面木材清漆(以固体计)
≥15重量%且≤60重量%的全部聚合物(=聚合物A和聚合物B之和)
≥0重量%且≤20重量%的成膜助剂
≥1重量%且≤40重量%的颜料
≥0重量%且≤50重量%的填料
≥0.1重量%且≤5重量%的分散助剂
≥0重量%且≤20重量%的增稠剂,以及
≥0重量%且≤30重量%的其它助剂,如缓冲物质、杀生物剂等,
基于所述水性涂料制剂的固含量计。
重要的是,有利地用碱、特别是氨或氨水溶液将涂料组合物A和/或B的pH值调节到≥7.5且≤10.0、特别有利地≥8.0且≤9.0范围内。
有利的是,首先将涂料组合物A和/或B施用到基材表面,然后在等于或大于本发明的水性聚合物分散体或其水性制剂的最低成膜温度(MFT)的温度T[T≥MFT]下干燥。有利的是,干燥温度T≥(MFT+5)℃,特别有利的是T≥(MFT+10)℃,尤其是T≥(MFT+20)℃。
在本文的上下文中,MFT应理解为指根据2001年4月的DIN ISO2115实验测定的温度,低于该温度时水性聚合物分散体不形成连续的聚合物膜。
优选阴离子聚合物A和B独立地具有在-20℃至60℃范围内的玻璃化转变温度,更优选聚合物A具有在-10℃至40℃范围内的玻璃化转变温度,第二种聚合物B具有在10℃至60℃范围内的玻璃化转变温度,最优选聚合物B具有在25℃至50℃范围内的玻璃化转变温度。
本领域技术人员知道根据Fox(T.G.Fox,Bull.am.Phys.Soc.1956
[Ser.II]1,第123页)和Ullmann’sder technischen Chemie,Bd.19,Seite 18,4.30Auflage,Verlag Chemie,Weinheim,1980)不交联或仅弱交联的聚合物的玻璃化转变温度可以很好地根据下式估算:
1/Tg=x1/Tg1+x2/Tg2+....xn/Tgn,
其中x1,x2,....xn是单体1,2,....n的摩尔分数,Tg1,Tg2,....Tgn为单体1,2,....n各自的均聚物的玻璃化转变温度,以开尔文计。大多数烯键式不饱和单体各自的均聚物的玻璃化转变温度是已知的,或者可以很容易地测量,例如在J.Brandrup,E.H.Immergut,Polymer Handbook第1版J.Wiley,New York,1966,第2版J.Wiley,NewYork,1975和第3版J.Wiley,New York,1989,或Ullmann’s Encyclopedia of IndustrialChemistry,第169页,Verlag Chemie,Weinheim,1992中所述。
根据本发明,重要的是,选择含水制剂的量,使得施用到基材上的涂层A和/或涂层B在干燥后具有≤2mm、有利地≥0.01mm且≤1.5mm,特别有利地≥0.05mm且≤0.5mm的层厚度。可以理解,根据本发明,可以将两层或更多相同或不同的涂层依次施用到基材上。
本发明提供了一种不透明涂层系统,其可容忍制造过程中的杂质。它还表现出较高的水稳定性。施用到木材上的涂层表现出较低的弄脏倾向或提升的耐着色性。
本发明提供了一种优选地基于聚丙烯酸酯或聚乙酸乙烯酯的透明底涂层,其防止在少单宁的木材(特别是松木节)上的白色面漆变色和变黄。
本发明还涉及根据本发明方法涂布的木材,优选松木。
本发明还涉及一种涂料组合物A作为涂布木材的底涂层的用途,该涂料组合物A包括Hansch参数≤1.6的水性阴离子聚合物A。以上描述了合适的阴离子聚合物A。优选阴离子聚合物A是被引为优选聚合物的那些聚合物,即以共聚形式包括作为单体A1的丙烯酸和/或甲基丙烯酸以及作为单体A2的乙酸乙烯酯、乙烯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯丙烯酸正丁酯、甲基丙烯酸正丁酯和/或丙烯酸2-乙基己酯的聚合物A。尤其优选的是上述聚合物A的优选实施方案。
最后,本发明提供了一种用于防污的方法,其包括应用本发明的方法。
本发明将通过以下非限制性实施例来阐明。
实施例
除非上下文另有说明,百分比总是以重量计。如果没有另外说明,报告的含量基于水溶液或分散体中的含量。
根据ISO 3251标准测定固含量。
根据ISO 976标准测定pH值。
根据ISO16808标准测定最低成膜温度。
根据DIN EN ISO 11357-2(2013-09)测定玻璃化转变温度(Tg)(差热分析,中点温度,升温速率20K/min)。
采用高性能粒度仪(Malvern)在22℃和633nm波长下,根据ISO13321标准测定聚合物分散体的重均粒径。
聚合物分散体D1的制备:
在4L反应器中通过氮气使其惰性化10分钟,然后加入700g去离子水、25g粒径为33nm的33%聚苯乙烯种子胶乳。将含有上述进料的反应器加热到85℃并在整个合成时间内进行搅拌。在85℃下加入5g7重量%的过氧硫酸钠水溶液。加入后,开始进行乳液进料,并在210分钟内进料。在乳液进料的同时,开始进料95g 7重量%的过氧硫酸钠水溶液,并在240分钟内进料到反应器中。引发剂进料结束后,反应混合物冷却至75℃。然后在5分钟内向反应混合物中加入43g 8重量%的氢氧化钠水溶液。之后,在60分钟内加入26g 10重量%的叔丁基过氧化氢水溶液和20g 13重量%的亚硫酸钠溶液。进料结束后,将反应混合物冷却至室温。
将520g去离子水、26g脂肪醇聚乙二醇醚硫酸酯的钠盐和6.5g十二烷基硫酸钠以及1278g由16重量%的丙烯酸正丁酯、14重量%的丙烯酸2-乙基己酯、57重量%的苯乙烯、10重量%的甲基丙烯酸甲酯和3重量%的丙烯酸组成的单体混合物混合以制备乳液进料。
所得的胶乳D1的固含量为48.1重量%,动态光散射法测定粒径为146nm。pH值为6.9。玻璃化转变温度测定为40℃。
分散体Dx(x=1至x=7)的制备
分散体Dx的制备与分散体D1的制备过程相同,只是使用了表1中的各单体混合物。结果汇总在表2中。
表1:聚合物A和B的单体组成
nBA=丙烯酸正丁酯
EHA=丙烯酸2-乙基己酯
EA=丙烯酸乙酯
S=苯乙烯
BMA=甲基丙烯酸正丁酯
MMA=甲基丙烯酸甲酯
AA=丙烯酸
MAA=甲基丙烯酸
wt%=重量%
表2:分散体D1至D7和比较分散体D8至D10的特性
Tg=玻璃化转变温度
*由Tg估计
分散体D8、D9和D10是基于单体乙酸乙烯酯的市售产品。单体组成是在聚合物仅由乙酸乙烯酯和乙烯组成的假设下,使用玻璃化转变温度和Fox方程计算出来的。根据该理论组成,计算出相应的Hansch参数。
D9:Mowilith LDM 1871(Celanese),理论单体组成:82重量%乙酸乙烯酯;18重量%乙烯;
TiO2-浆料的制备:
将14.6g自来水放入100ml容器中。在水中加入6.2g Dispex Ultra PX 4575(BASFSE)作为分散剂。然后加入0.3g Hydropalat WE 3650(BASF SE)作为润湿剂和0.3gFoamstar SI 2210(BASF SE)作为消泡剂。随后加入78g Kronos 2190,一种来自KronosWorldwide的二氧化钛(TiO2)。将混合物在Ultraturrax中以每分钟5000转搅拌10分钟以分散TiO2。
漆的制备
透明漆(CLx)的制备:
将100g分散体Dx用自来水稀释到200mPas的粘度(Brookfield,25℃,主轴2,每分钟20转)是必要的。然后加入10%的氨水溶液,使pH值达到8.5。随后,加入0.5%的WE 3221(BASF SE)作为润湿剂和0.5%的Byk 24(BYK)作为消泡剂。随后,加入6g乙二醇丁基醚作为聚结剂。搅拌10分钟,产生CLx。
着色(“白色”)漆(PLx)的制备:
用相应的透明漆CLX制备着色漆PLx。通过添加TiO2浆料,制备着色漆。向80g透明漆CLx中加入20g TiO2浆料,并搅拌10分钟。
涂布木材的方法:
使用新切割的含木节的木材种类,测试漆对木材中有色物质渗透的阻隔性能。以使木材中的木节减半的方式切割木片。使用的木材是松木,在德语中是“Zirbelkiefer”。
之后,对新切割的木材使用狭缝为200μm的狭缝式涂布机涂上相应的漆。整个表面包括切成两半的木节被涂上漆。
第一涂层(组合物A),即“底漆”在实验室中于25℃下干燥24小时。随后,施用第二涂层(组合物B),即“面漆”。涂有底漆和面漆的木片在实验室中于25℃下干燥14天。
测试
随后,将经涂布的木材放入试验室进行72小时人工风化。在试验室内,使用氙弧灯对经涂布的干燥木材照射102分钟,然后在木材上喷水18分钟。102分钟的照射和18分钟的喷水相当于1个周期。在72小时内,对经涂布的木材施以36个周期。该试验程序根据ENISO4892-2:2013程序A,周期1。
根据木节上白色涂层的变色,对经涂布的木材进行目测评级。
0级:无可见变色
1级:可见轻微的、黄褐色变色。
2级:可见明显的变色。
表3:用组合物A和组合物B进行涂布处理所得的涂层的应用测试结果
E:实施例
CE:比较例
HPA:聚合物A的Hansch参数;
HPB:聚合物B的Hansch参数
结果:风化后变色的评级
从实验数据可以看出,只有Hansch参数小于1.6的极性聚合物与Hansch参数大于1.6的非极性聚合物的组合才能阻止变色。两种Hansch参数均低于1.6的聚合物或Hansch参数低于1.6的单一聚合物作为底漆和面漆施用两次阻止变色。此外,两种聚合物或单一聚合物施用两次,其Hansch参数大于1.6也不能阻止变色。
Claims (14)
1.一种用至少两种水基涂料组合物涂布木材的方法,该方法包括:
a)施用包含至少一种Hansch参数≤1.6的阴离子聚合物A的涂料组合物A,并干燥所述水性涂料组合物A或允许其干燥,
b)施用含有至少一种Hansch参数≥1.7的阴离子聚合物B和颜料的涂料组合物B,并干燥所述水性涂料组合物B或允许其干燥,
条件是阴离子聚合物B和阴离子聚合物A的Hansch参数相差至少0.5。
2.根据权利要求1所述的方法,其中阴离子聚合物B和阴离子聚合物A的Hansch参数相差至少0.7。
3.根据权利要求1或2所述的方法,其中所述阴离子聚合物A通过包含烯键式不饱和单体A的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.1至≤5重量%的至少一种酸官能化单体作为单体A1,基于单体A的总量计,以及
-95至99.9重量%的至少一种非离子单体作为单体A2,基于单体A的总量计。
4.根据权利要求1-3中任一项所述的方法,其中所述阴离子聚合物A由以下物质形成:
-0.1至≤5重量%的至少一种酸官能化单体作为单体A1,基于单体A的总量计,以及
-95至99.9重量%的至少一种非离子单体作为单体A2,基于单体A的总量计,而至少60重量%的单体A2选自乙酸乙烯酯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸正丁酯、甲基丙烯酸正丁酯和丙烯酸2-乙基己酯,且至多40重量%的单体A2为其它单体A2。
5.根据权利要求1-4中任一项所述的方法,其中所述阴离子聚合物B通过包含烯键式不饱和单体B的混合物进行自由基水性乳液聚合而得到,其中所述单体混合物包括:
-0.5至≤5重量%的至少一种酸官能化单体作为单体B1,基于单体B的总量计,以及
-95至99.5重量%的至少一种非离子单体作为单体B2,基于单体B的总量计。
6.根据权利要求1-5中任一项所述的方法,其中所述阴离子聚合物B由以下物质形成:
-0.5至≤5重量%的至少一种酸官能化单体作为单体B1,基于单体B的总量计,以及
-95至99.5重量%的至少一种非离子单体作为单体B2,基于单体B的总量计,而至少60%的单体B2选自苯乙烯、α-甲基苯乙烯、甲基丙烯酸甲酯、丙烯酸正丁酯和丙烯酸2-乙基己酯,且至多40重量%的单体B2为其它单体B2。
7.根据权利要求3-6中任一项所述的方法,其中所述作为单体A1和/或B1的酸官能化单体是丙烯酸和/或甲基丙烯酸。
8.根据权利要求1-7中任一项所述的方法,其中所述颜料选自二氧化钛、碳酸钙、粘土和滑石。
9.根据权利要求1-8中任一项所述的方法,其中
-所述阴离子聚合物A是通过单体混合物进行自由基水性乳液聚合得到的,所述单体混合物包括基于单体A总量的0.1至≤5重量%的丙烯酸和基于单体A总量的95至99.1重量%的至少一种非离子单体A2,而至少60重量%的单体A2选自乙酸乙烯酯和丙烯酸乙酯;
-所述阴离子聚合物B是通过单体混合物进行自由基水性乳液聚合得到的,所述单体混合物包括基于单体B总量的0.5至≤5重量%的丙烯酸和/或甲基丙烯酸和基于单体B总量的95至99.5重量%的至少一种非离子单体B2,而至少60重量%的单体B2是苯乙烯。
10.根据权利要求1至9中任一项所述的方法,其中所述阴离子聚合物A和B独立地具有在-20℃至60℃范围内的玻璃化转变温度。
11.根据权利要求1-10中任一项所述的方法涂布的木材。
12.根据权利要求10所述的涂布的木材,其中所述木材是松木。
13.包含Hansch参数≤1.6的水性阴离子聚合物A的涂料组合物A作为涂布木材的底涂层的用途。
14.一种用于防污的方法,其包括应用根据权利要求1-10中任一项所述的方法。
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