CN105073816A - 基于可交联含氟聚合物的表面涂层 - Google Patents
基于可交联含氟聚合物的表面涂层 Download PDFInfo
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- CN105073816A CN105073816A CN201480013873.4A CN201480013873A CN105073816A CN 105073816 A CN105073816 A CN 105073816A CN 201480013873 A CN201480013873 A CN 201480013873A CN 105073816 A CN105073816 A CN 105073816A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/14—Homopolymers or copolymers of vinyl fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及用基于包含可交联含氟聚合物的配制剂的高级耐磨表面涂层处理暴露在户外使用的材料的技术。本发明还涉及该表面涂层的特定实施方案。
Description
技术领域
本发明涉及用基于包含可交联含氟聚合物的配制剂的高级耐磨表面涂层处理暴露在户外使用的材料的技术。本发明还涉及该表面涂层的特定实施方案。
背景技术
户外使用的材料不可避免地暴露在磨损下。这样的磨损特别由清洁工艺或由风载介质,如沙或灰尘造成。因此,未受保护的或表面涂布不足的材料失去它们的价值或长期粘合。热塑性聚合物材料的仅具有低的耐磨性,它们因此不适用于或仅极有限地适用于暴露在户外使用的材料的表面涂布。
户外使用的材料另外遭受由太阳辐射的UV部分导致的显著负荷。高级表面涂层因此必须同样确保对基底的显著防UV辐射的保护,而本身不受到由UV辐射造成的可能的内在破坏。
例如,柔性薄膜太阳能电池组件和柔性OLED或显示器材料另外在户外使用中遭受必要功能层的明显的可能的腐蚀。因此,在这些应用行业中,高性能表面涂层必须同样提供适当的防腐蚀保护以及对水分迁移的阻隔性质。
现有技术
户外使用的涂料用的已知材料的实例是聚硅氧烷,如SDCTechologiesInc.公司的CRYSTALCOATTMMP-100、都得自MomentivePerformanceMaterials公司的AS400-SHP401或UVHC3000K。但是,在如特别对于太阳光反射器或光伏电池所要求的那样在户外区域中经至少20年时间的长期使用中,此类材料没有表现出足够的耐磨性。
在US5,118,540中,通过粘合施加上基于氟碳聚合物,如PVDF的耐磨防潮膜片来改进表面保护。UV吸收剂以及缓蚀剂都是用于将该膜片与气相涂布的聚酯载体膜的金属表面接合的粘合剂层的组分。此处,粘合剂层又可类似于上述(甲基)丙烯酸酯双涂层由两个不同的层构成,以将缓蚀剂与UV吸收剂彼此分开。但是,这种涂层没有表现出足够的长期抗划伤性。
现有技术中的另一解决方案是无机防划涂层。EP1629053公开了用于涂布可用作耐候膜片的膜片层压材料的由直径小于1微米的二氧化硅粒子或氧化铝粒子构成的这种涂层。但是,此类无机涂层的一个缺点在于,它们在风化条件下仅耐用相对较短时间,即不超过数年。由吹沙或甚至沙尘暴,或在极热,尤其是干燥环境中的其它气候条件造成此类涂层的磨损。
EP2524802公开了用于太阳能装置的耐候保护的涂层,其包含采用异氰酸酯交联的、羟基官能的含氟聚合物。这些涂层已具有极好的耐磨性和耐候稳定性。但是,问题是可用性有限,因为这些涂层与许多基底的粘合性只是有限的。用于相同用途的类似体系可见于WO2011/105515。
WO98/44015公开了包含多异氰酸酯、羟基官能的含氟聚合物和羟基官能的未氟化多元醇(其除了是低分子量二醇外还是聚酯多元醇、聚醚多元醇或聚碳酸酯多元醇)的组合物。但是,尤其就耐候性而言,此类组合物还能改进。
EP2298842公开了用于例如汽车制造的涂料,其由聚醚基多异氰酸酯预聚物和不含氟的多元醇形成。此类组合物具有极好的耐候性质和对汽车制造而言足够的耐磨性。但是,对户外领域中处于机械负荷下的其它用途而言,耐磨性不足。
发明内容
技术问题
技术问题在于提供用于塑料表面或金属表面的新型的表面调质。在户外用途中使用这种表面调质应同时确保特别好的耐磨性、抗划伤性、耐候性和基底保护性质。
另外,这种表面调质应可以设计为透明和/或无色的。此外,这种表面调质应提供良好的耐化学性,对例如水蒸汽或氧气的阻隔性质,和防污性质。
另一问题在于该表面调质还在待涂布的基底和要用的涂布技术方面都应具有广泛可用性。
另一问题在于提供在制备和施加上容易且成本有效的用于户外用途的表面调质。
可以从本申请的说明书、权利要求书或实施例中看出没有明确提及的其它问题。
解决方案
在现有技术和其中描述的对于长期用途仅不足的技术方案的背景下,本发明中以本领域技术人员不可容易预见的方式成功提供了具有经长时间改进的表面品质的涂层。这借助用于涂布基底的新型组合物成功实现,所述组合物包含5至70重量%,优选10至55重量%的羟基官能的含氟聚合物,5至70重量%,优选10至55重量%的(甲基)丙烯酸酯多元醇,5至35重量%,优选10至30重量%的多异氰酸酯,0.001至0.2重量%,优选最多至1重量%的交联催化剂,0.5至20重量%的优选基于三嗪的紫外线吸收剂和0.5至10重量%的优选基于HALS的紫外线稳定剂和5至80重量%,优选最多至40重量%的溶剂。含氟聚合物和(甲基)丙烯酸酯多元醇在此总共构成该组合物的20至75重量%。此外,含氟聚合物和(甲基)丙烯酸酯多元醇一起具有50至400mgKOH/g,优选90至250mgKOH/g的OH值。
羟基官能的含氟聚合物特别优选是一方面为四氟乙烯(TFE)和/或氯三氟乙烯(CTFE)和另一方面为乙烯基酯、乙烯基醚和/或α-烯烃的共聚物。其特别优选是一方面为CTFE或TFE和另一方面为其它共聚单体的交替共聚物。在这样的聚合物中,通过羟基官能的乙烯基醚和/或α-烯烃的共聚获得羟基官能度。市售羟基官能的含氟聚合物的实例由AsahiGlass公司以产品名由SolvaySolexis公司以品名或由Daikin公司以产品名出售。
由于所用含氟聚合物以及聚(甲基)丙烯酸酯是完全无定形的,因此相应的配制剂和涂层具有良好的光学性质和高透明度。此外,含氟聚合物和聚(甲基)丙烯酸酯都甚至在极端条件下也具有经很长时间跨度的很好的耐候性。因此,本发明的涂层极其耐UV,还具有对空气氧和例如空气水分形式的水的很好阻隔性质。
为了调节该涂层的所需耐候稳定性以及基底保护性质,还必须添加0.5至20重量%,优选最多至15重量%的优选基于三嗪的紫外线吸收剂和/或0.5至10重量%,优选最多至7.5重量%的优选基于HALS的紫外线稳定剂。
该组合物还可额外包含5至40重量%的羟基官能的有机硅树脂。这种有机硅树脂具有50至300mgKOH/g,优选90至200mgKOH/g的OH值。采用这样的有机硅树脂额外提高该组合物的耐热性。此外,在相对较高比例的这些组分以及同时略微较低比例的其它聚合物组分的情况下,可以提高整个组合物的固含量。此类羟基官能的有机硅树脂的一个实例是DowCorning公司的RSN-0255。
所用聚(甲基)丙烯酸酯由至少60重量%的甲基丙烯酸酯基单体单元构成。特别优选涉及悬浮聚合物或溶液聚合物,其特别优选由至少70重量%的甲基丙烯酸甲酯(MMA)和/或甲基丙烯酸丁酯(BuMA)构成。在此可通过合适的单体,例如(甲基)丙烯酸羟乙酯或(甲基)丙烯酸羟丙酯的共聚,和/或通过使用羟基官能的链转移剂,例如巯基乙醇而实现羟基官能化。分子量为10000至300000g/mol且玻璃化转变温度为10至130℃。
所考虑的溶剂原则上包括适用于根据本发明使用的其它组分的所有溶剂或溶剂混合物。这些溶剂更特别可以是酮,如丙酮或甲乙酮,酯,如乙酸乙酯、乙酸丙酯或乙酸丁酯,芳族化合物,如甲苯或二甲苯,或醚,如二乙醚或乙氧基丙酸乙酯。
但是,更特别地,该溶剂也可以是水。已经令人惊讶地发现,本发明的组合物的其它成分特别在水中也形成稳定的分散体,并在以水为溶剂时,可以容易和环境友好地施加相应的漆。
该组合物中的多异氰酸酯通常是异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(H12MDI)、2-甲基戊烷二异氰酸酯(MPDI)、2,2,4-三甲基六亚甲基二异氰酸酯/2,4,4-三甲基六亚甲基二异氰酸酯(TMDI)和/或降冰片烷二异氰酸酯(NBDI)。
所用交联催化剂通常是二月桂酸二丁基锡(DBTDL)、辛酸锌、新癸酸铋和/或叔胺,优选1,4-二氮杂双环[2.2.2]辛烷。合适的此类交联剂的一个实例是Bayer公司的BL3175。一般而言,设定交联剂的量以使OH基团与NCO基团之间的比率为0.5至1.5,优选0.8至1.2,更优选0.9至1.1。这些示例性数值尤其基于包含HDI缩合物和DBTDL的体系。对于其组分各自的分子量或官能度数更明显偏离的其它体系,可以相应地适应性调节给出的极限范围。
此外,该组合物可另外还包含最多至20重量%的硅烷官能的异氰酸烷基酯或缩水甘油基官能的烷基硅烷。这些组分另外有助于与待涂布的基底的粘合性质。一种优选的硅烷官能的异氰酸烷基酯是异氰酸三甲氧基丙基甲硅烷基酯,其例如由EvonikInd.公司以品名VestanatEP-M95出售。缩水甘油基官能的烷基硅烷的一个优选实例是3-缩水甘油氧基丙基三甲氧基硅烷,其可以例如以品名DynasylanGLYMO获自EvonikInd.公司。
此外,特别还可以存在无机纳米粒子,尤其由氧化硅构成的那些,以额外改进该组合物中的抗划伤性和耐磨性。在此,可添加最多至40重量%,优选最多至30重量%的所述纳米粒子。在此尤其优选的是,所述纳米粒子没有光折射性质并且不使聚合物基体变浑浊。
除所述组合物外,用本发明的组合物涂布的基底也是本发明的一部分。在此,在干燥和交联后的涂层优选具有0.5至200微米,优选2微米至150微米,更优选5微米至50微米的厚度。
根据本发明涂布的基底与现有技术相比具有以下优点。
本发明的优选透明的涂层特别是颜色中性的并在水分的影响不会变浑浊。该涂层还表现出优异的耐候稳定性和很好的耐化学品性,例如对所有商业清洁剂的耐受性。这些方面也有助于获得经由长期的表面品质。
本发明的材料也可以在太阳辐射特别强的地点,例如美国西南部或撒哈拉沙漠在户外用途中使用至少15年,优选甚至至少20年,更优选至少25年的很长时间。
在此,本发明的涂层尤其在该表面经受机械负荷时具有很好性质。这甚至在定期经受沙尘暴或高含尘量的风的地区或在使用刷子定期清洁表面时也延长基底的寿命。
此外,本发明的涂层对水分特别稳定,尤其对雨水、空气水分或露水特别稳定。因此,该涂层没有表现出该涂层已知在水分影响下与基底的易层离性。此外,氟基涂层具有特别好的隔水效果。此外,氟基涂层表现出特别好的阻氧效果,因此在腐蚀保护方面具有很好的性质。
此外,本发明的涂层表现出很好的抗划伤性和耐磨性,因此这一效果另外有助于基底的长期寿命。
方法
除已描述的用于涂布的组合物外,涂布基底的方法也是本发明的一部分。
在这种涂布基底的方法中,用如上所述的本发明的组合物涂布基底并随后将涂层干燥和在此交联。
更特别使用下述方法:其中本发明的组合物在有机溶液中与其它配制剂成分一起以“有机溶胶”形式涂布到复合模制品上,随后将涂布的层干燥。在此借助例如刮刀涂布、辊涂、浸涂、幕涂、喷涂进行涂布。干燥过程中平行进行涂层的交联。
在涂布设备中在预制的未涂布复合模制品上进行涂布的这一方法步骤。优选地,也可直接在例如以复合模制品形式的基底制成后在线进行涂布。例如在一个实施方案中通过层压以多层膜片的形式制造基底。在这种情况下,上述涂布设备在线安装在层压设备下游并对新制基底进行涂布。
对于最终产品,在此有多种实施方案。在第一实施方案中,直接涂布到基底上。
在第二实施方案中,以带有本发明的涂料配制剂的表面涂层膜片的形式涂布到各自的基底材料上。在这种情况下,首先将本发明的涂料配制剂以牢固粘合的方式涂布到相应的膜片基底材料上。然后将这种表面涂层膜片施加到各自的最终基底材料上。该表面涂层膜片的底面在此被自粘性粘合剂配制剂涂布或带有热熔体或粘合剂层。底面的这种改性使其在温度和压力辅助的施加过程中“热塑性”或“反应性”粘接在最终基底材料上。
由此,通过该表面涂层膜片的材料性质,可以实现额外的产品特征,例如还有光学属性。此外,这种方法非常灵活,可以例如在相对较大的待涂布基底的情况下,现场不需要溶剂操作或高温而使用。
在第三种变体中,类似于第二实施方案,以热转移工艺的形式实现将本发明的涂料配制剂涂布到各自的基底材料上。在此,在第一涂布步骤中,为相应的膜片或纸载体材料提供防粘层,其使得可以将在第二涂布步骤中施加的本发明的涂料配制剂热转移到各自的基底材料上。
在此任选地,如果必要,在第三涂布步骤中,可以施加粘合剂层,其确保该热转移层构造恰当粘合到各自的基底材料上。
随后可任选为本发明的涂层提供一个或多个附加功能层。其例如可以是防划涂层、导电层、防污涂层和/或提高反射层或其它光学功能层。这些附加层可以例如借助物理气相沉积(PVD)或化学气相沉积(CVD)施加。
可任选涂布附加防划涂层以进一步改进抗划伤性。但是,一般而言,在本发明的复合模制品的良好品质下,这是不需要的。防划涂层可以是例如直接借助PVD或CVD涂布的氧化硅层。
此外,为了有利于清洁,可以为该复合模制品的表面提供拒污或污垢破坏涂层,所谓防污涂层。这种涂层也可以借助PVD或CVD施加。
作为另一示例性选项,在本发明的涂层上还存在另外的较薄的极耐磨层。其是厚度优选低于5微米,更优选为0.5至2.0微米的特别硬的热固性材料层。可以例如由聚硅氮烷配制剂制备这种层。
用途详述
本发明的表面调质技术可用于下列应用领域:
1.用于涂布热固性材料(所谓Thermosets),其例如确定作为用于房屋立面设计的高压层压板用于户外用途。
2.用于涂布装饰层压材料,其例如用于窗户型材、小酒馆家具或墙衬的表面设计。
3.OLED(有机发光二极管):
作为特别在柔性OLED上的涂层,可以实现更好的耐久性,明显的防划保护改进和在户外区域的长期可用性。OLED的一个特别实施方案是卷轴式显示器。这些特别受到高机械应力,借助本发明的涂层,该显示器具有更长的寿命。
4.外窗贴膜:
外窗的调质在隔热方面起很大作用,尤其是在室外温度高时。特别的耐候稳定性对此非常重要。此外,在这一用途中,涂层的高透明度特别起作用。
5.防腐蚀涂层(所谓“重防腐蚀涂层”(HeavyDutyCoatings)):
这些多层涂层体系在钢构造,如在桥梁建造或在建筑物中尤其重要。在此,使用本发明的涂布技术,设计这种多层涂层的顶层(顶涂层),由此可以实现与现有技术相比明显延长的腐蚀防护以及该涂层的特别改进的长期粘合。
同样有意义的应用领域是太阳能获取系统。这更特别地是:
6.薄膜太阳能电池
在此特别相关的是该涂层的高抗UV性以及甚至在极端风化作用,如沙尘暴或高温下也很好的耐候稳定性。
7.用于会聚太阳辐射的镜子,尤其是在集中式太阳能热电站中。
对于这些镜子,关注点也特别是该涂层的腐蚀防护、抗划伤性、透明度和长期粘合和很好的耐候稳定性。
8.光伏背板:光伏模块的背面调质层。在此非常重要的特别是防潮、防UV辐射和其它风化作用的防护。
具体实施方式
实施例
使用1-3N划痕力的划痕硬度研究
实施过程:在测试前,对样品仅表面清洁。用带有来自Bosch公司的0.75mm测试探针、ACC112手推车和各种压缩弹簧的ZHT2092Zehntner硬度测试划线器进行测试。在此,使用不同的指定压缩弹簧,在不同的力下,将测试探针在试样上画直线。
通过压缩弹簧的预张紧调节弹簧力,将硬度测试划线器的尖头置于表面上并抵抗弹簧压力将该测试仪器垂直压到该表面上。然后将手推车在试样上以大约10毫米/秒的速度从主体出发画直线。无论何时用改变的弹簧力重复这一操作,直至对受试表面的轻微损伤都是可见的。在试验循环后,要将压缩弹簧去除压力。
滑块的位置在刻度上显示力(N)并因此直接显示与硬度对应的测试值。使用在材料中产生可见划痕的最低力作为结果。任选地,借助触觉测量仪器,可以测定划痕深度。
预备阶段1
下列预备阶段示例性制备可用于会聚太阳辐射的镜子的基底。
借助适配器共挤制备由0.125mmPMMAPlexiglas7H(为了添加UV添加剂,含2%CGX006和0.6%Chimasorb119)以及0.025mmMakrolon2607聚碳酸酯构成的0.15毫米厚的复合膜片。
此后借助等离子体辅助的溅射工艺在该复合膜片的聚碳酸酯侧上施加反射涂层,其以下列次序(从聚碳酸酯膜片开始)由0.5nmZAO(氧化锌铝)、100nmAg和50nmCu构成。
对比例
将28.9重量%的LumiflonLF-9716预先加入由12.4重量%乙氧基丙酸乙酯和37.3重量%乙酸丁酯形成的溶剂混合物中并相继地在搅拌下与0.0013重量%的DBTDL(二月桂酸二丁基锡;交联催化剂)、3.4重量%的Tinuvin400(紫外线吸收剂)和1.1重量%的Tinuvin123(HALS化合物)混合直至形成均匀澄清的混合物。然后通过搅拌10分钟加入16.9重量%的DesmodurN3300(多异氰酸酯,交联剂)。
使用40μm绕线刮涂器,在标准气候条件下将涂料施加到得自预备阶段1的基底的PMMA侧上。干燥和预固化在强制通风炉中在80℃下进行2小时。该涂层在10分钟后就已经不发粘。后固化在室温下进行7天或在80℃下进行2小时。
实施例
在此,将30重量%的LumiflonLF9716替换成甲基丙烯酸酯基多元醇Degalan4800-L。
由此明显提高本发明的这种涂层的固化速率,尤其是在卷到卷工艺中(较低的不发粘时间),由此显著降低该涂层的成本。此外,由于比较昂贵的含氟聚合物多元醇被比较有利的甲基丙烯酸酯多元醇部分地替代,配制成本降低。
此外,可以实现该表面调质层在所述应用领域中的明显改进的经济性。
其它涂层性质仍不受影响。
根据所进行的划痕硬度测量,本发明的实施例的涂层表现出明显比对比例的涂层低的表面损伤。
Claims (16)
1.用于涂布基底的组合物,其特征在于所述组合物包含5至70重量%的羟基官能的含氟聚合物、5至70重量%的(甲基)丙烯酸酯多元醇、5至35重量%的多异氰酸酯、0.001至0.2重量%的交联催化剂、5至80重量%的溶剂、0.5至20重量%的紫外线吸收剂和0.5至10重量%的紫外线稳定剂,其中所述含氟聚合物和所述(甲基)丙烯酸酯多元醇总共构成所述组合物的20至75重量%并且一起具有50至400mgKOH/g的OH值。
2.根据权利要求1的组合物,其特征在于所述含氟聚合物和所述(甲基)丙烯酸酯多元醇的OH值总计为90至250mgKOH/g。
3.根据权利要求1或2的组合物,其特征在于所述羟基官能的含氟聚合物是由一方面为四氟乙烯(TFE)和/或氯三氟乙烯(CTFE)和另一方面为乙烯基酯、乙烯基醚和/或α-烯烃形成的共聚物,其中所述羟基官能的含氟聚合物通过羟基官能的乙烯基醚和/或α-烯烃的共聚获得。
4.根据权利要求1至3中至少一项的组合物,其特征在于所述组合物额外包含5至40重量%的羟基官能的有机硅树脂,且这种有机硅树脂具有50至300mgKOH/g的OH值。
5.根据权利要求1至4中至少一项的组合物,其特征在于所述组合物包含0.5至15重量%的三嗪作为紫外线吸收剂和0.5至7.5重量%的HALS化合物作为紫外线稳定剂。
6.根据权利要求1至5中至少一项的组合物,其特征在于所述(甲基)丙烯酸酯多元醇具有10000至300000g/mol的分子量和10至130℃的玻璃化转变温度。
7.根据权利要求1至6中至少一项的组合物,其特征在于所述多异氰酸酯是异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(H12MDI)、2-甲基戊烷二异氰酸酯(MPDI)、2,2,4-三甲基六亚甲基二异氰酸酯/2,4,4-三甲基六亚甲基二异氰酸酯(TMDI)和/或降冰片烷二异氰酸酯(NBDI),且所述交联催化剂是二月桂酸二丁基锡、辛酸锌、新癸酸铋和/或叔胺,优选1,4-二氮杂双环[2.2.2]辛烷。
8.根据权利要求1至7中至少一项的组合物,其特征在于所述组合物额外还包含最多至20重量%的硅烷官能的异氰酸烷基酯或缩水甘油基官能的烷基硅烷。
9.根据权利要求1至8中至少一项的组合物,其特征在于所述溶剂是水。
10.基底,其特征在于用根据权利要求1至9中任一项的组合物涂布这种基底,且所述涂层在干燥和交联后具有0.5至200微米的厚度。
11.涂布基底的方法,其特征在于用根据权利要求1至9中任一项的组合物涂布所述基底,且所述涂层随后干燥和交联。
12.根据权利要求11的方法,其特征在于所述基底是在一面上用根据权利要求1至9中至少一项的组合物涂布并在另一面上带有具有粘合性质的层的表面涂层膜片,并可以将这种表面涂层膜片粘接到第二基底上。
13.根据权利要求11的方法,其特征在于用根据权利要求1至9中任一项的组合物借助热转移技术涂布基底,并为此首先将所述组合物施加到带有防粘层的膜片或纸载体材料上。
14.根据权利要求11至13中至少一项的方法,其特征在于另外为所得涂层提供附加防划涂层、导电层、防污涂层和/或反射提高层或其它光学功能层。
15.根据权利要求1至9中至少一项的组合物用于装饰层压材料、OLED、热固性材料、卷轴式显示器、外窗贴膜的表面调质或作为防腐蚀涂层,更特别作为重防腐蚀涂层系统的顶涂层的用途。
16.根据权利要求1至9中至少一项的组合物用于薄膜太阳能电池、会聚太阳辐射的镜子或光伏背板的表面调质的用途。
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ES2808800T3 (es) | 2016-12-22 | 2021-03-01 | Evonik Operations Gmbh | Compuestos a base de aductos con isocianatos para composiciones de revestimiento |
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JP2016516843A (ja) | 2016-06-09 |
EP2970558A1 (de) | 2016-01-20 |
TW201500483A (zh) | 2015-01-01 |
US20160017165A1 (en) | 2016-01-21 |
WO2014139752A1 (de) | 2014-09-18 |
AR095382A1 (es) | 2015-10-14 |
DE102013204395A1 (de) | 2014-09-18 |
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