CN113861844A - 一种水性涂料组合物 - Google Patents
一种水性涂料组合物 Download PDFInfo
- Publication number
- CN113861844A CN113861844A CN202010616600.6A CN202010616600A CN113861844A CN 113861844 A CN113861844 A CN 113861844A CN 202010616600 A CN202010616600 A CN 202010616600A CN 113861844 A CN113861844 A CN 113861844A
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- Prior art keywords
- aqueous
- coating composition
- nano silicon
- resin
- aqueous coating
- Prior art date
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- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- SMUVTFSHWISULV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C(C)=C SMUVTFSHWISULV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
-
- 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
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Abstract
本发明涉及一种水性涂料组合物、组合物的制备和应用、包含该组合物的双组分涂料体系及其应用,以及使用该组合物或双组分涂料体系涂覆得到的制品。该水性涂料组合物包含:一水性UV树脂;一经过硅烷处理的纳米氧化硅化合物;和一光引发剂;每千克所述水性UV树脂的固体分包含不少于3mol的烯属不饱和基团,所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比为11∶20‑73∶100。本发明的水性涂料组合物形成的涂层具有高硬度和良好的附着力,特别适用于5G领域的电子、电气和通信设备。
Description
技术领域
本发明涉及一种水性涂料组合物、组合物的制备和应用、包含该组合物的双组分涂料体系及其应用,以及使用该组合物或双组分涂料体系涂覆得到的制品。本发明的水性涂料组合物形成的涂层具有高硬度和良好的附着力,特别适用于5G领域的电子、电气和通信设备。
背景技术
5G时代对电子、电气和通信设备特别是小型设备和便携式设备的外壳的通信信号穿透力具有较高的要求。目前上述设备的外壳常用的材料是金属,由于其对通信信号的屏蔽和衰减强,不能满足5G设备的要求。在便携式设备领域,例如手机行业,尝试采用塑料、玻璃或陶瓷为背盖材料。塑料由于其轻便、耐磨且不易碎等优点,被广泛研究。这其中PC/PMMA复合板由于其优异的仿玻璃效果,广受欢迎,为了增加PC/PMMA复合板的硬度,通常在其表面涂覆涂层。
UV涂料因其固化速度快,生产效率高,漆膜丰满度高等优点,广泛应用于众多应用中,例如电子、电器,如手机、笔记本等。UV涂料应用于手机塑料背盖,不仅可以实现亮光或者哑光的效果,还可以提高塑料背盖的硬度、耐磨耐刮擦、耐水煮、耐溶剂、耐冷热和耐特殊化学品性能。UV涂料有三种,溶剂型UV涂料、无溶剂型UV涂料和水性UV涂料。
CN106459616A公开了一种溶剂型涂布剂和用其涂布的薄膜,其中该涂层具有增强的机械和化学耐受性和对2D薄膜嵌入式成型法而言足够的可成形性。该涂布剂的组成物可含有无机粒子以提高机械耐久性,包括无机粒子在内的添加剂的总含量为0-20重量%。
EP2604660A1公开了一种用于塑料表面的硬涂层,勃姆石纳米颗粒的表面被烷氧基硅烷化合物改性,并与丙烯酸酯混合形成有机/无机杂化材料,达到较好的综合性能。该体系为溶剂型体系。
CN104736613A公开了一种具有高硬度和优异特性的层压预涂膜,该体系为溶剂型。
US20070238804A1公开了一种UV涂料,用于保护各种塑料基材如眼科镜片、聚碳酸酯板、CR-39板或聚苯乙烯。该UV涂料是无溶剂无水体系,整个工艺过程很复杂,不利于大型工业化生产。
CN105765002A公开了一种可成形的硬涂层组合物以及包含共挤出PC/PMMA膜和通过采用所述硬涂层组合物涂覆获得的涂层的涂膜。该组合物是溶剂型的,包含粘合剂和交联剂,粘合剂包含至少一种丙烯酸酯低聚物和至少一种单官能丙烯酸类单体,交联剂包含至少一种多官能丙烯酸类或甲基丙烯酸类单体。
US2010304113A提供了一种溶剂型涂料组合物及其形成的涂膜,包含含有UV可固化官能团的粘合剂、含有UV可固化含氟官能团的化合物、光敏引发剂和纳米粒子。该涂膜具有优异的耐磨性和耐污染性,例如指纹痕迹可除去性和抗涂写性。
溶剂型UV涂料和无溶剂型涂料因含有大量低闪点溶剂或活性单体,不利于环境和人体。水性UV涂料不但具备UV涂料的固化速度快,生产效率高,漆膜丰满度高等优点,而且以水作为分散介质,取代了有机溶剂,大大降低了VOC的挥发量,对人体无刺激及对环境也非常友好。但是,现有的水性UV涂料在对基材表面的附着力、涂层的铅笔硬度和耐水煮等方面与溶剂型或无溶剂型UV涂料相比还存在差距。
CN107109101A公开了一种光学膜涂覆组合物,包含可UV固化的丙烯酸酯树脂、含有无机纳米颗粒和炭黑的混合颗粒以及光引发剂。该涂覆组合物能改善可见性和光亮度。
US20090269568A1通过引入无机粒子来改善水性UV涂料的效果,可以实现UV涂料形成的涂层在变形之前表现出高的抗粘连性以至于该涂层能够毫无任何问题地被卷起,而在变形过程中仍然能达到高的拉伸比。当无机粒子的添加量在1重量%-60重量%时,UV涂料形成的涂层的750g铅笔硬度可以达到2H。但是该涂料仍然不能满足电子、电气和通信设备的外壳的硬度要求,尤其是手机塑料背盖对涂料的硬度要求。
因此,希望开发一种具有良好的附着力和高铅笔硬度的水性UV涂料,以满足5G设备外壳尤其是手机塑料背盖对涂料的性能要求。
发明内容
本发明的目的是提供一种水性涂料组合物、组合物的制备和应用、包含该组合物的双组分涂料体系及其应用,以及使用该组合物或双组分涂料体系涂覆得到的制品。
根据本发明的水性涂料组合物,包含:
至少一水性UV树脂;
至少一经过硅烷处理的纳米氧化硅化合物;和
至少一光引发剂;
其中,每千克所述水性UV树脂的固体分包含不少于3mol的烯属不饱和基团,所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比为11∶20-73∶100。
根据本发明的一个方面,提供了制备本发明所提供的水性涂料组合物的方法,以任意方式混合所述水性UV树脂、经过硅烷处理的纳米氧化硅化合物和光引发剂。
根据本发明的又一个方面,提供了根据本发明所提供的水性涂料组合物用于制备制品的用途。
根据本发明的再一个方面,提供了一种制品,包含一基材以及将根据本发明所提供的水性涂料组合物施加到所述基材上形成的涂层。
根据本发明的还一个方面,提供了制造制品的方法,包含以下步骤:将根据本发明所提供的水性涂料组合物施加到一基材表面,干燥并固化。
根据本发明的还一个方面,提供了一种双组分涂料体系,包含A组分和B组分,所述A组分是根据本发明所提供的水性涂料组合物,所述B组分是交联剂。
根据本发明的还一个方面,提供了根据本发明所提供的双组分涂料体系用于制备制品的用途。
根据本发明的还一个方面,提供了一种制品,包含一基材以及将根据本发明所提供的双组分涂料体系施加到所述基材上形成的涂层。
本发明的水性涂料组合物或双组分涂料体系,具有低VOC、低气味的优点。其中的水性UV树脂和经过硅烷处理的纳米氧化硅化合物可以形成密实的无机/有机杂化体系,水性涂料组合物或双组分涂料体系形成的涂层具有铅笔硬度高、常规附着力好和水煮附着力好的优点。常规附着力好说明涂料和基材的粘接性能好,水煮附着力好说明在高温高湿条件下涂料和基材的粘接性能好、耐水解性能好。铅笔硬度高说明涂料形成的涂层的耐刮擦性能好。本发明的水性涂料组合物或双组分涂料体系可以满足5G设备外壳尤其是手机塑料背盖对涂料的性能要求。
具体实施方式
本发明提供一种水性涂料组合物,包含:
至少一水性UV树脂;
至少一经过硅烷处理的纳米氧化硅化合物;和
至少一光引发剂;
其中,每千克所述水性UV树脂的固体分包含不少于3mol的烯属不饱和基团,所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比为11∶20-73∶100。本发明还提供了该组合物的制备方法和应用,特别是在涂料领域的应用,包含该组合物的双组分涂料体系及其应用,以及使用该组合物或双组分涂料体系涂覆得到的制品。
本文所用的术语“固化”是指水性涂料组合物或包含组合物的双组分涂料体系从液态到固态的过程。
本文所用的术语“涂料”是指能够用不同的施工工艺涂覆在物件表面,形成粘附牢固、具有一定强度、连续的固态涂层的化学物质。
术语水性UV树脂是指水性紫外光固化树脂。
术语紫外光固化树脂是指这样一种聚合物,其在暴露于紫外线(UV)辐射时能够与扩链剂、交联剂和其他聚合物分子形成共价键的官能团从而形成交联聚合物网络。
本文所用的术语“聚氨酯”是指聚氨酯脲和/或聚氨酯聚脲和/或聚脲和/或聚硫氨酯。
本文所用的术语“经过硅烷处理的纳米氧化硅化合物”是指由硅烷预处理过的纳米氧化硅化合物。
水性涂料组合物
所述组合物中的有机溶剂的量优选不超过5重量%,最优选不超过0.5重量%,相对于所述组合物的总重量计。
所述组合物是水性体系的,组合物具有低VOC的特点。
所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比优选3∶5-17∶25。
水性UV树脂
本发明的水性UV树脂是以分散体或乳化剂存在的,其中包含水。
本发明的水性UV树脂的固体分是指水性UV树脂的固体组分或有效组分。
每千克所述水性UV树脂的固体分包含不少于3mol,进一步优选包含不少于3.5mol,最优选包含不少于4mol的烯属不饱和基团。
所述水性UV树脂优选水性UV聚氨酯丙烯酸酯分散体。
所述水性UV树脂的固体分的量优选30重量%-50重量%,相对于所述水性UV树脂的总重量计。
所述水性UV树脂的量优选45重量%-50重量%,相对于所述水性涂料组合物的总重量计。
所述水性UV树脂中残留的有机溶剂的量优选低于1.0重量%,相对于所述水性UV树脂的固体分的总重量计。
所述水性UV聚氨酯丙烯酸酯分散体优选下列的一种或多种:Bayhydrol UV 2689/2和Bayhydrol UV 2720/1。
经过硅烷处理的纳米氧化硅化合物
本发明的纳米氧化硅化合物的固体分是指纳米氧化硅化合物的固体组分或有效组分。
所述纳米氧化硅化合物的粒径优选8nm-18nm,最优选8nm-10nm。
所述纳米氧化硅化合物优选下列的一种或多种:气相纳米二氧化硅、水性纳米二氧化硅分散体、水性纳米硅溶胶、溶剂型纳米二氧化硅溶液和溶剂型纳米硅溶胶;进一步优选下列的一种或多种:水性纳米二氧化硅分散体和水性纳米硅溶胶;最优选水性纳米二氧化硅分散体。
所述纳米氧化硅化合物优选中性的或碱性的。
所述纳米氧化硅化合物优选中性或碱性的表面经过硅烷处理的水性纳米二氧化硅分散体,进一步优选粒径为8nm-18nm的中性或碱性的表面经过硅烷处理的水性纳米二氧化硅分散体,最优选Dispercoll S 3030/1。
所述纳米氧化硅化合物的量为37-44重量%,相对于所述水性涂料组合物的总重量计。
光引发剂
所述光引发剂优选下列的一种或多种:单分子引发剂和双分子引发剂。
所述单分子引发剂优选芳香族酮化合物,最优选下列的一种或多种:与叔胺组合的二苯甲酮类、烷基二苯甲酮、4,4′-双(二甲基氨基)二苯甲酮(Michler酮)、蒽酮和卤化的二苯甲酮。
所述双分子引发剂优选下列的一种或多种:苯偶姻、苯偶姻的衍生物、苯偶酰缩酮、酰基氧化膦、双酰基氧化膦、苯基乙醛酸酯、樟脑醌、α-氨基烷基苯基酮、α,α-二烷氧基苯乙酮和α-羟基烷基苯基酮。所述酰基氧化膦优选2,4,6-三甲基苯甲酰基二苯基氧化膦。
所述光引发剂最优选下列的一种或多种:Omnirad、Irgacure、Darocur和Esacure。
所述光引发剂的量优选0.5重量%-5.0重量%,最优选0.5重量%-1.0重量%,相对于所述水性涂料组合物的总重量计。
其他
所述水性涂料组合物优选进一步包含下列的一种或多种:硅烷偶联剂、其他的水性聚合物分散体或乳液、活性稀释剂和添加剂。
所述硅烷偶联剂优选下列的一种或多种:烷基硅烷偶联剂、含不饱和基团的硅烷偶联剂、氨基硅烷偶联剂、环氧基硅烷偶联剂、巯基硅烷偶联剂、醚基硅烷偶联剂和硅烷低聚物;最优选含不饱和基团的硅烷偶联剂。
所述含不饱和基团的硅烷偶联剂优选下列的一种或多种:乙烯基硅烷偶联剂、丙烯酰氧基硅烷偶联剂和甲基丙烯酰氧基硅烷偶联剂,进一步优选下列的一种或多种:丙烯酰氧基硅烷偶联剂和甲基丙烯酰氧基硅烷偶联剂,最优选下列的一种或多种:3-丙烯酰氧基丙基三甲氧基硅烷和3-甲基丙烯酰氧基丙基三甲氧基硅烷。
所述硅烷偶联剂的量优选0.1重量%-3.0重量%,相对于所述水性涂料组合物的总重量计。
所述其他的水性聚合物分散体或乳液优选下列的一种或多种:聚氨酯分散体、聚丙烯酸酯一级分散体、聚丙烯酸酯二级分散体、乙烯-醋酸乙烯共聚物乳液、石油树脂聚合物乳液、松香聚合物乳液、聚丁二烯分散体、丙苯共聚物乳液、丁苯共聚物乳液、萜烯酚醛聚合物乳液、聚氯丁二烯分散体和聚偏1,1-二氯乙烯分散体。
所述其他的水性聚合物分散体或乳液的量优选0-50重量%,相对于所述水性涂料组合物的总重量计。
所述活性稀释剂优选丙烯酸酯单体活性稀释剂,进一步优选三官能度或三官能度以上的丙烯酸酯单体,最优选下列的一种或多种:三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(EOTMPTA)、甘油-丙氧基化三丙烯酸酯(GPTA)、季戊四醇四丙烯酸酯(PETA)、乙氧基化季戊四醇四丙烯酸酯(EOPETA)和二季戊四醇六丙烯酸酯(DPHA)。
所述活性稀释剂的量优选1.0重量%-20.0重量%,相对于所述水性涂料组合物的总重量计。
所述添加剂优选下列的一种或多种:消泡剂、润湿剂、流平剂、抗粘连剂、抗粘污助剂、抗指纹助剂和增稠剂。
所述添加剂的量可以是本领域的技术人员熟知的量,优选0重量%-20重量%,进一步优选0重量%-10重量%,最优选0.1重量%-10重量%,相对于所述水性涂料组合物的总重量计。
水性涂料组合物的制备方法
所述水性涂料组合物的制备方法,优选包含以下步骤:以任意方式混合所述水性UV树脂、经过硅烷处理的纳米氧化硅化合物、光引发剂、可选的硅烷偶联剂、可选的其他的水性聚合物分散体或乳液、可选的活性稀释剂和可选的添加剂。
所述制品优选5G产品的壳体,进一步优选5G产品的面盖或背盖,最优选手机背盖。
所述基材优选是由热塑性聚合物制成的。所述基材可以以板材形式存在,也可以以层合膜形式存在。所述层合膜可以是双层或多层的。
所述热塑性聚合物优选下列的一种或多种:聚甲基丙烯酸甲酯(PMMA)、聚酯、硬质PVC、纤维素酯、聚苯乙烯(PS)、聚苯乙烯共聚物、聚丙烯腈(PAN)、ABS塑料、丙烯腈甲基丙烯酸甲酯(AMMA)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚氨酯(PUR)、聚乙烯(PE、PE-HD、-LD、-LLD、-C)、聚丙烯(PP)、聚酰胺(PA)、聚碳酸酯(PC)和聚醚砜(PES)(根据DIN 7728第一部分的缩写),进一步优选下列的一种或多种:聚碳酸酯板和PC/PMMA复合板,最优选PC/PMMA复合板。
所述PC/PMMA复合板也称PC/亚克力复合板。
所述聚酯优选下列的一种或多种:PET(聚对苯二甲酸乙二醇酯)、PEN(聚萘二甲酸乙二醇酯)、PBTP(聚对苯二甲酸丁二醇酯)和UP(不饱和聚酯树脂)。
所述聚苯乙烯共聚物优选下列的一种或多种:SAN(苯乙烯-丙烯腈共聚物)、SB(苯乙烯-丁二烯共聚物)和MBS(甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物)。
优选的制造制品的方法,所述制品是5G产品的壳体,进一步优选5G产品的面盖或背盖,最优选手机背盖,所述方法包含以下步骤:
i)将本发明的水性涂料组合物施加到PC/PMMA复合板的PMMA面上;
ii)在50℃-100℃下干燥3分钟-10分钟;和
iii)以1m/min-10m/min的固化速率和100mJ/cm2-2000mJ/cm2的辐射强度光固化。
所述施加优选下列的一种或多种:淋涂、喷涂、辊涂、刀涂、丝印和转印。
所述干燥可以是行业内常用的方法,优选使用烘箱或者烘道。
所述涂层的干膜厚度优选5μm-20μm,最优选8μm-20μm。
所述步骤ii)的干燥温度优选60℃-80℃,干燥时间优选5分钟-10分钟。
所述固化优选紫外光固化,进一步优选UV辐射,最优选使用IST的M-40-2×1-URS-TR-SS型的UV装置。
所述步骤iii)的固化剂量使用EIT的EIT UV Power Pack II剂量器来测量。
所述步骤iii)优选是在5m/min的固化速率下一次通过UV装置,在700mJ/cm2的辐射强度下固化。
所述双组分涂料体系的有机溶剂的量优选不超过5重量%,最优选不超过0.5重量%,相对于所述双组分涂料体系的总重量计。
所述双组分涂料体系是水性的,双组分涂料体系的VOC含量低。
所述A组分和B组分优选独立储存,在使用前将两者混合。
所述A组分与所述B组分的重量比优选2∶1-100∶1,进一步优选5∶1-100∶1,最优选50∶1-65∶1。
所述交联剂优选下列的一种或多种:含异氰酸酯基团的化合物和碳化二亚胺。
所述含异氰酸酯基团的化合物优选水可分散的脂肪族聚异氰酸酯,最优选下列的一种或多种:水可分散的基于HDI的聚异氰酸酯和水可分散的基于IPDI的聚异氰酸酯。
所述含异氰酸酯基团的化合物的NCO基团含量优选10重量%-20重量%。
所述碳化二亚胺优选水性碳化二亚胺。
所述碳化二亚胺的NCN基团含量优选3重量%-5重量%。
实施例
除非另外限定,本文所使用的所有技术和科学术语具有本发明所属领域技术人员通常理解的相同意义。当本说明书中术语的定义与本发明所属领域技术人员通常理解的意义有矛盾时,以本文中所述的定义为准。
除非另有说明,否则在说明书和权利要求书中使用的表达成分的量、反应条件等的所有数值被理解为在被术语“约”修饰。因此,除非有相反指示,否则在这里阐述的数值参数是能够根据需要获得的所需性能来变化的近似值。
本文中所用的“和/或”是指所提及的要素之一或全部。
本文中所用“包括”和“包含”涵盖只有所提及要素的情形以及除了所提及要素还存在其它未提及要素的情形。
本发明中所有百分比均为重量百分比,另有说明的除外。
本发明的分析测量都在23℃下进行,另有说明的除外。
除非另有说明,否则在本说明书中所用的“一”、“一种”、“一个”和“该”意在包括“至少一种”或“一种或多种”。例如,“一组分”是指一种或多种组分,因此在所述实施方案的实施中可能考虑并可能采用或使用多于一种组分。
分散体的固体分使用Mettler Toledo公司的HS153水分测定仪根据DIN-EN ISO3251进行,测试时称取1g样品。
粒径的测试使用:分散体的粒度在用去离子水稀释后使用激光光谱法(Malvern仪器公司的Zatasizer Nano ZS 3600激光粒度仪测量)在23℃下测定。
pH值使用德国Sartorius公司的PB-10pH计在23℃下测量。
原料和试剂
Bayhydrol UV 2689/2:水性UV树脂,固体分含量为41.4%,pH值7.0-8.5,每千克水性UV树脂固体分的烯属不饱和基团的摩尔数为4mol-8mol,可购自科思创聚合物(中国)有限公司。
Bayhydrol UV 2282:水性UV树脂,固体分含量为39.6%,pH值7.0-8.5,每千克水性UV树脂固体分的烯属不饱和基团的摩尔数小于3.0mol,可购自科思创聚合物(中国)有限公司。
Bayhydrol UH XP 2648:水性UV树脂,固体分含量为35.6%,pH值8.0,不含烯属不饱和基团,可购自科思创聚合物(中国)有限公司。
Dispercoll S 3030/1:表面经过硅烷处理的水性纳米二氧化硅分散体,固体分为30.9%,pH值10.5,粒径8nm-9nm,可购自科思创聚合物(中国)有限公司。
Dispercoll S 2020:表面未经过处理的水性纳米二氧化硅分散体,固体分为20.3%,pH值3,粒径15nm,可购自科思创聚合物(中国)有限公司。
SNOWTEX-40:表面未经过处理的水性纳米二氧化硅分散体,固体分为40.2%,pH值9-10.5,粒径20nm-25nm,可购自日产化学。
Omnirad 500:α羟基酮,表层光固化引发剂,购自艾坚蒙。
BYK 093:消泡剂,购自毕克化学。
BYK 333:聚醚改性有机硅,润湿剂,购自毕克化学。
BYK 346:聚醚改性硅氧烷溶液,润湿剂,购自毕克化学。
TEGO Twin 4100:润湿剂,购自赢创工业集团。
TEGO Glide 410:润湿剂抗粘连剂,购自赢创工业集团。
Borchi Gel 0621:增稠剂,购自欧蒽吉(上海)贸易有限公司。
Desmodur XP 2802:亲水改性的碳化二亚胺交联剂,40重量%固含,NCN基团含量4.2重量%,购自科思创股份有限公司。
Bayhydur 305:聚异氰酸酯固化剂,水可分散的基于HDI的亲水性脂肪族聚异氰酸酯,NCO基团含量16.2重量%,购自科思创股份有限公司。
性能测试方法
1.常规附着力
参照国标GB/T 9286-1998《色漆和清漆漆膜的划格试验》,对UV固化后的涂层进行百格测试,胶带使用3M的Scotch 600。附着力评定方法结合GB/T 9286-1998《色漆和清漆漆膜的划格试验》和ASTM D 3359《胶带法测试附着力的标准方法》中的方法B的标准进行评定。表1展示了常规附着力的评定标准。常规附着力合格值为5B。
表1常规附着力评定标准
2.铅笔硬度
参照国标GB/T 6739-1996《涂膜硬度铅笔测定法》,使用MITSUBISHI UNI铅笔,装在专用的铅笔硬度测试仪上,施加在笔尖上的载荷为1kg,铅笔与水平面的夹角为45°,推动铅笔向前滑动约10mm长,共划5条在不同位置,再用橡皮将铅笔痕迹擦拭干净,检查涂层表面有无划痕,要求涂层表面留有的划痕不超过1条为通过。铅笔硬度不低于3H为合格。
3.水煮附着力
将UV固化后的涂层膜片完全浸没在80℃的热水中30分钟,取出轻轻吸干表面水分,观察涂层外观变化并进行百格测试。附着力评定方法和标准同常规附着力的方法和标准。水煮附着力≥4B为合格。
表2是实施例和对比例的水性涂料组合物或双组分涂料体系的组成,以及组合物或双组分涂料体系形成的涂层的性能测试结果。
对比例1-5,7,9-11和实施例1-2的水性涂料组合物的制备方法
根据表2所示的组分的含量,将树脂、光引发剂、可选的水性纳米二氧化硅分散体、可选的添加剂和去离子水加入容器中,搅拌直至所有组分均匀分散得到实施例和对比例的组合物。
对比例6、8和实施例3-4的双组分涂料体系的制备方法
A组分的制备:根据表2所示的组分的含量,将树脂、光引发剂、可选的水性纳米二氧化硅分散体、可选的添加剂和去离子水加入容器中,搅拌直至所有组分均匀分散。
混合A组分与B组分,并在200-500rpm下搅拌5min-10min,混合均匀后使用200目滤网过滤得到实施例和对比例的双组分涂料体系,待用。
涂层的制备方法
将水性涂料组合物或双组分涂料体系均匀辊涂在PC/PMMA膜的PMMA面上,涂层干膜厚约为8μm-15μm;在烘箱中60℃-80℃干燥约5分钟;使用来自IST的M-40-2×1-URS-TR-SS型的UV装置来固化(固化的剂量用EIT UV Power Pack II剂量器来测量),在5m/min的连续固化速率下一次通过上述UV装置,在约600mJ/cm2-800mJ/cm2的辐射强度下固化得到涂层。
表2实施例和对比例的组合物、双组分涂料体系的组成及性能测试结果
备注:重量比是指纳米氧化硅化合物的固体分与水性UV树脂的固体分的重量之比。
本发明的实施例1-4的水性涂料组合物或双组分涂料体系具有良好的常规附着力、水煮附着力和铅笔硬度。其中,实施例3-4是双组分涂料体系,分别选取了聚异氰酸酯型固化剂和碳化二亚胺固化剂,从表2的涂层性能测试结果来看,添加不同的固化剂都可以达到较高的铅笔硬度、常规附着力和水煮附着力。
对比例1的组合物不包含经过硅烷处理的纳米氧化硅化合物,组合物制备得到的涂层的常规附着力、水煮附着力和铅笔硬度都不合格。
对比例2-3,6-8的组合物或涂料体系的纳米氧化硅化合物的固体分与水性UV树脂的固体分的重量比都小于11∶20,对比例4-5的组合物的纳米氧化硅化合物的固体分与水性UV树脂的固体分的重量比都大于73∶100,上述组合物或涂料体系形成的涂层不能兼顾常规附着力、水煮附着力和铅笔硬度。
比较实施例1和对比例9-10,对比例9选用了pH值为碱性的未经硅烷处理的水性纳米二氧化硅分散体,对比例10选用了pH值为酸性的未经硅烷处理的水性纳米二氧化硅分散体,对比例9的水性涂料组合物制备得到的涂层的常规附着力、水煮附着力和铅笔硬度都不合格。对比例10的水性涂料组合物形成的涂层肉眼可见小颗粒,即组合物不相容,无法进行涂层性能测试。
比较实施例1和对比例11,对比例11选用的树脂为Bayhydrol UV 2282,每千克Bayhydrol UV 2282的固体组分的烯属不饱和基团的摩尔数小于3.0mol,包含其的组合物制备得到的涂层的常规附着力、水煮附着力和铅笔硬度都不合格。
所属领域的技术人员易知,本发明不仅限于前述的具体细节,且在不脱离本发明的精神或主要特性的前提下,本发明可实施为其他特定形式。因此从任何角度来说都应将所述实施例视作例示性而非限制性的,从而由权利要求书而非前述说明来指出本发明的范围;且因此任何改变,只要其属于权利要求等效物的含义和范围中,都应视作属于本发明。
Claims (23)
1.一种水性涂料组合物,包含:
至少一水性UV树脂;
至少一经过硅烷处理的纳米氧化硅化合物;和
至少一光引发剂;
其中,每千克所述水性UV树脂的固体分包含不少于3mol的烯属不饱和基团,所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比为11∶20-73∶100。
2.如权利要求1所述的水性涂料组合物,其特征在于,每千克所述水性UV树脂的固体分包含不少于3.5mol,最优选不少于4mol的烯属不饱和基团。
3.如权利要求1或2所述的水性涂料组合物,其特征在于,所述水性UV树脂是水性UV聚氨酯丙烯酸酯分散体。
4.如权利要求1-3任一项所述的水性涂料组合物,其特征在于,所述水性UV树脂的量为45重量%-50重量%,相对于所述水性涂料组合物的总重量计。
5.如权利要求1-4任一项所述的水性涂料组合物,其特征在于,所述纳米氧化硅化合物的固体分与所述水性UV树脂的固体分的重量比为3∶5-17∶25。
6.如权利要求1-5任一项所述的水性涂料组合物,其特征在于,所述纳米氧化硅化合物的粒径为8nm-18nm。
7.如权利要求1-6任一项所述的水性涂料组合物,其特征在于,所述纳米氧化硅化合物是下列的一种或多种:气相纳米二氧化硅、水性纳米二氧化硅分散体、水性纳米硅溶胶、溶剂型纳米二氧化硅溶液和溶剂型纳米硅溶胶;进一步优选下列的一种或多种:水性纳米二氧化硅分散体和水性纳米硅溶胶;最优选水性纳米二氧化硅分散体。
8.如权利要求1-7任一项所述的水性涂料组合物,其特征在于,所述纳米氧化硅化合物是中性或碱性的。
9.如权利要求1-8任一项所述的水性涂料组合物,其特征在于,所述光引发剂的量为0.5重量%-5.0重量%,相对于所述水性涂料组合物的总重量计。
10.如权利要求1-9任一项所述的水性涂料组合物,其特征在于,所述水性涂料组合物进一步包含下列的一种或多种:硅烷偶联剂、其他的水性聚合物分散体或乳液、活性稀释剂和添加剂。
11.如权利要求10所述的水性涂料组合物,其特征在于,所述其他的水性聚合物分散体或乳液的量不超过50重量%,相对于所述水性涂料组合物的总重量计。
12.制备如权利要求1-11任一项所述的水性涂料组合物的方法,以任意方式混合所述水性UV树脂、经过硅烷处理的纳米氧化硅化合物和光引发剂。
13.根据权利要求1-11任一项所述的水性涂料组合物用于制备制品的用途。
14.一种制品,包含一基材以及将根据权利要求1-11任一项所述的水性涂料组合物施加到所述基材上形成的涂层。
15.如权利要求14所述的制品,其特征在于,所述基材是PC/PMMA复合板。
16.如权利要求14或15所述的制品,其特征在于,所述制品是5G产品的壳体,特别是5G产品的面盖或背盖。
17.制造制品的方法,包含以下步骤:将如权利要求1-11任一项所述的水性涂料组合物施加到一基材表面,干燥并固化。
18.一种双组分涂料体系,包含A组分和B组分,所述A组分是根据权利要求1-11任一项所述的水性涂料组合物,所述B组分是交联剂。
19.如权利要求18所述的双组分涂料体系,其特征在于,所述交联剂是下列的一种或多种:含异氰酸酯基团的化合物和碳化二亚胺。
20.根据权利要求18或19所述的双组分涂料体系用于制备制品的用途。
21.一种制品,包含一基材以及将根据权利要求18或19所述的双组分涂料体系施加到所述基材上形成的涂层。
22.如权利要求21所述的制品,其特征在于,所述基材是PC/PMMA复合板。
23.如权利要求21或22所述的制品,其特征在于,所述制品是5G产品的壳体,特别是5G产品的面盖或背盖。
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CN116496683A (zh) * | 2023-03-09 | 2023-07-28 | 广州翔铭环保新材料有限公司 | 一种水性uv涂料的制备方法 |
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EP2215171B1 (en) | 2007-11-29 | 2013-07-03 | LG Chem, Ltd. | Coating composition and coating film having enhanced abrasion resistance and fingerprint traces removability |
PL2113527T3 (pl) | 2008-04-28 | 2014-10-31 | Bayer Ip Gmbh | Odkształcalna folia z powłoką utwardzalną radiacyjnie i wykonane z niej kształtki |
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US20140302251A1 (en) * | 2013-03-15 | 2014-10-09 | The Sherwin-Williams Company | Radiation polymerizable abrasion resistant aqueous coatings |
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CN114525050B (zh) * | 2022-03-31 | 2023-03-14 | 金发科技股份有限公司 | 疏水防雾涂料、其制备方法及防雾制品 |
CN116496683A (zh) * | 2023-03-09 | 2023-07-28 | 广州翔铭环保新材料有限公司 | 一种水性uv涂料的制备方法 |
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