CN104487497A - 硬涂膜 - Google Patents

硬涂膜 Download PDF

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Publication number
CN104487497A
CN104487497A CN201380039332.4A CN201380039332A CN104487497A CN 104487497 A CN104487497 A CN 104487497A CN 201380039332 A CN201380039332 A CN 201380039332A CN 104487497 A CN104487497 A CN 104487497A
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China
Prior art keywords
hard coat
coat film
film
photo curable
supporting substrate
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Granted
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CN201380039332.4A
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English (en)
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CN104487497B (zh
Inventor
姜俊求
张影来
沈载勋
洪性敦
李承贞
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LG Chem Ltd
LG Corp
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LG Chemical Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065After-treatment
    • B05D3/067Curing or cross-linking the coating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/3475Five-membered rings condensed with carbocyclic rings
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D135/00Coating 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 carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02Homopolymers or copolymers of esters
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    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract

本发明涉及一种硬涂膜,更具体而言涉及一种具有高硬度和其他优异性能的硬涂膜。本发明可提供一种具有低的卷曲发生率和高硬度的硬涂膜。

Description

硬涂膜
技术领域
本发明涉及一种硬涂膜。更具体而言,本发明涉及一种具有高硬度和优异性能的硬涂膜。
本申请要求于2012年5月31号提交的韩国专利申请第10-2012-0058634号、于2012年5月31号提交的韩国专利申请第10-2012-0058635号、于2012年5月31号提交的韩国专利申请第10-2012-0058636号、于2012年5月31号提交的韩国专利申请第10-2012-0058637号以及于2013年5月30号提交的韩国专利申请第10-2013-0062124号的优先权。所述在先申请的全部公开内容以引用的方式全部纳入本说明书。
背景技术
近来,随着移动设备如智能手机、平板电脑等的发展,需要显示器基板变得更薄和更轻。这些移动设备的显示窗或前面板一般由具有优异机械性能的玻璃或钢化玻璃制成。然而,玻璃材料由于它们自身的重量使得移动设备变的很重并且容易因外界冲击而受损。
作为玻璃的一种替代材料,已对塑料树脂薄膜进行了研究。塑料树脂因其质轻且不易破裂,所以与追求较轻质的移动设备的趋势相适应。具体而言,要求一种具有高硬度和耐磨性的薄膜。就此而言,提出了一种结构,其中基板上涂覆有硬涂膜。
可考虑将增加硬涂层的厚度的方法作为提高硬涂层的表面硬度的方法。为了保证硬涂层的表面硬度达到硬涂层可替代玻璃的程度,须调整硬涂层的厚度。然而,随着硬涂层厚度的增加,其表面硬度变高,但是硬涂层可能因为其固化收缩而起皱或卷曲,并且可能容易破裂或剥脱。因此,将硬涂层用于实际应用是不容易的。
近来,已提出了几种用于增加硬涂膜的硬度以及解决由于其固化收缩而造成的硬涂膜破裂或卷曲的问题的方法。
韩国专利申请公开第2010-0041992号公开了一种不含单体的硬涂膜组合物,其使用一种包括紫外线可固化的聚氨酯丙烯酸酯低聚物的粘合剂树脂。然而,此硬涂膜的铅笔硬度约为3H,不足以替代玻璃面板用于显示器。
发明内容
技术问题
因此,本发明用于解决上述问题,因而本发明的目的是提供一种具有高硬度且不会卷曲、弯曲或者破裂的硬涂膜。
技术方案
为了实现上述目的,本发明的一个方面提供了一种硬涂膜,包括:支撑基板;和形成于支撑基板的至少一面上的硬涂层,其中硬涂层包括包含三至六官能的丙烯酸酯系单体的可光固化的交联共聚物,以及分散在可光固化的交联共聚物中的无机颗粒。
有益效果
如上所述,本发明的硬涂膜在硬度、耐擦伤性以及透明度方面显示了优异的性能。此外,它具有很高的可加工性,并因而更不容易卷曲和破裂。因此,该硬涂膜可被有效地应用于移动设备、显示器、仪器等的前面板或显示面板。
实施本发明的最佳实施方式
根据本发明的一个方面,本发明提供了一种硬涂膜,包括:支撑基板;和形成于支撑基板的至少一面上的硬涂层,其中硬涂层包括包含三至六官能的丙烯酸酯系单体的可光固化的交联共聚物,以及分散在可光固化的交联共聚物中的无机颗粒。
在本发明中,术语“第一”、“第二”等用来描述各种成分,仅用于成分彼此区分的目的。
此外,本说明书中使用的术语仅用于说明本发明,并不意图限制本发明。单数包括复数,只要它们在上下文中明显不同于彼此。在本说明书中,术语“包括”、“包含”、“具有”等意指存在的特征、步骤、成分及其组合,并须理解,并未事先排除一种或多种其他特征、步骤、成分及其组合的存在或添加。
此外,在本发明中,当提及各成分形成于各成分“上”、“之上”或者“上方”时,它意指各成分直接形成于各自成分之上或另一种成分额外形成于层之间、物体上或基质上。
由于本发明可能以各种方式进行修饰,所以将详细描述本发明的优选实施方案。尽管公开了这些以说明性为目的的实施方案,但是应理解本发明不限于此,且本技术领域中的普通技术人员应理解,在未脱离本发明范围和精神的情况下,各种修改、添加和取代均可行。
下面将详细描述本发明的优选实施方案。
根据本发明的一个实施方案,硬涂膜包括:支撑基板;和形成于支撑基板的至少一面上的硬涂层,其中硬涂层包括包含三至六官能的丙烯酸酯系单体的可光固化的交联共聚物,以及分散在可光固化的交联共聚物中的无机颗粒。
在本发明的硬涂膜中,只要其是透明的,任何塑料树脂(无论能否被拉伸)均可用作其上形成有硬涂膜的支撑基板,但不限于此。根据本发明的一个实施方案,支撑基板可包括聚对苯二甲酸乙二醇酯(PET)、环烯烃共聚物(COC)、聚丙烯酸酯(PAC)、聚碳酸酯(PC)、聚乙烯(PE)、聚甲基丙烯酸甲酯(PMMA)、聚醚醚酮(PEEK)、聚萘二甲酸乙二醇酯(polyethylenenaphthalate,PEN)、聚醚酰亚胺(PEI)、聚酰亚胺(PI)、三乙酰基纤维素(TAC)和甲基丙烯酸甲酯(MMA)等。支撑基板可以是单层结构,如果需要,也可以是由相同或不同材料组成的多层结构,但是并无特殊限制。
根据本发明的一个实施方案,支撑基板可以是由聚对苯二甲酸乙二醇酯(PET)制成的多层基板,或者是通过聚甲基丙烯酸甲酯(PMMA)和聚碳酸酯(PC)的共挤压而形成的多层基板。
此外,根据本发明的一个实施方案,支撑基板可包括聚甲基丙烯酸甲酯(PMMA)和聚碳酸酯(PC)的共聚物。
支撑基板的厚度可为,但不限于,约30至约1200μm,或约50至约800μm。
在本发明的硬涂膜中,硬涂层形成于支撑基板的至少一面上。
此外,根据本发明的一个实施方案,支撑基板与硬涂层的厚度比可为约1:0.5至约1:2,或约1:0.5至约1:1.5。当它们的厚度比值处于上述范围时,可形成具有高硬度且不容易卷曲或破裂的硬涂膜。
在本发明的硬涂膜中,硬涂层包括三至六官能的丙烯酸酯系单体的可光固化的交联共聚物,以及分散在可光固化的交联共聚物中的无机颗粒。
在本说明书中,术语“丙烯酸酯系”意在包含丙烯酸酯、甲基丙烯酸酯及其带有各种取代基的衍生物。
三至六官能的丙烯酸酯系单体的实例包括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(trimethylolpropaneethoxy triacrylate)(TMPEOTA)、丙氧基化甘油三丙烯酸酯(glycerin-propoxylated triacrylate)(GPTA)、季戊四醇四丙烯酸酯(PETA)和二季戊四醇六丙烯酸酯(DPHA)等。三至六官能的丙烯酸酯系单体可单独使用或以其组合的方式使用。
根据本发明的一个实施方案,可光固化的交联共聚物可为其中三至六官能的丙烯酸酯系单体彼此交联聚合的共聚物。
根据本发明的另一个实施方案,可光固化的交联共聚物可为其中三至六官能的丙烯酸酯系单体与单至双官能的丙烯酸酯系单体交联共聚的共聚物。
单至双官能的丙烯酸酯系单体的实例可包括丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、己二醇二丙烯酸酯(HDDA)、二缩三丙二醇二丙烯酸酯(tripropyleneglycol diacrylate)(TPGDA)和二丙烯酸乙二醇酯(ethyleneglycol diacrylate)(EGDA)等。单至双官能的丙烯酸酯系单体也可单独使用或者以其组合的方式使用。
当可光固化的交联共聚物为其中单至双官能的丙烯酸酯系单体与三至六官能的丙烯酸酯系单体交联共聚的共聚物时,对于单至双官能的丙烯酸酯系单体与三至六官能的丙烯酸酯系单体的含量比没有特别限制。根据本发明的一个实施方案,可包括单至双官能的丙烯酸酯系单体和三至六官能的丙烯酸酯系单体,其重量比为约1:99至约50:50,约10:90至约50:50,或约20:80至约40:60。当所包括的单至双官能的丙烯酸酯系单体与三至六官能的丙烯酸酯系单体的重量比处于上述范围时,可赋予硬涂层高硬度和柔韧性,且未使其他物理性质如卷曲性、耐光性等劣化。
此外,在本发明的硬涂膜中,硬涂层包括分散在可光固化的交联共聚物中的无机微粒。
根据本发明的一个实施方案,可使用粒径为约100nm以下,约10至约100nm,或约10至约50nm的无机纳米颗粒作为无机颗粒。例如可使用,二氧化硅颗粒、氧化铝颗粒、氧化钛颗粒或氧化锌颗粒作为无机颗粒。
包含在硬涂料组合物中的无机颗粒进一步改善了硬涂膜的硬度。
根据本发明的一个实施方案,硬涂层可包括约40至约90重量份的可光固化的交联共聚物和约10至约60重量份的无机颗粒,以100重量份的硬涂层计,或可包括约50至约80重量份的可光固化的交联共聚物和约20至约50重量份的无机颗粒,以100重量份的硬涂层计。硬涂层包括处于上述范围内的可光固化的交联共聚物和无机颗粒,因此形成了具有优异物理性能的硬涂膜。
此外,根据本发明的一个实施方案,当硬涂层在垂直于支撑基板的方向上被切半时,与邻近支撑基板表面的切半的硬涂层相比,更多的无机颗粒分散在邻近硬涂层表面的切半的硬涂层中。
同时,除了上述可光固化的交联共聚物和无机颗粒外,硬涂层可进一步包括常用的添加剂例如表面活性剂、返黄抑制剂、均化剂、防污剂等。在此,未特别限制添加剂的含量,因为只要不使本发明硬涂膜的物理性质劣化,其含量可进行各种调整。例如,可包括的添加剂的量为约0.1至约10重量份,以100重量份的可光固化的交联共聚物计。
根据本发明的一个实施方案,例如,硬涂层可包括作为添加剂的表面活性剂。该表面活性剂可为单至双官能的氟系丙烯酸酯、氟系表面活性剂或硅系表面活性剂。在这种情况下,表面活性剂可以分散在可光固化的交联共聚物中或与可光固化的交联共聚物交联的形式存在。
此外,硬涂层可包括作为添加剂的返黄抑制剂。返黄抑制剂可为二苯甲酮化合物、苯并三唑化合物等。
硬涂层可通过使一种包括粘合剂(包含三至六官能的丙烯酸酯系单体)、无机颗粒、光引发剂以及添加剂(如果需要)的硬涂料组合物发生光固化而形成。
光引发剂的实例可包括,但不限于,1-羟基-环己基-苯基酮、2-羟基-2-甲基-1-苯基-1-丙酮、2-羟基-1-[4-(2-羟基乙氧基)苯基]-2-甲基-1-丙酮、苯甲酰甲酸甲酯、α,α-二甲氧基-α-苯基苯乙酮、2-苯甲酰基-2-(二甲氨基)-1-[4-(4-吗啉基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-(4-吗啉基)-1-丙酮、双(2,4,6-三甲基苯甲酰基)苯基氧化膦、双(2,4,6-三甲基苯甲酰基)苯基氧化膦等。此外,市售光引发剂的实例可包括Irgacure184、Irgacure 500、Irgacure 651、Irgacure 369、Irgacure 907、Darocur1173、Darocur MBF、Irgacure 819Darocur TPO、Irgacure 907、Esacure KIP 100F等。这些光引发剂可独立使用或以其混合物的形式使用。
此外,为了调整硬涂料组合物的黏度和流动性,并改进硬涂料组合物对支撑基板的涂布性能,硬涂层可通过将包括有机溶剂的硬涂料组合物涂布到支撑基板上而形成。
有机溶剂的实例包括:醇例如甲醇、乙醇、异丙醇、丁醇等;烷氧基醇例如2-甲氧基乙醇、2-乙氧基乙醇、1-甲氧基-2-丙醇等;酮例如丙酮、甲基乙基酮、甲基异丁基酮、甲基丙基酮、环己酮等;醚例如丙二醇单丙醚、丙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单丁醚、二乙二醇-2-乙基己基醚等;以及芳香族溶剂例如苯、甲苯、二甲苯等。这些有机溶剂可单独使用或以其混合物的形式使用。
在本发明的硬涂膜中,当包括有机溶剂的硬涂料组合物被涂布到支撑基板上时,有机溶剂可包括在硬涂料组合物中,以使有机溶剂与包括粘合剂、第一无机颗粒、光引发剂和添加剂的固体含量的重量比为约70:30至约99:1。
根据本发明的一个实施方案,本发明的硬涂膜可通过以下步骤获得:将包括上述组分的硬涂料组合物涂布到支撑基板的至少一面上,然后光固化该硬涂料组合物以形成硬涂层。
完全固化的硬涂层的厚度为约50μm以上,例如,约50至约150μm或约70至约100μm。根据本发明,可提供一种虽然包括上述硬涂层但不会卷曲或破裂的高硬度硬涂膜。
根据本发明的一个实施方案,硬涂层可形成于支撑基板的仅一面上。
根据本发明的另一个实施方案,硬涂层可形成于支撑基板的两面上。
根据本发明的一个实施方案,本发明的硬涂膜还可包括选自以下的至少一种层或膜:塑料树脂薄膜、粘合膜、剥离膜、导电膜、导电层、涂层、固化树脂层、非导电膜、金属网层以及有图案的金属层,其中每一个均形成于硬涂层的至少一面上。层或膜可为单层、双层、叠层(laminate)等。使用粘合剂或粘合膜,通过层压、涂布、沉积、溅射等,可在硬涂层上形成层或膜,但不限于此。
当硬涂层形成于支撑基板的两面上时,可将硬涂料组合物依序涂布到支撑基板的正面和反面上,或同时涂布到支撑基板的两面上。
当硬涂层形成于支撑基板的两面上时,硬涂层可通过下述方法形成。
根据本发明的一个实施方案,本发明的硬涂膜可通过包括下述步骤的两步法形成:1)将第一硬涂料组合物涂布到支撑基板的一面上,然后光固化第一硬涂料组合物;以及2)将第二硬涂料组合物涂布到支撑基板的另一面上,然后光固化第二硬涂料组合物。在这种情况下,第一和第二硬涂料组合物各自均与上述硬涂料组合物相同,并且这些第一和第二硬涂料组合物被分别涂布到支撑基板的一面和另一面上。
在步骤2)中,由于在涂布了第一硬涂料组合物的面的反面上照射了紫外线,因此在步骤1)中由第一硬涂料组合物的卷曲和收缩而引起的卷曲在反方向上被抵消,从而获得一种平坦的硬涂膜。因此,不再需要额外的整平步骤。
根据本发明的一个实施方案,当硬涂膜暴露在温度为50℃以上且湿度为80%以上的环境中70个小时以上并在之后被放置在平板上时,硬涂膜的每个边缘与平板分隔的最大距离可为约1.0mm以下,约0.6mm以下,或约0.3mm以下。更具体而言,当硬涂膜暴露在温度为50-90℃且湿度为80-90%的环境中70-100个小时并在之后被放置在平板上时,硬涂膜的每个边缘与平板分隔的最大距离可为约1.0mm以下,约0.6mm以下,或约0.3mm以下。
因为具有高硬度、耐擦伤性、透明性、耐久性、耐光性、透光性等,本发明的硬涂膜可用于各种不同的领域。
例如,本发明的硬涂膜在1kg负载下可具有的铅笔硬度为7H以上、8H以上或9H以上。
此外,当摩擦试验器安装有钢丝绒#0000,并且随后在500g负载下将钢丝绒#0000在本发明的硬涂膜上往复摩擦400次时,可在硬涂膜上形成的刮痕数为2以下。
此外,本发明的硬涂膜的透光率可为91%以上或92.0%以上,浊度可为1.0%以下,0.5%以下,或0.4%以下。
此外,本发明的硬涂膜的初始颜色b*值为1.0以下。此外,借助紫外灯,当硬涂膜暴露在UV-B下72小时以上时,硬涂膜的初始颜色b*值与暴露在UV-B之后的硬涂膜的颜色b*值的差值可为0.5以下或0.4以下。
如上所述,本发明的硬涂膜可用于多个领域。例如,本发明的硬涂膜可被用于移动终端、智能手机或平板电脑的触控面板以及显示器或器件的外壳。
下面将结合下述实施例更加详细地描述本发明。然而,这些实施例是为了说明本发明,并且本发明的范围不限于此。
<实施例>
实施例1
将2g丙烯酸羟乙酯(HEA)、分散有约40重量%的量的粒径为20~30nm的二氧化硅纳米颗粒的8g二氧化硅-二季戊四醇六丙烯酸酯(DPHA)复合物(二氧化硅4g,DPHA 4g)、0.2g光引发剂(商品名:Darocur TPO)、0.1g苯并三唑系返黄抑制剂(商品名:Tinuvin400)和0.05g氟系表面活性剂(商品名:FC4430)进行混合,以制备第一硬涂料组合物。通过同样的方法还制备了第二硬涂料组合物。
将第一硬涂料组合物涂布到大小为15cmx20cm且厚度为188μm的PET支撑基板的一面上。然后,使用黑光荧光灯,在波长为280~350nm的紫外线下照射涂布有第一硬涂料组合物的PET支撑基板,从而光固化第一硬涂料组合物。
将第二硬涂料组合物涂布到PET支撑基板的另一面上。然后,使用黑光荧光灯,在波长为280~350nm的紫外线下照射涂布有第二硬涂料组合物的PET支撑基板,以光固化第二硬涂料组合物,从而制备硬涂膜。在此,形成于PET支撑基板的两面上的各硬涂层的厚度为100μm。
实施例2
以与实施例1相同的方法制备硬涂膜,不同之处在于:使用2g 9-二丙烯酸乙二醇酯(9-EGDA),而非2g丙烯酸羟乙酯(HEA)。
实施例3
以与实施例1相同的方法制备硬涂膜,不同之处在于:使用1g丙烯酸羟乙酯(HEA)和分散有约50重量%的量的粒径为20~30nm的二氧化硅纳米颗粒的9g二氧化硅-三羟甲基丙烷三丙烯酸酯(TMPTA)复合物(二氧化硅4.5g,TMPTA 4.5g),而非2g丙烯酸羟乙酯(HEA)和8g二氧化硅-二季戊四醇六丙烯酸酯(DPHA)复合物。
实施例4
将2g丙烯酸羟乙酯(HEA)和分散有约40重量%的量的粒径为20~30nm的二氧化硅纳米颗粒的8g二氧化硅-二季戊四醇六丙烯酸酯(DPHA)复合物(二氧化硅3.2g,DPHA 4.8g)、0.2g光引发剂(商品名:Darocur TPO)、0.1g苯并三唑系返黄抑制剂(商品名:Tinuvin 400)和0.05g氟系表面活性剂(商品名:FC4430)溶解在2g甲基乙基酮(MEK)中,以制备第一和第二硬涂料组合物。
将第一和第二硬涂料组合物分别涂布在大小为15cmx20cm且厚度为188μm的PC/PMMA复合支撑基板上。其后,以与实施例1相同的方法制备硬涂膜。
实施例5
以与实施例1相同的方法制备硬涂膜,不同之处在于:使用大小为15cmx20cm且厚度为80μm的TAC树脂支撑基板作为支撑基板。
比较实施例1
以与实施例1相同的方法制备硬涂膜,不同之处在于:只使用10g二季戊四醇六丙烯酸酯(DPHA),而非丙烯酸羟乙酯(HEA)和二氧化硅-二季戊四醇六丙烯酸酯(DPHA)复合物。
比较实施例2和3
以与实施例1相同的方法制备硬涂膜,不同之处在于:调整第一和第二硬涂料组合物的组分,如下表1所示。
实施例1至5和比较实施例1至3的主要组分和支撑基板总结于下表1。
[表1]
<测试实施例>
<测试方法>
1)铅笔硬度
根据日本标准JIS K5400评估铅笔硬度。就此而言,将铅笔硬度计在1.0kg负载下在每个硬涂膜上往复运动3次,从而测定未观察到刮痕时的硬度。
2)耐擦伤性
在加载到摩擦试验器上后,将钢丝绒(#0000)在0.5kg负载下在每个硬涂膜上往复运动400次,并且计数由此形成的刮痕。借助标记评估膜的耐擦伤性:O代表刮痕数为2以下,Δ代表刮痕数为2至小于5,以及x代表刮痕数为5以上。
3)耐光性
测定硬涂膜暴露在来自UV灯的UVB下72小时之前和之后的颜色b*值的差值。
4)透明度和浊度
使用光度计(商品名:COH-400)检测硬涂膜的透明度和浊度。
5)温度和湿度下的卷曲性能
将每个硬涂膜切割成10cmx10cm的大小,在温度为85℃且湿度为85%的室内储存72小时,然后放置在平面上,测量每个硬涂膜的边缘与平面分隔的最大距离。
6)圆柱弯曲试验
将各硬涂膜缠绕到直径为3cm的圆柱轴上,然后测定各硬涂膜是否破裂。如果各硬涂膜未破裂,则标示为OK,如果破裂了,则标示为X。
7)抗冲击性
通过测定22g钢球从高度为40cm处落在硬涂膜上时,各硬涂膜是否破裂而评估个硬涂膜的抗冲击性。当各硬涂膜未破裂时,标示为OK,若破裂,则标示为X。
硬涂膜的物理性能的测定结果总结于下表2。
[表2]
如上表2所示,可确定,实施例1至5的所有硬涂膜都具有良好的物理性能。

Claims (19)

1.一种硬涂膜,包括:
支撑基板;以及
形成于支撑基板的至少一面上的硬涂层,
其中硬涂层包括包含三至六官能的丙烯酸酯系单体的可光固化的交联共聚物,以及分散在可光固化的交联共聚物中的无机颗粒。
2.权利要求1的硬涂膜,其中可光固化的交联共聚物是共聚物,其中三至六官能的丙烯酸酯系单体与单至双官能的丙烯酸酯系单体交联聚合。
3.权利要求1的硬涂膜,其中三至六官能的丙烯酸酯系单体包括至少一种选自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(trimethylolpropaneethoxy triacrylate)(TMPEOTA)、丙氧基化甘油三丙烯酸酯(GPTA)、季戊四醇四丙烯酸酯(PETA)和二季戊四醇六丙烯酸酯(DPHA)的化合物。
4.权利要求2的硬涂膜,其中单至双官能的丙烯酸酯系单体包括至少一种选自丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、己二醇二丙烯酸酯(HDDA)、二缩三丙二醇二丙烯酸酯(TPGDA)和二丙烯酸乙二醇酯(EGDA)的化合物。
5.权利要求1的硬涂膜,其中支撑基板包括至少一种选自聚对苯二甲酸乙二醇酯(PET)、环烯烃共聚物(COC)、聚丙烯酸酯(PAC)、聚碳酸酯(PC)、聚乙烯(PE)、聚甲基丙烯酸甲酯(PMMA)、聚醚醚酮(PEEK)、聚萘二甲酸乙二醇酯(PEN)、聚醚酰亚胺(PEI)、聚酰亚胺(PI)、三乙酰基纤维素(TAC)和甲基丙烯酸甲酯(MMA)的化合物。
6.权利要求1的硬涂膜,其中无机微颗粒的粒径为100nm以下。
7.权利要求1的硬涂膜,其中无机颗粒包括至少一种选自二氧化硅纳米颗粒、氧化铝纳米颗粒、氧化钛纳米颗粒和氧化锌纳米颗粒的颗粒。
8.权利要求1的硬涂膜,还包括分散在可光固化的交联共聚物中或与可光固化的交联共聚物交联的添加剂。
9.权利要求8的硬涂膜,其中添加剂分散在可光固化的交联共聚物中或与可光固化的交联共聚物交联,并包括至少一种选自单至双官能的氟系丙烯酸酯、氟系表面活性剂和硅系表面活性剂的化合物。
10.权利要求8的硬涂膜,其中添加剂分散在可光固化的交联共聚物中,并包括包含二苯甲酮化合物或苯并三唑化合物的返黄抑制剂。
11.权利要求1的硬涂膜,其中硬涂层包括40至90重量份的可光固化的交联共聚物和10至60重量份的无机颗粒。
12.权利要求1的硬涂膜,其中硬涂膜在1kg的负载下的铅笔硬度为7H以上。
13.权利要求1的硬涂膜,其中当硬涂层的表面在500g的负载下被钢丝绒#0000在其上往复摩擦400次时,形成的刮痕数为2以下。
14.权利要求1的硬涂膜,其中硬涂膜的透光率为91%以上,浊度为0.4以下,且b*值为1.0以下。
15.权利要求1的硬涂膜,其中当硬涂膜暴露在UV-B下72个小时时,硬涂层的b*变化值为0.5以下。
16.权利要求1的硬涂膜,还包括至少一种选自塑料树脂膜、粘合膜、剥离膜、导电膜、导电层、涂层、固化树脂层、非导电膜、金属网层以及图案化金属层的层,其各自形成于硬涂层上。
17.权利要求1的硬涂膜,其中硬涂层的厚度为50至150μm。
18.权利要求1的硬涂膜,其中当硬涂膜暴露在温度为50℃以上且湿度为80%以上的环境中70个小时以上并在之后被放置在平面上时,硬涂膜的每个边缘与平面分隔的最大距离为1.0mm以下。
19.权利要求1的硬涂膜,其中支撑基板与硬涂层的厚度比为1:0.5至1:2。
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US11161951B2 (en) 2015-08-03 2021-11-02 Lg Chem, Ltd. Coating composition for flexible plastic film
CN110066412A (zh) * 2015-08-03 2019-07-30 株式会社Lg化学 柔性塑料膜
US11168191B2 (en) 2015-08-03 2021-11-09 Lg Chem, Ltd. Flexible plastic film
CN110066412B (zh) * 2015-08-03 2022-06-28 株式会社Lg化学 柔性塑料膜
CN112702858A (zh) * 2015-08-11 2021-04-23 三星电子株式会社 用于制造外壳的方法和包括外壳的电子设备
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US11805611B2 (en) 2015-08-11 2023-10-31 Samsung Electronics Co., Ltd. Method for manufacturing exterior housing and electronic device comprising same
CN109232942A (zh) * 2017-06-06 2019-01-18 宁波惠之星新材料科技有限公司 一种高硬度的光固化型硬化膜及其制备方法
US10954409B2 (en) 2017-09-15 2021-03-23 Lg Chem, Ltd. Hard coating film
CN108749232A (zh) * 2018-07-28 2018-11-06 汕头海洋第聚酯薄膜有限公司 一种用于模内转印的易成型聚酯薄膜及其制备方法
CN109486432A (zh) * 2018-09-30 2019-03-19 张家港康得新光电材料有限公司 柔性导电膜用双面硬化膜
KR20220002197A (ko) * 2020-12-10 2022-01-06 삼성전자주식회사 외관 하우징, 이의 제작 방법 및 이를 구비한 전자 장치
KR102499790B1 (ko) * 2020-12-10 2023-02-16 삼성전자주식회사 외관 하우징, 이의 제작 방법 및 이를 구비한 전자 장치

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