CN104039899B - 硬涂用组合物及包含其的黄变得到改善的装饰用膜 - Google Patents
硬涂用组合物及包含其的黄变得到改善的装饰用膜 Download PDFInfo
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Abstract
本发明公开一种硬涂用组合物及其制备方法,上述硬涂用组合物的其特征在于,包含具有(甲基)丙烯酰(acryloyl)官能团的紫外线固化型树脂以及氟树脂。并且,本发明提供包含装饰用膜及其制备方法,其中,上述装饰用膜包含硬涂层、印刷层、粘结层,上述装饰用膜的特征在于,上述硬涂层由包含具有(甲基)丙烯酰(acryloyl)官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成。
Description
技术领域
本发明涉及一种用于改善注塑成型品表面的黄变的装饰用膜,更为详细地,涉及改善由于紫外线(UV)造成的黄变的硬涂组合物和包含着含有该硬涂组合物的硬涂层的装饰用膜及其制备方法。
背景技术
为了防止由于紫外线造成的黄变,一般对硬涂层引入紫外线吸收剂或者紫外线稳定剂,但在这种情况下,由于与硬涂液之间的兼容性差,因而存在产生凝胶化或者效果甚微的情况。而且,在注塑成型后经过紫外线固化,而在紫外线固化时,由于紫外线吸收剂或者紫外线稳定剂,使得原子团的形成受阻,因而有可能使硬涂层的固化密度下降。并且,由于根据种类只对特定波长的紫外线进行反应,因而存在需要混合多个种类来使用的缺点。
并且,在韩国公开公报第10-2011-0069436号中也只公开了由于包含由放射线固化型树脂以及热固化型树脂的混合物而形成的涂敷用组合物,因而硬涂层不会破碎或者被剥离,如表面硬度等的对注塑物所要求的物理性质卓越的成型膜,并没能提供改善在上述的注塑成型后,由紫外线引起的硬涂层的黄变的效果。
发明内容
本发明要解决的技术问题
本发明的目的在于,提供改善注塑成型后由紫外线引起的黄变的硬涂用组合物及其制备方法。
本发明的再一目的在于,提供包含由上述硬涂用组合物形成的硬涂层的装饰用膜及其制备方法。
技术方案
为达成上述一目的,本发明提供一种硬涂用组合物,其特征在于,包含具有(甲基)丙烯酰(acryloyl)官能团的紫外线固化型树脂以及氟树脂。
另一方面,上述硬涂用组合物可通过包括以下步骤的方法来制备:制备具有环氧官能团的(甲基)丙烯酸酯共聚物的步骤;使(甲基)丙烯酸单体与上述(甲基)丙烯酸酯共聚物进行加成反应,来制备具有丙烯酰官能团的紫外线固化型树脂的步骤;以及掺和(blend)上述紫外线固化型树脂及氟树脂的步骤。
为达成上述再一目的,本发明提供装饰用膜及其制备方法,其中,上述装饰用膜包括硬涂层、印刷层、粘结层,上述装饰用膜的特征在于,上述硬涂层由包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成;并提供该装饰用膜的制备方法。
有益效果
本发明的装饰用膜所包含的引入氟树脂的硬涂层能够阻断紫外线,因而具有能够防止注塑成型后的由紫外线引起的黄变现象的优点。
并且,由于上述氟树脂比重高,因而在形成硬涂层时向下方排列,但是由于在转印后向注塑品的表面方向排列,因而即使使用少量也能够对改善黄变具有卓越的效果。
附图说明
图1是简要表示本发明的实施例的装饰用膜的结构的图。
图2是简要表示本发明的再一实施例的装饰用膜的结构的图。
图3是简要表示本发明的再一实施例的转印后的装饰用膜的结构的图。
具体实施方式
以下参照多个实施例会让本发明的优点和特征以及实现这些优点和特征的方法更加明确。但是,本发明不局限于以下所公开的实施例,能够以互不相同的各种方式实施,本实施例只用于使本发明的公开内容更加完整,有助于本发明所属技术领域的普通技术人员完整地理解本发明的范畴,本发明根据发明要求保护的范围而定义。
以下,将对本发明的硬涂用组合物以及对包含该硬涂用组合物的改善黄变的装饰用膜进行详细说明。
本发明的硬涂用组合物,其特征在于,包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂。
具有(甲基)丙烯酰官能团的紫外线固化型树脂能够使本发明的硬涂用组合物借助紫外线来进行固化。在本发明中,可将紫外线固化看作在照射紫外线时借助包含于树脂的(甲基)丙烯酰官能团的反应形成固化反应。
优选地,上述紫外线固化型树脂的环氧当量优选为200g/eq~20000g/eq,(甲基)丙烯酰当量优选为100g/eq~1000g/eq。当紫外线固化型树脂的环氧当量以及(甲基)丙烯酰当量符合上述各自的范围时,热固化效率优秀,在热固化后能够适当抑制粘结性等,耐化学性、紫外线固化后的耐磨耗性等优秀。
并且,上述紫外线固化型树脂的重均分子量(Mw)优选为5000~100000。在紫外线固化型树脂的重均分子量小于5000的情况下,由于高分子的凝聚力不足,因而有可能使耐刮性、耐磨耗性等不充分。相反,在紫外线固化型树脂的重均分子量大于100000的情况下,表现出凝胶(Gelling)现象,因而导致自体聚合反应变得困难。
上述硬涂用组合物以包含氟树脂为特征,上述氟树脂作为含有氟的塑料,从而化学性质出色且种类多。虽然对能够在本发明中使用的氟树脂没有特别限制,例如能够使用聚四氟乙烯(PTFE,Polytetrafluoroethylene)、聚三氟氯乙烯(PCTFE,Polychlorotrifluoroethylene)、聚偏二氟乙烯(PVDF,Polyvinylidenefluoride)、聚氟乙烯(PVF,polyvinylfluoride),优选地,使用聚四氟乙烯。
上述聚四氟乙烯作为需求量最多的代表性的氟树脂,是以特氟纶的商品名为周知的结晶性树脂,具有能够承受在260℃下的长期使用的耐热性,耐药品性、电绝缘性、非粘合性、低摩擦系数、难燃性等特殊性,并且对人体无害。
上述氟树脂的特征在于,是阻断紫外线的粒子。由于与热干燥方法相比,具有高生产性、高硬度、表面光泽、电绝缘性等多种优点,因而引入紫外线固化方法,但在紫外线固化工序中或者紫外线固化后有可能引起包含透明树脂的涂敷层呈浅黄色或者土棕色的现象,将这种现象称为黄变现象。此时,能够借助包含作为紫外线阻断粒子的氟树脂的硬涂用组合物,来抑制在产生注塑成型后,由紫外线引起的黄变现象。
由于由上述氟树脂形成的紫外线阻断粒子的比重高达2.2左右,因而在形成硬涂层时向下方排列,但是转印后向注塑品的表面方向排列,因此适用少量也能够阻断紫外线,从而抑制黄变现象的效果优秀。
并且,优选地,相对于100重量份的上述紫外线固化型树脂,包含0.5重量份~10重量份的上述氟树脂。在上述氟树脂的含量小于0.5重量份的情况下,由于硬涂用组合物内的氟树脂的含量过少,因而紫外线阻断效果甚微,使得改善在注塑成型后由紫外线引起的黄变的效果下降,在上述氟树脂的含量大于10重量份的情况下,由于氟树脂粒子引发黑子,因而存在包含硬涂用组合物的硬涂层的透明度大大下降,在最终产品的紫外线固化时,存在降低反应性的忧虑。
本发明的氟树脂的粒径优选为0.2μm~10μm。在上述氟树脂的粒径小于0.2μm的情况下,由于粒子的大小太小,会使得紫外线阻断效果甚微,使得黄变改善效果下降,在上述氟树脂的粒径大于10μm的情况下,能够用肉眼观察到由氟树脂形成的紫外线阻断粒子,因而存在硬涂组合物的透明度大大下降的忧虑,在形成包含上述硬涂组合物的涂敷层时,由于阻断紫外线的氟树脂,而在上述硬涂层表面产生弯曲,有可能使平滑度变差。
本发明的硬涂用组合物,可还包括:溶剂,用于使上述紫外线固化型树脂以及紫外线阻断粒子分散;紫外线引发剂;以及抗氧化剂。上述紫外线引发剂可利用安息香类、羟基酮类、氨基酮类、氧化膦类等的化合物;上述抗氧化剂可利用苯酚类抗氧化剂、磷类抗氧化剂、螯合物类抗氧化剂等。
并且,本发明的硬涂用组合物根据需要可还包括润滑剂、紫外线、吸收剂、热固化用催化剂、填充物、异硫氰酸酯化合物等中的一种以上物质。
本发明的硬涂用组合物,可在制备具有环氧官能团的(甲基)丙烯酸酯共聚物后,使如同(甲基)丙烯酸单体一样具有(甲基)丙烯酰官能团的化合物与所制备的(甲基)丙烯酸酯共聚物进行加成反应,来制备具有丙烯酰官能团的紫外线固化型树脂,之后对所制备的上述紫外线固化型树脂掺和氟树脂来制备。
这时,具有环氧官能团的(甲基)丙烯酸酯共聚物可通过(甲基)丙烯酸甲酯和(甲基)丙烯酸缩水甘油酯共聚合来制备。(甲基)丙烯酸甲酯和(甲基)丙烯酸缩水甘油酯的共聚合可适用溶液聚合、光聚合、本体聚合等多种方式。
并且,(甲基)丙烯酸单体等的使用量,可根据所制备的紫外线固化型树脂的(甲基)丙烯酰当量来决定。并且,在制备组合物时,可添加紫外线固化剂、抗氧化剂、其他添加剂。
图1是简要表示本发明实施例的装饰用膜的结构的图。在此,装饰用膜意味着能够借助转印方法、注塑同时转印方法、插入方法或者附着方法等多种方法来在成型品的表面形成硬涂层的膜。
参照图1,所示的装饰用膜包括硬涂层120、印刷层130以及粘结层140。本发明的特征在于,上述硬涂层120由包含(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成。
上述硬涂层120是为了在注塑成型时,防止在将要后述的印刷层130产生刮痕而形成。包含本发明的硬涂组合物,并包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的上述硬涂组合物可在大约100℃~170℃左右的温度下,处理约30秒钟~2分钟而形成。
此时,硬涂层120厚度可以是3μm~10μm。在硬涂层的厚度小于3μm的情况下,可能使硬涂层的表面物理性质,即,使硬度、耐磨耗性等下降。相反,在硬涂层120的厚度大于10μm的情况下,由于硬涂层的物理性质变脆弱(Brittle),因而成型时不仅产生破裂(Crack),而且,有可能使制备费用过分增大,而没有再提高效果。
上述粘结层140形成于上述硬涂层120上,使装饰用膜附着到成型品。为了形成粘结层140,可利用聚丙烯类树脂、聚苯乙烯类树脂、聚酰胺类树脂、氯化聚烯烃类树脂、氯化乙烯-醋酸乙烯共聚物树脂、橡胶类树脂等。
上述粘结层140的厚度,在达成本发明的目的的范围内没有限制,为保护上述粘结层140,可在粘结层140上形成有保护膜(未图示)。
上述印刷层130可通过凹版印刷或者柔性版印刷中的某一方法来形成。由于印刷层130具有相同或者不同的图案,因而能够以所期望的形态自由体现人物照片、模式、多种颜色、多种图案等。
图2是简要表示本发明再一实施例的装饰用膜的结构的图。
参照图2,所示的装饰用膜包括基材层100、脱模层110、硬涂层120、印刷层130以及粘结层140。在本发明的装饰用膜的由包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成的硬涂层120的下部,可包含基材或者脱模层。
上述基材层100起到从整体上维持装饰用膜的形态的作用。优选地,上述基材层使用耐热性合成树脂,并且可包含选自聚酯类树脂、聚丙烯树脂、聚酰胺类树脂、聚乙烯类树脂以及三醋酸基类树脂中的一种或者两种以上的混合树脂。
尤其,优选地,上述基材层利用上述聚酯类树脂中的聚对苯二甲酸乙二酯(PET)树脂或者聚乙烯对苯乙二醇(PETG)树脂来制备。由于聚对苯二甲酸乙二酯或者聚乙烯对苯乙二醇具有比普通的基材原材料更优秀的延伸率,因而可使本发明的装饰用膜的成型性极大化。
并且,上述基材层100的厚度优选为20μm~200μm。在上述基材层100的厚度小于20μm的情况下,所产生的膜的收缩率大,因此难以作业,而大于200μm的情况下,在注塑成型时,可能使曲面成型难。
为了形成上述脱模层110,可使用环氧类、环氧-密胺类、氨基醇酸类、丙烯酸类、密胺类、硅类、氟类、纤维素类、尿素树脂类、聚烯烃类、石蜡类等的离型剂。
这样的脱模层110的厚度可以是0.1μm~5μm。在脱模层的厚度小于0.1μm的情况下,难以确保离型物理性质,相反,在脱模层的厚度大于5μm的情况下,在成型时可能会引发脱模层的破裂。
图3是简要表示本发明的再一实施例的转印后的装饰用膜的结构的图,将本发明的硬涂层划分为1/2,将1/2以上的部分即在注塑品露出的部分称为硬涂层的上部,将其相反一侧的1/2以下的部分称为硬涂层的下部,并且,上述硬涂层的下部可以与作为非注塑品的印刷层以及粘结层等相接处。此时,本发明的特征在于,硬涂层的上部的上述氟树脂的分布密度高于硬涂层的下部的上述氟树脂的分布密度。
更为具体地,本发明的硬涂层由包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成,而上述氟树脂在形成硬涂层时,向硬涂层的下部方向排列,但是在转印后,由于分布密度向硬涂层的上部方向提高,上述氟树脂的分布向注塑品表面方向倾斜排列,因而能够阻断紫外线来抑制黄变现象。并且,因转印后氟树脂的分布密度,即使适用少量的上述氟树脂,抑制黄变现象的效果也优秀。
上述的本发明的装饰用膜可以采用模内转印膜。模内转印膜在模内注塑工序中对成型物的质量起到非常重要的影响,通常,由具有离型性的基膜、在该基膜上依次层压的保护层、具有预定图案的印刷层以及粘结层形成模内转印膜。但是,在将本发明的上述装饰膜用作模内转印膜的情况下,包括由包含氟树脂的硬涂用组合物形成的硬涂层,与以往的模内转印膜相比,可改善由紫外线引起的黄变现象,因而能够制备质量优秀的注塑品,并且可减少由变色造成的不良品的生产。
本发明的装饰用膜的制备方法,其特征在于,包括以下步骤:在基材的上部形成脱模层的步骤,在上述脱模层的上部形成硬涂层的步骤,在上述硬涂层的上部形成印刷层的步骤,以及在上述印刷层的上部形成粘合剂层的步骤;此时,上述硬涂层由包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成。
在上述脱模层的上部形成硬涂层的步骤中,由于氟树脂的比重大,氟树脂的分布密度向下方排列,但是在转印后,由于在注塑品露出的硬涂层的上部的上述氟树脂的分布密度高于上述硬涂层的下部的上述氟树脂的分布密度,因而能够改善由紫外线引起的黄变现象。
以下,通过本发明的优选实施例,观察本发明的硬涂形成用片的特性。只是,该实施例是作为本发明的优选例示而提出的,在任何意义上也不能解释为本发明限定于该实施例。在本发明所属技术领域的普通技术人员,能够在技术上充分导出未在此记载的内容,因此省略其说明。
1.装饰用膜的制备
实施例1
将甲基丙烯酸缩水甘油酯(GMA)110g、甲基丙烯酸甲酯(MMA)30g、苯乙烯60g、醋酸丁酯(BA)1500g以及2,2'-偶单双(AIBN)2.5g放入设有搅拌装置、冷却管、装载组(lot)以及氮导入管的反应器中。
之后,在氮气流下,经过约1个小时,将反应器内的温度提升到约65℃后,进行约9小时保温。接着,使用装载组,在氮气流下,将包含甲基丙烯酸缩水甘油酯(GMA)430g、甲基丙烯酸甲酯(MMA)120g、苯乙烯250g、月桂硫醇5g以及偶氮二异丁腈(AIBN)10g的混合物经过约2个小时装载至反应装置,并在相同温度下进行了约3个小时保温。之后,放入偶氮二异丁腈(AIBN)2.5g,进行了2个小时保温。接着,将温度调整为约105℃,并将氮导入管替换为空气导入管后,放入丙烯酸(AA)370g、p-甲氧基苯酚(p-methoxyphenol)0.5g以及4-二甲氨基吡啶(DMAP)0.4g进行混合后,在空气起泡下维持在105℃。在相同温度下进行15小时保温后,放入p-甲氧基苯酚0.5g,进行冷却之后,添加甲基乙基酮,使不挥发份达到30%,由此制备了具有丙烯酰官能团的紫外线固化型树脂。
在用化学滴定法对所制备的紫外线固化型树脂进行测定的结果,环氧当量为6600g/eq、丙烯酰当量为349g/eq,用凝胶渗透色谱(GPC)测定的标准聚苯乙烯换算重均分子量为60000。
接着,对所制备的紫外线固化型树脂1000g,放入粒径为4μm的聚四氟乙烯20g,并混合紫外线引发剂80g、抗氧化剂10g、纳米硅200g、甲基乙基酮700g,来制备了硬涂用组合物。
之后,用凹版印刷方法,以约1μm的厚度将密胺类离型剂涂敷在厚度为50μm的聚对苯二甲酸乙二醇酯(PET)膜的一面,形成了脱模层。接着,用微凹版涂敷方法,以约6μm的厚度,将所制备的硬涂用组合物涂敷在脱模层上。之后,在150℃下将所涂敷的涂敷液加热30秒钟,形成含有上述硬涂用组合物的硬涂层,由此制备了装饰用膜。
实施例2
除了利用聚三氟氯乙烯来代替聚四氟乙烯之外,用与实施例1相同的方法来制备了装饰用膜。
比较例1
除了利用聚四氟乙烯之外,用与实施例1相同的方法制备了装饰用膜。
比较例2
除了利用氧化锌粉末来代替聚四氟乙烯之外,用与实施例1相同的方法来制备了装饰用膜。
2.物理性质评价
为了评价物理性质,在对上述实施例1、实施例2以及比较例1、比较例2的装饰用膜涂敷用于赋予装饰效果的印刷层以及粘结剂层后,实施了充分的时效处理(Aging)。之后,利用各个片注塑后,通过紫外线固化机来制备了物理性质评价用试片。
为了评价耐候性,一边在沃美(WOM,Weather-O-Meter)试验机中照射1000小时紫外线,一边改变温度及湿度,用肉眼观察了变色、脱色及光泽、表面的变化。
并且,将所制备的各个上述试片放入紫外加速老化(QUV)试验机,使用平均波长为313nm的紫外线灯,以辐照度(Irradiance)0.72W/m2、温度70℃的条件曝光100小时后,利用色差仪测定了初期和紫外线曝光后的色差(△E)。
表1
参照上表1,耐候性是指能够很好地承受外部环境变化的性质,从在实施例1及实施例2的情况下测定的耐候性,与比较例1及比较例2的情况相比优秀来看,能够确认紫外线阻断效果优秀。
另一方面,△E越小,光泽及颜色变化少,因而能够了解到△E越小,黄变也会降低。与耐候性结果相同,与比较例1及比较例2相比,实施例1及实施例2的由紫外线引起的变为黄色的变化少。
并且,虽然在使用包含聚三氟氯乙烯的硬涂组合物的情况下,耐候性良好、△E也小,但是在包含聚四氟乙烯的情况,就耐候性以及△E而言,表现出卓越的优秀性。
Claims (3)
1.一种装饰用膜,从上到下依次包括硬涂层、印刷层、粘结层,所述装饰用膜的特征在于,所述硬涂层由包含具有(甲基)丙烯酰官能团的紫外线固化型树脂以及氟树脂的硬涂用组合物形成,
上述紫外线固化型树脂的环氧当量为200g/eq~20000g/eq,(甲基)丙烯酰当量为100g/eq~1000g/eq,
所述硬涂层的上部的氟树脂分布密度大于所述硬涂层的下部的氟树脂分布密度;
所述氟树脂为阻断紫外线的粒子,其粒径为0.2μm~10μm;
相对于100重量份的所述紫外线固化型树脂,包含0.5重量份~10重量份的所述氟树脂。
2.根据权利要求1所述的装饰用膜,其特征在于,在所述硬涂层的下部包括基材或者脱模层。
3.根据权利要求1所述的装饰用膜,其特征在于,所述装饰用膜为模内转印膜。
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KR101964092B1 (ko) * | 2014-08-01 | 2019-04-02 | (주)엘지하우시스 | 폴리테트라플루오로에틸렌을 포함하는 하드코팅 조성물, 하드코팅층 및 이를 포함하는 바닥재 |
KR102264801B1 (ko) * | 2016-04-28 | 2021-06-11 | 아라까와 가가꾸 고교 가부시끼가이샤 | 열경화성 이형 코팅제, 이형필름, 이형필름의 제조방법 |
JP6929176B2 (ja) * | 2017-09-19 | 2021-09-01 | 藤森工業株式会社 | 立体成型物の製造方法 |
JP2021035723A (ja) * | 2017-12-20 | 2021-03-04 | Agc株式会社 | 加飾フィルムおよび加飾フィルム付き3次元成形品の製造方法 |
JP7151721B2 (ja) * | 2017-12-20 | 2022-10-12 | Agc株式会社 | 加飾フィルム、加飾フィルムの製造方法、加飾フィルム付き3次元成形品の製造方法および含フッ素重合体組成物 |
WO2019124490A1 (ja) * | 2017-12-20 | 2019-06-27 | Agc株式会社 | 加飾フィルムおよび加飾フィルム付き3次元成形品の製造方法 |
CN111100489B (zh) * | 2018-10-26 | 2022-03-15 | 3M创新有限公司 | 一种离型硬涂料、一种离型膜和一种光伏组件 |
EP3843625B1 (en) | 2018-11-18 | 2022-07-13 | Asociatia Transylvanian Institute of Neuroscience | Method, human machine interface, machine computing unit and computer programs to control at least one actuator to carry out at least one task |
TWI698336B (zh) * | 2019-05-10 | 2020-07-11 | 南亞塑膠工業股份有限公司 | 節能膜結構 |
TWI737442B (zh) * | 2020-08-11 | 2021-08-21 | 正清國際有限公司 | 熱轉印膜元件 |
KR20220164830A (ko) * | 2021-06-03 | 2022-12-14 | 삼성디스플레이 주식회사 | 윈도우 및 그 윈도우를 포함하는 표시 장치 |
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US20140349052A1 (en) | 2014-11-27 |
JP2015509997A (ja) | 2015-04-02 |
JP6085830B2 (ja) | 2017-03-01 |
CN104039899A (zh) | 2014-09-10 |
KR101426129B1 (ko) | 2014-08-05 |
TW201329169A (zh) | 2013-07-16 |
TWI516551B (zh) | 2016-01-11 |
EP2803706A1 (en) | 2014-11-19 |
WO2013105742A1 (ko) | 2013-07-18 |
KR20130082228A (ko) | 2013-07-19 |
EP2803706A4 (en) | 2015-09-02 |
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