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CN112839807B - 透明性树脂膜、装饰板和装饰板的制造方法 - Google Patents

透明性树脂膜、装饰板和装饰板的制造方法 Download PDF

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Publication number
CN112839807B
CN112839807B CN201980067162.8A CN201980067162A CN112839807B CN 112839807 B CN112839807 B CN 112839807B CN 201980067162 A CN201980067162 A CN 201980067162A CN 112839807 B CN112839807 B CN 112839807B
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layer
resin film
transparent resin
haze
laminated
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CN112839807A (zh
Inventor
古田哲
藤井亮
中岛智美
根津义昭
茅原利成
住田阳亮
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Abstract

本发明提供在基材所设置的图案层上叠层时能够目视确认密合状态的透明性树脂膜、以及使用该透明性树脂膜得到的装饰板以及该装饰板的制造方法。本发明涉及用于保护在基材的一侧叠层的图案层的透明性树脂膜,上述透明性树脂膜的特征在于,至少具有热塑性树脂层、和在上述图案层上叠层的一侧的外部雾度层。

Description

透明性树脂膜、装饰板和装饰板的制造方法
技术领域
本发明涉及透明性树脂膜、使用该透明性树脂膜得到的装饰板以及该装饰板的制造方法。
背景技术
近年来,由于使用喷墨打印机的喷墨印刷法的普及,在建材或装饰成型品等所使用的装饰片中,也能够应对多品种·小批量的生成,并且作为图案层能够印刷复杂的图案(文字、数字以及图形等)。并且,喷墨印刷法具有所印刷的基材不限于膜,对于平板或者具有凹凸或曲面的基材也能够印刷的优点。
但是,利用喷墨印刷法印刷的图案层通常位于基材的最表面,因而耐划伤性或耐污染性以及耐候性等表面性能不充分,为了保护该图案层,需要在图案层的表面叠层透明性树脂膜。
作为这样的透明性树脂膜,例如在专利文献1中公开了在含有三嗪系紫外线吸收剂和受阻胺系光稳定剂的透明聚丙烯的一侧表面设有保护层、在另一表面设有粘合层的覆层膜。
但是,现有的透明性树脂膜在与基材所设置的图案层叠层时,即使在上述基材所设置的图案层与透明性树脂膜之间夹入了空气的情况下,透明性树脂膜的表面的光泽的变化量也小,难以通过目视判断是否夹入空气,而在夹入了空气时,存在图案层与透明性树脂膜之间的密合力降低的问题。
现有技术文献
专利文献
专利文献1:日本特开2005-120255号公报
发明内容
发明要解决的技术问题
本发明的目的在于提供在基材所设置的图案层上叠层时能够目视确认密合状态的透明性树脂膜、以及使用该透明性树脂膜得到的装饰板以及该装饰板的制造方法。
用于解决技术问题的技术手段
为了解决上述技术问题,本发明的发明人进行了深入研究,结果发现在透明性树脂膜中,通过在与基材的图案层叠层的一侧的表面设置外部雾度层,在基材的图案层的表面叠层透明性树脂膜时,能够通过目视容易地判断是否夹入了空气,将与上述图案层的密合力因夹入空气而下降的产品排除在外,由此,能够得到容易制成与上述图案层的密合性优异的产品的透明性树脂膜,从而完成了本发明。
本发明是用于保护在基材的一侧叠层的图案层的透明性树脂膜,上述透明性树脂膜的特征在于,至少具有热塑性树脂层、和在上述图案层上叠层的一侧的外部雾度层。
优选上述外部雾度层的雾度值为4%以上且小于100%。
优选在上述外部雾度层的与热塑性树脂层侧相反的一侧隔着纯水层粘贴雾度值为0.1%以下的聚对苯二甲酸乙二醇酯膜,从上述热塑性树脂层侧测定的背面润湿的状态下的雾度值为90%以下。
优选上述外部雾度层的厚度为0.5μm以上20μm以下。
优选上述透明性树脂膜的与在上述图案层上叠层的一侧相反的一侧具有凹凸形状,雾度值(1)为70%以上,雾度值(2)为70%以下,雾度值(1)是去除与在上述图案层上叠层的一侧相反的一侧的表面雾度后的雾度值,雾度值(2)是去除在上述图案层上叠层的一侧的表面雾度、和与在上述图案层上叠层的一侧相反的一侧的表面雾度后的雾度值。
优选上述热塑性树脂层的与在上述图案层上叠层的一侧相反的一侧具有表面保护层。
并且,本发明还为一种装饰板,其特征在于,在厚度方向上依次具有基材、图案层和本发明的透明性树脂膜。
本发明还为装饰板的制造方法,其是本发明的装饰板的制造方法,其特征在于,包括:在透明性树脂膜的将叠层图案层的一侧的表面形成粘接剂层的工序;和通过上述粘接剂层将上述透明性树脂膜与上述图案层贴合的工序。
本发明还为装饰板的制造方法,其特征在于,包括:在透明性树脂膜的叠层图案层的一侧的表面形成粘接剂层的工序;和通过上述粘接剂层将上述透明性树脂膜与上述图案层贴合的工序。
发明效果
本发明的透明性树脂膜的在基材的图案层上叠层的一侧的表面具有外部雾度层,因而在基材的图案层的表面叠层透明性树脂膜时,能够通过目视容易地判断是否夹入了空气,将与上述图案层的密合力因夹入空气而下降的产品排除在外,由此,容易制成与上述图案层的密合性优异的产品。
在基材的图案层表面叠层这样的本发明的透明性树脂膜而得到的本发明地装饰板容易形成图案层与透明性树脂膜之间不夹入空气的状态,容易制成它们的密合力优异的产品。
附图说明
图1是表示本发明的透明性树脂膜的优选的一例的截面的示意图。
图2是表示本发明的透明性树脂膜的优选的另一例的截面的示意图。
图3是表示本发明的装饰板的优选的一例的截面的示意图。
具体实施方式
<透明性树脂膜>
先对本发明的透明性树脂膜进行说明。
其中,在以下记载中,“~”所示的数值范围的下限上限意指“以上以下”(例如α~β为α以上β以下)。
利用附图对本发明的透明性树脂膜的优选的一例进行说明。
如图1所示,本发明的透明性树脂膜10至少具有热塑性树脂层11和外部雾度层12。
(热塑性树脂层)
作为构成上述热塑性树脂层的热塑性树脂,包含1种以上的下列树脂,例如可以列举:聚乙烯(低密度聚乙烯、中密度聚乙烯、高密度聚乙烯)、乙烯-α-烯烃共聚物、聚丙烯、聚丁烯、聚甲基戊烯、乙烯-丙烯共聚物、丙烯-丁烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-乙酸乙烯酯共聚物皂化物、烯烃系热塑性弹性体、或者它们的混合物等烯烃树脂;聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、乙二醇-对苯二甲酸-间苯二甲酸共聚物、对苯二甲酸-乙二醇-1,4-环己烷二甲醇共聚物、聚酯系热塑性弹性体等聚酯树脂;聚(甲基)丙烯酸甲酯、(甲基)丙烯酸甲酯-(甲基)丙烯酸丁酯共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物等丙烯酸树脂;尼龙-6、尼龙-66等聚酰胺系热塑性树脂;聚碳酸酯树脂、聚氯乙烯、聚苯乙烯、离聚物等。其中,从拉伸强度高、耐药品性能优异、生产工序方面优异的观点考虑,优选使用聚丙烯。
其中,在本说明书中,(甲基)丙烯酸酯意指丙烯酸酯或甲基丙烯酸酯。
上述热塑性树脂层可以为未拉伸的层,也可以根据需要进行单轴拉伸或双轴拉伸。
另外,作为上述热塑性树脂层的厚度,没有特别限定,优选下限为20μm、优选上限为500μm,更优选下限为60μm、更优选上限为420μm以下。
上述热塑性树脂层的厚度低于20μm时,拉伸强度变得不充分,有时无法保护上述图案层的表面,而在超过500μm时,本发明的透明性树脂膜的透射率下降,有时会导致图案层的图案的辨视性下降。
上述热塑性树脂层只要基材所具备的图案层可视即可,没有特别限定,可以被着色。此时,可以在上述非卤系热塑性树脂中添加着色剂。作为着色剂,可以使用后述的图案层中使用的颜料或染料。
上述热塑性树脂层中也可以含有填充剂、消光剂、发泡剂、阻燃剂、润滑剂、抗静电剂、抗氧化剂、紫外线吸收剂、光稳定化剂、自由基捕捉剂、软质成分(例如橡胶)等各种添加剂。
在上述热塑性树脂层为2层以上的结构时,可以隔着透明性粘接剂层叠层,也可以通过热层压方式。
从不需要粘接剂、不会因粘接剂劣化而引起剥离等问题的观点出发,优选利用热层压方式叠层。
作为上述热层压方式,可以采用使用T模的熔融共挤出法等公知的方法。
作为上述透明性粘接剂层,可以使用公知的粘接剂。例如可以列举聚氨酯、丙烯酸、聚烯烃、聚乙酸乙烯酯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、离聚物等,此外还可以列举丁二烯-丙烯腈橡胶、氯丁橡胶、天然橡胶等。这些粘接剂可以单独使用,也可以将2种以上组合使用。
上述透明性粘接剂层的干燥后的厚度优选为0.1~30μm左右,更优选为1~5μm左右。
在利用上述热层压方式将2层以上的上述热塑性树脂层叠层之后,还可以通过进行骤冷来调节雾度值。
这里所说的骤冷意指透明性树脂膜以200℃/秒以上的速度冷却。
作为进行上述骤冷的方法,可以列举在利用热层压方式层压之后,立即与冷却至10℃以下的金属辊接触数秒的方法等。
作为上述骤冷的速度,优选以230℃/秒进行冷却,更优选以250℃/秒进行冷却。
上述热塑性树脂层的与设有上述外部雾度层的一侧的表面(以下也称为背面)相反一侧的表面(以下也称为正面)可以是平滑面,也可以具有凹凸形状。
通过上述表面为平滑面,在基材的一侧表面上叠层的图案层能够更鲜明地显现。
其中,上述平滑面意指JIS B 0601(1982)所规定的中心线平均粗糙度Ra为2.0μm以下的表面。
其中,上述“表面”意指透明性树脂膜的最表面(与在图案层上叠层的一侧相反的一侧),在透明性树脂膜具有后述的表面保护层的情况下,意指是具有表面保护层的一侧的最表面。
另外,通过上述表面具有凹凸形状,本发明的透明性树脂膜能够展现出设计感,能够使使用本发明的透明性树脂膜得到的装饰板的外观设计性更加优异。
另外,作为所形成的凹凸形状的深度,没有特别限定,优选适当调节例如使得JISB 0601(1982)所规定的中心线平均粗糙度Ra在5~20μm的范围内。
上述凹凸形状优选JIS B 0601(2001)所定义的最大高度Rz为20μm以上200μm以下。
通过本发明的透明性树脂膜具有上述凹凸形状,能够更适当地提升外观设计性。
另一方面,在上述最大高度Rz低于20μm时,有时无法充分地赋予外观设计性,而在超过200μm时,有时上述凹凸形状的赋形性下降。
上述最大高度Rz优选为50μm以上180μm以下,更优选为70μm以上150μm以下。
其中,在本说明书中,JIS B 0601(1982)所规定的中心线平均粗糙度Ra和JIS B0601(2001)所定义的最大高度Rz可以使用表面粗糙度测定器(“SURFCOM-FLEX-50A”、东京精密株式会社制)以下述条件进行测定而获得。
(测定条件)
测定次数:n=5(任选的5点)
算出标准:JIS’01
测定类别:粗糙度测定
评价长度:12.5mm
截止值:2.5mm
测定速度:0.60mm/s
滤波类别:Gaussian
去除形状:直线
λs值:8.0μm
在凹凸形状具有方向性的木纹导管或发纹样式的情况下,测定流动方向和其垂直方向,将两者数值大的作为最大高度(Rz)。
此时,测定部位选择具有凹凸形状的位置进行测定。
作为在上述热塑性树脂层的表面形成凹凸形状的方法,没有特别限定,例如可以列举利用热进行的压花加工、利用赋形片在热塑性树脂层上转印凹凸形状的方法等。
作为利用热进行的压花加工,例如可以列举公知的利用单片或旋转式压花机实施压花加工的方法。
另外,作为压花加工的图案花纹,例如可以列举砂纹、发纹、梨皮花样、木纹板导管槽、石板表面凹凸、布表面纹理、万线条槽等。
另外,作为进行压花加工时的温度,没有特别限定,优选加热压接成型时凹凸花纹消失的所谓的压花恢复减少的温度,例如可以以片材温度120℃~160℃、1.0~4.0MPa转印凹凸图案。
另外,在对透明性树脂膜实施压花加工的情况下,可以在形成后述的表面保护层之后进行,也可以在形成表面保护层之前进行。
例如,作为具体的方式,1)可以在形成热塑性树脂层后,形成表面保护层,最后实施压花加工。另外,作为另一具体的方式,2)也可以在形成热塑性树脂层后,实施压花加工,最后形成表面保护层。并且,作为又一具体的方式,3)可以在形成热塑性树脂层的同时实施压花加工后,最后形成表面保护层。
(表面保护层)
如图2所示,本发明的透明性树脂膜10可以在热塑性树脂层11的与外部雾度层12相反一侧的表面,进一步隔着表面保护层用底涂层13设置表面保护层14。
通过具有上述表面保护层,本发明的透明性树脂膜的耐久性(耐划伤性、耐污染性、耐候性等)更加优异,能够更适当地保护图案层的表面,能够适当地防止因本发明的透明性树脂膜本身的损伤而造成的外观设计性的下降。
其中,上述表面保护层可以为单一层的结构,也可以为由相同或不同的材料形成的多层的结构。
作为上述表面保护层,没有特别限定,例如可以列举由双液固化型树脂或电离射线固化型树脂组合物的交联固化物构成的保护层,该交联固化物优选透明,只要是透明的即可,在能够辨视后述的图案层的范围内,可以是半透明的,也可以被着色。
作为上述双液固化型树脂,例如可以列举双液固化型聚氨酯树脂、双液固化型聚酯树脂、双液固化型环氧树脂等。
作为上述电离射线固化型树脂组合物,例如优选使用分子中具有自由基聚合性不饱和键或阳离子聚合性官能团的低聚物(以下也包括所谓的预聚物、大分子单体等)和/或分子中具有自由基聚合性不饱和键或阳离子聚合性官能团的单体。其中,在此电离射线意指具有能够使分子聚合或交联的能量的电磁波或带电粒子,通常情况下,一般为电子射线(EB)或紫外线(UV)。
作为上述低聚物或单体,例如可以列举分子中具有(甲基)丙烯酰基、(甲基)丙烯酰氧基等自由基聚合性不饱和基团、环氧基等阳离子聚合性官能团等的化合物。这些低聚物、单体可以单独使用,或者将多种混合使用。其中,在本说明书中,上述(甲基)丙烯酰基意指丙烯酰基或甲基丙烯酰基。
作为上述分子中具有自由基聚合性不饱和基团的低聚物,例如优选使用聚氨酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、三聚氰胺(甲基)丙烯酸酯、三嗪(甲基)丙烯酸酯等低聚物,更优选聚氨酯(甲基)丙烯酸酯低聚物。作为分子量,通常使用250~10万左右的聚合物。
另外,作为上述分子中具有自由基聚合性不饱和基团的单体,例如优选多官能单体,更优选多官能(甲基)丙烯酸酯。
作为上述多官能(甲基)丙烯酸酯,例如可以列举二乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、双酚A环氧乙烷改性二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷环氧乙烷三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯{5官能(甲基)丙烯酸酯}、二季戊四醇六(甲基)丙烯酸酯{6官能(甲基)丙烯酸酯}等。在此,多官能单体是指具有多个自由基聚合性不饱和基团的单体。
在本发明中,更优选上述电离射线固化型树脂组合物含有由聚氨酯丙烯酸酯低聚物和多官能单体构成的电离射线固化型树脂成分,作为电离射线固化型树脂成分,特别优选聚氨酯丙烯酸酯低聚物/多官能单体(质量比)为6/4~9/1。在该质量比的范围内时,耐擦伤性更加优异。
并且,根据需要,除了上述电离射线固化型树脂成分之外,还可以在不违背本发明目的的范围内适当使用单官能单体。
作为上述单官能单体,例如可以列举(甲基)丙烯酸甲酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸苯氧基乙酯等。
在利用紫外线使上述电离射线固化型树脂组合物交联的情况下,优选在电离射线固化型树脂组合物中添加光聚合引发剂。
在上述电离射线固化型树脂组合物为具有自由基聚合性不饱和基团的树脂系的情况下,作为上述光聚合引发剂,可以将乙酰苯酮类、二苯甲酮类、噻吨酮类、苯偶姻、苯偶姻甲醚类单独使用或混合使用。
另外,在上述电离射线固化型树脂组合物为具有阳离子聚合性不饱和基团的树脂系的情况下,作为上述光聚合引发剂,可以将芳香族重氮盐、芳香族锍盐、芳香族碘鎓盐、茂金属化合物、苯偶姻磺酸酯等单独使用或作为混合物使用。其中,作为这些光聚合引发剂的添加量,相对于电离射线固化型树脂成分100质量份为0.1~10质量份左右。
并且,上述电离射线固化型树脂组合物中可以根据需要进一步添加各种添加剂。作为这些添加剂,例如有:聚氨酯树脂、聚乙烯醇缩醛树脂、聚酯树脂、聚烯烃树脂、苯乙烯系树脂、聚酰胺树脂、聚碳酸酯树脂、缩醛树脂、氯乙烯-乙酸乙烯酯共聚物、乙酸乙烯酯树脂、丙烯酸树脂、纤维素系树脂等热塑性树脂;有机硅树脂、蜡、含氟树脂等润滑剂;苯并三唑、二苯甲酮等紫外线吸收剂;受阻胺系自由基捕捉剂等光稳定剂;染料、颜料等着色剂等。
另外,作为电离射线的电子射线源,例如使用利用科克罗夫特-沃尔顿型、范德格拉夫型、共振变压器型、绝缘芯变压器型或直线型、高频高压型、高频型等的各种电子射线加速器照射具有70~1000keV的能量的电子的射线源。另外,电子射线的照射线量例如优选为1~10Mrad左右。
另外,作为上述电离射线的紫外线源,例如可以使用超高压汞灯、高压汞灯、低压汞灯、碳弧灯、黑光灯、金属卤素灯等光源,作为上述紫外线的波长,通常主要使用190~380nm的波长域。
(表面保护层用底涂层)
优选上述表面保护层用底涂层含有粘合剂树脂。
上述表面保护层用底涂层优选透明,只要是透明的即可,在能够辨视图案层的范围内,可以是半透明的,也可以被着色。
作为上述粘合剂树脂,例如可以列举聚氨酯树脂、丙烯酸树脂、丙烯酸-聚氨酯树脂(丙烯酸改性聚氨酯树脂)、丙烯酸-聚氨酯共聚物树脂(嵌段共聚物)、纤维素树脂、聚氨酯-纤维素系树脂(例如在聚氨酯与硝化棉的混合物中添加六亚甲基二异氰酸酯而成的树脂)、聚酯树脂、氯乙烯-乙酸乙烯酯共聚物树脂等。在上述的表面保护层的电离射线固化型树脂组合物中配合聚氨酯丙烯酸酯低聚物的情况下,从与表面保护层的密合性和生产时的效率考虑,优选聚氨酯树脂。
上述表面保护层用底涂层的厚度优选为0.5μm以上10μm以下。为0.5μm以上时,能够适当地确保本发明的透明性树脂膜与后述图案层的密合性,为10μm以下时,本发明的透明性树脂膜不会变得过厚,能够获得充分的透明性,能够适当地确保装饰板的外观设计性。并且还能够抑制制膜时的黏连。
其中,黏连是指将透明性树脂膜制膜或涂布粘接用底涂剂等并将其卷绕成辊状、再将其解卷时膜彼此之间不易分离的现象。并且,上述表面保护层用底涂层可以含有二氧化硅等无机微粒。
并且,上述表面保护层用底涂层中可以根据需要配合添加剂。作为添加剂,例如可以列举碳酸钙、黏土等填充剂、氢氧化镁等阻燃剂、抗氧化剂、润滑剂、发泡剂、紫外线吸收剂、光稳定剂等。添加剂的配合量可以根据产品特性适当设定。
(外部雾度层)
本发明的透明性树脂膜具有外部雾度层。
上述外部雾度层叠层在上述热塑性树脂层的背面,用于保护在后述的基材的一侧表面上叠层的图案层的表面。
本发明的透明性树脂膜中,上述外部雾度层的雾度值优选为4%以上且低于100%。上述雾度值低于4%时,在上述图案层表面叠层本发明的透明性树脂膜时,有时无法通过目视辨别咬气,有时密合性也不充分。上述外部雾度层的雾度值的更优选的下限为5%、进一步优选的下限为6%。
上述外部雾度层的雾度值时由透明性树脂膜整体的雾度减去背面润湿的状态下的雾度而得到的值。
上述透明性树脂膜整体的雾度,例如可以从外部雾度层的正面侧或透明树脂膜的正面侧照射光,使用公知的雾度计进行测定。
上述背面被润湿的状态下的雾度,可以在透明性树脂膜的背面侧隔着纯水粘贴有雾度值为0.1%以下的PET的状态下,从上述透明性树脂膜的正面侧照射光,使用公知的雾度计进行测定。这是因为通过这样能够算出从透明性树脂膜去除了外部雾度层的雾度值后的雾度值。
在本发明的透明性树脂膜中,优选在上述外部雾度层的与热塑性树脂层侧相反一侧隔着纯水层粘贴雾度为0.1%以下的聚对苯二甲酸乙二醇酯膜,从上述热塑性树脂层侧测定的背面润湿的状态下的雾度值为90%以下。
从上述热塑性树脂层侧测定的背面润湿的状态下的雾度值超过90%时,本发明的透明性树脂膜的透明性降低,在制成装饰板时有时图案层的辨视性变差。
上述背面润湿的状态下的雾度值的更优选的上限为80%、进一步优选的上限为60%。
作为构成上述外部雾度层的材料,是为了使与上述图案层的密合更好而使用的材料,例如可以列举聚氨酯树脂、丙烯酸树脂、聚氨酯-丙烯酸树脂、聚氨酯-丙烯酸共聚物树脂、纤维素树脂、聚酯树脂、氯乙烯-乙酸乙烯酯共聚物等。
上述外部雾度层的厚度优选为0.5μm以上20μm以下。在低于0.5μm时,基材与透明性树脂膜的密合性不充分,而在超过20μm时,在制作透明性树脂膜时制成辊状时,膜的表面和背面接触,有时会发生黏连。上述外部雾度层的厚度的更优选的下限为0.8μm、更优选的上限为15μm,进一步优选的下限为1μm、进一步优选的上限为10μm。
作为使上述背面润湿的状态下的雾度值在上述范围内的方法,例如可以考虑调节热塑性树脂层所含的添加剂量的方法、或使热塑性树脂层的厚度薄膜化的方法等。
为了使上述外部雾度层与上述热塑性树脂层的密合性更加牢固,可以对热塑性树脂层的设置外部雾度层的表面实施电晕放电处理或等离子体处理等表面处理。上述表面处理的方法、条件按照公知的方法实施即可。
并且,还可以在外部雾度层与基材层之间形成底涂层等来提高密合性。
并且,上述外部雾度层还可以具有用于使与基材层或热塑性树脂层的密合良好的作为底涂层的功能。作为上述底涂层,适合使用与上述的表面保护层用底涂层同样的底涂层。
上述外部雾度层可以在与热塑性树脂层侧相反一侧的表面上具有单层或多层的与上述热塑性树脂层同样的层。
并且,上述外部雾度层可以根据需要配合添加剂。作为添加剂,例如可以列举碳酸钙、黏土等填充剂、氢氧化镁等阻燃剂、抗氧化剂、润滑剂、发泡剂、紫外线吸收剂、光稳定剂等。添加剂的配合量可以根据产品特性适当设定。
(透明性树脂膜的雾度值)
本发明的透明性树脂膜的去除与在基材上叠层的一侧相反的一侧的表面雾度后的雾度值(以下也称为雾度值(1))优选为70%以上。
本发明的透明性树脂膜通过具有这样的雾度,能够提高热吸收率,因而凹凸形状的赋形性优异。
通常情况下,通过压花加工等形成的凹凸形状因热或时间经过等而消失,但通过上述雾度值(1)为规定的范围,能够抑制这样的凹凸形状的消失。
上述雾度值(1)更优选为75%以上,进一步优选为80%以上。
其中,在本说明书中,上述雾度是使用DIRECT READING HAZE METER(东洋精机株式会社制)测得的值。
上述雾度值(1)可以按照以下方法测定。
即,制作依次叠层有透明性树脂膜、纯水和PET膜(雾度值为3%以下)而成的片材。
此时,在透明性树脂膜的具有凹凸形状的一侧叠层上述纯水。
对于所得到的片材,使用DIRECT READING HAZE METER(东洋精机株式会社制)从透明性树脂膜的具有凹凸形状的一侧、更具体而言从在透明性树脂膜的具有凹凸形状的一侧叠层的PET膜的一侧测定雾度值,去除上述PET膜的雾度值,具体而言减去PET膜的雾度值(例如3%)而获得。
本发明的透明性树脂膜的去除在基材上叠层的一侧的表面雾度、和与在基材上叠层的一侧相反的一侧的表面雾度后的雾度值(以下也称为雾度值(2))优选为70%以下。
本发明的透明性树脂膜通过具有这样的雾度,后述的图案层上形成的图案清晰可见,因而外观设计性优异。
上述雾度值(2)更优选为65%以下,进一步优选为60%以下。
上述雾度值(2)可以按照下述方法测定。
即,制作依次叠层有PET膜(雾度值为3%以下)、纯水、透明性树脂膜、纯水和PET膜(雾度值为3%以下)的片材。
对于所得到的片材,使用DIRECT READING HAZE METER(东洋精机株式会社制)从透明性树脂膜的具有凹凸形状的一侧、更具体而言从在透明性树脂膜的具有凹凸形状的一侧叠层的PET膜的一侧测定雾度值,去除上述PET膜的雾度值,具体而言减去各个PET膜(例如PET膜的雾度值分别为3%、合计为6%)而获得。
(透明性树脂膜的制造方法)
作为本发明的透明性树脂膜的制造方法,没有特别限定,可以列举将上述的各层隔着上述透明性粘接剂层或表面保护层用底涂层等叠层的方法、或者利用热层压方式进行叠层的方法等。
作为上述热层压方式,可以采用利用T模的熔融共挤出法等公知的方法。
<装饰板>
本发明的透明性树脂膜用于保护上述图案层,在基材的图案层上叠层的一侧的表面具有外部雾度层,因而在基材的图案层的表面上叠层透明性树脂膜时,能够通过目视容易地判断是否夹入了空气,容易使与上述图案层的密合性优异。
这样的在厚度方向上依次具有基材、图案层和本发明的透明性树脂膜的装饰板也是本发明的方式之一。
下面,利用图3对本发明的装饰板的优选的一例进行说明。
本发明的装饰板20在基材25的一侧表面上叠层图案层24,在图案层24的与具有基材25的一侧相反的一侧叠层本发明的透明性树脂膜10。
并且,从使图案层24与本发明的透明性树脂膜10的密合性更加牢固的观点考虑,优选具有粘接剂层23。
下面对本发明的装饰板的各构成进行说明。
(基材)
作为构成上述基材的材料,没有特别限定,例如可以列举树脂材料、木质材料、金属材料等公知的材料。并且也可以为它们的复合材料。
作为上述树脂材料,例如优选含有热塑性树脂。
作为上述热塑性树脂,优选列举:聚氯乙烯树脂、聚乙酸乙烯酯树脂、聚乙烯醇树脂等聚乙烯基树脂、聚乙烯、聚丙烯、聚苯乙烯、乙烯-乙酸乙烯酯共聚物树脂(EVA)、乙烯-(甲基)丙烯酸系树脂等聚烯烃树脂、聚对苯二甲酸乙二醇酯树脂(PET树脂)等聚酯树脂、丙烯酸树脂、聚碳酸酯树脂、聚氨酯树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)、丙烯腈-苯乙烯共聚物等热塑性树脂的单体和共聚物、或者它们的混合树脂。其中,优选聚烯烃树脂或丙烯腈-丁二烯-苯乙烯共聚物、聚氯乙烯树脂、离聚物等。并且,上述树脂材料可以发泡。
另外,作为上述木质材料,例如可以列举杉木、扁柏、榉木、松木、柳桉、柚木、娑罗双木等各种原料等。另外,作为芯材,可以为由这些原料制作的平切单板、木材单板、木材胶合板(包括LVL)、刨花板、中密度纤维板(MDF)、高密度纤维板(HDF)、集成材等任一种、以及将它们叠层的叠层材料。
作为上述金属材料,例如可以列举铁等。
并且,上述基材也可以含有无机化合物。
另外,在上述基材具有多个热塑性树脂层的情况下,形成该多个热塑性树脂层的树脂的种类可以相同也可以不同,并且多个热塑性树脂层的厚度可以相同也可以不同。
在本发明中,上述基材可以为中空结构,也可以在基材的一部分设计缝隙槽或贯通孔,也可以为将上述材料组合而成的框状的结构。
作为上述基材的厚度,没有特别限定,例如优选为0.01mm以上,更优选为0.1mm以上50mm以下。
另外,基材也包括除平板以外的大致板状,还包括具有凹凸或曲面的基材。
(图案层)
另外,上述基材所具有的图案层是对使用本发明的透明性树脂膜得到的本发明的装饰板赋予装饰性的层,例如可以是均匀地实施了着色的遮蔽层(整面印刷层),可以是通过使用油墨和印刷机印刷各种花纹而形成的图案层,还可以是将遮蔽层与图案层组合而成的层(以下称为花纹层)。
通过设置上述遮蔽层,在上述基材着色或出现颜色不匀时,可以赋予意向色彩来调整表面的颜色。
另外,通过设置图案层,能够对装饰片赋予木纹花纹、模拟大理石花纹(例如石灰华大理石花纹)等岩石的表面的石纹花纹、模仿布纹或布样花纹的布质花纹、铺瓷砖花纹、砌砖花纹等、或者将它们复合维持的木片拼花、拼布等花纹。这些花纹可以通过通常的利用黄色、红色、蓝色和黑色的工艺颜料的多色印刷形成,此外,还可以通过准备构成花纹的各个颜色的版进行特殊色彩的多色印刷等形成。
作为上述图案层所使用的油墨组合物,可以使用在粘合剂树脂中适当混合有颜料、染料等着色剂、体质颜料、溶剂、稳定剂、增塑剂、催化剂、固化剂等的材料。作为该粘合剂树脂,没有特别限制,例如,优选列举聚氨酯树脂、氯乙烯/乙酸乙烯酯共聚物树脂、氯乙烯/乙酸乙烯酯/丙烯酸共聚物树脂、丙烯酸树脂、聚酯树脂、硝基纤维素树脂等。作为上述粘合剂树脂,可以将它们之中的任意1种单独使用或者将2种以上混合使用。
另外,作为上述着色剂,优选列举碳黑(墨)、铁黑、钛白、锑白、铬黄、钛黄、氧化铁红、镉红、群青、钴蓝等的无机颜料,喹吖啶酮红、异吲哚啉酮黄、酞菁蓝等的有机颜料或染料,铝、黄铜等的鳞片状箔片构成的金属颜料、二氧化钛包覆云母、碱性碳酸铅等的鳞片状箔片构成的珠光(珍珠)颜料等。
作为上述图案层的厚度,没有特别限定,例如优选为0.1μm以上,更优选为0.5μm以上600μm以下。上述图案层的厚度在上述范围内时,能够对本发明的装饰板赋予优异的外观设计性,还能够赋予遮蔽性。
其中,在如平切单板等那样上述基材本身预先具备外观设计性,并且想要利用基材本身的设计的情况下,基材本身兼做为图案层,因而可以不另外设置图案层。
本发明的透明性树脂膜的上述外部雾度层叠层于在上述基材的一侧表面上叠层的图案层的表面,用于保护该图案层的表面。
这样的在厚度方向上依次具有基材、图案层和本发明的透明性树脂膜的装饰板也是本发明之一。
作为本发明的装饰板的厚度,没有特别限定,例如优选为0.05mm以上,更优选为1mm以上50mm以下。
本发明的装饰板可以根据需要进一步具有支持层等。此时,被覆材料可以设置在透明性粘接剂层、底涂层、支持层等的背面侧。
上述透明性粘接剂层和上述底涂层适合使用与上述的透明性树脂膜中记载的层同样的层。
(支持层)
作为上述支持层,可以列举合成树脂支持层和发泡树脂支持层,优选存在于上述基材最下层(与叠层上述透明性树脂膜的一侧相反的一侧)。
通过上述基材具有上述支持层,装饰板的耐划伤性、耐冲击性更进一步提升。
作为构成上述合成树脂支持层的树脂,例如可以列举聚丙烯、乙烯-乙烯醇共聚物、聚乙烯、聚甲基戊烯、聚对苯二甲酸乙二醇酯、耐热性高的聚对苯二甲酸亚烷基酯〔例如乙二醇的一部分被1,4-环己烷二甲醇或二乙二醇等置换的聚对苯二甲酸乙二醇酯,所谓的商品名PET-G(Eastman Chemical Company生产)〕、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸-间苯二甲酸乙二醇酯共聚物、非晶性聚酯(A-PET)、聚碳酸酯、聚芳酯、聚酰亚胺、聚苯乙烯、聚酰胺、ABS等。这些树脂可以单独使用或使用2种以上。
上述合成树脂支持层可以含有中空珠。
上述中空珠的种类、粒径和含量等适用日本特开2014-188941号公报中记载的内容。
上述合成树脂支持层的厚度没有特别限定,例如优选为100~600μm,更优选为150~450μm。
作为形成上述合成树脂支持层的方法,可以列举压延成型、熔融树脂挤出成型等。其中,优选熔融树脂挤出成型,例如更优选使用T模的挤出成型。
上述发泡树脂支持层可以存在于比上述合成树脂支持层更下方的层(与具有凹凸形状的一侧相反的一侧)。
上述发泡树脂支持层可以应用日本特开2014-188941号公报中记载的内容。
(支承体)
上述基材可以为支承体。
作为上述支承体,没有特别限定,可以根据用途适当地选择各种纸类、塑料膜、木材等木质系的板、陶瓷系原料等。这些材料可以分别单独使用,但也可以为纸彼此之间的复合体或纸与塑料膜的复合体等任意组合而成的叠层体。
作为上述纸类,可以列举薄纸、牛皮纸、钛纸等。这些纸基材能够增强纸基材的纤维间以及其它层与纸基材之间的层间强度,为了防止起毛,还可以进一步在这些纸基材中添加丙烯酸树脂、苯乙烯丁二烯橡胶、三聚氰胺树脂、聚氨酯树脂等树脂(在抄造后浸渗树脂或在抄造时内填)。例如有纸间强化纸、树脂浸渗纸等。
除了这些之外,还可以列举绒纸、板纸、石膏板用原纸或在纸的表面设有氯乙烯树脂层的乙烯基壁纸筒等多在建材领域使用的各种纸。
并且,还可以使用在业务领域或通常的印刷、包装等中使用的铜板纸、双铜纸、硫酸纸、玻璃纸、羊皮纸、蜡纸或日本纸等。另外,区别于这些纸,具有类似于纸的外观和性状的各种纤维的织布或无纺布也能够作为基材使用。作为各种纤维,可以列举玻璃纤维、石棉纤维、钛酸钾纤维、氧化铝纤维、二氧化硅纤维或碳纤维等的无机质纤维、或者聚酯纤维、丙烯酸纤维或维尼纶纤维等的合成树脂纤维。
另外,在使上述纸类中浸渗热固化型树脂的情况下,能够广泛地使用一直以来公知的热固化型树脂。作为热固化型树脂,例如可以列举不饱和聚酯树脂、聚氨酯树脂(也包括双液固化型聚氨酯)、环氧树脂、氨基醇酸树脂、酚醛树脂、尿素树脂、苯二甲酸二烯丙酯树脂、三聚氰胺树脂、胍胺树脂、三聚氰胺-尿素共缩合树脂、硅树脂、聚硅氧烷树脂等。
这样操作使上述纸类中浸渗热固化型树脂得到的层也称为热固化型树脂层。并且,也有时该热固化型树脂最终还发挥作为表面保护层的功能。
作为形成上述热固化型树脂层的方法,例如,在上述支承体具有多孔质基材的情况下,可以列举在多孔质基材中浸渗上述热固化型树脂的方法。
浸渗可以通过从多孔质基材的正面侧、背面侧的任一方或双方供给上述热固化型树脂而进行。该方法没有特别限定,例如可以列举:使多孔质基材从形成有脱模层的表面或其相反面浸渍在加入了热固化型树脂的浴槽中的方法;利用吻涂机、逗号涂布机等涂布机在多孔性基材的形成有脱模层的表面、其相反面或这两面涂布热固化型树脂的方法;利用喷涂装置、喷淋装置等向多孔性基材的形成有脱模层的表面、其相反面或这两面喷出热固化型树脂的方法等。
作为构成上述塑料膜的树脂的具体例,可以列举聚乙烯、聚丙烯等聚烯烃系树脂、氯乙烯树脂、偏氯乙烯树脂、酚醛树脂、聚乙烯醇、乙烯-乙烯醇共聚物等乙烯基系树脂、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯树脂、聚甲基丙烯酸甲酯、聚丙烯酸甲酯、聚甲基丙烯酸乙酯等丙烯酸树脂、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)、三醋酸纤维素、聚碳酸酯等。这些之中,从耐候性、耐水性等各种物性、印刷适应性、成型加工适应性、价格等观点考虑,优选聚烯烃系树脂、氯乙烯树脂、聚酯树脂或丙烯酸树脂。
上述支承体的厚度没有特别限制,在支承体为塑料膜的情况下,优选为20~200μm,更优选为40~160μm,进一步优选为40~100μm。
在上述支承体为纸类的情况下,克重通常优选为20~150g/m2,更优选为30~100g/m2
上述支承体的形状并不限定于平板状,也可以为立体形状等特殊形状。
在上述支承体上,为了提高与支承体上设置的层的密合性,可以对单面或双面进行物理处理或化学表面处理等的易粘接处理。
(酚醛树脂浸渗纸)
上述装饰板可以根据需要叠层有酚醛树脂浸渗纸。
上述酚醛树脂浸渗纸叠层于多孔质基材的与形成有耐磨耗层和脱模层的一侧相反的一侧的表面即可。
上述酚醛树脂浸渗纸通常是指通过使酚醛树脂以浸渗率45~60%左右浸渗在作为芯纸的克重150~250g/m2左右的牛皮纸中,再使其以100~140℃左右干燥而制得的纸。酚醛树脂浸渗纸可以使用市售品。在叠层酚醛树脂浸渗纸时,可以根据需要对多孔质基材的背面实施电晕放电处理,或涂布上述的底涂层而形成背面底涂层。
(密封层)
在作为上述支承体使用纸类等具有浸渗性的基材时,在支承体与图案层之间等可以具有密封层。
在上述密封层中,优选含有热固化性树脂组合物或电离射线固化型树脂组合物等固化性树脂组合物的固化物,其中,更优选含有热固化性树脂组合物的固化物。
上述固化性树脂组合物的固化物的含量优选为密封层的全部固态成分的50质量%以上,更优选为65~95质量%。
上述密封层的热固化性树脂组合物和电离射线固化型树脂组合物可以列举与在上述表面保护层中例示的组合物同样的组合物。另外,作为热固化性树脂组合物,优选多元醇与异氰酸酯的双液固化性树脂,更优选丙烯酸多元醇与六亚甲基二异氰酸酯的双液固化性树脂。
在上述密封层中,从干燥适应性和粘度调节的观点考虑,优选含有颗粒。颗粒的含量优选为密封层的全部固态成分的5~50质量%,更优选为5~35质量%。
上述密封层的颗粒优选为无机颗粒,其中,优选二氧化硅。
该颗粒的平均粒径优选为0.1~2.0μm,更优选为0.2~1.5μm。
<被覆材料>
本发明的装饰板也能够以与具有凹凸形状的一侧相反的一侧接触的方式叠层在被覆材料上使用。
另一方面,在使用具有上述图案层的被覆材料的情况下,通过在该具有图案层的被覆材料上叠层上述透明性树脂膜,能够得到本发明的装饰板。
其中,作为上述图案层,适合使用上述的图案层。
上述被覆材料的材质例如可以列举:木材单板、木材胶合板、碎料热压板、MDF(中密度纤维板)等木质板;石膏板、石膏碎料板等石膏系板;硅酸钙板、石棉岩板、轻质发泡混凝土板、中空挤出水泥板等水泥板;纸浆水泥板、石棉水泥板、木片水泥板等纤维水泥板;陶器、瓷器、瓦器、玻璃、搪瓷等陶瓷板;铁板、镀锌钢板、聚氯乙烯溶胶涂布钢板、铝板、铜板等金属板;聚烯烃树脂板、丙烯酸树脂板、ABS板、聚碳酸酯板等热塑性树脂板;酚醛树脂板、尿素树脂板、不饱和聚酯树脂板、聚氨酯树脂板、环氧树脂板、三聚氰胺树脂板等热固化型树脂板;将酚醛树脂、尿素树脂、不饱和聚酯树脂、聚氨酯树脂、环氧树脂、三聚氰胺树脂、苯二甲酸二烯丙酯树脂等树脂浸渗在玻璃纤维无纺布、布帛、纸、其它的各种纤维质基材中固化并使其复合化而成的所谓的FRP板等。它们可以单独使用,也可以将它们的2种以上叠层形成复合基板使用。
并且,上述被覆材料的厚度没有特别限定。
作为在上述被覆材料上叠层的方法,没有特别限定,例如可以列举隔着上述底涂层叠层、或通过粘接剂叠层的手段等。
作为上述粘接剂,可以根据上述被覆材料的种类等从公知的粘接剂中适当选择。例如可以列举聚乙酸乙烯酯、聚氨酯、丙烯酸、聚氨酯丙烯酸(也包括共聚物)聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、离聚物等,此外还可以列举丁二烯-丙烯腈橡胶、氯丁橡胶、天然橡胶等。
<装饰板的制造方法>
作为本发明的装饰板的制造方法,例如可以列举加热熔融法或热层压法、以及使用水系粘接剂或热敏粘接剂、压敏粘接剂、或者热熔粘接剂、形成上述透明粘接剂层的粘接剂等,使上述基材、上述图案层和上述透明性树脂膜叠层的方法等。
其中,上述装饰板的制造方法优选包括在上述透明性树脂膜的叠层上述图案层的一侧的表面形成粘接剂层的工序;和通过上述粘接剂层将上述透明性树脂膜与上述图案层贴合的工序。
这样的制造本发明的装饰板的方法也是本发明的方式之一。
在上述透明性树脂膜中,在赋予与叠层上述图案层的一侧相反的一侧表面所具有的凹凸形状时,实施压花加工等形成凹凸形状,但追随实施了压花加工的表面一侧的凹凸形状,与实施了压花加工的表面相反侧的表面(与上述图案层叠层的一侧的表面)也会稍稍被赋予凹凸形状。在这种情况下,空气进入上述透明性树脂膜所形成的叠层上述图案层的一侧的凹凸形状,发生所谓的咬气,有时外观设计性下降。
在本发明的装饰板的制造方法中,包括在上述透明性树脂膜的具有上述图案层的一侧表面形成粘接剂层的工序,因而能够使粘接剂层还进入到具有上述图案层的一侧的凹凸形状的凹部,能够防止上述咬气的发生,能够抑制外观设计性下降。
实施例
下面利用实施例对本发明进行更详细的说明,但本发明完全不限定于这些示例。
(实施例1)
准备透明聚丙烯膜(厚度60μm),在该透明聚丙烯膜的一侧表面涂敷添加有二氧化硅的以异氰酸酯为固化剂的双液固化型聚氨酯树脂(厚度1μm),形成表面保护层用底涂层。
以挤出热层压方式在上述透明聚丙烯膜的另一侧表面(未涂敷表面保护层用底涂层的一侧)叠层透明聚丙烯系树脂(厚度200μm)。对其表面实施电晕处理之后,涂敷作为外部雾度层的以异氰酸酯为固化剂的双液固化型聚氨酯树脂(厚度2μm)。以凹版涂覆方式在该表面保护层用底涂层的涂敷面上以涂布量15μm涂敷作为电子射线固化型树脂的聚氨酯(甲基)丙烯酸酯,之后使用电子照射装置以加速电压165keV、5Mrad的条件照射电子射线,形成表面保护层。之后,以该面与压花版接触的方式进行热吸收式压花加工,赋予凹凸形状,制造透明性树脂膜。
然后,使用雾度测定机按照后述的方法测定透明性树脂膜整体的雾度值、背面润湿状态下的雾度。
另一方面,准备HDF(厚度3mm)。利用喷墨打印机在该HDF的一侧表面上形成图案层,使图案层厚度达到2μm,由此制备了基材。
在所得到的透明性树脂膜的与具有凹凸形状的一侧相反的一侧的表面涂布以异氰酸酯为固化剂的双液固化型聚酯树脂(厚度50μm),形成粘接剂层,通过上述粘接剂层将所得到的透明性树脂膜的与具有凹凸形状的一侧相反的一侧的表面、和上述基材的具有图案层的一侧的表面叠层。之后,施加10kg/m2的压力,在常温环境下养护3天。
(雾度值测定方法)
作为测定装置,使用DIRECT HAZE METER(东洋精机株式会社制)。
片材整体的雾度值:从透明性树脂膜的具有凹凸形状的表面的一侧、具体而言从在实施例1中赋予了凹凸形状的表面保护层的一侧照射光,测定雾度值。
背面润湿的状态下的雾度值:在透明性树脂膜的具有外部雾度层的表面的一侧滴加纯水,以不夹入空气的方式叠层PET膜(东丽株式会社生产Lumirror T60 50μm厚、雾度值0.1%),在该状态下,从透明性树脂膜的具有凹凸形状的表面的一侧、具体而言从实施例1中赋予了凹凸形状的表面保护层的一侧照射光,测定雾度值。
外部雾度层的雾度值:算出由片材整体的雾度值减去背面润湿的状态下的雾度值的值。
(能否通过目视确认咬气)
++···能够清晰地判断咬气
+···能够利用斜光确认来判断咬气
-···无法判断咬气
(密合时的外观设计性)
+++···层压后的设计看上去非常清晰
++···层压后的设计看上去稍稍模糊
+···层压后的设计看上去非常模糊
-···层压后的设计几乎看不到(实施例2~4、参考例1)
如表1所示,使用外部雾度层的雾度值不同的样品,除此以外,与实施例1同样操作制作透明性树脂膜。之后,进行与实施例1同样的评价。
[表1]
Figure BDA0003015938840000231
在实施例1~4中得到的透明性树脂膜中,能够容易地将咬气通过目视确认。
而在参考例1中得到的透明性树脂膜中,无法将咬气通过目视确认。
(实施例5)
准备聚丙烯系树脂(厚度60μm),在其一侧表面(在具有图案层的基材上叠层的一侧)涂敷底涂剂,形成外部雾度层(厚度2μm、以异氰酸酯为固化剂的双液固化型聚氨酯树脂)。以挤出热层压方式在上述聚丙烯系树脂的另一侧表面叠层聚丙烯系树脂(厚度60μm)。之后立即与温度设为10℃的金属辊接触0.5秒,以200℃/秒冷却(骤冷),得到形成有外部雾度层的透明性树脂层。
接着,对透明性树脂层的与具有外部雾度层的表面相反一侧的表面实施电晕处理后,涂敷底涂剂(厚度2μm),形成表面保护层用底涂层。以凹版涂覆方式在该表面涂敷电离射线固化型树脂(涂布量15μm)之后,使用电子照射装置以加速电压165keV、5Mrad的条件照射电子射线,形成表面保护层。
之后,利用红外线非接触方式的加热器对具有表面保护层的一侧进行加热,之后利用热压进行压花加工,得到具有凹凸形状的透明性树脂膜。
在透明性树脂膜的具有外部雾度层的表面涂敷双液固化型聚酯(厚度50μm)形成粘接剂层,在具有利用喷墨打印机设置的厚度2μm的图案层的基材(MDF(中密度纤维板)厚度3mm)上叠层,得到装饰板。
(实施例6)
除了将外部雾度层的厚度变更为1μm以外,与实施例5同样操作制作装饰板。
(实施例7)
除了将外部雾度层的厚度变更为5μm以外,与实施例5同样操作制作装饰板。
(参考例2)
除了将外部雾度层的厚度变更为0.5μm以外,与实施例5同样操作制作装饰板。
(参考例3)
准备聚丙烯系树脂(厚度60μm),在其一侧表面涂敷底涂剂(厚度2μm、以异氰酸酯为固化剂的双液固化型聚氨酯树脂),形成外部雾度层。以挤出热层压方式在上述聚丙烯系树脂的另一侧表面叠层聚丙烯系树脂(厚度60μm)。之后立即与50℃的金属辊接触0.5秒,之后在25℃的环境下放置,再以50℃/秒冷却(徐冷),得到形成有外部雾度层的透明性树脂层。
除了上述以外,与实施例5同样操作制作装饰板。
<雾度值>
实施例5~7和参考例2~3中得到的透明性树脂膜的去除与在基材上叠层的一侧相反的一侧的表面雾度后的雾度值(1)、以及去除在基材上叠层的一侧的表面雾度和与在基材上叠层的一侧相反的一侧的表面雾度后的雾度值(2)通过下述方法测定。
<雾度值(1)>
制作依次叠层有透明性树脂膜、纯水和PET膜(东丽株式会社生产Lumirror T60100μm厚、雾度值1.5%)的片材。
此时,在透明性树脂膜的具有凹凸形状的一侧叠层上述纯水。
对于所得到的片材,使用DIRECT READING HAZE METER(东洋精机株式会社制),从透明性树脂膜的具有凹凸形状的一侧、进一步具体而言从在透明性树脂膜的具有凹凸形状的一侧上叠层的PET膜一侧测定雾度值,去除上述PET膜的雾度值、具体而言通过减去PET膜的雾度值1.5%,从而得到的雾度值(1)。
<雾度值(2)>
制作依次叠层有PET膜(东丽株式会社生产、Lumirror T60 100μm厚、雾度值1.5%)、纯水、透明性树脂膜、纯水和PET膜(东丽株式会社生产、Lumirror T60、100μm厚、雾度值1.5%)的片材。
对于所得到的片材,使用DIRECT READING HAZE METER(东洋精机株式会社制),从透明性树脂膜的具有凹凸形状的一侧、进一步具体而言从在透明性树脂膜的具有凹凸形状的一侧上叠层的PET膜一侧测定雾度值,去除上述PET膜的雾度值、具体而言通过减去PET膜的雾度值各1.5%、合计3%,从而得到雾度值(2)。
(凹凸形状的赋形性)
对于实施例5~7和参考例2~3中得到的透明性树脂膜,测定形成有凹凸形状的一侧(具有表面保护层的一侧)的光泽值(GA)。
接着,将透明性树脂膜在100℃的甘油中浸渍30秒后,利用冷水冷却,再次测定形成有凹凸形状的一侧的光泽值(GB)。
按照以下评价基准评价凹凸形状的赋形性。(GA)与(GB)的值越接近,表示凹凸花纹的消失越少。
其中,在光泽值的测定中,使用光泽度计(村上色彩技术研究所株式会社制GMX-202(角度60°)。并且,该测定依照JIS Z8741进行。
++:(GB)/(GA)为80%以上。
+:(GB)/(GA)为60%以上且低于80%。
-:(GB)/(GA)低于60%。
(外观设计性)
目视观察实施例5~7和参考例2~3中得到的装饰板,按照以下基准进行评价。
++:图案层上形成的印刷图案看上去清晰。
+:图案层上形成的印刷图案看上去稍稍变色(模糊)。
-:图案层上形成的印刷图案看上去不清晰。
[表2]
实施例5 实施例6 实施例7 参考例2 参考例3
冷却方法 骤冷 骤冷 骤冷 骤冷 徐冷
外部雾度层的厚度(μm) 2 1 5 0.5 2
雾度值(1)(%) 82 75 86 68 89
雾度值(2)(%) 59 52 66 49 73
凹凸形状的赋形性 ++ + ++ - ++
外观设计性 ++ ++ + ++ -
可以确认实施例5~7中得到的透明性树脂膜的凹凸形状的赋形性优异,在实施例中得到的装饰板的外观设计性也优异。
而雾度(1)低于70%的参考例2的凹凸形状的赋形性差,雾度值(2)超过70%的参考例3中,外观设计性差。
产业上的可利用性
根据本发明,能够提供可以通过目视确认基材的图案层与透明性树脂膜是否粘接的透明性树脂膜。本发明的装饰板适合用于作为内部装饰用建材的隔扇或推拉门等的门、地板材料、墙壁、天井、以及各种各样的装饰成型体等。
符号说明
10:本发明的透明性树脂膜;11:热塑性树脂层;12:外部雾度层;13:表面保护层用底涂层;14:表面保护层;20:装饰板;23:粘接剂层;24:图案层;25:基材。

Claims (7)

1.一种透明性树脂膜,其用于保护在基材的一侧叠层的图案层,该透明性树脂膜的特征在于,
所述透明性树脂膜至少具有热塑性树脂层、和在与所述图案层叠层的一侧的外部雾度层,
在所述外部雾度层的与热塑性树脂层侧相反的一侧隔着纯水层粘贴雾度值为0.1%以下的聚对苯二甲酸乙二醇酯膜,从所述热塑性树脂层侧测定的在背面润湿的状态下的雾度值为90%以下。
2.如权利要求1所述的透明性树脂膜,其特征在于,
所述外部雾度层的雾度值为4%以上且小于100%。
3.如权利要求1或2所述的透明性树脂膜,其特征在于,
所述外部雾度层的厚度为0.5μm以上20μm以下。
4.一种透明性树脂膜,其用于保护在基材的一侧叠层的图案层,该透明性树脂膜的特征在于,
所述透明性树脂膜至少具有热塑性树脂层、和在与所述图案层叠层的一侧的外部雾度层,
所述透明性树脂膜的与在所述图案层上叠层的一侧相反的一侧具有凹凸形状,
雾度值(1)为70%以上,雾度值(1)是去除与在所述图案层上叠层的一侧相反的一侧的表面雾度后的雾度值,
雾度值(2)为70%以下,雾度值(2)是去除在所述图案层上叠层的一侧的表面雾度、和与在所述图案层上叠层的一侧相反的一侧的表面雾度后的雾度值。
5.如权利要求1或2所述的透明性树脂膜,其特征在于,
在所述热塑性树脂层的与在所述图案层上叠层的一侧相反的一侧具有表面保护层。
6.一种装饰板,其特征在于,
在厚度方向上依次具有基材、图案层和权利要求1、2、3、4或5所述的透明性树脂膜。
7.一种装饰板的制造方法,其是权利要求6所述的装饰板的制造方法,该制造方法的特征在于,包括:
在透明性树脂膜的将叠层图案层的一侧的表面形成粘接剂层的工序;和
通过所述粘接剂层将所述透明性树脂膜与所述图案层贴合的工序。
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