CN111132830A - 装饰片和装饰板 - Google Patents
装饰片和装饰板 Download PDFInfo
- Publication number
- CN111132830A CN111132830A CN201880061880.XA CN201880061880A CN111132830A CN 111132830 A CN111132830 A CN 111132830A CN 201880061880 A CN201880061880 A CN 201880061880A CN 111132830 A CN111132830 A CN 111132830A
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- CN
- China
- Prior art keywords
- decorative sheet
- layer
- halogen
- flame retardant
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
本发明提供一种即使在导热系数低的基材上叠层时火势也不易蔓延的装饰片、以及该装饰片叠层在基材上而成的装饰板。本发明是用于在粘贴装饰片一侧的导热系数低于0.1W/(m·K)的基材上叠层的装饰片,(1)具有多层含有非卤系热塑性树脂的层;(2)含有上述树脂的多层中的至少1层含有非卤系阻燃剂;(3)将含有上述树脂的多层的厚度合计(μm)设为x,并且将含有上述树脂的多层中的上述非卤系阻燃剂的质量合计相对于含有上述树脂的多层的质量合计100质量%的比例(质量%)设为y时,满足下述式(I):y≥0.00008x2+0.016x-2.51 (I);(4)含有上述非卤系阻燃剂的多层的各层中的上述非卤系阻燃剂的含量为8质量%以上。
Description
技术领域
本发明涉及装饰片和装饰板。
背景技术
一直以来,为了对各种各样的物品的表面赋予设计性而叠层装饰片。例如,作为建筑物的地板所使用的装饰板,在基材上叠层装饰片而使用。
这样的装饰片叠层在建筑物的表面,因而,有时需要表现出在火灾时不易燃烧的特性,满足能够获得不燃认定的条件。在此,上述的能够获得不燃认定的条件是指日本建筑基准法第2条第9款规定的、基于ISO5660-1的放热性试验对于总放热量、最大放热速度、龟裂和空穴的产生所规定的条件。
作为表现出上述那样的不燃性的装饰片,提出了基材片、透明性树脂层和表面保护层依次叠层而成的、各层的厚度在特定范围内、并且含有阻燃剂的装饰片(例如参照专利文献1)。
虽然上述装饰片也是不燃性优异的装饰片,但是对于火灾时在基材上的装饰片上火势不易蔓延的性质没有进行研究。关于地板用装饰材料那样的在水平面上施工的部件,抑制火灾时燃烧的装饰片的面积扩大、火势不易蔓延,这对于确保避险时间而言是重要的性能。
并且,在上述的装饰板中,大多情况下作为基材使用木质基材。作为木质基材,使用各种构成的木质基材,也有时使用在例如中密度纤维板(MDF)、高密度纤维板(HDF)等木质板的表面叠层软木以赋予保温性、缓冲性等的木质基材。
在使用上述基材的装饰板中,由于基材的表面使用导热系数低的软木,因而木质基材的导热系数低,低于0.1W/(m·K)。上述装饰板通过在上述那样的导热系数低的基材上叠层装饰片而形成,因而基材发挥隔热部件的作用,存在一旦基材上的装饰片着火而点燃,就会迅速燃烧,火势容易蔓延的问题。
因此,希望开发出即使在导热系数低的基材上叠层时火势也不易蔓延的装饰片、以及该装饰片叠层在基材上而成的火势不易蔓延的装饰板。
现有技术文献
专利文献
专利文献1:日本特开2015-182379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一种即使在导热系数低的基材上叠层时火势也不易蔓延的装饰片、以及该装饰片叠层在基材上而成的装饰板。
用于解决技术问题的技术手段
本发明的发明人反复进行了深入研究,结果发现一种用于在导热系数低于0.1W/(m·K)的基材上叠层的装饰片,其具有多层含有非卤系热塑性树脂的层,含有非卤系热塑性树脂的多层中的至少1层含有非卤系阻燃剂,含有非卤系热塑性树脂的多层的厚度合计x与非卤系阻燃剂的质量合计的比例y满足特定式,含有非卤系阻燃剂的多层的各层中的非卤系阻燃剂的含量在特定范围内,通过这样构成的装饰片,能够实现上述目的,从而完成了本发明。
即,本发明涉及下述的装饰片和装饰板。
1.一种装饰片,其是用于叠层在基材上的装饰片,上述基材的粘贴装饰片一侧的导热系数低于0.1W/(m·K),其中,
(1)具有多层含有非卤系热塑性树脂的层;
(2)含有上述非卤系热塑性树脂的多层中的至少1层含有非卤系阻燃剂;
(3)将含有上述非卤系热塑性树脂的多层的厚度合计(μm)设为x,并且将含有上述非卤系热塑性树脂的多层中的上述非卤系阻燃剂的质量合计相对于含有上述非卤系热塑性树脂的多层的质量合计100质量%的比例(质量%)设为y时,满足下述式(I):
y≥0.00008x2+0.016x-2.51(I);
(4)含有上述非卤系阻燃剂的多层的各层中的上述非卤系阻燃剂的含量为8质量%以上。
2.如项1所述的装饰片,其中,上述非卤系阻燃剂为选自磷系阻燃剂和氮系阻燃剂中的至少1种。
3.如项1或2所述的装饰片,其中,含有上述非卤系阻燃剂的多层的各层中的上述非卤系阻燃剂的含量为11质量%以上。
4.如项1~3中任一项所述的装饰片,含有上述非卤系热塑性树脂的多层中的上述非卤系阻燃剂的质量合计相对于含有上述非卤系热塑性树脂的多层的质量合计100质量%的比例y(质量%)为40质量%以下。
5.如项1~4中任一项所述的装饰片,其中,作为上述含有非卤系热塑性树脂的层,具有透明性树脂层,上述透明性树脂层的厚度为60μm以上。
6.如项1~5中任一项所述的装饰片,其中,所述装饰片还具有表面保护层。
7.如项6所述的装饰片,其中,上述表面保护层是电离放射线固化型树脂层。
8.如项7所述的装饰片,其中,上述电离放射线固化型树脂层是电子射线固化型树脂层。
9.如项6~8中任一项所述的装饰片,其中,上述表面保护层的厚度为15μm以上。
10.如项6~9中任一项所述的装饰片,其中,上述表面保护层含有微粒,上述微粒的平均粒径大于上述表面保护层的厚度。
11.如项10所述的装饰片,其中,上述微粒通过超临界逆相蒸发法被囊泡化。
12.如项1~11中任一项所述的装饰片,其中,上述装饰片的总厚度为150μm以上。
13.如项1~12中任一项所述的装饰片,其中,上述非卤系阻燃剂通过超临界逆相蒸发法被囊泡化。
14.一种装饰板,其是在基材上具有项1~13中任一项所述的装饰片的装饰板,上述基材的粘贴上述装饰片一侧的导热系数低于0.1W/(m·K)。
15.如项14所述的装饰板,其中,上述基材在上述装饰片一侧具有软木层。
发明效果
本发明的装饰片即使叠层在导热系数低的基材上时火势也不易蔓延。并且,本发明的装饰板由于在基材上叠层有该装饰片,所以火势不易蔓延。
附图说明
图1是表示本发明的装饰片的层结构的一例的示意图。
图2是表示构成本发明的装饰板的基材的层结构的一例的示意图。
图3是表示本发明的装饰板的层结构的一例的示意图。
图4是表示火势蔓延困难程度的试验方法的示意图。
图5是表示火势蔓延困难程度的试验方法的示意图。
图6是表示含有非卤系热塑性树脂的多层的总厚度(x)与含有非卤系热塑性树脂的多层的阻燃剂含量(y)的关系的图表。
具体实施方式
以下,对本发明的装饰片和装饰板进行详细说明。其中,本发明的装饰片中,装饰片的与叠层基材一侧相反侧的面是所谓的“正面”,是在地板等上施工时能够看到的面。因此,在本说明书中,将装饰片的与叠层基材一侧相反侧的面的方向称为“上”,而将其相反侧、即叠层基材一侧的面的方向称为“背”或“下”。同样,在本说明书中,将装饰板的装饰片一侧的面的方向称为“上”,而将其相反侧、即基材侧的面的方向称为“背”或“下”。
1.装饰片
本发明的装饰片是用于在粘贴装饰片一侧的导热系数低于0.1W/(m·K)的基材上叠层的装饰片,其特征在于:(1)具有多层含有非卤系热塑性树脂的层;(2)含有上述非卤系热塑性树脂的多层中的至少1层含有非卤系阻燃剂;(3)将含有上述非卤系热塑性树脂的多层的厚度合计(μm)设为x,并且将含有上述非卤系热塑性树脂的多层中的上述非卤系阻燃剂的质量合计相对于含有上述非卤系热塑性树脂的多层的质量合计100质量%的比例(质量%)设为y时,满足下述式(I):y≥0.00008x2+0.016x-2.51(I);(4)含有上述非卤系阻燃剂的多层的各层中的上述非卤系阻燃剂的含量为8质量%以上。
具有上述特征的本发明的装饰片满足上述(1)~(4)的构成,因而即使在导热系数低、低于0.1W/(m·K)的基材上叠层时,也能够抑制在火灾时燃烧的装饰片的面积扩大,火势不易蔓延。
本发明的装饰片只要满足上述(1)~(4)的条件即可,对于层结构没有限定。例如可以列举如下结构的装饰片:在基材片上依次叠层有图案花纹层、透明性粘接剂层、透明性树脂层、底涂层和表面保护层,在基材片的背面根据需要具有合成树脂制衬底层。另外,作为本发明的装饰片的层结构的一例,如图1所示,可以为合成树脂制衬底层11、基材片12、图案花纹层13、透明性树脂层14和表面保护层15依次叠层而成的层结构。其中,在该该层结构的示例中,含有非卤系热塑性树脂的层为透明性树脂层、基材片和合成树脂制衬底层。以下,以该层结构的装饰片为代表例进行具体说明。
本发明的装饰片具有多层含有非卤系热塑性树脂的层,含有该非卤系热塑性树脂的多层中的至少1层含有非卤系阻燃剂。作为含有非卤系热塑性树脂的层,可以列举后述的透明性树脂层、基材片和合成树脂制衬底层,这些层中只要至少1层含有非卤系阻燃剂即可。在图案花纹层从装饰片的表面更容易识别的观点上,优选基材片或合成树脂制衬底层含有非卤系阻燃剂,更优选基材片含有非卤系阻燃剂。
作为非卤系阻燃剂,只要是不含卤素的阻燃剂即可,没有特别限定,例如可以列举磷系阻燃剂、氮系阻燃剂、铝系阻燃剂、锑系阻燃剂、镁系阻燃剂、硼系阻燃剂、锆系阻燃剂等。这些之中,在装饰片的火势蔓延困难程度更进一步提高的观点上,优选磷系阻燃剂、氮系阻燃剂、镁系阻燃剂,更优选磷系阻燃剂、氮系阻燃剂,从非着色且减轻环境负荷的观点出发,进一步优选氮系阻燃剂。并且,还适合使用含有磷和氮的磷-氮系阻燃剂。这些非卤系阻燃剂可以使用1种或将2种以上组合使用。
作为磷系阻燃剂,可以列举磷酸酯类(例如磷酸三甲酚酯、磷酸三辛酯、磷酸三(单氯丙基)酯等)、多磷酸盐等。
作为氮系阻燃剂,可以列举碳酸铵等无机氮化合物系、三聚氰胺、硫酸三聚氰胺、三聚氰胺氰尿酸酯、双氰胺、三嗪化合物、胍化合物(氨基磺酸胍等)等有机氮化合物系等。其中,氮系阻燃剂中也包括磷系-氮系阻燃剂(例如磷酸二氢铵等)。
作为铝系阻燃剂,可以列举氢氧化铝等。
作为锑系阻燃剂,可以列举三氧化锑、五氧化锑、锑酸盐偏硼酸钡等。
作为镁系阻燃剂,可以列举氢氧化镁等。
作为硼系阻燃剂,可以列举硼酸锌等。
本发明的装饰片中,将含有非卤系热塑性树脂的多层的厚度合计设为(μm)x、并且将含有非卤系热塑性树脂的多层中的非卤系阻燃剂的质量合计相对于含有非卤系热塑性树脂的多层的质量合计100质量%的比例(质量%)设为y时,满足下述式(I)。
y≥0.00008x2+0.016x-2.51(I)
在不满足式(I)的情况下,装饰片的火势蔓延困难程度不充分。
在上述式中,x是含有非卤系热塑性树脂的多层的厚度合计。在上述层结构的示例的装饰片中,含有非卤系热塑性树脂的层为透明性树脂层、基材片和合成树脂制衬底层,是这些层的厚度合计。上述x优选为120~600μm,更优选为160~400μm。通过x在上述范围内,更容易调整上述x和y的值使其满足式(I)。
在上述式中,y是含有非卤系热塑性树脂的多层中的非卤系阻燃剂的质量合计相对于含有非卤系热塑性树脂的多层的质量合计100质量%的比例(质量%)。在上述层结构的示例的装饰片中,含有非卤系热塑性树脂的层为透明性树脂层、基材片和合成树脂制衬底层,将这些层的质量合计设为100质量%。是这些层中所含的非卤系阻燃剂的质量合计相对于这些层的质量合计100质量%的比例(质量%)。上述y优选为8质量%以上,更优选为11质量%以上。并且,上述y优选为40质量%以下,更优选为25质量%以下。通过y的下限在上述范围内,装饰片的火势蔓延困难程度进一步提高。另外,通过y的上限在上述范围内,含有非卤系阻燃剂的层的、对于印刷、层压等加工而言所必需的表面平滑性和拉伸强度进一步提高。
上述y所示的、含有非卤系热塑性树脂的多层中的非卤系阻燃剂的质量合计的比例(质量%)是按照以下方法算出的值。即,利用含有非卤系热塑性树脂的多层的各层的厚度和比重求出各层的质量,将它们合计,求出含有非卤系热塑性树脂的多层的总体质量的合计。接着,算出含有非卤系阻燃剂的层的厚度、比重和该层中的非卤系阻燃剂的比例之积,求出该层中的非卤系阻燃剂的质量。在含有非卤系阻燃剂的层具有多层的情况下,按照上述方法求出各个层中的非卤系阻燃剂的质量,再将它们合计。接着,用非卤系阻燃剂的质量合计除以含有非卤系热塑性树脂的多层的总体质量的合计,算出上述y。
对上述y的算出方法进行更具体的说明。例如,在透明性树脂层的厚度为100μm且比重为1.0、基材片的厚度为100μm且比重为1.0、合成树脂性衬底层的厚度为100μm且比重为1.0的情况下,含有非卤系热塑性树脂的多层的总体质量的合计为300(g/m2)。在基材片中添加30质量%的非卤系阻燃剂时,非卤系阻燃剂的质量为30(g/m2)。此时,算出上述y为10质量%。
另外,虽然本发明的装饰片也可以设置背面底涂层等固化型树脂层,但该固化型树脂层不同于非卤系热塑性树脂层,因而在式(I)中不考虑。
含有非卤系阻燃剂的多层的各层中的非卤系阻燃剂的含量为8质量%以上。如果上述非卤系阻燃剂的含量低于8质量%,则装饰片的火势蔓延困难程度不充分。上述非卤系阻燃剂的含量优选为11质量%以上,更优选为15质量%以上。并且,含有非卤系阻燃剂的层的各层中的非卤系阻燃剂的含量优选为50质量%以下,更优选为30质量%以下。上述非卤系阻燃剂的含量的上限在上述范围内时,含有非卤系阻燃剂的层表现出更优异的强度。
(基材片)
在本发明的装饰片中,基材片是多层的含有非卤系热塑性树脂的层中的一层。基材片是聚烯烃、聚酯、聚丙烯酸、聚酰胺、聚氨酯、聚苯乙烯等的合成树脂制片材。这些之中,在基材片是含有阻燃剂的层的情况下,在强度更优异的观点上,优选聚丙烯树脂的合成树脂制片材。
基材片优选为含有非卤系阻燃剂的层。通过基材片含有非卤系阻燃剂,能够制成具有优异的安全性、环境关注性的装饰片。
基材片的厚度优选为40~300μm,更优选为60~200μm。基材片可以根据需要进行着色。另外,可以对表面实施电晕放电处理、等离子体处理、臭氧处理等表面处理,也可以涂布用于提高与邻接层的密合性的作为基底涂料的底漆。
(图案花纹层)
图案花纹层由图案油墨层和/或全涂油墨层构成。图案花纹层可以通过凹版印刷、胶版印刷、丝网印刷等印刷法形成。图案油墨层的花纹例如可以列举木纹花纹、石纹花纹、布纹花纹、皮革花纹、几何学花纹、文字、符号、线条、各种抽象花纹等。全涂油墨层可以通过着色油墨的全涂印刷获得。图案花纹层由图案油墨层和全涂油墨层的一者或两者构成。
关于图案花纹层所使用的油墨,作为载色剂,可以使用氯化聚乙烯、氯化聚丙烯等氯化聚烯烃、聚酯、由异氰酸酯和多元醇形成的聚氨酯、聚丙烯酸、聚乙酸乙烯酯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、纤维素系树脂、聚酰胺系树脂等中的1种,或将2种以上混合使用,可以在这些之中添加颜料、溶剂、各种助剂等而制成油墨后使用。其中,从环境问题、与被印刷面的密合性等观点出发,优选聚酯、由异氰酸酯和多元醇形成的聚氨酯、聚丙烯酸、聚酰胺系树脂等中的1种或2种以上的混合物。
(透明性粘接剂层)
透明性粘接剂层根据需要设置在图案花纹层与透明性树脂层之间。透明性粘接剂层例如可以通过涂布双液固化型聚氨酯树脂等公知的干式层压用粘接剂并使其干燥而得到。
透明性粘接剂层优选干燥后的厚度为0.1~30μm左右,更优选为1~5μm左右。
(透明性树脂层)
在本发明的装饰片中,透明性树脂层是多层的含有非卤系热塑性树脂的层中的一层。透明性树脂层适合由透明性的非卤系热塑性树脂形成。
作为形成透明性树脂层的非卤系热塑性树脂,具体可以列举:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚酰胺、聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、离聚物、丙烯酸酯、甲基丙烯酸酯等合成树脂。上述之中,优选聚丙烯等聚烯烃系树脂。
透明性树脂层优选为含有非卤系阻燃剂的层。通过透明性树脂层含有非卤系阻燃剂,能够得到具有优异的安全性、环境关注性的装饰片。
透明性树脂层只要具有透明性即可,可以被着色。在这种情况下,在热塑性树脂中添加着色剂即可。作为着色剂,可以使用图案花纹层中使用的颜料或染料。
透明性树脂层可以含有填充剂、消光剂、发泡剂、润滑剂、抗静电剂、抗氧化剂、紫外线吸收剂、光稳定剂、自由基捕捉剂、软质成分(例如橡胶)等各种添加剂。
透明性树脂层的厚度优选为60μm以上,更优选为80μm以上。并且,透明性树脂层的厚度优选为300μm以下,更优选为200μm以下。通过透明性树脂层的厚度的下限在上述范围内,装饰片的耐擦伤性和耐磨损性进一步提高。另外,通过透明性树脂层的厚度的上限在上述范围内,装饰片的火势蔓延困难程度进一步提高。
可以根据需要对透明性树脂层的表面实施电晕放电处理、臭氧处理、等离子体处理、电离放射线处理、重铬酸处理等表面处理。表面处理可以按照各处理的常规方法进行。
透明性树脂层的表面可以形成有底涂层(用于使表面保护层的形成更容易的底涂层)。
底涂层通过在透明性树脂层上涂布公知的底漆而形成。作为底漆,例如可以列举由丙烯酸改性聚氨酯树脂等形成的聚氨酯树脂系底漆、由丙烯酸和聚氨酯的嵌段共聚物形成的树脂系底漆等。
底涂层的厚度没有特别限定,通常为0.1~10μm、优选为1~5μm左右。
(表面保护层)
表面保护层(透明性表面保护层)为了赋予装饰片所需求的耐擦伤性、耐磨损性、耐水性、耐污染性等表面物性而设置。作为形成该表面保护层的树脂,优选含有热固化型树脂或电离放射线固化型树脂等固化型树脂的至少1种。从高表面硬度、生产性等观点出发,特别优选电离放射线固化型树脂。从能够更进一步提高耐候性的观点出发,最优选电子射线固化型树脂。
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、邻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。
上述树脂中可以添加交联剂、聚合引发剂等固化剂、聚合促进剂。例如,作为固化剂,在不饱和聚酯树脂或聚氨酯树脂等中可以添加异氰酸酯、有机磺酸盐等,在环氧树脂中可以添加有机胺等,在不饱和聚酯树脂中可以添加过氧化甲乙酮等过氧化物、偶氮二异丁腈等自由基引发剂。
作为利用热固化型树脂形成表面保护层的方法,例如可以列举如下方法:利用辊涂法、凹版涂布法等涂布法涂布热固化型树脂的溶液,并使其干燥、固化。作为溶液的涂布量,以固态成分计约为5~50μm,优选为5~40μm左右。
电离放射线固化型树脂只要是通过照射电离放射线而发生交联聚合反应转变成三维高分子结构的树脂就没有限定。例如,可以使用分子中具有能够通过照射电离放射线而发生交联的聚合性不饱和键或环氧基的预聚物、低聚物和单体的1种以上。例如可以列举聚氨酯丙烯酸酯、聚酯丙烯酸酯、环氧丙烯酸酯等丙烯酸酯树脂;硅氧烷等硅树脂;聚酯树脂;环氧树脂等。
作为电离放射线,有可见光、紫外线(近紫外线、真空紫外线等)、X射线、电子射线、离子射线等,其中,优选紫外线、电子射线,更优选电子射线。
作为紫外线源,可以使用超高压汞灯、高压汞灯、低压汞灯、碳弧灯、黑光荧光灯、金属卤素灯的光源。作为紫外线的波长,为190~380nm左右。
作为电子射线源,例如可以使用科克罗夫特-沃尔顿型、范德格喇夫型、共振变压器型、绝缘芯变压器型、直线型、地那米(dynamitron)型、高频型等各种电子射线加速器。作为电子射线的能量,优选100~1000keV左右,更优选100~300keV左右。电子射线的照射量优选为20~150kGy左右。
对于电离放射线固化型树脂而言,在照射电子射线时能够充分固化,但在照射紫外线使其固化时,优选添加光聚合引发剂(敏化剂)。
在具有自由基聚合性不饱和基团的树脂系时,光聚合引发剂例如可以使用苯乙酮类、二苯甲酮类、噻吨酮类、苯偶姻、苯偶姻甲醚、米氏苯甲酰苯甲酸酯(Michler's benzoylbenzoate)、米氏酮(Michler's ketone)、二苯硫醚、二硫化二苄、乙醚、三苯基联咪唑、异丙基-N,N-二甲基氨基苯甲酸酯等的至少1种。另外,在具有阳离子聚合性官能团的树脂系的情况下,例如,可以使用芳香族重氮鎓盐、芳香族锍盐、茂金属化合物、苯偶姻磺酸酯、呋喃氧基氧化锍二烯丙基碘氧基盐等的至少1种。
光聚合引发剂的添加量没有特别限定,通常相对于电离放射线固化型树脂100质量份为0.1~10质量份左右。
作为利用电离放射线固化型树脂形成保护层的方法,例如可以利用凹版涂布法、辊涂法等涂布法涂布电离放射线固化型树脂的溶液。作为溶液的涂布量,以固态成分计约为10~50μm,优选为15~40μm左右。
优选具有表面保护层,表面保护层的厚度优选为10μm以上,更优选为15μm以上。并且,表面保护层的厚度优选为50μm以下,更优选为40μm以下。通过表面保护层的厚度的下限在上述范围内,装饰片的耐擦伤性和耐磨损性进一步提高。另外,通过表面保护层的厚度的上限在上述范围内,装饰片的火势蔓延困难程度进一步提高。
在对由电离放射线固化型树脂形成的表面保护层进一步赋予耐擦伤性、耐磨损性的情况下,配合微粒即可。作为微粒,可以列举无机填充材料。作为无机填充材料,例如可以列举粉末状的氧化铝、碳化硅、二氧化硅、钛酸钙、钛酸钡、焦硼酸镁、氧化锌、氮化硅、氧化锆、氧化铬、氧化铁、氮化硼、金刚石、金刚砂、玻璃纤维等。
微粒的平均粒径没有特别限定,优选大于表面保护层的厚度。通过微粒的平均粒径大于表面保护层的厚度,装饰片的耐擦伤性和耐磨损性进一步提高。微粒的平均粒径优选为5~30μm,更优选为10~20μm。
其中,在本说明书中,平均粒径是利用粒度分布测定器LS230(商品名:BeckmanCoulter公司制造)测得的值。
作为无机填充材料的添加量,相对于电离放射线固化型树脂100质量份为1~80质量份左右。
(合成树脂制衬底层)
在本发明的装饰片中,合成树脂制衬底层是多层的含有非卤系热塑性树脂的层中的一层。本发明的装饰片优选在装饰片的最下层、即装饰片的基材侧具有合成树脂制衬底层。通过具有合成树脂制衬底层,装饰材料的耐冲击性进一步提高。
作为构成合成树脂制衬底层的树脂,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、耐热性高的聚亚烷基对苯二甲酸酯〔例如,利用1,4-环己烷二甲醇或二乙二醇等取代乙二醇的一部分而得到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、聚亚乙基萘二甲酸酯-间苯二甲酸酯共聚物、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以两种以上使用。
合成树脂制衬底层的厚度优选为0.1~0.6mm,更优选为0.15~0.45mm,进一步优选为0.20~0.40mm。通过合成树脂制衬底层的厚度的下限在上述范围内,装饰片的耐冲击性进一步提高。另外,通过合成树脂制衬底层的厚度的上限在上述范围内,能够进一步抑制装饰片的翘曲。
以上说明的各层的叠层例如可以通过如下方法进行:通过印刷在基材片的一个面形成图案花纹层(全涂油墨层、图案油墨层)后,利用干式层压法、T模挤出法等,通过双液固化型聚氨酯树脂等公知的干式层压用粘接剂在图案花纹层上叠层透明性树脂,再形成表面保护层,制作中间体,利用热层压法将通过T模挤出法等制得的合成树脂层衬底层与中间体的基材片侧叠层。
装饰片的总厚度优选为150μm以上,更优选为160μm以上。另外,装饰片的总厚度优选为600μm以下,更优选为400μm以下。通过装饰片的总厚度的下限在上述范围内,装饰片的耐擦伤性和耐磨损性进一步提高。另外,通过装饰片的总厚度的上限在上述范围内,装饰片的火势蔓延困难程度进一步提高。
对于装饰片而言,可以通过从透明性树脂层侧或表面保护层侧实施压花加工而形成凹凸花纹。凹凸花纹能够通过热压、发纹加工等形成。作为凹凸花纹,可以列举导管槽、石板表面凹凸、布表面纹理、梨纹、砂纹、发纹、万线条槽等。
其中,在本说明书中,上述装饰片的总厚度等的层厚度是在未形成上述凹凸花纹的部位测得的值。
在本发明的装饰片的上述各层中添加的各种添加剂(表面保护层所含的微粒或含有非卤系热塑性树脂的层所含的非卤系阻燃剂等),优选该各种添加剂被囊泡化。作为将各种添加剂囊泡化的方法,没有特别限定,可以通过公知的方法进行囊泡化,其中,优选超临界逆相蒸发法。
以下,对超临界逆相蒸发法进行详细说明。超临界逆相蒸发法为如下方法:使形成囊泡的外膜的物质均匀地溶解在超临界状态的二氧化碳或临界点以上的温度或压力条件下的二氧化碳中形成混合物,在该混合物中添加含有水溶性或亲水性的作为封入物质的各种添加剂的水相,利用一层膜形成包含了作为封入物质的各种添加剂的胶囊状的囊泡。其中,超临界状态的二氧化碳是指处于临界温度(30.98℃)和临界压力(7.3773±0.0030MPa)以上的超临界状态的二氧化碳,临界点以上的温度或压力条件下的二氧化碳是指只有临界温度或只有临界压力超过临界条件的条件下的二氧化碳。利用该方法,能够得到直径50~800nm的单层层状囊泡。通常,囊泡是在具有封闭成球壳状的膜结构的小胞的内部包含液相的状态的总称,特别而言,将外膜由磷脂等生物体脂质构成的囊泡称为微脂粒。
作为上述磷脂,可以列举磷脂酰胆碱、磷脂酰乙醇胺、磷脂酰丝氨酸、磷脂酸、磷脂酰甘油、磷脂酰肌醇、心磷脂、蛋黄卵磷脂、氢化蛋黄卵磷脂、大豆卵磷脂、氢化大豆卵磷脂等甘油磷脂、鞘磷脂、磷酸乙醇胺神经酰胺、磷酸甘油神经酰胺等鞘磷脂。
作为构成外膜的物质,还可以使用非离子系表面活性剂、或者其与胆固醇类或三酰基甘油的混合物等的分散剂。
作为上述非离子系表面活性剂,可以使用聚甘油醚、二烷基甘油、聚氧亚乙基硬化蓖麻油、聚氧亚乙基烷基醚、聚氧亚乙基山梨糖醇酐脂肪酸酯、山梨糖醇酐脂肪酸酯、聚氧亚乙基聚氧亚丙基共聚物、聚丁二烯-聚氧亚乙基共聚物、聚丁二烯-聚2-乙烯基吡啶、聚苯乙烯-聚丙烯酸共聚物、聚环氧乙烷-聚乙基乙烯共聚物、聚氧亚乙基-聚己内酰胺共聚物等中的1种或2种以上。
作为上述胆固醇类,可以使用胆固醇、α-二氢胆固醇、β-二氢胆固醇、胆甾烷、链甾醇(5,24-胆甾二烯-3β-醇)、胆酸钠、胆钙化醇等中的1种或2种以上。
上述微脂粒的外膜可以由磷脂与分散剂的混合物形成。在本发明的装饰片中,通过制成由磷脂形成外膜的微脂粒,能够使作为各层的主要成分的树脂组合物与各种添加剂的相容性变得良好。
本发明的装饰片由于具有上述的结构,即使在导热系数低的基材上叠层时,火势也不易蔓延。因此,能够作为用于在导热系数低于0.1W/(m·K)的基材上叠层的装饰片使用,即使在该基材上叠层时火势也不易蔓延。因此,本发明的装饰片适合用作内部装饰材料用装饰片,特别适合用作地板用装饰片。
2.装饰板
本发明的装饰板是在基材上具有上述装饰片的装饰板,上述基材的粘贴上述装饰片一侧的导热系数低于0.1W/(m·K)。
作为构成本发明的装饰板的装饰片,可以使用上述说明的本发明的装饰片。
(基材)
构成本发明的装饰板的基材的导热系数低于0.1W/(m·K)。基材的导热系数也可以低于0.08W/(m·K)。其中,在本说明书中,基材的导热系数是通过Hot Disk法测得的值。
作为基材的材质,只要是表现出上述范围的导热系数的材质就没有特别限定。例如,可以使用如图2所示在地板用装饰板等装饰板通常所使用的木质板21上叠层有表现出上述范围的导热系数的材质的表面材料22的木质基材。另外,图3表示使用了图2的基材的本发明的装饰板的层结构的一例。在图3中,基材2的表面材料22与装饰片1的合成树脂制衬底层11贴合,在基材2上叠层装饰片1,形成装饰板。
作为表面材料,只要是表现出上述范围的导热系数的材质即可,没有特别限定,例如可以列举软木、桐木等。这些之中,从能够对装饰板赋予保温性、缓冲性的观点出发,适合使用软木。即,优选上述基材在装饰片一侧具有软木层。
表面材料的厚度没有特别限定,优选为1.0~5.0mm,更优选为1.0~2.0mm。
作为木质板,没有特别限定,例如可以列举中密度纤维板(MDF)、高密度纤维板(HDF)、胶合板等。这些之中,适合使用中密度纤维板(MDF)、高密度纤维板(HDF)。
木质板的厚度没有特别限定,优选为4.0~15.0mm,更优选为5.0~10.0mm。
作为将表面材料与木质板叠层的方法,没有特别限定,可以通过利用粘接剂叠层等现有公知的方法进行叠层。作为粘接剂,没有特别限定,能够广泛地使用公知的木工用粘接剂。作为粘接剂,例如可以列举以聚乙酸乙烯酯、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、丁二烯-丙烯腈橡胶、氯丁二烯橡胶、天然橡胶等为有效成分的粘接剂。另外,作为热固化型粘接剂,可以列举三聚氰胺系、酚醛系、脲系(乙酸乙烯酯-尿素系等)等的粘接剂。
作为在基材的正面叠层装饰片的方法,没有特别限定,可以通过在基材的正面形成粘接剂层再叠层装饰片等的现有公知的方法进行叠层。
粘接剂层的厚度没有特别限定,干燥后的厚度优选为0.1~100μm,更优选为0.1~30μm,进一步优选为1~20μm。
作为粘接剂层所使用的粘接剂,可以列举水溶性乳液系粘接剂、聚酯系粘接剂、丙烯酸系粘接剂、聚氨酯系粘接剂等。粘接剂可以使用1种或将2种以上组合使用。
本发明的装饰板由于具有上述构成,火势不易蔓延。因此,本发明的装饰板适合用作内装材料用装饰板,特别适合用作地板用装饰板。
实施例
以下例示实施例和比较例对本发明进行更详细的说明。但本发明并不限定于实施例。
实施例1
(装饰片的制造)
作为基材片,准备60μm厚的聚丙烯膜(比重1.02)。接着,对该基材片的两面实施电晕放电处理后,在该基材片的背面形成双液固化型聚氨酯树脂的背面底涂层,在该基材片的正面,利用含有丙烯酸聚氨酯系树脂的固化型印刷油墨,通过凹版印刷法形成图案花纹层。再在该图案花纹层上涂布双液固化型聚氨酯树脂的粘接剂,从而形成透明性的粘接剂层。再利用T模挤出机将聚丙烯树脂在粘接剂层上加热熔融挤出,形成热塑性的透明性树脂层(厚度100μm、比重0.90)。
接着,在该透明性树脂层上形成双液固化型聚氨酯树脂的底涂层。再利用凹版涂布法在该底涂层上涂布含有聚氨酯(甲基)丙烯酸酯低聚物的电子射线固化型树脂组合物,并进行干燥,之后,通过在加速电压175keV和5Mrad(50kGy)的条件下照射电子射线,形成厚度为15μm的表面保护层。其中,在表面保护层中作为微粒添加有二氧化硅。二氧化硅的平均粒径为18μm。
并且,从该表面保护层侧通过热压实施压花加工,从而形成木纹导管图案的凹凸花纹。
接着,制备含有聚丙烯酸树脂和磷-氮系阻燃剂(FP-2500S ADEKA公司生产)的树脂组合物。树脂组合物中的磷-氮系阻燃剂的含量为30质量%。在基材片的背面,使用该树脂组合物进行熔融挤出,以层压方式叠层树脂层,从而形成厚度为240μm的合成树脂制衬底层(比重1.08)。由此,制造实施例1的装饰片。
其中,上述装饰片设有背面底涂层等固化型树脂层,但该固化型树脂层不同于非卤系热塑性树脂层,因而在式(I)中不考虑。
(装饰板的制造)
使用粘接剂,在厚度为4mm的中密度纤维板(MDF)贴合厚度为1.5mm、导热系数为0.07W/(m·K)的软木片,制备木质基材。利用水溶性乳液系粘接剂在木质基材的软木片侧的表面贴合装饰片的合成树脂制衬底层侧的表面,制作装饰板。其中,水溶性乳液系粘接剂使用以下物质。
2水溶性乳液系粘接剂
主剂:“BA-10L”Japan Coating Resin Co.,Ltd.生产,改性乙烯-乙酸乙烯酯系固化剂:“BA-11B”Japan Coating Resin Co.,Ltd.生产,异氰酸酯系配合比:主剂∶固化剂=100∶2.5(质量比)
实施例2~23、比较例1~9和参考例1
除了按照表1~3所述改变装饰片的构成以外,与实施例1同样操作制造装饰片和装饰板。其中,表中衬底层的层厚度记作“0”时,表示未形成衬底层。
(评价)
对于如上所述制造的实施例和比较例的装饰片和装饰板,按照以下的方法进行评价。
(1)含有非卤系阻燃剂的层的强度
通过测定最大点强度来评价含有非卤系阻燃剂的层的强度。具体而言,按照JISK6732:2006将含有非卤系阻燃剂的层冲裁成哑铃型,制成试验片。使用拉伸试验机,以拉伸速度100mm/分钟、夹具间距离80mm的条件进行测定,按照以下的评价基准评价该试验片的最大点强度。
++:最大点强度在6N以上;
+:最大点强度在4N以上且小于6N;
-:最大点强度小于4N。
(2)火势蔓延困难程度
将装饰板切成9cm330cm的大小,制成试验片。如图4和5所示,将金属制的长方形的台103置于市售的家庭用加热器101(zaigle-handsome SJ-100(商品名))的台102上,在台上所设置的金属制的框104内放置试验片105,以加热器角度45°、加热器输出刻度4的条件进行火势蔓延困难程度的试验。详细而言,使用上述家庭用加热器将试验片预热2分钟。接着,如图4所示,利用点火器107在试验片的长度方向的加热器侧的端部106加热1分钟使其着火,如图5所示沿着试验片105的长度方向燃烧。接着,目测观察燃烧蔓延状态17分钟,测定燃烧距离(L1)。按照以下评价基准测定灭火性和燃烧距离,评价火势蔓延困难程度。
[灭火性]
++:自然灭火;
-:未自然灭火。
[燃烧蔓延距离(L1)]
++:L1在10cm以下;
+:L1超过10cm且在20cm以下;
-:L1超过20cm。
[火势蔓延困难程度评价]
+++:灭火性和燃烧蔓延距离判定为++;
++:灭火性判定为++,燃烧蔓延距离判定为+;
-:灭火性和燃烧蔓延距离的至少一方判定为-。
(3)耐擦伤性试验
使用霍夫曼划痕试验机(BYK-Gardner生产)确认装饰片的耐擦伤性。具体而言,使用粘接剂(水溶性乳液粘接剂(BA-10L/BA-11B))在2.5mm厚度的MDF上贴合装饰片,制成试验片。使刮擦刀(直径7mm的圆柱的边缘部)以45度的角度接触试验片的装饰片的表面保护层,拉着该刮擦刀使其移动,摩擦表面。此时,在100~700g荷重的范围内,使刮擦刀所受到的荷重以每100g进行变化,确认表面保护层是否出现损伤。将首次看到损伤的荷重作为划伤荷重,按照以下评价基准进行评价。
++:划伤荷重在600g荷重以上;
+:划伤荷重为400g荷重或500g荷重;
-:划伤荷重在300g荷重以下。
(4)耐磨损性试验
确认装饰片的耐磨损性。具体而言,使用粘接剂(水溶性乳液粘接剂(BA-10L/BA-11B))在2.5mm厚度的MDF上贴合装饰片,制成试验片。使用试验片,按照JAS地板磨损A试验进行试验,目测观察试验后的各试验片的装饰片的表面状态,按照以下评价基准进行评价。
++:500次旋转试验后,没有看到图案花纹被去除;
-:500次旋转试验后,看到图案花纹被去除。
将结果示于表1~3。并且,将含有非卤系热塑性树脂的多层的厚度合计(x)、与含有该非卤系热塑性树脂的多层中的非卤系阻燃剂的质量合计相对于含有非卤系热塑性树脂的多层的质量合计100质量%的比例(y)的关系示于图6。另外,在表1~3、图6中,为了参考,分别表示式(I)的表示y的阈值的y=0.00008x2+0.016x-2.51的值、和图表。
[表1]
[表2]
[表3]
符号说明
1.装饰片;11.合成树脂制衬底层;12.基材片;13.图案花纹层;14.透明性树脂层;15.表面保护层;2.基材;21.木质板;22.表面材料;101.家庭用加热器;102.家庭用加热器的台;103.金属制的长方形的台;104.金属制的框;105.试验片;106.试验片的长度方向的加热器侧的端部;107.点火器;L1.燃烧距离。
Claims (15)
1.一种装饰片,其是用于叠层在基材上的装饰片,所述基材的粘贴装饰片一侧的导热系数低于0.1W/(m·K),所述装饰片的特征在于:
(1)具有多层含有非卤系热塑性树脂的层;
(2)含有所述非卤系热塑性树脂的多层中的至少1层含有非卤系阻燃剂;
(3)将含有所述非卤系热塑性树脂的多层的厚度合计设为x、单位为μm,并且将含有所述非卤系热塑性树脂的多层中的所述非卤系阻燃剂的质量合计相对于含有所述非卤系热塑性树脂的多层的质量合计100质量%的比例设为y、单位为质量%时,满足下述式(I):
y≥0.00008x2+0.016x-2.51 (I);
(4)含有所述非卤系阻燃剂的多层的各层中的所述非卤系阻燃剂的含量为8质量%以上。
2.如权利要求1所述的装饰片,其特征在于:
所述非卤系阻燃剂为选自磷系阻燃剂和氮系阻燃剂中的至少1种。
3.如权利要求1或2所述的装饰片,其特征在于:
含有所述非卤系阻燃剂的多层的各层中的所述非卤系阻燃剂的含量为11质量%以上。
4.如权利要求1~3中任一项所述的装饰片,其特征在于:
含有所述非卤系热塑性树脂的多层中的所述非卤系阻燃剂的质量合计相对于含有所述非卤系热塑性树脂的多层的质量合计100质量%的比例y为40质量%以下。
5.如权利要求1~4中任一项所述的装饰片,其特征在于:
作为所述含有非卤系热塑性树脂的层,具有透明性树脂层,所述透明性树脂层的厚度为60μm以上。
6.如权利要求1~5中任一项所述的装饰片,其特征在于:
所述装饰片还具有表面保护层。
7.权利要求6所述的装饰片,其特征在于:
所述表面保护层是电离放射线固化型树脂层。
8.如权利要求7所述的装饰片,其特征在于:
所述电离放射线固化型树脂层是电子射线固化型树脂层。
9.如权利要求6~8中任一项所述的装饰片,其特征在于:
所述表面保护层的厚度为15μm以上。
10.如权利要求6~9中任一项所述的装饰片,其特征在于:
所述表面保护层含有微粒,所述微粒的平均粒径大于所述表面保护层的厚度。
11.如权利要求10所述的装饰片,其特征在于:
所述微粒通过超临界逆相蒸发法被囊泡化。
12.如权利要求1~11中任一项所述的装饰片,其特征在于:
所述装饰片的总厚度为150μm以上。
13.如权利要求1~12中任一项所述的装饰片,其特征在于:
所述非卤系阻燃剂通过超临界逆相蒸发法被囊泡化。
14.一种装饰板,其特征在于:
其是在基材上具有权利要求1~13中任一项所述的装饰片的装饰板,所述基材的粘贴所述装饰片一侧的导热系数低于0.1W/(m·K)。
15.如权利要求14所述的装饰板,其特征在于:
所述基材在所述装饰片一侧具有软木层。
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JP2007100045A (ja) * | 2005-10-07 | 2007-04-19 | Masamitsu Nagahama | ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用 |
JP2015182379A (ja) * | 2014-03-25 | 2015-10-22 | 大日本印刷株式会社 | 化粧シート及び化粧板 |
WO2016076360A1 (ja) * | 2014-11-11 | 2016-05-19 | 株式会社トッパン・コスモ | 化粧シート |
JP2017019274A (ja) * | 2015-07-10 | 2017-01-26 | 大日本印刷株式会社 | 化粧シート、化粧板及び化粧板の製造方法 |
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JP2007105964A (ja) | 2005-10-13 | 2007-04-26 | Toppan Cosmo Inc | 床用化粧材 |
CN104005538A (zh) * | 2007-11-19 | 2014-08-27 | 瓦林格创新股份有限公司 | 具有耐磨表面的基于纤维的镶板 |
US20130338280A1 (en) * | 2012-06-19 | 2013-12-19 | International Business Machines Corporation | Flame Retardant Material with Orthogonally Functional Capsules |
PT3446873T (pt) * | 2014-01-10 | 2021-08-10 | Dainippon Printing Co Ltd | Folha decorativa e placa decorativa, e processo de produção das mesmas |
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JP2007100045A (ja) * | 2005-10-07 | 2007-04-19 | Masamitsu Nagahama | ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用 |
JP2015182379A (ja) * | 2014-03-25 | 2015-10-22 | 大日本印刷株式会社 | 化粧シート及び化粧板 |
WO2016076360A1 (ja) * | 2014-11-11 | 2016-05-19 | 株式会社トッパン・コスモ | 化粧シート |
JP2017019274A (ja) * | 2015-07-10 | 2017-01-26 | 大日本印刷株式会社 | 化粧シート、化粧板及び化粧板の製造方法 |
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US20200223193A1 (en) | 2020-07-16 |
EP3689602A4 (en) | 2021-07-14 |
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