CN102369106A - 包含硬质、片状矿物的层压体 - Google Patents

包含硬质、片状矿物的层压体 Download PDF

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CN102369106A
CN102369106A CN2010800138007A CN201080013800A CN102369106A CN 102369106 A CN102369106 A CN 102369106A CN 2010800138007 A CN2010800138007 A CN 2010800138007A CN 201080013800 A CN201080013800 A CN 201080013800A CN 102369106 A CN102369106 A CN 102369106A
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N·罗什
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High Intellectual Property Co ltd
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Abstract

本发明涉及一种在覆盖层中含有由氧化铝构成的片状单晶颗粒的层压体，所述颗粒具有刚玉晶格。

Description

包含硬质、片状矿物的层压体
多层的、热固性塑料被称作层压体，其通过将相同或不同材料的至少两个层压制并粘合而形成。单个材料的性能可通过组合而得到补充。
常见的层状材料大约0.5-1.2mm厚并且通常在进一步加工中采用特殊粘结剂贴合到载体材料(例如HDF板或木屑板)上。这样的层压涂层的最常见应用类型是层压地板和厨房操作台。然而，也能够毫无问题地制造厚度为2-20cm的层压体。这类被称为“紧密层压体”的产品随厚度的增加是自支承的，并且例如用于室内装修而且在室外应用中用作立面饰面或阳台饰面。层压体具有许多有利的性能：表面是致密的并且耐冲击和耐磨损。它可以被设置成各种结构并且短时间耐受高温而不会受到损害。表面容易保养和清洁，耐热、耐光以及无气味，并且对于醇或者有机溶剂以及对于水蒸气的影响不敏感。
为了获得层压体，在压力和温度下将多层经树脂浸渍的纸彼此压制。作为树脂使用蜜胺-甲醛树脂、酚醛树脂、脲醛树脂和这些物质的组合。对于高级装饰性层状材料，例如应用在层压地板中的层状材料，使用下述层：芯由多层经酚醛树脂浸渍的纸构成，在其上设有用蜜胺树脂浸渍的装饰层。在最顶部的位置压制所谓“覆盖层”，其由两层透明的经蜜胺树脂浸渍的纸构成，二者之间可以包夹一层由粗刚玉(＞20μm)构成的刚玉层。也可应用填充刚玉的覆盖层。在下侧使用降低成品材料的弯曲的反作用层。粗刚玉具有保护装饰层免受磨损的功能，并且也带来所需要的稳定性。然而，抗划伤性能几乎没有提高。
对于多层结构，通常还会采用密封层，其为了保护冲压板并避免应用表面的粗糙性而没有配备刚玉。此外，在压制层压体时粗刚玉发生沉积。密封覆盖层因而在未受保护的情况下暴露于日常划伤。
在WO2008/101621中通过混入金属氧化物纳米颗粒来降低覆盖层的划伤敏感性。尽管如此，人们希望显著提升层压板覆盖层的划伤迟钝性。
该目的可以令人惊奇地通过将片状、单晶刚玉混入层压板的覆盖层中来实现。
本发明因此涉及在覆盖层中含有由氧化铝构成的片状、单晶颗粒的层压体，该颗粒具有刚玉晶格。本发明所使用的优选的颗粒具有1-50微米、优选2-20微米的平均直径，厚度为50-500nm。径厚比(直径∶厚度的比例)介于1∶10和1∶100之间，优选介于1∶20和1∶100之间，更优选介于1∶30和1∶100之间，最优选介于1∶50和1∶100之间。
每个小片都是一个对可见光完全透明的刚玉单晶。
将本发明的刚玉小片与由氧化铝构成的纳米颗粒进行混合也是有利的，所述纳米颗粒的细度处于纳米范围内，优选＜200nm。可以用纳米颗粒填充所述小片之间的空隙。在此，纳米刚玉和刚玉小片的混合比可以是任意的。
此外，存在这样的可能性，将通常用于改善耐磨性的球形粗刚玉(粒度为10-100μm)与本发明中所述的刚玉小片组合。在这种组合的情况下获得具有改进的耐划伤性和改进的耐磨性的层压体。
可以以1-20g/m2的量使用粗刚玉、片状刚玉或它们的组合。在此，视所期望的耐磨性和耐划伤性而定可采用任意的混合比例。
片状氧化铝的制备本身是公知的，并且例如在爱尔兰专利申请IE 903320中有详细描述。在该专利申请中，在无机氟化物，例如LiF、NaF、KF或CaF2的存下在介于900和1100℃之间的温度下煅烧氢氧化铝。
还可以根据WO 2004/060804A1进行制备，其中将氢氧化铝在盐基质，例如在NaCl或Na2SO4中进行煅烧，所述盐基质促进各向异性生长。
本发明所使用的片状氧化铝可以是纯刚玉或掺杂刚玉。所有不会干扰形成刚玉相的六边形晶格的小片形状的金属，例如化学元素周期表中的第II主组元素，硅，铁，钴，镍，铜，锌，锆，钛，铬，锰及镧系元素均可以考虑用于掺杂。在此，掺杂物的含量小于10重量％，特别是0.0001-5重量％。
在下述实施方式中，“小片状氧化铝”既指小片形状的纯刚玉也指小片形状的掺杂刚玉。
本发明也涉及制备本发明的层压体的方法，其特征在于，将具有刚玉晶格的小片状氧化铝与浸渍树脂溶液相混合，采用该混合物浸渍在顶涂覆盖层中的纸或纺织织物，优选装饰纸，并在热压机中将浸渍过的纸或纺织织物施加于载板上。
基于固体浸渍树脂计，小片状氧化铝的份额有利地为1-10重量％。在通常的10-50μm的覆盖层层厚下这对应于1-20g/m2的矿物含量。
优选使用甲醛-三聚氰胺树脂，脲醛树脂，酚醛树脂以及这些树脂的组合作为浸渍树脂。这些树脂一般溶解于水中并且可包含其它常规添加剂，如固化剂和流平剂。
在进行如本申请所述的顶涂覆盖层浸渍之前，有利的是在进行中间干燥的情况下将纸或纺织织物拖曳通过含有浸渍树脂溶液的浴一次或多次(底涂覆盖层)。为了改善耐磨性，可向浸渍树脂溶液中添加球形粗刚玉，有利的添加量为基于固体浸渍树脂计1-10重量％。顶涂浸渍可通过浸入含有本发明的小片状氧化铝颗粒的浴中来进行或者通过用相应的液态混合物喷涂来来进行。也可以仅采用含有本发明的小片状氧化铝颗粒的液剂(Flotte)将纸或纺织织物浸渍一次或多次。
热压机通常在介于100和180℃之间的温度以及介于80和200巴之间的压力下运行。
浸渍树脂溶液大多具有介于30和70重量％之间，优选介于40和60重量％之间的树脂浓度。
另一种运行方式中，采用所谓的覆盖层纸，其已经浸渍过树脂并在纸浆中含有本发明的小片状氧化铝颗粒及任选地球形粗刚玉。然后，将该覆盖层纸铺置于装饰纸上，并同样在热压机中施加于载板上。
也可以考虑使用含有小片状刚玉的UV漆料作为覆盖层。
此外，本发明的层压体还可以含有其他添加剂，如在漆料工业中常规的那些，例如反应性稀释剂，溶剂及助溶剂，蜡，消光剂，润滑剂，消泡剂，脱气剂，流平剂，触变剂，增稠剂，无机和有机颜料，填料，粘附促进剂，UV稳定剂，HALS化合物，自由基清除剂，抗静电剂，润湿剂以及分散剂和/或视固化类型而定的催化剂、助催化剂、引发剂、自由基生成剂、光引发剂、光敏剂。作为其他添加剂还考虑聚乙二醇和其他保水剂、PE蜡、PTFE蜡、PP蜡、酰胺蜡、FT石蜡、褐煤蜡、接枝蜡、天然蜡、粗晶和微晶石蜡、极性聚烯烃蜡、脱水山梨糖醇酯、聚酰胺、聚烯烃、PTFE、润湿剂或硅酸盐。
下述实施例中的百分数表示重量百分数。
实施例1
以与WO 2004/060804A1的实施例5相似的方式制备直径为1-30微米且厚度为50-200nm(径厚比为约1∶90)的小片状刚玉颗粒。
将刚玉小片与固化剂和流平剂一起混入水性浸渍树脂(8％刚玉小片，基于Kauramin
Figure BPA00001479868200041
773固体，BASF，约50％树脂溶液计)并使用该混合物来涂覆印刷的黑色装饰纸。将该装饰纸用所述液剂浸渍两次，并且每次均在120℃的干燥箱中进行预先浓缩。在浸渍体完全干燥之后，在热压机中于160℃及200巴压力下将所述装饰纸层压到载板(40×40cm，厚度为5mm的HD载板)上。压制持续时间为4分钟。
比较例1(无矿物添加)：
如实施例1中那样进行，但在浸渍树脂中无刚玉小片。
比较例2(纳米刚玉)
替代小片状刚玉，将根据DE-A-102007008468制备的d90为120nm的纳米刚玉以8％的量混入实施例1中所提到的浸渍树脂中。装饰纸的制备及层压同样如实施例1那样进行。
比较例3(粗刚玉)
替代小片状刚玉，将d90为80μm的球形粗刚玉以8％的量混入实施例1中所提到的浸渍树脂中。仅在第1次浸渍时使用配备有粗刚玉的液剂。第2次浸渍用无刚玉的Kauramin来实施。装饰纸的制备及层压同样如实施例1那样进行。
每次均采用划伤测试仪来检验成品层压件的耐划伤性。以5N(0.5kg重量)的负载力作用于96号Scotch-brite垫。该垫以线性方式进行200次往复运动。在每50次往复之后，采用MICRO-TRI-GLOSSμ光泽度测量装置(BYK Gardner)来测量由于出现的划痕而造成的光泽度下降。
刚玉颗粒由于其高透明度本身不会造成任何视觉性能的损害。
表中显示了200次往复(刻痕)后相应的残余光泽度。
  实施例  实施例1  比较例1   比较例2  比较例3
  形貌   小片   无矿物   纳米颗粒   粗刚玉
  相对残余光泽度[％]   90   40   72   62
耐划伤性可以通过本发明的刚玉小片得到明显改善。

Claims (11)

1.层压体，在覆盖层中含有由氧化铝构成的片状单晶颗粒，所述颗粒具有刚玉晶格。
2.如权利要求1所述的层压体，其特征在于，所述颗粒在厚度为50-500nm的情况下具有在1-50微米范围内的平均直径。
3.如权利要求1或2所述的层压体，其特征在于，所述颗粒具有介于1∶10和1∶100之间的径厚比。
4.如权利要求3所述的层压体，其特征在于，所述颗粒的径厚比介于1∶50和1∶100之间。
5.如权利要求1-4中一项或多项所述的层压体，其特征在于，所述颗粒为掺杂有金属的刚玉。
6.如权利要求1-5中一项或多项所述的层压体，其特征在于，在所述覆盖层中以1-20g/m2的量含有所述颗粒。
7.如权利要求1-6中一项或多项所述的层压体，其特征在于，所述片状颗粒与粒度为10-100μm的球形粗刚玉组合。
8.制备如权利要求1-7中一项或多项所述的层压体的方法，其特征在于，将具有刚玉晶格的片状氧化铝与浸渍树脂溶液混合，用该混合物浸渍在顶涂覆盖层中的纸或纺织织物，优选装饰纸，并将浸渍过的纸或纺织织物在热压机中施加于载板上。
9.如权利要求8所述的方法，其特征在于，在进行中间干燥的情况下，将所述纸或纺织织物拖曳通过含有浸渍树脂溶液的浴一次或多次，并随后进行顶涂覆盖层浸渍。
10.如权利要求8或9所述的方法，其特征在于，所述顶涂覆盖层浸渍通过浸入含有片状氧化铝颗粒的浴中，或者通过喷涂由片状氧化铝颗粒和浸渍树脂溶液组成的液态混合物来进行。
11.如权利要求8所述的方法，其特征在于，所述顶涂覆盖层浸渍采用已经用树脂浸渍过并在纸浆中含有片状氧化铝颗粒和任选地球形粗刚玉的覆盖层纸以如下方式进行：将所述覆盖层纸铺置于纸或纺织织物，优选装饰纸上，并且在热压机中施加于载板上。
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