CN109070541A - 具有改性的树脂层的载体材料和其制造 - Google Patents
具有改性的树脂层的载体材料和其制造 Download PDFInfo
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- CN109070541A CN109070541A CN201680084523.6A CN201680084523A CN109070541A CN 109070541 A CN109070541 A CN 109070541A CN 201680084523 A CN201680084523 A CN 201680084523A CN 109070541 A CN109070541 A CN 109070541A
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Abstract
本发明涉及一种载体材料，所述载体材料具有至少一个设置在载体材料的侧面中的至少一个侧面上的树脂层，其中至少一个树脂层包括：至少一种甲醛树脂；至少一种聚合物，所述聚合物选自：聚丙烯酸酯、聚环氧化物、聚酯、聚氨酯和长链的硅烷醇；和通式(I)RaSiX(4‑a)的至少一种含硅烷的化合物；和/或它们的水解产物，其中‑X是H、OH或者可水解的残基，其选自：卤素、烷氧基、羧基、氨基、单烷基氨基或二烷基氨基、芳氧基、酰氧基、烷基羰基，‑R是不可水解的有机残基，其选自：烷基、芳基、链烯基、取代和未取代的炔基、环烷基，所述环烷基能够通过‑O‑或‑NH‑中断，并且‑其中R能够具有至少一个官能团Q，所述官能团选自：羟基基团、醚基团、氨基基团、单烷基氨基基团、二烷基氨基基团、苯胺基基团、酰胺基基团、羧基基团、巯基基团、烷氧基基团、醛基基团、烷基羰基基团、环氧基基团、烯基基团、炔基基团、丙烯酸基团、丙烯酰氧基基团、甲基丙烯酸基团、甲基丙烯酰氧基基团、氰基基团和异氰基基团，并且‑a＝0、1、2、3，尤其是0、1或2。
Description
技术领域
本发明涉及一种根据权利要求1的前序部分所述的、设有树脂层的载体材料，一种根据权利要求9所述的包括这种载体材料的柔性层压板，一种根据权利要求13所述的用于制造这种层压板的方法和一种根据权利要求14所述的包括这种层压板的材料复合板(Werkstoffplatte)。
背景技术
目前，全世界每年生产和销售数亿平方米的人造板，所述人造板尤其呈层压地板形式或也作为墙板。这种人造板的成功和高度认可主要基于良好的特性轮廓和模仿自然表面，尤其木地板的可能性。
这种人造板通常具有由硬化的人造树脂构成的表面。尤其地，三聚氰胺覆层的表面在工业上的地板和家具领域中是最常出现的表面。
尤其在室内区域中，可使用的人造板能够具有许多不同的装饰面，例如，石头外观或木材外观。这些装饰面通过使用适合的装饰纸或也越来越多地以直接印刷方式施加在相应的载体板上。
除在视觉方面的仿效之外，也越来越多地致力于在触觉方面的仿效。在木材装饰面的领域中，适合的木材手感例如是值得期望的，所述木材手感是温暖宜人的并且是柔软的。而对于石头结构而言，近似天然的、冷的并且硬的手感是值得期望的。
用于改进或调整手感的方法途径在于将填充材料例如纤维素纤维或空心球结合到含三聚氰胺树脂的表面中。其它已知的解决方案是不含三聚氰胺的聚合物覆层。然而，这些聚合物覆层具有不太好的使用特性和加工特性并且是昂贵的以及并非是主流的。
用于改进手感的其它方法途径包括使用柔性的层压板，所述层压板例如通过胶合施加在载体板上。由于高柔性的层压板引起近似天然的视觉和触觉印象，所以其尤其适合用于制造现代的家具部件、地板和其它表面。这种层压板具有如下优点：所述层压板作为通常的层压板相对于更确切地说“刚性的并且脆性的实施方案”摸起来柔软并且有弹性以及显得“更温暖”。在此将层压板理解为层压材料，所述层压材料能够(例如通过胶合)施加在载体板上。尤其对于作为地板来使用而言，声响特性也是重要的方面。目前，在现有技术中已知的是例如柔性的层压板，其中层复合结构具有弹性薄膜，例如TPU薄膜。
用于获得柔性的表面的另一方法途径是所谓的LVT(豪华乙烯基板)。然而，所述LVT具有如下缺点：其是含PVC的，这例如由于增塑剂而对于一些应用是无法忍受的或仅受限制地容忍的。
相应地，始终存在对适合的解决方案的需求，所述解决方案用于使手感和其他表面特性匹配于相应的近似天然的装饰面。
发明内容
因此，本发明基于如下技术目的：将近似天然的、有弹性的和耐用的表面引入到地板面板或家具表面上。近似天然的表面例如包含下述特征：外观、手感、导热能力、硬度、表面结构、声响、抗冲击强度。
根据本发明，该目的通过具有权利要求1的特征的载体材料和具有权利要求9的特征的柔性的层压板实现。
相应地，提供一种载体材料，所述载体材料具有至少一个设置在载体材料的侧面中的至少一个侧面上的树脂层，其中至少一个树脂层包括改性的树脂和/或其水解产物，所述改性的树脂由以下构成
-至少一种甲醛树脂，
-至少一种聚合物，所述聚合物选自：聚丙烯酸酯、聚环氧化物、聚酯、聚氨酯和长链的硅烷醇，和
-通式(I)的至少一种含硅烷的化合物，所述通式(I)为
RaSiX(4-a) (I)，
其中
-X是H、OH或者可水解的残基，其选自：卤素、烷氧基、羧基、氨基、单烷基氨基或二烷基氨基、芳氧基、酰氧基、烷基羰基，
-R是不可水解的有机残基R，其选自：烷基、芳基、链烯基、炔基、环烷基，所述环烷基能够通过-O-或-NH-中断，并且
-其中R能够具有至少一个官能团Q，所述官能团选自：羟基基团、醚基团、氨基基团、单烷基氨基基团、二烷基氨基基团、苯胺基基团、酰胺基基团、羧基基团、巯基基团、烷氧基基团、醛基基团、烷基羰基基团、环氧基基团、烯基基团、炔基基团、丙烯酸基团、丙烯酰氧基基团、甲基丙烯酸基团、甲基丙烯酰氧基基团、氰基基团和异氰基基团，并且
-a＝0、1、2、3，尤其是0、1或2。
据此，在改性的树脂和尤其产生的树脂层中包含：至少两种有聚合能力的组分或聚合物组分，即甲醛树脂(例如呈氨基塑料树脂的形式，所述氨基塑料树脂即三聚氰胺-甲醛树脂)和另一反应性聚合物；和硅烷化合物。据此，树脂层是三组分体系。树脂层也能够表征为改性的(混合)树脂层。
就本申请而言，对于本领域技术人员显而易见的是：通式(I)的硅烷化合物的水解产物可通过通式(II)ObXc(OH)dReSiO(4-b-c-d-e)/2来概括，其中b,c,d＝0或1并且e＝1、2、3。通式(I)的化合物的水解和/或缩合受反应条件，尤其受树脂制备期间的酸性反应条件限定和影响。
在当前的树脂层中使用的甲醛树脂优选是尚未完全硬化的甲醛树脂并且相应地还具有游离的OH基团并且例如在三聚氰胺-甲醛树脂的情况下除了游离的OH基团之外也具有游离的NH2基团。所使用的甲醛树脂优选具有预缩合物和低聚物。所使用的甲醛树脂，尤其三聚氰胺-甲醛树脂的缩合度优选对应于在25℃时为1:1.7至2(树脂与水的体积比)的水兼容性。
在当前的树脂层中所使用的聚合物优选具有反应性基团，如羧基基团或OH基团。游离的OH基团在聚合物中所占的份额能够在5重量％和15重量％之间，优选在8重量％和12重量％之间。在使用聚氨酯作为聚合物的情况下，游离的OH基团的份额例如为9.5重量％。
根据所期望的触觉特性选择聚合物。如果例如应当在近似天然的柔软的表面如木材表面的情况下实现温暖的手感，那么优选使用长链的聚合物，所述聚合物不交联或仅以非常低的程度交联(也就是说，聚合物具有低的交联度)。在硬的表面例如具有更确切地说冷的手感的石头主题或瓷砖主题的情况下，优选使用具有较高的交联度(但小于三聚氰胺-甲醛树脂的交联度)的聚合物。
在当前的树脂层中所使用的、通式(I)的硅烷化合物或含硅烷的化合物用作为甲醛树脂和聚合物之间的中间体。因此，硅烷化合物的官能团实现与甲醛树脂和聚合物的相应的反应性基团的化学连接，由此保证不同组分的一致的并且均匀的混合。
在一个实施方式中，载体材料以载体板、纸层、薄膜层或织物层的形式存在。例如使用表层纸、装饰纸或牛皮纸作为纸层。
表层纸是薄的纸，所述表层纸通常已经用常规的三聚氰胺树脂浸渍。同样可购得如下表层纸，其中耐磨性颗粒，例如刚玉颗粒已经混入到表层的树脂中，以便提高耐磨强度。
装饰纸是用于人造板的表面精制的特殊纸张，所述装饰纸实现高度的装饰多样性。因此，除各种木材结构的典型的压印之外，可购得几何形状或艺术作品的广泛的压印。实际上不存在主题选择方面的限制。为了确保最佳的可印刷性，所使用的纸必须具有良好的光滑度和尺寸稳定性并且同样适合于人造树脂浸渍的渗透。
牛皮纸具有高的强度并且由纤维素纤维构成，向其添加淀粉、明矾和胶水，以便实现表面效应和强度提高。
在一个优选的实施方式中，载体材料部分地或完全地用改性的树脂浸渍，其中改性的树脂浸入或渗透到载体材料中。浸渍尤其在使用纸层作为载体材料时进行。当前，将术语“浸渍”理解为用由甲醛树脂、聚合物和硅烷化合物构成的改性的树脂完全地或部分地浸透纸层。这种浸渍例如能够在浸渍池中施用或通过刷涂、刮涂或喷涂方式施加。通过用改性的树脂浸渍纸层实现纸层的弹性化，所述纸层例如是装饰纸或表层纸。应注意的是：所使用的纸层已经能够用常规的树脂(例如三聚氰胺-甲醛树脂)预浸渍并且附加地施加改性的树脂。
在本发明的载体材料的另一实施方式中，也能够提出，树脂层不浸入到载体材料中，而是更确切地说涂覆在载体材料的表面上。在载体板用作载体材料的情况下尤其是这种情况。在这种情况下，至少一个树脂层设置在载体板的至少一个表面或至少一侧，即上侧和/下侧上。在此，将载体材料上的单层的或多层的构造理解为表面。
在载体板作为载体材料的情况下，该载体板优选是由木质材料(Holzwerkstoff)、塑料、木塑混合物或复合材料构成的板，尤其是刨花板、中密度纤维板(MDF)、高密度纤维板(HDF)、欧松板(OSB)或胶合板、水泥纤维板、石膏纤维板和/或WPC板(木塑复合材料)。涂覆在载体板上的树脂层的层厚度在10μm和100μm之间，优选在30μm和80μm之间，尤其优选在30μm和60μm之间。
载体材料的表面能够被表面处理，例如在木材载体板的情况下，表面能够被磨光。在塑料载体板的情况下，表面能够被电晕处理。
也可以考虑的是，在载体材料(尤其在载体板的情况下)的表面和改性的(混合)树脂层之间能够设置至少一个底漆层或至少一个底胶部。优选基于异氰酸酯的化合物作为底漆，其中尤其优选的是非芳香族的、脂肪族的异氰酸酯，如六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或包含这些异氰酸酯的预聚合物。
在一个优选的实施方式中，当前(混合)树脂层不设置在人造载体板的上述或下述树脂层上。特别地，当前的(混合)树脂层不设置在含甲醛的树脂层如三聚氰胺-甲醛树脂层上，所述三聚氰胺-甲醛树脂层位于载体材料(例如人造板)和(混合)树脂层之间。
在另一实施方式中，能够提出：至少一个树脂层设置在载体材料的上侧(即在装入载体材料之后朝向用户的一侧)上，并且在载体材料的背侧或下侧上，尤其在人造板作为载体材料的情况下，设置至少一个消声层。这种人造板优选用作地板面板、墙板、天花板、家具板或砧板。
在纸层作为载体材料的情况下，在进行覆层和/或浸渍之后，该纸层优选用作为装饰纸或表层纸。在这种情况下，尤其优选地，使用用改性的树脂浸渍过的纸层作为柔性的层压板或盖板的一部分，如接下来还将进一步详细阐述的那样。
在另一实施方式中，在至少一个树脂层中使用的甲醛树脂是三聚氰胺-甲醛树脂、三聚氰胺-尿素-甲醛树脂或尿素-甲醛树脂。
还提出：在至少一个树脂层中聚(甲基)丙烯酸酯用作为聚丙烯酸酯，脂肪族聚环氧化物(聚烷基二环氧化物)或芳香族聚环氧化物如基于双酚的聚环氧化物用作为聚环氧化物，脂肪族聚氨酯用作为聚氨酯。分子长度为至少20个单体单元，优选至少50个单体单元的长链的硅烷醇用作为硅烷醇。
聚合物优选用作含水的悬浮液，所述悬浮液以适当的方式被稳定。
在另一实施方式中，在当前的树脂层或改性的树脂中聚合物所占的数量份额为至少20重量％，优选至少30重量％，尤其优选至少50分量％。相应地，甲醛树脂和聚合物的质量比在20:80之间的范围中，优选在30:70之间的范围中，尤其优选在50:50之间的范围中。
树脂层中硅烷化合物所占的数量份额为至少3重量％，优选5重量％，还优选至少10重量％。特别地，在10重量％和20重量％之间的数量份额是优选的。
在通式(I)的硅烷化合物中所描述的残基X有利地选自：氟、氯、溴、碘；C1-6的烷氧基，尤其甲氧基、乙氧基、正丙氧基和丁氧基；C6-10的芳氧基，尤其苯氧基；C2-7的酰氧基，尤其乙酰氨基或丙酰氧基；C2-7的烷基羰基，尤其乙酰；具有C1至C12，尤其C1至C6的单烷基氨基或双烷基氨基。尤其优选可水解的基团是C1-4的烷氧基，尤其是甲氧基和乙氧基。
在一个优选的实施方式中，X选自：OH；C1-6的烷氧基，尤其甲氧基、乙氧基、正丙氧基和丁氧基。
不可水解的残基R优选选自：C1-C30烷基，尤其C5-C25烷基；C2-C6烯基；C2-C6炔基和C6-C10芳基。
在一个实施方式中，不可水解的残基R选自：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基、环己基、乙烯基、1-丙烯基、2-丙烯基、丁烯基、乙炔基、丙炔基、苯基和萘基。
当前将术语“不可水解的有机残基”理解为有机残基，所述有机残基在存在水时不引起与Si原子链接的OH基团或者NH2基团的形成。
能够包含在不可水解的有机残基R中的至少一个官能团Q有利地包括：环氧化物基团，尤其缩水甘油基团或缩水甘油醚氧基基团；氨基基团或异氰酸酯基团。
优选根据所使用的聚合物选择适合的官能团Q。因此，在使用聚丙烯酸酯作为聚合物的情况下，具有甲基丙烯酸基团或甲基丙烯酰氧基基团作为官能团Q的硅烷化合物是有利的。在使用聚环氧化物作为聚合物时，优选具有环氧化物基团作为官能团的硅烷化合物起作用。
在一个尤其优选的实施方式中，使用原硅酸四乙酯或甲基三乙氧基硅烷或还有γ-异氰酸丙基三乙氧基硅烷或缩水甘油醚氧基丙基三乙氧基硅烷作为硅烷。
如所描述的那样，不可水解的残基R具有至少一个官能团Q。此外，残基R也能够以被其他残基取代的方式存在。在此，能够存在下述残基或取代基：卤素、羟基、受保护的羟基、氧基、受保护的氧基、C3-C7环烷基、双环烷基、苯基、萘基、氨基、受保护的氨基、单取代的氨基、受保护的单取代的氨基、双取代的氨基、胍基、受保护的胍基、杂环、取代的杂环、咪唑基、吲哚基、吡咯烷基、C1-C12烷氧基、C1-C12酰基、C1-C12酰氧基、丙烯酰氧基、硝基、羧基、受保护的羧基、氨基甲酰基、氰基、甲基磺酰基氨基、巯基、C1-C10烷硫基和C1-C10烷基磺酰基。取代的烷基基团、芳基基团、烯基基团，能够一次或多次地被取代并且优选一次或两次地由相同的或不同的取代基取代。
术语“炔基”，如当前所使用的这样，表示式R-C≡C-的残基，尤其“C2-C6炔基”。C2-C6炔基的实例包括：乙炔基、丙炔基、2-丁炔基、2-戊炔基、3-戊炔基、2-己炔基、3-己炔基、4-己炔基、乙烯基以及直链和支链的烷基链的二炔和三炔。
术语“芳基”，如在这里所使用的这样，表示芳香烃，例如苯基、苄基、萘基或者蒽基。取代的芳基基团是如在上文中所限定的那样能够被一个或多个取代基取代的芳基基团。
术语“环烷基”包括如下基团：环丙基、环丁基、环戊基、环己基和环庚基。
在另一实施方式中提出，将多于一个的树脂层，优选两个、三个或四个树脂层设置在载体材料上。在树脂层多于一个的情况下，所述树脂层能够具有相同的或不同的成分。据此，在多层构造中，各个树脂层能够由不同的混合树脂构成并且以这种方式能够设定不同的特性。
在当前的载体材料的另一实施方式中提出，在树脂层中使用尺寸小于500nm的纳米颗粒。所使用的纳米颗粒具有在2nm和400nm之间，优选在2nm和100nm之间，尤其在2nm和50nm之间的尺寸。颗粒尤其能够是氧化性质的、氢氧化性质的或者氧化氢氧化性质的，所述颗粒经能够由不同的方法，例如离子交换工艺、等离子体工艺、溶胶-凝胶法、研磨或者还有火焰分离来制造。在一个优选的实施方式中，使用基于SiO2、A12O3、ZrO2、TiO2、SnO的颗粒。
同样提出：至少一个树脂层包括填充材料、交联剂或其他添加剂。
填充材料当前选自：纤维、抗磨材料、导电物质、导热材料、用于调整手感的材料或用于减少印痕例如指纹的材料。
为了改进树脂层的耐磨强度/抗磨强度，能够给树脂层添加抗磨颗粒。这些颗粒尤其能够由氧化铝(刚玉)、碳化物例如碳化硼、碳化硅、二氧化硅和/或玻璃球构成。在此，重要的是，颗粒的大小与树脂层的涂覆量相配合。抗磨颗粒的尺寸能够在1μm和20μm之间，优选5μm和15μm之间，尤其优选在7μm和12μm之间的范围中。在树脂层的层厚度例如为10μm至12μm的情况下，抗磨颗粒的颗粒尺寸应当不超过8μm至10μm。
除耐磨颗粒之外，在树脂层中也能够存在其他填充材料或添加剂，如天然纤维或合成纤维、阻燃剂和/或发光的抗菌物质。
适合的阻燃剂能够选自：磷酸盐、硼酸盐，尤其多磷酸铵、三(三溴新戊基)磷酸酯、硼酸锌或多元醇的硼酸络合物。
荧光物质或磷光物质，尤其亚硫酸锌能够用作为发光物质，并且亚硫酸锌和碱金属铝酸盐和银化合物能够用作抗菌剂。发光物质能够以多种几何形状通过模板涂覆到表面上。由此，通过将这些颜料加入到材料复合板的表面中，在照明装置失效时可以指示逃生路径和逃生方向，所述材料复合板例如在封闭的空间中能够用作为地板或墙板。
导电物质能够选自：炭黑、碳纤维、金属粉末，尤其碳纳米管或盐类。也能够使用这些物质的组合物。
所使用的天然纤维或合成纤维优选选自：木质纤维、纤维素纤维、部分漂白的纤维素纤维、羊毛纤维、大麻纤维以及有机的或无机的聚合物纤维。
尤其优选的填充材料或添加剂是：
·用于影响手感(导热能力、表面结构)、声波图和外观的纤维素纤维；
·用于影响导热能力的空心球；
·用于影响手感(导热能力、表面结构)、声波图和外观的木浆；
·用于提高抗划伤强度的刚玉；
·用于进一步调整手感的有机颗粒(例如不同尺寸的PUR小珠)或无机颗粒(例如Al2O3或SiO2实心颗粒)；
·不同的砂型，
·用于构造抗静电表面的导电颗粒；和/或
·用于改进抗指纹特性的硅树脂。
为了改进填充材料在树脂层中的分布，能够添加润湿剂或分散添加剂。典型的润湿剂是表面活性剂、脂肪酸或聚硅氧烷的衍生物。这种润湿剂也能够用于浸渍纸。
用于进行覆层和/或浸渍当前的载体材料的至少一种树脂以如下方法制造，所述方法包括下述步骤：
-提供至少一种甲醛树脂，
-将通式(I)的至少一种硅烷化合物添加给所述至少一种甲醛树脂；
-提供至少一种聚合物的悬浮液，所述聚合物选自聚丙烯酸酯、聚环氧化物、聚酯和聚氨酯；
-将聚合物悬浮液添加给由甲醛树脂和通式(I)的硅烷化合物构成的混合物；和
-将至少一种催化剂，尤其水解活性的化合物添加给混合物。
优选酸性反应的或碱性反应的化合物用作为水解活性的化合物。
酸性反应的化合物能够是以下物质，所述物质选自：饱和或不饱和的一元羧酸和多元羧酸，尤其十八烷酸、丙烯酸、甲基丙烯酸或巴豆酸；ss-二羰基化合物，尤其乙酰丙酮；或氨基酸、硫酸的有机衍生物如烷基硫酸盐或脂肪醇硫酸盐；磺酸酯如烷基磺酸和烷基磺酸盐；有机磷酸盐如(烷基)乙氧基化磷酸或卵磷脂；多元酸，尤其聚羟基天冬氨酸和多羟基硬脂酸。其它实例是，使用1H,1H-十五氟辛醇、辛醇、硬脂酸、油酸、己酰氯、己酸甲酯、己基氯和九氟丁基氯。
碱性反应的化合物优选选自：单胺和多胺，尤其甲胺或乙二胺；氨；碱金属氢氧化物和碱土金属氢氧化物，尤其NaOH。
在上述方法的一个变型形式中，树脂附加地与在上文中所说明的润湿剂、填充材料和/或其他添加剂混合。
如在上文中已经说明的那样，所期望的是，在柔性的层压板中使用设有改性的树脂，尤其用改性的树脂浸渍的纸层作为载体材料。相应地，也提供柔性的层压板(或盖板)，所述层压板包括至少一种设有改性的树脂的载体材料，其中载体材料是用改性的树脂浸渍的纸层，尤其牛皮纸层或装饰纸层。
在当前的层压板的一个实施方式中，除至少一个用改性的树脂浸渍的纸层之外，设有至少一个未用改性的树脂浸渍的纸层、至少一个透明纸层(玻璃纸)和/或至少一个塑料薄膜层。在层压板和层压板的层构造中用改性的树脂浸渍的纸层和其他纸层或薄膜层的使用和数量尤其以随后的应用为导向。不同的层或层片能够多次包含在层压板构造中、交替或交换其位置。然而，重要的是，在层压板中存在至少一个层片，用改性的树脂对所述层片覆层和/或浸渍所述层片。
当前在层压板中所使用的透明纸在术语上也叫玻璃纸。玻璃纸是由精细研磨的纤维素制成的、很大程度上防油的、但不耐湿的透明纸。通过非常强烈的压光获得其高的透明度。
在层压板中所使用的塑料薄膜层由聚合物构成，所述聚合物尤其来自聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、热塑性聚氨酯(TPU)或聚氨酯。
如已经表明的那样，当前的层压板能够具有多个，优选至少两个用改性的树脂浸渍的纸层，以及多个其它纸层或薄膜层。
如果使用两个或多个用改性的树脂浸渍的纸层，那么用于各个纸层的改性的树脂的成分能够是相同的或不同的。改性的树脂的量能够(按纸层计)在10重量％和50重量％之间，优选在20重量％和40重量％之间变动。在此，需注意的是，相对于在随后使用层压板时在载体板上不可见的纸层(例如45重量％)，形成与层压板压制在一起的载体板例如人造板的随后可见的表面的纸层，具有更少量的改性的树脂(例如10重量％)。换言之，，改性的层越靠近随后的表面，就能够越少地使用改性的树脂，因为这可能引起光学干扰(例如透明性)并且可能出现“多云奶白色的”外观。
据此，当前的层压板例如能够具有至少一个用改性的树脂浸渍的表层纸层和至少一个用改性的树脂浸渍的牛皮纸层；或至少一个用改性的树脂浸渍的装饰纸层和至少一个用改性的树脂浸渍的牛皮纸层。
在当前的柔性的层压板的第一变型形式中，设有至少一个用改性的树脂浸渍的表层纸层、至少一个未用改性的树脂浸渍的装饰纸层和至少一个用改性的树脂浸渍的牛皮纸层。
在当前的柔性的层压板的另一变型形式中，设有至少一个用改性的树脂浸渍的表层纸层、至少一个用改性的树脂浸渍的装饰纸层和至少一个用改性的树脂浸渍的牛皮纸层。
在当前的柔性的层压板的又一变型形式中，层压板包括：至少一个用改性的树脂浸渍的表层纸层；至少一个未用改性的树脂浸渍的装饰纸层；至少一个、优选至少两个透明纸层(玻璃纸)和至少一个用改性的树脂浸渍的牛皮纸层。可选地，能够设有至少一个反压部(Gegenzug)。这种层构造从上向下能够具有：用改性的树脂浸渍的表层纸层、未用改性的树脂浸渍的装饰纸层、玻璃纸层、用改性的树脂浸渍的牛皮纸层、玻璃纸层和可选的反压部。
在另一变型形式中，层压板包括：至少一个未用改性的树脂浸渍的表层纸层；至少一个用改性的树脂浸渍的装饰纸层；至少一个、优选至少两个透明纸层(玻璃纸)和至少一个用改性的树脂浸渍的牛皮纸层。这种层构造从上向下能够具有：未用改性的树脂浸渍的表层纸层、用改性的树脂浸渍的装饰纸层、玻璃纸层、用改性的树脂浸渍的牛皮纸层、玻璃纸层、用改性的树脂浸渍的牛皮纸层和可选的反压部。
在又一变型形式中，层压板包括：至少一个用改性的树脂浸渍的表层纸层；至少一个未用改性的树脂浸渍的装饰纸层、至少一个塑料薄膜层(例如PET层)；至少一个、优选两个用改性的树脂浸渍的牛皮纸层。在塑料薄膜层上，能够附加地在一侧或两侧上分别设置(例如基于异氰酸酯的)底漆。这种层构造从上向下能够具有：用改性的树脂浸渍的表层纸层、未用改性的树脂浸渍的装饰纸层、塑料薄膜层、两个相继用改性的树脂浸渍的牛皮纸层和可选的反压部。
在层压板的上述实施方式中所提及的反压部相应在需要时被吸收，如果这是必要的。
当前的层压板或盖板具有如下构造高度，所述构造高度具有在0.1mm和3mm之间，优选在0.1mm和2mm之间的厚度。
当前的载体材料以如下方法制造，所述方法包括下述步骤：
-制备上述的改性的树脂；
-将树脂涂覆到至少一种载体材料上，并且
-在热压机中压制覆层有树脂的载体材料。
为了制造层压板，在制备改性的树脂之后应用下述方法步骤：
-提供至少一个用改性的树脂浸渍的纸层，
-提供至少一个未用改性的树脂浸渍的纸层、至少一个透明纸层和/或至少一个塑料薄膜层，
-制造由用树脂浸渍的纸层、未用树脂浸渍的纸层、透明纸层和/或塑料薄膜层构成的成层部，并且
-在热压机中，尤其在连续式压力机或周期式压力机(例如，短周期压力机)或双带压力机中压制成层部。
紧接着，被压制的层压板(或盖板)铺设或胶合在适合的载体材料，尤其载体板上。利用至少一种粘合剂，尤其聚氨酯粘合剂或热塑性粘合剂进行胶合。这通常在胶合设施中发生。最后，被胶合的层压板和载体板彼此压制在一起。
在常规条件(周期时间、压制温度)下将树脂层或层压板与载体材料压制在一起。因此，树脂混合物能够在2MPa和8MPa之间的压力中并且在120℃和250℃之间的温度中硬化，以在载体材料上构成表面层。
在用于制备载体材料的方法的一个变型形式中也提出，在压制设置有树脂层的载体材料之前，将至少一种分离介质(例如聚硅氧烷如聚甲基硅氧烷，或氟改性的塑料如特氟龙)施加到树脂层上、施加到树脂层中和/或施加到压制板材的表面上。
设置在载体材料上的树脂层或层压板的进一步改性能够在于将例如为凹部或凸起的结构引入树脂层中。这种结构能够借助于结构化的涂覆辊在树脂层中产生，所述涂覆辊如果需要和/或如果期望的话能够与使用的装饰面相匹配。例如从EP 2 252 501 B1中已知这样的用于表面结构化的方法。
借助本发明，现在可以提供如下材料复合板，所述材料复合板具有耐用的但同时有弹性的、手感舒适的并且近似天然的表面。
因此，一方面，提供如下材料复合板，所述材料复合板由载体板构成，在其表面上(必要时在底漆或底胶部上)涂覆并且压制改性的树脂层。
另一方面，提供如下材料复合板，所述材料复合板由载体板与设置并且压制在其上的层压板构成。
在这两种情况下，优选使用由木质材料、塑料、木塑混合物或复合材料构成的板作为载体板，尤其是刨花板、中密度纤维板(MDF)、高密度纤维板(HDF)、欧松板(OSB)或胶合板、水泥纤维板、石膏纤维板和/或WPC板(木塑复合材料)。
附图说明
接下来，根据多个实施例参照附图详细阐述本发明。附图示出：
图1示出MDF板/HDF板，改性的树脂层设置在其上侧上；
图2示出柔性的层压板的第一实施方式；
图3示出柔性的层压板的第二实施方式；和
图4示出柔性的层压板的第三实施方式；
具体实施方式
实施例1：在MDF板/HDF板上构成近似木材的表面
将50g的三聚氰胺树脂混合物(无需引发剂)加热到50℃。紧接着，添加2.03g的原硅酸四乙酯。在搅拌条件下，还添加50g的BASF公司(Acronal DS 3591)的含羧基的水状的聚丙烯酸酯。在添加0.25g的对甲苯磺酸作为催化剂之后，开始水解反应和缩合反应。混合物仍继续搅拌30分钟。
通过添加3g的空心球(3M公司的K20)调节导热能力。在此，Acronal DS 3591用于提高弹性。
所制成的混合树脂在大约1天中是储存稳定的并且现在能够如常规的三聚氰胺那样进一步加工。
混合树脂涂覆在表面处理过的并且设置有底胶部的MDF板/HDF板上并且被压制。MDF板/HDF板的表面具有近似木材的温暖的手感。
在图1中示出由MDF板/HDF板1构成的、具有设置在表面上的改性的树脂层2的典型的层构造。
实例2：在MDF板/HDF板上构成石质的表面
将50g的三聚氰胺树脂混合物(无需引发剂)加热到50℃。紧接着，添加1.78g的甲基三乙氧基硅烷。在搅拌条件下，还添加50g的Alberdingk公司的U 9380。在添加0.2g的硫酸(1摩尔)作为催化剂之后，开始水解反应和缩合反应。混合物仍继续搅拌55分钟。
通过添加7g的石英砂和3g的刚玉(ZWSK 220，Treibacher)来调节硬度和导热能力以及耐磨强度。所添加的聚氨酯降低弹性。
所制成的混合树脂在大约1天中是储存稳定的并且现在能够如常规的三聚氰胺那样进一步加工。
混合树脂涂覆在表面处理过的并且设置有底胶部的MDF板/HDF板上并且压制。MDF板/HDF板的表面具有石质的冷的手感。
实施例3：层压板的第一实施方式
图2示出按照根据本发明的层压板的第一实施方式的层构造。
层构造从上向下具有：用改性的树脂浸渍的表层纸层3a-具有刚玉的、未用改性的树脂浸渍的装饰纸层4b-玻璃纸层5-用改性的树脂浸渍的牛皮纸层6a-玻璃纸层5和可选的反压部7。
原则上，用于浸渍不同的纸层的改性的树脂具有与在实施例1和2中提及的树脂成分类似的成分。
将50g的三聚氰胺树脂混合物(无需引发剂)加热到50℃。紧接着，添加1.78g的甲基三乙氧基硅烷。在搅拌条件下，还添加50g的Alberdingk公司的聚氨酯(U058)。在添加0.2g的硫酸(1摩尔)作为催化剂之后，开始水解反应和缩合反应。混合物仍继续搅拌55分钟。
改性的树脂用于浸渍表层纸层(10重量％树脂)和用于浸渍牛皮纸层(45重量％)。
紧接着，浸渍的和未浸渍的纸层以上述顺序相叠地铺设并且彼此压制成层压板。层压板例如根据EN 13329(Q5)以4.5mm的厚度和如下湿胀胶合到HDF板上并且进一步加工成地板面板，所述湿胀为5％边缘湿胀。
实施例4：层压板的第二实施方式
图3示出按照根据本发明的层压板的第二实施方式的层构造。
层构造从上向下具有：未用改性的树脂浸渍的表层纸层3a-用改性的树脂浸渍的装饰纸层4b-玻璃纸层5-用改性的树脂浸渍的牛皮纸层6a-玻璃纸层5-用改性的树脂浸渍的牛皮纸层6和可选的反压部7。
将50g的三聚氰胺树脂混合物(无需引发剂)加热到50℃。紧接着，添加2.03g的原硅酸四乙酯。在搅拌条件下，还添加50g的Alberdingk公司的聚氨酯(U058)。在添加0.25g的对甲苯磺酸作为催化剂之后，开始水解反应和缩合反应。混合物仍继续搅拌30分钟。
改性的树脂用于浸渍装饰纸层(15重量％树脂)并且用于浸渍牛皮纸层(45重量％)。
紧接着，浸渍的和未浸渍的纸层以上述顺序相叠地铺设并且彼此压制成层压板。层压板例如胶合到MDF板上并且进一步加工成家具板。
实施例5：层压板的第三实施方式
图4示出按照根据本发明的层压板的第三实施方式的层构造。
这种层构造从上向下能够具有：用改性的树脂浸渍的表层纸层3a-未用改性的树脂浸渍的装饰纸层4b-作为塑料薄膜层的PET层8，其中在塑料薄膜层的这两侧上分别设置有(例如基于异氰酸酯的)底漆-两个相继用改性的树脂浸渍的牛皮纸层6a和可选的反压部7。
将50g的三聚氰胺树脂混合物(无需引发剂)加热到50℃。紧接着，添加1.78g的原硅酸四乙酯。在搅拌条件下，还添加50g的Alberdingk公司的聚氨酯(U058)。在添加0.2g的硫酸(1摩尔)作为催化剂之后，开始水解反应和缩合反应。混合物仍继续搅拌55分钟。
改性的树脂用于浸渍表层纸层(10重量％树脂)并且用于浸渍牛皮纸层(45重量％)。
紧接着，浸渍的和未浸渍的纸层与PET层以上述顺序相叠地铺设并且彼此压制成层压板。
Claims (15)
1.一种载体材料，所述载体材料具有至少一个设置在所述载体材料的侧面中的至少一个侧面上的树脂层，
其特征在于，
所述至少一个树脂层包括改性的树脂和/或其水解产物，
所述改性的树脂由以下构成
-至少一种甲醛树脂，
-至少一种聚合物，所述聚合物选自：聚丙烯酸酯、聚环氧化物、聚酯、聚氨酯和长链的硅烷醇，和
-通式(I)的至少一种含硅烷的化合物，所述通式(I)为
RaSiX(4-a) (I)，
其中
-X是H、OH或者可水解的残基，其选自：卤素、烷氧基、羧基、氨基、单烷基氨基或二烷基氨基、芳氧基、酰氧基、烷基羰基，
-R是不可水解的有机残基R，其选自：烷基、芳基、链烯基、取代和未取代的炔基、环烷基，所述环烷基能够通过-O-或-NH-中断，并且
-其中R能够具有至少一个官能团Q，所述官能团选自：羟基基团、醚基团、氨基基团、单烷基氨基基团、二烷基氨基基团、苯胺基基团、酰胺基基团、羧基基团、巯基基团、烷氧基基团、醛基基团、烷基羰基基团、环氧基基团、烯基基团、炔基基团、丙烯酸基团、丙烯酰氧基基团、甲基丙烯酸基团、甲基丙烯酰氧基基团、氰基基团和异氰基基团，并且
-a＝0、1、2、3，尤其是0、1或2。
2.根据权利要求1所述的载体材料，
其特征在于，
所述载体材料以载体板、纸层、薄膜层或织物层的形式存在，所述纸层尤其是表层纸层、牛皮纸层或装饰纸层。
3.根据权利要求1或2所述的载体材料，
其特征在于，
所述载体材料部分地或完全地用所述树脂层浸渍。
4.根据上述权利要求中任一项所述的载体材料，
其特征在于，
所述甲醛树脂是三聚氰胺-甲醛树脂、三聚氰胺-尿素-甲醛树脂或尿素-甲醛树脂。
5.根据上述权利要求中任一项所述的载体材料，
其特征在于，
聚(甲基)丙烯酸酯用作为聚丙烯酸酯,脂肪族聚环氧化物(聚烷基二环氧化物)或芳香族聚环氧化物用作为聚环氧化物，脂肪族聚氨酯用作聚氨酯。
6.根据上述权利要求中任一项所述的载体材料，
其特征在于，
甲醛树脂和聚合物的质量比在20:80之间的范围中，优选在30:70的范围中，尤其优选在50:50之间的范围中。
7.根据上述权利要求中任一项所述的载体材料，
其特征在于，
多于一个的树脂层，优选两个、三个或四个树脂层设置在所述载体材料上。
8.根据上述权利要求中任一项所述的载体材料，
其特征在于，
所述树脂层包括纳米颗粒、填充材料、润湿剂或其它添加剂，所述纳米颗粒具有小于500nm的尺寸。
9.一种柔性的层压板，所述层压板包括至少一种根据权利要求1至7中任一项所述的载体材料，其中所述载体材料是用所述改性的树脂浸渍的牛皮纸层、表层纸层或装饰纸层。
10.根据权利要求9所述的层压板，
其特征在于，
除了至少一个用所述改性的树脂浸渍的纸层之外，设有至少一个未用所述改性的树脂浸渍的纸层、至少一个透明纸层(玻璃纸)和/或至少一个塑料薄膜层。
11.根据权利要求9或10所述的层压板，
其特征在于，设有至少两个用所述改性的树脂浸渍的纸层。
12.根据权利要求11所述的层压板，
其特征在于，设有至少一个用所述改性的树脂浸渍的表层纸层和至少一个用所述改性的树脂浸渍的牛皮纸层，或至少一个用所述改性的树脂浸渍的装饰纸层和至少一个用所述改性的树脂浸渍的牛皮纸层。
13.一种用于制造根据权利要求9至12中任一项所述的层压板的方法，所述方法包括如下步骤：
-提供至少一个用树脂浸渍的纸层，
-提供至少一个未用树脂浸渍的纸层，至少一个透明纸层和/或至少一个塑料薄膜层，
-制造成层部，所述成层部由用所述树脂浸渍的纸层、未用所述树脂浸渍的纸层、透明纸层和/或塑料薄膜层构成，和
-在热压机中，尤其在连续式压力机或周期式压力机(例如短周期压力机)或双带压力机中压制所述成层部。
14.一种材料复合板，所述材料复合板包括载体板与根据权利要求9至12中任一项所述的至少一个层压板，所述层压板设置在所述载体板的至少一侧上。
15.根据权利要求14所述的材料复合板，
其特征在于，
由木质材料、塑料、木塑混合物或复合材料构成的板用作为载体板，所述板尤其是刨花板、中密度纤维板(MDF)、高密度纤维板(HDF)、碎木板(OSB)或胶合板、水泥纤维板、石膏纤维板和/或WPC板(木塑复合材料)。
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| EP16164881.1A EP3231596B1 (de) | 2016-04-12 | 2016-04-12 | Trägermaterial mit modifizierter harzschicht und herstellung desselbigen |
| PCT/EP2016/079282 WO2017178083A1 (de) | 2016-04-12 | 2016-11-30 | Trägermaterial mit modifizierter harzschicht und herstellung desselbigen |
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|---|---|
| US (1) | US11951719B2 (zh) |
| EP (2) | EP3231596B1 (zh) |
| CN (1) | CN109070541B (zh) |
| CA (1) | CA3020624C (zh) |
| ES (2) | ES2702383T3 (zh) |
| PL (1) | PL3231596T3 (zh) |
| PT (2) | PT3231596T (zh) |
| RU (1) | RU2706649C1 (zh) |
| UA (1) | UA122922C2 (zh) |
| WO (1) | WO2017178083A1 (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL3718768T3 (pl) * | 2019-04-02 | 2022-05-02 | Flooring Technologies Ltd. | Impregnat o właściwościach antystatycznych |
| EP3718769B1 (de) | 2019-04-02 | 2023-06-07 | Flooring Technologies Ltd. | Holzwerkstoffplatte mit antistatischen eigenschaften |
| CN110790969B (zh) * | 2019-11-26 | 2022-06-21 | 东北林业大学 | 一种层层自组装阻燃木塑复合材料的制备方法 |
| HUE058953T2 (hu) | 2020-03-11 | 2022-09-28 | Flooring Technologies Ltd | Kompozit anyag termoplasztikus fóliával padlózat-panelben történõ alkalmazásra és eljárás annak elõállítására |
| EP3904463A1 (de) * | 2020-04-30 | 2021-11-03 | Flooring Technologies Ltd. | Zusammensetzung zur mattierung und reduzierung von anti-fingerprint-effekten von oberflächen auf trägermaterialien |
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- 2016-04-12 EP EP16164881.1A patent/EP3231596B1/de active Active
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- 2016-11-30 CN CN201680084523.6A patent/CN109070541B/zh active Active
- 2016-11-30 UA UAA201809760A patent/UA122922C2/uk unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| UA122922C2 (uk) | 2021-01-20 |
| CN109070541B (zh) | 2021-11-16 |
| CA3020624A1 (en) | 2017-10-19 |
| EP3231596B1 (de) | 2018-10-10 |
| CA3020624C (en) | 2021-02-02 |
| PT3231596T (pt) | 2019-01-17 |
| US20190126600A1 (en) | 2019-05-02 |
| EP3442791B1 (de) | 2020-10-28 |
| RU2706649C1 (ru) | 2019-11-19 |
| PT3442791T (pt) | 2020-12-18 |
| US11951719B2 (en) | 2024-04-09 |
| ES2836212T3 (es) | 2021-06-24 |
| EP3442791A1 (de) | 2019-02-20 |
| ES2702383T3 (es) | 2019-02-28 |
| PL3231596T3 (pl) | 2019-04-30 |
| EP3231596A1 (de) | 2017-10-18 |
| WO2017178083A1 (de) | 2017-10-19 |
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