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CN102076764B - 采用杂化树脂的浸渍 - Google Patents

采用杂化树脂的浸渍 Download PDF

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CN102076764B
CN102076764B CN2009801250001A CN200980125000A CN102076764B CN 102076764 B CN102076764 B CN 102076764B CN 2009801250001 A CN2009801250001 A CN 2009801250001A CN 200980125000 A CN200980125000 A CN 200980125000A CN 102076764 B CN102076764 B CN 102076764B
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P·莱特尼
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Abstract

本发明涉及一种杂化树脂，其尤其适于浸渍纸幅。根据本发明的杂化树脂有利地可用于改进多层板中反向拉伸的机械性能。

Description

采用杂化树脂的浸渍
本发明涉及一种杂化树脂，其尤其适于浸渍纸幅。本发明的杂化树脂有利地可用于改进多层板中反向拉伸的机械性能。
将木质材料，如刨花板、纤维板，例如MDF板(中密度纤维板)或HDF(高密度纤维板)或OSB板(定向结构板)用装饰纸覆盖是已知的，所述装饰纸优选用氨基塑料树脂浸渍。此外，将通过多个纸层叠置构成的层压材料(连续层压材料-CPL)用装饰纸覆盖是已知的，所述装饰纸优选用氨基塑料树脂浸渍。为此采用的装饰纸通常具有30-140g/m2的基重。通常，用于浸渍纸幅的树脂是由三聚氰胺和甲醛构成的缩聚产物。当然也使用脲或/和三聚氰胺与甲醛混缩聚的缩聚产物。
为平衡由树脂浸渍层施加到材料板上的拉伸作用，通常将反向拉伸层施加到材料板的背面。作为常规反向拉伸浸渍体的标准浸渍，例如使用三聚氰胺-甲醛树脂。这类树脂非常昂贵，因此需要寻找替代品。
三聚氰胺脲醛树脂在不同的领域使用，例如用于木质材料的防水施胶或者用于装饰纸的核心浸渍。相对于纯三聚氰胺树脂，它们尤其具有经济上的优势。但是在不同的领域中，它们不能替代纯三聚氰胺甲醛树脂，因为在直接比较中，MUF树脂的机械和化学性能更差并因此是不利的。因此，MUF树脂例如不能产生用于制备强化地板的反向拉伸浸渍体的必需的拉伸作用，以便在同样的原料投料的情况下使三聚氰胺表面保持平衡。相应地，作为反向拉伸浸渍体，要么使用纯三聚氰胺甲醛树脂，要么在使用MUF树脂时需要非常大的树脂量，这除了带来经济上的劣势外还带来技术上的劣势。
因此，本发明的一个目的是提供一种树脂体系，其比三聚氰胺甲醛树脂成本更低并且仍然具有足够的机械性能以用作反向拉伸浸渍。
根据本发明，该目的通过提供一种树脂体系得以实现，所述树脂体系包括
(i)脲醛树脂、三聚氰胺甲醛树脂或/和三聚氰胺脲醛树脂，和
(ii)不饱和聚酯树脂。
根据本发明发现，通过将不饱和聚酯树脂加入包括脲醛树脂、三聚氰胺甲醛树脂或/和三聚氰胺脲醛树脂的树脂体系，可实现与传统的MUF树脂(三聚氰胺脲醛树脂或者三聚氰胺-脲-甲醛缩聚物)相比，技术性能且尤其是强度的明显的改进。由此可以用本发明的树脂体系实现用更昂贵的三聚氰胺树脂才得以实现的同样的性能或者实现与相似廉价的MUF树脂相比更佳的技术性能。
根据本发明的树脂体系(其为杂化树脂，也就是由至少两种组分构成的树脂)包括作为组分(i)的脲醛树脂(UF树脂)、三聚氰胺甲醛树脂(MF树脂)或/和三聚氰胺脲醛树脂(MUF树脂)。这些树脂每种情况下均为缩聚物。组分(i)优选含有至少一定份额的衍生自脲的树脂，尤其是所述份额≥1重量％，优选≥5重量％，更优选≥10重量％，尤其更优选≥20重量％，还更优选≥40重量％且最优选≥50重量％，基于总的树脂体系计。
树脂体系特别优选含有作为组分(i)的三聚氰胺脲醛树脂，其通过将脲醛树脂和三聚氰胺甲醛树脂混合而形成。虽然原则上可以采用任意的UF树脂与MF树脂之间的重量比，例如体系优选在99∶1至1∶99的范围内，其中UF树脂构成主要部分。UF树脂与MF树脂的份额比优选，每种情况下基于重量计，＞1.1∶1，尤其是＞1.1∶0.9，更优选＞1.5∶1且还更优选＞2∶1。
在另一实施方式中，作为成分(i)，包含通过甲醛作用于三聚氰胺和脲的混合物而获得的三聚氰胺脲醛树脂(MUF树脂)，也就是通过单体型原料的缩聚而形成的树脂。
在该实施方式中，还优选脲的份额大于三聚氰胺的份额，即尤其是＞1.1∶1，优选＞1.1∶0.9且更优选＞1.5∶1。
根据本发明的杂化树脂体系作为第二组分(ii)包含不饱和聚酯树脂。不饱和聚酯是聚酯缩聚物，其还含有至少一个不饱和的C＝C双键。这样的C＝C双键是可自由基交联的。作为聚酯，原则上可使用任何由一种或多种二官能化或多官能化的酸与一种或多种二官能化或多官能化的醇构成的缩聚物，只要至少一种所使用的单体含有一个双键。这样的缩聚物经证明是特别合适的，其中将马来酸用作酸结构单元。用于制备组分(ii)的其它合适的酸包括例如邻苯二甲酸、四氢邻苯二甲酸、对苯二甲酸和/或它们的酸酐，此外还有富马酸。此外可以使用这些酸和/或它们的酸酐的混合物以及与己二酸或癸二酸的混合物。
作为用于形成不饱和聚酯的醇结构单元，有利地使用二醇，尤其是单乙二醇(Monoethelenglykol)、二乙二醇、1，2-丙二醇、2，3-丁二醇或1，3-丁二醇且特别优选单乙二醇。
另外的有利的可供使用的醇例如是山梨醇、新戊二醇、丙三醇、三羟甲基丙烷、丁二醇或己二醇。此外可使用所述的醇的混合物。聚酯树脂中多余的酸基团可以用有机和/或无机碱中和以改进杂化树脂体系中反应活性的可调节性。优选使用氨基碱，例如三乙胺或三乙醇胺。
不饱和聚酯特别优选为由马来酸和单乙二胺构成的缩聚物。
除组分(i)以及(ii)以外，根据本发明的树脂体系可以含有另外的聚合物成分。然而，优选的是除组分(i)以及(ii)以外不含另外的聚合物成分的树脂体系，即尤其是不含分子量＞10,000g/mol，例如＞5,000g/mol，优选＞1,000g/mol且更优选500g/mol的成分。
根据本发明的树脂体系可含有任意的对所使用的树脂而言合适的分散剂或溶剂。水性树脂体系是优选的，基于总重量计，其具有≥5重量％，更优选≥10重量％的水的份额。树脂体系可含有另外的成分，例如润湿剂、固化剂和其它的添加剂和助剂，诸如单乙二醇。
根据本发明的树脂体系例如可用作具有改进的防水性和粘合力的胶料体系或者用于表面涂料。
本发明的树脂体系尤其适合用作浸渍树脂，该浸渍树脂用于浸渍由纤维原料构成的幅面状材料。这样的幅面状材料例如是纸幅或织物幅面或织物纤维网(Gewebevliese)。在此，所述幅面状材料例如可以由天然纤维或/和由和人造纤维构成。
特别有利的是，树脂体系用于浸渍由纤维原料构成的幅面状材料，所述幅面状材料作为反向拉伸层，尤其在生产层合地板时使用。基于其技术性能且尤其是其强度，用根据本发明的树脂体系能够提供反向拉伸层，其在以相对低的树脂量进行施涂时显现优异的拉伸作用。在这种情况下，树脂的施涂量通常为介于50和150g/m2之间，更优选60-100g/m2。在这种情况下，浸渍体重量通常为介于50和250g/m2之间，更优选介于100和200g/m2之间。
本发明的主题还包括一种由纤维原料构成的幅面状材料，尤其是如上文所描述的、用本发明的树脂体系浸渍的那种。作为幅面状材料优选使用纸，尤其是基重为30-140g/m2，特别是40-100g/m2的那种。
本发明最后还涉及一种多层板，其包含一个材料板，该材料板在其可见表面上被至少一个用树脂浸透的纸层覆盖，且在所述材料板的背面被至少一个用树脂浸透的反向拉伸层覆盖，其中将所述至少一个纸层和/或至少一个反向拉伸层用根据本发明的树脂体系浸渍。
所述材料板优选是木质材料板，例如刨花板或纤维板，优选MDF板(中密度纤维板)或HDF板(高密度纤维板)或OSB板(定向结构板)。所述材料板还可以是通过将多个纸层叠置而形成的层压材料板(CPL板；连续层压材料)。位于多层板的可见面的纸层优选是可见的纸层且更有选是装饰纸层。可见的纸层优选具有按照Bekk测量的至少20s，优选至少25s的粗纸平滑度。可见的纸层例如可具有大约30g/m2，尤其是40-140g/m2的基重。
反向拉伸层优选是由纤维原料构成的幅面状材料，如本文上文所述，其被树脂浸渍或者浸透。根据本发明的树脂体系可以用于浸渍可见纸层、反向拉伸层或这两层。优选至少用根据本发明的树脂体系浸渍反向拉伸层。根据本发明的树脂体系在反向拉伸层中具有优异的拉伸作用。
根据本发明，由纤维原料构成的幅面状材料的浸渍以及多层板的形成可以通过高压压机或低压压机来进行。合适的例如是多层压机、短循环压机或连续工作的压机(诸如通过式压机)。
通过下列实施例和所附的图进一步阐释本发明。
图1展示了用于阐释根据本发明的多层板100的基本结构的粗略的示意性剖视图。此处，材料板20被树脂浸透的纸层30覆盖，所述材料板例如包括木质材料板，例如刨花板或纤维板，优选MDF板或HDF板，或OSB板，或通过将多个纸层叠置构成的层压材料板，所述纸层尤其是可见的纸层。
材料板20的另外一面上设置了反向拉伸层40，其同样被树脂浸透。该反向拉伸层抵消了由被树脂浸透的可见纸层所施加的拉伸作用。根据本发明，将纸层30和反向拉伸层40中的至少一层用根据本发明的杂化树脂浸渍。
实施例1：杂化树脂体系
一种根据本发明的树脂体系由以下构成
-61g尿素树脂(市售)
-29g三聚氰胺树脂(市售)
-13g由马来酸酐和单乙二醇构成的聚酯缩聚物，分子量约为1000g/mol
-25g水
-0.4g润湿剂、1.8g固化剂、5g单乙二醇。
实施例2：树脂体系-对比实施例
一种不含聚酯缩聚物的树脂体系由下列原料构成：
-61g尿素树脂(市售)
-29g三聚氰胺树脂(市售)
-25g水
-0.4g润湿剂、1.0g固化剂(同样的凝胶化时间)、5g单乙二醇。
实施例3：标准浸渍
用于反向拉伸的市售的浸渍树脂具有如下组成：
-100g三聚氰胺树脂
-25g水
-0.4g润湿剂、0.6g固化剂(同样的凝胶化时间)、5g单乙二醇
采用所述树脂与基重为80g/m2的市售纸张制备树脂施涂量为100g/m2和残余湿度为6.5％的反向拉伸浸渍体。
实施例4：拉伸作用测试
将基重为80g/m2的市售纸张用根据本发明实施例1的杂化树脂体系以及根据实施例2的对比树脂体系浸渍。将浸渍体在160℃下干燥至残余湿度为6.5％。树脂施涂量为100g/m2。在短循环压机上在180℃下将浸渍体压制到高密度纤维板(HDF)上30秒。每次在高密度纤维板的背面上施涂根据实施例3的标准浸渍体。将冷却样品之后，测得变形率(mm/200mm覆盖层)。
这表明，由于反向拉伸浸渍体较强的拉伸作用，对比实施例的板在市售反向拉伸浸渍体的方向上变形。与之相反，用按照实施例1的杂化树脂浸透的纸覆盖的板在试验浸渍体的方向上是弯曲的(曲率为+0.1mm/200mm)。也就是，同样的树脂用量可获得更强的拉伸作用。

Claims (13)

1.树脂体系，包含
(i)三聚氰胺脲醛树脂，和
(ii)不饱和聚酯树脂，
所述组分(i)包含通过甲醛作用于三聚氰胺和脲的混合物而得到的三聚氰胺脲醛树脂。
2.根据权利要求1的树脂体系，其特征在于，
该树脂体系作为成分(i)包含通过将脲醛树脂和三聚氰胺甲醛树脂混合而形成的三聚氰胺脲醛树脂。
3.根据权利要求2的树脂体系，其特征在于，
基于重量计，脲醛树脂与三聚氰胺甲醛树脂的份额比大于1.1∶0.9。
4.根据前述权利要求中任一项的树脂体系，其特征在于，
所述组分(ii)是由马来酸和二醇构成的缩聚物。
5.根据权利要求1至4中任一项的树脂体系作为用于浸渍由纤维原料构成的幅面状材料的浸渍树脂的用途。
6.根据权利要求5的用途，其特征在于，
所述幅面状材料是纸幅或/和织物幅面或/和织物纤维网。
7.根据权利要求1至4中任一项的树脂体系用于浸渍由纤维原料构成的幅面状材料的用途。
8.根据权利要求7的用途，用于浸渍用于在压机上覆盖片状材料的纸幅。
9.根据权利要求1至4中任一项的树脂体系用于浸渍由纤维原料构成的幅面状材料的用途，其在生产层合地板时用作反向拉伸。
10.根据权利要求9的用途，用于浸渍纸幅。
11.用根据权利要求1-4中任一项的树脂体系浸渍的由纤维原料构成的幅面状材料。
12.多层板，包括材料板，该材料板在其可见表面上被至少一个用树脂浸透的纸层覆盖，且该材料板在多元材料板的背面被至少一个用树脂浸透的反向拉伸层覆盖，其特征在于，
将所述至少一个纸层或/和至少一个反向拉伸层用根据权利要求1至4中任一项的树脂体系浸渍。
13.根据权利要求12的多层板，其特征在于，
将所述的反向拉伸层用根据权利要求1至4中任一项的树脂体系浸渍。
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