CN1336851A - 层压板用合成树脂膜及其生产方法 - Google Patents

层压板用合成树脂膜及其生产方法 Download PDF

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CN1336851A
CN1336851A CN00802938A CN00802938A CN1336851A CN 1336851 A CN1336851 A CN 1336851A CN 00802938 A CN00802938 A CN 00802938A CN 00802938 A CN00802938 A CN 00802938A CN 1336851 A CN1336851 A CN 1336851A
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A·X·刘
R·圭瓦瑙－马吉斯
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Abstract

公开了一种层压板用合成树脂膜的生产方法。该方法包括用含有未固化热固性树脂和低分布型添加剂的热固性树脂组合物浸渍基材并干燥,和对浸渍过的基材选择性地进行部分固化。低分布型添加剂典型地为惰性球状颗粒或粉末。本发明的方法生产的合成树脂膜有改进抗擦伤性。

Description

层压板用合成树脂膜及其生产方法
本发明涉及提高了抗擦伤性的层压板用合成树脂膜及其生产方法。
发明背景
合成树脂膜用于制造层压板。它最典型的用途是作为层压板的表面材料。合成树脂膜通常分为两种。第一种是浸渍纸，又称树脂浸渍纸或饱和纸。另一种是精制箔(finished foil)，又称装饰箔。浸渍纸与精制箔的区别在于树脂浸渍纸中的热固性树脂在层压前最多只是部分固化，而用于精制箔中的热固性树脂则为全部固化。这意味着在层压工艺中，浸渍纸不需要胶黏剂，而精制箔则需要。
合成树脂膜的生产是采用现有技术中熟知的方法和工艺。通常，浸渍纸的生产通过用含有热固性树脂的液态组合物浸渍基材，将树脂干燥，并在干燥的同时和/或在其后，对树脂进行部分固化以形成浸渍纸。通用的工业上的浸渍方法是把基材通过一个或多个包括含有热固性树脂的液体组合物的浴槽。然后，浸有树脂的基材典型地通过暴露向一升高了温度的干燥区，通常温度约为60-90℃进行干燥。在干燥的同时和/或在其后，通过加热来部分聚合树脂(部分固化)。部分固化所需的温度因树脂而不同，然而，典型的温度介于约100-170℃。组合物和浸渍纸生产的更多细节可在例如欧洲专利说明书No.0186257和UK专利说明书1591954中发现。制造精制箔的方法在现有技术中也已广泛知悉，这些方法和制造浸渍纸的方法大体相同，重要的区别是精制箔中的树脂基本上完全固化，而不是部分固化。
合成树脂膜主要用作制造层压板的表面材料，此类膜典型用作含木材料的表面材料，非限制性地举例，如，碎料板，中密度纤维板，复合板以及其他的木质材料。合成树脂膜尤其用于生产例如木器制造，家具，地板和汽车工业的装饰层压板。装饰层压板典型地采用已应用了彩色、经印刷等的基材生产的合成树脂膜以提供赏心悦目的美观质量。基材也可以是透明的，如在贴面中。
典型地，层压板是指“低压层压板”或“高压层压板”。根据本发明生产的合成树脂膜可用于低压层压板或高压层压板的生产。典型地，低压层压板的制造是通过把合成树脂膜，典型为树脂浸渍纸形式热压机层压到诸如纤维板，尤其是中密度纤维板，碎料板，复合板等“底板”或“板材”上。这会在板材或底板的表面上产生一层坚硬的、交联的热固材料。将板材或底板与合成树脂层压的一个主要原因是提供一个既赏心悦目又经久耐用的表面。因此，用于生产高压和低压层压用合成树脂膜的基材，典型地为彩色的，印刷的或有其它装饰的。因为这些用途，“树脂浸渍纸”有时被称作“树脂浸渍表面材料”。
常用于制造可在低压和高压下应用的合成树脂膜，尤其是树脂浸渍纸的树脂种类有蜜胺树脂(包括，例如蜜胺甲醛树脂)，脲树脂(包括，例如脲甲醛树脂)，和酚醛树脂(包括苯酚甲醛树脂)。当用于制造浸渍纸的树脂是蜜胺或脲树脂时，把树脂浸渍纸向底板进行热压来制造低压层压板，通常在温度介于约260°F(130℃)至约430°F(220℃)之间并在约200-430Psi(14-30千克/厘米2)的条件下进行。
另一方面，高压层压板习惯上通过在加热加压下对多层(至少为二层)的浸渍纸，织物和或其他的芯材料进行堆积和固化来制造。典型地，堆积组合件包括好几层(至少为2，但更为典型地为3至8)浸渍纸。所有这些层，装饰层除外，在正常情况下，虽非必须如此，都是牛皮纸基材浸渍酚醛树脂(包括苯酚甲醛树脂)或蜜胺树脂的树脂浸渍纸。如果装饰层置于其他层的顶部，那么它通常是由彩色的，印刷的或有其它装饰的纸质基材浸渍树脂形成的浸渍纸。为了能看到装饰层，可将透明或半透明的贴面置于装饰层上。形成高压层压板的堆积组合件通常在约230°F(110℃)至约340°F(170℃)之间并在约800Psi(56千克/厘米2)至1600Psi(112千克/厘米2)的条件下进行固化。关于层压板，尤其是装饰性高压层压板制造的更多信息可在例如上述的欧洲专利说明书No.0186257和UK专利说明书1591954中发现。
已知合成树脂膜的一些性能可以通过在用来浸渍基材的液态的热固性树脂中使用某些添加剂来改进。例如，可以添加丙烯酸类化合物来使浸渍纸更具柔性。此外，可以添加氧化铝(Al2O3)到树脂中来提高浸渍纸的抗磨性(EP0186257)。然而，提高合成树脂膜的抗擦伤性的这一需求的技术方案仍在研究探索之中。
令人奇怪的是，已经发现，在热固性树脂中使用低分布型(profile)添加剂，尤其是陶瓷微球体或低颗粒度的(粉末的)聚乙烯，能显著地改善由此得到的合成树脂膜的抗擦伤性。无需增加额外层数或不影响层压板的装饰性外观，就能够获得提高的抗擦伤性。
发明概述
本发明涉及层压板用合成树脂膜的生产方法，该合成树脂膜含有用热固性树脂组合物浸渍的基材，该方法包括
(a)用一含有热固性树脂和低分布型添加剂的热固性树脂组合物浸渍基材，和
(b)干燥(a)中浸渍过的基材。另外，在干燥的同时和/或在其之后，浸渍过的基材被至少部分固化。
优选的低分布型添加剂是陶瓷微球体。
本发明还涉及含有低分布型添加剂和液态热固性树脂的热固性树脂组合物的制备方法。
本发明进一步涉及含有被干燥且至少部分固化的热固性树脂和低分布型添加剂浸渍的基材的合成树脂膜。
还有，本发明涉及含有上述种类合成树脂膜的层压板。
发明详述
在一个实施方案中，本发明是一个生产合成树脂膜的方法，该方法通过用含有未固化热固性树脂和低分布型添加剂的热固性树脂组合物浸渍一基材，然后干燥浸渍过的基材来实现。在另一实施方案中，当浸渍完成后，在干燥过程中和/或其后对未固化的热固性树脂进行至少部分地固化。本发明也包括由此得到的合成树脂膜。已发现本文述及的低分布型添加剂的使用能显著地和令人吃惊地提高由此得到的合成树脂膜的抗擦伤性。
本发明工艺中，用于制造浸渍纸的基材，虽然通常是纸，可以是任何一种可浸渍基材，非限制的举例，如织造或非织造的织物。如果以装饰为目的，正常地，该基材应为印刷的，彩色的或有其它装饰的纸，该纸的基准重量为约20至约250克，更典型地为约70至130克。精制箔的典型基准重量为约30至90克/米2。打算用于高压层压板下层的浸渍纸最典型地应为牛皮纸基材且其基准重量为约30至约260克/米2。
原则上，任何未固化的热固性树脂或热固性树脂的混合物，均能用于根据本发明生产合成树脂膜的热固性树脂组合物。如今，最常用的树脂是蜜胺-甲醛，脲-甲醛，苯酚-甲醛，丙烯酸类和聚酯类树脂。此类树脂施用于基材时，典型地以水溶型或溶剂型溶液的形式，溶液中的树脂浓度为约40-60重量％，优选在约45至约55重量％。基材的树脂浸渍可通过多种施加树脂组合物的技术实施，例如，浸浴法、辊涂法、刮刀法、气刀法、线包柱法、计量辊轧法、刮片法等等。树脂组合物可以一个或多个阶段施加，在施加阶段之间可以进行干燥和/或部分固化。
树脂组合物中的“低分布型添加剂”是惰性的，基本上是球状颗粒，颗粒尺寸在约5至约60微米范围内，最优选范围在约10至约50微米。这些颗粒典型地为陶瓷或热塑性聚合物，例如聚乙烯。这些颗粒通常被称作微球体或粉末。商业上能够得到的低分布型添加剂，非限制地举例如Zeelan Industries，Inc.，St.Paul，MN生产的叫做Zeeospheres的陶瓷微球体和可从Baker Petrolite PolymerDivision得到的Po1ywax_牌的聚乙烯粉末(分子量为400-3000)。使用含有这些低分布型添加剂的未固化树脂组合物来生产合成树脂膜能令人吃惊地提供意外改进的抗擦伤性。低分布型添加剂所含的数量应能提供所需的抗擦伤性，通常为约2.5牛顿或更高，优选为约3.0牛顿或更高，最优选为约3.5牛顿或更高。为了产生所需的抗擦伤性，低分布型添加剂应典型地以至少约为0.5克/米2的数量存在于最终的合成树脂膜中，优选为至少约2克/米2，更优选为至少约5克/米2，最优选为至少约6克/米2。
本发明通过以下的非限制性实施例进一步地揭示和描述。所有的百分比，除非另外指出，均为重量百分比。
陶瓷微球体作为低分布型添加剂的样品的制备与测试
报告的实施例中的树脂浸渍纸通过下述的方法制备：
1.根据下面的配方制备的有50重量％的蜜胺甲醛树脂的未固化的热固性树脂组合物：
84％的蜜胺甲醛树脂水性组合物(固体含量59％)
33％Aricel 100(产自Borden Chemicals的催化剂)
10％水
3％Hypersal XT 793(产自Hoechst的润湿剂)
4.6％陶瓷微球体水性淤浆(见下)
在未固化热固性树脂组合物中含有低分布型添加剂的实施例中，低分布型添加剂以先行制成有67％固体的淤浆形式加入。通过把下述物质加入高速混合器来制备该淤浆：
80千克Zeeospheres W610陶瓷微球体
5千克Acumer9300(产自Rohm&Haas的分散剂)
35千克水
然后，在另一高速混合器中制备上述的未固化热固性树脂组合物(不含低分布型添加剂)。缓慢加入低分布型添加剂淤浆以形成混合良好的组合物。含有低分布型添加剂的实施例在表1中示出。表1实施例中的低分布型添加剂是Zeelan Industries，Inc.，St.Paul，MN生产的ZeeospheresW610的陶瓷微球体。
2. 400升上述制备好的热固性树脂组合物置于Babcock涂布机的第一浴槽中，该Babcock涂布机装有一卷1.5宽的装饰纸(每个实施例中的基准重量示于表1中)，且走纸速度为23米/分钟。如此处理过的纸在80℃空气中干燥。
3.根据下述配方制备第二种有55重量％蜜胺-甲醛树脂的未固化热固性树脂组合物：
90％蜜胺-甲醛树脂水性组合物(固体含量59％)
0.4％Aricel 100(产自Borden Chemicals的催化剂)
3.5％水
4.3％陶瓷微球体水性淤浆(固体含量67％)
0.8％Additiol VXT3750(产自Hoechst的脱模剂)
在第二种未固化热固性树脂组合物含有低分布型添加剂的实施例中，低分布型添加剂按与上述步骤1中描述的相同工艺添加到热固性树脂组合物中。含有低分布型添加剂的实施例示于表1中。所用的低分布型添加剂如上述的步骤1中所描述。在表1中，“有添加剂”的实施例在第一和第二种未固化热固性树脂组合物中都含有陶瓷微球体。
5.第二种未固化热固性树脂通过辊子施加到已经处理过一次的基材。然后，已处理过的装饰性树脂浸渍纸被传给一台有多种温度区的炉子：150℃，140℃和155℃。样品通过炉子的速度为22-24米/秒。最终的挥发物含量为约4.8％至约5.4％，合成树脂膜中的最终树脂含量为约56％至60％。
6.由此得到的合成树脂膜(在本案例中为树脂浸渍纸)，接下来通过使用一台Teledyne Taber擦伤测试机(Scratch Tester)来测试其抗擦伤性。首先，用Burkle压力机把树脂浸渍纸层压至一张5.5-6.0毫米厚的中密度纤维板上。通过在45巴和195℃操作压力机30秒实现层压。裁下一块10厘米×10厘米的层压板样品。在样品中心钻一个孔。把样品安装在Scratch Tester上。Scratch Tester利用一个增重的钻石指针在样品表面作圆形拖动。首先用5牛顿力，然后降低该力，(通常以0.5牛顿为增量)，直到钻石指针在样品上划出一个连续的圆。擦伤测试结果以牛顿为单位报告于表1。希望的抗擦伤性为2.5牛顿或更高，优选在约3.0牛顿或更高，更优选在约3.5牛顿或更高。
表1抗擦伤性测试结果：陶瓷微球体
样品序号 基准重量(克/米2) 添加剂含量(克/米2) 抗擦伤性有添加剂(牛顿) 抗擦伤性无添加剂(牛顿)
    1     80      6.8     4.0     2.5
    2     85      0.71     2.5     2.0
    3     85      5.0     3.0     2.0
    4     72      5.9     3.5     3.0
    5     83      2.73     4.0     3.5
    6     85      2.14     3.0     2.5
    7     85      3.01     3.5     3.0
    8     75      5.2     3.5     3.0
    9     80      5.7     4.5     3.5
    10     105      5.6     3.5     2.0
    11     80      5.9     3.5     2.0
    12     80      6.5     4.0     2.5
    13     130      3.7     4.5     3.0
    14     80      3.3     3.75     3.0
如上测试结果所示，根据本发明，低分布型添加剂的使用令人吃惊且出人意料的提高了树脂浸渍纸的抗擦伤性。
聚乙烯粉末作为低分布型添加剂的样品的制备和测试
报告的实施例中的树脂浸渍纸由下述方法制备。
1.根据下面的配方制备有50重量％蜜胺甲醛树脂的未固化热固性树脂组合物：
73.37％蜜胺甲醛树脂水性组合物(固体含量59％)
0.33％Aricel 100(产自Borden Chemicals的催化剂)
10％水
1.3％Hypersal XT793(产自Hoechst的润湿剂)
15％聚乙烯粉末(Polywax_，Baker Petrolite PolymerDivision)
各种成分在实验室混合器中混和。在未固化热固性树脂组合物中含有低分布型添加剂(聚乙烯粉末)的实施例中，低分布型添加剂直接分散到未固化的热固性树脂组合物中。在最终的未固化热固性树脂组合物中，低分布型添加剂占树脂液态成分的15重量％。含有低分布型添加剂的实施例示于表2中。
2.一块8英寸×10英寸的装饰纸，其基准重量示于表2中，置于盛有步骤1中的树脂组合物的浴槽中，直至树脂组合物已经渗透该纸片，由纸颜色变深所表示。如此处理过的纸片在炉中于130℃的温度干燥约40-50秒钟。
3.已经过步骤1处理过的一片装饰纸用辊涂布上述步骤1中制备的树脂组合物，来产生第二层树脂涂层。把处理后的纸置于炉中，于130℃的温度放置约120-130秒，完成由此获得的合成树脂膜。
4.由此获得的合成树脂膜(在此案例中为树脂浸渍纸)，接下来对其进行抗擦伤性测试，方法如上所述。结果报告于表2中。
表2
抗擦伤性测试结果：聚乙烯粉末
样品序号 基准重量(克/米2) 抗擦伤性有添加剂(牛顿) 抗擦伤性无添加剂(牛顿)
   15       85      3.0      1.5
   16       105      3.0      1.5
   17       130      3.5      2.0
如上面的测试结果所示，根据本发明，低分布型添加剂的使用令人吃惊且出人意料的提高了树脂浸渍纸的抗擦伤性。

Claims (40)

1.层压板用合成树脂膜的生产方法，该合成树脂膜含有一个浸渍有一种热固性树脂的基材，该方法包括
(a)用含有未固化热固性树脂和低分布型添加剂的热固性树脂组合物浸渍基材，和
(b)干燥(a)中浸渍过的基材。
2.权利要求1中的方法，进一步包括对浸渍基材中的未固化热固性树脂进行至少部分固化。
3.权利要求1的方法，其中该低分布型添加剂包括陶瓷微球体。
4.权利要求1的方法，其中该低分布型添加剂包括热塑性聚合物粉末。
5.权利要求1的方法，其中该低分布型添加剂包括聚乙烯粉末。
6.权利要求1的方法，其中该未固化热固性树脂从蜜胺-甲醛，脲-甲醛，苯酚-甲醛树脂及它们的混合物中选择。
7.权利要求1的方法，其中基材是纸。
8.权利要求1的方法，其中低分布型添加剂的含量应足够提供该合成树脂膜至少大约2.5牛顿的抗擦伤性。
9.层压板用合成树脂膜，根据权利要求1的方法生产。
10.权利要求1的方法，进一步包括
(c)用含有第二种未固化热固性树脂和低分布型添加剂的第二种热固性树脂组合物对(B)中的基材进行浸渍，和
(d)干燥(c)中浸渍过的基材。
11.权利要求10的方法，进一步包括对浸渍过的基材中的第二种未固化热固性树脂至少进行部分固化。
12.权利要求10的方法，其中该未固化热固性树脂和该第二种未固化树脂是相同的。
13.权利要求10的方法，其中该低分布型添加剂包括陶瓷微球体。
14.权利要求10的方法，其中该低分布型添加剂包括聚合物粉末。
15.权利要求10的方法，其中该低分布型添加剂包括聚乙烯粉末。
16.权利要求10的方法，其中该未固化热固性树脂和该第二种未固化热固性树脂独立从蜜胺-甲醛，脲-甲醛，苯酚-甲醛树脂及它们的混合物中选择。
17.权利要求10的方法，其中基材为纸。
18.权利要求10的方法，其中低分布型添加剂的含量应足够提供该合成树脂膜至少大约2.5牛顿的抗擦伤性
19.层压板用合成树脂膜，根据权利要求10的方法生产。
20.层压板用合成树脂膜，含有一用至少部分固化的热固性树脂和低分布型添加剂浸渍过的基材。
21.权利要求20的合成树脂膜，其中基材是纸。
22.权利要求20的浸渍纸，其中热固性树脂从蜜胺-甲醛，脲-甲醛，苯酚-甲醛树脂及它们的混合物中选择。
23.权利要求20的合成树脂膜，其中低分布型添加剂是陶瓷微球体。
24.权利要求20的合成树脂膜，其中低分布型添加剂是热塑性聚合物粉末。
25.权利要求20的合成树脂膜，其中低分布型添加剂是聚乙烯粉末。
26.权利要求20的合成树脂膜，其中低分布型添加剂的含量应足够提供该合成树脂膜至少大约2.5牛顿的抗擦伤性。
27.一种生产层压板的工艺，该工艺包括组装多层合成树脂膜，在这些层当中至少有一层是根据权利要求9的方法生产的合成树脂膜，并且使上述组装件经受足够的热与压力使所述各层固化，以生产层压板。
28.权利要求27的工艺，其中实现固化的必要加热温度为约230-340°F，且实现固化的必要压力为约800-1600Psi。
29.用权利要求27中的工艺制造的层压板。
30.一种制造层压板的工艺，该工艺包括组装多层合成树脂膜，这些层中最上的一层是权利要求10中的合成树脂膜，使该组装件经受足够的热与压力来使所述各层固化，以生产层压板。
31.权利要求30的工艺，其中实现固化的必要加热温度为约230-340°F，和实现固化的必要压力为约800-1600Psi。
32.用权利要求30的工艺生产的层压板。
33.一种层压板，含有与一基材层压的权利要求9中的合成树脂膜。
34.权利要求33的层压板，其中该基材包括木材。
35.权利要求33的层压板，其中该基材从碎料板、中密度纤维板和复合板中选择。
36.一种层压板，含有与一基材层压的权利要求10的合成树脂膜。
37.权利要求36的层压板，其中该基材包括木材。
38.权利要求36的层压板，其中该基材从碎料板、中密度纤维板和复合板中选择。
39.权利要求27的工艺，其中实现固化的必要加热温度是约260-430°F，和实现固化的必要压力是约200-430Psi。
40.权利要求30的工艺，其中实现固化的必要加热温度是约260-430°F，和实现固化的必要压力是约200-430Psi。
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CN1805846B (zh) * 2003-05-23 2010-07-21 酷瑞特表面控股有限公司 制备层状材料的方法和层状材料
CN109689345A (zh) * 2016-07-06 2019-04-26 威廉高级工程有限公司 纤维增强复合材料结构制造方法
US10987833B2 (en) 2016-07-06 2021-04-27 Williams Advanced Engineering Limited Manufacturing fiber-reinforced composite structures
CN109689345B (zh) * 2016-07-06 2021-07-02 威廉高级工程有限公司 纤维增强复合材料结构制造方法

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EP1169139B1 (en) 2010-12-08
AU2858900A (en) 2000-08-07
EP1169139A4 (en) 2003-05-21
DE60045334D1 (de) 2011-01-20
CA2358668A1 (en) 2000-07-27
US20060216536A1 (en) 2006-09-28
EP1169139A1 (en) 2002-01-09
BR0007620A (pt) 2002-01-15
WO2000043132A1 (en) 2000-07-27
CA2358668C (en) 2006-12-19
ATE490824T1 (de) 2010-12-15

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