CN101080371B - 泡沫大理石制品及其加工方法 - Google Patents

泡沫大理石制品及其加工方法 Download PDF

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CN101080371B
CN101080371B CN2005800429872A CN200580042987A CN101080371B CN 101080371 B CN101080371 B CN 101080371B CN 2005800429872 A CN2005800429872 A CN 2005800429872A CN 200580042987 A CN200580042987 A CN 200580042987A CN 101080371 B CN101080371 B CN 101080371B
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acrylic resin
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slurry
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朴应绪
罗焘春
田宰旭
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Samsung SDI Co Ltd
Lotte Advanced Materials Co Ltd
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Abstract

本发明披露一种泡沫大理石制品及其制备方法。用于制备泡沫大理石制品的组合物包括约100重量份的丙烯酸类树脂,约10到80重量份的固体颗粒以及约0.1到10重量份的引发剂。这种泡沫大理石制品包括第一层的丙烯酸人造大理石,和第二层的由丙烯酸类树脂制成的具有不规则孔洞的发泡结构,其中第二层结构被层压在第一层之上以形成一体。本发明的泡沫大理石制品由于其轻质和加工性的缘故要优于同等规格的传统人造大理石。

Description

泡沫大理石制品及其加工方法
技术领域
本发明涉及一种泡沫大理石制品及其加工方法。具体说,本发明涉及重量轻、可加工性好的泡沫人造大理石制品,其通过在经放热反应的丙烯酸类树脂固化过程中,使该丙烯酸类树脂发泡而形成。
背景技术
总的来说,人造大理石根据基本树脂材料类型分为两类:一类是丙烯酸型人造大理石;另一类是不饱和聚酯型人造大理石。与不饱和聚酯型人造大理石相比,丙烯酸型人造大理石因其具有优美的外观、高级的纹理和良好的耐候性而广泛应用于厨房台面板、洗脸池、梳妆台、浴盆、各种台面、墙面材料、内部制品等。
简单地说,丙烯酸型人造大理石是通过将树脂混合物注入模具并将该注入的树脂混合物固化而加工成的。该树脂混合物是通过将无机填充物、颜料、固化剂以及一些添加物如聚合引发剂、脱模剂、分散剂等加入到由甲基丙烯酸甲酯(MMA)和聚甲基丙烯酸甲酯(PMMA)构成的树脂浆料中制成的。
通常,市售的人造大理石的厚度约为13mm。尽管人造大理石与天然大理石相比具有质量轻、易加工的优势,但是还是比胶合板更重、更贵。因此,一种在人造大理石外附加一层3mm厚的胶合板构成的复合板已经商品化应用了。
然而,由于使用了粘接剂,这种结合有胶合板的人造大理石生产成本高、耐久性差、以及用途受限制。
因此,本发明通过制造用于人造大理石的特殊的发泡组合物、使该发泡组合物中的丙烯酸类树脂移到上半部形成上层、并通过放热反应固化该发泡组合物同时发泡上层的丙烯酸类树脂层而开发出一种重量轻、可加工性好的泡沫大理石制品。
发明内容
本发明的目的之一是提供轻质泡沫大理石制品。
本发明的另一目的是提供具有良好可加工性的泡沫大理石制品。
本发明进一步的目的是提供一种不使用发泡剂,而是通过丙烯酸酯聚合反应中的放热特性来制造泡沫大理石的方法。
本发明的其他目的和优点会在后面的说明书和所附权利要求中进行说明。
本发明的一个方面是提供一种用于泡沫人造大理石的组合物,包括约100重量份的丙烯酸类树脂,约10到80重量份的固体颗粒,和约0.1到10重量份的引发剂。
在一些实施方式中,该固体颗粒可选自由无机填料、大理石碎片和它们的混合物组成的组。
在一些实施方式中,该无机填料可选自由碳酸钙、氢氧化铝、硅土、氧化铝、氢氧化镁和它们的混合物组成的组。
在一些实施方式中,通过将约100重量份的丙烯酸类树脂,约100到200重量份的无机填料,约0.1到10重量份的交联剂以及约0.1到10重量份的引发剂混合,固化该混合物以形成固化的人造大理石,然后再粉碎该固化的人造大理石,来制备该大理石碎片。
在一些实施方式中,该组合物的流度在约13cm/min到约20cm/min的范围内。
在一些实施方式中,该丙烯酸类树脂是丙烯酸单体及聚丙烯酸酯的混合物。
另一个实施方式是用于制造泡沫大理石制品的方法,包括:混合丙烯酸类树脂、固体颗粒和引发剂,以形成用于人造大理石的可发泡浆料,放置该可发泡浆料一段时间,以使比重相对较小的丙烯酸类树脂充分移到上半部形成上层,同时比重相对较高的固体颗粒充分移到下部形成下层,然后通过放热反应固化该可发泡浆料同时发泡上层的丙烯酸类树脂。
在一些实施方式中,该固体颗粒可选自由无机填料、大理石碎片和它们的混合物组成的组。
在一些实施方式中,该组合物的流度在约13cm/min到约20cm/min的范围内。
在一些实施方式中,该丙烯酸类树脂是丙烯酸单体及聚丙烯酸酯的混合物。
在一些实施方式中,该可发泡浆料被倒在传统的固体人造大理石板的表面,然后放置一段时间以使丙烯酸类树脂充分移到上层。
本发明的另一方面提供一种泡沫大理石制品,包括第一层的丙烯酸人造大理石,第二层的由丙烯酸类树脂制成的具有不规则孔洞的发泡结构,其中,第二层层压在第一层的上并形成一体。
在一些实施方式中,该第二层由丙烯酸类树脂发泡形成。
附图说明
图1是显示在实施例1中得到的发泡人造大理石的侧视图的照片。
具体实施方式
本发明的泡沫大理石制品包括:第一层的丙烯酸人造大理石,和第二层的由丙烯酸类树脂制成的具有不规则孔洞的发泡结构,其中,该第二层层压在该第一层上形成一体。该第二层是通过发泡丙烯酸类树脂形成。本发明的泡沫大理石制品可以由用于人造大理石的发泡组合物制造。
本发明的用于人造泡沫大理石的可发泡组合物包括丙烯酸类树脂、固体颗粒和引发剂。
本发明所用的丙烯酸类树脂是丙烯酸单体及其聚合物、聚丙烯酸酯的混合物。该丙烯酸单体的典型例包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯等。该聚丙烯酸酯为上述单体的聚合物。其中,优选聚甲基丙烯酸甲酯(PMMA)。
优选地,该丙烯酸类树脂中丙烯酸单体的量以重量计约为80~95%,聚丙烯酸酯的量以重量计约为5~20%。如果该聚丙烯酸酯的含量以重量计超过20%,则不能获得充分的发泡。
在一些实施方式中,每100重量份的丙烯酸类树脂,固体颗粒的量约为从10重量份到约80重量份。如果固体颗粒量少于10重量份,那么浆料的黏度变低,使得过程往往难以控制。相反,如果该量超过了80重量份,丙烯酸类树脂中的丙烯酸单体则不能扩散。
该固体颗粒可选自由无机填料、大理石碎片和它们的混合物组成的组。
可以使用现有技术中熟知的任何无机填料。该无机填料的典型例包括碳酸钙、氢氧化铝、硅土、氧化铝、氢氧化镁等。其中,由于含有氢氧化铝的人造大理石具有美的外观,最优选氢氧化铝。
在一实施方式中,可以任选添加具有不同颜色的传统人造大理石碎片。该大理石碎片可由传统方法制备。如,大理石碎片这样制备:将100重量份的丙烯酸类树脂、100到200重量份的无机填料、0.1到10重量份的交联剂和0.1到10重量份的引发剂混合,固化该混合物并粉碎该固化的材料。作为交联剂,可以使用现有技术中熟知的传统交联剂。本领域普通技术人员能识别用于该混合物的合适的交联剂。在其它实施方式中,可以使用不饱和聚酯树脂基的人造大理石碎片。
引发剂的例子包括过氧化物,如过氧化苯甲酰、过氧化十二(烷)酰、丁基过氧化氢、过氧化氢异丙苯等,以及偶氮化合物,如偶氮二异丁腈及其类似物。该引发剂的含量为每100重量份丙烯酸类树脂在从约0.1到约10重量份的范围内,优选从约0.5到约5重量份。为了提供充分的发泡,该引发剂可以过量使用。
在一实施方式中,用于人造大理石的该可发泡组合物的流度在约13cm/min到约20cm/min的范围内。
本发明的泡沫大理石制品由下述方法制备。
首先,将丙烯酸类树脂、固体颗粒和引发剂混合形成人造大理石的可发泡浆料。其中,每100重量份丙烯酸类树脂,该固体颗粒的量为从约10重量份到约80重量份,该引发剂的量为从约0.1到约10重量份。该固体颗粒可选自由无机填料,大理石碎片和它们的混合物组成的组。
人造大理石的可发泡组合物的流度在从约13cm/min到约20cm/min的范围内。如果流度超过了20cm/min,那么该浆料的黏度变低,使得过程往往难以控制。相反,如果流度低于13cm/min,难以产生发泡。
用于人造大理石的可发泡组合物的黏度不能用传统的黏度计测量,这是因为组合物中无机填料和大理石碎片的缘故。作为替代方法,黏度可用流度来衡量。所以,这里用到的“流度”被定义为将30g的浆料滴在玻璃板上,使该浆料流动1min所测得的该浆料直径的值。流度的单位为:长度/时间。除非专门提示,“厘米/分钟”(cm/min)在本发明中被用作流度的单位。尽管“流度”这种描述不是本领域使用的“黏度”的倒数,但是高的流度显示出低的黏度。换言之,浆料的流度越高,该浆料的黏度越低。
一般地,当丙烯酸单体聚合时,由于放热聚合反应的缘故,其易于起泡,类似于沸腾现象,并产生气体。如果丙烯酸类树脂连续固化,就会形成坚固的泡沫结构。
该可发泡浆料放置一段时间,以使比重相对较小的丙烯酸类树脂充分移到上半部,同时比重相对较高的固体颗粒充分移到下部。这样,形成双层结构,丙烯酸类树脂为上层。在聚合和固化该可发泡浆料的过程中,上层的丙烯酸类树脂通过放热反应起泡从而在上层形成泡沫结构。另一方面,下层中的固体颗粒和微量丙烯酸类树脂固化形成丙烯酸人造大理石层。发泡的上层为具有不规则孔洞的泡沫结构。
在一些实施方式中,将该可发泡浆料倒在传统固体人造大理石板的表面上,静置使丙烯酸类树脂移到上半部后固化,使得该最终的泡沫大理石制品具有发泡的上层和在该层之下的传统固体人造大理石。这样,就得到了具有一体化泡沫层的理想式样的人造大理石。
在用于本发明的人造大理石的可发泡组合物中也可以加入其他添加物,这些添加物包括颜料、染料、光稳定剂、热稳定剂、抗静电剂、抗冲改性剂、增塑剂等。
本发明的泡沫人造大理石与传统的同规格人造大理石相比在轻质和可加工性方面具有优势,并且可以广泛应用。
通过下面的具体实施例能更好地理解本发明。具体实施例是为了更好地说明本发明,而不能理解为在任何方面限制本发明的范围,该范围由所附的权利要求限定。在这些具体实施例中,除非专门说明,所有份和百分比都以重量计。实施例
实施例1
将100重量份的丙烯酸类树脂浆料(其中10重量份的聚甲基丙烯酸甲酯和90重量份的甲基丙烯酸甲酯),10重量份的氢氧化铝,10重量份的大理石碎片,2重量份的过氧化苯甲酰混合,以得到用于制备泡沫人造大理石的浆料。该浆料的流度为13.8cm/min。将该浆料倒入模型中,静置,使丙烯酸类树脂移到上层。然后,该浆料缓慢固化。得到的固化后的泡沫人造大理石具有泡沫状上层。图1示出了固化后泡沫人造大理石的侧视图照片,被切成30cm x50cmx13mm的尺寸。该切割后的泡沫人造大理石重量为:1810g。
比较实施例1
将100重量份的丙烯酸类树脂浆料(其中30重量份的聚甲基丙烯酸甲酯和70重量份的甲基丙烯酸甲酯),100重量份的氢氧化铝,60重量份的大理石碎片和2份过氧化苯甲酰混合来得到浆料。该浆料的流度为11.3cm/min。将该浆料倒入模型中,然后固化以获得坚硬的表面的制品。这种坚硬的表面制品被切成与实施例1相同的尺寸,该制品重量为3330g。
本领域普通技术人员可以很容易地实施该发明。很多调整和变化均被认为在本发明权利要求所限定的范围内。

Claims (10)

1.一种用于泡沫人造大理石的组合物,包括:
100重量份的丙烯酸类树脂;
10到80重量份的固体颗粒,其中所述固体颗粒选自由无机填料、大理石碎片及它们的混合物组成的组;以及
0.1到10重量份的引发剂,
其中所述组合物的流度在13cm/min到20cm/min的范围内。
2.根据权利要求1所述的组合物,其中所述丙烯酸类树脂为丙烯酸单体和聚丙烯酸酯的混合物。
3.根据权利要求1所述的组合物,其中所述无机填料选自由碳酸钙、氢氧化铝、硅土、氧化铝、氢氧化镁及它们的混合物组成的组。
4.根据权利要求1所述的组合物,其中所述大理石碎片这样制备:将100重量份的丙烯酸类树脂,100到200重量份的无机填料,0.1到10重量份的交联剂和0.1到10重量份的引发剂相混合,固化该混合物形成固化的人造大理石,然后再粉碎所述固化的人造大理石。
5.一种使用根据权利要求1-4中任一项所述的用于泡沫人造大理石的组合物用于制备泡沫大理石制品的方法:
混合丙烯酸类树脂、固体颗粒和引发剂,以形成制备人造大理石的可发泡浆料;
静置所述可发泡浆料一段时间,使比重相对较小的丙烯酸类树脂充分移到上半部形成上层,同时比重相对较高的固体颗粒移到下部形成下层;以及
通过放热反应固化所述可发泡浆料,同时使上层的所述丙烯酸类树脂发泡。
6.根据权利要求5所述的方法,其中所述组合物的流度在13cm/min到20cm/min的范围内。
7.根据权利要求5所述的方法,其中所述丙烯酸类树脂为丙烯酸单体和聚丙烯酸酯的混合物。
8.根据权利要求5中所述的方法,其中所述可发泡浆料被倾倒在传统的固体人造大理石板的表面上,然后静置所述可发泡浆料一段时间,以使所述丙烯酸类树脂充分移到所述可发泡浆料上部。
9.一种使用根据权利要求1-4中任一项所述的用于泡沫人造大理石的组合物的泡沫大理石制品,包括:
第一层的丙烯酸人造大理石;以及
第二层的由丙烯酸类树脂制成的具有不规则孔洞的泡沫结构;
其中所述第二层被层压在所述第一层上以形成一体。
10.根据权利要求9所述泡沫大理石制品,其中所述第二层通过发泡所述丙烯酸类树脂形成。
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