CN1422211A - 具有无光泽外观的塑料片材制品及其制备方法 - Google Patents
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Abstract
一具有无光泽表面的塑料片材制品，包括一热塑性聚合物的芯层和至少一置于该芯层之上并且粘结到该芯层的至少一个表面的贴面组合物的层。贴面层组合物包括相同或不同的热塑性聚合物和含有大量的与贴面层组合物的热塑性聚合物不融和的且分散在该热塑性聚合物中的离散的颗粒。可以通过热塑性聚合物和贴面组合物的共挤来制造片材制品，和在典型的实施方案中，这种共挤可以通过一供料头的方式来实现。在另一实施方案中，芯层的热塑性聚合物与贴面层的热塑性聚合物可以是相同的，例如在甲基丙烯酸甲酯－丙烯酸甲酯共聚物的情况下。根据本发明制备的片材制品显示出改善的后－加工性能和表面维护的易操作性，并且能够制成包括光漫射器，投影屏等的各种产品。
Description
发明背景
技术领域
本发明涉及一种呈现无光泽外观的塑料片材制品，该片材包括一芯层和至少一覆盖在其上的且被粘接在芯层的至少一个表面上的贴面组合物层，其中该贴面组合物含有颗粒状的夹杂物，从而产生所需的外观和类似毛玻璃的外观。
现有技术
众所周知，能够使用纹饰或压花压延辊制造具有无光泽粗糙表面的塑料片材。但是，这种技术有许多缺点，例如需要频繁换辊，限制了可预见性和所生产的片材的纹理设计的最终均匀性，如果片材有热变形的话，纹理将会消逝等。
还已知的是制备半透明荧光屏，包括将一透明材料分散到基体材料中，其中透明材料的折射率略微不同于基体材料的折射率--见US专利2287556和公开的欧洲专利申请EP0464499A2。另外还已知的是共挤出一基层和一或两含有溶混的抗冲击改性剂颗粒的贴面组合物层--见US专利5318737。
在这些现有技术的缺点中，目前能够利用的片材材料在外观上存在易变性并且很难制备，因为经常出现不能接受的无光泽层的厚度变化。另外，在此情况下，在那些用表面纹理化获得的最终表面的地方，制品很难保持和清理。
没有已知技术能够有效地对付现有技术中涉及到的无光泽外观塑料片材在成片制备和合成质量中的缺陷，而本发明提供了一种制品的制备方法使其没有上述缺点。
发明概要
现在已经发现能够廉价地制备一种具有无光泽表面的塑料片材制品并且不具备上述缺点，该片材制品包括一热塑性聚合物的芯层和至少一赋予片材制品无光泽外观的贴面组合物层，并且该层覆盖和粘接在所述芯层的至少一面之上。该贴面组合物包括一热塑性聚合物，该聚合物可以与用于芯层的热塑性聚合物相同或不同并且含有大量离散的、与贴面热塑性聚合物不融和的并且分散在其中的颗粒。颗粒的折射率不同于贴面热塑性聚合物的折射率。
本发明的片材可以被制成具有一个或多个贴面层，并且能够用共挤来制备，该共挤使用了一种特别技术即采用了通过供料头系统的挤出。这些参数，例如在贴面层中的不融和颗粒的尺寸和加料，及所有层的厚度，可以在此处叙述的范围，也就是在本发明的范围之内改变，从而在最终制品中获得特殊的效果。
本发明的制品呈现出一种改善特性的组合，特别是耐久性和可清洁性，并且能够应用在各种需要无光泽或磨砂表面的应用中，例如用于光漫射器和照明器材，保密嵌板如淋浴门，零售陈列品和投影屏。
详细描述
为了实现本发明的目的，芯层可以由透明(是优选的)，半透明的或不透明的第一热塑性聚合物组成。适宜的第一热塑性聚合物的例子包括聚乙烯，聚丙烯，乙烯-丙烯共聚物，乙烯-醋酸乙烯酯共聚物，乙烯-丙烯酸甲酯共聚物，乙烯-丙烯酸乙酯共聚物，乙烯-甲基丙烯酸甲酯共聚物，乙烯-乙酸乙烯酯-甲基丙烯酸甲酯共聚物，聚氯乙烯，丙烯腈-苯乙烯共聚物，聚苯乙烯，苯乙烯-甲基丙烯酸甲酯共聚物，聚丙烯酸乙酯，聚甲基丙烯酸甲酯，甲基丙烯酸甲酯-丙烯酸甲酯共聚物，聚对苯二甲酸乙二醇酯，聚酰胺，聚碳酸酯，聚氨酯，硅树脂等。在那些聚合物是丙烯酸的情况下，典型的第一热塑性聚合物具有100000到约175000的重均分子量，优选125000到150000。
优选的，第一热塑性聚合物包括甲基丙烯酸甲酯-丙烯酸甲酯共聚物，其中甲基丙烯酸甲酯的用量是大约80-98wt％，优选93-97wt％和丙烯酸甲酯的用量是约2-20wt％，优选3-7wt％。
一个芯层包括至少一个贴面层，并且贴面层覆盖在芯层之上并且与芯层的至少一面粘接。这样，本发明的塑料片材制品可以具有一个置于和粘接在芯层的一个表面上的贴面层或该片材制品也可以具有两个分别置于芯层的每个表面上的贴面层。
贴面层组合物包括一含有大量的与聚合物不融和的且分散在其中的离散颗粒的第二热塑性聚合物。颗粒的折射率不同于第二热塑性聚合物的折射率。第二热塑性聚合物可以是任何一种上述列出的第一热塑性聚合物中的一种。第二热塑性聚合物可以与第一热塑性聚合物不同。在后一种情况中，可以这样选择第一和第二热塑性聚合物，它们彼此能够充分相容，这样的话贴面层将被粘接到芯层的表面，和在一个实施方案中，当层是通过供料头式共挤塑加工的时候，贴面层能够实现这样的粘接。在特定的实施方案中，第二热塑性聚合物与第一热塑性聚合物相同。
典型的，芯层具有大约2到13mm的厚度，和特别是，大约4-10mm的厚度，和贴面层的厚度可以是约10-400μm，和特别优选的是大约150到300μm。
颗粒可以是在第二热塑性聚合物中不融和的并且其典型的用量是大约4到30wt％，优选约22到26wt％。颗粒典型的具有颗粒尺寸直径范围是大约1到60μm，优选的是约30到50μm。颗粒可以包括聚合物或颜料。这种聚合物的实例包括交联的聚甲基丙烯酸甲酯，用丙烯酸酯或甲基丙烯酸酯单体改性的交联的聚甲基丙烯酸甲酯，甲基丙烯酸甲酯和苯乙烯的交联共聚物，硅树脂和聚甲基丙烯酸烯丙酯。这种颜料的非限定实例包括硫酸钡，二氧化硅，氧化铝，氢氧化铝和碳酸钙。
第二热塑性聚合物和颗粒典型的具有折射率的范围是约1.40到1.65，优选1.49到1.55。典型的颗粒和第二热塑性聚合物的折射率数值上的差异范围是约0.001到0.030，优选0.005到0.020。
下面非限定例子是说明本发明的。除非特别指示，所有的含量和百分比都是基于重量的。
实施例
实施例1
在该实施例中，制备一含有一粘接在芯层上的贴面层的塑料片材制品。用于芯层的第一热塑性聚合物与用于贴面层的第二热塑性聚合物是相同的：一大约94wt％甲基丙烯酸甲酯和大约6wt％丙烯酸甲酯的共聚物，其具有2.1的熔融指数，150000的重均分子量和1.490的折射率。用于芯层的第一热塑性组合物的量相对于用于贴面层的第二热塑性的聚合物的关系是这样的，在供料头式共挤塑两层之后，芯层的厚度是5.75mm和贴面层的厚度是250μm。包括具有1.488折射率的交联的聚甲基丙烯酸甲酯珠粒料的和大约40μm的平均颗粒直径的颗粒，以珠粒料25wt％的量与第二热塑性聚合物结合。
用于共挤芯层组合物和贴面层组合物料流的设备是一装备有熔融和挤出两股料流的装置的传统的挤出机。一传统的组合供料头将从挤出机出来的两股熔融状态的料流结合到一起和此后料流被送入到一传统的单-料道压片模头，和然后被送到一传统的装备有冷却架和引出辊的多辊上光机。在该实施例中，仅有一贴面层被粘接到芯层的一个表面上和因此，在供料头一侧的流道被封闭以便贴面层仅能够流动到芯层的一边。
设备被加热以便提供255℃的熔融温度和开始挤出加工。一旦确立料流通过模头，片材线以典型的方式被串在一起，同时速度逐渐增加以达到所需的生产率，该生产率的典型范围是200到5000磅/小时。
实施例2
为了制备在芯层的两面都具有贴面层的且总厚度是约6mm的塑料片材制品，重复实施例1。因此，如实施例1中的那样，芯层和贴面层的组成是相同的，总的制造工艺也是相同的，除了供料头的两侧的流道都是打开的之外-以便贴面层组合物能够流动到芯层的两面上。用于芯层的第一热塑性组合物的用量与用于贴面层的第二热塑性聚合物的量的关系是这样的，在供料头式共挤塑三层完成之后，芯层具有5.5mm的厚度和每个贴面层具有250μm的厚度。
在不违背本发明的精神或实质特征的前提下，可以以改进的方式或以其它方式实施本发明。因此现公开的内容应当被认为是对所有方面的说明而不是限制，通过附加的权利要求显示本发明的范围，和所有的包括等同方式和范围的变化均被认为是在保护范围之内。
Claims (25)
1.一种具有无光泽表面的塑料片材制品，包括一第一热塑性聚合物的芯层和至少一置于和粘接到所述芯层的至少一个表面上的贴面组合物层，所述贴面组合物包括一具有一折射率的第二热塑性聚合物和含有大量的与第二热塑性聚合物不融和的并且分散在第二热塑性聚合物中的且具有一折射率的离散的颗粒，其中颗粒的折射率不同于第二热塑性聚合物的折射率。
2.权利要求1的塑料片材制品，其中第一热塑性聚合物和第二热塑性聚合物分别独立地从下述组中选出，该组是由：聚乙烯，聚丙烯，乙烯-丙烯共聚物，乙烯-醋酸乙烯酯共聚物，乙烯-丙烯酸甲酯共聚物，乙烯-丙烯酸乙酯共聚物，乙烯-甲基丙烯酸甲酯共聚物，乙烯-乙酸乙烯酯-甲基丙烯酸甲酯共聚物，聚氯乙烯，丙烯腈-苯乙烯共聚物，聚苯乙烯，苯乙烯-甲基丙烯酸甲酯共聚物，聚丙烯酸乙酯，聚甲基丙烯酸甲酯，甲基丙烯酸甲酯-丙烯酸甲酯共聚物，聚对苯二甲酸乙二醇酯，聚酰胺，聚碳酸酯，聚氨酯和硅树脂组成的。
2.权利要求1的塑料片材制品，其中第一热塑性聚合物和第二热塑性聚合物都是透明的。
3.权利要求1的塑料片材制品，其中第二热塑性聚合物和第一热塑性聚合物相同。
4.权利要求3的塑料片材制品，其中第二和第一热塑性聚合物包括一甲基丙烯酸甲酯-丙烯酸甲酯共聚物。
5.权利要求4的塑料片材制品，其中共聚物包括大约80到98wt％甲基丙烯酸甲酯和大约2到20wt％丙烯酸甲酯。
6.权利要求5的塑料片材制品，其中共聚物包括93到97wt％甲基丙烯酸甲酯和3到7wt％丙烯酸甲酯。
7.权利要求1的塑料片材制品，其中贴面层组合物仅被粘接在芯层的一个表面上。
8.权利要求1的塑料片材制品，其中贴面层组合物被粘接在芯层的两个表面上。
9.权利要求1的塑料片材制品，其中第一和第二热塑性聚合物具有的重均分子量的范围是大约100000到大约175000。
10.权利要求9的塑料片材制品，其中第一和第二热塑性聚合物具有的重均分子量的范围是大约125000到大约150000。
11.权利要求1的塑料片材制品，其中芯层具有大约2到13mm的厚度和所述的至少一贴面层具有大约10到400μm的厚度。
12.权利要求11的塑料片材制品，其中芯层具有4到10mm的厚度和所述的至少一贴面层具有150到300μm的厚度。
13.权利要求1的塑料片材制品，其中颗粒具有颗粒尺寸直径的范围是大约1μm大约60μm。
14.权利要求13的塑料片材制品，其中颗粒具有颗粒尺寸直径的范围是30μm到50μm。
15.权利要求1的塑料片材制品，其中分散在第二热塑性聚合物中的颗粒的量的范围是约4到30wt％。
16.权利要求15的塑料片材制品，其中分散在第二热塑性聚合物中的颗粒的量的范围是22到26wt％。
17.权利要求1的塑料片材制品，其中颗粒和第二热塑性聚合物的折射率的范围是约1.40到1.65。
18.权利要求17的塑料片材制品，其中颗粒和第二热塑性聚合物的折射率的范围是1.49到1.55。
19.权利要求1的塑料片材制品，其中颗粒的折射率不同于第二热塑性聚合物的折射率，其差值的范围是大约0.001到大约0.030。
20.权利要求19的塑料片材制品，其中颗粒的折射率不同于第二热塑性聚合物的折射率，其差值的范围是0.005到0.020。
21.权利要求1的塑料片材制品，其中颗粒包括一聚合物或一颜料。
22.权利要求21的塑料片材制品，其中颗粒包括的聚合物选自下述组，该组是由交联的聚甲基丙烯酸甲酯，用丙烯酸酯或甲基丙烯酸酯单体改性的交联的聚甲基丙烯酸甲酯，甲基丙烯酸甲酯和苯乙烯的交联共聚物，硅树脂和聚甲基丙烯酸烯丙酯组成。
23.权利要求21的塑料片材制品，其中颜料选自由硫酸钡，二氧化硅，氧化铝，氢氧化铝和碳酸钙组成的组。
24.权利要求1的塑料片材制品，其中塑料片材是由供料头共挤塑形成的一芯层和贴面复合层组成。
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| US19205700P | 2000-03-24 | 2000-03-24 | |
| US60/192,057 | 2000-03-24 |
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| EP (1) | EP1272344A1 (zh) |
| JP (1) | JP2003528750A (zh) |
| KR (1) | KR100761677B1 (zh) |
| CN (1) | CN100360308C (zh) |
| AU (2) | AU2001247799B2 (zh) |
| WO (1) | WO2001072513A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510789C (zh) * | 2004-12-20 | 2009-07-08 | 三菱瓦斯化学株式会社 | 塑料片材 |
| CN102617967A (zh) * | 2012-03-09 | 2012-08-01 | 武汉正浩塑胶有限公司 | 一种表面具有磨砂效果的塑料异型材及其生产方法 |
| TWI668112B (zh) * | 2014-02-11 | 2019-08-11 | 美商陶氏全球科技有限責任公司 | 用於增強聚烯烴薄膜之無光澤外觀的丙烯酸系珠粒 |
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| US6861129B2 (en) * | 2002-03-26 | 2005-03-01 | Atofina | Mar resistance, non-glare transparent acrylic sheet with consistent optical properties at various sheet thicknesses |
| DE10233685A1 (de) * | 2002-07-24 | 2004-02-12 | Röhm GmbH & Co. KG | Verfahren zur Herstellung eines hochviskosen Sirups aus PMMA und Polystyrol mit einer schlagzähen Formmasse aus PMMA |
| US20040099369A1 (en) * | 2002-11-22 | 2004-05-27 | Sparks Darrell L. | Composite sheet with mirror finish |
| US20050233124A1 (en) * | 2003-12-12 | 2005-10-20 | Gilles Marot | Multilayer acrylic film with improved optical and mechanical properties |
| US7435462B2 (en) * | 2004-05-28 | 2008-10-14 | Arkema France | Thermoplastic article with a printable matte surface |
| WO2006057355A1 (ja) * | 2004-11-26 | 2006-06-01 | Denki Kagaku Kogyo Kabushiki Kaisha | 多層シート及び光拡散シート |
| ITUD20060126A1 (it) * | 2006-05-19 | 2007-11-20 | Tonello Armando | Cabina doccia e relativo procedimento di realizzazione |
| JP4888017B2 (ja) * | 2006-09-29 | 2012-02-29 | 凸版印刷株式会社 | 成型用積層樹脂シート |
| KR20080057582A (ko) * | 2006-12-20 | 2008-06-25 | 주식회사 케이.피 | 플라스틱 적층 시트 및 이의 제조 방법 |
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| JP2011225836A (ja) | 2010-04-08 | 2011-11-10 | Rohm & Haas Co | 不透明化粒子およびその粒子から形成される組成物 |
| US9085680B2 (en) * | 2011-01-27 | 2015-07-21 | Polyone Corporation | Low gloss capstock |
| CN103429654B (zh) | 2011-02-10 | 2016-06-15 | 普立万公司 | 基于离聚物的低光泽表面料 |
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| US6861129B2 (en) * | 2002-03-26 | 2005-03-01 | Atofina | Mar resistance, non-glare transparent acrylic sheet with consistent optical properties at various sheet thicknesses |
-
2001
- 2001-03-26 AU AU2001247799A patent/AU2001247799B2/en not_active Ceased
- 2001-03-26 EP EP01920779A patent/EP1272344A1/en not_active Withdrawn
- 2001-03-26 WO PCT/US2001/009680 patent/WO2001072513A1/en not_active Application Discontinuation
- 2001-03-26 KR KR1020027012582A patent/KR100761677B1/ko not_active IP Right Cessation
- 2001-03-26 AU AU4779901A patent/AU4779901A/xx active Pending
- 2001-03-26 US US09/817,788 patent/US20010036543A1/en not_active Abandoned
- 2001-03-26 CN CNB018070825A patent/CN100360308C/zh not_active Expired - Fee Related
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510789C (zh) * | 2004-12-20 | 2009-07-08 | 三菱瓦斯化学株式会社 | 塑料片材 |
| CN102617967A (zh) * | 2012-03-09 | 2012-08-01 | 武汉正浩塑胶有限公司 | 一种表面具有磨砂效果的塑料异型材及其生产方法 |
| CN102617967B (zh) * | 2012-03-09 | 2014-06-04 | 武汉正浩环保新材料科技有限公司 | 一种表面具有磨砂效果的塑料异型材及其生产方法 |
| TWI668112B (zh) * | 2014-02-11 | 2019-08-11 | 美商陶氏全球科技有限責任公司 | 用於增強聚烯烴薄膜之無光澤外觀的丙烯酸系珠粒 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1272344A1 (en) | 2003-01-08 |
| AU2001247799B2 (en) | 2005-03-17 |
| CN100360308C (zh) | 2008-01-09 |
| KR100761677B1 (ko) | 2007-10-04 |
| AU4779901A (en) | 2001-10-08 |
| US20010036543A1 (en) | 2001-11-01 |
| JP2003528750A (ja) | 2003-09-30 |
| KR20030017481A (ko) | 2003-03-03 |
| WO2001072513A1 (en) | 2001-10-04 |
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