CN102083623B - 多层制品和制备多层制品的方法 - Google Patents

多层制品和制备多层制品的方法 Download PDF

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CN102083623B
CN102083623B CN200980103217.2A CN200980103217A CN102083623B CN 102083623 B CN102083623 B CN 102083623B CN 200980103217 A CN200980103217 A CN 200980103217A CN 102083623 B CN102083623 B CN 102083623B
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sheet material
cap rock
basal layer
acrylic polymer
cycloaliphatic polyesters
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CN102083623A (zh
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桑迪普·特里帕西
施里瓦斯·查克拉瓦蒂
萨普纳·K·布莱克本
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SABIC Global Technologies BV
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明提供一种片材，包括：含有丙烯酸类聚合物的盖层；和基础层，其中所述片材是可热成型的。所述基础层包括脂环族聚酯共聚物和任选的芳族聚碳酸酯。所述脂环族聚酯共聚物可包括大于10wt％的脂环族二醇或酸或其组合，基于脂环族聚酯共聚物的总重量。

Description

多层制品和制备多层制品的方法
背景
模内装饰的热塑性膜正在在各种应用中获得广泛的接受，所述的各种应用例如家用消费电子品，用品，和印制的覆盖物。这些应用需要各种性质的组合，例如透明性，可印刷性，可热成型性，和硬度，以及耐刮擦性、耐化学性和耐冲击性。许多精选的材料都不能获得这些组合。最通常的解决方案是将功能型涂层作为盖层施涂到热塑性膜上，其中所述涂层赋予表面性质，同时基础膜提供大的机械整体性。但是，虽然涂层改善耐刮擦性，它会损害膜的可热成型性，这严重地限制了这种膜的有益应用。最难的挑战之一是仍然存在耐刮擦性和可热成型性之间的平衡。
因此，现有技术仍然需要能够容易地例如通过挤出成型的多层片材，并且该片材提供各种性质的期望组合，所述各种性质包括可热成型性和耐刮擦性。
发明内容
本发明总地涉及可热成型的材料，制备可热成型的片材的方法，和由其制备的制品。在一种实施方式中，所述片材包括：含有丙烯酸类聚合物的盖层；和基础层，其中所述片材是可热成型的。所述基础层包括脂环族聚酯共聚物和任选的芳族聚碳酸酯。所述脂环族聚酯共聚物可包括大于10wt％的脂环族二醇或酸或其组合，基于脂环族聚酯共聚物的总重量。
在一种实施方式中，制备制品的方法可包括：使丙烯酸类聚合物在挤出机中熔融；在挤出机中形成熔融的脂环族聚酯共聚物，和共挤出所述丙烯酸类聚合物和所述脂环族聚酯共聚物，从而形成片材。所述脂环族聚酯共聚物可包括含量为大于10wt％的脂环族聚酯，基于脂环族聚酯共聚物的总重量。所述脂环族聚酯共聚物可形成基础层，而所述丙烯酸类聚合物在所述基础层上形成盖层。
通过参考本公开的各种特征的以下详细描述和包括在其中的实施例，可更容易地理解本公开。
附图说明
现在参考附图，该附图仅是说明性的，并不是对本发明的限制。
图1是通过有型载荷(profile load)产生的刮擦的横截面说明。
图2是示例性共挤出系统的示意图。
具体实施方式
多层制品包括盖层和基础层。所述盖层可基于丙烯酸类聚合物例如聚(甲基)丙烯酸烷基酯的那些(例如，聚(甲基丙烯酸甲酯(“PMMA”))，而基础层可为脂环族聚酯共聚物和任选的芳族聚碳酸酯的组合。可将所述盖层和基础层共挤出形成多层片材。
这种制品的硬度、耐刮擦性、机械强度和可热成型性应该使得这些制品满足各种性质的期望组合，所述各种性质例如透明性，可印刷性，可热成型性，和硬度，以及耐刮擦性、耐化学性和耐冲击性。此外，所述基础层粘合至所述盖层，而不需要任何粘合剂或者粘合层，并且在所述盖层和所塑基础层之间提供实质上的流变性匹配，由此改善复合物膜的加工性。
在一种实施方式中，所述片材包括：含有丙烯酸类聚合物的盖层；和基础层，其中所述片材是可热成型的。所述基础层包括脂环族聚酯共聚物和任选的芳族聚碳酸酯。所述脂环族聚酯共聚物可包括大于10wt％的脂环族二醇或酸或其组合，基于脂环族聚酯共聚物的总重量。所述盖层可为总厚度的1％至50％，所述总厚度可为5mil至500mil。所述基础层可包括25wt％至100wt％脂环族聚酯和余量的聚碳酸酯的共混物，或者，尤其是，50wt％至90wt％脂环族聚酯和余量的聚碳酸酯的共混物。所述片材的铅笔硬度可为大于HB。铅笔硬度大于HB的片材还可包括：大于或等于120N/mm的撕裂引发强度(tear initiation strength)和/或大于5N/mm的撕裂蔓延强度，和/或大于40MPa的抗拉强度。丙烯酸类聚合物可为聚(甲基)丙烯酸烷基酯，或者尤其是，聚(甲基)丙烯酸甲酯。所述基础层可包括20wt％至90wt％的PCCD，余量的芳族聚碳酸酯。
在一种实施方式中，制备制品的方法可包括：使丙烯酸类聚合物在挤出机中熔融，在挤出机中形成熔融的脂环族聚酯共聚物，和共挤出所述丙烯酸类聚合物和所述脂环族聚酯共聚物，从而形成片材。所述脂环族聚酯共聚物可包括含量为大于10wt％的脂环族聚酯，基于脂环族聚酯共聚物的总重量。所述脂环族聚酯共聚物可形成基础层，而所述丙烯酸类聚合物在所述基础层上形成盖层。可使所述片材热成型。
所述脂环族聚酯具有下式：
其中R13和R14各自独立地为具有2至20个碳原子的芳族，脂肪族或者环烷烃，条件是R13和R14中的至少一个是脂环族基团。所述脂环族聚酯是缩合产物，其中R13是二醇或其化学等价物的残基，R14是二酸或其化学等价物的残基。在一种实施方式中，R13和R14都是含有环烷基的基团。这些聚酯通常含有至少50mol％的脂环族二酸和/或脂环族二醇组分，剩余物如果存在，则为芳族二酸和/或线性脂肪族二醇。
在一种实施方式中，R13和R14为环烷基，其独立地选自以下结构单元：
在具体的实施方式中，所述二醇是1，4-环己烷二甲醇或其化学等价物。可使用1，4-环己烷二甲醇的顺式或反式异构体的任一种或者两种。该二醇的化学等价物包括酯，例如C1-4二烷基酯，二芳基酯，等。二酸的具体的非限制性实例包括十氢化萘二羧酸，降冰片烯二羧酸，双环辛烷二羧酸，1，4-环己烷二羧酸或其化学等价物。最具体地，二酸包括反式-1，4-环己烷二羧酸或其化学等价物。这些二酸的化学等价物包括C1-4二烷基酯，二芳基酯，酸酐，盐，酰氯，酰溴，等。在一种实施方式中，所述化学等价物包括脂环族二酸的二烷基酯，和最具体地该酸的二甲基酯，例如1，4-环己烷-二羧酸二甲酯。
其它类型的单元可存在于所述脂环族聚酯共聚物中，包括源自芳族二羧酸组分和非-脂环族二醇，或其化学等价物的反应的单元。示例性的芳族二羧酸包括间苯二甲酸，对苯二甲酸，1，2-二(对羧基苯基)乙烷，4，4′-二羧基二苯基醚，4，4′-联苯甲酸，1，4-，1，5-，或者2，6-萘二羧酸，和包括至少一种前述酸的组合。具体的二羧酸是对苯二甲酸，间苯二甲酸，和包括两种前述酸的组合。所述非-脂环族二醇可为C1-4亚烷基二醇，例如乙二醇，丙二醇，1，4-丁二醇，等，以及包括至少一种前述二醇的组合。
所述脂环族聚酯共聚物更具体地包括至少50mol％的脂环族残基，更具体地至少70mol％的脂环族残基，剩余的是芳族酸或者C1-4亚烷基二醇残基。具体的脂环族聚酯是聚(环己烷-1，4-二亚甲基环己烷-1，4-二羧酸酯)，也称为聚(1，4-环己烷-二甲醇-1，4-二羧酸酯)(PCCD)。另一具体的酯是聚(1，4-亚环己基二亚甲基共聚-亚乙基对苯二甲酸酯)(PCTG)，其中大于50mol％的酯基团源自1，4-环己烷二甲醇；和聚(亚乙基-共聚-1，4-亚环己基二亚甲基对苯二甲酸酯)(PETG)，其中大于50mol％的酯基体源自亚乙基。也想到的用于本申请的是任何上述聚酯与少量例如0.5至5wt％的源自脂肪酸和/或脂肪族多元醇的单元形成共聚酯。所述脂肪族多元醇包括二醇，例如聚(乙二醇)或者聚(丁二醇)。
芳族聚碳酸酯具有下式：
其中R1基团总数的至少60％是芳族有机基团，其余为脂肪族、脂环族或芳族基团。本申请所用的术语“聚碳酸酯”包括共聚碳酸酯，即包括两种或者更多种不同R1基团的共聚物。在一种实施方式中，每个R1源自下式的双酚化合物：
其中Ra和Rb各自代表卤原子或一价烃基，并且可以相同或相异；p和q各自独立地为0～4的整数，Xa表示以下的基团之一：
其中Rc和Rd各自独立地为氢原子，或者一价线性或者环状烃基，Re为二价烃基。
双酚化合物的具体实例包括1，1-双(4-羟基苯基)甲烷，1，1-双(4-羟基苯基)乙烷，2，2-双(4-羟基苯基)丙烷(下文中称为“双酚A”或者“BPA”)，2，2-双(4-羟基苯基)丁烷，2，2-双(4-羟基苯基)辛烷，1，1-双(4-羟基苯基)丙烷，1，1-双(4-羟基苯基)正丁烷，2，2-双(4-羟基-1-甲基苯基)丙烷，1，1-双(4-羟基-叔丁基苯基)丙烷，3，3-双(4-羟基苯基)苯并[C]吡咯酮，2-苯基-3，3-双(4-羟基苯基)苯并[C]吡咯酮(PPPBP)，和1，1-双(4-羟基-3-甲基苯基)环己烷(DMBPC)。也可使用包括至少一种前述双酚化合物的组合。例如，可使用共聚物，包括源自双酚A和1，1-双(4-羟基-3-甲基苯基)环己烷的单元的混合物。
在具体的实施方式中，聚碳酸酯是源自双酚A的线性均聚物，其中p和q各自为0，Y1为异丙叉。
脂环族聚酯组分和芳族聚碳酸酯组分的相对量随着具体的应用而变化。在一种实施方式中，聚酯组分的量为大于10wt％，例如，25wt％至100wt％，剩余物为芳族聚碳酸酯。在另一实施方式中，脂环族聚酯的量为50wt％至90wt％，剩余物为芳族聚碳酸酯。所述基础层组合物可以以商购自GE Plastics。
所述盖层可基于丙烯酸类聚合物例如聚(甲基)丙烯酸烷基酯的那些(例如，聚(甲基丙烯酸甲酯(“PMMA”))。该层可包括大于或等于50wt％的丙烯酸类聚合物，或者具体地，大于或等于约70wt％的丙烯酸类聚合物，或者更具体地，大于或等于约90wt％的丙烯酸类聚合物，基于盖层的总重量。剩余物可为当与丙烯酸类聚合物共混时导致盖层具有大于或等于80％的透光率的任何其它聚合物，所述透光率根据ASTM D1003-00方法A测定，例如，使用来自BYK-Gardner的HAZE-GUARD DUAL，使用积分球(0°/散射几何结构(diffuse geometry))测量，其中光谱敏感性符合在标准灯D65下的CIE标准光谱值。
除了上述物质之外，所述基础层和/或盖层可独立地包括各种添加剂，条件是选择所述添加剂从而使得不显著有害地影响该层的期望性质例如可热成型性，耐刮擦性，等。可使用添加剂的组合。可以在混合用于形成每个层的组合物的组分的过程中，在合适的时间混合这些添加剂。可能的添加剂包括抗氧化剂，阻燃剂，防滴剂，染料，颜料，着色剂，稳定剂(例如，热稳定剂，紫外线稳定剂，等)，小粒子矿物(例如粘土，云母，和/或滑石)，防静电剂，增塑剂，润滑剂，脱模剂，增白剂，增强填料(例如，玻璃)，和包括至少一种前述物质的组合。添加剂的量可为小于或等于约20wt％，或者具体地约0.1wt％至约10wt％的添加剂，或者更具体地，约0.5wt％至约5wt％的添加剂，基于包括所述添加剂的层的总重量。
本发明的盖层和基础层通过共挤出形成。例如，该多层复合物可合适地通过使用图2中所示意地示出的连续压延共挤出方法形成。在该方法中，单螺杆挤出机1和2将各个层(即，顶层，第二层和任何另外的聚合物层)的树脂熔体供应到进料段3中。模头4形成熔融的聚合物网，其被进料到3辊-压延机5。通常，所述压延机包括2至4个反向旋转圆筒形辊，其中每个辊各自由金属(例如，钢)或者橡胶涂覆的金属制成。可根据需要将每个辊加热或者冷却。可将通过模头形成的熔融网在压延辊之间连续挤压。借以拉出该网的辊间的空隙或者″辊隙″决定各层的厚度。多层复合物也可由对应于聚合物层的单独的预成型膜形成，接着例如使用加热的辊和任选的粘性粘结层将所述单独的预成型膜层压到一起。
可共挤出各层从而形成各种盖层与基础层的厚度比(即，盖层厚度除以基础层厚度)。所述厚度比可为1％至50％，或者具体地，5％至40％，或者更具体地，10％至25％。通常，该片材的总厚度可为至多甚至是超过几毫米。更具体地，该片材的厚度(例如，精确计量)可为1mil(25.4微米(μm))至500mils(1,2700μm)，或者仍然更具体地，约5mils(127μm)至约40mils(1016μm)，和仍然更具体地，约5mils(127μm)至约30mils(762μm)。
以下实例仅是示例性的并不是本发明的限制。
实施例
实施例1
各种盖层组合物和膜结构的双层膜(表2中的样品1至13)使用根据图2所述的共挤出方法制备。每个样品的具体工艺参数随着各个层的厚度和总的膜厚度而变化，涉及到表2中所有的样品的工艺参数范围在表3中给出。应该理解，用于挤出这些膜的工艺窗口不限于表3中所列的那些。本实验的目的是确定是否存在“一种”条件，在该条件下可制备这些共挤出的膜，即这些膜是否是可挤出的。表3仅提供一组用于共挤出这些膜的条件。
该实例证明了所公开的用于模内装饰(IMD)应用的制品的适宜性。用于这些应用的膜应该可符合IMD的三个子工艺(sub-processes)：(a)可挤出性-由所选的材料以与可商购的抛光的图形膜(例如，Lexan 8010膜)相当的表面品质制备膜的能力；(b)可成型性-将膜拉成不同的几何形状的能力；和(c)修剪-干净利索地切割该膜而不导致任何破裂或者分层的能力。
表1含有化学描述和用于表2中所列的膜结构的树脂的来源。
1Mw＝重均分子量
2PS标样＝通过凝胶渗透色谱测得(GPC)
表2在以上3种性质量度方面评价了该样品：表面品质，可热成型性，和修剪。为了测量表面品质，通过三个操作者检测10个尺寸为12英寸x 12英寸(30.5cm x 30.5cm)的片，确定在长度方向上大于2mm的任何缺陷(线，凹痕，突起)。对于肉眼来说，没有任何这种缺陷就认为是“通过”。不意图测试该膜的光学品质，而是意图确定表明膜共挤出产生的任何问题的任何宏观缺陷。
为了测试可成型性，将该膜的12英寸x 12英寸样本预加热至140℃，然后在COMET Thermoformer上真空成型，其中阳成型工具处于120℃，最小曲率为5mm，和最大拖曳(maximum draw)为10mm。该测试的“合格”是，通过肉眼测定，在加工过程中不存在在该膜上的任何皱纹，变白，或者撕裂。(肉眼不包括使用用于放大的光学设备，例外是可使用正常视力所需的矫正透镜。)
使用相匹配的金属模头，包括硬化的阳模头部分和阴模头部分(American Iron and Steel Institute“AISI”Type A2 steel)对所述成型的部件进行修剪，所述阳模头部分和阴模头部分之间的间隙为片材厚度的10％；其中该部件在冲击时相对于刀片为90度角。修剪所述热成型的部件在IMD方法中是一个完整的步骤。具有差的层间粘着力的多层结构在该步骤的过程中易于脱胶(delaminate)。该测试的合格是在该步骤的过程中不存在任何可见的破裂迹象和任何可见的脱胶，可见性使用肉眼测定。
表2导致以下的结论：(1)共挤出的膜显示出显著改善的硬度，即使10％的盖层也具有超过H的硬度；(2)虽然增加盖层的厚度会改善铅笔硬度，但是它使得该膜变脆，这从修剪性能可看出(样品4，虽然它显示出4H的铅笔硬度，但是在修剪过程中破裂，而因此不适合用于IMD)；(3)基础层中的聚酯使得该膜是IMD友好的(基础层中100％的PC给盖层的共挤出带来了挑战。)。在10％的盖层厚度(样品6)，不能够挤出该膜，而在较高的盖层-基础层比下可以共挤出该膜(样品5)，它没有通过修剪测试，其中它导致了盖层和基础层之间的脱胶；和(4)例如为了便于共挤出，根据聚酯的类型，与PC共混可能是有用的，例如，共混的比为0％至20％以上，基于基础层的总重量。虽然100％PCTG作为基础层是可挤出的，但是将PCCD与PC共混使得能够进行挤出。因此，如果使用PCCD，那么基础层可包括20wt％至90wt％的PCCD，或者具体地，30wt％至80wt％的PCCD，或者更具体地，40wt％至60wt％的PCCD，余量为PC。此外，盖层厚度可为1％至50％，或者具体地，5％至40％，或者更具体地10％至30％，和仍然更具体地，15％至25％。
实施例2
本实施例说明多层膜的硬度和耐刮擦性。根据表4中所列的膜和树脂组合物制备两个样品。以与实施例1中相同的方式制备这些样品。样品14本质上是单层膜，将其包括进这里的比较是为了突出通过盖层所带来的性能改善。
将这两个样品与三个商业上可获得的用于图形应用的样品对比：2层共挤出的聚碳酸酯膜。该盖层是PC共聚物，而基础层是PC(具体地可商购自SABIC Innovative Plastics，Pittsfield，MA的Lexan ML 9735)(样品17)(称为1HD00，可商购自SABIC Innovative Plastics)；单层聚碳酸酯(样品18)聚碳酸酯(Lexan 8010，可商购自SABIC Innovative Plastics)；和涂覆的聚碳酸酯膜(样品19)，其包括以聚碳酸酯为基础的可固化二氧化硅涂层(具体地Lexan 8010)(称为HP92S，可商购自SABIC Innovative Plastics)，所有的都可商购自SABIC Innovative Plastics。必需指出，HP92S是涂覆的膜，其是不可成型的。
根据ASTM D3363-05测试所有样品的硬度，即铅笔硬度。两个样品15和16的铅笔硬度都为2H，而样品(17，18，19)具有较低的硬度：分别为1H，2B，和HB。样品14的硬度为2B，这突出了盖层的显著性。
也使用使用符合ISO 1518的Erichsen Scratch Tester Type 413测试样品的耐刮擦性。将2牛顿(N)和4N的力施加到半径为0.01毫米(mm)的圆锥形铁笔，导致在该部件表面上产生刻痕。接着用Dektak 6M表面光度仪测量刻痕的程度，并且记录为从刻痕的底部到样品表面所测得的刻痕高度。再次，样品15和16胜过了对比样品。样品15和16的刮擦深度分别为1.15微米(μm)和1.25μm。对比样品的刮擦深度分别为1.4μm，2.86μm，和2.95μm。没有任何盖层的样品(样品14)的刮擦深度为3.02微米(μm)。
(表5和7)中产生的数据是在重的载荷下产生的。仍然在另一情况下，使用Nano Indenter XP，MTS Systems进行微刮擦试验(轻载荷)，施加0至50微牛顿(mN)的正常载荷。刮擦速度为50微米每秒(μm/s)。使用标准的Berkovich金刚石压痕计(具有10纳米(nm)球面头部)，使其刀刃向前移动通过该材料。图1是这种刮擦的一种说明，相应测得的划痕形状显示出刮痕的形成。以下记录的是当载荷达到25mN时的点处该形状的瞬时深度(过程中的深度)。这给出了该材料的软度(softness)/硬度的量度。在完成了整个刮擦的情况下(载荷达到50mN)，划痕的一些去除物质复原了，结果刮擦深度减小。再在上述相同的点处测量划痕的深度和宽度。这是“后深度”。这给出了材料复原的量度(“容忍度(forgiveness)”)。
表5进一步强调了由所述双层结构导致的耐刮擦性改进(样品14与15/16比较)。样品15和16不仅性能比样品17和18好，它们相对于涂覆的对比样品HP92S(样品19)也是相当的。这是预料不到的，这是因为人们本来会预期该涂层由于它们的交联而在这种轻载荷下更具有耐性。
除了耐刮擦性和硬度之外，机械强度也是IMD应用的一个因素；例如，该膜应该耐压裂和撕裂。表6记录了以牛顿每毫米(N/mm)计的撕裂引发和蔓延强度，其分别使用ASTM D1004-03，D1938-02，和ASTM D882测得。
从表6可明显看出，在前面的实施例中看见的改善的耐刮擦性和硬度，没有损害制品的机械性质。
本申请披露的范围包括端点并且是可组合的(例如，范围“至多约25wt％，或者更具体地，约5wt％至约20wt％”包括端点，和“约5wt％至约25wt％，”范围的所有内部值等)。“组合”包括共混物，混合物，衍生物，合金，反应产物等。此外，本申请的术语“第一”、“第二”等不指代任何顺序，量，或者重要性，而是用来对元素彼此之间进行区别，术语“一(a)”和“一种(an)”在本申请中不指代量的限制，而是指代存在至少一个所指的对象。与数量联用的修饰语″约″包括所述的值，并且具有上下文所指出的意义(例如，包括与具体量的测量方法相关的误差等级)。本申请所用的后缀“(s)”意图同时包括单数和复数个它所修饰的术语，由此包括一个或者多个该术语(例如，着色剂(s)包括一种或者多种着色剂)。在整个说明书中所称的“一种实施方式”，“另一实施方式”，“实施方式”等意思是指与该实施方式相关联地描述的具体的元素(例如，特征，结构，和/或特性)包括在本申请所述的至少一种实施方式中，并且可以存在或者可以不存在于其它实施方式中。此外，应该理解，所述的元素可以在各种实施方式中以任何合适的方式结合。本申请所用的术语“(甲基)丙烯酸酯”包括丙烯酸酯和甲基丙烯酸酯基团。化合物使用标准术语描述。例如，任何没有被任何所述的基团所取代的位置理解为它的价键被所示的键或者氢原子填充。不在两个字母或者符号之间的短横线(“-“)用于表示取代的附着点。例如，-CHO是通过羰基的碳原子附接的。
将引用的所有专利、专利申请和其它参考文献的全部内容都通过参考并入本申请。但是，如果本申请中的术语与并入的参考文献的术语相反或相冲突时，来自本申请的术语优先于来自并入的参考文献的与之相冲突的术语。
虽然已经参考优选的实施方式描述了本发明，本领域技术人员应该理解，可以做出各种变化，并且等价物可代替其成分，而不偏离本发明的范围。此外，可以做出许多变化形式，以使具体的情况或材料适应于本发明的教导，而不偏离本发明的范围。因此，期望本发明不限于作为进行本发明的最佳方式公开的具体实施方式，而本发明将包括落入所附权利要求的范围内的所有实施方式。

Claims (14)

1.一种片材，其包括：
含有丙烯酸类聚合物的盖层，其中所述盖层为总厚度的1％至50％，所述总厚度为5mil至500mil；和
基础层，所述基础层包括脂环族聚酯共聚物和芳族聚碳酸酯，其中所述脂环族聚酯共聚物是聚(1，4-亚环己基二亚甲基共聚-亚乙基对苯二甲酸酯)，其中大于50mol％的酯基团源自1，4-环己烷二甲醇；
其中所述盖层和基础层共挤出，形成所述片材，所述片材是可热成型的。
2.权利要求1的片材，其中所述片材的撕裂蔓延强度为大于5N/mm。
3.权利要求1的片材，其中所述基础层包括含有50wt％至90wt％的脂环族聚酯共聚物和余量为芳族聚碳酸酯的共混物。
4.权利要求1的片材，其中所述片材的铅笔硬度大于HB。
5.权利要求1的片材，其中所述片材的撕裂引发强度为大于或等于120N/mm。
6.权利要求1的片材，其中所述片材的抗拉强度大于40MPa。
7.权利要求1的片材，其中所述丙烯酸类聚合物是聚(甲基)丙烯酸烷基酯。
8.权利要求7的片材，其中所述盖层是聚(甲基)丙烯酸甲酯。
9.权利要求1的片材，其中所述所述盖层与所述基础层的厚度比为10％至25％。
10.权利要求1的片材，其中所述盖层在基础层之上并与基础层接触。
11.权利要求1的片材，所述总厚度为5mil至40mil。
12.制造制品的方法，其包括：
使丙烯酸类聚合物在挤出机中熔融；
在挤出机中形成包含脂环族聚酯共聚物和芳族聚碳酸酯的熔融混合物，其中所述脂环族聚酯共聚物是聚(1，4-亚环己基二亚甲基共聚-亚乙基对苯二甲酸酯)，其中大于50mol％的酯基团源自1，4-环己烷二甲醇；
共挤出所述丙烯酸类聚合物和所述熔融混合物，从而形成片材，所述片材是可热成型的，其中所述熔融混合物形成基础层，而所述丙烯酸类聚合物在所述基础层上形成盖层，和
其中所述盖层为总片材厚度的1％至50％，所述总片材厚度为5mil至500mil。
13.权利要求12的方法，还包括热成型所述片材。
14.权利要求12的方法，其中所述丙烯酸类聚合物包含聚(甲基)丙烯酸烷基酯。
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7923100B2 (en) * 2008-01-28 2011-04-12 Sabic Innovative Plastics Ip B.V. Multilayer articles and methods for making multilayer articles
CN102905895B (zh) * 2010-08-04 2014-12-03 帝人化成株式会社 多层膜、装饰成型用膜以及成型体
JP2014518170A (ja) * 2011-06-17 2014-07-28 カラーマトリックス ホールディングス インコーポレイテッド ポリマー材料
DE102011113160A1 (de) * 2011-09-14 2013-03-14 Evonik Röhm Gmbh Polymere Materialien für Außenanwendungen mit selbstheilenden Oberflächeneigenschaften nach Verkratzen oder Abrasionsbeschädigung
US20130280535A1 (en) * 2012-04-23 2013-10-24 Sabic Innovative Plastics Ip B.V. Multilayer sheet and methods of making and articles comprising the multilayer sheet
KR20140119860A (ko) * 2013-03-27 2014-10-13 삼성디스플레이 주식회사 표시장치용 윈도우 및 이를 포함하는 표시 장치
KR101800482B1 (ko) * 2013-10-31 2017-12-21 (주)엘지하우시스 고경도 다층시트
KR20170091683A (ko) * 2014-12-04 2017-08-09 미츠비시 가스 가가쿠 가부시키가이샤 폴리에스터 수지를 포함하는 기능성 시트 및 그것을 이용한 렌즈
CN110709733A (zh) 2017-06-05 2020-01-17 沙特基础工业全球技术有限公司 多层聚合物膜及其制造方法
US11951720B2 (en) * 2018-10-26 2024-04-09 Mitsubishi Gas Chemical Company, Inc. Thermoplastic resin laminate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
US5783307A (en) * 1996-11-04 1998-07-21 Eastman Chemical Company UV stabilized multi-layer structures with detectable UV protective layers and a method of detection
WO1999048685A1 (en) * 1998-03-24 1999-09-30 General Electric Company Multilayer plastic articles
US6147162A (en) * 1996-02-16 2000-11-14 Sumitomo Chemical Company, Limited Acrylic film and moldings made using the same
US6649104B2 (en) * 1997-07-31 2003-11-18 Sumitomo Chemical Company, Limited Acrylic resin film and laminated film comprising the same
WO2004011254A1 (en) * 2002-07-30 2004-02-05 General Electric Company Polycarbonate/cycloali phatic polyester multilayered articles

Family Cites Families (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2465319A (en) * 1941-07-29 1949-03-22 Du Pont Polymeric linear terephthalic esters
US3947539A (en) * 1972-07-10 1976-03-30 The Dow Chemical Company Method for cold forming plastic article
US3830029A (en) * 1972-10-18 1974-08-20 L Vance Skylight construction
US4124652A (en) * 1976-12-14 1978-11-07 General Electric Company Thermoplastic molding composition
US4125572A (en) * 1976-12-14 1978-11-14 General Electric Company Thermoplastic molding composition
DE2721466A1 (de) * 1977-05-12 1978-11-16 Robugen Gmbh Verfahren zur herstellung von 2'-desoxyribofuranosylnucleosiden
NL181914C (nl) * 1977-07-05 1900-01-01 Toyo Seikan Kaisha Ltd Inrichting voor het vervaardigen van getrokken voorwerpen.
US4180651A (en) * 1978-02-28 1979-12-25 General Electric Company Polycarbonate composition having resistance to high heat distortion
US4304899A (en) * 1978-07-31 1981-12-08 General Electric Company Polycarbonate compositions having improved barrier properties
US4259478A (en) * 1979-12-14 1981-03-31 Eastman Kodak Company Process for preparing high molecular weight copolyesters
US4322455A (en) * 1980-09-15 1982-03-30 General Electric Company Process for producing an ultraviolet radiation stabilized polymeric article
US4355080A (en) * 1981-03-02 1982-10-19 Eastman Kodak Company Polyester-acrylic composite sheet having improved weatherability
US4380612A (en) * 1981-12-21 1983-04-19 General Electric High heat distortion resistant segment ester polycarbonates
DE3244953C2 (de) * 1982-12-04 1984-11-29 Röhm GmbH, 6100 Darmstadt Verfahren zur Herstellung einer Hohlkammerkunststofftafel
US4786692A (en) * 1982-12-20 1988-11-22 General Electric Company High strength, reduced heat distortion temperature thermoplastic composition
US4554309A (en) * 1982-12-27 1985-11-19 General Electric Company Polycarbonate from cycloalkylidene tetra alkyl substituted diphenol
US4608430A (en) * 1984-12-28 1986-08-26 General Electric Company Polycarbonate exhibiting improved heat resistance from diphenol containing disubstituted phenylene radical
GB8528545D0 (en) * 1985-11-20 1985-12-24 Minnesota Mining & Mfg Photothermographic materials
US4837254A (en) * 1988-03-02 1989-06-06 Eastman Kodak Company Poly(1,4-cyclohexylene dimethylene terephthalate) molding compositions
US4897448A (en) * 1988-04-01 1990-01-30 Eastman Kodak Company Polyester/polycarbonate blends
US4812534A (en) * 1988-04-04 1989-03-14 Eastman Kodak Company Impact toughened polyester nylon blends
DE3837589A1 (de) * 1988-11-05 1990-05-10 Roehm Gmbh Uv-absorber-haltige methacrylatschutzschicht fuer polycarbonat
US4879355A (en) * 1988-09-29 1989-11-07 Eastman Kodak Compatible tricomponent polymer blends
DE3837588A1 (de) * 1988-11-05 1990-05-10 Roehm Gmbh Schlagzaehe, uv-absorber-haltige methacrylatschutzschicht fuer polycarbonat
DE3926719A1 (de) * 1988-12-23 1990-07-05 Bayer Ag Polycarbonate aus alkylcyclohexylidenbisphenolen
US5051490A (en) * 1989-07-03 1991-09-24 General Electric Company Thermoplastic polyarylate compositions having improved oxygen barrier properties
DE3931771A1 (de) * 1989-09-23 1991-04-04 Bayer Ag Thermoplastische legierungen mit polyestern und polyestercarbonaten auf basis substituierter cycloalkylidenbisphenole
KR927003725A (ko) * 1989-12-28 1992-12-18 알프레드 피.로렌죠 향상된 투명성과 내충격성을 지니는 폴리에스테르/폴리카보네이트 배합물
US5159003A (en) * 1990-10-09 1992-10-27 Ferro Corporation Polyester-compatible alloys of polycarbonate
DE4102650A1 (de) * 1991-01-30 1992-08-06 Silver Plastics Gmbh & Co Kg Verfahren und vorrichtung zum herstellen eines spinnvlieses aus synthetischem polymer
US5242967A (en) * 1992-01-29 1993-09-07 Eastman Kodak Company Reinforced molding composition based on poly(1,4-cyclohexylene dimethylene terephthalate) containing a high molecular weight aliphatic polyester
US5207967A (en) * 1992-03-02 1993-05-04 Eastman Kodak Company Multicomponent polyester/polycarbonate blends with improved impact strength and processability
US5340907A (en) * 1993-06-28 1994-08-23 Eastman Chemical Company Copolyester of cyclohexanedimethanol and process for producing such polyester
US5382628A (en) * 1994-02-28 1995-01-17 Eastman Chemical Company High impact strength articles from polyester blends
US5420212A (en) * 1994-03-31 1995-05-30 Eastman Chemical Company Polyester/polycarbonate/polycaprolactone blends
US5461120A (en) * 1994-05-18 1995-10-24 Bayer Corporation Transparent thermoplastic molding compositions
US5491179A (en) * 1994-11-23 1996-02-13 Bayer Corporation Thermally stable, gamma radiation-resistant blend of polycarbonate with polyester
EP0763560B1 (en) * 1995-03-28 2003-05-28 Mitsubishi Rayon Co., Ltd. Molded article laminated with acrylic polymer film and acrylic polymer film
US6043322A (en) * 1996-12-28 2000-03-28 Eastman Chemical Company Clear polycarbonate and polyester blends
US5907026A (en) * 1997-08-27 1999-05-25 General Electric Company Polycarbonate compositions comprising polyester resins and ultraviolet light absorbers
WO1999063002A1 (en) 1998-05-29 1999-12-09 General Electric Company Polycarbonate polyester resin molding composition with good impact properties
US7388073B2 (en) * 1998-06-26 2008-06-17 Genentech, Inc. PRO9835 polypeptides
JP2000191804A (ja) * 1998-12-28 2000-07-11 Mitsubishi Rayon Co Ltd アクリルフイルム及びアクリル積層浴室内装壁材
US6232429B1 (en) * 1999-11-01 2001-05-15 General Electric Company Method for making polyester carbonates
TWI284092B (en) * 2000-02-01 2007-07-21 Sumitomo Chemical Co Recycled plastic product
US6486251B1 (en) * 2000-02-29 2002-11-26 General Electric Company Special visual effect polycarbonate-polyester composition
JP4695246B2 (ja) * 2000-06-19 2011-06-08 三菱レイヨン株式会社 アクリル樹脂フィルムの製造方法、積層シートおよび積層射出成形品
US6989190B2 (en) * 2000-10-17 2006-01-24 General Electric Company Transparent polycarbonate polyester composition and process
US20030032725A1 (en) * 2001-06-26 2003-02-13 General Electric Company Transparent polycarbonate polyester composition and process
US6569957B2 (en) * 2000-11-03 2003-05-27 Eastman Chemical Company Blends of polycarbonate and polyester and sheets and films formed therefrom
US20020111428A1 (en) * 2000-12-14 2002-08-15 General Electric Company Transparent polycarbonate polyester composition and process
US6448334B1 (en) * 2000-12-19 2002-09-10 General Electric Company Translucent polycarbonate composition, method for preparation thereof, and articles derived therefrom
KR20020062817A (ko) * 2001-01-24 2002-07-31 스미또모 가가꾸 고오교오 가부시끼가이샤 아크릴계 수지 적층 필름 및 이것을 사용한 적층 성형품
JP2003071996A (ja) * 2001-09-07 2003-03-12 Sumitomo Chem Co Ltd 積層体
US8057903B2 (en) * 2001-11-30 2011-11-15 Sabic Innovative Plastics Ip B.V. Multilayer articles comprising resorcinol arylate polyester and method for making thereof
US6723768B2 (en) * 2002-03-27 2004-04-20 Eastman Chemical Company Polyester/polycarbonate blends with reduced yellowness
US20030195295A1 (en) * 2002-04-16 2003-10-16 General Electric Company Miscible blends of polyesters and polycarbonates with good thermal characteristics, and related processes and articles
US6620509B1 (en) * 2002-04-22 2003-09-16 Mitsubishi Gas Chemical Company, Inc. Transparent resin laminate and molded article used the same
US6689863B1 (en) * 2002-10-08 2004-02-10 General Electric Company Polycarbonate copolymers and methods for producing the polycarbonate copolymers
US7270882B2 (en) * 2003-02-21 2007-09-18 General Electric Company Weatherable multilayer articles and method for their preparation
US7087682B2 (en) * 2003-05-02 2006-08-08 General Electric Polymeric blends for optical devices and method of manufacture thereof
US7258923B2 (en) * 2003-10-31 2007-08-21 General Electric Company Multilayered articles and method of manufacture thereof
DE10351535A1 (de) * 2003-11-03 2005-06-09 Röhm GmbH & Co. KG Mehrschichtfolie aus (Meth)acrylatcopolymer und Polycarbonat
US7210926B2 (en) * 2003-11-10 2007-05-01 General Electric Company Formable sheets for medical applications and methods of manufacture thereof
US7256228B2 (en) * 2003-11-21 2007-08-14 General Electric Company Stabilized polycarbonate polyester composition
US7199210B2 (en) * 2003-11-28 2007-04-03 Futura Polymers, A Division Of Futura Polyesters Limited Process for the preparation of polyethylene terephthalate (PET)
US7411021B2 (en) * 2003-12-18 2008-08-12 Sabic Innovative Plastics Ip B.V. Polycarbonate polyester molding composition
US20050137360A1 (en) * 2003-12-19 2005-06-23 General Electric Company Clear polycarbonate polyester blend
JP4256281B2 (ja) 2004-02-24 2009-04-22 株式会社ブリヂストン タイヤの製造方法およびビード部材供給装置
US20060040076A1 (en) * 2004-08-18 2006-02-23 Franzyshen Stephen K Formable film for cold-form, blister-type pharmaceutical packaging
US7718733B2 (en) * 2004-12-20 2010-05-18 Sabic Innovative Plastics Ip B.V. Optically clear polycarbonate polyester compositions
DE102005017023A1 (de) * 2005-04-13 2006-10-19 Bayer Materialscience Ag UV-stabilisierte Polycarbonatformkörper
US7399571B2 (en) * 2005-05-06 2008-07-15 General Electric Company Multilayered articles and method of manufacture thereof
JP2007012899A (ja) * 2005-06-30 2007-01-18 Brother Ind Ltd 配線基板及びインクジェットヘッド
US7521119B2 (en) * 2005-07-07 2009-04-21 Sabic Innovative Plastics Ip B.V. Windows and other articles made from DMBPC polycarbonate homopolymer and copolymer
US20070155913A1 (en) * 2006-01-04 2007-07-05 Shreyas Chakravarti Thermoplastic composition, method of making, and articles formed therefrom
US7700696B2 (en) * 2006-06-28 2010-04-20 Sabic Innovative Plastics Ip B.V. Polycarbonate composition having improved scratch resistance, and articles formed therefrom
US7655737B2 (en) * 2006-11-16 2010-02-02 Sabic Innovative Plastics Ip B.V. Polycarbonate-polyester blends, methods of manufacture, and methods of use
US7686998B2 (en) * 2006-11-22 2010-03-30 Sabic Innovative Plastics Ip B.V. Thermoplastic composition, method of manufacture thereof, and articles derived therefrom
US7691304B2 (en) * 2006-11-22 2010-04-06 Sabic Innovative Plastics Ip B.V. Thermoplastic composition, method of manufacture thereof, and articles derived therefrom
US20080161507A1 (en) * 2006-12-28 2008-07-03 Shreyas Chakravarti Polyester-polycarbonate blends
US7687583B2 (en) * 2007-04-30 2010-03-30 Sabic Innovative Plastics Ip B.V. Polyester polycarbonate compositions, methods of making, and articles formed therefrom
US7923100B2 (en) * 2008-01-28 2011-04-12 Sabic Innovative Plastics Ip B.V. Multilayer articles and methods for making multilayer articles
US20090191411A1 (en) * 2008-01-28 2009-07-30 Sandeep Tripathi Cycloaliphatic Polyester Copolymer Articles And Methods for Making Articles Therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
US6147162A (en) * 1996-02-16 2000-11-14 Sumitomo Chemical Company, Limited Acrylic film and moldings made using the same
US5783307A (en) * 1996-11-04 1998-07-21 Eastman Chemical Company UV stabilized multi-layer structures with detectable UV protective layers and a method of detection
US6649104B2 (en) * 1997-07-31 2003-11-18 Sumitomo Chemical Company, Limited Acrylic resin film and laminated film comprising the same
WO1999048685A1 (en) * 1998-03-24 1999-09-30 General Electric Company Multilayer plastic articles
WO2004011254A1 (en) * 2002-07-30 2004-02-05 General Electric Company Polycarbonate/cycloali phatic polyester multilayered articles
US6887573B2 (en) * 2002-07-30 2005-05-03 General Electric Company Polycarbonate polyester articles with enhanced adhesion between outer layer and base substrate

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