CN1105642C - 带有泡沫底层的密实表面材料 - Google Patents

带有泡沫底层的密实表面材料 Download PDF

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CN1105642C
CN1105642C CN96192909A CN96192909A CN1105642C CN 1105642 C CN1105642 C CN 1105642C CN 96192909 A CN96192909 A CN 96192909A CN 96192909 A CN96192909 A CN 96192909A CN 1105642 C CN1105642 C CN 1105642C
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D·E·斯瓦尔茨
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EIDP Inc
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    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • 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
    • B32B27/065—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 of foam
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00413—Materials having an inhomogeneous concentration of ingredients or irregular properties in different layers
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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  • Laminated Bodies (AREA)
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Abstract

本发明提供密实表面材料，所述材料的填充聚合物的薄层与空心填料填充聚合物背衬形成整体，在聚合物混合体中没有界面或过渡区。

Description

铸造复合物件
                          发明背景
本发明涉及具有添加填料的聚合物密实表面和还充填有空心填料的类似材料的底层的、在所说的层间没有未充填的聚合物的过渡区的复合铸造物件。
在本技术领域中密实表面材料是已知的，包括那些基于聚甲基丙烯酸甲酯和三水合氧化铝的材料。关于这些产物的基本工艺被技露在Duggins的美国专利第3847865号(1974)和Buser、Roedel和Vassiliou的美国专利第4085246号(1978)和Frank、Otremba、Pohl和Schlier的公开的PCT专利申请US88/14322(1988)中。
先前将这样的密实表面材料、空心填料-充填的底层和玻璃纤维增强材料层合起来的尝试使用昂贵的多步法而且层合的产品具有其各自性能明显不同的层。这样的层状产品与整体产品相比在某些条件下通常更易于由于界面而引起脱层和其他弱点。在这类多层产品中其代表是Schock的EP285046(1993)的多层产品。
此处引用上述所有文献的有关方法和产品的教导来作为制造密实表面充填聚合物材料的参考文献。希望能提供一种轻质片材，它具有整体形式的密实表面材料的表面特性，而在层间没有层过渡区，并且能以成本较低的方法制造。
                           发明简述
本发明提供铸造复合物件，所述铸造复合物件包括聚合物的基质和至少两个含不同填料的区，所说的物件基本上是扁平的并具有两个相对的表面，这样物件的第一区包括物件的一个含有填料量占填料加基质重量的10～80％的表面，而第二区包括与所说的第一表面相对的、具有填料量为5-60％和空心填料量为3-30％的第二表面，两者均以填料和空心填料加基质的重量计，所说的第一和第二区形成一个在两个区之间基本上没有未充填基质层的连续体。还可在所述第二区的相对侧包括与第一区相似的第三区。优选地，本发明的铸造复合物件在第一表面上还具有一硬表面，该硬表面含带有很硬的填料的聚合物基材，以提供耐刮和耐磨性。
在另一实施方案中，将组成在第一组合物限制范围内的第三层加到第二层上。而且在浇铸第一层之前，可以铺上一个硬表面，该硬表面具有比ATH更硬的填料，例如氧化铝、硅石、碳酸钙或天然的如花岗岩。此外，充填或未充填树脂的粉碎颗粒可被添加到第一层中。所说的粉碎颗粒参见美国专利第4085246号。
                           详细的说明
本发明的一个优点在于它提供一种重量轻、更经济，没有会引起脆性区或引起其他机械困难的聚合物过渡区的密实表面材料。该产物可以一步或两步法铸塑生产。
除了另有指出者外，份数，比例或百分比均以重量表示。
                           一步浇注法
通过添加二种或多种的填料到甲基丙烯酸甲酯单体，或此单体与溶于此单体中的20％聚甲基丙烯甲酯的浆液的掺合物中制备可聚合的混合物。在本实施例中填料是1)三水合铝，2)中空玻璃泡，优选为3M“Scotchlite”S-22-10～100μm，中值40μm，和3)米色着色颜料。所说的浆液包括单体中的约20％聚甲基丙烯酸甲酯。通过掺合下列成分而制备一种混合物：
                                                     重量％
甲基丙烯酸甲酯                                       50.5
浆液                                                 5.5
三水合氧化铝                                         33.0“Scotchlite”S-22(10-100μm，中值40μm)玻璃泡        11.0
                                                     100.0
添加少量的米色颜料(＜1.0％)以着色产物。添加引发剂和对所说的混合物抽真空以除掉空气。然后将混合物浇铸到模具中。
所说的混合物具有低的粘度(约100厘泊或0.1Psec.)，这有利于所述填料根据其比重与液相相比的不同进行分层。在较重的三水合氧化铝(比重为2.42)和米色颜料下沉到底部的同时，中空玻璃泡(比重为0.22)在液体(比重约为1)中上升。在固化之前振动混合物会加速混合物中填料的分离和使填料在其各自层中的分散更均匀。在3.8cm厚的模具中浇注和固化之后，出现两个分离的层：含有三水合氧化铝和着色料的0.8cm厚的丙烯酸聚合物的面层和含有玻璃泡与三水合氧化铝的3.0cm厚的底层。然而，在此两层之间不存在界面。它们借助于在整个结构中连续的聚合物基质而成为一体。在此结构中面层与泡沫底层的厚度比约为1∶4。73.8％的三水合氧化铝存在于面层中而9.7％的三水合氧化铝存在于泡沫层中(根据热失重分析法测定)。
在面层和泡沫层中含有较重的填料是令人希望的，这是由于这类填料能改进产品的性质，比如改进的强度和刚度、耐冲击性、阻燃性、色分布和尺寸稳定性。在浇注后和胶凝或固化之前发生较重填料的分离。通过不同的加工变量包括在初始的混合组合物的填料量、混合物粘度、混合温度和浇注后的振动强弱来确定和控制每一层中的填料量。较重填料在面层中的量为10-80％、优选为30-60％，而在泡沫层中的量为5～60％、优选为10～30％。
                         实施例2
                    “湿对湿”铸塑法
制备两种混合物以便能顺序地将它们浇铸到模具中。混合物(A)由填料，例如三水合氧化铝分散于由含约20％聚甲基丙烯酸甲酯在甲基丙烯酸单体中的浆液，与引发剂组成的液相中组成。可以添加另外的单体以调整混合物的粘度。还可以添加着色的颜料和/或颗粒以得到希望的颜色和图案。一种作为混合物(A)的典型的组合物包括：
                                                       重量％
甲基丙烯酸甲酯                                         4.0
树脂浆                                                 36.0
三水合氧化铝                                           42.0
着色的颗粒(30～150目，美国标准筛＝100～600μm)         18.0
                                                       100.0
混合物(B)由填料，通常是轻重量的，例如中空玻璃微球和碳酸钙，分散于由含约20％聚甲基丙烯酸甲酯在甲基丙烯酸单体中的浆液与引发剂组成的液相中组成。可以添加另外的单体以调整铸塑粘度。一种作为混合物(B)的典型的组合物包括：
                                                        重量％
甲基丙烯酸甲酯                                          44.0
浆液                                                      11.0
三水合氧化铝                                              37.0“Scotchlite”K-1玻璃泡(20～120μm，中值70μm，比重0.125)  8.0
                                                          100.0
混合物(A)抽真空以除去空气，然后将其浇入模具中而在模具的底部形成厚度为0.5cm的层。然后同样将抽真空的混合物(B)浇到模具中的由混合物(A)形成的仍为湿的尚未固化层的上面，以形成1.4cm厚的第二层。在此结构已固化之后，聚合形式的混合物(A)是面层而混合物(B)是泡沫底层。虽然好像是两个分立的层，但是在此两层之间没有界面。它们是一体的，聚合物基质在整个结构中是连续的。

Claims (6)

1.一种包括聚合物基质和两个不同填料的区的铸造复合物件，所述的物件基本上是扁平的，具有两个相对表面，这样物件的第一区包括物件的一个填料量占填料加基质的重量的10～80％的表面，而第二个填料区包括与所说的第一表面相对的、填料量为5～60％和中空微球量为3～30％的第二表面，两者均以填料和中空微球加基质的重量计，所说的第一和第二区形成一个在两个区之间基本上没有未充填基质的层的连续体。
2.权利要求1的铸造复合物件，其中填料选自三水合氧化铝、氧化铝、硅石、碳酸钙、充填或未充填树脂的磨制颗粒、玻璃和天然石料，以及选自玻璃和聚合物微球、飞灰、珍珠岩和其它中空微球形式的天然材料的中空微球，所述聚合物基质由选自丙烯酸、甲基丙烯酸、烷基中具有1-18个碳原子的丙烯酸或甲基丙烯酸烷基酯、苯乙烯、取代苯乙烯、乙酸乙烯酯、丙烯腈、甲基丙烯腈、马来酐、马来酸酯、衣康酸及衣康酸酯的至少一种单体任选与二官能、三官能或四官能单体制成。
3.权利要求1的铸造复合物件，其在第一表面上具有附加的硬表面层，该硬表面包含聚合物基质和选自氧化铝、硅石、碳酸钙和天然石料的比三水合氧化铝硬的填料。
4.权利要求1的铸造复合物件，其中在第一区，填料含约45-65％的平均粒度30-70μm的三水合氧化铝，在第二区，填料含约30-60％的平均粒度3-14μm的碳酸钙和5-15％的平均粒度30-100μm的中空玻璃微球。
5.权利要求4的铸造复合物件，其中组成与第一区相似的第三区与第二区的开放表面相邻，所述第一、二、三区形成各区之间没有未充填基质的层的连续体。
6.权利要求5的铸造复合物件，其中第一区的填料包含约10-50％的平均粒度3-100μm的三水合氧化铝和5-70％的平均粒度50μm-20mm的充填或未充填树脂的磨制颗粒。
CN96192909A 1995-03-29 1996-03-26 带有泡沫底层的密实表面材料 Expired - Fee Related CN1105642C (zh)

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WO2009044417A1 (en) * 2007-10-03 2009-04-09 Stone Italiana Spa Agglomerated material for floorings and coverings, as well as a method for obtaining the same
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TR199600257A2 (tr) 1996-10-21
KR19980703370A (ko) 1998-10-15
JPH10505031A (ja) 1998-05-19
CN1179749A (zh) 1998-04-22
DE69604164T2 (de) 2000-05-04
ATE184237T1 (de) 1999-09-15
US6004663A (en) 1999-12-21
AU5431896A (en) 1996-10-16
JP3020611B2 (ja) 2000-03-15
EP0817721B1 (en) 1999-09-08
WO1996030204A1 (en) 1996-10-03
KR100402336B1 (ko) 2004-02-11
DE69604164D1 (de) 1999-10-14
AU694652B2 (en) 1998-07-23

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