CN108204098A - 硬质聚氯乙烯地砖及其制造方法 - Google Patents

硬质聚氯乙烯地砖及其制造方法 Download PDF

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Publication number
CN108204098A
CN108204098A CN201611169521.5A CN201611169521A CN108204098A CN 108204098 A CN108204098 A CN 108204098A CN 201611169521 A CN201611169521 A CN 201611169521A CN 108204098 A CN108204098 A CN 108204098A
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China
Prior art keywords
layer
floor tile
pvc floor
hard pvc
weight
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CN201611169521.5A
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English (en)
Inventor
张明奇
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Ming Ho (lutai) Technology Co Ltd
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Ming Ho (lutai) Technology Co Ltd
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Publication date
Application filed by Ming Ho (lutai) Technology Co Ltd filed Critical Ming Ho (lutai) Technology Co Ltd
Priority to CN201611169521.5A priority Critical patent/CN108204098A/zh
Priority to EP17181789.3A priority patent/EP3336278A1/en
Priority to US15/652,556 priority patent/US20180171644A1/en
Publication of CN108204098A publication Critical patent/CN108204098A/zh
Pending legal-status Critical Current

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Abstract

本发明提供一种硬质聚氯乙烯地砖，其由上至下依次包括保护层、装饰层、支撑层和平衡层，所述硬质聚氯乙烯地砖以欧洲标准EN434测得的加热尺寸收缩率为0‑0.15％，邵氏D型硬度为60°‑90°。本发明还提供了制备该硬质聚氯乙烯地砖的方法。

Description

硬质聚氯乙烯地砖及其制造方法
技术领域
本发明涉及建筑材料及其制造方法，特别是涉及硬质聚氯乙烯(PVC)地砖及其制造方法。
背景技术
随着生活水平的提高，人们对于居家生活环境越来越关注。地砖作为室内装潢的最重要组成部分之一，理所当然地受到了更多关注。目前，广泛使用的传统地砖包括：木制地砖、石材地砖、复合地砖等。但是上述地砖的使用和铺砖方式均有明显的不足。木制地砖、石材地砖、复合地砖的代表性产品分别是强化地砖、瓷砖、实木复合地砖，但这些使用量较大的传统地材都属于超硬质地砖。此外，瓷砖脚感差、表面光滑，尤其是沾水后表面湿滑，人走在上面极易摔倒。强化地砖与实木复合地砖同属于木质类地砖，但都有甲醛含量不易控制的缺点，还有不防水等特点。
近年来聚氯乙烯地砖作为弹性地材的代表性产品，由于其防水、零甲醛等优点，逐步取代了传统地材，使用量越来越大。但其相对于传统的地材，最大的缺点就是对其要铺设的地面要求高。必须要做自流平才能体现其较好的装饰效果，这就在一定程度上限制了聚氯乙烯地砖的使用范围。因此急需开发一种对地面要求不高的新型聚氯乙烯地砖。
室内用木塑复合地砖(WPC，Wood Plastic Composites)在一定程度上解决了这个问题，其上层为一般的干底半硬质聚氯乙烯地砖，下层为挤出发泡硬板，二者用胶粘合，有的产品还在下部贴上了静音垫。室内用木塑复合地砖的整体厚度能达到5.0mm-7.5mm。但是其尺寸极不稳定，受温度与湿度的影响很大，在物理性能方面，加热尺寸变化率大，残余凹陷度大，易发生曲翘。在实际的使用过程中，由于锁扣部位长期受尺寸变化的影响，膨胀与收缩交替，产品极易出现脱扣、断裂、开胶、变形的情况。使用范围也有很大限制，一般不能铺设在大面积的施工现场。
发明内容
本发明提供一种硬质聚氯乙烯地砖，其由上至下依次包括保护层、装饰层、支撑层和平衡层，该硬质聚氯乙烯地砖的加热尺寸收缩率为0-0.15％(欧洲标准EN434)，邵氏D型硬度为60°-90°。
在本发明的硬质聚氯乙烯地砖的优选实施方式中，所述保护层可以是其上淋涂有UV涂料层的聚氯乙烯层，所述聚氯乙烯层作为保护层的衬底，包含65-100重量％的聚氯乙烯、0-35重量％的增塑剂、以及0-5重量％的钙锌稳定剂。所述增塑剂是选自邻苯二甲酸二异壬酯(DINP)、对苯二甲酸二辛脂(DOPT)、柠檬酸酯类、环氧大豆油(ESO)等的一种或多种增塑剂。所述保护层也可以仅仅是一层UV涂料层。对用于所述保护层的UV涂料没有特别限制，可以选自商购的已知UV涂料，如环氧丙烯酸酯、聚氨酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、丙烯酸酯化聚丙烯酸树脂和不饱聚酯等。所述保护层的厚度优选为0.05mm-1mm。所述保护层用于增加硬质聚氯乙烯地砖的耐磨性，减少磨损，使硬质聚氯乙烯地砖在长时间使用后仍有漂亮的外观。
在本发明的硬质聚氯乙烯地砖的优选实施方式中，所述装饰层是印有图案的聚氯乙烯薄膜，其是通过直接印刷或热转印方式将图案印到作为装饰层衬底的聚氯乙烯薄膜上而获得的。所述聚氯乙烯薄膜包含40-100重量％的聚氯乙烯、0-60重量％的选自碳酸钙和滑石粉的无机填料，其中还可以根据需要加入各色的颜料，例如钛白粉、碳黑、棕色色粉等。所述装饰层的聚氯乙烯薄膜的厚度为0.05-0.12mm。所述装饰层使得硬质聚氯乙烯地砖具有良好的视觉效果。
在本发明的硬质聚氯乙烯地砖的优选实施方式中，所述支撑层包含100重量份的聚氯乙烯、0-30重量份的增塑剂、100-750重量份的选自碳酸钙、高岭土、滑石粉等的无机填料、0-20重量份的增韧剂或抗冲击改性剂，以及0-5重量份的松香。其中所述增塑剂优选是选自邻苯二甲酸二异壬酯(DINP)、对苯二甲酸二辛脂(DOPT)、柠檬酸酯类、和环氧大豆油(ESO)等的一种或多种增塑剂。所述增韧剂或抗冲击改性剂优选选自氯化聚乙烯和丙烯酸酯类加工助剂，例如甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物(MBS)和丙烯酸酯类聚合物(ACR)。所述支撑层的厚度范围为0.1mm-10mm，邵氏D型硬度大于70°，优选为70-90°。所述支撑层可以是一层也可以是多层。
在本发明的硬质聚氯乙烯地砖的优选实施方式中，所述平衡层包含100重量份的聚氯乙烯、0-40重量份的增塑剂、100-550重量份的碳酸钙、0-20重量份的增韧剂或抗冲击改性剂，以及0-5重量份的松香。其中所述增塑剂优选是选自邻苯二甲酸二异壬酯(DINP)、对苯二甲酸二辛脂(DOPT)、柠檬酸酯类、和环氧大豆油(ESO)等的一种或多种增塑剂。所述增韧剂或抗冲击改性剂优选选自氯化聚乙烯和丙烯酸酯类加工助剂，例如甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物(MBS)和丙烯酸酯类聚合物(ACR)。所述平衡层的厚度范围是0.1mm-10mm，邵氏D型硬度为65-80°。硬质平衡层的设置降低了铺设地砖时对地面的要求。
在本发明的硬质聚氯乙烯地砖的一个优选实施方式中，在装饰层与支撑层之间、支撑层与平衡层之间、和/或平衡层下面，还附有发泡层，可达到静音和尺寸稳定性等效果。所述发泡层的材质选自聚氯乙烯发泡材质、EVA发泡材质、PP发泡材质、PE发泡材质和PS发泡材质等，其中任选加有纤维材料。
在本发明的硬质聚氯乙烯地砖的一个优选实施方式中，在地砖的四周边缘处形成大倒角，即，使地砖上平面和地砖垂直面相交的直角改变为斜角，形成15-60度的朝上的斜面，斜面的水平宽度最小为保护层厚度的0.5倍，最大为地砖厚度的3.8倍。
在本发明的硬质聚氯乙烯地砖的一个优选实施方式中，在具有大倒角的地砖的朝上的斜面上涂有装饰性的涂料，包括油漆、颜料和油墨等。所述涂料主要选自丙烯酸树脂、聚氨酯树脂和环氧树脂等。
本发明的硬质聚氯乙烯地砖整体的邵氏D型硬度为60-90°，并且以欧洲标准EN434测定的加热尺寸收缩率为0-0.15％，优选0-0.08％。
本发明还提供一种制备硬质聚氯乙烯地砖的方法，该方法包括如下步骤：
将用于支撑层的配方材料混合均匀、经密炼机密炼、扎轮机开炼和压延机压延的步骤，制备支撑层，然后将支撑层与预先制备好的平衡层、装饰层和任选存在的作为保护层衬底的聚氯乙烯层进行贴合、压花、然后进行渐进式冷却步骤，之后在线淋涂UV涂料形成保护层、经回火、在线成型制得聚氯乙烯地砖，其中
所述平衡层的制备工艺与支撑层的制备工艺相同，
所述装饰层通过在聚氯乙烯薄膜衬底上直接印刷或热转印图案而获得，
所述任选存在的作为保护层衬底的聚氯乙烯层和作为装饰层衬底的聚氯乙烯薄膜是通过把配方原料混合均匀、然后经挤出机塑化、再经压延机压延、之后冷却成型而制备的。
在本发明的制备硬质聚氯乙烯地砖的方法中，所述各层的密炼、开炼、塑化、贴合或压延等步骤的温度优选在130-145℃，特别优选140℃。
在本发明的制备硬质聚氯乙烯地砖的一个优选的实施方式中，所述将支撑层、平衡层、装饰层和保护层贴合的步骤是在制备支撑层的工艺步骤中在线完成的，贴合温度为130-145℃，特别优选140℃。
在本发明的制备硬质聚氯乙烯地砖的一个优选的实施方式中，所述将支撑层、平衡层、装饰层和保护层贴合的步骤是将制备好的上述各层在压延机上在130-145℃、40-80Kg压力下热压20-40分钟而完成的，其中支撑层是一层或多层。
在本发明的制备硬质聚氯乙烯地砖的优选方法中，所述渐进式冷却步骤包括将地砖温度逐段下降，例如第一段的温度为70-80℃，第二段的温度为40-50℃，第三段的温度为0-23℃。其原理是使地砖在维卡软化点温度下收缩，随后使分子流动逐渐下降，做好定型准备，最后定型。这样地砖再经历不同的温度时收缩率会明显下降。
在本发明的制备硬质聚氯乙烯地砖的优选方法中，所述回火温度为80-100℃，优选85-90℃，回火时间为1-10分钟，优选3-5分钟，然后逐渐冷却到23℃左右。经过上述处理的地砖减少了在不同温度变化下的收缩。
采用本发明的制备硬质聚氯乙烯地砖的生产方法，不仅提高了产量，而且地砖的稳定性大大提高，对温度的敏感性大大降低。
本发明的硬质聚氯乙烯地砖的支撑层和平衡层都具有高硬度，硬质平衡层降低了对地面的要求，聚氯乙烯保护层避免了强化地砖、实木复合地砖、和瓷砖等传统地材的噪音、光滑等问题。本发明的硬质聚氯乙烯地砖产品不但解决了传统地砖和室内用木塑复合地砖(WPC)的缺陷，而且成本较低，加工便利，具有很强的实际应用价值。
附图说明
图1为本发明的一个实施方式的硬质聚氯乙烯地砖的结构示意图。
图2为本发明的一个实施方式的硬质聚氯乙烯地砖的制造流程示意图。
图3为本发明的一个实施方式的硬质聚氯乙烯地砖的大倒角示意图。
具体实施方式
除非另外定义，本文所使用的所有技术和科学术语具有本发明所属领域普通技术人员通常所理解的相同含义。在相抵触的情况下，以本说明书中的定义为准。
除非另外说明，所有的百分数、份数、比例等都以重量计。
本发明中所使用的聚氯乙烯(PVC)选自任何可通过已知聚合方法所获得的聚氯乙烯或者任何可商购的聚氯乙烯，特别优选聚合度K值为K60和K67的市售聚氯乙烯。
下面结合附图对本发明的硬质聚氯乙烯地砖及其制备方法做进一步的示意性说明。
图1所示为本发明的硬质聚氯乙烯地砖的一个实施方式的结构示意图，该聚氯乙烯地砖由上至下依次包括保护层1、装饰层2、支撑层3和平衡层4。其中保护层1可以是在聚氯乙烯衬底上涂覆有UV涂料而形成的层，也可以仅是一层UV涂料层。装饰层2是在聚氯乙烯膜衬底上印刷上所需图案而形成的层。支撑层3可以是一层或多层。
图2所示为本发明硬质聚氯乙烯地砖的制造方法的一个实施方式的流程示意图。其中将支撑层配方材料通过自动计量系统1送入高速混合器2，使物料混合均匀，经过密炼机3密炼，扎轮机4开炼，进入两个双棍水平压延机5和6压延，保证支撑层的厚度且使厚度差小与0.1mm，双辊水平压延机能生产出厚度为0.1-10mm的支撑层；随后，通过在线贴合装置7使支撑层直接与预先制备好的作为保护层衬底的聚氯乙烯层、装饰层、平衡层在线贴合到一起，之后在压花机8中压花，把保护层衬底、装饰层、支撑层和平衡层牢牢压在一起，然后进入渐变式冷却装置9中进行冷却，之后在作为保护层衬底的聚氯乙烯层上淋涂UV涂料(未示出)，然后经回火和冷却后在收料装置10中获得产品。
图3所示为本发明硬质聚氯乙烯地砖的大倒角示意图。图3中地砖的上平面与侧面形成向上的斜面，其中A为地砖厚度，B为斜面水平宽度，C为倒角的角度，D为斜面的高度(有时D＝A)。在该斜面上优选涂覆带有装饰性的耐摩擦涂料，如：金色的环氧树脂，带有木纹效果的聚氨酯涂料等，使地砖整体更加美观。
实施例
下面以实施例的方式对本发明进行进一步的描述，但是不构成对本发明的限制。
实施例1：硬质聚氯乙烯地砖的制备
原料：
聚氯乙烯：南亚K60聚氯乙烯
DOTP(对苯二甲酸二辛酯)：齐鲁石化LF-30
Ca-Zn稳定剂：新加坡SUNACE SAK-CZL39-NP
钛白粉：杜邦公司R900
滑石粉：北京绿人奥粉体材料800目
CPE(氯化聚乙烯)：山东高信化学135A
松香：美国伊士曼Foral AX-E
保护层衬底的制备：
将135Kg聚氯乙烯、41.4Kg对苯二甲酸二辛酯、3.6Kg Ca-Zn稳定剂在高速混合机中混合均匀，通过行星式挤出机塑化，然后经四辊压延机压延成片，再经冷却辊冷却成型，获得作为保护层衬底的聚氯乙烯层。
装饰层的制备：
将81Kg聚氯乙烯、81Kg CaCO3、3.6Kg对苯二甲酸二辛酯、3.6Kg Ca-Zn稳定剂、1.8Kg钛白粉和5Kg滑石粉在高速混合机中混合均匀，通过行星式挤出机塑化，然后经四辊压延机压延成片，再经冷却辊冷却成型，获得作为装饰层衬底的聚氯乙烯薄膜。
通过热转印的方式将图案印刷到上述聚氯乙烯薄膜上，获得装饰层。
平衡层的制备：
将50Kg聚氯乙烯、13Kg对苯二甲酸二辛酯、90Kg CaCO3、1Kg Ca-Zn稳定剂、和1Kg松香通过自动计量系统送入高速混合器，使物料混合均匀，在140℃经密炼机密炼，扎轮机开炼，之后进入两个双辊水平压延机压延，冷却获得平衡层。
支撑层以及整个地砖的在线制备：
将40Kg聚氯乙烯、5Kg对苯二甲酸二辛酯、120Kg CaCO3、0.8Kg Ca-Zn稳定剂、3Kg氯化聚乙烯、和2Kg松香通过自动计量系统送入高速混合器，使物料混合均匀，在140℃经密炼机密炼，扎轮机开炼，之后进入两个双辊水平压延机压延，获得支撑层；随后，使支撑层直接与上述制备步骤中获得的保护层衬底、装饰层和平衡层于140℃在线贴合到一起，之后压花，使保护层衬底、装饰层、支撑层和平衡层牢牢贴在一起，然后进入渐变式冷却装置进行冷却，所述渐变式冷却装置的三段冷却温度分别为80℃、40℃和20℃；之后在线在保护层衬底上淋涂聚氨酯类UV涂料，形成最终的保护层，然后在90℃回火3分钟、在线成型，制得总厚度为5mm的聚氯乙烯地砖。
性能测试：
经欧洲标准EN434测试，上述获得的聚氯乙烯地砖的加热尺寸收缩率为0.08％。同时，所获得的聚氯乙烯地砖的邵氏D型硬度为72°。
采用本发明的生产工艺不仅提高了产量而且地砖的稳定性大大提高，对温度的敏感性大大降低。
本发明的方法中通过将支撑层直接与保护层、装饰层和平衡层在线贴合，与传统的通过模头挤出然后再用油压机层压的方法或者传统的压延方法相比，可以直接获得成品，提高了生产效率和产能，并且克服了模头挤出方法中出现的气泡、塑化不均等问题。
下表1给出了三种不同的地砖生产工艺的产能比较。
表1
上面通过实施例对本发明进行了具体的描述，但是该实施例不是对本发明的范围的限制，本领域技术人员应该明白的是，在本申请公开内容的基础上可以对聚氯乙烯地砖做出很多改变，这些都包括在本发明的精神范围内。

Claims (17)

1.硬质聚氯乙烯地砖，其由上至下依次包括保护层、装饰层、支撑层和平衡层，所述硬质聚氯乙烯地砖的以欧洲标准EN434测得的加热尺寸收缩率为0-0.15％，邵氏D型硬度为60°-90°。
2.如权利要求1所述的硬质聚氯乙烯地砖，其中所述保护层包括UV涂料层和任选存在的作为UV涂料层衬底的聚氯乙烯层，所述聚氯乙烯层包含65-100重量％的聚氯乙烯、0-35重量％的增塑剂、以及0-5重量％的钙锌稳定剂。
3.如权利要求1所述的硬质聚氯乙烯地砖，其中所述装饰层是印有图案的聚氯乙烯薄膜，所述聚氯乙烯薄膜包含40-100重量％的聚氯乙烯、0-60重量％的选自碳酸钙和滑石粉的无机填料，以及任选存在的颜料。
4.如权利要求1所述的硬质聚氯乙烯地砖，其中所述支撑层包含100重量份的聚氯乙烯、0-30重量份的增塑剂、100-750重量份的选自碳酸钙、高岭土、滑石粉的无机填料、0-20重量份的增韧剂或抗冲击改性剂，以及0-5重量份的松香，并且所述支撑层可以是一层或多层。
5.如权利要求4所述的硬质聚氯乙烯地砖，其中所述支撑层的厚度范围为0.1mm-10mm，邵氏D型硬度为70-90°。
6.如权利要求1所述的硬质聚氯乙烯地砖，其中所述平衡层包含100重量份的聚氯乙烯、0-40重量份的增塑剂、100-550重量份的碳酸钙、0-20重量份的增韧剂或抗冲击改性剂，以及0-5重量份的松香。
7.如权利要求6所述的硬质聚氯乙烯地砖，其中所述平衡层的厚度范围是0.1mm-10mm，邵氏D型硬度为65-80°。
8.如权利要求2、4或6所述的硬质聚氯乙烯地砖，其中所述增塑剂是选自邻苯二甲酸二异壬酯、对苯二甲酸二辛脂、柠檬酸酯类、和环氧大豆油中的一种或多种增塑剂。
9.如权利要求4或6所述的硬质聚氯乙烯地砖，其中所述增韧剂或抗冲击改性剂选自氯化聚乙烯和丙烯酸酯类加工助剂。
10.如权利要求1-7任一项所述的硬质聚氯乙烯地砖，其中在装饰层与支撑层之间、支撑层与平衡层之间、和/或平衡层下面，还附有发泡层，所述发泡层的材质选自聚氯乙烯发泡材质、EVA发泡材质、PP发泡材质、PE发泡材质和PS发泡材质，并且其中任选加有纤维材料。
11.如权利要求1-7任一项所述的硬质聚氯乙烯地砖，其中在地砖的四周边缘处形成15-60度的朝上的斜面，斜面的水平宽度最小为保护层厚度的0.5倍，最大为地砖厚度的3.8倍。
12.如权利要求11所述的硬质聚氯乙烯地砖，其中在具有大倒角的地砖的朝上的斜面上涂有装饰性的涂料。
13.制备如权利要求1-12任一项所述的硬质聚氯乙烯地砖的方法，包括如下步骤：
将用于支撑层的配方材料混合均匀、经密炼机密炼、扎轮机开炼和压延机压延的步骤，制备支撑层，然后将支撑层与预先制备好的平衡层、装饰层和任选存在的作为保护层衬底的聚氯乙烯层进行贴合、压花、然后进行渐进式冷却步骤，之后在线淋涂UV涂料形成保护层、经回火、在线成型制得聚氯乙烯地砖，其中
所述平衡层的制备工艺与支撑层的制备工艺相同，
所述装饰层通过在聚氯乙烯薄膜衬底上直接印刷或热转印图案而获得，
所述任选存在的作为保护层衬底的聚氯乙烯层和作为装饰层衬底的聚氯乙烯薄膜是通过把配方原料混合均匀、然后经挤出机塑化、再经压延机压延、之后冷却成型而制备的。
14.如权利要求13所述的制备硬质聚氯乙烯地砖的方法，其中所述将支撑层、平衡层、装饰层和保护层贴合的步骤是在制备支撑层的工艺步骤中在线完成的。
15.如权利要求13所述的制备硬质聚氯乙烯地砖的方法，其中所述将支撑层、平衡层、装饰层和保护层贴合的步骤是将制备好的上述各层在压延机上在130-145℃,40-80Kg压力下热压20-40分钟而完成的，其中支撑层是一层或多层。
16.如权利要求13-15任一项所述的制备硬质聚氯乙烯地砖的方法，其中所述渐进式冷却步骤包括将地砖温度逐段下降，第一段的温度为70-80℃，第二段的温度为40-50℃，第三段的温度为0-23℃。
17.如权利要求13-15任一项所述的制备硬质聚氯乙烯地砖的方法，其中所述回火温度为80-100℃，回火时间为1-10分钟。
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