CN103571322A - 防滑涂层材料及其制备、涂覆方法 - Google Patents

防滑涂层材料及其制备、涂覆方法 Download PDF

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CN103571322A
CN103571322A CN201210275481.8A CN201210275481A CN103571322A CN 103571322 A CN103571322 A CN 103571322A CN 201210275481 A CN201210275481 A CN 201210275481A CN 103571322 A CN103571322 A CN 103571322A
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nonskidcoating
acrylate
mixture
particle
methyl
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CN103571322B (zh
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孙美茹
薛茂谊
闫海龙
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PPG Coatings Tianjin Co Ltd
PPG Industries Ohio Inc
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PPG Industries Ohio Inc
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Priority to PL13825726T priority patent/PL2880109T3/pl
Priority to ES13825726.6T priority patent/ES2638662T3/es
Priority to EP13825726.6A priority patent/EP2880109B1/en
Priority to PCT/CN2013/080701 priority patent/WO2014019542A1/en
Priority to US14/419,304 priority patent/US10087334B2/en
Priority to TW102127990A priority patent/TWI619781B/zh
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Abstract

本发明涉及用于乙烯基地板的防滑涂层材料，所述防滑涂层材料采用PMU聚甲基脲作为防滑剂。本发明还涉及制备和涂覆所述防滑涂层材料的方法，利用所述防滑涂层材料得到的防滑涂层，其具有涂层厚度薄，防滑性能好的优点。

Description

防滑涂层材料及其制备、涂覆方法
技术领域
本发明涉及一种防滑涂层材料及其制备、涂覆方法，尤其是一种适用于乙烯基地板的防滑涂层材料及其制备、涂覆方法，以及由此得到的防滑涂层。
背景技术
近年来，乙烯基地板以性能优越、施工便捷、费用低廉等优点而广泛应用于家庭、商业和工业建筑中。通常要求其具有防滑功能，尤其当应用于走廊、楼梯、卫生间、洗手台、厨房、浴室、泳池、厂房等容易出现积水油污湿滑的场合。乙烯基地板的防滑功能通常通过在其表面涂覆防滑涂层来实现，目前市场上已有多种防滑涂层材料可供使用，但存在涂层较厚、防滑性能不高等缺点。
根据使用环境的要求，在一些情况下需要在防滑涂层材料中加入消光剂，降低涂层表面的光泽度，常见的消光剂包括超微细合成二氧化硅、微粉化蜡、铝、钙、镁、锌的硬脂酸盐等等。然而加入常规消光剂不会利于涂层的防滑性能。通常采用的防滑测试标准是德国DIN51130，目前常见的防滑涂层在DIN 51130测试中仅能达到R8-R9的水平，不能满足欧洲市场标准。因此需要提供一种能在DIN 51130测试中达到R10，甚至R11的防滑涂层。
PMU聚甲基脲是一种特殊的有机聚合物，具有高比表面积、低堆积密度的特点，在涂料行业中可用作消光剂，其具有消光效果显著、相对常规无机消光剂增稠不明显、且对触变性影响不大，除适合于溶剂型体系外还特别适合于水性体系、透明度高不吸收紫外线特别适用于UV固化体系的优点。本发明在防滑涂层中加入PMU聚甲基脲作为消光剂替代二氧化硅或者微粉化蜡不仅获得显著的消光效果，同时大幅提高了涂层的防滑性能，防滑性能优异。
发明内容
本发明的目的是提高用于乙烯基地板的防滑涂层，尤其是亚光防滑涂层的防滑性能，提供一种具有较高防滑性能的防滑涂层材料。
本发明的防滑涂层材料含有主体树脂、稀释剂、消光剂、防滑剂、光引发剂，和/或助剂。在本发明的防滑涂层材料中不含有溶剂。
本发明的防滑涂层材料的制备方法包括将将主体树脂、稀释剂、光引发剂和助剂在搅拌机中混合搅拌均匀得到混合物A；取部分量的消光剂和防滑剂，并取部分量的混合物A，在高速分散机中分散得到混合物B；取剩余量的消光剂和防滑剂，并取部分量的混合物A在高速分散机中分散得到混合物C；将剩余量的混合物A和得到的混合物B、C相混合得到最终防滑涂层材料。
本发明的防滑涂层材料的涂覆方法包括将防滑涂层材料涂覆在基材上；用红外照射处理防滑涂层材料；和通过紫外照射固化防滑涂层材料。
经检测，本发明的防滑涂层具有涂层厚度薄，防滑性能优异的特点。
具体实施方式
本发明的防滑涂层材料中采用PMU聚甲基脲颗粒材料替代现有防滑涂层中采用的大颗粒蜡材料，并任选地采用陶瓷微球颗粒作为辅助防滑颗粒。下文中的各成分含量，除特别注明之外，均以涂层材料总重量计算。
本发明的防滑涂层材料含有主体树脂、稀释剂、消光剂、防滑剂、光引发剂，和/或助剂。
所述主体树脂选自UV固化涂层材料中常用的主体树脂，包括但不限于聚酯丙烯酸酯和聚氨酯丙烯酸酯。优选为所述主体树脂是聚氨酯丙烯酸酯，更优选为所述主体树脂是脂肪族聚氨酯丙烯酸酯。脂肪族聚氨酯丙烯酸酯对PVC基材具有良好的附着力，兼具优异的硬度和柔韧性。所述主体树脂的含量为20-60%，优选为35-50%；
所述稀释剂是活性(甲基)丙烯酸酯，其包括选自杂环基(甲基)丙烯酸酯、双官能(甲基)丙烯酸酯和脂肪族(甲基)丙烯酸酯中的一种或多种。其中所述杂环基(甲基)丙烯酸酯可以选自四氢呋喃丙烯酸酯(THFA)、环三羟甲基丙烷甲缩醛丙烯酸酯(CTFA)或N-丙烯酰基吗啉(acrylmorpholide)，优选为所述杂环基(甲基)丙烯酸酯是四氢呋喃丙烯酸酯。所述双官能(甲基)丙烯酸酯可以选自二缩三丙二醇二丙烯酸酯(TPGDA)、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯(HDDA)、1,6-己二醇二甲基二丙烯酸酯(HDDMA)和二丙二醇二丙烯酸酯，优选为所述双官能(甲基)丙烯酸酯是二缩三丙二醇二丙烯酸酯。所述脂肪族(甲基)丙烯酸酯可以选自直链或支链的C8-C12烷基(甲基)丙烯酸酯，优选为所述脂肪族(甲基)丙烯酸酯是丙烯酸异癸酯。所述活性(甲基)丙烯酸酯作为稀释剂，用以稀释低聚物，参与光固化反应，对涂层材料的固化速度和固化涂层的柔韧性等各项性能有一定影响。所述稀释剂的含量为15-55%，优选为30-50%。
所述消光剂选自PMU聚甲基脲颗粒，其具有消光效果显著、增稠不明显、除适合于溶剂型体系外还特别适合于水性体系、透明度高不吸收紫外线特别适用于紫外固化体系的优点。所述PMU聚甲基脲颗粒具有50-200微米的平均分散粒径。所述PMU聚甲基脲的含量为3-25%，优选为8-15%。
所述光引发剂的种类和用量为本领域技术人员所公知，可以选自苯甲酮光引发剂、Irgacure 184、Irgacure 754、Irgacure 369、TPO、Darocur1173等本领域中所公知的光引发剂，其中Irgacure系列和Darocure系列是瑞士汽巴精化公司的产品，其产品型号为本领域技术人员所熟知。优选为所述光引发剂是一种或多种选自苯甲酮光引发剂、Darocure1173和Irgacure 754的光引发剂。所述光引发剂的含量为2-10％，优选为3-9%；
本发明的防滑涂层材料中还任选地含有陶瓷微球颗粒，其主要成分是二氧化硅，所述陶瓷微球颗粒也同时起到消光剂和防滑剂的作用。与PMU聚甲基脲用作主要消光剂和防滑剂相比，陶瓷微球颗粒起辅助作用，是辅助消光剂和辅助防滑剂。所述陶瓷微球颗粒具有3.5微米的D50平均粒径。所述陶瓷微球颗粒的含量为0.1-3%，优选为0.5-2%。
本发明的防滑涂层材料中还任选地含有助剂，所述助剂包括在UV固化涂层材料中常用的消泡剂、流平剂、润滑剂和分散剂中的一种或多种。所述助剂的种类和用量为本领域技术人员所公知，例如所述消泡剂可以选自EFKA2022、EFKA2527、BYK352、BYK354、AIREX910、AIREX920。其中EFKA系列是荷兰爱夫卡公司的产品，BYK系列是BYK公司的产品，AIREX系列是德国迪高公司的产品。所述助剂的含量为0.1-1%，优选为0.1-0.3%。
本发明的防滑涂层材料不含有溶剂，因此对人体的危害较小，火灾危险性较低，具有良好的环保性。
本发明的制备防滑涂层材料的方法包括：
a.将脂肪族聚氨酯(甲基)丙烯酸酯、活性(甲基)丙烯酸酯、光引发剂和助剂在搅拌机中混合搅拌均匀，得到混合物A；
b.取40-50%的所需重量的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲颗粒和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至赫格曼细度50-90微米，得到混合物B；
c.取剩余重量的的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲颗粒和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至至赫格曼细度大于90微米，得到混合物C。
d.将剩余的混合物A与上述步骤b和c中得到的混合物B和混合物C混合均匀，得到最终防滑涂层材料。
本发明的涂覆防滑涂层材料的方法包括：
a.将防滑涂层材料涂覆在基材上，涂覆量为6-35克/平方米的防滑涂层材料，优选为8-20克/平方米的防滑涂层材料；
b.用红外照射处理防滑涂层材料，照射温度通常为50-70℃，优选为60℃，照射时间通常为0.5-2分钟，优选为1分钟；和
c.通过紫外照射固化防滑涂层材料。
经计算，干燥后的本发明的防滑涂层材料具有6-35毫米的厚度，优选为具有8-20微米的厚度。经检测，本发明的防滑涂层具有优异的防滑性能。
实施例
实施例1：防滑涂层材料的制备
按照以下重量比例称取各种组分，以总重量计：
脂肪族聚氨酯丙烯酸酯      39%；
四氢呋喃丙烯酸酯          20.4%；
二缩三丙二醇二丙烯酸酯    8%；
丙烯酸异癸酯              9%；
PMU聚甲基脲颗粒           14%；
陶瓷微球颗粒              1%；
苯甲酮光引发剂            3.5%；
DAROCUR 1173              3%；
IRGACURE754               2%；和
消泡剂                    0.1%。
随后按照以下步骤进行混合制备防滑涂层材料，
a.将脂肪族聚氨酯丙烯酸酯、四氢呋喃丙烯酸酯、二缩三丙二醇二丙烯酸酯、丙烯酸异癸酯、光引发剂和消泡剂在搅拌机中混合搅拌均匀，得到混合物A；
b.取40-50%的所需重量的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲颗粒和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至赫格曼细度50-90微米，得到混合物B；
c.取剩余重量的的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至至赫格曼细度大于90微米，得到混合物C。
d.将剩余的混合物A和上述步骤b和c中得到的混合物B、混合物C混合均匀，得到最终防滑涂层材料。
实施例2：防滑涂层材料的制备
按照以下重量比例称取各种组分，以总重量计：
脂肪族聚氨酯丙烯酸酯            50%；
四氢呋喃丙烯酸酯                12.8%；
二缩三丙二醇二丙烯酸酯            9%；
丙烯酸异癸酯                      12%；
PMU聚甲基脲颗粒                   9%；
陶瓷微球颗粒                      2%；
苯甲酮光引发剂                    2%；
DAROCUR 1173                      2%；
IRGACURE754                       1%；和
消泡剂                            0.2%。
按照实施例1中描述的方法步骤制备防滑涂层材料。
实施例3：防滑涂层材料的制备
脂肪族聚氨酯丙烯酸酯              35%；
环三羟甲基丙烷甲缩醛丙烯酸酯      15%；
二缩三丙二醇二丙烯酸酯            15%；
丙烯酸异癸酯                      16.9%；
PMU聚甲基脲颗粒                   15%；
苯甲酮光引发剂                    2%；
DAROCUR 1173                      1%；和
消泡剂                            0.1%。
除了使用环三羟甲基丙烷甲缩醛丙烯酸酯替换四氢呋喃丙烯酸酯并且不使用陶瓷微球颗粒之外，按照实施例1中描述的方法步骤制备防滑涂层材料。
实施例4：防滑涂层材料的涂覆
将实施例1-3中制备得到的防滑涂层材料按照以下步骤进行涂覆干燥固化得到防滑涂层：
步骤1：将防滑涂层材料以8-20克/平方米的量涂覆在PVC地板上；
步骤2：于60℃，用红外照射处理防滑涂层材料1分钟；和
步骤3：通过紫外照射固化防滑涂层材料。
经计算，固化后的实施例1-3的防滑涂层材料具有8-20微米的厚度，并在DIN 51130测试中可以达到R10以上的标准。

Claims (10)

1.一种防滑涂层材料，其包括，以总重量计算的：
脂肪族聚氨酯(甲基)丙烯酸酯            20-60%；
活性(甲基)丙烯酸酯                    15-55%；
PMU聚甲基脲颗粒                       3-25%；和
光引发剂                              2-10%。
2.如权利要求1所述的防滑涂层材料，还包括
陶瓷微球颗粒                          0.1-3%；
助剂                                  0.1-1%。
3.如权利要求1所述的防滑涂层材料，其中所述PMU聚甲基脲颗粒具有50-200微米的平均分散粒径。
4.如权利要求1所述的防滑涂层材料，其中所述活性(甲基)丙烯酸酯包括选自杂环基(甲基)丙烯酸酯、双官能(甲基)丙烯酸酯和脂肪族(甲基)丙烯酸酯中的一种或多种。
5.如权利要求1所述的防滑涂层材料，其不包含溶剂。
6.一种制备防滑涂层材料的方法，所述制备方法包括：
a.将脂肪族聚氨酯(甲基)丙烯酸酯、活性(甲基)丙烯酸酯、光引发剂和助剂在搅拌机中混合搅拌均匀，得到混合物A；
b.取40-50%的所需重量的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲颗粒和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至赫格曼细度50-90微米，得到混合物B；
c.取剩余重量的的PMU聚甲基脲颗粒和陶瓷微球颗粒，以及取20%-50%重量的由步骤a得到的混合物A，在搅拌下将PMU聚甲基脲和陶瓷微球颗粒加入到混合物A中，并在分散机中分散至至赫格曼细度大于90微米，得到混合物C。
d.将剩余的混合物A和上述步骤b和c中得到的混合物B、混合物C混合均匀，得到最终防滑涂层材料。
7.一种涂覆基材的方法，所述涂覆方法包括：
a.将权利要求1的防滑涂层材料涂覆在基材上；
b.用红外照射处理防滑涂层材料；和
c.通过紫外照射固化防滑涂层材料。
8.如权利要求7所述的方法，其中所述基材是聚氯乙烯。
9.如权利要求7所述的方法，其中所述防滑涂层材料以6-35克/平方米的量涂覆到基材上。
10.如权利要求7所述的方法，其中所述经固化的防滑涂层材料具有6-35微米的厚度。
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CN106661349B (zh) * 2014-06-27 2019-05-28 陶氏环球技术有限责任公司 用于优化稀释乳液的Hegman等级的方法、通过该方法产生的稀释乳液以及由该稀释乳液制成的涂料
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CN107539589A (zh) * 2016-06-24 2018-01-05 孙力 一种防倾倒储物箱
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CN110885627A (zh) * 2019-12-20 2020-03-17 惠州市青蓝印材有限公司 一种apet滑爽可印刷加硬uv涂料
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WO2014019542A1 (en) 2014-02-06
PL2880109T3 (pl) 2018-01-31
TWI619781B (zh) 2018-04-01
US10087334B2 (en) 2018-10-02
CN103571322B (zh) 2015-12-09
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TW201412897A (zh) 2014-04-01
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