CN112622392B - 一种具有表面涂层的热塑性聚氨酯泡沫制品及其制备方法 - Google Patents
一种具有表面涂层的热塑性聚氨酯泡沫制品及其制备方法 Download PDFInfo
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Abstract
本发明泡沫制品的制备领域,具体的涉及一种具有表面涂层的热塑性聚氨酯泡沫制品及其制备方法。包括采用至少一种热塑性聚氨酯A制备的发泡粒子、采用至少一种热塑性聚氨酯B制备的薄膜和采用至少一种热塑性聚氨酯C制备的胶膜。热塑性聚氨酯A制备的发泡粒子用于制备获得成型制品,而热塑性聚氨酯B制备的薄膜贴合在成型制品上,得到具有表面涂层的热塑性聚氨酯泡沫制品。本泡沫制品的具有优异的拉伸强度,断裂伸长率等物理性能,并且比未在表面覆模的泡沫制品相比,具有改善的物理性能,本泡沫制品的光泽度以及耐磨性也得到改善。本发明的制备过程不需要使用有机溶剂,具有无环境污染问题且环保的特点。
Description
技术领域
本发明属于泡沫制品的制备领域,具体的涉及一种具有表面涂层的热塑性聚氨酯泡沫制品及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)具有较宽泛的硬度范围、优异的耐磨性、机械强度、耐水、耐油、耐化学腐蚀、耐霉菌,对环境友好和可回收利用等优点。目前通过将发泡热塑性聚氨酯粒子填充到模具中,利用水蒸气进行加热成型可得到模塑泡沫制品。此种制品在保留原基体优异的性能之外,同时拥有优异的回弹性、形状多样性、低密度和可以在较宽的温度范围内使用。基于上述优点,热塑性聚氨酯发泡粒子在许多工业领域(汽车工业、包装材料)以及日常生活领域(鞋材、枕头、床垫)具有非常广泛的应用前景。
目前在专利WO2007/082838A,CN103371564B,WO2010/136398A、CN102229709A、CN102276785A和CN103183805A中均报道了借助水蒸气模塑加工设备,利用水蒸气加热将热塑性聚氨酯发泡粒子熔结成泡沫制品,尤其是鞋底制品,所制备的泡沫制品具有优异的回弹性以及耐低温性能,例如具体应用于阿迪达斯boost系列产品中。另外,CN101583656A公开了一种含有聚氨酯的基体和包含在此基体中的热塑性聚氨酯发泡粒子的混合材料,其具有非常好的机械性能,例如与具有相同总体密度的类似材料相比,具有改进的弹性和更高的拉伸强度,例如应用于PUMA NAGY系列鞋子上。
但是,上述专利资料所公开的泡沫制品中发泡热塑性聚氨酯粒子在表面均是凸起的,并且颗粒之间容易存在缝隙,这样就导致最终制品表面不平整,并且粒子间的缝隙容易积存杂质和灰尘,造成清洗困难,尤其是应用于鞋底材料时。针对上述问题,虽然也提供了一些技术方案,但现有技术方案在施加涂层的过程中需要将热塑性聚氨酯颗粒溶解于有机溶剂中并继续后续的溶剂烘干操作,因而将导致环境污染等问题,另外由于CN101583656A此技术方案采用的是溶液涂覆工艺,为提高涂层与泡沫制品的界面粘结力,需要特定的涂层的结构与泡沫制品的结构组分,造成一定的使用受限。
发明内容
本发明为了解决上述背景技术中制品表面不平整,并且粒子间的缝隙容易积存杂质和灰尘,造成清洗困难的技术问题,提供一种表面平整,易清洗耐脏污并具有良好物理性能的成型制品的一种具有表面涂层的热塑性聚氨酯泡沫制品。
本发明解决上述技术问题的技术方案如下:一种具有表面涂层的热塑性聚氨酯泡沫制品,包括采用至少一种热塑性聚氨酯A制备的发泡粒子、采用至少一种热塑性聚氨酯B制备的薄膜和采用至少一种热塑性聚氨酯C制备的胶膜,其中:
所述热塑性聚氨酯A、所述热塑性聚氨酯B和所述热塑性聚氨酯C均包括多元醇、异氰酸酯和扩链剂。
本发明的有益效果是:热塑性聚氨酯A制备的发泡粒子用于制备获得成型制品,热塑性聚氨酯C制备的胶膜用于热塑性聚氨酯A制备的发泡粒子与热塑性聚氨酯B薄膜之间界面的粘结作用,即胶膜设置在所述发泡粒子和薄膜之间。所以热塑性聚氨酯B制备的薄膜贴合在发泡粒子制备的成型制品的表面上,得到具有表面涂层的热塑性聚氨酯泡沫制品。用于合成热塑性聚氨酯A、热塑性聚氨酯B和热塑性聚氨酯C的多元醇,异氰酸酯和扩链剂的种类可以相同或部分相同或全部不同。
本发明提供一种表面平整,易清洗耐脏污并具有良好物理性能的具有表面涂层的热塑性聚氨酯泡沫制品。本泡沫制品的具有优异的拉伸强度,断裂伸长率等物理性能,并且比未在表面覆模的泡沫制品相比,具有改善的物理性能。本发明的具有表面涂层的热塑性聚氨酯泡沫制品的光泽度以及耐磨性得到改善。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,所述多元醇为聚酯二元醇、聚醚二元醇或聚碳酸酯二元醇中的一种;所述异氰酸酯为二苯基甲烷-4,4’二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯或氢化苯基甲烷二异氰酸酯中的一种;所述扩链剂为脂肪族、芳香族或脂环族二醇化合物中的一种。
采用上述进一步方案的有益效果是,异氰酸酯为二苯基甲烷-4,4’二异氰酸酯、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯或氢化苯基甲烷二异氰酸酯中的一种,能够有效提升了本发明泡沫制品的品质。
多元醇优选摩尔质量为800-1200g/mol的聚酯多元醇与摩尔质量为500-2000g/mol聚醚多元醇,特别优选聚醚多元醇;其平均官能度为1.8-2.5,优选在1.9-2.0,特别优选为2。例如可以选取聚己二酸乙二醇酯二醇(PEA)、聚己二酸二甘醇酯二醇(PDA)、聚己二酸丁二醇酯二醇(PBA)、聚己二酸丙二醇酯二醇(PPA)、聚氧化丙烯二醇、聚四氢呋喃多元醇(PTMEG)中的一种。特别优选聚己二酸丁二醇酯二醇(PBA)或聚四氢呋喃多元醇(PTMEG)中的一种。
扩链剂为摩尔质量为50-500g/mol的脂肪族、芳香族或脂环族二醇化合物中的一种。例如乙二醇(EG)、1.4-丁二醇(BDO)、1,2-丙二醇(PG)、1,6-己二醇(HD)、氢醌双(2-羟乙基)醚(HQEE)、间苯二醇双(羟乙基)醚(HER)、一缩二丙二醇(DPG)、1,4-二羟甲基环己烷(CHDM)中的一种。特别优选1.4-丁二醇(BDO)。
进一步,所述热塑性聚氨酯A的邵氏硬度为70-90A。
采用上述进一步方案的有益效果是,其中邵氏硬度优选为75-88A,特别优选78-85A,邵氏硬度按照ASTM D2240测试得到。
进一步,所述热塑性聚氨酯B的邵氏硬度为65-95A。
采用上述进一步方案的有益效果是,其中邵氏硬度优选为70-90A,邵氏硬度按照ASTM D2240测试得到的。
进一步,所述热塑性聚氨酯C的起始软化温度小于等于120℃。
当热塑性聚氨酯C的起始软化温度高于120℃时,吸塑过程中需要更高的温度,势必导致热塑性聚氨酯A制备的发泡粒子出现收缩,密度增加的问题。所以当小于或等于120℃的时候,有利于产品成型。其中,起始软化温度是采用毛细管流变仪器(CFT-500EX/毛细管流变仪,岛津公司),从50℃按照5℃/min的升温速率升温至200℃,施加20kg的负载测试得到的。
进一步,所述热塑性聚氨酯C的数均分子量为50000-150000g/mol。
采用上述进一步方案的有益效果是,所述热塑性聚氨酯C的数均分子量是通过凝胶渗透色谱(GPC),以标准聚苯乙烯为标样测试得到的。
本发明为了解决现有技术中施工过程中容易造成环境污染的技术问题,提供了一种具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,包括以下步骤:
a、制备包含至少一种热塑性聚氨酯A的发泡粒子,制备包含至少一种热塑性聚氨酯B的薄膜和制备包含至少一种热塑性聚氨酯C的胶膜,将得到的所述薄膜和所述胶膜预热后复合在一起得到复合膜;
b、将步骤a中的发泡粒子投入到模具中,经过熔结或粘结成所需的形状得到成型制品;
c、将步骤a中制备的复合膜贴合在步骤b中制备的成型制品表面,得到具有表面涂层的热塑性聚氨酯泡沫制品。
本发明的有益效果是,本发明的制备方法在制备过程中不需要使用有机溶剂,无环境污染问题,具有环保的特点。解决了现有的容易造成环境污染的技术问题。制备工艺简单高效,得到的产品品质优良。
采用热塑性聚氨酯A制备发泡粒子的制备方法是本领域技术人员熟知的。发泡粒子可以通过釜压悬浮工艺或连续挤出水下切粒发泡工艺制备得到,具体的制备工艺记载在CN103709726A或CN103804889A中。其中本技术方案所采用的热塑性聚氨酯发泡粒子优选具有1-5mm的尺寸,密度优选具有0.1-0.25g/cm3,按照ASTM D792测试得到的。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,在步骤b中,所述熔结是通过水蒸气或电磁加热方式进行的。
采用上述进一步方案的有益效果是,熔结的具体步骤主要包括采用ETPU成型设备(Kurt生产)将热塑性聚氨酯发泡珠粒注入到成型模具中,合模压缩(厚度的10%),通入2-3bar压力的水蒸气是热塑性聚氨酯发泡珠粒表面适度熔化,然后冷却脱模得到泡沫制品。
进一步的,热塑性聚氨酯B制备薄膜的工艺可以选择采用流延工艺进行。
其中,优选的一个方案是将热塑性聚氨酯B颗粒、滑剂母粒、色母粒和功能性母粒(例如包括抗静电母粒,阻燃母粒等)按照一定的重量份比例投入混合设备如高混机中混合均匀,然后投入挤出流延设备中熔融塑化制备成薄膜状,该薄膜的厚度为0.01-0.5mm。其中,所述的各组分的重量比为:100重量份热塑性聚氨酯B颗粒、0.1-5重量份滑剂母粒、1-5重量份色母粒和0.1-5重量份的功能性母粒。
进一步的,热塑性聚氨酯C制备胶膜的工艺可以选择采用流延工艺,通常熔融塑化温度为100-200℃,通过模头挤出,同时将离型纸置于流延模头模唇两边,与热塑性聚氨酯C制备的胶膜一起通过压纹、冷却、裁边、收卷装置。
进一步的,在步骤a中,所述复合膜是通过所述薄膜和所述胶膜复合在一起,然后向其施加0.1-1bar的压力,接着升温至80-100℃保持1-10min,得到所述复合膜。
采用上述进一步方案的有益效果是,能够让复合膜的制备更加的顺利。
进一步,在步骤b中,所述熔结是通过水蒸气或电磁加热方式进行的,所述粘结是采用湿固化单组份聚氨酯作为粘结剂进行粘合。
采用上述进一步方案的有益效果是,将发泡粒子粘结在一起的合适方法是本领域技术人员熟知的,其中合适的粘结工艺方法记载于CN101583656或CN106626202A中。
进一步,在步骤c中,所述贴合是通过吸塑工艺进行的。
采用上述进一步方案的有益效果是,吸塑工艺采用现有吸塑工艺。
本发明的热塑性泡沫制品可以在热塑性聚氨酯B的薄膜上进一步包含一个印刷层,印制有各种纹理图案。所述印制印刷层的步骤可以采用本领域技术人员公知的方法进行,包括但不限于胶板印刷、丝网印刷、凸版印刷、凹板印刷、曲面印刷、渗透印刷、热转印等。
本发明还提供一种如上述所述的具有表面涂层的热塑性聚氨酯泡沫制品在作为鞋底、皮革、自行车座椅、沙发垫、汽车座椅、室内装饰品、缓冲垫、隔音垫、儿童玩具或地面覆盖物中作为制备材料的应用。
具有表面涂层的热塑性聚氨酯泡沫制品可以作为材料应用于鞋底、皮革、自行车座椅、沙发垫、汽车座椅、室内装饰品、缓冲垫、隔音垫、儿童玩具或地面覆盖物中。
具体实施方式
以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1、
本实施例的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,包括以下步骤:
a、制备包含至少一种热塑性聚氨酯A的发泡粒子,制备包含至少一种热塑性聚氨酯B的薄膜和制备包含至少一种热塑性聚氨酯C的胶膜,将得到的所述薄膜和所述胶膜复合在一起后经过加热得到复合膜;
b、将步骤a中的发泡粒子投入到模具中,经过熔结或粘结成所需的形状得到成型制品;
c、将步骤a中制备的复合膜贴合在步骤b中制备的成型制品表面,得到具有表面涂层的热塑性聚氨酯泡沫制品。
步骤a的具体制备过程如下:
1、制备包含热塑性聚氨酯A的发泡粒子
按照表1所示的各重量份和各组分投入双螺杆反应挤出机中生产热塑性聚氨酯弹性体颗粒,各组分重量份以及特性列在表1中。
表1
将100重量份表1所示的热塑性聚氨酯弹性体颗粒A-1或A-2、发泡剂和水加入到高压反应釜中形成悬浮液,然后升温至一定温度并保持一定的压力,将压力容器内的悬浮液排放到大气环境中,干燥处理,得到热塑性聚氨酯发泡粒子ETPU-1或ETPU-2,发泡工艺条件和所获得的弹性体发泡粒子的性能列在表2中。
表2
ETPU | 水(重量份) | 发泡剂 | 发泡剂(重量份) | 温度(℃) | 密度(g/cm3) |
1 | 200 | CO2 | 40 | 120 | 0.17 |
2 | 500 | 丁烷 | 25 | 80 | 0.1 |
2.制备含有热塑性聚氨酯B的薄膜
将100重量份基于分量为1000g/mol的聚四氢呋喃多元醇、丁二醇和MDI且邵氏硬度为80A的热塑性聚氨酯颗粒B,0.5重量份滑剂母粒,1重量份的色母粒,1重量份的抗静电母粒,1重量份的阻燃母粒投入高混机中混合3分钟,然后投入挤出流延机中,螺杆温度设定为100-200℃进行熔化塑化,熔体将口模挤出得到包含热塑性聚氨酯B的薄膜,薄膜厚度为0.1mm。
3.制备含有热塑性聚氨酯C的胶膜
将100重量份的热塑性聚氨酯C颗粒(牌号为Mirathane H570,购自美瑞新材料股份有限公司)投入流延设备,螺杆温度设定为150-180℃,通过模头挤出,同时将离型纸置于流延模头模唇两边,与热塑性聚氨酯C制备的胶膜一起通过压纹、冷却、裁边、收卷装置。
步骤b的具体操作过程如下:
1.制备复合膜
将包含热塑性聚氨酯C的胶膜平铺在包含热塑性聚氨酯B的薄膜表面,然后置于平板硫化机中,施加1bar的压力,然后升温至100℃并保持10分钟,然后去除压力并冷却至室温,得到复合膜。
2.含有热塑性聚氨酯A发泡粒子制备泡沫成型制品
一种优选方案是熔结成型:采用ETPU模塑设备,首先将模具预开一定的缝隙,采用压缩空气将上述发泡热塑性聚氨酯粒子ETPU-1或ETPU-2由料罐加压输送到10×10×10cm的模具中,然后闭合模具,接着向模具中引入水蒸气,按照设定的压力渐升曲线使水蒸气压力从初始值逐步升高至设定值并保持一定时间,水蒸气通入完毕后采用真空冷却水方式将模具温度将至70℃,最终通过开模通过模具顶杆将制品顶出,得到含有热塑性聚氨酯发泡粒子的泡沫制品S-1或S-2,具体的熔结成型工艺参数列于表3中。
表3
另一种优选方式是粘结成型:采用喷涂工艺将湿固化单组份聚氨酯胶(购自万化化学,6091)涂覆在热塑性聚氨酯发泡粒子表面ETPU1或ETPU2,然后将上述表面涂覆粘结剂的热塑性聚氨酯发泡粒子装填到制品模具中并置于平板硫化机中进行固化成型,最后将制品模具采用冷却水冷却至30℃,得到含有热塑性聚氨酯发泡粒子的泡沫制品A-1或A-2,各组分比例以及粘结固化工艺条件列在表4中。
表4
步骤C的具体操作过程如下:
首先将模具加热至80℃,将上述复合膜平铺到60℃的模具中,然后打开模具底部的真空泵开关,设定真空值为1pa,使复合膜紧密的与模具的模腔贴合在一起,薄膜表面平整无皱纹,随后将泡沫制品S-1放入模具中,模腔与泡沫制品S-1具有相同的形状,最后闭合模具,将模具升温至100℃,加热时间为1分钟后开模,得到表面具有薄膜的泡沫成型制品,及得到了具有表面涂层的热塑性聚氨酯泡沫制品。性能评价列于表5中。
实施例2、
实施例2与实施例1的区别在于,其中用泡沫制品S-2代替泡沫制品S-1。性能评价列于表5中。
实施例3、
实施例3与实施例1的区别在于,其中用泡沫制品A-1代替泡沫制品S-1。性能评价列于表5中。
实施例4、
实施例4与实施例1的区别在于,其中用泡沫制品A-2代替泡沫制品S-1。性能评价列于表5中。
对比实施例1、
对比实施例1与实施例1的区别在于,本对比实施例1未在模具中预先铺设上述由包含热塑性聚氨酯B的薄膜和包含热塑性聚氨酯C的胶膜组成的复合膜。
对比实施例2、
对比实施例2与实施例3的区别在于,本对比实施例2未在模具中预先铺设上述由包含热塑性聚氨酯B的薄膜和包含热塑性聚氨酯C的胶膜组成的复合膜。
对比实施例3、
对比实施例3与实施例1的区别在于,本对比实施例3在模具中预先铺设的是包含热塑性聚氨酯B的薄膜,而不是由包含热塑性聚氨酯B的薄膜和包含热塑性聚氨酯C的胶膜组成的复合膜。
对比实施例4、
对比实施例4与实施例3的区别在于,本对比实施例4在模具中预先铺设的是包含热塑性聚氨酯B的薄膜,而不是由包含热塑性聚氨酯B的薄膜和包含热塑性聚氨酯C的胶膜组成的复合膜。
表5
通过表5的对比数据可以看出,本发明所制备的表面具有涂层的热塑性聚氨酯泡沫制品相对于对比实施例1-4具有更加优异的拉伸强度,断裂伸长率以及撕裂强度,同时制品的表面光滑性,耐磨性能也得到提高。说明本发明的具有表面涂层的热塑性聚氨酯泡沫制品的品质优于现有产品。而且整个制备过程中不需要使用有机溶剂,无环境污染问题,具有环保的特点。在本说明书的描述中,术语“一个实施例”、“一些实施例”、“具体实施例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或实例。而且,描述的具体特征、结构、材料或特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种具有表面涂层的热塑性聚氨酯泡沫制品,其特征在于,包括采用至少一种热塑性聚氨酯A制备的发泡粒子、采用至少一种热塑性聚氨酯B制备的薄膜和采用至少一种热塑性聚氨酯C制备的胶膜,其中:
所述热塑性聚氨酯A、所述热塑性聚氨酯B和所述热塑性聚氨酯C均包括多元醇、异氰酸酯和扩链剂;
所述多元醇为聚酯二元醇、聚醚二元醇或聚碳酸酯二元醇中的一种;所述异氰酸酯为二苯基甲烷-4,4’二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯或氢化苯基甲烷二异氰酸酯中的一种;所述扩链剂为脂肪族、芳香族或脂环族二醇化合物中的一种;所述热塑性聚氨酯A的邵氏硬度为70-90A;所述热塑性聚氨酯B的邵氏硬度为65-95A;所述热塑性聚氨酯C的起始软化温度小于或等于120℃;所述热塑性聚氨酯C的数均分子量为50000-150000g/mol;
所述的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,包括以下步骤:
a、制备包含至少一种热塑性聚氨酯A的发泡粒子,制备包含至少一种热塑性聚氨酯B的薄膜和制备包含至少一种热塑性聚氨酯C的胶膜,将得到的所述薄膜和所述胶膜复合在一起后经过加热得到复合膜;
b、将步骤a中的发泡粒子投入到模具中,经过熔结或粘结成所需的形状得到成型制品;
c、将步骤a中制备的复合膜贴合在步骤b中制备的成型制品表面,得到具有表面涂层的热塑性聚氨酯泡沫制品。
2.一种如权利要求1所述的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,其特征在于,包括以下步骤:
a、制备包含至少一种热塑性聚氨酯A的发泡粒子,制备包含至少一种热塑性聚氨酯B的薄膜和制备包含至少一种热塑性聚氨酯C的胶膜,将得到的所述薄膜和所述胶膜复合在一起后经过加热得到复合膜;
b、将步骤a中的发泡粒子投入到模具中,经过熔结或粘结成所需的形状得到成型制品;
c、将步骤a中制备的复合膜贴合在步骤b中制备的成型制品表面,得到具有表面涂层的热塑性聚氨酯泡沫制品。
3.根据权利要求2所述的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,其特征在于,在步骤a中,所述复合膜是通过所述薄膜和所述胶膜复合在一起,然后向其施加0.1-1bar的压力,接着升温至80-100℃保持1-10min,得到所述复合膜。
4.根据权利要求2所述的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,其特征在于,在步骤b中,所述熔结是通过水蒸气或电磁加热方式进行的,所述粘结是采用湿固化单组份聚氨酯或热塑性聚氨酯弹性体热熔胶作为粘结剂进行粘合。
5.根据权利要求2至4任一项所述的具有表面涂层的热塑性聚氨酯泡沫制品的制备方法,其特征在于,在步骤c中,所述贴合是通过加热吸塑工艺进行的。
6.一种如权利要求1所述的具有表面涂层的热塑性聚氨酯泡沫制品在作为鞋底、皮革、自行车座椅、沙发垫、汽车座椅、室内装饰品、缓冲垫、隔音垫、儿童玩具或地面覆盖物中作为制备材料的应用。
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