CN105925167B - 一种触感油及使用该触感油的触感膜制备方法 - Google Patents

一种触感油及使用该触感油的触感膜制备方法 Download PDF

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CN105925167B
CN105925167B CN201610473255.9A CN201610473255A CN105925167B CN 105925167 B CN105925167 B CN 105925167B CN 201610473255 A CN201610473255 A CN 201610473255A CN 105925167 B CN105925167 B CN 105925167B
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oil
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CN105925167A (zh
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李英
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Shenzhen Lianchuang Industrial Co ltd
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Abstract

本发明提供了一种触感油及使用该触感油的触感膜制备方法,触感油的制备方法:将包含聚酯二元醇、聚醚二元醇的混合二元醇与异佛尔酮二异氰酸酯发生聚合反应,在催化剂作用下与亲水扩链剂、交联剂等进一步反应形成聚氨酯预聚体,预聚体在分散机中加去离子水乳化分散后,与纳米氧化铝水性溶液、流平剂、紫外吸收剂混合得到触感油。本发明还提供了一种使用该触感油的触感膜制备方法,该触感膜通过辊涂获得,涂层在烘道中充分固化,并在第三段进行充分结晶,使涂层热压后触感效果不消失。本发明制备的触感膜可用于汽车内饰板的热贴合,具有耐磨性好、透光率高、热压后触感不消失等优点,本发明提供的方法便于大规模生产,可以改善施工环境。

Description

一种触感油及使用该触感油的触感膜制备方法
技术领域
本发明属于功能性高分子薄膜技术领域,更具体地,涉及一种触感油及使用该触感油的触感膜制备方法。
背景技术
随着国内汽车工业的快速发展,越来越多的新材料被用于车内装饰。为了消除车内面板等装饰材料的反光带来的眩晕,工程技术人员采用了喷涂柔感涂料的方式,使汽车面板具有丝绸般的手感和柔和的光线反射功能。尽管研发人员尽量采取低毒性的溶剂,但仍给施工人员带来了危害,而且喷涂质量对最终产品影响较大,合格率较低。
触感膜也叫柔感膜,是一种表面有特殊丝绒光滑、细腻触感的贴合专用哑光膜。主要通过在薄膜表面涂布触感油实现,可用于奢侈品包装,高档书刊包装,高档吊牌等方面,具有耐摩擦、不留指纹印、有天鹅绒的手感等优点。但当触感膜用于高温、高压热贴合时,表面触感会在温度、压力作用下完全或部分消失,因此限制了触感膜的应用。
授权公告号为“CN103320004B”的发明专利公开了一种水性柔感哑油及其制作柔感膜的方法,该发明提供了一种解决柔感膜不耐磨,不具有柔软的手感效果的问题。该方法是以含有芳香族结构的水性聚氨酯分散体为主原料,通过加入消泡剂、交联剂等实现,在长时间光照下容易变黄,且该方法并未提供解决高温高压贴合后,触感消失的问题。授权公告号为“CN103589319B”的发明专利公开了一种机车内饰用聚氨酯柔感涂料及其制备方法,该发明以聚氨酯为主要成分,以混合有机物为溶剂,该方法获得的柔感涂料,可以使车内装饰具有丝绸般柔和的手感及高度防眩晕性。但该发明采用的有机溶剂气味较大,不利于施工。
发明内容
针对现有技术的缺点,本发明的主要目的在于提供一种触感油及使用该触感油的触感膜制备方法,采用该方案制备的触感膜热压贴合后触感不消失,具有耐磨性好、透光率高的优点,可用于车内装饰,减少工作环境的污染。
为达到以上目的,本发明采用的技术方案为:
本发明提供一种触感油的制备方法,包括以下步骤:
(1)将聚醚二元醇、聚酯二元醇在100℃-105℃条件下混合均匀,所述的聚醚二元醇包括平均分子量为3000-4000的聚氧化丙烯二醇和聚四氢呋喃二醇,聚酯二元醇为分子量为3500-4500的聚己内酯二元醇,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇10%-15%、聚四氢呋喃二醇5%-10%、聚己内酯二元醇75%-85%;在100℃-105℃下抽真空1-2小时,除去混合二元醇中的水分;
(2)降温至85℃-90℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2-3小时,加入量为混合二元醇重量的30%-45%,降温至60℃-70℃,加入亲水扩链剂、交联剂、催化剂反应2-3小时,得到水性聚氨酯预聚物,所述亲水扩链剂为1,2-二羟基-3-丙磺酸钠、交联剂为三羟甲基丙烷、催化剂为辛酸亚锡,加入量分别为异佛尔酮二异氰酸酯重量的3%-4%、2%-3%、1%-2%;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的80%-100%,分散机转速为3000-4000转/分钟、时间15-20分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂、紫外吸收剂按重量比为100:10-13:2-3:1-2:0.5-1混合均匀,得到所述触感油。
所述纳米氧化铝水性溶液中纳米氧化铝含量为50%-55%,粒径为3-7纳米;
所述流平剂为DC-62或BYK-333;
所述紫外吸收剂为2-羟基-4-正辛氧基二苯甲酮。
相应的本发明还提供了一种使用所述触感油制备触感膜的方法,包括以下步骤:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.5-0.6微米细砂辊,基膜为BOPP、BOPET、PC膜中的一种;
(2)对涂层进行固化,烘道固化温度分为三段,第一段60℃-75℃、第二段80℃-85℃、第三段65℃-70℃,其中在第三段中停留时间为60秒-80秒;
(3)收卷、分切得到触感膜。
有益效果:
本发明提供一种触感油制备方法,与现有技术相比,本发明采用了三种二元醇混合物作为软链段,分子链规整,具有较好的结晶性;以异佛尔酮二异氰酸酯作为硬链段进行扩链不仅使分子链形成物理交联点,还使触感涂层的耐黄变性提高,软链段与硬链段形成了相分离,使触感涂层在受热、压力状况下具有良好的回复性。
采用1,2-二羟基-3-丙磺酸钠作为亲水扩链剂,可以阻止胶粒的团聚,使触感油具有较高的固含量及较小的黏度,有利于后续的涂布。
采用纳米氧化铝水性溶液作为填料,与聚氨酯相容性好,可以使涂层具有较好的消光性、爽滑性及耐磨性。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。
本发明提供一种触感油的制备方法,包括以下步骤:
(1)将聚醚二元醇、聚酯二元醇在100℃-105℃条件下混合均匀,所述的聚醚二元醇包括平均分子量为3000-4000的聚氧化丙烯二醇和聚四氢呋喃二醇,聚酯二元醇为分子量为3500-4500的聚己内酯二元醇,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇10%-15%、聚四氢呋喃二醇5%-10%、聚己内酯二元醇75%-85%;在100℃-105℃下抽真空1-2小时,除去混合二元醇中的水分。采用三种二元醇混合使用,既有聚醚型也有聚酯型,可以使软链段结晶度能够达到35%-45%,并且玻璃化转变温度在65℃-70℃,软链段具有可回复性;
(2)降温至85℃-90℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2-3小时,加入量为混合二元醇重量的30%-45%,降温至60℃-70℃,加入亲水扩链剂、交联剂、催化剂反应2-3小时,得到水性聚氨酯预聚物,所述亲水扩链剂为1,2-二羟基-3-丙磺酸钠、交联剂为三羟甲基丙烷、催化剂为辛酸亚锡,加入量分别为异佛尔酮二异氰酸酯重量的3%-4%、2%-3%、1%-2%。异佛尔酮二异氰酸酯不含有苯环,具有耐黄变性,作为分子链中的硬链段,可以支撑触感涂层微观结构的稳定,与软链段形成相分离结构,从而使触感涂层在热、压力作用下触感效果不损失;1,2-二羟基-3-丙磺酸钠是一种磺酸盐型扩链剂,与聚氨酯反应后,会提高聚氨酯的亲水性,但由于用量少,胶粒上电荷少,可以减弱胶粒的团聚,从而使触感油在低黏度条件下具有较高的固含量,有利于涂布生产;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的80%-100%,分散机转速为3000-4000转/分钟、时间15-20分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂、紫外吸收剂按重量比为100:10-13:2-3:0.5-1混合均匀,得到所述触感油。
所述纳米氧化铝水性溶液是将表面亲水改性的纳米氧化铝溶于水中形成的透明溶液,具有分散性好,不团聚等优点,本发明使用的纳米氧化铝水性溶液中纳米氧化铝含量优选为50%-55%,粒径为3-7纳米;
所述流平剂用来改善涂层表面张力,避免涂层产生缩孔,同时不会使涂层表面光泽产生变化,本发明优选为DC-62或BYK-333;
所述紫外吸收剂为淡黄色粉末,可吸收波长在300-375纳米的紫外光,易溶解于聚氨酯溶液中,本发明优选为2-羟基-4-正辛氧基二苯甲酮。
相应的,本发明还提供了一种使用所述触感油制备触感膜的方法,包括以下步骤:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.5-0.6微米细砂辊,基膜为BOPP、BOPET、PC膜中的一种。使用细砂辊可以促进涂布过程中触感油中的纳米氧化铝的分散,起到研磨作用,本发明优先为粗糙度0.5-0.6微米细砂辊;涂布过程中采用的基膜要具有一定耐热性,涂布过程中不变形,本发明优选基膜为BOPP、BOPET、PC膜中的一种;
(2)对涂层进行固化,烘道固化温度分为三段,第一段60℃-75℃、第二段80℃-85℃、第三段65℃-70℃,其中在第三段中停留时间为60秒-80秒。分三段固化可以使水等低分子充分脱除,形成稳定的触感涂层,第三段温度设定在65℃-70℃、时间为60秒-80秒,可以使聚氨酯硬链段、软链段充分结晶、形成相分离结构,使触感涂层在热、压力作用下触感效果不损失;
(3)收卷、分切得到触感膜。
为了进一步理解本发明,下面结合实施例对本发明提供的技术方案进行详细说明,本发明的保护范围不受以下实施例的限制。
本发明下述实施例中所使用的聚氧化丙烯二醇、聚四氢呋喃二醇、聚己内酯二元醇由万华化学集团股份有限公司提供。
本发明下述实施例中所使用的异佛尔酮二异氰酸酯来自武汉市环球化工有限公司。
本发明下述实施例中所使用的亲水扩链剂来自苏州贝克生物科技有限公司。
本发明下述实施例中所使用的交联剂来自淄博鑫瑞化工有限公司。
本发明下述实施例中所使用的催化剂来自江苏雅克化工科技股份有限公司。
本发明下述实施例中所使用的纳米氧化铝水性溶液来自上海沪正纳米科技有限公司。
本发明下述实施例中所使用的流平剂来自于德国毕克化学。
本发明下述实施例中所使用的紫外吸收剂来自于上海海曲化工有限公司。
本发明下述实施例中所使用的BOPP膜来自于宿迁金田集团。
为了便于计量,实施例中的混合二元醇总重量统一为100KG
实施例1
触感油的制备:
(1)将聚氧化丙烯二醇、聚四氢呋喃二醇、聚己内酯二元醇在100℃条件下混合均匀,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇10%、聚四氢呋喃二醇5%、聚己内酯二元醇85%;在100℃下抽真空2小时,除去混合二元醇中的水分;
(2)降温至85℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应3小时,加入量为混合二元醇重量的45%,降温至60℃,加入亲水扩链剂1,2-二羟基-3-丙磺酸钠、交联剂三羟甲基丙烷、催化剂辛酸亚锡反应3小时,得到水性聚氨酯预聚物,加入量分别为异佛尔酮二异氰酸酯重量的3%、2%、1%;
(3)降温至20℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的80%,分散机转速为3000转/分钟、时间20分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂BYK-333、紫外吸收剂2-羟基-4-正辛氧基二苯甲酮按重量比为100:10:2:0.5混合均匀,得到所述触感油。
触感膜的制备:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.5微米细砂辊,基膜为BOPP膜;
(2)对涂层进行固化,烘道固化温度分为三段,第一段60℃、第二段80℃、第三段65℃,其中在第三段中停留时间为80秒;
(3)收卷、分切得到触感膜。
实施例2
触感油的制备:
(1)将聚氧化丙烯二醇、聚四氢呋喃二醇、聚己内酯二元醇在105℃条件下混合均匀,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇15%、聚四氢呋喃二醇10%、聚己内酯二元醇75%;在105℃下抽真空1小时,除去混合二元醇中的水分;
(2)降温至90℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2小时,加入量为混合二元醇重量的30%,降温至70℃,加入亲水扩链剂1,2-二羟基-3-丙磺酸钠、交联剂三羟甲基丙烷、催化剂辛酸亚锡反应2小时,得到水性聚氨酯预聚物,加入量分别为异佛尔酮二异氰酸酯重量的4%、3%、2%;
(3)降温至30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的100%,分散机转速为4000转/分钟、时间15分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂BYK-333、紫外吸收剂2-羟基-4-正辛氧基二苯甲酮按重量比为100:13:3:1混合均匀,得到所述触感油。
触感膜的制备:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.6微米细砂辊,基膜为BOPP膜;
(2)对涂层进行固化,烘道固化温度分为三段,第一段75℃、第二段85℃、第三段70℃,其中在第三段中停留时间为60秒;
(3)收卷、分切得到触感膜。
实施例3
触感油的制备:
(1)将聚氧化丙烯二醇、聚四氢呋喃二醇、聚己内酯二元醇在102℃条件下混合均匀,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇12%、聚四氢呋喃二醇8%、聚己内酯二元醇80%;在102℃下抽真空1.5小时,除去混合二元醇中的水分;
(2)降温至88℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2.5小时,加入量为混合二元醇重量的40%,降温至65℃,加入亲水扩链剂1,2-二羟基-3-丙磺酸钠、交联剂三羟甲基丙烷、催化剂辛酸亚锡反应2-3小时,得到水性聚氨酯预聚物,加入量分别为异佛尔酮二异氰酸酯重量的3.5%、2.5%、1.5%;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的90%,分散机转速为3500转/分钟、时间18分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂BYK-333、紫外吸收剂2-羟基-4-正辛氧基二苯甲酮按重量比为100:11:2.5:0.8混合均匀,得到所述触感油。
触感膜的制备:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.55微米细砂辊,基膜为BOPP膜;
(2)对涂层进行固化,烘道固化温度分为三段,第一段70℃、第二段82℃、第三段68℃,其中在第三段中停留时间为70秒;
(3)收卷、分切得到触感膜。
实施例4
触感油的制备:
(1)将聚氧化丙烯二醇、聚四氢呋喃二醇在102℃条件下混合均匀,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇12%、聚四氢呋喃二醇88%;在102℃下抽真空1.5小时,除去混合二元醇中的水分;
(2)降温至88℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2.5小时,加入量为混合二元醇重量的40%,降温至65℃,加入亲水扩链剂1,2-二羟基-3-丙磺酸钠、交联剂三羟甲基丙烷、催化剂辛酸亚锡反应2-3小时,得到水性聚氨酯预聚物,加入量分别为异佛尔酮二异氰酸酯重量的3.5%、2.5%、1.5%;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的90%,分散机转速为3500转/分钟、时间18分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂BYK-333、紫外吸收剂2-羟基-4-正辛氧基二苯甲酮按重量比为100:11:2.5:0.8混合均匀,得到所述触感油。
触感膜的制备:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.55微米细砂辊,基膜为BOPP膜;
(2)对涂层进行固化,烘道固化温度分为三段,第一段70℃、第二段82℃、第三段68℃,其中在第三段中停留时间为70秒;
(3)收卷、分切得到触感膜。
实施例5
触感油的制备:
(1)将聚氧化丙烯二醇、聚四氢呋喃二醇、聚己内酯二元醇在102℃条件下混合均匀,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇12%、聚四氢呋喃二醇8%、聚己内酯二元醇80%;在102℃下抽真空1.5小时,除去混合二元醇中的水分;
(2)降温至88℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2.5小时,加入量为混合二元醇重量的40%,降温至65℃,加入亲水扩链剂1,2-二羟基-3-丙磺酸钠、交联剂三羟甲基丙烷、催化剂辛酸亚锡反应2-3小时,得到水性聚氨酯预聚物,加入量分别为异佛尔酮二异氰酸酯重量的3.5%、2.5%、1.5%;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物的90%,分散机转速为3500转/分钟、时间18分钟;
(4)将水性聚氨酯分散体、流平剂BYK-333、紫外吸收剂2-羟基-4-正辛氧基二苯甲酮按重量比为100:2.5:0.8混合均匀,得到所述触感油。
触感膜的制备:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.55微米细砂辊,基膜为BOPP膜;
(2)对涂层进行固化,烘道固化温度分为三段,第一段70℃、第二段82℃、第三段68℃,其中在第三段中停留时间为70秒;
(3)收卷、分切得到触感膜。
分别对本发明实施例1-5的触感油进行检测,结果如表1所示。
表1 本发明实施例1-5制备的触感油性能测试结果
测试项目 单位 实施例1 实施例2 实施例3 实施例4 实施例5
黏度 mpa.s 20.3 20.6 20.5 21 26.6
固含量 % 53 51 52 53 54
注释:测试条件为23℃、湿度30%。
分别对本发明实施例1-5的触感膜进行检测,结果如表2所示。
表2 本发明实施例1-5制备的触感膜性能测试结果
测试项目 单位 依据标准 实施例1 实施例2 实施例3 实施例4 实施例5
透光率 % GB/T2410 89 89 89 89 89
光泽度 GB/T8807 6.7 6.5 6.2 6.9 12.6
耐磨性 HG/T4303 3000 3100 3140 3060 2180
热压后触感效果 无明显变化 无明显变化 无明显变化 触感消失 无明显变化
从表1测试结果可以看出本发明制备的触感油固含量较高,但黏度不大,适于涂布使用;实施例5的黏度有所提升主要是因为未加入纳米氧化铝溶液,而纳米氧化铝可以降低体系的黏度。
从表2实施例1-3测试结果可以看出采用本发明提供的触感油制备的触感膜具有高透光率、低光泽度、较好的耐磨性,热压后触感不消失。实施例4由于未使用聚己内酯二元醇,导致聚氨酯软链段结构不规整,结晶度不够,产生的触感效果热压后消失。实施例5测试结果可以看出,纳米氧化铝的加入可以提高触感涂层的耐磨性并降低涂层光泽度。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。

Claims (2)

1.一种触感油制备方法,其特征在于,包括以下步骤:
(1)将聚醚二元醇、聚酯二元醇在100℃-105℃条件下混合均匀,所述的聚醚二元醇包括平均分子量为3000-4000的聚氧化丙烯二醇和平均分子量为3000-4000的聚四氢呋喃二醇,聚酯二元醇为分子量为3500-4500的聚己内酯二元醇,三种原料在混合二元醇中重量占比为聚氧化丙烯二醇10%-15%、聚四氢呋喃二醇5%-10%、聚己内酯二元醇75%-85%;在100℃-105℃下抽真空1-2小时,除去混合二元醇中的水分;
(2)降温至85℃-90℃,在氮气保护情况下加入异佛尔酮二异氰酸酯反应2-3小时,加入量为混合二元醇重量的30%-45%,降温至60℃-70℃,加入亲水扩链剂、交联剂、催化剂反应2-3小时,得到水性聚氨酯预聚物,所述亲水扩链剂为1,2-二羟基-3-丙磺酸钠、交联剂为三羟甲基丙烷、催化剂为辛酸亚锡,加入量分别为异佛尔酮二异氰酸酯重量的3%-4%、2%-3%、1%-2%;
(3)降温至20℃-30℃,加入去离子水用分散机进行分散,得到水性聚氨酯分散体,所述去离子水用量为水性聚氨酯预聚物质量的80%-100%,分散机转速为3000-4000转/分钟、时间15-20分钟;
(4)将水性聚氨酯分散体、纳米氧化铝水性溶液、流平剂、紫外吸收剂按重量比为100:10-13:2-3:0.5-1混合均匀,得到所述触感油;
所述纳米氧化铝水性溶液中纳米氧化铝质量百分比为50%-55%,粒径为3-7纳米;
所述流平剂为DC-62或BYK-333;
所述紫外吸收剂为2-羟基-4-正辛氧基二苯甲酮。
2.一种使用权利要求1所述触感油的触感膜的制备方法,其特征在于,包括以下步骤:
(1)将触感油加入胶槽,通过涂布刚辊将触感油转移到基膜上,其中刚辊为表面镀铬的表面粗糙度为0.5-0.6微米细砂辊,基膜为BOPP、BOPET、PC膜中的一种;
(2)对涂层进行固化,烘道固化温度分为三段,第一段60℃-75℃、第二段80℃-85℃、第三段65℃-70℃,其中在第三段中停留时间为60秒-80秒;
(3)收卷、分切得到触感膜。
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