CN105619968A - 一种环保耐候耐污墙纸及制作方法 - Google Patents

一种环保耐候耐污墙纸及制作方法 Download PDF

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Publication number
CN105619968A
CN105619968A CN201610122444.1A CN201610122444A CN105619968A CN 105619968 A CN105619968 A CN 105619968A CN 201610122444 A CN201610122444 A CN 201610122444A CN 105619968 A CN105619968 A CN 105619968A
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China
Prior art keywords
proof
wallpaper
polysiloxane
environment
friendlyweather
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Pending
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CN201610122444.1A
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English (en)
Inventor
黄胜
谢朝辉
杨家昌
吴长林
焦冬生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Sailirone New Material Co Ltd
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Huizhou Sailirone New Material Co Ltd
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Application filed by Huizhou Sailirone New Material Co Ltd filed Critical Huizhou Sailirone New Material Co Ltd
Priority to CN201610122444.1A priority Critical patent/CN105619968A/zh
Publication of CN105619968A publication Critical patent/CN105619968A/zh
Priority to PCT/CN2016/105893 priority patent/WO2017148181A1/zh
Priority to US15/917,468 priority patent/US20180195234A1/en
Priority to US17/259,568 priority patent/US20210268447A1/en
Pending legal-status Critical Current

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Abstract

本发明公开了一种环保耐候耐污墙纸及制作方法，包括复合连接在一起的基材层和有机硅橡胶层。通过压延贴胶-压花-硫化工艺即可制备出该墙纸，此工艺简单且可连续生产，效率高，整个过程无有害物质无污染物，制备的有墙纸环保无毒，且可赋予墙纸优异的耐候防污防火防潮防霉性能。

Description

一种环保耐候耐污墙纸及制作方法
技术领域
本发明涉及一种环保耐候耐污的墙纸及制作方法，属于墙纸技术领域。
背景技术
墙纸是一种应用相当广泛的室内装饰材料。目前国内大多数墙纸材料生产或使用中都会使用用各种化学助剂：甲苯、环己酮、丙酮、汽油和醋酸丁酯为溶剂，并加以重金属盐等助剂，这些化学助剂即使在成品墙纸中仍会有大量残留，其会对周围环境不断释放出刺激性气体和致癌物质，对人体和环境造成持续性危害。
有机硅材料具有优异的耐高低温性能，耐候性，防污性，防水性，阻燃性，电气绝缘性以及生理惰性等并且对人体及环境友好，已广泛应用于航空航天，电子电气，建筑，汽车机械等工业以及医疗卫生，日常生活的各个领域。但还未有将有机硅应用于制造墙纸的报道。
发明内容
本发明针对上述问题的不足，提出一种对环境友好、对人体无害、且具有耐候、防水、防污、防火的环保耐候耐污墙纸及制作方法。
本发明为解决上述技术问题提出的技术方案是：
一种环保耐候耐污墙纸，包括复合连接在一起的基材层和有机硅橡胶层。
优选的：所述有机硅橡胶层的厚度在0.1-1mm。
优选的：所述基材层为纸胚，纺织布，或其它卷材。
优选的：所述有机硅橡胶层通过将有机硅原胶料原料设置在基材层上形成，所述有机硅胶料包括乙烯基聚硅氧烷生胶、填料、结构控制剂、塑炼剂、含氢硅油、铂催化剂以及延迟剂。
优选的：所述有机硅胶料的组分及质量配比如下：
乙烯基聚硅氧烷生胶90-110份
填料40-100份
结构控制剂1-15份
塑炼剂0.0001-2份
含氢硅油0.001-10份
铂催化剂0.0005-5份
延迟剂0.001-5份
色浆0-20份
功能性助剂0-30份。
优选的：所述乙烯基聚硅氧烷生胶为至少两个乙烯基直接与Si相连的聚硅氧烷，且其中的聚硅氧烷的链端或侧链含有乙烯基，或链端与侧链同时含有乙烯基。
所述填料为气相法白炭黑、沉淀法白炭黑、硅树脂、硅微粉、碳酸钙、铝硅酸盐、硅澡土、石墨烯、氧化铝、氢氧化铝、氢氧化镁、二氧化钛中的一种或多种的混合物。
所述结构控制剂为羟基或烷氧基封端小分子硅油、六甲基二硅氮烷、二乙烯基四甲基二硅氮烷、二苯基二羟基硅烷、烃基烷氧基硅烷中的一种或两种以上的混合物，其中羟基或烷氧基封端小分子硅油在25℃的粘度为5-100mm2/s，其中烃基烷氧基硅烷为二甲基二甲氧基硅烷、二乙基二甲氧基硅烷或者为二甲基二乙氧基硅烷。
所述塑炼剂为高级脂肪醇、高级脂肪酸及其金属盐、高级脂肪酸酯中的一种或两种以上的混合物，所述高级脂肪酸酯为硬脂酸、硬脂酸锌、十二醇、硬脂酸钙或者为硬酯酸甘油酯。
所述含氢聚硅氧烷为至少有3个氢原子与Si直接相连的聚硅氧烷，所述氢原子位于该聚硅氧烷链端或侧链，或链两端与侧链同时含有与Si直接相连的氢原子，所述氢原子含量为0.1～1.6％；所述含氢聚硅氧烷为直链状、枝状、环状的聚硅氧烷中的一种或多种的混合物。
所述铂催化剂为氯铂酸异丙醇溶液、氯铂酸四氢呋喃溶液、氯铂酸-二乙烯基四甲基二硅氧烷配合物、氯铂酸-1、3、5、7-四乙烯基-1、3、5、7-四甲基-环四硅氧烷中的一种或两种以上的混合物，所述铂催化剂中Pt原子的含量为100～500000ppm。
所述延迟剂为甲基丁炔醇、乙炔基环己醇、含炔基的马来酸或其衍生物、含炔基的富马来酸或其衍生物、多乙烯基聚硅氧烷、吡啶、不饱和酰胺类、有机膦或亚磷酸酯中的一种或两种以上的混合物。
所述色浆为以聚硅氧烷为分散介质的颜料。最优为以含乙烯基的聚硅氧为分散介质。
所述功能性助剂为抗静电剂、防霉剂、抗菌剂、导电填料、阻燃剂、夜光粉中的一种或多种的混合物。
优选的：所述乙烯基聚硅氧烷生胶的分子量为55-80万，且其中的乙烯基含量0.01-2％。
一种环保耐候耐污墙纸的制作方法，将有机硅胶料设置在基材层上形成有机硅橡胶层，经压花及硫化，进而得到墙纸。
具体包括以下步骤：
步骤1，配制有机硅胶料。
步骤2，将有机硅胶料与基材进行压延贴合。
步骤3，对压延贴合后的材料进行压花压印得到墙纸花纹。
步骤4，对压花压印后的材料在120-180℃下硫化5-15分钟即得成品墙纸。
本发明的一种环保耐候耐污墙纸及制作方法，相比现有技术，具有以下有益效果：
1.本发明的墙纸由复合连接在一起的基材层和有机硅橡胶层的组成，因此墙纸具有安全环保、对人体无害，耐候，防水，防污，防霉，防火特性。
2.将有机硅胶料设置在基材层上形成有机硅橡胶层，经压花及硫化，进而得到墙纸，制作工艺简单环保安全高效，整个过程无有害物释放，因此其制作工艺安全环保，制成的墙纸对人体无害。
附图说明
图1是本发明制作工艺示意图。
其中，1为基材，2为压延辊，3为固态胶，4为压花辊，5为烘道。
具体实施方式
附图非限制性地公开了本发明一个优选实施例的结构示意图，以下将结合附图详细地说明本发明的技术方案。
实施例1
本实施例的一种环保耐候耐污墙纸，包括复合连接在一起的基材层和有机硅橡胶层。所述有机硅橡胶层的厚度在0.1-1mm。
所述基材层为纸胚，纺织布或其它卷材。
所述有机硅橡胶层通过将有机硅胶料设置在基材层上形成，所述有机硅胶料包括乙烯基聚硅氧烷生胶、填料、结构控制剂、塑炼剂、含氢硅油、铂催化剂以及延迟剂。
所述乙烯基聚硅氧烷生胶为至少两个乙烯基直接与Si相连的聚硅氧烷，且其中聚硅氧烷的链端或侧链含有乙烯基，或链端与侧链同时含有乙烯基。所述乙烯基聚硅氧烷生胶的分子量为55-80万，且其中的乙烯基含量0.01-2％。
所述填料为气相法白炭黑、沉淀法白炭黑、硅树脂、硅微粉、碳酸钙、铝硅酸盐、硅澡土、石墨烯、氧化铝、氢氧化铝、氢氧化镁、二氧化钛中的一种或多种的混合物。
所述结构控制剂羟基或烷氧基封端小分子硅油、六甲基二硅氮烷、二乙烯基四甲基二硅氮烷、二苯基二羟基硅烷、烃基烷氧基硅烷中的一种或两种以上的混合物，其中羟基或烷氧基封端小分子硅油在25℃的粘度为5-100mm2/s，其中烃基烷氧基硅烷为二甲基二甲氧基硅烷、二乙基二甲氧基硅烷或者为二甲基二乙氧基硅烷。
所述塑炼剂为高级脂肪醇、高级脂肪酸及其金属盐、高级脂肪酸酯中的一种或两种以上的混合物，所述高级脂肪酸酯为硬脂酸、硬脂酸锌、十二醇、硬脂酸钙或者为硬酯酸甘油酯。
所述含氢聚硅氧烷为至少有3个氢原子与Si直接相连的聚硅氧烷，所述氢原子位于该聚硅氧烷的链端或侧链，或链两端也同时含有与Si直接相连的氢原子，所述氢原子含量为0.1～1.6％；所述含氢聚硅氧烷为直链状、枝状、环状的聚硅氧烷中的一种或多种的混合物。
所述铂催化剂为氯铂酸异丙醇溶液、氯铂酸四氢呋喃溶液、氯铂酸-二乙烯基四甲基二硅氧烷配合物、氯铂酸-1、3、5、7-四乙烯基-1、3、5、7-四甲基-环四硅氧烷中的一种或两种以上的混合物，所述铂催化剂中Pt原子的含量为100～500000ppm。
所述延迟剂为甲基丁炔醇、乙炔基环己醇、含炔基的马来酸或其衍生物、含炔基的富马来酸或其衍生物、多乙烯基聚硅氧烷、吡啶、不饱和酰胺类、有机膦或亚磷酸酯中的一种或两种以上的混合物。
所述色浆为以聚硅氧烷为分散介质的颜料。色浆为选择性添加物，方便制作不同颜色的墙纸，以含乙烯基的聚硅氧烷为分散介质为最佳。
所述功能性助剂为抗静电剂、防霉剂、抗菌剂、导电填料、阻燃剂、夜光粉中的一种或多种的混合物。
本实施例的有机硅胶料采用以下组分及质量配比：
乙烯基聚硅氧烷生胶：分子量为60万且乙烯基含量0.05％的乙烯基聚硅氧烷生胶50KG，分子量为60万且乙烯基含量0.5％的乙烯基聚硅氧烷生胶50KG
填料：白碳黑(A200)50KG
结构控制剂：短链羟基硅油4.5KG
塑炼剂：硬酯酸甘油酯0.25KG
经混炼后加入
含氢硅油(氢含量1.6％，黏度50)3.5KG
延迟剂：乙炔基环己醇0.007KG
铂催化剂(30000ppm)0.035KG
色浆5KG
功能性助剂：防霉剂0.5KG配制成有机硅胶料
一种环保耐候耐污墙纸的制作方法，如图1所示，将有机硅胶料设置在基材层上形成有机硅橡胶层，经压花及硫化，进而得到墙纸。
具体包括以下步骤：
步骤1，配制上述有机硅胶料
步骤2，将有机硅胶料通过压延辊2与纸胚1压延贴合，调整压延厚度为0.5mm，得到的有机硅橡胶层厚度为0.5mm，通过调整压延厚度即可得到不同厚度的有机硅橡胶层，在本发明的另一实施例中，调整压延厚度为0.15mm，得到的有机硅橡胶层厚度为0.15mm，在又另一实施例中，调整压延厚度为1mm，得到的有机硅橡胶层厚度为1mm。
步骤3，经过压花辊4对压延贴合后的材料进行压花压印得到墙纸花纹。
步骤4，经压花压印后的材料送入150℃烘道5硫化10分钟即得成品墙纸，在本发明的另一实施例中，压花压印后的材料送入180℃烘道5硫化5分钟即得成品墙纸，在又另一实施例中，压花压印后的材料送入120℃烘道5硫化15分钟即得成品墙纸。
实施例2
本实施例与实施例1的区别之处：有机硅原胶料原料采用以下组分及质量配比：
乙烯基聚硅氧烷生胶：分子量为80万且乙烯基含量0.1％的乙烯基聚硅氧烷生胶50KG，分子量为80万且乙烯基含量1％的乙烯基聚硅氧烷生胶50KG
填料：白碳黑(A200)40KG
结构控制剂：短链羟基硅油4.5KG
塑炼剂：硬酯酸甘油酯0.25KG
经混炼后加入
含氢硅油(氢含量1.6％，黏度50)5.5KG
延迟剂：甲基丁炔醇0.007KG
铂催化剂(30000ppm)0.035KG
色浆5KG
功能性助剂：防霉剂0.5KG抗菌剂0.1KG配制成有机硅胶料
本实施例与实施例1的另一个不同处在于，调整压延厚度为0.15mm
实施例3
本实施例与实施例1和2的区别之处：有机硅原胶料原料采用以下组分及质量配比：
乙烯基聚硅氧烷生胶：分子量为60万且乙烯基含量0.05％的乙烯基聚硅氧烷生胶50KG，分子量为60万且乙烯基含量0.5％的乙烯基聚硅氧烷生胶50KG
填料：沉淀法白碳黑(比表面积200)60KG
结构控制剂：短链羟基硅油4.5KG
塑炼剂：硬酯酸甘油酯0.25KG
经混炼后加入
含氢硅油(氢含量1.6％，黏度50)4KG
延迟剂：乙炔基环己醇0.007KG
铂催化剂(30000ppm)0.035KG
色浆5KG
功能性助剂：防霉剂0.5KG配制成有机硅胶料
本实施例与实施例1的另一个不同处在于，调整压延厚度为1mm
比较例：随机购买的一种市售常规PVC墙纸
对实施及比较例进行了如下测试：
环保性
GB18585-2001《室内装饰装修材料壁纸中有害物质限量》标准。
耐候性
GB/T1865-1997人工气候老化和人工辐射暴露
项目 耐候性
实施例1 600h无变化
实施例2 600h无变化
实施例3 600h无变化
比较例 表面粉化，开裂，褪色
阻燃性
GB8624-2006《建筑材料及制品燃烧性能分级》
项目 实施例1 实施例2 实施例3 比较例
阻燃等级 B1 B1 B1 B1
防霉防潮
GB/T2423.16-1999《长霉试验》
通过对实验菌种各种霉菌进行长霉试验：
防污性
用一些污渍24小时后用中性洗涤剂和酒精清理后对比：
5：无污点残留
4：稍许污点残留
3：一些污点残留
2：许多污点残留
1：脏的
项目 实施例1 实施例2 实施例3 比较例
防污等级 5 5 5 1
由上可知，本发明的环保耐侯耐污墙纸通过压延贴胶-压花-硫化工艺制作而成，其工艺简单且可连续生产，效率高，整个过程无有害物质无污染物，制备的有墙纸环保无毒，且可赋予墙纸优异的耐候防污防火防潮防霉性能。
上面结合附图所描述的本发明优选具体实施例仅用于说明本发明的实施方式，而不是作为对前述发明目的和所附权利要求内容和范围的限制，凡是依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰，均仍属本发明技术和权利保护范畴。

Claims (10)

1.一种环保耐候耐污墙纸，其特征在于：包括复合连接在一起的基材层和有机硅橡胶层。
2.根据权利要求1所述的环保耐候耐污墙纸，其特征在于：所述有机硅橡胶层的厚度在0.1-1mm。
3.根据权利要求1所述的环保耐候耐污墙纸，其特征在于：所述基材层为纸胚，或为纺织布。
4.根据权利要求1所述的环保耐候耐污墙纸，其特征在于：所述有机硅橡胶层通过将有机硅胶料设置在基材层上形成，所述有机硅胶料包括乙烯基聚硅氧烷生胶、填料、结构控制剂、塑炼剂、含氢硅油、铂催化剂以及延迟剂。
5.根据权利要求4所述的环保耐候耐污墙纸，其特征在于：所述有机硅胶料的组分及质量配比如下：
乙烯基聚硅氧烷生胶90-110份
填料40-100份
结构控制剂1-15份
塑炼剂0.0001-2份
含氢硅油0.001-10份
铂催化剂0.0005-5份
延迟剂0.001-5份
色浆0-20份
功能性助剂0-30份。
6.根据权利要求5所述的环保耐候耐污墙纸，其特征在于：所述乙烯基聚硅氧烷生胶为至少两个乙烯基直接与Si相连的聚硅氧烷，且其中聚硅氧烷的链端或侧链含有乙烯基，或链端与侧链同时含有乙烯基；
所述填料为气相法白炭黑、沉淀法白炭黑、硅树脂、硅微粉、碳酸钙、铝硅酸盐、硅澡土、石墨烯、氧化铝、氢氧化铝、氢氧化镁、二氧化钛中的一种或两种以上的混合物；
所述结构控制剂为羟基或烷氧基封端小分子硅油、六甲基二硅氮烷、二乙烯基四甲基二硅氮烷、二苯基二羟基硅烷、烃基烷氧基硅烷中的一种或两种以上的混合物，其中羟基或烷氧基封端小分子硅油在25℃的粘度为5-100mm2/s，其中烃基烷氧基硅烷为二甲基二甲氧基硅烷、二乙基二甲氧基硅烷或者为二甲基二乙氧基硅烷；
所述塑炼剂为高级脂肪醇、高级脂肪酸及其金属盐、高级脂肪酸酯中的一种或两种以上的混合物，所述高级脂肪酸酯为硬脂酸、硬脂酸锌、十二醇、硬脂酸钙或者为硬酯酸甘油酯；
所述含氢聚硅氧烷为至少有3个氢原子与Si直接相连的聚硅氧烷，所述氢原子位于该聚硅氧烷的链端或侧链，或链两端与侧链同时含有与Si直接相连的氢原子，所述氢原子含量为0.1～1.6％；所述含氢聚硅氧烷为直链状、枝状、环状的聚硅氧烷中的一种或多种的混合物；
所述铂催化剂为氯铂酸异丙醇溶液、氯铂酸四氢呋喃溶液、氯铂酸-二乙烯基四甲基二硅氧烷配合物、氯铂酸-1、3、5、7-四乙烯基-1、3、5、7-四甲基-环四硅氧烷中的一种或两种以上的混合物，所述铂催化剂中Pt原子的含量为100～500000ppm；
所述延迟剂为甲基丁炔醇、乙炔基环己醇、含炔基的马来酸或其衍生物、含炔基的富马来酸或其衍生物、多乙烯基聚硅氧烷、吡啶、不饱和酰胺类、有机膦或亚磷酸酯中的一种或两种以上的混合物；
所述色浆为以聚硅氧烷为分散介质的颜料；
所述功能性助剂为抗静电剂、防霉剂、抗菌剂、导电填料、阻燃剂、夜光粉中的一种或多种的混合物。
7.根据权利要求6所述的环保耐候耐污墙纸，其特征在于：所述乙烯基聚硅氧烷生胶的分子量为55-80万，且其中的乙烯基含量0.01-2％。
8.根据权利要求6所述的环保耐候耐污墙纸，其特征在于：所述色浆为以含乙烯基的聚硅氧烷为分散介质的颜料。
9.一种基于权利要求1至8任一所述的环保耐候耐污墙纸的制作方法，其特征在于：将有机硅胶料设置在基材层上形成有机硅橡胶层，经压花及硫化，进而得到墙纸。
10.根据权利要求9所述的制作方法，其特征在于，包括以下步骤：
步骤1:配制有机硅胶料；
步骤2:将有机硅胶料与基材进行压延贴合；
步骤3：对压延贴合后的材料进行压花压印得到墙纸花纹；
步骤4：对压花压印后的材料在120-180℃下硫化5-15分钟即得成品墙纸。
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