CN111501416A - 一种装饰纸用无醛浸渍胶黏剂及其制备方法 - Google Patents

一种装饰纸用无醛浸渍胶黏剂及其制备方法 Download PDF

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CN111501416A
CN111501416A CN202010394935.8A CN202010394935A CN111501416A CN 111501416 A CN111501416 A CN 111501416A CN 202010394935 A CN202010394935 A CN 202010394935A CN 111501416 A CN111501416 A CN 111501416A
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刘如
徐建峰
龙玲
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Research Institute of Forestry New Technology of Chinese Academy of Forestry
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Abstract

本发明要求保护一种物理强度达到国标要求的装饰纸用无醛浸渍胶黏剂及其制备方法,无醛胶黏剂包括以下组分:水性丙烯酸乳液40‑60份,有机胺5‑15份,交联剂1‑5份,聚乙烯醇1‑5份,填料5‑10份和水5‑10份,本申请制备的无醛胶黏剂无甲醛释放,安全环保,其中水性丙烯酸酯乳液粒径较小、分子量较小、黏度适中,使得浸渍胶黏剂能较好地渗透进入纸张内部,解决了普通树脂胶黏剂浸渍后装饰纸的纸间破坏问题,引入的有机胺、聚乙二醇、聚乙烯醇与丙烯酸酯树脂反应,所制备的胶黏剂浸渍装饰纸的挂胶量和物理强度比纯树脂胶黏剂浸渍装饰纸的相应值提高较大,达到了国标的要求。

Description

一种装饰纸用无醛浸渍胶黏剂及其制备方法
技术领域
本发明涉及一种装饰纸用无醛浸渍胶黏剂及其制备方法,属于人造板加工技术领域。
背景技术
装饰纸是一种重要的人造板饰面材料,对人造纸及其制品起着保护和美化作用。一般地,装饰纸是由装饰原纸经印刷、浸渍处理而成。一直以来,装饰纸浸渍处理多采用脲醛胶和三聚氰胺-甲醛胶两段浸胶工艺,生产的装饰纸饰面人造板产品的硬度、耐磨性、耐刮擦性等物理性能优异。但这种传统浸胶方式会在生产和产品使用过程中释放出游离甲醛,对操作工人和消费者的身体健康造成危害。随着人们对室内环境要求的提高及国家相关法律法规的出台,装饰纸饰面人造板产品的无醛化迫在眉睫。大豆胶等生物质胶黏剂的推广,实现了人造板的无醛化,因此开发装饰纸用无醛浸渍胶黏剂已成为解决问题的关键。
无醛浸渍胶黏剂主要包括天然胶黏剂(包括矿物质、动物胶和植物胶等)、改性生物基(大豆蛋白胶、植物油、木素等)胶黏剂、(改性)高分子树脂无醛浸渍胶黏剂(包括丙烯酸酯、聚氨酯、聚醋酸乙烯酯)等几类。这些胶黏剂在木材工业中主要用于刨花板、纤维板等人造板的制造,例如大亚人造板集团有限公司(CN 109575875 A)使用大豆分离蛋白、尿素、三聚磷酸钠、甲基纤维素等制备了无醛浸渍胶黏剂,用于纤维板的制造,甲醛释放量接近于0,但生物基胶黏剂遇水容易生霉,耐候性差、粘结强度较低。山东农业大学(CN 109593508A)利用生物油、异氰酸酯、植物多元醇制备了聚氨酯类的无醛浸渍胶黏剂,此类胶黏剂耐水性及热稳定性好、胶接强度大,但分子交联程度大、粒径大、粘度高。
上述无醛浸渍胶黏剂,生物基胶黏剂耐霉变、耐候性差,在装饰纸浸渍中的应用极少。目前仅有少量关于(改性)高分子树脂胶黏剂的报道,例如临沂市鲁源浸渍纸业有限公司(CN 109776717 A)获得了一种丙烯酸酯基的装饰纸浸渍胶黏剂,以此生产的预浸装饰纸和贴面纸无醛,装饰纸柔软、可收卷、可裁切。万华生态科技有限公司(CN 110450239 A)开发的聚氨酯类浸渍胶黏剂,也能实现装饰纸的无醛化。但上述有机高分子类树脂胶黏剂因其粘度大、粒径大、交联程度高,很难渗透进入装饰原纸内部,存在诸多问题。与传统的脲醛胶和三聚氰胺-甲醛胶相比,此类胶黏剂浸渍的装饰纸挂胶量低、物理性能较差,尤其是耐刮擦性能差、硬度低、光泽度和饱满度均不能达到相关国标要求,且由于胶液难以渗透至纸层间,存在着装饰纸纸间剥离的缺陷。相关产品还处在实验室研究阶段。
因此,制备一种纸张渗透性能好、粘接性高、胶膜物理强度优异、挂胶量高的装饰纸用无醛浸渍胶黏剂显得十分必要。
发明内容
本发明要解决的技术问题是,针对以上现有技术中的不足,提供一种物理强度达到国标要求的装饰纸用无醛浸渍胶黏剂及其制备方法。按质量分数计,组分包括:
水性丙烯酸乳液:40-60份
有机胺:5-15份
交联剂:1-5份
聚乙烯醇:1-5份
填料:5-10份
水:5-10份。
具体的,所述的有机胺为分子量小于300的一元胺、二元胺、三元胺,具体的,所述的有机胺为二乙胺、三乙胺、乙二胺、三乙烯二胺、二乙醇胺、三乙醇胺、甲酰胺、乙酰胺、氨基酸、哌嗪中的一种或几种。其作用为与丙烯酸酯反生交联反应,提高胶黏剂的粘结性及胶膜物理强度。
具体的,所述的交联剂为小分子量聚乙二醇,更为具体的,所述的交联剂为分子量100-700的聚乙二醇。其作用为与丙烯酸酯反生交联反应,提高胶黏剂的粘结性及胶膜物理强度。
具体的,所述的聚乙烯醇为低粘度聚乙烯醇水溶液,更为具体的,所述的聚乙烯醇为平均分子量16000~20000,黏度4-6cp,质量分数10%的水溶液。其作用为提高胶黏剂胶膜的耐刮擦性能,并适度提高胶黏剂的粘度,从而提高装饰纸的挂胶量。
具体的,所述的填料为粒径50-200nm的二氧化钛悬浮液,质量分数20%左右;粒径50-100nm的二氧化硅悬浮液,质量分数10%左右;50-100nm的二氧化锌悬浮液,质量分数10%左右;粒径50-200nm的三氧化二铝悬浮液,质量分数10%左右中的一种或者几种的组合。其作用为提高装饰纸的挂胶量和胶黏剂胶膜的耐刮擦、耐磨性能。
具体的,所述的水性丙烯酸乳液的配方为:软单体5-10份、硬单体5-10份、乳化剂0.5~5份、引发剂0.3~0.6份、水50~70份、pH调节剂0.05-0.1份。
更具体的,所述的软单体包括丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸正辛酯中的一种或几种。所述的硬单体包括丙烯酸、甲基丙烯酸、丙烯腈中的一种或几种。所述的乳化剂为NP、A-103、CO-436、X-405中的两种或多种。所述的引发剂为过硫酸铵或者过硫酸钾中的一种。所述的pH调节剂为氨水。
所述装饰纸用无醛浸渍胶黏剂的制备方法如下:
1)在反应器中加入全部的pH调节剂和去离子水、1/3软单体1/3硬单体、1/3引发剂和全部乳化剂,搅拌桨与水平面成50°-60°角,桨叶距离反应容器底部高度为液面高度的1/3-1/2处,搅拌速度150-200r/min,待泛蓝光后立即停止反应,制得预乳液;
2)将余量的软单体和硬单体混合均匀,与余量的引发剂在75-85℃的条件下,分别滴加至预乳液,在搅拌状态下升温至75-85℃,搅拌速度100-150r/min,30min滴完,滴加过程始终保持搅拌桨与水平面成50°-60°角,桨叶距离反应容器底部高度为液面高度的1/3-1/2处,滴加完毕后保温15-30min,制得水性丙烯酸酯乳液;乳液的固含量在20%左右,粒径100nm左右,黏度20-100cp,分子量300-2000。
3)按照配方比例,将有机胺、聚乙烯醇水溶液在50-60℃,200-300r/min条件下加入到水性丙烯酸乳液中,反应20-30min后加入交联剂,继续反应20-30min,然后加入填料和水,搅拌速度调为800-1000r/min,搅拌十分钟,静置,即得到装饰纸用无醛浸渍胶黏剂。
采用上述无醛浸渍胶黏剂对装饰原纸进行浸渍、干燥处理,得到浸渍装饰纸;将浸渍装饰纸热压至人造板表面,得到装饰纸饰面人造板。并依照国家标准GB/T 28995-2012、GB/T 15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
本发明具有以下优点:
1)所制备胶黏剂的各组分均无游离甲醛,且胶黏剂产品无游离甲醛释放,实现了浸渍装饰纸的无醛化。
2)在制备丙烯酸酯乳液时,所选的软硬单体为分子量小、分子链短的直链单体;乳化剂为特定的复配乳化剂体系;选择特定的搅拌桨位置和角度使搅拌更均匀,特定的搅拌速度和较短的反应时长使获得的丙烯酸酯乳液粒径较小、分子量较小、黏度适中,这使得浸渍胶黏剂能较好地渗透进入纸张内部,解决了普通树脂胶黏剂浸渍后装饰纸的纸间破坏问题。
3)引入有机胺、聚乙二醇、聚乙烯醇与丙烯酸酯树脂反应,所制备的胶黏剂浸渍装饰纸的挂胶量和物理强度比纯丙烯酸酯树脂胶黏剂浸渍装饰纸更优,达到了国标的要求。
4)引入填料使得胶黏剂体系在对粘度影响不大的条件下,提高了浸渍装饰纸的挂胶量;同时能一定程度上提高胶膜的耐刮擦性能。
具体实施方式
实施例1
1)在反应器中加入全部的pH调节剂和去离子水、1/3软单体1/3硬单体、1/3引发剂和全部乳化剂,搅拌桨与水平面成50°角,桨叶距离反应容器底部高度为液面高度的1/2处,搅拌速度200r/min,待泛蓝光后立即停止反应,制得预乳液。
2)将余量的软单体和硬单体混合均匀,与余量的引发剂在85℃的条件下,分别滴加至预乳液,在搅拌状态下升温至85℃,搅拌速度150r/min,30min滴完,滴加过程始终保持搅拌桨与水平面成50°角,桨叶距离反应容器底部高度为液面高度的1/2处,滴加完毕后保温20min,制得水性丙烯酸酯乳液。
3)一种装饰纸无醛胶黏剂,按照下面配方比例:
水性丙烯酸乳液:50份
乙二胺:10份
交联剂(分子量100):3份
聚乙烯醇(分子量16000):3份
二氧化钛(粒径100nm):5份
水:10份。
将有机胺、聚乙烯醇水溶液在50℃,200r/min条件下加入到水性丙烯酸乳液中,反应20min后加入交联剂,继续反应30min,然后加入填料和水,搅拌速度调为1000r/min,搅拌10分钟,静置,即得到装饰纸用无醛浸渍胶黏剂。
采用上述无醛浸渍胶黏剂对装饰原纸进行浸渍、干燥处理,得到浸渍装饰纸;将浸渍装饰纸热压至人造板表面,得到装饰纸饰面人造板。并依照国家标准GB/T 28995-2012、GB/T 15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
实施例2
1)在反应器中加入全部的pH调节剂和去离子水、1/3软单体1/3硬单体、1/3引发剂和全部乳化剂,搅拌桨与水平面成60°角,桨叶距离反应容器底部高度为液面高度的1/3处,搅拌速度150r/min,待泛蓝光后立即停止反应,制得预乳液。
2)将余量的软单体和硬单体混合均匀,与余量的引发剂在85℃的条件下,分别滴加至预乳液,在搅拌状态下升温至85℃,搅拌速度100r/min,30min滴完,滴加过程始终保持搅拌桨与水平面成60°角,桨叶距离反应容器底部高度为液面高度的1/3处,滴加完毕后保温30min,制得水性丙烯酸酯乳液。
3)一种装饰纸无醛胶黏剂,按照下面配方比例:
水性丙烯酸乳液:40份
三乙胺:15份
交联剂(分子量700);1份
聚乙烯醇(分子量20000):5份
二氧化硅(粒径100nm):10份
水:10份。
将有机胺、聚乙烯醇水溶液在60℃,300r/min条件下加入到水性丙烯酸乳液中,反应30min后加入交联剂,继续反应20min,然后加入填料和水,搅拌速度调为800r/min,搅拌10分钟,静置,即得到装饰纸用无醛浸渍胶黏剂。
采用上述无醛浸渍胶黏剂对装饰原纸进行浸渍、干燥处理,得到浸渍装饰纸;将浸渍装饰纸热压至人造板表面,得到装饰纸饰面人造板。并依照国家标准GB/T 28995-2012、GB/T 15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
实施例3
1)在反应器中加入全部的pH调节剂和去离子水、1/3软单体1/3硬单体、1/3引发剂和全部乳化剂,搅拌桨与水平面成50°角,桨叶距离反应容器底部高度为液面高度的1/2处,搅拌速度180r/min,待泛蓝光后立即停止反应,制得预乳液。
2)将余量的软单体和硬单体混合均匀,与余量的引发剂在85℃的条件下,分别滴加至预乳液,在搅拌状态下升温至85℃,搅拌速度120r/min,30min滴完,滴加过程始终保持搅拌桨与水平面成50°角,桨叶距离反应容器底部高度为液面高度的1/2处,滴加完毕后保温20min,制得水性丙烯酸酯乳液。
3)一种装饰纸无醛胶黏剂,按照下面配方比例:
水性丙烯酸乳液:60份
二乙醇胺:5份
交联剂(分子量300):5份
聚乙烯醇(分子量18000):1份
二氧化钛(粒径100nm)4份,三氧化二铝(50nm)3份
水:10份。
将有机胺、聚乙烯醇水溶液在50℃,260r/min条件下加入到水性丙烯酸乳液中,反应20min后加入交联剂,继续反应30min,然后加入填料和水,搅拌速度调为900r/min,搅拌10分钟,静置,即得到装饰纸用无醛浸渍胶黏剂。
采用上述无醛浸渍胶黏剂对装饰原纸进行浸渍、干燥处理,得到浸渍装饰纸;将浸渍装饰纸热压至人造板表面,得到装饰纸饰面人造板。并依照国家标准GB/T 28995-2012、GB/T 15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
对比例1
与实施例1的技术方案的区别仅在于不添加聚乙烯醇。
对比例2
与实施例1的技术方案的区别仅在于不添加有机胺。
对比例3
与实施例1的技术方案的区别仅在于不添加交联剂。
对比例4
与实施例1的技术方案的区别仅在于不添加填料。
性能测试
表1胶黏剂性能
粘胶剂a 胶黏剂b
粒径/nm 500 100
固含/wt% 30 50
黏度/cp 20 20
平均分子量 30000 1000
a.CN 109776717 A b.本发明胶黏剂
与已公布的装饰纸无醛胶黏剂相比,本发明制备的胶黏剂粒径更小,固含量更高,分子量更小,这有利于胶黏剂在纸张内部的渗透。
表2浸渍后装饰纸及饰面人造板物理性能对比
Figure BSA0000208465250000051
a.CN 109776717 A 测试参照国标:GB/T 28995-2012、GB/T 17657-2013、GB/T15102-2017
与已公布的装饰纸无醛胶黏剂相比,经本发明胶黏剂制备的装饰纸没有游离甲醛的释放,挂胶量更高,物理强度更好,且均满足相关国家标准的要求。胶黏剂配方中的聚乙烯醇提高了浸渍装饰纸饰面人造板的耐龟裂和耐划痕性能,有机胺和交联剂聚乙二醇提高了浸渍装饰纸饰面人造板的表结合强度、耐磨性等物理性能,填料提高了胶黏剂的固含及饰面人造板的耐刮擦和耐磨性能。

Claims (11)

1.一种装饰纸用无醛浸渍胶黏剂,其特征在于,按质量分数计,组分包括:
水性丙烯酸乳液:40-60份
有机胺:5-15份
交联剂:1-5份
聚乙烯醇:1-5份
填料:5-10份
水:5-10份。
2.根据权利要求1所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的水性丙烯酸乳液的配方为:软单体5-10份、硬单体5-10份、乳化剂0.5~5份、引发剂0.3~0.6份、水50~70份、pH调节剂0.05-0.1份。
3.根据权利要求2所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的软单体为丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸正辛酯中的一种或几种。
4.根据权利要求2所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的硬单体包括丙烯酸、甲基丙烯酸、丙烯腈中的一种或几种。
5.根据权利要求2所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的乳化剂为NP、A-103、CO-436、X-405中的两种或多种。
6.根据权利要求1-5任一项所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的有机胺为分子量小于300的一元胺、二元胺、三元胺,更为优选地,所述的有机胺为二乙胺、三乙胺、乙二胺、三乙烯二胺、二乙醇胺、三乙醇胺、甲酰胺、乙酰胺、氨基酸、哌嗪中的一种或几种。
7.根据权利要求1-6任一项所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的交联剂为小分子量聚乙二醇,更为优选地,所述的交联剂为分子量100-700的聚乙二醇。
8.根据权利要求1-7任一项所述的装饰纸用无醛浸渍胶黏剂,其特征在于,所述的聚乙烯醇为平均分子量16000~20000,黏度4-6cp,质量分数10%的水溶液。
9.根据权利要求2-8任一项所述的制备方法,其特征在于,所述的聚乙烯醇为平均分子量16000~20000,黏度4-6cp,质量分数10%的水溶液。
10.根据权利要求2-9任一项所述的制备方法,其特征在于,所述的填料为粒径50-200nm的二氧化钛悬浮液,质量分数20%左右;粒径50-100nm的二氧化硅悬浮液,质量分数10%左右;50-100nm的二氧化锌悬浮液,质量分数10%左右;粒径50-200nm的三氧化二铝悬浮液,质量分数10%左右中的一种或者几种的组合。
11.一种制备权利要求2-10任一项所述的装饰纸用无醛浸渍胶黏剂的制备方法,其特征在于,步骤如下:
1)在反应器中加入全部的pH调节剂和去离子水、1/3软单体1/3硬单体、1/3引发剂和全部乳化剂,搅拌桨与水平面成50°-60°角,桨叶距离反应容器底部高度为液面高度的1/3-1/2处,搅拌速度150-200r/min,待泛蓝光后立即停止反应,制得预乳液;
2)将余量的软单体和硬单体混合均匀,与余量的引发剂在75-85℃的条件下,分别滴加至预乳液,在搅拌状态下升温至75-85℃,搅拌速度100-150r/min,30min滴完,滴加过程始终保持搅拌桨与水平面成50°-60°角,桨叶距离反应容器底部高度为液面高度的1/3-1/2处,滴加完毕后保温15-30min,制得水性丙烯酸酯乳液;
3)按照配方比例,将有机胺、聚乙烯醇水溶液在50-60℃,200-300r/min条件下加入到水性丙烯酸乳液中,反应20-30min后加入交联剂,继续反应20-30min,然后加入填料和水,搅拌速度调为800-1000r/min,搅拌十分钟,静置,即得到装饰纸用无醛浸渍胶黏剂。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112900146A (zh) * 2021-03-03 2021-06-04 东莞市贝辉装饰材料有限公司 一种带有香味的浸渍胶膜纸及其制备方法
CN114293402A (zh) * 2022-01-06 2022-04-08 阳光王子(寿光)特种纸有限公司 一种无醛热压浸渍装饰纸及其制备方法
CN116289331A (zh) * 2023-03-03 2023-06-23 杭州锦宏装饰纸有限公司 一种抗菌耐磨装饰纸及其生产方法
CN117702532A (zh) * 2024-01-04 2024-03-15 东营市盛基环保工程有限公司 一种无甲醛浸渍装饰纸的制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313645A (en) * 1963-03-29 1967-04-11 Huyck Corp Papermaker's fabric with adhesive resin encased yarns
US5885719A (en) * 1993-12-21 1999-03-23 Arjo Wiggins S.A. Impregnated sheet substantially free of formaldehyde used as a basis for a decorative coating
CN1410498A (zh) * 2002-11-08 2003-04-16 江苏圣杰实业有限公司 人造板用水基共聚物胶粘剂及其制备方法
US20060134405A1 (en) * 1999-01-26 2006-06-22 Dieter Dohring Method of impregnating decorative papers
CN104263289A (zh) * 2014-09-09 2015-01-07 王义奎 汽车内饰件用水性胶粘剂及制备方法
CN105907343A (zh) * 2016-05-17 2016-08-31 湖南省和祥润新材料有限公司 一种水性丙烯酸复合胶粘剂及其制备方法
CN107722881A (zh) * 2017-10-18 2018-02-23 江西省林业科学院 一种醋丙乳液胶粘剂的制备方法
CN109354660A (zh) * 2018-11-23 2019-02-19 山东圣泉新材料股份有限公司 一种汽车滤纸用酚醛树脂及其制备方法以及汽车用滤纸
CN109706783A (zh) * 2018-12-26 2019-05-03 罗力诚 一种高性能无甲醛木纹纸浸渍胶水及制备方法
CN110079248A (zh) * 2019-04-30 2019-08-02 江苏艾科赛特新材料有限公司 一种水性无醛胶黏剂及其在人造板中的应用
CN110655620A (zh) * 2019-09-20 2020-01-07 中国林业科学研究院木材工业研究所 一种水性超支化聚丙烯酸酯乳液、制备方法及其应用
CN111320719A (zh) * 2020-03-24 2020-06-23 佛山祺祥合成材料有限公司 一种高渗透性丙烯酸乳液

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313645A (en) * 1963-03-29 1967-04-11 Huyck Corp Papermaker's fabric with adhesive resin encased yarns
US5885719A (en) * 1993-12-21 1999-03-23 Arjo Wiggins S.A. Impregnated sheet substantially free of formaldehyde used as a basis for a decorative coating
US20060134405A1 (en) * 1999-01-26 2006-06-22 Dieter Dohring Method of impregnating decorative papers
CN1410498A (zh) * 2002-11-08 2003-04-16 江苏圣杰实业有限公司 人造板用水基共聚物胶粘剂及其制备方法
CN104263289A (zh) * 2014-09-09 2015-01-07 王义奎 汽车内饰件用水性胶粘剂及制备方法
CN105907343A (zh) * 2016-05-17 2016-08-31 湖南省和祥润新材料有限公司 一种水性丙烯酸复合胶粘剂及其制备方法
CN107722881A (zh) * 2017-10-18 2018-02-23 江西省林业科学院 一种醋丙乳液胶粘剂的制备方法
CN109354660A (zh) * 2018-11-23 2019-02-19 山东圣泉新材料股份有限公司 一种汽车滤纸用酚醛树脂及其制备方法以及汽车用滤纸
CN109706783A (zh) * 2018-12-26 2019-05-03 罗力诚 一种高性能无甲醛木纹纸浸渍胶水及制备方法
CN110079248A (zh) * 2019-04-30 2019-08-02 江苏艾科赛特新材料有限公司 一种水性无醛胶黏剂及其在人造板中的应用
CN110655620A (zh) * 2019-09-20 2020-01-07 中国林业科学研究院木材工业研究所 一种水性超支化聚丙烯酸酯乳液、制备方法及其应用
CN111320719A (zh) * 2020-03-24 2020-06-23 佛山祺祥合成材料有限公司 一种高渗透性丙烯酸乳液

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赫庆鹏等: "丙烯酸酯乳液型压敏胶的制备及性能研究", 《山东理工大学学报(自然科学版)》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112900146A (zh) * 2021-03-03 2021-06-04 东莞市贝辉装饰材料有限公司 一种带有香味的浸渍胶膜纸及其制备方法
CN114293402A (zh) * 2022-01-06 2022-04-08 阳光王子(寿光)特种纸有限公司 一种无醛热压浸渍装饰纸及其制备方法
CN116289331A (zh) * 2023-03-03 2023-06-23 杭州锦宏装饰纸有限公司 一种抗菌耐磨装饰纸及其生产方法
CN117702532A (zh) * 2024-01-04 2024-03-15 东营市盛基环保工程有限公司 一种无甲醛浸渍装饰纸的制备方法
CN117702532B (zh) * 2024-01-04 2024-05-31 东营市盛基环保工程有限公司 一种无甲醛浸渍装饰纸的制备方法

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