CN115198557B - 一种抗菌降醛三聚氰胺饰面板及其制备方法 - Google Patents

一种抗菌降醛三聚氰胺饰面板及其制备方法 Download PDF

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CN115198557B
CN115198557B CN202210691532.9A CN202210691532A CN115198557B CN 115198557 B CN115198557 B CN 115198557B CN 202210691532 A CN202210691532 A CN 202210691532A CN 115198557 B CN115198557 B CN 115198557B
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titanium dioxide
formaldehyde resin
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赵明
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Chengdu Banxiansen Decoration Materials Co ltd
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Abstract

本发明提供一种抗菌降醛三聚氰胺饰面板的制备方法，其包括如下步骤：(1)将纳米二氧化钛、冬瓜皮乙醇提取物和甲壳素均匀的分散至三聚氰胺甲醛树脂中，其中，纳米二氧化钛和冬瓜皮乙醇提取物的质量之和低于三聚氰胺甲醛树脂的质量的0.2％，纳米二氧化钛和冬瓜皮乙醇提取物的质量之比为1:1～1:3；(2)将原纸浸泡在步骤(1)所得物中进行浸胶，制备三聚氰胺甲醛树脂浸渍纸；(3)将三聚氰胺甲醛树脂浸渍纸放置在基材板上，进行热压压制，即得。本发明所得的三聚氰胺饰面板具有优秀的抑菌性，抑菌效果可以达到99.9％；本发明具有良好的除醛效果，除醛效率达到75％以上；本发明仅需添加少量的抑菌剂，安全环保。

Description

一种抗菌降醛三聚氰胺饰面板及其制备方法
技术领域
本发明属于复合材料领域，涉及三聚氰胺饰面板，具体涉及一种抗菌降醛三聚氰胺饰面板及其制备方法。
背景技术
饰面人造板是用浸渍纸、薄木单板、热塑性覆膜材料、涂料或纹理影印技术(包括3D打印技术)在人造板素板表面进行加工装饰后的新型人造板产品。
在饰面人造板制备领域中，常用的浸渍用胶黏剂包括三聚氰胺甲醛树脂、脲醛树脂和酚醛树脂。三聚氰胺甲醛树脂具有合成工艺简单、固化快、黏接力强、颜色浅、耐划痕及耐高温等优点，占据浸渍胶膜纸用胶黏剂的主要份额。
过去，人们比较重视产品的耐用度和美观，相关的研究主要集中在提高面板的硬度、耐磨性、耐热性、耐腐蚀性和耐污等方面。例如CN101439524B提供了一种三聚氰胺饰面板及其制备方法，该方法能使得三聚氰胺树脂胶黏合剂能更均匀、彻底浸入装饰纸，经压制形成高亮度耐划伤无污染气味装饰板；再如CN106188450B提供了一种耐污型三聚氰胺饰面板的制备方法。
随着人们对家居用品的安全健康问题日益重视，使得如何提高相关产品的抗菌性和甲醛净化性能成为本领域的重要研究方向。
在抗菌性研究方面，2015年2月，唐朝发等人在《不同抗菌剂对浸渍薄木抗菌性能影响的研究》(唐朝发,李岩,李春风,刘明利,刘彦龙.不同抗菌剂对浸渍薄木抗菌性能影响的研究[J].林产工业,2015,42(02):29-31.)研究了添加不同抑菌剂对三聚氰胺甲醛树脂薄木的抗菌性的影响，结果发现仅添加水溶性壳聚糖或木聚糖，无法提高抗菌性，原因在于三聚氰胺甲醛树脂固化后阻挡了其与外界的接触；而添加纳米二氧化钛或者载银纳米二氧化钛作为抑菌剂，则能较好的提高抗菌性。同年，江苏中欧生态环境科技有限公司在其发明专利ZL201510966001.6中公布，将纳米二氧化钛、纳米银和蛋白石作为三聚氰胺甲醛的添加剂，可以使得所得复合材料的抗菌性达到90～99.9％，甲醛去除率24小时内达到60-85％。杜洪双等人在《浸渍方法对抗菌浸渍薄木抗菌性能的影响》(杜洪双,朱红霏,刘壮,唐朝发.浸渍方法对抗菌浸渍薄木抗菌性能的影响[J].林产工业,2015,42(12):21-22+35.)中研究了载银纳米二氧化钛在质量为三聚氰胺甲醛树脂的1～5％时，所得饰面板所具有的抗菌性能，结果显示在添加量为5％时，最高抗菌性为99.8，这一结果与ZL201510966001.6相近。
在净醛方面，ZL201510966001.6利用蛋白石(即二氧化硅的水合物)作为除醛物质，实现了65％～85％的除醛效率。类似的，德华兔宝宝装饰新材股份有限公司申请的专利ZL201510408082.8，采用了纳米硅片、甲壳素和电气石粉作为除醛剂，实现了75％以上的甲醛净化效率。
然而，包括上述举例的报道在内，现有技术为了实现良好的抗菌和降醛效果，往往需要添加较大比重的抑菌剂和除醛剂。一般而言，为了实现90％以上的抑菌性，抑菌剂的添加量往往占三聚氰胺甲醛树脂质量的0.5％以上，例如ZL201510966001.6中二氧化钛和纳米银的添加量甚至远超过1％，这就造成了相关的制备工艺的成本过高。重要的是，纳米级二氧化钛对机体是不利的，机体吸入后会破坏机体的免疫功能，相关发现可参考论文《Titanium Dioxide Nanoparticles Prime a Specific Activation State ofMacrophages》(Chao,Huang,Mayu,et al.Titanium dioxide nanoparticles prime aspecific activation state of macrophages[J].Nanotoxicology,2017.)；同时，最近研究发现，纳米银具有高毒性，人们对其在于人体直接接触的产品的使用方面是非常谨慎的。
因此，如何在确保优秀的抗菌性和降醛效果下，大幅的降低抑菌剂和除醛剂的使用，在本领域中显得十分的重要。
发明内容
针对现有技术的缺点，本发明的目的在于提供一种抗菌降醛三聚氰胺饰面板的制备方法，该方法可以制备得到抗菌性和净醛效果优异的饰面板。该方法目的在于解决现有技术中纳米二氧化钛添加量过高的问题。该方法中，抑菌剂的添加量非常少，可低于三聚氰胺甲醛树脂的质量的0.2％，抑菌剂中的纳米二氧化钛更可低至1/4，即纳米二氧化钛的添加量可低至三聚氰胺甲醛树脂的质量的0.05％。
为了实现上述目的，本发明提供如下技术方案：
一种抗菌降醛三聚氰胺饰面板的制备方法，所述制备方法包括如下步骤：
(1)将纳米二氧化钛、冬瓜皮乙醇提取物和甲壳素均匀的分散至三聚氰胺甲醛树脂中，其中，纳米二氧化钛和冬瓜皮乙醇提取物的质量之和低于三聚氰胺甲醛树脂的质量的0.2％，纳米二氧化钛和冬瓜皮乙醇提取物的质量之比为1:1～1:3；
(2)将原纸浸泡在步骤(1)所得物中进行浸胶，制备三聚氰胺甲醛树脂浸渍纸；
(3)将步骤(2)所得三聚氰胺甲醛树脂浸渍纸放置在基材板上，进行热压压制，即得所述抗菌降醛三聚氰胺饰面板。
优选的，步骤(1)中，甲壳素的质量为三聚氰胺甲醛树脂的质量的2～3％。
优选的，步骤(1)中，纳米二氧化钛和冬瓜皮乙醇提取物的质量之比为1:2。
在本发明中，步骤(1)中，所述冬瓜皮乙醇提取物的制备方法为：将冬瓜皮切碎，置于体积分数为70％的乙醇水溶液中，于55℃下进行提取，减压浓缩后进行冻干即得。
优选的，步骤(1)中，所述纳米二氧化钛的平均粒径为15～30nm。
优选的，步骤(2)中，在制备三聚氰胺甲醛树脂浸渍纸时，浸胶量为150～180g/m2。
在本发明中，步骤(3)中，所述基材板包括胶合板、刨花板、纤维板中的任何一种。
在本发明中，步骤(3)中，在进行压制时，温度为125～130℃，单位压力为0.8～1.5MPa，压制时间为1.5～10分钟。
优选的，所述基材板的含水量为6～12％。
本发明的另外一个目的在于提供由上述制备方法制备得到的抗菌降醛三聚氰胺饰面板。
本发明在研究的过程中，考虑到二氧化钛在实现抑菌方面的原理在于：二氧化钛可以在光照下产生羟基自由基和氧自由基，可以与细菌发生有机物质氧化反应，从而产生抑菌效果。因此，减少二氧化钛的用量的同时还能维持优秀的抑菌性，只能通过添加与之能在抑菌方面产生协同作用的物质。
目前，与纳米二氧化钛具有协同抑菌的物质不少，但这些物质的抑菌原理多是通过接触抑菌；而在制备饰面板时，这些物质由于被封埋在固化的三聚氰胺甲醛树脂中，无法实现与纳米二氧化碳的协同。通过不断的摸索，发明人发现在纳米二氧化钛的基础上，添加冬瓜皮乙醇提取物之后，可以大幅度的降低纳米二氧化钛的添加量并维持十分优秀的抑菌效果。
在采用冬瓜皮抗菌方面，人们发现利用乙醇对冬瓜皮进行提取后，再用其它有机试剂进行萃取，可以获得具有相应抑菌性的物质，见《冬瓜皮提取物抑菌活性研究》(范会平,李嘉,陈月华,许梦言,艾志录,郭毅.冬瓜皮提取物抑菌活性研究[J].医药论坛杂志,2018,39(01):126-128.)。不过，在本发明中，由于同样的原因，冬瓜皮乙醇提取物显然难以与细菌直接接触而发挥抑菌作用。因此，本发明中的冬瓜皮乙醇提取物很可能可以促进纳米二氧化钛进一步的产生羟基自由基和氧自由基，从而发挥更好的抑菌性。为了初步验证这一点，如本发明的一个对比例所示，当把纳米二氧化钛替换为水溶性壳聚糖之后，所得饰面板没有获得抑菌性的提高。另外，本发明的乙醇提取物与《冬瓜皮提取物抑菌活性研究》的抗菌产品相比，无需进行相应的萃取工作，节省了制备成本。
本发明的有益效果：
本发明所得的三聚氰胺饰面板具有优秀的抑菌性，抑菌效果可以达到99.9％；本发明同时具有良好的除醛效果，除醛效率达到除醛Ⅰ类标准(即75％以上)；本发明仅需添加少量的抑菌剂，安全环保。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员根据上述发明内容所做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
1.原料：纳米二氧化钛(平均粒径20nm)、乙醇、三聚氰胺甲醛树脂(黏度18～25MPa·s，固含量50～53％)、甲壳素(粒径60～100nm)、水溶性壳聚糖和冬瓜皮(对冬瓜削皮所得)均为市售所得；原纸(浸渍胶膜纸原纸)、基材板(刨花板)为自有。
冬瓜皮乙醇提取物的制备：将冬瓜皮切碎，置于体积分数为70％的乙醇水溶液中，于55℃下进行提取1小时，减压浓缩后进行冻干即得。
2.制备方法：
(1)按重量比1:2，取纳米二氧化钛和冬瓜皮乙醇提取物备用；取甲壳素备用；缓慢将纳米二氧化钛、冬瓜皮乙醇提取物和甲壳素与三聚氰胺甲醛树脂混合，并分散均匀，直至纳米二氧化钛和冬瓜皮乙醇提取物的添加量之和占三聚氰胺甲醛树脂质量的0.15％、甲壳素的添加量占三聚氰胺甲醛树脂质量的2％为止；
(2)将原纸放入步骤(1)中进行浸渍，浸胶量为150g/m2；
(3)平衡浸渍纸的含水量至13～15％，平衡刨花板的含水量至6～8％，之后将浸渍纸覆膜压制在刨花板上，在温度为125～130℃，单位压力为0.8～1.5MPa的条件下，压制2分钟，即得。
3.性能测定：
(1)抗菌性能测定：参考《浸渍方法对抗菌浸渍薄木抗菌性能的影响》中1.3.3的测试方法，测试时在光照条件下。
(2)除醛效率测定：参考《甲醛净化生态板的甲醛释放量和净化性能探讨》1.4中采用的“甲醛净化性能”测试方法。
测试结果：本实施例所得抗菌降醛三聚氰胺饰面板的抗菌性(取针对大肠杆菌和金黄色葡萄球菌抗菌性的最小值)为99.9％，甲醛净化性能为82％。
实施例2
在实施例1的基础上，将纳米二氧化钛和冬瓜皮乙醇提取物的添加量之和降低至占三聚氰胺甲醛树脂质量的0.1％，其余保持不变。
利用与实施例1同样的性能测定方法进行测试，所得抗菌降醛三聚氰胺饰面板的抗菌性为99.6％，甲醛净化性能为81％。
实施例3
在实施例1的基础上，将纳米二氧化钛和冬瓜皮乙醇提取物的质量之比调整为1:3，其余保持不变。
利用与实施例1同样的性能测定方法进行测试，所得抗菌降醛三聚氰胺饰面板的抗菌性为99.1％，甲醛净化性能为81％。
对比实施例1
在实施例1的基础上，将纳米二氧化钛替换为水溶性壳聚糖，其余与实施例1保持一致。
利用与实施例1同样的性能测定方法进行测试，所得抗菌降醛三聚氰胺饰面板的抗菌性为51.2％，该结果与《不同抗菌剂对浸渍薄木抗菌性能影响的研究》一致；甲醛净化性能为67％。

Claims (8)

1.一种抗菌降醛三聚氰胺饰面板的制备方法，其特征在于，所述制备方法包括如下步骤：
(1)将纳米二氧化钛、冬瓜皮乙醇提取物和甲壳素均匀的分散至三聚氰胺甲醛树脂中，其中，纳米二氧化钛和冬瓜皮乙醇提取物的质量之和低于三聚氰胺甲醛树脂的质量的0.2％，纳米二氧化钛和冬瓜皮乙醇提取物的质量之比为1:1～1:3；
(2)将原纸浸泡在步骤(1)所得物中进行浸胶，制备三聚氰胺甲醛树脂浸渍纸；
(3)将步骤(2)所得三聚氰胺甲醛树脂浸渍纸放置在基材板上，进行热压压制，即得所述抗菌降醛三聚氰胺饰面板；
步骤(1)中，所述冬瓜皮乙醇提取物的制备方法为：将冬瓜皮切碎，置于体积分数为70％的乙醇水溶液中，于55℃下进行提取，减压浓缩后进行冻干即得；
步骤(1)中，所述纳米二氧化钛的平均粒径为15～30nm。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，甲壳素的质量为三聚氰胺甲醛树脂的质量的2～3％。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，纳米二氧化钛和冬瓜皮乙醇提取物的质量之比为1:2。
4.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，在制备三聚氰胺甲醛树脂浸渍纸时，浸胶量为150～180g/m2。
5.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述基材板包括胶合板、刨花板、纤维板中的任何一种。
6.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，在进行压制时，温度为125～130℃，单位压力为0.8～1.5MPa，压制时间为1.5～10分钟。
7.根据权利要求5所述的制备方法，其特征在于，所述基材板的含水量为6～12％。
8.一种抗菌降醛三聚氰胺饰面板，其特征在于，所述一种抗菌降醛三聚氰胺饰面板由权利要求1～7任一项权利要求所述的制备方法制得。
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