CN115322317B - 一种装饰纸用抗刮水性聚氨酯树脂及其制备方法 - Google Patents

一种装饰纸用抗刮水性聚氨酯树脂及其制备方法 Download PDF

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CN115322317B
CN115322317B CN202210988812.6A CN202210988812A CN115322317B CN 115322317 B CN115322317 B CN 115322317B CN 202210988812 A CN202210988812 A CN 202210988812A CN 115322317 B CN115322317 B CN 115322317B
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庄启飞
庄启明
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Huangshan Haotai Plastic Co ltd
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Abstract

本发明公开了一种装饰纸用抗刮水性聚氨酯树脂及其制备方法，属于涂料技术领域，包括A组分和B组分，A组分包括消光水性聚氨酯乳液、流平剂和消泡剂；B组分为聚氨酯固化剂；将消光型聚酯预聚体加入与乙二胺基乙磺酸钠水溶液搅拌混合，然后加入羟基型水性聚氨酯预聚体搅拌混合，最后滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液；纳米γ‑Al2O3经过改性后其颗粒表面能降低，与预聚体的相容性增加，从而使改性消光粉具有较好的分散稳定性，有利于提高聚氨酯树脂的粘结度、附着力和硬度，聚氨酯树脂固化成膜后具有较好的耐磨性、柔韧性和展色性，反光小有利于呈现装饰纸原本的图案色泽，增加装饰纸的品质。

Description

一种装饰纸用抗刮水性聚氨酯树脂及其制备方法
技术领域
本发明属于涂料技术领域，具体涉及一种装饰纸用抗刮水性聚氨酯树脂及其制备方法。
背景技术
装饰纸是建材产品中常用的原料，如家具、橱柜用到的低压板、高压板，还有防火板和底板等，有些装饰纸印有花纹后表面浸渍或涂装有少量树脂，能够清晰地显示装饰纸的花纹，并且增加装饰纸的硬弹性和柔韧性，贴面后无需再进行涂饰，具有操作工艺简单、表面性能优良、花纹美观、价格便宜、耐高温和耐酸碱腐蚀等优点。常规的溶剂型树脂涂料一般采用挥发性有机溶剂，会给环境带来较大污染，水性聚氨酯树脂以水作为溶剂，无甲醛或有毒有机溶剂的挥发，更加环保。
装饰纸在后续板材加工过程和产品使用过程中容易出现划痕，影响美观，为了增加装饰纸的耐刮性，一般会在树脂涂料中添加耐刮剂和其他填充材料，现有技术中常用的有纳米二氧化硅，但是不易分散，并且固化后的漆膜有一定的反光性，在许多角度因为反光无法体现出装饰纸原有的图案和色彩，并且容易折射出细小划痕，观感不佳，所以提出一种具有消光效果的装饰纸用抗刮水性聚氨酯树脂及其制备方法。
发明内容
本发明的目的在于提供一种装饰纸用抗刮水性聚氨酯树脂及其制备方法，以解决背景技术中的问题。
本发明的目的可以通过以下技术方案实现：
一种装饰纸用抗刮水性聚氨酯树脂，包括A组分和B组分，B组分为聚氨酯固化剂；按质量份计，所述A组分包括如下原料：
消光水性聚氨酯乳液60-78份、流平剂0.5-0.8份和消泡剂0.5-0.8份。
进一步地，消光水性聚氨酯乳液通过如下步骤制备：
步骤一：将新戊二醇、2,2-二羟甲基丁酸、三羟甲基丙烷和分子量为1000的聚己二酸-1,4-丁二醇酯真空干燥后加入烧瓶中，然后加入适量丙酮降低反应体系的粘度，在50℃、250r/min的条件下搅拌15min，然后加入甲苯二异氰酸酯和二月桂酸二丁基锡，升温至65℃反应5h，降温至50℃后加入三乙胺调节pH值至7-8，旋转蒸除丙酮，得到羟基型水性聚氨酯预聚体。
步骤二：将真空干燥的2,2-羟甲基丁酸、分子量为2000的聚四氢呋喃醚二醇和异佛尔酮二异氰酸酯真空干燥，然后加入烧瓶中，滴加二月桂酸二丁基锡，在磁力搅拌的条件下升温至50℃，反应1h后升温至70℃反应1h，升温至75℃反应1h，升温至80℃加入环氧树脂继续反应1h，加入三乙胺调节pH值至7-8，降温后加入改性消光粉，超声分散10-15min后剪切分散20-30min，得到消光型聚氨酯预聚体；
步骤三：将消光型聚酯预聚体加入质量分数为16％的乙二胺基乙磺酸钠水溶液中，在250-500r/min的条件下搅拌15-20min，然后加入羟基型水性聚氨酯预聚体，在3500r/min的条件下搅拌20-30min，最后采用二正丁胺-丙酮法滴定测量出未反应的异氰酸酯基团含量，滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液。
进一步地，新戊二醇、2,2-二羟甲基丁酸、三羟甲基丙烷、聚己二酸-1,4-丁二醇酯、丙酮、甲苯二异氰酸酯和二月桂酸二丁基锡的用量比为85g：45g：45-55g：1000g：70-80g：210g：0.13g。
进一步地，2,2-羟甲基丁酸、聚四氢呋喃醚二醇、异佛尔酮二异氰酸酯、二月桂酸二丁基锡、环氧树脂和改性消光粉的用量比为90g：2000g：245g：0.15g：225g：180-200g。
进一步地，羟基型水性聚氨酯预聚体、消光型聚氨酯预聚体和乙二胺基乙磺酸钠水溶液的用量比为12g：25g：12.5g。
进一步地，改性消光粉通过如下步骤制备：
向烧瓶中加入3-(三甲氧基甲硅基)甲基丙烯酸丙酯和无水乙醇并搅拌混合，然后向烧瓶中加入纳米γ-Al2O3，在磁力搅拌的条件下回流1.5-2h，过滤后将滤饼在60-80℃的条件下烘干，粉碎，得到改性消光粉。
进一步地，3-(三甲氧基甲硅基)甲基丙烯酸丙酯、无水乙醇和纳米γ-Al2O3的用量比为10mL：18-20mL：7g。
进一步地，流平剂的型号为Glide450。
进一步地，消泡剂的型号为Silok4600。
进一步地，聚氨酯固化剂为TDI或HDI。
装饰纸用抗刮水性聚氨酯树脂的制备方法包括如下步骤：
将消光水性聚氨酯乳液、流平剂和消泡剂搅拌混合得到组分A，再将组分A和B组分按照5-6：1的质量比混合，得到装饰纸用抗刮水性聚氨酯树脂。
本发明的有益效果：
本发明装饰纸用抗刮水性聚氨酯树脂的流平性和粘附性适中，固化成膜后具有较好的耐磨性、柔韧性和展色性，有利于呈现装饰纸原本的图案色泽，增加装饰纸的品质。
纳米γ-Al2O3的粒径为20nm，比表面积大、尺寸稳定性好，其颗粒尺寸与纳米二氧化硅尺寸相近，但是硬度比纳米二氧化硅要大。纳米γ-Al2O3表面带有羟基，经过3-(三甲氧基甲硅基)甲基丙烯酸丙酯改性后，3-(三甲氧基甲硅基)甲基丙烯酸丙酯发生水解后与纳米γ-Al2O3表面的Al-OH发生缩合，从而接枝在纳米γ-Al2O3表面，最终制得改性消光粉。
纳米γ-Al2O3经过改性后其颗粒表面能降低，与预聚体的相容性增加，从而使改性消光粉具有较好的分散稳定性，有利于提高聚氨酯树脂的粘结度、附着力和硬度。消光型聚氨酯乳液在制备过程中加入环氧树脂并将环氧基团开环后引入到体系中，羟基与异氰酸酯基发生反应，形成网状结构，有利于提高消光型聚氨酯预聚体的稳定性，进一步防止改性消光粉的沉降，并且能够降低固化后聚氨酯树脂的光泽度和接触角，有利于展现装饰纸本身的图案和增加其耐水性和耐碱性。制备含有较多羟基的羟基型水性聚氨酯预聚体并将其与消光型聚氨酯预聚体混合，有利于增加消光水性聚氨酯乳液的水溶性和流平性，然后混入乙二胺基乙磺酸钠水溶液，乙二胺基乙磺酸钠水可以增加这两种预聚体乳的相容性并提供乳化剂和扩链剂的功能，提高消光水性聚氨酯乳液的固含量从而加快其干燥速度，有利于成膜固化；由于两种聚氨酯预聚体的固化速度又存在差异，可以使固化后聚氨酯树脂在微观上具有不平整性，进一步减少光的反射。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
制备消光水性聚氨酯乳液，包括如下步骤：
步骤一：向烧瓶中加入300mL 3-(三甲氧基甲硅基)甲基丙烯酸丙酯和540mL无水乙醇并搅拌混合，然后向烧瓶中加入210g纳米γ-Al2O3，在磁力搅拌的条件下回流1.5h，过滤后将滤饼在60℃的条件下烘干，粉碎，得到改性消光粉。
步骤二：将85g新戊二醇、45g 2,2-二羟甲基丁酸、45g三羟甲基丙烷和1000g分子量为1000的聚己二酸-1,4-丁二醇酯真空干燥后加入烧瓶中，然后加入70g丙酮降低反应体系的粘度，在50℃、250r/min的条件下搅拌15min，然后加入210g甲苯二异氰酸酯和0.13g二月桂酸二丁基锡，升温至65℃反应5h，降温至50℃后加入三乙胺调节pH值至7，旋转蒸除丙酮，得到羟基型水性聚氨酯预聚体。
步骤三：将真空干燥的90g 2,2-羟甲基丁酸、2000g分子量为2000的聚四氢呋喃醚二醇和245g异佛尔酮二异氰酸酯真空干燥，然后加入烧瓶中，滴加0.15g二月桂酸二丁基锡，在磁力搅拌的条件下升温至50℃，反应1h后升温至70℃反应1h，升温至75℃反应1h，升温至80℃加入225g环氧树脂继续反应1h，加入三乙胺调节pH值至7，降温后加入180g改性消光粉，超声分散10min后剪切分散20min，得到消光型聚氨酯预聚体；
步骤四：将2500g消光型聚酯预聚体加入1250g质量分数为16％的乙二胺基乙磺酸钠水溶液中，在2500r/min的条件下搅拌15min，然后加入1200g羟基型水性聚氨酯预聚体，在3500r/min的条件下搅拌20min，最后采用二正丁胺-丙酮法滴定测量出未反应的异氰酸酯基团含量，滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液。
实施例2
制备消光水性聚氨酯乳液，包括如下步骤：
步骤一：向烧瓶中加入300mL 3-(三甲氧基甲硅基)甲基丙烯酸丙酯和570mL无水乙醇并搅拌混合，然后向烧瓶中加入210g纳米γ-Al2O3，在磁力搅拌的条件下回流1.8h，过滤后将滤饼在70℃的条件下烘干，粉碎，得到改性消光粉。
步骤二：将85g新戊二醇、45g 2,2-二羟甲基丁酸、50g三羟甲基丙烷和1000g分子量为1000的聚己二酸-1,4-丁二醇酯真空干燥后加入烧瓶中，然后加入75g丙酮降低反应体系的粘度，在50℃、250r/min的条件下搅拌15min，然后加入210g甲苯二异氰酸酯和0.13g二月桂酸二丁基锡，升温至65℃反应5h，降温至50℃后加入三乙胺调节pH值至7.5，旋转蒸除丙酮，得到羟基型水性聚氨酯预聚体。
步骤三：将真空干燥的90g 2,2-羟甲基丁酸、2000g分子量为2000的聚四氢呋喃醚二醇和245g异佛尔酮二异氰酸酯真空干燥，然后加入烧瓶中，滴加0.15g二月桂酸二丁基锡，在磁力搅拌的条件下升温至50℃，反应1h后升温至70℃反应1h，升温至75℃反应1h，升温至80℃加入225g环氧树脂继续反应1h，加入三乙胺调节pH值至7.5，降温后加入190g改性消光粉，超声分散12min后剪切分散25min，得到消光型聚氨酯预聚体；
步骤四：将2500g消光型聚酯预聚体加入1250g质量分数为16％的乙二胺基乙磺酸钠水溶液中，在400r/min的条件下搅拌18min，然后加入1200g羟基型水性聚氨酯预聚体，在3500r/min的条件下搅拌25min，最后采用二正丁胺-丙酮法滴定测量出未反应的异氰酸酯基团含量，滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液。
实施例3
制备消光水性聚氨酯乳液，包括如下步骤：
步骤一：向烧瓶中加入300mL 3-(三甲氧基甲硅基)甲基丙烯酸丙酯和600mL无水乙醇并搅拌混合，然后向烧瓶中加入210g纳米γ-Al2O3，在磁力搅拌的条件下回流2h，过滤后将滤饼在80℃的条件下烘干，粉碎，得到改性消光粉。
步骤二：将85g新戊二醇、45g 2,2-二羟甲基丁酸、55g三羟甲基丙烷和1000g分子量为1000的聚己二酸-1,4-丁二醇酯真空干燥后加入烧瓶中，然后加入80g丙酮降低反应体系的粘度，在50℃、250r/min的条件下搅拌15min，然后加入210g甲苯二异氰酸酯和0.13g二月桂酸二丁基锡，升温至65℃反应5h，降温至50℃后加入三乙胺调节pH值至8，旋转蒸除丙酮，得到羟基型水性聚氨酯预聚体。
步骤三：将真空干燥的90g 2,2-羟甲基丁酸、2000g分子量为2000的聚四氢呋喃醚二醇和245g异佛尔酮二异氰酸酯真空干燥，然后加入烧瓶中，滴加0.15g二月桂酸二丁基锡，在磁力搅拌的条件下升温至50℃，反应1h后升温至70℃反应1h，升温至75℃反应1h，升温至80℃加入225g环氧树脂继续反应1h，加入三乙胺调节pH值至8，降温后加入200g改性消光粉，超声分散15min后剪切分散30min，得到消光型聚氨酯预聚体；
步骤四：将2500g消光型聚酯预聚体加入1250g质量分数为16％的乙二胺基乙磺酸钠水溶液中，在500r/min的条件下搅拌20min，然后加入1200g羟基型水性聚氨酯预聚体，在3500r/min的条件下搅拌30min，最后采用二正丁胺-丙酮法滴定测量出未反应的异氰酸酯基团含量，滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液。
实施例4
制备装饰纸用抗刮水性聚氨酯树脂，包括如下步骤：
将实施例1中制得的消光水性聚氨酯乳液、Glide450流平剂和Silok4600消泡剂搅拌混合得到组分A，再将组分A和TDI按照5：1的质量比混合，得到装饰纸用抗刮水性聚氨酯树脂。
实施例5
制备装饰纸用抗刮水性聚氨酯树脂，包括如下步骤：
将实施例2中制得的消光水性聚氨酯乳液、Glide450流平剂和Silok4600消泡剂搅拌混合得到组分A，再将组分A和TDI按照6：1的质量比混合，得到装饰纸用抗刮水性聚氨酯树脂。
实施例6
制备装饰纸用抗刮水性聚氨酯树脂，包括如下步骤：
将实施例3中制得的消光水性聚氨酯乳液、Glide450流平剂和Silok4600消泡剂搅拌混合得到组分A，再将组分A和HDI按照5：1的质量比混合，得到装饰纸用抗刮水性聚氨酯树脂。
对比例1：在实施例3的基础上，将纳米γ-Al2O3，替换为纳米二氧化硅，其余步骤保持不变，制备出聚氨酯乳液并按照实施例5的方法制备出聚氨酯树脂。
对比例2：在实施例3的基础上不添加羟基型水性聚氨酯预聚体制备出聚氨酯乳液，然后按照实施例5的方法制备出聚氨酯树脂。
对比例3：在实施例3的基础上，直接将改性消光粉与羟基型水性聚氨酯预聚体混合，然后按照步骤4的方法并用乙二胺基乙磺酸钠水溶液进行乳化，制备出聚氨酯乳液，然后按照实施例5的方法制备出聚氨酯树脂。
对实施例4-实施例6和对比例1-对比例3进行性能测试，首先将实施例1-实施例3和对比例1-对比例3中制备的聚氨酯乳液静置24h，观察聚氨酯乳液的分散情况。其中，实施例1-实施例3、对比例1和对比例2中制备的聚氨酯乳液均一，无沉降微粒，而对比例2中聚氨酯乳液出现沉降微粒，表明实施例1-实施例3中聚氨酯乳液分散性更好。
将实施例4-实施例5和对比例1-对比例3中聚氨酯树脂分别涂布在PVC装饰纸表面制备出试样，漆膜厚度为35±5μm，然后照GB/T 1743-1979、GB/T6739-2006和GB/T 9286-1998检测每组试样漆膜的光泽度、铅笔硬度和附着力，结果如表1所示：
表1
项目 实施例4 实施例5 实施例6 对比例1 对比例2 对比例3
光泽度 2.2 2.2 2.3 8 16 24
铅笔硬度 4H 4H 4H 3H 3H H
附着力 0级 0级 0级 1级 1级 1级
由表1可以看出，实施例4-实施例6中制备聚氨酯树脂具有较好的消光性、硬度和耐磨性。
需要说明的是，在本文中，诸如术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (8)

1.一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，包括A组分和B组分，按质量份计，所述A组分包括如下原料：
消光水性聚氨酯乳液60-78份、流平剂0.5-0.8份和消泡剂0.5-0.8份；
所述B组分为聚氨酯固化剂；
所述消光水性聚氨酯乳液通过如下步骤制备：
步骤一：将真空干燥的2,2-二羟甲基丁酸、聚四氢呋喃醚二醇和异佛尔酮二异氰酸酯混合，加入二月桂酸二丁基锡后在磁力搅拌的条件下升温至50℃反应1h，升温至70℃反应1h，升温至75℃反应1h，升温至80℃加入环氧树脂继续反应1h，加入三乙胺调节pH值至7-8，降温后加入改性消光粉，超声分散后再剪切分散，得到消光型聚氨酯预聚体；
步骤二：将消光型聚酯预聚体加入与乙二胺基乙磺酸钠水溶液搅拌混合，然后加入羟基型水性聚氨酯预聚体搅拌混合，最后采用二正丁胺-丙酮法滴定测量出未反应的异氰酸酯基团含量，滴加乙二胺除去剩余的异氰酸酯基团，得到消光水性聚氨酯乳液；
所述羟基型水性聚氨酯预聚体通过如下步骤制备：
将新戊二醇、2,2-二羟甲基丁酸、三羟甲基丙烷和聚己二酸-1,4-丁二醇酯真空干燥并加入烧瓶中，加入丙酮在50℃、250r/min的条件下搅拌15min，然后加入甲苯二异氰酸酯和二月桂酸二丁基锡，升温至65℃反应5h，降温至50℃后加入三乙胺调节pH值至7-8，旋转蒸除丙酮，得到羟基型水性聚氨酯预聚体；
所述改性消光粉通过如下步骤制备：
向烧瓶中加入3-(三甲氧基甲硅基)甲基丙烯酸丙酯和无水乙醇并搅拌混合，然后加入纳米γ-Al2O3，在磁力搅拌的条件下回流1.5-2h，过滤，将滤饼烘干，粉碎，得到改性消光粉。
2.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，所述新戊二醇、2,2-二羟甲基丁酸、三羟甲基丙烷、聚己二酸-1,4-丁二醇酯、丙酮、甲苯二异氰酸酯和二月桂酸二丁基锡的用量比为85g：45g：45-55g：1000g：70-80g：210g：0.13g。
3.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，步骤一中所述2,2-二羟甲基丁酸、聚四氢呋喃醚二醇、异佛尔酮二异氰酸酯、二月桂酸二丁基锡、环氧树脂和改性消光粉的用量比为90g：2000g：245g：0.15g：225g：180-200g。
4.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，步骤二中所述羟基型水性聚氨酯预聚体、消光型聚氨酯预聚体和乙二胺基乙磺酸钠水溶液的用量比为12g：25g：12.5g。
5.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，所述3-(三甲氧基甲硅基)甲基丙烯酸丙酯、无水乙醇和纳米γ-Al2O3的用量比为10mL：18-20mL：7g。
6.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，所述流平剂的型号为Glide450。
7.根据权利要求1所述的一种装饰纸用抗刮水性聚氨酯树脂，其特征在于，所述聚氨酯固化剂为TDI或HDI。
8.根据权利要求1-7任意一项所述的一种装饰纸用抗刮水性聚氨酯树脂的制备方法，其特征在于，包括如下步骤：
将消光水性聚氨酯乳液、流平剂和消泡剂搅拌混合得到组分A，再将组分A和B组分按照5-6：1的质量比混合，得到装饰纸用抗刮水性聚氨酯树脂。
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