CN111411543B - 一种无醛浸渍胶膜纸用胶黏剂及其制备方法 - Google Patents

一种无醛浸渍胶膜纸用胶黏剂及其制备方法 Download PDF

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CN111411543B
CN111411543B CN202010394895.7A CN202010394895A CN111411543B CN 111411543 B CN111411543 B CN 111411543B CN 202010394895 A CN202010394895 A CN 202010394895A CN 111411543 B CN111411543 B CN 111411543B
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徐建峰
龙玲
刘如
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Research Institute of Wood Industry 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无醛浸渍胶膜纸用胶黏剂及其制备方法，无醛胶黏剂包括以下组分：所述无醛浸渍胶黏剂包括：水性聚氨酯乳液30‑50份，纳米纤维素1‑5份，填料5‑10份，水200‑300份。按照配方比例，将纳米纤维素在室温条件下投入到水和水性聚氨酯乳液中，500‑800r/min条件下搅拌5‑10min；然后将搅拌速度调为1000‑3000r/min，同时向其中投入填料，继续搅拌10‑20min，静置，即得。本申请制备的无醛胶黏剂无甲醛释放，安全环保，其中聚氨酯乳液粒径较小、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纸张的纸间破坏问题，同时提高了浸渍胶膜纸的挂胶量，并在能一定程度上提高胶膜的耐刮擦性能。

Description

一种无醛浸渍胶膜纸用胶黏剂及其制备方法
技术领域
本发明涉及一种无醛浸渍胶膜纸用胶黏剂及其制备方法，属于人造板加工技术领域。
背景技术
作为装饰纸中应用最广泛的一种，浸渍胶膜纸一般是由原纸经浸渍或印刷、浸渍处理而成。一直以来，浸渍处理多采用脲醛胶和三聚氰胺-甲醛胶两段浸胶工艺，生产出来的浸渍胶膜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身体健康造成危害。随着人们对室内环境的要求提高及国家相关环保法律法规的出台，浸渍胶膜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，因此开发浸渍胶膜纸用无醛胶黏剂已成为解决问题的关键。
无醛胶黏剂主要包括天然胶黏剂、(改性)生物基胶黏剂、无醛(改性)高分子树脂胶黏剂(主要包括丙烯酸酯、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、胶合板等人造板的制造，例如中国林业科学研究院林产化学工业研究所(CN 108753208 A)开发了一种基于单宁基改性双组份豆粕胶黏剂，该胶黏剂具有良好的流动性、涂布性、渗透性、储存稳定性、胶合性和耐水性，用其制造的胶合板能够满足国家II类胶合板使用要求。西南林业大学(CN 110734731 A)制备了一种超支化聚脲无醛木材胶黏剂，此类胶黏剂具有合成简单、绿色环保、稳定性好、性能优异等优点，可用于胶合板、刨花板等人造板生产。但此类胶黏剂分子交联较多、粒径大、粘度高。
上述无醛胶黏剂，生物基胶黏剂耐霉变、耐候性差，在纸张浸渍中应用极少。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(CN109776717 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。南京林业大学(CN 109680544 A)开发的纳米纤维素/纳米ZnO复合材料改性丙烯酸胶黏剂，制造了一种疏水型无醛浸渍胶膜纸。但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、挂胶量大的浸渍胶膜纸用无醛胶黏剂显得十分必要。在高分子树脂类胶黏剂中，聚氨酯胶黏剂因其胶膜透明度、光泽度易调，物理强度更为优异，在保证其纸间渗透能力的情况下，是一种优选的胶黏剂。
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浸渍胶膜纸用无醛胶黏剂及其制备方法。按质量分数计，组分包括：
水性聚氨酯乳液：30-50份
纳米纤维素：1-5份
填料：5-10份
水：200-300份。
具体的，所述的纳米纤维素为双醛改性纳米纤维素，固含为0.5％-3％，粒径20-50nm。作为填料分散剂，使填料能均匀稳定地在水性聚氨酯乳液中存在。所述双醛改性纳米纤维素的结构如下：
Figure BSA0000208465090000021
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。其作用为提高浸渍胶膜纸的挂胶量和胶黏剂胶膜的耐刮擦、耐磨性能。
具体的，所述的水性聚氨酯乳液的配方为：二元醇与二异氰酸酯摩尔比为0.8-2，二元醇摩尔份数20-40份，扩链剂3-8份，亲水剂5-10份，冰醋酸0.1-1份，水50-80份。
更具体的，所述的二元醇包括不含脂肪环、芳香环的聚酯二元醇和聚醚二元醇中一种或几种。所述的二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的一种或几种。所述的扩链剂为乙二醇、丙二醇、1，4-丁二醇、一缩二乙二醇、1，4环己二醇中的一种。所述的亲水剂为N-甲基二乙醇胺(MDEA)。
所述水性聚氨酯乳液的制备方法如下：
1)将二元醇与二异氰酸酯按照比例加入到带有搅拌和回流装置的反应釜中，在高纯氮气的保护下，进行预聚反应，反应温度为40-60℃，反应时间为0.5-1h，制得聚氨酯预聚体。
2)将预聚体升温至65-80℃，向预聚体中滴加扩链剂，滴加时长10-20min，扩链反应时长0.5-1.5h，搅拌速度为50-100r/min。然后降温至40-60℃，添加亲水剂，30min内加完，该步反应时长0.5-1.5h。
3)冷却至室温，加入冰醋酸进行中和，同时用适量丙酮降粘，粘度合适后加水并高速剪切，剪切速度为2000-4000r/min，蒸发脱除丙酮即可制得水性聚氨酯乳液；乳液的固含量在20％左右，粒径50-100nm，黏度50-100cp，分子量500-2000。
按照配方比例，将纳米纤维素在室温条件下投入到水和水性聚氨酯乳液中，500-800r/min条件下搅拌5-10min；然后将搅拌速度调为1000-3000r/min，同时向其中投入填料，继续搅拌10-20min，静置，即得到浸渍胶膜纸用无醛胶黏剂。
采用上述无醛胶黏剂对原纸进行浸渍、干燥处理，得到浸渍胶膜纸；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/T15102-2017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)在制备水性聚氨酯乳液时，所选的多元醇为醇羟基少、分子量小的不带脂肪环和芳香环的二元醇；所选的异氰酸酯为分子量较小的二异氰酸酯；选定特定的搅拌速度和较短的反应时长使获得的聚氨酯乳液粒径较小、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。
3)引入绿色环保的改性纳米纤维素作为填料的分散剂，能使填料较好地在聚氨酯乳液中分散。因此引入的填料使得胶黏剂体系在对粘度影响不大的条件下，提高了浸渍胶膜纸的挂胶量，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)将聚乙二醇(分子量200)与异佛尔酮二异氰酸酯按照摩尔比0.8加入到带有搅拌和回流装置的反应釜中，在高纯氮气的保护下，进行预聚反应，反应温度为40℃，反应时间为1h，制得聚氨酯预聚体。
2)将预聚体升温至65℃，向预聚体中滴加1，4-丁二醇，滴加时长20min，扩链反应时长1.5h，搅拌速度为50r/min。然后降温至40℃，添加亲水剂，30min内加完，该步反应时长0.5h。
3)冷却至室温，加入冰醋酸进行中和，同时用适量丙酮降粘，粘度合适后加水并高速剪切，剪切速度为2000r/min，蒸发脱除丙酮即可制得水性聚氨酯乳液。
4)一种装饰纸无醛胶黏剂，按质量分数计，组分包括：
水性聚氨酯乳液：30份
纳米纤维素：5份
二氧化钛(粒径100nm)：10份
水：200份。
按照配方比例，将纳米纤维素在室温条件下投入到水和水性聚氨酯乳液中，500r/min条件下搅拌10min；然后将搅拌速度调为1000r/min，同时向其中投入填料，继续搅拌20min，静置，即得到浸渍胶膜纸用无醛胶黏剂。
采用上述无醛胶黏剂对原纸进行浸渍、干燥处理，得到浸渍胶膜纸；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/T15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
实施例2
1)将聚酯二元醇CMA-1024与异佛尔酮二异氰酸酯按照摩尔比2加入到带有搅拌和回流装置的反应釜中，在高纯氮气的保护下，进行预聚反应，反应温度为60℃，反应时间为0.5h，制得聚氨酯预聚体。
2)将预聚体升温至80℃，向预聚体中滴加乙二醇，滴加时长10min，扩链反应时长0.5h，搅拌速度为100r/min。然后降温至60℃，添加亲水剂，30min内加完，该步反应时长1.5h。
3)冷却至室温，加入冰醋酸进行中和，同时用适量丙酮降粘，粘度合适后加水并高速剪切，剪切速度为4000r/min，蒸发脱除丙酮即可制得水性聚氨酯乳液。
4)一种装饰纸无醛胶黏剂，按质量分数计，组分包括：
水性聚氨酯乳液：50份
纳米纤维素：1份
三氧化二铝(粒径100nm)：5份
水：300份。
按照配方比例，将纳米纤维素在室温条件下投入到水和水性聚氨酯乳液中，800r/min条件下搅拌5min；然后将搅拌速度调为3000r/min，同时向其中投入填料，继续搅拌10min，静置，即得到浸渍胶膜纸用无醛胶黏剂。
采用上述无醛胶黏剂对原纸进行浸渍、干燥处理，得到浸渍胶膜纸；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/T15102-2017和GB/T 17657-2013测试浸渍装饰纸的相关物理性能。
实施例3
1)将聚酯二元醇CMA-1024、聚乙二醇(二者摩尔比1∶1)与六亚甲基二异氰酸酯按照摩尔比1.3加入到带有搅拌和回流装置的反应釜中，在高纯氮气的保护下，进行预聚反应，反应温度为50℃，反应时间为0.7h，制得聚氨酯预聚体。
2)将预聚体升温至75℃，向预聚体中滴加丙二醇，滴加时长15min，扩链反应时长0.8h，搅拌速度为80r/min。然后降温至50℃，添加亲水剂，30min内加完，该步反应时长1h。
3)冷却至室温，加入冰醋酸进行中和，同时用适量丙酮降粘，粘度合适后加水并高速剪切，剪切速度为3000r/min，蒸发脱除丙酮即可制得水性聚氨酯乳液。
4)一种装饰纸无醛胶黏剂，按质量分数计，组分包括：
水性聚氨酯乳液：40份
纳米纤维素：3份
二氧化硅(粒径100nm)4份，二氧化锌(50nm)3份
水：250份。
按照配方比例，将纳米纤维素在室温条件下投入到水和水性聚氨酯乳液中，650r/min条件下搅拌7min；然后将搅拌速度调为2000r/min，同时向其中投入填料，继续搅拌15min，静置，即得到浸渍胶膜纸用无醛胶黏剂。
采用上述无醛胶黏剂对原纸进行浸渍、干燥处理，得到浸渍胶膜纸；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/T15102-2017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的技术方案的区别在于不添加纳米纤维素和填料。
性能测试
表1胶黏剂性能
粘胶剂a 对比例1 实施例1
粒径/nm 100 60 60
固含/wt％ 30 16 30
黏度/cp 300 70 100
平均分子量 60000 1000 800
a.CN 110734731 A
与已公布的聚氨酯无醛胶黏剂相比，本发明制备的胶黏剂粒径更小，分子量更小，这有利于胶黏剂在纸张内部的渗透。同时纳米纤维素分散的填料的添加，保证了胶黏剂的固含量和粘度，提高了浸渍纸的挂胶量。
表2装饰纸物理性能对比
Figure BSA0000208465090000051
a.CN 110450239 A 测试参照国标：GB/T 28995-2012、GB/T 17657-2013、GB/T15102-2017
经本发明胶黏剂制备的浸渍胶膜纸纸没有游离甲醛的释放，与已公布的聚氨酯无醛胶黏剂相比，胶液的渗透性以及由此生产的饰面人造板的表面结合性能、耐划痕性能更好，且均满足相关国家标准的要求。胶黏剂配方中的填料增加了浸渍胶膜纸的挂胶量，一定程度上提高了产品的耐刮擦、耐磨性能。

Claims (8)

1.一种浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，步骤如下：
1)将二元醇与二异氰酸酯按照比例加入到带有搅拌和回流装置的反应釜中，在高纯氮气的保护下，进行预聚反应，反应温度为40-60℃，反应时间为0.5-1h，制得聚氨酯预聚体；
2)将预聚体升温至65-80℃，向预聚体中滴加扩链剂，滴加时长10-20min，扩链反应时长0.5-1.5h，搅拌速度为50-100r/min，然后降温至40-60℃，添加亲水剂，30min内加完，该步反应时长0.5-1.5h；
3)冷却至室温，加入冰醋酸进行中和，同时用适量丙酮降粘，粘度合适后加水并高速剪切，剪切速度为2000-4000r/min，蒸发脱除丙酮即可制得水性聚氨酯乳液；乳液的固含量在20％，粒径50-100nm，黏度50-100cp，分子量500-2000；
4)按照配方比例，将纳米纤维素在室温条件下投入到水中，500-800r/min条件下搅拌5-10min；然后将搅拌速度调为1000-3000r/min，同时向其中投入填料，继续搅拌10-20min，静置，即得；
其中，按质量分数计，所述配方比例为：
水性聚氨酯乳液：30-50份
纳米纤维素：1-5份
填料：5-10份
水：200-300份；
所述的纳米纤维素为双醛改性纳米纤维素，固含为0.5％-3％，粒径20-50nm。
2.根据权利要求1所述的浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，所述二元醇与二异氰酸酯摩尔比为0.8-2，二元醇摩尔份数20-40份，扩链剂3-8份，亲水剂5-10份，冰醋酸0.1-1份，水50-80份。
3.根据权利要求2所述的浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，所述的二元醇包括不含脂肪环、芳香环的聚酯二元醇和聚醚二元醇中的一种或几种。
4.根据权利要求2所述的浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，所述的二异氰酸酯包括异佛尔酮二异氰酸酯IPDI、二苯基甲烷二异氰酸酯MDI、二环己基甲烷二异氰酸酯HMDI、六亚甲基二异氰酸酯HDI、赖氨酸二异氰酸酯LDI中的一种或几种。
5.根据权利要求1所述的浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，所述的扩链剂为乙二醇、丙二醇、1，4-丁二醇、一缩二乙二醇、1，4环己二醇中的一种。
6.根据权利要求1所述的浸渍胶膜纸用无醛胶黏剂的制备方法，其特征在于，所述的亲水剂为N-甲基二乙醇胺(MDEA)。
7.根据权利要求1所述的浸渍胶膜纸用无醛胶黏剂的制备方法，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％；粒径50-100nm的二氧化硅悬浮液，质量分数10％；50-100nm的二氧化锌悬浮液，质量分数10％；粒径50-200nm的三氧化二铝悬浮液，质量分数10％中的一种或者几种的组合。
8.根据权利要求1-7任一项所述的浸渍胶膜纸用无醛胶黏剂制备方法制备得到的无醛胶黏剂。
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Assignor: RESEARCH INSTITUTE OF WOOD INDUSTRY, CHINESE ACADEMY OF FORESTRY

Contract record no.: X2022990000186

Denomination of invention: The invention relates to an adhesive for aldehyde free impregnated adhesive film paper and a preparation method thereof

Granted publication date: 20220128

License type: Common License

Record date: 20220330