反复粘贴压敏胶与阀口袋用聚氨酯胶的制备应用
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摘要
便事贴产品中使用的压敏胶是一类具有特殊微球结构且能反复粘贴的胶粘剂,目前国内产业化的报导很少不能满足生产与市场的要求。本文采用悬浮聚合法制备了反复粘贴微球型丙烯酸压敏胶。以丙烯酸异辛酯(2-EHA)为软单体、三烯丙基异三聚氰酸酯(TAIC)为交联剂、在含有分散剂的水相中采用悬浮聚合的方法制备了粒径为10～100μm粘性聚合物微球。使用这种微球富集相按照一定比例调配自制的乳液,增稠剂及其他添加剂制得的压敏胶液用线棒涂布器涂布于纸等基材上烘干得具有良好再剥离性的反复粘贴压敏胶。其具体性能指标为：平均粒径：53μm；初粘：6号球；剥离强度：1.21 N/25mm;100次粘贴剥离强度：1.06N/25mm; 2 kg重压一周后仍能轻易剥离而不损伤纸面。样品适用于各种表面的粘贴,可以作为便事贴、各种难粘表面的表面保护膜、医用压敏胶使用。
在研究中发现：在有机相中添加一定量的单体A,无需在复杂的工艺条件下便能显著减小微球的粒径并使单分散性上升,比较合适的用量为单体质量的3%；通过实验确定了最适宜的工艺参数为：分散剂PVA的用量不大于1%、油水比1：3、搅拌速度为400-500r/min、水相pH值稳定在7～8。
通过剥离强度测试以及再剥离性能的测试,获得了微球粒径大小与此类胶粘剂性能的关系。并通过弹性力学中相关知识模拟推导了随时间和在重压下不同粒径大小的微球压敏胶剥离强度的增长情况,与实验结果印证一致。本文认为经过同样的时间和重压下,小粒径微球剥离强度增长幅度较之大粒径微球来的大,其性质更接近乳液压敏胶。
本文对阀口袋用双组份聚氨酯胶粘剂小试与中试工艺进行了研究,讨论了软段分子量对剥离强度以及胶液粘度、软段结构的规整性对胶粘剂结晶性能、催化剂的使用对固化过程、增粘剂的使用对胶粘剂性能的影响,以及在实际施胶过程中出现的一些问题如溶剂挥发速度的影响因素等。结果表明,使用分子量为2000的结晶性聚己二酸-1,4-丁二醇酯多元醇(PBA),配以部分非结晶性聚酯多元醇,TDI与MDI的异氰酸根指数R值范围为0.95～0.98,硬段含量Ch值范围12%～20%,采用一步法本体聚合制备出的聚氨酯胶粘剂胶粒,经乙酸乙酯溶解后加入固化剂与增粘剂,得到的胶液具有良好的综合性能。在15%固含的乙酸乙酯溶剂中胶液粘度为21s(涂四杯)；固化24h后剥离强度为32.5N/25mm;经过破坏性实验时PE膜破坏。根据该配方和工艺要求,我们自行设计了年产一千吨中试生产线,在一企业进行了中试生产,成功生产出合格产品,产品质量与实验室小试完全一致,并在日产8万条阀口袋全自动生产线上应用成功,获得了企业的认可。目前生产出的产品较之国内外产品价格更为低廉,性能优良,正逐渐走上市场,以取代国内外公司同类产品。
实际生产使用中发现胶粘剂因PBA类聚酯二元醇较高的结晶性会产生一些缺陷,如：胶膜过于致密影响溶剂的挥发和初粘性过大在机器涂布生产线上容易发生粘连的事故等。本文通过加入非结晶性聚酯多元醇共混的做法减少胶粘剂的结晶性,并运用DSC曲线图表征了样品的结晶性,通过积分峰面积计算出了结晶度的变化。用偏光显微镜观察了纯PBA样品和共混样品的结晶情况,证实了其结晶性的降低和结晶速度的下降。结果表明添加10%～30%质量比的非结晶性聚酯多元醇便可使干燥时间从原本的5～7d缩短至2d以内,并且剥离强度没有明显的减少。
研究了在胶液调配时添加0.1%的T-12催化剂对固化进程的影响,通过观察添加催化剂的量对胶粘剂剥离强度变化情况,发现T-12能显著加速双组份聚氨酯胶粘剂的固化,能使固化达标时间从2-3d缩短至1d以内。并且通过红外图谱分析了双组份聚氨酯胶粘剂的一些结构特征,通过-NCO的特征峰高度的变化情况进一步验证了T-12的催化效果。
研究了增粘剂对胶粘剂表干时间,固化时间,固化后剥离强度的影响。通过实验确定了最适合的增粘剂添加量,结果表明在调配时添加占胶液质量5%左右的增粘剂能有效的增加胶粘剂的剥离强度,能将未添加前的21.3N/25mm的剥离强度提升至32.5N/25mm。
The pressure-sensitive adhesive (PSA) used in POST ITTM products has special microspherical structure and repositionable.There are few reports of industrialization at present, and these peoducts can not meet the requirement of market. A series of acrylic PSA microspheres were prepared by suspension polymerization in this paper. Based on acrylic monomers, an initiator, a polymeric stabilizer, wherein the reaction occurs in water to yield a microsphere adhesive. The copolymer microspheres are having diameters in the range of about 10-100μm. By mixing the cream(the microsphere-rich phase) with certain percentage of the emulsion, thickeners and other additives, then coated it through a 100μm gap mayer bar onto the paper, after drying that have good repositionable PSA. In accordance with the detection of patents, the performance of PSA was similar to products abroad. The specific performance indicators were:average particle size:53μm, tack:6# Ball, peel strength:1.21 N/25mm,100 times paste peel strength:1.16 N/25mm; with 2 kg's pressure during a week it can be easily peeled without injury stripping paper. This adhesive can be used as Post-it self-stick notes or the surface protective film adhesive and even for medical use.
The amount of monomer A, the amount of dispersant, oil and water ratio, stirring speed, pH value of aqueous phase were studied in the paper. The results showed that the using of monomer A can significantly reduce the size of microspheres and improve the monodispersity without the complicated process conditions. The appropriate amount was about 3% of the monomer mass. Under laboratory conditions the most appropriate value of this experiment were: the amount of dispersant PVA:less than 1%, oil-water ratio of 1:3, stirring speed: 400-500r/min, pH values of aqueous phase stabilized at 7-8.
By the testing of peel strength and repositionability, we have found the influence of microsphere size on adhesive properties. And also derivate the increase of peel strength over time and under pressure of different sizes of microspheres by using the theory of elasticity, which was confirmed by the experimental results.
The pilot scale process of two-component polyurethane adhesive for valve bag was also studied in this paper. The factors such as the molecular weight of soft segment, the structure of soft segment, the using of catalyst and tackifiers were disscused. The results showed that the adhesive had the good integration performance including solvent:ethyl acetate, solids content: 15%, viscosity:21s (measured by TU-4 cup viscometer), curing time:24h, peel strength: 32.5N/25mm, destructive experiments:PE film damage, when crystalline PBA2000 and non crystalline polyester polyol were used as main material. The isocyanate index was 0.95-0.98, hard segment content was 12～20% through one-step bulk polymerization. According to the formula and process we have designed a production line which can output 1 thousand tons per year, and have produced the qualified products during pilot scale production, and running smoothly in the automated production line. Our products have excellent performance and lower price and which is gradually into the market to replace the products at home and abroad.
Some defects was found in actual production such as slow solvent evaporation and excessive tack because of the high crystalline of PBA. By blending the non-crystalline polyester polyol, we had reduced the crystallinity of adhesive. DSC was used to characterize the crystallinity of the sample and then observed the crystallization conditions by polarizing microscope. The results showed that the addition of 10%-30% ratio of non-crystalline polyester polyol can reduce the drying time from 5-7d to less than 2d, and there was no significant reduction in peel strength.
The effect of the catalyst T-12 on curing process was studied. By testing the peel strength of adhesive over time we had found that the T-12 could significantly speed up the curing of two-component polyurethane adhesive, which can shorten the curing time from 2-3d to less than 1d. Structural characteristics of infrared spectra for two-component polyurethane adhesive were analyzed to verify the catalytic effect of T-12 such as the changing of NCO peak.
The effect of the tackifier on dry time, curing time, the impact peel strength after curing were also studied in this paper. The most appropriate amount of tackifier was about 5% of glue. The result showed that it can improve the peel strength from 21.3N/25mm to 32.5N/25mm.
在研究中发现：在有机相中添加一定量的单体A,无需在复杂的工艺条件下便能显著减小微球的粒径并使单分散性上升,比较合适的用量为单体质量的3%；通过实验确定了最适宜的工艺参数为：分散剂PVA的用量不大于1%、油水比1：3、搅拌速度为400-500r/min、水相pH值稳定在7～8。
通过剥离强度测试以及再剥离性能的测试,获得了微球粒径大小与此类胶粘剂性能的关系。并通过弹性力学中相关知识模拟推导了随时间和在重压下不同粒径大小的微球压敏胶剥离强度的增长情况,与实验结果印证一致。本文认为经过同样的时间和重压下,小粒径微球剥离强度增长幅度较之大粒径微球来的大,其性质更接近乳液压敏胶。
本文对阀口袋用双组份聚氨酯胶粘剂小试与中试工艺进行了研究,讨论了软段分子量对剥离强度以及胶液粘度、软段结构的规整性对胶粘剂结晶性能、催化剂的使用对固化过程、增粘剂的使用对胶粘剂性能的影响,以及在实际施胶过程中出现的一些问题如溶剂挥发速度的影响因素等。结果表明,使用分子量为2000的结晶性聚己二酸-1,4-丁二醇酯多元醇(PBA),配以部分非结晶性聚酯多元醇,TDI与MDI的异氰酸根指数R值范围为0.95～0.98,硬段含量Ch值范围12%～20%,采用一步法本体聚合制备出的聚氨酯胶粘剂胶粒,经乙酸乙酯溶解后加入固化剂与增粘剂,得到的胶液具有良好的综合性能。在15%固含的乙酸乙酯溶剂中胶液粘度为21s(涂四杯)；固化24h后剥离强度为32.5N/25mm;经过破坏性实验时PE膜破坏。根据该配方和工艺要求,我们自行设计了年产一千吨中试生产线,在一企业进行了中试生产,成功生产出合格产品,产品质量与实验室小试完全一致,并在日产8万条阀口袋全自动生产线上应用成功,获得了企业的认可。目前生产出的产品较之国内外产品价格更为低廉,性能优良,正逐渐走上市场,以取代国内外公司同类产品。
实际生产使用中发现胶粘剂因PBA类聚酯二元醇较高的结晶性会产生一些缺陷,如：胶膜过于致密影响溶剂的挥发和初粘性过大在机器涂布生产线上容易发生粘连的事故等。本文通过加入非结晶性聚酯多元醇共混的做法减少胶粘剂的结晶性,并运用DSC曲线图表征了样品的结晶性,通过积分峰面积计算出了结晶度的变化。用偏光显微镜观察了纯PBA样品和共混样品的结晶情况,证实了其结晶性的降低和结晶速度的下降。结果表明添加10%～30%质量比的非结晶性聚酯多元醇便可使干燥时间从原本的5～7d缩短至2d以内,并且剥离强度没有明显的减少。
研究了在胶液调配时添加0.1%的T-12催化剂对固化进程的影响,通过观察添加催化剂的量对胶粘剂剥离强度变化情况,发现T-12能显著加速双组份聚氨酯胶粘剂的固化,能使固化达标时间从2-3d缩短至1d以内。并且通过红外图谱分析了双组份聚氨酯胶粘剂的一些结构特征,通过-NCO的特征峰高度的变化情况进一步验证了T-12的催化效果。
研究了增粘剂对胶粘剂表干时间,固化时间,固化后剥离强度的影响。通过实验确定了最适合的增粘剂添加量,结果表明在调配时添加占胶液质量5%左右的增粘剂能有效的增加胶粘剂的剥离强度,能将未添加前的21.3N/25mm的剥离强度提升至32.5N/25mm。
The pressure-sensitive adhesive (PSA) used in POST ITTM products has special microspherical structure and repositionable.There are few reports of industrialization at present, and these peoducts can not meet the requirement of market. A series of acrylic PSA microspheres were prepared by suspension polymerization in this paper. Based on acrylic monomers, an initiator, a polymeric stabilizer, wherein the reaction occurs in water to yield a microsphere adhesive. The copolymer microspheres are having diameters in the range of about 10-100μm. By mixing the cream(the microsphere-rich phase) with certain percentage of the emulsion, thickeners and other additives, then coated it through a 100μm gap mayer bar onto the paper, after drying that have good repositionable PSA. In accordance with the detection of patents, the performance of PSA was similar to products abroad. The specific performance indicators were:average particle size:53μm, tack:6# Ball, peel strength:1.21 N/25mm,100 times paste peel strength:1.16 N/25mm; with 2 kg's pressure during a week it can be easily peeled without injury stripping paper. This adhesive can be used as Post-it self-stick notes or the surface protective film adhesive and even for medical use.
The amount of monomer A, the amount of dispersant, oil and water ratio, stirring speed, pH value of aqueous phase were studied in the paper. The results showed that the using of monomer A can significantly reduce the size of microspheres and improve the monodispersity without the complicated process conditions. The appropriate amount was about 3% of the monomer mass. Under laboratory conditions the most appropriate value of this experiment were: the amount of dispersant PVA:less than 1%, oil-water ratio of 1:3, stirring speed: 400-500r/min, pH values of aqueous phase stabilized at 7-8.
By the testing of peel strength and repositionability, we have found the influence of microsphere size on adhesive properties. And also derivate the increase of peel strength over time and under pressure of different sizes of microspheres by using the theory of elasticity, which was confirmed by the experimental results.
The pilot scale process of two-component polyurethane adhesive for valve bag was also studied in this paper. The factors such as the molecular weight of soft segment, the structure of soft segment, the using of catalyst and tackifiers were disscused. The results showed that the adhesive had the good integration performance including solvent:ethyl acetate, solids content: 15%, viscosity:21s (measured by TU-4 cup viscometer), curing time:24h, peel strength: 32.5N/25mm, destructive experiments:PE film damage, when crystalline PBA2000 and non crystalline polyester polyol were used as main material. The isocyanate index was 0.95-0.98, hard segment content was 12～20% through one-step bulk polymerization. According to the formula and process we have designed a production line which can output 1 thousand tons per year, and have produced the qualified products during pilot scale production, and running smoothly in the automated production line. Our products have excellent performance and lower price and which is gradually into the market to replace the products at home and abroad.
Some defects was found in actual production such as slow solvent evaporation and excessive tack because of the high crystalline of PBA. By blending the non-crystalline polyester polyol, we had reduced the crystallinity of adhesive. DSC was used to characterize the crystallinity of the sample and then observed the crystallization conditions by polarizing microscope. The results showed that the addition of 10%-30% ratio of non-crystalline polyester polyol can reduce the drying time from 5-7d to less than 2d, and there was no significant reduction in peel strength.
The effect of the catalyst T-12 on curing process was studied. By testing the peel strength of adhesive over time we had found that the T-12 could significantly speed up the curing of two-component polyurethane adhesive, which can shorten the curing time from 2-3d to less than 1d. Structural characteristics of infrared spectra for two-component polyurethane adhesive were analyzed to verify the catalytic effect of T-12 such as the changing of NCO peak.
The effect of the tackifier on dry time, curing time, the impact peel strength after curing were also studied in this paper. The most appropriate amount of tackifier was about 5% of glue. The result showed that it can improve the peel strength from 21.3N/25mm to 32.5N/25mm.
引文
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