CN115109178B - 一种添加树脂及含有其的阻隔保护层、高阻隔膜和阻氧、阻水汽包装材料 - Google Patents
一种添加树脂及含有其的阻隔保护层、高阻隔膜和阻氧、阻水汽包装材料 Download PDFInfo
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- CN115109178B CN115109178B CN202210717313.3A CN202210717313A CN115109178B CN 115109178 B CN115109178 B CN 115109178B CN 202210717313 A CN202210717313 A CN 202210717313A CN 115109178 B CN115109178 B CN 115109178B
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Classifications
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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Abstract
本发明提供一种添加树脂及含有其的阻隔保护层、高阻隔膜和阻氧、阻水汽包装材料。所述添加树脂是2‑[(3,5‑二甲基‑1‑H‑吡唑基)羧氨基]乙基丙烯酸酯、乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)、丙烯酸(或甲基丙烯酸)通过共聚反应合成的高分子树脂。添加树脂与聚乙烯醇混合使用,能和聚乙烯醇的共混,能够减少聚乙烯醇的水汽溶涨性,作为阻隔保护层使用,能同时提高阻隔保护层的阻隔性和柔韧性;另外本发明的高阻隔膜采用二氧化硅和聚乙烯醇双阻隔,同时解决了聚乙烯醇的溶胀性、同二氧化硅层的结合力、以及聚乙烯层的韧性以及印刷适应性问题,大大提高了高阻隔膜材料的阻隔性能和后期应用适应性。
Description
一种添加树脂及含有其的阻隔保护层、高阻隔膜和阻氧、阻水汽包装材料
技术领域
本发明属于高功能膜材料技术领域,涉及一种添加树脂及含有其的阻隔保护层,具体涉及具有阻氧、阻水汽特性的透明高阻隔膜材料及阻氧、阻水汽包装材料。
背景技术
高分子薄膜材料被广泛应用于包装领域。
由于被包装产品的特殊性,对包装材料提出了特殊要求,如食品、医药、电子产品,对包装材料的气体透过率特别是氧气、水蒸气的透过率提出了特殊要求。满足上述阻隔气体透过要求的膜材料统称为高阻隔膜材料。
近年来多层复合、共混、共聚、蒸镀技术发展极为迅速产生了多层复合性、双向拉伸型、铝蒸镀型、黏合剂涂覆型等高阻隔膜。
为了提高阻隔材料的阻隔性能,目前常采用的技术手段主要有以下几种:
1、多层复合:多层复合是指通过一定的工艺将两种或几种阻隔性能不同的薄膜复合到一起。这样一来,渗透分子要想到达包装内部就得通过几层膜,相当于延长了渗透路径,从而使阻隔性能得到提高。该方法是综合了各种膜的优点而制备出的一种综合性能优异的复合薄膜,其工艺简单。但是与本征型高阻隔材料相比,用此方法制备薄膜较厚,容易出现气泡或开裂褶皱等影响阻隔性能的问题,而且多层共挤对设备要求相对复杂,成本较高。
2、双向拉伸:通过双向拉伸可使聚合物薄膜在纵横两个方向上进行取向,使分子链排列的有序度提高,堆砌更紧密,从而使小分子更难通过,进而改善阻隔性能,这种方法使本征型高阻隔聚合物薄膜的制备工艺复杂化,且阻隔性能也难有得到显著提高。
3、表面涂覆:表面涂覆即利用物理气象沉积(PVD)、化学气相沉积(CVD)、原子层沉积(ALD)、分子层沉积(MLD)、层层自组装(LBL)或磁控溅射沉积等技术在聚合物表面沉积金属氧化物或氮化物等材料,从而在薄膜表面形成致密且阻隔性能优异的涂层,上述技术路线,表面涂覆型工艺简单,成本较低,而且生产的高阻隔膜材料阻隔性能较好。
一种表面涂覆的方法是在薄膜上镀覆氧化硅,日本凸版印刷株式会社CN93120385公开了含二氧化硅沉积层的多层薄膜,具备一定的阻隔性,但其阻隔性能仍不高。
另一种方法是涂布聚乙烯醇。聚乙烯醇具有优异的气体阻隔性,越来越多的技术人员试图将其扩展到高阻隔膜领域,但是聚乙烯醇有个巨大的缺点:其耐蒸煮型差,直接影响膜后期的气体阻隔性。日本吴羽化学株式会社在CN9417893提出了改进方法,用聚乙烯醇和聚(甲基)丙烯酸部分中和产物混合制造隔气膜的方法,具备一定的阻隔性,但是其阻隔性能仍不高。
可以将上述两种技术结合,即同时涂布二氧化硅和聚乙烯醇两种阻隔层,但需要解决二氧化硅层和聚乙烯醇层的复合后的粘结牢度问题,同时要解决及乙烯醇的溶胀性、提高韧性和印刷适应性的问题。
发明内容
为解决上述问题,本发明提供一种添加树脂及含有其的阻隔保护层、高阻隔膜和阻氧、阻水汽包装材料。本发明提供的添加树脂与聚乙烯醇混合使用,能和聚乙烯醇的共混,能够减少聚乙烯醇的水汽溶涨性,作为阻隔保护层使用,能同时提高阻隔保护层的阻隔性和柔韧性;另外本发明的高阻隔膜采用二氧化硅和聚乙烯醇双阻隔,同时解决了聚乙烯醇的溶胀性、同二氧化硅层的结合力、以及聚乙烯层的韧性以及印刷适应性问题,大大提高了高阻隔膜材料的阻隔性能和后期应用适应性。
本发明的目的是以下述方式实现的:一种添加树脂,其特征在于:所述添加树脂是2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)、丙烯酸(或甲基丙烯酸)通过共聚反应合成的高分子树脂。
一种阻隔保护层,所述阻隔保护层的成分是聚乙烯醇和上述所述的添加树脂的混合物。
一种高阻隔膜,包括高分子基材,高分子基材的上方从下向上设有氧化硅沉积层、阻隔保护层,其中阻隔保护层是上述所述的阻隔保护层。
进一步地,高分子基材与氧化硅沉积层之间还设有粘结层。
首先描述高阻隔膜的高分子基材。
本发明的高阻隔膜选用的高分子基材选用各种高分子材料制造的薄膜材料,可以举例的高分子材料如聚对苯二甲酸乙二醇酯、聚萘二酸乙二醇酯、聚碳酸酯、聚酰亚胺、聚烯烃类树脂、聚氨酯类树脂、纤维素类高分子等等,它们制造的膜材都具备一定柔韧性,可以制造膜材料。用这些高分子材料制造的薄膜可以是由一种或者几种高分子材料共混或者多层共挤、甚至参杂无机材料如二氧化钛、二氧化硅等微粒制造的薄膜。本发明的高阻隔膜的高分子基材优先选用聚对苯二甲酸乙二醇酯、聚萘二酸乙二醇酯、聚碳酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯等高分子材料制造的薄膜,这种膜材料具有良好的柔韧性和透光性。这些高分子基材的厚度可以是5-500μm,本发明的高阻隔膜的高分子基材厚度优选10-125μm。
其次描述本发明的高阻隔膜的粘结层。
高阻隔膜的生产工艺大部分是在经过电晕或等离子处理的高分子基材上沉积二氧化硅层,该工艺有一个明显的不足,表现为高分子基材和二氧化硅沉积层的结合牢度不够。本发明的高阻隔膜设置粘结层,可以提高高分子基材和二氧化硅沉积层的结合牢度,同时可以增加膜材的气体阻隔效果。粘结层可以选用的粘合剂可以是聚丙烯酸类粘合剂、聚酯类粘合剂、聚醚类粘合剂、聚氨酯类粘合剂、硅烷类粘合剂、硅酮类粘合剂、酚醛类粘合剂、环氧类粘合剂、合成橡胶类等等。本发明的高阻隔膜的粘结层选用聚氨酯类粘合剂,它具有优异的粘结力、阻隔性、柔韧性和耐侯性。这类聚氨酯粘合剂一般是由异氰酸酯和羟基化合物合成。可以是单异氰酸酯、二异氰酸酯或多异氰酸酯和单羟基化合物、二羟基化合物以及多羟基化合物反应合成的线性或交联的粘合剂,它可以制作成单组份、双组分以及多组分粘合剂。异氰酸酯包括甲苯异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二异氰酸酯二环己基甲烷、苯二亚甲基二异氰酸酯以及它们的二聚体、缩聚体等等,单羟基化合物、二羟基化合物以及多羟基化合物,醇类如1,4-丁二醇、乙二醇、1,4-己二醇等;含羟基的羧酸化合物如二羟甲基丙酸、二羟乙基丙酸等等;含羟基的高分子化合物如聚乙二醇、聚丙二醇、聚乙烯醇、纤维素等等。本发明的高阻隔膜的粘结层是在经过电晕或等离子处理的高分子基材上涂布聚氨酯类粘合剂,涂布量为0.1—5g/m2,优选0.5—2g/m2。
以下描述本发明的高阻隔膜的氧化硅沉积层。
第一代阻隔包装材料主要为有机薄膜多层复合或共挤,虽然阻隔性能高,但工艺复杂,回收困难,污染环境,成本高;第二代阻隔包装材料采用铝箔或蒸镀薄膜铝作为阻隔层,这类阻隔薄膜的工艺相对简单,对空气、水分阻隔性也较高,但不透明性、不能用金属探测器检查等属性,同样回收困难、污染环境等,限制着其应用的范围。第三代阻隔包装材料,即在有机薄膜表面蒸镀或化学气相沉积氧化物。
本发明的高阻隔膜设置氧化硅沉积层。氧化硅沉积层对O2、水蒸汽和油脂等阻隔性高,可延长食品药品的存储期,同时,可以阻止聚合物基膜中小分子和助剂等有害物的热迁移,提高包装物品的安全性。本发明的高阻隔膜在粘结层上形成氧化硅沉积层,附着力牢、韧性好、耐蒸煮性好、可微波加工被包装物。
本发明的高阻隔膜氧化硅沉积层为等离子体增强化学气相沉积的二氧化硅沉积层。根据磁场对带电粒子的约束原理,等离子体增强化学气相沉积技术借助于磁场约束电子以提高气体分子的离解率达到提高薄膜沉积速率的目的。以有机硅化合物和氧气的混合气体来沉积氧化硅薄膜。可选择的有机硅化合物有六甲基二硅氧烷、四甲氧基硅烷、四乙氧基硅烷、二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二乙基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、四甲基硅烷等,优选六甲基二硅氧烷。当二氧化硅沉积层的厚度小于30nm时,膜材的气体阻隔性能明显下降,当二氧化硅沉积层的厚度大于100nm时,膜材的可卷曲性和透明性受影响,所以本发明的高阻隔膜的气体二氧化硅沉积层厚度为40-80nm,优选50-60nm。
最后描述高阻隔膜的阻隔保护层。
本发明的高阻隔膜等离子体增强化学气相沉积二氧化硅沉积层后,需要设置阻隔保护层,保护二氧化硅沉积层不被破坏,同时提高使用适应性,比如热合性、印刷性等等。最简单的方法是涂布一层聚乙烯醇保护层。聚乙烯醇(PVA)膜对氧气、氮气、氢气及二氧化碳都具有优秀的阻隔性,而且其价格低廉,但是其易受到后期环境湿气的影响,阻隔性和对二氧化硅沉积层防护性能均下降,另外聚乙烯醇的热合性和印刷适应性较差,可以通过加入添加树脂改善以上缺点。本发明的高阻隔膜的阻隔保护层采用聚乙烯醇和添加树脂的混合物,该添加树脂是2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)、丙烯酸(或甲基丙烯酸)通过共聚反应合成的高分子树脂,它含有3种遥爪功能基团:硅氧烷基、3,5-二甲基-1-H-吡唑基封闭型异氰酸酯基和羧基,3种遥爪功能基团在加热的作用下均能发生交联反应,硅氧烷基介于无机和有机界面之间,可形成有机基体-硅烷偶联剂-无机基体的结合层,大大提高阻隔保护层和二氧化硅沉积层的牢度;3,5-二甲基-1-H-吡唑基封闭型异氰酸酯基在热的作用下释放出活性异氰酸酯基,和聚乙烯醇的羟基反应形成氨酯键,减少聚乙烯醇的水汽溶涨性,形成的聚氨酯键能同时提高阻隔保护层的阻隔性和柔韧性;(甲基)丙烯酸的羧基能提供前期和聚乙烯醇的共混性,有利于在实现水性涂布,后期羧基能和聚乙烯醇的羟基在高温下发生热交联,进一步提高阻隔性。
本发明高阻隔膜的阻隔保护层中的聚乙烯醇水解度大于95%,聚合度大于500。
本发明高阻隔膜的阻隔保护层中添加树脂按重量百分比计算,三种共聚单体的优选比例为:2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯为10-30%,乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)为20-60%,丙烯酸(或甲基丙烯酸)为30-70%。
合成本发明所述的添加树脂采用溶液或乳液共聚的方法,共聚反应可选无规共聚或嵌段共聚,优选无规共聚。聚合的引发剂包括过氧化物如二叔丁基过氧化物、苯甲酰基过氧化物,过硫酸盐如过硫酸钾、过硫酸胺,偶氮化合物如偶氮二异丁腈等,共聚方式优选溶液聚合,可选用的反应溶剂有水、醇类、酮类、酯类、醚类等常见有机合成溶剂或者是它们的混合物。共聚反应温度优选40-100℃,最优为60-90℃。
本发明所述的添加树脂重均分子量为4000-150000,玻璃化转化温度为110-130℃。
阻隔保护层中:聚乙烯醇的重量百分比为70-90%,添加树脂的重量百分比为10-30%,本发明的阻隔保护层通常用该领域己知技术涂布如,刀涂,刮涂,条涂,辊涂,压涂等,涂布量为0.5—2g/m2。
本发明提供的添加树脂与聚乙烯醇混合使用,能和聚乙烯醇的共混,能够减少聚乙烯醇的水汽溶涨性,作为阻隔保护层使用,能同时提高阻隔保护层的阻隔性和柔韧性;另外本发明的高阻隔膜采用二氧化硅和聚乙烯醇双阻隔,同时解决了聚乙烯醇的溶胀性、同二氧化硅层的结合力、以及聚乙烯层的韧性以及印刷适应性问题,大大提高了高阻隔膜材料的阻隔性能和后期应用适应性。
具体地,本发明的高阻隔膜采用多种方式实现气体阻隔,粘结层、氧化硅沉积层和阻隔保护层都可以阻隔气体。阻隔保护层是聚乙烯醇和添加树脂的混合物,聚乙烯醇提供阻隔性,添加树脂是2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)、丙烯酸(或甲基丙烯酸)通过共聚反应合成的高分子树脂,它含有3种遥爪功能基团:硅氧烷基、3,5-二甲基-1-H-吡唑基封闭型异氰酸酯基和羧基,3种遥爪功能基团在加热的作用下均能发生交联反应,硅氧烷基介于无机和有机界面之间,可形成有机基体-硅氧烷基-无机基体(有机基体是指高阻隔膜保护层,无机基体是指氧化硅沉积层,硅氧烷基是桥梁,使二者结合更牢)的结合层,大大提高阻隔保护层和二氧化硅沉积层的牢固度;3,5-二甲基-1-H-吡唑基封闭型异氰酸酯基在热的作用下释放出活性异氰酸酯基,和聚乙烯醇的羟基反应生成聚氨酯键,减少聚乙烯醇的水汽溶涨性,形成的聚氨酯键能同时提高阻隔保护层的阻隔性和柔韧性;丙烯酸的羧基能提供前期和聚乙烯醇的共混性,有利于在实现水性涂布,后期羧基能和聚乙烯醇的羟基在高温下发生热交联,进一步提高阻隔性。
附图说明
图1是本发明高阻隔膜的结构示意图。
图2是含有粘结层的结构示意图。
其中,1、高分子基材,2、粘结层,3、氧化硅沉积层,4、阻隔保护层。
具体实施方式
下面结合具体实施例对本发明进行具体描述,有必要在此指出的是本实施例只用于对本发明进行进一步说明,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可以根据上述本发明的内容做出一些非本质的改进和调整。
一种添加树脂,其特征在于:所述添加树脂是2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、乙烯基三甲基硅氧烷(或乙烯基三乙基硅氧烷)、丙烯酸(或甲基丙烯酸)通过共聚反应合成的高分子树脂。
一种阻隔保护层,所述阻隔保护层的成分是聚乙烯醇和上述所述的添加树脂的混合物。
如图1所示,一种高阻隔膜,包括高分子基材1,高分子基材1的上方从下向上设有氧化硅沉积层3、阻隔保护层4,其中阻隔保护层4是上述所述的阻隔保护层。
如图2所示,进一步地,高分子基材1与氧化硅沉积层3之间还设有粘结层2。
下面是本发明的合成实例,但本发明并不局限于下述实例。
主要原材料可以从以下公司获得:
高分子基材:聚对苯二甲酸乙二醇酯(PET)、聚萘二酸乙二醇酯(PEN)、聚碳酸酯(PC)、聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚氯乙烯(PVC)薄膜均来自中国乐凯集团有限公司;
聚氨酯粘合剂:聚氨酯粘合剂U1:来自中国乐凯集团有限公四,为甲烷二异氰酸酯HMDI/聚丙二醇PPG/二羟甲基丙酸DMPA三元聚合聚氨酯粘合剂;聚氨酯粘合剂U2:六亚甲基二异氰酸酯缩二脲/聚丙二醇预交联聚氨酯粘合剂,合成原料异氰酸酯可以从德国科思创获得;六甲基二硅氧烷、乙烯基三甲基硅氧烷、乙烯基三乙基硅氧烷:来自默克Merck公司。2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯:来自日本昭和电工株式会社;聚乙烯醇PVA105(水解度95~99%、聚合度500)、PVA110(水解度95~99%、聚合度1100)、PVA117(水解度95~99%、聚合度1700)均来自日本可乐丽株式会社,聚乙烯醇缩丁醛PVB(SD-7,缩醛度75%,聚乙烯醇缩丁醛的质量分数98%)来自于中国乐凯集团有限公司研究院;
丙烯酸、甲基丙烯酸:来自上海百灵威科技有限公司,偶氮二异丁腈:来自天津福晨化学试剂厂,甲乙酮:来自齐鲁石化。
第一部分:添加树脂合成实例(代号T)T1-T9
添加树脂T1合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、10g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、20g乙烯基三甲基硅氧烷、70g甲基丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T2合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、20g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、30g乙烯基三乙基硅氧烷、50g丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T3合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g乙二醇甲醚、30g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、30g乙烯基三甲基硅氧烷、40g甲基丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T4合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、10g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、40g乙烯基三甲基硅氧烷、50g丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T5合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g丙二醇甲醚醋酸酯、20g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、50g乙烯基三乙基硅氧烷、30g甲基丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T6合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、10g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、60g乙烯基三甲基硅氧烷、30g甲基丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T7合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、20g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、20g乙烯基三甲基硅氧烷、60g丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T8合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、30g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、20g乙烯基三乙基硅氧烷、50g甲基丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T9合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、20g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、20g乙烯基三甲基硅氧烷、60g丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
添加树脂T10合成:
在500ml带温控加热、机械搅拌、冷凝回流和氮气保护装置的四口烧瓶中加300g甲乙酮、10g的2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯、20g乙烯基三甲基硅氧烷、70g丙烯酸、1g偶氮二异丁腈,搅拌均匀,70℃下反应8小时,降温结束反应,反应原液可直接使用。
阻隔保护层涂布液配置:先将聚乙烯醇配置成30%的水溶液,然后将上述添加树脂用均质分散机按不同的添加量加入,配置成阻隔保护层涂布液。
第二部分:高阻隔膜的制造实例:
本发明的高阻隔膜的制造基本工艺流程为:高分子基材电晕处理→电晕处理后的高分子基材上涂布粘结层→在粘结层上等离子体增强化学气相沉积氧化硅沉积层→在氧化硅沉积层上涂布阻隔保护层。
实施例1:本发明的高阻隔膜的制造基本工艺流程
1、高分子基材:高分子基材为厚度为30μm的聚对苯二甲酸乙二醇酯薄膜(聚对苯二甲酸乙二醇酯薄膜来自乐凯胶片股份有限公司),对高分子基材涂布表面实施电晕处理;为现有技术的常规处理;
2、粘结层:在经过电晕处理的高分子基材上涂布聚氨酯粘合剂PU-1,涂布量为1g/m2,烘干温度为130℃,烘干时间为5分钟;
3、氧化硅沉积层:等离子体增强化学气相沉积二氧化硅。具体为:在日本莎姆克株式会社PD3800L卷绕式等离子体增强化学气相沉积装置(PECVD),将经过电晕处理、涂布聚氨酯粘合剂的基材放置于PECVD真空室的上电极板表面,将真空室抽真空至本底真空度为1.0×10-3Pa,将Ar气通入等离子体增强化学气相沉积装置的等离子体产生室,然后开启射频电源,在5Pa的压强下利用Ar等离子体对基材进行活性处理,持续30秒,然后关闭射频电源并停止Ar气的通入,分别将六甲基二硅氧烷蒸气(10sccm)和O2(200sccm)通过不同的管路通入薄膜的等离子体增强化学气相沉积真空室,通过闸板阀调节工作气压为50Pa,开启粉尘粒子清除装置的电源,在捕集电极上施加+60V的电压,然后开启射频电源功率开关,馈入射频功率为350W,并调节阻抗匹配网络,激发气体放电产生等离子体,开始薄膜的等离子体增强化学气相沉积,薄膜沉积10分钟后,先关闭射频电源功率输出开关,并停止Ar气的通入,然后再关闭粉尘粒子清除装置的电源,停止真空抽气,待真空腔室放气完成后,完成等离子体增强化学气相沉积二氧化硅,二氧化硅沉积层厚度为55nm。
4、阻隔保护层:在经过等离子体增强化学气相沉积二氧化硅的高分子基材的二氧化硅沉积层上涂布阻隔保护层涂布液,涂布量为1g/m2,烘干温度为130℃,烘干时间为5分钟。
实施例2-21:
参照实施例1高阻隔膜制造工艺,按照表1高阻隔膜制造参数表给出的数据改变高分子基材、粘结层、氧化硅沉积层、阻隔保护层的参数制作实施例2-21高阻隔膜。
比较例1-8:
参照实施例1高阻隔膜制造工艺,减少粘结层、按照表1给出的数据改变高分子基材、粘结层、氧化硅沉积层、阻隔保护层的参数制作比较例1-8高阻隔膜。
以上实施例和比较例中高阻隔膜的性能按以下测试方法评价:
1、薄膜涂层厚度测定:
使用光学膜厚测量仪(美国Filmetrics公司制F20-UV型)进行测试,依据国家标准GB/T33051-2016《光学功能薄膜表面硬化薄膜硬化层厚度测定方法》测试。
2、薄膜透光率测定:
采用雾度计(英国DIFFUSION公司制M57D型)进行测试,依据国家标准GB/T 2410-2008《透明塑料透光率和雾度的测定》测试。
3、薄膜透氧率测定:
采用广州标记Y210氧气透过率测定仪,依据国家标准GB/T 19789-2005《包装材料塑料薄膜和薄片氧化透过性试验库伦计检测法》测试。
4、薄膜透水率测定:
采用美国MOCON透湿仪,依据国家标准GB/T 21529-2008《塑料薄膜和薄片水蒸气透过率的测定电解传感器法》测试。
5、薄膜涂层附着性测定:
依据国际标准ISO2409百格法测试其附着性,附着性为七级评分,分为0-6级,0级最好,6级最差。
6、薄膜涂层抗划伤测定:
采用上海今森KS-1084B尖顶划针型划伤测试仪,依据国家标准GB/T9279-2007《色漆和清漆划痕试验》,对高阻隔膜抗划伤性能进行5分制评分,分为1-5分,5分为最好,1分为最差。
7、薄膜耐弯折性测定:
使用揉折试验机揉折10次,测试弯折前后的阻隔性。
8、耐高温蒸煮性:
使用高压灭菌锅120℃蒸汽蒸煮30min,测试蒸煮前后阻隔性。
9、印刷适应性:
使用铸信ZXYT-41000四色柔版印刷机印刷高阻隔膜,采用爱色丽(X.rite)彩通eXact扫描分光光度仪,按照PantoneLIVE色彩数字工作流程对印品质量进行5分制评分,分为1-5分,5分为最好,1分为最差。
实施例和比较例的高阻隔膜性能评价结果见表2高阻隔膜性能评价表。
本发明的高阻隔膜具有优异气体阻隔性和水蒸气阻隔性能,可以用来制造的阻氧、阻水汽包装材料,可以用在食品包装、医药品包装、电子产品等封装领域。
表1高阻隔膜制造参数表
表2高阻隔膜性能参数表
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由表2的实施例和比较例高阻隔膜检测应用结果表明,与其它高阻隔膜相比较,本发明设计的高阻隔膜至下而上包括高分子基材、粘结层、氧化硅沉积层和阻隔保护层。聚氨酯粘合层能提高二氧化硅沉积层的牢度;氧化硅沉积层和阻隔保护层能有效阻隔气体;阻隔保护层中的聚乙烯醇有出色的气体阻隔性能,添加树脂含有硅氧烷基、封闭型异氰酸酯基和羧基三种遥爪功能基团,三种遥爪功能基团在加热的作用下均能发生交联反应:硅氧烷基介于无机和有机界面之间,可形成有机基体-硅烷偶联剂-无机基体的结合层,大大提高阻隔保护层和二氧化硅沉积层的牢度;封闭型异氰酸酯基在热的作用下释放出活性异氰酸酯基和聚乙烯醇的羟基反应形成聚氨酯键,减少聚乙烯醇的水汽溶涨性,聚氨酯键同时能提高阻隔保护层的阻隔性和柔韧性;(甲基)丙烯酸的羧基能提供和聚乙烯醇水溶液的共混性,有利于在实现水性涂布,后期羧基能和聚乙烯醇的羟基在高温下发生热交联,进一步提高膜的阻隔性。本发明的高阻隔膜具有良好的印刷适应性,是一种优秀的高阻隔膜,可以用在食品包装、药品包装、电子产品封装等领域。
以上所述的仅是本发明的优选实施方式,但本发明的保护范围并不局限于此,应当指出,对于本领域的及任何熟悉本技术领域的技术人员来说,在不脱离本发明整体构思前提下,根据本发明的技术方案及其发明构思加以等同替换或改变,及作出的若干改变和改进,这些也应该视为本发明的保护范围。
Claims (9)
1.一种添加树脂,其特征在于:所述添加树脂是2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯,乙烯基三甲基硅氧烷或乙烯基三乙基硅氧烷,丙烯酸或甲基丙烯酸,通过共聚反应合成的高分子树脂;
按重量百分比计算,三种共聚单体的比例为:2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯10-30%,乙烯基三甲基硅氧烷或乙烯基三乙基硅氧烷20-60%,丙烯酸或甲基丙烯酸30-70%。
2.一种阻隔保护层,其特征在于:所述阻隔保护层的成分是聚乙烯醇和权利要求1所述的添加树脂的混合物;所述的阻隔保护层中聚乙烯醇的重量百分比为70-90%,添加树脂的重量百分比为10-30%;所述阻隔保护层中的聚乙烯醇水解度大于95%,聚合度大于500。
3.一种高阻隔膜,包括高分子基材和高分子基材上方的氧化硅沉积层,其特征在于:氧化硅沉积层上方设有阻隔保护层,其中阻隔保护层是权利要求2所述的阻隔保护层;
所述的阻隔保护层涂布量为0.5—2g/m²;
所述的高分子基材为聚对苯二甲酸乙二醇酯、聚萘二酸乙二醇酯、聚碳酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯或聚氯乙烯薄膜之一;所述氧化硅沉积层为等离子体增强化学气相沉积的二氧化硅沉积层。
4.根据权利要求3所述的高阻隔膜,其特征在于:所述的高分子基材厚度为5-500μm,所述的氧化硅沉积层厚度为40-80nm。
5.根据权利要求4所述的高阻隔膜,其特征在于:所述的高分子基材厚度为10-125μm,所述的氧化硅沉积层厚度为50-60nm。
6.根据权利要求3所述的高阻隔膜,其特征在于:高分子基材与氧化硅沉积层之间还设有粘结层。
7.根据权利要求6所述的高阻隔膜,其特征在于:形成粘结层的粘合剂是聚丙烯酸类粘合剂、聚酯类粘合剂、聚醚类粘合剂、聚氨酯类粘合剂、硅烷类粘合剂、硅酮类粘合剂、酚醛类粘合剂、环氧类粘合剂、合成橡胶类中的至少一种;粘合剂涂布量为0.1—5g/m²。
8.根据权利要求7所述的高阻隔膜,其特征在于:形成粘结层的粘合剂为聚氨酯粘合剂,粘结层的聚氨酯粘合剂涂布量为0.5—2g/m²。
9.一种阻氧、阻水汽包装材料,其特征在于:阻氧、阻水汽包装材料为权利要求3-8任一权利要求所述的高阻隔膜制造的阻氧、阻水汽包装材料。
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