CN1408016A - 有双硅烷添加剂的烯化亚胺/有机阻隔涂料 - Google Patents
有双硅烷添加剂的烯化亚胺/有机阻隔涂料 Download PDFInfo
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- CN1408016A CN1408016A CN01806000.5A CN01806000A CN1408016A CN 1408016 A CN1408016 A CN 1408016A CN 01806000 A CN01806000 A CN 01806000A CN 1408016 A CN1408016 A CN 1408016A
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- silane
- polyamines
- coating
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- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 7
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- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
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- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 claims description 2
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
一种使基质阻隔气体、香味和香气透过的组合物,所述组合物通过烯属不饱和酸、双硅烷和多胺混合形成。
Description
发明领域
本发明涉及含多胺、双硅烷和烯属不饱和酸的涂料,具有适用于包装应用的阻隔性。
发明背景
公知含有多胺硅烷化合物和衣康酸的涂料改善有机聚合物薄膜基质抵抗气体、油和香味渗透的性能(参见PCT/BE98/00009,其US同族是1999年7月15日申请的USSN 09/341 252)。此外,使所述涂布薄膜受到电子束辐射大大地增强所述涂料与薄膜表面的粘附力以及所述硅烷涂料提供的改善的阻隔性。
这些涂料代表该领域的显著进步。但已观察到虽然现有技术涂料的阻隔性在80%或更低的相对湿度环境中极好,但在90%或更高的相对湿度下其性能显著受损。
本发明人意外地发现多胺、烯属不饱和酸、和双硅烷组合在低至中等相对湿度值下提供极好的阻气性,而且在90%或更高的极高相对湿度值下也提供极好的阻气性。关键的改进是添加双硅烷,导致在大于90%的湿度下阻隔性极好。可使所述组合物交联以进一步改善阻隔性。本文中所用术语“阻隔性”意指使按ASTM D3985-81测量在0%相对湿度下测量的透氧度为1191cc/m2/day、在90%相对湿度下测量的透氧度为1238cc/m2/day的30μm未涂布双轴取向电晕处理聚丙烯薄膜改善至至少750cc/m2/day。
现有技术均未教导本发明。例如,US4 761 435要求保护与多胺树脂组合的可UV固化的多烯属不饱和组合物,使用芳基酮光敏剂。该专利教导所述组合物中的酸官能团是不希望的(第5栏24行)。专利权人指出要避免形成胺盐,因为所述光敏剂仅与胺反应,不与胺盐反应。这与本发明相反,本发明教导希望形成酸盐,产生优异的阻隔性。
另一例,US4 943 600教导含叔胺的树脂、烯丙基封端的树脂、和马来酸官能树脂组合。同样该专利权人教导配制所述组合物减少或消除羧基官能团,这与本发明正相反。
US5 017 406要求保护含反应性不饱和化合物的可UV固化的组合物,但未教导象本发明一样使用多胺或不饱和酸。
JP-A-7-18221(1995年1月20日公开)教导一种用于阻挡气体的表面处理组合物,包含氨基硅烷和有芳环或加氢环的化合物。但本发明与之不同,因为本发明不需添加有芳环的环状化合物,而且该文献未教导添加烯属不饱和酸。
本发明与现有技术不同,因为现有技术未教导用多胺、双硅烷和烯属不饱和酸获得阻气性。
发明概述
本发明教导一种使基质抵抗气体、香味和香气渗透的组合物,所述组合物通过烯属不饱和酸、双硅烷和多胺混合形成,其中所述多胺可选地有在其中反应的交联剂,所述多胺有四个或更多A、B、或C单元,其中:
A为-R2-N(R1)2单元,B为-R1-N(R2-)2单元,C为(-R2)3N-单元,
其中:
R1独立地选自氢、烷基、取代的烷基、芳基、取代的芳基、芳烷基、和烷芳基,R2独立地选自有1至18个碳原子的线型或支化亚烷基或取代的亚烷基、和有6至18个碳原子的亚芳基或取代的亚芳基。
所述组合物涂布在基质上,然后可选地处理以引发自由基反应。本发明可以涂料形式涂于包装应用中所用各种基质上。
多胺
本发明的多胺是有四个或更多A、B、或C单元的聚合的(均聚或共聚的)多胺,其中:
A为-R2-N(R1)2单元,B为-R1-N(R2-)2单元,C为(-R2)3N-单元,
其中:
R1独立地选自氢、烷基、取代的烷基、芳基、取代的芳基、芳烷基、和烷芳基,R2独立地选自有1至18个碳原子的线型或支化亚烷基或取代的亚烷基、和有6至18个碳原子的亚芳基或取代的亚芳基。
R1独立地选自氢、烷基、取代的烷基、芳基、取代的芳基、芳烷基、和烷芳基,R2独立地选自有1至18个碳原子的线型或支化亚烷基或取代的亚烷基、和有6至18个碳原子的亚芳基或取代的亚芳基。例如R1或R2可被羟基取代。
本发明所述胺实际上是聚合的,优选分子量为150至2 000 000,优选400至400 000,最优选600至80 000。所述胺的高度聚合使最终组合物的粘合度较低。可通过本领域公知的方法如通过与二烷基卤(即二氯化乙烯)、二异氰酸酯(如甲苯二异氰酸酯、六亚甲基二异氰酸酯)、二(甲基)丙烯酸酯(如己二醇二丙烯酸酯、季戊四醇二丙烯酸酯)、双环氧化合物(乙二醇二缩水甘油醚)反应使所述较低分子量的多胺聚合形成较高分子量的多胺。
适用于本发明的多胺的例子包括聚乙烯胺、氨基官能的聚丙烯酰胺、poly-DADMAC’s聚乙烯吡咯烷酮共聚物、聚氮丙啶和乙二胺与表氯醇共聚物的反应产物。
可用于获得不同程度的粘合性的优选多胺是称为聚烯化亚胺的一类多胺,如聚氮丙啶,它易于以宽分子量范围和不同支化度获得。聚氮丙啶由一大族水溶性即亲水性的不同分子量和化学改性程度的多胺组成。公知氮丙啶的聚合不产生完全由线型结构单元组成的聚合物,而且聚氮丙啶中的支化度与酸浓度和聚合过程中的温度有关。例如,此支化度可在12和38%之间改变。聚氮丙啶的分子式可以A、B或C单元的形式表示,其中:
A为-R2-N(R1)2单元,B为-R1-N(R2-)2单元,C为(-R2)3N-单元,其中R1为氢,R2为-CH2CH2-基。A∶B∶C单元之比可为1∶0.5∶0.5至1∶2∶1,但优选1∶1∶1至1∶2∶1。
可用本领域公知方法在聚氮丙啶上接枝附加基团以改变所述涂料与基质的亲合性或粘合性。聚氮丙啶改性的例子包括与环氧乙烷结构(环氧乙烷、缩水甘油)反应引入羟基、与氰化物和醛反应然后水解引入羧酸基(“斯特雷克尔合成”)、接枝磷酸或磺酸基、和用烷基化剂如硫酸二甲酯接枝亲油的烷基链。
所述聚氮丙啶的优选分子量为600至80 000。所述聚氮丙啶的最优选分子量为600至25 000。
典型的聚氮丙啶是SZ-6050,来自Dow Corning ToraySilicone(Japan)的硅烷接枝的聚氮丙啶,及SP-103和SP-110,它们是来自Nippon Shokubai(Japan)的600和1000分子量的聚氮丙啶。
烯属不饱和酸
所述组合物中还加入预定量的烯属不饱和酸。“烯属不饱和酸”意指有乙烯基不饱和的任何酸。所述烯属不饱和酸的加入量可高达所述组合物的80%(重),最优选5至75%(重)。最优选用于本发明的烯属不饱和酸是衣康酸;但其它酸如富马酸、马来酸、柠康酸、丙烯酸、甲基丙烯酸、肉桂酸、衣康酸单甲酯、乙烯膦酸、山梨酸、中康酸、和乙烯磺酸也可使用。本文所用术语“烯属不饱和酸”意指包括一或多种上述酸的混合物。优选所述多胺中的氮与所述酸上的酸基克原子之摩尔比为10∶1至1∶100,优选5∶1至1∶10,最优选2∶1至1∶4。事实上,所述酸可加至所述烯属不饱和酸的溶解度极限,典型地高达所述组合物的80%(重)。
双硅烷
本发明的关键添加剂是以下通式所示双硅烷:
R3 bX3-bSi-Z-SiX3-bR3 b
其中Z为R4NH(R4NH)pR4。式中每个R优选为有1至10个碳原子的烃基,例如饱和或不饱和脂族或芳族基团,如烷基、链烯基、或苯基;优选甲基和乙基,最优选甲基。每个X为有1至4个碳原子的烷氧基、卤原子、肟基或酰氧基,优选甲氧基和乙氧基,最优选甲氧基。R4可以是有1至12个碳原子的二价烃基,优选每个R4有2至3个碳原子。每个b为0至3,但最优选0,p为0或1。使用其中每个X均为甲氧基、每个R4均为亚甲基、b为0和p为0的化合物即所述化合物为双-(γ-三甲氧基甲硅烷基丙基)胺时得到最佳结果。
用于本发明的可称为二甲硅烷基化仲胺的这些物质可通过本领域已知方法制备,例如US2 832 754、2 920 095和5 101 055中所公开的。
溶剂
本发明组分可选地在溶剂存在下混合。一般地,水、醇及其共混物是适合的溶剂,因为所述多胺和所述烯属不饱和酸可溶于其中。另一类非常优选的溶剂是单或聚乙二醇的醚衍生物如单或聚环氧烷,包括诸如乙二醇二甲醚等溶剂。此外,所选溶剂优选润湿所述基质。优选所述溶剂是无毒的,不使所述涂料的干燥时间延长超过工业上可接受的时间。溶剂的量可在所述组合物的20%至99%的范围内,优选60至95重量份。优选的溶剂是甲醇、乙醇、正丙醇、异丙醇、丁醇、和1-甲氧基-2-丙醇(以“Dowanol PM”购自The Dow Chemical Company,Midland,Michigan)。
可选的交联剂
虽然所述多胺、烯属不饱和酸和双硅烷可混合形成本发明组合物,但非常优选加入交联剂以改善阻隔性、减少反湿润、和改善外观。据信较高的交联密度导致这些性能改善。本文所用术语“交联剂”定义为意指可使所述多胺进一步扩链和/或交联的试剂。所述交联剂可以是有机交联剂或更优选的反应性硅烷交联剂、或其混合物。
有机交联剂
虽然所述多胺、烯属不饱和酸和双硅烷可单独混合形成本发明组合物,但优选加入使所述多胺链进一步扩链和交联的化合物。据信为使本发明涂料具有改善的阻隔性和外观希望所述多胺的聚合和交联度较高。适用于使所述多胺扩链和交联的化合物包括但不限于多官能丙烯酸酯、甲基丙烯酸酯、环氧化合物、异氰酸酯、硫氰酸酯、酰卤、酸酐、酯、烷基卤、醛、醌或其组合。具体实例包括但不限于己二醇二丙烯酸酯、甲基丙烯酸缩水甘油酯、乙二醇二缩水甘油醚、甲苯二异氰酸酯、及邻-和对-苯醌。
可在所述组合物涂布在基质上之前或之后使所述多胺扩链和交联。适用于使所述多胺涂料扩链和交联的化合物包括将与所述多胺的氮原子发生酸催化的缩合反应的那些物质如三羟甲基苯酚、醛如甲醛和乙二醛、及甲醛与将经历曼尼希反应的活性亚甲基化合物的混合物。
可与所述多胺无关地通过加入将与所述烯属不饱和酸共聚的多官能化合物使所述烯属不饱和酸交联。这些化合物包括多官能丙烯酸酯和甲基丙烯酸酯。此外,可通过加入丙烯酸酯和甲基丙烯酸酯官能的硅烷直接使所述烯属不饱和酸交联成交联的多胺结构。所述丙烯酸酯和甲基丙烯酸酯官能的硅烷化合物如丙烯酰氧基丙基三甲氧基硅烷和甲基丙烯酰氧基丙基三甲氧基硅烷可在所述烯属不饱和酸之前或之后加入本发明组合物中使所述多酸交联。涂布后所述烷氧基或丙烯酰氧基的水解和缩合将形成有多官能团的聚合物,它将与所述烯属不饱和酸共聚。
所述有机交联剂优选以100∶1至1∶10、优选10∶1至1∶1、最优选5∶1至2∶1的多胺/有机交联剂之比加入。
反应性硅烷交联剂
最优选的化合物是含有将在所述烯属不饱和酸加入本发明组合物之前与所述多胺链上的氮原子反应的官能团以及将在利用可选的含水溶剂涂布本发明组合物之后经历水解和缩合反应的三烷氧基或三酰氧基硅烷基的那些。
由于所述分子的硅烷部分末端是羟基或烷氧基,可与其它硅氧烷封端分子的羟基或烷氧基部分缩合形成Si-O-Si基。所述Si-O-Si键使所述组合物的交联密度增加。所述反应性硅烷可有以下通式:QSiRm(OR)3-m,其中Q为含有一或多个丙烯酸酯、醛、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、异氰酸酯、异硫氰酸酯、酐、环氧、酰氯、线型或支化的卤代烷基、和卤代芳基的基团,m为0、1或2,R为有1至4个碳原子的基团。具体地,所述反应性硅烷包括诸如γ-丙烯酰氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧丙基三甲氧基硅烷、3-环氧丙氧丙基三甲氧基硅烷、氯丙基三甲氧基硅烷、氯丙基三乙氧基硅烷、γ-异氰酸根合丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基-三(2-乙氧基环己基)硅烷、乙基三甲氧基硅烷、氯丙基三乙氧基硅烷、氯丙基乙基二甲氧基硅烷、甲基二甲氧基硅烷和环氧丙氧丙基甲基二甲氧基硅烷等分子。最优选的反应性硅烷是以Z-6076购自Dow Corning Corporation的氯丙基三甲氧基硅烷、以1-6376购自Dow Corning Corporation的氯丙基三乙氧基硅烷、和以Z-6040购自Dow Corning Corporation的γ-三甲氧基甲硅烷基丙基缩水甘油醚。其中所述卤烷基官能的交联剂反应之后可能需要中和所述多胺,例如通过添加甲醇钠并滤出所产生的沉淀。
所述反应性硅烷优选以100∶1至1∶10、优选10∶1至1∶1、最优选5∶1至2∶1的多胺/反应性硅烷之重量比加入。
涂层厚度
所述涂料可以任何需要量涂布,但优选涂布这样量的涂料使涂布量高达20μm总体厚,最优选的涂层厚度为0.5至10μm。涂层厚度可通过扫描电子显微术(SEM)分析测定。所述涂料可通过任何传统方法如喷涂、辊涂、缝模涂布、液面涂布、浸涂、及直接、转移式和逆式槽辊涂布涂于基质上。
基质
所述涂料可布置在各种基质上,包括但不限于聚烯烃如取向聚丙烯(OPP)、浇铸聚丙烯、聚乙烯和聚乙烯共聚物;聚苯乙烯;聚酯如聚对苯二甲酸乙二醇酯(PET)或聚萘二酸乙二酯(PEN);聚烯烃共聚物如乙烯-乙酸乙烯酯、乙烯-丙烯酸和乙烯-乙烯醇(EVOH);聚乙烯醇及其共聚物;聚酰胺如尼龙和MXD6;聚酰亚胺;聚丙烯腈;聚氯乙烯;聚偏氯乙烯;和聚丙烯酸酯;离子键聚合物;多糖如再生纤维素;和硅氧烷如橡胶或密封胶;其它天然或合成橡胶;薄玻璃纸或涂布粘土的纸、纸板或牛皮纸;及金属化聚合物薄膜和涂有气相沉积的金属氧化物的聚合物薄膜,如AlOx、SiOx或TiOx。
上述基质可以是薄膜或片材形式的,但这不是必须的。所述基质可以是共聚物、层压材料、共挤物、共混物、涂层或以上所列基质的任何组合,取决于所述材料之间的相容性。此外,所述基质可以是由诸如聚乙烯、聚丙烯、聚苯乙烯、聚酰胺、PET、EVOH、或含此类材料的层压材料等材料制成的硬质容器。
涂布之前上述基质还可通过电晕处理、等离子处理、酸处理和火焰处理进行预处理,这些均为本领域已知。
此外,本发明组合物可在各种包装容器如袋、管、瓶、小瓶、盒中袋、直立袋、屋形纸盒、热成型盘、块料包装、盒、香烟包装等上用作阻隔层。本发明组合物可用作层压粘合剂。
当然,本发明不限于包装应用,可用于要求抵抗气体或香味的阻隔性能的任何应用,如轮胎、助浮器、膨胀装置等。
任何上述基质都可涂有底漆。所述底漆通过本领域已知方法如喷涂、辊涂、缝模涂布、液面涂布、浸涂、及直接、转移式和逆式槽辊涂布法涂于所述基质上。适用的底漆包括但不限于碳二亚胺、聚氮丙啶、和硅烷,如N-(2-氨乙基)-3-氨丙基三甲氧基硅烷和氨丙基三乙氧基硅烷。
固化
虽然本发明组合物将在环境条件下成膜,但通过加热和/或自由基固化达到最佳效果。
所述组合物优选通过自由基发生器如紫外线、电子束、γ-辐射或化学自由基发生剂如偶氮化合物和过氧化物进行固化。低能电子束是优选的固化方法,因为比γ-源如Cobalt M-60便宜。作为固化系统它优于紫外线辐射的优点在于能在没有光引发剂的情况下产生自由基。还产生更高产率的涂料与基质的交联密度和化学接枝。各种类型的电子束加速器如van de Graaf型、调谐变压器型、直线型、dynamatron型和高频型均可用作电子束源。可以0.1至10Mr的剂量辐射由其放出的能量为5至2000KeV、优选50至300KeV的电子束。最优选的剂量是至少5Mr的150KeV。如果在真空中处理所述基质,则可使用低电子束电压。常用电子束源是来自Energy Sciences,Inc.(Wilmington,MA)的Electrocure CB-150。
如果在固化之前加入一或多种光引发剂,也可用紫外光使所述组合物固化。所述光引发剂无特殊限制,只要它们可通过吸收光能产生自由基。用于本发明组合物UV固化的对紫外光敏感的光引发剂或引发剂共混物包括EM Chemicals出售的2-羟基-2-甲基-1-苯基-丙-1-酮(Darocure 1173)和Ciba-Geigy Corporation,Hawthorne,New York出售的2,2-二甲氧基-2-苯基-乙酰苯酮(acetol phenone)(Irgacure651)。对于本发明而言,已发现基于所述组合物中总固体0.05至5%(重)的本文所述光引发剂将使所述组合物固化。
也可使用本领域技术人员已知的其它类型的自由基发生剂,如促进的过氧化物、偶氮化合物等。
此外,如果所述组合物中加入交联剂,则可能需要其它固化方法。例如,如果加入反应性硅烷交联剂,可通过缩合反应使所述组合物固化,需要存在水分。水分可存在于涂料溶液本身中,也可通过水蒸汽或以高湿度烘箱中加入。可通过加热使所述反应加速,例如在烘箱中在高达140℃的温度下加热,优选60至120℃的温度,最优选90至110℃的温度。加热时间与温度有关,在1至10秒内所述涂料将达到不粘的程度。所述加热步骤用于使溶剂蒸发,加速硅烷醇基之间的缩合反应。所需其它固化化学将取决于所用交联体系,这些均为本领域公知。
可选的添加剂
所述组合物中可加入各种可选的添加剂以根据需要改善各种性能。这些添加剂可根据需要以任何量加入,只要它们不降低本文所述阻隔涂料的性能。此类添加剂包括防粘连和增滑助剂,如硬脂酰胺、油酰胺或极性添加剂,如环氧化物、丙烯酸酯、甲基丙烯酸酯、多元醇、缩水甘油、甲基丙烯酸缩水甘油酯、乙二醇二缩水甘油醚、双酚A二缩水甘油醚、或多胺,如聚氮丙啶和其它硅烷。也可加入湿润剂如聚乙氧基化苯酚。
优选实施方案
在搅拌下将水(7g)和衣康酸(3.02g)加入N-(异丙氧基,甲氧基)甲硅烷基丙基聚乙烯亚胺(2g),搅拌15分钟。将8g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g N-(异丙氧基,甲氧基)甲硅烷基丙基聚乙烯亚胺、74g异丙醇和11g衣康酸一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为51.6cc,在80%RH下为17.1cc,湿值为26.1cc,测量涂层厚度为2.5μ。
实施例
试验1-10-A1170 & bis-TMSEDA加入1-6601/ITA(29∶71wt)配方中保持混合物中ITA含量恒定(其中ITA为衣康酸)
试验1-10中,使用重量比为29∶71wt的(1-6601/A1170/bis-TMSEDA):ITA配方,总固含量为30%。下述所有试验中所用溶剂均为普通工业级异丙醇和蒸馏水。所述N-(异丙氧基,甲氧基)甲硅烷基丙基聚乙烯亚胺(45%固体,在异丙醇中)(“1-6601”)来自Dow Corning Corporation(Midland,MI),所述双-(γ-三甲氧基甲硅烷基丙基)胺(Silquest A1170或“A1170”)来自Witco,所述双-[(3-三甲氧基甲硅烷基)丙基]乙二胺(“bis-TMSEDA”)来自Gelest,所述衣康酸(“ITA”)来自Acros Chemicals。所述涂料溶液全部用#18Myer棒涂于来自UCB Films的电晕处理过的30μm厚“Rayopp”取向聚丙烯薄膜上。将所述涂布薄膜在烘箱中于60℃干燥10分钟,再在环境条件下干燥2小时。然后在10 Megarads和165Kv下用EB机使所述干燥的涂布薄膜“固化”。
用MOCON Oxtran 2/20 Series测量各薄膜的透氧度,以cc/m2/24小时为单位记录,“干”值是在0%相对湿度下测量的,“湿”值是在90%相对湿度下测量的。某些涂布薄膜还在80%RH下评估。所述MOCON仪器来自Modern Controls Corporation。为进行对比,所述聚丙烯基膜在所有测量的相对湿度下透氧度为1200cc/m2/24小时。所述涂层厚度用扫描电子显微术(SEM)测量。
试验1-无A1170
将水(7g)加入1-6601(3.86g)和IPA(异丙醇,4.87g)的溶液中,将所述混合物搅拌5分钟。将衣康酸(4.26g)加入所述溶液中,将所述混合物搅拌2小时。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为107.5cc,在80%RH下为53.3cc,湿值为650.6cc,测量涂层厚度为2.4μm。
试验2-1%A1170
将1-6601(3.71g)和IPA(4.6g)一起搅拌10分钟。将水(7g)和ITA(4.21g)加入上述混合物中,搅拌15分钟。将0.48g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为118.3cc,在80%RH下为44.8cc,湿值为594.3cc,测量涂层厚度为2.35μm。
试验3-4%A1170
将1-6601(3.33g)和IPA(4g)一起搅拌10分钟。将水(7g)和ITA(4.08g)加入上述混合物中,搅拌15分钟。将1.6g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为121.6cc,在80%RH下为25.2cc,湿值为424.9cc,测量涂层厚度为2.8μm。
试验4-10%A1170
将1-6601(2.53g)和IPA(2.65g)一起搅拌10分钟。将水(7g)和ITA(3.82g)加入上述混合物中,搅拌15分钟。将4g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为68.8cc,在80%RH下为33.1cc,湿值为61.5cc,测量涂层厚度为2.2μm。
试验5-13%A1170
将1-6601(2.13g)和IPA(1.98g)一起搅拌10分钟。将水(7g)和ITA(3.69g)加入上述混合物中,搅拌15分钟。将5.2g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为37.9cc,在80%RH下为27.4cc,湿值为85.4cc,测量涂层厚度为2.1μm。
试验6-16%A1170
将1-6601(1.73g)和IPA(1.31g)一起搅拌10分钟。将水(7g)和ITA(3.56g)加入上述混合物中,搅拌15分钟。将6.4g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为6.3cc,在80%RH下为46.7cc,湿值为578.6cc,测量涂层厚度为1.7μm。
试验7-19%A1170
将1-6601(1.33g)和IPA(0.65g)一起搅拌10分钟。将水(7g)和ITA(3.42g)加入上述混合物中,搅拌15分钟。将7.6g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为4.2cc,在80%RH下为136.2cc,湿值为792.1cc,测量涂层厚度为2.3μm。
试验8-4%bis-TMSEDA
将1-6601(3.33g)和IPA(4g)一起搅拌10分钟。将水(7g)和ITA(4.08g)加入上述混合物中,搅拌15分钟。将1.6g Part B加入所述混合物中,搅拌2小时(其中Part B是通过24.2g bis-TMSEDA、64.8gIPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为77.8cc,湿值为472.1cc,测量涂层厚度为2.7μm。
试验9-10%bis-TMSEDA
将1-6601(2.53g)和IPA(2.65g)一起搅拌10分钟。将水(7g)和ITA(3.82g)加入上述混合物中,搅拌15分钟。将4g Part B加入所述混合物中,搅拌2小时(其中Part B是通过24.2g bis-TMSEDA、64.8gIPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为33cc,湿值为332.9cc,测量涂层厚度为1.05μm。
试验10-19%bis-TMSEDA
将1-6601(1.33g)和IPA(0.65g)一起搅拌10分钟。将水(7g)和ITA(3.42g)加入上述混合物中,搅拌15分钟。将7.6g Part B加入所述混合物中,搅拌2小时(其中Part B是通过24.2g bis-TMSEDA、64.8gIPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为7.9cc,湿值为209cc,测量涂层厚度为1.95μm。
实施例1至10的阻隔数据示于下表1中。
表1
试验# | 双硅烷类型 | 重量比1-6601/双硅烷/ITA | OTR190%RHcc/m2/day | OTR80%RHcc/m2/day | OTR0%RHcc/m2/day | 涂层厚度μm | OTR预计 23μm涂层90%RHcc/m2/day | OTR预计 33μm涂层80%RHcc/m2/day | OTR预计 43μm涂层0%RHcc/m2/day |
1 | 无 | 29/0/71 | 650.6 | 53.2 | 107.5 | 2.4 | 581.6 | 42.9 | 87.6 |
2 | A1170 | 27.8/1.2/71 | 594.3 | 44.8 | 118.3 | 2.35 | 519.6 | 35.4 | 94.7 |
3 | A1170 | 25/4/71 | 424.9 | 25.2 | 121.6 | 2.8 | 405.9 | 23.6 | 114.3 |
4 | A1170 | 19/10/71 | 61.5 | 33.1 | 68.8 | 2.2 | 45.7 | 24.4 | 51.2 |
5 | A1170 | 16/13/71 | 85.4 | 27.4 | 37.9 | 2.1 | 61.0 | 19.3 | 26.8 |
6 | A1170 | 13/16/71 | 578.6 | 46.7 | 6.3 | 1.7 | 411.1 | 26.9 | 3.6 |
7 | A1170 | 10/19/71 | 792.1 | 136.2 | 4.2 | 2.3 | 713.8 | 107.1 | 3.2 |
8 | bis-TMSEDA | 25/4/71 | 472.1 | - | 77.8 | 2.7 | 441.7 | - | 70.5 |
9 | bis-TMSEDA | 19/10/71 | 332.9 | - | 33 | 1.05 | 141.2 | - | 11.8 |
10 | bis-TMSEDA | 10/19/71 | 209 | - | 7.9 | 1.95 | 144.4 | - | 5.1 |
其中:
1:OTR是透氧速度或透氧度
2:OTR预计用以下通用复合材料渗透性等式计算:Tt/Pt=Ts/Ps+Tc/Pc,其中T表示厚度(μm),P表示复合材料(Tt,Pt)、基质(Ts,Ps)、和粘合剂(Tc,Pc)的渗透系数。测得所述基质OPP的厚度为30μm,在90%RH下测量的OTR为1238cc/m2/day。
3:与2相同,但在80%RH下测量所述透氧度为1266cc/m2/day
4:与2相同,但在0%RH下测量所述透氧度为1191cc/m2/day
从上表可见,与没有所述双硅烷的对照试验相比,有双硅烷的情况下透氧度得到显著改善。
试验11-14-A1170和bis-TMSEDA加入1-6601/ITA(35∶65wt)配方中保持混合物中ITA含量恒定(其中ITA为衣康酸)
试验11-14中,使用重量比为35∶65wt的(1-6601/A1170/bis-TMSEDA):ITA配方,总固含量为30%。下述所有试验中所用溶剂均为普通工业级异丙醇和蒸馏水。所述1-6601来自Dow Corning Corporation(Midland,MI),所述Silquest A1170来自Witco,所述bis-TMSEDA来自Gelest,所述衣康酸来自AcrosChemicals。所述涂料溶液全部用#18 Myer棒涂于来自UCB Films的电晕处理过的30μm厚“Rayopp”取向聚丙烯薄膜上。将所述涂布薄膜在烘箱中于60℃干燥10分钟,再在环境条件下干燥2小时。然后在10 Megarads和165Kv下用EB机使所述干燥的涂布薄膜“固化”。
试验11-无A1170
将水(7g)加入1-6601(4.67g)和IPA(4.43g)的溶液中,将所述混合物搅拌5分钟。将衣康酸(3.9g)加入所述溶液中,将所述混合物搅拌2小时。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为84.1cc,在80%RH下为155.6cc,湿值为993.9cc,测量涂层厚度为2μm。
试验12-15%A1170
将1-6601(2.67g)和IPA(1.09g)一起搅拌10分钟。将水(7g)和ITA(3.24g)加入上述混合物中,搅拌15分钟。将6g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15g A1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,湿值为559.7cc,测量涂层厚度为2.1μm。
试验13-20%A1170
在搅拌下将水(7g)和ITA(3.02g)加入1-6601(2g)中,搅拌15分钟。将8g Part A加入所述混合物中,搅拌2小时(其中Part A是通过15gA1170、74g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为51.6cc,在80%RH下为17.1cc,湿值为26.1cc,测量涂层厚度为2.5μm。
试验14-20%bis-TMSEDA
在搅拌下将水(7g)和ITA(3.02g)加入1-6601(2g)中,搅拌15分钟。将8g Part B加入所述混合物中,搅拌2小时(其中Part B是通过24.2gbis-TMSEDA、64.8g IPA和11g ITA一起混合制备的)。涂布、干燥和固化后,测量所述复合材料的渗透性,干值为28cc,湿值为689.7cc,测量涂层厚度为1.4μm。
表2示出试验11至14的阻隔数据。
表2
由上表可见,用双硅烷与不用双硅烷相比达到了对氧气阻隔的实际的改善。
试验# | 双硅烷类型 | 重量比1-6601/双硅烷/ITA | OTR190%RHcc/m2/day | OTR80%RHcc/m2/day | OTRO%RHcc/m2/day | 涂层厚度μm | OTR预计 23μm涂层90%RHcc/m2/day | OTR预计 33μm涂层80%RHcc/m2/day | OTR预计 43μm涂层0%RHcc/m2/day |
11 | 无 | 35/65 | 993.9 | 155.6 | 84.1 | 2 | 904.7 | 108.2 | 57.4 |
12 | A1170 | 20/15/65 | 559.7 | - | - | 2.1 | 453.3 | - | - |
13 | A1170 | 15/20/65 | 26.1 | 17.1 | 51.6 | 2.5 | 21.8 | 14.3 | 43.3 |
14 | bis-TMSEDA | 15/20/65 | 689.7 | - | 28 | 1.4 | 457.9 | - | 13.2 |
Claims (17)
1.一种组合物,所述组合物包括烯属不饱和酸、双硅烷和多胺,所述多胺可选地有在其中反应的交联剂,所述多胺有四个或更多A、B、或C单元,其中:
A为-R2-N(R1)2单元,B为-R1-N(R2-)2单元,C为(-R2)3N-单元,
其中:
R1独立地选自氢、烷基、取代的烷基、芳基、取代的芳基、芳烷基、和烷芳基,R2独立地选自有1至18个碳原子的线型或支化亚烷基或取代的亚烷基、和有6至18个碳原子的亚芳基或取代的亚芳基,所述双硅烷的通式为R3 bX3-bSi-Z-SiX3-bR3 b
其中Z为R4NH(R4NH)pR4,R3各自为烃基,X各自为有1-4个碳原子的烷氧基、卤原子、肟基或酰氧基,R4各自为有1-12个碳原子的二价烃基,b是0-3,p是0或1。
2.权利要求1的组合物,进一步包括选自水、醇、单或聚乙二醇的醚衍生物和它们的混合物。
3.权利要求1的组合物,其中所述烯属不饱和酸选自衣康酸、富马酸、马来酸、柠康酸、丙烯酸、甲基丙烯酸、肉桂酸、衣康酸单甲酯、乙烯膦酸、中康酸、山梨酸和乙烯磺酸及其混合物。
4.权利要求1的组合物,其中所述双硅烷是双-(γ-三甲氧基甲硅烷基丙基)胺(或双-[(3-三甲氧基甲硅烷基)丙基]乙二胺)。
5.权利要求1的组合物,其中所述多胺是分子量在600至25 000范围内的聚氮丙啶。
6.权利要求1的组合物,其中所述多胺上的氮原子与所述烯属不饱和酸上的酸基之摩尔比为10∶1至1∶100。
7.权利要求1的组合物,其中所述组合物涂于选自聚烯烃;取向聚丙烯;铸塑聚丙烯;聚乙烯和聚乙烯共聚物;聚苯乙烯;聚酯;聚对苯二甲酸乙二醇酯;聚萘二酸乙二酯;聚烯烃共聚物;乙烯-乙酸乙烯酯;乙烯-丙烯酸;乙烯-乙烯醇;聚乙烯醇及其共聚物;聚酰胺,尼龙;和MXD6;聚酰亚胺;聚丙烯腈;聚氯乙烯;聚二氯乙烯;聚偏氯乙烯;聚丙烯酸酯;离子键聚合物;多糖;再生纤维素;硅氧烷;橡胶或密封胶;天然或合成橡胶;薄玻璃纸或涂布粘土的纸;纸板;牛皮纸;金属化薄膜;和涂有气相沉积的金属氧化物的聚合物薄膜的基质上。
8.权利要求7的组合物,其中所述涂料组合物布置在一或多种附加基质上形成层压材料,所述附加基质可选地涂有底漆。
9.权利要求8的组合物,其中用于形成所述层压材料的附加基质选自聚烯烃;取向聚丙烯;铸塑聚丙烯;聚乙烯和聚乙烯共聚物;聚苯乙烯;聚酯;聚对苯二甲酸乙二醇酯;聚萘二酸乙二酯;聚烯烃共聚物;乙烯-乙酸乙烯酯;乙烯-丙烯酸;乙烯-乙烯醇;聚乙烯醇及其共聚物;聚酰胺,尼龙;和MXD6;聚酰亚胺;聚丙烯腈;聚氯乙烯;聚二氯乙烯;聚偏氯乙烯;聚丙烯酸酯;离子键聚合物;多糖;再生纤维素;硅氧烷;橡胶或密封胶;天然或合成橡胶;薄玻璃纸或涂布粘土的纸;纸板;牛皮纸;金属化薄膜;和涂有气相沉积的金属氧化物的聚合物薄膜。
10.权利要求8的组合物,其中所述底漆选自硅烷、聚氮丙啶、和碳二亚胺。
11.权利要求1的组合物,其中存在交联剂,所述交联剂是有以下通式的反应性硅烷:QSiRm(OR)3-m,其中Q含有选自丙烯酸酯、醛、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、异氰酸酯、异硫氰酸酯、酐、环氧、酰氯、线型或支化的卤代烷基、和卤代芳基的基团,m为1、2或3,R为有1至4个碳原子的基团,可选地使所述组合物中和。
12.权利要求7的组合物,其中所述涂布基质在水分存在下加热。
13.一种方法,包括以下步骤:
(I)使烯属不饱和酸、双硅烷、和可选地有在其中反应的交联剂的多胺混合,所述多胺有四个或更多A、B、或C单元,其中:
A为-R2-N(R1)2单元,B为-R1-N(R2-)2单元,C为(-R2)3N-单元,
其中:
R1独立地选自氢、烷基、取代的烷基、芳基、取代的芳基、芳烷基、和烷芳基,R2独立地选自有1至18个碳原子的线型或支化亚烷基或取代的亚烷基、和有6至18个碳原子的亚芳基或取代的亚芳基;所述双硅烷有以下通式:
R3 bX3-bSi-Z-SiX3-bR3 b
其中Z为R4NH(R4NH)pR4,每个R3为烃基,每个X为有1至4个碳原子的烷氧基、卤原子、肟基或酰氧基,每个R4为有1至12个碳原子的二价烷基;b为0至3,p为0或1;
(II)用步骤(I)的混合物涂布基质;和
(III)处理步骤(II)的涂布基质引发自由基反应。
14.权利要求13的方法,其中通过电子束辐射、γ-辐射或紫外线辐射引发所述自由基反应,可选地在光引发剂存在下进行,或者在自由基发生剂存在下加热引发所述自由基反应。
15.权利要求13的方法,其中将步骤(II)的涂布基质加热。
16.权利要求13的方法,其中存在交联剂,所述交联剂是有机交联剂。
17.一种包装容器,改进包括:至少一层阻隔层构成所述包装容器的整体部分,其中所述阻隔层是通过权利要求13所述方法形成的。
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WO2006069376A2 (en) * | 2004-12-22 | 2006-06-29 | University Of Cincinnati | Improved superprimer |
AU2011226768B2 (en) * | 2006-10-13 | 2012-12-20 | Cytec Technology Corp | Hydrophobically modified polyamine scale inhibitors |
US7999065B2 (en) | 2006-10-13 | 2011-08-16 | Cytec Technology Corp. | Hydrophobically modified polyamine scale inhibitors |
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