CN1656129A - 具有改进的气体阻挡性能的可光交联的多涂层体系 - Google Patents
具有改进的气体阻挡性能的可光交联的多涂层体系 Download PDFInfo
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- CN1656129A CN1656129A CNA038118025A CN03811802A CN1656129A CN 1656129 A CN1656129 A CN 1656129A CN A038118025 A CNA038118025 A CN A038118025A CN 03811802 A CN03811802 A CN 03811802A CN 1656129 A CN1656129 A CN 1656129A
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Classifications
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Abstract
本发明涉及具有气体阻挡性能的多涂层体系,该体系能通过紫外光辐射进行光交联,且特别适合于外部保护由热塑性聚合物制造的容器,如由PET制造的瓶子。该体系包括通过曝光于紫外光辐射下能进行光交联的溶液和通过曝光于紫外光辐射下能进行光交联的组合物,其中所述可光交联的溶液包括对紫外光辐射感光的物质,和所述可光交联的组合物包括可光交联树脂与光引发剂的混合物。
Description
本发明涉及具有气体阻挡性能的可光交联的多涂层体系,它特别适合于外保护由热塑性材料,如PE、PP、PET、PVC、PA等制造的容器。
特别地,本发明涉及对氧气、二氧化碳和对一般的气体提供阻挡效果的多涂层体系,它适合于由聚对苯二甲酸乙二酯(PET)制造的可弃置瓶子的表面处理。
目前存在于市场上的包装食品和盛装饮料的可弃置容器必须结合不可破坏和透明度的特征以及保护避免空气的氧化进攻的特征。
近年来已发现,日益增加的大量消费者调整了它们对包装在可弃置塑料容器内的食品的购买倾向。
表面与在其中包含的食品产品的体积之间呈现低比例的上述容器,对气体具有不令人满意的阻挡性能特征。
结果,包装在可弃置容器内的食品更容易遭到大气氧的进攻,并进而呈现出短的防腐时间。
为了限制上述缺点,在食品包装工业中已引入生物取向(bio-oriented)PET的使用,这是因为该聚合物呈现出固有地高的气体阻挡性能、无毒性和特别地对于几乎所有食品如此。
然而,已发现,尽管具有上述特征,但还没有证明PET适合于包装某些食品,如酱油、和一些饮料如啤酒和葡萄酒,这是因为它们进行由氧化现象引起的生物化学本性的改性所致。
为了限制上述缺点的出现,采用合适保护的油漆产品,设法限制氧气扩散到由PET制造的容器内部。
此外,存在涂布由PET制造的容器的已知体系,所述体系采用多层多聚偶合的材料和等离子体涂布的技术。
然而,目前可商购的用于涂布的油漆体系存在某些技术局限,如需要利用大量溶剂和对油漆生产线来说繁重,从环境角度看,使得它们远没有竞争性。
此外,已发现目前用于外涂布PET的油漆体系需要使用低罐储寿命和低聚合速度的生物组分产品。
广义上讲,本发明的一个目的因此在于显著防止或限制已有技术呈现的缺点出现。
本发明的另一目的在于提供具有气体阻挡性能的多涂层体系,它对工作环境无毒。
本发明进一步的目的在于提供具有气体阻挡性能的多涂层体系,它适合于由PET制造的包装食品和盛装饮料的容器的外保护。
鉴于上述目的和根据随后的内容更清楚地出现的另外的目的,根据本发明的第一方面,提供根据所附权利要求的具有气体阻挡性能的多涂层体系。
根据本发明的一个方面,提供可通过紫外光辐射交联的具有气体阻挡性能的多涂层体系,所述多涂层体系包括:
(I)通过曝光于紫外光辐射下能进行光交联的溶液;
(II)通过曝光于紫外光辐射下能进行光交联的组合物。
根据本发明的一个实施方案,所述可光交联的溶液(I)是含聚乙烯醇、对紫外光辐射感光的物质、酸化组分和整理剂的水-醇(hydro-alcoholic)溶液。
可光交联的溶液中的聚乙烯醇(PVOH)可具有不同的水解度,例如部分水解度,水解-皂化程度,用mol%表示,为81至92比较有利或要么具有完全水解度用mol%表示,97至99的水解-皂化程度比较有利。
在本发明的框架内,优选使用完全水解度的聚乙烯醇,所述聚乙烯醇有利地具有下述特征:
-用mol%表示的水解(皂化)度为98.4±0.4;
-用mg KOH/g表示的酯值(根据标准DIN 53401)为20±5;
-摩尔重量(MW)为60000至63000g/mol。
上述类型的醇例如是由CLARIANT生产的产品MOWIOL10-98。
优选将聚乙烯醇以2%至15%的百分用量加入到去离子水中,其中优选溶液含有3%-5%是根据本发明的用途给予最佳粘度的聚乙烯醇。作为在可光交联的溶液(I)内的光敏物质,尽管可使用一旦曝光于紫外光下进行交联的任何物质,但有利地上述物质应当在它的分子内包括至少一个醛官能团和至少一个碳碳双键(C=C)。优选使用4-[2-(4-甲酰基苯基)乙烯基]-1-甲基吡啶鎓甲基硫酸盐(经验式C16H17NO5S,CAS号74401-04-0),如由Materiali Sensibili s.r.l.生产的SBQ,它具有下述特征:
-物理状态:黄色粉末;和
-在250至400nm之间的光谱敏感度。
有利地,基于聚乙烯醇的干燥质量,以0.5%至20%的百分数,和优选以10%至16%的百分数添加可进行光交联的上述物质,这是因为这代表阻挡特征和价格的良好折衷。
交联溶液的酸化组分可由酸,优选由无机类型的酸组成,更优选由磷酸,例如80%磷酸组成。
将这一酸化组分以0.6%至0.8%的百分数引入到交联溶液中。
所述水醇交联溶液的整理剂是适合于改进基质润湿性特征的物质,和有利地包括正甲基吡咯烷酮、异丙醇,及其混合物,有利地以0.5wt%至1.5wt%的用量掺入到溶液中。
为了轻微提高对基质的粘着特征和所述可光交联溶液(I)的抗湿性,可任选结合乙酰丙酮合钛(例如由DuPont生产的商购产品TYZORAA95)。
上述产品是钛的螯合物,其中具有作为螯合剂的乙酰丙酮化物,和各种烷氧化物基团。
乙酰丙酮合钛的上述络合物与存在于聚乙烯醇(PVOH)分子内的OH官能团反应。
可在室温下,在数小时内,或要么在较高温度下(例如在80℃下数秒)发生交联反应。
为了使用上述络合物和能使其增溶,首先需要增溶它们并使它们在水溶液中稳定,如下所述:
在轻轻搅拌下,向10重量份乙酰丙酮合钛中添加20份冰醋酸,然后添加70重量份软化水。
乙酰丙酮合钛溶液的实例:
TYZORAA95: 10份
冰醋酸: 20份
轻轻混合5分钟
软化水: 70份
基于聚乙烯醇(PVOH)的干燥质量,待使用的百分数范围从最小5%的乙酰丙酮合钛到最大60%。
可加入到可光交联溶液(I)中以提高耐水性的一些特征的其它任选添加剂是DIAZO COMPOUNDS;若采用250-400nm之间波长的紫外光辐射激活的话,这些盐会起作用。
在可光交联溶液(I)中,尽管可使用一旦曝光于紫外光下会激活的任何重氮化合物,但优选使用在具有甲醛的1∶1溶液中的苯重氮鎓-4-(苯基氨基)氢磷酸盐聚合物,如由Materiali Sensibili s.r.l.生产的例如FSO。
这类敏化剂在室温下和在暗处稳定;若使温度达到高于35℃,则它被引发,且开始进行在可光交联溶液(I)中存在的PVOH中的OH的连接工艺。
由于该原因,优选在施加之前立即使用它。待使用的百分数,仍称为聚乙烯醇PVOH的固体质量,为0.5%至5%。
可通过紫外光辐射进行光交联的组合物(II)可以是“阳离子”类型(A)或要么是“自由基交联丙烯酸”类型(B)。
采用可光交联的组合物(II),其唯一目的是保护可光交联溶液(I)。
对于不同类型的应用来说,通过使用多层体系,来决定选择可光交联溶液(II)中两种不同类型的组合物,其中在所述多层体系内要求涂料的不同特征。
据估计,紫外光“阳离子”型可光交联溶液(II)呈现出更好的挠性和耐热处理性。
通过在加热到85℃的水中浸渍油漆过的样品约10分钟,进行模拟试验。
进行在涂层上的这种测定,目的是为了模拟适合于热填充容器的操作条件(例如瓶装HEAT-SET果汁用的由PET制造的瓶子)。
紫外光“自由基丙烯酸”型可光交联溶液(II)呈现出对用酸化学处理,尤其对过乙酸处理更好的抗性。
通过在0.1%的过乙酸溶液中浸渍油漆过的样品约5分钟,进行模拟试验。
进行在涂层上的这种测定,目的是为了模拟适合于在无菌条件下填充容器的操作条件(例如瓶装在无菌环境中填充果汁用的由PET制造的瓶子)。
根据本发明的一个实施方案,所述紫外光“阳离子”型可光交联组合物(A)包括选自双官能团脂环族环氧树脂、多元醇聚酯树脂及其混合物之间的树脂混合物,光引发剂体系,反应性稀释剂体系,和各种添加剂。
合适的双官能团脂环族环氧树脂的环氧当量(EEW)优选100至200,和更优选125至150,和在25℃下测量的粘度优选350至450cP。例如,这类树脂是3,4-环氧基环己基甲基-3′,4′-环氧基环己羧酸酯,如由DowChemical Company生产的可商购树脂CYRACURE紫外光R 6110。
有利地以60wt%至85wt%,优选65wt%至75wt%的用量使用上述双官能团脂环族环氧树脂。
可使用的多元醇聚酯树脂优选三元醇,特别地优选羟基当量(OHEW)为100至250,更优选170至190且在25℃下测量的粘度优选2000至2100cP的ε-己内酯三醇。特别合适的这类树脂是由Dow ChemicalCompany生产的产品TONE己内酯多元醇0305。
有利地以2wt%至15wt%,更优选5wt%至10wt%的用量使用上述多元醇聚酯树脂。
所述组合物的光引发剂体系通常包括阳离子光引发剂,例如生成三芳基锍型盐(TAS盐)或二芳基碘鎓型盐(DAI盐)的光致潜酸的类型。优选以1wt%至5wt%,更优选2wt%至4wt%的百分数,将阳离子光引发剂加入到光交联组合物中。
已证明,使用例如在50%碳酸亚丙酯溶液内的由Dow ChemicalCompany生产的CYRACURE紫外光I-6992类型的三芳基锍六氟磷酸盐的混合物,是特别合适的。
或者,可使用百分数为0.5%至4%,优选1%至3%的在75%碳酸亚丙酯溶液内的二芳基碘鎓盐,例如4-(异丁基苯基)-4-甲基苯基碘鎓六氟磷酸盐。
可紫外光光交联组合物(II)中的反应性稀释剂体系是适合于降低光交联组合物粘度、具有与该体系反应的能力的物质。有利地,该稀释剂拥有3-乙基-3-羟甲基氧基乙烷类型的羟基官能度,如由DowChemical Co.生产的产品CYRACURE紫外光R 6000,或1-甲氧基-2-丙醇类产品,如同样仍由Dow生产的DOWANOLPM,或其混合物。
有利地,以5wt%至20wt%,和优选10wt%至15wt%的用量,将所述反应性稀释剂体系加入到交联组合物中。
优选阳离子型(A)光交联组合物进一步包括为改进滑爽和铺展性能而添加的一种或多种添加剂。
事实上,已证明,在涂布膜的形成过程中,可能产生许多问题,如油漆过的区域不足的润湿性、流平性差、形成凹坑和其它缺点。在膜的表面上形成的该现象对缺陷的形成起着重要作用,和也可影响膜本身的性能。可通过添加小量的表面活性剂来显著地影响上述现象。
表面活性类的某些物质,即例如通过在与空气接触的界面上富集,从而降低液体表面张力的物质,已证明适于使用。
合适的表面活性剂包括用聚醚或聚酯改性的硅氧烷。已发现,上述添加剂的存在有助于改性下述性能的至少一种:
-改进流平和铺展性;
-控制波浪效果;
-控制在颜料上的分离;
-降低摩擦系数(改进表面滑爽);
-增加抗划伤性;和
-改进物质的润湿。
特别合适的添加剂是硅氧烷聚醚共聚物,例如由Tego DegussaAdditivi生产的TEGOGLIDE440类型的硅氧烷聚醚共聚物,其中优选以0.1wt%至1.0wt%,更优选0.2wt%至0.5wt%的用量加入到组合物中。
“自由基丙烯酸”型(B)可光交联的组合物(II)包括一种或多种脂族类型的聚氨酯丙烯酸酯树脂,一种或多种单体反应性稀释剂,光引发剂体系,和一种或多种添加剂。
合适的聚氨酯丙烯酸酯树脂包括一种或多种下述类型的树脂:
a)优选分子量为700至1500,更优选900至1100,和在60℃下的粘度有利地为1800至2200mPa.s的脂族类型的聚氨酯丙烯酸酯低聚物树脂。此外,已发现,该低聚物的官能度可以等于1或更高,即使如此优选的官能度为6。所述低聚物的商业产品可以是由UCB Chemicals生产的EBECRYL1290;或者可使用由Benasedo S.p.A.生产的Bencryl655。
在该配方中,该化合物可以是2wt%至15wt%,然而,优选以4wt%至8wt%的百分数使用它。
将它引入该配方中,以赋予涂层硬度、高的抗溶剂性和对外部试剂的耐用性(外部耐用性)的性能。
b)有利地用12%丙烯酸单体,1,6-己二醇二丙烯酸酯(HDDA)稀释的优选分子量为1000至1500,更优选1100至1300,和在60℃下的粘度有利地为1800至2200mPa.s的脂族类型的聚氨酯丙烯酸酯低聚物树脂。此外,已发现,该低聚物的官能度可以等于1或更高,即使如此优选的官能度为2。这种低聚物的商业实例是由UCB Chemicals生产的EBECRYL284。
在该配方中,该化合物可以是1wt%至10wt%,然而,优选以2%至5%的百分数使用它。
将它引入该配方中,以赋予涂层???皮革状性能和对外部试剂的优良耐用性(外部耐用性)。
c)有利地分子量为300至700,优选400至600,和在25℃下的粘度有利地为6500至7500mPa.s的脂族类型的聚氨酯丙烯酸酯低聚物树脂。此外,已发现,该低聚物的官能度可以等于1或更高,即使如此优选的官能度为2。所述低聚物的商业产品可以是由UCB Chemicals生产的EBECRYL4858。
在该配方中,该化合物的百分数可以是5%至25%,然而,优选以10%至18%的百分数使用它。
将它引入该配方中,以赋予涂层对外部试剂的优良耐用性和抗化学品的性能。
d)优选分子量为600至1000,更优选700至900,在60℃下的粘度有利地为600至800mPa.s的脂族类型的聚氨酯丙烯酸酯低聚物树脂。此外,已发现,该低聚物的官能度可以等于1或更高,即使如此优选的官能度为6。所述低聚物的商业实例是由Benasedo S.p.A.生产的Bencryl 646;或者可使用由UCB Chemicals生产的EBECRYL5129。
在该配方中,该化合物的百分数可以是10wt%至40wt%,然而,优选以15wt%至25wt%的百分数使用它。
将它引入该配方中,以赋予涂层抗磨损和挠性的性能。
特别合适的单体反应性稀释剂具有能优化所讨论涂层特征的丙烯酸官能度且作为粘度调节剂。
根据本发明的一个实施方案,特别合适的混合物由常规地存在量为25wt%至45wt%,优选30wt%至40wt%的多官能团丙烯酸单体反应性稀释剂,优选分子量常规地为200至400,和优选250至350,和在25℃下的粘度有利地为5至20mPa.s的三丙二醇二丙烯酸酯(TPGDA)类型的双官能团类型的多官能团丙烯酸单体反应性稀释剂,和常规地存在量为10wt%至30wt%,优选15wt%至20wt%的丙烯酸乙氧化多官能团单体反应性稀释剂,优选分子量常规地为350至500,和优选400至450,且在25℃下的粘度有利地为70至90mPa.s的三羟甲基丙烷乙氧化三丙烯酸酯(TMPEOTA)类型的三官能团类型的丙烯酸乙氧化多官能团单体反应性稀释剂组成。
所述可光交联组合物(II)中的光引发剂体系具有获得快速和有效交联组合物中各组分的基本功能。
合适的光引发剂包括对紫外光辐射感光的化合物作为自由基源,如二苯酮、以α-羟基烷基苯基酮形式衍生的乙酰苯、苯甲酰(benzoyn)烷基缩酮、单酰基氧化膦、双酰基氧化膦,及其混合物。
此外,已发现,在可光交联组合物配方内存在大于一种光引发剂,除了增加丙烯酸基聚合物混合物的聚合速度以外,还决定在表面和在深处平衡油漆的硬化程度。
根据优选的实施方案,使用两种光引发剂的混合物,常规地由双酰基氧化膦和α-羟基烷基苯基酮组成。
例如,光引发剂的特别合适的混合物由常规地存在量为0.5wt%至1.5wt%,优选0.8wt%至1.2wt%由Ciba Speciality Chemicals生产的IRGACURE819类型的双酰基氧化物,和常规地存在量为3wt%至5wt%,优选3.5wt%至4.5wt%由Ciba Speciality Chemicals生产的DAROCUR1173类型的α-羟基烷基苯基酮的混合物组成。
典型地,光引发剂以混合物的形式以4wt%至6wt%的用量范围存在于光交联组合物中。
根据本发明的一个实施方案,紫外光“自由基丙烯酸”型(B)可光交联组合物(II)包括在前面的紫外光“阳离子”型(A)可光交联组合物(II)中所述类型的为改进涂层的滑爽和铺展性用的一种或多种添加剂。
特别合适的添加剂是硅氧烷聚醚共聚物,例如由Tego DegussaAdditivi生产的TEGOGLIDE440型硅氧烷聚醚共聚物,其中以优选0.1wt%至1.0wt%,更优选0.2wt%至0.5wt%的百分数加入到组合物中。
根据本发明,适合于施加多涂层体系的基质包括其中通过紫外光光可进行交联的与涂层相容的基质。优选的聚合物基质包括热塑性材料,如PE、PP、PET、PVC和PA。根据一个实施方案,在施加到特别苛刻的基质上之前,优选进行处理,如火焰或要么电晕放电处理。基质的厚度优选10至2000微米。本发明的多涂布体系特别适合于通过在多涂布体系中浸涂待处理部件,有利地进行在三维部件,如由PET制造的瓶子上的施涂,随后离心该部件,除去过量的部分涂料。该施涂技术能使待获得的产品实际上全部转移到待处理的部件上,且没有造成喷雾施涂的转移和过度喷涂问题。在由PET制造的瓶子上施涂两种涂料体系的情况下,例如通过浸涂技术,通过浸渍瓶子来施涂有效量的可交联溶液(I),然后通过引起它以可变的速度绕其轴旋转离心它,以便获得1至4微米的干膜厚度。然后,为了获得在4至10微米范围内的干膜厚度,在首先交联的涂布层上施涂可光交联的组合物(II)。
根据本发明另一实施方案,提供在基质上施涂和硬化以上所述的涂料体系的方法。
在本发明上下文中使用的紫外光交联技术优选利用波长在200至400nm之间的辐射发射源。合适的紫外光辐射源包括中压汞蒸汽灯(Hg灯)。
认为该方法的第一步在基质上施涂如前所述的可光交联溶液(I),随后通过由紫外光灯产生的紫外光的辐射而交联。
有利地,交联步骤之前是闪蒸阶段的步骤,在所述闪蒸阶段的步骤中,将用油漆处理过的样品曝光于优选55℃至65℃的温度下,例如通过曝光于IR灯下,或要么曝光于热空气下可变的时间长度,和典型地30至50秒,以便能蒸发配方内的水相。
有利地,使用中压汞蒸汽灯(Hg灯)供交联。
仅仅通过例举,在其中需要进行在基质上施涂的2至3微米干燥的可光交联溶液(I)的交联的情况下,用汞灯处理样品,以便在辐照的样品上测量交联所需的剂量(用mJ/cm2表示),方便地具有下述数值:
-光谱区域:紫外光-A(320至390nm之间):480-500mJ/cm2
-光谱区域:紫外光-B(280至320nm之间):430-450mJ/cm2
-光谱区域:紫外光-C(250至260nm之间):70-90mJ/cm2
-光谱区域:紫外光-Vis(395至445nm之间):310-340mJ/cm2。
一旦通过交联溶液(I)获得第一保护层,则施涂可光交联的组合物(II)。在施加该组合物之后,通过由紫外光灯产生的紫外光辐射交联它。
方便地,交联步骤之前是闪蒸阶段的步骤,在所述闪蒸阶段的步骤中,将用油漆处理过的样品曝光于典型地55℃至65℃的温度下,例如通过曝光于IR灯下,或要么曝光于热空气下可变的时间长度,和典型地10至30秒的时间间隔,以便能使产品铺展。有利地,使用中压汞蒸汽灯(Hg灯)供交联。
仅仅通过例举,在其中需要进行在基质上施涂的6至8微米干燥的组合物(II)实施方案的交联的情况下,用汞灯处理基质,以便在辐照的基质上测量交联所需的剂量(用mJ/cm2表示),其具有下述数值:
-光谱区域:紫外光-A(320至390nm之间):260-280mJ/cm2
-光谱区域:紫外光-B(280至320nm之间):180-200mJ/cm2
-光谱区域:紫外光-C(250至260nm之间):30-50mJ/cm2
-光谱区域:紫外光-Vis(395至445nm之间):170-190mJ/cm2。
本发明的方法能制造构成阻挡层的涂层,所述阻挡层防止氧气进入和二氧化碳出来,具体地推荐所述涂层用于包装和瓶装食品与饮料用的部分材料。
此外,本发明的方法在高的交联速度和低的能耗情况下,能获得双涂层保护体系。此外,由于该涂布方法因减少溶剂的使用导致具有低的VOC,因此它呈现出有利的环境冲击。
仅通过阐述本发明来提供下述实施例,和因此一定不能在以任何方式限制保护范围的意义上理解下述实施例,这种保护范围由所附的权利要求来限定。
实施例1
根据本发明制备可光交联溶液(I)的实施方案:
1)制备15%的PVOH溶液-程度(皂化度):在水中为98:
-将无细菌含量的软化水倾入到清洁的反应器中;然后在搅拌下,加热该反应器到90-95℃;
-在维持在95-98℃的温度下,缓慢添加PVOH,为的是不生成聚集体,直到获得粘度与特性曲线一致的透明溶液;然后冷却该产品到40℃并用1微米的袋滤器过滤。
2)制备1kg具有16%SBQ的光聚合物的5%PVOH溶液(称为PVOH):
-将下述物质装在清洁的反应器内:约333g在1点中制备的PVOH溶液,约8g 80%磷酸,约8g SBQ,和视需要的软化水;
-加热上述到40℃,维持该温度24小时,通过测量吸光度证明缩合反应的进展。在这一制备步骤过程中,SBQ的醛部分与在聚乙烯醇PVOH结构内存在的羟基OH反应(缩醛化步骤),同时形成环状缩醛。
-在反应终点处,测量下述:粘度和pH。过滤产品,然后倾到出来;
-在完全黑暗的条件下进行所有上述操作,为的是不引起SBQ的降解。
向以上制备的溶液中添加百分数为约1wt%的正甲基吡咯烷酮或要么异丙醇,为的是改进基质的润湿性特征。
实施例2
适合于在由PET制造的基质上赋予氧气阻挡性能的可通过紫外光辐射交联的油漆产品。
按照在实施例1的说明中出现的指示配制它。
可光交联溶液的配方:
PVOH:Mowiol10-98在水中在15%浓度下 33.3%
SBQ 0.8%
80%磷酸 0.8%
去离子水 64.1%
润湿添加剂(异丙醇) 1.0%
固体含量 5-6%
在25℃下的粘度(cP) 130
颜色 <1(色调:红松色(cedar))
实施例3
通过阳离子型(A)紫外光辐射的可光交联组合物(II)配方
-脂环族环氧树脂-CYRACURE紫外光R 6110 75.0%
-多元醇聚酯树脂-TONE己内酯多元醇0305 10.0%
-锍盐光引发剂-CYRACURE紫外光I-6992 4.0%
反应性稀释剂(1-甲氧基-2-丙醇) 0.9%
添加剂(硅氧烷聚醚共聚物-TEGOGLIDE 440) 0.1%
实施例4
通过自由基丙烯酸型(B)紫外光辐射的可光交联组合物(II)配方
六官能团聚氨酯丙烯酸酯脂族树脂-PM 1000 4.0%
双官能团聚氨酯丙烯酸酯脂族树脂(在HDDA内的12%溶液) 5.0%
-PM1000
双官能团聚氨酯丙烯酸酯脂族树脂-PM500 15.0%
六官能团聚氨酯丙烯酸酯脂族树脂-PM800 20.0%
丙烯酸单体反应性稀释剂-TPGDA 35.0%
丙烯酸单体反应性稀释剂-TMP(EO)TA 17.3%
光引发剂(双酰基氧化膦) 0.5%
光引发剂(α-羟基烷基苯基酮) 3.0%
添加剂(硅氧烷聚醚共聚物,例如TEGO GLIDE 440) 0.2%
阻挡性能的测量
具有许多方法测量气体或液体传输或扩散穿过聚合物的比例。
在本发明的工作中,测量气体的传输度所使用的方法使用由ModernControls Inc.(MOCON)设计并开发的仪器,该方法确定在比其它评价方法(例如Dow Permeation Cell)的时间间隔明确地要短的时间间隔内氧气传输穿过聚合物样品的比例。仪器(例如OX-TRAN 220)是一种扩散元件,它使用对氧气特定的检测器。同样提供将水蒸汽引入到气体内的腔室,所述腔室提供有流动控制器。也可在与水接触的情况下测试该膜。
在适当位置放置样品的情况下,扩散元件的顶部与底部腔室开始用不含氧气的气体(99%氮气,1%氢气)清洗,从体系中除去所有残留的氧气和所有氧气从样品中解吸。
接下来,将纯氧气引入到顶部扩散腔室内,和使用次电流(subcurrent)检测器,通过测量传输穿过膜的氧气浓度来进行试验。
样品在测量装置上合适地调节之后获得的传输率的恒定值减去仪器的背景值,构成试验的结果。
调节时间必须使得能消除在样品内存在的和在测试膜的壁上合适增溶的氧气。
在1atm.的条件下,和在控制温度条件下,传输物质的相对湿度为0%的情况下,评估氧气传输速度(以cc/(m2*天)来表示)。
在油漆过的样品上氧气传输速度的下降也将表示为相对于参考标准的倍增因子(2×、5×、10×,等)。
评估的样品和结果
对于在前述说明框架内获得的各类混合物来说,在试验室中进行在平面塑料膜上的施涂。基于这是评估全部特征最快速和最实际的体系的事实,从而选择在平面塑料膜上施加油漆样品。
作为参考膜,使用厚度约36微米的聚酯膜。
采用下述样品:
-膜+实施例2的气体阻挡油漆(1微米干燥厚度)+实施例3的油漆(仅仅6微米);和
-膜+实施例2的气体阻挡油漆(1微米干燥厚度)+实施例4的油漆(仅仅6微米)。
没有油漆过的参考膜 | 膜+实施例2+实施例3 | 膜+实施例2+实施例4 | |
传输速度(cc/(m2.天)) | 37.7659 | 0.6227 | 0.7233 |
倍增因子 | 1 | 60.6 | 52.2 |
质量 | - | 良好 | 相当好 |
冰-热处理 | - | 良好 | 差 |
冰处理 | - | 差 | 良好 |
Claims (30)
1.一种能通过紫外光辐射进行交联的具有气体阻挡性能的多涂层体系,所述多涂层体系包括:
-通过曝光于紫外光辐射下可进行光交联的溶液(I);
-通过曝光于紫外光辐射下可进行光交联的组合物(II);
其中所述可光交联的组合物(II)包括可光交联树脂、反应性稀释剂和光引发剂的混合物;其特征在于:
所述可光交联的溶液(I)包括对紫外光辐射感光的物质,该物质在其分子内包括至少一个醛官能团和至少一个碳碳双键(C=C)。
2.权利要求1的多涂层体系,其特征在于所述对紫外光辐射感光的物质是4-[2-(4-甲酰基苯基)]乙烯基]-1-甲基吡啶鎓甲基硫酸盐。
3.权利要求1的多涂层体系,其特征在于所述可光交联的溶液(I)进一步包括:聚乙烯醇、对紫外光辐射感光的物质、酸化物质,和增加润湿性特征的整理剂。
4.权利要求1的多涂层体系,其特征在于所述可光交联的溶液(I)进一步包括乙酰丙酮合钛溶液。
5.权利要求4的多涂层体系,其特征在于所述乙酰丙酮合钛溶液由具有作为螯合剂的乙酰丙酮化物和各种烷氧基的钛螯合物组成。
6.权利要求1的多涂层体系,其特征在于所述可光交联的溶液(I)进一步包括重氮化合物。
7.权利要求4的多涂层体系,其特征在于所述重氮化合物由在具有甲醛的1∶1溶液中的苯重氮鎓-4-(苯基氨基)氢磷酸盐聚合物制成。
8.权利要求1的多涂层体系,其特征在于所述可光交联的组合物(II)包括可进行光交联的混合物,所述混合物由可通过紫外光辐射交联的至少一种阳离子树脂、至少一种反应性稀释剂和光引发剂组成。
9.权利要求1的多涂层体系,其特征在于所述可光交联的组合物(II)包括可进行光交联的混合物,所述混合物由至少一种自由基可交联的丙烯酸树脂的混合物、单体反应性稀释剂和光引发剂的混合物组成。
10.权利要求1的多涂层体系,其特征在于所述可光交联的溶液(I)是水醇溶液,在所述水醇溶液中,聚乙烯醇的存在量为2%至15%。
11.权利要求3的多涂层体系,其特征在于所述酸化物质是磷酸。
12.权利要求3的多涂层体系,其特征在于所述整理剂是正甲基吡咯烷酮、异丙醇或其混合物。
13.权利要求8的多涂层体系,其特征在于可通过紫外光辐射交联的阳离子树脂选自双官能团脂环族环氧树脂、多元醇聚酯树脂或其混合物。
14.权利要求13的多涂层体系,其特征在于所述双官能团脂环族环氧树脂的环氧当量为100至200。
15.权利要求13或14的多涂层体系,其特征在于所述双官能团脂环族环氧树脂是3,4-环氧基-环己基-甲基-3′,4′-环己羧酸酯。
16.权利要求13的多涂层体系,其特征在于所述多元醇聚酯是ε-己内酯三醇。
17.权利要求8的多涂层体系,其特征在于所述光引发剂是三芳基锍盐(TAS盐)或二芳基碘鎓盐(DAI盐)或其混合物。
18.权利要求8的多涂层体系,其特征在于所述反应性稀释剂含有羟基官能度。
19.权利要求18的多涂层体系,其特征在于所述反应性稀释剂是3-乙基-3-羟基-甲基-氧基乙烷、1-甲氧基-2-丙醇,或其混合物。
20.权利要求8的多涂层体系,其特征在于它进一步包括为改进滑爽用的添加剂,所述添加剂选自硅氧烷低聚物、用聚醚改性的硅氧烷,或用聚酯改性的硅氧烷。
21.权利要求9的多涂层体系,其特征在于所述丙烯酸树脂的混合物是脂族类型的聚氨酯-丙烯酸酯低聚物树脂的混合物。
22.权利要求21的体系,其特征在于所述脂族聚氨酯-丙烯酸酯低聚物树脂包括:
a)分子量为700至1500的脂族聚氨酯-丙烯酸酯低聚物树脂;
b)分子量为100至1500的脂族聚氨酯-丙烯酸酯低聚物树脂;
c)分子量为300至700的脂族聚氨酯-丙烯酸酯低聚物树脂;
d)分子量为600至1000的脂族聚氨酯-丙烯酸酯低聚物树脂。
23.权利要求22的体系,其特征在于所述树脂a)和d)是六官能团树脂和所述树脂b)和c)是双官能团树脂。
24.权利要求9的多涂层体系,其特征在于所述光引发剂选自二苯酮、以α-羟基烷基苯基酮形式衍生的乙酰苯、苯甲酰(benzoyn)烷基缩酮、单酰基氧化膦、双酰基氧化膦,或其混合物。
25.权利要求24的多涂层体系,其特征在于所述光引发剂是双酰基氧化膦与α-羟基烷基苯基酮的混合物。
26.权利要求9的多涂层体系,其特征在于提供所述单体反应性稀释剂丙烯酸官能度。
27.权利要求25的多涂层体系,其特征在于所述反应性稀释剂是一个官能团类型的丙烯酸多官能团单体反应性稀释剂和一个三官能团类型的丙烯酸-乙氧化多官能团单体反应性稀释剂的混合物。
28.一种由热塑性材料制造的基质,它包括通过紫外光交联权利要求1-27任何一项的体系获得的具有气体阻挡性能的层。
29.权利要求28的基质,其特征在于它由选自PE、PP、PET、PVC和PA中的热塑性材料制成。
30.权利要求28或29的基质,其特征在于它是由PET制造的瓶子。
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IT2002TO000362 ITTO20020362A1 (it) | 2002-04-30 | 2002-04-30 | Sistema multirivestimento con proprieta' di barriera ai gas, fotoreticolabile mediante radiazione uv particolarmente idoneo per la protezion |
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AU (1) | AU2003229700A1 (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN108192488A (zh) * | 2017-12-29 | 2018-06-22 | 广州立邦涂料有限公司 | 溶剂型双组分、高滑爽性的清漆组合物、制备方法及用途 |
CN108192488B (zh) * | 2017-12-29 | 2021-03-02 | 广州立邦涂料有限公司 | 溶剂型双组分、高滑爽性的清漆组合物、制备方法及用途 |
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KR100929053B1 (ko) | 2009-11-30 |
US20050171229A1 (en) | 2005-08-04 |
ITTO20020362A1 (it) | 2003-10-30 |
MXPA04010731A (es) | 2005-11-23 |
WO2003093329A1 (en) | 2003-11-13 |
CN100475859C (zh) | 2009-04-08 |
KR20050008700A (ko) | 2005-01-21 |
AU2003229700A1 (en) | 2003-11-17 |
CA2483637A1 (en) | 2003-11-13 |
ITTO20020362A0 (it) | 2002-04-30 |
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