CN101035844A - 阻隔涂层 - Google Patents
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Abstract
公开了包含聚合物材料和酸的反应产物的阻隔涂料。还公开了提高基材的阻隔性的方法,以及根据这一方法处理的基材。
Description
发明领域
本发明涉及包含聚合物材料和酸的反应产物的阻隔涂层。提高基材的阻隔性的方法也在本发明内。
背景信息
塑料在包装中已日益用作玻璃和金属容器的取代品。塑料包装好于玻璃包装的优点包括更轻质、降低的破损和可能更低的成本。塑料包装好于金属包装的优点是塑料可以更容易地设计为可再封闭的。当常用的塑料包装材料(例如,聚酯、聚烯烃和聚碳酸酯)用来包装氧气敏感性物品和/或碳酸饮料时,此类材料的气体阻隔性能方面的缺点可能会是问题。例如,一些氧气敏感性产品甚至在片刻暴露于氧气之后就可能变得变色和/或损坏,而如果二氧化碳出去的话,碳酸饮料可能损失它们的碳酸化作用或变得“淡而无味”。
具体而言,气体例如氧气和二氧化碳可以容易地穿透包装工业常用的大多数塑料材料。氧气渗透常数(“P(O2)”)将可以在具体设置的情况下穿过薄膜或涂层的氧气的量量化并通常用单位cm3-密耳/100英寸2/大气压/天表示。这是渗透率的标准单位,测量为在具体的温度和相对湿度(R.H.)条件下在一个大气压的分压差下,经过24小时,氧气穿透面积为100平方英寸(645平方厘米)厚度为1密耳(25.4微米)的样品的立方厘米数。除非另有说明,本文所使用的P(O2)值在23℃+/-5℃和50%的R.H.下报道。
目前食品和饮料工业使用的常用包装材料之一是聚(对苯二甲酸乙二醇酯)(“PET”)。虽然它被广泛使用,但是PET具有较高的P(O2)值(即,大约6.0)。其它包装材料例如聚酯、聚烯烃、聚碳酸酯等同样是气体可渗透的。食品和饮料包装工业已在寻求改进此类包装材料的P(O2)值的途径。
发明概述
本发明涉及包含聚合物材料和酸的反应产物的阻隔涂料,其中当该酸是有机二酸时该涂料不包含二缩水甘油醚或其残余物,该涂料不包含硅烷材料或其残余物,和当该酸是烯属不饱和酸时该涂料不包含多元胺。如本文所述,本发明进一步涉及使用阻隔涂层改进基材的阻隔性的方法,该阻隔涂层包含聚合物材料和酸的反应产物。
发明详述
本发明涉及包含聚合物材料和酸的反应产物的阻隔涂料,其中当该酸是有机二酸时该涂料不包含二缩水甘油醚或其残余物,该涂料不包含硅烷材料或其残余物,和当该酸是烯属不饱和酸时该涂料不包含多元胺。“阻隔涂层”是指具有低的气体(例如氧气和/或二氧化碳)渗透率的涂层;即,该涂层显示对氧气、二氧化碳和/或其它气体穿过该材料的通过进行阻挡。根据本发明,对任何气体的渗透进行任何阻挡就足以将该涂层称为“阻隔涂层”。
根据本发明,可以使用在上面给出的参量内的任何聚合物材料,包括聚合物材料的组合,即,当酸是有机二酸时,涂料不包含二缩水甘油醚或其残余物。“二缩水甘油醚或其残余物”应理解为是指具有或者由二缩水甘油醚制成的化合物。涂料不具有且不由硅烷材料例如SiH4制成,在该SiH4中一个或多个氢可以被烃代替。最后,当酸是烯属不饱和酸时,涂料不包含多元胺。
用于本发明的尤其合适的聚合物材料是当以涂层形式沉积到基材上并固化时将赋予阻隔效果的那些。“聚合物材料”通常是指具有一个或多个将与酸反应的官能团和多于一个重复基团的烃。在某些非限制性实施方案中,具体排除可以通过光化辐射固化的聚合物材料。具有芳香性的聚合物材料是尤其适合的。含环氧的材料和/或含胺的材料也是尤其适合的。本领域技术人员能将“含环氧”和同类术语理解为是指具有或由一种或多种环氧基团制成的任何材料。在本发明中可以使用多种的含环氧的材料,例如多环氧化物。环氧可以是饱和或不饱和、脂族、脂环族、芳族或杂环环氧并且可以被取代(如果需要的话),被非干扰性取代基例如羟基等取代。
有用的多环氧化物的实例是芳族多元醇,例如多酚的多缩水甘油醚。此类多环氧化物可以例如通过在碱的存在下用表氯醇或二氯丙醇将芳族多元醇醚化来制备。芳族多元醇可以是,例如,双(4-羟苯基)-2,2-丙烷(通常称为双酚A)、双(4-羟苯基)-1,1-乙烷、双(4-羟苯基)-1,1-异丁烷、双(4-羟基叔丁基苯基)-2,2-丙烷、双(2-羟基萘基)甲烷、4,4′-二羟基二苯甲酮、1,5-二羟基萘等。
其它适合的多环氧化物包括但不限于多羟基脂族醇例如1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、二甘醇、三甘醇、聚乙二醇、聚丙二醇等的聚缩水甘油醚。同样地,多羟基脂族醇可以是氢化的多酚例如2,2-双(4-羟基环己基)丙烷等。也可以使用各种多环氧化物的共混物,例如芳族多元醇和脂族多元醇的多环氧化物的共混物,或任何其它含环氧的材料。
在某些非限制性实施方案中,多环氧化物具有大于大约86,例如大约200到大约700,或大约200到大约400的分子量,并且具有大于大约43,例如大约100到大约350,或大约100到大约200的环氧当量重量。
含环氧的产品是可广泛商购的并且包括,例如,可从MitsubishiGas Chemical Co.以TETRAD-X商购的四缩水甘油基间二甲苯二胺,含环氧的材料也可从Resolution和Dow商购。
“含胺的化合物”以及同类术语应理解是指具有胺基和/或胺官能度的化合物,包括但不限于多元胺。在某些非限制性实施方案中,胺官能度可以例如直接地引到含环氧的化合物上。例如,可以使用TETRAD-X。在某些非限制性实施方案中,单独的含胺化合物可以与含环氧基的化合物结合起来使用。本发明中所使用的多元胺每个分子可以具有一个或多个伯氨基氮基团并且还可以具有其它的仲或叔氨基氮基团。此类多元胺可以是通式(R′)2N-(-RNH-R)nN(R′)2的脂族多元胺,其中R是C2-C6亚烷基,例如C2-C4亚烷基如亚乙基、亚异丙基等,R′是氢、低级烷基如甲基、乙基等,或其中烷基含大约1-4个碳原子的羟烷基,和n是0到大约10的整数,如大约1到大约5。此类多元胺的适合的实例包括乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、N-羟乙基乙二胺、N-羟乙基二亚乙基三胺、N,N-二羟乙基二亚乙基三胺、间二甲苯二胺等。多元胺也可以是芳族多元胺如对二氨基苯、4,4′-二氨基苯基苯胺等。多元胺也可以是酮封端的多元胺,有时称为酮亚胺,例如多元胺如四亚乙基五胺可以与酮如甲基异丁基酮等起反应,以产生具有封端的伯胺基和三个保持反应活性的仲胺基的多元胺。含二伯胺基的多元胺在形成非胶凝胺官能化聚合物树脂的反应中是适合的,三亚乙基四胺,四亚乙基五胺和四亚乙基五胺也是如此。
氨也可以是适合的多元胺的前体,例如,二摩尔氨可以与一摩尔适合的二环氧化物如双酚A的二缩水甘油醚起反应,以产生在本发明中有用的二伯胺官能化材料。多元胺也可以是聚乙烯亚胺等。更进一步地,多元胺也可以是聚氧化烯-多元胺,例如美国专利号4,423,166中描述的用于制备电淀积中所使用的非胶凝材料的材料。
尤其适合的多元胺是可从Mitsubishi Gas Chemical Co.以GASKAMINE商购的,它是低分子量多元胺。可以理解的是含胺的化合物(如果用于本发明的反应产物)实际上形成反应产物的一部分,而不是用作催化剂(其不会形成反应产物的一部分)。
如果同时使用含环氧的化合物和含胺的化合物,则可以按5.0∶1-0.20∶1的胺与环氧的当量比使用它们。
任何有机或无机酸可以用来形成本发明的反应产物。在某些非限制性实施方案中,酸是一元酸;实例包括但不限于乳酸、硝酸和乙酸。在其它非限制性实施方案中,使用多元酸。“多元酸”是指具有两个或更多个酸官能团的酸。实例包括但不限于柠檬酸、磷酸、酒石酸、衣康酸、琥珀酸、EDTA(乙二胺四乙酸)、抗坏血酸、丁烷四羧酸、四氢呋喃四羧酸、环戊烷四羧酸、苯四羧酸和柠康酸、中康酸、马来酸、富马酸、丙烯酸、甲基丙烯酸、山梨酸、乙烯基膦酸、乙烯基磺酸和肉桂酸。在某些非限制性实施方案中,可以理解的是,酸和聚合物材料形成反应产物,而不是形成具有聚合物骨架和接枝到该骨架上的酸的接枝共聚物。
本发明的反应产物可以在水或溶剂或它们的组合中制备。例如,根据本发明某些非限制性实施方案的反应产物可以如下制备:将酸与含环氧的化合物混合然后将该混合物添加到水中。放热反应将发生;当反应基本上完成时,可以将产物涂覆到基材上。或者,可以将酸投入水中,然后可以添加含环氧的化合物。当将酸和环氧一同添加到水中时,阻隔效果通常会更好。
在本发明范围内的另一种反应产物可以如下制备:将具有高固体含量的含胺化合物与酸混合,添加含环氧的化合物。与多元胺有关的“高固体”是指50%固体或更高,例如70%固体或更高,或基本上100%固体。
反应产物可以作为涂料施涂到下面将进一步描述的基材上。本发明的涂料可以进一步包含本领域技术人员已知的添加剂,包括无机填料颗粒、颜料、硅酮、表面活性剂和催化剂。除了为阻隔涂料赋予颜色和/或色调之外,无机填料和颜料还甚至可以进一步增强所得涂层的气体阻隔性能。如果使用,颜料与粘结剂的重量比可以不超过1∶1,例如不超过0.3∶1,或不超过0.1∶1。以这些比例使用的粘结剂重量是气体阻隔涂料组合物中的聚合物材料的总固体重量。尤其适合的是无机填料,包括片状填料例如云母、蛭石、粘土、滑石、云母氧化铁、二氧化硅、薄片状金属、薄片状石墨、薄片状玻璃等。
硅酮可以包括在本发明的阻隔涂料组合物中以帮助将阻隔材料施涂于其上的基材湿润。通常,对于这一目的有用的硅酮包括多种有机硅氧烷例如聚二甲基硅氧烷、聚甲基苯基硅氧烷等。这些的具体实例包括SF-1023硅酮(可以从General Electric Co.获得的聚甲基苯基硅氧烷)、AF-70硅酮(可以从General Electric Co.获得的聚二甲基硅氧烷)和DF-100S硅酮(可以从BASF Corp.获得的聚二甲基硅氧烷)。如果使用,基于气体阻隔涂料组合物中总树脂固体,通常以0.01到1.0wt%的量将此类硅酮添加到该气体阻隔涂料组合物中。
表面活性剂可以包括在本发明阻隔涂料组合物中。可以用于这一目的的表面活性剂的实例包括本领域已知的任何适合的非离子型或阴离子型表面活性剂。如果使用,基于阻隔涂料组合物的总重量,此类表面活性剂通常以0.01-2.0wt%的量存在。
催化剂也可以包括在本发明的阻隔涂料组合物中以帮助酸和包含聚合物材料的任何组分之间的反应。
涂料可以包含10-90,例如20-80或45-70wt%酸,和90-10,例如80-20或55-30wt%聚合物材料,其中wt%基于该涂料的总固体重量。如果包括其它添加剂,它们可以至多占15wt%,其中wt%基于涂料的总固体重量。在某些实施方案中,酸占50wt%或更大,例如60wt%或更大或70wt%或更大,其中wt%基于涂料的总固体重量。
本发明的涂料组合物可以在形成后立即涂覆到基材上,或保持八小时乃至更长的时间之后涂覆。本发明的特征在于,与相似的不用酸制备的组合物的适用期相比,本发明涂料的适用期得到显著提高。
本发明进一步涉及改进基材的阻隔性的方法,包括用上述任何涂料涂覆基材的至少一部分。该组合物可以通过任何常规方法涂覆,如喷涂、辊涂、浸涂、刷涂、流涂等。在涂覆到基材上之后,可以在环境温度或升温下将涂料组合物固化。
本发明的阻隔涂层可以具有任何适合的或合乎需要的干膜厚度。虽然更厚的涂层通常提供提高的气体阻隔性能,但是从经济上考虑更薄的涂层通常是优选的。通常,本发明的涂层将具有1密耳或更少,例如0.5密耳或更少或0.3密耳或更少的干膜厚度。
本发明的阻隔涂层可以具有0.5或更少,例如0.1或更少,0.01或更少,乃至0.001或更少的cm3-密耳/100英寸2/大气压/天的P(O2)。
如果需要的话,本发明的涂料组合物可以作为单个层或作为多个层涂覆在基材上,其中采用多个加热阶段以从每个后续的层中除去溶剂。
在本发明的某些非限制性实施方案中,本文描述的阻隔涂层是基材上唯一的阻隔涂层;即,本发明阻隔涂层没有和任何其它阻隔涂层一起使用。
可以根据本发明方法涂覆任何适合的基材。通常,基材将是具有气体透过性的那些,例如聚合物,包括但不限于,聚酯、聚烯烃、聚酰胺、纤维素塑料、聚苯乙烯、聚丙烯酸类和聚碳酸酯。根据本发明方法尤其适合于处理的聚酯是PET、聚(萘二甲酸乙二醇酯)(“PEN”)和/或它们的组合。
除非另有明确规定,本文所使用的所有数值,例如表示值、范围、量或百分率的那些可以当作前面有词语“大约”来理解,即使该术语没有明确出现。在此所述的任何数值范围旨在包括在其中包含的所有子范围。复数包括单数,反之亦然。还有,在此使用的术语“聚合物”是指预聚物、低聚物以及均聚物和共聚物;前缀“多”是指两个或更多。
实施例
以下实施例旨在说明本发明,且无论如何不应该认为是限制本发明。
实施例1
如表1所示,通过将环氧和共反应物(如果有的话)与有机酸混合制备气体阻隔涂料组合物。此时添加少量添加剂(如果使用的话)(例如控制流动)。然后缓慢地和逐渐地添加去离子水。发生放热。对于样品2,使用10g DOWANOL PM丙酮的90/10混合物作为共溶剂,对于样品5,使用44.6g 100% DOWANOL PM以获得40%固体。
表1
样品1 | 样品2 | 样品3 | 样品4 | 样品5 | |
环氧1 | 6.40g | 32.50g | 5.03g | 2.00g | 10.0g |
胺2 | 15.12g | -- | 5.03g | 1.50g | 19.7g |
柠檬酸 | 36.62g | 30.00g | -- | 6.50g | -- |
酒石酸 | -- | -- | 20.18g | -- | -- |
去离子水 | 41.86g | 37.50g | 19.76g | 4.90g | 1.2g |
1Mitsubishi Gas Chemical Company的TETRAD-X。
2Mitsubishi Gas Chemical Company的GASKAMINE 328。
然后使用09绕线式刮漆棒将样品涂覆到2密耳(50.8微米)的PET薄膜上。
在82℃下烘烤这些8分钟。最终涂膜厚度大约为0.25密耳(6.35微米)。使用OX-TRAN 2/20在23℃和50%的相对湿度下测试每个涂覆的PET薄膜的透氧性。气体阻隔涂层的氧气渗透常数(P(O2))使用公式1/Ra=1/Rb+DFT/P(O2)计算,其中Ra表示涂膜透过速度,单位是立方厘米/100英寸2/大气压/天;Rb表示PET的薄膜透过速度;DFT表示涂层的干膜厚度,单位是密耳;P(O2)表示涂层的氧气渗透常数,单位是立方厘米-密耳/100英寸2/大气压/天。结果在表2中给出。
表2
样品号 | P(O2)值 |
1 | 0.0003 |
2 | 0.0028 |
3 | 0.0024 |
4 | 0.0014 |
5 | 0.06(30℃,50%R.H.) |
从表2可以看出,根据本发明制备的涂层(样品1-4)产生比当使用没有酸(样品5)的涂层时获得的那些低至少一个数量级的P(O2)值。
虽然以上出于说明目的描述了本发明的特定实施方案,但是对本领域技术人员来说在不脱离所附权利要求书中所限定的本发明的情况下对本发明的细节作出许多改变是显而易见的。
Claims (14)
1.包含聚合物材料和酸的反应产物的阻隔涂料,其中当该酸是有机二酸时该涂料不包含二缩水甘油醚或其残余物,其中该涂料不包含硅烷材料或其残余物,和其中当该酸是烯属不饱和酸时该涂料不包含多元胺。
2.权利要求1的涂料组合物,其中该聚合物材料是芳族的。
3.权利要求1的涂料组合物,其中该聚合物材料包含含环氧的材料。
4.权利要求3的涂料组合物,其中该聚合物材料还包含含胺的材料。
5.权利要求4的涂料组合物,其中该聚合物材料包含四缩水甘油基间二甲苯二胺。
6.权利要求1的涂料组合物,其中该酸是一元酸。
7.权利要求1的涂料组合物,其中该酸是多元酸。
8.权利要求7的涂料组合物,其中该酸是柠檬酸。
9.改进基材的阻隔性的方法,包括用权利要求1的涂料涂覆基材的至少一部分。
10.权利要求9的方法,其中该基材包括PET。
11.根据权利要求9的方法处理的基材。
12.权利要求11的基材,其中该基材包括PET。
13.权利要求11的基材,其中该阻隔涂料的氧气渗透率小于0.01cm3-密耳/100英寸2/大气压/天。
14.权利要求11的基材,其中该阻隔涂料的氧气渗透率小于0.001cm3-密耳/100英寸2/大气压/天。
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US10/960,330 US20060078740A1 (en) | 2004-10-07 | 2004-10-07 | Barrier coatings |
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US20190351717A1 (en) | 2016-11-17 | 2019-11-21 | Bridgestone Americas Tire Operations, Llc | Pneumatic tire having dampening element adhered to air barrier layer |
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2004
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2005
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- 2005-10-04 MX MX2007004005A patent/MX2007004005A/es unknown
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- 2005-10-04 CN CNA200580034253XA patent/CN101035844A/zh active Pending
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CA2582190A1 (en) | 2006-04-20 |
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BRPI0516280A (pt) | 2008-09-02 |
AU2005294446A1 (en) | 2006-04-20 |
MX2007004005A (es) | 2007-05-24 |
KR20070092201A (ko) | 2007-09-12 |
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US20080152935A1 (en) | 2008-06-26 |
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