CN108291035B - 用于粘附水溶性聚合物膜的方法 - Google Patents

用于粘附水溶性聚合物膜的方法 Download PDF

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CN108291035B
CN108291035B CN201680070891.5A CN201680070891A CN108291035B CN 108291035 B CN108291035 B CN 108291035B CN 201680070891 A CN201680070891 A CN 201680070891A CN 108291035 B CN108291035 B CN 108291035B
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J·高
V·普拉萨德
S·J·菲茨克
A·S·卡里卡利
金鑫
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Rohm and Haas Co
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Abstract

一种用于通过向水溶性聚合物膜中的至少一个施加溶液来粘附所述膜的方法，所述溶液包含：(a)60至90wt％的水、(b)10至40wt％的异丙醇，和(c)0至5wt％的多价金属盐。

Description

用于粘附水溶性聚合物膜的方法
技术领域
本发明涉及用于粘附水溶性聚合物膜的方法。
背景技术
已知袋装洗涤剂配制物，例如聚乙烯醇袋中的高盐配制物。典型地，使用由用于聚合物体系的良好溶剂组成的密封剂来粘附水溶性聚合物膜以形成袋，所述聚合物体系容易地溶解聚合物以在两种聚合物膜(例如水)之间形成良好密封。WO2004/009335公开含有多元醇和醇的混合物的密封溶液。然而，这些材料的组合往往不能在膜之间提供良好粘结强度。
本发明解决的问题为需要改进的用于粘附水溶性聚合物膜的方法。
发明内容
本发明提供一种用于通过向水溶性聚合物膜中的至少一个施加溶液来粘附所述膜的方法，所述溶液包含：(a)60至90wt％的水、(b)10至40wt％的异丙醇，和(c)0至5wt％的金属盐。
本发明进一步提供一种用于通过向水溶性聚合物膜中的至少一个施加溶液来粘附所述膜的方法，所述溶液包含：(a)5至60wt％的水，和(b)40至95wt％的丙二醇。
具体实施方式
除非另有规定，否则百分比为重量百分比(wt％)并且温度以℃为单位。除非另有规定，否则操作在室温(20-25℃)下进行。术语“(甲基)丙烯酸”意指甲基丙烯酸或丙烯酸。
“玻璃化转变温度”或“Tg”是指玻璃状聚合物在所述温度下或高于所述温度时将经历聚合物链的片段运动的温度。聚合物的玻璃化转变温度可通过如下的福克斯方程(Foxequation)(《美国物理学会公报(Bulletin of the American Physical Society)》,1(3)第123页(1956))估算：
1/Tg＝w1/Tg(1)+w2/Tg(2)
对于共聚物，w1和w2是指两种共聚单体的重量分数，并且Tg(1)和Tg(2)是指由单体制成的两种相应均聚物的玻璃化转变温度。对于含有三种或更多种单体的聚合物，添加附加项(wn/Tg(n))。聚合物的T(g)也可通过使用适当的均聚物的玻璃化转变温度的值来计算，其可见于例如“《聚合物手册(Polymer Handbook)》”,J.Brandrup和E.H.Immergut编,国际科学出版社(Interscience Publishers)。聚合物的Tg也可通过各种技术测量，包括例如差示扫描量热法(“DSC”)。本文报道的Tg值通过DSC测量。
如本文所用，Mw是指如用凝胶渗透色谱法(gel permeation chromatography，GPC)和聚丙烯酸标准物以常规方式测量的重均分子量。GPC技术在《现代尺寸排阻色谱(Modem Size Exclusion Chromatography)》,W.W.Yau,J.J.Kirkland,D.D.Bly；威利-国际科学出版社(Wiley-Interscience),1979和《材料表征和化学分析指南(A Guide toMaterials Characterization and Chemical Analysis)》,J.P.Sibilia；德国化学学会出版社(VCH),1988年,第81-84页中详细讨论。本文以道尔顿为单位报道分子量。
优选地，将聚合物膜密封以形成封闭袋，优选其中含有清洁配制物或衣物洗涤剂，优选衣物洗涤剂的袋。
优选地，聚合物膜为丙烯酸类聚合物。“丙烯酸类聚合物”为具有至少60wt％的丙烯酸单体的聚合物，优选至少70wt％、优选至少80wt％、优选至少90wt％。丙烯酸单体包括(甲基)丙烯酸、其盐和其C1-C22烷基或羟烷基酯；丁烯酸、衣康酸、反丁烯二酸、顺丁烯二酸、顺丁烯二酸酐、(甲基)丙烯酰胺、(甲基)丙烯腈、和丁烯酸、衣康酸、反丁烯二酸或顺丁烯二酸的烷基或羟烷基酯。丙烯酸类聚合物还可包含其它聚合单体残基，包括例如非离子(甲基)丙烯酸酯、阳离子单体、单不饱和二羧酸酯、C1-C22烷基羧酸乙烯基酯、乙烯基酰胺(包括例如N-乙烯基吡咯烷酮)、磺化丙烯酸单体、乙烯基磺酸、卤化乙烯、含磷单体、杂环单体、苯乙烯和甲基取代的苯乙烯。
优选地，丙烯酸类聚合物包含50至90wt％的(甲基)丙烯酸C1-C10烷基酯单体的聚合单元；优选至少60wt％、优选至少65wt％；优选不超过85wt％、优选不超过80wt％。优选地，丙烯酸类聚合物包含10至50wt％的C3-C8单烯属不饱和羧酸单体的聚合单元；优选至少12wt；优选不超过40wt％、优选不超过35wt％、优选不超过30wt％、优选不超过25wt％。优选地，羧酸单体具有一个或两个羧酸基团，优选一个。优选地，C3-C8单烯属不饱和羧酸单体为(甲基)丙烯酸。优选地，丙烯酸类聚合物包含0至25wt％的(甲基)丙烯酸C2-C4羟烷基酯单体的聚合单元；优选至少5wt％、优选至少10wt％；优选不超过20wt％。
优选地，丙烯酸类聚合物包含10至35wt％丙烯酸正丁酯，优选10至30wt％、优选12至30wt％。优选地，单烯属不饱和羧酸单体为(甲基)丙烯酸C3-C6烷基酯单体，优选C3-C4。
优选地，丙烯酸类聚合物包含离子交联剂。合适的交联剂包括例如二价阳离子，如Ca2+、Mg2+、Al3+或Zn2+。优选Ca2+和Zn2+，其可例如由CaCl2、ZnO或可溶性锌络合物(例如碳酸氢铵锌)来提供。优选地，基于水溶性膜的总重量，交联剂(当存在时)的存在量为至少0.1wt％，优选至少0.2wt％、优选至少0.3wt％；优选不超过5wt％、优选不超过3wt％、优选不超过1wt％。
优选地，聚合物膜包含Tg为60至130℃的硬质聚合物和Tg为-20至40℃的软质聚合物。优选地，硬质聚合物具有70至100℃，优选75至85℃的Tg。优选地，软质聚合物具有5至35℃，优选10至30℃的Tg。优选地，软质聚合物包含5至25wt％的(甲基)丙烯酸C2-C4羟烷基酯单体的聚合单元，优选10至20wt％。优选地，硬质聚合物包含30至60wt％的甲基丙烯酸甲酯的聚合单元，优选40至55wt％。优选地，硬质聚合物包含20至50wt％的丙烯酸C1-C10烷基酯单体的聚合单元，优选25至45wt％；优选地，丙烯酸C1-C10烷基酯单体选自由以下组成的群组：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯。优选地，在软质聚合物中，(甲基)丙烯酸C1-C10烷基酯单体选自由以下组成的群组：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯。
优选地，硬质聚合物的Mw为40,000至120,000，优选40,000至90,000。优选地，软质聚合物的Mw为40,000至60,000，优选40,000至50,000。
优选地，丙烯酸类聚合物中多烯属不饱和单体的聚合单元的量不大于1wt％，优选不大于0.5wt％、优选不大于0.25wt％、优选不大于0.1wt％、优选不大于0.05wt％；所有百分比均基于干聚合物。
聚合物可通过本领域公知的常规乳液聚合技术来制备。优选地，硬质聚合物或软质聚合物或者硬质聚合物和软质聚合物两者上的羧酸基团的至少一部分被中和。羧酸可通过常规技术用至少一种碱中和。优选的碱包括例如胺、碱金属或碱土金属氢氧化物、氢氧化铵及其组合。合适的胺中和剂包括例如2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇、N,N-二甲基-2-氨基-2-甲基-1-丙醇、单异丙醇胺、三异丙醇胺、乙醇胺、三乙醇胺和吗啉。合适的碱金属或碱土金属氢氧化物包括例如氢氧化钠和氢氧化钾。优选地，中和剂选自氢氧化钾、氢氧化钠或其混合物。
添加到聚合物中的中和剂的量为提供期望水平的中和所需的量。基于摩尔当量，优选5至100％、优选10至100％、优选50至100％、优选75至100％、优选85至95％的丙烯酸类聚合物共混物中的酸基被中和。
优选地，单价和多价金属盐的阳离子选自由以下组成的群组：碱金属和碱土金属阳离子和Al+3；优选Ca+2、Mg+2、Zn2+、Pd2+、La3+、Ti4+、Ag+、K+、Li+和Na+；优选Ca+2、Mg+2、和Na+。多价金属盐的百分比基于盐的重量。优选地，阴离子为氯离子、硫酸根、溴离子、碘离子、碳酸根、硝酸根或乙酸根。
优选地，溶液包含：(a)70至90wt％的水、(b)10至30wt％的异丙醇，和(c)0至3wt％的单价和多价金属盐；优选(a)70至90wt％的水，和(b)10至30wt％的异丙醇。
优选地，溶液包含：(a)8至55wt％的水，和(b)45至92wt％的丙二醇；优选(a)8至50wt％的水，和(b)50至92wt％的丙二醇。
优选地，本发明的硬质和软质聚合物含有有限的结晶含量(即，它们为高度无定形的)，优选地，聚合物为完全无定形的，其中没有可结晶的含量。百分比结晶度可使用差示扫描量热法来测定。百分比结晶度可通过将每个样品的熔化热归一化至100％结晶参考标准的已知熔化热来计算。优选地，硬质和软质聚合物的百分比结晶度为5.0％或更少，更优选1.0％或更少。进一步优选地，百分比结晶度为零。
优选地，本发明的水溶性膜含有增塑剂。增塑剂可为亲水性的或疏水性的，尽管亲水性增塑剂可导致整个膜崩解时间稍微增加。优选地，使用疏水性和亲水性增塑剂的混合物。据信这类混合物提供改进的成膜和快速的膜破裂和崩解的适当平衡。合适的疏水性增塑剂的实例包括苯甲酸酯，如苯甲酸的C9-C11支链烷基酯和二苯甲酸酯封端的二乙二醇。合适的亲水性增塑剂的实例包括丙三醇、山梨糖醇、丙二醇、多元醇和聚乙二醇(例如PEG200或PEG400)。优选地，基于水溶性膜的总重量，增塑剂以1至30wt％，优选1至20wt％范围内的量存在于水溶性膜中。
本发明的水溶性膜可含有其它任选成分，包括但不限于增粘剂(例如松香酯)、交联剂(例如CaCl2、ZnO)、填充剂(例如硬脂酸锌、胶态二氧化硅粒子，在本文也称为二氧化硅溶胶，其可以由不同原料例如沉淀二氧化硅、微二氧化硅(硅石烟)、热解二氧化硅(热解法二氧化硅)或硅胶产生，并且它们可以被硅烷化)或聚结剂(例如二丙二醇甲醚，成膜助剂)。
优选地，袋含有洗涤剂组合物。优选地，洗涤剂组合物包含至少17wt％的表面活性剂，优选至少20wt％、优选至少23wt％、优选至少26wt％；优选不超过40wt％、优选不超过35wt％、优选不超过32wt％。优选地，洗涤剂包含至少40wt％的水，优选至少45wt％、优选至少50wt％、优选至少52wt％；优选不超过75wt％、优选不超过70wt％、优选不超过65wt％。
优选地，洗涤剂组合物包含至少4wt％的盐；优选至少5wt％、优选至少7wt％、优选至少9wt％；优选不超过20wt％、优选不超过17wt％、优选不超过15wt％、优选不超过13wt％。盐的量不包括洗涤剂中存在的任何阴离子或阳离子表面活性剂。优选地，盐具有不超过十个碳原子，优选不超过六个碳原子、优选不超过三个碳原子。优选地，盐选自由以下组成的群组：氯化物、柠檬酸盐、磷酸盐、硫酸盐、碳酸盐、偏硅酸盐和铝硅酸盐。优选地，盐的阳离子为碱金属离子或铵离子。优选地，洗涤剂包含选自由以下组成的群组的盐：氯化钠、氯化铵和硫酸铵；优选氯化钠或氯化铵。
(一种或多种)表面活性剂可为阳离子、阴离子、非离子、脂肪酸金属盐、两性离子或甜菜碱表面活性剂。优选地，配制物包含至少一种阴离子表面活性剂，优选至少两种。优选地，非离子表面活性剂具有含至少八个碳原子的烷基和至少五个聚合环氧乙烷或环氧丙烷残基。优选地，非离子表面活性剂具有至少五个聚合环氧乙烷残基，优选至少六个、优选至少七个；优选不超过十二个、优选不超过十一个、优选不超过十个。优选地，洗涤剂组合物包含至少5wt％的直链醇乙氧基化物，优选至少6wt％、优选至少8wt％；优选不超过15wt％、优选不超过13wt％、优选不超过11wt％。优选地，直链醇乙氧基化物具有C8-C18烷基，优选C10-C16、优选C12-C15。优选地，直链醇乙氧基化物含有六至十二个环氧乙烷的聚合单元，优选七至十个。优选地，阴离子表面活性剂具有含至少十个碳原子的烷基和阴离子基团，所述阴离子基团优选地选自磺酸根和硫酸根。阴离子表面活性剂也可具有环氧乙烷的聚合残基，和/或可具有芳香族环，例如直链烷基苯磺酸盐。一些阴离子表面活性剂为脂肪酸碱金属盐。优选地，洗涤剂组合物包含不超过5wt％的直链烷基苯磺酸盐，优选不超过3wt％、优选不超过1wt％。优选地，烷基苯磺酸盐具有C10-C14烷基。优选地，清洁剂组合物包含至少2wt％的烷基硫酸盐，优选至少3wt％、优选至少4wt％。优选地，洗涤剂组合物包含不超过12wt％的烷基硫酸盐，优选不超过10wt％、优选不超过8wt％。优选地，烷基硫酸盐每分子含有一至五个聚合环氧乙烷单元。优选地，洗涤剂组合物包含至少10wt％的直链烷基磺酸盐，优选至少13％、优选至少16％。优选地，组合物包含不超过25wt％的直链烷基磺酸盐，优选不超过22wt％。
优选地，洗涤剂组合物的pH为4至11、优选4.5至10、优选4.5至9。调节配制物pH值的合适碱包括无机碱如氢氧化钠和氢氧化钾；氢氧化铵；和有机碱如单乙醇胺、二乙醇胺或三乙醇胺；或2-二甲基氨基-2-甲基-1-丙醇(DMAMP)。可使用碱的混合物。调节含水介质pH值的合适酸包括无机酸如盐酸、磷酸和硫酸；和有机酸如乙酸。可使用酸的混合物。可用碱将配制物调节到较高pH，并且随后用酸反向滴定到上文所述的范围。
实例
缩写：
BA 丙烯酸正丁酯
EA 丙烯酸乙酯
EHA 丙烯酸2-乙基己酯
HEMA 甲基丙烯酸2-羟乙基酯
MAA 甲基丙烯酸
MMA 甲基丙烯酸甲酯
实例1-2：含有≥40wt％水、≤60wt％异丙醇(IPA)和<2wt％金属盐的密封溶液
通过在玻璃小瓶中将期望量的水、异丙醇和金属盐(CaCl2)混合在一起来制备具有表1中所示组成的两种密封溶液。在使用前将溶液在磁力搅拌板上搅拌10分钟并且超声处理30分钟。由通过刮涂将含有具有特定玻璃化转变温度的丙烯酸类聚合物和其它添加剂的共混物的配制物浇铸来制备约100μm水溶性膜(表2)。膜表现出各种期望的特性，包括高离子强度水溶液的稳定性，以及当离子强度降低时容易溶解的能力。然后通过按照ASTMF88(技术A)中规定的方法使用INSTRON拉伸试验测量制备的样本来表征每种密封溶液的密封强度。具体而言，使用棉签将密封溶液施加到尺寸为1"×0.5"(2.54×1.27cm)的水溶性膜上。在具有施加的密封溶液的膜上放置相同尺寸的另一膜，并且在5000psi(34.5MPa)的力下在压缩模塑机中夹在两块铝板之间1分钟。尝试对每个样本进行两次测量，并且在测试过程中报道最大负载值并列在表3中。结果表明，含有≥50wt％水、≤50wt％IPA和≤2wt％CaCl2的密封溶液的密封强度>6N，比比较例中所示的密封强度大。
表1.密封溶液的组成和密封条件。
Figure BDA0001683287340000061
表2.ACUDYNETM基水溶性膜的组成。
Figure BDA0001683287340000062
Figure BDA0001683287340000071
表2中的wt％聚合物对于膜的整个重量以固体为基准
聚合物1(wt％单体)：BA 20/EA 50/HEMA 15/MAA 15(Tg＝14℃)，40-44％固体；Mw＝45,000
聚合物2(wt％单体)：BA 25/MMA 47/EHA 10/MAA 18(Tg＝81℃)，40-44％固体；Mw＝90,000
表3.密封溶液的密封强度。
Figure BDA0001683287340000072
实例3-5：含有水和丙二醇(PG)的密封溶液
通过在玻璃小瓶中将溶剂混合在一起来制备具有表4中所示组成的两种密封溶液。在使用前将溶液在磁力搅拌板上搅拌10分钟并且超声处理30分钟。使用实例1中所述的方法制备含有表2中的水溶性涂料配制物的约100μm厚的膜。将所制备的膜在5000psi的力下在压缩模塑机中的两块铝板之间密封1分钟。使用ASTM F88中规定的方法将密封溶液的密封强度表征为>11N。
表4.密封溶液的密封强度。
Figure BDA0001683287340000073
实例6-8：密封力和时间的影响
使用实例1中所示的密封溶液在不同条件(表5)下密封相同的水溶性膜。通过将密封力降低到2000磅，平均密封强度从12.26增加到14.30N。增加密封力或时间稍微降低密封强度，但其值仍与水封聚乙烯醇膜/袋的值相似。组合>1000磅的密封力和>1分钟的密封时间得到密封水溶性膜的最佳条件。
表5.在不同密封条件下的密封强度。
Figure BDA0001683287340000081
实例9：装袋
为了测试实例中密封溶液的适用性，使用表2中的膜配制物和实例1中的密封溶液(图1)制备洗涤剂袋。在塑料原型中使用真空使水溶性聚合物膜变形。将密封溶液施加到三个边缘，并且将两个膜在5000psi(34.5MPa)下密封1分钟。接下来，将约13g洗涤剂配制物(表6)添加到袋中。最后，使用在5000psi(34.5MPa)下的密封溶液密封袋1分钟。洗涤剂袋在环境条件下留在实验室工作台上并且使其保持稳定，其中1个月内没有洗涤剂渗漏。
表6.用于装袋的洗涤剂配制物的组成。
组成wt％
水 53
Alpha Step PC 48 20
NaCl 10
Biosoft N25-7 10
Steol CS 270 7
比较例1-2：热封
使用实例1中所示的水溶性涂料配制物来制备两个热封样本。使用8"(20.3cm)的美国国际电气(American International Electric)AIE-200脉冲热封机来密封膜。热封样本的平均密封强度表征为<4N(表7)，这比实例1-8中呈现的平均密封强度低得多。
表7.热封水溶性膜的密封强度。
Figure BDA0001683287340000082
比较例3：含有100wt％水的密封溶液
实例1中所示的水溶性ACUDYNETM基膜通过水密封，并且样本的平均密封强度被表征为约1.35N(表8)，这比实例1-8中呈现的平均密封强度低得多。
表8.水封水溶性膜的密封强度。
Figure BDA0001683287340000091

Claims (4)

1.一种用于通过向水溶性聚合物膜中的至少一个施加溶液来粘附所述膜的方法，所述溶液包含：(a)70至90wt％的水、(b)10至30wt％的异丙醇，和(c)0至5wt％的多价金属盐，
其中所述水溶性膜为丙烯酸类聚合物，
其中所述丙烯酸类聚合物包含50至90wt％的(甲基)丙烯酸C1-C10烷基酯单体的聚合单元、10至50wt％的C3-C8单烯属不饱和羧酸单体的聚合单元，和0至25wt％的(甲基)丙烯酸C2-C4羟烷基酯单体的聚合单元。
2.根据权利要求1所述的方法，其中所述丙烯酸类聚合物包含0.1至3wt％的为二价阳离子的离子交联剂。
3.一种用于通过向水溶性聚合物膜中的至少一个施加溶液来粘附所述膜的方法，所述溶液包含：(a)8至55wt％的水，和(b)45至92wt％的丙二醇，
其中所述水溶性膜为丙烯酸类聚合物，
其中所述丙烯酸类聚合物包含50至90wt％的(甲基)丙烯酸C1-C10烷基酯单体的聚合单元、10至50wt％的C3-C8单烯属不饱和羧酸单体的聚合单元，和0至25wt％的(甲基)丙烯酸C2-C4羟烷基酯单体的聚合单元。
4.根据权利要求3所述的方法，其中所述丙烯酸类聚合物包含0.1至3wt％的为多价金属盐的离子交联剂。
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