CN1067092C - 由含有1,1-二氯乙烯共聚物的共混物制成的薄膜 - Google Patents
由含有1,1-二氯乙烯共聚物的共混物制成的薄膜 Download PDFInfo
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- CN1067092C CN1067092C CN97197312A CN97197312A CN1067092C CN 1067092 C CN1067092 C CN 1067092C CN 97197312 A CN97197312 A CN 97197312A CN 97197312 A CN97197312 A CN 97197312A CN 1067092 C CN1067092 C CN 1067092C
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Abstract
一种包括衍生自含PVDC组合物、具有各种性能如良好的热稳定性、增强的可挤塑性、改进的不透氧性能和降低的粘合到金属表面的粘性的一层的薄膜。所述组合物包括三种组分;含1,1-二氯乙烯的聚合物、加工助剂聚合物以及适用于防止PVDC降解的材料。
Description
本发明背景
1.本发明领域
本发明涉及由1,1-二氯乙烯聚合物或共聚物制成的薄膜,尤其是适用于包装食品如食用肉类的薄膜。更具体地说,本发明涉及具有作为不透氧层的聚(1,1-二氯乙烯)层的薄膜。
2.背景资料
由1,1-二氯乙烯共聚物制成的热塑性包装薄膜(通常称为“赛纶”或“PVDC”)已用于包装食品(如新鲜肉类和加工过的肉类)以及许多其它物品。
人们通过共挤塑、层合和挤出贴面已经生产出包括至少一层含有PVDC的多层薄膜。人们也已经生产出包含PVDC的、取向、热收缩的薄膜。人们已将1,1-二氯乙烯与氯乙烯、甲基丙烯酸甲酯和/或其它适宜的共聚物共聚。人们也将各种稳定剂和HCl清除剂与PVDC共混。
然而,仍需要提供一种可提供具有较低O2透射率(OTR)的包装薄膜的PVDC组合物,使得需要较少量的PVDC组合物来提供所需的不透氧性能。也需要提供一种具有改进热稳定性的PVDC组合物,使得在挤塑期间该组合物不易降解。同时还需要提供一种可在较高速度下挤塑的熔融PVDC组合物。最后,还需提供一种使粘合到加工设备上的粘度得到降低的PVDC组合物。这种组合物将可减少挤塑期间由于PVDC在挤塑机中发生降解而需要清理合/或清洗挤塑系统所导致的破裂。
本发明概要
简单地说,本发明提供一种包括一层或多层的薄膜,各层中至少有一层是衍生自一种具有至少三种组分的共混物。第一种组分是包括衍生自1,1-二氯乙烯的基本单元的聚合物。第二种组分是加工助剂聚合物,它包括衍生自(甲基)丙烯酸的C1-C12烷基酯的基本单元和衍生自一种或多种具有通式CH2=CR1C(O)R2(在该式中,R1为H或CH3,R2为OH、O(CH2)nR3或NH(CH2)nOH,其中n为1-8(包括1和8)的整数,R3为氨基、羟基或环氧乙烷基团)的单体的基本单元。第三种组分为清除HCl的化合物和/或亲双烯体。
该共混物在高度剪切如在挤塑机中所经历的条件下不易降解。人们相信,PVDC共混物优异的热稳定性是由于在高度剪切条件期间,因降低了机械剪切以及物料粘合到加工设备上的趋势得到降低而产生较少的热量所致。这些减少相信是存在加工助剂共聚物的结果。
此外,在生产包括PVDC不透氧层的薄膜中,这种共混物可以为不透氧层提供薄膜中存在的每单位量PVDC增加了的不透氧性能。该改进的不透氧性能相信是减少或消除共混物中常规液体稳定剂的结果。由于加工助剂共聚物的润滑效果,可以减少或消除常规液体稳定剂。结果,在薄膜生产期间我们可以保持挤塑速度和取向比,而同时薄膜的OTR得到改进。或者我们可以保持挤塑速度、取向比和薄膜的OTR,而同时提供厚度得到减少的含有PVDC的一层。
虽然本发明的薄膜可以仅包括单层(即衍生自上述共混物的一层),但优选包括两层或多层。根据本发明的优选多层薄膜结构至少具有四层。这种薄膜包括密封层、主体层、衍生自上述共混物的不透氧层以及机械损伤层(abuse layer)。所述薄膜层优选以所列举的顺序存在。
虽然含PVDC层可以是外层,但优选它是所述薄膜的内层。如果该组合物存在于内薄膜层中,则优选多层薄膜含有同时包括衍生自乙烯的基本单元的聚合物的外表面层。
薄膜可以是热收缩的或非热收缩的。当薄膜是热收缩的时,优选其在85℃(185°F)下的总自由收缩量约为10-100%。当薄膜是非热收缩的时,优选其在85℃(185°F)下的总自由收缩量约为1-9%。这种非热收缩的薄膜可以进行流延或吹塑。
不管本发明的薄膜是或不是热收缩的,它都可以用来包装各种各样的产品,特别是氧敏产品。
除非我们特地指出相反的意义,否则以下各种定义贯穿全文使用:
“(甲基)丙烯酸”包括丙烯酸和/或甲基丙烯酸;
“(甲基)丙烯酸酯”包括丙烯酸酯和甲基丙烯酸酯;
“聚合物”指聚合反应的产物,包括均聚物、共聚物、三聚物、四聚物等;
“共聚物”指由至少两种不同的单体通过聚合反应所形成的聚合物,包括无规共聚物、嵌段共聚物、接枝共聚物等;
“包装袋”指围绕一种产品使之成型的一种或多种包装材料(如薄膜);
“薄膜”在其最一般的意义上用来包括所有的塑料基料材料,虽然厚度不大于0.25mm的薄膜是最优选的;
“内层”指其两个主表面都直接粘合到薄膜其它层上的多层薄膜的任意层;
“外层”指其一个主表面直接粘合到薄膜另一层上或主表面都不直接粘合到薄膜另一层上的薄膜的任意层;
“内部层”指相对于多层薄膜的其它层而言,包装产品的多层薄膜靠近产品一侧的外层;
“外部层”指相对于多层薄膜的其它层而言,包装产品的多层薄膜离产品最远的一层;
“密封层”、“热密封层”和“密封剂层”:
(a)对于搭接型密封,指涉及薄膜与其自身、薄膜的另一层或其它薄膜和/或不是薄膜的其它物品之间密封的一个或多个外薄膜层(一般情况下高达薄膜外部75微米(3密尔)都可以涉及薄膜与其本身或另一层的密封),或
(b)对于飞边(fin)密封,包装袋的内部薄膜层以及最内层的内部表面75微米(3密尔)范围内的支撑层都涉及薄膜与其自身的密封;
“密封”指薄膜表面的第一区与通过将各区域加热(如通过加热杆、热空气、红外辐射、超声密封等)至至少其各自密封的起始温度时所产生的与薄膜表面的第二区之间的粘合;
当与薄膜和/或薄膜层一起使用时,“隔离层”指阻挡一种或多种气体(如O2)的一种能力;
“机械损伤层”(或“抗穿刺层”)指阻碍磨损、穿刺和其它各种降低包装袋整体性的潜在因素以及各种降低包装袋外观质量的潜在因素的外薄膜层和/或内薄膜层;
“粘结层”指提供粘合到包括另外不粘合聚合物的邻接层上的内层作为其主要目的的内薄膜层;
“主体层”指目的在于增加多层薄膜抗机械损伤、韧性、模量等的任何层,一般含有相对于薄膜中其它聚合物而言较廉价的、可以提供与抗机械损伤、模量等无关的一些特殊目的的聚合物;
“层压”和“层压制品”(或“层压薄膜”)指两个或多个薄膜层或其它材料的粘合的方法及其所得产物,并包括共挤塑及粘合;
“粘合”指:
(a)当与两种或多种薄膜有关时,指使用热密封或其它方法如采用薄膜之间一个粘合层的方法将各个薄膜彼此粘合,或
(b)当与薄膜层有关时,指在没有粘结层、粘合层或其间的其它层的情况下将主体薄膜层与客体层薄膜层粘合;
当与一个主体层和两个或多个客体层有关时,“之间”用来指主体层直接粘合到其间的另外两层上,还包括主体层不直接粘合到两个其它层中的一个或两个上的情况,即可以将一个或多个其它层安放到主体层与主体层位于其间的一层或多层的中间;
“总自由收缩量”指10cm×10cm薄膜试样在85℃(185°F)下收缩时的尺寸变化百分数,此定量测定是根据在《1990 AnnualBook of ASTM Standards》,第08.02卷,368-371页中提出的ASTMD2732(其整个公开的内容此处通过引用并入本文)来进行的。
“纵向”指沿着薄膜长度的方向即在挤塑和/或贴合过程期间形成的薄膜的方向;和
“横向”指横过薄膜的方向即与MD(纵向)垂直的方向。
示意性实施方案的详述
本发明的薄膜可以包括包含乙烯聚合物的一层或多层。近年来出现的单点类型的催化剂(如金属茂)使得必需进行进一步的明确阐明。非均相聚合物是那些分子量和组成分布变化较大的聚合物。采用例如常规齐格勒-纳塔型催化剂制备的聚合物是非均相聚合物。这种聚合物可用于本发明薄膜的各层中。
另一方面,均相聚合物具有较窄的分子量和组成分布。均相聚合物在结构上有别于非均相聚合物之处在于,它们表现出较为均匀的共聚用单体在链中的序列、在所有链中相同(mirroring)的序列分布以及链长的相似性即较窄的分子量分布。一般采用金属茂或其它单点类型的催化剂来制备均相聚合物。均相聚合物也可用于本发明薄膜的各层中。
术语“乙烯/α-烯烃共聚物”意指各种非均相材料如低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、线性低密度聚乙烯(LLDPE)和极低及超低密度聚乙烯(VLDPE和ULDPE)以及各种均相材料如金属茂催化的ExactTM树脂(Exxon Chemical Co.,Baytown,Texas)、基本上为线性的AffinityTM和EngageTM树脂(Dow Chemical Co.,Midland,Michigan)和TafmerTM线性树脂(Mitsui Petrochemical Corp.,Japan)。上述非均相聚合物和均相聚合物通常包括乙烯与一种或多种α-烯烃如1-丁烯、1-己烯、1-辛烯等的共聚物。
可以通过本领域技术人员公知的一种或多种方法如分子量分布(Mw/Mn)、组成分布宽度指数(CDBI)、窄的熔点范围以及单一的熔点行为来表征均相乙烯/α-烯烃共聚物。通过例如凝胶渗透色谱法可以测定分子量分布,也就是我们所公知的“多分散性”。用于本发明薄膜层中的均相乙烯/α-烯烃共聚物具有的Mw/Mn优选小于2.7,更优选约为1.9-2.5,仍更优选约为1.9-2.3。
均相乙烯/α-烯烃共聚物的CDBI通常大于约70%。我们将CDBI定义为共聚用单体含量为平均总摩尔共聚用单体含量的50%(即±50%)的共聚物分子的重量百分数。通过由例如Wild等人在《J.Poly.Sci.-Poly.Phys.Ed.》第20卷,第441页(1982年)中所述的升温洗脱分级来测定CDBI。我们将不合共聚用单体的线性聚乙烯定义为其CDBI为100%。CDBI测定清楚地将均相共聚物(CDBI值通常大于70%)与目前可得到的各种VLDPE(CDBI值通常小于55%)区分开来。
均相乙烯/α-烯烃共聚物也一般表现出基本上单一的熔点,通过差示扫描量热法(DSC)测定的峰值熔点(Tm)约为60℃-105℃,更准确地说DSC峰值Tm约为80℃-100℃。此处所用的短语“基本上单一的熔点”指该材料的至少约80%(重量)对应于约为60℃-105℃温度范围内的单一Tm,并且正如通过DSC分析(如在Perkin ElmerTM System 7Thermal Analysis System上进行分析)所测定的那样,基本上大部分该材料的峰值熔点没有超过约115℃。我们发现,较高熔解峰值的存在对薄膜各种性能如雾度和热合起始温度是不利的。
一般而言,通过使乙烯与一种或多种α-烯烃进行共聚合可以制备均相乙烯/α-烯烃共聚物。优选共聚用单体为C3-C20α-烯烃,更优选为C4-C12α-烯烃,仍更优选为C4-C8α-烯烃。特别优选的α-烯烃包括1-丁烯、1-己烯、1-辛烯及其混合物。用于制备和使用均相聚合物的方法见述于美国专利第5,206,075号和5,241,03l号以及PCT国际公开第WO 93/03093号和WO 90/03414号中。另一类均相乙烯/α-烯烃共聚物见述于美国专利第5,272,236号和5,278,272号中,这两个专利此处通过引用并入本文。一般而言,乙烯/α-烯烃共聚物是约80-99%(重量)乙烯与1-20%(重量)α-烯烃,优选约85-95%(重量)乙烯与5-15%(重量)α-烯烃进行聚合反应的产物。
现在我们来谈及本发明的薄膜,其含PVDC层衍生自包含三种组分的共混物。这些组分的第一种是含有1,1-二氯乙烯的聚合物,即包括衍生自1,1-二氯乙烯CH2=CCl2的基本单元的聚合物。这种聚合物也可以包括衍生自各种单体如氯乙烯、苯乙烯、乙烯基乙酸酯、丙烯腈和(甲基)丙烯酸C1-C12烷基酯(如丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸甲酯等)的基本单元。优选此第一种组分包括一种或多种1,1-二氯乙烯均聚物、1,1-二氯乙烯/氯乙烯共聚物、1,1-二氯乙烯/丙烯酸甲酯共聚物、1,1-二氯乙烯/丙烯腈共聚物、1,1-二氯乙烯/丙烯酸丁酯共聚物、1,1-二氯乙烯/苯乙烯共聚物以及1,1-二氯乙烯/乙烯基乙酸酯共聚物。这些聚合物可从各种渠道购得。
所述共混物的第二种组分是含有衍生自(甲基)丙烯酸C1-C12烷基酯的基本单元和衍生自一种或多种具有通式CH2=CR1C(O)R2的单体的基本单元的加工助剂聚合物。在该式中R1优选为H或CH3,虽然本领域技术人员可以想到其它有用的有机基团(如CH2CH3、CH2C(O)OH等)。当将R1限制为H或CH3而R2为OH时,所述单体为(甲基)丙烯酸;当将R1限制为H或CH3,R2为O(CH2)nR3(其中n为1-8的整数,包括1和8)和R3为氨基、羟基或环氧乙烷基团时,所述单体分别是(甲基)丙烯酸烷基氨基酯、(甲基)丙烯酸羟基烷基酯或(甲基)丙烯酸缩水甘油酯;而当将R1限制为H或CH3,R2为NH(CH2)nOH(其中n如上所定义)时,所述单体为(甲基)丙烯酰胺。在上述中的n优选为1-4(包括1和4),更优选为1-2(包括1和2)的整数。特别优选的加工助剂聚合物是那些包括衍生自甲基丙烯酸C1-C12烷基酯的基本单元的聚合物,特别是那些包括衍生自甲基丙烯酸C1-C4烷基酯(即甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯和甲基丙烯酸丁酯)的基本单元的聚合物。
可以通过本领域众所周知的各种方法来制备第二种组分(即加工助剂聚合物)。具体地说,如果选择的共聚用单体是(甲基)丙烯酸,则可以将其直接与所需的(甲基)丙烯酸C1-C12烷基酯进行聚合。如果所述共聚用单体是上述另一种化合物,则可以从工业供应商(如AldrichChemical Co.,Inc.,Milwaukee,Wisconsin)处订购或可通过使(甲基)丙烯酸与可以得到所需R2基团的化合物反应来制备。这些进行的反应和方法对于本领域化学工作者而言是众所周知的,感兴趣的读者可以查找例如各种大学水平的教科书以了解更详细的细节。
所述共混物的第三种组分是可以防止或抑制PVDC发生降解的化合物,即HCl清除剂或亲双烯体。衍生自1,1-二氯乙烯的基本单元具有通式-CH2CCl2-。在某些情况下(特别是当几个这种基本单元彼此接近时)这些基本单元可以进行反应,藉此将HCl作为副产物除去而生成不饱和的基本单元,即-CH=CCl-。
某些物质可有助于抑制PVDC的脱去氯化氢。广义来说,可将这些物质分类为HCl清除剂和亲双烯体。HCl清除剂是任何在PVDC共聚物的脱去氯化氢期间HCl形成时可以接受HCl的物质。有用的HCl清除剂的例子包括四甘醇二(2-乙基己酸酯)、脂肪酸皂盐(如蓖麻醇酸钙)、有机酸的金属盐(如焦磷酸四钠)和包括环氧乙烷(即环氧)基团的有机化合物,如环氧化的亚麻子油、环氧化的豆油、环氧化的α-烯烃、环氧化的酯、缩水甘油醚等。
亲双烯体是一种可与共轭二烯序列如1,3-丁二烯反应的化合物。它有助于使上述脱去氯化氢反应的速度减慢。有用的亲双烯体的例子包括含有衍生自一种或多种有机双酸如马来酸、富马酸和琥珀酸的酸酐的基本单元的聚合物。亲双烯体优选为乙烯/丙烯酸丁酯/马来酸酐共聚物和乙烯/乙烯基乙酸酯/接枝马来酸酐共聚物中的至少一种。
优选所述共混物第一种组分的量约为92-98%(重量),第二种组分的量约为1-4%(重量),第三种组分的量约为1-4%(重量)。与4%(重量)环氧化油和96%(重量)1,1-二氯乙烯的共聚物的组成相比,在大多数情况下这种共混物可以保持或改进组合物的热稳定性。
不管所述共混物中三种组分各自所用的量是多少,它们都可以在例如掺混机或挤塑机中进行混合。一旦混合后,我们可以用本领域技术人员所公知的各种方法将共混物进行挤塑和加工以形成薄膜或多层薄膜的一层。例如公开于美国专利第3,741,253号(Brax等)、第4,278,738号(Brax等)和第4,284,458号(Schirmer)中的各种方法,此处通过引用将其并入本文。当然,实际上可以使用任何制造具有不透氧层薄膜的方法来制造根据本发明的薄膜,只要该方法采用上述含有PVDC的组合物即可。
该共混物具有改进了PVDC热稳定性,可挤塑性因此而得到改进的优点。换言之,在必须中断挤塑过程以从挤塑机内除去降解了的PVDC之前,这种PVDC可以在挤塑机中挤塑一段更长的时间。此外,由于该种共混物对于每单位量的PVDC提供了更大的不透氧性,因此我们可以减少PVDC的量以符合不透氧性的先存程度(preexistingdegree)和/或对于给定量的PVDC,我们可以提高不透氧的程度。
通过使所述共混物在一对热辊之间或在热混合室内操作可以进行PVDC共混物的总热稳定性的测量。由于剪切降解和温度所引发的降解产生显著黑化的聚合物所需要的时间是加工助剂/HCl清除剂混合物在促进PVDC热稳定性中有效性的度量。市售1,1-二氯乙烯共聚物共混物表明,在约168℃(335°F)和63转/分运转的混合设备如BrabenderTM掺混机中,热稳定时间约为10分钟。
虽然本发明的薄膜可以仅包括单层(即衍生自上述共混物的一层),但优选包括至少两层。本发明的薄膜优选总共具有1-20层,更优选2-12层,最优选3-10层。只要本发明的多层薄膜对于具体的包装操作(所述薄膜用于其中)能提供所需的各种性能如不透氧特性、自由收缩量、收缩张力、光学、模量、热合强度等,它就可以具有任何总的层数及任何所需总的厚度。
根据本发明的优选多层薄膜结构至少具有四层。这种薄膜包括密封层、主体层、衍生自上述共混物的不透氧层以及机械损伤层。主体层优选位于密封层与不透氧层之间,不透氧层优选位于主体层与机械损伤层之间。如需要,粘结层可位于密封层与主体层之间以及位于不透氧层与机械损伤层之间。在约85℃下这种薄膜总的自由收缩量优选约为10-100%。
刚描述的四层和六层薄膜结构可以具有作为外层的机械损伤层。在这种结构中,优选的机械损伤层含有包括衍生自乙烯的基本单元和任选衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯中至少一种的基本单元的聚合物。特别优选的含乙烯的聚合物包括LDPE、LLDPE、VLDPE、均相乙烯/α-烯烃共聚物和离子键聚合物。
或者,所述机械损伤层可以是内层。在这样的一种结构中,表面层可以包括在与不透氧层相对的机械损伤层的侧面上。如需要,粘结层可以位于主体层与不透氧层之间以及位于不透氧层与机械损伤层之间。在约85℃下这种薄膜结构的总自由收缩量优选约为1-9%。
在刚描述的五层和七层薄膜结构中,优选的表面层含有包括衍生自乙烯的基本单元和任选衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯中至少一种的基本单元的聚合物。特别优选的含乙烯的聚合物包括LDPE、LLDPE、VLDPE、均相乙烯/α-烯烃共聚物和离子键聚合物。
在上述薄膜结构中的密封层优选含有包括衍生自乙烯的基本单元和任选衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯的基本单元的聚合物。特别优选的含乙烯的聚合物包括LDPE、LLDPE、VLDPE、均相乙烯/α-烯烃共聚物和离子键聚合物。
本发明的所有或部分薄膜可以通过辐射来引发交联。在辐射的过程中,对薄膜进行高能辐射处理,如进行电晕放电(例如参照美国专利第4,120,716号和第4,879,430号,此两文献此处通过引用并入本文)、等离子体、火焰、紫外线、X-射线、γ射线、β射线和在受辐射材料的分子之间引发交联的高能电子处理。适宜的剂量水平可以通过本领域技术人员公知的各种标准放射剂量测定方法来测定,所用的精确辐射量理所当然要取决于具体的薄膜结构及其最终用途。优选以0.5-15兆拉德(MR),更优选为1-12MR的剂量水平来辐射薄膜。有关聚合物薄膜辐射的进一步细节可见述于例如美国专利第4,064,296号(Bornstein等)中,此文献此处通过引用并入本文。
对包含PVDC的薄膜层优选不进行辐射处理。进行辐射,尤其进行超过约4MR的辐射可以导致PVDC的显著降解。正如本领域技术人员所公知的那样,使用包含衍生自1,1-二氯乙烯和丙烯酸甲酯的基本单元的聚合物降低了辐射对PVDC的降解影响。
优选本发明的薄膜是取向的,更优选是双轴取向。优选该薄膜为双轴取向及热收缩的。取向的薄膜一般在升高的温度(即取向温度)下伸长,然后通过冷却被“固定”在伸长的构型中。在升高的温度下伸长然后进行冷却的组合使聚合物链的顺序变成更加平行的构型,籍此显著改变薄膜的机械性能。当将不受限制的、未退火的、取向的薄膜随后加热至其取向温度时,薄膜几乎收缩到其原来即伸长前的尺寸。这种薄膜我们称之为热可收缩的。
当描述一给定薄膜的取向程度时,通常使用术语“取向比”(即薄膜在几个方向,通常是彼此互相垂直的两个方向取向的产品的程度)。在纵向上的取向称为“牵引”,而在横向上的取向称为“拉伸”。对于通过环形口模挤塑的薄膜而言,通过将薄膜吹塑产生膜泡来获得拉伸。对于这些薄膜而言,通过使薄膜经过两套有动力驱动的夹膜辊装置(其中后续装置比前续装置具有较高的(压辊)表面速度)来获得牵引,所得的牵引率为夹膜辊后续装置的表面速度除以夹膜辊前续装置的表面速度。
根据本发明的薄膜在生产用于新鲜红色肉、熏肉和加工肉类、猪肉、乳酪、家禽等的包装袋生产(如述于美国专利第3,741,253号(Brax等)、第3,891,008号(D'Entremont)、第4,048,428号(Baird)和第4,284,458号(Schirmer)中,此处通过引用并入本文)中特别有用。但该薄膜也可用于其它用途。
例如,可将该薄膜用作包装食物和非食物物品的包装用途的收缩薄膜。本发明可在其中得到有益使用的薄膜见述于例如美国专利第4,551,380号和第4,643,943号(都是Schoenberg)中,此处通过引用并入本文。
本发明也可与具有不透氧、不透湿气或不透臭气功能的薄膜(如见述于美国专利第4,064,296号(Bomstein等)、第4,724,185号(Shah)、第4,839,235号(Shah)和第5,004,647号(Shah),此处通过引用并入本文)一起使用。该薄膜也可用作补片(Patch)(如见述于美国专利第4,755,403号和第4,770,731号(都是Ferguson)中,此处通过引用并入本文)或与补片有关的用途。同时该薄膜也可用作辐射、取向、热定型的薄膜或与之有关的用途。
此外,可将本发明的薄膜通过层合、粘合性粘附、挤出贴面或挤塑层合到一底物上形成层合制品。可通过用粘合剂、用热和压力、甚至采用展涂和挤出贴面使各层接合在一起来完成层合。
本发明的薄膜特别适用于各种在其中被包装的产品最好不与空气中的氧接触的包装应用。更具体地说,根据本发明的薄膜特别适宜作为拉伸薄膜、作为适用于立式或卧式成型-灌装-封口最终用途的薄膜、作为盖薄膜、作为适用于真空表面包装的薄膜、适用作隔离袋、适用作修补袋的薄膜、作为适用于现包装用的薄膜、作为适用于热成型容器的薄膜(特别是用于在热成型盘如聚苯乙烯盘中作为衬里的薄膜)、作为香味/臭气隔离薄膜、作为适用于烹饪最终用途的薄膜(特别是热收缩袋、热收缩和非热收缩铸塑品和由非热收缩薄膜及片材热成型的容器)、作为医药薄膜以及其它许多在其中通常要求具有不透氧层的用途。
实施例
制备两种适用于薄膜生产的组合物,并测试其热稳定性。第一种组合物是对照组合物,而第二种组合物是根据本发明的组合物。两种组合物都适用于通过挤塑机加工生产薄膜。
下表Ⅰ提供了:(a)在两种组合物中每一种存在的各种组分的特性;(b)在每一种组合物中每一种组分的量;(c)使所述组合物在混合室如在335°F和63转/分下运转的BRABENDERTM掺混机中操作时所述组合物的热稳定性,结果以由于剪切降解和温度引发的降解产生显著的黑化聚合物时所需的时间来表示;和(d)在使用该组合物的薄膜中获得的相对氧传递速率。
正如我们从表Ⅰ中可看到的,没有加工助剂共聚物的对照组合物的热稳定性仅约为根据本发明的组合物(含有丙烯酸酯/羧酸加工助剂共聚物)的热稳定性的一半。此外,由根据本发明的组合物所提供的氧传递速率仅约为对照组合物的氧传递速率的一半。
表Ⅰ
组合物 | 组合物中各组分 | 组分量(重量份数) | 热稳定性(分钟) | OTR(cm3/天·m2atm) |
不包括加工助剂聚合物(对照) | PVDCHCl清除剂和/或亲双烯体 | 1004 | 10 | 7 |
包括加工助剂聚合物 | PVDC丙烯酸酯/羧酸加工助剂共聚物HCl清除剂和/或亲双烯体 | 10022 | 20 | 3 |
虽然本发明已根据某些优选的实施方案作了描述,但本领域技术人员可以容易地想到不背离本发明原理及范畴的各种修改和变化。因此,在以下各项权利要求书的范畴内可以实施这些修改。
Claims (19)
1.一种薄膜,它包括:
a)密封层;
b)主体层;
c)衍生自包括以下物质的共混物的不透氧层:
1)包括衍生自1,1-二氯乙烯的基本单元的聚合物;
2)包括衍生自(甲基)丙烯酸的C1-C12烷基酯的基本单元和衍生自一种或多种具有通式CH2=CR1C(O)R2体的基本单元的加工助剂聚合物,其中,R1为H或CH3,R2为
a)OH,
b)O(CH2)nR3或
c)NH(CH2)nOH,
其中n为1-8(包括1和8)的整数,R3为氨基、羟基或环氧乙烷基团;和
3)清除HCl化合物和亲双烯体中的至少一种;和
d)机械损伤层;所述主体层位于所述不透氧层与所述密封层之间,所述不透氧层位于所述主体层与所述机械损伤层之间。
2.权利要求1的薄膜,其中所述包含衍生自1,1-二氯乙烯的基本单元的聚合物还包括衍生自氯乙烯、(甲基)丙烯酸的C1-C12烷基酯、丙烯腈、苯乙烯和乙烯基乙酸酯中至少一种的基本单元。
3.权利要求1的薄膜,其中基于所述共混物的重量计,所述加工助剂共聚物的量约为1-4%(重量)。
4.权利要求1的薄膜,其中所述加工助剂聚合物包括衍生自甲基丙烯酸的C1-C12烷基酯的基本单元。
5.权利要求1的薄膜,其中R2为OH。
6.权利要求1的薄膜,其中R2为O(CH2)nR3。
7.权利要求6的薄膜,其中n为1-4(包括1和4)的整数。
8.权利要求6的薄膜,其中R3为氨基。
9.权利要求6的薄膜,其中R3为羟基。
10.权利要求6的薄膜,其中R3为环氧乙烷基团。
11.权利要求1的薄膜,其中R2为NH(CH2)nOH。
12.权利要求11的薄膜,其中n为1-4(包括1和4)的整数。
13.权利要求1的薄膜,其中所述机械损伤层是外层。
14.权利要求13的薄膜,其中所述机械损伤层包括包含衍生自乙烯的基本单元和任选衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯中至少一种的基本单元的聚合物。
15.权利要求13的薄膜,还包括:
e)位于所述密封层与所述主体层之间的粘结层,和
f)位于所述不透氧层与所述机械损伤层之间的粘结层。
16.权利要求1的薄膜,其中所述机械损伤层是内层。
17.权利要求16的薄膜,还包括:
e)在与所述不透氧层相对的所述机械损伤层侧面上的表面层;
f)位于所述主体层与所述不透氧层之间的粘结层;和
g)位于所述不透氧层与所述机械损伤层之间的粘结层。
18.权利要求17的薄膜,其中所述表面层包括包含衍生自乙烯的基本单元和任选衍生自乙烯的基本单元,还包括衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯中至少一种的基本单元的聚合物。
19.权利要求1的薄膜,其中所述密封层包括包含衍生自乙烯的基本单元和任选衍生自乙烯的基本单元还包括衍生自C4-C12α-烯烃、乙烯基乙酸酯、(甲基)丙烯酸和(甲基)丙烯酸的C1-C12烷基酯中至少一种的基本单元的聚合物。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66615296A | 1996-06-19 | 1996-06-19 | |
US666,152 | 1996-06-19 | ||
US799,748 | 1997-02-12 | ||
US08/799,748 US6045924A (en) | 1996-06-19 | 1997-02-12 | Film from a vinylidene chloride copolymer containing blend |
Publications (2)
Publication Number | Publication Date |
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CN1234813A CN1234813A (zh) | 1999-11-10 |
CN1067092C true CN1067092C (zh) | 2001-06-13 |
Family
ID=27099392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN97197312A Expired - Fee Related CN1067092C (zh) | 1996-06-19 | 1997-06-16 | 由含有1,1-二氯乙烯共聚物的共混物制成的薄膜 |
Country Status (11)
Country | Link |
---|---|
US (1) | US6045924A (zh) |
EP (1) | EP0918813B1 (zh) |
JP (1) | JP2001505932A (zh) |
KR (1) | KR20000022032A (zh) |
CN (1) | CN1067092C (zh) |
AR (1) | AR007426A1 (zh) |
AU (1) | AU734008B2 (zh) |
BR (1) | BR9709851A (zh) |
CA (1) | CA2258838A1 (zh) |
NZ (1) | NZ333439A (zh) |
WO (1) | WO1997048753A1 (zh) |
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US6673406B2 (en) | 2001-10-15 | 2004-01-06 | Cryovac, Inc. | High barrier polyvinylidene chloride composition and film |
RU2397183C2 (ru) | 2004-10-12 | 2010-08-20 | Дау Глобал Текнолоджиз Инк. | Пластификатор для полимера алкилакрилата-винилиденхлорида |
US9065664B2 (en) * | 2006-01-27 | 2015-06-23 | Cisco Technology, Inc. | Providing an announcement for a multiparty communication session |
US20060222797A1 (en) * | 2005-03-29 | 2006-10-05 | Cryovac, Inc. | Polyvinylidene chloride layered silicate nanocomposite and film made therefrom |
US20080138478A1 (en) * | 2006-12-12 | 2008-06-12 | Cryovac, Inc. | Vacuum packaging of a meat product using a film having a carbon dioxide scavenger |
ATE537964T1 (de) * | 2007-05-09 | 2012-01-15 | Baxter Int | Mehrschichtige strukturen mit einer poly(vinylidenchlorid)schicht |
US9452592B2 (en) | 2007-08-28 | 2016-09-27 | Cryovac, Inc. | Multilayer film having an active oxygen barrier layer with radiation enhanced active barrier properties |
US8815360B2 (en) | 2007-08-28 | 2014-08-26 | Cryovac, Inc. | Multilayer film having passive and active oxygen barrier layers |
SG179185A1 (en) * | 2009-09-16 | 2012-04-27 | Advanced Tech Materials | Vessel incorporating film with enhanced anti-static properties and related methods |
US9546446B2 (en) | 2009-10-23 | 2017-01-17 | Toyo Boseki Kabushiki Kaisha | Highly functional polyethylene fibers, woven or knit fabric, and cut-resistant glove |
US9828475B2 (en) | 2009-11-20 | 2017-11-28 | Dow Global Technologies Llc | Printable monolayer polyvinylidene chloride structures |
FR2957351B1 (fr) * | 2010-03-10 | 2013-06-28 | Solvay | Composition a base de copolymere du chlorure de vinylidene |
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EP3380322B1 (en) * | 2015-11-27 | 2020-11-04 | Solvay SA | Vinylidene chloride polymer composition comprising at least one sorbate ester |
JP2018177890A (ja) * | 2017-04-06 | 2018-11-15 | 旭化成株式会社 | 塩化ビニリデン系共重合体樹脂組成物 |
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EP0029316A1 (en) * | 1979-11-09 | 1981-05-27 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinylidene chloride copolymer resin composition, packaging film prepared therefrom and food packages using the film |
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1997
- 1997-02-12 US US08/799,748 patent/US6045924A/en not_active Expired - Fee Related
- 1997-06-16 JP JP50325698A patent/JP2001505932A/ja active Pending
- 1997-06-16 NZ NZ333439A patent/NZ333439A/en unknown
- 1997-06-16 KR KR1019980710430A patent/KR20000022032A/ko not_active Application Discontinuation
- 1997-06-16 AU AU33988/97A patent/AU734008B2/en not_active Ceased
- 1997-06-16 CA CA 2258838 patent/CA2258838A1/en not_active Abandoned
- 1997-06-16 BR BR9709851A patent/BR9709851A/pt not_active Application Discontinuation
- 1997-06-16 CN CN97197312A patent/CN1067092C/zh not_active Expired - Fee Related
- 1997-06-16 WO PCT/US1997/010502 patent/WO1997048753A1/en not_active Application Discontinuation
- 1997-06-16 EP EP19970930073 patent/EP0918813B1/en not_active Expired - Lifetime
- 1997-06-19 AR ARP970102693 patent/AR007426A1/es active IP Right Grant
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Also Published As
Publication number | Publication date |
---|---|
AR007426A1 (es) | 1999-10-27 |
CN1234813A (zh) | 1999-11-10 |
EP0918813A1 (en) | 1999-06-02 |
AU3398897A (en) | 1998-01-07 |
JP2001505932A (ja) | 2001-05-08 |
AU734008B2 (en) | 2001-05-31 |
EP0918813B1 (en) | 2001-10-10 |
NZ333439A (en) | 1999-09-29 |
CA2258838A1 (en) | 1997-12-24 |
US6045924A (en) | 2000-04-04 |
BR9709851A (pt) | 1999-08-10 |
KR20000022032A (ko) | 2000-04-25 |
WO1997048753A1 (en) | 1997-12-24 |
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