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Publication numberCN1068279 C
Publication typeGrant
Application numberCN 94193477
PCT numberPCT/US1994/009222
Publication date11 Jul 2001
Filing date15 Aug 1994
Priority date20 Aug 1993
Also published asCA2171199A1, CA2171199C, CN1131404A, DE69406798D1, DE69406798T2, EP0714352A1, EP0714352B1, US5462807, WO1995005942A1
Publication number94193477.2, CN 1068279 C, CN 1068279C, CN 94193477, CN-C-1068279, CN1068279 C, CN1068279C, CN94193477, CN94193477.2, PCT/1994/9222, PCT/US/1994/009222, PCT/US/1994/09222, PCT/US/94/009222, PCT/US/94/09222, PCT/US1994/009222, PCT/US1994/09222, PCT/US1994009222, PCT/US199409222, PCT/US94/009222, PCT/US94/09222, PCT/US94009222, PCT/US9409222
InventorsRW哈尔, DS戴维斯, CR哈里斯
Applicant埃克森化学专利公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Heat sealable films and articles
CN 1068279 C
Abstract  translated from Chinese
本发明涉及某些类型的聚合物、成膜方法及其应用。 The present invention relates to certain types of polymers, film-forming method and its application. 这些聚合物具有独特的性能,使它们特别适用于聚合物薄膜。 These polymers have unique properties, making them particularly suitable for the polymer film. 这些薄膜很适合于需要热合性的应用场合,特别是含有离聚物的应用场合。 These films are suited to applications requiring heat sealability applications, in particular applications comprising ionomer. 业已发现,与用传统的齐格勒-纳塔催化剂生产的聚合物相比,由金属茂催化剂体系生产的聚合物可令人吃惊的很好地热合到称为离聚物的一类聚合物上。 It has been found by the conventional Ziegler - Natta catalyst compared to the polymer produced by metallocene catalyst systems produce polymers can surprisingly good heat-sealing to a class of polymers known as ionomers on.
Claims(8)  translated from Chinese
1. 1. 一种至少有两层的聚合物薄膜,其特征在于,ⅰ)所述的第一层包括乙烯与至少一种α-烯烃的共聚物,其中所述共聚物采用金属茂催化剂制备,并且该共聚物的分子量分布(MWD)小于3.0和Mz/Mw小于2.0,以及ⅱ)所述的第二层含有离聚物,其中将所述的第一层和第二层挤压在一起形成热合,其中在80-110℃范围内的热合温度下,所述热合的峰值热粘力大于2牛顿。 A polymeric film has at least two layers, characterized in that, ⅰ) said first layer comprising ethylene and at least one α- olefin copolymer, wherein the copolymer prepared using a metallocene catalyst, and the copolymerization a molecular weight distribution (MWD) less than 3.0 and a Mz / Mw less than 2.0, and ⅱ) said second layer comprising an ionomer, the first and second layers are extruded together to form wherein the said heat sealing, wherein In the heat sealing temperature in the range 80-110 ℃, said heat peak hot tack force greater than 2 Newton.
2. 2. 根据权利要求1的薄膜,其中所述的聚合物含至少一种有2-20个碳原子的α-烯烃单体及其组合。 Film according to claim 1, wherein said polymer contains at least one α- olefin monomers have 2 to 20 carbon atoms and combinations thereof.
3. 3. 根据权利要求3的薄膜,其中所述的聚合物含有乙烯与至少一种有4-6个碳原子的α-烯烃单体。 Film according to claim 3, wherein said polymer comprises ethylene and at least one α- olefin monomers have 4-6 carbon atoms.
4. 4. 根据权利要求2的薄膜,其中所述的薄膜的热合初始温度为80℃-90℃。 Film according to claim 2, wherein said film is heat-combined initial temperature of 80 ℃ -90 ℃.
5. 5. 根据权利要求4的薄膜,其中所述的层被层压在一起。 Film according to claim 4, wherein said layers are laminated together.
6. 6. 根据权利要求5的薄膜,其中所述的聚合物和/或所述的离聚物与另外的聚烯烃共混。 Film according to claim 5, wherein said polymer and / or said ionomer blended with another polyolefin.
7. 7. 根据上述权利要求中任一项的薄膜,其中所述的聚合物的组成分布宽度指数(CDBI)为90%-95%。 A film according to any one of the preceding claims, wherein said polymer composition distribution breadth index (CDBI) of 90% -95%.
8. 8. 一种具有热合面的制品,通过在足以使至少一个制品部分软化的温度下将所述制品的至少两部分挤压在一起的方法形成所述的热合面,其特征在于,所述至少一个制品部分具有上述权利要求中任一项的薄膜。 An article having a heat-sealing surface, by at least one sufficient to lower the softening temperature of the article portion at least two parts of said article together extrusion method of forming the heat sealing surface, characterized in that said at least one article portion has a film according to any one of the preceding requirements.
Description  translated from Chinese
可热合的薄膜和制品 Heat-sealable films and articles

发明领域本发明涉及可热合的薄膜以及由这些薄膜制得的制品。 Field of the Invention The present invention relates to heat-sealable films and films obtained from these articles. 本发明的薄膜可热合到各种材料以及包括离聚物在内的聚合物上。 Film of the invention to a variety of heat-sealable material and comprises on the inner ionomer polymer.

发明背景目前在市场上可买到许多用热合法制造的制品。 Background of the Invention currently available on the market in many hot lawfully manufactured products. 通常,用将制品两分开的部分焊粘在一起的方法可用于这样制品的封合。 Typically, the article by welding two separate portions stuck together such methods can be used to seal the article. 例如,可用以下步骤将两个单独的塑料零件结合在一起,制成用于制造机器和玩具的塑料部件:将塑料零件中的一个或两个加热,再将它们压合在一起,然后使它们冷却。 For example, using the following steps to separate the two plastic parts together, for the manufacture of machines and toys made of plastic parts: the plastic parts in one or both of heating, and then they are pressed together, and then to make them cool down. 具体地说,热合在包装应用中是很重要的。 Specifically, heat sealing in packaging applications is important. 用热合法制成的包装制品用于有效地运输封装在包装制品中的消费品,用于促销消费品的包装,以及在食品工业中用于消费商品保鲜。 Hot legitimate packaging products made for effective transport of consumer goods packaging products packaged for sales of consumer goods packaging and consumer goods for preservation in the food industry. 从在较低的热合温度下产生强热合面的观点看,最重要的且与实际的热合法有关的是,这样的包装制品或其他需要热合的类似制品的制造者要求极好的加工性能。 From the viewpoint of generating a strong heat seal surface at a lower heat sealing temperature, the most important and relevant legal and practical heat is such packaging products or other similar products require heat sealing manufacturer requirements excellent processability.

各种类型的聚合物都可用于生产包括包装制品在内的各种制品,可通过施加热和/或压力将它们结合在一起或热合在一起。 Various types of polymers can be used to produce a variety of products, including packaging products, including, by the application of heat and / or pressure them together or heat together. 要选择使用用于制造这些制品的聚合物或聚合物共混物,因为它们应提供强的封合,通过短时间施加热和/或压力要能很容易且迅速产生封合。 To select the use for the manufacture of these articles polymer or polymer blends, since they should provide a strong sealing, application of heat and / or pressure through the short to be able to easily and quickly produce sealing. 有时,整个热合制品由相同的聚合物或各种聚合物的共混物或通过相同的或不同的聚合物共挤塑的方法制得。 Sometimes, the entire article by the same heat-sealable polymer or a blend of various polymers, or by the same or different polymer coextruded methods.

更通常的情况是,制得不同材料的区域或层的制品,仅在最终需要热合的区域或层使用能提供良好热合性能的聚合物。 More generally, the obtained regions or layers of different materials the article, can be used only to provide good heat-sealing properties of the polymer in the final zone or layer of heat required. 因为制品例如多层薄膜除有热合性能外,还需要具有物理和机械性能如透明性、强度、耐穿刺性和耐撕裂性,以及易于用高速设备加工,因此制品常采用这类结构。 Because products such as multilayer films in addition to a heat sealing properties, but also need to have the physical and mechanical properties such as transparency, strength, puncture resistance and tear resistance, and easy-to-use high-speed equipment, processing, and therefore often used in products such structures. 已知许多种塑料具有良好的物理和机械性能,但常常没有良好的热合性能。 Known to many types of plastic having good physical and mechanical properties, but often do not have good heat-sealing properties. 例如,聚丙烯有高的强度、良好的透明性和耐撕裂性,但在工业热合机中优选的温度下不易制成很好的热合制品。 For example, polypropylene, high strength, good transparency and tear resistance, but in the industrial heat sealing machine in a preferred temperature easily made good thermal laminate. 相反,一些有良好的热合性能的聚合物又没有足够的强度或透明性。 On the contrary, some have good heat-sealing properties of a polymer do not have enough strength or transparency.

WO93/11940公开了一种达到较好热合性能的方法,它采用包括烯烃聚合物与至多30%重量极低密度乙烯/α-烯烃共聚物的共混物的薄膜基底层以及基底层一面或两层上的热合层,该热合面包括乙烯与α-烯烃共聚单体的极低密度共聚物。 WO93 / 11940 discloses a method to achieve good heat-sealing properties of the method, which uses a polymer comprising olefin and at most 30% by weight of the blend of very low density film underlayer ethylene / α- olefin copolymer and a base layer of one or both layer on the heat seal layer, the heat seal surface comprises a very low density copolymer of ethylene and α- olefin comonomers.

所以,包装技术已开发了多层制品如多层薄膜,有一层或多层相同的或不同类型共混或共挤塑在一起的聚合物,它们有良好的机械性能和物理性能,以及由聚合物构成的另外的一层或多层,它使制品有良好的热合性能。 Therefore, packaging technology has been developed, such as the multilayer film multilayer article, with one or more layers of the same or different types of blended or coextruded with a polymer, they have good mechanical and physical properties, as well as by polymerizing Another one or more layers formed thereof, that the article has good heat-sealing properties. 用这一方法例如可制得有聚丙烯基层提供强度和透明度和聚乙烯层提供良好的热合性的薄膜。 Using this method, for example there can be obtained a polypropylene base layer provides strength and transparency, and a polyethylene layer to provide good heat-sealing properties of the film. 除了薄膜以外,其他制品也可用多种材料制得,选择每种材料为最终的制品提供一种或多种所需的性能。 In addition to film, other products can also be prepared by a variety of materials, each material to provide select one or more desired properties of the final product.

离聚物是柔韧、耐用和透明的热塑性塑料,它们广泛用作包装用薄膜、模塑体、挤塑产品和泡沫产品,以及各种消费产品和工业产品。 Ionomer is flexible, durable, and transparent thermoplastic, they are widely used as packaging films, molded body, extruded products and foam products, and a variety of consumer and industrial products. 在包装方面,特别是离聚物构成最大市场的食品包装薄膜。 In packaging, especially ionomer constitute the largest market for food packaging films. 离聚物有极好的热合特性,在较低的热合温度下就有高的热粘着性和热合强度。 Ionomers have excellent heat sealing properties, heat-sealing at lower temperature have a high hot tack and heat seal strength. 它广泛地在由共挤塑、挤塑贴面、层压以及这些技术的组合制得的各种软包装复合材料中用作热合层。 It is widely by coextrusion, extrusion composition prepared coating, laminating, and these techniques have a variety of flexible packaging composites used as heat seal layer. 应用例子包括肉类、乳酪、快餐食品和药物等的包装。 Example applications include meats, cheeses, snack food and medicine packaging.

各种聚合物当它们彼此热合时应是相当相容的,得到良好的热合性能。 Various polymers should be heat-sealable to each other when they are quite compatible, to obtain good heat sealing properties. 形成有效牢固的热合面通常需要两热合在一起的薄膜部分熔融,并在热合界面上这些熔融的薄膜产生某些混合。 Forming an effective heat seal surface of a solid film is typically required partial melting together of the two heat and melt the heat seal interface of these films have some mixing. 这一混合对于热粘着强度是重要的,在这种情况下热合强度被测量而热合面仍处于部分熔融的状态。 This mixing is important for hot tack strength, in which case the heat seal strength is measured while the heat seal surface is still in a partially molten state. 但是,离聚物由于其强的离子/极性官能度,它与传统的齐格勒-纳塔法生产的线型聚乙烯不特别相容。 However, due to its strong ionomer ionic / polar functionality, with the traditional Ziegler - Natta production of linear polyethylene is not particularly compatible. 所以,在工业上仍然需要得到能有效地与离聚物热合的薄膜。 Therefore, the industry is still in need of effective heat sealing with the ionomer membrane.

本发明概述一般来说,本发明涉及可热合到离聚物制成的薄膜上的聚合物薄膜以及涉及由这样的组合膜制成的制品。 Summary of the Invention The present invention generally relates to heat-sealable polymer film on the film and articles made from ionomers by such a combination film made involved.

在一实施方案中,本发明涉及含有至少两层的聚合物薄膜,其中第一层为分子量分布小于3.0和Mz/Mw小于约2.0的聚合物;而第二层为离聚物,其中所述的第一层和第二层被压制在一起形成热合面。 In one embodiment, the present invention relates to a polymeric film comprising at least two layers, wherein the first layer is less than 3.0 and a molecular weight distribution Mz / Mw of the polymer is less than about 2.0; and the second layer is an ionomer, wherein said The first and second layers are pressed together to form a heat seal surface.

在另一实施方案中,本发明涉及一种有热合面的制品,所述的热合面通过在足以使所述的制品的两部分中的至少一部分软化的温度下,将所述制品的至少两部分压制在一起的方法形成,其中至少一部分由至少一种Mz/Mw小于约2.0和分子量分布(MWD)小于3.0的聚合物构成,而另一部分为至少一种离聚物。 In another embodiment, the present invention relates to a heat-sealing surface of article, said engagement surface by heat sufficient to cause two portions of said article in at least part of the softening temperature of the lower, at least two of said article A method of forming portions are pressed together, wherein at least a portion of at least one by Mz / Mw of less than about 2.0 and a molecular weight distribution (MWD) of the polymer is less than 3.0, while the other part is at least one ionomer.

附图的简要说明当结合附图阅读以下更详细的说明后,本发明的上述方面、特征和优点将变得更清楚和更加全面地被理解。 After BRIEF DESCRIPTION OF THE DRAWINGS As described in more detail below, the above-mentioned aspects, features and advantages of the invention will become more apparent and more fully understood. 附图中:图1为热粘着力随热合温度的变化图,说明表2数据。 In the drawings: Figure 1 is a thermal adhesion with the heat-sealing temperature changes illustrating the data in Table 2.

图2为热合力随热合温度的变化图,说明表3数据。 Figure 2 is a hot heat together with changes in temperature illustrating the data in Table 3.

图3为热粘着力随热合温度的变化图,说明表5聚合物1的数据。 Figure 3 is a thermal adhesion with the heat-sealing temperature changes illustrating the data in Table 5 Polymer 1.

图4为热合力随热合温度的变化图,说明表6聚合物1的数据。 Figure 4 together with the thermal heat temperature changes illustrating the data in Table 6 polymer 1.

图5为热粘着力随热合温度的变化图,说明表5聚合物2的数据。 Figure 5 is a thermal adhesion with the heat-sealing temperature changes illustrating the data in Table 5 Polymer 2.

图6为热合力随热合温度的变化图,说明表6聚合物2数据。 Figure 6 is a hot heat together with changes in temperature illustrating the data in Table 6 Polymer 2.

图7为热粘着力随热合温度的变化图,说明表5聚合物3的数据。 Figure 7 is a thermal adhesion with the heat-sealing temperature changes illustrating the data in Table 5 Polymer 3.

图8为热合力随热合温度的变化图,说明表6聚合物3的数据。 Figure 8 is a hot heat together with changes in temperature illustrating the data in Table 6 Polymer 3.

本发明的详细说明本发明涉及某种类型的聚合物、它们的制膜生产方法及其应用。 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to certain types of polymers, their production methods and their application film. 这些聚合物具有一些独特的性质,使它们特别适用于聚合物薄膜。 These polymers have a number of unique properties, making them particularly suitable for the polymer film. 这些薄膜特别适用于需要热合性的应用场合,特别是薄膜热合到离聚物膜上的那些应用场合。 These films are particularly useful for heat sealing applications, especially film heat sealing ionomer film to those applications.

现已发现,由金属茂催化剂体系得到的聚合物与由传统的齐格勒-纳塔催化剂得到的聚合物相比,可令人吃惊地极好地热合到称为离聚物的一类聚合物上。 It has been found, by the metallocene catalyst system and polymers obtained by the conventional Ziegler - Natta catalyst obtained polymer, can surprisingly heat seal extremely well for a Class polymerization ionomer referred to thing on.

聚合物的制备本发明的聚合物用金属茂催化剂体系,以聚合法或共聚法在气相、浆液中或高压相中生产。 Polymers of the present invention is a polymer with a metallocene catalyst system, to polymerization or copolymerization in a gas phase, slurry phase or high pressure production.

聚合或共聚法涉及一种或多种有2-20个碳原子(优选2-15个碳原子)的a-烯烃的聚合。 Relates to the polymerization or copolymerization of one or more with a polymeric 2-20 carbon atoms (preferably 2 to 15 carbon atoms) of a- olefin. 本发明特别适合于涉及一种或多种单体聚合的共聚合反应,例如乙烯、丙烯、丁烯-1、戊烯-1、4-甲基戊烯-1、己烯-1、辛烯-1、癸烯-1等的α-烯烃以及如苯乙烯的环烯烃。 The present invention is particularly suitable for involving one or more monomers copolymerizable polymerization reaction, such as ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene 1, decene-1, etc. of α- olefins, and cyclic olefins such as styrene. 其他单体可包括极性乙烯基、二烯烃、降冰片烯、乙炔和醛类单体。 Other monomers can include polar vinyl, dienes, norbornene, acetylene and aldehyde monomers. 优选的是,这样来生产乙烯共聚物,调整乙烯和共聚单体的数量以便生产所需的聚合物产物。 Preferably, the number of such to produce ethylene copolymers of ethylene and comonomer adjusted to produce the desired polymer product. 优选的是,共聚单体为有3-15个碳原子的α-烯烃,更优选4-12个碳原子,最优选4-10个碳原子。 Preferably, there are α- olefin comonomer is 3-15 carbon atoms, more preferably 4-12 carbon atoms, most preferably 4-10 carbon atoms. 在另一实施方案中,乙烯至少与两种共聚单体聚合,生成三元聚合物等。 In another embodiment, the ethylene polymerized with at least two comonomers to produce terpolymers and the like. 如果使用共聚单体,那么单体按以下比例与共聚单体聚合:70.0-99.99(优选70-90,更优选80-95或90-95)%(摩尔)单体与0.01-30(优选3-30,最优选5-20、5-10)%(摩尔)共聚单体。 If comonomer is used, then the following ratio of monomers and comonomers: 70.0-99.99 (preferably 70-90, more preferably 80-95 or 90-95)% (mol) of monomer and 0.01 to 30 (preferably 3 -30, and most preferably 5-20,5-10)% (mol) comonomer.

对于本发明说明书来说,在这里术语“金属茂”指含有一个或多个环戊二烯基部分与元素周期表的过渡金属结合。 For the present invention, the specification, herein the term "metallocene" means a transition metal containing one or more cyclopentadienyl moiety in combination with the Periodic Table of Elements. 用通式(Cp)mMRnR′p表示金属茂催化剂组分,其中Cp为取代的或未取代的环戊二烯基环;M为第Ⅳ、Ⅴ或Ⅵ族过渡金属;R和R′各自独立选自卤素、有1-20个碳原子的烃基或烃氧基;m=1-3,n=0-3,p=0-3以及m+n+p的总和等于M的氧化态。 By the general formula (Cp) mMRnR'p represents metallocene catalyst component, wherein Cp is a substituted or unsubstituted cyclopentadienyl ring; M is the first Ⅳ, Ⅴ Ⅵ group or a transition metal; R and R 'are each independently selected from halogen, a hydrocarbon group or a hydrocarbon group having 1 to 20 carbon atoms; m = 1-3, n = 0-3, p = 0-3 and the sum of m + n + p equals the oxidation state of M. 金属茂原则上可用烃基取代基取代,但不排除含锗、磷、硅或氮原子的基团,或者不取代,桥连或不桥连或任何组合。 Available substituted hydrocarbyl substituent on the metallocene principle, but does not exclude a germanium, phosphorus, silicon or nitrogen atom, or unsubstituted, bridged or unbridged or any combination thereof. 各种形式的金属茂型催化剂体系都可用于本发明的聚合方法中。 Various forms of metallocene-type catalyst system can be used in the polymerization process of the present invention. 用于乙烯聚合的金属茂催化剂例如在US4871705(Hoel)、US4937299(Ewen等)、EP-A-0129368(1989年7月26日公开)和US5017714和5120867(Welborn,Jr)中可找到。 Metallocene catalyst for the polymerization of ethylene, such as US4871705 (Hoel), US4937299 (Ewen, etc.), EP-A-0129368 (1989 年 7 月 26 Publication Date) in and US5017714 and 5120867 (Welborn, Jr) can be found. 这些专利公开了这些金属茂催化剂的结构,并包括铝噁烷作为助催化剂。 These patents disclose structures of these metallocene catalysts and includes alumoxane as the cocatalyst. 有各种制备铝噁烷的方法,其中一种方法在US4665208中公开。 There are a variety of methods for preparing alumoxane, one of the methods disclosed in US4665208 in.

其他助催化剂也可与金属茂一起使用,如三烷基铝化合物;或离子化的离子活化剂或化合物如三(正丁基)铵四(五氟苯基)硼,它使中性的金属茂化合物离子化。 Other cocatalysts may be used with metallocenes, such as trialkylaluminum compounds; or ionizing ionic activators or compounds such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, which makes neutral metal metallocene compound ionization. 这样的离子化化合物可含有活性质子或一些与离子化的离子化合物的其余离子相连但不配位或仅松散配位的其他阳离子。 Such ionizing compounds may contain an active proton, or some connected to the remaining ion of the ionizing ionic compound but not coordinated or only loosely coordinated to the other cations. 这样的化合物在EP-A-0520732、EP-A-0277003和EP-A-0277004(两者都在1988年8月3日公开)和US5153151和5198401中公开。 Such compounds are disclosed in EP-A-0520732, EP-A-0277003 and EP-A-0277004 (both of which are disclosed in the August 3, 1988) and in US5153151 and 5198401.

另外,金属茂催化剂组分可为含杂原子单环戊二烯基化合物。 Further, the metallocene catalyst component can be monocyclopentadienyl heteroatom containing compound. 该杂原子用铝噁烷或离子活化剂活化,生成活性的聚合催化剂体系,以便生产用于本发明的聚合物。 The heteroatom aluminum dioxane or ionic activators activation, formation of the active polymerization catalyst system to produce polymers useful in the present invention. 这些类型的催化剂体系例如在WO92/00333(1992年1月9日公开)、US5096867和5055438、EP-A-0420436和WO91/04257中公开。 These types of catalyst systems such as (January 9, 1992 public) in WO92 / 00333, US5096867 and 5055438, EP-A-0420436 and WO91 / 04257 disclosed.

此外,用于本发明的金属茂催化剂还可包括非环戊二烯基催化剂组分,或辅助配体如boroles或carbollides与过渡金属结合。 In addition, the metallocene catalysts used in the present invention may also include non-cyclopentadienyl catalyst components, or ancillary ligands such as boroles or carbollides in combination with a transition metal. 此外,US5064802.WO92/08221和WO93/08199(1993年4月29日公开)中公开的催化剂和催化剂体系也在本发明的范围内。 In addition, US5064802.WO92 / 08221 and WO93 / 08199 (1993 年 4 月 29 Publication Date) within the scope of catalysts and catalyst systems are disclosed in the present invention. 上述所有的催化剂体系都可与添加剂或清除组分结合使用,以提高催化剂的产率。 All the above-mentioned catalyst system can be used in combination with additives or remove components, in order to improve the productivity of the catalyst.

在气相法中,催化剂颗粒可负载在适合的颗粒材料上,例如聚合物载体或无机氧化物如氧化硅、氧化铝或两者。 In the gas phase process, the catalyst particles may be supported on a suitable particulate material, such as a polymer or an inorganic oxide carrier such as silica, alumina or both. 使本发明的催化剂负载的方法在US4808561、4897455、4937301、4937217、4912075、5008228、5086025和5147949以及美国专利申请898255(1992年6月12日提交)和885170(1992年5月8日提交)中公开。 The catalyst loading method of the present invention in US4808561,4897455,4937301,4937217,4912075,5008228,5086025 and 5,147,949 and US Patent Application 898,255 (June 12, 1992 submission) and 885,170 (May 8, 1992 submission) in public.

本发明聚合物的特征本发明聚合物的重要特征是其组成分布。 Important features of the present invention is characterized in the present invention, the polymer is a polymer of its composition distribution. 如熟悉本专业的技术人员所熟知的,共聚物的组成分布与共聚物分子中共聚单体分布的均匀性有关。 As those skilled in the art in the art, the composition distribution of the copolymer molecules copolymer comonomer distribution uniformity related. 已知金属茂催化剂可使共聚单体很均匀地加到由它们生产的聚合物分子中。 The metallocene catalysts are known comonomer can be added to a very uniform polymer molecules they produce. 因此,由有单金属茂组分的催化剂体系生产的共聚物有很窄的组成分布一绝大多数聚合物分子有大致相同的共聚单体含量,而在每一分子中共聚单体将无规分布。 Thus, by having a single metallocene component of the catalyst system produced copolymer has a very narrow composition distribution of a majority of the polymer molecules have substantially the same comonomer content, and the random comonomer in each molecule distribution. 另一方面,齐格勒-纳塔催化剂通常得到有相当宽的组成分布的共聚物。 On the other hand, Ziegler - Natta catalysts are usually obtained copolymer has a rather broad composition distribution. 在聚合物分子中共聚单体加入量变化很大。 Comonomers in the polymer molecule is added a large amount of variation.

组成分布的一个量度是“组成分布宽度指数”(“CDBI”)。 A measure of composition distribution is the "Composition Distribution Breadth Index" ("CDBI"). CDBI规定为有中值总摩尔共聚单体含量的50%范围内(即每边25%)共聚单体含量的共聚物分子的重量百分数。 CDBI is defined as the 50% range have median total molar comonomer content (i.e. 25% per side) comonomer content by weight percent of the copolymer molecules. 共聚物的CDBI很容易用大家熟悉的分离共聚物样品的单一级分的技术来确定。 CDBI copolymer readily be determined by the familiar single stage separation copolymer sample points technique. 一种这样的技术是温升洗脱分级法(TREF),如在Wild et al.,J.Poly sci.,Poly.Phys Ed.,Vol2,p441(1982)和US5008204中描述的。 One such technique is the temperature rise elution fractionation method (TREF), as described in Wild et al., J.Poly sci., Poly.Phys Ed., Vol2, p441 (1982) and US5008204 described.

为了测定CDBI,首先作出共聚物的溶解度分布曲线。 In order to determine CDBI, a solubility distribution curve of the copolymer made first. 这一点可用上述的TREF技术得到的数据来完成。 This data can be used to obtain the above TREF technique to complete. 这一溶解度分布曲线是溶解的共聚物重量分数随温度变化的曲线。 This solubility distribution curve is the weight fraction of the copolymer dissolved versus temperature curve. 将它转换成重量分数对组成分布的曲线。 Convert it to the weight fraction of the composition distribution curve. 为了简化组成与洗脱温度的关系,小于15,000的重量级分数不考虑。 To simplify the relationship between the composition and temperature of the elution, fractions of less than 15,000 is not considered a heavyweight. 这些低重量级分通常表示本发明不重要的树脂部分。 These low weight fraction of the present invention is generally indicated resin portion unimportant. 在本说明书的其余部分和附后的权利要术中,在CDBI测量中不考虑低于15,000重量级分。 In the rest of the operation and the appended claims of the present specification, is not considered in the CDBI measurement less than 15,000 weight fraction.

从重量级分对组成分布的曲线上,由具有在中值共聚单体含量每边25%范围内的共聚单体含量的重量百分数来确定CDBI。 From the weight fraction of the composition distribution curve, by weight percent comonomer content has a value within the range of the comonomer content of 25% on each side to determine CDBI. 对于熟悉本专业的技术人员来说,测定共聚物的CDBI的进一步详细描述是已知的。 For those skilled in the art, the further detailed description of CDBI determination copolymers are known. 例如参见PCT专利申请WO93/03093,1993年2月18日公开。 See, for example PCT patent application WO93 / 03093,1993 on February 18 open.

本发明聚合物的CDBI一般在80-98%范围内,优选在85-98%范围内,最优选在90-95%范围内。 CDBI polymers of the invention is generally in the 80-98% range, preferably in the range of 85-98%, most preferably in the range of 90-95%. 显然,使用其他的催化剂体系,通过改变所用方法的操作条件可得到或高或低的CDBI。 Clearly, the use of other catalyst systems, the method by varying the operating conditions to obtain higher or lower CDBI.

根据分子量分布(MWD),本发明的薄膜也与由齐格勒-纳塔催化剂得到的已知薄膜有区别。 The molecular weight distribution (MWD), with the film of the invention also by Ziegler - Natta catalyst known films obtained are different. 本发明聚合物的MWD比用传统的齐格勒-纳塔催化剂制得的聚合物要窄得多。 MWD polymers of the invention than with conventional Ziegler - Natta catalyst obtained polymer is much narrower. 本发明的聚合物的多分散性指数(Mw/Mn)通常在1.5-3范围内,而相比之下最熟悉的齐格勒-纳塔催化的聚合物为3和大于3。 The polydispersity index of the polymer of the present invention (Mw / Mn) is generally in the range of 1.5-3, in contrast most familiar Ziegler - Natta catalyzed polymer of 3 and greater than 3. 在这方面,本发明的树脂与许多可商购的用齐格勒-纳塔催化剂制得的聚合物很不相同。 In this regard, the resin of the present invention and many commercially available with a Ziegler - Natta catalyst obtained polymer is very different. 另外,本发明聚合物的分子量分布曲线的拖尾比已知的齐格勒-纳塔LCDPE要小得多。 Further, the molecular weight distribution curve of the polymer of the present invention trailing than the known Ziegler - Natta LCDPE much smaller. 通过比较Mz/Mw比(第三矩与第二矩比)和Mz+1/Mw比(第四矩与第二矩比)很容易看出这一区别。 By comparing Mz / Mw ratio (ratio of the third moment of the second moment) and Mz + 1 / Mw ratio (ratio of the fourth moment of the second moment) it is easy to see the difference. 利用本发明,可生产Mz/Mw小于2.5的聚合物,优选小于2.0,最优选1.4-1.9。 With the present invention, can produce Mz / Mw of the polymer is less than 2.5, preferably less than 2.0, most preferably 1.4-1.9. 相反,齐格勒-纳塔聚合物的Mz/Mw比通常大于2.5。 In contrast, Ziegler - Natta polymers Mz / Mw ratio is typically greater than 2.5. 类似地,本发明聚合物的Mz+1/Mw值小于4.0,优选小于3.0,最优选在2.0-3.0范围内。 Similarly, the polymers of this invention Mz + 1 / Mw value of less than 4.0, preferably less than 3.0, most preferably in the 2.0 to 3.0 range. 对于齐格勒-纳塔聚合物,Mz+1/Mw通常要高得多,通常大于4.0。 For Ziegler - Natta polymers, Mz + 1 / Mw is generally much higher, generally greater than 4.0. 表Ⅰ提供了本发明聚合物以及一些商购聚合物的Mz、Mw、Mz+1的进一步数据。 Table Ⅰ present invention provides a polymer as well as some commercially available polymer Mz, Mw, Mz + 1 of the further data.

熟悉本专业的技术人员会知道有数种方法可用来测定聚乙烯样品的分子量分布。 Those skilled in the art will recognize that there are several methods used to determine the molecular weight distribution of polyethylene samples. 对于表Ⅰ和本申请说明书和附后的权利要求中提及的Mw、Mz和Mz+1,使用装有在145℃下操作的ultrastyro凝胶柱的水凝胶渗透色谱仪测定分子量分布。 For Mw Table Ⅰ and this specification and the appended claims mentioned, Mz and Mz + 1, using a gel permeation chromatograph equipped with water at 145 ℃ operated ultrastyro gel columns determine the molecular weight distribution. 三氯苯用作冲洗溶剂。 Trichlorobenzene is used as the washing solvent. 标定标准是16个准确已知分子量的聚苯乙烯样品,其分子量为从500到5200000。 Calibration standards are 16 accurate polystyrene samples of known molecular weight, a molecular weight of from 500 to 5,200,000. NBS1475聚苯乙烯也用作标定标准。 NBS1475 polystyrene is also used as calibration standards.

本发明树脂的熔体指数通常在0.1-1000分克/分钟之间,优选0.1-100分克/分钟,更优选0.1-20分克/分钟,甚至更优选0.1-10分克/分钟,最优选0.1-5分克/分钟。 Melt index resin of the invention is generally between 0.1 - 1000 dg / min, preferably 0.1 to 100 dg / min, more preferably 0.1 to 20 dg / min, even more preferably 0.1 to 10 dg / min, most preferably 0.1 to 5 dg / min.

离聚物的特征离聚物是含有链间离子键的聚合物的通称。 Copolymer ionomer from feature is known as a polymer containing interchain ionic bonds. 这些离子交联随机出现在长键聚合物分子间,产生通常与高的分子量有关的固态性质。 These ionically crosslinked random key between long polymer molecules to produce solid-state properties usually associated with high molecular weight.

但是,将离聚物加热到通常热塑性塑料加工温度会使离子力消失,使得能在传统的设备中加工。 However, the ionomer is heated to a normal thermoplastic processing temperatures can cause ion force disappears, so that can be processed in the conventional apparatus. 通常,离聚物基于乙烯/甲基丙烯酸共聚物或丙烯酸共聚物的金属盐,并且具有长链和半结晶结构。 Typically, ionomers based on metal salts of ethylene / methacrylic acid copolymer or acrylic copolymer, and having a long chain and a semi-crystalline structure.

有50种以上商品级的离聚物,具有各种性质。 There are more than 50 kinds of commercial grade ionomer, having a variety of properties. 随着新的低模量树脂的出现,商购未增强的离聚物的挠曲模量在139巴(2000磅/英寸2)(以前提供的最柔软级为约1042巴(15000磅/英寸2)至约5900巴(85000磅/英寸2)。 With the advent of new low-modulus resins, commercially available unreinforced flexural modulus ionomer at 139 bar (2000 lbs / in2) (previously provided by the softest level of about 1042 bar (15,000 lbs / inch 2) to about 5900 bar (85,000 lbs / in2).

离聚物的性质随金属阳离子的类型和数量、基础树脂的分子量和组成(即乙烯和甲基丙烯酸类的相对含量)以及添加的成分如增强剂或添加剂而变化。 From the nature of the homopolymer with the type and amount of metal cations, molecular weight and composition of the base resin (i.e., relative content of ethylene and methacrylic acid), and added ingredients such as reinforcing agents or additives vary. 长链、半结晶聚合物结构提供通常聚烯烃如下特性:良好的化学惰性、热稳定性、低的介电性和低的透水蒸汽性。 Long-chain, semicrystalline polymer structure provides the following features typically a polyolefin: good chemical inertness, thermal stability, low dielectric properties and low water vapor permeability. 羧酸盐结构提供与聚乙烯不同的性质。 Polycarboxylates and polyethylene structure provides different properties.

有关制备离聚物的详细内容可参见专利US3552638、3597887、3610501、4351931、4766174、4690981、4174358、4663383、4550141、4539263、4469754、4387188和4235980。 Concerning the preparation of the ionomer details can be found in patent US3552638,3597887,3610501,4351931,4766174,4690981,4174358,4663383,4550141,4539263,4469754,4387188 and 4,235,980. 在本发明的一个实施方案中,离聚物可以商品SurlynR从EIDupont公司(Wilmmgton,Delawaoe)购得。 In one embodiment of the present invention, the trade SurlynR ionomers commercially available from EIDupont Corporation (Wilmmgton, Delawaoe). 一些代表性SurlynR离聚物级树脂包括AD-8143、8144、8255、8066,EC-8577、8585、7930、7940、1555、1557、1558、1559、1560、1601、1604、1605、1652、1650、1655、1603、1606、1702、1705、1706、1707、1800和1855。 Some representative SurlynR grade ionomer resins include AD-8143,8144,8255,8066, EC-8577,8585,7930,7940,1555,1557,1558,1559,1560,1601,1604,1605,1652,1650, 1655,1603,1606,1702,1705,1706,1707,1800 and 1855.

在另一实施方案中,离聚物还可以商品IOTEKTM从EXXON化学公司(Baytown,Texas)购得。 In another embodiment, the ionomer is also commercially available from EXXON under the trade IOTEKTM Chemical Company (Baytown, Texas). 一些代表性IOTEKTM离聚物级树脂包括3110、4000、4200、7010、7020、7030、8000、8020、和8030。 Some representative IOTEKTM ionomer resins include 3110,4000,4200,7010,7020,7030,8000,8020 level, and 8030.

从这些聚合物制得的薄膜的性能用上述金属茂催化剂制得的聚合物在许多应用场合中都显著优于可商购的产品。 From the properties of these polymer films obtained by the above-described metallocene catalyst, the polymer in many applications are significantly better than the commercially available product. 这些聚合物特别适合于薄膜应用场合。 These polymers are particularly suited for film applications. 表Ⅰ列出本发明(聚合物1-5)薄膜的性质。 Nature of the invention are listed in Table Ⅰ (Polymer 1-5) films.

本发明聚合物的一个特性是有很低的可萃取组分含量。 A characteristic of the polymer of the present invention is very low extractable component content. 对于大多数品级的聚合物来说,可萃取物含量在5.5%至0.1%以下的范围内,优选2.6%以下,更优选1.0%以下,甚至更优选0.8%以下,最优选0.5%以下。 For most of the range of grades of polymer, the extractables content of 5.5 to 0.1% or less, preferably 2.6% or less, more preferably 1.0% or less, even more preferably 0.8% or less, most preferably 0.5% or less.

所描述的聚合物的可萃取物含量一般随分子量和密度的下降而增加。 Extractable content of the polymer is generally described with the molecular weight and decrease the density increases. 在任一给定的分子量和密度(或侧链分支)下,本发明树脂的可萃取物含量都显著低于对应的齐格勒-纳塔级聚合物。 In any given molecular weight and density (or side chain branching), the extractables content of the resin of the present invention are significantly lower than the corresponding Ziegler - Natta grade polymer. 对于本说明书和附后的权利要求来说,通过将由聚合物制得的薄膜在50℃下浸入正己烷中2小时来测量可萃取物含量。 For the present specification and the appended claims, the adoption by the polymer film obtained was immersed in n-hexane at 50 ℃ for 2 hours to measure extractables. 这一方法在21CFR177.1520(d)(3)(ⅱ)和FDA规格中有进一步的详细描述。 This approach is described in further detail 21CFR177.1520 (d) (3) (ⅱ) and FDA specifications. 对于熟悉本专业的技术人员来说,应当理解,可萃取物含量的试验可有很大的偏差。 For those skilled in the art, it should be understood that the content of the test extracts may have a great deviation. 这些偏差可能是由于薄膜厚度(最大4密耳)或其他任何可使表面与体积比变化的因素引起的。 These deviations may be due to film thickness (4 mils maximum) or any other factors that can change the surface to volume ratio caused. 薄膜的生产方法(例如吹塑、流延)和加工条件也可改变可萃取物数量。 The method of producing a thin film (e.g. blown, cast) and processing conditions may also change the number of extractables. 由这些树脂制得的低可萃取物薄膜使得它们很适合于食品应用场合。 So that they may be extracts from such low film resin obtained is suitable for food applications.

良好的热合聚合物有几个重要的特性。 Good heat sealing polymer has several important features. 一个重要的特性是热合初始温度。 An important feature is the initial temperature heat. 它是这样一个温度:聚合物在压力下本身进行有效粘合或粘合到某些其他聚合物上以前必须加热到的温度。 It is such a temperature: polymer under pressure itself effectively bonded or adhered to some other polymer must be heated to a temperature previously. 所以,超过热合初始温度的热合温度产生有相当大的可测得到的热合强度的热合。 Therefore, the initial temperature of the heat over the heat seal temperature yields considerable measurable heat seal strength of the obtained heat sealing. 在工业热合设备中,相对低的热合初始温度是希望的。 In industrial heat sealing equipment, the initial relatively low heat sealing temperature is desirable. 较低的热合温度在设备上有较高的包装生产率,因为不需将聚合物加热到太高的温度就能热合。 Lower heat sealing temperature on the device has a higher packing productivity, because the polymer need not be heated to too high a temperature can heat sealing. 在热合中控制生产率的重要因素是将热传递到界面并使聚合物薄膜熔融所需的时间。 Important factor controlling productivity in heat sealing is to transfer heat to the interface and the time required to melt the polymer film. 较低的热合初始温度使热传递时间变短,从而使聚合物熔融的时间缩短。 Lower heat seal initial temperature of the heat transfer time becomes shorter, thereby shortening the time to melt the polymer. 此外,热合面冷却达到适宜的强度也更快热合初始温度(SIT)被规定为热合产生可测量得到的强度所需的最低温度。 In addition, heat sealing surface cooling achieve optimum strength heat faster initial temperature (SIT) is defined as the lowest temperature measurable heat generated to get the desired strength. 在工业热合操作中控制生产率(单位时间的包装数)的限制因素是将热传递到界面并达到所需的热合温度所需的时间。 Control in industrial heat sealing operation productivity (number of packages per unit time) of the limiting factor is the heat transfer to the interface and the time required to reach the desired heat seal temperature. SIT越低,使热传递到热合表面的界面所需的时间越短。 The lower the SIT, the heat transfer to the time required to heat the interface surface is shorter. 定性地说,即使SIT下降10℃也可使生产率提高30%。 Qualitatively speaking, even if dropped 10 ℃ SIT also allows a 30% increase in productivity. 对于更详细地描述可参见PCT申请WO93/03093(1993年2月18日公开)。 For a more detailed description can be found in PCT application WO93 / 03093 (1993 年 2 月 18 Publication Date). 该文献讨论了某些聚合物当制成用于本发明的薄膜时的热合特性。 This document discusses the heat sealing characteristics of some polymers when prepared for when the film of the invention. 但是该申请未公开将这些薄膜热合到离聚物上。 However, this application does not disclose these polymer films to the heat away.

另一特性是热合温度范围,它是形成热合可接受的温度范围。 Another characteristic is the heat seal temperature range, which is the formation of an acceptable heat seal temperature range. 热合温度范围确定可接受的操作温度范围,在这一范围内热合强度基本上保持不变。 Heat sealing temperature range to determine the acceptable operating temperature range, in this range of heat seal strength remains substantially constant. 该范围的下限温度是热合初始温度,而上限温度是热合强度下降到可接受的水平以下或聚合物开始降解的温度。 The lower limit temperature of the heat sealing range is the initial temperature, while the upper limit temperature is the heat seal strength is reduced to an acceptable level or below the temperature of the polymer begins to degrade.

另一热合特性是在冷却过程中热合面固化以前粘合强度的大小。 Another characteristic of heat in the cooling process is heat sealing surface size before curing the adhesive strength. 在每一热合面形成后和它冷却前,立刻撕开样品,以测量热合强度。 After each heat seal surface is formed and before it cools, and immediately ripped sample to measure the heat seal strength. 在本专业中,这一强度称为热粘性,以每单位热合面宽度的力来量度。 In this profession, this is called hot tack strength to heat the surface force per unit width to measure. 热粘性越高越好。 The higher the hot tack the better. 还发现,在制成本发明的乙烯共聚物中使用的共聚单体影响热粘性。 Also found that the use of comonomers in the ethylene copolymer of the invention on heat cost tack. 随着共聚单体直链碳原子数目的增加,例如从丁烯-1到己烯-1到辛烯-1,热粘性也显著增加。 As the number of carbon atoms in a straight chain comonomer increases, e.g., to octene-1 the hot tack increases significantly from butene-1 to hexene-1. 这一显著的效果特别是在使用的共聚单体丁烯-1与己烯-1之间可以看出。 This effect is particularly remarkable in use between the comonomer butene-1 and hexene-1 can be seen.

这三个重要的热合特性:热合初始温度(SIT)、热合强度(SS)、热合温度范围与热粘性(HT)之间的相互关系对于薄膜等的用户来说极为重要。 The three important heat sealing characteristics: initial heat sealing temperature (SIT), heat seal strength (SS), the relationship between the temperature range of heat-sealing and hot tack (HT) are extremely important for the user between the film and the like is concerned. 特别是在包装领域,在此领域需很迅速加工和制成包装袋,这些特性变得很重要。 Especially in the field of packaging, the need is very rapid processing and packaging bags made in this area, these characteristics become very important. 低的SIT使包装者使用较少的热和/或较低的压力来完成热合;高热合强度能更坚固和更快形成热合;高的热粘性防止热合损坏和开口,并避免造成在高速包装下包装产品的损失。 Low SIT allows packaging to use less heat and / or lower pressure to complete the heat; heat sealing strength can be more robust and faster formation of heat; high hot tack and prevent heat damage to the opening, and avoid the high-speed packaging Loss of packaging products. 所有这些特性的组合使包装者能提高给定方法的线速。 All combinations of these characteristics can be improved to enable packer linear velocity given method. 通过提高生产率不仅给包装者带来好处,而且由于可在低得多的温度操作而节省了费用。 By increasing productivity benefits not only to the packer, and because the temperature can be much lower operating cost savings.

热合温度必须高到使聚合物部分熔融/软化,以致使它们粘着到要热合的材料上。 Heat sealing temperature must be high enough to make the polymer portion of the molten / softened, to cause them to adhere to the heat seal material. 热合温度可高达共聚物的熔点温度,甚至更高,但在这样高的温度下热合接触时间必须缩短。 Heat sealing temperature up to the melting point temperature of the copolymer, or even higher, but at such a high temperature heat-sealing contact time must be shortened.

本发明薄膜本发明的薄膜可用本专业中大家熟悉的方法由本发明的聚合物和离聚物制成。 Film of the present invention is a thin film of the present invention may be present in the professional familiar method from the polymer of the invention and ionomers. 例如,制法包括薄膜、片材和其他纤维挤塑和共挤塑,以及吹塑、注塑和滚塑。 For example, the manufacturing method including a film, sheet, and other fiber extrusion and co-extrusion as well as blow molding, injection molding and rotational molding. 薄膜包括用共挤塑或层压或挤贴面制成的单层或多层结构吹塑膜或流延膜。 Film comprises a monolayer or multilayer structure blown film or cast film made by coextrusion or extrusion lamination or veneer.

例如,本发明的聚合物可以熔融状态通过扁平模头挤塑,然后冷却形成片材或流延膜。 For example, the polymer of the present invention may be in a molten state through a flat die extrusion, sheet or then cooled to form a cast film. 另一方面,聚合物可以熔融状态通过环口模头挤塑,然后吹塑并冷却形成管状膜。 On the other hand, the polymer can be molten state extruded through a ring die head, and then blown and cooled to form a tubular film. 管状膜可沿轴向切开并展开形成平膜。 The tubular film may be slit and expand the flat film is formed in the axial direction. 本发明的薄膜可为未取向的、单轴向取向的或双轴向取向的。 Film of the invention may be unoriented, uniaxially oriented or biaxially oriented.

本发明的薄膜可为单层薄膜或多层薄膜。 Film of the present invention may be a monolayer film or multilayer film. 多层薄膜可由一层或多层由本发明聚合物形成的膜和至少一层其他的膜(其中一层是离聚物膜)组成。 The multilayer film of a polymer film formed by the present invention may be one or more layers and at least one other film (one of which is the ionomer membrane) composition. 薄膜也可具有由其他材料形成的其它的一层或多层,其他聚合物如为LLDPH、LDPE、HDPE、PP、PB、EVA、聚酯、EVOH以及金属箔、纸等。 Other films may also have one or more layers formed from other materials, other polymers such as LLDPH, LDPE, HDPE, PP, PB, EVA, polyester, EVOH and a metal foil, paper or the like.

多层薄膜可用本专业中大家熟悉的方法制成。 Multilayer films of the profession may be made to the familiar method. 如果所有的层都是聚合物,可将聚合物通过共挤塑供料头和模头组合共挤塑,制成有两层或两层以上粘合在一起的薄膜,但各层的聚合物组成不同。 If all layers are polymers, the polymer may be by co-extrusion feed block and die head assembly coextrusion, two or more layers formed have films bonded together, but the layers of polymer different composition. 多层薄膜也可用挤出贴面法制成,用这一方法使基质材料与刚挤出模头的热熔聚合物接触。 Multilayer films are also available for extrusion coating into the legal system, use this method to make contact with a rigid matrix material of hot-melt polymer extrusion die. 挤出贴面法适合使用这样一些基质材料,由天然纤维或合成纤维或纱纺织的或针织的基质材料如纺织品,或者由非聚合物制得的基质材料如玻璃、陶瓷、纸或金属。 Extrusion coating method is suitable for the use of such a number of the matrix material, from natural fibers or synthetic fibers or yarns woven or knitted base material such as textiles, or by a non-polymeric matrix material prepared such as glass, ceramic, paper or metal.

多层薄膜也可用上述制得的两种或多种单层薄膜组合的方法制成。 The multilayer film can also be used a method in combination of two or more single-layer film made of the above-obtained. 如此制得的两层薄膜可用粘合剂或用热和压力粘合在一起。 Thus obtained two-layer film can be bonded together with an adhesive or heat and pressure.

本发明热合面的峰值热粘着力在约2-约10牛顿范围内,优选约2至约8牛顿,最优选约2.5至约7牛顿。 Peak heat adhesion of the heat seal surface of the present invention is in the range of about 2 to about 10 Newtons, preferably from about 2 to about 8 Newtons, and most preferably from about 2.5 to about 7 Newtons. 在一个实施方案中,热合温度为约80至约110℃时,热合面的峰值热粘着力大于约2牛顿。 In one embodiment, the heat sealing temperature is from about 80 to about 110 ℃, the peak heat-adhesion of the heat seal surface is greater than about 2 Newtons. 在另一实施方案中,热合温度约为80至105℃时,热合面的峰值热粘力为约2牛顿。 In another embodiment, the heat sealing temperature is about 80 to about 105 ℃, the peak hot tack heat seal surface is about 2 Newtons. 在另一实施方案中,热合温度为约85至约100℃时,热合面的峰值热粘着力大于约2.5牛顿。 In another embodiment, the heat sealing temperature is from about 85 to about 100 ℃, peak heat adhesion of the heat seal surface is greater than about 2.5 Newtons.

在一优选的实施方案中,本发明的薄膜通过至少一层本发明聚合物热合到至少一层离聚物上的方法制得。 In a preferred embodiment, the polymer film of the invention by the present invention is thermally bonded to at least one layer from the at least one layer on the prepolymer was prepared. 表2-7给出了由本发明各种聚合物本身热合或热合到离聚物(即SurlynR)和传统的LLDPE(Dowlex2056)上得到的结果。 Table 2-7 shows the heat itself from a variety of polymers of the invention or the heat to ionomer (ie SurlynR) and the results of conventional LLDPE (Dowlex2056) get on. 在这些表中还给出了离聚物和Dowlex2056本身热合或彼此热合的数据。 In these tables also gives the ionomer itself and Dowlex2056 heat or heat sealing each other's data.

实施例提供以下的实施例,以便更好的理解本发明以及其代表性优点。 The embodiment provides the following examples, to better understand the present invention and representative advantages thereof.

在表2-7中试验的所有薄膜都基本上相同,但热合层的聚合物不同,它们或者是本发明的聚合物,或者是Dowlex2056,或者是离聚物。 In Table 2-7, all test films are substantially the same, but different polymer heat seal layer, polymers which are either present invention, either Dowlex2056, or ionomers. A/B/C结构的薄膜被共挤塑,A为HDPE,B为粘结层,C为热合层。 Film A / B / C structure is coextruded, A is a HDPE, B is an adhesive layer, C is the heat seal layer. 所用的H DPE为从Allicd Signal Inc得到的PAXON4700,粘结层为ESCOR ATX-310,由Exxon化学公司(Baytown,Texas)得到的酸性三元聚合物。 H DPE used for PAXON4700, an adhesive layer obtained from Allicd Signal Inc as ESCOR ATX-310, acid terpolymer from Exxon Chemical Company (Baytown, Texas) obtained. 该薄膜被流延在1英寸Killion Mini Cast Film Line,Model KLB 100上,得到厚度为约3密耳的薄膜,使得A/B/C三层中每一层大约为1密耳厚。 The film is cast on one inch Killion Mini Cast Film Line, Model KLB 100, having a thickness of about 3 mils of a film, such that A / B / C three layers in each layer is about 1 mil thick.

这些薄膜进行了两种试验,表2-7给出了试验结果。 These films were two tests, the test results are given in Table 2-7.

1)在DTC Model 52D Hot Tack Tester上用以下标准和设定进行热粘着力试验:样品宽度15毫米,热合面深5毫米横过薄膜横向(TD)热合,并沿纵向(MD)引出。 1) On the DTC Model 52D Hot Tack Tester with the following standards and settings were heat adhesion test: Sample width 15 mm, depth 5 mm heat seal across the surface of the film transverse direction (TD) heat, and the longitudinal direction (MD) leads.

热合压力=5巴(72磅/英寸2)热合时间=0.5秒延迟时间(热合棒开启到热合试验的时间)=0.4秒热粘性强度值为试验过程中测得的8个最高负荷的平均值。 Heat sealing pressure = 5 bar (72 lbs / in2) heat time = 0.5 seconds delay time (heat sealing bar open to the heat test of time) mean = 0.4 seconds hot tack strength value during the test measured eight highest load . 表中的每一数值是3-5次试验的平均值。 Each value in the table is the average of 3-5 experiments.

2)在Theller Model EB实验室热合机上由薄膜进行热合强度试验。 2) On the Theller Model EB laboratory heat sealing machine for heat sealing a film strength test. 约1秒压合时间和5巴(72磅/英寸2)热合压力用于热合。 Pressing time of about one second and 5 bar (72 lbs / in2) heat for heat stress. 沿横向热合并纵向拉出。 Pull along vertical transverse heat merger. 热合样品为12.7厘米(5英寸)宽,0.95厘米(3/8英寸)厚。 Heat-sealing sample was 12.7 cm (5 inches) wide, 0.95 cm (3/8 inch) thick. 热合面在United 6 Station Tensile Tester上以50.8厘米/分钟(20英寸/分钟)应变速率(剥离速度)用5.08厘米(2英寸)颚式固定夹具拉出。 Heat sealing surface on the United 6 Station Tensile Tester to 50.8 cm / min (20 inches / minute) strain rate (peel speed) with a 5.08 cm (2 inches) jaw fixture pulled out. 样品切成2.54厘米(1英寸)宽的片,用于热合强度试验。 Sample was cut into 2.54 cm (1 inch) wide pieces for heat seal strength test. 样品的自由端固定在颚式固定夹上,然后在这一应变速率下分开颚式固定夹一直到热合面破坏。 The free end of the sample is fixed in the jaw retaining clip, and then separate the jaw retaining clip until heat surface damage at the strain rate. 对于本发明说明书来说,峰值热粘着力为所达到的最高热粘强度。 For the present description of the invention, the adhesion of the heat peak of the highest hot tack strength.

3)表中的热合剥离/撕裂值是在热合试验过程中热合面破坏的量度。 3) a heat seal peel table / Tear value is a measure of the heat seal surface of the test damaged during heat sealing process. 剥离表示热合面剥离开,也就是热合面本身在薄膜层之间沿界面分开。 Peel peeled apart, said heat sealing surface, that is, heat sealing surface itself apart along the interface between the film layers. 撕裂表示在热合的一边薄膜破坏,但热合面仍完好。 Tear in the side of the film, said heat damage, but the heat sealing surface is still intact. 剥离一撕裂表示在试验过程中一些样品剥离和一些样品撕裂或一些样品开始剥离然后撕裂。 Peeling a tear during the test indicates some samples peeled and some samples or some samples began to peel tear and tear. 表中的每一数值为2-5个样品的平均值。 Each value in the table is the average of 2-5 samples.

对应于每一表有一代表性的图。 Each table has a corresponding representation in FIG.

图1对应于表2,图2对应于表3;图3对应于表5的聚合物1和图4对应于表6的聚合物1;图5对应于表5的聚合物2和图6对应于表6的聚合物2;图7对应于表5的聚合物3和图8对应于表6的聚合物3。 Polymer Figure 3 corresponds to Table 5, Polymer 1 and Figure 4 corresponds to Table 6, 1;; Figure 1 corresponds to Table 2, Table 3 in Figure 2 corresponds to Figure 5 corresponds to Table 5 of the corresponding 6 Polymer 2 and FIG. Polymer 6 in Table 2; Fig. 7 corresponds to Table 5, Polymer 3 and Figure 8 corresponds to Table 6 Polymer 3.

在图3-8中,由表1和2中的数据得出表示Surlyn/Surlyn、Surlyn/Dowlex和Dowlex/Dowlex薄膜的曲线。 In Fig. 3-8, by the data in Tables 1 and 2 derived graph Surlyn / Surlyn, Surlyn / Dowlex and Dowlex / Dowlex film.

由表2-7和图1-8可看出,当聚合物1-4热合到离聚物上时,它们在较低的热合温度下显示出高的热粘性和良好的热合强度。 1-8 can be seen in Table 2-7 and Fig., When the polymer is thermally bonded to the ionomer 1-4 on, they exhibit high hot tack and good heat seal strength at low heat sealing temperature. 这些结果与传统的LLDPE热合到离聚物上得到的结果有很大和意想不到的区别。 These results with the conventional heat sealing to the LLDPE copolymer obtained from the result of the great and unexpected difference.

如图1所示(为了对比在图3、5和7中重新绘出)离聚物((Surlyn 1652)本身热合(空心圆圈)和传统的LLDPE(Dowlex2056)本身热合(空心方块)两者都有高的热粘性,尽管在LLDPE例中需要更高的热合温度。当离聚物热合到传统的LLDPE(短划线)上时,测量得很低的热粘性。这两个不相容聚合物的峰值热粘性比它们本身热合的峰值热粘性低5倍。 Figure 1 (For comparison redrawn in Fig. 3, 5 and 7) ionomer ((Surlyn 1652) heat itself (open circles) and conventional LLDPE (Dowlex2056) heat itself (open squares) both high hot tack, although LLDPE embodiment requires a higher heat-sealing temperature. When the heat sealing ionomer to conventional LLDPE (dashes), the measurement of very low hot tack of these two incompatible polymerization peak heat stickies heat seal itself is lower than the peak hot tack them five times.

图1清楚地说明当聚合物4热合到离聚物上(实心圆圈)时,它有优良的热粘性。 Figure 1 clearly shows when the polymer is 4 to heat the oligomer (solid circle) is away, it has excellent hot-tack. 在这种情况下,聚合物4对离聚物的热粘性基本上与离聚物本身热合的热粘性相当。 In this case, four pairs away from the hot tack polymer copolymer ionomer itself is substantially heat hot tack fairly.

对于聚合物1,图3给出了类似的一组热粘性比较。 For polymers 1, Figure 3 shows a similar set of hot tack comparisons. 同样,聚合物1对离聚物热合(实心圆圈)有与离聚物自身热合基本上相同的峰值热粘性,但在较低的温度下达到。 Similarly, one pair of ionomer polymer heat seal (filled circles) and ionomers have their own heat substantially the same peak hot tack, but reached at a lower temperature.

在图5中示出聚合物2的热粘性能(空心三角)。 In Figure 5 is shown heat-adhesive properties of the polymer 2 (open triangles). 聚合物2的热粘性与传统的LLDPE大约相同,但聚合物2对离聚物(实心圆圈)的热粘性几乎比传统LLDPE对离聚物(短划线)热合的热粘性大3倍。 Polymer hot tack two conventional LLDPE with about the same, but two pairs of ionomer polymer (solid circles) than conventional hot tack almost LLDPE ionomer (dash) heat hot tack three times larger.

图7表示聚合物3对离聚物热合(实心圆圈)有极好的热粘性。 Figure 7 shows three pairs of ionomeric polymer heat-seal (closed circles) is excellent in hot tack.

图2表示与用来得到图1所示的热粘性曲线的相同的一组聚合物薄膜的热合强度随热合温度的变化。 Figure 2 shows the hot tack is used to obtain the curve shown in Fig. 1 the same set of polymer film heat seal strength with heat sealing temperature. 所有三种聚合物(聚合物4、离聚物、传统LLDPE)当本身热合时的最大热合强度是相等的。 All three polymers (Polymer 4, ionomer, the conventional LLDPE) when their maximum heat timely heat seal strength are equal. 传统的LLDPE比其他聚合物有更高的热合初始温度。 Conventional LLDPE has a higher initial temperature than the other heat-sealable polymer. 当传统的LLDPE热合到离聚物上时,一直到较高的热合温度都才达到最高平台热合强度;而在相当低的热合温度下聚合物4对离聚物热合就达到其最大强度。 When the conventional LLDPE heat sealing ionomer to the time until the higher heat seal temperatures to reach the highest platform heat seal strength; and at a relatively low heat sealing temperature of the polymer 4 pairs of heat sealing ionomer reached its maximum strength. 聚合物4对离聚物和传统的LLDPE对离聚物和传统的LLDPE对离聚物热合的较低的最高热合强度是由于它们的剥离破坏方式与撕裂方式,如表4所示。 Polymer four pairs of ionomer and ionomer traditional LLDPE LLDPE and traditions of the ionomer lower heat highest heat seal strength is due to the destruction of their way of stripping and tearing mode, as shown in Table 4.

图4、6和8表明,当聚合物1、2或3热合到离聚物上时,得到类似的热合性能。 Figures 4, 6 and 8 show that when two or three heat sealing polymer to the ionomer, you get a similar heat sealing properties. 在所有这些情况下,在比传统LLDPE对离聚物热合的情况低得多的热合温度下得到最高热合强度。 In all these cases, much more than in the case of conventional LLDPE to an ionomer heat of a low heat-sealing temperature to give the maximum heat seal strength.

本发明的薄膜可在食品接触和非食品接触应用中适用作可收缩薄膜、自粘薄膜、拉伸薄膜、热合薄膜、取向薄膜、快餐包装、重载袋、食品袋、烘烤和冷冻食品包装、药品包装、工业衬、薄膜等。 Film of the invention may be in contact with food and non-food contact applications useful as shrinkable films, self-adhesive film, stretched film, heat sealing films, oriented films, snack packaging, heavy duty bags, food bags, baked and frozen food packaging , pharmaceutical packaging, industrial liners, films and the like. 制纤维操作包括熔体纺丝、溶液纺丝和熔体吹塑纤维操作。 Made fiber operations include melt spinning, solution spinning and melt blown fiber operations. 这样的纤维可用于纺织或无纺形式制成滤布、卫生巾织物、医用外衣、生理织物(geotexfiles)等。 Such fibers may be used in the form of woven or non-woven cloth made of, sanitary napkins fabrics, medical coat, physiological fabric (geotexfiles) and the like. 一般挤型制品包括医药管道、金属丝和电缆涂层、土木用膜和槽衬。 General extrusion products, including pharmaceuticals pipes, wire and cable coatings, civil engineering and tank lining membrane. 成型制品包括单层和多层结构瓶、罐、大型空心制品、硬质食品容器、玩具等。 Molded products, including single and multi-layer structure bottles, cans, large hollow articles, rigid food containers and toys.

虽然已参考具体的实施方案描述和说明了本发明,但熟悉本专业的一般技术人员会理解,本发明适用于各种改变,在这里不一定说明。 Although reference to specific embodiments of the invention described and illustrated, but generally skilled in the art will appreciate that the present invention is applicable to all kinds of changes described here are not necessarily. 例如,本申请的薄膜加入添加剂或与其他聚合物共混或共挤塑或甚至将本申请的薄膜层压到其他材料上如金属箔、纸、其他聚合物膜上等都不超出本发明的范围。 For example, the present application film additives or blended with other polymers or coextruded or even laminated thin film of the present application to other materials such as metal foils, paper, other polymer films of the present invention, are not exceeded range. 由于这一原因,为了确定本发明的真正的范围,只能参照附后的权利要求书。 For this reason, in order to determine the true scope of the invention, only after reference to appended claims.

表1 Table 1

表2 Table 2

试验条件:样品宽度=15毫米 热合压力=5巴(72磅/英寸2)热合时间=0.5秒 延迟时间=0.4秒剥离速度=200毫米/秒表3 Test conditions: Sample width = 15 mm heat sealing pressure = 5 bar (72 lbs / in2) heat time = 0.5 seconds delay time = 0.4 seconds peeling speed = 200 mm / stopwatch 3

试验条件:样品宽度=2.54cm(1英寸) 热合压力=5巴(72磅/英寸2)热合时间=0.1秒剥离速度=50.8厘米/分钟(20英寸/分钟) Test conditions: sample width = 2.54cm (1 in) heat-sealing pressure = 5 bar (72 pounds / inch 2) the heat seal time = 0.1 seconds peeling speed = 50.8 cm / min (20 inches / minute)

表4 Table 4

试验条件:样品宽度=2.54cm(1英寸) 热合压力=5巴(72磅/英寸2)热合时间=1.0秒剥离速度=50.8厘米/分钟(20英寸/分钟) Test conditions: sample width = 2.54cm (1 in) heat-sealing pressure = 5 bar (72 pounds / inch 2) the heat seal time = 1.0 seconds peeling speed = 50.8 cm / min (20 inches / minute)

表5 Table 5

试验条件:样品宽度=15毫米 热合压力=5巴(72磅/英寸2)热合时间=0.5秒 延迟时间=0.4秒剥离速度=200毫米/秒表6 Test conditions: Sample width = 15 mm heat sealing pressure = 5 bar (72 lbs / in2) heat time = 0.5 seconds delay time = 0.4 seconds peeling speed = 200 mm / stopwatch 6

试验条件:样品宽度=2.54厘米(1英寸) 热合压力=5巴(72磅/英寸2)热合时间=1.0秒剥离速度=50.8厘米/分钟(20英寸/分钟) Test conditions: sample width = 2.54 cm (1 inch) heat-sealing pressure = 5 bar (72 pounds / inch 2) the heat seal time = 1.0 seconds peeling speed = 50.8 cm / min (20 inches / minute)

表7 Table 7

试验条件:样品宽度=2.54厘米(1英寸) 热合压力=5巴(72磅/英寸2)热合时间=1.0秒剥离速度=50.8厘米(20英寸/分钟) Test conditions: sample width = 2.54 cm (1 inch) heat-sealing pressure = 5 bar (72 pounds / inch 2) the heat seal time = 1.0 seconds peeling speed = 50.8 cm (20 inches / minute)

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