CN100333902C - 热层压制品的制备及其设备 - Google Patents
热层压制品的制备及其设备 Download PDFInfo
- Publication number
- CN100333902C CN100333902C CNB2004100376459A CN200410037645A CN100333902C CN 100333902 C CN100333902 C CN 100333902C CN B2004100376459 A CNB2004100376459 A CN B2004100376459A CN 200410037645 A CN200410037645 A CN 200410037645A CN 100333902 C CN100333902 C CN 100333902C
- Authority
- CN
- China
- Prior art keywords
- coating
- carrier film
- supporting carrier
- adhesive resin
- film coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
- A01C1/02—Germinating apparatus; Determining germination capacity of seeds or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/10—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using hot gases (e.g. combustion gases) or flames coming in contact with at least one of the parts to be joined
- B29C65/106—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using hot gases (e.g. combustion gases) or flames coming in contact with at least one of the parts to be joined using flames coming in contact with at least one of the parts to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
- B29C65/1432—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface direct heating of the surfaces to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
本发明涉及一种通过粘合剂树脂涂层将第一支持体薄膜涂层层压至第二支持体薄膜涂层的热层压制品的制备方法,其特征在于:将所述粘合剂涂层与所述第一支持体薄膜涂层结合,在氧气存在条件下,用热辐射加热所述粘合剂树脂涂层的表面,引入可增加粘度的功能性基团,然后,将第二支持体薄膜涂层叠加在所述粘合剂树脂涂层之上并通过压力使之粘接。所述热层压制品不需要用溶剂即具有强的层合力,并且具有极佳的安全性和食品卫生。
Description
技术领域
本发明涉及一种通过一个粘合树脂涂层将第一支持体薄膜涂层层压至第二支持体薄膜涂层上的包装材料及其设备。
背景技术
目前为止,广为应用的将第一支持体薄膜涂层层压至第二支持体薄膜涂层的代表性方法是挤出层压和干燥层压。挤出层压包括在第一支持体薄膜涂层上涂布一固定涂布液,如在溶剂中溶解亚胺基或尿烷基形成的涂布液,然后干燥,再在其上挤压叠合第二支持体薄膜涂层(荒木正义“层压方法手册”,PP25-32,加工技术研究会,1978)。干燥层压包括在第一支持体薄膜涂层上涂布粘合剂,如溶解在溶剂的尿烷粘合剂,然后干燥,再在其上叠合压制第二支持体薄膜涂层(同上,PP14-18)。
另外,关于不用溶剂的层压,有多羟基异氰酸盐型非溶剂层压和热熔层压。非溶剂层压包括在第一支持体薄膜涂层上涂布加热后其粘度降低的非溶剂型粘合剂树脂,然后在其上层压第二支持体薄膜涂层(同上,PP19-22)。
但是,在上述挤出层压和干燥层压方法中,为了溶解粘合剂,需要大量使用有机溶剂,如乙酸乙酯、甲苯或异丙醇,而且会在工作时造成有毒气味,恶化工作环境并且有爆炸的危险。另外,有机溶剂还会污染工厂周围的环境致使工厂迁移至郊区,以及因而导致更严格的规定。溶剂的蒸发导致能源消耗。而且除非溶剂完全蒸发,溶剂的气味还会留在涂层中。特别是,如果是用于包装食物,在食物卫生方面也会有问题。
至于挤出层压,尽管由于快速制造速度而有良好的产率,但与干燥层压相比,其层压的强度要差一些。所以它不适合消毒食品的包装材料。
另一方面,在干燥层压方法中,层压强度最高,大量用于沸腾食品和消毒食品的包装材料。但是与挤出层压相比,其产率低,并且聚尿烷粘合剂的老化必需在40℃-70℃的温度控制室中存放2-7天才能完成,这需要很大的温度控制室和很大的能量消耗。而且,用作老化剂的二异氰酸甲苯(TD1)有转变成具说是致癌物的甲苯二胺(TDA)的危险。为了避免这种危险,老化剂TD1改为老化速度低的脂肪异氰酸盐时,没有老化的聚尿烷粘合剂树脂就会渗入消毒食品,造成异味和臭味并且从食品卫生的角度看也不利。
在上述非溶剂层压和热熔层压方法中,为了适于涂布,涂布液的粘度必须低,而且这种对于粘度的限制也要求粘合剂树脂的分子量要低。结果,造成层压的强度比干燥层压的要低得多。因此,热熔层压经常用于制备容易剥离的材料。
另外,在非溶剂层压和热熔层压方法中,由于粘合剂树脂在熔融状态下涂布,在涂布时容易发生问题,如凝固。
本发明概述
如上所述,本发明的目的之一是解决挤出层压和干燥层压中溶解粘合所用溶剂引起的问题。即解决有毒气味和工作环境卫生,爆炸危险,环境污染,针对各种限制采取的措施,残留溶剂的气味以及能源浪费问题。另外,本发明开发了一种不需要温度控制室、不需要大量能源浪费、也不需要干燥层压中的老化时间并且可以获得具有极佳完全性和食品卫生保证的层压方法。
本发明的另一目的是开发一种解决非溶剂层压和热熔层压中的涂布问题的层压方法,该方法获得的涂层强度比挤出层压、非溶剂层压和热熔层压制备的层压制品的强度都高,并且与干燥层压方法制备的层压制品的强度相当。
为了达到上述目的,本发明人努力研究了无需溶剂的粘合剂树脂层压方法,发现当通过热辐射加热将粘合剂树脂涂层与第一支持体薄膜涂层层压在一起时,再在其上压制第二支持体薄膜涂层,该第二支持体薄膜涂层可以与第一支持体薄膜涂层强烈粘合在一起,从而完成本发明。
因此,本发明提供了一种通过粘合剂树脂涂层将第一支持体薄膜涂层层压至第二支持体薄膜涂层的热层压制品的制备方法,其特征在于:
将粘合剂涂层与第一支持体薄膜涂层结合,
在氧气存在条件下,用热辐射加热粘合剂树脂涂层的表面,引入可增加粘度的功能性基团,然后,
将第二支持体薄膜涂层叠加在粘合剂树脂涂层之上并通过压力使之粘接。
在上述方法中,由于是在氧气存在条件下用热辐射加热粘合剂树脂涂层的表面,粘合剂树脂涂层的双键位置在加热状态下被氧化形成具有强烈粘结力的功能基团,如羧基、醛基及羟基。在此状态下,第二支持体薄膜涂层叠合层压至粘合剂树脂涂层,所以,第二支持体薄膜涂层与第一支持体薄膜涂层发生强烈粘结。
本发明还提供了制备热层压制品的设备,包括,
用于传送第一支持体薄膜涂层和粘合剂树脂涂层结合在一起的层压制品的第一传送装置,
用于传送第二支持体薄膜涂层的第二传送装置,
通过热辐射对所述第一传送装置传送的层压制品的粘合剂涂层进行加热的加热装置,以及
用于将所述第二传送装置传送的所述第二支持体薄膜涂层粘结的粘结装置。
在上述设备中,所述加热装置加热第一传送装置传送的层压制品的粘合剂涂层表面,使之产生具有强烈粘结力的功能性基团如羧基、醛基及羟基。所述粘结装置将所述第二支持体薄膜涂层叠合层压至粘合剂树脂涂层从而使第二支持体薄膜涂层与第一支持体薄膜涂层发生强烈粘结。
附图的简要说明
图1是制备本发明具体热层压制品所用设备的结构示意图。
本发明的详细说明
第一支持体薄膜涂层可以是任何可以通过加热与粘合剂树脂涂层层压叠合的材料制成。由于组成粘合剂涂层的基本树脂是乙烯基树脂,组成第一支持体薄膜涂层的基本树脂可与粘合剂树脂涂层粘结,特别是与乙烯基树脂涂层粘结。优选树脂包括烯烃基聚合物,特别是乙烯基聚合物如低、中、高密度聚乙烯树脂,L-LDPE树脂,乙烯共聚物树脂如乙烯-丙烯共聚物树脂、乙烯-丁烯共聚物树脂等。第一支持体薄膜涂层可以是两个或多个涂层并且可以是单轴或双轴拉伸薄膜以及非拉伸薄膜。第一支持体薄膜涂层的适当厚度为10-150μm,优选20-100μm。
粘合剂涂层由乙烯基聚合物形成,如乙烯齐聚物或共聚物。优选的乙烯齐聚物是高压低密度聚乙烯,这是因为其富有易于被氧化的双键和支链。优选的乙烯共聚物之一是L-LDPE,因为它有易于被氧化的短的支链。除了L-LDPE以外的优选乙烯共聚物是乙烯-不饱合羧酸酐-不饱合羧酸酯共聚物,乙烯-不饱合羧酸酯共聚物以及乙烯-乙烯基酯共聚物。不饱合羧酸酐的实施例包括马来酸酐,衣康酸酐,柠康酐以及十二琥珀酸酐。不饱合羧酸酯的实施例包括甲乙酸酯,甲基丙烯酸脂或丙烯酸脂,乙基丙烯酸酯或丙烯酸脂,丙基丙烯酸酯或丙烯酸脂,丁基丙烯酸酯或丙烯酸脂,甲基延胡索酸酯,乙基延胡索酸酯,丙基延胡索酸酯,丁基延胡索酸酯,甲基马来酸酯,乙基马来酸酯,丙基马来酸酯和丁基马来酸酯。乙烯基酯的实施例包括乙烯基乙酸酯,乙烯基丙酸酯。两种或多种共聚用单体可以组合形成乙烯共聚物,并且两种或多种乙烯共聚物可以混合。
粘合剂树脂涂层优选熔点低于第一支持体薄膜涂层,因为所述粘合剂树脂涂层的表面通过加热与所述第一支持体薄膜涂层整合然后与第二支持体薄膜涂层层压。当粘合剂树脂涂层的熔点等于或高于第一支持体薄膜涂层的熔点时,要想使粘合剂树脂涂层粘结并使之热折叠或粘合在轴辊上,就必须将粘合剂树脂涂层加热至高温。所述粘合剂涂层的合适熔点为低于第一支持体薄膜涂层10℃以上,最好20℃以上。为了达到此目的,优选使用前述低熔点的乙烯共聚物,特别是乙烯-不饱合羧酸酐-不饱合羧酸酯共聚物,乙烯-不饱合羧酸酯共聚物以及乙烯-乙烯基酯共聚物。另一方面,粘合剂树脂涂层的熔点太低也不利,因为满足不了包装材料对耐热的要求。考虑到这一点,粘合剂树脂涂层的熔点优选50℃以上,最好55℃以上。
如上所述,尽管需要在低温下粘合,某些包装材料需要具有耐热性以便能够抵抗热处理如高温贮存或煮沸。在此情况下,优选的办法是将熔点为100℃以上的聚合烯烃和熔点为110℃以上的最好是120℃以上的粘合剂树脂涂层混合打底。聚合烯烃在粘合剂树脂涂层中的混合量为不超过70wt.%,优选不超过50wt.%,更优选不超过30wt.%,并且优选不低于5wt.%。混合量超过70wt.%就不好了,因为会导致与第二支持体薄膜涂层的粘结强度减弱。熔点为100℃以上的聚烯烃的实施例包括高压低密度聚乙烯,线性低密度聚乙烯,中密度聚乙烯,高密度聚乙烯,聚丙烯,聚-4-甲基-1-戊烯等。
为了改善耐热性,优选加入一个熔点为130℃以上的聚烯烃组成的耐热涂层,使涂层结构为第一支持体薄膜涂层/耐热涂层/粘合剂树脂涂层/第二支持体薄膜涂层/第二支持体薄膜涂层。熔点为130℃以上的聚烯烃的实施例包括高密度聚乙烯,聚丙烯,聚-4-甲基-1-戊烯等,并且高密度聚乙烯是特别优选,因为其与粘合剂树脂涂层的强粘结力。耐热涂层的合适厚度为1-100μm,优选3-20μm。
改进耐热性的另一种措施是将含有不饱合羧酸酐乙烯-共聚物与含有多羟基的化合物混合使之发生交联反应。乙烯共聚物的熔点低于第一支持体薄膜涂层,并且包括前述乙烯-不饱合羧酸酐-不饱合羧酸酯共聚物。为了使交联反应改进耐热性,所述含有多羟基的化合物的量不超过50wt.%,优选不超过30wt.%,并且不低于5wt.%,优选不低于10wt.%。量超过50wt.%就不好了,因为会导致与第二支持体薄膜涂层的粘合力减弱。
含有多羟基的化合物的实施例包括部分皂化的乙烯-乙烯基乙酸酯共聚物,乙烯-乙烯醇共聚物,聚乙烯醇,乙烯基乙二醇,丙三醇,1,4-丁二醇,1,6-己烷二醇,1,8-庚烷二醇,1,10-十二烷二醇,三羟甲基甲烷,三羟甲基乙烷,三羟甲基丙烷,季戊四醇,二乙烯乙二醇,三乙烯乙二醇,四乙烯,聚乙烯乙二醇,二丙三醇,三丙三醇等。
另外,通过在其中加入金属盐,可以提高交联的速度,并且可以防止形成共挤塑薄膜或可回收的薄膜,明胶。所述金属盐的合适量为不超过20wt.%,优选不超过10wt.%,并且不低于0.01wt.%,优选不低于0.1wt.%。金属盐的量超过20wt.%就不能使交联反应加速了,并且还会降低树脂强度。金属盐的实施例包括饱合或不饱合的脂肪酸如月桂酸锂,月桂酸钠,月桂酸钙,月桂酸铝,肉豆蔻酸钾,肉豆蔻酸钠,肉豆蔻酸铝,棕榈酸钠.,棕榈酸锌,棕榈酸镁,硬脂酸钠,硬脂酸钾,硬脂酸钙,硬脂酸锌,硬脂酸钠,离子交联聚合物等。
粘合剂树脂涂层的合适厚度为1-40μm,优选2-30μm。尽管从成本考虑,粘合剂树脂涂层越薄越好,但当厚度小于1μm时,由于挤压涂布机的共挤塑性和涂层性能,很难保持整体的均一性。
为了使粘合剂树脂与第一支持体薄膜涂层形成整体,可以通过挤压涂布机将它们共挤压涂布,也可以将粘合剂树脂涂层涂布在第一支持体薄膜上。
然后,在氧气存在条件下,通过热辐射加热使第一支持体薄膜涂层的表面与粘合剂树脂涂层之间快速层合在一起。通过加热,粘合剂树脂涂层中的分子的双键断开并且被空气中的氧气氧化,形成供粘接的功能性基团如羰基(-COOH),其中间物醛基(-CHO)以及羟基(-OH)。加热温度至少要使粘合剂树脂涂层表面熔化,即高于熔化点温度如高于熔化点10℃以上,优选熔化点20℃以上-50℃。合适的加热方法包括红外加热和火焰。
在红外加热时,红外线可以分为短波范围(1.0-2.0μm),中波范围(2.0-3.5μm),长波范围(3.5-5.0μm),由于中波范围红外线被粘合剂树脂涂层有效吸收,优选中波范围红外线。本发明中,快速加热很重要,集中熔化粘合剂树脂涂层表面,并且为此目的,用一个凹透镜或其它将红外线集中提高效率,优选对准粘合剂树脂涂层表面。这样一种非接触型辐射加热可以有效提高制备速度。
在火焰加热的情况下,可以用常规的火焰加热方法,以便满足上述条件。
另一方面,仅仅用电晕放电,还不能达到本发明改进层压强度的效果,因为粘合剂树脂涂层表面的熔化不充分。
加热在有氧条件下进行。可以是空气中的氧气,为了增加功能基团的产生,最好对加热的粘合剂树脂涂层表面吹佛臭氧。
经过热处理,与第二支持体薄膜涂层的层压强度提高1-12N/15mm宽,通常提高3-9N/15mm宽。
其次,当被加热的粘合剂树脂涂层仍处于热状态时将第二支持体薄膜涂层与之叠合并加压使它们粘结。
所述第二支持体薄膜涂层可以由任何能够与粘合剂树脂涂层层合的材料制成,并且根据热层压制品的用途选择。第二支持体薄膜涂层的实施例包括聚酯薄膜,如PET和PEN,聚烯烃薄膜,如高密度聚乙烯,聚丙烯,聚丁烯,聚酰胺薄膜,及其拉伸薄膜,其经过金属处理的薄膜,以及铝箔。优选PET,铝沉积PET,定向聚丙烯(OPP),定向尼龙(O-NY)以及铝箔。第二支持体薄膜涂层可以是两个或多个涂层。第二支持体薄膜涂层的度为5-50μm,通常为7-30μm。
第一支持体薄膜涂层,粘合剂树脂涂层以及第二支持体薄膜涂层可以含有抗氧化剂,润滑剂,阻燃剂,防粘连剂,填充剂,着色剂以及各种稳定剂等等。
叠层的压制可以通过挤压辊使第二支持体薄膜涂层与粘合剂树脂涂层粘结。合适的挤压压力为0.1-100千克-厘米,优选1-50千克-厘米的线性压力。为了便于粘结,所述挤压压力不能高,但合适的压力可以去除膨胀起皱。
本说明书中的热层压制品的意思是通过加热层压形成的层压制品。因此,制成的热层压制品可以用作各种物品如食品和药品的包装材料,尤其适用于蒸煮食品和蒸馏食品的包装材料。
下面,介绍一下制造热层压制品所用的设备。
图1是制造本发明具体热层压制品所用设备的结构示意图。图中,11表示作为第一传输装置的第一传输辊,它用于传输由第一支持体薄膜涂层1和粘合剂树脂涂层2相互叠合在一起形成的层制品3。21表示作为第二传输装置的第二传输辊,它用于传输第二支持体薄膜涂层4。30表示加热部分,用于加热上述层制品中的粘合剂树脂涂层2的表面。40表示粘结装置,用于通过加压使所述第二支持体薄膜涂层4与粘合剂树脂涂层2粘结。
12、13和14表示引导所述层压制品3通过加热部分到达所述粘结装置的导辊,并且导辊14位于所述加热部分30附近以便使层压制品3在所述加热部分30加热。22和23是使所述第二支持体薄膜涂层4引导至粘结装置40的导辊。
在加热部分30中,若干红外加热头31在与层压制品3移动方向垂直排列。每一个红外加热头31提供一个凹面反射镜32,并且红外线被凹面反射镜32反射并聚焦在所述粘合剂树脂涂层2的表面。所述红外加热头31被设计成当所述设备被意外事故等造成停车时会自动关闭。
在加热部分30的入口处,所述红外加热头31附近设有冷却空气嘴33。当红外加热头31关闭时,所述冷却空气嘴工作,向所述粘合剂树脂涂层2的表面吹佛冷空气。
所述粘结装置40上设有挤压辊41和加热辊42,并且它们被设计成当在其间通过时,所述第二支持体薄膜涂层4与所述被加热的层压制品3接触并加压使之强烈粘结。43是挤压辊41的备用辊。51和52导辊,用于将所述第二支持体薄膜涂层4与所述层压制品3粘结所形成的热层压制品5传输至下一步。
用上述设备制造热层压制品时,层压制品3通过所述第一传输辊11传输。所述层压制品3依次通过导辊12、13和14,并且在加热部分30被直接从红外加热头31发出的和被凹面反射镜32反射的红外线有效地和急剧地加热。结果,在所述粘合剂树脂涂层2上有效形成可用于粘合的功能基团。
另一方面,所述第二支持体薄膜涂层4通过所述第二传输辊21传输,并且通过导辊22、23传输至所述粘结装置40。然后,所述第二支持体薄膜涂层4与所述经过加热的层压制品3在所述粘结装置40的挤压辊41处接触并相互叠合,然后通过挤压辊41和加热辊42压紧粘合。结果,所述第二支持体薄膜涂层4通过所述粘合剂树脂涂层2与所述第一支持体薄膜涂层1紧紧粘结,形成热层压制品5。所述热层压制品5通过所述导辊51、52等传送至下一步。
实施例
按下述步骤将粘合剂树脂涂层与第一支持体薄膜涂层层合形成层压制品:
使用由一个主挤压机(90mmΦ)和两个副挤压机(50mmΦ)(由现代机械有限责任公司制造)组成的三涂层共挤压机。在所述主挤压机和所述其中一个副挤压机中加入聚乙烯树脂(“NC574R”,日本聚烯烃有限公司制造),所述另外一个副挤压机中加入粘合剂树脂(“Rexpesrl ET 184M”,日本聚烯烃有限公司制造)。然后,在240℃下挤出所有的树脂,形成所述层压制品,其由两个宽度为1000毫米厚度为70μm的聚乙烯树脂薄膜作为所述第一支持体薄膜涂层并且宽度为1000毫米厚度为20μm的聚乙烯-马来酸酐-乙基丙烯酸酯共聚物树脂涂层作为所述粘合剂树脂涂层。
然后,将第二支持体薄膜涂层与上面所述第一支持体薄膜涂层和所述粘合剂树脂涂层组成的层压制品进行层压,形成热层压制品。所述热层压制品的制造设备如图1所示。所用的红外加热头31是九个1300毫米长、3.2千瓦中型红外加热头(海莱屋斯株式会社(heraeus K.K))。所述导辊13和14加热至30℃,所述加热辊42加热至100℃。
然后,分别地,由第一支持体薄膜涂层1和粘合剂树脂涂层2组成的层压制品3从所述第一传输辊11传输,第二支持体薄膜涂层2被从所述第二传输辊21传输。层压制品3和第二支持体薄膜涂层4的传输速度,即热层压制品5的制造速度为150米/分钟。通过辐射温度计测量可知,用红外加热头31加热后的层压制品3的粘合剂树脂涂层2的表面温度达500-650℃。挤压辊41的线性压力为24千克-厘米。
用红外加热头加热后粘合剂树脂涂层表面中功能性基团如-COOH,-CHO以及-OH的量可以通过X-射线光电子光谱复制的方法(XPS)测量碳原子和氧原子的含量而得到,并且发现加热后氧原子的含量与加热前相比大大增加。其数据见下表1。
表1
加热前 | 加热后 | |||
侧1 | 中心 | 侧2 | ||
C-含量 | 97.63 | 90.29 | 90.55 | 91.21 |
O-含量 | 2.37 | 9.71 | 9.45 | 8.97 |
作为第二支持体薄膜涂层4,三涂层型薄膜涂层,即厚度为12μm的聚乙烯对苯二酸酯(PET)薄膜,厚度为15μm的定向尼龙(O-NY)薄膜,以及厚度为12μm的铝沉积PET薄膜是易于测试的三涂层型热层压制品。
测量所述三涂层型热层压制品的层压强度和剥离强度,其结果如表2所示:
表2
PET | O-NY | Al-PET | |
层压强度(N/15mm宽) | 7.0 | 7.4 | 6.0 |
剥离强度(N/15mm宽) | 41.1 | 46.7 | 26.4 |
层压强度的测量
沿着传输方向将每个热层压制品裁成15mm宽的窄条,用手将一端剥开,所述第二支持体薄膜涂层与所述第一支持体薄膜涂层分开。用常速拉力器的上夹盘和下夹盘固定剥离部分的两端。两个夹盘的初始距离为50毫米。以300毫米/分钟的速度进行T-剥离实验,保持未剥离部分水平状态,显示的层压强度的平均值为5倍。
剥离强度的测量
按照JIS Z 1707测量。
拉力速度为300毫米/分钟,初始长度为50毫米。
通过上述结果,可以确认,本发明获得的层压强度和剥离强度等于或高于那些由双组分卷曲型聚亚安酯粘合剂、涂布速度为:3.0克/平方米作为固体重量、层压后在40℃下老化4天的干燥层压方法所制造的层压制品,特别是,铝沉积PET薄膜的层压强度比2.0-3.0N/15mm宽的干燥层压法制造的层压制品要高得多。一般来说,铝沉积PET薄膜的层压强度不是第一支持体薄膜涂层与第二支持体薄膜涂层之间的层压强度,而是铝沉积膜从PET表面剥离的剥离强度。在本发明的热层压制品中,改善了铝在PET薄膜上的沉积强度。
因此制造的热层压制品,其中的第二支持体薄膜涂层为O-NY,很容量按照日本药典进行渗出试验,以及测量紫外吸收(-logT)。在对比例中,还测量了用含有一个脂族异氰酸酯的聚亚安酯粘合剂制造的层压制品(O-NY 15μm/聚亚安酯粘合剂3克/平方米/聚乙烯80μm)。结果见表3。
表3
紫外吸收(-logT) | ||
220-240nm | 241-250nm | |
热层压制品(O-NY 15μm/粘合剂20μm/PE 70μm | 0.03 | 0.01 |
聚亚安酯层压制品(O-NY 15μm/聚亚安酯粘合剂3克/平方米/PE 80μm) | 0.13 | 0.06 |
上述吸收在上述波长范围内是最大值。
紫外吸收的测量
按照日本药典第13修订版进行测量。即将热层压制品和聚亚安酯粘合剂层压制品制成袋子(内部面积:600平方厘米),在每个袋子中装200毫升蒸馏水,然后密封。在70℃萃取24小时,再测量蒸馏水的紫外吸收。
从上述结果可以看出,热层压制品袋子中的蒸馏水的紫外吸收比亚安酯粘合剂层压制品袋子中的蒸馏水的紫外吸收要小得多,这表明从热层压制品中萃取的有机物质比从聚亚安酯粘合剂层压制品中萃取的有机物质要少得多。因此,可以确认,从食品卫生的角度看,本发明的热层压制品比常规的聚亚安酯粘合剂层压制品更安全,包装食品染上异味和臭味的机会小。如果是聚亚安酯粘合剂层压制品,人们认为未硫化的聚亚安酯,残留的溶剂等通过聚乙烯涂层渗漏。
Claims (8)
1、一种通过粘合剂树脂涂层将第一支持体薄膜涂层层压至第二支持体薄膜涂层的热层压制品的制备方法,其包括,
将所述粘合剂涂层与所述第一支持体薄膜涂层结合,
在氧气存在条件下,用热辐射加热所述粘合剂树脂涂层的表面,引入可增加粘度的功能性基团,然后,
将第二支持体薄膜涂层叠加在所述粘合剂树脂涂层之上并通过压力使之粘接;
所述粘合剂树脂是乙烯-不饱合羧酸酐-不饱合羧酸酯共聚物,乙烯-不饱合羧酸酯共聚物或乙烯-乙烯基酯共聚物。
2、如权利要求1所述的方法,其特征在于:所述热辐射为红外线或火焰。
3、如权利要求1所述的方法,其特征在于:所述红外线为中波范围红外线。
4、如权利要求3所述的方法,其特征在于:所述中波范围红外线为集中的。
5、如权利要求4所述的方法,其特征在于:所述中波范围红外线聚焦在所述粘合剂树脂涂层的表面。
6、如权利要求1所述的方法,其特征在于:所述第一支持体薄膜涂层是乙烯基聚合物薄膜,并且所述第二支持体薄膜涂层是聚酯、聚烯烃或聚酰胺薄膜或铝箔。
7、如权利要求1所述的方法,其特征在于:所述粘合剂树脂是乙烯-不饱合羧酸酐-不饱合羧酸酯共聚物,乙烯-不饱合羧酸酯共聚物或乙烯-乙烯基酯共聚物的组合物,还包括熔点为100℃或以上的聚合烯烃,并且所述聚合烯烃树脂的含量为70wt.%或更少。
8、一种制备热层压制品的设备,其包括,
用于传送第一支持体薄膜涂层和粘合剂树脂涂层结合在一起的层压制品的第一传送装置,
用于传送第二支持体薄膜涂层的第二传送装置,
通过热辐射对第一传送装置传送的层压制品的粘合剂涂层进行加热的加热装置,以及
用于将所述第二传送装置传送的所述第二支持体薄膜涂层粘结的粘结装置。
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US20040261931A1 (en) | 2004-12-30 |
KR101083975B1 (ko) | 2011-11-22 |
US7959755B2 (en) | 2011-06-14 |
JP4023678B2 (ja) | 2007-12-19 |
TWI343871B (en) | 2011-06-21 |
TW200502095A (en) | 2005-01-16 |
BRPI0401500A (pt) | 2004-11-30 |
KR20040093449A (ko) | 2004-11-05 |
EP1475425A1 (en) | 2004-11-10 |
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