CN102575135B - 改进的粘合剂组合物 - Google Patents

改进的粘合剂组合物 Download PDF

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CN102575135B
CN102575135B CN201080045015.XA CN201080045015A CN102575135B CN 102575135 B CN102575135 B CN 102575135B CN 201080045015 A CN201080045015 A CN 201080045015A CN 102575135 B CN102575135 B CN 102575135B
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C·D·李
C·S·霍兰
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Equistar Chemicals LP
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Abstract

本发明提供粘合剂组合物，其适合用作多层薄膜和薄片中的连接层粘合剂。所述粘合剂组合物含有烯烃聚合物基础树脂、改性聚烯烃和链烷液态烃。

Description

改进的粘合剂组合物
发明领域
本发明涉及具有改进的性质的粘合剂组合物，其包含烯烃聚合物基础树脂、改性聚烯烃和链烷液态烃。
发明背景
含有阻挡膜的多层膜结构常用于食品包装工业，用于食品例如零食、肉和奶酪。在这些应用中，期望多层结构展示良好的粘合特征和透明度。差的粘合性质可在制造过程中或最终使用产品中导致薄膜层的分层。透明度是对消费者具有直接影响的重要美学性质。连接层常常被并入多层薄膜结构以粘合不能直接结合的不同层，然而，为了改进连接层提供的粘合的常规努力(比如通过提高连接层组合物中的接枝材料的水平)可导致相应的透明度变差。这个不幸的结果有时可发生于使用乙基乙烯基(乙烯乙烯基或乙烯-乙烯基)醇共聚物(″EVOH")阻挡层的应用中，其中，连接层树脂的马来酸酐官能度和阻挡层的EVOH官能度之间不期望的化学相互作用在产品薄膜中导致扭曲的外观，一般描述为″桔皮″或″粒状″。透明度也可在薄膜层共挤出的过程中受到影响，当组成相邻层的熔融树脂的粘度差异在层界面引起应力，导致起伏型(weavy-type)流动不稳定性时。
多种粘合剂混合物已经描述于美国专利No.4,087,587、4,298,712、4,487,885、4,774,144、5,367,022、5,439,974、5,525,672、5,597,865、6,716,928、6,838,520、7,125,929和专利申请公开No.2007/0054142、2008/0032148和2008/0163978。然而，在多层薄膜应用中对提供改进的粘合性，同时使薄膜透明度的变差最小化(或提高薄膜透明度)的连接层粘合剂组合物存在持续的需求。已意外发现，烯烃聚合物基础树脂、改性聚烯烃和链烷液态烃的混合物在连接层组合物中提供粘合性和透明度的优良的平衡。
发明概述
本发明涉及一种包含2-30重量％的改性聚烯烃、0.02-5重量％的链烷液态烃和65-98重量％的烯烃聚合物基础树脂的粘合剂组合物。本发明也涉及包含所述粘合剂组合物的多层薄膜或薄片。
发明详述
本发明的粘合剂组合物包含烯烃聚合物基础树脂、改性聚烯烃和链烷液态烃组合物。
烯烃聚合物基础树脂
可用于所述粘合剂组合物的烯烃聚合物基础树脂可为丙烯聚合物、乙烯聚合物或它们的混合物。当所述烯烃聚合物基础树脂为丙烯聚合物时，其选自丙烯均聚物、丙烯的无规共聚物或抗冲共聚物，所述共聚物含有最多约30重量％的选自乙烯或C4-8α-烯烃的共聚单体。当所述烯烃聚合物基础树脂为丙烯聚合物时，优选地，其为结晶度(通过广角X射线衍射测量)大于40％的丙烯均聚物或优选含有1-10重量％，更优选1-5重量％乙烯的丙烯共聚物。所述丙烯聚合物的熔体流速(MFR)(通过ASTM D1238，条件230/2.16测量)一般为0.1-100dg/min，优选为5-50dg/min。
当所述烯烃聚合物基础树脂为乙烯聚合物时，其优选为选自乙烯均聚物、乙烯共聚物或它们的混合物，其中共聚单体选自丙烯、C4-8α-烯烃、羧酸乙烯酯、丙烯酸及甲基丙烯酸和酯或它们的混合物。乙烯均聚物和乙烯-C4-8α-烯烃共聚物包括极低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、中密度聚乙烯(MDPE)和高密度聚乙烯(HDPE)。VLDPE限定为具有0.860-0.910g/cm3的密度(通过ASTM D792测量)。LDPE和LLDPE限定为具有0.910-0.930g/cm3范围内的密度。MDPE限定为具有0.930-0.945g/cm3的密度。HDPE限定为具有至少0.945g/cm3，优选0.945-0.969g/cm3的密度。乙烯均聚物和共聚物一般具有的熔体指数(MI)(通过ASTM D1238，条件190/2.16测量)为0.01-400dg/min，优选0.1-200dg/min，更优选1-100dg/min。
优选地，所述烯烃聚合物基础树脂选自乙烯均聚物、乙烯与丙烯的共聚物、乙烯与C4-8α-烯烃的共聚物或它们的混合物。优选地，所述烯烃聚合物基础树脂的结晶度(通过广角X射线衍射或者差示扫描量热法测量)大于30重量％。更优选地，所述烯烃聚合物基础树脂为结晶度大于50重量％，优选大于55重量％的HDPE，或者为结晶度大于40％，优选大于45重量％的LLDPE或者HDPE和LLDPE的混合物。
改性聚烯烃
改性聚烯烃含有酸或酸衍生物官能度，且通过使不饱和羧酸和羧酸酐(或其衍生物)与聚乙烯或聚丙烯在接枝条件下反应而获得。接枝单体(即酸、酸酐或衍生物)沿着所述聚乙烯或聚丙烯主链(backbone)并入。当改性聚烯烃通过接枝聚乙烯而获得时，待接枝的聚乙烯包括乙烯均聚物和乙烯与丙烯、丁烯、4-甲基戊烯、己烯、辛烯或它们的混合物的共聚物。当改性聚烯烃通过接枝聚丙烯而获得时，待接枝的聚丙烯包括丙烯均聚物和丙烯与乙烯或C4-C10α-烯烃的共聚物。优选地，改性聚烯烃通过接枝聚乙烯而获得。更优选地，待接枝的聚乙烯为HDPE或LLDPE。
可用作接枝单体的羧酸或酸酐包括以下化合物，比如丙烯酸、马来酸、富马酸、柠康酸(citaconic acid)、中康酸、马来酸酐、4-甲基环己-4-烯-1，2--二羧酸或酸酐、二环(2.2.2)辛-5-烯-2，3-二羧酸或酸酐、2-氧杂-1，3-二酮螺(4，4)壬-7-烯、二环(2.2.1)庚-5-烯-2，3-二羧酸或酸酐、四氢化邻苯二甲酸或酸酐、x-甲基二环(2.2.1)庚-5-烯-2，3-二羧酸或酸酐、纳迪克(nadic)酸酐、甲基纳迪克酸酐、NA酸酐和甲基NA酸酐。马来酸酐是特别有用的接枝单体。可用于接枝聚乙烯或聚丙烯的酸和酸酐衍生物包括马来酸二烷酯、富马酸二烷酯、衣康酸二烷酯、中康酸二烷酯、柠康酸二烷酯和巴豆酸烷基酯。
接枝根据已知程序通过热或机械方法，通常通过加热聚烯烃和接枝单体的混合物(有或没有溶剂)而完成。优选地，接枝的产物通过使聚乙烯或聚丙烯在实质上不存在溶剂时，在接枝单体存在下与产生自由基的催化剂(比如有机过氧化物)在产生剪切力的反应器(比如挤出机)中熔体共混而制备。双螺杆挤出机(比如由Werner-Pfleiderer以标识ZSK-30、ZSK-53、ZSK-83、ZSK-90和ZSK-92销售的那些)尤其可用于进行接枝操作。优选地，接枝于所述聚乙烯或聚丙烯上的酸或酸衍生物共聚单体的量可从约0.1到约4重量百分数，优选从0.5到3.0重量百分数变动。优选地，当马来酸酐接枝于HDPE或LLDPE上时，接枝的马来酸酐浓度为0.5-4重量百分数。改性乙烯聚合物的熔体指数优选为1-20dg/min。
接枝反应在选择为使快速汽化及随后的接枝单体和任何可能使用的催化剂的损失最小或避免的温度下进行。反应器中接枝单体浓度一般为基于反应混合物的总重量的约1到约5重量％。优选的温度分布是，其中聚烯烃熔体的温度通过挤出机/反应器的长度逐渐升高，直至接枝反应区的最大值，然后朝向反应器出口降低。反应器内的最高温度应使得任何过氧化物催化剂的显著的汽化损失和/或过早分解得以避免。所用的接枝单体和任何催化剂优选以纯净的形式加入挤出机/反应器。
链烷液态烃
可用于粘合剂组合物的链烷液态烃优选具有85-1600cSt的粘度(通过ASTM D445测量)，85-190的粘度指数(通过ASTM D2270测量)，225-310℃的闪点(通过ASTM D92测量)。优选地，所述链烷液态烃选自矿物油、聚α烯烃聚合物(PAO)或其混合物。矿物油是通过多种精炼步骤(比如蒸馏，萃取和结晶)获得，通过酸处理和/或催化加氢处理纯化的精制的链烷烃和环烷烃的混合物。PAO是通过高级α-烯烃(比如1-辛烯、1-壬烯和1-癸烯)的聚合形成的合成油，例如描述于美国专利No.5,171,908。当所述链烷液态烃是矿物油时，粘度优选为90-130cSt，粘度指数优选为90-110且闪点优选为240-275℃。所述矿物油也优选具有530-570的分子量(通过ASTM D2502测量)，780-820℃的5％点(5％point)(通过ASTM D2887测量)，及0.860-0.880g/cm3的比重(通过ASTM D4052测量)。当所述链烷液态烃是PAO时，粘度优选为375-1600cST，粘度指数优选为130-180，且闪点优选为260-300℃。所述PAO也优选具有2000-3200的分子量和0.840-0.860g/cm3的比重。
本发明的粘合剂组合物一般含有2-30重量％的改性聚烯烃、0.02-5重量％的链烷液态烃和65-98重量％的烯烃聚合物基础树脂。优选地，所述粘合剂组合物含有4-25重量％的改性聚烯烃、0.05-3重量％的链烷液态烃和72-96重量％的烯烃聚合物基础树脂。更优选地，所述粘合剂组合物含有7-15重量％的改性聚烯烃、0.1-2重量％的链烷液态烃和83-93重量％的烯烃聚合物基础树脂。
添加剂、稳定剂和填料
本发明的粘合剂组合物可进一步包含添加剂比如稳定剂、UV吸收剂、金属失活剂、硫协同剂、过氧化物清除剂、碱性共稳定剂、酸清除剂、成核剂、澄清剂、常规填料、分散剂、增塑剂、润滑剂、乳化剂、颜料、流动控制剂、荧光增白剂、耐火剂、抗静电剂、发泡剂和它们的混合物，所述添加剂可以本领域技术人员公知的量添加。
所述粘合剂可通过本领域技术人员公知的任何常规方法制备，其中组分的组合可以任何顺序进行。例如，所有组分可首先在常规共混设备中共混，然后将共混的材料挤出。或者，一些组分可在挤出之前共混，其余的组分在共混之后但在挤出机上游或在挤出机自身中引入。所述组分也可在一系列挤出步骤中组合。
多层薄膜
本发明的粘合剂组合物适合作为连接层，用于在多层结构中结合一种或多种聚烯烃、离聚物、聚酯、聚酰胺、乙烯-乙烯醇共聚物和金属层。所述粘合剂组合物可用于层叠、挤出和共挤出过程，例如，用于柔性结构的吹塑薄膜或流延薄膜挤出/共挤出、薄片挤出/共挤出、挤出/共挤出层叠、挤出/共挤出涂布、注射吹塑、熔体热成形等。可与本发明的粘合剂组合物粘合的聚烯烃树脂包括乙烯与丙烯均聚物和乙烯与C3-8α-烯烃、(甲基)丙烯酸烷基酯和羧酸乙烯基酯的共聚物。这类典型的树脂包括但不限于LDPE、LLDPE、HDPE、PP、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸甲酯共聚物(EMA)和乙烯-丙烯酸正丁酯共聚物(EnBA)。聚对苯二甲酸丁二醇酯是有用的聚酯树脂的一个实例。一般的聚酰胺可包括尼龙6、尼龙6，6、尼龙12、尼龙6，12和尼龙6，66。通过EVA的皂化/水解获得的EVOH也是给予阻挡性质的高度有用的树脂，特别对于薄膜应用。在多层构造中一般使用的金属主要是铝、铜和钢的薄片和箔。
所述粘合剂组合物也可用于刚性和半刚性的结构，所述结构含有如通常用于食品包装或食品贮藏应用的结构层。这类的典型结构可包括一个或多个食品接触层或密封层、阻挡层和一个或多个结构层。食品接触/密封层常常包括非极性聚烯烃(例如，LDPE)，而一般的阻挡层包含EVOH聚酰胺等的基底。结构层可包含苯乙烯聚合物，所述苯乙烯聚合物也可含有橡胶。考虑到(given)高抗冲聚苯乙烯(HIPS)期望的物理性质、易于挤出处理、热成形和切割，其广泛用作结构层。
以下实施例说明本发明；但是，本领域技术人员将认识到本发明的精神和权利要求的范围内的许多变化。
实施例的粘合剂组合物利用下列烯烃聚合物基础树脂、改性聚烯烃和链烷液态烃组分制备：
BR-1       密度为0.919g/cm3且MI为2.0dg/min.的LLDPE，可从Equistar Chemicals LP购得。
BR-2       密度为0.918g/cm3且MI为2.0dg/min.的LLDPE，可从Equistar Chemicals LP购得。
BR-3       密度为0.916g/cm3且MI为1.0dg/min.的LLDPE，可从Equistar Chemicals LP购得。
Mgraft-1   用1.9重量％马来酸酐接枝的HDPE，MI为9.5dg/min且密度为0.952g/cm3，可从Equistar Chemicals LP购得。
Mgraft-2   用1.65重量％马来酸酐接枝的HDPE，MI为6.5dg/min且密度为0.952g/cm3，可从Equistar Chemicals LP购得。
PLH-1      Duoprime-500，一种可从Equistar Chemicals LP购得的矿物油，粘度为103cSt，粘度指数为103，闪点为265℃，分子量为550g/g-摩尔，5％点为800°F且比重为0.870g/cm3。
PLH-2      Elevast C-30，一种可从ExxonMobil Chemical购得的聚α烯烃，粘度为396cSt，粘度指数为147，闪点为285℃，分子量为2200g/g-摩尔且比重为0.850g/cm3。
制备粘合剂组合物
除非另作说明，否则实施例中使用的粘合剂组合物通过使基础树脂(BR-1、BR-2、BR-3)、改性聚烯烃(Mgraft-1、Mgraft-2)、链烷液态烃(PLH-1、PLH-2)与添加剂熔体共混，利用以230rpm操作，具有以下温度分布的ZSK30双螺杆挤出机制备：
区 区1 区2 区3 区4 区5 区6 区7 转接器 模头
温度，℃ 160 210 215 220 220 220 220 215 215
随后将熔体共混的挤出物粒化。除非另作说明，否则当链烷液态烃包括在粘合剂共混物中时，链烷液态烃母料(MB)通过如下制备：首先使链烷液态烃与丙酮以1：1比例混合以形成均匀混合物，然后使之与基础树脂组合以生成含有1.5重量％的液体链烷烃的混合物。随后使所述混合物沉降过夜以使丙酮蒸发。蒸发之后，使20％的MB与基础树脂共混以形成混合物，所述混合物在粘合剂共混物中含有期望的液体链烷烃水平。
粘合试验-制备薄膜
在Killion挤出机上制备具有A/B/C/B/A结构的厚度为3或5密耳的五层共挤出流延薄膜，其中表层A是M6210，一种MI为0.95且比重为0.958g/cm3的HDPE，可从Equistar Chemicals LP购得，连接层B是粘合剂组合物，且阻挡层C是EVOH(Soarnol DC3203FB)，可从Nippon Gohsei Kagaku K.K购得。层分布为43％HDPE/3％连接/8％EVOH/3％连接/43％HDPE。各层的温度分布(华氏度)如下：
区1 区2 区3 转接器 模头
HDPE表层(A)，°F 360 390 410 410 410
连接层(B)，°F 350 380 400 410 410
EVOH(C)，°F 380 380 390 410 410
粘合测量
通过在共挤出的薄膜中心附近沿机器方向切割25.4mm宽条，通过ASTM方法D1876测定粘合。在连接/EVOH界面将各个条分离。利用Instron拉伸试验机测量以254(10″)mm/min将所述薄膜分离成T-剥离构型所需的力。五个试样的平均粘合记录为剥离强度(Ib/in)。
透明度试验-制备薄膜
在Killion挤出机上制备具有A/B/C/B/A结构的厚度5密耳的五层共挤出流延薄膜，其中表层A是UE624，一种含有18％乙酸乙烯酯且MI为2.1的乙基(乙烯乙烯基或乙烯-乙烯基)乙酸酯共聚物，可从Equistar Chemicals LP购得，连接层B是粘合剂组合物，且阻挡层C是EVOH(Soarnol DC3203FB)。层分布为36％EVA/7％连接/14％EVOH/7％连接/36％EVA。各层的温度分布(华氏度)如下：
区1 区2 区3 转接器 模头
EVA表层(A)，°F 350 390 400 410 410
连接层(B)，°F 350 390 400 410 410
EVOH(C)，°F 380 380 400 410 410
透明度试验-测量
薄膜透明度利用Zebedee CL-100透明度仪通过狭角散射(NAS)测量来测量。将多层薄膜试样切成10cm×10cm正方形并在光源前通过抽气粘附于试验单元。将薄膜在相同的方向取向并以相同的方式测试以使测试变量最小。对每个NAS样品最少运行七个试样。较高的NAS指示改进的薄膜样品透明度。
对照实施例1
一种粘合剂组合物，其含有90.0重量％BR-1和10.0重量％Mgraft-1。
实施例2
一种粘合剂组合物，其含有89.7重量％BR-1、10.0重量％Mgraft-1和0.3重量％PLH-1。
实施例3
一种粘合剂组合物，其含有89.7重量％BR-1、10.0重量％Mgraft-1和0.3重量％PLH-2。
根据对照实施例1和实施例2-3制备粘合剂组合物，并制备3-密耳和5-密耳薄膜。在所述薄膜上进行粘合和透明度试验，且其数据总结在表1中。
对照实施例4
一种粘合剂组合物，其含有89.84重量％BR-2、10.0重量％Mgraft-1、0.06重量％Irganox1076和0.1重量％Irgafos168，Irganox1076和Irgafos168两者均可从Ciba Specialty Chemical Company购得。
实施例5
一种粘合剂组合物，其含有89.54重量％BR-2、10.0重量％Mgraft-1、0.06重量％Irganox1076、0.1重量％Irgafos168和0.3重量％PLH-1。
对照实施例6
一种粘合剂组合物，其含有95.86重量％BR-2、4.0重量％Mgraft-2、0.03重量％Irganox1076、0.07重量％Irgafos168和0.04重量％Irganox1010。
实施例7
一种粘合剂组合物，其含有95.56重量％BR-2、4.0重量％Mgraft-2、0.03重量％Irganox1076、0.07重量％Irgafos168、0.04重量％Irganox1010和0.3重量％PLH-1，Irganox1010可从Ciba SpecialtyChemical Company购得。
根据对照实施例4和6及实施例5和7制备粘合剂组合物，对于混合部分利用Baker-Perkins125mm双螺杆挤出机，其中将PLH-1直接加入挤出机进料，随后利用Davis Standard单螺杆挤出机粒化。混合部分中的温度分布为350°F而粒化区的为370°F。然后制备3密耳和5密耳薄膜。在所述薄膜上进行粘合试验，且数据总结在表2-3中。
比较实施例8
一种粘合剂组合物，其含有90.0重量％BR-3和10.0重量％Mgraft-1。
比较实施例9
一种粘合剂组合物，其含有89.0重量％BR-3和11.0重量％Mgraft-1。
根据比较实施例8-9制备粘合剂组合物。在所述薄膜上进行粘合和透明度试验，且数据总结在表4中。这些实施例说明，增加的接枝的材料的百分比增大粘合，但代价是透明度变差。
对照实施例10
一种粘合剂组合物，其含有89.90重量％BR-1、10.0重量％Mgraft-1、0.05重量％Irganox1010和0.05重量％Irgafos168。
实施例11
一种粘合剂组合物，其含有89.87重量％BR-1、10.0重量％Mgraft-1、0.05重量％Irganox1010、0.05重量％Irgafos168和0.03重量％PLH-1。
实施例12
一种粘合剂组合物，其含有89.6重量％BR-1、10.0重量％Mgraft-1、0.05重量％Irganox1010、0.05重量％Irgafos168和0.3重量％PLH-1。
实施例13
一种粘合剂组合物，其含有88.4重量％BR-1、10.0重量％Mgraft-1、0.05重量％Irganox1010、0.05重量％Irgafos168和1.5重量％PLH-1。
根据对照实施例10和实施例11-13制备粘合剂组合物。然后制备3密耳和5密耳薄膜。在所述薄膜上进行粘合和透明度试验，且数据总结在表5中。数据说明保持透明度的同时改进了薄膜中的粘合。

Claims (2)

1.一种粘合剂组合物，其包含：
(a) 2-30重量%的改性聚烯烃；
(b) 0.02-5重量%的选自矿物油或聚α烯烃聚合物的链烷液态烃；和
(c) 65-98重量%的烯烃聚合物基础树脂；
条件是组分(a)、(b)和(c)的总量不超过100重量%，
其中所述烯烃聚合物基础树脂为乙烯均聚物；或乙烯共聚物，其共聚单体选自C4-8 α-烯烃。
2.权利要求1的粘合剂组合物，其中所述链烷液态烃存在的量为0.05-3重量%。
3. 权利要求2的粘合剂组合物，其中所述链烷液态烃存在的量为0.1-2重量%。
4. 权利要求1的粘合剂组合物，其中所述改性聚烯烃存在的量为4-25重量%。
5. 权利要求4的粘合剂组合物，其中所述改性聚烯烃存在的量为7-15重量%。
6. 权利要求1的粘合剂组合物，其中所述改性聚烯烃为用羧酸、羧酸酐或其衍生物接枝的聚合物，所述聚合物选自乙烯均聚物；乙烯与丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯或1-辛烯的共聚物；丙烯均聚物；丙烯与乙烯或C4-C10 α-烯烃的共聚物或它们的混合物。
7. 一种多层薄膜，其包含第一层和与第一层粘合性结合的连接层，所述连接层包含粘合剂组合物，其包含：
(a) 2-30重量%的改性聚烯烃；
(b) 0.02-5重量%的选自矿物油或聚α烯烃聚合物的链烷液态烃；和
(c) 65-98重量%的烯烃聚合物基础树脂；
条件是组分(a)、(b)和(c)的总量不超过100重量%，
其中所述烯烃聚合物基础树脂为乙烯均聚物；或乙烯共聚物，其共聚单体选自C4-8 α-烯烃。
8. 权利要求7的多层薄膜，其中所述链烷液态烃存在的量为0.05-3重量%。
9. 权利要求8的多层薄膜，其中所述链烷液态烃存在的量为0.1-2重量%。
10. 权利要求7的多层薄膜，其中所述改性聚烯烃为用羧酸、羧酸酐或其衍生物接枝的聚合物，所述聚合物选自乙烯均聚物；乙烯与丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯或1-辛烯的共聚物；丙烯均聚物；丙烯与乙烯或C4-C10 α-烯烃的共聚物或它们的混合物。
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