CN106459702B - 粘合性密封组合物 - Google Patents

粘合性密封组合物 Download PDF

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CN106459702B
CN106459702B CN201580033993.5A CN201580033993A CN106459702B CN 106459702 B CN106459702 B CN 106459702B CN 201580033993 A CN201580033993 A CN 201580033993A CN 106459702 B CN106459702 B CN 106459702B
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C.科凯
B.洛朗
S.德维姆
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Aiskai Zhixin Co.,Ltd.
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Abstract

本发明涉及一种粘合性组合物，其在宽的温度范围内可在用于在基材上施用的挤出‑涂布方法中使用或可在挤出‑层压方法中使用以将多个相同或不同物质种类的载体彼此粘合，该组合物包含：‑按所述组合物的重量计91％至98％的乙烯和丙烯酸烷基酯的共聚物；‑至少一种增粘树脂；‑加工添加剂，其特征在于增粘树脂占该组合物重量的1.5％至5％，和所述添加剂占该组合物重量的0.5％至3.5％，并且特征在于防粘剂在加工添加剂中至少占所述添加剂的60重量％。本发明还涉及由所述组合物组成的膜和包括这种膜的多层结构。

Description

粘合性密封组合物
技术领域
本发明涉及基于乙烯和丙烯酸烷基酯的共聚物的粘合剂或粘结剂组合物，其可用于挤出-涂布方法(应用于载体上)或用于挤出-层压方法(用于将多个为不同或相同种类的载体彼此粘合在一起，这些载体之一可以是热塑性塑料或金属，特别如铝)中。
因此，本发明还涉及由该粘合性组合物组成的密封膜或包括载体和所述密封膜的多层结构。
背景技术
在下文中，“密封”被理解为意指膜的两个表面或两个层的联合，而不管它们的种类如何。
存在各种各样的用于食品的包装，例如具有可剥离开口的包装。这些具有可剥开口的包装可以通过将盖子密封到容器上来生产，容器可以由不同的材料，特别是不同的聚合物(聚苯乙烯，聚醚对苯二甲酸酯，聚乙烯，聚丙烯等)组成。盖必须对容器具有足够强的粘附力，以防止包装的意外打开，但是也足够弱的粘附力以便可剥离。
所述盖是多层结构并且通常由多个层组成，至少包括(可剥离)粘合性密封层和常规由聚合物，纸或铝制成的“机械”层。这些盖可以通过挤出-涂覆或通过在吹塑薄膜挤出中获得的薄膜的热层压来生产。
该盖的生产受到以下多个可加工性问题的影响：
-在通过挤出-涂覆的生产期间粘附到冷却辊(“chill roll”)上，
-在通过吹膜制造膜期间膜打开的问题，
-在热层压之前和期间在卷盘操作期间，通过吹膜(也可通过例如平模，挤出-涂布或层压获得)产生的膜的粘连性(bloquant)和滑移。
粘连性和滑移是本领域技术人员公知的膜生产特有的问题。因此，在膜中使用滑爽剂使得可以降低摩擦系数(COF)，同时保持光泽，透明度和清澈性的光学性能，而使用防粘剂使得可以在膜的表面中产生促进膜在所有类型的载体上滑动的结节。
为了克服这些可加工性问题，本领域技术人员已知的是，必须向粘合性密封层中加入加工添加剂，即滑爽剂和防粘剂(anti-bloquant)。
粘合性密封(可剥离)层的配方取决于期望在其上密封该盖的容器。本领域技术人员已知的是，向聚乙烯(PE)，聚丙烯(PP)或乙烯和乙酸乙烯酯的共聚物(EVA)添加增粘树脂使得可以获得密封树脂配方，其密封性能在许多类型的载体上是优异的。文献US7495048或EP2166034示出了这种现有技术。
在文献US7495048中描述了一种密封树脂组合物，其包含：
-75重量％至99重量％的乙烯和不饱和酯的共聚物，优选具有大于5％的乙酸乙烯酯含量的EVA，
-5重量％至20重量％的具有高软化点的增粘树脂。
这些组合物使得可以降低最低密封温度。
目前使用的增粘树脂的含量在5％和20％之间。事实上，使用这样的增粘树脂含量，出现两种以下类型的问题：
-在与增粘树脂的存在相关的加工温度下的热稳定性的问题，
-与对于克服加工问题所需的大量添加(添加加工添加剂，即防粘剂和滑爽剂)相关的透明度损失。这是因为增粘树脂的加入使得可剥离的密封树脂配制剂非常粘，这导致在挤出涂布中或在薄膜吹制中薄膜开口时粘附到冷却辊(“chill roll”)上的问题。如上所述，本领域技术人员已知的是，为了克服这些问题，需要大量添加(加工添加剂)，但是这种添加会对组合物的透明度有害。
因此，目前寻找一种不具有上述缺点，同时保持由现有技术的粘合性组合物获得的良好性质的粘合性密封热塑性组合物。
发明内容
令人惊奇的是，本申请人已经发现特定类型的共聚物与至少一种增粘树脂以及特定比例的加工添加剂（特别是对于防粘剂和滑爽剂）的组合使得可以获得粘合性密封(可剥离的)组合物，其具有根据现有技术的粘合性组合物的所有性能，同时克服了这些组合物的主要在组合物的加工性能和透明性方面的缺点。
该发现与本领域技术人员可能预期到的情况背道而驰，因为本领域技术人员不会设想降低增粘树脂的含量，因为他知道这种降低无疑会对组合物的密封性能有害。然而，根据本发明的粘合性组合物，其含有小于5％(或任选地最多5％)的增粘树脂，使得可以保持良好的密封性能，同时保持所需的良好的热稳定性和光学性质。
本发明因此涉及一种粘合性组合物，其在宽的温度范围内可在用于在基材上施用的挤出-涂布方法中使用或可在挤出-层压方法中使用以将多个相同或不同物质种类的载体彼此粘合，该组合物包含：
-按所述组合物的重量计91％至98％的乙烯和丙烯酸烷基酯的共聚物；
-至少一种增粘树脂；
-加工添加剂，其包含至少一种防粘剂和滑爽剂，
其特征在于该增粘树脂占该组合物重量的1.5％至5％，和所述添加剂占该组合物重量的0.5％至3.5％，并且特征在于防粘剂在加工添加剂中占所述添加剂的至少60重量％。
本发明的其它特征或实施方式如下：
-有利地，增粘树脂占该组合物重量的3％至4％；
-优选地，乙烯和丙烯酸烷基酯的共聚物中的丙烯酸酯含量为所述共聚物重量的15％至30％；
-优选地，乙烯和丙烯酸烷基酯的共聚物由乙烯和丙烯酸甲酯的共聚物组成；
-根据本发明的具体特征，上述共聚物的MFI为5g/10min至15g/10min(在190℃，2.13kg)；
-有利地，加工添加剂以所述组合物的1.5重量％至2.5重量％存在；
-优选地，加工添加剂仅由至少一种防粘剂和至少一种滑爽剂组成，防粘剂占所述添加剂的至少70重量％；
-根据一个实施方案，根据本发明的组合物仅由上述共聚物，上述增粘树脂和所述加工添加剂组成。
本发明还涉及由上述组合物组成的密封膜，其特征在于其厚度为10-20微米(μm)。
本发明还涉及包括至少两个膜的多层结构，所述膜中之一是如上所述的密封膜，其特征在于，第二个膜选自铝，纸张或纸板，玻璃纸，基于聚乙烯，聚丙烯，聚酰胺，聚酯，聚氯乙烯(PVC)，聚偏二氯乙烯(PVDC)或聚丙烯腈(PAN)树脂的膜，这些膜是取向的或非取向的，金属化或非金属化的，通过物理或化学方法处理的或未处理的，和用无机薄阻挡层涂覆的膜，如聚酯(PET SiOx或AlOx)。
附图说明
下面的描述仅作为说明的并非限制性的方式通过参考附图给出，其中：
-图1a至1e示出了所述测试中的一种和这种测试(包括将试样粘附到冷却辊上)的测量。
发明详述
关于乙烯和丙烯酸酯的共聚物，可以涉及(甲基)丙烯酸烷基酯，烷基可以具有最高24个碳原子。作为该乙烯和丙烯酸酯共聚物的非限制性实例，可以提及C1-C8(具有1至8个碳原子)丙烯酸酯或丙烯酸烷基酯，例如(甲基)丙烯酸C1-C8烷基酯，丙烯酸正丁基酯或丙烯酸异丁基酯和甲基丙烯酸甲基乙基酯。
本申请人已经注意到，在本专利申请的目的的范围中，用其中丙烯酸烷基酯的含量为共聚物重量的15％至30％的共聚物获得更好的结果。
还应注意，下面的组合物都显示出为12g/10min(在190℃，2.13kg)的MFI(熔体流动指数)值，但申请人还证明所选择的共聚物的MFI应该在5g/10min至15g/10min之间(在190℃，2.13kg)，以便能够实现本发明的目的。
关于增粘树脂，其涉及选自以下三种类型的树脂(聚合物)的具有小于或等于10000g.mol-1(克/摩尔)的数均分子量的聚合物：
-氢化和二聚酸或酯类型松香树脂；
-脂族、氢化脂族、芳族、氢化芳族，脂族/芳族，氢化脂族/芳族，脂环族，氢化脂环族，脂环族/芳族和氢化脂环族/芳族类型烃树脂；
-多萜和苯酚萜烯类型树脂。
关于加工添加剂，在本发明的范围中，它们特定地且唯一地为两种种类，即防粘剂和滑爽剂。
“防粘剂”被理解为是指这样的添加剂，其使得可以降低在两个聚合物表面之间的粘合作用。根据本发明的防粘剂可以由有机类型的组分，例如山嵛酸酰胺(behenamide)，硬脂酰胺，亚乙基双油酰胺或亚乙基双硬脂酰胺，或无机类型的组分如二氧化硅，滑石，碳酸钙，高岭土或粘土组成。
“滑爽剂”被理解为是指这样的添加剂，其使得可以降低在其中加入它的产品的摩擦系数。根据本发明的防粘剂可以由芥酸酰胺，油酰胺，油基棕榈酰胺和硬脂酰芥子酰胺组成。
注意的是，在下文中，本发明仅用一种类型的增粘树脂即Régalite R1125进行说明，但申请人已经证明本发明使用上述增粘树脂之一也发挥作用。
根据本发明的粘合性组合物根据本领域技术人员熟知的方法进行制备。作为非限制性实例，这种粘合性组合物可传统地通过共旋转双螺杆挤出而获得。
包括根据本发明的组合物的膜的多层结构根据众所周知的方法之一，例如挤出-层压，由本领域技术人员毫无困难地获得。尽管这种合成路线，即挤出层压，特别适合于形成根据本发明的组合物的膜或包含这种膜的多层，但是本发明不限于这种合成方式，并且例如将可以设想在通过热层压通过吹膜获得的膜的热层压的制备方法中。
所测试组合物的配制剂的制备：
根据本发明和根据现有技术的所测试组合物的试样根据同一种方法精确地进行制备。事实上，制备了盖，即包括所测试组合物的多层。这些盖子通过在Collin®实验室生产线上在铝上共挤出-涂覆进行制备。
对于主剥离测试，所有试样的结构完全相同，当然除了待测试的粘合性组合物。因此，这些盖的结构由铝37μm/粘结剂6μm/粘合性组合物15μm组成。
对于粘合性密封组合物，要测试的物理化学性质为很多种。在这种情况下，下面进行和介绍的测试包括剥离测试，粘连性测量，静态和动态摩擦系数的测量，雾度，在冷却辊上的粘附性和热稳定性测试。
实施的测试：
剥离测试
在将盖(不同的上述目标试样)密封在不同的载体上之后测量剥离力。使用AINPACK®盖密封机(热封机)进行盖在表示容器的聚合物片材(特别是聚苯乙烯，聚醚对苯二甲酸酯等)上的焊接。夹爪的宽度为3毫米(mm)。
密封条件为：
施加的压力：2.26N/mm2
密封时间：1秒
可变温度：130℃，160℃，180℃，200℃和220℃
在“封盖样品”在50％HR(相对湿度)和23℃的气氛中调理至少24小时后，以恒定速率(100mm/分钟)经由配备有100N测力传感器（cellule de force）和90°板的Synergie200H测力计。
试样的粘连性的测量
粘连性根据名为“Plastics -- Film and sheeting -- Determination ofblocking resistance”的标准ISO 115-02在根据本发明或根据现有技术的粘合性组合物的单层膜上进行测量，该粘合性组合物的单层膜通过挤出涂布获得，厚度为50μm(微米)。
试样的静态和动态摩擦系数的测量
静态和动态摩擦系数根据名为“Standard test method for static andkinetic coefficients of friction of plastic film and sheeting”的标准ASTM D1894在根据本发明和根据现有技术的粘合性组合物的单层膜上进行测量，所述粘合性组合物的单层膜通过挤出涂布进行制备，厚度为50μm。
雾度测试
雾度根据名为“Standard test method for haze and luminous transmittanceof transparent plastics”的标准ASTM D-1003-007在根据本发明和现有技术的粘合性组合物的单层膜上进行测量，该单层膜厚度为50μm，通过挤出-涂布进行制备。
试样在冷却辊上的粘附作用的测量
在制备期间通过挤出-涂覆试样盖来评价在冷却辊上的粘附作用。盖在冷却辊的越上面进行分离，粘附作用越大。更确切地，施加用于拉扯存在于冷却辊上的膜的力，并且测量膜的拉扯容易性。为了更好地理解掌握这种测试和由此产生的测量，附图1使得可以清楚地理解测试的原理及其测量，即使知晓技术人员清楚地了解这种过程。
热稳定性测试
所述分析通过根据以下程序的热重分析(ATG)进行实施：
动态测量：
该测量在TG 209F1 Netzsch装置上进行
在空气和氮气下以10℃/min从25℃加热至600℃
等温测量：
该测量在TG 209F1 Netzsch装置上进行
以50℃/min的速率从25℃加热至230℃、250℃、280℃和300℃，然后在氮气下等温。
所测试组合物的原材料：
Lotryl® 20MA08：乙烯-丙烯酸甲酯共聚物，其丙烯酸酯含量为共聚物的20重量％，并且其MFI为8g/10min(190℃，2.13kg)。在下面给出的结果的表中，这种Lotryl®用首字母20MA08表示。
Lotryl® 40MA10：乙烯-丙烯酸甲酯共聚物，其丙烯酸酯含量为共聚物的40重量％，并且其MFI为8g/10min(190℃，2.13kg)。在下面给出的结果的表中，这种Lotryl®用首字母40MA08表示。
Lotryl® 10MA08：乙烯-丙烯酸甲酯共聚物，其丙烯酸酯含量为共聚物的10重量％，并且其MFI为8g/10min(190℃，2.13kg)。在下面给出的结果的表中，这种Lotryl®用首字母10MA08表示。
增粘树脂(市售)：低分子量的增粘树脂，其是完全氢化的，软化点为123℃。在下面给出的结果的表中，增粘树脂由首字母RT表示。
由Imerys公司出售的10MOOS滑石：该加工剂同时起到防粘剂和滑爽剂的作用。该组分在下文中被称为滑石。
EBS：由Croda公司提供的亚乙基双硬脂酰胺。该加工剂是防粘剂。该组分在下文中被表示为EBS。
Er：由Croda公司提供的Erucamide。该加工剂是滑爽剂。该组分在下文中被表示为Er。
使加工添加剂混合以构成三种添加，第一种添加占粘合性组合物重量的1％，第二种添加剂占粘合性组合物重量的2％，第三种添加剂占粘合性组合物重量的4.5％粘合性组合物。
添加a：0.25％Er+0.25％EBS+0.5％滑石
添加b：0.5％Er+0.5％EBS+1％滑石
添加c：1％Er+1％EBS+2.5％滑石。
测试结果：
粘合性密封组合物必须表现出某些有利的特性。
在这里不穷尽地给出关于根据本发明的粘合性组合物的结果。在这方面，更特别地目标针对四个特征，即：
-雾度必须小于15，理想地小于或等于12；和
-在通过挤出-涂覆的制备期间，在冷却辊(在下文用CR表示)上粘附作用必须是低的(表示为“-”)；
-所述极限膜开口温度(température limite d'ouverture de gain)为至少100℃；
-对于动态滑动的系数和对于静态滑动的系数必须为至少0.4；
-粘连性(bloquant)必须至少为150克。
配制剂 雾度 在CR上的粘附 极限膜开口T℃ Ks Kd 粘连性
20MA08 5 + 85 NM NM 640
20MA08+添加a 8 - 95 0.43 0.41 44
20MA08+添加b 12 - 105 0.25 0.24 24
20MA08+添加c 40 - 105 0.21 0.18 23
20MA08+3.5%RT 6 ++ 78 NM NM NM
20MA08+3.5%RT+添加b 11 - 105 0.4 0.42 70
40MA08+3.5%RT+添加b 12 - 104 0.62 0.59 76
10MA08+3.5%RT+添加b 11 - 107 0.35 0.39 65
20MA08+5%RT+添加b 10 + 102 0.41 0.44 170
20MA08+2%RT+添加b 12 - 108 0.32 0.31 40
20MA08+6%RT+添加b 10 + 95 NM NM 564
20MA08+10%RT 7 +++ 72 NM NM NM
20MA08+10%RT+添加c 40 - 100 0.39 0.40 210
NM：不可测量。
在将盖子密封在PET(聚醚对苯二甲酸酯)容器上时获得的扩展力(les forces depropagation)。在该测试期间发现，无论树脂的含量为10％还是在本发明的范围内的含量时，扩展值是几乎相同的。
还对其它类型的载体，特别是在聚苯乙烯和聚丙烯上进行了测试，并且显示与下表中给出的结果类似的结果。
下表中的配制剂No.1至No.8分别由以下组成：
No.1：20MA08+3.5%RT+添加b
No.2：20MA08+5%RT+添加b
No.3：20MA08+2%RT+添加b
No.4：20MA08+6%RT+添加b
No.5：40MA08+3.5%RT+添加b
No.6：10MA08+3.5%RT+添加b
No.7：20MA08+10%RT+添加c
No.8：20MA08+添加a。
密封温度(℃) No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8
130 2.5 2.7 2.6 2.4 2.7 2 2.4 1.7
145 2.8 2.9 2.8 2.7 2.9 2.3 2.7 2
160 3.3 3.2 3.2 3.4 3.4 2.7 3.3 2.3
180 3.4 3.3 3.4 3.3 3.4 3 3.4 2.4
220 3.5 3.4 3.5 3.3 3.4 3 3.5 2.5
热稳定性用在下表中提到的不同指标进行度量。发现根据本发明的组合物的稳定性的非常明显的增大，特别是相对于具有组合物的10重量％的增粘树脂含量的组合物。

Claims (11)

1.一种粘合性组合物，其在宽的温度范围内可在用于在基材上施用的挤出-涂布方法中使用或可在挤出-层压方法中使用以将多个相同或不同物质种类的载体彼此粘合，该组合物包含：
-按所述组合物的重量计91％至98％的乙烯和丙烯酸烷基酯的共聚物；
-至少一种增粘树脂；
-加工添加剂，其包含至少一种防粘剂和滑爽剂，
其特征在于该增粘树脂占该组合物重量的1.5％至5％，和所述添加剂占该组合物重量的0.5％至3.5％，并且特征在于防粘剂在加工添加剂中占所述添加剂的至少60重量％。
2.根据权利要求1所述的组合物，其特征在于所述增粘树脂占所述组合物重量的3％至4％。
3.根据权利要求1或2所述的组合物，其特征在于在所述乙烯和丙烯酸烷基酯的共聚物中的丙烯酸酯含量为所述共聚物重量的15％至30％。
4.根据权利要求1或2所述的组合物，其特征在于所述乙烯和丙烯酸烷基酯的共聚物由乙烯和丙烯酸甲酯的共聚物组成。
5.根据权利要求1或2所述的组合物，其特征在于所述共聚物的MFI为5g/10min至15g/10min，其在190℃和2.13kg测量。
6.根据权利要求1或2所述的组合物，其特征在于所述加工添加剂以所述组合物的1.5重量％至2.5重量％存在。
7.根据权利要求1或2所述的组合物，其特征在于所述加工添加剂仅由至少一种防粘剂和至少一种滑爽剂组成，所述防粘剂占所述添加剂的至少70重量％。
8.根据权利要求1或2所述的组合物，其特征在于其仅由上述共聚物，上述增粘树脂和所述加工添加剂组成。
9.一种由前述权利要求中任一项所述的组合物构成的密封膜，其特征在于其厚度为10-20微米(μm)。
10.一种包括至少两个膜的多层结构，所述膜中之一是根据权利要求9的密封膜，其特征在于第二个膜选自铝、纸张或纸板、玻璃纸、基于聚乙烯、聚丙烯、聚酰胺、聚酯、聚氯乙烯(PVC)、聚偏二氯乙烯(PVDC)或聚丙烯腈(PAN)树脂的膜，其中这些膜是取向的或非取向的、金属化或非金属化的、通过物理或化学方法处理的或未处理的，和用无机薄阻挡层涂覆的膜。
11.根据权利要求10的多层结构，其特征在于所述用无机薄阻挡层涂覆的膜为聚酯PETSiOx或AlOx膜。
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CA2951488C (fr) 2023-02-14
EP3161088A1 (fr) 2017-05-03
CN106459702A (zh) 2017-02-22
BR112016028999B1 (pt) 2022-03-29
JP6635951B2 (ja) 2020-01-29
CA2951488A1 (fr) 2015-12-30
DK3161088T3 (da) 2020-12-14
WO2015197933A1 (fr) 2015-12-30
JP2017524766A (ja) 2017-08-31
EP3161088B1 (fr) 2020-09-16
PL3161088T3 (pl) 2022-01-03
BR112016028999A2 (pt) 2017-08-22
US20170137676A1 (en) 2017-05-18

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