CN107267108A - 一种耐蒸煮无溶剂胶及其制备方法 - Google Patents

一种耐蒸煮无溶剂胶及其制备方法 Download PDF

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CN107267108A
CN107267108A CN201710443802.3A CN201710443802A CN107267108A CN 107267108 A CN107267108 A CN 107267108A CN 201710443802 A CN201710443802 A CN 201710443802A CN 107267108 A CN107267108 A CN 107267108A
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苏占军
龙来早
邹金鑫
张学敏
周贞飞
罗丽
陈声才
王宏峰
马福波
唐波
张强
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GUIZHOU PROVINCIAL INST OF CHEMICAL TECHNOLOGY
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Abstract

本发明涉及聚氨酯复合胶技术领域，尤其是一种耐蒸煮无溶剂胶及其制备方法，通过双组份复合胶的原料成分以及双组份混合时候采用摩尔比为NCO/OH＝1.3～2.0混合而成，使得其中无需加入溶剂，避免了溶剂在复合胶中的残留，提高了复合胶的品质，并且得到的复合胶的初始粘接力高，在130℃下能够持续20min无变化，能够满足众多食品包装的需求，尤其适用于多种基材之间的粘接，尤其是PET/PE，PE/CPP以及PE/Al之间剥离强度较高。

Description

一种耐蒸煮无溶剂胶及其制备方法
技术领域
本发明涉及聚氨酯复合胶技术领域，尤其是一种耐蒸煮无溶剂胶及其制备方法。
背景技术
国内，软包装复合胶大多为溶剂型双组份聚氨酯胶粘剂，复合过程中，存在能耗大，挥发物排放大，复合品中残留有部分有机溶剂，严重污染了环境，影响了人们的健康。
随着环保标准的要求越来越高，研究出能够替代溶剂胶的无溶剂胶势在必行，无溶剂胶在生产中是无需加入溶剂，避免在复合胶中残留溶剂的缺点；但是，在我国，无溶剂胶的起步比较晚，技术发展比较缓慢，使得当前市场上未见到有任何关于无溶剂的复合胶，即使在某些技术中，其提到了部分无溶剂胶的技术研究，但是其研究得出来的产品，其初始粘接力不强，耐蒸煮性能极差，使得在需要对产品包装之后，进行高温灭菌处理的行业应用前景较差。
发明内容
为了解决现有技术中存在的上述技术问题，本发明提供一种耐蒸煮无溶剂胶及其制备方法。
具体是：一种耐蒸煮无溶剂胶，原料组分由A组分与B组分混合是按照摩尔比为NCO/OH＝1.3～2.0混合而成；其中A组分原料成分为以重量份计为340-350份聚氧化丙烯二醇、140-150份聚酯多元醇、380-390份MDI-50、120-130份液化MDI；B组分原料成分为550-560份蓖麻油、440-450份苯酐聚酯多元醇、1.8-2.2份偶联剂。
所述的原料组分由A组分与B组分混合是按照摩尔比为NCO/OH＝1.8混合而成。
所述的A组分原料成分为以重量份计为345份聚氧化丙烯二醇、145份聚酯多元醇、385份MDI-50、125份液化MDI。
所述的B组分原料成分为555份蓖麻油、445份苯酐聚酯多元醇、2份偶联剂。
所述的组分中，聚氧化丙烯二醇为聚丙二醇PPG2000。
所述的A组分中，聚酯多元醇为苯酐聚酯多元醇RAYNOL-3152。
所述的B组分中，苯酐聚酯多元醇为苯酐聚酯多元醇XCPA-195。
所述的偶联剂为γ-甲基丙烯酰氧基丙基三甲氧基硅烷KH550。
本发明的目的之二是提供上述的耐蒸煮无溶剂胶制备方法，包括以下步骤：
(1)将聚氧化丙烯二醇、聚酯多元醇加入到反应釜中，加热到120℃，真空度为0.1MPa下，脱水，待含水量＜500ppm，降温到60℃，加入MDI-50升温至85℃反应2.5h，滴加液化MDI，搅拌40min，得到A组分；
(2)将蓖麻油、苯酐聚酯多元醇加入到反应釜中，加热到120℃，真空度为0.1MPa下，脱水至含水量＜500ppm，降温至40-55℃，加入偶联剂，搅拌30min，得到B组分；
(3)将A组分与B组分单独存放，使用时，按照摩尔比为NCO/OH＝1.3～2.0混合均匀后，在45℃下涂布处理。
本发明创造通过双组份复合胶的原料成分以及双组份混合时候采用摩尔比为NCO/OH＝1.3～2.0混合而成，使得其中无需加入溶剂，避免了溶剂在复合胶中的残留，提高了复合胶的品质，并且得到的复合胶的初始粘接力高，在130℃下能够持续20min无变化，能够满足众多食品包装的需求，尤其适用于多种基材之间的粘接，尤其是PET/PE，PE/CPP以及PE/Al之间剥离强度较高。
具体实施方式
下面结合具体的实施方式来对本发明的技术方案做进一步的限定，但要求保护的范围不仅局限于所作的描述。
实施例1
将25kg分子量为1000的聚氧化丙烯二元醇；15kg分子量为2000聚氧化丙烯二元醇，10kg苯酐聚酯多元醇混合均匀，加入反应釜中，开启搅拌器，加热使得温度达到60℃，启动真空泵，使得真空度为0.1MPa，继续加热至温度为120℃，脱水至含水量为500ppm，冷却至78℃，加50kg的MDI，反应2h，得到A组分；
将40kg蓖麻油，58kg苯酐聚酯多元醇混合均匀，加入反应釜，开动搅拌器，加热使温度达到60℃，启动真空泵，使得真空度为0.1MPa，加热至温度为120℃，真空脱水至500ppm，降温至48℃，加入2kg偶联剂，搅拌30min，得到B组分；
将A、B两组份按摩尔比为NCO/OH＝1.6:1，在复合机上复合PET/CPP上胶量为2.0g/m2左右，45℃左右下熟化24h后，T型剥离强度达到5.5N/15mm。对Nylon/PE进行复合，上胶量为2.4g/m2，45℃左右熟化12h后，T型剥离强度达到5N/15mm。复合膜制品放入反高压锅130℃蒸煮30min后，T型剥离强度达到5N/15mm。
实施例2
将20kg分子量1000的聚氧化丙烯二元醇，20kg分子量为2000的聚氧化丙烯二元醇，10kg的苯酐聚酯多元醇混合均匀，加入反应釜中，开动搅拌器，并加热使温度达50℃，启动真空泵，使其釜内真空度达到0.1MPa，继续加热控制物料温度为110℃，真空脱水3h，控制水分含量为300ppm，冷却至78℃，加40kg的入MDI，反应2h后，滴加液化MDI11kg，搅拌30min，得到A组分。
将60kg蓖麻油，38kg苯酐聚酯多元醇混合，加入反应釜，开动搅拌器，并加热使温度达55℃，启动真空泵，使其釜内真空度达到0.1MPa，继续加热控制物料温度为115℃，真空脱水2h，控制水分含量为400ppm，冷却至48℃，加入2kg偶联剂，搅拌30min，得到B组分。
将A、B组分按照摩尔比为NCO/OH＝1.8:1,在复合机上复合PET/CPP上胶量为2.0g/m2左右，45℃左右下熟化24h后，T型剥离强度达到5.8N/15mm。对Nylon/PE进行复合，上胶量为2.4g/m2，45℃左右熟化12小时后，T型剥离强度达到5.2N/15mm。复合膜制品放入反高压锅130℃蒸煮30min后，T型剥离强度达到5N/15mm。
实施例3-7
在其他均同实施例1的基础上，对于在制备过程中，其变化的指标如下表1所示：
表1
从表1中可见，对于本发明创造，其产品中无溶剂残留，改善了双组份胶的品质得到的复合胶的初始粘接力高，在130℃下能够持续30min，其粘接力依然较高，能够满足众多食品包装的需求；并且在130℃下处理20min，其粘接力基本无变化。
在此有必要说明的是：基于本发明的实施例，本领域普通技术的在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。

Claims (10)

1.一种耐蒸煮无溶剂胶，其特征在于，原料组分由A组分与B组分混合是按照摩尔比为NCO/OH＝1.3～2.0混合而成；其中A组分原料成分为以重量份计为340-350份聚氧化丙烯二醇、140-150份聚酯多元醇、380-390份MDI-50、120-130份液化MDI；B组分原料成分为550-560份蓖麻油、440-450份苯酐聚酯多元醇、1.8-2.2份偶联剂。
2.如权利要求1所述的耐蒸煮无溶剂胶，其特征在于，所述的原料组分由A组分与B组分混合是按照摩尔比为NCO/OH＝1.8混合而成。
3.如权利要求1或2所述的耐蒸煮无溶剂胶，其特征在于，所述的A组分原料成分为以重量份计为345份聚氧化丙烯二醇、145份聚酯多元醇、385份MDI-50、125份液化MDI。
4.如权利要求1或2所述的耐蒸煮无溶剂胶，其特征在于，所述的B组分原料成分为555份蓖麻油、445份苯酐聚酯多元醇、2份偶联剂。
5.如权利要求1所述的耐蒸煮无溶剂胶，其特征在于，所述的组分中，聚氧化丙烯二醇为聚丙二醇PPG2000。
6.如权利要求1所述的耐蒸煮无溶剂胶，其特征在于，所述的A组分中，聚酯多元醇为苯酐聚酯多元醇RAYNOL-3152。
7.如权利要求1所述的耐蒸煮无溶剂胶，其特征在于，所述的B组分中，苯酐聚酯多元醇为苯酐聚酯多元醇XCPA-195。
8.如权利要求1所述的耐蒸煮无溶剂胶，其特征在于，所述的偶联剂为γ-甲基丙烯酰氧基丙基三甲氧基硅烷KH550。
9.如权利要求1-9任一项所述的耐蒸煮无溶剂胶制备方法，其特征在于，包括以下步骤：
(1)将聚氧化丙烯二醇、聚酯多元醇加入到反应釜中，加热到120℃，真空度为0.1MPa下，脱水，待含水量＜500ppm，降温到60℃，加入MDI-50升温至85℃反应2.5h，滴加液化MDI，搅拌40min，得到A组分；
(2)将蓖麻油、苯酐聚酯多元醇加入到反应釜中，加热到120℃，真空度为0.1MPa下，脱水至含水量＜500ppm，降温至40-55℃，加入偶联剂，搅拌30min，得到B组分；
(3)将A组分与B组分单独存放，使用时，按照摩尔比为NCO/OH＝1.3～2.0混合均匀后，在45℃下涂布处理。
10.如权利要求1-9任一项所述的耐蒸煮无溶剂胶或如权利要求9所述的制备方法制备的耐蒸煮无溶剂胶用于PET与PE、PE与CPP、PE与Al之间的粘接。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109837055A (zh) * 2018-12-29 2019-06-04 安徽省阜阳市国泰彩印包装有限公司 一种凹面印刷包装膜多层复合用胶水的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1333045A2 (en) * 1997-11-05 2003-08-06 Asahi Glass Company Ltd. Reactive hot melt adhesive and adhesive composite sheet material
WO2014114957A1 (en) * 2013-01-28 2014-07-31 Lucite International Uk Limited Hot melt adhesive
CN104804697A (zh) * 2015-04-13 2015-07-29 上海天洋热熔粘接材料股份有限公司 一种纺织品复合用湿固化聚氨酯热熔胶的制备方法
CN106675499A (zh) * 2016-12-19 2017-05-17 江苏力合粘合剂有限公司 一种无溶剂双组份聚氨酯蒸煮胶及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1333045A2 (en) * 1997-11-05 2003-08-06 Asahi Glass Company Ltd. Reactive hot melt adhesive and adhesive composite sheet material
WO2014114957A1 (en) * 2013-01-28 2014-07-31 Lucite International Uk Limited Hot melt adhesive
CN104804697A (zh) * 2015-04-13 2015-07-29 上海天洋热熔粘接材料股份有限公司 一种纺织品复合用湿固化聚氨酯热熔胶的制备方法
CN106675499A (zh) * 2016-12-19 2017-05-17 江苏力合粘合剂有限公司 一种无溶剂双组份聚氨酯蒸煮胶及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109837055A (zh) * 2018-12-29 2019-06-04 安徽省阜阳市国泰彩印包装有限公司 一种凹面印刷包装膜多层复合用胶水的制备方法

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Application publication date: 20171020