CN111269686A - 胶印用高牢度水性聚氨酯转移胶水 - Google Patents

胶印用高牢度水性聚氨酯转移胶水 Download PDF

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CN111269686A
CN111269686A CN202010259927.2A CN202010259927A CN111269686A CN 111269686 A CN111269686 A CN 111269686A CN 202010259927 A CN202010259927 A CN 202010259927A CN 111269686 A CN111269686 A CN 111269686A
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董其兴
孙晓泽
崔秋菊
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Shandong Audmay High Molecular Material Co ltd
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Abstract

本发明提供了一种胶印用高牢度水性聚氨酯转移胶水，该聚氨酯转移胶水包括以下重量份的原料：二环己基甲烷‑4,4‑二异氰酸酯12‑15份、1,6‑六亚甲基二异氰酸酯16‑20份、苯聚氧亚烷基二醇20‑28份、聚四亚甲基醚二醇25‑32份、聚丙二醇3‑8份、环氧树脂2‑6份、小分子扩链剂3‑5份、亲水扩链剂3‑4份、催化剂1‑1.5份、中和剂2‑3.5份、氨基硅烷偶联剂0.3‑0.8份、消泡剂0.5‑0.8份、乙醇2‑4份、丙酮10‑15份。本发明水性聚氨酯转移胶水牢度高，稳定性强，具有优异的粘结强度和附着力，耐折性好，胶带反拉无透光点，抗倒光性好，UV胶印油墨不爆口。

Description

胶印用高牢度水性聚氨酯转移胶水
技术领域
本发明涉及转移胶技术领域，具体涉及一种胶印用高牢度水性聚氨酯转移胶水。
背景技术
胶印是平版印刷的一种，很简单的讲胶印就是借助于胶皮（橡皮布）将印版上的图文传递到承印物上的印刷方式，也正是橡皮布的存在，这种印刷方式得名。胶皮在印刷中起到了不可替代的作用 ，如：它可以很好的弥补承印物表面的不平整，使油墨充分转移，它可以减小印版上的水（水在印刷中的作用见后）向承印物上的传递等等。目前胶印所用转移胶水一般为丙烯酸体系，但是其仍具有一定缺陷，丙烯酸体系转移胶水附着力好的，油墨易爆口；而爆口好的，抗倒光就差。因此研发附着力好的同时不爆口且抗倒光性好的胶水十分必要。
水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系，也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯以水为分散介质，具有无毒、不易燃烧、不污染环境、节能、安全可靠等优点，符合绿色工业的发展要求，因此近年来水性聚氨酯获得了广泛的关注和国内外的重视。目前水性聚氨酯转移胶水已得到了一定的发展。
申请号为CN201610902229.3的国内专利公开了一种水性聚氨酯转移胶的制备方法，该涂料包括以下组分：聚碳酸酯二醇、聚酯二元醇、氢化苯基甲烷二异氰酸酯、亲水性扩链剂、扩链剂、中和剂、N-甲基吡咯烷酮；制备工艺包括：备料、原料混合加热脱水、预聚物合成、预聚物中和分散、扩链脱溶乳化。该发明的聚氨酯转移胶具有优良的抗热粘花、附着力好，耐折性好，适合胶印、凹印等各种印刷工艺。但是随着胶印技术打发展，对于转移胶水的附着力要求越来越高，因此对转移胶水进行进一步改进，而在改进附着力同时，制备的转移胶水不爆口且抗倒光性好也十分重要。
发明内容
本发明的目的在于提供一种胶印用高牢度水性聚氨酯转移胶水，稳定性强，具有优异的粘结强度和附着力，耐折性好，胶带反拉无透光点，抗倒光性好，UV胶印油墨不爆口。
为实现以上目的，本发明通过以下技术方案予以实现：
一种胶印用高牢度水性聚氨酯转移胶水，包括以下重量份的原料：二环己基甲烷-4,4-二异氰酸酯12-15份、1,6-六亚甲基二异氰酸酯16-20份、苯聚氧亚烷基二醇20-28份、聚四亚甲基醚二醇25-32份、聚丙二醇3-8份、环氧树脂2-6份、小分子扩链剂3-5份、亲水扩链剂3-4份、催化剂1-1.5份、中和剂2-3.5份、氨基硅烷偶联剂0.3-0.8份、消泡剂0.5-0.8份、乙醇2-4份、丙酮10-15份。
优选的，所述苯聚氧亚烷基二醇的羟值为150-300mgKOH/g。
优选的，所述聚四亚甲基醚二醇的分子量为1000-2000。
优选的，所述环氧树脂为环氧树脂604。
优选的，所述聚丙二醇为聚丙二醇2000或聚丙二醇3000。
优选的，所述小分子扩链剂为三羟甲基丙烷、 1,2-丙二醇、1,4-丁二醇中的一种或几种的组合。
优选的，所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸。
优选的，所述催化剂为辛酸亚锡；
所述中和剂为三乙胺或氨水；
所述氨基硅烷偶联剂为N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷或γ-氨丙基三乙氧基硅烷；
所述消泡剂为BYK-025或BYK-028。
本发明胶印用高牢度水性聚氨酯转移胶水的制备方法包括以下步骤：
（1）按配方比称取各原料；
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇、环氧树脂搅拌均匀，然后加入小分子扩链剂，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为75-85℃，搅拌10-15min后，滴加催化剂，然后搅拌反应60-90min；加入亲水扩链剂、氨基硅烷偶联剂以及乙醇，然后继续在75-85℃下搅拌反应60-90min，再加入丙酮，再继续在75-85℃下搅拌反应60-90min，得预聚物；
（3）将预聚物的温度降至40-50℃，加入中和剂，加水快速搅拌，水的用量为预聚物总质量1.8-2.5倍；持续搅拌60-90min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂搅拌均匀，制备得到所述水性聚氨酯转移胶水。
本发明的有益效果是：
1、本发明中的水性聚氨酯转移胶水具有优异的稳定性，其牢度高，具有优异的粘结强度和附着力，剥离性能好。
2、本发明产品在150次对折实验后未出现脱落、露底现象，表明耐折性能强，明显优于现有技术中转移胶水的耐折性。
3、由本发明水性聚氨酯转移胶水得到的胶带反拉无透光点， 抗倒光性好，UV胶印油墨不爆口。在胶印技术领域具有很好的使用效果。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
下述实施例中，苯聚氧亚烷基二醇为三井化学SKC聚氨酯公司生产的羟值为160mgKOH/g或281mgKOH/g的苯聚氧亚烷基二醇。
聚四亚甲基醚二醇为韩国巴斯夫BASF公司生产的分子量为1000或2000的聚四亚甲基醚二醇。
实施例1：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）称取各原料：二环己基甲烷-4,4-二异氰酸酯13份、1,6-六亚甲基二异氰酸酯18份、苯聚氧亚烷基二醇（羟值为281mgKOH/g）25份、聚四亚甲基醚二醇（分子量为2000）30份、聚丙二醇3000 5份、环氧树脂604 5份、三羟甲基丙烷4份、二羟甲基丙酸3份、辛酸亚锡1份、三乙胺3份、N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷0.5份、消泡剂BYK-025 0.6份、乙醇3份、丙酮12份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇3000、环氧树脂604 搅拌均匀，然后加入三羟甲基丙烷，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为80℃，搅拌12min后，滴加辛酸亚锡，然后搅拌反应80min；加入二羟甲基丙酸、N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷以及乙醇，然后继续在80℃下搅拌反应70min，再加入丙酮，再继续在80℃下搅拌反应70min，得预聚物。
（3）将预聚物得温度降至45℃，加入三乙胺，加水快速搅拌，水的用量为预聚物总质量2.2倍；持续搅拌80min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-025搅拌均匀，制备得到所述水性聚氨酯转移胶水。
实施例2：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）称取各原料：二环己基甲烷-4,4-二异氰酸酯12份、1,6-六亚甲基二异氰酸酯17份、苯聚氧亚烷基二醇（羟值为160KOH/g）26份、聚四亚甲基醚二醇（分子量为2000）28份、聚丙二醇2000 5份、环氧树脂604 5份、1,2-丙二醇4份、二羟甲基丁酸3份、辛酸亚锡1.5份、三乙胺3份、γ-氨丙基三乙氧基硅烷 0.5份、消泡剂BYK-025 0.5份、乙醇3份、丙酮13份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇2000、环氧树脂604 搅拌均匀，然后加入1,2-丙二醇，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为80℃，搅拌15min后，滴加辛酸亚锡，然后搅拌反应90min；加入二羟甲基丁酸、γ-氨丙基三乙氧基硅烷以及乙醇，然后继续在80℃下搅拌反应90min，再加入丙酮，再继续在80℃下搅拌反应70min，得预聚物。
（3）将预聚物得温度降至40℃，加入三乙胺，加水快速搅拌，水的用量为预聚物总质量2倍；持续搅拌80min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-025搅拌均匀，制备得到所述水性聚氨酯转移胶水。
实施例3：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）称取各原料：二环己基甲烷-4,4-二异氰酸酯15份、1,6-六亚甲基二异氰酸酯20份、苯聚氧亚烷基二醇（羟值为281mgKOH/g）25份、聚四亚甲基醚二醇（分子量为2000）30份、聚丙二醇3000 6份、环氧树脂604 4份、三羟甲基丙烷5份、二羟甲基丁酸3份、辛酸亚锡1.5份、三乙胺3份、N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷0.8份、消泡剂BYK-028 0.8份、乙醇3份、丙酮13份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇、环氧树脂604 搅拌均匀，然后加入三羟甲基丙烷，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为78℃，搅拌15min后，滴加辛酸亚锡，然后搅拌反应90min；加入二羟甲基丁酸、N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷以及乙醇，然后继续在78℃下搅拌反应70min，再加入丙酮，再继续在78℃下搅拌反应90min，得预聚物；
（3）将预聚物得温度降至50℃，加入三乙胺，加水快速搅拌，水的用量为预聚物总质量1.8倍；持续搅拌80min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-028搅拌均匀，制备得到所述水性聚氨酯转移胶水。
实施例4：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）称取各原料：二环己基甲烷-4,4-二异氰酸酯15份、1,6-六亚甲基二异氰酸酯20份、苯聚氧亚烷基二醇（羟值为281mgKOH/g）25份、聚四亚甲基醚二醇（分子量为2000）30份、聚丙二醇2000 3份、环氧树脂604 5份、三羟甲基丙烷5份、二羟甲基丙酸3份、辛酸亚锡1.2份、三乙胺2份、γ-氨丙基三乙氧基硅烷0.5份、消泡剂BYK-028 0.8份、乙醇3份、丙酮12份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇2000、环氧树脂604 搅拌均匀，然后加入三羟甲基丙烷，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为85℃，搅拌15min后，滴加辛酸亚锡，然后搅拌反应90min；加入二羟甲基丙酸、γ-氨丙基三乙氧基硅烷以及乙醇，然后继续在85℃下搅拌反应60min，再加入丙酮，再继续在85℃下搅拌反应80min，得预聚物。
（3）将预聚物得温度降至50℃，加入三乙胺，加水快速搅拌，水的用量为预聚物总质量2倍；持续搅拌80min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-028搅拌均匀，制备得到所述水性聚氨酯转移胶水。
实施例5：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）称取各原料：二环己基甲烷-4,4-二异氰酸酯12份、1,6-六亚甲基二异氰酸酯16份、苯聚氧亚烷基二醇（羟值为160mgKOH/g）28份、聚四亚甲基醚二醇（分子量为1000）32份、聚丙二醇3000 8份、环氧树脂604 2份、1,2-丙二醇5份、二羟甲基丙酸3份、辛酸亚锡1.5份、氨水3.5份、γ-氨丙基三乙氧基硅烷0.3份、消泡剂BYK-025 0.5份、乙醇2份、丙酮10份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇3000、环氧树脂604 搅拌均匀，然后加入1,2-丙二醇，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为75℃，搅拌10min后，滴加辛酸亚锡，然后搅拌反应60min；加入二羟甲基丙酸、γ-氨丙基三乙氧基硅烷以及乙醇，然后继续在75℃下搅拌反应90min，再加入丙酮，再继续在75℃下搅拌反应90min，得预聚物。
（3）将预聚物得温度降至40℃，加入氨水，加水快速搅拌，水的用量为预聚物总质量1.8倍；持续搅拌90min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-025搅拌均匀，制备得到所述水性聚氨酯转移胶水。
实施例6：
一种胶印用高牢度水性聚氨酯转移胶水，其制备方法包括以下步骤：
（1）按配方比称取各原料：二环己基甲烷-4,4-二异氰酸酯13份、1,6-六亚甲基二异氰酸酯18份、苯聚氧亚烷基二醇（羟值为281mgKOH/g）20份、聚四亚甲基醚二醇（分子量为2000）25份、聚丙二醇3000 7份、环氧树脂604 6份、1,4-丁二醇3份、二羟甲基丁酸4份、辛酸亚锡1份、三乙胺2份、γ-氨丙基三乙氧基硅烷0.8份、消泡剂BYK-028 0.6份、乙醇4份、丙酮15份。
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇3000、环氧树脂604 搅拌均匀，然后加入1,4-丁二醇，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为80℃，搅拌12min后，滴加辛酸亚锡，然后搅拌反应80min；加入二羟甲基丁酸、γ-氨丙基三乙氧基硅烷以及乙醇，然后继续在80℃下搅拌反应80min，再加入丙酮，再继续在80℃下搅拌反应60min，得预聚物。
（3）将预聚物得温度降至45℃，加入三乙胺，加水快速搅拌，水的用量为预聚物总质量2.5倍；持续搅拌60min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂BYK-028搅拌均匀，制备得到所述水性聚氨酯转移胶水。
性能测试：
1、根据GB/T2791-1995对实施例1-6中的转移胶水进行胶黏强度测试。结果如表1所示。
表1：
Figure DEST_PATH_IMAGE001
2、将本发明实施例1-6中的胶水喷涂成膜，然后进行对折实验，对所得产品进行150次对折后，观察其脱落、露底现象，具体结果如表2所示。
表2：
Figure 386052DEST_PATH_IMAGE002
由表1和表2可知，本发明制备得到的水性聚氨酯转移胶水粘结强度高，牢度高，具有高附着力，剥离性能好，且耐折性好，不露底。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (9)

1.胶印用高牢度水性聚氨酯转移胶水，其特征在于，包括以下重量份的原料：二环己基甲烷-4,4-二异氰酸酯12-15份、1,6-六亚甲基二异氰酸酯16-20份、苯聚氧亚烷基二醇20-28份、聚四亚甲基醚二醇25-32份、聚丙二醇3-8份、环氧树脂2-6份、小分子扩链剂3-5份、亲水扩链剂3-4份、催化剂1-1.5份、中和剂2-3.5份、氨基硅烷偶联剂0.3-0.8份、消泡剂0.5-0.8份、乙醇2-4份、丙酮10-15份。
2.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述苯聚氧亚烷基二醇的羟值为150-300mgKOH/g。
3.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述聚四亚甲基醚二醇的分子量为1000-2000。
4.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述环氧树脂为环氧树脂604。
5.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述聚丙二醇为聚丙二醇2000或聚丙二醇3000。
6.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述小分子扩链剂为三羟甲基丙烷、 1,2-丙二醇、1,4-丁二醇中的一种或几种的组合。
7.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸。
8.根据权利要求1所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，所述催化剂为辛酸亚锡；
所述中和剂为三乙胺或氨水；
所述氨基硅烷偶联剂为N-β-(氨乙基)-γ- 氨丙基甲基二乙氧基硅烷或γ-氨丙基三乙氧基硅烷；
所述消泡剂为BYK-025或BYK-028。
9.根据权利要求1-8任一项所述的胶印用高牢度水性聚氨酯转移胶水，其特征在于，其制备方法包括以下步骤：
（1）按配方比称取各原料；
（2）将苯聚氧亚烷基二醇、聚四亚甲基醚二醇、聚丙二醇、环氧树脂搅拌均匀，然后加入小分子扩链剂，搅拌均匀后，加入二环己基甲烷-4,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯，控制温度为75-85℃，搅拌10-15min后，滴加催化剂，然后搅拌反应60-90min；加入亲水扩链剂、氨基硅烷偶联剂以及乙醇，然后继续在75-85℃下搅拌反应60-90min，再加入丙酮，再继续在75-85℃下搅拌反应60-90min，得预聚物；
（3）将预聚物得温度降至40-50℃，加入中和剂，加水快速搅拌，水的用量为预聚物总质量1.8-2.5倍；持续搅拌60-90min，将预聚物充分分散；然后脱除丙酮，并加入消泡剂搅拌均匀，制备得到所述水性聚氨酯转移胶水。
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