CN107266636B - 一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法 - Google Patents
一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法。它由如下方法制备：先合成以聚乙二醇为软段、以1,6‑己二醇为扩链剂的聚氨酯大分子单体；将该聚氨酯大分子单体与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代‑1‑氨丙基‑3‑(α‑丙烯酸乙酯基)咪唑以及引发剂混合制得溶液A；将该溶液A与溶剂混合后于70～80℃下反应，反应后用碱中和，加入去离子水搅拌得到聚氨酯‑丙烯酸酯乳液。本聚氨酯丙烯酸酯可应用于电子束固化油墨或粘合剂的制备领域，能够得到高品质、耐划伤、耐化学腐蚀的电子束固化油墨涂层。
Description
技术领域
本发明属于油墨领域，具体涉及一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法。
背景技术
采用电子束能量固化的油墨称为电子束固化油墨（即EB油墨）。普通油墨印刷后墨膜层的干燥，一般是油墨中的连结料被承印物吸收和挥发，固态物质则保留在承印物表面，形成一层薄薄的墨层。而电子束固化则是借助电子束做照射能源，与活性液体化学配方进行辐射化学反应，在常温下迅速干燥固化的过程。
电子束固化和光固化两者所采用的树脂（预聚物）和单体是类似的，因此其聚合过程和产物也具有一定的相似性和可比性。但是，两者的差别也是明显的，这些差别决定了其不同的优势和市场需求。和光固化相比，电子束固化的优点包括：
１）电子束固化因电子的能量很高，可直接使树脂或单体等有机物解离，产生自由基和离子从而引发聚合反应，因此在电子束固化配方中不必使用光引发剂。这会带来许多好处。首先，光引发剂在光固化时不能完全分解，而它们一般都是含有羰基的化合物，这对光固化材料的耐老化性能极为不利；其次，不用光引发剂可使固化产物更加纯净，不会由于残留的光引发剂及其光分解产物的挥发而引起难闻的臭味，这对某此应用（例如生物、医学、食品等）是至关重要的；最后，由于光引发剂价格一般都比较贵，因此不用光引发剂在产品成本方面也是有利的；
2）电子束的穿透能力仅和物质的密度有关，对于油墨等着色物质不存在像光固化那样的光难以透过的问题，避免了在光固化中必须使用量大而价昂的光引发剂的缺点；
3）电子束的穿透深度比光的穿透深度大，因此，电子束固化不仅可用于薄的表面涂层，也可用于厚达数毫米甚至数厘米的复合材料的固化以及双面固化，这在光固化是比较难以做到的。
电子束固化油墨同UV油墨一样，在网印中也是最有发展前途的“绿色”油墨之一。由于电子束固化油墨不受墨层厚度的限制，操作起来也比紫外线光固化油墨更为安全。当然，作为一种发展中的新型固化技术，EB固化技术也存在着一些缺点。
在一些特定的UV油墨中为了达到某种性能会采用聚氨酯丙烯酸酯作为该类油墨的重要组分，现有技术中也有相关报道，然而由于电子束固化与UV固化的差别，该类聚氨酯丙烯酸酯很难直接应用于电子束固化油墨中，或是该类聚氨酯丙烯酸酯在电子束固化油墨中无法起到预期的效果。
发明内容
本发明的目的是在现有技术的基础上，提供一种电子束固化耐划伤改性聚氨酯丙烯酸酯。
本发明的另一目的是提供一种上述电子束固化耐划伤改性聚氨酯丙烯酸酯的制备方法。
本发明的目的可以通过以下措施达到：
一种电子束固化耐划伤改性聚氨酯丙烯酸酯，它由如下方法制备：先合成以聚乙二醇为软段、以1,6-己二醇为扩链剂的聚氨酯大分子单体；将该聚氨酯大分子单体与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑以及引发剂混合制得溶液A；将该溶液A与溶剂混合后于70～80℃下反应，反应后用碱中和，加入去离子水搅拌得到聚氨酯-丙烯酸酯乳液。
一种上述电子束固化耐划伤改性聚氨酯丙烯酸酯的制备方法：先合成以聚乙二醇为软段、以1,6-己二醇为扩链剂的聚氨酯大分子单体；将该聚氨酯大分子单体与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑以及引发剂混合制得溶液A；将该溶液A与溶剂混合后于70～80℃下反应，反应后用碱中和，加入去离子水搅拌得到聚氨酯-丙烯酸酯乳液。
本发明中的引发剂为偶氮二异丁腈和过氧化二苯甲酰；所述碱为氢氧化钠、氢氧化钾或三乙胺。
本发明的聚氨酯大分子单体以聚乙二醇为软段，以4,4-二苯基甲烷二异氰酸酯和1,6-己二醇为硬段，以环已酮肟为封端剂，其中硬段的质量含量占50%以上，所述聚乙二醇的数均分子量为200～500。
在一种优选方案中，聚氨酯大分子单体的制备方法为：将聚乙二醇、4,4-二苯基甲烷二异氰酸酯、1,6-己二醇和辛酸亚锡混合后，在80～90℃下反应10～80min，加入封端剂环已酮肟继续反应10～80min，再加入甲基丙烯酸羟乙酯降温至40～60℃反应0.5～3h，制得聚氨酯大分子单体。
本发明中脂肪醇聚氧乙烯醚甲基丙烯酸酯、氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑和聚氨酯大分子单体的质量比为50～80：10～20：4～9，优选55～75：12～17：5～8。
本发明中的溶剂选自二季戊四醇、聚乙二醇单甲醚、异丙醇中的一种或几种。
本发明中的溶液A在溶剂中的反应时间为0.1～2h，用碱中和至pH值为8.5～9.5。
本发明的电子束固化耐划伤改性聚氨酯丙烯酸酯可应用在制备电子束固化油墨方面。
本方法中通过合成以聚乙二醇为软段、以1,6-己二醇为扩链剂的聚氨酯大分子单体，并使其与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑进行共聚，使得到的改性聚氨酯丙烯酸酯能够形成互穿网络，有利于增加底涂层与聚酯薄膜的附着力，增加聚酯的柔韧性。本聚氨酯丙烯酸酯可应用于电子束固化油墨或粘合剂的制备领域，能够得到高品质、耐划伤、耐化学腐蚀的电子束固化油墨涂层。
具体实施方式
以下结合实施例对本发明做进一步说明，但本发明的保护范围并不局限于以下各实施例。
实施例1
在反应器中加入数均分子量为300的聚乙二醇20g、4,4-二苯基甲烷二异氰酸酯20g、1,6-己二醇3g，加入辛酸亚锡0.3g，在85℃下反应40min，加入3g环已酮肟，反应40min,再加入甲基丙烯酸羟乙酯15g，再降温至50℃反应1.5h，制得聚氨酯大分子单体；
称量脂肪醇聚氧乙烯醚甲基丙烯酸酯70g，氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑16g，聚氨酯大分子单体7g、偶氮二异丁腈0.5g、过氧化二苯甲酰0.5g混合均匀，制得溶液A；
加入异丙醇40g、聚乙二醇单甲醚40g，1/2溶液A于反应器中，升温至75℃反应30min，通过滴液漏斗滴加剩余部分的溶液A，反应3h后，降温至55℃，加入三乙胺中和至pH值为9，加入150g去离子水，搅拌40min后，制得聚氨酯-丙烯酸酯乳液。
实施例2
在反应器中加入数均分子量为300的聚乙二醇45g、4,4-二苯基甲烷二异氰酸酯46g、1,6-己二醇6.5g，加入辛酸亚锡0.7g，在85℃下反应40min，加入7g环已酮肟，反应40min,再加入甲基丙烯酸羟乙酯32g，再降温至50℃反应1.5h，制得聚氨酯大分子单体；
称量脂肪醇聚氧乙烯醚甲基丙烯酸酯68g，氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑17g，聚氨酯大分子单体6g、偶氮二异丁腈0.5g、过氧化二苯甲酰0.5g混合均匀，制得溶液A；
加入二季戊四醇40g、聚乙二醇单甲醚40g，1/2溶液A于反应器中，升温至75℃反应30min，通过滴液漏斗滴加剩余部分的溶液A，反应3h后，降温至55℃，加入三乙胺中和至pH值为9，加入150g去离子水，搅拌40min后，制得聚氨酯-丙烯酸酯乳液。
对比例1
将实施例1中的氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑移除，将脂肪醇聚氧乙烯醚甲基丙烯酸酯的用量改为86g，其他组分和制备同实施例1。
测试例
电子束固化油墨的各组分的重量份组成为：聚氨酯-丙烯酸酯乳液32份，聚醚胺15份，甲基丙烯酸正丁酯40份，稀释剂环己烷10份，稀释剂乙酸乙酯8份，二氧化钛15份，UNIQJET 9510分散剂0.2份，防腐蚀颜料20份。
制备方法，先主要组分和稀释剂在20～80℃下高速分散至得到分散均匀的溶液，再加入二氧化钛、分散剂和防腐蚀颜料并继续分散均匀，然后过滤即得。
将各实施例和对比例所得的乳液经由测试例所制备的油墨涂于马口铁基材上，置入电子束加速器内进行电子束辐照， 经0.1s辐照剂量1kgy后，墨膜固化。固化后墨膜各项性能测试结果如下：附着力、耐划伤性的表示方法：1为最差，5为最优，具体性能见下表。
| 性能 | 实施例1 | 实施例2 | 对比例1 |
| 附着力 | 4 | 4 | 1 |
| 耐划伤性 | 5 | 4 | 1 |
Claims (7)
1.一种电子束固化耐划伤改性聚氨酯丙烯酸酯，其特征在于它由如下方法制备：先合成以聚乙二醇为软段、以1,6-己二醇为扩链剂的聚氨酯大分子单体；将该聚氨酯大分子单体与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑以及引发剂混合制得溶液A；将该溶液A与溶剂混合后于70～80℃下反应，反应后用碱中和，加入去离子水搅拌得到聚氨酯-丙烯酸酯乳液；所述脂肪醇聚氧乙烯醚甲基丙烯酸酯、氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑和聚氨酯大分子单体的质量比为50～80：10～20：4～9；
其中所述聚氨酯大分子单体以聚乙二醇为软段，以4,4-二苯基甲烷二异氰酸酯和1,6-己二醇为硬段，以环已酮肟为封端剂，其中硬段的质量含量占50％以上，所述聚乙二醇的数均分子量为200～500。
2.根据权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯，其特征在于所述引发剂为偶氮二异丁腈和过氧化二苯甲酰；所述碱为氢氧化钠、氢氧化钾或三乙胺。
3.根据权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯，其特征在于所述聚氨酯大分子单体的制备方法为：将聚乙二醇、4,4-二苯基甲烷二异氰酸酯、1,6-己二醇和辛酸亚锡混合后，在80～90℃下反应10～80min，加入封端剂环已酮肟继续反应10～80min，再加入甲基丙烯酸羟乙酯降温至40～60℃反应0.5～3h，制得聚氨酯大分子单体。
4.根据权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯，其特征在于所述溶剂选自二季戊四醇、聚乙二醇单甲醚、异丙醇中的一种或几种。
5.根据权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯，其特征在于溶液A在溶剂中的反应时间为0.1～2h，用碱中和至pH值为8.5～9.5。
6.一种权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯的制备方法，其特征在于先合成以聚乙二醇为软段、以1,6-己二醇为扩链剂的聚氨酯大分子单体；将该聚氨酯大分子单体与脂肪醇聚氧乙烯醚甲基丙烯酸酯和氯代-1-氨丙基-3-(α-丙烯酸乙酯基)咪唑以及引发剂混合制得溶液A；将该溶液A与溶剂混合后于70～80℃下反应，反应后用碱中和，加入去离子水搅拌得到聚氨酯-丙烯酸酯乳液。
7.权利要求1所述的电子束固化耐划伤改性聚氨酯丙烯酸酯在制备电子束固化油墨方面的应用。
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