CN107286737A - 一种电子束固化高硬度水性聚氨酯丙烯酸酯及其制备方法 - Google Patents

一种电子束固化高硬度水性聚氨酯丙烯酸酯及其制备方法 Download PDF

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CN107286737A
CN107286737A CN201710429538.8A CN201710429538A CN107286737A CN 107286737 A CN107286737 A CN 107286737A CN 201710429538 A CN201710429538 A CN 201710429538A CN 107286737 A CN107286737 A CN 107286737A
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王景泉
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Abstract

本发明公开了一种电子束固化高硬度水性聚氨酯丙烯酸酯及其制备方法,它由脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂在50~70℃下反应后,再加入2‑羟基戊酸进一步反应,最后用碱中和后得到。本发明使聚氨酯丙烯酸酯能够形成水性分散体。本发明的水性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,经由电子束固化的加热方式除去水后可以得到清澈的膜结构,通过随后与其他组分的相互交联和其他作用,能够得到高品质、高硬度、耐化学腐蚀的电子束固化油墨涂层。

Description

一种电子束固化高硬度水性聚氨酯丙烯酸酯及其制备方法
技术领域
本发明属于油墨领域,具体涉及一种电子束固化高硬度水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高硬度水性聚氨酯丙烯酸酯。
本发明的另一目的是提供一种上述电子束固化高硬度水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:
一种电子束固化高硬度水性聚氨酯丙烯酸酯,它由脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂在50~70℃下反应后,再加入2-羟基戊酸进一步反应,最后用碱中和后得到。
本发明还公开了一种上述电子束固化高硬度水性聚氨酯丙烯酸酯的制备方法:将脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂在50~70℃下进行反应,然后加入2-羟基戊酸进一步反应,再加入碱进行中和反应,反应后将溶液加入水中得到电子束固化的高硬度水性聚氨酯丙烯酸酯分散体。
本发明中的催化剂优选采用二辛酸锡。
本发明中的碱采用碱为氢氧化钠或氢氧化钾。
本发明中脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油和异佛尔酮二异氰酸酯的质量比为20~40:1:15~25,优选25~35:1:18~22。异佛尔酮二异氰酸酯与2-羟基戊酸的质量比为2~5:1,优选3~4:1。
脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂的反应时间为0.3~3小时,加入2-羟基戊酸后的反应时间为0.2~2小时。加入2-羟基戊酸后的反应温度为50~70℃。
本方法中通过采用脂肪醇聚氧乙烯醚甲基丙烯酸酯和甘油以及2-羟基戊酸分别与异氰酸酯基团进行反应,使得聚氨酯丙烯酸酯中含有多种改性基团,通过这些改性基团的相互作用,使得该聚氨酯丙烯酸酯能够形成水性分散体。本发明的水性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,经由电子束固化的加热方式除去水后可以得到清澈的膜结构,通过随后与其他组分的相互交联和其他作用,能够得到高品质、高硬度、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
将3255份脂肪醇聚氧乙烯醚甲基丙烯酸酯A、100份甘油C、1900份异佛尔酮二异氰酸酯D、6份二辛酸锡溶于200份丙酮,在65℃下搅拌反应0.5~1小时,然后加入624份2-羟基戊酸并继续保温搅拌反应0.5~1小时,然后在搅拌下加入201份氢氧化钠进行中和。在搅拌下将得到的清澈溶液加入9200份水中,蒸馏除去丙酮,得到具有38重量%固体含量、8.0的pH值的电子束固化的高硬度水性聚氨酯丙烯酸酯分散体。
实施例2
将3167份脂肪醇聚氧乙烯醚甲基丙烯酸酯A、99份甘油C、1865份异佛尔酮二异氰酸酯D、6份二辛酸锡溶于200份丙酮,在65℃下搅拌反应0.5~1小时,然后加入605份2-羟基戊酸并继续保温搅拌反应0.5~1小时,然后在搅拌下加入197份氢氧化钠进行中和。在搅拌下将得到的清澈溶液加入9090份水中,蒸馏除去丙酮,得到具有38重量%固体含量、8.2的pH值的电子束固化的高硬度水性聚氨酯丙烯酸酯分散体。
对比例1
将实施例1中的脂肪醇聚氧乙烯醚甲基丙烯酸酯改为聚酯醚丙烯酸酯,其他组分和制备同实施例1,得到的分散体粘稠且难以蒸馏。
测试例
电子束固化油墨的各组分的重量份组成为:三羟甲基丙烷三丙烯酸酯22份,实施例1的水性聚氨酯丙烯酸酯分散体25份,甲基丙烯酸正丁酯20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,先将各主要组分和稀释剂在60℃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。附着力、耐划伤性、耐磨性的表示方法:1为最差,5为最优,具体性能见下表。
性能 含实施例1的电子束固化油墨 含对比例1的电子束固化油墨
铅笔硬度 2H-3H H
耐划伤性 3 1

Claims (9)

1.一种电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于它由脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂在50~70℃下反应后,再加入2-羟基戊酸进一步反应,最后用碱中和后得到。
2.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于所述催化剂为二辛酸锡。
3.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于加入2-羟基戊酸后的反应温度为50~70℃。
4.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油和异佛尔酮二异氰酸酯的质量比为20~40:1:15~25。
5.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于异佛尔酮二异氰酸酯与2-羟基戊酸的质量比为2~5:1。
6.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂的反应时间为0.3~3小时,加入2-羟基戊酸后的反应时间为0.2~2小时。
7.根据权利要求1所述的电子束固化高硬度水性聚氨酯丙烯酸酯,其特征在于所述碱为氢氧化钠或氢氧化钾。
8.一种权利要求1所述电子束固化高硬度水性聚氨酯丙烯酸酯的制备方法,其特征在于将脂肪醇聚氧乙烯醚甲基丙烯酸酯、甘油、异佛尔酮二异氰酸酯和催化剂在50~70℃下进行反应,然后加入2-羟基戊酸进一步反应,再加入碱进行中和反应,反应后将溶液加入水中得到电子束固化的高硬度水性聚氨酯丙烯酸酯分散体。
9.权利要求1所述电子束固化高硬度水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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US20210114967A1 (en) * 2018-06-29 2021-04-22 Kaneka Corporation Resist composition for pattern printing and pattern forming method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210114967A1 (en) * 2018-06-29 2021-04-22 Kaneka Corporation Resist composition for pattern printing and pattern forming method

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