CN108948232B - 新型光引发剂混合物 - Google Patents
新型光引发剂混合物 Download PDFInfo
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- CN108948232B CN108948232B CN201710376152.5A CN201710376152A CN108948232B CN 108948232 B CN108948232 B CN 108948232B CN 201710376152 A CN201710376152 A CN 201710376152A CN 108948232 B CN108948232 B CN 108948232B
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- irgacure
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
本发明涉及光固化(UV‑Curing)新材料化学品领域，特别涉及一类新型光引发剂混合物，其在含烯键不饱和型可辐射聚合体系作为光引发剂的用途，以及含有这种光引发剂混合物组分的含烯键不饱和型可辐射聚合体系。
Description
【技术领域】
本发明涉及光固化(UV-Curing)新材料化学品领域，特别涉及一类新型光引发剂混合物，其在含烯键不饱和型可辐射聚合体系作为光引发剂的用途，以及含有这种光引发剂混合物组分的含烯键不饱和型可辐射聚合体系。
【背景技术】
在光固化新材料技术领域，光引发剂(Photo-initiator)是吸收UV辐射光源能量而产生活性自由基或阳离子酸等聚合引发物种的关键材料，因此业界存在一种持续性的技术需求，即研发和产业化新型的光引发剂物质，能够应对性能提升，低成本经济竞争力，方便使用，和环境和健康友好等多种应用诉求。
光引发剂Darocur 1173(CAS号码7473-98-5)和Irgacure 184(CAS号码947-19-3)是为从业技术人员众所周知的两个广谱性光引发剂产品。二者在化学结构上均属于所谓羟基酮型光引发剂，但物态和应用性能差距很大，各自形成了相对独立的大规模下游应用市场。其中Darocur 1173室温下为液态，生产成本较低；而Irgacure 184室温下为固态，生产成本较高，环境污染风险相对显著。同时，Irgacure 184在光引发过程中会裂解产生一系列有害及有不良残留味道的化学物质，包括致癌性物质苯，苯甲醛，和环己酮等，导致为环境和用户健康不喜的气味问题和VOCs污染释放(即Volatile Organic Compounds)。
因此光固化新材料业界存在一种长期的强烈技术需求和愿望，即寻找一种Irgacure 184的有效替代品光引发剂，该引发剂不仅保有乃至提升Irgacure 184的原有优异性能，特别是高超的光引发活性和耐黄变性，而且消除或减轻Irgacure 184的原有突出不良性能，特别是不良残留气味以及作为固体材料(需要现场加热或搅拌溶解)不便于客户使用的麻烦。同时，更进一步的，作为一种成熟产品的替代品，必须适应产业链业已形成的成本格局，因此，新的替代品必须在经济竞争力上亦具备优势。
【发明内容】
本项申请现已意外地发现，将一种新型胺基酮型光引发剂APi-307(化学结构1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one，CAS号码94576-68-8，深圳市有为化学技术有限公司专利保护产品)和光引发剂Darocur 1173以合适的质量比例复配，可以制备一种新型光引发剂混合物，特别是室温为液态的光引发剂混合物，我们命名牌号为APi-184S，即超级184(184-Super)。该APi-184S光引发剂能够在应用性能上保有和提升传统Irgacure 184的原有特征，同时源头消除了其固有的不良残留气味和VOCs释放等长期瓶颈性难题。
所述的光引发剂混合物APi-184S的特征是含有a百分质量份的光引发剂APi-307，b百分质量份的光引发剂Darocur 1173，和c百分质量份的其他物质；其他物质是指其他文献已知光引发剂，活性胺助引发剂，含烯键(C＝C)不饱和化合物(单体或树脂)，或功能性添加剂。约束条件是：
(1)a+b+c三者之和是100％质量份；
(2)a和b取值均不为零，c取值可以为零或非零。
所述文献已知光引发剂是下述任意一种光引发剂化合物或任意两种或两种以上光引发剂化合物组成的复配混合物：羟基酮型(Hydroxyketones)，胺基酮型(Aminoketones)，膦酰型(Acylphosphine Oxides)，肟酯型(Oxime Esters)，二苯甲酮型(Benzophenones)，苯甲酰甲酸酯型(Phenylglyoxylates)，硫杂蒽酮型(Thioxanthones)，鎓盐型阳离子光引发剂(Sulfoniums或Iodoniums或Photo-Acid Generators，即所谓PAGs)，或染料作为实质性光敏化剂(Dye Sensitizers)的光引发剂物质。光引发剂的例子是Darocur 1173，Irgacure 184，APi-180(深圳有为化学公司产品，CAS号码1308332-52-6)，Irgacure 2959，Irgacure MBF，Irgacure 127，Irgacure 651，Esacure KIP-150，Esacure KIP-160，Esacure KIP-1001，Esacure 01，Irgacure907，Irgacure 500，Irgacure2200，Irgacure 2022，Irgacure 4500，Irgacure369，Irgacure 379，Irgacure 819，Irgacure TPO，Irgacure TPO-L，BP，甲基或乙基米蚩酮，Esacure TZT，Irgacure 754，Irgacure ITX，Irgacure DETX，Irgacure CPTX，Irgacure OXE-01，Irgacure OXE-02，Irgacure OXE-03，Irgacure250，ADEKA NCI-831，ADEKA N-1414，Irgacure 290，Irgacure270，以及香豆素型染料光敏化剂等，上述体系也可以复配相应的助引发剂(Co-initiator)，例如活性胺和/或氢硅烷类活性氢给体型助引发剂。
所述含烯键不饱和化合物(单体)是任何含烯键可聚合单体，包括但不限于(甲基)丙烯酸酯，丙烯醛，烯烃，共轭双烯烃，苯乙烯，马来酸酐，富马酸酐，乙酸乙烯酯，乙烯基吡咯烷酮，乙烯基咪唑，(甲基)丙烯酸，(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺，乙烯基卤化物，亚乙烯基卤化物等。
所述含烯键不饱和化合物(树脂)是任何含烯键预聚物和低聚物，包括但不限于(甲基)丙烯酰官能基的(甲基)丙烯酸共聚物，聚氨酯甲酸酯(甲基)丙烯酸酯，聚酯(甲基)丙烯酸酯，不饱和聚酯，聚醚(甲基)丙烯酸酯，硅氧烷(甲基)丙烯酸酯，环氧树脂(甲基)丙烯酸酯等，以及上述物质的水溶性或水分散性的类似物。
所述功能性添加剂是合适的各类添加剂，为本领域技术人员所知晓的是如下各类添加剂，包括但不限于阻聚剂，活性胺助引发剂，流平剂，消泡剂，抗流挂剂，增稠剂，增粘剂，分散剂，抗静电剂，增溶剂，稀释剂，水或有机溶剂，抗菌剂，阻燃剂，无机或有机填充剂(例如纳米氧化铝，二氧化硅，碳酸钙，硫酸钡等)和/或着色剂(例如颜料或染料等)，增强涂料油墨耐候性的紫外线吸收剂或/和光稳定剂，及上述组分的合适的水性分散体或水溶解性产品。
进一步的，我们披露一类新型的UV辐射固化材料配方体系，其特征是：
(3)含有至少一种APi-184S定义的光引发剂混合物；
(4)含有至少一种含烯键不饱和化合物(单体和/或树脂)。
所述的含烯键不饱和化合物(单体和/或树脂)定义与上相同。
本发明披露的上述新型UV辐射固化材料配方体系，包括光固化涂料或油墨材料，配合各种不同的施工方式(例如喷涂，滚涂，淋涂，擦涂，浸涂等)和/或施工工序(例如腻子，底涂，上色，中涂，面涂等)，在木器家具，塑胶产品，印刷包装，喷墨打印，电子消费品，机动车辆内外饰，管道型材，工业地坪，建筑幕墙，3D打印增材制作，以及船舶或集装箱体等下游市场均具有极为广阔的应用价值。特别有价值的示例性而非限定性应用例如，该等涂料或油墨用于制备着色和未着色的油漆和清漆、粉末涂料、印刷油墨、印版、胶粘剂、压敏胶粘剂、牙科组合物、凝胶涂料、电子器件用光致抗蚀剂、电锻抗蚀剂、蚀刻抗蚀剂、液态和干膜二者、焊接抗蚀剂、制造用于各种显示器应用的滤色器的抗蚀剂，制备等离子显示面板的制造方法中的结构、电致发光显示器和LCD的抗蚀剂，用于LCD、全息数据储存，用于包封电子组件的组合物，用于制备磁记录材料、微机械部件、波导、光学开关、锻覆掩膜、蚀刻掩膜、彩色打样体系、玻璃纤维电缆涂料、丝网印刷模版，用于借助立体光刻产生三维物体，作为图像记录材料，用于全息记录、微电子电路、脱色材料，用于图像记录材料的脱色材料，用于使用微胶囊的图像记录材料，作为光致抗蚀剂材料用于UV和可见激光直接成像体系，作为光致抗蚀剂材料用于形成印刷电路板的依序构建层中的介电层；特别地，使用上文所述的可光聚合组合物来制备着色和未着色的油漆和清漆、粉末涂料、印刷油墨(例如丝网印刷油墨、用于胶版、柔版或喷墨印刷的油墨)、印版、胶粘剂、密封件、灌封组分、牙科组合物、泡沫、模制复合物、复合材料组合物、玻璃纤维电缆涂料、丝网印刷模版，用于借助立体光刻产生三维物体，和作为图像记录材料、光致抗蚀剂组合物、脱色材料、用于图像记录材料的脱色材料，用于使用微胶囊的图像记录材料。
在实施例中我们将进一步说明。
【具体实施方式】
下面结合具体实施例进一步说明本发明要旨：
实施例：
含烯键(丙烯酸酯)UV辐射固化材料配方体系样品按下列配方制作(以重量百分比计)：双酚A环氧丙烯酸酯(Ebecryl 605)：32％；氨基丙烯酸酯(Ebecryl 7100)：10％；丙烯酰吗啉：54％；光引发剂：4％。
光固化性能评估：将上述实施例和对比例样品涂覆于卡纸板上形成约20-25微米的涂层，以UV高压汞灯(距离基材约20厘米)为辐照光源，变速传送带试验。以指甲反复压刻刮擦不产生印迹为光聚合固化完成的判据。
固化后残留气味评估：固化后膜体残余气味测试以5个人分别独立地评价气味级别，评估的标准以数字标示如下：0级：没有气味；1级：非常轻微的气味；2级：轻微的气味；3级：明显的气味；4级：强烈的气味；5级：非常强烈的气味。
固化黄变性能评估：固化后膜体黄变指数用Gardner Index法表征。
实施例和对比例样品结果如下：
当光引发剂是APi-184S(其中a＝10％和b＝90％)时，光固化完全最大线速度为36米/分钟，残留气味等级为1级，固化黄变性指数为0.8。
当光引发剂是APi-184S(其中a＝8％和b＝92％)时，光固化完全最大线速度为30米/分钟，残留气味等级为0-1级，固化黄变性指数为0.8。
当光引发剂是APi-184S(其中a＝5％和b＝90％和c＝5％且c是市售光引发剂TPO)时，光固化完全最大线速度为40米/分钟，残留气味等级为1级，固化黄变性指数为0.6。
当光引发剂是APi-184S(其中a＝5％和b＝90％和c＝5％且c是市售活性胺助引发剂EHA)时，光固化完全最大线速度为36米/分钟，残留气味等级为1级，固化黄变性指数为1.2。
当光引发剂是APi-184S(其中a＝10％和b＝80％和c＝10％且c是市售丙烯酸酯单体TMPTA)时，光固化完全最大线速度为30米/分钟，残留气味等级为1级，固化黄变性指数为0.6。
当光引发剂是市售Irgacure 184时，光固化完全最大线速度为24米/分钟，残留气味等级为4级，固化黄变性指数为1.4。
上述结果清晰地证明了APi-184S是综合性能显著优于传统Irgacure 184化合物的新型光引发剂。
需要强调的是，上述实施例仅仅为示例性而非限定性说明，基于本项申请披露，任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨，本专利的保护范围应以相关的权利书记载条目为准。
Claims (9)
1.一种光引发剂混合物APi-184S，其特征是含有质量份百分数为a的光引发剂APi-307，质量份百分数为b的光引发剂Darocur 1173，和质量份百分数为c的其他物质；其他物质是指其他光引发剂，活性胺助引发剂，含烯键不饱和化合物单体或含烯键不饱和化合物树脂，或功能性添加剂，其中：
（1）a + b + c三者之和是100%；
（2）a=10%，b=90%；或
a=8%，b=92%；或
a=5%，b=90%，c=5%；或
a=10%，b=80%，c=10%，
所述其他光引发剂是下述任意一种光引发剂化合物或任意两种或两种以上光引发剂化合物组成的复配混合物：羟基酮型，胺基酮型，膦酰型，肟酯型，二苯甲酮型，苯甲酰甲酸酯型，硫杂蒽酮型，鎓盐型阳离子光引发剂，和染料作为实质性光敏化剂的光引发剂物质，
所述功能性添加剂为阻聚剂，流平剂，消泡剂，抗流挂剂，增稠剂，增粘剂，分散剂，抗静电剂，增溶剂，稀释剂，水或有机溶剂，抗菌剂，阻燃剂，无机或有机填充剂和/或着色剂，增强涂料油墨耐候性的紫外线吸收剂或/和光稳定剂，或上述组分的水性分散体或水溶解性产品。
2.根据权利要求1所述的光引发剂混合物APi-184S，其特征是所述其他光引发剂为Irgacure 184，APi-180，Irgacure 2959，Irgacure MBF，Irgacure 127，Irgacure 651，Esacure KIP-150，Esacure KIP-160，Esacure KIP-1001，Esacure 01，Irgacure 907，Irgacure 500，Irgacure 2200，Irgacure 2022，Irgacure 4500，Irgacure 369，Irgacure379，Irgacure 819，Irgacure TPO，Irgacure TPO-L，BP，甲基或乙基米蚩酮，Esacure TZT，Irgacure 754，Irgacure ITX，Irgacure DETX，Irgacure CPTX，Irgacure OXE-01，Irgacure OXE-02，Irgacure OXE-03，Irgacure 250，ADEKA NCI-831，ADEKA N-1414，Irgacure 290，Irgacure 270，或香豆素型染料光敏化剂。
3.根据权利要求1所述的光引发剂混合物APi-184S，其特征是所述含烯键不饱和化合物的单体为（甲基）丙烯酸酯，丙烯醛，烯烃，苯乙烯，马来酸酐，富马酸酐，乙酸乙烯酯，乙烯基吡咯烷酮，乙烯基咪唑，（甲基）丙烯酸，（甲基）丙烯酰胺，乙烯基卤化物，或亚乙烯基卤化物。
4.根据权利要求3所述的光引发剂混合物APi-184S，其特征在于，所述烯烃为共轭双烯烃。
5.根据权利要求1所述的光引发剂混合物APi-184S，其特征是所述含烯键不饱和化合物树脂为（甲基）丙烯酰官能基的（甲基）丙烯酸共聚物，聚氨酯甲酸酯（甲基）丙烯酸酯，聚酯（甲基）丙烯酸酯，聚醚（甲基）丙烯酸酯，硅氧烷（甲基）丙烯酸酯，环氧树脂（甲基）丙烯酸酯。
6.根据权利要求1所述的光引发剂混合物APi-184S，其特征是所述无机填充剂为纳米氧化铝，二氧化硅，碳酸钙或硫酸钡。
7.根据权利要求1所述的光引发剂混合物APi-184S，其特征是所述着色剂为颜料或染料。
8.根据权利要求1所述的混合物APi-184S作为含烯键不饱和型可辐射聚合体系的光引发剂的用途。
9.一种UV辐射固化材料配方体系，其特征是：含有权利要求1所述的混合物APi-184S。
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| CN102282178A (zh) * | 2009-01-14 | 2011-12-14 | 巴斯夫欧洲公司 | 液体光引发剂共混物 |
| US20100256255A1 (en) * | 2009-04-07 | 2010-10-07 | Charles Stevens | Jettable ink composition |
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