CN109476943B - 光固化型喷墨印刷用透明墨水组合物 - Google Patents
光固化型喷墨印刷用透明墨水组合物 Download PDFInfo
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- CN109476943B CN109476943B CN201780045746.6A CN201780045746A CN109476943B CN 109476943 B CN109476943 B CN 109476943B CN 201780045746 A CN201780045746 A CN 201780045746A CN 109476943 B CN109476943 B CN 109476943B
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Abstract
透明墨水有如下课题:易因热引起微凝胶化,有贮藏稳定性下降的可能性,进而当透明墨水经时产生微凝胶时,喷墨性下降。作为解决方法,提供一种光固化型喷墨印刷用透明墨水组合物,其含有0.05~5.0质量%的光聚合性化合物、光聚合引发剂以及平均粒径为1~200nm的无机填料,且可见光透过率为30%以上。
Description
技术领域
本发明涉及一种光固化型喷墨印刷用透明墨水组合物。
背景技术
作为光固化型喷墨印刷用透明墨水组合物,专利文献1中记载的组合物已为公知。该组合物为透明墨水组合物中不含着色颜料或体质颜料,而只含固化性成分及固化剂等添加物的组合物。并且,通过将透明墨水组合物印刷于用了彩色墨水的记录物表面的更上方,可赋予该记录物表面亚光风格。
此外,专利文献2所记载的光固化型喷墨印刷用透明墨水组合物,不含金属粉末或着色剂,且通过在印刷含有金属粉末的墨水前印刷于记录介质上,可提高记录介质的平滑性,且可优化由含金属粉末的墨水而产生的光泽感和高级感。
另外,如专利文献3所记载,通过在光聚合性喷墨着色墨水中调配二氧化硅,来提高固化物的硬度从而提高耐磨擦性已为公知,进而如专利文献4所记载,在光固化型喷墨墨水中调配作为无机类紫外线吸收剂的氧化锌、氧化铈、金红石型氧化钛,可有效防止由紫外线引起的变色褪色也已为公知。
现有技术文献
专利文献
专利文献1日本专利特开2015-057330号公报
专利文献2日本专利特开2014-172986号公报
专利文献3日本专利特开2015-081294号公报
专利文献4日本专利特开2011-219648号公报
发明内容
通过以LED等为光源的光进行固化的光固化型喷墨印刷用透明墨水组合物,需要经由将丙烯酸酯进行自由基聚合而形成固化涂膜,因而要求高反应性。另一方面,若具有高反应性,则存在由热引起的反应性也增高的倾向。此时,对热的稳定性降低,从而使墨水的贮藏稳定性变差。因此,需要一方面提高对光的反应性一方面降低对热的反应性。
尤其透明墨水易因热引起微凝胶化,可能降低贮藏稳定性,并且一旦透明墨水经时产生微凝胶则可能导致喷出稳定性降低。
本发明人等发现,通过采用以下作为固化型喷墨印刷用透明墨水组合物,可解决上述问题,从而完成了本发明。
1.一种光固化型喷墨印刷用透明墨水组合物,其含有0.05质量%~5.0质量%的光聚合性化合物、光聚合引发剂、及平均粒径1~200nm的无机填料,且可见光透过率为30%以上;
2.根据1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,无机填料为二氧化硅和/或氧化铝;
3.根据1或2所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,含有具有氨基和/或酸基的颜料分散剂;
4.根据1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,在该光固化型喷墨印刷用透明墨水组合物中,作为光聚合性化合物,含有具有酰胺基的单官能单体与丙烯酸苄酯的合计量为50~75质量%;
5.根据4所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,具有酰胺基的单官能单体为N-乙烯基己内酰胺和/或丙烯酰基吗啉;
6.根据1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,透明墨水组合物在25℃的粘度为10mPa·s以下。
根据本发明,通过成为由特定组合构成的光固化型喷墨印刷用透明墨水组合物,从而使以紫外线、尤其是发光二极体(LED)作为光源的由紫外线产生的薄膜的固化性变优的同时使热稳定性升高,故而使墨水组合物的保存稳定性升高。
具体实施方式
以下,对本发明的光固化型喷墨印刷用透明墨水组合物(以下亦称为本发明的墨水组合物)进行详细说明。
本发明为:通过研究含有光聚合性化合物、光聚合引发剂及颜料的光固化型喷墨印刷用墨水组合物中的颜料的平均粒径和含量,而制成可见光透过率为30%以上的透明墨水组合物的发明。
(光聚合性化合物)
本发明的墨水组合物,可含有单官能单体或多官能单体作为光聚合性化合物。
(单官能单体)
作为单官能单体,可例示:甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-乙基己酯等(甲基)丙烯酸烷基酯;(甲基)丙烯酸异冰片酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸4-第三-丁基环己酯、(甲基)丙烯酸二环戊烯酯、(甲基)丙烯酸环己酯等脂环式单官能单体;甲基丙烯酸苄酯等(甲基)丙烯酸芳烷基酯;甲基丙烯酸丁氧基乙酯、丙烯酸丁氧基乙酯等(甲基)丙烯酸烷氧基烷基酯;三乙二醇单丁基醚、二丙二醇单甲基醚等聚烷二醇单烷基醚的(甲基)丙烯酸酯;六乙二醇单苯基醚等聚烷二醇单芳基醚的(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基乙酯等光聚合性单体;环氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯等光聚合性寡聚物;丙烯酰胺、甲基丙烯酰胺、二乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N,N-二乙基甲基丙烯酰胺、N,N'-亚甲基双丙烯酰胺、N,N-二甲基胺基丙基丙烯酰胺、N,N-二甲基胺基丙基甲基丙烯酰胺、二丙酮丙烯酰胺、(甲基)丙烯酰基吗啉、N-乙烯基己内酰胺、N-乙稀基吡咯啶酮等具有酰胺基和/或氨基的单官能单体;(甲基)丙烯酸胺基乙酯、N,N-二甲基胺基乙基(甲基)丙烯酸酯、N,N-二甲基胺基丙基(甲基)丙烯酸酯等具有氨基的单官能单体等。这些单官能单体可使用1种或2种以上。
单官能单体的含量,优选在透明墨水组合物中为40质量%以上,进而优选为50质量%以上。另外,单官能单体的含量,优选在透明墨水中为90质量%以下,进而优选为80质量%以下,更优选为75质量%以下。
单官能单体的含量不足40质量%时,所得的固化涂膜有密接性降低的可能性。另一方面,单官能单体的含量超过90质量%时,所得的固化涂膜有粘性、耐摩擦性降低的可能性。
这些单官能单体中,为了提升所得的固化涂膜的粘性及固化性,优选在组合物中以具有酰胺基的单官能单体与丙烯酸苄酯的合计量计而含有50~75质量%。
作为优选的具有酰胺基的单官能单体,可例示:N-乙烯基己内酰胺和/或丙烯酰基吗啉。
(多官能单体)
作为多官能单体,可例示:在分子内具有2个光聚合性官能基及2个氨基的丙烯酰基化胺化合物、(甲基)丙烯酸乙稀氧基乙氧基乙酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧基化1,6-己二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、乙氧基化双酚A二(甲基)丙烯酸酯、环己烷二甲醇二(甲基)丙烯酸酯、烷氧基化己二醇二(甲基)丙烯酸酯、烷氧基化环己烷二甲醇二(甲基)丙烯酸酯、烷氧基化二(甲基)丙烯酸酯、三环癸烷二甲醇二(甲基)丙烯酸酯、丙氧基化新戊二醇二(甲基)丙烯酸酯、烷氧基化新戊二醇二(甲基)丙烯酸酯、烷氧基化脂肪族二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三(2-羟基乙基)异氰脲酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二-三羟甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等。这些多官能单体可使用1种或2种以上。
多官能单体的含量,在透明墨水组合物中只要为15质量%以上即可,优选为20质量%以上。此外,多官能单体的含量,在透明墨水组合物中只要为50质量%以下即可,优选为35质量%以下。多官能单体的含量不足15质量%时,所得的固化涂膜的耐摩擦性、粘性易降低。另一方面,多官能单体的含量超过50质量%时,所得的固化涂膜的密接性易降低。
(光聚合引发剂)
作为光聚合引发剂,可采用酰基膦类光聚合引发剂或三嗪类光聚合引发剂等的任意一种。
酰基膦类光聚合引发剂为包含酰基膦基的光聚合引发剂,三嗪类光聚合引发剂为具有三嗪结构的光聚合引发剂。这些光聚合引发剂在450~300nm的波长全域中具有光吸收特性,受到这些特定波长的光(UV-LED)的照射而使透明墨水组合物聚合并进行高分子化。
作为酰基膦类光聚合引发剂,可例示:2,4,6-三甲基苯甲酰基二苯基氧化膦、2,6-二甲氧基苯甲酰基二苯基氧化膦、2,6-二氯苯甲酰基二苯基氧化膦、2,3,5,6-四甲基苯甲酰基二苯基氧化膦、2,6-二甲基苯甲酰基二甲基氧化膦、4-甲基苯甲酰基二苯基氧化膦、4-乙基苯甲酰基二苯基氧化膦、4-异丙基苯甲酰基二苯基氧化膦、1-甲基环己酰基苯甲酰基二苯基氧化膦、双(2,4,6三甲基苯甲酰基)-苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸甲酯、2,4,6-三甲基苯甲酰基苯基膦酸异丙酯、双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦、双(2,6-二甲氧基苯甲酰基)-2,3,3-三甲基-戊基氧化膦等。具体而言,作为2,4,6-三甲基苯甲酰基-二苯基-氧化膦,可例示TPO(Lamberti公司制),作为双(2,4,6三甲基苯甲酰基)-苯基氧化膦,可例示IRGACURE 819(BASF公司制)等。
作为三嗪类光聚合引发剂,可例示:2,4,6-三氯-均三嗪、2-苯基-4,6双(三氯甲基)-均三嗪、2-(对甲氧基苯基)-4,6-双(三氯甲基)-均三嗪、2-(对甲苯基)-4,6-双-(三氯甲基)均三嗪、2-胡椒基-4,6-双(三氯甲基)-均三嗪、2,4-双(三氯甲基)-6-苯乙烯基-均三嗪、2-(萘-1-基)-4,6-双(三氯甲基)-均三嗪、2-(4-甲氧基-萘-1-基)-4,6-双(三氯甲基)均三嗪、2,4-三氯甲基-(胡椒基)-6-三嗪、2,4-三氯甲基(4'-甲氧基苯乙烯基)-6-三嗪等。
光聚合引发剂的含量,优选在透明墨水组合物中为5.0质量%以上,进而优选为6.0质量%以上。此外,光聚合引发剂的含量,优选在透明墨水组合物中为15.0质量%以下,进而优选为12.0质量%以下。光聚合引发剂的含量不足5.0质量%时,透明墨水组合物有UV-LED固化性易降低的可能性。此外,通过设定为此范围,使固化涂膜中不易发生黄变。另一方面,当光聚合引发剂的含量超过15.0质量%时,则透明墨水组合物通过进而调配光聚合引发剂而产生的固化性的效果不会提升,且易过量添加。
再者,本实施方式的透明墨水组合物,优选调配5.0~15.0质量%的酰基膦类光聚合引发剂,也可在不降低性能的范围内合用其他光聚合引发剂。可使用所述光聚合引发剂中的1种或2种以上,进而作为其他光聚合引发剂,也可合用噻吨酮类光聚合引发剂、α-羟基酮类光聚合引发剂等。
(平均粒径1~200nm的无机填料)
作为本发明中使用的平均粒径1~200nm、优选平均粒径1~100nm的无机填料,优选体质颜料,进而优选使用二氧化硅、氧化铝、碳酸钙,更优选使用二氧化硅和氧化铝。此外,这些无机填料既可使用一种也可合用两种以上。
而且,视需要对这些颜料进行粉碎,使其平均粒径为1~200nm,优选为1~100nm。再者,此处提及的平均粒径是采用以下方法测定所得的值。平均粒径使用日机装公司制的Microtrac UPA-150进行测定。
平均粒径1~200nm的无机填料,以成为0.05~5.0质量%、优选为0.05~3.0质量%的方式调配于本发明的透明墨水组合物中。若调配量不足0.05质量%,则无法提升对热的稳定性,保存稳定性变差,易产生微凝胶。当调配量超过5.0质量%时,自重过滤试验结果及其促进试验结果不良。
此外,即使将平均粒径调为不足1nm,也无法期待对热的稳定性的进一步提升,且难以制造如此极微细粒径的无机填料。
此外,当平均粒径超过200nm时,难以使其均匀分散于墨水组合物中,并且无法提升对热的稳定性,保存稳定性变差,易产生微凝胶。且自重过滤试验的促进试验结果不良。
此外,鉴于本发明的墨水组合物为透明墨水,作为所添加的无机填料的种类及其调配量,是使其可见光透过率为30%以上、优选50%以上、更优选为70%以上、最优选为90%以上。
(颜料分散剂)
此外,本发明的光固化型喷墨印刷用透明墨水组合物,视需要也可含有颜料分散剂。
颜料分散剂是为了提升颜料的分散性、及本发明的光固化型喷墨印刷用墨水组合物的保存稳定性而使用的,可不特别限制地使用以往所用的颜料分散剂,其中优选使用高分子分散剂。作为此种颜料分散剂,可列举:碳二酰亚胺类分散剂、聚酯胺类分散剂、脂肪酸胺类分散剂、改性聚丙烯酸酯类分散剂、改性聚胺基甲酸酯类分散剂、多链型高分子非离子类分散剂、高分子离子活性剂等。这些颜料分散剂可单独使用或两种以上混合使用。
将所使用的所有颜料的量设定为100质量份时,优选为含有1~200质量份的所述颜料分散剂。若颜料分散剂的含量不足1质量份,则存在顔料分散性、及本发明的墨水组合物的保存稳定性降低的情况。另一方面,也可含有超过200质量份,但也存在效果无差别的情况。颜料分散剂含量的更优选下限为5质量份、更优选上限为60质量份。
(酮树脂)
为防止产生粘性,本发明的光固化型喷墨印刷用墨水组合物中也可含有酮树脂。
所述酮树脂,只要能溶解于所述光聚合性化合物中,则无特别限定,可使用公知的酮树脂。
作为酮树脂,优选具有羟基的酮树脂,具体而言,例如可列举:(1)将酮树脂加氢而获得的含羟基的酮树脂,所述酮树脂是使苯乙酮等芳香族类酮化合物、环己酮或三甲基环己酮等脂环族类酮化合物之类的含酮基的化合物,与甲醛等醛化合物进行反应而获得,(2)含有羟基的胺基甲酸酯改性酮树脂等,其为使异佛尔酮二异氰酸酯等聚异氰酸酯化合物,与具有能与异氰酸酯化合物反应的取代基的酮树脂反应而获得。这些可分别单独使用,此外也可两种以上组合使用。
而且,这些酮树脂已为市售,具体而言,例如有Evonik公司制的SK、PZZ-1201等。
当含有所述酮树脂时,为防止产生粘性,优选其含量在光固化型喷墨印刷用墨水组合物中为5.0~15.0质量%。
本发明的透明墨水组合物,可通过现有的公知方法进行制备。若列举一例,透明墨水组合物例如可通过将所述各成分及后述的任意成分全部混合并搅拌而制备。将所得的透明墨水组合物在25℃下的粘度调整为1.0mPa·s以上。此外,透明墨水组合物在25℃下的粘度调整为10.0mPa·s以下,优选为5.0mPa·s以下。此种透明墨水组合物通过喷墨记录装置印刷时的喷出稳定性优异。尤其,此种透明墨水组合物在常温下从喷墨记录装置的头部的喷出稳定性优异,所述喷墨记录装置的头部是为了实现节能化、高速化、高精细化而对应低粘度墨水进行设计的。
此外,本实施方式的透明墨水组合物,可通过现有的公知方法打印、固化。若列举一例,透明墨水组合物可通过如下方法进行打印、硬化:所述透明墨水组合物被喷出至基材或打印于基材上的印刷物(以下也简称为基材等)上之后,用UV-LED将着落于基材等上的透明墨水组合物的涂膜进行曝光并使其硬化。
作为基材,可无特别限制地使用以往用于UV-LED固化型喷墨印刷用透明墨水组合物的基材。具体而言,可例示:纸、塑胶膜、胶囊、金属箔、玻璃等。其中,作为地板材料而使用,优选氯乙烯、聚碳酸酯等。
将本实施方式的透明墨水组合物例如供给至喷墨记录装置(喷墨打印机)的对应低粘度的打印机头部,且自打印机头部喷出至基材。所喷出的透明墨水组合物以使膜厚成为例如1~60μm的方式着落于基材上。着落后的透明墨水组合物通过照射UV-LED而适当固化。此外,作为将本实施方式的透明墨水组合物进行打印的喷墨记录装置,可利用现有公知的喷墨记录装置。此时,在使用连续类型(continuous type)的喷墨记录装置时,透明墨水组合物更优选为添加导电性赋予剂且适当调整电导率。
(透明墨水组合物的任意成分)
继而,对本实施方式的透明墨水组合物适宜地含有的任意成分进行说明。本实施方式的透明墨水组合物除了所述成分以外,为了表现各种功能,也可适当调配任意成分。例如,透明墨水组合物也可含有表面活性剂、溶剂、染料、其他着色颜料等颜料、增感剂、颜料分散剂以及各种添加剂。
(表面活性剂)
为了提升透明墨水组合物的喷出稳定性等,可根据使用透明墨水组合物的喷墨记录装置的头部,适当调配表面活性剂。作为表面活性剂,可例示以往在光固化型喷墨印刷用墨水组合物中适当使用的硅酮类表面活性剂等。具体而言,作为硅酮类表面活性剂可例示:聚醚改性硅油、聚酯改性聚二甲基硅氧烷、聚酯改性甲基烷基聚硅氧烷等。这些表面活性剂也可合用。
表面活性剂的含量,优选在透明墨水组合物中为0.005质量%以上。此外,表面活性剂的含量,优选在透明墨水组合物中为1.0质量%以下。当表面活性剂的含量不足0.005质量%时,则透明墨水组合物的表面张力变大,喷出稳定性易降低。另一方面,当表面活性剂的含量超过1.0质量%时,透明墨水组合物易含有气泡,喷出稳定性易降低。
(溶剂)
溶剂也可适当调配于透明墨水组合物中。作为溶剂,可例示:酯类有机溶剂、醚类有机溶剂、醚酯类有机溶剂、酮类有机溶剂、芳香族烃溶剂、含氮类有机溶剂等。此外,作为溶剂,可例示常压(1.013×102kPa)下的沸点为150~220℃的溶剂。
从透明墨水组合物的固化性、环境问题等观点出发,优选尽量不使用有机溶剂。因此,有机溶剂的含量,优选在透明墨水组合物中为5质量%以下、更优选为2质量%以下、进而优选为不使用。
(其他颜料)
为了获得各种颜色的透明墨水组合物,也可适当调配除平均粒径1~200nm的无机填料以外的顔料。作为此种颜料,可为以往用于通常的光固化型喷墨印刷用墨水组合物中的颜料,具体而言,优选良好地分散于透明墨水组合物中且耐候性优异的有机颜料或无机填料。具体而言,作为所述有机颜料,可列举:染料色淀顔料、偶氮类、苯并咪唑酮类、酞菁类、喹吖啶酮类、蒽醌类、二恶嗪类、靛蓝类、硫靛蓝类、苝类、芘酮类、二酮吡咯并吡咯类、异吲哚啉酮类、硝基类、亚硝基类、黄蒽酮类、喹酞酮类、皮蒽酮类、阴丹酮类的顔料等。这些颜料也可合用。
但是,在调配这些颜料时,必须不会妨碍通过调配平均粒径1~200nm的无机填料而产生的效果。
(增感剂)
进一步地,为了促进针对以发光二极体(LED)为光源的紫外线的固化性,本发明的光固化型喷墨印刷用透明墨水组合物中可合用如下光增感剂(化合物):在400nm以上主要为紫外线的波长区域内具有光吸收特性,且籍由该范围的波长的光而表现出固化反应增感功能的光增感剂。
再者,所述“通过400nm以上的波长的光而表现出增感功能”,是指在400nm以上的波长区域内具有光吸收特性。通过使用此种增感剂,可促进本发明的光固化型喷墨印刷用透明墨水组合物的LED固化性。
作为所述光增感剂,为蒽类增感剂、噻吨酮类增感剂等,优选噻吨酮类增感剂。这些可单独使用或合用两种以上。
具体而言,可列举:9,10-二丁氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-双(2-乙基己基氧基)蒽等蒽类增感剂;2,4-二乙基噻吨酮、2-异丙基噻吨酮、4-异丙基噻吨酮等噻吨酮类增感剂。作为市售品的代表例,蒽类增感剂可例示己二酸二丁酯(dibutyladipate,DBA)、二乙醇胺(diethanol amine,DEA)(川崎化成工业公司制),噻吨酮类增感剂可例示2,4-二乙基噻吨酮(2,4-diethyl thioxanthone,DETX)、异丙基噻吨酮(isopropylthioxanthone,ITX)(LAMBSON公司制)等,但是,为了防止变色,最好不使用噻吨酮类增感剂。
(各种添加剂)
作为各种添加剂,也可适当调配热固化性树脂、光稳定化剂、表面处理剂、粘度降低剂、抗氧化剂、抗老化剂、交联促进剂、聚合抑制剂、塑化剂、防腐剂、pH调节剂、消泡剂、保湿剂等。
如上所述,本实施方式的透明墨水组合物,包含40~90质量%的单官能单体、15~50质量%的多官能单体、5~15质量%的酰基膦类光聚合引发剂。此种透明墨水组合物的UV-LED固化性优异。
此外,所得的固化涂膜对基材的密接性、耐摩擦性优异。
实施例
以下列举实施例来进一步详细说明本发明,但本发明并非仅限于这些实施例。再者,只要无特别声明,则“%”意味着“质量%”,“份”意味着“质量份”。
以下实施例、比较例中所使用的材料如下:
<颜料分散剂>
AJISPER(注册商标)PB821(味之素Fine Techno株式会社制)
<光聚合性化合物>
丙烯酸苄酯(大阪有机化学工业公司制)
乙烯基己内酰胺1,6-己二醇二丙烯酸酯
<光聚合引发剂>
TOP:2,4,6-三甲基苯甲酰基-二苯基-氧化膦(2,4,6-trimethylbenzoyldiphenyl phosphine oxide)(LAMBERTI公司制)
<添加剤>
BYK-315(硅酮添加剂,BYK Chemie公司制)
UV-5=顺丁烯二酸二辛酯(Kromachem公司制)
UV-22=醌类聚合抑制剂(Kromachem公司制)
<无机氧化物>
二氧化硅(粒径20nm,NANOCRYL C140,Evonik公司制,分散于1,6-己二醇二丙烯酸酯中的物质,固体成分50%)
氧化铝(粒径80nm,AEROXIDE Alu-C,日本Aerosil,本公司分散,固体成分10%)
<氧化铝分散物的制备>
在预磨机(ready mill)(珠径:0.2nm,填充率50%)中将10质量份的AEROXIDEAlu-C、1质量份的作为分散剂的PB-821、89质量份的丙烯酸苄酯研磨60分钟,获得粘度4.9cps、粒度分布80nm的固体成分10%的氧化铝分散物。
<实施例1~8及比较例1~3>
〔光固化型喷墨印刷用透明墨水组合物的制备〕
以成为表1调配组合(质量%)的方式将各成分调配,并搅拌混合,获得实施例1~8、比较例1~3的光固化型喷墨印刷用透明墨水组合物。
〔光固化型喷墨印刷用透明墨水组合物的粘度测定〕
针对实施例1~8及比较例1~3所得的各光固化型喷墨印刷用透明墨水组合物,使用E型粘度计(商品名:RE100L型粘度计,东机产业公司制),在温度25℃、转子旋转速度50rpm的条件下,测定粘度。
实施例1~8、比较例1~3的光固化型喷墨印刷用透明墨水组合物的粘度为约7mPa·s。
<可见光透过率>
可见光透过率通过紫外·可见分光光度计(商品名:UV-Vis RecordingSpectrophotometer,岛津制作所公司制)进行测定。
<自重过滤试验>
实施例1~8、比较例1~3的光固化型喷墨印刷用透明墨水组合物在刚刚制作后(初期)以及60℃保存1个月后,用2600目使40g各光固化型喷墨印刷用透明墨水组合物通过SPC滤光片架(filter holder)(φ25nm,柴田科学公司制)来测定通过率。
[表1]
根据依照本发明的例子即实施例1~8,虽然为可见光透过率高的透明墨水,但即便在60℃下促进(保存)1个月后,仍具备与刚刚制作后的初期状态相比几乎未变化的贮藏稳定性。相对于此,根据无机填料的含量不足的比较例1、过量添加的比较例2、添加有平均粒径大的无机填料的比较例3,在60℃促进(保存)1个月后发生了变质。当过量添加无机填料、或无机填料过大时,在刚刚制作后贮藏稳定性就已经变差。
Claims (6)
1.一种光固化型喷墨印刷用透明墨水组合物,其含有光聚合性化合物、光聚合引发剂、及平均粒径1~200nm的无机填料,其中所述无机填料在组合物中为0.05质量%~3.0质量%,且在680nm处测量的组合物的可见光透过率为30%以上。
2.根据权利要求1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,无机填料为二氧化硅和/或氧化铝。
3.根据权利要求1或2所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,含有具有氨基和/或酸基的颜料分散剂。
4.根据权利要求1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,在光固化型喷墨印刷用透明墨水组合物中,作为光聚合性化合物,含有具有酰胺基的单官能单体与丙烯酸苄酯的合计量为50~75质量%。
5.根据权利要求4所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,具有酰胺基的单官能单体为N-乙烯基己内酰胺和/或丙烯酰基吗啉。
6.根据权利要求1所述的光固化型喷墨印刷用透明墨水组合物,其特征在于,透明墨水组合物在25℃的粘度为10mPa·s以下。
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EP3498789A4 (en) | 2020-04-15 |
CN109476943A (zh) | 2019-03-15 |
WO2018030027A1 (ja) | 2018-02-15 |
US20190169454A1 (en) | 2019-06-06 |
AU2017310604A1 (en) | 2019-03-07 |
JP6869664B2 (ja) | 2021-05-12 |
CA3032915C (en) | 2024-01-16 |
JP2018024757A (ja) | 2018-02-15 |
EP3498789B1 (en) | 2024-01-24 |
TW201817828A (zh) | 2018-05-16 |
TWI733853B (zh) | 2021-07-21 |
KR20220009487A (ko) | 2022-01-24 |
KR102463006B1 (ko) | 2022-11-03 |
AU2017310604B2 (en) | 2021-07-22 |
CA3032915A1 (en) | 2018-02-15 |
KR20190038804A (ko) | 2019-04-09 |
ES2972163T3 (es) | 2024-06-11 |
US11230647B2 (en) | 2022-01-25 |
EP3498789A1 (en) | 2019-06-19 |
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