CN110804276A - 一种高分辨光固化三维打印复合物 - Google Patents
一种高分辨光固化三维打印复合物 Download PDFInfo
- Publication number
- CN110804276A CN110804276A CN201910995688.4A CN201910995688A CN110804276A CN 110804276 A CN110804276 A CN 110804276A CN 201910995688 A CN201910995688 A CN 201910995688A CN 110804276 A CN110804276 A CN 110804276A
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- CN
- China
- Prior art keywords
- photoacid generator
- salt type
- onium salt
- type photoacid
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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Abstract
本发明公开了一种高分辨光固化三维打印复合物，包括环氧单体及齐聚物或乙烯基醚单体及齐聚物，以及环氧树脂和乙烯基醚树脂的混合物、鎓盐型光酸剂、三取代有机胺酸扩散抑制剂、夺氢型自由基光引发剂和紫外光屏蔽吸收剂；鎓盐型光酸剂占复合物质量百分比的0.5～10％；夺氢型自由基光引发剂与鎓盐型光酸剂的质量比为1:10～1:1；三取代有机胺酸扩散抑制剂与鎓盐型光酸剂的质量比为1:100～1:2，紫外光屏蔽吸收剂占复合物质量的百分比为0.1～5％。本发明的复合物材料固化速度快，可获得横向亚微米以下的3D打印分辨率。
Description
技术领域
本发明涉及一种用于三维打印的光固化树脂复合物材料。
背景技术
光固化树脂固化速度快、固化后机械及抗腐蚀性能好、污染少，在科研、国防、工业生产、日常生活中均具有很大的需求与应用。3D打印技术是近年来发展迅猛的一种快速制造技术，其中光固化3D打印技术是3D打印技术中最重要的分支技术之一，光固化树脂是光固化3D打印技术的核心材料。
常用的紫外光固化树脂主要分为以下四类：(1)丙烯酸酯树脂；(2)甲基丙烯酸树脂；(3)环氧树脂；(4)乙烯基醚树脂。其中最常用的是丙烯酸酯树脂，丙烯酸酯树脂种类繁多，可选择范围宽，被广泛应用，在自由基引发下具有极快的聚合速率，但另一方面，该聚合过程由于环境中的氧易与自由基反应形成过氧自由基，并进一步终止聚合反应，因此反应常常需要在真空、惰性气氛下进行，或加入有活性氢的叔胺、硫醇、膦类化合物作为过氧自由基的清除剂。此外，丙烯酸酯具有较大的刺激性，对人体有害。甲基丙烯酸树脂与环氧树脂最主要的缺点就是聚合速率慢，聚合不完全。另外自由基聚合反应的特点是聚合反应不易即时、可控的阻聚和终止。
环氧树脂与乙烯基醚树脂基于阳离子引发聚合机理，聚合过程几乎不受氧的影响。阳离子聚合反应的另一个特点是，引发反应的质子酸与聚合后形成的碳正离子可与有机胺等碱性化合物迅速反应，从而聚合反应可即时、可控的阻聚与终止。
目前丙烯酸树脂已广泛用于光固化3D打印技术，但是由于自由基聚合反应可控性差，较难即时终止聚合反应从曝光区域向未曝光区域的扩散，因此获得的3D打印成品表面粗糙度大、分辨率低。环氧、乙烯基醚树脂由于聚合反应速率较低，还较少用于商品化的光固化3D打印树脂，但其聚合反应的良好可控性使实现亚微米高分辨的光固化3D打印成为可能。
发明内容
本发明的目的是提出一种光固化的3D打印复合物材料，以改善3D打印成品的分辨率和表面粗糙度。
本发明采用的技术方案是：
一种高分辨光固化三维打印复合物，包括环氧单体及齐聚物或乙烯基醚单体及齐聚物，以及环氧树脂和乙烯基醚树脂的混合物、鎓盐型光酸剂、三取代有机胺酸扩散抑制剂、夺氢型自由基光引发剂、紫外光屏蔽吸收剂和其他添加剂；所述鎓盐型光酸剂占复合物质量百分比的0.5～10％；所述夺氢型自由基光引发剂与鎓盐型光酸剂的质量比为1:10～1:1；所述三取代有机胺酸扩散抑制剂与鎓盐型光酸剂的质量比为1:100～1:2，所述紫外光屏蔽吸收剂占复合物质量的百分比为0.1～5％。
进一步地，所述复合物在25℃条件下，其粘度在10厘泊/秒～300厘泊/秒。
进一步地，所述鎓盐型光酸剂为二烷基苯甲酰硫盐、三芳基硫或者二芳基碘鎓盐型光酸生成剂。
优选地，所述鎓盐型光酸剂占复合物质量百分比的1～5％。
优选地，所述三取代有机胺酸扩散抑制剂与鎓盐型光酸剂的质量比为1:100～1:10。
本发明结合阳离子聚合反应链终止的良好可控性与夺氢型自由基光引发剂对阳离子聚合反应的加速作用，可以得到一种固化速度快、亚微米分辨率的光固化3D打印复合物。本发明核心是在基于阳离子引发聚合的光固化复合物中加入酸扩散抑制剂，防止曝光产生的质子酸从曝光区域向未曝光区域的自由扩散及聚合反应从曝光部分向未曝光部分扩散而引起的未曝光区域的材料固化、分辨率降低、成品表面粗糙度大的问题，可以获得横向亚微米以下的3d打印分辨率。
附图说明
图1是未加三取有机胺聚合反应从曝光区域向未曝光区域扩散的示意图；
图2是本发明加了三取代胺，抑制聚合反应从曝光区域向未曝光区域扩散的示意图。
具体实施方式
本实施例的3D打印光固化复合材料，由基于阳离子引发聚合机理的低粘度的环氧单体和齐聚物或乙烯基醚单体和齐聚物以及它们的混合物、鎓盐型光酸剂、三取代有机胺酸扩散抑制剂、夺氢型自由基光引发剂、紫外光吸收剂或染料等组成。阳离子引发聚合的体系中加入夺氢型自由基光引发剂，可以显著的提高环氧树脂与乙烯基醚树脂的聚合速率，同时加入对可见光响应的夺氢型自由基光引发剂，还可把阳离子引发聚合树脂的曝光波长从紫外光进一步拓展到可见光区域。
低粘度的单体或齐聚物是在室温下呈现低粘度的液体，在室温或以25℃为标准，单体或齐聚物的粘度在10厘泊/秒～300厘泊/秒；环氧单体的环氧基团包括环氧乙烷、环氧丙烷或环氧环己烷等，具体的环氧单体和齐聚物可以是1,2-环氧丙烷、1,2-环氧丁烷、1,2-环氧戊烷、1,2-环氧己烷、1,2-环氧环己烷、环氧丙基苯基醚、环氧丙基2-甲氧苯基醚、1,3-双[2-(3,4-环氧环己基-1-基)乙基]四甲基二硅氧烷、3,4-环氧环己基甲基3,4-环氧环己基甲酸酯、异氰尿酸三缩水甘油酯、间苯二酚二缩水甘油醚、双酚A二缩水甘油醚、聚[(苯基缩水甘油醚)-co-甲醛]等；具体的乙烯基醚单体和齐聚物可以是乙烯基乙基醚、乙烯基丙基醚、乙烯基丁基醚、乙烯基异丁基醚、乙烯基叔丁基醚、乙二醇单乙烯基醚、环己基乙烯基醚、4-羟丁基乙烯基醚、[4-(乙烯氧基)丁基]苯甲酸酯、[4-(乙烯氧基)甲基]环己烷苯甲酸酯、4-(乙烯氧基)硬脂酸丁酯、二乙二醇单乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、1,4-环己烷二甲醇二乙烯基醚、二[4-(乙烯氧基)丁基]己二酸酯、二[4-(乙烯氧基)丁基]琥珀酸酯、二[4-(乙烯氧基)丁基]异酞酸酯、二[4-(乙烯氧基甲基)环己基甲基]戊二酸酯、二[4-(乙烯基氧代)丁基]1,6-己二基二氨基甲酸酯、二[[4-[(乙烯基氧基)甲基]环己基]甲基]对苯二甲酸酯、二[[4-[(乙烯基氧基)甲基]环己基]甲基]间苯二甲酸酯、(4-甲基-1,3-亚苯基)二氨基甲酸-二[4-(乙烯氧基)丁基]酯、(亚甲基二-4,1-亚苯基)二氨基甲酸-二[4-(乙烯氧基)丁基]酯、三[4-(乙烯醚)丁基]三苯六甲酸酯等。
基于阳离子引发聚合机理的可紫外光固化材料的光引发剂为硫、碘鎓盐型光酸生成剂，即二烷基苯甲酰硫盐、三芳基硫或二芳基碘鎓盐型光酸生成剂，光酸生成剂的用量为光固化树脂质量百分比的0.5～10％，优选1～5％。
在光固化复合物材料中加入了光引发聚合反应抑制剂，来控制引发剂扩散和聚合反应扩散的问题，见图2所示。聚合反应抑制剂主要为三取代有机胺，通过碱与质子酸中和反应与碳正离子链的终止反应，实现抑制聚合反应从曝光区域向未曝光区域的扩散，实现横向高分辨率打印。光引发聚合反应抑制剂的用量与光引发剂的用量比为1:100～1:2，优选1:100～1:10。三取代有机胺酸扩散抑制剂可以是二丁基乙醇胺、二异丁基乙醇胺、二甲基十一烷基胺、三异丙醇胺、鹰爪豆碱、甲基二环己基胺、三异丁基胺、1,8-双(二甲基氨基)萘、N,N’-双(2,2-二乙氧基乙基)甲基胺、2,2’-二氮杂环[2.2.2]辛烷、2,4,6-三苯基-1,3,5-三嗪、二环己基甲胺等。
夺氢型自由基光引发剂在光照下可与给氢型单体发生反应，产生与单体相结合的自由基，该自由基可以迅速还原鎓盐型光酸剂，产生单体为中心的碳正离子，并继续引发其它环氧、乙烯基醚单体的聚合，显著提高聚合反应的速率。加入对可见光响应的自由基引发剂还可把鎓盐型光酸剂的曝光波长从紫外光延伸至可见光范围。自由基光引发剂与光酸剂的质量之比为1:10～1:1。夺氢型自由基光引发剂可以是二本甲酮及其衍生物、硫杂蒽酮及其衍生物、樟脑醌、苯偶酰、2-乙基蒽醌等。
紫外光吸收剂和染料的作用是吸收紫外光和可见光，屏蔽进入光固化材料内部的光线，控制3D打印纵向的打印厚度，提高纵向打印精度。紫外光吸收剂和染料用量为复合物质量百分比的0.5～10％。紫外光吸收剂或染料可以是邻羟基苯甲酸苯酯、2-(2’-羟基-5’-甲基苯基)苯并三氮唑、2,4-二羟基二苯甲酮、2-(2’-羟基-3’,5’-二叔苯基)-5-氯化苯并三唑、单苯甲酸间苯二酚酯、2-(2-羟基-3,5双(a,a-二甲基苄基)苯基)苯骈三唑、2-(2-羟基-3-特丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羟基-3-特丁基-5-甲基苯基)-5-氯苯并三唑、或尼罗红(Nile red)、奥丽色黄(Oracet Yellow)、奥丽色橙(Oracet Orang)、水性染料多甘酸黄XX-SF(Duasyn Acid Yellow XX-SF)、苏丹红、活性橙等。
以下给出几种优选复合材料的实例：
实施例1
光固化复合物材料1由如下质量百分比的组分组成：30％1,2-环氧己烷、30％1,2-环氧己烷、30％3,4-环氧环己基甲基3,4-环氧环己基甲酸酯、6％双酚A二缩水甘油醚、2％(4-辛烷氧基苯基)苯碘鎓六氟锑酸盐、1％2-异丙基硫杂蒽酮、0.5％1,8-双(二甲基氨基)萘、0.5％2-(2’-羟基-5’-甲基苯基)苯并三氮唑。
实施例2
光固化复合物材料2由如下质量百分比的组分组成：50％乙二醇单乙烯基醚、40％三乙二醇二乙烯基醚、5％三[4-(乙烯醚)丁基]三苯六甲酸酯、1.5％(4-辛烷氧基苯基)苯碘鎓六氟锑酸盐、0.5％2-异丙基硫杂蒽酮、0.5％1,8-双(二甲基氨基)萘、0.5％2-(2’-羟基-5’-甲基苯基)苯并三氮唑。
实施例3
光固化复合物材料3由如下质量百分比的组分组成：10％1,2-环氧戊烷、20％环氧丙基苯基醚、15％双酚A二缩水甘油醚、10％环己基乙烯基醚、20％4-羟丁基乙烯基醚、21％二[[4-[(乙烯基氧基)甲基]环己基]甲基]对苯二甲酸酯、2％(4-辛烷氧基苯基)苯碘鎓六氟锑酸盐、1％2-异丙基硫杂蒽酮、0.5％1,8-双(二甲基氨基)萘、0.5％2-(2’-羟基-5’-甲基苯基)苯并三氮唑。
Claims (5)
1.一种高分辨光固化三维打印复合物，其特征在于，包括环氧单体及齐聚物或乙烯基醚单体及齐聚物，以及环氧树脂和乙烯基醚树脂的混合物、鎓盐型光酸剂、三取代有机胺酸扩散抑制剂、夺氢型自由基光引发剂和紫外光屏蔽吸收剂；所述鎓盐型光酸剂占复合物质量百分比的0.5～10％；所述夺氢型自由基光引发剂与鎓盐型光酸剂的质量比为1:10～1:1；所述三取代有机胺酸扩散抑制剂与鎓盐型光酸剂的质量比为1:100～1:2，所述紫外光屏蔽吸收剂占复合物质量的百分比为0.1～5％。
2.根据权利要求1所述的一种高分辨光固化三维打印复合物，其特征在于，所述复合物在25℃条件下，其粘度在10厘泊/秒～300厘泊/秒。
3.根据权利要求1所述的一种高分辨光固化三维打印复合物，其特征在于，所述鎓盐型光酸剂为二烷基苯甲酰硫盐、三芳基硫或者二芳基碘鎓盐型光酸生成剂。
4.根据权利要求1所述的一种高分辨光固化三维打印复合物，其特征在于，所述鎓盐型光酸剂占复合物质量百分比的1～5％。
5.根据权利要求1所述的一种高分辨光固化三维打印复合物，其特征在于，所述三取代有机胺酸扩散抑制剂与鎓盐型光酸剂的质量比为1:100～1:10。
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| CN112500026A (zh) * | 2020-12-04 | 2021-03-16 | 西安交通大学 | 光固化用短切石英纤维增强氧化硅陶瓷膏料及其制备方法 |
| CN112500026B (zh) * | 2020-12-04 | 2021-11-30 | 西安交通大学 | 光固化用短切石英纤维增强氧化硅陶瓷膏料及其制备方法 |
| CN112429946A (zh) * | 2020-12-07 | 2021-03-02 | 西安交通大学 | 小尺寸内流道玻璃器件基于3d打印的一体成型制备方法 |
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