LED封装用UV光固化硅树脂的制备及性能研究

doi:10.19491/j.issn.1001-9278.2020.05.012

中国塑料 ›› 2020, Vol. 34 ›› Issue (5): 68-76.DOI: 10.19491/j.issn.1001-9278.2020.05.012

LED封装用UV光固化硅树脂的制备及性能研究

刘珠¹, 林子谦¹, 向洪平¹(), 容敏智², 章明秋²

^1.广东工业大学材料与能源学院，广东省功能软凝聚态物质重点实验室，广州 510006
^2.中山大学化学学院，聚合物复合材料及功能材料教育部重点实验室，广州 510275

收稿日期:2020-02-20 出版日期:2020-05-26 发布日期:2020-05-22
基金资助:
国家自然科学基金项目(51873043);广东省重大专项科技基金(2015B010122005)

Preparation and Properties of UV⁃curable Silicone Resin for LED Package

Zhu LIU¹, Ziqian LIN¹, Hongping XIANG¹(), Minzhi RONG², Mingqiu ZHANG²

^1.Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
^2.Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, GD HPPC Lab, School of Chemistry, Sun Yat?sen University, Guangzhou 510275, China

Received:2020-02-20 Online:2020-05-26 Published:2020-05-22
Contact: Hongping XIANG E-mail:xianghongping@gdut.edu.cn

摘要/Abstract

摘要：

通过水解?缩聚制备了不同分子结构的巯基硅树脂（MDT?SH），并将MDT?SH与乙烯基硅树脂和光引发剂配合，制备了紫外（UV）光固化硅树脂；然后对UV光固化树脂的光固化动力学进行了研究，对光固化制品的热稳定性、透光性和封装性能进行了详细分析。结果表明，当有机基团与硅的比值（R/Si）为1.88，巯基含量为0.34 mol/100 g时，MDT?SH硅树脂的相对分子质量分布较均匀且产率较高；当光引发剂2,4,6?三甲基苯甲酰基膦酸乙酯（TPO?L）的含量为1.0 %、辐照强度为80 mW/cm²、巯基与乙烯基摩尔比（SH/Vi）为1.5/1时，树脂可较快速交联成型；UV光固化树脂不仅具有优异的透光率和耐热性，且其封装发光二极管（LED）器件的性能明显优于市售道康宁封装胶OE?6550；有望替代传统热固型LED封装胶，实现规模化使用。

关键词: 紫外光固化, 巯基硅树脂, 发光二极管封装胶, 巯基?烯光点击反应

Abstract:

A type of thiol?functionalized MDT silicone resin (MDT?SH) with different molecular structures was synthesized by hydrolysis?polycondensation, and then the MDT?SH was mixed with vinyl?functionalized silicone resin and photo?initiator to prepare a UV?curable silicone resin. The UV?curing kinetics of this UV?curable silicone resin was studied, and its thermal stability, transmittance and package performance were analyzed in detail. The results indicated that the MDT?SH exhibited a more uniform molecular weight distribution and a higher yield when synthesized at the R/Si molar ratio of 1.88/1 and the thiol content of 0.34 mol/100 g. The UV?curable silicone resin with a TPO?L dosage of 1.0 % and an SH/Vi molar ratio of 1.5/1 could be instantly cured when exposed to UV irradiation at 80 mW/cm². The UV?cured resin exhibited an excellent thermal stability and transmittance. The LED packaged by this UV?cured silicone resin also showed much better performance than those packaged by the Dow Corning OE?6550 commercial counterpart. The UV?curable silicone resin developed by this work shows a great potential in LED package in future.

Key words: ultraviolet?curing, thiol?functionalized silicone resin, light emitting diode package, thiol?ene photo?click reaction

中图分类号:

TQ322.4⁺1

刘珠, 林子谦, 向洪平, 容敏智, 章明秋. LED封装用UV光固化硅树脂的制备及性能研究[J]. 中国塑料, 2020, 34(5): 68-76.

Zhu LIU, Ziqian LIN, Hongping XIANG, Minzhi RONG, Mingqiu ZHANG. Preparation and Properties of UV⁃curable Silicone Resin for LED Package[J]. China Plastics, 2020, 34(5): 68-76.

图/表 12

参考文献 15

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样品编号	KH580含量/g	DDS含量/g	MM含量/g	HCl含量^a）/g	H₂O含量^b）/g
SM?0.43	119.21（0.50 mol）	24.64（0.10 mol）	31.01（0.19 mol）	3.50	21.42（1.19 mol）
SM?0.39	143.05（0.60 mol）	49.28（0.20 mol）	36.54（0.22 mol）	4.58	27.72（1.54 mol）
SM?0.35	47.68（0.20 mol）	24.64（0.10 mol）	11.86（0.07 mol）	1.68	10.08（0.56 mol）
SM?0.26	23.84（0.10 mol）	24.64（0.10 mol）	5.52（0.03 mol）	1.08	6.30（0.35 mol）

样品编号	KH580含量/g	DDS含量/g	MM含量/g	HCl含量^a）/g	H₂O含量^b）/g
SM?0.43	119.21（0.50 mol）	24.64（0.10 mol）	31.01（0.19 mol）	3.50	21.42（1.19 mol）
SM?0.39	143.05（0.60 mol）	49.28（0.20 mol）	36.54（0.22 mol）	4.58	27.72（1.54 mol）
SM?0.35	47.68（0.20 mol）	24.64（0.10 mol）	11.86（0.07 mol）	1.68	10.08（0.56 mol）
SM?0.26	23.84（0.10 mol）	24.64（0.10 mol）	5.52（0.03 mol）	1.08	6.30（0.35 mol）

样品编号	MDT?SH		PSR?Vi含量/g	TPO?L含量/g ^b）
样品编号	类型	含量/g	PSR?Vi含量/g	TPO?L含量/g ^b）
UPA?1	SM?0.43	34.47（0.15 mol）	50.94 （0.10 mol ^a））	0.85
UPA?2	SM?0.39	39.28（0.15 mol）		0.90
UPA?3	SM?0.35	42.46（0.15 mol）		0.93
UPA?4	SM?0.26	57.41（0.15 mol）		1.08

样品编号	MDT?SH		PSR?Vi含量/g	TPO?L含量/g ^b）
样品编号	类型	含量/g	PSR?Vi含量/g	TPO?L含量/g ^b）
UPA?1	SM?0.43	34.47（0.15 mol）	50.94 （0.10 mol ^a））	0.85
UPA?2	SM?0.39	39.28（0.15 mol）		0.90
UPA?3	SM?0.35	42.46（0.15 mol）		0.93
UPA?4	SM?0.26	57.41（0.15 mol）		1.08

样品名称	巯基含量/mol·(100 g)^-1		M/D/T	R/Si	M_n^a）/g·mol^-1	M_w^b）/g·mol^-1	PDI ^c）	产率/%
样品名称	理论	实际	M/D/T	R/Si	M_n^a）/g·mol^-1	M_w^b）/g·mol^-1	PDI ^c）	产率/%
SM?0.43	0.43	0.40	0.78/0.23/1	1.83	1 541	1 957	1.27	73.82
SM?0.39	0.39	0.36	0.76/0.36/1	1.85	1 685	2 056	1.22	85.26
SM?0.35	0.35	0.34	0.73/0.51/1	1.88	1 329	1 568	1.18	90.16
SM?0.26	0.26	0.25	0.69/1.06/1	1.90	1 342	1 651	1.23	90.68

LED封装用UV光固化硅树脂的制备及性能研究

Preparation and Properties of UV⁃curable Silicone Resin for LED Package

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样品名称	黏度/ mPa·s	密度/ g·cm^–3	折射率 (25 ℃)	450 nm透光率/ %
SM?0.43	15 560	1.188 4	1.573 2	97.12
SM?0.39	13 820	1.167 2	1.572 8	96.88
SM?0.35	11 750	1.136 9	1.572 3	97.83
SM?0.26	10 890	1.124 3	1.570 5	97.48

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