Synthesis and stability study of anthraquinone dyes for color photoresist

doi:10.11949/0438-1157.20211726

Abstract

Abstract:

Color photoresist is the key material for the preparation of color filters. In order to develop the color filters with higher resolution, organic dyes replacing conventional pigment-based system offers a promising alternative. However, the photothermal stability of dye molecules is an urgent problem to be solved. Therefore, it is desirable to explore effective strategy to improve the stability of dye molecules from the perspective of molecular structure innovation. In this paper, we report nine blue dyes based on anthraquinone scaffold with different substituents. These dyes were prepared from the reaction between 1,4,9,10-anthracyl alcohol and amine-end substituents. The relationships between the dye molecular structures and the photophysical/photothermal properties were investigated. All dyes exhibit double-peaks absorption spectra with the maxima in the range of 590—600 nm and 630—650 nm, respectively, and high molar extinction coefficient. The dyes that contain triethylene glycol and triethylene glycol monomethyl ether chains show better photothermal stability than the alkyl and amine-alkyl substituted dyes. The decomposition temperature of the ether chain dyes reaches 300℃ and the mass loss ratio is about 2% after heating at 230℃ for 0.5 h. Meanwhile, the color difference value is below 1.73 after continuous illumination at 365 nm wavelength for 8 h. Our work laid the foundation for further developing dyes with good performance that can be used in color photoresist.

Key words: color filter, anthraquinone dye, molecular synthesis, solubility, stability

摘要：

为实现彩色滤光片更高分辨率的发展需求，作为关键原材料的彩色光刻胶着色剂从颜料向染料体系转变是重要的趋势。然而染料分子的光热稳定性较差，亟需从分子结构方面探索提升稳定性的有效策略。以1,4,9,10-蒽四醇为原料，合成了9种1,4-二氨基取代的蓝色蒽醌染料分子，探索了不同取代基对染料分子光物理性质、溶解性以及光热稳定性的影响。结果表明，所有染料分子在590~600 nm和630~650 nm波长范围内呈现双吸收峰性质，具有高的摩尔消光系数。其中三甘醇及单甲醚取代的染料分子热分解温度为300℃，在230℃加热0.5 h后失重约2%，365 nm波长光照射8 h后色差低于1.73，表现出优异的光热稳定性。研究为进一步制备光热稳定性优异的彩色光刻胶用染料分子奠定了基础。

关键词: 彩色滤光片, 蒽醌染料, 分子合成, 溶解性, 稳定性

CLC Number:

TQ 619.9

Yuxin REN, Runfeng XU, Wanying WANG, Pengzhong CHEN, Xiaojun PENG. Synthesis and stability study of anthraquinone dyes for color photoresist[J]. CIESC Journal, 2022, 73(5): 2251-2261.

任玉鑫, 徐润峰, 王婉颖, 陈鹏忠, 彭孝军. 彩色光刻胶用蒽醌染料的合成及稳定性研究[J]. 化工学报, 2022, 73(5): 2251-2261.

Figures/Tables 16

References 31

1	Kim Y D, Kim J P, Kwon O S, et al. The synthesis and application of thermally stable dyes for ink-jet printed LCD color filters[J]. Dyes and Pigments, 2009, 81(1): 45-52.
2	Kim Y D, Cho J H, Park C R, et al. Synthesis, application and investigation of structure-thermal stability relationships of thermally stable water-soluble azo naphthalene dyes for LCD red color filters[J]. Dyes and Pigments, 2011, 89(1): 1-8.
3	Choi J, Lee W, Chun S K, et al. Facile synthesis and characterization of novel coronene chromophores and their application to LCD color filters[J]. Dyes and Pigments, 2012, 94(1): 34-39.
4	Kim S H, Namgoong J W, Yuk S B, et al. Synthesis and characteristics of metal-phthalocyanines tetra-substituted at non-peripheral (α) or peripheral (β) positions, and their applications in LCD color filters[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2015, 82(1/2): 195-202.
5	郭景. 生产彩色滤光片用材料简介[J]. 科技创新导报, 2019, 16(31): 94, 96.
	Guo J. Brief introduction of materials used in producing color filter [J]. Science and Technology Innovation Herald, 2019, 16(31): 94, 96.
6	付学勇. 颜料分散机理的探讨及新的分散方法[J]. 涂料工业, 2010, 40(7): 67-68, 72.
	Fu X Y. Discussion on pigment dispersion mechanism and new dispersion method[J]. Paint & Coatings Industry, 2010, 40(7): 67-68, 72.
7	Sugiura T. Development of pigment-dispersed-type color filters for LCDs[J]. Journal of the Society for Information Display, 1993, 1(3): 341.
8	Sabnis R W. Color filter technology for liquid crystal displays[J]. Displays, 1999, 20(3): 119-129.
9	Fagelman K E, Guthrie J T. A study of pigment solubility in model compounds that represent a polycarbonate-poly(butylene terephthalate) blend[J]. Surface Coatings International Part B: Coatings Transactions, 2006, 89(2): 109-116.
10	Choi S H, Kil G H, Kim N R, et al. Preparation of red dyes derived from diketo-pyrrolo-pyrrole based pigment and their properties for LCD color filters[J]. Bulletin of the Korean Chemical Society, 2010, 31(11): 3427-3430.
11	张卓, 何璇, 李琳. 颜料分散用树脂的合成及性能研究[J]. 液晶与显示, 2010, 25(4): 481-485.
	Zhang Z, He X, Li L. Synthesis and performance of polyacrylate resin used on pigment-dispersion[J]. Chinese Journal of Liquid Crystals and Displays, 2010, 25(4): 481-485.
12	Chun S K, Kim Y D, Choi J H, et al. The synthesis of thermally-stable red dyes for LCD color filters and analysis of their aggregation and spectral properties[J]. Dyes and Pigments, 2011, 88(2): 166-173.
13	李宏彦, 杨久霞, 吕艳英, 等. TFT-LCD用彩色滤光片[J]. 现代显示, 2005(6): 41-44.
	Li H Y, Yang J X, Lyu Y Y, et al. Color filter for TFT-LCD[J]. Advanced Display, 2005(6): 41-44.
14	朱昌昌, 陈嵘. LCD用彩色滤色器的现状和进展[J]. 光电子技术, 1996, 16(4): 280-285.
	Zhu C C, Chen R. State-of-art and development trend of color filter for LCDs[J]. Optoelecfronic Technology, 1996, 16(4): 280-285.
15	张天庆, 杜健军, 陈鹏, 等. 1, 4-二氨基-2, 3-邻苯二甲酰亚胺蒽醌染料的合成与应用[J]. 精细化工, 2019, 36(9): 1949-1955.
	Zhang T Q, Du J J, Chen P, et al. Synthesis and application of 1, 4-diamino-2, 3-phthalimide-anthraquinone dyes[J]. Fine Chemicals, 2019, 36(9): 1949-1955.
16	Galagan Y, Su W F. Fadable ink for time-temperature control of food freshness: novel new time-temperature indicator[J]. Food Research International, 2008, 41(6): 653-657.
17	段孝宁, 潘鑫, 邓宏坡. 一种蓝色水暂溶性分散染料及其制法和应用: 102199364[P]. 2011-09-28.
	Duan X N, Pan X, Deng H P. A blue water temporarily solubilized disperse dye and preparation method and application: 102199364[P]. 2011-09-28.
18	盛明, 刘慧霞, 张燕柳. 米托蒽醌治疗进展型多发性硬化症的疗效观察[J]. 慢性病学杂志, 2014, 15(2): 143-144.
	Sheng M, Liu H X, Zhang Y L. Clinical observation of mitoxantrone in the treatment of progressive multiple sclerosis[J]. Chronic Pathematology Journal, 2014, 15(2): 143-144.
19	Qi F F, Zhang W, Xue Y Y, et al. Bienzyme-catalytic and dioxygenation-mediated anthraquinone ring opening[J]. Journal of the American Chemical Society, 2021, 143(40): 16326-16331.
20	宋晓燕, 何国庆, 毕艳兰, 等. 大豆油基印刷油墨连结料的制备研究[J]. 中国粮油学报, 2006, 21(4): 71-75.
	Song X Y, He G Q, Bi Y L, et al. Preparation of soybean oil based printing ink vehicle[J]. Journal of the Chinese Cereals and Oils Association, 2006, 21(4): 71-75.
21	杨涛, 马传国. 蒽醌催化大豆油热聚合反应的研究[J]. 中国油脂, 2007, 32(2): 78-81.
	Yang T, Ma C G. Heat polymerization of soybean oil catalyzed by anthraquinone[J]. China Oils and Fats, 2007, 32(2): 78-81.
22	Jing Y, Wu M, Wong A A, et al. In situ electrosynthesis of anthraquinone electrolytes in aqueous flow batteries[J]. Green Chemistry, 2020, 22(18): 6084-6092.
23	贾红玲, 周振勇, 杨倩, 等. 基于数字图像中LAB颜色空间的肉色质量评价方法研究[J]. 现代农业科技, 2016(2): 277, 281.
	Jia H L, Zhou Z Y, Yang Q, et al. Research on meat color quality evaluation method based on LAB color space in digital image [J]. Modern Agricultural Science and Technology, 2016(2): 277, 281.
24	Conway B R, Eskew R T, Martin P R, et al. A tour of contemporary color vision research[J]. Vision Research, 2018, 151: 2-6.
25	Park J, Park Y, Park J. Synthesis and physical property measurement of new red pigment based on anthraquinone derivatives for color filter pigments[J]. Molecular Crystals and Liquid Crystals, 2011, 551(1): 116-122.
26	Hansen C M. Hansen Solubility Parameters: A User’s Handbook[M]. 2nd ed. Boca Raton: CRC Press, 2012.
27	Gu K Z, Zhu W H, Peng X J. Enhancement strategies of targetability, response and photostability for in vivo bioimaging[J]. Science China-Chemistry, 2019, 6(2): 189-198.
28	Wu X M, Zhu W H. Stability enhancement of fluorophores for lighting up practical application in bioimaging[J]. Chemical Society Reviews, 2015, 44(13): 4179-4184.
29	胡永静. 醚链取代/桥联聚噻吩的热电及电致变色性能[D]. 南昌: 江西科技师范大学, 2017.
	Hu Y J. Thermoelectric and electrochromic properties of oligo(oxyethylene)-substituted/bridged polythiophene[D]. Nanchang: Jiangxi Science and Technology Normal University, 2017.
30	单斌. 高光稳定性聚乙烯胺型大分子自交联染料的合成及应用[D]. 大连: 大连理工大学, 2016.
	Shan B. Synthesis and application of polyvinylamine macromolecule self-crosslinking dyes with high light stability[D]. Dalian: Dalian University of Technology, 2016.
31	Kim T H, Lee B J, An S O, et al. The synthesis of red dyes based on diketo-pyrrolo-pyrrole chromophore to improve heat stability and solubility for colour filter fabrication[J]. Dyes and Pigments, 2020, 174: 108053.

溶剂	染料	λ_max/nm	ε/(10⁴ L/(mol·cm))	λ_max/nm	ε/(10⁴ L/(mol·cm))
DMF	A1	600	1.50	645	1.82
	A2	595	1.69	645	2.05
	A3	600	1.60	645	1.98
	A4	595	1.36	640	1.56
	A5	595	1.14	640	1.28
	A6	595	1.35	640	1.57
	A7	595	1.52	640	1.78
	A8	595	0.83	645	0.84
	A9	595	0.72	645	0.73
	溶剂蓝78	600	1.40	645	1.58
PGME	A1	598	1.41	648	1.68
	A2	598	1.59	646	1.91
	A3	598	1.44	646	1.76
	A4	595	1.51	640	1.71
	A5	594	1.11	638	1.23
	A6	594	1.44	640	1.66
	A7	594	1.34	640	1.54
	A8	598	0.51	640	0.49
	A9	594	0.40	642	0.39
	溶剂蓝78	598	1.20	646	1.38
PGMEA	A1	598	1.54	648	1.81
	A2	598	1.57	644	1.85
	A3	598	1.56	646	1.83
	A4	595	1.58	638	1.75
	A5	592	1.14	638	1.23
	A6	594	1.25	640	1.41
	A7	591	1.57	638	1.78
	A8	596	0.71	640	0.70
	A9	598	0.53	642	0.51
	溶剂蓝78	600	1.33	643	1.47

溶剂	染料	λ_max/nm	ε/(10⁴ L/(mol·cm))	λ_max/nm	ε/(10⁴ L/(mol·cm))
DMF	A1	600	1.50	645	1.82
	A2	595	1.69	645	2.05
	A3	600	1.60	645	1.98
	A4	595	1.36	640	1.56
	A5	595	1.14	640	1.28
	A6	595	1.35	640	1.57
	A7	595	1.52	640	1.78
	A8	595	0.83	645	0.84
	A9	595	0.72	645	0.73
	溶剂蓝78	600	1.40	645	1.58
PGME	A1	598	1.41	648	1.68
	A2	598	1.59	646	1.91
	A3	598	1.44	646	1.76
	A4	595	1.51	640	1.71
	A5	594	1.11	638	1.23
	A6	594	1.44	640	1.66
	A7	594	1.34	640	1.54
	A8	598	0.51	640	0.49
	A9	594	0.40	642	0.39
	溶剂蓝78	598	1.20	646	1.38
PGMEA	A1	598	1.54	648	1.81
	A2	598	1.57	644	1.85
	A3	598	1.56	646	1.83
	A4	595	1.58	638	1.75
	A5	592	1.14	638	1.23
	A6	594	1.25	640	1.41
	A7	591	1.57	638	1.78
	A8	596	0.71	640	0.70
	A9	598	0.53	642	0.51
	溶剂蓝78	600	1.33	643	1.47

染料	S_PGMEA	S_DMF
A1	8.41	2.50
A2	5.79	2.03
A3	1.87	0.94
A4	5.60	6.12
A5	5.32	5.92
A6	3.76	4.67
A7	3.72	9.90
A8	0.25	0.81
A9	0.18	1.20

染料	S_PGMEA	S_DMF
A1	8.41	2.50
A2	5.79	2.03
A3	1.87	0.94
A4	5.60	6.12
A5	5.32	5.92
A6	3.76	4.67
A7	3.72	9.90
A8	0.25	0.81
A9	0.18	1.20

染料	光照前			光照后			ΔE
染料	L	a	b	L	a	b	ΔE
A1	84.518	-18.715	-23.367	85.577	-16.489	-21.677	2.99
A2	81.446	-21,160	-30.003	82.039	-19.813	-28.698	1.96
A3	84.845	-17.406	-24.473	85.031	-16.055	-23.718	1.56
A4	79.305	-19.392	-33.490	79.678	-18.186	-32.311	1.73
A5	86.429	-12.869	-19.214	87.066	-11.554	-19.437	1.48
A6	82.322	-18.314	-27.970	82.493	-16.874	-26.368	2.16
A7	83.177	-15.160	-26.529	83.442	-13.973	-25.931	1.36
A8	85.299	-14.146	-21.558	87.386	-7.471	-16.721	8.50
A9	84.699	-16.060	-23.370	86.129	-9.713	-19.805	7.41
溶剂蓝78	83.923	-14.011	-23.774	84.963	-13.864	-22.040	1.40