彩色光刻胶用蒽醌染料的合成及稳定性研究

doi:10.11949/0438-1157.20211726

摘要/Abstract

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

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

中图分类号:

TQ 619.9

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.

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.

图/表 16

图1 彩色滤光片的基本构造

Fig.1 The basic structure of color filter

图2 彩色滤光片的制备过程

Fig.2 The fabrication process of color filter

图3 蒽醌的基本结构

Fig.3 Basic structure of anthraquinone dyes

图4 蒽醌类染料A1~A9的合成路线

Fig.4 Synthetic routes of anthraquinone dyes A1—A9

图5 染料分子在不同溶剂中(30 μmol/L)的紫外-可见吸收光谱及溶液照片

Fig.5 UV-vis absorption spectra of dyes (30 μmol/L) in different solvents and photograph of dyes

表1 染料在不同溶剂中的光谱数据

Table 1 Spectroscopic data of dyes in organic solvents

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

表2 染料在有机溶剂中的溶解度

Table 2 Solubility of dyes in organic solvents

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

图 6 A4、A7~A9染料分子的PGMEA溶液(33 μmol/L)在365 nm波长光下连续光照8 h的透射光谱for 8 h

Fig.6 UV-vis transmittance spectra of A4，A7—A9(33 μmol/L) dyes in PGMEA upon illumination at 365 nm light

图7 A4、A7~A9在CIE Yxy中的色系坐标变化

Fig.7 Variation of color coordinates (x,y) of A4,A7—A9 in CIE Yxy color space

表3 光照前后染料L、a、b数值以及色差变化（ΔE）

Table 3 L，a，b data and color difference value （ΔE） of dyes before and after accelerated irradiation

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

图8 染料的热重分析

Fig.8 Thermogravimetric analysis of dyes

表4 染料在230℃加热30 min后的失重率及分解温度

Table 4 The weight loss of dyes at 230℃ for 30 min and decomposition temperature

染料	失重率(230℃)/%	T_d/℃
A1	14.56	250
A2	55.24	250
A3	1.18	300
A4	2.13	300
A5	15.00	250
A6	5.63	300
A7	1.92	300
A8	5.77	200
A9	9.15	200
溶剂蓝78	43.95	250

图9 后烘前后染料薄膜的透射光谱及光照前后染料薄膜的透射光谱

Fig.9 Transmittance spectra of dye film before and after post-bake and transmittance spectra of dye film before and after irradiation

表5 后烘前后染料薄膜的色差

Table 5 The color difference of the dye film before and after post-bake

染料	后烘前			后烘后			ΔE
染料	L	a	b	L	a	b	ΔE
A4	97.17	-3.06	-4.42	98.43	-1.68	-2.52	2.66
A7	94.61	-4.61	-7.84	94.73	-4.41	-7.81	0.24

表6 光照前后染料薄膜的色差

Table 6 The color difference of the dye film before and after irradiation

染料	光照前			光照后			ΔE
染料	L	a	b	L	a	b	ΔE
A4	97.03	-3.19	-4.83	96.99	-3.22	-4.67	0.16
A7	94.74	-4.51	-8.02	94.71	-4.37	-7.93	0.17

图10 A4、A7染料薄膜在光学显微镜下的平面形貌

Fig.10 Planar morphology of A4 and A7 dye films under optical microscope

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