化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2251-2261.doi: 10.11949/0438-1157.20211726

• 材料化学工程与纳米技术 • 上一篇    下一篇

彩色光刻胶用蒽醌染料的合成及稳定性研究

任玉鑫1(),徐润峰1,王婉颖1,陈鹏忠1,2(),彭孝军1   

  1. 1.大连理工大学精细化工国家重点实验室,辽宁 大连 116024
    2.大连理工大学宁波研究院,浙江 宁波 315000
  • 收稿日期:2021-12-02 修回日期:2022-03-08 出版日期:2022-05-05 发布日期:2022-05-24
  • 通讯作者: 陈鹏忠 E-mail:renyuxin19970322@163.com;pzchen@dlut.edu.cn
  • 作者简介:任玉鑫(1997—),女,硕士研究生,renyuxin19970322@163.com
  • 基金资助:
    国家自然科学基金重大项目(22090011);中央高校基本科研业务费专项(DUT20RC(3)030)

Synthesis and stability study of anthraquinone dyes for color photoresist

Yuxin REN1(),Runfeng XU1,Wanying WANG1,Pengzhong CHEN1,2(),Xiaojun PENG1   

  1. 1.State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China
    2.Ningbo Institute of Dalian University of Technology, Ningbo 315000, Zhejiang, China
  • Received:2021-12-02 Revised:2022-03-08 Published:2022-05-05 Online:2022-05-24
  • Contact: Pengzhong CHEN E-mail:renyuxin19970322@163.com;pzchen@dlut.edu.cn

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

图1

彩色滤光片的基本构造"

图2

彩色滤光片的制备过程"

图3

蒽醌的基本结构"

图4

蒽醌类染料A1~A9的合成路线"

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"

表1

染料在不同溶剂中的光谱数据"

溶剂染料λmax/nmε/(104 L/(mol·cm))λmax/nmε/(104 L/(mol·cm))
DMFA16001.506451.82
A25951.696452.05
A36001.606451.98
A45951.366401.56
A55951.146401.28
A65951.356401.57
A75951.526401.78
A85950.836450.84
A95950.726450.73
溶剂蓝786001.406451.58
PGMEA15981.416481.68
A25981.596461.91
A35981.446461.76
A45951.516401.71
A55941.116381.23
A65941.446401.66
A75941.346401.54
A85980.516400.49
A95940.406420.39
溶剂蓝785981.206461.38
PGMEAA15981.546481.81
A25981.576441.85
A35981.566461.83
A45951.586381.75
A55921.146381.23
A65941.256401.41
A75911.576381.78
A85960.716400.70
A95980.536420.51
溶剂蓝786001.336431.47

表2

染料在有机溶剂中的溶解度"

染料SPGMEASDMF
A18.412.50
A25.792.03
A31.870.94
A45.606.12
A55.325.92
A63.764.67
A73.729.90
A80.250.81
A90.181.20

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"

图7

A4、A7~A9在CIE Yxy中的色系坐标变化"

表3

光照前后染料L、a、b数值以及色差变化(ΔE)"

染料光照前光照后ΔE
LabLab
A184.518-18.715-23.36785.577-16.489-21.6772.99
A281.446-21,160-30.00382.039-19.813-28.6981.96
A384.845-17.406-24.47385.031-16.055-23.7181.56
A479.305-19.392-33.49079.678-18.186-32.3111.73
A586.429-12.869-19.21487.066-11.554-19.4371.48
A682.322-18.314-27.97082.493-16.874-26.3682.16
A783.177-15.160-26.52983.442-13.973-25.9311.36
A885.299-14.146-21.55887.386-7.471-16.7218.50
A984.699-16.060-23.37086.129-9.713-19.8057.41
溶剂蓝7883.923-14.011-23.77484.963-13.864-22.0401.40

图8

染料的热重分析"

表4

染料在230℃加热30 min后的失重率及分解温度"

染料失重率(230℃)/%Td/℃
A114.56250
A255.24250
A31.18300
A42.13300
A515.00250
A65.63300
A71.92300
A85.77200
A99.15200
溶剂蓝7843.95250

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"

表5

后烘前后染料薄膜的色差"

染料后烘前后烘后ΔE
LabLab
A497.17-3.06-4.4298.43-1.68-2.522.66
A794.61-4.61-7.8494.73-4.41-7.810.24

表6

光照前后染料薄膜的色差"

染料光照前光照后ΔE
LabLab
A497.03-3.19-4.8396.99-3.22-4.670.16
A794.74-4.51-8.0294.71-4.37-7.930.17

图10

A4、A7染料薄膜在光学显微镜下的平面形貌"

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