CN115304511A - 查尔酮结构的肟酯类光引发剂及其制备方法与应用 - Google Patents

查尔酮结构的肟酯类光引发剂及其制备方法与应用 Download PDF

Info

Publication number
CN115304511A
CN115304511A CN202110501130.3A CN202110501130A CN115304511A CN 115304511 A CN115304511 A CN 115304511A CN 202110501130 A CN202110501130 A CN 202110501130A CN 115304511 A CN115304511 A CN 115304511A
Authority
CN
China
Prior art keywords
reaction
oxime ester
photoinitiator
substituted
chalcone
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
Application number
CN202110501130.3A
Other languages
English (en)
Inventor
钱晓春
张学龙
汪雷
于培培
金晓蓓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Original Assignee
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changzhou Tronly New Electronic Materials Co Ltd, Changzhou Tronly Advanced Electronic Materials Co Ltd filed Critical Changzhou Tronly New Electronic Materials Co Ltd
Priority to CN202110501130.3A priority Critical patent/CN115304511A/zh
Priority to PCT/CN2022/091212 priority patent/WO2022237644A1/zh
Priority to JP2023568742A priority patent/JP2024523053A/ja
Priority to KR1020237041599A priority patent/KR20240005843A/ko
Publication of CN115304511A publication Critical patent/CN115304511A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
    • C07D513/14—Ortho-condensed systems
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明提供了一种查尔酮结构的肟酯类光引发剂及其制备方法与应用。该引发剂具有以下结构，Ar1、Ar2为含有芳香环或杂芳香环的取代基，R1为C1～C20的直链或支链烷基、C3～C20的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C1～C20的烷基取代的C3～C8环烷基、C6～C20的芳基、C1～C5烷基取代的C6～C20芳基、C4～C20的杂芳基或C1～C5烷基取代的C6～C20杂芳基。该查尔酮结构的肟酯类光引发剂其具有大共轭结构，感度优异，固化后碎片不易迁移，抗黄变性能优异。除此之外，该光引发剂还具有合成简单，合成过程无需昂贵催化剂，且固化速度优异等特点，能够广泛应用于光固化领域。

Description

查尔酮结构的肟酯类光引发剂及其制备方法与应用
技术领域
本发明涉及有机化学领域，具体而言，涉及一种查尔酮结构的肟酯类光引发剂及其制备方法与应用。
背景技术
具有肟酯结构的化合物作为光引发剂在光固化领域中具有广泛的用途，设计合成新型的具有更佳应用性能的肟酯类光引发剂一直是光固化领域的研究热点。由于肟酯类光引发剂具有较高的灵敏度，因而可以将其用于彩色电视机、液晶显示器、固体摄像元件、照相机等中使用的彩色滤光片、黑色矩阵等用途中含有着色剂的光聚合组合物中。如公开号为CN99108598A、CN101508744A、CN10565472A、CN103293855A等专利文献公开了不同的咔唑肟酯和酮肟酯类光引发剂，这些公开的光引发剂具有良好的感光性和存储稳定性，可在不同程度上满足当前显示面板及彩色滤光片等光固化领域的一般性应用要求，然而其在感度和黄变性能上一直无法均衡。
CN107344918A、CN110066352A、CN110066225A分别公开了不同含可聚合基团的肟酯光引发剂，但是其合成过程复杂，这类化合物的合成需要用到昂贵的钯催化剂，且后处理工艺复杂，提纯很困难，生产成本很高，极大地限制了它们的应用。
因此，提供新的肟酯类光引发剂，使其兼顾合成简单、感度和黄变性能优异，是本领域亟需解决的问题。
发明内容
本发明的主要目的在于提供一种查尔酮结构的肟酯类光引发剂及其制备方法与应用，以解决现有技术中肟酯类光引发剂无法兼顾感度和黄变性能优异、以及合成路线简单的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种查尔酮结构的肟酯类光引发剂，其具有以下通式I所示结构：
Figure BDA0003056532950000011
其中，Ar1、Ar2为含有芳香环或杂芳香环的取代基，R1为C1～C20的直链或支链烷基、C3～C20的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C1～C20的烷基取代的C3～C8环烷基、C6～C20的芳基、C1～C5烷基取代的C6～C20芳基、C4～C20的杂芳基或C1～C5烷基取代的C6～C20杂芳基。
根据本发明的另一方面，提供了上述查尔酮结构的肟酯类光引发剂的制备方法，其包括以下步骤：将Ar1-H和三氯氧磷进行甲酰化反应，得到中间体1
Figure BDA0003056532950000021
将中间体1与
Figure BDA0003056532950000022
进行缩合反应，得到中间体2
Figure BDA0003056532950000023
将中间体2与盐酸羟胺发生肟化反应，得到中间体3为
Figure BDA0003056532950000024
将中间体3与含有
Figure BDA0003056532950000025
的酰氯或酸酐发生酯化反应，得到上述查尔酮结构的肟酯类光引发剂；其中Ar1、Ar2、R1具有与前文所述相同的定义。
根据本发明的又一方面，提供了一种光固化组合物，包括光引发剂，其为上述查尔酮结构的肟酯类光引发剂。
本发明提供的查尔酮结构的肟酯类光引发剂，其具有大共轭结构，相比于现有的肟酯类引发剂感度优异，固化后碎片不易迁移，抗黄变性能优异。除此之外，该光引发剂还具有合成简单，合成过程无需使用昂贵催化剂，且使用后固化速度优异等特点，能够广泛应用于光固化领域。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术部分所描述的，现有技术中肟酯类光引发剂存在无法兼顾感度和黄变性能优异、以及合成路线简单的问题。
为了解决上述问题，本发明提供了一种查尔酮结构的肟酯类光引发剂，其具有以下通式I所示结构：
Figure BDA0003056532950000026
其中，Ar1、Ar2为含有芳香环或杂芳香环的取代基，R1为C1～C20的直链或支链烷基、C3～C20的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C1～C20的烷基取代的C3～C8环烷基、C6～C20的芳基、C1～C5烷基取代的C6～C20芳基、C4～C20的杂芳基或C1～C5烷基取代的C6～C20杂芳基。
查尔酮是一种共轭程度很高的结构，具有优秀的吸光性能及光学性能，有其作为聚合物单体的使用报道，然而其作为光引发剂母体基团的使用确显见报道。本发明人惊喜地发现，将查尔酮结构应用于肟酯光引发剂的制作中，合成简单，且得到的产品具有长波长吸收的特点，应用于彩色滤光片和黑色矩阵感度优异，并可进一步解决现有技术中存在的引发剂感度高导致高黄变的问题。
本发明提供的查尔酮结构的肟酯类光引发剂，其具有大共轭结构，相比于现有的肟酯类引发剂感度优异，固化后碎片不易迁移，抗黄变性能优异。除此之外，该光引发剂还具有合成简单，合成过程无需使用昂贵催化剂，且使用后固化速度优异等特点，能够广泛应用于光固化领域。
为了进一步提高光引发剂的感度，改善应用后的抗黄变性能，同时使光引发剂具有更好的引发效率，在一种优选的实施方式中，Ar1、Ar2各自独立地选自
Figure BDA0003056532950000031
Figure BDA0003056532950000032
Figure BDA0003056532950000033
任选地，以上基团中的-CH2-可被-O-或-S-取代；R3为H、硝基、羟基、C1～C20的直链或支链烷基、C3～C20的环烷基、C4～C20的烷基环烷基或环烷基烷基、C2～C20的链烯基、C5～C10的取代或未取代的环状或杂环状烯基、C6～C12的芳基或杂芳基、C6～C12的芳基或杂芳基取代的C1～C4的烷基，任选地，这些基团中的-CH2-可被-O-或-C(＝O)-取代；R4代表H、C1～C6的直链或支链烷基、C1～C6的链烯基、苯基或取代苯基。
更优选地，Ar1、Ar2各自独立地选自
Figure BDA0003056532950000041
Figure BDA0003056532950000042
Figure BDA0003056532950000051
Figure BDA0003056532950000052
选用以上类型的基团作为Ar1、Ar2基团，形成的光引发剂能够更好地发挥查尔酮类结构和肟酯结构的双重作用，进一步改善光引发剂的各项性能。
在一种优选的实施方式中，R1为C1～C5的直链或支链烷基或C6～C12的芳基。
示例性地，光引发剂为以下化合物中的一种或多种：
Figure BDA0003056532950000061
Figure BDA0003056532950000071
Figure BDA0003056532950000081
Figure BDA0003056532950000091
Figure BDA0003056532950000101
Figure BDA0003056532950000111
根据本发明的另一方面，还提供了一种上述查尔酮结构的肟酯类光引发剂的制备方法，其包括以下步骤：将Ar1-H和三氯氧磷进行甲酰化反应，得到中间体1，中间体1为
Figure BDA0003056532950000112
将中间体1与
Figure BDA0003056532950000113
进行缩合反应，得到中间体2，中间体2为
Figure BDA0003056532950000114
将中间体2与盐酸羟胺发生肟化反应，得到中间体3，中间体3为
Figure BDA0003056532950000115
将中间体3与含有
Figure BDA0003056532950000116
的酰氯或酸酐发生酯化反应，得到查尔酮结构的肟酯类光引发剂；其中Ar1、Ar2、R1、R2具有与前文所述相同的定义。
利用该制备方法，将Ar1-H依次通过甲酰化反应、与乙酰化芳基化合物的缩合反应、肟化反应、酯化反应，即可制备得到查尔酮结构的肟酯类光引发剂。该合成方法路线简单，各步骤条件温和，方便操作，合成过程中也无需采用昂贵催化剂等原料，在合成路线和合成成本上均具有优势。制备得到的光引发剂在感度、抗黄变性能、固化速度等方面表现优异。
需说明的是，以上Ar1-H、含有
Figure BDA0003056532950000117
的酰氯或酸酐、三氯氧磷、盐酸羟胺等均为现有技术中的已知化合物，可以商购也可以采用现有方法自制。
以上甲酰化反应过程中，底物Ar1-H中引入甲酰基团，为后续反应做准备。为使反应过程更为稳定，并尽量提高反应效率，在一种优选的实施方式中，甲酰化反应的过程中，反应温度为60～120℃，优选为100℃，反应时间为1～5h；更优选地，甲酰化反应在第一溶剂中进行，第一溶剂为DMF。
在一种优选的实施方式中，缩合反应在第一类碱的催化作用下进行，优选第一类碱选自氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、叔丁醇钠及叔丁醇钾中的一种或多种。使用碱作为催化剂能够有效改善反应效率，更优选使用氢氧化钠作为催化剂。
为使反应更稳定，优选地，缩合反应过程中的反应温度为20～60℃，反应时间为2～6h；优选地，缩合反应在第二溶剂中进行，第二溶剂选自甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、DMF及DMSO中的一种或多种，更优选为甲醇。
在一种优选的实施方式中，肟化反应的反应温度为60～90℃，反应时间为10～16℃；优选地，肟化反应在第三溶剂中进行，第三溶剂选自甲醇、乙醇、异丙醇及叔丁醇中的一种或多种，更优选为乙醇。
在一种优选的实施方式中，酯化反应在第二类碱的作用下进行，优选第二类碱选自三乙胺、吡啶、二异丙基乙基胺、氢氧化钾、氢氧化钠及氢化钠中的一种或多种。选用碱催化酯化反应，有利于酯化反应高效进行。优选地，酯化反应的反应温度为-10～60℃，更优选为0～25℃；优选地，酯化反应在第四溶剂中进行，第四溶剂选自二乙基醚、乙腈、叔丁基甲基醚、四氢呋喃、乙酸乙烯酯、甲苯、二甲苯、丙酮、甲乙酮、二氯甲烷、氯仿、氯苯、二甲基乙酰胺及二甲基甲酰胺中的一种或多种。
根据本发明的又一方面，还提供了上述光引发剂在光固化领域的应用。介于该光引发剂优异的感度和抗黄变性能，非常适合应用在光固化领域的各种光聚合组合物。
根据本发明的又一方面，还提供了一种光固化组合物，包括光引发剂，其为上述查尔酮结构的肟酯类光引发剂。
进一步地，上述所述的查尔酮肟酯引发剂可应用于在塑料、金属、玻璃、陶瓷、木材、墙体、光纤等基材上进行涂布的涂料；硬涂层剂、防污膜、防反射膜、冲击缓冲膜等保护膜材料；光固化黏合剂、黏着剂，光分解型涂料、涂膜、成型物；全息影像材料等的光记录介质；光学成型树脂，例如，3D打印用油墨(树脂)，电子电路和半导体制造用光刻胶，显示器中彩色滤光片、黑色矩阵、干膜等电子材料用光刻胶等；层间绝缘膜，光提取膜，增亮膜，密封材料；丝网印刷、胶板印刷、凹版印刷等印刷用油墨，喷墨打印用光固化油墨；镜片、透镜阵列、光导波路、导光板、光扩散板、衍射元件等光学部件；光间隙物，肋壁，纳米压印用材料等。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
化合物1的制备
Figure BDA0003056532950000131
步骤(1)中间体1a的制备
Figure BDA0003056532950000132
向1L三口瓶中加入150mL DMF，冰浴，降温至0℃，缓慢加入100mL POCl3，保温搅拌半小时；将55.7g二丁基芴(0.2mol)溶于150mL DMF中，然后加入到反应液中。升温至100℃，保温搅拌2h。原料反应完全，加入500g冰水淬灭反应，反应液用500mL DCM萃取，有机相用500mL水洗涤3次，浓缩，所得固体溶于500mL正己烷，室温搅拌半小时，过滤，得到43.3g类白色固体，即中间体1a，收率70.6％。
步骤(2)中间体1b的制备
Figure BDA0003056532950000133
向500mL三口瓶中加入40g中间体1a(0.13mol)、15.7g苯乙酮(0.13mol)、5.7g氢氧化钠(0.14mol)和400g甲醇，室温搅拌3h，原料反应完全。反应液中加入400mL水，用200mLDCM萃取，有机相浓缩，得到36.4g类白色固体，即中间体1b，收率68.6％。
步骤(3)中间体1c的制备
Figure BDA0003056532950000141
向500mL三口瓶中加入30g中间体1b(0.07mol)、15.3g盐酸羟胺(0.21mol)、29.8g硫酸钠(0.21mol)和300g乙醇，加热至回流，搅拌12h，原料反应完全。反应液降温至室温，过滤，滤液浓缩，所得油状物用120mL DCM溶解，用120mL水洗3次，有机相浓缩，所得固体溶于50mL丙酮，冰浴，降温至0-10℃，搅拌2h，过滤，得到25.9g浅黄色固体，即中间体1c，收率87.4％。
步骤(4)化合物1的制备
Figure BDA0003056532950000142
向250mL反应瓶中加入20g中间体1c(0.05mol)、8.1g TEA(0.08mol)和100mL二氯甲烷，搅拌溶清。滴加6.1g乙酸酐(0.06mol)，滴完，室温搅拌2h。往反应液中加入100mL水，搅拌半小时，静置分层，分出下层有机相，水洗至中性，有机相浓缩，所得固体用100mL甲醇溶解，回流搅拌1h。冷却至室温，搅拌1h，再冰浴，降温至5-10℃，搅拌1h。过滤，滤饼用100mL甲醇洗涤，得粗品。粗品溶于60mL丙酮，加入到180mL甲醇中，搅拌析晶，冰浴下继续搅拌1h，过滤，滤饼用100mL甲醇淋洗，所得固体放入60℃真空干燥箱中干燥24h，得到19.2g类白色固体，收率82.3％，纯度99.64％。
化合物1的结构由如下核磁数据确认：
1H NMR(500MHz,Chloroform-d)δ7.69(d,J＝7.3Hz,1H),7.56(ddd,J＝7.8,4.3,2.2Hz,3H),7.50–7.44(m,1H),7.44–7.37(m,5H),7.33–7.26(m,2H),7.24(dd,J＝15.2,0.6Hz,1H),7.17(d,J＝15.0Hz,1H),2.15(s,3H),2.04–1.95(m,2H),1.93(d,J＝7.1Hz,1H),1.91(d,J＝7.0Hz,1H),1.60–1.44(m,4H),1.37(dtd,J＝15.0,8.0,7.0Hz,4H),0.88(t,J＝7.9Hz,6H).
实施例2
化合物2的制备
Figure BDA0003056532950000151
反应路线如下：
Figure BDA0003056532950000152
向250mL反应瓶中加入20g中间体1c(0.05mol)、8.1g TEA(0.08mol)和100mL二氯甲烷，搅拌溶清。滴加8.4g苯甲酰氯(0.06mol)，滴完，室温搅拌2h。往反应液中加入100mL水，搅拌半小时，静置分层，分出下层有机相，水洗至中性，有机相浓缩，所得固体用100mL甲醇溶解，回流搅拌1h。冷却至室温，搅拌1h，再冰浴，降温至5-10℃，搅拌1h。过滤，滤饼用100mL甲醇洗涤，得粗品。粗品溶于60mL丙酮，加入到180mL甲醇中，搅拌析晶，冰浴下继续搅拌1h，过滤，滤饼用100mL甲醇淋洗，所得固体放入60℃真空干燥箱中干燥24h，得到19.5g类白色固体，收率73.9％，纯度98.72％。
化合物2的结构由如下核磁数据确认：
1H NMR(500MHz,Chloroform-d)δ8.17–8.10(m,2H),7.69(d,J＝7.5Hz,1H),7.63–7.57(m,1H),7.57–7.52(m,3H),7.52–7.37(m,8H),7.36–7.22(m,3H),7.09(d,J＝15.0Hz,1H),2.08(dt,J＝12.3,7.1Hz,2H),1.98(dt,J＝12.4,7.0Hz,2H),1.60–1.44(m,4H),1.43–1.31(m,4H),0.88(t,J＝8.0Hz,6H).
实施例3
进一步的，可选用不同的原料进行反应及不同的反应条件，从而得到不同结构的化合物，但不限于如此，见表1。
表1
Figure BDA0003056532950000161
Figure BDA0003056532950000171
Figure BDA0003056532950000181
Figure BDA0003056532950000191
Figure BDA0003056532950000201
性能评价
通过配制代表性光固化树脂组合物，对本发明式(I)所示光引发剂的固化速度、迁移性、溶解性、迁移性等应用性能进行评价，具体步骤如下：
(1)配制如下组成的光固化树脂组合物：
Figure BDA0003056532950000211
上述组合物中，光引发剂为本发明的式(I)化合物或现有技术中已知光引发剂(作为对比)。
(2)固化速度
将上述组合物在黄光灯下搅拌，取料于PET模板上利用滚涂成膜，在90℃下干燥2min，得到干膜厚为2μm的涂膜，然后冷却至室温，用LED灯(光源波长：385nm，曝光机型号：RW.LED-YT200sg1，单次曝光量50mJ/cm2)照射对涂膜进行曝光，使其固化成膜。
以涂膜固化成固化膜所经过履式曝光带的次数评价，经过次数越多，表明固化速度越不理想。
(3)迁移性
剪碎固化膜，称取0.5g固化膜样品置于50mL烧杯中，加入4.5mL甲醇，并利用超声波超声溶解30min，将所得甲醇溶液移至10mL容量瓶中，将样品继续用甲醇清洗两次(2mL×2)，倒入容量瓶中，用移液管移取0.1mL甲苯为内标物，加入甲醇定溶，摇晃均匀，静置。
采用日本岛津LC-20A液相色谱(shim pack柱，150×6.0nm，检测器SPD-20A，检测限20ppm，检测波长254nm)，在25℃下使用，流速1.0mL/min,流动相(甲醇/水＝90/10)，观察是否能检测到光引发剂的存在。以相对甲苯的液相出峰面积比的百分量计，液相中引发剂含量越高，说明迁移性越大。
(4)黄变性
使用线棒将组合物涂布于马口铁上，制成20μm的涂膜，履带式曝光机曝光，接收1000mJ/cm2的能量，固化完置于烘箱230℃后烘烤30min，采用爱色丽色差仪进行黄变测试，根据b值判断黄变情况，值越高，黄变越明显。
表征结果如表3中所示。
表2
Figure BDA0003056532950000221
表3
Figure BDA0003056532950000222
Figure BDA0003056532950000231
表2、3中，光引发剂A为1-(7-硝基-9,9-二烯丙基芴-2-基)-1-(2-甲基苯基)甲酮-乙酸肟酯，光引发剂B为1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-3-环戊基-丙烷-1-酮-乙酸肟酯，光引发剂C为1-(9-(2-降冰片烯)甲基-9-甲基-9H-芴-2-基)-1,2-丙二酮-2-肟-O-乙酸酯。
从表2、3的测试结果可以看出，本发明的通式(I)所示的查尔酮肟酯类光引发剂在光固化应用中引发剂效率高、固化速度快，且不发生迁移，黄变性较小，综合性能优异。
需指出，化合物3的黄变性能较本发明其他化合物略差，是由于其分子结构中携带了硝基，而对于同样含有硝基的光引发剂A和C而言，化合物3的黄变性能明显得到了显著改善，这也足以说明本发明提供的这种具有查尔酮肟酯类结构的光引发剂取得的有益效果。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

1.一种查尔酮结构的肟酯类光引发剂，其特征在于，所述光引发剂具有以下通式I所示结构：
Figure FDA0003056532940000011
其中，Ar1、Ar2为含有芳香环或杂芳香环的取代基，R1为C1～C20的直链或支链烷基、C3～C20的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C1～C20的烷基取代的C3～C8环烷基、C6～C20的芳基、C1～C5烷基取代的C6～C20芳基、C4～C20的杂芳基或C1～C5烷基取代的C6～C20杂芳基。
2.根据权利要求1所述的查尔酮结构的肟酯类光引发剂，其特征在于，Ar1、Ar2各自独立地选自
Figure FDA0003056532940000012
Figure FDA0003056532940000013
任选地，基团中的-CH2-可被-O-或-S-取代；
R3为H、硝基、羟基、C1～C20的直链或支链烷基、C3～C20的环烷基、C4～C20的烷基环烷基或环烷基烷基、C2～C20的链烯基、C5～C10的取代或未取代的环状或杂环状烯基、C6～C12的芳基或杂芳基、C6～C12的芳基或杂芳基取代的C1～C4的烷基，任选地，这些基团中的-CH2-可被-O-或-C(＝O)-取代；
R4代表H、C1～C6的直链或支链烷基、C1～C6的链烯基、苯基或取代苯基。
3.根据权利要求1所述的查尔酮结构的肟酯类光引发剂，其特征在于，Ar1、Ar2各自独立地选自
Figure FDA0003056532940000014
Figure FDA0003056532940000021
Figure FDA0003056532940000031
4.根据权利要求1至3中任一项所述的查尔酮结构的肟酯类光引发剂，其特征在于，R1为C1～C5的直链或支链烷基或C6～C12的芳基。
5.根据权利要求1所述的查尔酮结构的肟酯类光引发剂，其特征在于，所述光引发剂为以下化合物中的一种或多种：
Figure FDA0003056532940000032
Figure FDA0003056532940000041
Figure FDA0003056532940000051
Figure FDA0003056532940000061
Figure FDA0003056532940000071
Figure FDA0003056532940000081
6.一种权利要求1至5中任一项所述的查尔酮结构的肟酯类光引发剂的制备方法，其特征在于，包括以下步骤：
将Ar1-H和三氯氧磷进行甲酰化反应，得到中间体1，所述中间体1为
Figure FDA0003056532940000091
将所述中间体1与
Figure FDA0003056532940000092
进行缩合反应，得到中间体2，所述中间体2为
Figure FDA0003056532940000093
将所述中间体2与盐酸羟胺发生肟化反应，得到中间体3，所述中间体3为
Figure FDA0003056532940000094
将所述中间体3与含有
Figure FDA0003056532940000095
的酰氯或酸酐发生酯化反应，得到所述查尔酮结构的肟酯类光引发剂；
其中Ar1、Ar2、R1具有与权利要求1至5任一项中相同的定义。
7.根据权利要求6所述的查尔酮结构的肟酯类光引发剂的制备方法，其特征在于，所述甲酰化反应的过程中，反应温度为60～120℃，优选为100℃，反应时间为1～5h；
优选地，所述甲酰化反应在第一溶剂中进行，所述第一溶剂为DMF。
8.根据权利要求6所述的查尔酮结构的肟酯类光引发剂的制备方法，其特征在于，所述缩合反应在第一类碱的催化作用下进行，优选所述第一类碱选自氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、叔丁醇钠及叔丁醇钾中的一种或多种，更优选为氢氧化钠；
优选地，所述缩合反应过程中的反应温度为20～60℃，反应时间为2～6h；
优选地，所述缩合反应在第二溶剂中进行，所述第二溶剂选自甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、DMF及DMSO中的一种或多种，更优选为甲醇。
9.根据权利要求6所述的查尔酮结构的肟酯类光引发剂的制备方法，其特征在于，所述肟化反应的反应温度为60～90℃，反应时间为10～16℃；
优选地，所述肟化反应在第三溶剂中进行，所述第三溶剂选自甲醇、乙醇、异丙醇及叔丁醇中的一种或多种，更优选为乙醇。
10.根据权利要求6所述的查尔酮结构的肟酯类光引发剂的制备方法，其特征在于，所述酯化反应在第二类碱的作用下进行，优选所述第二类碱选自三乙胺、吡啶、二异丙基乙基胺、氢氧化钾、氢氧化钠及氢化钠中的一种或多种；
优选地，所述酯化反应的反应温度为-10～60℃，更优选为0～25℃；
优选地，所述酯化反应在第四溶剂中进行，所述第四溶剂选自二乙基醚、乙腈、叔丁基甲基醚、四氢呋喃、乙酸乙烯酯、甲苯、二甲苯、丙酮、甲乙酮、二氯甲烷、氯仿、氯苯、二甲基乙酰胺及二甲基甲酰胺中的一种或多种。
11.一种光固化组合物，包括光引发剂，其特征在于，所述光引发剂为权利要求1至5中任一项所述的查尔酮结构的肟酯类光引发剂。
12.根据权利要求11所述的光固化组合物，其特征在于，所述光固化组合物应用于以下领域：在塑料、金属、玻璃、陶瓷、木材、墙体或光纤基材上进行涂布的涂料；硬涂层剂、防污膜、防反射膜或冲击缓冲膜材料；光固化黏合剂、黏着剂，光分解型涂料、涂膜、成型物；光记录介质；光学成型树脂；层间绝缘膜，光提取膜，增亮膜，密封材料；印刷用油墨，喷墨打印用光固化油墨；光学部件；光间隙物，肋壁，纳米压印用材料；
优选所述光学成型树脂为3D打印用油墨或树脂，电子电路和半导体制造用光刻胶，电子材料用光刻胶；
优选所述印刷用油墨为丝网印刷、胶板印刷或凹版印刷用油墨；
优选所述光学部件为镜片、透镜阵列、光导波路、导光板、光扩散板或衍射元件；
优选所述光记录介质为全息影像材料。
CN202110501130.3A 2021-05-08 2021-05-08 查尔酮结构的肟酯类光引发剂及其制备方法与应用 Pending CN115304511A (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202110501130.3A CN115304511A (zh) 2021-05-08 2021-05-08 查尔酮结构的肟酯类光引发剂及其制备方法与应用
PCT/CN2022/091212 WO2022237644A1 (zh) 2021-05-08 2022-05-06 查尔酮结构的肟酯类光引发剂及其制备方法与应用
JP2023568742A JP2024523053A (ja) 2021-05-08 2022-05-06 カルコン構造のオキシムエステル類光開始剤及びその製造方法ならびに使用
KR1020237041599A KR20240005843A (ko) 2021-05-08 2022-05-06 칼콘 구조의 옥심 에스테르계 광개시제 및 이의 제조 방법과 응용

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110501130.3A CN115304511A (zh) 2021-05-08 2021-05-08 查尔酮结构的肟酯类光引发剂及其制备方法与应用

Publications (1)

Publication Number Publication Date
CN115304511A true CN115304511A (zh) 2022-11-08

Family

ID=83853547

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110501130.3A Pending CN115304511A (zh) 2021-05-08 2021-05-08 查尔酮结构的肟酯类光引发剂及其制备方法与应用

Country Status (4)

Country Link
JP (1) JP2024523053A (zh)
KR (1) KR20240005843A (zh)
CN (1) CN115304511A (zh)
WO (1) WO2022237644A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118184557A (zh) * 2024-05-17 2024-06-14 上海交通大学 一种基于查尔酮的肟酯类光引发剂及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632987A (en) * 1982-04-28 1986-12-30 Mitsui Toatsu Chemicals Incorporated Process for the preparation of triarylmethane compounds
CN108752239A (zh) * 2018-07-12 2018-11-06 维思普新材料（苏州）有限公司 肟酯化合物及其制造方法
CN108822135A (zh) * 2018-08-25 2018-11-16 湘潭大学 一种氮杂环取代的噻吩并[3,2-d]噻唑及其衍生物的合成方法
CN109456424A (zh) * 2018-09-11 2019-03-12 广东工业大学 一种二苯硫醚肟酯类光引发剂及其制备方法与应用
CN110483387A (zh) * 2019-09-17 2019-11-22 广东医科大学 一种一锅法合成烟酰亚胺酰胺衍生物的方法
CN112358443A (zh) * 2020-11-09 2021-02-12 巢湖学院 一种吡啶化合物及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632987A (en) * 1982-04-28 1986-12-30 Mitsui Toatsu Chemicals Incorporated Process for the preparation of triarylmethane compounds
CN108752239A (zh) * 2018-07-12 2018-11-06 维思普新材料（苏州）有限公司 肟酯化合物及其制造方法
CN108822135A (zh) * 2018-08-25 2018-11-16 湘潭大学 一种氮杂环取代的噻吩并[3,2-d]噻唑及其衍生物的合成方法
CN109456424A (zh) * 2018-09-11 2019-03-12 广东工业大学 一种二苯硫醚肟酯类光引发剂及其制备方法与应用
CN110483387A (zh) * 2019-09-17 2019-11-22 广东医科大学 一种一锅法合成烟酰亚胺酰胺衍生物的方法
CN112358443A (zh) * 2020-11-09 2021-02-12 巢湖学院 一种吡啶化合物及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118184557A (zh) * 2024-05-17 2024-06-14 上海交通大学 一种基于查尔酮的肟酯类光引发剂及其制备方法和应用

Also Published As

Publication number Publication date
WO2022237644A1 (zh) 2022-11-17
JP2024523053A (ja) 2024-06-26
KR20240005843A (ko) 2024-01-12

Similar Documents

Publication Publication Date Title
US5847156A (en) Polymerizable diketopyrrolopyrroles and polymers prepared therewith
KR20200043404A (ko) 비나프틸 화합물
CN112110847A (zh) 一种新的二芳酰基咔唑化合物及其作为增感剂的应用
CN115304511A (zh) 查尔酮结构的肟酯类光引发剂及其制备方法与应用
CN110041254B (zh) 黄色系化合物、含有该化合物的着色组合物、滤色器用着色剂及滤色器
CN113508106A (zh) 一种含有酰基咔唑衍生物和咔唑基肟酯的光引发剂组合物及其在光固化组合物中的应用
JP2019104897A (ja) 黄色系化合物、該化合物を含有する着色組成物、カラーフィルター用着色剤およびカラーフィルター
KR20160129385A (ko) 컬러필터용 착색 염료 및 이를 포함하는 감광성 수지 조성물
CN110066352A (zh) 肟酯类光引发剂、制备方法、感光性树脂组合物及应用
TW202302770A (zh) 二苯并哌喃色素、含有該色素之著色組合物、彩色濾光片用著色劑及彩色濾光片
CN112063194B (zh) 呫吨系色素、含有该色素的着色组合物、滤色器用着色剂及滤色器
CN114560840B (zh) 2,7-二芳基呫吨螺芴二醇衍生物及其制备方法
JP6378011B2 (ja) ビニル基含有化合物の製造方法
CN113248939B (zh) 呫吨色素、含有该色素的着色组合物、滤色器用着色剂及滤色器
CN111378295B (zh) 呫吨系色素、含有该色素的着色组合物、滤色器用着色剂及滤色器
CN111377945B (zh) 一种色阻材料、滤光片及其制备方法
CN115707681B (zh) 萘系增感剂、其制备方法以及光固化组合物和光固化产品
CN114230515A (zh) 黄色系化合物、含有该化合物的着色组合物、滤色器用着色剂及滤色器
JP2024046614A (ja) トリアリールメタン色素、該色素を含有する着色組成物、カラーフィルター用着色剤およびカラーフィルター
JP6378022B2 (ja) ビニル基含有化合物の製造方法
KR101796993B1 (ko) 플루오렌 유도체, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물
CN117986231A (zh) 肟酯光引发剂、其制备方法及应用
CN116135889A (zh) 肟酯光引发剂、光固化树脂组合物及应用
KR20230146678A (ko) 광학소재용 고굴절 모노머 화합물 및 이를 포함하는 열경화성 또는 감광성 조성물
CN117510396A (zh) 肟酯光引发剂、其制备方法及应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination