CN114149517B - Oxime ester photoinitiator containing thiophene structure, preparation method and photosensitive resin composition - Google Patents

Oxime ester photoinitiator containing thiophene structure, preparation method and photosensitive resin composition Download PDF

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CN114149517B
CN114149517B CN202010928182.4A CN202010928182A CN114149517B CN 114149517 B CN114149517 B CN 114149517B CN 202010928182 A CN202010928182 A CN 202010928182A CN 114149517 B CN114149517 B CN 114149517B
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钱晓春
汪雷
张学龙
于培培
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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    • 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
    • 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
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • 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
    • C07D409/12—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 chain containing hetero atoms as chain links
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • 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
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    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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Abstract

The invention discloses an oxime ester photoinitiator containing a thiophene structure, a preparation method thereof and a photosensitive resin composition containing the photoinitiator and capable of being used for alkaline development. The photosensitive resin composition does not overflow gas after exposure, and has excellent film forming properties such as line width, side line uniformity, development process margin and the like.

Description

Oxime ester photoinitiator containing thiophene structure, preparation method and photosensitive resin composition
Technical Field
The invention belongs to the technical field of photoelectricity and chemistry intersection, and particularly relates to an oxime ester photoinitiator containing a thiophene structure, a preparation method of the oxime ester photoinitiator, and a photosensitive resin composition containing the photoinitiator and capable of being used for alkaline development.
Background
The oxime ester photoinitiator is a novel cracking free radical photoinitiator which is formed in recent years, has the advantages of high light sensitivity, good component compatibility and stability, high polymerization rate, conversion rate and transparency of photosensitive materials, less photoetching residues and the like, and is widely used in photoresist. The prior art such as CN101014569A, CN102112438A, CN102093282A, CN101735344A, CN101525393A, CN101528694A, CN102015633A, CN101048377A, CN101243057A and CN103998422A, etc. by introducing suitable substituents into oxime ester compounds, industrial requirements of various purposes are met, such as: high sensitivity to long-wavelength light between 365nm and 435nm, good curing reactivity, higher thermal stability and storage stability, good solubility, and the like. However, the oxime ester compounds are known to be used as photoinitiators, and most of them have the problem that the initiator components overflow and volatilize after exposure to pollute optical components, which not only affects the overall application performance of the composition, but also cannot be applied to the preparation of high-precision devices. Therefore, there is a need to develop a photoinitiator and a photosensitive composition having excellent properties and no gas overflow after exposure, and to solve the possible defects in applications such as line width, side line uniformity, and development process margin after application of the composition.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention is directed to an oxime ester photoinitiator containing a thiophene structure, which has a structure represented by formula a, B, C, D or E:
Figure BDA0002669201130000021
wherein,
R 1 and R 1 ’ May be the same or different, each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkylalkyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted heterocyclic group;
R 2 represents hydrogen, nitro, cyano, hydroxyl, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl;
in the general formulas A and B, n independently represents 1, 2,3 or 4;
in the general formulae C, D and E, m and n may be the same or different and each independently represents 0, 1, 2,3 or 4, and at least one of m and n is not 0.
As a preferred embodiment, R 1 And R 1 ’ May be the same or different and each independently represents C 1 -C 8 Is optionally substituted by 1-3C 1 -C 6 Alkyl substituted C 6 -C 12 Aryl of (C) 3 -C 12 Cycloalkyl of, C 4 -C 18 Cycloalkylalkyl of (C) 7 -C 16 An arylalkyl group containing O or S, a five-or six-membered heterocyclic group containing O or S.
Most preferably, R 1 And R 1 ’ May be the same or different and each independently represents C 1 -C 4 Alkyl, phenyl, substituted by 1-3C 1 -C 4 Alkyl-substituted phenyl, C 3 -C 8 Cycloalkyl, C monosubstituted by phenyl 1 -C 4 Alkyl, furyl, thienyl.
As a preferred embodiment, R 2 Represents hydrogen, nitro, optionally substituted by 1-3C 1 -C 6 Alkyl substituted C 6 -C 12 Arylformyl, five-or six-membered heterocyclic formyl group containing O or S, C 3 -C 12 Alkyl formyl group, C 4 -C 16 Cycloalkyl alkylcarboxyl radical of (A), C 3 -C 12 In which-CH attached to the carbonyl group in the alkylcarboxyl fragment of the last three groups 2 -may optionally be substituted by-O-, -S-or-C (= N-O-CO-CH) 3 ) -substitution.
Most preferably, R 2 Represents hydrogen, nitro, benzoyl, or a substituted or unsubstituted C1-3 1 -C 4 Alkyl-substituted benzoyl, furoyl, thenoyl, C 4 -C 10 Alkyl formyl group, C 6 -C 12 Cycloalkyl alkylcarboxyl radical of (A), C 4 -C 9 Heterocyclylalkylformyl of (2), wherein the alkyl moiety of the last three groups has a-CH attached to the carbonyl group 2 -may optionally be substituted by-C (= N-O-CO-CH) 3 ) -takingAnd (4) generation.
In the general formulas A and B, n represents 1 or 2 independently.
In the general formulae C, D and E, m and n may be the same or different and each independently represents 1 or 2.
More specifically, the oxime ester photoinitiator containing a thiophene structure of the present invention may have the following structure:
Figure BDA0002669201130000041
Figure BDA0002669201130000051
Figure BDA0002669201130000061
Figure BDA0002669201130000071
Figure BDA0002669201130000081
Figure BDA0002669201130000091
Figure BDA0002669201130000101
correspondingly, the invention also aims to provide a preparation method of the oxime ester photoinitiator containing the thiophene structure.
The preparation method of the compound represented by the general formula a is shown in the following scheme 1, and comprises:
[ scheme 1]
Figure BDA0002669201130000111
(1) Under the conditions of ice water bath and catalyst existence and nitrogen atmosphere, carrying out cyclization reaction on the raw material and an acylation reagent;
(2) Carrying out oximation reaction on the product obtained in the step (1) and nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula A.
In step (1), the catalyst used may be selected from AlCl 3 、H 2 SO 4 、AlBr 3 、BF 3 、GaCl 3 、FeCl 3 、SbCl 5 、ZrCl 4 、SnCl 4 、BCl 3 、SbCl 3 Preferably AlCl 3 . The acylating agent used is a haloacyl halide such as 3-chloropropionyl chloride, 3-bromopropionyl bromide, and the like.
In the step (2), the nitrite used is methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite or the like. The reaction temperature is controlled between-15 ℃ and 50 ℃, preferably between 0 ℃ and 25 ℃.
In the step (3), the esterifying reagent used is R 1 -CO-X or R 1 -CO-O-CO-R 1 Wherein X represents halogen. Illustratively, the esterifying agent may be selected from: cyclohexanecarbonyl chloride, 2-propylvaleryl chloride, 3, 5-trimethylhexanoyl chloride, 3-chloropropionyl chloride, 5-chloropentanoyl chloride, 3-chlorotetradecanoyl chloride, 6-bromohexanoyl chloride, methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, 3- (methylthio) propionyl chloride, (2-butoxyethoxy) acetyl chloride, benzoyl chloride, toluoyl chloride, 3, 5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride, chlorophenylacetyl chloride, 4-phenylbutyryl chloride, 6-phenylhexanoyl chloride, nitrophenylacetyl chloride, phenoxyacetyl chloride, phenoxypropionyl chloride, chlorophenoxyacetyl chloride, nitrophenoxyacetyl chloride, nitroxyacetyl chloride, nitrobenzoyloxy chloride, etcAcyl halides such as phenoxyacetyl chloride, 2-thenoyl chloride, thiophene-2-acetyl chloride, chloronicotinoyl chloride, 2-furoyl chloride, quinolinoyl chloride, naphthoyl chloride, 2-ethoxy-1-naphthoyl chloride, anthraceneoyl chloride, etc.; anhydrides such as acetic anhydride, propionic anhydride, decanoic anhydride, stearic anhydride, isobutyric anhydride, t-valeric anhydride and 4-methoxyphenylacetic anhydride.
In the step (3), the base used may be selected from triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide or sodium hydride, etc. The inert solvent is not particularly limited as long as it can dissolve the reaction raw material and does not adversely affect the reaction, and may be selected from, for example, diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, dimethylacetamide, dimethylformamide and the like. The reaction temperature is controlled at-10 to 60 ℃, preferably 0 to 25 ℃.
The preparation method of the compound represented by the general formula B is shown in the following scheme 2, and includes:
[ scheme 2]
Figure BDA0002669201130000121
(1) The carboxylic acid reactant as the starting material generates cyclic ketone through Friedel-Crafts cyclization reaction;
(2) Carrying out oximation reaction with nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula B.
In step (1), the carboxylic acid reactant as a starting material may be synthesized according to the Heck coupling-reduction-hydrolysis reaction scheme (but is not limited to such methods). With R as shown below 2 Substituted dibenzothiophenes 2-propionate are examples which can be synthesized with reference to the following reaction scheme:
Figure BDA0002669201130000131
specifically, 2-iododibenzothiophene is subjected to Heck coupling reaction and then reduction reaction under the catalysis of Raney nickel to obtain 2-methyl propionate dibenzothiophene, and then the 2-methyl propionate dibenzothiophene is hydrolyzed in an alcohol solution under an alkaline condition to generate a carboxylic acid reactant serving as a starting material.
In the Friedel-Crafts cyclization reaction in the step (1), the used catalyst comprises concentrated sulfuric acid, polyphosphoric acid, trifluoromethanesulfonic acid and the like; the reaction temperature is controlled to 20-100 deg.C, preferably 60-80 deg.C.
In the step (2), the nitrite used is methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite or the like. The reaction temperature is controlled between-15 ℃ and 50 ℃, preferably between 0 ℃ and 25 ℃.
In step (3), the esterification reagent, inert solvent and base used have the same meanings as described in step (3) of scheme 1.
The preparation method of the compound represented by the general formula C is shown in the following scheme 3, and includes:
[ scheme 3]
Figure BDA0002669201130000141
(1) Under the conditions of ice water bath and catalyst existence and in nitrogen atmosphere, carrying out cyclization reaction on a raw material dibenzothiophene and an acylation reagent;
(2) Carrying out oximation reaction on the product obtained in the step (1) and nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula C.
The preparation of the compounds of formula C is similar to the compounds of formula a, and the reaction conditions can be performed with reference to scheme 1.
The preparation process of the compound represented by the general formula D is shown in the following scheme 4, and comprises:
[ scheme 4]
Figure BDA0002669201130000142
(1) The dicarboxylic acid reactant as starting material undergoes Friedel-Crafts cyclization to form a cyclic ketone;
(2) Carrying out oximation reaction with nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula D.
The preparation of compounds of formula D is similar to compounds of formula B, and the reaction conditions can be performed with reference to scheme 2.
The dicarboxylic acid reactant as the starting material in step (1) can also be synthesized according to the Heck coupling-reduction-hydrolysis reaction scheme (but is not limited to such methods). The dibenzothiophene dipropionate can be synthesized by taking the dibenzothiophene dipropionate as an example, according to the following reaction scheme:
Figure BDA0002669201130000151
specifically, 2' -diiododibenzothiophene is subjected to Heck coupling reaction and then reduction reaction under the catalysis of raney nickel to obtain 2,2' -dipropionate methyl ester dibenzothiophene, and then the 2,2' -dipropionate methyl ester dibenzothiophene is hydrolyzed in an alcohol solution under an alkaline condition to generate a dicarboxylic acid reactant serving as a starting material.
The preparation method of the compound represented by the general formula E is shown in the following scheme 5, and comprises:
[ scheme 5]
Figure BDA0002669201130000161
(1) The dicarboxylic acid reactant as the starting material undergoes Friedel-Crafts cyclization to form a cyclic ketone;
(2) Carrying out oximation reaction with nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula E.
The preparation of compounds of formula E is similar to compounds of formula B, and the reaction conditions can be performed with reference to scheme 2.
The dicarboxylic acid reactant as the starting material in step (1) can also be synthesized according to the Heck coupling-reduction-hydrolysis reaction scheme (but is not limited to such methods). The dibenzothiophene dipropionate can be synthesized by taking the dibenzothiophene dipropionate as an example, according to the following reaction scheme:
Figure BDA0002669201130000162
specifically, 2,3' -diiododibenzothiophene is utilized to carry out Heck coupling reaction, and then reduction reaction is carried out under the catalysis of raney nickel to obtain 2,3' -dipropionate methyl dibenzothiophene, and then the 2,3' -dipropionate methyl dibenzothiophene is hydrolyzed in alcohol solution under alkaline conditions to generate dicarboxylic acid reactant serving as a starting material.
After providing the oxime ester photoinitiator containing the thiophene structure and the preparation method thereof, the invention also relates to the application of the oxime ester photoinitiator containing the thiophene structure in the photosensitive resin composition.
Further, an object of the present invention is to provide an alkali developable photosensitive resin composition comprising:
(A) An alkali-soluble resin;
(B) A photopolymerizable compound;
(C) Oxime ester photoinitiators containing thiophene structures as described above.
In the photosensitive resin composition of the present invention, the alkali-soluble resin of component (a) is preferably a compound obtained by polymerizing a carboxyl group-containing unsaturated monomer and other copolymerizable unsaturated monomer.
As the carboxyl group-containing unsaturated monomer, the following compounds can be mentioned: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; three or more membered unsaturated polycarboxylic acids or anhydrides thereof; mono [ (meth) acryloyloxyalkyl ] esters of dibasic or higher polycarboxylic acids such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-methacryloyloxyethyl); and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone monoacrylate and ω -carboxy polycaprolactone monomethacrylate. These carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more.
Examples of other copolymerizable unsaturated monomers include: aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; unsaturated carboxylic acid glycidyl esters such as indene-based glycidyl acrylates and glycidyl methacrylates, e.g., indene and 1-methylindene; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, or the like. These copolymerizable unsaturated monomers may be used alone or in combination of two or more.
In the present invention, the alkali-soluble resin of component (a) may be used alone or in combination of two or more.
In order to improve the developability and the liquid viscosity, the alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC) of 1000 to 200000, more preferably 2000 to 100000, and most preferably 5000 to 50000.
Without limitation but particularly preferably, alkali-soluble resins such as those disclosed in patent documents with patent publication numbers CN106554459A, CN 10639660A, CN110066391A and CN110389498A may be used.
The alkali-soluble resin of component (a) is contained in an amount of 5 to 85%, preferably 10 to 70%, based on the total weight of solids of the photosensitive resin composition.
The photopolymerizable compound of component (B) is a photopolymerizable compound which can be polymerized by active radicals, acids, etc. generated from a photoinitiator by irradiation, has one or more functional groups, and is recorded as a monofunctional polymerizable compound, a bifunctional polymerizable compound, or a polyfunctional polymerizable compound according to the number of functional groups.
Specific examples of the monofunctional polymerizable compound may include: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like.
Specific examples of the bifunctional polymerizable compound may include: 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butanediol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate and the like.
Specific examples of the trifunctional polymerizable compound may include: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glyceryl propoxylated triacrylate, isocyanurate triacrylate, and the like.
Specific examples of the tetrafunctional polymerizable compound may include: pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, and the like.
Specific examples of the pentafunctional polymerizable compound may include: dipentaerythritol penta (meth) acrylate; and specific examples of the hexafunctional polymerizable compound may include: dipentaerythritol hexa (meth) acrylate.
Among them, a polyfunctional polymerizable compound having two or more functional groups is preferably used, and a polyfunctional polymerizable compound having five or more functional groups is particularly more preferably used.
The photopolymerizable compound of component (B) is preferably used in an amount of 5 to 50%, and more preferably 10 to 30%, based on the total weight of the solids of the photosensitive resin composition.
In the photosensitive resin composition, the photoinitiator of component (C) is preferably used in an amount of 1 to 10%, and more preferably 3 to 5%, based on the total weight of the solids of the composition.
Further, other components commonly used in the art, including but not limited to solvents, pigments, sensitizers, dispersants, surfactants, and the like, may also be optionally added as required by the application of the composition.
The photosensitive resin composition of the present invention is polymerized by applying energy generated by ultraviolet rays, visible rays, near infrared rays, electron beams, or the like during polymerization reaction, and a target polymer can be obtained. As the energy-imparting light source, a light source having a dominant wavelength that emits light in a wavelength region of 250nm to 450nm is preferable. Examples of the light source having a dominant wavelength that emits light in a wavelength region of 250 to 450nm include various light sources such as an ultra-high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a pulse light-emitting xenon lamp, a deuterium lamp, a Led lamp, a fluorescent lamp, an Nd-YAG3 double wave laser, a He-Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a Xe-F excimer laser, and a semiconductor excited solid state laser.
The photosensitive resin composition of the present invention can be obtained by weighing the components in a certain amount and mixing them uniformly, which is a well-known conventional technique for those skilled in the art.
The invention also aims to provide application of the photosensitive resin composition in preparation of color filters, black matrixes and photo spacers.
Techniques for preparing RGB, BM, photo spacers, etc. by photo-curing and photolithography processes using the photosensitive resin composition are well known to those skilled in the art. Generally comprising the steps of:
i) Dissolving the photosensitive resin composition in a proper organic solvent, and uniformly mixing to obtain a liquid composition;
ii) uniformly coating the liquid composition on the substrate using a coater such as a spin coater, a wire bar coater, a spin coater, a spray coater, or a spray coater;
iii) Pre-baking and drying to remove the solvent;
iv) attaching a mask to the sample for exposure followed by development to remove the unexposed areas;
v) post-baking to obtain the photoresist dry film with the desired shape.
The photoresist film containing black pigment is the black matrix BM, and the photoresist film containing red, green and blue pigments is the corresponding R, G and B photoresists.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Examples of preparation of Compounds
EXAMPLE 1 preparation of Compound A-1
Figure BDA0002669201130000221
Step (1) preparation of intermediate A-1-1
Figure BDA0002669201130000222
Dibenzothiophene (18.4 g,0.1 mol) and carbon disulfide (200 mL) were added to a 500mL round-bottomed flask, 3-bromopropionyl bromide (21.6 g,0.1 mol) was added under nitrogen, the mixture was dissolved with stirring, then cooled in an ice water bath, aluminum trichloride (33.3 g, 0.25mol) was added in portions under nitrogen for 2 hours, and then the mixture was stirred at room temperature for 8 hours. After the reaction is completed, 500mL of distilled water is added for quenching, then the mixture is washed for 3 times by 500mL of distilled water, the mixture is kept stand for layering, an organic phase is dried by anhydrous magnesium sulfate, and the organic solvent is removed by reduced pressure distillation, so that 19.6g of light yellow solid, namely the intermediate A-1-1 is obtained, and the yield is 82.3%.
Step (2) preparation of intermediate A-1-2
Figure BDA0002669201130000231
A1-L round-bottomed flask was charged with intermediate A-1-1 (38.1g, 0.16mol) and tetrahydrofuran (400 mL), the temperature was controlled to 5 ℃ or lower, 30mL of concentrated hydrochloric acid was added, isoamyl nitrite (22.5g, 0.19mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 500mL of a saturated aqueous solution of sodium chloride, extraction was performed with 500mL of ethyl acetate, and the organic phase was washed with water (300 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to obtain 32.8g of a pale yellow solid, i.e., intermediate A-1-2, in a yield of 76.6%.
Step (3) preparation of Compound A-1
Figure BDA0002669201130000232
A1L reaction flask was charged with intermediate A-1-2 (29.4 g, 0.11mol), TEA (16.7g, 0.11mol) and 300mL of methylene chloride, and stirred to dissolve the resulting mixture. Acetic anhydride (13.5g, 0.13mol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 500mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 180mL of methanol to obtain a crude product. Dissolving the crude product in 120mL of acetone, adding the acetone into 360mL of methanol, stirring for crystallization, continuously stirring for 1h in ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 23.4g of light yellow solid, wherein the yield is 68.7%, and the purity is 99.29%.
The structure of compound a-1 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.37-8.32(m,1H),8.25(s,1H),7.78(s,1H),7.71(dd,J＝7.5,1.6Hz,1H),7.44(td,J＝7.5,1.5Hz,1H),7.34(td,J＝7.4,1.6Hz,1H),3.32(s,2H),2.14(s,3H).
EXAMPLE 2 preparation of Compound A-2
Figure BDA0002669201130000241
A1L reaction flask was charged with intermediate A-1-2 (29.4 g, 0.11mol), TEA (16.7g, 0.11mol) and 300mL of methylene chloride, and stirred to dissolve the resulting mixture. Benzoyl chloride (18.3g, 0.13mol) was added dropwise and stirred at room temperature for 3h. Adding 500mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 180mL of methanol to obtain a crude product. Dissolving the crude product in 120mL of acetone, adding into 360mL of methanol, stirring for crystallization, continuing stirring for 1h in ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h. 25.0g of a pale yellow solid are obtained in 61.3% yield and 99.17% purity.
The structure of compound a-2 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.34(dd,J＝7.4,1.7Hz,1H),8.27(s,1H),8.16–8.09(m,2H),7.82(s,1H),7.73(dd,J＝7.5,1.5Hz,1H),7.66–7.59(m,1H),7.47(td,J＝7.5,1.2Hz,3H),7.35(td,J＝7.5,1.7Hz,1H),3.31(s,2H).
EXAMPLE 3 preparation of other Compounds
The following compounds A3 to A15, whose structures and corresponding nuclear magnetic characterization data are shown in Table 1 below, were prepared by replacing the corresponding starting materials according to the method of example 1 or 2.
TABLE 1
Figure BDA0002669201130000251
Figure BDA0002669201130000261
Figure BDA0002669201130000271
EXAMPLE 4 preparation of Compound B-1
Figure BDA0002669201130000272
Step (1) preparation of intermediate B-1-4
Figure BDA0002669201130000273
A1L round-bottomed flask was charged with B-1-1 (46.5g, 0.15mol), sodium carbonate (23.9g, 0.23mol), palladium acetate (0.675g, 3.0 mmol), PPh 3 (0.79g, 3 mmol) and methyl acrylate (25.8g, 0.3 mol). Under the protection of nitrogenNext, dry DMF (N, N-dimethylformamide) (500 mL) was added, and the mixture was heated to 90 ℃ and stirred overnight. After the reaction was cooled to room temperature, the excess methyl acrylate was removed under reduced pressure, 2L of water was added, ethyl acetate was further added for extraction (500 mL × 3), the organic phases were combined, washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated, and the crude product was purified by column chromatography using petroleum ether/ethyl acetate (5) as an eluent to give a pale yellow solid, which was recrystallized from ethanol to give 30.7g of an off-white solid (i.e., intermediate B-1-2) in 76.2% yield.
B-1-2 (26.8g, 0.1mol), raney nickel (8.2 g) and ethanol (300 mL) were charged in a 1-L round-bottom flask under a nitrogen atmosphere, and the mixture was replaced with nitrogen gas for 3 times, and then hydrogen gas was introduced and the reaction was stirred at room temperature. After the reaction was completed, the reaction mixture was replaced with nitrogen 3 times, and the catalyst was removed by filtration, and the filtrate was concentrated to obtain 26.7g of a white solid (i.e., intermediate B-1-3) with a yield of 98.6%.
B-1-3 (13.5g, 0.05mol), potassium hydroxide (2.8g, 0.05mol), water (50 mL) and ethanol (50 mL) were charged into a 250mL round-bottomed flask, and the mixture was stirred, heated to reflux and stirred for 1 hour. Concentration removed ethanol, in an ice-water bath, hydrochloric acid was slowly added to the aqueous residue until pH =2, the corresponding acid was precipitated out, the precipitate was collected by filtration, washed three times with water and dried under vacuum to give 12.0g of a white solid, intermediate B-1-4, yield 93.7%.
Step (2) preparation of intermediate B-1-5
Figure BDA0002669201130000281
To a 500mL round-bottomed flask were added B-1-4 (10.3 g, 0.04mol) and 100mL dichloromethane with stirring in an ice-water bath, oxalyl chloride (25.4 g, 0.2mol) was slowly added dropwise thereto, and after completion of the addition, the mixture was allowed to warm to room temperature and stirred for 2 hours. The remaining oxalyl chloride and dichloromethane were removed under reduced pressure, anhydrous carbon disulfide (100 mL) was added under nitrogen protection, anhydrous aluminum chloride (8.0 g, 0.06mol) was added in an ice-water bath, the mixture was refluxed for 2h, then quenched into 12% dilute hydrochloric acid, the aqueous layer was extracted three times with chloroform, the combined extracts were washed successively with water, sodium bicarbonate solution and saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated to remove the solvent, and then column chromatography purification was performed using ethyl acetate/petroleum ether to give a crude product, which was recrystallized with ethanol to give 6.5g of a pale yellow solid product, i.e., intermediate B-1-5, in a yield of 68.6%.
Step (3) preparation of intermediate B-1-6
Figure BDA0002669201130000291
A1L round-bottomed flask was charged with intermediate B-1-5 (19.1g, 0.08mol) and tetrahydrofuran (200 mL), the temperature was controlled at 5 ℃ or lower, 15mL of concentrated hydrochloric acid was added, isoamyl nitrite (11.3 g, 0.10mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 250mL of a saturated aqueous solution of sodium chloride, extraction was performed with 250mL of ethyl acetate, and the organic phase was washed with water (150 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to obtain 14.4g of a pale yellow solid, i.e., intermediate B-1-6, in a yield of 67.4%.
Step (4) preparation of intermediate B-1
Figure BDA0002669201130000292
To a 1L reaction flask were added intermediate B-1-6 (20.6 g, 77mmol), TEA (11.7 g, 112mmol) and 200mL of dichloromethane, and the solution was stirred. Acetic anhydride (9.5g, 91mmol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 300mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 120mL of methanol to obtain a crude product. Dissolving the crude product in 100mL of acetone, adding the acetone into 250mL of methanol, stirring for crystallization, continuously stirring for 1h in ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 17.2g of light yellow solid, wherein the yield is 72.1% and the purity is 99.32%.
The structure of compound B-1 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.72(s,1H),8.34(dd,J＝7.4,1.6Hz,1H),7.83(s,1H),7.71(dd,J＝7.5,1.6Hz,1H),7.45(td,J＝7.4,1.6Hz,1H),7.34(td,J＝7.4,1.5Hz,1H),3.31(s,2H),2.14(s,3H).
EXAMPLE 5 preparation of other Compounds
Other compounds of the general formula B as shown in table 2 below were synthesized by changing the corresponding raw materials according to the method of example 4.
TABLE 2
Figure BDA0002669201130000301
Figure BDA0002669201130000311
Figure BDA0002669201130000321
EXAMPLE 6 preparation of Compound C-1
Figure BDA0002669201130000331
Step (1) preparation of intermediate C-1-1
Figure BDA0002669201130000332
After dibenzothiophene (18.4 g,0.1 mol) and carbon disulfide (200 mL) were added to a 500mL round-bottomed flask, 3-bromopropionyl bromide (64.8g, 0.3 mol) was added under nitrogen, the mixture was dissolved with stirring, cooled in an ice-water bath, and aluminum trichloride (99.9g, 0.75mol) was added in portions under nitrogen for 2 hours, and then the mixture was stirred at room temperature for 18 hours. After the reaction was completed, 500mL of distilled water was added to quench, and then the mixture was washed with 500mL of distilled water for 3 times, allowed to stand for separation, and the organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the organic solvent, whereby 16.0g of a pale yellow solid, i.e., intermediate C-1-1 was obtained in 54.6% yield.
Step (2) preparation of intermediate C-1-2
Figure BDA0002669201130000333
A1L round-bottomed flask was charged with intermediate C-1-1 (35.1g, 0.12mol) and tetrahydrofuran (400 mL), the temperature was controlled at 5 ℃ or lower, 36mL of concentrated hydrochloric acid was added, isoamyl nitrite (42.2g, 0.36mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 500mL of a saturated aqueous solution of sodium chloride, extraction was performed with 500mL of ethyl acetate, and the organic phase was washed with water (300 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to obtain 31.5g of a pale yellow solid, i.e., intermediate C-1-2, in a yield of 74.9%.
Step (3) preparation of Compound C-1
Figure BDA0002669201130000341
A1L reaction flask was charged with intermediate C-1-2 (9.6g, 27.5mmol), TEA (8.4 g,80.0 mol), and 75mL of dichloromethane, and stirred to dissolve. Acetic anhydride (6.8g, 65.0 mol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 500mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 180mL of methanol to obtain a crude product. Dissolving the crude product in 120mL of acetone, adding the acetone into 360mL of methanol, stirring for crystallization, continuously stirring for 1h in an ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 7.4g of yellow solid, wherein the yield is 62.1% and the purity is 98.62%.
The structure of compound C-1 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.21(s,2H),7.80(s,2H),3.29(s,4H),2.12(s,6H).
EXAMPLE 7 preparation of other Compounds
Referring to the procedure of example 6, other compounds of the general formula C as shown in table 3 below were synthesized by replacing the corresponding starting materials.
TABLE 3
Figure BDA0002669201130000351
EXAMPLE 8 preparation of Compound D-1
Figure BDA0002669201130000361
Step (1) preparation of intermediate D-1-4
Figure BDA0002669201130000362
A1L round-bottomed flask was charged with D-1-1 (78.5g, 0.18mol), sodium carbonate (57.4g, 0.55mol), palladium acetate (1.62g, 7.2mmol), PPh 3 (1.9g, 7.2mmol) and methyl acrylate (61.9g, 0.72mol). Dry DMF (N, N-dimethylformamide) (600 mL) was added under nitrogen blanket, then the mixture was heated to 90 ℃ and stirred overnight. After the reaction was cooled to room temperature, the excess methyl acrylate was removed under reduced pressure, 2L of water was added, ethyl acetate was further added for extraction (500 mL × 3), the organic phases were combined, washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated, and the crude product was purified by column chromatography using petroleum ether/ethyl acetate (3).
D-1-2 (17.6 g, 0.05mol), raney nickel (8.2 g) and ethanol (300 mL) were charged into a 1-L round-bottom flask under a nitrogen atmosphere, and the mixture was replaced with nitrogen 3 times, and then hydrogen was introduced thereinto to conduct the reaction with stirring at room temperature. After the reaction was completed, the reaction mixture was replaced with nitrogen gas 3 times, and then the catalyst was removed by filtration, and the filtrate was concentrated to obtain 17.2g of a white solid (i.e., intermediate D-1-3) with a yield of 96.3%.
D-1-3 (14.3g, 0.04mol), potassium hydroxide (5.6 g, 0.1mol), water (80 mL) and ethanol (80 mL) were added to a 250mL round-bottom flask, mixed with stirring, warmed to reflux and stirred for 1h. Concentration removed ethanol, hydrochloric acid was slowly added to the aqueous residue in an ice water bath until pH =2, the corresponding acid was precipitated, the precipitate was collected by filtration, washed three times with water and dried under vacuum to give 12.4g of white solid, intermediate D-1-4, yield 94.1%.
Step (2) preparation of intermediate D-1-5
Figure BDA0002669201130000371
D-1-4 (13.1 g, 0.04mol) and 100mL of methylene chloride were added to a 500mL round-bottomed flask with stirring in an ice-water bath, oxalyl chloride (50.8g, 0.4 mol) was slowly added dropwise thereto, and after the addition was completed, the mixture was allowed to warm to room temperature and stirred for 2 hours. The remaining oxalyl chloride and dichloromethane were removed under reduced pressure. Anhydrous carbon disulfide (100 mL) was added under nitrogen protection, anhydrous aluminum chloride (16.0 g, 0.12mol) was added in an ice-water bath, the mixture was refluxed for 2h, then quenched into 12% diluted hydrochloric acid, the aqueous layer was extracted three times with chloroform, the combined extracts were washed with water, sodium bicarbonate solution and saturated aqueous sodium chloride solution in this order, then dried over anhydrous magnesium sulfate, filtered, concentrated to remove the solvent, and then column-chromatographed using ethyl acetate/petroleum ether to give the crude product, which was recrystallized with ethanol to give 5.6g of pale yellow solid product, i.e., intermediate D-1-5, in 47.6% yield.
Step (3) preparation of intermediate D-1-6
Figure BDA0002669201130000381
A500L round-bottom flask was charged with intermediate D-1-5 (14.6 g, 0.05mol) and tetrahydrofuran (200 mL), and controlled at a temperature of 5 ℃ or lower, 23mL of concentrated hydrochloric acid was added, isoamyl nitrite (17.0 g, 0.15mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 250mL of a saturated aqueous sodium chloride solution, extracted with 250mL of ethyl acetate, and the organic phase was washed with water (150 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to give 10.5g of a pale yellow solid, i.e., intermediate D-1-6, in 59.8% yield.
Step (4) preparation of intermediate D-1
Figure BDA0002669201130000382
To a 1L reaction flask were added intermediate D-1-6 (28.0 g, 0.08mol), TEA (24.5 g, 0.24mol) and 250mL of methylene chloride, and the solution was stirred. Acetic anhydride (24.5g, 0.24mol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 300mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 120mL of methanol to obtain a crude product. And dissolving the crude product in 100mL of acetone, adding the acetone into 250mL of methanol, stirring for crystallization, continuously stirring for 1h in ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 23.6g of light yellow solid, wherein the yield is 68.0% and the purity is 98.79%.
The structure of compound D-1 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.08(s,2H),7.90(s,2H),3.31(s,4H),2.15(s,6H).
EXAMPLE 9 preparation of other Compounds
Referring to the procedure of example 8, other compounds of the general formula D as shown in table 4 below were synthesized by replacing the corresponding starting materials.
TABLE 4
Figure BDA0002669201130000391
EXAMPLE 10 preparation of Compound E-1
Figure BDA0002669201130000392
Step (1) preparation of intermediate E-1-4
Figure BDA0002669201130000401
A1L round-bottomed flask was charged with E-1-1 (78.5g, 0.18mol), sodium carbonate (57.4g, 0.55mol), palladium acetate (1.62g, 7.2mmol), PPh 3 (1.9g, 7.2mmol) and methyl acrylate (61.9g, 0.72mol). Dry DMF (N, N-dimethylformamide) (600 mL) was added under nitrogen blanket, then the mixture was heated to 90 ℃ and stirred overnight. After the reaction was cooled to room temperature, the excess methyl acrylate was removed under reduced pressure, 2L of water was added, ethyl acetate was further added for extraction (500 mL × 3), the organic phases were combined, washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated, and the crude product was purified by column chromatography using petroleum ether/ethyl acetate (3).
E-1-2 (21.1g, 0.06mol), raney nickel (9.8 g) and ethanol (360 mL) were charged into a 1-L round-bottomed flask under a nitrogen atmosphere, and the mixture was replaced with nitrogen gas for 3 times, and then hydrogen gas was introduced thereinto to conduct a reaction at room temperature with stirring. After the reaction was complete, the reaction was replaced with nitrogen 3 times, the catalyst was removed by filtration, and the filtrate was concentrated to give 20.9g of a white solid (i.e., intermediate E-1-3) with a yield of 97.6%.
E-1-3 (14.3g, 0.04mol), potassium hydroxide (5.6 g, 0.1mol), water (80 mL) and ethanol (80 mL) were added to a 250mL round-bottom flask, mixed with stirring, warmed to reflux and stirred for 1h. Concentration removed ethanol, in an ice-water bath, hydrochloric acid was slowly added to the aqueous residue until pH =2, the corresponding acid was precipitated out, the precipitate was collected by filtration, washed three times with water and dried under vacuum to give 12.3g of a white solid, intermediate E-1-4, yield 93.4%.
Step (2) preparation of intermediate E-1-5
Figure BDA0002669201130000411
E-1-4 (19.7 g, 0.06mol) and 150mL of methylene chloride were added to a 500mL round-bottom flask with stirring in an ice-water bath, oxalyl chloride (76.2g, 0.6 mol) was slowly added dropwise thereto, and after completion of the addition, the mixture was allowed to warm to room temperature and stirred for 2 hours. The remaining oxalyl chloride and dichloromethane were removed under reduced pressure. Anhydrous carbon disulfide (150 mL) was added under nitrogen blanket, anhydrous aluminum chloride (24.0 g, 0.18mol) was added in an ice-water bath, the mixture was refluxed for 2h, then quenched into 12% dilute hydrochloric acid, the aqueous layer was extracted three times with chloroform, and the combined extracts were washed with water, sodium bicarbonate solution, and saturated aqueous sodium chloride solution in this order, then dried over anhydrous magnesium sulfate, filtered, concentrated to remove the solvent, and then purified by column chromatography using ethyl acetate/petroleum ether to give a crude product, which was recrystallized from ethanol to give 9.0g of a pale yellow solid product, intermediate E-1-5, in 51.3% yield.
Step (3) preparation of intermediate E-1-6
Figure BDA0002669201130000412
Intermediate E-1-5 (23.4 g, 0.08mol) and tetrahydrofuran (320 mL) were charged into a 500L round-bottomed flask, 37mL of concentrated hydrochloric acid was added while controlling the temperature at 5 ℃ or lower, isoamyl nitrite (27.2g, 0.24mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 400mL of a saturated aqueous solution of sodium chloride, extracted with 400mL of ethyl acetate, and the organic phase was washed with water (240 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to give 18.2g of a pale yellow solid, i.e., intermediate E-1-6, in a yield of 64.8%.
Step (4) preparation of intermediate E-1
Figure BDA0002669201130000421
A1L reaction flask was charged with intermediate E-1-6 (21.0g, 0.06mol), TEA (18.4g, 0.18mol) and 200mL of methylene chloride, and the solution was stirred. Acetic anhydride (18.4g, 0.18mol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 250mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 400mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 90mL of methanol to obtain a crude product. And dissolving the crude product in 90mL of acetone, adding the acetone into 250mL of methanol, stirring for crystallization, continuously stirring for 1h in an ice bath, filtering, leaching a filter cake with 90mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 17.4g of light yellow solid, namely the compound E-1, wherein the yield is 66.7% and the purity is 99.06%.
The structure of compound E-1 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.10(d,J＝16.5Hz,2H),7.94(s,1H),7.90(s,1H),3.31(d,J＝1.3Hz,4H),2.15(s,6H).
EXAMPLE 11 preparation of other Compounds
Referring to the procedure of example 10, other compounds of the general formula E as shown in table 5 below were synthesized by replacing the corresponding starting materials.
TABLE 5
Figure BDA0002669201130000431
EXAMPLE 12 preparation of Compound B-17
Figure BDA0002669201130000432
Step (1) preparation of intermediate B-17-4
Figure BDA0002669201130000433
A1L round-bottomed flask was charged with B-1-1 (46.5g, 0.15mol), sodium carbonate (23.9g, 0.23mol), palladium acetate (0.675g, 3.0mmol), PPh 3 (0.79g, 3mmol) and methyl 3-butenoate (30.0 g, 0.3mol). Dry DMF (N, N-dimethylformamide) (500 mL) was added under nitrogen blanket, then the mixture was heated to 90 ℃ and stirred overnight. After the reaction was cooled to room temperature, the excess methyl acrylate was removed under reduced pressure, 2L of water was added, ethyl acetate was further added for extraction (500 mL × 3), the organic phases were combined, washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated, and the crude product was purified by column chromatography using petroleum ether/ethyl acetate (5) as an eluent to give a pale yellow solid, which was recrystallized from ethanol to give 31.6g of an off-white solid (i.e., intermediate B-17-2) in 74.5% yield.
B-17-2 (28.2 g,0.1 mol), raney nickel (8.2 g) and ethanol (300 mL) were added to a 1-L round-bottom flask under a nitrogen atmosphere, the mixture was replaced with nitrogen gas for 3 times, hydrogen gas was introduced, and the reaction was stirred at room temperature. After the reaction was completed, the reaction mixture was replaced with nitrogen 3 times, and then the catalyst was removed by filtration, and the filtrate was concentrated to obtain 27.3g of a white solid (i.e., intermediate B-17-3) with a yield of 96.1%.
B-17-3 (14.2g, 0.05mol), potassium hydroxide (2.8g, 0.05mol), water (50 mL) and ethanol (50 mL) were charged into a 250mL round-bottomed flask, and the mixture was stirred, heated to reflux, and stirred for 1 hour. Concentration removed ethanol, hydrochloric acid was slowly added to the aqueous residue in an ice water bath until pH =2, allowing the corresponding acid to precipitate out, the precipitate was collected by filtration, washed three times with water and dried under vacuum to give 13.4g of a white solid, intermediate B-17-4, in 98.8% yield.
Step (2) preparation of intermediate B-17-5
Figure BDA0002669201130000451
To a 500mL round-bottomed flask were added B-17-4 (10.8g, 0.04mol) and 100mL dichloromethane with stirring in an ice-water bath, oxalyl chloride (25.4 g, 0.2mol) was slowly added dropwise thereto, and after completion of the addition, the mixture was allowed to warm to room temperature and stirred for 2h. The remaining oxalyl chloride and dichloromethane were removed under reduced pressure, anhydrous carbon disulfide (100 mL) was added under nitrogen blanket, anhydrous aluminum chloride (8.0 g, 0.06mol) was added in an ice-water bath, the mixture was refluxed for 2h, then quenched into 12% dilute hydrochloric acid, the aqueous layer was extracted three times with chloroform, the combined extracts were washed successively with water, sodium bicarbonate solution and saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, concentrated to remove the solvent, and then column chromatography purification was performed using ethyl acetate/petroleum ether to give a crude product, which was recrystallized with ethanol to give 7.4g of a pale yellow solid product, intermediate B-17-5, yield 73.6%.
Step (3) preparation of intermediate B-17-6
Figure BDA0002669201130000452
B-17-5 (7.6 g, 0.03mol) and dichloromethane (80 mL) were added to a 500mL round bottom flask, anhydrous aluminum chloride (8.0 g, 0.06mol) was added to the flask in an ice-water bath, octanoyl chloride (5.4 g, 0.033mol) was added dropwise thereto, stirring was continued until the reaction was completed after the dropwise addition was completed, the material was slowly poured into a mixed solution of ice water and 12% dilute hydrochloric acid, allowed to stand for separation into layers, the lower dichloromethane layer was separated, the aqueous layer was further washed with 50mL dichloromethane, the dichloromethane layers were combined, washed with an aqueous sodium bicarbonate solution (150 mL. Times.3 times), washed with water until the pH was neutral, dried over anhydrous magnesium sulfate, filtered, dichloromethane was removed, recrystallized from methanol, and dried to obtain 8.9g of a pale yellow solid, i.e., intermediate B-17-6, in a yield of 78.5%.
Step (4) preparation of intermediate B-17-7
Figure BDA0002669201130000461
A500L round-bottomed flask was charged with intermediate B-17-6 (15.1g, 0.04mol) and tetrahydrofuran (160 mL), the temperature was controlled at 5 ℃ or lower, 19mL of concentrated hydrochloric acid was added thereto, isoamyl nitrite (13.6 g, 0.12mol) was added dropwise under a nitrogen atmosphere, and after completion of the addition, the reaction was continued at 5 ℃ for 4 hours. To the reaction solution was added 200mL of a saturated aqueous solution of sodium chloride, extraction was performed with 200mL of ethyl acetate, and the organic phase was washed with water (1200 mL. Times.3 times), dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from methylene chloride petroleum ether to obtain 10.4g of a pale yellow solid, i.e., intermediate B-17-7, in 59.7% yield.
Step (5) preparation of intermediate B-17
Figure BDA0002669201130000462
A1L reaction flask was charged with intermediate B-17-7 (10.5g, 0.03mol), TEA (9.2g, 0.09mol), and 100mL of methylene chloride, and the mixture was stirred to dissolve the precipitate. Acetic anhydride (9.2g, 0.09mol) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Adding 100mL of water into the reaction solution, stirring for 10min, standing for layering, separating out a lower organic phase, washing with water to be neutral, concentrating the organic phase, dissolving the obtained solid with 100mL of methanol, and refluxing and stirring for 1h. Cooling to room temperature, stirring for 1h, cooling to 5-10 deg.C in ice bath, and stirring for 1h. Filtering, washing a filter cake by 90mL of methanol to obtain a crude product. And dissolving the crude product in 90mL of acetone, adding the acetone into 100mL of methanol, stirring for crystallization, continuously stirring for 1h in an ice bath, filtering, leaching a filter cake with 100mL of methanol, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain 8.3g of light yellow solid, namely the compound B-17, wherein the yield is 52.9%, and the purity is 98.92%.
The structure of compound B-17 was confirmed by the following nuclear magnetic data:
1 H NMR(500MHz,Chloroform-d)δ8.40–8.33(m,2H),7.97(dd,J＝7.5,1.5Hz,1H),7.88–7.81(m,2H),2.90(t,J＝7.1Hz,2H),2.76(t,J＝7.1Hz,2H),2.69(t,J＝7.0Hz,2H),2.15(s,6H),1.67(p,J＝7.1Hz,2H),1.39–1.24(m,6H),0.93–0.84(m,3H).
EXAMPLE 13 preparation of other Compounds
Other compounds as shown in table 6 below were synthesized by changing the corresponding raw materials according to the method of example 12.
TABLE 6
Figure BDA0002669201130000471
Figure BDA0002669201130000481
Preparation and evaluation of the compositions
Exemplary photosensitive resin compositions were formulated according to the formulations shown in table 7, and the application properties of the compositions were evaluated.
TABLE 7 formulation of the compositions (values in parts by weight)
Figure BDA0002669201130000482
Figure BDA0002669201130000491
The structures of the conventional photoinitiators, i.e. compounds 1, 2,3, are as follows:
Figure BDA0002669201130000492
1. evaluation of line width, sideline uniformity and development process tolerance performance
Stirring the photosensitive resin composition with the composition under a yellow light, taking the photosensitive resin composition out of a clean glass sheet, and gluing the photosensitive resin composition on the clean glass sheet by using a rotary gluing machine to obtain a coating film with the dry film thickness of 2 mu m; pre-baking at 95 deg.C for 120s, and exposing with 365nm ultraviolet light (exposure of 30 mJ/cm) 2 ) The distance between the mask plate and the coating film is 180 mu m; the image was developed at 25 ℃ for 40s and then hard baked at 220 ℃ for 30min to fix the image.
And testing the line width, the sideline regularity and the development process tolerance. Wherein, the line width and the side line uniformity are tested by multiplying 500 times OM, and the line width of the mask plate is 140 μm; during the evaluation of the process tolerance, other process conditions are fixed, and the edge line uniformity and the edge residue or edge peeling condition of the image obtained in the development time of 40-100s are considered.
The line width evaluation criteria were as follows:
o: the difference between the developed line width and the heat-treated line width is less than 10 μm;
and (delta): the difference between the line width after development and the line width after heat treatment is greater than 10 μm.
The evaluation criteria for the edge line uniformity are as follows:
o: the 50s developed sideline is neat and no residue is left at the edge;
and (delta): burrs exist on the edge lines of the developed 50s image, and the burrs are irregular or residues exist at the edges;
x: the image is missing.
The evaluation criteria of the development process latitude are as follows:
o: the lines of the developing process are regular for 40-100s, and no residue or stripping exists at the edges;
and (delta): the developing lines are neat in 50-80s, and no residue or stripping exists at the edges;
x: the developing lines are irregular for 50-80s, or residues exist at the edges, or the edges are stripped.
The evaluation results are shown in table 8.
TABLE 8
Figure BDA0002669201130000501
Figure BDA0002669201130000511
2. Evaluation of the amount of overflowed gas
Photosensitive resin compositions were prepared according to the formulation shown in Table 7, and the compositions were applied by suspension coating onto a glass substrate to form a film having a thickness of 20 μm, using a hot air circulation type drying furnaceDrying at 80 deg.C for 30min, and exposing with high-pressure mercury lamp (60 mJ/cm) 2 )。
Cutting two equivalent samples of about 1.0000g from the cured film, taking one sample as a sample before heat curing, curing the other sample at 150 ℃ for 60min, and weighing; the two samples before and after thermal curing were then heated at 250 ℃ for 30min, respectively, and then further weighed. The weight difference before and after heating is the amount of the overflowed gas, and the ratio of the weight difference to the weight before heating is used as an evaluation index.
The evaluation results are shown in table 9.
TABLE 9 evaluation of overrun
Figure BDA0002669201130000512
Figure BDA0002669201130000521
As can be seen from tables 8 and 9, compared with the existing oxime ester photoinitiator, the photosensitive resin composition using the initiator of the invention has excellent curing and film-forming properties, obviously better line width, side line regularity and developing process wide margin, no out-flowing gas is detected when the photosensitive resin composition is heated at 150 ℃ and 250 ℃, and the photosensitive resin composition shows outstanding stability, and is particularly suitable for manufacturing parts with high precision requirements.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. An oxime ester photoinitiator containing a thiophene structure, which has a structure shown as a general formula C, D or E:
Figure FDA0003929239420000011
wherein,
R 1 and R 1 ’ May be the same or different, each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkylalkyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted heterocyclic group;
m and n may be the same or different, each independently represent 0, 1, 2,3 or 4, and at least one of m and n is not 0.
2. The oxime ester photoinitiator according to claim 1 wherein: r is 1 And R 1 ’ May be the same or different and each independently represents C 1 -C 8 Optionally substituted by 1 to 3C 1 -C 6 Alkyl substituted C 6 -C 12 Aryl of (C) 3 -C 12 Cycloalkyl of, C 4 -C 18 Cycloalkylalkyl of (C) 7 -C 16 An arylalkyl group containing O or S, a five-or six-membered heterocyclic group containing O or S.
3. The oxime ester photoinitiator according to claim 1 or 2 wherein: r 1 And R 1 ’ May be the same or different and each independently represents C 1 -C 4 Alkyl, phenyl, or 1-3C 1 -C 4 Alkyl-substituted phenyl, C 3 -C 8 Cycloalkyl, C monosubstituted by phenyl 1 -C 4 Alkyl, furyl, thienyl.
4. The oxime ester photoinitiator according to claim 1 wherein: in the general formulae C, D and E, m and n may be the same or different and each independently represents 1 or 2.
5. A process for the preparation of oxime ester photoinitiators of the general formula C as defined in any one of claims 1 to 4, as illustrated in scheme 3 below, comprising:
[ scheme 3]
Figure FDA0003929239420000021
(1) Under the conditions of ice water bath and catalyst existence and in nitrogen atmosphere, carrying out cyclization reaction on a raw material dibenzothiophene and an acylation reagent;
(2) Carrying out oximation reaction on the product obtained in the step (1) and nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and the esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula C.
6. A process for the preparation of oxime ester photoinitiators of general formula D according to any of claims 1 to 4, as shown in scheme 4 below, comprising:
[ scheme 4]
Figure FDA0003929239420000031
(1) The dicarboxylic acid reactant as the starting material undergoes Friedel-Crafts cyclization to form a cyclic ketone;
(2) Carrying out oximation reaction with nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula D.
7. A process for the preparation of oxime ester photoinitiators of general formula E according to any of claims 1 to 4, as shown in scheme 5 below, comprising:
[ scheme 5]
Figure FDA0003929239420000032
(1) The dicarboxylic acid reactant as the starting material undergoes Friedel-Crafts cyclization to form a cyclic ketone;
(2) Carrying out oximation reaction with nitrous acid or nitrous acid ester under alkaline or acidic conditions to generate an oxime compound;
(3) The oxime compound and an esterification reagent are subjected to esterification reaction in an inert solvent in the presence of alkali to generate the compound with the general formula E.
8. Use of an oxime ester photoinitiator according to any one of claims 1 to 4 in a photosensitive resin composition.
9. An alkali developable photosensitive resin composition comprising:
(A) An alkali-soluble resin;
(B) A photopolymerizable compound;
(C) The oxime ester photoinitiator of any one of claims 1 to 4.
10. The photosensitive resin composition according to claim 9, wherein: the alkali-soluble resin of component (A) is selected from compounds obtained by polymerizing a carboxyl-containing unsaturated monomer and other copolymerizable unsaturated monomers.
11. The photosensitive resin composition according to claim 9, wherein: the photopolymerizable compound of component (B) is selected from polyfunctional polymerizable compounds having two or more functional groups.
12. The photosensitive resin composition according to claim 9, wherein: the photopolymerizable compound of component (B) is selected from polyfunctional polymerizable compounds having five or more functional groups.
13. Use of the oxime ester photoinitiator according to any one of claims 1 to 4 or the photosensitive resin composition according to any one of claims 9 to 12 for the preparation of a color filter, a black matrix, a photo spacer.
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