CN-121990976-A - High-sensitivity oxime ester compound and preparation method and application thereof

CN121990976ACN 121990976 ACN121990976 ACN 121990976ACN-121990976-A

Abstract

The invention provides a high-sensitivity oxime ester compound and a preparation method and application thereof, wherein the high-sensitivity oxime ester compound has a structure shown in a formula I, a symbol E shows that O-N bonds in oxime groups are distributed in trans and are opposite to carbonyl groups, R 1 is selected from methyl, ethyl, isopropyl or sec-butyl, R 2 is selected from hydrogen or methyl, and R 3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl. The compound has remarkably high sensitivity in a photo-curing composition formula, particularly a high-sensitivity photoresist formula, the performance is remarkably superior to that of the prior art, and the sensitivity of the cis-isomer is very low. Formula I

Inventors

MA ZHONGLI
YANG JINXIN
WANG DONGFANG
HANG DEYU

Assignees

北京云基科技股份有限公司

Dates

Publication Date: 20260508
Application Date: 20251103
Priority Date: 20241106

Claims (14)

1. A high sensitivity oxime ester compound has a structure shown in a formula I, I is a kind of Wherein, in the formula I, the symbol E represents that O-N bonds in the oxime group are distributed in trans and are positioned at the opposite side of the carbonyl; R 1 is selected from methyl, ethyl, isopropyl or sec-butyl; R 2 is selected from hydrogen or methyl; R 3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl.
2. The high sensitivity oxime ester compound according to claim 1, R 1 is selected from ethyl, isopropyl or sec-butyl; R 3 is selected from ethyl or cyclohexylmethyl.
3. The high sensitivity oxime ester compound according to claim 1 wherein the compound is selected from the group consisting of:
4. a method for producing the high sensitivity oxime ester compound according to any one of claims 1 to 3, comprising the steps of: Step (1), performing Friedel-crafts acylation reaction on a raw material M 1 and benzoyl chloride substituted by R 2 to obtain an intermediate M 2 ; raw material M 1 has the following structure: The R 2 substituted benzoyl chloride has the following structure: intermediate M 2 has the following structure: , Step (2), performing Friedel-crafts acylation reaction on the intermediate M 2 and an acyl chloride compound R 3 CH 2 COCl to obtain an intermediate M 3 ; The acyl chloride compound R 3 CH 2 COCl has the following structure: intermediate M 3 has the following structure: , Step (3), reacting the intermediate M 3 with nitrous acid ester or nitrous acid under an acidic condition to obtain a mixture of a trans isomer M 4 and a cis isomer M 4 , ; The trans isomer M 4 has the following structure: Cis isomer M 4 , has the following structure: , Step (4), purifying the product obtained in the step (3) to obtain a pure trans isomer M 4 ; Step (5), carrying out esterification reaction on a trans isomer M 4 and CH 3 COCl or (CH 3 CO) 2 O) to obtain a compound shown in a formula I; Wherein in M 4 and formula I, symbol E represents that O-N bond in oxime group is distributed as trans and is opposite to carbonyl, and Z in M 4 ' represents that O-N bond in oxime group is distributed as cis and is same as carbonyl; r 1 is selected from methyl, ethyl, isopropyl or sec-butyl, R 2 is selected from hydrogen or methyl, R 3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl.
5. The process according to claim 4, wherein in the step (1) and the step (2), the Friedel-crafts acylation is carried out in a chlorinated hydrocarbon solvent in the presence of a catalyst, Preferably, the molar ratio of the benzoyl chloride substituted by the raw material M 1 to the R 2 is 1 (1-1.1); and/or the molar ratio of the intermediate M 2 to the acyl chloride R 3 CH 2 COCl is 1 (1-1.1); Preferably, in the step (1) and the step (2), the temperature of the friedel-crafts acylation reaction is-15-25 ℃ independently; And/or in step (1) and step (2), the chlorinated hydrocarbon solvent is selected from 1, 2-dichloroethane, dichloromethane or o-dichlorobenzene; And/or, in step (1) and step (2), the catalyst comprises aluminum trichloride; And/or in step (1) and step (2), the molar ratio of the catalyst to R 2 substituted benzoyl chloride or acyl chloride R 3 CH 2 COCl is (0.5-2) 1, preferably 1:1, and/or the molar ratio of the raw material M 3 to nitrous acid ester or nitrous acid in step (3) is (1-1.5), preferably the nitrous acid ester is selected from isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite or propyl nitrite; And/or the reaction is carried out in an organic solvent, preferably selected from DMSO, an alcoholic solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent or a chlorinated alkane solvent, more preferably selected from methanol, ethanol, isopropanol, propanol and 2, 3-tetrafluoropropanol, the ether solvent is selected from diethyl ether, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, diisopropyl ether, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and polyethylene glycol dimethyl ether, the ester solvent is selected from ethyl acetate, butyl acetate, sec-butyl acetate, ethyl butyrate, ethylene glycol methyl ether acetate and propylene glycol methyl ether acetate, the aromatic hydrocarbon solvent is selected from benzene, toluene and chlorobenzene, the chlorinated alkane is selected from dichloromethane, 1, 2-dichloroethane, chlorobenzene and fluorobenzene, and/or the reaction temperature is 0-35 ℃; And/or, in the step (4), recrystallizing the mixture of the intermediates M 4 and M 4 , obtained in the step (3) in an organic solvent to obtain a high-purity intermediate M 4 ; And/or, in the step (4), separating and purifying the mixture of the intermediates M 4 and M 4 , obtained in the step (3) by using a silica gel column chromatography to obtain a high-purity intermediate M 4 ; And/or, in the step (5), the high purity intermediate M 4 obtained in the step (4) and CH 3 COCl or (CH 3 CO) 2 O) are in a molar ratio of 1 (1-1.5), wherein the esterification reaction is carried out in an aprotic solvent, preferably the aprotic solvent is selected from dichloromethane, ethyl acetate, toluene and methyl tertiary butyl ether; And/or when the reaction raw material is CH 3 COCl, an acid-binding agent is required to be added into the reaction system, preferably, the acid-binding agent is selected from pyridine and triethylamine, and more preferably, the molar ratio of the acid-binding agent to the CH 3 COCl is (1-1.2): 1; And/or the temperature of the esterification reaction is 20-60 ℃.
6. A photocurable composition comprising a photoinitiator and a free-radically polymerizable compound, wherein the photoinitiator comprises the high sensitivity oxime ester compound of any one of claims 1 to 3 or the high sensitivity oxime ester compound obtained by the production process of any one of claims 4 to 5; preferably, the free radically polymerizable compound is selected from the group consisting of acrylate compounds, methacrylate compounds, and combinations thereof; Preferably, the free radically polymerizable compound comprises one or more of alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylated epoxy resin, acrylated polyester resin, unsaturated polyester resin, acrylated polyether resin, acrylated polyurethane resin; More preferably, the free radically polymerizable compound comprises one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, silicone acrylate, diacrylate of vinyl acetate, diacrylate of styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1, 6-hexanediol, tri-hydroxy methane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, triallyl isocyanurate; And/or the mass ratio of the high sensitivity oxime ester compound in the photo-curing composition is 0.1-8.0%.
7. A photoresist, the preparation raw materials of which comprise a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and an organic solvent, wherein the photoinitiator comprises the high-sensitivity oxime ester compound as defined in any one of claims 1 to 3 or the high-sensitivity oxime ester compound obtained by the preparation method as defined in any one of claims 4 to 5; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with functionality of more than or equal to 3, more preferably dipentaerythritol hexaacrylate and/or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin with an acidic group, more preferably a polyacrylate or methacrylate with a carboxylic acid group, further preferably a copolymer of one or more of methacrylic acid, itaconic acid, and maleic acid with one or more of methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, for example, a methyl methacrylate and methacrylic acid copolymer, a benzyl methacrylate and methacrylic acid copolymer, a methyl methacrylate and butyl methacrylate, and a methacrylic acid and styrene copolymer; Preferably, the organic solvent is selected from one or more of an ester solvent, an aromatic hydrocarbon solvent and a halogenated hydrocarbon solvent, preferably one or more of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, toluene, xylene and tetrachloroethane; Optionally, the photoinitiator also comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) -1-butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) -1-butanone, 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone, 2,4, 6-trimethylbenzoyl benzene-diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide, 2-isopropyl thioxanthone, 2, 4-diethyl thioxanthone and bis (2, 6-difluoro-3-pyrrolyl) titanocene; Optionally, the photoresist is prepared from a raw material further containing pigment, preferably, the pigment is red pigment, green pigment, blue pigment or black pigment, more preferably, the red pigment comprises C.I. pigment red 177, the green pigment comprises C.I. pigment green 7, the blue pigment comprises C.I. pigment blue 15:6 and solvent blue 25, and the black pigment comprises carbon black, titanium black and C.I. pigment black 1; preferably, the photoresist is prepared from a raw material further comprising a heat stabilizer or a light stabilizer.
8. A black matrix prepared from a photoresist comprising the photoresist of claim 7, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.
9. A color filter device prepared from the photoresist comprising claim 7 or the black matrix of claim 8, wherein the pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.
10. A display obtained by photocuring a high sensitivity oxime ester compound according to any one of claims 1 to 3 or a high sensitivity oxime ester compound obtained by the production process according to any one of claims 4 to 5 as a photoinitiator, preferably comprising a PCB display, an LCD display and an OLED display.
11. Use of a high sensitivity oxime ester compound according to any one of claims 1 to 3, a high sensitivity oxime ester compound obtained by the production process according to any one of claims 4 to 5, a photocurable composition according to claim 6 or a photoresist according to claim 7 for producing colored or uncolored inks, paints, adhesives, filters, displays, pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder resists, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film resist materials, sealants, dental materials, optical films, optical fiber coatings, barrier films, polarizers, microlenses and recording materials.
12. An adhesive comprising the photocurable composition of claim 6, Preferably, the adhesive further comprises one or more of a polymer, a stabilizer, a surfactant, a leveling agent, a dispersant, Preferably, the weight average molecular weight of the polymer is 5000-100000.
13. A photo spacer comprising the photoresist of claim 7, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.
14. A printed article obtained by photocuring the high sensitivity oxime ester compound according to any one of claims 1 to 3 or the high sensitivity oxime ester compound obtained by the production method according to claim 4 or 5 as a photoinitiator; Preferably, the printed article comprises a printed circuit board, a color filter.

Description

High-sensitivity oxime ester compound and preparation method and application thereof Technical Field The invention relates to a high-sensitivity oxime ester compound, and a preparation method and application thereof. Background The photoinitiator is also called a photosensitizer or a photo-curing agent, and is a compound capable of absorbing energy with a certain wavelength in an ultraviolet light region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate polymerization, crosslinking and curing of monomers. The photo-initiator in the prior art has generally low photosensitivity and has great limitation on the type of applicable light source, and most of the photo-initiator is only applicable to ultraviolet excitation. The oxime ester compound is known to be suitable for preparing a photoresist composition as a photoinitiator, can show anti-oxidation polymerization resistance, has good sensitivity in a very thin coating film, is a photoinitiator product commonly used in the photoresist industry, but a person skilled in the art continuously searches for oxime ester compounds with higher sensitivity so as to improve the service performance of the photoresist. Disclosure of Invention In order to solve the technical problems, the invention provides a high-sensitivity oxime ester compound, a preparation method and application thereof, wherein the oxime ester group has a trans structure, and the exposure sensitivity of the oxime ester group is obviously higher than that of a corresponding cis-isomer compound. In a first aspect of the present invention, there is provided a high sensitivity oxime ester compound having a structure as shown in formula I, I is a kind of Wherein, in the formula I, the symbol E represents that O-N bonds in the oxime group are distributed in trans and are positioned at the opposite side of the carbonyl; R 1 is selected from methyl, ethyl, isopropyl or sec-butyl; R 2 is selected from hydrogen or methyl; R 3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl. According to some embodiments of the high sensitivity oxime ester compounds described herein, R 1 in formula I is selected from ethyl, isopropyl or sec-butyl. According to some embodiments of the high sensitivity oxime ester compounds described herein, R 3 in formula I is selected from ethyl or cyclohexylmethyl. According to some embodiments of the high sensitivity oxime ester compounds of the present invention, the compounds are selected from: In a second aspect of the present invention, there is provided a method for producing the high sensitivity oxime ester compound of the first aspect of the present invention, comprising the steps of: Step (1), performing Friedel-crafts acylation reaction on a raw material M 1 and benzoyl chloride substituted by R 2 to obtain an intermediate M 2; raw material M 1 has the following structure: The R 2 substituted benzoyl chloride has the following structure: intermediate M 2 has the following structure: , The friedel-crafts acylation of starting material M 1 with R 2 is shown below: Step (2), performing Friedel-crafts acylation reaction on the intermediate M 2 and an acyl chloride compound R 3CH2 COCl to obtain an intermediate M 3; The acyl chloride compound R 3CH2 COCl has the following structure: intermediate M 3 has the following structure: , The Friedel-crafts acylation of intermediate M 2 with the acid chloride compound R 3CH2 COCl is shown below: Step (3), reacting the intermediate M 3 with nitrous acid ester or nitrous acid under an acidic condition to obtain a mixture of a trans isomer M 4 and a cis isomer M 4,; The trans isomer M 4 has the following structure: Cis isomer M 4, has the following structure: , The reaction of intermediate M 3 with nitrous acid or nitrous acid is as follows: Step (4), purifying the product obtained in the step (3) to obtain a pure trans isomer M 4; Step (5), carrying out esterification reaction on a trans isomer M 4 and CH 3 COCl or (CH 3CO)2 O) to obtain a compound shown in a formula I; Wherein in M 4 and formula I, symbol E represents that O-N bond in oxime group is distributed as trans and is opposite to carbonyl, and Z in M 4' represents that O-N bond in oxime group is distributed as cis and is same as carbonyl; r 1 is selected from methyl, ethyl, isopropyl or sec-butyl, R 2 is selected from hydrogen or methyl, R 3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl. According to some embodiments of the preparation process of the present invention, R 1 is selected from ethyl, isopropyl or sec-butyl, and R 3 is selected from ethyl or cyclohexylmethyl. According to some embodiments of the preparation process of the present invention, in step (1) and step (2), the friedel-crafts acylation reaction is carried out in chlorinated hydrocarbon solvent in the presence of a catalyst. According to some embodime