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CN-121990975-A - Low-exhaust-gas high-sensitivity oxime ester compound and preparation method and application thereof

CN121990975ACN 121990975 ACN121990975 ACN 121990975ACN-121990975-A

Abstract

The invention provides a low-exhaust-gas-quantity high-sensitivity oxime ester compound as well as a preparation method and application thereof. The low-exhaust-gas-amount high-sensitivity oxime ester compound has a structure shown in a formula I, wherein a symbol E represents that O-N bonds in oxime groups are distributed in trans and are opposite to carbonyl groups, R 1 is selected from C1-C6 alkyl, R 1 'OCH 2 CH 2 ;R 1 ' is selected from C1-C4 alkyl, and R 2 is selected from C1-C7 alkyl and C5-C7 cycloalkyl substituted C1-C2 alkylene. The compounds of the present invention have significantly reduced outgassing in photo-curable composition formulations, particularly high sensitivity photoresist formulations, and have significantly better performance than the prior art. 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. 1. A low-exhaust-gas 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 C1-C6 alkyl or R 1 'OCH 2 CH 2 ;R 1 ' is selected from C1-C4 alkyl; R 2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl substituted C1-C2 alkylene.
  2. 2. The low-displacement, high-sensitivity oxime ester compound according to claim 1, R 1 is selected from methyl, ethyl, isopropyl, 2-methoxyethyl; r 2 is selected from C1-C3 alkyl, C5 or C6 cycloalkyl substituted methylene, C5 or C6 cycloalkyl substituted ethylene.
  3. 3. The low-displacement, high-sensitivity oxime ester compound according to claim 1 wherein said compound is selected from the group consisting of:
  4. 4. A method for producing a low-displacement, 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 2,4, 6-trimethylbenzoyl chloride to obtain an intermediate M 2 ; raw material M 1 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 2 CH 2 COCl to obtain an intermediate M 3 ; The acyl chloride compound R 2 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 C1-C6 alkyl, R 1 'OCH 2 CH 2 ;R 1 ' is selected from C1-C4 alkyl; R 2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl substituted C1-C2 alkylene.
  5. 5. The process according to claim 4, wherein in step (1) and 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 raw material M 1 to the 2,4, 6-trimethylbenzoyl chloride is 1 (1-1.1), And/or the molar ratio of the intermediate M 2 to the acyl chloride R 2 CH 2 COCl is 1 (1-1.1), And/or the chlorinated hydrocarbon solvent is selected from 1, 2-dichloroethane, dichloromethane or o-dichlorobenzene; And/or, the catalyst comprises aluminum trichloride; And/or the molar ratio of the catalyst to the 2,4, 6-trimethylbenzoyl chloride or acyl chloride R 2 CH 2 COCl is (0.5-2): 1; And/or the temperature of the Friedel-crafts acylation reaction is-15-25 ℃, preferably-10 ℃; And/or the molar ratio of the raw material M 3 to the nitrous acid ester or the nitrous acid in the step (3) is 1 (1-1.5); preferably, the nitrite is selected from the group consisting of isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite or propyl nitrite, the reaction is carried out in an organic solvent, preferably selected from the group consisting of DMSO, an alcoholic solvent, an ether solvent, an ester solvent, an aromatic solvent or a chlorinated alkane solvent, more preferably selected from the group consisting of methanol, ethanol, isopropanol, propanol and 2, 3-tetrafluoropropanol, an ether solvent selected from the group consisting of 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, an aromatic solvent selected from the group consisting of ethyl acetate, butyl acetate, sec-butyl acetate, ethyl butyrate, ethylene glycol methyl ether acetate and propylene glycol methyl ether acetate, and an aromatic solvent selected from the group consisting of benzene, toluene and chlorobenzene, and chlorinated alkanes selected from the group consisting of dichloromethane, 1, 2-dichloroethane and chlorobenzene, and/or a temperature of 0-35 DEG; 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. 6. A photocurable composition comprising a photoinitiator and a radically polymerizable compound, wherein the photoinitiator comprises the low-displacement, high-sensitivity oxime ester compound according to any one of claims 1 to 3 or the oxime ester compound obtained by the production process according to 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 low-exhaust-gas-amount high-sensitivity oxime ester compound in the photo-curing composition is 0.1-8.0%.
  7. 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 low-exhaust-gas-amount high-sensitivity oxime ester compound as claimed in any one of claims 1 to 3 or the oxime ester compound obtained by the preparation method as claimed 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. 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. 9. A color filter device prepared from the photoresist comprising the photoresist of claim 7, wherein the pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.
  10. 10. A display obtained by photocuring the low-displacement high-sensitivity oxime ester compound according to any one of claims 1 to 3 or the oxime ester compound obtained by the production method 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. 11. Use of a low-displacement, high-sensitivity oxime ester compound according to any one of claims 1 to 3, oxime ester compound obtained by the production process according to any one of claims 4 to 5, photocurable composition according to claim 6 or 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 resist inks, 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. 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. 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. 14. A printed article comprising the low-displacement high-sensitivity oxime ester compound according to any one of claims 1 to 3 or the low-displacement high-sensitivity oxime ester compound obtained by the production process according to any one of claims 4 to 5 as a photoinitiator, which is photocured; preferably, the printed article comprises a printed circuit board, a color filter.

Description

Low-exhaust-gas high-sensitivity oxime ester compound and preparation method and application thereof Technical Field The invention relates to a low-exhaust-gas-amount high-sensitivity oxime ester compound as well as a preparation method and application thereof. Background The carbazole oxime ester compounds are known to have higher sensitivity and are photoinitiator products commonly used in the photoresist industry, but based on the photodecomposition process of oxime ester compounds, the bisoxime ester compounds with high sensitivity also have higher carbon dioxide gas yield and are main components of photoresist photodecomposition exhaust gas quantity, the higher exhaust gas quantity is one of factors affecting the photoresist using effect, and the technical personnel in the industry require that the used photoinitiator not only has high sensitivity, but also has lower exhaust gas quantity so as to reduce adverse effects of gas emission on the photoresist using effect such as film retention quality. Disclosure of Invention In order to solve the technical problems, the invention provides a low-exhaust-gas-quantity high-sensitivity oxime ester compound as well as a preparation method and application thereof. In a first aspect of the present invention, there is provided a low-displacement, 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 C1-C6 alkyl or R 1'OCH2CH2;R1' is selected from C1-C4 alkyl; R 2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl substituted C1-C2 alkylene. According to some embodiments of the low-displacement, high-sensitivity oxime ester compounds described herein, R 1 is selected from methyl, ethyl, isopropyl, 2-methoxyethyl, R 2 is selected from C1-C3 alkyl, C5 or C6 cycloalkyl-substituted methylene, C5 or C6 cycloalkyl-substituted ethylene. According to some embodiments of the low-displacement, high-sensitivity oxime ester compound of the present invention, the compound is selected from the group consisting of: in a second aspect of the present invention, there is provided a method for producing a high-sensitivity oxime ester compound having a low displacement, comprising the steps of: Step (1), performing Friedel-crafts acylation reaction on a raw material M 1 and 2,4, 6-trimethylbenzoyl chloride to obtain an intermediate M 2; raw material M 1 has the following structure: Intermediate M 2 has the following structure: ; The reaction of starting material M 1 with 2,4, 6-trimethylbenzoyl chloride is as follows: Step (2), performing Friedel-crafts acylation reaction on the intermediate M 2 and an acyl chloride compound R 2CH2 COCl to obtain an intermediate M 3; The acyl chloride compound R 2CH2 COCl has the following structure: Intermediate M 3 has the following structure: ; The reaction of intermediate M 2 with the acid chloride compound R 2CH2 COCl is as follows: 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 C1-C6 alkyl, R 1'OCH2CH2;R1' is selected from C1-C4 alkyl; R 2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl substituted C1-C2 alkylene. According to some embodiments of the preparation method of the present invention, R 1 is selected from methyl, ethyl, isopropyl, 2-methoxyethyl. According to some embodiments of the preparation methods of the present invention, R 2 is selected from the group consisting of C1-C3 alkyl, C5 or C6 cycloalkyl-substituted methylene, C5 or C6 cycloalkyl-substituted ethylene. 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 embodiments of the preparation process of the present invention, the molar ratio of starting material M 1 to 2,4, 6-trimethylbenzoyl chloride is 1 (1-1.1), for example 1:1, 1:1.02, 1:1.04, 1:1.05, 1:1.07, 1:1.1 or any value in between. According to some embodiments of the preparation process of the present invention, the molar ratio of