Trans-oxime ester compound and preparation method and application thereof

Abstract

The application provides a trans-oxime ester compound and a preparation method and application thereof. The trans-oxime ester compound has a structure as shown in formula I: wherein, in the formula I, a symbol E represents that the O-N bond in the oxime group is in a trans form, R1 is selected from H, C1-C6 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and phenyl; and R2 is selected from methyl and phenyl. The compound has a significantly high sensitivity performance in a photo-curing composition formula, especially a photoresist, and the performance is significantly better than that of a cis-isomer thereof.

Description

Technical Field

[0001] This invention relates to a trans-oxime ester compound, its preparation method, and its application. Background Technology

[0002] Since its emergence in the 1970s, photocuring technology has been widely used, for example in the fields of coatings, printing inks, and electronic device manufacturing. One of the most important concerns for photocuring engineers is curing efficiency or sensitivity, and the key factor affecting curing efficiency is the structure of the photoinitiator.

[0003] Oxime ester compounds are excellent photoinitiators for preparing negative photoresists, such as BASF's OXE01. However, cis-trans isomers exist within the oxime ester group. Example 26 in document CN1241562A describes the trans (E) and cis (Z) ratios of the intermediate oxime and the oxime ester product, but does not provide data or explanations regarding the performance differences between the two isomers. Other documents also describe the preparation of mixtures of the two isomers; for example, page 23 of the specification in CN100528838C states that "mixtures of isomers can be used as photoinitiators." Furthermore, many other documents, such as CN101565472B, do not specify which isomer of the oxime ester compound it contains. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a trans-oxime ester compound, its preparation method, and its application.

[0005] In a first aspect, the present invention provides a trans-oxime ester compound having a structure as shown in Formula I.

[0006]

[0007] In Equation I, the symbol (E) indicates that the ON bond distribution in the oxime group is in the trans form;

[0008] R1 is selected from: H, C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, tert-hexyl, etc.), cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl;

[0009] R2 is selected from methyl or phenyl.

[0010] In some embodiments, the symbol (E) indicates that the ON bond distribution in the oxime group is trans, i.e., on the different side of the C=N double bond from that of the carbonyl group.

[0011] The inventors unexpectedly discovered that the trans isomer of the compound shown in Formula I (taking the compound shown in Formula I-1 as an example) is significantly different from its cis isomer (taking the compound shown in Formula II-1 as an example) not only in terms of physical properties, but also in terms of extremely significant differences when used as a photoinitiator in negative photoresist formulation testing, that is, the sensitivity of the trans isomer is much higher than that of the cis isomer.

[0012]

[0013] In some embodiments, the trans-oxime ester compound has any of the following structures:

[0014]

[0015] A second aspect of the present invention provides a method for preparing a trans-oxime ester compound, comprising the following steps:

[0016] Step (1): The raw material M1 is subjected to Friedel-Crafts acylation reaction with R1CH2CH2COCl to obtain intermediate M2; wherein R1 is selected from: H, C1-C6 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl;

[0017]

[0018] Step (2): The intermediate M2 obtained in step (1) is reacted with nitrite or nitrous acid under acidic conditions to obtain the trans isomer M3 and the cis isomer M3. ， The mixture was purified to obtain the pure trans isomer M3.

[0019]

[0020] Wherein, the symbol E indicates that the ON bond distribution in the oxime group is trans, and Z indicates that the ON bond distribution in the oxime group is cis;

[0021] Step (3): The trans isomer M3 is esterified with R2COCl or (R2CO)2O to obtain the compound of formula I, where R2 is selected from methyl, phenyl, preferably methyl.

[0022]

[0023] According to some embodiments of the preparation method of the present invention, in step (1), the catalyst for the Friedel-Crafts acylation reaction of the raw material M1 with R1CH2CH2COCl is anhydrous aluminum trichloride.

[0024] According to some embodiments of the preparation method described in this invention, the solvent for the Friedel-Crafts acylation reaction in step (1) is selected from 1,2-dichloroethane or dichloromethane.

[0025] According to some embodiments of the preparation method described in this invention, the temperature of the Friedel-Crafts acylation reaction in step (1) is -20°C to 30°C; for example, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C.

[0026] According to some embodiments of the preparation method of the present invention, in step (1), the molar ratio of raw material M1 to R1CH2CH2COCl is 1:(1-1.2), for example 1:1, 1:1.05, 1:1.1, 1:1.2 or any value between them.

[0027] According to some embodiments of the preparation method of the present invention, in step (2), the molar ratio of intermediate M2 to nitrite or nitrite is 1:(1-1.5); for example, 1:1, 1:1.05, 1:1.1, 1:1.2, 1:1.3, 1:1.5, etc., or any value within the above range.

[0028] According to some embodiments of the preparation method of the present invention, the nitrite is selected from one or more of isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite, or propyl nitrite.

[0029] According to some embodiments of the preparation method of the present invention, in step (2), the reaction is carried out in an organic solvent.

[0030] According to some embodiments of the preparation method of the present invention, the organic solvent is selected from one or more of DMSO, alcohols, ethers, esters, aromatic hydrocarbons or chlorinated alkane solvents.

[0031] According to some embodiments of the preparation method of the present invention, the alcohol solvent is selected from one or more of methanol, ethanol, isopropanol, propanol and 2,2,3,3-tetrafluoropropanol.

[0032] According to some embodiments of the preparation method of the present invention, the ether solvent is selected from one or more 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.

[0033] According to some embodiments of the preparation method of the present invention, the ester solvent is selected from one or more of ethyl acetate, butyl acetate, sec-butyl acetate, and ethyl butyrate.

[0034] According to some embodiments of the preparation method of the present invention, the aromatic solvent is selected from one or more of benzene, toluene, and chlorobenzene.

[0035] According to some embodiments of the preparation method described in this invention, the chloroalkane is selected from one or more of dichloromethane and 1,2-dichloroethane.

[0036] According to some embodiments of the preparation method of the present invention, the acidic conditions in step (2) are derived from hydrochloric acid gas or concentrated hydrochloric acid.

[0037] According to some embodiments of the preparation method of the present invention, the reaction temperature is 5-25°C; for example, 5°C, 10°C, 20°C, 25°C, etc., or any value within the above range.

[0038] According to some embodiments of the preparation method described in this invention, the purification operation involves obtaining the trans isomer M3 by column chromatography or recrystallization, achieving an HPLC purity of over 99%, and the cis isomer M3. ， Content less than 1%.

[0039] According to some embodiments of the preparation method of the present invention, in step (3), the molar ratio of the trans isomer M3 to CH3COCl or (CH3CO)2O is 1:(1-1.5); for example, 1:1, 1:1.1, 1:1.15, 1:1.2, 1:1.25, 1:1.5 or any value between them.

[0040] According to some embodiments of the preparation method described in this invention, the esterification reaction is carried out in an aprotic solvent.

[0041] According to some embodiments of the preparation method of the present invention, the aprotic solvent is selected from one or more of dichloromethane, ethyl acetate, toluene, methyl tert-butyl ether, and dimethyl carbonate.

[0042] According to some embodiments of the preparation method described in this invention, when the reaction raw material is CH3COCl, an acid-binding agent needs to be added to the reaction system.

[0043] According to some embodiments of the preparation method described in this invention, the acid-binding agent is selected from pyridine, triethylamine, 1-methylimidazole, etc.

[0044] According to some embodiments of the preparation method of the present invention, the molar ratio of the acid-binding agent to the CH3COCl is (1-1.2):1; for example, 1:1, 1.1:1, 1.2:1, etc., or any value within the above range.

[0045] According to some embodiments of the preparation method of the present invention, the temperature of the esterification reaction is 20-60°C; for example, 20°C, 30°C, 35°C, 40°C, 50°C, 60°C, etc., or any value within the above range.

[0046] A third aspect of the present invention provides a photocurable composition comprising a photoinitiator and a free radical polymerizable compound, wherein the photoinitiator comprises the trans-oxime ester compound described in the first aspect of the present invention or the trans-oxime ester compound prepared by the method of the second aspect of the present invention.

[0047] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0048] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound includes one or more of alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, acrylic epoxy resins, acrylic polyester resins, unsaturated polyester resins, acrylic polyether resins, and acrylic polyurethane resins.

[0049] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound includes one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, vinyl acetate, styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate.

[0050] According to some embodiments of the photocurable composition of the present invention, the trans-oxime ester compound is present in the photocurable composition at a mass percentage of 0.1-5.0%, for example 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or any value therebetween.

[0051] According to some embodiments of the photocurable composition of the present invention, the photocurable composition of the present invention may also include other photoinitiators or co-initiators. The present invention does not specifically limit the specific types of the other initiators or co-initiators, and any photoinitiator or co-initiator that is helpful to the photocuring performance can be selected.

[0052] This invention also provides an adhesive that, in addition to containing the photocurable composition described in the third aspect of this invention, may also contain other necessary components, such as polymers with a molecular weight of 5,000-100,000, to improve adhesive properties, for bonding glass, plastics, metal components, etc., according to the performance requirements of the adhesive. Furthermore, those skilled in the art can easily identify products that require the addition of other necessary components, such as stabilizers, surfactants, leveling agents, and dispersants, based on existing technology and the intended use of the photocurable composition.

[0053] In a fourth aspect, the present invention provides a photoresist, wherein the raw materials for preparing the photoresist include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, and an organic solvent, wherein the photoinitiator includes the trans-oxime ester compound described in the first aspect of the present invention or the trans-oxime ester compound obtained by the preparation method described in the second aspect of the present invention.

[0054] According to some embodiments of the photoresist of the present invention, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality ≥3. The present invention does not specifically limit the type of the multifunctional acrylate monomer, and those skilled in the art can select from conventional multifunctional acrylate monomers.

[0055] According to some embodiments of the photoresist of the present invention, the multifunctional acrylate monomer includes dipentaerythritol hexaacrylate and / or pentaerythritol acrylate.

[0056] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin is a resin having acidic groups, which can be dissolved or dispersed when exposed to an alkaline solution. The present invention does not specifically limit the type of alkali-soluble resin, and those skilled in the art can select from conventional alkali-soluble resins.

[0057] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin includes polyacrylate or methacrylate having carboxylic acid groups.

[0058] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin includes one or more of methacrylic acid, itaconic acid, and maleic acid, and one or more of methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymer.

[0059] According to some embodiments of the photoresist of the present invention, the organic solvent is selected from one or more of ester solvents, aromatic solvents, and haloalkane solvents.

[0060] According to some embodiments of the photoresist of the present invention, the organic solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, toluene, xylene, and tetrachloroethane.

[0061] According to some embodiments of the photoresist of the present invention, the photoinitiator further includes one or more of the following: 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-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthonone, 2,4-diethylthioxanthonone, and bis(2,6-difluoro-3-pyrrolephenyl)dicenoctanetane.

[0062] According to some embodiments of the photoresist of the present invention, the photoinitiator further includes commercially available oxime ester photoinitiators, such as OXE01, OXE02, OXE03, OXE04, NCI1919, NCI831, or compounds with the same molecular structure.

[0063] According to some embodiments of the photoresist of the present invention, the raw materials for preparing the photoresist further contain pigments.

[0064] According to some embodiments of the photoresist of the present invention, the pigment is a red pigment, a green pigment, a blue pigment, or a black pigment.

[0065] According to some embodiments of the photoresist of the present invention, the red pigment includes CI Pigment Red 177, the green pigment includes CI Pigment Green 7, the blue pigment includes CI Pigment Blue 15:6 and Solvent Blue 25, and the black pigment includes carbon black, titanium black and CI Pigment Black 1.

[0066] According to some embodiments of the photoresist of the present invention, the raw materials for preparing the photoresist further include heat stabilizers or light stabilizers, such as p-methoxyphenol. Other resins may also be added, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, linear phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.

[0067] Using the photoresist of this invention as raw material, and through existing technology processes such as multiple coatings, exposures, and developments of different colored photoresists, a color filter device with excellent optical performance can be obtained. This device is an important component of a color display screen, in which the color units exhibit pure color and high light transmittance, while the colorless parts exhibit low yellowing and high light transmittance.

[0068] Photoresist is typically applied using a spin-coating method to evenly distribute it onto a substrate. After drying at 80-90°C, volatile components such as solvents are separated, leaving a solid film. A mask is placed on top of this film, and the substrate is exposed to appropriate exposure levels under a 365nm mercury lamp or LED light source. The exposed material is then developed in an alkaline solution such as sodium carbonate or sodium hydroxide to remove unexposed portions, leaving the exposed image. Following this, a cleaning and post-baking process at 200-230°C further ensures better adhesion of the image to the substrate. By following the designed procedure and fabricating different colors and patterns, or combining this with necessary protective film processing, a photofilter device is obtained.

[0069] In a fifth aspect, the present invention provides a black matrix prepared from a photoresist comprising the photoresist described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0070] The present invention also provides an optical spacer, which is prepared from a photoresist including the one described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0071] In a sixth aspect, the present invention provides a color filter device prepared from a photoresist comprising the photoresist described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.

[0072] In a seventh aspect, the present invention provides a display obtained by photocuring a trans-oxime ester compound as a photoinitiator, which is obtained by photocuring a trans-oxime ester compound as described in the first aspect of the present invention or a trans-oxime ester compound prepared by the method of the second aspect of the present invention.

[0073] According to some embodiments of the display described in this invention, the display includes a PCB display, an LCD display, and an OLED display.

[0074] The eighth aspect of the present invention provides the application of the trans-oxime ester compound described in the first aspect of the present invention, the trans-oxime ester compound obtained by the preparation method of the second aspect of the present invention, the photocurable composition described in the third aspect of the present invention, or the photoresist described in the fourth aspect of the present invention in the preparation of colored or uncolored inks, coatings, adhesives, filters, displays, pattern printing, printing plates, 3D printing, PCB photoresist, PCB solder resist ink, substrate protective coating, electronic device protective coating, passivation film, liquid or dry film resist material, sealant, dental material, optical material, optical film, optical fiber coating, insulating film, polarizer, microscope lens, and recording material.

[0075] Using the compound of Formula I of this invention or a photoinitiator composition containing Formula I and a photoresist containing Formula I as raw materials, color filters, LCD color displays, OLED color displays, PCBs, and printed materials can be obtained through necessary processing steps.

[0076] The ninth aspect of the present invention also provides a printed article obtained by photocuring a trans-oxime ester compound as a photoinitiator, which is obtained by photocuring a trans-oxime ester compound as described in the first aspect of the present invention or a trans-oxime ester compound prepared by the preparation method of the second aspect of the present invention.

[0077] According to some embodiments of the printed article of the present invention, the printed article includes a printed circuit board and a color filter.

[0078] The beneficial effects of the present invention include: the trans-oxime ester compound of the present invention has significantly different photosensitive properties from its cis isomer, and exhibits significantly higher sensitivity in photocurable composition formulations, especially in photoresists. Detailed Implementation

[0079] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and techniques have also been described in many publications.

[0080] Experimental materials and equipment:

[0081] Light source equipment:

[0082] 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.

[0083] Test equipment:

[0084] Differential scanning calorimeter: HSC-1, Beijing Hengjiu Experimental Equipment Co., Ltd.;

[0085] Stereo microscope: HY-950S, Beijing Huanyu Technology Co., Ltd., linewidth unit is μm;

[0086] Yellowness meter: SC-80C fully automatic colorimeter, Beijing Jingyi Kangguang Optical Instrument Co., Ltd.

[0087] Experimental materials:

[0088] Genomer 4212: Aliphatic polyurethane acrylate, a product of RAHN Corporation;

[0089] DPHA: Dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0090] HDDA: 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0091] Comparative compounds:

[0092]

[0093] Compound preparation

[0094] Preparation of Compound I-1 (Example 1)

[0095]

[0096] Step 1a. In a 250 mL three-necked flask, add 10 g (0.054 mol) of diphenyl sulfide and 100 g of dichloromethane (hereinafter referred to as DCM), cool to -10 °C, add 7.52 g (0.056 mol) of anhydrous aluminum trichloride, stir, and add 9.78 g (0.056 mol) of 3-cyclohexylpropionyl chloride dropwise over 30 min. Then stir the reaction at 0 °C for 4 h. The reaction solution is acid-hydrolyzed and washed with water until neutral, and DCM is removed by rotary evaporation to obtain 17.2 g of colorless liquid as intermediate I-1A; yield 98.1%, HPLC purity 99.10%;

[0097]

[0098] Step 1b. Add 10.2 g (31.4 mmol) of intermediate I-1A obtained in step 1a and 100 mL of toluene to a 250 mL three-necked flask, cool to 5-10 °C, add 3.56 g (34.4 mmol) of butyl nitrite dropwise, stir and keep warm at 5-10 °C, then continuously introduce small amounts of HCl gas and react for 5 h. The reaction solution was added to 100 mL of 5% sodium carbonate aqueous solution and stirred for 30 min. The lower aqueous phase was separated, and the upper organic phase was washed once with 30 mL of water. The organic phase was dried with 2 g of Na2SO4 for 4 h, filtered to remove the desiccant, and the filtrate was rotary evaporated to dryness. The residue weighed 10.1 g of yellow solid crude product. HPLC analysis showed that it contained 8.2% minor isomers and 83.5% major isomers. The product was recrystallized twice with ethanol as solvent to obtain 7.20 g of white crystals. The HPLC content was 99.48% major isomers and 0.041% minor isomers, with a yield of 65% and a DSC melting point of 119.6 °C. The mother liquor contained minor isomers, which were extracted by column chromatography. 1 H-NMR data confirm that it is the compound shown in formula I-1B; 1 H-NMR data (CDCl3, δ[ppm])0.9744-1.2409(m,5H,Cy-CH2), 1.5943-1.72777(m,6H,Cy-CH2+CH), 2.6578-2.6751(d,2H,1CH2), 7.1774 -7.1989(d,2H,2ArH), 7.3723-7.4228(m,3H,3ArH), 7.4778-7.5115(m,2H,2ArH), 7.7917-7.8130(d,2H,2ArH), 7.9332(broad peak, 1H,OH).

[0099]

[0100] Step 1c: In a 100 mL single-necked flask, add 3.54 g (10 mmol) of intermediate I-1B obtained in step 1b, add 15 mL of DCM, and then add 1.17 g (11.5 mmol) of acetic anhydride. Heat the mixture in an oil bath to 40 °C and stir magnetically for 6 h. Wash three times with pure water, 10 mL each time, until pH = 6-7. Evaporate the DCM under reduced pressure to dryness. Recrystallize the residue with an acetone-n-heptane mixed solvent, precipitating white crystals. Filter and dry to obtain 3.39 g of white powder, yield 85.7%; HPLC purity 99.88%, DSC melting point 59.3 °C.

[0101] 1 H-NMR data confirm that it is the compound shown in Formula I-1; 1H-NMR data (CDCl3, δ[ppm])0.9674-1.2240(m,5H,Cy-CH2), 1.5709-1.6799(m,6H,Cy-CH2+CH), 2.2416(s,3H,COCH3), 2.7186-2.7357( d,2H,1CH2), 7.1709-7.1924(d,2H,2ArH), 7.3964-7.4203(m,3H,3ArH), 7.5147-7.5385(m,2H,2ArH), 7.9544-7.9759(d,2H,2ArH).

[0102] Preparation Example 2: Preparation of Compound II

[0103]

[0104] Step 2a. The mother liquor obtained from step 1b of Preparation Example 1 contained 31.74% minor isomers. It was separated and extracted by column chromatography. The eluent composition was ethyl acetate-heptane (volume ratio 6:100). The minor isomers were obtained. After evaporating the solvent, the liquid was viscous and weighed 0.40 g, with a yield of 3.6%. HPLC content: minor isomers 98.02%. 1 H-NMR data confirm that the minor isomer is the compound shown in formula II-1B; 1 H-NMR data (CDCl3, δ [ppm]): 0.8641-1.2098 (m, 5H, Cy-CH2), 1.5152-1.5613-1. 6074(m,1H,OH),1.5795-1.6878(m,4H,Cy-CH2+CH),1.7684-1.7989(d,2H,Cy -CH2), 2.6706-2.6881(d,2H,1CH2), 7.1925-7.2139(d,2H,2ArH), 7.4068-7. 4431(m,3H,3ArH), 7.5104-7.5557(m,2H,2ArH), 7.7288-7.7501(d,2H,2ArH).

[0105]

[0106] Step 2b. Following step 1c of Preparation Example 1, add 0.30 g (0.85 mmol) of intermediate II-1B obtained in step 2a to a 50 mL single-necked flask, add 5 mL of DCM, and then add 0.095 g (1 mmol) of acetic anhydride. Heat the mixture in an oil bath to 35-40 °C and stir magnetically for 6 h. Wash three times with pure water, 5 mL each time, until pH = 6-7. Evaporate the DCM under reduced pressure, and after esterification, wash with water to remove the DCM. The solvent is then removed under vacuum to obtain 0.33 g of a light yellow oily product, with a yield of 98.2% and an HPLC purity of 98.01%. 1 H-NMR data confirm that it is the compound shown in Formula II-1; 1 H-NMR data (CDCl3, δ[ppm]): 0.9371-1.2547(m,5H,Cy-CH2), 1.5941-1.7050(m,4H,Cy-CH2+CH), 1.7684-1.7989(d,2H,Cy-CH2), 1.9123(s,3H,COCH3), 2.4333-2.4510(d,2H,1CH2), 7.1800-7.2012(d,2H,2ArH), 7.4429-7.467 8(m,3H,3ArH), 7.5277-7.5623(m,2H,2ArH), 7.6645-7.6857(d,2H,2ArH).

[0107] Preparation of alkali-soluble resins

[0108] 20g of benzyl methacrylate, 3g of methacrylic acid, 7g of hydroxyethyl methacrylate, 1.4g of azobisisobutyronitrile, and 0.4g of dodecanethiol were dissolved in 200mL of toluene and placed in a constant-pressure dropping funnel. 100mL of toluene was added to a 500mL four-necked flask, purged with nitrogen, and the temperature was raised to 80℃. The solution from the funnel was added dropwise, and after reacting for 6 hours, the mixture was cooled and filtered to obtain 24g of a white, alkali-soluble resin.

[0109] Preparation of black pigment

[0110] Take 50g of the alkali-soluble resin prepared by the above method, 50g of Mitsubishi PK7 carbon black, 100g of DPHA, and 250g of propylene glycol methyl ether acetate and put them into a 500mL beaker. Mix them for 15 minutes at 5000r / min using a high-speed shear mixer to obtain a black color paste.

[0111] Preparation of red pigment

[0112] Take 50g of the alkali-soluble resin prepared by the above method, 50g of DIC Corporation PR122 pink pigment, 100g of DPHA, and 250g of propylene glycol methyl ether acetate and put them into a 500mL beaker. Mix them for 15min at 5000r / min using a high-speed shear mixer to obtain a red pigment paste.

[0113] Examples and Comparative Examples of Photoresist Compositions

[0114] Compounds of Formula I-1 and Formula II-1 were used as photoinitiators and dissolved in PMA according to the proportions in Table 1. They were then mixed with black pigment according to the proportions in Table 1. The amount is measured in grams.

[0115] After thoroughly mixing all components, a film was coated onto a glass slide using a 10μm wire rod. The film was then dried in a 90℃ oven for 5 minutes. Using a 365nm surface light source and a 41-level exposure scale as a mask, development was performed using a 0.0425% KOH aqueous solution at 25℃. The film was then rinsed with purified water for 10 seconds and dried in a 90℃ oven for 30 minutes. The film retention level was observed and recorded. A higher film retention level after curing indicates higher formulation sensitivity and better photoinitiator sensitivity.

[0116] The formulation mixtures of the examples and comparative examples in Table 1 were coated, cured, developed, and measured, and the film retention levels were recorded.

[0117] Table 1

[0118]

[0119] As can be seen from the film retention order data in Table 1, the compound provided by this invention, under the same dosage conditions, exhibits a significantly higher film retention order after curing in a black system compared to the comparative compound. It was found that the sensitivity of the trans-oxime ester compound (Formula I-1) is significantly higher than that of the cis-oxime ester compound (Formula II-1).

[0120] Compounds of Formula I-1 and Formula II-1 were used as photoinitiators and dissolved in propylene glycol methyl ether acetate (PMA) according to the amounts in Table 2. They were then mixed with red pigment in the proportions in Table 2. The amounts are in grams.

[0121] After mixing all components evenly, a film was coated on a glass slide using a 10μm wire rod, dried in a 90℃ oven for 5 min, cured with a 365nm surface light source using a 41-level exposure ruler, developed with 0.0425% KOH solution at 25℃, rinsed with pure water for 10 s, dried in a 90℃ oven for 30 min, and the film retention level was observed and recorded in Table 2.

[0122] Table 2

[0123]

[0124] As can be seen from the film retention order data in Table 2, the film retention order of the compound of formula I-1 provided by this invention is significantly higher than that of the comparative compound of formula II-1 after curing in the red formulation system under the same dosage conditions; it was found that the sensitivity of the trans-oxime ester compound is significantly higher than that of the cis-oxime ester compound of formula II-1.

[0125] In summary, whether in black photoresist formulations or in color photoresist formulations such as red photoresist formulations, the sensitivity of Formula I, which is a trans-oxime ester compound, is significantly higher than the sensitivity of Formula II, which is a cis-oxime ester compound.

[0126] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A trans-oxime ester compound having the structure shown in Formula I, in, In Equation I, the symbol E indicates that the ON bond distribution in the oxime group is in the trans form; R1 is selected from: H, C1-C6 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl; R2 is selected from methyl or phenyl.

2. The trans-oxime ester compound according to claim 1, characterized in that, The trans-oxime ester compound has any of the following structures:

3. A method for preparing the trans-oxime ester compound according to claim 1 or 2, comprising the following steps: Step (1): The raw material M1 is subjected to a Friedel-Crafts acylation reaction with R1CH2CH2COCl to obtain intermediate M2; R1 is selected from: H, C1-C6 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl; Step (2): The intermediate M2 obtained in step (1) is reacted with nitrite or nitrous acid under acidic conditions to obtain the trans isomer M3 and the cis isomer M3. ， The mixture was purified to obtain the pure trans isomer M3. Wherein, the symbol E indicates that the ON bond distribution in the oxime group is trans, and Z indicates that the ON bond distribution in the oxime group is cis; Step (3): The trans isomer M3 is esterified with R2COCl or (R2CO)2O to obtain the compound of formula I, wherein R2 is selected from methyl, phenyl, preferably methyl; Preferably, in step (1), the catalyst for the Friedel-Crafts acylation reaction of the raw material M1 with R1CH2CH2COCl is anhydrous aluminum trichloride; And / or, the acidic conditions in step (2) are derived from hydrochloric acid gas or concentrated hydrochloric acid.

4. A photocurable composition comprising a photoinitiator and a free radical polymerizable compound, wherein the photoinitiator comprises at least the trans-oxime ester compound of claim 1 or 2 or the trans-oxime ester compound obtained by the preparation method of claim 3; Preferably, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof; Preferably, the free radical polymerizable compound includes one or more of the following: alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylic epoxy resin, acrylic polyester resin, unsaturated polyester resin, acrylic polyether resin, and acrylic polyurethane resin. More preferably, the free radical polymerizable compound includes one or more of the following: methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, vinyl acetate, styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate. And / or, the trans-oxime ester compound accounts for 0.1-5.0% by mass in the photocurable composition.

5. A photoresist, wherein the raw materials for preparing the photoresist include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, and an organic solvent, wherein, The photoinitiator includes the trans-oxime ester compound of claim 1 or 2 or the trans-oxime ester compound obtained by the preparation method of claim 3; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality of ≥3, more preferably dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin having acidic groups, more preferably a polyacrylate or methacrylate having carboxylic acid groups, and even more preferably a copolymer formed by one or more of methacrylic acid, itaconic acid, and maleic acid with methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as methyl methacrylate and methacrylate copolymer, benzyl methacrylate and methacrylate copolymer, methyl methacrylate and butyl methacrylate, and methacrylate and styrene copolymer; Preferably, the organic solvent is selected from one or more of ester solvents, aromatic solvents and haloalkane solvents, and more preferably from one or more of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, toluene, xylene and tetrachloroethane.

6. The photoresist according to claim 5, characterized in that, The photoresist further contains pigments, i.e., colored or black photoresist, wherein the pigments are red pigments, green pigments, blue pigments or black pigments; more preferably, the red pigments include CI pigment red 177, the green pigments include CI pigment green 7, the blue pigments include CI pigment blue 15:6 and solvent blue 25, and the black pigments include carbon black, titanium black and CI pigment black 1.

7. A black matrix prepared from the photoresist of claim 6, wherein, The pigment in the photoresist is a black pigment, preferably carbon black or titanium black.

8. A color filter device, which is prepared from the photoresist according to claim 6, wherein, The pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.

9. A display obtained by photocuring a trans-oxime ester compound as a photoinitiator, as described in claim 1 or 2, or a trans-oxime ester compound obtained by the preparation method described in claim 3; preferably, the display includes a PCB display, an LCD display, and an OLED display.

10. The use of the trans-oxime ester compound of claim 1 or 2, the trans-oxime ester compound obtained by the preparation method of claim 3, the photocurable composition of claim 4, or the photoresist of claim 5 or 6 in the preparation of colored or uncolored inks, coatings, adhesives, filters, displays, pattern printing, printing plates, 3D printing, PCB photoresist, PCB solder resist ink, substrate protective coating, electronic device protective coating, passivation film, liquid or dry film resist material, sealant, dental material, optical material, optical film, fiber optic coating, insulating film, polarizer, microscope lens, and recording material.

11. A printed article, comprising a trans-oxime ester compound as described in claim 1 or 2 or a trans-oxime ester compound obtained by the preparation method described in claim 3, as a photoinitiator and then photocured; Preferably, the printed article includes a printed circuit board and / or a color filter.

Images