Silicon oxime ester-containing photoinitiator as well as preparation method and application thereof

Abstract

The invention provides a photoinitiator containing silicon oxime ester. The silicon oxime ester-containing photoinitiator has a chemical structure as shown in a formula (I), and in the formula (I), R1 is selected from C1-C8 alkylene; a, B and C are respectively and independently selected from C1-C8 alkyl groups or C6-C10 aryl groups; r2 is selected from hydrogen or alkyl of C1-C8; r3 is selected from C1-C8 alkyl groups and is cut off by 1-3 oxygen atoms; and R4 is selected from alkyl groups of C1-C8 or aryl groups of C6-C10. The silicon-containing oxime ester initiator with the structure has the characteristic of high sensitivity, and the solubility of the silicon-containing oxime ester initiator in the application process can be greatly improved by introducing the R3 group, so that the resistance of the silicon-containing oxime ester initiator in the application process is improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of photocuring, and in particular to a silicon-containing oxime ester photoinitiator, a preparation method thereof and application thereof. Background Art

[0002] Oxime ester compounds, as effective type I photoinitiators, have long been used in free radical photopolymerization due to their superior photoreactivity. After the N-O bond of oxime esters is broken, the acyloxy group may undergo decarboxylation to produce carbon dioxide, which solves the problem of inhibition of the photopolymerization process caused by oxygen in the air. It is a widely used photoinitiator.

[0003] Oxime ester photoinitiators are widely used in the production of various photoresists due to their relatively excellent performance. In the color filters of traditional LCD panels, oxime ester initiators can be applied to BM photoresists (Black Matrix). The next generation of displays has higher requirements on the resolution, optical density, surface impedance, etc. of BM photoresists, which also puts higher requirements on initiators. Summary of the invention

[0004] The main purpose of the present invention is to provide a silicon-containing oxime ester photoinitiator, a preparation method and application thereof, so as to further improve the resolution, optical density and surface impedance of the oxime ester photoinitiator during the application process.

[0005] In order to achieve the above object, the present invention provides a silicon-containing oxime ester photoinitiator on the one hand, wherein the silicon-containing oxime ester photoinitiator has a chemical structure shown in formula (I):

[0006]

[0007] wherein R1 is selected from a C1-C8 alkylene group; A, B, and C are independently selected from a C1-C8 alkyl group or a C6-C 10 Aryl; R2 is selected from hydrogen or C1-C8 alkyl; R3 is selected from C1-C8 alkyl and is cut off by 1-3 oxygen; R4 is selected from C1-C8 alkyl or C6-C 10 Aryl.

[0008] In order to achieve the above object, another aspect of the present invention further provides that in the presence of a third type of base and a fourth solvent, the fourth intermediate and the acylating agent are subjected to an esterification reaction to obtain the silicon-containing oxime ester photoinitiator, and the first intermediate, the second intermediate, the third intermediate and the fourth intermediate have the following structures:

[0009]

[0010] wherein X is a halogen, and R1, A, B, C, R2, R3, and R4 have the same definitions as above.

[0011] Another aspect of the present invention provides the use of the above silicon-containing oxime ester photoinitiator in photoresists, paints, coatings, inks or molding materials.

[0012] By applying the technical solution of the present invention, the silicon-containing oxime ester initiator having the above structure has the characteristic of high sensitivity, and the introduction of the R3 group can greatly improve the solubility of the silicon-containing oxime ester initiator during the application process, thereby improving its resistance during the application process. DETAILED DESCRIPTION

[0013] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0014] As described in the background technology, oxime ester initiators can be applied to BM photoresists, and the next generation of displays has higher requirements on the resolution, optical density, surface impedance, etc. of BM photoresists. In order to solve the above technical problems, the present application provides a silicon-containing oxime ester photoinitiator, characterized in that the silicon-containing oxime ester photoinitiator has a chemical structure shown in formula (I):

[0015]

[0016] wherein R1 is selected from a C1-C8 alkylene group; A, B, and C are independently selected from a C1-C8 alkyl group or a C6-C 10 Aryl; R2 is selected from hydrogen or C1-C8 alkyl; R3 is selected from C1-C8 alkyl and is cut off by 1-3 oxygen; R4 is selected from C1-C8 alkyl or C6-C 10 Aryl.

[0017] The silicon-containing oxime ester initiator having the above structure has the characteristic of high sensitivity, and the introduction of the R3 group can greatly improve the solubility of the silicon-containing oxime ester initiator during the application process, thereby improving its resistance during the application process.

[0018] In order to reduce the difficulty of its synthesis and improve its yield, sensitivity and resistance, preferably, R1 includes but is not limited to C1-C4 alkylene; R2 includes but is not limited to methyl, ethyl or propyl; A, B, C independently include but are not limited to methyl, ethyl, propyl or phenyl, R3 includes but is not limited to C4-C6 alkyl, and is cut off by 2 or 3 oxygens; R4 includes but is not limited to methyl, ethyl, propyl, phenyl, methylphenyl, ethylphenyl or naphthyl.

[0019] In order to further improve the resistance of its application process, preferably, R3 includes but is not limited to -O-(CH2)2-O-CH2-CH3, -O-(CH2)2-O-(CH2)2-O-CH2-CH3 or -O-CH(CH3)-CH2-O-CH3.

[0020] In order to further improve the comprehensive performance of the silicon-containing oxime ester initiator, the structure of each substituent group can be optimized. Preferably, the silicon-containing oxime ester photoinitiator includes but is not limited to one or more of the following compounds:

[0021]

[0022]

[0023] The second aspect of the present application also provides a method for preparing the above-mentioned silicon-containing oxime ester photoinitiator, comprising: in the presence of a first base and a first solvent, subjecting carbazole and a silane to an alkylation reaction to obtain a first intermediate; in the presence of a catalyst, subjecting the first intermediate to a Friedel-Crafts reaction with an acyl chloride to obtain a second intermediate; in the presence of a second solvent, subjecting the second intermediate to a nitration reaction with a nitro reagent to obtain a third intermediate; in the presence of a second base and a third solvent, subjecting the third intermediate to an oximation reaction with hydroxylamine hydrochloride to obtain a fourth intermediate; in the presence of a third base and a fourth solvent, subjecting the fourth intermediate to an acylating reagent to an esterification reaction to obtain a silicon-containing oxime ester photoinitiator, wherein the first intermediate, the second intermediate, the third intermediate and the fourth intermediate have the following structures:

[0024]

[0025] Wherein X is halogen, and R1, A, B, C, R2, R3, and R4 have the same definitions as above.

[0026] A preferred synthetic route is as follows:

[0027]

[0028] Preferably, in the alkylation reaction, the first base includes but is not limited to one or more of potassium hydroxide, sodium hydroxide and sodium hydride, the first solvent includes but is not limited to one or more of tetrahydrofuran, dimethylformamide or toluene, and the reaction temperature is 0 to 100°C.

[0029] Preferably, in the Friedel-Crafts reaction, the catalyst includes but is not limited to Lewis acid and / or protonic acid. Preferably, the Lewis acid includes but is not limited to one or more of aluminum chloride, tin chloride, zinc chloride and ferric chloride. The protonic acid includes but is not limited to one or more of hydrogen fluoride, sulfuric acid and phosphoric acid. The reaction temperature is -10 to 30°C.

[0030] Preferably, in the nitration reaction, the nitration reagent includes but is not limited to one or more of concentrated nitric acid, fuming nitric acid, sodium nitrate and nitrate esters, and the reaction temperature is -10 to 30°C.

[0031] Preferably, in the oximation reaction, the second base includes but is not limited to one or more of ammonium acetate, sodium acetate, potassium acetate, triethylamine, sodium hydroxide and potassium hydroxide, the second solvent includes but is not limited to one or more of methanol, ethanol, N,N-dimethylformamide, and the reaction temperature is 50-100°C.

[0032] Preferably, in the esterification reaction, the acylating agent is an acyl halide and / or anhydride, the third base includes but is not limited to one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and sodium hydride, the fourth solvent includes but is not limited to one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane (DCM), chloroform, chlorobenzene, dimethylacetamide and dimethylformamide, and the reaction temperature is -10 to 60°C.

[0033] Preferably, the acyl halide is selected from cyclohexanecarbonyl chloride, 2-propylpentanoyl chloride, 3,5,5-trimethylhexanoyl chloride, 3-chloropropionyl chloride, 5-chlorovaleryl chloride, 3-chloropivaloyl 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, phenylacetyl chloride, The acid anhydride includes, but is not limited to, one or more of acetic anhydride, propionic anhydride, decanoic anhydride, stearic anhydride, isobutyric anhydride, tert-valeric anhydride and 4-methoxyphenylacetic anhydride.

[0034] In the process of preparing the above silicon-containing oxime ester photoinitiator, the reaction reagents used are all known compounds in the prior art and can be obtained commercially or conveniently prepared by existing synthesis methods.

[0035] The initiator represented by formula (I) of the present invention can be used in UV-LED light curing system, and is particularly suitable for initiation under the action of 365nm light source, has excellent sensitivity, and has the characteristics of resistance after application.

[0036] The third aspect of the present application also provides an application of the above-mentioned silicon-containing oxime ester photoinitiator in photoresist, paint, coating, ink or molding material.

[0037] The above silicon-containing oxime ester photoinitiator can be used in photoresist products. At the same time, the above-mentioned silicon oxime ester photoinitiator can also be used in paints, coatings, inks and molding materials, etc., specifically, it can be used to make: coatings applied on substrates such as plastics, metals, glass, ceramics, wood, walls, etc.; protective film materials such as hard coating agents, anti-fouling films, anti-reflective films, impact buffer films, etc.; photocuring adhesives, adhesives, photodegradable coatings, coatings, moldings; optical recording media such as holographic imaging materials; optical molding resins, for example, inks (resins) for 3D printing, photoresists for electronic circuits and semiconductor manufacturing, photoresists for electronic materials such as color filters, black matrices, dry films in displays, etc.; interlayer insulating films, light extraction films, brightening films, sealing materials; printing inks such as screen printing, offset printing, gravure printing, etc., photocuring inks for inkjet printing; optical components such as lenses, lens arrays, optical waveguides, light guide plates, light diffusers, diffraction elements, etc.; optical spacers, rib walls, materials for nanoimprinting, quantum dots, OLEDs, etc.

[0038] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0039] Preparation Example

[0040] Example 1

[0041]

[0042] (1) Preparation of intermediate 1b

[0043]

[0044] 100g carbazole was added to a 1000mL three-necked flask, dissolved with 400g DMF, and then 100g (3-chloropropyl) trimethylsilane was added. 36g sodium hydride was added in an ice-water bath, and the temperature was raised to 80°C for reaction after the addition. The reaction was completed in 2h. The reaction solution was slowly poured into ice water to quench, and 400mL dichloromethane (DCM) was added for extraction. After standing and separating the water layer, the organic phase was washed with water 5 times, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a brown oil. 400g methanol was added for crystallization in an ice-water bath, filtered, and dried to obtain 153g of off-white powder with HPLC purity of 98.71% and a yield of 91.07wt%.

[0045] (2) Preparation of intermediate 1c

[0046]

[0047] In a 2000mL three-necked flask, 140g of intermediate 1b and 700mL of dichloromethane were added, stirred to dissolve, and then 73g of aluminum chloride was added. The temperature was cooled to 0°C with ice water, and 127g of acyl chloride was added dropwise. The temperature was controlled at 0-5°C. After the addition was completed in 2h, the reaction was continued for 1h. The reaction was controlled to be finished by HPLC, and the reaction solution was slowly poured into 700g of ice water for hydrolysis. After stirring for 1h, the water layer was separated and the organic phase was washed with water (300g×3 times), dried over anhydrous sodium sulfate, concentrated, and 500g of methanol was added to obtain 207g of off-white solid intermediate 1c. The yield was 85.12% and the HPLC purity was 98.02wt%.

[0048] (3) Preparation of Compound 1d

[0049]

[0050] Add 48.8g of intermediate 1c and 300g of dichloromethane to a 500mL three-necked flask, stir to dissolve, cool to 0°C, drop 8.3g of fuming nitric acid and 40g of dichloromethane, add dropwise, complete the dropwise addition for 2h, keep warm for 2h, and the reaction is completed by HPLC. Slowly pour the reaction solution into 300g of ice water to quench, stir for 1h, let stand to separate the water layer, wash the organic layer with water (200g×3 times), dry with anhydrous sodium sulfate, and concentrate until no liquid is discharged. Dissolve the residue with 200g of ethyl acetate, cool to 0-5°C, and stir to crystallize for 2h. Filter by suction to obtain 43.3g of yellow solid, with a yield of 81.27wt% and a purity of 98.14%.

[0051] (4) Preparation of Compound 1e

[0052]

[0053] 53.3 g of intermediate 1d, 400 g of ethanol, 34.8 g of hydroxylamine hydrochloride and 49.2 g of sodium acetate were added to a 1000 mL three-necked flask, and the temperature was raised and refluxed for 240 h. The reaction was controlled to be complete by HPLC. The temperature was lowered to 5-10 ° C, filtered, rinsed with methanol, and dried to obtain 47.2 g of yellow solid with a yield of 86.20 wt% and a purity of 97.43%.

[0054] (5) Preparation of Compound 1

[0055]

[0056] Add 27.4g of intermediate 1e and 150g of dichloromethane, and 0.3g of dimethylaminopyridine to a 250mL three-necked flask, add 7.6g of acetic anhydride dropwise at 20-25℃, add dropwise for 0.5h, keep warm for 2h, and control the reaction to end in HPLC. Slowly pour the reaction solution into 200g of ice water to quench, stir for 1h and let stand to separate the water layer, wash the organic layer with water (100g×3 times), dry with anhydrous sodium sulfate and concentrate until no liquid comes out, add 150g of acetone at 0-5℃ for crystallization for 2h, filter and dry to obtain 25.7g of light yellow solid, with a yield of 87.31wt% and a purity of 99.23%. The H NMR spectrum is as follows:

[0057] 1H NMR(500MHz,Chloroform-d)δ9.18(d,J=1.6Hz,1H),8.18(d,J=1.4Hz,1H),8.10(dd,J=7.4,1.4Hz,1H),7.78(d,J=7 .5Hz,1H),7.58(d,J=7.4Hz,1H),7.50(dd,J=7.5,1.5Hz,1H),7.27(dq,J=7.4,1.0Hz,1H),7.06(dd,J=7.6,1.5Hz,1H ),6.76(d,J=1.5Hz,1H),4.12(t,J=7.1Hz,2H),4.01(t,J=7.1Hz,2H),3.76(t,J=7.0Hz,2H),3.55(q,J=8.0Hz,2H),2 .47(d,J=1.1Hz,3H),2.15(s,3H),1.61(p,J=7.1Hz,2H),1.17(t,J=8.0Hz,3H),0.68(t,J=7.1Hz,2H),-0.14(s,9H).

[0058] Example 2

[0059]

[0060] (1) Preparation of intermediate 2b (same as Example 1)

[0061]

[0062] 100g carbazole was added to a 1000mL three-necked flask, dissolved with 400g DMF, and then 100g (3-chloropropyl) trimethylsilane was added. 36g sodium hydride was added in an ice-water bath, and the temperature was raised to 80°C for reaction after addition. The reaction was completed after 2h. The reaction solution was slowly poured into ice water for quenching, and 400mL dichloromethane was added for extraction. After standing and separating the water layer, the organic phase was washed with water 5 times, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a brown oil. 400g methanol was added for crystallization in an ice-water bath, filtered, and dried to obtain 153g of gray-white powder, HPLC purity 98.71%, yield 91.07wt%.

[0063] (2) Preparation of intermediate 2c

[0064]

[0065] In a 500mL three-necked flask, 56.2g of intermediate 2b and 250mL of dichloromethane were added, stirred to dissolve, and then 29.3g of aluminum chloride was added. The temperature was cooled to 0°C with ice water, and 63.1g of acyl chloride was added dropwise. The temperature was controlled within the range of 0-5°C. After the addition was completed within 2h, the reaction was continued for 1h. The reaction was controlled to be finished by HPLC, and the reaction solution was slowly poured into 300g of ice water for hydrolysis. After stirring for 1h, the water layer was separated and the organic phase was washed with water (200g×3 times), dried over anhydrous sodium sulfate, and concentrated to obtain brown oily intermediate 1c with HPLC purity of 97.54%. No crystallization purification was required, and the next step was performed directly.

[0066] (3) Preparation of compound 2d

[0067]

[0068] Add the oily intermediate 2c from the previous step and 250g of dichloromethane to a 500mL three-necked flask, stir to dissolve, cool to 0°C, drop 15.1g of fuming nitric acid and 60g of dichloromethane, add dropwise, complete the dropwise addition for 2h, keep warm for 2h, and the reaction is completed by HPLC control. Slowly pour the reaction solution into 300g of ice water to quench, stir for 1h, let stand to separate the water layer, wash the organic layer with water (200g×3 times), dry with anhydrous sodium sulfate, and concentrate until no liquid is discharged. Dissolve the residue with 200g of ethyl acetate, cool to 0-5°C, and stir to crystallize for 2h. Filter by suction to obtain 83.7g of yellow solid, with a two-step yield of 72.58wt% and a purity of 98.03%.

[0069] (4) Preparation of Compound 2e

[0070]

[0071] 57.7 g of intermediate 1d, 400 g of ethanol, 34.8 g of hydroxylamine hydrochloride and 49.2 g of sodium acetate were added to a 1000 mL three-necked flask, and the temperature was raised and refluxed for 300 h. The reaction was controlled to be complete by HPLC. The temperature was lowered to 5-10 ° C, filtered, rinsed with methanol, and dried to obtain 49.4 g of yellow solid with a yield of 83.45 wt% and a purity of 97.28%.

[0072] (5) Preparation of Compound 2

[0073]

[0074] In a 250 mL three-necked flask, add 29.6 g of intermediate 2e, 150 g of dichloromethane and 0.3 g of dimethylaminopyridine, and add 7.6 g of acetic anhydride dropwise at 20-25 °C. The addition is completed in 0.5 h. Keep warm.

[0075] After 2 hours of reaction, the reaction was controlled to be complete by HPLC. The reaction solution was slowly poured into 200g of ice water to quench, stirred for 1 hour, and then allowed to stand to separate the water layer. The organic layer was washed with water (100g×3 times), dried over anhydrous sodium sulfate, and concentrated until no liquid was discharged. 150g of acetone was added at 0-5℃ for crystallization for 2 hours, filtered, and dried to obtain 26.9g of light yellow solid, with a yield of 85.03wt% and a purity of 99.07%. The H-NMR spectrum is as follows:

[0076] 1 H NMR(500MHz,Chloroform-d)δ9.18(d,J=1.6Hz,1H),8.17(d,J=1.4Hz,1H),8.10(dd,J=7.4,1.4Hz,1H),7.78(d,J=7.5Hz,1H) ,7.61(d,J=7.4Hz,1H),7.46(dd,J=7.4,1.4Hz,1H),7.27(dq,J=7.7,1.1Hz,1H),7.06(dd,J=7.6,1.5Hz,1H),6.77(d,J=1.5Hz ,1H),4.13(t,J=7.1Hz,2H),4.01(t,J=7.1Hz,2H),3.77(t,J=7.0Hz,2H),3.69–3.63(m,2H),3.63–3.56(m,2H),3.54(q,J=8.0 Hz, 2H), 2.47 (d, J = 1.1Hz, 3H), 2.15 (s, 3H), 1.61 (p, J = 7.1Hz, 2H), 1.15 (t, J = 8.1Hz, 3H), 0.68 (t, J = 7.1Hz, 2H), -0.14 (s, 9H).

[0077] Example 3-12

[0078] According to the method of Example 1 or 2, the corresponding raw materials were replaced to prepare the following compounds 3-12, whose structures and corresponding NMR characterization data are listed in Table 1 below.

[0079] Table 1

[0080]

[0081]

[0082]

[0083] Performance evaluation 1. Photosensitivity test

[0084] It should be noted that the photocurable composition used in the photosensitivity test in all the embodiments and comparative examples of the present application is prepared according to the following ratio. Wherein, the photocurable composition includes, by weight: 200 parts of acrylate copolymer, 100 parts of dipentaerythritol hexaacrylate, 5 parts of photoinitiator, 900 parts of butanone (solvent), 5 parts of carbon black, and the above-mentioned acrylate copolymer (manufacturer: Changzhou Qiangli Electronic New Materials Co., Ltd.) is a copolymer of benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio of 70:10:20), Mw=10000.

[0085] In the above-mentioned photocurable composition, the photoinitiator is the oxime ester compound represented by the general formula (I) in the above content of the present application or a similar photoinitiator known in the prior art for comparison. The specific formulas of all the embodiments and comparative examples of the present application are shown in Table 2.

[0086] Table 2

[0087]

[0088]

[0089]

[0090] (1) Sensitivity test

[0091] The above composition was stirred in the dark and coated on a 21-step gradient ruler using a 6# wire rod to form a coating with a thickness of about 15 μm. The coating was exposed to light with an LED lamp (385 nm) to give 191 mJ / cm 2 The light was cured with 2% NaOH aqueous solution for 2 min, then rinsed with tap water for 1 min, and the test results of the gradient ruler were observed.

[0092] Table 3

[0093]

[0094] (2) Test of formula resistance performance

[0095] Referring to the specific formula shown in Table 2, a photocurable composition was prepared, and the coating was placed in an oven at 230° C. and baked for 150 min. After being taken out, the surface impedance was measured using a Hiresta-UX MCP-HT800 impedance meter, with the test probe URS and the test voltage being 10 V.

[0096] Table 4

[0097]

[0098] In summary, the silicon-containing oxime ester initiator represented by formula (I) disclosed in the present invention has the characteristics of high sensitivity and excellent resistance performance after application.

[0099] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0100] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A silicon-containing oxime ester photoinitiator, characterized in that: The silicon-containing oxime ester photoinitiator has a chemical structure shown in formula (I): wherein R1 is selected from a C1-C8 alkylene group; A, B, and C are independently selected from a C1-C8 alkyl group or a C6-C 10 Aryl; R2 is selected from hydrogen or C1-C8 alkyl; R3 is selected from C1-C8 alkyl and is cut off by 1-3 oxygen; R4 is selected from C1-C8 alkyl or C6-C 10 Aryl.

2. The silicon-containing oxime ester photoinitiator according to claim 1, characterized in that: The R1 is selected from C1-C4 alkylene; the R2 is selected from methyl, ethyl or propyl; A, B, C are independently selected from methyl, ethyl, propyl or phenyl, the R3 is selected from C4-C6 alkyl and is cut off by 2 or 3 oxygens: R4 is selected from methyl, ethyl, propyl, phenyl, methylphenyl, ethylphenyl or naphthyl.

3. The silicon-containing oxime ester photoinitiator according to claim 2, characterized in that: The R3 is selected from -O-(CH2)2-O-CH2-CH3, -O-(CH2)2-O-(CH2)2-O-CH2-CH3 or -O-CH(CH3)-CH2-O-CH3.

4. The silicon-containing oxime ester photoinitiator according to any one of claims 1 to 3, characterized in that: The silicon-containing oxime ester photoinitiator is selected from one or more of the following compounds:

5. A method for preparing the silicon-containing oxime ester photoinitiator according to any one of claims 1 to 4, characterized in that: The preparation method of the silicon-containing oxime ester photoinitiator comprises: In the presence of a first base and a first solvent, alkylating carbazole and a silane halide to obtain a first intermediate; In the presence of a catalyst, the first intermediate is subjected to Friedel-Crafts reaction with an acyl chloride to obtain a second intermediate; In the presence of a second solvent, the second intermediate is subjected to a nitration reaction with a nitro reagent to obtain a third intermediate; In the presence of a second base and a third solvent, the third intermediate is subjected to an oximation reaction with hydroxylamine hydrochloride to obtain a fourth intermediate; In the presence of a third base and a fourth solvent, the fourth intermediate and the acylating agent are subjected to an esterification reaction to obtain the silicon-containing oxime ester photoinitiator. The first intermediate, the second intermediate, the third intermediate and the fourth intermediate have the following structures: Wherein X is halogen, and R1, A, B, C, R2, R3, and R4 have the same definitions as in claim 1.

6. The method for preparing the silicon-containing oxime ester photoinitiator according to claim 5, characterized in that: In the alkylation reaction, the first base is selected from one or more of potassium hydroxide, sodium hydroxide and sodium hydride, the first solvent is selected from one or more of tetrahydrofuran, dimethylformamide or toluene, and the reaction temperature is 0-100°C.

7. The method for preparing the silicon-containing oxime ester photoinitiator according to claim 5, characterized in that: In the Friedel-Crafts reaction, the catalyst is selected from Lewis acid and / or protonic acid. Preferably, the Lewis acid is selected from one or more of aluminum chloride, tin chloride, zinc chloride and ferric chloride, and the protonic acid is selected from one or more of hydrogen fluoride, sulfuric acid and phosphoric acid. The reaction temperature is -10 to 30°C.

8. The method for preparing the silicon-containing oxime ester photoinitiator according to claim 5, characterized in that: In the nitration reaction, the nitration reagent is selected from one or more of concentrated nitric acid, fuming nitric acid, sodium nitrate and nitrate ester, and the reaction temperature is -10 to 30°C.

9. The method for preparing the silicon-containing oxime ester photoinitiator according to claim 5, characterized in that: In the oximation reaction, the second base is selected from one or more of ammonium acetate, sodium acetate, potassium acetate, triethylamine, sodium hydroxide and potassium hydroxide, the second solvent is selected from one or more of methanol, ethanol and N,N-dimethylformamide, and the reaction temperature is 50-100°C.

10. The method for preparing the silicon-containing oxime ester photoinitiator according to claim 5, characterized in that: In the esterification reaction, the acylating agent is an acyl halide and / or anhydride, the third base is selected from one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and sodium hydride, the fourth solvent is selected from one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide and dimethylformamide, and the reaction temperature is -10 to 60°C; Preferably, the acyl halide is cyclohexanecarbonyl chloride, 2-propylpentanoyl chloride, 3,5,5-trimethylhexanoyl chloride, 3-chloropropionyl chloride, 5-chlorovaleryl chloride, 3-chloropivaloyl 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, 2-thiophenecarbonyl chloride, thiophene-2-acetyl chloride, chloronicotinoyl chloride, 2-furocarbonyl chloride, quinolinecarbonyl chloride, naphthoyl chloride, 2-ethoxy-1-naphthoyl chloride and anthracenecarbonyl chloride, and the acid anhydride is selected from one or more of acetic anhydride, propionic anhydride, capric anhydride, stearic anhydride, isobutyric anhydride, tert-valeric anhydride and 4-methoxyphenylacetic anhydride.

11. Use of the silicon-containing oxime ester photoinitiator according to any one of claims 1 to 4 in photoresists, paints, coatings, inks or molding materials.

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