Allyl carbazole ketoxime ester compound, product containing same and application of allyl carbazole ketoxime ester compound

Abstract

The invention belongs to the technical field of photocuring, and relates to an allyl carbazole ketoxime ester compound, a product containing the allyl carbazole ketoxime ester compound and application of the allyl carbazole ketoxime ester compound. Specifically, the structure of the compound disclosed by the invention is shown as a formula (I), not only is the relative low activity of carbazole acyl free radicals overcome, but also the problems of toxicity, odor and the like in a photocuring system are solved, and the compound has the advantages of wide applicable wavelength range, high photolysis efficiency, good compatibility with monomers or resins and the like. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and relates to an allylcarbazole ketoxime ester compound, a product containing the same, and an application of the allylcarbazole ketoxime ester compound in the field of photocuring. Background Art

[0002] Photopolymerization has a wide range of applications in many fields, such as adhesives or coatings for UV curing, and is also commonly used in microelectronics, three-dimensional micro-construction and other fine structure processing fields. In order to meet various functional applications, the modification and research of each component in the photopolymerization formula has always been the focus of scholars. For example, with the widespread use of new LED light sources, the use of some photosensitive formulas with shorter working wavelengths is restricted. Therefore, as one of the most important components in UV curing reactions, the research on photoinitiators that can produce active species under light to induce monomer polymerization is particularly important. The oxime ester initiators OXE-01 and OXE-02 currently on the market are very widely used, but they also have certain deficiencies and disadvantages. For example, the benzoyl radicals generated by OXE-01 after photolysis have an odor after capturing hydrogen, and the radical initiation activity is low, which is more suitable for initiation at 365nm and 405nm wavelengths, and there is a certain difficulty in deep curing. Therefore, the design and development of photoinitiators that match the LED emission wavelength or are suitable for long wavelengths and safe wavelengths has gradually become a research hotspot. Summary of the invention

[0003] Problem that the invention aims to solve

[0004] In view of the above problems existing in the prior art, the present invention provides a series of novel allylcarbazole ketoxime ester compounds, products containing the same, and applications thereof in the field of photocuring, in order to solve the above problems.

[0005] Solutions for solving problems

[0006] In a first aspect, the present invention provides an allylcarbazole ketoximate compound as shown in formula (I),

[0007]

[0008] in,

[0009] Each R1 is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl and C 6-20 Aryl, the alkyl, cycloalkyl or aryl is unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C1-20 Alkyl, halogen and cyano;

[0010] Each R2 is independently selected from C 1-20 Alkyl and C 3-20 Cycloalkyl, the alkyl or cycloalkyl is unsubstituted or substituted with one or more R b Replace; each R b Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C 1-20 Alkyl, halogen and cyano;

[0011] R3, R4, R5, R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, nitro, cyano, C 1-20 Alkyl, C 6-20 Aryl, 4-20 membered heterocyclic group, -C(=O)C 1-20 Alkyl, -C(=O)C 6-20 Aryl and The aryl or heterocyclic group is unsubstituted or substituted by one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-20 Alkyl, -OC 1-20 Alkyl and halogenated C 1-20 Substitution of alkyl groups;

[0012] R 10 , R 11 and R 12 are each independently selected from hydrogen and methyl.

[0013] In a second aspect, the present invention provides a photosensitive composition comprising the compound in the first part.

[0014] Preferably, the photosensitive composition further comprises at least one of the following components:

[0015] a) alkali soluble resin;

[0016] b) photopolymerizable compounds;

[0017] c) Solvent.

[0018] More preferably, the photosensitive composition comprises the following components in parts by weight: 1-5 parts of the compound in the first part; 10-20 parts of the alkali-soluble resin; 5-10 parts of the photopolymerizable compound; and 80-100 parts of the solvent.

[0019] In the third part, the present invention provides a photoresist comprising the following components:

[0020] i) the compounds in Part I;

[0021] ii) alkali soluble resin;

[0022] iii) photopolymerizable compounds;

[0023] iv) Auxiliary agents.

[0024] Preferably, the auxiliary agent is selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

[0025] In the fourth part, the present invention provides the application of the compound in the first part, the photosensitive composition in the second part or the photoresist in the third part in the field of photocuring.

[0026] Effects of the Invention

[0027] The allyl carbazole ketoxime ester compound of the present invention introduces an allyl structure at the N position of the carbazole ring and a ketoxime ester structure at the 1 position, and decomposes after light excitation to obtain an allyl carbazole acyl radical, which then undergoes intramolecular cyclization to form a highly active carbon-centered free radical, thereby overcoming the relatively low activity of the carbazole acyl radical and solving the problems of toxicity and odor in the photocuring system. In addition, due to the strong conjugation effect of the carbazole ring, a good absorption intensity is generated in the visible light region, and good sensitivity is obtained within the light radiation range, thereby having the advantages of a wide range of applicable wavelengths, high photolysis efficiency, and good compatibility with monomers or resins. DETAILED DESCRIPTION

[0028] Allylcarbazole ketone oxime ester compounds

[0029] The present invention provides an allylcarbazole ketoxime ester compound, the structure of which can be shown as formula (I):

[0030]

[0031] in,

[0032] Each R1 is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl and C 6-20 Aryl, the alkyl, cycloalkyl or aryl is unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C 1-20 Alkyl, halogen and cyano;

[0033] Each R2 is independently selected from C 1-20 Alkyl and C 3-20Cycloalkyl, the alkyl or cycloalkyl is unsubstituted or substituted with one or more R b Replace; each R b Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C 1-20 Alkyl, halogen and cyano;

[0034] R3, R4, R5, R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, nitro, cyano, C 1-20 Alkyl, C 6-20 Aryl, 4-20 membered heterocyclic group, -C(=O)C 1-20 Alkyl, -C(=O)C 6-20 Aryl and The aryl or heterocyclic group is unsubstituted or substituted by one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-20 Alkyl, -OC 1-20 Alkyl and halogenated C 1-20 Substitution of alkyl groups;

[0035] R 10 , R 11 and R 12 are each independently selected from hydrogen and methyl.

[0036] In one embodiment of the present invention, in formula (I), each R1 is independently selected from C 1-10 Alkyl, C 3-10 Cycloalkyl and C 6-10 Aryl, the alkyl, cycloalkyl or aryl is unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-10 Alkyl, -OC 1-10 Alkyl, halogenated C 1-10 Alkyl, halogen and cyano.

[0037] In one embodiment of the present invention, in formula (I), each R1 is independently selected from C 1-6 Alkyl, C 3-10 Cycloalkyl and phenyl, the alkyl, cycloalkyl or phenyl being unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-6 Alkyl, -OC 1-6 Alkyl, halogenated C 1-6 Alkyl, halogen and cyano.

[0038] In one embodiment of the present invention, in formula (I), each R1 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl.

[0039] In one embodiment of the present invention, in formula (I), each R1 is independently selected from methyl and phenyl.

[0040] In one embodiment of the present invention, in formula (I), each R1 is independently methyl.

[0041] In one embodiment of the present invention, in formula (I), each R2 is independently selected from C 1-9 Alkyl and C 5-9 Cycloalkyl, the alkyl or cycloalkyl is unsubstituted or substituted with one or more R b Replace; each R b Each independently selected from C 1-9 Alkyl, -OC 1-9 Alkyl, halogenated C 1-9 Alkyl, halogen and cyano.

[0042] In one embodiment of the present invention, in formula (I), each R2 is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and the methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl is unsubstituted or replaced by one or more R b Replace; each R b Each independently selected from C 1-6 Alkyl, -OC 1-6 Alkyl, halogenated C 1-6 Alkyl, halogen and cyano.

[0043] In one embodiment of the present invention, in formula (I), R2 is selected from methyl,

[0044] In one embodiment of the present invention, in formula (I), R2 is selected from methyl.

[0045] In one embodiment of the present invention, in formula (I), R3, R5, R6, R8 and R9 are each independently selected from hydrogen and C 1-10 alkyl.

[0046] In one embodiment of the present invention, in formula (I), R5 is hydrogen, R3, R6, R8 and R9 are each independently selected from hydrogen and C 1-4 alkyl.

[0047] In one embodiment of the present invention, in formula (I), R5 is hydrogen, and R3, R6, R8 and R9 are each independently selected from hydrogen, methyl, ethyl, n-propyl and n-butyl.

[0048] In one embodiment of the present invention, in formula (I), R5 is hydrogen, and R3, R6, R8 and R9 are each independently selected from hydrogen and methyl.

[0049] In one embodiment of the present invention, in formula (I), R4 and R7 are each independently selected from hydrogen, halogen, nitro, cyano, C 1-10 Alkyl, C 6-10 Aryl, -C(=O)C 1-10 Alkyl, -C(=O)C 6-10 Aryl and The aryl group is unsubstituted or substituted with one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-10 Alkyl, -OC 1-10 Alkyl and halogenated C 1-10 The alkyl group is substituted with a substituent.

[0050] In one embodiment of the present invention, in formula (I), R4 and R7 are each independently selected from hydrogen, nitro, C 1-6 Alkyl, -C(=O)C 1-6 Alkyl, -C(=O)C 6-10 Aryl and The aryl group is unsubstituted or substituted with one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-6 Alkyl, -OC 1-6 Alkyl and halogenated C 1-6 The alkyl group is substituted with a substituent.

[0051] In one embodiment of the present invention, in formula (I), R4 and R7 are each independently selected from hydrogen, nitro, methyl, ethyl, n-propyl, n-butyl,

[0052] In one embodiment of the present invention, in formula (I), R4 and R7 are each independently selected from hydrogen, nitro,

[0053] In one embodiment of the present invention, in formula (I), R4 and R7 are not hydrogen or nitro at the same time, and when one of them is hydrogen, the other is

[0054] In one embodiment of the present invention, in formula (I), R 10 , R 11 and R 12 are each independently hydrogen.

[0055] In one embodiment of the present invention, the structure of the allylcarbazole ketoximate ester compound may be as shown in formula (II):

[0056]

[0057] Among them, R 1 , R 2 , R 4 and R 7 As defined in formula (I).

[0058] In one embodiment of the present invention, the allylcarbazole ketoximate compound can be selected from the following compounds:

[0059]

[0060]

[0061]

[0062] Products containing allylcarbazole ketoxime ester photoinitiators

[0063] The allylcarbazole ketoxime ester compound of the present invention can be used as a photopolymerization initiator (or photoinitiator) in the field of photocuring, for example, as a photoinitiator component in a photosensitive composition or a photoresist.

[0064] To this end, the present invention provides a photosensitive composition, which may contain the above-mentioned allylcarbazole ketoximate ester compound of the present invention as a photoinitiator.

[0065] In one embodiment of the present invention, the photosensitive composition may further comprise at least one of the following components:

[0066] a) alkali soluble resin;

[0067] b) photopolymerizable compounds;

[0068] c) Solvent.

[0069] In one embodiment of the present invention, the alkali-soluble resin may be an acrylic copolymer, for example, a copolymer of (meth)acrylic acid and one or more esters thereof, or a copolymer of two or more (meth)acrylic esters.

[0070] In one embodiment of the present invention, the alkali-soluble resin may be a copolymer of methacrylic acid, alkyl methacrylate and hydroxyalkyl methacrylate, for example, a copolymer of methacrylic acid, methyl methacrylate, n-butyl methacrylate and hydroxyethyl methacrylate, especially a copolymer in which the weight ratio of the four is 4:2:11:3.

[0071] In one embodiment of the present invention, the photopolymerizable compound may be a photopolymerizable compound having an ethylenically unsaturated structure, for example, may be a (meth)acrylate polyol ester.

[0072] In one embodiment of the present invention, the photopolymerizable compound may be trimethylolpropane triacrylate.

[0073] In one embodiment of the present invention, the solvent may be a glycol monoether, for example, a glycol monofatty ether.

[0074] In one embodiment of the present invention, the solvent may be ethyl cellosolve (ie, ethylene glycol monoethyl ether).

[0075] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0076] 1-5 parts of the above-mentioned allylcarbazole ketoxime ester compound of the present invention as a photoinitiator;

[0077] 10-20 parts of alkali soluble resin;

[0078] 5-10 parts of photopolymerizable compound;

[0079] 80-100 parts of solvent.

[0080] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0081] 2-4 parts of the above-mentioned allylcarbazole ketoxime ester compound of the present invention as a photoinitiator;

[0082] 12-18 parts of alkali soluble resin;

[0083] 6-8 parts of photopolymerizable compound;

[0084] 80-90 parts of solvent.

[0085] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0086] 3.0 parts of the allylcarbazole ketoxime ester compound of the present invention as a photoinitiator;

[0087] 15.5 parts of alkali soluble resin;

[0088] 6.4 parts of photopolymerizable compound;

[0089] 87.7 parts of solvent.

[0090] In one embodiment of the present invention, the photosensitive composition may be composed of the above-mentioned allylcarbazole ketooxime ester compound of the present invention as a photoinitiator, an alkali-soluble resin, a photopolymerizable compound and a solvent.

[0091] The present invention also provides a photoresist, which may include the following components:

[0092] i) the above-mentioned allylcarbazole ketoximate compound of the present invention as a photoinitiator;

[0093] ii) alkali soluble resin;

[0094] iii) photopolymerizable compounds;

[0095] iv) Auxiliary agents.

[0096] In one embodiment of the present invention, the auxiliary agent in the photoresist can be selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

[0097] In one embodiment of the present invention, the photoresist may comprise the following components:

[0098] i-1) the above-mentioned allylcarbazole ketoxime ester compound of the present invention as a photoinitiator;

[0099] ii-1) alkali-soluble resin;

[0100] iii-1) a photopolymerizable compound;

[0101] iv-1) Solvent and optionally colorant.

[0102] Application of products in the field of light curing

[0103] The present invention provides application of the allylcarbazole ketoxime ester compound, photosensitive composition or photoresist in the field of photocuring.

[0104] Curing reaction mechanism

[0105]

[0106] The allylcarbazole ketoxime ester compound of the present invention decomposes after light excitation, the NO bond is homolytically cleaved, carbon dioxide and nitrile small molecules are removed, and allylcarbazole acyl radicals are obtained, which then undergo intramolecular cyclization to form highly active carbon-centered free radicals, thereby increasing the polymerization rate.

[0107] The present invention is described in more detail below by specific examples, but the present invention is not limited to these examples. Unless otherwise specified, the reagents, materials and instruments used in these examples can be obtained by conventional commercial means.

[0108] Example 1: Synthesis of Compound 1

[0109]

[0110] Step 1: Coupling reaction

[0111] In a 1L three-necked flask, m-bromopropiophenone (50 g), anhydrous potassium carbonate (64.86 g), 1,4-dioxane (250 mL) and water (250 mL) were added, replaced with nitrogen three times, stirred, o-nitrophenylboric acid (47.01 g) and Pd(PPh3)4 (2.71 g) were added, and the temperature was raised to 85°C under nitrogen protection for reaction. After the reaction was complete by monitoring the TLC spot plate, the water phase was separated first, the organic phase was washed twice with hot water, separated, the organic phase was concentrated, and solid compound 1-1 (50 g) was separated by column chromatography, with a yield of 83.47%, EI-MS: m / z 255.27 [M+H] + .

[0112] Step 2: Ring Closure Reaction

[0113] Compound 1-1 (50 g) was added to a 1L three-necked flask, and dichlorobenzene (500 mL) was added and stirred to dissolve. After nitrogen replacement three times, triphenylphosphine (154 g) was added, and the temperature was raised to 170°C under nitrogen protection for reaction. After the reaction was complete by TLC spot plate monitoring, the organic phase was concentrated and separated by column chromatography to obtain solid compound 1-2 (32 g) with a yield of 73.17%, EI-MS: m / z 223.28 [M+H] + .

[0114] Step 3: Alkylation reaction

[0115] Compound 1-2 (32 g) was added to a 1L three-necked flask, tetrahydrofuran (300 mL) was added and stirred to dissolve, and then the atmosphere was replaced with nitrogen three times, potassium carbonate (59.44 g) was added, and after activation for 1 h, allyl bromide (26.01 g) was added dropwise. After the addition was complete, the mixture was reacted at room temperature. After the reaction was completed by monitoring the TLC spot plate, the organic phase was concentrated and separated by column chromatography to obtain solid compound 1-3 (35 g) with a yield of 92.73%. EI-MS: m / z 263.34 [M+H] + .

[0116] Step 4: Oxime reaction

[0117] Compound 1-3 (35 g) was added to a 1L reaction bottle, tetrahydrofuran (300 mL) and concentrated hydrochloric acid (66.38 g) were added and stirred to dissolve, and then cooled to below 5°C with an ice-water bath. Under nitrogen protection and stirring, isopentyl nitrite (20.24 g) dissolved in tetrahydrofuran (50 mL) was slowly added dropwise through a constant pressure dropping funnel. After the addition was completed for 1 h, the mixture was stirred at room temperature for 5 h. After the reaction was completed by monitoring the reaction by TLC spot plate, it was diluted with water, extracted with ethyl acetate, washed with saturated brine for several times, and the organic phase was concentrated and purified by column chromatography to obtain solid compound 1-4 (33 g) with a yield of 84.93%. EI-MS: m / z 292.34 [M+H] + .

[0118] Step 5: Oxime ester reaction

[0119] Compound 1-4 (33 g) and triethylamine (22.85 g) were added to a 1L reaction bottle and dissolved in dichloroethane (300 mL). The temperature was then lowered to 0-5°C, and acetyl chloride (10.63 g) dissolved in dichloroethane (50 mL) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 1 (35 g) with a yield of 92.73%. EI-MS: m / z 334.38 [M+H] + .

[0120] Experimental Example 2: Synthesis of Compound 11

[0121]

[0122] The experimental steps Step 1-3 refer to the synthesis scheme of Step 1-3 of compound 1 and will not be described in detail.

[0123] Step 4: Nitration reaction

[0124] Compound 2-3 (35 g) and dichloroethane (300 mL) were added to a 1 L reaction bottle, and concentrated nitric acid (18.05 g) was added dropwise. The temperature was controlled between 35-45 ° C. After the addition was completed, the temperature was kept at 45 ° C for reaction. The raw material was monitored by TLC spot plate. After the reaction was completed, water was added to wash until neutral, and the liquid was separated. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 2-4 (37 g) with a yield of 90.29%. EI-MS: m / z 308.34 [M+H] + .

[0125] Step 5: Oxime reaction

[0126] Compound 2-4 (37 g) was added to a 1L reaction bottle, tetrahydrofuran (300 mL) and concentrated hydrochloric acid (59.93 g) were added and stirred to dissolve, and then cooled to below 5°C with an ice-water bath. Under nitrogen protection and stirring, isopentyl nitrite (18.27 g) dissolved in tetrahydrofuran (50 mL) was slowly added dropwise through a constant pressure dropping funnel. After the addition was completed for 1 h, the mixture was stirred at room temperature for 5 h. After the reaction was completed by monitoring the reaction by TLC spot plate, it was diluted with water, extracted with ethyl acetate, washed with saturated brine for several times, and the organic layer was concentrated and purified by column chromatography to obtain solid compound 2-5 (35 g) with a yield of 86.26%. EI-MS: m / z 337.33 [M+H] + .

[0127] Step 6: Oxime ester reaction

[0128] Compound 2-5 (35 g) and triethylamine (21 g) were added to a 1L reaction bottle and dissolved in dichloroethane (300 mL). The temperature was then lowered to 0-5°C, and acetyl chloride (9.77 g) dissolved in dichloroethane (50 mL) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 11 (36 g, yield 91.46%), EI-MS: m / z 379.37 [M+H] + .

[0129] Experimental Example 3: Synthesis of Compound 16

[0130]

[0131] The experimental steps Step 1-3 refer to the synthesis scheme of Step 1-3 of compound 1 and will not be described in detail.

[0132] Step 4: Nitration reaction

[0133] Compound 3-3 (35 g) and dichloroethane (300 mL) were added to a 1 L reaction bottle, and concentrated nitric acid (38.65 g) was added dropwise. The temperature was controlled between 35-45 ° C. After the addition was completed, the temperature was kept at 45 ° C for reaction. The reaction of the raw material was monitored by TLC spot plate. After washing with water until neutral, the liquid was separated, and the organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 3-4 (38 g) with a yield of 90.92%. EI-MS: m / z 353.33 [M+H] + .

[0134] Step 5: Oxime reaction

[0135] Compound 3-4 (38 g) was added to a 1L reaction bottle, tetrahydrofuran (300 mL) and concentrated hydrochloric acid (53.71 g) were added and stirred to dissolve, and then cooled to below 5°C with an ice-water bath. Under nitrogen protection and stirring, isopentyl nitrite (16.38 g) dissolved in tetrahydrofuran (50 mL) was slowly added dropwise through a constant pressure dropping funnel. After the addition was completed for 1 h, the mixture was stirred at room temperature for 5 h. After the reaction was completed by monitoring the reaction by TLC spot plate, it was diluted with water, extracted with ethyl acetate, washed with saturated brine for several times, and the organic layer was concentrated and purified by column chromatography to obtain solid compound 3-5 (35 g) with a yield of 85.12%. EI-MS: m / z 382.33 [M+H] + .

[0136] Step 6: Oxime ester reaction

[0137] Compound 3-5 (35 g) and triethylamine (18.53 g) were added to a 1L reaction bottle and dissolved in dichloroethane (300 mL). The temperature was then lowered to 0-5°C, and acetyl chloride (8.62 g) dissolved in dichloroethane (50 mL) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 16 (36 g) with a yield of 92.67%. EI-MS: m / z 424.37 [M+H] + .

[0138] Experimental Example 4: Synthesis of Compound 21

[0139]

[0140] The experimental steps Step 1-4 refer to the synthesis scheme of Step 1-4 of compound 1 and will not be described in detail.

[0141] Step 5: Oxime ester reaction;

[0142] Compound 4-4 (33 g) and dichloroethane (300 mL) were added to a 1L reaction bottle, and aluminum chloride solid (19.97 g) was added, and then the temperature was lowered to 0-5°C, and acetyl chloride (29.4 g) was added dropwise. After the reaction was completed, alkali solution was added for neutralization, and then washed with water until neutral, and the liquid was separated. After the organic phase was concentrated, column chromatography was performed to obtain yellow-white solid compound 21 (38 g), with a yield of 87.36%, EI-MS: m / z 348.40 [M+H] + .

[0143] Experimental Example 5: Synthesis of Compound 26

[0144]

[0145] The experimental steps Step 1-4 refer to the synthesis scheme of Step 1-4 of compound 1 and will not be described in detail.

[0146] Step 5: Oxime ester reaction

[0147] Compound 5-4 (33 g) and dichloroethane (300 mL) were added to a 1L reaction bottle, and aluminum chloride solid (41.61 g) was added, and then the temperature was lowered to 0-5°C, and acetyl chloride (39.2 g) was added dropwise. After the reaction was completed, alkali solution was added for neutralization, and then washed with water until neutral, and the liquid was separated. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 26 (30 g) with a yield of 61.55%. EI-MS: m / z 390.44 [M+H] + .

[0148] Experimental Example 6: Synthesis of Compound 31

[0149]

[0150] Experimental steps Step 1-5 refer to the synthesis scheme of Step 1-5 of compound 2 and will not be described in detail.

[0151] Step 6: Oxime ester reaction;

[0152] Compound 6-5 (35 g) and dichloroethane (300 mL) were added to a 1L reaction bottle, and aluminum chloride solid (16.6 g) was added. The temperature was then lowered to 0-5°C, and acetyl chloride (17.92 g) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 31 (32 g) with a yield of 81.30%. EI-MS: m / z 379.37 [M+H] + .

[0153] Experimental Example 7: Synthesis of Compound 41

[0154]

[0155] The experimental steps Step 1-3 refer to the synthesis scheme of Step 1-3 of compound 1 and will not be described in detail.

[0156] Step 4: Acylation reaction

[0157] Compound 7-3 (35 g) and dichloroethane (300 mL) were added to a 1L reaction bottle, and aluminum chloride solid (21.26 g) was added, then cooled to 0-5°C, and benzoyl chloride (24.29 g) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and then washed with water until neutral, and the liquid was separated. The organic phase was concentrated and purified by column chromatography to obtain solid compound 7-4 (42 g) with a yield of 86.00%, EI-MS: m / z 367.45 [M+H] + .

[0158] Step 5: Oxime reaction

[0159] Compound 7-4 (42 g) was added to a 1L reaction bottle, tetrahydrofuran (300 mL) and concentrated hydrochloric acid (57.09 g) were added and stirred to dissolve, and then cooled to below 5°C with an ice-water bath. Under nitrogen protection and stirring, isopentyl nitrite (16.07 g) dissolved in tetrahydrofuran (50 mL) was slowly added dropwise through a constant pressure dropping funnel. After the addition was completed for 1 h, the mixture was stirred at room temperature for 5 h. After the reaction was completed by monitoring the reaction by TLC spot plate, it was diluted with water, extracted with ethyl acetate, washed with saturated brine for several times, and the organic layer was concentrated and purified by column chromatography to obtain solid compound 7-5 (38 g) with a yield of 83.86%. EI-MS: m / z 396.45 [M+H] + .

[0160] Step 6: Oxime ester reaction

[0161] Compound 7-5 (38 g) and triethylamine (19.4 g) were added to a 1L reaction bottle and dissolved in dichloroethane (300 mL). The temperature was then lowered to 0-5°C, and acetyl chloride (9.03 g) dissolved in dichloroethane (50 mL) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and purified by column chromatography to obtain a yellow-white solid compound 41 (37 g) with a yield of 88.03%. EI-MS: m / z 438.48 [M+H] + .

[0162] Experimental Example 8: Synthesis of Compound 46

[0163]

[0164] The experimental steps Step 1-4 refer to the synthesis scheme of Step 1-4 of compound 2 and will not be described in detail.

[0165] Step 5: Acylation reaction

[0166] Compound 8-4 (37 g) and dichloroethane (300 mL) were added to a 1L reaction bottle, and solid aluminum chloride (19.20 g) was added, then cooled to 0-5°C, and benzoyl chloride (21.23 g) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and then washed with water until neutral, and the liquid was separated. The organic phase was concentrated and purified by column chromatography to obtain solid compound 8-5 (42 g) with a yield of 84.86%. EI-MS: m / z 412.44 [M+H] + .

[0167] Step 6: Oxime reaction

[0168] Compound 8-5 (42 g) was added to a 1L reaction bottle, tetrahydrofuran (300 mL) and concentrated hydrochloric acid (50.56 g) were added and stirred to dissolve, and then cooled to below 5°C with an ice-water bath. Under nitrogen protection and stirring, isopentyl nitrite (15.51 g) dissolved in tetrahydrofuran (50 mL) was slowly added dropwise through a constant pressure dropping funnel. After the addition was completed for 1 h, the mixture was stirred at room temperature for 5 h. After the reaction was completed by monitoring the reaction by TLC spot plate, it was diluted with water, extracted with ethyl acetate, washed with saturated brine for several times, and the organic layer was concentrated and purified by column chromatography to obtain solid compound 8-6 (39 g) with a yield of 86.95%. EI-MS: m / z 440.46 [M+H] + .

[0169] Step 7: Oxime ester reaction

[0170] Compound 8-6 (39 g) and triethylamine (17.92 g) were added to a 1L reaction bottle and dissolved in dichloroethane (300 mL). The temperature was then lowered to 0-5°C, and acetyl chloride (8.34 g) dissolved in dichloroethane (50 mL) was added dropwise. After the reaction was completed, an alkali solution was added for neutralization, and the mixture was washed with water until neutral. The organic phase was concentrated and separated by column chromatography to obtain a yellow-white solid compound 46 (38 g) with a yield of 88.95%. EI-MS: m / z 482.49 [M+H] + .

[0171] Example 9: Preparation of Photosensitive Composition 1

[0172] Trimethylolpropane triacrylate (6.4 g), compound 1 (3 g) and ethyl cellosolve (87.7 g) were added to the acrylic copolymer (15.5 g), and the mixture was sufficiently stirred to obtain a photosensitive composition 1.

[0173] The acrylic copolymer is obtained by the following method: 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate are dissolved in 300 parts by mass of ethyl cellosolve, 0.75 parts by mass of azobisisobutyronitrile is added under a nitrogen atmosphere, and then reacted at 70° C. for 5 hours to obtain an acrylic copolymer.

[0174] Examples 10-16: Preparation of Photosensitive Composition 2-8

[0175] Except that Compound 1 was replaced by the compounds in Table 1, the photosensitive compositions in Examples 10-16 and Comparative Examples 1-5 were obtained by referring to the method in Example 9.

[0176] Table 1

[0177] Example Acrylic copolymer Trimethylolpropane triacrylate Photoinitiator compounds Ethyl Cellosolve Example 9 15.5 g 6.4g 1(3g) 87.7g Example 10 15.5g 6.4g 11(3g) 87.7g Embodiment 11 15.5g 6.4g 16(3g) 87.7g Example 12 15.5g 6.4g 21(3g) 87.7g Example 13 15.5g 6.4g 26(3g) 87.7g Embodiment 14 15.5g 6.4g 31(3g) 87.7g Embodiment 15 15.5g 6.4g 41(3g) 87.7g Example 16 15.5g 6.4g 46(3g) 87.7g Comparative Example 1 15.5g 6.4g OXE01(3g) 87.7g Comparative Example 2 15.5g 6.4g OXE02(3g) 87.7g Comparative Example 3 15.5g 6.4g 339(3g) 87.7g Comparative Example 4 15.5g 6.4g 340(3g) 87.7g Comparative Example 5 15.5g 6.4g 341(3g) 87.7g

[0178] Among them, as a control compound, the structure of the compound used as a photoinitiator in Comparative Examples 1-5 is shown below.

[0179]

[0180] <Hardness test>

[0181] The photosensitive compositions of Examples 9-16 and Comparative Examples 1-5 were coated on a polyethylene terephthalate film having a thickness of 50 μm using a #3 rod coater. A light irradiation device with a belt conveyor was used to irradiate the film with light from a high-pressure mercury lamp having a line power of 80 W / cm. The distance from the lamp to the belt conveyor was set to 10 cm, and the line speed of the belt conveyor was set to 8 cm / min. After curing, the film was placed at room temperature for 24 hours, and then the pencil hardness was measured at a load of 1 kg using a pencil hardness tester. The test results are shown in Table 2.

[0182] Table 2

[0183] Example Photoinitiator compounds Pencil hardness Example 9 1 3H Example 10 11 3H Embodiment 11 16 3H Example 12 21 3H Example 13 26 3H Embodiment 14 31 3H Embodiment 15 41 3H Example 16 46 3H Comparative Example 1 OXE01 1H Comparative Example 2 OXE02 1H Comparative Example 3 339 3H Comparative Example 4 340 3H Comparative Example 5 341 3H

[0184] As can be seen from Table 2, the curing hardness of the photosensitive compositions based on the compounds of the present invention in Examples 9-16 is significantly higher than that of the photosensitive compositions based on OXE01 and OXE02 in Comparative Examples 1-2, and is comparable to the curing hardness of the photosensitive compositions based on 339, 340 and 341 in Comparative Examples 3-5, indicating that the compounds of the present invention are suitable for application in the field of photocuring.

[0185] <Evaluation of photosensitivity under irradiation with blue and green light sources>

[0186] The photosensitive compositions of Examples 9-16 and Comparative Examples 1-5 were coated on a glass substrate using a spin coater, heated to 100°C for 2 minutes at a rotation speed of 1500 rpm using a coating machine, and cooled to room temperature to form a coating film on the surface of the glass substrate. Then, the photosensitive compositions of Examples 9-16 and Comparative Examples 1-5 were cured under irradiation with a blue light source and a green light source, respectively. Table 3 shows the exposure required for curing, and the smaller the value, the better the photosensitivity.

[0187] Table 3

[0188]

[0189] As shown in Table 3, under the irradiation of blue and green light sources, the energy required for curing the photosensitive composition to which the compound of the present invention is added is significantly less than the energy required for curing the photosensitive composition to which the reference compounds (OXE01, OXE02, 339, 340 and 341) are added. Compared with the compounds (OXE01, OXE02, 339, 340 and 341) used in Comparative Examples 1-5, the compounds of the present invention have more excellent photosensitivity and are useful as photoinitiators for optical purposes.

[0190] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention.

Claims

1. A compound of formula (I), in, Each R1 is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl and C 6-20 Aryl, the alkyl, cycloalkyl or aryl is unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C 1-20 Alkyl, halogen and cyano; Each R2 is independently selected from C 1-20 Alkyl and C 3-20 Cycloalkyl, the alkyl or cycloalkyl is unsubstituted or substituted with one or more R b Replace; each R b Each independently selected from C 1-20 Alkyl, -OC 1-20 Alkyl, halogenated C 1-20 Alkyl, halogen and cyano; R3, R4, R5, R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, nitro, cyano, C 1-20 Alkyl, C 6-20 Aryl, 4-20 membered heterocyclic group, -C(=O)C 1-20 Alkyl, -C(=O)C 6-20 Aryl and The aryl or heterocyclic group is unsubstituted or substituted by one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-20 Alkyl, -OC 1-20 Alkyl and halogenated C 1-20 Substitution of alkyl groups; R 10 , R 11 and R 12 are each independently selected from hydrogen and methyl.

2. The compound according to claim 1, characterized in that Each R1 is independently selected from C 1-10 Alkyl, C 3-10 Cycloalkyl and C 6-10 Aryl, the alkyl, cycloalkyl or aryl is unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-10 Alkyl, -OC 1-10 Alkyl, halogenated C 1-10 Alkyl, halogen and cyano; Preferably, each R1 is independently selected from C 1-6 Alkyl, C 3-10 Cycloalkyl and phenyl, the alkyl, cycloalkyl or phenyl being unsubstituted or substituted by one or more R a Replace; each R a Each independently selected from C 1-6 Alkyl, -OC 1-6 Alkyl, halogenated C 1-6 Alkyl, halogen and cyano; More preferably, each R1 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl; Further preferably, each R1 is independently selected from methyl and phenyl; More preferably, each R1 is independently methyl.

3. The compound according to claim 1 or 2, characterized in that Each R2 is independently selected from C 1-9 Alkyl and C 5-9 Cycloalkyl, the alkyl or cycloalkyl is unsubstituted or substituted with one or more R b Replace; each R b Each independently selected from C 1-9 Alkyl, -OC 1-9 Alkyl, halogenated C 1-9 Alkyl, halogen and cyano; Preferably, each R2 is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and the methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl is unsubstituted or replaced by one or more R b Replace; each R b Each independently selected from C 1-6 Alkyl, -OC 1-6 Alkyl, halogenated C 1-6 Alkyl, halogen and cyano; More preferably, R2 is selected from methyl, Further preferably, R2 is selected from methyl.

4. The compound according to any one of claims 1 to 3, characterized in that R3, R5, R6, R8 and R9 are each independently selected from hydrogen and C 1-10 alkyl; Preferably, R5 is hydrogen, and R3, R6, R8 and R9 are each independently selected from hydrogen and C 1-4 alkyl; More preferably, R5 is hydrogen, and R3, R6, R8 and R9 are each independently selected from hydrogen, methyl, ethyl, n-propyl and n-butyl; Further preferably, R5 is hydrogen, and R3, R6, R8 and R9 are each independently selected from hydrogen and methyl.

5. The compound according to any one of claims 1 to 4, characterized in that R4 and R7 are each independently selected from hydrogen, halogen, nitro, cyano, C 1-10 Alkyl, C 6-10 Aryl, -C(=O)C 1-10 Alkyl, -C(=O)C 6-10 Aryl and The aryl group is unsubstituted or substituted with one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-10 Alkyl, -OC 1-10 Alkyl and halogenated C 1-10 Substitution of alkyl groups; Preferably, R4 and R7 are each independently selected from hydrogen, nitro, C 1-6 Alkyl, -C(=O)C 1-6 Alkyl, -C(=O)C 6-10 Aryl and The aryl group is unsubstituted or substituted with one or more R c Replace; each R c are independently selected from halogen, nitro, cyano, C 1-6 Alkyl, -OC 1-6 Alkyl and halogenated C 1-6 Substitution of alkyl groups; More preferably, R4 and R7 are each independently selected from hydrogen, nitro, methyl, ethyl, n-propyl, n-butyl, Further preferably, R4 and R7 are each independently selected from hydrogen, nitro, More preferably, R4 and R7 are not both hydrogen or nitro, and when one of them is hydrogen, the other is 6. The compound according to any one of claims 1 to 5, characterized in that R 10 , R 11 and R 12 are each independently hydrogen.

7. The compound according to any one of claims 1 to 6, characterized in that The compound is shown in formula (II): Among them, R 1 , R 2 , R 4 and R 7 As defined in any one of claims 1 to 6.

8. A compound selected from:

9. A photosensitive composition comprising the compound according to any one of claims 1 to 8; Preferably, the photosensitive composition further comprises at least one of the following components: a) alkali soluble resin; b) photopolymerizable compounds; c) solvent; More preferably, the photosensitive composition comprises the following components in parts by weight: 1-5 parts of the compound according to any one of claims 1-8; 10-20 parts of an alkali-soluble resin; 5-10 parts of a photopolymerizable compound; and 80-100 parts of solvent.

10. A photoresist comprising the following components: i) a compound according to any one of claims 1 to 8; ii) alkali soluble resin; iii) photopolymerizable compounds; iv) auxiliary agents; Preferably, the auxiliary agent is selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

11. Use of the compound according to any one of claims 1 to 8, the photosensitive composition according to claim 9 or the photoresist according to claim 10 in the field of photocuring.

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