Photoinitiating composition, photocurable composition, photoresist, use of photocurable composition and photoresist

Abstract

The application provides a photoinitiating composition, a photocuring composition, a photoresist, application of the photocuring composition and application of the photoresist. The photoinitiating composition comprises at least one diacyl diphenyl sulfide derivative and at least one oxime ester compound, the diacyl diphenyl sulfide derivative is selected from a compound as shown in formula I, and the oxime ester compound is selected from a compound as shown in formula II. The photoinitiating composition has good photosensitivity and yellowing resistance when applied.

Description

Technical Field

[0001] This invention relates to the field of photocurable materials technology, and more specifically, to a photoinitiating composition, a photocurable composition, a photoresist, the application of the photocurable composition, and the application of the photoresist. 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 issues that technicians are most concerned about is curing efficiency or sensitivity. The key factors affecting curing efficiency are the structure of the photoinitiator and the components of the co-initiator used in conjunction with it.

[0003] For example, the thioether oxime ester compounds proposed in the patent with authorization announcement number CN1241562B are among the most successful photoinitiators used in photoresist formulations, such as commercial products. OXE 01, with its relatively good sensitivity and low yellowing, is well-known, widely studied, and used by those skilled in the art, especially in transparent photoresist and RGB color photoresist formulations. Later, international patent application WO2002 / 100903 disclosed oxime ester compounds with more complex substituents on the diphenyl sulfide parent structure, and also disclosed oxime ester compounds with carbazole as the parent structure. Commercially available products include those from BASF. While OXE 02 offers improved sensitivity, its stronger yellowing tendency severely limits its use in both transparent and colored photoresists. Chinese patent applications CN101565472A and CN103833872A, based on the aforementioned patented compounds, modified the side chains but did not fundamentally alter the sensitivity and yellowing properties of the corresponding oxime ester compounds. Examples include PBG305 and PBG304 from Changzhou Qiangli Co., Ltd., and diketone oxime ester compounds 1, 3, and 4 disclosed in patent application CN103833872A. Patent application CN101528694A discloses oxime ester compounds with nitrocarbazole as the parent compound, and patent application CN103153952A discloses oxime ester compounds with benzo[a]carbazole as the parent compound. Due to the introduction of the chromophore nitro group or the highly conjugated structure of benzo[a]carbazole, the UV absorption spectra of the corresponding oxime ester compounds show a significant red shift, as seen in NCI-831 from Idicco Co., Ltd. and BASF. The two commercially available OXE 03 products exhibit more effective absorption of the 365nm emitted light from the light source, demonstrating higher sensitivity. However, the significantly red-shifted ultraviolet absorption spectrum also imparts a yellowish color to the compound and significant yellowing in photoresists. Therefore, they are more suitable for use in black photoresist formulations and are difficult to use in transparent and RGB color photoresists.

[0004] To improve color saturation or hiding power, the pigment content in photocurable formulations is increasing, especially in high-pigment-content black photoresists. However, the light energy utilization during curing is reduced due to pigment absorption, necessitating the development of photoinitiators or photoinitiator compositions with higher sensitivity. Sensitizing existing photoinitiators is one method to improve sensitivity. Sensitizers have become frequently used components in photocurable compositions, especially photoresist formulations. Sensitizers described in the prior art, such as those disclosed in patent application CN1241562A, include benzophenone and its derivatives, such as 4-(4-methylphenylthio)benzophenone (trade name Omnirad BMS) or 4,4'-di(diethylamino)benzophenone, thioxanthrone and its derivatives, such as 2-isopropylthioxanthrone, anthraquinone and its derivatives, such as 2-ethylanthrquinone, coumarin derivatives, such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin (Esacure 3644 from IGM Resins), camphorquinone, phenothiazine and its derivatives, 3-(aromaticylmethylene)thiazoline, razotanine and its derivatives, eosin, rhodamine, acridine, anthocyanins, tertiary amine compounds; among which benzophenone and its derivatives, thioxanthrone and its derivatives, anthraquinone and its derivatives, and coumarin derivatives are preferred. Experiments have shown that these sensitizers, when used in combination with thioether oxime esters, do not exhibit satisfactory sensitizing effects. Some compounds, due to the presence of phenolic hydroxyl or aniline groups such as eosin, anthocyanins, and phenothiazines, reduce the photocuring efficiency of the photocurable composition. Among the four preferred classes of compounds, although they are also photoinitiators themselves, their photoinitiating efficiency is much lower than that of thioether oxime ester compounds, and they do not exhibit a synergistic sensitizing effect when used in combination with thioether oxime esters. Moreover, some varieties, such as 2-isopropylthioxanthone and 2-ethylanthraquinone, cause severe yellowing of the formulation due to their long-wavelength UV absorption spectra, rendering them unusable. Therefore, in reality, there are no ideal sensitizers in the existing technology.

[0005] However, technicians' pursuit of improving performance such as exposure sensitivity, resolution, and thermal stability is endless, and existing products and formulation technologies are constantly facing new challenges.

[0006] To improve the light transmittance of transparent photoresists and the color purity of colored photoresists, the photoinitiator used needs to have lower yellowing properties. Therefore, it is still necessary to develop new photoinitiator products with higher sensitivity and lower yellowing properties. Summary of the Invention

[0007] The main objective of this invention is to provide a photoinitiator composition, a photocurable composition, a photoresist, the application of the photocurable composition, and the application of the photoresist, in order to solve the problems of insufficient photosensitivity and yellowing resistance of photoinitiators in the prior art.

[0008] To achieve the above objectives, according to one aspect of the present invention, a photoinitiating composition is provided, the photoinitiating composition comprising at least one diacyl diphenyl sulfide derivative and at least one oxime ester compound, wherein the diacyl diphenyl sulfide derivative is selected from compounds shown in Formula I, and the oxime ester compound is selected from compounds shown in Formula II.

[0009]

[0010] In Formula I, R1 and R2 are each independently selected from any one of the following groups: C6-C20 substituted or unsubstituted aromatic group, C4-C20 substituted or unsubstituted heteroaromatic group, C6-C20 substituted or unsubstituted aromatic acyl group, C4-C20 substituted or unsubstituted heteroaromatic acyl group, C1-C12 substituted or unsubstituted alkoxy acyl group, R 11 R 12 R 13 R 14 R 15 R 16 R 18 and R 19 Each is independently selected from any one of H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, and CN; in Formula II, R3 is selected from any one of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20 OOC-substituted C1-C16 alkyl groups, C3-C16 alkyl groups substituted with one or more halogen atoms, C4-C7 cycloalkyl groups, C4-C7 heterocyclic groups, phenyl groups, or hydroxyl groups, and simultaneously inserted with one or more oxygen atoms or sulfur atoms; phenyl groups substituted with one or more halogen atoms, C1-C12 alkyl groups, C1-C4 alkoxy groups, or CN groups; C4-C7 cycloalkyl groups; R3 can be connected to the adjacent Ar1 to form any of the five-membered to seven-membered rings; R4 is selected from any of the following groups: C1-C11 substituted or unsubstituted alkyl groups, C3-C5 alkenyl groups, substituted or unsubstituted phenyl groups, C1-C4 alkoxy groups, or phenoxy groups; Ar1 ​​is a group whose parent is a C6-C20 aromatic group, a C4-C30 heteroaromatic group, or a coumarin group, and the parent is unsubstituted, or substituted with one or more halogen atoms, nitro groups, or R groups. 10 X-、 Replace, where R 10Selected from any one of the following groups: C1-C12 alkyl, C3-C12 alkyl with one or more oxygen or sulfur atoms inserted, C3-C8-cycloalkyl, C3-C8 heterocyclic, C2-C7 alkenylmethyl, C6-C15 aromatic, C4-C15 heteroaromatic, wherein the hydrogen atoms of the C6-C15 aromatic and C4-C15 heteroaromatic groups may be substituted by fluorine, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio or C1-C4 alkylsulfonyl; the hydrogen atoms of the C1-C12 alkyl, C3-C12 alkyl with one or more oxygen or sulfur atoms inserted, and C3-C8-cycloalkyl may be substituted by F, C1-C4 alkoxy, OH, OOCR4, COOR9, (R9O)2P(O), (CH3)3Si or phenyl; R9 is a C1-C4 alkyl; R 10 Or R 10 It can optionally connect with atoms on adjacent parent atoms to form any of the five-membered to seven-membered rings, where X is a straight bond, O, S, CO, or R. 10 'N, R 10 ' is a C1-C12 alkyl group, or X is R 10 When 'N, R 10 R 10 'N is R3' is selected from any of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20 OOC-substituted C1-C16 alkyl groups, C3-C16 alkyl groups substituted with one or more halogen atoms, C4-C7 cycloalkyl groups, C4-C7 heterocyclic groups, phenyl groups, or hydroxyl groups, and simultaneously inserted with one or more oxygen atoms or sulfur atoms; phenyl groups substituted with one or more halogen atoms, C1-C12 alkyl groups, C1-C4 alkoxy groups, or CN groups; C4-C7 cycloalkyl groups; R3' can be connected to an adjacent Ar1 to form any of the five-membered to seven-membered rings; R 20 Selected from any of the following groups: H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl, C3-C8 alkyl containing one or more O, S spacers and hydroxyl groups and substituted with OOCR4, five- or six-membered ring containing one or two O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; m1 and n are each 0 or 1; substituents on Ar1 can be arbitrarily combined with adjacent substituents and atoms on the parent to form any of the five- to seven-membered rings.

[0011] To achieve the above objectives, according to one aspect of the present invention, a photocurable composition is provided, comprising a photocurable resin and an initiator, wherein the initiator is any of the above-described photoinitiating compositions.

[0012] To achieve the above objectives, according to one aspect of the present invention, an application of any of the above-mentioned photocurable compositions is provided, the application including using the photocurable composition as an ink, coating, sealant, optical film or adhesive, preferably as a negative passivation film, photocurable photosensitive surface coating, barrier film or polarizer coating.

[0013] To achieve the above objectives, according to one aspect of the present invention, a photoresist is provided, comprising a multifunctional acrylate monomer, an alkali-soluble resin, an initiator, and a solvent, wherein the initiator is a photoinitiating composition of any of the above-mentioned types.

[0014] To achieve the above objectives, according to one aspect of the present invention, the application of any of the above-mentioned photoresists is provided, the photoresist further comprising pigments, the application including using the photoresist as a sealant, optical film, colored matrix, optical spacer or filter, preferably as a negative passivation film, photocurable photosensitive surface coating, barrier film or polarizer coating.

[0015] When the above-mentioned photoinitiating composition is applied using the technical solution of the present invention, it exhibits good photosensitivity and resistance to yellowing. Detailed Implementation

[0016] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0017] As analyzed in the background section of this application, the sensitivity and resistance to yellowing of photoinitiators in the prior art still need to be improved. In order to solve this problem, this application provides a photoinitiating composition, a photocuring composition, a photoresist, and the application of the photoresist.

[0018] In one typical embodiment of this application, a photoinitiating composition is provided, comprising at least one diacyldiphenyl sulfide derivative and at least one oxime ester compound, wherein the diacyldiphenyl sulfide derivative is selected from compounds shown in Formula I, and the oxime ester compound is selected from compounds shown in Formula II.

[0019]

[0020] In formula I,

[0021] R1 and R2 are each independently selected from any of the following groups: C6-C20 substituted or unsubstituted aromatic group, C4-C20 substituted or unsubstituted heteroaromatic group, C6-C20 substituted or unsubstituted aromatic acyl group, C4-C20 substituted or unsubstituted heteroaromatic acyl group, C1-C12 substituted or unsubstituted alkoxy acyl group; R 11 R 12 R 13 R 14 R 15 R 16 R 18 and R 19 Each is independently selected from any one of H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, and CN;

[0022] In Formula II, R3 is selected from any of the following groups: C1-C16 substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, C4-C7 cycloalkyl; R3 may be connected to the adjacent Ar1 to form any of the five-membered to seven-membered rings; R4 is selected from any of the following groups: C1-C11 substituted or unsubstituted alkyl, C3-C5 alkenyl, substituted or unsubstituted phenyl, C1-C4 alkoxy, phenoxy; Ar1 ​​is a group whose parent is a C6-C20 aromatic group, a C4-C30 heteroaromatic group, or a coumarin group, and the parent is unsubstituted, or is surrounded by one or more halogen atoms, nitro groups, or R groups. 10 X-、 Replace, where R 10 Selected from any one of the following groups: C1-C12 alkyl, C3-C12 alkyl with one or more oxygen or sulfur atoms inserted, C3-C8-cycloalkyl, C3-C8 heterocyclic, C2-C7 alkenylmethyl, C6-C15 aromatic, C4-C15 heteroaromatic, wherein the hydrogen atoms of the C6-C15 aromatic and C4-C15 heteroaromatic groups may be substituted by fluorine, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio or C1-C4 alkylsulfonyl; the hydrogen atoms of the C1-C12 alkyl, C3-C12 alkyl with one or more oxygen or sulfur atoms inserted, and C3-C8-cycloalkyl may be substituted by F, C1-C4 alkoxy, OH, OOCR4, COOR9, (R9O)2P(O), (CH3)3Si or phenyl; R9 is a C1-C4 alkyl; R 10 Or R 10 It can optionally connect with atoms on adjacent parent atoms to form any of the five-membered to seven-membered rings, where X is a straight bond, O, S, CO, or R. 10 'N, R 10 ' is a C1-C12 alkyl group, or X is R 10 When 'N, R 10 R10 'N is R3' is selected from any of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20 OOC-substituted C1-C16 alkyl groups, C3-C16 alkyl groups substituted with one or more halogen atoms, C4-C7 cycloalkyl groups, C4-C7 heterocyclic groups, phenyl groups, or hydroxyl groups, and simultaneously inserted with one or more oxygen atoms or sulfur atoms; phenyl groups substituted with one or more halogen atoms, C1-C12 alkyl groups, C1-C4 alkoxy groups, or CN groups; C4-C7 cycloalkyl groups; R3' can be connected to an adjacent Ar1 to form any of the five-membered to seven-membered rings; R 20 Selected from any of the following groups: H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl, C3-C8 alkyl containing one or more O, S spacers and hydroxyl groups and substituted with OOCR4, five- or six-membered ring containing one or two O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; m1 and n are each 0 or 1; substituents on Ar1 can be arbitrarily combined with adjacent substituents and atoms on the parent to form any of the five- to seven-membered rings.

[0023] The photoinitiating composition of this application exhibits good photosensitivity and resistance to yellowing when applied.

[0024] In one embodiment, the C1-C12 substituted alkoxyacyl groups in R1 and R2 are selected from any one of the following groups: substituted with one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, R 20 OOC-substituted C1-C12 alkoxyacyl groups, with one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic groups, phenyl, C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy-C2-C4 alkoxy, phenoxy-C2-C4 alkoxy, R4COO, R 20 OOC-substituted C2-C12 alkoxyacyl groups; wherein C6-C20 substituted aromatic groups, C4-C20 substituted heteroaryl groups, and C6-C20 substituted aromatic acyl groups, and the substituents on the C4-C20 substituted heteroaryl acyl groups include halogen atoms, R 20 -OR 30 -SR 30 -NR 31 R 32 -COOR 30 -CONR 31 R 32Furthermore, the substituents can arbitrarily combine with atoms on the parent ring to form five- to seven-membered rings; R 20 and R 30 Each group is independently selected from any of the following groups: H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, or C3-C7 cycloalkyl groups, C3-C8 alkyl containing one or more O, S spaces and hydroxyl groups substituted with OOCR4, five- or six-membered rings containing one or two O, S, or N heteroatoms, phenyl, C1-C4 alkylphenyl; R 31 and R 32 Each group is independently selected from any of the following groups: C1-C4 alkyl, C1-C4 alkyl substituted with a hydroxyl group; or NR 31 R 32 for

[0025] Alternatively, in R4 above, the C1-C11 substituted alkyl group is a C1-C11 alkyl group substituted by one or more halogen atoms, C4-C7 cycloalkyl groups, or CN, and the substituted phenyl group is a phenyl group substituted by one or more halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, or CN.

[0026] Preferably, R1 and R2 are each independently selected from any one of the following groups: phenyl, phenyl substituted with one or more F, methyl, or C1-C4 alkoxyacyl groups, thienyl, benzoyl, benzoyl substituted with one or more F, methyl, or C1-C4 alkoxyacyl groups, C1-C4 alkoxyacyl, phenyl substituted with one or more C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, R 20 The C1-C4 alkoxyacyl group substituted with OOC is replaced by a C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy-C2-C4 alkoxy, 2-phenoxyethoxy, CH3COO, or R. 20 OOC-substituted C2-C4 alkoxyacyl group; R 11 R 12 R 13 R 14 R 15 R 16 R 18 R 19 Each of the following is independently any one of H, C1-C4 alkyl, C1-C4 alkoxy, and F; R 20 It is a C1-C8 alkyl group.

[0027] For oxime ester compounds, preferably, the parent structure of the Ar1 is selected from any one of the following groups: benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, thiaanthracene, thioxanthone, fluorene, benzofluorene, carbazole, benzocarbazole, and dibenzocarbazole.

[0028] In one embodiment, at least one of the above-mentioned oxime ester compounds is selected from compounds shown in Formula III:

[0029]

[0030] Wherein, n1 is 1 or 0; R3 is selected from any of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20 OOC-substituted C1-C16 alkyl, C3-C16 alkyl substituted with one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic group, phenyl, hydroxyl group and simultaneously inserted with one or more oxygen or sulfur atoms, phenyl, phenyl substituted with one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN group, C4-C7 cycloalkyl; R3 can be connected to an adjacent benzene ring to form any of five-membered to seven-membered rings; R4 is selected from any of the following groups: C1-C11 alkyl, C1-C16 alkyl substituted with one or more halogen atoms, C4-C7 cycloalkyl, CN group, C3-C5 alkenyl group, phenyl, phenyl substituted with one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN group, C1-C4 alkoxy, phenoxy; R 21 R 22 R 23 R 24 Each is independently H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, or CN; R 25 R 26 R 27 R 28 R 29 Each of these can be independently represented by H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, NO2, or C1-C8 substituted or unsubstituted alkyl acyl groups. The C6-C15 substituted or unsubstituted aromatic acyl group, the C4-C15 substituted or unsubstituted heteroaromatic acyl group, and the substituents of the substituted C1-C8 alkyl group are selected from any one or more of halogen atoms, C4-C7 cycloalkyl groups, hydroxyl groups, CN, and R4COO. The substituents on the substituted C6-C15 aromatic group and the substituted C4-C15 heteroaromatic group are each independently selected from halogen atoms, CN, R4COO. 20 OR 30 SR 30 NR31 R 32 COOR 30 CONR 31 R 32 Any one of them, R 31 ,R 32 Each is independently a C1-C4 alkyl group, a C1-C4 alkyl group substituted with a hydroxyl group; or NR 31 R 32 For

[0031] Preferably, when the oxime ester compound has Formula III above, R3 is selected from any one of C1-C6 alkyl, C1-C3 alkyl, and C4-C7 cycloalkyl substituted with a C4-C7 cycloalkyl group; R4 is methyl or phenyl; R 21 R 22 R 23 R 24 Each is independently selected from any one of H, C1-C4 alkyl, C1-C4 alkoxy, and F; R 25 R 26 R 27 R 28 R 29 Each is independently selected from H, C1-C8 substituted or unsubstituted alkyl, F, C1-C8 alkyl acyl. The substituted or unsubstituted benzoyl group, the substituted or unsubstituted thiophene-2-formyl group, and the substituted or unsubstituted benzofuran-2-formyl group, wherein the substituent of the C1-C8 alkyl group is one or more F, the substituent of the C4-C7 cycloalkyl group, the substituent of the substituted benzoyl group, the substituted thiophene-2-formyl group, and the substituent of the substituted benzofuran-2-formyl group is F, R 20 OR 30 COOR 30 CONR 31 R 32 R3' is selected from any one of C1-C6 alkyl groups, C1-C3 alkyl groups substituted with a C4-C7 cycloalkyl group, and any one of C4-C7 cycloalkyl groups; R 20 R 30 Each is independently selected from H, C1-C8 alkyl, C1-C4 alkyl substituted with one or more F, C3-C7 cycloalkyl, C3-C8 alkyl containing one or more O, S spacers and hydroxyl, OOCR4 substituted, five- or six-membered rings containing one or two O, S, N heteroatoms, phenyl, and any one of C1-C4 alkylphenyl; R 31 ,R 32 Each is independently selected from any one of C1-C4 alkyl groups; or NR 31R 32 It has a ring structure. The above substitutions can be either mono- or poly-substituted.

[0032] In another embodiment, at least one of the above-mentioned oxime ester compounds is selected from any one of the compounds shown in Formula IV, Formula V, and Formula VI:

[0033]

[0034]

[0035] Among them, Y1, Y2, and Y3 are each independently selected from H, Ar2CO, Any one of the following, or Y3 is NO2; wherein m2, n2, n3, n4 are each independently 1 or 0; R3 is selected from any one of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20 OOC-substituted C1-C16 alkyl groups, C3-C16 alkyl groups substituted with one or more halogen atoms, C4-C7 cycloalkyl groups, C4-C7 heterocyclic groups, phenyl groups, or hydroxyl groups, and simultaneously inserted with one or more oxygen atoms or sulfur atoms; phenyl groups substituted with one or more halogen atoms, C1-C12 alkyl groups, C1-C4 alkoxy groups, or CN groups; C4-C7 cycloalkyl groups; R3 can be connected to an adjacent Ar1 to form any of five-membered to seven-membered rings; R4 is selected from any of the following groups: C1-C11 alkyl groups, C1-C16 alkyl groups substituted with one or more halogen atoms, C4-C7 cycloalkyl groups, or CN groups, C3-C5 alkenyl groups, phenyl groups, phenyl groups substituted with one or more halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, or CN groups, C1-C4 alkoxy groups, or phenoxy groups; R5, R6, R7, and R8 are each independently selected from any of the following groups: H, C1-C8 alkyl, C3-C8 alkyl with one or two oxygen atoms inserted, C2-C7 alkenylmethyl, phenyl; the hydrogen atoms of the alkyl and phenyl groups are optionally replaced by halogen atoms, C4-C7 cycloalkyl, hydroxyl, R4COO, COOR9, (R9O)2P(O), (CH3)3Si, or phenyl; R9 is a C1-C4 alkyl; R5, R6, R7, and R8 can each independently form any of five-membered to seven-membered rings together with adjacent substituents and atoms on the parent group; Ar2 is selected from any of the following groups: C6-C15 aromatic groups, C4-C15 heteroaromatic groups; wherein the hydrogen atom on the carbon atom can be replaced by any of the following: fluorine atom, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, or C1-C4 alkylsulfonyl, and the hydrogen atom on the C1-C4 alkyl group is optionally replaced by any of the following: fluorine atom, C1-C4 alkoxy, or R4COO; R41 R 42 R 43 R 44 R 45 Each group is independently selected from any one of the following groups: H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, C1-C8 substituted or unsubstituted alkyl acyl group. The substituents of the C6-C15 substituted or unsubstituted aromatic acyl groups, the C4-C15 substituted or unsubstituted heteroaryl acyl groups, and the C1-C8 substituted alkyl groups are selected from any one or more of halogen atoms, C4-C7 cycloalkyl groups, hydroxyl groups, CN, and R4COO; the substituents of the C6-C15 substituted aromatic acyl groups and the C4-C15 heteroaryl acyl groups are selected from H, halogen atoms, CN, and R. 20 OR 30 SR 30 NR 31 R 32 COOR 30 CONR 31 R 32 Any one or more of the following; R 20 R 30 Each independently is H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, or C3-C7 cycloalkyl groups, C3-C8 alkyl groups containing one or more O, S intercalators and hydroxyl or acetoxy substitutions, five-membered or six-membered rings containing one or two O, S, or N heteroatoms, phenyl, C1-C4 alkylphenyl; R 31 R 32 Each is independently a C1-C4 alkyl group, any one of C1-C4 alkyl groups substituted with a hydroxyl group; or NR 31 R 32 For

[0036] In one embodiment, at least one of the above-mentioned oxime ester compounds is selected from any one of the compounds shown in Formula IV, Formula V, and Formula VI: wherein Y1, Y2, and Y3 are each independently selected from Ar2CO, Any one of the following groups, wherein m2, n2, n3, n4 are each independently 1 or 0; or Y3 is NO2; R3 is selected from any one of the following groups: C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, benzyl, substituted or unsubstituted phenyl; R4 is selected from any one of the following groups: methyl, phenyl, C1-C4 alkoxy; R5, R6, R7, R8 are each independently selected from any one of the following groups: C1-C4 alkyl, phenyl, the hydrogen of the alkyl and phenyl groups is substituted by COOR9, (R9O)2P(O), (CH3)3Si, or phenyl; R9 is a C1-C4 alkyl; Ar2 is selected from any one of the following groups: phenyl, thiophene, benzofuranyl; the hydrogen on the phenyl group may be substituted by any one of fluorine, C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 alkylsulfonyl, and the hydrogen on the C1-C4 alkyl group is substituted by any one of fluorine or C1-C4 alkoxy; R 41 R 42 R 43 R 44 R 45 Each is independently selected from any one of the following groups: H, C1-C4 alkyl, C1-C4 alkoxy, halogen atom, CN.

[0037] When these oxime ester compounds are used in combination with compounds of Formula I in a certain proportion, they can produce a higher sensitivity effect. However, when Y1 is nitro, for example, the combination of NCI 831, a product of ADEKA Corporation of Japan, with compounds of Formula I-14 does not have an effect on increasing sensitivity.

[0038] In another embodiment, at least one of the above-mentioned oxime ester compounds is selected from compounds shown in Formula VII:

[0039]

[0040] Wherein, R3 is selected from any one of the following groups: C1-C16 alkyl, surrounded by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl, CN, R4COO, R 20OOC-substituted C1-C16 alkyl, C3-C16 alkyl substituted with one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclic, phenyl, hydroxyl and simultaneously inserted with one or more oxygen atoms or sulfur atoms, phenyl, phenyl substituted with one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; R4 is selected from any of the following groups: C1-C11 alkyl, C1-C16 alkyl substituted with one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl, phenyl substituted with one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN, C1-C4 alkoxy, phenoxy; R 51 R 52 R 53 R 54 R 55 Each is independently selected from any one of the following groups: H, halogen atom, CN, R. 20 OR 30 SR 30 NR 31 R 32 COOR 30 CONR 31 R 32 Adjacent substituents together can arbitrarily form any of the five- to seven-membered ring structures; R 20 R 30 Each is independently selected from any of the following groups: H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, or C3-C7 cycloalkyl groups, C3-C8 alkyl groups containing one or more O, S spaces and hydroxyl or acetoxy substitutions, five-membered or six-membered rings containing one or two O, S, or N heteroatoms, phenyl, C1-C4 alkylphenyl; R 31 ,R 32 Each is independently a C1-C4 alkyl group, any one of C1-C4 alkyl groups substituted with a hydroxyl group; or NR 31 R 32 for

[0041] Preferably, at least one of the above-mentioned oxime ester compounds is selected from compounds shown in Formula VII: wherein R3 is selected from any one of the following groups: C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, benzyl, substituted or unsubstituted phenyl; R4 is selected from any one of the following groups: methyl, phenyl, C1-C4 alkoxy; R 51 R 52 R 53 R 54 R 55Each group is independently selected from any one of the following groups: H, methoxy, methylthio.

[0042] When these oxime ester compounds are used in specific proportions with compounds of Formula I, they can produce a higher sensitivity effect.

[0043] In one embodiment, the above-mentioned diacyl diphenyl sulfide derivative is selected from one of the following compounds or any mixture thereof.

[0044]

[0045]

[0046] When diacyl diphenyl sulfide derivatives with the above structure are used in combination with certain oxime ester compounds in a certain proportion, they can produce additional high sensitivity effects.

[0047] In one embodiment, the above-mentioned oxime ester compound is selected from one of the following compounds or any mixture thereof:

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] When the oxime ester compound having the above structure is combined with the above diacyl diphenyl sulfide derivative, the photocuring sensitivity value is significantly higher than the sensitivity value of the oxime ester compound used alone.

[0056] To further enhance the synergistic sensitizing effect of the two substances, the molar ratio of the diacyl diphenyl sulfide derivative to the oxime ester compound is preferably 0.1:1 to 3:1, more preferably 0.3:1 to 1.4:1. Different optimal combination ratios exist depending on the diacyl diphenyl sulfide derivative and different combinations of substances.

[0057] The following provides an example illustrating the preparation method of the diacyl diphenyl sulfide derivative of this application.

[0058] One of the preparation methods is as follows:

[0059] Step 1, sulfide raw materials It undergoes a Friedel-Crafts acylation reaction with R1COX, followed by a second Friedel-Crafts acylation reaction with R2COX. The reaction solution is then hydrolyzed to obtain Formula I or an intermediate of Formula I.

[0060] The second step involves a substitution reaction when R1 or R2 has an active group, for example, R1 or R2 is p-fluorophenyl, to obtain the final formula I, such as formula I-11 and formula I-12.

[0061] The sulfide raw material Any compound that meets the requirements from the existing literature can be used, such as diphenyl sulfide, 2-methyl diphenyl sulfide, etc.; R1 and R2 in R1COX or R2COX can be the same or different, and X is Cl or Br;

[0062] Another method for preparing diacyl diphenyl sulfide derivatives is as follows:

[0063] The first step, preparation of intermediate formula III, involves using formula IX as the starting material and R1COX as the acylation reagent, followed by a Friedel-Crafts acylation reaction to obtain intermediate formula X, which is then reacted with formula XI. Thiophenol compounds undergo thioetherification to yield intermediate formula III (I-A); thioetherification reactions usually need to be carried out under alkaline conditions in polar solvents, and the reaction solution is purified by necessary steps such as washing with water and crystallization to obtain intermediate formula I-A;

[0064]

[0065] The second step involves the intermediate formula I-A undergoing a Friedel-Crafts acylation reaction with the acylation reagent R2COX to obtain formula I.

[0066] When R1 or R2 is a C6-C20 aryl group and has an ortho-substituent COOR 30 For example, equations I-7 to I-9,

[0067] The third method for preparing diacyl diphenyl sulfide derivatives is as follows:

[0068] Step 1, sulfide raw materials It undergoes a Friedel-Crafts acylation reaction with one or two moles of phthalic anhydride to give a diacylated or monoacylated product; the monoacylated product then undergoes a second Friedel-Crafts acylation reaction with R2COX, and the reaction solution is hydrolyzed to give an intermediate of formula I containing a carboxyl group;

[0069] The second step involves subjecting the intermediate of Formula I containing a carboxyl group to esterification, amidation, or other possible reactions such as condensation to obtain the final product of Formula I.

[0070] One method for preparing oxime ester compounds is as follows: using R4COCl or (R4CO)2O as esterifying agents, the oxime compound of formula II-A is esterified to obtain formula II.

[0071]

[0072] The specific operating conditions for each of the above preparation methods can be obtained by those skilled in the art through experimentation based on existing technology and the specific preparation examples of this application below, and will not be repeated here.

[0073] In another typical embodiment of this application, a photocurable composition is provided, comprising a photocurable resin and an initiator, wherein the initiator is any of the above-described photoinitiating compositions.

[0074] Because the photoinitiating composition of this application has high photosensitivity and high resistance to yellowing, the photocurable composition of this application has high sensitization efficiency and thermal stability.

[0075] The aforementioned photocurable resin may contain at least one free radical polymerizable compound. The free radical polymerizable compound may be selected from acrylates, methacrylate compounds, resins containing acrylate or methacrylate groups, or any mixture thereof.

[0076] Preferably, among the above-mentioned free radical polymerizable compounds, examples of low molecular weight double-bonded compounds include alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, and dialkylaminoalkyl methacrylates, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, and polysiloxane acrylates; other examples include acrylonitrile, vinyl acetate, vinyl ethers, styrene, and N-vinylpyrrolidone. Examples of compounds containing two or more double bonds include diacrylates of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate. Examples of high molecular weight double-bonded compounds include a large class of substances commonly known as oligomers, such as acrylic epoxy resins, acrylic polyester resins, unsaturated polyester resins, acrylic polyether resins, and acrylic polyurethane resins, with molecular weights generally ranging from 500 to 3000.

[0077] The above-mentioned photocurable compositions are used to produce colored or uncolored inks, coatings, and adhesives. Specific applications include printing, dental materials, optical materials, optical films, insulating films, polarizers, cylindrical gaskets, microscope lenses, fiber optic coatings, substrate protective coatings, electronic device protective coatings, passivation films, sealants, PCB solder resist layers, liquid or dry film anti-corrosion materials, 3D printing, recording materials, and bonding of glass, plastics, and metal components.

[0078] In addition to the examples given here, those skilled in the art can readily add other necessary components, such as stabilizers, surfactants, leveling agents, and dispersants, depending on the existing technology and the intended use of the photocurable composition.

[0079] To improve initiation efficiency, it is preferable that the initiator has a mass content of 0.1-10% in the solids of the photocurable composition.

[0080] Furthermore, this application also provides an application of any of the above-mentioned photocurable compositions, including using the photocurable composition as an ink, coating, or adhesive. Those skilled in the art can add other necessary components according to the performance requirements such as ink color and printing application. The ink or coating can be used for pattern printing, 3D printing, PCB solder resist layers, liquid or dry film resist materials, substrate protective coatings, etc. In addition to containing the above-mentioned photocurable compositions, other necessary components can be added according to the performance requirements of the adhesive. It can be used for bonding glass, plastics, metal components, etc.

[0081] In another typical embodiment of this application, a photoresist is provided, comprising a multifunctional acrylate monomer, an alkali-soluble resin, an initiator, and a solvent, wherein the initiator is a photoinitiating composition of any of the above.

[0082] Because the photoinitiator composition of this application has high photosensitivity and high resistance to yellowing, the photoresist of this application has high sensitization efficiency and thermal stability, and therefore the photoresist pattern formed after patterning has a high development linewidth.

[0083] Unpigmented transparent photoresists can be used to manufacture high-transmittance films such as protective coatings, sealants, polarizers, and lenses.

[0084] This application also provides a colored photoresist, which, based on the aforementioned transparent photoresist, further contains: a pigment; when the pigment is red, a red photoresist is obtained; when the pigment is green, a green photoresist is obtained; when the pigment is blue, a blue photoresist is obtained; these can be collectively referred to as colored photoresist. When the pigment is black, such as carbon black or titanium black, a black photoresist is obtained. Black photoresist can be used to fabricate black matrices and columnar spacers for cell gaps. Furthermore, using transparent photoresist, colored photoresist, or black photoresist as raw materials, a color filter device can be obtained through a color filter processing procedure, which is an important component of a color display screen.

[0085] To improve initiation efficiency, the mass content of the above-mentioned initiator in the solid part of the photoresist is preferably 0.1-10%, and more preferably 1-8%.

[0086] Examples of the aforementioned multifunctional acrylates include dipentaerythritol hexaacrylate and pentaerythritol acrylate; examples of alkali-soluble resins are polyacrylates with carboxylic acid groups, such as methacrylic acid, itaconic acid, maleic acid, etc., copolymerized with common monomers in the required proportions, such as methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, etc.; preferred examples of copolymers are methyl methacrylate and methacrylic acid copolymers, benzyl methacrylate and methacrylic acid copolymers, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymers.

[0087] The pigments can be CI Pigment Red 177, CI Pigment Green 7, CI Pigment Blue 15:6, Solvent Blue 25, Carbon Black, Titanium Black, and CI Pigment Black 1.

[0088] In addition to using the diacyl diphenyl sulfide derivatives and oxime ester compounds in the photoinitiating composition of this application, other existing commercial or prior art photoinitiators or co-initiators may be added to the above-mentioned photocurable composition and photoresist, as long as they are beneficial to the performance of the photocurable composition, especially the photoresist. Examples include 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-isopropylthioxanthrone, 2,4-diethylthioxanthrone, and bis(2,6-difluoro-3-pyrrolephenyl)dicenoctanetane.

[0089] In addition to the components mentioned above, other resins that may be added include polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, linear phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, and polyimide.

[0090] Any article obtained by using any material containing the photoinitiating composition of the present invention as a raw material and processing it through necessary steps, including finished products such as negative passivation films, photocurable photosensitive surface coatings, barrier films, polarizer coatings, etc.

[0091] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0092] Light source equipment used for curing:

[0093] 365nm LED surface light source, Zhuozhou Lantian Special Lighting Development Co., Ltd.;

[0094] Test equipment:

[0095] Stereo microscope, COVS-50G, Guangzhou Mingmei Optoelectronic Technology Co., Ltd., linewidth unit is μm;

[0096] Yellowness meter, fully automatic color difference meter SC-80C.

[0097] Experimental materials:

[0098] Compound of Formula I-2: 4,4'-bis(2-methylbenzoyl)diphenyl sulfide, from Compound Preparation Example 1;

[0099] Compound of Formula I-3: 4,4'-bis(2-fluorobenzoyl)diphenyl sulfide, from Compound Preparation Example 2;

[0100] Compound I-5: 4-(2-fluorobenzoyl)-4'-(3-methylbenzoyl)diphenyl sulfide, from Compound Preparation Example 3;

[0101] Compound I-6: 4,4'-bis(3-methylbenzoyl)diphenyl sulfide, from Compound Preparation Example 4;

[0102] Compound of Formula I-10: 3-fluoro-4-(3-methylbenzoyl)-4'-benzoyl diphenyl sulfide, from Compound Preparation Example 5;

[0103] Compound of Formula I-12: 4,4'-bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]diphenyl sulfide, from Compound Preparation Example 6;

[0104] Compound of Formula I-13: 4-(3-methylbenzoyl)-4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide, from Compound Preparation Example 7;

[0105] Compound of Formula I-14: 4,4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide, from Compound Preparation Example 8;

[0106] Compound of Formula I-15: 4-(2-methoxy-2-oxoacetyl)-4'-(2-ethoxy-2-oxoacetyl)diphenyl sulfide, from Compound Preparation Example 9;

[0107] Compound of Formula I-18: 4-(2-methoxy-2-oxoacetyl)-4'-(thiophene-2-formyl)diphenyl sulfide, from Compound Preparation Example 10;

[0108] Compound of Formula I-19: 4,4'-(2-cyclohexylmethoxy-2-oxoacetyl)diphenyl sulfide, from Compound Preparation Example 14;

[0109] 4-Benzoyl-4'-methyldiphenyl sulfide: Omnirad BMS, a photoinitiator product from IGM Resins;

[0110] 5,7-Dimethoxy-3-(4-Dodecylbenzoyl)coumarin: Esacure 3644, a photoinitiator product from IGM Resins.

[0111] 4-(2-benzoyloxyiminooctanoyl)diphenyl sulfide: Compound of formula II-1, BASF photoinitiator product OXE01;

[0112] 9-Ethyl-3-(1-acetoxyiminoethyl)-6-(2-methylbenzoyl)carbazole: Compound II-26, BASF photoinitiator product OXE 02;

[0113] 11-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-8-(1-acetoxyimino-1-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methylbenzo[a]carbazole: compound of formula II-43, BASF photoinitiator product OXE03;

[0114] Compound of Formula II-4: 1-(4-phenylthiophenyl)-3-cyclopentylpropane-1,2-dione-2-oxime benzoate, PBG 305, a photoinitiator product of Changzhou Tronly Company;

[0115] Compound of Formula II-6: 1-(4-phenylthiophenyl)-3-cyclohexylpropane-1,2-dione-2-oxime acetate, photoinitiator product PBG 3057 from Changzhou Tronly Company;

[0116] Compound of Formula II-27: 9-ethyl-3-(1-acetoxyimino-3-cyclopentylpropyl)-6-(2-methylbenzoyl)carbazole, photoinitiator product PBG 304 from Changzhou Tronly Company;

[0117] Compound of Formula II-17: 4-(2-acetoxyiminopropionyl)-4'-(3-methylbenzoyl)diphenyl sulfide, from Compound Preparation Example 11;

[0118] Compound of Formula II-18: 4-(2-acetyloxyimino-2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide, from Compound Preparation Example 12;

[0119] Compound of Formula II-15: 4,4'-bis(2-acetoxyiminopropionyl)diphenyl sulfide, from Compound Preparation Example 13;

[0120] Photomer 6010: Aliphatic polyurethane triacrylate, a product of IGM Resins, Netherlands;

[0121] Photomer 4149: Trimethylolpropaneethoxy(3)triacrylate, a product of IGM Resins;

[0122] DPHA: Dipentaerythritol penta- and hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0123] HPMA: Polymaleic acid, a product of Aladdin Industries, Inc., USA.

[0124] Preparation Example

[0125] Preparation of diacyl diphenyl sulfide derivatives

[0126] Example 1: Preparation of 4,4'-bis(2-methylbenzoyl)diphenyl sulfide (compound of formula I-2)

[0127] Add 80g of dichloroethane and 28g of anhydrous aluminum trichloride to a 250ml four-necked flask, cool to 0℃, then add 15g of diphenyl sulfide, and then add 27.4g of o-methylbenzoyl chloride dropwise while maintaining the temperature below 10℃; continue stirring at room temperature for 4h; after the reaction is complete, add the reaction solution dropwise to 30g of concentrated hydrochloric acid and 100g of ice water, keeping the temperature below 30℃; continue stirring for 30min, then allow to stand and separate the liquids; wash the obtained organic phase with 100ml of water for 30min, allow to stand and separate the liquids; remove dichloroethane by vacuum distillation, giving 37.5g of solid residue; dissolve the solid residue in 90g of anhydrous ethanol by heating, then cool to precipitate crystals, filter the precipitated crystals, and dry to give 28g of white solid with a purity of 98.58% and a yield of 82.4%; melting range 68.7~71.2℃; 1 H-NMR (CDCl3) confirmed the structure, δ [ppm]: 2.337 (s, 6H, 2CH3); 7.245-7.401 (m, 8H, 8ArH); 7.401 / 7.429 (d, 4H, 4ArH); 7.741 / 7.769 (d, 4H, 4ArH).

[0128] Example 2: Preparation of 4,4'-bis(2-fluorobenzoyl)diphenyl sulfide (compound of formula I-3)

[0129] Add 40 ml of dichloroethane, 8.67 g of anhydrous aluminum trichloride, and 3.73 g of diphenyl sulfide to a 100 ml four-necked flask, and cool to -5 °C. Then, add 7.54 g of o-fluorobenzoyl chloride dropwise to the flask. After the addition is complete, maintain the reaction temperature at 10 °C for 15 hours. Add the reaction solution dropwise to 12.0 g of concentrated hydrochloric acid and 24.0 g of ice water for acid hydrolysis. After the addition is complete, heat to 20 °C and stir for 1 hour. The separated organic phase is washed once with 24 g of water. Then, remove the organic phase by vacuum distillation, leaving a residue of 8.92 g. Dissolve the residue in a mixture of 36 g of ethanol and 12 g of tetrahydrofuran, and cool to precipitate crystals. Filter the precipitated crystals, dry the filter cake to obtain 7.4 g of white crystalline solid, yield 86%. Purity 98.17%, melting range: 114.5–116.6 °C. 1 ¹H-NMR (CDCl₃) confirmed the structure, with δ [ppm]: 7.134 / 7.163 / 7.194 (t, 2H, 2ArH); 7.250-7.303 (m, 2H, 2ArH); 7.422 / 7.427 / 7.444 / 7.450 (dd, 4H, 4ArH); 7.502-7.585 (m, 4H, 4ArH); 7.778 / 7.781 / 7.806 / 8.809 (dd, 4H, 4ArH).

[0130] Example 3: Preparation of 4-(2-fluorobenzoyl)-4'-(3-methylbenzoyl)diphenyl sulfide (compound of formula I-5)

[0131] Preparation of 3a.4-(3-methylbenzoyl)diphenyl sulfide

[0132] Add 90 ml of dichloroethane and 14.5 g of anhydrous aluminum trichloride to a 250 ml four-necked flask, stir and cool to -5 °C, then add 20.0 g of diphenyl sulfide to the four-necked flask; then slowly add 15.5 g of 3-methylbenzoyl chloride, and stir the reaction at below 0 °C for 6 h. Add the reaction solution dropwise to 30 ml of concentrated hydrochloric acid and 60 ml of ice water for acid hydrolysis, with the temperature not exceeding 20 °C. After stirring for 30 min, let stand to separate the organic phase, then wash the organic phase once with 10 ml of concentrated hydrochloric acid and once with 40 ml of water, and let stand to separate the layers.

[0133] The organic phase obtained by separation was washed once with 40 ml of water; the separated organic phase was distilled under reduced pressure to remove dichloroethane, yielding 32.7 g of a light yellow oily substance; the light yellow oily substance was dissolved in 90 ml of anhydrous ethanol, and a white solid precipitated upon cooling. The solid was kept at -9℃ for 1.5 h; the solid was filtered off, dried, and weighed 28 g, with a yield of 85.6%, a purity of 98.86%, and a melting range of 57.9℃~60.5℃;

[0134] 3b. Preparation of 4-(2-fluorobenzoyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0135] Add 15 ml of dichloroethane, 2.0 g of anhydrous aluminum trichloride and 1.52 g of product 3a to a 50 ml four-necked flask, cool to -5 °C, add 0.88 g of o-fluorobenzoyl chloride dropwise, and after the addition is complete, slowly raise the temperature to 20 °C and keep it at that temperature for 2 h.

[0136] The reaction solution was added dropwise to 4.0 g concentrated hydrochloric acid and 8.0 g ice water for acid hydrolysis, then stirred at 20 °C for 1 h, allowed to stand and separate, and the organic phase was washed with 10 ml of water. The obtained organic phase was subjected to vacuum distillation to remove dichloroethane, yielding a residue of 2.0 g. A mixed solvent of 8.0 g ethanol and 2.0 g tetrahydrofuran was added to the residue, heated until completely dissolved, and then cooled to allow crystallization. The crystals were filtered off, dried, and yielded 1.6 g of white crystals, with a yield of 75%, purity of 98.5%, and melting range of 109.5–113.4 °C. 1 ¹H-NMR (CDCl₃) confirmed that the structure is 4-(2-fluorobenzoyl)-4'-(3-methylbenzoyl)diphenyl sulfide, δ [ppm]: 2.427 (s, 3H, CH₃); 7.134 / 7.163 / 7.194 (t, 1H, ArH); 7.253-7.274 (t, 1H, ArH); 7.299-7.403 (m, 2H, 2ArH); 7.403 / 7.431 (d, 2H, 2ArH); 7.471 / 7.499 (d, 2H, 2ArH); 7.517-7.577 (m, 3H, 3ArH); 7.618 (s, 1H, ArH); 7.767 / 7.773 / 7.795 / 7.801 (dd, 4H, 4ArH).

[0137] Example 4: Preparation of 4,4'-bis(3-methylbenzoyl)diphenyl sulfide (compound of formula I-6)

[0138] Add 3.0 g of diphenyl sulfide and 60 ml of dichloroethane to a 100 ml three-necked flask, stir and cool to -5 °C, then add 6.5 g of anhydrous aluminum trichloride; add 5.5 g of 3-methylbenzoyl chloride dropwise. After the addition is complete, raise the temperature to 10 °C and stir for 15 h. Hydrolyze the reaction solution dropwise in 20 g of concentrated hydrochloric acid and 60 ml of ice water. Wash the separated organic phase with 60 ml of water, then concentrate under reduced pressure to remove some dichloroethane. White crystals precipitate from the solution. Continue cooling to room temperature, precipitating a large amount of white solid. Wash, filter, and dry the white solid, yielding 5.6 g, with a yield of 82.2%, HPLC purity of 98.53%, and melting range of 138.6 °C–142.4 °C. 1¹H-NMR (CDCl₃) confirmed that the structure is 4,4'-bis(3-methylbenzoyl)diphenyl sulfide, δ [ppm]: 2.427 (s, 6H, 2CH₃); 7.366-7.426 (m, 4H, 4ArH); 7453 / 7.481 (d, 4H, 4ArH); 7.553 / 7.577 (d, 2H, 2ArH); 7.618 (s, 2H, 2ArH); 7.763 / 7.791 (d, 4H, 4ArH).

[0139] Example 5: Preparation of 3-fluoro-4-(3-methylbenzoyl)-4'-benzoyl diphenyl sulfide (compound of formula I-10)

[0140] 5a. Preparation of 3-fluoro-4'-benzoyl diphenyl sulfide

[0141] 2.0 g of 3-fluorothiophenol, 1.85 g of NaOH powder, 3.40 g of 4-chlorobenzophenone, and 20 ml of DMSO were placed in a 100 ml single-necked flask. Under nitrogen protection, the mixture was stirred at 80 °C for 10 h. The reaction solution was then added dropwise to 120 ml of ice water, stirred for 1 h, filtered, and the filter cake was dried. The mixture was recrystallized from 45 ml of anhydrous ethanol to obtain 3.15 g of dry white crystals, with a yield of 63.8% and a purity of 99.1%. The melting range was 82.5–83.9 °C. The structure was confirmed by 1H-NMR spectroscopy to be 3-fluoro-4'-benzoyl diphenyl sulfide. δ[ppm, CDCl3]:7.019 / 7.024 / 7.027 / / 7.047 / 7.052 / 7.055 / / 7.074 / 7.080 / 7.083(tt,1H,ArH); 7.155 / / 7.185(dt,1H,ArH); 7.234 / / 7.264(dt,1H,ArH );7.319-7.392(m,3H,ArH);7.457 / 7.481 / 7.506(t,2H,ArH);7.567 / / 7.59 1 / / 7.616(tt,1H,ArH); 7.724 / 7.752(d,2H,ArH); 7.769 / 7.793(d,2H,ArH).

[0142] 5b. Preparation of 3-fluoro-4-(3-methylbenzoyl)-4'-benzoyl diphenyl sulfide

[0143] In a 100ml three-necked flask, 20ml of 1,2-dichloroethane and 2.05g of the product from step 5a were added, stirred, and cooled to 5°C. 3.0g of anhydrous aluminum chloride was added, and the mixture was kept at 10°C. 1.05g of 3-methylbenzoyl chloride was added dropwise. The reaction mixture was stirred for 12 hours. The reaction solution was then added dropwise to 5ml of concentrated hydrochloric acid and 10ml of ice water, stirred at 10–30°C for 1 hour, and allowed to stand for separation. The resulting organic phase was washed with 20ml of water for 30 minutes, and allowed to stand for separation. The organic phase was distilled under reduced pressure to remove 1,2-dichloroethane. The residue was dissolved in 20ml of ethanol, cooled to -15°C, and the precipitated crystals were filtered. The crystals were dried to obtain 2.15g of a white solid. The yield was 76.4%, the purity was 97.8%, and the melting range was 139.0–142.0°C. 1 ¹H-NMR spectroscopy confirmed the structure as 3-fluoro-4-(3-methylbenzoyl)-4'-benzoyl diphenyl sulfide, δ [ppm, CDCl₃]: 2.416 (s, 3H, CH₃); 7.090 / 7.095 / / 7.123 / 7.128 (dd, 1H, ArH); 7.207 / 7.212 / / 7.234 / 7.239 (dd, 1H, ArH); 7.357 / 7.38 (d, 1H, ArH);7.412 / 7.437(d,1H,ArH);7.480-7.538(m,4H,ArH);7.544(s,1H,ArH);7.586 / 7.591 / / 7 .609 / 7.615(dd,2H,ArH); 7.662(s,1H,ArH); 7.795 / 7.800 / 7.805 / / 7.826 / 7.833(m.4H,ArH).

[0144] Example 6: Preparation of 4,4'-bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]diphenyl sulfide (compound of formula I-12)

[0145] Preparation of 6a.4,4'-bis(4-fluorobenzoyl)diphenyl sulfide (compound of formula I-4)

[0146] In a 100ml four-necked flask, 3.7g of diphenylsulfide, 50g of 1,2-dichloroethane, and 6.1g of anhydrous aluminum trichloride were placed and cooled to 0℃. 7.0g of p-fluorobenzoyl chloride was added dropwise, and the mixture was naturally heated to 25℃ and stirred for 20 hours. The reaction solution was then added in portions to 30g of 10% HCl solution at 0℃, stirred for 30 minutes after each addition, allowed to stand for 30 minutes, and then separated. The organic phase was washed once with 30ml of water, then once with 30ml of 2% sodium hydroxide solution, and then once with 30ml of water. The organic phase was then distilled under reduced pressure to remove the 30g dichloroethane solution, cooled to crystallize, filtered, and the filter cake was dried to obtain 7.5g of white powder, with a yield of 87.1%, a purity of 98.5%, and a melting range of 227.3–230.6℃.1 ¹H-NMR spectroscopy confirmed the structure as 4,4'-bis(4-fluorobenzoyl)diphenyl sulfide, δ [ppm, CDCl₃]: 7.377 / 7.407 / 7.436 (t, 4H, ArH); 7.548 / 7.576 (d, 4H, ArH); 7.755 / 7.783 (d, 4H, ArH); 7.825 / 7.844 / 7.854 / 7.873 (dd, 4H, ArH).

[0147] Preparation of 6b.4,4'-bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]diphenyl sulfide (compound of formula I-12)

[0148] In a 50 ml reaction flask, 2.0 g of the product from step 6a was dissolved in 15 ml of pyridine, followed by the addition of 2.6 g of 2,2,3,3-tetrafluoropropanol and 0.9 g of solid NaOH. The mixture was stirred at 50 °C for 6 h. The reaction solution was then added to 100 ml of water, and the precipitated solid was filtered. Recrystallization was performed with 25 ml of ethyl acetate to obtain white flaky crystals. After drying, 2.5 g of the crystals were obtained, with a purity of 98.0% and a yield of 82.6%. The melting range was 205.3–208.6 °C. ¹H-NMR spectroscopy confirmed the structure to be 4,4'-bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]diphenyl sulfide. δ[ppm, CDCl3]:4.701 / 4.745 / 4.790(t,4H,2OCH2);6.530 / 6.548 / 6.566 / / 6.702 / 6.721 / 6.739 / / 6.875 / 6.894 / 6.912(t t,2H,2CHF2); 7.210 / 7.240(d,4H,ArH); 7.542 / 7.570 / (d,4H,ArH); 7.729 / 7.757(d,4H,ArH); 7.780 / 7.809(d,4H,ArH).

[0149] Example 7: Preparation of 4-(3-methylbenzoyl)-4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-13)

[0150] In a 100ml three-necked flask, 30g of dichloroethane and 5.5g of aluminum trichloride were placed, along with 5g of the compound used in Preparation Example 3a. The mixture was kept at 10°C, and 1.8g of monomethyl oxaloyl chloride was added dropwise. The reaction mixture was stirred for 3 hours. The reaction solution was then added dropwise to 10ml of concentrated hydrochloric acid and 30ml of ice water, and stirred at 10–30°C for 1 hour. The mixture was allowed to stand and separated. The organic phase was washed with 50ml of water for 30 minutes, and the mixture was allowed to stand and separated. Dichloroethane was removed by vacuum distillation. The residue was dissolved in 20g of ethanol, cooled to -15°C, and the precipitated crystals were filtered and dried to obtain 5.4g of a pale yellow crystalline solid, with a yield of 84%. The purity was 97.84%, and the melting range was 121.4–122.7°C.1 ¹H-NMR spectroscopy confirmed the structure as 4-(3-methylbenzoyl)-4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide. δ [ppm, CDCl₃]: 2.435 (s, 3H, CH₃); 3.974 (s, 3H, OCH₃); 7.372 / 7.415 (d+m, 4H, 4ArH); 7.524-7.588 (d+d, 3H, 3ArH); 7.631 (s, 1H, ArH); 7.795 / 7.823 (d, 2H, 2ArH); 7.947 / 7.975 (d, 2H, 2ArH).

[0151] Example 8: Preparation of 4,4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-14)

[0152] Add 50g of dichloromethane and 16.1g of anhydrous aluminum trichloride to a 100ml three-necked flask, cool to 0℃, and add 5g of diphenyl sulfide; add 7.2g of oxaloyl chloride monomethyl ester dropwise, and stir the reaction at no more than 10℃ for 6h; add 20g of concentrated hydrochloric acid and 50g of ice water to a 250ml four-necked flask, add all the reaction solution dropwise, stir at room temperature for 30min, and then let stand and separate the layers; wash the organic phase with 50ml of water for 30min, and then let stand and separate the layers; remove some of the dichloromethane by vacuum distillation of the organic phase; cool the remaining solution to -15℃, filter the precipitated crystals, and dry to obtain 8.0g of yellow needle-like crystals with a purity of 99.30%, a yield of 84%, and a melting range of 106.8~110.0℃. 1 ¹H-NMR spectroscopy confirmed the structure as 4,4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide, δ [ppm,CDCl3]: 3.985 (s, 6H, 2CH3); 7.451 / 7.480 (d, 4H, 4ArH); 7.987 / 8.015 (d, 4H, 4ArH).

[0153] Example 9: Preparation of 4-(2-methoxy-2-oxoacetyl)-4'-(2-ethoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-15)

[0154] Preparation of 9a.4-(2-ethoxy-2-oxoacetyl)diphenyl sulfide

[0155] In a 100ml three-necked flask, 20g of dichloroethane and 10.7g of anhydrous aluminum trichloride were placed and cooled to 0℃. 10g of diphenyl sulfide was added. 8.1g of oxaloyl chloride monoethyl ester was added dropwise, and the reaction was maintained at 5-10℃ for 4 hours. In a 250ml four-necked flask, 40g of water and 10g of concentrated hydrochloric acid were placed and cooled to 0℃. The reaction solution was added dropwise to ice water, and the temperature was controlled not to exceed 30℃. After stirring for 30 minutes, the mixture was allowed to stand and separated. The organic phase was washed with 50ml of water for 30 minutes and then allowed to stand and separate. The organic phase was desolventized by vacuum distillation to obtain 12g of a yellow liquid with a purity of 98.56% and a yield of 78%.

[0156] Preparation of 9b.4-(2-methoxy-2-oxoacetyl)-4'-(2-ethoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-15)

[0157] In a 100ml three-necked flask, 50g of dichloroethane and 10.5g of anhydrous aluminum trichloride were placed and cooled to 0℃. 5g of the product from operation 9a was added. 2.4g of oxaloyl chloride monoethyl ester was added dropwise, keeping the reaction solution temperature below 10℃, and then the reaction was continued with stirring for 4 hours. In a 250ml four-necked flask, 40g of water and 10g of 36% hydrochloric acid were placed and cooled to 0℃. The reaction solution was added dropwise, keeping the temperature below 30℃, and the mixture was stirred for 30 minutes before being allowed to stand and separate. The organic phase was washed with 50ml of 3% sodium bicarbonate aqueous solution for 30 minutes, and then allowed to stand and separate. The organic phase was washed again with 50ml of water. The separated organic phase was desolvated by vacuum distillation to remove the solvent, yielding 5g of a yellow liquid with a yield of 83%. After standing at room temperature, the liquid solidified into light yellow crystals. The HPLC purity was 98.43%, and the melting range was 36.4–40.3 °C. The structure was confirmed by 1H-NMR spectroscopy to be 4-(2-methoxy-2-oxoacetyl)-4'-(2-ethoxy-2-oxoacetyl)diphenyl sulfide, with δ [ppm, CDCl3]: 1.404 / 1.428 / 1.452 (t, 3H, CH3); 3.985 (s, 6H, 2CH3); 4.417 / 4.441 / 4.464 / 4.488 (quartet, 2H, OCH2); 7.449 / 7.455 / 7.472 / 7.478 (dd, 4H, 4ArH); 7.976 / / 7.982 / 7.999 / 8.005 (dd, 4H, 4ArH).

[0158] Example 10: Preparation of 4-(2-methoxy-2-oxoacetyl)-4'-(thiophene-2-formyl)diphenyl sulfide (compound of formula I-18)

[0159] 10a. Preparation of 4-(thiophene-2-formyl)diphenyl sulfide

[0160] Add 5.18 g of diphenyl sulfide and 25 ml of o-dichlorobenzene to a 100 ml three-necked flask, and cool to ℃; add 3.7 g of anhydrous aluminum trichloride, stir and maintain 0-5 ℃, add 4.1 g of thiophene-2-formyl chloride dropwise, and then keep the reaction at this temperature for 10 h. Acidify the reaction solution in hydrochloric acid aqueous solution, wash with water, concentrate and recover o-dichlorobenzene to obtain 8.2 g of light yellow solid, recrystallize with 50 ml of ethanol to obtain 6.85 g of dry white crystals, yield 83.1%, HPLC purity 99.31%, melting range 106.1-109.4 ℃.

[0161] 10b. Preparation of 4-(2-methoxy-2-oxoacetyl)-4'-(thiophene-2-formyl)diphenyl sulfide

[0162] Following the procedure in Example 7 of Compound Preparation, 4.05 g of product 10a and 5.65 g of anhydrous aluminum trichloride were dissolved in 20 ml of 1,2-dichloroethane in a 100 ml three-necked flask. 1.76 g of monomethyl oxalyl chloride was added dropwise at a temperature below 10 °C. The reaction was carried out for 5 h. After acid hydrolysis, washing with water, and concentration, 4.4 g of yellow crystals were obtained. After recrystallization with 35 ml of ethanol, 3.95 g of dry, pale yellow crystals were obtained, with a yield of 75.4%, a purity of 98.0%, and a melting range of 105–107 °C. 1 ¹H-NMR spectroscopy confirmed the structure as 4-(2-methoxy-2-oxoacetyl)-4'-(thiophene-2-formyl)diphenyl sulfide. δ (ppm, CDCl₃) values: 3.976 (s, 3H, OCH₃); 7.171 / 7.190 / 7.193 / 7.206 (dd, 1H, ArH); 7.367 / 7.396 (d, 2H, ArH); 7.547 / 7.576 (d, 2H, 2ArH); 7.663-7.675 (d, 1H, ArH); 7.754 / 7.757 / 7.770 / 7.773 (dd, 1H, ArH); 7.867 / 7.895 (d, 2H, ArH); 7.948 / 7.976 (d, 2H, ArH).

[0163] Example 11: Preparation of 4-(2-acetoxyiminopropionyl)-4'-(3-methylbenzoyl)diphenyl sulfide (compound of formula II-17)

[0164] 11a. Preparation of 4-(3-methylbenzoyl)diphenyl sulfide

[0165] From Compound Preparation Example 3a

[0166] 11b. Preparation of 4-propionyl-4'-(3-methylbenzoyl)diphenyl sulfide

[0167] 2.28 g of aluminum trichloride and 20 g of dichloroethane were placed in a 100 ml three-necked flask. The mixture was kept at 0 °C, and 4 g of the product from preparation example 3a and a solution of 10 g of dichloroethane were added dropwise. 1.34 g of propionyl chloride was added dropwise at 0 °C, and the reaction was carried out at 0–5 °C for 3 h. The reaction mixture was then added dropwise to a solution of 20 ml hydrochloric acid and 50 ml water at 0 °C, stirred for 1 h, and allowed to stand before separation. The organic phase was washed with 50 ml water for 30 min, allowed to stand, and then separated. The solvent was evaporated under reduced pressure to dryness, yielding 4 g of a pale yellow solid. The yield was 84.45%. The HPLC purity was 98.87%, and the melting range was 96.0–98.0 °C. 1 ¹H-NMR, δ(CDCl₃, ppm) values: 1.206 / 1.230 / 1.254 (t, 3H, CH₃); 2.426 (s, 3H, CH₃); 2.953 / 2.977 / 3.001 / 3.025 (quartet, 2H, CH₂); 7.339-7.420 (m, 2H, 2ArH); 7.426 / 7. 442 / 7.448 / 7.454(dd,4H,4ArH);7.549 / 7.573(d,1H,ArH);7.614(s,1H,ArH);7.7 49 / 7.755 / 7.772 / 7.778(dd,2H,2ArH); 7.911 / 7.917 / 7.934 / 7.940(dd,2H,2ArH).

[0168] 11c. Preparation of 4-(2-hydroxyiminopropionyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0169] 4g of the product from operation 11b, 20g of DMSO, 0.3g of hydrochloric acid, and 1.37g of n-butyl nitrite were placed in a 100ml single-necked flask and reacted at 40℃ for 5h. The reaction solution was then added dropwise to 100g of water at 5℃, stirred for 30min, and filtered. The filter cake was dried to obtain 4g of a yellow solid product, with a yield of 92.55%. The HPLC purity was 97.73%, and the melting range was 147.6–149.0℃. 1 ¹H-NMR (CDCl₃), δ (ppm) values: 2.182 (s, 3H, CH₃); 2.422 (s, 3H, CH₃); 7.361-7.445 (d, 6H, 6ArH); 7.546 / 7.570 (d, 1H, ArH); 7.611 (s, 1H, ArH); 7.740 / 7.768 (d, 2H, 2ArH); 7.871 / 7.899 (d, 2H, 2ArH); 8.344 (s, 1H, OH).

[0170] 11d. Preparation of 4-(2-acetoxyiminopropionyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0171] Place 4g of 11C product, 30g of toluene, and 4.5g of acetic anhydride into a 100ml single-necked flask and react at 45℃ for 2 hours.

[0172] The reaction solution was cooled to room temperature, and 80 ml of water was added. The mixture was stirred for 30 min, then allowed to stand and separate. The toluene phase was washed with 50 ml of water for 30 min, and then allowed to stand and separate. Toluene was removed by vacuum distillation, yielding 4.5 g of a yellow crude solid. This crude solid was dissolved in a mixed solvent of 8 g ethyl acetate and 10 g n-hexane, then cooled to -15 °C, filtered, and the filter cake was dried to give 3.8 g of pale yellow crystals, with a yield of 85.74%. HPLC purity was 99.63%, melting range 98.0-100 °C. 1 H-NMR (CDCl3), δ (ppm) value data: 2.271 (s, 3H, CH3); 2.289 (s, 3H, CH3); 2.431 (s, 3H, CH3); 7.381-7.410 (d, 4H, 4ArH ); 7.487 / 7.515(d,2H,2ArH); 7.545-7.624(d,2H,2ArH); 7.771 / 7.799(d,2H,2ArH); 8.47 / 8.075(d,2H,2ArH).

[0173] Example 12: Preparation of 4-(2-acetoxyimino-2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide (compound of formula II-18)

[0174] 12a. Preparation of 4-(2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0175] Following the procedure of Example 11b, 2-phenylacetyl chloride was used instead of propionyl chloride for the Friedel-Crafts reaction. After hydrolysis and purification, pale yellow crystals were obtained with a melting range of 141.8–145.0 °C and a yield of 86.1%. 1 ¹H-NMR confirmed it to be 4-(2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide; δ (CDCl₃, ppm) values: 2.427 (s, 3H, CH₃); 4.259 (s, 2H, CH₂); 7.233-7.463 (m, 11H, ArH); 7.550 / 7.574 (d, 1H, ArH); 7.616 (s, 1H, ArH); 7.754 / 7.781 (d, 2H, 2ArH); 7.943 / 7.972 (d, 2H, 2ArH).

[0176] 12b. Preparation of 4-(2-hydroxyimino-2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0177] Following the method of operation 11c in Example 11, the product of operation 12a was used instead of the product of operation 11b for oxime reaction, followed by purification to obtain white crystals with a melting range of 155.0–160.1 °C. HPLC analysis showed a cis-trans isomer ratio of 2:98. δ(CDCl3, ppm) values ​​were: 2.423 (s, 3H, CH3); 7.233–7.463 (m, 7H, ArH); 7.498 (s, 1H, ArH); 7.526–7.565 (m, 4H, ArH); 7.618 (s, 1H, ArH); 7.772 / 7.799 (d, 2H, 2ArH); 7.878 / 7.907 (d, 2H, 2ArH).

[0178] 12c. Preparation of 4-(2-acetoxyimino-2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide

[0179] Add 2.2 g of the product from operation 12b and 20 ml of dichloroethane to a 50 ml three-necked flask. Incubate in a water bath at 25 °C. Add 0.6 g of acetic anhydride dropwise. After the addition is complete, react at 25 °C for 0.5 h. Add 20 ml of water dropwise to the reaction flask and stir for about 1 h. Separate the organic phase. Wash the organic phase twice with 10 ml of 5% sodium bicarbonate aqueous solution, and then wash with water until neutral. Desolvate the organic phase to obtain 2.2 g of an oily substance. Separate the oily substance by column chromatography with a 1:10 mixture of ethyl acetate and n-hexane. After desolvation, the eluent yields 1.95 g of solid. Recrystallize from ethanol to obtain 1.72 g of white crystals, yield 76.8%. Melting range: 91.5–93.6 °C. 1 ¹H-NMR confirmed it to be 4-(2-acetoxyimino-2-phenylacetyl)-4'-(3-methylbenzoyl)diphenyl sulfide; δ (CDCl₃, ppm) values: 2.035 (s, 3H, CH₃); 2.432 (s, 3H, CH₃); 7.342–7.430 (m, 6H, 6ArH); 7.471 / 7.495 (d, 1H, ArH); 7.541–7.569 (m, 3H, 3ArH); 7.628 (s, 1H, ArH); 7.690 / 7.718 (d, 2H, 2ArH); 7.797 / 7.824 (d, 2H, 2ArH); 7.824 / 7.852 (d, 2H, 2ArH).

[0180] Example 13: Preparation of 4,4'-bis(2-acetoxyiminopropionyl)diphenyl sulfide (compound of formula II-15)

[0181] 13a. Preparation of 4,4'-dipropionyl diphenyl sulfide

[0182] Weigh 79.0 g (0.424 mol) of diphenyl sulfide and dissolve it in 600 g of 1,2-dichloroethane. Add 124.4 g (0.933 mol) of anhydrous aluminum trichloride and stir while cooling to 0°C. Keep the temperature below 5°C and add 82.4 g (0.891 mol) of propionyl chloride dropwise over 2 hours. Continue stirring at 0°C for another 2 hours. Add the reaction mixture dropwise to 450 ml of 10% dilute hydrochloric acid, keeping the acid solution temperature below 30°C. Stir for 1 hour after the addition is complete, and separate the lower organic layer. The organic phase was washed three times with 300 ml of water. The solvent was recovered by vacuum distillation of the organic phase, yielding 126 g of residue. While still hot, 240 ml of n-hexane was added, and the solution was kept hydrated until clear. The solution was allowed to cool naturally to crystallize. When the solution temperature was below 30°C, the crystallization flask was placed in an ice-water bath to further cool to 0°C. The solution was filtered to obtain a white filter cake, which was dried under reduced pressure at 50°C to obtain 117.6 g of white crystals, with a yield of 93%. HPLC analysis showed a purity of 98.5% and a melting range of 123.1-130.3°C. 1 H-NMR data indicate that the product obtained is 4,4'-dipropionyl diphenyl sulfide.

[0183] 13b. Preparation of 4,4'-bis(2-hydroxyiminopropionyl)diphenyl sulfide

[0184] 30 g (0.1 mol) of the product 4,4'-dipropionyl diphenyl sulfide obtained in 13a was dissolved in 100 g of dimethyl sulfoxide. 3.0 g of 36% concentrated hydrochloric acid was added, and the mixture was kept in a water bath at 20-25℃ with stirring. 25 g (0.24 mol) of n-butyl nitrite was added dropwise over 30 min, and the mixture was stirred for 10 h. The reaction solution was then added dropwise to 1 L of ice water, precipitating a pale yellow solid. The solid was filtered, dried under reduced pressure, and weighed 27 g. HPLC analysis showed a purity of 97.80% and a yield of 75%. The melting range was 162.8-169.5℃. 1 ¹H-NMR data indicate that the product obtained is 4,4'-bis(2-hydroxyiminopropionyl)diphenyl sulfide. δ (CDCl₃, ppm) values: 2.022 (s, 6H, 2CH₃); 7.425 / 7.452 (d, 4H, 4ArH); 7.823 / 7.851 (d, 4H, 4ArH); 12.450 (s, 2H, 2NOH).

[0185] 13c. Preparation of 4,4'-bis(2-acetoxyiminopropionyl)diphenyl sulfide

[0186] 24.5 g (0.068 mol) of product 4,4'-bis(2-hydroxyiminopropionyl)diphenyl sulfide and 150 ml of toluene were added to a reaction flask. The reaction flask was placed in a water bath at 20-25 °C. 19.6 g (0.19 mol) of acetic anhydride was added dropwise to the reaction flask through a constant pressure dropping funnel, and the mixture was stirred for 6 h. 100 ml of water was added to the reaction solution, and the mixture was stirred for 30 min. The toluene phase was washed successively with 100 ml of 1% sodium bicarbonate solution, 50 ml of water, and 50 ml of water. The toluene solution was filtered, and the toluene was recovered by vacuum distillation to obtain 28.5 g of yellow solid crude product. 55 ml of hot ethyl acetate was added to dissolve the solid, and then 85 ml of hot n-hexane was added. The mixture was allowed to cool naturally to precipitate crystals. The crystals were filtered, and the filter cake was dried under vacuum to obtain 27.2 g of light yellow solid crystalline product. HPLC analysis showed a purity of 99.2% and a yield of 90.8%. The melting range was 108.0-111.5 °C. 1 H-NMR (CDCl3), δ (ppm) values: 2.274 (s, 6H, 2CH3); 2.293 (s, 6H, 2COCH3); 7.417 / 7.445 (d, 4H, 4ArH); 8.050 / 8.078 (d, 4H, 4ArH).

[0187] Example 14: Preparation of 4,4'-(2-cyclohexylmethoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-19)

[0188] In a 50 ml single-necked flask, 2 g (5.6 mmol) of 4,4'-(2-methoxy-2-oxoacetyl)diphenyl sulfide (compound of formula I-14), the product of Compound Preparation Example 8, was weighed. 20 ml of cyclohexylethanol and 20 mg of zirconium acetylacetonate catalyst were added. A magnetic stir bar was added, and the mixture was heated to 80 °C and stirred electromagnetically for 18 h. The cyclohexylethanol was removed by vacuum distillation, and the residue was purified by silica gel column chromatography to give 1.85 g of a pale yellow viscous substance with a purity of 98.9% and a yield of 63.4%. 1 ¹H-NMR (CDCl₃) confirmed it as 4,4'-(2-cyclohexylmethoxy-2-oxoacetyl)diphenyl sulfide, with δ (ppm) values ​​of: 1.010-1.294 (m, 10H, 2cyclohexyl); 1.679-1.808 (m, 12H, 2cyclohexyl); 4.187 / 4.208 (d, 4H, 2CH₂); 7.452 / 7.480 (d, 4H, 4ArH); 7.960 / 7.989 (d, 4H, 4ArH).

[0189] Example 1 of preparation of photoinitiator composition:

[0190] Take 3g of the compound shown in Formula I-14 and 7g of OXE 01 sample, grind and mix them in a mortar to obtain 10g of composition, with a molar ratio of diacyl diphenyl sulfide derivative and oxime ester compound of 0.53:1.

[0191] Example 2 of preparation of photoinitiator composition:

[0192] Take 4.5g of the compound shown in Formula I-14 and 5.5g of OXE 01 sample, grind and mix them in a mortar to obtain 10g of composition, with a molar ratio of 1:1 between the diacyl diphenyl sulfide derivative and the oxime ester compound.

[0193] Example 3 of photoinitiator composition preparation:

[0194] Take 5g of the compound shown in Formula I-14 and 5g of OXE 01 sample, grind and mix them in a mortar to obtain 10g of composition, with a molar ratio of diacyl diphenyl sulfide derivative and oxime ester compound of 1.24:1.

[0195] Example 4 of photoinitiator composition preparation:

[0196] Take 5.3g of the compound shown in Formula I-14 and 4.7g of OXE-01 sample, grind and mix them in a mortar to obtain 10g of composition, with a molar ratio of diacyl diphenyl sulfide derivative and oxime ester compound of 1.4:1.

[0197] Example 5 of photoinitiator composition preparation:

[0198] Take 3g of the compound shown in Formula I-14 and 7g of the compound shown in Formula II-19, grind and mix them in a mortar to obtain 10g of the composition, with a molar ratio of 0.53:1.

[0199] Preparation of alkali-soluble resins

[0200] 18g of benzyl methacrylate, 6g of methacrylic acid, 6g of hydroxyethyl methacrylate, 1.5g of azobisisobutyronitrile, 0.6g of dodecyl mercaptan, and 200ml of toluene were placed in a constant pressure dropping funnel in 1L. 100ml of toluene was placed in a 500ml four-necked flask, the mixture was purged with nitrogen, and the temperature was raised to 80℃. The solution in the funnel was added dropwise, and after reacting for 6 hours, the mixture was cooled and filtered to obtain 24g of white alkali-soluble resin.

[0201] Preparation of black pigment

[0202] Take 50g of the above-mentioned white alkali-soluble resin, 50g of P25 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 3000r / min using a high-speed shear mixer to obtain a black color paste.

[0203] Preparation of red pigment

[0204] Take 50g of the above-mentioned white alkali-soluble resin, 50g of Ciba IRGALITE RED 2BXL-Q pigment, 100g of DPHA, and 250g of propylene glycol methyl ether acetate and put them into a 500ml beaker. Mix them for 15 minutes at 3000r / min using a high-speed shear mixer to obtain a red pigment paste.

[0205] Photoresist Examples

[0206] The photoresists for each example and comparative example were prepared according to the groupings described in Tables 1-7. The initiator and sensitizer could be the compositions in the photoinitiator composition preparation examples or mixed according to the weight ratios in the table below and then dissolved in PMA to form a composition solution. The composition solution was then mixed with black or red pigment in a specific ratio. After uniform mixing of all components, a film was coated onto a glass slide using a 10 μm wire rod, dried in a 90°C oven for 5 min, cured using a 365 nm light source with a mask, developed using a 1% NaOH solution at 25°C, rinsed with purified water for 10 s, dried in a 90°C oven for 30 min, and the linewidth of the developed image was measured under a microscope. The results are shown in Tables 1-7.

[0207] Table 1

[0208]

[0209] Table 1 shows that the development linewidth of the example using OXE 01 and the photoinitiator composition formulated with compound I-14 was significantly greater than that of the comparative example using OXE 01 alone, and the sensitivity was significantly higher than that of the comparative example using OXE 01 alone.

[0210] Table 2

[0211]

[0212]

[0213] Table 2 shows that the development linewidth of the examples using the photoinitiator composition formulated with compound II-15 and compound I-14 was significantly greater than that of the comparative examples using compound II-15 alone, and the sensitivity was significantly higher than that of the comparative examples using the initiator alone.

[0214] Table 3

[0215]

[0216] Table 3 shows that the development linewidth values ​​of the examples in which OXE 01 was formulated with compounds of formulas I-2, I-6, I-14, and I-15 to form photoinitiator compositions were significantly greater than those of the comparative examples using OXE 01 alone and using Esacure 3644 and Omnirad BMS for sensitization.

[0217] Table 4

[0218]

[0219]

[0220] Table 5

[0221]

[0222] Tables 4 and 5 show that photoinitiator compositions formulated with compounds of formula II-1, II-4, II-15, II-17, and II-18 in combination with compound I-14 exhibit significantly higher curing and developing linewidth values ​​than the corresponding comparative examples, and significantly higher sensitivity than the comparative examples using only the corresponding single initiator. Furthermore, comparisons between Example 5 and Comparative Example 2, Example 13 and Comparative Example 6, and Example 14 and Comparative Example 7 demonstrate that compositions using a combination of diacyldiphenyl sulfide derivatives and oxime ester compounds as initiators exhibit significantly higher photosensitivity than initiators possessing both diacyldiphenyl sulfide and oxime ester groups.

[0223] Table 6

[0224]

[0225] Table 6 shows that the development linewidth of the examples using the photoinitiator composition provided by the present invention in the red system is significantly higher than that of the comparative examples using the same initiator alone.

[0226] Table 7

[0227]

[0228]

[0229] Table 7 shows that when compound I-14 is combined with photoinitiators of various carbazole structures, the curing and developing linewidth values ​​are significantly greater than those of the corresponding comparative examples, and the sensitivity is significantly higher than that of the comparative examples using the corresponding single oxime ester initiator alone.

[0230] Examples of transparent light-curing compositions

[0231] Each example and comparative example was prepared according to the group allocation in Table 8. After the components were mixed evenly, a film was coated on a glass slide using a 50 μm wire rod and cured using a 365 nm light source. After curing, the film weight was measured. Then, the film weight was measured again after soaking in acetone at room temperature for 36 h. The gel conversion rate was calculated to evaluate the carbon-carbon double bond conversion rate. The higher the conversion rate, the better the initiation efficiency of the initiator.

[0232] Each example and comparative example was prepared according to the groupings in Table 8. After the components were mixed evenly, a film was coated on a glass plate using a 25μm wire rod and cured using a 365nm LED light source. After baking in an oven at 230℃ for 30 minutes, the film was cooled to room temperature, and the yellowness value of each example and comparative example was measured using a fully automatic colorimeter.

[0233] Table 8

[0234] Photomer 6010 5 5 5 HPMA 4.5 4.5 4.5 Compound II-1 0.35 0.35 0.5 Compounds of Formula I-6 0.15 0 0 Compound I-14 0 0.15 0 gel conversion rate 94.2％ 94.0％ 85.2％ Yellowing value 6.22 6.45 7.08

[0235] As can be seen from the data, the photogel conversion rate of the transparent photocurable composition using the photoinitiator composition provided by the present invention is significantly higher than that of the comparative example using oxime ester photoinitiator alone, and the yellowness value is also lower than that of the corresponding comparative example.

[0236] As can be seen from the above description, the above embodiments of the present invention achieve the following technical effects: the photoinitiator composition containing diacyl diphenyl sulfide derivative and oxime ester compound provided by the present invention has significantly higher curing activity or sensitivity in the photocurable composition than using the same oxime ester photoinitiator alone, and also has significantly lower yellowing after photocuring and post-heating processing.

[0237] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photoinitiating composition, characterized in that, The photoinitiating composition comprises at least one diacyl diphenyl sulfide derivative and at least one oxime ester compound; the molar ratio of the diacyl diphenyl sulfide derivative to the oxime ester compound is 0.1:1 to 3:1; The diacyl diphenyl sulfide derivative is selected from compounds shown in Formula I: Formula I In formula I, R1 and R2 are each independently selected from any one of the following groups: phenyl, methyl-substituted phenyl, C1-C4 alkoxyacyl, C1-C4 alkoxyacyl substituted with a C4-C7 cycloalkyl group; R 11 R 12 R 13 R 14 R 15 R 16 R 18 and R 19 Each is independently represented by H; At least one of the oxime ester compounds is selected from compounds shown in Formula III: （Ⅲ） in, n1 is either 1 or 0; R3 is selected from any one of the following groups: C1-C16 alkyl, C1-C16 alkyl substituted with C4-C7 cycloalkyl, phenyl; R4 is selected from any one of the following groups: C1-C11 alkyl, phenyl; R 21 R 22 R 23 R 24 Each is independently represented by H; R 25 R 26 R 27 R 28 R 29 Each is independently represented by H. substituted or unsubstituted benzoyl group, wherein the substituent of the substituted benzoyl group is R. 20 R 20 R3' is selected from C1-C8 alkyl groups, and R3' is selected from C1-C6 alkyl groups; Alternatively, at least one of the oxime ester compounds is selected from any one of the compounds shown in Formula IV or Formula V: Ⅳ， Ⅴ， Wherein, Y1 and Y2 are each independently selected from Ar2CO; n2 and n3 are each independently 1 or 0; R3 is selected from any of the following groups: C1-C16 alkyl, C1-C16 alkyl substituted with C4-C7 cycloalkyl, phenyl substituted with one or more halogen atoms or C1-C4 alkoxy groups; R4 is selected from any one of the following groups: C1-C11 alkyl; R5 and R6 are each independently selected from any one of the following groups: H, C1-C8 alkyl; Ar2 is selected from phenyl, and the hydrogen on the phenyl group can be replaced by C1-C4 alkyl groups; R 41 R 42 R 43 Each is independently represented by H.

2. The photoinitiating composition according to claim 1, characterized in that, The diacyl diphenyl sulfide derivative is selected from one of the following compounds or any mixture thereof. Ⅰ-1、 Ⅰ-2、 Ⅰ-6、 Ⅰ-14、 Ⅰ-15、 Ⅰ-16、 Ⅰ-19。 3. The photoinitiating composition according to claim 1, characterized in that, The oxime ester compound is selected from one of the following compounds or any mixture thereof: Ⅱ-1、 Ⅱ-2、 Ⅱ-4、 Ⅱ-6、 Ⅱ-12、 Ⅱ-14、 Ⅱ-15、 Ⅱ-16、 Ⅱ-17、 Ⅱ-18、 Ⅱ-20、 Ⅱ-23、 Ⅱ-26、 Ⅱ-27、 Ⅱ-39、 Ⅱ-42、 Ⅱ-43 。 4. The photoinitiating composition according to claim 1, characterized in that, The molar ratio of the diacyl diphenyl sulfide derivative to the oxime ester compound is 0.3:1 to 1.4:

1.

5. A photocurable composition comprising a photocurable resin and an initiator, characterized in that, The initiator is the photoinitiating composition according to any one of claims 1 to 4.

6. The photocurable composition according to claim 5, characterized in that, The initiator has a mass content of 0.1-10% in the solids of the photocurable composition.

7. An application of the photocurable composition of claim 5 or 6, the application comprising using the photocurable composition as an ink, coating, sealant, optical film or adhesive.

8. The application of the photocurable composition according to claim 7, characterized in that, The applications include using the photocurable composition as a negative passivation film, a photocurable photosensitive surface coating, a barrier film, or a polarizer coating.

9. A photoresist comprising a multifunctional acrylate monomer, an alkali-soluble resin, an initiator, and a solvent, characterized in that, The initiator is the photoinitiating composition according to any one of claims 1 to 4.

10. The photoresist according to claim 9, characterized in that, The photoresist also includes pigments, which are selected from any one of black, red, green and blue pigments.

11. The photoresist according to claim 10, characterized in that, The black pigment is dispersed carbon black or titanium black.

12. The photoresist according to claim 9 or 10, characterized in that, The initiator has a mass content of 0.1-10% in the solid portion of the photoresist.

13. An application of the photoresist according to any one of claims 9 to 12, the photoresist further comprising pigment, the application comprising using the photoresist as a sealant, optical film, colored matrix, optical spacer or filter.

14. The application of the photoresist according to claim 13, characterized in that, The applications include using the photoresist as a negative passivation film, a photocurable photosensitive surface coating, a barrier film, or a polarizer coating.

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