CN114369178A

CN114369178A - Photoinitiating composition, photocuring composition, photoresist, photocuring composition and application of photoresist

Info

Publication number: CN114369178A
Application number: CN202011098687.9A
Authority: CN
Inventors: 王辰龙; 赵文超; 麻忠利; 王永林; 张珏
Original assignee: Insight High Technology Jiangsu Co ltd; Insight High Technology Beijing Co Ltd
Current assignee: Insight High Technology Jiangsu Co ltd; Insight High Technology Beijing Co Ltd
Priority date: 2020-10-14
Filing date: 2020-10-14
Publication date: 2022-04-19

Abstract

The invention provides a photoinitiating composition, a photocuring composition, a photoresist, application of the photocuring composition and application of the photoresist. The photoinitiation composition comprises 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 a formula I, and the oxime ester compound is selected from compounds shown in a formula II. When the photoinitiation composition is applied, the photoinitiation composition has good sensitizationDegree and resistance to yellowing.

Description

Photoinitiating composition, photocuring composition, photoresist, photocuring composition and application of photoresist

Technical Field

The invention relates to the technical field of photocuring materials, and particularly relates to a photoinitiation composition, a photocuring composition, a photoresist, application of the photocuring composition and application of the photoresist.

Background

Photocuring technology has been widely used since the 70 s, for example, UV photocuring technology is commonly used in the fields of coatings, printing inks, and electronic device manufacturing, wherein one of the most important concerns of the skilled person is curing efficiency or sensitivity, and the key factor influencing curing efficiency is photoinitiator structure and co-initiator components used in cooperation with the photoinitiator structure.

For example, the thioether oxime ester compounds proposed in patent publication No. CN1241562B are the most successful photoinitiators in photoresist formulations, such as commercial products

OXE01 has relatively good sensitivity and low yellowing, is well known to those skilled in the art, is widely studied and used, and is particularly effective in clear photoresist and RGB color photoresist formulations. Later International publication No. WO2002/100903 discloses oxime ester compounds having more complex substituents on the parent structure of diphenyl sulfide, and also discloses carbazole-parent oxime ester compounds, commercially available products such as those from BASF corporation

OXE 02, although having improved sensitivity, also has a stronger yellowing, making its use in clear and color photoresists very limited. The Chinese patent applications with application publication numbers CN101565472A and CN103833872A are based on the above-mentioned patent compounds, and do not fundamentally change the sensitivity and yellowing of the corresponding oxime ester compounds, such as PBG305 and the corresponding oxime ester compoundsBis-ketoxime ester compounds 1, 3 and 4 disclosed in the PBG304 and CN103833872A patent application specifications; the CN101528694A patent application discloses oxime ester compounds with nitro carbazole as the parent, and the CN103153952A patent application discloses oxime ester compounds with benzo carbazole as the parent, because of the introduction of chromophore nitro group or the large conjugated structure of benzo carbazole, the ultraviolet absorption spectrum of corresponding oxime ester compounds is significantly red-shifted, such as NCI-831 of the company Aidicco and BASF

Two commercial products of OXE 03 have more efficient absorption of the 365nm emission from the light source, showing higher sensitivity, but at the same time, the significantly red shifted uv absorption spectrum also imparts a yellowish color to the compound and significant yellowing in the photoresist, so they are more suitable for use in black photoresist formulations and difficult to use in clear and RGB color photoresists.

In order to improve the color saturation or hiding power, the pigment content in the photocuring formula is higher and higher, especially for the black photoresist with high pigment content, the light energy utilization rate in the curing process is reduced due to the absorption of the pigment, a photoinitiator or a photoinitiator composition with higher sensitivity needs to be developed, and the sensitization of the existing photoinitiator is also one of the methods for improving the sensitivity. Sensitizers are frequently used in photocurable compositions, especially photoresist formulations. Sensitizers described in the prior art, such as disclosed in the CN1241562A patent application, are benzophenone and its derivatives, such as 4- (4-methylphenylthio) benzophenone (trade name Omnirad BMS) or 4, 4' -bis (diethylamino) benzophenone, thioxanthone and its derivatives, such as 2-isopropylthioxanthone, anthraquinone and its derivatives, such as 2-ethylanthraquinone, coumarin derivatives, such as 5, 7-dimethoxy-3- (4-dodecylbenzoyl) coumarin (Esacure 3644 from IGM resins), camphorquinone, phenothiazine and its derivatives, 3- (aroylmethylene) thiazoline, rhodanine and its derivatives, rhodamine, acridine, anthocyanidins, merocyanine dyes, eosin; among them, benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin derivatives are preferable. Experiments prove that the sensitizing agents do not show satisfactory sensitizing effects when used in combination with thioether oxime esters, and some compounds reduce the photocuring efficiency of the formula of the photocuring composition due to containing phenolic hydroxyl groups or anilino groups such as eosin, anthocyanin and phenothiazine; among the four preferred classes of compounds, although they are themselves photoinitiators, the photoinitiation efficiency is much lower than with the thiolyximide compounds, they do not exhibit synergistic sensitization when used in combination with thiolyximides, and some species such as 2-isopropyl thioxanthone and 2-ethylanthraquinone, for their own longer wavelength UV absorption spectrum, give severe yellowing to the formulation and are rendered unusable. There is no ideal sensitizer in the prior art.

However, the pursuit of the technicians for improving the properties such as exposure sensitivity, resolution, thermal stability and the like is never limited, and the existing products and formulation technologies face new challenges.

In order to improve the light transmittance of transparent photoresists and the color purity of color photoresists, the photoinitiator used needs to have lower yellowing, and thus there is still a need to develop new photoinitiator products with higher sensitivity and lower yellowing.

Disclosure of Invention

The invention mainly aims to provide a photoinitiation composition, a photocuring composition, a photoresist, application of the photocuring composition and application of the photoresist, so as to solve the problem of insufficient light sensitivity and yellowing resistance of a photoinitiator in the prior art.

In order to achieve the above objects, according to one aspect of the present invention, there is provided a photoinitiating composition comprising at least one bisacyldiphenyl sulfide derivative selected from compounds represented by formula i and at least one oxime ester compound selected from compounds represented by formula ii:

in the formula I, R₁、R₂Each 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, R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₈And R₁₉Each independently selected from any one of H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom and CN; in the formula II, R₃Any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃May be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₄Any one selected from the following groups: C1-C11 substituted or unsubstituted alkyl, C3-C5 alkenyl, substituted or unsubstituted phenyl, C1-C4 alkoxy, phenoxy; ar (Ar)₁Is a radical whose parent is a C6-C20 aromatic radical, a C4-C30 heteroaromatic radical, a coumarin radical, and which parent is unsubstituted or substituted by one or more halogen atoms, nitro groups, R₁₀X-、

Is substituted in which R₁₀Any one selected from the following groups: C1-C12 alkyl, C3-C12 alkyl interrupted by one or more oxygen or sulfur atoms, C3-C8 cycloalkyl, C3-C8 heterocyclyl, C2-C7 alkenylmethyl, C6-C15 aromatic, C4-C15 heteroaromatic, wherein the hydrogens of the C6-C15 aromatic and C4-C15 heteroaromatic groups are replaced by fluorine atoms, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio or C1-C4 alkylsulfonyl; C1-C12 alkyl substituted by oneOr C3-C12 alkyl and C3-C8-cycloalkyl interrupted by more than one oxygen or sulfur atom may optionally be substituted by F, C1-C4 alkoxy, OH, OOCR₄、COOR₉、(R₉O)₂P(O)、(CH₃)₃Si or phenyl substitution; r₉Is C1-C4 alkyl; r₁₀Or R₁₀' optionally linked to an atom on an adjacent parent to form any of a five-membered ring to a seven-membered ring, X is a direct bond, O, S, CO or R₁₀’N，R₁₀' is C1-C12 alkyl, or X is R₁₀When N is' N, R₁₀R₁₀' N is

R₃' is selected from any one of the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃' may be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₂₀Any one selected from the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl groups, containing one or more O, S spacers and hydroxyl groups and being OOCR₄Substituted C3-C8 alkyl, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; m is₁N is each 0 or 1; ar (Ar)₁The substituents above may optionally form any of a five-membered ring to a seven-membered ring together with the adjacent substituents and the parent atom.

In order to achieve the above object, according to one aspect of the present invention, there is provided a photocurable composition comprising a photocurable resin and an initiator, the initiator being a photoinitiating composition of any one of the above.

In order to achieve the above object, according to an aspect of the present invention, there is provided a use of the photocurable composition of any one of the above, which comprises using the photocurable composition as an ink, a coating material, a sealant, an optical film or an adhesive, preferably as a negative passivation film, a photocurable photosensitive surface coating, a barrier film or a polarizer coating.

In order to achieve the above object, according to one aspect of the present invention, there is provided a photoresist comprising a multifunctional acrylate monomer, an alkali-soluble resin, an initiator and a solvent, the initiator being a photoinitiating composition of any one of the above.

In order to achieve the above object, according to an aspect of the present invention, there is provided a use of the photoresist of any one of the above, further comprising a pigment, the use comprising using the photoresist as a sealant, an optical film, a colored matrix, a photo spacer or a filter, preferably as a negative passivation film, a photo-curable photosensitive surface coating, an insulating film or a polarizer coating.

By applying the technical scheme of the invention, the photoinitiation composition has good light sensitivity and yellowing resistance when being applied.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As analyzed by the background of the present application, the sensitivity and yellowing resistance of the prior art photoinitiators still need to be improved, and in order to solve the problem, the present application provides a photoinitiating composition, a photocurable composition, a photoresist and applications of the photoresist.

In one exemplary embodiment of the present application, a photoinitiating composition is provided, which includes at least one bisacyldiphenyl sulfide derivative selected from compounds represented by formula i and at least one oxime ester compound selected from compounds represented by formula ii:

in the formula I, the compound is shown in the specification,

R₁、R₂each 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; r₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₈And R₁₉Each independently selected from any one of H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom and CN;

in the formula II, R₃Any one selected from the following groups: C1-C16 substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, C4-C7 cycloalkyl; r₃May be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₄Any one selected from the following groups: C1-C11 substituted or unsubstituted alkyl, C3-C5 alkenyl, substituted or unsubstituted phenyl, C1-C4 alkoxy, phenoxy; ar (Ar)₁Is a radical whose parent is a C6-C20 aromatic radical, a C4-C30 heteroaromatic radical, a coumarin radical, and which parent is unsubstituted or substituted by one or more halogen atoms, nitro groups, R₁₀X-、

Is substituted in which R₁₀Any one selected from the following groups: C1-C12 alkyl, C3-C12 alkyl interrupted by one or more oxygen or sulfur atoms, C3-C8 cycloalkyl, C3-C8 heterocyclyl, C2-C7 alkenylmethyl, C6-C15 aromatic, C4-C15 heteroaromatic, wherein the hydrogens of the C6-C15 aromatic and C4-C15 heteroaromatic groups are replaced by fluorine atoms, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio or C1-C4 alkylsulfonyl; hydrogen of C1-C12 alkyl, C3-C12 alkyl interrupted by one or more oxygen or sulfur atoms, and C3-C8 cycloalkylOptionally F, C1-C4 alkoxy, OH, OOCR₄、COOR₉、(R₉O)₂P(O)、(CH₃)₃Si or phenyl substitution; r₉Is C1-C4 alkyl; r₁₀Or R₁₀' optionally linked to an atom on an adjacent parent to form any of a five-membered ring to a seven-membered ring, X is a direct bond, O, S, CO or R₁₀’N，R₁₀' is C1-C12 alkyl, or X is R₁₀When N is' N, R₁₀R₁₀' N is

The photoinitiating compositions of the present application, when applied, have good photosensibility and resistance to yellowing.

In one embodiment, R is as defined above₁And R₂The C1-C12 substituted alkoxy acylThe group is selected from any one of the following groups: by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, R₂₀OOC-substituted C1-C12 alkoxyacyl, substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy, C2-C4 alkoxy, phenoxy C2-C4 alkoxy, R₄COO、R₂₀OOC-substituted C2-C12 alkoxyacyl; wherein the substituents on the C6-C20 substituted aryl, C4-C20 substituted heteroaryl and C6-C20 substituted aryl acyl, and the substituents on the C4-C20 substituted heteroaryl acyl comprise halogen atoms and R₂₀、-OR₃₀、-SR₃₀、-NR₃₁R₃₂、-COOR₃₀、-CONR₃₁R₃₂And the substituent can be arbitrarily combined with the parent ring atom to form a five-membered ring to a seven-membered ring; r₂₀And R₃₀Each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl groups, containing one or more O, S spacers and hydroxyl groups and being OOCR₄Substituted C3-C8 alkyl, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; r₃₁And R₃₂Each independently selected from any one of the following groups: C1-C4 alkyl, C1-C4 alkyl substituted with hydroxy; or NR₃₁R₃₂Is composed of

Or the above R₄In the formula, the C1-C11 substituted alkyl is C1-C11 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl and CN, and the substituted phenyl is phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy and CN.

Preferably, R is as defined above₁And R₂Each independently selected from any one of the following groups: phenyl, phenyl substituted by one or more F, methyl, C1-C4 alkoxyacyl, thienyl, benzoyl substituted by one or more F, methyl, C1-C4 alkoxyacyl, C1-C4 alkoxyacylSubstituted by a C4-C7 cycloalkyl group, C4-C7 heterocyclyl group, phenyl group, R₂₀OOC-substituted C1-C4 alkoxyacyl substituted by a C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy C2-C4 alkoxy, 2-phenoxyethoxy, CH₃COO、R₂₀OOC-substituted C2-C4 alkoxyacyl; r₁₁，R₁₂，R₁₃，R₁₄，R₁₅，R₁₆，R₁₈，R₁₉Each independently is any one of H, C1-C4 alkyl, C1-C4 alkoxy and F; r₂₀Is C1-C8 alkyl.

For oxime ester compounds, preferably, Ar mentioned above₁The parent structure of (a) is selected from any one of the following groups: benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, thianthrene, thioxanthone, fluorene, benzofluorene, carbazole, benzocarbazole, dibenzocarbazole.

In one embodiment, at least one of the oxime ester compounds described above is selected from the group consisting of compounds represented by formula III:

wherein n is₁Is 1 or 0; r₃Any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen or sulfur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃Can be connected with adjacent benzene rings to form any one of five-membered ring to seven-membered ring; r₄Any one selected from the following groups: C1-C11 alkyl, C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl, C1-C4 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, phenyl, C1-C4 alkyl, C3832-C3 alkenyl, C3-C3 alkenyl, C1-C4 alkyl, C3-C3 alkenylC1-C4 alkoxy, CN substituted phenyl, C1-C4 alkoxy, phenoxy; r₂₁，R₂₂，R₂₃，R₂₄Each independently is H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom or CN; r₂₅，R₂₆，R₂₇，R₂₈，R₂₉Each independently of the others being H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, NO₂C1-C8 substituted or unsubstituted alkanoyl,

C6-C15 substituted or unsubstituted aromatic acyl, C4-C15 substituted or unsubstituted heteroaromatic acyl, and the substituent of substituted C1-C8 alkyl is selected from halogen atom, C4-C7 cycloalkyl, hydroxyl, CN, R₄Any one or more of COO, substituted C6-C15 aryl and substituted C4-C15 heteroaryl is/are independently selected from halogen atom, CN and R₂₀、OR₃₀、SR₃₀、NR₃₁R₃₂、COOR₃₀、CONR₃₁R₃₂Any one of (1), R₃₁,R₃₂Each independently is C1-C4 alkyl, C1-C4 alkyl substituted with hydroxy; or NR₃₁R₃₂Is to be

Preferably, when the oxime ester compound has the formula III above, R above is₃Any one selected from C1-C6 alkyl, C1-C3 alkyl substituted by C4-C7 cycloalkyl, and C4-C7 cycloalkyl; r₄Is methyl or phenyl; r₂₁，R₂₂，R₂₃，R₂₄Each independently selected from any one of H, C1-C4 alkyl, C1-C4 alkoxy and F; r₂₅，R₂₆，R₂₇，R₂₈，R₂₉Each independently selected from H, C1-C8 substituted or unsubstituted alkyl, F, C1-C8 alkanoyl,

any one of substituted or unsubstituted benzoyl, substituted or unsubstituted thiophene-2-formyl and substituted or unsubstituted benzofuran-2-formyl, wherein the substituent of C1-C8 substituted alkyl is one or more of F, C4-C7 cycloalkyl, hydroxyl, R₄COO, substituted benzoyl, substituted thiophene-2-formyl, substituted benzofuran-2-formyl having a substituent of F, R₂₀、OR₃₀、COOR₃₀、CONR₃₁R₃₂Any one of the above; r₃' any one selected from the group consisting of C1-C6 alkyl, C1-C3 alkyl substituted with one C4-C7 cycloalkyl, C4-C7 cycloalkyl; r₂₀，R₃₀Each independently selected from H, C1-C8 alkyl, C1-C4 alkyl substituted with one or more F, C3-C7 cycloalkyl groups, having one or more O, S spacers and hydroxyl groups, OOCR₄Substituted C3-C8 alkyl, five-or six-membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; r₃₁,R₃₂Each independently selected from any one of C1-C4 alkyl; or NR₃₁R₃₂Is of a ring structure

The substitution may be mono-substitution or poly-substitution.

In another embodiment, at least one of the oxime ester compounds is selected from any one of the compounds of formula IV, formula V, and formula VI:

wherein, Y₁，Y₂，Y₃Each independently selected from H, Ar₂CO、

Or Y is₃Is NO₂(ii) a Wherein m is₂，n₂，n₃，n₄Each independently is 1 or 0; r₃Any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃May be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₄Any one selected from the following groups: C1-C11 alkyl, C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN, C1-C4 alkoxy, phenoxy; r₅，R₆，R₇，R₈Each independently selected from any one of the following groups: h, C1-C8 alkyl, C3-C8 alkyl interrupted by one or 2 oxygen atoms, C2-C7 alkenylmethyl, phenyl; the hydrogen of the alkyl and phenyl groups being optionally substituted by halogen atoms, C4-C7 cycloalkyl, hydroxy, R₄COO、COOR₉、(R₉O)₂P(O)、(CH₃)₃Si and phenyl substitution; r₉Is C1-C4 alkyl; r₅，R₆，R₇，R₈Each independently can form any one of five-membered ring to seven-membered ring together with adjacent substituent and atom on the parent; ar (Ar)₂Any one selected from the following groups: a C6-C15 aromatic group, a C4-C15 heteroaromatic group; wherein the hydrogen on carbon atom is substituted by fluorine atom, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, and the hydrogen on C1-C4 alkyl is substituted by fluorine atom, C1-C4 alkoxy, R4 alkylsulfonyl₄COO is substituted by any one of COO; r₄₁，R₄₂，R₄₃，R₄₄，R₄₅Each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, C1-C8 substituted or unsubstituted alkylacyl,

C6-C15 substituted or unsubstituted aroyl, C4-C15 substituted or unsubstituted heteroaryl acyl, and C1-C8 substituted alkyl substituents selected from halogen atom, C4-C7 cycloalkyl, hydroxy, CN, R₄Any one or more of COO; the substituents of C6-C15 substituted aroyl and C4-C15 heteroarylacyl are selected from H, halogen atom, CN, R₂₀、OR₃₀、SR₃₀、NR₃₁R₃₂、COOR₃₀、CONR₃₁R₃₂Any one or more of; r₂₀，R₃₀Each independently is 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, acetoxy substituted, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; r₃₁，R₃₂Each independently is any one of C1-C4 alkyl and C1-C4 alkyl substituted by hydroxyl; or NR₃₁R₃₂Is to be

In one embodiment, at least one of the oxime ester compounds is selected from any one of the compounds of formula IV, formula V, and formula VI: wherein, Y₁，Y₂，Y₃Each independently selected from Ar₂CO、

Wherein m is₂，n₂，n₃，n₄Each independently is 1 or 0; or Y₃Is NO₂；R₃Any one selected from the following groups: C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, benzyl, substituted or unsubstituted phenyl; r₄Any one selected from the following groups: methyl, phenyl, C1-C4 alkoxy; r₅，R₆，R₇，R₈Each independently selected from any one of the following groups: C1-C4 alkyl, phenyl, alkyl and phenyl hydrogen optionally substituted by COOR₉、(R₉O)₂P(O)、(CH₃)₃Si and phenyl substitution; r₉Is C1-C4 alkyl; ar (Ar)₂Any one selected from the following groups: phenyl, thienyl, benzofuranyl; the hydrogen on the phenyl is replaced by any one of a fluorine atom, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 alkylsulfonyl, and the hydrogen on the C1-C4 alkyl is replaced by a fluorine atom and C1-C4 alkoxy; r₄₁，R₄₂，R₄₃，R₄₄，R₄₅Each independently selected from any one of the following groups: h, C1-C4 alkyl, C1-C4 alkoxy, halogen atom, CN.

These oxime ester compounds are used in combination with the compounds of formula I in a ratio which gives a higher sensitivity effect, but when Y is used₁In the case of the nitro group, for example, the combination of NCI 831, a product of ADEKA of Japan, with the compound of formula I-14 has no sensitivity-increasing effect.

In another embodiment, at least one of the oxime ester compounds described above is selected from the group consisting of compounds represented by formula VII:

wherein R is₃Any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulfur atoms, phenyl, byOne or more halogen atoms, C1-C12 alkyl groups, C1-C4 alkoxy groups, CN-substituted phenyl groups, C4-C7 cycloalkyl groups; r₄Any one selected from the following groups: C1-C11 alkyl, C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN, C1-C4 alkoxy, phenoxy; r₅₁，R₅₂，R₅₃，R₅₄，R₅₅Each independently selected from any one of the following groups: h, halogen atom, CN, R₂₀，OR₃₀，SR₃₀，NR₃₁R₃₂，COOR₃₀，CONR₃₁R₃₂Adjacent substituents together optionally form any of a five to seven membered ring structure; r₂₀，R₃₀Each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted by one or more F, Cl, OH, C3-C7 cycloalkyl, C3-C8 alkyl substituted by one or more O, S spacers and hydroxyl, acetoxy, five-membered or six-membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl; r₃₁,R₃₂Each independently is any one of C1-C4 alkyl and C1-C4 alkyl substituted by hydroxyl; or NR₃₁R₃₂Is composed of

Preferably, at least one of the oxime ester compounds is selected from the group consisting of compounds represented by formula VII: wherein R is₃Any one selected from the following groups: C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, benzyl, substituted or unsubstituted phenyl; r₄Any one selected from the following groups: methyl, phenyl, C1-C4 alkoxy; r₅₁，R₅₂，R₅₃，R₅₄，R₅₅Each independently selected from any one of the following groups: h, methoxy, methylthio.

These oxime ester compounds are used in combination with the compounds of formula I in specific proportions to give a higher sensitivity effect.

In one embodiment, the bisacyldiphenyl sulfide derivative is selected from one of the following compounds or any mixture thereof,

the diacyl diphenyl sulfide derivative with the structure is combined with certain oxime ester compounds according to a certain proportion to produce an additional high-sensitivity effect.

In one embodiment, the oxime ester compound is selected from one of the following compounds or any mixture thereof:

when the oxime ester compound with the structure is matched with the diacyl diphenyl sulfide derivative, the photo-curing sensitivity value is obviously higher than that of the oxime ester compound used alone.

In order to further improve the synergistic sensitization of the two substances, the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound is preferably 0.1:1 to 3:1, preferably 0.3:1 to 1.4:1, and the bisacyldiphenyl sulfide derivative and the oxime ester compound are preferably combined in different optimal ratios according to different combinations of the bisacyldiphenyl sulfide derivative and the substance compound.

The preparation process of the bisacyldiphenyl sulfide derivatives of the present application is illustrated below.

One preparation method comprises the following steps:

first, a thioether feedstock

And R₁COX is subjected to a friedel-crafts acylation reaction, then is subjected to a second friedel-crafts acylation reaction with R2COX, and the reaction liquid is hydrolyzed to obtain an intermediate of a formula I or a formula I;

second step, when R is₁Or R₂When there is an active group, e.g. R₁Or R₂For the p-fluorophenyl group, further substitution reactions take place to give the final compounds of formula I, for example of formulae I-11 and I-12.

Wherein the thioether is as a starting material

As the compounds disclosed in the prior art, there may be used, for example, diphenyl sulfide, 2-methyldiphenyl sulfide and the like; r₁COX or R₂R in COX₁And R₂Can be the same or different, and X is Cl or Br;

another preparation method of the diacyl diphenyl sulfide derivative comprises the following steps:

the first step, the preparation of intermediate III, starting from the compound of formula IX, R₁COX is acylating agent, and is subjected to Friedel-crafts acylation reaction to obtain intermediate formula X, and then is reacted with formula XI

Carrying out thioetherification reaction on the thiophenol compound to obtain an intermediate shown as formula III (I-A); the thioetherification reaction is usually carried out under the alkaline condition of a polar solvent, and the reaction solution is purified through the necessary steps of water washing, crystallization and the like to obtain an intermediate shown as formula I-A;

in the second step, the intermediate of formula I-A is reacted with an acylating agent R₂COX undergoes a Friedel-crafts acylation reaction to obtain a formula I;

when R is₁Or R₂Is a C6-C20 aryl group having an ortho substituent COOR₃₀When, for example, formula I-7 to I-9,

the third preparation method of the diacyl diphenyl sulfide derivative comprises the following steps:

first, a thioether feedstock

Carrying out Friedel-crafts acylation reaction with one or two moles of phthalic anhydride to obtain a diacylate or monoacylate; wherein monoacylate is further reacted with R₂COX is subjected to secondary friedel-crafts acylation reaction, and the reaction liquid is hydrolyzed to obtain an intermediate with carboxyl in the formula I;

in a second step, the intermediate of formula I with carboxyl groups is subjected to esterification or amidation and possibly other reactions such as condensation to give the final product of formula I.

One method for preparing oxime ester compounds is: with R₄COCl or (R)₄CO)₂O is an esterification reagent, and the oximate II-A is esterified to obtain the formula II.

The specific operating conditions of the above preparation methods can be obtained by those skilled in the art through experimental investigation based on the prior art and in combination with the following specific preparation examples of the present application, and are not described herein again.

In another exemplary embodiment of the present application, there is provided a photo-curable composition comprising a photo-curable resin and an initiator, the initiator being any one of the photo-initiation compositions described above.

Because the photoinitiation composition has the characteristics of high photosensitivity and high yellowing resistance, the photocuring composition has higher sensitization efficiency and thermal stability.

The above-mentioned photocurable resin may comprise at least one radically polymerizable compound. Wherein the free radical polymerizable compound may be selected from acrylate, methacrylate based compounds, resins containing acrylate or methacrylate groups or any mixture thereof.

Preferably, among the above radically polymerizable compounds, examples of the low-molecular-weight double bond compound are alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate; other examples are acrylonitrile, vinyl acetate, vinyl ethers, styrene, N-vinylpyrrolidone. Examples of the compound having two or more double bonds are diacrylate esters of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1, 6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, triallyl isocyanurate, and the like. Examples of higher molecular weight double bond compounds are a broad class of materials known as oligomers, such as acrylated epoxy resins, acrylated polyester resins unsaturated polyester resins, acrylated polyether resins, acrylated polyurethane resins, typically having a molecular weight of 500-3000.

The light-cured composition is used for producing colored or non-colored ink, paint and adhesive, and specific applications comprise printing, dental materials, optical films, isolating films, polaroids, cylindrical gaskets, microlenses, optical fiber coatings, substrate protective coatings, electronic device protective coatings, passivation films, sealants, PCB solder masks, liquid or dry film corrosion-resistant materials, 3D printing, recording materials, bonded glass, plastics and metal components.

With the exception of those mentioned here, it is easy for the person skilled in the art to add further essential ingredients, such as stabilizers, surfactants, levelling agents, dispersants, as required by the prior art and the use of the photocurable compositions.

In order to improve the initiation efficiency, the mass content of the above-mentioned initiator in the solid content of the photocurable composition is preferably 0.1 to 10%.

Further, the present application provides a use of the photocurable composition of any one of the above, which comprises using the photocurable composition as an ink, a coating or an adhesive. Other necessary components can be added by those skilled in the art according to the requirements of ink color, printing application and the like. The ink or coating can be used for pattern printing, 3D printing, PCB solder mask, liquid or dry film corrosion resistant material, substrate protective coating and the like. In addition to the above-mentioned photocurable composition, other essential ingredients may be added according to the performance requirements of the adhesive. For bonding glass, plastic, metal members, etc.

In yet another exemplary embodiment of the present application, there is provided a photoresist comprising a multifunctional acrylate monomer, an alkali-soluble resin, an initiator, and a solvent, the initiator being a photoinitiating composition of any of the above.

Because the photoinitiation composition has the characteristics of high photosensitivity and high yellowing resistance, the photoresist has higher sensitization efficiency and thermal stability, and the photoresist pattern formed after the patterning treatment has higher development line width.

The transparent photoresist without pigment can be used for manufacturing high-transmittance films such as protective coatings, sealants, polaroids, lenses and the like.

The application also provides a colored photoresist, which further comprises the following components on the basis of the transparent photoresist: a pigment; when the pigment is a red pigment, obtaining a red photoresist; when the pigment is a green pigment, obtaining a green photoresist; when the pigment is a blue pigment, obtaining a blue photoresist; they may be collectively referred to as color photoresists. When the pigment is a black pigment such as carbon black or titanium black, a black photoresist is obtained. A black matrix, a column spacer of a Cell gap (Cell gap), may be manufactured using a black photoresist. In addition, a color filter device can be obtained by using a transparent photoresist, a color photoresist or a black photoresist as a raw material through a color filter processing process, and is an important component of a color display screen.

In order to improve the initiation efficiency, the mass content of the above initiator in the solid matter of the resist is preferably 0.1 to 10%, preferably 1 to 8%.

Examples of the above multifunctional acrylates are dipentaerythritol hexaacrylate, pentaerythritol acrylate; examples of the alkali-soluble resin are polyacrylates having a carboxylic acid group, such as copolymers obtained by copolymerizing methacrylic acid, itaconic acid, maleic acid, etc. with common monomers such as methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, etc. in a desired ratio; examples of the copolymer are preferably a methyl methacrylate and methacrylic acid copolymer, a benzyl methacrylate and methacrylic acid copolymer, a methyl methacrylate and butyl methacrylate, and a methacrylic acid and styrene copolymer.

The pigment may be c.i. pigment red 177, c.i. pigment green 7, c.i. pigment blue 15:6, solvent blue 25, carbon black, titanium black, c.i. pigment black 1.

In the above-mentioned photocurable composition and photoresist, in addition to the above-mentioned bisacyldiphenyl sulfide derivative and oxime ester compound in the photoinitiating composition of the present application, other photoinitiator or co-initiator which is commercially available or known in the art may be added, as long as the properties of the photocurable composition, especially photoresist, are advantageous. For example 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-isopropylthioxanthone, 2, 4-diethylthioxanthone, bis (2, 6-difluoro-3-pyrrolylphenyl) titanocene.

Examples of other resins which may be added in addition to the above-mentioned components are polyalkylmethacrylates, ethylcellulose, carboxymethylcellulose, novolak resins, polyvinyl butyral, polyvinyl acetate, polyesters, polyimides.

Any article obtained by processing any material containing the photoinitiation composition of the present invention through necessary processes, including finished products such as a negative passivation film, a photocuring photosensitive surface coating, an insulating film, a polarizer coating, etc.

The advantageous effects of the present application will be further described below with reference to examples and comparative examples.

Curing light source equipment used:

365nm LED area light source, 28095Fuzhou blue sky lamp development Limited;

testing equipment:

stereo microscope, COVS-50G, Mingmei photoelectricity technologies, Guangzhou, with line width in μm;

a yellowness meter and a full-automatic color difference meter SC-80C.

Experimental materials:

a compound of formula I-2: 4, 4' -bis (2-methylbenzoyl) diphenyl sulfide from compound preparation 1;

a compound of formula I-3: 4, 4' -bis (2-fluorobenzoyl) diphenyl sulfide from compound preparation 2;

a compound of formula I-5: 4- (2-fluorobenzoyl) -4' - (3-methylbenzoyl) diphenyl sulfide from compound preparation 3;

a compound of formula I-6: 4, 4' -bis (3-methylbenzoyl) diphenyl sulfide from compound preparation 4;

compounds of formula I-10: 3-fluoro-4- (3-methylbenzoyl) -4' -benzoyldiphenyl sulfide from compound preparation 5;

compounds of formula I-12: 4, 4' -bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] diphenyl sulfide from compound preparation 6;

a compound of formula I-13: 4- (3-methylbenzoyl) -4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide from compound preparation 7;

compounds of formula I-14: 4, 4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide, from compound preparation 8;

compounds of formula I-15: 4- (2-methoxy-2-oxoacetyl) -4' - (2-ethoxy-2-oxoacetyl) diphenyl sulfide from compound preparation 9;

compounds of formula I-18: 4- (2-methoxy-2-oxoacetyl) -4' - (thiophene-2-formyl) diphenyl sulfide from compound preparation 10;

compounds of formula I-19: 4, 4' - (2-cyclohexylmethoxy-2-oxoacetyl) diphenyl sulfide from compound preparation 14;

4-benzoyl-4' -methyldiphenylsulfide: omnirad BMS, a photoinitiator product of IGM resins;

5, 7-dimethoxy-3- (4-dodecylbenzoyl) coumarin: photoinitiator product Esacure 3644 from IGM resins corporation;

4- (2-benzoyloxyiminooctanoyl) diphenyl sulfide: a compound of formula II-1, photoinitiator product OXE01 from BASF;

9-ethyl-3- (1-acetoxyiminoethyl) -6- (2-methylbenzoyl) carbazole: a compound of formula II-26, photoinitiator product OXE 02 from BASF;

11- (2-ethylhexyl) -5- (2,4, 6-trimethylbenzoyl) -8- (1-acetoxyimino-1- [2- (2,2,3, 3-tetrafluoropropoxy) phenyl ] methylbenzo [ a ] carbazole, a compound of formula II-43, product OXE 03, a photoinitiator from BASF;

a compound of formula II-4: 1- (4-thiophenylphenyl) -3-cyclopentylpropane-1, 2-dione-2-oxime benzoate, photoinitiator product PBG305 from Tronly, usa;

a compound of formula II-6: 1- (4-thiophenylphenyl) -3-cyclohexylpropane-1, 2-dione-2-oxime acetate, photoinitiator product PBG 3057 from Tronly, Van;

compounds of formulae II-27: 9-ethyl-3- (1-acetoxyimino-3-cyclopentylpropyl) -6- (2-methylbenzoyl) carbazole, photoinitiator product PBG304 from Tronly, usa;

compounds of formulae II-17: 4- (2-acetoxyiminopropionyl) -4' - (3-methylbenzoyl) diphenyl sulfide from compound preparation 11;

compounds of formulae II-18: 4- (2-Acetoxyimino-2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide from Compound preparation 12;

compounds of formulae II-15: 4, 4' -bis (2-acetoxyiminopropionyl) diphenyl sulfide from compound preparation 13;

photomer 6010: aliphatic polyurethane triacrylate, product of IGM resins, Netherlands;

photomer 4149: trimethylolpropane ethoxy (3) triacrylate, a product of IGM resin company;

DPHA: dipentaerythritol penta-and hexa-acrylate, a product of Tianjin Tianjiao chemical Co., Ltd;

HPMA: polymaleic acid, a product of alatin industries, usa.

Preparation example

Preparation of diacyl diphenyl sulfide derivatives

Compound preparation example 14, 4' -bis (2-methylbenzoyl) diphenyl sulfide (compound of formula I-2)

Adding 80g of dichloroethane and 28g of anhydrous aluminum trichloride into a 250ml four-mouth bottle, cooling to 0 ℃, adding 15g of diphenyl sulfide into the four-mouth bottle, and then dropwise adding 27.4g of o-methylbenzoyl chloride within 10 ℃; continuously stirring and reacting for 4 hours at room temperature; after the reaction was completed, the reaction solution was added dropwise to 30g of concentrated hydrochloric acid and 100g of ice waterMedium, temperature not higher than 30 ℃; continuously stirring for 30min, and standing for liquid separation; washing the obtained organic phase with 100ml of water for 30min, and standing for liquid separation; the dichloroethane is removed by reduced pressure distillation to obtain 37.5g of solid residue; heating 90g of absolute ethyl alcohol to dissolve the solid residues, then cooling to separate out crystals, filtering the separated crystals, and drying to obtain 28g of white solid with the content of 98.58% and the yield of 82.4%; the melting range is 68.7-71.2 ℃; warp beam¹H-NMR(CDCl₃) Confirmation of the structure, delta [ 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)。

Compound preparation example 24, 4' -bis (2-fluorobenzoyl) diphenyl sulfide (compound of formula I-3)

Adding 40ml of dichloroethane, 8.67g of anhydrous aluminum trichloride and 3.73g of diphenyl sulfide into a 100ml four-mouth bottle, and reducing to-5 ℃; then 7.54g of o-fluorobenzoyl chloride is dripped into the four-mouth bottle, and after the addition is finished, the reaction is carried out for 15 hours at the temperature of 10 ℃; dropwise adding the reaction solution into 12.0g of concentrated hydrochloric acid and 24.0g of ice water for acidolysis, and heating to 20 ℃ after dropwise adding, and stirring for 1 hour; the separated organic phase is washed once more with 24g of water; then removing the organic phase by vacuum distillation, wherein the mass of the remainder is 8.92 g; dissolving the residue with a mixture of 36g of ethanol and 12g of tetrahydrofuran, and cooling to separate out crystals. The precipitated crystals were filtered, and the filter cake was dried to obtain 7.4g of a white crystalline solid with a yield of 86%. Content 98.17%, melting range: 114.5 to 116.6 ℃. Warp beam¹H-NMR(CDCl₃) Confirmation of the structure, delta [ 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)。

PREPARATION OF COMPOUNDS EXAMPLE 34- (2-FLUOROBENZOYL) -4' - (3-METHYLBENZOYL) BENZOLE SULFIDE (COMPOUND OF FORMULA I-5)

Preparation of 4- (3-methylbenzoyl) diphenyl sulfide

Adding 90ml of dichloroethane and 14.5g of anhydrous aluminum trichloride into a 250ml four-mouth bottle, stirring and cooling to-5 ℃, and adding 20.0g of diphenyl sulfide into the four-mouth bottle; slowly dropwise adding 15.5g of 3-methylbenzoyl chloride, keeping the temperature below 0 ℃, stirring and reacting for 6 hours, dropwise adding the reaction liquid into 60ml of 30ml of concentrated hydrochloric acid and ice water for acidolysis, keeping the temperature not more than 20 ℃, stirring for 30 minutes, standing to separate out an organic phase, washing the organic phase once by using 10ml of concentrated hydrochloric acid and 40ml of water, standing and layering;

the organic phase obtained by layering was washed once with 40ml of water; the separated organic phase was subjected to distillation under reduced pressure to remove dichloroethane to give 32.7g of a pale yellow oil; dissolving the light yellow oily substance with 90ml of absolute ethyl alcohol, cooling to separate out a white solid, and preserving heat for 1.5h at-9 ℃; filtering out solid, drying and weighing 28g, wherein the yield is 85.6%, the content is 98.86%, and the melting range is 57.9-60.5 ℃;

preparation of 4- (2-fluorobenzoyl) -4' - (3-methylbenzoyl) diphenyl sulfide

Adding 15ml of dichloroethane, 2.0g of anhydrous aluminum trichloride and 1.52g of the 3a product into a 50ml four-mouth bottle, cooling to-5 ℃, dropwise adding 0.88g of o-fluorobenzoyl chloride, slowly raising the temperature to 20 ℃ after the addition, and carrying out heat preservation reaction for 2 hours;

dropwise adding the reaction solution into 4.0g of concentrated hydrochloric acid and 8.0g of ice water for acidolysis, then stirring for 1h at 20 ℃, standing for liquid separation, and washing the organic phase with 10ml of water; the obtained organic phase is subjected to reduced pressure distillation to remove dichloroethane, and 2.0g of residue is obtained; adding a mixed solvent of 8.0g of ethanol and 2.0g of tetrahydrofuran into the residue, heating for complete dissolution, cooling for crystallization, filtering out crystals, and drying to obtain 1.6g of white crystals, wherein the yield is 75%, the content is 98.5%, and the melting range is 109.5-113.4 ℃. Warp beam¹H-NMR (CDCl3) confirmed the structure as 4- (2-fluorobenzoyl) -4' - (3-methylbenzoyl) diphenyl sulfide, [ delta ] 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)。

Compound preparation example 44, 4' -bis (3-methylbenzoyl) diphenyl sulfide (compound of formula I-6)

Adding 3.0g of diphenyl sulfide and 60ml of dichloroethane into a 100ml three-necked flask, stirring and cooling to-5 ℃, and adding 6.5g of anhydrous aluminum trichloride; dropwise adding 5.5g of 3-methylbenzoyl chloride, heating to 10 ℃, and stirring for reacting for 15 hours; dropping the reaction solutionHydrolyzing 20g of concentrated hydrochloric acid and 60ml of ice water, washing the separated organic phase with 60ml of water, then concentrating part of dichloroethane under reduced pressure, separating out white crystals from the solution, continuously cooling to room temperature, separating out a large amount of white solids, washing and filtering the white solids, drying, weighing 5.6g, obtaining the yield of 82.2%, the HPLC content of 98.53% and the melting range of 138.6-142.4 ℃. Warp beam¹H-NMR (CDCl3) confirmed the structure to be 4, 4' -bis (3-methylbenzoyl) diphenyl sulfide, delta [ 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)。

Preparation of Compound 53-fluoro-4- (3-methylbenzoyl) -4' -benzoyldiphenyl sulfide (Compound of formula I-10)

Preparation of 5 a.3-fluoro-4' -benzoyldiphenyl sulfide

Putting 2.0g of 3-fluorobenzothiophenol, 1.85g of NaOH powder, 3.40g of 4-chlorobenzophenone and 20ml of DMSO into a 100ml single-neck bottle, stirring and reacting for 10h at 80 ℃ under the protection of nitrogen, dropwise adding the reaction liquid into 120ml of ice water, stirring for 1h, filtering and drying a filter cake, and recrystallizing by using 45ml of absolute ethyl alcohol to obtain 3.15g of dry white crystals with the yield of 63.8%; the content is 99.1 percent, and the melting range is 82.5-83.9 ℃; the structure was confirmed to be 3-fluoro-4' -benzoyldiphenyl sulfide by 1H-NMR spectrum. Delta [ 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//7.591//7.616(tt,1H,ArH)；7.724/7.752(d,2H,ArH)；7.769/7.793(d,2H,ArH)。

Preparation of 3-fluoro-4- (3-methylbenzoyl) -4' -benzoyldiphenyl sulfide

Putting 20ml of 1, 2-dichloroethane and 2.05g of the product obtained in the step 5a into a 100ml three-necked bottle, stirring and cooling to 5 ℃, adding 3.0g of anhydrous aluminum chloride, keeping the temperature at 10 ℃, and dropwise adding 1.05g of 3-methylbenzoyl chloride; continuously stirring and reacting for 12 h; dripping the reaction solution into 5ml of concentrated hydrochloric acid and 10ml of ice water, stirring for 1h at 10-30 ℃, and standing for liquid separation; washing the obtained organic phase with 20ml of water for 30min, and standing for liquid separation; the organic phase is distilled under reduced pressure toRemoving 1, 2-dichloroethane; dissolving the obtained residue with 20ml ethanol, cooling to-15 deg.C, filtering to obtain crystal, and oven drying the crystal to obtain white solid 2.15 g; the yield is 76.4%, the content is 97.8%, and the melting range is 139.0-142.0 ℃. By passing¹H-NMR spectrum confirmed the structure to be 3-fluoro-4- (3-methylbenzoyl) -4' -benzoyldiphenyl sulfide, delta [ 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)。

Compound preparation example 64, 4' -bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] diphenyl sulfide (Compound of formula I-12) preparation

Preparation of 4a, 4' -bis (4-fluorobenzoyl) diphenyl sulfide (compound of formula I-4)

3.7g of diphenyl sulfide, 50g of 1, 2-dichloroethane and 6.1g of anhydrous aluminum trichloride are put into a 100ml four-mouth bottle and cooled to 0 ℃; 7.0g of p-fluorobenzoyl chloride is dripped in, and the temperature is naturally raised to 25 ℃ to be stirred and react for 20 hours; adding the reaction solution into 30g of 10% HCl solution at 0 ℃ in batches, stirring for 30min after the addition is finished, standing for 30min, separating liquid, washing an organic phase once by using 30ml of water, washing once by using 30ml of 2% sodium hydroxide solution, and washing once by using 30ml of water; removing 30g of dichloroethane solution by vacuum distillation of the organic phase, cooling for crystallization, filtering and drying a filter cake to obtain 7.5g of white powder with the yield of 87.1 percent, the content of 98.5 percent and the melting range of 227.3-230.6 ℃, and passing through¹H-NMR spectrum confirmed the structure of 4, 4' -bis (4-fluorobenzoyl) diphenylsulfide, [ delta ] 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)。

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

Dissolving 2.0g of the product of step 6a in 15ml of pyridine in a 50ml reaction flask, adding 2.6g of 2,2,3, 3-tetrafluoropropanol and 0.9g of NaOH solid, stirring and reacting at 50 ℃ for 6h, adding the reaction solution into 100ml of water, filtering and separatingRecrystallizing the solid with 25ml ethyl acetate to obtain white flaky crystals, drying the white flaky crystals to obtain 2.5g of the white flaky crystals with the content of 98.0 percent, the yield of 82.6 percent and the melting range of 205.3-208.6 ℃; the structure was confirmed to be 4, 4' -bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl group by 1H-NMR spectrum]Diphenyl sulfide,. delta. [ ppm, CDCl ]₃]: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(tt,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)。

Compound preparation example 74- (3-methylbenzoyl) -4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide (Compound of formula I-13)

30g of dichloroethane and 5.5g of aluminum trichloride were put into a 100ml three-necked flask, 5g of the product 3a of the compound preparation 3 was added thereto, and 1.8g of oxalyl chloride monomethyl ester was added dropwise while maintaining the temperature at 10 ℃; continuously stirring and reacting for 3 hours; dripping the reaction solution into 10ml of concentrated hydrochloric acid and 30ml of ice water, stirring for 1h at 10-30 ℃, and standing for liquid separation; washing the organic phase with 50ml of water for 30min, and standing for liquid separation; distilling under reduced pressure to remove dichloroethane; after the remainder was dissolved in 20g of ethanol, the temperature was reduced to-15 ℃, crystals precipitated were filtered, and 5.4g of pale yellow crystalline solid was obtained by drying with a yield of 84%. The content is 97.84%, and the melting range is 121.4-122.7 ℃. By passing¹The structure was confirmed by H-NMR spectrum to be 4- (3-methylbenzoyl) -4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide. Delta [ 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)。

Compound preparation example 84 preparation of 4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide (Compound of formula I-14)

Adding 50g of dichloromethane and 16.1g of anhydrous aluminum trichloride into a 100ml three-necked bottle, cooling to 0 ℃, and adding 5g of diphenyl sulfide; 7.2g of oxalyl chloride monomethyl ester is dripped, and the mixture is stirred and reacts for 6 hours at the temperature of no more than 10 ℃; adding 20g of concentrated hydrochloric acid and 50g of ice water into a 250ml four-mouth bottle, dropwise adding all reaction liquid into the bottle, stirring the mixture at room temperature for 30min, and standing and separating the liquid; washing the organic phase with 50ml of water for 30min, and standing for liquid separation; subjecting the organic phase to vacuum distillationRemoving part of dichloromethane; cooling the residual solution to-15 ℃, filtering the separated crystals, and drying to obtain 8.0g of yellow needle-shaped crystals with the content of 99.30 percent, the yield of 84 percent and the melting range of 106.8-110.0 ℃.¹H-NMR spectrum confirmed the structure 4, 4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide,. delta. [ ppm, CDCl₃]:3.985(s,6H,2CH₃)；7.451/7.480(d,4H,4ArH)；7.987/8.015(d,4H,4ArH)。

Compound preparation example 94 preparation of- (2-methoxy-2-oxoacetyl) -4' - (2-ethoxy-2-oxoacetyl) diphenyl sulfide (Compound of formula I-15)

9 a.preparation of 4- (2-ethoxy-2-oxoacetyl) diphenyl sulfide

20g of dichloroethane and 10.7g of anhydrous aluminum trichloride are put into a 100ml three-necked bottle, the temperature is reduced to 0 ℃, and 10g of diphenyl sulfide is added; 8.1g of oxalyl chloride monoethyl ester is dripped, and the reaction is kept at the temperature of 5-10 ℃ for 4 hours; putting 40g of water and 10g of concentrated hydrochloric acid into a 250ml four-mouth bottle, cooling to 0 ℃, dropwise adding the reaction liquid into ice water, controlling the temperature to be not higher than 30 ℃, stirring for 30min, and standing for liquid separation; washing the organic phase with 50ml of water for 30min, and standing for liquid separation; the organic phase was subjected to reduced pressure distillation to remove the solvent, to obtain 12g of yellow liquid, the content of which was 98.56%, and the yield was 78%.

9 b.preparation of 4- (2-methoxy-2-oxoacetyl) -4' - (2-ethoxy-2-oxoacetyl) diphenyl sulfide (Compound of formula I-15)

50g of dichloroethane and 10.5g of anhydrous aluminum trichloride are placed in a 100ml three-necked flask, the temperature is reduced to 0 ℃, and 5g of the product obtained in the operation 9a is added; dropwise adding 2.4g of oxalyl chloride monoethyl ester, keeping the temperature of the reaction solution not more than 10 ℃, and then continuously stirring for reaction for 4 hours; putting 40g of water and 10g of 36% hydrochloric acid into a 250ml four-mouth bottle, cooling to 0 ℃, dropwise adding the reaction liquid into the bottle, controlling the temperature to be not higher than 30 ℃, stirring for 30min, and standing for liquid separation; washing the organic phase with 50ml of 3% sodium bicarbonate water solution for 30min, and standing for liquid separation; the organic phase was washed with 50ml of water; the separated organic phase was subjected to reduced pressure distillation to remove the solvent, to obtain 5g of a yellow liquid, yield 83%, and solidified at room temperature to pale yellow crystals. The HPLC content is 98.43 percent, and the melting range is 36.4-40.3 ℃; the structure was confirmed by 1H-NMR spectroscopy to be 4- (2-methoxy-2-oxoacetyl) -4' - (2-ethoxy-2-oxoacetyl) diphenyl sulfide,. delta. [ ppm, CDCl3]:1.404/1.428/1.452(t,3H, CH 3); 3.985(s,6H,2CH 3); 4.417/4.441/4.464/4.488 (quartz, 2H, OCH 2); 7.449/7.455/7.472/7.478(dd,4H,4 ArH); 7.976//7.982/7.999/8.005(dd,4H,4 ArH).

PREPARATION OF COMPOUNDS EXAMPLE 104- (2-METHOXY-2-OXOACETYL) -4' - (THIOPHENE-2-FORMYL) Diphenyl sulfide (Compound of formula I-18)

Preparation of 4- (thiophene-2-formyl) diphenyl sulfide

Adding 5.18g of diphenyl sulfide and 25ml of o-dichlorobenzene into a 100ml three-necked bottle, and cooling to the temperature; adding 3.7g of anhydrous aluminum trichloride, stirring and keeping the temperature at 0-5 ℃, dropwise adding 4.1g of thiophene-2-formyl chloride, then carrying out heat preservation reaction for 10 hours, carrying out acidolysis on the reaction solution in a hydrochloric acid aqueous solution, washing with water, concentrating and recovering o-dichlorobenzene to obtain 8.2g of light yellow solid, and recrystallizing with 50ml of ethanol to obtain 6.85g of dry white crystal, wherein the yield is 83.1%, the HPLC purity is 99.31%, and the melting range is 106.1-109.4 ℃.

Preparation of 4- (2-methoxy-2-oxoacetyl) -4' - (thiophene-2-formyl) diphenyl sulfide

Referring to the operation of preparation example 7 of the compound, 4.05g of 10a product and 5.65g of anhydrous aluminum trichloride are dissolved in 20ml of 1, 2-dichloroethane in a 100ml three-necked flask, 1.76g of oxalyl chloride monomethyl ester is added dropwise at a temperature of 10 ℃ for reaction for 5 hours, and then the mixture is subjected to acidolysis, water washing and concentration to obtain 4.4g of yellow crystals, and the yellow crystals are recrystallized by 35ml of ethanol to obtain 3.95g of dry light yellow crystals, wherein the yield is 75.4%, the purity is 98.0%, and the melting range is 105-107 ℃;¹the structure was confirmed by H-NMR spectrum to be 4- (2-methoxy-2-oxoacetyl) -4' - (thiophene-2-formyl) diphenyl sulfide. Delta (ppm, CDCl)₃) Value data: 3.976(s,3H, OCH)₃)；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)。

Compound preparation example 114- (2-acetoxyiminopropionyl) -4' - (3-methylbenzoyl) diphenyl sulfide (Compound of formula II-17)

Preparation of 4- (3-methylbenzoyl) diphenyl sulfide

From Compound preparation 3a

Preparation of 4-propionyl-4' - (3-methylbenzoyl) diphenyl sulfide

2.28g of aluminum trichloride and 20g of dichloroethane were placed in a 100ml three-necked flask, and a solution of 4g of the product of preparation example 3, run 3a and 10g of dichloroethane were added dropwise while maintaining the temperature at 0 ℃; dropwise adding 1.34g of propionyl chloride at 0 ℃, and reacting for 3h at 0-5 ℃; dropwise adding the reaction solution into a solution of 20ml of hydrochloric acid and 50ml of water while keeping the temperature at 0 ℃, stirring for 1 hour, standing, and separating liquid; washing the organic phase with 50ml of water for 30min, standing and separating liquid; the solvent was rotary evaporated under reduced pressure to dryness to give 4g of a pale yellow solid; the yield thereof was found to be 84.45%. The HPLC content is 98.87%, and the melting range is 96.0-98.0 ℃;¹H-NMR，δ(CDCl₃ppm) value data: 1.206/1.230/1.254(t,3H, CH)₃)；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)；7.749/7.755/7.772/7.778(dd,2H,2ArH)；7.911/7.917/7.934/7.940(dd,2H,2ArH)。

Preparation of 4- (2-Hydroxyiminopropionyl) -4' - (3-methylbenzoyl) diphenyl sulfide

4g of the product obtained in the step 11b, 20g of DMSO, 0.3g of hydrochloric acid and 1.37g of n-butyl nitrite are placed in a 100ml single-neck flask, and the mixture is reacted for 5 hours at the temperature of 40 ℃; dripping the reaction solution into 100g of water at the temperature of 5 ℃, stirring for 30min and filtering; the filter cake was dried to give 4g of a yellow solid product in 92.55% yield. The HPLC content is 97.73%, and the melting range is 147.6-149.0 ℃;¹H-NMR(CDCl₃) δ (ppm) value data: 2.182(s,3H, CH)₃)；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)。

Preparation of 4- (2-acetoxyiminopropionyl) -4' - (3-methylbenzoyl) diphenyl sulfide

4g of the 11c product, 30g of toluene and 4.5g of acetic anhydride are put into a 100ml single-mouth bottle, and the reaction is kept at 45 ℃ for 2 hours;

cooling the reaction solution to room temperature, adding 80ml of water, stirring for 30min, and standing for liquid separation; the toluene phase is washed with 50ml of water for 30min, standing and separating liquid; reduced pressure distillation is carried out to remove toluene, and 4.5g of yellow solid crude product is obtained; dissolving the mixture with a mixed solvent of 8g of ethyl acetate and 10g of n-hexane, cooling to-15 ℃, filtering, and drying a filter cake to obtain 3.8g of light yellow crystals with the yield of 85.74%. HPLC content is 99.63%, melting range is 98.0-100 ℃;¹H-NMR(CDCl₃) δ (ppm) value data: 2.271(s,3H, CH)₃)；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)。

Compound preparation example 124- (2-acetoxyimino-2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide (Compound of formula II-18)

Preparation of 4- (2-Phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide

Carrying out Friedel-crafts reaction by using 2-phenylacetyl chloride instead of propionyl chloride according to the method of the operation 11b in the embodiment 11, and carrying out hydrolysis treatment and purification to obtain light yellow crystals, wherein the melting range is 141.8-145.0 ℃, and the yield is 86.1%;¹H-NMR confirmed as 4- (2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide; delta (CDCl)₃Ppm) value data: 2.427(s,3H, CH)₃)；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)。

Preparation of 4- (2-hydroxyimino-2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide

The process of example 11, run 11c, was followed using the product of run 12a in place of the product of run 11b for the oximation reaction and purification to give white crystals, melting range: the ratio of cis-trans isomers of the purity of the mixture is 2:98 by HPLC analysis at the temperature of 155.0-160.1 ℃; delta (CDCl)₃Ppm) value data: 2.423(s,3H, CH)₃)；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)。

Preparation of 4- (2-acetoxyimino-2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide

Adding 2.2g of the product obtained in the step 12b and 20ml of dichloroethane into a 50ml three-necked bottle, keeping the temperature in a water bath at 25 ℃, dropwise adding 0.6g of acetic anhydride, and reacting for 0.5h at 25 ℃ after dropwise adding; dropping 20ml of water into the reaction bottle, stirring for about 1h, separating out an organic phase, washing the organic phase for 2 times by using 10ml of 5% sodium bicarbonate aqueous solution, washing the organic phase to be neutral by using water, desolventizing the organic phase to obtain 2.2g of an oily object, and adding ethyl acetate: n-hexane ═ 1: 10, carrying out column chromatography separation on the mixed solution, and desolventizing the eluate to obtain 1.95g of solid; recrystallizing with ethanol to obtain white crystal 1.72g with yield 76.8%; melting range: 91.5-93.6 ℃;¹H-NMR confirmed to be 4- (2-acetoxyimino-2-phenylacetyl) -4' - (3-methylbenzoyl) diphenyl sulfide; delta (CDCl)₃Ppm)) value data: 2.035(s,3H, CH)₃)；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。

PREPARATION OF COMPOUND EXAMPLE 134, 4' -BIS (2-ACETOXYLIMINO PROPIONYL) DIPHENYLSULFIDE (COMPOUND OF FORMULA II-15)

Preparation of 4, 4' -Diproyl diphenyl sulfide

Weighing 79.0g (0.424mol) of diphenyl sulfide, dissolving the diphenyl sulfide in 600g of 1, 2-dichloroethane, adding 124.4g (0.933mol) of anhydrous aluminum trichloride, stirring and cooling to 0 ℃; keeping the temperature below 5 ℃, dropwise adding 82.4g (0.891mol) of propionyl chloride, after finishing dropwise adding for 2h, keeping the temperature below 0 ℃ and stirring for 2 h; dropwise adding the reaction solution into 450ml of 10% diluted hydrochloric acid, controlling the temperature of the acid solution to be not higher than 30 ℃, stirring for 1h after the addition is finished, and separating a lower organic phase; the organic phase is washed three times by 300ml of water in sequence; the organic phase is subjected to reduced pressure distillation to recover the solvent, and 126g of residues are obtained; adding 240ml of n-hexane while the solution is hot, and keeping the temperature to clarify the solution; naturally cooling to crystallize, and cooling the crystallization bottle to 0 deg.C when the temperature of the solution is lower than 30 deg.C; filtering to obtain white filter cake, drying at 50 deg.C under reduced pressure to obtain 117.6g of white crystal with yield 93%, HPLC analysis purity 98.5%, melting range 123.1-130.3 deg.C,¹H-NMR data show that the obtained product is 4, 4' -dipropionyl diphenyl sulfide.

Preparation of 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide

Taking 30g (0.1mol) of the product 4, 4' -dipropionyl diphenyl sulfide obtained in the step 13a, dissolving the product in 100g of dimethyl sulfoxide, adding 3.0g of 36% concentrated hydrochloric acid, stirring in a water bath at the temperature of 20-25 ℃, dropwise adding 25g (0.24mol) of n-butyl nitrite within 30min, and stirring for 10 h; dropwise adding the reaction solution into 1L of ice water, precipitating light yellow solid, performing suction filtration, drying under reduced pressure, weighing 27g, and analyzing by HPLC (high performance liquid chromatography) to obtain 97.80% purity and 75% yield; the melting range is between 162.8 and 169.5 ℃,¹the H-NMR data showed that the product was 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide. Delta (CDCl)₃Ppm) value data 2.022(s,6H,2CH 3); 7.425/7.452(d,4H,4 ArH); 7.823/7.851(d,4H,4 ArH); 12.450(s,2H,2 NOH).

Preparation of 4, 4' -bis (2-acetoxyiminopropionyl) diphenyl sulfide

Putting 24.5g (0.068mol) of 13b product 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide and 150ml of toluene into a reaction bottle, putting the reaction bottle into a water bath at 20-25 ℃, dropwise adding 19.6g (0.19mol) of acetic anhydride into the reaction bottle through a constant-pressure dropping funnel, and stirring for 6 hours; adding 100ml of water into the reaction solution, and stirring for 30 min; washing the toluene phase with 100ml of 1% sodium bicarbonate solution, 50ml of water and 50ml of water in sequence; filtering the toluene solution, and carrying out reduced pressure distillation to recover toluene to obtain 28.5g of a yellow solid crude product; adding 55ml of hot ethyl acetate to dissolve the solid, then adding 85ml of hot n-hexane, naturally cooling to separate out crystals, carrying out suction filtration, and drying a filter cake in vacuum to obtain 27.2g of a light yellow solid crystal product, wherein the HPLC analysis content is 99.2%, and the yield is 90.8%; the melting range is 108.0-111.5 ℃;¹H-NMR(CDCl₃) δ (ppm) value data: 2.274(s,6H,2 CH)₃)；2.293(s,6H,2COCH₃)；7.417/7.445(d,4H,4ArH)；8.050/8.078(d,4H,4ArH)。

Preparation of Compound 144, 4' - (2-cyclohexylmethoxy-2-oxoacetyl) diphenyl sulfide (Compound of formula I-19)

In a 50ml single-neck flask, 2g (5.6mmol) of 4, 4' - (2-methoxy-2-oxoacetyl) diphenyl sulfide (compound of formula I-14) which was the product of preparation example 8 was weighed, 20ml of cyclohexylmethanol was added, 20mg of zirconium acetylacetonate as a catalyst was added, stirring magneton was added, the temperature was raised to 80 ℃,electromagnetically stirring for 18h, distilling the reactant under reduced pressure to remove the cyclohexylmethanol, and purifying the residue by silica gel column chromatography to obtain 1.85g of light yellow sticky substance with the purity of 98.9% and the yield of 63.4%; warp beam¹H-NMR(CDCl₃) Identified as 4, 4' - (2-cyclohexylmethoxy-2-oxoacetyl) diphenyl sulfide, delta (ppm) value data: 010-1.294(m,10H,2 cyclohexyl); 1.679-1.808(m,12H,2 cyclohexyl); 4.187/4.208(d,4H,2 CH)₂)；7.452/7.480(d,4H,4ArH)；7.960/7.989(d,4H,4ArH)。

Photoinitiator composition preparation example 1:

3g of the compound represented by the formula I-14 and 7g of sample OXE01 were put into a mortar and mixed by grinding to obtain 10g of a composition, wherein the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound was 0.53: 1.

Photoinitiator composition preparation example 2:

4.5g of the compound represented by the formula I-14 and 5.5g of a sample of OXE01 were put into a mortar and ground to mix, thereby obtaining 10g of a composition, wherein the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound was 1: 1.

Photoinitiator composition preparation example 3:

5g of the compound represented by the formula I-14 and 5g of a sample of OXE01 were put into a mortar and mixed by grinding to obtain 10g of a composition, wherein the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound was 1.24: 1.

Photoinitiator composition preparation example 4:

5.3g of the compound represented by the formula I-14 and 4.7g of a sample OXE-01 were put into a mortar and ground to mix them, whereby 10g of a composition was obtained, and the molar ratio of bisacyldiphenyl sulfide derivative to oxime ester compound was 1.4: 1.

Photoinitiator composition preparation example 5:

3g of the compound represented by the formula I-14 and 7g of the compound represented by the formula II-19 were put into a mortar and ground to mix, thereby obtaining 10g of a composition having a molar ratio of 0.53: 1.

Alkali soluble resin preparation

18g of benzyl methacrylate, 6g of methacrylic acid, 6g of hydroxyethyl methacrylate, 1.5g of azobisisobutyronitrile, 0.6g of dodecanethiol and 200ml of toluene are put into a constant-pressure dropping funnel for 1L, 100ml of toluene is put into a 500ml four-mouth bottle, nitrogen is replaced, the temperature is increased to 80 ℃, the solution in the funnel is dropped, and after 6 hours of reaction, the solution is cooled and filtered, so that 24g of white alkali-soluble resin is obtained.

Preparation of black color paste

50g of the white alkali-soluble resin, 50g P25 g of carbon black, 100g of DPHA and 250g of propylene glycol methyl ether acetate are put into a 500ml beaker and mixed for 15min at the rotating speed of 3000r/min by a high-speed shearing mixer to prepare black paste.

Preparation of red color paste

50g of the white alkali-soluble resin, 50g of Ciba IRGALITE RED 2BXL-Q pigment, 100g of DPHA and 250g of propylene glycol monomethyl ether acetate are put into a 500ml beaker and mixed for 15min at the rotating speed of 3000r/min by using a high-speed shearing mixer to prepare red color paste.

Photoresist embodiments

The photoresists of the examples and comparative examples were prepared according to the compositions described in tables 1 to 7. The initiator and the sensitizer can be prepared by using the composition in the preparation example of the photoinitiation composition or mixing the composition according to the weight ratio in the following table, dissolving the mixture in PMA to form a composition solution, and mixing the composition solution with the black color paste or the red color paste according to the ratio. After the components are uniformly mixed, a 10-micron wire rod is used for coating a film on a glass slide, the glass slide is dried in a 90-DEG C oven for 5min, a 365-nm light source is used for matching with a mask plate for curing, a 1% NaOH solution is used for developing at 25 ℃, pure water is used for soaking and cleaning for 10s, the line width of a developed image is measured by a microscope after the glass slide is dried in the 90-DEG C oven for 30min, and the results are shown in tables 1 to 7.

TABLE 1

Table 1 the results show that: the developed linewidth values for the examples using OXE01 formulated with the compounds of formulas i-14 were significantly greater than the comparative example using OXE01 alone and significantly more sensitive than the comparative example using OXE01 alone.

TABLE 2

Table 2 the results show: the developed line width values of the examples using the compounds of formulae II-15 and I-14 formulated into photoinitiator compositions are significantly greater than the corresponding comparative examples using the compounds of formulae II-15 alone and significantly more sensitive than the comparative examples using the initiator alone.

TABLE 3

The results in Table 3 show that the developed linewidth values for the examples using OXE01 formulated with the compounds of formulas I-2, I-6, I-14, and I-15, respectively, are significantly greater than the comparative examples using OXE01 alone and enhanced with Esacure 3644 and Omnirad BMS.

TABLE 4

TABLE 5

The results in tables 4 and 5 show that when photoinitiator compositions prepared using compounds of formula II-1, formula II-4, formula II-15, formula II-17, and formula II-18, respectively, with compounds of formula I-14, cured and developed line widths were significantly greater than the corresponding comparative examples, and sensitivity was significantly greater than the comparative examples using the corresponding initiator alone. And as can be seen from comparison of example 5 with comparative example 2, example 13 with comparative example 6, example 14 with comparative example 7, the sensitivity of the composition formed using the combination of the bisacyldiphenyl sulfide derivative and the oxime ester compound as the initiator was significantly higher than that of one having both the bisacyldiphenyl sulfide group and the oxime ester group.

TABLE 6

Table 6 the results show: the developed linewidth of the examples using the photoinitiator composition provided by the present invention in a red system is significantly higher than the comparative examples using the same initiator alone.

TABLE 7

Table 7 the results show: the I-14 compound and the photoinitiators with various carbazole structures form the composition, the curing and developing line width values of the composition are obviously larger than those of corresponding comparative examples, and the sensitivity of the composition is obviously higher than that of the comparative example in which a corresponding single oxime ester initiator is used alone.

Transparent photocurable composition examples

Each example and comparative example was prepared according to the composition shown in Table 8, and the compositions were mixed uniformly, coated on a glass slide using a 50 μm wire bar, cured using a 365nm light source, and the film weight was measured after curing, and then the film weight was measured again after soaking in acetone at room temperature for 36 hours, and 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.

The examples and comparative examples were prepared according to the components in Table 8, and after mixing the components homogeneously, the glass plate was coated with a film using a 25 μm wire bar and cured with a 365nm LED light source. After baking in an oven at 230 ℃ for 30min, the temperature was lowered to room temperature, and the yellowness index of each example and comparative example was measured with a full-automatic color difference meter.

TABLE 8

	Example 22	Example 23	Comparative example 12
				Photomer 6010	5	5	5
HPMA	4.5	4.5	4.5
				Compounds of formula II-1	0.35	0.35	0.5
Compounds of formula I-6	0.15	0	0
				Compounds of formula I-14	0	0.15	0
Gel conversion	94.2％	94.0％	85.2％
				Yellow value	6.22	6.45	7.08

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

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the curing activity or sensitivity of the photoinitiator composition containing the diacyl diphenyl sulfide derivative and the oxime ester compound in the photocuring composition is obviously higher than that of the photoinitiator composition containing the same oxime ester compound, and the photoinitiator composition also has obviously low yellowing property after photocuring and postbaking processing.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A photoinitiating composition comprising at least one bisacyldiphenyl sulfide derivative selected from compounds of formula i and at least one oxime ester compound selected from compounds of formula ii:

in the formula I, the compound has the following structure,

R₁、R₂each 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,

R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₈and R₁₉Each independently selected from any one of H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom and CN;

in the formula II, the compound is shown in the specification,

R₃any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃May be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₄Any one selected from the following groups: C1-C11 substituted or unsubstituted alkyl, C3-C5 alkenyl, substituted or unsubstituted phenyl, C1-C4 alkoxy, phenoxy;

Ar₁is a radical whose parent is a C6-C20 aromatic radical, a C4-C30 heteroaromatic radical, a coumarin radical, said parent being unsubstituted or substituted by one or more halogen atoms, nitro groups, R₁₀X-、

Is substituted in which R₁₀Any one selected from the following groups: C1-C12 alkyl, C3-C12 alkyl interrupted by one or more oxygen or sulfur atoms, C3-C8 cycloalkyl, C3-C8 heterocyclyl, C2-C7 alkenylmethyl, C6-C15 aromatic, C4-C15 heteroaromatic, wherein the hydrogens of the C6-C15 aromatic and C4-C15 heteroaromatic groups are replaced by fluorine atoms, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio or C1-C4 alkylsulfonyl; the hydrogen of the C1-C12 alkyl, C3-C12 alkyl interrupted by one or more oxygen or sulfur atoms, and C3-C8 cycloalkyl can be optionally interrupted by F, C1-C4 alkoxy, OH, OOCR₄、COOR₉、(R₉O)₂P(O)、(CH₃)₃Si or phenyl substitution; r₉Is C1-C4 alkyl; r₁₀Or R₁₀' optionally linked to an atom on an adjacent parent to form any of a five-membered ring to a seven-membered ring, X is a direct bond, O, S, CO or R₁₀’N，R₁₀' is C1-C12 alkyl, or X is R₁₀When N is' N, R₁₀R₁₀' N is

R₃' is selected from any one of the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃' may be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring; r₂₀Any one selected from the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl groups, containing one or more O, S spacers and hydroxyl groups and being OOCR₄Substituted C3-C8 alkyl, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl;

m₁n is each 0 or 1;

Ar₁the substituents above may optionally form any of a five-membered ring to a seven-membered ring together with the adjacent substituents and the parent atom.

2. The photoinitiating composition of claim 1, wherein,

the R is₁And said R₂The C1-C12 substituted alkoxy acyl is selected from any one of the following groups: by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, R₂₀OOC-substituted C1-C12 alkoxyacyl, substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy, C2-C4 alkoxy, phenoxy C2-C4 alkoxy, R₄COO、R₂₀OOC-substituted C2-C12 alkoxyacyl; wherein the C6-C20 substituted aryl, C4-C20 substituted heteroaryl, C6-C20 substituted aryl acyl, and the substituent on the C4-C20 substituted heteroaryl acyl comprises halogen atom, R₂₀、-OR₃₀、-SR₃₀、-NR₃₁R₃₂、-COOR₃₀、-CONR₃₁R₃₂And the substituent can be optionally combined with the atom on the mother ring to form a five-membered ring to a seven-membered ring; r₂₀And R₃₀Each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted with one or more F, Cl, OH, C3-C7 cycloalkyl groups, containing one or more O, S spacers and hydroxyl groups and being OOCR₄Substituted C3-C8 alkyl, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl;

R₃₁and R₃₂Each independently selected from any one of the following groups: C1-C4 alkyl, C1-C4 alkyl substituted with hydroxy; or NR₃₁R₃₂Is composed of

Or said R is₄In the formula, the C1-C11 substituted alkyl is C1-C11 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl and CN, and the substituted phenyl is phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy and CN.

3. The photoinitiating composition of claim 2, wherein said R is₁And said R₂Each independently selected from any one of the following groups: phenyl, phenyl substituted by one or more F, methyl, C1-C4 alkoxyacyl, thienyl, benzoyl substituted by one or more F, methyl, C1-C4 alkoxyacyl, C1-C4 alkoxyacyl, phenyl, R substituted by one C4-C7 cycloalkyl, C4-C7 heterocyclyl, R₂₀OOC-substituted C1-C4 alkoxyacyl substituted by a C1-C4 alkoxy, C1-C4 alkylthio, phenoxy, phenylthio, C1-C4 alkoxy C2-C4 alkoxy, 2-phenoxyethoxy, CH₃COO、R₂₀OOC-substituted C2-C4 alkoxyacyl;

R₁₁，R₁₂，R₁₃，R₁₄，R₁₅，R₁₆，R₁₈，R₁₉each independently is any one of H, C1-C4 alkyl, C1-C4 alkoxy and F;

R₂₀is C1-C8 alkyl.

4. The photoinitiating composition of claim 1, wherein said Ar is₁The parent structure of (a) is selected from any one of the following groups: benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, thianthrene, thioxanthone, fluorene, benzofluorene, carbazole, benzocarbazole, dibenzocarbazole.

5. The photoinitiating composition of claim 1 or 2 wherein at least one of said oxime ester compounds is selected from the group consisting of compounds represented by formula iii:

wherein the content of the first and second substances,

n₁is 1 or 0;

R₃any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen or sulfur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃Can be connected with adjacent benzene rings to form any one of five-membered ring to seven-membered ring;

R₄any one selected from the following groups: C1-C11 alkyl, C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN, C1-C4 alkoxy, phenoxy;

R₂₁，R₂₂，R₂₃，R₂₄each independently is H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom or CN;

R₂₅，R₂₆，R₂₇，R₂₈，R₂₉each independently of the others being H, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, NO₂C1-C8 substituted or unsubstituted alkanoyl,

C6-C15 substituted or unsubstituted aromatic acyl, C4-C15 substituted or unsubstituted heteroaromatic acyl, wherein the substituent of the substituted C1-C8 alkyl is selected from halogen atom, C4-C7 cycloalkyl, hydroxyl, CN, R₄COO, the substituted C6-C15 aryl and the substituted C4The substituents on the heteroaromatic radical-C15 are each independently selected from the group consisting of halogen atoms, CN, R₂₀、OR₃₀、SR₃₀、NR₃₁R₃₂、COOR₃₀、CONR₃₁R₃₂Any one of the above-mentioned (a) and (b),

R₃₁,R₃₂each independently is C1-C4 alkyl, C1-C4 alkyl substituted with hydroxy;

or NR₃₁R₃₂Is composed of

6. The photoinitiating composition of claim 5, wherein,

R₃any one selected from C1-C6 alkyl, C1-C3 alkyl substituted by C4-C7 cycloalkyl, and C4-C7 cycloalkyl;

R₄is methyl or phenyl;

R₂₁，R₂₂，R₂₃，R₂₄each independently selected from any one of H, C1-C4 alkyl, C1-C4 alkoxy and F;

R₂₅，R₂₆，R₂₇，R₂₈，R₂₉each independently selected from H, C1-C8 substituted or unsubstituted alkyl, F, C1-C8 alkanoyl,

any one of substituted or unsubstituted benzoyl, substituted or unsubstituted thiophene-2-formyl and substituted or unsubstituted benzofuran-2-formyl, wherein the substituent of the C1-C8 substituted alkyl is one or more of F, C4-C7 cycloalkyl, hydroxyl, R₄COO, substituted benzoyl, substituted thiophene-2-formyl, substituted benzofuran-2-formyl having a substituent of F, R₂₀、OR₃₀、COOR₃₀、CONR₃₁R₃₂Any one of the above;

R₃' is selected from C1-C6 alkyl, C1-C3 alkyl substituted by a C4-C7 cycloalkyl, C4-C7 a cycloalkyl group;

R₂₀，R₃₀each independently selected from H, C1-C8 alkyl, C1-C4 alkyl substituted with one or more F, C3-C7 cycloalkyl groups, having one or more O, S spacers and hydroxyl groups, OOCR₄Substituted C3-C8 alkyl, five-or six-membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl;

R₃₁,R₃₂each independently selected from any one of C1-C4 alkyl;

or NR₃₁R₃₂Is composed of

7. The photoinitiating composition of claim 1 or 2 wherein at least one of said oxime ester compounds is selected from any one of the compounds of formula iv, formula v, formula vi:

wherein the content of the first and second substances,

Y₁，Y₂，Y₃each independently selected from H, Ar₂CO、

Wherein m is₂，n₂，n₃，n₄Each independently is 1 or 0; or Y₃Is NO₂；

R₃Any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen and sulfur atomsC3-C16 alkyl, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl; r₃May be adjacent to Ar₁Connected to form any one of five-membered ring to seven-membered ring;

R₅，R₆，R₇，R₈each independently selected from any one of the following groups: h, C1-C8 alkyl, C3-C8 alkyl interrupted by one or 2 oxygen atoms, C2-C7 alkenylmethyl, phenyl; the hydrogen of the alkyl and phenyl groups being optionally substituted by halogen atoms, C4-C7 cycloalkyl, hydroxy, R₄COO、COOR₉、(R₉O)₂P(O)、(CH₃)₃Si and phenyl substitution; r₉Is C1-C4 alkyl; r₅，R₆，R₇，R₈Each independently can form any one of five-membered ring to seven-membered ring together with adjacent substituent and atom on the parent;

Ar₂any one selected from the following groups: a C6-C15 aromatic group, a C4-C15 heteroaromatic group; wherein hydrogen on carbon atom is substituted by any one of fluorine atom, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio and C1-C4 alkylsulfonyl, and hydrogen on C1-C4 alkyl is substituted by any one of fluorine atom, C1-C4 alkoxy and R3552 alkylsulfonyl₄COO is substituted by one;

R₄₁，R₄₂，R₄₃，R₄₄，R₄₅each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkoxy, halogen atom, CN, C1-C8 substituted or unsubstituted alkylacyl,

C6-C15 substituted or unsubstituted aroyl, C4-C15 substituted or unsubstituted heteroarylacylThe substituent of the C1-C8 substituted alkyl is selected from halogen atoms, C4-C7 cycloalkyl, hydroxyl, CN, R₄Any one or more of COO; the substituents of the C6-C15 substituted aroyl and the C4-C15 heteroaryl acyl are selected from H, halogen atoms, CN and R₂₀、OR₃₀、SR₃₀、NR₃₁R₃₂、COOR₃₀、CONR₃₁R₃₂Any one or more of;

R₂₀，R₃₀each independently is 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, acetoxy substituted, five or six membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl;

R₃₁,R₃₂each independently is any one of C1-C4 alkyl and C1-C4 alkyl substituted by hydroxyl;

or NR₃₁R₃₂Is composed of

8. The photoinitiating composition of claim 7 wherein at least one of said oxime ester compounds is selected from any one of the group consisting of compounds of formula IV, formula V and formula VI:

wherein the content of the first and second substances,

Y₁，Y₂，Y₃each independently selected from Ar₂CO、

R₃Any one selected from the following groups: C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, benzyl, substituted or unsubstituted phenyl;

R₄any one selected from the following groups: methyl, phenyl, C1-C4 alkoxy;

R₅，R₆，R₇，R₈each independently selected from any one of the following groups: C1-C4 alkyl, phenyl, alkyl and phenyl hydrogen optionally substituted by COOR₉、(R₉O)₂P(O)、(CH₃)₃Si and phenyl substitution; r₉Is C1-C4 alkyl;

Ar₂any one selected from the following groups: phenyl, thienyl, benzofuranyl; the hydrogen on the phenyl is substituted by any one of a fluorine atom, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 alkylsulfonyl, and the hydrogen on the C1-C4 alkyl is substituted by a fluorine atom and C1-C4 alkoxy;

R₄₁，R₄₂，R₄₃，R₄₄，R₄₅each independently selected from any one of the following groups: h, C1-C4 alkyl, C1-C4 alkoxy, halogen atom, CN.

9. The photoinitiating composition of claim 1 or 2 wherein at least one of said oxime ester compounds is selected from the group consisting of compounds represented by formula vii:

wherein the content of the first and second substances,

R₃any one selected from the following groups: C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy, CN, R₄COO、R₂₀OOC-substituted C1-C16 alkyl, C3-C16 alkyl which is substituted by one or more halogen atoms, C4-C7 cycloalkyl, C4-C7 heterocyclyl, phenyl, hydroxy and interrupted by one or more oxygen atoms, sulphur atoms, phenyl substituted by one or more halogen atoms, C1-C12 alkyl, C1-C4 alkoxy, CN, C4-C7 cycloalkyl;

R₄any one selected from the following groups: C1-C11 alkaneA group, C1-C16 alkyl substituted by one or more halogen atoms, C4-C7 cycloalkyl, CN, C3-C5 alkenyl, phenyl substituted by one or more halogen atoms, C1-C4 alkyl, C1-C4 alkoxy, CN, C1-C4 alkoxy, phenoxy;

R₅₁，R₅₂，R₅₃，R₅₄，R₅₅each independently selected from any one of the following groups: h, halogen atom, CN, R₂₀，OR₃₀，SR₃₀，NR₃₁R₃₂，COOR₃₀，CONR₃₁R₃₂Adjacent substituents together optionally form any of a five to seven membered ring structure;

R₂₀，R₃₀each independently selected from any one of the following groups: h, C1-C8 alkyl, C1-C8 alkyl substituted by one or more F, Cl, OH, C3-C7 cycloalkyl, C3-C8 alkyl substituted by one or more O, S spacers and hydroxyl, acetoxy, five-membered or six-membered ring containing one or 2O, S, N heteroatoms, phenyl, C1-C4 alkylphenyl;

or NR₃₁R₃₂Is composed of

10. The photoinitiating composition of claim 9 wherein at least one of said oxime ester compounds is selected from the group consisting of compounds represented by formula vii:

wherein the content of the first and second substances,

R₄any one selected from the following groups: methyl, phenyl, C1-C4 alkoxy;

R₅₁，R₅₂，R₅₃，R₅₄，R₅₅each independently selected from any one of the following groups: h, methoxy, methylthio.

11. Photoinitiating composition according to claim 1 or 2, wherein the diacyl diphenyl sulfide derivative is selected from one of the following compounds or any mixture thereof,

12. the photoinitiating composition according to claim 1 wherein the oxime ester compound is selected from one of the following compounds or any mixture thereof:

13. the photoinitiating composition of any one of claims 1 to 12, wherein the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound is 0.1:1 to 3: 1.

14. The photoinitiation composition according to claim 13, wherein the molar ratio of the bisacyldiphenyl sulfide derivative to the oxime ester compound is 0.3:1 to 1.4: 1.

15. A photo-curable composition comprising a photo-curable resin and an initiator, wherein the initiator is a photo-initiation composition according to any one of claims 1 to 14.

16. The photocurable composition of claim 15 wherein the initiator is present in an amount of 0.1 to 10% by mass of the solids of the photocurable composition.

17. Use of the photocurable composition according to claim 15 or 16 as an ink, coating, sealant, optical film or adhesive, preferably as a negative passivation film, photocurable photosensitive surface coating, barrier film or polarizer coating.

18. A photoresist comprising a multifunctional acrylate monomer, an alkali soluble resin, an initiator and a solvent, wherein the initiator is the photoinitiating composition of any one of claims 1 to 14.

19. The photoresist of claim 18, further comprising a pigment, preferably the pigment is selected from any one of a black pigment, a red pigment, a green pigment and a blue pigment, further preferably the black pigment is dispersed carbon black or titanium black.

20. A photoresist according to claim 18 or 19 wherein the mass content of the initiator in the solid matter of the photoresist is 0.1-10%.

21. Use of the photoresist of any one of claims 18 to 20, further comprising a pigment, said use comprising using said photoresist as a sealant, optical film, colored matrix, photo spacer or optical filter, preferably as a negative passivation film, photo-curable photosensitive surface coating, barrier film or polarizer coating.