Photoinitiator, photopolymerizable composition, and use thereof

Abstract

The present invention relates to the technical field of photoinitiators, and to a photoinitiator, a photopolymerizable composition, and a use thereof. The photoinitiator is a compound having a structure represented by formula (1): wherein one or two structures of R1-R8 in formula (1) are selected from groups represented by formula (2) or (3). The compound of the present invention remains relatively strong absorption capacity and high OD in a dark color system, exhibits excellent I-line photosensitivity, and is well matched with an emission spectrum of an ultraviolet light source. Therefore, the compound is a highly photosensitive, readily soluble and cost-effective photoinitiator having excellent overall performance, and has excellent prospects of application in display, semiconductors, and inks.

Description

A photoinitiator, a photopolymerization composition and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of photoinitiators, and particularly relates to a photoinitiator, a photopolymerization composition and application thereof. BACKGROUND

[0002] The photoinitiator is one of the key components in the photocuring system, plays a decisive role in the curing rate, and has wide application in multiple fields, including microelectronic industry, UV coating, PCB ink, etc. Various types are known, such as phenylacetone derivatives, benzophenone derivatives, a-hydroxy ketones, acyl phosphine oxides, triazine derivatives, bisimidazole derivatives, acyl phosphine oxide derivatives and oxime ester derivatives, etc. Among them, the oxime ester photoinitiator performs well in storage stability, photosensitivity, development and pattern integrity, etc. For example, oxime ester compounds containing a carbazole skeleton are known. However, when the traditional photopolymerization initiator forms a pattern, in the exposure process of pattern formation, due to low sensitivity, the amount of photopolymerization initiator or the exposure dose needs to be increased, which causes pollution of the mask during the exposure process and the by-products produced after the photopolymerization initiator decomposes during crosslinking at high temperature, resulting in a decrease in yield and an increase in the time of the exposure process with the increase in the exposure dose. Therefore, it is expected to develop a photopolymerization initiator with more excellent sensitivity to active energy rays, better solubility and lower cost compared with these compounds. In view of this, the present application provides a photoinitiator, a photopolymerization composition and application thereof. SUMMARY

[0003] The technical problem to be solved by the present application is to provide a photoinitiator, a photopolymerization composition and application thereof. The purpose is to provide a photoinitiator with high photosensitivity, good solubility and low cost, and excellent comprehensive performance.

[0004] In a first aspect, a photoinitiator is provided, which is a compound represented by the structure of formula (1):

[0005] In formula (1), 1-2 structures of R1-R8 are selected from the groups represented by formula (2) or formula (3):

[0006] The structures of the remaining R1-R8 are independently selected from any one of the following structures: hydrogen, cyano, nitro, halogen, alkylone with carbon atom number of 2-15, cycloalkylone with carbon atom number of 4-15, heterocycloalkylone with carbon atom number of 3-15, arylone with carbon atom number of 7-25, heteroarylone with carbon atom number of 4-25, substituted arylone with carbon atom number of 7-25 and substituted heteroarylone with carbon atom number of 4-25;

[0007] 1 to 3 hydrogen atoms in the substituted aryl group having 6 to 25 carbon atoms, the substituted heteroaryl group having 3 to 25 carbon atoms are independently substituted by the following structure: cyano, nitro, halogen, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms, alkylthio group having 1 to 15 carbon atoms, alkyl ether group having 1 to 15 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms, heterocycloalkyl group having 2 to 15 carbon atoms, heterocycloalkoxy group having 2 to 15 carbon atoms, alkyl group having 1 to 15 carbon atoms substituted by fluorine atom, alkoxy group having 1 to 15 carbon atoms substituted by fluorine atom, alkylthio group having 1 to 15 carbon atoms substituted by fluorine atom, or alkyl ether group having 1 to 15 carbon atoms substituted by fluorine atom;

[0008] the cycloalkyl group having 4 to 15 carbon atoms, the heterocycloalkyl group having 3 to 15 carbon atoms contain part or all of carbon chain as cyclic or heterocyclic, 0 to 3 hydrogen atoms in the carbon chain are substituted by alkyl group having 1 to 8 carbon atoms;

[0009] X1, X2 are independently selected from any one of the following structure: oxygen atom, keto group, sulfonyl group, N(R 13 ), C(R 14 )(R 15 ), and 1 to 2 of X1, X2 are selected from sulfonyl group;

[0010] R9-R 12 are independently selected from any one of the following structure: hydrogen, alkyl group having 1 to 15 carbon atoms, alkyl ether group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms, alkylthio group having 1 to 15 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms, heterocycloalkyl group having 2 to 15 carbon atoms, heterocycloalkoxy group having 2 to 15 carbon atoms, aryl group having 6 to 25 carbon atoms, heteroaryl group having 3 to 25 carbon atoms, alkyl group having 1 to 15 carbon atoms substituted by fluorine atom, alkoxy group having 1 to 15 carbon atoms substituted by fluorine atom, alkylthio group having 1 to 15 carbon atoms substituted by fluorine atom, or alkyl ether group having 1 to 15 carbon atoms substituted by fluorine atom, substituted aryl group having 6 to 25 carbon atoms, substituted heteroaryl group having 3 to 25 carbon atoms;

[0011] 1 to 3 hydrogen atoms in the substituted aryl group having 6 to 25 carbon atoms, the substituted heteroaryl group having 3 to 25 carbon atoms are independently substituted by the following structure: cyano, nitro, halogen, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms, alkylthio group having 1 to 15 carbon atoms, alkyl ether group having 1 to 15 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms, heterocycloalkyl group having 2 to 15 carbon atoms, heterocycloalkoxy group having 2 to 15 carbon atoms, alkyl group having 1 to 15 carbon atoms substituted by fluorine atom, alkoxy group having 1 to 15 carbon atoms substituted by fluorine atom, alkylthio group having 1 to 15 carbon atoms substituted by fluorine atom, or alkyl ether group having 1 to 15 carbon atoms substituted by fluorine atom;

[0012] The cycloalkyl group having 3 to 15 carbon atoms, the heterocycloalkyl group having 2 to 15 carbon atoms, and the heterocycloalkoxy group having 2 to 15 carbon atoms include some or all of the carbon chains being cyclic or heterocyclic, wherein 1 to 3 hydrogen atoms in the carbon chain are replaced by alkyl groups having 1 to 15 carbon atoms.

[0013] R 13 Selected from the following structures: alkyl with 1 to 15 carbon atoms, alkyl ether group with 1 to 15 carbon atoms, aryl group with 6 to 25 carbon atoms, 1 to 3 hydrogen atoms replaced by cyano, nitro, halogen, alkyl with 1 to 6 carbon atoms, aryl group with 6 to 25 carbon atoms substituted by alkyl ether group with 1 to 6 carbon atoms;

[0014] R 14 R 15 Same or different, R 14 R 15 Each is independently selected from alkyl groups having an atomic number of 1 to 15, or R 14 R 15 They fuse together to form a ring structure.

[0015] Furthermore, when one of the structures in R1-R8 is selected from the group shown in formula (2) or formula (3), the structure of any one of R5-R8 is the group shown in formula (2) or formula (3), and the rest of R1-R8 are hydrogen.

[0016] When two of the structures in R1-R8 are selected from the groups shown in formula (2) or formula (3), the structures of any one of R1-R4 and any one of R5-R8 are the groups shown in formula (2) or formula (3), and the remaining R1-R8 are all hydrogen; and the substitution sites in R1-R8 that are not hydrogen are symmetrical or asymmetrical.

[0017] Furthermore, the cyclic structure in the cycloalkanone group with 4 to 15 carbon atoms, the aryl ketone group with 7 to 25 carbon atoms, the heterocycloalkanone group with 3 to 15 carbon atoms, the cycloalkyl group with 3 to 15 carbon atoms, the heterocycloalkyl group with 2 to 15 carbon atoms, the heterocycloalkoxy group with 2 to 15 carbon atoms, and the aryl group with 6 to 25 carbon atoms is a monocyclic structure;

[0018] The cyclic structures in the heteroaryl groups with 4 to 25 carbon atoms and the heteroaryl groups with 3 to 25 carbon atoms are each independently unsaturated five-membered heterocycles, or fused ring structures formed by an unsaturated five-membered heterocycle and a benzene ring sharing a pair of chemical bonds.

[0019] Furthermore, the cycloalkane group having 4 to 15 carbon atoms is a group formed by a five-membered or six-membered ring linked to a carbonyl group via a single bond or a C1-C6 alkylene group;

[0020] The heterocycloalkyl group having 2 to 15 carbon atoms is a saturated five- or six-membered heterocyclic group having 1 to 2 heteroatoms selected from O, S, and N, or a group formed by combining a saturated five- to six-membered heterocyclic group having 1 to 2 heteroatoms selected from O, S, and N with a C1-C6 alkylene group;

[0021] The aryl group having 6 to 25 carbon atoms is a phenyl group.

[0022] The heteroaroyl group having 4 to 25 carbon atoms is an unsaturated five-membered heteroaroyl group having one heteroatom selected from O, S, and N, or a benzene- fused five-membered heteroaroyl group having one heteroatom selected from O, S, and N.

[0023] The cycloalkyl group having 3 to 15 carbon atoms is a saturated five-membered ring group, a saturated six-membered ring group, or a group formed by combining a saturated five- to six-membered ring with a C1-C6 alkylene group.

[0024] The heterocycloalkyl group having 2 to 15 carbon atoms is a saturated five- or six-membered heterocyclic group having 1 to 2 heteroatoms selected from O, S, and N, or a group formed by combining a saturated five- to six-membered heterocyclic group having 1 to 2 heteroatoms selected from O, S, and N with a C1-C6 alkylene group.

[0025] The heterocycloalkoxy group having 2 to 15 carbon atoms is a group formed by combining a saturated five- to six-membered heterocyclic group having 1 to 2 heteroatoms selected from O, S, and N with a C1-C6 alkyloxy group.

[0026] The aryl group having 6 to 25 carbon atoms is a phenyl group.

[0027] The heteroaryl group having 3 to 25 carbon atoms is an unsaturated five-membered heteroaryl group having one heteroatom selected from O, S, and N, or a benzene-fused five-membered heteroaryl group having one heteroatom selected from O, S, and N.

[0028] Further, the photoinitiator is selected from any one of the following structures:

[0029] In a second aspect, a photopolymerization composition includes the following components: at least one ethylenically unsaturated photopolymerizable compound, a photoinitiator; the photoinitiator includes the photoinitiator.

[0030] Further, the total amount of the photopolymerization composition is 100 wt%, and the weight of the photoinitiator accounts for 0.01 to 10% of the weight of the photopolymerization composition.

[0031] Further, the photoinitiator further comprises a second photoinitiator and / or an additive.

[0032] Further, the second photoinitiator comprises at least one of a benzophenone photoinitiator, an a-hydroxy ketone photoinitiator, an a-aminoketone photoinitiator, a dimethylamino phenone photoinitiator, a thioxanthone photoinitiator, an xanthone photoinitiator, a bisimidazole photoinitiator, a triazine photoinitiator, and an O-acyl oxime photoinitiator.

[0033] The additive comprises at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

[0034] In a third aspect, an application of the photopolymerization composition, the photopolymerization composition is used in a color resist, a black matrix, a photo spacer, a planarization layer, a semiconductor photoresist, or an ink of a display element.

[0035] The present application has the following beneficial effects:

[0036] (1) The photoinitiator provided by the present application has significantly enhanced rigidity of the dioxylated diphenylhexa-membered ring core molecular structure and significantly improved optical absorption capacity, so that the compound maintains high solubility, exhibits high OD value and high photosensitivity to 365 nm wavelength light in a dark curing system, and can be better applied in a dark system such as a color resist and a black matrix of a display element, thereby realizing high contrast or realizing deep curing in the fields of a photo spacer, a planarization layer, a semiconductor photoresist, and an ink.

[0037] (2) The photoinitiator of the present application has significantly improved thermal stability and excellent exposure and development characteristics under low exposure (<1 s), and can prepare excellent photoetching patterns in a short exposure time, which is beneficial to improve industrial production efficiency and has broad commercialization prospects. BRIEF DESCRIPTION OF DRAWINGS

[0038] FIG. 1 is a nuclear magnetic spectrum of the compound (6) synthesized in Example 1;

[0039] FIG. 2 is a mass spectrum of the compound (6) synthesized in Example 2;

[0040] FIG. 3 is a graph of the photo-curing efficiency of the compound (6) (corresponding to SP1-S05) and P-3 (corresponding to oxe-02) on the acrylic double bond in a black resist with increasing exposure; DETAILED DESCRIPTION

[0041] To aid the understanding of the present application, a preferred embodiment is set forth, it being understood that this description is given solely by way of exemplification and that modifications of the preferred embodiments as well as embodiments based on other concepts from the present application are intended to fall within the scope of the present application. Unless otherwise indicated, the specific conditions (i.e., reaction solvents, reaction times, reaction temperatures, etc.) are chosen based on their convenience and are not intended to be limiting. Unless otherwise indicated, conventional methods of chemical synthesis are used to synthesize the compounds described herein. Unless otherwise indicated, the reagents and solvents used are commercially available and are used without further purification. Unless otherwise indicated, the reagents and solvents used are commercially available and are used without further purification.

[0042] Example 1: Preparation of compound (6)

[0043] The synthesis of the compound involved in this example is as follows:

[0044] S1. 30 g of phenothiazine was dissolved in 300 mL of N,N-dimethylformamide, 9.0 g of sodium hydroxide was added at 0°C, after stirring for 1 h, 29.8 g of chloro octane was added, and the reaction was stirred at room temperature overnight, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 39.6 g of 10-octyl phenothiazine;

[0045] S2. 30 g of 10-octyl phenothiazine and 12.8 g of aluminum chloride were dissolved in 300 mL of dichloromethane, 15.7 g of octanoyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h, 150 mL of 20 wt% ice dilute hydrochloric acid was used for quenching, the product was extracted with dichloromethane 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 23.2 g of (10-octyl phenothiazine-3-yl)-1-octyl ketone;

[0046] S3. 20 g of 1-(10-octyl phenothiazine-3-yl)-1-octyl ketone was dissolved in 250 mL of acetic acid, 3.3 g of hydrogen peroxide was added, the temperature was raised to 70°C, and the reaction was carried out for 6 h, the reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 19.3 g of (10-octyl phenothiazine sulfone-3-yl)-1-octyl ketone;

[0047] S4. 15 g of 1-(10-octyl phenothiazine sulfone-3-yl)-1-octyl ketone was dissolved in 200 mL of N,N-dimethylformamide, 2.6 mL of concentrated hydrochloric acid and 2.85 g of isobutyl nitrite were added in sequence, the reaction was stirred at room temperature for 6 h, and ice water was used for quenching, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 11.5 g of 1-(10-octyl phenothiazine sulfone-3-yl)-1,2-octanedione-2-oxime;

[0048] S5. 10 g of 1-(10-octylphenothiazine sulfone-3-yl)-1,2-octanedione-2-oxime, 2.23 g of triethylamine were dissolved in 30 mL of dichloromethane, 1.73 g of acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h, 10 mL of 20 wt% ice dilute hydrochloric acid was quenched, extracted with ethyl acetate twice, dried with magnesium sulfate, concentrated, and dried to obtain 8.35 g of compound (6) (Figures 1 to 3).

[0049] Example 2: Preparation of compound (10)

[0050] The synthesis steps of the compound involved in this example are as follows:

[0051] S1. 30 g of phenothiazine was dissolved in 300 mL of N,N-dimethylformamide, 9.0 g of sodium hydroxide was added at 0°C, and after stirring for 1 h, 29.8 g of chloroiso-octane was further added, and the reaction was stirred at room temperature overnight, washed with water, and the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 38.9 g of 10-(2-ethylhexyl)phenothiazine;

[0052] S2. 30 g of 10-(2-ethylhexyl)phenothiazine and 12.8 g of aluminum chloride were dissolved in 300 mL of dichloromethane, 16.8 g of 3-cyclohexylpropionyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h, 150 mL of 20 wt% ice dilute hydrochloric acid was quenched, the product was extracted with dichloromethane 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 22.5 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1-cyclohexylpropyl ketone;

[0053] S3. 20 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1-cyclohexylpropyl ketone was dissolved in 250 mL of acetic acid, 3.2 g of hydrogen peroxide was added, and the temperature was raised to 70°C, and the reaction was performed for 6 h, the reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 19.5 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1-cyclohexylpropyl ketone;

[0054] S4. 15 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1-cyclohexylpropyl ketone was dissolved in 200 mL of N,N-dimethylformamide, 2.6 mL of concentrated hydrochloric acid and 4.2 g of isobutyl nitrite were sequentially added, and the reaction was stirred at room temperature for 6 h, and the reaction mixture was quenched with ice water, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 15.9 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1,2-cyclohexylpropyl diketone-2-oxime;

[0055] S5. 10 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1,2- cyclohexylpropyl diketone-2-oxime, 2.12 g of triethylamine were dissolved in 30 mL of dichloromethane, 1.65 g of acetyl chloride dissolved in 10 mL of dichloromethane was slowly added dropwise at 0 °C, and the reaction was stirred for 2 h, 10 mL of 20 wt% ice dilute hydrochloric acid was quenched, extracted with ethyl acetate twice, dried over magnesium sulfate, concentrated, and dried to obtain 7.90 g of compound (10).

[0056] MS: 553.2464 (MS+1), accurate molecular mass: 552.2658.

[0057] Example 3: Preparation of compound (12)

[0058] The synthesis steps of the compound involved in this example are as follows:

[0059] S1. 10-octylphenothiazine in S2 of Example 1 was replaced with 10-(2- ethylhexyl)phenothiazine, octanoyl chloride was replaced with 2,2-dimethyl-1,3- dioxolane acetyl chloride, and the same way as S2 of Example 1 was prepared except for this, to obtain 22.3 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1- cyclohexylpropanone;

[0060] S2. 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in S3 of Example 1 was replaced with the product of S1 above, and the same way as S3 of Example 1 was prepared except for this, to obtain 18.4 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-(2,2- dimethyl-1,3-dioxolane)ethyl-1-ketone;

[0061] S3. 1-(10-octylphenothiazine sulfone-3-yl)-1-octyl ketone in S4 of Example 1 was replaced with the product of S2 above, and the same way as S4 of Example 1 was prepared except for this, to obtain 11.0 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1,2-(2,2-dimethyl-1,3- dioxolane)ethyl diketone-2-oxime;

[0062] S4. 1-octylphenothiazine sulfone-3-yl)-1,2-octanedione-2-oxime in S5 of Example 1 was replaced with the product of S3 above, and the same way as S5 of Example 1 was prepared except for this, to obtain 8.45 g of compound (12).

[0063] MS: 553.2464 (MS+1), accurate molecular mass: 552.2658.

[0064] Example 4: Preparation of compound (13)

[0065] The synthesis steps of the compound involved in this example are as follows:

[0066] S1. 30 g of 10-(2-ethylhexyl) phenothiazine was dissolved in 350 mL of acetic acid, 6.9 g of hydrogen peroxide was added, the temperature was raised to 70°C, and the reaction was carried out for 6 h. The reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted with ethyl acetate for 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 30.8 g of 10-(2-ethylhexyl) phenothiazine sulfone;

[0067] S2. 25 g of 10-(2-ethylhexyl) phenothiazine sulfone and 9.7 g of aluminum chloride were dissolved in 300 mL of dichloromethane, 11.7 g of 2-thiophene acetyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h. 150 mL of 20 wt% ice dilute hydrochloric acid was used for quenching, the product was extracted with dichloromethane for 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 18.0 g of 1-(10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-(thiophene-2-yl) ethyl ketone;

[0068] S3. 15 g of 1-(10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-(thiophene-2-yl) ethyl ketone was dissolved in 200 mL of N,N-dimethylformamide, 2.6 mL of concentrated hydrochloric acid and 3.3 g of isobutyl nitrite were added in sequence, the reaction was stirred at room temperature for 6 h, ice water was used for quenching, the reaction mixture was extracted with ethyl acetate for 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 10.4 g of 1-(10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1,2-(thiophene-2-yl) ethyl ketone-2-oxime;

[0069] S4. 10 g of 1-(10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1,2-(thiophene-2-yl) ethyl ketone-2-oxime and 2.24 g of triethylamine were dissolved in 30 mL of dichloromethane, 1.74 g of acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h. 10 mL of 20 wt% ice dilute hydrochloric acid was used for quenching, extracted with ethyl acetate twice, dried over magnesium sulfate, concentrated, and dried to obtain 8.24 g of compound (13).

[0070] MS: 539.5541 (MS+1), accurate molecular mass: 538.1596.

[0071] Example 5: Preparation of compound (16)

[0072] The synthesis steps of the compound involved in this example are as follows:

[0073] S1. Replace the chloro-octane in Example 1S1 with chloro-isohexane, and otherwise prepare in the same manner as Example 1S1 to give 36.3 g of 10-(2-ethylbutyl)phenothiazine;

[0074] S2. Replace the 10-octylphenothiazine in Example 1S2 with the product of S1 above, and replace the octanoyl chloride with o-(2,2,3,3-tetrafluoropropoxy)phenylacetyl chloride, and otherwise prepare in the same manner as Example 1S2 to give 27.3 g of l-(10-(2-ethylbutyl)phenothiazin-3-yl)-l-o-(2,2,3,3-tetrafluoropropoxy)phenylacetophenone;

[0075] S3. Replace the l-(10-octylphenothiazin-3-yl)-l-octylketone in Example 1S3 with the product of S2 above, and otherwise prepare in the same manner as Example 1S3 to give 21.2 g of l-(10-(2-ethylbutyl)phenothiazin-3-yl)-l-o-(2,2,3,3-tetrafluoropropoxy)phenylacetophenone;

[0076] S4. Replace the l-(10-octylphenothiazin-3-yl)-l-octylketone in Example 1S4 with the product of S3 above, and otherwise prepare in the same manner as Example 1S4 to give 9.8 g of l-(10-(2-ethylbutyl)phenothiazin-3-yl)-l,2-o-(2,2,3,3-tetrafluoropropoxy)phenylpropanedione-2-oxime;

[0077] S5. Replace the 10 g of l-(10-octylphenothiazin-3-yl)-l,2-octanedione-2-oxime in Example 1S5 with the 5 g of product of S4 above, and otherwise prepare in the same manner as Example 1S5 to give 4.23 g of compound (16).

[0078] MS: 635.1247 (MS + 1), exact molecular mass: 634.1761.

[0079] Example 6: Preparation of compound (17)

[0080] The synthesis of the compound involved in this example is as follows:

[0081] S1. Replace the chloro-octane in Example 1S1 with chloro-isohexane, and otherwise prepare in the same manner as Example 1S1 to give 36.3 g of 10-(2-ethylbutyl)phenothiazine;

[0082] S2. Replace 1 -(10-octylphenothiazine-3-yl)-1 -p-(methoxy-3- methylbutoxy) acetophenone in Example 1S3 with the product of S1 above and prepare in the same manner as Example 1S3 except for this to give 18.8 g of 1 -(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)-1 -p-(methoxy-3- methylbutoxy) acetophenone;

[0083] S3. Replace 1 -(10-octylphenothiazine sulfone-3-yl)-1 -octyl ketone in Example 1S4 with the product of S2 above and prepare in the same manner as Example 1S4 except for this to give 10.0 g of 1 -(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)-1,2-p-(methoxy-3- methylbutoxy) benzil-2-oxime;

[0084] S4. Replace 1 -(10-octylphenothiazine sulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above and prepare in the same manner as Example 1S5 except for this to give 8.1 g of compound (17).

[0085] MS: 649.3591 (MS + 1), exact molecular mass: 648.2869.

[0086] Example 7: Preparation of compound (18)

[0087] The synthesis of the compound involved in this example is as follows:

[0088] S1. Replace 10-octylphenothiazine in Example 1S2 with 10-(2-ethylhexyl)phenothiazine and pivaloyl chloride with p-(2,2-dimethyl-1,3-dioxolan) o-toluoyl chloride and prepare in the same manner as Example 1S2 except for this to give 28.7 g of 1 -(10-(2-ethylhexyl)phenothiazine-3-yl)-1 -p-(2,2-dimethyl-1,3- dioxolan) o-toluene ketone;

[0089] S2. Replace 1 -(10-octylphenothiazine-3-yl)-1 -octyl ketone in Example 1S3 with the product of S1 above and prepare in the same manner as Example 1S3 except for this to give 19 g of 1 -(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1 -p-(2,2-dimethyl-1,3- dioxolan) o-toluene ketone;

[0090] S3. Replace 1 -(10-octylphenothiazine-3-yl)-1 -octyl ketone in Example 1S4 with the product of S2 above, and otherwise prepare in the same manner as Example 1S4 to give 9.6 g of 1 -(10-(2-ethylhexyl)phenothiazine-3-yl)-1,2-p- (2,2-dimethyl-1,3-dioxolane)toluylenedione-2-oxime;

[0091] S4. Replace 1 -(10-octylphenothiazine-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with 5 g of the product of S3 above, and otherwise prepare in the same manner as Example 1S5 to give 4.2 g of compound (18).

[0092] MS: 677.1276 (MS + 1), exact molecular mass: 676.2818.

[0093] Example 8: Preparation of compound (27)

[0094] The synthesis of the compound involved in this example is as follows:

[0095] S1. Replace 10-octylphenothiazine in Example 1S2 with 10-ethylphenothiazine, and replace octanoyl chloride with hexanoyl chloride, and otherwise prepare in the same manner as Example 1S2 to give 24.5 g of (10-ethyl-10H-phenothiazin-3-yl)-1 -hexyl ketone;

[0096] S2. Replace 1 -(10-octylphenothiazine-3-yl)-1 -octyl ketone in Example 1S3 with the product of S1 above, and otherwise prepare in the same manner as Example 1S3 to give 20.2 g of (10-ethyl-10H-phenothiazine-3-yl)-1 -hexyl ketone;

[0097] S3. Replace 1 -(10-octylphenothiazine-3-yl)-1 -octyl ketone in Example 1S4 with the product of S2 above, and otherwise prepare in the same manner as Example 1S4 to give 11.0 g of (10-ethyl-10H-phenothiazine-3-yl)-1,2-hexanedione-2-oxime;

[0098] S4. Replace 1 -(10-octylphenothiazine-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above, and replace acetyl chloride with p-methoxybenzoyl chloride, and otherwise prepare in the same manner as Example 1S5 to give 9.4 g of compound (27).

[0099] MS: 521.6852 (MS + 1), exact molecular mass: 520.1668.

[0100] Example 9: Preparation of compound (28)

[0101] The synthesis steps of the compound involved in this example are as follows:

[0102] S1. 30 g of 10-(2-ethylhexyl) phenothiazine and 12.8 g of aluminum chloride were dissolved in 300 mL of dichloromethane, 14.9 g of o-toluene acetyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h. After the reaction was completed, 12.8 g of aluminum chloride was continuously added, and after the solution was fully stirred, 17.2 g of octanoyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C. After the dropwise addition was completed, the reaction was continuously stirred for 3 h. 150 mL of 20 wt% ice dilute hydrochloric acid was used for quenching, the product was extracted with dichloromethane 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 22.5 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine-3-yl)-1-octyl ketone;

[0103] S2. 20 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine-3-yl)-1-octyl ketone was dissolved in 250 mL of acetic acid, 2.6 g of hydrogen peroxide was added, and the temperature was raised to 70°C. The reaction was carried out for 6 h. The reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 18.8 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octyl ketone;

[0104] S3. 15 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octyl ketone was dissolved in 200 mL of N,N-dimethylformamide, 2.2 mL of concentrated hydrochloric acid and 3.4 g of isobutyl nitrite were sequentially added, and the reaction was stirred at room temperature for 6 h. The reaction mixture was quenched with ice water, and the product was extracted with ethyl acetate 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 10.2 g of 15 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxy imino-1-octyl ketone;

[0105] S4. 10 g of (6-o-methyl phenone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxy imino-1-octyl ketone and 1.8 g of triethylamine were dissolved in 30 mL of dichloromethane, 1.4 g of acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h. 10 mL of 20 wt% ice dilute hydrochloric acid was used for quenching, the product was extracted with ethyl acetate twice, dried with magnesium sulfate, concentrated, and dried to obtain 7.8 g of compound (28).

[0106] MS: 659.6871 (MS+1), accurate molecular mass: 658.3077.

[0107] Example 10: Preparation of compound (31)

[0108] The synthesis steps of the compound involved in this example are as follows:

[0109] S1. Replace o-toluoyl chloride in Example 9 S1 with 2-methyl-2-morpholinopropanoyl chloride, and prepare in the same manner as Example 9 S1 except for this, to obtain 22.84 g of (6-(2-methyl-2-morpholinopropanoyl)-10-(2-ethylhexyl) phenothiazin-3-yl)-1-octanone;

[0110] S2. Replace (6-o-toluoyl-10-(2-ethylhexyl) phenothiazin-3-yl)-1-octanone in Example 9 S2 with the product of S1 above, and prepare in the same manner as Example 9 S2 except for this, to obtain 18.3 g of (6-(2-methyl-2-morpholinopropanoyl)-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octanone;

[0111] S3. Replace (6-o-toluoyl-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octanone in Example 9 S3 with the product of S2 above, and prepare in the same manner as Example 9 S3 except for this, to obtain 10.5 g of (6-(2-methyl-2-morpholinopropanoyl)-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octanone;

[0112] S4. Replace (6-o-toluoyl-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octanone in Example 9 S4 with the product of S2 above, and prepare in the same manner as Example 9 S4 except for this, to obtain 8.3 g of compound (31).

[0113] MS: 696.3217 (MS+1), accurate molecular mass: 695.3604.

[0114] Example 11: Preparation of compound (43)

[0115] The synthesis steps of the compound involved in this example are as follows:

[0116] S1. Replace 10-(2-ethylhexyl) phenothiazine in Example 9 S1 with 10-ethyl phenothiazine, and replace octanoyl chloride with formyl chloride, and prepare in the same manner as Example 9 S1 except for this, to obtain 22.3 g of (6-o-toluoyl-10-butyl phenothiazin-3-yl)-1-ethyl ketone;

[0117] S2. Replace (6-o-tolylketone-10-(2-ethylhexyl)phenothiazin-3-yl)-1- octanone in Example 9S2 with the product of S2 above, and otherwise prepare in the same manner as Example 9S2 to give 19.5 g of (6-o-tolylketone-10- butylphenothiazine-3-yl)-1-ethyl ketone;

[0118] S3. Dissolve 15 g of (6-o-tolylketone-10-butylphenothiazine-3-yl)-1- ethyl ketone in 150 mL of toluene, add 3.7 g of sodium acetate and 3.3 g of hydroxylamine hydrochloride, heat to reflux for 8 h, cool the reaction to room temperature, wash with water, extract the product 1-2 times with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to give 11.2 g of (6-o-tolylketone-10- butylphenothiazine-3-yl)-ethanone oxime;

[0119] S5. Replace (6-o-tolylketone-10-(2-ethylhexyl)phenothiazine-3-yl)-2- hydroxyimino-1-octanone in Example 9S4 with the product of S4 above, and replace acetyl chloride with formyl chloride, and otherwise prepare in the same manner as Example 9S4 to give 8.8 g of compound (43).

[0120] MS: 477.5741 (MS + 1), accurate molecular mass: 476.1406.

[0121] Example 12: Preparation of compound (45)

[0122] The synthesis of the compound involved in this example is as follows:

[0123] S1. Dissolve 30 g of phenothiazine in 300 mL of N,N-dimethylformamide, add 9.0 g of sodium hydroxide at 0 °C, stir for 1 h, then add 16.7 g of chlorobutane, stir at room temperature overnight, wash with water, extract the product 1-2 times with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to give 33.0 g of 10-butylphenothiazine;

[0124] S2. Replace o-tolylacetyl chloride in Example 11S1 with benzofuran-2- acetyl chloride, and replace formyl chloride with valeryl chloride, and otherwise prepare in the same manner as Example 11S1 to give 23.3 g of (6-(benzofuran-2- ketone)-10-butylphenothiazin-3-yl)-1-pentyl ketone;

[0125] S3. Replace (6-o-tolyl-10-butylphenothiazin-3-yl)-1-ethyl ketone in Example 11 S2 with the product of S2 above and prepare in the same manner as Example 11 S2 except for this change to give 16.5 g of (6-(benzofuran-2-yl)-10-butylphenothiazine sulfone-3-yl)-1-pentyl ketone;

[0126] S4. Replace (6-o-tolyl-10-butylphenothiazine sulfone-3-yl)-1-ethyl ketone in Example 11 S3 with the product of S3 above and prepare in the same manner as Example 11 S3 except for this change to give 10.8 g of (6-(benzofuran-2-yl)-10-butylphenothiazine sulfone-3-yl)-pentanone oxime;

[0127] S5. Replace (6-o-tolyl-10-butylphenothiazine sulfone-3-yl)-pentanone oxime in Example 11 S4 with the product of S4 above and replace formyl chloride with chloroformyl propyl ester and prepare in the same manner as Example 11 S4 except for these changes to give 8.2 g of compound (45).

[0128] MS: 585.3187 (MS + 1), exact molecular mass: 584.2345.

[0129] Example 13: Preparation of compound (91)

[0130] The synthesis of the compound involved in this example is as follows:

[0131] S1. Replace phenothiazine in Example 1 S1 with 3-nitro-10H-phenothiazine and replace chloro octane with chloro butane and prepare in the same manner as Example 1 S1 except for these changes to give 30.2 g of 3-nitro-10-butylphenothiazine;

[0132] S2. Replace 10-octylphenothiazine in Example 1 S2 with the product of S1 above and replace octanoyl chloride with p-nitrophenyl acetyl chloride and prepare in the same manner as Example 1 S2 except for these changes to give 22.4 g of (6-nitro-10-butylphenothiazin-3-yl)-1-p-nitrophenyl ketone;

[0133] S3. Replace (10-octylphenothiazin-3-yl)-1-octyl ketone in Example 1 S3 with the product of S2 above and prepare in the same manner as Example 1 S3 except for this change to give 19.0 g of (6-nitro-10-butylphenothiazine sulfone-3-yl)-1-p-nitrophenyl ketone;

[0134] S4. Replace (6-o-tolylketone-10-butylphenothiazine sulfone-3-yl)-1- ethyl ketone oxime in Example 11 S4 with the product of S3 above, and otherwise prepare in the same manner as Example 11 S4 to give 10.5 g of (6-nitro-10- butylphenothiazine-3-yl)-1-p-nitrobenzophenone oxime.

[0135] S5. Replace (6-o-tolylketone-10-butylphenothiazine sulfone-3-yl)- ethyl ketone oxime in Example 11 S5 with the product of S4 above, and otherwise prepare in the same manner as Example 11 S5 to give 8.0 g of compound (91).

[0136] MS: 539.6975 (MS + 1), exact molecular mass: 538.1158.

[0137] Example 14: Preparation of compound (96)

[0138] The synthesis of the compound involved in this example is as follows:

[0139] S1. Replace chloro octane in Example 1 S1 with chloro 2-ethylbutane, and otherwise prepare in the same manner as Example 1 S1 to give 35.8 g of 10-(2- ethylbutyl)phenothiazine.

[0140] S2. Dissolve 30 g of 10-(2-ethylbutyl)phenothiazine and 28.3 g of aluminum chloride in 300 mL of dichloromethane, slowly add a solution of 31.3 g of propionyl chloride dissolved in 50 mL of dichloromethane at 0 °C, and stir the reaction for 2 h, quench with 150 mL of 20 wt% ice cold dilute hydrochloric acid, extract the product 1-2 times with dichloromethane, dry over magnesium sulfate, concentrate, and dry to give 24.6 g of 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)dipropionitrile.

[0141] S3. Replace (10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1 S3 with the product of S2 above, and otherwise prepare in the same manner as Example 1 S3 to give 19.7 g of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropionitrile.

[0142] S4. 15 g of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone was dissolved in 200 mL of N,N-dimethylformamide, 2.6 mL of concentrated hydrochloric acid and 7.8 g of isobutyl nitrite were sequentially added, and the reaction was stirred at room temperature for 6 h. The reaction mixture was quenched with ice water, and the product was extracted with ethyl acetate 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 11.3 g of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)bis(propanone-2-oxime);

[0143] S5. 10 g of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)bis(propanone-2-oxime) and 4.64 g of triethylamine were dissolved in 100 mL of dichloromethane, and 2.7 g of an acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h. The reaction was quenched with 10 mL of 20 wt% ice dilute hydrochloric acid, extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 8.4 g of compound (96).

[0144] MS: 570.5246 (MS+1), accurate molecular mass: 569.1832.

[0145] Example 15: Preparation of compound (99)

[0146] The synthesis steps of the compound involved in this example are as follows:

[0147] S1. 10-(2-ethylbutyl)phenothiazine in Example 14 S2 was replaced with 10-octylphenothiazine, and propionyl chloride was replaced with octanoyl chloride, and the same method as in Example 14 S2 was used, except for the above, to obtain 24.6 g of 1,1'-(10-octylphenothiazine-3,6-diyl)dioctanone;

[0148] S2. 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone in Example 14 S3 was replaced with the product of S1 above, and the same method as in Example 14 S3 was used, except for the above, to obtain 19.7 g of 1,1'-(10-(octylphenothiazine sulfone-3,6-diyl)dioctanone;

[0149] S3. 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone in Example 14 S4 was replaced with the product of S2 above, and the same method as in Example 14 S4 was used, except for the above, to obtain 11.4 g of 1,1'-(10-octylphenothiazine sulfone-3,6-diyl)bis(octanone-2-oxime);

[0150] S4. Replace 1,1'-(10-(2-ethylbutyl)phenothiazine-3-yl)bis(propanone-2-oxime) in Example 14S5 with the product of S3 above, and otherwise prepare in the same manner as Example 14S5 to give 8.5 g of compound (99).

[0151] MS: 738.5794 (MS + 1), exact mass: 737.3710.

[0152] Example 16: Preparation of compound (102)

[0153] The synthesis steps for the compound of this example are as follows:

[0154] S1. Replace 10-(2-ethylbutyl)phenothiazine in Example 14S2 with 10- ethylphenothiazine, and replace propionyl chloride with 2-(2- ethoxyethoxy)acetyl chloride, and otherwise prepare in the same manner as Example 14S2 to give 28.3 g of 1,1'-(10- ethylphenothiazine-3,6-diyl)bis(2-ethoxyethoxyethanone);

[0155] S2. Replace 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)bispropanone in Example 14S3 with the product of S1 above, and otherwise prepare in the same manner as Example 14S3 to give 19.1 g of 1,1'-(10- ethylphenothiazine-3,6-diyl)bis(2-ethoxyethoxyethanone);

[0156] S3. Replace 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)bispropanone in Example 14S4 with the product of S2 above, and otherwise prepare in the same manner as Example 14S4 to give 11.7 g of 1,1'-(10- ethylphenothiazine-3,6-diyl)bis(2-ethoxyethoxyethanone-2-oxime);

[0157] S4. Replace 1,1'-(10-(2-ethylbutyl)phenothiazine-3-yl)bis(propanone-2-oxime) in Example 14S5 with the product of S3 above, and otherwise prepare in the same manner as Example 14S5 to give 8.8 g of compound (102).

[0158] MS: 662.3975 (MS + 1), exact mass: 661.1941.

[0159] Example 17: Preparation of compound (107)

[0160] The synthesis steps for the compound of this example are as follows:

[0161] S1. Instead of aluminum chloride in Example 4S2, 17 g of 2-thiopheneacetyl chloride is used, and the rest is prepared in the same manner as Example 4S2 to obtain 14.5 g of 1,1'-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl) bis((thiophene-2-yl)ethyl ketone);

[0162] S2. The input amount of the product of S1 above is adjusted to 10 g, and instead of isobutyl nitrite in Example 4S3, 5.2 g of is used, and the rest is prepared in the same manner as Example 4S3 to obtain 6.6 g of 1,1'-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl) bis((thiophene-2-yl)ethyl ketone-2-oxime);

[0163] S3. The input amount of the product of S2 above is adjusted to 5 g, and instead of triethylamine in Example 4S4, 2.4 g of is used, and instead of acetyl chloride, 1.4 g of is used, and the rest is prepared in the same manner as Example 4S4 to obtain 4.0 g of compound (107).

[0164] MS: 734.5248 (MS+1), accurate molecular mass: 733.1586.

[0165] Example 18: Preparation of compound (129)

[0166] The synthesis steps of the compound involved in this example are as follows:

[0167] S1. Instead of 10-octylphenothiazine in Example 1S2, thioxanthone is used, and the rest is prepared in the same manner as Example 1 to obtain 23.9 g of (thioxanthone-3-yl)-1-octyl ketone;

[0168] S2. Instead of 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3, the product of S1 above is used, and the rest is prepared in the same manner as Example 1 to obtain 19.7 g of (10,10-dioxothioxanthone-3-yl)-1-octyl ketone;

[0169] S3. Instead of 1-(10-octylphenothiazine sulfone-3-yl)-1-octyl ketone in Example 1S4, the product of S2 above is used, and the rest is prepared in the same manner as Example 1 to obtain 9.1 g of (10,10-dioxothioxanthone-3-yl)-1-octyl ketone-2-oxime;

[0170] S4. Instead of 1-(10-octylphenothiazine sulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5, the product of S3 above is used, and the input amount is adjusted to 5 g, and the rest is prepared in the same manner as Example 1 to obtain 4.2 g of compound (129).

[0171] MS: 442.3587 (MS + 1), exact mass: 441.1246.

[0172] Example 19: Preparation of compound (138)

[0173] The synthetic procedure of the compound involved in this example is as follows:

[0174] S1. Replace 10-(2-ethylhexyl)phenothiazine in Example 9 S1 with thioxanthone, replace o-toluoyl chloride with furanoyl chloride, replace octanoyl chloride with propionyl chloride, and prepare in the same manner as Example 9 S1 except for the above, to obtain 20.5 g of (6-furanoyl-thioxanthone-3-yl)-1-propyl ketone;

[0175] S2. Replace (6-o-toluyloyl-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octyl ketone in Example 9 S2 with the product of S1 above, and prepare in the same manner as Example 9 S2 except for the above, to obtain 18.9 g of (6-furanoyl-10,10-dioxo-thioxanthone-3-yl)-1-propyl ketone;

[0176] S3. Replace (6-o-toluyloyl-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1-octyl ketone in Example 9 S3 with the product of S2 above, and prepare in the same manner as Example 9 S3 except for the above, to obtain 9.2 g of (6-furanoyl-10,10-dioxo-thioxanthone-3-yl)-1-propyl ketone-2-oxime;

[0177] S4. Replace (6-o-toluyloyl-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone in Example 9 S4 with the product of S3 above, and prepare in the same manner as Example 9 S4 except for the above, to obtain 3.9 g of compound (138) with a 5 g input.

[0178] MS: 442.3587 (MS + 1), exact mass: 441.1246.

[0179] Example 20: Preparation of compound (167)

[0180] The synthetic procedure of the compound involved in this example is as follows:

[0181] S1. Replace 10-(2-ethylbutyl)phenothiazine in Example 14 S2 with thioxanthone, replace propionyl chloride with octanoyl chloride, and prepare in the same manner as Example 14 S2 except for the above, to obtain 28.9 g of 1,1'-(thioxanthone-3,6-diyl) dioctanone;

[0182] S2. Replace 1,1 '-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone in Example 14S3 with the product of S1 above and otherwise prepare in the same manner as Example 14S3 to give 19.0 g of 1,1 '-(10,10-dioxothioxanthone-3,6-diyl)dioctanone;

[0183] S3. Replace 1,1 '-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone in Example 14S4 with the product of S2 above and otherwise prepare in the same manner as Example 14S4 to give 10.1 g of 1,1 '-(10,10-dioxothioxanthone-3,6-diyl)bis(octanone-2-oxime);

[0184] S4. Replace 1,1 '-(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)bis(propanone-2-oxime) in Example 14S5 with the product of S3 above and otherwise prepare in the same manner as Example 14S5 to give 8.6 g of compound (167).

[0185] MS: 567.2384 (MS + 1), exact molecular mass: 566.1359.

[0186] Example 21: Preparation of compound (237)

[0187] The synthesis of the compound involved in this example is as follows:

[0188] S1. Replace 10-ethylphenothiazine in Example 11S2 with phenoxathiine, replace o-toluoyl chloride with 2,4,6-trimethylbenzoyl chloride, replace formyl chloride with propionyl chloride and otherwise prepare in the same manner as Example 11S2 to give 22.9 g of (8-(2,4,6-trimethylphenone)-phenoxathiine-2-yl)-1- propyl ketone;

[0189] S2. Replace (6-o-methylphenone-10-butylphenothiazine-3-yl)-1-ethyl ketone in Example 11S3 with the product of S1 above and otherwise prepare in the same manner as Example 11S3 to give 17.4 g of (8-(2,4,6-trimethylphenone)-10,10-dioxophenoxathiine-2-yl)-1- propyl ketone;

[0190] S3. Replace (6-o-methylphenone-10-butylphenothiazine sulfone-3-yl)-1-ethyl ketone in Example 11S4 with the product of S2 above and otherwise prepare in the same manner as Example 11S4 to give 10.4 g of (8-(2,4,6-trimethylphenone)-10,10-dioxophenoxathiine-2-yl)-1- propyl ketone-2-oxime;

[0191] S4. Instead of (6-o-tolyl-10-butylphenothiazine sulfone-3-yl)-ethanone oxime in Example 11S5, the product of S3 above is used, and the same manner as Example 11S4 is followed, except that, to give 7.8 g of compound (237).

[0192] MS: 476.2152 (MS + 1), exact mass: 475.1453.

[0193] Example 22: Preparation of compound (245)

[0194] The synthetic steps of the compound involved in this example are as follows:

[0195] S1. Instead of 10-(2-ethylbutyl)phenothiazine in Example 14S2, 9,9-dimethyl-9H-thioxanthene is used, and the same manner as Example 14S2 is followed, except that, to give 20.2 g of 1,1'-(9,9-dimethyl-9H-thioxanthene-3,6-diyl)dipropanone;

[0196] S2. Instead of 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)dipropanone in Example 14S3, the product of S1 above is used, and the same manner as Example 14S3 is followed, except that, to give 19.9 g of 1,1'-(9,9-dimethyl-9H-thioxanthene sulfone-3,6-diyl)dipropanone;

[0197] S3. Instead of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3,6-diyl)dipropanone in Example 14S4, the product of S2 above is used, and the same manner as Example 14S4 is followed, except that, to give 12.1 g of 1,1'-(9,9-dimethyl-9H-thioxanthene sulfone-3,6-diyl)bis(propanone-2-oxime);

[0198] S4. Instead of 1,1'-(10-(2-ethylbutyl)phenothiazine sulfone-3-yl)bis(propanone-2-oxime) in Example 14S5, the product of S3 above is used, and the same manner as Example 14S5 is followed, except that, to give 9.2 g of compound (245).

[0199] MS: 513.5714 (MS + 1), exact mass: 512.1253.

[0200] Comparative Examples 1 to 6

[0201] As the photopolymerization initiator, a compound represented by the following formula is used:

[0202] Test Example

[0203] The compounds obtained in the above synthesis examples were subjected to the following physical property evaluation. Also, for comparison, the photopolymerization initiators of Comparative Examples 1 to 4 were also subjected to the same physical property evaluation, and the results are shown in Table 1.

[0204] The photoinitiation performance of the compounds of the above examples and comparative examples was tested using the following method, as follows:

[0205] (1) Maximum absorption wavelength and molar absorption coefficient

[0206] The photoinitiator of the present application was prepared as a 10 -5 moL / L solution in propylene glycol methyl ether acetate (PMA), and its UV-Vis absorption spectrum was tested to obtain its maximum absorption wavelength (λ max ), and the molar absorption coefficient (ε max ) at the maximum absorption wavelength was calculated according to the Beer's law.

[0207] (2) Solubility

[0208] Taking the widely used active diluent propylene glycol methyl ether acetate (PMA) as an example, the maximum weight of the photoinitiator of the present application that can be completely dissolved in 100 g of solvent at 25°C was taken as the evaluation standard.

[0209] (3) Photosensitivity

[0210] 20 wt% of bisphenol fluorene resin, 60 wt% of carbon black, 0.5 wt% of the compound of the present application as a photopolymerization initiator, and 0.1 wt% of FC-430 (3M leveling agent), 19.4 wt% of PMA were put into a reaction mixing tank with a UV shield and a stirrer, and after stirring at room temperature, a photopolymerization composition was prepared. The photopolymerization composition was spin-coated on a glass substrate and dried on a hot plate at 100°C for 1 minute, then exposed using a step mask and developed in 0.04% KOH aqueous solution, the photosensitivity was evaluated based on the exposure dose at which the thickness of the step mask pattern was maintained at 80% of the initial thickness, and the exposure dose at which the thickness of the P-1 pattern was maintained at 80% of the initial thickness was defined as 1, and other photoinitiators were evaluated, and at the same residual thickness, the exposure dose was less, and the sensitivity was higher.

[0211] Table 1

[0212] As can be seen from Table 1, the oxime ester photoinitiator constructed by the double-oxidized dibenzo-hexacyclic core in the application shows significant enhancement of molecular structure rigidity and significant improvement of optical absorption capacity, so that the compound maintains high solubility, and in the deep color curing system, relative to the unoxidized or single-oxidized dibenzo-hexacyclic core or the commercial mainstream product, it shows high OD value, high photosensitivity and certain inhibition of oxygen inhibition, thereby better applying in the deep color system such as color resist and black matrix of display elements to realize high contrast, or realizing deep curing in the field of photo spacer, planarization layer, semiconductor photoresist and ink, etc. In addition, relative to the unoxidized or single-oxidized dibenzo-hexacyclic core, the thermal stability of the photoinitiator of the application is also significantly improved, and it has excellent exposure and development characteristics under the condition of low exposure amount (<2s), and excellent photoetching patterns are prepared under short exposure time, which is conducive to improving the industrial production efficiency and has broad commercialization prospects.

[0213] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and belong to the protection scope of the application.

Claims

1. A photoinitiator characterized by, The photoinitiator is a compound of the structure shown in formula (1): R3, R6in formula (1) are selected from the group consisting of radicals of formula (2) or (3): or R3 is selected from a group represented by formula (2) or formula (3), and R6 is selected from any one of the following structures: nitro, heterocyclic alkanoyl with carbon atoms number of 3-15, aromatic ketone group with carbon atoms number of 7-25, heteroaromatic ketone group with carbon atoms number of 4-25, substituted aromatic ketone group with carbon atoms number of 7-25; the rest of R1-R8 are all hydrogen; 1-3 hydrogen atoms in the substituted aromatic ketone group with carbon atoms number of 7-25 are independently substituted by the following structures: alkyl with carbon atoms number of 1-8; the heterocyclic alkanoyl with carbon atoms number of 3-15 comprises a part or whole carbon chain as a cyclic or heterocyclic ring, and 0-3 hydrogen atoms in the carbon chain are substituted by alkyl with carbon atoms number of 1-8; X1is selected from any one of the following structures: an oxygen atom, a ketone group, N(R 13 ), C(R 14 )(R 15 ), and X2is selected from a sulfonyl group; R9, R 11 each independently selected from any one of the following structures: an alkyl group having 1 to 15 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a heterocycloalkyl group having 2 to 15 carbon atoms, an aryl group having 6 to 25 carbon atoms, a heteroaryl group having 3 to 25 carbon atoms, a substituted aryl group having 6 to 25 carbon atoms; R 10 , R 12 are each independently selected from any one of the following structures: an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an aryl group having 6 to 25 carbon atoms; 1-3 hydrogen atoms in the substituted aromatic ketone group with carbon atoms number of 7-25 are independently substituted by the following structures: cyano, nitro, halogen, alkyl with carbon atoms number of 1-15, alkoxy with carbon atoms number of 1-15, alkyl ether with carbon atoms number of 1-15, heterocyclic alkoxy with carbon atoms number of 2-15, alkyl with carbon atoms number of 1-15 substituted by fluorine atom, alkoxy with carbon atoms number of 1-15 or alkyl ether with carbon atoms number of 1-15; the cycloalkyl with carbon atoms number of 3-15, the heterocyclic alkyl with carbon atoms number of 2-15, and the heterocyclic alkoxy with carbon atoms number of 2-15 comprise a part or whole carbon chain as a cyclic or heterocyclic ring, and 1-3 hydrogen atoms in the carbon chain are substituted by alkyl with carbon atoms number of 1-15; R 13 selected from an alkyl group having 1 to 15 carbon atoms; R 14 , R 15 are the same and are selected from an alkyl group having an atomic number of 1 to 15.

2. Photoinitiator according to claim 1, characterized in that the cyclic structure in the aromatic ketone group with carbon atoms number of 7-25, the heterocyclic alkanoyl with carbon atoms number of 3-15, the cycloalkyl with carbon atoms number of 3-15, the heterocyclic alkyl with carbon atoms number of 2-15, and the heterocyclic alkoxy with carbon atoms number of 2-15 is a monocyclic structure; the cyclic structure in the heteroaromatic ketone group with carbon atoms number of 4-25 and the heteroaryl group with carbon atoms number of 3-25 is independently an unsaturated five-membered heterocyclic ring, or a fused ring structure formed by an unsaturated five-membered heterocyclic ring and a benzene ring sharing a pair of chemical bonds.

3. Photoinitiator according to claim 1, characterized in that the heterocyclic alkanoyl with carbon atoms number of 3-15 is a five-membered or six-membered heterocyclic ring containing 1-2 heteroatoms of O, S and N, which is bonded to the carbonyl group via a single bond or a C1-C6 alkylene group; the aromatic ketone group with carbon atoms number of 7-25 is a benzophenone group; the heteroaromatic ketone group with carbon atoms number of 4-25 is an unsaturated five-membered heterocyclic ketone group containing one heteroatom of O, S and N, or a benzene five-membered heterocyclic ketone group containing one heteroatom of O, S and N; the cycloalkyl with carbon atoms number of 3-15 is a saturated five-membered ring group, a saturated six-membered ring group, or a group formed by a combination of a saturated five-membered to six-membered ring and a C1-C6 alkylene group; the heterocyclic alkyl with carbon atoms number of 2-15 is a saturated five-membered heterocyclic ring group containing 1-2 heteroatoms of O, S and N, or a saturated six-membered heterocyclic ring group containing 1-2 heteroatoms of O, S and N, or a group formed by a combination of a saturated five-membered to six-membered heterocyclic ring and a C1-C6 alkylene group; The heterocyclic alkoxy group having 2 to 15 carbon atoms is a group formed by combining a saturated five- to six-membered heterocyclic ring containing 1 to 2 kinds of heteroatoms selected from O, S, and N with a C1-C6 alkyleneoxy group; The aryl group having 6 to 25 carbon atoms is a phenyl group; The heteroaryl group having 3 to 25 carbon atoms is an unsaturated five-membered heterocyclic group containing one kind of heteroatom selected from O, S, and N, or a benzo five-membered heterocyclic group containing one kind of heteroatom selected from O, S, and N.

4. The photoinitiator according to claim 1, characterized in that The photoinitiator is selected from any of the following structures:

5. A photopolymerizable composition, characterized by, The photopolymerizable composition comprises the following components: at least one olefinically unsaturated photopolymerizable compound, a photoinitiator; the photoinitiator comprises the photoinitiator according to any one of claims 1 to 4.

6. The photopolymerization composition according to claim 5, wherein The weight of the photoinitiator accounts for 0.01 to 10% of the weight of the photopolymerizable composition.

7. The photopolymerization composition according to claim 5, wherein The photoinitiator further comprises a second photoinitiator and / or an additive.

8. The photopolymerization composition according to claim 7, wherein The second photoinitiator comprises at least one of a benzophenone-based photoinitiator, an α-hydroxy ketone-based photoinitiator, an α-amino ketone-based photoinitiator, a dimethylamino phenone-based photoinitiator, a thioxanthone-based photoinitiator, an xanthone-based photoinitiator, a bisimidazole-based photoinitiator, a triazine-based photoinitiator, and an O-acyl oxime-based photoinitiator. The additive comprises at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

9. Use of a photopolymerizable composition, characterized in that The photopolymerizable composition according to any one of claims 5 to 8 is used in a color resist, a black matrix, a photo spacer, a planarization layer, a semiconductor photoresist, or an ink for a display element.

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