Photoinitiator, photopolymerization composition and application thereof

Abstract

The present invention relates to a photoinitiator, a photopolymerization composition and an application thereof, and relates to the technical field of photoinitiators. The photoinitiator is a compound having a structure represented by formula (1): #imgabs0# wherein one or two structures of R1-R8 in formula (1) are selected from a group represented by formula (2) or formula (3): #imgabs1# The compound of the present invention still has a strong absorption capacity and a high OD in a dark system, has excellent I-line photosensitivity, and is more compatible with the emission spectrum of an ultraviolet light source. Therefore, the compound is a photoinitiator having excellent comprehensive performance with high photosensitivity, good solubility and lower cost, and has excellent application prospects in displays, semiconductors and inks.

Description

Technical Field

[0001] The present invention belongs to the technical field of photoinitiators, and in particular relates to a photoinitiator, a photopolymerization composition and applications thereof. Background Art

[0002] Photoinitiators are key components in photocuring systems, decisive for the curing rate. They are widely used in various fields, including the microelectronics industry, UV coatings, and PCB inks. Various types are known, including acetophenone derivatives, benzophenone derivatives, α-hydroxyketones, acylphosphine oxides, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. Oxime ester photoinitiators, for example, are known to exhibit excellent storage stability, sensitivity, developability, and pattern integrity. Oxime ester compounds containing a carbazole skeleton are examples. However, when forming patterns using conventional photopolymerization initiators, the low sensitivity necessitates increasing the amount of photopolymerization initiator or exposure dose during the exposure step. This can contaminate the mask during the exposure step, and the byproducts produced by the decomposition of the photopolymerization initiator during crosslinking at high temperatures reduce the yield. The exposure time also increases with increasing exposure dose. Therefore, there is a desire to develop a photopolymerization initiator that exhibits superior sensitivity to active energy rays, improved solubility, and lower cost compared to these compounds. In view of this, the present invention provides a photoinitiator, a photopolymerization composition and applications thereof. Summary of the Invention

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

[0004] In the first aspect, a photoinitiator is a compound having a structure shown in formula (1):

[0005]

[0006] In formula (1), one or two structures of R1 to R8 are selected from the group represented by formula (2) or formula (3):

[0007]

[0008] The structures of the remaining R1-R8 are independently selected from any one of the following structures: hydrogen, cyano, nitro, halogen, an alkanone group having 2 to 15 carbon atoms, a cycloalkanone group having 4 to 15 carbon atoms, a heterocycloalkanone group having 3 to 15 carbon atoms, an arylone group having 7 to 25 carbon atoms, a heteroarylone group having 4 to 25 carbon atoms, a substituted arylone group having 7 to 25 carbon atoms, and a substituted heteroarylone group having 4 to 25 carbon atoms;

[0009] 1-3 hydrogen atoms in the substituted aryl ketone group having 7 to 25 carbon atoms and the substituted heteroaryl ketone group having 4 to 25 carbon atoms are independently substituted by the following structures: cyano, nitro, halogen, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms, alkyl ether group having 1 to 8 carbon atoms, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms or alkyl ether group having 1 to 8 carbon atoms substituted by fluorine atoms;

[0010] The cycloalkanone group having 4 to 15 carbon atoms and the heterocycloalkanone group having 3 to 15 carbon atoms contain a portion or all of a carbon chain that is cyclic or heterocyclic, and 0 to 3 hydrogen atoms in the carbon chain are substituted by an alkyl group having 1 to 8 carbon atoms;

[0011] X1 and X2 are independently selected from any one of the following structures: oxygen atom, keto group, sulfonyl group, N(R 13 ), C(R 14 )(R 15 ), and 1-2 of X1 and X2 are selected from sulfonyl;

[0012] R9-R 12 Each independently selected from the following structures: hydrogen, an alkyl group having 1 to 15 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkylthio 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, a heterocycloalkoxy 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, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms or an alkyl ether group having 1 to 15 carbon atoms substituted with a fluorine atom, a substituted aryl group having 6 to 25 carbon atoms, or a substituted heteroaryl group having 3 to 25 carbon atoms;

[0013] 1-3 hydrogen atoms in the substituted aryl group having 6 to 25 carbon atoms and the substituted heteroaryl group having 3 to 25 carbon atoms are independently substituted by the following structures: 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, alkylether 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, alkoxy group having 1 to 15 carbon atoms, or alkylether group having 1 to 15 carbon atoms substituted by fluorine atoms;

[0014] 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 a group in which part or all of the carbon chain is cyclic or heterocyclic, and 1 to 3 hydrogen atoms in the carbon chain are replaced by an alkyl group having 1 to 15 carbon atoms;

[0015] R 13 Selected from the following structures: an alkyl group having 1 to 15 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, an aryl group having 6 to 25 carbon atoms, an aryl group having 6 to 25 carbon atoms in which 1 to 3 hydrogen atoms are substituted with a cyano group, a nitro group, a halogen group, an alkyl group having 1 to 6 carbon atoms, or an alkyl ether group having 1 to 6 carbon atoms;

[0016] R 14 、R 15 Same or different, R 14 、R 15 are independently selected from an alkyl group having 1 to 15 atoms, or R 14 、R 15 fused to form a ring structure.

[0017] Furthermore, when one structure among R1-R8 is selected from the group represented by formula (2) or formula (3), the structure of any one of R5-R8 is the group represented by formula (2) or formula (3), and the remaining R1-R8 are hydrogen;

[0018] When two structures among R1-R8 are selected from the groups shown in formula (2) or formula (3), the structure of any one of R1-R4 and the structure of any one of R5-R8 are the groups shown in formula (2) or formula (3), respectively, and the remaining R1-R8 are all hydrogen; and each substitution site in R1-R8 that is not hydrogen is symmetrical or asymmetrical.

[0019] Furthermore, the ring structure in the cycloalkanone group having 4 to 15 carbon atoms, the aryl ketone group having 7 to 25 carbon atoms, the heterocycloalkanone group having 3 to 15 carbon atoms, the cycloalkyl group having 3 to 15 carbon atoms, the heterocycloalkyl group having 2 to 15 carbon atoms, the heterocycloalkoxy group having 2 to 15 carbon atoms, and the aryl group having 6 to 25 carbon atoms is a monocyclic structure;

[0020] The ring structures in the heteroaryl ketone group having 4 to 25 carbon atoms and the heteroaryl group having 3 to 25 carbon atoms are independently unsaturated five-membered heterocyclic rings, or condensed ring structures formed by an unsaturated five-membered heterocyclic ring and a benzene ring sharing a pair of chemical bonds.

[0021] Furthermore, the cycloalkanone group having 4 to 15 carbon atoms is a group formed by a five-membered ring or a six-membered ring linked to a carbonyl group via a single bond or a C1-C6 alkylene group;

[0022] The heterocycloalkanone group having 3 to 15 carbon atoms is a group formed by a five-membered or six-membered heterocyclic ring containing 1 to 2 heteroatoms selected from O, S, and N, linked to a carbonyl group via a single bond or a C1-C6 alkylene group;

[0023] The aromatic ketone group having 7 to 25 carbon atoms is a phenone group;

[0024] The heteroaromatic ketone group having 4 to 25 carbon atoms is an unsaturated five-membered heterocyclic ketone group containing one heteroatom selected from O, S, and N, or a benzo five-membered heterocyclic ketone group containing one heteroatom selected from O, S, and N;

[0025] 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 a combination of a saturated five-membered to six-membered ring and a C1-C6 alkylene group;

[0026] The heterocycloalkyl group having 2 to 15 carbon atoms is a saturated five-membered heterocyclic group containing 1-2 heteroatoms selected from O, S, and N, or a saturated six-membered heterocyclic group containing 1-2 heteroatoms selected from O, S, and N, or a group formed by combining a saturated five-membered to six-membered heterocyclic ring containing 1-2 heteroatoms selected from O, S, and N with a C1-C6 alkylene group;

[0027] The heterocycloalkoxy group having 2 to 15 carbon atoms is a group formed by combining a saturated five-membered to six-membered heterocycle containing 1-2 heteroatoms selected from O, S, and N and a C1-C6 alkyleneoxy group;

[0028] The aryl group having 6 to 25 carbon atoms is a phenyl group;

[0029] The heteroaryl group having 3 to 25 carbon atoms is an unsaturated five-membered heterocyclic group containing one heteroatom selected from O, S, and N, or a benzo five-membered heterocyclic group containing one heteroatom selected from O, S, and N.

[0030] Furthermore, the photoinitiator is selected from any one of the following structures:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] In a second aspect, a photopolymerizable composition is provided, comprising the following components: at least one ethylenically unsaturated photopolymerizable compound and a photoinitiator; the photoinitiator comprises the photoinitiator.

[0041] Furthermore, the total weight of the photopolymerizable composition is 100 wt %, and the weight of the photoinitiator accounts for 0.01 to 10% of the weight of the photopolymerizable composition.

[0042] Furthermore, the photoinitiator further includes a second photoinitiator and / or additives.

[0043] Further, the second photoinitiator includes at least one of a benzophenone photoinitiator, an α-hydroxyketone photoinitiator, an α-aminoketone photoinitiator, a dimethylaminobenzophenone photoinitiator, a thioxanthone photoinitiator, a xanthone photoinitiator, a biimidazole photoinitiator, a triazine photoinitiator, and an O-acyl oxime photoinitiator;

[0044] The additives include at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

[0045] In a third aspect, a photopolymerizable composition is used in a color photoresist, a black matrix, a photospacer, a planarization layer, a semiconductor photoresist or an ink of a display element.

[0046] The beneficial effects of the present invention are:

[0047] (1) The photoinitiator provided by the present invention has a significantly enhanced rigidity of the dibenzodioxide hexacyclic core molecular structure and a significantly improved optical absorption capacity, so that the compound maintains high solubility. At the same time, in a dark curing system, it exhibits a high OD value and high photosensitivity to 365nm wavelength light, thereby being better able to be used in dark systems such as color photoresist and black matrix of display elements to achieve high contrast, or to achieve deep curing in the fields of photospacers, planarization layers, semiconductor photoresists and inks.

[0048] (2) The thermal stability of the photoinitiator of the present invention is significantly improved, and it has excellent exposure and development characteristics under low exposure conditions (<1s). Excellent photolithographic patterns can be prepared in a shorter exposure time, which is conducive to improving industrial production efficiency and has broad commercial prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1This is the NMR spectrum of compound (6) synthesized in Example 1;

[0050] Figure 2 The mass spectrum of compound (6) synthesized in Example 2;

[0051] Figure 3 The graph shows the photocuring efficiency of compound (6) (corresponding to SP1-S05) relative to P-3 (corresponding to oxe-02) on acrylic double bonds in black photoresist as the exposure dose increases. DETAILED DESCRIPTION

[0052] To facilitate understanding of the present invention, preferred embodiments are provided. It should be understood that the specific embodiments described herein are intended only to illustrate and explain the present invention and are not intended to limit the present invention. Where specific conditions are not specified in the examples, the experiments were performed under conventional conditions or the conditions recommended by the manufacturer. Where the manufacturer of the reagents or instruments is not specified, all are commercially available conventional products.

[0053] Example 1: Preparation of compound (6)

[0054] The synthesis steps of the compound involved in this embodiment are as follows:

[0055] 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 hour, then add 29.8 g of chlorooctane. Stir and react at room temperature overnight. Wash with water, extract the product 1-2 times with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 39.6 g of 10-octylphenothiazine.

[0056] S2. 30 g of 10-octylphenothiazine and 12.8 g of aluminum chloride were dissolved in 300 mL of dichloromethane. A solution of 15.7 g of octanoyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C and stirred for 2 h. The mixture was quenched with 150 mL of 20 wt% glacial dilute hydrochloric acid. The product was extracted with dichloromethane 1-2 times, dried over magnesium sulfate, concentrated, and dried to give 23.2 g of (10-octylphenothiazine-3-yl)-1-octyl ketone.

[0057] S3. Dissolve 20 g of 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in 250 mL of acetic acid, add 3.3 g of hydrogen peroxide, heat to 70°C, react for 6 h, filter the reaction solution through a silica gel funnel, wash the filtrate with water, extract the product 1-2 times with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 19.3 g of (10-octylphenothiazinesulfone-3-yl)-1-octyl ketone;

[0058] S4. 15 g of 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone was dissolved in 200 mL of N,N-dimethylformamide, and 2.6 mL of concentrated hydrochloric acid and 2.85 g of isobutyl nitrite were added sequentially. The reaction mixture was stirred at room temperature for 6 h, quenched with ice water, and the product was extracted 1-2 times with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 11.5 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime;

[0059] S5. 10 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime and 2.23 g of triethylamine were dissolved in 30 mL of dichloromethane, and 1.73 g of acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0°C and stirred for 2 h. The mixture was quenched with 10 mL of 20 wt% glacial dilute hydrochloric acid, extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 8.35 g of compound (6) ( Figures 1 to 3 ).

[0060] Example 2: Preparation of compound (10)

[0061] The synthesis steps of the compound involved in this embodiment are as follows:

[0062] 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 29.8 g of chloroisooctane. Stir and react at room temperature overnight. Wash with water, extract the product 1-2 times with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 38.9 g of 10-(2-ethylhexyl)phenothiazine.

[0063] S2. 30 g of 10-(2-ethylhexyl)phenothiazine and 12.8 g of aluminum chloride were dissolved in 300 mL of dichloromethane. A solution of 16.8 g of 3-cyclohexylpropionyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C and stirred for 2 h. The mixture was quenched with 150 mL of 20 wt% glacial dilute hydrochloric acid. The product was extracted with dichloromethane 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 22.5 g of 1-(10-(2-ethylhexyl)phenothiazin-3-yl)-1-cyclohexylpropyl ketone.

[0064] 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, the temperature was raised to 70°C, the reaction was allowed to react 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 over magnesium sulfate, concentrated, and dried to obtain 19.5 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-cyclohexylpropyl ketone;

[0065] S4. 15 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-cyclohexylpropyl ketone was dissolved in 200 mL of N,N-dimethylformamide, and 2.6 mL of concentrated hydrochloric acid and 4.2 g of isobutyl nitrite were added sequentially. The reaction mixture was stirred at room temperature for 6 h, quenched with ice water, and the product was extracted 1-2 times with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 15.9 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-cyclohexylpropyldione-2-oxime;

[0066] S5. Dissolve 10 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-cyclohexylpropyldione-2-oxime and 2.12 g of triethylamine in 30 mL of dichloromethane, slowly add dropwise 1.65 g of acetyl chloride solution dissolved in 10 mL of dichloromethane at 0°C, and stir the reaction for 2 h. Quench the mixture with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to obtain 7.90 g of compound (10).

[0067] MS: 553.2464 (MS+1), exact molecular mass: 552.2658.

[0068] Example 3: Preparation of compound (12)

[0069] The synthesis steps of the compound involved in this embodiment are as follows:

[0070] S1. In Example 1S2, 10-octylphenothiazine was replaced with 10-(2-ethylhexyl)phenothiazine, and octanoyl chloride was replaced with 2,2-dimethyl-1,3-dioxolaneacetyl chloride. The same method as in Example 1S2 was used to obtain 22.3 g of 1-(10-(2-ethylhexyl)phenothiazin-3-yl)-1-cyclohexylpropyl ketone.

[0071] S2. The product of S1 was used to replace 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3, and the same method as Example 1S3 was used to obtain 18.4 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-(2,2-dimethyl-1,3-dioxolane)ethyl-1-one.

[0072] S3. The 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S2 above. The same method as Example 1S4 was used to obtain 11.0 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-(2,2-dimethyl-1,3-dioxolane)ethyldione-2-oxime.

[0073] S4. Replace the 1-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above. Otherwise, prepare in the same manner as Example 1S5 to obtain 8.45 g of compound (12).

[0074] MS: 557.3245 (MS+1), exact molecular mass: 556.2243.

[0075] Example 4: Preparation of compound (13)

[0076] The synthesis steps of the compound involved in this embodiment are as follows:

[0077] S1. Dissolve 30 g of 10-(2-ethylhexyl)phenothiazine in 350 mL of acetic acid, add 6.9 g of hydrogen peroxide, heat to 70°C, react for 6 h, filter the reaction solution through a silica gel funnel, wash the filtrate with water, extract the product 1-2 times with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 30.8 g of 10-(2-ethylhexyl)phenothiazine sulfone;

[0078] S2. 25 g of 10-(2-ethylhexyl)phenothiazine sulfone and 9.7 g of aluminum chloride were dissolved in 300 mL of dichloromethane. A solution of 11.7 g of 2-thiopheneacetyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C and stirred for 2 h. The mixture was quenched with 150 mL of 20 wt% glacial dilute hydrochloric acid. The product was extracted with dichloromethane 1-2 times, dried over magnesium sulfate, concentrated, and dried to give 18.0 g of 1-(10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1-(thiophen-2-yl) ethyl ketone.

[0079] S3. 15 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-(thiophen-2-yl)ethyl ketone was dissolved in 200 mL of N,N-dimethylformamide, and 2.6 mL of concentrated hydrochloric acid and 3.3 g of isobutyl nitrite were added in sequence. The reaction mixture was stirred at room temperature for 6 h, and then quenched with ice water. The product was extracted with ethyl acetate 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 10.4 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-(thiophen-2-yl)ethyl ketone-2-oxime;

[0080] S4. Dissolve 10 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-(thiophene-2-yl)ethylketone-2-oxime and 2.24 g of triethylamine in 30 mL of dichloromethane, slowly add dropwise 1.74 g of acetyl chloride solution dissolved in 10 mL of dichloromethane at 0°C, and stir the reaction for 2 h. Quench the mixture with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 8.24 g of compound (13).

[0081] MS: 539.5541 (MS+1), exact molecular mass: 538.1596.

[0082] Example 5: Preparation of compound (16)

[0083] The synthesis steps of the compound involved in this embodiment are as follows:

[0084] S1. The octane chloride in Example 1S1 was replaced with isohexane chloride, and the same method as in Example 1S1 was used to obtain 36.3 g of 10-(2-ethylbutyl)phenothiazine;

[0085] S2. 27.3 g of 1-(10-(2-ethylbutyl)phenothiazin-3-yl)-1-o-(2,2,3,3-tetrafluoropropoxy)acetophenone was obtained by the same method as in Example 1S2, except that 10-octylphenothiazine in Example 1S2 was replaced with the product of S1 above and octanoyl chloride was replaced with o-(2,2,3,3-tetrafluoropropoxy)phenylacetyl chloride.

[0086] S3. 21.2 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1-o-(2,2,3,3-tetrafluoropropoxy)acetophenone was obtained by the same method as in Example 1S3, except that the 1-(10-octylphenothiazin-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above.

[0087] S4. 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S3 above. The same method as Example 1S4 was used to obtain 9.8 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1,2-o-(2,2,3,3-tetrafluoropropoxy)phenanedione-2-oxime.

[0088] S5. Replace 10 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with 5 g of the product of S4 above. Otherwise, prepare in the same manner as Example 1S5 to obtain 4.23 g of compound (16).

[0089] MS: 635.1247 (MS+1), exact molecular mass: 634.1761.

[0090] Example 6: Preparation of compound (17)

[0091] The synthesis steps of the compound involved in this embodiment are as follows:

[0092] S1. In Example 1S2, 10-octylphenothiazine was replaced with 10-(2-ethylhexyl)phenothiazine, and octanoyl chloride was replaced with p-(methoxy-3-methylbutyloxy)phenylacetyl chloride. 29.4 g of 1-(10-(2-ethylbutyl)phenothiazin-3-yl)-1-p-(methoxy-3-methylbutyloxy)acetophenone was obtained in the same manner as in Example 1S2.

[0093] S2. The product of S1 was used to replace 1-(10-octylphenothiazin-3-yl)-1-(p-methoxy-3-methylbutyloxy)acetophenone in Example 1S3, and the same method as Example 1S3 was used to obtain 18.8 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1-(p-methoxy-3-methylbutyloxy)acetophenone.

[0094] S3. The product of S2 was used to replace the 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4, and the same method as Example 1S4 was used to obtain 10.0 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1,2-p-(methoxy-3-methylbutyloxy)phenanedione-2-oxime.

[0095] S4. 8.1 g of compound (17) was obtained by replacing 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above.

[0096] MS: 649.3591 (MS+1), exact molecular mass: 648.2869.

[0097] Example 7: Preparation of compound (18)

[0098] The synthesis steps of the compound involved in this embodiment are as follows:

[0099] S1. In Example 1S2, 10-octylphenothiazine was replaced with 10-(2-ethylhexyl)phenothiazine, and octanoyl chloride was replaced with p-(2,2-dimethyl-1,3-dioxolane)-o-tolueneacetyl chloride. 28.7 g of 1-(10-(2-ethylhexyl)phenothiazin-3-yl)-1-p-(2,2-dimethyl-1,3-dioxolane)-o-tolueneacetophenone was obtained in the same manner as in Example 1S2.

[0100] S2. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above. The same method as Example 1S3 was used to obtain 19 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-p-(2,2-dimethyl-1,3-dioxolane)-o-methylbenzene acetophenone.

[0101] S3. 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S2 above, and the same method as Example 1S4 was used to obtain 9.6 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-p-(2,2-dimethyl-1,3-dioxolane)-o-toluenedione-2-oxime;

[0102] S4. Replace 10 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with 5 g of the product of S3 above. Otherwise, prepare in the same manner as Example 1S5 to obtain 4.2 g of compound (18).

[0103] MS: 677.1276 (MS+1), exact molecular mass: 676.2818.

[0104] Example 8: Preparation of compound (27)

[0105] The synthesis steps of the compound involved in this embodiment are as follows:

[0106] S1. 24.5 g of (10-ethyl-10H-phenothiazin-3-yl)-1-hexyl ketone was obtained by the same method as in Example 1S2 except that 10-octylphenothiazine was replaced with 10-ethylphenothiazine and octanoyl chloride was replaced with hexanoyl chloride.

[0107] S2. 20.2 g of (10-ethyl-10H-phenothiazinesulfone-3-yl)-1-hexyl ketone was obtained by the same method as in Example 1S3 except that 1-(10-octylphenothiazin-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above.

[0108] S3. 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S2 above, and the same method as Example 1S4 was used to obtain 11.0 g of (10-ethyl-10H-phenothiazine-3-yl)-1,2-hexyldione-2-oxime;

[0109] S4. Replace 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above, and replace acetyl chloride with p-methoxybenzoyl chloride. Otherwise, prepare in the same manner as Example 1S5 to obtain 9.4 g of compound (27).

[0110] MS: 521.6852 (MS+1), exact molecular mass: 520.1668.

[0111] Example 9: Preparation of compound (28)

[0112] The synthesis steps of the compound involved in this embodiment are as follows:

[0113] S1. 30g 10-(2-ethylhexyl)phenothiazine and 12.8g aluminum chloride were dissolved in 300mL dichloromethane, and 14.9g o-tolueneacetyl chloride solution dissolved in 50mL dichloromethane was slowly added dropwise at 0°C and stirred for 2h. After the reaction was completed, 12.8g aluminum chloride was added and stirred to dissolve. Then, 17.2g octanoyl chloride solution dissolved in 50mL dichloromethane was slowly added dropwise at 0°C. After the addition was completed, the reaction was continued with stirring for 3h. The mixture was quenched with 150mL 20wt% glacial dilute hydrochloric acid, and the product was extracted with dichloromethane 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 22.5g (6-o-methylphenyl ketone-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octyl ketone;

[0114] S2. Dissolve 20 g of (6-o-methylphenyl-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octyl ketone in 250 mL of acetic acid, add 2.6 g of hydrogen peroxide, heat to 70°C, react for 6 h, filter the reaction solution through a silica gel funnel, wash the filtrate with water, extract the product 1-2 times with ethyl acetate, dry it with magnesium sulfate, concentrate, and dry it to obtain 18.8 g of (6-o-methylphenyl-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-octyl ketone;

[0115] S3. 15 g (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl) -1-octyl ketone was dissolved in 200 mL of N, N-dimethylformamide, and 2.2 mL of concentrated hydrochloric acid and 3.4 g of isobutyl nitrite were added sequentially. The reaction mixture was stirred at room temperature for 6 h, quenched with ice water, and the product was extracted 1-2 times with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 10.2 g 15 g (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl) -2-hydroxyimino-1-octyl ketone;

[0116] S4. Dissolve 10 g of (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone and 1.8 g of triethylamine in 30 mL of dichloromethane, slowly add dropwise 1.4 g of acetyl chloride solution dissolved in 10 mL of dichloromethane at 0°C, and stir the reaction for 2 h. Quench the mixture with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 7.8 g of compound (28).

[0117] MS: 659.6871 (MS+1), exact molecular mass: 658.3077.

[0118] Example 10: Preparation of compound (31)

[0119] The synthesis steps of the compound involved in this embodiment are as follows:

[0120] S1. Except that o-tolueneacetyl chloride in Example 9S1 was replaced with 2-methyl-2-morpholinopropionyl chloride, the same method as Example 9S1 was used to obtain 22.84 g of (6-(2-methyl-2-morpholinopropanone)-10-(2-ethylhexyl)phenothiazin-3-yl)-1-octyl ketone;

[0121] S2. 18.3 g of (6-(2-methyl-2-morpholinopropanone)-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-octyl ketone was obtained by the same method as in Example 9S2, except that the product of S1 was used instead of (6-o-methylphenylketone-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-octyl ketone.

[0122] S3. Except that the (6-o-methylphenyl ketone-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-1-octyl ketone in Example 9S3 was replaced with the product of S2 above, the same method as Example 9S3 was used to obtain 10.5 g of (6-(2-methyl-2-morpholinopropanone)-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone;

[0123] S4. Replace the (6-o-methylphenyl ketone-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone in Example 9S4 with the product of S2 above. Otherwise, prepare in the same manner as Example 9S4 to obtain 8.3 g of compound (31).

[0124] MS: 696.3217 (MS+1), exact molecular mass: 695.3604.

[0125] Example 11: Preparation of Compound (43)

[0126] The synthesis steps of the compound involved in this embodiment are as follows:

[0127] S1. 22.3 g of (6-o-methylphenyl-10-butyl-3-phenothiazin-1-yl)-1-ethyl ketone was obtained by the same method as in Example 9S1 except that 10-(2-ethylhexyl)phenothiazine was replaced with 10-ethylphenothiazine and octanoyl chloride was replaced with formyl chloride.

[0128] S2. 19.5 g of (6-o-methylphenyl-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octyl ketone was obtained by the same method as in Example 9S2, except that the product of S2 was replaced with the (6-o-methylphenyl-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octyl ketone.

[0129] S3. 15 g (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl) -1-ethyl ketone was dissolved in 150 mL of toluene, 3.7 g of sodium acetate and 3.3 g of hydroxylamine hydrochloride were added, and the reaction was refluxed for 8 h. The reaction solution was cooled to room temperature, washed with water, and the product was extracted with ethyl acetate 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 11.2 g (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl) - ethyl ketone oxime;

[0130] S5. Replace (6-o-methylphenyl ketone-10-(2-ethylhexyl)phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone in Example 9S4 with the product of S4 above, and replace acetyl chloride with formyl chloride. Otherwise, prepare in the same manner as Example 9S4 to obtain 8.8 g of compound (43).

[0131] MS: 477.5741 (MS+1), exact molecular mass: 476.1406.

[0132] Example 12: Preparation of Compound (45)

[0133] The synthesis steps of the compound involved in this embodiment are as follows:

[0134] 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 and react at room temperature overnight. Wash with water, extract the product 1-2 times with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 33.0 g of 10-butylphenothiazine.

[0135] S2. In Example 11S1, except that o-tolueneacetyl chloride was replaced with benzofuran-2-acetyl chloride and formyl chloride was replaced with valeryl chloride, the same method as in Example 11S1 was used to obtain 23.3 g of (6-(benzofuran-2-one)-10-butylphenothiazin-3-yl)-1-pentyl ketone.

[0136] S3. Prepare the product in the same manner as in Example 11S2, except that the (6-o-methylphenylketone-10-butylphenothiazine-3-yl)-1-ethyl ketone in Example 11S2 was replaced with the product in S2 above, to obtain 16.5 g of (6-(benzofuran-2-one)-10-butylphenothiazinesulfone-3-yl)-1-pentyl ketone;

[0137] S4. The product of S3 was used in the same manner as in Example 11S3, except that the (6-o-methylphenylketone-10-butylphenothiazinesulfone-3-yl)-1-ethylketone in Example 11S3 was replaced with the product of S3 above, to obtain 10.8 g of (6-(benzofuran-2-one)-10-butylphenothiazinesulfone-3-yl)-pentanone oxime.

[0138] S5. Replace (6-o-methylphenylketone-10-butylphenothiazinesulfone-3-yl)-pentanone oxime in Example 11S4 with the product of S4 above, and replace formyl chloride with chloroformylpropyl ester. Otherwise, prepare in the same manner as Example 11S4 to obtain 8.2 g of compound (45).

[0139] MS: 585.3187 (MS+1), exact molecular mass: 584.2345.

[0140] Example 13: Preparation of Compound (91)

[0141] The synthesis steps of the compound involved in this embodiment are as follows:

[0142] S1. The phenothiazine in Example 1S1 was replaced with 3-nitro-10H-phenothiazine and chlorooctane was replaced with chlorobutane. Otherwise, the same method as in Example 1S1 was used to obtain 30.2 g of 3-nitro-10-butylphenothiazine.

[0143] S2. 22.4 g of (6-nitro-10-butylphenothiazin-3-yl)-1-p-nitrobenzophenone was obtained by the same method as in Example 1S2, except that 10-octylphenothiazine in Example 1S2 was replaced with the product of S1 above and octanoyl chloride was replaced with p-nitrophenylacetyl chloride.

[0144] S3. 19.0 g of (6-nitro-10-butylphenothiazinesulfone-3-yl)-1-p-nitrobenzophenone was obtained by the same method as in Example 1S3 except that the (10-octylphenothiazin-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above.

[0145] S4. 10.5 g of (6-nitro-10-butylphenothiazin-3-yl)-1-p-nitrobenzophenone oxime was obtained by the same method as in Example 11S4, except that the (6-o-methylphenylketone-10-butylphenothiazin-3-yl)-1-ethylketone in Example 11S4 was replaced with the product of S3 above.

[0146] S5. Replace the (6-o-methylphenylketone-10-butylphenothiazinesulfone-3-yl)-ethanone oxime in Example 11S5 with the product of S4 above. Prepare in the same manner as Example 11S5 to obtain 8.0 g of compound (91).

[0147] MS: 539.6975 (MS+1), exact molecular mass: 538.1158.

[0148] Example 14: Preparation of Compound (96)

[0149] The synthesis steps of the compound involved in this embodiment are as follows:

[0150] S1. The chlorooctane in Example 1S1 was replaced with chloro-2-ethylbutane, and the same method as in Example 1S1 was used to obtain 35.8 g of 10-(2-ethylbutyl)phenothiazine;

[0151] S2.30g 10-(2-ethylbutyl)phenothiazine and 28.3g aluminum chloride were dissolved in 300mL dichloromethane. 31.3g propionyl chloride solution dissolved in 50mL dichloromethane was slowly added dropwise at 0°C and stirred for 2h. The mixture was quenched with 150mL 20wt% glacial dilute hydrochloric acid. The product was extracted with dichloromethane 1-2 times, dried over magnesium sulfate, concentrated, and dried to obtain 24.6g 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)diacetone.

[0152] S3. Except that the (10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above, the same method as Example 1S3 was used to obtain 19.7 g of 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone;

[0153] S4. Dissolve 15 g of 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in 200 mL of N,N-dimethylformamide, add 2.6 mL of concentrated hydrochloric acid and 7.8 g of isobutyl nitrite in sequence, and stir the reaction at room temperature for 6 h. Quench with ice water, and extract the product 1-2 times with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to obtain 11.3 g of 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime);

[0154] S5. Dissolve 10 g of 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) and 4.64 g of triethylamine in 100 mL of dichloromethane, slowly add dropwise 2.7 g of acetyl chloride solution dissolved in 10 mL of dichloromethane at 0°C, and stir the reaction for 2 h. Quench with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to obtain 8.4 g of compound (96).

[0155] MS: 570.5246 (MS+1), exact molecular mass: 569.1832.

[0156] Example 15: Preparation of Compound (99)

[0157] The synthesis steps of the compound involved in this embodiment are as follows:

[0158] S1. In Example 14S2, 10-(2-ethylbutyl)phenothiazine was replaced with 10-octylphenothiazine, and propionyl chloride was replaced with octanoyl chloride. The same method as in Example 14S2 was used to obtain 24.6 g of 1,1'-(10-octylphenothiazine-3,6-diyl)dioctanone.

[0159] S2. 19.7 g of 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)dioctanone was obtained by the same method as in Example 14S3 except that the 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above.

[0160] S3. The product of S2 was used to replace 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4, and the same method as Example 14S4 was used to obtain 11.4 g of 1,1'-(10-octylphenothiazinesulfone-3,6-diyl)di(octanone-2-oxime);

[0161] S4. 8.5 g of compound (99) was obtained by replacing 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) in Example 14S5 with the product of S3 above.

[0162] MS: 738.5794 (MS+1), exact molecular mass: 737.3710.

[0163] Example 16: Preparation of Compound (102)

[0164] The synthesis steps of the compound involved in this embodiment are as follows:

[0165] S1. In Example 14S2, 10-(2-ethylbutyl)phenothiazine was replaced with 10-ethylphenothiazine, and propionyl chloride was replaced with 2-(2-ethoxyethoxy)acetyl chloride. The same method as in Example 14S2 was used to obtain 28.3 g of 1,1'-(10-ethylphenothiazine-3,6-diyl)bis(2-ethoxyethoxyethanone).

[0166] S2. The product of S1 was used to replace 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3, and the mixture was prepared in the same manner as in Example 14S3, to obtain 19.1 g of 1,1'-(10-ethylphenothiazinesulfone-3,6-diyl)bis(2-ethoxyethoxyethanone);

[0167] S3. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4 was replaced with the product of S2 above. The same method as Example 14S4 was used to obtain 11.7 g of 1,1'-(10-ethylphenothiazinesulfone-3,6-diyl)bis(2-ethoxyethoxyethanone-2-oxime).

[0168] S4. 8.8 g of compound (102) was obtained by replacing 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) in Example 14S5 with the product of S3 above.

[0169] MS: 662.3975 (MS+1), exact molecular mass: 661.1941.

[0170] Example 17: Preparation of Compound (107)

[0171] The synthesis steps of the compound involved in this embodiment are as follows:

[0172] S1. In Example 4S2, the aluminum chloride was replaced by 17 g, and the 2-thiopheneacetyl chloride was replaced by 18.7 g. Otherwise, the same method as in Example 4S2 was used to obtain 14.5 g of 1,1'-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)bis((thiophene-2-yl)ethyl ketone);

[0173] S2. The amount of the product in S1 was adjusted to 10 g, and the isobutyl nitrite in Example 4S3 was replaced with 5.2 g. The same method as Example 4S3 was used to obtain 6.6 g of 1,1'-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)bis((thiophene-2-yl)ethylketone-2-oxime);

[0174] S3. Adjust the input amount of the above-mentioned S2 product to 5 g, replace the triethylamine in Example 4S4 with 2.4 g, and replace acetyl chloride with 1.4 g. Otherwise, prepare in the same manner as Example 4S4 to obtain 4.0 g of compound (107).

[0175] MS: 734.5248 (MS+1), exact molecular mass: 733.1586.

[0176] Example 18: Preparation of Compound (129)

[0177] The synthesis steps of the compound involved in this embodiment are as follows:

[0178] S1. 10-octylphenothiazine in Example 1S2 was replaced with thioxanthone, and the same method as in Example 1 was used to obtain 23.9 g of (thioxanthone-3-yl)-1-octyl ketone;

[0179] S2. 19.7 g of (10,10-dioxothioxanthone-3-yl)-1-octyl ketone was obtained by the same method as in Example 1 except that the 1-(10-octylphenothiazin-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above.

[0180] S3. 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S2 above, and the same method as Example 1 was used to obtain 9.1 g of (10,10-dioxothioxanthone-3-yl)-1-octyl ketone-2-oxime;

[0181] S4. Replace 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime in Example 1S5 with the product of S3 above, adjust the input amount to 5 g, and prepare in the same manner as Example 1 except for this, to obtain 4.2 g of compound (129).

[0182] MS: 442.3587 (MS+1), exact molecular mass: 441.1246.

[0183] Example 19: Preparation of Compound (138)

[0184] The synthesis steps of the compound involved in this embodiment are as follows:

[0185] S1. 20.5 g of (6-furanone-3-yl-thioxanthone)-1-propyl ketone was obtained by the same method as in Example 9S1 except that 10-(2-ethylhexyl)phenothiazine in Example 9S1 was replaced with thioxanthone, o-tolueneacetyl chloride was replaced with furoyl chloride, and octanoyl chloride was replaced with propionyl chloride.

[0186] S2. Prepare 18.9 g of (6-furanone-10,10-dioxothioxanthone-3-yl)-1-propyl ketone by the same method as in Example 9S2, except that the product of S1 was used instead of (6-o-methylphenyl-10-(2-ethylhexyl)phenothiazin-3-yl)-1-octyl ketone in Example 9S2.

[0187] S3. 9.2 g of (6-furanone-10,10-dioxothioxanthone-3-yl)-1-propyl ketone-2-oxime was obtained by the same method as in Example 9S3, except that the product of S2 was used instead of (6-o-methylphenylketone-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-octyl ketone in Example 9S3.

[0188] S4. In Example 9S4, (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone is replaced by the product of S3 above, and the input amount is adjusted to 5 g. Otherwise, the preparation is carried out in the same manner as in Example 9S4 to obtain 3.9 g of compound (138).

[0189] MS: 480.6858 (MS+1), exact molecular mass: 479.0675.

[0190] Example 20: Preparation of Compound (167)

[0191] The synthesis steps of the compound involved in this embodiment are as follows:

[0192] S1. In Example 14S2, 10-(2-ethylbutyl)phenothiazine was replaced by thioxanthone and propionyl chloride was replaced by octanoyl chloride. The same method as in Example 14S2 was used to obtain 28.9 g of 1,1'-(thioxanthone-3,6-diyl)dioctanone.

[0193] S2. 19.0 g of 1,1'-(10,10-dioxothioxanthone-3,6-diyl)dioctanone was obtained by the same method as in Example 14S3, except that the 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above.

[0194] S3. The product of S2 was used to replace 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4, and the same method as Example 14S4 was used to obtain 10.1 g of 1,1'-(10,10-dioxothioxanthone-3,6-diyl)di(octanone-2-oxime);

[0195] S4. 8.6 g of compound (167) was obtained by replacing 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) in Example 14S5 with the product of S3 above.

[0196] MS: 567.2384 (MS+1), exact molecular mass: 566.1359.

[0197] Example 21: Preparation of Compound (237)

[0198] The synthesis steps of the compound involved in this embodiment are as follows:

[0199] S1. In Example 11S2, 10-ethylphenothiazine was replaced with phenoxathiol, o-toluoyl chloride was replaced with 2,4,6-trimethylbenzoyl chloride, and formyl chloride was replaced with propionyl chloride. 22.9 g of (8-(2,4,6-trimethylbenzophenone)-phenoxathiol-2-yl)-1-propyl ketone was obtained in the same manner as in Example 11S2.

[0200] S2. Prepare the product in the same manner as in Example 11S3, except that the (6-o-methylphenylketone-10-butylphenothiazin-3-yl)-1-ethyl ketone in Example 11S3 was replaced with the product in S1 above, to obtain 17.4 g of (8-(2,4,6-trimethylphenylketone)-10,10-dioxophenoxathiazin-2-yl)-1-propyl ketone;

[0201] S3. The product of S2 was used to replace the (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl)-1-ethyl ketone in Example 11S4. The mixture was prepared in the same manner as Example 11S4, yielding 10.4 g of (8-(2,4,6-trimethylphenyl ketone-10,10-dioxophenoxathiazine-2-yl)-1-propyl ketone-2-oxime.

[0202] S4. Replace the (6-o-methylphenylketone-10-butylphenothiazinesulfone-3-yl)-ethanone oxime in Example 11S5 with the product of S3 above. Otherwise, prepare in the same manner as Example 11S4 to obtain 7.8 g of compound (237).

[0203] MS: 476.2152 (MS+1), exact molecular mass: 475.1453.

[0204] Example 22: Preparation of Compound (245)

[0205] The synthesis steps of the compound involved in this embodiment are as follows:

[0206] S1. 10-(2-ethylbutyl)phenothiazine in Example 14S2 was replaced with 9,9-dimethyl-9H-thioxanthenes. 20.2 g of 1,1'-(9,9-dimethyl-9H-thioxanthenes-3,6-diyl)diacetone was obtained in the same manner as in Example 14S2.

[0207] S2. 19.9 g of 1,1'-(9,9-dimethyl-9H-thioxanthanesulfone-3,6-diyl)diacetone was obtained by the same method as in Example 14S3, except that the 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above.

[0208] S3. The product of S2 was used to replace 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4, and the same method as Example 14S4 was used to obtain 12.1 g of 1,1'-(9,9-dimethyl-9H-thioxanthensulfone-3,6-diyl)di(acetone-2-oxime);

[0209] S4. 9.2 g of compound (245) was obtained by replacing 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) in Example 14S5 with the product of S3 above.

[0210] MS: 513.5714 (MS+1), exact molecular mass: 512.1253.

[0211] Comparative Example 1

[0212] As a photopolymerization initiator, a compound represented by the following formula was used:

[0213]

[0214] Comparative Example 2

[0215] As a photopolymerization initiator, a compound represented by the following formula was used:

[0216] Comparative Example 3

[0217] As a photopolymerization initiator, a compound represented by the following formula was used:

[0218] Comparative Example 4

[0219] As a photopolymerization initiator, a compound represented by the following formula was used:

[0220] Comparative Example 5

[0221] As a photopolymerization initiator, a compound represented by the following formula was used:

[0222] Comparative Example 6

[0223] As a photopolymerization initiator, a compound represented by the following formula was used:

[0224]

[0225] Test example

[0226] The following physical property evaluations were performed on the compounds obtained in the above synthesis examples. For comparison, the physical property evaluations were also performed on the photopolymerization initiators of Comparative Examples 1 to 4 below. The results are shown in Table 1.

[0227] The photoinitiator properties of the compounds of the above examples and comparative examples were tested using the following method, as follows:

[0228] (1) Maximum absorption wavelength and molar absorptivity

[0229] The photoinitiator of the present invention is prepared as 10 -5 mol / L propylene glycol methyl ether acetate (PMA) solution, and test its UV-visible absorption spectrum to obtain its maximum absorption wavelength (λ max ), and calculate the molar absorptivity (ε) at the maximum absorption wavelength according to Beer's law max )

[0230] (2) Solubility

[0231] Taking propylene glycol methyl ether acetate (PMA), a reactive diluent widely used in the art, as an example, the maximum weight that can be completely dissolved in 100 g of solvent at 25° C. is used as the evaluation standard for the photoinitiator of the present invention.

[0232] (3)Light sensitivity

[0233] 20 wt% of bisphenol fluorene resin, 60 wt% of carbon black, 0.5 wt% of the compound of the present invention as a photopolymerization initiator, 0.1 wt% of FC-430 (3M leveling agent), and 19.4 wt% of PMA were placed in a reaction mixing tank equipped with a UV shield and a stirrer and stirred at room temperature to prepare a photopolymerizable composition. The photopolymerizable composition was spin-coated on a glass substrate and dried on a hot plate at 100°C for 1 minute. The composition was then exposed using a stepper mask and developed in a 0.04% KOH aqueous solution. The sensitivity was evaluated based on an exposure dose that maintained the thickness of the stepper mask pattern at 80% of the initial thickness. The exposure dose was defined as 1, which maintained the thickness of the P-1 pattern at 80% of the initial thickness. Other photoinitiators were evaluated and found that, at the same residual thickness, a lower exposure dose resulted in higher sensitivity.

[0234] Table 1

[0235]

[0236]

[0237]

[0238] As can be seen from Table 1, the oxime ester photoinitiator constructed with a di-oxidized dibenzo hexacyclic ring core in the present invention exhibits a significant enhancement of molecular structural rigidity and a significant improvement in optical absorption capacity, allowing the compound to maintain high solubility. At the same time, in a dark curing system, compared to unoxidized or mono-oxidized dibenzo hexacyclic ring cores, or commercial mainstream products, it exhibits high OD values, high photosensitivity, and a certain degree of oxygen inhibition. Therefore, it can be better applied in dark systems such as color photoresists and black matrices of display devices to achieve high contrast, or in areas such as photospacers, planarization layers, and semiconductor photoresists and inks to achieve deep curing polymerization. In addition, the photoinitiator of the present invention has significantly improved thermal stability compared to unoxidized or mono-oxidized dibenzo hexacyclic ring cores, and has excellent exposure and development characteristics under low exposure conditions (<2s). Excellent photolithographic patterns can be prepared with a short exposure time, which is conducive to improving industrial production efficiency and has broad commercial prospects.

[0239] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A photoinitiator, characterized in that The photoinitiator is a compound having the structure shown in formula (1): In formula (1), R3 and R6 are selected from the group represented by formula (2) or formula (3): or R3 is selected from the group represented by formula (2) or formula (3), and R6 is selected from any one of the following structures: nitro, heterocycloalkanone group having 3 to 15 carbon atoms, aromatic ketone group having 7 to 25 carbon atoms, heteroaromatic ketone group having 4 to 25 carbon atoms, and substituted aromatic ketone group having 7 to 25 carbon atoms; The remaining R1-R8 are hydrogen; 1-3 hydrogen atoms in the substituted aryl ketone group having 7 to 25 carbon atoms are independently substituted by the following structures: an alkyl group having 1 to 8 carbon atoms; The heterocycloalkanone group having 3 to 15 carbon atoms comprises a carbon chain that is partially or entirely cyclic or heterocyclic, and 0 to 3 hydrogen atoms in the carbon chain are substituted by an alkyl group having 1 to 8 carbon atoms; X1 is selected from any one of the following structures: oxygen atom, keto group, N(R 13 ), C(R 14 )(R 15 ), and X2 is selected from sulfonyl; 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, and a substituted aryl group having 6 to 25 carbon atoms; R 10 、R 12 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, and an aryl group having 6 to 25 carbon atoms; 1-3 hydrogen atoms in the substituted aryl group having 6 to 25 carbon atoms are independently substituted by the following structures: cyano, nitro, halogen, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms, alkyl ether group having 1 to 15 carbon atoms, heterocycloalkoxy group having 2 to 15 carbon atoms, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms or alkyl ether group having 1 to 15 carbon atoms substituted by fluorine atoms; 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 a group in which part or all of the carbon chain is cyclic or heterocyclic, and 1 to 3 hydrogen atoms in the carbon chain are replaced by an alkyl group having 1 to 15 carbon atoms; R 13 An alkyl group having 1 to 15 carbon atoms; R 14 、R 15 The same is selected from alkyl groups having 1 to 15 atoms.

2. The photoinitiator according to claim 1, characterized in that The cyclic structure in the aromatic ketone group having 7 to 25 carbon atoms, the heterocycloalkanone group having 3 to 15 carbon atoms, the cycloalkyl group having 3 to 15 carbon atoms, the heterocycloalkyl group having 2 to 15 carbon atoms, the heterocycloalkoxy group having 2 to 15 carbon atoms, and the aryl group having 6 to 25 carbon atoms is a monocyclic structure; The ring structures in the heteroaryl ketone group having 4 to 25 carbon atoms and the heteroaryl group having 3 to 25 carbon atoms are independently unsaturated five-membered heterocyclic rings, or condensed ring structures formed by an unsaturated five-membered heterocyclic ring and a benzene ring sharing a pair of chemical bonds.

3. The photoinitiator according to claim 1, characterized in that The heterocycloalkanone group having 3 to 15 carbon atoms is a group formed by a five-membered or six-membered heterocyclic ring containing 1 to 2 heteroatoms selected from O, S, and N, linked to a carbonyl group via a single bond or a C1-C6 alkylene group; The aromatic ketone group having 7 to 25 carbon atoms is a phenone group; The heteroaromatic ketone group having 4 to 25 carbon atoms is an unsaturated five-membered heterocyclic ketone group containing one heteroatom selected from O, S, and N, or a benzo five-membered heterocyclic ketone group containing one heteroatom selected from O, S, and N; 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 a combination of a saturated five-membered to six-membered ring and a C1-C6 alkylene group; The heterocycloalkyl group having 2 to 15 carbon atoms is a saturated five-membered heterocyclic group containing 1-2 heteroatoms selected from O, S, and N, or a saturated six-membered heterocyclic group containing 1-2 heteroatoms selected from O, S, and N, or a group formed by combining a saturated five-membered to six-membered heterocyclic ring containing 1-2 heteroatoms selected from O, S, and N with a C1-C6 alkylene group; The heterocycloalkoxy group having 2 to 15 carbon atoms is a group formed by combining a saturated five-membered to six-membered heterocycle containing 1-2 heteroatoms selected from O, S, and N and 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 heteroatom selected from O, S, and N, or a benzo five-membered heterocyclic group containing one heteroatom selected from O, S, and N.

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

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

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

7. The photopolymerizable composition according to claim 5, wherein The photoinitiator further includes a second photoinitiator and / or additives.

8. The photopolymerizable composition according to claim 7, wherein The second photoinitiator includes at least one of a benzophenone photoinitiator, an α-hydroxyketone photoinitiator, an α-aminoketone photoinitiator, a dimethylaminobenzophenone photoinitiator, a thioxanthone photoinitiator, a xanthone photoinitiator, a biimidazole photoinitiator, a triazine photoinitiator, and an O-acyl oxime photoinitiator; The additives include at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

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

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