Photoinitiator, photopolymerization composition and application thereof

Abstract

The invention relates to a photoinitiator, a photopolymerization composition and application thereof, and relates to the technical field of photoinitiators, the photoinitiator is a compound with a structure as shown in a formula (1): # imgabs 0 #: 1-2 structures in R1-R8 in the formula (1) are selected from groups as shown in a formula (2) or a formula (3): # imgabs 1 #. The compound provided by the invention still has relatively strong absorption capacity in a dark color system, has high OD (optical density), and can be used for preparing a photoinitiator. The photoinitiator has excellent I-line photosensitivity, and is more matched with the emission spectrum of an ultraviolet light source, so that the photoinitiator is high in photosensitivity, good in solubility, lower in cost and excellent in comprehensive performance, and has excellent application prospects in display, semiconductors and printing ink.

Description

Technical Field

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

[0002] Photoinitiator is one of the key components in the photocuring system, plays a decisive role in the curing rate, and is widely used in many fields, including microelectronics industry, UV coatings, PCB inks, etc. Various types are known, such as acetophenone derivatives, benzophenone derivatives, α-hydroxy ketones, acyl phosphine oxides, triazine derivatives, biimidazole derivatives, acyl phosphine oxide derivatives and oxime ester derivatives, and oxime ester photoinitiators are excellent in storage stability, sensitivity, developability and pattern integrity, such as oxime ester compounds containing carbazole skeletons. However, when traditional photopolymerization initiators form patterns, in the exposure process of pattern formation, due to low sensitivity, the amount of photopolymerization initiator or exposure dose needs to be increased, so that the mask is contaminated during the exposure process, and the byproducts produced after the photopolymerization initiator decomposes during crosslinking at high temperature reduce the yield, and the exposure process time also increases with the increase of exposure dose. Therefore, it is expected to develop a photopolymerization initiator that has better sensitivity to active energy rays, better solubility and lower cost than 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, and to provide a photoinitiator with high photosensitivity, good solubility, low cost and excellent comprehensive performance.

[0004] In a 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 aromatic ketone group having 7 to 25 carbon atoms, a heteroaromatic ketone group having 4 to 25 carbon atoms, a substituted aromatic ketone group having 7 to 25 carbon atoms, and a substituted heteroaromatic ketone group having 4 to 25 carbon atoms;

[0009] 1-3 hydrogen atoms in the substituted aromatic ketone group having 7 to 25 carbon atoms and the substituted heteroaromatic 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, alkylether 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 alkylether 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 include a part or all of the carbon chain being 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 of the following structures is independently selected from the group consisting of 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, and 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, alkylthio group having 1 to 15 carbon atoms or alkylether group having 1 to 15 carbon atoms substituted by fluorine atoms;

[0014] The cycloalkyl group with 3 to 15 carbon atoms, the heterocycloalkyl group with 2 to 15 carbon atoms, and the heterocycloalkoxy group with 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 with 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 replaced by cyano, nitro, halogen, 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] Further, 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 the substitution sites in R1-R8 that are not hydrogen are symmetrical or asymmetrical.

[0019] Furthermore, the ring structure in the cycloalkanone group having 4 to 15 carbon atoms, 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;

[0020] The ring structures in the heteroaromatic 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, connected 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 benzophenone 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 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 to 2 heteroatoms selected from O, S, and N, or a saturated six-membered heterocyclic group containing 1 to 2 heteroatoms selected from O, S, and N, or a group formed by a combination of a saturated five-membered to six-membered heterocyclic ring containing 1 to 2 heteroatoms selected from O, S, and N and 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 heterocyclic ring containing 1 to 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] Further, 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] A third aspect provides an application of a photopolymerizable composition, wherein the 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 core molecular structure of the dioxydibenzo hexacyclic ring and a significantly improved optical absorption capacity, so that the compound maintains high solubility and exhibits a high OD value and high photosensitivity to 365nm wavelength light in a dark curing system, thereby being better used in dark systems such as color photoresists and black matrices 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 photoinitiator of the present invention has significantly improved thermal stability and has excellent exposure and development characteristics under low exposure conditions (<1s). Excellent photolithography patterns can be prepared in a shorter exposure time, which is beneficial to improving industrial production efficiency and has broad commercial prospects. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0050] Figure 2 is 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 increases. DETAILED DESCRIPTION

[0052] In order to help the understanding of the present invention, preferred embodiments are proposed. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention. If specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[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 continue to add 29.8 g of chlorooctane, stir and react overnight at room temperature, wash with water, extract the product with ethyl acetate 1-2 times, 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, and 15.7 g of octanoyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0 ° C. The reaction was stirred for 2 h, and 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 23.2 g (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 hours, filter the reaction solution with a silica gel funnel, wash the filtrate with water, extract the product with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry to obtain 19.3 g of (10-octylphenothiazine sulfone-3-yl)-1-octyl ketone;

[0058] S4. Dissolve 15 g of 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in 200 mL of N,N-dimethylformamide, add 2.6 mL of concentrated hydrochloric acid and 2.85 g of isobutyl nitrite in sequence, stir the reaction at room temperature for 6 h, quench with ice water, extract the product from the reaction mixture with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry to obtain 11.5 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime;

[0059] S5. Dissolve 10 g of 1-(10-octylphenothiazinesulfone-3-yl)-1,2-octanedione-2-oxime and 2.23 g of triethylamine in 30 mL of dichloromethane, slowly dropwise add 1.73 g of acetyl chloride solution dissolved in 10 mL of dichloromethane at 0°C, and stir to react for 2 h, quench with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry with magnesium sulfate, concentrate, and dry to obtain 8.35 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. 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 chloroisooctane was 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;

[0063] 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, quenched with 150 mL of 20 wt% glacial dilute hydrochloric acid, and 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)phenothiazine-3-yl)-1-cyclohexylpropyl ketone;

[0064] S3. Dissolve 20 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1-cyclohexylpropyl ketone in 250 mL of acetic acid, add 3.2 g of hydrogen peroxide, heat to 70 ° C, react for 6 hours, filter the reaction solution with a silica gel funnel, wash the filtrate with water, extract the product with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry 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 in sequence. The reaction mixture was stirred for 6 h at room temperature, and then quenched with ice water. The product was extracted with ethyl acetate 1-2 times from the reaction mixture, 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 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. The 10-octylphenothiazine in Example 1S2 was replaced by 10-(2-ethylhexyl)phenothiazine, and the octanoyl chloride was replaced by 2,2-dimethyl-1,3-dioxolaneacetyl chloride. Otherwise, the method was the same as that in Example 1S2 to obtain 22.3 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1-cyclohexylpropyl ketone;

[0071] S2. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above, 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-ketone;

[0072] S3. The 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 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-(2,2-dimethyl-1,3-dioxolane)ethyldione-2-oxime;

[0073] S4. Replace the 1-octylphenothiazine sulfone-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 hours, filter the reaction solution with a silica gel funnel, wash the filtrate with water, extract the product with ethyl acetate 1-2 times, 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, and 11.7 g of 2-thiopheneacetyl chloride solution dissolved in 50 mL of dichloromethane was slowly added dropwise at 0°C, and the reaction was stirred for 2 h, quenched with 150 mL of 20 wt% ice-dilute hydrochloric acid, and the product was extracted with dichloromethane 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;

[0079] S3. Dissolve 15 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-(thiophene-2-yl)ethylketone in 200 mL of N,N-dimethylformamide, add 2.6 mL of concentrated hydrochloric acid and 3.3 g of isobutyl nitrite in sequence, stir the reaction at room temperature for 6 h, quench with ice water, extract the product from the reaction mixture with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry to obtain 10.4 g of 1-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1,2-(thiophene-2-yl)ethylketone-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 with 10 mL of 20 wt% glacial dilute hydrochloric acid, extract twice with ethyl acetate, dry over magnesium sulfate, concentrate, and dry to obtain 8.24 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 octyl chloride in Example 1S1 was replaced with isohexyl chloride, and the same method as in Example 1S1 was used to obtain 36.3 g of 10-(2-ethylbutyl)phenothiazine;

[0085] S2. The 10-octylphenothiazine in Example 1S2 was replaced by the product of S1, and the octanoyl chloride was replaced by o-(2,2,3,3-tetrafluoropropoxy)phenylacetyl chloride. The same method as Example 1S2 was used to obtain 27.3 g of 1-(10-(2-ethylbutyl)phenothiazine-3-yl)-1-o-(2,2,3,3-tetrafluoropropoxy)acetophenone;

[0086] S3. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above, and the same method as Example 1S3 was used to obtain 21.2 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1-o-(2,2,3,3-tetrafluoropropoxy)acetophenone;

[0087] S4. The 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S3 above, and 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)phenethyldione-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. Prepare in the same manner as Example 1S5 to obtain 4.23 g of compound (16).

[0089] MS: 635.1247 (MS+1), accurate 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. The 10-octylphenothiazine in Example 1S2 was replaced by 10-(2-ethylhexyl)phenothiazine, and the octanoyl chloride was replaced by p-(methoxy-3-methylbutyloxy)phenylacetyl chloride. The same method as Example 1S2 was used to obtain 29.4 g of 1-(10-(2-ethylbutyl)phenothiazine-3-yl)-1-p-(methoxy-3-methylbutyloxy)acetophenone;

[0093] S2. The 1-(10-octylphenothiazine-3-yl)-1-p-(methoxy-3-methylbutyloxy)acetophenone in Example 1S3 was replaced with the product of S1 above, 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 1-(10-octylphenothiazinesulfone-3-yl)-1-octyl ketone in Example 1S4 was replaced with the product of S2 above, and the mixture was prepared in the same manner as Example 1S4 to obtain 10.0 g of 1-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)-1,2-p-(methoxy-3-methylbutyloxy)phenylethanedione-2-oxime;

[0095] S4. Replace the 1-(10-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 8.1 g of compound (17).

[0096] MS: 649.3591 (MS+1), accurate 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. The 10-octylphenothiazine in Example 1S2 was replaced by 10-(2-ethylhexyl)phenothiazine, and the octanoyl chloride was replaced by p-(2,2-dimethyl-1,3-dioxolane)-o-tolueneacetyl chloride. The same method as Example 1S2 was used to obtain 28.7 g of 1-(10-(2-ethylhexyl)phenothiazine-3-yl)-1-p-(2,2-dimethyl-1,3-dioxolane)-o-tolueneacetyl chloride;

[0100] S2. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above, and the mixture was prepared in the same manner as Example 1S3, 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. The 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-tolueneethylenedione-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. Prepare in the same manner as Example 1S5 to obtain 4.2 g of compound (18).

[0103] MS: 677.1276 (MS+1), accurate 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. The 10-octylphenothiazine in Example 1S2 was replaced with 10-ethylphenothiazine, and octanoyl chloride was replaced with hexanoyl chloride. The same method as Example 1S2 was used to obtain 24.5 g of (10-ethyl-10H-phenothiazine-3-yl)-1-hexyl ketone;

[0107] S2. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above, and the same method as Example 1S3 was used to obtain 20.2 g of (10-ethyl-10H-phenothiazine sulfone-3-yl)-1-hexyl ketone;

[0108] S3. The 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 the 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, 14.9g o-tolueneacetyl chloride solution dissolved in 50mL dichloromethane was slowly added dropwise at 0°C, and the mixture was stirred for 2h. After the reaction was completed, 12.8g aluminum chloride was added and stirred to dissolve, and 17.2g octanoyl chloride solution dissolved in 50mL dichloromethane was slowly added dropwise at 0°C. After the addition was completed, the mixture was stirred for 3h, and 150mL 20wt% glacial dilute hydrochloric acid was used to quench the mixture. The product was extracted with dichloromethane 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 22.5g (6-o-methylbenzoyl-10-(2-ethylhexyl) phenothiazine-3-yl)-1-octyl ketone;

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

[0115] S3. Dissolve 15 g (6-o-methylbenzoyl-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octyl ketone in 200 mL N, N-dimethylformamide, add 2.2 mL concentrated hydrochloric acid and 3.4 g isobutyl nitrite in turn, stir the reaction at room temperature for 6 h, quench with ice water, extract the product 1-2 times with ethyl acetate from the reaction mixture, dry with magnesium sulfate, concentrate, and dry to obtain 10.2 g 15 g (6-o-methylbenzoyl-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 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. The o-tolueneacetyl chloride in Example 9S1 was replaced with 2-methyl-2-morpholinepropionyl chloride, and the same method as Example 9S1 was used to obtain 22.84 g of (6-(2-methyl-2-morpholinepropionyl)-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octanone;

[0121] S2. The (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine-3-yl)-1-octyl ketone in Example 9S2 was replaced with the product of S1 above, and the same method as Example 9S2 was used to obtain 18.3 g of (6-(2-methyl-2-morpholinoacetone)-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-1-octyl ketone;

[0122] S3. 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, and the mixture was prepared in the same manner as Example 9S3 to obtain 10.5 g of (6-(2-methyl-2-morpholinoacetone)-10-(2-ethylhexyl) phenothiazine sulfone-3-yl)-2-hydroxyimino-1-octyl ketone;

[0123] S4. Replace the (6-o-methylbenzoyl-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-2-hydroxyimino-1-octanone 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), accurate 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 ketone-10-butyl phenothiazine-3-yl)-1-ethyl ketone was obtained by replacing 10-(2-ethylhexyl) phenothiazine in Example 9S1 with 10-ethyl phenothiazine and replacing octanoyl chloride with formyl chloride.

[0128] S2. The (6-o-methylphenyl ketone-10-(2-ethylhexyl) phenothiazine-3-yl)-1-octyl ketone in Example 9S2 was replaced with the product of S2 above, and the same method as Example 9S2 was used to obtain 19.5 g of (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl)-1-ethyl ketone;

[0129] S3. Dissolve 15 g (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl)-1-ethyl ketone in 150 mL toluene, add 3.7 g sodium acetate and 3.3 g hydroxylamine hydrochloride, and reflux for 8 h. Cool the reaction solution to room temperature, wash with water, extract the product with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry to obtain 11.2 g (6-o-methylphenyl ketone-10-butyl phenothiazine sulfone-3-yl)-ethanone oxime;

[0130] S5. Replace the (6-o-methylbenzoyl-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-2-hydroxyimino-1-octanone in Example 9S4 with the product of S4 above, and replace acetyl chloride with formyl chloride. Other than that, prepare in the same manner as Example 9S4 to obtain 8.8 g of compound (43).

[0131] MS: 477.5741 (MS+1), accurate 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 hour, then continue to add 16.7 g of chlorobutane, stir and react overnight at room temperature, wash with water, extract the product with ethyl acetate 1-2 times, dry with magnesium sulfate, concentrate, and dry to obtain 33.0 g of 10-butylphenothiazine;

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

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

[0137] S4. The (6-o-methylbenzophenone-10-butylphenothiazinesulfone-3-yl)-1-ethyl ketone in Example 11S3 was replaced with the product of S3 above, and the same method as Example 11S3 was used to obtain 10.8 g of (6-(benzofuran-2-one)-10-butylphenothiazinesulfone-3-yl)-pentanone oxime;

[0138] S5. Replace the (6-o-methylbenzoyl-10-butylphenothiazinesulfone-3-yl)-pentanone oxime in Example 11S4 with the product of S4 above, and replace the formyl chloride with chloroformylpropyl ester. Other than this, 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 by 3-nitro-10H-phenothiazine, and the chlorooctane was replaced by chlorobutane. Otherwise, the same method as in Example 1S1 was used to obtain 30.2 g of 3-nitro-10-butylphenothiazine;

[0143] S2. The 10-octylphenothiazine in Example 1S2 was replaced by the product of S1, and octanoyl chloride was replaced by p-nitrobenzeneacetyl chloride. Otherwise, the same method as Example 1S2 was used to obtain 22.4 g of (6-nitro-10-butylphenothiazine-3-yl)-1-p-nitrobenzophenone;

[0144] S3. The (10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above, and the same method as Example 1S3 was used to obtain 19.0 g of (6-nitro-10-butylphenothiazine sulfone-3-yl)-1-p-nitrobenzophenone;

[0145] S4. The (6-o-methylbenzoyl-10-butylphenothiazine-3-yl)-1-ethyl ketone in Example 11S4 was replaced with the product of S3 above, and the same method as Example 11S4 was used to obtain 10.5 g of (6-nitro-10-butylphenothiazine-3-yl)-1-p-nitrobenzophenone oxime;

[0146] S5. Replace the (6-o-methylbenzoyl-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 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 are dissolved in 300mL dichloromethane, 31.3g propionyl chloride solution dissolved in 50mL dichloromethane is slowly added dropwise at 0°C, and the reaction is stirred for 2h, quenched with 150mL 20wt% glacial dilute hydrochloric acid, and the product is extracted with dichloromethane 1-2 times, dried with magnesium sulfate, concentrated, and dried to obtain 24.6g 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)diacetone;

[0152] S3. The (10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S2 above, and 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, stir the reaction at room temperature for 6 h, quench with ice water, extract the product from the reaction mixture with ethyl acetate 1-2 times, dry with 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 with 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. The 10-(2-ethylbutyl)phenothiazine in Example 14S2 was replaced by 10-octylphenothiazine, and propionyl chloride was replaced by octanoyl chloride. The same method as Example 14S2 was used to obtain 24.6 g of 1,1'-(10-octylphenothiazine-3,6-diyl)dioctanone;

[0159] S2. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above, and the same method as Example 14S3 was used to obtain 19.7 g of 1,1'-(10-(octylphenothiazinesulfone-3,6-diyl)dioctanone;

[0160] S3. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4 was replaced with the product of S2 above, 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. Replace 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3-yl)di(acetone-2-oxime) in Example 14S5 with the product of S3 above. Prepare in the same manner as Example 14S5 to obtain 8.5 g of compound (99).

[0162] MS: 738.5794 (MS+1), accurate 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. The 10-(2-ethylbutyl)phenothiazine in Example 14S2 was replaced by 10-ethylphenothiazine, and the propionyl chloride was replaced by 2-(2-ethoxyethoxy)acetyl chloride. The same method as Example 14S2 was used to obtain 28.3 g of 1,1'-(10-ethylphenothiazine-3,6-diyl)bis(2-ethoxyethoxyethyl ketone);

[0166] S2. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above, and the same method as Example 14S3 was used to obtain 19.1 g of 1,1'-(10-ethylphenothiazinesulfone-3,6-diyl)bis(2-ethoxyethoxyethyl ketone);

[0167] S3. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4 was replaced with the product of S2 above, and 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. The aluminum chloride in Example 4S2 was replaced by 17 g, and 2-thiopheneacetyl chloride was replaced by 18.7 g. The same method as Example 4S2 was used to obtain 14.5 g of 1,1'-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)di((thiophene-2-yl)ethylketone);

[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. Otherwise, the same method as in Example 4S3 was used to obtain 6.6 g of 1,1'-(10-(2-ethylhexyl)phenothiazinesulfone-3-yl)di((thiophene-2-yl)ethylketone-2-oxime);

[0174] S3. The input amount of the above S2 product is adjusted to 5 g, the triethylamine in Example 4S4 is replaced by 2.4 g, and the acetyl chloride is replaced by 1.4 g. Other than this, the same method as Example 4S4 is used to prepare, and 4.0 g of compound (107) can be obtained.

[0175] MS: 734.5248 (MS+1), accurate 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. The 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. The 1-(10-octylphenothiazine-3-yl)-1-octyl ketone in Example 1S3 was replaced with the product of S1 above, and the same method as Example 1 was used to obtain 19.7 g of (10,10-dioxothioxanthone-3-yl)-1-octyl ketone;

[0180] S3. The 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 the 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 to obtain 4.2 g of compound (129).

[0182] MS: 442.3587 (MS+1), accurate 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. The 10-(2-ethylhexyl)phenothiazine in Example 9S1 was replaced by thioxanthone, the o-tolueneacetyl chloride was replaced by furanoyl chloride, and the octanoyl chloride was replaced by propionyl chloride. The same method as Example 9S1 was used to obtain 20.5 g of (6-furanmethanone-thioxanthone-3-yl)-1-propyl ketone;

[0186] S2. The (6-o-methylbenzoyl-10-(2-ethylhexyl)phenothiazine-3-yl)-1-octanone in Example 9S2 was replaced with the product of S1 above, and the same method as Example 9S2 was used to obtain 18.9 g of (6-furanone-10,10-dioxothioxanthone-3-yl)-1-propyl ketone;

[0187] S3. The (6-o-methylbenzoyl-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-1-octyl ketone in Example 9S3 was replaced with the product of S2 above, and the same method as Example 9S3 was used to obtain 9.2 g of (6-furanmethanone-10,10-dioxothioxanthone-3-yl)-1-propyl ketone-2-oxime;

[0188] S4. In Example 9S4, the (6-o-methylbenzoyl-10-(2-ethylhexyl)phenothiazinesulfone-3-yl)-2-hydroxyimino-1-octanone is replaced by the product of S3 above, and the input amount is adjusted to 5 g. Other than this, 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), accurate 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. The 10-(2-ethylbutyl)phenothiazine in Example 14S2 was replaced by thioxanthone, and propionyl chloride was replaced by octanoyl chloride. Otherwise, the same method as in Example 14S2 was used to obtain 28.9 g of 1,1'-(thioxanthone-3,6-diyl)dioctanone;

[0193] S2. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above, and the same method as Example 14S3 was used to obtain 19.0 g of 1,1'-(10,10-dioxothioxanthone-3,6-diyl)dioctanone;

[0194] S3. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4 was replaced with the product of S2 above, 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 by phenoxathiol, o-toluoyl chloride was replaced by 2,4,6-trimethylbenzoyl chloride, and formyl chloride was replaced by propionyl chloride. The same method as in Example 11S2 was used to obtain 22.9 g of (8-(2,4,6-trimethylbenzoyl)-phenoxathiol-2-yl)-1-propyl ketone;

[0200] S2. Replace the (6-o-methylbenzophenone-10-butylphenothiazine-3-yl)-1-ethyl ketone in Example 11S3 with the product of S1 above, and prepare in the same manner as Example 11S3 to obtain 17.4 g of (8-(2,4,6-trimethylbenzophenone)-10,10-dioxothiophenone-2-yl)-1-propyl ketone;

[0201] S3. The (6-o-methylbenzophenone-10-butylphenothiazinesulfone-3-yl)-1-ethyl ketone in Example 11S4 was replaced with the product of S2 above, and the same method as Example 11S4 was used to obtain 10.4 g of (8-(2,4,6-trimethylbenzophenone)-10,10-dioxothiophenone-2-yl)-1-propyl ketone-2-oxime;

[0202] S4. Replace the (6-o-methylbenzoyl-10-butylphenothiazinesulfone-3-yl)-ethanone oxime in Example 11S5 with the product of S3 above. 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. The 10-(2-ethylbutyl)phenothiazine in Example 14S2 was replaced with 9,9-dimethyl-9H-thioxanthine, and the same method as Example 14S2 was used to obtain 20.2 g of 1,1'-(9,9-dimethyl-9H-thioxanthine-3,6-diyl)diacetone;

[0207] S2. The 1,1'-(10-(2-ethylbutyl)phenothiazine-3,6-diyl)diacetone in Example 14S3 was replaced with the product of S1 above, and the same method as Example 14S3 was used to obtain 19.9 g of 1,1'-(9,9-dimethyl-9H-thioxanthinesulfone-3,6-diyl)diacetone;

[0208] S3. The 1,1'-(10-(2-ethylbutyl)phenothiazinesulfone-3,6-diyl)diacetone in Example 14S4 was replaced with the product of S2 above, and the same method as Example 14S4 was used to obtain 12.1 g of 1,1'-(9,9-dimethyl-9H-thioxanthinesulfone-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. In addition, for comparison, the physical property evaluations were also performed on the photopolymerization initiators of the following Comparative Examples 1 to 4. 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 absorption coefficient

[0229] The photoinitiator of the present invention is prepared as 10 -5 mol / L propylene glycol methyl ether acetate (PMA) solution, 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] 20wt% of bisphenol fluorene resin, 60wt% of carbon black, 0.5wt% of the compound of the present invention as a photopolymerization initiator, 0.1wt% of FC-430 (3M leveling agent), and 19.4wt% of PMA were placed in a reaction mixing tank with a UV protective cover and a stirrer, and stirred at room temperature to prepare a photopolymer composition. The photopolymer 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 a 0.04% KOH aqueous solution. The sensitivity was evaluated based on an exposure dose in which the thickness of the step mask pattern was maintained at 80% of the initial thickness, and the exposure dose in which the thickness of the P-1 pattern was maintained at 80% of the initial thickness was defined as 1. Other photoinitiators were evaluated. Under the same residual thickness, the exposure dose was small and the sensitivity was high.

[0234] Table 1

[0235]

[0236]

[0237]

[0238] As can be seen from Table 1, the oxime ester photoinitiator constructed with the di-oxidized dibenzo hexacyclic core in the present invention shows a significant enhancement of the rigidity of the molecular structure and a significant improvement in the optical absorption capacity, so that the compound maintains high solubility, and at the same time, under a dark curing system, relative to the unoxidized or mono-oxidized dibenzo hexacyclic core, or a commercial mainstream product, it shows a high OD value, high photosensitivity and certain inhibition of oxygen inhibition, and can be better used in dark systems such as color photoresist and black matrix of display elements to achieve high contrast, or in the fields of photospacers, planarization layers, semiconductor photoresists and inks to achieve deep curing polymerization. In addition, the photoinitiator of the present invention has significantly improved thermal stability relative to the unoxidized or mono-oxidized dibenzo hexacyclic core, and has excellent exposure and development characteristics under low exposure conditions (<2s), and can prepare excellent photolithography patterns in 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 are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A photoinitiator, characterized in that The photoinitiator is a compound having a structure shown in formula (1): In formula (1), one or two structures of R1 to R8 are selected from the group represented by formula (2) or formula (3): 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 aromatic ketone group having 7 to 25 carbon atoms, a heteroaromatic ketone group having 4 to 25 carbon atoms, a substituted aromatic ketone group having 7 to 25 carbon atoms, and a substituted heteroaromatic ketone group having 4 to 25 carbon atoms; 1-3 hydrogen atoms in the substituted aromatic ketone group having 7 to 25 carbon atoms and the substituted heteroaromatic 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, alkylether 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 alkylether group having 1 to 8 carbon atoms substituted by fluorine atoms; The cycloalkanone group having 4 to 15 carbon atoms and the heterocycloalkanone group having 3 to 15 carbon atoms include a part or all of the carbon chain being 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 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; R9-R 12 Each of the following structures is independently selected from the group consisting of 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, and a substituted heteroaryl group having 3 to 25 carbon atoms; 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, alkylthio group having 1 to 15 carbon atoms or alkylether group having 1 to 15 carbon atoms substituted by fluorine atoms; The cycloalkyl group with 3 to 15 carbon atoms, the heterocycloalkyl group with 2 to 15 carbon atoms, and the heterocycloalkoxy group with 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 with 1 to 15 carbon atoms; 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 replaced by cyano, nitro, halogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl ether group having 1 to 6 carbon atoms; 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.

2. The photoinitiator according to claim 1, characterized in that 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; 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 the substitution sites in R1-R8 that are not hydrogen are symmetrical or asymmetrical.

3. The photoinitiator according to claim 1, characterized in that The ring structure in the cycloalkanone group having 4 to 15 carbon atoms, 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 heteroaromatic 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.

4. The photoinitiator according to claim 3, characterized in that The cycloalkanone group having 4 to 15 carbon atoms is a group formed by a five-membered ring or a six-membered ring connected to a carbonyl group via a single bond or a C1-C6 alkylene group; 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, connected 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 benzophenone 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 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 to 2 heteroatoms selected from O, S, and N, or a saturated six-membered heterocyclic group containing 1 to 2 heteroatoms selected from O, S, and N, or a group formed by a combination of a saturated five-membered to six-membered heterocyclic ring containing 1 to 2 heteroatoms selected from O, S, and N and 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 heterocyclic ring containing 1 to 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.

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

6. 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 5.

7. The photopolymerizable composition according to claim 6, characterized in that The weight of the photoinitiator accounts for 0.01-10% of the weight of the photopolymerizable composition.

8. The photopolymerizable composition according to claim 6, characterized in that The photoinitiator further includes a second photoinitiator and / or additives.

9. The photopolymerizable composition according to claim 8, characterized in that 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.

10. An application of a photopolymerizable composition, characterized in that: The photopolymerizable composition according to any one of claims 6 to 9 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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