Oxime ester compound, photocuring material and application

Abstract

The invention relates to an oxime ester compound, a photocuring material and application, and belongs to the field of photoinitiators. The oxime ester compound is a compound with a structure as shown in a formula (1): # imgabs0 #, wherein R3 in the formula (1) is C6-C20 heteroaryl containing 1-3 Ns. The nitrogen-containing heterocyclic ring is introduced into the original structure, so that the conjugacy of molecules is enhanced, the ultraviolet absorption peak is subjected to red shift, and the compound is more suitable for an LED light source; in addition, due to the introduction of the nitrogen-containing heterocyclic ring, the solubility of molecules in a solvent is improved, so that the photoinitiator is dispersed more uniformly in the solvent, the system is clearer, the photosensitivity of the photoinitiator is improved, and a better effect can be realized by using a small amount of the photoinitiator.

Description

Technical Field

[0001] The invention relates to the field of photoinitiators, and in particular to an oxime ester compound, a photocurable material and applications. Background Art

[0002] Photocuring technology is an advanced curing method that uses the energy of light or electron beams to cause chemically active liquid materials to quickly cure into solid materials through the action of photoinitiators. Compared with traditional curing technologies (such as solvent evaporation curing, air oxidation curing, thermal curing, etc.), photocuring technology has significant advantages such as fast curing speed, energy saving and high efficiency, and environmental friendliness. Therefore, it has been widely used in many fields, including furniture decoration, printed circuit boards, 3D printing, biomedical materials, automotive industry, and inks, and is regarded as a green technology for sustainable development in the 21st century.

[0003] As one of the key components of photocuring technology, photoinitiators are a class of light-sensitive compounds that can absorb light energy of specific wavelengths in the ultraviolet or visible light regions to produce active particles such as free radicals and cations, thereby initiating the cross-linking and curing reaction of oligomers. Although the amount of photoinitiators added to the photocuring formula is very small, they are crucial for controlling the speed and conversion rate of the polymerization process. Free radical photoinitiators are one of the most widely used types. According to the way and mechanism of generating active particles, they can be further divided into cleavage type (Norrish I type) and hydrogen abstraction type (Norrish II type).

[0004] There are some photoinitiators such as Irgacure 369 and OXE-01 that can work under LED light sources, but they have some disadvantages, such as low initiation efficiency, complex synthesis process and high cost. Irgacure 369 can absorb light at wavelengths of 365nm and 405nm, which is suitable for LED light sources, but its photosensitivity and initiation efficiency are low, and it is expensive. OXE-01 faces problems in the industry, such as it can only be used for transparent photoresists, and the maximum UV absorption wavelength does not match the LED light source.

[0005] In view of this, the present invention provides an oxime ester compound, a photocurable material and an application, which are expected to have the characteristics of easy synthesis, low cost, high photosensitivity, ability to effectively match the wavelength of LED light sources, and good biocompatibility. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide an oxime ester compound, a photocurable material and an application thereof.

[0007] In a first aspect, an oxime ester compound is provided, wherein the oxime ester compound is a compound having a structure shown in formula (1):

[0008]

[0009] In formula (1), the structure of Ar1 is C containing N 12 -C 30 A dibenzo six-membered heteroaromatic ring, and R3 is connected to the N atom in the structure of Ar1;

[0010] In formula (1), R1 is a structure shown in formula (2):

[0011] In formula (1), R2 is selected from any one of the following groups: hydrogen, nitro, cyano, C1-C 20 Alkyl ketones, C3-C 20 Heterocyclic alkyl ketones, C6-C 20 Aromatic ketones, C3-C 20 A heteroaryl ketone having a structure shown in formula (2);

[0012] In formula (1), R3 is a C6-C 20 heteroaryl;

[0013] Where R3 is C6-C containing 1-3 N 20 The heteroaryl group refers to non-adjacent 1, 2, and 3;

[0014] In formula (2), R4 and R5 are independently selected from any one of the following structures: C1-C 20 Alkyl, halogen-substituted C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 20 Cycloalkyl, C3-C 20 The heterocycloalkyl group, C1-C 20 Alkyl, C1-C 20 The alkoxy group is at least one substituted C3-C 20 Cycloalkyl or C3-C 20 Heterocycloalkyl, C6-C 20 Aryl, C3-C 20 The heteroaryl group, through C1-C 20 Alkyl, C1-C 20 Alkoxy, C3-C 20 Heterocycloalkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 The alkoxy group is at least one substituted C6-C 20 Aryl or C3-C 20 Heteroaryl, C1-C 20 Alkyl, C1-C 10The alkoxy groups are uninterrupted or are interrupted by at least one O;

[0015] The value range of a in formula (2) is 0-1.

[0016] Furthermore, in formula (1), Ar1 is a structure represented by formula (3) or formula (4):

[0017]

[0018] In formula (3) and formula (4), X1 is any one of the following structures: C(R6R7), O, S(O) b , C(=0O), N(R8);

[0019] The value range of b is 0-2;

[0020] R6 and R7 are independently selected from any one of the following structures: C1-C 20 Alkyl, C1-C 20 Alkoxyl groups;

[0021] R8 is selected from the following structures: C1-C 20 of alkyl.

[0022] Furthermore, in formula (1), R3 is the structure described in formula (5):

[0023] In formula (5) is the substitution site;

[0024] In formula (5), X2 is selected from N and / or CH;

[0025] The hydrogen on CH in R3 is unsubstituted or substituted by R9;

[0026] R9 is selected from any one of the following structures: hydrogen, nitro, thio, cyano, N(R 10 R 11 )、C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 The halogenated alkyl

[0027] R 10 , R 11 Selected from the following structures: C1-C 20 The alkyl group;

[0028] X3 is selected from N, O or CH;

[0029] X4 is selected from N, CH;

[0030] The value range of n and m is 1-3, and m+n is 3-4.

[0031] Further, when R2 in formula (1) is selected from C1-C 20 Alkyl ketones, C3-C 20 Heterocyclic alkyl ketones, C6-C 20 Aryl ketone or C3-C 20 When the heteroaryl ketone is R2, the structure is:

[0032] R 18 Selected from C1-C 10 or R 18 Selected from phenyl, C1-C 10 alkyl-substituted phenyl; or R 18 Selected from C3-C 15 The heteroaryl group is a five-membered heteroaromatic ring or a benzo five-membered heteroaromatic ring, and C3-C 15 The heteroaryl group contains at least one of O, S, and N; or R 18 Selected from C3-C 10 The heterocycloalkane is a six-membered heterocyclic group, and C3-C 10 The heterocyclic alkane contains at least one of O and N, through C1-C 10 An alkyl group is attached to it.

[0033] Furthermore, in formula (2), C6-C 20 The aromatic group is a six-membered ring structure, and the hydrogen atoms separated from each other on the ring are R 12 -R 14 replaced by;

[0034] R 12 -R 14 Independently of each other, at least one of the following structures is selected: C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 15 Heterocycloalkoxy, C1-C 10 Halogenated alkoxy, C1-C 10 The alkoxy groups are uninterrupted or are interrupted by at least one O.

[0035] Furthermore, C6-C 20 The aryl group is selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthryl, pyrene, tetracene, triphenylene, etc., and the hydrogen atoms spaced apart on the ring are R 12 -R 14 substituted; preferably C6-C 20 The aryl group is phenyl.

[0036] Furthermore, in formula (2), C3-C 20The heteroaryl group is a monocyclic or bicyclic structure, C3-C 20 The heteroaryl group contains at least one O, S, or N.

[0037] Furthermore, C3-C 20 The heteroaryl group is selected from the group consisting of thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzopyranyl, tert-anthrenyl, thioxanthenyl, phenothiazine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perylene-1,1-diazophenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, phenoxazinyl; preferably C3-C 20 The heteroaryl group is selected from the group consisting of thienyl, benzo[b]thienyl, furanyl, benzofuranyl, thiazolyl, and benzothiazolyl.

[0038] Furthermore, in formula (2), C3-C 20 The cycloalkyl group is C1-C 10 Alkyl, C1-C 10 Alkoxy or single-bonded monocyclic structure, C3-C 20 The hydrogen atoms on the cycloalkyl group are unsubstituted or replaced by C1-C 20 Alkyl, C1-C 20 Alkoxy substitution.

[0039] Furthermore, C3-C 20 The cycloalkyl radicals are preferably: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, in particular cyclopentyl and cyclohexyl.

[0040] Furthermore, in formula (2), C3-C 20 The heterocycloalkyl group is C1-C 10 Alkyl, C1-C 10 Alkoxy or single-bonded monocyclic structure, C3-C 20 The heterocycloalkyl group contains at least one O, S, N, C3-C 20 The hydrogen atoms on the heterocycloalkyl group are replaced by C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 The alkylthio group is substituted.

[0041] Furthermore, C3-C 20 The preferred heterocycloalkyl group is:

[0042] C1-C 20 The alkyl group is selected from: C1-C 18 -, C1-C 14 -, C1-C 12 -, C1-C8-, C1-C6- or C1-C4-alkyl or C4-C 12 - or C4-C8-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tetrabutyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl;

[0043] C1-C 10 The alkyl group has the same 20 The same definition as for alkyl;

[0044] C1-C 20 Alkoxy is selected from: C1-C 18 Alkoxy, C1-C 14 Alkoxy, C1-C 12 Alkoxy, C1-C8 alkoxy, C1-C6 alkoxy or C1-C4 alkoxy or C4-C 12 Alkoxy or C4-C8 alkoxy, preferably C1-C6 alkoxy or C1-C4 alkoxy, further preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy;

[0045] C1-C 20 The alkylthio group is selected from: C1-C 18 Alkylthio, C1-C 14 Alkylthio, C1-C 12 Alkylthio, C1-C8 alkylthio, C1-C6 alkylthio or C1-C4 alkylthio or C4-C 12 Alkylthio or C4-C8 alkylthio, preferably C1-C6 alkylthio or C1-C4 alkylthio.

[0046] Furthermore, the halogen in the haloalkyl and haloalkoxy groups is selected from fluorine.

[0047] All of the above "at least one" means: 1, 2, 3.

[0048] Further, the structure of the oxime ester compound is any one of the following:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] In a second aspect, an application of an oxime ester compound is used to prepare a photocurable material.

[0055] In a third aspect, a photocurable material comprises the following raw materials: a prepolymerized photosensitive resin, an active monomer and a photoinitiator;

[0056] The photoinitiator includes the oxime ester compound.

[0057] Furthermore, the prepolymerized photosensitive resin includes a resin having a vinyl group; and the reactive monomer includes a monomer having a vinyl group. In the present invention, the raw material of the photocurable material preferably undergoes a photocuring reaction under ultraviolet light.

[0058] Furthermore, the monomer having a vinyl group is selected from epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate, ethylenically unsaturated polyester, amino (meth) acrylate resin, photoimageable alkali-soluble resin, etc. Advantageously, epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate or a combination thereof is used according to the present invention.

[0059] Furthermore, the prepolymerized photosensitive resin is preferably a methacrylate / methacrylic acid / methyl methacrylate copolymer, the molar ratio of methacrylate, methacrylic acid and methyl methacrylate is 20-50:10-15:10-30, and the Mw of the prepolymerized photosensitive resin is preferably 50000-70000. In the present invention, the active monomer is preferably tripropylene glycol diacrylate (TPGDA).

[0060] Furthermore, the raw materials of the photocurable material preferably further include one or more of a colorant, a solvent, a photocrosslinking agent, a photosensitizer, an antioxidant, a surfactant, a curing accelerator and a thermal polymerization inhibitor.

[0061] Furthermore, the photocurable material preferably includes the following raw materials in parts by weight: 100 parts of prepolymerized photosensitive resin, 70 parts of active monomer, and 0.017-15 parts of photoinitiator; the raw materials of the photocurable material preferably also include a solvent, and the solvent is selected from: ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol-1-monomethyl ether-2-acetate; methanol, ethanol, iso- or n-butyl acetate; Alcohol solvents such as propanol, iso- or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, and propylene glycol methyl acetate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; paraffin solvents such as mineral spirits; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used alone or as a mixed solvent of two or more.

[0062] Furthermore, the photoinitiator accounts for 1%-10% of the total amount of the photocurable material, preferably 1%-8%, more preferably 11%-5%, and specifically preferably 3%, 2%, 5% or 4%.

[0063] Furthermore, the preparation method of the photocurable material comprises the following steps: dissolving the prepolymerized photosensitive resin, the active monomer and the photoinitiator in an organic solvent to obtain a mixture; applying the mixture to the surface of the PET template to obtain a wet film; baking the wet film to remove the solvent to obtain a dry film; exposing the dry film to light cure to obtain a photocurable material. The thickness of the wet film is preferably 1-20 μm, and the temperature of the solvent removal is preferably 90°C; during the light curing, the present invention preferably attaches a mask to the dry film. The light source for the exposure is preferably a 365nm LED surface light source.

[0064] Beneficial effects of the present invention:

[0065] (1) The introduction of the nitrogen-containing heteroaryl group of the present invention increases the reactivity of the photoinitiator through the electronic effect, thereby improving the speed of the photocuring reaction;

[0066] (2) The nitrogen-containing heteroaryl group of the present invention contains π electrons, which causes the ultraviolet absorption peak to red-shift, making it more suitable for LED light sources;

[0067] (3) The introduction of the nitrogen-containing heteroaryl group of the present invention can significantly reduce the surface oxygen inhibition effect. On the one hand, the nitrogen-containing heteroaryl group is insensitive to oxygen, so that the photoinitiator of the present invention can maintain a high level of activity in an oxygen environment; on the other hand, the introduction of the nitrogen-containing heteroaryl group accelerates the rate of generating free radicals, accelerates the reaction, shortens the time window of oxygen interference, thereby promoting the polymerization reaction and accelerating the surface curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0069] Figure 1 This is the NMR of Example 1. DETAILED DESCRIPTION

[0070] The embodiments of the present invention will be clearly and completely described below in conjunction with the examples, and the described examples are only some examples of the present invention, rather than all examples. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the examples in the present invention, all other examples obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0071] Embodiment 1:

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

[0073]

[0074] Step 1: Add 9,9-dimethyl-9,10-dihydroacridine (20 g), 2-chloro-4,6-dimethoxy-1,3,5-triazine (16.78 g), PD2DBA3 (0.08 g), triphenylphosphine (5.01 g), sodium tert-butoxide (18.37 g), and 200 ml of toluene to a three-necked flask, and react at 100°C for 8-12 hours. When the reaction is complete, extract with water and 200 ml of ethyl acetate, wash the aqueous phase with 50 ml of ethyl acetate 2-3 times, combine the organic layers, and spin dry to obtain intermediate 1 (25.37 g);

[0075] 1H NMR (deuterated chloroform): δ7.33 (m, 2H), 7.28-7.18 (m, 3H), 7.16-7.02 (m, 1H), 3.95 (s, 2H), 1.56 (s, 12H).

[0076] MS (m / e) +1:349;

[0077] Step 2: Add intermediate 1 (25.37 g) and aluminum chloride (19.42 g) to 200 ml of dichloromethane in a three-necked flask, stir, lower the system temperature to -20°C with dry ice, slowly drop propionyl chloride (8.08 g) dissolved in 75 ml of dichloromethane, warm to room temperature after the addition is complete, stir for 6-10 hours, and after the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (23.64 g);

[0078] 1 H NMR (deuterated chloroform): δ7.90-7.79 (m, 2H), 7.33 (m, 1H), 7.26-7.17 (m, 2H), 7.13 (dd, 1H), 7.10-7.02 (m, 1H), 3.95 (s, 6H), 2.94 (q, 2H), 1.57 (s, 6H), 1.21 (t, 3H).

[0079] MS (m / e) +1:405;

[0080] Step 3: Add intermediate 2 (23.64 g), isobutyl nitrite (9.04 g), and concentrated hydrochloric acid (2.96 g) to 200 ml of DMF in a three-necked flask and stir at room temperature for 3-5 h. After the reaction is completed, add 1000 ml of water, stir, and stand. The organic phase is retained. The aqueous phase is washed 1-2 times with 100 ml of n-heptane. The organic phases are combined, 300 ml of water is added, stirred, and the pH is adjusted to neutral with 0.5 mol / L sodium bicarbonate. The organic phase is retained, spin-dried, ethanol is added and refluxed for 1 h, filtered while hot, spin-dried, and dried to obtain intermediate 3 (22.33 g);

[0081] 1 H NMR (deuterated chloroform): δ9.75 (s, 1H), 8.01 (dd, 1H), 7.90 (d, 1H), 7.37-7.28 (m, 2H), 7.23 (dd, 1H), 7.13 (dd, 1H), 7.10-7.02 (m, 1H), 3.95 (s, 6H), 2.38 (s, 3H), 1.57 (s, 6H).

[0082] MS (m / e) +1:434;

[0083] Step 4: Intermediate 3 (22.33 g) and acetyl chloride (4.85 g) were added to 200 ml of dichloromethane, triethylamine (10.43 g) was slowly added dropwise at 0°C, the temperature was raised to room temperature, and the reaction was carried out at room temperature for 4-6 hours. After confirming that the reaction was complete, 500 ml of water at 0°C was slowly added dropwise and stirred for 1 hour, then the mixture was allowed to stand for stratification and the organic phase was retained. The pH of the organic phase was adjusted to neutral with 0.1 mol / L dilute hydrochloric acid, and the organic phase was retained again after washing with water once. It was dried with 30 g of anhydrous magnesium sulfate and spun into a viscous liquid; the viscous liquid was dissolved in 100 ml of ethanol, heated to reflux for 1 h, and cooled to room temperature to precipitate a white solid product. The final product was obtained by filtration and drying, and 18.94 g of the final product was obtained;

[0084] 1 H NMR (deuterated chloroform): δ7.99 (dd, 1H), 7.88 (d, 1H), 7.37-7.28 (m, 2H), 7.23 (dd, 1H), 7.13 (dd, 1H), 7.11-7.02 (m, 1H), 3.95 (s, 6H), 2.44 (s, 3H), 2.17 (s, 3H), 1.57 (s, 6H).

[0085] MS(m / e)+1:476.

[0086] Embodiment 2-9:

[0087] In Examples 2 to 9, the feed amount, feed ratio, reaction conditions, and post-treatment are the same as those in Example 1, so Examples 2 to 9 can be prepared according to the method of Example 1. The structures and test data of Examples 2 to 9 are shown in Table 1.

[0088] Table 1

[0089]

[0090]

[0091] Embodiment 10:

[0092] The synthesis steps of the compound involved in this embodiment are as follows:

[0093]

[0094] Step 1: Add 9,9-dimethyl-9,10-dihydroacridine (20 g), 2,4-di-tert-butyl-6-chloro-1,3,5-triazine (21.76 g), PD2DBA3 (0.08 g), triphenylphosphine (5.01 g), sodium tert-butoxide (18.37 g), and 200 ml of toluene to a three-necked flask, and react at 100°C for 8-12 hours. When the reaction is complete, extract with water and 200 ml of ethyl acetate, wash the aqueous phase with 50 ml of ethyl acetate 2-3 times, combine the organic layers, and spin dry to obtain intermediate 1 (29.39 g);

[0095] 1 H NMR (deuterated chloroform): δ7.33 (m, 2H), 7.26-7.18 (m, 3H), 7.15-7.02 (m, 3H), 1.56 (s, 6H), 1.44 (s, 18H).

[0096] MS (m / e) +1:401;

[0097] Step 2: Add intermediate 1 (29.39 g) and aluminum chloride (29.89 g) to 200 ml of dichloromethane in a three-necked flask, stir, lower the system temperature to -20°C with dry ice, slowly drop toluoyl chloride (11.55 g) dissolved in 75 ml of dichloromethane, warm to room temperature after completion of the addition, stir for 6-10 h, lower the system temperature to -20°C with dry ice, slowly drop propionyl chloride (7.04 g) dissolved in 75 ml of dichloromethane, warm to room temperature after completion of the addition, stir for 6-10 h, after the reaction is complete, add 100 ml of 0°C 0.2 mol / L HCl, stir, stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (31.68 g);

[0098] 1 H NMR (deuterated chloroform): δ7.90-7.74 (m, 4H), 7.51-7.40 (m, 2H), 7.40-7.29 (m, 2H), 7.28-7.19 (m, 2H), 2.60 (s, 3H), 2.43-2.39 (m, 3H), 1.58 (s, 6H), 1.44 (s, 18H).

[0099] MS (m / e) +1:561;

[0100] Step 3: Add intermediate 2 (31.68 g), hydroxylamine hydrochloride (5.89), and sodium acetate (6.95 g, 1.5 eq) to 200 g of tetrahydrofuran in a three-necked flask and react for 6-12 h. After the reaction is complete as detected by TLC, the reaction solution is added to 1000 ml of water, kept at 0°C overnight, and filtered to obtain a powdery solid. The powdery solid is dissolved in 100 ml of THF, and 20 g of anhydrous magnesium sulfate is added for drying. The mixture is filtered, rotary evaporated, and dried to obtain intermediate 3 (28.14 g).

[0101] 1 H NMR (deuterated chloroform): δ7.90-7.74 (m, 2H), 7.51-7.40 (m, 6H), 7.40-7.29 (m, 3H), 2.60 (s, 3H), 2.43-2.39 (m, 3H), 1.58 (s, 6H), 1.44 (s, 18H).

[0102] MS (m / e) +1:576;

[0103] Step 4: In a three-necked flask, intermediate 3 (28.14 g) and acetyl chloride (4.60 g) were added to 200 ml of dichloromethane, triethylamine (9.89 g) was slowly added dropwise at 0°C, the temperature was raised to room temperature, and the reaction was carried out at room temperature for 4-6 hours. After confirming that the reaction was complete, 500 ml of water at 0°C was slowly added dropwise and stirred for 1 hour, then allowed to stand for stratification and the organic phase was retained, the pH of the organic phase was adjusted to neutral with 0.1 mol / L dilute hydrochloric acid, the organic phase was retained again after washing once, and dried with 30 g of anhydrous magnesium sulfate, and vortexed into a viscous liquid; the viscous liquid was dissolved in 100 ml of ethanol, heated to reflux for 1 h, and cooled to room temperature to precipitate a white solid product, which was filtered and dried to obtain the final product, and 22.57 g of the final product was obtained.

[0104] 1 H NMR (deuterated chloroform): δ7.87 (dd, 2H), 7.57-7.41 (m, 3H), 7.40-7.29 (m, 3H), 7.21 (dd, 2H), 2.47-2.39 (m, 6H), 2.20 (s, 3H), 1.58 (s, 6H), 1.44 (s, 18H).

[0105] MS(m / e)+1:618.

[0106] Examples 11-17

[0107] For Examples 11 to 17, the feed amount, feed ratio, reaction conditions, and post-treatment are the same as those of Example 10. Therefore, Examples 11 to 17 can be prepared according to the method of Example 10. The structures and test data of Examples 11 to 17 are shown in Table 2.

[0108] Table 2

[0109]

[0110]

[0111]

[0112] Embodiment 18

[0113] The synthesis steps of the compound involved in this embodiment are as follows:

[0114]

[0115] Step 1: Add acridin-9(10H)-one (20 g), 2,2-chloro-5-methylpyridine (13.07 g), PD2DBA3 (0.09 g), triphenylphosphine (5.91 g), sodium tert-butoxide (19.69 g), and 200 ml of toluene into a three-necked flask, and react at 100°C for 8-12 hours. When the reaction is complete, extract with water and 200 ml of ethyl acetate, wash the aqueous phase with 50 ml of ethyl acetate 2-3 times, combine the organic layers, and spin dry to obtain intermediate 1 (22.81 g);

[0116] 1 H NMR (deuterated chloroform): δ 8.07-8.00 (m, 3H), 7.51 (m, 2H), 7.38 (dd, 1H), 7.36-7.30 (m, 1H), 7.34-7.23 (m, 2H), 7.26-7.21 (m, 1H), 6.75 (d, 1H), 2.30 (d, 3H).

[0117] MS (m / e) +1:287;

[0118] Step 2: Add intermediate 1 (22.81 g) and aluminum chloride (31.86 g) to 200 ml of dichloromethane in a three-necked flask, stir, lower the system temperature to -20°C with dry ice, slowly drop propionyl chloride (16.22 g) dissolved in 75 ml of dichloromethane, warm to room temperature after the addition is complete, stir for 6-10 hours, and after the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (23.66 g);

[0119] 1H NMR (deuterated chloroform): δ8.44 (d, 2H), 8.06-7.99 (m, 3H), 7.36-7.27 (m, 3H), 6.67 (m, 1H), 2.94 (q, 4H), 2.30 (s, 3H), 1.21 (t, 6H).

[0120] MS (m / e) +1:399;

[0121] Step 3: Add intermediate 2 (23.66 g), isobutyl nitrite (18.37 g), and concentrated hydrochloric acid (6.01 g) to 200 ml of DMF in a three-necked flask, heat to 50° C., and stir at 50° C. for 3-5 h. After the reaction is completed, add 1000 ml of water, stir, and let stand. The organic phase is retained. The aqueous phase is washed 1-2 times with 100 ml of petroleum ether. The organic phases are combined, 300 ml of water is added, stirred, and the pH is adjusted to 7 with 0.5 mol / L sodium bicarbonate. The organic phase is retained, the aqueous phase is washed 1-2 times with 100 ml of n-heptane, and the organic phases are combined, spin-dried, methylcyclohexane is added, and refluxed for 1 h. Filter while hot, spin-dried, and dried to obtain intermediate 3 (22.12 g);

[0122] 1 H NMR (deuterated chloroform): δ 9.85 (s, 1H), 9.75 (s, 1H), 8.50 (d, 2H), 8.19 (dd, 2H), 8.03 (d, 1H), 7.43 (dd, 2H), 7.36-7.29 (m, 1H), 6.75 (d, 1H), 2.38 (d, 6H), 2.30 (s, 3H).

[0123] MS (m / e) +1:457;

[0124] Step 4: In a three-necked flask, intermediate 3 (22.12 g) and acetyl chloride (2.20 g) were added to 200 ml of dichloromethane, triethylamine (14.71 g) was slowly added dropwise at 0°C, the temperature was raised to room temperature, and the reaction was carried out at room temperature for 4-6 hours. After confirming that the reaction was complete, 500 ml of water at 0°C was slowly added dropwise and stirred for 1 hour, then allowed to stand for stratification and the organic phase was retained, the pH of the organic phase was adjusted to neutral with 0.1 mol / L dilute hydrochloric acid, the organic phase was retained again after washing once, and dried with 30 g of anhydrous magnesium sulfate, and vortexed into a viscous liquid; the viscous liquid was dissolved in 100 ml of ethanol, heated to reflux for 1 h, and cooled to room temperature to precipitate a white solid product, which was filtered and dried to obtain the final product, and 18.04 g of the final product was obtained.

[0125] 1H NMR (deuterated chloroform): δ8.50 (d, 2H), 8.17 (dd, 2H), 8.03 (d, 1H), 7.43 (dd, 2H), 7.36-7.29 (m, 1H), 6.75 (d, 1H), 2.44 (d, 6H), 2.30 (s, 3H), 2.17 (s, 6H).

[0126] MS(m / e)+1:541

[0127] Embodiment 19

[0128] The synthesis steps of the compound involved in this embodiment are as follows:

[0129]

[0130] Step 1: Add 10H phenoxazine (20 g), 4-chloro-2-methyl-6-(methylthio)pyrimidine (19.07 g), PD2DBA3 (0.09 g), triphenylphosphine (5.73 g), sodium tert-butoxide (20.98 g), and 200 ml of toluene into a three-necked flask, and react at 100°C for 8-12 hours. When the reaction is complete, extract with water and 200 ml of ethyl acetate, wash the aqueous phase with 50 ml of ethyl acetate 2-3 times, combine the organic layers, and spin dry to obtain intermediate 1 (27.67 g);

[0131] 1 H NMR (deuterated chloroform): δ 7.30-7.16 (m, 6H), 6.81 (dd, 2H), 6.27 (s, 1H), 2.56 (s, 3H), 2.43 (s, 3H).

[0132] MS (m / e) +1:322;

[0133] Step 2: Add intermediate 1 (27.67 g) and aluminum chloride (34.44 g) to 200 ml of dichloromethane in a three-necked flask, stir, lower the system temperature to -20°C with dry ice, slowly drop acetyl chloride (14.87 g) dissolved in 75 ml of dichloromethane, warm to room temperature after the addition is complete, stir for 6-10 hours, and after the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (26.15 g);

[0134] 1H NMR (deuterated chloroform): δ7.73 (dd, 2H), 7.62 (d, 1H), 7.36 (d, 2H), 7.24 (s, 1H), 6.27 (s, 1H), 2.58 (d, 9H), 2.43 (s, 3H).

[0135] MS (m / e) +1:406;

[0136] Step 3: Add intermediate 2 (26.15 g), hydroxylamine hydrochloride (13.44 g), and sodium acetate (15.87 g) to 200 g of tetrahydrofuran in a three-necked flask and react for 6-12 h. After the reaction is complete as detected by TLC, the reaction solution is added to 1000 ml of water, kept at 0°C overnight, and filtered to obtain a powdery solid. The powdery solid is dissolved in 100 ml of THF, and 20 g of anhydrous magnesium sulfate is added to dry, filtered, rotary evaporated, and dried to obtain intermediate 3 (22.80 g);

[0137] 1 H NMR (deuterated chloroform): δ7.73 (dd, 3H), 7.62 (d, 2H), 7.36 (d, 1H), 7.24 (s, 2H), 6.27 (s, 1H), 2.56 (s, 3H), 2.58 (d, 6H), 2.43 (s, 3H).

[0138] MS (m / e) +1:436;

[0139] Step 4: In a three-necked flask, intermediate 3 (22.80 g) and acetyl chloride (9.04 g) were added to 200 ml of dichloromethane, triethylamine (15.89 g) was slowly added dropwise at 0°C, the temperature was raised to room temperature, and the reaction was carried out at room temperature for 4-6 hours. After confirming that the reaction was complete, 500 ml of water at 0°C was slowly added dropwise and stirred for 1 hour, then allowed to stand for stratification and the organic phase was retained, the pH of the organic phase was adjusted to neutral with 0.1 mol / L dilute hydrochloric acid, the organic phase was retained again after washing once, and dried with 30 g of anhydrous magnesium sulfate, and vortexed into a viscous liquid; the viscous liquid was dissolved in 100 ml of ethanol, heated to reflux for 1 h, and cooled to room temperature to precipitate a white solid product, which was filtered and dried to obtain the final product, and 21.69 g of the final product was obtained.

[0140] 1 H NMR (deuterated chloroform): δ7.56 (d, 1H), 7.40 (dd, 2H), 7.15 (s, 1H), 6.97 (d, 2H), 6.27 (s, 1H), 2.56 (s, 3H), 2.44 (d, 6H), 2.29 (s, 3H), 2.18 (d, 6H).

[0141] MS(m / e)+1:520.

[0142] Embodiment 20

[0143] The synthesis steps of the compound involved in this embodiment are as follows:

[0144]

[0145] Step 1: Add 9-oxo-9,10-dihydroacridine-2-carbonitrile (20 g), 3-chloro-2,5-dimethylpyrazine (19.07 g), PD2DBA3 (0.09 g), triphenylphosphine (5.73 g), sodium tert-butoxide (20.98 g), and 200 ml of toluene to a three-necked flask, and react at 100°C for 8-12 hours. When the reaction is complete, extract with water and 200 ml of ethyl acetate, wash the aqueous phase with 50 ml of ethyl acetate 2-3 times, combine the organic layers, and spin dry to obtain intermediate 1 (21.68 g);

[0146] 1 H NMR (deuterated chloroform): δ8.18 (d, 1H), 8.09-8.00 (m, 1H), 7.89-7.84 (m, 1H), 7.79 (dd, 1H), 7.55-7.47 (m, 2H), 7.41-7.39 (m, 1H), 7.26 (m, 1H), 2.42 (d, 6H).

[0147] MS (m / e) +1:327;

[0148] Step 2: Add intermediate 1 (21.68 g) and aluminum chloride (17.71 g) to 200 ml of dichloromethane in a three-necked flask, stir, lower the system temperature to -20°C with dry ice, slowly drop acetyl chloride (6.26 g) dissolved in 75 ml of dichloromethane, warm to room temperature after the addition is complete, stir for 6-10 hours, and after the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (18.74 g);

[0149] 1 H NMR (deuterated chloroform): δ8.42 (d, 1H), 8.22 (d, 1H), 8.02 (dd, 1H), 7.89-7.84 (m, 1H), 7.79 (dd, 1H), 7.43-7.33 (m, 2H), 2.61 (s, 3H), 2.44 (d, 3H), 2.40 (s, 3H).

[0150] MS (m / e) +1:369;

[0151] Step 3: Add intermediate 2 (18.74 g), hydroxylamine hydrochloride (1.5 g), and sodium acetate (6.26 g) to 200 g of tetrahydrofuran in a three-necked flask and react for 6-12 h. After the reaction is complete as detected by TLC, add the reaction solution to 1000 ml of water, keep at 0°C overnight, and filter to obtain a powdery solid. Dissolve the powdery solid in 100 ml of THF, add 20 g of anhydrous magnesium sulfate to dry, filter, rotary evaporate, and dry to obtain intermediate 3 (17.58 g);

[0152] 1 H NMR (deuterated chloroform): δ8.19 (dd, 2H), 7.89-7.84 (m, 1H), 7.79 (dd, 1H), 7.67 (dd, 1H), 7.56 (s, 1H), 7.40 (d, 1H), 7.32 (s, 1H), 2.48-2.42 (m, 6H), 2.40 (s, 3H).

[0153] MS (m / e) +1:384;

[0154] Step 4: In a three-necked flask, intermediate 3 (17.58 g) and acetyl chloride (4.32 g) were added to 200 ml of dichloromethane, triethylamine (9.28 g) was slowly added dropwise at 0°C, the temperature was raised to room temperature, and the reaction was carried out at room temperature for 4-6 hours. After confirming that the reaction was complete, 500 ml of water at 0°C was slowly added dropwise and stirred for 1 hour, then the mixture was allowed to stand for stratification and the organic phase was retained. The pH of the organic phase was adjusted to neutral with 0.1 mol / L dilute hydrochloric acid, and the organic phase was retained again after washing with water once. It was dried with 30 g of anhydrous magnesium sulfate and spun into a viscous liquid; the viscous liquid was dissolved in 100 ml of ethanol, heated to reflux for 1 h, and cooled to room temperature to precipitate a white solid product. The final product was obtained by filtration and drying, and 15.37 g of the final product was obtained;

[0155] 1 H NMR (deuterated chloroform): δ8.22 (dd, 2H), 7.89-7.84 (m, 1H), 7.79 (dd, 1H), 7.72 (dd, 1H), 7.40 (d, 1H), 7.31 (s, 1H), 2.45 (s, 6H), 2.40 (s, 3H), 2.20 (s, 3H).

[0156] MS(m / e)+1:426.

[0157] Examples 21-22

[0158] In Examples 21 to 22, the feed amount, feed ratio, reaction conditions, and post-treatment are the same as those in Example 20. Therefore, Examples 21 to 22 can be prepared according to the method of Example 20. The structures and test data of Examples 21 to 22 are shown in Table 3.

[0159] Table 3

[0160]

[0161] Comparative Example 1:

[0162] The compound of Comparative Example 1 is:

[0163] Comparative Example 2:

[0164] The compound of Comparative Example 2 is:

[0165] Comparative Example 3

[0166] The compound of Comparative Example 3 is:

[0167] Test example

[0168] 1. Maximum absorption wavelength and molar absorption coefficient

[0169] 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 )

[0170] 2. Solubility

[0171] Taking propylene glycol methyl ether acetate (PMA), a reactive diluent widely used in the art, as an example, the maximum weight that can be dissolved in 100 g of solvent at 25° C. is used as the evaluation standard for the photoinitiator of the present invention.

[0172] 3.Light sensitivity

[0173] 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 pattern of comparative example 1 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. The results are shown in Table 4.

[0174] Table 4

[0175]

[0176]

[0177] In summary, the introduction of nitrogen-containing heteroaryl groups in the present invention can significantly reduce the surface oxygen inhibition effect. On the one hand, nitrogen-containing heteroaryl groups are insensitive to oxygen, so that the photoinitiator of the present invention can maintain a high level of activity in an oxygen environment; on the other hand, the introduction of nitrogen-containing heteroaryl groups accelerates the rate of free radical generation, accelerates the reaction, shortens the time window of oxygen interference, thereby promoting the polymerization reaction and accelerating the surface curing.

[0178] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. An oxime ester compound, characterized in that: The oxime ester compound is a compound having a structure shown in formula (1): In formula (1), the structure of Ar1 is C containing N 12 -C 30 A dibenzo six-membered heteroaromatic ring, and R3 is connected to the N atom in the structure of Ar1; In formula (1), R1 is a structure shown in formula (2): In formula (1), R2 is selected from any one of the following groups: hydrogen, nitro, cyano, C1-C 20 Alkyl ketones, C3-C 20 Heterocyclic alkyl ketones, C6-C 20 Aromatic ketones, C3-C 20 A heteroaryl ketone having a structure shown in formula (2); In formula (1), R3 is C3-C 20 heteroaryl; In formula (2), R4 and R5 are independently selected from any one of the following structures: C1-C 20 Alkyl, halogen-substituted C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 20 Cycloalkyl, C3-C 20 The heterocycloalkyl group, C1-C 20 Alkyl, C1-C 20 The alkoxy group is at least one substituted C3-C 20 Cycloalkyl or C3-C 20 Heterocycloalkyl, C6-C 20 Aryl, C3-C 20 The heteroaryl group, through C1-C 20 Alkyl, C1-C 20 Alkoxy, C3-C 20 Heterocycloalkoxy, C1-C 20 The haloalkoxy group is substituted with at least one C6-C 20 Aryl or C3-C 20 Heteroaryl, C1-C 20 Alkyl, C1-C 10 The alkoxy groups are uninterrupted or are interrupted by at least one O; The value range of a in formula (2) is 0-1.

2. An oxime ester compound according to claim 1, characterized in that: In formula (1), Ar1 is a structure represented by formula (3) or formula (4): In formula (3) and formula (4), X1 is any one of the following structures: C(R6R7), O, S(O) b , C(=O), N(R8); The value range of b is 0-2; R6 and R7 are independently selected from any one of the following structures: C1-C 20 Alkyl, C1-C 20 Alkoxyl groups; R8 is selected from the following structures: C1-C 20 of alkyl.

3. An oxime ester compound according to claim 1, characterized in that: In formula (1), R3 is a structure shown in formula (5): In formula (5) is the substitution site; In formula (5), X2 is selected from N and / or CH; The hydrogen on CH in R3 is unsubstituted or substituted by R9; R9 is selected from any one of the following structures: hydrogen, nitro, thio, cyano, N(R 10 R 11 )、C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 The halogenated alkyl R 10 , R 11 Selected from the following structures: C1-C 20 The alkyl group; X3 is selected from N, O or CH; X3 is selected from N, CH; The value range of n and m is 1-3, and m+n is 3-4.

4. An oxime ester compound according to claim 1, characterized in that: When R2 in formula (1) is selected from C1-C 20 Alkyl ketones, C3-C 20 Heterocyclic alkyl ketones, C6-C 20 Aryl ketone or C3-C 20 When the heteroaryl ketone is R2, the structure is: R 18 Selected from C1-C 10 or R 18 Selected from phenyl, C1-C 10 alkyl-substituted phenyl; or R 18 Selected from C3-C 15 The heteroaryl group is a five-membered heteroaromatic ring or a benzo five-membered heteroaromatic ring, and C3-C 15 The heteroaryl group contains at least one of O, S, and N; or R 18 Selected from C3-C 10 The heterocycloalkyl group is a six-membered heterocyclic group, and C3-C 10 The heterocyclic alkane contains at least one of O and N, through C1-C 10 An alkyl group is attached to it. R 19 Selected from C1-C 10 of alkyl.

5. An oxime ester compound according to any one of claims 1 to 4, characterized in that: In formula (2), C6-C 20 The aromatic group is a six-membered ring structure, and the hydrogen atoms separated from each other on the ring are R 12 -R 14 replaced by; R 12 -R 14 Independently of each other, at least one of the following structures is selected: C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 15 Heterocycloalkoxy, C1-C 10 Halogenated alkoxy, C1-C 10 The alkoxy groups are uninterrupted or are interrupted by at least one O; In formula (2), C3-C 20 The heteroaryl group is a monocyclic or bicyclic structure, C3-C 20 The heteroaryl group contains at least one O, S, or N; In formula (2), C3-C 20 The cycloalkyl group is C1-C 10 Alkyl, C1-C 10 Alkoxy or single-bonded monocyclic structure, C3-C 20 The hydrogen atoms on the cycloalkyl group are unsubstituted or replaced by C1-C 20 Alkyl, C1-C 20 Alkoxy substitution; In formula (2), C3-C 20 The heterocycloalkyl group is C1-C 10 Alkyl, C1-C 10 Alkoxy or single-bonded monocyclic structure, C3-C 20 The heterocycloalkyl group contains at least one O, S, N, C3-C 20 The hydrogen atoms on the heterocycloalkyl group are replaced by C1-C 20 Alkyl, C1-C 20 Alkoxy substitution.

6. An oxime ester compound according to any one of claims 1 to 4, characterized in that: The structure of the oxime ester compound is any one of the following:

7. An application of an oxime ester compound, characterized in that: The oxime ester compound according to any one of claims 1 to 6 is used in preparing a photocurable material.

8. A photocurable material, characterized in that: The photocurable material comprises the following raw materials: prepolymerized photosensitive resin, active monomer and photoinitiator; The photoinitiator comprises the oxime ester compound according to any one of claims 1 to 6.

9. The photocurable material according to claim 8, characterized in that: The prepolymerized photosensitive resin includes a resin having a vinyl group; The active monomers include monomers having vinyl groups; The photoinitiator accounts for 0.1%-10% of the total amount of the photocurable material.

10. A photocurable material according to claim 8 or 9, characterized in that: The raw materials of the photocurable material further include at least one of a colorant, a solvent, a photocrosslinking agent, a photosensitizer, an antioxidant, a surfactant, a curing accelerator and a thermal polymerization inhibitor.

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