Oxime ester photoinitiator and photopolymerization composition

Abstract

The invention belongs to the technical field of photoinitiators, and particularly relates to an oxime ester photoinitiator and a photopolymerization composition. According to the invention, groups such as thiophene sulfone, thiophene sulfoxide, benzothiophene sulfone, benzothiophene sulfoxide and the like are introduced into the photoinitiator, so that not only is the sensitivity of the photoinitiator improved, but also the solubility of the photoinitiator in a solvent is enhanced.

Description

Technical Field

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

[0002] A photosensitive composition containing an oxime ester photopolymerization initiator can be cured by irradiation with active energy rays and can therefore be used in a variety of applications such as photocurable adhesives, photocurable inks, photosensitive printing plates, and various photoresists.

[0003] Commonly used oxime ester photoinitiators use carbazole or diphenyl sulfide groups as the main groups, among which BASF products OXE-01 and OXE-02 are two common oxime ester representative products on the market. These two products have high photosensitivity, but their ultraviolet absorption wavelength is short and is not suitable for the needs of (UV-vis) LED light sources (emission wavelength 300-450nm). There are also some patents on oxime ester photoinitiators in China, such as CN102775527A discloses a diphenyl sulfide ketone oxime ester photoinitiator and a preparation method thereof, and CN102492059A discloses a substituted diphenyl sulfide ketone oxime ester photoinitiator, etc. However, the ultraviolet absorption wavelength of most initiators is 250-350nm, which cannot match the increasingly developed LED light source, which greatly limits the application of oxime ester photoinitiators. These compounds also have room for improvement in solubility, photosensitivity, etc.

[0004] Summary of the invention

[0005] In order to solve the deficiencies of the prior art, the present invention provides an oxime ester photoinitiator and a photopolymerization composition. The present invention provides a photoinitiator that can replace OXE-01 and OXE-02 for (UV-vis) LED light source (emission wavelength 280nm-400nm) radiation curing, and is more suitable for (UV-vis) LED light source curing and has excellent photosensitivity, good thermal stability and good solubility.

[0006] The technical solution provided by the present invention is as follows:

[0007] An oxime ester photoinitiator is a compound having a structure shown in formula (I):

[0008]

[0009] Wherein, Ar1 is selected from the structure shown in formula (II), is the substitution site,

[0010]

[0011] X1 is a heteroaryl group containing a sulfinyl group or a sulfonyl group;

[0012] R1 is hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, C3-C6 heterocyclic aryl, or C6-C 12 The aryl group, the C6-C 12 The aryl group is unsubstituted or substituted by one or more of nitro, cyano, C1-C8 alkyl, and C1-C8 alkoxy;

[0013] R2 is hydrogen, or C1-C8 alkyl, which is unsubstituted or substituted by halogen, or C1-C8 alkoxy, which is unsubstituted or substituted by halogen, or C3-C 10 The cycloalkyl group is unsubstituted or substituted with a C1-C8 alkyl group, or a C3-C 10 The heterocycloalkyl group is unsubstituted or substituted with a C1-C8 alkyl group and contains 1-2 O or S, or C6-C 12 Aryl, which is unsubstituted or substituted by 1 to 2 groups selected from C1-C8 alkyl, C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, and the C1-C8 alkyl is interrupted by one or more O, and / or substituted by halogen, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl;

[0014] R3 and R4 form a fused ring structure with -CH=CH-CH=CH- through a shared chemical bond;

[0015] R5 is connected to X1 in formula (I);

[0016] R6 is selected from: hydrogen, C1-C8 alkyl, C1-C8 alkoxy;

[0017] The remaining R7-R9 are the same or different and are independently hydrogen, nitro, cyano, C1-C8 alkyl, C1-C8 alkoxy;

[0018] Y1 is C(R 10 )(R 11 )、C(=O)、N(R 12 ), O, S, S(=O) or S(=O)2;

[0019] Y2 is empty, a direct bond, O or S;

[0020] R 10 -R 11 The same or different, independently of each other, are hydrogen, C1-C9 alkyl;

[0021] R 12Selected from: C1-C9 alkyl, dibenzoketo;

[0022] a1 and a2 are the same or different, and are independently 0 or 1.

[0023] According to the above technical solution: R1 is C6-C 12 When the aryl group is substituted, the substituent is one or more substituents selected from nitro, cyano, C1-C8 alkyl, and C1-C8 alkoxy;

[0024] When R1 is C6-C 12 The aryl group is preferably: phenyl, tolyl, mesityl;

[0025] When R2 is a substituted C1-C8 alkyl group, the substituent is a halogen;

[0026] When R2 is C1-C8 alkyl, it is preferably: methyl, ethyl, propyl, C4, C8 alkyl, fluoromethyl, ethyl, propyl, C4, C8 alkyl;

[0027] When R2 is a substituted C1-C8 alkoxy group, the substituent is a substituent selected from the group consisting of halogen, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, and C3-C6 heterocyclic aryl;

[0028] When R2 is a C1-C8 alkoxy group, it is preferably: methoxy, ethoxy, propoxy, C4, C8 alkoxy, fluoromethoxy, ethoxy, propoxy, C4, C8 alkoxy;

[0029] R2 is substituted C3-C 10 When the cycloalkyl group is substituted with a C1-C8 alkyl group;

[0030] When R2 is C3-C 10 The cycloalkyl group is preferably: cyclopropane, cyclohexane, cyclopentane, cyclopropane, cyclohexane, cyclopentane substituted with 1-2 methyl groups;

[0031] R2 is substituted C3-C 10 When the heterocycloalkyl group is a C1-C8 alkyl group, the substituent is a C1-C8 alkyl group and contains 1-2 O, S, or N atoms;

[0032] When R2 is C3-C 10 The heterocycloalkyl group is preferably a C3-C6 heterocycloalkyl group containing 1-2 Os and substituted by 1-2 methyl groups in the cyclopropyl, cyclohexyl, and cyclopentyl groups;

[0033] R2 is substituted C6-C 12When the aryl group is substituted with 1-2 carbon atoms, the substituents are 1 to 2 substituents selected from C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C3-C6 cycloalkyl, and C3-C6 heterocycloalkyl, and the carbon atoms in the substituents are not interrupted or are interrupted by at least one O;

[0034] When R2 is C6-C 12 The aryl group is preferably: phenyl, tolyl, mesityl, ethylphenyl, methoxyphenyl, ethoxyphenyl, pentafluoropropoxyphenyl;

[0035] The above technical solution introduces groups such as thiophene sulfone, thiophene sulfoxide, benzothiophene sulfone and benzothiophene sulfoxide into the photoinitiator, which not only improves the photosensitivity of the photoinitiator, but also enhances its solubility in the solvent.

[0036] According to the above technical solution, X1 is represented by the following structural formula (VI):

[0037]

[0038] Y3 is sulfinyl or sulfonyl;

[0039] R 13 -R 15 are the same or different, all are hydrogen, or one of them is nitro, cyano, C1-C8 alkyl, C1-C8 alkoxy, or, R 13 and R 14 , R 14 and R 15 One pair is -CH=CH-CH=CH-, wherein H is unsubstituted or substituted by C1-C8 alkyl or C1-C8 alkoxy.

[0040] The preferred structure of X1 is:

[0041]

[0042] According to the above technical solution, the structure shown in formula (II) is selected from one of the following formulas (III)-(V):

[0043]

[0044] According to the above technical solution, R2 is C6-C 12 When the aryl group is , it is represented by the following structural formula (VII):

[0045]

[0046] Among them, R 16 -R 201 to 3 non-adjacent groups are independently one or two of C1-C8 alkyl, C1-C8 alkoxy, fluorinated C1-C8 alkyl, fluorinated C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, and the C1-C8 alkyl and C1-C8 alkoxy groups are not interrupted or are interrupted by 1-2 Os.

[0047] Preferred:

[0048] The C3-C6 cycloalkyl group is a monocyclic cycloalkyl group selected from a saturated five-membered ring or a six-membered ring;

[0049] The C3-C6 heterocycloalkyl is a monocyclic heterocycloalkyl selected from a saturated five-membered ring or a six-membered ring containing an O or N heteroatom;

[0050] The C3-C6 heterocyclic aromatic group is a five-membered ring, a six-membered ring or a benzo five-membered ring, and the heteroatom is selected from O, N, and S;

[0051] C6-C 12 The aryl group is a benzene ring, or a polycyclic ring formed by a condensed unsaturated five-membered ring containing O, N, S heteroatoms and a benzene ring.

[0052] According to the above technical scheme, the alkyl group of C1-C8 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2-ethylpentyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3-ethylhexyl, 2-ethylhexyl;

[0053] The C1-C8 alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, n-hexyloxy, 2-methylpentoxy, 3-methylpentoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy, n-heptyloxy, 2-methylhexyloxy, 3-methylhexyloxy, 4-methylhexyloxy, 2,2- dimethylpentyloxy, 2,3-dimethylpentyloxy, 2,4-dimethylpentyloxy, 3,3-dimethylpentyloxy, 3-ethylpentyloxy, 2-ethylpentyloxy, n-octyloxy, 2-methylheptyloxy, 3-methylheptyloxy, 4-methylheptyloxy, 2,2-dimethylhexyloxy, 2,3-dimethylhexyloxy, 2,4-dimethylhexyloxy, 2,5-dimethylhexyloxy, 3,3-dimethylhexyloxy, 3,4-dimethylhexyloxy, 3-ethylhexyloxy, 2-ethylhexyloxy;

[0054] The C3-C6 heterocycloalkyl group is selected from the group consisting of: oxacyclopropyl, thicyclopropyl, oxetanyl, thicyclobutyl, oxolyl, thiolyl, oxhexyl, thicyclohexyl, sulfone heterocyclopropyl, sulfone heterocyclobutyl, sulfone heterocyclopentyl, sulfone heterocyclohexyl, sulfoxide heterocyclopropyl, sulfoxide heterocyclobutyl, sulfoxide heterocyclopentyl, sulfoxide heterocyclohexyl, and 1-2 hydrogen atoms in each of the above groups may be replaced by a C1-C4 alkyl group;

[0055] The C3-C6 cycloalkyl group is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0056] According to the above technical solution, the halogen is selected from fluorine and bromine, preferably fluorine.

[0057] According to the above technical solution, "through more than one, through one or more," is represented by 1 or 2.

[0058] The oxime ester photoinitiator can be selected from the following compounds:

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] The present invention also provides a photopolymerizable composition comprising: (a) at least one ethylenically unsaturated photopolymerizable compound;

[0065] (b) the oxime ester photoinitiator provided by the present invention;

[0066] (c) Additives.

[0067] Specifically, the weight ratio of the oxime ester photoinitiator to the photopolymerizable composition is 0.05-25%.

[0068] Alternatively, the weight ratio of the total weight of the oxime ester photoinitiator and the auxiliary agent to the weight of the photopolymerizable composition is 0.05-25%.

[0069] Specifically, the auxiliary agent is selected from one or more of a photosensitizer, an adhesive polymer, a dispersant or a pigment.

[0070] Specifically, the photosensitizer includes, but is not limited to, compounds of benzophenone and its derivatives, thiazone and its derivatives, anthraquinone and its derivatives, or coumarin and its derivatives.

[0071] Specifically, the binder polymer includes, but is not limited to, copolymers of methacrylate and methacrylic acid.

[0072] Furthermore, component (a) further comprises a resin obtained by reacting an unsaturated polyacid anhydride, an epoxy resin and an unsaturated monocarboxylic acid.

[0073] Furthermore, component (a) further comprises an alkali-developable resin.

[0074] The polymerizable composition may optionally contain a photopolymerizable compound in an amount of 2 to 98 wt % based on the total solid components of the polymerizable composition.

[0075] Preferably, it is 4-96wt%.

[0076] Optionally, the alkali-developable resin has free carboxyl groups. The acid value may be 10-600 mg KOH / g, 10-600 mg NaOH, and the acid value stated herein is the acid value according to DIN EN12634.

[0077] Preferably, the acid value is 100-300 mg KOH / g, 100-300 mg NaOH / g.

[0078] Examples of base-developable resins are acrylic polymers having carboxylic acid functions as pendant groups.

[0079] According to the above technical requirements, examples of alkali-developable resins are acrylic polymers having carboxylic acid functions as pendant groups, including ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid monoesters, (meth)acrylates, vinyl aromatic compounds, amide unsaturated compounds, acetal esters or ketal ester compounds, polycyclic compounds or anhydrides, vinyl or allyl esters, and vinyl or allyl ethers.

[0080] The dispersant should be a high molecular weight polymer with pigment-affinity groups. It is selected from: statistical copolymers from styrene derivatives, (meth)acrylates, and (meth)acrylamide, and such statistical copolymers after post-modification; block copolymers and / or comb polymers from styrene derivatives, (meth)acrylates and (meth)acrylamide, and such block copolymers and / or comb polymers after post-modification; polyethyleneimines modified with polyesters; polyamines modified with polyesters; and many types of (modified) polyurethanes;

[0081] Optionally, the content of the dispersant is 1-80 wt % based on the mass of the pigment.

[0082] Preferably, the content of the dispersant is 5-70 wt % based on the mass of the pigment.

[0083] Optionally, the concentration of the pigment in the total solid component is in the range of 5 wt % to 80 wt %.

[0084] Preferably, the concentration of the pigment in the total solid component is in the range of 20 wt% to 65 wt%.

[0085] The binder polymer is a copolymer of methacrylate and methacrylic acid.

[0086] The present invention provides a photopolymerizable composition, which comprises at least one photoinitiator of formula (I) as described above, and is obtained by irradiation with electromagnetic radiation, in particular light with a wavelength of 280nm-400nm, electron beam, or X-ray.

[0087] The compounds of the present invention are used to manufacture pigmented and unpigmented paints and varnishes, powder coatings, printing inks, printed circuit boards, adhesives, dental materials, gel coatings, photoresists in electronic devices, packaging of electronic components, magnetic recording materials, micromechanical components, waveguides, optical switches, electroplating shielding and etching shielding materials, color proofing systems, glass fiber cable coatings, screen printing templates, three-dimensional object manufacturing materials, image recording materials, microelectronic circuits, decolorizers, OLED boundary and pixel definition layers, LCD and OLED sealants, LCD and OLED insulation and passivation layers, metal wiring in touch panels and insulating layers of transparent conductive films, touch panel coatings, decorative inks, protective films and anti-corrosive agents.

[0088] Compared with the prior art, the present invention has the following advantages and effects:

[0089] Compared with the prior art, the present invention introduces groups such as thiophene sulfone, thiophene sulfoxide, benzothiophene sulfone and benzothiophene sulfoxide into the photoinitiator, which is conducive to forming a rigid conjugated system. This conjugated effect can disperse the electron cloud in the molecule, thereby increasing the sensitivity of the photoinitiator, so that the photoinitiator designed by the present invention has good matching performance with the (UV-vis) LED light source of 320nm-400nm. At the same time, the stability of the chemical bond between Ar1 and the oxime ester is enhanced, thereby effectively preventing some adverse reactions that may occur under high temperature conditions, such as chemical bond breakage or structural rearrangement, thereby ensuring the reliability and efficiency of the photoinitiator in a variety of application environments, so that it can be widely used in the fields involved in (UV-vis) LED photocuring, such as coatings, inks, microelectronics, printing, 3D printing, dental materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0090] Figure 1 This is the NMR image of Example 1 in the present invention. DETAILED DESCRIPTION

[0091] The principles and features of the present invention are described below. The embodiments are only used to explain the present invention and are not used to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0092] The reagents or instruments used in the present invention, if the manufacturer is not specified, are all conventional products that can be purchased from the market. For process parameters not specifically specified, conventional techniques can be used.

[0093] Example 1

[0094] Synthesis of 1-(((1-(9-ethyl-6-(1-oxothiophene-2-carbonyl)-9H-carbazole-3-yl)ethylidene)amino)oxy)ethan-1-one

[0095]

[0096] Step 1: N-ethylcarbazole (20 g, 1 eq) and AlCl3 (27.31 g, 2 eq) were added to 200 g of dichloromethane, and 75 ml of dichloromethane solution of 2-thiophenecarbonyl chloride (18.02 g, 1.2 eq) was slowly added dropwise, and the mixture was added at -20 to 10 ° C. The reaction was allowed to proceed at room temperature. After the reaction was complete, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HCl at 0 ° C. and stirred for 30 min. The organic phase was retained and the aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic phases were combined and 100 ml of 0.1 mol / L sodium bicarbonate solution, stir and shake, adjust the pH to neutral, retain the organic phase, dry with 20g anhydrous magnesium sulfate, filter, rotary evaporate, add the solid to acetic acid (43.06g, 7.0eq), slowly add hydrogen peroxide (6.97g, 2eq), heat the reaction to 35°C and stir for 1h, rotary dry, add 200ml n-heptane, stir for 1-3h, filter, and dry to obtain 26.61g of the reaction intermediate;

[0097] Step 2: The product of step 1 (26.61 g, 1.0 eq) and AlCl3 (22.08 g, 2.0 eq) were added to 200 g of dichloromethane, and acetyl chloride (7.80 g, 1.2 eq) was slowly added dropwise at 0°C, and the mixture was added at -20 to 10°C and reacted at room temperature. After the reaction was complete, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HCl at 0°C, stirred for 30 min, and separated at rest. The organic phase was retained, and the aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic phases were combined, and 100 ml of 0.1 mol / L sodium bicarbonate solution was added. The mixture was stirred and shaken, and the pH was adjusted to neutral. The organic phase was retained, and dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain 24.42 g of the intermediate;

[0098] Step 3: The product of step 2 (24.42 g, 1.0 eq), hydroxylamine hydrochloride (8.27 g, 1.5 eq), and sodium acetate (7.00 g, 1.5 eq) were added to 200 g of tetrahydrofuran and reacted for 6-12 h. After the reaction was completed by TLC, the reaction solution was added to 1000 ml of water, kept at 0°C overnight, and filtered to obtain a powdery solid. The powdery solid was dissolved in 100 ml of ethyl acetate, and 20 g of anhydrous magnesium sulfate was added for drying. The mixture was filtered, rotary evaporated, and dried to obtain 20.34 g of the intermediate.

[0099] Step 4: Add the product of step 3 (16.52g, 1.0eq) and acetyl chloride (5.06g, 1.2eq) to 200ml of dichloromethane, slowly add triethylamine (8.16g, 1.5eq) at 0℃, react at room temperature for 4-6h, after the reaction is complete, slowly add 500ml of water at 0℃, stir for 1h, let stand and separate, retain the organic phase, then adjust the pH of the organic phase to neutral with 0.1mol / L dilute hydrochloric acid, wash once with water, retain the organic phase, add 30g of anhydrous magnesium sulfate to the organic phase, dry, filter, and evaporate the solvent by rotation to obtain a viscous liquid with a purity greater than 93%. Dissolve the viscous liquid in 100ml of ethanol, and then add the ethanol solution dropwise to a large amount of water under high-speed stirring to precipitate a white solid product, filter, and dry to obtain 18.67g of the product;

[0100] Mass spectrometer MALDI-TOF-MS (m / z) = 420.1241, theoretical molecular weight: 420.1144. NMR image Figure 1 shown.

[0101] Example 2

[0102] Synthesis of 1-(((4-cyclopentyl-1-(9,9-dimethyl-6-(1-oxyenamide)-9H-fluoren-3-yl)butylene)amino)oxy)ethan-1-one

[0103]

[0104] The thiophene-2-carbonyl chloride in step 1 of Synthesis Example 1 was replaced with benzothiophene-2-carbonyl chloride, the N-ethylcarbazole in step 1 was replaced with 9,9-dimethyl-9H-fluorene, and the acetyl chloride in step 2 was replaced with 4-cyclopentylbutyryl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 1 (same reaction molar ratio and reaction conditions) to obtain 18.65 g of the target product;

[0105] Mass spectrometer MALDI-TOF-MS (m / z) = 565.2387, theoretical molecular weight: 565.2287.

[0106] Example 3

[0107] Synthesis of 1-(((1-(11-ethyl-8-(1-oxothiophene-2-carbonyl)-11H-benzo[a]carbazole-5-yl)ethylidene)amino)oxy)ethan-1-one

[0108]

[0109] The N-ethylcarbazole in step 1 of Synthesis Example 1 was replaced with 11-ethyl-11H-benzo[a]carbazole, and the target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 1 (same reaction molar ratio and reaction conditions) to obtain 21.94 g of the target product;

[0110] Mass spectrometer MALDI-TOF-MS (m / z) = 470.1367, theoretical molecular weight: 470.1300.

[0111] Example 4

[0112] Synthesis of 1-(((6-(1,1-dioxythiophene-2-carbonyl)-9-ethyl-9H-carbazole-3-yl)(thiophene-2-yl)methylene)amino)oxy)-3-methoxypropan-1-one

[0113]

[0114] The molar ratio of hydrogen peroxide in step 1 of Synthesis Example 1 was replaced with 2.2eq 4.08g, the acetyl chloride in step 2 was replaced with 2-thiopheneacetyl chloride, and the acetyl chloride in step 4 was replaced with 3-methoxypropionyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 1 (same reaction molar ratio and reaction conditions) to obtain 25.48g of the target product;

[0115] Mass spectrometer MALDI-TOF-MS (m / z) = 548.6387, theoretical molecular weight: 548.6280.

[0116] Example 5

[0117] Synthesis of (6-(1-(Benzoyloxy)imino)butyl)-9-ethyl-9H-carbazole-3-yl)(1,1-dioxidothiophene-2-yl)methanone

[0118]

[0119] The 2-thiopheneacetyl chloride in step 2 of Synthesis Example 4 was replaced with butyryl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with benzoyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 23.42 g of the target product;

[0120] Mass spectrometer MALDI-TOF-MS (m / z) = 526.1652, theoretical molecular weight: 526.1562.

[0121] Example 6

[0122] Synthesis of 1-(((8-(1,1-dioxyalkyleneamido)dibenzo[b,d]thiophen-2-yl)(4-(2,2,3,3,3-pentafluoropropoxy)phenyl)methylene)amino)oxy)ethan-1-one

[0123]

[0124] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced with dibenzothiophene, the thiophenecarbonyl chloride in step 1 was replaced with benzothiopheneacetyl chloride, the 2-thiopheneacetyl chloride in step 2 was replaced with 4-(2,2,3,3,3-pentafluoropropoxy)benzoyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 32.68 g of the target product;

[0125] Mass spectrometer MALDI-TOF-MS (m / z) = 685.0641, theoretical molecular weight: 685.0630.

[0126] Example 7

[0127] Synthesis of 1-((4-cyclopentyl-1-(6-(1,1-dioxythiophene-2-carbonyl)-9-ethyl-9H-carbazole-3-yl)butylidene)amino)propan-2-one

[0128]

[0129] The 2-thiopheneacetyl chloride in step 2 of Synthesis Example 4 was replaced with 4-cyclopentylbutyryl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 20.71 g of the target product.

[0130] Mass spectrometer MALDI-TOF-MS (m / z) = 530.2244, theoretical molecular weight: 530.2239.

[0131] Example 8

[0132] Synthesis of (1,1-dioxidothiophene-2-yl)(9-(2-ethylpentyl)-6-(1-(((thiophene-2-carbonyl)oxy)imino)ethyl)-9H-carbazole-3-yl)methanone

[0133]

[0134] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced with 9-(2-ethylpentyl)-9H-carbazole, the 2-thiopheneacetyl chloride in step 2 was replaced with acetyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with 2-thiopheneacetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 25.65 g of the target product;

[0135] Mass spectrometer MALDI-TOF-MS (m / z) = 574.1675, theoretical molecular weight: 574.1596.

[0136] Example 9

[0137] Synthesis of 1-(((4-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)phenyl)(6-(1,1-dioxooctanoyl)-9-ethyl-9H-carbazol-3-yl)methylene)amino)oxy)ethan-1-one

[0138]

[0139] The thiophene-2-carbonyl chloride in step 1 of Synthesis Example 4 was replaced with benzothiophene-2-carbonyl chloride, the 2-thiopheneacetyl chloride in step 2 was replaced with 4-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)benzoyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 22.37 g of the target product;

[0140] Mass spectrometer MALDI-TOF-MS (m / z) = 678.2055, theoretical molecular weight: 678.2036.

[0141] Example 10

[0142] Synthesis of (8-(1-(((cyclohexanecarbonyl)oxy)imino)butyl)dibenzo[b,d]thiophen-2-yl)(1,1-dioxybenzo[b]thiophen-2-ylmethanone

[0143]

[0144] The thiophene-2-carbonyl chloride in step 1 of Synthesis Example 4 was replaced by benzothiophene-2-carbonyl chloride, the N-ethylcarbazole in step 1 was replaced by dibenzo[b,d]thiophene, the 2-thiopheneacetyl chloride in step 2 was replaced by butyryl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced by cyclohexaneacetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 18.67 g of the target product;

[0145] Mass spectrometer MALDI-TOF-MS (m / z) = 571.1548, theoretical molecular weight: 571.1487.

[0146] Embodiment 11

[0147] Synthesis of 1-(((8-(1,1-dioxyalkyleneamido)-5,5-dioxydibenzo[b,d]thiophen-2-yl)(furan-2-yl)methylene)amino)oxy)ethan-1-one

[0148]

[0149] The thiophene-2-carbonyl chloride in step 1 of Synthesis Example 4 was replaced by benzothiophene-2-carbonyl chloride, the N-ethylcarbazole in step 1 was replaced by dibenzothiophene, and the 3-methoxypropionyl chloride in step 4 was replaced by acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 17.47 g of the target product;

[0150] Mass spectrometer MALDI-TOF-MS (m / z) = 575.0187, theoretical molecular weight: 575.0167.

[0151] Example 12

[0152] Synthesis of 1-(((1-(9-(4-benzoylphenyl)-6-(1,1-dioxycarbonyl)-9H-carbazole-3-yl)ethylidene)amino)oxy)ethyl-1-

[0153]

[0154] The thiophene-2-carbonyl chloride in step 1 of Synthesis Example 4 was replaced with benzothiophene-2-carbonyl chloride, the N-ethylcarbazole in step 1 was replaced with (4-(9H-carbazole-9-yl)phenyl)(phenyl)methanone, the 2-thiopheneacetyl chloride in step 2 was replaced with acetyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 19.51 g of the target product;

[0155] Mass spectrometer MALDI-TOF-MS (m / z) = 638.1252, theoretical molecular weight: 638.1542.

[0156] Embodiment 13

[0157] Synthesis of 1-((4-cyclopentyl-1-(6-(1,1-dioxythiophene-2-carbonyl)-9,9-diethyl-9H-fluoren-3-yl)butylidene)amino)propan-2-one

[0158]

[0159] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced by 9,9-diethylfluorene, the 2-thiopheneacetyl chloride in step 2 was replaced by 4-cyclopentylbutyryl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced by acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 24.52 g of the target product;

[0160] Mass spectrometer MALDI-TOF-MS (m / z) = 557.2676, theoretical molecular weight: 557.2600.

[0161] Embodiment 14

[0162] Synthesis of 1-(1-(9,9-dibutyl-6-(1,1-dioxyenoyl)-9H-fluoren-3-yl)-2-(thiophen-2-yl)ethylidene)amino)oxy)ethan-1-one

[0163]

[0164] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced by 9,9-dibutylfluorene, the thiophene-2-carbonyl chloride in step 1 was replaced by benzothiophene-2-carbonyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced by acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 21.62 g of the target product;

[0165] Mass spectrometer MALDI-TOF-MS (m / z) = 651.2147, theoretical molecular weight: 651.2113.

[0166] Embodiment 15

[0167] Synthesis of 1-(((1-(7-(1,1-dioxyalkyleneamido)-10-ethyl-10H-phenothiazin-3-yl)-2-methoxyethylidene)amino)oxy)ethan-1-one

[0168]

[0169] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced by 10-ethyl-10H-phenothiazine, the thiophene-2-carbonyl chloride in step 1 was replaced by benzothiophene-2-carbonyl chloride, the 2-thiopheneacetyl chloride in step 2 was replaced by propionyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced by acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 18.57 g of the target product;

[0170] Mass spectrometer MALDI-TOF-MS (m / z) = 548.6351, theoretical molecular weight: 548.6280.

[0171] Example 16

[0172] Synthesis of 1-((1-(4-(4-(1,1-dioxythiophene-2-carbonyl)benzoyl)phenyl)ethylidene)amino)oxy)ethan-1-one

[0173]

[0174] The target compound of the formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) except that N-ethylcarbazole in step 1 was replaced with dibenzophenone, 2-thiopheneacetyl chloride in step 2 was replaced with acetyl chloride, and 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride, to obtain 19.41 g of the target product;

[0175] Mass spectrometer MALDI-TOF-MS (m / z) = 423.0835, theoretical molecular weight: 423.0777.

[0176] Embodiment 17

[0177] Synthesis of 1-((1-(6-(1,1-dioxythiophene-2-carbonyl)-9,9-dimethyl-9H-thioxanthene-3-yl)ethylidene)amino)oxy)ethan-1-one

[0178]

[0179] The N-ethylcarbazole in step 1 of Synthesis Example 4 was replaced with 9,9-dimethyl-9h-thioxanthine, the 2-thiopheneacetyl chloride in step 2 was replaced with acetyl chloride, and the 3-methoxypropionyl chloride in step 4 was replaced with acetyl chloride. The target compound of the above formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) to obtain 20.48 g of the target product;

[0180] Mass spectrometer MALDI-TOF-MS (m / z) = 467.0965, theoretical molecular weight: 467.0861.

[0181] Embodiment 18

[0182] Synthesis of 2-((Benzoyloxy)imino)-1-(8-(1,1-dioxybenzo[b]thiophen-2-yl)dibenzo[b,d]thiophen-2-alkyl)pentan-1-one

[0183]

[0184] Step 1: Add dibenzothiophene-2-boric acid (20 g, 1.0 eq) and 2-bromo-6,7-dihydrobenzo[b]thiophene (22.64 g, 1.2 eq) to a 200 ml toluene:water solution of 1:3, turn on nitrogen protection, add tetraphenylphosphine palladium (101.34 mg, 0.001 eq), heat to 90 ° C, react for 12 h, stand, retain the organic phase, wash the aqueous phase with 50 ml toluene 2-3 times, combine the organic phases, spin dry, dissolve the solid in 100 ml ethanol, heat under reflux and stir for 1 h, filter while hot, cool the filtrate for crystallization, filter, dry, dissolve the solid in acetic acid (36.86 g, 7.0 eq), slowly add hydrogen peroxide (5.97 g, 2 eq), react at room temperature for 5-6 h, spin dry to obtain 25.67 g of solid;

[0185] Step 2: The product of step 1 (25.67 g, 1.0 eq) and aluminum chloride (19.56 g, 2.0 eq) were dissolved in 200 ml of dichloromethane, butyryl chloride (29.42 g, 1.2 eq) was slowly added dropwise at 0°C, and reacted at room temperature. After the reaction was complete, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HCl at 0°C, stirred for 30 min, and separated at rest. The organic phase was retained, and the aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic phases were combined, 100 ml of 0.1 mol / L sodium bicarbonate solution was added, stirred and shaken, and the pH was adjusted to neutral. The organic phase was retained, dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain 26.37 g of the intermediate;

[0186] Step 3: Add the product of step 2 (26.37, 1eq), isobutyl nitrite (8.17g, 1.3eq), and concentrated hydrochloric acid (6.17g, 1.0eq) to 140ml DMF, stir at 45°C for 3-5h. After the reaction is completed, add 1000ml of water, stir, let stand, retain the organic phase, wash the aqueous phase with 100ml of n-heptane 1-2 times, combine the organic phases, add 300ml of water, stir, adjust the pH to 7 with 0.5mol / L sodium bicarbonate, retain the organic phase, wash the aqueous phase with 100ml of n-heptane 1-2 times, combine the organic phases, spin-dry, add methylcyclohexane and heat reflux for 1h, filter while hot, spin-dry, and dry to obtain 24.69g of the intermediate;

[0187] Step 4: The product of step 3 (24.69g, 1.0eq) and phenylacetyl chloride (9.02g, 1.2eq) were added to 200ml of dichloromethane, and triethylamine (8.12g, 1.5eq) was slowly added dropwise at 0℃, and the reaction was carried out at room temperature for 4-6h. After the reaction was complete, 500ml of water at 0℃ was slowly added dropwise, stirred for 1h, and the organic phase was retained. The pH of the organic phase was then adjusted to neutral with 0.1mol / L dilute hydrochloric acid, washed once with water, and the organic phase was retained. 30g of anhydrous magnesium sulfate was added to the organic phase for drying, filtering, and rotating to evaporate the solvent to obtain a viscous liquid with a purity greater than 93%. The viscous liquid was dissolved in 100ml of ethanol, and then the ethanol solution was added dropwise to a large amount of water under high-speed stirring to precipitate a white solid product, which was filtered and dried to obtain 26.26g of the product;

[0188] Mass spectrometer MALDI-TOF-MS (m / z) = 565.1017, theoretical molecular weight: 565.1018.

[0189] Embodiment 19

[0190] Synthesis of 2-((Benzoyloxy)imino)-1-(6-(1,1-dioxythiophene-2-carbonyl)-9-ethyl-9H-carbazol-3-yl)pentan-1-one

[0191]

[0192] Step 1: N-ethylcarbazole (20 g, 1.0 eq) and aluminum chloride (27.31 g, 2.0 eq) were dissolved in 200 ml of dichloromethane, and thiopheneacetyl chloride (18.02 g, 1.2 eq) was slowly added dropwise at 0°C. The mixture was reacted at room temperature. After the reaction was complete, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HCl at 0°C, stirred for 30 min, and separated at rest. The organic phase was retained. The aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic phases were combined, 100 ml of 0.1 mol / L sodium bicarbonate solution was added, stirred and shaken, the pH was adjusted to neutral, the organic phase was retained, and dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain 28.69 g of the intermediate;

[0193] Step 2: The product of step 1 (28.69 g, 1.0 eq) and aluminum chloride (22.68 g, 2.0 eq) were dissolved in 200 ml of dichloromethane, and valeryl chloride (12.30 g, 1.2 eq) was slowly added dropwise at 0°C, and reacted at room temperature. After the reaction was complete, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HCl at 0°C, stirred for 30 min, and separated at rest, and the organic phase was retained. The aqueous phase was washed 2-3 times with 50 ml of dichloromethane, the organic phases were combined, 100 ml of 0.1 mol / L sodium bicarbonate solution was added, stirred and shaken, the pH was adjusted to neutral, the organic phase was retained, and dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain 28.75 g of the intermediate;

[0194] Step 3: Add the product of step 2 (28.75g, 1eq), isobutyl nitrite (10.55g, 1.3eq), and concentrated hydrochloric acid (6.91g, 1.0eq) to 140ml DMF, stir at 45°C for 3-5h. After the reaction is completed, add 1000ml of water, stir, let stand, retain the organic phase, wash the aqueous phase with 100ml of n-heptane 1-2 times, combine the organic phases, add 300ml of water, stir, adjust the pH to 7 with 0.5mol / L sodium bicarbonate, retain the organic phase, wash the aqueous phase with 100ml of n-heptane 1-2 times, combine the organic phases, spin-dry, add methylcyclohexane and heat reflux for 1h, filter while hot, spin-dry, and dry to obtain 26.38g of the intermediate;

[0195] Step 4: The product of step 3 (24.69g, 1.0eq) and phenylacetyl chloride (9.88g, 1.2eq) were added to 200ml of dichloromethane, and triethylamine (11.85g, 1.5eq) was slowly added dropwise at 0℃, and the reaction was carried out at room temperature for 4-6h. After the reaction was complete, 500ml of water at 0℃ was slowly added dropwise, stirred for 1h, and the organic phase was retained. The pH of the organic phase was then adjusted to neutral with 0.1mol / L dilute hydrochloric acid, washed once with water, and the organic phase was retained. 30g of anhydrous magnesium sulfate was added to the organic phase for drying, filtering, and rotating to evaporate the solvent to obtain a viscous liquid with a purity greater than 93%. The viscous liquid was dissolved in 100ml of ethanol, and then the ethanol solution was added dropwise to a large amount of water under high-speed stirring to precipitate a white solid product, which was filtered and dried to obtain 24.26g of the product;

[0196] Mass spectrometer MALDI-TOF-MS (m / z) = 554.1524, theoretical molecular weight: 554.1512.

[0197] Embodiment 20

[0198] Synthesis of 2-((Benzoyloxy)imino)-1-(4-((4-(1,1-dioxyalkyleneamido)phenyl)thio)phenyl)octan-1-one

[0199]

[0200] The target compound of the formula was prepared in substantially the same manner as in Synthesis Example 4 (same reaction molar ratio and reaction conditions) except that N-ethylcarbazole in Step 1 of Synthesis Example 19 was replaced by dibenzosulfide, thiopheneyl chloride in Step 1 was replaced by benzothiopheneyl chloride, and valeryl chloride in Step 2 was replaced by octanoyl chloride, and 20.48 g of the target product was obtained;

[0201] Mass spectrometer MALDI-TOF-MS (m / z) = 777.1736, theoretical molecular weight: 777.1622.

[0202] 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.

[0203] (Comparative Example 1) (Comparative Example 2)

[0204] (Comparative Example 3) (Comparative Example 4)

[0205] 1. Maximum absorption wavelength and molar absorption coefficient

[0206] 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 ).

[0207] 2.Light sensitivity

[0208] 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 the exposure dose that the thickness of the step mask pattern was maintained at 80% of the initial thickness, and the exposure dose that 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 1.

[0209] Table 1

[0210]

[0211] According to the data in Table 1, it can be clearly seen that the compounds of the present invention are significantly better than those of Comparative Examples 1 to 4 in terms of photosensitivity. Specifically, the photoinitiator of the present invention has excellent light absorption capacity in the wavelength range of 280-400nm, and can rapidly generate free radicals or other active substances under such light irradiation. These active substances will effectively initiate polymerization or cross-linking reactions, thereby significantly improving the efficiency and speed of the reaction. Compared with the comparative examples, the photoinitiator of the present invention has stronger photosensitivity, so that the required photoinitiator concentration can be significantly reduced, thereby reducing interference with other ingredients in the formula, and is particularly suitable for dark light curing systems, thereby improving the performance of the final product.

[0212] Sulfone and sulfoxide can act as free radical scavengers, which can react with free radicals generated during photoinitiation, thereby reducing the formation of peroxy radicals between free radicals and oxygen, thereby overcoming oxygen inhibition.

[0213] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An oxime ester photoinitiator, characterized in that: A compound having a structure shown in formula (I): Wherein, Ar1 is selected from the structure shown in formula (II), is the substitution site, X1 is a C4-C 12 heteroaryl; R1 is hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, C3-C6 heterocyclic aryl, or a substituted or unsubstituted C6-C 12 The aromatic group; R2 is hydrogen, or C1-C8 alkyl, which is unsubstituted or substituted by halogen, or C1-C8 alkoxy, which is unsubstituted or substituted by halogen, or C3-C 10 The cycloalkyl group is unsubstituted or substituted with a C1-C8 alkyl group, or a C3-C 10 The heterocycloalkyl group is unsubstituted or substituted with a C1-C8 alkyl group and contains 1-2 O or S, or C6-C 12 Aryl, which is unsubstituted or substituted by 1 to 2 groups selected from C1-C8 alkyl, C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, and the C1-C8 alkyl is interrupted by one or more O, and / or substituted by halogen, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl; R3 and R4 form a fused ring structure with -CH=CH-CH=CH- through a shared chemical bond; R5 is connected to X1 in formula (I); R6 is selected from: hydrogen, C1-C8 alkyl, C1-C8 alkoxy; The remaining R7-R9 are the same or different and are independently hydrogen, nitro, cyano, C1-C8 alkyl, C1-C8 alkoxy; Y1 is C(R 10 )(R 11 ), C(=O), N(R 12 ), O, S, S(=O) or S(=O)2; Y2 is empty, a direct bond, O or S; R 10 -R 11 The same or different, independently of each other, are hydrogen, C1-C9 alkyl, C6-C 12 Aromatic ketone group; R 12 Alkyl selected from C1-C9, C6-C 12 Aromatic ketone group; a1 and a2 are the same or different, and are independently 0 or 1.

2. The oxime ester photoinitiator according to claim 1, characterized in that: R1 is C6-C 12 When the aryl group is C1-C8, the substituent is one or more substituents selected from C1-C8 alkyl and C1-C8 alkoxy groups; R2 is substituted C3-C 10 When the cycloalkyl group is substituted with a C1-C8 alkyl group; R2 is substituted C3-C 10 When the heterocycloalkyl group is a C1-C8 alkyl group, the substituent is a C1-C8 alkyl group and contains 1-2 O, S, or N atoms; R2 is substituted C6-C 12 When the aryl group is an aryl group, the substituents are 1 to 2 substituents selected from C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C3-C6 cycloalkyl, and C3-C6 heterocycloalkyl, and the carbon atoms in the substituents are not interrupted or are interrupted by at least one O.

3. The oxime ester photoinitiator according to claim 1, characterized in that: X1 is represented by the following structural formula (VI): Y3 is sulfinyl or sulfonyl; R 13 -R 15 are the same or different, all are hydrogen, or one of them is nitro, cyano, C1-C8 alkyl, C1-C8 alkoxy, or, R 13 and R 14 , R 14 and R 15 One pair is -CH=CH-CH=CH-, wherein H is unsubstituted or substituted by C1-C8 alkyl or C1-C8 alkoxy.

4. The oxime ester photoinitiator according to claim 1, characterized in that: The structure represented by formula (II) is selected from one of the following formulas (III)-(V):

5. The oxime ester photoinitiator according to claim 1, characterized in that: R2 is C6-C 12 When the aryl group is R2, R2 is represented by the following structural formula (VII): Among them, R 16 -R 20 1 to 3 non-adjacent groups are independently one or two of C1-C8 alkyl, C1-C8 alkoxy, fluorinated C1-C8 alkyl, fluorinated C1-C8 alkoxy, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, and the C1-C8 alkyl and C1-C8 alkoxy groups are not interrupted or are interrupted by 1-2 Os.

6. The oxime ester photoinitiator according to claim 1 or 5, characterized in that: The C3-C6 cycloalkyl group is a monocyclic cycloalkyl group selected from a saturated five-membered ring or a six-membered ring; The C3-C6 heterocycloalkyl is a monocyclic heterocycloalkyl selected from a saturated five-membered ring or a six-membered ring containing O and N heteroatoms; The C3-C6 heterocyclic aromatic group is a five-membered ring, a six-membered ring or a benzo five-membered ring, and the heteroatom is selected from O, N, and S; C6-C 12 The aryl group is a benzene ring.

7. The oxime ester photoinitiator according to claim 1, characterized in that: The oxime ester photoinitiator shown is one of the following structural formulas:

8. A photopolymerizable composition, characterized in that include: (a) at least one ethylenically unsaturated photopolymerizable compound; (b) an oxime ester photoinitiator according to any one of claims 1 to 7; (c) Additives.

9. The photopolymerizable composition according to claim 8, characterized in that: The weight ratio of the oxime ester photoinitiator to the photopolymerizable composition is 0.05-25%; Alternatively, the weight ratio of the total weight of the oxime ester photoinitiator and the auxiliary agent to the weight of the photopolymerizable composition is 0.05-25%; The auxiliary agent is selected from one or more of a photosensitizer, an adhesive polymer, a dispersant or a pigment.

10. The photopolymerizable composition according to claim 8 or 9, characterized in that: The photosensitizer is selected from benzophenone and its derivatives, thiazone and its derivatives, anthraquinone and its derivatives, or coumarin and its derivatives; And / or, the binder polymer is selected from one or more of methacrylate or methacrylic acid copolymers.

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