Ketoxime ester photoinitiator, application thereof and photosensitive composition

Abstract

The invention belongs to the technical field of photoinitiators, and particularly relates to a ketoxime ester photoinitiator as well as application and a photosensitive combination thereof. Compared with the prior art, the novel photoinitiator has the advantages that by introducing a sulfone phenyl specific structure to a ketoxime ester group and the like, excellent photosensitivity can be shown in the optical wavelength range of 280-400 nanometers, and compared with OXE-01 and OXE-02 commonly used in the market, the novel photoinitiator can show better photoinitiation efficiency under an ultraviolet visible (UV-Vi s) LED light source.

Description

Technical Field

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

[0002] Photoinitiator compounds are important fine organic chemical materials and are widely used in the field of radiation curing technology, which uses ultraviolet light, visible light or new (UV-VIS) LED light sources to achieve curing. Under light conditions, these photoinitiators can generate free radicals, thereby catalyzing efficient photopolymerization reactions of olefin-containing unsaturated systems. Photocuring technology has the advantages of energy saving and environmental protection, high efficiency and speed, and time and space controllability. It has been applied to traditional fields such as coatings, inks, adhesives, as well as high-tech products such as 3D printing. The formulation of photosensitive resins used for photocuring usually contains photoinitiators, active diluents, oligomers and a variety of additives. The activity of the photoinitiator directly affects the rate of photocuring, the degree of curing and the performance of the final product. Compared with traditional ultraviolet light curing methods, the use of photocuring technology has significant advantages such as higher energy utilization, lower thermal effects and no ozone generation. However, traditional photoinitiators are mainly targeted at shorter wavelength ultraviolet light curing, which is difficult to effectively match with (UV-VIS) LED light sources. Therefore, through rational molecular design and systematic study of its structure-activity relationship, a series of highly efficient (UV-VIS) LED photoinitiators have been developed, showing broad application prospects.

[0003] Ketoximate esters are a class of photoinitiators with a wide range of uses. The most widely used photoinitiators on the market are OXE-01 and OXE-02. However, OXE-01 and OXE-02 have problems with poor solubility and low photosensitivity. Good solubility and high photosensitivity have become important trends in the application and development of technology in this field.

[0004] Summary of the invention

[0005] To address the deficiencies of the prior art, the present invention provides a ketoxime ester photoinitiator and its application and a photosensitive composition. The present invention also improves the solubility of the photoinitiator in the solvent, and can use less solvent to achieve the same effect, thereby improving the overall production efficiency and economy.

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

[0007] A ketoxime ester photoinitiator is a compound shown in Chemical Formula 1:

[0008]

[0009] is the substitution site;

[0010] a is 0 or 1;

[0011] d is 0 or 1; when d is 0, R1 is hydrogen, nitro or cyano; when d is 1, R1 is a substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 An aryl group or a group represented by Chemical Formula 3;

[0012] R2, R3 are substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C3-C 20 Heterocycloalkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C3-C 20 Heteroaryl, or a group represented by Chemical Formula 3;

[0013] At least one of R1, R2 and R3 is a group represented by Chemical Formula 3;

[0014] The alkoxy group or alkyl group is not interrupted or interrupted by one or more oxygen atoms, and part or all of the carbon chain of the cycloalkyl group, heterocycloalkyl group, aryl group or heteroaryl group is a ring;

[0015] Ar1 is a diaromatic ring and a five-membered ring or a diaromatic ring and a six-membered ring, the five-membered ring or the six-membered ring contains one or two of CR7R8, NR9, SO, SO2, O, CO, S; or Ar1 is a diaromatic ring bridged by a heteroatom, the heteroatom is SO, SO2, O, CO;

[0016] R7 and R8 are the same or different and are independently selected from hydrogen, C1-C 20 alkyl;

[0017] R9 is C1-C 20 Alkyl or C6-C 20 Aromatic ketone group;

[0018] in:

[0019]

[0020] b is 1 or 2;

[0021] R4 is C1-C 20 alkyl;

[0022] R 4a Selected from: C1-C 20 alkyl.

[0023] The above technical solution can exhibit excellent photosensitivity in the light wavelength range of 280-400 nanometers by introducing a specific structure of sulfone phenyl (shown in Chemical Formula 3) at the ketoxime ester group, etc. Compared with the commonly used OXE-01 and OXE-02 on the market, this new photoinitiator can show better reaction efficiency under ultraviolet visible (UV-Vis) LED light source.

[0024] Specifically, R1 is substituted C1-C 20 Alkyl, substituted C1-C 20 Alkoxy, substituted C3-C8 cycloalkyl, substituted C6-C 20 In the case of an aryl group, the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group.

[0025] Specific:

[0026] R2 is substituted C1-C 20 Alkoxy or substituted C1-C 20 When it is alkyl, the substituent is halogen, and the number of substituents is one or more;

[0027] Alternatively, R2 is substituted C3-C 20 When it is a cycloalkyl group, the substituent group is a C1-C6 alkyl group, and the number of the substituent groups is one or more;

[0028] Alternatively, R2 is substituted C6-C 20 When it is an aryl group, the substituent group is cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C8 heterocycloalkoxy, and the number of the substituent groups is one or more;

[0029] Alternatively, R2 is substituted C3-C 20 In the case of a heteroaryl group, the substituent group is a C1-C6 alkyl group, a C1-C6 alkoxy group or a C1-C6 haloalkyl group, and the number of the substituent group is one or more.

[0030] Specific:

[0031] R3 is substituted C6-C 20 Aryl or substituted C3-C 20 In the case of heteroaryl, the substituent is CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, the alkyl and alkoxy are uninterrupted or interrupted by at least one O, and the number of the substituent is one or more;

[0032] Alternatively, R3 is substituted C1-C 20When it is alkyl, the substituent is halogen, and the number of the substituent is one or more;

[0033] Alternatively, R3 is substituted C3-C 20 In the case of heteroaryl, the substituent is C1-C6 alkyl, C1-C6 alkoxy;

[0034] Alternatively, R3 is substituted C3-C 20 When it is a cycloalkyl group, the substituent group is a C1-C6 alkyl group;

[0035] Alternatively, R3 is substituted C3-C 20 In the case of a heterocycloalkyl group, the substituent group is a C1-C6 alkyl group.

[0036] Preferred:

[0037] R2 is C1-C8 alkyl, C1-C8 alkoxy, which is uninterrupted or interrupted by one or more oxygen atoms;

[0038] or R2 is C6-C 15 The phenyl group is unsubstituted or 1 to 3 non-adjacent hydrogen atoms are substituted by C1-C8 alkyl or C1-C8 alkoxy;

[0039] Preferred C6-C 15 The phenyl group is: phenyl, tolyl, ethylphenyl, methoxyphenyl, ethoxyphenyl;

[0040] or R2 is a C3-C8 monocyclic alkyl group, part or all of which is a ring;

[0041] Preferred C3-C8 monocycloalkyl groups are: cyclopropane, cyclohexane, cyclobutane;

[0042] or R2 is a C3-C8 monoheterocycloalkyl, part or all of which is a ring, and the monoheterocycloalkyl is a five-membered heterocycloalkyl or a six-membered heterocycloalkyl which is unsubstituted or has 1 to 3 hydrogen atoms substituted by a C1-C6 alkyl;

[0043] Preferred C3-C8 monoheterocycloalkyl groups are: cyclopropane, cyclohexane, cyclobutane containing 1-2 O, unsubstituted or substituted with at least 1-2 methyl groups;

[0044] Or R2 is a C5-C8 monoheteroaryl group, which is a five-membered aromatic ring containing one or more heteroatoms of O, S, and N.

[0045] Preferred are: thiophene, furan, pyrrole, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole;

[0046] More preferred are: thiophene and furan.

[0047] Preferred:

[0048] R3 is C1-C8 alkyl or C1-C8 alkoxy, which is uninterrupted or interrupted by one or more oxygen atoms;

[0049] Or R3 is C6-C 15 The phenyl group is unsubstituted or 1-3 non-adjacent hydrogen atoms of the phenyl group are substituted by C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy or C3-C8 cycloalkyl, each substituent is uninterrupted or is interrupted by one or more oxygen atoms, and part or all of the carbon chain of the C3-C8 cycloalkyl group is a ring.

[0050] Preferred C6-C 15 The phenyl group is phenyl, tolyl, mesityl, ethylphenyl, methoxyphenyl, ethoxyphenyl, pentafluoropropoxyphenyl;

[0051] Specific:

[0052] The chemical formula of Ar1 is selected from one of Chemical Formula 4 to Chemical Formula 6:

[0053]

[0054] Y1 is CR7R8, NR9, SO, SO2, O, CO, S;

[0055] Z1 is O, CO, SO, SO2, S;

[0056] Z1 and Y1 are not S, O, CO, NR9 at the same time;

[0057] n is 0 or 1;

[0058] R0 represents nitro, C1-C 20 Alkyl, C3-C 20 Cycloalkyl which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio.

[0059] Preferred:

[0060] When Ar1 is in chemical formula 4, R0 is H or It forms a condensed ring structure with the benzene ring connected thereto by sharing a chemical bond;

[0061] or when Ar1 is of Chemical Formula 5, R0 is H, C1-C5 alkyl, or C1-C5 alkoxy;

[0062] Or when Ar1 is of Chemical Formula 6, R0 is H, C1-C5 alkyl, C1-C5 alkoxy, and the C1-C5 alkyl is interrupted by multiple O or S or none.

[0063] C3-C20 The monocyclic alkyl group is a 3-membered to 6-membered cycloalkyl group, or a 3-membered to 5-membered cycloalkyl group connected via a C1-C6 alkyl group.

[0064] C3-C 20 The heterocycloalkyl group is a three-membered to six-membered heterocycloalkyl group, or a three-membered to five-membered heterocycloalkyl group connected via a C1-C6 alkyl group, and contains 1-2 O or N in the molecule.

[0065] Preferred C1-C5 alkyl groups are selected from: methyl and ethyl.

[0066] Preferred C1-C5 alkoxy groups are selected from: methoxy and ethoxy.

[0067] According to the above technical solution:

[0068] The C1-C8 alkyl group is selected from the group consisting of C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, and C1-C2 alkyl groups;

[0069] Preferred C1-C8 alkyl groups are: methyl, ethyl, propyl, C8, C6, C4 alkyl groups;

[0070] The C1-C8 alkoxy group is selected from the group consisting of C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, and C1-C2 alkoxy groups;

[0071] Preferred C1-C8 alkoxy groups are: methoxy, ethoxy, propoxy, butoxy;

[0072] Halogen is selected from: fluorine, chlorine, bromine;

[0073] Preferred is: fluorine.

[0074] All of the above “at least one, more than 1, at least one” are selected from: 1, 2, 3.

[0075] Specifically, the ketoxime ester photoinitiator is selected from the following compounds:

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] The present invention also provides a polymerization initiator, which at least contains the ketoxime ester photoinitiator provided by the present invention.

[0082] The compound provided by the present invention can be used as a photoinitiator in the fields of coatings, inks, microelectronics, printing and the like.

[0083] The present invention also provides a photosensitive composition, which contains the ketoxime ester photoinitiator and the ethylenically unsaturated compound provided by the present invention. Furthermore, the photosensitive composition contains a colorant.

[0084] The compound provided by the present invention has strong absorption in the wavelength range of 280-400nm, so it can be applied to (UV-VIS) LED light curing system.

[0085] The present invention also provides an alkali-developable photosensitive resin composition, which contains the ketoxime ester photoinitiator provided by the present invention and an alkali-developable compound, and further contains a colorant.

[0086] The present invention also provides an alkali-developable photosensitive resin composition, which contains the ketoxime ester photoinitiator, ethylenically unsaturated compound and alkali-developable compound provided by the present invention, and further contains a colorant.

[0087] Optionally, the amount of photoinitiator used is 0.01-10wt%, for example 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.2wt%, 2.5wt%, 2.8wt%, 3wt%, 3.2wt%, 3.5wt%, 3.8wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%.

[0088] Preferably, the photoinitiator is used in an amount of 0.1-6 wt %, such as 0.2-5 wt %, based on the amount of active ingredients in the photosensitive composition.

[0089] In the disclosed context, active ingredients refer to ingredients in the photosensitive composition other than the solvent. In addition to the photoinitiator of the present invention, the photosensitive composition further comprises a photocurable resin.

[0090] In the present invention, the photocurable resin refers to an oligomer or prepolymer containing unsaturated carbon-carbon double bonds. After being irradiated with light, the oligomer or prepolymer can be polymerized by a photoinitiator, and then cross-linked and cured. The photocurable resin is the main component of the photocurable product.

[0091] According to the above technical solution, the photocurable resin may be epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate, ethylenically unsaturated polyester, amino (meth) acrylate resin, photo-imaging alkali-soluble resin, etc. Advantageously, according to the present invention, epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate or a combination thereof is used;

[0092] The epoxy (meth) acrylate resin is preferably bisphenol A epoxy (meth) acrylate, bisphenol A epoxy acrylate diluted with tripropylene glycol di(meth) acrylate, or a combination thereof;

[0093] The polyester (meth)acrylate is preferably a hyperbranched polyester acrylate resin with high functionality, especially a hyperbranched polyester acrylate resin with a functionality of 5-30, such as a hyperbranched polyester acrylate prepolymer with a functionality of 6-20;

[0094] The urethane (meth)acrylate is preferably an aliphatic urethane acrylate.

[0095] According to the above technical solution, the amount of the photocurable resin in the photosensitive composition is 10-90wt%, for example, 15wt%, 20wt%, 25wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 85wt%;

[0096] Preferably, the amount of the photocurable resin in the photosensitive composition is 55-80 wt %.

[0097] In the context of this disclosure, active ingredients refer to ingredients in the photosensitive composition other than the solvent.

[0098] The photosensitive composition of the present invention may also optionally contain an organic solvent. The selection of the organic solvent is conventional. The optional organic solvents include: benzene, toluene, chloroform, dichloromethane, ethyl chloride, acetone, butanone, amyl ketone, methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol ether acetate.

[0099] The photosensitive composition of the present invention may also optionally contain other additives, such as a leveling agent, an antioxidant, an anti-settling agent, a colorant, a microbicide, such as an antibacterial agent, and a heat preservation material additive.

[0100] The preparation of the photosensitive composition of the present invention is conventional, and each component of the photosensitive composition of the present invention is uniformly mixed together.

[0101] The photoinitiator of the present invention is suitable for red photoresist, green photoresist, blue photoresist, black photoresist, dry film photoresist, liquid photosensitive solder resist ink, photosensitive character ink, temporary protective photoresist, etc.

[0102] The photoinitiator is preferably black photoresist.

[0103] According to one aspect of the present invention, a cured material obtained from the photosensitive composition of the present invention is provided. The obtained cured material can be a photocurable coating, which includes a coating containing a functional material, a coating of a color filter of UV light and / or visible light; a sealant; a photolithographic material; a holographic recording material; a 3D printing material; a lithographic printing material; a material for preparing an optical device and a material for improving mechanical properties, such as a carbon fiber composite material and / or an inorganic nanoparticle and / or an organic nanoparticle, etc.

[0104] The advantages of the present invention are:

[0105] 1. The present invention introduces sulfone phenyl groups into the photoinitiator molecules, which causes changes in the electron distribution within the molecules, thereby affecting the optical properties of the molecules. The sulfone group is a strong electron-withdrawing group, which pulls away part of the electron density through the inductive effect, affecting the electron cloud density distribution in the molecule. The introduction of the sulfone phenyl group strengthens the conjugated system within the molecule or changes the conjugation path, affecting the degree of delocalization of the π electrons. A stronger conjugation effect will lead to a decrease in the energy difference between the electron transition energy levels, so the wavelength of light absorbed by the photoinitiator will become longer, making the photoinitiator more suitable for LED light sources, which usually emit light waves of 280-400 nanometers;

[0106] 2. The present invention introduces sulfone phenyl into the photoinitiator molecule, thereby increasing its own polarity, and it will be more inclined to interact with polar or semi-polar small molecule organic solvents, thereby increasing the dipole-dipole interaction between the photoinitiator and the solvent, thereby improving the solubility of the photoinitiator in the solvent;

[0107] 3. The introduction of sulfone phenyl group enhances the electron withdrawal effect and conjugation effect of the photoinitiator molecule, increases the electron delocalization of the molecule, thereby expanding its absorption spectrum range and improving the sensitivity in organic solvents; at the same time, the sulfone group also improves the solubility and molecular dispersibility of the photoinitiator in the solvent, further enhancing its light absorption efficiency. The improvement of sensitivity makes the photoinitiator more sensitive to light, and can more effectively generate sufficient initiator molecules at lower light intensity, thereby increasing the speed of the polymerization reaction;

[0108] 4. The ketoxime ester photoinitiator of the present invention can initiate a photochemical reaction in a short time under weak light irradiation, and is more suitable for black photoresist. The photoresist prepared by using the photoinitiator of the present invention has a shortened exposure time, reduces pattern blurring caused by diffusion effect, and thus achieves higher resolution patterning;

[0109] 5. The raw materials for preparing the compounds provided by the present invention are all less toxic and easy to obtain. BRIEF DESCRIPTION OF THE DRAWINGS

[0110] Figure 1 This is the NMR of Example 1. DETAILED DESCRIPTION

[0111] 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.

[0112] 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.

[0113] Example 1

[0114]

[0115] Step 1: In a 500 ml three-necked flask, add 4-(methylsulfonyl)benzoyl chloride (1.2 eq, 20 g) shown in Chemical Formula 1-1 and N-ethylcarbazole (1 eq, 14.88 g) shown in Chemical Formula 1-2, dissolve in 200 ml of dichloromethane, lower the temperature of the reaction system to between -20 and 10 ° C with dry ice, slowly add aluminum chloride (2.0 eq, 20.33 g), wait for the reaction temperature to rise to 25 ± 5 ° C, and stir for 4-6 hours;

[0116] Post-treatment: slowly add the material to 0.1 mol / L dilute hydrochloric acid at 0°C, and then use a separatory funnel to separate the lower layer of the liquid; then extract the upper layer with dichloroethane, and combine the extract with the liquid; then wash with a solution containing 5% sodium bicarbonate water, and continue to wash with 200 ml of water three times until the pH value is neutral; then add 30 g of anhydrous magnesium sulfate to dry and remove water, and select to get a crude product; then dissolve the obtained crude product in 150 ml of anhydrous ethanol, heat to reflux state, cool to room temperature, and freeze in a refrigerator for 2 hours; finally, collect the product by suction filtration and dry at 75°C for 2 hours to obtain a white powder solid, and dry to get 23.61 g of the intermediate;

[0117] Step 2: In a 500 ml three-necked flask, add the product of step 1 (1 eq, 23.61 g) and acetyl chloride (1.2 eq, 5.89 g) shown in chemical formula 1-3 and dissolve them in 200 ml of dichloromethane. Use dry ice to lower the temperature of the reaction system to between -20 and 10 ° C., slowly add aluminum chloride (2.0 eq, 16.68 g), wait for the reaction temperature to rise to 25 ± 5 ° C, and stir for 4-6 hours;

[0118] Post-treatment: slowly add the material to 0.1 mol / L dilute hydrochloric acid at 0°C, and then use a separatory funnel to separate the lower layer of liquid; then extract the upper layer with 50 ml of dichloroethane, and combine the extract with the liquid; then wash with a solution containing 5% sodium bicarbonate water, and continue to wash with 200 ml of water three times until the pH value is neutral; then add 30 g of anhydrous magnesium sulfate to dry and remove water, and remove dichloroethane by a rotary evaporator; after evaporation, pour the solid powder in the bottle into 200 ml of n-heptane and filter; then dissolve the obtained crude product in 150 ml of anhydrous ethanol, heat to reflux state, cool to room temperature, and freeze in a refrigerator for 2 hours; finally, collect the product by suction filtration and dry at 75°C for 2 hours to obtain a white powder solid, and dry to obtain 21.57 g of the intermediate;

[0119] Step 3: Add the product of step 2 (21.57 g, 1.0 eq), hydroxylamine hydrochloride (6.33 g, 1.5 eq), and sodium acetate (5.36 g, 1.5 eq) to 200 g of tetrahydrofuran and react for 6-12 h;

[0120] Post-treatment: 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 THF, and dried by adding 20 g of anhydrous magnesium sulfate. The mixture was filtered, rotary evaporated, and dried to obtain 20.11 g of the intermediate.

[0121] Step 4: Add the product of step 3 (20.11 g, 1.0 eq) and 1-4-acetyl chloride (4.36 g, 1.2 eq) to 200 ml of dichloromethane, slowly add triethylamine (7.03 g, 1.5 eq) dropwise at 0°C, and react at room temperature for 4-6 hours;

[0122] Post-treatment: slowly add 500 ml of 0°C water and stir for 1 hour, then let stand to separate and retain the organic phase; next, use 0.1 mol / L dilute hydrochloric acid to adjust the pH of the organic phase to neutral, wash once and retain the organic phase again; then add 30 g of anhydrous magnesium sulfate to the organic phase for drying, filter and remove the solvent by rotary evaporator to obtain a viscous liquid; dissolve the viscous liquid in 100 ml of ethanol, and add its ethanol solution dropwise to a large amount of water under high-speed stirring to precipitate a white solid product, filter and dry to obtain the final product, and obtain 18.67 g of the product.

[0123] 1H NMR (400MHz, CDCl3): δ8.59(d,1H),8.27(d,1H),8.08-8.01(m,2H),7.97-7.89(m,2H),7.82(dd,1H),7 .73-7.66(m,1H),7.58-7.46(m,2H),4.28(q,2H),3.24(s,3H),2.30(s,3H),2.17(s,3H),1.37(t,3H).

[0124] MS: 476.1517 (accurate molecular mass: 476.1406).

[0125] NMR Figure 1 shown.

[0126] The synthesis steps of Example 2 to Example 18 are different from those of Example 1 except that one or more structures of 1-2, 1-3, and 1-4 are different. The target compounds of the above formula are prepared in basically the same manner (same reaction molar ratio and reaction conditions) as in Synthesis Example 1. The specific structures of 1-2, 1-3, and 1-4 are shown in Table 1.

[0127] Table 1

[0128]

[0129]

[0130]

[0131]

[0132] The synthesis steps of Example 19 to Example 26 are different from those in Example 1 except for one or more structures of 1-2, 1-3, and 1-4. Example 19 to Example 22 replace 1-1 in Example 1 with 4-(methylsulfinyl)benzoyl chloride, Example 23 replaces 1-1 in Example 1 with 4-(pentylsulfonyl)benzoyl chloride, and the synthesis of Example 24-25 does not require 1-1 in Example 1. Otherwise, the target compounds of the above formula are prepared in substantially the same manner as in Synthesis Example 1 (same reaction molar ratio and reaction conditions). The specific structures of 1-2, 1-3, and 1-4 are shown in Table 2.

[0133] Table 2

[0134]

[0135]

[0136] Embodiment 26

[0137]

[0138] Step 1: In a 500 ml three-necked flask, add 4-(methylsulfonyl)benzoyl chloride (1.2 eq, 20 g) and N-ethylcarbazole (1 eq, 14.88 g) shown in chemical formula 1-2 and dissolve in 200 ml of dichloromethane, lower the temperature of the reaction system to between -20 and 10 ° C with dry ice, slowly add aluminum chloride (2.0 eq, 20.33 g), and stir at 25 ± 5 ° C for 4-6 hours;

[0139] Post-treatment: slowly add the material to 0.1 mol / L dilute hydrochloric acid at 0°C, and use a separatory funnel to separate the lower layer of liquid; then extract the upper layer with 50 ml of dichloroethane, and combine the extract with the liquid; then wash with 5% sodium bicarbonate aqueous solution, and continue to wash with 200 ml of water three times until the pH value is neutral; then add 30 g of anhydrous magnesium sulfate to dry and remove water, and remove dichloroethane by rotary evaporator; after evaporation, pour the solid powder in the bottle into 200 ml of n-heptane and filter; then dissolve the obtained crude product in 150 ml of anhydrous ethanol, heat to reflux state, cool to room temperature, and freeze in a refrigerator for 2 hours; finally, collect the product by suction filtration and dry at 75°C for 2 hours to obtain a white powdery solid, 22.91 g of the intermediate;

[0140] Step 2: The product of step 1 (1 eq, 22.91 g) and acetyl chloride (1.2 eq, 6.74 g) shown in chemical formula 1-3 are dissolved in 200 ml of dichloromethane, the temperature of the reaction system is lowered to between -20 and 10 ° C with dry ice, aluminum chloride (2.0 eq, 16.19 g) is slowly added, and the reaction temperature is raised to 25 ± 5 ° C, and stirred for 4-6 hours;

[0141] Post-treatment: slowly add the material to 0.1 mol / L dilute hydrochloric acid at 0°C, and then use a separatory funnel to separate the lower layer of the feed liquid; then extract the upper layer with 50 ml of dichloroethane, and combine the extract with the feed liquid; then wash with a solution containing 5% sodium bicarbonate water, and continue to wash with 200 ml of water three times until the pH value is neutral; then add 30 g of anhydrous magnesium sulfate to dry and remove water, and remove dichloroethane by a rotary evaporator; after evaporation, pour the solid powder in the bottle into 200 ml of n-heptane and filter; then dissolve the obtained crude product in 150 ml of anhydrous ethanol, heat to reflux state, cool to room temperature, and freeze in a refrigerator for 2 hours; finally, collect the product by suction filtration and dry at 75°C for 2 hours to obtain a white powder solid, and dry to obtain 20.55 g of the intermediate;

[0142] Step 3: Add the product of step 2 (20.55 g, 1 eq), isobutyl nitrite (6.35 g, 1.3 eq), and concentrated hydrochloric acid (4.80 g, 1.0 eq) to 140 ml of DMF, and stir at 45°C for 3-5 h;

[0143] Post-treatment: add 1000ml of water, stir, 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 reflux for 1h, filter while hot, spin-dry, and dry to obtain 18.64g of the intermediate;

[0144] Step 4: In a 500 ml three-necked flask, the product of step 3 (18.64 g, 1.0 eq) and acetyl chloride (3.80 g, 1.2 eq) were added to 200 ml of dichloromethane, and triethylamine (6.12 g, 1.5 eq) was slowly added dropwise at 0°C and reacted at room temperature for 4-6 hours;

[0145] Post-treatment: slowly drop 500 ml of 0°C water and stir for 1 hour, then stand to separate and retain the organic phase; next, use 0.1 mol / L dilute hydrochloric acid to adjust the pH of the organic phase to neutral, wash once and retain the organic phase again; then add 30 g of anhydrous magnesium sulfate to the organic phase for drying, filter and remove the solvent by rotary evaporator to obtain a viscous liquid with a purity greater than 93%; dissolve the viscous liquid in 100 ml of ethanol, and 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 the final product, and obtain 17.29 g of the product;

[0146] 1 H NMR(400 MHz, CDCl3): δ8.60(dd,2H),8.08-8.01(m,2H),7.99-7.89(m,3H),7.82(dd,2H),7 .58-7.51(m,1H),4.28(q,2H),3.24(s,3H),2.44(s,3H),2.17(s,3H),1.37(t,3H).

[0147] MS: 504.1462 (accurate molecular mass: 504.1355).

[0148] 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 3.

[0149] (Comparative Example 1) (Comparative Example 2)

[0150] 1. Maximum absorption wavelength and molar absorption coefficient

[0151] 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 ).

[0152] 2. Solubility

[0153] 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.

[0154] 3. Light sensitivity

[0155] 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 photopolymerizable composition. The photopolymerizable 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.

[0156] Table 3

[0157]

[0158] 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. A ketoxime ester photoinitiator, characterized in that , is the compound shown in Chemical Formula 1: is the substitution site; a is 0 or 1; d is 0 or 1; when d is 0, R1 is hydrogen, nitro or cyano; when d is 1, R1 is a substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 An aryl group or a group represented by Chemical Formula 3; R2, R3 are substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C3-C 20 Heterocycloalkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C3-C 20 Heteroaryl, or a group represented by Chemical Formula 3; At least one of R1, R2 and R3 is a group represented by Chemical Formula 3; The alkoxy group or alkyl group is not interrupted or interrupted by one or more oxygen atoms, and part or all of the carbon chain of the cycloalkyl group, heterocycloalkyl group, aryl group or heteroaryl group is a ring; Ar1 is a diaromatic ring and a five-membered ring or a diaromatic ring and a six-membered ring, the five-membered ring or the six-membered ring contains one or two of CR7R8, NR9, SO, SO2, O, CO, S; or Ar1 is a diaromatic ring bridged by a heteroatom, the heteroatom is SO, SO2, O, CO; R7 and R8 are the same or different and are independently selected from hydrogen, C1-C 20 alkyl; R9 is C1-C 20 Alkyl or C6-C 20 Aromatic ketone group; in: Chemical formula 3 is as follows: b is 1 or 2; R4, R 4a C1-C 20 alkyl.

2. The ketoxime ester photoinitiator according to claim 1, characterized in that: R2 is substituted C1-C 20 Alkoxy or substituted C1-C 20 When it is alkyl, the substituent is halogen, and the number of substituents is one or more; Alternatively, R2 is substituted C3-C 20 When it is a cycloalkyl group, the substituent group is a C1-C6 alkyl group, and the number of the substituent groups is one or more; Alternatively, R2 is substituted C6-C 20 When it is an aryl group, the substituent group is cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C8 heterocycloalkoxy, and the number of the substituent groups is one or more; Alternatively, R2 is substituted C3-C 20 In the case of a heteroaryl group, the substituent group is a C1-C6 alkyl group, a C1-C6 alkoxy group or a C1-C6 haloalkyl group, and the number of the substituent group is one or more.

3. The ketoxime ester photoinitiator according to claim 1, characterized in that: R3 is substituted C6-C 20 Aryl or substituted C3-C 20 In the case of heteroaryl, the substituent is CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, the alkyl and alkoxy are uninterrupted or interrupted by at least one O, and the number of the substituent is one or more; Alternatively, R3 is substituted C1-C 20 When it is alkyl, the substituent is halogen, and the number of the substituent is one or more; Alternatively, R3 is substituted C3-C 20 In the case of heteroaryl, the substituent is C1-C6 alkyl, C1-C6 alkoxy; Alternatively, R3 is substituted C3-C 20 When it is a cycloalkyl group, the substituent group is a C1-C6 alkyl group; Alternatively, R3 is substituted C3-C 20 In the case of a heterocycloalkyl group, the substituent group is a C1-C6 alkyl group.

4. The ketoxime ester photoinitiator according to claim 1, characterized in that: The chemical formula of Ar1 is selected from one of Chemical Formula 4 to Chemical Formula 6: Y1 is CR7R8, NR9, SO, SO2, O, CO, S; Z1 is O, CO, SO, SO2, S; Z1 and Y1 are not S, O, CO, NR9 at the same time; n is 0 or 1; R0 is H or The adjacent benzene rings form a fused ring structure by sharing chemical bonds.

5. The ketoxime ester photoinitiator according to claim 1, characterized in that: R2 is C1-C8 alkyl, C1-C8 alkoxy, which is uninterrupted or interrupted by one or more oxygen atoms; Or R2 is C6-C 15 The phenyl group is unsubstituted or 1 to 3 non-adjacent hydrogen atoms are substituted by C1-C8 alkyl or C1-C8 alkoxy; or R2 is a C3-C8 monocyclic alkyl group, part or all of which is a ring; or R2 is a C5-C8 monoheteroaryl group, wherein the monoheteroaryl group is a five-membered aromatic ring containing one or more heteroatoms of O, S, and N; or R2 is a C3-C8 monocyclic alkyl group, part or all of which is a ring, and the monocyclic alkyl group is a five-membered cycloalkyl group or a six-membered cycloalkyl group which is unsubstituted or has 1 to 3 hydrogen atoms substituted by a C1-C6 alkyl group; R3 is C1-C8 alkyl or C1-C8 alkoxy, which is uninterrupted or interrupted by one or more oxygen atoms; Or R3 is C6-C 15 phenyl, the phenyl group is unsubstituted or 1-3 non-adjacent hydrogen atoms are substituted by C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy, or C3-C8 cycloalkyl, each of the substituent groups is uninterrupted or is interrupted by one or more oxygen atoms, and part or all of the carbon chain of the C3-C8 cycloalkyl group is a ring; or R3 is substituted C3-C 10 The heterocycloalkyl group contains at least one O atom in the molecule and is unsubstituted or substituted with at least one C1-C8 alkyl group.

6. The ketoxime ester photoinitiator according to claim 1, characterized in that: C3-C 20 The monocyclic alkyl group is a three-membered to six-membered cycloalkyl group, or a three-membered to five-membered cycloalkyl group connected via a C1-C6 alkyl group; C3-C 20 The heterocycloalkyl group is a three-membered to six-membered heterocycloalkyl group, or a three-membered to five-membered heterocycloalkyl group connected via a C1-C6 alkyl group, and contains 1-2 O or N in the molecule.

7. The ketoxime ester photoinitiator according to claim 1, characterized in that: Selected from the following compounds:

8. A polymerization initiator, characterized in that: Contains at least the ketoxime ester photoinitiator according to any one of claims 1 to 7.

9. A photosensitive composition, characterized in that: Contains the ketoxime ester photoinitiator according to any one of claims 1 to 7 and an ethylenically unsaturated compound, and may or may not contain a colorant.

10. An alkali-developable photosensitive resin composition, characterized in that: Containing the ketoxime ester photoinitiator according to any one of claims 1 to 7 and an alkali-developable compound; Or, containing the ketoxime ester photoinitiator and ethylenically unsaturated compound and alkali-developable compound according to any one of claims 1 to 7; The alkali-developable photosensitive resin composition may or may not contain a colorant.

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