Nitrocarbazole (ketone) oxime ester compounds, products containing the same, and use thereof

Abstract

The present application belongs to the technical field of photocuring, and relates to a nitrocarbazole (ketone) oxime ester compound, a product containing the same and application thereof. Specifically, the structure of the compound of the present application is, compared with existing and commercial photoinitiators, improved in photosensitivity, especially at a long wavelength.

Description

Technical Field

[0001] This invention belongs to the field of photocuring technology, and relates to nitrocarbazole (ketone) oxime compounds, products containing the same, and their applications in the field of photocuring. Background Technology

[0002] With the rapid development of the display industry towards higher color gamut, higher resolution, and larger sizes, color filters, as core components for achieving full-color displays in liquid crystal displays (LCDs) and organic light-emitting diode (OLEDs), face increasingly stringent performance requirements. Color photoresist, as a key material constituting color filters, directly determines the color reproduction, contrast ratio, and lifespan of the display. Currently, the mainstream method for preparing color photoresist is the pigment dispersion method. This process requires uniformly mixing components such as pigments, alkali-soluble resins, monomers, photoinitiators, and solvents, followed by coating, exposure, and development processes to form a precise pixel array. Among these, the photoinitiator, as the core component of the photocuring system, has a decisive influence on the photosensitivity, resolution, development characteristics of the photoresist, and the final film properties of the color photoresist (such as transmittance, heat resistance, and chemical resistance) due to its photoreactivity, stability, and compatibility with the system.

[0003] Early photoinitiators used in color photoresist systems, such as benzoin ethers, acetophenones, benzophenones, and phosphine oxides, while meeting basic photocuring requirements to some extent, generally suffered from drawbacks such as narrow ultraviolet absorption bands, low photosensitivity, poor thermal storage stability, and insufficient solubility in resin systems. These problems easily lead to particle defects in the photoresist during coating, incomplete cross-linking during exposure, low film retention after development, or rough pattern edges, making it difficult to meet the high precision and low defect rate process requirements of high-generation panel lines.

[0004] Oxime esters have attracted widespread attention due to their unique photodecomposition mechanism—the breaking of NO bonds within the molecule under light irradiation to generate highly reactive imine and acyloxy radicals—exhibiting excellent photoinitiation efficiency. Since oxime esters were first used as photoinitiators in the 1970s, their structures have undergone multiple rounds of optimization. Early products, such as oxyacyl oxime esters (Quanta cure PDO), while exhibiting high photoinitiation activity, suffered from poor molecular structural stability and were prone to thermal decomposition during storage or processing, leading to photoresist quality degradation and limiting their commercial application.

[0005] To address the aforementioned issues, researchers have modified the structure of oxime esters using molecular engineering strategies. This primarily involves introducing electron-donating groups with large conjugated systems, such as carbazole, diphenyl sulfide, and triphenylamine groups, to construct D-π-A type molecular structures. This design not only broadens the molecule's ultraviolet absorption spectrum, making it more effectively matched to the high-pressure mercury lamp's wavelength, but also... iLine (365 nm) and h The main emission lines, such as the 405 nm line, are enhanced, and the intramolecular charge transfer (ICT) effect is improved, effectively reducing the bond dissociation energy of the NO bond, thereby significantly improving the photoinitiation efficiency and free radical generation rate. In addition, the introduction of the large conjugated structure also significantly improves the thermal and storage stability of the oxime ester compounds.

[0006] However, with the continuous iteration of display technology, especially the application of new technologies such as Mini-LED backlighting, quantum dot (QD) films, and flexible displays, higher requirements have been placed on the weather resistance, optical transmittance, and environmental friendliness of color photoresists. Existing oxime ester photoinitiators still face the following technical bottlenecks that urgently need to be overcome: current molecular designs mostly focus on absorption in specific wavelength bands (such as 365 nm), lacking adaptability to broadband light sources or new LED light sources (such as 385 nm and 405 nm).

[0007] Therefore, research on novel high-sensitivity initiators for long wavelengths is ongoing. Summary of the Invention

[0008] In view of the above-mentioned problems existing in the prior art, the present invention provides a series of novel nitrocarbazole (ketone) oxime compounds, products containing the same, and their applications in the field of photocuring, in order to solve the above problems.

[0009] In a first aspect, the present invention provides a nitrocarbazole (ketone) oxime compound as shown in formula (A).

[0010]

[0011] in,

[0012] A is selected from a single bond or a carbonyl group;

[0013] R1 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl groups and substituted or unsubstituted C 6-20 Aryl;

[0014] R2 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl groups and substituted or unsubstituted C 6-20 Aryl;

[0015] R3 is selected from substituted or unsubstituted C3. 2-20 alkenyl, substituted or unsubstituted C 5-20 Cycloalkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20Cycloalkyl groups and substituted or unsubstituted C 6-20 Aryl;

[0016] R4 is selected from substituted or unsubstituted C4. 2-20 alkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, C 1-20 Alkyl carbonyl, substituted or unsubstituted C 6-20 Aryl carbonyl groups and substituted or unsubstituted 4-20 membered heteroaryl carbonyl groups;

[0017] The heteroaryl group contains 1 to 3 heteroatoms, each independently selected from N, O and S.

[0018] In a second aspect, the present invention provides a polymerizable composition / photosensitive composition comprising the nitrocarbazole (ketone) oxime compound described in the present invention.

[0019] Preferably, the polymerizable composition further comprises at least one of the following components:

[0020] a) Resin;

[0021] b) Monomer.

[0022] Thirdly, the present invention provides a photoresist comprising the following components:

[0023] i) The polymeric composition / photosensitive composition of the present invention;

[0024] ii) Additives.

[0025] Part Four: This invention provides the application of the nitrocarbazole (ketone) oxime ester compounds, polymerizable compositions / photosensitive compositions, or photoresists described in this invention in the field of photocuring.

[0026] The effects of the invention

[0027] Compared with existing and commercial photoinitiators, the nitrocarbazole (ketone) oxime esters of the present invention exhibit high sensitivity and good development performance at long wavelengths, such as 405 nm, making them novel photoinitiators with high sensitivity and efficient absorption of long-wavelength light sources. Attached Figure Description

[0028] Figure 1 The image shows the UV absorption spectrum of the oxime ester compound; the solvent is acetonitrile, with a concentration of 0.001 wt%. Detailed Implementation

[0029] Nitrocarbazole (ketone) oxime compounds

[0030] To address the problem of low sensitivity at long wavelengths in existing technologies, this invention provides a nitrocarbazole (ketoxime) ester compound with the structure shown in formula (A):

[0031]

[0032] in,

[0033] A is selected from a single bond or a carbonyl group;

[0034] R1 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl groups and substituted or unsubstituted C 6-20 Aryl;

[0035] R2 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl groups and substituted or unsubstituted C 6-20 Aryl;

[0036] R3 is selected from substituted or unsubstituted C3. 2-20 alkenyl, substituted or unsubstituted C 5-20 Cycloalkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C3-20 cycloalkyl, and substituted or unsubstituted C 6-20 Aryl;

[0037] R4 is selected from substituted or unsubstituted C4. 2-20 alkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, C 1-20 Alkyl carbonyl, substituted or unsubstituted C 6-20 Aryl carbonyl groups and substituted or unsubstituted 4-20 membered heteroaryl carbonyl groups;

[0038] The heteroaryl group contains 1 to 3 heteroatoms, each independently selected from N, O and S.

[0039] In one embodiment of the invention, "substituted" in "substituted or unsubstituted" means substituted by one or more substituents, each substituent being independently selected from deuterium, halogen, C. 1-20 Alkyl, C 1-20 Alkoxy, C 1-20 Alkyl carbonyloxy, C 1-20 Alkoxy C 1-20 Alkoxy, C 1-20 alkoxycarbonyl, C 1-20 Alkyl carbonyloxy, C 3-20 cycloalkyl, C 6-20 Aryl groups and 4-20 heteroaryl groups.

[0040] In one embodiment of the present invention, the structure of the nitrocarbazole (ketoxime) ester compound is shown in formulas (A-1) to (A-2):

[0041]

[0042] A, R1, R2, R3 and R4 are defined as in equation (A).

[0043] In one embodiment of the present invention, the structure of the nitrocarbazole (ketoxime) ester compound is shown in formulas (I) to (X):

[0044]

[0045] R1, R2, R3 and R4 are defined as in equation (A).

[0046] In one embodiment of the present invention, R1 is selected from C. 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 cycloalkyl C 1-6 Alkylenes and substituted or unsubstituted C 6-10 Aryl, the “substituted or unsubstituted C” 6-10 The substituents in "aryl" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy, C 1-6 Alkyl carbonyloxy, C 1-6 alkoxycarbonyl, C 3-6 Cycloalkyl, phenyl.

[0047] In one embodiment of the present invention, R1 is selected from C. 1-10 Alkyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl C 1-2 Alkylene and substituted or unsubstituted phenyl groups, wherein the substituents in "substituted or unsubstituted phenyl groups" are selected from halogens, C... 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkyl carbonyloxy, C 1-6 Alkoxycarbonyl group.

[0048] In one embodiment of the present invention, R1 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cycloheptylmethylene, cyclooctylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, cyclooctylethylene, and halogenated compounds, C 1-6 Alkyl-substituted or unsubstituted phenyl groups.

[0049] In one embodiment of the present invention, R1 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cyclopropylethylidene, cyclobutylethylidene, cyclopentylethylidene, cyclohexylethylidene, and halogenated compounds, C 1-6 Alkyl-substituted or unsubstituted phenyl groups.

[0050] In one embodiment of the invention, R1 is selected from methyl, ethyl, 2,4,4-trimethylpentyl, cyclohexyl, cyclopentylmethylene, cyclohexylmethylene, cyclopentylethylene, cyclohexylethylene, and halogenated, C 1-6 Alkyl-substituted or unsubstituted phenyl groups.

[0051] In one embodiment of the present invention, R2 is selected from C. 1-20 Alkyl, C 3-20 cycloalkyl and substituted or unsubstituted C 6-20 Aryl.

[0052] In one embodiment of the present invention, R2 is selected from C. 1-6 Alkyl, C 3-8 cycloalkyl and substituted or unsubstituted C 6-10 Aryl, the “substituted or unsubstituted C” 6-10 The substituents in "aryl" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy, C 1-6 Alkyl carbonyloxy, C 1-6 alkoxycarbonyl, C 3-6 Cycloalkyl, phenyl.

[0053] In one embodiment of the invention, R2 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, wherein the substituent in "substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl" is selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C1-6 Alkyl carbonyloxy, C 1-6 Alkoxycarbonyl group.

[0054] In one embodiment of the invention, R2 is selected from methyl and phenyl.

[0055] In one embodiment of the invention, the Choose one of the following structures:

[0056] .

[0057] In one embodiment of the present invention, R3 is selected from C. 2-8 alkenyl, cyclohexyl-1-enylmethylene, C 1-10 Alkyl, C 3-8 cycloalkyl C 1-2 Alkylene, substituted or unsubstituted C 6-10 Aryl and substituted or unsubstituted C 6-10 Aryl C 1-2 Alkylene, the “substituted or unsubstituted C 6-10 Aryl and substituted or unsubstituted C 6-10 Aryl C 1-2 The substituents in "alkylene" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy, C 1-6 Alkyl carbonyloxy, C 1-6 alkoxycarbonyl, C 3-6 Cycloalkyl, phenyl.

[0058] In one embodiment of the present invention, R3 is selected from allyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenylmethylene, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cycloheptylmethylene, cyclooctylmethylene, cyclopropylethylmethylene, cyclobutylethylmethylene, cyclopentylethylmethylene, cyclohexylethylmethylene, cycloheptylethylmethylene, cyclooctylethylmethylene, substituted or unsubstituted phenyl groups, and substituted or unsubstituted benzyl groups, wherein the substituents in "substituted or unsubstituted phenyl groups and substituted or unsubstituted benzyl groups" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkyl carbonyloxy, C 1-6 Alkoxycarbonyl group.

[0059] In one embodiment of the invention, R3 is selected from allyl, cyclopentenyl, cyclohexenyl, cyclopentenylmethylene, cyclohexenylmethylene, methyl, ethyl, propyl, butyl, 3-methylbutyl, 2-ethylhexyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentenylmethylene, cyclohexylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentenylethylene, cyclohexylethylene, and halogenated compounds, C 1-6 Alkyl-substituted or unsubstituted phenyl or benzyl groups.

[0060] In one embodiment of the present invention, R3 is selected from allyl, cyclopent-1-enylmethylene, cyclohex-1-enylmethylene, methyl, ethyl, 3-methylbutyl, and 2-ethylhexyl.

[0061] In one embodiment of the present invention, R4 is selected from allyl, C 1-20 Alkyl, C 3-20 cycloalkyl, C 1-20 alkyl carbonyl, C 6-10 aryl carbonyl, C 6-10 Aryl C 1-2 Alkylene carbonyl group.

[0062] In one embodiment of the present invention, R4 is selected from allyl, C 1-6 Alkyl, C 3-8 cycloalkyl, C 1-6 alkyl carbonyl, C 6-10 aryl carbonyl, C 6-10 Aryl C 1-2 Alkylene carbonyl group.

[0063] In one embodiment of the present invention, R4 is selected from allyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, octyl, nonyl, decyl, methyl carbonyl, ethyl carbonyl, propyl carbonyl, butyl carbonyl, phenyl carbonyl, naphthyl carbonyl, and benzyl carbonyl.

[0064] In one embodiment of the present invention, R4 is selected from allyl, methyl, ethyl, n-butyl, n-pentyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, methylcarbonyl, and phenylcarbonyl.

[0065] In one embodiment of the present invention, the nitrocarbazole (ketone) oxime compound may be selected from the following compounds:

[0066] .

[0067] In this invention, the term "halogen" or "halogenated" refers to F, Cl, Br, and I.

[0068] In this invention, the alkyl group can have 1 to 40 carbon atoms and can be a straight-chain or branched alkyl group. Preferably, the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40. Based on the linkage site, the alkyl group can be classified as primary alkyl (linked by CH2), secondary alkyl (linked by CH), and tertiary alkyl (linked by C). Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertiary butyl, pentyl, hexyl, octyl (such as n-octyl and isooctyl), nonyl, decyl, etc.

[0069] In this invention, the alkylene group is a group formed by further removing one hydrogen atom from an alkyl group.

[0070] In this invention, the cycloalkyl group is a saturated cyclic aliphatic hydrocarbon group with a specific number of carbon atoms, preferably containing 3 to 40 carbon atoms. Preferably, the number of carbon atoms can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornel, etc.

[0071] In this invention, the alkenyl group can have 2 to 40 carbon atoms, can be straight-chain or branched, and can contain one or more (e.g., 2, 3, 4 or more) carbon-carbon double bonds. When the number of carbon-carbon double bonds is more than 2, the carbon-carbon double bonds can be conjugated or non-conjugated. The position of the carbon-carbon double bonds can be at the linking end, in the middle of the chain, or at the end. The linking site of the alkenyl group can be on the carbon-carbon double bond or on a saturated carbon atom. Preferably, the number of carbon atoms can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40. Examples include, but are not limited to, vinyl, propenyl, and allyl groups.

[0072] In this invention, the cycloalkenyl group can have 3 to 40 carbon atoms and may contain one or more (e.g., 2, 3, 4 or more) carbon-carbon double bonds. When the number of carbon-carbon double bonds is more than two, the carbon-carbon double bonds can be conjugated or non-conjugated. The linkage site of the alkenyl group can be on the carbon-carbon double bond or on a saturated carbon atom. Preferably, the number of carbon atoms can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40. Examples include, but are not limited to, cyclopentenyl, cyclohexenyl, and cycloheptenyl.

[0073] In this invention, the aryl group represents the presence of 6 30 carbon atoms, or 6 25 carbon atoms, or 6 14 carbon atoms, or 6 Aromatic carbocyclic systems consisting of 10 carbon atoms, whether monocyclic, polycyclic, or fused rings, are referred to by the term "aryl" or "aromatic ring." Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, tetraphenyl, 1-phenylnaphthyl, 2-phenylnaphthyl, naphthyl, anthraceneyl, phenanthrene, triphenylene, pyrene, perylene, fluoranyl, benzo[a]fluorenyl, spirofluorenyl, and spirodifluorenyl.

[0074] In this invention, the heteroaryl group represents a group having 4-20 ring atoms, or 5-14 ring atoms, or 6 ring atoms. 13 ring atoms, or 3 A cyclic system of monocyclic, polycyclic, or fused rings with eight ring atoms, wherein one, two, three, or more ring atoms are heteroatoms and the remaining atoms are carbon atoms, the heteroatoms being independently selected from oxygen, sulfur, nitrogen, silicon, selenium, or phosphorus atoms. Examples of heteroaryl groups include, but are not limited to, pyrroleyl, furanyl, thiopheneyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyridazinyl, triazinyl, bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, spirofluorenoxanthyl, spirofluorenthionthanthyl, acridineyl, 9,10-dihydroacridyl, naphridyl, indolyl, isoyindolyl, phenoxazinyl, phenthiazinyl, phenoxthiazyl, quinolinyl, isoquinolinyl, and benzoquinoline. The following are listed: benzoisoquinolinyl, quinazolinyl, benzoquinazolinyl, quinoxalinyl, benzoquinoxalinyl, o-phenanthrolinel, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, benzothiopheneyl, isobenzothiopheneyl, benzothiazolyl, dibenzothiazolyl, naphthobenzothiazolyl, benzooxazolyl, naphthooxazolyl, benzoimidazolyl, naphthoimidazolyl, benzothiazolyl, naphthothiazolyl, carbazole, benzocarbazole, etc.

[0075] In this invention, "substituted or unsubstituted" means unsubstituted or substituted by a single or multiple group selected from the following: halogens such as chlorine / bromine / iodine / fluorine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-20 cycloalkyl (the C 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-20 Cycloalkyl groups can be further reacted with halogens such as chlorine / bromine / iodine / fluorine, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkyl thio, carboxyl, cyano, -SO2- C 1-6 Alkyl, -CF3, -OCF3, hydroxyl, mercapto substituted), -COOR or -OCOR (R is independently selected from C) 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group), C 6-20 Aryl groups (which can be further converted by halogens such as chlorine / bromine / iodine / fluorine, C) 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkyl thio, carboxyl, cyano, -SO2-C 1-6 Alkyl, -CF3, -OCF3, hydroxyl, mercapto, amino, amide, imide, cyclic imide, carbonyl, nitro substituted), 4-20 membered heteroaryl groups (which can be further substituted with halogens such as chlorine / bromine / iodine / fluorine, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkyl thio, carboxyl, cyano, -SO2- C 1-6 Alkyl, -CF3, -OCF3, hydroxyl, mercapto, amino, amide, imide, cyclic imide, carbonyl, nitro substituted). Further, in this invention, "substituted or unsubstituted" means unsubstituted or substituted by a single or multiple group selected from the following: chlorine, bromine, iodine, fluorine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, vinyl, propenyl, allyl, ethynyl, acrylate (-OCOCH=CH2), methacrylate (-OCOC(CH3)=CH2), allyloxycarbonyl (-COOCH2CH=CH2).

[0076] Preparation method of nitrocarbazole (ketoxime) ester compounds

[0077] The present invention also provides a method for preparing the nitrocarbazole (ketone) oxime ester compound, wherein the method is selected from one of the following methods:

[0078] When A is a single bond:

[0079] Method 1:

[0080]

[0081] Method 2:

[0082]

[0083] When A is a carbonyl group:

[0084] Method 3:

[0085]

[0086] Method 4:

[0087] .

[0088] Products containing nitrocarbazole (ketone) oxime photoinitiators

[0089] The above-mentioned nitrocarbazole (ketone) oxime compounds of the present invention can be used as photopolymerization initiators (or photoinitiators) in the field of photocuring, for example as photoinitiator components in polymerizable compositions (or photosensitive compositions) or photoresists.

[0090] Therefore, the present invention provides a polymerizable composition / photosensitive composition comprising the above-described nitrocarbazole (ketone) oxime compounds of the present invention.

[0091] In one embodiment of the present invention, the polymeric composition / photosensitive composition may further comprise at least one of the following components:

[0092] a) Resin;

[0093] b) Monomer.

[0094] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 1-10 parts of the carbazole (ketone) oxime compound of the present invention; 20-100 parts of resin; and / or 10-100 parts of monomer.

[0095] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 1-10 parts of the carbazole (ketoxime) ester compound of the present invention; 50-100 parts of resin; and / or 10-50 parts of monomer.

[0096] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 2-4 parts of the carbazole (ketone) oxime compound of the present invention; 70-80 parts of resin; and / or 35-50 parts of monomer.

[0097] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 2 parts of the carbazole (ketoxime) ester compound of the present invention; 70 parts of resin; and / or 40 parts of monomer.

[0098] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 1.5 parts of the carbazole (ketone) oxime compound of the present invention; 80 parts of resin; and / or 20 parts of monomer.

[0099] In one embodiment of the invention, the resin comprises an acrylic polymer.

[0100] In one embodiment of the invention, the acrylic polymer may be a polymer of an acrylic mixture, such as a polymer of a mixture of (meth)acrylic acid and one or more of its esters, or a polymer of a mixture of two or more (meth)acrylates.

[0101] In one embodiment of the present invention, the acrylic polymer may be a polymer of a mixture of methacrylic acid and methacrylate, for example, a polymer of a mixture of methacrylic acid, methyl methacrylate and isobornyl methacrylate, especially a polymer of a mixture in which the weight ratio of the three is 1:1:1.

[0102] In one embodiment of the present invention, the acrylic polymer may be a polymer of a mixture of methacrylic acid and methacrylates, such as a polymer of a mixture of methacrylic acid, hydroxyethyl methacrylate, methyl methacrylate and benzyl methacrylate, especially a polymer of a mixture in the weight ratio of the four components being 10-30:10-30:5-20:20-60, or a polymer of a mixture in the weight ratio of the four components being 30:20:15:35.

[0103] In one embodiment of the invention, the resin comprises a (meth)acrylate-styrene copolymer.

[0104] In one embodiment of the present invention, the (meth)acrylate-styrene copolymer may be a copolymer of (meth)acrylate and / or (meth)acrylate with styrene.

[0105] In one embodiment of the present invention, the (meth)acrylate-styrene copolymer may be a copolymer of methacrylic acid, butyl methacrylate and styrene, especially a polymer in which the weight ratio of the three is 15-50:20-70:10-35, or a polymer in which the weight ratio of the three is 30:50:20.

[0106] In one embodiment of the present invention, the acrylic polymer can be prepared by dissolving (meth)acrylates and a mixture of one or more of their esters, or a mixture of two or more (meth)acrylates, in a solvent and reacting them under the catalysis of an initiator to obtain the acrylic polymer.

[0107] In one embodiment of the present invention, the (meth)acrylate-styrene copolymer can be prepared by dissolving (meth)acrylic acid and / or (meth)acrylate and styrene in a solvent and reacting them under the catalysis of an initiator to obtain the (meth)acrylate-styrene copolymer.

[0108] Preferably, the solvent is selected from ketone solvents (e.g., acetone, butanone) and ethyl cellosolve (i.e., ethylene glycol monoethyl ether); the initiator is selected from azobisisobutyronitrile.

[0109] In one embodiment of the invention, the monomer is selected from at least one of (meth)acrylic acid and crosslinked (meth)acrylates.

[0110] In one embodiment of the invention, the crosslinked (meth)acrylate is selected from trimethylolpropane triacrylate.

[0111] In one embodiment of the invention, the monomer comprises, by weight, 5-20 parts of (meth)acrylic acid and / or 5-80 parts by weight of crosslinked (meth)acrylate. Preferably, it comprises, by weight, 5-15 parts of (meth)acrylic acid and 10-40 parts by weight of crosslinked (meth)acrylate; or 8-12 parts of (meth)acrylic acid and 25-35 parts by weight of crosslinked (meth)acrylate; or 10 parts of (meth)acrylic acid and 30 parts by weight of crosslinked (meth)acrylate. Alternatively, preferably, it comprises, by weight, 10-40 parts by weight of crosslinked (meth)acrylate; or 15-25 parts by weight of crosslinked (meth)acrylate; or 20 parts by weight of crosslinked (meth)acrylate.

[0112] In another embodiment of the invention, the polymeric composition / photosensitive composition may further comprise at least one of the following components:

[0113] a) Alkali-soluble resins;

[0114] b) Photopolymerizable compounds.

[0115] Preferably, the alkali-soluble resin includes the aforementioned acrylic polymers and (meth)acrylate-styrene copolymers.

[0116] Preferably, the photopolymerizable compound comprises a resin and a monomer. The resin includes polyester acrylate resin, polyurethane acrylate, bisphenol A epoxy acrylate, etc.; the monomer includes the monomers mentioned above herein.

[0117] In one embodiment of the invention, the polymeric composition / photosensitive composition may further contain additives.

[0118] Preferably, the additives are selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators, and thermal polymerization inhibitors.

[0119] The present invention also provides a photoresist comprising the following components:

[0120] i) The polymeric composition / photosensitive composition of the present invention;

[0121] ii) Additives.

[0122] In one embodiment of the present invention, the additives in the photoresist are selected from solvents, pigments, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators, and thermal polymerization inhibitors.

[0123] Applications of the product in the field of photocuring

[0124] This invention provides the application of the aforementioned nitrocarbazole (ketone) oxime compounds, polymerizable compositions / photosensitive compositions, or photoresists in the field of photocuring.

[0125] The present invention will be described in more detail below through specific embodiments, but the present invention is not limited to these embodiments. Unless otherwise stated, the reagents, materials and instruments used in these embodiments can be obtained by conventional commercial means.

[0126] Example 1: Synthesis of Compound 1

[0127] (1) Synthesis of compound S1:

[0128]

[0129] Under a nitrogen atmosphere, 7.5 g of 60% sodium hydride (NaH) and 7.5 g of anhydrous tetrahydrofuran were added to a dry three-necked flask. 14 g of 4-hydroxycarbazole was dissolved in a solution of 11 mL of N,N-dimethylformamide and 150 mL of anhydrous tetrahydrofuran and added dropwise. After 10 minutes, 13 g of iodoethane (as compound A) was added. The reaction mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was hydrolyzed and neutralized with 15% hydrochloric acid. After extraction with dichloromethane, the organic phase was dried over anhydrous sodium sulfate (Na₂SO₄) and concentrated under reduced pressure. The residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 9:1) to give 10.2 g of product S1, with a yield of 63.2%. MS (ESI+): m / z 212.2 [M+H] + .

[0130] (2) Synthesis of compound S2:

[0131]

[0132] S1 (10 g) and dichloroethane (50 mL) were added to a reaction flask, followed by aluminum trichloride (6.3 g) at 0-10 °C. After half an hour, propionyl chloride (4.4 g), representing compound B, was added dropwise at 0-10 °C, and the mixture was then heated to 60 °C for 2 h. After the reaction was complete, the reaction solution was poured into ice water, separated, and the organic phase was dried over anhydrous sodium sulfate (Na2SO4) and concentrated under reduced pressure. The residue was purified by column chromatography (eluent: petroleum ether: dichloromethane = 1:1) to give 9.5 g of product S2, with a yield of 75.1%.

[0133] MS (ESI+): m / z 268.3 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 13.82 (s,1H), 8.42 (d, J = 7.8Hz, 1H), 7.78 (d, J = 8.8 Hz, 1H), 7.50-7.44 (m, 1H),7.44-7.36 (m, 1H), 7.31 (d, J = 8.0 Hz, 1H), 6.87 (d, J = 8.8 Hz, 1H), 4.33(q, J = 7.3 Hz, 2H), 3.07 (q, J = 7.3 Hz, 2H), 1.44 (t, J = 7.2 Hz, 3H), 1.29(t, J = 7.3 Hz, 3H).

[0134] (3) Synthesis of compound S3:

[0135]

[0136] S2 (6 g), potassium carbonate (6.3 g), allyl bromide (3.3 g) as compound C, and DMF (50 mL) were added to the reaction flask, and the mixture was then heated to 80 °C and reacted for 4 h. After the reaction was completed, the reaction solution was poured into ice water, extracted with dichloromethane, dried with anhydrous sodium sulfate (Na2SO4), and concentrated under reduced pressure for later use.

[0137] (3) Synthesis of compound S4:

[0138]

[0139] Add S3 (10 g) and dichloroethane (50 mL) to the reaction flask, heat to 55-65 °C, and add 68% nitric acid (4.2 g) dropwise. After the addition is complete, maintain the temperature for 1 h. Add water, wash once with water, and then wash once with saturated sodium carbonate aqueous solution. After separation, concentrate the organic phase under reduced pressure to dryness, add 50 g of ethanol, and purify by heating to obtain 9.3 g of S4 product, with a yield of 81.7%.

[0140] MS (ESI+): m / z 353.3 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.62 (s,1H), 8.34 (d, J = 7.8 Hz, 1H), 8.06 (d, J = 8.5 Hz, 1H), 7.47 (d, J = 8.5 Hz,1H), 7.36-7.24 (m, 2H), 6.19-6.07 (m, 1H), 5.55 (d, J = 17.2 Hz, 1H), 5.37(d, J = 10.7 Hz, 1H), 4.72 (s, 2H), 4.33 (q, J = 7.3 Hz, 2H), 3.08 (q, J =7.3 Hz, 2H), 1.45 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.3 Hz, 3H).

[0141] (4) Synthesis of compound S5:

[0142]

[0143] Add 9 g of compound S4 and tetrahydrofuran (45 mL) to the reaction flask, stir until completely dissolved, then add 3.1 g of concentrated hydrochloric acid (30 wt%) at 0-10℃, stir until completely dissolved, cool to 0-5℃, add isoamyl nitrite (3.0 g), continue to keep warm for 2 h, quench the reaction with water, separate the liquid and liquid phases, extract the aqueous phase with dichloromethane, combine the two organic phases, dry with anhydrous sodium sulfate (Na2SO4), concentrate under reduced pressure for later use.

[0144] (5) Synthesis of Compound 1:

[0145]

[0146] The concentrated phase of compound S4 was added to the reaction flask, followed by 50 mL of dichloromethane. The mixture was then cooled to 5-15 °C, and triethylamine (2.6 g) was added dropwise. The mixture was then cooled to 0-5 °C, and acetyl chloride (2.0 g) was added dropwise. The reaction was allowed to proceed for 1 h. After the reaction was complete, the mixture was washed with water until neutral, separated, and the organic phase was concentrated to dryness. The solution was then slurried with ethanol to give solid compound 1 (9.0 g), with a yield of 83.2%.

[0147] MS (ESI+): m / z 424.3 [M+H] + .

[0148] Example 2: Synthesis of Compound 17

[0149] (1) Synthesis of compound S6:

[0150]

[0151] In the synthesis of compound 1 (1) In the synthesis of compound S1, compound A iodoethane is replaced with 2-ethyl iodohexane, so that S6 can be synthesized.

[0152] (2) Synthesis of compound S7:

[0153]

[0154] S6 (10 g), potassium carbonate (6.7 g), iodomethane (4.8 g) as compound D, and DMF (50 mL) were added to the reaction flask, and the mixture was then heated to 80 °C and reacted for 4 h. After the reaction was completed, the reaction solution was poured into ice water, extracted with dichloromethane, dried with anhydrous sodium sulfate (Na2SO4), concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: dichloromethane = 9:1) to give 9 g of product S7.

[0155] MS (ESI+): m / z 310.3 [M+H] + .

[0156] (3) Synthesis of compound S8:

[0157]

[0158] 9 g of S7 was added to the reaction flask, followed by 4.0 g of aluminum trichloride at 0-10 °C. After half an hour, 2.4 g of acetyl chloride (representing compound E) was added dropwise at 0-10 °C, and the mixture was then heated to room temperature for 2 h. After the reaction was complete, the reaction solution was poured into ice water, separated, and the organic phase was dried over anhydrous sodium sulfate (Na2SO4). After concentration under reduced pressure, the residue was purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1) to give 9.1 g of S8 product, with a yield of 89%.

[0159] MS (ESI+): m / z 352.4 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.94 (s,1H), 8.10 (d, J = 8.7, Hz, 1H), 7.42 (t, J = 8.1 Hz, 1H), 7.35 (d, J = 8.7Hz, 1H), 7.03 (d, J = 8.1 Hz, 1H), 6.74 (d, J = 8.0 Hz, 1H), 4.15 (d, J = 7.5Hz, 2H), 4.11 (s, 3H), 2.73 (s, 3H), 2.04 (p, J = 6.5 Hz, 1H), 1.46-1.18 (m,8H), 0.97-0.75 (m, 6H).

[0160] (2) Synthesis of compound S9:

[0161]

[0162] Add 9 g of S8 to the reaction flask, heat to 25-35 °C, and add 3.3 g of 68% nitric acid dropwise. After the addition is complete, maintain the temperature for 1 h. Add water, wash once with water, then wash once with saturated sodium carbonate aqueous solution, and concentrate to dryness under reduced pressure. Add methanol (150 mL), heat to 50-60 °C, stir for 1 h, cool to room temperature, and filter to obtain a yellow solid compound S9 (9.0 g), with a yield of 88.6%.

[0163] MS (ESI+): m / z 397.4 [M+H] + . 1H NMR (400 MHz, Chloroform-d) δ 8.95 (s,1H), 8.24-8.15 (m, 2H), 7.46 (d, J = 8.7 Hz, 1H), 7.19 (d, J = 9.0 Hz, 1H), 4.24 (s, 3H), 4.22 (d, J = 7.7 Hz, 2H), 2.74 (s, 3H), 2.06-1.99 (m, 1H), 1.46-1.21 (m, 8H), 0.93 (t, J = 7.4 Hz, 3H), 0.85 (t, J = 7.8Hz, 3H).

[0164] (4) Synthesis of compound S10:

[0165]

[0166] Compound S9 (11 g) and dichloroethane (50 mL) were added to the reaction flask, followed by hydroxylamine hydrochloride (2.1 g) and sodium acetate (2.7 g). The mixture was heated to reflux and reacted for 3 h. After the reaction was completed, the mixture was cooled and filtered to remove inorganic salts. The filter cake was washed with a small amount of dichloroethane, and the organic phase was reserved.

[0167] (3) Synthesis of compound 17:

[0168]

[0169] The organic phase of compound S10 was added to the reaction flask, and the temperature was raised to 60-65℃. Acetic anhydride (2.8 g) was added dropwise, and the reaction was allowed to proceed for 1 h. After the reaction was complete, the mixture was neutralized with alkali, washed with water until neutral, separated, and the organic phase was concentrated to dryness. The mixture was then slurried with ethanol to give a yellow solid compound 17 (10 g), with a yield of 79.5%.

[0170] MS (ESI+): m / z 454.4 [M+H] + .

[0171] 1H NMR (400 MHz, Chloroform-d) δ 8.62 (s, 1H), 8.19 (d, J = 9.0 Hz,1H), 8.10 (d, J = 8.7, 1H), 7.45 (d, J = 8.7 Hz, 1H), 7.18 (d, J = 9.0 Hz,1H), 4.22 (s, 3H), 3.73 (q, J = 7.0 Hz, 2H), 2.55 (s, 3H), 2.33 (s, 3H), 2.05-1.99 (m, 1H), 1.37-1.24 (m, 8H), 0.93 (t, J = 7.4 Hz, 3H), 0.87 (t, J =6.8 Hz, 3H).

[0172] Example 3: Synthesis of Compound 18

[0173] (1) Synthesis of compound S11:

[0174]

[0175] The synthesis of compound S11 was performed following the synthesis of compound S4, yielding a yellow solid compound S11 (9.0 g) in 70.25% yield.

[0176] MS (ESI+): m / z 397.4 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.99 (s,1H), 8.17 (d, J = 8.8 Hz, 1H), 8.11 (d, J = 8.9 Hz, 1H), 7.53 (d, J = 8.8 Hz,1H), 6.79 (d, J = 9.0 Hz, 1H), 4.4 (d, J = 8.4 Hz, 2H), 4.23 (s, 3H), 2.74(s, 3H), 1.58-1.51 (m, 1H) 1.18 -0.92 (m, 8H), 0.73 (dt, J = 10.8, 7.1 Hz, 6H).

[0177] (2) Synthesis of compound 18:

[0178]

[0179] The synthesis of compound S12 was performed with reference to the synthesis of compound S10; the synthesis of compound 18 was performed with reference to the synthesis of compound 17, yielding a yellow solid compound 18 (9.0 g) in 87.4% yield.

[0180] MS (ESI+): m / z 454.6 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.69 (s,1H), 8.11 (d, J = 8.9 Hz, 1H), 8.03 (d, J = 8.8Hz, 1H), 7.52 (d, J = 8.9 Hz,1H), 6.77 (d, J = 8.9 Hz, 1H), 4.44 (d, J = 8.0 Hz, 2H), 4.21 (s, 3H), 2.55(s, 3H), 2.33 (s, 3H), 1.58-1.51 (m, 1H), 1.18-0.89 (m, 8H), 0.74 (dt, J =17.3, 7.1 Hz, 6H).

[0181] Examples 4-6: Synthesis of compounds 16, 22 and 47

[0182] Referring to the synthetic routes in Examples 1-3, and selecting the corresponding compounds A, B, C, D, and E, the compounds in Examples 4-6 in Table 1 were prepared respectively.

[0183] Table 1

[0184]

[0185] Example 7: Preparation of Photosensitive Composition 1

[0186] In an acrylic copolymer (70 g), trimethylolpropane triacrylate (30 g), compound 1 (2 g) and methacrylic acid (10.0 g) were added and stirred thoroughly to obtain photosensitive composition 1.

[0187] The above-mentioned acrylic copolymer was obtained by the following method: 30 parts by mass of methacrylic acid, 20 parts by mass of hydroxyethyl methacrylate, 15 parts by mass of methyl methacrylate and 35 parts by mass of benzyl methacrylate were dissolved in 300 parts by mass of ethyl cellosolve. 0.75 parts by mass of azobisisobutyronitrile were added under a nitrogen atmosphere and the mixture was reacted at 70°C for 5 h to obtain the acrylic copolymer.

[0188] Examples 8-12: Preparation of photosensitizing compositions 2-6

[0189] Except by replacing compound 1 with the various compounds in Table 2, the photosensitive compositions of Examples 8-12 and Comparative Examples 1-2 were obtained by referring to the method in Example 7.

[0190] Table 2

[0191]

[0192] The structures of the compounds used as photoinitiators in Comparative Examples 1-2, which serve as control compounds, are shown below.

[0193]

[0194] <Sensitivity Test>

[0195] 365 nm High-Pressure Mercury Lamp Light Source: The above-mentioned photocurable resin composition was stirred in the dark and coated onto a PET film using a No. 6 wire rod to form a wet film with a thickness of approximately 6 µm. Exposure was performed using a light irradiation device with a belt conveyor and a 365 nm high-pressure mercury lamp conveyor light source (at a light intensity of 500 mJ / cm²). 2 (Exposure once). Observe the curing and film formation, and evaluate it using the finger touch method. The test results are shown in Table 3.

[0196] 405 nm UV-LED light source: The above-mentioned photocurable resin composition was stirred in the dark and coated onto a PET film using a No. 6 wire rod to form a wet film with a thickness of approximately 6 µm. Exposure was performed using a light irradiation device with a belt conveyor and a 405 nm UV-LED belt-mounted light source (at a light intensity of 500 mJ / cm²). 2 (Exposure once). Observe the curing and film formation, and evaluate it using the finger touch method. The test results are shown in Table 3.

[0197] The evaluation criteria are as follows:

[0198] 1: Oily, not solid; 2: Oily surface, solidified base; 3: Sticky surface, fingerprints are more noticeable after touching; 4: Basically dry, slightly rough to the touch, faint fingerprints; 5: Fully cured, smooth surface, no fingerprints after touching.

[0199] Table 3

[0200]

[0201] As shown in Table 3, the photosensitivity of the photosensitive compositions based on the compounds of the present invention in Examples 7-12 is significantly higher than that of the photosensitive compositions based on comparative compounds 1-2 in Comparative Examples 1-2, especially at a long wavelength of 405 nm, the advantage is more obvious. This indicates that the compounds of the present invention are not only suitable for short-wavelength photocuring, but also for long-wavelength photocuring.

[0202] Example 13: Preparation of Polymerizable Composition (Photosensitive Resin) 1

[0203] 80 g of an alkali-soluble resin, 20 g of trimethylolpropane triacrylate, 1.5 g of Compound 1, and 80 g of methyl ethyl ketone were added to a reaction vessel at 35 °C, and the mixture was reacted for 6 h and stirred evenly to obtain Polymerizable Composition 1.

[0204] The above alkali-soluble resin was obtained by the following method: 30 parts by mass of methacrylic acid, 50 parts by mass of butyl methacrylate, and 20 parts by mass of styrene were dissolved in 300 parts by mass of ethyl cellosolve. After adding 0.75 parts by mass of azobisisobutyronitrile under a nitrogen atmosphere, the mixture was reacted at 70 °C for 5 h to obtain the alkali-soluble resin.

[0205] Examples 13 - 18: Preparation of Polymerizable Compositions 2 - 6

[0206] Except for replacing Compound 1 with each compound in Table 4, the polymerizable compositions in Examples 13 - 18 and Comparative Examples 3 - 4 were obtained by referring to the method in Example 13.

[0207] Table 4

[0208]

[0209] According to the following method, the photosensitive activities of the polymerizable compositions in Examples 13 - 18 and Comparative Examples 3 - 4 were evaluated.

[0210] <Evaluation of Photosensitive Activity under UV-LED 405 nm Irradiation>[

[0211] Using a spin coater, the polymerizable compositions of Examples 13 - 18 and Comparative Examples 3 - 4 were coated on a glass substrate. Using a spin coater, the temperature was heated to 100 °C and maintained for 2 min at a rotation speed of 1500 rpm, and then cooled to room temperature to form a 10-μm coating film on the surface of the glass substrate. Then, under UV-LED 405 nm, the polymerizable compositions in Examples 13 - 18 and Comparative Examples 4 - 6 were cured at the required exposure dose. The cured coating film was immersed in 1 L of 1 wt% Na2CO3 aqueous solution, washed with ultrapure water, air-dried, and baked and shaped at 200 °C. Table 5 shows the exposure dose required for curing. The smaller this value is, the better the photosensitive activity.

[0212] <Film Formation Performance: Development Property Evaluation>[

[0213] The cured coating film was immersed in 1 L of 1 wt% Na2CO3 aqueous solution and sprayed for 5 hours using a circulating spraying device at a spraying pressure of 0.1 MPa. Then, the developing solution was left to stand for 1 day, and the appearance of agglomerates was observed.

[0214] No clumps: The spraying device produces almost no clumps, and only a very small amount of clumps float in the developing solution; these can be easily rinsed away with water.

[0215] Trace amounts of aggregates: The spray device contains trace amounts of aggregates that are visible to the naked eye, and trace amounts of aggregates float in the developer; these aggregates cannot be completely removed by water washing.

[0216] Table 5 shows the evaluation of the developability of the coated film.

[0217] Table 5

[0218]

[0219] As shown in Table 5, under irradiation with a 405 nm light source, the energy required for curing the polymeric composition containing the compounds of the present invention is significantly less than that required for curing the polymeric composition containing the control compounds (Comparative Compounds 1 and 2). Compared with the compounds used in Comparative Examples 3-4 (Comparative Compound 1 and Comparative Compound 2), the compounds of the present invention exhibit superior photosensitivity and better development performance. They are useful as photoinitiators for photocuring applications.

[0220] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A nitrocarbazole (ketoxime) ester compound, the structure of which is shown in formula (A): in, A is selected from a single bond or a carbonyl group; R1 is selected from C 1-10 Alkyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl C 1-3 Alkylenes and substituted or unsubstituted C 6-10 Aryl, the "substituted or unsubstituted C" 6-10 The substituents in "aryl" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy; R2 is selected from C 1-6 Alkyl, C 3-8 cycloalkyl and substituted or unsubstituted C 6-10 Aryl, the "substituted or unsubstituted C" 6-10 The substituents in "aryl" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy; R3 is selected from C 2-8 alkenyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenylmethylene, C 1-10 Alkyl, substituted C 1-3 Alkyl, the "substituted C 1-3 The word "substituted" in "alkyl" indicates that the alkyl group is replaced by a substituent selected from C10. 3-8 cycloalkyl; R4 is selected from C 2-8 alkenyl, C 1-10 Alkyl, C 3-8 cycloalkyl, C 1-6 alkyl carbonyl, C 6-10 Aryl carbonyl group.

2. The compound according to claim 1, characterized in that, The structures of the nitrocarbazole (ketoxime) ester compounds are shown in formulas (A-1) to (A-2): A, R1, R2, R3 and R4 are defined as in equation (A).

3. The compound according to claim 1, characterized in that, The structures of the nitrocarbazole (ketone) oxime ester compounds are shown in formulas (I) to (X): R1, R2, R3 and R4 are defined as in equation (A).

4. The compound according to any one of claims 1-3, characterized in that, R1 is selected from C 1-10 Alkyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl C 1-2 Alkylene and substituted or unsubstituted phenyl groups, wherein the substituents in "substituted or unsubstituted phenyl groups" are selected from halogens, C... 1-6 Alkyl, C 1-6 Alkyl group.

5. The compound according to any one of claims 1-3, characterized in that, R2 is selected from C 1-6 Alkyl, substituted or unsubstituted C 6-10 Aryl, the "substituted or unsubstituted C" 6-10 The substituents in "aryl" are selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkyl group.

6. The compound according to any one of claims 1-3, characterized in that, The Choose one of the following structures: 。 7. The compound according to any one of claims 1-3, characterized in that, R3 is selected from allyl, cyclohex-1-enylmethylene, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cycloheptylmethylene, cyclooctylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, and cyclooctylethylene.

8. The compound according to any one of claims 1-3, characterized in that, R4 is selected from allyl, C 1-6 Alkyl, C 1-6 alkyl carbonyl, C 6-10 Aryl carbonyl group.

9. A nitrocarbazole (ketone) oxime compound, characterized in that, The nitrocarbazole (ketone) oxime ester compounds are selected from the following compounds: 。 10. A method for preparing the nitrocarbazole (ketone) oxime ester compound of claim 1, wherein the oxime is selected from one of the following methods: When A is a single bond: Method 1: Method 2: When A is a carbonyl group: Method 3: Method 4: 。 11. A polymerizable composition / photosensitive composition comprising the compound according to any one of claims 1-9.

12. The polymerizable composition / photosensitive composition according to claim 11, characterized in that, The polymerizable composition further comprises at least one of the following components: a) Resin; b) Monomer.

13. A photoresist comprising the following components: i) The polymerizable composition / photosensitive composition according to any one of claims 11-12; ii) Additives.

14. The application of the compound according to any one of claims 1-9, the polymeric composition / photosensitive composition according to any one of claims 11-12, or the photoresist according to claim 13 in the field of photocuring.

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