Carbazole (keto) oxime ester compounds, products containing them and their use

Abstract

The present application belongs to the technical field of photocuring, and relates to a carbazole (ketone) oxime ester compound, a product containing the same and application thereof. The structure of the compound of the present application is, compared with existing and commercial photoinitiators, better in sensitivity and stability.

Description

Technical Field

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

[0002] Color photoresist is a crucial material in color filters, primarily composed of red, green, and blue polymers. In recent years, with increasing demand for televisions and continuous expansion of panel manufacturing, the demand for color photoresist has steadily grown. Traditional methods for producing color photoresist include dyeing and electroprecipitation, both of which require the use of metallic chromium (Cr). However, Cr is highly toxic. Therefore, the more advanced pigment dispersion method is currently employed, offering a simpler process and excellent color properties, heat resistance, and lightfastness. Pigment photoresist production is a key technology in the pigment dispersion method, and photoinitiators are essential raw materials. However, traditional photoinitiators such as benzoin and its derivatives, biphenyl ketals, phosphine oxides, and benzophenone / amines suffer from low photosensitivity, poor solubility, and weak storage stability, directly affecting the transparency and heat resistance of color photoresist and failing to meet the requirements for producing high-quality pigment photoresist.

[0003] In 1904, A. Werner first reported the photochemical properties of oxime esters. In 1970, oxime esters began to be used as photoinitiators. Among them, the oxime ester photoinitiator Quanta cure PDO was widely commercialized. Although this compound has high photoinitiating activity, its poor stability led to its rapid replacement by other free radical initiators. In recent years, researchers have introduced groups that increase the conjugated surface area of ​​oxime ester molecules, further improving the initiation efficiency and stability of oxime ester derivatives, thus attracting attention to the preparation and application of oxime ester photoinitiators. Typical examples include the research by Hisatoshi Kura et al. on introducing diphenyl sulfide groups into oxime esters and the research by Dietliker K et al. on introducing carbazole groups into oxime esters. Due to the large conjugated system and strong intramolecular electron transfer characteristics of these groups, the stability and photosensitivity of these oxime esters are greatly improved.

[0004] The yellowing problem of oxime ester photoinitiators, especially carbazole oxime ester photoinitiators (CN114369178A), has limited their use in LCD photoresist formulations, primarily in black photoresist formulations, making them unsuitable for transparent and RGB color photoresists. Meanwhile, with the development of photocurable light sources, the pigment content in photocurable formulations is increasing, necessitating ongoing research into novel initiators with low yellowing and high sensitivity at long wavelengths. Summary of the Invention

[0005] In view of the above-mentioned problems in the prior art, the present invention provides a series of novel carbazole (ketone) oxime compounds, products containing the same, and their applications in the field of photocuring, in order to solve the above problems.

[0006] In a first aspect, the present invention provides a carbazole (ketone) oxime ester compound as shown in formula (A).

[0007]

[0008] in,

[0009] A is selected from a single bond or a carbonyl group;

[0010] R1 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl;

[0011] R2 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C6-20 aryl;

[0012] R3 is selected from substituted or unsubstituted C3. 2-20 alkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C 6-20 Aryl;

[0013] 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, substituted or unsubstituted 4-20 membered heteroaryl carbonyl;

[0014] R5 is selected from hydrogen, cyano, ... -CO-R6;

[0015] R6 is selected from substituted or unsubstituted C. 6-20 Aryl groups and substituted or unsubstituted 4-20 membered heteroaryl groups;

[0016] The heteroaryl group contains 1 to 3 heteroatoms, each independently selected from N, O and S.

[0017] In a second aspect, the present invention provides a polymerizable composition / photosensitive composition comprising the carbazole (ketone) oxime ester compound described in the present invention.

[0018] Preferably, the polymerizable composition further comprises at least one of the following components:

[0019] a) Resin;

[0020] b) Monomer.

[0021] Thirdly, the present invention provides a photoresist comprising the following components:

[0022] i) The polymeric composition / photosensitive composition of the present invention;

[0023] ii) Additives.

[0024] Part Four: This invention provides the application of the carbazole (ketone) oxime ester compounds, polymerizable compositions / photosensitive compositions, or photoresists described in this invention in the field of photocuring.

[0025] The effects of the invention

[0026] Compared with existing and commercial photoinitiators, the carbazole (ketoxime) ester compounds of the present invention exhibit a significant red shift in the ultraviolet absorption spectrum by introducing an alkoxy group and its derivatives at the 4-position, thereby improving sensitivity, development performance and resistance to yellowing, making them novel high-sensitivity photoinitiators that efficiently absorb long-wavelength light sources. Attached Figure Description

[0027] 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

[0028] Carbazole (keto) oxime compounds

[0029] To address the problems of poor resistance to yellowing and low sensitivity under long wavelengths in existing technologies, this invention provides a carbazole (ketone) oxime ester compound with the structure shown in formula (A):

[0030]

[0031] in,

[0032] A is selected from a single bond or a carbonyl group;

[0033] R1 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl;

[0034] R2 is selected from substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C6-20 aryl;

[0035] R3 is selected from substituted or unsubstituted C3. 2-20 alkenyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C 6-20 Aryl;

[0036] 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, substituted or unsubstituted 4-20 membered heteroaryl carbonyl;

[0037] R5 is selected from hydrogen, cyano, ... -CO-R6;

[0038] R6 is selected from substituted or unsubstituted C. 6-20 Aryl groups and substituted or unsubstituted 4-20 membered heteroaryl groups;

[0039] The heteroaryl group contains 1 to 3 heteroatoms, each independently selected from N, O and S.

[0040] 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 group, C 3-20 cycloalkyl, C 6-20 Aryl groups and 4-20 heteroaryl groups.

[0041] In one embodiment of the present invention, the structure of the carbazole (keto) oxime ester compound is shown in formulas (I) to (VI):

[0042]

[0043] R1, R2, R3, R4, and R6 are defined as in equation (A).

[0044] In one embodiment of the present invention, R1 is selected from C. 1-20 Alkyl, C 3-20 cycloalkyl and C 3-20 cycloalkyl C 1-6 Alkylene.

[0045] In one embodiment of the present invention, R1 is selected from C. 1-10 Alkyl, C 3-8 cycloalkyl and C 3-8 cycloalkyl C 1-2 Alkylene.

[0046] In one embodiment of the present invention, R1 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cycloheptylmethylene, cyclooctylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, and cyclooctylethylene.

[0047] In one embodiment of the present invention, R1 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 3-methylbutyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cyclopropylethylidene, cyclobutylethylidene, cyclopentylethylidene and cyclohexylethylidene.

[0048] In one embodiment of the present invention, R1 is selected from methyl, ethyl, 2,4,4-trimethylpentyl, cyclohexyl, cyclopentylmethylene, cyclohexylmethylene, cyclopentylethylene, and cyclohexylethylene.

[0049] 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.

[0050] 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 The aryl group, wherein the substituent in the “substituted or unsubstituted C6-10 aryl” is selected from halogens, C1-6 alkyl, C1-6 alkoxy, C1-6 alkoxy-C1-6 alkoxy, C1-6 alkyl carbonyloxy, C1-6 alkoxy carbonyl, C3-6 cycloalkyl, and phenyl.

[0051] 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 and substituted or unsubstituted naphthyl" is selected from halogens, C 1-6 Alkyl, C1-6 Alkoxy, C 1-6 alkyl carbonyloxy group, C 1-6 Alkoxycarbonyl group.

[0052] In one embodiment of the invention, R2 is selected from methyl and phenyl.

[0053] In one embodiment of the present invention, R3 is selected from allyl, C 1-20 Alkyl and C 3-20 cycloalkyl C 1-6 Alkylene, substituted or unsubstituted C 6-20 Aryl and substituted or unsubstituted C 6-10 Aryl C 1-2 Alkylene.

[0054] In one embodiment of the present invention, R3 is selected from allyl, 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 group, C 1-6 alkoxycarbonyl, C 3-6 Cycloalkyl, phenyl.

[0055] In one embodiment of the present invention, R3 is selected from allyl, 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 group, C 1-6 Alkoxycarbonyl group.

[0056] In one embodiment of the invention, R3 is selected from allyl, methyl, ethyl, propyl, butyl, 3-methylbutyl, 2-ethylhexyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, and halogenated compounds, C 1-6 Alkyl-substituted or unsubstituted phenyl or benzyl groups.

[0057] In one embodiment of the present invention, R3 is selected from allyl, ethyl, 3-methylbutyl, and 2-ethylhexyl.

[0058] 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 6-14 aryl carbonyl, C 6-10 Aryl C 1-2 Alkyl carbonyl group.

[0059] In one embodiment of the present invention, R4 is selected from allyl, C 1-10 Alkyl, C 3-8 cycloalkyl, C 1-6 alkyl carbonyl, C 6-10 Aryl carbonyl group.

[0060] 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.

[0061] 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.

[0062] In one embodiment of the present invention, R5 is selected from hydrogen, cyano, and C. 1-20 Alkyl group, -CO-R6, wherein R6 is selected from C 1-20 Alkyl, C 1-20 Alkoxy, C 1-20 alkyl carbonyloxy group, C 1-20 alkoxycarbonyl, C 3-20 cycloalkyl, C 6-20 Aryl or 4-20 heteroaryl substituted or unsubstituted: C 6-20 Aryl carbonyl, 4-20 membered heteroaryl carbonyl.

[0063] In one embodiment of the present invention, R5 is selected from hydrogen, cyano, and C. 1-6 Alkyl group, -CO-R6, wherein R6 is selected from C1-6 Alkyl, C 1-6 Alkoxy, C 1-6 alkyl carbonyloxy group, C 1-6 alkoxycarbonyl, C 3-6 cycloalkyl, C 6-10 Aryl or 4-10 heteroaryl substituted or unsubstituted: C 6-10 Aryl carbonyl, 4-10 heteroaryl carbonyl.

[0064] In one embodiment of the invention, R6 is selected from phenyl, biphenyl, naphthyl, indoleyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, isobenzothiophenyl, furanyl, thiophenyl, pyrroleyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl (more preferably 1-naphthyl, 2-naphthyl, indole-1-yl, indole-2-yl, isoindole-2-yl, isoindole-1-yl, benzofuran-2-yl, isobenzofuran-1-yl, benzothiophen-2-yl, isobenzothiophen-1-yl, furanyl-2-yl, furanyl-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrole-2-yl, pyrrole-3-yl); optionally, it is selected from one or more of halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 alkyl carbonyloxy group, C 1-6 alkoxycarbonyl, C 3-6 Substitution of cycloalkyl and phenyl groups.

[0065] In one embodiment of the present invention, R5 is selected from hydrogen, cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, -CO-R6; wherein R6 is selected from phenyl, tolyl, xylyl, trimethylyl, naphthyl-1-yl, naphthyl-2-yl, indol-2-yl, benzofuran-2-yl, benzothiophene-2-yl, furan-2-yl, and thiophene-2-yl.

[0066] In one embodiment of the invention, the Choose one of the following structures:

[0067] .

[0068] In one embodiment of the invention, the structure of the carbazole (keto) oxime ester compound is shown in any one of formulas (1-1) to (1-6):

[0069]

[0070] R1, R2, R3 and R6 are as defined in this invention.

[0071] In one embodiment of the present invention, the carbazole (ketone) oxime compound is selected from the following compounds:

[0072] .

[0073] 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 1-6Alkyl, -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).

[0074] 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.

[0075] In this invention, the alkylene group is a group formed by further removing one hydrogen atom from an alkyl group.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] Unless otherwise specified, the terms “halogen” or “halogenated” refer to F, Cl, Br, and I.

[0081] Preparation method of carbazole (keto) oxime compounds

[0082] The present invention also provides a method for preparing the carbazole (ketoxime) ester compound, wherein the method is selected from one of the following methods:

[0083] When A is a single bond:

[0084] Method 1:

[0085]

[0086] Method 2:

[0087]

[0088] Method 3:

[0089]

[0090] When A is a carbonyl group

[0091] Method 4:

[0092]

[0093] Method 5:

[0094]

[0095] Method Six:

[0096] .

[0097] Products containing carbazole (keto) oxime ester photoinitiators

[0098] The carbazole (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.

[0099] Therefore, the present invention provides a polymerizable composition / photosensitive composition comprising the above-described carbazole (ketone) oxime ester compound of the present invention.

[0100] In one embodiment of the present invention, the polymeric composition / photosensitive composition may further comprise at least one of the following components:

[0101] a) Resin;

[0102] b) Monomer.

[0103] 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.

[0104] 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.

[0105] In one embodiment of the invention, the polymerizable 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 30-40 parts of monomer.

[0106] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 3 parts of the carbazole (ketone) oxime compound of the present invention; 75.5 parts of resin; and / or 36.5 parts of monomer.

[0107] In one embodiment of the invention, the polymeric composition / photosensitive composition comprises the following components in parts by weight: 2 parts of the carbazole (ketone) oxime compound of the present invention; 70 parts of resin; and / or 30 parts of monomer.

[0108] In one embodiment of the invention, the resin comprises an acrylic polymer.

[0109] 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.

[0110] 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.

[0111] 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 butyl methacrylate, especially a polymer of a mixture in the weight ratio of the four components being 10-30:5-25:5-20:20-70, or a polymer of a mixture in the weight ratio of the four components being 20:15:10:55.

[0112] In one embodiment of the invention, the resin comprises a (meth)acrylate-styrene copolymer.

[0113] 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.

[0114] In one embodiment of the present invention, the (meth)acrylate-styrene copolymer may be a copolymer of methacrylic acid, methyl methacrylate and styrene, especially a polymer in which the weight ratio of the three is 15-40:20-70:15-40, or a polymer in which the weight ratio of the three is 26:49:25.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] In one embodiment of the invention, the monomer is selected from at least one of (meth)acrylic acid and crosslinked (meth)acrylates.

[0119] In one embodiment of the invention, the crosslinked (meth)acrylate is selected from trimethylolpropane triacrylate.

[0120] 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 5-35 parts by weight of crosslinked (meth)acrylate; or 8-12 parts of (meth)acrylic acid and 22-28 parts by weight of crosslinked (meth)acrylate; or 10 parts of (meth)acrylic acid and 26.5 parts by weight of crosslinked (meth)acrylate. Alternatively, preferably, it comprises, by weight, 10-40 parts by weight of crosslinked (meth)acrylate; or 25-35 parts by weight of crosslinked (meth)acrylate; or 30 parts by weight of crosslinked (meth)acrylate.

[0121] In another embodiment of the invention, the polymeric composition / photosensitive composition may further comprise at least one of the following components:

[0122] a) Alkali-soluble resins;

[0123] b) Photopolymerizable compounds.

[0124] Preferably, the alkali-soluble resin includes the aforementioned acrylic polymers and (meth)acrylate-styrene copolymers.

[0125] 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.

[0126] In one embodiment of the invention, the polymeric composition / photosensitive composition may further contain additives.

[0127] Preferably, the additives are selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators, and thermal polymerization inhibitors.

[0128] The present invention also provides a photoresist comprising the following components:

[0129] i) The polymeric composition / photosensitive composition of the present invention;

[0130] ii) Additives.

[0131] 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.

[0132] Applications of the product in the field of photocuring

[0133] This invention provides the application of the above-mentioned carbazole (ketone) oxime compounds, polymeric compositions / photosensitive compositions, or photoresists in the field of photocuring.

[0134] 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.

[0135] Example 1: Synthesis of Compound 42

[0136] (1) Synthesis of compound S1:

[0137]

[0138] 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] + .

[0139] (2) Synthesis of compound S2:

[0140]

[0141] 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%.

[0142] 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).

[0143] (3) Synthesis of compound S3:

[0144]

[0145] 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.

[0146] (4) Synthesis of compound S4:

[0147]

[0148] Add the organic phase of the above compound S3 and tetrahydrofuran (50 mL) to the reaction flask. After stirring until completely dissolved, add 30wt% concentrated hydrochloric acid (2.7 g) at 0-10℃. After stirring until completely dissolved, cool to 0-5℃ and add isoamyl nitrite (2.6 g). Continue to keep the reaction at this temperature for 2 h. Quench the reaction with water and separate the liquids. Extract the aqueous phase with dichloromethane. Combine the two organic phases and dry them with anhydrous sodium sulfate (Na2SO4). Concentrate under reduced pressure for later use.

[0149] (5) Synthesis of compound 42:

[0150]

[0151] 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 (2.7 g) was added dropwise. The mixture was then cooled to 0-5 °C, and acetyl chloride (1.9 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 42 (6.9 g), with a yield of 81.8%.

[0152] MS (ESI+): m / z 379.3 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.15 (d,J = 7.9 Hz, 1H), 7.99 (d, J = 8.7 Hz, 1H), 7.55-7.42 (m, 2H), 7.34-7.21 (m,2H), 6.17-6.05 (m, 1H), 5.53 (d, J = 17.2 Hz, 1H), 5.35 (d, J = 10.7 Hz, 1H), 4.70 (s, 2H), 4.38 (q, J = 7.6 Hz, 2H), 2.34 (s, 3H), 2.21 (s, 3H), 1.50-1.42(m, 3H).

[0153] Example 2: Synthesis of Compound 85

[0154] (1) The synthetic route of compound S5 is shown below:

[0155]

[0156] S3 (10 g) and dichloroethane (50 mL) were added to a reaction flask, followed by aluminum trichloride (4.7 g) at 0-10 °C. After half an hour, propionyl chloride (3.3 g) as compound H was added dropwise at 0-10 °C, and the mixture was then heated to room temperature for 2 h. After the reaction was completed, the reaction solution was poured into ice water, separated, and the organic phase was dried over anhydrous sodium sulfate (Na2SO4). The organic phase was concentrated and purified with ethanol to give 11 g of white solid S5, with a yield of 93.0%.

[0157] MS (ESI+): m / z 364.6 [M+H] + . 1 H NMR (400 MHz, Chloroform-d) δ 8.92 (s,1H), 8.21 (d, J = 8.7 Hz, 1H), 7.92 (d, J = 8.6 Hz, 1H), 7.46 (d, J = 8.7 Hz,1H), 7.24 (d, J = 8.7,1H), 6.32-6.22 (m, 1H), 5.65 (dq, J = 17.2, 1.7 Hz, 1H), 5.45 (dq, J = 10.5, 1.4 Hz, 1H), 4.69 (dt, J = 5.3, 1.6 Hz, 2H), 4.40(q, J = 7.2 Hz, 2H), 3.15 (dq, J = 25.6, 7.3 Hz, 4H), 1.47 (t, J = 7.3 Hz, 3H), 1.27 (dt, J = 15.9, 7.3 Hz, 6H).

[0158] (2) The synthetic route of compound 85 is shown below:

[0159]

[0160] The synthesis of compound S6 was performed with reference to the synthesis of compound S4; the synthesis of compound 85 was performed with reference to the synthesis of compound 42, yielding a pale yellow solid compound 85 (11.5 g) in 75.1% yield.

[0161] MS (ESI+): m / z 506.3 [M+H] + . 1H NMR (400 MHz, Chloroform-d) δ 8.86 (s,1H), 8.29 (d, J = 8.7 Hz, 1H), 7.98 (d, J = 8.6 Hz, 1H), 7.49 (d, J = 8.8 Hz,1H), 7.28 (d, J = 8.6 Hz, 1H), 6.12-6.03 (m, 1H), 5.50 (dq, J = 17.3, 1.7 Hz,1H), 5.33 (dq, J = 10.6, 1.5 Hz, 1H), 4.69 (dt, J = 5.0, 1.7 Hz, 2H), 4.41(q, J = 7.3 Hz, 2H), 2.34 (d, J = 7.9 Hz, 6H), 2.28 (s, 3H), 2.22 (s, 3H), 1.47 (t, J = 7.2 Hz, 3H).

[0162] Example 3: Synthesis of Compound 82

[0163] (1) The synthetic route of compound S7 is shown below:

[0164]

[0165] Add S3 (10 g) and dichloroethane (50 mL) to the reaction flask, followed by aluminum trichloride (4.7 g) at 0-10 °C. After half an hour, add o-methylbenzoyl chloride (5.0 g) as compound G dropwise at 0-10 °C, then raise the temperature to room temperature and react for 2 h. After the reaction is complete, pour the reaction solution into ice water, separate the layers, and dry the organic phase with anhydrous sodium sulfate (Na2SO4) for later use.

[0166] (2) The synthetic route of compound S8 is shown below:

[0167]

[0168] The organic phase of compound S16 was added to the reaction flask, followed by hydroxylamine hydrochloride (3.2 g) and sodium acetate (4.8 g). The mixture was heated to reflux and reacted for 6 h. After the reaction was completed, the mixture was cooled and filtered. The filter cake was washed with a small amount of dichloroethane, and the organic phase was reserved for later use.

[0169] (3) Synthesis of compound 82:

[0170]

[0171] The organic phase of compound S8 was added to the reaction flask, and the temperature was raised to 60-65 °C. Acetic anhydride (4.2 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 white solid compound 82 (12.1 g), with a yield of 77.2%. MS (ESI+): m / z 483.5 [M+H] + .

[0172] Examples 4-8: Synthesis of compounds 8, 26, 50, 56 and 76

[0173] Referring to the synthetic routes in Examples 1-3, and selecting the corresponding compounds A, B, C, D, E, and G, the compounds in Examples 4-8 in Table 1 were prepared respectively.

[0174] Table 1

[0175]

[0176] Example 9: Preparation of Photosensitive Composition 1

[0177] In an acrylic copolymer (75.5 g), trimethylolpropane triacrylate (26.5 g), compound 42 (3 g) and acrylic acid (10.0 g) were added and stirred thoroughly to obtain photosensitive composition 1.

[0178] The above-mentioned acrylic copolymer was obtained by the following method: 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl 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.

[0179] Examples 10-18: Preparation of photosensitizing compositions 2-8

[0180] Except for replacing compound 42 with the various compounds in Table 2, the photosensitive compositions of Examples 10-18 and Comparative Examples 1-3 were obtained by referring to the method in Example 9.

[0181] Table 2

[0182]

[0183] Among them, the structures of the compounds used as photoinitiators in Comparative Examples 1-3, which serve as control compounds, are shown below.

[0184]

[0185] <Sensitivity Test>

[0186] 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.

[0187] 395 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 395 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.

[0188] The evaluation criteria are as follows:

[0189] 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.

[0190] Table 3

[0191]

[0192] As shown in Table 3, the photosensitivity of the photosensitive compositions based on the compounds of the present invention in Examples 9-16 is significantly higher than that of the photosensitive compositions based on OXE02, AMO and OMES in Comparative Examples 1, 2 and 3, especially at a longer wavelength of 395 nm, where 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.

[0193] Example 17: Preparation of polymeric composition (photosensitive resin) 1

[0194] Alkali-soluble resin (70 g), trimethylolpropane triacrylate (30 g), compound 42 (2 g), and butanone (80 g) were added to a reaction vessel at 35°C and reacted for 6 h. After stirring until homogeneous, polymeric composition 1 was obtained.

[0195] The above alkali-soluble resin is obtained by the following method: 26 parts by mass of methacrylic acid, 49 parts by mass of methyl methacrylate, and 25 parts by mass of styrene are dissolved in 300 parts by mass of ethyl cellosolve. After adding 0.75 parts by mass of azobisisobutyronitrile under a nitrogen atmosphere, the reaction is carried out at 70 °C for 5 h to obtain the alkali-soluble resin.

[0196] Examples 18 - 24: Preparation of Polymerizable Compositions 2 - 8

[0197] Except for replacing Compound 42 with each compound in Table 4, referring to the method in Reference Example 17, the polymerizable compositions in Examples 18 - 24 and Comparative Examples 4 - 6 are obtained.

[0198] Table 4

[0199]

[0200] According to the following method, the polymerizable compositions in the above Examples 17 - 24 and Comparative Examples 4 - 6 are evaluated for photosensitive activity.

[0201] <Evaluation of Photosensitive Activity under UV - LED 385 nm Irradiation>

[0202] Using a spin coater, the polymerizable compositions of Examples 17 - 24 and Comparative Examples 4 - 6 are coated on a glass substrate. Using a spin coater, at a rotation speed of 1500 rpm, it is heated to 100 °C and held for 2 min, then cooled to room temperature to form a 10 - μm coating film on the surface of the glass substrate. Then, under UV - LED 385 nm, at the required exposure amount, the polymerizable compositions in the above Examples 17 - 24 and Comparative Examples 4 - 6 are cured. The cured coating film is immersed in 1 L of 1 wt% Na2CO3 aqueous solution, washed with ultrapure water, air - dried, and baked at 200 °C. Table 5 shows the exposure amount required for complete curing. The smaller this value is, the better the photosensitive activity.

[0203] <Film - forming Performance: Development Property Evaluation>

[0204] The cured coating film is immersed in 1 L of 1 wt% Na2CO3 aqueous solution, and sprayed for 5 h using a circulating jet device at a spray pressure of 0.1 MPa. Then, the developer is left for 1 day to observe the appearance of aggregates.

[0205] No aggregates: There are almost no aggregates in the jet device, and there are extremely trace aggregates floating in the developer; they can be easily rinsed off by water washing.

[0206] Trace aggregates: There are visually visible trace to small amounts of aggregates in the jet device, and there are trace to small amounts of aggregates floating in the developer; they cannot be completely washed off by water washing.

[0207] Table 5 shows the evaluation of the developability of the coated film.

[0208] <Film Forming Properties: Evaluation of Yellowing Resistance>

[0209] The cured coating film on the glass substrate was placed on a heating plate heated to 260°C for 5 minutes. The transmittance of the cured coating film before and after heating was measured by a UV spectrophotometer (Shimadzu UV-1900i) at a wavelength of 450nm (transmittance change = transmittance of the cured coating film before heating - transmittance of the cured coating film after heating) for evaluation.

[0210] Table 5 shows the evaluation of the yellowing resistance of the coated film. The higher the value, the better the yellowing resistance.

[0211] 5: Transmittance variation is 0-5%.

[0212] 4: Transmittance varies by 5-10%.

[0213] 3: The transmittance varies by 10-15%.

[0214] 2: The transmittance varies by 15-20%.

[0215] 1: The transmittance change is more than 20%.

[0216] Table 5

[0217]

[0218] As shown in Table 5, under irradiation at 385 nm, the energy required for curing the polymerizable composition containing the compounds of this invention is significantly less than that required for curing the polymerizable composition containing the control compounds (OXE02, AMO, and OMES). Compared with the compounds (OXE02, AMO, and OMES) used in Comparative Examples 4-6, the compounds of this invention exhibit superior photosensitivity, better resistance to yellowing, and improved developability. They are useful as photoinitiators for photocuring applications.

[0219] 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 carbazole (keto) oxime 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 and C 3-8 cycloalkyl C 1-3 Alkylene; 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 1-10 Alkyl, C 3-8 cycloalkyl C 1-3 Alkylene; 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; R5 is selected from hydrogen, cyano, -CO-R6; R6 is selected from phenyl, naphthyl, indolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, isobenzothiophenyl, furanyl, thiophenyl, pyrroleyl; it may optionally be selected from one or more halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy C 1-6 Alkoxy group substitution.

2. The compound according to claim 1, characterized in that, The structures of the carbazole (ketone) oxime ester compounds are shown in formulas (I) to (VI): R1, R2, R3, R4, and R6 are defined as in equation (A).

3. The compound according to claim 1 or 2, characterized in that, R1 is selected from C 1-10 Alkyl, C 3-8 cycloalkyl and C 3-8 cycloalkyl C 1-2 Alkylene.

4. The compound according to claim 1 or 2, 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 Alkyl group.

5. The compound according to claim 1 or 2, characterized in that, R3 is selected from allyl, C 1-10 Alkyl, C 3-8 cycloalkyl C 1-2 Alkylene.

6. The compound according to claim 1 or 2, characterized in that, R4 is selected from allyl, C 1-10 Alkyl, C 1-6 alkyl carbonyl, C 6-10 Aryl carbonyl group.

7. The compound according to claim 1, characterized in that, R5 is selected from hydrogen, cyano, -CO-R6.

8. The compound according to claim 1, 2 or 7, characterized in that, R6 is selected from phenyl, naphthyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, isobenzothiophenyl, furanyl, and thiophenyl.

9. The compound according to claim 1 or 2, characterized in that, The structures of the carbazole (keto) oxime ester compounds are shown in any one of formulas (1-1) to (1-6): R1, R2, R3, and R6 are defined as in equation (A).

10. A carbazole (ketone) oxime ester compound, characterized in that, The carbazole (ketone) oxime ester compounds are selected from the following compounds: 。 11. The method for preparing the carbazole (ketone) oxime ester compound according to claim 1, wherein the carbazole is selected from one of the following methods: When A is a single bond: Method 1: Method 2: Method 3: When A is a carbonyl group Method 4: Method 5: Method Six: 。 12. A polymerizable composition / photosensitive composition comprising the compound according to any one of claims 1-10.

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

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

15. The application of the compound according to any one of claims 1-10, the polymeric composition / photosensitive composition according to any one of claims 12-13, or the photoresist according to claim 14 in the field of photocuring.

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