Dioxime ester compound, photoresist and application thereof

Abstract

The invention provides a dioxime ester compound, a photoresist and application of the dioxime ester compound. The dioxime ester compound disclosed by the invention has a structure as shown in a formula (I), and the photoresist prepared by using the dioxime ester compound as a photoinitiator shows a higher sensitivity characteristic. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry and photocuring, and in particular relates to a new dioxime ester compound, a photoresist containing the dioxime ester compound and application thereof. Background Art

[0002] Since the emergence of photocuring technology in the 1970s, it has been widely used. For example, UV photocuring technology is widely used in the fields of coatings, printing inks, and electronic device manufacturing. One of the issues that technicians are most concerned about in photocuring technology is the curing efficiency or sensitivity. The key factors affecting the curing efficiency are the photoinitiator structure and the auxiliary initiator components used in conjunction with it. Patent WO2002 / 100903 discloses oxime ester compounds with more complex substituents on the diphenyl sulfide parent structure and oxime ester compounds based on carbazole. Among them, commercial products such as BASF's OXE 02, although its sensitivity is improved, its yellowing is also stronger, which makes its use in transparent photoresists and color photoresists very limited. Based on the aforementioned patent compounds, the Chinese patent CN101565472B changes the side chain, but does not fundamentally change the corresponding oxime ester compound. Patent CN101528694A discloses an oxime ester compound with nitrocarbazole as the parent, and patent CN103153952A discloses an oxime ester compound with benzocarbazole as the parent. Due to the introduction of the chromophore nitro group or the large conjugated structure of benzocarbazole, the ultraviolet absorption spectrum of the corresponding oxime ester compound is significantly red-shifted. For example, NCI-831 of Japan Aidi Co., Ltd. and BASF's The two commercial products of OXE 03 have more effective absorption of the 365nm emission light of the light source and show higher sensitivity. Patent CN102459171A discloses a novel substituted phenylcarbazole series compound used as an initiator for a photoresist composition.

[0003] In order to improve the exposure sensitivity of photoresist, technicians are constantly seeking new photoinitiator products with higher sensitivity, which prompts the industry to still need to develop new photoinitiators with higher sensitivity. Summary of the invention

[0004] In order to solve one of the above technical problems existing in the prior art, the present invention provides a new dioxime ester compound, that is, a compound having a dioxime ester group with an aromatic compound as a parent skeleton. The dioxime ester compound provided by the present invention is used as a photoinitiator in a photocurable composition, especially a photoresist composition, and shows high sensitivity characteristics. The photoresist composition can be used for the manufacture of color displays.

[0005] In a first aspect, the present invention provides a dioxime ester compound having a structure as shown in formula (I):

[0006]

[0007] in,

[0008] R 1 Selected from hydrogen atom, nitro group, R 4 C(=O)-、R 5 ,

[0009] R 2 Selected from hydrogen atoms, deuterium atoms, C1-C10 alkyl groups, substituted or unsubstituted C1-C10 alkyl groups, C3-C10 alkyl groups inserted by one or more O atoms, C3-C7 cycloalkyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, wherein the substituents in the C1-C10 alkyl groups are selected from one or more of phenyl groups, C3-C7 cycloalkyl groups, C3-C7 heterocyclic groups, C1-C4 alkoxy groups or C1-C4 alkyl acyloxy groups;

[0010] Optionally, R 2 with Ar 1 The carbon atom or nitrogen atom on the ring is connected to R 2 The side chain is Ar 1 The two atoms in the ring together form a five-membered ring, a six-membered ring, or a seven-membered ring;

[0011] R 2 The C3-C7 cycloalkyl and C3-C7 heterocyclic groups are unsubstituted or selected from F, Cl, C1-C4 alkyl, C1-C4 alkoxy, R 4 C(═O)O- is substituted with one or more substituents;

[0012] R 3 Selected from C1-C3 alkyl, C1-C4 alkoxy, phenyl, R 4 OC(=O)- or R 4 C(=O)-;

[0013] R 4 is selected from C1-C8 alkyl, C3-C7 cycloalkyl, C1-C3 alkyl substituted with C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, R 5 O(C=O)- or -C(=O)NR 5 R 5 ′;

[0014] R 5 , R 5 ' are each independently selected from substituted or unsubstituted C1-C8 alkyl, cyclopentyl, cyclohexyl, wherein the substituent in the C1-C8 alkyl is selected from one or more of F atom, phenyl, C3-C7 cycloalkyl;

[0015] Optionally, R 5 R 5 'N forms the following ring structure:

[0016] R 6 is selected from C1-C11 alkyl, C3-C7 cycloalkyl, C1-C3 alkyl substituted with C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, R 5 O(C=O)- or -C(=O)NR 5 R 5 ′;

[0017] R 7 Selected from C1-C10 alkyl, C3-C7 cycloalkyl, C1-C2 alkyl substituted by C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl;

[0018] Ar 1 is selected from substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C4-C20 heteroarylene, each connected to R 1 and Two groups;

[0019] The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=)CR 3 One or more of;

[0020] The substituents in the C6-C20 arylene group and the C4-C20 heteroarylene group are selected from C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=C)R 3 One or more of .

[0021] In some embodiments, R 2 Selected from C1-C6 alkyl, cyclopentylmethyl, cyclohexylmethyl, phenyl, methyl substituted phenyl, C1-C4 alkoxy substituted phenyl, polyfluoro C2-C4 alkoxy substituted phenyl.

[0022] In some embodiments, R 3 Selected from methyl or phenyl.

[0023] In some embodiments, R 4is selected from C1-C4 alkyl, C5-C6 cycloalkyl, C1-C2 alkyl substituted by C5-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted thienyl; the substituents in the phenyl and thienyl are selected from C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=)CR 3 One or more of .

[0024] In some embodiments, R 5 Selected from C1-C8 alkyl.

[0025] In some embodiments, R 6 Selected from C1-C11 alkyl, cyclohexyl, 2-cyclohexylethyl, phenyl, 4-fluorophenyl, thiophen-2-yl.

[0026] In some embodiments, R 7 Selected from C1-C10 alkyl, cyclohexylmethyl, phenyl, 4-fluorophenyl.

[0027] In the present invention, any alkyl group having three or more carbon atoms may be a straight chain or a branched chain structure.

[0028] In some embodiments, the compound has a structure shown in Formula I-(1) or Formula I-(2),

[0029]

[0030]

[0031] in,

[0032] R 1 Selected from R 4 C(=O), nitro,

[0033] R 8 Selected from C1-C8 alkyl,

[0034] R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are independently a hydrogen atom, F, a C1-C4 alkyl group or F 3 C;

[0035] R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The same as the definition of formula (I).

[0036] In some embodiments, in Formula I-(1) and / or Formula I-(2), R 4 Selected from C1-C6 alkyl, phenyl substituted with one or more C1-C4 alkyl groups.

[0037] In some embodiments, in Formula I-(1) and / or Formula I-(2), R 6 Selected from C1-C6 alkyl, phenyl substituted with one or more C1-C4 alkyl groups.

[0038] In some embodiments, in Formula I-(1) and / or Formula I-(2), R 7 Selected from hydrogen or C1-C6 alkyl.

[0039] In some embodiments, in Formula I-(1) and / or Formula I-(2), R 2 Selected from hydrogen atom, C1-C8 alkyl group, C1-C3 alkyl group substituted by C3-C7 cycloalkyl group, C6-C10 aryl group, for example, hydrogen atom, C1-C6 alkyl group, cyclopentylmethyl group, cyclohexylmethyl group or phenyl group.

[0040] In some embodiments, in Formula I-(1) and / or Formula I-(2), R 3 Selected from methyl, ethyl or phenyl.

[0041] In some embodiments, in Formula I-(1), R 1 Selected from nitro, R 2 is selected from C5-C7 cycloalkyl substituted C1-C3 alkyl (e.g. cyclopentylmethyl or cyclohexylmethyl), R 3 is selected from methyl or ethyl, R 8 is selected from C6-C8 alkyl, R 11 , R 12 , R 13 , R 14 , R 15 and R 16 All are hydrogen atoms.

[0042] In some embodiments, the compound has a structure shown in Formula I-(3),

[0043]

[0044] in,

[0045] R 1 Selected from hydrogen atoms, R 4 C(=O)-,R 5 , nitro,

[0046] R 11 , R12 , R 13 , R 14 , R 15 and R 16 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, F 3 C or C1-C4 alkoxy, or optionally R 11 , R 12 , R 13 , R 14 , R 15 and R 16 The two adjacent benzene rings form a five-membered ring, a six-membered ring or a seven-membered ring;

[0047] R 21 , R 22 , R 23 and R 24 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, F 3 C or C1-C4 alkoxy;

[0048] R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The same as the definition of formula (I).

[0049] In some embodiments, in Formula I-(3), R 4 Selected from C1-C6 alkyl, phenyl substituted with one or more C1-C4 alkyl groups.

[0050] In some embodiments, in Formula I-(3), R 5 Selected from C1-C8 alkyl, cyclopentyl or cyclohexyl.

[0051] In some embodiments, in Formula I-(3), R 6 Selected from C1-C10 alkyl, phenyl substituted with one or more C1-C4 alkyl, C4-C10 heteroaryl, such as thienyl.

[0052] In some embodiments, in Formula I-(3), R 7 Selected from hydrogen or C1-C10 alkyl.

[0053] In some embodiments, in Formula I-(3), R 2Selected from hydrogen atom, C1-C10 alkyl group, C1-C3 alkyl group substituted by C3-C7 cycloalkyl group, C1-C3 alkyl group substituted by phenyl group, C6-C10 aryl group, fluorinated C6-C10 aryl group, for example, hydrogen atom, C1-C8 alkyl group, cyclopentylmethyl group, cyclohexylmethyl group, phenyl group, benzyl group or monofluorophenyl group.

[0054] In some embodiments, in Formula I-(3), R 3 Selected from methyl, ethyl or phenyl.

[0055] In some embodiments, in Formula I-(3), R 1 Selected from hydrogen atom, nitro or Among them, R 6 is selected from C6-C10 alkyl, R 2 is selected from C1-C5 alkyl, C6-C10 alkyl, R 3 is selected from methyl or ethyl, R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are all hydrogen atoms, R 21 , R 22 , R 23 and R 24 are selected from hydrogen atoms.

[0056] In some embodiments, the compound has a structure shown in Formula I-(4),

[0057]

[0058] R 1 Selected from hydrogen atoms, R 4 C(=O)-、R 5 , nitro,

[0059] R 9 and R 10 Each is independently selected from hydrogen or C1-C8 alkyl;

[0060] R 11 , R 12 , R 13 , R 16 , R 17 and R 18 are each independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, a trifluoromethyl group, a C1-C4 alkoxy group, and optionally, R 11 , R 12 , R 13 , R 16 , R 17 and R18 The two adjacent rings form a five-membered, six-membered or seven-membered ring with the connected benzene ring;

[0061] R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The same as the definition of formula (I).

[0062] In some embodiments, in Formula I-(4), R 4 Selected from C1-C6 alkyl, phenyl substituted with one or more C1-C4 alkyl groups.

[0063] In some embodiments, in Formula I-(4), R 5 Selected from C1-C8 alkyl.

[0064] In some embodiments, in Formula I-(4), R 6 is selected from C1-C10 alkyl, one or more C1-C4 alkyl or fluorine-substituted phenyl,

[0065] In some embodiments, in Formula I-(4), R 7 Selected from hydrogen, C1-C10 alkyl, C3-C7 cycloalkyl substituted C1-C2 alkyl, for example cyclohexylmethyl.

[0066] In some embodiments, in Formula I-(4), R 2 Selected from hydrogen atom, C1-C10 alkyl group, C1-C3 alkyl group substituted by C3-C7 cycloalkyl group, C1-C3 alkyl group substituted by phenyl group, C6-C10 aryl group, fluorinated C6-C10 aryl group, for example, hydrogen atom, C1-C8 alkyl group, cyclopentylmethyl group, cyclohexylmethyl group, phenyl group, benzyl group or monofluorophenyl group.

[0067] In some embodiments, in Formula I-(4), R 3 Selected from methyl, ethyl or phenyl.

[0068] In some embodiments, the dioxime ester compound is selected from the group consisting of the following compounds:

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] Preparation of key raw materials:

[0075] Carbazole or substituted carbazole formula II and nitrobenzene compound formula III undergo substitution reaction under alkaline conditions to obtain M 1 ,

[0076]

[0077] In some embodiments, the bioxime ester compound of formula (I) is 1 When it is a hydrogen atom, the preparation method comprises the following steps:

[0078] The first step reaction: HAr 1 H and acyl chloride compound R 2 CH 2 C(=O)Cl or the corresponding anhydride compound reacts under Friedel-Crafts acylation conditions to obtain the intermediate L 1 ;

[0079]

[0080] The second step reaction: make the intermediate L 1 It reacts with nitrite or nitrous acid under the corresponding acid conditions to obtain intermediate L 2 ;

[0081]

[0082] The third step reaction: make the intermediate L 2 React with hydroxylamine hydrochloride under alkaline conditions to obtain intermediate L 3 ;

[0083]

[0084] Step 4: Make intermediate L 3 With R 3 C(=O)Cl or (R 3 C=O) 2 O reacts to obtain a compound of formula Ⅰ-1;

[0085]

[0086] Among them, Ar 1 , R 2 and R 3 The same as defined in formula (I).

[0087] In some embodiments, the dioxime ester compound of formula (I) is 1 For R 4 C(=O)-、R5 When the compound is substituted with nitro, the preparation method of the compound comprises the following steps:

[0088] The first step reaction: HAr 1 H and acyl chloride compound R 2 CH 2 C(=O)Cl or the corresponding anhydride compound reacts under Friedel-Crafts acylation conditions to obtain the intermediate L 1 ;

[0089]

[0090] The second step reaction: make the intermediate L 1 With R 4 C(=O)X undergoes acylation reaction or reacts with R 5 The precursor compound, i.e., the hydroxy compound or the olefin compound, is subjected to an alkylation reaction, or a nitration reaction is performed with nitric acid to obtain the intermediate L 1 ',

[0091]

[0092] The third step reaction: make the intermediate L 1 'React with nitrite or nitrous acid under the corresponding acid conditions to obtain intermediate L 2 ';

[0093]

[0094] Step 4: Make intermediate L 2 'React with hydroxylamine hydrochloride under alkaline conditions to obtain intermediate L 3 ';

[0095]

[0096] Step 5: Make intermediate L 3 'With R 3 C(=O)Cl or (R 3 C=O) 2 O to react to obtain an oxime ester product, a compound of formula Ⅰ-2;

[0097]

[0098] Among them, Ar 1 , R 2 , R 3 , R 4 and R 5 The same as defined in formula (I).

[0099] In some embodiments, the dioxime ester compound of formula (I) is 1for When the compound is prepared, the method comprises the following steps:

[0100] The first step reaction: HAr 1 H and acyl chloride compound R 2 CH 2 C(=O)Cl or the corresponding anhydride compound reacts under Friedel-Crafts acylation conditions to obtain the intermediate L 1 ;

[0101]

[0102] The second step reaction: make the intermediate L 1 With R 6 C(=O)X undergoes acylation reaction to obtain intermediate L 1 ", X is Cl or Br;

[0103]

[0104] The third step reaction: make the intermediate L 1 "React with nitrite or nitrous acid under the corresponding acid conditions to obtain intermediate L 2 ”;

[0105]

[0106] Step 4: Make intermediate L 2 " reacts with hydroxylamine hydrochloride under alkaline conditions to obtain intermediate L 3 ”;

[0107]

[0108] Step 5: Make intermediate L 3 ” and R 3 C(=O)Cl or (R 3 C=O) 2 O reacts to obtain a compound of formula Ⅰ-3;

[0109]

[0110] Among them, Ar 1 , R 2 , R 3 and R 6 The same as defined in formula (I).

[0111] In some embodiments, the dioxime ester compound of formula (I) is 1 for When the compound is prepared, the method comprises the following steps:

[0112] The first step reaction: HAr 1 H and acyl chloride compound R 2 CH 2 C(=O)Cl or the corresponding anhydride compound reacts under Friedel-Crafts acylation conditions to obtain the intermediate L 1 ;

[0113]

[0114] The second step reaction: make the intermediate L 1 With R 7 CH 2 C(=O)X or R 7 C(=O)C(=O)X undergoes acylation reaction to obtain intermediate K 1 or K 1 ', X is Cl or Br;

[0115]

[0116] The third step reaction: make intermediate K 1 or K 1 'React with nitrite or nitrous acid under corresponding acid conditions to obtain intermediate K 2 or K 2 ';

[0117]

[0118] Step 4: Make intermediate K 2 or K 2 'React with hydroxylamine hydrochloride under alkaline conditions to obtain intermediate K 3 ;

[0119]

[0120] Step 5: Make intermediate K 3 With R 3 C(=O)Cl or (R 3 C=O) 2 O reacts to obtain a compound of formula Ⅰ-4;

[0121]

[0122] Among them, Ar 1 , R 2 , R 3 and R 7 The same as defined in formula (I).

[0123] In the present invention, any alkyl group having three or more carbon atoms may be a straight chain or a branched chain structure.

[0124] In the present invention, the NO bond of the oxime group may have both cis and trans configurations relative to the connected C=N. In most cases, the trans configuration may be dominant. Therefore, from the first oximation reaction product to the second oximation reaction product and the esterification product thereof, cis-trans isomers and trans-trans, trans-cis, cis-trans, and cis-cis isomers may or actually exist. However, in actual high pressure liquid chromatography analysis, some isomers may not be completely separated from other isomers.

[0125] In a second aspect, the present invention further provides a photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the dioxime ester compound described in the first aspect.

[0126] In some embodiments, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0127] The photocurable composition of the present invention may further include other photoinitiators or co-initiators. The present invention does not specifically limit the specific types of the other initiators or co-initiators. It is sufficient to select photoinitiators or co-initiators that are helpful for photocuring performance in the art.

[0128] The free radical polymerizable compounds of the present invention include low molecular weight double bond compounds, compounds containing two or more double bonds, and double bond compounds with relatively high molecular weight (eg, 500-3000).

[0129] Examples of the low molecular weight double bond compound include: alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, silicone acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, etc.

[0130] Examples of the compound containing two or more double bonds include: diacrylates of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, triallyl isocyanurate, and the like.

[0131] Examples of the relatively high molecular weight double bond compounds include a large class of substances generally referred to as oligomers, such as acrylated epoxy resins, acrylated polyester resins, unsaturated polyester resins, acrylated polyether resins, and acrylated polyurethane resins.

[0132] The acrylate group in the double bond compound of the present invention may also be replaced by a methacrylate group.

[0133] In some embodiments, the mass proportion of the dioxime ester compound in the photocurable composition is 0.1%-8.0%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or any value therebetween.

[0134] In a third aspect, the present invention further provides an ink or coating, which, in addition to containing the photocurable composition of the second aspect of the present invention, may also contain other necessary ingredients according to the ink color, printing application and other performance requirements.

[0135] In a fourth aspect, the present invention further provides an adhesive which, in addition to containing the photocurable composition of the second aspect of the present invention, may also add other necessary components such as a polymer with a molecular weight of 5000-100000 to improve the adhesive properties according to the performance requirements of the adhesive, and is used for bonding glass, plastic, metal components, etc.

[0136] In addition to the examples given here, those skilled in the art can easily add other necessary ingredients, such as stabilizers, surfactants, leveling agents, and dispersants according to the prior art and the application requirements of the photocurable composition.

[0137] In a fifth aspect, the present invention further provides a photoresist, the raw materials of which include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and a solvent, wherein the photoinitiator includes the dioxime ester compound described in the first aspect of the present invention.

[0138] The multifunctional acrylate monomer in the photoresist raw material of the present invention refers to a trifunctional or higher functionality acrylate monomer. The present invention does not specifically limit the specific type of the multifunctional acrylate monomer, and those skilled in the art can select and use from conventional multifunctional acrylate monomers in the art. Examples of the multifunctional acrylate include, but are not limited to: dipentaerythritol hexaacrylate, pentaerythritol acrylate.

[0139] The alkali-soluble resin in the photoresist raw material of the present invention refers to a polymer with an acidic group, which can be dissolved or dispersed when encountering an alkaline solution. The present invention does not specifically limit the specific type of the alkali-soluble resin, and those skilled in the art can select and use it from the conventional alkali-soluble resins in the art. Examples of the alkali-soluble resin include, but are not limited to, polyacrylates or methacrylates with carboxylic acid groups, such as copolymers obtained by copolymerizing methacrylic acid, itaconic acid, maleic acid, etc. with common monomers in a suitable proportion, and examples of common monomers include, but are not limited to, methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, etc. Examples of alkali-soluble resins include, but are not limited to, copolymers of methyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and butyl methacrylate, and copolymers of methacrylic acid and styrene.

[0140] In some embodiments, the photoresist is a transparent photoresist without pigment. The transparent photoresist can be used to manufacture optical films, polarizers, insulating films, passivation films, sealing protective layers, etc.

[0141] In some embodiments, the photoresist is a colored photoresist containing a pigment. The colored photoresist includes a colored photoresist and a black photoresist, wherein the colored photoresist includes a red photoresist, a green photoresist, and a blue photoresist. The pigment in the raw material of the red photoresist includes a red pigment such as CI Pigment Red 177. The pigment in the raw material of the green photoresist includes a green pigment, such as CI Pigment Green 7. The pigment in the raw material of the blue pigment photoresist includes a blue pigment, such as CI Pigment Blue 15:6 and Solvent Blue 25. The pigment in the raw material of the black photoresist includes a black pigment, such as carbon black, titanium black, CI Pigment Black 1, etc. Black photoresist can be used to manufacture black matrix and cell gap spacers.

[0142] The present invention does not specifically limit the solvent of the photoresist raw material, and those skilled in the art can select it according to needs, such as propylene glycol monomethyl ether acetate.

[0143] In some embodiments, the photoinitiator may also include other photoinitiators or co-initiators known in the art, such as 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene.

[0144] In addition, those skilled in the art may also add a heat stabilizer or a light stabilizer, such as p-methoxyphenol, to the raw materials as needed. Other resins may also be added, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.

[0145] By using the photoresist of the present invention as a raw material, through the color filter processing process such as multiple coating, exposure, development and other existing technical processes of different color photoresists, a color filter device with excellent optical properties can be obtained, which is an important component of a color display screen, wherein the color unit has pure color and high transmittance, and the colorless part has low yellowing and high transmittance.

[0146] The photoresist coating is usually evenly distributed on the substrate by spin coating, and then dried at 80-90℃ to separate the volatile components such as solvents, leaving the solids as films, and placing a mask on the top of the film. The film is exposed to a radiation light source such as a 365nm mercury lamp or LED lamp for a suitable exposure amount. The exposed material is developed in a solution of alkaline substances such as sodium carbonate or sodium hydroxide to remove the unexposed film and leave the exposed image. After that, it is washed and baked at 200-230℃ to make the image better adhere to the substrate. According to the designed procedure, different colors and patterns are produced, or combined with the necessary protective film processing procedures to obtain the filter device.

[0147] In a sixth aspect, the present invention provides a black matrix or photo spacer, which is prepared from a raw material including the photoresist described in the fifth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0148] In a seventh aspect, the present invention provides a color filter device, which is prepared from a raw material including the photoresist described in the fifth aspect of the present invention, wherein the pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

[0149] In an eighth aspect, the present invention provides a printed article or display, which is obtained by photocuring the oxime oxalate compound described in the first aspect of the present invention as a photoinitiator.

[0150] In some embodiments, the printed article comprises a printed circuit board.

[0151] In some embodiments, the display comprises an LCD display or an OLED display.

[0152] In the ninth aspect, the present invention provides the use of the dioxime ester compound described in the first aspect or the photocurable composition described in the second aspect or the photoresist described in the fifth aspect in the preparation of colored or non-colored inks, coatings, adhesives, filters, displays or in pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder mask inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film corrosion-resistant materials, sealants, dental materials, optical materials, optical films, optical fiber coatings, insulating films, polarizers, microlenses, and recording materials.

[0153] Any article such as a color filter, an LCD color display, an OLED color display, a PCB, or a printed matter obtained by using the compound of formula (I) of the present invention or the photoinitiator composition containing the compound of formula (I) as a raw material and processing through necessary steps.

[0154] Compared with the prior art, the present invention has the following beneficial effects:

[0155] The compound of the present invention has significantly high sensitivity in the formulation of photocurable composition, especially photoresist, and its performance is significantly better than that of the prior art. DETAILED DESCRIPTION

[0156] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation to the present invention.

[0157] The term "C1-C10 alkyl" as used herein refers to a straight or branched chain alkyl group having 1 to 10 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

[0158] As used herein, the term "C3-C10 alkyl group interrupted by one or more O atoms or S atoms" or "C3-C10 alkyl group interrupted by one or more oxygen atoms or sulfur atoms" has the same meaning and refers to a C3-C10 alkyl group interrupted by O or S one or more times, for example 1-9 times, 1-5 times, 1-3 times or 2 times or 1 time. If there is more than one spacer group, they are of the same type or different. Two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). These alkyl groups are linear or branched. For example: -CH 2 -CH 2 -O-CH 2 CH 3 -、-CH 2 -CH(CH 3 )-O-CH 2 -CH 2 O-CH 3 -、-CH 2 -CH 2 -S-CH 2 CH 3 wait.

[0159] The term "alkoxy" used herein refers to an alkyl group separated by one O atom, for example, C1-C4 alkoxy refers to an alkyl group having 1-4 carbon atoms separated by one O atom, including but not limited to methoxy, ethoxy, propoxy and the like.

[0160] The term "alkylthio" as used herein is an alkyl group interrupted by one S atom, for example, C1-C4 alkylthio is an alkyl group having 1-4 carbon atoms interrupted by one S atom.

[0161] The term "cycloalkyl" as used herein refers to an alkyl group containing at least one ring, and C3-C7 cycloalkyl refers to a cyclic alkyl group having 3 to 7 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.

[0162] The term "heterocyclic group" as used herein is used interchangeably with "heterocycle", "carbocyclic ring", and "carboheterocyclic group", and includes aromatic cyclic groups and non-aromatic cyclic groups. Aromatic cyclic groups include heteroaromatic cyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-10 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, including at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxirane, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolane, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepineyl, azepineyl and tetrahydrothiazolyl. In addition, the heterocyclic group may be optionally substituted.

[0163] The term "aryl or aromatic group" as used herein includes both non-fused and fused systems. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quadrenyl. In addition, the aryl group may be optionally substituted.

[0164] As used herein, the term "heteroaryl" includes monocyclic or polycyclic ring systems, such as fused ring systems. C4-C20 heteroaryl includes, but is not limited to, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzopyranyl, xanthene, thioxanthenyl, phenothiazine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinolyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenanthrolinyl, oxazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiol, 2,7-phenothiol, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl- 5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl , 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinolyl, 6-quinolyl, 2,3-dimethyl-6-quinolyl, 2,3-dimethoxy-6-quinolyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1-methyl-5-perylene-1-methyl-5-perylene-1-methyl-6-phenanthridinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenazinyl, 10-methyl-2-phenazinyl, and the like. Preferably, it is thienyl, benzo[b]thienyl, thianthrenyl, thioxanthenyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl; more preferably, it is thienyl. In addition, the heteroaryl group may be optionally substituted.

[0165] Experimental materials and equipment:

[0166] Light source equipment:

[0167] 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.;

[0168] Test equipment:

[0169] Stereo microscope: HY-950S, Beijing Huanyu Technology Co., Ltd., line width unit is μm.

[0170] Compound preparation

[0171] Preparation Example 1 1-[9-(4-nitrophenyl)carbazole-3-yl]-1,2-octanedione-1,2-dioxime, O,O'-diacetate

[0172]

[0173] Step 1a. Add 4g (13.8mmol) of N-(4-nitrophenyl) carbazole and 30g of o-dichlorobenzene (hereinafter referred to as DCB) into a 100mL three-necked flask and cool to -10°C. Add 2.2g (16.6mmol) of anhydrous aluminum chloride, stir, add 2.53g (15.5mmol) of octanoyl chloride dropwise within 30min, and then stir and react at 10°C overnight. The reaction solution is acidified and washed with water until neutral, and DCB is removed by vacuum rotary evaporation to obtain 6g of yellow solid. Recrystallize with 40g of ethanol, dry the filter cake to obtain 5.33g of yellow crystalline powder, with a yield of 93.2%, HPLC purity of 99.4%, and DSC melting point of 130.6°C; the intermediate 3-octanoyl-N-(4-nitrophenyl) carbazole;

[0174] Step 1b. First add 2.04g (5mmol) of the product obtained in step 1a, 15g DMSO, and 0.56g (5.4mmol) of n-butyl nitrite into a 100mL three-necked flask; slowly introduce dry hydrogen chloride gas at 20°C; stir and react for 5 hours. Pour the reaction solution into 100g of water and add 20g of dichloromethane for extraction. Wash the dichloromethane phase with water three times until pH = 7, and evaporate the dichloromethane under reduced pressure to obtain 1.88g of crude product. Recrystallize from 15mL of toluene to obtain 1.65g of dry yellow solid, with a yield of 74.4%, HPLC purity of 96.81%, and DSC melting point of 160.2°C; it is the intermediate 3-(2-hydroxyiminooctanoyl)-N-(4-nitrophenyl)carbazole;

[0175] Step 1c. Add 1.0g (2.2mmol) of the product obtained in step 1b, 0.18g (2.4mmol) of hydroxylamine hydrochloride, 5g of ethanol, and 0.4g (5mmol) of pyridine into a 50mL single-mouth bottle, put in a magnetic bar, install a reflux condenser, and turn on magnetic stirring. Stir and react for 12 hours at an oil bath temperature of 80°C; evaporate the ethanol and pyridine under reduced pressure, add 10mL of dichloromethane to dissolve, and wash with water until neutral. Evaporate the dichloromethane, and recrystallize the crude product with ethyl acetate and heptane to obtain 0.85g of a dried yellow solid with a yield of 81.7%. HPLC analysis showed that the total content of the two main isomers was 96.3%; this is the intermediate 3-(1,2-dihydroxyiminooctyl)-N-(4-nitrophenyl)carbazole;

[0176] Step 1d. Add 0.5g (1.1mmol) of the product obtained in step 1c, 0.12g (1.2mmol) of acetic anhydride, and 2.5g of toluene into a 50mL single-mouth bottle, put in a magnetic bar, install a reflux condenser, and turn on magnetic stirring. Stir and react at an oil bath temperature of 40°C for 9 hours; add 2g to the reaction solution, stir for 30min, separate the aqueous phase, and wash with water three times until neutral. Evaporate toluene to obtain 0.51g of crude product, which is recrystallized from ethyl acetate and heptane to obtain 0.42g of yellow solid, with a yield of 71.2%, HPLC content of 96.06%, and a melting point of 60.5-65°C, which is the target 1-[9-(4-nitrophenyl)carbazole-3-yl]-1,2-octanedione-1,2-dioxime, O,O'-diacetate.

[0177] 1 H-NMR (CDCl 3 , ppm): 0.8588-0.8886 (t, 3H, CH 3 ), 1.2740-1.4545(m,6H,3CH 2 ), 1.6077-1.6747(quintet,2H,CH 2 ), 2.2946-2.2987(s+s,6H,2COCH3 ),2.8624-2.8801-2.8970(t,2H,CH 2 ),7.4689-7.5091(m,4H,ArH),7.7928-7.8110(d,2H,ArH),7.8243-7.8420( d,0.56H,ArH), 8.1845-8.2008(d,0.44H,ArH), 8.501-8.5195(s+d,4H,ArH).

[0178] Preparation Example 2 1-[6-(3,5,5-trimethyl-1-acetoxyiminohexyl)-9-(4-nitrophenyl)carbazole-3-yl]-1,2-propanedione-1,2-dioxime, O,O'-diacetate

[0179]

[0180] Step 2a. Add 4g (13.8mmol) of N-(4-nitrophenyl) carbazole and 30g of DCB into a 100mL three-necked flask and cool to -10°C. Add 3.14g (23.6mmol) of anhydrous aluminum chloride, stir, add 2.46g (13.8mmol) of 3,5,5-trimethylhexanoyl chloride dropwise within 30min, and then stir and react at 10°C overnight. The reaction solution is acidified and washed with water until neutral, and DCB is removed by vacuum rotary evaporation to obtain a yellow solid, which is recrystallized with 4g of dichloromethane (hereinafter referred to as DCM) and 10g of ethanol, and the filter cake is dried to obtain 5.02g of yellow powder, with a yield of 84.5%, HPLC purity of 99.2%, and DSC melting point of 112.7°C; the intermediate 3-(3,5,5-trimethylhexanoyl)-N-(4-nitrophenyl) carbazole;

[0181] Step 2b. Add 2.5g (5.8mmol) of the product obtained in step 2a and 30g of DCM into a 100mL three-necked flask, add 3.1g (6.4mmol) of anhydrous aluminum chloride after dissolving, and cool to 0°C with stirring. Then add 0.5g of pre-prepared pyruvic acid chloride (heated with pyruvic acid and dichlorothionyl) dropwise, and react at 5-10°C for 3h. Add the reaction solution dropwise to a solution of 5g of hydrochloric acid and 20mL of water at 0°C, stir for 1h, and stand to separate. Add 20 mL of water to the organic phase, stir for 30 min, and stand to separate; distill the separated organic phase under reduced pressure to 60° C., and the residue is 2.1 g of a yellow solid; add 30 g of ethanol, recrystallize, and dry the filter cake to obtain 2.2 g of yellow crystals with a yield of 76%, a purity of 98.0%, and a DSC melting point of 135.5° C., which is the intermediate 3-(2-oxo-propionyl)-6-(3,5,5-trimethylhexanoyl)-N-(4-nitrophenyl)carbazole.

[0182] Step 2c. Add 2.g (4mmol) of the product obtained in step 2b into a 50mL three-necked flask, add 15g of dimethyl sulfoxide (code name DMSO) to dissolve, add 1.3g (18mmol) of hydroxylamine hydrochloride, and 1.5g (19mmol) of pyridine. Stir and react in an oil bath at 80℃ for 10h; drop the reaction solution into 60mL of water at 5℃, stir for 30min, filter the precipitated solid, wash with water and drain. The wet weight is 2.5g, heat and dissolve it with 15ml of ethanol, filter it at 50℃, cool the filtrate to -15℃, filter the precipitated crystals, and dry them to obtain 1.5g of yellow solid powder, with a yield of 69% and a content of 95.6%, which is the tricarbonyl oxime of the intermediate 3-(2-oxo-propionyl)-6-(3,5,5-trimethylhexanoyl)-N-(4-nitrophenyl)carbazole;

[0183] Step 2d. Place 0.7 g (1.1 mmol) of 2c product, 0.9 g (8.8 mmol) of acetic anhydride, and 15 g of DCM in a 50 mL single-mouth bottle, and stir at 40-45 ° C for 4 h. Add 15 mL of water to the reaction solution, stir and wash with water for 1 h, and let stand to separate. The separated organic phase is washed with water 3 times, each time with 15 mL of water; filter the organic phase, and then remove DCM by vacuum distillation. The residue is a light yellow oil, which is recrystallized by adding 10 g of ethanol, and the precipitated crystals are filtered and dried under reduced pressure to obtain 0.5 g of yellow crystals, with a yield of 66.7%, a content of 95.85%, and a DSC melting point of 149.1 ° C.

[0184] 1 H-NMR (CDCl 3 , ppm):0.8854(s,12H,4CH 3 ), 1.2522-1.2837(m,5H,2CH 2 +CH), 2.2946-2.3106(m,9H,3COCH 3 ),2.5444(s,3H,CH 3 ),7.4608-7.4871(d+d,2H,ArH), 7.7948-7.8131(d,1.2H,ArH), 7.8493-7.8670(d,0.4 H,ArH), 7.9438-7.9616(d,0.4H,ArH), 8.5241-8.5423(d,2H,ArH), 8.5647(s,4H,ArH).

[0185] Preparation Example 3 1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-3-cyclohexyl-1,2-propanedione-1,2-dioxime, O,O'-diacetate

[0186]

[0187] Step 3a. Add 6.4g (0.02mol) of isooctylcarbazole, 32.0g of 1,2-dichloroethane (hereinafter referred to as DCE), and 2.92g (0.022mol) of anhydrous aluminum chloride to a 100mL three-necked flask, and cool to -10°C with stirring. Add 3.48g (0.02mol) of 3-cyclohexylpropionyl chloride dropwise, and keep warm for 4 hours after the addition is complete. Acid hydrolysis and water washing are performed, and the solvent is evaporated to obtain 8.51g of crude product, which is separated by column chromatography to obtain 5.5g of intermediate 3-(3-cyclohexylpropionyl)-9-(2-ethylhexyl)carbazole, with HPLC purity of 98.1% and yield of 66.1%.

[0188] Step 3b. Add 4.18g (0.01mol) of the product obtained in step 3a and 20g of DCE to a 100mL three-necked flask, stir to dissolve, keep the water bath at 25°C, dropwise add 1.15g (0.011mol) of 65% concentrated nitric acid, and stir to react for 3 hours. Wash the reaction solution with water, evaporate the solvent to obtain a crude product. The crude product is first slurried with heptane, then recrystallized with ethyl acetate and heptane to obtain 3.56g of a dried yellow solid, with a yield of 76.95%, a HPLC purity of 98.8%, and a DSC melting point of 112°C, which is the intermediate 6-nitro-3-(3-cyclohexylpropionyl)-9-(2-ethylhexyl)carbazole.

[0189] Step 3c. First add 3.0g (6.4mmol) of the product obtained in step 3b, 15.0g DMSO, and 1.0g (9.7mmol) butyl nitrite into a 50mL two-necked bottle; keep the temperature in a water bath at 35°C and stir to react for 5 hours. Pour the reaction solution into 100g water, add 20.0g DCE to extract, separate the liquids, wash the organic phase with water 4 times until pH=7, using 5.0g water each time; evaporate to dryness under reduced pressure to obtain a crude product. Add 15g heptane to the crude product to slurry, and obtain 3.0g of yellow solid, with a yield of 94.3% and a HPLC purity of 97.54% (90.66% for trans isomers + 6.88% for cis isomers); the intermediate 6-nitro-3-(3-cyclohexyl-2-hydroxyiminopropionyl)-9-(2-ethylhexyl)carbazole.

[0190] Step 3d. First, add 3.0g (6.1mmol) of the product obtained in step 3c, 15.0g of ethanol, 0.5g (7.2mmol) of hydroxylamine hydrochloride, and 0.6g (7.6mmol) of pyridine into a 50mL two-necked bottle, and stir in an oil bath at 80°C for 24h. Evaporate the solvent and low-boiling substances under reduced pressure, dissolve the residue in 15ml of DCM, wash with water, evaporate the DCM again, and recrystallize the residue with a mixed solvent of ethanol and ethyl acetate to obtain 2.5g of a dry yellow powder, with a yield of 80.9%, HPLC content of 98.25% (91.25% of the main isomer + 7.0% of the minor isomer), and DSC melting point: 219.5°C, which is the intermediate 6-nitro-3-(3-cyclohexyl-1,2-dihydroxyiminopropyl)-9-(2-ethylhexyl)carbazole.

[0191] Step 3e. Add 1.28g (2.4mmol) of the product obtained in step 3d, 0.6g (6mmol) of acetic anhydride, 20g of DCM, and a magnetic bar into a 50ml single-mouth bottle, keep warm in a water bath at 25°C, and stir magnetically for 5h. Add 4.0g of deionized water to the reaction solution, wash the separated liquid, and then wash with water 3 times until the pH of the aqueous phase is 6-7; evaporate the DCM to dryness to obtain 1.36g of crude product. The crude product was added with 5.0 g of ethanol and 5 g of heptane, heated until completely dissolved, cooled to -10°C for crystallization, filtered, and the filter cake was dried to obtain 1.04 g of a yellow solid; the yield was 73.3%, HPLC content: 98.59% (major isomer 96.49%, minor isomer 2.1%), DSC melting point: 122.8°C; the target compound was 1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-3-cyclohexyl-1,2-propanedione-1,2-dioxime, O,O'-diacetate.

[0192] 1 H-NMR (CDCl 3 , ppm):0.8439-0.8590-0.8740(t,6H,2CH 3 ), 0.9308-1.8113 (m, 20H, CH of cyclohexane and 2-ethylhexyl 2 +CH), 2.1413 (s, 3H, COCH 3 ), 2.1648(s,3H,COCH 3 ), 2.8545-2.8702(d,2H,CH 2 ), 4.2182-4.2395(d,2H,CH 2),7.4215-7.4406(d,1H,ArH), 7.4785-7.4965(d,1H,ArH), 7.5782-7.5973(d,1H,ArH), 7.82 43-7.8420(d,1H,ArH), 8.1848(d,1H,ArH), 8.3942-8.4125(d,1H,ArH), 9.0054(s,1H,ArH).

[0193] Preparation Example 4 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-3,5,5-trimethyl-1,2-hexanedione-1,2-dioxime, O,O'-diacetate

[0194]

[0195] Step 4a. Add 4g (13.8mmol) of N-(4-nitrophenyl) carbazole and 30g of DCB into a 100mL three-necked flask, cool to -10°C, add 3.14g (23.6mmol) of anhydrous aluminum chloride, stir, dropwise add 2.46g (13.8mmol) of 3,5,5-trimethylhexanoyl chloride within 30min, and then stir and react overnight at 10°C. The reaction solution is acidified and washed with water until neutral, and DCB is removed by vacuum rotary evaporation to obtain a yellow solid, which is recrystallized with 4g of dichloromethane (hereinafter referred to as DCM) and 10g of ethanol, and the filter cake is dried to obtain 5.02g of yellow powder, with a yield of 84.5%, HPLC purity of 99.2%, and DSC melting point of 112.7°C; the intermediate 3-(3,5,5-trimethylhexanoyl)-9-(4-nitrophenyl) carbazole.

[0196] Step 4b. Add 4.29g (10mmol) of the product obtained in step 4a and 20g of DCE to a 100mL three-necked flask, stir to dissolve, keep the water bath at 25°C, dropwise add 1.26g (13mmol) of 65% concentrated nitric acid, and stir to react for 3 hours. Wash the reaction solution with water, evaporate the solvent to obtain a crude product, first slurry it with heptane, then recrystallize it with ethyl acetate and heptane, and dry it to obtain 3.3g of yellow solid, with a yield of 70%, HPLC purity of 97.72%, and DSC melting point of 257.1°C, which is the intermediate 6-nitro-3-(3,5,5-trimethylhexanoyl)-9-(4-nitrophenyl)carbazole.

[0197] Step 4c. First add 3.0g (6.3mmol) of the product obtained in step 4b, 15.0g of tetrahydrofuran (THF), and 0.71g (6.93mmol) of butyl nitrite to a 50mL two-necked bottle; keep the water bath at 35°C and stir to react for 5 hours. Pour the reaction solution into 100g of water, add 20.0g of DCM to extract, separate the liquid, wash the organic phase with water 4 times until pH=7, using 5.0g of water each time; evaporate to dryness under reduced pressure to obtain a crude product. Add 15g of heptane to the crude product to slurry, and obtain 3.0g of yellow solid, with a yield of 94.7% and a HPLC purity of 99% (isomer 1 content 50.72%; isomer 2 content 24.32%; isomer 3 content 23.98%); the intermediate 6-nitro-3-(3,5,5-trimethyl-2-hydroxyiminohexanoyl)-9-(4-nitrophenyl)carbazole.

[0198] Step 4d. First add 2.1g (4.18mmol) of the product obtained in step 4c, 4.5g of pyridine, and 0.42g (6mmol) of hydroxylamine hydrochloride into a 50mL two-necked bottle, and stir in an oil bath at 80°C for 24h. Evaporate the solvent and low-boiling substances under reduced pressure, dissolve the residue in 15ml of DCM, wash with water, evaporate the DCM again, and recrystallize the residue with a mixed solvent of heptane and ethyl acetate to obtain 1.8g of a dry yellow powder, with a yield of 83.2%, HPLC content of 95.25% (isomer 1 content of 53.36%, isomer 2 content of 23.78%; isomer 3 content of 18.09%), DSC melting point: 176.9°C, which is the intermediate 6-nitro-3-(3,5,5-trimethyl-1,2-dihydroxyiminohexyl)-9-(2-ethylhexyl)carbazole.

[0199] Step 4e. Add 1.04 g (2 mmol) of the product obtained in step 4d, 0.44 g (4.3 mmol) of acetic anhydride, 15 g of DCM, and a magnetic bar into a 50 mL single-mouth bottle, keep warm in a water bath at 25°C, and stir magnetically for 5 hours. Add 4.0 g of deionized water to the reaction solution, wash the separated liquid, and then wash with water 3 times until the pH of the aqueous phase is 6-7; evaporate the DCM to dryness to obtain 1.16 g of crude product. The crude product was recrystallized from a mixture of heptane and ethyl acetate, and the filter cake was dried to obtain 0.76 g of a yellow solid; the yield was 63.1%, HPLC content: 96.58% (86.92% major isomer, 9.66% minor isomer), melting range: 76.9-80.1°C; the target compound was 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-3,5,5-trimethyl-1,2-hexanedione-1,2-dioxime, O,O'-diacetate.

[0200] 1 H-NMR (CDCl 3 , ppm): 0.88862(s,3H,CH 3 ),0.8944(s,3H,CH3 ), 0.9676(s,3H,CH 3 ),1.2573-1.3676(m.3H,CH 2 +CH),2.0149-2.2713(s+s+s+s,6H,2COCH 3 ), 7.4789-7.4970(d), 7.8026-7.8137-7.8214-7.8317(m), 8.2540(s), 8.3762-8.3982-8.4204(t), 8.5323-8.6039(m), 9.0648(s), 9.1200(s).

[0201] Comparison compounds:

[0202] 1-(6-o-methylbenzoyl-9-ethyl-9H-carbazole-3-yl)-ethanone oxime-O-acetate (BASF photoinitiator product OXE 02)

[0203] Comparative Compound A

[0204] Comparative compound B was prepared with reference to Example 4 of the specification of patent CN102459171A.

[0205] Preparation of alkali soluble resin

[0206] Dissolve 20 g of benzyl methacrylate, 3 g of methacrylic acid, 7 g of hydroxyethyl methacrylate, 1.5 g of azobisisobutyronitrile, and 0.5 g of dodecanethiol in 200 mL of toluene and put into a constant pressure dropping funnel. Put 100 mL of toluene in a 500 mL four-necked bottle, replace with nitrogen, heat to 80°C, add the solution in the funnel dropwise, react for 6 hours, then cool and filter to obtain 24 g of white alkali-soluble resin.

[0207] Black color paste preparation

[0208] 50 g of the alkali-soluble resin prepared by the above method, 50 g of P30 carbon black, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate were put into a 500 mL beaker, and mixed at a speed of 5000 r / min for 15 min using a high-speed shear mixer to obtain a black color paste.

[0209] Preparation of red color paste

[0210] 50 g of the alkali-soluble resin prepared by the above method, 50 g of Ciba IRGALITE RED 2BXL-Q pigment, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate were put into a 500 mL beaker, and mixed at a speed of 5000 r / min for 15 min using a high-speed shear mixer to obtain a red color paste.

[0211] Photoresist composition examples and comparative examples

[0212] The compounds prepared in Preparation Examples 1-4 and comparative compounds A and B were used as initiators, mixed and dissolved in the solvent PMA according to the proportions in Table 1, and then mixed with black color paste according to the proportions in Table 1, with the dosage unit being grams.

[0213] After mixing all the components evenly, use a 10 μm wire rod to coat the film on a glass slide, dry it in a 90°C oven for 5 min, use a 365 nm light source, use a 41-step gray gradient ruler as a mask, and use 1% Na 2 CO 3 The solution was developed at 25°C, and then washed with pure water for 10 seconds. After drying in an oven at 90°C for 10 minutes, the number of film stages remaining was observed and recorded.

[0214] Table 1

[0215]

[0216]

[0217] The mixtures of the examples and comparative examples in Table 1 were coated, cured, developed, and measured, and the data are shown in Table 2. Under the same dosage conditions, the larger the number of film retention steps after curing, the higher the sensitivity of the formula. All the preparation example compounds were significantly more sensitive than the comparative compound A.

[0218] Table 2

[0219]

[0220] It can be seen from the data in Table 2 that, compared with the comparative compound A, the compound provided by the present invention, under the same dosage conditions, has a larger number of development film retention stages after curing of the photoresist composition, and a higher formulation sensitivity. The compound of general formula I of the present invention has the characteristic of high sensitivity.

[0221] The compounds prepared in Preparation Examples 1-4 and comparative compounds A and B were used as initiators, mixed and dissolved in the solvent PMA according to the proportions in Table 3, and then mixed with red color paste according to the proportions in Table 3, with the dosage unit being grams.

[0222] After mixing all the components evenly, use a 10 μm wire rod to coat the film on a glass slide, dry it in a 90°C oven for 5 min, use a 365 nm light source with a 41-step gray gradient ruler as a mask, and use 1% Na 2 CO 3 The solution was developed at 25°C, and then washed with pure water for 10 seconds. After drying in an oven at 90°C for 10 minutes, the number of film stages remaining was observed and recorded.

[0223] Table 3

[0224] Photoinitiator Photoinitiator dosage Black color paste dosage Solvent PMA dosage Example 5 Compound 11 0.08 2 4.5 Example 6 Compound 25 0.08 2 4.5 Example 7 Compound 8 0.08 2 4.5 Example 8 Compound 15 0.08 2 44.5 Comparative Example 3 Comparative Compound A 0.08 2 4.5 Comparative Example 4 Comparative Compound B 0.08 2 4.5

[0225] The examples and comparative examples in Table 3 were coated, cured, developed, and measured, and the data were shown in Table 4.

[0226]

[0227] It can be seen from Table 4 that the compounds provided by the present invention, under the same dosage conditions, have significantly better curing sensitivity than the comparative compound A in the red formulation system.

[0228] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A dioxime ester compound having a structure as shown in formula (I), in, R1 is selected from hydrogen atom, nitro, R4C(=O)-, R5, R2 is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a C3-C10 alkyl group inserted by one or more O atoms, a C3-C7 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group, wherein the substituent in the C1-C10 alkyl group is selected from one or more of a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, a C1-C4 alkoxy group, or a C1-C4 alkyl acyloxy group; Optionally, R2 is connected to a carbon atom or a nitrogen atom on the ring of Ar1, so that the side chain where R2 is located and the two atoms on the ring of Ar1 together form a five-membered to seven-membered ring; The C3-C7 cycloalkyl and C3-C7 heterocyclic groups involved in R2 are unsubstituted or substituted by one or more substituents selected from F, Cl, C1-C4 alkyl, C1-C4 alkoxy, R4C(=O)O-; R3 is selected from C1-C3 alkyl, C1-C4 alkoxy, phenyl, R4OC(=O)- or R4C(=O)-; R4 is selected from C1-C8 alkyl, C3-C7 cycloalkyl, C1-C3 alkyl substituted by C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, R5O(C=O)- or -C(=O)NR5R5′; R5, R5' are each independently selected from substituted or unsubstituted C1-C8 alkyl, cyclopentyl, cyclohexyl, and the substituent in the C1-C8 alkyl is selected from one or more of F atom, phenyl, and C3-C7 cycloalkyl; Optionally, R5R5′N forms the following cyclic structure: R6 is selected from C1-C11 alkyl, C3-C7 cycloalkyl, C1-C3 alkyl substituted by C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, R5O(C=O)- or -C(=O)NR5R5′; R7 is selected from C1-C10 alkyl, C3-C7 cycloalkyl, C1-C2 alkyl substituted by C3-C7 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; Ar1 is selected from substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C4-C20 heteroarylene; The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=C)R3; The substituents in the C6-C20 arylene group and the C4-C20 heteroarylene group are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=C)R3.

2. The dioxime ester compound according to claim 1, wherein The compound has a structure shown in Formula I-(1) or Formula I-(2), in, R1 is selected from R4C(=O)-, nitro, R8 is selected from C1-C8 alkyl, R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each is independently selected from a hydrogen atom, F, a C1-C4 alkyl group or a trifluoromethyl group; R2, R3, R4, R5, R6 and R7 are defined in the same manner as in formula (I); Preferably, R4 is selected from C1-C6 alkyl, one or more C1-C4 alkyl substituted phenyl, R6 is selected from C1-C6 alkyl, one or more C1-C4 alkyl substituted phenyl, R7 is selected from hydrogen or C1-C6 alkyl; Preferably, R2 is selected from a hydrogen atom, a C1-C8 alkyl group, a C1-C3 alkyl group substituted with a C3-C7 cycloalkyl group, a C6-C10 aryl group; for example, a hydrogen atom, a C1-C6 alkyl group, a cyclopentylmethyl group, a cyclohexylmethyl group or a phenyl group; Preferably, R3 is selected from methyl, ethyl or phenyl.

3. The dioxime ester compound according to claim 1, wherein The compound has a structure shown in formula I-(3), in R1 is selected from hydrogen atom, R4C(=O)-, R5, R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, a trifluoromethyl group or a C1-C4 alkoxy group, and optionally, R 11 , R 12 , R 13 , R 14 , R 15 and R 16 The two adjacent ones form a five-membered to seven-membered ring with the connected benzene ring; R 21 , R 22 , R 23 and R 24 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, a trifluoromethyl group or a C1-C4 alkoxy group; The definitions of R2, R3, R4, R5, R6 and R7 are the same as those in formula (I), Preferably, R4 is selected from C1-C6 alkyl, one or more C1-C4 alkyl-substituted phenyl, R5 is selected from C1-C8 alkyl, cyclopentyl or cyclohexyl, R6 is selected from C1-C10 alkyl, one or more C1-C4 alkyl-substituted phenyl, C4-C10 heteroaryl, such as thienyl, R7 is selected from hydrogen or C1-C10 alkyl; Preferably, R2 is selected from a hydrogen atom, a C1-C10 alkyl group, a C1-C3 alkyl group substituted with a C3-C7 cycloalkyl group, a C1-C3 alkyl group substituted with a phenyl group, a C6-C10 aryl group, a fluorinated C6-C10 aryl group, such as a hydrogen atom, a C1-C8 alkyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group or a monofluorophenyl group; Preferably, R3 is selected from methyl, ethyl or phenyl.

4. The dioxime ester compound according to claim 1, wherein The compound has a structure shown in formula I-(4) in R1 is selected from hydrogen atom, R4C(=O)-, R5, nitro, R9 and R 10 Each is independently selected from hydrogen or C1-C8 alkyl; R 11 , R 12 , R 13 , R 16 , R 17 and R 18 are each independently selected from a hydrogen atom, a deuterium atom, F, Cl, a C1-C4 alkyl group, a trifluoromethyl group, a C1-C4 alkoxy group, and optionally, R 11 , R 12 , R 13 , R 16 , R 17 and R 18 The two adjacent ones form a five-membered to seven-membered ring with the connected benzene ring; R2, R3, R4, R5, R6 and R7 are defined in the same manner as in formula (I); Preferably, R4 is selected from C1-C6 alkyl, one or more C1-C4 alkyl substituted phenyl, R5 is selected from C1-C8 alkyl, R6 is selected from C1-C10 alkyl, one or more C1-C4 alkyl or fluorine substituted phenyl, R7 is selected from hydrogen, C1-C10 alkyl, C1-C2 alkyl substituted by C3-C7 cycloalkyl, for example cyclohexylmethyl; Preferably, R2 is selected from a hydrogen atom, a C1-C10 alkyl group, a C1-C3 alkyl group substituted with a C3-C7 cycloalkyl group, a C1-C3 alkyl group substituted with a phenyl group, a C6-C10 aryl group, a fluorinated C6-C10 aryl group, such as a hydrogen atom, a C1-C8 alkyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group or a monofluorophenyl group; Preferably, R3 is selected from methyl, ethyl or phenyl.

5. The dioxime ester compound according to any one of claims 1 to 4, wherein R1 is selected from hydrogen atom, R4C(=O)-, nitro, R2 is selected from C1-C6 alkyl, cyclopentylmethyl or cyclohexylmethyl; R3 is selected from methyl or phenyl; R4 is selected from C1-C8 alkyl, C3-C7 cycloalkyl, C1-C3 alkyl substituted with C3-C7 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted thienyl; R5 is selected from C1-C8 alkyl, R6 is selected from C1-C11 alkyl, cyclohexyl, 2-cyclohexylethyl, phenyl, 4-fluorophenyl, thiophen-2-yl; R7 is selected from C1-C10 alkyl, cyclohexylmethyl, phenyl, 4-fluorophenyl; The substituents in the phenyl group and the thienyl group are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -O(O=)CR3.

6. The dioxime ester compound according to any one of claims 1 to 5, wherein The compound is selected from the group consisting of the following compounds:

7. The dioxime ester compound according to claim 1, characterized in that: When R1 is a hydrogen atom, the preparation method of the compound comprises the following steps: Step (1): reacting HAr1H with an acyl chloride compound R2CH2C(=O)Cl or a corresponding anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate L1; Step (2): reacting the intermediate L1 of step (1) with a nitrite or nitrous acid under acid conditions corresponding to the nitrous acid to obtain an intermediate L2; Step (3): reacting the intermediate L2 of step (2) with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate L3; Step (4): reacting the intermediate L3 of step (3) with R3C(=O)Cl or (R3C=O)2O to obtain a compound of formula Ⅰ-1; wherein Ar1, R2 and R3 are defined the same as in formula (I).

8. The dioxime ester compound according to claim 1, characterized in that: When R1 is selected from R4C(=O)-, R5 or nitro, the preparation method of the compound comprises the following steps: Step (1): reacting HAr1H with an acyl chloride compound R2CH2C(=O)Cl or a corresponding anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate L1; Step (2): subjecting the intermediate L1 of step (1) to an acylation reaction with R4C(=O)X or an alkylation reaction with a precursor compound of R5, such as a hydroxyl compound or an olefin compound, or a nitration reaction with nitric acid to obtain an intermediate L1'. Step (3): reacting the intermediate L1' in step (2) with a nitrite or nitrous acid under acid conditions corresponding to the nitrous acid to obtain an intermediate L2'; Step (4): reacting the intermediate L2' in step (3) with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate L3'; Step (5): reacting the intermediate L3' in step (4) with R3C(=O)Cl or (R3C=O)2O to obtain a compound of formula Ⅰ-2; wherein Ar1, R2, R3, R4 and R5 are defined the same as in formula (I).

9. The dioxime ester compound according to claim 1, characterized in that: When R1 is When the compound is prepared, the method comprises the following steps: Step (1): reacting HAr1H with an acyl chloride compound R2CH2C(=O)Cl or a corresponding anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate L1; Step (2): subjecting the intermediate L1 of step (1) to an acylation reaction with R6C(=O)X to obtain an intermediate L1", wherein X is Cl or Br; Step (3): reacting the intermediate L1" in step (2) with a nitrite or nitrous acid under acid conditions corresponding to the nitrite to obtain an intermediate L2"; Step (4): reacting the intermediate L2" in step (3) with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate L3"; Step (5): reacting the intermediate L3" of step (4) with R3C(=O)Cl or (R3C=O)2O to obtain a compound of formula Ⅰ-3; wherein Ar1, R2, R3 and R6 are defined the same as in formula (I).

10. The dioxime ester compound according to claim 1, characterized in that: When R1 is When the compound is prepared, the method comprises the following steps: Step (1): reacting HAr1H with an acyl chloride compound R2CH2C(=O)Cl or a corresponding anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate L1; Step (2): subjecting the intermediate L1 to an acylation reaction with R7CH2C(=O)X or R7C(=O)C(=O)X to obtain the intermediate K1 or K1', wherein X is Cl or Br; Step (3): reacting the intermediate K1 or K1' in step (2) with a nitrite or nitrous acid under corresponding acid conditions to obtain an intermediate K2 or K2', respectively; Step (4): reacting the intermediate K2 or K2' in step (3) with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate K3; Step (5): reacting the intermediate K3 of step (4) with R3C(=O)Cl or (R3C=O)2O to obtain a compound of formula Ⅰ-4; wherein Ar1, R2, R3 and R7 are defined the same as in formula (I).

11. A photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the dioxime ester compound according to any one of claims 1 to 10; Preferably, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds and combinations thereof; Preferably, the free radical polymerizable compound comprises one or more of alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylated epoxy resin, acrylated polyester resin, unsaturated polyester resin, acrylated polyether resin, acrylated polyurethane resin; More preferably, the free radical polymerizable compound comprises one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate; More preferably, the mass proportion of the dioxime ester compound in the photocurable composition is 0.1%-8.0%.

12. A photoresist, the raw materials of which include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and an organic solvent, wherein: The photoinitiator comprises the dioxime ester compound according to any one of claims 1 to 10; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality ≥ 3, more preferably dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin having an acidic group, more preferably a polyacrylate or methacrylate having a carboxylic acid group, and further preferably a copolymer formed by one or more of methacrylic acid, itaconic acid, and maleic acid and one or more of methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as a copolymer of methyl methacrylate and methacrylic acid, a copolymer of benzyl methacrylate and methacrylic acid, a copolymer of methyl methacrylate and butyl methacrylate, and a copolymer of methacrylic acid and styrene; Preferably, the organic solvent is selected from ester solvents, aromatic hydrocarbon solvents and halogenated alkane solvents, preferably propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, toluene, xylene, tetrachloroethane; Optionally, the photoinitiator further includes one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene; Optionally, the photoresist raw material also contains a pigment; preferably, the pigment is a red pigment, a green pigment, a blue pigment or a black pigment; more preferably, the red pigment includes CI Pigment Red 177, the green pigment includes CI Pigment Green 7, the blue pigment includes CI Pigment Blue 15:6 and Solvent Blue 25, and the black pigment includes carbon black, titanium black and CI Pigment Black 1.

13. A black matrix or photo spacer, prepared from a raw material comprising the photoresist according to claim 12, wherein: The pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

14. A color filter device, prepared from a raw material comprising the photoresist according to claim 12, wherein: The pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

15. A printed article or display, obtained by photocuring the dioxime ester compound according to any one of claims 1 to 10 as a photoinitiator; preferably, the printed article comprises a printed circuit board, and the display comprises a PCB display, an LCD display, or an OLED display.

16. Use of the dioxime ester compound according to any one of claims 1 to 10, the photocurable composition according to claim 11, or the photoresist according to claim 12 in the preparation of colored or non-colored inks, coatings, adhesives, filters, displays, or in pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder mask inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film corrosion-resistant materials, sealants, dental materials, optical materials, optical films, optical fiber coatings, insulating films, polarizers, microlenses, and recording materials.

Images