Oxime ester photoinitiator and photosensitive composition containing the same

Abstract

The present invention provides an oxime ester photoinitiator and a photosensitive composition containing the same. The oxime ester photoinitiator has a structure shown in the following general formula (I), (II) or (III). The oxime ester photoinitiator provided in the present invention has good heat resistance and high sensitivity.

Description

Technical Field

[0001] The present invention belongs to the technical field of liquid crystal display, and specifically relates to an oxime ester photoinitiator and a photosensitive composition containing the same, and more specifically relates to an oxime ester photoinitiator with full-band high sensitivity, a preparation method thereof, and a photosensitive composition containing the same. Background Art

[0002] With the development of electronic technology, the photosensitive compositions provided in the prior art have begun to show their shortcomings in some application fields. With the in-depth research on photosensitive compositions, people have also put forward higher requirements for the photoinitiators in the photosensitive compositions. For example, the photosensitive compositions currently used for gap control materials are mostly poor in heat resistance. This is mainly due to the poor heat resistance of the photoinitiators in the photosensitive compositions, which makes the electronic products easy to collapse during the baking or packaging process, and the gap materials shrink. In the coating, exposure and development processes, deliberately increasing the height of the gap control material will increase its cost. When it collapses due to heat, the small molecules melted out will pollute the liquid crystal; for example, in the production of high-end color filters, on the one hand, the photoinitiator needs to meet the basic requirements of high solubility and good thermal stability. On the other hand, its high color quality performance requires highly colored resists. As the pigment content increases, the curing of the color resist becomes more difficult, and the clarity and integrity of the image after curing also have higher requirements. This requires a higher sensitivity initiator to solve the above problems.

[0003] Therefore, how to provide a photoinitiator with better heat resistance and higher sensitivity has become a technical problem that needs to be solved urgently. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide an oxime ester photoinitiator and a photosensitive composition containing the same. In the present invention, an oxime ester photoinitiator with good heat resistance and high sensitivity is obtained through structural design.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides an oxime ester photoinitiator, characterized in that the oxime ester photoinitiator has a structure as shown in formula (I), (II) or (III):

[0007]

[0008]

[0009] Wherein, R1 is selected from any one of C1-C20 straight or branched alkyl, C1-C20 straight or branched fluoroalkyl, C3-C20 cycloalkyl, C3-C20 fluorocycloalkyl, substituted or unsubstituted C6-C30 aryl or camphoryl;

[0010] R2 is selected from unsubstituted or fluorinated C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl or substituted acyl Any one of, R′ is selected from C1-C10 alkyl or C6-C10 aryl, * represents the connection site;

[0011] R3 and R4 are each independently selected from any one of a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C20 straight or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylthio group, a substituted or unsubstituted C2-C20 hydrocarbon derivative group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C5-C30 heteroaryl group, wherein the C2-C20 hydrocarbon derivative group contains at least one of -O-, -S-, and -O-CO-, or a combination of any two of them, and -O-, -S-, and -O-CO- are not located at the terminal position of the C2-C20 hydrocarbon derivative group; or R3 and R4 may be connected to each other to form a ring;

[0012] R5-R7 are each independently selected from hydrogen, nitro, cyano, hydroxyl, halogen, C1-C20 straight-chain or branched alkyl, wherein the hydrogen atoms in the chain of the C1-C20 straight-chain or branched alkyl may be substituted by halogen atoms, hydroxyl, C2-C20 straight-chain or branched alkenyl, C2-C20 straight-chain or branched alkynyl, C1-C20 straight-chain or branched alkyl, or -CH2- in the C1-C20 straight-chain or branched alkyl may be replaced by -O-, -S-, - -CO-, -COO- or -OCO- substituted; C3-C30 cycloalkyl, the hydrogen atoms in the C3-C30 cycloalkyl may be substituted by halogen, C1-C20 straight or branched alkyl, C2-C20 straight or branched alkyl interrupted by one or more -O-, -S-, -OCO- or -COO-; bridged cycloalkyl, the hydrogen atoms in the bridged cycloalkyl may be substituted by halogen, C1-C20 straight or branched alkyl, interrupted by one or more -O-, -S-, -OCO- or - A C2-C20 straight-chain or branched alkyl group interrupted by COO- is substituted; a C6-C30 aryl group, wherein at least one hydrogen atom in the phenyl group of the C6-C30 aryl group is substituted by a C1-C20 straight-chain or branched alkyl group, a C1-C20 straight-chain or branched alkoxy group, a C1-C20 alkoxy group substituted by a C6-C20 aryl group, a C1-C20 straight-chain or branched alkylthio group, a C1-C20 acyl group, a C1-C20 acyloxy group or a C1-C20 oxyacyl group. a C3-C20 heterocyclic group containing N, O and / or S, wherein the hydrogen atoms in the C3-C20 heterocyclic group containing N, O and / or S may be replaced by halogen atoms or hydroxyl groups, C2-C20 straight-chain or branched alkenyl groups, C2-C20 straight-chain or branched alkynyl groups, C1-C20 straight-chain or branched alkyl groups, or -CH2- in C1-C20 straight-chain or branched alkyl groups may be replaced by -O-, -S-, -CO-, -COO- or -OCO-;

[0013] Alternatively, R5-R7 are each independently R8 is selected from the following groups: C1-C20 straight-chain or branched alkyl or halogenated alkyl or hydroxy-substituted alkyl, C3-C20 cycloalkyl, C2-C20 straight-chain or branched alkenyl, C2-C20 straight-chain or branched alkynyl, C1-C20 straight-chain or branched alkoxy or alkylthio, C2-C20 straight-chain or branched hydroxyalkoxy-substituted alkyl, C1-C20 alkyl substituted by C6-C10 aryl or aryloxy, a C2-C20 straight-chain or branched alkyl group interrupted by one or more -O-, -S-, -O-CO- or -CO-O-; a C6-C30 aryl group, a substituent formed by replacing at least one hydrogen atom in the phenyl group of the C6-C30 aryl group with a C1-C20 straight-chain or branched alkyl group, an alkoxy group, an alkylthio group, a C1-C20 acyl group, a C1-C20 acyloxy group or a C1-C20 oxyacyl group; a C2-C20 heterocyclic group containing N, O and / or S;

[0014] Alternatively, R5-R7 are each independently R9 is selected from the following groups: hydrogen, C1-C20 straight-chain or branched alkyl or halogenated alkyl, wherein -CH2- can be replaced by -O-, -S-, -CO-, -COO- or -OCO- to form a substituent; C3-C20 cycloalkyl, wherein the hydrogen atom can be replaced by a halogen atom or a hydroxyl group; C1-C20 straight-chain or branched alkyl (-CH2- in the chain is replaced by -O-, -S-, -CO-, -COO- or -OCO-), C2-C20 straight-chain or branched alkenyl, C2-C20 straight-chain or branched alkynyl; C2-C20 straight-chain or branched alkenyl; C2-C20 straight-chain or branched alkynyl; C1-C20 straight-chain or branched hydroxy-substituted alkyl C2 -C20 linear or branched hydroxyalkoxy substituted alkyl, C1-C20 alkyl substituted by C6-C10 aryl or aryloxy, C2-C20 linear or branched alkyl or alkoxy interrupted by one or more -O-, -S-, -O-CO- or -CO-O-; C6-C30 aryl, a substituent formed by replacing at least one hydrogen atom in the phenyl group of C6-C30 aryl with C1-C20 linear or branched alkyl, C1-C20 linear or branched alkoxy, C1-C20 linear or branched alkylthio, C1-C20 acyl, C1-C20 acyloxy or C1-C20 oxyacyl; C6-C20 arylthio, C2-C20 heterocyclic group containing N, O and / or S;

[0015] Alternatively, R5-R7 are each independently R 10 , R 11 With R 12Selected from the following groups: hydrogen, C6-C30 aryl, C6-C30 aryl substituted by C1-C20 alkyl or alkoxy, C1-C20 straight or branched alkyl, or C1-C20 straight or branched alkyl in which -CH2- can be substituted by -O-, -S-, -CO-, -COO- or -OCO- to form a substituent; connected to each other to form a ring or to form a ring with the alternate alkenyl carbon atoms;

[0016] Alternatively, R5-R7 are each independently L=O、S、NR 13 ', R 13 , R 13 'are each independently selected from the following groups: C1-C20 straight-chain or branched alkyl or halogenated alkyl or hydroxy-substituted alkyl, C3-C20 cycloalkyl, C2-C20 straight-chain or branched alkenyl, C2-C20 straight-chain or branched alkynyl, C1-C20 straight-chain or branched alkoxy or alkylthio, C2-C20 straight-chain or branched hydroxyalkoxy-substituted alkyl, C1-C20 alkyl substituted by C6-C10 aryl or aryloxy, A C2-C20 straight-chain or branched alkyl group interrupted by one or more -O-, -S-, -O-CO- or -CO-O- groups; a C6-C30 aryl group, a substituent formed by replacing at least one hydrogen atom in the phenyl group of the C6-C30 aryl group with a C1-C20 straight-chain or branched alkyl group, an alkoxy group, an alkylthio group, a C1-C20 acyl group, a C1-C20 acyloxy group or a C1-C20 oxyacyl group; a C2-C20 heterocyclic group containing N, O and / or S;

[0017] R6 and R7 may be connected to each other to form a ring;

[0018] n is 0 or 1.

[0019] The present invention obtains an oxime ester photoinitiator with good heat resistance, solubility and high sensitivity through structural design.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0021] As a preferred technical solution of the present invention, the R1 is selected from any one of methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl, preferably methyl or ethyl.

[0022] As a preferred technical solution of the present invention, when R3 and R4 are the same, and both R3 and R4 are C1-C20 straight chain or branched alkyl, the oxime ester photoinitiator is selected from any one of the following compounds 1-84:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028] The oxime ester photoinitiator further comprises a compound in which R3 and R4 are the same, and R3 and R4 are selected from any one of C2-C20 alkenyl or alkoxy, alkylthio, cycloalkane, aryl, and heterocycle, and R3 (R4) can be exemplarily selected from the following structures:

[0029] The oxime ester photoinitiator further comprises R3 and R4 connected to form a ring, and the group after R3 and R4 are connected to form a ring includes, but is not limited to:

[0030] The oxime ester photoinitiator also includes compounds with different R3 and R4, illustratively including but not limited to the following substituents:

[0031]

[0032] As a preferred technical solution of the present invention, the oxime ester photoinitiator absorbs energy within the light wavelength range of 300 to 450 nm to generate highly active free radicals.

[0033] The compound of the general formula (I), (II) and (III) of the present invention has a photosensitive group, and can break NO and CC bonds to generate CO2 and alkyl free radicals under the irradiation of active energy rays. The oxime ester photoinitiator has high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm, and can generate active free radicals more quickly under a lower exposure amount. At the same time, it also has good solubility, thermal stability and chemical stability.

[0034] In a second aspect, the present invention provides a method for preparing the oxime ester photoinitiator as described in the first aspect, wherein the method for preparing the compound of formula (I) comprises the following steps:

[0035] (1) 2-X indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound;

[0036] (2) reacting the 4,4'-R3,R4 indenothiophene compound obtained in step (1) with an acyl halide R2COX to generate a 2-R2 acyl compound;

[0037] (3) the 2-R2 acyl compound obtained in step (2) reacts with a compound having an R5 group to generate a 6-R5 compound;

[0038] (4) the 6-R5 compound obtained in step (3) undergoes an oxime reaction with hydroxylamine hydrochloride to generate an oxime compound;

[0039] (5) in step (4), the oxime compound and the acylating agent undergo esterification reaction in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O;

[0040] The reaction process is as follows:

[0041]

[0042] Wherein, R1, R2, R3, R4 and R5 have the same protection scope as described above, and X is a halogen atom;

[0043] The preparation method of the compound of formula (II) comprises the following steps:

[0044] (A) 6-X indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound;

[0045] (B) reacting the 4,4'-R3,R4 indenothiophene compound obtained in step (A) with Bu3SnCl to generate a tin reagent;

[0046] (C) the tin reagent obtained in step (B) is subjected to a coupling reaction to generate a 6-R2 methylene acyl compound;

[0047] (D) the hydrogen atoms at positions 2 and / or 3 of the 6-R2 methylene acyl compound obtained in step (C) undergo substitution reaction to generate 2-R7 and / or 3-R6 compounds;

[0048] (E) subjecting the 2-R7 and / or 3-R6 compound obtained in step (D) to an oxime reaction with a nitrite or an alkyl nitrite to generate an oxime compound;

[0049] (F) the oxime compound obtained in step (E) undergoes an esterification reaction with an acylating agent in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O;

[0050] The reaction process is as follows:

[0051]

[0052] Wherein, R1, R2, R3, R4 and R5 have the same protection scope as above, and X is a halogen atom;

[0053] The preparation method of the compound of formula (III) comprises the following steps:

[0054] (S1) indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound;

[0055] (S2) the 4,4'-R3,R4 indenothiophene compound of step (S1) is subjected to Friedel-Crafts reaction to generate a 2,6-R2 acyl compound;

[0056] (S3) the 2,6-R2 acyl compound of step (S2) undergoes an oxime reaction with hydroxylamine hydrochloride to generate an oxime compound;

[0057] (S4) the oxime compound of step (S3) undergoes an esterification reaction with an acylating agent in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O;

[0058] The reaction process is as follows:

[0059]

[0060] Wherein, R1, R2, R3, and R4 have the same protection scope as above, and X is a halogen atom.

[0061] In a third aspect, the present invention provides a use of the oxime ester photoinitiator as described in the first aspect in a photosensitive composition, wherein the photosensitive composition comprises the oxime ester photoinitiator as described in the first aspect, an alkali-soluble resin, a photopolymerizable compound, a colorant and a solvent.

[0062] As a preferred technical solution of the present invention, relative to the total weight of the total solid content of the photosensitive composition, it includes 0-30 (w / w)% of a colorant, 20-80 (w / w)% of an alkali-soluble resin, and 10-45 (w / w)% of a photopolymerizable compound;

[0063] Based on the total weight of the colorant, the alkali-soluble resin and the photopolymerizable compound as 100%, the content of the oxime ester photoinitiator is 0.1-25 (w / w) %;

[0064] Preferably, based on 100% of the total weight of the photosensitive composition, the content of the solvent is 10-90 (w / w) %.

[0065] In the present invention, by selecting a photoinitiator with a specific structure, the prepared photosensitive composition has good storage stability, high sensitivity, good development effect and good thermal stability.

[0066]

Alkali soluble resin

[0067] There is no special restriction on the alkali-soluble resin in the present invention, and all alkali-soluble resins commonly used in the art are applicable, and are selected from the viewpoints of heat resistance, developability, and availability. The alkali-soluble resin is preferably an alkali-soluble resin having acidic groups such as carboxyl groups and phenolic hydroxyl groups, and is further preferably an alkali-soluble resin of a carboxyl-containing copolymer, and is particularly preferably a copolymer of an ethylenically unsaturated monomer having more than one carboxyl group [hereinafter referred to as "carboxyl-containing unsaturated monomer" (P)] and other copolymerizable ethylenically unsaturated monomers [hereinafter referred to as "copolymerizable unsaturated monomers" (Q)] [hereinafter referred to as "carboxyl-containing copolymer" (R)].

[0068] Examples of the carboxyl group-containing unsaturated monomer (P) include the following compounds: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or their anhydrides; unsaturated polycarboxylic acids or their anhydrides that are trivalent or higher; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), phthalic acid mono(2-acryloyloxyethyl), and phthalic acid mono(2-methacryloyloxyethyl); mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as ω-carboxyl polycaprolactone monoacrylate and ω-carboxyl polycaprolactone monomethacrylate, etc. These carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more.

[0069] In addition, examples of the copolymerizable unsaturated monomer (Q) include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; acrylic acid esters such as benzyl methacrylate and methyl methacrylate; and carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate. ; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinyl cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysiloxane, etc. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

[0070] The preferred carboxyl-containing copolymer in the present invention [hereinafter referred to as "carboxyl-containing copolymer" (R)] is obtained by polymerizing (P) and (Q). The (P) is a carboxyl-containing unsaturated monomer component containing acrylic acid and / or methacrylic acid as essential components, and further containing at least one compound selected from succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), ω-carboxyl polycaprolactone monoacrylate and ω-carboxyl polycaprolactone monomethacrylate, etc., depending on the situation; and the (Q) is at least one monomer selected from styrene, methyl acrylate, methyl methacrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer.

[0071] Specific examples of the carboxyl group-containing copolymer (R) include (meth)acrylic acid / methyl (meth)acrylate copolymers, (meth)acrylic acid / benzyl (meth)acrylate copolymers, (meth)acrylic acid / hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymers, (meth)acrylic acid / methyl (meth)acrylate / benzyl (meth)acrylate copolymers, (meth)acrylic acid / methyl (meth)acrylate / polystyrene macromonomer copolymers, (meth)acrylic acid / methyl (meth)acrylate / polymethyl methacrylate macromonomer copolymers, (meth)acrylic acid / benzyl (meth)acrylate / polystyrene macromonomer copolymers, (meth)acrylic acid / benzyl (meth)acrylate / polymethyl methacrylate macromonomer copolymers, (meth)acrylic acid / benzyl (meth)acrylate / polystyrene macromonomer copolymers, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / polystyrene macromonomer copolymers, (meth)acrylic acid / (meth)acrylate- Substituents present in carboxyl-containing copolymer molecules such as 2-hydroxyethyl ester / benzyl (meth)acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / styrene / allyl (meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / styrene / benzyl (meth)acrylate / glycerol mono(meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / ω-carboxypolycaprolactone mono(meth)acrylate / styrene / benzyl (meth)acrylate / glycerol mono(meth)acrylate / N-phenylmaleimide copolymer, can also be modified by other materials.

[0072] In the present invention, the alkali-soluble resin further includes an alkali-soluble resin containing sulfur atoms, and the alkali-soluble resin containing sulfur atoms includes a repeating unit as shown in formula A:

[0073]

[0074] Wherein, Z1 is a hydrogen atom or a methyl group, Z2 is an alkylene group having 1 to 5 carbon atoms, Z3 has a structure as shown in formula B, and Z4 is a hydrogen atom or a residue of a carboxylic acid derived from an acid anhydride.

[0075] The alkali-soluble resin containing the repeating unit of formula A can be prepared by copolymerizing unsaturated monomers containing carboxylic acids connected by sulfur atoms, and can be prepared by adding glycidyl methacrylate to a copolymer of unsaturated monomers containing carboxylic acids connected by sulfur atoms; in addition, it can be prepared by adding anhydride reaction.

[0076] The acid anhydride is one or more acid anhydrides selected from the group consisting of the following acid anhydrides: succinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1,1-cyclopentanediacetic anhydride, (2-methyl-2-propenyl)succinic anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclohexanediacetic anhydride, 2-butene-1-ylsuccinic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 5 -norbornene-2,3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, n-octylsuccinic anhydride, allylsuccinic anhydride, bicyclo[2.2.2]-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,2-naphthalene dicarboxylic anhydride, 3-methylphthalic anhydride, biphenyl anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 5,6-dihydro-1,4-dithiene-2,3-dicarboxylic anhydride, 2,3-dimethylmaleic anhydride, maleic anhydride, 4-tert-butylphthalic anhydride and citraconic anhydride.

[0077] The unsaturated monomer may be any one of the copolymerizable unsaturated monomers (Q) mentioned above or a combination of at least two of them.

[0078] In the present invention, the alkali-soluble resin may be used alone or in combination of at least two kinds.

[0079] In order to improve the developability and liquid viscosity, the alkali-soluble resin is preferably a polymer having a weight average molecular weight of 1,000-100,000, and more preferably a polymer having a weight average molecular weight of 5,000-50,000.

[0080]

Photopolymerizable compounds

[0081] The photopolymerizable compound of the present invention is a compound that can be polymerized by the action of the oxime ester photoinitiator provided by the present invention. These compounds can be used alone or in combination of at least two or more.

[0082] The photopolymerizable compound includes a monofunctional compound and a polyfunctional compound.

[0083] The monofunctional compound illustratively includes, but is not limited to: (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid The monofunctional monomers may be used alone or in combination of two or more thereof.

[0084] The multifunctional compound illustratively includes, but is not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., a reaction product of a diisocyanate such as toluene diisocyanate, trimethyl-1,6-hexane diisocyanate or 1,6-hexane diisocyanate and 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, a condensate of a polyol and N-hydroxymethyl(meth)acrylamide, and 1,3,5-triacryloylhexahydro-1,3,5-triazine (triacrylformal). The multifunctional monomers may be used alone or in combination of at least two.

[0085]

Solvent

[0086] The photosensitive composition provided by the present invention also includes a solvent. In the present invention, there is no special restriction on the specific selection of the solvent, and the commonly used solvents in the art are all applicable, including, but not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dipropyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ethers, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, methoxy butyl acetate, methoxy pentyl acetate, benzene, toluene, xylene, trimethylbenzene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, 3-ethoxyethyl propionate, 3-methoxymethyl propionate, γ-butyrolactone.

[0087] The content of the solvent is 10-90 (w / w) % of the photosensitive composition.

[0088]

Colorant

[0089] The colorant includes a pigment and / or a dye.

[0090] There is no special restriction on the pigment in the present invention, and all commonly used pigments in the art are applicable. The pigment includes inorganic pigments and organic pigments. The organic pigments include, but are not limited to, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolinone pigments, perylene pigments, peroxycyclic ketone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthraquinone pigments, indanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments and diketopyrrolopyrrole pigments; the inorganic pigments include, but are not limited to, metal compounds such as metal oxides or metal complex salts, such as metal oxides or composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black.

[0091] Preferably, the pigments exemplarily include but are not limited to: CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122 , 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; CI Pigment Brown 28; CI Pigment Black 1 and 7.

[0092] The present invention has no special requirements for the specific selection of dyes, and dyes commonly used in the art are applicable, including, but not limited to, red dyes such as CI Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179; blue dyes such as CI Solvent Blue 5, 35, 36, 37, 44, 59, 67, 70; purple dyes such as CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49; yellow dyes such as CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; orange dyes such as CI Solvent Orange 2, 7, 11, 15, 26, 56; and green dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35.

[0093] The content of the colorant is 0-30 (w / w) % of the solid content in the photosensitive composition.

[0094] The photosensitive composition provided by the present invention also includes additives, and the additives include any one or a combination of at least two of a dispersant, a leveling agent, a curing agent, a sensitizer, an antioxidant, and an ultraviolet light absorber.

[0095] There is no special restriction on the specific selection of additives in the present invention, and any additive commonly used in the art is applicable.

[0096]

Dispersant

[0097] The dispersant includes cationic, anionic, nonionic, amphoteric, polyester, polyamine and other surfactants, and the dispersant can be used alone or in combination of two or more.

[0098] The content of the curing agent is 0.01-3 (w / w) % of the photosensitive composition.

[0099]

Curing agent

[0100] The curing agent illustratively includes, but is not limited to: bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins or brominated derivatives of these epoxy resins, other aliphatic, aromatic or alicyclic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, (meth)acrylate glycidyl ester (co)polymer, triglycidyl isocyanurate, carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, terephthalic acid dioxetane, cyclohexane dicarboxylic acid dioxetane.

[0101] The content of the curing agent is 0.01-3 (w / w) % of the photosensitive composition.

[0102] It should be noted that the preparation method of the photosensitive composition of the present invention is: the photosensitive composition can be prepared by mixing all the above components by pneumatic stirring. It should be noted that when the prepared photosensitive composition contains insoluble components such as pigments, it can be filtered using a filter to make the photosensitive composition uniform.

[0103] In a fourth aspect, the present invention provides use of the photosensitive composition as described in the third aspect in a process, wherein the photosensitive composition is used to prepare a flat panel display device.

[0104] Preferably, the photosensitive composition is used to prepare columnar spacers, color filters, color resists or photoresists in flat panel display devices.

[0105] The photosensitive composition provided by the invention has good chemical stability, thermal stability, high sensitivity and other properties, and is suitable for preparing columnar spacers, color filters, color resists or photoresists in flat panel display devices.

[0106] In the present invention, the photosensitive composition can be used as a protective film, an interlayer insulating material or a pattern transfer material, and is suitable for preparing columnar spacers, color filters, etc. in the field of liquid crystal display.

[0107] In a fifth aspect, the present invention provides an electronic component, comprising a protective film, an interlayer insulating material or a pattern transfer material prepared from the photosensitive composition as described in the third aspect.

[0108] In a sixth aspect, the present invention provides a use of the photosensitive composition as described in the third aspect in a display device, wherein the display device includes a liquid crystal display device, a field luminescence display device, a plasma display device, and a field emission display device.

[0109] Compared with the prior art, the present invention has the following beneficial effects:

[0110] In the present invention, the structure of the oxime ester photoinitiator is designed, and the prepared oxime ester photoinitiator has good heat resistance and high sensitivity, and is suitable for use as a photoinitiator of a photosensitive composition. The photosensitive composition prepared in this way has good storage stability, high sensitivity, good development effect and good thermal stability. DETAILED DESCRIPTION

[0111] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0112] Synthesis Example 1

[0113] This synthesis example provides an oxime ester photoinitiator 3 and a preparation method thereof. The preparation method of the oxime ester photoinitiator 3 is as follows:

[0114]

[0115] Add 251.15g 2-bromo-indenothiophene, 32.24g tetrabutylammonium bromide and 1200.00g DMSO to a four-necked flask, start stirring and cool to -5-0°C, then slowly add 1066.67g liquid alkali (30% w / w) and stir for 0.5h, add 301.45g 1-bromobutane dropwise to the system, after the addition is complete, warm to room temperature and keep warm for 6 hours; pour in 650.00 pure water and 1200.00 dichloromethane (DCM), stir for 0.5h. Separate the organic phase, extract the aqueous phase with 200.00g DCM 3 times; combine the organic phases and wash once with 200.00g water. 7.53 g of activated carbon was added, and the mixture was stirred for 0.5 h and then filtered; the filtrate was collected, DCM was distilled, and 800.00 g of n-hexane was added at -5-0°C for crystallization to obtain 347.00 g of 2-bromo-9,9-dibutylindenothiophene.

[0116] Coupling: Under nitrogen protection, 327.00g 2-bromo-4,4-dibutylfluorene was dissolved in 1500g DMF, stirring was started, 7.20g NiCl2`dtbbpy and 4.19g (TES) 3SiH, 461.44g cyclohexylpropionyl chloride were added, the temperature was raised to 110°C, and the reaction was carried out until the raw material was <0.5%, the temperature was lowered to 50°C, and the mixture was passed through a silica gel column; 300.00g water was added to the filtrate, the mixture was stirred and cooled to 0°C, crystallized, and filtered; the filter cake was slurried twice with 1000.00g methanol, and concentrated to obtain 192.76g of solid.

[0117] Slowly add 150.00g of concentrated sulfuric acid to 26.72g of fuming nitric acid to form a nitric acid solution. Add 169.00g of the coupling product and 900.20g of DCM to a 1000ml four-necked flask, and stir to dissolve. Cool to 5-10°C, add nitric acid solution dropwise, and add after about 2h. When the remaining raw material is <0.1% in the sampling, stop the reaction, pour the reaction solution into 600g of ice water, stir for 20min, stand for separation, take the lower organic phase, wash with 200.00g of pure water 3 times, distill the organic phase at normal pressure until no obvious liquid flows out, add 180.45g of acetone, cool to 5-15°C, stir for crystallization, and air dry at 60°C to obtain 114.11g of light yellow solid.

[0118] Put 101.05g of the above solid into a 1000ml four-necked flask, add 500.00g of DCM and stir to dissolve, then add 18.77g of hydroxylamine hydrochloride and 22.49g of ammonium acetate, heat and reflux for 15h, stop the reaction and cool down when the residual raw material is less than 0.5%. Add 200.00g of pure water, stir and separate, wash the organic phase with 100.00g of water, distill the organic phase at normal pressure until no obvious liquid flows out, add 450.00g of methanol, cool to 10-15℃, stir and crystallize, and dry at 50℃ with air blast to obtain 95.95g of yellow solid.

[0119] 400.00g of DCM was put into a four-necked flask, and then 78.71g of hydroxylation product and 0.40g of DMAP were added, the temperature was lowered to 15-20°C, 19.98g of acetic anhydride was added dropwise, and the mixture was stirred for 1h after the addition was completed. After the reaction was completed, 100.00g of water was added, stirred and separated, the lower organic phase was taken, the pH was adjusted to 7-8 with an aqueous sodium carbonate solution, and then the organic phase was washed 3 times with 100.00g of water respectively, the organic phase was distilled at normal pressure until no obvious liquid flowed out, 250.00g of methanol was added, the temperature was lowered to 0-5°C for crystallization, and the mixture was dried in an oven at 60°C to obtain 76.61g of yellow powder, which was the compound shown in the above structural formula 3.

[0120] pass 1 The product structure was characterized by H NMR, and the test results are as follows: 1 H-NMR (CDCl3, 400MHz): δ8.29(dd,J=8.4,2.2Hz,1H),7.84(d,J=2.2Hz,1H),7.61(d,J=8.4Hz,1H),7.07(s,1H),3.08(t,J=7.9Hz,2H),2.0 8(s,3H),1.96(td,J=6.3,2.4Hz,4H),1.73(td,J=8.0,6.3Hz,2H),1.59(dq,J=12.3,6.1Hz,1H),1.50-1.29(m,18H),0.88(t,J=7.6Hz,6H).

[0121] Synthesis Example 2

[0122] This synthesis example provides an oxime ester photoinitiator 61 and a preparation method thereof. The preparation method of the oxime ester photoinitiator 61 is as follows:

[0123]

[0124] The first step reaction is carried out as in Synthesis Example 1 to obtain 2-bromo-9,9-dibutylindenothiophene.

[0125] 181.68g of 2-bromo-9,9-dibutylindenothiophene was put into a flask, 900.00g of THF was added, nitrogen was passed, stirring was started and the temperature was lowered to -40°C, 220mL of tert-butyl lithium solution (2.5mol / L) and 112.85g of tripropyl borate were added dropwise, and the reaction was kept warm for 0.5h after the addition was completed, and the temperature was raised to room temperature. The reaction was stopped when the residual raw material of the central control HPLC was <0.5%, and 560.00mL of HCl aqueous solution (1mol / L) was added dropwise to the solution. After the addition was completed, stirring was continued, the temperature was raised to room temperature, 600.00g of tert-methyl ether was added, and the liquid was separated. The organic phase was washed with 100.00g of pure water for 3 times, and the solvent was distilled at 58°C until fluorene was obviously distilled, 420.00g of n-hexane was added, and the temperature was lowered to 0°C with stirring. Crystallization and filtration were performed to obtain 130.65g of solid.

[0126] Under nitrogen protection, 114.92g of the above product was dissolved in 551.20g of toluene, stirring was started, 12.16g of Pd(PPh3)4, 148.62g of potassium phosphate, 67.26g of cyclohexylpropionyl chloride were added, the temperature was raised to 110°C, and the reaction was continued until the raw material was <0.5%, the temperature was lowered to 50°C, and the mixture was passed through a silica gel column; 400.00g of pure water was added to the filtrate, the mixture was stirred and cooled to 0°C, crystallized, and filtered; the filter cake was slurried twice with 1000.00g of methanol, and concentrated to obtain 110.87g of solid.

[0127] Add 100.00g of Friedel-Kettering substance and 500.00g of ethyl acetate into a 1L four-necked flask, stir and dissolve, cool to below 15°C, add 208.00g of hydrochloric acid, pass hydrogen chloride gas, stir for 30min, a white solid precipitates, add 26.09g of sodium nitrite in batches, then keep warm and react for 1h, stop the reaction when the remaining raw material is <0.5%, pour the reaction solution into 120.00g of ice water, separate the layers, add 120.00g of water to the organic phase, adjust the pH to 8-9 with sodium carbonate, separate the organic phase, wash with 60.00g of pure water, and concentrate the organic phase to dryness under reduced pressure at 50°C. Add 450.60g of dichloromethane, stir to dissolve, cool to 10-15°C, add 30.20g of acetic anhydride dropwise, add dropwise, keep warm for 30min, warm to room temperature, stop the reaction when the remaining raw material is <0.5%, add 100.00g of water, stir to separate the liquid, take the lower organic phase, adjust the pH to 7-8 with sodium carbonate aqueous solution, then wash the organic phase with 100.00g of water twice, distill the organic phase under reduced pressure at 55°C until no obvious liquid flows out, add 200.00g of methanol, cool to room temperature, The mixture was warmed to 5-10°C, stirred and crystallized, and filtered to obtain a yellow solid, which was dissolved in 165.00 g of acetone, stirred to dissolve, 2.50 g of activated carbon was added, stirred and filtered, and the filtrate was distilled to dryness under reduced pressure at 55°C, 200.00 g of dichloromethane was added, and the mixture was washed 3 times with 80.00 g of pure water respectively. The organic phase was evaporated to dryness under reduced pressure at 55°C, 200.00 g of methanol was added, the temperature was lowered to 5-10°C, stirred and crystallized, and filtered, and dried at 60°C to obtain 46.76 g of a light yellow solid, which is the compound shown in the above structural formula 61.

[0128] The oxime ester photoinitiator 61 was tested by hydrogen nuclear magnetic resonance spectrum, and the test results were as follows: 1H-NMR (CDCl3, 400MHz): δ7.91 (dd, J = 8.4, 1.8Hz, 1H), 7.66 (d, J = 6.2Hz, 1H), 7.60-7.51 (m, 2H), 6.77 (d, J = 6.0Hz, 1H), 2.96 (d, J = 7.6Hz, 2H), 2.19 (p, J = 6.2Hz, 1H), 2.12 (s, 3H), 1.94 (td, J = 6.3, 0.9Hz, 4H), 1.59-1.30 (m, 18H), 0.88 (t, J = 7.5Hz, 6H)

[0129] Synthesis Example 3

[0130] This synthesis example provides an oxime ester photoinitiator 82 and a preparation method thereof. The preparation method of the oxime ester photoinitiator 82 is as follows:

[0131]

[0132] Add 172.28g indenothiophene, 32.25g tetrabutylammonium bromide and 1000.00g DMSO to a four-necked flask, start stirring and cool to 0-5°C, then slowly add 800.00g liquid alkali (50% w / w) and stir for 0.5h, add 287.76g 1-bromobutane dropwise to the system, after the addition is complete, warm to room temperature and keep warm for 6-10 hours; pour in 200.00 pure water and 1000.00 dichloromethane (DCM), stir for 0.5h, and separate the liquids. Wash the organic phase once with 200.00g water. Add 5.00g activated carbon, stir for 0.5h and filter; collect the filtrate, distill DCM, add 700.00g methanol -5-0°C for crystallization, and obtain 253.77g 9,9-dibutylindenothiophene.

[0133] 241.79g of dibutylindenothiophene, 1000.00g of DCM and 312.79g of cyclohexyl propionyl chloride were put into a 2L four-necked flask, placed in a cold well and cooled to 0-5°C, 249.78g of aluminum chloride was added in batches, and the reaction was kept warm for 1 hour. The reaction was stopped when the control raw material was <1%, and the reaction solution was slowly poured into the prepared 500.00g of hydrochloric acid and 1800.00g of ice water mixture, stirred for 1h and then separated, and the organic phase was washed 3 times with 500.00g of water respectively. The organic phase was distilled at atmospheric pressure until no obvious liquid flowed out, cooled to 35°C, 1000.00g of methanol was slowly added, stirred and cooled to 0-5°C, crystallized and filtered, and dried at 60°C for 8h to obtain 452.96g of light yellow solid.

[0134] Add 200.00g of the above solid to a 1000ml four-necked flask, add 500.00g of DCM and stir to dissolve, then add 31.00g of hydroxylamine hydrochloride and 37.12g of ammonium acetate, heat and reflux for 12h, stop the reaction and cool down when the residual raw material is less than 1.0%. Add 200.00g of pure water, stir and separate, wash the organic phase with 100.00g of water, distill the organic phase at normal pressure until no obvious liquid flows out, add 450.00g of methanol, cool to 10-15°C, stir and crystallize, and dry at 50°C to obtain 189.66g of yellow solid.

[0135] 600.00g of DCM was put into a four-necked flask, and then 150.00g of hydroxylation product and 0.76g of DMAP were added, the temperature was lowered to 5-10°C, 31.11g of acetic anhydride was added dropwise, and the mixture was kept warm and stirred for 1h after the addition was completed. After the reaction was completed, 150.00g of water was added, stirred and separated, the lower organic phase was taken, the pH was adjusted to 7-8 with sodium carbonate aqueous solution, and then the organic phase was washed 3 times with 150.00g of water respectively, the organic phase was distilled at atmospheric pressure until no obvious liquid flowed out, 450.00g of methanol was added, the temperature was lowered to 0-5°C for crystallization, and after suction filtration, it was dried in an oven at 60°C to obtain 68.56g of yellow powder, which is the compound shown in the above structural formula 82.

[0136] The oxime ester photoinitiator 82 was tested by nuclear magnetic resonance hydrogen spectrum, and the test results are as follows: 1 H-NMR (CDCl3, 400MHz): δ7.59-7.50(m,2H),7.23-7.18(m,1H),7.16(s,1H),3.11(td,J=7.9,6.0Hz,4H),2.11(s, 6H), 2.02-1.90 (m, 4H), 1.74 (qd, J=8.1, 6.1Hz, 4H), 1.66-1.54 (m, 2H), 1.50-1.27 (m, 28H), 0.88 (t, J=7.5Hz, 6H).

[0137] Synthesis Example 4-16

[0138] The oxime ester photoinitiators provided in Synthesis Examples 4-16 were prepared according to the preparation methods of the oxime ester photoinitiators described in Synthesis Examples 1-3. The specific structural formulas and hydrogen nuclear magnetic resonance spectrum data of the compounds provided in Synthesis Examples 4-16 are shown in Table 1.

[0139] Table 1

[0140]

[0141]

[0142]

[0143] In the following comparative examples, the structural formula of the compound used is as follows:

[0144]

[0145] Application Example 1

[0146] This application example provides an uncolored photosensitive composition, which includes the following components in parts by weight: 100 parts of acrylate copolymer, 50 parts of trimethylolpropane triacrylate, 33 parts of oxime ester photoinitiator provided in Synthesis Example 1, and 30 parts of butanone;

[0147] The acrylic ester copolymer is prepared from benzyl methacrylate, methacrylic acid and hydroxyethyl methacrylate in a molar ratio of 70:10:20, and has a weight average molecular weight of 10,000.

[0148] Application Examples 2-16

[0149] Application Examples 2-16 respectively provide an uncolored photosensitive composition, which differs from Application Example 1 only in that the oxime ester photoinitiator 3 is replaced by other oxime ester photoinitiators provided by the present invention (see Table 2 for details), and other conditions are the same as those of Application Example 1.

[0150] Comparative Example 1-2

[0151] Comparative Examples 1-2 respectively provide an uncolored photosensitive composition, which differs from Application Example 1 only in that the oxime ester photoinitiator 3 is replaced by OXE-01 or OXE-01 (see Table 2 for details), and other conditions are the same as those of Application Example 1.

[0152] Exposure and development: The uncolored photosensitive compositions provided in the above-mentioned application examples 1-16 and comparative examples 1-2 were stirred and shaken overnight in a dark place. After defoaming, the materials were coated on a PET template using a wire rod and dried at 90°C for 5 minutes to form a film with a thickness of 2μm. Cool to room temperature, attach a mask plate, and use a 1PCS high-pressure mercury lamp as a light source to achieve long-wavelength radiation through a FWHM filter. The coating film was exposed to ultraviolet rays with a wavelength of 370 to 420nm through the gap of the mask plate, and then immersed in a 2.5% sodium carbonate solution at 25°C for 30s for development, then washed with ultrapure water, air-dried, and hard-baked at 220°C for 30min to fix the pattern, and the obtained pattern was evaluated.

[0153] The performance of the photosensitive compositions provided in the above application examples and comparative examples and the patterns after exposure and development were tested, and the specific testing methods are as follows:

[0154] Storage stability: After the liquid photosensitive composition was naturally stored at room temperature for 1 month, the degree of precipitation of the substance was visually evaluated according to the following criteria: A: no precipitation was observed; B: precipitation was slightly observed; C: obvious precipitation was observed.

[0155] Sensitivity: During exposure and development, the minimum exposure amount at which the residual film rate of the light-irradiated area after development is 90% or more in the exposure step is evaluated as the exposure requirement. The smaller the exposure requirement, the higher the sensitivity.

[0156] Developability and pattern integrity: The substrate pattern was observed using a scanning electron microscope (SEM) to evaluate the developability and pattern integrity;

[0157] The developability was evaluated according to the following criteria: ○: no residue was observed in the unexposed portion; ◎: a small amount of residue was observed in the unexposed portion, but the residue was acceptable; ●: obvious residue was observed in the unexposed portion.

[0158] The pattern integrity was evaluated according to the following criteria: ◇: no pattern defects were observed; □: some defects were observed in a small part of the pattern; ◆: many pattern defects were clearly observed.

[0159] Thermal stability: Use a thickness gauge to test the change in film thickness before and after hard baking to evaluate the thermal stability of the material.

[0160] The performance test results of the uncolored photosensitive compositions provided in the above-mentioned application examples 1-16 and comparative examples 1-2 and the graphics after exposure and development are shown in Table 2 below:

[0161] Table 2

[0162]

[0163] As shown in Table 2, the uncolored curable composition prepared by using the oxime ester photoinitiator provided by the present invention has good storage stability, sensitivity, developability, pattern integrity and thermal stability. After natural storage at room temperature for 1 month, no precipitation was observed. The exposure requirement is 36-54 mJ / cm 2 No residue was observed in the unexposed part, and no pattern defects were observed. The change in film thickness before and after hard baking was only 4.8-5.2% as tested by a thickness gauge.

[0164] Compared with Application Example 1, if other photoinitiators are selected (Comparative Examples 1-2), the storage stability, sensitivity, developability, pattern integrity and thermal stability of the prepared uncolored cured composition are poor. After natural storage at room temperature for 1 month, slight precipitation is observed; the exposure requirement is 85-105 mJ / cm 2 A small amount of residue is observed in the unexposed part, and many pattern defects are obviously observed. The thickness change of the film before and after hard baking is as large as 20% when tested by a thickness gauge.

[0165] Application Example 17

[0166] This application example provides a colored photosensitive composition, which comprises the following components in parts by weight: 100 parts of acrylate copolymer, 50 parts of dipentaerythritol hexaacrylate, 33 parts of oxime ester photoinitiator provided in Synthesis Example 1, 25 parts of butanone and 155 parts of dye blue;

[0167] The acrylic acid ester copolymer is prepared from benzyl methacrylate, methacrylic acid and methyl methacrylate in a molar ratio of 50:15:30, and has a weight average molecular weight of 10,000-15,000.

[0168] Application Examples 18-32

[0169] Application Examples 18-32 respectively provide a colored photosensitive composition, which differs from Application Example 17 only in that the oxime ester photoinitiator 3 is replaced by other oxime ester photoinitiators provided by the present invention (see Table 3 for details), and other conditions are the same as those of Application Example 17.

[0170] Comparative Examples 3-4

[0171] Comparative Examples 3-4 respectively provide a colored photosensitive composition, which differs from Application Example 17 only in that the oxime ester photoinitiator 3 is replaced by OXE-01 or OXE-01 (see Table 3 for details), and other conditions are the same as those of Application Example 17.

[0172] Exposure and development: The colored photosensitive compositions provided in the above-mentioned application examples 17-32 and comparative examples 3-4 were mixed and shaken overnight in the dark, and after defoaming, they were coated on a PET template using a wire rod, and dried at 90°C for 5 minutes to form a film with a thickness of 2μm. Cool to room temperature, attach a mask plate, and use a 1PCS high-pressure mercury lamp as a light source to achieve long-wavelength radiation through a FWHM filter. The coating film was exposed to ultraviolet rays with a wavelength of 370-420nm through the gap of the mask plate, and then immersed in a 2.5% sodium carbonate solution at 25°C for 30s for development, then washed with ultrapure water, air-dried, and hard-baked at 220°C for 30min to fix the pattern, and the obtained pattern was evaluated.

[0173] The performance of the photosensitive compositions provided in the above application examples 17-32 and comparative examples 3-4 and the patterns after exposure and development were tested, and the specific testing methods are as above:

[0174] The performance test results of the colored photosensitive compositions provided in the above-mentioned application examples 17-32 and comparative examples 3-4 and the graphics after exposure and development are shown in Table 3 below:

[0175] Table 3

[0176]

[0177]

[0178] As shown in Table 3, the colored curable composition prepared by using the oxime ester photoinitiator provided by the present invention has good storage stability, sensitivity, developability, pattern integrity and thermal stability. After natural storage at room temperature for 1 month, no precipitation was observed. The exposure requirement is 39-53 mJ / cm 2 No residue was observed in the unexposed part, and no pattern defects were observed. The change in film thickness before and after hard baking was only 4.0-5% as tested by a thickness gauge.

[0179] Compared with Application Example 17, if other photoinitiators (Comparative Examples 3-4) are selected, the storage stability, sensitivity, developability, pattern integrity and thermal stability of the prepared colored curable composition are poor. After natural storage at room temperature for 1 month, slight precipitation is observed; the exposure requirement is 98-117 mJ / cm 2 A small amount of residue is observed in the unexposed part, and many pattern defects are obviously observed. The thickness change of the film before and after hard baking is tested by a thickness gauge, which is as large as 10-21%.

[0180] From the above content, it can be seen that the oxime ester photoinitiator prepared by the present invention has good heat resistance and high sensitivity by designing the structure of the oxime ester photoinitiator, and is suitable for use as a photoinitiator of a photosensitive composition. The photosensitive composition prepared in this way has good storage stability, high sensitivity, good development effect and good thermal stability.

[0181] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An oxime ester photoinitiator, characterized in that: The oxime ester photoinitiator has a structure as shown in Formula I, Formula II or Formula III: Wherein, R1 is selected from methyl; R2 is selected from C1-C20 branched alkyl, C6 aryl or Any one of, R′ is selected from C6 aryl, * represents the connection site; R3 and R4 are each independently selected from any one of a C1-C20 straight or branched alkyl group, a C2-C20 alkenyl group or a C6 aryl group; R5-R7 are each independently selected from any one of hydrogen, nitro or a C3-C20 heterocyclic group containing S; n is 0 or 1.

2. The oxime ester photoinitiator according to claim 1, characterized in that: The oxime ester photoinitiator absorbs energy within the light wavelength range of 300 to 450 nm to generate highly active free radicals.

3. An oxime ester photoinitiator, characterized in that: The oxime ester photoinitiator has any one of the following structures:

4. A method for preparing an oxime ester photoinitiator according to claim 1 or 2, characterized in that: The preparation method of the compound of general formula I comprises the following steps: (1) 2-X indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound; (2) reacting the 4,4'-R3,R4 indenothiophene compound obtained in step (1) with an acyl halide R2COX to generate a 2-R2 acyl compound; (3) the 2-R2 acyl compound obtained in step (2) reacts with a compound having an R5 group to generate a 6-R5 compound; (4) the 6-R5 compound obtained in step (3) undergoes an oxime reaction with hydroxylamine hydrochloride to generate an oxime compound; (5) in step (4), the oxime compound and the acylating agent undergo esterification reaction in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O; The reaction process is as follows: Wherein, R1, R2, R3, R4 and R5 have the same protection scope as that of claim 1, and X is a halogen atom; The preparation method of the compound of general formula II comprises the following steps: (A) 6-X indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound; (B) reacting the 4,4'-R3,R4 indenothiophene compound obtained in step (A) with Bu3SnCl to generate a tin reagent; (C) the tin reagent obtained in step (B) is subjected to a coupling reaction to generate a 6-R2 methylene acyl compound; (D) the hydrogen atoms at positions 2 and / or 3 of the 6-R2 methylene acyl compound obtained in step (C) undergo substitution reaction to generate 2-R7 and / or 3-R6 compounds; (E) subjecting the 2-R7 and / or 3-R6 compound obtained in step (D) to an oxime reaction with a nitrite or an alkyl nitrite to generate an oxime compound; (F) the oxime compound obtained in step (E) undergoes an esterification reaction with an acylating agent in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O; The reaction process is as follows: Wherein, R1, R2, R3, R4, R6 and R7 have the same protection scope as that of claim 1, and X is a halogen atom; The preparation method of the compound of formula III comprises the following steps: (S1) indenothiophene reacts with R3X and / or R4X under alkaline conditions to prepare a 4,4'-R3,R4 indenothiophene compound; (S2) the 4,4'-R3,R4 indenothiophene compound of step (S1) is subjected to Friedel-Crafts reaction to generate a 2,6-R2 acyl compound; (S3) the 2,6-R2 acyl compound of step (S2) undergoes an oximation reaction with hydroxylamine hydrochloride to generate an oxime compound; (S4) the oxime compound of step (S3) undergoes an esterification reaction with an acylating agent in an inert solvent under alkaline conditions to generate an oxime ester photoinitiator, wherein the acylating agent is R1-COX or (R1CO)2O; The reaction process is as follows: Wherein, R1, R2, R3, and R4 have the same protection scope as that of claim 1, and X is a halogen atom.

5. A photosensitive composition, characterized in that The photosensitive composition comprises the oxime ester photoinitiator according to any one of claims 1 to 3, an alkali-soluble resin, a photopolymerizable compound, a colorant and a solvent.

6. The photosensitive composition according to claim 5, characterized in that The photosensitive composition comprises 0-30 (w / w)% of a colorant, 20-80 (w / w)% of an alkali-soluble resin, and 10-45 (w / w)% of a photopolymerizable compound, relative to the total weight of the solid content of the photosensitive composition; Based on the total weight of the colorant, the alkali-soluble resin and the photopolymerizable compound as 100%, the content of the oxime ester photoinitiator is 0.1-25 (w / w)%.

7. The photosensitive composition according to claim 5, characterized in that Based on the total weight of the photosensitive composition being 100%, the content of the solvent is 10-90 (w / w) %.

8. Use of the photosensitive composition according to any one of claims 5 to 7, characterized in that: The photosensitive composition is used for preparing a flat panel display device.

9. The use according to claim 8, characterized in that: The photosensitive composition is used for preparing columnar spacers, color filters, color resists or photoresists in flat panel display devices.

10. An electronic component, characterized in that: The electronic component comprises a protective film, an interlayer insulating material or a pattern transfer material prepared from the photosensitive composition according to any one of claims 5 to 7.

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