An oxime ester photoinitiator, a photoresist composition and its application

Abstract

The application belongs to the technical field of photoinitiators, and particularly relates to an oxime ester photoinitiator, a photoresist composition and application thereof. The initiator provided by the application is an oxime ester compound, the main body structure of the photoinitiator has the ability to absorb light of different wavelengths, has good molecular stability, reduces blue light absorption, and inhibits the risk of yellowing of the system. Through modification of substituent groups, the absorption activity of the photoinitiator to light and the initiation efficiency can be ensured on the premise of improving the stability of the photoinitiator, the photocuring reaction can be efficiently promoted, the dual demands of speed and quality of production can be met, and synergistic optimization of expansion of absorption wavelength, improvement of stability and guarantee of initiation efficiency is realized.

Description

Technical Field

[0001] This invention belongs to the field of photoinitiator technology, specifically relating to an oxime ester photoinitiator, a photoresist composition, and their applications. Background Technology

[0002] Photoinitiators are key substances in photopolymerization reactions and have wide applications in many fields such as photocurable coatings, inks, and adhesives. Under the influence of light, photoinitiators can absorb light energy of specific wavelengths and generate active free radicals through reactions such as cracking or hydrogen abstraction. These free radicals then initiate polymerization reactions of monomer molecules, causing the system to rapidly transform from a liquid to a solid state, thereby altering the material's properties.

[0003] As the performance requirements for photocurable materials in various application fields continue to increase, higher challenges are also posed to the performance of photoinitiators. Currently, most photoinitiators have relatively limited absorption wavelength ranges. In practical applications, such as some special photocuring processes, it is difficult to perfectly match the emission spectrum of the light source with the absorption spectrum of the photoinitiator. Moreover, during the photocuring process and the use of the cured material, the photocured system induced by the photoinitiator is prone to yellowing. On the one hand, when the photoinitiator absorbs light energy and reacts, some side reactions produce some chromophores with conjugated structures. These chromophores absorb visible light, making the material appear yellow. On the other hand, the structural stability of the photoinitiator itself is insufficient. Under the influence of light, heat, and other factors, it will undergo decomposition or oxidation reactions, and the products generated may also have color, leading to yellowing of the system. Yellowing of the system not only affects the appearance quality of the material but may also change the optical properties of the material. In applications with strict color requirements, such as optical devices and transparent coatings, this greatly limits the use of photocurable materials.

[0004] The present invention aims to develop a novel photoinitiator that can effectively broaden the absorption wavelength range, achieve efficient absorption of various wavelengths of light, and at the same time, the photoinitiator has good stability, suppresses yellowing of the photocurable system during the photocuring process and subsequent use, improves the overall performance of the photocurable material, and meets the urgent needs of various application fields for high-performance photocurable materials. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an oxime ester photoinitiator, a photoresist composition, and its applications.

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

[0007] An oxime ester photoinitiator having a structure as shown in general formula (I): R1 has the structure shown in general formula (II): Where X and Y are each independently empty, O, S, S=0, S=(0)2, C=0, NR 11 C1-C5 alkylene groups, wherein R 11 It is a hydrogen group, a straight-chain or branched alkyl group with 1-20 carbon atoms, or a cycloalkyl group with 3-20 carbon atoms. Either X or Y is selected from S=0, * is the linking site; Z is selected from carbonyl or direct bond.

[0008] R2 and R3 are each independently hydrogen, an alkyl group with 1-20 carbon atoms, a cycloalkyl group with 3-20 carbon atoms, an aryl group with 6-30 carbon atoms (substituted or unsubstituted), or a heteroaryl group with 6-30 carbon atoms (substituted or unsubstituted).

[0009] R4 to R 10 Each of the following groups is independently hydrogen, nitro, cyano, cycloalkanone group with 3-20 carbon atoms, heterocycloalkanone group with 3-20 carbon atoms, substituted or unsubstituted aromatic ketone group with 6-30 carbon atoms, or substituted or unsubstituted heteroaromatic ketone group with 6-30 carbon atoms.

[0010] In this invention, "substitution" means that the hydrogen atom on the compound group is replaced by another atom or group, and the substitution position is arbitrary; "unsubstitution" means that the hydrogen atom on the compound group is not replaced by another atom or group.

[0011] In this invention, "substituted or unsubstituted" means either unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium, tritium, halogen atom, heteroatom, cyano, amino, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C 3–30 heteroaryl groups, substituted or unsubstituted C1–30 alkoxy groups, substituted or unsubstituted C6–30 aryloxy groups, and silyl groups, specifically including deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, amino, nitro, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, cyclopentenyl, and cyclohexene. Benzyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocyclopentenyl, benzocyclohexenyl, phenyl, tolyl, pentadeuterated phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzophenanthrene, pyrene, perylene, fluoranyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirodifluorenyl, diphenylamino, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinoline Substituents include, but are not limited to, quinoxalinyl, quinoxalinyl, quinazolinyl, indolyl, furanyl, thiopheneyl, oxazolyl, thiazolyl, imidazolyl, benzofuranyl, benzothiopheneyl, benzooxazolyl, benzothiazolyl, benzoimidazolyl, dibenzofuranyl, dibenzothiopheneyl, carbazolyl, N-phenylcarbazolyl, acridineyl, phenoxazinyl, phenoxazinyl, phenoxthiazolyl, etc. In the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other.

[0012] X is selected from S=0.

[0013] R2 or R3 is preferably a straight-chain or branched alkyl group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, or a substituted or unsubstituted aryl group with 6-30 carbon atoms.

[0014] That is, in this invention, there are schemes in which R2 is a straight-chain or branched alkyl group with 1-20 carbon atoms, and R3 is a straight-chain or branched alkyl group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, or a substituted or unsubstituted aryl group with 6-30 carbon atoms; schemes in which R2 is a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, and R3 is a straight-chain or branched alkyl group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, or a substituted or unsubstituted aryl group with 6-30 carbon atoms; and schemes in which R2 is a substituted or unsubstituted aryl group with 6-30 carbon atoms, and R3 is a straight-chain or branched alkyl group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, or a substituted or unsubstituted aryl group with 6-30 carbon atoms.

[0015] Furthermore, R3 is preferably a straight-chain or branched alkyl group with 1-20 substituted or unsubstituted carbon atoms, or an aryl group with 6-30 substituted or unsubstituted carbon atoms.

[0016] The alkyl group having 1-20 carbon atoms is a straight-chain or branched alkyl group, preferably having 1-15 carbon atoms, and more preferably having 1-10 carbon atoms.

[0017] Preferably, the alkyl group having 1-20 carbon atoms is replaced or interrupted 1-5 times by unsaturated bonds, ether bonds, thioether bonds, ester bonds, thioester bonds, carbonyl bonds, amide bonds, or urethane bonds.

[0018] When R2 or R3 is selected from cyclic alkyl groups with 3-20 carbon atoms (substituted or unsubstituted), it has the following structural formula: m is a natural integer from 1 to 5, and n is a natural integer from 0 to 5.

[0019] m is preferably 3 or 4.

[0020] Here, the heteroatom is any one or more of N, O, and S.

[0021] The aryl group having 6-30 carbon atoms, whether substituted or unsubstituted, is preferably unsubstituted, and more preferably phenyl.

[0022] R4 to R 10 Each of the following groups is independently hydrogen, nitro, cyano, cycloalkanone group with 3-20 carbon atoms, heterocycloalkanone group with 3-20 carbon atoms, substituted or unsubstituted aromatic ketone group with 6-30 carbon atoms, or substituted or unsubstituted heteroaromatic ketone group with 6-30 carbon atoms.

[0023] The cycloalkyl, cycloalkanone, and heterocycloalkanone groups with 3-20 carbon atoms include cases where some or all of the carbon chains are cyclic or heterocyclic.

[0024] In this embodiment, 1-3 hydrogen atoms in the aryl group with 6-30 carbon atoms, the heteroaryl group with 6-30 carbon atoms, the aromatic ketone group with 6-30 carbon atoms, and the heteroaryl ketone group with 6-30 carbon atoms are replaced by Ra or ORa.

[0025] Ra can independently represent cyano, nitro, halogen atom, alkyl with 1-20 carbon atoms, haloalkyl with 1-20 carbon atoms, and heterocyclic alkyl with 3-20 carbon atoms.

[0026] The heterocyclic alkyl group having 3-20 carbon atoms includes cases where some or all of the carbon chains are cyclic or heterocyclic.

[0027] The methylene group of the alkylene moiety represented by Ra is interrupted 1-5 times by an ether bond, thioether bond, ester bond, thioester bond, carbonyl bond, amide bond, or urethane bond.

[0028] The R4 to R 10 One of them is selected from nitro, cyano, or cycloalkanone group with 3-20 carbon atoms, heterocycloalkanone group with 3-20 carbon atoms, substituted or unsubstituted aromatic ketone group with 6-30 carbon atoms, or substituted or unsubstituted heteroaromatic ketone group with 6-30 carbon atoms, and the rest are hydrogen.

[0029] The heteroatoms in heteroaryl groups with 6-30 carbon atoms, cycloalkanone groups with 3-20 carbon atoms, and heteroarylone groups with 6-30 carbon atoms are 1-2 of O, S, and N.

[0030] In this invention, "halogen" refers to fluorine, chlorine, bromine and iodine.

[0031] In this invention, the alkyl groups having 1-20 carbon atoms are preferred to be 1-12, more preferably 1-8, particularly preferably 1-6, and especially preferably branched or unbranched saturated hydrocarbon groups with 1-4 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpropyl The alkyl groups are methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, and their isomers. C1-C8 alkyl groups can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, and their isomers. C1-C6 alkyl groups can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, and their isomers. C1-C4 alkyl groups can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, and their isomers.

[0032] In this invention, the aryl groups having 6-30 carbon atoms are preferred, with 6-18 carbon atoms, and particularly preferred are monocyclic, bicyclic, or tricyclic aromatic hydrocarbon groups having 6-10 carbon atoms. Examples of C6-C30 aryl groups include phenyl, biphenyl, naphthyl, anthracene, etc.; phenyl or naphthyl are preferred, especially phenyl.

[0033] In this invention, the aryl group refers to a heteroaryl group with 6-30 carbon atoms and containing one or more heteroatoms. Heteroatoms refer to N, O, and S.

[0034] The oxime ester photoinitiator is selected from any one of the following structures:

[0035] .

[0036] In a second aspect, the present invention provides a photoresist composition comprising the oxime ester photoinitiator, a polymeric compound having olefinic unsaturated bonds, and a solvent.

[0037] The content of the oxime ester photoinitiator component is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. The above upper and lower limits can be combined in any way. For example, a content of 10 to 90% by mass is preferred, more preferably 15 to 50% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass is preferred.

[0038] Polymerizable compounds having olefinic unsaturated bonds can be polymerizable monomers or oligomers. Examples include (meth)acrylate monomers or oligomers with olefinic unsaturated bonds at the end, formed by copolymerizing one or more (meth)acrylates with resin monomers having reactive groups.

[0039] Monomers of (meth)acrylate compounds that can be mentioned include epoxy (meth)acrylate resins, polyester (meth)acrylates, polyurethane (meth)acrylates, olefin unsaturated polyesters, amino (meth)acrylate resins, etc.

[0040] The content of the polymeric compound component having olefinic unsaturated bonds is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. The above upper and lower limits can be combined in any way. For example, a content of 10 to 90% by mass is preferred, more preferably 15 to 50% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass is preferred.

[0041] The solvent is a solvent capable of dissolving or dispersing the components contained in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition according to the present invention.

[0042] Solvents can be used alone or in combination of two or more.

[0043] The solvent content is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits can be combined in any way. For example, a content of 10 to 70% by mass is preferred, more preferably 15 to 70% by mass, and even more preferably 20 to 50% by mass is preferred. By setting the content to the lower limit or above, there is a tendency to suppress the occurrence of uneven coating. By setting the content to the upper limit or lower, there is a tendency to suppress the occurrence of foreign matter, shrinkage, etc.

[0044] It also includes photosensitizers and / or other additives.

[0045] There are no specific requirements for the photosensitizer here. Options include benzophenone-based photosensitizers, α-hydroxyketone-based photosensitizers, α-aminoketone-based photosensitizers, dimethylaminobenzophenone-based photosensitizers, thioxanone-based photosensitizers, thioxanone-based photosensitizers, biimidazole-based photosensitizers, triazine-based photosensitizers, and O-acyloxime-based photosensitizers.

[0046] The photosensitizer content is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 2.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less. The above upper and lower limits can be combined in any way. For example, the preferred content is 0.1 to 10% by mass, 2 to 10% by mass, further preferably 1 to 8% by mass, and particularly preferably 1 to 5% by mass.

[0047] Other additives include pigments, dispersants, leveling agents, fillers, and surfactants. There are no particular restrictions; they are added according to actual needs.

[0048] For the pigment portion, the following compounds can be used: nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthracene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolineone compounds, isoindoline compounds, quinacrine compounds, diazoanone compounds, violet ketone compounds, dinaphthalene-phenylene compounds, dioxopyrrole-pyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinoline ketone compounds, naphthalenetetracarboxylic acid; metal complexes of azo dyes and cyanine dyes; lake pigments; processed by furnace, tank, or thermal decomposition methods. Carbon black obtained by means of chemical processes, or acetylene black, Ketjen black, or lampblack, etc.: substances obtained by subjecting the above carbon blacks to acidic or alkaline surface treatment; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotubes, spiral carbon fiber, carbon nanotubes, carbon aerogel, fullerene, aniline black, pigment black, titanium black; hydrophobic resins, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cobalt sky blue, deep green pigments, emerald green, lead sulfate, chrome yellow, zinc yellow, iron oxide, pot red, synthetic iron black, brown clay, and other organic or inorganic pigments. These pigments can be used alone or in mixtures.

[0049] Commercially available pigments can also be used as the pigments mentioned above.

[0050] The amount of pigment added is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 2.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less. The above upper and lower limits can be combined in any way. For example, a content of 0.1 to 10% by mass, 2 to 10% by mass, further preferably 1 to 8% by mass, and particularly preferably 1 to 5% by mass is preferred.

[0051] Thirdly, the present invention provides a method for preparing a photoresist composition.

[0052] The photoresist composition of the present invention is prepared by mixing the components contained in the photoresist composition using a stirrer.

[0053] Fourthly, the application of a photoresist composition, wherein the photoresist composition is used in color photoresist, black matrix, photospacer, planarization layer, semiconductor photoresist or ink of a display element.

[0054] The oxime photoinitiator molecule of this invention has a high compatibility with conventional light sources (such as medium-pressure mercury lamps and LEDs), and its maximum absorption wavelength is closer to the light source wavelength (365nm) used in photoresist production lines, resulting in higher photosensitivity. Simultaneously, it exhibits good solubility, and after baking, its blue light absorption is significantly reduced compared to photoinitiators in existing technologies, effectively mitigating the yellowing effect caused by photoinitiators in photoresist compositions. Furthermore, containing only one oxime ester group, compared to photoinitiator molecules substituted with two oxime ester groups, it eliminates the need for symmetry control during synthesis, significantly reducing process difficulty and production costs. It also avoids problems such as precipitation in the formulation, increased system viscosity, or accelerated yellowing caused by large molecular weight, making it more suitable for large-scale production and commercial applications. Attached Figure Description

[0055] Figure 1 This is the 1H NMR spectrum of intermediate II during the synthesis of compound 3.

[0056] Figure 2 This is the 1H NMR spectrum of intermediate III during the synthesis of compound 3.

[0057] Figure 3 This is the hydrogen NMR spectrum of compound 3.

[0058] Figure 4 These are the UV-Vis absorption spectra of compound 3 at different baking times.

[0059] Figure 5 These are the UV-Vis absorption spectra of OXE-02 at different baking times.

[0060] Figure 6 This is a graph showing the changes in yellowness index of compound 3 and OXE-02 at 230℃ due to baking time. Detailed Implementation

[0061] The principles and features of the present invention are described below. The embodiments given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0062] Taking acyl halide compounds containing Cl as an example, this invention provides a method for preparing oxime ester photoinitiators:

[0063]

[0064] S1: Synthesis of Intermediate I: Starting material I and an acyl halide compound containing Z (carbonyl group) and R2 (starting material II) are reacted by Friedel-Crafts acylation reaction in the presence of aluminum trichloride or zinc chloride to obtain intermediate I.

[0065]

[0066] S2: Synthesis of Intermediate II: Intermediate I is oxidized with hydrogen peroxide to obtain Intermediate II.

[0067]

[0068] S3(1): Synthesis of intermediate III: Intermediate II reacts with isoamyl nitrite under the catalysis of hydrogen chloride, sodium alkoxide or potassium alkoxide to generate hydroxylamine compound, i.e. intermediate III.

[0069]

[0070] S3(2): Synthesis of intermediate III: Intermediate II reacts with hydroxylamine hydrochloride under the catalysis of anhydrous sodium acetate or hydrochloric acid to generate hydroxylamine compound, i.e., intermediate III.

[0071]

[0072]

[0073] S4: Synthesis of photoinitiators: Intermediate III is esterified with an acyl halide compound containing R3 (raw material III) or acetic anhydride to synthesize oxime ester photoinitiators.

[0074] The amount of catalyst used is conventional and can be determined by common sense in the field or by a few routine preliminary experiments.

[0075] Preparation Example:

[0076] Example 1: Preparation of Compound 3

[0077]

[0078] S1: Synthesis of Intermediate I: 22.7 g of starting material I and 13.3 g of aluminum chloride were dissolved in 300 mL of dichloromethane. A solution of 9.25 g of propionyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0 °C, and the reaction was stirred for 2 h. The reaction was quenched with 150 mL of 20 wt% icy dilute hydrochloric acid. The product was extracted twice with dichloromethane, dried over magnesium sulfate, concentrated, and dried again to obtain 22.1 g of Intermediate I, with a yield of 78%.

[0079] S2: Synthesis of Intermediate II: 19.8 g of Intermediate I was dissolved in 250 mL of acetic acid, 2.4 g of hydrogen peroxide was added, the temperature was raised to 70 °C, and the reaction was carried out for 6 h. The reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 16.9 g of Intermediate II, with a yield of 81%.

[0080] S3: Synthesis of Intermediate III: 15g of intermediate II was dissolved in 200mL of N,N-dimethylformamide, and 7mL of concentrated hydrochloric acid and 7g of isobutyl nitrite were added sequentially. The mixture was stirred at room temperature for 6h, quenched with ice water, and the reaction mixture was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 13.63g of intermediate III, with a yield of 83%.

[0081] S4: Synthesis of photoinitiator: 9.8 g of intermediate III and 3 g of triethylamine were dissolved in 30 mL of dichloromethane. 2.4 g of acetyl chloride solution dissolved in 10 mL of dichloromethane was slowly added dropwise at 0 °C, and the reaction was stirred for 2 h. The reaction was quenched with 10 mL of 20 wt% icy dilute hydrochloric acid, extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 8.11 g of compound (3), with a yield of 73%. Mass spectrometer: MALDI-TOF-MS (m / z) = 370.23.

[0082] Example 2: Preparation of Compound 75

[0083]

[0084] S1: Synthesis of Intermediate I-1: 45g of raw material 2-1 and 26.7g of aluminum chloride were dissolved in 300mL of dichloromethane. A solution of 36.1g of 3-cyclohexylpropionyl chloride dissolved in 50mL of dichloromethane was slowly added dropwise at 0℃, and the mixture was stirred for 2h. Then, 26.7g of aluminum chloride and a solution of 34.9g of 1-benzofuran-2-carbonyl chloride dissolved in 50mL of dichloromethane were added, and the mixture was stirred for 2h. The mixture was quenched with 150mL of 20wt% icy dilute hydrochloric acid. The product was extracted twice with dichloromethane, dried over magnesium sulfate, concentrated, and dried again to obtain 43.4g of intermediate I-1, with a yield of 71%.

[0085] S2: Synthesis of intermediate II-1: 25.5 g of intermediate I-1 was dissolved in 250 mL of acetic acid, 1.7 g of hydrogen peroxide was added, the temperature was raised to 70 °C, and the reaction was carried out for 6 h. The reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 20 g of intermediate II-1, with a yield of 76%.

[0086] S3: Synthesis of intermediate III-1: 15.7 g of intermediate II-1 was dissolved in 200 mL of N,N-dimethylformamide, and 4 mL of concentrated hydrochloric acid and 4.2 g of isobutyl nitrite were added sequentially. The mixture was stirred at room temperature for 6 h, quenched with ice water, and the reaction mixture was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 13.6 g of intermediate III-1, with a yield of 82%.

[0087] S4: Synthesis of photoinitiator 75: 11 g of intermediate III-1 and 2.1 g of triethylamine were dissolved in 30 mL of dichloromethane. A solution of 1.57 g of acetyl chloride dissolved in 10 mL of dichloromethane was slowly added dropwise at 0 °C, and the reaction was stirred for 2 h. The reaction was quenched with 10 mL of 20 wt% icy dilute hydrochloric acid, extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried again to obtain 8.95 g of compound (75), with a yield of 75%. Mass spectrometry: MALDI-TOF-MS (m / z) = 596.41.

[0088] Example 3: Preparation of Compound 20

[0089]

[0090] S1: Synthesis of Intermediate I-2: 28.3 g of starting material I and 13.3 g of aluminum chloride were dissolved in 300 mL of dichloromethane. A solution of 7.9 g of acetyl chloride dissolved in 50 mL of dichloromethane was slowly added dropwise at 0 °C, and the mixture was stirred for 2 h. Then, 26.7 g of aluminum chloride and a solution of 34.9 g of benzoyl chloride dissolved in 50 mL of dichloromethane were added, and the mixture was stirred for 2 h. The reaction was quenched with 150 mL of 20 wt% icy dilute hydrochloric acid. The product was extracted twice with dichloromethane, dried over magnesium sulfate, concentrated, and dried again to obtain 33.08 g of intermediate I-2, with a yield of 77%.

[0091] S2: Synthesis of intermediate II-2: 30.1 g of intermediate I-2 was dissolved in 250 mL of acetic acid, 2.4 g of hydrogen peroxide was added, the temperature was raised to 70 °C, and the reaction was carried out for 6 h. The reaction solution was filtered through a silica gel funnel, the filtrate was washed with water, the product was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 21.21 g of intermediate II-2, with a yield of 68%.

[0092] S3: Synthesis of intermediate III-2: 17.8 g of intermediate II-2 was dissolved in 200 mL of N,N-dimethylformamide, and 3.1 g of hydroxylamine hydrochloride and 5.3 g of anhydrous sodium acetate were added sequentially. The mixture was stirred at room temperature for 6 h, quenched with ice water, and the reaction mixture was extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 13.45 g of intermediate III-2, with a yield of 73%.

[0093] S4: Synthesis of photoinitiator: 9.2 g intermediate III-2 and 2.0 g triethylamine were dissolved in 30 mL dichloromethane. 1.6 g acetyl chloride solution dissolved in 10 mL dichloromethane was slowly added dropwise at 0 °C, and the reaction was stirred for 2 h. The reaction was quenched with 10 mL 20 wt% icy dilute hydrochloric acid, extracted twice with ethyl acetate, dried over magnesium sulfate, concentrated, and dried to obtain 7.54 g of compound (3), with a yield of 75%. Mass spectrometer: MALDI-TOF-MS (m / z) = 502.11.

[0094] Example 4-19:

[0095] Following the preparation methods of Examples 1 and 2, other compounds as shown in Table 1 were synthesized using the corresponding raw materials. Compound 18 is from Example 4, and so on.

[0096] Table 1

[0097]

[0098] Comparative Examples 1-6:

[0099] .

[0100] Performance testing:

[0101] 1. Film-forming performance test:

[0102] (1) Maximum absorption wavelength and molar absorptivity: The photoinitiator of this invention is prepared with a wavelength of 10. -5 A mol / L propylene glycol methyl ether acetate (PMA) solution was used to test its UV-Vis absorption spectrum, thereby obtaining its maximum absorption wavelength (λmax).

[0103] (2) Photoresist sensitivity: 2g of bisphenol fluorene resin, 0.1g of the compound of the present invention as a photopolymerization initiator, 0.06g of BYK-333, and 3.9g of PMA were placed in a reaction mixing tank equipped with a UV shield and a stirrer, and stirred at room temperature to prepare a photoresist composition. The photoresist composition was spin-coated onto a glass substrate and dried at 100°C on a hot plate for 1 minute to prepare a sample. Then, it was exposed using a step mask and developed in a 0.04% KOH aqueous solution. The sensitivity was evaluated based on the exposure dose when the thickness of the step mask pattern remained at 80% of the initial thickness. The exposure dose when the thickness of the P-1 pattern remained at 80% of the initial thickness was defined as 1. Other photoinitiators were evaluated. Under the same residual thickness, the lower the exposure dose, the higher the sensitivity.

[0104] (3) Molar absorptivity: The molar absorptivity (ε) at 365 nm was calculated according to Beer's Law.

[0105] 2. Yellowing resistance test: The sample is placed in a 365nm UV lamp box at 200mJ / cm². 2Deeply cure for 60 seconds, then bake continuously in an oven at 230℃ for 2 hours, and then test using a colorimeter (test standard is ASTM D1925).

[0106] The experimental results are shown in Table 2 below:

[0107] Table 2

[0108]

[0109] As shown in the table above, the oxime ester photoinitiator of this invention exhibits high photosensitivity (i.e., low exposure requirement), high light absorption at 365nm, and good anti-yellowing properties, demonstrating excellent developability and pattern integrity. The oxime ester photoinitiator of this invention exhibits excellent solubility in applications, and whether used alone or in combination with other conventional photoinitiators, it demonstrates superior developability and pattern integrity at the same exposure requirement. The film obtained using the oxime ester photoinitiator of this invention is colorless, a characteristic that makes it particularly advantageous in applications such as color photoresists, enabling the acquisition of pure colors and thus meeting the requirements of large-screen high-definition displays.

[0110] like Figure 6 The figure shows the changes in yellowness index of compound 3 and OXE-02 after baking at 230℃. It can be seen that the compounds provided by this invention are less prone to yellowing.

[0111] Figure 4 In the diagram, 04# is the test number for compound 3.

[0112] Figure 5 In the text, 02# is the test number for OXE-02.

[0113] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An oxime ester photoinitiator characterized in that, It has the structure as shown in general formula (I): R1 has the structure as shown in general formula (II): Y is O, C=O, N-R 11 , C1 alkylene, wherein R 11 is hydrogen, linear or branched alkyl with carbon atom number of 1-20, cycloalkyl with carbon atom number of 3-20, X is selected from S=O, * is a connection site; Z is selected from a carbonyl group or a direct bond; R2, R3 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms can be substituted or interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, a carbonyl bond, an amide bond or a urethane bond 1 to 5 times; R4to R 10 all are hydrogen, or one of R4to R 10 is selected from a nitro group, a cyano group, or a cycloalkanoyl group having 3 to 20 carbon atoms, a heterocycloalkanoyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aranoyl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaroyl group having 6 to 30 carbon atoms, and the rest are hydrogen; the substitution is that 1 to 3 hydrogen atoms in the aryl group having 6 to 30 carbon atoms, the heteroaryl group having 6 to 30 carbon atoms, the aryl ketone group having 6 to 30 carbon atoms, the heteroaryl ketone group having 6 to 30 carbon atoms are substituted by Ra or ORa; Ra respectively independently represents a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms; the methylene group of the alkylene moiety of the substituent represented by Ra is interrupted by an ether bond, a thioether bond, an ester bond, a thioester bond, a carbonyl bond, an amide bond or a urethane bond 1 to 5 times; the cycloalkyl group having 3 to 20 carbon atoms, the cycloalkyl ketone group having 3 to 20 carbon atoms, the heterocycloalkyl ketone group having 3 to 20 carbon atoms include the case that part or all of the carbon chain is cyclic or heterocyclic.

2. The oxime ester photoinitiator according to claim 1, characterized in that: the heteroatom in the heteroaryl group having 6 to 30 carbon atoms, the heterocycloalkyl ketone group having 3 to 20 carbon atoms, the heteroaryl ketone group having 6 to 30 carbon atoms is 1 to 2 kinds of O, S, N.

3. The oxime ester photoinitiator according to claim 1, wherein The cycloalkyl group having 3-20 carbon atoms has the following structural formula: , m is a natural integer of 1-5, and n is a natural integer of 0-5.

4. An oxime ester photoinitiator characterized in that, the oxime ester photoinitiator is selected from any one of the following structures: 。 5. A photoresist composition comprising the oxime ester photoinitiator according to any one of claims 1 to 4, a polymerizable compound having an ethylenically unsaturated bond and a solvent.

6. The photoresist composition of claim 5, wherein a photosensitizer and / or an additive are further included.

7. The photoresist composition of claim 6, wherein the additive includes any one or more of a pigment, a dispersant, a leveling aid, a filler or a surfactant.

8. Use of a photoresist composition characterized in that, the photopolymerization composition according to any one of claims 5 to 7 is used in a color resist, a black matrix, a photo spacer, a planarization layer, a semiconductor photoresist or an ink for a display element. the photopolymerization composition according to any one of claims 5 to 7 is used in a color resist, a black matrix, a photo spacer, a planarization layer, a semiconductor photoresist or an ink for a display element.

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