A triazine-based positive photoresist composition for organic insulating films

Abstract

The present application belongs to the technical field of photoresist, and particularly relates to a triazine-based positive photoresist composition for organic insulating film, which comprises the following components in parts by mass: triazine structure-containing acrylic polymer 30-100 parts; photoacid generator 0.05-20 parts; acid generator or base generator 0.05-10 parts; surfactant 0.005-5 parts; adhesion promoter 0.005-5 parts; and solvent 100-2000 parts. The present application introduces triazine structure containing double bond as a precursor, and makes it copolymerize with (methyl) acrylic acid and its ester or styrene and its derivatives and other monomers by free radical, the polymerization system has high reactivity, the obtained polymer has excellent hydrophobic property, heat resistance and dielectric property, the stability of the product in long-term storage and transportation is significantly improved, and the production cost is effectively reduced.

Description

Technical Field

[0001] This invention relates to a triazine-based positive photoresist composition for use in organic insulating films, belonging to the field of photoresist technology. Background Technology

[0002] Thin-film transistor liquid crystal displays (TFT-LCDs), as a mainstream display technology, are widely used in various electronic devices. Their basic structure equips each pixel with a thin-film transistor (TFT) as a semiconductor switching device to precisely control the voltage of the pixel unit, thereby adjusting the alignment of liquid crystal molecules to control light transmittance and achieve image display. In the multilayer wiring structure of TFTs, to prevent short circuits between different layers, inorganic materials with high dielectric constants, such as silicon dioxide (SiO2) or silicon nitride (SiN), are traditionally used to prepare the gate insulating layer. However, the use of such inorganic insulating materials leads to complex manufacturing processes and high costs, limiting the improvement of overall manufacturing efficiency.

[0003] To address these issues, the industry has attempted to develop various organic insulating materials to replace traditional inorganic dielectrics. For example, companies such as Japan's JSR and the US's Dow have successively launched interlayer insulating films based on organic materials such as acrylic resins, polysiloxanes, and photosensitive polyimides. These materials have, to some extent, improved the light transmittance, resolution, and array planarization performance of TFT devices.

[0004] However, existing organic materials still have significant limitations: the polysiloxane negative photoresist disclosed in Korean invention patent application No. KR10-2006-0022757A, although possessing high transmittance, is prone to component efflux during application, leading to decreased film uniformity and consequently affecting the yield of the display screen; photosensitive polyimide, due to the presence of chromophores in its molecular structure, causes coloration in the film, thereby reducing the optical transparency of the device; and the traditional acrylic resin disclosed in Korean invention patent application No. KR10-2004-0032468A has poor heat resistance, making it difficult to meet the requirements of high-temperature processes. Due to the poor compatibility between its linear structure and the benzene ring structure of the photosensitive agent, the photosensitive agent is unevenly distributed, resulting in an overall transmittance of <95%@400 nm. On the other hand, as the crosslinking density of C=C double bonds increases, the transmittance of this type of composition further decreases, thus affecting the long-term reliability and service life of TFT-LCD products. Chinese invention patent application CN119039241A discloses a method of condensing a triazine derivative with a diazononaphthoquinone sulfonyl chloride compound to obtain a diazononaphthoquinone-type photoinitiator, which is used by physical blending to improve the resolution of photoresist formulated with phenolic resin; however, there is still a risk of uneven mixing between the small molecule photosensitizer and the linear acrylic resin.

[0005] Therefore, it is still necessary to develop a new type of insulating material that combines high light transmittance, excellent thermal stability, and good film-forming properties to solve the various defects existing in the current technology. Summary of the Invention

[0006] In view of the above-mentioned technical problems in the prior art, the present invention provides a triazine-based positive photoresist composition for organic insulating films.

[0007] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: A triazine-based positive photoresist composition for organic insulating films, comprising the following components in parts by weight: 30-100 parts of acrylic polymers containing triazine structures; Photoacid-producing agent: 0.05–20 parts; 0.05 to 10 parts of acid-forming agent or alkali-forming agent; Surfactant 0.005 to 5 parts; Adhesive aid 0.005 to 5 parts; Solvent: 100-2000 parts.

[0008] Based on the above technical solution, the present invention can also be improved as follows: Furthermore, the acrylic polymer containing the triazine structure has the structure shown in general formula II:

[0009] General Formula II; in, a is a positive integer from 1 to 100; b is a positive integer from 1 to 100; c is a positive integer from 1 to 100; X is any one of O, NH or S; R1 is a methyl group or a hydrogen atom; R2 is selected from -OH, -NH2, -SH, alkyl, hydroxyalkyl, or alkyl chains with an epoxy group, or alkenyl groups containing a double bond and having 2 to 15 carbon atoms; or R2 is selected from aromatic groups and their derivatives; or R2 is selected from any of the following structures and their derived structures: , , , , , , Where m ≥ 1; R4 is a hydrogen atom or a methyl group; R3 is selected from any one of phenyl and its derivatives, pyridyl and its derivatives, cyclohexyl and its derivatives, pyrazolyl and its derivatives, imidazoleyl and its derivatives, triazineyl and its derivatives, or triazolyl and its derivatives; and the terminal group of R3 contains a reactive functional group II, wherein the reactive functional group II is any one or two or more of hydroxyl, carboxyl, epoxy, amino, and C=C. R5 and R6 are each independently selected from one or two of the following: methyl, alkyl chain containing 1 to 20 -CH2 groups, aromatic groups and their derivatives, ether, amide, amide-amine or ester, and the terminal groups of R5 and R6 each contain a reactive functional group I, wherein the reactive functional group I is selected from any one of hydroxyl, carboxyl, epoxy, amino, C=C.

[0010] Furthermore, the raw materials used to synthesize the acrylic polymer containing the triazine structure include: triazine derivatives containing multiple functional groups, (meth)acrylic acid and its ester monomers, and monomers with ethylene unsaturated bonds.

[0011] Furthermore, the triazine derivative containing multiple functional groups has the structure shown in general formula I:

[0012] General Formula I in, Y can be any one of O, NH, or S; Ra can be a hydrogen atom or a methyl group; Rb and Rc are each independently selected from one or two of the following: methyl, alkyl chain containing 1 to 20 -CH2 groups, aromatic groups and their derivatives, ether, amide, amide-amine or ester, and the terminal groups of Rb and Rc respectively contain a reactive functional group III, wherein the reactive functional group III is selected from any one of hydroxyl, carboxyl, epoxy, amino, C=C.

[0013] Furthermore, the triazine derivative containing multiple functional groups is obtained by reacting cyanuric chloride, cyanuric bromide, or cyanuric iodide with hydroxyethyl methacrylate, 2-mercaptoethyl methacrylate, or 2-aminoethyl methacrylate under alkaline conditions, followed by reaction with a substance containing hydroxyl, amino, or mercapto groups.

[0014] Furthermore, the alkaline conditions can be achieved using either an organic or an inorganic base. The organic base is selected from one or more of triethylamine, trimethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The inorganic base is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0015] Furthermore, in the synthesis of the triazine derivative containing multiple functional groups, the solvent used in the system can be a protic solvent or aprotic solvent, preferably water, methanol, ethanol, propanol, ethylene glycol, butanol, pentanol, tert-amyl alcohol, diethylene glycol, acetone, acetylacetone, ethyl acetate, n-hexane, N,N-dimethylformamide (DMF), N,N-diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, ethyl acetoacetate, diethylene glycol dimethylformamide, etc. One or more of the following: dimethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, methyl acrylate, propyl acrylate, methylcellulose, ethylcellulose, diethylene glycol methyl acetate, diethylene glycol ethyl ether acetate, methyl isobutyl ketone, cyclohexanone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,4-epoxyhexacyclohexane, glyphosate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether.

[0016] Furthermore, the reaction temperature for synthesizing the triazine derivative containing multiple functional groups is -20℃ to 120℃, preferably -10℃ to 100℃, and more preferably 0℃ to 80℃; the reaction time for synthesizing the triazine derivative containing multiple functional groups is 1h to 72h, preferably 2h to 48h, and more preferably 3h to 24h.

[0017] Furthermore, the (meth)acrylic acid and its ester monomers are selected from any one or more of the following: (meth)acrylic acid, (meth)acrylic acid-2-hydroxyethyl ester, (meth)acrylic acid glycidyl ester, N-((5-hydroxy-6-methylbicyclo[2.2.1]hept-2-yl)methyl)methacrylamide, (meth)acrylic acid diethylaminoethyl ester, diethylene glycol monoethyl ether (meth)acrylic acid ester, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid isopropyl ester, ethylene glycol di(meth)acrylic acid ester, polyethylene glycol (meth)acrylic acid ester, trimethylolpropane di(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylic acid ester, pentylenetetrol tetra(meth)acrylic acid ester, diethylene glycol phthalate-based (meth)acrylic acid ester, bisphenol A type (meth)acrylic acid ester and its derivatives, and (meth)acrylic acid cyclohexyl ester.

[0018] Furthermore, the monomer having ethylene unsaturated bonds is any one or a combination of two or more of the following: difunctional or trifunctional acrylates, maleic acid and its derivatives, norbornene and its derivatives, styrene and its derivatives, styrene and its derivatives, styrene-cinnamic acid and its derivatives.

[0019] Furthermore, the initiator used to synthesize the acrylic polymer containing the triazine structure is selected from azo compounds, acyl oxime compounds, biimidazole compounds, or acetophenone compounds.

[0020] Furthermore, the azo compound is selected from any one of azoisoheptanenitrile, azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0021] Further, the acyl oxime compound is selected from acetophenone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), acetophenone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-aminoazole-3-yl]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]octane-1-oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-formoxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-aminoazole-3-yl]ethane-1-benzyl Ester, ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-piperazol-3-yl]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-furan-3-yl]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0022] Furthermore, the acetophenone compounds are amino ketone compounds or hydroxy ketone compounds.

[0023] Furthermore, the aminoketone compound is selected from any one or more of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-ylphenyl)-butane-1-one, or 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one.

[0024] Furthermore, the hydroxy ketone compound is selected from any one or two or more of 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-hydroxyphenyl)-2-methylpropane-1-one, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropanone, or 1-hydroxycyclohexylphenyl ketone.

[0025] Furthermore, the biimidazole compound is preferably any one of 2,2'-bis(2-chlorophenyl)-4,4',5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5'-tetraphenyl-1,2'-biimidazole, or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5'-tetraphenyl-1,2'-biimidazole.

[0026] When biimidazole compounds are selected as free radical polymerization initiators, aliphatic or aromatic compounds having dialkylamino groups can be added as amino sensitizers. The amino sensitizer is preferably any one or a combination of 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. When biimidazole compounds and amino sensitizers are used in combination, the ratio of amino sensitizer to biimidazole compound is preferably (0.05:1) to (100:1), more preferably (0.1:1) to (60:1). By increasing the mass ratio of amino sensitizer to biimidazole compound from 0.05:1 to 100:1, the curing reactivity of the polymer can be improved, and the abrasion resistance of the obtained cured film can be improved.

[0027] Furthermore, a thiol compound can be added as a chain transfer agent. The thiol compound serving as a hydrogen radical donor is preferably an aromatic thiol compound or an aliphatic thiol compound. The aromatic thiol compound is preferably any one of 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, or 2-mercapto-5-methoxybenzothiazole; the aliphatic thiol compound is preferably any one or more of dodecanethiol, 3-mercaptopropionic acid or methyl 3-mercaptopropionate, pentaerythritol tetra(mercaptoacetate), or pentaerythritol tetra(3-mercaptopropionate).

[0028] Furthermore, the reaction temperature for synthesizing the acrylic polymer containing the triazine structure is 30℃~120℃, preferably 40℃~100℃, and more preferably 50℃~90℃; the reaction time for synthesizing the acrylic polymer containing the triazine structure is 1h~48h, preferably 2h~36h, and more preferably 3h~24h.

[0029] Furthermore, the triazine-containing acrylic polymer was tested for its molecular weight using GPC (gel permeation chromatography) with tetrahydrofuran as the mobile phase. The average molecular weight (based on polystyrene) was between 2,000 and 40,000, the dispersity was between 1.0 and 4.5, and the acid value was between 0 and 300 mg KOH / g.

[0030] Further, the solvent used for synthesizing the acrylic polymer containing triazine structure is selected from organic solvents; the organic solvent is selected from one or more of N,N-dimethylformamide (DMF), N,N-diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, ethyl acetoacetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, methyl acrylate, propyl acrylate, methyl cellulose, ethyl cellulose, diethylene glycol methyl acetate, diethylene glycol ethyl ether acetate, methyl isobutyl ketone, cyclohexanone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,4-dioxane, diglyme, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether.

[0031] Further, the photoacid generator is selected from commonly used photosensitizers.

[0032] Still further, selecting the photoacid generator from one or more of the substances represented by the following general formula III or general formula IV can improve the alkali etching resistance of the resin in the non-exposed area:

[0033] General formula III, General formula IV; In the above general formula III, n is a positive integer satisfying 1<n<10; In the above general formula III or general formula IV, R' is a hydrogen atom or any one of the structures represented by the following structural formula: ; R7 and R8 are each independently selected from a hydrogen atom, an alkyl group with 1 to 6 carbon atoms and derivatives thereof, an alkoxy group with 1 to 6 carbon atoms and derivatives thereof, a cycloalkyl group with 4 to 6 carbon atoms and derivatives thereof, or a phenyl group and derivatives thereof; R d and R e are each independently selected from a hydrogen atom, an alkyl group with 1 to 6 carbon atoms and derivatives thereof, an alkoxy group with 1 to 6 carbon atoms and derivatives thereof, a cycloalkyl group with 4 to 6 carbon atoms and derivatives thereof, or a phenyl group and derivatives thereof, or R d and R e is -OR'.

[0034] Further, the surfactant is selected from any one or a combination of two or more of fluorine-based surfactants, organosilicon-based surfactants, and nonionic surfactants.

[0035] Furthermore, the adhesive is selected from any one or a combination of two or more of the following: benzoyltrimethoxysilane, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0036] Furthermore, the acid-generating agent is selected from any one or more of the following: triphenylsulfonium salt, 2-[(2,3-dimethylphenyl)thio]benzoic acid and its esters, 4-hydroxybenzoic acid and its esters, 2-methylbenzyl-4-benzylmethanesulfonate, trifluoromethanesulfonate, succinate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-nitrobenzylcyclohexylcarbamate, 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate, p-toluenesulfonate, hexafluorophosphate, benzoate, and acetylcarbamate compounds; or any one or more of the following: halogen-containing compounds and sulfonate compounds.

[0037] Furthermore, the alkali generating agent is selected from one or more of the following: metals and their complexes, aromatic dimethylureas, aliphatic dimethylureas, organophosphorus salts, organic amines and their quaternary ammonium salts.

[0038] Furthermore, the solvents of the compositions of the present invention include high-boiling-point solvents with a boiling point of 180°C or higher at atmospheric pressure and low-boiling-point solvents with a boiling point of less than 180°C.

[0039] Furthermore, the high-boiling-point solvent has a boiling point of at least 180°C at atmospheric pressure, preferably 180°C to 250°C, and more preferably 190°C to 210°C. In the solvent of the present invention, the content of the high-boiling-point solvent is preferably 5% to 60%, more preferably 10% to 50%, and most preferably 15% to 40% (by weight of the solvent). Within the above ranges, a highly smooth film can be prepared during the coating process. The high-boiling-point solvent is selected from any one of γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, propylene carbonate, and methyl acetate. Preferably, in terms of developing performance, the high-boiling-point solvent of the present invention is selected from one or more of γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

[0040] Furthermore, the low-boiling-point solvent is compatible with but does not react with the components of the positive photoresist composition of the present invention, and has a boiling point of less than 180°C, preferably 100°C. The low-boiling-point solvent is selected from propylene glycol monomethyl ether acetate (PGMEA), N,N-dimethylformamide, ethyl acetone, ethyl carbonate, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, cyclohexanone, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, propylene glycol monomethyl ether, etc. Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, methyl ethyl ether, 2-heptanone, 3-heptanone, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxybutanol, and cyclopentanone are among one or more of these.

[0041] The beneficial effects of this invention are as follows: This invention employs precise molecular design, using a triazine ring as the core framework and introducing an acrylic compound with a triazine structure containing double bonds as the matrix. This allows for free radical copolymerization with (meth)acrylic acid and its ester monomers. The resulting polymerization system exhibits high reactivity, and the resulting polymer possesses both excellent hydrophobic and heat-resistant properties, significantly improving the stability of the product during long-term storage and transportation, while effectively reducing production costs.

[0042] This invention introduces triazine units with a stable, planar structure at the nanoscale into the traditional poly(meth)acrylate (meth)acrylate (acrylate) system and applies them to photoresist materials. This not only further enhances the transparency of the material but also helps to improve the aperture ratio and resolution of the insulating film material. Simultaneously, the low polarity of the triazine groups effectively reduces the dielectric constant of the organic insulating film. Furthermore, the C–N and C=N bonds contained in the triazine structure significantly improve the thermal stability, mechanical strength, chemical resistance, and etching tolerance of the resin material, meeting the comprehensive requirements of low-dielectric-constant insulating films for high residual film yield, excellent pattern flatness, and aperture ratio.

[0043] This invention synthesizes an acrylic polymer containing a triazine structure by using triazine derivatives containing multiple functional groups to participate in a free radical addition reaction. By controlling the type and number of functional groups of the monomers participating in the reaction, the length of the alkyl chain, and the introduction of aromatic or cycloalkyl structures, the hydrophilicity / hydrophobicity, temperature resistance, and chemical resistance of the polymer can be effectively adjusted.

[0044] This invention describes a positive photoresist composition prepared by compounding an acrylic polymer containing a triazine structure with a solvent, a free radical polymerization initiator, a monomer with ethylene unsaturated bonds, and other additives. After spin coating, pre-baking, exposure, development, and post-baking processes, the resulting organic insulating film exhibits good adhesion to the metal substrate, high UV transmittance, high residual film rate, and excellent pattern stability.

[0045] The organic insulating film prepared by this invention has comprehensive performance advantages, including high yield, low manufacturing cost, excellent light transmittance, high film flatness, stable pattern morphology, low dielectric constant, and strong adhesion to the underlying matrix. Attached Figure Description

[0046] Figure 1 The infrared spectrum of cyanuric chloride; Figure 2 The infrared spectrum of triazine derivative 1. Detailed Implementation

[0047] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0048] Synthesis of acrylic polymers containing triazine structures as shown in Formula II Synthesis example 1 6.51 g (50 mmol) of hydroxyethyl methacrylate (Mr=130.14), 100 g of methanol, and 9.22 g (50 mmol) of cyanuric chloride (Mr=184.15) were added to a three-necked flask. At -10 °C, 30 g (approximately 150 mmol) of 20% NaOH solution was added dropwise. After stirring for 2 h, the reaction temperature was raised to 40 °C and reacted for 16 h. The temperature was then further raised to reflux temperature and reacted for another 24 h. After cooling, the product was poured into ice water to obtain a viscous liquid substance, designated as triazine derivative 1. After washing with water, it was dried under vacuum at 40 °C for later use.

[0049] .

[0050] 2.55 g of triazine derivative 1 (Mr=255.09), 2.31 g of methacrylic acid (Mr=86.09), 2.01 g of methyl methacrylate (Mr=100.12), 1.71 g of glycidyl methacrylate (Mr=142.15), and 1.22 g of styrene (Mr=104.15) were added to a three-necked reactor. 100 g of dipropylene glycol dimethyl ether, 1.5 g of 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) were added as a free radical initiator, and 0.01 g of dodecanethiol was added as a chain transfer agent. The free radical copolymerization reaction was carried out at 80 °C for 18 h to obtain an acrylic polymer containing a triazine structure. The polymer had an average molecular weight of 4900, a molecular weight distribution of 1.59, and an acid value of 97.48 mgKOH / g, which can be used as the main resin material for positive photoresists.

[0051] Its synthesis process is as follows: .

[0052] Synthesis example 2 12.91 g (approximately 100 mmol) of 2-aminoethyl methacrylate (Mr = 129.08), 200 g of methanol, and 15.89 g (50 mmol) of cyanuric bromide (Mr = 317.76) were added to a three-necked flask. At -5 °C, 15.17 g (approximately 150 mmol) of triethylamine (Mr = 101) was added dropwise. After stirring for 2 h, the reaction temperature was raised to 60 °C, and the reaction was carried out at this temperature for 6 h. The temperature was then further raised to reflux temperature and reacted for 18 h. After cooling, the product was poured into ice water to obtain a viscous liquid substance, designated as triazine derivative 2. After washing with water, it was dried under vacuum at 40 °C for later use.

[0053] .

[0054] 6.09 g of triazine derivative 2 (Mr=365.17), 10.34 g of methacrylic acid (Mr=86.09), 10.42 g of 4-hydroxystyrene (Mr=120.15), and 17.05 g of tetrahydrofuran methacrylate (Mr=170.21) were added to a three-necked reactor. 180 g of N,N-dimethylformamide was added, and the reaction was carried out at 30 °C for 1 h. Then, 0.5 g of azoisoheptanenitrile and 0.01 g of dodecanethiol were added as chain transfer agents. The reaction temperature was raised to 60 °C, and a free radical copolymerization reaction was carried out for 24 h. The resulting acrylic polymer containing a triazine structure had an average molecular weight of 16,000, a molecular weight distribution of 2.3, and an acid value of 153.5 mgKOH / g. It can be used as the main resin material for positive photoresists. In positive photoresist systems, the secondary amino group attached to the triazine ring of this substance can act as a photoacid scavenger, significantly improving the photoresist's resistance to alkaline etching by absorbing or quenching some of the photoacid.

[0055] Its synthesis process is as follows: .

[0056] Synthesis example 3 21.91 g (approximately 150 mmol) of 2-mercaptoethyl methacrylate (Mr = 146.04), 200 g of N-methylpyrrolidone, and 22.94 g (50 mmol) of cyanuric acid triiodocyanide (Mr = 458.76) were added to a three-necked flask. At -5 °C, 22.83 g (approximately 150 mmol) of DBU (Mr = 152.24) was added dropwise. After stirring for 4 h, the reaction temperature was raised to 80 °C and reacted for 4 h. The temperature was then further raised to reflux temperature and reacted for another 4 h. After cooling, the product was poured into ice water to obtain a viscous liquid substance, designated as triazine derivative 3. After washing with water, it was dried under vacuum at 40 °C for later use.

[0057] .

[0058] 2.14 g of triazine derivative 3 (Mr=513.11), 8.37 g of maleic anhydride (Mr=98.06), and 26.53 g of hydroxyethyl methacrylate (Mr=130.14) were added to 200 g of ethylene glycol monoethyl ether acetate. 0.5 g of acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) and 0.01 g of dodecanethiol were added as chain transfer agents. The mixture was stirred, and the reaction temperature was raised to 70 °C for free radical copolymerization for 8 h. The resulting acrylic polymer containing a triazine structure had an average molecular weight of 22,500, a molecular weight distribution of 3.5, and an acid value of 255.6 mgKOH / g. This resin can be used as the main resin material for positive photoresists.

[0059] Its synthesis process is as follows: .

[0060] The components of the triazine-based positive photoresist composition for use in organic insulating films are as follows: Acrylic polymers containing triazine structures as shown in Formula II The components used to prepare the compositions of the examples and comparative examples are as follows: A-1: The polymer from Synthetic Example 1; A-2: Polymer of Synthetic Example 2; A-3: Polymer of Synthetic Example 3; Photoacid-producing agents: B-1: A condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (3 mol); B-2: A condensate of 1,3,5-p-hydroxyphenyltriazine (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (2.0 mol). <c>Acid-forming agent or base-forming agent C-1: Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate; C-2: 2-Nitrobenzylcyclohexylcarbamate; C-3: 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate; <d>surfactants FZ-2122, Dow Corning Toray Silicone; <e>Adhesive γ-Isocyanate-propyltriethoxysilane, Shin-Etsu; <f>solvent F-1: Propylene glycol monomethyl ether acetate (20℃, 3.75mmHg); Example 1 100g of the triazine-containing acrylic polymer (A-1) synthesized in Synthesis Example 1, 4g of photoacid-generating agent (B), 1g of acid-generating agent or alkali-generating agent (C-1), 1g of (C-2), 1g of (C-3), 0.3g of surfactant (D), and 1g of adhesive (E) were added to a container. Then, propylene glycol monomethyl ether acetate solvent (F-1) was added to make the solids concentration 20% to prepare a positive photoresist composition.

[0061] Examples 2-11 and Comparative Examples 1-2 Examples 2-11 and Comparative Examples 1-2 were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Tables 1 and 2. Additionally, <-> in Tables 1 and 2 indicate that the corresponding component was not used.

[0062] Furthermore, in Comparative Examples 1-2, an adhesive resin (average molecular weight 12000) represented by Formula 3 was used instead of the polymer with the structure shown in Formula II of Example 1 above. Except that the composition and content of the composition varied according to the composition described in Table 2 below, the positive photoresist composition for organic insulating film of liquid crystal display element was manufactured using the same method.

[0063]

[0064] Formula 3 In Equation 3 above, p is 0.3, q is 0.2, and r is 0.5.

[0065] The performance of the positive photoresist compositions prepared as described in the above examples and comparative examples was evaluated as follows.

[0066] I. Evaluation of the photosensitivity of positive photoresist compositions On a silicon substrate, after spin-coating the compositions of Examples 1-11 and Comparative Examples 1-2 using a spin coater, pre-baking was performed at 100°C for 2 minutes using a hot plate to form a coating film with a thickness of 1.5 μm. For the obtained coating film, a Canon PLA-501F exposure unit (ultra-high pressure mercury lamp) was used to expose the silicon wafer under a mask with a pattern of 3.0 μm linewidth. By varying the exposure time, unexposed material was removed by washing in a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) solution at 25°C for 80 seconds. Then, the substrate was washed in ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this point, the spatial linewidth (lower portion) was 0.30 μm. The minimum required exposure was measured, and the photosensitivity results are shown in Tables 1 and 2. When the minimum exposure was less than 200 (J / m²), the photosensitivity was significantly reduced. 2 When the light sensitivity is good, it is considered to be good.

[0067] II. Evaluation of the refractive index of interlayer insulating films A cured film was formed on a silicon substrate, and the refractive index of the cured film was obtained. The refractive index of the cured film was measured at 633 nm using an Auto EL IV NIR III spectrometer. When the refractive index is higher than 1.50, the material is considered suitable for use as an interlayer insulating film.

[0068] III. Evaluation of the heat resistance of interlayer insulating films A cured film was formed on a silicon substrate, and the thickness (T2) of the cured film was measured. Then, the silicon substrate with the cured film was further baked in a clean oven at 240°C, and the thickness (t2) of the cured film was measured again. The film thickness change rate was calculated using the following formula after further baking: [(t2-T2) / T2]×100%. The results are shown in Tables 1 and 2. A heat resistance of less than or equal to 3% is considered good.

[0069] IV. Evaluation of the transmittance of interlayer insulating film Similar to the "Photosensitivity Evaluation" described above, a thin film was formed on a glass substrate. The resulting thin film was then exposed using a Canon PLA±501F exposure lamp (ultra-high pressure mercury lamp) with a cumulative irradiation dose of 3000 J / m². 2 After exposure, the film is heated at 220°C for 1 hour in a clean drying oven to obtain a cured film. The transmittance of the glass substrate with this cured film was measured using a spectrophotometer "TU-1810" (manufactured by Beijing General Analytical Instrument Co., Ltd.) in the wavelength range of 400-800 nm. The results are shown in Tables 1 and 2. When the minimum transmittance exceeds 92%, the light transmittance is considered good.

[0070] V. Evaluation of the dry etching resistance of the interlayer insulating film A cured film was formed on a silicon substrate and dry etched using a CDE-80N dry etching apparatus (manufactured by Shibaura Mechatronics Co., Ltd.). The etching gases were CF4: 50 mL / min, O2: 10 mL / min, and output 400 mW. Dry etching was performed for 90 seconds, and the film head was measured before and after the process. The results are shown in Tables 1 and 2. A film thickness reduction of less than 1.0 μm was considered to indicate good dry etching resistance.

[0071] VI. Determination of dielectric constant Photoresist is coated onto a substrate forming aluminum electrodes using a spin coater, and a dielectric constant measurement unit is fabricated. The dielectric constant is then determined using an impedance matching device.

[0072] Table 1 Examples and their physical property test results

[0073] Table 2 Comparative Examples and Their Physical Property Test Tables

[0074] As can be seen from the results in Tables 1 and 2, compared with positive photoresist compositions using only the polymer shown in Formula 3, the positive photoresist composition of the present invention containing an acrylic polymer with a triazine structure as shown in General Formula II exhibits superior overall performance in the cured film, including significantly improved heat resistance, higher transmittance, and good dry etching performance. This is mainly attributed to the stable hydrophobic properties and high transparency of the introduced triazine structure itself, which helps to enhance the aperture ratio and water resistance of the photoresist. Simultaneously, the low polar group content in the triazine groups of the present invention effectively reduces the dielectric constant of the resin material, thereby helping to reduce the parasitic capacitance formed between the pixel electrode and the wiring, meeting the application requirements of low dielectric constant organic insulating films. Furthermore, the triazine structure also endows the material with good thermal stability, mechanical properties, and chemical stability, making it meet the various performance requirements of insulating film materials. This indicates that within the scope defined by General Formula II of the present invention, the triazine core framework is the key to dominant performance; therefore, combinations of different monomers can all guarantee the lower limit of excellent performance. This invention further improves the adhesion between the resin and the matrix by controlling the type and number of functional groups in the triazine derivative and (meth)acrylate monomer, while also improving the residual film rate, pattern flatness, and aperture ratio. Through precise molecular design, this invention uses the triazine ring as the core framework, chemically bonded to (meth)acrylate segments via ether, thioether, and secondary amine groups, forming a novel polymer architecture. This structure ensures that the stability and hydrophobicity of the triazine ring are fully utilized, while its nanoscale planar structure effectively avoids light scattering, thus significantly improving heat resistance and chemical resistance while unexpectedly maintaining extremely high transparency. This "win-win" effect overcomes a long-standing technical bias in the field—that increasing crosslinking density and heat resistance often sacrifices the optical transparency and processability of the material.

[0075] contrast< / f> < / e> < / d> < / c> Figure 1 (Infrared spectrum of cyanuric chloride) and Figure 2 Infrared spectral analysis of (the infrared spectrum of triazine derivative 1) confirmed the successful synthesis of the target triazine derivative: at 1722 cm⁻¹ -1 The absorption peak at 1636 cm⁻¹ is attributed to the carbonyl group in the ester group, indicating that a carbonyl-containing substance was successfully introduced into the triazine structure; -1 The absorption peak observed at 3503 cm⁻¹ can be attributed to the C=C double bond, confirming the presence of a double bond structure in the product; -1 The absorption peak at 2874 cm⁻¹ corresponds to a hydroxyl group, indicating the synthesis of a triazine derivative with a hydroxyl group; while at 2874 cm⁻¹... -1 The absorption peak at that location indicates the presence of a methyl or methylene structure. In summary, Figure 2 The results confirmed the formation of the target product, triazine derivative 1.

[0076] 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. A triazine-based positive photoresist composition for use in organic insulating films, characterized in that, Based on parts by weight, it includes the following components: 30-100 parts of acrylic polymers containing triazine structures; Photoacid-producing agent: 0.05–20 parts; 0.05 to 10 parts of acid-forming agent or alkali-forming agent; Surfactant 0.005 to 5 parts; Adhesive aid 0.005 to 5 parts; Solvent: 100–2000 parts; The acrylic polymer containing a triazine structure is selected from the following structures: ； ； 。 2. The triazine-based positive photoresist composition for organic insulating films according to claim 1, characterized in that, The surfactant is selected from any one or a combination of two or more of fluorinated surfactants, organosilicon surfactants, and nonionic surfactants. The adhesive is selected from any one or a combination of two or more of the following: benzoyltrimethoxysilane, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Images