A multi-acid anhydride-based positive photoresist composition for organic insulating films

Abstract

The application belongs to the technical field of photoresists and specifically relates to a multi-acid anhydride-based positive photoresist composition for an organic insulating film, which comprises the following components in parts by mass: acrylic polymer based on polycarboxylic acid derivative 20-100 parts; photoacid generator 0.03-20 parts; acid generator or base generator 0.01-10 parts; surfactant 0.01-5 parts; adhesion promoter 0.01-5 parts; and solvent 100-2000 parts. The application introduces the structure of polycarboxylic acid, uses R soft segment as the polycarboxylic acid structure with a double bond to carry out a free radical polymerization reaction with (meth) acrylic acid and ester monomers, improves the long-term storage and transportation stability of the product, applies the product to a photoresist material, further improves the transparency of the material, improves the aperture ratio and resolution of the insulating film material, and reduces the dielectric constant of the organic insulating film.

Description

Technical Field

[0001] This invention relates to a polyacid anhydride-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) are a type of liquid crystal display solution based on active matrix driving technology. Their core feature is the use of an independent TFT semiconductor switching device for each pixel. By adjusting the voltage signal applied between the TFT gate and source, the alignment of liquid crystal molecules is precisely controlled, thereby adjusting the backlight transmittance to achieve image display. Since its commercialization in the 1990s, this technology has become the dominant technology in the flat panel display field due to its advantages of high resolution, low power consumption, and thinness, and is widely used in smartphones, televisions, and automotive displays.

[0003] In the manufacturing process of TFT array substrates, the interlayer insulating film, as a key functional layer, must simultaneously meet requirements such as high dielectric constant (to improve TFT switching performance), high light transmittance (to reduce light loss), and good thermal stability. Traditional processes use inorganic materials such as SiO2 (silicon oxide) or SiN (silicon nitride) as gate insulating films. Although these materials can meet basic functional requirements, their high hardness and brittleness increase the complexity of thin film deposition and etching processes. Furthermore, the interfacial stress between the film and organic semiconductor layers can easily cause problems such as TFT threshold voltage drift, thus restricting the improvement of display device performance.

[0004] To address the aforementioned bottlenecks, the industry has attempted to explore solutions through materials innovation, but the following technical shortcomings still exist: 1. Acrylic resin materials (such as those developed by JSR in Japan): Although they improve the transparency and planarization properties of the insulating film, their high temperature resistance is insufficient (usually below 200°C), making it difficult to meet the process requirements such as high temperature photoresist curing in TFT array manufacturing.

[0005] 2. Polysiloxane materials (such as those proposed by Dow Chemical in the United States): Although they have excellent flexibility, their molecular chain segments are prone to phase separation, which leads to an increase in the surface roughness of the insulating film and affects the orientation effect of liquid crystal molecules.

[0006] 3. Photosensitive polyimide materials: Although they can simplify the process, residual chromophores can introduce optical scattering centers, reducing the light transmittance of the display panel.

[0007] The limitations of existing material systems in terms of overall performance highlight the urgent need to develop new interlayer insulation materials with high stability, high light transmittance, and excellent process compatibility. Summary of the Invention

[0008] To address the aforementioned deficiencies in the prior art, this invention provides a multi-acid anhydride-based positive photoresist composition for use in organic insulating films.

[0009] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: A polyacid anhydride-based positive photoresist composition for use in organic insulating films, comprising, by weight, the following components: 20-100 parts of acrylic polymer based on polycarboxylic acid derivatives; Photoacid-producing agent 0.03-20 parts; 0.01-10 parts of acid-forming agent or alkali-forming agent; Surfactant 0.01-5 parts; Adhesive aid 0.01-5 parts; Solvent: 100-2000 parts.

[0010] Based on the above technical solution, the present invention can also be improved as follows: Furthermore, the acrylic polymer based on polycarboxylic acid derivatives is a homopolymer, having the structure shown in general formula I or general formula II:

[0011] General Formula I 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 selected from any one of O, NH, or S; R1 is a methyl group or a hydrogen atom; R2 and R3 are each independently selected from any one or more of the following structures and their derivatives: -OH, -NH2, -SH, alkyl groups having 1 to 15 carbon atoms and their derivatives, olefinic groups having 2 to 15 carbon atoms, aromatic groups and their derivatives, maleic anhydride and its derivatives, pyridyl and its derivatives, cyclohexyl and its derivatives, pyrazolyl and its derivatives, imidazole and its derivatives, polyacid anhydride and its derivatives, or triazolyl and its derivatives; or R2 and R3 are each independently selected from any one of the following structures and their derived structures: , , , , , , Where m≥1, and R4 is a hydrogen atom or a methyl group; The terminal group of R3 may contain a reactive functional group II, wherein the reactive functional group II is any one or two or more of hydroxyl, carboxyl, epoxy, amino, C=C, etc. R5 may be selected, either alone or simultaneously, as hydrogen, methyl, alkyl containing 1 to 20 -CH2 groups, aromatic groups and their derivatives, ether, amide, amide-amine, ester, or carboxylic acid; or R5 may be selected, either alone or simultaneously, as the following structures: ; In the above formula, the definitions of R1, R2, R3, a, b, and c are the same as the definitions of R1, R2, R3, a, b, and c in general formula I and general formula II, respectively. R6 is selected from any one of hydrogen, methyl, alkyl groups containing 1 to 20 -CH2 groups, aromatic groups and their derivatives, ethers, amides, amide-amines, esters, and carboxylic acids; or, R6 has the following structure: ; In the above formula, the definitions of R1, R2, R3, a, b, and c are the same as the definitions of R1, R2, R3, a, b, and c in general formula I and general formula II, respectively.

[0012] Furthermore, the acrylic polymer based on polycarboxylic acid derivatives is synthesized by reacting polycarboxylic acid derivatives containing multiple functional groups, (meth)acrylic acid and its ester monomers, monomers with ethylene unsaturated bonds, initiators, and solvents.

[0013] Furthermore, the polycarboxylic acid derivative containing multiple functional groups has the structure shown in general formula III or general formula IV:

[0014] General Formula III General Formula IV in, X is selected from any one of O, NH, or S; R1 is a hydrogen atom or a methyl group; R5 and R6 are each independently selected from any one or two of hydrogen, methyl, alkyl containing 1 to 20 -CH2 groups, aromatic groups and their derivatives, ether, amide, amide-amine, and ester. The terminal groups of R5 and R6 contain a reactive functional group I, which is selected from any one or two or more of hydroxyl, carboxyl, epoxy, amino, and C=C groups. Alternatively, R5 can be selected, either simultaneously or individually, in the following structure: ; In the above formula, the definitions of R1, R2, R3, a, b, and c are the same as the definitions of R1, R2, R3, a, b, and c in general formula I and general formula II, respectively. Alternatively, R6 can have the following structure: ; In the above formula, the definitions of R1, R2, R3, a, b, and c are the same as the definitions of R1, R2, R3, a, b, and c in general formula I and general formula II, respectively.

[0015] Furthermore, the polycarboxylic acid derivative containing multiple functional groups is obtained by reacting phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, tetrahydrophthalic anhydride, trimellitic phthalic anhydride, or hydrogenated pyromellitic dianhydride with hydroxyethyl methacrylate, 2-mercaptoethyl methacrylate, or 2-aminoethyl methacrylate, and then reacting it with other substances containing reactive groups such as hydroxyl, amino, or mercapto groups.

[0016] Furthermore, the solvent used to synthesize the polycarboxylic acid derivative containing multiple functional groups is 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, and diethylene glycol dimethyl ether. One or more of the following: 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.

[0017] Furthermore, the reaction temperature for synthesizing the polycarboxylic acid derivative containing multiple functional groups is -10℃ to 150℃, preferably 0℃ to 120℃, and more preferably 10℃ to 100℃.

[0018] Furthermore, the reaction time for synthesizing the polycarboxylic acid derivative containing multiple functional groups is 1 h to 48 h, preferably 2 h to 36 h, and more preferably 3 h to 24 h.

[0019] Furthermore, the (meth)acrylic acid and its ester monomers used to synthesize the acrylic polymer based on the polycarboxylic acid derivative are selected from (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofuran (meth)acrylate, norbornyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, and N-((5-hydroxy-6-methylbicyclo[2.2]). 1] Hept-2-yl)methyl)methacrylamide, diethylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, butyl (meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylate, trimethylpropane di(meth)acrylate, trimethylpropane tri(meth)acrylate, pentaerythritol tetraacrylate (meth)acrylate, ethylene glycol (meth)acrylate, α,β-unsaturated (meth)acrylate, bisphenol A dipropylene glycol ether (meth)acrylate, (methyl) The first one or more of the following: β-hydroxyethyl acrylate, diethylene glycol (meth)acrylate, dipropylene glycol (meth)acrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, or pentaerythritol trimethacrylate.

[0020] Furthermore, the monomers having ethylene unsaturated bonds in the synthesis of the acrylic polymer based on polycarboxylic acid derivatives are selected from any one or a combination of two or more of (meth)acrylic acid and its ester derivatives, maleic acid and its derivatives, norbornene and its derivatives, styrene, styrene and its derivatives, and styrene-cinnamic acid derivatives.

[0021] Furthermore, the reaction temperature for synthesizing the acrylic polymer based on polycarboxylic acid derivatives is 30℃~120℃, preferably 40℃~90℃, more preferably 50℃~80℃; the reaction time is 1h~48h, preferably 2h~36h, more preferably 3h~24h.

[0022] Furthermore, the initiator used to synthesize the acrylic polymer based on polycarboxylic acid derivatives is an azo compound, an acyl oxime compound, a biimidazole compound, or an acetophenone compound.

[0023] Furthermore, the azo photoinitiator is any one of 2,2'-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and its dosage is between 0.01% and 5% of the total monomer dosage.

[0024] Furthermore, the acetophenone compounds are amino ketone compounds or hydroxy ketone compounds.

[0025] 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.

[0026] 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-dipropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one or 1-hydroxycyclohexylphenyl ketone.

[0027] Further, the acyl oxime compound is selected from acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-aminoazol-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-aminoazol-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).

[0028] Furthermore, the biimidazole compound is selected from 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.

[0029] When biimidazole compounds are selected as free radical polymerization initiators, aliphatic or aromatic compounds having a dialkylamino group can be added as amino sensitizers. The amino sensitizer is preferably any one of 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone, or a combination thereof.

[0030] When biimidazole compounds and amino sensitizers are used in combination, thiols can be added as hydrogen radical donors. Biimidazole compounds generate imidazole radicals under the action of amino sensitizers, enhancing their polymerization initiation ability. By adding thiols to the system where biimidazole compounds and amino sensitizers coexist, hydrogen radicals from the thiols are donated to the imidazole radicals. This not only converts the imidazole radicals into neutral imidazoles but also generates a component of sulfur radicals with high polymerization initiation ability. Therefore, even with low irradiation doses, hardened films with high frictional resistance can be formed.

[0031] 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 3-mercaptopropionic acid or methyl 3-mercaptopropionate, pentaerythritol tetra(mercaptoacetate), or pentaerythritol tetra(3-mercaptopropionate).

[0032] When biimidazole compounds and amino sensitizers are used in combination, the preferred ratio of amino sensitizer to biimidazole compound is 0.05-100, more preferably 0.1-60. By increasing the mass ratio of amino sensitizer to biimidazole compound from 0.05 to 100, the curing reactivity of the polymer can be improved, and the abrasion resistance of the obtained cured film can be improved.

[0033] Furthermore, the acrylic polymer based on polycarboxylic acid derivatives is synthesized using an organic solvent selected from any 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 propionate, 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.

[0034] Furthermore, the acrylic polymer based on polycarboxylic acid derivatives shown in Formula I or Formula II of the present invention, when tested by GPC (gel dialysis chromatography) with tetrahydrofuran as the mobile phase, has an average molecular weight (based on polystyrene) of 2000 to 40,000, a dispersity of 1.0 to 4.5, and an acid value of 0 mg KOH / g to 300 mg KOH / g.

[0035] Furthermore, the photoacid-generating agent in the polyacid anhydride-based positive photoresist composition of the organic insulating film is selected from condensates of 1,2-naphthoquinone diazido-5-sulfonyl chloride or 1,2-naphthoquinone diazido-4-sulfonyl chloride and phenolic derivatives in different proportions. The phenolic derivatives are selected from phenol, catechol, hydroquinone, 1,1,1-tris(p-hydroxyphenyl)ethane, phenolic resin (molecular weight less than 2000), naphthol, tannic acid, 2,3,4,4'-tetrahydroxybenzophenone, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-dimethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,6- Di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamine)phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,5-xylenol, etc., xylenol, 2,3,5-trimethylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3,5-triethylphenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol or 3-methyl-4-isopropylphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene One or more of the following: 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-hydroxyanthracene, 2-hydroxyanthracene, 9-hydroxyanthracene, etc.; 1,4-dihydroxyanthracene, 9,10-dihydroxyanthracene, etc.; 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2,7-trihydroxyanthracene; and A,A,A'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene.

[0036] Furthermore, the surfactant in the polyacid anhydride-based positive photoresist composition of the organic insulating film is selected from any one or a combination of two or more fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0037] Furthermore, the fluorinated surfactants are selected from commercially available products, such as one or more of DuPont's Capstone FS-3100 and FS-61, Wuhan Bolite Chemical's Fc-43, and Fujian Sanmei's SMF1720.

[0038] Furthermore, the silicone surfactant is selected from commercially available polydimethylsiloxane (PDMS), polyether-modified polydimethylsiloxane (such as PEG-15 / PPG-10 polydimethylsiloxane), alkyl polydimethylsiloxane (such as cetyl polydimethylsiloxane, stearyl polydimethylsiloxane), etc., for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345 to BYK-349 from BYK Chemical, and KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640 to KF-643, KF-6020, KF-6011 to KF-6017 from Shin-Etsu Chemical, etc., one or more of these.

[0039] Furthermore, the nonionic surfactant is selected from one or more of the following commercially available polyoxyethylene types (such as fatty alcohol polyoxyethylene ether type, alkylphenol polyoxyethylene ether type), polyoxyethylene fatty acid ester type, and polyoxyethylene alkylphenol ether type.

[0040] Furthermore, the adhesion promoter in the polyacid anhydride-based positive photoresist composition of the organic insulating film is any one or a mixture of two or more of the following: trimethoxysilylbenzoic acid, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The adhesion promoter used in this invention can improve the adhesion between the organic insulating film and the substrate.

[0041] Furthermore, the solvent of the organic insulating film's polyacid anhydride-based positive photoresist composition includes 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 below 180°C.

[0042] 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 5%-60%, preferably 10%-50%, and more preferably 15%-40% (referring to the total weight of the solvent). Within the above range, a highly smooth film can be prepared during the coating process.

[0043] Furthermore, 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,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, ethyl acetone, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate, propylene carbonate, and benzoyl acetate. Preferably, in terms of improving developing performance, the high-boiling-point solvent of the present invention is selected from any one or a mixture of two 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.

[0044] Furthermore, the low-boiling-point solvent is compatible with the components of the composition but does not react with them, and has a boiling point of less than 180°C, preferably 100°C.

[0045] Furthermore, the low-boiling-point solvent is selected from any one or more of propylene glycol monomethyl ether acetate (PGMEA), 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, 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, N-methylpyrrolidone, N-ethylpyrrolidone, and cyclopentanone.

[0046] Furthermore, the acid-generating agent of the polyacid anhydride-based positive photoresist composition of the organic insulating film is an ionic compound or a nonionic compound; the ionic compound is selected from any one or two or more of the following: triphenylsulfonamide, 1-dimethylthiobenzoate, 4-hydroxybenzoate, benzyl-4-hydroxyphenylmethylsulfonamide, 2-methylphenyl-4-hydroxyphenylmethylsulfonamide, 2-methylbenzylmethylsulfonamide, 2-methylbenzyl-4-benzylmethanesulfonate, trifluoromethanesulfonate, tetrahydrothiophene sulfonate, succinate, p-toluenesulfonate, hexafluorophosphate, benzoate, and acetylcarbamate compounds; the nonionic compound is selected from any one or two or more of the following: halogen-containing compounds, tertiary amine compounds, sulfonamide compounds, sulfonate compounds, carbonate compounds, and phosphate compounds.

[0047] Furthermore, the halogen-containing compound is a halogen-containing hydrocarbon or a heterocyclic cyclic compound containing a halogen group.

[0048] Furthermore, the halogen-containing compound is selected from any one or more of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, or 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

[0049] Furthermore, the tertiary amine compound is selected from any one or more of xylene(trifluoromethylsulfonyl)diazamide, dimethane(cyclohexane)diazamide, xylyldiazamide, xylene(p-methanol)diazamide, dimethane(2,4-phospholipid)diazamide, xylene(p-chlorobenzenesulfonamide)diazamide, methylsulfonyl-p-toluenesulfonamide, cyclohexane(1,1-dimethylethylsulfonamide)diazamide, N,N-dimethylethylsulfonamide, xylene(1,1-dimethylethylsulfonyl)diazamide, and benzyl(benzoyl)diazamide.

[0050] Furthermore, the sulfonamide compound is selected from any one of β-ketosulfonamide compounds, β-sulfonamide compounds, and diphenylsulfonamide compounds; preferably, it is any one or more of 4-triphenylsulfonamide, sulfathiazole, bisphenol (phenylphenyl)methane, or 4-chlorophenyl-4-methylbenzyldisulfonamide.

[0051] Furthermore, the sulfonate compound is selected from alkyl sulfonates, haloalkyl sulfonates, or aryl sulfonates. Preferably, it is any one or more of benzyl sulfonate, methanesulfonic acid, nitrophenyl-9,10-dioxytetraene-2-sulfonic acid, 2,6-phenylbenzenesulfonate, and N-(trifluoromethylsulfonyloxy)naphthyldicarboximide.

[0052] Furthermore, the acid generating agent is tetrahydrothiophene sulfonate, preferably any one of 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthyl-1-yl)tetrahydrothiophene trifluoromethanesulfonate, or 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiophenyl trifluoromethanesulfonate.

[0053] Furthermore, the alkali-generating agent of the polyacid anhydride-based positive photoresist composition of the organic insulating film is selected from any one or two or more of metals or their complexes, and organic amine compounds.

[0054] Furthermore, the metal or its complex is selected from any one of bromide cobalt bromide perchlorate, bromophenylmethylamine cobalt bromide perchlorate, bromofenpropylamine cobalt bromide perchlorate, hexamethylamine cobalt bromide perchlorate, and hexapropylamine cobalt bromide perchlorate.

[0055] The acid-generating agent or alkali-generating agent of the present invention can release acid-active substances or alkali-active substances as catalysts when heated. When the components undergo polymerization and curing reactions, these compounds can be used to promote the axial reaction of the effective components of the resin during the heating process to form an interlayer insulating film with good surface hardness and heat resistance.

[0056] Furthermore, the organic insulating film's polyacid anhydride-based positive photoresist composition also includes any one or two or more of antioxidants, stabilizers, and free radical scavengers.

[0057] The beneficial effects of this invention are as follows: This invention directly introduces a stable planar polycarboxylic acid structure into the traditional poly(meth)acrylate (ester) system. Utilizing the R-segment, which is a polycarboxylic acid structure with double bonds, it undergoes a free radical polymerization reaction with (meth)acrylate and its ester monomers. This system exhibits high reactivity, excellent hydrophobicity, and temperature resistance, improving the stability required for long-term storage and transportation of products, while reducing production costs. When applied to photoresist materials, it further improves the transparency of the material, increasing the aperture ratio and resolution of the insulating film. Furthermore, by utilizing the characteristic of polyanhydride groups containing fewer polar groups, the dielectric constant of the organic insulating film is reduced. Simultaneously, after modification, the branched structure derivative of the polyanhydride group can contain CN and CS bonds, endowing the resin material with good thermal stability, mechanical properties, chemical properties, and etching resistance. The combination of the low dielectric constant and comprehensive performance allows the material of this invention to meet the application requirements of low-dielectric-constant insulating film materials, such as improved residual film yield, pattern flatness, and aperture ratio, significantly reducing the decline in battery efficiency. Attached Figure Description

[0058] Figure 1 The infrared spectrum of hydrogenated pyromellitic dianhydride; Figure 2 The infrared spectrum is shown for polycarboxylic acid derivative 1 containing multiple functional groups in Synthesis Example 1. Detailed Implementation

[0059] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0060] Synthesis of acrylic polymers based on polycarboxylic acid derivatives as shown in Formula I or Formula II Synthesis example 1 29.4 g (approximately 200 mmol) of 2-mercaptoethyl methacrylate (Mr=146.2), 200 g of N-methylpyrrolidone, and 11.21 g (50 mmol) of hydrogenated pyromellitic dianhydride (Mr=224.17) were added to a three-necked flask. After stirring for 4 h, the reaction temperature was raised to 80 °C and reacted at this temperature for 24 h. The temperature was then raised to 110 °C and reacted for another 4 h. After cooling, a viscous liquid substance was obtained, which was designated as target polycarboxylic acid derivative 1 containing multiple functional groups, for later use.

[0061] .

[0062] 2.14 g of a polycarboxylic acid derivative 1 containing multiple functional groups (Mr=772.17), 3.27 g of maleic anhydride (Mr=98.06), and 8.68 g of hydroxyethyl methacrylate (Mr=130.14) were added to 100 g of ethylene glycol monoethyl ether acetate, along with 0.25 g of acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime). The mixture was stirred, and the reaction temperature was raised to 70 °C. Free radical copolymerization was carried out for 8 h. The resulting acrylic polymer based on the polycarboxylic acid derivative had an average molecular weight of 7900, a molecular weight distribution of 3.5, and an acid value of 282.6 mgKOH / g. This resin can be used as the main resin material for positive photoresists.

[0063] Its synthesis process is as follows: .

[0064] Synthesis example 2 At 20°C, 6.51 g (approximately 50 mmol) of hydroxyethyl methacrylate (Mr=130.14), 50 g of toluene, and 7.41 g (approximately 50 mmol) of phthalic anhydride (Mr=148.12) were added to a three-necked flask, stirred, and the temperature was raised to 120°C within 1 h. The reaction was carried out at this temperature for 16 h. At this temperature, the solvent was removed by vacuum. After cooling, a viscous liquid substance was obtained, which was designated as target polycarboxylic acid derivative 2 containing multiple functional groups, for later use.

[0065] .

[0066] 2.78 g of polycarboxylic acid derivative 2 (Mr=278.08) containing multiple functional groups, 4.18 g of methyl methacrylate (Mr=100.12), 6.17 g of methacrylic acid (Mr=86.09), 3.70 g of glycidyl methacrylate (Mr=142.15), and 2.26 g of styrene (Mr=104.15) were added to a three-necked reactor. Then, 120 g of dipropylene glycol dimethyl ether and 0.5 g of 2,2'-azoisobutyronitrile were added as free radical initiators. The free radical copolymerization reaction was carried out at 80 °C for 18 h to obtain a methacrylate copolymer containing a polycarboxylic acid structure. The average molecular weight of the polymer was 11,000, the molecular weight distribution of the polymer was 1.49, and the acid value was 134.14 mgKOH / g. It can be used as the main resin material for positive photoresist.

[0067] Its synthesis process is as follows: .

[0068] Synthesis example 3 12.91 g (approximately 100 mmol) of 2-aminoethyl methacrylate (Mr=129.08), 200 g of methanol, and 9.61 g (approximately 50 mmol) of trimellitic anhydride (Mr=192.01) were added to a three-necked flask. The reaction temperature was raised to 60 °C, and the reaction was carried out at this temperature for 24 h. At this temperature, excess solvent was removed by vacuum. After cooling, a viscous liquid substance was obtained, which was designated as the target polycarboxylic acid derivative 3 containing multiple functional groups, for later use.

[0069] .

[0070] 9.67 g of a polycarboxylic acid derivative 3 (Mr=446.17) containing multiple functional groups, 14.35 g of methacrylic acid (Mr=86.09), 14.42 g of 4-hydroxystyrene (Mr=120.15), and 25.88 g of tetrahydrofuran methacrylate (Mr=170.21) were added to a three-necked reactor. 210 g of N,N-dimethylformamide was added, and the reaction was carried out at 30 °C for 1 h. Then, 0.5 g of 2,2'-azoisoheptanenitrile was added, and the reaction temperature was raised to 60 °C for free radical polymerization for 36 h. The resulting acrylic polymer based on the polycarboxylic acid derivative had an average molecular weight of 36,000, a molecular weight distribution of 2.13, and an acid value of 145.4 mgKOH / g, which can be used as the main resin material for positive photoresists.

[0071] Its synthesis process is as follows: .

[0072] Examples of components in a positive photoresist composition for organic insulating films Acrylic polymers based on polycarboxylic acid derivatives as shown in Formula I or Formula II The components used to prepare the compositions of the examples and comparative examples are as follows: A-1: Synthetic Example 1; A-2: Synthetic Example 2; A-3: Synthetic Example 3; Photoacid-producing agents: A condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (3.0 mol); <c>Acid-forming agent or base-forming agent C-1: Benzyl-4-hydroxyphenylmethylsulfonamide; C-2: Cyclohexane(1,1-dimethylethylsulfonamide)diazamide; C-3: 1-(4-n-butoxynaphthyl-1-yl)tetrahydrothiophene trifluoromethanesulfonate; <d>surfactants FS-3100; <e>Adhesive γ-isocyanate propyltriethoxysilane; <f>solvent Propylene glycol monomethyl ether acetate; Example 1 100 g of the polycarboxylic acid derivative-based acrylic polymer (A-1) synthesized in Synthesis Example 1, 3 g of photoacid-generating agent (B), 1.5 g of acid-generating agent or alkali-generating agent (C-1), 1.5 g of (C-2), 1.5 g of (C-3), 0.2 g of surfactant (D), and 0.5 g of adhesion promoter (E) were added to a container. Then, solvent (F-1) was added to make the solids concentration 20% to prepare a positive photoresist composition.

[0073] 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.

[0074] Furthermore, in Comparative Examples 1-2, the adhesive resin represented by Formula 3 (average molecular weight 9000) was used instead of the one in Example 1 above.< / f> < / e> < / d> < / c> The acrylic polymer based on polycarboxylic acid derivatives shown in Formula I or Formula II was used to manufacture a positive photoresist composition for an organic insulating film of a high aperture ratio liquid crystal display element using the same method, except that the composition and content of the composition vary according to the composition described in Table 2 below.

[0075]

[0076] Formula 3 In Equation 3 above, p is 0.3, q is 0.2, and r is 0.5.

[0077] The performance of the positive photoresist compositions prepared as described in the above examples and comparative examples was evaluated as follows.

[0078] 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, a 1.5 μm thick coating was formed by pre-baking at 100°C for 2 minutes using a hot plate. For the obtained coating, a Canon PLA-501F exposure unit (ultra-high pressure mercury lamp) was used to expose the silicon wafer under a mask with a 3.0 μm linewidth pattern. 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.

[0079] 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 Auto EL IV NIR III. When the refractive index is higher than 1.50, the material is considered suitable for use as an interlayer insulating film.

[0080] III. Evaluation of the heat resistance of interlayer insulating films A cured film was formed on a silicon substrate, and the thickness (T1) 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: [(T1-T2) / T1]×100%. The results are shown in Tables 1 and 2. A heat resistance of less than or equal to 3% is considered good.

[0081] 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.

[0082] 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.) with etching gas CF 450 mL / min, O2 10 mL / min, and output 400 mW for 90 seconds. Measurements were taken of the film before and after the etching 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.

[0083] Table 1 Examples and their physical property test results

[0084] Table 2 Comparative Examples and Their Physical Property Test Tables

[0085] As can be seen from the results in Tables 1 and 2, since the positive photoresist composition of the present invention uses acrylic polymers based on polycarboxylic acid derivatives as shown in Formula I and / or Formula II, compared with the positive photoresist compositions in Table 2 that only use polymers with the structure shown in Formula 3, the cured film formed by the present invention has the characteristics of good heat resistance, high transmittance and good dry etching properties.

[0086] The polycarboxylic acid structure used in this invention has a stable hydrophobic structure and good transparency, which is beneficial for improving the aperture ratio and water resistance of acrylic photoresists. The polyanhydride groups in this invention contain fewer polar groups, which can reduce the dielectric constant of the resin. Low-dielectric-constant organic insulating films are crucial for reducing parasitic capacitance between pixel electrodes and wiring. The polyanhydride groups in this invention have good thermal stability, mechanical properties, and chemical properties, and the low-dielectric-constant material formed by them also meets the application requirements of insulating film materials. By adjusting the type and number of functional groups in the polycarboxylic acid derivatives and (meth)acrylic acid monomers, this invention can effectively improve the adhesion between the resin and the matrix, while simultaneously improving the residual film rate, pattern flatness, and aperture ratio.

[0087] Comparison Appendix Figure 1 and attached Figure 2 It can be seen that at 1700 cm -1 The absorption peak near the carbonyl group showed a significant blue shift, indicating that a ring-opening reaction occurred at 1630 cm⁻¹. -1 The presence of an absorption peak at 2870 cm⁻¹ at a C=C double bond confirms the synthesis of a polycarboxylic acid derivative with a double bond structure. -1 The presence of absorption peaks in the vicinity that can be attributed to -CH3 or -CH2- confirms the synthesis of polycarboxylic acid derivatives with methyl or methylene structures. In summary, [the following is a continuation of the previous sentence]. Figure 2 It was confirmed that a polycarboxylic acid derivative 1 containing multiple functional groups was obtained.

[0088] 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 polybasic acid anhydride-based positive photoresist composition for use in organic insulating films, characterized in that, Based on parts by weight, it includes the following components: 20-100 parts of acrylic polymer based on polycarboxylic acid derivatives; Photoacid-producing agent: 0.03–20 parts; 0.01 to 10 parts of acid-forming agent or alkali-forming agent; Surfactant 0.01 to 5 parts; Adhesive aid 0.01 to 5 parts; Solvent: 100–2000 parts; The acrylic polymer based on polycarboxylic acid derivatives has one of the following structures: 、 、 。 2. The polybasic acid anhydride-based positive photoresist composition for organic insulating films according to claim 1, characterized in that, It also includes any one or a combination of two or more antioxidants, stabilizers, and free radical scavengers.

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