Positive photosensitive resin composition

Abstract

The invention discloses a positive photosensitive resin composition. The photosensitive resin composition comprises the following components: (A) alkali-soluble resin, (B) a photosensitive compound, (C) an organic solvent and (D) an auxiliary agent, the photosensitive compound (B) is a compound formed by reacting a phenolic hydroxyl compound with a general formula (1) and / or (2) as shown in the specification; the photosensitive compound # imgabs0 # imgabs1 # is free of sulfonyl ester groups, and can further reduce the residual S element in a cured film, thereby reducing the influence of the S element on the device life in long-term use, and further producing an organic EL display device which does not cause reduction of light emission brightness and pixel shrinkage and has excellent long-term reliability.

Description

Technical Field

[0001] The present invention relates to the field of organic light emission, and particularly to a positive photosensitive resin composition. Background Art

[0002] As a next-generation flat panel display, an organic EL display device has attracted attention. The organic EL display device is a self-luminous display device that utilizes electroluminescence achieved by an organic compound, and can perform image display with a wide viewing angle, high-speed response, and high contrast. The organic EL display device also has the characteristics of being able to achieve thinning and light weight, and therefore, in recent years, research and development on it have been actively carried out.

[0003] The long-term reliability of a device can be regarded as one of the important performances of an organic EL display device. The decline in device reliability is usually due to the fact that organic light-emitting materials are generally intolerant to organic gas components and moisture. When exposed to organic gas components and moisture, it will cause a decrease in emission brightness and pixel shrinkage. The so-called pixel shrinkage refers to the phenomenon that the emission brightness starts to decrease from the end of the pixel or becomes unable to light up. In order to improve the long-term reliability of such a display element, in addition to improving the durability of the organic light-emitting material itself, it is also possible to improve the materials used in the planarization layer covering the driving circuit TFT and the insulating layer on the first electrode.

[0004] For the above-mentioned planarization layer and insulating layer materials, by using a photosensitive resin composition, a desired pattern can be easily obtained. Among them, considering the performance of being able to perform inorganic base development and high resolution, a positive photosensitive resin composition is ideal.

[0005] The positive photosensitive resin compositions proposed so far include a positive photosensitive resin composition obtained by mixing an o-quinonediazide compound as a photosensitive component in an alkali-soluble resin, including a composition using a polyimide precursor as the resin (for example, CN104854508B), and a composition using a polybenzoxazole precursor as the resin (for example, CN109563353B). At present, the photosensitive resin composition generally uses a sulfur-containing o-quinonediazide compound as a photosensitizer for suppressing the resin dissolution performance (for example, CN108604061B), but this sulfur-containing o-quinonediazide compound will decompose to generate sulfur-containing compounds during the long-term use of the device, which will affect the lifespan of the organic light-emitting material, thereby leading to a decrease in the long-term reliability of the device. Summary of the Invention

[0006] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a positive photosensitive resin composition with high sensitivity, which does not cause a decrease in emission brightness and pixel shrinkage, and can suppress the generation of outgassing after curing, thereby improving the long-term reliability of the organic EL device and having broad application prospects.

[0007] To solve the above technical problems, the present invention adopts the following technical means:

[0008] A positive photosensitive resin composition comprising the following components: (A) an alkali-soluble resin, (B) a photosensitive compound, (C) an organic solvent, and (D) an auxiliary agent;

[0009] Wherein the (B) photosensitive compound is a compound formed by the reaction of the following general formula (1) and / or (2) with a phenolic hydroxyl compound;

[0010]

[0011] In general formulas (1) and (2), R 1 represents an alkyl group having 1 to 4 carbon atoms, and X represents an element of Group VIIA (halogen element), including F, Cl, Br, and I.

[0012] Examples of the (A) alkali-soluble resin include, but are not limited to, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyaminoamide, and polyamide resin. Two or more of the above resins may be contained. Among these alkali-soluble resins, an alkali-soluble resin having excellent heat resistance and low outgassing at high temperatures is preferred. Specifically, one or more of polyimide, polyimide precursor, and polybenzoxazole precursor are preferred.

[0013] For the alkali-soluble resin or their copolymer selected from polyimide, polyimide precursor, or polybenzoxazole precursor that can be used as the (A) alkali-soluble resin of the present invention, in order to impart the above-mentioned alkali solubility, it is preferred to have an acidic group in the structural unit of the resin and / or at the end of its main chain. Examples of the acidic group include carboxyl group, phenolic hydroxyl group, sulfonic acid group, etc. Among these acidic groups, carboxyl group or phenolic hydroxyl group is preferred in consideration of the absence of sulfur atoms.

[0014] In addition, the alkali-soluble resin preferably has fluorine atoms, which can impart waterproofness to the interface between the film and the substrate during development with an alkaline aqueous solution and inhibit the penetration of the alkaline aqueous solution into the interface. From the viewpoint of the effect of preventing the penetration of the alkaline aqueous solution into the interface, the fluorine atom content in the alkali-soluble resin is preferably 5% by weight or more, and from the viewpoint of solubility in the alkaline aqueous solution, the fluorine atom content in the alkali-soluble resin is preferably 20% by weight or less.

[0015] As a preferred embodiment, the polyimide has a structural unit represented by the following general formula (3),

[0016]

[0017] In general formula (3), R 1 represents an organic aromatic group with a valence of 2 to 8, and R 2 represents an organic aromatic group with a valence of 2 to 8, and R 3 and R 4 represent a carboxyl group or a phenolic hydroxyl group, and p and q represent integers from 0 to 6.

[0018] As a preferred embodiment, the polyimide precursor and the polybenzoxazole precursor have a structural unit represented by the following general formula (4),

[0019]

[0020] As a preferred embodiment, the alkali-soluble resin can be a polyimide precursor and / or a polybenzoxazole precursor, or a resin obtained by copolymerizing a polyimide precursor and a polybenzoxazole precursor.

[0021] In general formula (4), R 5 represents an organic aromatic group with a valence of 2 to 8, and R 6 represents an organic aromatic group with a valence of 2 to 8; R 7 and R 8 independently represent a phenolic hydroxyl group or COOR 9 ; R 9 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; r or s represents an integer from 0 to 6, where r + s > 0.

[0022] The alkali-soluble resin selected from polyimide, polyimide precursor, or polybenzoxazole precursor or their copolymers. Additionally, in addition to the structural unit represented by general formula (3) or (4), other structural units may also be present. In this case, it is preferred to have 50 mol% or more of the structural units represented by general formula (3) or (4) among all the structural units.

[0023] In the above general formula (3), R 1 -(R 3 )p represents the residue of an acid dianhydride. R 1 represents an organic aromatic group with a valence of 2 to 8, and the number of carbon atoms of the aromatic group is preferably 5 to 40.

[0024] As the acid dianhydride, specifically, examples thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and other aromatic tetracarboxylic dianhydrides, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides, and one or more of these. Two or more of the above acid dianhydrides can be used.

[0025] R in the above general formula (3) 2 -(R 4 )q and R in the above general formula (4) 6 -(R 8 )s represent the residues of diamines. R 2 and R 8 are organic groups with a valence of 2 to 8, and among them, organic groups with 5 to 40 carbon atoms containing an aromatic ring are preferred.

[0026] Specific examples of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or a compound obtained by substituting at least a part of hydrogen atoms in the aromatic ring thereof with an alkyl group and / or a halogen atom, etc. Two or more of the above diamines can be used.

[0027] In addition, by using a monoamine, an acid anhydride, an acyl chloride, or a monocarboxylic acid having to cap the terminals of these resins, a resin having an acidic group at the main chain terminal can be obtained.

[0028] Preferred examples of such a monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, etc. Two or more of the above monoamines can be used.

[0029] In addition, preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include: acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride; monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxybenzenethiol, 4-carboxybenzenethiol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, and 1-mercapto-5-carboxynaphthalene, and monoacyl chloride compounds obtained by acyl chlorination of their carboxyl groups; monoacyl chloride compounds obtained by acyl chlorination of only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene; and active ester compounds obtained by reacting N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide with monoacyl chloride compounds. Two or more of the above compounds can be used.

[0030] Regarding the content of the above-mentioned end-capping agents such as monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids, based on the total of the acid dianhydride and diamine components constituting the resin being 100 mol%, it is preferably 2 to 25 mol% of the total.

[0031] The end-capping agent introduced into the resin can be easily detected by the following method. For example, the resin into which the end-capping agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid component that are structural units of the resin, and measured by gas chromatography (GC) or NMR, whereby the end-capping agent can be easily detected. In addition, it can be detected by directly performing pyrolysis gas chromatography (PGC), infrared spectroscopy, and 13 C-NMR spectroscopy on the resin into which the end-capping agent has been introduced.

[0032] The (A) alkali-soluble resin of the present invention can be synthesized by a known method. In the case of polyamic acid or polyamic acid ester, as a manufacturing method, for example, it can be synthesized by the following methods: a method of reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature; a method of obtaining a diester using a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of an amine and a condensing agent; a method of obtaining a diester using a tetracarboxylic dianhydride and an alcohol, then acyl chlorinating the remaining dicarboxylic acid, and reacting with an amine; and so on.

[0033] In the case of a polyhydroxyamide, as a production method, it can be obtained by subjecting a bisphenolamine compound and a dicarboxylic acid to a condensation reaction. Specifically, it includes the following methods: a method of reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisphenolamine compound thereto; a method of dropping a solution of a dicarboxylic acid dichloride into a solution of a bisphenolamine compound to which a tertiary amine such as pyridine has been added; and so on.

[0034] In the case of a polyimide, it can be obtained by dehydrating and cyclizing the polyamic acid or polyamic acid ester obtained by the above method by heat treatment or chemical treatment with an acid, a base, or the like.

[0035] Regarding the addition amount of the (A) resin component, it is preferably 5% by weight or more and preferably 20% by weight or less of the positive photosensitive resin composition.

[0036] The positive photosensitive resin composition used in the present invention contains a (B) photosensitive compound. The photosensitive compound is a compound in which a compound having an azidonaphthoquinone group and a compound having a phenolic hydroxyl group are bonded through an ester bond.

[0037] Examples of the compounds having phenolic hydroxyl groups used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and other compounds.

[0038] The photosensitive compound can be synthesized by the esterification reaction of the above-mentioned compounds having phenolic hydroxyl groups with the general formulas (1) and (2). By using these photosensitive compounds, the resolution, sensitivity, and residual film ratio can be further improved. Optionally, the reaction product of other diazoquinone sulfonic acid compounds and phenolic hydroxyl compounds can also be contained.

[0039] Since the photosensitive compound formed by the general formulas (1) and (2) has no sulfonyl ester group, the residual S element in the cured film can be further reduced, and thus an organic EL display device that does not cause a decrease in emission brightness and pixel shrinkage and has excellent long-term reliability can be manufactured.

[0040] Regarding the addition amount of the component (B), it is preferably 2% by weight or more, preferably 12% by weight or less, and more preferably 10% by weight or less of the positive photosensitive resin composition. By making it 2% by weight or more, pattern formation can be carried out with excellent sensitivity, and by making it 10% by weight or less, pixel shrinkage caused by the sulfur atom of the o - quinonediazide compound can be suppressed, improving the long - term reliability of the organic EL device.

[0041] The positive photosensitive resin composition used in the present invention contains (C) an organic solvent. Thereby, it can be in a varnish state, and the coatability can be improved.

[0042] Regarding the above - mentioned organic solvent, the following solvents can be used alone or in combination: polar aprotic solvents such as γ - butyrolactone; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2 - heptanone, 3 - heptanone, diacetone alcohol; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate; other esters such as ethyl 2 - hydroxy - 2 - methylpropionate, methyl 3 - methoxypropionate, ethyl 3 - methoxypropionate, methyl 3 - ethoxypropionate, ethyl 3 - ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2 - hydroxy - 3 - methylbutyrate, 3 - methoxybutyl acetate, 3 - methyl - 3 - methoxybutyl acetate, 3 - methyl - 3 - methoxybutyl propionate, ethyl acetate, n - propyl acetate, isopropyl acetate, n - butyl acetate, isobutyl acetate, n - amyl formate, isoamyl acetate, n - butyl propionate, ethyl butyrate, n - propyl butyrate, isopropyl butyrate, n - butyl butyrate, methyl pyruvate, ethyl pyruvate, n - propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2 - oxobutyrate; aromatic hydrocarbons such as toluene, xylene; amides such as N - methylpyrrolidone, N,N - dimethylformamide, N,N - dimethylacetamide; and so on.

[0043] Regarding the amount of the above-mentioned organic solvent used, there is no particular limitation, preferably 100 to 3000% by weight of the positive photosensitive resin composition, more preferably 70 to 90% by weight. In addition, the proportion of the solvent having a boiling point of 180 °C or higher in the total amount of the organic solvents is preferably 20% by weight or less, more preferably 10% by weight or less. By making the proportion of the solvent having a boiling point of 180 °C or higher 30% by weight or less, the amount of exhaust gas from the planarization layer or the insulating layer after thermal curing can be suppressed to a low level, and as a result, the long-term reliability of the organic EL device can be improved.

[0044] The positive photosensitive resin composition used in the present invention contains (D) an auxiliary agent. Thereby, the coatability of the resin composition, the adhesion type to the substrate, and the thermal stability of the cured film can be further improved.

[0045] The auxiliary agent (D) in the positive photosensitive resin composition used in the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent is a compound having at least two thermal reactive functional groups represented by alkoxymethyl, hydroxymethyl, and epoxy groups in the molecule. The thermal crosslinking agent can crosslink the resin of the component (A) or other added components, can improve the heat resistance, chemical resistance, and hardness of the film after thermal curing, and in addition, can reduce the amount of exhaust gas from the cured film and improve the long-term reliability of the organic EL display device. Therefore, it is preferably contained.

[0046] As a preferred example of a thermal crosslinking agent for a compound having at least two alkoxymethyl or hydroxymethyl groups, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are trade names, manufactured by SANWA CHEMICAL CO., LTD.).

[0047] As preferred examples of the thermal crosslinking agent for the compound having at least two epoxy groups, for example, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 80MF, Epolight 4000, Epolight 3002 (manufactured by Kyoeisha Chemical Co., Ltd. above), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L (manufactured by Nagase ChemteX Corporation above), GAN, GOT (manufactured by Nippon Kayaku Co., Ltd. above), Epikote 828, Epikote 1002, Epikote 1750, Epikote 1007, YX8100-BH30, E1256, E4250, E4275 (manufactured by Japan Epoxy Resins Co., Ltd. above), EPICLON EXA-9583, HP4032 (manufactured by Dainippon Ink and Chemicals, Inc. above), VG3101 (manufactured by Mitsui Chemicals, Inc.), TEPIC S, TEPIC G, TEPIC P (manufactured by Nissan Chemical Industries, Ltd. above), Denacol EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), EPOTOHTOYH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), EPICLON N695, HP7200 (manufactured by Dainippon Ink and Chemicals, Inc. above), etc. can be cited.

[0048] As preferred examples of the thermal crosslinking agent for the compound having at least two oxetanyl groups, for example, ETERNACOLL EHO, ETERNACOLL OXBP, ETERNACOLL OXTP, ETERNACOLL OXMA (manufactured by Ube Industries, Ltd. above)

[0049] As a preferred embodiment, two or more kinds of thermal crosslinking agents can be used in combination.

[0050] Regarding the content of the thermal crosslinking agent, it is preferably 1% by weight or more and 10% by weight or less relative to the total amount of the resin composition (excluding the solvent). When the content of the thermal crosslinking agent is 1% by weight or more and 10% by weight or less, the chemical resistance and hardness of the film after firing or curing can be improved. In addition, the amount of exhaust gas from the cured film can be reduced, the long-term reliability of the organic EL display device can be improved, and the storage stability of the photosensitive resin composition is also excellent.

[0051] For the purpose of improving the wettability with the substrate, the positive photosensitive resin composition used in the present invention may contain a surfactant as needed. Commercially available compounds can be used as the surfactant. Specifically, as silicone-based surfactants, the SH series, SD series, ST series of Dow Corning Toray Co., Ltd., the BYK series of BYK Japan KK, the KP series of Shin-Etsu Chemical Co., Ltd., the disk Home series of Nippon Oil & Fats Co., Ltd., the TSF series of Toshiba Silicones Ltd., etc. can be mentioned; as fluorine-based surfactants, the "Megafac (registered trademark)" series of Dainippon Ink and Chemicals, Inc., the Fluorad series of Sumitomo 3M Limited, the "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series of Asahi Glass Co., Ltd., the EF series of Shin-Akita Kasei Co., Ltd., the PolyFox series of OMNOVA Solutions, Inc., etc. can be mentioned; as surfactants formed from acrylic acid-based and / or methacrylic acid-based polymers, the POLYFLOW series of Kyoeisha Chemical Co., Ltd., the "DISPARLON (registered trademark)" series of Kusumoto Chemicals, Ltd., etc. can be mentioned, but the surfactants are not limited to these.

[0052] Regarding the content of the surfactant, it is preferably 1 to 10% by weight relative to the total amount of the resin composition (excluding the solvent).

[0053] As an alternative, the positive photosensitive resin composition used in the present invention may contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device. The thermal acid generator generates acid by heating, which can not only promote the crosslinking reaction of the thermal crosslinking agent, but also promote the cyclization of the resin of component (A) when it has an unclosed imide ring structure or oxazole ring structure, further improving the mechanical properties of the cured film.

[0054] The thermal decomposition starting temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, more preferably 250°C or lower. In addition, when the following thermal acid generator is selected, a decrease in sensitivity during development can be suppressed, and thus it is preferred that the thermal acid generator does not generate acid when the positive photosensitive resin composition of the present invention is coated on a substrate and then dried (pre-baking: about 70 to 140°C), and generates acid when finally heated (cured: about 100 to 400°C) after pattern formation by subsequent exposure and development.

[0055] The acid generated by the thermal acid generator used in the present invention is preferably a strong acid. For example, it is preferably an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid, a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid, etc. They can be used in the form of salts such as onium salts or covalent bond compounds such as imide sulfonates. Two or more of them can be contained.

[0056] Regarding the content of the thermal acid generator used in the present invention, relative to the total amount of the resin composition (excluding the solvent), it is preferably 1% by weight or more. By containing 1% by weight or more, the crosslinking reaction and the cyclization of the unclosed ring structure of the resin are promoted. Therefore, the mechanical properties and chemical resistance of the cured film can be further improved. In addition, from the viewpoint of the long-term reliability of the organic EL display device, the content of the thermal acid generator is preferably 10% by weight or less.

[0057] The positive photosensitive resin composition of the present invention is applicable to the surface protective film or interlayer insulating film of semiconductor elements, the insulating film of organic electroluminescence (hereinafter referred to as EL) elements, the planarizing film of the driving thin film transistor (hereinafter referred to as TFT) substrate of a display device using an organic EL element, the wiring protection insulating film of a circuit substrate, the on-chip microlens of a solid-state imaging element, or the planarizing film for various display solid-state imaging elements, etc.

[0058] The positive photosensitive resin composition of the present invention can be used to fabricate an organic EL display device that does not cause a decrease in emission luminance and pixel shrinkage and has excellent long-term reliability. Detailed Embodiments

[0059] The present invention provides a method for preparing a positive photosensitive resin composition and its application in an organic EL display device. The present invention will be further described below with reference to specific examples. The examples described in the present invention are only for further elaboration of the present invention and do not limit the scope of the present invention.

[0060] The main raw materials used in the preparation examples and the examples include: diphenyl ether diamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, diphenyl ether dianhydride, pyromellitic dianhydride, N-methylpyrrolidone, 5-hydroxy-1-naphthoic acid, acetone, dioxane, etc., all of which are purchased from companies such as InnoChem; ethanol, m-aminophenol, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, etc., are purchased from companies such as Aladdin; ethylene glycol, diazonaphthoquinone sulfonyl chloride, etc., are purchased from companies such as Macklin. Unless otherwise specified, the raw materials used are obtained through commercial channels.

[0061] The test methods for the products in the examples and comparative examples include:

[0062] Coating film method

[0063] The resin composition was coated on a 6-inch wafer by spin coating, baked on a hot plate at 120 °C for 3 minutes to produce a pre-baked film with a film thickness of 4.0 μm. Then, using an exposure machine (i-line stepper), through a mask with a pattern having contact holes of 8 μm, exposure was carried out with an exposure dose of 100 - 600 mJ / cm2. After exposure, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH, manufactured by Suzhou Jingrui) was used for development for 2 min, then rinsed with distilled water, and then spin-dried to obtain a pattern. Then, it was treated in a nitrogen-filled oven at 250 °C for 2 h to obtain a cured film, and various properties of the cured film and the lithography performance during the exposure process were further tested.

[0064] Sensitivity test

[0065] Using a microscope (manufactured by Olympus), the pattern of the developed film obtained by the above method was observed at a magnification of 20 times, and the minimum necessary exposure dose required for the opening diameter of the contact hole to reach 8 μm was obtained and taken as the sensitivity.

[0066] Film loss test

[0067] Using a profilometer (manufactured by Bruker), the film thickness before and after development was measured, and the film loss was obtained by subtracting the film thickness after development from the film thickness before development.

[0068] 5% thermal weight loss temperature test

[0069] Using a thermogravimetric analyzer TGA-50 (manufactured by Shimadzu), under a nitrogen atmosphere, pre-drying was carried out at 150 °C for 30 minutes, and then the temperature was raised at a heating rate of 10 °C / minute. During this heating process, the temperature at which the weight decreased by 5% relative to the initial weight was measured.

[0070] S content test in the cured film

[0071] The film obtained after development is heat-treated to obtain a cured film. The sulfur content in the cured film is measured using X-ray fluorescence analysis (XRF).

[0072] (Synthesis Example 1) Synthesis of polyimide precursor (A-1)

[0073] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3’,4,4’-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. To this, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (hereinafter referred to as m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-1) as the target alkali-soluble resin.

[0074] (Synthesis Example 2) Synthesis of polyimide precursor (A-2)

[0075] Under a dry nitrogen stream, 31.0 g (0.10 mol) of ODPA was dissolved in 500 g of NMP. To this, 27.47 g (0.075 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as 6FAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-2) as the target alkali-soluble resin.

[0076] (Synthesis Example 3) Synthesis of Polyimide Precursor (A-3)

[0077] Under a dry nitrogen stream, 31.0 g (0.10 mol) of ODPA was dissolved in 500 g of NMP. To this, 15.00 g (0.075 mol) of oxydianiline (hereinafter referred to as ODA), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-3) as the target alkali-soluble resin.

[0078] (Synthesis Example 4) Synthesis of Polyimide Precursor (A-4)

[0079] Under a dry nitrogen stream, 21.8 g (0.10 mol) of pyromellitic dianhydride was dissolved in 500 g of NMP. To this, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (hereinafter referred to as m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-4) as the target alkali-soluble resin.

[0080] (Synthesis Example 5) Synthesis of Polyimide Precursor (A-5)

[0081] Under a dry nitrogen stream, 21.8 g (0.10 mol) of pyromellitic dianhydride was dissolved in 500 g of NMP. To this, 27.47 g (0.075 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as 6FAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-5) as the target alkali-soluble resin.

[0082] (Synthesis Example 6) Synthesis of polyimide precursor (A-6)

[0083] Under a dry nitrogen stream, 21.8 g (0.10 mol) of pyromellitic dianhydride was dissolved in 500 g of NMP. To this, 15.00 g (0.075 mol) of oxydianiline (hereinafter referred to as ODA), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour. Next, the reaction was carried out at 50 °C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 °C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the polyimide precursor (A-3) as the target alkali-soluble resin.

[0084] (Synthesis Example 7) Synthesis of compound of general formula (1)

[0085] Add 100 g (0.38 mol) of 1-naphthol-5-carboxylic acid and 510 g (28.3 mol) of water into a four-necked flask equipped with a condenser, a thermometer, mechanical stirring, and a tail gas absorber. Stir and cool down to 0 - 5 °C, and simultaneously add a certain amount of sodium nitrite and hydrochloric acid dropwise. After the addition is completed, keep the temperature for reaction for 3 hours. Monitor the reaction process by liquid chromatography. After the reaction is completed, filter, wash the filter cake with water, dry and weigh to obtain 92.9 g of 2-nitroso-1-naphthol-5-carboxylic acid, with a yield of 97%.

[0086] Add 96 g (0.38 mol) of 2-nitroso-1-naphthol-5-carboxylic acid and 384 g (21.3 mol) of water into a four-necked flask equipped with a condenser, a thermometer, mechanical stirring, and a tail gas absorber. Add sodium hydroxide and stir until dissolved. Add sodium dithionite in batches and heat up to 60 - 65 °C for heat preservation reaction for 2 hours. Detect the reaction process by liquid chromatography. After the reaction is completed, cool down to 20 °C, add hydrochloric acid dropwise, stir for 1 hour, filter by suction, wash the filter cake, dry and weigh to obtain 94.0 g of the hydrochloride of 2-amino-1-naphthol-5-carboxylic acid, with a yield of 90%.

[0087] Add 94 g (0.34 mol) of the hydrochloride of 2-amino-1-naphthol-5-carboxylic acid, 5.1 g (0.02 mol) of copper sulfate pentahydrate, and 670 g (37.2 mol) of water into a 1 L four-necked flask (equipped with a condenser, a thermometer, and a tail gas absorber). Stir and cool down to 0 - 5 °C, first add dropwise a mixture of 32.5 g (0.47 mol) of sodium nitrite and 92.5 g of water (5.14 mol). After stirring and reacting for 1 hour, then add dropwise 124.3 g (1.23 mol) of concentrated hydrochloric acid and stir and react for 1.5 hours. Add 128.5 g (2.20 mol) of sodium chloride, stir for crystallization, and filter to obtain the product 2-diazo-1-naphthoquinone-5-carboxylic acid. The product is an orange-yellow solid, with a yield of 96%.

[0088] Place 102.7 g (0.86 mol) of thionyl chloride into a 500 mL four-necked flask equipped with a thermometer, a condenser, and connected to a tail gas absorption device. Add the raw material 2-diazo-1-naphthoquinone-5-carboxylic acid slowly in batches under mechanical stirring. After the addition is completed, stir for half an hour, then add dropwise a mixture of 4.5 g (0.03 mol) of phosphorus trichloride and 685 g (0.58 mol). Heat up to 50 - 55 °C and stir and react for 2 hours, then cool down to room temperature. Slowly add the reaction solution dropwise into ice water for ice precipitation and crystallization, filter, wash the filter cake with water until neutral to obtain the crude product of 2-diazo-1-naphthoquinone-5-carbonyl chloride (general formula (1)). The crude product is recrystallized with dioxane to obtain the pure product, with a purity greater than 99%, an orange-yellow color, and a yield of 75%. 1HNMR(600MHz, DMSO / TMS): δ 8.14 (d, J = 7.9 Hz, 1H), 7.95 (d, J = 7.6 hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.54 (t, J = 7.3 Hz, 1H), 7.34 (d, J = 7.5 Hz, 1H)

[0089] (Synthesis Example 8) Synthesis of the compound of general formula (2)

[0090] 100 g (0.38 mol) of 1-naphthol-4-carboxylic acid and 510 g (28.3 mol) of water were added to a four-necked flask equipped with a condenser, thermometer, mechanical stirrer and tail gas absorber. The temperature was lowered to 0 - 5 °C with stirring, and a certain amount of sodium nitrite and hydrochloric acid were added dropwise simultaneously. After the addition was completed, the reaction was kept warm for 3 hours. The reaction progress was monitored by liquid chromatography. After the reaction was completed, the mixture was filtered, the filter cake was washed with water, dried and weighed to obtain 92.9 g of 2-nitroso-1-naphthol-4-carboxylic acid, with a yield of 97%.

[0091] 96 g (0.38 mol) of 2-nitroso-1-naphthol-4-carboxylic acid and 384 g (21.3 mol) of water were added to a four-necked flask equipped with a condenser, thermometer, mechanical stirrer and tail gas absorber. Sodium hydroxide was added and stirred until dissolved. Sodium dithionite was added in batches, and the temperature was raised to 60 - 65 °C and the reaction was kept warm for 2 hours. The reaction progress was detected by liquid chromatography. After the reaction was completed, the temperature was lowered to 20 °C, hydrochloric acid was added dropwise, and the mixture was stirred for 1 hour, filtered by suction, the filter cake was washed, dried and weighed to obtain 94.0 g of the hydrochloride salt of 2-amino-1-naphthol-4-carboxylic acid, with a yield of 90%.

[0092] 94 g (0.34 mol) of the hydrochloride salt of 2-amino-1-naphthol-4-carboxylic acid, 5.1 g (0.02 mol) of copper sulfate pentahydrate and 670 g (37.2 mol) of water were added to a 1 L four-necked flask (equipped with a condenser, thermometer and tail gas absorber). The temperature was lowered to 0 - 5 °C with mechanical stirring. First, a mixture of 32.5 g (0.47 mol) of sodium nitrite and 92.5 g of water ((5.14 mol)) was added dropwise. After stirring and reacting for 1 hour, 124.3 g (1.23 mol) of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and reacted for 1.5 hours. 128.5 g (2.20 mol) of sodium chloride was added and stirred for crystallization. The product 2-diazo-1-naphthoquinone-4-carboxylic acid was obtained by filtration. The product was an orange-yellow solid, with a yield of 96%.

[0093] In a 500 mL four-necked flask equipped with a thermometer, a condenser, and a tail gas absorption device, 102.7 g (0.86 mol) of thionyl chloride was added to the reaction flask, and the raw material 2-diazo-1-naphthoquinone-4-carboxylic acid was slowly added in batches under mechanical stirring. After the addition, stirring was continued for half an hour, and a mixed solution of 4.5 g (0.03 mol) of phosphorus trichloride and 685 g (0.58 mol) was added dropwise. The temperature was raised to 50 - 55 °C, and after stirring and reacting for 2 hours, the temperature was lowered to room temperature. The reaction solution was slowly added dropwise to ice water for ice precipitation and crystallization, filtered, and the filter cake was washed with water until neutral to obtain the crude product of 2-diazo-1-naphthoquinone-4-carbonyl chloride (general formula (2)). The crude product was recrystallized with dioxane to obtain the pure product with a purity greater than 99%, an orange-yellow color, and a yield of 75%. 1 HNMR(600MHz,DMSO / TMS): δ8.04(d, J = 8.0Hz, 1H), 7.90(d, J = 7.8hz, 1H), 7.67(s, 1H), 7.54 - 7.43(m, 1H), 7.34(t, J = 7.3Hz, 1H)

[0094] (Synthesis Example 9) Synthesis of photosensitive compound (B-1)

[0095] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 31.59 g (0.135 mol) of the compound in Synthesis Example (7) were dissolved in 450 g of 1,4-dioxane, and the temperature was restored to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35 °C. After the addition, stirring was carried out at 30 °C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. The precipitate was dried using a vacuum dryer to obtain the photosensitive compound (B-1).

[0096] (Synthesis Example 10) Synthesis of photosensitive compound (B-2)

[0097] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 31.59 g (0.135 mol) of the compound in Synthesis Example (8) were dissolved in 450 g of 1,4-dioxane, and the temperature was restored to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35 °C. After the addition, stirring was carried out at 30 °C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. The precipitate was dried using a vacuum dryer to obtain the photosensitive compound (B-2).

[0098] (Synthesis Example 11) Synthesis of Photosensitive Compound (B-3)

[0099] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of diazoquinone-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was returned to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto in such a manner that the temperature inside the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered off, and the filtrate was poured into water. Then, the precipitated solid was collected by filtration. The solid was dried using a vacuum dryer to obtain the photosensitive compound (B-3).

[0100] (Synthesis Example 12) Synthesis of Photosensitive Compound (B-4)

[0101] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of diazoquinone-4-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was returned to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto in such a manner that the temperature inside the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered off, and the filtrate was poured into water. Then, the precipitated solid was collected by filtration. The solid was dried using a vacuum dryer to obtain the photosensitive compound (B-4).

[0102] Example 1

[0103] 10.0 g of the alkali-soluble resin (A-1) obtained in Synthesis Example 1 above and 2.5 g of the photosensitive compound (B-1) in Synthesis Example 9 above were dissolved in 28.0 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and 12.0 g of γ-butyrolactone (hereinafter referred to as GBL), and then filtered through a 0.22-μm polytetrafluoroethylene filter head to obtain a positive photosensitive resin composition A.

[0104] Examples 1-11 and Comparative Examples 1-6

[0105] Using the same method as in Example 1, the types and amounts of the compounds were changed as shown in Table 1 to obtain varnishes B to Q. Note that the names and structures of the other compounds in Table 1 are as follows.

[0106] D-1: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)

[0107] D-2: NC6000 (trade name, manufactured by Nippon Kayaku Co., Ltd.)

[0108] E-1: PAG-103 (trade name, manufactured by Merck, Germany)

[0109] Surfactant: KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., Japan)

[0110]

[0111] Table 1

[0112]

[0113]

[0114] Examples 1-16

[0115] The resin compositions A-Q in the above examples and comparative examples were coated on an 8-inch wafer by spin coating, baked on a hot plate at 120 °C for 3 minutes to prepare a pre-baked film with a film thickness of 4.0 μm. Then, using an exposure machine (i-line stepper), through a mask with a pattern having contact holes of 5 μm, exposure was performed at an exposure dose of 100-600 mJ / cm 2 . After exposure, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH, manufactured by Suzhou Jingrui) was used for development for 2 min, then rinsed with distilled water, and then spin-dried to obtain a pattern. Then, it was treated in a nitrogen-filled oven at 250 °C for 2 h to obtain a cured film, and various properties of the cured film and lithography performance during the exposure process were tested, as shown in Table 2.

[0116] Table 2

[0117]

[0118] Performance test

[0119] According to the above method, the sensitivity, film loss, 5% thermal weight loss temperature, sulfur content in the cured film, and other properties of the resin composition were measured, and the results are shown in Table 2. By comparing Examples 6-11 with Comparative Examples 1-6, it can be seen that for the photosensitive compounds provided by the present invention, the sulfur content in the resin composition prepared can be significantly reduced, thereby improving the long-term stability of the OLED device. At the same time, it also has good performance in terms of sensitivity, film loss, and thermal stability.

[0120] By comparing Comparative Examples 1-3 with Examples 4-6, it can be seen that by using one or a mixture of two photosensitive compounds, the sensitivity of the resin composition can be improved, thereby reducing the size of the exposed pattern. Therefore, in order to improve photosensitivity, two photosensitive compounds can be used in combination.

[0121] Comparing Examples 5-11 and Comparative Examples 1-6, it can be seen that using alkali-soluble resins with different structures will affect the 5% thermal weight loss temperature of the resin composition, thereby affecting its thermal stability. Therefore, it is necessary to design different alkali-soluble resin structures according to requirements.

[0122] The present invention uses the above examples to illustrate the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A positive photosensitive resin composition, comprising the following components: (A) An alkali-soluble resin, (B) A photosensitive compound, (C) An organic solvent, (D) An auxiliary agent; wherein the (B) photosensitive compound is a compound formed by the reaction of the following general formula (1) and / or (2) with a phenolic hydroxyl group-containing compound; In General Formulas (1) and (2), R 1 represents an alkyl group having 1 to 4 carbon atoms, and X represents F, Cl, Br, or I.

2. The resin composition according to claim 1, characterized in that wherein the (A) alkali-soluble resin is selected from one or more of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

3. The resin composition according to claim 1, characterized in that the phenolic hydroxyl group-containing compound is selected from one or more of Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP.

4. The resin composition according to claim 1, characterized in that the addition amount of the (B) component is 2 wt% - 12 wt% of the positive photosensitive resin composition.

5. The resin composition according to claim 1, characterized in that the (D) auxiliary agent contains a thermal crosslinking agent, and the thermal crosslinking agent has at least 2 alkoxymethyl, hydroxymethyl, epoxy, or oxetanyl groups.

6. The resin composition according to claim 5, characterized in that the content of the thermal crosslinking agent is 1 wt% - 10 wt% relative to the total amount of the resin composition excluding the solvent.

7. The resin composition according to claim 1, characterized in that The component (D) contains a surfactant, and the surfactant is selected from one or more of silicone surfactants, fluorine surfactants, and surfactants formed from polymers of acrylic acid-based and / or methacrylic acid-based.

8. The resin composition according to claim 7, wherein, the content of the surfactant is 1-10 wt%, based on the total amount of the resin composition excluding the solvent.

9. The resin composition according to claim 1, wherein, the additive (D) contains a thermal acid generator, preferably one or more of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, or their onium salts and imide sulfonates.

10. The resin composition according to claim 9, wherein, the content of the acid generator is 1-10 wt%, based on the total amount of the resin composition excluding the solvent.

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