Alkali-soluble resin and use thereof

Abstract

An alkali-soluble resin and a use thereof. The alkali-soluble resin comprises a compound represented by general formula (1) and a compound represented by general formula (2), wherein the diamine residue in general formula (2) comprises at least two structural units, one of which is represented by general formula (3) or (4). By introducing a phenolic hydroxyl group, a sulfonyl group, or a combination thereof, and the structural unit represented by general formula (3) or (4) into an alkali-soluble resin structure, a fluorine-element-free alkali-soluble resin having a good organic solvent solubility is obtained. The alkali-soluble resin can be applied to a photosensitive resin composition to prepare a photosensitive curing film having good transmittance and heat resistance.

Description

Alkali-soluble resin and its application

[0001] Cross-references

[0002] This application claims priority to Chinese patent application No. 202410037523.7, filed on January 10, 2024, entitled “An alkali-soluble resin and its application,” the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to the field of polymer materials, in particular to an alkali-soluble resin and applications thereof. Background Art

[0004] Due to its unique aromatic ring conjugation and imide ring structure, polyimide exhibits good heat resistance, high insulation, chemical resistance and good mechanical properties, and is widely used in surface passivation layers, stress buffer layers and interlayer insulation layers of semiconductor devices; it also has important application value in signal line distribution, α-particle shielding layers, micro-solder ball processes, stress buffer layers of plastic-encapsulated circuits, flexible packaging substrates, etc. in semiconductor advanced packaging (BGA, CSP, SiP, WLP, etc.); at the same time, in display devices such as organic EL display devices or liquid crystal display devices, photosensitive polyimide resins are widely used in the flat layer and pixel definition layer of the display device to improve interlayer insulation and reduce display color difference.

[0005] The unique aromatic ring conjugation structure within polyimide (PI) films leads to the formation of intramolecular and intermolecular charge transfer complexes (CTCs), significantly impacting the light transmittance of polyimide (PI) films, resulting in a brownish-yellow color and poor transmittance, limiting the development of PI films in the optoelectronics field. To achieve good organic solvent solubility and excellent optical properties (such as transmittance), fluorine elements or fluorine-containing structures are often introduced to disrupt the conjugation in the polyimide structure, thereby improving optical performance.

[0006] However, with the international community's regulation of PFAS (full name: polymeric perfluoroalkane sulfonates) in recent years, the demand for fluorine-free materials has become increasingly apparent. Summary of the Invention

[0007] The present invention provides an alkali-soluble resin for solving the problems of poor solubility in organic solvents, low transmittance and poor heat resistance in the prior art without the presence of fluorine.

[0008] The present invention also provides application of the alkali-soluble resin.

[0009] In a first aspect, the present invention provides an alkali-soluble resin comprising a compound represented by general formula (1) and a compound represented by general formula (2).

[0010] Wherein, in the general formula (1), Ar1 represents a dianhydride residue; Ar2 represents a diamine residue, and Ar1 and Ar2 contain at least one phenolic hydroxyl group or one sulfonyl group; R1 represents a fluorine-free organic group having 1 to 10 H or C atoms; m is an integer from 10 to 10000, and r is an integer from 0 to 2;

[0011] Wherein, in the general formula (2), Ar3 represents a dianhydride residue; Ar4 represents a diamine residue, and the diamine residue Ar4 includes at least two structural units, one of which is as shown in the general formula (3) or the general formula (4);

[0012] Wherein, in the general formula (3), R2 and R3 are the same or different and independently represent -(CH2)- or -(CH2CH2)-; L1, L2, L3, and L4 are the same or different and independently represent H or a non-fluorine halogen element;

[0013] Wherein, in the general formula (4), R4 and R5 are the same or different and independently represent -(CH2)- or -(CH2CH2)-; L5, L6, L7, and L8 are the same or different and independently represent H or a non-fluorine halogen element;

[0014] Ar1, Ar2, Ar3 and Ar4 do not contain fluorine element.

[0015] It should be noted that the "non-fluorine halogen elements" mentioned in the above technical solution refer to chlorine, bromine or iodine.

[0016] The dianhydride residues (Ar1 and Ar3) are residues obtained by removing two anhydride groups from a dianhydride. The dianhydrides include, but are not limited to, the following dianhydrides, such as pyromellitic dianhydride (PMDA), 3,3,3',4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), p-phenylene-triphenylene dianhydride (TAHQ), 3,3',4 , one or more of 4'-diphenylsulfonetetracarboxylic dianhydride (BSDA), cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride (HPMDA), N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide and 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride (DSDA).

[0017] The diamine residues (Ar2 and Ar4) are residues obtained by removing two amino groups from a diamine. The diamines include but are not limited to the following diamines, such as 2,2-bis(4-hydroxy-3-aminophenyl)propane (BAP), 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone (BAHS), N,N'-[(1-methylethylidene)bis(6-hydroxy-3,1-phenylene)]bis[3-aminobenzamide, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis [3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]ether, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propan-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propan-2-yl]benzamide ]phenyl]-sulfone-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide, 1,4-p-phenylenediamine (PDA), m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (ODA), 4,4'-diamino-p-terphenyl (DATP), 4,4'-methylenedianiline (MDA), 2,2'- One or more of dimethyl-4,4'-diaminobiphenyl (m-TB), p-aminophenyl para-aminobenzoate (APAB), 1,4-bis(4'-aminophenoxy)benzene (1,4,4-APB), 1,3,4-APB:1,3-bis(4'-aminophenoxy)benzene (1,3,4-APB), 1,3-bis(3'-aminophenoxy)benzene (1,3,3-APB) and 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP).

[0018] Ar1 and Ar2 contain at least one phenolic hydroxyl group or one sulfonyl group (-S(=O)2-). In other words, among the raw dianhydrides and diamines used to form general formula (1), at least one raw material monomer contains a phenolic hydroxyl group or a sulfonyl group (-S(=O)2-) structure, or both structures may be present. These two structures may appear simultaneously on the same monomer or on different monomers. In addition, during the preparation of the compound represented by general formula (1), the weight proportion of monomers containing phenolic hydroxyl groups, sulfonyl groups, or a combination of the two groups in the total monomers is ≥20%.

[0019] It should be noted that when R1 represents H, the alkali-soluble resin is a polyamic acid soluble in an alkaline aqueous solution; when R1 represents a fluorine-free organic group with 1 to 10 C atoms, the alkali-soluble resin is a polyamide ester soluble in an alkaline aqueous solution, and preferably, the organic group is an alkyl group.

[0020] The present invention has found that when the structure contains phenolic hydroxyl groups, the resulting alkali-soluble resin has better alkali solubility; when the structure contains sulfonyl groups (-S(=O)2-) and alicyclic structures, the resulting alkali-soluble resin has better organic solvent solubility and better optical transmittance.

[0021] In a specific embodiment of the present invention, good alkali solubility is achieved by adjusting the structural ratio of general formula (1) and general formula (2); by introducing phenolic hydroxyl group, sulfonyl group (-S(=O)2-) or a combination of the two, and structural units represented by general formula (3) or general formula (4) into the alkali-soluble resin structure, an alkali-soluble resin with good organic solvent solubility is obtained under the condition of not containing fluorine element.

[0022] Specifically, the alkali-soluble resin has good solubility in organic solvents, which is embodied in that it is soluble in one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, propylene glycol methyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, γ-butyrolactone, methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

[0023] In some embodiments of the present invention, the proportion of the compound represented by general formula (1) to the sum of the mass of the compound represented by general formula (1) and the compound represented by general formula (2) is 10% to 50%.

[0024] The present invention has found that the higher the specific gravity of the compound represented by general formula (1) in the alkali-soluble resin, the better. If the specific gravity is too high, it is difficult to achieve both good organic solvent solubility and light transmittance, and if the specific gravity is too low, it is difficult to achieve alkali dissolution.

[0025] In order to further improve the transmittance, during the preparation of the compound represented by general formula (2), the proportion of the diamine monomers formed by general formula (3) and the diamine monomers formed by general formula (4) in the total mass of the diamine monomers (Ar4 is connected to an amino group at each end) is ≥50%.

[0026] In some embodiments of the present invention, the diamine forming the general formula (3) is selected from the group consisting of the following structures:

[0027] In some embodiments of the present invention, the diamine structure forming the general formula (4) is as follows:

[0028] The preparation method of the alkali-soluble resin of the present invention comprises the following steps:

[0029] (1) preparing the desired diamine (a diamine represented by two amino groups connected at both ends of the general formula (3) or (4)) according to the self-designed structure and process, and performing purification and other post-treatments for use;

[0030] (2) Under the protection of inert gas, materials such as phenolic hydroxyl group, sulfonyl group (-S(=O)2-) monomer, other diamine (optionally added) and dianhydride (optionally added) are successively dissolved in an organic solvent, and a polyimide precursor solution 1 with a solid content of 10-50% is obtained by polymerization reaction, or a diester solution is obtained by esterification of dianhydride with alcohol, and then further reacted with diamine after chlorination or DCC treatment to obtain a polyimide precursor solution 1 with a solid content of 10-50%; alicyclic diamine (a diamine represented by two amino groups connected at both ends of the general formula (3) or (4), other diamine (optionally added) and dianhydride (optionally added) are successively dissolved in an organic solvent, and a polyimide solution 2 with a solid content of 10-50% is obtained by high-temperature polymerization reaction; the two are mixed and stirred at room temperature to obtain a polyimide resin solution (a small amount of copolymerization occurs under room temperature mixing);

[0031] (3) The resin is precipitated using a precipitant, and the target alkali-soluble resin is obtained after filtering, washing and drying.

[0032] In a second aspect, the present invention provides a photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photosensitizer, (c) a cross-linking agent, (d) an adhesion modifier, and (e) a solvent; wherein the (a) alkali-soluble resin comprises the above-mentioned alkali-soluble resin of the present invention.

[0033] In some embodiments of the present invention, the (b) photosensitizer is a naphthoquinone azide-type photosensitizer.

[0034] The naphthoquinone azide photosensitizer is an esterified product of a phenolic hydroxyl group-containing compound and naphthoquinone azide sulfonyl chloride. The phenolic hydroxyl group-containing compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

[0035] In some embodiments of the present invention, the cross-linking agent (c) has no particular requirements and can be a thermally cross-linkable compound capable of undergoing a cross-linking reaction with the alkali-soluble resin. Specifically, the cross-linking agent (c) can be selected from one or more of epoxy compounds, alkoxymethylol compounds, and alkoxymethylol triazine ring compounds; and the functionality of the cross-linking agent (c) is greater than or equal to 2.

[0036] The epoxy compound is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and propylene glycol diglycidyl ether.

[0037] The alkoxymethylol compound is selected from polyalkoxymethylolated phenolic hydroxyl compounds, wherein the phenolic hydroxyl compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

[0038] The alkoxy hydroxymethyl triazine ring compound is selected from one or more compounds represented by general formula (5);

[0039] wherein R8 and R9 independently represent H, CH2OCH3 or CH2OCH2CH3, and not all of them are H.

[0040] In some embodiments of the present invention, the (d) adhesion modifier includes but is not limited to one or more of the following: γ-glycidoxypropyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550), γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-aminophenyltrimethoxysilane, 3-(m-aminophenoxy)trimethoxysilane, 3-mercaptomethyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

[0041] In some embodiments of the present invention, the (e) solvent is one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents and other solvents.

[0042] By way of example but not limitation, the ketone solvent is one of acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone.

[0043] The ester solvent is one or more of ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and gamma-butyrolactone.

[0044] The ether solvent is one or more of propylene glycol methyl ether, propylene glycol monoethyl ether, and ethylene glycol monomethyl ether.

[0045] The aromatic hydrocarbon solvent may be one or more of toluene and xylene.

[0046] The other solvents are one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0047] In a third aspect, the present invention provides a photosensitive cured film formed by curing any one of the above-mentioned photosensitive resin compositions.

[0048] Those skilled in the art will appreciate that curing the photosensitive resin composition to form a cured film typically involves some pre-treatment, such as coating, hot plate drying, exposure, and development before curing. Each step employs conventional techniques in the art. For example, coating may be performed using a rotational viscometer, drying may be performed using a hot plate, and curing may be performed thermally under nitrogen.

[0049] Due to the specific structure of the alkali-soluble resin in the photosensitive resin composition, the photosensitive cured film of the present invention has good light transmittance and heat resistance; the average light transmittance of the photosensitive cured film at 380-780nm is ≥70%; and the thermal weight loss temperature T5% is ≥300°C.

[0050] The photosensitive cured film of the present invention can be applied to surface protective films and interlayer insulating films of semiconductor elements, insulating layers of organic electroluminescent elements, and insulating layers of thin film transistors.

[0051] The present invention provides an alkali-soluble resin and its application. By introducing a phenolic hydroxyl group, a sulfonyl group or a combination of the two, and a structural unit represented by general formula (3) or general formula (4) into the structure of the alkali-soluble resin, an alkali-soluble resin having good solubility in organic solvents without the presence of fluorine is provided. The alkali-soluble resin can be applied to a photosensitive resin composition to prepare a photosensitive cured film having good transmittance and heat resistance. DETAILED DESCRIPTION

[0052] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0053] Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art. Unless otherwise specified, the materials and reagents used in the examples of the present invention can be obtained through regular commercial channels.

[0054] Abbreviations of the compounds in the following examples are: PDA: p-phenylenediamine BAP: 2,2-bis(4-hydroxy-3-aminophenyl)propane BAHS: 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone ODPA: 4,4'-oxydiphthalic anhydride DSDA: 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride DMFDEA: N,N'-dimethylformamide diethyl acetal MAP: m-aminophenol TrisP-HAP: 1,1,1-tris(4-hydroxyphenyl)ethane

[0055] Synthesis Example 1 Synthesis of diamines (I-1) and (I-2)

[0056] The synthesis route is as follows:

[0057] (1) Synthesis of Compound I-1

[0058] 25.4 g of compound I-1-1 and 200 ml of tetrahydrofuran were added to the reactor, ammonia gas was introduced to a pressure of 0.5-1.0 MPa at room temperature, the temperature was raised to 200 ° C and the reaction was carried out for 6 hours. The temperature was lowered and the pressure was reduced. The reaction was quenched with saturated sodium bicarbonate aqueous solution and conventional post-treatment was performed. The mixture was recrystallized from n-heptane to obtain 25.1 g of an off-white solid (compound I-1), HPLC: 99.6%, and a yield of 87.2%.

[0059] The obtained white solid compound I-1 was analyzed by GC-MS, and the m / z of the product was 246.2 (M+).

[0060] (2) Synthesis of Compound I-2

[0061] Compound I-2 was prepared using the same mechanism as above, but the yield was low, so the subsequent synthesis example 9 is currently in the laboratory stage.

[0062] Synthesis Example 2 Synthesis of diamine (I-3)

[0063] The synthesis route is as follows:

[0064] (1) Synthesis of Compound I-3-2

[0065] Under nitrogen protection, 36.0 g of compound I-3-1 and 200 ml of tetrahydrofuran were added to the reaction flask, and 68.3 g of hydrogen fluoride pyridine was added dropwise at a temperature of -10 to 0 ° C. After the addition, the reaction was kept warm for 2 hours, and a saturated aqueous sodium bicarbonate solution was added to quench the reaction. Conventional post-treatment was performed and recrystallized from n-heptane to obtain 30.5 g of a light yellow solid (compound I-3-2), HPLC: 99.3%, and a yield of 72.6%.

[0066] (2) Synthesis of Compound I-3

[0067] Under nitrogen protection, 14.2 g of ammonium formate, 200 ml of methanol, 30.0 g of compound I-3-2, 10 ml of acetic acid, and 0.001 g of iridium catalyst (Ir-3) were added to the reaction flask, and the reaction was refluxed for 8 hours at a temperature of 75 ° C. The temperature was cooled to room temperature and quenched by adding a saturated aqueous sodium hydroxide solution. The mixture was then subjected to conventional post-processing operations, dissolved in dichloromethane and separated, purified by chromatography, and recrystallized from a mixed solution of n-heptane and toluene in a volume ratio of 3: 1 to obtain 23.7 g of a white solid (compound I-3), HPLC: 99.8%, yield: 78.5%.

[0068] The obtained white solid compound I-3 was analyzed by GC-MS, and the m / z of the product was 246.2 (M+).

[0069] Synthesis Example 3 Synthesis of photosensitizer (PAC-1)

[0070] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 260 g of dioxane (water was removed with molecular sieves 24 hours in advance) was added, and then 10.60 g (0.025 mol) of TrisP-PA (trade name, made by Honshu Chemical) and 20.1 g (0.075 mol) of naphthoquinone azidosulfonyl chloride were added respectively. A mixed solution of triethylamine (6.3 g) and dioxane (20 g) was slowly added dropwise, and the temperature was controlled within 30°C. After the addition was completed, the mixture was kept at 30°C for 2 hours. The mixture was filtered, washed with deionized water 3 times, rinsed with dilute hydrochloric acid and deionized water 3 times respectively, and dried in a vacuum at 60°C for 24 hours.

[0071] Synthesis Example 4 Synthesis of photosensitizer (PAC-2)

[0072] The photosensitizer PAC-2 was prepared by a similar synthesis method to that in Synthesis Example 3, except that TrisP-PA (trade name, manufactured by Honshu Chemical) was replaced by Trisp-HAP (trade name, manufactured by Honshu Chemical).

[0073] Synthesis Example 5 Synthesis of Crosslinking Agent (C-1)

[0074] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 200 g of water was added, and then 20 g (0.5 mol) of NaOH and 25.8 g (0.1 mol) of 1,1,1-tris(4-hydroxyphenyl)ethane were added respectively. After they were fully dissolved, 18 eq of formaldehyde solution was slowly added dropwise, and the temperature was controlled within 20°C. After the addition was completed, the temperature was kept at 20°C for 24 hours. Sulfuric acid and water were added to neutralize the product to obtain a white product, which was washed with deionized water three times and dried in a vacuum at 50°C for 72 hours.

[0075] The dried white product was further reacted with methanol at room temperature for 24 h, and the methanol was removed by distillation under reduced pressure to obtain cross-linking agent C-1.

[0076] Synthesis Example 6 Synthesis of Crosslinking Agent (C-2)

[0077] Crosslinking agent C-2 was prepared by a similar synthesis method to that in Synthesis Example 5, except that Trisp-HAP (trade name, manufactured by Honshu Chemical) was replaced with melamine.

[0078] Synthesis Example 7 Synthesis of Polyimide Resin A-1

[0079] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 86.25 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours in advance) was added, followed by 5.17 g (0.02 mol) of BAP, and the mixture was stirred at 25°C until completely dissolved. 8.96 g (0.025 mmol) of DSDA was then added, and the mixture was stirred at room temperature for 12 hours. 1.09 g (0.01 mol) of MAP was added, and the mixture was kept warm for 12 hours. 11.66 g of DMFDEA was added, and the temperature was raised to 60°C, kept warm for 4 hours, and then cooled to room temperature to obtain resin solution A-1-1.

[0080] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 78.82 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours in advance) was added, followed by 6.16 g (0.025 mol) of I-1. The mixture was stirred at 25°C until completely dissolved. Then, 7.75 g (0.025 mmol) of compound ODPA was added. The mixture was stirred at room temperature for 12 hours. 16 g of toluene was added, the temperature was raised to 160°C, refluxed to remove water, and the temperature was maintained for 4 hours. The mixture was then cooled to room temperature to obtain resin solution A-1-2.

[0081] Resin solutions A-1-1 and A-1-2 were mixed and stirred at room temperature for 12 hours to obtain polyimide resin A-1 solution, which was added into 3 L of deionized water, precipitated, filtered, and washed three times; and vacuum dried at 80°C for 72 hours to obtain polyimide resin A-1.

[0082] Synthesis Examples 8 to 12 Synthesis of Polyimide Resins A-2 to A-6

[0083] As shown in Table 1, resin solutions A-2-1, A-3-1, A-4-1, A-5-1, and A-6-1 were prepared by replacing 40 parts of BAP with 40 parts of BAHS or PDA, respectively, and using the same formula and process as resin solution A-1-1;

[0084] Resin solutions A-2-2, A-3-2, A-4-2, A-5-2, and A-6-2 were prepared by replacing 50 parts of I-1, I-2, I-3, PDA, and PDA with 50 parts of I-1, and replacing 50 parts of DSDA with 50 parts of ODPA, respectively, using the same formula and process as resin solution A-2-1;

[0085] In the same manner as A-1-2 and A-2-2, the mixtures were mixed and stirred at room temperature for 12 h to obtain polyimide resins A-2 to A-6 solutions, which were then added into 3 L of deionized water, precipitated, filtered, and washed three times; and vacuum dried at 80 ° C for 72 h to obtain polyimide resins A-2 to A-6.

[0086] Synthesis Example 13 Synthesis of Polyimide Resin A-7

[0087] As shown in Table 1, resin solution A-7 was prepared by replacing 40 parts of BAP with 90 parts of PDA, and replacing 50 parts of ODPA and 50 parts of DSDA with 100 parts of ODPA, and using the same formula and process as resin solution A-1-1;

[0088] The reaction was continued under stirring at room temperature for 12 h to obtain a polyimide resin A-7 solution, which was then added into 3 L of deionized water, precipitated, filtered, and washed three times; and vacuum dried at 80° C. for 72 h to obtain a polyimide resin A-7.

[0089] Table 1

[0090] Example 1

[0091] 10 g of the polyimide resin A-1 prepared in Synthesis Example 7, 1 g of PAC-1 prepared in Synthesis Example 3, 2 g of PAC-2 prepared in Synthesis Example 4, 0.1 g of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 0.8 g of the cross-linking agent C-1 prepared in Synthesis Example 5, and 0.2 g of the cross-linking agent C-2 prepared in Synthesis Example 6 were dissolved in 30 g of γ-butyrolactone and thoroughly mixed to obtain a photosensitive resin composition.

[0092] Examples 2 to 4

[0093] In Examples 2 to 4, polyimide resins A-2 to A-4 were used to replace polyimide resin A-1, respectively, and photosensitive resin compositions were prepared in the same manner as in Example 1.

[0094] Comparative Examples 1 to 3

[0095] In Comparative Examples 1 to 3, polyimide resins A-5 to A-7 were used to replace polyimide resin A-1, respectively, and photosensitive resin compositions were prepared in the same manner as in Example 1.

[0096] Resins A-1 to A-7 obtained in Synthesis Examples 7 to 13 were tested for their solubility in organic solvents. 1 g of each resin was dissolved in 9 g of solvent and stirred for 12 hours. The solubility was observed. The results are summarized in Table 2. Among them, amides include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; ethers include: propylene glycol methyl ether, propylene glycol monoethyl ether, and ethylene glycol monomethyl ether; and esters include: γ-butyrolactone, methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

[0097] Table 2

[0098] The photosensitive resin compositions obtained in the examples and comparative examples were used to prepare photocured films according to the following preparation methods, and the properties of the obtained photocured films were measured according to the following methods. The results are summarized in Table 3.

[0099] Preparation of photosensitive curing film: Use a rotational viscometer (Mikasa: MS-B150+DA-60S) for wet film coating, pre-dry on a hot plate, and then transfer to a nitrogen oven for further curing after exposure and development. Cure at 150-250°C for 30-180 minutes, then cool to room temperature and take out.

[0100] (1) Transmittance (T%)

[0101] The results were obtained using an Agilent UV-visible spectrophotometer Cary 4000 in transmission mode.

[0102] (2) Thermal weight loss temperature (T5%)

[0103] The thermal decomposition temperature was measured using a thermogravimetric analyzer (model TGA-55) at a heating rate of 10°C / min, with a sample size of 3-5 mg and a temperature range of RT to 500°C.

[0104] Table 3

[0105] As can be seen from the data in Table 2, the alkali-soluble resin provided by the present invention has good solubility in organic solvents and is well soluble in solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, propylene glycol methyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, γ-butyrolactone, methyl lactate, ethyl lactate, propyl lactate and butyl lactate. It is suitable for providing an alkali-soluble resin solution with good organic solvent solubility without the presence of fluorine element; and provides an environmentally friendly photosensitive resin composition solution.

[0106] As can be seen from the data in Table 3, the photosensitive resin composition, after rotational viscometer coating, hot plate drying, exposure, development, and heat curing under nitrogen, produces a photocured film exhibiting excellent light transmittance and good heat resistance; an average light transmittance (380-780 nm) of ≥70%; and a thermal weight loss temperature (T5%) of ≥300°C. The composition is suitable for use as surface protective films and interlayer insulating films for semiconductor devices, insulating layers for organic electroluminescent devices, and insulating layers for thin-film transistors.

[0107] However, it is necessary to control the ratio of the structures of general formula (1) and general formula (2). By adjusting the ratio of the structures of general formula (1) and general formula (2), good alkali solubility can be achieved. When the structure of general formula (1) accounts for more than 50%, it is difficult to achieve good organic solvent solubility and transmittance, and it is difficult to achieve alkali solubility when it is too low. At the same time, by introducing phenolic hydroxyl groups, sulfonyl groups (-S(=O)2-) or a combination of the two, as well as structural units represented by general formula (3) or general formula (4) into the alkali-soluble resin structure, it can be used to solve the problems of poor organic solvent solubility, low transmittance and poor heat resistance in the prior art without fluorine element.

[0108] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention. Industrial Applicability

[0109] The present invention relates to the field of polymer materials and provides an alkali-tolerant resin and its application. The present invention provides an alkali-soluble resin having good solubility in organic solvents without the presence of fluorine by introducing a phenolic hydroxyl group, a sulfonyl group or a combination of the two, and a structural unit represented by general formula (3) or general formula (4) into the structure of the alkali-soluble resin. The alkali-soluble resin can be applied to a photosensitive resin composition to prepare a photosensitive cured film having good transmittance and heat resistance.

Claims

1. An alkali-soluble resin, characterized in that, Comprising a compound represented by general formula (1) and a compound represented by general formula (2), Among them, in general formula (1), Ar1 represents a dianhydride residue; Ar2 represents a diamine residue, and at least one of Ar1 and Ar2 contains a phenolic hydroxyl group or a sulfonyl group; R1 represents H or a fluorine-free organic group with 1 to 10 carbon atoms; m is an integer from 10 to 10,000, and r is an integer from 0 to 2; Among them, Ar3 in the general formula (2) represents a dianhydride residue; Ar4 represents a diamine residue, and the diamine residue Ar4 includes at least two structural units, and one of the structural units is represented by the general formula (3) or the general formula (4); Among them, R2 and R3 in the general formula (3) are the same or different and independently represent -(CH2)- or -(CH2CH2)-; L1, L2, L3, and L4 are the same or different and independently represent H or a non-fluorine halogen element; Among them, R4 and R5 in the general formula (4) are the same or different and independently represent -(CH2)- or -(CH2CH2)-; L5, L6, L7, and L8 are the same or different and independently represent H or a non-fluorine halogen element; Ar1, Ar2, Ar3, and Ar4 do not contain fluorine elements.

2. The alkali-soluble resin according to claim 1, wherein, The proportion of the compound represented by the general formula (1) in the total mass of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 10% - 50%.

3. The alkali-soluble resin according to claim 1 or 2, characterized in that, During the preparation of the compound represented by the general formula (1), the monomer containing a phenolic hydroxyl group, a sulfonyl group, or a combination of both accounts for ≥20% of the total monomer by mass.

4. The alkali-soluble resin according to any one of claims 1 to 3, characterized in that, During the preparation of the compound represented by the general formula (2), the diamine monomer forming the general formula (3) and the diamine monomer forming the general formula (4) account for ≥50% of the total mass of the diamine monomers.

5. The alkali-soluble resin according to any one of claims 1-4, characterized in that, The diamine forming the general formula (3) is selected from the group consisting of the following structures: And / or, the diamine having the general formula (4) is formed as follows:

6. The alkali-soluble resin according to any one of claims 1 to 5, characterized in that, The alkali-soluble resin has good solubility in organic solvents and is soluble in one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, propylene glycol methyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, γ-butyrolactone, methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

7. A photosensitive resin composition, characterized in that, It includes (a) an alkali-soluble resin, (b) a photosensitizer, (c) a crosslinking agent, (d) a binder modifier, and (e) a solvent; the (a) alkali-soluble resin includes the alkali-soluble resin according to any one of claims 1-6.

8. A photosensitive curing film, characterized in that, It is formed by curing the photosensitive resin composition according to claim 7.

9. The photosensitive curable film according to claim 8, wherein The average light transmittance of the photosensitive cured film at 380 - 780 nm is ≥70%; the thermal weight loss temperature T5% ≥ 300 °C.

10. The photosensitive cured film according to claim 9, wherein, The photosensitive cured film is applicable to the surface protective film and interlayer insulating film of semiconductor elements, the insulating layer of organic light-emitting elements, and the insulating layer of thin-film transistors.

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