A polyimide and polyamic acid and a positive polyimide photosensitive resin composition for a display device

Abstract

This invention provides a polyimide, a polyamic acid, and a positive polyimide photosensitive resin composition for display devices, belonging to the field of materials science and technology. This invention synthesizes a polyamide ester containing structural unit (1) and a polyamic acid having structural unit (2), and then mixes the polyimide resin, diazo-naphthoquinone, a thermally crosslinking compound, a silane coupling agent, a surfactant, and a solvent to obtain a positive polyimide photosensitive resin composition, wherein the polyimide resin is composed of polyamide ester and polyamic acid. The organic insulating layer prepared from the positive photosensitive polyimide composition of this invention can be cured at temperatures of 200°C and below, has high solubility in organic solvents, and exhibits excellent adhesion to the substrate and high resolution.

Description

Technical Field

[0001] The present invention relates to the field of material science and technology, and in particular to a polyimide and a polyamic acid and a positive polyimide photosensitive resin composition for a display device. Background Art

[0002] Polyimide is a kind of polymer material with excellent comprehensive performance containing imide rings on the main chain of the molecule. This kind of material has excellent mechanical, dielectric, insulation, radiation resistance, corrosion resistance, high and low temperature resistance and other properties, and has been widely used in various fields such as thin films, adhesives, coatings, laminated composite materials, molding compounds and electronic packaging. Especially in the field of electronics, the advantages of photosensitive polyimide are its physical properties such as high heat resistance, high mechanical strength, high resistivity, etc., and it has excellent electrical properties such as low dielectricity and high insulation, so it is usually used as a protective material in integrated circuit boards, thin films, and electronic packaging materials.

[0003] The common polyimide main chain contains a large number of imide ring structures. Due to the electronic polarization and crystallinity, there is a strong force between the polyimide molecular chains, which makes the polyimide molecular chains stacked tightly, making them difficult to dissolve and melt, seriously affecting their application value. Therefore, in order to solve the solubility problem, it is usually processed into the precursor polyamic acid of polyimide or esterified into polyamide ester, and then converted into the final polyimide material by thermal imidization or chemical imidization. And polyimide is widely used in surface protection films, interlayer insulating films and leveling films of semiconductor elements, such as insulating films for organic EL elements, and the substrate size is usually very large, so slit coating is usually used to apply resin composition. Slit coating is a coating method using a slit nozzle. Unlike the previous spin coating, slit coating does not require a rotating substrate. Therefore, from the perspective of reducing the amount of resin composition used and process safety, slit coating is widely used. Slit coating has high requirements on the solubility of the resin composition, so a resin composition with high performance and excellent solubility is needed by the market.

[0004] Photosensitive polyimide can be divided into positive photosensitive polyimide and negative photosensitive polyimide. Many studies have shown that positive photosensitive polyimide has better resolution than negative photosensitive polyimide and has a relatively small light radiation area, so the probability of defects is lower. The use of alkaline aqueous solution as the developing solution greatly reduces the finished product and reduces pollution to the environment.

[0005] In the prior art, polyimide compositions usually use polyamic acid and polyimide. The composition has poor solubility in alkaline aqueous solution, and the film surface is uneven after film formation. It is more prone to deterioration during storage, resulting in a significant decrease in the resolution of the film formed by coating the composition after exposure and development.

[0006] Therefore, how to provide a positive polyimide photosensitive resin composition that has good solubility in alkaline aqueous solution and high resolution after film formation is a technical problem that those skilled in the art need to solve urgently. Summary of the invention

[0007] The purpose of the present invention is to provide a polyimide and a polyamic acid and a positive polyimide photosensitive resin composition for a display device to solve the technical problems in the prior art that the polyimide composition has poor solubility in alkaline aqueous solution and the resolution of the film is greatly reduced after exposure and development.

[0008] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0009] The present invention provides a polyamide ester, wherein the polyamide ester comprises a structural unit (1):

[0010]

[0011] In the structural unit (1), X1 and X2 represent the residue of tetravalent alicyclic tetracarboxylic dianhydride, Y1 represents the residue of divalent aromatic diamine, and R1 represents C 1～5 Alkyl, C 3～10 The cycloalkyl group or aromatic group is selected from the group consisting of:

[0012] Preferably, the residue of the tetravalent alicyclic tetracarboxylic dianhydride is selected from one of the structures of C1 to C6:

[0013]

[0014] The Y1 is selected from one of the structures of E1 to E16:

[0015]

[0016] The present invention provides a polyamic acid, wherein the polyamic acid comprises a structural unit (2), wherein the structural unit (2) comprises two isomers (c) and (d):

[0017]

[0018]

[0019] Wherein X3 represents a residue of a tetravalent aromatic tetracarboxylic dianhydride, Y2 represents a residue of a divalent aromatic diamine, and n is an integer between 50 and 1000.

[0020] Preferably, the residue of the tetravalent aromatic tetracarboxylic dianhydride is selected from one of the structures D1 to D9:

[0021]

[0022] The Y2 is selected from one of the structures of E1 to E16:

[0023]

[0024] The present invention also provides a positive polyimide photosensitive resin composition for a display device, comprising the following components in parts by weight: 100 parts of a polyimide resin, 1 to 50 parts of diazonaphthoquinone, 5 to 50 parts of a thermally crosslinkable compound, 0.01 to 5 parts of a silane coupling agent, 0.01 to 10 parts of a surfactant, and 20 to 2000 parts of a solvent; the polyimide resin is composed of polyamide ester and polyamic acid, wherein the mass ratio of polyamide ester to polyamic acid is 10:90 to 70:30.

[0025] Preferably, the diazonaphthoquinone comprises a compound obtained by sulfonamide bonding of the sulfonic acid of diazidequinone with a polyamino compound, or a compound obtained by ester bonding of the sulfonic acid of diazidequinone with a polyhydroxy compound, or a compound obtained by ester bonding and / or sulfonamide bonding of the sulfonic acid of diazidequinone with a polyhydroxypolyamino compound.

[0026] Preferably, the heat-crosslinkable compound comprises one or more of a compound having an epoxy structure, a compound having an oxetane structure, a compound having an alkoxymethyl group, and a compound having a benzoxazine structure.

[0027] Preferably, the silane coupling agent comprises one or more of aminopropyltrimethoxysilane, trimethoxyepoxysilane, vinyltrimethoxysilane and mercaptopropyltrimethoxysilane.

[0028] Preferably, the surfactant comprises one or more of a silicon-based surfactant, a fluorine-based surfactant and a nonionic surfactant.

[0029] Preferably, the solvent comprises one or more of an amide solvent, a ketone solvent, an ester solvent, an ether solvent, a sulfoxide solvent, a sulfone solvent, a phenol solvent and an aromatic hydrocarbon solvent.

[0030] Technical effects of the present invention:

[0031] (1) The organic insulating layer prepared using the positive photosensitive polyimide composition of the present invention can be cured at a temperature of 200° C. or below, has high solubility in organic solvents, and has excellent adhesion to the substrate and high resolution.

[0032] (2) The present invention blends fluorine-containing or fluorine-free polyamide ester resin and polyamide acid resin, and utilizes the hydrophobicity and carboxyl groups of the fluorine-rich surface to enable the film to maintain a high film retention rate and high resolution in an alkaline developer, and ensure that there is no residue on the edge of the pattern after development, making it of great value in industrial applications. DETAILED DESCRIPTION

[0033] The present invention provides a polyamide ester, wherein the polyamide ester comprises a structural unit (1):

[0034]

[0035] In the structural unit (1), X1 and X2 represent the residue of tetravalent alicyclic tetracarboxylic dianhydride, Y1 represents the residue of divalent aromatic diamine, and R1 represents C 1～5 Alkyl, C 3～10 The cycloalkyl group or aromatic group is selected from the group consisting of:

[0036] In the present invention, R1 represents C 1～5 Alkyl, C 3～10 A cycloalkyl or aromatic group, preferably C 1～5 Alkyl or C 3～10 The cycloalkyl group is further preferably one of methyl, ethyl, isopropyl and tert-butyl; the m is an integer between 100 and 1000, preferably an integer between 200 and 900, and further preferably an integer between 300 and 800.

[0037] In the present invention, the residue of the tetravalent alicyclic tetracarboxylic dianhydride is preferably selected from one of the structures of C1 to C6:

[0038]

[0039] In the present invention, Y1 is preferably selected from one of the structures of E1 to E16:

[0040]

[0041] The polyamide ester provided by the present invention significantly reduces the curing temperature of the polyimide resin by introducing ester bonds or amide bonds on the side chains of its repeating units. Compared with some polyamide esters containing polyimide compositions or whose side chains are not esterified, the polyamide ester can be directly cured at 200° C. or below.

[0042] In the present invention, the polyamide ester containing the structural unit (1), wherein the polyamide ester having excellent physical properties may contain a phenolic hydroxyl group. Due to the phenolic hydroxyl group, it can be further functionalized or cross-linked to obtain a functional polyimide or a polyimide having higher thermal stability and mechanical properties. The phenolic hydroxyl group can make the positive polyimide resin composition more soluble in alkaline aqueous solution and achieve high sensitivity.

[0043] In the present invention, the preparation method of the polyamide ester preferably comprises the following steps: under a nitrogen protective atmosphere, an aromatic diamine and an organic solvent are mixed and then a first-stage reaction is carried out until a homogeneous solution is formed; then alicyclic dianhydride is added to the aromatic diamine solution, a second-stage reaction is carried out, and a polyamic acid resin solution is generated through a condensation reaction; finally, an excess amount of an organic fatty alcohol compound is added to the polyamic acid resin solution, and a third-stage reaction is carried out to obtain the polyamide ester.

[0044] In the present invention, the organic solvent is preferably NMP (N-methyl-2-pyrrolidone).

[0045] In the present invention, after the aromatic diamine and the organic solvent are mixed, the concentration of the aromatic diamine is preferably 10 to 15 wt %, more preferably 11 to 14 wt %, and more preferably 13 to 14 wt %.

[0046] In the present invention, the molar ratio of the aromatic diamine, the aliphatic dianhydride and the organic aliphatic alcohol compound is 1:(0.8-1):(2-2.2), preferably 1:0.8:2, 1:0.9:2.2, 1:0.88:2.12 or 1:1:2.1.

[0047] In the present invention, the temperature of the first stage reaction is 20-60°C, preferably 20°C, 25°C, 28°C, 30°C, 36°C, 38°C, 40°C, 45°C, 47°C, 55°C or 60°C; the time of the first stage reaction is 0.5-1h, preferably 0.5h, 0.6h, 0.8h or 1h.

[0048] In the present invention, the temperature of the second stage reaction is 40-80°C, preferably 40°C, 50°C, 60°C, 70°C or 80°C; the time of the second stage reaction is 2-10h, preferably 2h, 4h, 6h, 8h or 10h.

[0049] In the present invention, the temperature of the third stage reaction is room temperature, preferably 20-30°C, more preferably 25°C; the time of the third stage reaction is 1-4h, preferably 1h, 1.5h, 2h, 3h or 4h.

[0050] The third stage reaction in the present invention is carried out under acidic conditions, the alcohol hydroxyl group and the carboxyl group undergo esterification reaction to obtain a polyamide ester resin solution, and then the polyamide ester resin solution is slowly dropped into a large amount of water for precipitation, the precipitated solution is filtered, the solid is collected, and then the solid is soaked and rinsed twice with a large amount of ethanol and filtered, and dried under reduced pressure in a vacuum oven at 50-70° C. for at least 10 hours to obtain a polyamide ester solid powder for standby use.

[0051] The present invention provides a polyamic acid, wherein the polyamic acid comprises a structural unit (2), wherein the structural unit (2) comprises two isomers (c) and (d):

[0052]

[0053]

[0054] wherein X3 represents a residue of a tetravalent aromatic tetracarboxylic dianhydride, Y2 represents a residue of a divalent aromatic diamine, and n is an integer between 50 and 1000, preferably an integer between 100 and 900, and more preferably an integer between 200 and 800.

[0055] In the present invention, the residue of the tetravalent aromatic tetracarboxylic dianhydride is preferably selected from one of the structures D1 to D9:

[0056]

[0057] In the present invention, Y2 is preferably selected from one of the structures of E1 to E16:

[0058]

[0059] In the present invention, the preparation method of polyamic acid preferably comprises the following steps: under a nitrogen protective atmosphere, mixing a fluorine-containing aromatic diamine and an organic solvent to form a homogeneous solution; adding an aromatic dianhydride to the homogeneous solution for reaction to obtain polyamic acid.

[0060] In the present invention, the molar ratio of the fluorinated aromatic diamine to the aromatic dianhydride is 1 mol:0.7-1.1 mol, preferably 1 mol:0.8-1.0 mol, and more preferably 1 mol:0.9 mol; the concentration of the fluorinated aromatic diamine after mixing the fluorinated aromatic diamine and the organic solvent to form a homogeneous solution is 5-15wt%, preferably 6-14wt%, and more preferably 7-12wt%.

[0061] In the present invention, the temperature at which the fluorinated aromatic diamine and the organic solvent are mixed is preferably room temperature, more preferably 20 to 30°C, and further preferably 25°C.

[0062] In the present invention, the reaction temperature is room temperature, preferably 20 to 30° C., and more preferably 25° C.; the reaction time is 3 to 5 h, preferably 3.5 to 4.5 h, and more preferably 4 h.

[0063] In the present invention, the polyamic acid resin solution obtained by adding aromatic dianhydride to a homogeneous solution for reaction is preferably poured into a large amount of water for precipitation, the precipitated solution is filtered, the solid is collected, and then the solid is soaked and washed with a large amount of anhydrous ethanol for two or more times, filtered, and dried under reduced pressure at 50-70° C. for at least 10 hours to obtain a polyamic acid solid powder for standby use.

[0064] In the present invention, the polyamide ester and polyamic acid can add a terminal functional group to adjust the molecular weight or improve the storage stability of the resin composition. The end-capping agent is preferably a monoamine, anhydride or monoacyl chloride compound, and is more preferably one or more of aniline, phthalic anhydride, maleic anhydride, 2-carboxyphenol, 3-carboxyphenol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol and 4-aminothiophenol.

[0065] The present invention also provides a positive polyimide photosensitive resin composition for a display device, comprising the following components in parts by weight: 100 parts of a polyimide resin, 1 to 50 parts of diazonaphthoquinone, 5 to 50 parts of a thermally crosslinkable compound, 0.01 to 5 parts of a silane coupling agent, 0.01 to 10 parts of a surfactant, and 20 to 2000 parts of a solvent; the polyimide resin is composed of polyamide ester and polyamic acid, wherein the mass ratio of polyamide ester to polyamic acid is 10:90 to 70:30, preferably 10:90, 30:70, 50:50, 70:30, and further preferably 70:30 and 50:50.

[0066] In the present invention, the content of the diazonaphthoquinone is preferably 5 to 45 parts, more preferably 10 to 40 parts.

[0067] In the present invention, the diazonaphthoquinone comprises a compound obtained by sulfonamide bonding of the sulfonic acid of diazidoquinone with a polyamino compound, or a compound obtained by ester bonding of the sulfonic acid of diazidoquinone with a polyhydroxy compound, or a compound obtained by ester bonding and / or sulfonamide bonding of the sulfonic acid of diazidoquinone with a polyhydroxy polyamino compound; preferably, a compound obtained by ester bonding of the sulfonic acid of diazidoquinone with a polyhydroxy compound; more preferably, an ester formed by a polyhydroxy compound and diazidonaphthoquinone-5-sulfonyl, 4-naphthoquinone diazidosulfonyl. The diazonaphthoquinone used in the present invention is a photoactive compound, which refers to a compound that can generate an acid when light is irradiated thereon. By using diazonaphthoquinone, a positive polyimide photosensitive resin composition that is sensitive to general ultraviolet rays, i.e., i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) of a mercury lamp can be obtained. Among them, 4-naphthoquinone diazide sulfonyl ester compounds have absorption effect in the i-ray region of mercury lamp and can obtain high sensitivity under i-line exposure.

[0068] In the present invention, the preparation method of the diazonaphthoquinone is preferably: under the protection of a dry nitrogen atmosphere, TrisP-PA (21.22 g, 0.05 mol) (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and diazidonaphthoquinone-5-sulfonyl chloride (26.8 g, 0.1 mol) are dissolved in 1,4-dioxane (450 g). The solution is maintained at 40°C, 1,4-dioxane (50 g) and triethylamine (12.65 g) are mixed evenly and then dropped in, and stirred at 40°C for 2 hours. The triethylamine salt is filtered and the filtrate is poured into water. The precipitate is collected, washed with 1 L of 1% hydrochloric acid aqueous solution, and then washed twice with 2 L of water. The precipitate is dried in a vacuum dryer to obtain a quinone diazide compound (F) shown in formula (3).

[0069]

[0070] Among them, Q in formula (3) is independent Or H, and Q is not H at the same time.

[0071] In the present invention, the content of the thermal crosslinking compound is preferably 10 to 45 parts, and more preferably 15 to 40 parts; the thermal crosslinking compound comprises one or more of a compound having an epoxy structure, a compound having an oxetane structure, a compound having an alkoxymethyl group, and a compound having a benzoxazine structure, preferably one or more of a compound having an epoxy structure, a compound having an oxetane structure, and a compound having an alkoxymethyl group, and more preferably a compound having an epoxy structure. The thermal crosslinking compound used in the embodiment of the present invention is CYDCN-200 (trade name, manufactured by Sinopec Baling Petrochemical Company). The present invention uses a thermal crosslinking compound, which can not only improve the crosslinking density of the cured film, but also improve the chemical resistance and mechanical properties of the cured film.

[0072] In the present invention, the content of the silane coupling agent is 1 to 4 parts, more preferably 2 to 3 parts; the silane coupling agent comprises one or more of aminopropyl trimethoxysilane, trimethoxy epoxy silane, vinyl trimethoxy silane and mercaptopropyl trimethoxy silane, preferably one or more of aminopropyl trimethoxy silane, trimethoxy epoxy silane and vinyl trimethoxy silane, more preferably aminopropyl trimethoxy silane and / or trimethoxy epoxy silane. The silane coupling agent used in the embodiment of the present invention is γ-glycidyl ether oxypropyl trimethoxy silane. The use of a silane coupling agent can make the positive polyimide photosensitive resin composition have a higher adhesion to the substrate.

[0073] In the present invention, the amount of surfactant added is preferably 1 to 9 parts, and more preferably 2 to 8 parts; the surfactant includes one or more of a silicon-based surfactant, a fluorine-based surfactant and a nonionic surfactant, the silicon-based surfactant is preferably KP341 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso Corporation), Polyflow, Glanol (trade name, Kyoeisha Chemical Co., Ltd.), BYK (trade name, BYK-Chemie GmbH), the fluorine-based surfactant is preferably Fluorad (trade name, Sumitomo 3M Co., Ltd.), Megafac (trade name, DIC Co., Ltd.), Surflon (trade name, Asahi Glass Co., Ltd.), and the nonionic surfactant is preferably Polyflow (trade name, Kyoeisha Chemical Co., Ltd.). The present invention can improve the coverage performance, construction performance and uniformity of the positive polyimide photosensitive resin composition by adding a surfactant.

[0074] In the present invention, the solvent comprises one or more of an amide solvent, a ketone solvent, an ester solvent, an ether solvent, a sulfoxide solvent, a sulfone solvent, a phenol solvent and an aromatic hydrocarbon solvent, wherein the amide solvent is preferably one or more of N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide and hexamethylphosphoric acid triamide; the ketone solvent is preferably one or more of N-methyl-2-pyrrolidone, cyclopentanone and cyclohexanone; the ester solvent is one or more of γ-butyrolactone, ethyl acetate, butyl acetate and ethyl lactate; the ether solvent is preferably one or more of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and p-cresol methyl ether; the sulfoxide solvent is preferably dimethyl sulfoxide; the sulfone solvent is preferably diphenyl sulfone and / or tetramethyl sulfone; the phenol solvent is preferably phenol and / or cresol; the aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene. Among them, ester solvents such as ethyl lactate can improve the wettability between the positive polyimide photosensitive resin composition and the substrate, and ether solvents such as tetrahydrofuran can improve the stability of the solution.

[0075] The method for coating the positive polyimide photosensitive resin composition provided by the present invention on a substrate is preferably a slit coating method, a spin coating method, a dip coating method, a roller coating method, a screen coating method, a spray coating method, a flow coating method, a screen printing method, an inkjet method or a nozzle coating method. The positive polyimide photosensitive resin composition of the present invention has high solvent properties and is suitable for the slit coating method.

[0076] The positive polyimide photosensitive composition of the present invention can use an aqueous solution of alkali as a developing solution, and the aqueous solution of alkali is selected from an aqueous solution of tertiary ammonium hydroxide or an aqueous solution of amine; the tertiary ammonium hydroxide is preferably tetramethylammonium hydroxide or tetraethylammonium hydroxide; the aqueous solution of amine is preferably an aqueous ammonia solution, an ethylamine solution, a propylamine solution, a diethylamine solution or a triethylamine solution. When evaluating the resolution of the positive polyimide photosensitive composition of the present invention, a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 2.38wt% is used. Compared with organic solvents, the developing solution is environmentally friendly and economical.

[0077] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0078] The evaluation method of the positive polyimide photosensitive composition of the present invention is as follows:

[0079] (1) Evaluation of the solubility of resin in organic solvents:

[0080] The positive polyimide photosensitive composition and the mixed solvent (GBL / PM=10 / 90) were mixed to obtain a mixture with a mass concentration of 30%, stirred at room temperature for 1 hour, and then visually observed to confirm whether there was insoluble resin. If no insoluble resin was observed, it was judged as "dissolved", and if insoluble resin was confirmed, it was judged as "insoluble". The resin solution was then refrigerated at -15°C for 24 hours to observe whether there were abnormal conditions such as precipitation or gelation. If there was precipitation or gelation, it was judged as "insoluble".

[0081] (2) Resolution evaluation:

[0082] The positive polyimide photosensitive composition solution of the present invention is coated on the surface of a 6-inch or 8-inch silicon wafer by spin coating or spray coating, and pre-baked at 110° C. for 2 to 3 minutes to make the cornea thickness after pre-baking 4.8 to 5.5 μm. An exposure machine (i-line stepper) is used for exposure treatment. A 2.38% TMAH aqueous solution is used for development for 90 to 120 seconds, and after high-purity water washing, the positive pattern is blown dry to obtain a positive pattern. The resolution is determined by observation under a microscope and the film retention rate is measured by a step profiler. The minimum distinguishable hole size is used as the resolution.

[0083] (3) Evaluation of film retention rate:

[0084] The film retention rate is calculated according to the following formula:

[0085] Film retention rate (%) = film thickness after development ÷ film thickness after pre-baking × 100%

[0086] (4) Evaluation of residual film rate:

[0087] The prepared photosensitive polyimide film was baked in a blast oven at 250°C for 1 hour to obtain a cured polyimide film. The residual film rate was calculated according to the following formula:

[0088] Residual film rate (%) = film thickness after curing ÷ film thickness after development × 100%

[0089] (5) Evaluation of curing film forming temperature:

[0090] The prepared photosensitive polyimide film is baked in a forced air oven at a temperature and time of 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, or 350°C for 1 hour, and then immersed in 1% hydrofluoric acid to determine whether the film can be peeled off. The curing temperature used when the film can be formed is used as the evaluation.

[0091] The following are the structures and abbreviations of the main compounds used in the examples: [Solvent]

[0092] NMP: N-methyl-2-pyrrolidone

[0093] GBL: gamma-butyrolactone

[0094] PM: Propylene glycol monomethyl ether

[0095]

Diamine

[0096] DA-1: (428.19)

[0097]

[0098] DA-2: ODA: 4,4-diphenyl ether diamine (200.12)

[0099]

[0100] DA-3: (292.18)

[0101]

[0102] DA-4: (109.06)

[0103] 3-Aminophenol (capping agent)

[0104]

Dianhydride

[0105] DG-1: ODPA: 4,4-diphenyl ether dianhydride (310.17)

[0106]

[0107] DG-2: CBDA: Cyclobutanetetracarboxylic dianhydride (196.09)

[0108]

[0109] DG-3: HPMDA: Hydrogenated pyromellitic dianhydride (224.11)

[0110]

[0111]

Other additives

[0112] Compounds having epoxy groups: CYDCN-200 (trade name, manufactured by Sinopec Baling Petrochemical Company)

[0113] Silane coupling agent: KH560, γ-glycidyloxypropyltrimethoxysilane

[0114] Surfactant: KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0115] Synthesis example 1

[0116] Non-fluorinated polyamide ester PAE-1: Under a nitrogen atmosphere, add DA-3 (29.22 g, 0.1 mol) and NMP (191.84 g) to a dry three-necked bottle, stir and react at 60°C for 0.5 hour to form a homogeneous solution; then add DG-2 (17.65 g, 0.09 mol) to the solution, stir and react at 60°C for 3 hours, then add 3-aminophenol (1.09 g, 0.01 mol), and continue to react at room temperature for 2 hours.

[0117] Add excess butanol (14.82 g, 0.2 mol) to the polyamic acid resin solution obtained by the above reaction, react at room temperature for 4 hours to obtain a polyamide ester solution; slowly drop the reaction solution into a large amount of water for precipitation, filter the precipitated solution, collect the solid, then soak and rinse the solid twice with a large amount of ethanol and filter it, and dry it in a vacuum oven at 60°C under reduced pressure for 12 hours to obtain polyamide ester PAE-1 for standby use.

[0118] Synthesis example 2

[0119] Non-fluorinated polyamide ester PAE-2: Under a nitrogen atmosphere, add DA-3 (29.22 g, 0.1 mol) and NMP (196.84 g) to a dry three-necked bottle, stir and react at 60°C for 0.5 hour to form a homogeneous solution; then add DG-2 (8.82 g, 0.045 mol) and DG-3 (10.08 g, 0.045 mol) to the solution, stir and react at 60°C for 3 hours, then add 3-aminophenol (1.09 g, 0.01 mol), and continue to react at room temperature for 2 hours.

[0120] Add excess butanol (14.82 g, 0.2 mol) to the polyamic acid resin solution obtained by the above reaction, and react at room temperature for 4 hours to obtain a polyamide ester solution; slowly drop the reaction solution into a large amount of water for precipitation, filter the precipitated solution, collect the solid, and then soak and rinse the solid twice with a large amount of ethanol and filter it, and dry it in a vacuum oven at 60°C under reduced pressure for 12 hours to obtain a polyamide ester resin powder PAE-2 for standby use.

[0121] Synthesis example 3

[0122] Fluorinated polyamic acid PAA-1: Under a nitrogen atmosphere, add DA-1 (4.28 g, 0.01 mol), DA-2 (18.01 g, 0.09 mol) and NMP (205.20 g) to a dry three-necked flask and stir at room temperature for 30 minutes to form a homogeneous solution; then add DG-1 (27.92 g, 0.09 mol) to the solution, stir at room temperature for 3 hours, then add 3-aminophenol (1.09 g, 0.01 mol), and continue to react at room temperature for 2 hours.

[0123] The reaction solution was poured into a large amount of water for precipitation, the precipitated solution was filtered, the solid was collected, and then the solid was soaked and rinsed with a large amount of anhydrous ethanol for two or more times, filtered, and dried under reduced pressure at 60° C. for 12 hours to obtain a polyamic acid solid powder PAA-1 for standby use.

[0124] Synthesis example 4

[0125] Fluorinated polyamic acid PAA-2: Under a nitrogen atmosphere, add DA-1 (38.54 g, 0.09 mol), DA-2 (2.00 g, 0.01 mol) and NMP (278.20 g) to a dry three-necked flask and stir at room temperature for 30 minutes to form a homogeneous solution; then add DG-1 (27.92 g, 0.09 mol) to the solution, stir at room temperature for 3 hours, then add 3-aminophenol (1.09 g, 0.01 mol), and continue to react at room temperature for 2 hours.

[0126] The reaction solution was poured into a large amount of water for precipitation, the precipitated solution was filtered, the solid was collected, and then the solid was soaked and rinsed with a large amount of anhydrous ethanol for two or more times, filtered, and dried under reduced pressure at 60° C. for 12 hours to obtain a polyamic acid solid powder PAA-2 for standby use.

[0127] Synthesis example 5

[0128] Non-fluorinated polyimide PI-1: Under a nitrogen atmosphere, add DA-3 (29.22 g, 0.1 mol) and NMP (196.84 g) to a dry three-necked bottle, stir at 60 ° C for 0.5 hour to form a homogeneous solution; then add DG-2 (8.82 g, 0.045 mol) and DG-3 (10.08 g, 0.045 mol) to the solution, stir at 60 ° C for 3 hours, then add 3-aminophenol (1.09 g, 0.01 mol), and continue to react at room temperature for 2 hours.

[0129] Acetic anhydride (16.33 g) and pyridine (12.66 g) were further added to the polyamic acid solution, and the reaction was carried out at room temperature for 2 h. After the reaction was completed, the reaction solution was poured into a large amount of ethanol for precipitation, the precipitated solution was filtered, the solid was collected, and the solid was rinsed twice with a large amount of ethanol, filtered, and dried under reduced pressure in a vacuum oven at 60° C. for 12 h to obtain a polyimide solid powder PI-1 (imidization rate was 80%).

[0130] Example 1

[0131] 50 parts of PAA-1 resin, 50 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0132] Example 2

[0133] 90 parts of PAA-1 resin, 10 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0134] Example 3

[0135] 50 parts of PAA-2 resin, 50 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts by weight of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, and 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0136] Example 4

[0137] 50 parts of PAA-1 resin, 50 parts of PAE-2 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts by weight of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0138] Example 5

[0139] 50 parts of PAA-2 resin, 50 parts of PAE-2 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts by weight of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0140] Example 6

[0141] 70 parts of PAA-1 resin, 30 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0142] Example 7

[0143] 30 parts of PAA-2 resin, 70 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of thermal crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0144] Example 8

[0145] 50 parts of PAA-1 resin, 50 parts of PAE-1 resin, 30 parts of quinonediazide compound (F), 5 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0146] Comparative Example 1

[0147] 100 parts of PAA-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0148] Comparative Example 2

[0149] 100 parts of PAE-2 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the weight ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0150] Comparative Example 3

[0151] 100 parts of PI-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0152] Comparative Example 4

[0153] 50 parts of PAA-1 resin, 50 parts of PI-1 resin, 25 parts of quinonediazide compound (F), 10 parts of thermal crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0154] Comparative Example 5

[0155] 90 parts of PAA-2 resin, 10 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0156] Comparative Example 6

[0157] 10 parts of PAA-2 resin, 90 parts of PAE-1 resin, 25 parts of quinonediazide compound (F), 10 parts of heat-crosslinking compound CYDCN-200, 5 parts of γ-glycidyloxypropyltrimethoxysilane, 15 parts of surfactant KP34, 560 parts of GBL / PM solvent, wherein the mass ratio of GBL to PM is 10:90, are mixed to obtain a positive polyimide photosensitive composition, which is used to prepare a varnish; wherein Q in the quinonediazide compound (F) is

[0158] The compositions of the positive polyimide photosensitive compositions of Examples 1 to 8 and Comparative Examples 1 to 6 of the present invention are shown in Table 1.

[0159] Table 1 Composition of positive polyimide photosensitive composition

[0160]

[0161]

[0162] The present invention evaluates the performance of the positive polyimide photosensitive compositions of Examples 1 to 8 and Comparative Examples 1 to 6. The results are shown in Table 2:

[0163] Table 2 Performance evaluation results

[0164]

[0165] The results of Table 2 show that, by comparing Examples 1 to 8 with Comparative Examples 3 and 4, it can be seen that the addition of polyamide ester will increase the solubility of the film-forming resin, while the resin with the addition of polyimide has poor solubility in the solvent and is easily precipitated after refrigeration at -15°C for 24 hours. By comparing Examples 1 to 8 with Comparative Examples 1 to 3, it can be seen that only one resin component is added to the film-forming resin, whether it is polyimide, polyamic acid, or polyamide ester, it is impossible to develop an ideal pattern. By comparing Examples 1, 3 with Examples 6 and 7, it can be seen that when the film-forming resin contains high fluorine atoms, the film retention rate will increase, but the resolution will decrease, and the appropriate ratio will enable the film-forming resin to maintain a high resolution while having a high film retention rate. By comparing Examples 4, 5 and 1, it can be seen that the structure of polyamide ester is multi-element, which will increase the residual film rate of the film-forming resin. By comparing Example 2 with Comparative Examples 5 and 6, it can be seen that when the polyamic acid content in the film-forming resin is high, the high fluorine atoms will make the resolution extremely low and difficult to develop, while when the polyamic acid content is low, it will lead to an inability to develop. By comparing Example 1 with Example 8, it can be seen that increasing the amount of quinone diazide compound will increase the film retention rate, and the corresponding residual film rate will decrease.

[0166] As can be seen from the above embodiments, the present invention provides a polyimide and polyamic acid and a positive polyimide photosensitive resin composition for a display device. The present invention synthesizes a polyamide ester containing a structural unit (1) and a polyamic acid having a structural unit (2), and then mixes a polyimide resin, a diazo naphthoquinone, a thermal crosslinking compound, a silane coupling agent, a surfactant, and a solvent to prepare a positive polyimide photosensitive resin composition, wherein the polyimide resin is composed of polyamide ester and polyamic acid. The organic insulating layer prepared by the positive photosensitive polyimide composition of the present invention can be cured at a temperature of 200°C or below, has high solubility in an organic solvent, and has excellent adhesion to a substrate and high resolution.

[0167] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A positive polyimide photosensitive resin composition for a display device, characterized in that: The invention comprises the following components in parts by weight: 100 parts of polyimide resin, 1 to 50 parts of diazo naphthoquinone, 5 to 50 parts of thermal crosslinking compound, 0.01 to 5 parts of silane coupling agent, 0.01 to 10 parts of surfactant, and 20 to 2000 parts of solvent; the polyimide resin is composed of polyamide ester and polyamic acid; the mass ratio of the polyamide ester to the polyamic acid is 30:70 to 70:30; The polyesteramide comprises the structural unit (1): In the structural unit (1), X1 represents a tetravalent alicyclic tetracarboxylic dianhydride residue, Y1 represents a divalent aromatic diamine residue, and R1 represents C 1～5 Alkyl, C 3～10 A cycloalkyl or aromatic group, m is an integer between 100 and 1000; The preparation method of polyamide ester comprises the following steps: in a nitrogen protective atmosphere, an aromatic diamine and an organic solvent are mixed to carry out a first-stage reaction until a homogeneous solution is formed; then alicyclic dianhydride is added to the aromatic diamine solution to carry out a second-stage reaction to generate a polyamide acid resin solution through a condensation reaction; Finally, an excess amount of organic alcohol compound is added to the polyamic acid resin solution to carry out a third stage reaction to obtain polyamide ester; The Y1 is selected from one of the structures of E9 to E16: ； The polyamic acid comprises a structural unit (2), wherein the structural unit (2) comprises two isomers (c) and (d): wherein X3 represents a residue of a tetravalent aromatic tetracarboxylic dianhydride, Y2 represents a residue of a divalent aromatic diamine, and n is an integer between 50 and 1000; The Y2 is selected from one of the structures of E1 to E8: 。 2. The positive polyimide photosensitive resin composition for a display device according to claim 1, characterized in that: The residue of the tetravalent alicyclic tetracarboxylic dianhydride is selected from one of the structures of C1 to C6: 。 3. The positive polyimide photosensitive resin composition for a display device according to claim 1, characterized in that: The residue of the tetravalent aromatic tetracarboxylic dianhydride is selected from one of the structures of D1 to D9: 。 4. The positive polyimide photosensitive resin composition for a display device according to claim 1, characterized in that: The diazonaphthoquinone includes a compound obtained by sulfonamide bonding of sulfonic acid of quinonediazide to a polyamino compound, a compound obtained by ester bonding of sulfonic acid of quinonediazide to a polyhydroxy compound, or a compound obtained by ester bonding and / or sulfonamide bonding of sulfonic acid of quinonediazide to a polyhydroxypolyamino compound.

5. The positive polyimide photosensitive resin composition for a display device according to claim 4, characterized in that: The heat-crosslinkable compound includes one or more of a compound having an epoxy structure, a compound having an alkoxymethyl group, and a compound having a benzoxazine structure.

6. The positive polyimide photosensitive resin composition for a display device according to claim 1, characterized in that: The thermally crosslinkable compound includes a compound having an oxetane structure.

7. A positive polyimide photosensitive resin composition for a display device according to any one of claims 1 to 6, characterized in that: The silane coupling agent comprises one or more of aminopropyltrimethoxysilane, trimethoxyepoxysilane, vinyltrimethoxysilane and mercaptopropyltrimethoxysilane.

8. The positive polyimide photosensitive resin composition for a display device according to claim 7, characterized in that: The surfactant comprises one or more of a silicon-based surfactant, a fluorine-based surfactant and a non-ionic surfactant.

9. The positive polyimide photosensitive resin composition for a display device according to claim 8, characterized in that: The solvent comprises one or more of an amide solvent, a ketone solvent, an ester solvent, an ether solvent, a sulfoxide solvent, a sulfone solvent, a phenol solvent and an aromatic hydrocarbon solvent.

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