Photosensitive resin compound for insulating flat layer of display device as well as preparation method and application of photosensitive resin compound

Abstract

The invention discloses a photosensitive resin compound for an insulating flat layer of a display device as well as a preparation method and application of the photosensitive resin compound. The photosensitive ink comprises the following components in parts by weight: 10-30 parts of styrene acrylic resin, 1-15 parts of a siloxane compound, 1-10 parts of a photosensitive compound, 0.5-2 parts of an auxiliary agent and 150-300 parts of a solvent, wherein the photosensitive compound is diazo naphthoquinone ester containing a plurality of phenolic hydroxyl groups; the styrene acrylic resin is prepared according to the following steps: mixing a functional monomer, a hydrophilic monomer, a crosslinking monomer, a hydrophobic monomer and styrene, and carrying out polymerization reaction under the action of an initiator, so as to obtain the styrene acrylic resin. After film formation, the photosensitive resin compound has excellent insulativity, flatness and visible light permeability, also has good chemical stability, weather resistance and high heat resistance, and can be used for interlayer insulating films in display products or other electronic products.

Description

Technical Field

[0001] The present invention belongs to the field of photosensitive resin composites, and specifically comprises a photosensitive resin composite for an insulating flat layer of a display device, a preparation method thereof, and an application thereof. Background Art

[0002] In display components and certain electronic consumer products, an insulating layer is required to separate different functional layers such as circuit components and wiring layers. For example, an insulating material is required to separate the TFT transistor and the ITO wiring layer. Although high-purity inorganic non-metallic materials have good insulation properties, they are expensive, so organic materials are used as interlayer insulating layers. This interlayer insulating film needs to have good insulation, flatness and reliability. For the display panel industry, it may also need to have good visible light transmittance. In order to maintain normal connection between the upper and lower functional layers, the film layer also needs to transfer the circuit pattern through a photolithography process, so the film layer needs to be photosensitivity.

[0003] The general process for preparing the film layer is to apply the interlayer insulating film glue on the base transistor circuit board, and then undergo vacuum drying, pre-baking, exposure, development, photobleaching, and finally a post-baking process to completely solidify the resin composition film layer to become an insoluble and infusible tough film layer.

[0004] The resin used in traditional interlayer insulation materials is acrylic resin or modified acrylic resin. Pure acrylic resin has poor chemical resistance and heat resistance after film formation. Modified acrylic resin is obtained by adding styrene monomers during the resin preparation process. The modified acrylic resin has improved chemical resistance and heat resistance, but with the miniaturization of panels and electronic products, the requirements for materials are gradually increasing, and the film layer prepared by modified acrylic resin is difficult to meet application requirements. In order to meet more stringent usage requirements, technicians have developed interlayer insulation film products with silicone resin as the main body. Silicone resin has better chemical resistance, heat resistance and flatness, but silicone-based insulation film products also face other problems during use: silicone resin has a high cross-linking density, is hard and brittle in nature, and the film layer is easily damaged during use and processing. In addition, due to its special silanol structure, silicone resin is very easy to cross-link, resulting in failure of the glue gel. At present, silicone-based insulation film products have not been actually promoted and applied.

[0005] Therefore, a tough, insulating, heat-resistant, transparent, photosensitive, chemical-resistant and reliable film layer is needed to meet the interlayer insulation requirements in electronic products such as display products. Summary of the Invention

[0006] In response to the aforementioned problems in the prior art, the first object of the present invention is to provide a photosensitive resin composite for use in insulating and planarizing layers of display devices. This photosensitive resin composite, after film formation, exhibits excellent insulation, planarization, and visible light transmittance. It also exhibits good chemical stability, weather resistance, and high heat resistance, and can be used as an interlayer insulating film in display products and other electronic products.

[0007] The second object of the present invention is to provide a method for preparing the photosensitive resin composite as described above.

[0008] A third object of the present invention is to provide a planarization layer prepared using the photosensitive resin composite described above.

[0009] A fourth object of the present invention is to provide a display device comprising the planarization layer as described above.

[0010] To achieve the above first object, the technical solution adopted by the present invention includes:

[0011] The present invention discloses a photosensitive resin composite for an insulating flat layer of a display device, which comprises, by weight, 10 to 30 parts of a styrene acrylic resin, 1 to 15 parts of a siloxane compound, 1 to 10 parts of a photosensitive compound, 0.5 to 2 parts of an auxiliary agent, and 150 to 300 parts of a solvent;

[0012] Wherein, the photosensitizing compound is a diazonaphthoquinone ester containing multiple phenolic hydroxyl groups;

[0013] The styrene acrylic resin is prepared according to the following steps:

[0014] Functional monomers, hydrophilic monomers, cross-linking monomers, hydrophobic monomers and styrene are mixed and polymerized under the action of an initiator to obtain styrene acrylic resin.

[0015] The functional monomer is selected from one of the following structural formulas:

[0016]

[0017] Wherein, A is hydrogen or methyl, n is a positive integer of 1 to 6, and R is selected from one or more of hydrogen, an alkyl group or alkoxy group having carbon atoms of C1-C3, and a hydroxyl group.

[0018] This photosensitive resin composite is based on a highly thermally stable styrene acrylic resin, with a silicone compound added. During the post-curing process, the silicone compound condenses into polysiloxane, which, together with the highly heat-resistant styrene acrylic resin, forms an interpenetrating polymer network (IPN) structure. This structure retains the heat resistance, weather resistance, and high reliability of silicone resin while overcoming its film brittleness and storage difficulties. The resulting film exhibits excellent storage stability, good coating application, smooth and flawless coating, and a tough film. It also exhibits excellent visible light transmittance, chemical resistance, and heat resistance.

[0019] It should be noted that, based on a large number of experimental screenings, it was found that in the preparation process of styrene acrylic resin, the introduction of at least one functional monomer of formulas I-1 to I-4 and cross-linking with other common acrylic monomers and styrene to form a styrene acrylic resin is beneficial to the formation of a strong cross-linked structure of the styrene acrylic resin in the subsequent film curing process, thereby greatly improving the heat resistance, chemical resistance and reliability of the film.

[0020] Furthermore, the functional monomer is selected from one of the following structures:

[0021]

[0022] Furthermore, other conventional acrylic monomers are selected from hydrophilic monomers such as methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylamide, acrylamide, acryloylmorpholine, 3-methacryloyloxypropionic acid, and 2-sulfonic acid ethyl methacrylate; cross-linking monomers such as glycidyl methacrylate, ethylene glycol acetoacetate methacrylate, allyl methacrylate, diacetone acrylamide, oxetane methacrylate, methacryloyloxypropyltrimethoxysilane, vinyl methacrylate, and N-methoxyacrylamide; and hydrophobic monomers such as isobornyl methacrylate, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, and adamantyl methacrylate.

[0023] Furthermore, the styrene acrylic resin is prepared according to the following steps:

[0024] The functional monomer, the hydrophilic monomer, the cross-linking monomer, the hydrophobic monomer and styrene are mixed, tetrahydrofuran and an initiator are added to the monomer mixture obtained above, and the mixture is stirred to be fully mixed;

[0025] Heat to 60-68°C in an inert atmosphere for polymerization reaction. After reacting for 2-6 hours, cool to room temperature. Then slowly pour the cooled reaction liquid into stirring n-heptane to obtain a resin precipitate. Filter and vacuum dry to obtain styrene acrylic resin.

[0026] Furthermore, the monomer mixture comprises 5 to 20 wt% of functional monomers, 15 to 40% of hydrophilic monomers, 10 to 30 wt% of cross-linking monomers, 20 to 40 wt% of hydrophobic monomers, and 15 to 50 wt% of styrene. When the content of the hydrophilic group introduced by the hydrophilic monomer is too high, the retention rate of the photosensitive resin composition film layer during the development process will be reduced, low-molecular substances will be dissolved, or other defects will occur. When the content of the hydrophobic group introduced by the hydrophobic monomer is too high, the photosensitive resin composition film layer will be difficult to dissolve, and problems such as development residues and bottom residues will occur. When the content of the cross-linking monomer is too high, the cross-linking density of the photosensitive resin composition film layer will be too high, the film layer will be hard and brittle, and the storage stability and reliability will be reduced. When the content is too low, the photosensitive resin composition film layer will not be sufficiently cross-linked, and the insulation, chemical resistance, and thermal stability of the film layer will be reduced. The content of the hydrophobic acrylic monomer should be adjusted according to the content of styrene. If the content is too high, the photosensitive resin composition film will be too hydrophobic, making it difficult to remove during the development process. If the content is too low, the photosensitive resin composition film will be too hydrophilic, causing rapid dissolution during the development process or forming other defects. In general, the total content of the hydrophobic acrylic monomer and styrene should be 10-60wt% of the monomer mixture, preferably 30-50wt%.

[0027] Furthermore, the mass ratio of the monomer mixture, tetrahydrofuran and initiator is 1:2-4:0.03-0.15.

[0028] Furthermore, the mass ratio of the siloxane compound to the styrene acrylic resin is 1 to 50%:1, preferably 10 to 40%:1.

[0029] Furthermore, the photosensitive resin composite comprises, by weight, 10 to 20 parts of styrene acrylic resin, 1 to 10 parts of siloxane compound, 2 to 5 parts of photosensitive compound, 0.5 to 2 parts of auxiliary agent and 150 to 300 parts of solvent.

[0030] Furthermore, the weight average molecular weight of the styrene acrylic resin is 5,000 to 20,000, with a molecular weight distribution of 1.5 to 2.5. If the weight average molecular weight is too high, the formed film layer will be difficult to remove during development, resulting in development residues. If the weight average molecular weight is too low, development defects such as low film retention and rough film surface will occur after development.

[0031] Furthermore, the siloxane compound is selected from one or more of trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxydimethylsilane, and diethoxydiphenylsilane. The above siloxanes can be used alone or in combination as needed. When used, the siloxane monomer should be selected based on the properties of the styrene acrylic resin and have good compatibility and a moderate crosslinking rate.

[0032] Furthermore, the photosensitive compound is selected from one of the following structures:

[0033]

[0034] Where D is H or And D is not H at the same time.

[0035] The above-mentioned photosensitive compounds all contain multiple non-conjugated benzene rings in their structures to prevent the absorption of visible light, which leads to a decrease in the transmittance of the film. In a specific embodiment, the degree of esterification of the above-mentioned photosensitive compounds is 50% to 100%, depending on the content of diazonaphthoquinone. In addition, the above-mentioned photosensitive compounds can be used alone or in combination, and their usage is further limited to 10wt% to 30wt% of the sum of the weight of the styrene acrylic resin and the siloxane compound in the resin composition. Too low a content will cause the film to dissolve too quickly, reduce the film retention rate, and cause soluble matter in the film to precipitate. Too high a content will increase the exposure energy used in the exposure process of the film, affecting production efficiency, and will also cause the acidity of the film to increase, reducing the chemical stability and moisture resistance of the film.

[0036] The photosensitive resin composite provided by the present invention may also require the addition of appropriate additives based on the workability requirements. For example, the additives include leveling agents, defoaming agents, anti-blocking agents, crosslinking agents, antioxidants, UV absorbers, free radical scavengers, and other additives used to improve the workability, heat resistance, and storage stability of the photosensitive resin composite.

[0037] For example, the leveling agent can be one or more of FC4431 (3M), S366 (Troy), BYK-333 (Bick), etc., the defoaming agent can be one or more of DF-103T (Dow), AFE-3168 (Dow), Defom 6800 (Hemmingsdeqian), etc.; the antioxidant can be Irganox168, Irganox 1010, Irganox1076, Irganox B225 (BASF), etc.; the free radical scavenger can be selected from one or more of 2,2-biphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl nitroxide free radical, tetramethylpiperidinyl nitroxide free radical phosphite triester, etc.; the opening agent can be selected from one or more of oleamide, erucamide, etc.; the cross-linking agent can be selected from one or more of triallyl isocyanurate, tetramethoxymethyl glycoluril, 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, P-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, diglycidyl ether, etc.; the UV absorber can be selected from one or more of tinuvin 571, HS-508, UV-P, UV-328, etc.

[0038] Furthermore, the solvent is selected from one or more of propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, anisole, propylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethylene glycol monoacetate, ethylene glycol diacetate, ethyl lactate, γ-butyrolactone, butanone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone.

[0039] To achieve the above second purpose, the technical solutions adopted by the present invention include:

[0040] The present invention discloses a method for preparing the above-mentioned photosensitive resin composite, comprising the following steps:

[0041] Styrene acrylic resin, silicone compound, photosensitive compound, additive and solvent are mixed, stirred at room temperature to completely dissolve them, and filtered through 0.5μm, 0.1μm and 0.05μm filter elements in sequence for 36-48 hours to obtain a photosensitive resin composite.

[0042] To achieve the third objective, the present invention employs the following technical solutions:

[0043] The present invention discloses a planarization layer for a display device. The planarization layer is obtained by coating the above-mentioned photosensitive resin composite on a substrate by spin coating, roller coating or blade coating, and then drying under reduced pressure, pre-baking, exposing, developing and curing.

[0044] Furthermore, the reduced pressure drying can remove most of the solvent. In one embodiment, the reduced pressure drying temperature is 20-40°C, and the reduced pressure drying pressure is 20-400Pa.

[0045] Furthermore, the pre-baking can not only completely remove the solvent, but also preliminarily bake the film. In one embodiment, the pre-baking temperature is 75-120°C, the pre-baking time is 180-300 seconds, and the thickness of the pre-baked film is between 1 micron and 5 microns.

[0046] Furthermore, the exposure is to expose the film layer with near-ultraviolet and visible light of 330-450nm wavelength through a mask, and the energy used for exposure is 40-300mJ / cm 2 .

[0047] Furthermore, the development is to immerse the exposed film layer in a developer, or to evenly spray the developer on the surface of the film layer to remove the exposure pattern. The developer can be an alkaline aqueous solution, including inorganic solutions such as potassium hydroxide and potassium carbonate, or organic alkaline solutions such as tetramethylammonium hydroxide and triethylamine, and the concentration of these alkaline solutions is between 0.1% and 5%. And an appropriate amount of water-soluble organic solvents such as ethanol and N-methylpyrrolidone can be added to increase the wettability of the developer. In a specific embodiment, the development time is 30 to 150 seconds, and after the development is completed, the film layer is washed with deionized water for 20 to 90 seconds, and the surface of the film layer is blown dry with a clean air flow or placed on a 100°C surface for drying.

[0048] Furthermore, the curing is carried out with 150 to 800 mJ / cm 2 After irradiation with 365nm ultraviolet light, it is placed on a heating device such as a hot plate or an oven and heat treated at a temperature of 200-250°C for 15-45 minutes to obtain the final patterned film layer.

[0049] To achieve the fourth objective, the present invention employs the following technical solutions:

[0050] The present invention discloses a display device comprising the planarization layer described above.

[0051] Beneficial effects of the present invention:

[0052] The present invention provides a photosensitive resin composite for an insulating flat layer of a display device, and its preparation method and application. By selecting a highly thermally stable styrene acrylic resin with a specific structure as a crosslinking main body and using it in combination with a corresponding siloxane compound, a polysiloxane formed by condensation of the siloxane compound and the highly heat-resistant styrene acrylic resin can be formed into an interpenetrating polymer network (IPN) structure during the post-curing process. This structure retains the heat resistance, weather resistance, and high reliability advantages of silicone resin while overcoming the defects of its film brittleness and difficulty in preservation. The resulting film has good storage stability and good coating construction properties, with a flat and flawless coating, a tough film layer, and good visible light transmittance, chemical resistance, and heat resistance. It achieves performance comparable to that of a photosensitive polysiloxane resin composite, and its storage stability is even better than that of a photosensitive polysiloxane resin composite. Therefore, it is expected to be widely used in the preparation of interlayer insulating films in display products or other electronic products.

[0053] In addition, the preparation of styrene acrylic resin is also very critical for achieving the above-mentioned effects. It is precisely because of the selection of suitable functional monomers that the prepared styrene acrylic resin has excellent properties such as good heat resistance, chemical resistance, reliability, and visible light transmittance, which is conducive to the preparation of photosensitive resin composites that meet application requirements. DETAILED DESCRIPTION

[0054] In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the content described below is illustrative and non-restrictive and should not be used to limit the scope of protection of the present invention. The preparation methods in the present invention are all conventional methods unless otherwise specified. The raw materials used can be obtained from public commercial sources or prepared according to the prior art unless otherwise specified.

[0055] Example 1

[0056] Preparation of Styrene Acrylic Resin

[0057] 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 10 parts by weight of azobisisoheptonitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer, and 20 parts by weight of 2-methyl-2-[(phenoxycarbonyl)amino]ethyl methacrylate was added.

[0058] The flask was vacuum-purged with nitrogen while stirring. After the materials dissolved, the temperature was raised to 66°C and maintained at this temperature for 6 hours. The mixture was then cooled to room temperature to obtain a styrene acrylic resin solution. The styrene acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the styrene acrylic resin solution precipitated, and the solution was filtered and vacuum-dried to obtain a pure styrene acrylic resin having a weight-average molecular weight of approximately 8000 and a molecular weight distribution of 1.82.

[0059] Preparation of photosensitive resin composites

[0060] 100 parts by weight of the styrene acrylic resin prepared above, 30 parts by weight of the ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 10 parts by weight of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane and 10 parts by weight of methacryloxypropyltrimethoxysilane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid 5 parts by weight of ester, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate and 180 parts by weight of propylene glycol methyl ether are mixed together and stirred to dissolve. After thorough dissolution to form a uniform solution, the resulting solution is filtered in series through 0.5 micron, 0.1 micron and 0.05 micron filter elements for 48 hours to obtain a photosensitive resin composite.

[0061] Example 2

[0062] Preparation of Styrene Acrylic Resin

[0063] 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 10 parts by weight of azobisisoheptonitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer, and 10 parts by weight of the following monomers were added:

[0064]

[0065] The flask was vacuum-purged with nitrogen while stirring. After the materials dissolved, the temperature was raised to 66°C and maintained at this temperature for 6 hours. The mixture was then cooled to room temperature to obtain a styrene acrylic resin solution. The styrene acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the styrene acrylic resin solution precipitated, and the solution was filtered and vacuum-dried to obtain a pure styrene acrylic resin having a weight-average molecular weight of 8000 and a molecular weight distribution of 1.87.

[0066] Preparation of photosensitive resin composites

[0067] 100 parts by weight of the styrene acrylic resin prepared above, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 20 parts by weight of 3-glycidyloxypropyltrimethoxysilane, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (Bick) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 micron, 0.1 micron, and 0.05 micron filter cartridges in series for 48 hours to obtain a photosensitive resin composite.

[0068] Example 3

[0069] Preparation of Styrene Acrylic Resin

[0070] 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 10 parts by weight of azobisisoheptonitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer, and 10 parts by weight of the following monomers were added:

[0071]

[0072] The flask was vacuum-purged with nitrogen while stirring. After the materials dissolved, the temperature was raised to 66°C and maintained at this temperature for 6 hours. The mixture was then cooled to room temperature to obtain a styrene acrylic resin solution. The styrene acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the styrene acrylic resin solution precipitated, and the solution was filtered and vacuum-dried to obtain a pure styrene acrylic resin having a weight-average molecular weight of 8000 and a molecular weight distribution of 1.81.

[0073] Preparation of photosensitive resin composites

[0074] 100 parts by weight of the styrene acrylic resin prepared above, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 20 parts by weight of vinyltrimethoxysilane, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 μm, 0.1 μm, and 0.05 μm filter cartridges in series for 48 hours to obtain a photosensitive resin composite.

[0075] Comparative Example 1

[0076] Photosensitive acrylic resin composition

[0077] 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 15 parts by weight of methyl methacrylate, 30 parts by weight of styrene, 10 parts by weight of azobisisoheptanenitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer for resin synthesis.

[0078] The flask was then vacuum-purged with nitrogen while stirring. The temperature was raised to 66°C and maintained at this temperature for 6 hours. The solution was then cooled to room temperature to obtain an acrylic resin solution. The acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the acrylic resin solution precipitated, and the solution was filtered and vacuum-dried to obtain an acrylic resin having a weight-average molecular weight of approximately 8000 and a molecular weight distribution of 1.88.

[0079] Preparation of photosensitive resin composites

[0080] 100 parts by weight of the acrylic resin prepared above, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 μm, 0.1 μm, and 0.05 μm filter cartridges in series for 48 hours to obtain a photosensitive resin composite.

[0081] Comparative Example 2

[0082] Photosensitive resin composite

[0083] 100 parts by weight of the styrene acrylic resin prepared in Example 3, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 20 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (Bick) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered in series through 0.5 μm, 0.1 μm, and 0.05 μm filter cartridges for 48 hours to obtain a photosensitive resin composite.

[0084] Comparative Example 3

[0085] Photosensitive acrylic resin composition

[0086] 10 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 25 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 10 parts by weight of azobisisoheptonitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer, and 10 parts by weight of the following monomers were added:

[0087]

[0088] The flask was vacuum-purged with nitrogen while stirring. After all materials dissolved, the temperature was raised to 66°C and maintained at this temperature for 6 hours. The mixture was then cooled to room temperature to obtain a styrene acrylic resin solution. The styrene acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the styrene acrylic resin solution precipitated. After filtration, the solution was vacuum-dried to obtain a styrene acrylic resin having a weight-average molecular weight of approximately 8000 and a molecular weight distribution of 1.88.

[0089] Preparation of photosensitive resin composites

[0090] 100 parts by weight of the acrylic resin prepared above, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 15 parts by weight of 3-glycidyloxypropyltrimethoxysilane, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 μm, 0.1 μm, and 0.05 μm filter cartridges in series for 48 hours to obtain a photosensitive resin composite.

[0091] Comparative Example 4

[0092] Photosensitive acrylic resin composition

[0093] 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 10 parts by weight of azobisisoheptonitrile, and 250 parts by weight of tetrahydrofuran were added to a flask equipped with a condenser reflux and a stirrer, and 10 parts by weight of the following acrylic acid monomer was added:

[0094]

[0095] The flask was vacuum-purged with nitrogen while stirring. After all materials dissolved, the temperature was raised to 66°C and maintained at this temperature for 6 hours. The mixture was then cooled to room temperature to obtain a styrene acrylic resin solution. The styrene acrylic resin solution was then added dropwise to 4000 parts by weight of stirring n-heptane. The resin in the styrene acrylic resin solution precipitated. After filtration, the solution was vacuum-dried to obtain a styrene acrylic resin having a weight-average molecular weight of approximately 8000 and a molecular weight distribution of 1.88.

[0096] Preparation of photosensitive resin composites

[0097] 100 parts by weight of the styrene acrylic resin prepared above, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 μm, 0.1 μm, and 0.05 μm filter cartridges in series for 48 hours to obtain a photosensitive resin composite.

[0098] Comparative Example 5

[0099] Preparation of resin-free composites

[0100] 100 parts by weight of 3-glycidyloxypropyltrimethoxysilane, 30 parts by weight of an ester of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 4,4',4"-ethylenetriphenol, 5 parts by weight of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 0.2 parts by weight of BYK-333 (Bick) leveling agent, 0.2 parts by weight of antioxidant 1010 (BASF), 360 parts by weight of propylene glycol methyl ether acetate, and 180 parts by weight of propylene glycol methyl ether were mixed and stirred to dissolve. After the above substances were completely dissolved to form a uniform solution, the resulting solution was filtered through 0.5 micron, 0.1 micron, and 0.05 micron filter cartridges in sequence for 48 hours to obtain a photosensitive resin composite.

[0101] Comparative Example 6

[0102] Photosensitive polysiloxane resin composition

[0103] To a flask equipped with a condenser and a stirrer, 10 parts by weight of 3-glycidyloxypropyltrimethoxysilane, 45 parts by weight of phenyltriethoxysilane, 30 parts by weight of a mixed solution of tetraethyl silicate and 15 parts by weight of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane were added, and the mixed solution was fully mixed at a speed of 600 rpm. 100 parts by weight of methanol and 50 parts by weight of ultrapure water and 4 parts by weight of oxalic acid as a catalyst were added and stirred for 1 hour. The temperature was then gradually raised to 60 degrees Celsius and maintained at this temperature for 10 hours, and then cooled to room temperature to terminate the reaction. The reaction product was rapidly cooled to below 0°C to precipitate the reaction product, and the unreacted monomers, catalyst and solvent were removed by filtration. The product was rinsed with frozen methanol and vacuum dried at room temperature to obtain a polysiloxane resin.

[0104] Take 100 parts by weight of the above-mentioned polysiloxane resin, 30 parts by weight of 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid ester with 4,4',4"-ethylenetriphenol, 0.2 parts by weight of BYK-333 (BYK) leveling agent, 360 parts by weight of propylene glycol methyl ether acetate and 180 parts by weight of propylene glycol methyl ether, mix and dissolve them together with stirring, and filter the resulting solution in series through 0.5 micron, 0.1 micron, and 0.05 micron filter cartridges for 48 hours to obtain a photosensitive polysiloxane resin composite.

[0105] Performance Testing

[0106] The photosensitive resin composites prepared in Examples 1-3 and Comparative Examples 1-6 were respectively coated on an alkali-free glass substrate by spin coating into a 10 μm liquid film, vacuum dried at a pressure of 260 Pa for 60 s to obtain a dry film, pre-baked at 100°C for 150 s, cooled, and then contact-exposed under a photomask. The light source was ultraviolet light from a mercury lamp I / G / H line, and a 2.38% TMAH solution was used as the developer. The film was developed for 60 s, rinsed with pure water for 30 s to remove the developer, and the surface moisture of the film layer was dried with air. The film was cured in a convection oven at 200°C to form a film. The test data is shown in Table 1.

[0107] Table 1

[0108]

[0109]

[0110] It can be seen that the performance of the photosensitive resin composite of the present invention is far superior to that of the pure acrylic resin photosensitive resin composite of Comparative Example 1. Comparative Examples 2 and 3 use improper formulations, which affect the film-forming property and pattern performance. Comparative Example 4 that does not use a siloxane monomer has a poor heat resistance. Comparative Example 5 that does not use a resin cannot form a film. The storage stability is better than that of the photosensitive polysiloxane resin composite of Comparative Example 6, and the other properties are comparable to those of the photosensitive polysiloxane resin composite.

[0111] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A photosensitive resin composite for an insulating flat layer of a display device, characterized in that: The composition comprises, by weight, 10 to 30 parts of styrene acrylic resin, 1 to 15 parts of siloxane compound, 1 to 10 parts of photosensitive compound, 0.5 to 2 parts of auxiliary agent and 150 to 300 parts of solvent; Wherein, the photosensitizing compound is a diazonaphthoquinone ester containing multiple phenolic hydroxyl groups; The styrene acrylic resin is prepared according to the following steps: Functional monomers, hydrophilic monomers, cross-linking monomers, hydrophobic monomers and styrene are mixed and polymerized under the action of an initiator to obtain styrene acrylic resin. The functional monomer is selected from one of the following structural formulas: Wherein, A is hydrogen or methyl, n is a positive integer of 1 to 6, and R is selected from one or more of hydrogen, an alkyl group with carbon atoms of C1-C3, and a hydroxyl group.

2. The photosensitive resin composite according to claim 1, wherein The functional monomer is selected from one of the following structures: The hydrophilic monomer is selected from one or more of methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylamide, acrylamide, acryloylmorpholine, 3-methacryloyloxypropionic acid, and 2-sulfonic acid ethyl methacrylate; The crosslinking monomer is selected from one or more of glycidyl methacrylate, ethylene glycol methacrylate, allyl methacrylate, diacetone acrylamide, oxetane methacrylate, methacryloxypropyltrimethoxysilane, vinyl methacrylate, and N-methoxyacrylamide; The hydrophobic monomer is selected from one or more of isobornyl methacrylate, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, and adamantyl methacrylate.

3. The photosensitive resin composite according to claim 1, wherein The styrene acrylic resin is prepared according to the following steps: The functional monomer, the hydrophilic monomer, the cross-linking monomer, the hydrophobic monomer and styrene are mixed, tetrahydrofuran and an initiator are added to the monomer mixture obtained above, and the mixture is stirred to be fully mixed; Heat to 60-68°C in an inert atmosphere for polymerization reaction. After reacting for 2-6 hours, cool to room temperature. Then slowly pour the cooled reaction liquid into stirring n-heptane to obtain a resin precipitate. Filter and vacuum dry to obtain styrene acrylic resin.

4. The photosensitive resin composite according to claim 3, wherein The monomer mixture comprises 5-20 wt% of functional monomers, 15-40 wt% of hydrophilic monomers, 10-30 wt% of crosslinking monomers, 20-40 wt% of hydrophobic monomers and 15-50 wt% of styrene.

5. The photosensitive resin composite according to claim 3, wherein The mass ratio of the monomer mixture, tetrahydrofuran and initiator is 1:2-4:0.03-0.

15.

6. The photosensitive resin composite according to claim 1, wherein The weight average molecular weight of the styrene acrylic resin is 5000-20000, and the molecular weight distribution is 1.5-2.

5.

7. The photosensitive resin composite according to claim 1, wherein The siloxane compound is selected from one or more of trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxydimethylsilane, and diethoxydiphenylsilane.

8. The photosensitive resin composite according to claim 1, wherein The photosensitive compound is selected from one of the following structures: Where D is H or And D is not H at the same time.

9. The photosensitive resin composite according to claim 1, wherein The auxiliary agent comprises one or more of a leveling agent, a defoaming agent, an opening agent, a cross-linking agent, an antioxidant, a UV absorber, and a free radical scavenger.

10. The photosensitive resin composite according to claim 1, wherein The solvent is selected from one or more of propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, anisole, propylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethylene glycol monoacetate, ethylene glycol diacetate, ethyl lactate, γ-butyrolactone, butanone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone.

11. The method for preparing a photosensitive resin composite according to any one of claims 1 to 10, wherein: The steps include: Styrene acrylic resin, silicone compound, photosensitive compound, additive and solvent are mixed, stirred at room temperature to completely dissolve them, and filtered through 0.5μm, 0.1μm and 0.05μm filter elements in sequence for 36-48 hours to obtain a photosensitive resin composite.

12. A planarization layer of a display device, characterized in that: The planarization layer is obtained by coating the photosensitive resin composite according to any one of claims 1 to 10 on a substrate, followed by reduced pressure drying, pre-baking, exposure, development, and curing.

13. A display device, characterized in that The planarization layer according to claim 12 is included.

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