Modified epoxy resins, resin compositions, films, and methods for their preparation

Abstract

This invention discloses a silane coupling agent modified epoxy resin, comprising, by weight: 100 parts epoxy resin, 100-400 parts first solvent, 0.1-0.5 parts polymerization inhibitor, 1-5 parts catalyst, acrylic compound, acid anhydride, and 3-10 parts first coupling agent, wherein the molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the acid anhydride is 1:(1.05-1.3):(0.1-0.9). This invention also provides a method for preparing the silane coupling agent modified epoxy resin and a low-temperature curable negative-type radiosensitive linear resin composition prepared using the modified epoxy resin. The resin composition prepared using the modified epoxy resin of this invention can complete the pre-baking and post-baking processes at a lower temperature to obtain an insulating planarization film that meets resolution requirements and has good ethanol chemical resistance and heat resistance.

Description

Technical Field

[0001] This invention relates to the field of radiosensitive linear materials technology. More specifically, this invention relates to a modified epoxy resin, a resin composition, an insulating planarization film, and methods for preparing the same. Background Technology

[0002] Flexible displays are display devices made of soft, deformable, and bendable materials. With the development of display technology, display devices are now widely used, leading to increasingly higher performance requirements for screens. Flexible screens are bendable, allowing for bending or folding, thus improving portability and usability. As one of the light-emitting elements developed in recent years, organic electroluminescence (EL) elements with a stacked structure including an anode layer, an organic light-emitting layer, and a cathode layer are known. Display devices with organic EL elements include those with a touchscreen on the front surface. Organic EL devices with touchscreens are manufactured, for example, by bonding the touchscreen to a substrate forming the organic EL element via an adhesive or bonding layer. Touchscreens are typically manufactured by placing touchscreen components such as sensor electrodes on a support substrate. When curing the insulating planarization film used to form the touchscreen, the linear emissive resin composition needs to be heated to temperatures exceeding 120°C; however, heating above 120°C can easily lead to degradation of the organic light-emitting layer. This places new demands on photosensitive resin compositions, requiring curing at low temperatures to form films with excellent heat and chemical resistance and meeting resolution requirements. Summary of the Invention

[0003] One object of the present invention is to solve at least the above-mentioned problems and to provide at least the advantages that will be described later.

[0004] Another objective of this invention is to provide a silane coupling agent modified epoxy resin. The epoxy resin is first modified with an acrylic compound and an anhydride, and then a silane group is introduced to obtain a silane coupling agent modified epoxy resin. The negative-type radiosensitive linear resin composition prepared from the silane coupling agent modified epoxy resin can complete the pre-baking and post-baking processes at low temperature to obtain an insulating planarization film that meets the resolution requirements and has good ethanol chemical resistance and heat resistance.

[0005] To achieve these objectives and other advantages according to the present invention, a first aspect of the present invention provides a silane coupling agent modified epoxy resin, comprising, by weight: 100 parts epoxy resin, 100-400 parts first solvent, 0.1-0.5 parts polymerization inhibitor, 1-5 parts catalyst, acrylic compound, acid anhydride, and 3-10 parts first coupling agent, wherein the molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the acid anhydride is 1:(1.05-1.3):(0.1-0.9).

[0006] A second aspect of this invention provides a method for preparing a silane coupling agent modified epoxy resin, comprising the following steps according to the above-mentioned mass parts and molar ratio:

[0007] S1. Add epoxy resin and the first solvent into the reactor, heat and stir until the epoxy resin is completely dissolved, add polymerization inhibitor, heat to 80-110℃ and add catalyst, and add acrylic compound dropwise into the reactor. After the addition is complete, react for 3-6 hours to obtain epoxy acrylate.

[0008] S2. Heat the reaction system of step S1 to 90-120℃, add acid anhydride, and react for 2-4 hours to obtain acid anhydride modified epoxy acrylate.

[0009] S3. Cool the reaction system of step S2 to 50-70°C, add the first coupling agent, and react for 6-18 hours to obtain the epoxy resin modified with silane coupling agent.

[0010] A third aspect of the present invention provides a low-temperature curable negative-type radiosensitive linear resin composition, comprising, by weight, 100 parts of epoxy resin modified with silane coupling agent, 80-170 parts of reactive diluent, 5-20 parts of photoinitiator, 5-15 parts of second coupling agent, 1-8 parts of curing agent, 600-900 parts of second solvent, and 0.5-3 parts of leveling agent.

[0011] Preferably, it also includes 5 to 20 parts of ultraviolet absorber.

[0012] Preferably, the mass ratio of the ultraviolet absorber to the photoinitiator is 1:(1.1 to 1.5).

[0013] Specifically, the reactive diluent is an acrylate compound;

[0014] The photoinitiator is one of O-acyl oxime compounds, α-hydroxy ketone derivatives, α-amino ketone derivatives, acylphosphine oxides, benzophenone and their derivatives;

[0015] The second solvent is one or more of the following: alcohol-based solvents, ether-based solvents, ester-based solvents, and ketone-based solvents;

[0016] The curing agent is an acid anhydride compound.

[0017] A fourth aspect of the present invention provides a method for preparing a low-temperature curable negative-type radiosensitive linear resin composition, comprising the following steps based on the above-mentioned parts by weight:

[0018] S1. Dissolve the silane coupling agent-modified epoxy resin in the second solvent and stir until homogeneous;

[0019] S2. Then add the reactive diluent, the second coupling agent, the photoinitiator, the curing agent, and the leveling agent in sequence, and stir until well mixed.

[0020] S3. Dilute to a solid content of 15-35 wt%, filter using a microporous membrane filter, and degas under vacuum to obtain a negative-type radiosensitive linear resin composition.

[0021] The fifth aspect of the present invention provides an insulating planarization film for a touch layer of a flexible OLED display device, which is formed from the negative-emissivity linear resin composition or the negative-emissivity linear resin composition prepared by the preparation method described above.

[0022] Preferably, the resolution of the low-temperature insulating planarization film is 5-15 μm, and the heat resistance Td, 1wt% of the low-temperature insulating planarization film is >120℃;

[0023] When the thickness of the insulating planarization film is between 2 and 5 μm, the film thickness change rate after immersion in ethanol at room temperature for 3 minutes is ≤10%.

[0024] The sixth aspect of the present invention provides a method for preparing a low-temperature insulating planarization film, comprising the following steps: coating, pre-baking, exposure, development, IUV, and post-baking;

[0025] The pre-baking process involves baking at 75–90℃ for 90–180 seconds.

[0026] After baking, bake at 75-90℃ for 60-120 minutes.

[0027] The present invention has at least the following beneficial effects:

[0028] This invention introduces carboxyl and silane groups onto epoxy resin, enabling the resin composition prepared using modified epoxy resin to complete the pre-baking and post-baking processes at a lower temperature, thereby obtaining an insulating planarization film that meets resolution requirements and has good ethanol chemical resistance and heat resistance.

[0029] The ratio of epoxy groups in epoxy resin to carboxyl groups in acrylic compounds affects the membrane resolution and thickness variation rate; the ratio of epoxy groups in epoxy resin to acid anhydrides also affects the membrane resolution and thickness variation rate.

[0030] In the preparation of silane coupling agent modified epoxy resin, this invention adds a polymerization inhibitor to avoid the polymerization of double bonds on acrylic compounds, silane coupling agents and modified epoxy resin.

[0031] The addition of ultraviolet absorbers can improve the development residue at the boundary between exposure and non-exposure, and improve the resolution of the insulating planarization film; controlling the ratio of ultraviolet absorbers to photoinitiators can further improve the resolution of the insulating planarization film to a certain extent.

[0032] When the thickness of the insulating planarization film is between 2 and 5 μm, the film thickness change rate after immersion in ethanol at room temperature for 3 min is small, indicating that the insulating planarization film has good ethanol resistance.

[0033] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Detailed Implementation

[0034] The present invention will now be described in detail. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Furthermore, the term "~" in this specification is used to mean both a lower and upper limit value, including the values ​​described before and after it.

[0035] <Silane Coupling Agent Modified Epoxy Resins>

[0036] This invention provides a silane coupling agent modified epoxy resin, comprising, by weight: 100 parts epoxy resin, 100-400 parts first solvent, 0.1-0.5 parts polymerization inhibitor, 1-5 parts catalyst, acrylic compound, acid anhydride, and 3-10 parts first coupling agent, wherein the molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the acid anhydride is 1:(1.05-1.3):(0.1-0.9).

[0037] The molecular structure of epoxy resins is characterized by the presence of reactive epoxy groups in the molecular chain. These epoxy groups can be located at the ends, in the middle, or in a cyclic structure. Due to the presence of reactive epoxy groups, they can undergo cross-linking reactions with various types of curing agents to form insoluble, infusible polymers with a three-dimensional network structure. The epoxy resins used in the embodiments of this invention are selected from at least one of the following: cresol phenolic epoxy resins, phenolic epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, bisphenol A phenolic epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, hydrogenated bisphenol A type epoxy resins, and triphenol methane type epoxy resins.

[0038] In some embodiments of the present invention, the first solvent is at least one selected from propylene glycol methyl ether, ethylene glycol ethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, diacetone alcohol, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, butyl acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, and ethylene glycol diacetate.

[0039] Polymerization inhibitors are industrial additives commonly used to prevent polymerization. In some embodiments of this invention, the polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, and 2,5-dimethylhydroquinone, used to prevent the polymerization of double bonds on acrylic compounds, silane coupling agents, and modified epoxy resins.

[0040] In some embodiments of the present invention, the catalyst is at least one selected from triethylamine, triethanolamine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine, and triphenylphosphine.

[0041] In some embodiments of the present invention, the acrylic compound is a monofunctional acrylic compound, and the acrylic compound is at least one of acrylic acid, methacrylic acid, β-(acryloyloxy)propionic acid, and mono(2-acryloylethyl ether)succinic acid.

[0042] In some embodiments of the present invention, the acid anhydride is at least one selected from maleic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, nonenylsuccinic anhydride, 2-octenylsuccinic anhydride, succinic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, and methylnadic anhydride; generally, in order to reduce steric hindrance and improve reaction efficiency, the unsaturated acid anhydride is preferably a monobasic acid anhydride.

[0043] In some embodiments of the present invention, the first coupling agent is at least one selected from vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0044] <Preparation method of epoxy resin modified with silane coupling agent>

[0045] This invention provides a method for preparing a silane coupling agent modified epoxy resin. One embodiment of this invention provides a specific method for preparing a silane coupling agent modified epoxy resin, comprising the following steps:

[0046] S1. Add 100 parts by weight of epoxy resin and 100-400 parts by weight of the first solvent into the reactor. First, heat the reactor to 70-90°C and stir until the epoxy resin is completely dissolved. Then, add 0.1-0.5 parts by weight of polymerization inhibitor. After heating the reactor to 80-110°C, add 1-5 parts by weight of catalyst and add acrylic acid compound dropwise into the reactor. After the addition is complete, react for 3-6 hours to obtain epoxy acrylate.

[0047] S2. Heat the reaction system of step S1 to 90-120℃, add acid anhydride, and react for 2-4 hours to obtain acid anhydride modified epoxy acrylate.

[0048] S3. Cool the reaction system of step S2 to 50-70°C, add 3-10 parts by mass of the first coupling agent, and react for 6-18 hours to obtain silane coupling agent modified epoxy resin.

[0049] The molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the acid anhydride is 1:

[0050] (1.05~1.3):(0.1~0.9); preferably, the molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the anhydride is 1:(1.1~1.25):(0.12~0.6); more preferably, the molar ratio of the epoxy groups of the epoxy resin, the carboxyl groups of the acrylic compound, and the anhydride is 1:(1.1~1.25):(0.12~0.4). The amount relationship between the epoxy groups of the epoxy resin and the carboxyl groups of the acrylic compound affects the resolution and thickness variation rate of the membrane; the amount relationship between the epoxy groups of the epoxy resin and the anhydride also affects the resolution and thickness variation rate of the membrane.

[0051] In some embodiments of this invention, a flexible epoxy resin is obtained by introducing double bonds through a ring-opening reaction between the epoxy group portion of the epoxy resin and acrylic acid. Simultaneously, side hydroxyl groups are formed during the ring-opening process of the epoxy group. Then, a carboxyl group is introduced by reacting the side hydroxyl group in the flexible epoxy resin with an acid anhydride, resulting in an alkali-soluble flexible epoxy resin. Finally, a silane group is introduced by reacting the side hydroxyl group in the flexible epoxy resin with a silane coupling agent, yielding a silane-modified epoxy resin. The negative-type radiosensitive linear resin composition prepared using the silane-modified epoxy resin as a raw material can undergo pre-baking and post-baking processes at low temperatures to obtain an insulating planarization film that meets resolution requirements and exhibits good ethanol resistance and heat resistance.

[0052] The reaction steps of one of the structural phenolic epoxy resins in the above preparation method of the present invention are as follows:

[0053]

[0054] Based on the reaction steps of the phenolic epoxy resin modified with the above silane coupling agent, the silane modification steps of other epoxy resins in this invention are the same as those of the phenolic epoxy resin.

[0055] <Negative-sensitivity radioactive linear resin composition>

[0056] This invention provides a negative-type radiosensitive linear resin composition, comprising, by weight, 100 parts of epoxy resin modified with silane coupling agent, 80-170 parts of reactive diluent, 5-20 parts of photoinitiator, 5-15 parts of second coupling agent, 1-8 parts of curing agent, 600-900 parts of second solvent, and 0.5-3 parts of leveling agent.

[0057] The negative-type radiosensitive linear resin composition provided by this invention further includes 5-20 parts of ultraviolet absorber. The addition of ultraviolet absorber can improve the development residue at the boundary between exposure and non-exposure, and improve the resolution of the insulating planarization film.

[0058] As polymerizable reactive diluents, some embodiments of the present invention may include, for example: trimethylolpropane tri(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tri(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane polypropylene glycol tri(meth)acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, diphenylethyl acrylate, ethoxyphenoxy acrylate, o-phenylphenoxy acrylate, 2-(p-isopropylbenzene) The following are some of the following: (-phenoxy)-ethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, laurate acrylate, laurate methacrylate, cyclotrimethylolpropane methyl acetal acrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol acrylate, neopentyl glycol acrylate, propoxylated neopentyl glycol acrylate, 1,6-hexanediol diacrylate, tricyclodecanediethanol diacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate.

[0059] In some embodiments of the present invention, the photoinitiator is an O-acyl oxime compound, an α-hydroxy ketone derivative, an α-amino ketone derivative, an acylphosphine oxide, benzophenone and its derivatives;

[0060] Examples of O-acyl oxime compounds include: 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-acetate, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime), 1 -[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketooxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketooxime-O-benzoate Formate esters, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]-,1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropy ... [9-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9.H.-carbazole-3-yl]-,1-(O-acetyl oxime), acetone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9.H.-carbazole-3-yl]-,1-(O-acetyl oxime), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] etc.

[0061] Examples of α-hydroxy ketone compounds include: 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylpropanone, etc.

[0062] Examples of α-aminoketone compounds include: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, 1-[4-(2-hydroxyethyl mercapto)phenyl]-2-methyl-2-(4-morpholino)propan-1-one, etc.

[0063] Examples of acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0064] Examples of hydrogen-abstracting free radical photoinitiators include benzophenone and 4-benzoyl-4'-methyl-diphenyl sulfide.

[0065] From the viewpoint of further promoting the hardening reaction carried out by radiosensitive linear free radical polymerization, O-acyl oxime compounds, α-amino ketone compounds, and acylphosphine oxide compounds are preferred as radiosensitive linear free radical polymerization initiators, more preferably O-acyl oxime compounds and α-amino ketone compounds, and even more preferably O-acyl oxime compounds.

[0066] In some embodiments of the present invention, the second coupling agent is an unsaturated silane coupling agent, such as: vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0067] In some embodiments of the present invention, the curing agent is an acid anhydride compound; for example, it can be succinic anhydride, itaconic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhydrophthalic anhydride, etc.

[0068] The second solvent is not particularly limited. Examples of second solvents in some embodiments of the present invention include alcohol-based solvents, ether-based solvents, ester-based solvents, and ketone-based solvents. Furthermore, the second solvent can be used alone or in combination of two or more.

[0069] Examples of alcohol-based solvents include: methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, diacetone alcohol, and other alkyl alcohols; and benzyl alcohol and other aromatic alcohols.

[0070] Examples of ether-based solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and other diethylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and other diethylene glycol dialkyl ethers; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and other dipropylene glycol monoalkyl ethers, etc.

[0071] Examples of ester-based solvents include: ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and other carboxylic acid esters; propylene glycol diacetate and other polyol carboxylic acid esters; and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other polyol partial ether carboxylic acid esters.

[0072] Examples of ketone solvents include: acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, etc.

[0073] Among these, ether-based solvents and ester-based solvents are preferred, more preferably ester-based solvents, and even more preferably polyol partial ether carboxylic acid ester solvents. Furthermore, among ether-based and ester-based solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0074] In some embodiments of the present invention, the leveling agent is one of polyacrylate, silicone resin, and fluorosurfactant; examples include: polyacrylate Deqian 495, modified polysiloxane Deqian 810, polyether-modified polydimethylsiloxane Byk 333, polyether-modified polydimethylsiloxane Byk 330, polyether-modified hydroxyl-functionalized polydimethylsiloxane Byk 373, fluorocarbon-modified acrylic Efka 3600, polyether-modified polysiloxane Deqian 431, modified polysiloxane Deqian 432, polyether-siloxane copolymer Glide 100, polyether-siloxane copolymer Glide 440, polyacrylate Flow 300, polyether-siloxane polymer Flow 425, polyacrylate Flow 460, polyester-modified polydimethylsiloxane containing acrylic functional groups Byk 371, and silicone-modified polymer Efka 3883.

[0075] In some embodiments of the present invention, the leveling agent is leveling agent BYK330.

[0076] In some embodiments of the present invention, the ultraviolet absorbers are salicylate esters and benzotriazole compounds; examples include: phenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2H-benzotriazole-2)-4,6-di(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol.

[0077] The negative-type radiosensitive linear resin composition in some embodiments of the present invention may further include a polymerization inhibitor, which is a phenolic, quinone, or aromatic amine compound, such as p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, and 2,5-dimethylhydroquinone.

[0078] <Preparation Method of Negative-Type Radiation-Induced Linear Resin Composition>

[0079] This invention provides a method for preparing a negatively induced radiosensitive linear resin composition. One embodiment of this invention provides a method for preparing a negatively induced radiosensitive linear resin composition, comprising the following steps based on the above-mentioned parts by weight:

[0080] S1. Dissolve 100 parts by weight of the epoxy resin modified with silane coupling agent in 600-900 parts by weight of the second solvent and stir until homogeneous;

[0081] S2. Then add 80-170 parts by weight of reactive diluent and 5-15 parts by weight of second coupling agent in sequence, stir evenly, then add 5-20 parts by weight of photoinitiator, 1-8 parts by weight of curing agent and 0.5-3 parts by weight of leveling agent, and stir evenly.

[0082] S3. Dilute to a solid content of 15-35 wt%, filter using a microporous membrane filter, and degas under vacuum to obtain a negative-type radiosensitive linear resin composition.

[0083] Preferably, when adding the curing agent, 5 to 20 parts by weight of ultraviolet absorber can also be added, and 0.01 to 0.5 parts by weight of polymerization inhibitor can also be added.

[0084] The mass ratio of the ultraviolet absorber to the photoinitiator is 1:(1.1~1.5). Controlling the ratio of the ultraviolet absorber to the photoinitiator can further improve the resolution of the insulating planarization film.

[0085] <Insulating Planarization Film>

[0086] The present invention provides an insulating planarization film, which is formed from the negative-type radiosensitive linear resin composition or the negative-type radiosensitive linear resin composition prepared by the preparation method of the negative-type radiosensitive linear resin composition.

[0087] In some embodiments of the present invention, the insulating planarization film for a display device is a hardened film formed from the aforementioned radiosensitive linear resin composition. The insulating planarization film for a display device may be a patterned film. The insulating planarization film for a display device is a hardened film that exhibits good heat resistance and chemical resistance even when heated at relatively low temperatures.

[0088] Besides serving as an insulating planarization film, it can also be used as a protective film in low-temperature color filters, and as an insulating bridge between the transparent conductive layers of touch screens and displays.

[0089] The insulating planarization film for the display device is unlikely to crack even when it is relatively thick. Therefore, the insulating planarization film for the display device can be made into a thick film. The lower limit of the average thickness of the insulating planarization film for the display device is, for example, 0.1 μm, sometimes preferably 0.5 μm, more preferably 1 μm, and even more preferably 2 μm. On the other hand, the upper limit of the average thickness is, for example, 10 μm, but can be 6 μm, 5 μm, or 4 μm.

[0090] <Preparation method of insulating planarization film>

[0091] This invention provides a method for preparing an insulating planarization film, comprising the following steps: coating, pre-baking, exposure, development, IUV, and post-baking;

[0092] (1) Coating process of applying composition onto substrate

[0093] In step (1), after coating the negative-type radiosensitive linear resin composition of the embodiment of the present invention onto the substrate, it is preferable to vacuum-extract a portion of the solvent at room temperature to allow the film to initially set and increase the adhesion of the coating layer to the substrate. Examples of substrates that can be used include glass, quartz, silicon, and resin. The coating method of the composition of this embodiment is not particularly limited, and suitable methods such as spraying, roller coating, spin coating, slot die coating, and bar coating can be used. Among these coating methods, spin coating or slot die coating is particularly preferred.

[0094] (2) Pre-baking process for coating

[0095] In step (2), the coating film formed in step (1) is baked at 75-90°C for 90-180 seconds. In this embodiment of the invention, if the coating film formed by the negative-type radiosensitive linear resin composition is baked at a temperature higher than 90°C, the development will be poor, the resolution will decrease, and an insulating planarization film with the resolution required by the present invention will not be obtained.

[0096] (3) The process of irradiating at least a portion of the coating with radiation.

[0097] In step (3), at least a portion of the coating film on the substrate formed in step (2) is exposed. In this case, when exposing a portion of the coating film, exposure is performed, for example, through a photomask with a predetermined pattern. When the hardened film of this embodiment is used as the gate insulating planarization film of the semiconductor device of this embodiment, the pattern of the photomask corresponds to the pattern of the gate insulating planarization film.

[0098] The radiation used during exposure can be, for example, visible radiation, ultraviolet radiation, far ultraviolet radiation, electron beams, X-rays, etc. Among these radiations, radiation with wavelengths in the range of 190 nm to 450 nm is preferred, and radiation containing 365 nm ultraviolet radiation is particularly preferred.

[0099] Regarding the exposure amount in this process, it is preferably 100 J / m², based on the value obtained by measuring the intensity of radiation at a wavelength of 365 nm using an illuminometer. 2 ~10000J / m 2 More preferably 300J / m 2 ~1500J / m 2 .

[0100] (4) Developing process

[0101] In step (4), the exposed coating obtained from step (3) is developed, thereby removing unwanted portions (radiation-irradiated portions in the case of a positive image, and non-radiation-irradiated portions in the case of a negative image) to form a predetermined pattern. The developer used in the developing step is preferably an aqueous solution of an alkali (alkaline compound). Examples of alkalis include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0102] Alternatively, an appropriate amount of water-soluble organic solvents or surfactants such as methanol or ethanol can be added to this alkaline aqueous solution. From the viewpoint of obtaining suitable developability, the concentration of alkali in the alkaline aqueous solution is preferably set to 0.1 wt% to 5 wt%. Developing methods can include, for example, liquid accumulation, immersion, shaking immersion, spraying, and other suitable methods. The developing time varies depending on the composition of the composition of this embodiment, but is preferably around 10 to 180 seconds.

[0103] (5) IUV process

[0104] Following the development process, such as a 30-90 second water rinse, the product is then dried using compressed air or compressed nitrogen, thereby forming the desired pattern.

[0105] After air drying, it is exposed using a 365nm i-line with an exposure energy of 0–600 mJ.

[0106] (6) Post-drying process

[0107] In step (5), a heating device such as a hot plate or oven is used to heat the patterned film at a relatively high temperature, thereby promoting the reaction of the composition of this embodiment and obtaining a hardened film. Moreover, the hardened film obtained by patterning in a predetermined shape can be used as an insulating planarization film for the element of this embodiment.

[0108] The post-baking process involves drying at 75–90℃ for 60–120 minutes.

[0109] The insulating planarization film has a resolution of 5–15 μm; the thickness of the insulating planarization film is 2–5 μm, and the film thickness change rate after immersion in ethanol at room temperature for 3 min is ≤10%; the insulating planarization film has excellent heat resistance (Td, 1wt% >120℃); the insulating planarization film has a transmittance of >95% at 550 nm.

[0110] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0111] It should be noted that, unless otherwise specified, the experimental methods described in the following implementation plan are all conventional methods, and the reagents and materials described are all commercially available unless otherwise specified.

[0112] EPN: Phenolic epoxy resin

[0113] ECN: Cresol Phenolic Epoxy Resin

[0114] PGMEA: Propylene Glycol Methyl Ether Acetate

[0115] HQ: Hydroquinone

[0116] PPh3: Triphenylphosphine

[0117] AA: Acrylic acid

[0118] MAA: Methacrylic acid

[0119] M158642: Mono(2-Acryloylethyl ether)succinic acid, purchased from Aladdin Reagent (Shanghai) Co., Ltd.

[0120] MA: Maleic anhydride

[0121] PDMA: Pyromellitic anhydride

[0122] IA: Itaconic anhydride

[0123] KH570: 3-Methacryloxypropyltrimethoxysilane, purchased from Shin-Etsu Chemical Co., Ltd.

[0124] Z6036: 3-Methacryloxypropyltriethoxysilane

[0125] A-171: Vinyltrimethoxysilane

[0126] TMPTA: Trimethylolpropane triacrylate, purchased from Nippon Kayaku Co., Ltd.

[0127] DPHA: Dipentaerythritol hexaacrylate

[0128] Photoinitiator 819: Phenylenol bis(2,4,6-trimethylbenzoyl)phosphine oxide, purchased from BASF AG

[0129] BYK330 leveling agent, purchased from BYK Chemicals.

[0130] UV-P, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole

[0131] <Synthesis example>

[0132] Synthesis Example 1: Synthesis Method of Modified Resin A-1

[0133] In a 250 mL three-necked flask equipped with a thermometer, 40 g of phenolic epoxy resin (EPN) was added, followed by 40 mL of propylene glycol methyl ether acetate (PGMEA). The mixture was heated and stirred until dissolved. Hydroquinone (HQ) was added, and the temperature was raised to 95 °C. 0.5 g of triphenylphosphine (PPh3) was added, and acrylic acid (AA) was added dropwise. After the addition was complete, the mixture was kept at 95 °C for 6 h to obtain o-cresol epoxy acrylate. The temperature was then raised to 100 °C, and 4 g of maleic anhydride was added. The mixture was kept at this temperature for 3 h to obtain anhydride-modified o-cresol epoxy acrylate. Finally, the temperature was lowered to 60 °C, and silane coupling agent KH570 was added. The mixture was kept at this temperature for 12 h to obtain a silane coupling agent-modified resin solution.

[0134] The silane coupling agent-modified resin was added dropwise to 1000 mL of n-hexane, causing resin precipitation. After filtration, the resin was separated and dried under vacuum to obtain modified epoxy resin solid powder A-1. Gel permeation chromatography (GPC) determined the resin's weight-average molecular weight to be 6000 g / mol.

[0135] The synthesis methods of the compositions in Synthetic Examples 2-8 and the compositions in Comparative Examples 1-5 are the same as those in Synthetic Example 1. The specific names of raw materials and specific process parameters are recorded in Table 1.

[0136] Table 1

[0137]

[0138] <Preparation Example>

[0139] Preparation Example 1: Preparation method of low-temperature curable negative photosensitive resin composition Z-1

[0140] A radiosensitive linear composition (Z-1) was prepared by diluting 100 parts by weight of modified resin solid powder A-1, 30 parts by weight of trimethylolpropane triacrylate (TMPTA), 50 parts by weight of dipentaerythritol hexaacrylate (DPHA), 12 parts by weight of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), 8 parts by weight of coupling agent KH570, and 2 parts by weight of curing agent maleic anhydride (MA) with propylene glycol methyl ether acetate (PGMEA) to a total solid content concentration of 30 wt%, and then filtering the solution through a membrane filter with a pore size of 0.2 μm.

[0141] Preparation Example 14: Preparation method of low-temperature curable negative photosensitive resin composition Z-14

[0142] A radiosensitive linear composition (Z-14) was prepared by diluting 100 parts by weight of modified resin solid powder A-1, 30 parts by weight of trimethylolpropane triacrylate (TMPTA), 50 parts by weight of dipentaerythritol hexaacrylate (DPHA), 12 parts by weight of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), 8 parts by weight of coupling agent KH570, 2 parts by weight of curing agent maleic anhydride (MA), 0.5 parts by weight of leveling agent BYK330, and 8 parts by weight of ultraviolet absorber UV-P with propylene glycol methyl ether acetate (PGMEA) to a total solid content concentration of 30 wt%, and then filtering through a membrane filter with a pore size of 0.2 μm.

[0143] The preparation methods of the compositions in Preparation Examples 2-13 and the compositions in Comparative Examples 1-2 are the same as those in Preparation Example 1. The preparation methods of the compositions in Preparation Examples 14-17 are the same as those in Preparation Example 14. The specific names of the raw materials in Preparation Examples 1-17 and Comparative Examples 1-6 are listed in Table 2.

[0144] Table 2

[0145]

[0146] <Example>

[0147] Example 1: Preparation of insulating planarization film using composition Z-1

[0148] The method for preparing an insulating planarization film using the aforementioned low-temperature curing negative photosensitive resin composition includes the following steps in sequence: coating, pre-baking, exposure, development, IUV, and post-baking.

[0149] 1) Coating: The negative-type radiation-sensitive resin composition is coated on the corresponding layer of the device using the Slit method. The film thickness after pre-baking is controlled to be between 2 and 5 μm. At room temperature, the substrate after coating is vacuumed to remove part of the solvent.

[0150] 2) Pre-baking: After removing the solvent, the substrate is baked at 75-90℃ for 90-180 seconds;

[0151] 3) Exposure: Exposure energy 300~1500J / m 2 ;

[0152] 4) Development: Use 2.38% TMAH alkaline developer to develop for 40-120 seconds to produce the corresponding pattern on the mask plate;

[0153] 5) IUV: The film after development and washing is exposed to a 365nm i-line with an exposure dose of 0-600mJ;

[0154] 6) Post-baking: 75~90℃, bake for 60~120min.

[0155] <Examples 2-17 and Comparative Examples 1-6>

[0156] The insulating planarization films in Examples 2 to 17 were prepared from the corresponding compositions Z-2 to Z-17, and the insulating planarization films formed in Comparative Examples 1 to 2 were prepared from the corresponding compositions A'-1. Examples 2 to 17 and Comparative Examples 1 to 6 all adopted the preparation method disclosed in Example 1.

[0157] The membranes in Examples 1-17 and Comparative Examples 1-6 were evaluated respectively.

[0158] The following indicators are used to evaluate the membrane:

[0159] 1) Resolution

[0160] A patterned film is formed on a glass substrate, and the linewidth of the smallest pattern in the patterned film is observed using a scanning electron microscope (SEM).

[0161] 2) Ethanol resistance

[0162] The low-temperature curing negative photosensitive resin composition was coated on a glass substrate, baked and then cut into 4*4cm pieces. Three points were selected and pierced with tweezers. The film thickness D was measured using a confocal microscope. The pieces were then immersed in ethanol at room temperature for 3 minutes and the film thickness d at each point was measured again. The film thickness change rate ΔTHK% before and after ethanol immersion was calculated as (Dd) / D*100%.

[0163] ΔTHK% absolute value >10%, indicating poor ethanol resistance;

[0164] The absolute value of ΔTHK% is between 5% and 10%, indicating good ethanol resistance.

[0165] ΔTHK% absolute value <5%, excellent ethanol resistance.

[0166] 3) Heat resistance

[0167] A low-temperature curing negative photosensitive resin composition was coated onto a glass substrate and then baked. The film on the glass surface was scraped into a uniform and fine powder with a knife. The powder was then subjected to TGA testing under the following conditions: N2 atmosphere, temperature increased from room temperature to 500℃ at a rate of 10℃ / min, and the temperature Td, 1wt%, of 1% thermal weight loss was recorded.

[0168] Td, 1wt% <120℃, poor heat resistance;

[0169] Td, 1wt%, exhibits good heat resistance between 120℃ and 150℃;

[0170] Td, 1wt% > 150℃, excellent heat resistance.

[0171] Table 3

[0172]

[0173] As can be seen from the data of Examples 1-13 and Comparative Examples 1-2 in Table 3, the epoxy resin modified with acrylic acid compound, acid anhydride and silane coupling agent, and the resin composition prepared by it can complete the pre-baking and post-baking processes at 75-90°C, and can form an insulating planarization film with the required resolution, and the insulating planarization film has good ethanol resistance and heat resistance.

[0174] As can be seen from Examples 14-17 in Table 3, the resolution of the film is improved when the mass ratio of ultraviolet absorber to photoinitiator is between 1:(1.1 to 1.5).

[0175] As can be seen from Example 1 and Comparative Examples 3-4 in Table 3, both excessive and insufficient amounts of acrylic acid will affect the membrane resolution and membrane thickness change rate; as can be seen from Example 1 and Comparative Examples 5-6, both excessive and insufficient amounts of acid anhydride will also affect the membrane resolution and membrane thickness change rate.

[0176] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and embodiments shown and described herein.

Claims

1. A silane coupling agent modified epoxy resin, characterized in that, According to the mass parts, it comprises: epoxy resin 100 parts, first solvent 100-400 parts, polymerization inhibitor 0.1-0.5 parts, catalyst 1-5 parts, acrylic compound, acid anhydride, first coupling agent 3-10 parts, wherein the molar ratio of epoxy group of the epoxy resin, carboxyl of the acrylic compound and the acid anhydride is 1:(1.05-1.3):(0.1-0.9); the first coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane.

2. The method for producing a silane coupling agent-modified epoxy resin according to Claim 1, wherein According to the above mass parts and molar ratio, it comprises the following steps: S1, the epoxy resin and the first solvent are added into the reactor, and the temperature is raised to dissolve the epoxy resin completely, then the polymerization inhibitor is added, the temperature is raised to 80-110 DEG C, then the catalyst is added, and the acrylic compound is added dropwise into the reactor, after the dropwise addition is completed, the reaction is carried out for 3-6 hours, and the epoxy acrylate resin is obtained; S2, the reaction system of step S1 is heated to 90-120 DEG C, the acid anhydride is added, and the reaction is carried out for 2-4 hours, and the acid anhydride modified epoxy acrylate resin is obtained; S3, the reaction system of step S2 is cooled to 50-70 DEG C, the first coupling agent is added, and the reaction is carried out for 6-18 hours, and the silane coupling agent modified epoxy resin is obtained.

3. A negative-working radiation-sensitive resin composition, characterized by comprising: According to the mass parts, it comprises the silane coupling agent modified epoxy resin of claim 1 100 parts, active diluent 80-170 parts, photoinitiator 5-20 parts, second coupling agent 5-15 parts, curing agent 1-8 parts, second solvent 600-900 parts, leveling agent 0.5-3 parts.

4. The negative-type radiation-sensitive resin composition according to claim 3, wherein It also comprises: Ultraviolet absorber 5-20 parts.

5. The negative-type radiation-sensitive resin composition according to claim 4, wherein The mass ratio of the ultraviolet absorber to the photoinitiator is 1:(1.1-1.5).

6. The negative-type radiation-sensitive resin composition according to claim 3, wherein The active diluent is an acrylate compound; The photoinitiator is one of O-acyloxime compound, alpha-hydroxy ketone derivative, alpha-amino ketone derivative, acyl phosphine oxide, benzophenone and its derivative; The second solvent is one or more of alcohol solvent, ether solvent, ester solvent, ketone solvent; The curing agent is an acid anhydride compound.

7. The method for producing a negative-type radiation-sensitive resin composition according to claim 3 or 6, wherein According to the above mass parts, it comprises the following steps: S1, the silane coupling agent modified epoxy resin is dissolved in the second solvent, and stirred uniformly; S2, the active diluent, the second coupling agent, the photoinitiator, the curing agent and the leveling agent are added in turn, and stirred uniformly; S3, dilute to 15-35wt% of solid content ratio, filter with microporous membrane filter, vacuum degassing, and obtain the negative radio-sensitive resin composition.

8. An insulating planarization film for a flexible OLED display device touch layer, which is formed by the negative radio-sensitive resin composition of any one of claims 3-6 or the negative radio-sensitive resin composition prepared by the preparation method of claim 7.

9. The insulating planarization film of claim 8 wherein, The resolution of the insulating planarization film is 5 to 15 μm, and the heat resistance Td,1wt% of the insulating planarization film is higher than 120°C; The thickness change rate of the insulating planarization film is ≤10% after soaking in ethanol at room temperature for 3 minutes when the thickness of the insulating planarization film is between 2 to 5 μm.

10. A method for producing the insulating planarization film according to claim 8 or 9, characterized by, The method comprises the following steps: coating, pre-baking, exposure, development, IUV, post-baking; The pre-baking is baked at 75 to 90°C for 90 to 180 seconds; The post-baking is baked at 75 to 90°C for 60 to 120 minutes.

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