Thermosetting composition, cured film obtained by curing the same, and display device containing the cured film.

Abstract

To provide a thermosetting composition which enables formation of a protective film that is excellent in adhesion while satisfying request characteristics such as flatness and low gas generating property.SOLUTION: A thermosetting composition contains (A) an epoxy compound represented by the following general formula (1), (B) a curing agent or (C) a hardening accelerator, and (D) a solvent. In formula (1), a and d represent an epoxy group, and b and c represent an alicyclic hydrocarbon skeleton having 5 or more carbon atoms. The two adjacent b and c mutually share two atoms, and carbon atoms constituting the b or the c may be mutually crosslinked in the rings. n represents 0 or a natural number. When n is two or more, each c may be different.SELECTED DRAWING: None

Description

Technical Field

[0004] , , , , ,

[0003]

[0001] The present invention relates to a thermosetting composition, a cured film obtained by curing the composition, and a display device including the cured film.

Background Art

[0002] Generally, a transparent cured film (hereinafter also referred to as a "protective film") is formed as a protective layer on the surface of a color filter used in the manufacture of a color liquid crystal display (LCD). The protective film of the color filter is formed for the purpose of flattening the unevenness generated between the pixels of the color filter, improving the durability of the color filter against heat treatment and chemical treatment in subsequent processes, and improving the reliability of the color liquid crystal display. As the protective film of the color filter, it is required to be excellent in flatness, heat resistance, adhesion, and the like.

[0003] For example, as flatness, it is required to make the unevenness with a height of about 1 to 2 μm generated by the overcoating of the coloring composition when forming pixels to be 1.0 μm or less. As heat resistance, when a transparent electrode such as ITO is formed on the protective film by sputtering, the protective film may be subjected to a high heat of about 200 to 270 °C, and it is required that the protective film be stable under this temperature condition. As adhesion, when manufacturing a liquid crystal display panel, the substrate may be bonded on the protective film, and it is required that the protective film at that part does not peel off from the base.

[0004] In recent years, display methods similar to IPS (In-plane Switching) mode, which offer wide viewing angles and fast response times, have come into use, and the requirements for the protective film have become more stringent. In display methods such as IPS mode, if gaseous or liquid components or water generated or bleed out from the color filter layer enter the liquid crystal layer via the protective layer, it can increase the concentration of water and ionic impurities in the liquid crystal layer, or cause the above components to form bubbles in the liquid crystal layer, leading to display defects. Therefore, the protective layer must not only prevent the passage of the above impurity components into the liquid crystal layer, but also, since gas generation from the protective film in direct contact with the liquid crystal layer directly leads to display defects, the low gas emission properties of the protective film are considered particularly important. Furthermore, with the thinning of LCD panels, there is a demand for thinner protective films, and the requirements for the flatness of these thin protective films are also becoming stricter. In other words, a new challenge has arisen: achieving both low gas emission and flatness.

[0005] Furthermore, in recent years, in addition to RGB, color filters (RGBW type) have been developed that have white (W) pixels on which the coloring composition for the pixels of the color filter is not applied. The protective film of the color filter (RGBW type) is required to fill the spaces of the W that are not coated with the above-mentioned coloring composition while also satisfying flatness. In other words, in addition to the conventional unevenness on pixels of about 1 to 2 μm, it is now required that even larger concave spaces of 2 to 3 μm be flattened with a thin film thickness of 2 μm or less on the colored pixel formation area. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2000-103937 [Patent Document 2] Japanese Patent Publication No. 2000-143772 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, according to the inventors' findings, the curable compositions described in Patent Documents 1 and 2 were unable to produce a protective film for color filters that met the required characteristics of low gas emission and flatness while also exhibiting excellent adhesion.

[0008] The present invention has been made in view of the above, and aims to provide a thermosetting composition that can form a protective film with excellent adhesion while satisfying the required characteristics of flatness and low gas emission, a cured film obtained by curing the composition, and a display device containing the cured film. [Means for solving the problem]

[0009] The inventors of the present invention conducted studies to solve the problems required for protective films of color filters as described above, and as a result found that the above problems can be solved by a thermosetting composition having a specific formulation, thus completing the present invention.

[0010] The thermosetting composition of the present invention contains (A) an epoxy compound, (B) a curing agent or (C) a curing accelerator, and (D) a solvent, wherein component (A) is an epoxy compound represented by the following general formula (1).

[0011] [ka]

[0012] In formula (1), a and d represent epoxy groups, and b and c represent alicyclic hydrocarbon skeletons having 5 or more carbon atoms. Two adjacent b and c members share two atoms with each other, and the carbon atoms constituting b or c may be bridged with each other within their respective rings. n represents 0 or a natural number. However, if n is 2 or greater, each c may be different.

[0013] The cured film of the present invention is obtained by curing the above-mentioned thermosetting composition.

[0014] The display device of the present invention has the above-mentioned cured film. [Effect of the Invention]

[0015] According to the present invention, it is possible to provide a thermosetting composition capable of forming a protective film that satisfies the required characteristics of flatness and low gas emission and also has excellent adhesion, a cured film obtained by curing the composition, and a display device including the cured film. [Embodiments for Carrying out the Invention]

[0016] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component has a first decimal place of 0, the notation after the decimal point may be omitted.

[0017] 1. Thermosetting Composition The thermosetting composition according to an embodiment of the present invention has (A) an epoxy compound, (B) a curing agent or (C) a curing accelerator, and (D) a solvent. Each component will be described below.

[0018] [Component (A)] Component (A) is an epoxy compound represented by the following general formula (1). Since the epoxy compound represented by the general formula (1) has a low viscosity, it easily enters the concave portions of the irregularities generated between the pixels of the color filter, and the flatness of the cured film can be improved. Further, since the epoxy compound represented by the following general formula (1) is difficult to shrink during curing, the adhesion of the cured film to the color filter substrate can be improved.

[0019] [Chemical Formula]

[0020] In the above general formula (1), a and d represent epoxy groups, b and c represent alicyclic hydrocarbon skeletons having 5 or more carbon atoms, and it is more preferable that b and c represent alicyclic hydrocarbon skeletons having 5 to 7 carbon atoms. Among the above b and c, two adjacent ones share two atoms with each other, and the carbon atoms constituting b or c may be crosslinked with each other within their respective rings, and it is preferable that at least one of b or c is crosslinked within the ring. Examples of the alicyclic hydrocarbon skeletons represented by b and c include cyclopentane, cyclohexane, cycloheptane, norbornane, and the like. n is preferably 0 or a natural number, more preferably 0 to 2, and even more preferably 1 to 2. However, when n is 2 or more, each c may be different.

[0021] Furthermore, it is more preferable that at least one of a or d of the epoxy compound represented by the above general formula (1) is a compound having an epoxy group represented by the following general formula (2), and it is more preferable that both a and d are compounds having an epoxy group represented by the general formula (2).

[0022]

Chemical formula

[0023] Examples of the epoxy compound represented by the above general formula (1) include epoxy compounds represented by the following formulas (4) to (11).

[0024]

Chemical formula

[0025]

Chemical formula

[0026]

Chemical formula

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] The epoxy equivalent of the epoxy compound represented by the above general formula (1) is preferably 60 g / eq to 300 g / eq, and more preferably 60 g / eq to 250 g / eq. When the epoxy equivalent is 60 g / eq or more, the reactivity is high and a sufficient crosslinking structure can be formed, thereby improving the heat resistance of the cured film. Furthermore, when the epoxy equivalent is 300 g / eq or less, unreacted epoxy compounds are less likely to remain in the cured film, so gas generation can be suppressed more effectively.

[0033] The epoxy equivalent can be determined, for example, by dissolving the curing composition solution in dioxane, then adding an acetic acid solution of tetraethylammonium bromide, and titrating with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0034] The content of component (A) is preferably 10% by mass or more and 85% by mass or less, and more preferably 20% by mass or more and 80% by mass or less, relative to the total mass of solids. By setting the content of component (A) to 10% by mass or more, a sufficient cross-linked structure can be formed, maintaining adhesion to the substrate, while the viscosity of the composition can be reduced and the flatness of the cured film can be further improved. In addition, by setting the content of component (A) to 10% by mass or more, the adverse effects on gas generation and various properties of the cured product by excess component (B) or (C) that did not contribute to the reaction can be suppressed. By setting the content of component (A) to 85% by mass or less, the adverse effects on gas generation by excess component (A) that did not react can be suppressed.

[0035] [(a) component] Component (a) is an epoxy compound other than component (A) above. By including component (a) in addition to component (A), the amount of gas generated from the cured product can be reduced more effectively.

[0036] (a) Examples of components include epoxy compounds having aromatic structures such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, and glycidyl ethers of polyhydric carboxylic acids. Epoxy compounds having a glycidyl group, such as sterols, copolymers of monomers containing (meth)acryloyl group as a unit, including copolymers of methacrylic acid and glycidyl methacrylate, hydrogenated bisphenol A diglycidyl ether (e.g., Licarezin HBE-100: manufactured by Shin Nippon Rika Co., Ltd., "Licarezin" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128 (manufactured by Dow Chemical), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation, "Celoxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolid GT401: manufactured by Daicel Corporation, "Epolid" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1: manufactured by Shikoku Chemicals, Inc.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 2,This includes alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton. In this invention, from the viewpoint of flatness and low gasification, epoxy compounds having the above-mentioned aromatic structure are preferred.

[0037] Among the epoxy compounds having the above aromatic structure, from the viewpoint of balancing flatness and low gasification properties, bisphenol fluorene type epoxy compounds or bisnaphthol fluorene type epoxy compounds are preferred, and bisaryl fluorene type epoxy compounds represented by the following general formula (3) are more preferred.

[0038] [ka]

[0039] In formula (3), Ar is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and some of the hydrogen atoms of the divalent aromatic hydrocarbon group may be substituted with a group selected from the group consisting of a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, and a halogen group. The average value of m is preferably between 0 and 2. By setting the average value to 2 or less, the properties of the cured film can be made satisfactory.

[0040] The average value of m above can be calculated from the epoxy equivalent of component (a) using the following formulas (1) and (2). When the epoxy compound represented by the above general formula (3) is a bisnaphthol fluorene type epoxy compound without substituents Equation (1) (Epoxy equivalent) × 2 = (Average value of m) × 506.6 + 562.7 When the epoxy compound represented by the above general formula (3) is a bisphenol fluorene type epoxy compound without substituents... Equation (2) (Epoxy equivalent) × 2 = (Average value of m) × 406.5 + 462.5

[0041] The epoxy compound represented by the above general formula (3) can be synthesized by known methods. For example, it can be synthesized by condensing 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxynaphthyl)fluorene with epichlorohydrin in the presence of an alkali, as described in Japanese Patent Application Publication No. 9-328534.

[0042] Furthermore, from the viewpoint of improving the chemical resistance of the cured film, it is preferable to include the above-mentioned alicyclic epoxy compound or hydrogenated bisphenol A diglycidyl ether. Among the above-mentioned alicyclic epoxy compounds, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 1,4-cyclohexanedimethanol-bis3,4-epoxycyclohexane carboxylate, and 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol are preferred. Among these, 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate and 2,2-bis(hydroxymethyl)-1-butanol are more preferred.

[0043] Furthermore, from the viewpoint of further improving chemical resistance while ensuring a balance between flatness and low gasification, it is more preferable to use an epoxy compound represented by general formula (3) in combination with the alicyclic epoxy compound described above.

[0044] (a) The content of component (a) is preferably more than 0% by mass and 80% by mass or less, and more preferably 10% by mass or more and 70% by mass or less, relative to the total mass of solids. (a) A content greater than 0% by mass can further improve low gasification. (a) A content of component (a) of 80% by mass or less can sufficiently exhibit flatness.

[0045] Furthermore, in the present invention, the total content of component (A) and component (a) is preferably 20% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 85% by mass or less, based on the total mass of solids. By having a total content of 20% by mass or more, sufficient properties as a cured film can be obtained. Also, by having a total content of 90% by mass or less, a sufficient amount of curing agent can be added, so the curing reaction can proceed sufficiently, the amount of unreacted epoxy compound remaining can be reduced, and gas generation can be suppressed.

[0046] [(B) Component] Component (B) is a curing agent. By including a curing agent, the curing reaction can proceed sufficiently, improving the low gas emission of the cured film.

[0047] Examples of component (B) include amine compounds that contribute to the curing of epoxy resins, polycarboxylic acid compounds or their anhydrides, thermally decomposable esters of polycarboxylic acids, phenolic resins, amino resins, dicyandiamides, Lewis acid complex compounds, etc. Among these, it is preferable to select from the group consisting of polycarboxylic acids or their anhydrides and thermally decomposable esters of polycarboxylic acids.

[0048] Polycarboxylic acids are compounds that have two or more carboxyl groups in one molecule. Examples of polycarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid This includes tetracarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ethertetracarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, and butane-1,2,3,4-tetracarboxylic acid, among others.

[0049] Examples of polycarboxylic acid anhydrides include the acid anhydrides of the polycarboxylic acids mentioned above. These may be intermolecular acid anhydrides, but generally intramolecularly cyclized acid anhydrides are used. Trimellitus anhydride is preferred as the acid anhydride.

[0050] Examples of pyrolytic esters of polycarboxylic acids include t-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylsulfanyl)ethyl esters of the above-mentioned polycarboxylic acids (wherein alkyl refers to a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and such hydrocarbon groups may have branched or cyclic structures and may be substituted with any substituent).

[0051] Furthermore, component (B) may also be a polymer or copolymer having two or more carboxyl groups, and the carboxyl groups of the polymer or copolymer may be anhydrides or pyrolytic esters. Examples of such polymers or copolymers include polymers or copolymers containing (meth)acrylic acid as a component, copolymers containing maleic anhydride as a component, and compounds obtained by reacting a tetracarboxylic dianhydride with a diamine or diol to open the ring of an acid anhydride.

[0052] The content of component (B) is preferably 5% by mass or more and 55% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, relative to the total mass of solids. When the content of component (B) is 5% by mass or more, the curing reaction proceeds sufficiently and the physical properties of the cured product, such as heat resistance, are sufficiently improved. In addition, the generation of gas due to the volatilization of unreacted component (A) can be suppressed. When the content of component (B) is 55% by mass or less, the adverse effects of excess component (B) that does not contribute to the curing reaction on gas generation and various properties of the cured product can be suppressed.

[0053] [(C) component] Component (C) is a curing accelerator. The inclusion of a curing accelerator accelerates the curing reaction, allowing a cured film to form in a short time.

[0054] Known compounds can be used as curing accelerators. Examples of curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, and 1,5-diazabicyclo[4.3.0]nona-5-ene; phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphinetriphenylborane; and metal compounds such as tin octylate. Among these, 1,8-diazabicyclo[5.4.0]undeca-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or their salts are preferred.

[0055] When using component (C), its content is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 3% by mass or less, relative to the total mass of solids. When the content of component (C) is 0.01% by mass or more, the curing reaction is accelerated and the reaction can be completed in a short time. When the content of component (C) is 5% by mass or less, sufficient storage stability is obtained and adverse effects on coloring during curing can be suppressed.

[0056] [(D) component] Component (D) is a solvent. By including a solvent, a liquid thermosetting composition can be obtained.

[0057] Any known solvent can be used as the solvent. Examples of solvents include terpenes such as α- or β-terpineol; ester solvents such as butyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, and 1,3-butylene glycol diacetate; ketone solvents such as acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, and cyclohexanone; ether solvents having an ethylene glycol skeleton such as diethylene glycol ethyl methyl ether, methyl cellosolve, ethyl cellosolve, methyl carbitol, dimethyl carbitol, ethyl carbitol, and butyl carbitol; and propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol monoethyl ether. These include ester and ether solvents having a propylene glycol skeleton, such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diacetate; acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, and butyl carbitol acetate; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxybutanol, and ethylene glycol mono-t-butyl ether; aromatic solvents such as toluene, xylene, and tetramethylbenzene; aliphatic solvents; amine solvents, and amide solvents. From a safety standpoint, ester and ether solvents having a propylene glycol skeleton are preferred. Two or more of these solvents may be used in combination.

[0058] The content of component (D) is preferably 50% to 95% by mass, and more preferably 70% to 90% by mass, based on the total mass of the thermosetting composition. A content of component (D) of 50% by mass or more allows for a viscosity that facilitates application of the thermosetting composition onto the color filter substrate. A content of component (D) of 95% by mass or less allows for a reduction in the drying time required after application of the thermosetting composition onto the color filter substrate.

[0059] [(E) component] Component (E) is a coupling agent. By including a coupling agent, adhesion not only to the color filter substrate but also to the glass substrate can be improved.

[0060] Examples of coupling agents include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane, as well as titanium-based coupling agents and aluminum-based coupling agents. Among these, 3-glycidoxypropyltrimethoxysilane, a silane coupling agent, is preferred.

[0061] The content of component (E) is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less, relative to the total mass of solids. A content of component (E) of 0.1% by mass or more allows for sufficient adhesion to the surface of the color filter substrate and the glass substrate. A content of component (E) of 20% by mass or less allows for a reduction in the amount of residual coupling agent, thereby suppressing gas generation.

[0062] [(F) component] The thermosetting composition of the present invention may contain a surfactant as component (F).

[0063] Examples of surfactants include fluorinated surfactants, silicone surfactants, nonionic surfactants, anionic surfactants, cationic surfactants, and betaine surfactants. Among these, fluorinated surfactants are preferred.

[0064] Examples of fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains.

[0065] Examples of silicone-based surfactants include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane.

[0066] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate.

[0067] Examples of anionic surfactants include ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate.

[0068] Examples of cationic surfactants include stearylamine acetate and lauryltrimethylammonium chloride.

[0069] Examples of betaine-based surfactants include lauryldimethylamine oxide and laurylcarboxymethylhydroxyethylimidazolinium betaine.

[0070] The surfactant content is preferably 0.001% by mass or more and 5% by mass or less, relative to the total mass of solids. When the content of component (E) is 0.001% by mass or more, good coatability is achieved, and when the content of component (E) is 5% by mass or less, good coating film properties are obtained.

[0071] [Other ingredients] Furthermore, the thermosetting composition of the present invention may optionally include other components such as resins, fillers, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoamers, and ultraviolet absorbers.

[0072] Examples of fillers include silica and talc.

[0073] Examples of resins include vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, and melamine resin.

[0074] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds.

[0075] Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina.

[0076] Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds.

[0077] Examples of UV absorbers include benzotriazole compounds, benzophenone compounds, and triazine compounds.

[0078] The thermosetting composition of the present invention can be obtained by mixing the above-described components (A) to (F) and (a).

[0079] Furthermore, the solid content concentration of the thermosetting composition of the present invention is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. By setting the solid content concentration to 5% by mass or more and 50% by mass or less, the viscosity can be made suitable for coating the thermosetting composition onto the color filter substrate.

[0080] 2.Cured film The cured film of the present invention is obtained by curing the thermosetting composition described above. Since the cured film of the present invention is obtained by curing the thermosetting composition described above, it satisfies the required properties of flatness and low gas emission while also having good adhesion.

[0081] Furthermore, known methods can be used to produce the cured film of the thermosetting composition of the present invention. For example, the thermosetting composition can be applied or injected onto a suitable substrate or mold according to the purpose and application, and then the solvent can be removed and cured by heating. Vacuum drying or the like may be applied to remove the solvent.

[0082] The cured film of the thermosetting composition of the present invention can be in the form of a film. By applying it to the surface of a coloring composition for pixels applied to a substrate of a color filter and curing it, it can be used as a protective film for the color filter. In this case, when creating a color filter that has white (W) pixels in addition to RGB pixels, where no coloring composition for pixels of the color filter is applied, applying and curing the thermosetting composition of the present invention to create a protective film allows for filling the W space of about 1.0 to 3.0 μm in depth that was formed because the coloring composition was not applied, while also satisfying flatness between the surface of the protective film formed on the RGB coloring composition applied to the substrate and the surface of the protective film formed on the W space.

[0083] The cured film obtained by curing the thermosetting composition of the present invention can be applied not only as a protective film for the color filter of LCDs, including RGBW type LCDs, but also to display devices that require a transparent cured film with particularly excellent flatness and low gas emission. In other words, it can be suitably applied as a component of organic EL display devices other than LCDs, μLED display devices, and quantum dot display devices, especially when a transparent film that flattens unevenness and steps is required. Furthermore, it can also be applied to sensors such as CMOS equipped with a color filter layer. In addition, since the cured film of the thermosetting composition of the present invention can fill holes in the steps as described above while achieving high surface flatness, it can be used in resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers such as multilayer printed circuit boards, gas barrier films, encapsulants for semiconductor light-emitting elements such as lenses and light-emitting diodes (LEDs), topcoats for paints and inks, hardcoats for plastics, and rust-preventive films for metals. Moreover, it is extremely useful not only as a coating agent, but also because the thermosetting composition itself can be molded and used to manufacture films, substrates, plastic parts, optical lenses, etc.

[0084] 3.Display device The display device of the present invention has the cured film described above. Because the display device of the present invention has the cured film described above, it is possible to make the LCD panel thinner. [Examples]

[0085] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto.

[0086] Note that when the same model of measuring instrument is used, the manufacturer's name is omitted from the second measurement onwards. Also, all glass substrates used in the examples have undergone the same treatment. Furthermore, when the first decimal place of the content of each component is 0, the decimal part may be omitted.

[0087] [Epoxy equivalent] The curing composition solution was dissolved in dioxane, then an acetic acid solution of tetraethylammonium bromide was added, and the result was determined by titration with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0088] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0089] (Preparation of thermosetting compositions) The components (A) to (F) and (a) shown in Tables 1 and 2 were stirred and mixed at room temperature for 3 hours to dissolve the solid components in the solvent. Refer to Examples 1-7. Examples 8 ~16. Thermosetting compositions according to comparative examples were prepared.

[0090] The values ​​for each component shown in Tables 1 and 2 are in parts by mass, and are listed so that the total solid content equals 100 parts by mass. Some of the solid components were synthesized already dissolved in a solvent (propylene glycol monomethyl ether acetate); in such cases, the composition values ​​are shown in parts by mass as solid content, and the solvent content introduced is included in the parts by mass of the solvent. The components used in Tables 1 and 2 are as follows:

[0091] [(A) Epoxy compounds represented by general formula (1)] (A)-1: In the above general formula (1), n=1, b has a cyclohexyl skeleton, c has a cyclopentyl skeleton, and a and d are represented by the above general formula (2), the epoxy compound represented by the following formula (4) (epoxy equivalent 80 g / eq)

[0092] [ka] (A)-2: In the above general formula (1), n=2, b has a cyclohexyl skeleton, c1 adjacent to b has a norbornane skeleton, c2 adjacent to c1 has a cyclopentyl skeleton, and a and d are represented by the general formula (2), the epoxy compound represented by the following formula (5) (epoxy equivalent 122 g / eq)

[0093] [ka] (A)-3: In the above general formula (1), n=2, b and c1 adjacent to b have a norbornane skeleton, c2 adjacent to c1 has a cyclopentyl skeleton, and a and d are represented by general formula (2), the epoxy compound represented by the following formula (6) (epoxy equivalent 115 g / eq)

[0094] [ka]

[0095] [(a) Other epoxy compounds] (a)-1: Fluorene-type epoxy resin (In general formula (3), Ar is a phenylene group, and m has an average value of 0 to 2. Epoxy equivalent weight 235-260 g / eq) (a)-2: 3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (Celoxide 2021P, manufactured by Daicel Corporation, epoxy equivalent 128-133 g / eq, "Celoxide" is a registered trademark of the company) (a)-3: 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150, manufactured by Daicel Corporation, epoxy equivalent 170-190 g / eq) (a)-4: Glycidyl methacrylate copolymer polymer with a copolymer composition of glycidyl methacrylate:methyl methacrylate:n-butyl methacrylate = 5:3:2 (Mw: approximately 9000, epoxy equivalent 730-1030 g / eq)

[0096] [(B) Hardener] (B): Trimellitus anhydride

[0097] [(C) Curing accelerator] Octylate of 1,8-diazabicyclo[5.4.0]undec-7-ene

[0098] [(D) Solvent] (D)-1: Propylene glycol monomethyl ether acetate (D)-2: Cyclohexanone

[0099] [(E) Coupling agent] (E): 3-Glycidoxypropyltrimethoxysilane

[0100] [(F) Surfactants] (F): Fluorine-based surfactant (manufactured by DIC Corporation, Megafac F-556; "Megafac" is a registered trademark of the company)

[0101] [Table 1]

[0102] [Table 2]

[0103] Tables 1 and 2 are shown below. Refer to Examples 1-7. Examples 8~16. The following evaluations were performed on the comparative example thermosetting compositions.

[0104] (Preparation of substrates with cured film for flatness evaluation) The thermosetting compositions shown in Tables 1 and 2 were applied to a color filter substrate using a spin coater so that the film thickness on the pixels after heat curing was 1.5 μm. A dried film was then prepared by drying it on a hot plate at 90°C for 2 minutes. Next, the dried film was baked in a hot air oven at 230°C for 30 minutes to obtain a substrate with a cured film for flatness evaluation. The color filter substrate used had a black matrix and red, green, and blue pixels, as well as a mosaic pattern with no blue pixels, and a recessed space of 2.5 μm in height was created in the areas where there were no blue pixels.

[0105] [Evaluation of flatness] (Evaluation method) The heights of the surface irregularities at two arbitrarily selected points on the surface of the cured film formed on the above substrate were measured using the micro-shape measuring instrument "SurfCorder ET4000A" (manufactured by Kosaka Research Institute Co., Ltd.), and the average value was calculated. A score of △ or higher was considered acceptable.

[0106] (Evaluation Criteria) ◎: The difference in height between the bumps and irregularities is 0.1 μm or less. ○: The difference in height between the bumps and ridges is greater than 0.1 μm and less than or equal to 0.15 μm. △: The difference in height between the bumps and ridges is greater than 0.15 μm and less than 0.2 μm. ×: The difference in height between the bumps and ridges is greater than 0.2 μm.

[0107] (Preparation of substrates with cured films for gas emission evaluation) The thermosetting compositions shown in Tables 1 and 2 were applied to a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning) using a spin coater to achieve a film thickness of 1.5 μm after heat curing. A dried film was then prepared by drying on a hot plate at 90°C for 2 minutes. Next, the dried film was baked in a hot air oven at 230°C for 30 minutes to obtain a substrate with a cured film for gas emission evaluation.

[0108] [Gas emission assessment] (Evaluation method) A 10 mg sample was scraped off the above-mentioned cured film and measured its weight loss using the "Thermo plus EVO2" simultaneous thermogravimetric analyzer (manufactured by Rigaku Corporation). The sample was heated from room temperature to 120°C at a rate of 10°C / min under an airflow, held at 120°C for 30 minutes, and then heated from 120°C to 230°C at a rate of 10°C / min, held at 230°C for 3 hours.

[0109] (Evaluation Criteria) ◎: Weight loss is less than 5% ○: The weight loss is between 5% and less than 7%. △: Weight loss is between 7% and 10%. ×: Weight loss is 10% or more.

[0110] (Preparation of substrates with cured film for adhesion evaluation) Using the same method as for preparing the substrates for gas emission evaluation described above, substrates with cured films for adhesion evaluation were prepared using the thermosetting compositions shown in Tables 1 and 2.

[0111] [Adhesion evaluation] (Evaluation method) Using the environmental testing machine "EHS-211MD" (manufactured by ESPEC), the cured film was held at 121°C and 100% humidity for 5 hours. After that, a cross-cut tape peel test was performed on the cured film, and it was evaluated on a 6-point scale from 5B to 0B according to the ASTM D3359 standard.

[0112] [Table 3]

[0113] [Table 4]

[0114] Examples 8From the results of examples 16 and the comparative examples, it was found that the thermosetting compositions of each example exhibited excellent flatness and adhesion, which are required for protective films of color filters. [Industrial applicability]

[0115] The thermosetting composition of the present invention can be applied not only as a protective film for color filters of LCDs, including RGBW systems, but also to display devices that require a transparent cured film with excellent flatness and low gas emission.

Claims

1. (A) Epoxy compounds and (B) a hardening agent and / or (C) a curing accelerator, (D) Solvent and It contains, The aforementioned component (A) is a thermosetting composition in which an epoxy compound represented by the following general formula (1) is 【Chemistry 1】 (In formula (1), a and d represent epoxy groups, and b and c represent alicyclic hydrocarbon skeletons having 5 or more carbon atoms. Two adjacent b and c members may share two atoms with each other, and the carbon atoms constituting b or c may be bridged with each other within their respective rings. n represents 0 or a natural number. However, if n is 2 or greater, each c may be different, and a and d are epoxy groups represented by the following general formula (2).) 【Chemistry 2】 (In formula (2), the dashed line indicates that the bond to which the dashed line is attached is part of the bonds that constitute the alicyclic hydrocarbon skeleton represented by b or c.) (a) Other epoxy compounds, including a compound represented by the following general formula (3): 【Transformation 3】 (In formula (3), Ar is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and some of the hydrogen atoms of the divalent aromatic hydrocarbon group may be substituted with a group selected from the group consisting of a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, and a halogen group. m is a number whose average value is between 0 and 2.) The content of the solvent (D) is 70% by mass or more and 90% by mass or less, based on the total mass of the thermosetting composition. Thermosetting composition.

2. The thermosetting composition according to claim 1, wherein the content of component (a) is more than 0% by mass and 80% by mass or less, relative to the total mass of solids.

3. The thermosetting composition according to claim 1 or claim 2, wherein component (B) is selected from the group consisting of polycarboxylic acids or their acid anhydrides, and thermally decomposable esters of polycarboxylic acids.

4. The content of component (A) is 10% by mass or more and 85% by mass or less, relative to the total mass of solids. The content of component (B) is 5% by mass or more and 55% by mass or less, relative to the total mass of solids. The thermosetting composition according to any one of claims 1 to 3, wherein the solid content concentration is 10% by mass or more and 30% by mass or less.

5. A thermosetting composition according to any one of claims 1 to 4, comprising (E) a coupling agent, wherein the content of the (E) coupling agent is 0.1% by mass or more and 20% by mass or less based on the total mass of solids.

6. A cured film obtained by curing a thermosetting composition according to any one of claims 1 to 5.

7. A display device having the cured film described in claim 6.

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