Curable resin composition

Abstract

To provide a curable resin composition capable of forming a patterned cured film.SOLUTION: The curable resin composition according to one aspect of the present invention contains a resin, a polymerizable compound, and a photoinitiator. The resin is a polymer of a monomer component containing a vinyltrialkoxysilane represented by formula (I), a trialkoxysilane represented by formula (II), and a tetraalkoxysilane represented by formula (III). (In the formulae, R1A-R1C, R2A-R2C and R3A-R3D each independently represent an optionally substituted alkyl group; and Q represents an optionally substituted hydrocarbon group (excluding a vinyl group).)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition, a cured film thereof, and a display device. [Background technology]

[0002] In display devices such as liquid crystal display devices and organic electroluminescence (EL) display devices, low refractive index components such as anti-reflection films and color mixing prevention walls are used. As a material that can be used to manufacture such low refractive index components, for example, the resin composition of Patent Document 1 is known. The resin composition of Patent Document 1 is a resin composition containing a specific fluorine-containing polysiloxane and a ketone-based compound, and contains 50% by mass or more of the ketone-based compound in 100% by mass of the resin composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-70758 Summary of the Invention [Problem to be solved by the invention]

[0004] Since the resin composition of Patent Document 1 is not photosensitive, it is not possible to form a patterned cured film by a method such as photolithography.

[0005] An object of the present invention is to provide a curable resin composition capable of forming a patterned cured film. [Means for solving the problem]

[0006] The present invention is as follows. [1] A composition comprising a resin, a polymerizable compound, and a photoinitiator; The resin is a curable resin composition which is a polymer of monomer components including a vinyltrialkoxysilane represented by formula (I), a trialkoxysilane represented by formula (II), and a tetraalkoxysilane represented by formula (III). [ka] (In the formula, R 1A ~R 1C , R 2A ~R 2C , and R 3A ~R 3D each independently represents an alkyl group which may have a substituent, Q is a hydrocarbon group which may have a substituent (excluding vinyl groups). [2] Q, R 1A ~R 1C , R 2A ~R 2C , and R 3A ~R 3D each independently represents an alkyl group having 1 to 4 carbon atoms. [3] The curable resin composition according to [1] or [2], further comprising a silane coupling agent. [4] A cured film obtained by curing the curable resin composition according to any one of [1] to [3]. [5] A display device comprising the cured film according to [4]. Effect of the Invention

[0007] According to the present invention, it is possible to provide a curable resin composition capable of forming a patterned cured film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this specification, unless otherwise specified as "optionally having a substituent", the terms "alkyl group", "phenyl group", and "hydrocarbon group" mean "alkyl group", "phenyl group", and "hydrocarbon group", respectively, that do not have a substituent.

[0009] In this specification, the term "total amount of solids in the curable resin composition" refers to the total amount of components other than the solvent in the curable resin composition. The total amount of solids and the content of each component relative to the total amount of solids can be measured by known analytical means such as liquid chromatography and gas chromatography.

[0010] In this specification, the weight average molecular weight is represented by the weight average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as the standard substance.

[0011] <Curable resin composition> A curable resin composition according to one aspect of the present invention includes a specific resin (A), a polymerizable compound (B), and a photoinitiator (C) described later. The curable resin composition may further include one or more components selected from the group consisting of a silane coupling agent (D), a leveling agent (E), and a solvent (F). As each of the components (A) to (F), a single compound may be used alone, or a combination of a plurality of compounds may be used. The curable resin composition according to this aspect can form a patterned cured film having a low refractive index, and therefore can be used for applications such as anti-reflection films and color mixing prevention walls in display devices. As described later, the curable resin composition according to this aspect does not require high temperatures (e.g., 200 to 230° C.) for curing, and therefore is particularly suitable for applications in organic EL display devices. In addition, the curable resin composition according to this aspect can form a cured film having excellent developability and storage stability (e.g., storage stability under high temperature and high humidity environments).

[0012] <Resin (A)> Resin (A) is a polymer of monomer components including vinyltrialkoxysilane represented by formula (I), trialkoxysilane represented by formula (II), and tetraalkoxysilane represented by formula (III). More specifically, resin (A) is a polysiloxane obtained by hydrolyzing and condensing the monomer components. [ka]

[0013] In formulas (I) to (III), R 1A ~R 1C , R 2A ~R 2C , and R 3A ~R 3D Each of R is independently an alkyl group which may have a substituent. 1A ~R 1C , R 2A ~R 2C , and R 3A ~R 3D are each independently preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group, and is preferably a methyl group or an ethyl group. The substituent on the alkyl group may be, for example, a halogen atom or a phenyl group.

[0014] In formula (II), Q is a hydrocarbon group which may have a substituent (excluding vinyl group). Q is preferably an alkyl group which may have a substituent or a phenyl group which may have a substituent, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and even more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group, and is preferably a methyl group or an ethyl group.

[0015] From the viewpoint of pattern forming, the substituent on the hydrocarbon group in Q is preferably a substituent other than an acidic group. In this specification, the acidic group means a group that shows acidity according to the Bronsted definition, and examples thereof include a hydroxyl group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The substituent other than the acidic group may be, for example, a halogen atom.

[0016] The content of the vinyltrialkoxysilane represented by formula (I) in the monomer component may be, for example, 10 to 80 mass%, 20 to 60 mass%, 25 to 50 mass%, or 25 to 35 mass%. The content of the trialkoxysilane represented by formula (II) in the monomer component may be, for example, 10 to 80 mass%, 20 to 60 mass%, 25 to 50 mass%, or 30 to 50 mass%. The content of the tetraalkoxysilane represented by formula (III) in the monomer component may be, for example, 10 to 80 mass%, 20 to 60 mass%, 25 to 50 mass%, or 25 to 35 mass%.

[0017] The monomer component may consist of only the vinyltrialkoxysilane represented by formula (I), the trialkoxysilane represented by formula (II), and the tetraalkoxysilane represented by formula (III), or may further contain other monomers in addition to these monomers. From the viewpoints of pattern formability, developability, and viscosity, the content of other monomers in the monomer component is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less. The monomer component may not contain other monomers.

[0018] When the monomer component contains a dialkoxysilane as another monomer, the content of the dialkoxysilane in the monomer component may be 5% by mass or less, preferably 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.75% by mass or less, or 0.5% by mass or less, from the viewpoint of pattern formability. From the viewpoint of pattern formability, it is more preferable that the monomer component does not contain a dialkoxysilane. Also, from the viewpoint of pattern formability, it is preferable that the other monomer does not contain the above-mentioned acidic group (excluding silanol group).

[0019] The weight average molecular weight of the resin (A) is not particularly limited, but may be, for example, 500 to 50,000 or 800 to 10,000.

[0020] The content of the resin (A) is preferably from 10 to 90 mass %, more preferably from 20 to 80 mass %, and further preferably from 35 to 75 mass %, based on the total amount of solids in the curable resin composition.

[0021] <Polymerizable compound (B)> The polymerizable compound (B) is a compound that can be polymerized by active radicals generated from the photoinitiator (C). The polymerizable compound (B) may be, for example, a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth)acrylic acid ester compound. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid, "(meth)acryloyl" refers to at least one selected from the group consisting of acryloyl and methacryloyl, and "(meth)acrylate" refers to at least one selected from the group consisting of acrylate and methacrylate.

[0022] The polymerizable compound (B) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tri(meth)acrylate ... pentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated alkoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate), alkoxylated dipentaerythritol poly(meth)acrylates (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol caprolactone-modified pentaerythritol poly(meth)acrylate (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylate (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate). Among these, it is preferable to include at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkoxylated pentaerythritol poly(meth)acrylate, and alkoxylated dipentaerythritol poly(meth)acrylate, and it is more preferable to include at least one selected from the group consisting of trimethylolpropane triacrylate, dipentaerythritol polyacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated dipentaerythritol polyacrylate.

[0023] The weight average molecular weight of the polymerizable compound (B) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

[0024] The content of the polymerizable compound (B) is preferably 1 to 65 mass%, more preferably 5 to 60 mass%, and further preferably 10 to 55 mass%, based on the total amount of solids in the curable resin composition. When the content of the polymerizable compound (B) is within the above range, the residual film rate during pattern formation and the chemical resistance of the cured film of the curable resin composition tend to be improved.

[0025] <Photoinitiator (C)> The photoinitiator (C) is not particularly limited as long as it is a compound that can generate active radicals or the like by light and initiate polymerization, and any known photoinitiator can be used.

[0026] Examples of photoinitiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

[0027] Examples of the O-acyloxime compound include O-acyloxime compounds having a diphenyl sulfide skeleton such as N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-one-2-imine; imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and other O-acyloxime compounds having a carbazole skeleton; and O-acyloxime compounds having a fluorene skeleton, such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime. Commercially available products such as Irgacure (registered trademark) OXE01 or OXE02 (manufactured by BASF), ADEKA ARCLES NCI-930 or N-1919 (manufactured by ADEKA CORPORATION), and DFI-091 (manufactured by Daito Chemistry Corporation) may also be used.As the O-acyloxime compound, at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime is preferred. In terms of the brightness and sensitivity of the resulting cured film, it is preferred to use these O-acyloxime compounds.

[0028] Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. Commercially available products such as Omnirad (registered trademark) (formerly Irgacure (registered trademark)) 369, 907, and 379 (all manufactured by IGM Resins BV) may also be used.

[0029] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0030] The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Omnirad (registered trademark) 819 (manufactured by IGM Resins BV) may also be used.

[0031] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0032] Further examples of the photoinitiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone; benzyl; methyl phenylglyoxylate; and titanocene compounds.

[0033] As the photoinitiator (C), a photoinitiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound is preferable, and a photoinitiator containing an O-acyloxime compound is more preferable.

[0034] The content of the photoinitiator (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). When the content of the photoinitiator (C) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, thereby improving the productivity of the cured film of the curable resin composition.

[0035] <Silane coupling agent (D)> Examples of the silane coupling agent (D) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Examples of commercially available products of these silane coupling agents include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, etc., manufactured by Shin-Etsu Chemical Co., Ltd. By including the silane coupling agent (D), the adhesion of the obtained cured film becomes better.

[0036] The content of the silane coupling agent (D) may be, for example, 0.1 to 50 parts by mass, 0.5 to 30 parts by mass, or 1 to 10 parts by mass relative to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B).

[0037] <Leveling agent (E)> Examples of the leveling agent (E) include silicone surfactants, fluorine-based surfactants, etc. These surfactants may have a polymerizable group in the side chain.

[0038] Examples of silicone surfactants include surfactants having siloxane bonds in the molecule.Specific examples of silicone surfactants include DOWSIL (registered trademark) (formerly Toray Silicone) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0039] Alternatively, the silicone surfactant may be a silicone surfactant having a fluorine atom. Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, examples of the silicone surfactant include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0040] The above-mentioned fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in its molecule.Specifically, fluorine-based surfactants include Fluorard (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited); Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation); F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.)); and E5844 (manufactured by Daikin Fine Chemicals Research Institute Co., Ltd.).

[0041] The content of the leveling agent (E) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, and even more preferably 0.005% by mass or more and 0.2% by mass or less, based on the total amount of the curable resin composition. When the content of the leveling agent (E) is within the above range, the flatness of the cured film of the curable resin composition is improved.

[0042] <Solvent (F)> The solvent (F) is not particularly limited, and one or more solvents commonly used in the field can be used. Examples of the solvent (F) include ester solvents (i.e., solvents that contain -COO- in the molecule and do not contain -O-), ether solvents (i.e., solvents that contain -O- in the molecule and do not contain -COO-), ether ester solvents (i.e., solvents that contain -COO- and -O- in the molecule), ketone solvents (i.e., solvents that contain -CO- in the molecule and do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0043] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0044] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran (THF), tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0045] The ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methyl ... Examples of the alkyl ether acetates include ethyl 2-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0046] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0047] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0048] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0049] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0050] Among the above solvents, from the viewpoint of coatability and drying property, preferred are organic solvents having a boiling point at 1 atm of 120° C. or more and 180° C. or less. As the solvent (F), preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide, and more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate.

[0051] The content of the solvent (F) may be, for example, 65 to 95 mass%, preferably 70 to 95 mass%, and more preferably 75 to 92 mass%, based on the total amount of the curable resin composition. In other words, the total amount of solids in the curable resin composition may be, for example, 5 to 35 mass%, preferably 5 to 30 mass%, and more preferably 8 to 25 mass%. When the content of the solvent (F) is within the above range, the flatness during application is improved.

[0052] <Other ingredients> The curable resin composition according to this aspect may contain additives known in the art, such as polymerization initiators, fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents, as necessary. However, from the viewpoint of use in applications such as anti-reflection films or color mixing prevention walls, it is preferable that the curable resin composition does not contain a colorant. In addition, the curable resin composition may or may not contain particles (e.g., hollow or porous particles, specifically, hollow silica). In general, the addition of particles is known as a method for lowering the refractive index of a resin composition containing polysiloxane, but the curable resin composition according to this aspect can achieve a low refractive index even without containing particles, and the refractive index can be further reduced by adding particles. In addition, an antioxidant and / or an ultraviolet absorber may be added.

[0053] <Method for producing curable resin composition> The curable resin composition according to this aspect can be prepared by mixing a resin (A), a polymerizable compound (B), and a photoinitiator (C), and optionally a silane coupling agent (D), a leveling agent (E), a solvent (F), and other components.

[0054] <Cured film and its manufacturing method> A cured film according to one aspect of the present invention is a film obtained by curing the curable resin composition according to the above aspect, that is, a cured product of the film of the curable resin composition according to the above aspect. Since such a cured film has a low refractive index, it can be used as a member that requires a low refractive index, such as an anti-reflection film or a color mixing prevention wall of a display device. Examples of the display device include a liquid crystal display device, an organic EL display device, a plasma display, and electronic paper. As described later, the cured film according to this aspect does not require a high temperature (e.g., 200 to 230° C.) for curing, and is therefore particularly suitable as a member used in an organic EL display device. In addition, the cured film according to this aspect is also excellent in developability and storage stability (e.g., storage stability under high temperature and high humidity conditions).

[0055] The refractive index of the cured film is preferably 1.20 to 1.55, more preferably 1.30 to 1.50, and even more preferably 1.40 to 1.50. In this specification, the refractive index of the cured film is indicated as a refractive index at a wavelength of 550 nm. The refractive index can be measured by spectroscopic ellipsometry using an appropriate instrument such as M-2000 manufactured by J.A. Woollam Japan Co., Ltd.

[0056] The thickness of the cured film is not particularly limited and can be appropriately adjusted depending on the application of the cured film. The thickness of the cured film is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0057] The cured film may have a pattern such as a line and space pattern, etc. The pattern is not particularly limited and can be appropriately determined depending on the application of the cured film.

[0058] The cured film can be produced by forming the curable resin composition into a film and curing the film of the curable resin composition by irradiating it with light. Specifically, the cured film can be formed on any substrate by a known method such as a photolithography method, an inkjet method, or a printing method. Among these, the photolithography method is preferred.

[0059] The substrate may be, for example, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate, or silicon. Substrates having a thin film of aluminum, silver, or a silver / copper / palladium alloy on these substrates may also be used. Substrates having another resin layer, transistor, circuit, or the like on these substrates may also be used.

[0060] In the photolithography method, first, the above-mentioned curable resin composition is applied to a substrate, and the curable resin composition is dried to form a layer of the curable resin composition. The application of the curable resin composition can be performed, for example, by a spin coating method, a slit coating method, or a slit-and-spin coating method. The thickness of the layer of the curable resin composition can be appropriately adjusted according to the desired thickness of the cured film. The drying of the curable resin composition can be performed, for example, by heat drying (pre-baking) and / or reduced pressure drying. The temperature of the heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. The reduced pressure drying is preferably performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

[0061] Next, the curable resin composition layer is exposed through a photomask having a desired pattern, and then developed by contacting with a developer to form a pattern (i.e., a patterned cured film) made of a cured product of the curable resin composition on the substrate. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. Light of such a wavelength can be obtained, for example, by cutting light of a specific wavelength range (for example, less than 350 nm) from a predetermined light source using a filter that cuts this wavelength range, or by selectively extracting light of a specific wavelength (for example, near 436 nm, near 408 nm, or near 365 nm) using a bandpass filter that extracts these wavelength ranges. The light source may be, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, or a halogen lamp. It is preferable to use an exposure device such as a mask aligner or a stepper, because it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to accurately align the photomask and the substrate.

[0062] The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant. Development may be performed by, for example, a puddle method, a dipping method, or a spray method. The substrate may be tilted at any angle during development. By development, the unexposed portion of the layer of the curable resin composition is dissolved in the developer and removed.

[0063] The obtained cured film is preferably post-baked. The post-baking temperature can be appropriately determined depending on the application of the cured film. For example, when the cured film is used as a member for an organic EL display device, the post-baking temperature is preferably 80 to 130°C. In general, in consideration of the heat resistance temperature of an organic EL, a cured film that requires a high temperature (e.g., 200 to 230°C) for curing is not suitable as a member for an organic EL display device, but the cured film according to this aspect does not require a high temperature for curing, and is therefore suitable as a member for an organic EL display device. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0064] In the above photolithography method, a cured film having no pattern can be obtained by not using a photomask during exposure and / or not developing.

[0065] <Display device> A display device according to one aspect of the present invention includes the cured film according to the above aspect. Specifically, the display device may include the cured film according to the above aspect as a member that requires a low refractive index, such as an anti-reflection film or a color mixing prevention wall. The display device is not particularly limited, and examples thereof include a liquid crystal display device, an organic electroluminescence display device, a plasma display, and electronic paper. The display device is preferably an organic electroluminescence display device. EXAMPLES

[0066] The present invention will be described in more detail below with reference to examples. In the following, "%" and "parts" are by mass % and parts by mass, respectively, unless otherwise specified.

[0067] In the following synthesis examples, the weight average molecular weight of the resin was measured using a GPC method as follows. First, the solvent of the resin solution was distilled off under reduced pressure, and the resulting resin was dissolved in THF to prepare a 0.02% by mass solution. Then, after passing through a filter (GL Sciences, GL Chromatodisc, water-based 25A, pore size 0.2 μm), the weight average molecular weight was measured under the following conditions using Alliance (Nihon Waters, Inc.) consisting of a size exclusion chromatograph and a refractive index detector. Column: pLgelmixedD (Agilent) x 2 connected in series Detector: Alliance (manufactured by Nihon Waters K.K.) Eluent:THF Flow rate: 1.0mL / min Injection volume: 100μL

[0068] (Synthesis Example 1: Resin a1) 150 parts of tetraethoxysilane, 143 parts of methyltriethoxysilane, 160 parts of vinyltrimethoxysilane, and 600 parts of propylene glycol monomethyl ether (PGME) were mixed in a suitable container. 180 parts of 0.090 mol / L nitric acid solution was added and the reaction was carried out at 60°C for 60 minutes under a nitrogen stream to obtain a solution of a resin (hereinafter referred to as resin a1). The obtained solution was free of precipitate, had a solids concentration of 17.5%, and had a viscosity of 3.3 mPa·s. The acid value of resin a1 calculated as solids was 37.2 mg KOH / g, and the weight average molecular weight was 2000.

[0069] (Comparative synthesis example 2: resin a2) A solution of a resin (hereinafter referred to as resin a2) was obtained in the same manner as in Synthesis Example 1, except that vinyltrimethoxysilane was changed to methacryloxypropyltriethoxysilane. The obtained solution was free of precipitates, had a solids concentration of 15.9%, and had a viscosity of 3.1 mPa s. The weight-average molecular weight was 1000.

[0070] <Preparation of Curable Resin Composition> The resin (A), polymerizable compound (B), photoinitiator (C), silane coupling agent (D), leveling agent (E), solvent (F), and other components were mixed in the amounts (parts by mass) shown in Table 1 to prepare a curable resin composition. [Table 1] The details of the ingredients in the table are as follows: Polymerizable compound b1: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Photoinitiator c1: Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) Silane coupling agent d1: KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd.) Leveling agent e1: Polyether modified silicone oil (TORAY SILICONE (registered trademark) SH 8400; manufactured by Dow Corning Toray Co., Ltd.) Solvent F1: Propylene glycol monomethyl ether Solvent F2: Propylene glycol monomethyl ether acetate Antioxidant: 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumilizer® GP; manufactured by Sumitomo Chemical Co., Ltd.) Ultraviolet absorber: 2-(2,4-dihydroxyphenyl)-2H-benzotriazole (Dynesorb (registered trademark) T-0; manufactured by Daiwa Kasei Co., Ltd.) Particles: Hollow silica (HS-20; manufactured by Nano New Materials Co., Ltd.)

[0071] <Preparation of cured film> A curable resin composition was applied by spin coating onto a 4-inch square glass substrate so that the film thickness after post-baking was 1 μm, and then pre-baked at 80° C. for 3 minutes to obtain a curable resin composition layer. This curable resin composition layer was exposed to 100 mJ / cm 2 in air using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultra-high pressure mercury lamp) with a distance of 200 μm between the curable resin composition layer and a quartz glass photomask. 2 The layer was irradiated with light at an exposure dose (365 nm standard). The light irradiation was performed by passing the light emitted from an ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a 1:1 line and space pattern with a line width of 100 μm, 50 μm, or 40 μm was used. The curable resin composition layer after the light irradiation was developed by immersing it in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23° C. for 60 seconds. After washing with water, the layer was post-baked on a hot plate at 85° C. for 30 minutes to produce a cured film having a line and space pattern formed thereon.

[0072] <Refractive index measurement> The refractive index of the cured film at a wavelength of 550 nm was measured by spectroscopic ellipsometry using an M-2000 manufactured by J.A. Woollam Japan Co., Ltd. The results are shown in Table 1. The cured films of Examples 1 and 2 and Comparative Example 1 all had a low refractive index.

[0073] <Pattern Formation Evaluation> The cured film having a line and space pattern was observed using a microscope (magnification 500 times, VF-7510; manufactured by Keyence Corporation). The case where a 1:1 line and space pattern without chipping was formed at any line width was evaluated as "good", and the case where a 1:1 line and space pattern without chipping was not formed at any line width was evaluated as "bad". The results are shown in Table 1. From the curable resin compositions of Examples 1 and 2, a cured film having a pattern without chipping could be produced, but when the curable resin composition of Comparative Example 1 was used, the curable resin composition peeled off during development, and a pattern without chipping could not be formed.

[0074] <Storage stability test> A storage stability test was performed by leaving the cured film for three days in an environment of 60°C and 90% relative humidity. The film thickness was measured before and after the test, and the rate of change in film thickness after the test relative to the film thickness before the test was calculated. The results are shown in Table 1.

Claims

1. A composition comprising a resin, a polymerizable compound, and a photoinitiator, The resin is a curable resin composition which is a polymer of monomer components including a vinyltrialkoxysilane represented by formula (I), a trialkoxysilane represented by formula (II), and a tetraalkoxysilane represented by formula (III). 【Chemistry 1】 (In the formula, R １Ａ ~R １Ｃ , R ２Ａ ~R ２Ｃ , and R ３Ａ ~R ３Ｄ each independently represents an alkyl group which may have a substituent, Q is a hydrocarbon group which may have a substituent (excluding vinyl groups).

2. Q, R １Ａ ~R １Ｃ , R ２Ａ ~R ２Ｃ , and R ３Ａ ~R ３Ｄ The curable resin composition according to claim 1, wherein each independently represents an alkyl group having 1 to 4 carbon atoms.

3. The curable resin composition according to claim 1 or 2, further comprising a silane coupling agent.

4. A cured film obtained by curing the curable resin composition according to claim 1.

5. A display device comprising the cured film according to claim 4.

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