JP2019183024A - Thermosetting composition - Google Patents

Abstract

To provide a thermosetting composition that gives a cured film excellent in heat resistance, barrier properties, tackless, adhesion, surface smoothness, and transparency, and a cured film formed of the thermosetting composition, and provide an electronic component having the cured film.SOLUTION: A thermosetting composition contains a copolymer (A) that is a reaction product of a monomer (a) represented by the formula (1) and a monomer (b) other than (a), a compound (B) having three or more epoxy groups, a compound (C) having four or more (meth) acryloyl groups and a solvent (D). In the formula (1), Rand Rindependently represent hydrogen, C1-3 alkyl or phenyl.SELECTED DRAWING: None

Description

  The present invention can be used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, a protective film for a color filter, and the like. The present invention relates to a curable composition, a transparent film thereby, and an electronic component having the film.

  The manufacturing process of an element such as a liquid crystal display element includes a process of forming an organic thin film having various functions. For example, black matrix resist film formation / patterning / heat treatment process, color filter resist film formation / patterning / heat treatment process, color filter protective film formation / patterning / heat treatment process, ITO conductive film formation process, for ITO patterning Photoresist film formation / patterning / wet etching / resist stripping process, ITO annealing process, alignment film formation / heat treatment / rubbing (polarization exposure) process, and the like. In these various processes, the device has an opportunity to contact various chemicals such as organic solvents, acids, alkaline solutions, etc., and when the electrode is formed by sputtering, the surface is locally exposed to high temperature. In some cases. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, applicability, flatness, light resistance Etc. are required. In particular, in recent years, the color gamut has been required to be expanded to improve display quality, and the required characteristics of color filters have become stricter, resulting in the problem of elution of pigments and dyes from the color filters. There is an increasing demand for improving the barrier properties of the film.

  Until now, in order to provide a protective film, the proposal which utilizes a polyimide material as a protective film is made (patent document 1). A protective film using a siloxane material characterized by high heat resistance and transparency has also been proposed (Patent Documents 2 and 3). Alternatively, a protective film using an epoxy resin and a melamine resin, and a protective film using an acrylic resin or a polyester resin have been proposed (Patent Documents 4, 5, and 6). Thermosetting materials containing polyfunctional acrylates in the composition have also been proposed (Patent Documents 7, 8, and 9).

  However, in a protective film using a polyimide material, in order to prepare a polyimide or polyimide precursor (polyamic acid) solution, it is necessary to use a so-called polyimide solvent having a strong dissolving power such as N-methylpyrrolidone or γ-butyrolactone. There is a problem that the underlying organic thin film is dissolved. This is a big problem especially when used as a protective film for a color filter, and becomes a factor of lowering barrier properties. In addition, polyimide also has a problem of coloring because the bottom of the light absorption band extends in the visible light region due to charge transfer interaction (CT interaction). On the other hand, when a siloxane material (sol-gel material) is used, the heat resistance and transparency are sufficient, but the temperature required for completing the reaction of the silanol group is 300 ° C. or higher, so that the underlying organic thin film There is also a problem that causes deterioration and a problem that cracks occur in the thin film due to curing shrinkage. In addition, the -Si-O-Si- bond of the siloxane material has a difficulty that it is easily hydrolyzed by alkali. In the case of a material using an epoxy resin and a melamine resin, there is no problem with the solvent used and the heat treatment temperature, but there is also a problem of yellowing. Although barrier properties can be improved with materials using acrylic resin, problems are likely to occur due to compatibility with other properties. In addition, the material containing a polyfunctional acrylate can improve the barrier property, but the film obtained by drying the solvent after coating has tackiness, and dust from the environment adheres to the surface to generate a film defect. There was a problem such as.

  From the above situation, there has been a demand for a material that has both barrier properties and other properties, particularly tackiness, flatness, adhesion to a base substrate, and transparency.

Patent Document 1 JP-A-62-163016
Patent Document 2 Japanese Patent Laid-Open No. 62-242918
Patent Document 3 Japanese Patent Laid-Open No. 7-331178
Patent Document 4 JP 63-131103 A
Patent Document 5 JP-A-8-50289
Patent Document 6 JP2013-253263A
Patent Document 7 JP2009-203364A
Patent Document 8 JP2011-68779A
Patent Document 9 JP 2012-41535 A

  The subject of this invention is providing the thermosetting composition which gives the cured film excellent in barrier property, tacklessness, adhesiveness, flatness, and transparency, and the cured film formed by this thermosetting composition. Furthermore, it is to provide an electronic component having the cured film.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a copolymer obtained by copolymerizing a monomer having an acid anhydride group and another monomer, and at least three or more The present invention has been completed by using a thermosetting composition containing a compound having an epoxy group, a compound having at least four (meth) acryloyl groups, and a solvent. The present invention includes the following configurations.

式（１）において、Ｒ^１及びＲ^２は独立して水素、炭素数１〜３のアルキル又はフェニルである。 [1] Copolymer (A) which is a reaction product from monomers (b) other than monomers (a) and (a) represented by the following formula (1), three or more epoxy groups A thermosetting composition containing a compound (B) having a compound, a compound (C) having four or more (meth) acryloyl groups, and a solvent (D).

In the formula (1), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbon atoms, or phenyl.

式（２）において、Ｒ^１及びＲ^２は独立して水素、炭素数１〜３のアルキル又はフェニルであり、Ｒ^３は１価の有機基である。 [2] The thermosetting composition according to item [1], wherein the monomer (b) is at least one selected from a compound represented by the following formula (2) and indene.

In Formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbons or phenyl, and R ³ is a monovalent organic group.

[3] The thermosetting composition according to item [1], wherein the compound (B) having three or more epoxy groups is a compound having an aromatic ring.

[4] A cured film formed from the thermosetting composition according to any one of [1] to [3].

[5] A color filter having the cured film according to the item [4] as a transparent protective film.

  The thermosetting composition according to a preferred embodiment of the present invention is a material that is excellent in barrier properties, tacklessness, adhesion, flatness, transparency, and can form a cured film that is particularly excellent in barrier properties, and is a color liquid crystal When used as a color filter protective film of a display element, display quality can be improved. In particular, it is useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. Thermosetting composition of the present invention The thermosetting composition of the present invention comprises a copolymer (A) containing a compound represented by the formula (1), a compound having three or more epoxy groups (B), 4 It is a thermosetting composition containing the compound (C) which has a 1 or more (meth) acryloyl group, and a solvent (D). In the thermosetting composition of the present invention, 10 to 500 parts by weight of the compound (B) having 3 or more epoxy groups is contained per 100 parts by weight of the copolymer (A). ) The compound (C) having an acryloyl group is preferably 50 to 200 parts by weight.

1-1. Copolymer (A)
The copolymer (A) is represented by the compound represented by the formula (1) as the monomer (a) and the formula (2) as another monomer (b) other than the monomer (a). And a raw material that necessarily contains a compound selected from indene and radical copolymerization in the presence of a radical initiator. Further, the other monomer (b) may contain a compound other than the above compounds.

  In the other monomer (b), when a compound represented by the formula (2) and a compound other than indene are used, from the viewpoint of heat resistance, preferably 0 to 40 wt% of the whole monomer used for radical polymerization More preferably, the addition amount is 0 to 20 wt%.

  Further, at least a solvent is required for the synthesis of the copolymer (A). The solvent may be left as it is, and it may be a liquid or gel composition considering handling properties, or the solvent may be removed and a solid composition considering transportability may be used.

  Other compounds than the above may be contained within a range not impairing the object of the present invention. Examples of other raw materials may include a radical polymerizable monomer and a chain transfer agent.

1-1-1. Monomer (a) and monomer (b)
In this invention, the compound represented by Formula (1) is included as a monomer (a) as a material for obtaining a copolymer (A). Further, the other monomer (b) contains one or more compounds selected from the compound represented by the formula (2) and indene. Specific examples of Formula (1) include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, phenylmaleic anhydride, and 2,3-diphenylmaleic anhydride. Specific examples of the compound represented by the formula (2) include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. Moreover, you may also contain monomers (b) other than the compound represented by Formula (2) and indene in the range which does not impair the characteristic of this invention. Specific examples in that case are methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate. , Isobornyl methacrylate, dicyclopentanyl methacrylate, 2,2,2-trifluoroethyl methacrylate.

1-1-2. Solvents used for the synthesis of copolymer (A) Specific examples of solvents used for the synthesis to obtain copolymer (A) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-Ethoxyp Ethyl lopionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone Cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, and the like. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

1-1-3. Radical initiator used for the synthesis of copolymer (A) When synthesizing copolymer (A), a commercially available azo or peroxide radical initiator can be used as a radical initiator for initiating the polymerization reaction. Specific examples of the azo radical reaction initiator include, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2 , 4-dimethoxyvaleronitrile) and 2,2′-azobis (4-dimethoxy-2,4-dimethylvaleronitrile). Specific examples of the peroxide radical initiator include benzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, and bis (4-t-butylcyclohexyl) peroxydicarbonate. A radical initiator may be used independently and may be used in mixture of 2 or more types.

1-1-4. Molecular weight regulator used for the synthesis of the copolymer (A) When the copolymer (A) is synthesized, the molecular weight regulator is further contained in order to suppress an increase in the molecular weight and to exhibit excellent storage stability. May be. Examples of the molecular weight modifier include mercaptans, xanthogens, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene.

  Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-t-butylhydroquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid Dimethylxanthogen sulfide, diisopropylxanthogen disulfide, and 2,4-diphenyl-4-methyl-1-pentene.

  A molecular weight modifier may be used independently and may be used in combination of 2 or more.

1-1-5. Method for Synthesizing Copolymer (A) The copolymer (A) used in the present invention is a monomer selected from the compound represented by the formula (1), the compound represented by the formula (2), and indene. The polymer is polymerized in the solvent in the presence of a thermal radical initiator.

  In the synthesis of the copolymer (A), the polymerization heat is large because the monomers of the formulas (1) and (2) are copolymerized. When the polymerization control is difficult due to the polymerization heat, the heat of polymerization can be reduced by using a chain transfer agent. The chain transfer agent is not particularly limited, but 2,4-diphenyl-4-methyl-1-pentene is preferably used.

  The reaction solvent is preferably used in an amount of 80 parts by weight or more with respect to 100 parts by weight of the solute since the reaction proceeds smoothly. The reaction is carried out at 40 to 200 ° C. for 0.2 to 20 hours.

  In the radical polymerization, a reaction temperature of 40 ° C to 120 ° C is preferable, and a reaction temperature of 60 ° C to 80 ° C is more preferable.

  The weight average molecular weight of the obtained copolymer is preferably 1,000 to 1,000,000, and more preferably 3,000 to 500,000. If it exists in these ranges, applicability | paintability and flatness will be favorable.

  The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). For standard polystyrene, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies) is used, and PLgel MIXED-D (Agilent Technology, Inc.) is used for the column. It can be measured using THF as the mobile phase. The weight average molecular weight of the commercial product in this specification is a catalog publication value.

1-2. Compound (B) having three or more epoxies
The epoxy compound used in the present invention is a compound having three or more epoxy groups per molecule. The epoxy compound (B) may be one type or two or more types.

1-2. Example of Compound (B) Having Three or More Epoxy Groups As an example of the compound (B) having three or more epoxy groups, TECHMORE VG3101L (trade name, Printec Co., Ltd.), EHPE3150 ( (Trade name, Daicel Corporation), EPPN-501H, 502H (all trade names, Nippon Kayaku Co., Ltd.), jER 1032H60 (trade name, Mitsubishi Chemical Corporation), Denacol EX-313, EX-314, EX-321 , EX-411, EX-421, EX-512, EX-521, EX-612, EX-614, EX-614B, DLC-302, DLC-402 (trade name, Nagase ChemteX Corporation), NC-3000 NC-3000-L, NC-3000-H, NC-3100 (all trade names, Nippon Kayaku Co., Ltd. ), EPPN-201 (trade name, Nippon Kayaku Co., Ltd.), jER 152, jER 154 (both trade names, Mitsubishi Chemical Corporation), EOCN-102S, 103S, 104S, 1020 (all trade names, Nippon Kayaku) Yakuhin Co., Ltd.), jER 157S65, 157S70 (both trade names, Mitsubishi Chemical Corporation), 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name, Gerest Incorporated) ), TSL 9906 (trade name, Momentive Performance Materials LLC), COATOSIL MP200 (trade name, Momentive Performance Materials Japan LLC), Composeran SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES- 1023 (Product name, trust Chemical Industry Co., Ltd.) and the like.

  TECHMORE VG3101L (trade name, Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy). Propoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2, 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; EHPE3150 (trade name, Daicel Corporation) is 2,2-bis (hydroxymethyl) -1- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol, COATOSIL MP200 (trade name, Momentive Performance) Month Materials Japan GK) is a polymer that uses 3-glycidoxypropyltrimethoxysilane as a raw material component.

1-2-2. Ratio of compound (B) having three or more epoxy groups to copolymer (A) Compound having three or more epoxy groups to 100 parts by weight of copolymer (A) in the thermosetting composition of the present invention ( The ratio of the total amount of B) is 10 to 500 parts by weight. When the ratio of the total amount of the compound (B) having three or more epoxy groups is within this range, the balance of flatness, heat resistance, chemical resistance and base adhesion is good. The total amount of the compound (B) having three or more epoxy groups is preferably in the range of 50 to 300 parts by weight, but this is determined by adjusting the molar ratio of the copolymer and the epoxy curing agent.

1-3. Compound (C) having four or more (meth) acryloyl groups
The compound having a (meth) acryloyl group used in the present invention is a compound having four or more (meth) acryloyl groups per molecule. Compound (C) may be one type or two or more types.

1-3 Examples of compounds having at least one (meth) acryloyl group Specific examples of the compound (C) in the present invention include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta Erythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, many Basic acid-modified (meth) acryloyl oligomer, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, polyfunctional urethane acrylate oligomer, etc. Can be mentioned.

  The above compounds may be used alone or in combination of two or more. In addition to these, a compound having a trifunctional or lower (meth) acryloyl group may be used as long as the characteristics of the present invention are not impaired.

  Among the compounds having four or more (meth) acryloyl groups, it is possible to use pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid-modified (meth) acryloyl oligomer, or a mixture thereof. It is preferable from the viewpoint of heat resistance and chemical resistance of the cured film.

  The following commercially available products can be used as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid-modified (meth) acryloyl oligomer, or a mixture thereof.

  A specific example of pentaerythritol tetraacrylate is M-450 (trade name; Toagosei Co., Ltd., Tri body <10%). Specific examples of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (pentabody 50 to 60% by weight), M-400 (pentabody 40 to 50% by weight), M-402 (penta). 30-40 wt%), M-404 (30-40 wt% penta), M-406 (25-35 wt% penta), and M-405 (10-20 wt% penta) Product name: Toagosei Co., Ltd. Specific examples of the polybasic acid-modified (meth) acryloyl oligomer include Aronix M-510 and M-520 (both trade names: Toagosei Co., Ltd.).

1-3-2. Ratio of compound (C) having four or more (meth) acryloyl groups to copolymer (A) Four or more (meth) to 100 parts by weight of copolymer (A) in the thermosetting composition of the present invention The ratio of the total amount of the compound (C) having an acryloyl group is 50 to 300 parts by weight. When the ratio of the total amount of the compound (C) having four or more (meth) acryloyl groups is within this range, the balance of flatness, heat resistance, chemical resistance and base adhesion is good. The total amount of the compound (C) having four or more (meth) acryloyl groups is preferably in the range of 50 to 200 parts by weight, but this is determined by adjusting the molar ratio with the copolymer and the epoxy curing agent. To do.

1-4. Solvent (D)
A solvent is added to the thermosetting composition of the present invention. The solvent (D) added to the composition of the present invention comprises a copolymer (A), a compound (B) having three or more epoxy groups, and a compound (C) having four or more (meth) acryloyl groups. A solvent capable of dissolving is preferable. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3 -Methyl oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2- Propyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropyl Methyl pionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl Ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these, or a mixture of two or more of these.

  A common compound can be used for the solvent (D) and the solvent used for the synthesis of the copolymer (A) described above. Therefore, the reaction solvent used in the synthesis of the copolymer (A) may be used as it is as the solvent (D). After the synthesis, the reaction solvent is distilled off under reduced pressure, and the residue is dissolved in another solvent (D). And it can also use for the thermosetting composition of this invention.

1-5. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesion, transparency, flatness, and chemical resistance. Additives include epoxy curing agents, solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines. Mainly mentioned are antioxidants such as phosphorous, phosphorus and sulfur compounds, molecular weight modifiers, and epoxy curing agents.

1-5-1. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (all trade names, Kyoeisha Chemical Co., Ltd.), Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-166, Dispersake-170, Dispersake-180 , Disper Bake-181, Disper Bake-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (All trade names, Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names, Shin-Etsu Chemical Co., Ltd.), Surflon-S611 (Products) Name AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, 602A, Aftergent 650A, FTX-218 (all trade names) Neos), Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-472SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-94, Mega Fuck RS-75, Mega Fat RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 (all trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (both trade names, Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, Diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, Polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether , Polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laur Rate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearete DOO, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

  Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon-S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, When it is at least one selected from fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amino sulfonate The coating uniformity of the thermosetting composition is preferably increased.

  The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-5-2. Coupling Agent The thermosetting composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate.

  As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Silaace S510, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Silaace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name: Silaace S810, JNC Corporation), 3-glycidyloxypropyl Silane coupling agents such as copolymers of trimethoxysilane (for example, trade name: COATOSIL MP200 (trade name, Momentive Performance Materials Japan GK)), acetoalkoxy aluminum Aluminum coupling agent Muzi isopropylate and the like, and tetraisopropyl bis (dioctyl phosphite) can be mentioned titanate coupling agents such as titanates.

  Among these, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  Since the content of the coupling agent is 0.01 parts by weight or more and 10 parts by weight or less with respect to the total amount of the thermosetting composition, adhesion between the formed cured film and the substrate is improved. preferable.

1-5-3. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to high temperatures.

  You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the thermosetting composition of this invention. Of these, hindered phenols are preferred from the viewpoint of weather resistance. As a specific example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD (all trade name, BASF Japan stock Company), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all are trade names) ADEKA Co., Ltd.). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

  The antioxidant is used by adding 0.1 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-5-4. Epoxy Curing Agent The composition of the present invention may further contain an epoxy curing agent in order to improve flatness and chemical resistance. Epoxy curing agents include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, DBU salt curing agents, pyrazole curing agents, triazole curing agents, sulfonium salts, benzothia There are thermosensitive acid generators such as zonium salts, ammonium salts, phosphonium salts, etc., but from the viewpoint of avoiding coloring of the cured film and the reliability of the cured film, an acid anhydride-based curing agent or an imidazole-based curing agent, Or the combined use is preferable.

  Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride; Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride having a good balance between heat resistance and solubility in solvents are preferable.

  Specific examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2- a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole. Among these, 2-undecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole, which have a good balance between curability and solubility in solvents, are preferable.

  When using an epoxy curing agent, the ratio of the epoxy curing agent to 100 parts by weight of the compound (B) having three or more epoxy groups is 0.1 to 60 parts by weight. About the addition amount in case an epoxy hardening agent is an acid anhydride type hardening | curing agent, in detail, the carboxylic acid anhydride group or carboxyl group in an epoxy hardening agent is 0.1-1.5 with respect to an epoxy group. It is preferable to add so that it may become a double equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. If the carboxylic acid anhydride group or carboxyl group is added so as to have an equivalent amount of 0.15 to 0.8 times, the chemical resistance is further improved, which is more preferable.

1-5-5. Ultraviolet Absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration preventing ability of the formed transparent film.

  Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names are BASF Japan Ltd.).

  The ultraviolet absorber is used by adding 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-5-6. Anti-flocculating agent The composition of the present invention may contain an anti-flocculating agent from the viewpoint of blending the solid content with a solvent and preventing aggregation.

  Specific examples of the anti-aggregation agent include Disperbak-145, Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-182, Dispersake-184, Dispersake-185 , Disper Bake-2163, Disper Bake-2164, BYK-220S, Disper Bake-191, Disper Bake-199, Disper Bake-2015 (all trade names; Big Chemie Japan Co., Ltd.), FTX-218, Footent 710FM, They are Footgent 710FS (all trade names, Neos Co., Ltd.), Floren G-600, and Floren G-700 (all trade names, Kyoeisha Chemical Co., Ltd.).

  The aggregation inhibitor is used by adding 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-5-7. Thermal Crosslinker The composition of the present invention may contain a thermal crosslinker from the viewpoint of further improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility and elasticity.

  Specific examples of the thermal crosslinking agent include Nicarak MW-30HM, Nicarak MW-100LM, Nicarax MX-270, Nicarak MX-280, Nicarax MX-290, Nicarac MW-390, Nicarac MW-750LM (all are trade names, ( Sanwa Chemical Co., Ltd.).

The thermal crosslinking agent is used by adding 0.1 to 10 parts by weight with respect to the total amount of the composition.

1-6. Storage of Thermosetting Composition When the thermosetting composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the stability over time of the composition becomes good. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured film of thermosetting composition The thermosetting composition of the present invention comprises a copolymer (A), a compound having three or more epoxy groups (B), a compound having four or more (meth) acryloyl groups. (C) and solvent (D) are prepared by mixing, but depending on the desired properties, an epoxy curing agent, surfactant, adhesion improver, antioxidant, and other additives are selected as necessary. Can be added.

  When the thermosetting composition prepared as described above is applied to the substrate surface and the solvent is removed, for example, by heating or the like, a coating film can be formed. Application of the thermosetting composition to the substrate surface can form a coating film by a conventionally known method such as spin coating, roll coating, dipping, or slit coating. Next, this coating film is temporarily baked by a hot plate or an oven. Temporary baking conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, this baking is performed in order to cure the coating film. The main firing conditions vary depending on the types and blending ratios of the respective components, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, 5 to 30 minutes for a hot plate, and heat treatment. Thus, a cured film can be obtained.

  The cured film thus obtained is subjected to thermal reaction with the compound (B) in which the copolymer has 3 or more epoxy groups and the compound (C) having 4 or more (meth) acryloyl groups during heating. In order to form a three-dimensional network, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness and adhesion. Further, regarding light resistance, sputtering resistance, scratch resistance, and coating property, it is expected to be excellent for the same reason. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be produced using this color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. It is. Furthermore, the cured film of the present invention is also effective when used as a protective film for LED light emitters.

  Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

  The compounds used in Synthesis Examples, Examples, and Comparative Examples are described for each component.

[Synthesis Example 1] Synthesis of copolymer (A1) solution In a four-necked flask equipped with a stirrer, methyl 3-methoxypropionate (MMP), N-cyclohexylmaleimide, maleic anhydride, radical initiator V-65 (Wako Pure) Yakuhin Kogyo Co., Ltd.) and α-methylstyrene dimer were charged at the following weights, and heated and stirred at 80 ° C. for 2 hours under a dry nitrogen stream to obtain a radical copolymer.
MMP 23.627g
N-cyclohexylmaleimide 6.464 g
Maleic anhydride 3.537g
V-65 0.100g
α-Methylstyrene dimer 0.025g

  The polymerization solution was cooled to room temperature to obtain a 30% by weight solution of a pale yellow transparent copolymer (A1). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight Mw of the obtained copolymer (A1) was 13,000.

[Synthesis Examples 2 to 5] Synthesis of Copolymers (A2) to (A5) Solutions According to the method of Synthesis Example 1, each component was reacted at the temperatures, times, and ratios (unit: g) shown in Table 1. To obtain copolymers (A2) to (A5) solutions.

[Comparative Synthesis Example 1] Synthesis of polymethacrylate (R1) solution General epoxy group-containing polymethacrylate having no specific structure included in the claims is reacted at the temperature, time, and ratio shown in Table 1, ( R1) A solution was obtained. However, the reaction temperature was 80 ° C. for 2 hours.

The compounds used in the synthesis examples and comparative synthesis examples indicated by abbreviations in Table 1 are as follows.
MMP: methyl 3-methoxypropionate CHMI: N-cyclohexylmaleimide NPM: N-phenylmaleimide IN: indene MAH: maleic anhydride V-65: 2,2′-azobis (2,4-dimethylvaleronitrile); Α-MSD: α-methylstyrene dimer GMA: Glycidyl methacrylate MMA: Methyl methacrylate

[Example 1]
30% by weight solution of copolymer (A1) obtained in Synthesis Example 1 VG3101L as trifunctional epoxy compound, trimellitic anhydride (TMA) as curing agent, S510 as silane coupling agent, F as surfactant -556 and propylene glycol monomethyl ether acetate (PGMEA) as a dilution solvent are mixed and dissolved in the proportions (parts by weight) shown in Table 2, and filtered through a membrane filter (pore size 0.2 μm) to obtain a thermosetting composition. It was.

[Examples 2 to 7 and Comparative Example 1]
According to the method of Example 1, each component was mixed and dissolved in the proportions (parts by weight) shown in Table 2 to obtain a thermosetting composition. According to the method of Example 1, the barrier properties, tack properties, planarization rate, base adhesion, and heat resistance were measured, and the evaluation results are shown in Table 3.

  Using each of the obtained thermosetting compositions, the heat resistance, planarization rate, and base adhesion were evaluated by the methods described below. The evaluation result of the cured film of Examples 1-13 was put together in Table 3, and was described. Moreover, as Comparative Examples 1 and 2, the heat resistance, planarization rate, and base adhesion of a cured film formed using a thermosetting composition containing a normal polyester having no branched structure were evaluated. The evaluation results are shown in Table 3.

[Evaluation method for barrier properties]
A thermosetting composition was spin-coated at 600 rpm for 10 seconds on a substrate of a color filter having RGB pixels with an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, JASCO Corporation), and 90 ° C. Pre-baked on hot plate for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average protective film thickness of 1.5 μm.

  Next, a certain amount of 1-methyl-2-pyrrolidone is dropped on the color filter with a cured film, and a cover glass covering 60% of the area of the color filter substrate with the cured film is placed on the color filter substrate with the cured film. And heated at 160 ° C. for 5 minutes using a hot plate. After the heating was completed, the cover glass was removed, the cover glass and the color filter substrate with a cured film were washed with a certain amount of 1-methyl-2-pyrrolidone, and the washing solution was used as an eluate for the color filter substrate with a cured film.

  Then, the transmittance | permeability of the eluate was measured with the said ultraviolet visible near-infrared spectrophotometer by making 1-methyl-2-pyrrolidone into a reference sample. From the measurement results, the case where the transmittance at 560 nm was 90% or more was rated as ◯, and the case where it was less than 90% was rated as x.

[Tacking evaluation method]
The thermosetting composition was spin-coated on a glass substrate at 60 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C. for 2 minutes. The case where the surface of the coating film was touched with a finger and no trace of the finger was left on the surface was marked with ◯.

[Evaluation method of flatness]
Concave and convex substrate (pattern with a line of 100 μm, space of 50 μm, film thickness of 1 μm) including a resist pattern whose surface step is measured using a step / surface roughness / fine shape measuring device (trade name; P-17, KLA Tencor Corporation). The obtained thermosetting composition was spin-coated at 650 rpm for 10 seconds on a substrate and pre-baked on an 80 ° C. hot plate for 2 minutes. Subsequently, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having an average protective film thickness of 1.5 μm. Then, the surface level | step difference was measured with respect to the obtained color filter substrate with a cured film. The flattening rate was calculated from the maximum surface level difference (hereinafter abbreviated as “maximum level difference”) of the color filter substrate without cured film and the color filter substrate with cured film using the following formula, and the results are shown in Table 3. It was. As a result of flatness, 100 to 80% was evaluated as ◎, 79 to 60% as ◯, and less than 60% as ×.

Flattening rate (%) = ((maximum step of uneven substrate−maximum step of uneven substrate with cured film) / maximum step of uneven substrate) × 100

[Adhesion evaluation method]
The obtained thermosetting composition was spin-coated on an uneven substrate (line: 100 μm, space: 50 μm, film thickness: 1.0 μm) at 650 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film. A cross-cut test (JIS K 5400, release tape: 3M No. 361 was used) was performed on both the obtained concavo-convex substrate with a cured film and a similarly prepared glass substrate with a cured film, and the following classifications 0 to 5 were performed. According to the evaluation, classifications 0 to 1 were evaluated as ◯, classifications 2 through 3 as Δ, and classifications 4 through 5 as x. The adhesion evaluation on the concavo-convex substrate with a cured film was “adhesion 1”, and the adhesion evaluation on the glass substrate with a cured film was “adhesion 2”.

<Category 0>: The edges of the cut are completely smooth, and there is no peeling to the eyes of any lattice.
<Category 1> ... Small peeling of the coating film at the intersection of cuts. The cross-cut portion is clearly not affected by more than 5%.
<Category 2> The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut part is clearly affected by more than 5%, but not more than 15%.
<Category 3>: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross cut part is clearly affected by more than 15%, but not more than 35%.
<Category 4>: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly not affected by more than 35%.
<Category 5>... Any of the degree of peeling that cannot be classified even in Category 4.

[Evaluation method of heat resistance]
The thermosetting composition was spin-coated on a glass substrate at 60 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C. for 2 minutes. Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film (this is made into the film thickness after PB). In the obtained glass substrate with a cured film, the film thickness was measured using a step / surface roughness / fine shape measuring device (trade name: P-17, KLA TENCOR Co., Ltd.) to obtain an initial film thickness. Thereafter, the glass substrate with a cured film was post-baked in an oven at 230 ° C. for 60 minutes, and the film thickness was measured in the same manner (this film thickness is referred to as post-EB film thickness). The remaining film ratio was calculated using the following formula, and the film with a remaining film ratio between PB and EB of 98% or more was marked with ◯, and the film with less than 98% was marked with x.

Residual film ratio (%) = (film thickness after EB / film thickness after PB) × 100

[Transparency evaluation method]
The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, it heat-processed for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film which is a film thickness of 1.5 micrometers. In the obtained glass substrate with a cured film, the light transmittance at 400 nm of the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, JASCO Corporation). In this case, only the glass substrate was used as a reference, and the light transmittance of the cured film alone was calculated (in this case, interference due to multiple reflection was not considered). The case where the light transmittance was 98% or more was evaluated as transparency ○, the case where the transmittance was less than 95% was evaluated as transparency ×, and the space between them was evaluated as Δ.

  As is clear from the results shown in Table 3, it can be seen that the thermosetting compositions of Examples 1 to 7 satisfy heat resistance, flatness, and adhesion. On the other hand, Comparative Example 1 could not satisfy all the characteristics.

  The cured film obtained from the thermosetting composition of the present invention has good heat resistance, flatness, and underlying adhesion, and is a protective film for various optical materials such as color filters, LED light emitting elements, and light receiving elements. And an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (5)

Copolymer (A) which is a reaction product from monomers (b) other than monomers (a) and (a) represented by the following formula (1), a compound having three or more epoxy groups (B) A thermosetting composition containing a compound (C) having four or more (meth) acryloyl groups and a solvent (D).

In the formula (1), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbon atoms, or phenyl. The thermosetting composition according to claim 1, wherein the monomer (b) is at least one selected from a compound represented by the following formula (2) and indene.

In Formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbons or phenyl, and R ³ is a monovalent organic group.   The thermosetting composition according to claim 1, wherein the compound (B) having three or more epoxy groups is a compound having an aromatic ring.   The cured film formed from the thermosetting composition of any one of Claims 1-3.   A color filter having the cured film according to claim 4 as a transparent protective film.