JP6947102B2 - Thermosetting composition - Google Patents

Description

The present invention can be used to form an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a flattening 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 thereof, and an electronic component having the film.

The manufacturing process of an element such as a liquid crystal display element includes a step 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 step, color filter protective film film formation / patterning / heat treatment step, ITO conductive film film formation process, ITO patterning Photoresist film formation / patterning / wet etching / resist peeling step, ITO annealing step, alignment film film formation / heat treatment / rubbing (polarization exposure) step and the like. In these various steps, the device has an opportunity to come into contact with various chemicals such as organic solvents, acids and alkaline solutions, and the surface is locally exposed to high temperatures when the electrodes are formed by sputtering. In some cases. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various properties capable of withstanding various treatments during the manufacturing process as described above. Specifically, it has heat resistance, solvent resistance, acid resistance, alkali resistance, and other chemical resistance, water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, coatability, flatness, and light resistance. Etc. are required. In particular, as the required characteristics of reliability required for a display element are improved, the heat resistance required for a display element member, specifically, reduction of outgas during heat treatment is regarded as important. This is because when the various organic thin films described above are formed, the thin films are always crosslinked and densified by heat treatment, so that heat is applied to the device many times throughout the process. Therefore, if a protective film that generates a large amount of outgas is used, the thin film formation of the upper layer is affected by the outgas from the lower layer, resulting in deterioration of display quality and reliability.

So far, in order to provide a protective film having high heat resistance, it has been proposed to use a polyimide material as a protective film (Patent Document 1). Further, 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, or a protective film using an acrylic resin or a polyester resin has been proposed (Patent Documents 4, 5 and 6).

However, in the protective film using a polyimide material, in order to prepare a polyimide or a polyimide precursor (polyamide 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 becomes a big problem especially when it is used as a protective film for a color filter. In addition, polyimide has a problem of being colored because the hem 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, heat resistance and transparency are sufficient, but the temperature required to complete the reaction of silanol groups is as high as 300 ° C or higher, so that the underlying organic thin film is used. There is also a problem of causing deterioration of the thin film and a problem of cracking in the thin film due to curing shrinkage during thermosetting. In addition, there is a drawback that the −Si—O—Si− bond of the siloxane material is easily hydrolyzed by the alkaline solution. Further, in the case of a material using an epoxy resin and a melamine resin, although there is no problem with the solvent used and the heat treatment temperature, the heat resistance is not sufficient and the problem of yellowing also occurs. Even when an acrylic material or a polyester resin was used, the heat resistance of the acrylic part and the polyester part, which are the basic skeletons, was not sufficient, causing a problem of outgassing. In particular, polyester materials have a problem that some of the raw materials remain unreacted and can be removed in the refining process, but because of the high cost, reduction of outgas without the refining process has been required.

On the other hand, a protective film using a polyester amic acid having both a polyester and an amic acid structure is also disclosed (Patent Document 7). In this case, the outgas reduction effect was limited due to the non-uniform presence of the ester moiety and the amic acid moiety in the polymer and the residual raw material alcohol component.

From the above situation, there has been a demand for a material that has both high heat resistance (low outgassing property) and other properties, particularly flatness, transparency, and adhesion to a substrate.

Japanese Patent Application Laid-Open No. 62-163016 Japanese Patent Application Laid-Open No. 62-242918 Japanese Patent Application Laid-Open No. 7-331178 JP-A-63-131103 Japanese Patent Application Laid-Open No. 8-50289 JP 2013-253263 Japanese Patent Application Laid-Open No. 2008-156546

An object of the present invention is to provide a thermosetting composition that provides a cured film having excellent heat resistance (low outgassing property), flatness, transparency, and adhesion, and a cured film formed by the thermosetting composition. Further, it is to provide an electronic component having the cured film.

As a result of diligent studies to solve the above problems, the present inventor has obtained a copolymer obtained by thermally reacting a compound having two or more acid anhydride groups with a compound having an amino group and a hydroxyl group in the same molecule. The present invention has been completed by using a thermosetting composition containing a compound having two or more epoxy groups and a solvent capable of dissolving them. The present invention includes the following configurations.

式（１）において、Ｒ^１は２価の有機基である。 [1] A polymer (a) which is a product of a compound (a) having two or more acid anhydride groups and a compound (b) having an amino group and a hydroxyl group in the same molecule represented by the following formula (1). A), a thermosetting composition containing a compound (B) having two or more epoxy groups and a solvent (C).

In formula (1), R ¹ is a divalent organic group.

[2] The compound (a) having two or more acid anhydride groups is at least one selected from polymers containing aromatic acid dianhydride, aliphatic acid dianhydride and maleic anhydride in the copolymer composition. The thermocurable composition according to item [1].

^{[3] The heat according to item [1], wherein R 1} of the compound (b) is an alkylene having 1 to 10 carbon atoms which may be branched or a divalent group represented by the following formula (2). Curable composition;

−CH ₂ CH ₂ (OCH ₂ CH ₂ ) _m − (2)

In equation (2), m is an integer of 1-9.

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

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

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

The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in heat resistance, flatness, transparency, adhesion, and particularly heat resistance, and when used as a color filter protective film for a color liquid crystal display element. , The display quality can be improved. In particular, it is useful as a protective film for color filters manufactured 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. 1. Thermosetting Composition of the Present Invention The thermosetting composition of the present invention is represented by the compound (a) having two or more acid anhydride groups (-CO-O-CO-) and the formula (1). A thermosetting composition comprising a polymer (A) which is a product obtained by thermally reacting with a compound (b), a compound (B) having two or more epoxy groups, and a solvent (C). A) The thermosetting composition is characterized in that the amount of the compound (B) having two or more epoxy groups is 10 to 500 parts by weight with respect to 100 parts by weight.

1-1. Polymer (A)
The polymer (A) is obtained by thermally reacting a compound (a) having two or more acid anhydride groups with a compound (b) represented by the formula (1). The range in which the compound (a) was selected included aromatic acid dianhydride and aliphatic acid dianhydride, and maleic anhydride and other polymerizable monomers other than maleic anhydride were copolymerized. A polymer (which may have two or more acid anhydride groups) is included, and at least one selected from these can be used. Hereinafter, "other polymerizable monomers other than maleic anhydride" will be referred to as "other polymerizable monomers" in the present specification. The other polymerizable monomer copolymerized with maleic anhydride is not particularly limited, but from the viewpoint of heat resistance, N-substituted maleimide, indene, styrene and the like are preferable.

Radical copolymerization can be used for the copolymerization of maleic anhydride and other polymerizable monomers, and it is preferable to use a thermal radical initiator as the initiator.

Further, at least a solvent is required for the synthesis of the polymer (A). The solvent may be left as it is to form a liquid or gel-like composition in consideration of handleability and the like, or the solvent may be removed to form a solid composition in consideration of transportability and the like.

Other compounds other than the above may be contained as long as the object of the present invention is not impaired. Examples of other raw materials may include chain transfer agents.

1-1-1. Compound (a) having two or more acid anhydride groups
In the present invention, an acid dianhydride is used as a raw material for obtaining the polymer (A). As the acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-Benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic acid dianhydride, 2 , 3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyl ether tetracarboxylic acid Dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3 , 4-Butantetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimeritate) (trade name; TMEG-100, Shin Nihon Rika Co., Ltd.), Cyclobutanetetracarboxylic hydride, Methylcyclobutanetetracarboxylic dianhydride Examples thereof include anhydrides, cyclopentanetetracarboxylic acid dianhydrides, cyclohexanetetracarboxylic acid dianhydrides, ethanetetracarboxylic acid dianhydrides, and butanetetracarboxylic acid dianhydrides. One or more of these can be used.

Further, in the present invention, a copolymer of maleic anhydride and other polymerizable monomers can be used as a compound having two or more acid anhydride groups. In this case, examples of other polymerizable monomer that can be used include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. .. In addition, isobutene, styrene, inden, 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. Compound having an amino group and a hydroxyl group in the same molecule (b)
In the present invention, a compound having an amino group and a hydroxyl group in the same molecule is used as a material for obtaining the polymer (A). Such compounds include 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 8-amino-1-octanol, 10-amino-1- Examples thereof include decanol, 12-amino-1-dodecanol, 2- (2-aminoethoxy) ethanol, 2- (4-aminophenyl) ethanol, 2- (4-aminocyclohexyl) ethanol, and 4-aminocyclohexanol. 2-Aminoethanol and 2- (2-aminoethoxy) ethanol are preferable from the viewpoint of availability and heat resistance. A plurality of the compounds listed here can be used in combination.

1-1-3. Solvent used for synthesis of polymer (A) Specific examples of the solvent used for synthesis to obtain polymer (A) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, and methoxyacetic acid. Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, Propropylene 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 them.

1-1-4. Molecular Weight Adjusting Agent Used for Synthesis of Copolymer Containing Maleic anhydride When synthesizing a copolymer containing maleic anhydride, a molecular weight adjusting agent is used in order to suppress an increase in molecular weight and exhibit excellent storage stability. May be further contained. Examples of the molecular weight adjusting agent include mercaptans, xanthogens, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene and the like.

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, and methylhydroquinone. t-butylhydroquinone, methquinone, 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, 2,4-diphenyl-4-methyl-1-pentene and the like.

The molecular weight adjusting agent may be used alone or in combination of two or more.

1-1-5. Method for synthesizing polymer (A) In the polymer (A) used in the present invention, a compound (a) having two or more acid anhydrides and a compound (b) represented by the formula (1) are thermally reacted. You can get it. At this time, the number of moles per functional group of the acid anhydride and the number of moles per functional group of the compound (b) represented by the formula (1) need to be in the following ranges. Here, the functional group means an acid anhydride group, an amino group, and a hydroxyl group.

0.5 ≤ X ≤ 5.0
X = number of moles of acid anhydride / (number of moles of amino group + number of moles of hydroxyl group)

Within this range, the solubility of the polymer in the solvent is high, and the heat resistance, flatness, and adhesion of the composition are good, but more preferably 0.7 ≦ X ≦ 4.0, and further. Preferably 1.0 ≦ X ≦ 3.0.

It is preferable to use 80 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the solute because the reaction proceeds smoothly. The reaction is carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours.

On the other hand, as the compound having an acid anhydride, a polymer obtained by copolymerizing maleic anhydride and other polymerizable monomers can also be used as described above. In the case of this radical polymerization, the reaction temperature of 40 ° C. to 120 ° C. is preferable, and the reaction temperature of 60 ° C. to 80 ° C. is more preferable. After completion of radical polymerization, the mixture is cooled to room temperature, the compound represented by the formula (1) is added, and the mixture is reacted at 40 to 200 ° C. for 0.1 to 6 hours.

In the polymer (A) synthesized in this way, even if the compound (b) represented by the formula (1) has low solubility in the copolymer or the solvent used, it is uniformly transparent after the thermal reaction. It becomes a liquid and can form a uniform thin film without defects. On the contrary, when a compound having two or more hydroxyl groups is simply added to the system after the polymerization of the radical copolymer without thermal reaction, precipitation of the compound having two or more hydroxyl groups may occur. In that case, a uniform thin film cannot be formed. Therefore, it is possible to form a defect-free thin film by inducing the polymer (A).

The weight average molecular weight of the obtained polymer (A) is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000. Within these ranges, the coatability and flatness are good.

The weight average molecular weight in the present specification is a polystyrene-equivalent value obtained by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies, Ltd.) was used as the standard polystyrene, and PLgel MIXED-D (Agilent Technologies, Ltd.) was used for the column. It can be measured using THF as the mobile phase. The weight average molecular weight of the commercially available product in the present specification is a value listed in the catalog.

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

1-2-1. Example of compound (B) having two or more epoxy groups Examples of compound (B) having two or more epoxy groups are bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidyl ether type epoxy compound, and glycidyl ester type epoxy. Compound, biphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, aliphatic polyglycidyl ether compound, cyclic aliphatic epoxy compound, polymer of monomer having epoxy group , A copolymer of a monomer having an epoxy group and another monomer, and an epoxy compound having a siloxane bond site.

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004, and 1009 (trade names: Mitsubishi Chemical Corporation). Specific examples of commercially available bisphenol F-type epoxy compounds are jER 806 and 4005P (both trade names; Mitsubishi Chemical Corporation). Specific examples of commercially available glycidyl ether type epoxy compounds include TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE3150 (trade name; Daicel Co., Ltd.), EPPN-501H, 502H (trade name; Nippon Kayaku Co., Ltd.). Company) and jER 1032H60 (trade name; Mitsubishi Chemical Corporation). Specific examples of commercially available glycidyl ester-type epoxy compounds are Denacol EX-721 (trade name: Nagase ChemteX Corporation) and diglycidyl 1,2-cyclohexanedicarboxylic acid (trade name: Tokyo Chemical Industry Co., Ltd.). Specific examples of commercially available biphenyl type epoxy compounds include jER YX4000, YX4000H, YL6121H (all trade names; Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000-H, NC-3100. (Both are product names; Nippon Kayaku Corporation). Specific examples of commercially available phenol novolac type epoxy compounds are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152, 154 (both trade names; Mitsubishi Chemical Corporation) and the like. Specific examples of commercially available cresol novolac type epoxy compounds are EOCN-102S, 103S, 104S, 1020 (trade names: Nippon Kayaku Co., Ltd.) and the like. Specific examples of commercially available bisphenol A novolak type epoxy compounds are jER 157S65, 157S70 (both trade names; Mitsubishi Chemical Corporation). Specific examples of commercially available cyclic aliphatic epoxy compounds are celloxide 2021P and 3000 (both trade names; Daicel Co., Ltd.). Specific examples of commercially available epoxy compounds having a siloxane binding site include 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name: Jerest Incorporated), TSL9906 (commodity). Name: Momentive Performance Materials Japan LLC), COATOSIL MP200 (Product Name; Momentive Performance Materials Japan LLC), Composelan SQ506 (Product Name: Arakawa Chemical Co., Ltd.), ES-1023 (Product Name) Shin-Etsu Chemical Industry Co., Ltd.).

TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy) bis] 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 is a mixture. EHPE3150 (trade name; Daicel Co., Ltd.) is a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. Celoxide 2021P (trade name; Daicel Corporation) is a 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. Celoxide 3000 (trade name; Daicel Corporation) is 1-methyl-4- (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane. COATOSIL MP200 (trade name; Momentive Performance Materials Japan LLC) is a polymer containing 3-glycidoxypropyltrimethoxysilane as a raw material component.

As the compound (B) having two or more epoxy groups, the above-mentioned compound may be used alone, or two or more kinds may be mixed and used.

1-2-2. Ratio of compound (B) having two or more epoxy groups to polymer (A) Total amount of compound (B) having two or more epoxy groups to 100 parts by weight of polymer (A) in the thermosetting composition of the present invention The ratio of is 10 to 500 parts by weight. When the ratio of the total amount of the compound (B) having two or more epoxy groups is within this range, the balance of flatness, heat resistance, chemical resistance, and substrate adhesion is good. The total amount of the compound (B) having two 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 with the polymer (A) and the epoxy curing agent.

1-3. Solvent (C)
A solvent (C) is used in the thermosetting composition of the present invention. The solvent (C) used in the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polymer (A) and the compound (B) having two or more epoxy groups. 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, methyl 2-hydroxy-2-methylpropionate , 2-Hydroxy-2-methylpropionate ethyl, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2-methylpropionate ethyl, pyruvate methyl, pyruvate ethyl, pyruvate propyl, methyl acetoacetate, Ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, 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 them.

1-4. Other Ingredients Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesiveness, transparency, flatness, and chemical resistance. Additives include epoxy hardeners, solvents, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, and hindered amines. Antioxidants such as system, phosphorus and sulfur compounds, molecular weight modifiers, and epoxy curing agents are mainly mentioned.

1-4-1. 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 (trade name, Kyoeisha Chemical Co., Ltd.), Disperbak-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-166, Disperbake-170, Disperbake-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 product names, Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (All product names, Shin-Etsu Chemical Industry Co., Ltd.), Surflon- S611 (trade name, AGC Seimi Chemical Co., Ltd.), Footgent 222F, Footgent 208G, Footgent 251 and Footgent 710FL, Footgent 710FM, Footgent 710FS, Footgent 601AD, Footgent 650A, FTX-218, (any of them) Also trade name, Neos Co., Ltd.), Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552 , Mega Fuck 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 Fuck RS-72-K, Mega Fuck RS-76-NS, Mega Fuck DS-21 (all trade names, DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450 , TEGO Rad 2200N (trade name, Ebonic Japan Co., Ltd.), Fluoroalkylbenzene sulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylammonium iodide, Fluoroalkylbetaine, Fluoroalkylsulfonate , Diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroal Killaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl 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 laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonates, and alkyldiphenyl ether disulfonates. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surfron-S611, Footergent 710FL, Footergent 710FM, Footergent 710FS, Footergent 601AD, Footergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkyl Carboxate, At least one selected from fluoroalkylpolyoxyethylene ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonate enhances the coating uniformity of the thermosetting composition. Therefore, it is preferable.

The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01 to 10% by weight based on the total amount of the thermosetting composition.

1-4-2. 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 cured film to be formed 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, Sila Ace S510, JNC Co., Ltd.), 2- (3). , 4-Epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name, Silaace S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (for example, trade name; Silaace S810, JNC Co., Ltd.), 3-glycidyloxypropyl Silane-based coupling agents such as a copolymer of trimethoxysilane (for example, trade name, COATOSIL MP200, Momentive Performance Materials Japan LLC), aluminum-based coupling agents such as acetalkoxyaluminum diisopropylate, and aluminum-based coupling agents. Examples thereof include titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

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

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

1-4-3. 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 a high temperature.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Of these, the hindered phenol type is preferable 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 trade names, ADEKA Corporation). Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-4-4. Epoxy curing agent The thermosetting 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-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, pyrazole-based curing agents, triazole-based curing agents, catalytic curing agents, sulfonium salts, and benzothiazo. There are heat-sensitive acid generators such as nium salt, ammonium salt, and phosphonium salt, but from the viewpoint of avoiding coloring of the cured film and heat resistance 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 acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimeric acid anhydride; Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride, which have a good balance between heat resistance and solubility in a solvent, are preferable.

Specific examples of the imidazole-based 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 trimeritate. Among these, 2-undecylimidazole, which has a good balance between curability and solubility in a solvent, is preferable.

When an epoxy curing agent is used, the ratio of the epoxy curing agent to 100 parts by weight of the compound (B) having two or more epoxy groups is 0.1 to 60 parts by weight. Regarding the amount added when the epoxy curing agent is an acid anhydride-based curing agent, more specifically, the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 with respect to the epoxy group. It is preferable to add in a double equivalent amount. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group in an equivalent amount of 0.15 to 0.8 times because the chemical resistance is further improved.

1-4-5. Ultraviolet absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the ability to prevent deterioration 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, 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.

1-4-6. Anti-aggregation agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of blending the solid content with the solvent to prevent aggregation.

Specific examples of the anti-aggregation agent are Disperbak-145, Disperbake-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-182, Disperbake-184, Disperbake-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, Futergent 710FM, Futergent 710FS (trade name, Neos Co., Ltd.), Floren G-600, Floren G-700 (trade name, Kyoeisha Chemical Co., Ltd.).

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

1-4-7. Thermosetting agent The thermosetting composition of the present invention may contain a thermosetting agent from the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity.

Specific examples of the thermal cross-linking agent include Nicarac MW-30HM, Nicarac MW-100LM, Nicarac MX-270, Nicarac MX-280, Nicarac MX-290, Nicarac MW-390, and Nicarac MW-750LM. Sanwa Chemical Co., Ltd.).

The thermosetting agent is used by adding 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

1-5. Preservation of Thermosetting Composition When the thermosetting composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the stability of the composition with time becomes good. When the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured film formed from a thermosetting composition The thermosetting composition of the present invention is intended by mixing a polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C). Depending on the properties, epoxy curing agents, surfactants, coupling agents, antioxidants, and other additives can be additionally selected and added as necessary.

When the thermosetting composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate and the solvent is removed by, for example, heating, a coating film is formed. Can be formed. The thermosetting composition can be applied to the surface of the substrate by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is tentatively fired on a hot plate, an oven, or the like. The pre-baking conditions vary depending on the type and blending 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, the main firing is performed to cure the coating film. The main firing conditions vary depending on the type and blending ratio of each component, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, and 5 to 30 minutes for a hot plate, and heat treatment is performed. As a result, a cured film can be obtained.

The cured film thus obtained is extremely tough because the polymer (A) reacts with the compound (B) having two or more epoxy groups to form a three-dimensional network when heated. It has excellent transparency, heat resistance, chemical resistance, flatness, and adhesion. Further, the light resistance, the spatter resistance, the scratch resistance, and the coating property are also 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 image sensor can be manufactured using this color filter. Further, the cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or as a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Is. Further, the cured film of the present invention is also effective when used as a protective film for an LED light emitter.

Next, the present invention will be specifically described with reference to Synthetic Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

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

[Synthesis Example 1] Synthesis of Polymer (A1) Solution In a four-necked flask equipped with a stirrer, diethylene glycol methyl ethyl ether (EDM), 4,4'-oxydiphthalic anhydride (ODPA), and 2-aminoethanol (AE) are placed. The mixture was charged under the following weight and heated and stirred at 150 ° C. under a dry nitrogen stream for 3 hours to obtain a polymer solution.
EDM 10.01g
ODPA 8.360g
AE 1.646g

Then, the solution was cooled to room temperature to obtain a 50% by weight solution of the pale yellow transparent polymer (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 of the obtained polymer (A1) was 3,000.

[Synthesis Example 2] Synthesis of Polymer (A2) As shown below, methyl 3-methoxypropionate (MMP, 70% of the total amount charged), N-cyclohexylmaleimide, and maleic anhydride are mixed with a stirrer and a cooler. It was charged into a four-necked flask and heated and stirred at 80 ° C. under a nitrogen stream. Next, an MMP solution of a mixture of radical initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) and α-methylstyrene dimer (using 30% of the total amount charged) was placed in a dropping funnel, and dropping polymerization was carried out over 1 hour. rice field. Then, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a radical copolymer.
MMP 25.90g
N-cyclohexylmaleimide 6.464g
Maleic anhydride 3.537g
V-65 0.1000g
α-Methylstyrene dimer 0.0500g

After cooling to room temperature, 1.102 g of 2-aminoethanol (AE) was added, and the mixture was heated and stirred at 150 ° C. for 3 hours to obtain a polymer (A2) solution. 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 of the obtained polymer (A2) was 16,100.

[Synthesis Examples 3 to 5] Synthesis of Polymer (A3) to (A5) Solutions According to the methods of Synthesis Examples 1 and 2, each component was prepared at the temperature, time, and ratio (unit: g) shown in Table 1. The reaction was carried out to obtain a polymer solution.

[Comparative Synthesis Example 1] Synthesis of Polyester Amidic Acid (R1) Solution Polyester amic acid was reacted at the temperature, time, and ratio shown in Table 1 to obtain a polyester amic acid (R1) solution. However, the first-stage reaction is a reaction of ODPA and 1,4-butanediol (BD) at 150 ° C. for 3 hours, and then the second-stage reaction is a reaction with 3,3'-diaminodiphenyl sulfone. It was carried out at 120 ° C. for 1 hour.

The compounds used in the synthetic example and the comparative synthetic example, which are abbreviated in Table 1, are as follows.
ODPA: 4,4'-oxydiphthalic anhydride CHMI: N-cyclohexylmaleimide IN: inden MAH: maleic anhydride AE: 2-aminoethanol AEE: 2- (2-aminoethoxy) ethanol BD: 1,4-butanediol mDDS: 3,3'-diaminodiphenyl sulfone V-65: 2,2'-azobis (2,4-dimethylvaleronitrile); manufactured by Wako Pure Chemical Industries, Ltd. α-MSD: α-methylstyrene dimer EDM: diethylene glycol Methyl ethyl ether MMP: Methyl 3-methoxypropionate

[Example 1]
A 50% by weight solution of the polymer (A1) obtained in Synthesis Example 1, VG3101L as a trifunctional epoxy compound, trimellitic acid anhydride (TMA) as a curing agent, S510 as a silane coupling agent, and ADK STAB as an antioxidant. AO-60, F-556 as a surfactant, and methyl 3-methoxypropionate (MMP) as a diluting solvent were mixed and dissolved at the ratios (parts by weight) shown in Table 2, and were mixed and dissolved with a polymer filter (pore size 0.2 μm). The mixture was filtered to obtain a thermosetting composition.

[Examples 2 to 5 and Comparative Example 1]
According to the method of Example 1, each component was mixed and dissolved at the ratio (part by weight) shown in Table 2 to obtain a thermosetting composition.

Using each of the obtained thermosetting compositions, heat resistance, flatness, and substrate adhesion were evaluated by the methods described below. The evaluation results of the cured films of Examples 1 to 5 are summarized in Table 3. Further, as Comparative Example 1, the heat resistance, flattening property, and substrate adhesion of the thermosetting composition containing polyesteramidic acid were evaluated. The evaluation results are shown in Table 3.

[Evaluation method of heat resistance]
The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 2 minutes. Subsequently, heat treatment was performed in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film. The film thickness of the obtained glass substrate with a cured film is measured using a step / surface roughness / fine shape measuring device (trade name: P-17, KLA TENCOR Co., Ltd.), and the film thickness becomes 1.5 μm. The spin coating conditions were adjusted so as to be. After that, the cured film is scraped off from the glass substrate with the cured film, and hold measurement is performed at 230 ° C. for 60 minutes with a thermogravimetric / differential thermal measurement device (TG-DTA), and the weight loss from reaching 230 ° C. is 0.5%. If it was less than or equal to ◯, and if it was more than that, it was shown as x together with the measured values.

[Evaluation method of flatness]
Concavo-convex substrate (line 100 μm, space 50 μm, film thickness 1 μm) including a resist pattern whose surface step is measured in advance using a step / surface roughness / fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) The resulting thermocurable composition was spin-coated on a substrate) at 650 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 2 minutes. Subsequently, heat treatment was performed in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of 1.5 μm. Then, the surface step was measured with respect to the obtained color filter substrate with a cured film. From the maximum value of the surface step of the color filter substrate without the cured film and the color filter substrate with the cured film (hereinafter abbreviated as "maximum step"), the flattening rate was calculated using the following formula, and the results are shown in Table 3. rice field. As for the flatness result, 100 to 80% was evaluated as ⊚, 79 to 60% was evaluated as ◯, and less than 60% was evaluated as x.

Flattening rate (%) = ((maximum step of uneven substrate-maximum step of concave-convex 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 a hot plate at 80 ° C. for 2 minutes. Subsequently, heat treatment was performed in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film. A cross-cut test (JIS K 5400, using 3M No. 361) was performed on both the obtained uneven substrate with a cured film and the glass substrate with a cured film produced in the same manner, and the following classifications 0 to 5 were performed. Classifications 0 to 1 were evaluated as ◯, categories 2 to 3 were evaluated as Δ, and categories 4 to 5 were evaluated as ×.

<Category 0> ... The edges of the cut are completely smooth, and there is no peeling in the eyes of any grid.
<Category 1> ... Small peeling of the coating film at the intersection of cuts. The cross-cut area is clearly not affected by more than 5%.
<Category 2> ... The coating film is peeled off along the edge of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
<Category 3> ... The coating film is partially or wholly peeled off along the edge of the cut, and / or various parts of the eyes are partially or wholly peeled off. The cross-cut area is clearly affected by more than 15% but not more than 35%.
<Category 4> ... The coating film has partially or completely peeled off along the edge of the cut, and / or some eyes have 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.

[Transparency evaluation method]
The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 2 minutes. Subsequently, heat treatment was performed in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film having a film thickness of 1.5 μm. In the obtained glass substrate with a cured film, the light transmittance of the cured film at 400 nm was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, JASCO Corporation). In this case, using only the glass substrate as a reference, the light transmittance of the cured film alone was calculated (in this case, interference due to multiple reflections is not considered). When the light transmittance was 98% or more, the transparency was evaluated as ◯, when the transmittance was less than 95%, the transparency was evaluated as ×, and the interval 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 5 satisfy heat resistance, flatness, adhesion, and transparency. On the other hand, in Comparative Example 1, not all the characteristics could be satisfied.

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

Claims (5)

A polymer (A), which is a product of a compound (a) having two or more acid anhydride groups and a compound (b) having an amino group and a hydroxyl group in the same molecule represented by the following formula (1). A thermocurable composition containing a compound (B) having two or more epoxy groups and a solvent (C) , wherein the compound (a) having two or more acid anhydride groups is N-methylmaleimide, N. A polymer containing at least one selected from the group consisting of -ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and inden, and maleic anhydride in the copolymer composition. Thermocurable composition.

In formula (1), R ¹ is a divalent organic group. ^{The thermosetting composition according to claim 1, wherein R 1} of the compound (b) is an alkylene having 1 to 10 carbon atoms which may be branched or a divalent group represented by the following formula (2). ;

−CH ₂ CH ₂ (OCH ₂ CH ₂ ) _m − (2)

In equation (2), m is an integer of 1-9. The thermosetting composition according to claim 1, wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring. A cured film formed from the thermosetting composition according to any one of claims 1 to 3. A color filter having the cured film according to claim 4 as a transparent protective film.