TWI691542B - Thermosetting resin compositions, the cured films and display device - Google Patents

Abstract

The present invention provides a thermosetting resin composition containing a polymer (c), which is a compound (a) having a trifunctional or more polymerizable double bond in a chain transfer agent (b) It is obtained by radical polymerization in the presence. The thermosetting resin composition of the present invention is excellent in storage stability and can be cured at a low temperature to obtain a cured film.

Description

Thermosetting resin composition, its cured film and display element

The present invention relates to a thermosetting resin composition that can be cured at a low temperature and has good storage stability and a cured film thereof.

With the development of information terminals and liquid crystal display elements, the development of electronic circuits, displays, sensors and other products that use organic materials in areas where inorganic materials such as glass or metals are currently used has been rapidly advanced.

The advantage of using organic materials is not only that the molecular design or synthesis conditions can be used to easily adjust the characteristics, but also the realization of lightweight products or process improvement. In particular, replacing the existing glass substrate with an organic material substrate not only has the advantages of light weight, but also has high suitability for flexibility due to the mechanical flexibility of the organic material, so that roll-to-roll to roll) and other printing methods, which can be expected to reduce the cost of the process. On the other hand, by replacing the existing glass with an organic material as the base material, there arises a problem that the heat resistance of the base material decreases.

Based on the development of organic materials as the base material, and in order to form a color filter protective film, or between the thin film transistor (Thin Film Transistor, TFT) and the alignment film or between the TFT and the transparent electrode In the case where a curable resin composition is used for the insulating film, in order to prevent deterioration due to thermal overload on the substrate, it is desired that curing at a low temperature (a temperature lower than the glass transition temperature of the substrate) be easy and organic Material with high suitability. In addition, from the viewpoint of reducing process energy, curing of the curable resin at a low temperature is also required.

In the past, many studies have been conducted to cope with low-temperature hardening, and the use of soluble polymers (see Patent Document 1) and the use of hardening accelerators (see Patent Document 2 and Patent Document 3) have been proposed.

However, in a system using a soluble polymer, polymer synthesis is complicated, and the solubility of the polymer in the solvent is low, so energy is required to remove the solvent. In addition, the system using a hardening accelerator gradually undergoes a hardening reaction even at room temperature, so the storage stability of the resin composition deteriorates. Therefore, a low-temperature-curable resin composition that is easy to synthesize a polymer and excellent in storage stability is required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-203414 [Patent Document 2] International Publication 2009/011304 [Patent Document 3] Japanese Patent Laid-Open No. 2002-69311

[Problems to be Solved by the Invention] An object of the present invention is to provide a thermosetting resin composition which is excellent in storage stability and hardens at a low temperature. [Technical means to solve the problem]

The inventors found that a thermosetting resin composition containing a polymer (c) obtained by radically polymerizing a compound (a) having a trifunctional or more polymerizable double bond in the presence of a chain transfer agent (b) The product has excellent storage stability and becomes a cured film at a low temperature, and the present invention has been completed based on this knowledge. The present invention includes the following items.

[1] A thermosetting resin composition containing a polymer (c) in which a compound (a) having a trifunctional or more polymerizable double bond is added to a chain transfer agent (b) It is obtained by radical polymerization in the presence.

[2] The thermosetting resin composition as described in [1], wherein the compound (a) is a trifunctional or more (meth)acrylate.

[3] The thermosetting resin composition according to item [1] or [2], wherein the chain transfer agent (b) is an addition cleavage type chain transfer agent.

[4] The thermosetting resin composition according to any one of items [1] to [3], wherein the chain transfer agent (b) is 2,4-diphenyl-4-methyl-1- Pentene.

[5] The thermosetting resin composition according to any one of items [1] to [4], wherein the polymer (c) is produced by batch polymerization.

[6] The thermosetting resin composition according to any one of items [1] to [5], wherein the weight average molecular weight of the polymer (c) is 2,000 to 200,000.

[7] A cured film obtained by thermally curing the thermosetting resin composition according to any one of items [1] to [6].

[8] A cured film obtained by thermosetting the thermosetting resin composition according to any one of items [1] to [6] at 100°C to 150°C.

[9] A display element comprising the cured film according to [7] or [8]. [Effect of invention]

The thermosetting resin composition of the present invention has good storage stability and low-temperature curability, and can be used to form a color filter protective film, a transparent insulating film provided between a TFT and an alignment film, or between a TFT and a transparent electrode.

In this specification, in order to show both acrylic acid and methacrylic acid, it may be expressed as "(meth)acrylic acid". In addition, similarly, it is sometimes expressed as "(meth)acrylate" in order to indicate one or both of acrylate and methacrylate.

In the present specification, the “alkyl group” is a linear or branched alkyl group, and examples thereof include methyl, ethyl, propyl, n-butyl, tertiary butyl, pentyl, and hexyl groups.

<1. Thermosetting resin composition of the present invention> The thermosetting resin composition of the present invention is characterized by containing a polymer (c) which is a polymerizable double bond having trifunctional or more The compound (a) is obtained by radical polymerization in the presence of a chain transfer agent (b).

<1-1. Compound (a) having a polymerizable double bond of trifunctional or more> The “compound having a polymerizable double bond of trifunctional or more” contained in the thermosetting resin composition of the present invention means The compound having three or more polymerizable double bonds in the molecule is not particularly limited as long as it has the characteristics of the structure.

The compound (a) having a trifunctional or higher polymerizable double bond of the present invention is preferably selected from a compound having a trifunctional or more (meth)acryloyl group and a compound having a trifunctional or more α-ethylacryloyl group , A compound having a trifunctional or higher styrene group and a compound having a trifunctional or higher vinyl group, more preferably selected from a compound having a trifunctional or higher (meth)acryloyl group and having a trifunctional In the above group of α-ethylacryloyl compounds.

It is preferable to use (meth)acrylic acid, α-ethylacrylic acid, or the ester of these acids for the compound which has trifunctional or more (meth)acryloyl group and the compound which has trifunctional or more in α-ethylacryloyl group.

Examples of the ester of (meth)acrylic acid or α-ethylacrylic acid include alkyl esters and halogenated alkyl esters.

Specific examples of the compound (a) having a polymerizable double bond of more than three functions are: trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, tri Hydroxymethyl propane propylene oxide (PO) modified triacrylate, trimethylol propane ethylene oxide (EO) modified triacrylate, glycerol tri(meth)acrylate , Ethoxylated glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerol EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylic acid Ester, alkyl-modified dipentaerythritol tetra(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, ethoxylated isocyanurate-based tri(meth)acrylate, ε- Caprolactone modified tri-(2-acryloyloxyethyl) isocyanurate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylol Propane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid EO modified di/triacrylate, pentaerythritol tri/tetraacrylate, dipentaerythritol penta/hexaacrylate Ester, diglycerin EO modified acrylate, ethoxylated isocyanurate triacrylate, tri[(meth)acryloyloxyethyl] isocyanurate, ethoxylated glycerol triacrylate, And ethoxylated pentaerythritol tetraacrylate.

Among the above compounds, dipentaerythritol penta/hexaacrylate and pentaerythritol tri/tetraacrylate are preferred from the viewpoint of the low-temperature curability of the polymer.

The compound (a) having a polymerizable double bond of trifunctional or more may be used alone, or two or more kinds may be used in combination.

<1-2. Chain transfer agent (b)> Specific examples of the chain transfer agent (b) used in the present invention are: thioglycolic acid, thioglycolic acid, 2,4-diphenyl-4 -Methyl-1-pentene, Quinoxter QE-2014 (trade name) manufactured by Kawasaki Chemical Industry Co., Ltd., and Quinoxterer manufactured by Kawasaki Chemical Industry Co., Ltd. QE-3214 (trade name).

The chain transfer agent (b) may be used alone or in combination of two or more.

The chain transfer agent (b) is more preferably an addition cleavage type chain transfer agent, and the addition cleavage type chain transfer agent is more preferably from the viewpoint of the stability of polymerization and the curability of the thermosetting resin composition. 2,4-diphenyl-4-methyl-1-pentene.

<1-3. Polymerization method of polymer (c)> The polymerization method of polymer (c) contained in the thermosetting resin composition of the present invention is preferably radical polymerization in solution, which uses one or more types of Compound (a) having a polymerizable double bond of more than three functions. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator used, but it is usually in the range of 50°C to 110°C, and from the viewpoint of suppressing gelation, it is preferably 90°C the following. The polymerization time is also not particularly limited, but it is usually in the range of 1 hour to 24 hours, and from the viewpoint of workability, it is preferably 8 hours or less. In addition, the polymerization can be carried out under any pressure of increased pressure, reduced pressure, or atmospheric pressure.

The solvent used in the polymerization reaction is preferably a compound (a) having a polymerizable double bond of trifunctional or more, a chain transfer agent (b) used together with the polymer (c) obtained Dissolved solvent. Specific examples of such solvents are: methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, Butyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether Ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N,N-dimethylformamide, acetic acid , And water. The solvent may be one kind of these, or a mixture of two or more kinds of these.

The polymerization initiator used in the production of the polymer (c) can be a compound that generates radicals by heat, an azo-based initiator such as azobisisobutyronitrile, or a peroxide-based system such as benzoyl peroxide Starter.

Examples of thermal radical generators include: 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile )) (V-70 (trade name) manufactured by Wako Pure Chemical Industries Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) (2,2'-Azobis(2, 4-dimethylvaleronitrile)) (V-65 (trade name) manufactured by Wako Pure Chemical Industries Ltd.), 2,2'-azobis (isobutyronitrile) (2,2'-Azobis (isobutyronitrile)) (and V-60 (trade name) manufactured by Kodak Pharmaceutical Co., Ltd.), 2,2'-azobis (2-methylbutyronitrile) (2,2'-Azobis (2-methylbutyronitrile)) (Wako Pure Chemicals V-59 (trade name) manufactured by industry (shares), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide] (2,2'-Azobis[N -(2-propenyl)-2-methylpropionamide]) (VF-096 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(N-butyl-2-methylpropane) Acetamide) (2,2'-Azobis (N-butyl-2-methylpropionamide)) (VAm-110 (trade name) manufactured by Wako Pure Chemical Industries (Shares)), 2,2'-azobis (isobutyl) Acid) dimethyl (Dimethyl 2,2'-Azobis (isobutyrate)) (V-601 (trade name) manufactured by Wako Pure Chemical Industries Ltd.), VPE-0201, VPE-0401, VPE-0601, VPS- 1001 (the above are trade names, Wako Pure Chemical Industries (shares)), etc.

The weight average molecular weight of the polymer (c) is preferably from 2,000 to 200,000, and from the viewpoint of film-forming property, it is more preferably from 10,000 to 100,000.

The weight average molecular weight in this specification is a polystyrene-converted value obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) method (column temperature: 35°C, flow rate: 1 mL/min). The standard polystyrene is polystyrene with a molecular weight of 645-285,300 (for example: Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, Agilent Technology (Agilent Technology) Co., Ltd. )), the column was measured using PLgel MIXED-D (trade name, Agilent Technology Co., Ltd.) and tetrahydrofuran (THF) as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is the value shown in the catalog.

From the viewpoint of the curability of the thermosetting resin composition, it is preferable that the polymer (c) obtained by the above-mentioned method removes unreacted materials by the reprecipitation method. As a purification method using reprecipitation, a non-polar solvent of 3 to 10 times the volume of the obtained polymer solution is stirred, and the polymer solution is added dropwise to precipitate the polymer. After removing the supernatant, it can be purified by redissolving in the polymerization solvent.

The non-polar solvent used in the reprecipitation method is preferably hexane or heptane.

<1-4. Other components> From the viewpoint of adding further characteristics, the thermosetting resin composition of the present invention may contain other components other than the above, if necessary. Examples of the other components include solvents and additives.

<1-4-1. Solvent> A solvent may be added to the thermosetting resin composition of the present invention. The solvent optionally added to the thermosetting resin composition of the present invention is preferably a solvent that can dissolve the polymer and other additives. Specific examples of solvents that can be added are: water, acetone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, 2-butanone, ethyl acetate, acetic acid Propyl ester, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionate Propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion Ethyl acid ester, 2-oxy-2-methyl propionic acid methyl ester, 2-oxy-2-methyl propionic acid ethyl ester, 2-methoxy-2-methyl propionic acid methyl ester, 2-ethyl Ethyloxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetate, methyl 2-oxobutanoate, 2- Ethyl oxobutyrate, tetrahydrofuran, acetonitrile, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexane Ketone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Ethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, toluene, xylene, γ-butyl Lactone, N,N-dimethylacetamide, and N,N-dimethylformamide. These solvents may be used alone or in combination of two or more.

From the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention, the solvent is preferably selected from propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol At least one of dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate and butyl acetate. Furthermore, from the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention and the viewpoint of safety to the human body, it is more preferably selected from propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. At least one of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether, ethyl lactate and butyl acetate.

In the thermosetting resin composition of the present invention, the solvent is preferably prepared so that the polymer (c) as a solid component and other additives are 5 to 90% by weight based on the total amount.

<1-4-2. Additives> The thermosetting resin composition of the present invention may contain additives. The additives arbitrarily added to the thermosetting resin composition of the present invention are added from the viewpoint of improving the characteristics of the thermosetting resin composition of the present invention such as coating uniformity, adhesion, and stability. Examples of the additives include polymerization inhibitors, acrylic-based, styrene-based, polyethyleneimine-based or urethane-based polymer dispersants, anionic, cationic, nonionic, or fluorine-based interfaces. Activator, silicone resin coating improver, adhesion improver such as silane coupling agent, anti-agglomeration agent such as sodium polyacrylate, thermal crosslinking agent such as epoxy compound, melamine compound or diazide compound, hindered system Antioxidants such as phenol, and hardening accelerators such as imidazole or polyfunctional acrylate.

In the thermosetting resin composition of the present invention, a surfactant and a coating improver may be added. The surfactant and the coating improver are used to improve the wettability, leveling, or coating of the base substrate. Surfactants and coating improvers optionally added to the thermosetting resin composition of the present invention include Polyflow No. 45, Polyflow KL-245, and Poly Polyflow No.75, Polyflow No.90, Polyflow No.95 (the above are trade names, Kyoeisha Chemical Industry Co., Ltd.), BYK ( BYK)-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK -346 (the above are trade names, BYK-Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are all It is a trade name, Shin-Etsu Chemical Industry Co., Ltd., Surflon SC-101, Surflon KH-40, Surflon S-611 (the above are trade names, AGC Qingmei AGC Seimi Chemical Co., Ltd., Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 251FL, Ftergent 710FL, Ftergent 710FM , Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (the above are trade names, Neos shares Co., Ltd., EFTOP (EFTOP) EF-351, EFTOP (EFTOP) EF-352, EFTOP (EFTOP) EF-601, EFTOP (EFTOP) EF-801, EFTOP (EFTOP) EF-802 (the above are trade names, Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Mega Method (Megafac) F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F- 552, Megafac F-553, Megafac F-554, Megafac F-555, Megafa c) F-556, Megafac F-558, Megafac R-30, Megafac R-94, Megafac RS-75, Megafac RS-72 -K, Megafac RS-76-NS (the above are trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad ) 2200N, TEGO Rad 2250N (the above are trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, Fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, Fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, poly Oxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurel Amine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan Alcohol laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate Acid salt, or alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these for additives.

Among these surfactants and coating improvers, if selected from fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl beet Alkali, fluoroalkyl sulfonate, diglycerol tetra(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, Megafac R-08, Mega (Megafac) R-30, Megafac F-477, Megafac F-556, Megafac F-554 and other fluorine-based surfactants, BYK-306, Bi At least one of BYK-342, BYK 344, BYK 346, KP-341, KP-358, or KP-368 silicone resin-based coating improver It is preferable from the viewpoint of improving the uniformity of application of the thermosetting resin composition of the present invention.

The content of the surfactant and the coating enhancer in the thermosetting resin composition of the present invention is preferably 0.001% to 0.1% by weight relative to the total amount of the composition.

A hardening accelerator may be added to the thermosetting resin composition of the present invention. The hardening accelerator is used to promote the hardening reaction of the thermosetting resin composition and improve the hardness, heat resistance, and chemical resistance of the cured film. The hardening accelerators optionally added to the thermosetting resin composition of the present invention are: trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylol Propane PO modified triacrylate, trimethylolpropane EO modified triacrylate, glycerol tri(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, epichlorohydrin modification Glycerin tri(meth)acrylate, diglycerin EO modified acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol tetra(meth)acrylate, alkyl modified Quality dipentaerythritol tri(meth)acrylate, ethoxylated isocyanurate-based tri(meth)acrylate, ε-caprolactone modified tri-(2-propenyloxyethyl)isocyanide Urate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth) Base) acrylate, isocyanurate modified EO di/triacrylate, pentaerythritol tri/tetraacrylate, dipentaerythritol penta/hexaacrylate, diglycerol EO modified acrylate, ethoxylated isocyanurate tri Acrylate, tri[(meth)acryloyloxyethyl] isocyanurate, ethoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, 2-undecyl imidazole, 2- Heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, etc.

The hardening accelerator may be used alone or in combination of two or more.

To the thermosetting resin composition of the present invention, an adhesion improving agent may be added. The adhesion improving agent is used to improve the adhesion of the thermosetting resin composition to the substrate. As the adhesion improving agent optionally added to the thermosetting resin composition of the present invention, a coupling agent can be suitably used. The adhesion improving agent may be one kind, or two or more kinds. Silane-based, aluminum-based, or titanate-based compounds can be used as the coupling agent. Examples of such coupling agents include 3-glycidoxypropyl dimethyl ethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl trimethoxy Silane, acetoalkoxy aluminum diisopropylate (acetoalkoxy aluminum diisopropylate), and bis (dioctylphosphite) tetraisopropyl titanate (tetraisopropyl bis (dioctylphosphite) titanate). Among these compounds, 3-glycidoxypropyltrimethoxysilane is preferable because of its large effect of improving adhesion.

An anti-agglomeration agent may be added to the thermosetting resin composition of the present invention. The anti-agglomeration agent is used to be compatible with the solvent to prevent agglomeration. Specific examples of the coagulation inhibitor optionally added to the thermosetting resin composition of the present invention are: DISPERBYK-145, DISPERBYK-161, DISPERBYK (161 DISPERBYK)-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-182, DISPERBYK-184, Di DISPERBYK-185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191 , DISPERBYK-199, DISPERBYK-2015 (all trade names, BYK-Chemie Japan Co., Ltd.), FTX-218, FJT (Ftergent) 710FM, Ftergent 710FS (both trade names, Neos Co., Ltd.), Flolen (Flowlen) G-600, Floren (Flowlen) G-700 (both Is a trade name, Gongrongshe Chemical Industry Co., Ltd.).

An antioxidant may be added to the thermosetting resin composition of the present invention. As the antioxidant, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds can be suitably used. Antioxidants can be used alone or in combination of two or more. From the viewpoint of weather resistance, the antioxidant is preferably an antioxidant of a hindered phenol compound.

As the antioxidant optionally added to the thermosetting resin composition of the present invention, hindered amine-based, hindered phenol-based and the like can be used. Specific examples include: IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (both trade names, manufactured by BASF (Japan)), ADK STAB AO-20, AI ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 , ADK STAB AO-80 (trade name; ADEKA) Co., Ltd. Among these compounds, from the viewpoint of suppressing the discoloration of the thermosetting resin composition of the present invention, IRGANOX 1010 and ADK STAB AO-60 are more preferred.

From the viewpoint of improving heat resistance, chemical resistance, film surface uniformity, flexibility, flexibility, and elasticity, the thermosetting resin composition of the present invention may optionally include a crosslinking agent.

Specific examples of the thermal crosslinking agent optionally added to the thermosetting resin composition of the present invention include: jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (all are trade names, Mitsubishi Chemical Corporation). jER1004, jER1256, YX8000 (all trade names, Mitsubishi Chemical Corp.), Araldite CY177, Araldite CY184 (all trade names, Huntsman Japan) ), Celloxide 2021P, EHPE-3150 (both trade names, Daicel Chemical industries (shares)), Techmore VG3101L (trade name, Principe) (Printec Co., Ltd.), Nikalak MW-30HM, Nikarac MW-100LM, Nikarac MW-270, Nikarac MW-280, Nika Nikalac MW-290, Nikalac MW-390, Nikalac MW-750LM (all are trade names, Sanwa Chemical (share)).

<1-5. Storage of Thermosetting Resin Composition> If the thermosetting resin composition of the present invention is stored in a light-shielding range of -30°C to 25°C, the stability of the composition over time becomes good, Therefore, it is preferred. More preferably, it is stored at -10°C to 20°C.

<2. Cured film obtained from the thermosetting resin composition> The thermosetting resin composition of the present invention can include the polymer (c), and according to the target characteristics, further add a solvent, a coupling agent, and an interface as needed Active agents, antioxidants and other additives are obtained by uniformly mixing and dissolving them. If the thermosetting resin of the present invention or the thermosetting composition using the same (after dissolving in a solvent in a solid state without a solvent) is applied to the surface of a substrate, for example, the solvent is removed by heating, then Coating film can be formed.

The coating method of the thermosetting resin composition of the present invention can use conventionally known methods such as spin coating method, roll coating method, dipping method, slit coating method, inkjet method, flexographic printing method, and gravure printing method. Method to form a coating film.

Examples of the substrate used in the film formation include plastics, glass, and substrates with transparent electrodes such as Fluorine-doped Tin Oxide (FTO) or Indium Tin Oxide (ITO). Specific examples of plastics include polycarbonate, poly(meth)acrylate, polyurethane, polyethylene terephthalate, cycloolefin, and triethyl cellulose.

The coating film is heated (pre-baked) using a hot plate or an oven. The heating conditions vary depending on the type of each component and the mixing ratio, and are usually 60°C to 100°C for 1 minute to 15 minutes. Then, in order to harden the coating film, a cured film can be obtained by performing heat treatment (post-baking) at 100° C. to 150° C., preferably 120° C. to 150° C. for 5 to 60 minutes.

The thermosetting resin composition of the present invention can obtain a cured film even if it is thermally cured at a low temperature of 120°C to 150°C, which is the temperature at which the coating film is cured. Therefore, if the thermosetting resin composition of the present invention is applied to a substrate having a low glass transition point, such as plastic, the substrate does not deteriorate or break, and a cured film can be obtained. [Example]

Hereinafter, the present invention will be further described by examples, but the present invention is not limited by these examples. The evaluation method of the thermosetting resin composition of the present invention is shown below.

[Evaluation method of thermosetting resin composition] 1) The thickness of the film is on a glass substrate (Eagle XG (trade name) manufactured by Corning Co., Ltd., 40 mm×40 mm×0.7 mm) , The thermosetting resin composition was spin-coated at a predetermined number of revolutions for 10 seconds, and pre-baked on a hot plate at 90°C for 2 minutes. The substrate was baked on a hot plate at a predetermined temperature for 10 minutes, and the film thickness was measured. The film thickness is measured using a step difference, surface roughness, and fine shape measuring device (P-16+ (trade name), KLA-Tencor Japan) Co., Ltd., and the average value of the three measurements As the film thickness. The rotation speed is adjusted so that the film thickness after baking becomes 3.0 μm. 2) The coating properties were visually observed for the formed cured film, and the case where there was no unevenness was set to "○", and the case where unevenness was generated was set to "△", which caused repulsion and insufficient formation. The case where the film is on the substrate is set to "×". 3) Curability The resin film substrate measured by the film thickness is immersed in the solvent used for the thermosetting resin composition maintained at 24°C for 2 minutes. After taking out from the solvent and removing the solvent by blowing air, the film thickness was measured, and the residual film ratio=(film thickness after immersion/film thickness before immersion)×100 was calculated. The post-baking temperature was measured at a curing temperature of 100°C, 120°C, 140°C, and 230°C, and it was confirmed that the residual film rate became 95% or more. A person who could not make a cured film was set to "×", and a person whose residual film rate did not reach 95% or more even at 230°C was set to ">230". 4) Transparency For the obtained glass substrate with a cured film, using an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, manufactured by Japan Spectroscopy Co., Ltd.), only the wavelength of light of the cured film at 400 nm was measured Under the light transmittance. If the light transmittance is 95% or more, it is determined that the transparency is good. A sample in which the film cannot be formed sufficiently and the transmittance cannot be measured is indicated as "-". 5) Storage stability The viscosity at the time of preparation of the thermosetting resin composition is set to 100, the viscosity after storage at room temperature for 7 days, 14 days, and 30 days is 110 or more is set to "×", and the storage at room temperature is 7 The viscosity after days, 14 days, and 30 days is 95 to 105, and is set to "○".

[Polymerization Example 1] In a four-necked flask equipped with a stirrer, while bubbling nitrogen, 18.0 g of propylene glycol methyl ether as a polymerization solvent and 4.51 g of Aronix M-402 as a monomer were added (Trade name, East Asia Synthetic Co., Ltd.), 0.90 g of 2,4-diphenyl-4-methyl-1-pentene (α-MSD) as a chain transfer agent, and 0.23 g as a polymerization initiator V-65 (trade name, Wako Pure Chemical Industries, Ltd.), after stirring at 35°C for 5 minutes to confirm the dissolution of the contents, the temperature was raised to 80°C in 15 minutes. Then, it heated at 80 degreeC for 3 hours, and polymerized.

The polymerization solution was cooled to room temperature to obtain a polymer (c1). A part of the polymerization solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 11,800.

[Polymerization Example 2 to Polymerization Example 6] A polymer (c2) was obtained by the same method as Polymerization Example 1 except that the compound (a) having a trifunctional or more polymerizable double bond and the polymerization conditions were changed as described in Table 1. ) ~ Polymer (c6).

[Comparative Polymerization Example 1] As described in Table 1, the compound (a) having a trifunctional or more polymerizable double bond was changed to a compound having a monofunctional polymerizable double bond to obtain a polymer (c7).

[Comparative Polymerization Example 2] As described in Table 1, the polymer (c8) was obtained so that the weight average molecular weight of the obtained polymer exceeded 200,000.

[Comparative Polymerization Example 3] As described in Table 1, the polymerization was carried out in the same manner as in Polymerization Example 1, except that the chain transfer agent was not used. Gelation was confirmed at the stage of temperature increase during polymerization, and a polymer solution could not be obtained.

Table 1

The abbreviations in the table indicate the following monomers, polymerization initiators, chain transfer agents, solvents, etc., respectively. M-402: Aronix M-402 (trade name, East Asia Synthesizing Co., Ltd.) M-450: Aronix M-450 (trade name, East Asia Synthesizing Co., Ltd.) M-520: Aronix M-520 (trade name, East Asia Synthetic Co., Ltd.) BMA: butyl methacrylate MMA: methyl methacrylate V-65: azo polymerization initiator V-65 (trade name, Wako Pure Chemical Industries Co., Ltd.) VPE-0201: high molecular azo initiator VPE-0201 (trade name, Wako Pure Chemical Industries Co., Ltd.) α-MSD: 2,4-diphenyl-4-methyl -1-pentene PGME: methyl propylene glycol (trade name, Japan Emulsifier Co., Ltd.)

[Example 1 to Example 6] For 10 g of the polymerization solution (c1 to c6), 0.0011 g of surfactant BYK-342 (trade name, BYK-Chemie Japan) was added Co., Ltd.), conducted the evaluation, and obtained the results in Table 2.

[Comparative Example 1 and Comparative Example 2] In the same manner as in the example, 0.0011 g of BYK-342 (trade name, BYK Chemicals, Japan) was added to the polymerization solution (c7) and the polymerization solution (c8), respectively. (BYK-Chemie Japan) Co., Ltd., performed the evaluation, and obtained the results in Table 2.

Table 2

As is clear from the results in Table 2, the thermosetting compositions containing the polymers of Examples 1 to 6 showed excellent low-temperature curability and storage stability.

In Comparative Example 1, a compound having a monofunctional polymerizable double bond was used as a polymer monomer. Although Comparative Example 1 has good storage stability, it does not exhibit low-temperature curability as shown in Examples 1 to 6. Therefore, it has been shown that it is effective to use a polymer having trifunctionality or more as a polymer monomer Compound (a).

Comparative Example 2 increases the weight average molecular weight of the polymer. Comparative Example 2 does not show good characteristics as shown in Examples 1 to 6 in terms of storage stability and coatability, and shows that the weight average molecular weight of the polymer is important.

Comparative polymerization example 3 is polymerization without using a chain transfer agent (b). In Comparative Polymerization Example 3, gelation occurred at the time of polymerization, indicating that no polymerization liquid was obtained. Therefore, it was shown that in order to obtain polymers exhibiting good characteristics as shown in Examples 1 to 6, a chain transfer agent is effective. [Industry availability]

The thermosetting resin composition and its cured film used in the present invention can be applied to the production of a cured film on a substrate requiring low-temperature processing. For example, it can be used as a material for protecting surfaces.

no

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Claims (8)

A thermosetting resin composition comprising a polymer (c) having a weight-average molecular weight of 2,000 to 200,000 and a solvent, the polymer (c) is a compound (a) having a polymerizable double bond of trifunctional or more in In the presence of a chain transfer agent (b), it is obtained by heating in a solution at a temperature of 50° C. to 90° C. for 1 hour to 8 hours for radical polymerization. The thermosetting resin composition as described in item 1 of the patent application, wherein the compound (a) is a (meth)acrylate having more than three functions. The thermosetting resin composition as described in Item 1 or Item 2 of the patent application, wherein the chain transfer agent (b) is an addition-breaking type chain transfer agent. The thermosetting resin composition as described in item 1 or item 2 of the patent application, wherein the chain transfer agent (b) is 2,4-diphenyl-4-methyl-1-pentene. The thermosetting resin composition according to item 1 or item 2 of the patent application scope, wherein the polymer (c) is manufactured by batch polymerization. A cured film obtained by thermally curing the thermosetting resin composition according to any one of claims 1 to 5 of the patent application. A cured film obtained by thermally curing the thermosetting resin composition according to any one of claims 1 to 5 at 100°C to 150°C. A display element comprising the cured film as described in item 6 or 7 of the patent application.