JP2013224373A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in low temperature curability, flexibility and printability.SOLUTION: A resin composition includes (A) a polybutadiene resin having an epoxy group and an urethane structure, and (B) a thiol-based curing agent, where (A) the polybutadiene resin having an epoxy group and an urethane structure is 50-95 mass% when the total solid content of the resin composition is made 100 mass%.

Description

The present invention relates to a resin composition. Furthermore, an overcoat agent for protecting the electronic circuit surface of a flexible printed circuit board, an organic EL display, electronic paper, other members for forming an interlayer insulating film used in the field of various display devices such as a touch panel, and an organic TFT (thin film transistor) ) Related to the members used in the field.

Particularly in recent years, a thin film transistor (TFT) using an organic semiconductor layer has attracted attention in the field of various display devices such as an organic EL display and electronic paper, and is called an organic TFT. Organic TFTs are regarded as promising devices that can replace conventional inorganic TFTs using inorganic semiconductor layers, and their applications include various electronic devices such as the above-described display devices. In the organic TFT, since the organic semiconductor layer can be formed at a temperature lower than that of the vapor deposition method or the like as compared with the inorganic TFT, it is expected that the organic TFT can be mounted on a substrate such as a low heat-resistant plastic film.

In particular, by mounting an organic TFT on a flexible substrate such as a plastic film, it is possible to realize an electronic device that can be bent utilizing its flexibility. In this case, it is possible to prevent the base material and the organic TFT element from being thermally damaged by forming the organic semiconductor layer at a low temperature and simultaneously forming the insulating film at a low temperature. Therefore, it has been proposed to form an organic semiconductor layer or an insulating film using a printing method or the like. As in Patent Document 1, a method of printing a desired pattern by screen printing of a varnish-like resin composition (overcoat agent) and curing it is known, but its performance is not sufficient.

International Publication No. 2009/051209 Pamphlet

The problem to be solved by the present invention is to provide a resin composition excellent in low-temperature curability, flexibility and printability.

As a result of intensive studies, the present inventors have found that the above problems can be solved in a resin composition containing a specific polybutadiene resin and a thiol-based curing agent, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a polybutadiene resin having an epoxy group and a urethane structure, and (B) a thiol-based curing agent, wherein the total solid content of the resin composition is 100% by mass, A) A polybutadiene resin having an epoxy group and a urethane structure is 50 to 95% by mass.
[2] The resin composition according to [1] above, wherein the polybutadiene resin (A) having an epoxy group and a urethane structure has a number average molecular weight of 500 to 200,000.
[3] The resin composition as described in [1] or [2] above, wherein the polybutadiene resin (A) having an epoxy group and a urethane structure has an epoxy equivalent of 300 to 10,000.
[4] (A) A polybutadiene resin having an epoxy group and a urethane structure is (a) a polydiene polyol compound having two or more hydroxyl groups in the molecule, and (b) one or more hydroxyl groups and one or more epoxy groups in the molecule. The resin composition as described in any one of [1] to [3] above, which is obtained by reacting an epoxy compound having a polyisocyanate compound having (c) two or more isocyanate groups in the molecule.
[5] When the total solid content of the resin composition is 100% by mass, the thiol-based curing agent (B) is 0.5 to 15% by mass, according to the above [1] to [4] Any resin composition.
[6] The resin composition as described in any one of [1] to [5] above, further comprising (C) an inorganic filler.
[7] The resin composition as described in [6] above, wherein the inorganic filler (C) has an average particle size of 0.005 to 1 μm.
[8] The resin composition as described in any one of [1] to [7] above, further comprising (D) a curing accelerator.
[9] The resin composition as described in any one of [1] to [8] above, which is a resin composition for an overcoat agent or a resin composition for forming an interlayer insulating film.
[10] The resin composition as described in [9] above, which is a resin composition for an overcoat agent for sealing an organic TFT element.
[11] A liquid resin composition or a film-like resin composition using the resin composition according to any one of [1] to [10].
[12] A cured product of the resin composition according to any one of [1] to [11], wherein the cured product has an elongation of 20% or more and an elastic modulus of 1000 MPa or less.
[13] A flexible printed wiring board or an organic TFT device using a cured product of the resin composition as described in [12] above.
[14] An electronic device incorporating the flexible printed wiring board or the organic TFT device according to [13].

A resin composition containing a specific polybutadiene resin and a thiol-based curing agent can provide a resin composition excellent in low-temperature curability, flexibility, and printability.

The present invention is a resin composition comprising (A) a polybutadiene resin having an epoxy group and a urethane structure, and (B) a thiol-based curing agent.

<(A) Polybutadiene resin having epoxy group and urethane structure>
(A) Polybutadiene resin having an epoxy group and a urethane structure (referred to as component (A)) is not particularly limited. For example, (a) a polydiene polyol compound having two or more hydroxyl groups in the molecule (referred to as compound (a)) ), (B) an epoxy compound having one or more hydroxyl groups and one or more epoxy groups in the molecule (referred to as compound (b)), and (c) a polyisocyanate compound having two or more isocyanate groups in the molecule ( Compound (c)) can be obtained by reaction.

Although it does not restrict | limit especially as a compound (a), A polybutadiene polyol, a polyisoprene polyol, etc. are mentioned, These hydrogenated polydiene polyols can also be used. In particular, hydrogenated polydiene polyol is preferable from the viewpoints of improving heat resistance, improving printability, and improving insulation reliability. As polybutadiene polyol, hydroxyl-terminated liquid polybutadiene mainly having 1,4-bonds, Poly bd R-45HT, R-15HT (manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl-terminated polybutadiene hydride polytail H, polytail HA (Mitsubishi) Chemical Co., Ltd.), hydroxyl-terminated polybutadienes G-1000, G-2000, G-3000 (above Nippon Soda Co., Ltd.) mainly having 1,2-bonds, hydroxyl groups mainly having 1,2-bonds Examples include terminal polybutadiene hydrides GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.). Examples of the polyisoprene polyol include hydroxyl-terminated liquid isoprene Poly ip, Epol (manufactured by Idemitsu Kosan Co., Ltd.) and the like. These may be used alone or in combination of two or more. Therefore, considering from the viewpoints of improving heat resistance, improving printability, and improving insulation reliability, it can be said that (A) component is preferably a hydrogenated polybutadiene resin having an epoxy group and a urethane structure.

The number average molecular weight of the compound (a) is preferably 10,000 or less, more preferably 7000 or less, and still more preferably 4000 or less, from the viewpoint of improving compatibility with an organic solvent. On the other hand, from the viewpoint of improving the flexibility of the cured product of the resin composition, 300 or more is preferable, 600 or more is more preferable, and 900 or more is more preferable. In the present invention, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). The number average molecular weight according to the GPC method is specifically shown by GPC-101 manufactured by Showa Denko KK as a measuring device, Shodex KF-800RH / LF-804 manufactured by Showa Denko KK as a column, and tetrahydrofuran as a mobile phase. Can be calculated at a column temperature of 40 ° C. using a standard polystyrene calibration curve.

Although it does not restrict | limit especially as a compound (b), It is 1 type chosen from the group which consists of 1 or more hydroxyl groups in a molecule | numerator, a glycidyl ether structure, a glycidyl ester structure, a glycidyl amine structure, an alicyclic epoxy structure, and an oxirane ring structure. The epoxy compound which has the above epoxy group is mentioned. Examples of commercially available compounds include JER-1001, JER-1002, JER-1003, JER-1004 (Mitsubishi Chemical Corporation) as epoxy compounds having one or more hydroxyl groups and one or more glycidyl ether structures in the molecule. In addition, examples of the epoxy compound having one or more hydroxyl groups and one or more oxirane ring structures in the molecule include hydroxyl group-terminated epoxidized polybutadiene PB-3600 (Daicel Chemical Industries, Ltd.).

Compound (b) includes (d) an epoxy compound having two or more epoxy groups in the molecule (referred to as compound (d)) and (e) a compound having at least one active hydrogen group that reacts with an epoxy group in the molecule ( It can also be obtained by reacting with compound (e).

As the compound (d), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type Epoxy resin, dicyclopentadiene type epoxy resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, epoxidized product of condensation product of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate, Epoxy such as alicyclic epoxy resin, glycidylamine resin, glycidyl ester resin, diglycidyl ether of aliphatic diol, diglycidyl ether of alicyclic diol Resins. These may be used alone or in combination of two or more.

Examples of the compound (e) include compounds having one or more phenolic hydroxyl groups and compounds having one or more carboxyl groups. Since the number of active hydrogen groups reduces the possibility of gelation during the reaction with the compound (d), the compound (e) preferably has 1 or 2 active hydrogen groups. Examples of the compound having one active hydrogen group include a phenol compound, a thiophenol compound, and a carboxylic acid compound. Examples of the compound having two active hydrogen groups include bisphenol A, bisphenol F, bisphenol S, biphenol, hydroquinone, adipic acid, sebacic acid, dodecanedioic acid, 8,12-eicosadienedioic acid, and eicosadioic acid. These may be used alone or in combination of two or more.

Compound (d) and compound (e) can be reacted at a reaction temperature of 80 ° C. to 180 ° C. for 1 hour to 8 hours. An organic solvent may be added to the reaction as necessary, and a catalyst may be added if necessary. Examples of the catalyst include nitrogen compounds and phosphorus compounds.

The compound (c) is not particularly limited, but 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hydrogenated xylylene. Examples include diisocyanate, tetramethylene xylylene diisocyanate, trimethylhexamethylene diisocyanate, and norbornene diisocyanate. These may be used alone or in combination of two or more.

As the reaction conditions for the compound (a), the compound (b), and the compound (c), for example, the reaction is performed in an organic solvent at a reaction temperature of 15 ° C. to 120 ° C. and a reaction time of 1 to 8 hours. it can. Moreover, you may react by adding a catalyst if needed.

The reaction ratio of the compound (a), the compound (b), and the compound (c) is such that the number of hydroxyl groups in the compound (a) is Xa, the number of hydroxyl groups in the compound (b) is Xb, and the number of hydroxyl groups in the compound (c) is When the number is Y, the range where the value of (Xa + Xb) / Y is 1 to 3 is preferable, and the range where 1.0 to 2 is more preferable. When this ratio is 1 or more, the isocyanate group is prevented from becoming excessive, and the molecular weight is easily controlled. Moreover, it becomes easy to make molecular weight high because it is 3 or less.

Further, the compound (a) and the compound (b) are preferably used in a mass ratio of the compound (a): the compound (b) = 90: 10 to 10:90, and the range of 80:20 to 30:70. It is more preferable to use it. When the weight ratio of the compound (a) is larger than 90:10, the heat resistance of the cured body tends to be lowered. When the weight ratio of the compound (b) is larger than 10:90, the flexibility of the cured body is increased. There is a tendency to become insufficient.

Examples of the organic solvent used in the reaction include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, and tetramethyl. Nitrogen-containing solvent such as urea, sulfur-containing compound solvent such as dimethyl sulfoxide and diethyl sulfoxide, cyclic ester compound solvent such as γ-butyrolactone, ketone solvent such as cyclopentanone and cyclohexanone, ether such as diglyme and triglyme Examples thereof include polar solvents such as ester solvents such as solvent based solvents, carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more. Further, if necessary, a nonpolar solvent such as an aromatic hydrocarbon can be appropriately mixed and used.

The reaction may be carried out by adding a catalyst as necessary. Examples of the catalyst include tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N, N-dimethylpiperidine, α-methylbenzyldimethylamine, N- Examples thereof include tertiary amines such as methylmorpholine and triethylenediemine, and organometallic catalysts such as dibutyltin laurate, dimethyltin dichloride, cobalt naphthenate and zinc naphthenate.

The number average molecular weight of the component (A) in the present invention is preferably 200000 or less, more preferably 150,000 or less, and even more preferably 100000 or less from the viewpoint of preventing the viscosity of the resin composition from increasing and handling properties from decreasing. 80,000 or less is still more preferable, 60000 or less is particularly preferable, and 40000 or less is particularly preferable. On the other hand, from the viewpoint of improving the flexibility of the cured product, 500 or more is preferable, 4000 or more is more preferable, 8000 or more is further preferable, 12000 or more is further more preferable, 16000 or more is particularly preferable, and 20000 or more is particularly preferable. The number average molecular weight can be measured in the same manner as described above.

From the viewpoint of improving solvent resistance, the epoxy equivalent of the component (A) in the present invention is preferably 10,000 or less, more preferably 7000 or less, and still more preferably 4000 or less. On the other hand, 300 or more are preferable, 500 or more are more preferable, and 1000 or more are still more preferable from the viewpoint of preventing the crosslinkability of the cured body from becoming too high and reducing flexibility. The epoxy equivalent (g / eq) is the molecular weight of the epoxy resin per epoxy group, and is measured according to JIS K7236.

In the present invention, the blending amount of the component (A) is preferably 50% by mass or more and more preferably 55% by mass or more when the total solid content of the resin composition is 100% by mass from the viewpoint of improving the flexibility of the cured product. Preferably, 60 mass% or more is further more preferable, and 65 mass% or more is still more preferable. On the other hand, from the viewpoint of improving the compatibility and printability of the resin composition, when the total solid content of the resin composition is 100% by mass, it is preferably 95% by mass or less, more preferably 93% by mass or less, and 91% by mass. The following is more preferable, and 89% by mass or less is even more preferable.

<(B) Thiol-based curing agent>
In the present invention, low temperature curability can be improved by using (B) a thiol-based curing agent (referred to as component (B)). The component (B) is not particularly limited as long as it is a compound that crosslinks or polymerizes an epoxy group. For example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipenta Examples include erythritol hexakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, and the like. Commercially available products include OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP, Sakai Chemical Industry Co., Ltd. TEMP, PEMP, TEMPIC, DPMP, Showa Denko Corporation PE-1 , BD-1, NR-1, TPMB, TEMB, and the like.

The blending amount of the component (B) in the present invention is preferably 0.5% by mass or more when the total solid content of the resin composition is 100% by mass from the viewpoint of efficiently curing the resin composition at low temperature. 1 mass% or more is more preferable, 1.5 mass% or more is still more preferable, and 2 mass% or more is still more preferable. On the other hand, from the viewpoint of improving the storage stability of the resin composition, when the total solid content of the resin composition is 100% by mass, 15% by mass or less is preferable, 13% by mass or less is more preferable, and 10% by mass or less. Is more preferable, 7 mass% or less is still more preferable, and 5 mass% or less is especially preferable.

<(C) Inorganic filler>
The resin composition of this invention can adjust the viscosity of a resin composition and can improve a handleability by further containing (C) inorganic filler as needed. The inorganic filler is not particularly limited, and silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium Examples thereof include barium oxide, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, fumed silica is particularly preferable. You may use these 1 type or in combination of 2 or more types. As commercially available inorganic fillers, hydrophilic fumed silica such as “200”, “200CF”, “300”, “300CF”, “380” manufactured by Nippon Aerosil Co., Ltd., “R-805”, “R” Hydrophobic fumed silica such as “-812”, “RY-200”, “RY-300”, “RX-200”, “RX-300”, “SOC2”, “SOC1” manufactured by ADMATEX It is done.

The average particle size of the inorganic filler (C) in the present invention is preferably 1 μm or less, more preferably 0.7 μm or less, from the viewpoint of improving the insulation reliability and facilitating the viscosity adjustment of the resin composition. 0.5 μm or less is more preferable, 0.3 μm or less is even more preferable, and 0.1 μm or less is particularly preferable. On the other hand, it is preferably 0.005 μm or more from the viewpoint of preventing aggregation of the inorganic filler. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used. In addition, in order to improve moisture resistance and dispersibility, inorganic fillers have silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.), titanate coupling agents, and silazanes. Those that have been surface treated with a surface treating agent such as a compound are preferred. You may use these 1 type or in combination of 2 or more types.

Epoxysilane coupling agents include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxy Examples of aminosilane coupling agents include aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) aminopropyltrimethoxysilane. Examples of the mercaptosilane coupling agent include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. You may use these 1 type or in combination of 2 or more types.

Titanium coupling agents include butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (Dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl) Phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite tita Isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzene sulfonyl titanate, Examples thereof include isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-amidoethyl / aminoethyl) titanate, and the like. You may use these 1 type or in combination of 2 or more types.

Examples of the silazane compound include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (t-butyl) disilazane, hexabutyldisilazane, hexaoctyldi Silazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3- Diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethyl Silazane, trisilazane, cyclotrisilazane, 1,1,3,3 , 5,5-hexamethylcyclotrisilazane and the like, with hexamethyldisilazane being particularly preferred. You may use these 1 type or in combination of 2 or more types.

The treatment amount of the surface treatment agent is preferably 0.1 to 6% by mass, more preferably 0.3 to 4% by mass, when the inorganic filler is 100% by mass.

(C) The content in the case of blending the inorganic filler is preferably 1% by mass or more when the total solid content of the resin composition is 100% by mass from the viewpoint of facilitating the viscosity adjustment of the resin composition. 3 mass% or more is more preferable, and 5 mass% or more is still more preferable. On the other hand, from the viewpoint of preventing a decrease in the elastic modulus and elongation of the cured product of the resin composition, the total solid content of the resin composition is 100% by mass, preferably 30% by mass or less, and 25% by mass or less. Is more preferable, and 20 mass% or less is still more preferable.

<(D) Curing accelerator>
The resin composition of this invention can improve the heat resistance, adhesiveness, chemical resistance, etc. of a hardening body by further containing (D) hardening accelerator as needed. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s -Triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2- Examples thereof include imidazole compounds such as methylimidazoline, 2-phenylimidazoline, 1- (2-hydroxy) -3-phenoxypropyl-2-methylimidazole, and adducts of imidazole compounds and epoxy resins. You may use these 1 type or in combination of 2 or more types.

Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.

In the resin composition of the present invention, the content of the curing accelerator is 7% by mass or less from the viewpoint of improving the storage stability of the resin composition when the total solid content of the resin composition is 100% by mass. Preferably, 6 mass% or less is more preferable, and 5 mass% or less is still more preferable. On the other hand, from the viewpoint of efficiently curing the resin composition and improving the low-temperature curability, when the total solid content of the resin composition is 100% by mass, 0.005% by mass or more is preferable, and 0.01 More preferably, it is more preferably 0.1% by mass or more.

<Other ingredients>
The resin composition of the present invention comprises an antifoaming agent such as a silicone-based antifoaming agent, a fluorine-based antifoaming agent, an acrylic polymer-based antifoaming agent, an inorganic pigment such as titanium oxide or zinc oxide, phthalocyanine blue, phthalocyanine green, eye Odin green, disazo yellow, carbon black and other organic pigments, organic dyes and other colorants, hindered phenolic compounds, phosphorus compounds, sulfur compounds, hydrazide compounds and other antioxidants, benzotriazole compounds, hindered amines UV absorbers such as compounds, phosphorus compounds, flame retardants such as aluminum hydroxide and magnesium hydroxide, leveling agents, thixotropic agents, 2,4,6-trimercapto-s-triazole, 2,5-dimercapto- Examples thereof include adhesion improvers such as 1,3,4-thiadiazole.

The elastic modulus of the cured product of the resin composition of the present invention can be measured by <evaluation of flexibility> described later. The elastic modulus is preferably 5 MPa or more, more preferably 10 MPa or more, and still more preferably 15 MPa or more from the viewpoint of improving the mechanical strength of the cured body and extending the usage time of the device. Moreover, 1000 MPa or less is preferable, 600 MPa or less is preferable, and 400 MPa or less is still more preferable from a viewpoint that it becomes easy to apply to a flexible use by improvement in a softness | flexibility and bending resistance.

The elongation of the cured product of the resin composition of the present invention can also be measured by <evaluation of flexibility> described later. The elongation is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 60% or more, and particularly preferably 80% or more from the viewpoint of preventing cracks in the cured product. Moreover, although there is no restriction | limiting in particular in an upper limit, from a viewpoint of handleability, 500% or less is preferable, 400% or less is more preferable, and 300% or less is still more preferable.

Although the form of the resin composition of this invention is not specifically limited, It is suitable to use as a liquid resin composition and a film-form resin composition.

Applications of the resin composition of the present invention include overcoat agent, interlayer insulating film formation, prepreg, solder resist, underfill material, die bonding material, semiconductor sealing material, hole filling resin, component embedding resin, TAB use, COF use Etc., and can be used in a wide range of insulating applications where a resin composition is required. In particular, a resin composition for an overcoat agent or a resin composition for forming an interlayer insulating film is preferable, and is preferably used as an overcoat agent for a flexible printed wiring board or a resin composition for forming an interlayer insulating film of a display device. Especially, since the cured body of the resin composition of the present invention has excellent flexibility, it is a resin composition for an overcoat agent for sealing an organic TFT element, an organic EL display, electronic paper, and others. More preferably, it is used as a member for forming an interlayer insulating film used in the field of various display devices such as a touch panel. And by using the cured body of the resin composition of the present invention, the flexible printed wiring board or the organic TFT device has excellent performance, and an electronic device incorporating these flexible printed wiring board or organic TFT device is used. For example, mobile phones, digital cameras, video cameras, game machines, personal computers, printers, hard disk drives, plasma televisions, liquid crystal televisions, liquid crystal displays, car navigation systems, copiers, fax machines, AV equipment, measuring equipment , Medical equipment, organic EL display, electronic paper and the like.

The resin composition of the present invention is a mixture of components (A) and (B), and kneading means such as a three roll, ball mill, bead mill, sand mill, or agitation such as a super mixer or planetary mixer. A resin varnish can be prepared by dissolving or dispersing by means. In the preparation, if necessary, an organic solvent for adjusting the viscosity may be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more.

<Liquid resin composition>
The resin composition of the present invention is dissolved or dispersed in various organic solvents as described above to obtain a liquid resin composition necessary for forming an insulating protective film of a printed wiring board. can do. Although the organic solvent used here is not particularly limited, it is preferable to use a solvent having a boiling point of 100 ° C. or higher in terms of suppressing the volatilization of the solvent and improving the printability. It is more preferable to use a solvent having a temperature of 0 ° C. or higher. In particular, when used as an overcoat for a flexible printed wiring board, it is preferably prepared as a liquid resin composition.

<Film-like resin composition>
The resin composition of the present invention can be used to produce a film-shaped resin composition according to a method known to those skilled in the art. For example, the resin resin varnish prepared as described above is applied onto a support, and the organic solvent is dried by heating or hot air blowing to form a film resin composition. A film-like resin composition with a support called a product (A layer) and a support (B layer) can be produced. The support serves as a support when the film-shaped resin composition is produced, and is finally peeled off or removed in the production of the circuit board. Examples of the support include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polyimide films, and release paper and copper foil. The metal foil can be mentioned.

The drying conditions of the resin varnish are not particularly limited, but it is important that the resin composition is not cured as much as possible during drying in order to maintain the adhesive ability. In addition, if a large amount of the organic solvent remains in the film-shaped resin composition, it may cause swelling after curing. Therefore, the ratio of the organic solvent in the film-shaped resin composition is 5% by mass or less, preferably 3% by mass. Dry to: Specific drying conditions are preferably dried at, for example, 50 to 120 ° C. for 3 to 15 minutes.

The thickness of the film-like resin composition (A layer) is not particularly limited, but is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less in terms of improving the bending resistance of the cured product. Moreover, 1 micrometer or more is preferable from the point of a handleability improvement, 3 micrometers or more are more preferable, and 10 micrometers or more are still more preferable.

<Flexible printed wiring board or organic TFT device>
The liquid resin composition of the present invention is applied to a predetermined portion of a flexible printed wiring board or an organic TFT device, and the coated surface is cured, so that the entire surface or a part of the surface is protected with the resin composition of the present invention. A printed wiring board or an organic TFT device can be obtained. The curing condition is that at least the solvent constituting the liquid resin composition is sufficiently dried and the resin composition is sufficiently heat-cured, so that the curing condition is 80 to 200 ° C. for 1 to 120 minutes. It is preferable to dry. Although the thickness of the surface protective film formed is not specifically limited, 1-100 micrometers is preferable.

In addition, the resin composition of the present invention is obtained by laminating a film-like resin composition on a predetermined portion of a flexible printed wiring board or an organic TFT device with a vacuum laminator and curing the resin composition so that the entire surface or a part of the surface is the resin composition of the present invention A flexible printed wiring board or an organic TFT device protected with can be obtained. At this time, by using the film-shaped resin composition with a support, the laminating apparatus can be prevented from being soiled. The lamination conditions at this time can be easily set as appropriate by those skilled in the art depending on the type of the film-like resin composition to be used, but the temperature is 80 to 200 ° C., the pressure is 1 to 40 kgf / cm ² , and the time is 5 Lamination is preferably performed under a reduced pressure of ˜180 seconds and an air pressure of 20 mmHg or less. The laminating method may be a batch method or a continuous method using a roll. The curing conditions can be appropriately set by those skilled in the art depending on the type of the film-shaped resin composition (layer A) to be used, but at least the conditions for the resin composition to be sufficiently heat-cured. is necessary. In particular, when elements are disposed, in order not to deteriorate the elements disposed on the substrate, 150 ° C. or lower is preferable, 130 ° C. or lower is more preferable, and 110 ° C. or lower is even more preferable. On the other hand, from the viewpoint of improving the chemical resistance of the cured body, 40 ° C. or higher is preferable, 45 ° C. or higher is more preferable, and 50 ° C. or higher is even more preferable.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the following description, “part” means “part by mass”.

<Production Example 1>
A polydiene polyol “GI-1000” (manufactured by Nippon Soda Co., Ltd., hydroxyl value 70 mg KOH / g) 157.8 g, “Swazole # 1000” (organic solvent, Daicel Chemical) 26.2 g manufactured by Kogyo Co., Ltd. and 17.1 g ethyl diglycol acetate were added and stirred under a nitrogen atmosphere at room temperature, “Coronate T-100” (2,4-tolylene diisocyanate, Nippon Polyurethane Industry Co., Ltd.) A mixture of 34.4 g and 23.0 g of ethyl diglycol acetate was added and reacted at room temperature for 45 minutes. Next, 2.74 g of a 1% solution of Swazol # 1000 of “Neostan U-810” (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) was added, and the reaction was carried out at 45 ° C. for 1 hour. Then, after cooling to room temperature, a mixture of 17.8 g of 1,4-butanediol and 21 g of ethyl diglycol acetate was added with stirring, and the product temperature was raised to 80 ° C. and reacted for 90 minutes. It was confirmed by infrared spectroscopic analysis that absorption based on isocyanate groups (2274 cm-1) had disappeared, and reaction product 1 was obtained.
Subsequently, 229.5 g of the reaction product 1, 28.5 g of ethyl diglycol acetate, and 23.4 g of “Swazole # 1000” were charged into a 1 liter flask equipped with a stirrer, a thermometer, and a condenser, and stirred at room temperature in a nitrogen atmosphere. While adding 26.3 g of “Coronate T-100”, 20.1 g of ethyl diglycol acetate and 11.7 g of “Swazole # 1000”, the temperature of the product was raised to 45 ° C. and reacted for 1 hour. . After cooling to room temperature, “JER-1001” (manufactured by Mitsubishi Chemical Corporation) dissolved in 70% ethyl diglycol acetate with stirring was 59.8 g in terms of solid content, 3.4 g of 1,4-butanediol, A mixture of 44.4 g of ethyl diglycol acetate and 10.9 g of “Swazole # 1000” was added, the temperature of the product was raised to 45 ° C., and the mixture was reacted for 45 minutes. Thereafter, a mixture of 0.84 g of isobutyl alcohol and 13.4 g of ethyl diglycol acetate was added, and the mixture was further reacted at a product temperature of 45 ° C. for 1 hour. Finally, 1.3 g of “Neostan U-810” “swazol # 1000” 1% solution was added, the product temperature was raised to 110 ° C., and infrared spectroscopic analysis confirmed that absorption based on isocyanate groups had disappeared. Thus, the reaction was terminated to obtain a polybutadiene resin (Product 1) having an epoxy group and a urethane structure.

Properties of product 1 Solid content 50.2%
Number average molecular weight 9975
Epoxy equivalent 1957

<Production Example 2>
Hydrogenated polydiene polyol “G-1000” (manufactured by Nippon Soda Co., Ltd., hydroxyl value 73 mgKOH / g) 157.8 g, “Swazole # 1000” (Daicel Chemical Industries, Ltd.) in a 500 ml flask equipped with a stirrer, thermometer and condenser 26.2 g, manufactured by Co., Ltd. and 17.1 g of ethyl diglycol acetate, 34.4 g of “Coronate T-100” (manufactured by Nippon Polyurethane Industry Co., Ltd.) and ethyl diglycol while stirring at room temperature in a nitrogen atmosphere A mixture of 23.0 g of acetate was added and reacted at room temperature for 45 minutes. Subsequently, 2.74 g of a 1% solution of Swazol # 1000 of “Neostan U-810” was further added, and the reaction was carried out at 45 ° C. for 1 hour. Then, after cooling to room temperature, a mixture of 17.8 g of “GI-1000” and 21 g of ethyl diglycol acetate was added with stirring, and the product temperature was raised to 80 ° C. and reacted for 90 minutes. It was confirmed that the absorption (2274 cm-1) based on the isocyanate group disappeared by infrared spectroscopic analysis, and a reaction product 2 was obtained.
Subsequently, 229.5 g of the reaction product 1, 28.5 g of ethyl diglycol acetate, and 23.4 g of “Swazole # 1000” were charged into a 1 liter flask equipped with a stirrer, a thermometer, and a condenser, and stirred at room temperature in a nitrogen atmosphere. While adding 26.3 g of “Coronate T-100”, 20.1 g of ethyl diglycol acetate and 11.7 g of “Swazole # 1000”, the temperature of the product was raised to 45 ° C. and reacted for 1 hour. . After cooling to room temperature, “JER-1001” dissolved in ethyl diglycol acetate 70% with stirring was 59.8 g in terms of solids, 3.4 g of 1,4-butanediol, 44.4 g of ethyl diglycol acetate, A mixture of 10.9 g of “Swazole # 1000” was added, the product temperature was raised to 45 ° C., and the mixture was reacted for 45 minutes. Thereafter, a mixture of 0.84 g of isobutyl alcohol and 13.4 of ethyl diglycol acetate was added, and the mixture was further reacted at a product temperature of 45 ° C. for 1 hour. Finally, 1.3 g of “Neostan U-810” “swazol # 1000” 1% solution was added, the product temperature was raised to 110 ° C., and infrared spectroscopic analysis confirmed that absorption based on isocyanate groups had disappeared. Thus, the reaction was terminated to obtain a polybutadiene resin (Product 2) having an epoxy group and a urethane structure.

Properties of product 2
49.9% solids
Number average molecular weight 10468
Epoxy equivalent 1974

<Production Example 3>
A 500 ml flask equipped with a stirrer, thermometer and condenser was charged with 36.8 g of “Coronate T-100”, 15.0 g of ethyl diglycol acetate, and 28.8 g of “Swazole # 1000” and stirred at room temperature in a nitrogen atmosphere. . To this was added a mixture of 9.5 g of 1,4-butanediol and 15.0 g of ethyl diglycol acetate, and 0.78 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was added. The temperature was raised to 80 ° C. and reacted for 90 minutes. After cooling to 60 ° C. or lower, hydrogenated polybutadiene “GI-2000” (manufactured by Nippon Soda Co., Ltd., hydroxyl value = 47 mg KOH / g) 124.1, ethyl diglycol acetate 15.0 g, “Swazole # 1000” 28.8 g Then, 1.56 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was added, and the product temperature was raised to 45 ° C. and reacted for 90 minutes. A mixture of 9.5 g of 1,4-butanediol and 15.0 g of ethyl diglycol acetate was added thereto, the product temperature was raised to 80 ° C., and the mixture was further reacted for 90 minutes. Infrared spectroscopic analysis confirmed that the absorption based on the isocyanate group (2274 cm-1) had disappeared, and reaction product 3 was obtained.
Subsequently, 265.5 g of the reaction product 3 synthesized in a 1 liter flask equipped with a stirrer, a thermometer, and a condenser was charged with 265.5 g of ethyl diglycol acetate, and 69.2 g of “Swazole # 1000”. A mixture of 16.3 g of “Coronate T-100”, 6.1 g of ethyl diglycol acetate and 4.1 g of “Swazol # 1000” was added with stirring, and the temperature was raised to 80 ° C. for 90 minutes. I let you. After cooling to room temperature, “JER-1001”, 70% dissolved in ethyl diglycol acetate with stirring, was added with a mixture of 74.0 g in terms of solid content and 19.0 g of ethyl diglycol acetate, and the product temperature was 45 The temperature was raised to ° C. and reacted for 60 minutes. Next, a mixture of 1.0 g of isobutyl alcohol and 3.2 g of ethyl diglycol acetate was added and allowed to react for 20 minutes while maintaining the product temperature at 45 ° C. Further, a 1% solution of “Swazole # 1000” of “Neostan U-810” 1 .2 g was added and the product temperature was raised to 110 ° C. and reacted for 90 minutes.
Infrared spectroscopic analysis confirmed that the absorption based on the isocyanate group (2274 cm-1) had disappeared, and terminated the reaction to obtain a polybutadiene resin (Product 3) having an epoxy group and a urethane structure.

Property of product 3 Solid content 51.1%
Number average molecular weight 26833
Epoxy equivalent 1405

<Production Example 4>
A 1-liter flask equipped with a stirrer, a thermometer, and a condenser was charged with 23.6 g of “Coronate T-100”, 13.3 g of ethyl diglycol acetate, and 31.9 g of “Swazole # 1000” and stirred at room temperature in a nitrogen atmosphere. . A mixture of 6.1 g of 1,4-butanediol and 13.3 g of ethyl diglycol acetate was added thereto, and 0.7 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was further added. The temperature was raised to 80 ° C. and reacted for 90 minutes. After cooling to 60 ° C. or lower, hydrogenated polybutadiene “GI-3000” (manufactured by Nippon Soda Co., Ltd., hydroxyl value = 30 mg KOH / g) 129.1 g, ethyl diglycol acetate 13.3 g, “Swazole # 1000” 47.8 g In addition, 1.4 g of a 1% “Swazole # 1000” solution of “Neostan U-810” was added, the product temperature was raised to 80 ° C., and the mixture was reacted for 80 minutes. After cooling to 40 ° C., a mixture of 6.1 g of 1,4-butanediol and 13.3 g of ethyl diglycol acetate was added, the product temperature was raised to 80 ° C., and the mixture was further reacted for 90 minutes. Infrared spectroscopic analysis confirmed that the absorption (2274 cm-1) based on the isocyanate group had disappeared, and the reaction was completed to obtain a reaction product 4.
Subsequently, 311.1 g of the reaction product 4, 7.4 g of ethyl diglycol acetate, and 55.8 g of “Swazole # 1000” were charged into a 1 liter flask equipped with a stirrer, a thermometer, and a condenser, and stirred at room temperature in a nitrogen atmosphere. While adding 12.3 g of “Coronate T-100” and 9.3 g of ethyl diglycol acetate, the product temperature was raised to 80 ° C. and reacted for 90 minutes. After cooling to room temperature, “JER-1001” dissolved in ethyl diglycol acetate 70% with stirring was added to a mixture of 55.9 g in terms of solid content and 17.5 g of ethyl diglycol acetate, and the product temperature was 45. The temperature was raised to 0 ° C. and reacted for 1 hour. Thereafter, 0.78 g of isobutyl alcohol and 3.0 g of ethyl diglycol acetate were added and reacted for 30 minutes. Then, 3.1 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was added, and the product temperature was changed to 110 ° C. The mixture was heated up to react for 2 hours. Infrared spectroscopic analysis confirmed that absorption based on isocyanate groups (2274 cm −1) had disappeared, and terminated the reaction to obtain a polybutadiene resin (Product 4) having an epoxy group and a urethane structure.

Property of product 4 Solid content 47.8%
Number average molecular weight 20859
Epoxy equivalent 1999

<Production Example 5>
A 1 l flask equipped with a stirrer, a thermometer and a condenser was charged with 205.1 g of the reaction product 1, 16.9 g of ethyl diglycol acetate and 45.9 g of “Swazole # 1000”, and stirred at room temperature in a nitrogen atmosphere. A mixture of 23.5 g of Coronate T-100 and 10.1 g of ethyl diglycol acetate was added, and the product temperature was raised to 80 ° C. and reacted for 90 minutes. After cooling to room temperature, a mixture of 107.1 g in terms of solid content and 29.0 g of ethyl diglycol acetate dissolved in 70% of ethyl diglycol acetate with stirring was added, and the product temperature was 45. The temperature was raised to ° C. and reacted for 1 hour. Thereafter, a mixture of 1.5 g of isobutyl alcohol and 4.7 g of ethyl diglycol acetate was added, and the mixture was further reacted at a product temperature of 45 ° C. for 30 minutes. Finally, 1.3 g of a 1% solution of “Neostan U-810” “Swazole # 1000” was added, the temperature of the product was raised to 110 ° C., and the mixture was reacted for 90 minutes. Infrared spectroscopic analysis confirmed that the absorption based on the isocyanate group (2274 cm-1) had disappeared, and terminated the reaction to obtain a polybutadiene resin (Product 5) having an epoxy group and a urethane structure.

Property of product 5 Solid content 56.1%
Number average molecular weight 6343
Epoxy equivalent 1202

<Production Example 6>
A 1-liter flask equipped with a stirrer, a thermometer, and a condenser was charged with 253.2 g of the reaction product 1, 31.8 ethyl diglycol acetate, and 29.0 g of “Swazole # 1000” and stirred at room temperature under a nitrogen atmosphere. A mixture of 29.0 g of Coronate T-100 and 27.9 g of ethyl diglycol acetate was added, and the product temperature was raised to 40 ° C. and reacted for 2 hours. After cooling to room temperature, “JER-1001” dissolved in ethyl diglycol acetate 70% with stirring was 51.8 g in terms of solid content, 5.0 g of 1,4-butanediol, 19.9 g of ethyl diglycol acetate, A mixture of 29.0 g of “Swazole # 1000” was added, the product temperature was raised to 80 ° C., and the mixture was reacted for 90 minutes. Thereafter, 1.1 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was added, the product temperature was raised to 110 ° C., and the mixture was reacted for 90 minutes. Infrared spectroscopic analysis confirmed that the absorption based on the isocyanate group (2274 cm-1) had disappeared, and terminated the reaction to obtain a polybutadiene resin (Product 6) having an epoxy group and a urethane structure.

Properties of product 6 Solid content 54.1%
Number average molecular weight 19967
Epoxy equivalent 2369

<Production Example 7>
A 1 liter flask equipped with a stirrer, a thermometer, and a condenser was charged with 197.4 g of polybutadiene “G-3000” (Nippon Soda Co., Ltd., hydroxyl value = 30 mg KOH / g), “Swazole # 1000” 90, 6 g, nitrogen atmosphere The product temperature was raised to 60 ° C. and stirred until uniform. 19.4 g of Coronate T-100 was added thereto, and stirring was continued for about 10 minutes. Then, 2.2 g of a 1% solution of “Swazole # 1000” of Neostan U-100 (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) was added. The product temperature was raised to 75 ° C. and reacted for 2 hours. After the reaction, a suspension of 35.8 g of tetrabasic acid dianhydride BTDA (manufactured by Daicel Corporation) in 157.1 g of ethyl diglycol acetate was added at a product temperature of 75 ° C. and stirred for 10 minutes. Ethyl diglycol acetate in which 10% of triethylenediamine was dissolved was added in an amount of 0.25 g in terms of solid content, and the product temperature was raised to 140 ° C. and reacted for 180 minutes. Infrared spectroscopic analysis confirmed that absorption based on isocyanate groups (2274 cm-1) had disappeared, and a polybutadiene resin (Product 7) having an acid anhydride group and a urethane structure was obtained.

Properties of product 7 Solid content 50.8%
Number average molecular weight 10369
Acid anhydride group equivalent 1136

<Production Example 8>
Polycarbonate diol “UM-90 (1/1)” (Ube Industries hydroxyl value = 126 mg KOH / g) 132.3 g, ethyl diglycol acetate 18.9 g, “Swazole #” in a 1 l flask equipped with a stirrer, thermometer and condenser 1000 ”27.0 g was charged and stirred at room temperature under a nitrogen atmosphere. A solution prepared by mixing 51.2 g of “Coronate T-100” and 22.0 g of ethyl diglycol acetate was added thereto, and the product temperature was raised to 80 ° C. and reacted for 2 hours. After cooling to 30 ° C., a mixture of 26.5 g of 1,4-butanediol and 22.0 g of ethyl diglycol acetate was added, and the product temperature was raised to 120 ° C. and reacted for 90 minutes. Infrared spectroscopic analysis confirmed that absorption based on the isocyanate group (2274 cm-1) had disappeared, and reaction product 6 was obtained.
Subsequently, 194.2 g of the reaction product 6, 30.6 g of ethyl diglycol acetate, and 26.7 g of “Swazole # 1000” were charged into a 1 liter flask equipped with a stirrer, a thermometer, and a condenser, and stirred at room temperature in a nitrogen atmosphere. While adding 33.1 g of “Coronate T-100”, 20.4 g of ethyl diglycol acetate, and 13.4 g of “Swazole # 1000”, the product temperature was raised to 70 ° C. and reacted for 2 hours. . After cooling to 40 ° C., 75.5 g of “JER-1001” dissolved in ethyl diglycol acetate with stirring, 4.3 g of 1,4-butanediol, 40.7 g of ethyl diglycol acetate, “Swazole # 1000 13.4 g of the mixture was added, the product temperature was raised to 80 ° C., and the mixture was reacted for 1 hour. Thereafter, a mixture of 1.1 g of isobutyl alcohol and 10.2 g of ethyl diglycol acetate was added, and the mixture was further reacted at 80 ° C. for 1 hour. Lastly, 4.1 g of a 1% solution of “Swazole # 1000” of “Neostan U-810” was added, and the product temperature was reacted at 80 ° C. for 1 hour. Infrared spectroscopic analysis confirmed that the absorption (2274 cm −1) based on the isocyanate group had disappeared, and terminated the reaction to obtain a polycarbonate resin (Product 8) having an epoxy group and a urethane structure.

Property of product 8 Solid content 51.8%
Number average molecular weight 20101
Epoxy equivalent 1545

<Manufacture of thiol compounds>
As tris (3-mercaptopropyl) isocyanurate, the one synthesized by the method described in JP-A-1981-120671 was used as it was. That is, triallyl isocyanurate (manufactured by Nippon Kasei Chemical Co., Ltd.) and thiolpropionic acid (manufactured by City Chemical LLC) were reacted by irradiation with ultraviolet rays in a mixed solvent of acetone and acetic acid. After removing the solvent under reduced pressure, the residue of the reaction solution was boiled in concentrated hydrochloric acid and neutralized with anhydrous sodium carbonate. Thereafter, the solution was passed through a medium activated alumina column and the solvent was removed to obtain tris (3-mercaptopropyl) isocyanurate.

<Example 1>
44.4 parts of product 1 in terms of solid content, 2.6 parts of synthesized tris (3-mercaptopropyl) isocyanurate, hydrophobic silica “R-805” (manufactured by Nippon Aerosil Co., Ltd., average) After mixing 4.6 parts of a particle size of 0.012 μm and kneading with a three-roll mill, 2.0 parts of “Swazole # 1000” was added to adjust the viscosity to about 35 Pa · s. Finally, 2.2 parts of “Nichigoimidazole 1,2-DMI” (Nippon Gosei Kagaku Kogyo Co., Ltd.) was added as a curing catalyst and stirred with Nertaro AR-100 “Sinky Co., Ltd.” to prepare a resin varnish. did.

<Example 2>
A resin varnish was prepared in exactly the same manner as in Example 1, except that the product 1 of Example 1 was changed to the product 2.

<Example 3>
Except that the product 1 of Example 1 was changed to the product 3, the blending amount of tris (3-mercaptopropyl) isocyanurate was 3.7 parts, and the blending amount of “R-805” was 6.2 parts, A resin varnish was prepared in exactly the same manner as in Example 1.

<Example 4>
A resin varnish was prepared in exactly the same manner as in Example 1 except that the product 1 of Example 1 was changed to the product 4.

<Example 5>
Except that the product 1 of Example 1 was changed to the product 5, the blending amount of tris (3-mercaptopropyl) isocyanurate was 4.4 parts, and the blending amount of “R-805” was 7.6 parts, A resin varnish was prepared in exactly the same manner as in Example 1.

<Example 6>
The product 1 of Example 1 is the product 6, the blending amount is 49 parts, the blending amount of tris (3-mercaptopropyl) isocyanurate is 2.2 parts, and the blending amount of “R-805” is 3. A resin varnish was produced in the same manner as in Example 1 except that the content was changed to 7 parts.

<Example 7>
The amount of tris (3-mercaptopropyl) isocyanurate of Example 1 is 9.6 parts, the amount of “R-805” is 16.3 parts, and the amount of “Nitgoimidazole 1,2-DMI” A resin varnish was prepared in exactly the same manner as in Example 1 except that was changed to 3.7 parts.

<Example 8>
The amount of tris (3-mercaptopropyl) isocyanurate of Example 1 is 1.6 parts, the amount of “R-805” is 2.7 parts, and the amount of “Nitgoimidazole 1,2-DMI” is 1. A resin varnish was produced in the same manner as in Example 1 except that the content was changed to 0.56 part.

<Example 9>
A resin varnish was prepared in exactly the same manner as in Example 1, except that 2.6 g of tris (3-mercaptopropyl) isocyanurate in Example 1 was changed to 3.0 g of “TMTP” (manufactured by Sakai Chemical Co., Ltd.). did.

<Comparative Example 1>
Example 1 except that 2.6 parts of tris (3-mercaptopropyl) isocyanurate in Example 1 was changed to 2.4 parts (in terms of solid content) of “TD2090” (manufactured by DIC Corporation, MEK solution). A resin varnish was prepared in the same manner as described above.

<Comparative example 2>
44.4 g of product 7 in terms of solid content, 7.8 g of hydrophobic silica “R-805” as an inorganic filler were mixed, kneaded with a three-roll mill, and then ethyl diglycol acetate as a curing agent. Add 18.6 g of dissolved JER-1001 in terms of solid content and 2.2 g of “Nitgoimidazole 1,2-DMI” and stir with Nertaro AR-100 “Sinky Corp.” to prepare a resin varnish did.

<Comparative Example 3>
Example 1 except that product 1 of Example 1 was changed to product 8, the amount of tris (3-mercaptopropyl) isocyanurate was changed to 3.3 g, and the amount of “R-805” was changed to 5.7 g. A resin varnish was prepared in exactly the same manner as in Example 1.

Next, measurement methods and evaluation methods in physical property evaluation will be described.

<Evaluation of low temperature curability>
The resin varnishes prepared in Examples and Comparative Examples were screen printed using a 200 mesh plate on a 50 μm thick polyimide film (Upilex 50S: manufactured by Ube Industries, Ltd.) and cured at 80 ° C. for 60 minutes. Using a cotton swab soaked with acetone, the cured surface was rubbed on the fifth floor with a force indicating a weight of 10 g, and the surface of the cured surface was observed. A sample with no discoloration was evaluated as “◎”, a sample with almost no discoloration was evaluated as “◯”, a sample with clear discoloration was evaluated as “Δ”, and a cured product was melted and the film was exposed as “x”. In Comparative Example 2, the reaction proceeded at room temperature, and gelation was observed, so evaluation could not be performed. For the same reason, further evaluations could not be performed. The results are shown in Table 1.

<Evaluation of printability>
The resin varnishes prepared in Examples and Comparative Examples were combed with a L / S = 15/15 μm and a circuit thickness of 8 μm on a 50 μm thick polyimide film (Upilex 50S: manufactured by Ube Industries) using a 200 mesh plate. Screen printing was performed on the 38 μm-thick polyimide film on which the electrode pattern was formed so as to cover the entire surface of the comb-shaped electrode pattern. After standing at 20 ° C. for 10 minutes, it was cured at 80 ° C. for 60 minutes (only Comparative Example 1, 130 ° C. for 60 minutes). The thickness of the cured body was 50 μm. Immediately after printing, the surface of the printed part up to 10 minutes and the cured body surface after curing were observed with a metal microscope (MF-UD2017B, manufactured by Mitutoyo Corporation, objective lens × 5, total magnification × 150). The case where bubbles disappeared within 5 minutes immediately after printing was indicated as “◎”, the case where bubbles disappeared within 5 minutes to 10 minutes, and “X” when bubbles remained after curing. The results are shown in Table 1.

<Evaluation of flexibility>
(Elastic modulus and elongation)
The resin varnishes prepared in Examples and Comparative Examples were applied on a release PTFE film (Aflex 50N: manufactured by Asahi Glass Co., Ltd.) using a bar coater, and 80 ° C. for 60 minutes (Comparative Example 1 only, 130 ° C. 60 Cured). The thickness of the cured body was 50 μm. Thereafter, the PTFE film was peeled off. In accordance with Japanese Industrial Standard (JIS K7161), a tensile test was conducted using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) at a temperature of 25 ° C., a humidity of 40% RH, and a pulling speed of 50 mm / min. . The elastic modulus and elongation were measured by measuring the yield point of the evaluation sample. The results are shown in Table 1.
(Bendability)
The resin varnishes prepared in Examples and Comparative Examples were coated on a 50 μm thick polyimide film (Upilex 50S: Ube Industries, Ltd.) using a bar coater, and 80 ° C. for 60 minutes (Comparative Example 1 only, 130 ° C. for 60 minutes). ). The thickness of the cured body was 50 μm. The cured surface was bent outward by 180 degrees and 360 degrees in the opposite direction. The case where no whitening or cracking occurred on the hardened surface was indicated as “◯”, the case where whitening was observed on the hardened surface was indicated as “Δ”, and the case where whitening and cracking was observed on the hardened surface was indicated as “X”. The results are shown in Table 1.

<Evaluation of insulation reliability>
The resin varnishes prepared in Examples and Comparative Examples were used on a 38 μm thick polyimide film on which a comb electrode pattern with L / S = 15/15 μm and circuit thickness of 8 μm was formed using a 200 mesh plate. Screen printing was performed so as to cover the entire surface of the pattern, and curing was performed at 80 ° C. for 60 minutes (only Comparative Example 1, 130 ° C. for 60 minutes). While applying a voltage of 100 V to this, it was left for 1000 hours in an atmosphere of 85 ° C. and a relative humidity of 85%. The holding time until ion migration or a decrease in insulation resistance value (up to 10 ⁶ Ω or less) was observed was measured, and this was defined as the HHBT durability time. The HHBT endurance time of 1000 hours or more was evaluated as ◯, the 500 hours or more as Δ, and the less than 500 hours as X. The results are shown in Table 1.

  As can be seen from Table 1, the examples are resin compositions that can be cured at a low temperature of 80 ° C., and it was found that the cured film has excellent flexibility, printability, and insulation reliability. On the other hand, in Comparative Example 1, curing at low temperature was insufficient and the elongation of the cured film was inferior. Comparative Example 2 gelled immediately and could not be used in terms of pot life. The cured film of Comparative Example 3 lacked flexibility and was inferior in printability and insulation reliability.

  A resin composition having excellent low-temperature curability, flexibility, and printability can be provided. Furthermore, an overcoat agent, a flexible printed wiring board, and a semiconductor device using the same can be provided. In addition, mobile phones, digital cameras, video cameras, game machines, personal computers, printers, hard disk drives, plasma TVs, liquid crystal TVs, liquid crystal displays, car navigation systems, copiers, fax machines, AV equipment, measurement equipment Vehicles such as equipment, medical equipment, motorcycles, automobiles, trains, ships, airplanes, etc. can now be provided.

Claims (14)

(A) A resin composition containing a polybutadiene resin having an epoxy group and a urethane structure, and (B) a thiol-based curing agent, and when the total solid content of the resin composition is 100% by mass, (A) epoxy A polybutadiene resin having a group and a urethane structure is 50 to 95% by mass. (A) The polybutadiene resin which has an epoxy group and a urethane structure is number average molecular weight 500-200000, The resin composition of Claim 1 characterized by the above-mentioned. (A) Polybutadiene resin which has an epoxy group and a urethane structure is epoxy equivalent 300-10000, The resin composition of Claim 1 or 2 characterized by the above-mentioned. (A) A polybutadiene resin having an epoxy group and a urethane structure has (a) a polydiene polyol compound having two or more hydroxyl groups in the molecule, and (b) one or more hydroxyl groups and one or more epoxy groups in the molecule. The resin composition according to any one of claims 1 to 3, which is obtained by reacting an epoxy compound and (c) a polyisocyanate compound having two or more isocyanate groups in the molecule. When the whole solid content of a resin composition is 100 mass%, (B) thiol type hardening | curing agent is 0.5-15 mass%, The any one of Claims 1-4 characterized by the above-mentioned. Resin composition. Furthermore, (C) inorganic filler is contained, The resin composition of any one of Claims 1-5 characterized by the above-mentioned. The resin composition according to claim 6, wherein the inorganic filler (C) has an average particle size of 0.005 to 1 µm. Furthermore, (D) hardening accelerator is contained, The resin composition of any one of Claims 1-7 characterized by the above-mentioned. The resin composition according to claim 1, which is a resin composition for an overcoat agent or a resin composition for forming an interlayer insulating film. The resin composition according to claim 9, which is a resin composition for an overcoat agent for sealing an organic TFT element. A liquid resin composition or a film-like resin composition using the resin composition according to any one of claims 1 to 10. A cured product of the resin composition according to claim 1, wherein the cured product has an elongation of 20% or more and an elastic modulus of 1000 MPa or less. A flexible printed wiring board or an organic TFT device, wherein the cured product of the resin composition according to claim 12 is used. The electronic device which incorporates the flexible printed wiring board or organic TFT device of Claim 13.