TWI589614B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to a resin composition. More specifically, it relates to a resin composition suitable for use as a material for surface protection or insulation in devices, devices, members, and the like in various technical fields.

In recent years, thin film transistors (TFTs) using an organic semiconductor layer in the field of various display devices such as organic EL displays and electronic papers have been attracting attention, and are called organic TFTs. An organic TFT is exemplified as a device for replacing a conventional inorganic TFT using an inorganic semiconductor layer, and various electronic devices such as the aforementioned display device are listed for use. Since the inorganic TFT can form an organic semiconductor layer at a lower temperature than the vapor deposition method, it is expected that the TFT can be mounted on a substrate such as a plastic film having low heat resistance.

In particular, by mounting the organic TFT on a flexible substrate such as a plastic film, a bendable electronic device can be realized. In this case, not only the organic semiconductor layer is formed at a low temperature, but also the insulating film is formed at a low temperature, whereby the substrate or the organic TFT element can be prevented from being thermally damaged. Therefore, it has been proposed to form an organic semiconductor layer or an insulating film using a printing method or the like. For example, the country In the publication No. 2009/051209, the varnish-like resin composition (overcoating agent) is printed by a screen printing method into a desired pattern and hardened, but the properties of the resin composition (ie, There is insufficient room for improvement in low-temperature hardening property, softness of cured product, printability, and the like.

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

The inventors of the present invention have found that the above-described problems can be solved by a resin composition containing a specific polybutadiene resin and a thiol-based curing agent, and the present invention has been completed.

That is, the present invention is intended to include the following.

[1] A resin composition comprising (A) a polybutadiene resin having an epoxy group and a urethane structure, and (B) a resin composition of a thiol-based curing agent, characterized in that When the total solid content of the resin composition is 100% by mass, the content of the (A) polybutadiene resin having an epoxy group and a urethane structure is 50 to 95% by mass.

[2] The resin composition according to the above [1], wherein (A) the polybutadiene resin having an epoxy group and a urethane structure has a number average molecular weight of 500 to 200,000.

[3] The resin composition according to the above [1] or [2] wherein (A) the epoxy equivalent of the polybutadiene resin having an epoxy group and a urethane structure is from 300 to 10,000.

[4] The resin composition as described in any one of the above [1] to [3], (A) The polybutadiene resin having an epoxy group and a urethane structure is a polydiene polyol compound having (a) two or more hydroxyl groups in the molecule, and (b) one or more molecules in the molecule. The hydroxyl group is obtained by reacting an epoxy compound having one or more epoxy groups and (c) a polyisocyanate compound having two or more isocyanate groups in the molecule.

[5] The resin composition according to any one of the above [1], wherein the content of the (B) thiol-based curing agent is when the total solid content of the resin composition is 100% by mass. 0.5 to 15% by mass.

[6] The resin composition according to any one of [1] to [5] further comprising (C) an inorganic filler.

[7] The resin composition according to [6] above, wherein (C) the inorganic filler has an average particle diameter of 0.005 to 1 μm.

[8] The resin composition according to any one of [1] to [7] further comprising (D) a curing accelerator.

[9] The resin composition according to any one of the above [1] to [8], which is used for an overcoating agent or an interlayer insulating film.

[10] The resin composition according to [9] above, wherein the overcoating agent is used for encapsulating the organic TFT element with a coating agent.

[11] A liquid resin composition or a film-like resin composition, which is obtained by using the resin composition according to any one of the above [1] to [10].

[12] A hardened body of the resin composition according to any one of the above [1] to [8], which has an elongation of 20% or more and an elastic modulus of 1000 MPa or less.

[13] A flexible printed wiring board comprising the cured body according to [12] above.

[14] An organic TFT device comprising the hardened body according to [12] above.

[15] An electronic device comprising the flexible printed wiring board according to [13] or the organic TFT device according to [14] above.

According to the invention, it is possible to provide a resin composition which is excellent in low-temperature curability, flexibility, and printability.

Further, since the resin composition of the present invention is excellent in low-temperature curability, flexibility, and printability, it does not cause thermal deterioration of elements or substrates in, for example, a flexible printed wiring board or an organic TFT device, and can be easily applied. In order to achieve such surface protection or insulation, as a result, thermal degradation, flexibility, bendability, and the like of the element or substrate are not reduced, and flexible wiring for achieving desired surface protection or insulation can be provided. Board, organic TFT device, etc.

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

<(A) Polybutadiene Resin having an epoxy group and a urethane structure>

(A) a polybutadiene resin having an epoxy group and a urethane structure ( The "(A) component") is a polymer having an epoxy group, a urethane structure, and a polybutadiene skeleton, and is not particularly limited, and for example, (a) has 2 in the molecule. a polydiene polyol having a hydroxyl group or more (hereinafter also referred to as "compound (a)"), and (b) an epoxy compound having one or more hydroxyl groups and one or more epoxy groups in the molecule (hereinafter also referred to as "a compound" (b) ") and (c) a polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also referred to as "compound (c)") is obtained by a reaction.

The compound (a) is not particularly limited, and examples thereof include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like. One type or a combination of two or more types can be used. In particular, the compound (a) is preferably a hydrogenated product, that is, a hydrogenated polydiene polyol, from the viewpoints of improvement in heat resistance of the target resin composition, improvement in printability, improvement in insulation reliability, and the like. Accordingly, in the present invention, the component (A) is preferably a hydrogenated polybutadiene resin having a polybutadiene skeleton, that is, a hydrogenated polybutadiene resin having an epoxy group and a urethane structure.

The compound (a) can be synthesized by a conventional method, but a commercially available product can be used. The polybutadiene polyol is exemplified by Poly bd R-45HT, R-15HT (manufactured by Idemitsu Kosan Co., Ltd.) having a hydroxyl group-terminated liquid polybutadiene mainly having a 1,4-bond, and hydroxyl group-end polycondensation. Butadiene hydride of POLYTAIL H, POLYTAIL HA (above is Mitsubishi Chemical Co., Ltd.), G-1000, G-2000, G-3000 (mainly having hydroxyl terminated polybutadiene with 1,2-bonds) GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.), which is a hydride of a hydroxyl group-terminated polybutadiene mainly having 1,2-bonds. In addition, polyisoprene polyols are listed as hydroxyl terminal liquids. Poly ip, EPOLE of isoprene (above is produced by Idemitsu Kosan Co., Ltd.).

The compound (a) has a number average molecular weight of preferably 10,000 or less, more preferably 7,000 or less, and still more preferably 4,000 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 body of the resin composition, the number average molecular weight is preferably 300 or more, more preferably 600 or more, still more preferably 900 or more. The number average molecular weight in the present invention is a value in terms of polystyrene measured by a gel permeation chromatography (GPC). Specifically, the number average molecular weight measured by the GPC method is GPC-101 manufactured by Showa Denko Co., Ltd., and Shodex KF-800RH/LF-804 manufactured by Showa Denko Co., Ltd. is used as a column, and tetrahydrofuran is used. The mobile phase was measured at a column temperature of 40 ° C and calculated using a calibration line of standard polystyrene.

The compound (b) is not particularly limited as long as it has one or more hydroxyl groups and one or more epoxy groups in the molecule, and may be a glycidyl ether skeleton, a glycidyl ester skeleton, a glycidylamine skeleton, or an alicyclic group. Either of an epoxy skeleton or an epoxy compound of an oxirane ring. The compound (b) can be used alone or in combination of two or more. The compound (b) can be synthesized by a conventional method, but a commercially available product can also be used. The epoxy compound having a glycidyl ether skeleton is exemplified by JER-1001, JER-1002, JRR-1003, JER-1004 (manufactured by Mitsubishi Chemical Corporation), and the epoxy compound having ethylene oxide is exemplified as a hydroxyl terminal ring. Oxidized polybutadiene PB-3600 (Daicel Chemical Industry Co., Ltd.).

The compound (b) can be obtained by (b) an epoxy compound having two or more epoxy groups in the molecule (hereinafter referred to as "compound (d)") and (e) It is obtained by reacting a compound having one or more active hydrogen groups reactive with an epoxy group (hereinafter referred to as "compound (e)").

The compound (d) is exemplified by a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, and a phenol. Novolak type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phenol Epoxide, triglycidyl isocyanurate, alicyclic epoxy resin, glycidylamine resin, glycidyl ester resin, aromatic two with a condensate of an aromatic aldehyde having a phenolic hydroxyl group An epoxy resin such as an diglycidyl ether of an alcohol or a diglycidyl ether of an alicyclic glycol ester. These may be used alone or in combination of two or more.

The compound (e) is exemplified by a compound having one or more phenolic hydroxyl groups, a compound having one or more carboxyl groups, and the like. The number of active hydrogen groups is preferably one or two active hydrogens in order to reduce the possibility of gelation in the reaction with the compound (d). The compound having one active hydrogen group is exemplified by a phenol compound, a thiophenol compound, a carboxylic acid compound, and the like. The compound having two active hydrogen groups is exemplified by bisphenol A, bisphenol F, bisphenol S, biphenol, hydroquinone, adipic acid, sebacic acid, dodecanedioic acid, 8, 12- 20 carbon two. Aenedioic acid, eicosadioic acid, and the like. The compound (e) can be used alone or in combination of two or more.

The compound (d) and the compound (e) can be reacted at a reaction temperature of from 80 ° C to 180 ° C for a period of from 1 hour to 8 hours. The reaction may also be carried out by adding an organic solvent as needed, and may also be carried out by adding a catalyst as needed. The catalyst is listed as nitrogen A compound, a phosphorus compound, or the like.

The compound (c) is not particularly limited and is exemplified by 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and bicyclo ring. Hexyl methane diisocyanate, naphthalene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, tetramethylene xylene diisocyanate, trimethyl hexamethylene diisocyanate, norbornene diisocyanate, and the like. These may be used alone or in combination of two or more.

The reaction conditions of the compound (a), the compound (b) and the compound (c) can be, for example, a reaction in an organic solvent at a reaction temperature of from 15 ° C to 120 ° C and a reaction time of from 1 to 8 hours. In addition, it is also possible to add a catalyst to react as needed.

The reaction ratio of the compound (a), the compound (b) and the compound (c) is such that the number of hydroxyl groups of the compound (a) is Xa, the number of hydroxyl groups of the compound (b) is Xb, and the isocyanate of the compound (c) When the base is set to Y, the value of (Xa+Xb)/Y is preferably in the range of 1 to 3, more preferably in the range of 1.01 to 2. By setting the ratio to 1 or more, the amount of the isocyanate group is prevented from being excessive, and the molecular weight is easily controlled. Further, the molecular weight is easily increased by 3 or less.

Further, the compound (a) and the compound (b) are preferably used in the range of the compound (a): compound (b) = 90:10 to 10:90 by mass ratio, more preferably 80:20 to 30:70. The scope is used. When the mass ratio exceeds 90:10 and the ratio of the compound (a) is large, the heat resistance of the cured body tends to decrease, and when the mass ratio exceeds 10:90 and the ratio of the compound (b) is large, there is a hardened body. The tendency for the softness to become insufficient.

The organic solvent used in the reaction may, for example, be N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethyl a solvent containing a nitrogen-containing compound such as acetamide, N-methyl-2-pyrrolidone or tetramethylurea, a solvent such as a sulfur-containing compound such as dimethyl hydrazine or diethyl hydrazine, or a ring such as γ-butyrolactone. Ester compound solvent, ketone solvent such as cyclopentanone or cyclohexanone, ether solvent such as diglyme or triglyme, carbitol acetate, propylene glycol monomethyl ether acetate A polar solvent such as an ester solvent such as propylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more. Further, a non-polar solvent such as an aromatic hydrocarbon may be appropriately mixed as needed.

The reaction may be carried out by adding a catalyst as needed, and the catalyst may be exemplified by tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N,N-dimethylpiperidine, α- a tertiary amine such as methylbenzyldimethylamine, N-methylmorpholine or tri-ethylenediamine, or dibutyltin laurate, dibutyltin dichloride, cobalt naphthenate, zinc naphthenate, etc. Organometallic catalysts, etc.

The number average molecular weight of the component (A) in the present invention is preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less, from the viewpoint of preventing the viscosity of the resin composition from increasing and the workability from decreasing. It is preferably 80,000 or less, and more preferably 60,000 or less, and preferably 40,000 or less. On the other hand, from the viewpoint of improving the flexibility of the cured body of the resin composition, it is preferably 500 or more, more preferably 4,000 or more, still more preferably 8,000 or more, still more preferably 12,000 or more, and further preferably More than 16,000, preferably more than 20,000. The number average molecular weight can be measured in the same manner as the above method.

The epoxy equivalent of the component (A) in the present invention is preferably 10,000 or less, more preferably 7,000 or less, still more preferably 4,000 or less from the viewpoint of improving solvent resistance. On the other hand, from the viewpoint of preventing the crosslinkability (crosslinking density) of the cured resin composition from being too high and reducing the flexibility, it is preferably 300 or more, more preferably 500 or more, and more preferably 1000 or more. In addition, the epoxy equivalent (g/eq) is a molecular weight of the component (A) (polybutadiene resin having an epoxy group and a urethane structure) per one epoxy group, and is based on JIS K7236. Determination.

In the resin composition of the present invention, the amount of the component (A) is preferably 50% by mass of the entire solid content of the resin composition, from the viewpoint of improving the flexibility of the cured resin composition. More than %, more preferably 55% by mass or more, still more preferably 60% by mass or more, and even more preferably 65% by mass or more. On the other hand, when the total solid content of the resin composition is 100% by mass, the content of the resin composition is preferably 95% by mass or less, more preferably 93% by mass or less. Further, it is preferably 91% by mass or less, and more preferably 89% by mass or less.

<(B) mercaptan-based hardener>

In the present invention, by using the (B) thiol-based curing agent (hereinafter referred to as "component (B)"), the low-temperature curability can be improved. The component (B) is not particularly limited as long as it is a compound which can crosslink or polymerize an epoxy group, and is exemplified by, for example, trimethylolpropane ginseng (3-mercaptopropionate) or pentaerythritol ruthenium (3-mercaptopropionate). , dipentaerythritol tert-(3-mercaptopropionate), gins-[(3-mercaptopropoxy)-ethyl]- Isocyanurate, ginseng (3-mercaptopropyl) isocyanurate, and the like. Commercially available products are OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP, TEMP, PEMP, TEMPIC, DPMP, and Showa Denko Co., Ltd., manufactured by Dian Chemical Co., Ltd. PE-1, BD-1, NR-1, TPMB, TEMB, and the like.

In the case where the resin composition is effectively cured at a low temperature, the amount of the component (B) in the present invention is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the resin composition. It is 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more. On the other hand, when the solid content of the resin composition is 100% by mass, the solid content of the resin composition is preferably 15% by mass or less, more preferably 13% by mass or less, and more preferably It is preferably 10% by mass or less, more preferably 7% by mass or less, and most preferably 5% by mass or less.

<(C) Inorganic filler>

The resin composition of the present invention further contains (C) an inorganic filler as needed, and the viscosity of the resin composition can be adjusted to improve workability. The inorganic filler is not particularly limited, and is exemplified by cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate. , barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, etc., among these, preferably cerium oxide, preferably fuming Yttrium oxide. Moreover, the fumed cerium oxide may be hydrophobic or hydrophilic, but hydrophobic. Sexual fuming cerium oxide is better. For the inorganic filler, a commercially available product can be used, and for example, "200", "200CF", "300", "300CF", "380", etc., manufactured by Japan AEROSIL Co., Ltd., which are hydrophilic fuming cerium oxide, are used. "R-805", "R-812", "RY-200", "RY-300", "RX-200", "RX-300", etc., manufactured by Japan AEROSIL Co., Ltd. "SOC2" and "SOC1" manufactured by Adematech Co., Ltd. of cerium oxide.

The average particle diameter 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 easily improving the insulation reliability and adjusting the viscosity of the resin composition. It is 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.1 μm or less. On the other hand, from the viewpoint of preventing aggregation of the inorganic filler, it is preferably 0.005 μm or more. (C) The average particle size of the inorganic filler can be based on the Mie scattering theory, by laser diffraction. Determined by scattering method. Specifically, the laser diffraction type particle size distribution measuring apparatus can be used to determine the particle size distribution of the inorganic filler on a volume basis, and the median diameter is used as the average particle diameter. It is preferable to use a sample in which the inorganic filler is dispersed in water by ultrasonic waves. As for the laser diffraction scattering type particle size distribution measuring apparatus, the LA-500 manufactured by Seisakusho Co., Ltd., etc. can be used. Further, in order to improve moisture resistance and dispersibility, the inorganic filler is preferably a decane coupling agent (epoxy decane coupling agent, an amine decane coupling agent, a mercapto decane coupling agent, or the like) or a titanate coupling. A surface treatment agent such as a mixture or a guanidinium compound is surface-treated.

The epoxy decane coupling agent is exemplified by glycidoxypropyl trimethoxy decane, glycidoxypropyl triethoxy decane, and glycidol. Oloxypropylmethyldiethoxydecane, glycidylbutyltrimethoxydecane, (3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., and an amine-based decane coupling agent is exemplified as Aminopropyl methoxy decane, aminopropyl triethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-2 (aminoethyl) aminopropyl trimethoxy The decyl decane coupling agent is decyl propyl trimethoxy decane, decyl propyl triethoxy decane, and the like. These may be used alone or in combination of two or more.

Titanium coupling agents are exemplified by butyl titanate dimer, octanediol titanium, diisopropoxy titanium bis(triethanolamine), dihydroxy titanium dilactate, dihydroxy bis(ammonium lactate) titanium, bis ( Dioctyl pyrophosphate) ethyl titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanium Acid ester, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(di-tridecylphosphite) titanate , tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, isopropyl trioctadecyl titanate, isopropyl triiso Propyl phenyl titanate, isopropyl triisostearyl decyl titanate, isopropyl isostearyl decyl bis decyl decyl titanate, isopropyl dimethyl propylene decyl isostearyl Mercapto titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl tri-dodecylbenzenesulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) Titanate, isopropyl tris(N-nonylamine ethyl.aminoethyl) titanate, and the like. These may be used alone or in combination of two or more.

The indane alkane compounds are exemplified by hexamethyldiazepine, 1,3-divinyl-1,1,3,3-tetramethyldiazepine, octamethyltriazane, and six (third Butyl)dioxane, hexabutyldioxane, hexaoctyldioxane, 1,3-Diethyltetramethyldiazepine, 1,3-di-n-octyltetramethyldiazide, 1,3-diphenyltetramethyldiazide, 1,3- Dimethyltetraphenyldiazepine, 1,3-diethyltetramethyldiazepine, 1,1,3,3-tetraphenyl-1,3-dimethyldiazepine, 1,3-Dipropyltetramethyldiazepine, hexamethylcyclotriazane, hexaphenyldioxane, dimethylaminotrimethylguanidine, triazane, ring three A decazane, 1,1,3,3,5,5-hexamethylcyclotriazane or the like is preferably hexamethyldioxane. These may be used alone or in combination of two or more.

When the amount of the surface treatment agent to be treated is 100% by mass based on the inorganic filler, it is preferably from 0.1 to 6% by mass, more preferably from 0.3 to 4% by mass.

In the present invention, the inorganic filler (C) may be used alone or in combination of two or more. In addition, when the content of the (C) inorganic filler is adjusted, the viscosity of the resin composition is easily adjusted. When the total solid content of the resin composition is 100% by mass, it is preferably 1% by mass or more. It is 3% by mass or more, and more preferably 5% by mass or more. On the other hand, when the total modulus of the solid content of the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25, from the viewpoint of the reduction of the modulus of elasticity or the elongation of the cured resin composition. The mass% or less is more preferably 20% by mass or less.

<(D) hardening accelerator>

The resin composition of the present invention can further improve the heat resistance, adhesion, chemical resistance, and the like of the cured body by further containing (D) a curing accelerator as needed. The curing accelerator is not particularly limited, and examples thereof include an amine-based curing accelerator, an lanthanum-based curing accelerator, an imidazole-based curing accelerator, and an lanthanum-based curing accelerator. These may be used alone or in combination of two or more.

The amine-based hardening accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-gin ( An amine compound such as dimethylaminomethyl)phenol or 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

The lanthanide hardening accelerator is not particularly limited and is exemplified by dicyanamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-tolyl).胍, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] fluorene-5-ene, 7- Methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecyl Biguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole-based hardening accelerator is not particularly limited and is exemplified by 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 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-phenyl Imidazole, 1-cyanoethyl-2-undecyl imidazolium phthalate, 1-cyanoethyl-2-benzene Imidazolium pyromellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanide Uric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 ,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2 An imidazole compound such as phenylimidazoline or 1-(2-hydroxy)-3-phenoxypropyl-2-methylimidazole; and an adduct of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

The lanthanum hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, lanthanum borate, tetraphenylphosphonium tetraphenylborate, n-butyl fluorene tetraphenylborate, tetrabutyl citrate, 4-methylphenyl)triphenylsulfonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, when the content of the hardening accelerator (D) is 100% by mass based on the total solid content of the resin composition, it is preferably 7 mass% from the viewpoint of improving the storage stability of the resin composition. Hereinafter, it is more preferably 6% by mass or less, and still more preferably 5% by mass or less. On the other hand, when the resin composition is effectively cured and the low-temperature curability is improved, the total solid content of the resin composition is preferably 100% by mass or more, more preferably 0.01% by mass, based on 100% by mass of the total solid content of the resin composition. The above is more preferably 0.1% by mass or more.

<Other ingredients>

The resin composition of the present invention is exemplified by a polyfluorene-based defoaming agent, a fluororesin-based antifoaming agent, an antifoaming agent such as an acrylic polymer defoaming agent, an inorganic pigment such as titanium oxide or zinc oxide, phthalocyanine blue, and phthalocyanine. Organic pigments such as green, iodine green, disazo yellow, carbon black, colorants such as organic dyes, hindered phenol compounds, phosphorus compounds, sulfur compounds, uramine compounds, etc., benzotriazole A UV absorber such as a compound or a hindered amine compound, a flame retardant such as a phosphorus compound, aluminum hydroxide or magnesium hydroxide, a flow agent, a thixotropic agent, and 2,4,6-tridecyl-s-triazole. A adhesion promoter such as 2,5-dimercapto-1,3,4-thiadiazole or the like.

The elastic modulus of the cured body of the resin composition of the present invention can be measured by <Evaluation of Softness> which will be described later. The elastic modulus of the hardened body is preferably 5 MPa or more, more preferably 10 MPa or more, and more preferably 15 MPa from the viewpoint of improving the mechanical strength of the hardened body and prolonging the use time of the device, device, member, and the like to which the hardened body is applied. the above. Further, from the viewpoint of improving the flexibility of the device, the device, the member, and the like to which the hardened body is applied and improving the bending resistance, it is preferably 1000 MPa or less, more preferably 600 MPa or less, and still more preferably 400 MPa or less.

The elongation of the cured body of the resin composition of the present invention can be measured by the <softness evaluation> described later. The elongation of the hardened body is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 60% or more, and most preferably 80, from the viewpoint of preventing cracking of the hardened body. %the above. Moreover, the upper limit of the elongation of the hardened body is not particularly limited, and the operability is From the viewpoint of the above, it is preferably 500% or less, more preferably 400% or less, and still more preferably 300% or less.

The resin composition of the present invention can be prepared by mixing a component containing the components (A) and (B) (including components other than the components (A) and (B) as necessary), and using a triaxial roll, a ball mill, and a bead. A mixing mechanism such as a grain grinder or a sand mill, or a stirring mechanism such as an ultra-grinding machine or a planetary kneading machine dissolves or disperses to prepare a resin paint. In the preparation, an organic solvent for adjusting the viscosity may also be used as needed. The organic solvent is exemplified by ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, and butyl. Glycol ethers such as carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve Esters such as acetate and carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. These may be used alone or in combination of two or more.

The form of the resin composition of the present invention is not particularly limited, and it is preferably used as a liquid resin composition or a film-like resin composition. Moreover, "liquid" means a liquid at room temperature.

<Liquid resin composition>

The resin composition of the present invention can be produced into a liquid resin by dissolving or dispersing it in various organic solvents as described above. The organic solvent to be used herein is not particularly limited, but from the viewpoint of suppressing volatilization of the solvent and improving printability, a solvent having a boiling point of 100 ° C or higher is preferably used. Further, a solvent having a boiling point of 120 ° C or higher is more preferably used. When the resin composition is used as an overcoating agent (coating agent for a flexible printed wiring board, a coating agent for encapsulating an organic TFT element, etc.) or an insulating protective film for a printed wiring board, It is prepared into a liquid resin composition.

<film-like resin composition>

The resin composition of the present invention can be produced into a film-like resin composition according to a method known to those skilled in the art. For example, the resin paint adjusted as described above is applied onto a support, and the organic solvent is dried by heating or blowing hot air to form a film, thereby obtaining a film-like resin composition, and producing a film-like resin composition as a support. Things. The support is a support when the film-form resin composition is produced, and is used when the resin composition of the present invention is applied to a desired portion of a device, a device, a member, or the like, and is peeled off or removed. Examples of the support include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester such as polyethylene naphthalate, and polyimine. A film, a metal foil such as a release paper or a copper foil, or the like.

The drying conditions of the resin paint are not particularly limited, but in order to maintain the adhesive ability of the resin composition, it is important that the resin composition is hardened as much as possible during drying. In addition, when a large amount of the organic solvent remains in the film-form resin composition, the amount of the organic solvent to be dried in the film-like resin composition is 5 mass% or less, preferably 3 Below mass%. The specific drying conditions are preferably, for example, drying at 50 to 120 ° C for 3 to 15 minutes.

In addition, the thickness of the film-like resin composition is not particularly limited. In view of improving the bending resistance of the hardened body, it is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. Moreover, from the viewpoint of improving workability, it is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more.

The use of the resin composition of the present invention can be used for an overcoating agent, an interlayer insulating film, a prepreg, a solder resist, an underfill, a solid crystal, a semiconductor package, a buried resin, a part embedding resin, TAB Various parts of equipment, devices, components, and the like that require insulation or protection in various fields such as applications and COF applications. Among them, it is preferably applied to an overcoating agent (especially a coating agent on a flexible printed wiring board, a coating agent for encapsulating an organic TFT element), an interlayer insulating film (especially an organic EL display) , interlayer insulating film of various display devices such as electronic paper and touch panel). In other words, the resin composition of the present invention is excellent in low-temperature curability and printability, and the cured body has excellent flexibility. Therefore, the resin composition of the present invention is coated on the flexible printed wiring board by using the resin composition of the present invention. An interlayer insulating film for a display device such as an overlying coating agent for an organic TFT element or an organic EL display, which does not cause thermal deterioration of an organic TFT element, or a component or substrate in a flexible printed wiring board or a display device. The heat is deteriorated, and the flexibility or bending property of the flexible printed wiring board or the display device is not impaired, and a desired protective structure, insulating structure, and package structure can be easily formed. According to this, the flexible printed wiring board, the organic TFT device, and the like thus obtained have excellent performance, and it is also expected to improve electronic equipment or performance such as a built-in flexible printed wiring board or an organic TFT device. As for electronic devices, such as mobile phones, digital cameras, and video recordings Cameras, game consoles, personal computers, printers, hard disk drives, plasma TVs, LCD TVs, LCD monitors, car navigation systems, photocopiers, fax machines, AV equipment, measuring equipment, medical equipment, organic EL displays , electronic paper, etc.

<Flexible printed wiring board or organic TFT device>

The liquid resin composition of the present invention is applied onto a specific portion of a flexible printed wiring board or an organic TFT device to harden the coated surface, and the entire surface or a part of the surface can be obtained to be protected by the resin composition of the present invention. Printed wiring board or organic TFT device. The curing conditions are preferably at least 80 to 200 ° C for 1 to 120 minutes because at least the solvent constituting the liquid resin composition is sufficiently dried and the resin composition is sufficiently thermally cured. The thickness of the surface protective film to be formed is not particularly limited, but is preferably from 1 to 100 μm.

Further, the film-like resin composition is laminated on a flexible printed wiring board or a specific portion of the organic TFT device by a vacuum laminator to cure the resin composition, and the entire surface or a part of the surface can be obtained as the resin of the present invention. A flexible printed wiring board or an organic TFT device protected by a composition. At this time, it is completed by using a film-like resin composition with a support without contaminating the vacuum laminator. The lamination conditions at this time may be appropriately set depending on the type of the film-form resin composition to be used, but the temperature is preferably 80 to 200 ° C, the pressure is 1 to 40 kgf/cm ² , the time is 5 to 180 seconds, and the air pressure is 20 mmHg or less. Laminating under reduced pressure. Moreover, the lamination method may be a batch type or a continuous type using a roll. Further, the curing conditions may be appropriately set by those skilled in the art depending on the kind of the film-form resin composition to be used, but at least the conditions for sufficiently curing the resin composition. In particular, when the device is placed, it is preferably 150 ° C or less, more preferably 130 ° C or less, and still more preferably 110 ° C or less in order not to deteriorate the element disposed on the substrate. On the other hand, from the viewpoint of improving the chemical resistance of the cured body, it is preferably 40 ° C or higher, more preferably 45 ° C or higher, and still more preferably 50 ° C or higher.

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, the "parts" in the following description means "parts by mass".

<Manufacturing Example 1>

In a 500 ml flask equipped with a stirring device, a thermometer, and a condenser, a polydiene polyol "GI-1000" (manufactured by Nippon Soda Co., Ltd., hydroxyl group 70 mgKOH/g), 157.8 g, "SWASOLVE #1000" (organic solvent) was fed. , Daicel Chemical Industry Co., Ltd.) 26.2g, diethylene glycol diethyl ether acetate 17.1g, and added under a nitrogen atmosphere at room temperature with stirring to make "CORONATE T-100" (2,4-toluene) The isocyanate, which was prepared by mixing 34.4 g of Japan Polyurethane Co., Ltd. and 23.0 g of diethylene glycol diethyl ether acetate, was reacted at room temperature for 45 minutes. Next, 2.74 g of "NEOSTANN U-810" (dioctyltin dilaurate, 1% solution of SWASOLVE #1000 manufactured by Nitto Kasei Co., Ltd.) was added, and the temperature of the article was set to 45 ° C for 1 hour. After cooling to room temperature, 17.8 g of 1,4-butanediol and 21 g of diethylene glycol diethyl ether acetate were added while stirring, and the temperature of the article was raised to 80 ° C for 90 minutes. Spectroscopic analysis confirmed that the isocyanate group-based absorption (2274 cm ^-1 ) disappeared, and the reactant 1 was obtained. Next, 229.5 g of the reactant 1, diethylene glycol diethyl ether was fed into a 1-liter flask equipped with a stirring device, a thermometer, and a condenser. 28.5 g of acetate and 23.4 g of "SWASOLVE #1000", and added 26.3 g of "CORONATE T-100" and 20.1 g of diethylene glycol diethyl ether acetate under stirring in a nitrogen atmosphere at room temperature, "SWASOLVE"#1000"11.7g was mixed, and the temperature of the article was raised to 45 ° C, and the reaction was carried out for 1 hour. After cooling to room temperature, 70% of the solid content conversion of 59.8 g was dissolved in diethylene glycol diethyl ether. "JER-1001" (Mitsubishi Chemical Co., Ltd.), 1,4-butanediol 3.4g, diethylene glycol B in the acid ester 44.4 g of acetate and 10.9 g of "SWASOLVE #1000" were mixed, and the temperature of the article was raised to 45 ° C for 45 minutes. Then, 0.84 g of isobutanol and 13.4 g of diethylene glycol diethyl ether acetate were added. The product was reacted for an additional hour at an article temperature of 45 ° C. Finally, 1.3 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added, and the temperature of the article was raised to 110 ° C. The absorption of the isocyanate group disappears and the reaction is terminated, and a polybutadiene resin having an epoxy group and a urethane structure (Product 1) is obtained.

Manufacture 1 trait

<Manufacturing Example 2>

In a 500 ml flask equipped with a stirring device, a thermometer, and a condenser, a hydrogenated polydiene polyol "G-1000" (manufactured by Nippon Soda Co., Ltd., hydroxyl group: 73 mgKOH/g), 157.8 g, "SWASOLVE #1000" (Daicel) was fed. Chemical Industry Co., Ltd., 26.2 g, 17.1 g of diethylene glycol ethyl ether acetate, and added under a nitrogen atmosphere at room temperature with stirring to make "CORONATE T-100" (made by Japan Polyurethane Industrial Co., Ltd.) 34.4 G and 2,300 g of diethylene glycol diethyl ether acetate were mixed and reacted at room temperature for 45 minutes. Next, 2.74 g of a 1% solution of "WAOSTANN U-810" of SWASOLVE #1000 was added, and the temperature of the article was changed to 45 ° C for 1 hour. Subsequently, after cooling to room temperature, 17.8 g of "GI-1000" and 21 g of diethylene glycol diethyl ether acetate were mixed with stirring, and the temperature of the article was raised to 80 ° C for 90 minutes. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared, and the reactant 2 was obtained. Next, 229.5 g of the reactant 1, 28.5 g of diethylene glycol diethyl ether acetate, and 23.4 g of "SWASOLVE #1000" were fed into a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, and the mixture was placed under a nitrogen atmosphere. To the mixture, 26.3 g of "CORONATE T-100", 20.1 g of diethylene glycol diethyl ether acetate, and 11.7 g of "SWASOLVE #1000" were mixed at room temperature, and the temperature of the article was raised to 45 ° C for 1 hour. After cooling to room temperature, "JER-1001", 1,4-butanediol 3.4 g, and diethyl ether, which were dissolved in diethylene glycol diethyl ether acetate in an amount of 70.8% by weight of 59.8 g in terms of solid content, were added thereto while stirring. 44.4 g of diol ether acetate and 10.9 g of "SWASOLVE #1000" were mixed, and the temperature of the article was raised to 45 ° C for 45 minutes. Subsequently, 0.84 g of isobutanol and 13.4 g of diethylene glycol diethyl ether acetate were added, and the mixture was further reacted at an article temperature of 45 ° C for 1 hour. Finally, 1.3 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added, and the temperature of the article was raised to 110 ° C. The infrared spectroscopy analysis confirmed that the absorption based on the isocyanate group disappeared and the reaction was terminated to obtain an epoxy group. A polybutadiene resin of the urethane structure (manufacture 2).

Manufacture 2 properties

<Manufacturing Example 3>

In a 500 ml flask equipped with a stirring device, a thermometer, and a condenser, 36.8 g of "CORONATE T-100", 15.0 g of diethylene glycol diethyl ether acetate, and 28.8 g of "SWASOLVE #1000" were fed, and under a nitrogen atmosphere, Stir at room temperature. Next, a mixture of 9.5 g of 1,4-butanediol and 15.0 g of diethylene glycol diethyl ether acetate was added, and 0.78 g of a 1% solution of "SWASOLVE #1000" of "NEOSTANN U-810" was added. The temperature of the article was raised to 80 ° C for 90 minutes. After cooling to 60 ° C or lower, hydrogenated polybutadiene "GI-2000" (manufactured by Nippon Soda Co., Ltd., hydroxyl value = 47 mgKOH/g) 124.1 g, diethylene glycol diethyl ether acetate 15.0 g, "SWASOLVE" was added. #1000" 28.8g of the mixture was added, and 1.56g of "NEOSTANN U-810" 1% solution of "SWASOLVE #1000" was added, and the temperature of the article was raised to 45 ° C for 90 minutes. 9.5 g of 1,4-butanediol and 15.0 g of diethylene glycol diethyl ether acetate were added thereto, and the temperature of the article was raised to 80 ° C, and the reaction was further carried out for 90 minutes. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared, and the reactant 3 was obtained.

Next, 265.5 g of the synthesized reactant 3, diethylene glycol diethyl ether acetate 8.1 g, and "SWASOLVE #1000" 69.2 g were fed into a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, in a nitrogen atmosphere. Next, a mixture of 16.3 g of "CORONATE T-100", 6.1 g of diethylene glycol diethyl ether acetate, and 4.1 g of "SWASOLVE #1000" was added while stirring at room temperature, and the temperature of the article was raised to 80 ° C. 90 minutes. After cooling to room temperature, "JER-1001" and 19.0 g of diethylene glycol diethyl ether acetate dissolved in diethylene glycol ethyl ether acetate in a solid content of 74.0 g of 70% were added thereto while stirring. In the case of the article, the temperature of the article was raised to 45 ° C for 60 minutes. Then, 1.0 g of isobutanol and 3.2 g of diethylene glycol diethyl ether acetate were added, and the reaction was carried out at an article temperature of 45 ° C for 20 minutes, and then "SWASOLVE #1000" of "NEOSTANN U-810" was added. 1.2 g of the solution was allowed to warm the article to 110 ° C for 90 minutes.

The infrared spectroscopy analysis confirmed that the isocyanate group-based absorption (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a polybutadiene resin having an epoxy group and a urethane structure (Product 3).

Manufacture 3 properties

<Manufacturing Example 4>

In a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, 23.6 g of "CORONATE T-100", 13.3 g of diethylene glycol diethyl ether acetate, and 31.9 g of "SWASOLVE #1000" were fed under a nitrogen atmosphere. Stir at room temperature. A 1% solution of "SWASOLVE #1000" of "NEOSTANN U-810" of 0.7 g of 1,4-butanediol and 13.3 g of diethylene glycol diethyl ether acetate was added thereto. The temperature of the article was raised to 80 ° C for 90 minutes. After cooling to 60 ° C or lower, hydrogenated polybutadiene "GI-3000" (manufactured by Nippon Soda Co., Ltd., hydroxyl value = 30 mgKOH/g) 129.1 g, diethylene glycol diethyl ether acetate 13.3 g, "SWASOLVE" was added. #1000" 47.8g of a mixture was added, and a 1% solution of "SWASOLVE #1000" of "NEOSTANN U-810" of 1.4 g was added, and the temperature of the article was raised to 80 ° C for 80 minutes. After cooling to 40 ° C, 6.1 g of 1,4-butanediol and 13.3 g of diethylene glycol diethyl ether acetate were added, and the temperature of the article was raised to 80 ° C, and the reaction was further carried out for 90 minutes. It was confirmed by infrared spectroscopy that the isocyanate group-based absorption (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a reactant 4. Next, 311.1 g of the reactant 4, 7.4 g of diethylene glycol diethyl ether acetate, and 55.8 g of "SWASOLVE #1000" were fed into a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, and the mixture was placed under a nitrogen atmosphere. To the mixture, 12.3 g of "CORONATE T-100" and 9.3 g of diethylene glycol diethyl ether acetate were added while stirring at room temperature, and the temperature of the article was raised to 80 ° C for 90 minutes. After cooling to room temperature, a mixture of "JER-1001" and 17.5 g of diethylene glycol diethyl ether acetate dissolved in diethylene glycol ethyl ether acetate in an amount of 55.9 g of solid content was added thereto while stirring. The temperature of the article was raised to 45 ° C for 1 hour. Then, 0.78 g of isobutanol and 3.0 g of diethylene glycol diethyl ether acetate were added, and after reacting for 30 minutes, 3.1 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added to raise the temperature of the article to 110 ° C. Reaction for 2 hours. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a polybutadiene resin having an epoxy group and a urethane structure (Production 4).

Manufacture 4 properties

<Manufacturing Example 5>

Into a 1 liter flask equipped with a stirring device, a thermometer, and a condenser, 205.1 g of the reactant 1, diethylene glycol diethyl ether acetate (16.9 g, and "SWASOLVE #1000" 45.9 g were fed in a nitrogen atmosphere at room temperature. To the mixture, 23.5 g of "CORONATE T-100" and 10.1 g of diethylene glycol diethyl ether acetate were added while stirring, and the temperature of the article was raised to 80 ° C for 90 minutes. After cooling to room temperature, "JER-1001" and 29.0 g of diethylene glycol diethyl ether acetate dissolved in diethylene glycol diethyl ether acetate in an amount of 707.1% in terms of solid content were added thereto while stirring. The temperature of the article was raised to 45 ° C for 1 hour. Subsequently, 1.5 g of isobutanol and 4.7 g of diethylene glycol diethyl ether acetate were added, and the mixture was further reacted at an article temperature of 45 ° C for 30 minutes. Finally, 1.3 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added, and the temperature of the article was raised to 110 ° C for 90 minutes. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a polybutadiene resin having an epoxy group and a urethane structure (Product 5).

Manufacture 5 properties

<Manufacturing Example 6>

Into a 1 liter flask equipped with a stirring device, a thermometer, and a condenser, 253.2 g of the reactant 1, 31.8 g of diethylene glycol diethyl ether acetate, and 29.0 g of "SWASOLVE #1000" were fed in a nitrogen atmosphere at room temperature. To the mixture, 29.0 g of "CORONATE T-100" and 27.9 g of diethylene glycol diethyl ether acetate were added while stirring, and the temperature of the article was raised to 40 ° C for 2 hours. After cooling to room temperature, "JER-1001", 1,4-butanediol 5.0 g, and 2, which are dissolved in diethylene glycol diethyl ether acetate in an amount of 71.8 g of solid content, are added thereto while stirring. 19.9 g of diol ether acetate and 29.0 g of "SWASOLVE #1000" were mixed, and the temperature of the article was raised to 80 ° C for 90 minutes. Subsequently, 1.1 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added, and the temperature of the article was raised to 110 ° C for 90 minutes. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a polybutadiene resin having an epoxy group and a urethane structure (Production 6).

Manufacture 6 properties

<Manufacturing Example 7>

In a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, polybutadiene "G-3000" (manufactured by Nippon Soda Co., Ltd., hydroxyl value = 30 mgKOH/g), 197.4 g, "SWASOLVE #1000", 90.6 g, was fed. The temperature was raised to a temperature of the article = 60 ° C under a nitrogen atmosphere, and stirred until uniform. After adding 19.4 g of CORONATE T-100 and stirring for 10 minutes, a 1% solution of "SWASOLVE #1000" of NEOSTANN U-100" (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) was added. The temperature of the article was raised to 75 ° C for 2 hours. After the reaction, 35.8 g of tetrabasic acid dianhydride BTDA (manufactured by Daicel Co., Ltd.) was suspended in 157.1 g of diethylene glycol diethyl ether acetate at a temperature of 75 ° C, and stirred for 10 minutes. Thereafter, diethylene glycol diethyl ether acetate in which 10% of triethylethylene diamine was dissolved in a solid content of 0.25 g was added, and the temperature of the article was raised to 140 ° C for 180 minutes. In the infrared spectroscopy analysis, it was confirmed that the isocyanate group-based absorption (2274 cm ^-1 ) disappeared, and a polybutadiene resin having an acid anhydride group and a urethane structure (Product 7) was obtained.

Manufacture 7 properties

<Manufacturing Example 8>

Into a 1 liter flask equipped with a stirring device, a thermometer, and a condenser, a polycarbonate diol "UM-90 (1/1)" (Ube Industries, hydroxyvalence = 126 mg KOH/g) 132.3 g, diethylene glycol was fed. 18.9 g of diethyl ether acetate and 27.0 g of "SWASOLVE #1000" were stirred at room temperature under a nitrogen atmosphere. A mixture of 51.2 g of "CORONATE T-100" and 22.0 g of diethylene glycol diethyl ether acetate was added thereto. The temperature of the article was raised to 80 ° C for 2 hours. After cooling to 30 ° C, 26.5 g of 1,4-butanediol and 22.0 g of diethylene glycol diethyl ether acetate were added, and the temperature of the article was raised to 120 ° C for 90 minutes. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared, and the reactant 6 was obtained. Next, 194.2 g of the reactant 6, 30.6 g of diethylene glycol diethyl ether acetate, and 26.7 g of "SWASOLVE #1000" were fed into a 1-liter flask equipped with a stirring device, a thermometer, and a condenser, and the mixture was placed under a nitrogen atmosphere. To the mixture, 33.1 g of "CORONATE T-100", 20.4 g of diethylene glycol diethyl ether acetate, and 13.4 g of "SWASOLVE #1000" were mixed at room temperature, and the temperature of the article was raised to 70 ° C for 2 hours. After cooling to 40 ° C, 75.5 g of "JER-1001", 4.3 g of 1,4-butanediol, and diethylene glycol diethyl ether acetate, which were 70% dissolved in diethylene glycol diethyl ether acetate, were added with stirring. 40.7 g of the ester and 13.4 g of "SWASOLVE #1000" were mixed, and the temperature of the article was raised to 80 ° C for 1 hour. Subsequently, 1.1 g of isobutanol and 10.2 g of diethylene glycol diethyl ether acetate were added, and the mixture was further reacted at 80 ° C for 1 hour. Finally, 4.1 g of "SWASOLVE #1000" 1% solution of "NEOSTANN U-810" was added, and the temperature of the article was reacted at 80 ° C for 1 hour. It was confirmed by infrared spectroscopic analysis that the absorption based on the isocyanate group (2274 cm ^-1 ) disappeared and the reaction was terminated to obtain a polycarbonate resin having an epoxy group and a urethane structure (Product 8).

Manufacture 8 properties

<Manufacture of thiol compound>

The ginseng (3-mercaptopropyl) isocyanurate is used as it is in the method described in JP-A-56-120671. In other words, the reaction was carried out by irradiating ultraviolet rays with a mixed solution of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) and thiol propionic acid (manufactured by City Chemical LLC) in acetone or acetic acid. After removing the solvent under reduced pressure, the residue of the reaction solution was boiled in concentrated hydrochloric acid and neutralized by adding anhydrous sodium carbonate. The solvent was then removed through a medium activated alumina column to obtain ginseng (3-mercaptopropyl)isocyanurate.

<Example 1>

Manufactured as a solid content of 44.4 parts, 2.6 parts of synthetic ginseng (3-mercaptopropyl)isocyanurate, and hydrophobic cerium oxide "R-805" as an inorganic filler (Japan AEROSIL ( )), the average particle size of 0.012μm) 4.6 parts, after mixing with a three-roll mill, add "SWASOLVE #1000" 2.0 parts to adjust the viscosity to about 35Pa. s. Finally, 2.2 parts of "NICHIGO IMIDAZOLE 1,2-DMI" (Japan Synthetic Chemical Industry Co., Ltd.) as a hardening catalyst were added to rotate. The AWATORY RITAR AR-100 (manufactured by THINKY Co., Ltd.) was stirred to produce a resin paint.

<Example 2>

A resin paint was produced in the same manner as in Example 1 except that the product 1 of Example 1 was changed to the product 2.

<Example 3>

In addition, when the product 1 of the first embodiment was changed to the product 3, the amount of ginseng (3-mercaptopropyl) isocyanurate was changed to 3.7 parts, and the amount of "R-805" was changed to 6.2 parts. A resin paint was produced in the same manner as in Example 1 except for the remainder.

<Example 4>

Except that the product 1 of the first embodiment is changed to the product 4, A resin paint was produced in the same manner as in Example 1.

<Example 5>

In addition, when the product 1 of the first embodiment was changed to the product 5, the amount of ginseng (3-mercaptopropyl) isocyanurate was changed to 4.4 parts, and the amount of "R-805" was changed to 7.6 parts. A resin paint was produced in the same manner as in Example 1 except for the remainder.

<Example 6>

In addition, the product 1 of the first embodiment was changed to the product 6, and the amount of the compound 1 was changed to 49 parts, and the amount of ginseng (3-mercaptopropyl) isocyanurate was changed to 2.2 parts, and "R- A resin paint was produced in the same manner as in Example 1 except that the blending amount of 805" was changed to 3.7 parts.

<Example 7>

In addition, the amount of the ginseng (3-mercaptopropyl) isocyanurate of Example 1 was changed to 9.6 parts, and the amount of "R-805" was changed to 16.3 parts, and "NICHIGO IMIDAZOLE 1, 2-DMI" was added. A resin paint was produced in the same manner as in Example 1 except that the blending amount was changed to 3.7 parts.

<Example 8>

In addition, the amount of the ginseng (3-mercaptopropyl) isocyanurate of Example 1 was changed to 1.6 parts, and the amount of "R-805" was changed to 2.7 parts, and "NICHIGO IMIDAZOLE 1, 2-DMI" was added. The allocation is changed to 0.56 A resin paint was produced in the same manner as in Example 1 except for the remainder.

<Example 9>

A resin paint was produced in the same manner as in Example 1 except that 2.6 g of the ginseng (3-mercaptopropyl)isocyanurate of Example 1 was changed to 3.0 g of "TMTP" (manufactured by Seiki Chemical Co., Ltd.). .

<Comparative Example 1>

In addition, 2.6 g of ginseng (3-mercaptopropyl)isocyanurate of Example 1 was changed to "TD2090" (MEK solution of DIC (manufactured by DIC)) (solid content conversion), and the remainder and examples 1 Similarly, a resin paint was produced.

<Comparative Example 2>

The product 7 was converted into a solid content of 44.4 g, and 7.8 g of hydrophobic cerium oxide "R-805" was used as an inorganic filler. After kneading in a three-roll mill, the solid content was added as a curing agent. 18.6g of JER-1001, 2.2g of "NICHIGO IMIDAZOLE 1,2-DMI" dissolved in diethylene glycol ether acetate, for rotation. The AWATORY RITAR AR-100 (manufactured by THINKY Co., Ltd.) was stirred to produce a resin paint.

<Comparative Example 3>

In addition, when the product 1 of the first embodiment was changed to the product 8, the amount of the ginseng (3-mercaptopropyl) isocyanurate was changed to 3.3 g, and the amount of the "R-805" was changed to 5.7 g. Other than the same as in the first embodiment, the production tree Grease paint.

Next, for the measurement method in the physical property evaluation. The evaluation method will be explained.

<Evaluation of low temperature hardenability>

The resin paint prepared in the examples and the comparative examples was screen-printed on a 50 μm thick polyimine film (UPILEX 50S: manufactured by Ube Industries, Ltd.) using a 200 mesh plate, and hardened at 80 ° C for 60 minutes. The sponge was immersed in acetone on the hardened surface, and the force of 10 g of the load was rubbed and rubbed 5 times to observe the surface of the hardened surface. The colorlessness was evaluated as "◎", the slightly discolored was evaluated as "○", the apparently discolored was evaluated as "△", and the hardened body was dissolved to expose the film as "X". Further, in Comparative Example 2, gelation was observed at room temperature due to the progress of the reaction, so that it could not be evaluated. For the same reason, future evaluations will not be possible. The results are shown in Table 1.

<Evaluation of printability>

Using a 200-mesh plate, a 38 μm thick polyimide film having a comb-shaped electrode pattern of L/S=15/15 μm and a circuit thickness of 8 μm was formed to cover the entire surface of the comb-shaped electrode pattern. The resin paint prepared in the examples and the comparative examples was screen-printed on a 50 μm-thick polyimide film (UPILEX 50S: manufactured by Ube Industries, Ltd.). After standing at 20 ° C for 10 minutes, it was hardened at 80 ° C for 60 minutes (only Comparative Example 1 was cured at 130 ° C for 60 minutes). The thickness of the hardened body was 50 μm. After a metal microscope (MF-UD2017B, manufactured by Mitsu Toyo Co., Ltd., objective lens × 5, total magnification × 150), it was observed immediately after printing ~ to 10 minutes of the surface of the printed part, and the surface of the hardened body after hardening. When there is no bubble within ~5 minutes immediately after printing, it is marked as "◎". When there is no bubble within 5 minutes to 10 minutes, it is marked as "○", and when it is left after curing, it is marked as "X". The results are shown in Table 1.

<Evaluation of softness> (elastic modulus and elongation)

The resin paint prepared in the examples and the comparative examples was applied to a release PTFE (polyethylene terephthalate) film (AFLEX 50N: manufactured by Asahi Glass Co., Ltd.) using a bar coater, and hardened at 80 ° C. 60 minutes (Comparative Example 1 was cured at 130 ° C for 60 minutes). The thickness of the hardened body was 50 μm. Subsequently, the PTFE film was peeled off. The tensile test was carried out 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 tensile speed of 50 mm/min according to Japanese Industrial Standards (JIS K7161). The measurement of the modulus of elasticity and the elongation are determined by measuring the drop point of the sample. The results are shown in Table 1.

(bending)

The resin paint prepared in the examples and the comparative examples was applied to a 50 μm-thick polyimine film (UPILEX 50S: manufactured by Ube Industries, Ltd.) using a bar coater, and hardened at 80 ° C for 60 minutes (only Comparative Example 1 was cured at 130 ° C for 60 minutes). The thickness of the hardened body was 50 μm. The hardened surface is bent 180 degrees on the outside and 360 degrees in the opposite direction. Those who have not been whitened on the hardened surface and have not caused cracks are marked as "○", those who have been cured on the hardened surface are marked as "△", and those who have been whitened and cracked on the hardened surface are marked as "X". The results are shown in Table 1.

<Evaluation of insulation reliability>

Using a 200 mesh plate, on a 38 μ thick polyimine film formed with a comb-shaped electrode pattern of L/S=15/15 μm and a circuit thickness of 8 μm, covering the entire surface of the comb-shaped electrode pattern, the screen The resin varnish prepared in the printing examples and the comparative examples was cured at 80 ° C for 60 minutes (only Comparative Example 1 was cured at 130 ° C for 60 minutes). While applying a voltage of 100 V to it, it was allowed to stand for 1000 hours at 85 ° C and a relative humidity of 85%. The holding time until the ion migration or the insulation resistance value was decreased (to 106 Ω or less) was measured, and this was used as the HHBT (high temperature and high humidity reference test) durability time. When the HHBT endurance time is 1000 hours or longer, it is recorded as ○, when it is 500 hours or longer, it is recorded as Δ, and when it is less than 500 hours, it is recorded as ×. The results are shown in Table 1.

As understood from Table 1, the examples are resin compositions which can be cured at a low temperature of 80 ° C, and it is understood that the cured film has excellent flexibility, printability, and insulation reliability. On the other hand, in Comparative Example 1, the hardening at a low temperature was insufficient, and the elongation of the cured film was poor. Comparative Example 2 gelled immediately and was not user resistant in terms of time. The cured film of Comparative Example 3 lacked flexibility and was inferior in printability and insulation reliability.

The present application is based on Japanese Patent Application No. 2012-097637, the entire contents of which is incorporated herein.

Claims (17)

A resin composition comprising (A) a polybutadiene resin having an epoxy group and a urethane structure, and (B) a thiol-based hardener, wherein (B) a thiol-based hardener The agent is selected from the group consisting of trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptopropionate), dipentaerythritol tert-(3-mercaptopropionate), gins-[(3-mercaptopropionate)醯oxy)-ethyl]-isocyanurate, ginseng (3-mercaptopropyl)isocyanurate, octyl thioglycolate, ethylene glycol bis(mercaptoacetate), trimethylol Propane ginseng (mercaptoacetate), pentaerythritol hydrazide (mercaptoacetate), 3-mercaptopropionic acid, pentaerythritol bismuth (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy) butyl Alkane, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1 H,3 H,5 H)-trione, three A compound of the group consisting of methylolpropane ginseng (3-mercaptobutyrate) and trimethylolethane ginate (3-mercaptobutyrate). In the resin composition of claim 1, when the total solid content of the resin composition is 100% by mass, the content of the (A) polybutadiene resin having an epoxy group and a urethane structure is 50. ~95% by mass. The resin composition of claim 1 or 2, wherein (A) the polybutadiene resin having an epoxy group and a urethane structure has a number average molecular weight of from 500 to 200,000. The resin composition of claim 1 or 2, wherein (A) the polybutadiene resin having an epoxy group and a urethane structure has an epoxy equivalent of from 300 to 10,000. The resin composition of claim 1 or 2, wherein (A) the polybutadiene resin having an epoxy group and a urethane structure is such that (a) has intramolecular a polydiene polyol compound having two or more hydroxyl groups, (b) an epoxy compound having one or more hydroxyl groups and one or more epoxy groups in the molecule, and (c) a polyisocyanate compound having two or more isocyanate groups in the molecule The reaction comes. In the resin composition of the item 1 or 2, when the total solid content of the resin composition is 100% by mass, the content of the (B) thiol-based curing agent is 0.5 to 15% by mass. The resin composition of claim 1 or 2, which further contains (C) an inorganic filler. The resin composition of claim 7, wherein (C) the inorganic filler has an average particle diameter of 0.005 to 1 μm. The resin composition of claim 1 or 2, which further contains (D) a hardening accelerator. The resin composition of claim 1 or 2, which is used for an overcoating agent or an interlayer insulating film. The resin composition of claim 10, wherein the overcoating agent is used for encapsulating the organic TFT element with a coating agent. A liquid resin composition obtained by using the resin composition of claim 1 or 2. A film material obtained by using the resin composition according to any one of claims 1 to 12. A hardened body of the resin composition according to any one of claims 1 to 9, which has an elongation of 20% or more and an elastic modulus of 1000 MPa or less. A flexible printed wiring board comprising the hard as claimed in Chemical body. An organic TFT device comprising the hardened body as claimed in claim 14. An electronic device incorporating a flexible printed wiring board as claimed in claim 15 or an organic TFT device as claimed in claim 16.