JP2011084667A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is cured at 100°C or less, has both of low moisture permeability and high adhesiveness, has high storage stability, and is tolerant enough to be formed into films. <P>SOLUTION: The resin composition contains a specific blocked isocyanate curing agent, an epoxy resin and a phenoxy resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a specific resin composition, a sealing resin composition film, and an organic EL device using the film.

  An organic EL (Electroluminescence) element is an extremely useful material capable of obtaining light emission with high luminance at a low voltage. However, since it has a fatal defect of being weak against moisture, it is made of a resin composition that is inexpensive and easy to process. In many cases, a stopper is used in combination. On the other hand, since the organic EL element also has a drawback of being weak against heat, the resin composition used has been required to have low temperature curability.

  Patent Document 1 discloses a resin composition that can be cured at low temperature by using a blocked isocyanate obtained by blocking an isocyanate compound with an imidazole as a curing agent. However, it has been found that this composition may cause a new problem that the film cannot be formed.

  Patent Document 2 discloses a sealing film using imidazole as a curing agent. However, the storage stability of the sealing film is not always satisfactory.

JP 59-227925 A JP 2000-297199 A

  An object of the present invention is to provide a resin composition that is cured at less than 100 ° C., has low moisture permeability and high adhesiveness, has high storage stability, and can withstand film formation.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by including a specific blocked isocyanate curing agent, epoxy resin, and phenoxy resin, and have completed the present invention.

That is, the present invention includes the following aspects.
[1] A resin composition comprising a blocked isocyanate obtained by blocking an isocyanate compound with an imidazole, an epoxy resin, and a phenoxy resin.
[2] A resin composition comprising an inorganic filler in the resin composition according to [1].
[3] A resin composition comprising a reaction modifier in the resin composition according to [1] or [2].
[4] A resin composition comprising a hygroscopic metal oxide in the resin composition according to the above [1] to [3].
[5] A sealing resin composition film obtained by coating a support with the resin composition described in [1] to [4] above.
[6] An organic EL device obtained by sealing or laminating the sealing resin composition film described in [5] above on an organic EL element.

  By containing a specific blocked isocyanate curing agent, epoxy resin, and phenoxy resin, it cures at less than 100 ° C, has low moisture permeability and high adhesiveness, has high storage stability, and can withstand film formation I was able to offer things.

  The film of the present invention is a resin composition comprising (A) a blocked isocyanate obtained by blocking an isocyanate compound with imidazoles, (B) an epoxy resin, and (C) a phenoxy resin.

[(A) Blocked isocyanate with isocyanate compound blocked with imidazoles]
The blocked isocyanate obtained by blocking the isocyanate compound (A) used in the present invention with imidazoles can stably maintain other physical properties while improving the storage stability of the resin composition. The component (A) is obtained through a reaction for blocking an isocyanate compound with an imidazole compound (hereinafter referred to as “this reaction”), and can be obtained by a known method. This reaction can proceed regardless of whether it is a non-solvent system or a solvent system. In the case of a solvent system, it is preferable to use an aprotic solvent inert to the isocyanate group, for example, toluene, hexane, chloroform, methylene chloride and the like.

Isocyanates used for the synthesis of the blocked isocyanate are not particularly limited, but for example, monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, isobutyl isocyanate, hexyl isocyanate, phenyl isocyanate, methane diisocyanate, 1,2-ethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2, Alkylene diisocyanates such as 2,4-trimethylhexamethylene diisocyanate, 3,3′-diisocyanate dipropyl ether, and similar alkylene diisocyanates Aliphatic diisocyanates such as acrylate, cyclopentane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate and other alicyclic diisocyanates, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyl ether diisocyanate, naphthalene diisocyanate, fluorene Mention may also be made of diisocyanates, aromatic diisocyanates such as 4,4′-biphenyl diisocyanate, and prepolymers that are both terminal isocyanates. Among them, alicyclic diisocyanates and aromatic diisocyanates are preferable from the viewpoint of solubility and reactivity, and cyclohexane diisocyanate and phenylene diisocyanate are more preferable from the viewpoint of good solubility of the block body.

Although it does not restrict | limit especially as imidazole used for the synthesis | combination of blocked isocyanate, For example, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl- An imidazole compound leaving an active hydrogen group such as 4-methylimidazole may be mentioned. Among them, 2-methyltylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 2-undecylimidazole are preferable because the melting point of the block body is high and the storage stability of the resin composition is good. -Phenylimidazole and 2-ethyl-4-methylimidazole are more preferred.
Moreover, Shikoku Chemicals Co., Ltd. 2MZ, 2E4MZ, 2PHZ, 1B2MZ, 1BZ, 2P4HZ etc. are mentioned as what can be procured in a market.

0.1-3 equivalent is preferable with respect to 1 equivalent of isocyanate groups in an isocyanate compound, and, as for the usage-amount of imidazole, 0.2-2 equivalent is more preferable. The unreacted isocyanate compound and imidazoles are preferably removed by a method such as filtration or recrystallization after completion of the blocking reaction.

  In the blocking reaction, a reaction catalyst can be used for the purpose of promoting the reaction. As the reaction catalyst, those having basicity are generally preferred. Specifically, tetraalkylammonium hydroxides such as tetramethylammonium, organic weak acid salts such as acetic acid, alkylcarboxylic acids such as tin, zinc, lead and other metals Examples include salts, metal alcoholates such as sodium and potassium, aminosilyl group-containing compounds such as hexamethyldisilazane, and phosphorus compounds such as tributylphosphine. These may use 1 type (s) or 2 or more types.

The amount of the catalyst is usually preferably from 10 to 10000 ppm, more preferably from 20 to 5000 ppm based on the total weight of the isocyanate compound and the imidazoles.

Since these reaction catalysts may deteriorate the storage stability and cured product characteristics of the resin composition or resin film, it is desirable to neutralize the catalyst with an acidic compound or the like. Examples of acidic compounds in this case include inorganic acids such as hydrochloric acid and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid methyl ester, and derivatives thereof, and ethyl phosphate. These may use 1 type (s) or 2 or more types.
This neutralization reaction is preferably performed in the range of −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. If it exceeds 150 ° C., side reaction may occur, and if it is −20 ° C. or lower, the reaction tends to be slow.

The upper limit of the content of the blocked isocyanate in the resin composition is preferably 10% by weight, more preferably 8% by weight, and still more preferably 6% by weight from the viewpoint of preventing impairing storage stability. On the other hand, the lower limit of the content of the blocked isocyanate in the resin composition is preferably 0.1% by weight, more preferably 0.5% by weight, and still more preferably 1% by weight, from the viewpoint of obtaining sufficient curability. .

[(B) Epoxy resin]
The epoxy resin used in the present invention is not particularly limited, but those having an average of 2 or more epoxy groups per molecule are preferable. For example, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine Type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, diglycidyl etherified product of bisphenol, naphthalenediol Diglycidyl ethers of Le, glycidyl ethers of phenols, and diglycidyl ethers of alcohols, and alkyl substituted derivatives of these epoxy resins, halides and hydrogenated products or the like. These may use 1 type (s) or 2 or more types.

  Among these, the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type from the viewpoint of maintaining the high heat resistance and low moisture permeability of the resin composition of the present invention. Epoxy resins, phenol aralkyl type epoxy resins, aromatic glycidyl amine type epoxy resins, epoxy resins having a dicyclopentadiene structure, and the like are preferable.

  The epoxy resin may be liquid, solid, or both liquid and solid. Here, “liquid” and “solid” are states of the epoxy resin at normal temperature (25 ° C.). From the viewpoint of coatability, workability, and adhesiveness, it is preferable that at least 10% by weight or more of the entire epoxy resin to be used is liquid. Specific examples of the liquid resin include liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032” manufactured by Dainippon Ink and Chemicals, Inc.) and “HP4032D”. ], Liquid bisphenol AF type epoxy resin (“ZX1059” manufactured by Tohto Kasei Co., Ltd.), and an epoxy resin having a hydrogenated structure (“Epicoat YX8000” manufactured by Japan Epoxy Resin Co., Ltd.). Among them, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd., which has high heat resistance and low viscosity, is preferable. Specific examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin (“HP4700” manufactured by DIC Corporation), dicyclopentadiene type polyfunctional epoxy resin (“HP7200” manufactured by DIC Corporation), and naphthol type epoxy resin. (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having a biphenyl structure (manufactured by Nippon Kayaku Co., Ltd. NC3000H "," NC3000L "," YX4000 "manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Among them, the cured product has a low viscosity that gives a cured product with low water absorption and low moisture permeability. HP7200 "is preferred.

  In the present invention, the epoxy resin preferably has an epoxy equivalent in the range of 100 to 1000, more preferably in the range of 120 to 1000, from the viewpoint of reactivity. Here, the epoxy equivalent is the mass (g) of the resin containing an epoxy group, and is measured according to the method defined in JIS K 7236.

[(C) Phenoxy resin]
The phenoxy resin used in the present invention is not particularly limited, and is bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. Examples thereof include one having at least one skeleton selected from a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. These may use 1 type (s) or 2 or more types.

  Specific examples of commercially available phenoxy resins include 1256, 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., Japan YX6954 manufactured by Epoxy Resin Co., Ltd. (phenoxy resin containing bisphenolacetophenone skeleton), PKHH manufactured by Union Carbide Corporation (weight average molecular weight (Mw) 42600, number average molecular weight (Mn) 11200), FX280, FX293 manufactured by Tohto Kasei Co., Ltd., Japan Examples include YL7553BH30, YL6794, YL7213, YL7290, YL7482 manufactured by Epoxy Resin Co., Ltd., and 1256 manufactured by Japan Epoxy Resin Co., Ltd. (phenoxy resin containing bisphenol A skeleton) YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd. YX6954 (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., PKHH (weight average molecular weight (Mw) 42600, manufactured by Union Carbide Corporation Average molecular weight (Mn) 11200) is preferred.

The upper limit of the content of the phenoxy resin in the resin composition prevents the low moisture permeability of the cured product from being impaired with respect to the nonvolatile content of 100% by weight in the resin composition, and the adhesion strength after humidification decreases. From the viewpoint of preventing this, 30% by weight is preferable, and 20% by weight is more preferable. On the other hand, the lower limit of the content of the phenoxy resin in the resin composition is preferably 1% by weight from the viewpoint of obtaining sufficient flexibility with respect to 100% by weight of the nonvolatile content in the resin composition, and preferably 5% by weight. % Is more preferable.

The upper limit of the weight average molecular weight of the phenoxy resin is preferably 150,000, more preferably 80000, still more preferably 50000, still more preferably 45000, even more preferably 40000, and particularly preferably 35000, from the viewpoint of compatibility with the epoxy resin. On the other hand, the lower limit of the weight average molecular weight of the phenoxy resin is preferably 2000, more preferably 10,000, still more preferably 12,000, and even more preferably 15000 from the viewpoints of moldability during film processing and mechanical strength of the cured composition. 17000 is particularly preferable, and 20000 is particularly preferable. The number average molecular weight is a value measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using a solution of 0.4% by weight of lithium bromide dissolved in N-methylpyrrolidone as a mobile phase, and can be calculated using a standard polystyrene calibration curve. .

[(D) Inorganic filler]
The resin composition of the present invention may further contain an inorganic filler from the viewpoints of improving moisture permeability of the cured product, improving adhesion, preventing repelling during film processing, and the like. Examples of inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and strontium titanate. , Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, talc and mica are preferable and talc is particularly preferable from the viewpoint of maintaining low moisture permeability of the cured resin. These may use 1 type (s) or 2 or more types.

  The upper limit of the average particle diameter of the inorganic filler is preferably 10 μm, more preferably 5 μm, from the viewpoint of maintaining good moisture permeability or avoiding damage to the organic EL device during the molding of the organic EL device. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm, more preferably 0.05 μm, from the viewpoint of preventing the viscosity of the composition from increasing and handling properties from decreasing.

  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 type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  In the resin composition of the present invention, when an inorganic filler is used, the upper limit of the content of the inorganic filler prevents the viscosity of the composition from increasing, and the strength of the cured product decreases and becomes brittle. From the viewpoint of preventing the above, 50% by weight is preferable and 40% by weight is more preferable with respect to 100% by weight of the nonvolatile content in the resin composition. On the other hand, the lower limit of the content of the inorganic filler is preferably 1% by weight, preferably 5% by weight with respect to 100% by weight of the nonvolatile content in the resin composition, from the viewpoint of sufficiently obtaining the effect of blending the inorganic filler. More preferred.

[(E) Reaction modifier]
The resin composition of the present invention may further contain a reaction modifier from the viewpoint of controlling the reactivity and balancing low temperature curability and storage stability. Examples of the reaction modifier used in the resin composition of the present invention include ionic liquids and Lewis bases. Among these, an ionic liquid is preferable in terms of a balance between low-temperature curability and storage stability. The ionic liquid is a salt of a cation and an anion, and the cation constituting the ionic liquid includes ammonium cation such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion, pyridinium ion; tetraalkylphosphonium cations (e.g., tetrabutylphosphonium ion, tributyl ethylhexyl phosphonium ion) phosphonium cations such as, sulfonium based cationic such as triethyl sulfonium ion.

  Examples of the anion constituting the ionic liquid include halide anions such as fluoride ion, chloride ion, bromide ion and iodide ion; alkyl sulfate anions such as methanesulfonate ion; trifluoromethanesulfonate ion, Fluorine-containing compound anions such as hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion; phenol ion, 2-methoxy Phenolic anions such as phenol ion and 2,6-di-tertbutylphenol ion; acidic amino acid ions such as aspartate ion and glutamate ion; glycine ion, alanine ion and phenylaion Neutral amino acid ion such as nin ion; N-acyl amino acid ion represented by the following general formula (1) such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion; formate ion, acetate ion, decanoic acid Carboxylic acid anions such as ions, 2-pyrrolidone-5-carboxylic acid ions, α-lipoic acid ions, lactic acid ions, tartrate ions, hippuric acid ions, N-methyl hippuric acid ions, benzoic acid ions, and the like.

(However, R-CO- is an acyl group derived from a linear or branched fatty acid having 1 to 5 carbon atoms, or a substituted or unsubstituted benzoyl group, and -NH-CHX-CO2 is aspartic acid or glutamic acid. Or acidic amino acid ions such as glycine, alanine, phenylalanine, etc.)

  Among the above, the cation is preferably an ammonium cation or a phosphonium cation, and more preferably an imidazolium ion or a phosphonium ion. More specifically, the imidazolium ion is 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, or the like.

  The anion is preferably a phenolic anion, an N-acylamino acid ion or a carboxylic acid anion represented by the general formula (1), and more preferably an N-acylamino acid ion or a carboxylic acid anion.

  Specific examples of the phenolic anion include 2,6-di-tertbutylphenol ion. Specific examples of the carboxylic acid anion include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, α-lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N- Methyl hippurate ion, and the like. Among them, acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion, and N-methylhippurate ion are preferable, acetate ion, N -Methyl hippurate ion and formate ion are particularly preferred. Specific examples of the N-acylamino acid ion represented by the general formula (1) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion, and the like. Among these, N-benzoylalanine ion, N-acetylphenylalanine ion, and N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.

  Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium 2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoro Acetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL-alanine Tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tertbutylphenoltetrabutylphosphonium L-aspartic acid monotetrabutylphosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, formic acid 1 -Ethyl-3-methylimidazolium salt, hippuric acid 1-ethyl-3-methylimidazolium salt, N-methylhippuric acid 1-ethyl-3-methylimidazolium salt, bis (1-ethyl-3-methylimidazolium tartrate) Preferred), N-acetylglycine 1-ethyl-3-methylimidazolium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazole formate Lium salt, hippuric acid 1-ethyl-3-me Tyrimidazolium salt, 1-ethyl-3-methylimidazolium salt of N-methylhippuric acid is particularly preferred. These may use 1 type (s) or 2 or more types.

  As a method for synthesizing the ionic liquid, a precursor composed of a cation moiety such as an alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions and an anion moiety containing a halogen is added to NaBF4, NaPF6, CF3SO3Na or LiN (SO2CF3 ) Anion exchange method in which 2 etc. are reacted, an acid ester method in which an organic acid residue becomes a counter anion while introducing an alkyl group by reacting an amine substance with an acid ester, and amines with an organic acid There is a neutralization method for obtaining a salt by neutralization, but it is not limited thereto. In the neutralization method using an anion, a cation, and a solvent, an anion and a cation are used in an equivalent amount, and the solvent in the obtained reaction solution can be distilled off and used as it is, or an organic solvent (methanol, toluene, etc.). , Ethyl acetate, acetone, etc.) may be concentrated.

  In the resin composition of the present invention, when a reaction regulator is used, the upper limit of the content of the reaction regulator is 100% by weight of the nonvolatile content in the resin composition from the viewpoint of preventing the storage stability from being impaired. The content is preferably 10% by weight, more preferably 5% by weight, and still more preferably 3% by weight. On the other hand, the lower limit of the content of the reaction modifier is preferably 0.5% by weight and preferably 2% by weight with respect to 100% by weight of the nonvolatile content in the resin composition, from the viewpoint of sufficiently obtaining the effect of the reaction modifier. Is more preferable.

[(F) Hygroscopic metal oxide]
The resin composition of the present invention may further contain a hygroscopic metal oxide in order to further improve the moisture permeability resistance of the cured product. Here, the “hygroscopic metal oxide” means a metal oxide that has a capability of absorbing moisture and chemically reacts with moisture that has been absorbed to become a hydroxide. Specifically, it is one kind selected from calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, or the like, or a mixture or solid solution of two or more kinds. Among these, calcium oxide and magnesium oxide are preferable from the viewpoint of high hygroscopicity, cost, and stability of raw materials. Specific examples of the mixture or solid solution of two or more types include calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (a solid solution of calcium oxide and aluminum oxide), and the like. It is done. Such a hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercially available product can be used. Specifically, calcium oxide (“Moystop # 10” manufactured by Sankyo Flour Mills Co., Ltd.), magnesium oxide (“Kyowa Mag MF-150”, “Kyowa Mag MF-30” manufactured by Kyowa Chemical Industry Co., Ltd., “Pure Mag” manufactured by Tateho Chemical Industry Co., Ltd. FNMG ”, etc.), lightly burned magnesium oxide (“ # 500 ”,“ # 1000 ”,“ # 5000 ”, etc., manufactured by Tateho Chemical Industries, Ltd.), calcined dolomite (“ KT ”, etc., produced by Yoshizawa Lime), calcined hydrotalcite (“Hydrotalcite” manufactured by Toda Kogyo Co., Ltd.) and the like. These may use 1 type (s) or 2 or more types.

The average particle diameter of the hygroscopic metal oxide is not particularly limited, but the upper limit value of the average particle diameter of the hygroscopic metal oxide prevents the coarse particles from damaging the organic EL element in the sealing step. From the viewpoint of increasing the interfacial bond strength with the resin component, it is preferably 10 μm, more preferably 5 μm or less, and even more preferably 1 μm or less. On the other hand, the lower limit value of the average particle diameter of the hygroscopic metal oxide tends to cause aggregation of the particles, and it becomes difficult to impart sufficiently high moisture resistance to the cured product due to poor dispersion in the composition. From the viewpoint of preventing the above, 0.001 μm is preferable, 0.01 μm is more preferable, and 0.1 μm is still more preferable.

  If the average particle size of the hygroscopic metal oxide is 10 μm or less, it can be used as it is, but if the average particle size of the commercial product exceeds 10 μm, the average particle size is 10 μm or less by pulverization, classification, etc. It is preferable to use after preparing the granular material.

  Further, the hygroscopic metal oxide preferably has an average particle diameter in the above-mentioned preferred range and does not contain coarse particles having a particle diameter of 20 μm or more. More preferably, it does not contain coarse particles of 5 μm or more. By not including such coarse particles, it is advantageous in that the EL element is hardly damaged in the sealing process.

  The average particle diameter of the hygroscopic metal oxide can be measured by a laser diffraction / scattering method based on the 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, a hygroscopic metal oxide dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  As the hygroscopic metal oxide, a surface treated with a surface treatment agent can be used. The surface treatment agent may be directly blended in the resin composition varnish. By using such a surface-treated hygroscopic metal oxide, there is an advantage that the hygroscopic metal oxide can be prevented from absorbing moisture in the resin mixing step, and the cured product can retain hygroscopicity. Thereby, the adhesion stability of the cured product can be further increased.

  As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids or alkylsilanes are preferable.

  The higher fatty acid is preferably a higher fatty acid having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid and palmitic acid. These can be used by selecting one or more. Of these, stearic acid is preferred.

  Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( 3- (trimethoxysilyl) propyl) ammonium chloride and the like. These may use 1 type (s) or 2 or more types.

  Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrime Amino silane cups such as xylsilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ring agent; Ureido silane coupling agent such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanatopropyltrimethoxy Isocyanate-based silane coupling agents such as silane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. These may use 1 type (s) or 2 or more types.

  For example, the surface treatment may be performed by adding and spraying a surface treatment agent (higher fatty acid, alkylsilane, or silane coupling agent) while stirring and dispersing untreated hygroscopic metal oxide at room temperature using a mixer. This can be done by stirring for a minute. As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. Further, when the hygroscopic material is pulverized with a ball mill or the like, a method of surface treatment by mixing the higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent (higher fatty acid, alkylsilanes or silane coupling agent) varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, but 1 to 10 with respect to the hygroscopic metal oxide. % By weight is preferred.

  The upper limit of the content of the hygroscopic metal oxide is, in the case of using the hygroscopic metal oxide, from the viewpoint of preventing the resin composition from increasing in viscosity and preventing the strength of the cured product from being reduced and becoming brittle. In addition, 40% by weight is preferable, 30% by weight is more preferable, and 20% by weight is still more preferable with respect to 100% by weight of the nonvolatile content in the resin composition. On the other hand, the lower limit of the content of the hygroscopic metal oxide is preferably 1% by weight with respect to 100% by weight of the nonvolatile content in the resin composition from the viewpoint of sufficiently obtaining the effect of the hygroscopic metal oxide. 5 wt% is more preferable, and 10 wt% is still more preferable.

[Additive]
The resin composition of the present invention may optionally contain various resin additives other than the components described above as long as the effects of the present invention are exhibited. Examples of such resin additives include organic fillers such as rubber particles, silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, and polymer-based antifoaming agents. Alternatively, adhesion promoters such as leveling agents, triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds, and the like can be given.

  The use of the resin composition of the present invention is not particularly limited, but it can be used for various devices such as semiconductors, solar cells, high-brightness LEDs, LCD seals, organic ELs, and particularly preferably used for organic EL devices. it can.

[Resin composition film for sealing]
The sealing resin composition film is a method known to those skilled in the art, for example, preparing a varnish in which the resin composition is dissolved in an organic solvent, applying the varnish on the support, and further heating or blowing hot air, etc. Can be produced by drying the organic solvent to form a resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter abbreviated as “MEK”), cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more, but those having a low boiling point are preferred for curing at less than 100 ° C.

  The drying conditions are not particularly limited, but 3 to 15 minutes are preferable within the range of 50 to 100 ° C. When the temperature is lower than 50 ° C., the amount of the solvent remaining in the film increases, and the organic EL element after lamination tends to be damaged. When the temperature is 100 ° C. or higher, the sealing resin composition film The storage stability tends to be poor.

  The thickness of the resin composition layer formed after drying is preferably 3 μm to 200 μm, more preferably 5 μm to 100 μm, and still more preferably 5 μm to 50 μm.

  As will be described later, in the structure in which the sealing base material is laminated on the resin composition layer, since the intrusion of moisture is only from the side of the resin composition layer, the resin composition layer should be thinned. The contact area with the outside air is reduced, which is desirable for blocking moisture. In addition, if the layer thickness is too small, after transferring onto the organic EL element forming substrate, the uniformity of the thickness of the coating film is reduced, so that the element is damaged or the sealing substrate is bonded. Tend to decrease.

As the support used for the sealing resin composition film, it is preferable to use a moisture-proof support (sealing substrate). Examples of the sealing substrate include a moisture-proof plastic film or a metal foil such as a copper foil and an aluminum foil. Examples of the plastic film having moisture resistance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, or amorphous silicon is deposited on the surface. As the plastic film, for example, a polyolefin film such as polyethylene, polypropylene and polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), a polyester such as polyethylene naphthalate, a plastic film such as polycarbonate and polyimide can be used. . As the plastic film, PET is particularly preferable. Examples of commercially available moisture-proof plastic films include Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and X-BARRIER (Mitsubishi Resin Co., Ltd.) with a further improved moisture-proof effect. It is done. A sealing substrate having a multilayer structure of two or more layers may be used. Also, a support of the type in which the plastic film and the metal foil are bonded to each other with an adhesive in order to improve handling properties is inexpensive and industrially convenient.
In addition, although it is also possible to use a plastic film or the like having no moisture resistance as a support, in that case, after forming the resin composition layer on the substrate on which the organic EL element is formed with the sealing resin composition film, It is preferable to peel the support and then laminate a sealing substrate separately on the resin composition layer.

  Although the thickness of a support body is not specifically limited, From viewpoints, such as the handleability of the resin composition film for sealing, 10-150 micrometers is preferable and 20-100 micrometers is more preferable.

    In addition, the film of the present invention is preferably protected with a protective film in order to prevent adhesion and scratches of dust and the like on the surface of the resin composition layer until it is actually used for forming a sealing structure. As the protective film, the plastic film exemplified for the support can be used. The protective film may be subjected to a mold release treatment in addition to a mat treatment and a corona treatment. Specific examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used.

  The thickness of the protective film is not particularly limited, but is preferably 1 to 40 μm, and more preferably 10 to 30 μm.

[Organic EL device manufacturing method]
In sealing the organic EL element using the resin composition varnish of the present invention, the resin composition layer is formed so as to be applied directly to the substrate on which the organic EL element is formed and to cover the organic EL element. The above-described solvents and the like may be added as necessary to the extent that they do not affect the organic EL element. When a solvent is used, drying is performed after coating to form a resin composition layer. The thickness of the resin composition layer is the same as the thickness of the resin composition layer in the above-described sealing resin composition film.

  The sealing of the organic EL element using the sealing resin composition film of the present invention is performed by laminating the sealing resin composition film on the substrate on which the organic EL element is formed, and placing the resin composition layer on the substrate. The organic EL element may be covered with a resin composition layer by transferring to the resin composition layer. Industrially, a method using such a sealing resin composition film is suitable. When using the resin composition film for sealing, when the resin composition layer of the resin composition film for sealing is protected with a protective film, the resin composition layer is directly applied to the substrate after peeling off the protective film. A sealing resin composition film is laminated on the substrate so as to be in contact with each other. The laminating method may be a batch method or a continuous method using a roll. In addition, when the sealing base material is used as a support for the resin composition film for sealing, after laminating the resin composition film for sealing on the organic EL element forming substrate, the support is not peeled off, and it will be described later. The resin composition layer can be thermally cured, whereby the sealing of the organic EL element is completed.

  On the other hand, when a support that does not have moisture resistance is used, the support is peeled off, the sealing substrate is pressure-bonded to the exposed resin composition layer, and a thermosetting operation of the resin composition layer described below is performed. preferable. In this case, as the sealing substrate, a sealing substrate having no flexibility such as a glass plate or a metal plate which is unsuitable for use as a support for the sealing resin composition film can be used. The pressure at the time of pressure bonding of the sealing substrate is preferably about 0.5 to 10 kgf / cm 2, and the temperature is about 50 to 130 ° C. when pressure bonding is performed under heating. As the sealing substrate, for example, a glass plate, a plastic plate (sheet, film) on which a moisture-proof layer is formed, a metal plate such as a mild steel plate, or the like is used. The thickness of the sealing substrate is preferably 5 mm or less from the viewpoint of making the organic EL device itself thin and light, more preferably 1 mm or less, particularly preferably 100 μm or less, and 5 μm or more from the viewpoint of preventing moisture permeation. More preferably, it is 10 μm or more, and particularly preferably 20 μm or more. Two or more sealing substrates may be bonded together.

  When an organic EL element is formed on a transparent substrate, if the transparent substrate side is used as a display surface of a display or a light emitting surface of a lighting fixture, it is not always necessary to use a transparent material for the support. A foil, an opaque plastic film or a plate may be used. On the other hand, when the organic EL element is formed on a substrate made of an opaque or low-transparency material, the sealing substrate side needs to be the display surface of the display or the light emitting surface of the lighting fixture. A glass plate, a transparent plastic film, a transparent plastic plate, etc. are used for a base material.

There is no restriction | limiting in particular in the method of thermosetting a resin composition layer, A various thing can be used. For example, a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, heating by pressure bonding of a heat tool, and the like can be mentioned. The resin composition of the present invention has extremely good low-temperature curability and is 120 ° C. or lower, preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and approximately 120 minutes or shorter, preferably It can be cured in a short time of 90 minutes or less, more preferably 60 minutes or less. Therefore, the deterioration of the organic EL element due to heat can be extremely reduced. The lower limit of each of the curing temperature and the curing time is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of ensuring sufficiently satisfactory adhesiveness (adhesiveness) of the cured product. The curing time is preferably 20 minutes or longer, and more preferably 30 minutes or longer.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to a following example.

[Synthesis of blocked isocyanate]
As shown in Table 1 below, 200 ml of dichloromethane was added to 0.2 mol of imidazole, and a small amount of dibutyltin dilaurate was added as a catalyst. Then, 0.2 mol of isocyanate was added dropwise with sufficient stirring and left at room temperature for 1 hour. The end point of the reaction was confirmed by disappearance near the isocyanate peak (2250 / cm ⁻¹ ) by IR measurement of the reaction solution.
The white solid precipitated by applying the reaction solution to an evaporator was washed with hexane, and a purified white solid was obtained by suction filtration (yield 97%). The structure of the purified white solid was confirmed by 1H-NMR and C13-NMR. 1H-NMR confirmed the urethane bond NH (near 5.3 ppm) and C13-NMR confirmed the urethane bond carbonyl (near 152 ppm).

[Materials used]
The materials used in the experiment will be described.
(A) Block isocyanate / Synthetic product (B) Epoxy resin / Solid epoxy resin (“HP7200H” manufactured by DIC: dicyclopentadiene type solid epoxy resin, epoxy equivalent (278 g / eq))
・ Rubber fine particle-dispersed liquid epoxy resin (“BPA328” manufactured by Nippon Shokubai Co., Ltd.) A composition comprising 17% by weight of bisphenol A type epoxy resin having an epoxy equivalent of 185 and two-layer acrylic resin particles having a primary particle size of 0.3 μm Epoxy equivalent 230g / eq))
(C) Phenoxy resin-"YL7213-B35" manufactured by Japan Epoxy Resin Co., Ltd. (MEK solution having a weight average molecular weight of 35000 and a resin solid content of 35%)
(D) Inorganic filler-Talc: MEK slurry (38% as solid content, average particle diameter: 1.3 μm) of wet pulverized “FG-15” manufactured by Nippon Talc Co., Ltd.
(E) Reaction modifier ・ Ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt)
(F) Hygroscopic metal oxide-Hydrotalcite oxide: Completely fired "Hydrotalcite" manufactured by Toda Kogyo Co., Ltd. (average particle size: 0.4 μm).
(G) Coupling agent ・ Silane coupling agent: “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[Measurement and evaluation method]
Next, a measurement / evaluation method will be described.

(Evaluation of film)
The varnishes obtained in Examples and Comparative Examples were coated with a bar coater so that the film thickness after drying was 40 um, and after drying for 8 minutes at 50 to 75 ° C., there was no separation of the resin composition, and the flexibility of the film A case where cracks or the like did not occur due to a shortage was evaluated as ◯, and a case where the resin composition was separated to form a film or a case where handling properties were difficult was evaluated as ×.

(Measurement of adhesive strength )
Two aluminum foils (width 50 mm, length 50 mm, thickness 50 um) were prepared, and the resin composition layer (width 40 mm, length 50 mm) on the support was superimposed on one surface of the first aluminum foil. The laminate was laminated by a vacuum laminator under the conditions of a temperature of 80 ° C. and a pressure of 1 kgf / cm ² (9.8 × 10 ⁴ Pa). Then, the support is peeled off, and a second aluminum foil is laminated on the exposed resin composition layer and laminated under the same conditions, and a test piece having a three-layer structure of the aluminum foil, the resin composition layer, and the aluminum foil. It was created. The test piece was heat-cured at 95 ° C. for 30 minutes, then cut into a rectangular test piece having a width of 10 mm and a length of 50 mm, and the length of the test piece was measured according to the T-type peel test method of JIS K-6854. Directional adhesion was measured. Adhesive strength of 2.0 to 3.4 N / cm was evaluated as ◯, and 3.5 N / cm or more was evaluated as ◎. Moreover, the thing of the film which cannot be formed into a film, or the film which could be formed into a film but cannot endure the subsequent evaluation was described as "-".

(Evaluation of moisture permeability)
About the hardened | cured material which heat-cured the resin composition film for 95 degreeC / 30 minute (s), the water-vapor transmission rate in 85 degreeC / 85% RH and 24hr was measured by the method based on JISZ208. A moisture permeability of less than 230 g / cm 2 · 24 hr was evaluated as “◎”, and 230 to 350 g / cm 2 · 24 hr was evaluated as “◯”. Moreover, the thing of the film which cannot be formed into a film, or the film which could be formed into a film but cannot endure the subsequent evaluation was described as "-".

(Evaluation of storage stability)
Using a model Rheosol-G3000 manufactured by UBM Co., Ltd. as a dynamic viscoelasticity measuring apparatus, the melt viscosity of the resin composition film was measured (measuring condition: 5 ° C./minute temperature rise) resin composition film Was stored at 23 ° C., the melt viscosity after storage for 24 hours was measured, and the minimum value of the melt viscosity was obtained. Storage stability was evaluated from the viscosity increase rate relative to the minimum melt viscosity before storage. When the thickening ratio was less than 1.3, it was evaluated as ◎, when 1.3 to 1.5 was evaluated as ◯, and when it exceeded 1.5, it was evaluated as ×. Moreover, the thing of the film which cannot be formed into a film, or the film which could be formed into a film but cannot endure the subsequent evaluation was described as "-".

  The following procedures prepared curable resin composition varnishes A to G having the composition shown in Table 2 below, and Table 3 shows the evaluation results. In addition, the numerical value of the compounding quantity of each material shown in Table 1 is a weight part.

Example 1
A solid epoxy resin (“HP7200H” manufactured by DIC) is dissolved in MEK to form a 75% MEK solution. A liquid epoxy resin dispersed with rubber fine particles (“BPA328” manufactured by Nippon Shokubai Co., Ltd.) and a silane coupling agent (“KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -403 ") was added to make a mixture A. On the other hand, a mixed solution B prepared by dissolving the synthesized isocyanate block imidazole “2PZ-C” in a 35% MEK solution of phenoxy resin (“YL7213” manufactured by Japan Epoxy Resin Co., Ltd.) is prepared. To obtain varnish A. Next, uniformly on a mold release treatment surface of a PET film (thickness 38 μm) obtained by treating varnish A with an alkyd mold release agent with a die coater so that the thickness of the resin composition layer after drying becomes 40 μm. And a resin composition film was obtained by drying at 50 to 75 ° C. for 8 minutes.

(Example 2)
Talc ("FG-15" manufactured by Nippon Talc Co., Ltd. was wet-ground and mixed with MEK slurry with a solid content of 38%) was mixed with Mixture A, and uniformly mixed with an Ajihomo mixer Robomix type mixing stirrer (Primics Co., Ltd.). Dispersed and mixed. This and the mixed solution B were combined and uniformly mixed with a high-speed rotary mixer to obtain varnish B. Next, a varnish B was used to obtain a resin composition film in exactly the same manner as in Example 1.

(Example 3)
Varnish C was prepared according to the recipe shown in Table 1 below in the same manner as Varnish B in Example 2 except that the ionic liquid (N-acetylglycine tetrabutylphosphonium salt) was added to mixed solution B. Next, a varnish C was used to obtain a resin composition film in exactly the same manner as in Example 1.

Example 4
Mixture A and talc ("FG-15" manufactured by Nippon Talc Co., Ltd., wet-ground, MEK slurry with a solid content of 38%), hydrotalcite oxide ("Hydrotalcite" manufactured by Toda Kogyo Co., Ltd.) ) And was uniformly dispersed and mixed with an Ajihomo mixer Robomix type mixing stirrer (manufactured by Primics). The mixed solution B and ionic liquid (N-acetylglycine tetrabutylphosphonium salt) were added to this and dispersed uniformly with a high-speed rotary mixer to obtain varnish D. Next, a varnish D was used to obtain a resin composition film in exactly the same manner as in Example 1.

(Comparative Example 1)
The synthesized blocked isocyanate “2PZ-C” was dissolved in the mixture A and dispersed uniformly with a high-speed rotary mixer to obtain varnish E. Next, the varnish E was used to obtain a resin composition film in exactly the same manner as in Example 1, but after drying at 50 to 75 ° C. for 8 minutes, the resin composition separated and became a film. There wasn't.

(Comparative Example 2)
Varnish F was prepared in the same manner as varnish B in Example 2 except that imidazole (“2PZ” manufactured by Shikoku Kasei Co., Ltd.) was used instead of the synthesized blocked isocyanate “2PZ-C”. Was prepared. Next, a varnish F was used to obtain a resin composition film in exactly the same manner as in Example 1.

(Comparative Example 3)
By the same method as varnish C in Example 3, except that acid anhydride Ricacid MH-700 (methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) is used instead of the synthesized blocked isocyanate “2PZ-C”. Varnish G was prepared according to the recipe in Table 1 below. Next, a varnish G was used to obtain a resin composition film in exactly the same manner as in Example 1, but it was difficult to handle due to insufficient strength and could not withstand the subsequent evaluation.

  From Examples 1 to 4, the resin composition of the present invention is a range that can be cured in a short time even at a low temperature of 95 ° C. and adheres with a high adhesive force, and the storage stability of the resin composition film can be used. It can be seen that the cured product has a sufficiently low moisture permeability for practical use. Therefore, according to the present invention, a resin composition serving as a sealing material capable of forming a highly reliable sealing structure without causing deterioration of the organic EL element, with respect to the organic EL element that is likely to be deteriorated by moisture or heat. It can be seen that a sealing resin composition film can be obtained and a highly reliable organic EL display device can be provided. On the other hand, in Comparative Example 1, since no phenoxy resin was used, film formation was difficult. In Comparative Example 2, since imidazole was used, the storage stability was poor, and it was found that there was a fatal defect in order to distribute in the form of a sealing resin composition film. In Comparative Example 3, since an acid anhydride curing agent was used, a film could be formed, but cracking and chipping occurred and evaluation could not be performed.

  The resin composition of the present invention contains a specific blocked isocyanate curing agent, epoxy resin, and phenoxy resin, so that it cures at less than 100 ° C., has both low moisture permeability and high adhesiveness, and has high storage stability. A resin composition that can withstand film formation, or a resin film using the composition, a resin composition film for sealing, and an organic EL device can be provided. In addition, electrical equipment such as TVs, mobile phones, digital cameras, etc. that can be applied to applications such as sealing resins for flat panels, moisture-proof protective films for printed circuit boards, moisture-proof films for lithium-ion batteries, and laminate films for packaging. Products and vehicles such as motorcycles, automobiles, trains, ships, and aircraft can be provided.

Claims (6)

  A resin composition comprising a blocked isocyanate obtained by blocking an isocyanate compound with imidazoles, an epoxy resin, and a phenoxy resin.   A resin composition comprising an inorganic filler in the resin composition according to claim 1.   A resin composition comprising a reaction regulator in the resin composition according to claim 1.   A resin composition comprising a hygroscopic metal oxide in the resin composition according to claim 1. A sealing resin composition film obtained by coating the support with the resin composition according to claim 1.   An organic EL device obtained by sealing or laminating the sealing resin composition film according to claim 5 on an organic EL element.