TWI473854B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to a resin composition and a film for sealing an organic EL element using the same.

The organic EL (Electroluminescence) element is weak in moisture, and when the display device or the illumination device is formed using an organic EL element, the organic material itself is deteriorated by moisture, the brightness is lowered, and the light is not emitted, and the electrode and the organic EL layer are The interface is peeled off by the influence of moisture, and the metal is oxidized to have a high resistance. Therefore, for example, as shown in FIG. 4, the glass 4 with the moisture absorbing material 3 is placed on the organic EL element 2 formed on the glass substrate 1 at a predetermined interval, and the substrate 1 and the glass plate 4 are placed at opposite intervals. An inert gas atmosphere or a vacuum state is formed to perform a sealed can closure process. However, since the thickness of the closed structure portion including the organic EL element and the two glass sheets is increased, it is impossible to sufficiently reduce the thickness of the display device or the illumination device.

Therefore, as shown in Fig. 1, it is proposed to form the curable resin composition layer 6 under the entire organic EL element 2 coated on the glass substrate 1 on which the organic EL element 2 is formed, and to be bonded thereto. In the base material 7, the curable resin composition layer 6 is cured to form a closed structure of the hardened layer (hereinafter, the closed structure is referred to as "total sealing of the organic EL element" or simply "completely closed") (Patent Document 1). However, in the patent document 1, the curable resin composition is an acrylic ultraviolet curable resin composition, which may cause a problem of deterioration of the organic EL element or a portion (unhardened portion) where ultraviolet rays do not reach, and it is not easy. The problem of a closed structure with high reliability is obtained. Further, when compared with an epoxy resin, acrylic resin is not preferable in terms of physical properties such as heat resistance.

Therefore, in recent years, a thermosetting composition mainly composed of an epoxy resin has been reviewed (for example, Patent Document 2). However, in order to suppress the deterioration of the heat of the organic EL element, it is necessary to have excellent low-temperature curability, and when the cured product of the epoxy resin is compared with the cured product of the acrylic resin, the moisture permeability is not good. Therefore, it is necessary to improve the moisture permeability resistance of the cured product, but it has not yet reached a curable resin composition containing an epoxy resin as a main agent which can sufficiently satisfy the requirement.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-182059

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-70221

An object of the present invention is to provide a resin composition which is rapidly cured at a low temperature, has excellent adhesion, and can form a cured product excellent in moisture permeability resistance.

In order to solve the above problems, the present inventors have further studied the results of the review and found that the present invention can be completed by using a resin composition containing an epoxy resin and an ionic liquid.

In other words, the present invention encompasses the following.

(1) A resin composition characterized by containing an epoxy resin and an ionic liquid.

(2) The resin composition according to (1) above, wherein the ionic liquid system is composed of an ammonium cation or a lanthanide cation, and an N-mercaptoamino acid ion or a carboxylic acid anion.

(3) The resin composition according to (1) or (2) above which further contains a hygroscopic metal oxide.

(4) The resin composition according to any one of (1) to (3) above which further contains an inorganic filler.

(5) A resin composition sheet which is formed by forming a layer of the resin composition according to any one of (1) to (4) on a support.

(6) A resin composition sheet according to the above (5), which is used for sealing an organic EL element.

(7) An organic EL device comprising the sheet of the resin composition for sealing an organic EL element according to the above (6).

[Effect of the invention]

The resin composition of the present invention is rapidly cured at a low temperature of 140 ° C or lower (preferably 120 ° C or lower) to form a cured product excellent in moisture permeability resistance and excellent in adhesion strength. In addition, the resin composition of the present invention and the resin composition sheet using the same can be suitably used as a coating material, a bonding material, and a sealing material which are used for various devices and components thereof which are susceptible to heat deterioration and which have a moisture-proof effect. A material, etc., can easily form a covering structure, a bonding structure, a closed structure, and the like which have high moisture resistance and high reliability. In particular, an organic EL display device or an organic EL illumination device with high reliability can be provided.

[In order to implement the invention]

In the following, the invention will be described in a suitable embodiment.

The resin composition of the present invention is characterized by containing an epoxy resin and an ionic liquid.

The term "ionic liquid" as used herein generally means "a salt composed of an anion and a cation which melts in a temperature range of about 100 ° C or lower", but in the present specification means "by an anion and a cation" a salt that is formed to melt in a temperature range below the hardening temperature." In other words, the salt is melted in a temperature range of 140 ° C or lower (preferably 120 ° C or lower), and has an epoxy resin hardening action.

[Epoxy resin]

The epoxy resin used in the present invention may be any one having two or more epoxy groups per molecule. 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 epoxy propylamine type epoxy resin (for example, tetraglycidyldiamine diphenylmethane, triepoxypropyl-p-aminophenol, diepoxy Propyl toluidine, diepoxypropyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A phenolic Varnish type epoxy resin, epoxy resin having butadiene structure, diepoxypropoxy ether compound of bisphenol, diepoxypropoxy ether compound of naphthalene glycol, epoxidized ether of phenol, and alcohol Di-glycidoxy ether compounds, and alkyl substituents, halides, hydrides, and the like of such epoxy resins. The epoxy resin may be used singly or in combination of two or more.

The epoxy resin maintains high heat resistance and low moisture permeability of the resin composition of the present invention, among which bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolak type ring An oxy resin, a biphenyl aralkyl type epoxy resin, a phenol aralkyl type epoxy resin, an aromatic glycidoxy amide type epoxy resin, an epoxy resin having a dicyclopentadiene structure, or the like is preferable.

Further, the epoxy resin may be in the form of a liquid, and may be in the form of a solid or a liquid or a solid. Here, the "liquid" and "solid" are in the state of an epoxy resin at normal temperature (25 ° C). In terms of coatability, workability, and adhesiveness, it is preferred to use at least 10% by weight or more of the entire epoxy resin as a liquid.

Further, in the present invention, in terms of reactivity, the epoxy resin preferably has an epoxy equivalent of from 100 to 1,000, more preferably from 120 to 1,000. Here, the epoxy equivalent is a number (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured based on the method defined in JIS K 7236.

[ionic liquid]

The ionic liquid used in the present invention has a function as a resin hardener. In the resin composition of the present invention, it is preferred to use the ionic liquid in a state of being uniformly dissolved in an epoxy resin.

a cation constituting an ionic liquid, such as an imidazolium salt, a piperidinium salt, a pyrrolidinium ion, a pyrazinium ion, a sulfonium ion, a pyridinium ion or the like; an tetraalkyl phosphonium cation ( For example, an anthraquinone cation such as a tetrabutylphosphonium ion or a tributylhexylphosphonium ion; an anthracene cation such as a triethylsulfonium ion;

An anion forming an ionic liquid, such as a halide anion such as a fluoride ion, a chloride ion, a bromide ion or an iodide ion; an alkylsulfate anion such as a methanesulfonate ion; a trifluoromethanesulfonate ion, hexafluoro Fluoride ion, fluorine trioxide (pentafluoroethyl) phosphonic acid ion a phenolic anion such as 2-methoxyphenol ion or 2,6-di-tert-butylphenol ion; an acidic amino acid ion such as aspartic acid ion or glutamic acid ion; glycine ion , aminic acid ion such as alanine ion or phenylalanine ion; N-benzhydryl propylamine ion, N-acetyl phenylalanine ion, N-acetylglycine ion, etc. N-decylamino acid ion represented by the following general formula (1); formic acid ion, acetic acid ion, citric acid ion, 2-pyrrolidone-5-carboxylic acid ion, α-lipoic acid ion, lactate ion, tartaric acid ion Carboxylic acid ion, N-methyl hippurate ion, benzoic acid ion, etc. An anion.

(wherein R-CO- is a fluorenyl group derived from a linear or branched fatty acid having 1 to 5 carbon atoms, or a substituted or unsubstituted benzamidine group, and -NH-CHX-CO ₂ is An acidic amino acid ion such as aspartic acid or glutamic acid, or a neutral amino acid ion such as glycine acid, alanine ion or phenylalanine ion.

In the above, the cation constituting the ionic liquid is preferably an ammonium cation or a lanthanoid cation, and more preferably an imidazolium ion or a ruthenium ion. More specifically, the imidazolium salt has 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium salt Ions, etc.

Further, the anion constituting the ionic liquid is preferably a phenol-based anion, an N-mercaptoamino acid ion or a carboxylic acid anion represented by the general formula (1), and an N-decylamino acid ion or a carboxylic acid. The anion is better.

Specific examples of the phenolic anion are, for example, 2,6-di-tert-butylphenol ion. Further, specific examples of the carboxylic acid anion such as acetate ion, citric acid ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, α-lipoic acid, lactate ion, tartaric acid ion, hippuric acid ion, N-methyl group Horse uric acid ion, etc., wherein acetate ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, lactate ion, tartaric acid ion, hippuric acid ion, N-methyl hippuric acid ion are preferred, and acetate ion, N- Methyl hippuric acid ion and formic acid ion are more preferable. Further, specific examples of the N-mercaptoamino acid ion represented by the general formula (1), such as N-benzhydryl propylamine ion, N-acetyl phenylalanine ion, aspartate ion , Glycine ion, N-ethinylglycine ion, etc., among which N-benzhydryl propylamine ion, N-ethyl phenyl phenylalanine ion, N-ethyl methionine ion Preferably, the N-acetylglycolate ion is better.

Specific ionic liquids, such as lauric acid-1-butyl-3-methylimidazolium salt, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium citrate Salt, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis(tetrabutylphosphonium) tartarate, tetrabutylurate Strontium salt, tetrabutyl phosphonium salt of N-methyl horse urate, tetrabutyl sulfonium salt of benzylidene-DL-alanine, tetrabutyl phosphonium salt of N-acetyl phenylalanine, 2,6-di - 3-butylphenol tetrabutyl phosphonium salt, L-aspartic acid monotetrabutyl phosphonium salt, tetrabutyl phosphonium glycinate, tetrabutyl phosphonium N-acetylglycine, lactic acid 1-ethyl-3-methylimidazolium salt, acetic acid-1-ethyl-3-methylimidazolium salt, formic acid-1-ethyl-3-methylimidazolium salt, hippuric acid-1-B 3-methylimidazolium salt, N-methyl horse uric acid-1-ethyl-3-methylimidazolium salt, bis(1-ethyl-3-methylimidazolium) tartaric acid, N-B Mercaptoglycine-1-ethyl-3-methylimidazolium salt is preferably N-ethyl decyl glycine tetrabutyl phosphonium salt, acetic acid-1-ethyl-3-methylimidazolium salt , formic acid-1-B More preferably, the base 3-methylimidazolium salt, the hippuric acid-1-ethyl-3-methylimidazolium salt, and the N-methyl hippuric acid-1-ethyl-3-methylimidazolium salt are preferred.

The method for synthesizing an ionic liquid used in the present invention is a precursor composed of a cationic moiety such as an alkylimidazolium salt, an alkylpyridinium salt, an alkylammonium salt, an alkyl phosphonium salt ion, and an anion site containing a halogen. An anion exchange method for reacting with NaBF ₄ , NaPF ₆ , CF ₃ SO ₃ Na or LiN(SO ₂ CF ₃ ) _{2 ,} etc.; reacting an amine-based substance with an acid ester to introduce an alkyl group, and causing an organic acid residue The base forms an anion ester method; and the amine is neutralized with an organic acid to obtain a salt neutralization method, etc., but is not limited thereto. The anion and the cation can be used in a solvent neutralization method, and an equal amount of anion and a cation can be used, and the solvent in the obtained reaction liquid can be directly distilled; an organic solvent (methanol, toluene, ethyl acetate, acetone, etc.) can also be added. ), concentrate the liquid.

The amount of the ionic liquid to be added is not particularly limited as long as it can cure the epoxy resin, and is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight per 100 parts by weight of the epoxy resin. When the amount is less than 0.1 part by weight, the curing property tends to be lowered. When the amount is more than 10 parts by weight, the service life of the composition and the moisture permeability resistance of the cured product tend to be lowered.

[polythiol compound]

The resin composition of the present invention may further contain an ionic liquid and a polythiol compound having at least two or more thiol groups in the molecule. By containing a thiol compound having two or more thiol groups in the molecule, the curing rate can be increased. Specifically, for example, trimethylolpropane ginseng (thioglycolate), pentaerythritol bismuth (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane ginseng (β-thio Propionate), pentaerythritol bismuth (β-thiopropionate), dipentaerythritol poly(β-thiopropionate). For example, a thiol compound obtained by esterification reaction of a polyhydric alcohol with a mercapto organic acid does not necessarily use a basic substance, and has a thiol compound having two or more thiol groups in the molecule.

Similarly, an alkyl polythiol compound such as 1,4-butane dithiol, 1,6-hexane dithiol, 1,10-decanedithiol or the like; a terminal thiol group-containing polyether a polythioether having a terminal thiol group; a thiol compound obtained by reacting an epoxy compound with hydrogen sulfide; a thiol compound having a terminal thiol group obtained by reacting a polythiol compound with an epoxy compound When a basic substance is used as the reaction catalyst in the production step, a thiol compound having a base metal ion concentration of 50 ppm or less and having two or more thiol groups in the molecule can be used. In the method of the alkali removal treatment, for example, the treated polythiol compound is dissolved in an organic solvent such as acetone or methanol, neutralized by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then subjected to extraction and washing. A method of desalting or a method of adsorbing using an ion exchange resin, a method of purifying by distillation, etc., but is not limited thereto.

In the resin composition of the present invention, when the polythiol compound is used, the mixing ratio of the epoxy resin to the polythiol compound is preferably from 0.2 to 1.2 in terms of the number of SH equivalents/epoxy equivalent. When it is less than 0.2, sufficient quick-curing property cannot be obtained, and when it is more than 1.2, the physical properties of the cured product such as heat resistance are impaired. In terms of adhesive stability, it is preferably 0.5 to 1.0.

[hygroscopic metal oxide]

In the resin composition of the present invention, in order to further improve the moisture permeability resistance of the cured product, an ionic liquid and a hygroscopic metal oxide may be blended. Here, the "hygroscopic metal oxide" means a metal oxide which has the ability to absorb moisture and chemically reacts with the moisture absorbed to form a hydroxide. Specifically, for example, calcium oxide, magnesium oxide, cerium oxide, cerium oxide, or the like. These may be used singly or in combination of two or more kinds. Among them, calcium oxide is preferred in terms of high hygroscopicity, cost, and stability of raw materials.

When the particle size of the hygroscopic metal oxide is too large, there is a fear that the coarse particles damage the organic EL element in the sealing step, and the particle size is increased as the interface strength between the resin component and the resin component is increased. It is advantageous, however, that the smaller the particle size is, the more likely it is to cause agglomeration between the particles, and it may be difficult to sufficiently impart a high moisture permeability to the cured product due to poor dispersion in the composition. Further, the average particle diameter of the hygroscopic metal oxide is preferably in the range of 0.001 to 10 μm, and more preferably the average particle diameter is in the range of 0.001 to 5 μm.

Further, when the average particle diameter of the hygroscopic metal oxide is within the above preferred range, it is more preferable that the coarse particles having a particle diameter of 20 μm or more are not contained. By not containing the coarse particles, it is advantageous in that the EL element is not damaged in the sealing step.

The average particle size of the hygroscopic metal oxide can be determined by the laser scatter method based on the Mie scattering theory. Specifically, the particle size distribution of the hygroscopic metal oxide is determined on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the medium diameter can be measured as an average particle diameter. The measurement sample may preferably be one in which the hygroscopic metal oxide is dispersed in water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

The hygroscopic metal oxide can be used as a surface treatment agent. By using the surface-treated hygroscopic metal oxide, the adhesion stability of the cured product can be further enhanced, and the moisture in the resin can be prevented from reacting with the hygroscopic metal oxide or the composition of the composition in the stage before the hardening. Time to increase the viscosity.

As the surface treatment agent used for the surface treatment, for example, a higher fatty acid, an alkyl decane, a decane coupling agent or the like can be used, and among them, a higher fatty acid or a alkyl decane is 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 or palmitic acid. These may be used alone or in combination of two or more. Among them, stearic acid is preferred.

Alkanodecanes such as methyltrimethoxydecane, ethyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane,octadecyltrimethoxydecane,dimethyl Dimethoxy decane, octyl triethoxy decane, n-octadecyl dimethyl (3-(trimethoxymethyl decyl) propyl) ammonium chloride, etc., one or two of these may be selected More than one kind.

Decane coupling agents such as 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyl(dimethoxy)methyl Epoxy decane coupling agent of decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyltriethoxy An anthraquinone coupling agent such as decane, 3-mercaptopropylmethyldimethoxydecane or 11-decylundecyltrimethoxydecane; 3-aminopropyltrimethoxydecane, 3-amino group Propyltriethoxydecane, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane , N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane and amines such as N-(2-aminoethyl)-3-aminopropyldimethoxymethyldecane Base decane coupling agent; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane and vinyl methyl diethoxy decane Vinyl decane coupling agent; p-styryl trimethoxy decane, etc. Styrene-based decane coupling agent; acrylate-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane and 3-methylpropoxypropyltrimethoxydecane; 3-isocyanatepropyltrimethoxy a thiol decane coupling agent such as an isocyanate-based decane coupling agent such as decane, bis(triethoxymethyl sulfonylpropyl) disulfide or bis(triethoxymethyl sulfonylpropyl) tetrasulfide; Trimethoxy decane, methacryloxypropyl trimethoxy decane, imidazolium, triazine decane, and the like. These may be used alone or in combination of two or more.

The surface treatment can be carried out, for example, by subjecting an untreated hygroscopic metal oxide to a stirring and dispersing at a normal temperature by a mixer, and adding a surface treatment agent (higher fatty acid, alkyl decane or decane coupling agent) to spray treatment, and stirring 5 It will be carried out in ~60 minutes. As the mixer, a conventional mixer such as a mixer of a V mixer, a bow mixer, a cone mixer, a mixer such as a manual mixer or a cement mixer, a ball mill, a cutting mill or the like can be used. Further, when the moisture absorbing material is pulverized by a ball mill or the like, the above-mentioned higher fatty acid, alkyl decane or decane coupling agent is mixed and subjected to a surface treatment. The treatment amount of the surface treatment agent (higher fatty acid, alkyl decane or decane coupling agent) varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, and is relative to the hygroscopic metal oxide. It is preferably from 1 to 10% by weight, more preferably from 1 to 5% by weight.

In the resin composition of the present invention, the content of the hygroscopic metal oxide is preferably from 1 to 40% by weight, based on the nonvolatile content of 100% by weight of the resin composition, and is from 1 to 30% by weight. The range of % is more preferably in the range of 5 to 20% by weight, particularly preferably in the range of 7 to 18% by weight, and most preferably in the range of 9 to 16% by weight. When the content is too small, the effect of sufficiently incorporating the hygroscopic metal oxide cannot be obtained. When the content is too large, the viscosity of the composition tends to increase, and the strength of the cured product tends to decrease and become brittle.

[Inorganic Filling Material]

In the resin composition of the present invention, an inorganic filler may be contained in terms of moisture permeability resistance of the cured product, prevention of rebound during film processing, improvement of adhesion, and the like. Inorganic filler materials such as cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, barium titanate, titanium Calcium acid, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these, in order to maintain low moisture permeability and high adhesion of the cured resin, talc and mica are preferred, and talc is more preferable. The inorganic filler may be used alone or in combination of two or more.

When the inorganic filler is used in the resin composition of the present invention, the content of the inorganic filler is preferably from 1 to 50% by weight based on 100% by weight of the nonvolatile component of the resin composition. The range of ～40% by weight is more preferably in the range of 5 to 30% by weight, particularly preferably in the range of 10 to 20% by weight. When the content is too small, the effect of sufficiently incorporating the hygroscopic metal oxide cannot be obtained. When the content is too large, the viscosity of the composition tends to increase, and the strength of the cured product tends to decrease and become brittle.

The upper limit of the average particle diameter of the inorganic filler used in the present invention is preferably 10 μm in terms of handleability, more preferably 5 μm, more preferably 2.5 μm, and most preferably 1.5 μm. Further, the lower limit of the average particle diameter of the inorganic filler is preferably 0.5 μm in order to prevent the viscosity of the resin composition from becoming high.

The average particle diameter of the inorganic filler 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 determined on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the particle diameter of the medium can be measured as an average particle diameter. It is preferred to measure the sample to disperse the inorganic filler in water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, a LA-500 manufactured by Horiba, Ltd., or the like can be used.

[Rubber particles]

In the resin composition of the present invention, rubber particles may be contained for the purpose of improving the mechanical strength of the cured product or relieving stress. The rubber particles are not dissolved in the organic solvent in the preparation of the resin composition, and are not compatible with the components in the resin composition such as an epoxy resin, and are preferably dispersed in the varnish of the resin composition. . The rubber particles are generally prepared such that the molecular weight of the rubber component is not dissolved in the organic solvent or the resin, and is, for example, a core-shell type rubber particle or a crosslinked acrylonitrile butadiene. Rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particle-based particles have rubber particles of a core layer and a shell layer, and for example, a shell layer of an outer layer is a glassy polymer, and a shell layer of an inner layer is a rubber-like polymer, or an outer layer. The shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glass layer is composed of, for example, a polymer of methyl methacrylate or the like, and a rubbery polymer layer such as butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3822, AC3816N (manufactured by Ganz Chemical Co., Ltd.), Metablen KW-4426 (manufactured by Mitsubishi Rayon Co., Ltd.), and F351 (manufactured by Zeon, Japan). Specific examples of the acrylonitrile butadiene rubber (NBR) particles are, for example, XER-91 (manufactured by JSR Co., Ltd.). Specific examples of the styrene butadiene rubber (SBR) particles are, for example, XSK-500 (manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles are Metablen W300A and W450A (above, manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles can be measured by a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.) is used to prepare the particle size distribution of the rubber particles on a weight basis, and the media particle diameter is averaged. The particle size is determined.

When the rubber particles are used in the resin composition of the present invention, the content of the rubber particles is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, based on 100% by weight of the nonvolatile component of the resin composition. good. When the amount is less than 0.1% by weight, the effect of sufficiently blending the rubber particles is not obtained, and when it is more than 20% by weight, the heat resistance and the moisture permeability resistance may be lowered.

[Thermoplastic resin]

In the resin composition of the present invention, the cured product can be provided with flexibility, and the thermoplastic resin can be contained in order to impart flexibility to the cured resin composition and maintain good processability when the resin composition is applied. The thermoplastic resin is, for example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, a polyfluorene resin or the like. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin can impart flexibility and prevent peeling during coating, and the weight average molecular weight is preferably 30,000 or more, more preferably 50,000 or more. However, when the weight average molecular weight is too large, the compatibility with the epoxy resin tends to decrease, and the weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less.

Further, the "weight average molecular weight of the thermoplastic resin" referred to herein is measured by gel permeation chromatography (GPC) (polystyrene conversion). By using the weight average molecular weight of the GPC method, specifically, using Shimadzu Corporation's LC-9A/RID-6A as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. was used. The column was measured for movement using chloroform as the movement, and the measurement was carried out at a column temperature of 40 ° C, using a standard polystyrene calibration line.

In the foregoing examples, the thermoplastic resin is more preferably a phenoxy resin. The phenoxy resin is excellent in compatibility with the "phenoxy resin", and is less preferred in terms of the adhesion to the cured product of the resin composition of the present invention and the moisture resistance.

The phenoxy resin has, for example, one or more selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak resin skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentadiene. A skeleton, a raw spinel skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, or a skeleton of a trimethylcyclohexane skeleton. The phenoxy resin may be used in combination of two or more kinds.

A commercially available product of a phenoxy resin, for example, 1256, 4250 (a phenoxy resin containing a bisphenol A skeleton) manufactured by Japan Epoxy Resin Co., Ltd., and YX8100 (a phenoxy group containing a bisphenol S skeleton) made by Japan Epoxy Resin Co., Ltd. Base resin), YX6954 (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Japan Epoxy Resin Co., Ltd., PKHH (weight average molecular weight (Mw) 42600, number average molecular weight (Mn) 11200) manufactured by Union Carbide Co., Ltd., etc. , Dongdu Chemical Co., Ltd. FX280, FX293, Japan Epoxy Resin (shares) YL7553BH30, YL6794, YL7213, YL7290, YL7482 and so on.

When a thermoplastic resin is used in the resin composition of the present invention, the content of the thermoplastic resin is preferably from 1 to 50% by weight, based on 100% by weight of the nonvolatile component of the resin composition, and is preferably from 3 to 5% by weight. A range of 25 wt% is more preferred. When the amount is less than 1% by weight, the effect of sufficiently blending the thermoplastic resin is not obtained, and when it is more than 50% by weight, the moisture permeability of the cured product tends to be lowered.

[coupler]

In the resin composition of the present invention, a coupling agent may be contained in terms of adhesion to a binder, a cured product, moisture permeability resistance, and the like. The coupling agent is, for example, a titanium coupling agent, an aluminum coupling agent, a decane coupling agent or the like. Among them, a decane coupling agent is preferred. Further, the coupling agent may be used singly or in combination of two or more kinds.

Decane coupling agents such as 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyl(dimethoxy)methyl Epoxy decane coupling agent of decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane , a mercapto decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane and 11-decylundecyltrimethoxydecane; 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, 3-aminopropyl dimethoxymethyl decane, N-phenyl-3-aminopropyl trimethoxy decane, N-methylaminopropyl trimethoxy decane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane and amine-based decane such as N-(2-aminoethyl)-3-aminopropyldimethoxymethyl decane a coupling agent; a urea-based decane coupling agent such as 3-ureidopropyltriethoxysilane or the like, vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl vinyl diethoxy decane Base decane coupling agent; benzene such as p-styryl trimethoxy decane Alkenyl decane coupling agent; acrylate-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane and 3-methylpropoxypropyltrimethoxydecane; 3-isocyanatepropyltrimethoxydecane a thioether decane coupling agent such as an isocyanate-based decane coupling agent, bis(triethoxymethyl sulfonylpropyl) disulfide or bis(triethoxymethyl sulfonylpropyl) tetrasulfide; Trimethoxy decane, methacryloxypropyl trimethoxy decane, imidazolium, triazine decane, and the like. Among these, an epoxy group-based decane coupling agent is more preferable.

When a coupling agent is used in the resin composition of the present invention, the content of the coupling agent is preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, based on 100% by weight of the nonvolatile component of the resin composition. good. When the content is outside this range, the effect of improving the adhesion by the addition of the coupling agent cannot be obtained.

The resin composition of the present invention may optionally contain various resin additives other than the above components insofar as the effects of the present invention are exerted. The resin additive is, for example, an organic filler such as strontium powder, nylon powder or fluoro powder, a tackifier such as white stone or organic binder, a polyoxyalkylene system, a fluorine-based or a polymer-based antifoaming agent. An adhesion imparting agent such as a leveling agent, a triazole compound, a thiazole compound, a triazine compound, or a porphyrin compound.

[Resin composition sheet]

The resin composition of the present invention can be directly applied to a coated object or a bonded object to form a resin composition film (layer), but a resin composition in which a layer of the resin composition of the present invention is formed on a support is prepared. The sheet is laminated on the object to be coated or the object to be bonded, and the resin composition layer is transferred to the object to be coated or the object to be bonded. Industrially, a method of using the sheet of the resin composition is preferred.

The resin composition sheet can be dried by applying a varnish in which the resin composition is dissolved in an organic solvent, a varnish is applied to the support, and the organic solvent is dried by heating or hot air blowing, by a conventional method. A resin composition layer is formed and manufactured.

The support used in the resin composition sheet, for example, polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate Plastic films such as polyester, polycarbonate, and polyimide. The plastic film is better with PET. In addition to the gasket treatment and the corona treatment, the support body can also be subjected to mold release treatment. The mold release treatment is carried out by, for example, a release treatment of a release agent such as a polyoxyalkylene resin-based release agent, an alkoxide resin-based release agent, or a fluororesin-based release agent.

The thickness of the support is not particularly limited, and it is preferably in the range of 10 to 150 μm, more preferably in the range of 20 to 100 μm, in terms of rationality of the resin composition sheet.

Organic solvents such as acetone, methyl ethyl ketone (hereinafter referred to as "MEK"), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, card An acetate such as a cellulose acetate, a cellosolve, a carbitol such as butyl carbitol, an aromatic hydrocarbon such as toluene or xylene, dimethylformamide or dimethylacetone. Amine, N-methylpyrrolidone, and the like. The organic solvent may be used singly or in combination of two or more.

The drying conditions are not particularly limited, and it is preferably carried out at 50 to 100 ° C for 3 to 15 minutes.

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 most preferably 5 μm to 50 μm. In addition, when a resin composition sheet for encapsulating an organic EL element is used as described below, in the closed structure, a resin composition layer (hardened layer) is laminated on the substrate (see FIG. 1), and moisture is invaded due to When the resin composition layer is thinned from the side of the resin composition layer (hardened layer), it is preferable that the contact area with the outside air is small and the moisture is blocked. In addition, when the thickness of the layer is too small, the film is transferred onto a substrate on which an organic EL element is formed (hereinafter referred to as "organic EL element forming substrate"), and the uniformity of the thickness of the coating film is lowered, and the operation of sealing the substrate is performed. The tendency to reduce sexuality.

The resin composition layer can protect the film from protection, and can also be protected by a protective film to prevent dust from adhering or scratching the surface of the resin composition layer. It is preferable that the protective film is made of the same plastic film as the support. Further, the protective film may be subjected to a mold release treatment in addition to the gasket treatment and the corona treatment. The thickness of the protective film is not particularly limited, and is preferably in the range of 1 to 40 μm, more preferably in the range of 10 to 30 μm.

[Enclosure of Organic EL Components]

Specific examples of the use of the resin composition and the resin composition sheet of the present invention include a resin composition for sealing an organic EL element or a resin composition sheet for sealing an organic EL element. When the organic EL element is sealed by using the resin composition or the resin composition sheet of the present invention, the resin composition layer is first formed on the organic EL element forming substrate under the organic EL element.

When the resin composition is used as it is, the material is applied to form a resin composition layer. The resin composition is preferably in a varnish state in which an epoxy resin, an ionic liquid, and other materials which are required to be blended are used. To the extent that the organic EL element is not affected, the aforementioned solvent or the like may be added as needed. When a solvent is used, it is dried after coating to form a resin composition layer. The thickness of the resin composition layer is the same as the thickness of the aforementioned resin composition sheet.

When a resin composition sheet is used, it is sufficient to use a moisture-proof property on a support of a resin composition sheet, and this material is used as a sealing substrate (that is, a substrate specified by reference numeral 7 in Fig. 1). The moisture-proof support (closed substrate) is a plastic film having moisture resistance, a metal foil such as copper foil or aluminum foil, or the like. A plastic film having moisture resistance, for example, a plastic film obtained by vapor-depositing an inorganic substance such as cerium oxide (cerium oxide), cerium nitride, SiCN or amorphous cerium on the surface. The plastic film herein may be the same as the above-described examples. A commercially available plastic film having moisture resistance, such as Techbarrier HX, AX, LX, L series (manufactured by Mitsubishi Plastics Co., Ltd.) or X-BARRIER (manufactured by Mitsubishi Plastics Co., Ltd.) having improved moisture resistance. As the closed substrate, a multilayer structure having two or more layers can also be used.

When the resin composition layer of the resin composition sheet is peeled off by the protective film, the resin composition layer is directly bonded to the organic EL element forming substrate, and the resin composition sheet is laminated on the organic EL element forming substrate. The method of laminating may be a batch type or a continuous type of rolls. When the support of the resin composition sheet has moisture resistance (that is, a closed substrate), after the resin composition sheet is laminated on the organic EL element forming substrate, the following resin composition layer is directly applied without the release support. Thermal hardening operation (by thereby completing the sealing treatment of the organic EL element).

Further, when the support is not moisture-proof, the support material is peeled off and the sealing base material is pressure-molded on the exposed resin composition layer, and the heat hardening operation of the resin composition layer described below is preferably performed. In this case, the sealing substrate may be a plastic film having a moisture-proof property, a metal foil such as a copper foil or an aluminum foil, or a glass plate or a metal plate which is not suitable for use as a support for the resin composition sheet. Flexible substrate. The pressure at which the substrate is sealed at the time of pressure fusion is preferably about 0.5 to 10 kgf/cm ² , and when it is melted under heating, the temperature is about 50 to 130 ° C. Further, the thickness of the sealing substrate is preferably 5 mm or less, more preferably 1 mm or less, and most preferably 100 μm or less, in terms of thickness and lightness of the organic EL device itself, and preferably 5 μm or more for preventing moisture permeation. More preferably, it is 10 μm or more, and more preferably 20 μm or more. The closed substrate may be bonded using two or more sheets.

As shown in Fig. 1, when the organic EL element 2 is formed on the glass substrate 1, when the glass substrate 1 side is used as the display surface of the display device or the light-emitting surface of the lighting fixture, the sealing substrate 7 does not necessarily have to use a transparent material. Use metal plates, metal foils, etc. Conversely, when the organic EL element is formed on a substrate formed of a material having low opacity or low transparency, when the substrate side is closed as a display surface of a display device or a light-emitting surface of a lighting fixture, the substrate is usually closed using a glass plate or Transparent plastic film (or board), etc.

After the base material is melted by the sealing material (when the support of the resin sheet for sealing the organic EL element is used as the sealing substrate, after the resin composition sheet for the organic EL element sealing is laminated), the resin composition layer can be formed. The heat hardening treatment forms a closed structure (the closed structure shown in Fig. 1). The method of thermally curing the resin composition layer is not particularly limited, and various methods can be used. For example, a hot air circulating oven, an infrared heater, a heating tube, a high-frequency induction heating device, heating by a heat of a heat tool, or the like. The resin composition of the present invention has excellent low-temperature curability, and is in the low temperature range of 140 ° C or lower (preferably 120 ° C or lower, more preferably 110 ° C or lower), and is preferably about 120 minutes or shorter (preferably 90 minutes or less, More preferably, it is hardened within a short period of time of 60 minutes or less. Therefore, the situation in which the organic EL element is deteriorated due to heat becomes extremely small. Further, the lower limit of the curing temperature and the curing time can ensure that the adhesion (adhesiveness) of the cured product is sufficiently satisfied, and the curing temperature is preferably 50 ° C or higher, more preferably 55 ° C or higher, and the curing time is 20 More preferably, it is more preferably more than 30 minutes.

According to the examples and comparative examples described below, the resin composition of the present invention is a resin composition containing an epoxy resin and an ionic liquid, and can be rapidly cured at a low temperature to form an excellent moisture permeability resistance and obtainable. Excellent hardening strength of adhesion. In particular, it is possible to realize a cured film (layer) having excellent moisture permeability resistance, no deterioration of adhesion over time, and stable adhesiveness. Further, by blending an ionic liquid and a hygroscopic metal oxide in the epoxy resin, a cured product having improved moisture permeability can be formed.

[Examples]

In the following, the invention will be more specifically illustrated by the examples and comparative examples, but the invention is not limited by the examples.

The materials (raw materials) used in the examples and comparative examples are as follows.

(A) Epoxy resin

‧828EL (manufactured by Japan Epoxy Resin Co., Ltd.): liquid bisphenol A type epoxy resin, epoxy equivalent (185 g/eq), low chlorine type epoxy resin.

‧NC3000 (manufactured by Nippon Kayaku Co., Ltd.): a biphenyl aralkyl type epoxy resin, an epoxy equivalent (275 g/eq), and a MEK solution prepared to have a 70 wt% solid content.

‧GOT (manufactured by Nippon Kayaku Co., Ltd.): m-toluidine diglycidylamine (liquid), epoxy equivalent (135 g/eq).

‧ Epiclon EXA835LV (manufactured by DIC): liquid bisphenol F-type epoxy resin, epoxy equivalent 160-170g / eq.

‧Epicot 828 (made by Japan Epoxy Resin Co., Ltd.): Bisphenol A type epoxy resin is low in chlorine type.

‧Epicot 1001 (manufactured by Japan Epoxy Resin Co., Ltd.): solid bisphenol A type epoxy resin, epoxy equivalent (475 g/eq).

(B) Hardener (ionic liquid)

‧N-Ethyl glycine tetrabutyl phosphonium salt

‧N-methyl horse uric acid-1-ethyl-3-methylimidazolium salt

‧Acetyl-1-ethyl-3-methylimidazolium salt (-1-ethyl-3-methylimidazolium acetate)

‧Toluene-1-ethyl-3-methylimidazolium salt

(solid dispersion type hardener)

‧Amicure MY-24 (Ajinomoto Fine Techno company, average particle size 10μm)

‧2PZ-CNS-PW (manufactured by Shikoku Chemical Co., Ltd.): pulverized product of trimellitic acid-1-cyanoethyl-2-phenylimidazolium salt, average particle size 10 μm

(anhydride type hardener)

‧Rikacid MH-700 (manufactured by Nippon Chemical and Chemical Co., Ltd.): methyl hexahydrophthalic anhydride

(liquid hardener)

‧2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.): 2-ethyl-4-methylimidazole

‧1B2MZ (manufactured by Shikoku Chemical Co., Ltd.): 1-Benzyl-2-methylimidazole

(C) phenoxy resin

‧YX6954 (manufactured by Japan Epoxy Resin Co., Ltd.): a high heat-resistant phenoxy resin, a weight average molecular weight (40000), and a MEK solution prepared to have a solid content of 35 wt%.

‧ YL7213 (manufactured by Japan Epoxy Resin Co., Ltd.): a high heat-resistant phenoxy resin, a weight average molecular weight (35,000), and a MEK solution prepared to have a solid content of 35 wt%.

‧PKHH (manufactured by InChem): A high heat-resistant phenoxy resin, a weight average molecular weight (42,600), and a MEK solution prepared to have a solid content of 20% by weight.

(D) Rubber particles

‧F351 (made by Zeon, Japan): Acrylic core-shell resin particles, average particle size (0.3 μm)

(E) hygroscopic metal oxides

‧Moistop #10 (manufactured by Sankyo Powder Co., Ltd.): calcium oxide, average particle size (4 μm), maximum particle size (15 μm)

‧Breaked dolomite: MEK slurry of the wet pulverizer made by the "light burnt dolomite" made by the Yoshizawa Lime Company (solid content: 40 wt%, average particle diameter: 0.87 μm)

(F) Inorganic filler

‧SG95S (made by Nippon Talc Co., Ltd.): talc, average particle size (1.4 μm)

‧D-600 (made by Nippon Talc Co., Ltd.): MEK slurry for wet pulverization of talc (solid content: 30 wt%, average particle diameter: 0.72 μm)

(G) Surface treatment agent

‧KBM3103 (made by Shin-Etsu Silicon Co., Ltd.): mercaptotrimethoxydecane

‧ Stearic acid (made by Pure Chemical Co., Ltd.)

(H) coupling agent

‧KBM-403 (made by Shin-Etsu Silicon Co., Ltd.): 3-glycidoxypropyltrimethoxydecane

The respective compositions of the examples and comparative examples were adjusted in the order shown below. The blending was carried out in the amounts shown in Tables 1 and 2.

(Example 1)

In the liquid bisphenol A type epoxy resin ("828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and the liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), acrylic core resin (Japanese Zeon Co., Ltd.) was blended. "F351") roll-dispersed mixture (mixture G), biphenyl aralkyl type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.), 70% by weight of solid component MEK solution, phenoxy resin (Japan Epoxy) MEK solution of 35 wt% solid content of "YX6954" manufactured by Resin Co., Ltd., talc powder ("SG95S" manufactured by Nippon Talc Co., Ltd.), coupling agent ("KBM-403" manufactured by Shin-Etsu Silicon Co., Ltd.), and AGI Homomixer Robomix type mixer ( Mixed by Primix (mixture H). Then, the mixture (mixture H), ionic liquid hardener (N-acetylglycolic acid tetrabutylphosphonium salt) and organic solvent (MEK, acetone) are uniformly dispersed in a high-speed rotary mixer to obtain a varnish-like resin. Composition. Next, the release surface of the PET film (thickness: 38 μm) treated with the varnish-like resin composition as an alkyd-based release agent was dried at a thickness of 40 μm after drying. The die coater was uniformly applied and dried at 60 to 80 ° C for 6 minutes to obtain a resin composition sheet.

(Example 2)

A varnish-like resin composition was prepared in the same manner as in Example 1 except that N-methyluric acid imidazolium salt was used for the ionic liquid hardener to prepare a resin composition sheet.

(Example 3)

A varnish-like resin composition was prepared in the same manner as in Example 1 except that an imidazolium acetate salt was used for the ionic liquid curing agent to prepare a resin composition sheet.

(Example 4)

A varnish-like resin composition was prepared in the same manner as in Example 1 except that an imidazolium formate salt was used for the ionic liquid hardener to prepare a resin composition sheet.

(Example 5)

The surface of the calcium oxide ("Moistop #10" manufactured by Sankyo Powder Co., Ltd.) and the surface treatment agent ("stearic acid" of Pure Chemical Co., Ltd.) were stirred by a cutting mill pulverizing device. Then, in addition to the liquid bisphenol A type epoxy resin ("828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and the liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), an acrylic core-shell resin (Japanese Zeon) was used. "F351" manufactured by the company, a mixture of a roll dispersion, a surface-treated calcium oxide, a biphenyl aralkyl type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.), a 70% by weight solid content MEK solution, benzene Ethoxy resin ("YX6954" manufactured by Japan Epoxy Resin Co., Ltd.), a MEK solution of 35 wt% solid content, talc powder ("SG95S" manufactured by Nippon Talc Co., Ltd.), and a coupling agent ("KBM-403" manufactured by Shin-Etsu Silicon Co., Ltd.), AGI A varnish-like resin composition was prepared in the same manner as in the method described in Example 1 except that the mixture of the Homomixer Robomix type mixer (manufactured by Primix) was used in place of the mixture H of Example 1, and a resin composition sheet was produced.

(Comparative Example 1)

In addition to the liquid bisphenol A type epoxy resin ("828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and the liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), an acrylic core-shell resin (manufactured by Zeon Corporation, Japan) "F351"), a solid dispersion type hardener ("MY-24" manufactured by Ajinomoto Fine Techno Co., Ltd.) replaced the mixture G of Example 1 with a roll-dispersed mixture, and did not use an ionic liquid hardener (N-ethinylamine) A varnish-like resin composition was prepared in the same manner as in the method described in Example 1 except that the tetrabutylphosphonium salt was used to prepare a resin composition sheet.

(Comparative Example 2)

In addition to the liquid bisphenol A type epoxy resin ("828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and the liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), an acrylic core-shell resin (manufactured by Zeon Corporation, Japan) "F351"), a cationic polymerization catalyst type hardener (2-ethyl-4-methylimidazole, "2E4MZ" manufactured by Shikoku Kasei Co., Ltd.) was replaced with a mixture of roll dispersions, and the mixture G of Example 1 was used, and no ions were used. A varnish-like resin composition was prepared in the same manner as in the method described in Example 1 except that a liquid hardener (N-ethyl decyl glycine tetrabutyl phosphonium salt) was used to prepare a resin composition sheet.

(Comparative Example 3)

Solid dispersion hardening uniformly dispersed in a liquid bisphenol F type epoxy resin ("EXA-835LV" manufactured by DIC Corporation) and bisphenol A type epoxy resin ("Epicot 1001" manufactured by Japan Epoxy Resin Co., Ltd.) a mixture of a pulverized product of trimellitic acid-1-cyanoethyl-2-phenylisoimidazolium salt and "2PZ-CNS-PW" manufactured by Shikoku Chemicals Co., Ltd., and a phenoxy resin (manufactured by InChem) A 20 wt% solid content MEK solution and a decane coupling agent ("KBM403" manufactured by Shin-Etsu Silicon Co., Ltd.) of "PKHH") were used to prepare a resin composition. Using this resin composition, a resin composition sheet was produced in the same manner as in the method described in Example 1.

(Comparative Example 4)

Epiclon EXA-835LA (liquid bisphenol F type epoxy resin, DIC company), Rikacid MH-700 (methyl hexahydrophthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.), 1B2MZ (1-benzene) Methyl-2-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.), to obtain a resin composition. Using this resin composition, a sheet-like cured product having a thickness of 40 μm was obtained using a mold.

(Comparative Example 5)

Epicot 828 (liquid bisphenol A epoxy resin low chlorine type, manufactured by Japan Epoxy Resin Co., Ltd.), Rikacid MH-700 (methyl hexahydrophthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.), 1B2MZ (1B2MZ) 1-Benzyl-2-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.), to obtain a resin composition. Using this resin composition, a sheet-like cured product having a thickness of 40 μm was obtained using a mold.

(Example 6)

Acrylic core-shell resin ("F351" manufactured by Zeon Corporation, Japan) in liquid bisphenol A epoxy resin ("828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.) In the mixture dispersed by the roll (mixture G), 70% by weight of calcium oxide ("Moistop #10" manufactured by Sankyo Powder Co., Ltd.) and biphenyl aralkyl type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.) MEK solution, phenoxy resin ("YX6954" manufactured by Japan Epoxy Resin Co., Ltd.), 35 wt% MEK solution, talc powder ("SG95S" manufactured by Nippon Talc Co., Ltd.), and coupling agent ("KBM-403" manufactured by Shin-Etsu Silicon Co., Ltd.) AGI Homomixer Robomix type mixing mixer (manufactured by Primix) was mixed (mixture H). Then, the mixture (mixture H), an ionic liquid hardener (N-acetylglycolic acid tetrabutylphosphonium salt) and an organic solvent (MEK, acetone) are mixed and uniformly dispersed in a high-speed rotary mixer to obtain a varnish. Resin composition. Next, by using a release film of a PET film (thickness: 38 μm) treated with an alkyd-based release agent in the varnish-like resin composition, the thickness of the resin composition layer after drying was 40 μm, and molding was carried out. The applicator was uniformly coated and dried at 60 to 80 ° C for 6 minutes to obtain a resin composition sheet.

(Example 7)

Using a stirring type surface treatment apparatus, the surface treatment was carried out on a calcium oxide ("Moistop #10" manufactured by Sankyo Powder Co., Ltd.) by sulfhydryltrimethoxydecane ("KBM3103" manufactured by Shin-Etsu Silicon Co., Ltd.), and Example 6 In the same manner, a varnish-like resin composition was prepared to prepare a resin composition sheet. Further, the treatment amount of mercaptotrimethylnonane in the surface treatment of calcium oxide was 2% by weight based on the calcium oxide.

(Example 8)

N-methyl as an ionic liquid hardener was used after surface treatment with stearic acid (manufactured by Junsei Chemical Co., Ltd.) on calcium oxide ("Moistop #10" manufactured by Sankyo Co., Ltd.) using a stirring surface treatment apparatus. A varnish-like resin composition was prepared in the same manner as in Example 6 except that the 1-ethyl-3-methylimidazolium salt of horse uric acid was used to prepare a resin composition sheet. Further, the amount of stearic acid treated in the surface treatment of calcium oxide was 2% by weight based on the calcium oxide.

(Example 9)

A mixture A in which a solid epoxy resin ("HP7200H" manufactured by DIC Corporation) was dissolved in a phenoxy resin ("EL7213" manufactured by Japan Epoxy Resin Co., Ltd., and a MEK solution of 35 wt% solid content) was prepared. In addition, a mixture B in which stearic acid was dispersed was added to the MEK slurry (solid content: 40% by weight) of the fired dolomite (the wet pulverizer manufactured by Yoshizawa Lime Co., Ltd.). Mixture mixture A, mixture B, talc ("D-600" manufactured by Japan Talc Co., Ltd., wet-type pulverizer, 30% by weight of MEK slurry), and rubber fine particle dispersion liquid epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd. "), a latent curing accelerator for epoxy resin ("U-CAT3502T" manufactured by Sunpro Co., Ltd.), a liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), and a decane coupling agent ("KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 403"), mixed with an AGI Homomixer Robomix type mixer (manufactured by Primix). An ionic liquid hardener (tetrabutylphosphonium N-acetamidoglycolate) was added thereto, and uniformly dispersed in a high-speed rotary mixer to obtain a varnish-like resin composition. Using this resin composition, a resin composition sheet was produced in the same manner as in the method described in Example 1.

(Embodiment 10)

In the same manner as in Example 9, a varnish-like resin composition was prepared on the basis of the following Table 3. Using this resin composition, a resin composition sheet was produced in the same manner as in the method described in Example 1.

(Example 11)

In the same manner as in Example 9, a varnish-like resin composition was prepared on the basis of the following Table 3. Using this resin composition, a resin composition sheet was produced in the same manner as in the method described in Example 1.

Further, Comparative Examples 4 and 5 correspond to Examples 1 and 2 of Patent Document 2 (JP-A-2006-70221).

Explain the various methods of measurement and methods of assessment.

1. Low temperature hardening ‧ Determination and evaluation of preservation stability

In the resin compositions obtained in the examples and the comparative examples, the low-temperature hardenability and the storage stability of the soft steel sheet when the resin composition layer was heat-cured at 120 ° C for 90 minutes were evaluated.

First, a soft steel plate (JISG3141, SPCCD, first width: 100 mm × second width: 25 mm × thickness: 1.6 mm) whose surface shape is polished by an endless belt (JIS #120) is used, as shown in Fig. 2 A resin composition layer 12A having a rectangular resin composition sheet (first width: 12.5 mm × second width: 25 mm) 12 is superposed on one end portion of the surface 11A of the soft steel sheet 11 in the longitudinal direction. The test piece 13 was produced by laminating under the conditions of a temperature of 80 ° C and a pressure of 1 kgf / cm ² (9.8 × 104 Pa) by a vacuum laminator. Further, two identical ones were produced in the test piece 13.

Next, as shown in Fig. 3, the PET film 12B on both sides of the two test pieces 13 was peeled off, and the resin composition layer 12A was opposed to each other and laminated under a width of 12 mm, and was pressed under a pressure of about 300 g/cm ² . Fixing with a holder and performing heat hardening treatment at 120 ° C / 90 minutes. Then, the tensile shear bond strength between the two test pieces was measured by a tenter universal testing machine (TENSILON UTM-5T manufactured by Toyo Seiki Co., Ltd.). The measurement conditions were a measurement temperature of 25 ° C and a tensile speed of 1 mm/min. After the hardening treatment (initial) and after the hardening treatment, the tensile shear strength after storage for 24 hours at room temperature (25 ° C, 40% RH) was measured.

When the initial tensile shear bond strength after the hardening treatment is less than 17 MPa, the low-temperature hardenability is judged to be poor (×), and when it is 17 MPa or more and less than 19 MPa, it is judged to be good “○”, and when it is 19 MPa or more, it is judged to be excellent “◎”. "."

In addition, the storage stability is maintained by the "stretch shear bond strength after 24 hours of storage" / "initial tensile shear bond strength" × 100 (%) as the adhesion retention ratio, and the retention ratio is less than 70%. When the stability is judged to be insufficient (×), it is judged to be "△" when it is 70% or more and less than 85%, and is preferably "○" when it is 85% or more and less than 100%, and is excellent when it is 100% or more. "." However, when the tensile shear bond strength after 24 hours of storage is lowered to less than 15 MPa, the adhesive strength is not suitable for "X", and when it is 15 MPa or more, it is preferably "○".

2. Determination and evaluation of moisture permeability (560μm)

14 sheets of the resin composition sheets having the resin composition layers having a thickness of 40 μm obtained in the examples and the comparative examples were used, and the laminates of the above-mentioned conditions described above were sequentially laminated, and the laminate layer of the resin layer layer of 14 layers was laminated to have a total thickness of 560 μm. Shape. The cured product obtained by subjecting the product to a heat hardening treatment at 120 ° C for 90 minutes was subjected to a method based on JIS Z0208 at a temperature of 85 ° C and a humidity of 85% RH for 24 hours, and the amount of water vapor permeation was measured to obtain a water vapor per 1 m ² . Throughput. When the water vapor permeation amount is 250 g/m ² ‧24 hr or more, the moisture permeability resistance (560 μm) is judged to be poor "×", and when it is less than 250 g/m ² ‧24 hr and 150 g/m ² ‧24 hr or more When it is less than 150g/m ² ‧24hr and 100g/m ² ‧24hr or more, it is preferably "○", and when it is less than 100g/m ² ‧24hr, it is excellent "◎". "-" when no evaluation is performed.

In the measurement sample, a cured product of a laminate sheet having a thickness of 560 μm was used, and the entire closed structure of the organic EL element shown in Fig. 1 was observed, and the thickness (560 μm) of the cured product of the laminated sheet was observed. 1 is a width (W1 in Fig. 1) of a portion where the gas is in contact with the side of the organic EL element 2 of the curable resin composition layer (hardened layer) 6.

3. Determination and evaluation of moisture permeability (40μm)

The resin composition layer (thickness: 40 μm) of the resin composition sheet produced in the examples and the comparative examples was subjected to a thermosetting treatment at 120 ° C for 90 minutes, and the hardened layer peeled off from the support (PET film) was JIS Z0208 is a standard method, and the water vapor permeation amount is measured under the conditions of a temperature of 85 ° C, a humidity of 85% RH, and 24 hours, and a water vapor permeation amount per 1 m ² is obtained.

When the water vapor permeation amount is 300 g/m ² ‧24 hr or longer, the moisture permeability resistance is judged to be "X", and it is preferably "○" when it is less than 300 g/m ² ‧24 hr and 250 g/m ² ‧24 hr or more. It is excellent "◎" when it reaches 250g/m ² ‧24hr. "-" when no evaluation is performed.

4. Evaluation of laminating processability

The lamination processability of the resin composition layer of the resin composition sheet obtained in the examples and the comparative examples was evaluated at the value of the lowest melt viscosity at the time of temperature measurement. The lowest melt viscosity is a type of rheosol-G3000 manufactured by UBM, a parallel plate having a resin content of 1 g and a diameter of 18 mm, and a measurement start temperature of 60 ° C, a temperature increase rate of 5 ° C / min, a measurement temperature of 60 ° C to 200 ° C, and a vibration number of 1 Hz / Dego was measured. The lowest viscosity value (η) is used as the lowest melt viscosity. The lowest melt viscosity of the laminating process is preferably less than 20,000 poise (○), and 20,000 poise or more is not good (×). "-" when no evaluation is performed.

5. Determination of adhesion to the substrate

Two sheets of aluminum foil (width: 50 mm, length: 50 mm, thickness: 50 μm) were used, and a resin composition layer (width: 40 mm, length: 50 mm) provided on the support was superposed on one surface of the first aluminum foil, and the temperature was maintained by a vacuum laminator. Lamination was carried out under conditions of 80 ° C and a pressure of 1 kgf/cm ² (9.8 × 104 Pa). Then, the support was peeled off, and the second aluminum foil was superposed on the exposed resin composition layer, and laminated under the same conditions to prepare a test piece having a three-layer structure of an aluminum foil, a resin composition layer, and an aluminum foil. The test piece was heat-cured at 110 ° C for 30 minutes, and then cut into a rectangular test piece having a width of 10 mm and a length of 50 mm, and the length direction of the test piece was measured based on the T-peel test method of JIS K-6854. Adhesiveness.

The test results described above are shown in Tables 1 and 2.

[Table 1]

[Table 2]

[table 3]

It can be seen from the comparison between the examples and the comparative examples that the resin composition of the present invention is hardened at a low temperature of 120 ° C for a short period of time, and is bonded at a high adhesive strength to obtain a stable adhesiveness, and the cured product is practical. Fully low moisture permeability. Further, from Examples 9 to 11, it is understood that the adhesion to the substrate is improved by containing an inorganic filler. From this, it is understood that it is more useful by the sealing of the organic EL element. Therefore, the resin composition of the present invention and the resin composition sheet using the same can be suitably used as a coating material, a binder, a sealing material, and the like which are used for various devices which are susceptible to heat deterioration and which are required to have moisture resistance, and constituent elements thereof. A coating structure, a bonding structure, a closed structure, and the like having high reliability against high moisture resistance can be easily formed. In particular, it is suitable to provide an organic EL display device.

[Industry use value]

The resin composition of the present invention can form a cured product having excellent adhesion and low moisture permeability by being rapidly cured at a low temperature, and can be suitably used for a sealing resin for a flat panel, for example, in addition to the sealing use of the organic EL element. The use of a moisture-proof protective film for a printed circuit board, a moisture-proof film for a lithium ion battery, and a laminated film for packaging.

The present invention is based on Japanese Patent Application No. 2009-013684 and Japanese Patent Application No. 2009-013686, the entire contents of which are hereby incorporated herein.

1, 4‧‧‧ glass substrate

2‧‧‧Organic EL components

3‧‧‧Hydrautic materials

5‧‧‧Enclosed materials

6‧‧‧ hardened resin composition layer (hardened layer)

7‧‧‧Closed substrate

11‧‧‧Soft steel plate

12‧‧‧Resin composition sheet

12A‧‧‧ resin composition layer

12B‧‧‧PET film

13‧‧‧Test piece

[Fig. 1] Fig. 1 is a typical cross-sectional view showing a completely closed structure of an organic EL element.

[Fig. 2] Fig. 2 is a typical view showing the steps of producing the test piece used in the evaluation tests of the examples and the comparative examples.

[Fig. 3] Fig. 3 is a typical view of a sample (a laminate of two test pieces) supplied to a tensile test in the evaluation tests of the examples and the comparative examples.

[Fig. 4] Fig. 4 is a typical cross-sectional view showing a closed structure of a can of an organic EL element.

1. . . glass substrate

2. . . Organic EL element

6. . . Curable resin composition layer (hardened layer)

7. . . Closed substrate

W1. . . The width of the portion of the organic EL element 2 of the curable resin composition layer (hardened layer) 6 that is in contact with the outside of the air

Claims (9)

A resin composition comprising an epoxy resin and an ionic liquid, and the ionic liquid system is composed of an ammonium cation or a lanthanide cation and an N-decylamino acid ion. The resin composition of claim 1, wherein the resin composition further contains a hygroscopic metal oxide. The resin composition of claim 1, which further contains an inorganic filler. The resin composition of claim 1, wherein the talc is further contained. The resin composition of claim 1, wherein the talc having an average particle diameter of 10 μm or less is further contained. The resin composition according to any one of claims 1 to 5, which is used for sealing an organic EL element. A resin composition sheet formed by forming a layer of a resin composition according to any one of claims 1 to 5 on a support. A resin composition sheet according to item 7 of the patent application, which is used for sealing an organic EL element. An organic EL device characterized by using a sheet of a resin composition for sealing an organic EL element of claim 8 of the patent application.