TWI654785B - Film - Google Patents

Abstract

The present invention is a film having a support, a protective resin composition layer, and a moisture absorbent resin composition layer. By this, it is possible to realize a film which can achieve both sufficient moisture permeability resistance and damage resistance of the element (that is, a function of preventing damage of the element). The film of the present invention is particularly suitable for the sealing of an organic EL device, and the film of the present invention can not only damage the organic EL element during the sealing operation, but also sufficiently suppress the thermal deterioration of the organic EL element, thereby obtaining a highly reliable organic EL element. Device.

Description

film

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

The organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and can obtain high-intensity light emission at a low voltage, and has attracted attention in recent years. However, the organic EL element is extremely weak in moisture, and the organic material itself is deteriorated by moisture, and the brightness is lowered or does not emit light, or the interface between the electrode and the organic EL layer is peeled off due to the influence of moisture, and the metal oxidation becomes a problem of high resistance.

On the other hand, in Patent Document 1, it is proposed to form an organic EL layer on a glass substrate, and to laminate a cured resin layer to cover the entire organic EL layer, and then to bond the water-impermeable glass substrate. However, since the acrylic resin-based ultraviolet curable resin composition is used, the problem of deterioration of the organic EL element due to ultraviolet rays or the inability of ultraviolet rays to reach is caused, and an unhardened portion is generated, and a highly reliable closed structure is hardly obtained.

Further, Patent Document 2 proposes to completely seal the thermosetting type curable resin composition of the organic EL element. However, the moisture permeability of the resulting cured layer Still not enough.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 5-182059

[Patent Document 2] JP-A-2006-70221

[Summary of the Invention]

An object of the present invention is to provide a film which is advantageous in forming a highly reliable sealing structure and having sufficient moisture permeability resistance and damage resistance of the element.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a film having a support, a protective resin composition layer, and a moisture-absorbing resin composition layer, and the present invention has been completed.

In other words, the present invention contains the following aspects.

(1) A film characterized by having a support, a protective resin composition layer, and a moisture-absorbing resin composition layer.

(2) The film according to (1) above, wherein the moisture-absorbing resin composition layer contains a hygroscopic metal oxide.

(3) The film according to the above item (1) or (2), wherein the moisture-absorbing resin composition layer contains an inorganic filler (but does not include a hygroscopic metal oxide).

(4) The film according to any one of the above items (1) to (3), wherein the protective resin composition layer contains an inorganic filler (but does not include a hygroscopic metal oxide).

(5) The film according to any one of the above items (1) to (4), wherein the moisture absorbing resin composition layer and the protective resin composition layer are at a laminating temperature set in a range of from 40 ° C to 130 ° C The difference in melt viscosity (melting viscosity of the moisture-absorbing resin composition layer - the melt viscosity of the protective resin composition layer) is 300 poise to 100,000 poise.

(6) An organic EL device characterized by having the film according to any one of the above items (1) to (5).

By the film having the support, the protective resin composition layer, and the moisture-absorbing resin composition layer, it is possible to provide a film which has both sufficient moisture permeability resistance and resistance to damage of the element (that is, a function of preventing damage of the element).

[Formation of the Invention]

The film of the present invention has a support, a moisture-absorbing resin composition layer, and a protective resin composition layer.

[support]

The support system used in the present invention is a "substance supporting the protective resin composition layer or the moisture-absorbing resin composition layer", and is not particularly limited as long as the function can be exhibited.

Support systems are classified as exfoliation support and closed support.

The peeling system support system refers to a peelable support (that is, a support which can be peeled off (separated) from the film of the present invention at the time of production of various devices) at the time of production of various devices. Specific examples of the release-based support include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), and polyethylene naphthalate. A film made of a plastic such as polyester, polycarbonate or polyimine, such as ester (hereinafter sometimes referred to as "PEN"). From the viewpoint of cost, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and polyethylene terephthalate is more preferable.

The thickness of the release-based support is not limited. From the viewpoint of the usability of the film of the present invention, the upper limit of the thickness of the support is preferably 150 μm or less, more preferably 120 μm or less, still more preferably 90 μm or less. In addition, the lower limit of the thickness is preferably 10 μm or more, more preferably 40 μm or more, and still more preferably 70 μm or more from the viewpoints of usability of the film of the present invention, moisture resistance and the like.

The release-type support is preferably a release agent which is previously subjected to a release treatment and is used for a release treatment, and specific examples thereof include a fluorine-based release agent, a polyoxymethylene-based release agent, and an alkyd-based release agent. The release agent may be used alone or in combination of two or more. The surface of the release-system support may be subjected to a matting treatment, a corona treatment, or the like, and the surface of the treatment may be subjected to a release treatment.

A closed system support system refers to a support having a moisture-proof property that can be directly used as part of various devices (i.e., for the manufacture of various devices, and finally incorporated into the device to be fabricated). More specific In the closed structure of various devices, the support system is used as a sealing material disposed on the outermost layer of the substrate formed by the element formed on the surface of the element (semiconductor element, LED element, organic EL element, etc.). The support includes, for example, a metal foil, a laminated film in which a metal foil or an inorganic deposited film is laminated on at least one side of the plastic film. The metal foil is, for example, a copper foil or an aluminum foil, and the inorganic vapor deposited film is, for example, a vapor deposited film of silica, tantalum nitride, SiCN or amorphous germanium. As the support, a commercially available plastic film having moisture resistance can be used, for example, a techbarrier HX, AX, LX, L series (manufactured by Mitsubishi Plastics Co., Ltd.) or X-BARRIER (manufactured by Mitsubishi Plastics Co., Ltd.) which improves the moisture-proof effect. Further, a glass plate, a metal plate or the like can be used from the viewpoint of imparting rigidity. When an organic EL device is produced using the film of the present invention using a closed support, the light-emitting surface of the produced organic EL device is a surface opposite to the surface of the organic EL element on which the element-forming substrate is formed.

When the closed-type support is a metal foil or a laminated film in which at least one side of a plastic film is laminated with an inorganic vapor-deposited film or a metal foil, the thickness of the support is not particularly limited, and from the viewpoint of the usability of the film of the present invention, The upper limit of the thickness of the support is preferably 150 μm or less, more preferably 120 μm or less, still more preferably 90 μm or less. In addition, the lower limit of the thickness is preferably 10 μm or more, more preferably 40 μm or more, and still more preferably 70 μm or more from the viewpoints of usability of the film of the present invention, moisture resistance and the like.

The upper limit of the thickness of the support when the glass plate or the metal plate is used for the closed-type support is preferably 5 mm or less, more preferably 1 mm or less, and still more preferably 100 μm or less from the viewpoint of making the organic EL device itself light and thin. this In addition, the lower limit of the thickness of the support is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more from the viewpoint of preventing moisture permeation and the rigidity of the organic EL device.

A laminated film in which at least one side of a plastic film is laminated with a metal foil is a coating head which can coat a film such as a gravure coater, and an adhesive is applied onto a plastic film such as a PET film, and the adhesive is used. The coated surface is obtained by laminating a metal foil such as aluminum. The thickness of the metal foil is preferably 5 μm or more from the viewpoints of lamination property, moisture permeability resistance, etc., and is preferably 125 μm or less from the viewpoint of usability. The total thickness of the laminated film of the three-layer structure is preferably in the range of 10 μm to 150 μm.

[hygroscopic resin composition layer]

The moisture-absorbing resin composition layer used in the film of the present invention is composed of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a hygroscopic metal oxide, and has moisture permeability resistance. Thereby, in the closed structure of the intended device (organic EL device or the like), the moisture intrusion element (organic EL element or the like) can be blocked.

(thermosetting resin and hardener)

The thermosetting resin and the curing agent are not particularly limited, and specific examples thereof include an epoxy resin, a cyanate resin, a phenol resin, a bismaleimide-triazine resin, a polyimine resin, an acrylic resin, and a vinyl group. Various thermosetting resins such as benzoin resin and their hardeners. Among them, from the viewpoints of low-temperature curability and adhesion of a cured product, etc., epoxy resin and hardening thereof are preferred. Agent.

The epoxy resin may have two or more epoxy groups per molecule, and specifically, for example, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, or a 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 glycidyl amine type epoxy resin (specifically There are tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic lock Epoxy resin, novolak type epoxy resin, methyl phenolic epoxy resin, bisphenol A phenolic epoxy resin, epoxy resin with butadiene structure, phenol aralkyl epoxy resin, with two rings An epoxy resin having a pentadiene structure, a diglycidyl ether of bisphenol, a diglycidyl etherate of naphthalenediol, a glycidyl etherate of a phenol, and a diglycidyl ether of an alcohol, And alkyl substituents, halides, hydrides and the like of the epoxy resins. These may be used alone or in combination of two or more.

Among these, from the viewpoints of high heat resistance and low moisture permeability of the resin composition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, and biphenyl are preferable. An aralkyl type epoxy resin, a phenol aralkyl type epoxy resin, an aromatic glycidyl amine type epoxy resin, an epoxy resin having a dicyclopentadiene structure, or the like.

The epoxy resin may be in a liquid or solid shape, or both liquid and solid shapes may be used. The term "liquid" and "solid shape" refer to the state of the epoxy resin at 25 ° C. From the viewpoints of coating, workability, adhesion, etc., the ring to be used It is preferred that 10% by weight or more of the entire oxygen resin is liquid.

The epoxy resin preferably has an epoxy equivalent of from 100 to 1,000, more preferably from 120 to 1,000, from the viewpoint of reactivity. The epoxy equivalent is the number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method specified in JIS K-7236.

The curing agent of the epoxy resin is not particularly limited as long as it has a function of curing the epoxy resin, and the resin composition is controlled from the viewpoint of suppressing thermal deterioration of an element (particularly, an organic EL element) during curing of the resin composition. The hardening treatment is preferably performed at 140 ° C or lower, more preferably 120 ° C or lower, and the hardener is preferably used in the temperature region to have an epoxy resin hardening action.

Specifically, a primary amine, a secondary amine, a tertiary amine hardener, a polyamine amide amine hardener, dicyandiamide, an organic acid bismuth or the like, and among them, an amine addition is preferred from the viewpoint of quick-curing property. Compounds (AJICUREPN-23, AJICUREMY-24, AJICUREPN-D, AJICUREMY-D, AJICUREPN-H, AJICUREMY-H, AJICUREPN-31, AJICUREPN-40, AJICUREPN-40J, etc. (made by ajinomoto-fine-techno)) An organic acid diterpene (AJICUREVDH-J, AJICUREUDH, AJICURELDH, etc. (manufactured by ajinomoto-fine-techno)). These may be used alone or in combination of two or more.

Further, it is particularly preferable to use an ionic liquid capable of curing an epoxy resin at a temperature of 140 ° C or lower, preferably 120 ° C or lower, that is, a salt which can be melted at a temperature of 140 ° C or lower, preferably 120 ° C or lower, and has a ring. A salt of hardening of an oxygen resin. The ionic liquid can be used to improve the moisture permeability resistance of the cured product of the moisture absorbing resin composition layer. The ionic liquid is preferably uniform for the ionic liquid It is used in a state of being dissolved in an epoxy resin.

The cation constituting the ionic liquid, for example, an ammonium cation such as an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, a pyrazolium ion, a pulse ion, a pyridinium ion or the like; a tetraalkyl phosphonium cation (specifically There are ruthenium cations such as tetrabutylphosphonium ion and tributylhexyl ruthenium ion; and ruthenium cations such as triethylsulfonium ion.

Examples of the anion constituting the ionic liquid include halide anions such as fluoride ions, chloride ions, bromide ions, and iodide ions; alkylsulfate anions such as methanesulfonate ions; trifluoromethanesulfonate ions; a fluorine-containing compound anion such as a hexafluorophosphonic acid ion, a trifluorotris(pentafluoroethyl)phosphonic acid ion, a bis(trifluoromethanesulfonyl)phosphonium ion, a trifluoroacetic acid ion or a tetrafluoroboric acid ion; a phenolic anion such as a phenol ion, a 2-methoxyphenol ion or a 2,6-di-tert-butylphenol ion; an acid amino acid ion such as aspartic acid ion or glutamic acid ion; glycine acid Neutral amino acid ions such as ions, alanine ions, and phenylalanine ions; N-benzamide ionic acid ions, N-ethyl phenyl phenylalanine ions, N-ethlyl glycine acid ions, etc. The following general formula (1) represents N-decylamino acid ion; formic acid ion, acetic acid ion, decanoic acid ion, 2-pyrrolidone-5-carboxylic acid ion, α-lipoic acid ion, lactate ion, tartaric acid ion , uric acid ion, N-methyl hippuric acid ion, benzoic acid ion, etc. child.

(Wherein, R-CO- based carbon linear or branched chain fatty acid having 1 to 5 of the derived acyl, or substituted or unsubstituted benzoyl group, -NH-CHX-CO ₂ ^- based aspartame Acidic amino acid ions such as acid and glutamic acid, or neutral amino acid ions such as glycine, alanine or phenylalanine.)

In the above, the cation is preferably an ammonium cation or a lanthanoid cation, more preferably an imidazolium ion or a cerium ion. The imidazolium ion is more specifically 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-decylamino acid ion represented by the general formula (1) or a carboxylic acid anion, more preferably an N-decylamino acid ion or a carboxylic acid anion.

A specific example of the phenolic anion is 2,6-di-tert-butylphenol ion. Further, specific examples of the carboxylic acid anion include acetate ion, citric acid ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, α-lipoic acid ion, lactate ion, tartaric acid ion, hippuric acid ion, N-methyl group The horse uric acid ion or the like is more preferably an acetate ion, a 2-pyrrolidone-5-carboxylic acid ion, a formic acid ion, a lactate ion, a tartaric acid ion, a hippuric acid ion, or an N-methyl hippuric acid ion. Further, specific examples of the N-mercaptoamino acid ion represented by the general formula (1) include N-benzylidene propylamine ion, N-acetyl phenylalanine ion, aspartic acid ion, and glycine Acid ions, N-ethinylglycine ion, etc., among which N-benzhydryl propylamine ion, N-ethyl phenyl phenylalanine ion, N-ethyl methionine ion, etc. It is preferably N-ethinylglycine ion.

The specific ionic liquid is preferably 1-butyl-3-methylimidazolium lactide Salt, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonate, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium a-lipoate , tetrabutyl phosphonium formate, tetrabutyl phosphonium lactate, bis(tetrabutyl phosphonium) tartrate, tetrabutyl phosphonium salt, N-methyluric acid tetrabutyl phosphonium salt, benzamidine- DL-tetrabutyl phosphonium arinate, tetrabutyl phosphonium salt of N-ethyl phenyl phenylalanine, 2,6-di-tert-butyl phenol tetrabutyl sulfonium salt, L-aspartic acid monotetrazide Butyl sulfonium salt, tetrabutyl phosphonium glutamate, tetrabutyl phosphonium salt of N-acetyl glutamine, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methyl Imidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium salt, N-methyluric acid 1-ethyl-3-methyl Imidazolium salt, bis(1-ethyl-3-methylimidazolium) tartaric acid, 1-ethyl-3-methylimidazolium salt of N-ethyl glutamic acid, more preferably N-ethyl fluorenyl Tetrabutyl phosphonium glutamate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium Salt, N-methyl Acid 1-ethyl-3-methylimidazolium salt.

The method for synthesizing the ionic liquid is, for example, a precursor composed of a cationic moiety such as an alkylimidazolium, an alkylpyridinium, an alkylammonium or an alkylphosphonium ion, and an anion containing a halogen, and NaBF ₄ and NaPF _{6 .} An anion exchange method of a reaction such as CF ₃ SO ₃ Na or LiN(SO ₂ CF ₃ ) ₂ , an reaction between an amine-based substance and an acid ester, introduction of an alkyl group, and an organic acid residue as an anion ester method and an amine The neutralization method of neutralizing a salt with an organic acid, etc., is not limited to this. Anion and cation, the solvent in the obtained reaction liquid is distilled off by using an equal amount of anions and cations in a solvent neutralization system, or may be used as it is, or an organic solvent (methanol, toluene, ethyl acetate, Acetone, etc.) is concentrated in a liquid.

The hardener is preferably used in an amount of from 0.1 to 50% by weight, more preferably from 0.5 to 25% by weight, even more preferably from 1 to 15% by weight, based on 100% by weight of the nonvolatile content in the resin composition. More preferably, it is in the range of 1.5 to 10% by weight. When it is less than this range, sufficient hardenability may not be obtained, and when it is more than 50% by weight, not only the storage stability of the resin composition is impaired, but also the moisture permeability and heat resistance of the cured product may be lowered. When the ionic liquid is used, from the viewpoint of moisture permeability resistance of the cured product of the resin composition, etc., it is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight based on 100% by weight of the nonvolatile matter of the epoxy resin. % is more preferably 1 to 6% by weight, still more preferably 1.5 to 5% by weight.

In the resin composition constituting the moisture-absorbing resin composition layer in the present invention, a curing accelerator may be further contained in order to adjust the curing temperature, the curing time, and the like. The hardening accelerator is, for example, a 4-grade ammonium salt such as a tetramethylammonium bromide or a tetrabutylammonium bromide, a tetraphenylphosphonium bromide or a tetrabutylphosphonium bromide, or a DBU (1,8). -diazabicyclo (5.4.0) undecene-7), DBN (1,5-diazabicyclo(4.3.0)nonene-5), DBU-phenolate, DBU-octanoate, DBU- a diazabicyclo compound such as p-toluenesulfonate, DBU-formate, DBU-novolac resin salt, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2 - an imidazole compound such as ethyl-4-methylimidazole, a tertiary amine such as tris(dimethylaminomethyl)phenol or benzyldimethylamine, an aromatic dimethyl urea, or an aliphatic dimethyl group A dimethyl urea compound such as urea or aromatic dimethyl urea.

The content when using the hardening accelerator is relative to the total amount of the epoxy resin. A range of 0.01 to 7 wt%.

(hygroscopic metal oxide)

The term "hygroscopic metal oxide" as used in the present invention means a metal oxide which has the ability to absorb moisture and chemically reacts with moisture-absorbing water to form a hydroxide, and is not particularly limited as long as it can achieve the object of the invention. Specifically, for example, a mixture or a solid solution of one or more selected from the group consisting of calcium oxide, magnesium oxide, cerium oxide, aluminum oxide, and cerium oxide, or two or more selected metal oxides. Examples of the mixture or solid solution of two or more kinds of metal oxides include, for example, calcined dolomite (containing a mixture of calcium oxide and magnesium oxide) and calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide) Things). Such hygroscopic metal oxides are known as hygroscopic materials in various technical fields, and commercially available products can be used. Specifically, for example, fired dolomite ("KT" manufactured by Yoshizawa Lime Co., Ltd.), calcium oxide ("moistop #10" manufactured by Sankyo Powder Co., Ltd.), and magnesium oxide (KYOWAMAG MF-150 manufactured by Kyowa Chemical Industry Co., Ltd.) "KYOWAMAG MF-30", "PUREMAG FNMG" manufactured by Tateho Chemical Co., Ltd.), lightly burned magnesia ("#500", "#1000", "#5000", etc., manufactured by Tateho Chemical Industry Co., Ltd.).

The average particle diameter of the hygroscopic metal oxide is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less. The use of such a small size not only imparts a high moisture permeability resistance to the hardened layer of the moisture absorbing resin composition, but also improves the adhesion. When the average particle diameter of the hygroscopic metal oxide is too small, the particles aggregate with each other, and the sheet processing tends to be difficult. The average particle diameter of the hygroscopic metal oxide is preferably 0.01 μm or more, and more preferably 0.1 μm or more.

When the average particle diameter of the commercially available product of the hygroscopic metal oxide is 10 μm or less, it can be used as it is. However, when the average particle diameter of the commercially available product exceeds 10 μm, the granules having an average particle diameter of 10 μm or less are prepared by pulverization or classification. After that, the use is better.

Here, the "average particle diameter" is an equal diameter of the particle size distribution when the particle size distribution of the measurement target (granular material) is prepared on a volume basis. The particle size distribution of the volume basis can be measured by a laser diffraction or scattering method according to the Mie scattering theory, and a laser diffraction type particle size distribution measuring apparatus, specifically, LA-500 manufactured by Horiba, Ltd. can be used. The measurement sample is preferably one in which the hygroscopic metal oxide is dispersed in water by ultrasonic waves.

The hygroscopic metal oxide can be used as a surface treatment agent. By using such a surface-treated hygroscopic metal oxide, the storage stability of the resin composition constituting the moisture absorbing resin composition layer can be improved, and the moisture in the resin and the hygroscopic metal oxide can be prevented at the stage before the hardening. reaction.

As the surface treatment agent used for the surface treatment, specifically, 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, octadecanoic acid, myristic acid or palmitic acid, and more preferably stearic acid. These may be used alone or in combination of two or more.

The alkyl decanes are, for example, methyltrimethoxydecane or ethyltrimethoxy. Decane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, octadecyltrimethoxydecane, dimethyldimethoxydecane, octyltriethoxydecane, n- Octadecyldimethyl(3-(trimethoxycarbamidino)propyl)ammonium chloride or the like. These may be used alone or in combination of two or more.

The decane coupling agent is specifically, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxypropyl (dimethoxy) Epoxy decane coupling agent such as methyl decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; 3-hydrothiopropyltrimethoxydecane, 3-hydrogenthio a thiol-based decane coupling agent such as propyl triethoxy decane, 3-hydrothiopropylmethyldimethoxy decane or 11-hydrothioundecyltrimethoxy decane; 3-amino group Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N -Methylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane and N-(2-aminoethyl)-3-aminopropyl Amino decane coupling agent such as dimethoxymethyl decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane, vinyl trimethoxy decane, vinyl triethoxy Vinyl decane coupling of decane and vinylmethyldiethoxy decane Styrene-based decane coupling agent such as p-styryltrimethoxydecane; acrylate such as 3-propenyloxypropyltrimethoxydecane and 3-methylpropoxypropyltrimethoxydecane a decane coupling agent; an isocyanate decane coupling agent such as 3-isocyanate propyl trimethoxy decane, bis(triethoxymethyl sulfonylpropyl) disulfide, bis (triethoxymethyl sulfonyl propyl acrylate) a sulfide-based decane coupling agent such as tetrasulfide; phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium, triazine decane, and the like. These may be used alone or in combination of two or more.

Specifically, the surface treatment is carried out by dispersing the untreated hygroscopic metal oxide at a normal temperature using a mixer, while adding a surface treatment agent for spraying, and stirring for 5 to 60 minutes. As the mixer, a known mixer can be used. Specifically, for example, a mixer such as a V mixer, a belt mixer or a W-type mixer, a mixer such as a Henshell mixer or a cement mixer, a ball mill, a cutting mill, etc. . Further, when the absorbent material is pulverized by a ball mill or the like, the above-mentioned higher fatty acid, alkyldecane or decane coupling agent may be mixed and subjected to a surface treatment. The amount of the surface treatment agent to be treated varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, and is preferably from 1 to 10% by weight based on the hygroscopic metal oxide.

The upper limit of the content of the hygroscopic metal oxide in the resin composition is such that when the content of the hygroscopic metal oxide is too large, the viscosity of the resin composition rises, and the strength of the cured product decreases and becomes brittle. The nonvolatile content in the resin composition is 100% by weight, preferably 40% by weight or less, more preferably 35% by weight or less, still more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight or less. the following. The lower limit of the content of the hygroscopic metal oxide is preferably 100% by weight, preferably 1% by weight, based on the nonvolatile content in the resin composition, from the viewpoint of sufficiently obtaining the effect of containing the hygroscopic metal oxide. The above is more preferably 5% by weight or more, and still more preferably 10% by weight or more.

(inorganic filler)

The resin composition constituting the moisture absorbing resin composition layer may further contain an inorganic filler (but not a hygroscopic metal oxide). By containing the inorganic filler, the moisture permeability of the cured product of the resin composition can be improved, and the small depression of the composition at the time of film formation can be prevented, and the adhesion to the support or the sealing material can be improved. Specific examples of the inorganic filler include cerium oxide, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, and titanic acid. Magnesium, barium titanate, titanium oxide, barium zirconate, calcium zirconate, talc, clay, mica, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, strontium Run soil and so on. The inorganic filler may be used alone or in combination of two or more. In the above, from the viewpoint that the inorganic filler is not easily transferred to the other layer during lamination, it is preferable that the particles in the form of talc, clay, mica, and boehmite are flat-shaped fillers, and the particle form is used as a flat plate. The filler of the shape can further improve the moisture permeability of the hardened layer obtained by hardening the moisture-absorbing resin composition layer.

The upper limit of the average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, from the viewpoint of improving dispersibility or preventing deterioration of mechanical strength or laminating, and the inorganic filler is less likely to migrate to the other layer. Preferably, it is 0.6 μm or less. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, from the viewpoint of preventing a decrease in dispersibility due to aggregation or preventing a decrease in viscosity of the resin composition. It is 0.3 μm or more. The average particle diameter therein means the same meaning as the average particle diameter in the above-mentioned hygroscopic metal oxide.

The upper limit of the content of the inorganic filler in the resin composition is such that when the content of the inorganic filler is too large, the viscosity of the resin composition increases, and the strength of the cured product decreases and becomes brittle, and the non-volatile matter in the resin composition It is 100% by weight, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, still more preferably 30% by weight or less. The lower limit of the content of the inorganic filler is preferably 1% by weight or more, and more preferably 5% by weight or more based on 100% by weight of the nonvolatile content in the resin composition, from the viewpoint of sufficiently obtaining the effect of the inorganic filler. More preferably, it is 10% by weight or more.

(rubber particles)

The resin composition constituting the moisture-absorbing resin composition layer may further contain rubber particles, and the rubber particles may improve the mechanical strength and stress relaxation of the cured product of the resin composition. The rubber particles are not dissolved in the organic solvent in the varnish of the resin composition, and are also incompatible with the components in the resin composition such as an epoxy resin, and are present in a dispersed state in the varnish of the resin composition. Better.

In general, such rubber particles are obtained by increasing the molecular weight of the rubber component to such an extent that it is not dissolved in an organic solvent or a resin, and specifically, for example, a core-shell type rubber particle or a cross-linked acrylonitrile Ethylene 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 specific examples thereof include a two-layer structure in which a shell layer of an outer layer is a glassy polymer, a core 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 rubber-like polymer, and the core layer is a three-layer structure composed of a glassy polymer. Specifically, the glass layer is composed of a polymer of methyl methacrylate or the like, and the rubber-like polymer layer is specifically composed of a butyl acrylate polymer (butyl acrylate rubber) or the like. The upper limit of the average particle diameter of the primary particles of the rubber particles is preferably 2 μm or less from the viewpoint of maintaining the effect of stress relaxation or preventing the resin composition from damaging the element when the organic EL element is sealed. In addition, the lower limit of the average particle diameter of the primary particles of the rubber particles is preferably 0.05 μm or more from the viewpoint of preventing the viscosity at the time of mixing with the resin from increasing and causing deterioration in usability. 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 Japan Zeon Co., Ltd.). Specific examples of the acrylonitrile butadiene rubber (NBR) particles include XER-91 (manufactured by JSR Corporation). Specific examples of the styrene butadiene rubber (SBR) particles include XSK-500 (manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include metablen W300A and W450A (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles can be measured by dynamic light scattering. Specifically, the rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is produced by weight using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.) as the average particle diameter. To determine.

The upper limit of the content of the rubber particles is preferably 20% by weight or less based on 100% by weight of the nonvolatile matter in the moisture absorbing resin composition layer from the viewpoint of preventing the heat resistance and moisture permeability of the moisture absorbing resin composition layer from being lowered. Better yet 10% by weight or less. The lower limit of the content of the rubber particles is preferably 0.1% by weight or more based on 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer from the viewpoint of sufficiently obtaining the effect of blending the rubber particles.

A rubber particle-dispersed epoxy resin in which rubber particles are dispersed in an epoxy resin in a state of primary particles is commercially available, and a rubber particle-dispersed epoxy resin is used as the epoxy resin, and rubber particles may be contained in the resin composition. Specifically, the rubber particle-dispersed epoxy resin is, for example, "BPA328" manufactured by Nippon Shokubai Co., Ltd. (rubber particles: acrylic core-shell resin, average particle diameter of rubber particles: 0.3 μm, rubber particle content: 17 weight %, epoxy resin: epoxy equivalent of 185 bisphenol A epoxy resin), "MX120" manufactured by Kaneka Co., Ltd. (rubber particles: SBR resin, average particle diameter of rubber particles: 0.1 μm, rubber particle content: 25 Weight%, epoxy resin: epoxy equivalent of 185 bisphenol A type epoxy resin) and the like.

(thermoplastic resin)

The resin composition constituting the moisture absorbing resin composition layer may further contain a thermoplastic resin. By containing a thermoplastic resin, flexibility can be imparted to the cured product of the resin resin composition, and good workability in coating the resin composition can be imparted. Specific examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, a polyamidoximine resin, a polyether oxime resin, a polyfluorene resin, and the like. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin is preferably 10,000 or more, and more preferably 30,000 or more, from the viewpoint of imparting flexibility and preventing dents during coating. But when the weight average molecular weight is too large, The compatibility of the oxygen resin tends to decrease, and the weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less.

The "weight average molecular weight of the thermoplastic resin" is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight of the GPC method, specifically, LC-9A/RID-6A manufactured by Shimadzu Corporation, the Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd., and chloroform in the mobile phase. Etc., measured at a column temperature of 40 ° C, calculated using a standard polystyrene calibration line.

The thermoplastic resin is particularly preferably a phenoxy resin in the above examples. The phenoxy resin is preferably compatible with the "epoxy resin" and has little effect on the adhesion and moisture resistance of the cured product of the resin composition.

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

A commercially available product of a phenoxy resin is specifically 1256, 4250 (a phenoxy resin containing a bisphenol A skeleton) manufactured by Japan Epoxy Resins Co., Ltd., and YX8100 (a benzene containing a bisphenol S skeleton) manufactured by Japan Epoxy Resins Co., Ltd. Oxygen resin), YX6954 (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Japan Epoxy Resins Co., Ltd., PKHH (weight average molecular weight (Mw) 42600, number average molecular weight (Mn) 11200) manufactured by Union Carbide Co., Ltd., etc. In addition, Dongdu Chemical Co., Ltd. FX280, FX293, Japan Epoxy Resins company YL7553BH30, YL6794, YL7213, YL7290, YL7482 and so on.

The upper limit of the content of the thermoplastic resin is preferably 50% by weight or less, more preferably 25% by weight based on 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer from the viewpoint of preventing deterioration of moisture permeability of the cured product. %the following. In addition, the lower limit of the content of the thermoplastic resin is preferably 1% by weight or more, more preferably 1% by weight or more, based on 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer from the viewpoint of obtaining a sufficient effect of containing the thermoplastic resin. It is 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more.

(coupling agent)

The moisture absorbing resin composition layer used in the present invention further contains a coupling agent to improve the adhesion of the adherend (support, protective resin composition layer, sealing material, etc.) of the cured product or the penetration resistance of the cured product. Wet. Specific examples of the coupling agent include a titanium coupling agent, an aluminum coupling agent, and a decane coupling agent. Among them, a decane coupling agent is preferred. These may be used alone or in combination of two or more.

The decane coupling agent is specifically, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxypropyl (dimethoxy) Epoxy decane coupling agent such as methyl decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; 3-hydrothiopropyltrimethoxydecane, 3-hydrogenthio a thiol-based decane coupling agent such as propyl triethoxy decane, 3-hydrothiopropylmethyldimethoxy decane or 11-hydrothioundecyltrimethoxy decane; 3-amino group Propyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N-methylamino Propyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane and N-(2-aminoethyl)-3-aminopropyldimethoxy An amine-based decane coupling agent such as methyl decane; a urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl Vinyl decane coupling agent such as bis ethoxy decane; styryl decane coupling agent such as p-styryl trimethoxy decane; 3-propenyloxypropyltrimethoxy decane and 3-methyl Acrylate-based decane coupling agent such as acryloxypropyltrimethoxydecane; isocyanate-based decane coupling agent such as 3-isocyanate propyltrimethoxydecane, bis(triethoxymethyl sulfonylpropyl) disulfide a sulfide-based decane coupling agent such as bis(triethoxymethanealkylpropyl)tetrasulfide; phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium , triazine decane, and the like. Among these, an epoxy decane coupling agent is particularly preferred.

The upper limit of the content of the coupling agent is preferably 10% by weight or less, more preferably 10% by weight or less, based on 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer, from the viewpoint of obtaining the adhesion improving effect by the coupling agent. 5% by weight or less. The lower limit of the content of the coupling agent is preferably 0.5% by weight or more based on 100% by weight of the nonvolatile content in the moisture-absorbing resin composition layer from the viewpoint of obtaining the adhesion improving effect by the coupling agent.

In the hygroscopic resin composition layer used in the present invention, various additives other than the above components may be optionally contained within the range in which the effects of the present invention are exerted. Specific examples of such additives are polyfluorene oxide powder, nylon powder, and fluorine powder. Such as organic fillers, olben, benton, etc., tackifiers, polyfluorene, fluorine, polymer defoamers or flat agents, triazole compounds, thiazole compounds, three An adhesion imparting agent such as a azine compound or a porphyrin compound.

The thickness of the moisture-absorbing resin composition layer used in the present invention is not particularly limited, and in the structure in which the support is laminated on the resin composition layer, the moisture is immersed only on the side of the resin composition layer, thereby lowering the moisture-absorbing resin composition. The thickness of the layer is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less, from the viewpoint of reducing the contact area with the outside air and blocking the moisture. The lower limit of the thickness is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more from the viewpoint of ensuring a concentration of the moisture absorbent for obtaining a sufficient moisture absorption effect.

[Protective Resin Composition Layer]

The protective resin composition layer used for the film of the present invention is composed of a thermosetting resin composition containing a thermosetting resin or a curing agent, and is used in a closed structure of a device (organic EL device or the like). The directly coated element (organic EL element or the like) has a function of preventing the hygroscopic metal oxide contact element in the moisture absorbing resin composition layer from damaging the element.

(thermosetting resin and hardener)

The thermosetting resin and the curing agent are the same as those of the thermosetting resin and the curing agent used in the moisture-absorbing resin composition layer. The thermosetting resin and the hardener used for the protective resin composition layer may also be composed of a hygroscopic resin. When the thermosetting resin and the curing agent used in the material layer are different from each other, the resin is protected from the viewpoint of suppressing the interfacial stress between the two layers after hardening due to the difference in adhesion between the two layers, the curing shrinkage, and the curing speed. The thermosetting resin and the curing agent used for the composition layer are preferably the same as the thermosetting resin and the curing agent used for the moisture-absorbing resin composition layer.

(hygroscopic metal oxide)

The protective resin composition layer used in the present invention may further contain a hygroscopic metal oxide within a range that does not affect the damage prevention function of the organic EL element. The moisture permeability resistance can be improved by containing a hygroscopic metal oxide.

When the protective resin composition layer contains a hygroscopic metal oxide, the upper limit of the content of the hygroscopic metal oxide is 100% by weight relative to the non-volatile content in the protective resin composition layer from the viewpoint of damage prevention of the organic EL element. Preferably, it is 5% by weight or less. In addition, the lower limit of the content of the moisture-absorbing metal oxide is preferably 0.5% by weight or more based on 100% by weight of the nonvolatile content in the protective resin composition layer from the viewpoint of obtaining an effect of improving moisture permeability.

When the hygroscopic metal oxide contains a hygroscopic metal oxide in a range of not more than 5% by weight in the protective resin composition layer, the particle size of the hygroscopic metal oxide may be damaged. The EL element, therefore, the average particle diameter of the hygroscopic metal oxide is preferably less than 1 μm. In addition, even if the average particle diameter is less than 1 μm, when the particle size distribution is broad, coarse particles are contained, and the organic EL element may be damaged. Therefore, the average particle diameter is more preferably less than 1 μm, and particles having a particle diameter of 3 μm or more are not contained. By.

Further, the hygroscopic metal oxide contained in the protective resin composition layer may be the same metal oxide as the hygroscopic metal oxide contained in the moisture-absorbing resin composition layer, or may be the same as the surface treatment. The situation is implemented. When the average particle diameter of the commercial product is less than 1 μm, the commercially available product of the hygroscopic metal oxide can be used as it is, and when the average particle diameter of the commercially available product is 1 μm or more, pulverization, classification, and the like are carried out to prepare an average particle diameter. A pellet of less than 1 μm is used. The "average particle diameter" herein has the same meaning as the average particle diameter of the hygroscopic metal oxide contained in the moisture-absorbing resin composition layer.

(inorganic filler)

The protective resin composition layer used in the present invention further contains an inorganic filler (but does not contain a hygroscopic metal oxide), and can retard the moisture permeability at the interface between the layer and the EL element side, thereby improving the adhesion to the substrate. force. The inorganic filler can be the same as the inorganic filler used in the above-mentioned absorbent resin composition layer. From the viewpoint of the fact that the inorganic filler is not easily exposed at the time of lamination, it is preferable that the particles in the form of talc, clay, mica, and boehmite are flat-shaped fillers. When the inorganic filler is used, the upper limit of the content of the inorganic filler is preferably from 100% by weight to the nonvolatile content in the resin composition from the viewpoint that the viscosity of the resin composition increases and the strength of the cured product decreases and becomes brittle. 15% by weight or less, more preferably 10% by weight or less. The lower limit of the content of the inorganic filler is not related to the effect of the moisture permeability of the interface between the resin composition layer and the EL element side. The volatile matter is 100% by weight, preferably 1% by weight or more, more preferably 3% by weight or more. When the inorganic filler is used together with the hygroscopic metal oxide, the total amount of the inorganic filler and the hygroscopic metal oxide is in the range of 15% by weight or less based on 100% by weight of the nonvolatile content in the resin composition. use.

(rubber particles, thermoplastic resin, coupling agent, etc.)

The protective resin composition layer used in the present invention further contains rubber particles to improve the mechanical strength and stress relaxation of the cured product. Further, in the moisture-absorbing resin composition layer used in the present invention, by further containing a thermoplastic resin, flexibility can be imparted to the cured product, and good workability in coating the resin composition can be imparted. The moisture absorbing resin composition layer used in the present invention further contains a coupling agent to improve the adhesion of the adherend to the cured product and the moisture permeability resistance of the cured product. The rubber particles, the thermoplastic resin, the coupling agent, and the like may be the same as the rubber particles, the thermoplastic resin, the coupling agent, and the like used in the moisture-absorbing resin composition layer, and the coupling agent is preferably a decane coupling agent, and the thermoplastic resin is more preferable. Jia is a phenoxy resin. The content of the thermosetting resin composition is basically the same as that of the rubber particles, the thermoplastic resin, and the coupling agent in the thermosetting resin composition constituting the moisture absorbent resin composition layer.

In the protective resin composition layer used in the present invention, various additives other than the above components may be optionally contained within the range in which the effects of the present invention are exerted. Specific examples of the additives include organic fillers such as polyfluorene oxide powder, nylon powder, and fluorine powder, and viscosities such as olben and benton. An agent, a polyfluorene-based, a fluorine-based, a polymer-based antifoaming agent, a flattening agent, a triazole compound, a thiazole compound, a triazine compound, a porphyrin compound, or the like.

The thickness of the protective resin composition layer used in the present invention is not particularly limited, and the upper limit of the thickness is preferably 40 μm or less, and more preferably 20 μm or less from the viewpoint of an increase in the moisture permeability. Further, from the viewpoint of the thickness sufficient to have the damage preventing effect of the organic EL element, the lower limit of the thickness is preferably 1 μm or more.

[protective film]

The film of the present invention is actually used until the formation of the closed structure. In order to prevent adhesion or scratches on the surface of the resin composition layer, it is preferable to protect the film. The protective film may be a plastic exemplified by the above-mentioned peeling support. film. The protective film is preferably subjected to a release treatment in advance, and the release agent is specifically, for example, a fluorine-based release agent, a polyoxymethylene-based release agent, or an alkyd-based release agent. The release agent can be mixed with different types of people. The thickness of the protective film is not particularly limited, but is preferably 1 to 100 μm, more preferably 10 to 75 μm, still more preferably 15 to 50 μm.

[Film manufacturing method]

The film of the present invention is not particularly limited, and can be used for various devices such as semiconductors, solar cells, high-brightness LEDs, LCD seals, and organic ELs, and is particularly suitable for use in organic EL devices for sealing, and is applicable to organic EL devices. Further, when the film of the present invention is transported, protective film transport can be added. In other words The composition of the film of the present invention includes the following six aspects.

(1) Peeling support + hygroscopic resin composition layer + protective resin composition layer + protective film

(2) Closed system support + hygroscopic resin composition layer + protective resin composition layer + protective film

(3) Peeling support + protective resin composition layer + hygroscopic resin composition layer + protective film

(4) Peeling support + moisture absorbing resin composition layer + protective resin composition layer

(5) Closed system support + hygroscopic resin composition layer + protective resin composition layer

(6) Peeling support + protective resin composition layer + hygroscopic resin composition layer

The above indicates the lamination order of each layer.

In the constitution of (1) and (2) of the film of the present invention, specifically, the first varnish in which the resin composition constituting the moisture absorbing resin composition layer is dissolved and the resin constituting the protective resin composition layer are separately prepared. The first varnish is coated on the release support or the seal support, and the organic solvent is dried to form a moisture-absorbing resin composition layer, and the second varnish is applied thereon to dry the organic solvent. A protective resin composition layer is formed and then a protective film is used. Further, the structure of the film (3) of the present invention is obtained by inversely forming a protective resin composition layer and a moisture-absorbing resin composition layer. The configuration of (4), (5), and (6) of the film of the present invention means that when a film composed of (1), (2), and (3) is produced, no protective film is used. The composition of the film.

When the film of the present invention has the constitutions of (1) and (3), the relationship between the release-based support and the protective film is that the protective film must be peeled off first, and the protective film is thinner than the release-based support, or the release film is applied to the protective film. Processing or embossing is preferred. Further, the release-system support is preferably a polyethylene terephthalate (PET) film, and the protective film is preferably a 2-axis stretched polypropylene.

The organic solvent used for the varnish is exemplified by acetone, methyl ethyl ketone (hereinafter referred to as "MEK"), ketones such as cyclohexanone, ethyl acetate, butyl acetate, serosu acetate, and propylene glycol. Acetate such as methyl ether acetate or carbitol acetate, carbitol such as celecoxib or butyl carbitol, aromatic hydrocarbon such as toluene or xylene, and dimethylformamidine Amine, dimethylacetamide, N-methylpyrrolidone, and the like. These may be used alone or in combination of two or more.

The drying conditions are not particularly limited, but are preferably 50 to 100 ° C for 3 to 15 minutes.

The method for producing the film of the present invention in the order of the moisture absorbing resin composition layer and the protective resin composition layer on the support, or in the reverse order, in the moisture absorbing resin composition layer and the protective resin composition layer In the boundary between the two layers of the resin composition, the protective resin composition layer may be damaged and the damage prevention effect of the organic EL element may be caused. Therefore, the first varnish is used to form the first resin composition sheet in which the moisture absorbing resin composition layer is formed, and the second varnish is used in the second support to form the protective resin. a second resin composition sheet of the composition layer, and a moisture absorbing resin composition layer of the first resin composition sheet The method of laminating the protective resin composition layer of the second resin composition sheet to obtain the film of the present invention is preferred. Further, at this time, any of the first support and the second support is a support of the film of the present invention, and the other is a protective film of the film of the present invention.

When the film of the present invention is obtained by this method, the melt viscosity of the protective resin composition layer is preferably lower than the melt viscosity of the moisture-absorbing resin composition layer at the laminating temperature of the moisture-absorbing resin composition layer and the protective resin composition layer. In other words, at the laminating temperature of the moisture absorbing resin composition layer and the protective resin composition layer, the melt viscosity of the resin composition constituting the protective resin composition layer is lower than that of the moisture absorbing resin composition layer, and the hygroscopic resin can be avoided. The filler contained in the composition layer moves to the protective resin composition layer at the time of lamination, or damages the EL element by protecting the resin composition layer.

The term "melt viscosity" refers to the type of Rheosol-G3000 manufactured by UBM, the resin amount is 1 g, and a parallel plate having a diameter of 18 mm is used. The measurement start temperature is 60 ° C, the temperature increase rate is 5 ° C / min, and the measurement temperature is 60 ° C to 200 ° C. The value measured at a vibration number of 1 Hz/deg.

The laminating temperature is not particularly limited, and may be appropriately set in accordance with the required properties, and is required to be lower than the curing temperature of the moisture-absorbing resin composition layer and the protective resin composition layer. Therefore, the upper limit of the lamination temperature is preferably 130 ° C or lower. Preferably, it is 120 ° C or less, more preferably 110 ° C or less, more preferably 100 ° C or less. Further, the lower limit of the lamination temperature is preferably 40° C. or higher, more preferably 45° C. or higher, more preferably 50° C. or higher, still more preferably 55° C. or higher, and particularly preferably 60, from the viewpoint of good usability at normal temperature. Above °C. The hygroscopic resin composition layer and the protective resin composition layer are not mixed with each other at a set laminating temperature The viewpoint of preventing the hygroscopic metal oxide from moving to the protective resin composition layer, the difference between the melt viscosity of the moisture-absorbing resin composition layer and the melt viscosity of the protective resin composition layer (melting viscosity of the moisture-absorbing resin composition layer) The lower limit of the melt viscosity of the protective resin composition layer is preferably 300 poise or more, more preferably 1000 poise or more, more preferably 5,000 poise or more, still more preferably 10,000 poise or more, particularly preferably 15,000 poise or more, and most preferably 30,000 poise or more. Further, at the set laminating temperature, the viewpoint of effectively fixing the moisture absorbing resin composition layer and the protective resin composition layer at one time, and efficiently attaching the moisture absorbing resin composition layer and the protective resin composition layer, suction The upper limit of the difference between the melt viscosity of the wet resin composition layer and the melt viscosity of the protective resin composition layer (the melt viscosity of the moisture-absorbing resin composition layer - the melt viscosity of the protective resin composition layer) is preferably 1,000,000 poise or less, more preferably Below 500000poise, more preferably below 100000poise.

The method for adjusting the melt viscosity of the protective resin composition layer and the moisture-absorbing resin composition layer, for example, a method of changing the degree of hardening by drying conditions, a method of changing the blending ratio of the liquid resin, changing the particle diameter of the inorganic filler, and containing A method such as a ratio or the like can be carried out by combining two or more of these. Therefore, by adjusting the viscosity of the protective resin composition layer and the moisture-absorbing resin composition layer by such a method, the melt viscosity of the protective resin composition layer at a predetermined temperature can be made lower than the melt viscosity of the moisture-absorbing resin composition layer. .

The film of the present invention is suitable for forming a closed structure of various semiconductor elements (individual semiconductors, optical semiconductors, logic ICs, analog ICs, memories, etc.), and is particularly suitable for the sealing of organic EL elements.

[Method of Manufacturing Organic EL Device]

A method of producing an organic EL device by using the film-sealed organic EL device of the present invention will be described below. In the closed structure of the apparatus, an element for forming a substrate by covering the element with the protective resin composition layer is disposed, and the moisture-absorbing resin composition layer is disposed on a surface opposite to the side surface of the element forming substrate of the protective resin composition layer. The structure of the film of the present invention contains the following six aspects as described above.

(1) Peeling support + hygroscopic resin composition layer + protective resin composition layer + protective film

(2) closed system support + hygroscopic resin composition layer + protective resin composition layer + protective film,

(3) peeling support + protective resin composition layer + hygroscopic resin composition layer + protective film,

(4) Peeling support + moisture absorbing resin composition layer + protective resin composition layer

(5) Closed system support + hygroscopic resin composition layer + protective resin composition layer

(6) Peeling support + protective resin composition layer + hygroscopic resin composition layer

(a) When the film of the present invention has the constitution (1), the protective film is first removed, and the protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed. Then, the release-system support is peeled off, and the sealing material is laminated on the exposed moisture-absorbing resin composition layer to perform a protective resin composition. The organic EL device can be manufactured by a thermal hardening operation of the layer and the moisture absorbing resin composition layer.

(b) When the film of the present invention has the constitution of (2), the protective film is first removed, and the protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed, and the protective resin composition layer and the moisture absorbing resin are formed. The organic EL device can be manufactured by a thermal hardening operation of the layer.

(c) When the film of the present invention has the constitution (3), the protective film is first removed, and the moisture-absorbing resin composition layer is laminated on the sealing material. Then, the release-system support is peeled off, and the exposed protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed, and the protective resin composition layer and the moisture-absorbing resin composition layer are thermally hardened. An organic EL device is manufactured.

(d) When the film of the present invention has the configuration of (4), the protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed. Then, the release-type support is peeled off, and the sealing material is laminated on the exposed moisture-absorbing resin composition layer to perform a heat-hardening operation of the protective resin composition layer and the moisture-absorbing resin composition layer, whereby an organic EL device can be produced.

(e) When the film of the present invention is in the configuration of (5), the protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed, and the protective resin composition layer and the moisture absorbent resin composition layer are formed in this state. The organic EL device can be manufactured by a heat hardening operation.

(f) When the film of the present invention has the configuration of (6), the moisture-absorbing resin composition layer is laminated on the sealing material, and then the release-type support is peeled off, and the exposed protective resin composition layer is laminated. Organic EL element On the transparent substrate, a thermal curing operation of the protective resin composition layer and the moisture-absorbing resin composition layer is performed, whereby an organic EL device can be manufactured.

In the organic EL device, it is preferable to produce the organic EL device by the method of (b), (c), (e) or (f) from the viewpoint of not applying the heat history more than necessary.

The sealing material used in the methods (a), (c), (d) and (f) is different from the film of the present invention, and is additionally prepared to form a material for a closed structure, for example, having a moisture-proof property. Metal foil, glass plate, metal plate, etc. of plastic film, copper foil, aluminum foil, and the like. The upper limit of the thickness of the sealing material is preferably 5 mm or less, more preferably 1 mm or less, and still more preferably 100 μm or less from the viewpoint of making the organic EL device itself light and thin. In addition, the lower limit of the thickness of the sealing material is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more from the viewpoint of preventing moisture permeation and the rigidity of the organic EL device. The sealing material can be used in combination of two or more sheets. In this case, the total thickness after lamination is preferably in the range of 5 μm or more and 5 mm or less.

The lamination method carried out in the above methods (a) to (f) may be a batch type or a continuous type of rolls. The lamination conditions can be carried out under reduced pressure, and lamination can be preferably carried out using a vacuum laminator or the like. The lamination is preferably carried out under conditions of a pressure of 10 ^-3 (10 hPa) MPa or less, a temperature of 50 to 130 ° C, and a pressure of 0.5 to 10 kgf / cm ² . Specific examples of the vacuum laminator include a vacuum press laminator manufactured by a company, a vacuum coater manufactured by Nichigo-morton Co., Ltd., and the like.

The protective resin composition layer and the moisture absorbent resin composition layer are thermally hardened The method is not particularly limited, and a known method can be used. Specifically, there are, for example, a hot air circulation type oven, an infrared heater, a heat gun, a high frequency induction heating device, and a pressure-sensitive heating of a heating tool. The film of the present invention has extremely excellent low-temperature curability, and the upper limit of the curing temperature is preferably 140 ° C or lower, more preferably 120 ° C or lower, still more preferably 110 ° C or lower. Further, from the viewpoint of ensuring the adhesion of the cured product, the lower limit of the curing temperature is preferably 50 ° C or higher, more preferably 55 ° C or higher. The upper limit of the hardening time is preferably 120 or less, more preferably 90 or less, and still more preferably 60 or less. From the viewpoint of surely hardening the cured product, the lower limit of the curing time is preferably 20 minutes or more, more preferably 30 minutes or more. Thereby, the thermal deterioration of the organic EL element can be reduced to an extremely low level.

In the organic EL device of the present invention, when the organic EL element is formed on the transparent substrate, when the transparent substrate side is the display surface of the display or the light-emitting surface of the lighting fixture, the sealing member or the sealing material does not have to use a transparent material. Use metal plates, metal foils, opaque plastic films or plates.

1‧‧‧Enclosed material (glass plate)

2‧‧‧Moisture-absorbing resin composition layer (inorganic filler, hygroscopic metal oxide)

3‧‧‧Protective resin composition layer (inorganic filler, no hygroscopic metal oxide)

4‧‧‧Organic EL components

5‧‧‧Substrate

6‧‧‧Resin composition layer (containing inorganic fillers, no hygroscopic metal oxides)

7‧‧‧Hygroscopic metal oxides

[figure 1]

Fig. 1(a) is a schematic cross-sectional view showing an organic EL device of the first embodiment, and Figs. 1(b) to 1(e) are schematic cross-sectional views of the organic EL devices of Comparative Examples 1 to 4.

[figure 2]

SEM photograph of the film cross section of Test Example 4.

[image 3]

SEM photograph of the film cross section of Test Example 5.

[Figure 4]

SEM photograph of the cross section of the film of Test Example 6.

[Examples]

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

[Use materials]

The materials used in the experiment are explained below.

(A) Epoxy resin

‧Solid epoxy resin (HP7200H made by DIC: dicyclopentadiene type solid epoxy resin, epoxy equivalent (278g/eq))

‧ Rubber microparticle dispersion liquid epoxy resin (BPA328 manufactured by Nippon Shokubai Co., Ltd.): Acrylic resin particles of two-layer structure with a primary particle diameter of 0.3 μm contain 17 weights in an epoxy equivalent of 185 bisphenol A epoxy resin. % composition. Epoxy equivalent (230g/eq))

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

(B) phenoxy resin

‧Japan Epoxy Resins company "YL7213-35M" (weight average molecular weight 35000) solid content of 35 wt% MEK solution

(C) hardener

‧Efficient hardening accelerator for epoxy resin ("U-CAT3502T" manufactured by San-apro Co., Ltd.)

‧Ionic liquid hardener ("TBP/N-Ac-gly", N-acetylglycolic acid tetrabutyl phosphonium salt)

(D) hygroscopic metal oxide

‧Breaked Dolomite: MEK glue for wet pulverizers made by Giza lime Co., Ltd. (solid weight: 40% by weight, average particle size: 0.87μm)

(E) Inorganic filler

‧ talc: MEK cement for wet pulverization "D-600" manufactured by Japan Talc Co., Ltd. (solid weight: 30% by weight, average particle diameter: 0.72 μm)

(F) surface treatment agent

‧ Stearic acid

(G) coupling agent

‧ Decane coupling agent: "KBM-403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd.

〔test methods〕

Next, the measurement method will be described.

[Adhesion between the support and the resin composition layer]

Two sheets of aluminum foil (width 50 mm, length 50 mm, thickness 50 μm) were prepared, and a resin composition layer (width 40 mm, length 50 mm) on the substrate was superposed on one surface of the first aluminum foil, and the temperature was increased by a vacuum laminator. Lamination was carried out under the conditions of 80 ° C and a pressure of 1 kgf/cm ² (9.8 × 10 ⁴ Pa). The base material was peeled off, and two aluminum foils were 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-hardened 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 adhesion force in the longitudinal direction of the test piece was measured in accordance with the T-peel test method of JIS K-6854. (Peel force).

[Evaluation method]

Next, the evaluation method will be described.

[Evaluation of moisture permeability]

The moisture resistance of the film was evaluated by subjecting the organic EL device to a constant temperature of 60 ° C / 90% RH for 1000 hours. The moisture permeability of the film is determined by the shrinkage of the light-emitting area generated by the light-emitting portion of the organic EL element and the state of DS (dark spot), and the relative change rate of the brightness at the initial stage (0 hours) and after 1000 hours is evaluated. . In other words, when shrinkage or many DSs are generated, the light-emitting area is reduced, and the brightness of the light-emitting portion is increased. The relative change rate of the brightness of the initial state of the trap becomes large. In addition, the brightness was measured at a constant current drive (15 mA) at 2 points, and the average value was calculated. When the relative change rate was less than 1.1, the evaluation was ○, and when the relative change rate was 1.1 or more, the evaluation was ×.

[Evaluation of damage resistance of components]

The degree of damage of the organic EL element was evaluated by the dark current value of the driving voltage of 3V. When the dark current value was less than 0.2 μA, it was evaluated as ○, and when it was 0.2 μA or more, it was evaluated as ×.

The curable resin composition varnishes A to E of the blending compositions shown in Table 1 below were prepared in the order shown below. The numerical values of the amounts of the materials shown in Table 1 are parts by weight.

(Manufacturing Example 1)

A mixed solution of a solid epoxy resin ("HP7200H" manufactured by DIC Corporation) dissolved in a phenoxy resin (MEK solution of 35 wt% of a solid content of "YL7213-35M" manufactured by Japan Epoxy Resins Co., Ltd.) was prepared and dissolved in the mixture. A rubber fine particle dispersion liquid epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd.), a liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), and a latent curing accelerator for epoxy resin (san-) "U-CAT3502T" manufactured by Apro Co., Ltd., decane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), ionic liquid hardener (tetrabutylphosphonium N-acetamidoglycolate), and MEK, using high-speed rotation The mixer was uniformly dispersed to obtain varnish A.

(Manufacturing Example 2)

A mixture A in which a solid epoxy resin ("HP7200H" manufactured by DIC Corporation) was dissolved in a phenoxy resin (MEK solution of 35 wt% of a solid content of "YL7213-35M" manufactured by Japan Epoxy Resins Co., Ltd.) was prepared. In addition, stearic acid was added to the MEK dope (solid content: 40% by weight) of the fired dolomite (manufactured by Yoshizawa Lime Co., Ltd.) to prepare a mixture B. Mixture mixture A, mixture B, talc (D-600 from Japan Talc Co., Ltd., wet pulverizer, 30% by weight of MEK cement), and rubber fine particle dispersion liquid epoxy resin (manufactured by Nippon Shokubai Co., Ltd.) BPA328"), a latent curing accelerator for epoxy resin ("U-CAT3502T" manufactured by San-apro Co., Ltd.), a liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), and a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) "KBM-403") was mixed using an ultra-high speed vacuum emulsifier type mixer (manufactured by PRIMIX Co., Ltd.). An ionic liquid hardener (N-ethinyl glycine tetrabutylphosphonium salt) was added thereto and uniformly dispersed using a high-speed rotary mixer to obtain a varnish B.

(Manufacturing Example 3)

The same method as the varnish A of Production Example 1 was carried out in accordance with the following Table 1, except that the talc (the wet pulverization of "D-600" manufactured by Nippon Talc Co., Ltd., 30% by weight of MEK cement) was added. Table varnish C.

(Manufacturing Example 4)

The varnish D was prepared according to the preparation table of the following Table 1 by the method similar to the varnish B of the manufacturing example 2.

(Manufacturing Example 5)

The varnish E was prepared in the same manner as in the varnish B of Production Example 2 in accordance with the preparation table of Table 1 below.

(Test Examples 1 to 3)

The adhesion to the support was measured for each of the resin composition layers produced by the varnishes B, D, and E. The results are shown in Table 2.

From the results of Table 2, it was found that the talc was blended in the resin composition layer of the film of the present invention, and the adhesion of the resin composition layer to the support was greatly improved.

(Test Examples 4 to 6)

The varnish A was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was set to 10 μm, and then The film was dried at 60 to 95 ° C for 12 minutes to obtain a protective resin composition layer A1. The protective resin composition layer A1 had a melt viscosity at 100 ° C of 6170 poise.

The varnish A was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was set to 10 μm, and then The mixture was dried at 60 to 80 ° C for 6 minutes to obtain a protective resin composition layer A2. Protective resin composition layer The melt viscosity of A2 at 100 ° C is 1030 poise.

The varnish B was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 30 μm, and then The film was dried at 60 to 95 ° C for 12 minutes to obtain a moisture-absorbing resin composition layer B1. The moisture absorption resin composition layer B1 had a melt viscosity at 100 ° C of 23,700 poise.

The varnish B was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 30 μm, and then The mixture was dried at 60 to 80 ° C for 6 minutes to obtain a moisture-absorbing resin composition layer B2. The moisture-absorbing resin composition layer B2 had a melt viscosity at 100 ° C of 4,460 poise.

In the combination shown in Table 3, a protective resin composition layer with a PET film and a moisture-absorbing resin composition layer with a PET film were attached to protect the resin composition layer from the moisture-absorbing resin composition layer by a vacuum layer. The film was laminated at a temperature of 100 ° C and a pressure of 1 kg/cm ² (9.8 × 10 ⁴ Pa) to prepare a film having a support, a protective resin composition layer and a moisture-absorbing resin composition layer (Test Example 4~) 6). Then, the vicinity of the boundary between the protective resin composition layer and the moisture-absorbing resin composition layer of the cross section of each film after the production by SEM (scanning electron microscope) was observed. Fig. 2 is a SEM photograph of a film cross section of Test Example 4, Fig. 3 is a SEM photograph of a film cross section of Test Example 5, and Fig. 4 is a SEM photograph of a film cross section of Test Example 6.

The difference in melt viscosity between the moisture absorbing resin composition layer and the protective resin composition layer in the film (melting viscosity of the moisture absorbing resin composition layer - protective resin group) The melt viscosity of the product layer was 17530 poise for the film of Test Example 4, 3430 poise for the film of Test Example 5, and -1710 poise for the film of Test Example 6. In the film of Test Example 4 (Fig. 2), the interface between the moisture-absorbing resin composition layer (upper layer) and the protective resin composition layer (lower layer) was slightly horizontal, and the moisture-absorbing metal oxide layer was not found to be composed of the moisture-absorbing resin. (Upper layer) Move to the protective resin composition layer (lower layer). The film of Test Example 5 (Fig. 3) also did not find that the hygroscopic metal oxide was moved from the moisture-absorbing resin composition layer (upper layer) to the protective resin composition layer (lower layer). In the film of Test Example 6 (Fig. 4), it was found that the hygroscopic metal oxide (light spot) 7 was moved from the moisture-absorbing resin composition layer (upper layer) to the protective resin composition layer (lower layer).

Next, an organic EL device was produced by the following procedure.

[Production of Organic EL Device] (cleaning of ITO substrate and sealing glass plate)

The cleaning system of the ITO (indium ‧ tin oxide) substrate and the sealing glass plate was carried out in a quiet room of class 10000 and a quiet room of class 100, respectively. The washing solvent used was a semiconductor washing lotion and ultrapure water (18 MΩ or more, and all organic carbon (TOC): less than 10 ppb), and an ultrasonic cleaner and a UV washing machine were used.

(evaporation step)

The degree of vacuum is 1~2×10 ^-4 Pa, and the evaporation rate is 1.0~2.0 Å/s. On a 30 mm square (longitudinal 30 mm × horizontal 30 mm), 0.7 mm thick glass substrate, Glass/SiO ₂ [53 nm] /ITO [55 nm] / PEDOT‧ PSS [40 nm] / α-NPD [50 nm] / Alq ₃ [50 nm] / LiF [0.8 nm] / Al [15 nm] The layers were vapor-deposited to prepare an organic EL device. The area of the light-emitting portion is 10 × 10 mm ² .

Further, "PEDOT‧PSS" is an abbreviation for "poly(3,4-extended ethyldioxythiophene)) ‧ (polystyrene sulfonic acid), "α-NPD" system (double [N-(1-naphthyl)" Abbreviation for -N-phenyl]benzidine and "Alq ₃ " is an abbreviation for tris(8-quinolinol)aluminum.

(closed organic EL element)

First, the film of the present invention was laminated on a glass plate (21 mm × 28 mm, 0.7 mm thick) of a sealing material. The lamination system was carried out in a quiet room of class 100 by vacuum pressing at 80 ° C under reduced pressure (1 × 10 ^-3 MPa or less) for 20 seconds and pressing for 20 seconds.

Next, the support was peeled off, and the resin composition layer exposed on the glass plate was placed in a toolbox having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less, and under a load of 80 ° C and 0.04 MPa, and a reduced pressure (1 × 10 ^{-3 )} MPa or less) Under the conditions of suction for 20 seconds and pressing for 20 seconds, vacuum pressing was performed on the organic EL element forming substrate.

Thereafter, the film of the present invention was thermally hardened by heating on a hot plate at 110 ° C for 30 minutes in a tool case.

In the above resin composition layer, the protective resin composition layer and the moisture absorbing resin composition layer are laminated, and the laminate of the glass plate of the sealing material is laminated on the glass plate to the organic EL element. The laminate forming the substrate laminates the protective resin composition to the organic EL element forming substrate on.

(Example 1)

The varnish A was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was set to 10 μm, and then It was dried at 60 to 95 ° C for 12 minutes to obtain a protective resin composition layer.

Similarly, the varnish B was uniformly applied to the release-treated surface of the PET film (thickness: 38 μm) treated with the alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 30 μm. Then, it was dried at 60 to 95 ° C for 12 minutes to obtain a moisture-absorbing resin composition layer.

The protective resin composition layer of the PET film and the moisture absorbing resin composition layer of the PET film are attached to protect the resin composition layer from the moisture absorbing resin composition layer, and the temperature is 80 ° C by a vacuum laminator. The film of the present invention was produced by laminating under the conditions of a pressure of 1 kg/cm ² (9.8 × 10 ⁴ Pa). The melt viscosity of the protective resin composition layer at 80 ° C was 27,500 poise, and the melt viscosity of the moisture-absorbing resin composition layer at 80 ° C was 63,400 poise. Next, the PET film on the side of the moisture-absorbing resin composition layer of the film is peeled off, and the moisture-absorbing resin composition layer is laminated on the glass plate of the sealing material, and the PET film on the side of the protective resin composition layer is peeled off to make the protective resin. The composition layer was laminated on a glass plate having an organic EL element to fabricate an organic EL device.

Fig. 1(a) is a schematic view showing a cross section of an organic EL device produced in the form of a protective resin composition layer (inorganic filler, not in the formation surface of the organic EL element 4 on which the substrate 5 of the organic EL element 4 is formed. Hygroscopic gold Oxide) 3, moisture absorbing resin composition layer (inorganic filler, hygroscopic metal oxide containing) 2 and sealing material (glass plate) 1 laminated in this order.

(Comparative Example 1)

The varnish B was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 40 μm, and then It was dried at 60 to 95 ° C for 12 minutes to obtain a resin composition layer. After the resin composition layer of the PET film was laminated on the glass plate of the sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element to fabricate an organic EL device.

Fig. 1(b) is a schematic cross-sectional view of the organic EL device produced by the substrate, and the surface of the organic EL element 4 on which the substrate 5 of the organic EL element 4 is formed is made of a resin composition layer (inorganic filler, containing a suction). Wet metal oxide 2) and the sealing material (glass plate) 1 are laminated in sequence.

(Comparative Example 2)

The varnish A was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 40 μm, and then It was dried at 60 to 95 ° C for 12 minutes to obtain a resin composition layer. After laminating the resin composition layer of the PET film on the glass plate of the sealing material, the PET film is peeled off, and the resin composition layer is laminated on the glass plate having the organic EL element. Organic EL device.

Fig. 1(c) is a schematic view showing a cross section of the organic EL device produced by the substrate, and the surface of the organic EL element 4 on which the substrate 5 of the organic EL element 4 is formed is made of a resin composition layer (inorganic filler, not included). The order laminate of the hygroscopic metal oxide 3 and the sealing material (glass plate) 1.

(Comparative Example 3)

A film was produced in the same manner as in Example 1 except that varnish C was used instead of varnish B. The PET film from the resin composition layer side of the varnish C of the film is peeled off, and the resin composition layer is laminated on the glass plate of the sealing material, and the PET film from the resin composition layer side of the varnish A is peeled off. This resin composition layer was laminated on a glass plate having an organic EL element to fabricate an organic EL device.

Fig. 1(d) is a schematic view showing a cross section of the organic EL device produced in the form of a resin composition layer (inorganic filler, not included) on the surface of the organic EL element 4 on which the substrate 5 of the organic EL element 4 is formed. The hygroscopic metal oxide 3, the resin composition layer (containing an inorganic filler, no hygroscopic metal oxide) 6 and a sealing material (glass plate) 1 are laminated in this order.

(Comparative Example 4)

The varnish C was uniformly applied to a release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd-based release agent using a die coater, and the thickness of the dried resin composition layer was 40 μm, and then It was dried at 60 to 95 ° C for 12 minutes to obtain a resin composition layer. PET film with PET film After the product layer was laminated on the glass plate of the sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element to fabricate an organic EL device.

Fig. 1(e) is a schematic view showing a cross section of an organic EL device produced by the organic EL device 4, and a surface of the organic EL device 4 on which the organic EL device 4 is formed, according to a resin composition layer (containing an inorganic filler, not A sequential laminate of a hygroscopic metal oxide 6 and a sealing material (glass plate) 1.

The performance evaluation results of the organic EL devices of Example 1 and Comparative Examples 1 to 4 are shown in Table 4.

It is understood from the first embodiment that the use of the film of the present invention can alleviate the damage of the organic EL element, and can form a high level of isolation by simply forming the organic EL element. A closed structure of a moisture-containing organic EL element. Further, in the first embodiment, the moisture absorbing resin composition layer and the protective resin composition layer are hardened at a low temperature to block the organic EL element, so that not only the damage of the organic EL element in the sealing operation but also the heat of the organic EL element can be sufficiently suppressed. Degradation, and a highly reliable organic EL element device is obtained.

On the other hand, Comparative Example 1 contained a large amount of hygroscopic metal oxide and damaged the organic EL element. Since Comparative Examples 2, 3, and 4 do not contain a hygroscopic metal oxide, the organic EL element is not damaged by moisture. Comparative Example 4 contained talc, but it was difficult to move due to the flat filler, and the damage resistance of the element was maintained.

[Industrial availability]

By providing a film having a support, a protective resin composition layer, and a moisture-absorbing resin composition layer, a film having both moisture permeability resistance and resistance to damage of the element can be realized, and the film can provide a highly reliable organic EL device.

The present application is based on Japanese Patent Application No. 2009-182827, the entire contents of which are incorporated herein.

Claims (6)

A film for sealing an organic EL element, which comprises a support, a protective resin composition layer, a moisture-absorbing resin composition layer, and a protective film, and is a laminated film in which a protective resin composition layer and a moisture-absorbing resin composition layer are adjacent to each other, The protective resin composition layer is a layer directly coating the organic EL element, the protective resin composition layer is a thermosetting resin composition containing a thermosetting resin and a curing agent, and the moisture absorbent resin composition layer is a thermosetting resin. And a thermosetting resin composition of a curing agent and a hygroscopic metal oxide, which are composed of a support, a hygroscopic resin composition layer, a protective resin composition layer, a protective film, or a support or a protective resin. The layer of the material layer, the layer of the moisture absorbing resin, and the protective film are laminated in this order, and the protective film is a plastic film which is subjected to release treatment by a releasing agent. The film of claim 1, wherein the adjacent protective resin composition layer and the moisture absorbent resin composition layer have a melt viscosity of the protective resin composition layer at a laminating temperature set in a range of 40 ° C to 130 ° C. The melt viscosity of the composition layer of the absorbent resin is lower, and the difference of the melt viscosity of the two layers is 300 poise to 1,000,000 poise. The film of claim 2, wherein the adjacent protective resin composition layer and the moisture-absorbing resin composition layer have a melt viscosity of the protective resin composition layer at a laminating temperature set in a range of 40 ° C to 130 ° C. The melt viscosity of the layer of the absorbent resin is lower, and the difference between the melt viscosities of the two layers is 3,430 poise to 1,000,000 poise. A film according to claim 1 or 2, wherein the moisture-absorbing resin composition layer contains an inorganic filler (but does not contain a hygroscopic metal oxide). A film according to claim 1 or 2, wherein the protective resin composition layer contains an inorganic filler (but does not contain a hygroscopic metal oxide). An organic EL device characterized by having a film according to any one of claims 1 to 5.