KR102121724B1 - Film - Google Patents

Abstract

The present invention is a film having a support, a protective resin composition layer and a moisture absorption resin composition layer. By such a structure, a film having sufficient moisture permeability and damage resistance of the device (that is, a function of preventing damage to the device) can be realized. The film of the present invention is particularly suitable for encapsulation of organic EL devices, and by using the film of the present invention, not only damage to the organic EL devices in the sealing operation, but also thermal deterioration of the organic EL devices is sufficiently suppressed, and the reliability is high. An EL element device can be obtained.

Description

Film {Film}

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

The organic EL (Electroluminescence) device is a light-emitting device using an organic material as a light-emitting material, and is a material that has recently been spotlighted to obtain high-intensity light emission at a low voltage. However, the organic EL element is very weak to moisture, the organic material itself is deteriorated by moisture, the luminance is lowered, the light is not emitted, the interface between the electrode and the organic EL layer is peeled off under the influence of moisture, or the metal is oxidized. There was a problem of becoming high resistance.

On the other hand, Patent Document 1 proposes that an organic EL layer is formed on a glass substrate, a curable resin layer is laminated to cover the entire organic EL layer, and a non-permeable glass substrate is pasted. However, since an acrylic ultraviolet-curable resin composition is used for the curable resin layer, there is a problem of deterioration of the organic EL device due to ultraviolet rays, or an uncured portion occurs in the absence of ultraviolet rays, and a highly reliable sealing structure is obtained. In terms of difficulty, it was not satisfactory.

Moreover, in patent document 2, the thermosetting type curable resin composition which performs the whole sealing of an organic EL element is proposed. However, it was not satisfactory in that the moisture permeability of the obtained cured product layer was insufficient.

Patent Document 1: Japanese Patent Application Publication No. (Pyeong) 5-182759 Patent Document 2: Japanese Patent Application Publication No. 2006-70221

An object of the present invention is to provide a film having both moisture permeability and damage resistance of a device, which are advantageous for forming a highly reliable sealing structure.

As a result of earnest research conducted by the inventors of the present invention, the present invention has been solved by a film having a support, a protective resin composition layer, and a moisture absorption resin composition layer, thereby completing the present invention.

That is, the present invention includes the following forms.

(1) A film comprising a support, a protective resin composition layer, and a moisture absorption resin composition layer.

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

(3) The film according to (1) or (2) above, wherein the moisture-absorbing resin composition layer contains an inorganic filler (except for a hygroscopic metal oxide).

(4) The film according to any one of (1) to (3) above, wherein the protective resin composition layer contains an inorganic filler (except for a hygroscopic metal oxide).

(5) At the lamination temperature set in the range of 40 to 130° C., the difference in melt viscosity between the moisture absorption resin composition layer and the protective resin composition layer (melt viscosity of the moisture absorption resin composition layer-melt viscosity of the protective resin composition layer) is 300 to The film according to any one of (1) to (4) above, which is 100000 poise.

(6) An organic EL device comprising the film according to any one of (1) to (5) above.

The film having the support, the protective resin composition layer, and the moisture absorption resin composition layer can provide a film having sufficient moisture permeability and damage resistance of the device (that is, a function of preventing damage to the device).

1A is a schematic cross-sectional view of the organic EL device of Example 1, and FIGS. 1B to 1E are schematic cross-sectional views of an organic EL device of Comparative Examples 1 to 4.
2 is an SEM photograph of a film cross section of Test Example 4.
3 is an SEM photograph of a film cross-section of Test Example 5.
4 is an SEM photograph of a film cross-section of Test Example 6.

The film of this invention has a support body, a moisture absorption resin composition layer, and a protective resin composition layer.

[Support]

The support used in the present invention means "a material supporting the protective resin composition layer or the moisture absorbing resin composition layer", but there is no particular limitation as long as it exhibits its function.

The support is classified into a peeling support and a sealing support.

The peeling-type support means a support that can be peeled at the time of production of various devices (i.e., support peeled (separated) from the film of the present invention at the time of production of various devices). As such a peeling-type support body, specifically, polyolefins, such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (it may be abbreviated as "PET" hereafter.), polyethylene naphthalate (hereinafter abbreviated as "PEN".) There may be cases.) Films made of plastics such as polyester, polycarbonate, polyimide, and the like. From the viewpoint of cost performance, a polyethylene terephthalate film and a polyethylene naphthalate film are preferred, and a polyethylene terephthalate film is more preferred.

Although the thickness of the peeling-based support is not particularly limited, from the viewpoint of the handleability 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, and even more preferably 90 μm or less. Do. On the other hand, the lower limit of the thickness is preferably 10 µm or more, more preferably 40 µm or more, and even more preferably 70 µm or more from the viewpoints of handleability and moisture resistance of the film of the present invention.

The release-based support is preferably subjected to a release treatment in advance, and specific examples of the release agent used for the release treatment include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. The mold release agent may be used alone or in combination of two or more. Further, the surface of the release-based support may be subjected to a matte treatment, corona treatment, or the like, and may be subjected to a release treatment again on the surface subjected to such treatment.

The encapsulation-based support means a support having moisture resistance, which can be used as part of various devices as it is when manufacturing various devices (i.e., provided in the manufacture of various devices and embedded in a device to be finally produced). More specifically, in the encapsulation structure of various devices, the support material is an encapsulation material in which elements (semiconductor elements, LED elements, organic EL elements, etc.) are disposed on the outermost layer separated from the element forming substrate formed on the surface. Is used as Examples of the support include a metal foil or a laminated film in which a metal foil or an inorganic vapor-deposited film is laminated on at least one surface of a plastic film. Here, as a metal foil, copper foil, aluminum foil, etc. are mentioned, As a vapor deposition film of an inorganic substance, vapor deposition films, such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon, are mentioned. In addition, commercially available plastic films having moisture resistance can be used for the support, for example, Tech Barrier HX, AX, LX, L series (reference: manufactured by Mitsubishi Corporation) or X-BARRIER, which further enhances the moisture-proof effect. [Reference: Mitsubishi Jushi Co., Ltd. product) etc. are mentioned. Moreover, a glass plate, a metal plate, etc. can also be used from a viewpoint that rigidity can be provided. In addition, when an organic EL device is produced using the film of the present invention using a sealing-based support, the light emitting surface of the produced organic EL device is a surface opposite to the surface on which the organic EL device is formed on the element forming substrate.

The thickness of the support is not particularly limited when using a metal foil for the encapsulation support, or a laminated film in which an inorganic vapor-deposited film or a metal foil is laminated on at least one side of a plastic film, but from the viewpoint of handleability 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, and even more preferably 90 μm or less. On the other hand, the lower limit of the thickness is preferably 10 µm or more, more preferably 40 µm or more, and even more preferably 70 µm or more from the viewpoints of handleability and moisture resistance of the film of the present invention.

The upper limit of the thickness of the support in the case of using a glass plate or a metal plate for the encapsulation support is preferably 5 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less from the viewpoint of making the organic EL device itself thin and light. Do. On the other hand, the lower limit of the thickness of the support is preferably 5 µm or more, more preferably 10 µm or more, and even more preferably 20 µm or more, from the viewpoints of preventing water permeation and rigidity of the organic EL device.

A laminated film in which a metal foil is laminated on at least one side of a plastic film is coated with an adhesive on a plastic film such as a PET film using a coating head capable of thin film coating such as gravure coater, and a metal foil such as aluminum on the coating surface of this adhesive. It can be obtained by laminating. The thickness of the metal foil is preferably 5 µm or more from the viewpoints of laminate properties and moisture permeability, and preferably 125 µm or less from the viewpoint of handling properties. Moreover, it is preferable to make the total thickness of the laminated film of this three-layer structure into the range of 10-150 micrometers.

(Moisture absorption resin composition layer)

The hygroscopic resin composition layer used for the film of the present invention is constituted by a thermosetting resin composition containing a thermosetting resin, a curing agent, and a hygroscopic metal oxide, and has moisture resistance. Thereby, the intrusion of moisture from the sealing structure of the target device (organic EL device or the like) into the element (organic EL element or the like) is prevented.

(Thermosetting resin and curing agent)

The thermosetting resin and curing agent are not particularly limited, and specifically, various thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinylbenzyl resins, and the like. And a curing agent. Among these, an epoxy resin and a curing agent thereof are preferred from the viewpoints of low temperature curing property and adhesiveness of the cured product.

As an epoxy resin, what is necessary is just to have two or more epoxy groups per average molecule, Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy Resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, aromatic glycidylamine-type epoxy resin (specifically, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol , Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, butadiene structure Epoxy resin having, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalene diol, glycidyl etherate of phenols, and alcohol And diglycidyl ether compounds of the above, and alkyl substituents of these epoxy resins, halides and hydrogenated products. These may be used alone or in combination of two or more.

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

Further, the epoxy resin may be either liquid or solid, or both liquid and solid. Here, "liquid phase" and "solid phase" are states of the epoxy resin at 25°C. From the viewpoints of coatability, workability, adhesiveness, etc., it is preferable that at least 10% by weight of the entire epoxy resin used is a liquid.

In addition, the epoxy resin, from the viewpoint of reactivity, the epoxy equivalent is preferably in the range of 100 to 1000, more preferably in the range of 120 to 1000. Here, the epoxy equivalent is the number of grams (g/eq) of the resin containing 1 g equivalent of epoxy group, and is measured according to the method specified in JIS K-7236.

The curing agent for the epoxy resin is not particularly limited as long as it has a function of curing the epoxy resin, but from the viewpoint of suppressing thermal deterioration of the element (especially the organic EL element) during the curing treatment of the resin composition, the curing treatment of the resin composition Is preferably carried out at 140°C or lower, more preferably at 120°C or lower, and the curing agent preferably has a curing action of the epoxy resin in this temperature range.

Specifically, primary amines, secondary amines, tertiary amine curing agents, polyaminoamide curing agents, dicyandiamides, organic acid dihydrazides, and the like, among these, from the viewpoint of fast curing property, amines Duct-based compounds (Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN- 40, Amicure PN-40J, etc. (all manufactured by Ajinomoto Fine Techno), organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine Techno)) Do. These may be used alone or in combination of two or more.

In addition, as an ionic liquid capable of curing the epoxy resin at a temperature of 140° C. or less, preferably 120° C. or less, that is, a salt capable of melting in a temperature range of 140° C. or less, preferably 120° C. or less, the epoxy resin Salts having a curing action of are particularly suitably used. The ionic liquid advantageously acts to improve the moisture permeability of the cured product of the moisture absorption resin composition layer. In addition, the ionic liquid is preferably used in a state in which the ionic liquid is uniformly dissolved in the epoxy resin.

Examples of the cation constituting the ionic liquid include ammonium-based cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion, and pyridinium ion; Phosphonium-based cations such as tetraalkylphosphonium cations (specifically, tetrabutylphosphonium ion, tributylhexylphosphonium ion, etc.); And sulfonium-based cations such as triethylsulfonium ion.

Further, examples of the anion constituting the ionic liquid include halide-based anions such as fluoride ions, chloride ions, bromide ions, and iodide ions; Alkyl sulfate-based anions such as methanesulfonic acid ions; Trifluoromethanesulfonic acid ion, hexafluorophosphonic acid ion, trifluorotris(pentafluoroethyl)phosphonic acid ion, bis(trifluoromethanesulfonyl)imide ion, trifluoroacetic acid ion, tetrafluoroboric acid Fluorine-containing anions such as ions; Phenolic anions such as phenol ion, 2-methoxyphenol ion, and 2,6-di-tert-butylphenol ion; Acidic amino acid ions such as aspartic acid ion and glutamate ion; Neutral amino acid ions such as glycine ion, alanine ion, and phenylalanine ion; N-acylamino acid ion represented by the following general formula (1), such as N-benzoylalanine ion, N-acetylphenylalanine ion, and N-acetylglycine ion; Carboxylic acid anions such as formic acid ion, acetic acid ion, decanoic acid ion, 2-pyrrolidone-5-carboxylic acid ion, α-lipoic acid ion, lactic acid ion, tartaric acid ion, manoic acid ion, N-methylmanoic acid ion, and benzoic acid ion Can be heard.

(In the above formula, R-CO- is an acyl group derived from a straight or branched chain fatty acid having 1 to 5 carbon atoms, or a substituted or unsubstituted benzoyl group, -NH-CHX-CO ₂ -is, for example, aspartic acid, glutamic acid, etc. Acidic amino acid ions, or neutral amino acid ions such as glycine, alanine, and phenylalanine.)

Among the above, cations are preferably ammonium-based cations and phosphonium-based cations, and more preferably imidazolium ions and phosphonium ions. Imidazolium ions are more specifically 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, and the like.

Further, the anion is preferably a phenolic anion, an N-acylamino acid ion of Formula 1 or a carboxylic acid anion, and more preferably an N-acylamino acid ion or a carboxylic acid anion.

2,6-di-tert-butylphenol ion is mentioned as a specific example of a phenol type anion. Further, specific examples of the carboxylic acid anion, acetic acid ion, decanoic acid ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, α-lipoic acid ion, lactic acid ion, tartaric acid ion, manoic acid ion, N-methylmanoic acid Ions etc. are mentioned, Among these, acetic acid ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, lactic acid ion, tartaric acid ion, uric acid ion, N-methylmanoic acid ion are preferable, and acetic acid ion, N-methylmanorate ion and formate ion are particularly preferred. Further, specific examples of the N-acylamino acid ion of Formula 1 include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartic acid ion, glycine ion, N-acetylglycine ion, and the like, and among these, N-benzoylalanine Ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferred, and N-acetylglycine ion is particularly preferred.

As specific ionic liquids, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutyl Phosphonium trifluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate salt, tetrabutylphosphonium lactate, bis tartarate (tetrabutylphosphonium) salt, tetrabutylphosphonate urate, N- Tetrabutylphosphonium methyl manarate, benzoyl-DL-alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenoltetrabutylphosphonium salt, L-aspartic acid mono Tetrabutylphosphonium salt, glycinetetrabutylphosphonium salt, N-acetylglycinetetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, formic acid 1 -Ethyl-3-methylimidazolium salt, manoic acid-1-ethyl-3-methylimidazolium salt, N-methylmanoic acid 1-ethyl-3-methylimidazolium salt, bis tartarate (1-ethyl- 3-methylimidazolium) salt, N-acetylglycine1-ethyl-3-methylimidazolium salt is preferred, N-acetylglycinetetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, Particularly preferred are 1-ethyl-3-methylimidazolium salt of formic acid, 1-ethyl-3-methylimidazolium salt of uric acid, and 1-ethyl-3-methylimidazolium salt of N-methylmanoic acid.

As a method for synthesizing the ionic liquid, a precursor composed of a cation moiety such as alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions, and an anion moiety containing halogen, NaBF ₄ , NaPF ₆ , CF ₃ SO ₃ Anion exchange method of reacting Na or LiN(SO ₂ CF ₃ ) _2, etc., while introducing an alkyl group by reacting an amine-based material with an acid ester, acid ester method in which an organic acid residue becomes a dianion, and neutralizing amines with an organic acid There is a neutralization method for obtaining a salt, and the like, but is not limited thereto. In the neutralization method with anions, cations, and solvents, anions and cations are used in equivalent amounts, and the solvent in the obtained reaction solution is distilled off to be used as it is, and organic solvents (methanol, toluene, ethyl acetate, acetone, etc.) ), and it may be concentrated.

The curing agent is preferably used in the range of 0.1 to 50% by weight, more preferably 0.5 to 25% by weight, and more preferably 1 to 15% by weight, relative to 100% by weight of the nonvolatile matter in the resin composition. And, the range of 1.5 to 10% by weight is more preferable. When less than this range, sufficient curability may not be obtained, and if it is more than 50% by weight, not only the storage stability of the resin composition is impaired, but the moisture permeability and heat resistance of the cured product may be lowered. In addition, in the case of using an ionic liquid, from the viewpoint of moisture permeability and the like of the cured product of the resin composition, 0.1 to 10% by weight is preferable, and 0.5 to 8% by weight is more preferable with respect to 100% by weight of the nonvolatile content of the epoxy resin. , 1 to 6% by weight is more preferable, and 1.5 to 5% by weight is more preferable.

In the resin composition constituting the hygroscopic resin composition layer in the present invention, a curing accelerator may be further included for adjustment of curing temperature, curing time, and the like. As the curing accelerator, quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, quaternary sulfonium salts such as tetraphenylphosphonium bromide and tetrabutylphosphonium bromide, DBU (1,8-diazabicyclo (5.4.0) Undecen-7), DBN(1,5-diazabicyclo(4.3.0)nonen-5), DBU-phenol salt, DBU-octyl acid salt, DBU-p-toluenesulfonate, DBU-formate, DBU- Diazabicyclo compounds such as phenol novolak resin salts, imidazole compounds such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-ethyl-4-methylimidazole, And tertiary amines such as tris(dimethylaminomethyl)phenol and benzyldimethylamine, dimethylurea compounds such as aromatic dimethylurea, aliphatic dimethylurea, and aromatic dimethylurea.

The content in the case of using a curing accelerator is in the range of 0.01 to 7% by weight relative to the total amount of the epoxy resin.

(Hygroscopic metal oxide)

The term "hygroscopic metal oxide" referred to in the present invention is a metal oxide that has the ability to absorb moisture and is chemically reacted with moisture absorbed to be a hydroxide, and is not particularly limited as long as it can achieve the object of the present invention. , One kind selected from calcium oxide, magnesium oxide, strontium oxide, aluminum oxide and valium oxide, or a mixture or solid solution of two or more metal oxides selected from them. As an example of a mixture or a solid solution of two or more metal oxides, specifically, calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide), and the like are mentioned. Such a hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and commercial products can be used. Specifically, calcined dolomite ("KT" manufactured by Yoshizawa Sekiga Co., Ltd.), calcium oxide ("Moistop #10" manufactured by Sankyo Sehun Co., Ltd.), magnesium oxide (Kyowa Mag MF Co., Ltd. manufactured by Kyowa Chemical Industry Co., Ltd.) 150'', ``Kyowa Mag MF-30'', ``Pure Mag FNMG'' manufactured by Tate Hogaku Kogyo Co., Ltd.), light magnesium oxide (``#500'' and ``#1000'' manufactured by Tate Hogaku Kogyo Kogyo) , "#5000", and the like.

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 even more preferably 1 µm or less. By using such a micro-sized thing, not only can a high degree of moisture permeability be provided to the cured layer of the moisture absorption resin composition, but also adhesion can be enhanced. In addition, when the average particle diameter of the hygroscopic metal oxide is too small, the particles tend to aggregate to become difficult to process sheets, and the average particle diameter of the hygroscopic metal oxide is preferably 0.01 µm or more, and 0.1 µm or more. This is preferred.

If the average particle diameter of a commercial article of hygroscopic metal oxide is 10 µm or less, it can be used as it is, but when the average particle diameter of a commercial article exceeds 10 µm, pulverization, classification, etc. are performed to obtain granular products having an average particle diameter of 10 µm or less It is preferable to use after preparing with.

The "average particle diameter" referred to herein is the median diameter of the particle size distribution when the particle size distribution of the measurement object (granular object) is created on a volume basis. The particle size distribution on a volume basis can be measured by a laser diffraction/scattering method based on the Mie scattering theory, and specifically, as a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Sesakusho Can be used. As the measurement sample, it is preferable to use one in which hygroscopic metal oxide is dispersed in water by ultrasonic waves.

As the hygroscopic metal oxide, one surface-treated with a surface treatment agent can be used. By using such a surface-treated hygroscopic metal oxide, the storage stability of the resin composition constituting the hygroscopic resin composition layer can be further improved, and it is possible to prevent the moisture in the resin and the hygroscopic metal oxide from reacting before the curing.

As a surface treatment agent used for surface treatment, specifically, higher fatty acids, alkylsilanes, silane coupling agents, etc. can be used, and among these, higher fatty acids or alkylsilanes are suitable.

Specifically, higher fatty acids having 18 or more carbon atoms, such as stearic acid, montanic acid, millistic acid, and palmitic acid, are preferred, and stearic acid is more preferable. These may be used alone or in combination of two or more.

Examples of the alkylsilanes include methyl trimethoxysilane, ethyl trimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, and octyltrie And oxysilane, n-octadecyldimethyl(3-(trimethoxysilyl)propyl)ammonium chloride, and the like. These may be used alone or in combination of two or more.

As a silane coupling agent, specifically, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2-( Epoxy-based silane coupling agents such as 3,4-epoxycyclohexyl)ethyl trimethoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; Ureide-based silane coupling agents such as 3-ureidpropyl triethoxysilane, vinyl-based silane coupling agents such as vinyl trimethoxysilane, vinyl triethoxysilane and vinyl methyl diethoxysilane; styryl-based silane coupling agents such as p-styryl trimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanatepropyl trimethoxysilane, sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; And phenyltrimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, and triazine silane. These may be used alone or in combination of two or more.

Specifically, the surface treatment can be carried out by stirring and dispersing the untreated hygroscopic metal oxide with a mixer at room temperature while adding and spraying a surface treatment agent and stirring for 5 to 60 minutes. As a mixer, a well-known mixer can be used, and specifically, blenders, such as a V blender, a ribbon blender, and a bubble cone blender, a mixer, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. In addition, when pulverizing the hygroscopic material with a ball mill or the like, a method of mixing the above-described higher fatty acid, alkylsilanes or silane coupling agent and surface treatment is also possible. The treatment amount of the surface treatment agent varies depending on the type of the hygroscopic metal oxide, the type of the surface treatment agent, and the like, but is preferably 1 to 10% by weight relative to the hygroscopic metal oxide.

The upper limit of the content of the hygroscopic metal oxide in the resin composition is 100% by weight of the non-volatile content in the resin composition, from the viewpoint that when the content of the hygroscopic metal oxide is excessively large, the viscosity of the resin composition increases and the strength of the cured product decreases and collapses. It is preferably 40% by weight or less, more preferably 35% by weight or less, more preferably 30% by weight or less, even more preferably 25% by weight or less, and particularly preferably 20% by weight or less. On the other hand, the lower limit of the content of the hygroscopic metal oxide is preferably 1% by weight or more with respect to 100% by weight of the nonvolatile matter in the resin composition, from the viewpoint of sufficiently obtaining the effect by containing the hygroscopic metal oxide, and 5% by weight or more More preferably, 10% by weight or more is more preferable.

(Weapon filler)

The resin composition constituting the hygroscopic resin composition layer may further contain an inorganic filler (except for hygroscopic metal oxides). By containing the said inorganic filler, moisture permeability of the hardened|cured material of a resin composition improves, and also, the bounce of the composition at the time of film production is prevented, and the adhesive force with a support body or sealing material can be improved. As an inorganic filler, specifically, silica, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, And barium zirconate, calcium zirconate, talc, clay, mica, boehmite, zeolite, apatite, kaolin, mullite, spinel, oribin, sericite, bentonite and the like. The inorganic filler may be used alone or in combination of two or more. Among these, from the viewpoint of difficulty in transferring inorganic fillers to other layers during lamination, fillers having a flat particle shape such as talc, clay, mica, and boehmite are preferable, and by using a filler having a flat particle shape, moisture absorption is achieved. The moisture permeability of the cured layer obtained by curing the resin composition layer can be further increased.

The upper limit of the average particle diameter of the inorganic filler is preferably 1 µm or less, and more preferably 0.8 µm or less, from the viewpoint of improving dispersibility and preventing reduction of mechanical strength, or from the viewpoint that the inorganic filler is difficult to migrate to another layer during lamination. And more preferably 0.6 µm or less. Further, 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 deterioration of dispersibility due to agglomeration and preventing deterioration of handleability due to increase in viscosity of the resin composition, 0.3 µm or more is more preferable. In addition, the average particle diameter here means the same as the average particle diameter in the hygroscopic metal oxide mentioned above.

The upper limit of the content of the inorganic filler in the resin composition is relative to 100% by weight of the non-volatile content in the resin composition, from the viewpoint 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 collapses. 50 weight% or less is preferable, 40 weight% or less is more preferable, 35 weight% or less is more preferable, and 30 weight% or less is still more preferable. On the other hand, from the viewpoint of sufficiently obtaining the effect of the inorganic filler, the lower limit of the content of the inorganic filler is preferably 1% by weight or more, more preferably 5% by weight or more, and more preferably 10% by weight with respect to 100% by weight of nonvolatile matter in the resin composition. % Or more is more preferred.

(Rubber particles)

The resin composition constituting the moisture absorbing resin composition layer may further contain rubber particles, and by containing the rubber particles, mechanical strength improvement, stress relaxation, and the like of the cured product of the resin composition can be achieved. It is preferable that the said rubber particle does not melt|dissolve in the organic solvent at the time of preparing the varnish of a resin composition, is not compatible with the components in resin compositions, such as an epoxy resin, and exists in a dispersed state in the varnish of a resin composition. These rubber particles can generally be prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in organic solvents or resins to form particles, and specifically, core-shell rubber particles, crosslinked acrylonitrile butadiene rubber And particles, crosslinked styrene-butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles in which the particles have a core layer and a shell layer. Specifically, a two-layer structure in which the shell layer of the outer layer is composed of a rubbery polymer, and the core layer of the inner layer is a rubbery polymer, or the shell layer of the outer layer is glassy And a three-layer structure composed of a polymer, a rubber polymer in the middle layer, and a glass polymer in the core layer. The glass layer is specifically 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 these rubber particles is preferably 2 µm or less from the viewpoint of maintaining the effect of stress relaxation or preventing damage to the element when sealing the organic EL element with the resin composition. Do. On the other hand, 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 handleability from deteriorating due to an increase in viscosity when mixed with the resin. Examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (reference: manufactured by Gantz Chemical Co., Ltd.), Metablen KW-4426 (reference: manufactured by Mitsubishi Rayon Co., Ltd.), and F351 (reference: manufactured by Nippon Zeon Co., Ltd.). have. As a specific example of acrylonitrile-butadiene rubber (NBR) particles, XER-91 (reference: manufactured by JSR Corporation), etc. may be mentioned. As a specific example of a styrene-butadiene rubber (SBR) particle, XSK-500 (reference: the JSR company make) etc. are mentioned. As specific examples of the acrylic rubber particles, Metablen W300A and W450A (see Mitsubishi Rayon Co., Ltd.) are listed.

The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. Specifically, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is prepared by weight using FPRA-1000 (manufactured by Otsuka Denshi Co., Ltd.), and the median diameter is averaged. It is measured by setting the particle diameter.

The upper limit of the content of the rubber particles is preferably 20% by weight or less, and 10% by weight or less, with respect to 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 from deteriorating. It is more preferable. On the other hand, the lower limit of the content of the rubber particles is preferably 0.1% by weight or more with respect to 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.

Further, a rubber particle-dispersed epoxy resin in which rubber particles are dispersed in an epoxy resin in the form of primary particles is commercially available, and by using a rubber particle-dispersed epoxy resin as the epoxy resin, the resin composition may contain rubber particles. As such a rubber particle-dispersed epoxy resin, specifically, "BPA328" manufactured by Nihon Shokubai Co., Ltd. (rubber particles: acrylic core shell type resin, average particle diameter of rubber particles: 0.3 µm, rubber particle content: 17% by weight, epoxy resin : Epoxy equivalent of 185 bisphenol A type epoxy resin), manufactured by Kaneka Co., Ltd. "MX120" (rubber particles: SBR-based resin, average particle diameter of rubber particles: 0.1 µm, rubber particle content: 25% by weight, epoxy resin: epoxy equivalent 185 bisphenol A type epoxy resin) and the like.

(Thermoplastic resin)

The resin composition constituting the moisture absorption 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 composition, and good processability when coating the resin composition can be imparted. Specific examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether sulfone resin, and polysulfone resin. Any one of these thermoplastic resins may be used in combination of two or more. The thermoplastic resin has a weight average molecular weight of 10,000 or more, and more preferably 30,000 or more, from the viewpoint of providing flexibility and preventing bouncing during coating. However, if the weight average molecular weight is too large, since compatibility with the epoxy resin tends to decrease, the weight average molecular weight is preferably 1,000,000 or less, and more preferably 800,000 or less.

In addition, the "weight average molecular weight of a thermoplastic resin" mentioned here is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by GPC method is LC-9A/RID-6A manufactured by Shimadzu Corporation, as a measuring device, and Shodex K-800P/K-804L/K- manufactured by Showa Denko Corporation as a column. 804L can be calculated using chloroform or the like as the mobile phase, measuring at a column temperature of 40°C, and using a calibration curve of standard polystyrene.

Among the above-described examples, the thermoplastic resin is particularly preferably a phenoxy resin. The phenoxy resin is also preferred in that it has good compatibility with the "epoxy resin" and has little influence on the adhesion and moisture resistance of the cured product of the resin composition.

As a phenoxy resin, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, And those having one or more skeletons selected from adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The phenoxy resin may be used by mixing two or more kinds.

As a commercial item of phenoxy resin, specifically, 1,256,4250 (the phenoxy resin containing a bisphenol A skeleton) manufactured by Japan Epoxy Resin, YX8100 (the phenoxy resin containing a bisphenol S skeleton) manufactured by Japan Epoxy Resin, Japan epoxy resin YX6954 (bisphenol acetphenone skeleton-containing phenoxy resin), PKHH (weight average molecular weight (Mw) 42600, number average molecular weight (Mn) 11200) manufactured by Union Carbide, etc.) are suitable, FX280, manufactured by Toto Kasei Co., Ltd. FX293, YL7553BH30, YL6794, YL7213, YL7290, YL7482 by Japan Epoxy Resin, etc. are mentioned.

The upper limit of the content of the thermoplastic resin is preferably 50% by weight or less, and more preferably 25% by weight or less, with respect to 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. On the other hand, from the viewpoint of obtaining a sufficient effect by containing the thermoplastic resin, the lower limit of the content of the thermoplastic resin is preferably 1% by weight or more, and 3% by weight or more, with respect to 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer. More preferably, 5% or more is more preferable, and 10% or more is still more preferable.

(Coupling agent)

The moisture absorption resin composition layer used in the present invention can further improve adhesion to the adherend (support, protective resin composition layer, encapsulation material, etc.) of the cured product and moisture permeability of the cured product by further containing a coupling agent. Specific examples of the coupling agent include a titanium-based coupling agent, an aluminum-based coupling agent, and a silane coupling agent. Among these, silane coupling agents are preferred. These may be used alone or in combination of two or more.

As a silane coupling agent, specifically, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2-( Epoxy-based silane coupling agents such as 3,4-epoxycyclohexyl)ethyl trimethoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; Ureide-based silane coupling agents such as 3-ureidpropyl triethoxysilane, vinyl-based silane coupling agents such as vinyl trimethoxysilane, vinyl triethoxysilane and vinyl methyl diethoxysilane; styryl-based silane coupling agents such as p-styryl trimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanatepropyl trimethoxysilane, sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; And phenyltrimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, and triazine silane. Among these, epoxy-based silane coupling agents are particularly suitable.

The upper limit of the content of the coupling agent is preferably 10% by weight or less, and more preferably 5% by weight or less, with respect to 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer, from the viewpoint of obtaining the effect of improving the adhesion by adding the coupling agent. . On the other hand, from the viewpoint of obtaining the effect of improving the adhesion by adding the coupling agent and the lower limit of the content of the coupling agent, 0.5% by weight or more with respect to 100% by weight of the nonvolatile matter in the moisture-absorbing resin composition layer is preferable.

The hygroscopic resin composition layer used in the present invention may optionally contain various additives other than the above-described components within a range in which the effects of the present invention are exhibited. As such additives, specifically, organic fillers such as silicon powder and nylon powder or fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, triazole compounds, thiazole compounds, and triazine compounds And adhesion-providing agents such as porphyrin compounds.

The thickness of the moisture absorption resin composition layer used in the present invention is not particularly limited, but in the structure in which the support is stacked on the resin composition layer, moisture penetrates only from the side of the resin composition layer, so that the thickness of the moisture absorption resin composition layer is reduced. From the viewpoint of blocking moisture by reducing the contact area with the outside air, the upper limit of the thickness is preferably 200 µm or less, more preferably 150 µm or less, and even more preferably 100 µm or less. On the other hand, from the viewpoint of securing the concentration of the absorbent material to obtain a sufficient moisture absorbing effect, the lower limit of the thickness is preferably 3 µm or more, more preferably 5 µm or more, and even more preferably 10 µm or more.

(Protective resin composition layer)

The protective resin composition layer used for the film of the present invention is composed of a thermosetting resin and a thermosetting resin composition containing a curing agent, and in the sealing structure of the target device (organic EL device, etc.), an element (organic EL element, etc.) By directly coating, the hygroscopic metal oxide in the hygroscopic resin composition layer has a role of preventing the device from being damaged due to contact with the device.

(Thermosetting resin and curing agent)

As the thermosetting resin and the curing agent, the same thermosetting resin and curing agent used for the above-mentioned moisture absorbing resin composition layer is used. The thermosetting resin and curing agent used for the protective resin composition layer and the thermosetting resin and curing agent used for the moisture absorption resin composition layer may be different from each other, but both layers after curing due to differences in adhesion between the two layers, curing shrinkage, or curing speed. It is preferable that the thermosetting resin and hardener used for the protective resin composition layer and the thermosetting resin and hardener used for the moisture absorption resin composition layer are the same from the viewpoint of suppressing the interfacial stress of.

(Hygroscopic metal oxide)

The protective resin composition layer used in the present invention may further contain a hygroscopic metal oxide within a range not impairing the damage preventing function of the organic EL element. By containing a hygroscopic metal oxide, moisture permeability can be improved.

When the hygroscopic metal oxide is contained in the protective resin composition layer, the upper limit of the content of the hygroscopic metal oxide is 5% by weight or less with respect to 100% by weight of the nonvolatile matter in the protective resin composition layer from the viewpoint of preventing damage to the organic EL device. desirable. On the other hand, from the viewpoint of obtaining the effect of improving moisture permeability, the lower limit of the content of the hygroscopic metal oxide is preferably 0.5% by weight or more with respect to 100% by weight of the nonvolatile matter in the protective resin composition layer.

Further, even if the hygroscopic metal oxide is contained within a range of 5% by weight or less with respect to 100% by weight of the nonvolatile content in the protective resin composition layer, the organic EL element may be damaged if the particle diameter of the hygroscopic metal oxide is large. , The hygroscopic metal oxide preferably has an average particle diameter of less than 1 μm. Further, even if the average particle diameter is less than 1 µm, if the particle size distribution is broad, there is a possibility that the organic EL element is damaged by containing coarse particles, and the average particle diameter is less than 1 µm, and the particle diameter is 3 µm or more. It is more preferable not to contain particles.

In addition, as the hygroscopic metal oxide contained in the protective resin composition layer, a metal oxide such as hygroscopic metal oxide contained in the hygroscopic resin composition layer can be used, and surface treatment or the like can be applied in the same form. Further, commercially available products of hygroscopic metal oxides can be used as long as their average particle diameter is less than 1 µm, but when the average particle diameter of commercially available products is 1 µm or more, pulverization, classification, etc. are performed to obtain granular products having an average particle diameter of less than 1 µm. Prepare it before use. The "average particle diameter" as used herein also has the same meaning as the average particle diameter of the hygroscopic metal oxide contained in the moisture absorption resin composition layer.

(Weapon filler)

The protective resin composition layer used in the present invention also contains an inorganic filler (except for hygroscopic metal oxides), so that the moisture permeation rate at the interface between the layer and the EL element side can be delayed to improve adhesion to the substrate. Can be. As the said inorganic filler, the thing similar to the inorganic filler used for the said moisture absorption resin composition layer can be used. In view of the difficulty in exposing the inorganic filler during lamination, a filler having a flat plate shape such as talc, clay, mica, and boehmite is preferred. In addition, when using an inorganic filler, the upper limit of the content of the inorganic filler is 15% by weight with respect to 100% by weight of the nonvolatile matter in the resin composition layer, from the viewpoint that the viscosity of the resin composition rises and the strength of the cured product decreases and retreats. % Or less is preferable, and 10 wt% or less is more preferable. On the other hand, the lower limit of the content of the inorganic filler is preferably 1% by weight or more with respect to 100% by weight of the nonvolatile matter in the resin composition, from the viewpoint of obtaining an effect of retarding the moisture permeation rate of the interface between the resin composition layer and the EL element side, 3 weight% or more is more preferable. Moreover, when using an inorganic filler with a hygroscopic metal oxide, it is used in the range which the total amount of an inorganic filler and a hygroscopic metal oxide becomes 15 weight% or less with respect to 100 weight% of nonvolatile matter in a resin composition.

(Rubber particles, thermoplastic resins, coupling agents, etc.)

By adding rubber particles to the protective resin composition layer used in the present invention, the mechanical strength of the cured product, stress relaxation, and the like can be performed. In addition, by containing a thermoplastic resin in the moisture-absorbing resin composition layer used in the present invention, flexibility can be imparted to the cured product, and good workability when coating the resin composition can be imparted. In addition, by containing a coupling agent in the moisture absorption resin composition layer used in the present invention, adhesion to the adherend of the cured product and moisture permeability of the cured product can be improved. The rubber particles, thermoplastic resins, and coupling agents can be used such as the rubber particles, thermoplastic resins, and coupling agents used in the hygroscopic resin composition layer, the coupling agent is preferably a silane coupling agent, and the thermoplastic resin is phenoxy City resins are preferred. Content in the thermosetting resin composition basically follows the content in the thermosetting resin composition constituting the moisture absorption resin composition layer.

The protective resin composition layer used in the present invention may optionally contain various additives other than the above-described components within a range in which the effects of the present invention are exhibited. Specifically, organic fillers such as silicon powder, nylon powder, fluorine powder, thickeners such as olben, benton, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds Adhesives, etc., etc. are mentioned.

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

[Protective film]

It is preferable that the film of the present invention is protected with a protective film to prevent adhesion or scratches on the surface of the resin composition layer until it is actually used for forming the encapsulation structure. The plastic film exemplified in the support can be used. The protective film is preferably subjected to a release treatment in advance, and specific examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. You may mix and use different types of mold release agents. Further, the thickness of the protective film is also not particularly limited, but is preferably 1 to 100 μm, more preferably 10 to 75 μm, and even 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, organic ELs, and particularly suitable for encapsulating organic EL elements, and organic EL devices. It can be used suitably. In addition, in the case of distributing the film of the present invention, a protective film can be pasted. That is, the structure of the film of the present invention includes the following six forms.

(1) Peeling system support body + moisture absorption resin composition layer + protective resin composition layer + protective film

(2) Encapsulation system support + moisture absorption resin composition layer + protective resin composition layer + protective film

(3) Peeling system support + protective resin composition layer + moisture absorption resin composition layer + protective film

(4) Peeling system support + moisture absorption resin composition layer + protective resin composition layer

(5) Encapsulation system support + moisture absorption resin composition layer + protective resin composition layer

(6) Peeling system support + protective resin composition layer + moisture absorption resin composition layer

In addition, the above shows the lamination order of each layer.

(1) and (2) of the film of this invention are specifically, the 1st varnish which melt|dissolved the resin composition which comprises the moisture absorption resin composition layer, and the 2nd varnish which melt|dissolved the resin composition which comprises the protective resin composition layer. Each was prepared, and on the release-based support or on the encapsulation-based support, the first varnish was applied and the organic solvent was dried to form a layer of hygroscopic resin composition, on which the second varnish was applied and the organic solvent was dried to protect the protective resin composition. It can be obtained by forming a layer and also using a protective film. Moreover, the structure of (3) of the film of this invention can be obtained by forming the protective resin composition layer and the moisture absorption resin composition layer in reverse. The structures (4), (5), and (6) of the film of the present invention show the configuration when the protective film is not used in the production of the films of the structures (1), (2), and (3). .

When the film of the present invention is composed of (1) and (3), the relationship between the release-based support and the protective film should be such that the protection film is first peeled, or the protective film is made thinner than the release-based support or It is preferable to apply a release treatment or an embossing process. In addition, the release-based support is preferably a polyethylene terephthalate (PET) film, and the protective film is preferably biaxially stretched polypropylene.

As an organic solvent used for the varnish, specifically, acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK"), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether Acetic acid esters such as acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. have. These may be used alone or in combination of two or more.

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

In addition, in the method for producing the film of the present invention by sequentially forming the moisture absorbent resin composition layer and the protective resin composition layer on the support in this order or in the reverse order, at the boundary between the moisture absorbent resin composition layer and the protective resin composition layer. Therefore, there is a concern that a mixed layer in which the resin composition of both layers is mixed is formed, and the effect of preventing damage to the organic EL device by the protective resin composition layer may be impaired. Accordingly, a first resin composition sheet was prepared on the first support using the first varnish to form a hygroscopic resin composition layer, and separately from this, a protective resin composition layer was formed on the second support using the second varnish. A method of producing a film of the present invention by producing a second resin composition sheet, and laminating the moisture absorption resin composition layer of the first resin composition sheet and the protective resin composition layer of the second resin composition sheet is preferable. In this case, either of the first support and the second support becomes the support of the film of the present invention, and the other becomes the protective film of the film of the present invention.

When the film of this invention is obtained by such a method, it is preferable that the melt viscosity of the protective resin composition layer is lower than the melt viscosity of the moisture absorption resin composition layer at the lamination temperature of the moisture absorption resin composition layer and the protective resin composition layer. That is, at the lamination temperature of the moisture absorption 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 the melt viscosity of the moisture absorption resin composition layer, so that the filler contained in the moisture absorption resin composition layer This is because it is possible to avoid damage to the EL element by moving to the protective resin composition layer at the time of lamination or passing through the protective resin composition layer.

As for the "melt viscosity" used here, a model Rheosol-G3000 manufactured by UBIM was used, and a resin amount of 1 g and a parallel plate of 18 mm in diameter was used, the measurement start temperature was 60°C, and the temperature increase rate was 5°C/min. , Measurement temperature is 60 to 200 ℃, the value measured by the frequency of 1Hz / deg.

The lamination temperature is not particularly limited, and can be appropriately set depending on the required performance, but since it is required to be lower than the curing temperature of the moisture absorption resin composition layer and the protective resin composition layer, the upper limit of the lamination temperature is preferably 130° C. or less, 120 degrees C or less is more preferable, 110 degrees C or less is more preferable, and 100 degrees C or less is still more preferable. On the other hand, 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, and even more preferably 55°C or higher, from the viewpoint of good handling at room temperature. , 60°C or higher is particularly preferred. In addition, at a set lamination temperature, from the viewpoint of preventing the hygroscopic resin composition layer and the protective resin composition layer from being mixed with each other, and from the viewpoint of preventing the hygroscopic metal oxide from being transferred to the protective resin composition layer, the melt viscosity of the hygroscopic resin composition layer The lower limit of the difference between the melt viscosity of the protective resin composition layer (the melt viscosity of the hygroscopic resin composition layer-the melt viscosity of the protective resin composition layer) is preferably 300 poise or more, more preferably 1000 poise or more, and 5000 pouch or more. More preferably, more than 10000 poise is more preferable, more preferably 15000 poise or more, and most preferably 30000 poise or more. On the other hand, at a set lamination temperature, from the viewpoint of effectively hardening the moisture absorbent resin composition layer and the protective resin composition layer at once, and from the viewpoint of efficiently bonding the moisture absorbent resin composition layer and the protective resin composition layer, melting of the moisture absorbent resin composition layer The upper limit of the difference between the viscosity and the melt viscosity of the protective resin composition layer (melt viscosity of the hygroscopic resin composition layer-melt viscosity of the protective resin composition layer) is preferably 1000000 poise or less, more preferably 500000 poise or less, and 100000 Poise or less is more preferable.

In addition, as a method for adjusting the melt viscosity of the protective resin composition layer and the moisture absorbing resin composition layer, a method of changing the curing degree by drying conditions, a method of changing the blending ratio of the liquid resin, a particle diameter of the inorganic filler, a content ratio, etc. are changed. And the like, and these may be performed in combination of two or more. Therefore, by these methods, the viscosity of the protective resin composition layer and the moisture absorption resin composition layer is adjusted, so that the melt viscosity at a predetermined temperature of the protective resin composition layer becomes lower than the melt viscosity at a predetermined temperature of the moisture absorption resin composition layer. .

The film of the present invention can be applied to the formation of a sealing structure for various semiconductor elements (individual semiconductors, optical semiconductors, logic ICs, analog ICs, memories, etc.), but among them, it can be particularly suitably used for sealing organic EL elements. have.

(Method for manufacturing organic EL device)

A method of sealing the organic EL element using the film of the present invention and manufacturing the organic EL device will be described below. In the encapsulation structure of the device, the protective resin composition layer is arranged to cover the elements of the element forming substrate, and the moisture absorption resin composition layer is disposed on the side opposite to the surface of the protective resin composition layer on the element forming substrate side. The structure of the film of the present invention includes the following six forms, as described above.

(1) Peeling system support body + moisture absorption resin composition layer + protective resin composition layer + protective film

(2) Encapsulation system support + moisture absorption resin composition layer + protective resin composition layer + protective film

(3) Peeling system support + protective resin composition layer + moisture absorption resin composition layer + protective film

(4) Peeling system support + moisture absorption resin composition layer + protective resin composition layer

(5) Encapsulation system support + moisture absorption resin composition layer + protective resin composition layer

(6) Peeling system support + protective resin composition layer + moisture absorption resin composition layer

(a) When the film of the present invention has the structure (1), the protective film is first removed, and the protective resin composition layer is laminated on a transparent substrate on which an organic EL element is formed. Thereafter, the release-based support is peeled off, the encapsulation material is laminated on the exposed moisture-absorbing resin composition layer, and a thermal curing operation of the protective resin composition layer and the moisture-absorbing resin composition layer can be performed to produce an organic EL device.

(b) When the film of the present invention has the structure (2), first the protective film is removed, the protective resin composition layer is laminated on a transparent substrate on which an organic EL element is formed, and the heat of the protective resin composition layer and the moisture absorption resin composition layer An organic EL device can be manufactured by performing a curing operation.

(c) When the film of the present invention has the structure (3), the protective film is first removed, and the moisture-absorbing resin composition layer is laminated to the sealing material. After that, the release-based support is peeled off, the exposed protective resin composition layer is laminated on a transparent substrate on which an organic EL element is formed, and thermal curing of the protective resin composition layer and the moisture absorption resin composition layer is performed to produce an organic EL device. have.

(d) When the film of the present invention has the structure (4), the protective resin composition layer is laminated on a transparent substrate on which an organic EL element is formed. Thereafter, the release-based support is peeled off, the encapsulation material is laminated on the exposed moisture-absorbing resin composition layer, and a thermal curing operation of the protective resin composition layer and the moisture-absorbing resin composition layer can be performed to produce an organic EL device.

(e) When the film of the present invention has the structure of (5), the protective resin composition layer is laminated on a transparent substrate on which an organic EL element is formed, and the protective resin composition layer and the moisture absorption resin composition layer are thermally cured as they are. An EL device can be manufactured.

(f) When the film of the present invention has the structure (6), the moisture absorbing resin composition layer is laminated to the encapsulating material, and then the peeling support is peeled off, and the exposed protective resin composition layer is transparent with an organic EL element formed thereon. The organic EL device can be manufactured by laminating on a substrate to perform a thermal curing operation of the protective resin composition layer and the moisture absorbing resin composition layer.

It is preferable to manufacture an organic EL device by the method of (b), (c), (e) or (f) from the viewpoint of not applying a heat history more than necessary to the organic EL element.

In addition, the sealing material used in the method of (a), (c), (d), and (f) is a material for forming the sealing structure, prepared separately from the film of the present invention, and as the sealing material , Metal films such as plastic films having moisture resistance, copper foil, aluminum foil, glass plates, metal plates, and the like. From the viewpoint of making the organic EL device itself thin and light, the upper limit of the thickness of the encapsulating material is preferably 5 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the encapsulating material is preferably 5 µm or more, more preferably 10 µm or more, and even more preferably 20 µm or more from the viewpoint of preventing moisture permeation and the rigidity of the organic EL device. Two or more sheets may be used as a sealing material, and in that case, the total thickness after bonding is preferably in the range of 5 µm or more and 5 mm or less.

The method of lamination performed in the above methods (a) to (f) may be a batch type or a continuous type in a roll. Lamination conditions can be performed under reduced pressure, and it is preferable to use a vacuum laminator or the like. It is preferable to laminate under reduced pressure of 10 ^-3 (10 hPa) MPa or less, under conditions of 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 vacuum pressurized laminators manufactured by Meiki Sesakusho Co., Ltd., and vacuum applicators manufactured by Nichigo Morton.

The method for thermally curing the protective resin composition layer and the moisture absorption resin composition layer is not particularly limited, and a known one can be used. Specifically, a hot air circulation type oven, an infrared heater, a heat gun, a high frequency induction heating device, heating by crimping of a heat tool, etc. are mentioned. The film of the present invention has a very good low-temperature curing property, and the upper limit of the curing temperature is preferably 140°C or less, more preferably 120°C or less, and even more preferably 110°C or less. On the other hand, from the viewpoint of securing the adhesiveness of the cured product, the lower limit of the curing temperature is preferably 50°C or higher, and more preferably 55°C or higher. In addition, the upper limit of the curing time is preferably 120 minutes or less, more preferably 90 minutes or less, and even more preferably 60 minutes or less. On the other hand, from the viewpoint of reliably curing the cured product, the lower limit of the curing time is preferably 20 minutes or more, and more preferably 30 minutes or more. Thereby, thermal deterioration of an organic EL element can be made very small.

In addition, in the organic EL device of the present invention, when the organic EL element is formed on the transparent substrate, if the transparent substrate side is the display surface of the display or the light emitting surface of the lighting fixture, it is necessarily a transparent material for the encapsulation support or sealing material. It is not necessary to use a metal plate, a metal foil, an opaque plastic film or plate, or the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Materials used)

The materials used in the experiment will be described.

(A) Epoxy resin

ㆍ Solid epoxy resin ("HP7200H" manufactured by DIC: dicyclopentadiene solid epoxy resin, epoxy equivalent (278g/eq))

ㆍ Rubber fine particle dispersion liquid epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd.): A composition comprising 17 weight percent of bisphenol A type epoxy resin having an epoxy equivalent of 185 in a two-layer acrylic resin particle having a primary particle diameter of 0.3 µm. Epoxy equivalent (2309/eq)

ㆍ Liquid epoxy resin ("GOT" manufactured by Nihon Kayaku Co., Ltd.: orthotoluidine diglycidylamine, epoxy equivalent (135 g/eq))

(B) Phenoxy resin

ㆍ MEK solution of 35% by weight of solid content of "YL7213-35M" (weight average molecular weight 35000) manufactured by Japan Epoxy Resin Co., Ltd.

(C) curing agent

ㆍ Potential curing accelerator for epoxy resin ("U-CAT3502T" manufactured by San-Apro)

ㆍ Ionic liquid curing agent ("TBP/N-Ac-gly", N-acetylglycinetetrabutyl phosphonium salt)

(D) hygroscopic metal oxide

ㆍ Calcined dolomite: MEK slurry obtained by wet grinding of "light dolomite" manufactured by Yoshizawa Sekigais (40% by weight as a solid content, average particle diameter: 0.87 µm)

(E) Inorganic filler

ㆍ Talc: MEK slurry of wet grinding of "D-600" manufactured by Nihon Tarku (30% by weight as a solid content, average particle diameter: 0.72㎛)

(F) Surface treatment agent

ㆍ Stearic acid

(G) Coupling agent

ㆍ Silane coupling agent: "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd. (3-glycidoxypropyl trimethoxysilane)

〔How to measure〕

Next, the measurement method will be described.

[Adhesion between support body and resin composition layer]

Two pieces 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 superimposed on one side of the first aluminum foil, and by a vacuum laminator, It was laminated under the conditions of a temperature of 80°C and a pressure of 1 kgf/cm 2 (9.8 x 10 ⁴ Pa). Then, the substrate was peeled off, and a second piece of aluminum foil was superimposed on the exposed resin composition layer to laminate under the same conditions to prepare a test piece having a three-layer structure of aluminum foil, resin composition layer, and aluminum foil. After heat-hardening the test piece under the conditions of 110°C and 30 minutes, the test piece was cut into a rectangular test piece having a width of 10 mm and a length of 50 mm, and adhered to the T-type peel test method of JIS K-6854 in the longitudinal direction of the test piece. ) Was measured.

〔Assessment Methods〕

Next, the evaluation method will be described.

[Evaluation of moisture resistance]

The organic EL device was exposed to a 60° C./90% RH constant temperature environment for 1000 hours, and the moisture permeability of the film was evaluated. The moisture permeability of the film was determined from the state of shrinkage (shrink) and DS (dark spot) of the light emitting area generated in the light emitting portion of the organic EL element, and the relative change rate of luminance after the initial (0 hour) and 1000 hours was evaluated. That is, when a large amount of shrink or DS occurs, the light emitting area decreases, and the luminance of the light emitting unit increases, thereby increasing the relative change rate with respect to the luminance in the initial state without defects. In addition, the luminance was measured by two points with constant current driving (15 mA), and the average value was calculated. As an evaluation, when the relative change rate was less than 1.1, it was set to ○, and when it was 1.1 or more, it was set to ×.

[Evaluation of device damage resistance]

The degree of damage of the organic EL device was evaluated by the dark current value at the driving voltage of 3V. As an evaluation, it was set as ○ when the dark current value was less than 0.2 mV, and was set as x when it was 0.2 mV or more.

Curable resin composition varnishes A to E of the blending composition shown in Table 1 below were prepared in the following order. In addition, the numerical value of the compounding quantity of each material shown in Table 1 is a weight part.

(Production Example 1)

A mixed lysate was prepared by dissolving a solid epoxy resin ("HP7200H" manufactured by DIC Corporation) in a phenoxy resin (35% by weight of a MEK solution of "YL7213-35M" manufactured by Japan Epoxy Resin Corporation). E, rubber fine particle dispersion liquid epoxy resin ("BPA328" by Nippon Shokubai Co., Ltd.), liquid epoxy resin ("GOT" by Nippon Kayaku Co., Ltd.), and latent curing accelerator for epoxy resin ("U-CAT3502T by San-Apro Corporation") ), a silane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), an ionic liquid curing agent (N-acetylglycine tetrabutyl phosphonium salt), and MEK are added to uniformly disperse the varnish with a high-speed rotary mixer. A was obtained.

(Production Example 2)

A mixture A in which a solid epoxy resin ("HP7200H" manufactured by DIC Corporation) was dissolved in a phenoxy resin (35% by weight MEK solution of "YL7213-35M" manufactured by Japan Epoxy Resin Corporation) was prepared. On the other hand, stearic acid was added and dispersed in a MEK slurry (40% by weight as a solid content) of calcined dolomite (wet milled by Yoshizawa Sekigais Co., Ltd.) to prepare mixture B. Mixture A, mixture B, talc (MED slurry of 30% by weight of solids by wet grinding of "D-600" manufactured by Nihon Tarku), rubber fine particle dispersion liquid epoxy resin ("BPA328" manufactured by Nihon Shokubai) , Potential curing accelerator for epoxy resin ("U-CAT3502T" manufactured by San Apro), liquid epoxy resin ("GOT" manufactured by Nihon Kayaku Co.), and silane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) Then, the mixture was mixed with an azihomixer robomix type mixing stirrer (refer to Flymix Corporation). To this, an ionic liquid curing agent (N-acetylglycinetetrabutyl phosphonium salt) was added and uniformly dispersed with a high-speed rotary mixer to obtain varnish B.

(Production Example 3)

By the same method as the varnish A in Production Example 1, except for adding talc ("D-600" manufactured by Nihon Tarku, wet-milled, MEK slurry having a solid content of 30% by weight) to the formulation table in Table 1 below. Accordingly, varnish C was prepared.

(Production Example 4)

A varnish D was prepared in the same manner as in varnish B in Production Example 2, according to the formulation table in Table 1 below.

(Production Example 5)

A varnish E was prepared in the same manner as in varnish B in Production Example 2, according to the formulation table in Table 1 below.

(Test Examples 1 to 3)

For each resin composition layer produced by varnishes B, D, and E, the adhesion to the support was measured. Table 2 shows the results.

From the results in Table 2, it can be seen that by mixing talc in the resin composition layer of the film of the present invention, the adhesion of the resin composition layer to the support is greatly improved.

(Test Examples 4 to 6)

Varnish A was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent, so that the thickness of the resin composition layer after drying was 10 µm, for 12 minutes at 60 to 95° C. By drying, the protective resin composition layer A1 was obtained. The melt viscosity at 100°C of the protective resin composition layer A1 was 6170 poise.

Varnish A was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent so that the thickness of the resin composition layer after drying was 10 µm, for 6 minutes at 60 to 80° C. By drying, the protective resin composition layer A2 was obtained. The melt viscosity at 100°C of the protective resin composition layer A2 was 1030 poise.

Varnish B was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent, so that the thickness of the resin composition layer after drying was 30 µm, for 12 minutes at 60 to 95° C. By drying, the moisture absorption resin composition layer B1 was obtained. The melt viscosity at 100°C of the moisture absorbing resin composition layer B1 was 23700 poise.

Varnish B was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent so that the thickness of the resin composition layer after drying was 30 µm, for 6 minutes at 60 to 80°C. By drying, the moisture absorption resin composition layer B2 was obtained. The melt viscosity at 100°C of the moisture absorbing resin composition layer B2 was 4460 poise.

With the combination shown in Table 3, the protective resin composition layer with PET film and the moisture absorption resin composition layer with PET film face the protective resin composition layer and the moisture absorption resin composition layer with a vacuum laminator, temperature 100° C., pressure 1 Kg/ Lamination was performed under the condition of cm 2 (9.8×10 ⁴ Pa) to prepare films (Test Examples 4 to 6) having a support, a protective resin composition layer, and a moisture absorption resin composition layer. Then, the vicinity of the boundary between the protective resin composition layer and the moisture absorption resin composition layer on the cross section of each produced film was observed by SEM (scanning electron microscope) (magnification 2000 times). 2 is a SEM photograph of a film section of Test Example 4, FIG. 3 is a SEM photograph of a film section of Test Example 5, and FIG. 4 is a SEM photograph of a film section of Test Example 6.

The difference between the melt viscosity of the hygroscopic resin composition layer and the protective resin composition layer in the film (melt viscosity of the hygroscopic resin composition layer-melt viscosity of the protective resin composition layer) is that the film of Test Example 4 is 17530 poise, the film of Test Example 5 This 3430 poise, the film of Test Example 6 is -1710 poise. In the film of Test Example 4 (Fig. 2), the interface between the hygroscopic resin composition layer (upper layer) and the protective resin composition layer (lower layer) is approximately horizontal, and the protective resin composition layer (lower layer) from the hygroscopic resin composition layer (upper layer). The migration of the hygroscopic metal oxide to was not confirmed. Also in the film (Fig. 3) of Test Example 5, the migration of the hygroscopic metal oxide from the hygroscopic resin composition layer (upper layer) to the protective resin composition layer (lower layer) was not confirmed. On the other hand, in the film of Test Example 6 (FIG. 4), the migration of the hygroscopic metal oxide (light spots) 7 from the hygroscopic resin composition layer (upper layer) to the protective resin composition layer (lower layer) was confirmed.

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

(Preparation of organic EL device)

(Cleaning of ITO substrate and glass plate for sealing)

The ITO (indium-tin oxide) substrate and the glass plate for sealing were cleaned in a clean room of class 10000 and a clean booth of class 100, respectively. As the cleaning solvent, a detergent for semiconductor cleaning and ultrapure water (over 18 MΩ, total organic carbon (TOC): less than 10 ppb) were used, and an ultrasonic cleaner and a UV cleaner were used.

(Deposition process)

Vacuum degree of 1 to 2×10 ^-4 Pa, deposition rate of 1.0 to 2.0 kPa/s, 30 mm square (30 mm vertical × 30 mm horizontal), 0.7 mm thick glass base, Glass/SiO ₂ [53 nm]/ITO [55 nm] An organic EL device was fabricated by depositing each layer in the composition of /PEDOTㆍPSS[40nm]/α-NPD[50nm]/Alq ₃ [50nm]/LiF[0.8nm]/Al[15nm]. The light emitting area is 10×10 mm 2.

In addition, "PEDOT•PSS" is an abbreviation of (poly(3,4-ethylenedioxythiophene))-(polystyrenesulfonic acid), and "α-NPD" is (bis[N-(1-naphthyl)-N -Phenyl] benzidine), "Alq ₃ " is an abbreviation of tris(8-quinolinolato)aluminum.

(Encapsulation of organic EL elements)

First, the film of the present invention was laminated to a glass plate (21 mm×28 mm, 0.7 mm thick) as a sealing material. Lamination was carried out in a clean booth of class 100 by vacuum pressing under conditions of 80° C., reduced pressure (1×10 ⁻³ MPa or less) suction 20 seconds, and press 20 seconds.

Next, the support was peeled off, and the resin composition layer exposed to the glass plate was depressurized (1×10 ^-3 MPa or less) under a load of 80° C. and 0.04 MPa in a glove box having an oxygen concentration of 10 ppm or less and a moisture concentration of 10 ppm or less. ) Vacuum-pressed toward the organic EL element formation substrate under conditions of suction 120 seconds and press 20 seconds.

Thereafter, in the glove box, the film of the present invention was heat cured by heating on a hot plate at 110° C. for 30 minutes.

In addition, the resin composition layer is a laminate of a protective resin composition layer and a moisture absorption resin composition layer, and the laminate to the glass plate as a sealing material compresses the moisture absorption resin composition layer to the glass plate, and the laminate to the organic EL element forming substrate is a protective resin. The composition layer was pressed onto the organic EL element forming substrate.

(Example 1)

Varnish A was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent, so that the thickness of the resin composition layer after drying was 10 µm, for 12 minutes at 60 to 95° C. By drying, a protective resin composition layer was obtained.

Likewise, varnish B was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent, so that the thickness of the resin composition layer after drying was 30 µm, and 12 at 60 to 95° C. By drying for minutes, a moisture absorption resin composition layer was obtained.

The protective resin composition layer with PET film and the moisture absorption resin composition layer with PET film face the protective resin composition layer and the moisture absorption resin composition layer with a vacuum laminator, temperature 80° C., pressure 1Kg/cm 2 (9.8×10 ⁴ pa) It was laminated under the conditions of to produce a film of the present invention. Moreover, the melt viscosity at 80 degreeC of the protective resin composition layer was 27500 poise, and the melt viscosity at 80 degreeC of the moisture absorption resin composition layer was 63400 poise. Next, the PET film on the moisture-absorbing resin composition layer side of the film is peeled off, the moisture-absorbing resin composition layer is laminated on a glass plate as a sealing material, and then the PET film on the protective resin composition layer side is peeled off, and the protective resin composition layer is an organic EL device. The organic EL device was produced by laminating on a glass plate having a.

1A is a diagram schematically showing a cross-section of a fabricated organic EL device, and a protective resin composition layer (inorganic filler, on the formation surface of the organic EL element 4 of the substrate 5 on which the organic EL element 4 is formed) The hygroscopic metal oxide-free (3), the hygroscopic resin composition layer (inorganic filler, hygroscopic metal oxide containing) 2 and the encapsulation material (glass plate) 1 are laminated in this order.

(Comparative Example 1)

The varnish B was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent so that the thickness of the resin composition layer after drying was 40 µm, 12 minutes at 60 to 95° C. By drying for a while, a resin composition layer was obtained. After laminating the resin composition layer with a PET film on a glass plate as a 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 produce an organic EL device.

1B is a view schematically showing a cross-section of the produced organic EL device, and a resin composition layer (inorganic filler, hygroscopicity) on the formation surface of the organic EL element 4 of the substrate 5 on which the organic EL element 4 is formed. The metal oxide containing) 2 and the sealing material (glass plate) 1 are stacked in this order.

(Comparative Example 2)

The varnish A was uniformly coated with a die coater on the release surface of the PET film (38 µm thick) treated with an alkyd release agent so that the thickness of the resin composition layer after drying was 40 µm, 12 minutes at 60 to 95° C. By drying for a while, a resin composition layer was obtained. After the resin composition layer with PET film was laminated on a glass plate as a 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 produce an organic EL device.

1C is a diagram schematically showing a cross-section of a fabricated organic EL device, and a resin composition layer (inorganic filler, hygroscopicity) on the formation surface of the organic EL element 4 of the substrate 5 on which the organic EL element 4 is formed. The metal oxide-free) 3 and the sealing material (glass plate) 1 are laminated in this order.

(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. After peeling the PET film on the resin composition layer side derived from the varnish C of this film, and laminating the resin composition layer on a glass plate as a sealing material, the PET film on the resin composition layer side derived from the varnish A is peeled off, and the resin composition layer is removed. The organic EL device was produced by laminating on a glass plate having an organic EL element.

1D is a diagram schematically showing a cross-section of a fabricated organic EL device, and a resin composition layer (inorganic filler, hygroscopicity) on the formation surface of the organic EL element 4 of the substrate 5 on which the organic EL element 4 is formed. Metal oxide-free (3), resin composition layer (inorganic filler-containing, hygroscopic metal oxide-free) 6 and sealing material (glass plate) 1 are laminated in this order.

(Comparative Example 4)

The varnish C was uniformly coated with a die coater so that the thickness of the resin composition layer after drying was 40 μm on the release surface of the PET film (38 μm thick) treated with an alkyd release agent, and 12 minutes at 60 to 95° C. By drying for a while, a resin composition layer was obtained. After the resin composition layer with PET film was laminated on a glass plate as a sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element, thereby producing an organic EL device.

1E is a diagram schematically showing a cross-section of the produced organic EL device, and a resin composition layer (containing an inorganic filler) on the formation surface of the organic EL element 4 of the substrate 5 on which the organic EL element 4 is formed. The hygroscopic metal oxide free) 6 and the encapsulation material (glass plate) 1 are laminated in this order.

Table 4 shows the results of the performance evaluation of the organic EL devices of Examples 1 and Comparative Examples 1 to 4.

From Example 1, it can be seen that, by using the film of the present invention, it is possible to easily form an encapsulation structure of an organic EL element that achieves a high level of blocking from moisture in the organic EL element while reducing damage to the organic EL element. Can be. In addition, in Example 1, the moisture absorbing resin composition layer and the protective resin composition layer are cured at low temperature to seal the organic EL element, so that not only the damage to the organic EL element in the sealing operation but also the thermal degradation of the organic EL element is sufficiently suppressed. As a result, a highly reliable organic EL device device could be obtained.

On the other hand, Comparative Example 1 contained a large amount of hygroscopic metal oxides, and the organic EL device was damaged. In addition, since Comparative Examples 2, 3, and 4 did not contain a hygroscopic metal oxide, the organic EL device was damaged by moisture. Further, Comparative Example 4 contained talc, but was difficult to migrate due to the flat filler, and thus the damage resistance of the device was observed.

[Industrial availability]

The film having the support, the protective resin composition layer, and the moisture absorbing resin composition layer can realize a film having both moisture permeability and damage resistance of the device, and such a film makes it possible to provide a highly reliable organic EL device.

This application is based on Japanese Patent Application No. 2009-182827 filed in Japan, the contents of which are all incorporated herein.

1 bag material (glass plate)
2 layer of hygroscopic resin composition (containing inorganic filler and hygroscopic metal oxide)
3 Protective resin composition layer (no inorganic filler, hygroscopic metal oxide-free)
4 Organic EL device
5 substrate
6 Resin composition layer (with inorganic filler, without hygroscopic metal oxide)
7 Hygroscopic metal oxide

Claims (11)

A laminated film having a support, a protective resin composition layer, and a moisture absorption resin composition layer, wherein the protective resin composition layer and the moisture absorption resin composition layer are adjacent to each other, wherein the protective resin composition layer is composed of a thermosetting resin composition containing a thermosetting resin and a curing agent, and a moisture absorption resin The composition layer is composed of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a hygroscopic metal oxide, the thermosetting resin is an epoxy resin, the average particle diameter of the hygroscopic metal oxide is 10 µm or less, and the content of the hygroscopic metal oxide in the resin composition is 1 to 40% by weight relative to 100% by weight of the nonvolatile matter in the resin composition, and at a lamination temperature set in the range of 40°C to 130°C, the difference in melt viscosity between the moisture absorption resin composition layer and the protective resin composition layer (hygroscopic resin composition layer The melt viscosity of the protective resin composition layer) is 3430 poise to 1000000 poise, characterized in that the film. The method according to claim 1, further comprising a protective film, in the order of a support, a moisture absorption resin composition layer, a protective resin composition layer, a protective film, or, in the order of a support, a protective resin composition layer, a moisture absorption resin composition layer, a protective film The film characterized by being laminated. The film according to claim 1 or 2, wherein the hygroscopic resin composition layer contains an inorganic filler (except for hygroscopic metal oxides). The film according to claim 1 or 2, wherein the protective resin composition layer contains an inorganic filler (except for hygroscopic metal oxides). The film according to claim 1 or 2, wherein the protective resin composition layer is a film for sealing an organic EL element, which is used to cover the organic EL element. An organic EL device comprising the film according to claim 1 or 2. Has a support and a protective resin composition layer and a moisture absorption resin composition layer,
The protective resin composition layer and the hygroscopic resin composition layer are composed of a thermosetting resin composition containing a thermosetting resin and a curing agent, the resin composition constituting the hygroscopic resin composition layer contains a hygroscopic metal oxide, and the thermosetting resin is an epoxy resin , The average particle diameter of the hygroscopic metal oxide is 10 µm or less, and the content of the hygroscopic metal oxide in the resin composition constituting the hygroscopic resin composition layer is 1 to 40% by weight relative to 100% by weight of the nonvolatile matter in the resin composition,
A film for organic EL device encapsulation is produced comprising a structure laminated in the order of a support, a moisture absorption resin composition layer, and a protective resin composition layer, or a structure laminated in a order of a support, a protective resin composition layer and a moisture absorption resin composition layer. As a way to do,
It has a process of laminating the moisture absorption resin composition layer and the protective resin composition layer at a lamination temperature set in the range of 40 ℃ to 130 ℃,
The difference between the melt viscosity of the hygroscopic resin composition layer and the protective resin composition layer at a lamination temperature set in the range of 40°C to 130°C (melt viscosity of the hygroscopic resin composition layer-melt viscosity of the protective resin composition layer) is 3430 bags. A method of manufacturing a film for sealing an organic EL device, characterized in that it is from 1 to 1000000 poise. The organic EL device encapsulating film according to claim 7, further comprising a protective film, a support, a moisture-absorbing resin composition layer, a protective resin composition layer, a structure laminated in this order, or a support, a protective resin composition. A layer, a moisture absorption resin composition layer, and a method of manufacturing a film for encapsulating an organic EL device, characterized in that it comprises a structure laminated in this order. The method for manufacturing a film for sealing an organic EL device according to claim 7 or 8, wherein the hygroscopic resin composition layer contains an inorganic filler (except for hygroscopic metal oxides). The content of the inorganic filler (except for the hygroscopic metal oxide) in the resin composition constituting the hygroscopic resin composition layer is 1 wt% or more and 50 wt% or less with respect to 100 wt% of the nonvolatile matter in the resin composition according to claim 9, Method for manufacturing a film for sealing an organic EL device. delete

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