KR20120039753A - Film - Google Patents

Abstract

This invention is a film which has a support body, a protective resin composition layer, and a moisture absorption resin composition layer. By such a structure, the film which has sufficient moisture permeability and damage resistance (namely, the function which prevents damage to an element) of an element can be implement | achieved. The film of the present invention is particularly suitable for encapsulation of an organic EL element, and by using the film of the present invention, not only the damage of the organic EL element in the sealing operation but also the thermal degradation of the organic EL element are sufficiently suppressed and the organic material having high reliability 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.

BACKGROUND OF THE INVENTION An organic EL (Electrolumiinescence) 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 luminance light emission at low voltage. However, the organic EL element is very weak to moisture, and the organic material itself is deteriorated by moisture, so that the brightness is lowered or does not emit light, or the interface between the electrode and the organic EL layer is peeled off due to moisture, or the metal is oxidized. There has been a problem of 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 so as to cover the entire organic EL layer, and a non-permeable glass substrate is bonded. However, since an acrylic ultraviolet curable resin composition is used for the curable resin layer, a problem of deterioration of the organic EL element due to ultraviolet rays or an uncured portion is generated in a place where ultraviolet rays do not reach, and a highly reliable sealing structure is obtained. It was not satisfactory in that it was difficult.

Moreover, in patent document 2, the thermosetting type curable resin composition which performs the whole surface sealing of organic electroluminescent element is proposed. However, it was not satisfactory in the point that the moisture permeability of the obtained hardened | cured material layer was not enough.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-182759 Patent Document 2: Japanese Unexamined Patent Publication No. 2006-70221

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly research, this inventor discovered that the said subject was solved by the film which has a support body, a protective resin composition layer, and a moisture absorption resin composition layer, and completed this invention.

That is, this invention includes the following forms.

(1) It has a support body, a protective resin composition layer, and a moisture absorption resin composition layer, The film characterized by the above-mentioned.

(2) Hygroscopic resin composition layer contains a hygroscopic metal oxide, The film as described in said (1) characterized by the above-mentioned.

(3) The moisture absorption resin composition layer contains an inorganic filler (except a hygroscopic metal oxide), The film as described in said (1) or (2) characterized by the above-mentioned.

(4) The film as described in any one of said (1)-(3) characterized by the protective resin composition layer containing an inorganic filler (except a hygroscopic metal oxide).

(5) At the lamination temperature set in the range of 40-130 degreeC, the difference (melt viscosity of a moisture absorption resin composition layer-melt viscosity of a protection resin composition layer) of the moisture absorption resin composition layer and a protective resin composition layer is 300-300 It is 100000 poise, The film in any one of said (1)-(4) characterized by the above-mentioned.

(6) The organic EL device containing the film in any one of said (1)-(5) characterized by the above-mentioned.

The film which has a support body, a protective resin composition layer, and a moisture absorption resin composition layer can provide the film which has sufficient moisture permeability and damage resistance (namely, the function which prevents damage to an element) of an element.

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 the organic EL device of Comparative Examples 1 to 4. FIG.
2 is a SEM photograph of the cross section of the film of Test Example 4.
3 is a SEM photograph of a film cross section of Test Example 5. FIG.
4 is a SEM photograph of a cross section of a film of Test Example 6. FIG.

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

[Support]

Although the support body used for this invention means "the substance which supports a protective resin composition layer or a moisture absorption resin composition layer", there is no restriction | limiting in particular as long as it exhibits the function.

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

A peeling system support body means the support body which can peel at the time of manufacture of various devices (namely, the support body peeled (separated) from the film of this invention at the time of preparation of various devices). As such a peeling system support body, specifically, polyolefin, such as polyethylene, a polypropylene, polyvinyl chloride, polyethylene terephthalate (it may abbreviate as "PET" hereafter.), And polyethylene naphthalate (it abbreviates as "PEN" hereafter). The film which consists of plastics, such as polyester, polycarbonate, and polyimide, etc. may be mentioned. From a cost performance viewpoint, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film is more preferable.

Although the thickness of a peeling system support body is not specifically limited, From a viewpoint of the handleability of the film of this invention, 150 micrometers or less are preferable, as for the upper limit of the thickness of the said support body, 120 micrometers or less are more preferable, 90 micrometers or less are still more preferable. Do. On the other hand, as for the minimum of thickness, 10 micrometers or more are preferable from a viewpoint of the handleability, moistureproofness, etc. of the film of this invention, 40 micrometers or more are more preferable, and its 70 micrometers or more are more preferable.

It is preferable to perform a mold release process previously, and as a mold release agent used for a mold release process, a fluorine type mold release agent, a silicone type mold release agent, an alkyd resin mold release agent, etc. are mentioned specifically ,. You may use a mold release agent 1 type or in mixture of 2 or more types. In addition, the surface of a peeling system support body may be a mat process, a corona treatment, etc., and may release-process on the surface on which such a process was carried out again.

The encapsulation-based support means a support having moisture resistance that can be used as a part of various devices as it is during the production of various devices (that is, provided in the manufacture of various devices and embedded in a device to be finally manufactured). More specifically, the support is a sealing material in which the elements (semiconductor element, LED element, organic EL element, etc.) are disposed in the outermost layer separated from the element formation substrate formed on the surface thereof in the sealing structure of various devices. Used as As said support body, metal foil or the laminated | multilayer film in which metal foil or the inorganic vapor deposition film was laminated on at least one surface of a plastic film is mentioned, for example. Examples of the metal foil include copper foil and aluminum foil, and examples of the inorganic vapor deposition film include vapor deposition films such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon. In addition, a commercially available plastic film having moisture resistance can be used for the support, and for example, TechBarrier HX, AX, LX, L series (see Mitsubishi Jushi Co., Ltd.) and X-BARRIER which further improved the moisture-proofing effect. [Reference: Mitsubishi Jushi Co., Ltd.] 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 manufacturing an organic EL device using the film of this invention using the sealing type support body, the light emitting surface of the organic electroluminescent device produced becomes a surface opposite to the surface in which the organic electroluminescent element of the element formation substrate was formed.

Although the thickness of a support body is not specifically limited when metal foil is used for an encapsulation support body, or when an inorganic vapor deposition film or a metal foil is laminated on at least one surface of a plastic film, From a viewpoint of the handleability of the film of this invention 150 micrometers or less are preferable, as for the upper limit of the thickness of the said support body, 120 micrometers or less are more preferable, and 90 micrometers or less are more preferable. On the other hand, as for the minimum of thickness, 10 micrometers or more are preferable from a viewpoint of the handleability, moistureproofness, etc. of the film of this invention, 40 micrometers or more are more preferable, and its 70 micrometers or more are more preferable.

5 mm or less is preferable from a viewpoint of making thin and light organic EL device itself as the upper limit of the thickness of the said support body, when using a glass plate or a metal plate for a sealing support body, More preferably, 1 mm or less is more preferable, and 100 micrometers or less are more preferable. 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 viewpoint of preventing moisture permeation, rigidity of the organic EL device, and the like.

The laminated film in which metal foil is laminated on at least one side of the plastic film is coated on a plastic film such as a PET film using an application head capable of coating a thin film such as a gravure coater, and a metal foil such as aluminum on the coated surface of the adhesive. It can be obtained by laminating. 5 micrometers or more are preferable from a viewpoint of lamination property, moisture permeability, etc., and, as for the thickness of metal foil, 125 micrometers or less are preferable from a viewpoint of handleability. Moreover, it is preferable to make the total thickness of the laminated | multilayer film of this 3-layered structure into the range of 10-150 micrometers.

[Moisture absorption resin composition layer]

The moisture absorption resin composition layer used for the film of this invention is comprised by the thermosetting resin composition containing a thermosetting resin, a hardening | curing agent, and a hygroscopic metal oxide, and has moisture permeability. This prevents the intrusion of moisture into the element (organic EL element, etc.) in the sealing structure of the target device (organic EL device, etc.).

(Thermosetting resin and hardener)

The thermosetting resin and the 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, vinyl benzyl resins and the like The hardening | curing agent of is mentioned. Among these, an epoxy resin and its hardening | curing agent are preferable from a viewpoint of low temperature curability, adhesiveness of hardened | cured material, etc.

As an epoxy resin, what is necessary is just to have two or more epoxy groups per average molecule, and specifically, a bisphenol-A epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy Resin, bisphenol F-type epoxy resin, phosphorus containing epoxy resin, bisphenol S-type epoxy resin, aromatic glycidyl amine type epoxy resin (specifically, tetraglycidyl diamino diphenylmethane, 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 etherification of bisphenol Water, diglycidyl ethers of naphthalenediol, glycidyl ethers of phenols, and diglycidyl ethers of alcohols, and alkyl substituents, halides and hydrogenated products of these epoxy resins. . You may use these 1 type or in combination of 2 or more types.

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

The epoxy resin may be either liquid or solid, or both liquid and solid. Here, "liquid phase" and "solid state" are states of an epoxy resin at 25 ° C. It is preferable that 10 weight% or more of the whole epoxy resin to be used is liquid form from a viewpoint of applicability | paintability, processability, adhesiveness, etc.

In addition, the epoxy resin is preferably in the range of 100 to 1000 epoxy equivalent, more preferably 120 to 1000 in view of reactivity. Epoxy equivalent is the number of grams (g / eq) of resin containing an epoxy group of 1 g equivalent here, and is measured according to the method prescribed | regulated to JISK-7236.

Although it will not specifically limit, if it has a function which hardens an epoxy resin as a hardening | curing agent of an epoxy resin, From a viewpoint of suppressing thermal deterioration of the element (especially organic electroluminescent element) at the time of the hardening process of a resin composition, hardening process of a resin composition Preferably, it is preferable to carry out at 140 degrees C or less, More preferably, it is 120 degrees C or less, and it is preferable that a hardening | curing agent has the hardening effect of an epoxy resin in this temperature range.

Specific examples thereof include primary amine, secondary amine, tertiary amine curing agent, polyaminoamide curing agent, dicyandiamide, organic acid dihydrazide, and the like. Duct-based compound (Amicure PN-23, Amcure MY-24, Amcure PN-D, Amcure MY-D, Amcure PN-H, Amcure MY-H, Amcure PN-31, Amcure PN- 40, Amicure PN-40J, etc. (all are manufactured by Ajinomoto Fine-Techno Co., Ltd.), organic acid dehydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH etc. (all are manufactured by Ajinomoto Fine-Techno Co., Ltd.)), etc. are preferable. Do. You may use these 1 type or in combination or 2 or more types.

Further, an epoxy resin as an ionic liquid capable of curing the epoxy resin at a temperature of 140 ° C. or lower, preferably 120 ° C. or lower, that is, a salt that can be melted in a temperature range of 140 ° C. or lower, preferably 120 ° C. or lower. Salts having a curing action of are particularly suitably used. The ionic liquid works advantageously to improve the moisture permeability of the cured product of the hygroscopic resin composition layer. In addition, it is preferable that an ionic liquid is used in the state which melt | dissolves the said ionic liquid uniformly in an epoxy resin.

Examples of the cation constituting such an ionic liquid include ammonium cations such as imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guanidinium ions and pyridinium ions; Phosphonium-based cations such as tetraalkylphosphonium cations (specifically, tetrabutylphosphonium ions, tributylhexyl phosphonium ions and the like); Sulfonium cations such as triethylsulfonium ion; and the like.

Moreover, as an anion which comprises such an ionic liquid, Halide type | system | group anions, such as a fluoride ion, chloride ion, bromide ion, and iodide ion; Alkyl sulfate type | system | group anions, such as methanesulfonic acid ion; 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; Phenol anions such as phenol ions, 2-methoxyphenol ions and 2,6-di-tert-butylphenol ions; Acidic amino acid ions such as aspartic acid ions and glutamic acid ions; Neutral amino acid ions such as glycine ions, alanine ions and phenylalanine ions; N-acylamino acid ions of the following formula (1), such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion; Carboxylic 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, manic acid ion, N-methylmanic acid ion and benzoic acid ion Can be mentioned.

Wherein R-CO- is an acyl group derived from a linear or branched fatty acid having 1 to 5 carbon atoms, or a substituted or unsubstituted benzoyl group, and -NH-CHX-CO ₂ -is an aspartic acid, glutamic acid, or the like. Acidic amino acid ions or neutral amino acid ions such as glycine, alanine, phenylalanine, etc.)

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

The anion is preferably a phenol anion, an N-acylamino acid ion or a carboxylic acid anion of formula (1), and more preferably an N-acylamino acid ion or a carboxylic acid anion.

Specific examples of the phenol-based anion include 2,6-di-tert-butylphenol ions. Specific examples of the carboxylic acid anion include acetate ions, decanoate ions, 2-pyrrolidone-5-carboxylic acid ions, formic acid ions, α-lipoic acid ions, lactic acid ions, tartaric acid ions, manuric acid ions, and N-methylmanic acid. Ions and the like, among these, acetate ions, 2-pyrrolidone-5-carboxylic acid ions, formic acid ions, lactic acid ions, tartaric acid ions, manic acid ions, and N-methylmanic acid ions are preferable, and acetate ions, N-methylmanic acid ions and formic acid ions are particularly preferred. Specific examples of the N-acylamino acid ions of the general formula (1) include N-benzoylalanine ions, N-acetylphenylalanine ions, asparagine ions, glycine ions, N-acetylglycine ions and the like. Among these, N-benzoylalanine Ions, N-acetylphenylalanine ions, N-acetylglycine ions are preferred, and N-acetylglycine ions are particularly preferred.

Specific ionic liquids include 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutyl Phosphonium trifluoroacetate, tetrabutyl phosphonium α-lipoate, tetrabutyl phosphonium salt formate, tetrabutyl phosphonium lactate, bis (tetrabutyl phosphonium) salt, tungstate tetrabutyl phosphonium salt, N- Methyl manganese tetrabutylphosphonium salt, benzoyl-DL-alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenoltetrabutylphosphonium salt, L-aspartic acid mono Tetrabutylphosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, form 1-ethyl-3-methylimidazolium salt, urinary acid-1-ethyl-3-methylimidazolium salt, N-methylmanic acid 1-ethyl-3-methylimidazolium salt, bis tartaric acid bis (1-ethyl 3-methyl imidazolium) salt and N-acetylglycine 1-ethyl-3-methyl imidazolium salt are preferable, and N-acetylglycine tetrabutyl phosphonium salt and 1-ethyl-3- methyl imidazolium acetate , 1-ethyl-3-methylimidazolium salt, formic acid 1-ethyl-3-methylimidazolium salt, and N-methylmanic acid-1-ethyl-3-methylimidazolium salt are particularly preferred.

As a method for synthesizing the ionic liquid, NaBF ₄ , NaPF ₆ , CF ₃ SO is applied to a precursor composed of a cation moiety such as alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions and an anion moiety containing a halogen. ₃ Anion exchange method for reacting Na or LiN (SO ₂ CF ₃ ) _2, etc., an acid ester method in which an organic acid residue becomes a monoanion while introducing an alkyl group by reacting an amine-based substance with an acid ester, and neutralizing the amine with an organic acid. Although there exists a neutralization method etc. which obtain a salt, it is not limited to these. In the neutralization method using an anion, a cation, and a solvent, an equivalent amount of an anion and a cation can be used, and the solvent in the obtained reaction solution can be distilled off and used as it is. ) May be injected to concentrate the liquid.

It is preferable to use a hardening | curing agent in 0.1-50 weight% with respect to 100 weight% of non volatile matters in a resin composition, The range of 0.5-25 weight% is more preferable, The range of 1-15 weight% is further more preferable. And the range of 1.5 to 10 weight% is further more preferable. When less than this range, sufficient sclerosis | hardenability may not be obtained, and when more than 50 weight%, not only the storage stability of a resin composition may be impaired, but also the moisture permeability and heat resistance of hardened | cured material may fall. In addition, when using an ionic liquid, 0.1-10 weight% is preferable with respect to 100 weight% of non volatile matters of an epoxy resin, and 0.5-8 weight% is more preferable at the point of moisture permeability, etc. of the hardened | cured material of a resin composition. , 1 to 6% by weight is more preferable, and 1.5 to 5% by weight is more preferable.

In the resin composition which comprises a moisture absorption resin composition layer in this invention, in order to adjust hardening temperature, hardening time, etc., you may contain the hardening accelerator further. As a curing accelerator, quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, quaternary sulfonium salts such as tetraphenylphosphonium bromide and tetrabutylphosphonium bromide, and DBU (1,8-diazabicyclo (5.4.0)) Undecene-7), DBN (1,5-diazabicyclo (4.3.0) nonen-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU- Imidazole compounds such as diazabicyclo compounds such as phenol novolac resin salts, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, Tertiary amines such as tris (dimethylaminomethyl) phenol and benzyldimethylamine, dimethylurea compounds such as aromatic dimethylurea, aliphatic dimethylurea, aromatic dimethylurea and the like.

Content in the case of using a hardening accelerator is 0.01-7 weight% with respect to the total amount of an epoxy resin.

(Hygroscopic metal oxide)

The term "hygroscopic metal oxide" as used in the present invention is a metal oxide which has the ability to absorb moisture and chemically reacts with moisture that is absorbed to form a hydroxide, and the object of the present invention is not particularly limited. , Calcium oxide, magnesium oxide, strontium oxide, aluminum oxide and barium oxide, or a mixture or solid solution of two or more metal oxides selected from these. Specific examples of the mixture or solid solution of two or more metal oxides include calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide), and the like. Such a hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercial item can be used. Specifically, calcined dolomite ("KT" made by Yoshizawa Sekigaisa Co., Ltd.), calcium oxide ("Moistop # 10" made by Sankyo Sehun Co., Ltd.), magnesium oxide ("Kyowa Maku MF-" made by Kyowa Kagaku Kogyo Co., Ltd.) 150 "," Kyowa mug MF-30 ", Tatehogagaku Kogyo Co., Ltd." pure mug FNMG ", etc., light magnesium oxide (" # 500 "," # 1000 "made by Tatehogagaku Co., Ltd.) , "# 5000", and the like.

Although the average particle diameter of a hygroscopic metal oxide is not specifically limited, 10 micrometers or less are preferable, 5 micrometers or less are more preferable, and 1 micrometer or less is more preferable. By using such a micro sized thing, not only a high moisture permeability can be provided to the hardened layer of a moisture absorption resin composition, but adhesive force can be improved. In addition, when the average particle diameter of the hygroscopic metal oxide is too small, the particles tend to aggregate and become difficult to perform sheet processing, 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 item of a hygroscopic metal oxide is 10 micrometers or less, it can be used as it is, but when an average particle diameter of a commercial item exceeds 10 micrometers, it grinds, classifies, etc., and granulates with an average particle diameter of 10 micrometers or less It is preferable to use after preparing.

The "average particle diameter" here is the median diameter of the said particle size distribution at the time of creating the particle size distribution of a measurement object (granular material) 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 Sesaku Sho Co., Ltd. Can be used. It is preferable that the measurement sample uses what disperse | distributed the hygroscopic metal oxide in water by the ultrasonic wave.

As a hygroscopic metal oxide, what surface-treated with the surface treating agent can be used. By using such a surface treated hygroscopic metal oxide, the storage stability of the resin composition which comprises a hygroscopic resin composition layer can be improved more, and it can prevent that the moisture in a resin and a hygroscopic metal oxide react at the pre-curing step.

As a surface treating agent used for surface treatment, a higher fatty acid, an alkylsilane, a silane coupling agent, etc. can be used specifically, Among these, a higher fatty acid or alkylsilane is suitable.

Specifically, the higher fatty acid is preferably a C18 or higher higher fatty acid such as stearic acid, montanic acid, millic acid or palmitic acid, and stearic acid is more preferable. You may use these 1 type or in combination of 2 or more types.

Examples of the alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane and octyltrie. Oxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, and the like. You may use these 1 type or in combination or 2 or more types.

Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- Epoxy silane coupling agents such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptodecyltrimethoxysilane; 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; Vinyl silane coupling agents such as urea-based silane coupling agents such as 3-ureidepropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatepropyltrimethoxysilane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; Phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, a triazine silane, etc. are mentioned. You may use these 1 type or in combination or 2 or more types.

Surface treatment can be performed by adding and spraying a surface treating agent and stirring for 5 to 60 minutes, stirring and dispersing an untreated hygroscopic metal oxide at normal temperature with a mixer specifically ,. As a mixer, a well-known mixer can be used, Specifically, blenders, such as a V blender, a ribbon blender, a bubble cone blender, a mixer, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. Moreover, when grind | pulverizing a moisture absorber with a ball mill etc., the method of mixing and surface-treating said higher fatty acid, alkylsilanes, or a silane coupling agent is also possible. Although the treatment amount of the surface treating agent is also different depending on the kind of the hygroscopic metal oxide, the kind of the surface treating agent, and the like, it is preferably 1 to 10% by weight based on the hygroscopic metal oxide.

If the upper limit of the content of the hygroscopic metal oxide in the resin composition is too high, the content of the hygroscopic metal oxide increases, the viscosity of the resin composition increases, and the strength of the cured product is lowered, so that the content of the nonvolatile matter in the resin composition is 100% by weight. 40 weight% or less is preferable, 35 weight% or less is more preferable, 30 weight% or less is more preferable, 25 weight% or less is still more preferable, 20 weight% or less is especially preferable. On the other hand, the lower limit of the content of the hygroscopic metal oxide is preferably 1% by weight or more, and preferably 5% by weight or more, based on 100% by weight of the nonvolatile matter in the resin composition from the viewpoint of sufficiently obtaining the effect of containing the hygroscopic metal oxide. More preferably, 10 weight% or more is more preferable.

(Inorganic filler)

The resin composition constituting the hygroscopic resin composition layer can further contain an inorganic filler (except for the hygroscopic metal oxide). By containing the said inorganic filler, the moisture permeability-proof of the hardened | cured material of a resin composition improves, the repellence of the composition at the time of film preparation is prevented, and the adhesive force with a support body or sealing material can be improved. Specific examples of the inorganic fillers include 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, Barium zirconate, calcium zirconate, talc, clay, mica, boehmite, zeolite, apatite, kaolin, mullite, spinel, oribin, sericite, bentonite and the like. You may use an inorganic filler 1 type or in combination of 2 or more types. Among these, from the viewpoint that the inorganic filler is difficult to transfer to another layer during the lamination, a filler having a flat platelet shape such as talc, clay, mica and boehmite is preferable, and by using a filler having a flat platelet shape of such particles, The moisture permeability of the hardened layer obtained by hardening a resin composition layer can be improved further.

The upper limit of the average particle diameter of the inorganic filler is preferably 1 µm or less, more preferably 0.8 µm or less, from the viewpoint of improving dispersibility and preventing the lowering of mechanical strength or from moving the inorganic filler to another layer during lamination. And 0.6 micrometer or less is more preferable. Moreover, as for the minimum of the average particle diameter of an inorganic filler, 0.01 micrometer or more is preferable, and 0.1 micrometer or more is preferable from a viewpoint of the prevention of the fall of dispersibility by aggregation, and the fall of the handleability by the viscosity increase of a resin composition. 0.3 micrometers or more are more preferable. In addition, an average particle diameter here is synonymous with the average particle diameter in said hygroscopic metal oxide.

The upper limit of the content of the inorganic filler in the resin composition is 100% by weight of the nonvolatile matter in the resin composition from the viewpoint of increasing the viscosity of the resin composition and decreasing the strength of the cured product when the content of the inorganic filler is excessively increased. 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 further more preferable. On the other hand, as for the minimum of content of an inorganic filler, 1 weight% or more is preferable with respect to 100 weight% of non volatile matters in a resin composition from a viewpoint of fully obtaining the effect of an inorganic filler, 5 weight% or more is more preferable, 10 weight More than% is more preferable.

(Rubber particles)

The resin composition which comprises a moisture absorption resin composition layer can be made to contain rubber particle further, and by including rubber particle, improvement of the mechanical strength of the hardened | cured material of a resin composition, stress relaxation, etc. can be aimed at. 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 component in resin compositions, such as an epoxy resin, and exists in a dispersion state in the varnish of a resin composition. Generally, such rubber particles can be prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or resin to form a particulate, and specifically, core-shell rubber particles and crosslinked acrylonitrile butadiene rubber. Particles, crosslinked styrene-butadiene rubber particles, acrylic rubber particles, and the like. The core-shell rubber particles are rubber particles in which the particles have a core layer and a shell layer. Specifically, the shell layer of the outer layer is made of glassy polymer, the core layer of the inner layer is made of rubbery polymer, or the shell layer of the outer layer is glassy. The polymer, the intermediate | middle layer, a rubber | gum polymer, and the core layer consist of a three layer structure comprised from a glassy polymer etc. are mentioned. The glass layer is specifically comprised by the polymer of methyl methacrylate, etc., and a rubbery polymer layer is specifically comprised by butylacrylate polymer (butyl acrylate rubber) etc. 2 micrometers or less are preferable from a viewpoint of the upper limit of the average particle diameter of the primary particle of these rubber particles holding the effect of stress relaxation, or preventing damage to the element at the time of sealing an organic EL element with a 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 the increase in the viscosity when mixed with the resin. Specific examples of the core-shell rubber particles include staphyloid AC3832, AC3816N (reference: manufactured by Gantz Kasei Co., Ltd.), metablen KW-4426 (reference: Mitsubishi Rayon Co., Ltd.), F351 (reference: Nihon Zeon Co., Ltd.), and the like. have. As an example of acrylonitrile butadiene rubber (NBR) particle | grains, XER-91 (made by JSR Corporation) etc. are mentioned. As an example of styrene-butadiene rubber (SBR) particle | grains, XSK-500 (reference: the JSR Corporation make), etc. are mentioned. As a specific example of an acryl rubber particle, metablene W300A and W450A (reference: the Mitsubishi Rayon company make) is mentioned.

The average particle diameter of a rubber particle can be measured using a dynamic light scattering method. Specifically, the rubber particles are uniformly dispersed by an ultrasonic wave or the like in a suitable organic solvent, 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 measures by making it a particle diameter.

As for the upper limit of content of a rubber particle, 20 weight% or less is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint of preventing the fall of the heat resistance and moisture permeability of a moisture absorption resin composition layer, and 10 weight% or less More preferred. On the other hand, as for the minimum of content of a rubber particle, 0.1 weight% or more is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint of fully obtaining the effect of mix | blending rubber particle.

Moreover, the rubber particle dispersion | distribution epoxy resin which disperse | distributed rubber particle to the epoxy particle in the state of a primary particle is marketed, You may contain rubber particle in a resin composition by using a rubber particle dispersion epoxy resin as an epoxy resin. Specifically as such a rubber particle-dispersed epoxy resin, Nippon Shokubai Co., Ltd. make "BPA328" (rubber particle: acrylic core shell type resin, average particle diameter of rubber particle: 0.3 micrometer, rubber particle content: 17 weight%, epoxy resin) : Bisphenol A type epoxy resin of epoxy equivalent 185, "MX120" by Kaneka Corporation (rubber particle: SBR resin, average particle diameter of rubber particle: 0.1 micrometer, rubber particle content: 25 weight%, epoxy resin: epoxy equivalent 185 bisphenol A epoxy resin) etc. are mentioned.

(Thermoplastic)

The resin composition constituting the hygroscopic resin composition layer can further contain a thermoplastic resin. By containing a thermoplastic resin, flexibility can be provided to the hardened | cured material of a resin composition, and the favorable workability at the time of coating a resin composition can be provided. Specific examples of the thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, and polysulfone resins. Any one of these thermoplastic resins may be used, or two or more thereof may be mixed and used. The thermoplastic resin has a weight average molecular weight of preferably 10,000 or more, more preferably 30,000 or more, from the viewpoint of providing flexibility and preventing splashing during coating. However, when a weight average molecular weight is too big | large, since there exists a tendency for compatibility with an epoxy resin to fall, etc., it is preferable that a weight average molecular weight is 1,000,000 or less, and 800,000 or less are more preferable.

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

Among the above-mentioned examples, the thermoplastic resin is particularly preferably a phenoxy resin. A phenoxy resin is preferable also in the point that compatibility with "epoxy resin" is good, and there is little influence on the adhesiveness and moisture resistance of the hardened | cured material of a resin composition.

Examples of the phenoxy resin include 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, The thing which has 1 or more types of frame | skeleton chosen from an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton is mentioned. You may use phenoxy resin in mixture of 2 or more types.

As a commercial item of the phenoxy resin, 1256, 4250 (bisphenol A frame | skeleton containing phenoxy resin) made by Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S frame containing phenoxy resin) made by Japan Epoxy Resin company, 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 Totogase Co., Ltd. YL7553BH30, YL6794, YL7213, YL7290, and YL7482 by FX293 and the Japan epoxy resin company are mentioned.

As for the upper limit of content of a thermoplastic resin, 50 weight% or less is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint of the prevention of the moisture permeability-proof fall of hardened | cured material, and 25 weight% or less is more preferable. On the other hand, 1 weight% or more is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint that the minimum of content of a thermoplastic resin acquires sufficient effect by containing a thermoplastic resin, and 3 weight% or more More preferably, 5 weight% or more is more preferable, and 10 weight% or more is further more preferable.

(Coupling agent)

By containing a coupling agent further in the moisture absorption resin composition layer used for this invention, adhesiveness with the to-be-adhered body (support body, protective resin composition layer, sealing material, etc.) and moisture permeability of hardened | cured material can be improved. Specific examples of the coupling agent include titanium coupling agents, aluminum coupling agents, silane coupling agents, and the like. Among these, a silane coupling agent is preferable. You may use these 1 type or in combination or 2 or more types.

Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- ( Epoxy silane coupling agents such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane; Mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptodecyltrimethoxysilane; 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; Vinyl silane coupling agents such as urea-based silane coupling agents such as 3-ureidepropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatepropyltrimethoxysilane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; Phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, a triazine silane, etc. are mentioned. Among these, an epoxy silane coupling agent is especially suitable.

10 weight% or less is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint of obtaining the adhesive improvement effect by addition of a coupling agent, and, as for the upper limit of content of a coupling agent, 5 weight% or less is more preferable. . On the other hand, 0.5 weight% or more is preferable with respect to 100 weight% of non volatile matters in a moisture absorption resin composition layer from a viewpoint of obtaining the lower limit of content of a coupling agent and the adhesive improvement effect by addition of a coupling agent.

In the moisture absorption resin composition layer used for this invention, you may arbitrarily contain various additives other than said component in the range in which the effect of this invention is exhibited. Specific examples of such additives include organic fillers such as silicone powder and nylon powder fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, high-density defoamers or leveling agents, triazole compounds, thiazole compounds, triazine compounds, and the like. And adhesive agents such as porphyrin compounds.

Although the thickness of the moisture absorption resin composition layer used for this invention is not specifically limited, In the structure which laminated | stacked the support body on the resin composition layer, since moisture penetrates only in the resin composition layer side surface, the thickness of a moisture absorption resin composition layer is made small, From the viewpoint of blocking moisture by reducing the contact area with outside air, the upper limit of the thickness is preferably 200 µm or less, more preferably 150 µm or less, further preferably 100 µm or less. On the other hand, from the viewpoint of securing a moisture absorbent concentration for obtaining a sufficient moisture absorption 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 this invention is comprised by the thermosetting resin composition containing a thermosetting resin and a hardening | curing agent, and is an element (organic EL element etc.) by the sealing structure of the target device (organic EL device etc.). By directly coating the film, the moisture-absorbing metal oxide in the moisture-absorbing resin composition layer comes into contact with the device and prevents the device from being damaged.

(Thermosetting resin and hardener)

The same thing as the thermosetting resin and hardening | curing agent used for said hygroscopic resin composition layer is used for a thermosetting resin and a hardening | curing agent. Although the thermosetting resin and hardening | curing agent used for a protective resin composition layer, and the thermosetting resin and hardening | curing agent used for a hygroscopic resin composition layer may differ from each other, both layers after hardening resulting from the difference of adhesiveness, hardening shrinkage, or hardening rate between both layers It is preferable that the thermosetting resin and hardening | curing agent used for a protective resin composition layer, and the thermosetting resin and hardening | curing agent used for a moisture absorption resin composition layer are the same from a viewpoint of suppressing the interfacial stress.

(Hygroscopic metal oxide)

The protective resin composition layer used for this invention may contain a hygroscopic metal oxide further in the range which does not impair the damage prevention function of an organic EL element. By containing a hygroscopic metal oxide, moisture permeability can be improved.

When containing a hygroscopic metal oxide in a protective resin composition layer, the upper limit of content of a hygroscopic metal oxide is 5 weight% or less with respect to 100 weight% of non volatile matters in a protective resin composition layer from a viewpoint of preventing damage of an organic electroluminescent element. desirable. On the other hand, as for the minimum of content of a hygroscopic metal oxide, 0.5 weight% or more is preferable with respect to 100 weight% of non volatile matters in a protective resin composition layer from a viewpoint of obtaining the effect of the moisture permeability improvement.

In addition, even when the hygroscopic metal oxide is contained within the 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 average particle diameter of the hygroscopic metal oxide is preferably less than 1 µm. In addition, even if the average particle diameter is less than 1 µm, if the particle size distribution is broad, the organic EL element may be damaged by containing coarse particles. Therefore, 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 particle | grains.

In addition, the hygroscopic metal oxide contained in a protective resin composition layer can use the same metal oxide as the hygroscopic metal oxide contained in said moisture absorption resin composition layer, and surface treatment etc. can also be added in the same form. In addition, if the average particle diameter of a hygroscopic metal oxide is less than 1 micrometer, it can be used as it is, but when an average particle diameter of a commercial item is 1 micrometer or more, it grinds, classifies, etc., and granulates with an average particle diameter of less than 1 micrometer. It is prepared after using. The "average particle diameter" here is also synonymous with the average particle diameter of the hygroscopic metal oxide contained in the said moisture absorption resin composition layer.

(Inorganic filler)

By containing an inorganic filler (except hygroscopic metal oxide) in the protective resin composition layer used for this invention, the moisture permeation rate of an interface in a layer and an EL element side can be delayed, and adhesive force with a board | substrate can be improved. Can be. As said inorganic filler, the same thing as the inorganic filler used for said moisture absorption resin composition layer can be used. From the viewpoint that the inorganic filler is difficult to be exposed at the time of lamination, a filler in which the form of particles such as talc, clay, mica and boehmite is flat is preferable. In addition, when using an inorganic filler, the upper limit of content of an inorganic filler is 15 weight with respect to 100 weight% of non volatile matters in a resin composition layer from a viewpoint that the viscosity of a resin composition rises and the strength of hardened | cured material falls and falls off. % Or less is preferable and 10 weight% or less is more preferable. On the other hand, 1 weight% or more is preferable with respect to 100 weight% of non volatile matters in a resin composition from a viewpoint that the minimum of content of an inorganic filler acquires the effect which retards the water vapor transmission rate of the interface of a resin composition layer and an EL element side, 3 weight% or more is more preferable. In addition, when using an inorganic filler with a hygroscopic metal oxide, it is used in the range whose total amount of an inorganic filler and a hygroscopic metal oxide becomes 15 weight% or less with respect to 100 weight% of non volatile matters in a resin composition.

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

By containing rubber particle further, the protective resin composition layer used for this invention can implement improvement of the mechanical strength of the hardened | cured material, stress relaxation, etc. In addition, by containing a thermoplastic resin, the moisture absorption resin composition layer used for this invention can provide flexibility to the hardened | cured material, and can provide favorable workability at the time of coating a resin composition. Moreover, adhesiveness with the to-be-adhered body of the hardened | cured material and moisture permeability of hardened | cured material can be improved by containing a coupling agent further in the moisture absorption resin composition layer used for this invention. As the rubber particles, the thermoplastic resin, the coupling agent, and the like, rubber particles, thermoplastic resins, coupling agents, and the like used in the moisture absorption resin composition layer can be used. The coupling agent is preferably a silane coupling agent, and the thermoplastic resin is phenoxy. Resin is preferred. As for content in this thermosetting resin composition, content in the thermosetting resin composition which comprises a moisture absorption resin composition layer basically follows.

You may arbitrarily contain in the protective resin composition layer used for this invention the various additives other than said component in the range in which the effect of this invention is exhibited. Specifically, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, antifoaming agents or leveling agents, triazole compounds, thiazole compounds, triazine compounds and porphyrin compounds Adhesion-imparting agents, such as these, etc. are mentioned.

Although the thickness of the protective resin composition layer used for this invention is not specifically limited, From an viewpoint of preventing the increase of a moisture permeability, 40 micrometers or less are preferable and, as for the upper limit of thickness, 20 micrometers or less are more preferable. On the other hand, the lower limit of the thickness is preferably 1 µm or more, from the viewpoint of making the thickness sufficiently exhibit the damage preventing effect of the organic EL element.

[Protective film]

Until the film of this invention is actually used for formation of a sealing structure, it is preferable to be protected by the protective film in order to prevent adhesion | attachment and a damage of the dust etc. to the resin composition layer surface, As a protective film, said peeling system The plastic film exemplified for the support can be used. It is preferable to apply a mold release process to a protective film beforehand, and a fluorine mold release agent, a silicone type mold release agent, an alkyd resin mold release agent etc. are mentioned specifically as a mold release agent. You may use a mold release agent in mixture of a different kind. Moreover, the thickness of a protective film is not specifically limited, either, 1-100 micrometers is preferable, 10-75 micrometers is more preferable, 15-50 micrometers is still more preferable.

[Film manufacturing method]

The film of this invention is not specifically limited, It can be used for various devices, such as a semiconductor, a solar cell, a high brightness LED, LCD seal, organic EL, etc., Especially it can be used suitably for organic electroluminescent element sealing, Organic EL device It can be used suitably. In addition, when making the film of this invention circulate, a protective film can be stuck and circulated. That is, the structure of the film of this invention contains the following six forms.

(1) Peeling System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer + Protective Film

(2) Encapsulation System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer + Protective Film

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

(4) Peeling System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer

(5) Encapsulation System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer

(6) Peeling System Support + Protective Resin Composition Layer + Hygroscopic Resin Composition Layer

In addition, the above has shown the lamination order of each layer.

Specifically, the structure of (1) and (2) of the film of this invention has the 1st varnish which melt | dissolved the resin composition which comprises a moisture absorption resin composition layer, and the 2nd varnish which melt | dissolved the resin composition which comprises a protective resin composition layer. , Respectively, apply a first varnish on a peeling support or an encapsulating support, dry the organic solvent to form a hygroscopic resin composition layer, apply a second varnish thereon, and dry the organic solvent to protect the protective resin composition. It can be obtained by forming a layer and also using a protective film. In addition, the structure of (3) of the film of this invention can be obtained by reversely forming a protective resin composition layer and a moisture absorption resin composition layer. The structure of (4), (5), (6) of the film of this invention has shown the structure at the time of not using a protective film in the film preparation of the structure of (1), (2), (3). .

When the film of this invention is a structure of (1) and (3), although the relationship of a peeling system support body and a protective film should be made to peel a protective film first, if a protective film is made thinner than a peeling system support body, It is preferable to apply a mold release process or an embossing process. The release system support is preferably a polyethylene terephthalate (PET) film, and the protective film is preferably a biaxially stretched polypropylene.

Specifically as an organic solvent used for a varnish, ketones, such as acetone, methyl ethyl ketone (henceforth "MEK"), cyclohexanone, ethyl acetate, butyl acetate, a cellosolve acetate, a 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, N-methylpyrrolidone and the like. have. You may use these 1 type or in combination or 2 or more types.

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

In the method for forming the film of the present invention by sequentially forming the moisture absorbent resin composition layer and the protective resin composition layer in this order or in the reverse order on the support, at the boundary between the moisture absorbent resin composition layer and the protective resin composition layer. There exists a possibility that the mixed layer which mixed the resin composition of both layers is formed, and the damage prevention effect of the organic electroluminescent element by a protective resin composition layer may be impaired. Therefore, the 1st resin composition sheet which formed the moisture absorption resin composition layer using the 1st varnish on the 1st support body is produced, and, separately from this, the protective resin composition layer was formed on the 2nd support body using the 2nd varnish. The method of producing the 2nd resin composition sheet, laminating the moisture absorption resin composition layer of a 1st resin composition sheet, and the protective resin composition layer of a 2nd resin composition sheet, and obtaining the film of this invention is preferable. In addition, in this case, either one of a 1st support body and a 2nd support body becomes a support body of the film of this invention, and the other one becomes a protective film of the film of this invention.

When obtaining the film of this invention by such a method, it is preferable that the melt viscosity of a protective resin composition layer is lower than the melt viscosity of a moisture absorption resin composition layer in the lamination temperature of a moisture absorption resin composition layer and a protective resin composition layer. That is, at the lamination temperature of a moisture absorption resin composition layer and a protective resin composition layer, the filler contained in a moisture absorption resin composition layer because melt viscosity of the resin composition which comprises a protective resin composition layer is lower than the melt viscosity of a moisture absorption resin composition layer. It is because it can avoid moving to a protective resin composition layer at the time of lamination, or damaging an EL element through a protective resin composition layer.

The "melt viscosity" used here uses the model Rheosol-G3000 manufactured by Ubi M Corporation, and the resin amount is 1 g and a parallel plate having a diameter of 18 mm, using a measurement start temperature of 60 ° C. and a heating rate of 5 ° C./min. , Measured at a measurement temperature of 60 to 200 ° C and a frequency of 1 Hz / deg.

There is no restriction | limiting in particular and lamination temperature can be set suitably according to the performance requested | required, but since lower than the hardening temperature of a moisture absorption resin composition layer and a protective resin composition layer is calculated | required, the upper limit of a lamination temperature is preferable at 130 degrees C or less, 120 degrees C or less is more preferable, 110 degrees C or less is further more preferable, and 100 degrees C or less is further 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, still more preferably 50 ° C or higher, even more preferably 55 ° C or higher, from the viewpoint of good handleability at normal temperature. , 60 ° C or more is particularly preferred. Moreover, the melt viscosity of a moisture absorption resin composition layer from a viewpoint of not mixing a moisture absorption resin composition layer and a protective resin composition layer with each other at a set lamination temperature, and preventing a hygroscopic metal oxide from moving to a protective resin composition layer. The lower limit of the difference between the melt viscosity of the resin layer and the protective resin composition layer (melt viscosity of the hygroscopic resin composition layer-melt viscosity of the protective resin composition layer) is preferably 300 poise or more, more preferably 1000 poise or more, Az or more is more preferable, 10,000 or more is more preferable, 15000 or more is especially preferable, and 30000 or more is most preferable. On the other hand, at the set lamination temperature, the moisture absorption resin composition layer is melted from the viewpoint of solidifying the moisture absorption resin composition layer and the protective resin composition layer at once, and the bonding of the moisture absorption resin composition layer and the protection resin composition layer efficiently. 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 1 million poise or less, more preferably 500000 poise or less, and 100000. The poise or less is more preferable.

Moreover, as an adjustment method of the melt viscosity of a protective resin composition layer and a moisture absorption resin composition layer, the method of changing hardening degree by drying conditions, the method of changing the compounding ratio of liquid resin, the particle diameter of an inorganic filler, a content rate, etc. are changed. The method of making it make them etc. are mentioned, These may be implemented in combination of 2 or more. Therefore, the viscosity adjustment of a protective resin composition layer and a moisture absorption resin composition layer is performed by these methods, and melt viscosity at the predetermined temperature of a protective resin composition layer becomes lower than the melt viscosity at the predetermined temperature of a moisture absorption resin composition layer. .

Although the film of this invention can be applied to formation of the sealing structure of various semiconductor elements (individual semiconductor, an optical semiconductor, a logic IC, an analog IC, a memory, etc.), it can use especially suitably for the sealing of organic electroluminescent element among these. have.

[Organic EL Device Manufacturing Method]

The method of sealing an organic electroluminescent element using the film of this invention and manufacturing an organic electroluminescent device is demonstrated below. In the sealing structure of a device, a protective resin composition layer is arrange | positioned so that the element of an element formation substrate may be coat | covered, and a moisture absorption resin composition layer is arrange | positioned on the surface on the opposite side to the surface of the element formation substrate side of a protective resin composition layer. As mentioned above, the structure of the film of this invention contains the following six forms.

(1) Peeling System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer + Protective Film

(2) Encapsulation System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer + Protective Film

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

(4) Peeling System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer

(5) Encapsulation System Support + Hygroscopic Resin Composition Layer + Protective Resin Composition Layer

(6) Peeling System Support + Protective Resin Composition Layer + Hygroscopic Resin Composition Layer

(a) When the film of this invention is a structure of (1), a protective film is removed first and a protective resin composition layer is laminated on the transparent substrate in which the organic electroluminescent element was formed. Thereafter, the release system supporter is peeled off, the sealing material is laminated on the exposed moisture absorbent resin composition layer, and a thermosetting operation of the protective resin composition layer and the moisture absorbent resin composition layer can be performed to manufacture an organic EL device.

(b) When the film of this invention is a structure of (2), first, a protective film is removed, a protective resin composition layer is laminated on the transparent substrate in which the organic electroluminescent element was formed, and the heat of a protective resin composition layer and a moisture absorption resin composition layer is carried out. Hardening operation can be performed and an organic EL device can be manufactured.

(c) When the film of this invention is a structure of (3), a protective film is removed first and a moisture absorption resin composition layer is laminated to a sealing material. Thereafter, the release system supporter is peeled off, the exposed protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed, and the thermosetting operation of the protective resin composition layer and the hygroscopic resin composition layer can be performed to manufacture an organic EL device. have.

(d) When the film of this invention is a structure of (4), a protective resin composition layer is laminated on the transparent substrate in which the organic electroluminescent element was formed. Thereafter, the release system supporter is peeled off, the sealing material is laminated on the exposed moisture absorbent resin composition layer, and a thermosetting operation of the protective resin composition layer and the moisture absorbent resin composition layer can be performed to manufacture an organic EL device.

(e) When the film of this invention is a structure of (5), a protective resin composition layer is laminated on the transparent substrate in which the organic electroluminescent element was formed, the thermosetting operation of a protective resin composition layer and a moisture absorption resin composition layer is carried out, and organic EL devices can be manufactured.

(f) When the film of this invention is a structure of (6), the moisture absorption resin composition layer is laminated on the sealing material, the peeling system support body is peeled after that, and the exposed protective resin composition layer was transparent in which the organic electroluminescent element was formed. It laminates on a board | substrate, can perform the thermosetting operation of a protective resin composition layer and a moisture absorption resin composition layer, and can manufacture an organic EL device.

It is preferable to manufacture an organic electroluminescent device by the method of (b), (c), (e) or (f) from a viewpoint of not applying more than the required heat history with respect to an organic electroluminescent 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 this invention, As the said sealing material And metal foils such as plastic films, copper foils, and aluminum foils having moisture resistance, glass plates, and metal plates. From the viewpoint of making the organic EL device itself thin and light, the upper limit of the thickness of the sealing material is preferably 5 mm or less, more preferably 1 mm or less, still more preferably 100 μm or less. The lower limit of the thickness of the sealing 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 sealing materials may be bonded together, and in that case, it is preferable that the total thickness after joining exists in the range of 5 micrometers or more and 5 mm or less.

The method of lamination performed in the method of said (a)-(f) may be batch type or continuous type in a roll. Laminating conditions can be performed under reduced pressure, and it is preferable to carry out using a vacuum laminator or the like. It is preferable to laminate on the conditions of the temperature of 50-130 degreeC, and the pressure of 0.5-10 kgf / cm <2> under reduced pressure of 10 <^-3> (10hPa) MPa or less. Specific examples of the vacuum laminator include a vacuum pressurized laminator manufactured by Meiki Sesaku Sho Co., Ltd. and a vacuum applicator manufactured by Nichigo Morton Co., Ltd., and the like.

The method of thermosetting a protective resin composition layer and a moisture absorption resin composition layer does not have a restriction | limiting in particular, A well-known thing can be used. Specific examples thereof include hot air circulation ovens, infrared heaters, heat guns, high frequency induction heating devices, and heating by crimping heat tools. The film of the present invention has very good low temperature curability, the upper limit of the curing temperature is preferably 140 ° C or lower, more preferably 120 ° C or lower, and even more preferably 110 ° C or lower. On the other hand, from a viewpoint of ensuring the adhesiveness of hardened | cured material, 50 degreeC or more is preferable and, as for the minimum of hardening temperature, 55 degreeC or more is more preferable. Moreover, 120 minutes or less are preferable, as for the upper limit of hardening time, 90 minutes or less are more preferable, and 60 minutes or less are more preferable. On the other hand, from a viewpoint of hardening hardened | cured material reliably, 20 minutes or more are preferable and, as for the minimum of hardening time, 30 minutes or more are more preferable. Thereby, the thermal deterioration of organic electroluminescent 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 used as the display surface of the display or the light emitting surface of the lighting apparatus, the transparent material is necessarily a transparent material. It is not necessary to use a metal plate, metal foil, an opaque plastic film or plate may be used.

Example

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

[Use materials]

The used material used for experiment is demonstrated.

(A) epoxy resin

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

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

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

(B) phenoxy resin

-MEK solution of 35 weight% of solid content of "YL7213-35M" (weight average molecular weight 35000) by the Japan epoxy resin company

(C) curing agent

ㆍ Latent curing accelerator for epoxy resin ("U-CAT3502T" by San Apro Corporation)

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

(D) hygroscopic metal oxide

Calcined dolomite: MEK slurry obtained by wet pulverization of "small dolomite" manufactured by Yoshizawa Sekikai Co., Ltd. (40 wt% as solid content, average particle diameter: 0.87 mu m)

(E) inorganic filler

Talc: MEK slurry (30 weight% as solid content, average particle diameter: 0.72 micrometer) of the wet grinding | pulverization of "D-600" by Nippon Tark Corporation.

(F) surface treatment agent

Stearic acid

(G) coupling agent

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

〔How to measure〕

Next, a measuring method is demonstrated.

 Adhesion between Support and Resin Composition Layer

Two pieces of aluminum foil (50mm in width, 50mm in length, 50micrometer in thickness) are prepared, the resin composition layer (40mm in width, 50mm in length) on a base material is piled on one side of the 1st aluminum foil, and it is vacuum-laminated, It laminated on the conditions of the temperature of 80 degreeC, and the pressure of 1 kgf / cm <2> (9.8x10 <^4> Pa). And the base material was peeled off, it laminated | stacked the 2nd aluminum foil on the exposed resin composition layer, and laminated under the same conditions, and created the test piece of the three layer structure of aluminum foil, a resin composition layer, and aluminum foil. After heat-hardening on 110 degreeC and the conditions for 30 minutes, this test piece was cut into the rectangular test piece of width 10mm and length 50mm, and the adhesive force (peel force) of the test piece in the longitudinal direction based on the T-type peeling test method of JISK-6854. ) Was measured.

〔Assessment Methods〕

Next, the evaluation method is described.

 [Evaluation of moisture permeability]

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 organic EL element light emitting portion, and the relative rate of change of luminance after initial (0 hours) and 1000 hours was evaluated. That is, when a large number of shrinks or DSs are generated, the light emitting area is reduced to increase the luminance of the light emitting unit, thereby increasing the relative change rate with respect to the luminance of the initial state without defects. In addition, the brightness | luminance measured two points by constant current drive (15mA), and computed the average value. As evaluation, when the relative change rate was less than 1.1, it was set as (circle) and when it was 1.1 or more, it was set as x.

[Evaluation of Damage Resistance of Devices]

The degree of damage of the organic EL element was evaluated by the dark current value at the driving voltage of 3V. As an evaluation, it was set as (circle) when dark current value was less than 0.2 mA, and × when it was 0.2 mA or more.

Curable resin composition varnish A-E of the compounding composition shown in following Table 1 was prepared by the procedure shown next. In addition, the numerical value of the compounding quantity of each material shown in Table 1 is a weight part.

(Production Example 1)

The mixed melt which melt | dissolved solid epoxy resin ("HP7200H" by DIC Corporation) in phenoxy resin (35% by weight of MEK solution of "YL7213-35M" by Japan Epoxy Resin company) was created, and the mixed melt Rubber fine particle dispersion liquid epoxy resin ("BPA328" by Nihon Shokubai company), liquid epoxy resin ("GOT" by Nihon Kayaku Co., Ltd.), and latent hardening accelerator (U-CAT3502T by San Apro Corporation) for epoxy resin ), 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 disperse uniformly with a high speed rotary mixer, and varnish. A was obtained.

(Production Example 2)

The mixture A which melt | dissolved solid epoxy resin ("HP7200H" by DIC Corporation) in phenoxy resin (35% by weight of MEK solution of "YL7213-35M" by Japan Epoxy Resin company) was created. On the other hand, stearic acid was added and dispersed in the MEK slurry (40 weight% as solid content) of calcined dolomite (wet-crushed by Yoshizawa Sekikai Co., Ltd. make), and mixture B was created. Mixture A, mixture B, talc (wet-pulverized "D-600" by Nippon Tar Company, MEK slurry having a solid content of 30% by weight), rubber fine particle dispersion liquid epoxy resin ("BPA328" by Nihon Shokubai Co., Ltd.) and , Latent curing accelerator for epoxy resin ("U-CAT3502T" by San Apro Corporation), liquid epoxy resin ("GOT" by Nihon Kayaku Co., Ltd.), silane coupling agent ("KBM-403" by Shin-Etsu Chemical Co., Ltd.) are mix | blended. The mixture was mixed with an Aji homomixer robomix type mixing stirrer (manufactured by Flymix Co., Ltd.). An ionic liquid curing agent (N-acetylglycine tetrabutyl phosphonium salt) was added thereto and uniformly dispersed in a high speed rotary mixer to obtain varnish B.

(Production Example 3)

Except for adding talc (wet-pulverized "D-600" manufactured by Nihon Tark Co., Ltd., MEK slurry having a solid content of 30% by weight), by the same method as varnish A in Production Example 1, to the compounding table of Table 1 Thus, varnish C was prepared.

(Production Example 4)

Varnish D was prepared according to the compounding table of following Table 1 by the method similar to varnish B in the manufacture example 2.

(Manufacture example 5)

Varnish E was prepared according to the compounding table of following Table 1 by the method similar to varnish B in the manufacture example 2.

(Test Examples 1 to 3)

About each resin composition layer produced by varnish B, D, and E, the adhesive force with the support body was measured. The results are shown in Table 2.

From the result of Table 2, it turns out that the adhesive force with respect to the support body of a resin composition layer improves significantly by mix | blending talc in the resin composition layer of the film of this invention.

(Test Examples 4 to 6)

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

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

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

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

By the combination shown in Table 3, the protective resin composition layer with PET film and the moisture absorption resin composition layer with PET film are made to face a protective resin composition layer and a moisture absorption resin composition layer, and the temperature is 100 degreeC, and the pressure 1Kg / by a vacuum laminator. It laminated on the conditions of cm <2> (9.8x10 <^4> Pa), and produced the films (Test Examples 4-6) which have a support body, a protective resin composition layer, and a moisture absorption resin composition layer. Then, the vicinity of the boundary of the protective resin composition layer and the moisture absorption resin composition layer in the cross section of each produced film was observed with SEM (scanning electron microscope) (2000x magnification). 2 is an SEM photograph of the film cross section of Test Example 4, FIG. 3 is an SEM photograph of the film cross section of Test Example 5, and FIG. 4 is an SEM photograph of the film cross section of Test Example 6. FIG.

As for the difference (melt viscosity of a moisture absorption resin composition layer-melt viscosity of a protective resin composition layer) of the moisture absorption resin composition layer and protective resin composition layer in a film, the film of Test Example 4 is 17530 poise, the film of Test Example 5 This 3430 poise and the film of Test Example 6 were -1710 poises. In the film (FIG. 2) of the test example 4, the interface of a moisture absorption resin composition layer (upper layer) and a protective resin composition layer (lower layer) becomes substantially horizontal, and is a protective resin composition layer (lower layer) from a moisture absorption resin composition layer (upper layer). The transition of the hygroscopic metal oxide to was not confirmed. Also in the film (FIG. 3) of the test example 5, 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 (FIG. 4) of the test example 6, migration of the hygroscopic metal oxide (light spot) 7 from the hygroscopic resin composition layer (upper layer) to the protective resin composition layer (lower layer) was confirmed.

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

[Production of organic EL device]

(Cleaning of ITO substrate and sealing glass plate)

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

(Deposition process)

Vacuum degree 1 to 2 × 10 ⁻⁴ Pa, deposition rate 1.0 to 2.0 μs / s, 30 mm square (30 mm × 30 mm wide), on 0.7 mm thick glass base, Glass / SiO ₂ [53 nm] / ITO [55 nm] Each layer was deposited in the structure of /PEDOT.PSS[40nm]/α-NPD[50nm]/Alq ₃ [50nm] / LiF [0.8nm] / Al [15nm] to produce an organic EL device. The light emitting portion area is 10 × 10 mm 2.

In addition, "PEDOTPSS" is abbreviation of (poly (3, 4- ethylene dioxythiophene)) (polystyrene sulfonic acid), and "(alpha) -NPD" is (bis [N- (1-naphthyl) -N -Phenyl] benzidine), "Alq ₃ ", is an abbreviation for tris (8-quinolinolato) aluminum.

(Bag of organic EL element)

First, the film of this invention was laminated on the glass plate (21 mm x 28 mm, 0.7 mm thickness) which is a sealing material. Lamination was performed by vacuum-pressing on the conditions of 80 degreeC, pressure reduction (1 * 10 <^-3> MPa or less) suction 20 second, press 20 second in the clean booth of class 100.

Next, the support was peeled off, and the resin composition layer exposed on the glass plate was decompressed (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 pressing was conducted 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 thermoset by heating on a hot plate at 110 ° C. for 30 minutes.

In addition, the said resin composition layer is what laminated | stacked the protective resin composition layer and the moisture absorption resin composition layer, The laminate to the glass plate which is a sealing material presses a moisture absorption resin composition layer to a glass plate, and the laminate to an organic EL element formation board | substrate is a protective resin. The composition layer was pressed onto the organic EL element formation substrate.

(Example 1)

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

Similarly, varnish B was uniformly applied on a mold release surface of a PET film (38 μm in thickness) treated with an alkyd-based release agent with a die coater 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 hygroscopic resin composition layer was obtained.

The protective resin composition layer with PET film and the hygroscopic resin composition layer with PET film are made to face a protective resin composition layer and a moisture absorption resin composition layer, and the temperature is 80 degreeC and pressure 1Kg / cm <2> (9.8 * 10 <^4> pa) by a vacuum laminator. It laminated with the conditions of and produced the film of this invention. The melt viscosity at 80 ° C of the protective resin composition layer was 27,500 poises, and the melt viscosity at 80 ° C of the hygroscopic resin composition layer was 63400 poises. Next, after peeling the PET film of the moisture absorption resin composition layer side of the said film, laminating the moisture absorption resin composition layer to the glass plate which is a sealing material, the PET film of the protection resin composition layer side is peeled off, and a protective resin composition layer is an organic electroluminescent element It laminated on the glass plate which has the, and produced the organic electroluminescent device.

1: A is a figure which shows typically the cross section of the produced organic electroluminescent device, and has a protective resin composition layer (inorganic filler, in the formation surface of the organic electroluminescent element 4 of the board | substrate 5 in which the organic electroluminescent element 4 was formed. Hygroscopic metal oxide-free) (3), hygroscopic resin composition layer (inorganic filler, hygroscopic metal oxide containing) 2, and sealing material (glass plate) 1 are laminated | stacked in this order.

(Comparative Example 1)

Varnish B was uniformly coated on a mold release surface of a PET film (38 μm thick) treated with an alkyd type release agent with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and 12 minutes at 60 to 95 ° C. By drying for a while, a resin composition layer was obtained. After laminating this resin composition layer with PET film on the glass plate which is a sealing material, the PET film was peeled off, the resin composition layer was laminated on the glass plate which has an organic EL element, and the organic EL device was produced.

FIG. 1B is a diagram schematically showing a cross section of a manufactured organic EL device, wherein the resin composition layer (inorganic filler, hygroscopicity) is formed 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 containing) 2 and the sealing material (glass plate) 1 are laminated in this order.

(Comparative Example 2)

Varnish A was uniformly applied on a mold release surface of a PET film (38 μm thick) treated with an alkyd type release agent with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and 12 minutes at 60 to 95 ° C. By drying for a while, a resin composition layer was obtained. After laminating this resin composition layer with PET film on the glass plate which is a sealing material, the PET film was peeled off, the resin composition layer was laminated on the glass plate which has an organic EL element, and the organic electroluminescent device was produced.

FIG. 1C is a diagram schematically showing a cross section of the produced organic EL device, wherein the resin composition layer (inorganic filler, hygroscopicity) is formed 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 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 of the resin composition layer derived from varnish C of this film, and laminating the said resin composition layer to the glass plate which is a sealing material, the PET film of the resin composition layer side derived from varnish A was peeled off, and the said resin composition layer was It laminated on the glass plate which has an organic electroluminescent element, and produced the organic electroluminescent device.

1D is a diagram schematically showing a cross section of a manufactured organic EL device, wherein the resin composition layer (inorganic filler, hygroscopicity) is formed 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 (containing inorganic filler, hygroscopic metal oxide free) 6, and sealing material (glass plate) 1 are laminated in this order.

(Comparative Example 4)

Varnish C was uniformly coated on a mold release surface of a PET film (38 μm thick) treated with an alkyd type release agent with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and 12 minutes at 60 to 95 ° C. By drying for a while, a resin composition layer was obtained. After laminating this resin composition layer with PET film on the glass plate which is a sealing material, the PET film was peeled off, the resin composition layer was laminated on the glass plate which has an organic EL element, and the organic EL device was produced.

FIG. 1E is a diagram schematically showing a cross section of the produced organic EL device, wherein the resin composition layer (containing inorganic filler) is formed 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 sealing material (glass plate) 1 are laminated in this order.

About the organic EL device of Example 1 and Comparative Examples 1-4, the performance evaluation result is shown in Table 4.

It is understood from Example 1 that by using the film of the present invention, it is possible to easily form the sealing structure of the organic EL element in which the blocking is achieved at a high level from moisture of the organic EL element while reducing damage to the organic EL element. Can be. In Example 1, since the moisture absorbing resin composition layer and the protective resin composition layer are cured at low temperatures and the organic EL element is sealed, not only the damage of the organic EL element in the sealing operation but also the thermal deterioration of the organic EL element are sufficiently suppressed. Thus, highly reliable organic EL element devices could be obtained.

On the other hand, the comparative example 1 contains many hygroscopic metal oxides, and has damaged the organic electroluminescent element. In addition, Comparative Examples 2, 3, and 4 did not contain a hygroscopic metal oxide, so that the organic EL device was damaged by moisture. Moreover, although the comparative example 4 contained talc, it was difficult to implement | transform with a flat plate filler, and the damage resistance of the element was observed.

[Industrial Availability]

By the film which has a support body, a protective resin composition layer, and a moisture absorption resin composition layer, the film which combined moisture permeability and damage resistance of an element can be implement | achieved, and such a film can provide the highly reliable organic EL device.

This application is based on the JP Patent application 2009-182827 for which it applied in Japan, The content is altogether included in this specification.

1 bag material (glass plate)
2 moisture absorption resin composition layer (containing inorganic filler, hygroscopic metal oxide)
3 protective resin composition layer (inorganic filler, hygroscopic metal oxide free)
4 organic EL elements
5 substrate
6 resin composition layer (containing inorganic filler, non-hygroscopic metal oxide)
7 Hygroscopic Metal Oxide

Claims (6)

It has a support body, a protective resin composition layer, and a moisture absorption resin composition layer, The film characterized by the above-mentioned. The moisture absorption resin composition layer contains a hygroscopic metal oxide, The film of Claim 1 characterized by the above-mentioned. The moisture absorption resin composition layer contains an inorganic filler (except a hygroscopic metal oxide), The film of Claim 1 or 2 characterized by the above-mentioned. The film according to any one of claims 1 to 3, wherein the protective resin composition layer contains an inorganic filler (except for hygroscopic metal oxides). The difference in the melt viscosity of the hygroscopic resin composition layer and the protective resin composition layer at the lamination temperature set in the range of 40-130 degreeC (melt viscosity of a hygroscopic resin composition layer-in any one of Claims 1-4). Melt viscosity of a protective resin composition layer) is 300-1 million poise, The film characterized by the above-mentioned. It has a film in any one of Claims 1-5, The organic electroluminescent device characterized by the above-mentioned.

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