JP2016207661A - Film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film combining sufficient moisture permeation resistance and damage resistance of an element, advantageous for formation of a highly reliable sealing structure.SOLUTION: A film has a support and a protective resin composition layer. With such a configuration, a film combining sufficient moisture permeation resistance and damage resistance of an element (i.e., a function for preventing impairment of an element) can be achieved. The film is especially suitable for sealing of an organic EL element, and by using the inventive film, a highly reliable organic EL element device, where not only impairment but also thermal deterioration of the organic EL element are suppressed sufficiently in the sealing work, can be obtained.SELECTED DRAWING: None

Description

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

  An organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and is a material that has been attracting attention in recent years because it can emit light with high luminance at a low voltage. However, organic EL elements are extremely sensitive to moisture, and the organic material itself is altered by moisture, resulting in a decrease in brightness, no light emission, the interface between the electrode and the organic EL layer being peeled off due to moisture, metal There is a problem that the metal oxide is oxidized to increase the 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 surface of the organic EL layer, and a non-permeable glass substrate is bonded. Has been. However, since an acrylic ultraviolet curable resin composition is used for the curable resin layer, there is a problem of deterioration of the organic EL element due to ultraviolet rays, and an uncured portion is generated in a place where the ultraviolet rays do not reach. It was not satisfactory in that it was difficult to obtain a highly sealing structure.

  Patent Document 2 proposes a thermosetting curable resin composition that seals the entire surface of an organic EL element. However, the obtained cured product layer was not satisfactory in that the moisture permeability resistance was not sufficient.

JP-A-5-182759 JP 2006-70221 A

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

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

That is, the present invention includes the following aspects.
(1) A film comprising a support, a protective resin composition layer, and a hygroscopic resin composition layer.
(2) The film according to (1) above, wherein the hygroscopic resin composition layer contains a hygroscopic metal oxide.
(3) The film according to (1) or (2) above, wherein the hygroscopic resin composition layer contains an inorganic filler (excluding a hygroscopic metal oxide).
(4) The film according to any one of (1) to (3) above, wherein the protective resin composition layer contains an inorganic filler (excluding a hygroscopic metal oxide).
(5) At the lamination temperature set in the range of 40 ° C. to 130 ° C., the difference in melt viscosity between the hygroscopic resin composition layer and the protective resin composition layer (melt viscosity of the hygroscopic resin composition layer−the protective resin composition layer The film according to any one of (1) to (4) above, wherein the melt viscosity is from 300 poise to 100,000 poise.
(6) An organic EL device comprising the film according to any one of (1) to (5) above.

  A film having a support, a protective resin composition layer, and a hygroscopic resin composition layer provides a film having both sufficient moisture permeation resistance and element damage resistance (that is, a function for preventing element damage). I was able to do that.

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 devices of Comparative Examples 1 to 4. FIG. 6 is a SEM photograph of a film cross section of Test Example 4. 10 is a SEM photograph of a film cross section of Test Example 5. 10 is a SEM photograph of a film cross section of Test Example 6.

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

[Support]
The support used in the present invention means “a substance that supports the protective resin composition layer or the hygroscopic resin composition layer”, but is not particularly limited as long as it exhibits its function.
The support is classified into a peeling system support and a sealing system support.

  The release system support means a support that can be peeled off during production of various devices (that is, a support that is peeled (separated) from the film of the present invention during the production of various devices). Specific examples of such a release support include polyethylene, polypropylene, polyolefins such as polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), and polyethylene naphthalate (hereinafter abbreviated as “PEN”). And a film made of a plastic such as polyester, polycarbonate, and polyimide. From the viewpoint of cost performance, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film is more preferable.

  The thickness of the release support is not particularly limited, but from the viewpoint of the handleability of the film of the present invention, the upper limit of the thickness of the support is preferably 150 μm or less, more preferably 120 μm or less, and still more preferably 90 μm or less. On the other hand, the lower limit of the thickness is preferably 10 μm or more, more preferably 40 μm or more, and even more preferably 70 μm or more from the viewpoints of the handleability and moisture resistance of the film of the present invention.

  The release support is preferably subjected to a release treatment in advance. Specifically, as a release agent used for the release treatment, specifically, a fluorine release agent, a silicone release agent, an alkyd resin type Examples include mold release agents. You may use a mold release agent 1 type or in mixture of 2 or more types. In addition, the surface of the release support may be subjected to mat treatment, corona treatment, or the like, and a release treatment may be further performed on the surface subjected to these treatments.

  The sealing support can be used as a part of various devices as they are at the time of manufacturing various devices (that is, used for manufacturing various devices and incorporated into devices finally manufactured), and has moisture resistance. It means a support. More specifically, the support is arranged in the outermost layer separated from the element formation substrate on which the elements (semiconductor elements, LED elements, organic EL elements, etc.) are formed in the sealing structure of various devices. Used as a sealing material. Examples of the support include metal foil and a laminated film in which a metal foil or an inorganic vapor deposition film is laminated on at least one surface of a plastic film. Here, examples of the metal foil include copper foil and aluminum foil, and examples of the inorganic deposited film include deposited films of silicon oxide (silica), silicon nitride, SiCN, amorphous silicon, and the like. Moreover, the said support body can use the plastic film which has a moisture-proof property marketed, for example, the tech barrier HX, AX, LX, L series (made by Mitsubishi resin company) and further improved the moisture-proof effect. X-BARRIER (Mitsubishi Resin 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 producing an organic EL device using the film of the present invention using a sealing system support, the light emitting surface of the produced organic EL device is the surface on which the organic EL element of the element formation substrate is formed. It will be the opposite side.

  The thickness of the support is not particularly limited when a metal foil is used for the sealing support or a laminated film in which an inorganic vapor deposition film or a metal foil is laminated on at least one surface of a plastic film. However, from the viewpoint of the handleability of the film of the present invention, the upper limit of the thickness of the support is preferably 150 μm or less, more preferably 120 μm or less, and still more preferably 90 μm or less. On the other hand, the lower limit of the thickness is preferably 10 μm or more, more preferably 40 μm or more, and even more preferably 70 μm or more from the viewpoints of the handleability and moisture resistance of the film of the present invention.

  The upper limit of the thickness of the support in the case of using a glass plate or a metal plate for the sealing support is preferably 5 mm or less, more preferably 1 mm or less, and 100 μm from the viewpoint of making the organic EL device itself thin and light. The following is more preferable. 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 still more preferably 20 μm or more from the viewpoint of preventing moisture permeation and the rigidity of the organic EL device.

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

[Hygroscopic resin composition layer]
The hygroscopic resin composition layer used for the film of the present invention is composed of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a hygroscopic metal oxide, and has moisture permeability resistance. Thereby, in the sealing structure of the target device (organic EL device or the like), moisture intrusion into the element (organic EL device or the like) is blocked.

(Thermosetting resin and curing agent)
The thermosetting resin and the curing agent are not particularly limited, and specifically, various thermosettings such as epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, vinyl benzyl resin, etc. Resins and their curing agents. Of these, an epoxy resin and its curing agent are preferable from the viewpoints of low-temperature curability and adhesiveness of a cured product.

  As an epoxy resin, those having an average of two or more epoxy groups per molecule may be used. Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol type epoxy are used. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin Epoxy resin having butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, and diglycidyl alcohol Examples include etherified products, and alkyl-substituted products, halides, and hydrogenated products of these epoxy resins. These may be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy from the viewpoint of maintaining high heat resistance and low moisture permeability of the resin composition. A resin, an aromatic glycidylamine type epoxy resin, an epoxy resin having a dicyclopentadiene structure, and the like are preferable.

  The epoxy resin may be liquid, solid, or both liquid and solid. Here, “liquid” and “solid” are states of the epoxy resin at 25 ° C. From the viewpoint of coatability, workability, adhesiveness, etc., it is preferable that 10% by weight or more of the entire epoxy resin to be used is liquid.

  The epoxy resin preferably has an epoxy equivalent in the range of 100 to 1000, more preferably in the range of 120 to 1000, from the viewpoint of reactivity. Here, the epoxy equivalent is the gram number (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K-7236.

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

  Specific examples include primary amines, secondary amines, tertiary amine-based curing agents, polyaminoamide-based curing agents, dicyandiamide, and organic acid dihydrazides. Among these, amine adduct-based compounds ( Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40, Amicure PN-40J, etc. (all Ajinomoto Fine Techno)), organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine Techno Co.)) and the like are preferable. You may use these 1 type or in combination of 2 or more types.

  Further, 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, A salt having a curing action is particularly preferably used. The ionic liquid has an advantageous effect on improving the moisture permeation resistance of the cured product of the hygroscopic resin composition layer. The ionic liquid is preferably used in a state where the ionic liquid is uniformly dissolved in the epoxy resin.

  Examples of cations constituting such an ionic liquid include imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guanidinium ions, pyridinium ions, and other ammonium cations; tetraalkylphosphonium cations (specifically, tetrabutyl Phosphonium cations such as phosphonium ions and tributylhexylphosphonium ions; and sulfonium cations such as triethylsulfonium ions.

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

(In the formula, 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 asparagine. Acidic amino acid ions such as acid and glutamic acid, or neutral amino acid ions such as glycine, alanine and phenylalanine.)

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

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

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

  Specific ionic liquids include 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate Tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL-alanine Tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, -Monotetrabutylphosphonium aspartate, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl formate -3-methylimidazolium salt, 1-ethyl-3-methylimidazolium salt of hippuric acid, 1-ethyl-3-methylimidazolium salt of N-methylhippuric acid, bis (1-ethyl-3-methylimidazolium) tartrate N-acetylglycine 1-ethyl-3-methylimidazolium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate salt Hippuric acid 1-ethyl-3-methyl The imidazolium salt, 1-ethyl-3-methylimidazolium salt of N-methylhippuric acid is particularly preferred.

As a method for synthesizing the ionic liquid, a precursor composed of a cation moiety such as an alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions and an anion moiety containing a halogen is added to NaBF ₄ , NaPF ₆ , CF ₃ SO ₃ Anion exchange method in which Na, LiN (SO ₂ CF ₃ ) ₂ or the like is reacted, an acid ester in which an organic acid residue becomes a counter anion while introducing an alkyl group by reacting an amine substance with an acid ester Methods, and neutralization methods in which amines are neutralized with an organic acid to obtain a salt, but are not limited thereto. In the neutralization method using an anion, a cation, and a solvent, an anion and a cation are used in an equivalent amount, and the solvent in the obtained reaction solution can be distilled off and used as it is, or an organic solvent (methanol, toluene, etc.). , Ethyl acetate, acetone, etc.) may be concentrated.

  The curing agent is preferably used in the range of 0.1 to 50% by weight, more preferably in the range of 0.5 to 25% by weight, with respect to 100% by weight of the nonvolatile content in the resin composition. The range of wt% is more preferred, and the range of 1.5-10 wt% is even more preferred. If the amount is less than this range, sufficient curability may not be obtained. If the amount is more than 50% by weight, not only the storage stability of the resin composition is impaired, but also the moisture permeability and heat resistance of the cured product are lowered. There are things to do. 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 from points, such as moisture permeability of the hardened | cured material of a resin composition, 0.5- 8 weight% is more preferable, 1-6 weight% is still more preferable, and 1.5-5 weight% is still more preferable.

  The resin composition constituting the hygroscopic resin composition layer in the present invention may further contain a curing accelerator for adjusting the curing temperature, the curing time, and the like. Examples of the curing accelerator include quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, quaternary sulfonium salts such as tetraphenylphosphonium bromide and tetrabutylphosphonium bromide, DBU (1,8-diazabicyclo (5.4.0). ) Undecene-7), DBN (1,5-diazabicyclo (4.3.0) nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, Diazabicyclo compounds such as DBU-phenol novolak resin salt, imidazole compounds such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, Benzyl Examples thereof include tertiary amines such as dimethylamine, dimethylurea compounds such as aromatic dimethylurea, aliphatic dimethylurea, and aromatic dimethylurea.

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

(Hygroscopic metal oxide)
The “hygroscopic metal oxide” as used in the present invention is a metal oxide that has the ability to absorb moisture and chemically reacts with moisture that has been absorbed to become a hydroxide, so long as the object of the present invention can be achieved. Although there is no particular limitation, specifically, one kind selected from 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. It is a thing. As an example of a mixture or solid solution of two or more metal oxides, specifically, calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide) ) And the like. Such a hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercially available product can be used. Specifically, calcined dolomite (such as “KT” manufactured by Yoshizawa Lime Co., Ltd.), calcium oxide (such as “Moystop # 10” manufactured by Sankyo Flour Mills), magnesium oxide (“Kyowa Mag MF-150” manufactured by Kyowa Chemical Industry Co., Ltd.), “ Kyowa Mag MF-30 ”,“ Pure Mag FNMG ”manufactured by Tateho Chemical Industry Co., Ltd.), lightly burned magnesium oxide (“ # 500 ”,“ # 1000 ”,“ # 5000 ”etc. manufactured by Tateho Chemical Industry Co., Ltd.) and the like.

  The average particle diameter of the hygroscopic metal oxide is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. By using such a fine size, not only a high moisture permeation resistance can be imparted to the cured layer of the hygroscopic resin composition, but also the adhesive strength can be increased. In addition, if the average particle diameter of the hygroscopic metal oxide is too small, the average particle diameter of the hygroscopic metal oxide is 0.01 μm from the viewpoint that the particles are aggregated and the sheet processing tends to be difficult. The above is preferable, and 0.1 μm or more is preferable.

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

  The “average particle size” here is the median diameter of the particle size distribution when the particle size distribution of the measurement target (granular material) is created on a volume basis. The volume-based particle size distribution can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, as a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. Can be used. It is preferable to use a measurement sample in which a hygroscopic metal oxide is dispersed in water by ultrasonic waves.

  As the hygroscopic metal oxide, a surface treated with a surface treatment agent can be used. By using such a surface-treated hygroscopic metal oxide, the storage stability of the resin composition constituting the hygroscopic resin composition layer can be further increased, and moisture and moisture absorption in the resin can be improved before curing. The reactive metal oxide can be prevented from reacting.

  Specific examples of the surface treatment agent used for the surface treatment include higher fatty acids, alkylsilanes, silane coupling agents, and the like. Among these, higher fatty acids or alkylsilanes are preferable.

  Specifically, the higher fatty acid is preferably a higher fatty acid having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, and stearic acid is more preferable. These may be used alone or in combination of two or more.

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

  Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl). Epoxy silane coupling agents such as ethyltrimethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane Coupling agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropylto Amino silanes such as methoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Coupling agents; ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents such as; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate-based silane coupling agents such as xysilane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. You may use these 1 type or in combination of 2 or more types.

  Specifically, the surface treatment can be performed by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated hygroscopic metal oxide at room temperature with a mixer. As the mixer, known mixers can be used. Specific examples include blenders such as V blenders, ribbon blenders and bubble cone blenders, mixers such as Henschel mixers and concrete mixers, ball mills and cutter mills. It is done. Further, when the hygroscopic material is pulverized with a ball mill or the like, a method of surface treatment by mixing the higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, but is preferably 1 to 10% by weight with respect to the hygroscopic metal oxide.

  The upper limit of the content of the hygroscopic metal oxide in the resin composition is that when the content of the hygroscopic metal oxide is excessive, the viscosity of the resin composition increases, and the strength of the cured product decreases and becomes brittle. In view of the above, it is preferably 40% by weight or less, more preferably 35% by weight or less, still more preferably 30% by weight or less, still more preferably 25% by weight or less, based on 100% by weight of the nonvolatile content in the resin composition. The weight percent or less is particularly preferred. On the other hand, the lower limit of the content of the hygroscopic metal oxide is 1% by weight or more with respect to 100% by weight of the non-volatile content in the resin composition from the viewpoint of sufficiently obtaining the effect of containing the hygroscopic metal oxide. Is preferable, 5% by weight or more is more preferable, and 10% by weight or more is still more preferable.

(Inorganic filler)
The resin composition constituting the hygroscopic resin composition layer may further contain an inorganic filler (however, excluding the hygroscopic metal oxide). By containing the inorganic filler, the moisture permeability of the cured product of the resin composition is improved, and the composition is prevented from being repelled during film production, and the adhesive strength with the support or the sealing material is increased. Can be improved. Specific examples of the inorganic filler include silica, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, titanium Examples thereof include magnesium oxide, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, talc, clay, mica, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite and the like. The inorganic filler may be used alone or in combination of two or more. Among these, from the viewpoint that the inorganic filler does not easily migrate to another layer during lamination, the talc, clay, mica, boehmite and the like are preferably in the form of a flat plate, and the particle form is preferably a flat plate. By using, the moisture permeability resistance of the cured layer obtained by curing the moisture-absorbing resin composition layer can be further enhanced.

  The upper limit of the average particle size 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 reduction in mechanical strength and from the viewpoint that the inorganic filler is difficult to migrate to other layers during lamination. Preferably, it is 0.6 μm or less. Further, the lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, from the viewpoint of preventing dispersibility from being reduced due to aggregation and preventing deterioration in handleability due to increased viscosity of the resin composition. Preferably, 0.3 μm or more is more preferable. In addition, the average particle diameter here is synonymous with the average particle diameter in the above-mentioned hygroscopic metal oxide.

  From the viewpoint that the upper limit of the content of the inorganic filler in the resin composition is that when the content of the inorganic filler is excessively increased, the viscosity of the resin composition increases, and the strength of the cured product decreases and becomes brittle. It is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, and even more preferably 30% by weight or less with respect to 100% by weight of the nonvolatile content in the resin composition. On the other hand, the lower limit of the content of the inorganic filler is preferably 1% by weight or more, preferably 5% by weight or more with respect to 100% by weight of the nonvolatile content in the resin composition, from the viewpoint of sufficiently obtaining the effect of the inorganic filler. More preferred is 10% by weight or more.

(Rubber particles)
The resin composition constituting the moisture-absorbing resin composition layer can further contain rubber particles, and by including the rubber particles, the mechanical strength of the cured product of the resin composition can be improved and the stress can be relaxed. Can do. The rubber particles do not dissolve in the organic solvent when preparing the varnish of the resin composition, are incompatible with the components in the resin composition such as epoxy resin, and exist in a dispersed state in the varnish of the resin composition Those that do are preferred. Such rubber particles can generally be prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or resin and making it into particles. Specifically, core-shell type rubber particles, Examples thereof include acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particle is a rubber particle having a core layer and a shell layer. Specifically, the outer shell layer is a glassy polymer, and the inner core layer is a rubbery polymer. Alternatively, a three-layer structure in which the outer shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer can be used. Specifically, the glass layer is composed of a polymer of methyl methacrylate or the like, and the rubbery polymer layer is specifically composed of a butyl acrylate polymer (butyl acrylate rubber) or the like. The upper limit of the average particle size of the primary particles of these rubber particles is 2 μm or less from the viewpoint of maintaining the stress relaxation effect and preventing damage to the device when the organic EL device is sealed with the resin composition. preferable. On the other hand, the lower limit of the average particle size of the primary particles of the rubber particles is preferably 0.05 μm or more from the viewpoint of preventing the handleability from deteriorating due to an increase in viscosity when mixed into the resin. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (manufactured by Ganz Kasei Co., Ltd.), Metabrene KW-4426 (manufactured by Mitsubishi Rayon Co., Ltd.), F351 (manufactured by Nippon Zeon Co., Ltd.), and the like. Specific examples of acrylonitrile butadiene rubber (NBR) particles include XER-91 (manufactured by JSR). Specific examples of the styrene butadiene rubber (SBR) particles include XSK-500 (manufactured by JSR). Specific examples of the acrylic rubber particles include Methbrene W300A and W450A (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle size of the rubber particles can be measured using a dynamic light scattering method. Specifically, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of the rubber particles is created on a weight basis using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.). Is the average particle size.

  The upper limit of the content of the rubber particles is preferably 20% by weight or less with respect to 100% by weight of the nonvolatile content in the moisture absorbent resin composition layer, from the viewpoint of preventing the heat resistance and moisture permeability of the moisture absorbent resin composition layer from being lowered. 10 weight% or less is more preferable. On the other hand, the lower limit of the content of the rubber particles is preferably 0.1% by weight or more with respect to 100% by weight of the nonvolatile content in the moisture absorbent resin composition layer from the viewpoint of sufficiently obtaining the effect of blending the rubber particles. .

  A rubber particle-dispersed epoxy resin in which rubber particles are dispersed in the state of primary particles in an epoxy resin is commercially available. By using a rubber particle-dispersed epoxy resin as an epoxy resin, the resin composition contains rubber particles. May be. As such a rubber particle-dispersed epoxy resin, specifically, “BPA328” manufactured by Nippon Shokubai Co., Ltd. (rubber particles: acrylic core-shell type resin, average particle diameter of rubber particles: 0.3 μm, rubber particle content: 17% by weight, epoxy resin: bisphenol A type epoxy resin having an epoxy equivalent of 185), “MX120” manufactured by Kaneka Corporation (rubber particles: SBR resin, average particle size of rubber particles: 0.1 μm, rubber particle content: 25 Weight%, epoxy resin: bisphenol A type epoxy resin having an epoxy equivalent of 185) and the like.

(Thermoplastic resin)
The resin composition constituting the hygroscopic resin composition layer can further contain a thermoplastic resin. By containing a thermoplastic resin, flexibility can be imparted to the cured product of the resin fat composition, and good processability when coating the resin composition can be imparted. Specific examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. Any one of these thermoplastic resins may be used, or two or more thereof may be mixed and used. The thermoplastic resin preferably has a weight average molecular weight of 10,000 or more, more preferably 30,000 or more, from the viewpoint of imparting flexibility and preventing repelling during coating. However, if the weight average molecular weight is too large, the compatibility with the epoxy resin tends to be reduced. Therefore, the weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less. .

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

  Of the above-mentioned examples, the phenoxy resin is particularly preferable as the thermoplastic resin. The phenoxy resin is preferable because it has good compatibility with the “epoxy resin” and has little influence on the adhesiveness and moisture resistance of the cured product of the resin composition.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. Two or more phenoxy resins may be mixed and used.

  Specific examples of commercially available phenoxy resins include 1256 and 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin, YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin, and manufactured by Japan Epoxy Resin. YX6954 (bisphenolacetophenone skeleton-containing phenoxy resin), Union Carbide PKHH (weight average molecular weight (Mw) 42600, number average molecular weight (Mn) 11200) and the like are suitable. FX280, FX293, Toto Kasei Co., Ltd., Japan Epoxy Resin YL7553BH30, YL6794, YL7213, YL7290, YL7482 etc. can also be mentioned.

  The upper limit of the content of the thermoplastic resin is preferably 50% by weight or less, preferably 25% by weight or less, with respect to 100% by weight of the nonvolatile content in the moisture absorbent resin composition layer, from the viewpoint of preventing moisture permeability deterioration of the cured product. Is more preferable. On the other hand, the lower limit of the content of the thermoplastic resin is 1% by weight or more with respect to 100% by weight of the nonvolatile content in the hygroscopic resin composition layer from the viewpoint of obtaining a sufficient effect by including the thermoplastic resin. It is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more.

(Coupling agent)
The moisture-absorbing resin composition layer used in the present invention further contains a coupling agent, thereby allowing the cured product to adhere to an adherend (support, protective resin composition layer, sealing material, etc.). And the moisture resistance of the cured product can be improved. Specific examples of the coupling agent include a titanium coupling agent, an aluminum coupling agent, and a silane coupling agent. Among these, a silane coupling agent is preferable. You may use these 1 type or in combination of 2 or more types.

  Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl). Epoxy silane coupling agents such as ethyltrimethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane Coupling agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropylto Amino silanes such as methoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Coupling agents; ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents such as; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate-based silane coupling agents such as xysilane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. Among these, an epoxy-based silane coupling agent is particularly suitable.

  The upper limit of the content of the coupling agent is preferably 10% by weight or less with respect to 100% by weight of the nonvolatile content in the hygroscopic resin composition layer, from the viewpoint of obtaining an adhesion improving effect by adding the coupling agent. The following is more preferable. On the other hand, the lower limit of the content of the coupling agent is also preferably 0.5% by weight or more with respect to 100% by weight of the non-volatile content in the hygroscopic resin composition layer from the viewpoint of obtaining the effect of improving the adhesion by adding the coupling agent. .

  The moisture-absorbing resin composition layer used in the present invention may optionally contain various additives other than the above-described components within the range where the effects of the present invention are exhibited. Specific examples of such additives include organic fillers such as silicone powder, nylon powder, and fluorine powder, thickeners such as Orben and Benton, silicone-based, fluorine-based, and polymer-based antifoaming agents. Examples thereof include adhesion promoters such as leveling agents, triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds.

  The thickness of the hygroscopic resin composition layer used in the present invention is not particularly limited. However, in the structure in which a support is laminated on the resin composition layer, moisture permeation is only from the side of the resin composition layer. From the viewpoint of blocking moisture by reducing the thickness of the composition layer and reducing the contact area with the outside air, the upper limit of the thickness is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. On the other hand, from the viewpoint of securing 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 the present invention is composed of a thermosetting resin and a thermosetting resin composition containing a curing agent, and in a sealing structure of a target device (such as an organic EL device), By directly covering an element (such as an organic EL element), the hygroscopic metal oxide in the hygroscopic resin composition layer has a role of preventing the element from being damaged due to contact with the element.

(Thermosetting resin and curing agent)
As the thermosetting resin and the curing agent, those similar to the thermosetting resin and the curing agent used in the moisture absorbent resin composition layer described above are used. The thermosetting resin and curing agent used for the protective resin composition layer and the thermosetting resin and curing agent used for the moisture absorbent resin composition layer may be different from each other. The thermosetting resin and curing agent used for the protective resin composition layer and the thermosetting property used for the hygroscopic resin composition layer from the viewpoint of suppressing the interfacial stress between both layers after curing due to the difference in curing speed The resin and the curing agent are preferably the same.

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

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

  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 particle size of the hygroscopic metal oxide is large. Since the organic EL element may be damaged, the average particle diameter of the hygroscopic metal oxide is preferably less than 1 μm. Even if the average particle size is less than 1 μm, if the particle size distribution is broad, coarse particles are included and the organic EL element may be damaged. Therefore, the average particle size is less than 1 μm, and the particle size Is more preferable that does not contain particles of 3 μm or more.

  The hygroscopic metal oxide contained in the protective resin composition layer can be the same metal oxide as the hygroscopic metal oxide contained in the above-described hygroscopic resin composition layer, and the surface treatment and the like can also be performed. It can be applied in a similar manner. Moreover, if the average particle diameter of the hygroscopic metal oxide is less than 1 μm, it can be used as it is, but if the average particle diameter of the commercially available product is 1 μm or more, pulverization, classification, etc. are performed to obtain the average particle It is used after preparing a granular material having a diameter of less than 1 μm. The “average particle size” here is also synonymous with the average particle size of the hygroscopic metal oxide contained in the above-described hygroscopic resin composition layer.

(Inorganic filler)
The protective resin composition layer used in the present invention further contains an inorganic filler (excluding hygroscopic metal oxides), thereby delaying the moisture transmission rate at the interface between the layer and the EL element side. And the adhesive strength with the substrate can be improved. The said inorganic filler can use the same thing as the inorganic filler used for the above-mentioned moisture absorption resin composition layer. From the viewpoint that the inorganic filler is difficult to be exposed at the time of lamination, a filler having a flat plate shape such as talc, clay, mica and boehmite is preferable. In the case where an inorganic filler is used, the upper limit of the content of the inorganic filler is that the viscosity of the resin composition increases, and the strength of the cured product decreases and the non-volatile content in the resin composition layer becomes weak. It is preferably 15% by weight or less, more preferably 10% by weight or less, with respect to 100% by weight. On the other hand, the lower limit of the content of the inorganic filler is based on 100% by weight of the nonvolatile content in the resin composition from the viewpoint of obtaining an effect of delaying the moisture transmission rate at the interface between the resin composition layer and the EL element side. 1% by weight or more is preferable, and 3% by weight or more is more preferable. When the inorganic filler is used together with the hygroscopic metal oxide, the total amount of the inorganic filler and the hygroscopic metal oxide is 15% by weight or less with respect to 100% by weight of the nonvolatile content in the resin composition. Used in.

(Rubber particles, thermoplastic resins, coupling agents, etc.)
When the protective resin composition layer used in the present invention further contains rubber particles, the mechanical strength of the cured product can be improved, stress can be relaxed, and the like. In addition, the moisture-absorbing resin composition layer used in the present invention further includes a thermoplastic resin, thereby imparting flexibility to the cured product and providing good workability when coating the resin composition. Can be granted. Moreover, the moisture-absorbing resin composition layer used in the present invention can further improve the adhesion of the cured product to the adherend and the moisture resistance of the cured product by further containing a coupling agent. . The rubber particles, the thermoplastic resin, the coupling agent, and the like can be the same as the rubber particles, the thermoplastic resin, the coupling agent, etc. used in the moisture absorbent resin composition layer described above. A silane coupling agent is preferred, and the thermoplastic resin is preferably a phenoxy resin. The contents in these thermosetting resin compositions are basically the same as those in the thermosetting resin composition constituting the hygroscopic resin composition layer.

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

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

〔Protective film〕
Before the film of the present invention is actually used for forming a sealing structure, the protective film is preferably protected with a protective film in order to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. As the plastic film, the plastic film exemplified in the above-mentioned release type support can be used. The protective film is preferably subjected to a release treatment in advance, and specific examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used. The thickness of the protective film is not particularly limited, but is preferably 1 to 100 μm, more preferably 10 to 75 μm, and still more preferably 15 to 50 μm.

[Film production method]
The film of the present invention is not particularly limited, and can be used for various devices such as semiconductors, solar cells, high-brightness LEDs, LCD seals, organic ELs, and particularly preferably used for sealing organic EL elements. And can be suitably used for an organic EL device. Moreover, when distribute | circulating the film of this invention, a protective film can be attached and distribute | circulated. That is, the structure of the film of the present invention includes the following six aspects.
(1) Release system support + moisture absorbent resin composition layer + protective resin composition layer + protective film (2) Sealing system support + moisture absorbent resin composition layer + protective resin composition layer + protective film (3) Release system Support + protective resin composition layer + moisture absorbent resin composition layer + protective film (4) Release system support + moisture absorbent resin composition layer + protective resin composition layer (5) Sealing support + moisture absorbent resin composition layer + Protective Resin Composition Layer (6) Release System Support + Protective Resin Composition Layer + Hygroscopic Resin Composition Layer The above shows the order of lamination of the layers.

  Specifically, the constitutions (1) and (2) of the film of the present invention are the first varnish in which the resin composition constituting the hygroscopic resin composition layer is dissolved and the resin constituting the protective resin composition layer. A second varnish in which the composition is dissolved is prepared, and the first varnish is applied to the release system support or the sealing system support, and the organic solvent is dried to form a hygroscopic resin composition layer. It can be obtained by applying the second varnish thereon, drying the organic solvent to form a protective resin composition layer, and further using a protective film. Moreover, the structure of (3) of the film of this invention can be obtained by forming a protective resin composition layer and a moisture absorption resin composition layer reversely. The configurations of (4), (5), and (6) of the film of the present invention show the configuration when a protective film is not used in the film production of the configurations of (1), (2), and (3). .

  When the film of the present invention has the constitutions (1) and (3), the relationship between the release system support and the protection film must be such that the protection film is peeled off first. It is preferable to make it thinner or to give a release treatment or embossing to the protective film. The release support is preferably a polyethylene terephthalate (PET) film, and the protective film is preferably biaxially oriented polypropylene.

  Specific examples of the organic solvent used in the varnish include acetone, methyl ethyl ketone (hereinafter abbreviated as “MEK”), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbite. Examples thereof include acetates such as tol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use these 1 type or in combination of 2 or more types.

  There are no particular restrictions on the drying conditions, but 3 to 15 minutes at 50 to 100 ° C. are preferred.

  In the method for producing the film of the present invention by sequentially forming the hygroscopic resin composition layer and the protective resin composition layer in this order or in the reverse order on the support, the hygroscopic resin composition layer and A mixed layer in which the resin compositions of both layers are mixed is formed at the boundary of the protective resin composition layer, and the damage preventing effect of the organic EL element by the protective resin composition layer may be impaired. Therefore, a first resin composition sheet in which a moisture-absorbing resin composition layer is formed on the first support using the first varnish is produced, and separately from this, the second resin is formed on the second support. A second resin composition sheet having a protective resin composition layer formed thereon using the varnish of the first resin composition sheet, and a hygroscopic resin composition layer of the first resin composition sheet and a protective resin composition of the second resin composition sheet A method of laminating physical layers to obtain the film of the present invention is preferred. In this case, one of the first support and the second support is the support for the film of the present invention, and the other is the protective film for the film of the present invention.

  When the film of the present invention is obtained by such a method, the melt viscosity of the protective resin composition layer is preferably lower than the melt viscosity of the hygroscopic resin composition layer at the lamination temperature of the hygroscopic resin composition layer and the protective resin composition layer. . That is, at the lamination temperature of the hygroscopic resin composition layer and the protective resin composition layer, the hygroscopic resin composition has a lower melt viscosity than that of the hygroscopic resin composition layer. This is because it is possible to avoid the filler contained in the physical layer from moving to the protective resin composition layer at the time of lamination, and further passing through the protective resin composition layer and damaging the EL element.

  As used herein, “melt viscosity” refers to a model Rheosol-G3000 manufactured by UBM, using a parallel plate having a resin amount of 1 g and a diameter of 18 mm, a measurement start temperature of 60 ° C., and a temperature increase rate of 5 ° C./min. It is a value measured at a temperature of 60 ° C. to 200 ° C. and a frequency of 1 Hz / deg.

  The laminating temperature is not particularly limited and can be appropriately set according to the required performance, but it is required to be lower than the curing temperature of the hygroscopic resin composition layer and the protective resin composition layer. Is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower. 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, and still more preferably 60 ° C. or higher, from the viewpoint of good handleability at room temperature. Is particularly preferred. Also, from the viewpoint of preventing the hygroscopic resin composition layer and the protective resin composition layer from being mixed together at the set laminating temperature, preventing the hygroscopic metal oxide from moving to the protective resin composition layer. The lower limit of the difference between the melt viscosity of the hygroscopic resin composition layer 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 300 poise or more. Is more preferably 1000 poise or more, more preferably 5000 poise or more, still more preferably 10,000 poise or more, still more preferably 15000 poise or more, and most preferably 30000 poise or more. On the other hand, at the set laminating temperature, the hygroscopic resin composition layer and the protective resin composition layer are efficiently bonded at once, and the hygroscopic resin composition layer and the protective resin composition layer are efficiently bonded together. From the viewpoint, the upper limit of the difference between the melt viscosity of the hygroscopic resin composition layer 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 1,000,000 poise or less. 500,000 poise or less is more preferable, and 100,000 poise or less is more preferable.

  In addition, as a method for adjusting the melt viscosity of the protective resin composition layer and the hygroscopic resin composition layer, a method of changing the degree of curing depending on drying conditions, a method of changing the blending ratio of the liquid resin, the particle diameter of the inorganic filler, and content The method etc. which change a ratio etc. are mentioned, You may implement these combining 2 or more. Therefore, by these methods, the viscosity of the protective resin composition layer and the hygroscopic resin composition layer is adjusted, and the melt viscosity of the protective resin composition layer at a predetermined temperature is higher than the melt viscosity of the hygroscopic resin composition layer at the predetermined temperature. To be low.

  The film of the present invention can be applied to the formation of a sealing structure for various semiconductor elements (individual semiconductors, optical semiconductors, logic ICs, analog ICs, memories, etc.), and is particularly preferably used for sealing organic EL elements. be able to.

[Organic EL device manufacturing method]
A method for producing an organic EL device by sealing an organic EL element using the film of the present invention will be described below. In the sealing structure of the device, the protective resin composition layer is disposed so as to cover the element of the element forming substrate, and the hygroscopic resin composition layer is a surface opposite to the surface of the protective resin composition layer on the element forming substrate side. Placed in. The structure of the film of the present invention includes the following six aspects as described above.
(1) Release system support + moisture absorbent resin composition layer + protective resin composition layer + protective film (2) Sealing system support + moisture absorbent resin composition layer + protective resin composition layer + protective film,
(3) Peeling support + protective resin composition layer + hygroscopic resin composition layer + protective film,
(4) Release system support + moisture absorbent resin composition layer + protective resin composition layer (5) Sealing system support + moisture absorbent resin composition layer + protective resin composition layer (6) Release system support + protective resin composition Physical layer + hygroscopic resin composition layer

  (A) When the film of this invention is the 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 EL element was formed. Thereafter, the release support is peeled off, the sealing material is laminated on the exposed moisture absorbent resin composition layer, and the thermosetting operation of the protective resin composition layer and the moisture absorbent resin composition layer is performed to manufacture an organic EL device. can do.

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

  (C) When the film of this invention is the structure of (3), a protective film is removed first and a hygroscopic resin composition layer is laminated on a sealing material. Thereafter, the release support 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 is performed. An organic EL device can be manufactured.

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

  (E) When the film of the present invention has the configuration of (5), the protective resin composition layer is laminated on the transparent substrate on which the organic EL element is formed, and the heat of the protective resin composition layer and the hygroscopic resin composition layer is left as it is. A curing operation can be performed to produce an organic EL device.

  (F) When the film of the present invention has the configuration of (6), the hygroscopic resin composition layer is laminated on the sealing material, and then the release support is peeled off, and the exposed protective resin composition layer is formed into an organic EL element. The organic EL device can be manufactured by laminating on the transparent substrate on which the protective resin composition layer and the hygroscopic resin composition layer are thermally cured.

  From the viewpoint of not applying excessive heat history to the organic EL element, it is preferable to produce an organic EL device by the method (b), (c), (e) or (f).

  The sealing material used in the methods (a), (c), (d), and (f) is a material for forming a sealing structure that is prepared separately from the film of the present invention. Examples of the sealing material include a plastic film having moisture resistance, a metal foil such as a copper foil and an aluminum foil, a glass plate, and a metal plate. The upper limit of the thickness of the sealing material is preferably 5 mm or less, more preferably 1 mm or less, and still more preferably 100 μm or less from the viewpoint of making the organic EL device itself thin and light. Further, the lower limit of the thickness of the sealing material is preferably 5 μm or more, more preferably 10 μm or more, and further 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, the total thickness after bonding is preferably in the range of 5 μm or more and 5 mm or less.

The laminating method performed in the above methods (a) to (f) may be a batch method or a continuous method using a roll. Lamination conditions can be carried out under reduced pressure, preferably using a vacuum laminator or the like. It is preferable to perform lamination under conditions of a temperature of 50 to 130 ° C. and a pressure of 0.5 to 10 kgf / cm ² under a reduced pressure of 10 ⁻³ (10 hPa) MPa or less. Specific examples of the vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  There is no restriction | limiting in particular in the method of thermosetting a protective resin composition layer and a moisture absorption resin composition layer, A well-known thing can be used. Specific examples include a hot-air circulating oven, an infrared heater, a heat gun, a high-frequency induction heating device, and heating by pressure bonding of a heat tool. The film of the present invention has very good low-temperature curability, and 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 the viewpoint of securing the adhesiveness of the cured product, the lower limit of the curing temperature is preferably 50 ° C. or higher, and more preferably 55 ° C. or higher. Moreover, 120 minutes or less is preferable, as for the upper limit of hardening time, 90 minutes or less are more preferable, and 60 minutes or less are still more preferable. On the other hand, from the viewpoint of surely curing the cured product, the lower limit of the curing time is preferably 20 minutes or more, and more preferably 30 minutes or more. Thereby, the thermal deterioration of the organic EL element can be extremely reduced.

  In the organic EL device of the present invention, when the organic EL element is formed on the transparent substrate, if the transparent substrate side is the display surface of the display or the light emitting surface of the lighting fixture, the sealing system support or the sealing A transparent material is not necessarily used for the material, and a metal plate, a metal foil, an opaque plastic film, or a plate may be used.

  EXAMPLES 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.

[Materials used]
The materials used in the experiment will be described.
(A) Epoxy resin Solid epoxy resin (“HP7200H” manufactured by DIC: dicyclopentadiene type solid epoxy resin, epoxy equivalent (278 g / eq))
・ Rubber fine particle-dispersed liquid epoxy resin (“BPA328” manufactured by Nippon Shokubai Co., Ltd.) A composition comprising 17% by weight of bisphenol A type epoxy resin having an epoxy equivalent of 185 and two-layer acrylic resin particles having a primary particle size of 0.3 μm Epoxy equivalent (230 g / eq))
Liquid epoxy resin (“GOT” manufactured by Nippon Kayaku Co., Ltd .: orthotoluidine diglycidylamine, epoxy equivalent (135 g / eq))
(B) Phenoxy resin-Japan Epoxy Resin "YL7213-35M" (weight average molecular weight 35000) solid content 35% by weight MEK solution (C) curing agent-Epoxy resin latent curing accelerator (Sanapuro " U-CAT3502T ")
・ Ionic liquid curing agent ("TBP / N-Ac-gly", N-acetylglycine tetrabutylphosphonium salt)
(D) Hygroscopic metal oxide Firing dolomite: MEK slurry (40% by weight as solid content, average particle size: 0.87 μm) obtained by wet grinding of “light calcined dolomite” manufactured by Yoshizawa Lime
(E) Inorganic filler-Talc: MEK slurry of wet pulverized "D-600" manufactured by Nippon Talc Co., Ltd. (30 wt% as solid content, average particle size: 0.72 µm)
(F) Surface treatment agent ・ Stearic acid (G) coupling agent ・ Silane coupling agent: “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

〔Measuring method〕
Next, a measurement method will be described.
[Adhesive strength between support and resin composition layer]
Two aluminum foils (width 50 mm, length 50 mm, thickness 50 μm) were prepared, and the resin composition layer (width 40 mm, length 50 mm) on the substrate was superimposed on one surface of the first aluminum foil. The laminate was laminated by a vacuum laminator under the conditions of a temperature of 80 ° C. and a pressure of 1 kgf / cm ² (9.8 × 10 ⁴ Pa). Then, the base material is peeled off, and a second aluminum foil is laminated on the exposed resin composition layer and laminated under the same conditions, and a test piece having a three-layer structure of aluminum foil, resin composition layer, and aluminum foil. It was created. The test piece was heat-cured at 110 ° C. for 30 minutes, then cut into a rectangular test piece having a width of 10 mm and a length of 50 mm, and the length of the test piece was measured in accordance with the T-type peel test method of JIS K-6854. The direction adhesive strength (peeling force) was measured.

〔Evaluation method〕
Next, the evaluation method will be described.
[Evaluation of moisture permeability]
The organic EL device was exposed to a constant temperature environment of 60 ° C./90% RH for 1000 hours, and the moisture permeation resistance of the film was evaluated. The moisture permeation resistance of the film was judged from the state of shrinkage (shrink) and DS (dark spot) of the light emitting area generated in the light emitting part of the organic EL element, and the relative change rate of luminance after the initial (0 hour) and 1000 hours was evaluated. . That is, when a large amount of shrinkage or DS occurs, the light emitting area decreases, the luminance of the light emitting portion increases, and the relative change rate with respect to the luminance in the initial state without defects increases. The luminance was measured at two points with constant current drive (15 mA), and the average value was calculated. As an evaluation, when the relative change rate was less than 1.1, it was rated as “◯”, and when it was 1.1 or more, it was marked as “x”.

[Evaluation of device damage resistance]
The degree of damage of the organic EL element was evaluated by a dark current value at a driving voltage of 3V. As an evaluation, when the dark current value was less than 0.2 μA, it was evaluated as ◯, and when it was 0.2 μA or more, it was rated as x.

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

(Production Example 1)
A mixed solution prepared by dissolving a solid epoxy resin (“HP7200H” manufactured by DIC) in a phenoxy resin (a MEK solution having a solid content of 35% by weight of “YL7213-35M” manufactured by Japan Epoxy Resin Co., Ltd.) was prepared. In addition, a rubber fine particle-dispersed liquid epoxy resin (“BPA328” manufactured by Nippon Shokubai Co., Ltd.), a liquid epoxy resin (“GOT” manufactured by Nippon Kayaku Co., Ltd.), and a latent curing accelerator for epoxy resin (“U-CAT3502T manufactured by Sun Apro Co., Ltd.) )), A silane coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), an ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt), and MEK are added and dispersed uniformly with a high-speed rotating mixer. Thus, varnish A was obtained.

(Production Example 2)
A mixture A was prepared by dissolving a solid epoxy resin (“HP7200H” manufactured by DIC) in a phenoxy resin (a MEK solution having a solid content of 35% by weight of “YL7213-35M” manufactured by Japan Epoxy Resin). On the other hand, stearic acid was added to and dispersed in MEK slurry (40% by weight as a solid content) of calcined dolomite (wet crushed by Yoshizawa Lime Co., Ltd.) to prepare a mixture B. Mixture A, mixture B, talc ("D-600" manufactured by Nippon Talc Co., Ltd., wet pulverized, MEK slurry having a solid content of 30% by weight), rubber fine particle-dispersed liquid epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd.) , Latent curing accelerator for epoxy resin ("U-CAT3502T" manufactured by Sun Apro), liquid epoxy resin ("GOT" manufactured by Nippon Kayaku Co., Ltd.), silane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) It mix | blended and mixed with the azimuthal mixer Robomix type | mold mixing stirrer (made by Primex). An ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt) was added thereto and dispersed uniformly with a high-speed rotary mixer to obtain varnish B.

(Production Example 3)
Table 1 below shows the same method as in Varnish A in Production Example 1 except that talc ("D-600" manufactured by Nippon Talc Co., Ltd. was wet pulverized and MEK slurry having a solid content of 30% by weight) was added. Varnish C was prepared according to the recipe of

(Production Example 4)
Varnish D was prepared by the same method as varnish B in Production Example 2 according to the formulation in Table 1 below.

(Production Example 5)
Varnish E was prepared in the same manner as in Varnish B in Production Example 2 according to the recipe shown in Table 1 below.

(Test Examples 1 to 3)
About each resin composition layer produced by varnish B, D, and E, the adhesive force with a support body was measured. The results are shown in Table 2.

  From the results in Table 2, it was found that the adhesive force of the resin composition layer to the support was greatly improved by blending talc in the resin composition layer of the film of the present invention.

(Test Examples 4 to 6)
Varnish A was uniformly applied on the release treated surface of a PET film (thickness 38 μm) treated with an alkyd mold release agent with a die coater so that the thickness of the resin composition layer after drying was 10 μm. The protective resin composition layer A1 was obtained by drying at 60 to 95 ° C. for 12 minutes. The melt viscosity at 100 ° C. of the protective resin composition layer A1 was 6170 poise.

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

  Uniform coating with a die coater so that the thickness of the resin composition layer after drying is 30 μm on the release-treated surface of a PET film (thickness 38 μm) treated with varnish B with an alkyd release agent. Then, moisture-absorbing resin composition layer B1 was obtained by drying at 60 to 95 ° C. for 12 minutes. The melt viscosity at 100 ° C. of the hygroscopic resin composition layer B1 was 23700 poise.

  Uniform coating with a die coater so that the thickness of the resin composition layer after drying is 30 μm on the release-treated surface of a PET film (thickness 38 μm) treated with varnish B with an alkyd release agent. Then, moisture-absorbing resin composition layer B2 was obtained by drying at 60 to 80 ° C. for 6 minutes. The melt viscosity at 100 ° C. of the hygroscopic resin composition layer B2 was 4460 poise.

In the combination shown in Table 3, the protective resin composition layer with PET film and the hygroscopic resin composition layer with PET film are placed at a temperature of 100 ° C. with a vacuum laminator with the protective resin composition layer and the hygroscopic resin composition layer facing each other. And a film (Test Examples 4 to 6) having a support, a protective resin composition layer, and a hygroscopic resin composition layer were laminated under conditions of a pressure of 1 Kg / cm ² (9.8 × 10 ⁴ Pa). . Thereafter, the vicinity of the boundary between the protective resin composition layer and the hygroscopic resin composition layer in the cross section of each produced film was observed with an SEM (scanning electron microscope) (magnification 2000 times). 2 is an SEM photograph of the film section of Test Example 4, FIG. 3 is an SEM photograph of the film section of Test Example 5, and FIG. 4 is an SEM photograph of the film section of Test Example 6.

  The difference in melt viscosity between the hygroscopic resin composition layer and the protective resin composition layer in the film (melt viscosity of the hygroscopic resin composition layer−melt viscosity of the protective resin composition layer) was 17530 poise for the film of Test Example 4, and the test The film of Example 5 is 3430 poise and the film of Test Example 6 is -1710 poise. In the film of Test Example 4 (FIG. 2), the interface between the hygroscopic resin composition layer (upper layer) and the protective resin composition layer (lower layer) is substantially horizontal, and the protective resin composition from the hygroscopic resin composition layer (upper layer). No migration of the hygroscopic metal oxide to the physical layer (lower layer) was observed. Also in the film of Test Example 5 (FIG. 3), no hygroscopic metal oxide was transferred from the hygroscopic resin composition layer (upper layer) to the protective resin composition layer (lower layer). On the other hand, in the film of FIG. 6 (FIG. 4), the migration of the hygroscopic metal oxide (light spots) 7 was observed from the hygroscopic resin composition layer (upper layer) to the protective resin composition layer (lower layer). .

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

[Creation of organic EL devices]
(Washing of ITO substrate and sealing glass plate)
The cleaning of the ITO (indium / tin oxide) substrate and the sealing glass plate was performed in a class 10000 clean room and a class 100 clean booth, respectively. The cleaning solvent used 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)
On a glass substrate of 30 mm square (length 30 mm x width 30 mm) and 0.7 mm thickness at a vacuum degree of 1 to 2 × 10 ⁻⁴ Pa and a deposition rate of 1.0 to 2.0 mm / s, Glass / SiO Each layer is vapor-deposited in a configuration of ₂ [53 nm] / ITO [55 nm] / PEDOT / PSS [40 nm] / α-NPD [50 nm] / Alq ₃ [50 nm] / LiF [0.8 nm] / Al [15 nm] An EL element was produced. The area of the light emitting part is 10 × 10 mm ² .
“PEDOT · PSS” is an abbreviation for (poly (3,4-ethylenedioxythiophene)) · (polystyrene sulfonic acid), and “α-NPD” is (bis [N- (1-naphthyl) -N— (Phenyl) benzidine), “Alq ₃ ” is an abbreviation for tris (8-quinolinolato) aluminum.

(Sealing of organic EL elements)
First, the film of the present invention was laminated on a glass plate (21 mm × 28 mm, 0.7 mm thickness) as a sealing material. Lamination was performed in a Class 100 clean booth by vacuum pressing under conditions of 80 ° C., reduced pressure (1 × 10 ⁻³ MPa or less) suction 20 seconds, and press 20 seconds.
Next, the support is peeled off, and the resin composition layer exposed on the glass plate is subjected to reduced pressure (1 × under a 0.04 MPa load at 80 ° C. in a glove box having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less. 10 ⁻³ MPa or less) Vacuum pressing was performed toward the organic EL element forming substrate under the conditions of suction 20 seconds and press 20 seconds.
Then, in the glove box, it heated on the 110 degreeC hotplate for 30 minutes, and the film of this invention was thermosetted.
The resin composition layer is formed by laminating a protective resin composition layer and a hygroscopic resin composition layer. Lamination to a glass plate as a sealing material is performed by pressing the hygroscopic resin composition layer onto a glass plate, For laminating the EL element forming substrate, the protective resin composition layer was pressure-bonded to the organic EL element forming substrate.

Example 1
Varnish A was uniformly applied on the release treated surface of a PET film (thickness 38 μm) treated with an alkyd mold release agent with a die coater so that the thickness of the resin composition layer after drying was 10 μm. The protective resin composition layer was obtained by drying at 60 to 95 ° C. for 12 minutes.

  Similarly, a die coater is used so that the thickness of the resin composition layer after drying is 30 μm on the release treatment surface of a PET film (thickness 38 μm) obtained by treating varnish B with an alkyd mold release agent. It apply | coated uniformly and was dried at 60-95 degreeC for 12 minutes, and the moisture absorption resin composition layer was obtained.

A protective resin composition layer with a PET film and a hygroscopic resin composition layer with a PET film, and a protective resin composition layer and a hygroscopic resin composition layer face each other with a vacuum laminator at a temperature of 80 ° C. and a pressure of 1 kg / cm ² (9. The film of the present invention was produced by laminating under conditions of 8 × 10 ⁴ Pa). The protective resin composition layer had a melt viscosity at 80 ° C. of 27500 poise, and the hygroscopic resin composition layer had a melt viscosity at 80 ° C. of 63400 poise. Next, the PET film on the moisture absorbent resin composition layer side of the film is peeled off, the moisture absorbent resin composition layer is laminated on a glass plate as a sealing material, and then the PET film on the protective resin composition layer side is peeled off for protection. The resin composition layer was laminated on a glass plate having an organic EL element to produce an organic EL device.

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

(Comparative Example 1)
Varnish B is uniformly applied by a die coater on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd release agent so that the thickness of the resin composition layer after drying is 40 μm. The resin composition layer was obtained by applying and drying at 60 to 95 ° C. for 12 minutes. After laminating this resin composition layer with a PET film on a glass plate as a sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element to produce an organic EL device. .

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

(Comparative Example 2)
Varnish A is uniformly applied by a die coater on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd release agent so that the thickness of the resin composition layer after drying is 40 μm. The resin composition layer was obtained by applying and drying at 60 to 95 ° C. for 12 minutes. After laminating this resin composition layer with a PET film on a glass plate as a sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element to produce an organic EL device. .

  FIG. 1C is a diagram schematically showing a cross section of the produced organic EL device. A resin composition layer (inorganic) is formed on the surface of the substrate 5 on which the organic EL element 4 is formed. A filler, no hygroscopic metal oxide) 3 and a 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. The PET film on the resin composition layer side derived from varnish C of this film is peeled off, and the resin composition layer is laminated on a glass plate as a sealing material, and then the PET film on the resin composition layer side derived from varnish A is peeled off. And this resin composition layer was laminated on the glass plate which has an organic EL element, and the organic EL device was produced.

  FIG. 1 (d) is a diagram schematically showing a cross section of the produced organic EL device. A resin composition layer (inorganic) is formed on the surface of the substrate 5 on which the organic EL element 4 is formed. A filler, no hygroscopic metal oxide) 3, a resin composition layer (containing an inorganic filler, no hygroscopic metal oxide) 6 and a sealing material (glass plate) 1 are laminated in this order.

(Comparative Example 4)
Varnish C is uniformly applied by a die coater on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd release agent so that the thickness of the resin composition layer after drying is 40 μm. The resin composition layer was obtained by applying and drying at 60 to 95 ° C. for 12 minutes. After laminating this resin composition layer with a PET film on a glass plate as a sealing material, the PET film was peeled off, and the resin composition layer was laminated on a glass plate having an organic EL element to produce an organic EL device. .

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

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

From Example 1, by using the film of the present invention, the organic EL element sealing structure that achieves a high level of isolation from the moisture of the organic EL element while reducing damage to the organic EL element can be simplified. It can be seen that it can be formed. Moreover, in Example 1, since the hygroscopic resin composition layer and the protective resin composition layer are cured at a low temperature to seal the organic EL element, not only the damage of the organic EL element in the sealing operation but also the organic EL element is sealed. The thermal deterioration of was sufficiently suppressed, and a highly reliable organic EL element device could be obtained.
On the other hand, Comparative Example 1 contained a large amount of hygroscopic metal oxide and damaged the organic EL element. Moreover, since Comparative Examples 2, 3, and 4 did not contain a hygroscopic metal oxide, the organic EL element was damaged by moisture. In addition, although the comparative example 4 contained talc, it was difficult to transfer due to the flat filler, and the damage resistance of the device was maintained.

  A film having a support, a protective resin composition layer, and a moisture absorption resin composition layer can realize a film having both moisture permeation resistance and element damage resistance, and such a film provides a highly reliable organic EL device. I can do it now.

  This application is based on patent application No. 2009-182827 filed in Japan, the contents of which are incorporated in full herein.

1 Sealing material (glass plate)
2 Hygroscopic resin composition layer (containing inorganic filler and hygroscopic metal oxide)
3 Protective resin composition layer (inorganic filler, hygroscopic metal oxide free)
4 Organic EL element 5 Substrate 6 Resin composition layer (containing inorganic filler, no hygroscopic metal oxide)
7 Hygroscopic metal oxide

Claims (7)

  A laminated film having a support, a protective resin composition layer and a hygroscopic resin composition layer, wherein the protective resin composition layer and the hygroscopic resin composition layer are adjacent to each other, wherein the protective resin composition layer is a thermosetting resin and a cured resin The moisture-absorbing resin composition layer is composed of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a hygroscopic metal oxide. ,the film.   It further has a protective film, and is laminated in the order of the support, the hygroscopic resin composition layer, the protective resin composition layer, and the protective film, or in the order of the support, the protective resin composition layer, the hygroscopic resin composition layer, and the protective film. The film according to claim 1, wherein the film is formed.   The film according to claim 1 or 2, wherein the hygroscopic resin composition layer contains an inorganic filler (excluding a hygroscopic metal oxide).   The film according to any one of claims 1 to 3, wherein the protective resin composition layer contains an inorganic filler (excluding a hygroscopic metal oxide).   Difference in melt viscosity between the hygroscopic resin composition layer and the protective resin composition layer (melt viscosity of the hygroscopic resin composition layer−melt viscosity of the protective resin composition layer) at the laminating temperature set in the range of 40 ° C. to 130 ° C. The film according to any one of claims 1 to 4, wherein is from 300 poise to 1,000,000 poise.   The film of any one of Claims 1-5 which is a film for sealing of an organic EL element used so that a protective resin composition layer may coat | cover an organic EL element.   An organic EL device comprising the film according to claim 1.