KR20000071821A - Laminate, method for manufacturing the same, and the use therefor - Google Patents

Abstract

The laminate according to the present invention comprises a surface-treated polyethylene terephthalate film having a thin film layer composed of a metal oxide or a metal oxide and a metal fluoride on a polyethylene terephthalate film, and a metal oxide or a metal oxide and a metal fluoride on a polyvinyl alcohol film. A surface-treated polyvinyl alcohol film having a thin film layer formed is bonded by an adhesive containing a polyurethane resin and a polyepoxy compound having an amino group. The laminated body of this invention is used suitably as a sealing material of a display element.

Description

Laminate, method for manufacturing the same and use thereof {Laminate, method for manufacturing the same, and the use therefor}

The present invention provides a laminate which is suitably used for encapsulating display elements such as liquid crystal display elements, electroluminescence (hereinafter referred to as EL) elements among display materials constituting a flat panel display, a manufacturing method thereof, and displays using the same. A device sealing structure, the laminated body for display element formation, and an unsealed display element structure.

BACKGROUND OF THE INVENTION With the rapid progress of electronic technology, flat panel displays such as liquid crystal displays, plasma displays, EL displays, and light emitting diode displays have been put into practical use. In addition, the EL element has been put into practical use as a backlight of a liquid crystal display, and has attracted particular attention.

As an EL element, there is an organic EL element composed of an inorganic EL element whose light emitting material is an inorganic compound and an organic compound thin film. Among these, the light source portion of the group EL element is made of a light emitting material such as zinc sulfide, and the light emitting material has a low light emission function due to moisture. In addition, in the organic EL device, the organic thin film is also affected by moisture, but since the metal used as the cathode is oxidized by moisture, the light emitting function is significantly reduced. Therefore, the light source part of the EL element is sealed with heat-sealing plastic having high moisture resistance such as a fluorine film.

In recent years, an unsealed type inorganic EL device, which is improved to have moisture proof performance even without a sealing film, which uses a material having a moisture-proof treatment for the light emitting material itself and a material having a low moisture absorption rate and moisture permeability, has been put into practical use. have.

However, from the expansion of the use of an EL element, it cannot be said that it is enough in the moisture proof property of a fluororesin film, and the market demands more high moisture proof property. In addition, since the fluororesin film is extremely poor in productivity, the fluororesin film has a high price and is one of the causes of preventing the spread of the EL element.

Moreover, in order to protect the light source part of an EL element, high moisture proof property is required, and since it is necessary to thicken a fluororesin film, transparency (light transmissivity) of the film itself falls, and the light emission capability of the light source part of an EL element is not fully exhibited. There was a flaw.

Moreover, since the moisture proof property of the non-sealing type inorganic EL element is not perfect, it is the present situation that use is limited and such moisture proof property is calculated | required.

Accordingly, it is an object of the present invention to provide a laminate and a method for manufacturing the same, which are suitably used for the formation of an encapsulated and non-encapsulated display element of a display element having a high water vapor barrier property having little temperature dependency.

Further, another object of the present invention is to provide a display element encapsulation structure without deterioration in light emitting function.

Furthermore, another object of the present invention is to provide a laminate and an unsealed display element structure which are used for forming an unsealed type inorganic EL element which is excellent in moisture resistance and is not limited in use.

1 is a cross-sectional view of an EL element encapsulation structure of the present invention.

2 is a cross-sectional view of an unsealed type inorganic EL element (an unsealed display element structure) using the laminate for forming a display element of the present invention.

* Description of the symbols for the main parts of the drawings *

DESCRIPTION OF SYMBOLS 1: Laminated body for sealing display elements 2: Heat-sealing interface

3: transparent conductive film having transparent electrode layer 4: light emitting layer

5: insulation layer 6: aluminum (back electrode layer)

7 Lead Wire 8 Barrier Properties Substrate

9: laminate for forming display element 10: laminate

11: plastic film 12: ITO membrane

13 emitting layer 14 insulating layer

15 back electrode layer 16 protective layer

100 display element encapsulation structure

200: sealed type inorganic EL element (unsealed display element structure)

The present inventors have a surface-treated polyethylene terephthalate film having a thin film layer made of a metal oxide or a metal oxide and a metal fluoride on a polyethylene terephthalate film, and a thin film layer made of a metal oxide or a metal oxide and a metal fluoride on a polyvinyl alcohol film. The laminate obtained by laminating the surface-treated polyvinyl alcohol film through an adhesive containing a polyurethane resin and a polyepoxy compound having an amino group has a water vapor barrier performance exceeding the fluororesin film, and the barrier performance is almost at a temperature. The present invention was found to have an excellent appearance without depending on and without foaming of the adhesive.

That is, the present invention provides a surface-treated polyethylene terephthalate film having a thin film layer of metal oxide or metal oxide and metal fluoride on a polyethylene terephthalate film, and a thin film layer of metal oxide or metal oxide and metal fluoride on polyvinyl alcohol film. It is a laminated body formed by laminating | stacking the surface-treated polyvinyl alcohol film which has an adhesive through the adhesive agent containing the polyurethane resin and polyepoxy compound which have an amino group.

Moreover, this invention is the said laminated body formed by laminating | stacking a heat-sealable plastic film preferably on the surface-treated polyvinyl alcohol film side.

Moreover, this invention is the surface-treated polyethylene terephthalate film which has a thin film layer which consists of a metal oxide or a metal oxide, and a metal fluoride on a polyethylene terephthalate film; On at least one of the surface treatment polyvinyl alcohol film which has a metal oxide or a thin film layer which consists of a metal oxide and a metal fluoride on a polyvinyl alcohol film, the adhesive agent containing the polyurethane resin and polyepoxy compound which have an amino group is apply | coated, and the surface It is a manufacturing method of the laminated body which laminates a treated polyethylene terephthalate film and a surface-treated polyvinyl alcohol film.

In addition, the present invention provides a barrier substrate, a display element laminated on the barrier substrate so that the light emitting surface is an outer surface of the barrier substrate, and a surface treatment of the light emitting surface of the display element on the display element. It is a display element sealing structure which consists of the said laminated body of this invention laminated | stacked so that an ethylene terephthalate film may become an outer surface, and bonds a barrier base material and a laminated body around the said display element.

Moreover, this invention is the polyurethane resin which has an amino group on the plastic film side of the transparent conductive film which has a transparent electrode in one side of a plastic film so that the said laminated body of this invention may be an outer surface of a surface-treated polyethylene terephthalate film. And a laminate for forming display elements formed by laminating through an adhesive including a polyepoxy compound.

Moreover, this invention is an unsealed type display element structure by which the said display element formation laminated body of this invention is laminated | stacked in the light emitting direction of a display element.

The polyethylene terephthalate film (hereinafter referred to as PET film) as the base material of the surface-treated polyethylene terephthalate film may be either a biaxially oriented film, a uniaxially oriented film, or an unoriented film. In addition, an amorphous PET film is also applicable. Among these, a biaxially stretched film is especially preferable at the point of water vapor barrier property. In addition, it is preferable that nothing is given to the surface of the PET film, but surface treatment, easy adhesion treatment or organic barrier treatment for improving the adhesion with the thin film layer may be applied to one or both surfaces.

Examples of the surface treatment of the PET film for improving the adhesiveness with the thin film layer include a colon, a discharge treatment, a plasma treatment, a frame treatment and the like. Moreover, as an easy adhesion | attachment process, organic coating processes, such as polyethyleneimine, a polyurethane, an acrylic resin, polybutadiene polyester, are mentioned. Moreover, as an organic barrier process, organic barrier coating processes, such as polyvinylidene chloride and ethylene vinyl alcohol copolymer saponification (EVOH), are mentioned.

6-500 micrometers is preferable and, as for the thickness of PET film, 12-25 micrometers is suitable especially.

The polyvinyl alcohol film (henceforth PVA film) which is a base material of a surface treatment polyvinyl alcohol film may be a biaxially stretched film, a uniaxially stretched film, or an unstretched film. Among these, a biaxially stretched film is especially preferable at the point of water vapor barrier property. In addition, like PET film, it is preferable that nothing is given to the surface of the PVA film, but even if surface treatment, easy adhesion treatment, or organic barrier treatment for improving adhesion with the thin film layer is applied to one or both surfaces, it does not matter. none. In addition, the contents of surface treatment, easy adhesion treatment, and organic barrier treatment are the same as in the case of PET film.

The metal oxide formed on PET film and PVA film, or the thin film layer which consists of a metal oxide and a metal fluoride has especially high water vapor barrier property, gas barrier property, and little expansion with respect to temperature.

Here, especially when the transparency of a film is to be considered as important, the thin film layer which consists of a metal oxide and a metal fluoride is preferable.

In addition, the thin film layer should be in close contact with the PET film or PVA film as the base material.

Examples of the metal oxide constituting the thin film layer include silicon oxide, aluminum oxide, magnesium oxide, tin oxide, indium tin oxide, and the like. Among them, silicon oxide is most excellent in terms of water vapor barrier performance. Silicon oxide is a compound represented by SiOx (X = 1 or more, 2 or less), and the like _{SiO, Si 2 O 3, Si} 3 O 4, SiO 2. Especially, when colorless transparency is important especially, it is preferable that x of SiOx is larger than 1.8 and is 2.0 or less. In this case, since silicon oxide approaches colorless transparent SiO ₂ , the light transmittance (transparency) of the thin film layer obtained increases. On the contrary, when x of SiOx is 1.8 or less, the silicon oxide becomes slightly brown, and further, when x of SiOx is 1.5 or less, it becomes completely brown. When used for formation of an element, it becomes a cause of reducing the light emission luminance of an EL element.

As a metal fluoride which comprises a thin film layer, the fluoride of an alkaline earth metal, the fluoride of an alkali metal, and aluminum fluoride are mentioned. Specifically, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride and the like can be given. Among these, magnesium fluoride, calcium fluoride, strontium fluoride, and barium fluoride are preferable, and magnesium fluoride and calcium fluoride are excellent in particular in terms of barrier property.

Since the metal fluoride is contained in the thin film layer, the water vapor barrier performance is improved and the transparency of the thin film layer can be obtained.

When the metal fluoride is a fluoride of alkaline earth metal, high barrier properties and high transparency can be achieved. In the case of the fluoride of an alkali metal, although transparency is the same as that of the fluoride of an alkaline earth metal, barrier property is slightly inferior.

The composition ratio of the metal oxide: metal fluoride constituting the thin film layer is preferably in the range of 98 to 80 mol%: 2 to 20 mol%, particularly 95 to 90 mol%: 5 to 10 mol%.

When the thin film layer is composed of silicon oxide or silicon oxide and a metal fluoride, an appropriate amount of magnesium oxide may be contained. Examples of the magnesium oxides include magnesium oxide, co-oxides of magnesium oxide and silicon dioxide (coates called forsterite and steatite), and composite compounds of magnesium oxide and metal fluoride.

The composition ratio of silicon oxide: magnesium oxide constituting the thin film layer is preferably in the range of 99.5 to 80 mol%: 0.5 to 20 mol%, particularly 98 to 90 mol%: 2 to 10 mol%.

When the thin film layer is composed of silicon oxide, metal fluoride, and magnesium oxide, the composition ratio of silicon oxide: metal fluoride: magnesium oxide is 80 to 97 mol%: 2 to 19 mol%: 1 to 18 mol%, Especially the range of 80-93 mol%: 5-18 mol%: 2-15 mol% is preferable.

The raw material for forming the thin film layer may be any one or a mixture of metal oxides, metal fluorides, metals, and organometallic compounds, but especially a mixture of silicon oxides and metal fluorides, or silicon oxides, metal fluorides, and silicon dioxides and oxides. It is preferable to use a mixture of magnesium cooxides as raw materials from the viewpoint of transparency and barrier properties of the thin film layer.

In addition, it is needless to say that when a thin film layer of metal oxide alone is to be obtained, the raw material is also the metal oxide alone.

As an example of the silicon oxide used as a raw material, the mixture of silicon and silicon dioxide, single silicon monoxide, and the mixture of silicon, silicon dioxide, and silicon monoxide are mentioned. In the case of using a mixture of silicon (Si) and silicon dioxide (SiO ₂ ), the composition ratio thereof is basically preferably equimolar, but Si: SiO ₂ = 40 to 60 mol%: 60 to 40 mol%. Further, when the silicon oxide used as a raw material, a mixture of Si, SiO, SiO ₂ is, Si: and if the SiO ₂ in almost equimolar, (SiO + SiO _2): the ratio of the SiO are not particularly limited.

As a method of forming a thin film layer in a PET film or a PVA film, a vacuum thin film formation system is preferable, and a vacuum vapor deposition, ion plating, sputtering etc. are mentioned as a vacuum thin film formation system. According to the vacuum thin film formation method, such as vacuum deposition, a thin film layer can be directly formed on a plastic film.

Moreover, as a heating method of vacuum deposition, there is no particular limitation as long as the deposition droplet called splash does not occur during the deposition, or if it is small enough that it can be removed without difficulty, and high frequency induction heating, resistance heating, Known heating methods such as electron beam heating can be used. When a large amount of deposition droplets are generated, the droplets remain as foreign matter on the surface-treated PET or surface-treated PVA film, and when the display element-encapsulated structure or the unsealed-type display element is manufactured using the obtained laminate, the foreign matters are formed as black spots ( In this case, the display element encapsulation structure and the display element itself become defective.

As an evaporation source for vacuum evaporation, a general crucible method may be used, but the evaporation raw materials described in Japanese Patent Application Laid-Open No. Hei 1-252786 and Hei 2-277774 can be vacuum deposited uniformly at different sublimation and melting points. Can also be used to supply and discharge.

In addition, when forming a thin film layer in PET film or PVA film, although a raw material composition may be reflected in the composition of a thin film layer as it is by the method of vacuum deposition etc., you may form a thin film layer, reacting 2 or more types of raw materials by reaction vapor deposition. .

As a method for forming a thin film layer according to reaction deposition, a method of vacuum deposition while oxidizing or fluorinating a compound containing a metal such as a metal or an organometallic compound, depositing a metal fluoride on a plastic film and oxidizing the deposition layer in a later step How to do this. The method of the oxidation treatment is not particularly limited as long as it is a method of performing the treatment within the usable temperature range of the plastic film. Examples thereof include an oxygen gas introduction method, a discharge treatment method, an oxygen plasma method, a thermal oxidation method, and the like.

Although the thickness of a thin film layer is calculated according to the PET film or PVA film used, 5 nm-200 nm per side, especially 10 nm-100 nm are preferable. In addition, the thin film layer may have a laminated structure of two or more layers, and at this time, different kinds of metal oxides and metal fluorides may be laminated.

The laminated body of this invention is a surface-treated PET film which has a thin film layer which consists of a metal oxide or a metal oxide, and a metal fluoride on a PET film; A surface-treated PVA film having a metal oxide or a thin film layer composed of a metal oxide and a metal fluoride on a PVA film; an adhesive comprising a polyurethane resin and a polyepoxy compound having an amino group is applied to the surface-treated PET film; It can manufacture by laminating a surface-treated PVA film.

In general, in dry lamination processing using an adhesive, a two-component curable urethane adhesive containing a resin having a hydroxyl group and a polyisocyanate is often used. However, this two-component curable urethane adhesive is generally not equivalent in number of hydroxyl groups and isocyanate groups, and in most cases, polyisocyanate is quite excessive. As a result, excess polyisocyanate and moisture in atmosphere react, and urea bond and carbonic acid gas generate | occur | produce.

When laminating films that do not have high gas barrier properties, or when laminating films having high gas barrier properties and films having low gas barrier properties, carbonic acid generated from the hydroxyl group-isocyanate group two-liquid curable urethane adhesive The gas exits from both sides or one side of the adhesive layer. However, in the case of laminating films having a high gas barrier property using this adhesive, since there is no place where carbon gas escapes, the adhesive layer foams over the entire surface, and this foaming is surely defective in appearance. .

In addition, not only that but also the cohesive strength of the adhesive decreases due to foaming, the most important adhesive strength inherently decreases. Moreover, although the detailed reason is not clear, it is known that gas barrier property itself also falls.

On the other hand, if it is the adhesive agent containing the polyurethane resin and polyepoxy compound which have an amino group, since it is hardening by reaction of an amino group and an epoxy group, foaming of an adhesive bond layer by generation | occurrence | production of such a gas containing carbon gas does not occur. Therefore, especially in the manufacture of the laminated body of this invention which sticks the films which have a high gas barrier property, the adhesive agent containing the polyurethane resin and polyepoxy compound which have an amino group is used.

As a polyurethane resin which has an amino group, the polyurethane resin whose at least one of the terminal of a molecule | numerator obtained by making a polyol, polyisocyanate, and polyamine react is mentioned, for example is mentioned. It is preferable that it is about 5000-100,000, and, as for the weight average molecular weight of a polyurethane resin, it is especially preferable that it is 10,000-50,000. In the case where the weight average molecular weight is less than 5000, the adhesiveness of the adhesive becomes low, and in the case of more than 100,000, the viscosity of the adhesive becomes high, so there is a fear that the coatability is lowered.

Examples of the polyols include polytetramethylene glycol, polyester polyols, polyether polyols, polycarbonate polyols, polar acetar polyols, polyacrylate polyols, polyesteramide polyols, and polythioether polyols.

As polyisocyanate, a conventionally well-known thing, for example, 2, 4- triylene diisocyanate, 2, 6- triylene diisocyanate, m-phenylenedi isocyanate, p-phenylene diisocyanate, 4,4'- diphenylmethane diisocyanate , 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3, 3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4, 4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-detrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1 , 6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetra Tyl xylene diisocyanate, hydrogenated xylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexyl methane di Polyisocyanate monomers such as isocyanate; And reactants of the aforementioned monomers such as dimers, trimers, biurets, arophanates, and polyisocyanates of adducts with polyols.

Moreover, the said polycyanate can also be used together 2 or more types.

It is preferable to make the ratio of the OH group in a polyol and the NCO group in a polyisocyanate react on the conditions of NCO group: OH group = 1: 1-2: 1 when the said polyol and polyisocyanate are made to react.

Examples of the polyamine include those conventionally known, for example, ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3 Diamines such as, 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, aminoethylethanolamine, amino Aminoalkyl alkanolamines such as propylethanolamine, aminohexyl ethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, aminohexylpropanolamine, dihydrazide hydroxide, dicarboxylic acid dihydrazide, malic acid dihydrazide, glutaric acid dihydra And hydrazides such as azide, adipic acid dihydrazide, sebatin acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide.

As the polyepoxy compound, a polyepoxy compound having at least two glycidyl groups is preferable. Specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylol propane triglycidyl ether, trimethylol ethane triglycidyl Aliphatic polyepoxy compounds such as dil ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, bisphenol A or bisphenol F type aromatic polyepoxy compounds, tetraglycidylaminophenylmethane, triglycidyl isocyanur And glycidylamine type epoxy compounds such as 1,3-bis (N, N-glycidylaminomethyl) cyclohexane.

As for the adhesive agent containing the polyurethane resin and polyepoxy compound which have an amino group, the polyurethane resin crosslinks by addition reaction of the amino group and the glycidyl group in a polyepoxy compound in a polyurethane resin, and thereby expresses performance, such as excellent heat resistance and the like. It is possible. Therefore, it is preferable that the ratio of the number of an amino group and glycidyl group is 20-300 glycidyl groups, especially 70-150 with respect to the amino group 100.

In addition, when the other component contained in an adhesive agent has an amino group or glycidyl group, it adjusts so that the total number of amino groups and the total number of glycidyl groups in an adhesive may be the said ratio.

A well-known adhesion promoter can also be contained in an adhesive agent. Examples of the adhesion promoter include a titanate coupling agent, a zircoaluminum coupling agent, and an aluminum coupling agent. It is particularly preferable to use a silane coupling agent.

Examples of the silane coupling agent include a hydrocarbon group bonded directly to a silicon atom or through -O- or -OCO-, and at least one of these hydrocarbon groups is a double bond, a halogen atom, an epoxy group, an acid anhydride group, an alkoxycarbonyl group, an amino group, The thing containing an acryl oil group, a methacryl oil group, an acrylamino group, a methacrylamino group, or a haloacylamino group is mentioned. Of the silane coupling agents, compounds having an epoxy group and an amino group are particularly effective.

Specific examples of the silane coupling agent include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ- Glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propylmethyl diethoxysilane, etc. are mentioned. Among these, it is particularly preferable to use (N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane) or γ-glycidoxypropyltrimethoxysilane.

The silane coupling agent is preferably contained in the adhesive at a ratio of 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the total amount of the adhesive. When content of a silane coupling agent is less than 0.1 weight%, sufficient adhesion promoting effect cannot be acquired, and when it exceeds 5 weight%, the cohesive strength of an adhesive will fall and adhesive strength will become low.

In addition, a well-known filler, a softener, a stabilizer, a leveling agent, an antifoamer, a plasticizer, an inorganic filler, tackifier resin, coloring agents, such as a tackifier, fibers, a pigment, a usable time extender etc. are used suitably for an adhesive agent. It can mix.

When it demonstrates more concretely about the lamination method of each film, first, the polyurethane resin and polyepoxy compound which have an amino group are mix | blended in a predetermined ratio, and an adhesive agent is prepared. Subsequently, the treated surface (surface with a thin film layer) or untreated surface of the surface-treated PET film or surface-treated PVA film so that the coating amount at the time of drying the adhesive is 0.1 to 20 g / m 2, preferably 1.0 to 10 g / m 2. It is apply | coated to (the surface which does not have a thin film layer), it is made to dry in the dryer of 40-150 degreeC, Preferably it is 50-100 degreeC, and a dilute solvent is evaporated. Finally, the adhesive coated surface of the surface-treated film coated with the adhesive and the surface-treated PVA film or surface-treated PET film are overlapped on the treated surface or untreated surface of the film, and the temperature is 30 to 120 ° C. and the pressure is 60 to 60. Laminate with a nipple roll of 300 kg / cm 2. It is preferable to age the laminate (laminate) for promoting crosslinking of the adhesive after the lamination, and it is economically preferable to perform the aging at 30 to 50 ° C. for 1 to 3 days. It is also possible to laminate by applying an adhesive to both the surface-treated PET film and the surface-treated PVA film.

Prior to the lamination, an easy adhesion treatment such as a corona treatment, a plasma treatment, a frame treatment, or the like may be performed on the surface (that is, the adhesive surface) of the surface-treated PET film or the surface-treated PVA film.

In addition, although the adhesive agent of this invention is basically a laminated body of (PET surface side) surface-treated PET / surface-treated PVA (PVA surface side), between surface-treated PET and surface-treated PVA and or PVA surface side, surface-treated PET Alternatively, the surface treated PVA may be further laminated. The lamination direction at that time is not particularly limited except that the thin film layer of the surface-treated PET of the outermost layer on the PET surface side is the inner side (PVA surface side), and the treatment of each film so that the adhesive strength and the gas barrier property are good. The surface side and the untreated surface side can be arbitrarily selected and laminated.

For example, the laminated body of the following structures also exists in the range of the laminated body of this invention.

(PET surface side) Surface treatment PET / Surface treatment PET / Surface treatment PVA (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PVA / Surface treatment PET (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PVA / Surface treatment PVA (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PVA / Surface treatment PVA / Surface treatment PET (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PET / Surface treatment PVA / Surface treatment PVA (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PVA / Surface treatment PET / Surface treatment PVA (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PVA / Surface treatment PVA / Surface treatment PVA (PVA surface side)

(PET surface side) Surface treatment PET / Surface treatment PET / Surface treatment PET / Surface treatment PVA (PVA surface side)

In the case where the laminate of the present invention is used for sealing an EL element or forming an encapsulation type EL element, the (PET surface side) surface-treated PET (thin film layer) is particularly excellent from the viewpoint of excellent water vapor barrier properties and lamination strength of each layer. Surface) / (thin layer surface) surface treatment PVA / (thin layer surface) surface treatment PVA / surface treatment It is preferable that it is a structure of PET (thin layer layer surface) (PVA surface side).

The heat-sealing plastic film can be laminated on the surface-treated PVA film side of the laminate of the present invention (the PVA surface side may be the treated surface side or the non-treated surface side). By using a laminate formed by laminating a heat-sealing plastic film on the PVA plane side, when manufacturing the display element encapsulation structure, the barrier base material around the display element and the laminate of the present invention can be easily melted and adhered together. .

As the heat-sealing plastic film, there is no limitation as long as it is heat-sealing (heat sealability). Polyolein such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ionomer, polyvinyl chloride, polyvinylidene chloride , Polyurethane, fluororesin, polyacrylonitrile, polystyrene, polyethylene terephthalate, maleic acid modified polyolefin, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate Films, such as a copolymer and ethylene-ethylacrylate copolymer, can be used.

Among them, in view of adhesion to the lead wire portion (metal) of the display element, an ethylene-vinyl acetate copolymer, an ionomer, a maleic acid-modified polyolefin, an ethylene-acrylic acid copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-methacryl Films of a late copolymer, an ethylene-methyl acrylate copolymer, and an ethylene-ethyl acrylate copolymer are preferable.

The thickness of the heat sealable plastic film is preferably about 5 μm to 500 μm, particularly 30 μm to 100 μm. When the thickness is less than 5 µm, the adhesive strength when thermally bonding the heat-sealing plastic films is significantly lowered. When the thickness is greater than 500 µm, the bending property of the film is impaired. Not.

As a lamination method of the laminate of the present invention and the heat-sealing plastic, the dry lamination method of attaching the heat-sealing plastic in a film state using an adhesive is preferable, but in the method of attaching the heat-sealing plastic while fusing it into a film, It is also possible to laminate by.

As the adhesive, a conventionally known adhesive, for example, a two-component curable urethane adhesive, can be used, but an adhesive containing a polyurethane resin having an amino group and a polyepoxy compound described above is suitably used.

In addition, when laminating by the dry lamination method, you may perform the easy adhesion | attachment process, such as a corona treatment, a plasma treatment, a frame treatment, on the surface (namely, adhesive surface) of a heat-sealable plastic film before lamination.

The laminate of the laminate of the present invention and the heat-sealable plastic can be performed by the same method as the laminate of the surface-treated PET film and the surface-treated PVA film described above.

Moreover, you may laminate | stack a hydrophilic film, such as nylon, a polyvinyl alcohol, a cellophane, and an ethylene vinyl alcohol copolymer saponification, between each film, or between a heat-seal plastic and an EL element. In particular, when the nylon is laminated, it is preferable to trap moisture that has invaded and to improve the deterioration preventing effect of the display element.

By using the laminated body of this invention, the display element sealing structure 100 as shown in FIG. 1 can be obtained. Specifically, the inorganic EL element, the organic EL element, and the liquid crystal are formed on the barrier substrate 8 so that the light emitting surface becomes the outer surface with respect to the barrier substrate (that is, the laminate of the present invention is laminated in the light emitting direction of the light emitting element). Display elements, such as a display element, are arrange | positioned and laminated | stacked, The laminated body 1 of this invention is arrange | positioned so that the surface treatment PET film (PET surface side) may become an outer surface with respect to the light emitting surface of the display element, The display element encapsulation structure 100 can be obtained by adhering a barrier base material and a laminated body.

In this case, a water-retaining material such as a nylon film may be formed between the barrier base material and the non-light-emitting surface of the display element as a water retention layer.

The barrier base material is not particularly limited as long as the gas barrier property is high and can be adhered to the laminate of the present invention. However, lamination of various plastic films or the like on the metal foil or the metal foil is preferable in the barrier property and handling. Moreover, it is also preferable to use the laminated body of this invention as a barrier base material.

The method of adhering the barrier base material and the laminate around the display element (or all directions) is not limited, and in general, a hot laminate, a hot press, or the like can be used, but it may be bonded using an adhesive. At this time, the area of the laminate and the barrier substrate should be larger than the area of the display element. This is because if the area of the laminate or barrier substrate is smaller than the area of the display element, the four sides of the display element cannot be completely adhered, and the display element cannot be blown out of the laminate and sealed.

Since the laminated body of this invention has much higher water vapor barrier property which a conventional film does not have, it is used suitably especially for sealing of EL element.

The inorganic EL device comprises a light emitting layer containing zinc sulfide (reference numeral 4 in FIG. 1), an insulating layer 5 using barium titanate, a transparent conductive film 3 having a surface transparent electrode layer using ITO, a back film forming using carbon, and the like. Although comprised by the electrode layer 6 and a moisture absorption layer (not shown), it is not specifically limited.

In addition, an organic EL element is an element in which one or multiple organic thin films are formed between an anode and a cathode. In the case of the two-layer type, although a positive electrode, an aromatic amine, etc. are used for a transparent conductive material, such as ITO, a hole injection layer, an aluminum quinoline complex, etc. are used for a light emitting layer, magnesium, silver alloy, etc. for a cathode, This is not specifically limited, either.

In addition, the laminated body (10 in FIG. 2) of this invention is made so that the surface treatment PET film may be an outer surface on the plastic film 11 side of the transparent conductive film which has the transparent electrode layer 12 on one side of a plastic film, An unsealed type inorganic EL as shown in FIG. 2 by using a laminate (laminate for forming display elements; 9) formed by laminating through an adhesive containing a polyurethane resin having an amino group and a polyepoxy compound described above. The device 200 may be formed. The unsealed type inorganic EL element 200 is formed by stacking the display element formation laminate 9 in the light emitting direction of the display element, and insulating the light emitting layer 13 and the transparent electrode layer 12 on the transparent conductive film. A layer 14, a back electrode layer 15 such as carbon, and a protective layer 16 are formed, and moisture-repellent treatment is performed on the phosphor in the light emitting layer, and a resin having a low moisture absorption is applied to the resin used for the light emitting layer and the insulating layer. Although it uses and performs moisture proof processing, it is not specifically limited.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded. In addition, the test method in an Example is as follows. In addition, "part" in an Example means a "weight part."

Water vapor barrier property: The water vapor transmission rate of the laminated body was measured on condition of 40 degreeC90% RH based on JISZ0222. The smaller this value, the better the water vapor barrier property.

Appearance: The state of the laminate was visually evaluated.

EL device structure test: The EL device structure was exposed for 500 hours under an environment of 60 ° C and 95% RH. Thereafter, the EL element was made to emit light and evaluated visually whether the EL element was damaged.

Luminescence luminance: Measured using a luminance meter ("LS-110" manufactured by Minorta Co., Ltd.).

Example 1

Silicon and dioxide are on one side of a 25-micrometer-thick PET film using a vacuum evaporation apparatus of a continuous draw-down resistance heating method of continuously supplying and discharging the evaporation raw material described in Japanese Patent Application Laid-open No. Hei 1-252786. A mixture of silicon and magnesium fluoride (mixing ratio of 46 mol%: 46 mol%: 8 mol%) was vacuum-deposited by heating to obtain a surface treated PET film (the thickness of the thin film layer was 60 nm).

Next, using the same vacuum evaporation apparatus, the same raw material mixture was vacuum-deposited on one side of the biaxially-stretched PVA film of thickness 14 micrometers, and the surface treatment PVA film was obtained (thickness of the thin film layer is 80 nm).

235.0 parts of polytetramethylene glycol of number average molecular weight 1000, 100.0 parts of polypropylene glycol of number average molecular weight 1000, 220.0 parts of polypropylene glycol of number average molecular weight 2000, 5.2 parts of dimethylolpropionic acid, 170.7 parts of ethyl acetate, and 12ylene diisocyanate 121.8 Part was added and reacted at 80 degreeC for 9 hours, and the solution of the prepolymer (content of NCO is 2.46%) which has an isocyanate group in the terminal was obtained. Subsequently, after cooling the solution of this prepolymer at 50 degreeC, 201.0 parts of ethyl acetate were added and stirred, and after mixing completely uniformly, 371.7 parts of isopropyl alcohol were added and stirred again. After sufficiently stirring to form a homogeneous system, 61.3 parts of isophorone diamine were added to the prepolymer solution at a high stirring speed, followed by positive reaction at 50 ° C for 2 hours to obtain a polyurethane resin solution having a solid content of 50% by weight (weight average molecular weight: 3 million).

100 parts of obtained polyuritan resin, 110 parts of isopropyl alcohol, and 10 parts of diluting ethylene glycol diglycidyl ether to 50 weight% of solid content with acetone and ethyl acetate were mix | blended, and the adhesive agent of 25 weight% of solid content was obtained. (Number of amino groups in the adhesive: number of glycidyl groups = 100: 173). Using a gravure-coated dry laminator, the surface-treated PET film and the surface-treated PVA film were dry laminated with the obtained adhesive (4 g / m 2 of dry coating amount of the adhesive), and the (PET surface side) surface-treated PET film (thin layer surface) The laminated body of the structure of / adhesive / (thin film layer surface) surface treatment PVA film / adhesive / (thin film layer surface) surface treatment PET film (PVA side surface) was obtained.

Example 2

Dry lamination was carried out using the same surface-treated PET film, surface-treated PVA film, and adhesive as in Example 1, and the surface-treated PET film (thin layer layer) / adhesive / surface-treated PVA film (thin layer layer surface) / adhesive The laminated body of the structure of / (thin film layer surface) surface-treated PVA film / adhesive agent / (thin film layer surface) surface-treated PET film (PVA surface side) was obtained.

Example 3

A silicon monoxide was vacuum-deposited on one side of a 12-micrometer-thick polyethylene terephthalate film using the vacuum-winding apparatus of the continuous-winding-type vacuum evaporation system of an electron beam heating method, and the surface treatment PET film was obtained (The thickness of a thin film layer is 100 nm. ).

Next, silicon monoxide was vacuum-deposited on one side of the biaxially stretched polyvinyl alcohol film with a thickness of 14 micrometers using the same vacuum vapor deposition apparatus, and the surface treatment PVA film was obtained (thickness of the thin film layer is 80 nm).

Dry lamination was carried out using the same adhesive as in Example 1, and the surface treated PET film (thin layer surface) / adhesive / surface treated PVA film (thin layer surface) / adhesive / surface treated PVA film (thin layer surface) / adhesive / (Thin film layer surface) The laminated body of the structure of surface treatment PET film (PVA surface side) was obtained.

Example 4

Dry lamination was performed using the same surface-treated PET film, surface-treated PVA film, and adhesive as in Example 1, and the surface-treated PET film (thin layer layer) / adhesive / (thin layer layer) surface-treated PVA film (PVA) The laminated body of the surface side) was obtained.

Example 5

Dry lamination was performed using the same surface-treated PET film, surface-treated PVA film, and adhesive as in Example 1, and a nylon film having a thickness of 15 μm, and the surface-treated PET film (thin layer surface) / adhesive / surface treatment PVA film (thin film layer surface) / adhesive agent / (thin film layer surface) surface treatment The laminated body of the structure of PVA film / adhesive agent / (thin film layer surface) surface treatment PET film / adhesive agent / nylon film (PVA surface side) was obtained.

Example 6

100 parts of the polyuritan resin solution obtained in Example 1, 2 parts of a silane coupling agent (N-β- (aminoethyl)-(gamma)-aminopropyl trimethoxysilane), 110 parts of isopropyl alcohol, ethylene glycol digly 10 parts of dilution of cylyl ether to 50% by weight of solid with acetone and ethyl acetate were combined to obtain an adhesive having a solid content of 25.7% by weight (number of amino groups in the adhesive: number of glycidyl groups = 100: 104). Dry lamination was performed using the same surface-treated PET film, surface-treated PVA film, and the adhesive as in Example 1, and the surface-treated PET film (thin layer surface) / adhesive / (thin layer surface) surface treated PVA film / The laminated body of adhesive agent / (thin layer surface) surface treatment PVA film / adhesive agent / surface treatment PET film (thin layer layer surface) (PVA surface side) was obtained.

Comparative Example 1

Using the same surface treated PVA film as in Example 1 and an adhesive (surface treated PET film is not used), dry lamination was performed, and the surface treated PVA film (thin layer surface) / adhesive / (thin layer surface) surface treated PVA film The laminated body of the structure of was obtained.

Comparative Example 2

Dry lamination was carried out using a urethane-based adhesive for dry laminate (polyethylene and polyisocyanate) (adduct AD590 manufactured by Dongyang Moton Co., Ltd.), the same surface-treated PET film as in Example 1, and a surface-treated PVA film. Surface side) The laminated body of the structure of surface-treated PET film (thin-film layer surface) / adhesive / (thin-film layer surface) surface-treated PVA film / adhesive / (thin-layer layer surface) surface-treated PET film (PVA surface side) was obtained.

Using the laminates obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the EL element encapsulation structure and the non-sealing type inorganic EL element were prepared by the following methods, respectively.

(Creation of EL element encapsulation structure)

Example 1 was used on the PVA side of the laminate obtained in Examples 1 to 5 and Comparative Example 2 using a maleic acid-modified polypropylene film (hereinafter referred to as an MPP film) subjected to colonization as a heat-sealing plastic film. The MPP film was dry laminated using the adhesive obtained in the above, to obtain a laminate.

Moreover, about the laminated body obtained in Example 6, the MPP film was dry-laminated to the PVA surface side of a laminated body using the laminated body obtained in Example 6, and the laminated body was obtained.

Moreover, about the laminated body obtained by the comparative example 1, MPP film was dry-laminated using the adhesive agent obtained in Example 1 so that it might become the following structure, and the laminated body was obtained.

Comparative example 1: surface treatment PVA film (thin layer surface) / adhesive / (thin layer surface) surface treatment PVA film / adhesive / MPP film

Furthermore, as Comparative Example 3, the surface-treated PET film, the surface-treated PVA film, and the MPP film obtained in Example 1 were dry laminated using the adhesive obtained in Example 1 so as to have the following structure, to obtain a laminate.

Comparative example 3: surface treatment PVA film (thin layer surface) / adhesive / (thin layer surface) surface treatment PET film / adhesive / MPP film

About the laminated body which laminated | stacked the MPP film, water vapor barrier property and external appearance were evaluated. The results are shown in Table 1.

Each laminated body which laminated | stacked the obtained said MPP film was used as a sealing laminated body and a barrier base material, an EL sealing structure is manufactured by thermocompression bonding using an inorganic EL element and an organic EL element, and an EL element structure test is performed. It was. The results are shown in Table 1.

As the inorganic EL element, an insulating layer made of barium titanate and a light emitting layer made of zinc sulfide and manganese were formed on the ITO electrode, and other aluminum was formed as a back electrode.

In addition, what was created as follows was used as an organic EL element.

On the film with the cleaned ITO electrode, oligo (p-triimino-1,4-phenylene-1,1-cyclohexylene-1,4-phenylene) was vacuum-deposited to obtain a film thickness of 50 nm. A hole injection layer of was obtained. Subsequently, vacuum deposition was performed using a tris (8-hydroxyquinoline) aluminum complex as a light emitting material to prepare a light emitting layer having a thickness of 50 nm. By co-deposition thereon, a film thickness cathode having a thickness of 200 nm was made of an alloy of Mg: Ag: 10: 1. The hole injection layer, the light emitting layer, and the cathode were deposited under conditions of a substrate temperature of room temperature with a vacuum of 10 ⁻⁶ torr.

(Making of an unsealed type inorganic EL element)

The adhesive obtained in Example 1 was used for the PET film side of the transparent electrode film which has an ITO transparent electrode (indium-tin-oxide) in a PET film, and the PVA surface side of each laminated body obtained in Examples 1-5 and Comparative Example 2. And dry lamination to obtain a laminate for display element formation. In addition, as this laminated body for inorganic sealing element preparation of an unsealed type, the thing in which MPP film was not laminated was used.

In addition, about the laminated body of Example 6, the PET film side of the transparent conductive film which has an ITO transparent electrode in a PET film, and the PVA surface side of the laminated body obtained in Example 6 were dried using the adhesive agent obtained in Example 6. It laminated and obtained the laminated body for display element formation.

About the laminated body of the comparative example 1, using the adhesive agent obtained in Example 1, the PET film side of the transparent conductive film which has an ITO transparent electrode in a PET film, and the PVA surface side of a laminated body are dry-laminated so that it may become the following structure, And the laminated body for display element formation were obtained.

Comparative example 1: surface treatment PVA film (thin layer surface) / adhesive / (thin layer surface) surface treatment PVA film / adhesive / PET film / ITO transparent electrode

Furthermore, as Comparative Example 3, the surface-treated PET film and the surface obtained in Example 1 on the PET film side of the transparent conductive film having the ITO transparent electrode on the PET film using the adhesive obtained in Example 1 so as to have the following constitution. The processed PVA film was dry laminated and the laminated body for display element formation was obtained.

Comparative Example 3 Surface Treatment PVA Film (Thin Film Surface) / Adhesive / (Thin Film Layer Surface) Surface Treatment PET Film / Adhesive / PET Film / ITO Transparent Electrode

On the ITO transparent electrode of the obtained display element formation laminated body, the light emitting layer which consists of zinc sulfide and a resin binder is formed, the insulating layer which consists of barium titanate, a carbon back electrode layer, and a protective layer are formed one by one, and an unsealed type EL element is manufactured. An EL device structure test was carried out. The results are shown in Table 1.

Laminated Structure Water vapor barrier properties * 1 Exterior EL element encapsulation structure test Sealless Type EL Device Structure Testing Inorganic EL Element Organic EL element Light emitting surface state after exposure Luminance luminance * 2 Light emitting surface state after exposure Light emitting surface state after exposure Early After exposure Example 1 0.07 normal Uniform emission 200 190 Uniform emission Uniform emission Example 2 0.02 normal Uniform emission 210 210 Uniform emission Uniform emission Example 3 0.07 normal Uniform emission 200 190 Uniform emission Uniform emission Example 4 0.10 normal Uniform emission 200 180 Uniform emission Uniform emission Example 5 0.01 normal Uniform emission 200 200 Uniform emission Uniform emission Example 6 0.02 normal Uniform emission 210 210 Uniform emission Uniform emission Comparative Example 1 4.0 normal discoloration 210 10 Sunspot Many discoloration parts Comparative Example 2 0.1 firing Uniform emission 200 180 Uniform emission Uniform emission Comparative Example 3 2.0 normal discoloration 200 50 Sunspot Many discoloration parts * 1 g / ㎡ 24hrs 40 ℃ 90% RH * 2 cd / ㎡

By using the laminated body which has the high colorless transparency and the high water vapor barrier property of this invention, it becomes possible to obtain a display element sealing structure, without using an expensive thick fluororesin film.

Moreover, by using the laminated body for display element formation of this invention formed by laminating | stacking the laminated body of this invention so that a surface-treated polyethylene terephthalate film may become an outer surface on the plastic film side of a transparent conductive film, it is highly colorless and transparent conventionally. Furthermore, an unsealed display element structure having a higher water vapor barrier property can be obtained.

Claims (11)

Surface treatment polyvinyl chloride having a thin film layer of metal oxide or metal oxide and metal fluoride on a polyethylene terephthalate film and surface treatment polyvinyl chloride having a thin film layer of metal oxide or metal oxide and metal fluoride on a polyvinyl alcohol film The laminated body formed by laminating | stacking an alcohol film through the adhesive agent containing the polyurethane resin which has an amino group, and a polyepoxy compound. The laminate according to claim 1, wherein the thin film layer of the surface-treated polyethylene terephthalate film and / or the surface-treated polyvinyl alcohol film is a thin film layer made of silicon oxide. The laminate according to claim 1, wherein the thin film layer of the surface-treated polyethylene terephthalate film and / or the surface-treated polyvinyl alcohol film is a thin film layer made of silicon oxide, metal fluoride and / or magnesium oxide. The laminate according to any one of claims 1 to 3, wherein the adhesive further comprises a silane coupling agent. The laminate according to any one of claims 1 to 4, wherein a heat-sealable plastic film is further laminated on the surface-treated polyvinyl alcohol film side. A surface treated polyethylene terephthalate film having a metal oxide or a thin film layer made of a metal oxide and a metal fluoride on the polyethylene terephthalate film; And an adhesive comprising a polyurethane resin having an amino group and a polyepoxy compound on at least one of a surface treated polyvinyl alcohol film having a metal oxide or a thin film layer made of a metal oxide and a metal fluoride on the polyvinyl alcohol film. The manufacturing method of the laminated body which laminates the said surface-treated polyethylene terephthalate film and the said surface-treated polyvinyl alcohol film. Barrier substrates; A display element laminated on the barrier substrate such that a light emitting surface thereof is an outer surface of the barrier substrate; And It consists of the laminated body of any one of Claims 1-5 laminated | stacked so that the surface-treated polyethylene terephthalate film may become an outer surface with respect to the light emitting surface of the said display element on the said display element, A display element encapsulation structure formed by adhering a barrier substrate around said display element and said laminate. The display element encapsulation structure of claim 7, wherein the display element is an electroluminescence element. Poly having an amino group on the plastic film side of the transparent conductive film having a transparent electrode on one side of the plastic film, so that the surface-treated polyethylene terephthalate film becomes the outer surface of the laminate according to any one of claims 1 to 4. The laminated body for display element formation characterized by laminating | stacking through the adhesive agent containing a urethane resin and a polyepoxy compound. An unsealed display element structure, wherein the laminate for forming a display element according to claim 9 is laminated in the light emitting direction of the display element. The unsealed display element structure according to claim 10, wherein the display element is an electric field light emitting element.