WO2016009778A1 - Composite film - Google Patents
Composite film Download PDFInfo
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- WO2016009778A1 WO2016009778A1 PCT/JP2015/067578 JP2015067578W WO2016009778A1 WO 2016009778 A1 WO2016009778 A1 WO 2016009778A1 JP 2015067578 W JP2015067578 W JP 2015067578W WO 2016009778 A1 WO2016009778 A1 WO 2016009778A1
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- WIPO (PCT)
- Prior art keywords
- film
- layer
- organic
- adhesive layer
- gas barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
Definitions
- the present invention relates to a composite film used for an organic EL device or the like.
- Organic EL devices OLED devices
- organic EL Electro-Luminescence
- the organic EL material used for this organic EL device is very sensitive to moisture. Therefore, in an organic EL device, a sealing member having a low water vapor transmission rate such as a metal plate, a glass plate, or a gas barrier film is bonded to seal the organic EL element.
- a sealing member having a low water vapor transmission rate such as a metal plate, a glass plate, or a gas barrier film is bonded to seal the organic EL element.
- an adhesive is used to adhere the sealing member to the organic EL device. Therefore, supply is performed in a form in which an adhesive layer is laminated on the sealing member, and in order to prevent deterioration of the adhesive layer, a peelable release film is attached to the adhesive layer and supplied. To be done.
- Patent Document 1 describes a film composite having a photocurable adhesive layer on one surface of a gas barrier film and a protective film laminated on the photocurable adhesive layer. And when sealing an electronic element using this film composite_body
- the adhesive layer of the sealing member used for sealing the organic EL element is required to have a low moisture content.
- the gas barrier property of the release film is not considered. Therefore, if the release film passes water vapor, the adhesive layer may absorb moisture in the air and contain water. Therefore, there has been a problem that the organic EL material is deteriorated due to moisture contained in the adhesive layer. In order to prevent this, it is conceivable to impart a gas barrier property to the release film. However, since the release film after use is generally discarded, there is a problem in that the cost is greatly increased. is there.
- An object of the present invention is to solve such problems of the prior art, and can prevent water content of the adhesive layer without increasing the cost, and is used for sealing an organic EL device. It is an object of the present invention to provide a composite film that can stably protect an organic EL element for a long time and prevent the element from deteriorating.
- the present inventors have laminated a sealing laminate formed by laminating a moisture-proof film and an adhesive layer on both sides of the release film with the adhesive layer inside.
- Moisture-proof films placed on both outer surfaces prevent moisture in the air from reaching the adhesive layer and prevent moisture content of the adhesive layer, thereby, when used for sealing organic EL devices,
- the organic EL element can be stably protected for a long time to prevent the element from deteriorating, and the sealing laminate laminated on both sides of the release film can be used for sealing the organic EL device, respectively. Since only the release film has to be discarded, it has been found that an increase in cost can be prevented and the present invention has been completed. That is, this invention provides the composite film of the following structures.
- the water vapor permeability of the first moisture-proof film and the second moisture-proof film is 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)] or less, according to any one of (1) to (4) Composite film.
- the first moisture-proof film and the second moisture-proof film are gas barrier films each having at least a gas barrier substrate, a smooth layer, and a barrier layer.
- the release film comprises a film base and release layers formed on both surfaces of the film base.
- the moisture content of the pressure-sensitive adhesive layer is prevented without causing an increase in cost, whereby the organic EL element can be stably stabilized for a long time when used for sealing an organic EL device.
- a composite film that can be protected and prevented from deteriorating can be provided.
- FIG. 1 conceptually shows an example of the composite film of the present invention.
- the composite film 10 shown in FIG. 1 has a first gas barrier film 22a, a first adhesive layer 20a, a release film 12, a second adhesive layer 20b, and a second gas barrier film 22b laminated in this order. It has the structure which consists of.
- the first gas barrier film 22a and the first adhesive layer 20a constitute the first sealing laminate 14a
- the second gas barrier film 22b and the second adhesive layer 20b are the first 2 sealing laminated body 14b is comprised.
- the 1st sealing laminated body 14a and the 2nd sealing laminated body 14b are peeled from the release film 12, respectively, and are used for sealing of an organic EL element.
- the composite film 10 of this invention has the structure which stuck the sealing laminated body which is a laminated body of a gas barrier film and an adhesion layer on both surfaces of the release film 12 with the adhesion layer inside. . Therefore, since the 1st adhesion layer 20a and the 2nd adhesion layer 20b stuck on both sides of release film 12 are pinched by the 1st gas barrier film 22a and the 2nd gas barrier film 22b, it is in the air Can be prevented from reaching the first adhesive layer 20a and the second adhesive layer 20b, and water content of the adhesive layer can be prevented. Moreover, both the 1st sealing laminated body 14a and the 2nd sealing laminated body 14b can peel from the release film 12, and can be used for sealing of an organic EL apparatus. Accordingly, since only the release film 12 is discarded after use, an increase in cost can be prevented.
- the composite film 10 shown in FIG. 1 includes five of the first gas barrier film 22a, the first adhesive layer 20a, the release film 12, the second adhesive layer 20b, and the second gas barrier film 22b.
- the composite film 10 of this invention is not limited to this, You may have another layer. For example, you may have a hard-coat layer, an optical compensation layer, a transparent conductive layer, etc.
- each layer which comprises the composite film of this invention is demonstrated in detail.
- Both surfaces of the release film 12 are detachably attached to the first adhesive layer 20a and the second adhesive layer 20b. That is, it is a film-like member that exhibits appropriate tackiness with the adhesive layer.
- the release film 12 The various well-known release film used as a release film of a sealing laminated body can be utilized.
- the release film 12 is made of polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylonitrile.
- PAN polyimide
- PI polymethyl methacrylate resin
- PC polycarbonate
- PP polypropylene
- PS polystyrene
- ABS cyclic olefin copolymer
- COC Cycloolefin polymer
- TAC triacetyl cellulose
- the release film 12 is good also as a structure which has a release layer on the surface of the base material which consists of a resin film.
- the adhesive strength between the adhesive layer and the adhesive layer can be adjusted to an appropriate level of adhesiveness that can be peeled off. Silicone resin, fluororesin, polyethylene vinyl acetate, etc. can be used as the release layer material.
- the thickness of the release film 12 is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m from the viewpoint of preventing moisture from entering the adhesive layer through the release film 12 and ease of lamination. .
- 1st sealing laminated body 14a and 2nd sealing laminated body 14b are each stuck to the release film 12 so that peeling is possible. As shown in FIG. 1, the first sealing laminate 14 a is attached to one main surface of the release film 12, and the second sealing laminate 14 b is attached to the other main surface of the release film 12. Worn.
- the first sealing laminate 14a is formed by laminating the first gas barrier film 22a and the first adhesive layer 20a
- the second sealing laminate 14b includes the second sealing laminate 14b.
- the gas barrier film 22b and the second adhesive layer 20b are laminated.
- the 1st adhesion layer 20a and the 2nd adhesion layer 20b are affixed on the release film 12, respectively, as for the 1st sealing laminated body 14a and the 2nd sealing laminated body 14b. Therefore, the first sealing laminate 14a and the second sealing laminate 14b are affixed to the release film 12 so that the first gas barrier film 22a and the second gas barrier film 22b are respectively arranged outside. It is worn.
- both the sealing laminated bodies differ only in the arrangement position and the direction of the front and back, and the configuration is the same, in the following description, the first sealing laminated body 14a and the second sealing laminated body When it is not necessary to distinguish the body 14b, both the sealing laminated bodies are collectively called the sealing laminated body 14.
- the first gas barrier film 22a and the second gas barrier film 22b are collectively referred to as a gas barrier film 22.
- the first adhesive layer 20a and the second adhesive layer 20b are collectively referred to as an adhesive layer 20.
- the gas barrier film 22 is a moisture-proof film in the present invention, and is a member having gas barrier properties. That is, the gas barrier film 22 is a part that mainly suppresses the entry of moisture from the outside when the organic EL element is sealed as the sealing laminate 14. Moreover, in the form of the composite film 10 of the present invention, the gas barrier film 22 prevents moisture in the air from reaching the adhesive layer 20 and prevents moisture content of the adhesive layer 20.
- the gas barrier film 22 preferably has a water vapor permeability of 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)] or less.
- a water vapor permeability of 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)] or less.
- the gas barrier film 22 preferably has at least one smooth layer and at least one barrier layer on the gas barrier substrate.
- FIG. 2 is a schematic sectional view showing an example of the configuration of the gas barrier film 22.
- a gas barrier film 22 shown in FIG. 2 has a smooth layer 27 on a gas barrier substrate 26 and a barrier layer 28 on the smooth layer 27.
- the gas barrier film 22 preferably has one or more combinations of a barrier layer 28 and a smooth layer 27 serving as a base of the barrier layer 28 on the gas barrier base material 26. Accordingly, the gas barrier film 22 may have two combinations of the barrier layer 28 and the underlying smooth layer 27, or may have three or more.
- the smooth layer 27 functions as a base layer for properly forming the barrier layer 28. The greater the number of laminated layers of the base smooth layer 27 and the barrier layer 28, the better the gas barrier property. The gas barrier film which has is obtained.
- the gas barrier film 22 has the outermost surface as the barrier layer 28, and it is preferable that the adhesion layer 20 is laminated
- gas barrier substrate 26 of the gas barrier film 22 various types of known gas barrier films that are used as supports can be used.
- films made of various plastics are preferably used in that they are easy to reduce the thickness and weight, and are suitable for making the organic EL device flexible.
- polyethylene polyethylene
- PEN polyethylene naphthalate
- PA polyethylene terephthalate
- PVC polyvinyl chloride
- PVA polyvinyl alcohol
- PAN polyacrylonitrile
- PI polyacrylonitrile
- PC polycarbonate
- PC polyacrylate
- PP polypropylene
- PS polystyrene
- ABS cyclic olefin copolymer
- COC cycloolefin polymer
- COP plastic film made of triacetyl cellulose
- the thickness of the gas barrier substrate 26 may be set as appropriate depending on the use and size of the organic EL device.
- the thickness of the gas barrier substrate 26 is preferably about 10 ⁇ m to 200 ⁇ m.
- the gas barrier base material 26 may be provided with functions such as antireflection, phase difference control, and light extraction efficiency improvement on the surface of such a plastic film.
- the smooth layer 27 is a base layer of the barrier layer 28 that mainly exhibits gas barrier properties in the gas barrier film 22.
- the smooth layer 27 various types of known gas barrier films that are used as the smooth layer 27 can be used.
- the smooth layer 27 is a film containing an organic compound as a main component, and basically formed by crosslinking monomers and / or oligomers. Since the gas barrier film 22 has the smooth layer 27 serving as the base, the smooth layer 27 also functions as a cushion for the barrier layer 28. For this reason, the barrier layer 28 is damaged by the cushioning effect of the smooth layer 27 at the time of pressing when the sealing laminate 14 is bonded to the organic EL element or when the sealing laminate 14 receives an impact from the outside. Can be prevented.
- gas barrier film 22 expresses gas barrier performance appropriately, and can prevent the deterioration of the adhesion layer 20 by a water
- the gas barrier film 22 has a smooth layer 27 as a base of the barrier layer 28, thereby embedding irregularities on the surface of the gas barrier base material 26, foreign matters adhering to the surface, and the like.
- the film formation surface can be made appropriate. As a result, it is possible to form an appropriate barrier layer 28 without any gaps and without cracks or cracks on the entire film formation surface. Thereby, it is possible to obtain high gas barrier performance such that the water vapor transmission rate is 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)] or less.
- various organic compounds can be used as a material for forming the smooth layer 27.
- polyester acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc.
- An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.
- the smooth layer 27 composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.
- the glass transition temperature is 120 ° C. mainly composed of acrylate and / or methacrylate monomers and oligomer polymers in terms of low refractive index, high transparency and excellent optical properties.
- the above acrylic resin and methacrylic resin are preferably exemplified as the smooth layer 27.
- DPGDA dipropylene glycol di (meth) acrylate
- TMPTA trimethylolpropane tri (meth) acrylate
- DPHA dipentaerythritol hexa (meth) acrylate
- Acrylic resin and methacrylic resin which are mainly composed of acrylate and / or methacrylate monomers and oligomer polymers, are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.
- the barrier layer 28 can be formed on the base having a solid skeleton, so that the barrier layer 28 having higher density and higher gas barrier properties can be formed. .
- the thickness of the smooth layer 27 is preferably 0.5 ⁇ m to 5 ⁇ m.
- the barrier layer 28 sufficiently exhibits an effect as a cushion at the time of pressing when the sealing laminate 14 is bonded to the organic EL device. Can be more reliably prevented.
- the thickness of the smooth layer 27 it is possible to make the film-forming surface of the barrier layer 28 more suitable and to form an appropriate barrier layer 28 free from cracks and cracks on the entire film-forming surface. A film can be formed across.
- the thickness of the smooth layer 27 is more preferably 1 ⁇ m to 5 ⁇ m.
- each smooth layer may be the same, or may mutually differ.
- the formation material of each smooth layer 27 may be the same or different. However, from the viewpoint of productivity and the like, it is preferable to form all the smooth layers 27 with the same material.
- the smooth layer 27 may be formed by a known method such as a coating method or flash vapor deposition. Further, in order to improve the adhesion with the barrier layer 28 which is the lower layer of the smooth layer 27, the smooth layer 27 preferably contains a silane coupling agent.
- a barrier layer 28 is formed with the smooth layer 27 as a base.
- the barrier layer 28 is a film containing an inorganic compound as a main component, and the gas barrier film 22 mainly exhibits gas barrier properties.
- various kinds of films made of an inorganic compound such as oxide, nitride, oxynitride and the like that exhibit gas barrier properties can be used.
- metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Films made of inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
- a film made of a silicon compound such as silicon oxide, silicon nitride, silicon oxynitride and silicon oxide is preferably exemplified in that it has high transparency and can exhibit excellent gas barrier properties.
- a film made of silicon nitride is preferable because it has high transparency in addition to more excellent gas barrier properties.
- the formation material of the barrier layer 28 may mutually differ. However, in consideration of productivity and the like, it is preferable to form all the barrier layers 28 with the same material.
- the thickness of the barrier layer 28 may be appropriately determined according to the forming material so that the target gas barrier property can be exhibited. According to the study of the present inventor, the thickness of the barrier layer 28 is preferably 10 to 200 nm. By setting the thickness of the barrier layer 28 to 10 nm or more, the barrier layer 28 that stably exhibits sufficient gas barrier performance can be formed. In addition, the barrier layer 28 is generally brittle, and if it is too thick, there is a possibility that cracking, cracking, peeling, etc. may occur. However, if the thickness of the barrier layer 28 is 200 nm or less, cracking may occur. Can be prevented.
- the thickness of the barrier layer 28 is preferably 10 nm to 100 nm, and more preferably 15 nm to 75 nm.
- the thickness of each barrier layer 28 may be the same or different.
- the barrier layer 28 may be formed by a known method according to the forming material. Specifically, vapor phase deposition methods such as plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vacuum deposition are preferably exemplified.
- plasma CVD such as CCP-CVD and ICP-CVD
- sputtering such as magnetron sputtering and reactive sputtering
- vacuum deposition are preferably exemplified.
- the pressure-sensitive adhesive layer 20 is a component that is laminated on the gas barrier film 22 and has adhesiveness that becomes an adhesive layer when sealing the organic EL element as the sealing laminate 14. Moreover, in the composite film 10 of this invention, the adhesion layer 20 is a site
- the adhesive force between the adhesive layer 20 and the release film 12 is such that the adhesive layer 20 and the release film 12 can be peeled off and does not unintentionally peel off when being transported or rolled up. If there is, there is no limitation in particular.
- the adhesive force between the adhesive layer 20 and the sticking surface of the sealing member such as the organic EL device is not particularly limited as long as the sealing laminate 14 and the organic EL device are sufficiently adhered to each other. .
- the adhesive layer 20 preferably has a moisture content of 200 ppm or less by mass ratio.
- the organic EL element is deteriorated due to moisture contained in the adhesive layer 20 when the organic EL element is sealed as the sealing laminate 14. Can be prevented.
- the gas barrier film 22 laminated on both outer surface sides can suppress moisture in the air from reaching the adhesive layer 20 during storage or the like. It can suppress that the moisture content of a layer becomes high, and can maintain the low moisture content of 200 ppm or less.
- the adhesion layer 20 is equipped with a water absorption capability.
- the water absorption capacity of the adhesive layer 20 is preferably 1 wt% or more in terms of mass ratio.
- the adhesive layer 20 has a water absorption capability, when the organic EL element is sealed as the sealing laminate 14, it absorbs moisture that enters from the end face of the sealing laminate 14 or a defect in the gas barrier film 22, It is possible to more suitably prevent deterioration of the organic EL element due to moisture.
- the gas barrier film 22 laminated on both outer surface sides can suppress moisture in the air from reaching the adhesive layer 20 during storage or the like. In the form of the film 10, it is possible to sufficiently exhibit the water absorption capability after suppressing the water absorption of the adhesive layer 20 and sealing the organic EL element as the sealing laminate 14.
- a moisture content is a value of the mass ratio of the water
- the moisture contained by swelling can be dried by heating or the like. That is, the moisture content is a ratio of moisture reversibly contained in the adhesive layer 20.
- the water absorption capacity is a value of a mass ratio of moisture that can be absorbed into the adhesive layer 20 by chemical bonding. Moisture contained by chemical bonding cannot basically be removed by heating. That is, the water absorption capacity is a value of the mass ratio of the amount of water that can be irreversibly included in the adhesive layer 20.
- the moisture content and the water absorption capacity are measured by the following measuring method.
- a sample piece is cut out from the adhesive layer 20 in a glove box and weighed.
- the mass of the sample piece at this time is defined as x (g).
- the moisture content measured by the Karl Fischer method immediately after taking this sample piece out of the glove box is taken as the moisture content of the sample.
- the sample piece cut out in the glove box and weighed in the same manner is taken out from the glove box, weighed for 48 hours or more in an environment of temperature 25 ° C. and humidity 50% RH, and weighed.
- Let y (g) be the mass of the sample piece after humidity control.
- the sample piece after humidity adjustment is in a state containing moisture due to water content due to swelling and water absorption due to chemical bonding.
- the sample piece after humidity adjustment is put again in the glove box, and is weighed after being vacuum-dried at a temperature of 80 ° C. for 50 hours or more.
- Let the mass of the sample piece after drying be z (g). That is, the sample piece after drying is in a state where moisture due to swelling is removed and only moisture due to chemical bonding is included. From the mass of the sample piece in each of these states, the water absorption capacity is calculated by (z ⁇ x) / x.
- the thickness of the pressure-sensitive adhesive layer 20 is not particularly limited, but is preferably 1 to 100 ⁇ m from the viewpoint of adhesiveness, water absorption capacity, cost, and the like.
- the adhesive layer 20 may be an adhesive sheet such as an OCA (Optically Clear Adhesive) sheet, or may be an organic layer obtained by curing a resin by polymerization or heat.
- the curable resin include silicone resin, acrylic resin, methacrylic resin, epoxy resin, melamine resin, polyester resin, urethane resin, epoxy acrylate resin, and cyclic olefin resin.
- acrylic resins, epoxy resins, epoxy acrylate resins, and cyclic olefin resins are preferable. Moreover, it is preferable that it is resin which consists of a 3 or more polyfunctional acrylate / methacrylate compound.
- hardenability may be mixed by making these curable resins into a main component. For example, a styrene / butadiene block copolymer may be included for viscosity adjustment.
- these curable resins may be used independently and 2 or more types may be used together.
- a bifunctional epoxy resin from the viewpoint that the curing shrinkage stress is small and the adhesiveness of the cured product is high. Furthermore, from the viewpoint of low moisture permeability and moisture content, it is preferable to use polybutadiene epoxy resin or the like.
- a photoinitiator e.g., a photosensitizer, etc.
- curable resin used as the adhesion layer 20 contains an inorganic filler for the purpose of further improving the moisture resistance of hardened
- the inorganic filler is not particularly limited, for example, talc, asbestos, silica, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, Examples include barium sulfate, gypsum, calcium silicate, and sericite activated clay.
- the adhesive layer 20 in order to provide the adhesive layer 20 with water absorption capability, it is preferable to include a desiccant in the curable resin.
- a desiccant in the curable resin.
- the pressure-sensitive adhesive layer 20 contains a desiccant
- the adhesive layer 20 absorbs moisture that enters from the end face of the sealing laminate 14, the defect of the gas barrier film 22, and the like.
- the desiccant may be an organometallic complex or an inorganic desiccant.
- an organometallic compound having a structure represented by the chemical formula of Chemical Formula 1 is preferred, a structure represented by-[M (OR) -O] n- is more preferred, and cyclic AlO acylate is particularly preferred.
- R 1 , R 2 , and R 3 represent hydrogen, an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, or a heterocyclic group.
- R1, R2, and R3 may be different groups or the same group, and may be linked to each other. Alternatively, it may be a polymer.
- aluminum oxide 2-ethylhexanoate (Olep AOO, Hope Pharmaceutical Co., Ltd.), aluminum oxide isopropylate (Algomer 7 manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum oxide stearate (Olep AOS, Hope Pharmaceutical Co., Ltd.) ), Aluminum oxide ethylate and the like.
- Non-cyclic aluminum-triisopropoxide (AIP) is also preferred.
- a water absorbent described in JP-A-2005-298598 and a desiccant described in JP-A-2006-297380 can also be used.
- Examples of the inorganic desiccant include alkaline earth metal oxides such as calcium oxide (CaO), barium oxide (BaO), and magnesium oxide (MgO); lithium sulfate (Li 2 SO 4 ), sodium sulfate ( Na 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), cobalt sulfate (CoSO 4 ), gallium sulfate (Ga 2 (SO 4 ) 3 ), titanium sulfate (Ti (SO 4 ) 2 ), Sulfates such as nickel sulfate (NiSO 4 ), calcium chloride (CaCl 2 ), phosphorus pentoxide (P 2 O 5 ), potassium hydroxide (KOH), sodium hydroxide (NaOH), potassium bromide (KBr), odor Examples thereof include calcium chloride (CaBr 2 ), copper sulfate (CuSO 4 ), zinc chloride (ZnCl 2 ),
- the content of the desiccant in the adhesive layer 20 may be appropriately set according to the type of desiccant and the required performance. Specifically, it is preferably 1 to 60% by mass, more preferably 2 to 40% by mass, and particularly preferably 5 to 20% by mass.
- the adhesive layer 20 preferably has transparency. Specifically, the adhesive layer 20 preferably has a visible light (400 to 800 nm) light transmittance of 85% or more, and a haze value of 3.0% or less.
- the adhesive layer 20 is preferably formed on the gas barrier film 22 by coating. Therefore, it is preferable to prepare a coating composition by mixing the material for forming the adhesive layer 20 and a solvent. Moreover, there is no limitation in particular in the coating method at the time of forming the adhesion layer 20, and slit coating, die coating, roll coating, dip coating, blade coating, knife coating, bar coating, screen printing, spin coating, etc. can be used. . Moreover, when forming the adhesion layer 20 on the elongate gas barrier film 22, what is called the adhesion layer 20 is formed by application
- FIG. 3 shows a schematic cross-sectional view of an example of an organic EL device in which an organic EL element is sealed using the sealing laminate 14.
- the organic EL device 50 shown in FIG. 3 has a configuration in which the sealing laminate 14 is laminated on the element substrate 52 on which the organic EL element 54 is formed. As shown in FIG. 3, the organic EL device 50 has a configuration in which the pressure-sensitive adhesive layer 20 side and the organic EL element 54 side of the sealing laminate 14 are laminated facing each other.
- the sealing laminate 14 is the sealing laminate 14 of the composite film 10 and is peeled off from the release film 12 and attached onto the organic EL element 54. By stacking the sealing laminate 14 on the organic EL element 54 and sealing the organic EL element 54, the organic EL element 54 is prevented from being deteriorated by moisture.
- the composite film 10 of the present invention has a configuration in which the sealing laminate 14 is laminated on both surfaces of the release film 12 with the adhesive layer 20 on the inside, moisture in the air adheres during storage or the like. Prevents the moisture content of the adhesive layer 20 from reaching the layer 20, and thereby stably protects the organic EL element 54 for a long period of time when used for sealing the organic EL element 54. Can be prevented from deteriorating.
- the composite film 10 can use the sealing laminate 14 laminated on both sides of the release film 12 for sealing the organic EL element 54. Therefore, since only the release film 12 has to be discarded, an increase in cost can be prevented.
- the element substrate 52 all element substrates used in various organic EL devices can be used. Specifically, an element substrate made of glass, plastic, metal, ceramic, or the like is exemplified.
- the element substrate 52 is preferably a substrate made of a material having a low content of moisture and the like and a low transmittance of moisture and the like, such as glass and metal.
- the gas barrier film 22 of the sealing laminated body 14 can also be used suitably as the element substrate 52 at the point with the low transmittance
- the organic EL device 50 is opposite to the element substrate 52, that is, sealed. It can be used as a top emission type organic EL device 50 that emits light from the stop laminate 14 side.
- the organic EL device 50 is a top emission type
- the element substrate 52 does not need to have light transmittance. Therefore, when the organic EL device 50 is used as a top emission type, the element substrate 52 is a flexible material having an insulating layer such as an aluminum foil having an anodic oxide film on its surface or a laminate of aluminum foil and polyimide. A metallic film may be used. At this time, the flexible organic EL device 50 can be obtained.
- the element substrate 52 can be used as a bottom emission type organic EL device 50 that emits light from the element substrate 52 side. Or it is good also as a structure which emits light from both surfaces using the light-transmitting material for both the sealing laminated body 14 and the element substrate 52.
- the organic EL element 54 is formed on the element substrate 52.
- the organic EL element 54 is a known organic EL element having, for example, an organic electroluminescent layer and a transparent electrode and a reflective electrode that are an electrode pair that holds the organic electroluminescent layer.
- a transparent electrode is disposed on the sealing laminate 14 side
- a reflective electrode is disposed on the element substrate 52 side.
- a reflective electrode is disposed on the sealing laminate 14 side
- a transparent electrode is disposed on the element substrate 52 side.
- the organic electroluminescent layer may be any layer having a known layer structure including a light emitting layer made of an organic EL material, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like.
- the transparent electrode for example, various known electrodes having light transmissivity for transmitting light emitted from the organic electroluminescent layer, such as conductive metal oxide such as indium tin oxide (ITO), can be used. is there.
- the reflective electrode various known electrodes used as an electrode of an organic EL element can be used.
- ITO indium tin oxide
- the reflective electrode various known electrodes used as an electrode of an organic EL element can be used.
- what is necessary is just to form an organic electroluminescent layer, a transparent electrode, and a reflective electrode by a well-known method according to the use of the organic EL apparatus 50, a magnitude
- the organic EL device 50 may have a protective film or the like that covers the organic EL element 54 between the organic EL element 54 and the sealing laminate 14.
- a protective film various films (layers) made of a material exhibiting gas barrier properties, which are used in known organic EL devices, can be used.
- a film made of an inorganic compound having gas barrier properties is exemplified, and among these, a film made of a silicon compound such as silicon nitride, silicon oxide, and silicon oxynitride is preferably exemplified.
- Example 1 As Example 1, the composite film 10 shown in FIG. 1 was prepared, and then the sealing laminate 14 was peeled off, and the organic EL element was sealed using the sealing laminate 14 and the organic EL shown in FIG. A device 50 was produced.
- ⁇ Composite film> As the gas barrier film 22, a film having two combinations of the smooth layer 27 and the barrier layer 28 on the gas barrier substrate 26 was used. As the gas barrier substrate 26, a polyethylene naphthalate film (PEN film, Teonex Q65FA manufactured by Teijin DuPont Films Ltd.) having a thickness of 100 ⁇ m was used.
- PEN film polyethylene naphthalate film
- Teijin DuPont Films Ltd. Teijin DuPont Films Ltd.
- a smooth layer 27 was formed on the gas barrier substrate 26.
- a material was applied to the gas barrier substrate 26 by a coating method, dried, and then polymerized by irradiation with ultraviolet rays to form a film having a thickness of 0.6 ⁇ m.
- a paint for forming a smooth layer 14.9 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.7 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. SC-1), an ultraviolet polymerization initiator (Lamberti)
- TMPTA polymerizable compound
- silane coupling agent Shin-Etsu Chemical Co., Ltd. SC-1
- an ultraviolet polymerization initiator Liberti
- the prepared polymerizable composition was applied on a base film using a wire bar so that the liquid thickness was 5 ⁇ m, and the high pressure mercury lamp was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method.
- the smooth layer 27 was formed by irradiating with ultraviolet rays (accumulated dose of about 1 J / cm 2 ) and curing.
- a barrier layer 28 was formed on the smooth layer 27 having a thickness of 40 nm using a CCP (capacitively coupled plasma) -CVD apparatus.
- Silane gas (SiH 4 ), ammonia gas (NH 3 ), nitrogen gas (N 2 ), and hydrogen gas (H 2 ) were used as source gases.
- the supply amounts of gas were 160 sccm for silane gas, 370 sccm for ammonia gas, 240 sccm for nitrogen gas, and 590 sccm for hydrogen gas.
- the film forming pressure was 40 Pa. That is, the barrier layer 28 is a silicon nitride film.
- the plasma excitation power was 2.5 kW at a frequency of 13.56 MHz.
- the smooth layer 27 was formed on the barrier layer 28.
- This smooth layer was formed by laminating two organic layers.
- a film having a thickness of 0.6 ⁇ m was formed as the first organic layer.
- As a coating material for forming the first organic layer 14.1 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.5 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd.
- PA of an acidic compound A polymerizable composition comprising 1.0 g (KARAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.), 1.4 g UV polymerization initiator (ESACURE KTO46 manufactured by Lamberti Co., Ltd.) and 180 g 2-butanone was prepared.
- the prepared polymerizable composition was applied on the inorganic layer 28 using a wire bar so that the liquid thickness was 5 ⁇ m, and the high pressure mercury lamp was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method.
- the first organic layer was formed by irradiating with ultraviolet rays (accumulated dose of about 1 J / cm 2 ) and curing.
- a film having a thickness of 0.6 ⁇ m was formed as a second organic layer on the first organic layer.
- a coating material for forming the second organic layer 14.9 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.7 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. SC-1), an ultraviolet polymerization initiator A polymerizable composition consisting of 1.4 g of 2-lamone 180 g (ESACURE KTO 46, manufactured by Lamberti Co., Ltd.) was prepared.
- the prepared polymerizable composition was coated on the first organic layer using a wire bar so that the liquid thickness was 5 ⁇ m, and high-pressure mercury was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method.
- the lamp was irradiated with ultraviolet rays (accumulated dose of about 1 J / cm 2 ) and cured to form a second organic layer, thereby forming a smooth layer 27 composed of two organic layers.
- a barrier layer 28 having a thickness of 40 nm was formed by the same method as above, and a gas barrier film 22 was produced.
- the produced gas barrier film 22 had a water vapor transmission rate of 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)].
- Adhesive layer Next, a material was applied onto the barrier layer 28 of the gas barrier film 22 by a coating method, dried and cured, to form an adhesive layer 20 having a thickness of 10 ⁇ m, and the sealing laminate 14 was produced.
- a material for the adhesive layer 20 a two-component thermosetting acrylic ester liquid resin (SK Dyne 1831 manufactured by Soken Chemical Co., Ltd.) was used.
- application coating was performed using the applicator. The thickness after drying was adjusted to 10 ⁇ m and applied. Curing conditions were 30 minutes at a temperature of 80 ° C.
- release film As the release film 12, a film in which a silicone resin was installed on both sides of a PET film having a thickness of 100 ⁇ m was used.
- the sealing laminate 14 was adhered to both surfaces of the release film 12 with the pressure-sensitive adhesive layer 20 facing the release film 12, thereby producing a composite film 10.
- the sealing laminate 14 was heated and dried at a temperature of 80 ° C. for 24 hours in a glove box having a dew point temperature of ⁇ 60 ° C. or lower.
- the sealing laminate 14 was conditioned for 50 hours in an environment of a temperature of 25 ° C. and a humidity of 50% RH. After humidity control, a sample piece was cut out from the sealing laminate 14 and the water absorption capacity and moisture content of the adhesive layer were measured. The water absorption capacity was 0 wt%, and the water content was 120 ppm.
- the organic EL device 50 shown in FIG. 3 was produced.
- the element substrate 52 a conductive glass substrate (surface resistance value 10 ⁇ / ⁇ ) having an ITO film was washed with 2-propanol and then subjected to UV-ozone treatment for 10 minutes.
- the thickness of the element substrate 52 was 700 ⁇ m.
- a passivation film made of a silicon nitride film having a thickness of 5 ⁇ m was formed on the element substrate 52 on which the organic EL element 54 was formed by a parallel plate CVD method.
- the sealing laminate 14 of the composite film 10 was bonded to the element substrate 52 on which the passivation film was formed, and the organic EL element 54 was sealed, whereby the organic EL device 50 was manufactured.
- Example 2 A composite film 10 was produced in the same manner as in Example 1 except that a desiccant was included in the adhesive layer 20, and an organic EL device 50 was produced using the sealing laminate 14 of the composite film 10.
- a desiccant aluminum oxide 2-ethylhexanoate (Hope Pharmaceutical Co., Ltd. Olipe A00) was used, and 15 wt% was contained in the material of the adhesive layer 20.
- the water absorption capability and moisture content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capability was 1.2 wt%, and the moisture content was 0 ppm.
- Example 1 As shown in FIG. 4, an organic EL device was produced in the same manner as in Example 1 except that the sealing laminate was adhered to only one surface of the release film to produce a composite film. Further, when the water absorption capacity and water content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capacity was 0 wt% and the water content was 520 ppm.
- Example 2 An organic EL device was produced in the same manner as in Example 2 except that the sealing laminate was adhered to only one surface of the release film to produce a composite film. Moreover, when the water absorption capacity and moisture content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capacity was 1.2 wt%, and the water content was 230 ppm.
- the organic EL device sealed with the composite film of the present invention has less dark spots and higher durability than the comparative example. Since the organic EL device sealed using the composite film of the present invention has no observed dark spots or a small number of the organic EL devices, the organic EL device of the present invention used for sealing the organic EL element is used. It can be seen that the amount of water in the adhesive layer is small. On the other hand, in the comparative example, many dark spots were observed on the entire surface of the organic EL element. This is because moisture is contained in the adhesive layer of the sealing laminate used for sealing the organic EL element. From the above results, the effects of the present invention are clear.
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Abstract
Description
そのため、封止部材に接着剤層を積層した形態での供給が行われており、また、接着剤層の劣化を防止するため、接着剤層に剥離可能な離型フィルムを貼着して供給することが行われている。 The organic EL material used for this organic EL device is very sensitive to moisture. Therefore, in an organic EL device, a sealing member having a low water vapor transmission rate such as a metal plate, a glass plate, or a gas barrier film is bonded to seal the organic EL element. When sealing an organic EL element using such a sealing member, an adhesive is used to adhere the sealing member to the organic EL device.
Therefore, supply is performed in a form in which an adhesive layer is laminated on the sealing member, and in order to prevent deterioration of the adhesive layer, a peelable release film is attached to the adhesive layer and supplied. To be done.
そのため、接着剤層に含まれる水分に起因して有機EL材料が劣化するという問題があった。
これを防止するために、離型フィルムにガスバリア性を付与することが考えられるが、一般に、使用後の離型フィルムは廃棄されるものであるため、大幅なコスト増を招いてしまうという問題がある。 However, in the film composite as a conventional sealing member, the gas barrier property of the release film is not considered. Therefore, if the release film passes water vapor, the adhesive layer may absorb moisture in the air and contain water.
Therefore, there has been a problem that the organic EL material is deteriorated due to moisture contained in the adhesive layer.
In order to prevent this, it is conceivable to impart a gas barrier property to the release film. However, since the release film after use is generally discarded, there is a problem in that the cost is greatly increased. is there.
すなわち、本発明は以下の構成の複合フィルムを提供する。 As a result of earnest research to achieve the above-mentioned problems, the present inventors have laminated a sealing laminate formed by laminating a moisture-proof film and an adhesive layer on both sides of the release film with the adhesive layer inside. Moisture-proof films placed on both outer surfaces prevent moisture in the air from reaching the adhesive layer and prevent moisture content of the adhesive layer, thereby, when used for sealing organic EL devices, The organic EL element can be stably protected for a long time to prevent the element from deteriorating, and the sealing laminate laminated on both sides of the release film can be used for sealing the organic EL device, respectively. Since only the release film has to be discarded, it has been found that an increase in cost can be prevented and the present invention has been completed.
That is, this invention provides the composite film of the following structures.
(2) 第1の粘着層および第2の粘着層が吸水能力を有する(1)に記載の複合フィルム。
(3) 第1の粘着層および第2の粘着層の吸水能力が、0.5wt%以上である(2)に記載の複合フィルム。
(4) 第1の粘着層および第2の粘着層の含水率が、200ppm以下である(1)~(3)のいずれかに記載の複合フィルム。
(5) 第1の防湿フィルムおよび第2の防湿フィルムの水蒸気透過率が、1×10-3[g/(m2・day)]以下である(1)~(4)のいずれかに記載の複合フィルム。
(6) 第1の防湿フィルムおよび第2の防湿フィルムが、少なくともガスバリア基材と、平滑層と、バリア層とを有してなるガスバリアフィルムである(1)~(5)のいずれかに記載の複合フィルム。
(7) バリア層が酸化物、窒化物、酸窒化物の少なくとも1つからなる(6)に記載の複合フィルム。
(8) 離型フィルムが、フィルム基材と、フィルム基材の両側の表面に形成された離型層とを有してなる(1)~(7)のいずれかに記載の複合フィルム。 (1) A composite film obtained by laminating a first moisture-proof film, a first adhesive layer, a release film, a second adhesive layer, and a second moisture-proof film in this order.
(2) The composite film according to (1), wherein the first adhesive layer and the second adhesive layer have water absorption ability.
(3) The composite film according to (2), wherein the water absorption capacity of the first adhesive layer and the second adhesive layer is 0.5 wt% or more.
(4) The composite film according to any one of (1) to (3), wherein the moisture content of the first adhesive layer and the second adhesive layer is 200 ppm or less.
(5) The water vapor permeability of the first moisture-proof film and the second moisture-proof film is 1 × 10 −3 [g / (m 2 · day)] or less, according to any one of (1) to (4) Composite film.
(6) The first moisture-proof film and the second moisture-proof film are gas barrier films each having at least a gas barrier substrate, a smooth layer, and a barrier layer. Composite film.
(7) The composite film according to (6), wherein the barrier layer is made of at least one of oxide, nitride, and oxynitride.
(8) The composite film according to any one of (1) to (7), wherein the release film comprises a film base and release layers formed on both surfaces of the film base.
また、第1のガスバリアフィルム22aと第1の粘着層20aとは、第1の封止積層体14aを構成するものであり、第2のガスバリアフィルム22bと第2の粘着層20bとは、第2の封止積層体14bを構成するものである。第1の封止積層体14aおよび第2の封止積層体14bがそれぞれ、離型フィルム12から剥離されて、有機EL素子の封止に用いられる。 The
The first
そのため、離型フィルム12の両側に貼着される第1の粘着層20aおよび第2の粘着層20bは、第1のガスバリアフィルム22aおよび第2のガスバリアフィルム22bに挟まれているので、空気中の水分が第1の粘着層20aおよび第2の粘着層20bに到達するのを抑制することができ、粘着層の含水を防止できる。
また、第1の封止積層体14aおよび第2の封止積層体14b共に、離型フィルム12から剥離して有機EL装置の封止に用いることができる。従って、使用後に廃棄されるのは、離型フィルム12のみであるので、コストの増加を防止できる。 Thus, the
Therefore, since the
Moreover, both the 1st sealing laminated body 14a and the 2nd sealing laminated
以下、本発明の複合フィルムを構成する各層について詳細に説明する。 In addition, the
Hereinafter, each layer which comprises the composite film of this invention is demonstrated in detail.
離型フィルム12としては特に限定はなく、封止積層体の離型フィルムとして用いられる種々の公知の離型フィルムが利用可能である。
具体的には、離型フィルム12は、ポリエチレン(PE)、ポリエチレンナフタレート(PEN)、ポリアミド(PA)、ポリエチレンテレフタレート(PET)、ポリ塩化ビニル(PVC)、ポリビニルアルコール(PVA)、ポリアクリトニトリル(PAN)、ポリイミド(PI)、透明ポリイミド、ポリメタクリル酸メチル樹脂(PMMA)、ポリカーボネート(PC)、ポリアクリレート、ポリメタクリレート、ポリプロピレン(PP)、ポリスチレン(PS)、ABS、環状オレフィン・コポリマー(COC)、シクロオレフィンポリマー(COP)、および、トリアセチルセルロース(TAC)などのフィルムが各種利用可能である。 Both surfaces of the
There is no limitation in particular as the
Specifically, the
離型層の材料としてはシリコーン樹脂、フッ素樹脂、ポリエチレンビニルアセテート等が利用可能である。 Moreover, the
Silicone resin, fluororesin, polyethylene vinyl acetate, etc. can be used as the release layer material.
従って、第1の封止積層体14aおよび第2の封止積層体14bは、第1のガスバリアフィルム22aおよび第2のガスバリアフィルム22bがそれぞれ外側に配置されるように、離型フィルム12に貼着されている。
なお、両封止積層体は、配置位置、および、表裏の向きが異なるのみで、構成は同じであるので、以下の説明においては、第1の封止積層体14aおよび第2の封止積層体14bを区別する必要がない場合には、両封止積層体をまとめて、封止積層体14ともいう。同様に、第1のガスバリアフィルム22aおよび第2のガスバリアフィルム22bをまとめて、ガスバリアフィルム22ともいう。同様に、第1の粘着層20aおよび第2の粘着層20bをまとめて、粘着層20ともいう。 As described above, the first sealing laminate 14a is formed by laminating the first
Therefore, the first sealing laminate 14a and the
In addition, since both the sealing laminated bodies differ only in the arrangement position and the direction of the front and back, and the configuration is the same, in the following description, the first sealing laminated body 14a and the second sealing laminated body When it is not necessary to distinguish the
水蒸気透過率が低い、すなわち、ガスバリア性が高いガスバリアフィルム22用いることで、粘着層20への水分の浸入を防止して粘着層20の含水をより好適に防止することができる。 Here, the
By using the
図2にガスバリアフィルム22の構成の一例を表す概略断面図を示す。
図2に示すガスバリアフィルム22は、ガスバリア基材26の上に平滑層27を有し、この平滑層27の上にバリア層28を有するものである。 Here, the
FIG. 2 is a schematic sectional view showing an example of the configuration of the
A
なお、平滑層27は、バリア層28を適正に形成するための下地層として作用するものであり、下地の平滑層27とバリア層28との組み合わせの積層数が多いほど、優れたガスバリア性を有するガスバリアフィルムを得られる。 The
The
ガスバリアフィルム22の最表面をバリア層28とすることにより、ガスバリア基材26や平滑層27からアウトガスが放出されても、このアウトガスはバリア層28で遮蔽され、粘着層20や有機EL素子に至ることを防止できる。 Moreover, it is preferable that the
By forming the outermost surface of the
中でも、薄手化や軽量化が容易である、有機EL装置のフレキシブル化に好適である等の点で、各種のプラスチック(高分子材料/樹脂材料)からなるフィルムが好適に利用される。
具体的には、ポリエチレン(PE)、ポリエチレンナフタレート(PEN)、ポリアミド(PA)、ポリエチレンテレフタレート(PET)、ポリ塩化ビニル(PVC)、ポリビニルアルコール(PVA)、ポリアクリトニトリル(PAN)、ポリイミド(PI)、透明ポリイミド、ポリメタクリル酸メチル樹脂(PMMA)、ポリカーボネート(PC)、ポリアクリレート、ポリメタクリレート、ポリプロピレン(PP)、ポリスチレン(PS)、ABS、環状オレフィン・コポリマー(COC)、シクロオレフィンポリマー(COP)、および、トリアセチルセルロース(TAC)からなるプラスチックフィルムが、好適に例示される。 As the
Among these, films made of various plastics (polymer materials / resin materials) are preferably used in that they are easy to reduce the thickness and weight, and are suitable for making the organic EL device flexible.
Specifically, polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyimide ( PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), ABS, cyclic olefin copolymer (COC), cycloolefin polymer ( COP) and a plastic film made of triacetyl cellulose (TAC) are preferably exemplified.
なお、ガスバリア基材26は、このようなプラスチックフィルムの表面に、反射防止や位相差制御、光取り出し効率向上等の機能が付与されていてもよい。 The thickness of the
In addition, the gas
平滑層27は、公知のガスバリアフィルムで平滑層27として用いられているものが、各種、利用可能である。例えば、平滑層27は、有機化合物を主成分とする膜で、基本的に、モノマーおよび/またはオリゴマを、架橋して形成されるものが利用できる。
ガスバリアフィルム22は、この下地となる平滑層27を有することにより、この平滑層27が、バリア層28のクッションとしても作用する。そのため、封止積層体14を有機EL素子に接着する際の押圧時や、封止積層体14が外部から衝撃を受けた場合などに、この平滑層27のクッション効果によって、バリア層28の損傷を防止できる。
これにより、封止積層体14において、ガスバリアフィルム22が適正にガスバリア性能を発現して、水分による粘着層20の劣化、ならびに、水分による有機EL素子の劣化を、好適に防止できる。 The
As the
Since the
Thereby, in the sealing
具体的には、ポリエステル、アクリル樹脂、メタクリル樹脂、メタクリル酸-マレイン酸共重合体、ポリスチレン、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、セルロースアシレート、ポリウレタン、ポリエーテルエーテルケトン、ポリカーボネート、脂環式ポリオレフィン、ポリアリレート、ポリエーテルスルホン、ポリスルホン、フルオレン環変性ポリカーボネート、脂環変性ポリカーボネート、フルオレン環変性ポリエステル、アクリロイル化合物、などの熱可塑性樹脂、あるいはポリシロキサン、その他の有機ケイ素化合物の膜が好適に例示される。これらは、複数を併用してもよい。 In the
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.
中でも特に、上記強度に加え、屈折率が低い、透明性が高く光学特性に優れる等の点で、アクリレートおよび/またはメタクリレートのモノマーやオリゴマの重合体を主成分とする、ガラス転移温度が120℃以上のアクリル樹脂やメタクリル樹脂は、平滑層27として好適に例示される。
その中でも特に、ジプロピレングリコールジ(メタ)アクリレート(DPGDA)、トリメチロールプロパントリ(メタ)アクリレート(TMPTA)、ジペンタエリスリトールヘキサ(メタ)アクリレート(DPHA)などの、2官能以上、特に3官能以上のアクリレートおよび/またはメタクリレートのモノマーやオリゴマの重合体を主成分とする、アクリル樹脂やメタクリル樹脂は、好適に例示される。また、これらのアクリル樹脂やメタクリル樹脂を、複数、用いるのも好ましい。
平滑層27を、このようなアクリル樹脂やメタクリル樹脂で形成することにより、骨格がしっかりした下地の上にバリア層28を成膜できるので、より緻密でガスバリア性が高いバリア層28を成膜できる。 Of these, the
In particular, in addition to the above strength, the glass transition temperature is 120 ° C. mainly composed of acrylate and / or methacrylate monomers and oligomer polymers in terms of low refractive index, high transparency and excellent optical properties. The above acrylic resin and methacrylic resin are preferably exemplified as the
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resin and methacrylic resin, which are mainly composed of acrylate and / or methacrylate monomers and oligomer polymers, are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.
By forming the
平滑層27の厚さを0.5μm以上とすることにより、有機EL装置に封止積層体14とを接着する際の押圧時などにおける、クッションとしての効果を十分に発揮して、バリア層28の損傷を、より確実に防止できる。また、平滑層27の厚さを1μm以上とすることにより、より好適にバリア層28の成膜面を適正にして、割れやヒビ等の無い適正なバリア層28を、成膜面の全面に渡って成膜できる。
また、平滑層27の厚さを5μm以下とすることにより、平滑層27が厚すぎることに起因する、平滑層27のクラックや、ガスバリアフィルム22のカール等の問題の発生を、好適に防止することができる。
以上の点を考慮すると、平滑層27の厚さは、1μm~5μmとするのが、より好ましい。 The thickness of the
By setting the thickness of the
In addition, by setting the thickness of the
Considering the above points, the thickness of the
また、複数の平滑層27を有する場合には、各平滑層27の形成材料は、同じでも異なってもよい。しかしながら、生産性等の点からは、全ての平滑層27を、同じ材料で形成するのが好ましい。 In addition, when a gas barrier film has the some
Moreover, when it has the some
また、平滑層27の下層となるバリア層28との密着性を向上するために、平滑層27は、シランカップリング剤を含有するのが好ましい。 The
Further, in order to improve the adhesion with the barrier layer 28 which is the lower layer of the
バリア層28は、無機化合物を主成分とする膜で、ガスバリアフィルム22において、ガスバリア性を主に発現するものである。 On the
The barrier layer 28 is a film containing an inorganic compound as a main component, and the
具体的には、酸化アルミニウム、酸化マグネシウム、酸化タンタル、酸化ジルコニウム、酸化チタン、酸化インジウムスズ(ITO)などの金属酸化物; 窒化アルミニウムなどの金属窒化物; 炭化アルミニウムなどの金属炭化物; 酸化ケイ素、酸化窒化ケイ素、酸炭化ケイ素、酸化窒化炭化ケイ素などのケイ素酸化物; 窒化ケイ素、窒化炭化ケイ素などのケイ素窒化物; 炭化ケイ素等のケイ素炭化物; これらの水素化物; これら2種以上の混合物; および、これらの水素含有物等の、無機化合物からなる膜が、好適に例示される。
特に、透明性が高く、かつ、優れたガスバリア性を発現できる点で、ケイ素酸化物、ケイ素窒化物、ケイ素酸窒化物およびケイ素酸化物等のケイ素化合物からなる膜は、好適に例示される。その中でも特に、窒化ケイ素からなる膜は、より優れたガスバリア性に加え、透明性も高く、好適に例示される。 As the barrier layer 28, various kinds of films made of an inorganic compound such as oxide, nitride, oxynitride and the like that exhibit gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Films made of inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
In particular, a film made of a silicon compound such as silicon oxide, silicon nitride, silicon oxynitride and silicon oxide is preferably exemplified in that it has high transparency and can exhibit excellent gas barrier properties. Among these, in particular, a film made of silicon nitride is preferable because it has high transparency in addition to more excellent gas barrier properties.
バリア層28の厚さを10nm以上とすることにより、十分なガスバリア性能を安定して発現するバリア層28が形成できる。また、バリア層28は、一般的に脆く、厚過ぎると、割れやヒビ、剥がれ等を生じる可能性が有るが、バリア層28の厚さを200nm以下とすることにより、割れが発生することを防止できる。
また、このような点を考慮すると、バリア層28の厚さは、10nm~100nmにするのが好ましく、特に、15nm~75nmとするのが好ましい。
なお、ガスバリアフィルムが複数のバリア層28を有する場合には、各バリア層28の厚さは、同じでも異なってもよい。 The thickness of the barrier layer 28 may be appropriately determined according to the forming material so that the target gas barrier property can be exhibited. According to the study of the present inventor, the thickness of the barrier layer 28 is preferably 10 to 200 nm.
By setting the thickness of the barrier layer 28 to 10 nm or more, the barrier layer 28 that stably exhibits sufficient gas barrier performance can be formed. In addition, the barrier layer 28 is generally brittle, and if it is too thick, there is a possibility that cracking, cracking, peeling, etc. may occur. However, if the thickness of the barrier layer 28 is 200 nm or less, cracking may occur. Can be prevented.
In consideration of such points, the thickness of the barrier layer 28 is preferably 10 nm to 100 nm, and more preferably 15 nm to 75 nm.
When the gas barrier film has a plurality of barrier layers 28, the thickness of each barrier layer 28 may be the same or different.
粘着層20は、ガスバリアフィルム22に積層され、封止積層体14として有機EL素子を封止する際の接着層となる接着性を備える構成要素である。また、本発明の複合フィルム10においては、粘着層20は、離型フィルム12に剥離可能に貼着される部位である。 Next, the
The pressure-
また、粘着層20と有機EL装置等の被封止部材の貼着面との粘着力は、封止積層体14と有機EL装置とが十分に接着される粘着力であれば特に限定はない。 The adhesive force between the
In addition, the adhesive force between the
粘着層20の含水率を200ppm以下とすることにより、封止積層体14として有機EL素子を封止した際に、粘着層20中に含まれる水分に起因して、有機EL素子が劣化するのを防止することができる。
また、本発明の複合フィルム10の形態においては、両外面側に積層されるガスバリアフィルム22により、保管中などに空気中の水分が粘着層20に到達するのを抑制することができるので、粘着層の含水率が高くなるのを抑制して、200ppm以下の低い含水率を維持することができる。 The
By setting the moisture content of the
Moreover, in the form of the
粘着層20が吸水能力を備えることにより、封止積層体14として有機EL素子を封止した際に、封止積層体14の端面やガスバリアフィルム22の欠陥等から浸入する水分を吸収して、有機EL素子の水分による劣化をより好適に防止できる。
また、本発明の複合フィルム10の形態においては、両外面側に積層されるガスバリアフィルム22により、保管中などに空気中の水分が粘着層20に到達するのを抑制することができるので、複合フィルム10の形態時には、粘着層20が吸水することを抑制して、封止積層体14として有機EL素子を封止した後に、吸水能力を十分に発揮することが可能となる。 Moreover, it is preferable that the
When the
Moreover, in the form of the
一方、吸水能力とは、化学的結合により粘着層20中に吸水することができる水分の質量比の値である。化学的結合により含まれる水分は、基本的には加熱によって除去することができない。すなわち、吸水能力とは、粘着層20中に不可逆的に包含することができる水分量の質量比の値である。 Here, in this invention, a moisture content is a value of the mass ratio of the water | moisture content contained in the
On the other hand, the water absorption capacity is a value of a mass ratio of moisture that can be absorbed into the
まず、粘着層20から、サンプル片をグローブボックス内で切り出し、秤量する。このときのサンプル片の質量をx(g)とする。このサンプル片をグローブボックスから出した直後にカールフィッシャー法で測定した水分量を、サンプルの含水率とする。
次に、同様にグローブボックスで切り出し、秤量を行ったサンプル片をグローブボックスから取り出し、温度25℃、湿度50%RHの環境下で48時間以上、調湿した後に秤量する。調湿後のサンプル片の質量をy(g)とする。すなわち、調湿後のサンプル片は、膨潤による含水と、化学的結合による吸水とによる水分を含んだ状態である。
次に、調湿後のサンプル片を再度、グローブボックス内に入れ、温度80℃で50時間以上、真空乾燥した後に秤量する。乾燥後のサンプル片の質量をz(g)とする。すなわち、乾燥後のサンプル片は、膨潤による水分を除去し、化学的結合による水分のみを含んだ状態である。
これら各状態でのサンプル片の質量から、吸水能力は、(z-x)/xにより算出される。 In the present invention, the moisture content and the water absorption capacity are measured by the following measuring method.
First, a sample piece is cut out from the
Next, the sample piece cut out in the glove box and weighed in the same manner is taken out from the glove box, weighed for 48 hours or more in an environment of temperature 25 ° C. and
Next, the sample piece after humidity adjustment is put again in the glove box, and is weighed after being vacuum-dried at a temperature of 80 ° C. for 50 hours or more. Let the mass of the sample piece after drying be z (g). That is, the sample piece after drying is in a state where moisture due to swelling is removed and only moisture due to chemical bonding is included.
From the mass of the sample piece in each of these states, the water absorption capacity is calculated by (z−x) / x.
具体的には、粘着層20としては、OCA(Optically Clear Adhesive)シート等の粘着シートを用いてもよく、あるいは、重合や熱などにより樹脂を硬化させた有機層であってもよい。
硬化性樹脂としては、シリコーン樹脂、アクリル樹脂、メタクリル樹脂、エポキシ樹脂、メラミン樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシアクリレート樹脂、環状オレフィン系樹脂等が挙げられる。中でも、アクリル樹脂、エポキシ樹脂、エポキシアクリレート樹脂、環状オレフィン系樹脂が好ましい。また、3以上の多官能アクリレート/メタクリレート化合物からなる樹脂であるのが好ましい。
また、これらの硬化性樹脂を主成分として、粘度や硬化性を調整するための樹脂が混合されてもよい。例えば、粘度調整のためにスチレン・ブタジエンブロック共重合体を含んでも良い。
また、これらの硬化性樹脂は、単独で用いられてもよく、2種以上が併用されてもよい。 As a material for forming the pressure-
Specifically, the
Examples of the curable resin include silicone resin, acrylic resin, methacrylic resin, epoxy resin, melamine resin, polyester resin, urethane resin, epoxy acrylate resin, and cyclic olefin resin. Among these, acrylic resins, epoxy resins, epoxy acrylate resins, and cyclic olefin resins are preferable. Moreover, it is preferable that it is resin which consists of a 3 or more polyfunctional acrylate / methacrylate compound.
Moreover, resin for adjusting a viscosity and sclerosis | hardenability may be mixed by making these curable resins into a main component. For example, a styrene / butadiene block copolymer may be included for viscosity adjustment.
Moreover, these curable resins may be used independently and 2 or more types may be used together.
また、必要に応じてシランカップリング剤又はシラン変性エポキシ樹脂を含有してもよい。シランカップリング剤とシラン変性エポキシ樹脂とを併用することも可能である。それら成分を粘着層20としての硬化性樹脂に配合することによって、加湿による接着力の低下を抑えることが可能となる。 Furthermore, you may mix a photoinitiator, a photosensitizer, etc. in said curable resin.
Moreover, you may contain a silane coupling agent or a silane modified epoxy resin as needed. It is also possible to use a silane coupling agent and a silane-modified epoxy resin in combination. By blending these components into the curable resin as the pressure-
上記無機フィラーは特に限定されず、例えば、タルク、石綿、シリカ、スメクタイト、ベントナイト、炭酸カルシウム、炭酸マグネシウム、アルミナ、モンモリロナイト、珪藻土、酸化マグネシウム、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、ガラスビーズ、硫酸バリウム、石膏、珪酸カルシウム、セリサイト活性白土等が挙げられる。 Moreover, it is preferable that curable resin used as the
The inorganic filler is not particularly limited, for example, talc, asbestos, silica, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, Examples include barium sulfate, gypsum, calcium silicate, and sericite activated clay.
粘着層20が乾燥剤を含有することにより、封止積層体14として有機EL素子を封止した際に、封止積層体14の端面やガスバリアフィルム22の欠陥等から浸入する水分を吸収して、有機EL素子の水分による劣化をより好適に防止できる。 Moreover, in order to provide the
When the pressure-
有機金属錯体としては、化1の化学式で示される構造の有機金属化合物が好ましく、-[M(OR)-O]n-で示される構造であるのがより好ましく、環状AlOアシレートが特に好ましく、六員環構造を2以上もつ3価金属の有機金属化合物であって、3価金属がアルミニウムである有機金属化合物が好ましい。
ここで、化1の化学式において、R1、R2、R3は、水素、炭素数1個以上のアルキル基、アリール基、シクロアルキル基、複素環基を示す。また、それぞれの基の、水素の一部をハロゲン基に置換したものでもよい。R1、R2、R3は異なる基であっても、同じ基であってもよく、また、それぞれが連結されてもよい。あるいは、ポリマーでもよい。 The desiccant may be an organometallic complex or an inorganic desiccant.
As the organometallic complex, an organometallic compound having a structure represented by the chemical formula of Chemical Formula 1 is preferred, a structure represented by-[M (OR) -O] n- is more preferred, and cyclic AlO acylate is particularly preferred. An organometallic compound of a trivalent metal having two or more six-membered ring structures, in which the trivalent metal is aluminum, is preferable.
Here, in the chemical formula of Chemical Formula 1 , R 1 , R 2 , and R 3 represent hydrogen, an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, or a heterocyclic group. Moreover, what substituted a part of hydrogen of each group by the halogen group may be sufficient. R1, R2, and R3 may be different groups or the same group, and may be linked to each other. Alternatively, it may be a polymer.
また、環状ではないアルミニウム-トリイソプロポキシド(AIP)も好ましい。
また、特開2005-298598号公報に記載される水分吸収剤、および、特開2006-297380号公報に記載される乾燥剤も用いることができる。 Specifically, for example, aluminum oxide 2-ethylhexanoate (Olep AOO, Hope Pharmaceutical Co., Ltd.), aluminum oxide isopropylate (Algomer 7 manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum oxide stearate (Olep AOS, Hope Pharmaceutical Co., Ltd.) ), Aluminum oxide ethylate and the like.
Non-cyclic aluminum-triisopropoxide (AIP) is also preferred.
In addition, a water absorbent described in JP-A-2005-298598 and a desiccant described in JP-A-2006-297380 can also be used.
無機系の乾燥剤を用いる場合には、粘着層20のヘイズ値や透明性への影響を考慮して粒径を小さくするのがこのましく、10nm以下とするのが好ましい。 Examples of the inorganic desiccant include alkaline earth metal oxides such as calcium oxide (CaO), barium oxide (BaO), and magnesium oxide (MgO); lithium sulfate (Li 2 SO 4 ), sodium sulfate ( Na 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), cobalt sulfate (CoSO 4 ), gallium sulfate (Ga 2 (SO 4 ) 3 ), titanium sulfate (Ti (SO 4 ) 2 ), Sulfates such as nickel sulfate (NiSO 4 ), calcium chloride (CaCl 2 ), phosphorus pentoxide (P 2 O 5 ), potassium hydroxide (KOH), sodium hydroxide (NaOH), potassium bromide (KBr), odor Examples thereof include calcium chloride (CaBr 2 ), copper sulfate (CuSO 4 ), zinc chloride (ZnCl 2 ), zeolite, silica gel, activated alumina, and the like.
In the case of using an inorganic desiccant, it is preferable to reduce the particle size in consideration of the haze value of the
また、粘着層20を形成する際の塗布方法には特に限定はなく、スリットコート、ダイコート、ロールコート、ディップコート、ブレードコート、ナイフコート、バーコート、スクリーン印刷、スピンコートなどを用いることが出来る。
また、長尺なガスバリアフィルム22上に粘着層20を形成する場合には、長尺なガスバリアフィルム22を長手方向に搬送しつつ、塗布組成物の塗布、乾燥により粘着層20を形成する、いわゆるロール・ツー・ロールにより形成してもよい。 The
Moreover, there is no limitation in particular in the coating method at the time of forming the
Moreover, when forming the
図3に、封止積層体14を用いて有機EL素子を封止した有機EL装置の一例の概略断面図を示す。 Next, an organic EL device in which the sealing
FIG. 3 shows a schematic cross-sectional view of an example of an organic EL device in which an organic EL element is sealed using the sealing
封止積層体14を有機EL素子54上に積層して、有機EL素子54を封止することにより、有機EL素子54の水分による劣化を防止する。 The sealing
By stacking the sealing
ここで、本発明の有機EL装置50においては、水分等による有機EL素子54の劣化を防止するために、水分等が素子基板52を透過して有機EL素子54に至るのを防止できるのが好ましい。そのため、素子基板52は、ガラスや金属等のように、水分等の含有量が低く、かつ、水分等の透過率が低い材料からなる基板を用いるのが好ましい。あるいは、封止積層体14のガスバリアフィルム22も、水分等の透過率が低い点で素子基板52として好適に用いることができる。 As the
Here, in the
有機EL装置50がトップエミッション型である場合には、素子基板52が光透過性を有する必要は無い。従って、有機EL装置50を、トップエミッション型として利用する場合には、素子基板52として、表面に陽極酸化膜を有するアルミニウム箔や、アルミニウム箔とポリイミドとの積層体など、絶縁層を有する可撓性の金属フィルムを用いてもよい。この際、フレキシブルな有機EL装置50とすることができる。 Here, when the
When the
あるいは、封止積層体14、および、素子基板52共に光透過性のある材料を用いて、両面から光を発する構成としてもよい。 On the other hand, by using a light-transmitting material such as glass or a gas barrier film as the
Or it is good also as a structure which emits light from both surfaces using the light-transmitting material for both the sealing
有機EL素子54は、例えば、有機電界発光層と、有機電界発光層を挾持する電極対である透明電極および反射電極とを有する公知の有機EL素子である。
なお、有機EL装置50がトップエミッション型である場合には、封止積層体14側に透明電極が配置され、素子基板52側に反射電極が配置される。また有機EL装置50がボトムエミッション型である場合には、封止積層体14側に反射電極が配置され、素子基板52側に透明電極が配置される。 An
The
When the
透明電極としては、例えば、酸化インジウム錫(ITO)等の導電性金属酸化物等の、有機電界発光層から発せられた光を透過する光透過性を有する、種々の公知の電極が利用可能である。
また、反射電極としては、有機EL素子の電極として用いられる、種々の公知の電極が利用可能である。
また、有機電界発光層、透明電極、および、反射電極は、有機EL装置50の用途や大きさ等に応じて、公知の方法で形成すればよい。 The organic electroluminescent layer may be any layer having a known layer structure including a light emitting layer made of an organic EL material, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like.
As the transparent electrode, for example, various known electrodes having light transmissivity for transmitting light emitted from the organic electroluminescent layer, such as conductive metal oxide such as indium tin oxide (ITO), can be used. is there.
In addition, as the reflective electrode, various known electrodes used as an electrode of an organic EL element can be used.
Moreover, what is necessary is just to form an organic electroluminescent layer, a transparent electrode, and a reflective electrode by a well-known method according to the use of the
保護膜としては、公知の有機EL装置に利用される、ガスバリア性を発現する材料からなる各種の膜(層)が利用可能である。具体的には、ガスバリア性を有する無機化合物からなる膜が例示され、中でも、窒化ケイ素、酸化ケイ素および酸化窒化ケイ素等のケイ素化合物からなる膜が好適に例示される。 The
As the protective film, various films (layers) made of a material exhibiting gas barrier properties, which are used in known organic EL devices, can be used. Specifically, a film made of an inorganic compound having gas barrier properties is exemplified, and among these, a film made of a silicon compound such as silicon nitride, silicon oxide, and silicon oxynitride is preferably exemplified.
実施例1として、図1に示す複合フィルム10を作製した後、封止積層体14を剥離して、この封止積層体14を用いて有機EL素子を封止して図3に示す有機EL装置50を作製した。 [Example 1]
As Example 1, the
(ガスバリアフィルム)
ガスバリアフィルム22としては、ガスバリア基材26上に、平滑層27およびバリア層28の組み合わせを2つ有するフィルムを用いた。
ガスバリア基材26として、厚さ100μmのポリエチレンナフタレートフィルム(PENフィルム、帝人デュポンフィルム株式会社製 テオネックスQ65FA)を用いた。 <Composite film>
(Gas barrier film)
As the
As the
平滑層を形成する塗料として、重合性化合物のTMPTA(ダイセル・サイテック株式会社製)14.9g、シランカップリング剤(信越化学工業株式会社 SC-1)3.7g、紫外線重合開始剤(ランベルティ社製、ESACURE KTO46)1.4g、2-ブタノン180gからなる重合性組成物を調製した。
調製した重合性組成物を液厚が5μmとなるようにワイヤーバーを用いて基材フィルム上に塗布し、窒素置換法により酸素濃度が0.1%となったチャンバー内にて高圧水銀ランプの紫外線を照射(積算照射量約1J/cm2)して硬化させ平滑層27を形成した。 A
As a paint for forming a smooth layer, 14.9 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.7 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. SC-1), an ultraviolet polymerization initiator (Lamberti) A polymerizable composition comprising 1.4 g of ESACURE KTO 46) and 180 g of 2-butanone was prepared.
The prepared polymerizable composition was applied on a base film using a wire bar so that the liquid thickness was 5 μm, and the high pressure mercury lamp was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method. The
原料ガスは、シランガス(SiH4)、アンモニアガス(NH3)、窒素ガス(N2)および水素ガス(H2)を用いた。ガスの供給量は、シランガスが160sccm、アンモニアガスが370sccm、窒素ガスが240sccm、水素ガスが590sccmとした。また、成膜圧力は40Paとした。すなわち、バリア層28は、窒化珪素膜である。
プラズマ励起電力は、周波数13.56MHzで2.5kWとした。 Next, a barrier layer 28 was formed on the
Silane gas (SiH 4 ), ammonia gas (NH 3 ), nitrogen gas (N 2 ), and hydrogen gas (H 2 ) were used as source gases. The supply amounts of gas were 160 sccm for silane gas, 370 sccm for ammonia gas, 240 sccm for nitrogen gas, and 590 sccm for hydrogen gas. The film forming pressure was 40 Pa. That is, the barrier layer 28 is a silicon nitride film.
The plasma excitation power was 2.5 kW at a frequency of 13.56 MHz.
まず、第1の有機層として厚さ0.6μmの膜を形成した。
第1の有機層を形成する塗料として、重合性化合物のTMPTA(ダイセル・サイテック株式会社製)14.1g、シランカップリング剤(信越化学工業株式会社 SC-1)3.5g、酸性化合物のPA(日本化薬株式会社製 KARAMER PM-21)1.0g、紫外線重合開始剤(ランベルティ社製、ESACURE KTO46)1.4g、2-ブタノン180gからなる重合性組成物を調整した。
調製した重合性組成物を液厚が5μmとなるようにワイヤーバーを用いて無機層28上に塗布し、窒素置換法により酸素濃度が0.1%となったチャンバー内にて高圧水銀ランプの紫外線を照射(積算照射量約1J/cm2)して硬化させ第1の有機層を形成した。 Next, the
First, a film having a thickness of 0.6 μm was formed as the first organic layer.
As a coating material for forming the first organic layer, 14.1 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.5 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. SC-1), PA of an acidic compound A polymerizable composition comprising 1.0 g (KARAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.), 1.4 g UV polymerization initiator (ESACURE KTO46 manufactured by Lamberti Co., Ltd.) and 180 g 2-butanone was prepared.
The prepared polymerizable composition was applied on the inorganic layer 28 using a wire bar so that the liquid thickness was 5 μm, and the high pressure mercury lamp was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method. The first organic layer was formed by irradiating with ultraviolet rays (accumulated dose of about 1 J / cm 2 ) and curing.
第2の有機層を形成する塗料として、重合性化合物のTMPTA(ダイセル・サイテック株式会社製)14.9g、シランカップリング剤(信越化学工業株式会社 SC-1)3.7g、紫外線重合開始剤(ランベルティ社製、ESACURE KTO46)1.4g、2-ブタノン180gからなる重合性組成物を調整した。
調製した重合性組成物を液厚が5μmとなるようにワイヤーバーを用いて第1の有機層上に塗布し、窒素置換法により酸素濃度が0.1%となったチャンバー内にて高圧水銀ランプの紫外線を照射(積算照射量約1J/cm2)して硬化させ第2の有機層を形成し、2層の有機層からなる平滑層27とした。 Next, a film having a thickness of 0.6 μm was formed as a second organic layer on the first organic layer.
As a coating material for forming the second organic layer, 14.9 g of a polymerizable compound TMPTA (manufactured by Daicel Cytec Co., Ltd.), 3.7 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. SC-1), an ultraviolet polymerization initiator A polymerizable composition consisting of 1.4 g of 2-lamone 180 g (ESACURE KTO 46, manufactured by Lamberti Co., Ltd.) was prepared.
The prepared polymerizable composition was coated on the first organic layer using a wire bar so that the liquid thickness was 5 μm, and high-pressure mercury was used in a chamber in which the oxygen concentration was 0.1% by the nitrogen substitution method. The lamp was irradiated with ultraviolet rays (accumulated dose of about 1 J / cm 2 ) and cured to form a second organic layer, thereby forming a
作製したガスバリアフィルム22の水蒸気透過率は、1×10-3[g/(m2・day)]であった。 Further, on the second organic layer, a barrier layer 28 having a thickness of 40 nm was formed by the same method as above, and a
The produced
次に、塗布法によりガスバリアフィルム22のバリア層28上に、材料を塗布し、乾燥・硬化させて、厚さ10μmの粘着層20を形成し、封止積層体14を作製した。
粘着層20の材料としては、二液熱硬化型のアクリル酸エステルの液状樹脂(綜研化学株式会社製 SKダイン1831)を用いた。
また、塗布はアプリケーターを用いて行った。乾燥後の厚さが10μmとなるように調整して塗布した。また、硬化条件は、温度80℃で30分とした。 (Adhesive layer)
Next, a material was applied onto the barrier layer 28 of the
As a material for the
Moreover, application | coating was performed using the applicator. The thickness after drying was adjusted to 10 μm and applied. Curing conditions were 30 minutes at a temperature of 80 ° C.
離型フィルム12として、厚さ100μmのPETフィルムの両側にシリコーン樹脂を設置したフィルムを用いた。
この離型フィルム12の両面に、上記封止積層体14を、粘着層20側を離型フィルム12に対面させて貼着し、複合フィルム10を作製した。
なお、離型フィルム12への貼り合わせ前に、露点温度-60℃以下のグローブボックス内で、封止積層体14を温度80℃で24時間、加熱処理して乾燥した。 (Release film)
As the
The sealing
In addition, before bonding to the
調湿後、封止積層体14からサンプル片を切り出し、粘着層の吸水能力および含水率を測定した。吸水能力は0wt%、含水率は120ppmであった。 Next, the sealing
After humidity control, a sample piece was cut out from the sealing
次に、図3に示す有機EL装置50を作製した。
素子基板52として、ITO膜を有する導電性のガラス基板(表面抵抗値10Ω/□)を2-プロパノールで洗浄した後、10分間UV-オゾン処理を行った。素子基板52の厚さは700μmとした。 <Organic EL device>
Next, the
As the
(第1正孔輸送層)
銅フタロシアニン 膜厚10nm
(第2正孔輸送層)
N,N’-ジフェニル-N,N’-ジナフチルベンジジン 膜厚40nm
(発光層兼電子輸送層)
トリス(8-ヒドロキシキノリナト)アルミニウム 膜厚60nm
さらにフッ化リチウムを1nm、金属アルミニウムを100nm順次蒸着して陰極として形成し、有機EL素子54を形成した。 Next, the following organic compound layers were sequentially deposited on the anode of the
(First hole transport layer)
Copper phthalocyanine film thickness 10nm
(Second hole transport layer)
N, N'-diphenyl-N, N'-dinaphthylbenzidine film thickness 40nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum film thickness 60nm
Further, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode, thereby forming an
粘着層20中に乾燥剤を含有させた以外は、実施例1と同様にして複合フィルム10を作製し、この複合フィルム10の封止積層体14を用いて有機EL装置50を作製した。
乾燥剤としては、アルミニウムオキサイド2-エチルヘキサノエート(ホープ製薬株式会社オリープ A00)を用い、粘着層20の材料中に15wt%含有させた。
また、調湿後の粘着層の吸水能力および含水率を測定しところ、吸水能力は1.2wt%、含水率は0ppmであった。 [Example 2]
A
As the desiccant, aluminum oxide 2-ethylhexanoate (Hope Pharmaceutical Co., Ltd. Olipe A00) was used, and 15 wt% was contained in the material of the
Moreover, when the water absorption capability and moisture content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capability was 1.2 wt%, and the moisture content was 0 ppm.
図4に示すように、離型フィルムの片面のみに、封止積層体を貼着し、複合フィルムを作製した以外は、実施例1と同様にして有機EL装置を作製した。
また、調湿後の粘着層の吸水能力および含水率を測定しところ、吸水能力は0wt%、含水率は520ppmであった。 [Comparative Example 1]
As shown in FIG. 4, an organic EL device was produced in the same manner as in Example 1 except that the sealing laminate was adhered to only one surface of the release film to produce a composite film.
Further, when the water absorption capacity and water content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capacity was 0 wt% and the water content was 520 ppm.
離型フィルムの片面のみに、封止積層体を貼着し、複合フィルムを作製した以外は、実施例2と同様にして有機EL装置を作製した。
また、調湿後の粘着層の吸水能力および含水率を測定しところ、吸水能力は1.2wt%、含水率は230ppmであった。 [Comparative Example 2]
An organic EL device was produced in the same manner as in Example 2 except that the sealing laminate was adhered to only one surface of the release film to produce a composite film.
Moreover, when the water absorption capacity and moisture content of the pressure-sensitive adhesive layer after humidity control were measured, the water absorption capacity was 1.2 wt%, and the water content was 230 ppm.
<耐久性試験>
作製した実施例1、2および比較例1、2の有機EL装置について、耐久性試験を行った。
具体的には、まず、作製直後の有機EL装置の有機EL素子を、Keithley社製SMU2400型ソースメジャーユニットを用いて7Vの電圧を印加して発光させた。顕微鏡を用いて発光面状を観察したところ、いずれの素子もダークスポットの無い均一な発光を与えることが確認された。
次に、温度60℃の暗い室内に24時間静置した後、先と同様にして、発光面状を観察し、直径300μmよりも大きいダークスポット有無を評価した。
さらに、温度60℃湿度90%RHの環境下で100時間静置した後に、先と同様にして、発光面状を観察し、直径300μmよりも大きいダークスポット有無を評価した。 [Evaluation]
<Durability test>
Durability tests were performed on the organic EL devices of Examples 1 and 2 and Comparative Examples 1 and 2 that were produced.
Specifically, first, the organic EL element of the organic EL device immediately after fabrication was made to emit light by applying a voltage of 7 V using an SMU2400 type source measure unit manufactured by Keithley. When the surface of the light emitting surface was observed using a microscope, it was confirmed that all the elements gave uniform light emission without dark spots.
Next, after standing in a dark room at a temperature of 60 ° C. for 24 hours, the surface of the light emitting surface was observed in the same manner as described above, and the presence or absence of a dark spot larger than 300 μm in diameter was evaluated.
Furthermore, after leaving still for 100 hours in an environment of temperature 60 ° C. and humidity 90% RH, the surface of the light-emitting surface was observed in the same manner as described above, and the presence or absence of dark spots larger than 300 μm in diameter was evaluated.
300μm以上のダークスポットが観察されない場合を『A』、
300μm以上のダークスポットが10個未満観察された場合を『B』、
300μm以上のダークスポットが10個以上観察された場合を『C』とした。
結果を下記の表1に示す。 Evaluation,
A case where a dark spot of 300 μm or more is not observed is “A”.
When less than 10 dark spots of 300 μm or more are observed, “B”,
The case where 10 or more dark spots of 300 μm or more were observed was designated as “C”.
The results are shown in Table 1 below.
本発明の複合フィルムを用いて封止された有機EL装置は、観察されるダークスポットが無い、または、数が少ないことから、有機EL素子の封止に用いた本発明の封止積層体の粘着層中の水分量が少ないことがわかる。
一方、比較例においては、有機EL素子全面に多数のダークスポットが観察された。これは、有機EL素子の封止に用いた封止積層体の粘着層中に水分が含まれているためである。
以上の結果より、本発明の効果は明らかである。 As shown in Table 1 above, it can be seen that the organic EL device sealed with the composite film of the present invention has less dark spots and higher durability than the comparative example.
Since the organic EL device sealed using the composite film of the present invention has no observed dark spots or a small number of the organic EL devices, the organic EL device of the present invention used for sealing the organic EL element is used. It can be seen that the amount of water in the adhesive layer is small.
On the other hand, in the comparative example, many dark spots were observed on the entire surface of the organic EL element. This is because moisture is contained in the adhesive layer of the sealing laminate used for sealing the organic EL element.
From the above results, the effects of the present invention are clear.
12、106 離型フィルム
14 封止積層体
20、102 粘着層
22、104 ガスバリアフィルム
26 ガスバリア基材
27 平滑層
28 バリア層
50 有機EL装置
52 素子基板
54 有機EL素子 DESCRIPTION OF SYMBOLS 10,100 Composite film 12,106
Claims (8)
- 第1の防湿フィルムと、第1の粘着層と、離型フィルムと、第2の粘着層と、第2の防湿フィルムとをこの順に積層されてなる複合フィルム。 A composite film obtained by laminating a first moisture-proof film, a first adhesive layer, a release film, a second adhesive layer, and a second moisture-proof film in this order.
- 前記第1の粘着層および前記第2の粘着層が吸水能力を有する請求項1に記載の複合フィルム。 The composite film according to claim 1, wherein the first adhesive layer and the second adhesive layer have a water absorption ability.
- 前記第1の粘着層および前記第2の粘着層の吸水能力が、0.5wt%以上である請求項2に記載の複合フィルム。 The composite film according to claim 2, wherein the water absorption capacity of the first adhesive layer and the second adhesive layer is 0.5 wt% or more.
- 前記第1の粘着層および前記第2の粘着層の含水率が、200ppm以下である請求項1~3のいずれか1項に記載の複合フィルム。 The composite film according to any one of claims 1 to 3, wherein the moisture content of the first adhesive layer and the second adhesive layer is 200 ppm or less.
- 前記第1の防湿フィルムおよび前記第2の防湿フィルムの水蒸気透過率が、1×10-3[g/(m2・day)]以下である請求項1~4のいずれか1項に記載の複合フィルム。 5. The water vapor transmission rate of the first moisture-proof film and the second moisture-proof film is 1 × 10 −3 [g / (m 2 · day)] or less, according to any one of claims 1 to 4. Composite film.
- 前記第1の防湿フィルムおよび前記第2の防湿フィルムが、少なくともガスバリア基材と、平滑層と、バリア層とを有してなるガスバリアフィルムである請求項1~5のいずれか1項に記載の複合フィルム。 6. The gas barrier film according to claim 1, wherein each of the first moisture-proof film and the second moisture-proof film is a gas barrier film having at least a gas barrier substrate, a smooth layer, and a barrier layer. Composite film.
- 前記バリア層が酸化物、窒化物、酸窒化物の少なくとも1つからなる請求項6に記載の複合フィルム。 The composite film according to claim 6, wherein the barrier layer is made of at least one of oxide, nitride, and oxynitride.
- 前記離型フィルムが、フィルム基材と、前記フィルム基材の両側の表面に形成された離型層とを有してなる請求項1~7のいずれか1項に記載の複合フィルム。 The composite film according to any one of claims 1 to 7, wherein the release film comprises a film base and release layers formed on both surfaces of the film base.
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WO2019189932A1 (en) * | 2018-03-30 | 2019-10-03 | 東洋製罐グループホールディングス株式会社 | Electronic device barrier film |
WO2019189825A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for producing optical member |
CN113439241A (en) * | 2019-02-19 | 2021-09-24 | 株式会社理光 | Photoelectric conversion element, organic photoconductor, image forming method, image forming apparatus, and organic EL element |
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JP2007169519A (en) * | 2005-12-22 | 2007-07-05 | Mitsubishi Plastics Ind Ltd | Pressure-sensitive adhesive sheet |
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JP2011056775A (en) | 2009-09-09 | 2011-03-24 | Fujifilm Corp | Electronic element panel sealing method, film composite body, electronic element panel, and method for manufacturing the same |
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Cited By (7)
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WO2019189825A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for producing optical member |
JP2019174777A (en) * | 2018-03-29 | 2019-10-10 | ホヤ レンズ タイランド リミテッドHOYA Lens Thailand Ltd | Method for manufacturing optical member |
EP3778203A4 (en) * | 2018-03-29 | 2021-12-15 | Hoya Lens Thailand Ltd. | Method for producing optical member |
WO2019189932A1 (en) * | 2018-03-30 | 2019-10-03 | 東洋製罐グループホールディングス株式会社 | Electronic device barrier film |
JP2019177645A (en) * | 2018-03-30 | 2019-10-17 | 東洋製罐グループホールディングス株式会社 | Barrier film for electronic device |
US11479018B2 (en) | 2018-03-30 | 2022-10-25 | Toyo Seikan Group Holdings, Ltd. | Barrier film for electronic devices |
CN113439241A (en) * | 2019-02-19 | 2021-09-24 | 株式会社理光 | Photoelectric conversion element, organic photoconductor, image forming method, image forming apparatus, and organic EL element |
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