[go: up one dir, main page]

WO2016009778A1 - Film composite - Google Patents

Film composite Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
film
layer
organic
adhesive layer
gas barrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/067578
Other languages
English (en)
Japanese (ja)
Inventor
賢志 狩野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020177001005A priority Critical patent/KR101917543B1/ko
Priority to JP2016534335A priority patent/JP6142091B2/ja
Publication of WO2016009778A1 publication Critical patent/WO2016009778A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un film composite qui est apte à empêcher une couche adhésive de contenir de l'humidité en son sein sans provoquer une augmentation du coût, et qui est par conséquent apte à empêcher la détérioration d'un élément EL organique en protégeant l'élément de manière stable pendant une longue période dans les cas où le film composite est utilisé pour l'étanchéité d'un dispositif EL organique. Ce film composite est obtenu par stratification séquentielle d'un premier film résistant à l'humidité, d'une première couche adhésive, d'un film de démoulage, d'une seconde couche adhésive et d'un second film résistant à l'humidité dans cet ordre.
PCT/JP2015/067578 2014-07-14 2015-06-18 Film composite Ceased WO2016009778A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020177001005A KR101917543B1 (ko) 2014-07-14 2015-06-18 복합 필름
JP2016534335A JP6142091B2 (ja) 2014-07-14 2015-06-18 複合フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-144187 2014-07-14
JP2014144187 2014-07-14

Publications (1)

Publication Number Publication Date
WO2016009778A1 true WO2016009778A1 (fr) 2016-01-21

Family

ID=55078279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/067578 Ceased WO2016009778A1 (fr) 2014-07-14 2015-06-18 Film composite

Country Status (3)

Country Link
JP (1) JP6142091B2 (fr)
KR (1) KR101917543B1 (fr)
WO (1) WO2016009778A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189825A1 (fr) * 2018-03-29 2019-10-03 ホヤ レンズ タイランド リミテッド Procédé de production d'élément optique
WO2019189932A1 (fr) * 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 Film barrière de dispositif électronique
CN113439241A (zh) * 2019-02-19 2021-09-24 株式会社理光 光电转换元件、有机光电导体、图像形成方法、图像形成设备和有机el元件

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169519A (ja) * 2005-12-22 2007-07-05 Mitsubishi Plastics Ind Ltd 粘着シート

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100580351B1 (ko) * 1997-04-17 2006-05-16 가부시끼가이샤 구레하 방습 필름 및 전기 발광 소자
JP2007026682A (ja) * 2005-07-12 2007-02-01 Sony Corp 非水電解質二次電池
JP2011056775A (ja) 2009-09-09 2011-03-24 Fujifilm Corp 電子素子パネルの封止方法、フィルム複合体、電子素子パネルおよびその製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169519A (ja) * 2005-12-22 2007-07-05 Mitsubishi Plastics Ind Ltd 粘着シート

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189825A1 (fr) * 2018-03-29 2019-10-03 ホヤ レンズ タイランド リミテッド Procédé de production d'élément optique
JP2019174777A (ja) * 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 光学部材の製造方法
EP3778203A4 (fr) * 2018-03-29 2021-12-15 Hoya Lens Thailand Ltd. Procédé de production d'élément optique
WO2019189932A1 (fr) * 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 Film barrière de dispositif électronique
JP2019177645A (ja) * 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 電子デバイス用バリアフィルム
US11479018B2 (en) 2018-03-30 2022-10-25 Toyo Seikan Group Holdings, Ltd. Barrier film for electronic devices
CN113439241A (zh) * 2019-02-19 2021-09-24 株式会社理光 光电转换元件、有机光电导体、图像形成方法、图像形成设备和有机el元件

Also Published As

Publication number Publication date
KR101917543B1 (ko) 2018-11-09
JP6142091B2 (ja) 2017-06-07
JPWO2016009778A1 (ja) 2017-06-01
KR20170018918A (ko) 2017-02-20

Similar Documents

Publication Publication Date Title
TWI586774B (zh) 壓敏性黏著組成物、壓敏性黏著膜、及使用彼製造有機電子裝置之方法
TWI588028B (zh) 封裝膜
KR101777488B1 (ko) 유기 el 적층체
CN108778715B (zh) 封装膜
JP6170627B2 (ja) 電子デバイスの製造方法および複合フィルム
CN106062988A (zh) 包封薄膜以及含有该包封薄膜的有机电子器件
JP6377541B2 (ja) フレキシブルデバイスの製造方法、および、フレキシブルデバイス積層体
JP6321169B2 (ja) 封止積層体および有機電子装置
JP2015103389A (ja) 有機ｅｌ素子
JP5580561B2 (ja) バリア性積層体、ガスバリアフィルムおよびバリア性積層体の製造方法
JP6142091B2 (ja) 複合フィルム
JP2009196318A (ja) 積層体とバリア性フィルム基板の製造方法、バリア材料、デバイスおよび光学部材
JP5453719B2 (ja) ガスバリア性シート
CN114902439A (zh) 封装膜
JP6196944B2 (ja) 封止部材および電子デバイスの製造方法
CN113474435A (zh) 封装膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15822001

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016534335

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20177001005

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15822001

Country of ref document: EP

Kind code of ref document: A1