WO2014119551A1 - Film-shaped sealing material, sealing sheet, and electronic device - Google Patents

Film-shaped sealing material, sealing sheet, and electronic device Download PDF

Info

Publication number
WO2014119551A1
WO2014119551A1 PCT/JP2014/051790 JP2014051790W WO2014119551A1 WO 2014119551 A1 WO2014119551 A1 WO 2014119551A1 JP 2014051790 W JP2014051790 W JP 2014051790W WO 2014119551 A1 WO2014119551 A1 WO 2014119551A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
resin layer
sealing material
water vapor
adhesive resin
Prior art date
Application number
PCT/JP2014/051790
Other languages
French (fr)
Japanese (ja)
Inventor
佳明 萩原
田矢　直紀
智史 永縄
Original Assignee
リンテック株式会社
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 リンテック株式会社 filed Critical リンテック株式会社
Publication of WO2014119551A1 publication Critical patent/WO2014119551A1/en

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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to a film-like sealing material and a sealing sheet that can seal an electronic element and the like, and an electronic device in which the electronic element is sealed by them.
  • an electronic device for example, a display module having a liquid crystal element, a light emitting diode (LED element), or a solar battery module having a solar cell
  • moisture and oxygen enter the electronic element inside the device and have an adverse effect.
  • the electronic element is covered using a glass plate or a resin film.
  • a film-like sealing material for sealing the electronic element is used.
  • the sealing material for example, as shown in Patent Documents 1 and 2, etc., ethylene-vinyl acetate copolymer (EVA) and polyvinyl butyral (PVB) are mainly used.
  • Patent Document 3 discloses that an ethylene-methacrylic acid copolymer (EMAA) can be used
  • Patent Document 4 discloses that an ionomer resin can be used
  • Patent Document 5 discloses that an alicyclic structure-containing polymer can be used.
  • Patent Document 6 discloses a three-layer structure solar cell filler sheet having an intermediate layer made of a low-density polyethylene resin or a linear low-density polyethylene resin, and adhesive layers on both sides thereof. The solar cell filler sheet having a three-layer structure described in Patent Document 6 prevents thermal shrinkage and is excellent in adhesiveness as compared with a conventional single-layer sheet.
  • Japanese Patent Application Laid-Open No. 6-177412 Japanese Patent Laid-Open No. 10-233521 JP 2000-252491 A JP 2006-66762 A JP 2003-59645 A JP 2012-216805 A
  • the present invention has been made in view of such a situation, and an object thereof is to provide a film-shaped sealing material, a sealing sheet, and an electronic device excellent in water vapor barrier properties and adhesiveness.
  • the present invention includes first and second adhesive resin layers exhibiting adhesion to an adherend, the first adhesive resin layer, and the second adhesive layer.
  • It is a film-form sealing material provided with the water vapor
  • the adhesive strength to the glass plate is 3 N / 25 mm or more, and converted into a thickness of 50 ⁇ m (the thickness of the film-like sealing material) in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH.
  • the film-like sealing material is characterized in that the water vapor transmission rate W is 10 g / m 2 ⁇ day or less (Invention 1).
  • the film-shaped sealing material according to the above invention includes the first and second adhesive resin layers and the water vapor barrier resin layer positioned therebetween, whereby the adhesive force and the water vapor transmission rate are obtained. Is controlled as described above, and is excellent in adhesion and water vapor barrier properties.
  • the water vapor transmission rate of the first adhesive resin layer converted to a thickness of 50 ⁇ m in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH is W1 (g / m 2 ⁇ day)
  • the water vapor transmission rate of the second adhesive resin layer in terms of thickness 50 ⁇ m is W2 (g / m 2 ⁇ day)
  • the water vapor transmission rate of the water vapor barrier resin layer in terms of thickness 50 ⁇ m is W 3 (g / m 2 ⁇ day).
  • W1, W2, and W3 satisfy the following relationship: W1> W3, W2> W3, and W3 ⁇ 10 It is preferable (Invention 2).
  • the thickness of the first adhesive resin layer is T1 ( ⁇ m)
  • the thickness of the second adhesive resin layer is T2 ( ⁇ m)
  • the water vapor barrier resin When the layer thickness is T3 ( ⁇ m), T1, T2 and T3 satisfy the following relationship: 0.1 ⁇ T3 / (T1 + T2 + T3) ⁇ ⁇ 0.99 1 ⁇ T1 ⁇ 100 1 ⁇ T2 ⁇ 100 5 ⁇ T3 ⁇ 300 (Invention 3)
  • the first and second adhesive resin layers are directly laminated on the water vapor barrier resin layer, and preferably have a three-layer structure thereof (Invention 4). .
  • the present invention provides a sealing sheet comprising the film-like sealing material (Inventions 1 to 4) and a gas barrier film laminated on one surface of the film-like sealing material. (Invention 5).
  • the present invention provides an electronic device characterized by being sealed with the film-like sealing material (Invention 1 to 4) (Invention 6).
  • the present invention provides an electronic device characterized by being sealed by the sealing sheet (Invention 5) (Invention 7).
  • the film-shaped sealing material according to the present invention includes first and second adhesive resin layers exhibiting adhesiveness to an adherend, a first adhesive resin layer, and a second adhesive resin layer.
  • the adhesive strength to the glass plate is controlled to 3 N / 25 mm or more, and the thickness is converted to 50 ⁇ m in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH (
  • the water vapor transmission rate W is controlled to 10 g / m 2 ⁇ day or less, and the adhesiveness and the water vapor barrier property are excellent.
  • the performance of the sealing material is caused by the adhesive strength to the adherend and the water vapor transmission rate of the sealing material.
  • the electronic device can be reliably sealed. Can do.
  • the film-shaped sealing material 1 which concerns on this embodiment is 1st and 2nd adhesive resin layer 11A, 11B, 1st adhesive resin layer 11A, and 2nd adhesive resin. And a water vapor barrier resin layer 12 positioned between the layer 11B.
  • the first and second adhesive resin layers 11A and 11B are directly laminated on the water vapor barrier resin layer 12, and the film-shaped sealing material 1 according to the present embodiment includes those layers. Although it consists of a three-layer structure, this invention is not limited to this.
  • the film-shaped sealing material 1 has a water vapor transmission rate controlled by disposing the water vapor barrier resin layer 12 between the first adhesive resin layer 11A and the second adhesive resin layer 11B.
  • first and second adhesive resin layers 11A and 11B are disposed on both sides of the water vapor barrier resin layer 12, high adhesiveness is achieved.
  • the film-shaped sealing material 1 has an adhesive force with respect to the glass plate of 3N / when either one surface of the first adhesive resin layer 11A or the second adhesive resin layer 11B is bonded to the glass plate. It is 25 mm or more.
  • a sealing member such as a glass plate or a resin film and a sealing object such as an electronic element are firmly bonded to each other through the film-like sealing material 1 and sealed. While sealing an object reliably, a water
  • the adhesive strength is preferably 3 N / 25 mm or more, particularly preferably 5 N / 25 mm or more, and more preferably 10 N / 25 mm or more.
  • the upper limit of the adhesive force is not particularly limited, but usually it is preferably 500 N / 25 mm or less.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • the film-form sealing material 1 has a water vapor transmission rate W of 10 g in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH in terms of a thickness of 50 ⁇ m (when the thickness of the film-shaped sealing material 1 is 50 ⁇ m). / M 2 ⁇ day or less.
  • W water vapor transmission rate
  • the water vapor transmission rate W is preferably 7 g / m 2 ⁇ day or less, particularly preferably 5 g / m 2 ⁇ day or less, and more preferably 3 g / m 2 ⁇ day or less.
  • the water vapor transmission rate of the first adhesive resin layer 11A in terms of a thickness of 50 ⁇ m (when the thickness of the first adhesive resin layer 11A is 50 ⁇ m) in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH is
  • the water vapor transmission rate of the second adhesive resin layer 11B in terms of W1 (g / m 2 ⁇ day) and 50 ⁇ m thickness (when the thickness of the second adhesive resin layer 11B is 50 ⁇ m) is W2 (g / m 2 Day)
  • W1 W2 and W3 are W1> W3, W2> W3 and W3 ⁇ 10 It is preferable to satisfy the relationship.
  • W1, W2, and W3 are within the above range, the film-shaped sealing material 1 can easily achieve the water vapor transmission rate
  • the water vapor transmission rates W1 and W2 are preferably 200 g / m 2 ⁇ day or less, particularly preferably 100 g / m 2 ⁇ day or less, and more preferably 50 g / m 2 ⁇ day or less.
  • the measuring method of water-vapor-permeation rate W, W1, W2, and W3 is as showing to the test example mentioned later.
  • the values of water vapor permeability W, W1, W2, and W3 in terms of thickness 50 ⁇ m can be obtained by conversion from the thickness of each layer. For example, when the thickness is A ⁇ m and the water vapor transmission rate is Bg / (m 2 ⁇ day), the water vapor transmission rate in terms of the thickness of 50 ⁇ m can be obtained by applying the formula B ⁇ A / 50.
  • T1 thickness of the first adhesive resin layer
  • T2 thickness of the second adhesive resin layer
  • T3 thickness of the water vapor barrier resin layer
  • T1, T2 and T3 are 0.1 ⁇ T3 / (T1 + T2 + T3) ⁇ ⁇ 0.99 1 ⁇ T1 ⁇ 100 1 ⁇ T2 ⁇ 100 5 ⁇ T3 ⁇ 300 It is preferable to satisfy the relationship.
  • T1, T2, and T3 satisfy the above relationship, the film-shaped sealing material 1 can easily achieve the water vapor transmission rate and the adhesive force as described above.
  • the upper limit value of ⁇ T3 / (T1 + T2 + T3) ⁇ is more preferably 0.95, particularly preferably 0.9, and further preferably 0.8.
  • the lower limit value is more preferably 0.3, particularly preferably 0.4, and further preferably 0.5. If the lower limit of ⁇ T3 / (T1 + T2 + T3) ⁇ is less than 0.1, the desired water vapor barrier property may not be obtained. On the other hand, if the upper limit of ⁇ T3 / (T1 + T2 + T3) ⁇ exceeds 0.99, the desired adhesiveness may not be obtained.
  • T3 fill desired water vapor permeability as T3 is less than 5 micrometers
  • T3 is 5 micrometers or more, and it is especially 10 micrometers or more. Preferably, it is 15 ⁇ m or more.
  • T3 is preferably 300 ⁇ m or less, particularly preferably 200 ⁇ m or less, and further preferably 100 ⁇ m or less.
  • T1 and T2 are preferably 1 ⁇ m or more, and 3 ⁇ m or more. Is particularly preferable and is more preferably 5 ⁇ m or more.
  • T1 and T2 are preferably 100 ⁇ m or less, particularly preferably 80 ⁇ m or less, and 50 ⁇ m or less. Is more preferable.
  • the film-like encapsulant 1 preferably has a total light transmittance in the visible light region of 85% or more, particularly preferably 88% or more, and more preferably 90% or more.
  • the total light transmittance is a value measured in accordance with JIS K 7361: 1996.
  • Adhesive resin layer The first adhesive resin layer 11A and the second adhesive resin layer 11B are layers exhibiting adhesiveness to the adherend, and in this embodiment, a film-like sealing material 1 is provided on the outermost layer of both sides.
  • the resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it satisfies the above-mentioned range of adhesive force.
  • a thermoplastic resin, a thermosetting resin, an energy beam examples thereof include curable resins.
  • the first and second adhesive resin layers 11 ⁇ / b> A and 11 ⁇ / b> B contain a thermoplastic resin from the viewpoint of excellent adhesion to the water vapor barrier resin layer 12.
  • thermoplastic resins include acid-modified polyolefin resins, silane-modified polyolefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers.
  • examples include polymers, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins, and rubber resins.
  • acid-modified polyolefin resins silane-modified polyolefin resins, ionomers, and ethylene- (meth) acrylic acid copolymers that can easily satisfy the above-described adhesive force range and have a relatively low water vapor permeability are preferable.
  • These can be used individually by 1 type or in mixture of 2 or more types.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • the first and second adhesive resin layers 11A and 11B are an acid-modified polyolefin resin, from the viewpoint of excellent adhesion to the glass plate and excellent adhesion to the water vapor barrier resin layer 12. It is preferable to include at least one selected from the group consisting of silane-modified polyolefins, ionomers, and ethylene- (meth) acrylic acid copolymers. It is particularly preferable to include a modified polyolefin resin and / or a silane-modified polyolefin resin.
  • the acid-modified polyolefin resin means a polyolefin resin graft-modified with an acid, and examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and introducing a carboxyl group (graft modification).
  • the unsaturated carboxylic acid includes the concept of a carboxylic acid anhydride
  • the carboxyl group includes the concept of an anhydrous carboxyl group.
  • the polyolefin resin refers to a polymer (including the concept of a copolymer) containing olefin as a monomer component constituting the polymer, and the monomer component is a polymer composed of only one or two or more olefins. Alternatively, it may be a polymer (copolymer) containing one or more olefins and other monomers as monomer components.
  • the olefin is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and examples thereof include ethylene, propylene, butylene, isobutylene and 1-hexene. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable.
  • the other monomer is not particularly limited as long as the purpose of the film-shaped sealing material 1 according to the present embodiment is not impaired, and examples thereof include vinyl acetate and (meth) acrylic acid ester.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • ultra low density polyethylene VLDPE, density: 880 kg / m 3 or more and less than 910 kg / m 3
  • low density polyethylene LDPE, density: 910 kg / m 3 or more, 930 kg / m 3
  • medium density polyethylene MDPE, density: 930 kg / m 3 or more, 942Kg / m 3
  • high density polyethylene HDPE, density: 942kg / m 3 or higher
  • linear low density polyethylene such as polyethylene Resin, polypropylene resin, ethylene-propylene copolymer, olefin elastomer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc.
  • polyethylene resins such as ultra-low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene are preferable, and ultra low density polyethylene is particularly preferable.
  • Examples of the unsaturated carboxylic acid to be reacted with the polyolefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, Citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, (meth) acrylic acid and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among the above, maleic anhydride, which is particularly excellent in adhesive strength, is preferable.
  • the acid-modified polyolefin resin is preferably a maleic anhydride-modified polyolefin resin, particularly preferably a maleic anhydride-modified polyethylene resin.
  • the amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5.0 parts by mass, particularly 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the polyolefin resin. Preferably, the amount is 0.2 to 1.0 part by mass.
  • the amount of the unsaturated carboxylic acid to be reacted is in the above range, the resulting acid-modified polyolefin resin is excellent in adhesive strength.
  • the acid-modified polyolefin resin preferably has a Vicat softening point (Sp) of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C.
  • a Vicat softening point of 30 ° C. or higher is preferable because the adhesiveness is not expressed at room temperature, and the handleability of the film-shaped sealing material 1 is excellent.
  • the Vicat softening point is 90 ° C. or lower, it becomes possible to bond by thermocompression bonding in a relatively short time, so that the organic element can be prevented from being deteriorated by heat during thermocompression bonding, and has an organic EL element.
  • Electronic devices such as modules for display devices, electronic paper, and organic thin-film solar cells can be efficiently manufactured.
  • the Vicat softening point is a value measured based on ASTM D1525.
  • the acid-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly preferably 1 to 15 g / 10 minutes. Further, it is preferably 2 to 10 g / 10 minutes.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • MFR in this specification shall be the value measured based on ASTMD1238.
  • Admer registered trademark
  • BondyRam manufactured by Polyram
  • orevac registered trademark
  • Modic registered trademark
  • the silane-modified polyolefin resin is obtained by graft-modifying a polyolefin resin by reacting an unsaturated silane compound with the polyolefin resin.
  • a silane-modified polyolefin resin is preferable because it can be firmly bonded, particularly when the adherend is a glass plate, and the adhesive force hardly decreases even under wet heat conditions.
  • polyolefin resin of the silane-modified polyolefin resin examples include the polyolefin resins exemplified as the polyolefin resin to be graft-modified with the above-mentioned acid.
  • the silane-modified polyolefin-based resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and in particular, silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • a modified polyethylene resin is preferred.
  • a vinyl silane compound is preferable.
  • the amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, the content is 0.5 to 5 parts by mass.
  • the amount of the unsaturated silane compound to be reacted is in the above range, the resulting silane-modified polyolefin resin is excellent in adhesive strength.
  • the silane-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.1 to 30 g / 10 minutes, particularly 0.3 to 15 g / 10 minutes. More preferably, it is 0.5 to 10 g / 10 min.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.1 g / 10 minutes, extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • silane-modified polyolefin resin Commercially available products can also be used as the silane-modified polyolefin resin.
  • Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based.
  • Linklon registered trademark
  • Low density polyethylene-based linklon linear low-density polyethylene-based linkron
  • ultra-low-density polyethylene-based ultra-low-density polyethylene-based.
  • Rincron of ethylene-vinyl acetate copolymer system can be preferably used.
  • the ionomer is not particularly limited, but for example, an olefin resin molecule such as an ethylene- (meth) acrylic acid copolymer or an ethylene-fumaric acid copolymer is preferably bonded with a metal ion.
  • an olefin resin molecule such as an ethylene- (meth) acrylic acid copolymer or an ethylene-fumaric acid copolymer is preferably bonded with a metal ion.
  • the ethylene- (meth) acrylic acid copolymer is a copolymer of ethylene and acrylic acid and / or methacrylic acid.
  • an ethylene-methacrylic acid copolymer that is a copolymer of ethylene and methacrylic acid is used.
  • the content of (meth) acrylic acid as a monomer unit in the ethylene- (meth) acrylic acid copolymer is preferably 2 to 20% by mass, particularly preferably 3 to 15% by mass. .
  • the content of (meth) acrylic acid is less than 2% by mass, the crystallinity of the resin becomes high and there is a possibility that the resin becomes opaque.
  • the content of (meth) acrylic acid exceeds 20% by mass, the desired water vapor barrier property may not be obtained.
  • first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, if desired. You may contain various additives, such as a lubricant, an antiblocking agent, and a silane coupling agent.
  • first and second adhesive resin layers 11A and 11B may be the same or different.
  • the water vapor barrier resin layer 12 is a resin layer for preventing / suppressing permeation of water vapor in the film sealing material 1.
  • the water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
  • the resin constituting the water vapor barrier resin layer 12 is not particularly limited as long as it satisfies the above water vapor transmission rate range.
  • cycloolefin resin, linear low density polyethylene, low density polyethylene, medium It is preferably at least one thermoplastic resin selected from the group consisting of density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer and rubber resin.
  • the film-shaped sealing material 1 can easily achieve the water vapor transmission rate described above.
  • the water vapor barrier resin layer 12 is composed of a cycloolefin resin, a low density polyethylene, a linear low density polyethylene, and a rubber resin because the water vapor permeability is low and the desired water vapor permeability is easily achieved. It is preferable to include at least one selected from the group consisting of
  • the cycloolefin-based resin refers to a polymer resin (including the concept of copolymer) containing cycloolefin as a monomer component constituting the polymer, and the monomer component may be a polymer composed only of cycloolefin. Further, it may be a polymer (copolymer) containing cycloolefin and other monomers as monomer components.
  • the other monomer is not particularly limited as long as it does not hinder the purpose of the film-like sealing material 1 according to the present embodiment, and examples thereof include ⁇ -olefins having 2 or more carbon atoms such as ethylene and propylene, and (meth) acrylic acid esters. Etc.
  • the cycloolefin resin is a monomer component because it has excellent adhesion to the first and second adhesive resin layers 11A and 11B and can prevent delamination of the film-shaped sealing material 1.
  • a copolymer containing cycloolefin and ethylene is preferred.
  • the cycloolefin resin does not have a hydrophilic group.
  • the water vapor barrier property may be lowered.
  • the hydrophilic group include a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a sulfonic acid group, and a mercapto group.
  • the cycloolefin-based resin may have a hydrophobic group. If it is a hydrophobic group, there is no possibility that water vapor
  • the hydrophobic group include an alkyl group and an aryl group.
  • cycloolefin-based resin As a preferred cycloolefin-based resin, the following structural formula (a) (In the formula (a), m and n are .R 1 and R 2 is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.)
  • R 1 and R 2 May be bonded to form a ring.
  • a polymer containing only cycloolefin as a monomer component; COP), and the following structural formula (d) (In formula (d), n is an integer of 1 or more, and R 1 and R 2 represent a hydrogen atom or an alkyl group, and may be the same or different. R 1 and R 2 May be bonded to form a ring.)
  • a cycloolefin polymer polymer containing only cycloolefin as a monomer component; COP).
  • a commercially available product can also be used as the cycloolefin polymer.
  • Examples of commercially available products include ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd., ring-opening metathesis polymer hydrogenated polymer of norbornene monomer), TOPAS (registered trademark) (manufactured by Polyplastics Co., Ltd., copolymer of norbornene and ethylene).
  • ZEONOR registered trademark
  • Apel registered trademark
  • Mitsui Chemicals ethylene and tetracyclododecene Copolymer
  • Arton registered trademark
  • rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, halogenated butyl rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate -Butadiene copolymer, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-nonconjugated diene ternary copolymer Examples
  • the polyisobutylene-based resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), and the monomer component may be a homopolymer composed only of isobutylene, or isobutylene and others as the monomer component. It may be a copolymer obtained by polymerizing these monomers.
  • the polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.
  • Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more.
  • isobutylene resin is a copolymer
  • isobutylene is the maximum amount of monomer as a main component in the raw material monomer.
  • the polyisobutylene-based resin is preferably a homopolymer whose monomer component is composed only of isobutylene, and an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component from the viewpoint of excellent water vapor barrier properties. .
  • the water vapor barrier resin layer 12 may contain other resin components in the range satisfying the range of the water vapor transmission rate in addition to the above-described resin.
  • Other resin components include polyethylene, polypropylene, polybutene, ethylene- ⁇ olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer Olefin resins such as coalescence (excluding cycloolefin resins), urethane resins, rubber resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins And silane-based resins.
  • the water vapor barrier resin layer 12 is made of various materials such as a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, and an antiblocking agent, if desired. You may contain an additive etc.
  • the film-shaped sealing material 1 can be manufactured by a conventional method. For example, a method in which the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B are co-extruded so as to be laminated in that order, the first adhesive property A single-layer film (first adhesive resin film) as the resin layer 11A and a single-layer film (second adhesive resin film) as the second adhesive resin layer 11B are prepared, respectively.
  • the film-form sealing material 1 can also be manufactured by the method of laminating
  • steam barrier resin layer 12 The method for forming the film (water vapor barrier resin film) is not particularly limited, and examples thereof include a melt extrusion method, a calendar method, a dry method, and a solution method.
  • each layer may be formed by applying a solution obtained by dissolving the resin constituting each layer described above in an organic solvent by a known application method and drying the obtained coating film as appropriate.
  • first and second adhesive resin layers 11A, 11B contain a thermoplastic resin
  • the first and second adhesive resin layers 11A, 11B first adhesive resin film, second adhesive resin film
  • the water vapor barrier resin layer 12 water vapor barrier resin film
  • the heating temperature is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B (first adhesive resin film and second adhesive resin film) are softened.
  • the film-shaped sealing material 1 according to the present embodiment has an adhesive strength to a glass plate of 3 N / 25 mm or more, a temperature of 40 ° C., and a relative humidity of 90% RH. Under the environment, the water vapor transmission rate W in terms of a thickness of 50 ⁇ m is controlled to 10 g / m 2 ⁇ day or less, and is excellent in water vapor barrier properties and adhesiveness.
  • the performance of the sealing material is due to the adhesive strength to the adherend and the water vapor transmission rate of the sealing material, and according to the film-shaped sealing material 1 according to the present embodiment, it is used for sealing various things. In particular, it can be suitably used for sealing an electronic element in an electronic device.
  • a module for a display device having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, an electronic paper, a solar cell module, and the like can be given.
  • the film-like sealing material 1 according to this embodiment is suitably used. Can be used.
  • the method of sealing an electronic element using the film-form sealing material 1 which concerns on this embodiment is demonstrated by the term of the below-mentioned electronic device.
  • the sealing sheet 2 As shown in FIG. 2, the sealing sheet 2 according to this embodiment includes the above-described film-shaped sealing material 1 and a gas barrier film 21 laminated on one surface of the film-shaped sealing material 1.
  • the gas barrier film 21 is a film having characteristics that make it difficult for gas such as water vapor and oxygen to pass therethrough. Further, when the sealing sheet 2 is used for applications that require transparency, such as a display device module, electronic paper, a solar cell module, and a top emission type electronic device described later, the gas barrier film 21 is transparent. It is preferable.
  • the gas barrier film 21 is preferably a laminate of a base film and a gas barrier layer. As such a gas barrier film 21, for example, one having a gas barrier layer formed directly or via another layer on one or both sides of a base film, or having a gas barrier layer in the middle of a base film is used. can do. Among them, the gas barrier film 21 is preferably one in which a gas barrier layer is formed directly or via another layer on one side or both sides of a base film.
  • the base film examples include polyolefin such as polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyester such as polyethylene terephthalate and polybutylene terephthalate, polychlorinated Acrylic resins such as vinyl, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, Examples thereof include a film made of a resin such as an ABS resin or an ionomer resin, or a laminated film thereof.
  • a resin such as an ABS resin or an ionomer resin, or a laminated film thereof.
  • a film made of polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate and the like is preferable.
  • the base film may be a stretched film or an unstretched film. Further, the base film may contain various additives such as an ultraviolet absorber.
  • the thickness of the base film is preferably 1 to 500 ⁇ m, particularly preferably 5 to 300 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • the gas barrier layer is laminated for the purpose of imparting gas barrier properties to the base film.
  • the material of the gas barrier layer is not particularly limited as long as the gas barrier property of the gas barrier film 21 can be set to a desired level.
  • the material of the gas barrier layer include inorganic oxides such as silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide and tin oxide, and inorganic nitrides such as silicon nitride and aluminum nitride.
  • inorganic oxynitrides such as silicon oxynitride, and metals such as aluminum, magnesium, zinc, and tin. These can be used individually by 1 type or in combination of 2 or more types.
  • the gas barrier layer may be a polysilazane compound converted into a siliceous film by a known method. Further, the gas barrier layer may be a layer obtained by plasma ion implantation into a layer containing a silicon compound such as a polysilazane compound, a polycarbosilane compound, a polysilane compound, a polyorganosiloxane compound, or a tetraorganosilane compound.
  • Examples of ions implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, Examples include ions of metals such as silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
  • the thickness of the gas barrier layer is preferably 1 nm to 10 ⁇ m, more preferably 10 to 1000 nm, particularly preferably 20 to 500 nm, and further preferably 50 to 200 nm.
  • the gas barrier layer may be a single layer or a plurality of layers, but from the viewpoint of obtaining higher gas barrier properties, the gas barrier layer is preferably a plurality of layers.
  • the method for forming the gas barrier layer may be appropriately selected according to the material to be used.
  • the gas barrier layer material is formed on a base film by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like, or the gas barrier layer material is dissolved in an organic solvent.
  • coating a solution to a base film is mentioned.
  • the water vapor permeability of the gas barrier film 21 is preferably 0.5 g / m 2 ⁇ day or less, particularly preferably 0.1 g / m 2 ⁇ day or less at 40 ° C. and 90% RH, It is preferably 0.05 g / m 2 ⁇ day or less.
  • the film-like sealing material 1 and the gas barrier film 21 may be laminated and laminated. Since the film-shaped sealing material 1 according to the present embodiment has the first and second adhesive resin layers 11A and 11B excellent in adhesive strength, the adhesive resin layer (first adhesive property in FIG. 2). The resin layer 11A) adheres firmly to the gas barrier film 21. Therefore, when an electronic device or the like is sealed using the sealing sheet 2, it is possible to effectively prevent water vapor from entering between the gas barrier film 21 and the film-shaped sealing material 1. In addition, when the gas barrier film 21 has a gas barrier layer on one side, the gas barrier film 21 and the film-shaped sealing material 1 are preferably laminated so that the gas barrier layer is on the film-shaped sealing material 1 side.
  • first and second adhesive resin layers 11A and 11B contain a thermoplastic resin
  • the heating temperature is preferably equal to or higher than the temperature at which the adhesive resin layer (the first adhesive resin layer 11A in FIG. 2) of the film-like sealing material 1 is softened.
  • the sealing sheet 2 according to the present embodiment can be used for the same application as that of the film-shaped sealing material 1 described above, and particularly has a display having an organic EL element or the like that requires high water vapor barrier properties and adhesiveness. It can use suitably for sealing of the electronic element in electronic devices, such as an apparatus module, electronic paper, and a solar cell module.
  • the adhesive resin layer (second adhesive resin layer 11 ⁇ / b> B in FIG. 2) opposite to the side on which the gas barrier film 21 is laminated and the adherend are bonded. Sealing can be performed by thermocompression bonding.
  • the electronic device according to one embodiment of the present invention is sealed with the film-shaped sealing material 1 according to the above-described embodiment.
  • the electronic device 3 ⁇ / b> A according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a film-like sealing material that seals the electronic element 32. 1 and the sealing member 33 laminated
  • the sealing member 33 For example, a glass plate etc. are mentioned.
  • an electronic device is sealed with the sealing sheet 2 according to the above-described embodiment.
  • the electronic device 3 ⁇ / b> B according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a sealing sheet 2 that seals the electronic element 32.
  • the sealing sheet 2 is a laminated body of the film-shaped sealing material 1 and the gas barrier film 21 laminated on one surface of the film-shaped sealing material 1.
  • These electronic devices 3A and 3B include, for example, a liquid crystal element, an LED element, an organic EL element, and the like as an electronic element 32, an electrophoretic element, an electronic granular element, and a cholesteric liquid crystal element as the electronic element 32.
  • the electronic devices 3A and 3B may be top emission type electronic devices or bottom emission type electronic devices.
  • the substrate 31 is preferably a transparent substrate.
  • the sealing member 33 and the gas barrier film 21 are preferably transparent.
  • the substrate 31 is appropriately selected according to the type of the electronic devices 3A and 3B, and for example, a glass plate or a resin film is preferably exemplified.
  • a glass plate or a resin film is preferably exemplified.
  • the material of the glass plate include non-alkali glass, soda lime glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, barium / strontium-containing glass, inorganic glass made of quartz, hybrid glass, and the like.
  • a resin film the base film illustrated with the gas barrier film 21 is mentioned, for example.
  • the thickness of the substrate 31 is appropriately set according to the types of the electronic devices 3A and 3B.
  • the method for manufacturing the electronic device 3A is not particularly limited.
  • the electronic element 32 is formed on the substrate 31 by a conventional method.
  • the film-shaped sealing material 1 is placed so as to cover the electronic element 32, and a sealing member 33 such as a glass plate is placed on the film-shaped sealing material 1, and they are bonded together.
  • the electronic device 3 ⁇ / b> A can be manufactured by sealing the electronic element 32.
  • the laminated body which bonded the film-form sealing material 1 and the sealing member 33 beforehand may be obtained, and this laminated body may be bonded with the electronic element 32, and the electronic device 3A may be manufactured.
  • the method for manufacturing the electronic device 3B is not particularly limited.
  • the sealing sheet 2 is placed so as to cover the electronic element 32 formed on the substrate 31 so that the film-shaped sealing material 1 is on the electronic element 32 side, and the sealing sheet 2 is bonded to the electronic element 32.
  • the electronic device 3B can be manufactured by sealing.
  • Sealing may be performed at normal pressure, may be performed while applying pressure, may be performed in a reduced pressure atmosphere, or may be performed in combination. Further, when the first and second adhesive resin layers 11A and 11B contain a thermoplastic resin, when the film-like sealing material 1 and the electronic element 32 are bonded together, they are heated (thermocompression bonded). Preferably, the film-shaped sealing material 1 and the electronic element 32, the substrate 31, and the sealing member 33 or the gas barrier film 21 are firmly bonded by heating.
  • the heating temperature at the time of bonding is usually preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 are softened.
  • the first and second adhesive resin layers 11A and 11B in the present embodiment contain both an acid-modified polyolefin resin and a silane-modified polyolefin resin, so that thermocompression bonding in a relatively short time, specifically, Can be sealed in 1 second to 5 minutes.
  • the film-form sealing material 1 which concerns on this embodiment is the thing excellent in the productivity at the time of device manufacture.
  • the electronic element 32 since the electronic element 32 is covered with the film-shaped sealing material 1 according to the present embodiment, the water vapor from the outside is the water vapor of the film-shaped sealing material 1. Since it is blocked and suppressed by the barrier resin layer 12 and reaches the electronic element 32, the electronic element 32 is hardly affected by moisture. Moreover, since the film-form sealing material 1 is equipped with the 1st and 2nd adhesive resin layers 11A and 11B excellent in adhesive force, the film-form sealing material 1 and the board
  • the first adhesive resin layer 11A and / or the second adhesive resin layer 11B is laminated on the water vapor barrier resin layer 12 via other layers. Also good. Further, a release sheet may be laminated on the first adhesive resin layer 11A and / or the second adhesive resin layer 11B. The release sheet is used for forming the adhesive resin layer or is provided for the purpose of protecting the adhesive resin layer, and is peeled off when the film-shaped sealing material 1 is used.
  • Example 1 ⁇ Production of film-like encapsulant>
  • the materials constituting the first adhesive resin layer, the second adhesive resin layer, and the water vapor barrier resin layer shown in Table 1 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the thickness was 10 ⁇ m.
  • a film-like encapsulant was produced by laminating a first adhesive resin layer, a 30 ⁇ m thick water vapor barrier resin layer, and a 10 ⁇ m thick second adhesive resin layer in that order.
  • a polysilazane compound (a coating material mainly composed of perhydropolysilazane, Clariant Japan Co., Ltd., Aquamica NL110-20) is spun. It was applied by a coating method and heated at 120 ° C. for 1 minute to form a polysilazane layer containing perhydropolysilazane having a thickness of 150 nm. Next, using a plasma ion implantation apparatus, argon was ion-implanted on the surface of the polysilazane layer under the following conditions to form a gas barrier layer, thereby producing a gas barrier film A.
  • the plasma ion implantation apparatus and the plasma ion implantation conditions used for forming the gas barrier layer are as follows.
  • sealing sheet B ⁇ Preparation of sealing sheet B>
  • the obtained film-shaped encapsulant and gas barrier film B laminated film made by Aya Aluminum Co., Ltd. having a 12 ⁇ m thick polyethylene terephthalate sheet bonded to both sides of a 7 ⁇ m thick aluminum foil (gas barrier layer) with a urethane adhesive layer Were bonded together while heating at 130 ° C. to obtain a sealing sheet B.
  • Al aluminum (manufactured by High Purity Chemical Laboratory Co., Ltd.) was deposited at a rate of 0.1 nm / s to 100 nm to form a cathode.
  • an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50 ⁇ / ⁇ ) was formed by sputtering to produce an anode, whereby an organic EL device was obtained.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • the sealing sheet A is dried by heating at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet A, and then left as it is to room temperature. Cooled down. And the sealing sheet A is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, and they are thermocompression-bonded at 100 degreeC, and organic The EL element was sealed to obtain a top emission type electronic device.
  • ITO indium tin oxide
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (manufactured by Luminescence Technology) was 60 nm
  • Tris (8- Hydroxy-quinolinate) Aluminum (manufactured by Luminescence Technology) at 40 nm
  • 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminesense Technology) at 10 nm
  • (8-hydroxy-quinolinolate) lithium was sequentially deposited at a rate of 10 nm and 0.1 to 0.2 nm / s to form a light emitting layer.
  • Al aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, thereby obtaining an organic EL device.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • the sealing sheet B was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet B, and then left to cool to room temperature. . And the sealing sheet B is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, and they are thermocompression-bonded at 100 degreeC, and organic The EL element was sealed to obtain a bottom emission type electronic device.
  • Examples 2 to 10, Comparative Examples 1 to 4 A film-like sealing material was produced in the same manner as in Example 1 except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer and the thickness of each layer were changed as shown in Table 1. Using this film-shaped encapsulant, encapsulating sheets A and B were produced in the same manner as in Example 1 to obtain top emission type and bottom emission type electronic devices.
  • Admer SF731 Maleic anhydride-modified polyethylene resin (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point: 43 ° C., 190 ° C., MFR at load 20.2 N: 2.6 g / 10 min)
  • Linkron XLE815N Silane-modified linear low-density polyethylene (Mitsubishi Chemical Co., Ltd., trade name “Linklon XLE815N”, MFR at 190 ° C.
  • Ultrasen 630 Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, trade name “Ultrasen 630”) ⁇ Nucleel N1207C: ethylene-methacrylic acid copolymer (Mitsui-DuPont Polychemical Co., Ltd., trade name “Nucrel N1207C”) ⁇ High Milan 1650: Ethylene ionomer (Zn type) (Mitsui-DuPont Polychemical Co., Ltd., trade name “High Milan 1650”) [Water vapor barrier resin layer] TOPAS9506F-04: Cycloolefin polymer represented by the structural formula (a) described above (trade name “TOPAS9506F-04”, glass transition temperature 65 ° C., manufactured by Polyplastics Co., Ltd.) APL8008T: Cycloolefin polymer represented by the above structural formula (b) (Mitsui Chemicals,
  • the obtained test piece was allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours after being bonded, and then in that environment, using a tensile tester (manufactured by Orientec, Tensilon), a peeling rate of 300 mm. / Min, a peel test was performed under the conditions of a peel angle of 180 °, and the adhesive strength (N / 25 mm) was measured. The results are shown in Table 1. In Table 1, when the adhesive strength was 1 N / 25 mm or less, it was expressed as “ ⁇ 1”.
  • the film-shaped encapsulant obtained in the examples is controlled to a specific range of water vapor transmission rate and adhesive force, and is sealed by the film-form encapsulant obtained in the examples.
  • the produced organic EL element had almost no dark spots, and the performance of the electronic device was good.
  • the film-shaped sealing material of the comparative example has a high water vapor transmission rate, the organic EL element sealed with the film-shaped sealing material has many dark spots, and the performance of the electronic device is inferior. .
  • the film-form sealing material of the comparative example 3 had too low adhesive force, and could not seal an organic EL element.
  • the film-like sealing material and the sealing sheet according to the present invention are suitably used for, for example, an organic EL module and electronic paper.
  • the electronic device according to the present invention is suitable as an organic EL module or electronic paper, for example.

Abstract

　A film-shaped sealing material (1) provided with: first and second adhesive resin layers (11A, 11B) that are adhesive with respect to an item that is to be adhered to; and a resin layer (12) having water vapour barrier properties that is located between the first adhesive resin layer (11A) and the second adhesive resin layer (11B), wherein the surface of either the first adhesive resin layer (11A) or the second adhesive resin layer (11B) has an adhesive strength with respect to a glass plate, when bonded to the glass plate, of at least 3N/25mm, and has a water vapour transmission rate (W) of 10g/m2·day or less for a thickness of 50μm (when the thickness of the film-shaped sealing material is 50μm) at 40°C and in an environment having a relative humidity (RH) of 90%. This film-shaped sealing material (1) has excellent water vapour barrier properties and adhesive properties.

Description

フィルム状封止材、封止シートおよび電子デバイスFilm-like sealing material, sealing sheet, and electronic device
　本発明は、電子素子等を封止することのできるフィルム状封止材および封止シート、ならびにそれらによって電子素子が封止された電子デバイスに関するものである。 The present invention relates to a film-like sealing material and a sealing sheet that can seal an electronic element and the like, and an electronic device in which the electronic element is sealed by them.
　電子デバイス、例えば、液晶素子、発光ダイオード（ＬＥＤ素子）等を有する表示装置用モジュール、太陽電池セルを有する太陽電池モジュールなどにおいては、デバイス内部の電子素子に水分や酸素が浸入して悪影響が及ぼされることを防止するために、ガラス板や樹脂フィルムを使用して電子素子をカバーしている。 In an electronic device, for example, a display module having a liquid crystal element, a light emitting diode (LED element), or a solar battery module having a solar cell, moisture and oxygen enter the electronic element inside the device and have an adverse effect. In order to prevent this, the electronic element is covered using a glass plate or a resin film.
　そして、ガラス板や樹脂フィルムと、電子素子とを複合する際には、電子素子を封止するフィルム状の封止材が用いられる。封止材としては、例えば特許文献１，２等に示されるように、エチレン－酢酸ビニル共重合体（ＥＶＡ）や、ポリビニルブチラール（ＰＶＢ）が主に使用される。 And when a glass plate or a resin film is combined with an electronic element, a film-like sealing material for sealing the electronic element is used. As the sealing material, for example, as shown in Patent Documents 1 and 2, etc., ethylene-vinyl acetate copolymer (EVA) and polyvinyl butyral (PVB) are mainly used.
　上記の樹脂以外にも、例えば、特許文献３には、エチレン－メタクリル酸共重合体（ＥＭＡＡ）が使用できることが開示されており、特許文献４には、アイオノマー樹脂が使用できることが開示されており、特許文献５には、脂環式構造含有重合体が使用できることが開示されている。また、特許文献６には、低密度ポリエチレン樹脂または直鎖状低密度ポリエチレン樹脂からなる中間層と、その両面に接着剤層を有する三層構造の太陽電池用充填材シートが開示されている。特許文献６に記載の三層構造の太陽電池用充填材シートは、従来の単層のシートに比べ、熱収縮を防ぎ、かつ接着性に優れるものである。 In addition to the above resins, for example, Patent Document 3 discloses that an ethylene-methacrylic acid copolymer (EMAA) can be used, and Patent Document 4 discloses that an ionomer resin can be used. Patent Document 5 discloses that an alicyclic structure-containing polymer can be used. Patent Document 6 discloses a three-layer structure solar cell filler sheet having an intermediate layer made of a low-density polyethylene resin or a linear low-density polyethylene resin, and adhesive layers on both sides thereof. The solar cell filler sheet having a three-layer structure described in Patent Document 6 prevents thermal shrinkage and is excellent in adhesiveness as compared with a conventional single-layer sheet.
特開平６－１７７４１２号公報Japanese Patent Application Laid-Open No. 6-177412 特開平１０－２３３５２１号公報Japanese Patent Laid-Open No. 10-233521 特開２０００－２５２４９１号公報JP 2000-252491 A 特開２００６－６６７６２号公報JP 2006-66762 A 特開２００３－５９６４５号公報JP 2003-59645 A 特開２０１２－２１６８０５号公報JP 2012-216805 A
　しかしながら、近年注目されている有機エレクトロルミネッセンス（有機ＥＬ）素子を有する表示装置用モジュールや、電子ペーパー、有機薄膜太陽電池等の電子デバイスにおいては、より高い水蒸気バリア性および接着性を有する封止材が求められており、従来の封止材では、依然として水蒸気バリア性は不十分である。また、従来の封止材は、ガラス板や樹脂フィルムに対する接着性が不十分であるため、ガラス板や樹脂フィルムと封止材との間に水蒸気が浸入したり、ガラス板や樹脂フィルムが剥離したりすることにより、電子素子に悪影響が及んでしまうことが懸念される。 However, in an electronic device such as a display device module having an organic electroluminescence (organic EL) element that has been attracting attention in recent years, electronic paper, an organic thin film solar cell, etc., a sealing material having higher water vapor barrier properties and adhesiveness Therefore, the conventional sealing material still has insufficient water vapor barrier properties. In addition, since conventional sealing materials have insufficient adhesion to glass plates and resin films, water vapor enters between the glass plates and resin films and the sealing materials, and the glass plates and resin films peel off. It is feared that the electronic device will be adversely affected.
　本発明は、このような実状に鑑みてなされたものであり、水蒸気バリア性および接着性に優れたフィルム状封止材、封止シートおよび電子デバイスを提供することを目的とする。 The present invention has been made in view of such a situation, and an object thereof is to provide a film-shaped sealing material, a sealing sheet, and an electronic device excellent in water vapor barrier properties and adhesiveness.
　上記目的を達成するために、第１に本発明は、被着体に対して接着性を示す第１および第２の接着性樹脂層と、前記第１の接着性樹脂層と前記第２の接着性樹脂層との間に位置する水蒸気バリア性樹脂層とを備えたフィルム状封止材であって、前記第１の接着性樹脂層または前記第２の接着性樹脂層のいずれか一方の面をガラス板に貼り合わせた際の前記ガラス板に対する接着力が、３Ｎ／２５ｍｍ以上であり、温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算（フィルム状封止材の厚みを５０μｍとしたとき）の水蒸気透過率Ｗが、１０ｇ／ｍ２・ｄａｙ以下であることを特徴とするフィルム状封止材を提供する（発明１）。 In order to achieve the above object, first, the present invention includes first and second adhesive resin layers exhibiting adhesion to an adherend, the first adhesive resin layer, and the second adhesive layer. It is a film-form sealing material provided with the water vapor | steam barrier resin layer located between adhesive resin layers, Comprising: Either one of the said 1st adhesive resin layer or the said 2nd adhesive resin layer When the surface is bonded to the glass plate, the adhesive strength to the glass plate is 3 N / 25 mm or more, and converted into a thickness of 50 μm (the thickness of the film-like sealing material) in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH. The film-like sealing material is characterized in that the water vapor transmission rate W is 10 g / m 2 · day or less (Invention 1).
　上記発明（発明１）に係るフィルム状封止材は、第１および第２の接着性樹脂層と、それらの間に位置する水蒸気バリア性樹脂層とを備えることにより、接着力および水蒸気透過率が上記のように制御されており、接着性および水蒸気バリア性に優れる。 The film-shaped sealing material according to the above invention (Invention 1) includes the first and second adhesive resin layers and the water vapor barrier resin layer positioned therebetween, whereby the adhesive force and the water vapor transmission rate are obtained. Is controlled as described above, and is excellent in adhesion and water vapor barrier properties.
　上記発明（発明１）においては、温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算の前記第１の接着性樹脂層の水蒸気透過率をＷ１（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算の前記第２の接着性樹脂層の水蒸気透過率をＷ２（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算の前記水蒸気バリア性樹脂層の水蒸気透過率をＷ３（ｇ／ｍ２・ｄａｙ）としたときに、Ｗ１、Ｗ２およびＷ３が次の関係を満たす
　Ｗ１＞Ｗ３、Ｗ２＞Ｗ３、かつＷ３≦１０
ことが好ましい（発明２）。 In the above invention (Invention 1), the water vapor transmission rate of the first adhesive resin layer converted to a thickness of 50 μm in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH is W1 (g / m 2 · day), The water vapor transmission rate of the second adhesive resin layer in terms of thickness 50 μm is W2 (g / m 2 · day), and the water vapor transmission rate of the water vapor barrier resin layer in terms of thickness 50 μm is W 3 (g / m 2 · day). ), W1, W2, and W3 satisfy the following relationship: W1> W3, W2> W3, and W3 ≦ 10
It is preferable (Invention 2).
　上記発明（発明１，２）においては、前記第１の接着性樹脂層の厚さをＴ１（μｍ）、前記第２の接着性樹脂層の厚さをＴ２（μｍ）、前記水蒸気バリア性樹脂層の厚さをＴ３（μｍ）としたときに、Ｔ１、Ｔ２およびＴ３が次の関係を満たす
　０．１＜{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}＜０．９９
　１≦Ｔ１≦１００
　１≦Ｔ２≦１００
　５≦Ｔ３≦３００
ことが好ましい（発明３）。 In the above inventions (Inventions 1 and 2), the thickness of the first adhesive resin layer is T1 (μm), the thickness of the second adhesive resin layer is T2 (μm), and the water vapor barrier resin When the layer thickness is T3 (μm), T1, T2 and T3 satisfy the following relationship: 0.1 <{T3 / (T1 + T2 + T3)} <0.99
1 ≦ T1 ≦ 100
1 ≦ T2 ≦ 100
5 ≦ T3 ≦ 300
(Invention 3)
　上記発明（発明１～３）において、前記第１および第２の接着性樹脂層は、前記水蒸気バリア性樹脂層に直接積層されており、それらの３層構造からなることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the first and second adhesive resin layers are directly laminated on the water vapor barrier resin layer, and preferably have a three-layer structure thereof (Invention 4). .
　第２に本発明は、前記フィルム状封止材（発明１～４）と、前記フィルム状封止材の片面に積層されたガスバリアフィルムとを備えたことを特徴とする封止シートを提供する（発明５）。 Secondly, the present invention provides a sealing sheet comprising the film-like sealing material (Inventions 1 to 4) and a gas barrier film laminated on one surface of the film-like sealing material. (Invention 5).
　第３に本発明は、前記フィルム状封止材（発明１～４）によって封止されたことを特徴とする電子デバイスを提供する（発明６）。 Thirdly, the present invention provides an electronic device characterized by being sealed with the film-like sealing material (Invention 1 to 4) (Invention 6).
　第４に本発明は、前記封止シート（発明５）によって封止されたことを特徴とする電子デバイスを提供する（発明７）。 Fourthly, the present invention provides an electronic device characterized by being sealed by the sealing sheet (Invention 5) (Invention 7).
　本発明に係るフィルム状封止材は、被着体に対して接着性を示す第１および第２の接着性樹脂層と、第１の接着性樹脂層と第２の接着性樹脂層との間に位置する水蒸気バリア性樹脂層とを備えることにより、ガラス板に対する接着力が、３Ｎ／２５ｍｍ以上に制御されるとともに、温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算（フィルム状封止材の厚みを５０μｍとしたとき）の水蒸気透過率Ｗが、１０ｇ／ｍ２・ｄａｙ以下に制御されており、接着性および水蒸気バリア性に優れる。封止材の性能は、被着体に対する接着力と、封止材の水蒸気透過率とに起因しており、本発明のフィルム状封止材によれば、電子素子を確実に封止することができる。 The film-shaped sealing material according to the present invention includes first and second adhesive resin layers exhibiting adhesiveness to an adherend, a first adhesive resin layer, and a second adhesive resin layer. By providing the water vapor barrier resin layer positioned between them, the adhesive strength to the glass plate is controlled to 3 N / 25 mm or more, and the thickness is converted to 50 μm in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH ( When the thickness of the film-shaped sealing material is 50 μm), the water vapor transmission rate W is controlled to 10 g / m 2 · day or less, and the adhesiveness and the water vapor barrier property are excellent. The performance of the sealing material is caused by the adhesive strength to the adherend and the water vapor transmission rate of the sealing material. According to the film-shaped sealing material of the present invention, the electronic device can be reliably sealed. Can do.
本発明の一実施形態に係るフィルム状封止材の概略断面図である。It is a schematic sectional drawing of the film-form sealing material which concerns on one Embodiment of this invention. 本発明の一実施形態に係る封止シートの概略断面図である。It is a schematic sectional drawing of the sealing sheet which concerns on one Embodiment of this invention. 本発明の一実施形態に係る電子デバイスの概略断面図である。It is a schematic sectional drawing of the electronic device which concerns on one Embodiment of this invention. 本発明の他の実施形態に係る電子デバイスの概略断面図である。It is a schematic sectional drawing of the electronic device which concerns on other embodiment of this invention.
　以下、本発明の実施形態について説明する。
〔フィルム状封止材〕
　図１に示すように、本実施形態に係るフィルム状封止材１は、第１および第２の接着性樹脂層１１Ａ，１１Ｂと、第１の接着性樹脂層１１Ａと第２の接着性樹脂層１１Ｂとの間に位置する水蒸気バリア性樹脂層１２とを備える。なお、本実施形態では、第１および第２の接着性樹脂層１１Ａ，１１Ｂは、水蒸気バリア性樹脂層１２に直接積層されており、本実施形態に係るフィルム状封止材１は、それらの３層構造からなるが、本発明はこれに限定されるものではない。 Hereinafter, embodiments of the present invention will be described.
[Film sealant]
As shown in FIG. 1, the film-shaped sealing material 1 which concerns on this embodiment is 1st and 2nd adhesive resin layer 11A, 11B, 1st adhesive resin layer 11A, and 2nd adhesive resin. And a water vapor barrier resin layer 12 positioned between the layer 11B. In the present embodiment, the first and second adhesive resin layers 11A and 11B are directly laminated on the water vapor barrier resin layer 12, and the film-shaped sealing material 1 according to the present embodiment includes those layers. Although it consists of a three-layer structure, this invention is not limited to this.
　フィルム状封止材１は、水蒸気バリア性樹脂層１２が、第１の接着性樹脂層１１Ａと第２の接着性樹脂層１１Ｂとの間に配置されることにより、水蒸気透過率が制御されており、かつ、水蒸気バリア性樹脂層１２の両側に第１および第２の接着性樹脂層１１Ａ，１１Ｂが配置されることにより、高い接着性を達成している。 The film-shaped sealing material 1 has a water vapor transmission rate controlled by disposing the water vapor barrier resin layer 12 between the first adhesive resin layer 11A and the second adhesive resin layer 11B. In addition, since the first and second adhesive resin layers 11A and 11B are disposed on both sides of the water vapor barrier resin layer 12, high adhesiveness is achieved.
　フィルム状封止材１は、第１の接着性樹脂層１１Ａまたは第２の接着性樹脂層１１Ｂのいずれか一方の面をガラス板に貼り合わせた際の当該ガラス板に対する接着力が、３Ｎ／２５ｍｍ以上である。接着力が上記範囲内にあることにより、フィルム状封止材１を介して、ガラス板や樹脂フィル等の封止部材と電子素子等の封止対象物とを強固に貼り合わせ、封止対象物を確実に封止するとともに、ガラス板や樹脂フィルム等の封止部材とフィルム状封止材１との間に水分が浸入することがなく、また、フィルム状封止材１と封止対象物との間で、浮きや剥がれ等が発生することを防止することができる。 The film-shaped sealing material 1 has an adhesive force with respect to the glass plate of 3N / when either one surface of the first adhesive resin layer 11A or the second adhesive resin layer 11B is bonded to the glass plate. It is 25 mm or more. When the adhesive force is within the above range, a sealing member such as a glass plate or a resin film and a sealing object such as an electronic element are firmly bonded to each other through the film-like sealing material 1 and sealed. While sealing an object reliably, a water | moisture content does not penetrate between sealing members, such as a glass plate and a resin film, and the film-form sealing material 1, and the film-form sealing material 1 and sealing object It is possible to prevent floating and peeling between objects.
　上記接着力は、３Ｎ／２５ｍｍ以上であることが好ましく、特に５Ｎ／２５ｍｍ以上であることが好ましく、さらには１０Ｎ／２５ｍｍ以上であることが好ましい。接着力の上限は特に制限はないが、通常は、５００Ｎ／２５ｍｍ以下であることが好ましい。なお、接着力の測定方法は、後述する試験例に示す通りである。 The adhesive strength is preferably 3 N / 25 mm or more, particularly preferably 5 N / 25 mm or more, and more preferably 10 N / 25 mm or more. The upper limit of the adhesive force is not particularly limited, but usually it is preferably 500 N / 25 mm or less. In addition, the measuring method of adhesive force is as showing to the test example mentioned later.
　また、フィルム状封止材１は、厚み５０μｍ換算（フィルム状封止材１の厚みを５０μｍとしたとき）の、温度４０℃、相対湿度９０％ＲＨの環境下における水蒸気透過率Ｗが、１０ｇ／ｍ２・ｄａｙ以下である。水蒸気透過率Ｗが上記範囲内にあることにより、電子素子等の封止対象物を封止したときに、外部からの水蒸気が、当該フィルム状封止材１で効果的にブロックされて、封止対象物に到達することが防止・抑制され、封止対象物が水分の悪影響を受け難くなる。 Moreover, the film-form sealing material 1 has a water vapor transmission rate W of 10 g in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH in terms of a thickness of 50 μm (when the thickness of the film-shaped sealing material 1 is 50 μm). / M 2 · day or less. When the water vapor transmission rate W is within the above range, when sealing an object to be sealed such as an electronic element, water vapor from the outside is effectively blocked by the film-shaped sealing material 1 and sealed. Reaching the object to be stopped is prevented / suppressed, and the object to be sealed is hardly affected by moisture.
　上記水蒸気透過率Ｗは、７ｇ／ｍ２・ｄａｙ以下であることが好ましく、特に５ｇ／ｍ２・ｄａｙ以下であることが好ましく、さらには３ｇ／ｍ２・ｄａｙ以下であることが好ましい。 The water vapor transmission rate W is preferably 7 g / m 2 · day or less, particularly preferably 5 g / m 2 · day or less, and more preferably 3 g / m 2 · day or less.
　また、温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算（第１の接着性樹脂層１１Ａの厚みを５０μｍとしたとき）の第１の接着性樹脂層１１Ａの水蒸気透過率をＷ１（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算（第２の接着性樹脂層１１Ｂの厚みを５０μｍとしたとき）の第２の接着性樹脂層１１Ｂの水蒸気透過率をＷ２（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算（水蒸気バリア性樹脂層１２の厚みを５０μｍとしたとき）の水蒸気バリア性樹脂層１２の水蒸気透過率をＷ３（ｇ／ｍ２・ｄａｙ）としたときに、Ｗ１、Ｗ２およびＷ３は、
　Ｗ１＞Ｗ３、Ｗ２＞Ｗ３、かつＷ３≦１０
の関係を満たすことが好ましい。Ｗ１、Ｗ２およびＷ３が上記範囲内にあることにより、フィルム状封止材１は、上記のような水蒸気透過率を達成し易くなる。 Further, the water vapor transmission rate of the first adhesive resin layer 11A in terms of a thickness of 50 μm (when the thickness of the first adhesive resin layer 11A is 50 μm) in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH is The water vapor transmission rate of the second adhesive resin layer 11B in terms of W1 (g / m 2 · day) and 50 μm thickness (when the thickness of the second adhesive resin layer 11B is 50 μm) is W2 (g / m 2 Day), when the water vapor permeability of the water vapor barrier resin layer 12 in terms of 50 μm thickness (when the thickness of the water vapor barrier resin layer 12 is 50 μm) is W3 (g / m 2 · day), W1, W2 and W3 are
W1> W3, W2> W3 and W3 ≦ 10
It is preferable to satisfy the relationship. When W1, W2, and W3 are within the above range, the film-shaped sealing material 1 can easily achieve the water vapor transmission rate as described above.
　水蒸気透過率Ｗ１およびＷ２は、２００ｇ／ｍ２・ｄａｙ以下であることが好ましく、特に１００ｇ／ｍ２・ｄａｙ以下であることが好ましく、さらには５０ｇ／ｍ２・ｄａｙ以下であることが好ましい。なお、水蒸気透過率Ｗ、Ｗ１、Ｗ２およびＷ３の測定方法は、後述する試験例に示す通りである。厚み５０μｍ換算の水蒸気透過率Ｗ、Ｗ１、Ｗ２およびＷ３の値は、各層の厚みから換算して求めることができる。例えば、厚みがＡμｍで、水蒸気透過率がＢｇ／（ｍ２・ｄａｙ）の場合、厚み５０μｍ換算の水蒸気透過率は、Ｂ×Ａ／５０という式に当てはめて求めることができる。 The water vapor transmission rates W1 and W2 are preferably 200 g / m 2 · day or less, particularly preferably 100 g / m 2 · day or less, and more preferably 50 g / m 2 · day or less. In addition, the measuring method of water-vapor-permeation rate W, W1, W2, and W3 is as showing to the test example mentioned later. The values of water vapor permeability W, W1, W2, and W3 in terms of thickness 50 μm can be obtained by conversion from the thickness of each layer. For example, when the thickness is A μm and the water vapor transmission rate is Bg / (m 2 · day), the water vapor transmission rate in terms of the thickness of 50 μm can be obtained by applying the formula B × A / 50.
　また、第１の接着性樹脂層の厚さをＴ１（μｍ）、第２の接着性樹脂層の厚さをＴ２（μｍ）、水蒸気バリア性樹脂層の厚さをＴ３（μｍ）としたとき、Ｔ１、Ｔ２およびＴ３は、
　０．１＜{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}＜０．９９
　１≦Ｔ１≦１００
　１≦Ｔ２≦１００
　５≦Ｔ３≦３００
の関係を満たすことが好ましい。Ｔ１、Ｔ２およびＴ３が上記の関係を満たすことにより、フィルム状封止材１は、上記のような水蒸気透過率および接着力を達成し易くなる。 When the thickness of the first adhesive resin layer is T1 (μm), the thickness of the second adhesive resin layer is T2 (μm), and the thickness of the water vapor barrier resin layer is T3 (μm). , T1, T2 and T3 are
0.1 <{T3 / (T1 + T2 + T3)} <0.99
1 ≦ T1 ≦ 100
1 ≦ T2 ≦ 100
5 ≦ T3 ≦ 300
It is preferable to satisfy the relationship. When T1, T2, and T3 satisfy the above relationship, the film-shaped sealing material 1 can easily achieve the water vapor transmission rate and the adhesive force as described above.
　{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}の上限値は、より好ましくは０．９５であり、特に好ましくは０．９であり、さらに好ましくは０．８である。一方、下限値は、より好ましくは０．３であり、特に好ましくは０．４であり、さらに好ましくは０．５である。{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}の下限値が０．１未満であると、所望の水蒸気バリア性が得られないおそれがある。一方、{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}の上限値が０．９９を超えると、所望の接着性が得られないおそれがある。 The upper limit value of {T3 / (T1 + T2 + T3)} is more preferably 0.95, particularly preferably 0.9, and further preferably 0.8. On the other hand, the lower limit value is more preferably 0.3, particularly preferably 0.4, and further preferably 0.5. If the lower limit of {T3 / (T1 + T2 + T3)} is less than 0.1, the desired water vapor barrier property may not be obtained. On the other hand, if the upper limit of {T3 / (T1 + T2 + T3)} exceeds 0.99, the desired adhesiveness may not be obtained.
　また、Ｔ３が５μｍ未満であると、フィルム状封止材１は所望の水蒸気透過率を満たすことができないおそれがあるため、Ｔ３は、５μｍ以上であることが好ましく、１０μｍ以上であることが特に好ましく、１５μｍ以上であることがさらに好ましい。一方、Ｔ３が３００μｍを超えると透過率やハンドリング性が低下するおそれがあるため、Ｔ３は、３００μｍ以下であることが好ましく、２００μｍ以下であることが特に好ましく、１００μｍ以下であることがさらに好ましい。 Moreover, since there exists a possibility that the film-form sealing material 1 may not satisfy | fill desired water vapor permeability as T3 is less than 5 micrometers, it is preferable that T3 is 5 micrometers or more, and it is especially 10 micrometers or more. Preferably, it is 15 μm or more. On the other hand, if T3 exceeds 300 μm, the transmittance and handling properties may be lowered. Therefore, T3 is preferably 300 μm or less, particularly preferably 200 μm or less, and further preferably 100 μm or less.
　一方、Ｔ１およびＴ２が１μｍ未満であると、フィルム状封止材１は所望の接着力が得られないおそれがあるため、Ｔ１およびＴ２は、１μｍ以上であることが好ましく、３μｍ以上であることが特に好ましく、５μｍ以上であることがさらに好ましい。一方、Ｔ１およびＴ２が１００μｍを超えると透過率やハンドリング性が低下するおそれがあるため、Ｔ１およびＴ２は、１００μｍ以下であることが好ましく、８０μｍ以下であることが特に好ましく、５０μｍ以下であることがさらに好ましい。 On the other hand, if T1 and T2 are less than 1 μm, the film-like sealing material 1 may not obtain a desired adhesive force. Therefore, T1 and T2 are preferably 1 μm or more, and 3 μm or more. Is particularly preferable and is more preferably 5 μm or more. On the other hand, if T1 and T2 exceed 100 μm, the transmittance and handling properties may decrease. Therefore, T1 and T2 are preferably 100 μm or less, particularly preferably 80 μm or less, and 50 μm or less. Is more preferable.
　フィルム状封止材１は、可視光領域における全光線透過率が８５％以上であることが好ましく、特に８８％以上であることが好ましく、さらには９０％以上であることが好ましい。なお、全光線透過率は、ＪＩＳ Ｋ７３６１：１９９６に準拠して測定した値とする。 The film-like encapsulant 1 preferably has a total light transmittance in the visible light region of 85% or more, particularly preferably 88% or more, and more preferably 90% or more. The total light transmittance is a value measured in accordance with JIS K 7361: 1996.
（１）接着性樹脂層
　第１の接着性樹脂層１１Ａおよび第２の接着性樹脂層１１Ｂは、被着体に対して接着性を示す層であり、本実施形態では、フィルム状封止材１の両面の最外層に設けられている。 (1) Adhesive resin layer The first adhesive resin layer 11A and the second adhesive resin layer 11B are layers exhibiting adhesiveness to the adherend, and in this embodiment, a film-like sealing material 1 is provided on the outermost layer of both sides.
　第１および第２の接着性樹脂層１１Ａ，１１Ｂを構成する樹脂としては、上記の接着力の範囲を満たすものであれば特に限定されず、例えば、熱可塑性樹脂、熱硬化性樹脂、エネルギー線硬化型樹脂などが挙げられる。これらの中でも、第１および第２の接着性樹脂層１１Ａ，１１Ｂは、水蒸気バリア性樹脂層１２との密着性に優れるという点から、熱可塑性樹脂を含むことが好ましい。 The resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it satisfies the above-mentioned range of adhesive force. For example, a thermoplastic resin, a thermosetting resin, an energy beam Examples thereof include curable resins. Among these, it is preferable that the first and second adhesive resin layers 11 </ b> A and 11 </ b> B contain a thermoplastic resin from the viewpoint of excellent adhesion to the water vapor barrier resin layer 12.
　熱可塑性樹脂としては、例えば、酸変性ポリオレフィン系樹脂、シラン変性ポリオレフィン系樹脂、アイオノマー、エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体、ポリエステル系樹脂、ポリウレタン系樹脂、ポリエステルウレタン系樹脂、アクリル系樹脂、アミド系樹脂、スチレン系樹脂、シラン系樹脂、ゴム系樹脂等が挙げられる。これらの中でも、上記の接着力の範囲を満たし易く、水蒸気透過率の比較的低い、酸変性ポリオレフィン系樹脂、シラン変性ポリオレフィン系樹脂、アイオノマーおよびエチレン－（メタ）アクリル酸共重合体が好ましい。これらは、１種を単独でまたは２種以上を混合して使用することができる。なお、本明細書において、（メタ）アクリル酸とは、アクリル酸およびメタクリル酸の両方を意味する。他の類似用語も同様である。 Examples of thermoplastic resins include acid-modified polyolefin resins, silane-modified polyolefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers. Examples include polymers, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins, and rubber resins. Among these, acid-modified polyolefin resins, silane-modified polyolefin resins, ionomers, and ethylene- (meth) acrylic acid copolymers that can easily satisfy the above-described adhesive force range and have a relatively low water vapor permeability are preferable. These can be used individually by 1 type or in mixture of 2 or more types. In addition, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
　上記の中でも、ガラス板に対する接着力に優れ、水蒸気バリア性樹脂層１２との密着性にも優れるという点から、第１および第２の接着性樹脂層１１Ａ，１１Ｂは、酸変性ポリオレフィン系樹脂、シラン変性ポリオレフィン系、アイオノマーおよびエチレン－（メタ）アクリル酸共重合体からなる群より選ばれる少なくとも１種を含むことが好ましく、湿熱条件下においたときに接着力が低下しにくいという点から、酸変性ポリオレフィン系樹脂および／またはシラン変性ポリオレフィン系樹脂を含むことが特に好ましい。 Among the above, the first and second adhesive resin layers 11A and 11B are an acid-modified polyolefin resin, from the viewpoint of excellent adhesion to the glass plate and excellent adhesion to the water vapor barrier resin layer 12. It is preferable to include at least one selected from the group consisting of silane-modified polyolefins, ionomers, and ethylene- (meth) acrylic acid copolymers. It is particularly preferable to include a modified polyolefin resin and / or a silane-modified polyolefin resin.
　酸変性ポリオレフィン系樹脂とは、酸でグラフト変性したポリオレフィン系樹脂を意味し、例えば、ポリオレフィン系樹脂に不飽和カルボン酸を反応させ、カルボキシル基を導入（グラフト変性）したものが挙げられる。なお、本明細書において、不飽和カルボン酸とは、カルボン酸無水物の概念を含み、カルボキシル基とは、無水カルボキシル基の概念を含むものである。 The acid-modified polyolefin resin means a polyolefin resin graft-modified with an acid, and examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and introducing a carboxyl group (graft modification). In the present specification, the unsaturated carboxylic acid includes the concept of a carboxylic acid anhydride, and the carboxyl group includes the concept of an anhydrous carboxyl group.
　上記ポリオレフィン系樹脂とは、重合体を構成するモノマー成分としてオレフィンを含む重合体（共重合体の概念を含む）をいい、モノマー成分が１種または２種以上のオレフィンのみからなる重合体であってもよいし、モノマー成分として１種または２種以上のオレフィンおよび他のモノマーを含む重合体（共重合体）であってもよい。 The polyolefin resin refers to a polymer (including the concept of a copolymer) containing olefin as a monomer component constituting the polymer, and the monomer component is a polymer composed of only one or two or more olefins. Alternatively, it may be a polymer (copolymer) containing one or more olefins and other monomers as monomer components.
　上記オレフィンとしては、炭素数２～８のα－オレフィンが好ましく、例えば、エチレン、プロピレン、ブチレン、イソブチレン、１－ヘキセン等が挙げられる。中でもエチレンおよびプロピレンが好ましく、特にエチレンが好ましい。上記他のモノマーとしては、本実施形態に係るフィルム状封止材１の目的を阻害しない限り特に限定されず、例えば、酢酸ビニル、（メタ）アクリル酸エステル等が挙げられる。なお、本明細書において、（メタ）アクリル酸とは、アクリル酸およびメタクリル酸の両方を意味する。他の類似用語も同様である。 The olefin is preferably an α-olefin having 2 to 8 carbon atoms, and examples thereof include ethylene, propylene, butylene, isobutylene and 1-hexene. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable. The other monomer is not particularly limited as long as the purpose of the film-shaped sealing material 1 according to the present embodiment is not impaired, and examples thereof include vinyl acetate and (meth) acrylic acid ester. In addition, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
　上記ポリオレフィン系樹脂としては、具体的には、超低密度ポリエチレン（ＶＬＤＰＥ，密度：８８０ｋｇ／ｍ３以上、９１０ｋｇ／ｍ３未満）、低密度ポリエチレン（ＬＤＰＥ，密度：９１０ｋｇ／ｍ３以上、９３０ｋｇ／ｍ３未満）、中密度ポリエチレン（ＭＤＰＥ，密度：９３０ｋｇ／ｍ３以上、９４２ｋｇ／ｍ３未満）、高密度ポリエチレン（ＨＤＰＥ，密度：９４２ｋｇ／ｍ３以上）、直鎖状低密度ポリエチレン等のポリエチレン樹脂、ポリプロピレン樹脂、エチレン－プロピレン共重合体、オレフィン系エラストマー、エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体などが挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。上記の中でも、超低密度ポリエチレン、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン等のポリエチレン樹脂が好ましく、特に超低密度ポリエチレンが好ましい。 As the polyolefin-based resin, specifically, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more and less than 910 kg / m 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more, 930 kg / m 3), medium density polyethylene (MDPE, density: 930 kg / m 3 or more, 942Kg / m 3), high density polyethylene (HDPE, density: 942kg / m 3 or higher), linear low density polyethylene, such as polyethylene Resin, polypropylene resin, ethylene-propylene copolymer, olefin elastomer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. . These can be used individually by 1 type or in combination of 2 or more types. Among these, polyethylene resins such as ultra-low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene are preferable, and ultra low density polyethylene is particularly preferable.
　上記ポリオレフィン系樹脂に反応させる不飽和カルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グルタコン酸、テトラヒドロフタル酸、アコニット酸、無水マレイン酸、無水イタコン酸、無水グルタコン酸、無水シトラコン酸、無水アコニット酸、ノルボルネンジカルボン酸無水物、テトラヒドロフタル酸無水物、（メタ）アクリル酸等が挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。上記の中でも、特に接着力に優れる無水マレイン酸が好ましい。 Examples of the unsaturated carboxylic acid to be reacted with the polyolefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, Citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, (meth) acrylic acid and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among the above, maleic anhydride, which is particularly excellent in adhesive strength, is preferable.
　上記酸変性ポリオレフィン系樹脂としては、無水マレイン酸変性ポリオレフィン系樹脂が好ましく、特に無水マレイン酸変性ポリエチレン樹脂が好ましい。 The acid-modified polyolefin resin is preferably a maleic anhydride-modified polyolefin resin, particularly preferably a maleic anhydride-modified polyethylene resin.
　ポリオレフィン系樹脂に反応させる不飽和カルボン酸の量としては、ポリオレフィン系樹脂１００質量部に対して、０．１～５．０質量部であることが好ましく、特に０．２～３．０質量部であることが好ましく、さらには０．２～１．０質量部であることが好ましい。反応させる不飽和カルボン酸の量が上記の範囲にあることで、得られる酸変性ポリオレフィン系樹脂は、接着力に優れる。 The amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5.0 parts by mass, particularly 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the polyolefin resin. Preferably, the amount is 0.2 to 1.0 part by mass. When the amount of the unsaturated carboxylic acid to be reacted is in the above range, the resulting acid-modified polyolefin resin is excellent in adhesive strength.
　酸変性ポリオレフィン系樹脂は、ビカット軟化点（Ｓｐ）が９０℃以下であることが好ましく、特に３０～７０℃であることが好ましく、さらには３０～６０℃であることが好ましい。ビカット軟化点が３０℃以上であると、室温においては接着性が発現しないため、フィルム状封止材１の取扱性に優れるため好ましい。また、ビカット軟化点が９０℃以下であると、比較的短時間での熱圧着で接着が可能となるため、有機素子が熱圧着時の熱により劣化することを防止でき、有機ＥＬ素子を有する表示装置用モジュールや、電子ペーパー、有機薄膜太陽電池等の電子デバイスを効率よく製造することが出来る。なお、ビカット軟化点は、ＡＳＴＭ Ｄ１５２５に基づいて測定した値とする。 The acid-modified polyolefin resin preferably has a Vicat softening point (Sp) of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C. A Vicat softening point of 30 ° C. or higher is preferable because the adhesiveness is not expressed at room temperature, and the handleability of the film-shaped sealing material 1 is excellent. In addition, when the Vicat softening point is 90 ° C. or lower, it becomes possible to bond by thermocompression bonding in a relatively short time, so that the organic element can be prevented from being deteriorated by heat during thermocompression bonding, and has an organic EL element. Electronic devices such as modules for display devices, electronic paper, and organic thin-film solar cells can be efficiently manufactured. The Vicat softening point is a value measured based on ASTM D1525.
　酸変性ポリオレフィン系樹脂は、１９０℃、荷重２０．２Ｎにおけるメルトフローレート（ＭＦＲ）が、０．５～３０ｇ／１０分であることが好ましく、特に１～１５ｇ／１０分であることが好ましく、さらには２～１０ｇ／１０分であることが好ましい。第１および第２の接着性樹脂層１１Ａ，１１Ｂを押出成形により形成する場合、ＭＦＲが０．５ｇ／１０分未満であると、押出成形が困難となるおそれがあり、ＭＦＲが３０ｇ／１０分を超えると、押出成形により製膜した際に、厚み精度が低下するおそれがある。なお、本明細書におけるＭＦＲは、ＡＳＴＭＤ１２３８に基づいて測定した値とする。 The acid-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly preferably 1 to 15 g / 10 minutes. Further, it is preferably 2 to 10 g / 10 minutes. When the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion. In addition, MFR in this specification shall be the value measured based on ASTMD1238.
　酸変性ポリオレフィン系樹脂は、市販品を用いることもできる。市販品としては、例えば、アドマー（登録商標）（三井化学社製）、ＢｏｎｄｙＲａｍ（Ｐｏｌｙｒａｍ社製）、ｏｒｅｖａｃ（登録商標）（ＡＲＫＥＭＡ社製）、モディック（登録商標）（三菱化学社製）等が挙げられる。 Commercially available products can be used as the acid-modified polyolefin resin. Examples of commercially available products include Admer (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like. Can be mentioned.
　シラン変性ポリオレフィン系樹脂とは、ポリオレフィン系樹脂に不飽和シラン化合物を反応させることにより、ポリオレフィン系樹脂をグラフト変性したものである。シラン変性ポリオレフィン系樹脂は、特に被着体がガラス板の場合に強固に接着することができるとともに、湿熱条件下においたときにも接着力が低下し難いため、好ましい。 The silane-modified polyolefin resin is obtained by graft-modifying a polyolefin resin by reacting an unsaturated silane compound with the polyolefin resin. A silane-modified polyolefin resin is preferable because it can be firmly bonded, particularly when the adherend is a glass plate, and the adhesive force hardly decreases even under wet heat conditions.
　シラン変性ポリオレフィン系樹脂のポリオレフィン系樹脂としては、前述の酸でグラフト変性させるポリオレフィン系樹脂として例示したポリオレフィン系樹脂が挙げられる。 Examples of the polyolefin resin of the silane-modified polyolefin resin include the polyolefin resins exemplified as the polyolefin resin to be graft-modified with the above-mentioned acid.
　シラン変性ポリオレフィン系樹脂は、シラン変性ポリエチレン樹脂およびシラン変性エチレン－酢酸ビニル共重合体が好ましく、特に、シラン変性低密度ポリエチレン、シラン変性超低密度ポリエチレン、シラン変性直鎖状低密度ポリエチレン等のシラン変性ポリエチレン樹脂が好ましい。 The silane-modified polyolefin-based resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and in particular, silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene. A modified polyethylene resin is preferred.
　上記ポリオレフィン系樹脂に反応させる不飽和シラン化合物としては、ビニルシラン化合物が好ましく、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルトリペンチロキシシラン、ビニルトリフェノキシシラン、ビニルトリベンジルオキシシラン、ビニルトリメチレンジオキシシラン、ビニルトリエチレンジオキシシラン、ビニルプロピオニルオキシシラン、ビニルトリアセトキシシラン、ビニルトリカルボキシシラン等が挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。 As the unsaturated silane compound to be reacted with the polyolefin-based resin, a vinyl silane compound is preferable. For example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyl. Examples include loxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. These can be used individually by 1 type or in combination of 2 or more types.
　ポリオレフィン系樹脂に反応させる不飽和シラン化合物の量としては、ポリオレフィン系樹脂１００質量部に対して、０．１～１０質量部であることが好ましく、特に０．３～７質量部であることが好ましく、さらには０．５～５質量部であることが好ましい。反応させる不飽和シラン化合物の量が上記の範囲にあることで、得られるシラン変性ポリオレフィン系樹脂は、接着力に優れる。 The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, the content is 0.5 to 5 parts by mass. When the amount of the unsaturated silane compound to be reacted is in the above range, the resulting silane-modified polyolefin resin is excellent in adhesive strength.
　シラン変性ポリオレフィン系樹脂は、１９０℃、荷重２０．２Ｎにおけるメルトフローレート（ＭＦＲ）が、０．１～３０ｇ／１０分であることが好ましく、特に０．３～１５ｇ／１０分であることが好ましく、さらには０．５～１０ｇ／１０分であることが好ましい。第１および第２の接着性樹脂層１１Ａ，１１Ｂを押出成形により形成する場合、ＭＦＲが０．１ｇ／１０分未満であると、押出成形が困難となるおそれがあり、ＭＦＲが３０ｇ／１０分を超えると、押出成形により製膜した際に、厚み精度が低下するおそれがある。 The silane-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.1 to 30 g / 10 minutes, particularly 0.3 to 15 g / 10 minutes. More preferably, it is 0.5 to 10 g / 10 min. When the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.1 g / 10 minutes, extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
　シラン変性ポリオレフィン系樹脂は、市販品を用いることもできる。市販品としては、例えば、リンクロン（登録商標）（三菱化学社製）等が挙げられ、中でも、低密度ポリエチレン系のリンクロン、直鎖状低密度ポリエチレン系のリンクロン、超低密度ポリエチレン系のリンクロン、およびエチレン－酢酸ビニル共重合体系のリンクロンを好ましく使用することができる。 Commercially available products can also be used as the silane-modified polyolefin resin. Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based. Of these, Rincron of ethylene-vinyl acetate copolymer system can be preferably used.
　アイオノマーとしては、特に限定されないが、例えば、エチレン－（メタ）アクリル酸共重合体、エチレン－フマル酸共重合体等のオレフィン系樹脂の分子間を金属イオンで結合したものが好ましい。 The ionomer is not particularly limited, but for example, an olefin resin molecule such as an ethylene- (meth) acrylic acid copolymer or an ethylene-fumaric acid copolymer is preferably bonded with a metal ion.
　エチレン－（メタ）アクリル酸共重合体は、エチレンとアクリル酸および／またはメタクリル酸との共重合体であるが、特にエチレンとメタクリル酸との共重合体であるエチレン－メタクリル酸共重合体が好ましい。エチレン－（メタ）アクリル酸共重合体中における単量体単位としての（メタ）アクリル酸の含有量は、２～２０質量％であることが好ましく、特に３～１５質量％であることが好ましい。（メタ）アクリル酸の含有量が２質量％未満であると、樹脂の結晶化度が高くなり、不透明になるおそれがある。一方、（メタ）アクリル酸の含有量が２０質量％を超えると、所望の水蒸気バリア性が得られないおそれがある。 The ethylene- (meth) acrylic acid copolymer is a copolymer of ethylene and acrylic acid and / or methacrylic acid. In particular, an ethylene-methacrylic acid copolymer that is a copolymer of ethylene and methacrylic acid is used. preferable. The content of (meth) acrylic acid as a monomer unit in the ethylene- (meth) acrylic acid copolymer is preferably 2 to 20% by mass, particularly preferably 3 to 15% by mass. . When the content of (meth) acrylic acid is less than 2% by mass, the crystallinity of the resin becomes high and there is a possibility that the resin becomes opaque. On the other hand, if the content of (meth) acrylic acid exceeds 20% by mass, the desired water vapor barrier property may not be obtained.
　なお、第１および第２の接着性樹脂層１１Ａ，１１Ｂは、上記樹脂以外に、所望により、例えば粘着付与剤、紫外線吸収剤、紫外線安定剤、帯電防止剤、顔料、難燃剤、可塑剤、滑剤、ブロッキング防止剤、シランカップリング剤等の各種添加剤等を含有してもよい。 In addition, the first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, if desired. You may contain various additives, such as a lubricant, an antiblocking agent, and a silane coupling agent.
　なお、第１および第２の接着性樹脂層１１Ａ，１１Ｂの材料は、それぞれ同じであってもよいし、異なっていてもよい。 Note that the materials of the first and second adhesive resin layers 11A and 11B may be the same or different.
（２）水蒸気バリア性樹脂層
　水蒸気バリア性樹脂層１２は、フィルム状封止材１において水蒸気が透過することを防止・抑制するための樹脂層である。水蒸気バリア性樹脂層１２は、単層であってもよく、複数層であってもよい。 (2) Water Vapor Barrier Resin Layer The water vapor barrier resin layer 12 is a resin layer for preventing / suppressing permeation of water vapor in the film sealing material 1. The water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
　水蒸気バリア性樹脂層１２を構成する樹脂としては、上記の水蒸気透過率の範囲を満たすものであれば特に限定されないが、例えば、シクロオレフィン系樹脂、直鎖状低密度ポリエチレン、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体およびゴム系樹脂からなる群から選ばれる少なくとも１種の熱可塑性樹脂であることが好ましい。水蒸気バリア性樹脂層１２がこれらの樹脂を含むことにより、フィルム状封止材１は前述した水蒸気透過率を達成し易いものとなる。 The resin constituting the water vapor barrier resin layer 12 is not particularly limited as long as it satisfies the above water vapor transmission rate range. For example, cycloolefin resin, linear low density polyethylene, low density polyethylene, medium It is preferably at least one thermoplastic resin selected from the group consisting of density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer and rubber resin. When the water vapor barrier resin layer 12 contains these resins, the film-shaped sealing material 1 can easily achieve the water vapor transmission rate described above.
　上記の中でも、水蒸気透過率が低く、所望の水蒸気透過率を達成し易いという点から、水蒸気バリア性樹脂層１２は、シクロオレフィン系樹脂、低密度ポリエチレン、直鎖状低密度ポリエチレンおよびゴム系樹脂からなる群から選ばれる少なくとも１種を含むことが好ましい。 Among these, the water vapor barrier resin layer 12 is composed of a cycloolefin resin, a low density polyethylene, a linear low density polyethylene, and a rubber resin because the water vapor permeability is low and the desired water vapor permeability is easily achieved. It is preferable to include at least one selected from the group consisting of
　シクロオレフィン系樹脂とは、重合体を構成するモノマー成分としてシクロオレフィンを含む重合体（共重合体の概念を含む）樹脂をいい、モノマー成分がシクロオレフィンのみからなる重合体であってもよいし、モノマー成分としてシクロオレフィンおよび他のモノマーを含む重合体（共重合体）であってもよい。上記他のモノマーとしては、本実施形態に係るフィルム状封止材１の目的を阻害しない限り特に限定されず、例えば、エチレン、プロプレンなど炭素数２以上のα－オレフィン、（メタ）アクリル酸エステル等が挙げられる。 The cycloolefin-based resin refers to a polymer resin (including the concept of copolymer) containing cycloolefin as a monomer component constituting the polymer, and the monomer component may be a polymer composed only of cycloolefin. Further, it may be a polymer (copolymer) containing cycloolefin and other monomers as monomer components. The other monomer is not particularly limited as long as it does not hinder the purpose of the film-like sealing material 1 according to the present embodiment, and examples thereof include α-olefins having 2 or more carbon atoms such as ethylene and propylene, and (meth) acrylic acid esters. Etc.
　上記の中でも、シクロオレフィン系樹脂は、前述した第１および第２の接着性樹脂層１１Ａ，１１Ｂとの密着性に優れ、フィルム状封止材１の層間剥離を防止できるという点から、モノマー成分としてシクロオレフィンとエチレンとを含む共重合体であることが好ましい。 Among the above, the cycloolefin resin is a monomer component because it has excellent adhesion to the first and second adhesive resin layers 11A and 11B and can prevent delamination of the film-shaped sealing material 1. A copolymer containing cycloolefin and ethylene is preferred.
　シクロオレフィン系樹脂は、親水性基を有さないことが好ましい。親水性基を有すると、水蒸気バリア性が低下するおそれがある。親水性基としては、例えば、ヒドロキシ基、カルボキシル基、アミノ基、アミド基、イミド基、スルホン酸基、メルカプト基等が挙げられる。一方、シクロオレフィン系樹脂は、疎水性基を有していてもよい。疎水性基であれば、水蒸気バリア性が低下するおそれはない。疎水性基としては、例えば、アルキル基、アリール基等が挙げられる。 It is preferable that the cycloolefin resin does not have a hydrophilic group. When it has a hydrophilic group, the water vapor barrier property may be lowered. Examples of the hydrophilic group include a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a sulfonic acid group, and a mercapto group. On the other hand, the cycloolefin-based resin may have a hydrophobic group. If it is a hydrophobic group, there is no possibility that water vapor | steam barrier property will fall. Examples of the hydrophobic group include an alkyl group and an aryl group.
　好ましいシクロオレフィン系樹脂としては、下記構造式（ａ）
Figure JPOXMLDOC01-appb-C000001
（式（ａ）中、ｍおよびｎは１以上の整数である。Ｒ１およびＲ２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ１およびＲ２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンとエチレンとを含む共重合体；ＣＯＣ）、下記構造式（ｂ）
Figure JPOXMLDOC01-appb-C000002
（式（ｂ）中、ｍおよびｎは１以上の整数である。Ｒ１およびＲ２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ１およびＲ２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンとエチレンとを含む共重合体；ＣＯＣ）、下記構造式（ｃ）
Figure JPOXMLDOC01-appb-C000003
（式（ｃ）中、ｎは１以上の整数であり、Ｒ１およびＲ２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ１およびＲ２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンのみを含む重合体；ＣＯＰ）、および下記構造式（ｄ）
Figure JPOXMLDOC01-appb-C000004
（式（ｄ）中、ｎは１以上の整数であり、Ｒ１およびＲ２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ１およびＲ２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンのみを含む重合体；ＣＯＰ）が挙げられる。これらのシクロオレフィン重合体は、水蒸気バリア性に非常に優れ、入手も容易である。これらのシクロオレフィン重合体は、１種を単独でまたは２種以上を組み合わせて使用することができる。 As a preferred cycloolefin-based resin, the following structural formula (a)
Figure JPOXMLDOC01-appb-C000001
(In the formula (a), m and n are .R 1 and R 2 is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.)
A cycloolefin polymer represented by the formula (a copolymer containing cycloolefin and ethylene as monomer components; COC), the following structural formula (b)
Figure JPOXMLDOC01-appb-C000002
(In the formula (b), m and n are .R 1 and R 2 is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.)
A cycloolefin polymer represented by the formula (a copolymer containing cycloolefin and ethylene as monomer components; COC), the following structural formula (c)
Figure JPOXMLDOC01-appb-C000003
(In the formula (c), n is an integer of 1 or more, and R 1 and R 2 represent a hydrogen atom or an alkyl group, and may be the same or different. R 1 and R 2 May be bonded to form a ring.)
(A polymer containing only cycloolefin as a monomer component; COP), and the following structural formula (d)
Figure JPOXMLDOC01-appb-C000004
(In formula (d), n is an integer of 1 or more, and R 1 and R 2 represent a hydrogen atom or an alkyl group, and may be the same or different. R 1 and R 2 May be bonded to form a ring.)
And a cycloolefin polymer (polymer containing only cycloolefin as a monomer component; COP). These cycloolefin polymers are extremely excellent in water vapor barrier properties and are easily available. These cycloolefin polymers can be used singly or in combination of two or more.
　シクロオレフィン重合体は、市販品を用いることもできる。市販品としては、例えば、ＺＥＯＮＥＸ（登録商標）（日本ゼオン社製，ノルボルネン系モノマーの開環メタセシス重合体水素化ポリマー）、ＴＯＰＡＳ（登録商標）（ポリプラスチックス社製，ノルボルネンとエチレンとのコポリマー）、ＺＥＯＮＯＲ（登録商標）（日本ゼオン社製，ジシクロペンタジエンとテトラシクロペンタドデセンとの開環重合に基づくコポリマー）、アペル（登録商標）（三井化学社製，エチレンとテトラシクロドデセンとのコポリマー）、アートン（登録商標）（ＪＳＲ社製，ジシクロペンタジエンおよびメタクリル酸エステルを原料とする極性基を含む環状オレフィン樹脂）などが挙げられる。 A commercially available product can also be used as the cycloolefin polymer. Examples of commercially available products include ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd., ring-opening metathesis polymer hydrogenated polymer of norbornene monomer), TOPAS (registered trademark) (manufactured by Polyplastics Co., Ltd., copolymer of norbornene and ethylene). ), ZEONOR (registered trademark) (manufactured by Nippon Zeon Co., Ltd., a copolymer based on ring-opening polymerization of dicyclopentadiene and tetracyclopentadecene), Apel (registered trademark) (manufactured by Mitsui Chemicals, ethylene and tetracyclododecene) Copolymer), Arton (registered trademark) (manufactured by JSR, cyclic olefin resin containing a polar group using dicyclopentadiene and methacrylic acid ester as raw materials).
　ゴム系樹脂としては、例えば、天然ゴム、天然ゴムに（メタ）アクリル酸アルキルエステル、スチレンおよび（メタ）アクリロニトリルから選ばれる１種又は２種以上の単量体をグラフト重合させた変性天然ゴム、ポリイソブチレン系樹脂、ブタジエンゴム、クロロプレンゴム、イソプレンゴム、ハロゲン化ブチルゴム、スチレン－ブタジエン共重合体（ＳＢＲ）、スチレン－イソプレン共重合体、アクリロニトリル－ブタジエンの共重合体（ニトリルゴム）、メタクリル酸メチル－ブタジエン共重合体、ウレタンゴム、スチレン－１，３－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、エチレン－プロピレン－非共役ジエン三元共重合体等が挙げられる。これらは１種単独で、あるいは２種以上を組み合わせて用いることができる。上記の中でも、水蒸気透過率が低く、所望の水蒸気透過率を達成しやすいという点から、ゴム系樹脂は、ポリイソブチレン系樹脂であることが好ましい。 Examples of rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, halogenated butyl rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate -Butadiene copolymer, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-nonconjugated diene ternary copolymer Examples include coalescence. These can be used alone or in combination of two or more. Among these, the rubber-based resin is preferably a polyisobutylene-based resin from the viewpoint that the water vapor transmission rate is low and a desired water vapor transmission rate is easily achieved.
　上記ポリイソブチレン系樹脂は、モノマー成分としてイソブチレンを含む重合体（共重合体の概念を含む）をいい、モノマー成分がイソブチレンのみからなる単独重合体であってもよいし、モノマー成分としてイソブチレンと他のモノマーを重合して得られる共重合体であってもよい。ポリイソブチレン系樹脂は、一部を臭素化又は塩素化したハロゲン化ポリイソブチレン系樹脂であってもよく、一部を水酸基、カルボキシル基等の官能基で置換したものであってもよい。上記他のモノマーとしては、例えば、イソプレン、ｎ－ブテン、ブタジエン、イソプレン、スチレン等が挙げられる。他のモノマーは単独で又は２種以上を併用して用いてもよい。なお、ポリイソブチレン系樹脂が共重合体である場合は、原料モノマー中、イソブチレンは主成分として最大量のモノマーである。ポリイソブチレン系樹脂は、水蒸気バリア性に優れるという点から、モノマー成分がイソブチレンのみからなる単独重合体、モノマー成分としてイソブチレンとイソプレンとを重合して得られるイソブチレン－イソプレン共重合体であることが好ましい。 The polyisobutylene-based resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), and the monomer component may be a homopolymer composed only of isobutylene, or isobutylene and others as the monomer component. It may be a copolymer obtained by polymerizing these monomers. The polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group. Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more. When the polyisobutylene resin is a copolymer, isobutylene is the maximum amount of monomer as a main component in the raw material monomer. The polyisobutylene-based resin is preferably a homopolymer whose monomer component is composed only of isobutylene, and an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component from the viewpoint of excellent water vapor barrier properties. .
　水蒸気バリア性樹脂層１２は、前述の樹脂以外に、上記の水蒸気透過率の範囲を満たす範囲で、他の樹脂成分を含有してもよい。他の樹脂成分としては、ポリエチレン、ポリプロピレン、ポリブテン、エチレン－αオレフィン共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸エステル共重合体等のオレフィン系樹脂（ただし、シクロオレフィン系樹脂を除く。）、ウレタン系樹脂、ゴム系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリエステルウレタン系樹脂、アクリル系樹脂、アミド系樹脂、スチレン系樹脂、シラン系樹脂などが挙げられる。 The water vapor barrier resin layer 12 may contain other resin components in the range satisfying the range of the water vapor transmission rate in addition to the above-described resin. Other resin components include polyethylene, polypropylene, polybutene, ethylene-α olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer Olefin resins such as coalescence (excluding cycloolefin resins), urethane resins, rubber resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins And silane-based resins.
　また、水蒸気バリア性樹脂層１２は、上記樹脂以外に、所望により、粘着付与剤、紫外線吸収剤、紫外線安定剤、帯電防止剤、顔料、難燃剤、可塑剤、滑剤、ブロッキング防止剤等の各種添加剤等を含有してもよい。 Further, the water vapor barrier resin layer 12 is made of various materials such as a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, and an antiblocking agent, if desired. You may contain an additive etc.
（３）フィルム状封止材の製造方法
　フィルム状封止材１は、常法によって製造することができる。例えば、第１の接着性樹脂層１１Ａと、水蒸気バリア性樹脂層１２と、第２の接着性樹脂層１１Ｂとを、その順で積層されるように共押出成形する方法、第１の接着性樹脂層１１Ａとしての単層のフィルム（第１の接着性樹脂フィルム）および第２の接着性樹脂層１１Ｂとしての単層のフィルム（第２の接着性樹脂フィルム）をそれぞれ用意し、第１の接着性樹脂フィルムに水蒸気バリア性樹脂層１２を形成した後、当該水蒸気バリア性樹脂層１２に第２の接着性樹脂フィルムを積層する方法、水蒸気バリア性樹脂層１２としての単層のフィルム（水蒸気バリア性樹脂フィルム）を用意し、その水蒸気バリア性樹脂フィルムの両面に、第１および第２の接着性樹脂層１１Ａ，１１Ｂを形成する方法、第１の接着性樹脂フィルムと、水蒸気バリア性樹脂フィルムと、第２の接着性樹脂フィルムとを用意し、それら３枚の樹脂フィルムをその順で重ねて積層する方法などの方法によって、フィルム状封止材１を製造することができる。また、剥離シート上に、第１および第２の接着性樹脂層１１Ａ，１１Ｂを形成し、第１および第２の接着性樹脂層１１Ａ，１１Ｂ付きの剥離シートをそれぞれ用意し、あらかじめ用意した水蒸気バリア性樹脂フィルムの両面に、第１および第２の接着性樹脂層１１Ａ，１１Ｂ付きの剥離シートを積層する方法によって、フィルム状封止材１を製造することもできる。 (3) Manufacturing method of film-shaped sealing material The film-shaped sealing material 1 can be manufactured by a conventional method. For example, a method in which the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B are co-extruded so as to be laminated in that order, the first adhesive property A single-layer film (first adhesive resin film) as the resin layer 11A and a single-layer film (second adhesive resin film) as the second adhesive resin layer 11B are prepared, respectively. A method of laminating the second adhesive resin film on the water vapor barrier resin layer 12 after forming the water vapor barrier resin layer 12 on the adhesive resin film, a single layer film (water vapor as the water vapor barrier resin layer 12) Barrier resin film) is prepared, and the first and second adhesive resin layers 11A and 11B are formed on both surfaces of the water vapor barrier resin film, the first adhesive resin film, and the water vapor barrier. Prepare and sex resin film, and a second adhesive resin film, by a method such as a method of laminating overlapping those three resin film in that order, it is possible to produce a film-like sealing material 1. Further, the first and second adhesive resin layers 11A and 11B are formed on the release sheet, and the release sheets with the first and second adhesive resin layers 11A and 11B are prepared, respectively. The film-form sealing material 1 can also be manufactured by the method of laminating | stacking the peeling sheet with 1st and 2nd adhesive resin layer 11A, 11B on both surfaces of a barrier resin film.
　なお、第１および第２の接着性樹脂層１１Ａ，１１Ｂとしての単層のフィルム（第１の接着性樹脂フィルム，第２の接着性樹脂フィルム）、水蒸気バリア性樹脂層１２としての単層のフィルム（水蒸気バリア性樹脂フィルム）を形成する方法としては、特に限定されず、溶融押出法、カレンダー法、乾式法、溶液法などが例示される。溶液法の場合には、上述した各層を構成する樹脂を有機溶剤に溶解した溶液を、公知の塗布方法により塗布し、得られた塗膜を適宜乾燥することで各層を形成すればよい。 In addition, the single-layer film (1st adhesive resin film, 2nd adhesive resin film) as the 1st and 2nd adhesive resin layers 11A and 11B, the single-layer film as the water vapor | steam barrier resin layer 12 The method for forming the film (water vapor barrier resin film) is not particularly limited, and examples thereof include a melt extrusion method, a calendar method, a dry method, and a solution method. In the case of the solution method, each layer may be formed by applying a solution obtained by dissolving the resin constituting each layer described above in an organic solvent by a known application method and drying the obtained coating film as appropriate.
　第１および第２の接着性樹脂層１１Ａ，１１Ｂが熱可塑性樹脂を含む場合、第１および第２の接着性樹脂層１１Ａ，１１Ｂ（第１の接着性樹脂フィルム，第２の接着性樹脂フィルム）と水蒸気バリア性樹脂層１２（水蒸気バリア性樹脂フィルム）とを積層する際には、加熱しながら積層することが好ましい。加熱温度は、第１および第２の接着性樹脂層１１Ａ，１１Ｂ（第１の接着性樹脂フィルム，第２の接着性樹脂フィルム）が軟化する温度以上であることが好ましい。 When the first and second adhesive resin layers 11A, 11B contain a thermoplastic resin, the first and second adhesive resin layers 11A, 11B (first adhesive resin film, second adhesive resin film) ) And the water vapor barrier resin layer 12 (water vapor barrier resin film) are preferably laminated while heating. The heating temperature is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B (first adhesive resin film and second adhesive resin film) are softened.
（４）フィルム状封止材の用途
　本実施形態に係るフィルム状封止材１は、ガラス板に対する接着力が、３Ｎ／２５ｍｍ以上に制御されるとともに、温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算の水蒸気透過率Ｗが、１０ｇ／ｍ２・ｄａｙ以下に制御されており、水蒸気バリア性および接着性に優れる。封止材の性能は、被着体に対する接着力および封止材の水蒸気透過率に起因しており、本実施形態に係るフィルム状封止材１によれば、種々のものの封止に使用することができ、特に電子デバイスにおける電子素子の封止に好適に使用することができる。具体的には、液晶素子、発光ダイオード（ＬＥＤ素子）、有機エレクトロルミネッセンス（有機ＥＬ）素子等を有する表示装置用モジュール、電子ペーパー、太陽電池モジュールなどが挙げられる。中でも、有機ＥＬ素子を有する表示装置用モジュール（有機ＥＬモジュール）や電子ペーパーにおいては、高い水蒸気バリア性および接着性が求められているため、本実施形態に係るフィルム状封止材１を好適に使用することができる。なお、本実施形態に係るフィルム状封止材１を用いて電子素子を封止する方法については、後述の電子デバイスの項で説明する。 (4) Use of film-shaped sealing material The film-shaped sealing material 1 according to the present embodiment has an adhesive strength to a glass plate of 3 N / 25 mm or more, a temperature of 40 ° C., and a relative humidity of 90% RH. Under the environment, the water vapor transmission rate W in terms of a thickness of 50 μm is controlled to 10 g / m 2 · day or less, and is excellent in water vapor barrier properties and adhesiveness. The performance of the sealing material is due to the adhesive strength to the adherend and the water vapor transmission rate of the sealing material, and according to the film-shaped sealing material 1 according to the present embodiment, it is used for sealing various things. In particular, it can be suitably used for sealing an electronic element in an electronic device. Specifically, a module for a display device having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, an electronic paper, a solar cell module, and the like can be given. Among these, since a high water vapor barrier property and adhesiveness are required for a display module (organic EL module) or electronic paper having an organic EL element, the film-like sealing material 1 according to this embodiment is suitably used. Can be used. In addition, the method of sealing an electronic element using the film-form sealing material 1 which concerns on this embodiment is demonstrated by the term of the below-mentioned electronic device.
〔封止シート〕
　図２に示すように、本実施形態に係る封止シート２は、前述したフィルム状封止材１と、フィルム状封止材１の片面に積層されたガスバリアフィルム２１とを備える。 [Sealing sheet]
As shown in FIG. 2, the sealing sheet 2 according to this embodiment includes the above-described film-shaped sealing material 1 and a gas barrier film 21 laminated on one surface of the film-shaped sealing material 1.
　ガスバリアフィルム２１は、水蒸気、酸素等のガスを透過させ難い特性を有するフィルムである。また、封止シート２を、表示装置用モジュール、電子ペーパー、太陽電池モジュール、後述のトップエミッション型の電子デバイスなどの透明性が必要とされる用途に用いる場合は、ガスバリアフィルム２１は透明であることが好ましい。ガスバリアフィルム２１としては、基材フィルムとガスバリア層との積層体が好ましい。このようなガスバリアフィルム２１としては、例えば、基材フィルムの片面または両面に、直接またはその他の層を介してガスバリア層を形成したもの、基材フィルムの中間にガスバリア層を設けたものなどを使用することができる。なかでも、ガスバリアフィルム２１は、基材フィルムの片面または両面に、直接またはその他の層を介してガスバリア層を形成したものが好ましい。 The gas barrier film 21 is a film having characteristics that make it difficult for gas such as water vapor and oxygen to pass therethrough. Further, when the sealing sheet 2 is used for applications that require transparency, such as a display device module, electronic paper, a solar cell module, and a top emission type electronic device described later, the gas barrier film 21 is transparent. It is preferable. The gas barrier film 21 is preferably a laminate of a base film and a gas barrier layer. As such a gas barrier film 21, for example, one having a gas barrier layer formed directly or via another layer on one or both sides of a base film, or having a gas barrier layer in the middle of a base film is used. can do. Among them, the gas barrier film 21 is preferably one in which a gas barrier layer is formed directly or via another layer on one side or both sides of a base film.
　基材フィルムとしては、例えば、ポリエチレン、ポリプロピレン、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体等のポリオレフィン、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリ塩化ビニル、ポリスチレン、ポリウレタン、ポリカーボネート、ポリアミド、ポリイミド、ポリスルフォン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリアリレート、ポリメタクリル酸メチル等のアクリル系樹脂、ポリブテン、ポリブタジエン、ポリメチルペンテン、エチレン酢酸ビニル共重合体、ＡＢＳ樹脂、アイオノマー樹脂などの樹脂からなるフィルム、またはそれらの積層フィルム等が挙げられる。それらの中でも、強度の観点から、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリカーボネート、ポリアミド、ポリイミド、ポリスルフォン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリアリレートなどからなるフィルムが好ましい。基材フィルムは、延伸フィルムであってもよいし、無延伸フィルムであってもよい。また、基材フィルムは、紫外線吸収剤等の各種添加剤を含んだものであってもよい。 Examples of the base film include polyolefin such as polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyester such as polyethylene terephthalate and polybutylene terephthalate, polychlorinated Acrylic resins such as vinyl, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, Examples thereof include a film made of a resin such as an ABS resin or an ionomer resin, or a laminated film thereof. Among these, from the viewpoint of strength, a film made of polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate and the like is preferable. The base film may be a stretched film or an unstretched film. Further, the base film may contain various additives such as an ultraviolet absorber.
　基材フィルムの厚さは、１～５００μｍであることが好ましく、特に５～３００μｍであることが好ましく、さらには１０～１００μｍであることが好ましい。 The thickness of the base film is preferably 1 to 500 μm, particularly preferably 5 to 300 μm, and more preferably 10 to 100 μm.
　ガスバリア層は、基材フィルムにガスバリア性を付与することを目的として積層される。ガスバリア層の材料としては、ガスバリアフィルム２１のガスバリア性を所望のレベルにすることができるものであれば、特に限定されることはない。ガスバリア層の材料としては、例えば、酸化ケイ素、酸窒化ケイ素、酸化アルミニウム、酸窒化アルミニウム、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ等の無機酸化物、窒化ケイ素、窒化アルミニウム等の無機窒化物、酸化窒化ケイ素等の無機酸化窒化物等、アルミニウム、マグネシウム、亜鉛、スズ等の金属などが挙げられる。これらは、１種を単独で、または２種以上を組み合わせて使用することができる。 The gas barrier layer is laminated for the purpose of imparting gas barrier properties to the base film. The material of the gas barrier layer is not particularly limited as long as the gas barrier property of the gas barrier film 21 can be set to a desired level. Examples of the material of the gas barrier layer include inorganic oxides such as silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide and tin oxide, and inorganic nitrides such as silicon nitride and aluminum nitride. And inorganic oxynitrides such as silicon oxynitride, and metals such as aluminum, magnesium, zinc, and tin. These can be used individually by 1 type or in combination of 2 or more types.
　また、ガスバリア層は、ポリシラザン化合物を公知の方法によりシリカ質膜に転化させたものであってもよい。さらに、ガスバリア層は、ポリシラザン化合物、ポリカルボシラン化合物、ポリシラン化合物、ポリオルガノシロキサン化合物、テトラオルガノシラン化合物等のケイ素化合物を含む層にプラズマイオン注入して得られる層であってもよい。プラズマイオン注入にて注入されるイオンとしては、例えば、アルゴン、ヘリウム、ネオン、クリプトン、キセノン等の希ガス、フルオロカーボン、水素、窒素、酸素、二酸化炭素、塩素、フッ素、硫黄等のイオン；金、銀、銅、白金、ニッケル、パラジウム、クロム、チタン、モリブデン、ニオブ、タンタル、タングステン、アルミニウム等の金属のイオンなどが挙げられる。 The gas barrier layer may be a polysilazane compound converted into a siliceous film by a known method. Further, the gas barrier layer may be a layer obtained by plasma ion implantation into a layer containing a silicon compound such as a polysilazane compound, a polycarbosilane compound, a polysilane compound, a polyorganosiloxane compound, or a tetraorganosilane compound. Examples of ions implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, Examples include ions of metals such as silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
　ガスバリア層の厚さは、１ｎｍ～１０μｍであることが好ましく、１０～１０００ｎｍであることがより好ましく、２０～５００ｎｍであることが特に好ましく、５０～２００ｎｍであることがさらに好ましい。 The thickness of the gas barrier layer is preferably 1 nm to 10 μm, more preferably 10 to 1000 nm, particularly preferably 20 to 500 nm, and further preferably 50 to 200 nm.
　ガスバリア層は、単層であってもよく、複数層であってもよいが、より高いガスバリア性が得られるという観点から、ガスバリア層は複数層であることが好ましい。 The gas barrier layer may be a single layer or a plurality of layers, but from the viewpoint of obtaining higher gas barrier properties, the gas barrier layer is preferably a plurality of layers.
　ガスバリア層を形成する方法は、使用する材料に応じて適宜選択すればよい。例えば、上記ガスバリア層の材料を、蒸着法、スパッタリング法、イオンプレーティング法、熱ＣＶＤ法、プラズマＣＶＤ法等により基材フィルム上に形成する方法、あるいは上記ガスバリア層の材料を有機溶剤に溶解した溶液を、基材フィルムに塗布する方法などが挙げられる。 The method for forming the gas barrier layer may be appropriately selected according to the material to be used. For example, the gas barrier layer material is formed on a base film by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like, or the gas barrier layer material is dissolved in an organic solvent. The method of apply | coating a solution to a base film is mentioned.
　ガスバリアフィルム２１の水蒸気透過率は、４０℃、９０％ＲＨにおいて、０．５ｇ／ｍ２・ｄａｙ以下であることが好ましく、特に０．１ｇ／ｍ２・ｄａｙ以下であることが好ましく、さらには０．０５ｇ／ｍ２・ｄａｙ以下であることが好ましい。 The water vapor permeability of the gas barrier film 21 is preferably 0.5 g / m 2 · day or less, particularly preferably 0.1 g / m 2 · day or less at 40 ° C. and 90% RH, It is preferably 0.05 g / m 2 · day or less.
　封止シート２を製造するには、フィルム状封止材１とガスバリアフィルム２１とを重ね合わせて積層すればよい。本実施形態に係るフィルム状封止材１は、接着力に優れた第１および第２の接着性樹脂層１１Ａ，１１Ｂを有するため、その接着性樹脂層（図２中では第１の接着性樹脂層１１Ａ）がガスバリアフィルム２１と強固に接着する。したがって、封止シート２を用いて電子デバイス等の封止をした場合に、ガスバリアフィルム２１とフィルム状封止材１との間に水蒸気が浸入することを効果的に防止することができる。なお、ガスバリアフィルム２１がその片面にガスバリア層を有する場合、ガスバリア層がフィルム状封止材１側となるように、ガスバリアフィルム２１とフィルム状封止材１とを積層することが好ましい。 In order to manufacture the sealing sheet 2, the film-like sealing material 1 and the gas barrier film 21 may be laminated and laminated. Since the film-shaped sealing material 1 according to the present embodiment has the first and second adhesive resin layers 11A and 11B excellent in adhesive strength, the adhesive resin layer (first adhesive property in FIG. 2). The resin layer 11A) adheres firmly to the gas barrier film 21. Therefore, when an electronic device or the like is sealed using the sealing sheet 2, it is possible to effectively prevent water vapor from entering between the gas barrier film 21 and the film-shaped sealing material 1. In addition, when the gas barrier film 21 has a gas barrier layer on one side, the gas barrier film 21 and the film-shaped sealing material 1 are preferably laminated so that the gas barrier layer is on the film-shaped sealing material 1 side.
　第１および第２の接着性樹脂層１１Ａ，１１Ｂが熱可塑性樹脂を含む場合、フィルム状封止材１とガスバリアフィルム２１とを積層する際には、加熱しながら積層することが好ましい。加熱温度は、フィルム状封止材１の接着性樹脂層（図２中では第１の接着性樹脂層１１Ａ）が軟化する温度以上であることが好ましい。 When the first and second adhesive resin layers 11A and 11B contain a thermoplastic resin, it is preferable to laminate the film-shaped sealing material 1 and the gas barrier film 21 while heating. The heating temperature is preferably equal to or higher than the temperature at which the adhesive resin layer (the first adhesive resin layer 11A in FIG. 2) of the film-like sealing material 1 is softened.
　本実施形態に係る封止シート２は、前述したフィルム状封止材１の用途と同様の用途に用いることができ、特に、高い水蒸気バリア性および接着性が求められる有機ＥＬ素子等を有する表示装置用モジュール、電子ペーパー、太陽電池モジュールなどの電子デバイスにおける電子素子の封止に好適に使用することができる。封止シート２を用いて封止を行う場合、ガスバリアフィルム２１が積層された側とは反対側の接着性樹脂層（図２中では第２の接着性樹脂層１１Ｂ）と被着体とを熱圧着することで、封止することができる。 The sealing sheet 2 according to the present embodiment can be used for the same application as that of the film-shaped sealing material 1 described above, and particularly has a display having an organic EL element or the like that requires high water vapor barrier properties and adhesiveness. It can use suitably for sealing of the electronic element in electronic devices, such as an apparatus module, electronic paper, and a solar cell module. When sealing is performed using the sealing sheet 2, the adhesive resin layer (second adhesive resin layer 11 </ b> B in FIG. 2) opposite to the side on which the gas barrier film 21 is laminated and the adherend are bonded. Sealing can be performed by thermocompression bonding.
〔電子デバイス〕
　本発明の一実施形態に係る電子デバイスは、上述した実施形態に係るフィルム状封止材１によって封止されている。本実施形態に係る電子デバイス３Ａは、具体的には、図３に示すように、基板３１と、基板３１上に形成された電子素子３２と、電子素子３２を封止するフィルム状封止材１と、フィルム状封止材１の電子素子３２とは反対側に積層された封止部材３３とを備える。封止部材３３としては、特に制限はなく、例えばガラス板等が挙げられる。 [Electronic device]
The electronic device according to one embodiment of the present invention is sealed with the film-shaped sealing material 1 according to the above-described embodiment. Specifically, as shown in FIG. 3, the electronic device 3 </ b> A according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a film-like sealing material that seals the electronic element 32. 1 and the sealing member 33 laminated | stacked on the opposite side to the electronic element 32 of the film-form sealing material 1 are provided. There is no restriction | limiting in particular as the sealing member 33, For example, a glass plate etc. are mentioned.
　また、本発明の他の実施形態に係る電子デバイスは、上述した実施形態に係る封止シート２によって封止されている。本実施形態に係る電子デバイス３Ｂは、具体的には、図４に示すように、基板３１と、基板３１上に形成された電子素子３２と、電子素子３２を封止する封止シート２とを備える。なお、封止シート２は、フィルム状封止材１と当該フィルム状封止材１の片面に積層されたガスバリアフィルム２１との積層体である。 Further, an electronic device according to another embodiment of the present invention is sealed with the sealing sheet 2 according to the above-described embodiment. Specifically, as shown in FIG. 4, the electronic device 3 </ b> B according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a sealing sheet 2 that seals the electronic element 32. Is provided. In addition, the sealing sheet 2 is a laminated body of the film-shaped sealing material 1 and the gas barrier film 21 laminated on one surface of the film-shaped sealing material 1.
　これらの電子デバイス３Ａ，３Ｂは、例えば、電子素子３２として液晶素子、ＬＥＤ素子、有機ＥＬ素子等を有する表示装置用モジュール、電子素子３２として電気泳動型素子、電子粉粒体型素子、コレステリック液晶素子等を有する電子ペーパー、電子素子３２として太陽電池セルを有する太陽電池モジュールなどであるが、これらに限定されるものではない。また、電子デバイス３Ａ，３Ｂは、トップエミッション型の電子デバイスであってもよいし、ボトムエミッション型の電子デバイスであってもよい。例えば、電子デバイス３Ａ，３Ｂがボトムエミッション型のデバイスである場合には、基板３１は、透明基板であることが好ましい。また、電子デバイス３Ａ，３Ｂがトップエミッション型の電子デバイスである場合には、封止部材３３およびガスバリアフィルム２１は、透明であることが好ましい。 These electronic devices 3A and 3B include, for example, a liquid crystal element, an LED element, an organic EL element, and the like as an electronic element 32, an electrophoretic element, an electronic granular element, and a cholesteric liquid crystal element as the electronic element 32. However, the present invention is not limited to these. The electronic devices 3A and 3B may be top emission type electronic devices or bottom emission type electronic devices. For example, when the electronic devices 3A and 3B are bottom emission type devices, the substrate 31 is preferably a transparent substrate. Further, when the electronic devices 3A and 3B are top emission type electronic devices, the sealing member 33 and the gas barrier film 21 are preferably transparent.
　基板３１としては、電子デバイス３Ａ，３Ｂの種類に応じて適宜選択されるが、例えば、ガラス板や樹脂フィルムが好ましく挙げられる。ガラス板の材料としては、例えば、無アルカリガラス、ソーダライムガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、バリウム・ストロンチウム含有ガラス、石英等からなる無機ガラス、ハイブリッドガラス等が挙げられる。樹脂フィルムとしては、例えば、ガスバリアフィルム２１で例示した基材フィルムが挙げられる。 The substrate 31 is appropriately selected according to the type of the electronic devices 3A and 3B, and for example, a glass plate or a resin film is preferably exemplified. Examples of the material of the glass plate include non-alkali glass, soda lime glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, barium / strontium-containing glass, inorganic glass made of quartz, hybrid glass, and the like. Can be mentioned. As a resin film, the base film illustrated with the gas barrier film 21 is mentioned, for example.
　基板３１の厚さは、電子デバイス３Ａ，３Ｂの種類に応じて適宜設定される。 The thickness of the substrate 31 is appropriately set according to the types of the electronic devices 3A and 3B.
　電子デバイス３Ａを製造する方法は特に限定されない。例えば、まず常法によって基板３１上に電子素子３２を形成する。その後、当該電子素子３２を覆うようにして、フィルム状封止材１を載置し、さらにフィルム状封止材１の上にガラス板等の封止部材３３を載置し、それらを貼り合わせ、電子素子３２を封止することで電子デバイス３Ａを製造することができる。なお、あらかじめ、フィルム状封止材１と封止部材３３とを貼り合わせた積層体を得て、この積層体を電子素子３２と貼り合わせて電子デバイス３Ａを製造してもよい。 The method for manufacturing the electronic device 3A is not particularly limited. For example, first, the electronic element 32 is formed on the substrate 31 by a conventional method. Thereafter, the film-shaped sealing material 1 is placed so as to cover the electronic element 32, and a sealing member 33 such as a glass plate is placed on the film-shaped sealing material 1, and they are bonded together. The electronic device 3 </ b> A can be manufactured by sealing the electronic element 32. In addition, the laminated body which bonded the film-form sealing material 1 and the sealing member 33 beforehand may be obtained, and this laminated body may be bonded with the electronic element 32, and the electronic device 3A may be manufactured.
　一方、電子デバイス３Ｂを製造する方法についても特に限定されない。例えば、基板３１上に形成された電子素子３２を覆うようにして、フィルム状封止材１が電子素子３２側となるように封止シート２を載置し、それらを貼り合わせ、電子素子３２を封止することで電子デバイス３Ｂを製造することができる。 On the other hand, the method for manufacturing the electronic device 3B is not particularly limited. For example, the sealing sheet 2 is placed so as to cover the electronic element 32 formed on the substrate 31 so that the film-shaped sealing material 1 is on the electronic element 32 side, and the sealing sheet 2 is bonded to the electronic element 32. The electronic device 3B can be manufactured by sealing.
　封止は、常圧で行ってもよいし、加圧しながら行ってもよく、減圧雰囲気で行ってもよく、またはこれらを組み合わせて行ってもよい。また、第１および第２の接着性樹脂層１１Ａ，１１Ｂが熱可塑性樹脂を含む場合、フィルム状封止材１と電子素子３２とを貼り合わせる際には、加熱する（熱圧着する）ことが好ましく、加熱することにより、フィルム状封止材１と電子素子３２、基板３１、および封止部材３３またはガスバリアフィルム２１とが強固に接着する。 Sealing may be performed at normal pressure, may be performed while applying pressure, may be performed in a reduced pressure atmosphere, or may be performed in combination. Further, when the first and second adhesive resin layers 11A and 11B contain a thermoplastic resin, when the film-like sealing material 1 and the electronic element 32 are bonded together, they are heated (thermocompression bonded). Preferably, the film-shaped sealing material 1 and the electronic element 32, the substrate 31, and the sealing member 33 or the gas barrier film 21 are firmly bonded by heating.
　貼り合わせる時の加熱温度は、通常、第１および第２の接着性樹脂層１１Ａ，１１Ｂならびに水蒸気バリア性樹脂層１２が軟化する温度以上であることが好ましい。本実施形態における第１および第２の接着性樹脂層１１Ａ，１１Ｂは、酸変性ポリオレフィン系樹脂およびシラン変性ポリオレフィン系樹脂の両者を含有することで、比較的短時間での加熱圧着、具体的には１秒～５分で封止することができる。このように、本実施形態に係るフィルム状封止材１は、デバイス製造時の生産性に優れたものとなっている。 The heating temperature at the time of bonding is usually preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 are softened. The first and second adhesive resin layers 11A and 11B in the present embodiment contain both an acid-modified polyolefin resin and a silane-modified polyolefin resin, so that thermocompression bonding in a relatively short time, specifically, Can be sealed in 1 second to 5 minutes. Thus, the film-form sealing material 1 which concerns on this embodiment is the thing excellent in the productivity at the time of device manufacture.
　本実施形態に係る電子デバイス３Ａ，３Ｂにおいては、電子素子３２が、本実施形態に係るフィルム状封止材１で覆われているため、外部からの水蒸気が、フィルム状封止材１の水蒸気バリア性樹脂層１２によってブロックされて、電子素子３２に到達することが防止・抑制されるため、電子素子３２が水分の悪影響を受け難いものとなっている。また、フィルム状封止材１は接着力に優れた第１および第２の接着性樹脂層１１Ａ，１１Ｂを備えているため、フィルム状封止材１と基板３１、フィルム状封止材１と電子素子３２、フィルム状封止材１と封止部材３３、フィルム状封止材１とガスバリアフィルム２１とは強固に接着し、それらの間で浮きや剥がれ等が発生したり、それらの間に水蒸気が浸入したりすることが防止・抑制されている。さらには、第１の接着性樹脂層１１Ａと水蒸気バリア性樹脂層１２との間、第２の接着性樹脂層１１Ｂと水蒸気バリア性樹脂層１２との間で層間剥離することが防止・抑制されている。 In the electronic devices 3A and 3B according to the present embodiment, since the electronic element 32 is covered with the film-shaped sealing material 1 according to the present embodiment, the water vapor from the outside is the water vapor of the film-shaped sealing material 1. Since it is blocked and suppressed by the barrier resin layer 12 and reaches the electronic element 32, the electronic element 32 is hardly affected by moisture. Moreover, since the film-form sealing material 1 is equipped with the 1st and 2nd adhesive resin layers 11A and 11B excellent in adhesive force, the film-form sealing material 1 and the board | substrate 31, the film-form sealing material 1 and The electronic element 32, the film-shaped sealing material 1 and the sealing member 33, the film-shaped sealing material 1 and the gas barrier film 21 are firmly bonded, and floating or peeling is generated between them. Invasion of water vapor is prevented and suppressed. Furthermore, delamination between the first adhesive resin layer 11A and the water vapor barrier resin layer 12 and between the second adhesive resin layer 11B and the water vapor barrier resin layer 12 is prevented / suppressed. ing.
　以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
　例えば、上記フィルム状封止材１において、第１の接着性樹脂層１１Ａおよび／または第２の接着性樹脂層１１Ｂは、水蒸気バリア性樹脂層１２に、その他の層を介して積層されていてもよい。また、第１の接着性樹脂層１１Ａおよび／または第２の接着性樹脂層１１Ｂ上には、剥離シートが積層されていてもよい。なお、剥離シートは、接着性樹脂層を形成する時に利用されたり、接着性樹脂層を保護する目的で設けられ、フィルム状封止材１を使用する際には剥離される。 For example, in the film-shaped sealing material 1, the first adhesive resin layer 11A and / or the second adhesive resin layer 11B is laminated on the water vapor barrier resin layer 12 via other layers. Also good. Further, a release sheet may be laminated on the first adhesive resin layer 11A and / or the second adhesive resin layer 11B. The release sheet is used for forming the adhesive resin layer or is provided for the purpose of protecting the adhesive resin layer, and is peeled off when the film-shaped sealing material 1 is used.
　以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔実施例１〕
＜フィルム状封止材の作製＞
　表１に示す第１の接着性樹脂層、第２の接着性樹脂層および水蒸気バリア性樹脂層を構成する材料を、押出機（東洋精機製作所社製）によって共押出成形し、厚さ１０μｍの第１の接着性樹脂層と、厚さ３０μｍの水蒸気バリア性樹脂層と、厚さ１０μｍの第２の接着性樹脂層とをその順で積層してなるフィルム状封止材を製造した。 [Example 1]
<Production of film-like encapsulant>
The materials constituting the first adhesive resin layer, the second adhesive resin layer, and the water vapor barrier resin layer shown in Table 1 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the thickness was 10 μm. A film-like encapsulant was produced by laminating a first adhesive resin layer, a 30 μm thick water vapor barrier resin layer, and a 10 μm thick second adhesive resin layer in that order.
＜ガスバリアフィルムの作製＞
　基材としてのポリエチレンテレフタレートフィルム（東洋紡績社製，コスモシャインＡ４１００，厚さ５０μｍ）上に、ポリシラザン化合物（ペルヒドロポリシラザンを主成分とするコーティング材，クラリアントジャパン社製，アクアミカＮＬ１１０－２０）をスピンコート法により塗布し、１２０℃で１分間加熱して、厚さ１５０ｎｍの、ペルヒドロポリシラザンを含むポリシラザン層を形成した。次に、プラズマイオン注入装置を用いて、ポリシラザン層の表面に、下記の条件にてアルゴンをプラズマイオン注入してガスバリア層を形成し、ガスバリアフィルムＡを作製した。 <Production of gas barrier film>
On a polyethylene terephthalate film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 50 μm) as a base material, a polysilazane compound (a coating material mainly composed of perhydropolysilazane, Clariant Japan Co., Ltd., Aquamica NL110-20) is spun. It was applied by a coating method and heated at 120 ° C. for 1 minute to form a polysilazane layer containing perhydropolysilazane having a thickness of 150 nm. Next, using a plasma ion implantation apparatus, argon was ion-implanted on the surface of the polysilazane layer under the following conditions to form a gas barrier layer, thereby producing a gas barrier film A.
　上記のガスバリア層を形成するために用いたプラズマイオン注入装置及びプラズマイオン注入条件は以下の通りである。
〔プラズマイオン注入装置〕
ＲＦ電源：日本電子社製，型番号「ＲＦ」５６０００
高電圧パルス電源：栗田製作所社製，「ＰＶ－３－ＨＳＨＶ－０８３５」
〔プラズマイオン注入条件〕
プラズマ生成ガス：Ａｒ
ガス流量：１００ｓｃｃｍ
Ｄｕｔｙ比：０．５％
印加電圧：－１５ｋＶ
ＲＦ電源：周波数　１３．５６ＭＨｚ，印加電力　１０００Ｗ
チャンバー内圧：０．２Ｐａ
パルス幅：５μｓｅｃ
処理時間（イオン注入時間）：２００秒 The plasma ion implantation apparatus and the plasma ion implantation conditions used for forming the gas barrier layer are as follows.
[Plasma ion implantation system]
RF power supply: manufactured by JEOL Ltd., model number “RF” 56000
High-voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.
[Plasma ion implantation conditions]
Plasma generation gas: Ar
Gas flow rate: 100sccm
Duty ratio: 0.5%
Applied voltage: -15 kV
RF power supply: frequency 13.56 MHz, applied power 1000 W
Chamber internal pressure: 0.2 Pa
Pulse width: 5μsec
Processing time (ion implantation time): 200 seconds
＜封止シートＡの作製＞
　得られたフィルム状封止材とガスバリアフィルムＡとを、１３０℃で加熱しながら貼り合わせて、封止シートＡを得た。 <Preparation of sealing sheet A>
The obtained film-shaped sealing material and the gas barrier film A were bonded together while heating at 130 ° C. to obtain a sealing sheet A.
＜封止シートＢの作製＞
　一方、得られたフィルム状封止材とガスバリアフィルムＢ（厚み７μｍのアルミニウム箔（ガスバリア層）の両面に、厚み１２μｍのポリエチレンテレフタレートシートをウレタン系接着剤層で接着した積層フィルム，アジヤアルミ社製）を、１３０℃で加熱しながら貼り合わせて、封止シートＢを得た。 <Preparation of sealing sheet B>
On the other hand, the obtained film-shaped encapsulant and gas barrier film B (laminated film made by Aya Aluminum Co., Ltd.) having a 12 μm thick polyethylene terephthalate sheet bonded to both sides of a 7 μm thick aluminum foil (gas barrier layer) with a urethane adhesive layer Were bonded together while heating at 130 ° C. to obtain a sealing sheet B.
＜トップエミッション型の電子デバイスの製造＞
　下記の方法により、ガラス基板上に陰極、発光層および陽極をこの順で積層し、電子素子（有機ＥＬ素子）を形成した。 <Manufacture of top emission type electronic devices>
By the following method, the cathode, the light emitting layer, and the anode were laminated | stacked in this order on the glass substrate, and the electronic element (organic EL element) was formed.
　まず、ガラス基板を溶媒洗浄およびＵＶ／オゾン処理で洗浄した後、アルミニウム（Ａｌ）（高純度化学研究所社製）を０．１ｎｍ／ｓの速度で１００ｎｍ蒸着させて陰極を形成した。 First, after the glass substrate was cleaned by solvent cleaning and UV / ozone treatment, aluminum (Al) (manufactured by High Purity Chemical Laboratory Co., Ltd.) was deposited at a rate of 0.1 nm / s to 100 nm to form a cathode.
　得られた陰極（Ａｌ膜）上に、（８－ヒドロキシ－キノリノレート）リチウム（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を１０ｎｍ、２，９－ジメチル－４，７－ジフェニル－１，１０－フェナントロリン（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を１０ｎｍ、トリス（８－ヒドロキシ－キノリネート）アルミニウム（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を４０ｎｍ、Ｎ，Ｎ’－ビス（ナフタレン－１－イル）－Ｎ，Ｎ’－ビス（フェニル）－ベンジデン）（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を６０ｎｍ、０．１～０．２ｎｍ／ｓの速度で順次蒸着させ、発光層を形成した。 On the obtained cathode (Al film), (8-hydroxy-quinolinolate) lithium (manufactured by Luminescence Technology) 10 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminescence Technology) ) 10 nm, Tris (8-hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) 40 nm, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (Luminescence) Technology (manufactured by Technology) was sequentially deposited at a rate of 60 nm and 0.1 to 0.2 nm / s to form a light emitting layer.
　得られた発光層上に、酸化インジウムスズ（ＩＴＯ）膜（厚さ：１００ｎｍ、シート抵抗：５０Ω／□）をスパッタリング法により形成して陽極を作製し、有機ＥＬ素子を得た。なお、蒸着時の真空度は、全て１×１０－４Ｐａ以下であった。 On the obtained light emitting layer, an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50Ω / □) was formed by sputtering to produce an anode, whereby an organic EL device was obtained. The degree of vacuum at the time of vapor deposition was 1 × 10 −4 Pa or less.
　次いで、上記封止シートＡを、窒素雰囲気下で、ホットプレートを用いて１２０℃で３０分間加熱して乾燥し、封止シートＡ中に含まれる水分を除去した後、そのまま放置して室温まで冷却した。そして、ガラス基板上に形成された有機ＥＬ素子を覆うように、フィルム状封止材が有機ＥＬ素子側になるように封止シートＡを載置し、それらを１００℃で熱圧着して有機ＥＬ素子を封止し、トップエミッション型の電子デバイスを得た。 Next, the sealing sheet A is dried by heating at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet A, and then left as it is to room temperature. Cooled down. And the sealing sheet A is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, and they are thermocompression-bonded at 100 degreeC, and organic The EL element was sealed to obtain a top emission type electronic device.
＜ボトムエミッション型の電子デバイスの製造＞
　下記の方法により、ガラス基板上に陽極、発光層および陰極をこの順で積層し、電子素子（有機ＥＬ素子）を形成した。 <Manufacture of bottom emission type electronic devices>
By the following method, an anode, a light emitting layer, and a cathode were laminated in this order on a glass substrate to form an electronic element (organic EL element).
　まず、ガラス基板の表面に酸化インジウムスズ（ＩＴＯ）膜（厚さ：１５０ｎｍ、シート抵抗：３０Ω／□）をスパッタリング法により形成し、次いで、溶媒洗浄およびＵＶ／オゾン処理を行うことで陽極を作製した。 First, an indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30Ω / □) is formed on the surface of the glass substrate by sputtering, and then an anode is prepared by solvent cleaning and UV / ozone treatment. did.
　得られた陽極（ＩＴＯ膜）上に、Ｎ，Ｎ’－ビス（ナフタレン－１－イル）－Ｎ，Ｎ’－ビス（フェニル）－ベンジデン）（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を６０ｎｍ、トリス（８－ヒドロキシ－キノリネート）アルミニウム（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を４０ｎｍ、２，９－ジメチル－４，７－ジフェニル－１，１０－フェナントロリン（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を１０ｎｍ、（８－ヒドロキシ－キノリノレート）リチウム（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を１０ｎｍ、０．１～０．２ｎｍ／ｓの速度で順次蒸着させ、発光層を形成した。 On the obtained anode (ITO film), N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (manufactured by Luminescence Technology) was 60 nm, Tris (8- Hydroxy-quinolinate) Aluminum (manufactured by Luminescence Technology) at 40 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminesense Technology) at 10 nm, (8-hydroxy-quinolinolate) lithium (Luminescence) Technology) was sequentially deposited at a rate of 10 nm and 0.1 to 0.2 nm / s to form a light emitting layer.
　得られた発光層上に、アルミニウム（Ａｌ）（高純度化学研究所社製）を０．１ｎｍ／ｓの速度で１００ｎｍ蒸着させて陰極を形成し、有機ＥＬ素子を得た。なお、蒸着時の真空度は、全て１×１０－４Ｐａ以下であった。 On the obtained light-emitting layer, aluminum (Al) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, thereby obtaining an organic EL device. The degree of vacuum at the time of vapor deposition was 1 × 10 −4 Pa or less.
　次いで、上記封止シートＢを、窒素雰囲気下で、ホットプレートを用いて１２０℃で３０分間加熱して、封止シートＢ中に含まれる水分を除去した後、そのまま放置して室温まで冷却した。そして、ガラス基板上に形成された有機ＥＬ素子を覆うように、フィルム状封止材が有機ＥＬ素子側になるように封止シートＢを載置し、それらを１００℃で熱圧着して有機ＥＬ素子を封止し、ボトムエミッション型の電子デバイスを得た。 Next, the sealing sheet B was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet B, and then left to cool to room temperature. . And the sealing sheet B is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, and they are thermocompression-bonded at 100 degreeC, and organic The EL element was sealed to obtain a bottom emission type electronic device.
〔実施例２～１０，比較例１～４〕
　接着性樹脂層および水蒸気バリア性樹脂層を構成する材料および各層の厚みを表１に示すように変更する以外、実施例１と同様にしてフィルム状封止材を製造した。このフィルム状封止材を使用して、実施例１と同様にして封止シートＡ，Ｂを作製し、トップエミッション型およびボトムエミッション型の電子デバイスを得た。 [Examples 2 to 10, Comparative Examples 1 to 4]
A film-like sealing material was produced in the same manner as in Example 1 except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer and the thickness of each layer were changed as shown in Table 1. Using this film-shaped encapsulant, encapsulating sheets A and B were produced in the same manner as in Example 1 to obtain top emission type and bottom emission type electronic devices.
　なお、表１に記載の略号等の詳細は以下の通りである。
［接着性樹脂層］
・ＡｄｍｅｒＳＦ７３１：無水マレイン酸変性ポリエチレン系樹脂（三井化学社製，商品名「ＡｄｍｅｒＳＦ７３１」，ビカット軟化点：４３℃，１９０℃・荷重２０．２ＮにおけるＭＦＲ：２．６ｇ／１０分）
・リンクロンＸＬＥ８１５Ｎ：シラン変性直鎖状低密度ポリエチレン（三菱化学社製，商品名「リンクロンＸＬＥ８１５Ｎ」，１９０℃・荷重２０．２ＮにおけるＭＦＲ：０．５ｇ／１０分）
・ウルトラセン　６３０：エチレン－酢酸ビニル共重合体（東ソー社製，商品名「ウルトラセン　６３０」）
・ニュクレル　Ｎ１２０７Ｃ：エチレン－メタクリル酸共重合体（三井－デュポンポリケミカル社製，商品名「ニュクレル　Ｎ１２０７Ｃ」）
・ハイミラン　１６５０：エチレン系アイオノマー（Ｚｎタイプ）（三井－デュポンポリケミカル社製，商品名「ハイミラン　１６５０」）
［水蒸気バリア性樹脂層］
・ＴＯＰＡＳ９５０６Ｆ－０４：前述した構造式（ａ）で示されるシクオロレフィン重合体（ポリプラスチックス社製，商品名「ＴＯＰＡＳ９５０６Ｆ－０４」，ガラス転移温度６５℃）
・ＡＰＬ８００８Ｔ：前述した構造式（ｂ）で示されるシクオロレフィン重合体（三井化学社製，商品名「アペル８００８Ｔ」，ガラス転移温度７０℃）
・ＺＥＯＮＯＲ１０６０Ｒ：前述した構造式（ｄ）で示されるシクオロレフィン重合体（日本ゼオン社製，商品名「ＺＥＯＮＯＲ１０６０Ｒ」，ガラス転移温度１００℃）
・Ｅｘｘｏｎ　Ｂｕｔｙｌ　３６５：イソブチレン－イソプレン共重合体（日本ブチル社製，商品名「Ｅｘｘｏｎ　Ｂｕｔｙｌ　３６５」）
・エクセレンＶＬ　ＥＵＬ７３１：超低密度ポリエチレン（住友化学社製，商品名「エクセレンＶＬ　ＥＵＬ７３１」）
・スミカセンＬ７０５：低密度ポリエチレン（住友化学社製，商品名「スミカセンＬ７０５」） Details of the abbreviations and the like described in Table 1 are as follows.
[Adhesive resin layer]
Admer SF731: Maleic anhydride-modified polyethylene resin (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point: 43 ° C., 190 ° C., MFR at load 20.2 N: 2.6 g / 10 min)
・ Linkron XLE815N: Silane-modified linear low-density polyethylene (Mitsubishi Chemical Co., Ltd., trade name “Linklon XLE815N”, MFR at 190 ° C. and load 20.2 N: 0.5 g / 10 min)
・ Ultrasen 630: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, trade name “Ultrasen 630”)
・ Nucleel N1207C: ethylene-methacrylic acid copolymer (Mitsui-DuPont Polychemical Co., Ltd., trade name “Nucrel N1207C”)
・ High Milan 1650: Ethylene ionomer (Zn type) (Mitsui-DuPont Polychemical Co., Ltd., trade name “High Milan 1650”)
[Water vapor barrier resin layer]
TOPAS9506F-04: Cycloolefin polymer represented by the structural formula (a) described above (trade name “TOPAS9506F-04”, glass transition temperature 65 ° C., manufactured by Polyplastics Co., Ltd.)
APL8008T: Cycloolefin polymer represented by the above structural formula (b) (Mitsui Chemicals, trade name “Apel 8008T”, glass transition temperature 70 ° C.)
ZEONOR1060R: Cycloolefin polymer represented by the structural formula (d) described above (manufactured by Zeon Corporation, trade name “ZEONOR1060R”, glass transition temperature 100 ° C.)
Exxon Butyl 365: Isobutylene-isoprene copolymer (Nippon Butyl Co., Ltd., trade name “Exxon Butyl 365”)
・ Excellen VL EUL731: Ultra-low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name “Excellen VL EUL731”)
・ Sumikasen L705: Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikasen L705”)
〔試験例１〕（水蒸気透過率の測定）
　実施例または比較例で得られたフィルム状封止材の厚み５０μｍ換算の水蒸気透過率Ｗを測定した。また、第１の接着性樹脂層、第２の接着性樹脂層および水蒸気バリア性樹脂層を構成する材料を、それぞれ押出機（東洋精機製作所社製）により押出成形して、厚さ５０μｍの単層の樹脂フィルムを製膜した。得られた単層の樹脂フィルムを用いて、各層の厚み５０μｍ換算の水蒸気透過率Ｗ１、Ｗ２およびＷ３を測定した。具体的には、ＬＹＳＳＹ社製の透過率測定機「Ｌ８０－５０００」を用い、４０℃、９０％ＲＨの条件で測定を行った。結果を表１に示す。 [Test Example 1] (Measurement of water vapor transmission rate)
The water vapor permeability W in terms of a thickness of 50 μm of the film-like sealing material obtained in the examples or comparative examples was measured. In addition, the materials constituting the first adhesive resin layer, the second adhesive resin layer, and the water vapor barrier resin layer are respectively extruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a single unit having a thickness of 50 μm. A layer resin film was formed. Using the obtained single-layer resin film, the water vapor transmission rates W1, W2 and W3 of each layer in terms of a thickness of 50 μm were measured. Specifically, the measurement was performed under the conditions of 40 ° C. and 90% RH using a transmittance measuring device “L80-5000” manufactured by LYSSY. The results are shown in Table 1.
〔試験例２〕（接着力の測定）
　実施例または比較例で得られた封止シートＢの接着性樹脂層を、被着体としてのガラス板（ソーダライムガラス，日本板硝子社製）と重ね合わせ、１３０℃で加熱しながら貼り合わせて、試験片を得た。 [Test Example 2] (Measurement of adhesive strength)
The adhesive resin layer of the sealing sheet B obtained in the example or the comparative example is overlaid on a glass plate (soda lime glass, manufactured by Nippon Sheet Glass Co., Ltd.) as an adherend, and bonded while heating at 130 ° C. A test piece was obtained.
　得られた試験片を、貼り合わせ後２４時間、２３℃、５０％ＲＨの環境下で放置した後、同環境下で、引張試験機（オリエンテック社製，テンシロン）を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で剥離試験を行い、接着力（Ｎ／２５ｍｍ）を測定した。結果を表１に示す。なお、表１中、接着力が１Ｎ／２５ｍｍ以下の場合は、「＜１」と表記した。 The obtained test piece was allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours after being bonded, and then in that environment, using a tensile tester (manufactured by Orientec, Tensilon), a peeling rate of 300 mm. / Min, a peel test was performed under the conditions of a peel angle of 180 °, and the adhesive strength (N / 25 mm) was measured. The results are shown in Table 1. In Table 1, when the adhesive strength was 1 N / 25 mm or less, it was expressed as “<1”.
〔試験例３〕（電子デバイスの評価）
　実施例または比較例で得られたトップエミッション型およびボトムエミッション型の電子デバイスを、２３℃、５０％ＲＨの環境下で１００時間放置した後、有機ＥＬ素子を起動させ、ダークスポット（非発光箇所）の有無を観察し、以下の基準で評価した。結果を表１に示す。
Ａ：ダークスポットが発光面積の５％未満
Ｂ：ダークスポットが発光面積の５％以上１０％未満
Ｃ：ダークスポットが発光面積の１０％以上９０％未満 [Test Example 3] (Evaluation of electronic device)
After leaving the top emission type and bottom emission type electronic devices obtained in the examples or comparative examples in an environment of 23 ° C. and 50% RH for 100 hours, the organic EL element is activated and dark spots (non-light emitting points) ) Was observed and evaluated according to the following criteria. The results are shown in Table 1.
A: Dark spot is less than 5% of light emission area B: Dark spot is 5% or more and less than 10% of light emission area C: Dark spot is 10% or more and less than 90% of light emission area
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１から分かるように、実施例で得られたフィルム状封止材は、特定の範囲の水蒸気透過率および接着力に制御されており、実施例で得られたフィルム状封止材によって封止された有機ＥＬ素子は、ダークスポットがほとんど見られず、電子デバイスの性能が良好であった。一方、比較例のフィルム状封止材は、水蒸気透過率が高いため、当該フィルム状封止材によって封止された有機ＥＬ素子は、ダークスポットが多く見られ、電子デバイスの性能が劣っていた。また、比較例３のフィルム状封止材は、接着力が低すぎて、有機ＥＬ素子を封止することができなかった。 As can be seen from Table 1, the film-shaped encapsulant obtained in the examples is controlled to a specific range of water vapor transmission rate and adhesive force, and is sealed by the film-form encapsulant obtained in the examples. The produced organic EL element had almost no dark spots, and the performance of the electronic device was good. On the other hand, since the film-shaped sealing material of the comparative example has a high water vapor transmission rate, the organic EL element sealed with the film-shaped sealing material has many dark spots, and the performance of the electronic device is inferior. . Moreover, the film-form sealing material of the comparative example 3 had too low adhesive force, and could not seal an organic EL element.
　本発明に係るフィルム状封止材および封止シートは、例えば有機ＥＬモジュールや電子ペーパーに好適に用いられる。また、本発明に係る電子デバイスは、例えば有機ＥＬモジュールや電子ペーパーとして好適である。 The film-like sealing material and the sealing sheet according to the present invention are suitably used for, for example, an organic EL module and electronic paper. The electronic device according to the present invention is suitable as an organic EL module or electronic paper, for example.
１…フィルム状封止材
　１１Ａ…第１の接着性樹脂層
　１１Ｂ…第２の接着性樹脂層
　１２…水蒸気バリア性樹脂層
２…封止シート
　２１…ガスバリアフィルム
３Ａ，３Ｂ…電子デバイス
　３１…基板
　３２…電子素子
　３３…封止部材 DESCRIPTION OF SYMBOLS 1 ... Film-form sealing material 11A ... 1st adhesive resin layer 11B ... 2nd adhesive resin layer 12 ... Water vapor | steam barrier resin layer 2 ... Sealing sheet 21 ... Gas barrier film 3A, 3B ... Electronic device 31 ... Board | substrate 32 ... Electronic element 33 ... Sealing member

Claims (7)

  1. 　被着体に対して接着性を示す第１および第２の接着性樹脂層と、
    　前記第１の接着性樹脂層と前記第２の接着性樹脂層との間に位置する水蒸気バリア性樹脂層とを備えたフィルム状封止材であって、
    　前記第１の接着性樹脂層または前記第２の接着性樹脂層のいずれか一方の面をガラス板に貼り合わせた際の前記ガラス板に対する接着力が、３Ｎ／２５ｍｍ以上であり、
    　温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算の水蒸気透過率Ｗが、１０ｇ／ｍ２・ｄａｙ以下である
    ことを特徴とするフィルム状封止材。     First and second adhesive resin layers exhibiting adhesion to an adherend;
    A film-like sealing material comprising a water vapor barrier resin layer positioned between the first adhesive resin layer and the second adhesive resin layer,
    Adhesive force with respect to the glass plate when either one surface of the first adhesive resin layer or the second adhesive resin layer is bonded to the glass plate is 3 N / 25 mm or more,
    A film-like sealing material having a water vapor transmission rate W converted to a thickness of 50 μm in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH is 10 g / m 2 · day or less.
  2. 　温度４０℃、相対湿度９０％ＲＨの環境下における、厚み５０μｍ換算の前記第１の接着性樹脂層の水蒸気透過率をＷ１（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算の前記第２の接着性樹脂層の水蒸気透過率をＷ２（ｇ／ｍ２・ｄａｙ）、厚み５０μｍ換算の前記水蒸気バリア性樹脂層の水蒸気透過率をＷ３（ｇ／ｍ２・ｄａｙ）としたときに、Ｗ１、Ｗ２およびＷ３が次の関係を満たす
    　Ｗ１＞Ｗ３、Ｗ２＞Ｗ３、かつＷ３≦１０
    ことを特徴とする請求項１に記載のフィルム状封止材。     In an environment of a temperature of 40 ° C. and a relative humidity of 90% RH, the water vapor permeability of the first adhesive resin layer in terms of thickness 50 μm is W1 (g / m 2 · day), and the second adhesion in terms of thickness 50 μm. W1 and W2 when the water vapor transmission rate of the water-soluble resin layer is W2 (g / m 2 · day) and the water vapor transmission rate of the water vapor barrier resin layer converted to a thickness of 50 μm is W3 (g / m 2 · day). And W3 satisfy the following relationship: W1> W3, W2> W3, and W3 ≦ 10
    The film-like sealing material according to claim 1.
  3. 　前記第１の接着性樹脂層の厚さをＴ１（μｍ）、前記第２の接着性樹脂層の厚さをＴ２（μｍ）、前記水蒸気バリア性樹脂層の厚さをＴ３（μｍ）としたときに、Ｔ１、Ｔ２およびＴ３が次の関係を満たす
    　０．１＜{Ｔ３／（Ｔ１＋Ｔ２＋Ｔ３）}＜０．９９
    　１≦Ｔ１≦１００
    　１≦Ｔ２≦１００
    　５≦Ｔ３≦３００
    ことを特徴とする請求項１または２に記載のフィルム状封止材。     The thickness of the first adhesive resin layer was T1 (μm), the thickness of the second adhesive resin layer was T2 (μm), and the thickness of the water vapor barrier resin layer was T3 (μm). Sometimes T1, T2, and T3 satisfy the following relationship: 0.1 <{T3 / (T1 + T2 + T3)} <0.99
    1 ≦ T1 ≦ 100
    1 ≦ T2 ≦ 100
    5 ≦ T3 ≦ 300
    The film-shaped sealing material according to claim 1 or 2, wherein
  4. 　前記第１および第２の接着性樹脂層は、前記水蒸気バリア性樹脂層に直接積層されており、それらの３層構造からなることを特徴とする請求項１～３のいずれか一項に記載のフィルム状封止材。 The first and second adhesive resin layers are directly laminated on the water vapor barrier resin layer, and have a three-layer structure thereof. Film-like sealing material.
  5. 　請求項１～４のいずれか一項に記載のフィルム状封止材と、
    　前記フィルム状封止材の片面に積層されたガスバリアフィルムと
    を備えたことを特徴とする封止シート。     A film-like sealing material according to any one of claims 1 to 4,
    A sealing sheet comprising a gas barrier film laminated on one side of the film-shaped sealing material.
  6. 　請求項１～４のいずれか一項に記載のフィルム状封止材によって封止されたことを特徴とする電子デバイス。 An electronic device sealed with the film-like sealing material according to any one of claims 1 to 4.
  7. 　請求項５に記載の封止シートによって封止されたことを特徴とする電子デバイス。 An electronic device sealed with the sealing sheet according to claim 5.
PCT/JP2014/051790 2013-01-31 2014-01-28 Film-shaped sealing material, sealing sheet, and electronic device WO2014119551A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013017311A JP2016064499A (en) 2013-01-31 2013-01-31 Film-like encapsulating material, encapsulating sheet, and electronic device
JP2013-017311 2013-01-31

Publications (1)

Publication Number Publication Date
WO2014119551A1 true WO2014119551A1 (en) 2014-08-07

Family

ID=51262265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/051790 WO2014119551A1 (en) 2013-01-31 2014-01-28 Film-shaped sealing material, sealing sheet, and electronic device

Country Status (3)

Country Link
JP (1) JP2016064499A (en)
TW (1) TW201437038A (en)
WO (1) WO2014119551A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015098648A1 (en) * 2013-12-26 2015-07-02 リンテック株式会社 Sheet-shaped sealing material, sealing sheet, electronic-device seal, and organic electroluminescent element
JP2018525773A (en) * 2015-06-09 2018-09-06 エルジー・ケム・リミテッド Organic electronic equipment
US10647890B2 (en) 2015-06-09 2020-05-12 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, and organic electronic device comprising same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011108600A1 (en) * 2010-03-02 2011-09-09 三菱樹脂株式会社 Solar cell sealing material, and solar cell module manufactured using same
WO2012073971A1 (en) * 2010-11-30 2012-06-07 三菱樹脂株式会社 Laminate for solar cell and solar cell module produced using same
JP2012216805A (en) * 2011-03-25 2012-11-08 Sekisui Chem Co Ltd Solar cell module filler sheet
WO2013002288A1 (en) * 2011-06-28 2013-01-03 リンテック株式会社 Adhesive composition and adhesive sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011108600A1 (en) * 2010-03-02 2011-09-09 三菱樹脂株式会社 Solar cell sealing material, and solar cell module manufactured using same
WO2012073971A1 (en) * 2010-11-30 2012-06-07 三菱樹脂株式会社 Laminate for solar cell and solar cell module produced using same
JP2012216805A (en) * 2011-03-25 2012-11-08 Sekisui Chem Co Ltd Solar cell module filler sheet
WO2013002288A1 (en) * 2011-06-28 2013-01-03 リンテック株式会社 Adhesive composition and adhesive sheet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015098648A1 (en) * 2013-12-26 2015-07-02 リンテック株式会社 Sheet-shaped sealing material, sealing sheet, electronic-device seal, and organic electroluminescent element
JP2018525773A (en) * 2015-06-09 2018-09-06 エルジー・ケム・リミテッド Organic electronic equipment
US10647890B2 (en) 2015-06-09 2020-05-12 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, and organic electronic device comprising same
JP2021005567A (en) * 2015-06-09 2021-01-14 エルジー・ケム・リミテッド Organic electronic device

Also Published As

Publication number Publication date
TW201437038A (en) 2014-10-01
JP2016064499A (en) 2016-04-28

Similar Documents

Publication Publication Date Title
JP6061707B2 (en) Film-shaped sealing material for electronic device, sealing sheet for electronic device, and electronic device
JP5997043B2 (en) Film-like sealing material, sealing sheet, and electronic device
JP6734955B2 (en) Adhesive sheet, electronic device and manufacturing method thereof
WO2014119543A1 (en) Film-shaped sealing material for electronic device, sealing sheet for electronic device, and electronic device
US11162003B2 (en) Adhesive composition, sealing sheet, and sealed body
WO2010104069A1 (en) Underside protective sheet for solar cell, solar cell module, and gas-barrier film
US20180346763A1 (en) Adhesive composition, sealing sheet, and sealed body
WO2016056625A1 (en) Film-form sealant, sealing sheet, and electronic device
KR20170116232A (en) Element-sealing resin composition for organic electronic device, element-sealing resin sheet for organic electronic device, organic electroluminescence element, and image display apparatus
KR20190046839A (en) An adhesive composition, a sealing sheet,
JP2012076291A (en) Gas barrier film laminate, and packaging bag
JP2016087791A (en) Film-like encapsulating material, encapsulating sheet and electronic device
WO2014119551A1 (en) Film-shaped sealing material, sealing sheet, and electronic device
JP6144635B2 (en) Film-shaped sealing material for electronic device, sealing sheet for electronic device, and electronic device
JP6061706B2 (en) Film-shaped sealing material for electronic device, sealing sheet for electronic device, and electronic device
WO2014103866A1 (en) Film-like sealing material, sealing sheet and electronic device
JP6468810B2 (en) Film-like sealing material, sealing sheet, and electronic device
JP5659667B2 (en) Gas barrier film laminate and packaging bag
WO2014119566A1 (en) Film-shaped sealing material, sealing sheet, and electronic device
JP5659668B2 (en) Gas barrier film laminate and packaging bag
CN112752813B (en) Gas barrier laminate
JP2014148077A (en) Film-like sealing material, sealing sheet and electronic device
JP2016078260A (en) Film-like sealing material, sealing material and electronic device
JP6530900B2 (en) Film-like sealing material, sealing sheet and electronic device
JP2016078261A (en) Film-like sealing material, sealing material and electronic device

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: 14745858

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14745858

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP