WO2020067488A1 - Stratifié faisant barrière aux gaz - Google Patents

Stratifié faisant barrière aux gaz Download PDF

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Publication number
WO2020067488A1
WO2020067488A1 PCT/JP2019/038313 JP2019038313W WO2020067488A1 WO 2020067488 A1 WO2020067488 A1 WO 2020067488A1 JP 2019038313 W JP2019038313 W JP 2019038313W WO 2020067488 A1 WO2020067488 A1 WO 2020067488A1
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WO
WIPO (PCT)
Prior art keywords
gas barrier
adhesive layer
layer
film
barrier laminate
Prior art date
Application number
PCT/JP2019/038313
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English (en)
Japanese (ja)
Inventor
樹 長谷川
章生 加太
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
Priority to KR1020217008351A priority Critical patent/KR20210068018A/ko
Priority to JP2020549468A priority patent/JP7356442B2/ja
Priority to CN201980062627.0A priority patent/CN112752813B/zh
Publication of WO2020067488A1 publication Critical patent/WO2020067488A1/fr

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Classifications

    • 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
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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

Definitions

  • the present invention relates to a gas barrier laminate.
  • Patent Literature 1 discloses a technique for sealing an organic EL element using a sealing film in which a gas barrier film is laminated on an adhesive film.
  • An object to be sealed such as an electronic device such as an organic EL element, which needs to be prevented from being deteriorated by oxygen, moisture, or the like, has an adhesive layer, such as a sealing film having a layer configuration described in Patent Document 1. It may be sealed by a gas barrier laminate having a laminated structure in which a gas barrier film is laminated.
  • the gas barrier film is disposed on the outermost surface. Therefore, the gas barrier film may be damaged or cracked, and the gas barrier property of the gas barrier film may be reduced. Further, when the object to be sealed is a light emitting element such as an organic EL element and is used for a display or the like, if the gas barrier film is scratched or cracked, the scratched or cracked becomes a defect and a bright spot or the like is generated. Sometimes it becomes.
  • the present inventors have proposed a process of storing and transporting the gas barrier laminate until use, a process of sealing the object to be sealed with the gas barrier laminate to produce a sealed body, and the sealing.
  • the process of processing and transporting the body in order to prevent the gas barrier film from being damaged or cracked, the whole surface of the gas barrier film was protected with a protect film, and the protect film was peeled at a desired timing.
  • the desired timing means, for example, a timing at which the protection of the gas barrier film becomes unnecessary, a timing at which the gas barrier film needs to be exposed, and the like.
  • the present invention has been made in view of such a problem, and processes such as storage and transportation until use of the gas barrier laminate, sealing the object to be sealed with the gas barrier laminate to form a sealed body.
  • Gas barrier laminate capable of improving the durability of an object to be sealed without forming a gap between the stopper and the adhesive layer, and a method of manufacturing a sealed body using the gas barrier laminate The purpose is to provide.
  • the present inventors have conducted intensive studies based on the above idea of protecting a gas barrier film with a protection film.
  • the gas barrier laminate having a laminated structure in which the adhesive layer, the gas barrier film, and the protect film are arranged in this order is attached to the glass plate under specific conditions with the adhesive layer as a bonding surface.
  • the adhesive force between the glass plate and the adhesive layer, and the adhesive force between the gas barrier film and the protection film, by adjusting so as to satisfy a specific relationship it is possible to solve the above problem I found that.
  • a gas barrier laminate having a laminated structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order, The gas barrier laminate is pressed against a glass plate with a roller using the adhesive layer as a bonding surface under the following condition ( ⁇ ), and the gas barrier laminate and the glass plate are adhered to each other. ⁇ ), and the other conditions are measured in accordance with JIS Z0237: 2000. The adhesive force a between the glass plate and the adhesive layer, and the adhesive strength a between the gas barrier film and the protection film are measured.
  • a gas barrier laminate in which the adhesive strength b satisfies the following formula (1). a> b ...
  • the curable adhesive layer is a layer formed from an adhesive composition containing a polyolefin-based resin (A).
  • the polyolefin-based resin (A) includes a modified polyolefin-based resin (A1).
  • the curable adhesive layer contains a curable component (B), and the curable component (B) contains a polyfunctional epoxy compound (BL) that is liquid at 25 ° C. [2] to [2].
  • the gas barrier laminate according to any one of [4].
  • Mw weight average molecular weight
  • processes such as storage and transport until the gas barrier laminate is used, a process of manufacturing a sealed body by sealing an object to be sealed with the gas barrier laminate, and a process of manufacturing the sealed body In the process of processing and transporting, etc., while preventing the gas barrier film from being damaged or cracked by the protect film, when peeling the protect film at a desired timing, between the sealed object and the adhesive layer It is possible to provide a gas barrier laminate having no gaps and good durability of the object to be sealed, and a method for manufacturing a sealed body using the gas barrier laminate.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. Is a value measured based on the method described in Examples.
  • the gas barrier laminate of the present invention is a gas barrier laminate having a laminated structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order.
  • the gas-barrier laminate of the present invention is obtained by pressing the gas-barrier laminate with a roller against a glass plate under the following condition ( ⁇ ) with the adhesive layer as a bonding surface. And then peeled off under the following condition ( ⁇ ), and the other conditions were measured according to JIS Z0237: 2000, the adhesive force a between the glass plate and the adhesive layer, the gas barrier film and the protect film. Is adjusted so as to satisfy the following equation (1). a> b ...
  • the force a is measured by peeling the gas barrier laminate adhered to the glass plate from the glass plate.
  • the adhesive strength b between the gas barrier film and the protection film is measured by peeling the protection film from the gas barrier laminate adhered to the glass plate.
  • the term “gas barrier” refers to a function of preventing transmission of a gas such as oxygen or water vapor.
  • the gas barrier laminate of the present invention is not particularly limited as long as it has a laminated structure in which an adhesive layer, a gas barrier film, and a protection film are laminated in this order.
  • the layer configuration of the gas barrier laminate of one embodiment of the present invention includes, for example, the following embodiments in which only an adhesive layer, a gas barrier film, and a protect film are laminated in this order, and further, arbitrarily laminated on the adhesive layer.
  • the following embodiments having a release sheet to be performed are exemplified.
  • Adhesive layer / gas barrier film / protect film ⁇ Release sheet / adhesive layer / gas barrier film / protect film
  • the aspect of the layer configuration having the release sheet indicates a state before using the gas barrier laminate as a sealing material. It was done.
  • the release sheet When used as a sealing material, the release sheet is peeled off and removed, and the surface of the exposed adhesive layer and the object to be sealed are attached to cover and seal the object to be sealed. Then, the removal of the protection film laminated on the gas barrier film is performed in the process of manufacturing the sealed body by sealing the object to be sealed with the gas barrier laminate, or in the process of processing or transporting the sealed body. Done.
  • the layer configuration of the gas barrier laminate of the present invention is, for example, in the following mode after the surface of the exposed adhesive layer and the object to be sealed are bonded to cover the object to be sealed.
  • the adhesive layer of the gas barrier laminate of one embodiment of the present invention may be a curable adhesive layer.
  • the layer configuration of the gas barrier laminate after curing the curable adhesive layer is as follows. -Cured adhesive layer / gas barrier film / protect film
  • curable adhesive layer means an uncured adhesive layer.
  • the sealed body produced by sealing the object to be sealed with the gas barrier laminate of the present invention is protected by the protective film until the protective film is peeled off, and the gas barrier film is damaged or broken. Is prevented from occurring.
  • the following mode is adopted.
  • Adhesive layer / gas barrier film In addition, when the adhesive layer is a curable adhesive layer, after curing the curable adhesive layer, and after peeling the protective film from the sealing body, It becomes an aspect.
  • -Cured adhesive layer / gas barrier film In the present specification, the object to be sealed is sealed by bonding the exposed surface of the adhesive layer and the object to cover the object to be sealed. Is referred to as a “sealed body”.
  • the adhesive layer may be uncured, may be cured, or may be in an intermediate state between uncured and cured, that is, a semi-cured state.
  • the adhesive layer of the sealing body is uncured or in a semi-cured state, it can be said that the sealing body is a “sealing precursor”.
  • the process of processing the sealing body also includes a process of curing the adhesive layer of the sealing body.
  • the present inventors have performed processes such as storage and transportation until the gas barrier laminate is used, sealing the object to be sealed with the gas barrier laminate to produce a sealed body, and the sealing body.
  • processes such as storage and transportation until the gas barrier laminate is used, sealing the object to be sealed with the gas barrier laminate to produce a sealed body, and the sealing body.
  • the whole surface of the gas barrier film was protected with a protect film, and the protect film was peeled at a desired timing.
  • the protection film is peeled off after sealing the object to be sealed with the gas barrier laminate, a gap is generated between the object to be sealed and the adhesive layer, and oxygen, water vapor, and the like enter from the gap. It became clear that the object to be sealed might be deteriorated. It was also found that the appearance was poor.
  • the present inventors have conducted intensive studies in order to find out the cause.
  • the present inventors have found that the object to be sealed is protected at any timing of the process of manufacturing the sealed body by sealing the object with the gas barrier laminate, and the process of processing and transporting the sealed body. Even when the film was peeled off, no gap was generated between the object to be sealed and the adhesive layer, and it was found that a gas barrier laminate which was extremely easy to use in various processes could be provided. Was.
  • the gas-barrier laminate of the present invention is obtained by pressing the gas-barrier laminate with a roller under the following condition ( ⁇ ) by using a roller with the adhesive layer as a bonding surface, and bonding the gas-barrier laminate to the glass plate. After that, the film was peeled off under the following condition ( ⁇ ), and the other conditions were measured according to JIS Z0237: 2000, and the adhesive force a between the glass plate and the adhesive layer, and the gas barrier film and the protection film were compared. The adhesive force b between them is adjusted so as to satisfy the following expression (1). a> b ...
  • the adhesive strength a between the glass plate and the adhesive layer is larger than the adhesive strength b between the gas barrier film and the protection film, and is preferably 1.0 N / 50 mm or more. It is preferably at least 2.0 N / 50 mm, more preferably at least 3 N / 50 mm, even more preferably at least 4 N / 50 mm, even more preferably at least 5 N / 50 mm.
  • the upper limit of the adhesive force a between the glass plate and the adhesive layer is not particularly limited, but is usually 20 N / 50 mm.
  • the adhesive strength b between the gas barrier film and the protection film is smaller than the adhesive strength a between the glass plate and the adhesive layer, preferably 1 N / 50 mm or less, more preferably It is 0.5 N / 50 mm or more, more preferably 0.4 N / 50 mm or less, even more preferably 0.3 N / 50 mm or less.
  • the lower limit of the adhesive force b between the gas barrier film and the protection film is not particularly limited, but is usually 0.05 N / 50 mm.
  • the difference (ab) between the adhesive strength a between the glass plate and the adhesive layer and the adhesive strength b between the gas barrier film and the protection film is: , Preferably 0.1 N / 50 mm or more, more preferably 0.3 N / 50 mm or more, and still more preferably 0.7 N / 50 mm or more.
  • the adhesive layer, the gas barrier film, and the protect film that constitute the laminated structure of the gas barrier laminate of the present invention the adhesive force a between the glass plate and the adhesive layer and the adhesive strength between the gas barrier film and the protect film This will be described in detail with reference to a specific method for satisfying the above formula (1) regarding the adhesive force b.
  • the gas barrier laminate of the present invention has an adhesive layer.
  • the adhesive composition constituting the adhesive layer is not particularly limited as long as it satisfies the above formula (1).
  • a dry-solidified adhesive composition for example, a heat-melt adhesive composition, a curable adhesive Agent compositions, pressure-sensitive adhesive compositions, and the like.
  • Specific examples of the adhesive composition constituting the adhesive layer include an adhesive composition containing an acrylic resin, an adhesive composition containing a urethane resin, an adhesive composition containing a silicone resin, Examples include a rubber-based adhesive composition, an adhesive composition containing a polyolefin-based resin, and an adhesive composition containing an epoxy-based resin. These can be used alone or in combination of two or more.
  • the adhesive composition may include a binder resin other than the above resin. Further, the adhesive composition may include at least one selected from a curable component, a silane coupling agent, a catalyst, a polymerization initiator, a tackifier, and the like.
  • the thickness of the adhesive layer is preferably 0.5 to 300 ⁇ m, more preferably 3 to 200 ⁇ m, still more preferably 5 to 150 ⁇ m, and still more preferably, from the viewpoint of ensuring excellent sealing properties for the object to be sealed. Is 5 to 80 ⁇ m.
  • water vapor permeability of the adhesive layer from the viewpoint of ensuring good gas barrier properties, preferably 100g / m 2 ⁇ day or less, more preferably 85g / m 2 ⁇ day or less, more preferably 70 g / m 2 ⁇ day or less.
  • water vapor permeability of the adhesive layer means a value measured using a gas permeability measuring device (product name “PERMATRAN” manufactured by mocon), but other general-purpose values are used. The measured value using the water vapor transmission rate measuring device shows the same value.
  • the adhesive layer included in the gas barrier laminate of one embodiment of the present invention is preferably a curable adhesive layer. Since the adhesive layer is curable, the adhesive layer is in an uncured state at the time of application, and can be easily attached to an object to be sealed, and has good followability to irregularities of the object to be sealed. I can do it. Then, after the curable adhesive layer is attached to the object to be sealed and then cured, the object to be sealed and the adhesive layer are firmly adhered to each other. As a result, the gas barrier laminate is excellent in performance of preventing deterioration of an object to be sealed due to entry of oxygen, water vapor, and the like.
  • the water vapor transmission rate of the curable adhesive layer is preferably in the same range as the above-mentioned “water vapor transmission rate of the adhesive layer” from the viewpoint of ensuring good gas barrier properties.
  • the “water vapor transmission rate of the curable adhesive layer” can be measured by the same measurement method as the “water vapor transmission rate of the adhesive layer” described above.
  • the curable adhesive layer is a curable adhesive composition, specifically, for example, a thermosetting adhesive composition or an energy ray-curable adhesive composition that can be cured by heat or energy rays.
  • the energy ray means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include an ultraviolet ray and an electron beam, and preferably an ultraviolet ray.
  • the curable adhesive layer is preferably a thermosetting adhesive layer formed from a thermosetting adhesive composition.
  • the curable adhesive layer is formed of an adhesive composition containing the curable component (B).
  • the curable adhesive layer is more preferably formed of an adhesive composition containing both the polyolefin-based resin (A) and the curable component (B).
  • the adhesive composition for forming a curable adhesive layer may contain components other than the polyolefin-based resin (A) and the curable component (B). .
  • a cationic polymerization initiator (D ′) a tackifier ( One or more selected from E).
  • polyolefin resin (A) “binder resin other than polyolefin resin (A ′)”, “curable component (B)”, “silane coupling agent (C)”, “ The “curing catalyst (D)”, “cationic polymerization initiator (D ′)”, and “tackifier (E)” are respectively referred to as “component (A)”, “component (A ′)”, and “component (B)”.
  • the total content of the components (A) and (B) in the adhesive composition containing both the polyolefin-based resin (A) and the curable component (B) is determined by determining the total content of the adhesive composition. It is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, even more preferably 99% by mass or more, based on the total amount of the active ingredient (100% by mass). % By mass, and usually 100% by mass or less.
  • the adhesive composition is selected from components (A ′), (C), (D), (D ′), and (E) in addition to the polyolefin resin (A) and the curable component (B).
  • the composition contains one or more of the following components, it is selected from the components (A) and (B) in the adhesive composition and the components (A ′), (C), (D), (D ′), and (E).
  • the total content of the adhesive composition and one or more components is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, based on the total amount (100% by mass) of the active ingredients of the adhesive composition. More preferably, it is 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the active ingredient of an adhesive composition means the component (solid content) except the diluting solvent contained in the adhesive composition.
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a polyolefin-based resin (A).
  • polyolefin-based resin means a polymer having a repeating unit derived from an olefin-based monomer.
  • the content of the polyolefin resin (A) in the adhesive composition is preferably from 30 to 95% by mass, more preferably from 40 to 90% by mass, based on the total amount (100% by mass) of the active ingredients of the adhesive composition. %, More preferably 50 to 80% by mass.
  • the content of the polyolefin-based resin (A) is in the above range, the water vapor permeability of the adhesive layer after curing is more easily reduced.
  • the adhesive force a between the glass plate and the curable adhesive layer tends to decrease. By adjusting the adhesive force b between the film and the film to a value lower than the adhesive force a, the above expression (1) can be satisfied.
  • the content of the polyolefin resin (A) in the adhesive composition is reduced to the extent that the required water vapor barrier property is satisfied, so that the adhesive force a between the glass plate and the curable adhesive layer is reduced.
  • the above expression (1) can be satisfied.
  • the olefin monomer contained in the polyolefin resin (A) is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and among them, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1- Pentene and 1-hexene are preferred.
  • the polyolefin resin (A) may have two or more ⁇ -olefin-derived units.
  • the polyolefin-based resin (A) may be a polymer composed of only an olefin-based monomer-derived repeating unit, or a copolymer of an olefin-based monomer with an olefin-based monomer.
  • (meth) acrylic acid means both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • polyolefin resin (A) examples include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene ( PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer , Polyisobutylene, polyisoprene and the like. These can be used alone or in combination of two or more.
  • VLDPE very low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • PP ethylene-propylene copolymer
  • TPO olefin-based elastomer
  • EVA ethylene-vinyl acetate copolymer
  • the polyolefin resin (A) when the adhesive layer is a curable adhesive layer, the polyolefin resin (A) is modified from the viewpoint of further improving the sealing performance of the cured adhesive layer. It is preferable to include the polyolefin-based resin (A1).
  • the “modified polyolefin resin (A1)” means that the polyolefin resin (A) serving as a precursor reacts with a modifier, and the polyolefin resin (A) serving as a main chain has a functional property of the modifier. It means a polymer in which the group is introduced as a side chain.
  • the modifier may have two or more functional groups in the molecule.
  • Examples of the functional group of the modifier which can be introduced as a side chain into the polyolefin resin (A) as a main chain, include, for example, a carboxyl group, a group derived from a carboxylic anhydride, and a carboxylic acid. Ester group, hydroxyl group, epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphon group, nitro group, urethane group, Examples include a halogen atom and an alkoxysilyl.
  • a carboxyl group a group derived from a carboxylic anhydride, a carboxylic ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate, and an alkoxysilyl group are preferable. Derived groups are preferred.
  • the modified polyolefin-based resin (A1) is preferably an acid-modified polyolefin-based resin from the viewpoint of increasing the reactivity with the curable component (B).
  • the “acid-modified polyolefin resin” means that a polyolefin resin (A) serving as a precursor reacts with a compound having an acid group, and the acid group is linked to the polyolefin resin (A) serving as a main chain. It means a polymer introduced as a chain.
  • the method and conditions for introducing the acid group of the compound having an acid group as a side chain into the polyolefin resin (A) serving as a main chain are not particularly limited, and a known side chain introduction method may be employed. it can.
  • the compound having an acid group is not particularly limited as long as it can be introduced as a side chain into the polyolefin resin (A) serving as a main chain, but preferably includes unsaturated carboxylic acids and anhydrides thereof.
  • unsaturated carboxylic acids and anhydrides thereof 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 anhydride, tetrahydrophthalic anhydride and the like.
  • unsaturated carboxylic acids and their anhydrides can be used alone or in combination of two or more.
  • maleic anhydride is preferred from the viewpoint of further improving the sealing performance of the adhesive layer after curing.
  • the acid-modified polyolefin-based resin may be a commercially available product.
  • Commercially available acid-modified polyolefin-based resins include, for example, Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orrevac (registered trademark) (Manufactured by ARKEMA), Modick (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.
  • the amount of the compound having an acid group to be reacted with the precursor polyolefin resin (A) is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the precursor polyolefin resin (A). , More preferably 0.2 to 3 parts by mass, even more preferably 0.2 to 1.0 part by mass.
  • the compounding amount of the compound having an acid group is in the above range, it is easy to improve the sealing performance of the cured adhesive layer.
  • the weight average molecular weight (Mw) of the polyolefin-based resin (A) and the modified polyolefin-based resin (A1) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and still more preferably. Is from 25,000 to 250,000, even more preferably from 30,000 to 150,000.
  • Mw weight average molecular weight
  • the polyolefin resin (A) may be composed of only the modified polyolefin resin (A1), or may be composed of the modified polyolefin resin (A1) and a non-modified polyolefin resin. May be done.
  • the content of the modified polyolefin-based resin (A1) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably 80 to 100% by mass with respect to the total amount (100% by mass) of the polyolefin-based resin (A). -100% by mass, more preferably 90-100% by mass.
  • the sealing performance of the cured adhesive layer can be more easily improved.
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition contains a curable component (B).
  • the “curable component (B)” means a component which becomes a network structure and is cured in an insoluble and infusible state by heating or irradiation with energy rays.
  • the adhesive composition contains the curable component (B)
  • the adhesive layer becomes curable, and the sealing performance of the adhesive layer after curing is improved.
  • the curable component (B) may be a thermosetting component or an energy ray-curable component, but is preferably a thermosetting component.
  • the content of the curable component (B) in the adhesive composition is preferably 5 to 50% by mass, more preferably 5 to 48% by mass based on the total amount (100% by mass) of the active ingredients in the adhesive composition. %, More preferably 5 to 45% by mass, even more preferably 10 to 40% by mass.
  • the content of the curable component (B) is in the above range, the sealing performance of the adhesive layer after curing can be more easily improved.
  • the adhesive composition contains the polyolefin resin (A)
  • the content of the curable component (B) in the adhesive composition relative to 100 parts by mass of the polyolefin resin (A) is preferably from 5 to 110. It is part by mass, more preferably 10 to 100 parts by mass.
  • an adhesive layer formed from an adhesive composition having a curable component (B) content within this range is cured, the cured adhesive layer is more excellent in water vapor barrier properties.
  • the curable component (B) examples include a curable epoxy resin, a melamine resin, a urea resin, and a maleimide resin. These can be used alone or in combination of two or more. Among these, it is preferable to include the curable epoxy resin (B1).
  • the “curable epoxy resin (B1)” means an epoxy compound which is cured into an insoluble and infusible state by forming a network structure by heating or irradiation with energy rays.
  • the curable epoxy resin (B1) preferably contains a polyfunctional epoxy resin (B2).
  • polyfunctional epoxy resin (B2) means a compound having at least two epoxy groups in a molecule.
  • the polyfunctional epoxy resin (B2) a bifunctional epoxy resin having two epoxy groups in the molecule is preferable from the viewpoint of further improving the sealing performance of the adhesive layer after curing.
  • the bifunctional epoxy resin include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether.
  • aromatic epoxy compounds such as novolak epoxy resins (eg, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated phenol novolak epoxy resin); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F Alicyclic epoxy compounds such as glycidyl ether and hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hexyl Diol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane, dimethyloltricyclo Aliphatic epoxy compounds such as decane diglycidyl ether; and the like.
  • These bifunctional epoxy resins can be used alone or in combination of two or more.
  • the adhesive composition preferably contains, as the component (B), a polyfunctional epoxy compound (BL) that is liquid at 25 ° C.
  • the polyfunctional epoxy compound (BL) that is liquid at 25 ° C. is also referred to as “component (BL)”.
  • the component (BL) has an effect of lowering the storage modulus of the adhesive composition when the temperature of the adhesive composition becomes high (hereinafter, also referred to as a “storage modulus lowering effect”). Therefore, in one embodiment of the present invention, when the adhesive composition contains such a component (BL), an adhesive layer excellent in unevenness followability can be efficiently formed.
  • the weight average molecular weight (Mw) of the component (BL) is preferably at least 1,000, more preferably at least 1,200, further preferably at least 1, from the viewpoint of suppressing outgassing caused by the component (BL). It is at least 500, more preferably at least 1,800, even more preferably at least 2,100.
  • the weight average molecular weight (Mw) of the component (BL) is preferably 5,000 or less, more preferably 4,500 or less.
  • the weight average molecular weight (Mw) of the component (BL) in the adhesive composition is larger, the adhesive strength a tends to decrease, but the adhesive strength b between the gas barrier film and the protection film is reduced.
  • the weight average molecular weight (Mw) of the component (BL) is reduced to the extent that the required outgas generation suppression performance is satisfied, so that the adhesive force a between the glass plate and the curable adhesive layer is larger than the adhesive force b.
  • the above equation (1) can be satisfied.
  • the epoxy equivalent of the component (BL) is preferably 100 to 1,500 g / eq, more preferably 150 to 1500 g / eq, still more preferably 200 to 1,400 g / eq, and still more preferably 240 to 1,300 g / eq. It is.
  • epoxy equivalent means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and is a value measured according to JIS K 7236: 2009.
  • the content of the component (BL) in the adhesive composition is preferably 5 to 40% by mass, more preferably 8 to 36% by mass, based on the total amount (100% by mass) of the active ingredients in the adhesive composition. More preferably, the content is 10 to 34% by mass.
  • the content of the component (BL) is within this range, the generation of outgas due to the component (BL) is suppressed while the storage elastic modulus lowering effect is obtained.
  • the adhesive force a between the glass plate and the curable adhesive layer changes depending on the increase or decrease of the content of the component (BL). When the content of the component (BL) in the adhesive composition is small, the adhesive strength a tends to decrease.
  • Equation (1) can be satisfied by adjusting the adhesive strength b between the gas barrier film and the protection film to a value lower than the adhesive strength a. Further, by increasing the content of the component (BL) in the adhesive composition and adjusting the adhesive force a between the glass plate and the curable adhesive layer to a value higher than the adhesive force b, Equation (1) may be satisfied.
  • the adhesive composition may contain a binder resin (A ′) other than the polyolefin-based resin (A).
  • the binder resin (A ′) other than the polyolefin-based resin include a phenoxy-based resin and an acetal-based resin.
  • the binder resin (A ′) other than the polyolefin resin (A) may be used together with the polyolefin resin (A), or may be used instead of the polyolefin resin (A).
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a silane coupling agent (C).
  • silane coupling agent (C) means an organosilicon compound having two or more different reactive groups in a molecule.
  • the adhesive composition may contain a silane coupling agent (C). Also in this case, good sealing performance of the adhesive layer is easily ensured.
  • the content of the silane coupling agent in the adhesive composition is preferably 0.01 to 0.1% by mass, more preferably 0.02 to 0.1% by mass, based on the total amount (100% by mass) of the adhesive composition. 09% by mass.
  • the adhesive composition contains the polyolefin resin (A)
  • the content of the silane coupling agent (C) in the adhesive composition is preferably based on 100 parts by mass of the polyolefin resin (A).
  • the amount is 0.01 to 5.0 parts by mass, and more preferably 0.05 to 1.0 part by mass.
  • the content of the silane coupling agent (C) is within the above range, even when the silane coupling agent (C) is exposed to a high-temperature and high-humidity environment for a long time, the sealing performance of the cured adhesive layer is easily ensured. .
  • silane coupling agent (C) at least one alkoxysilyl group in the molecule is preferably used at both room temperature and high temperature environment, from the viewpoint of easily securing the sealing performance of the adhesive layer after curing.
  • examples of such a silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, Silicon compounds having an epoxy structure such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane; 3-aminopropyltrimethoxysilane; Amino-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxys
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a curing catalyst (D).
  • curing catalyst (D) means a catalyst that promotes a reaction for curing the curable component (B) by heat or energy rays.
  • the content of the curing catalyst (D) contained in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass based on 100 parts by mass of the curable component (B). It is.
  • the content of the curing catalyst (D) is in the above range, the sealing performance of the cured adhesive layer at a high temperature can be more easily improved.
  • an imidazole-based curing catalyst which is a thermosetting curing catalyst, is preferable from the viewpoint of suitably promoting curing by heating.
  • the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, -Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
  • One of these imidazole-based curing catalysts can be used alone, or two or more can be used in combination. Among these imidazole-based curing catalysts, 2-ethyl-4-methylimidazole is preferred.
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition preferably further contains a cationic polymerization initiator (D ′).
  • the cationic polymerization initiator (D ′) is preferably a thermal cationic polymerization initiator, and the adhesive layer is an energy ray-curable adhesive layer.
  • it it is preferred that it is a photocationic polymerization initiator.
  • thermal cationic polymerization initiator examples include a sulfonium salt, a quaternary ammonium salt, a phosphonium salt, a diazonium salt, an iodonium salt and the like, and a sulfonium salt is preferable.
  • a sulfonium salt for example, sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, oxonium salt compounds And a bromine salt compound, and a sulfonium salt compound is preferable.
  • the curable component (B) is preferably a curable epoxy resin (B1).
  • the adhesive composition when the adhesive layer is a curable adhesive layer, the adhesive composition may contain a tackifier (E).
  • the tackifier (E) used in one embodiment of the present invention is a component that assists in improving the adhesive properties of the curable adhesive layer, and includes an oligomer having a weight average molecular weight (Mw) of usually less than 10,000. It is different from the resin (X) contained in the pressure-sensitive adhesive composition described below.
  • the adhesive composition may contain a tackifier (E).
  • the weight average molecular weight (Mw) of the tackifier (E) is usually less than 10,000, but is preferably from 400 to 8000, more preferably from 500 to 5,000, more preferably from 800 to 3,500.
  • the content of the tackifier (E) in the adhesive composition is preferably reduced from the viewpoint of suppressing outgassing caused by the tackifier (E), and the total amount of the active ingredients in the adhesive composition (100% by mass), preferably more than 0% by mass and 30% by mass or less, more preferably more than 0% by mass and 15% by mass or less, still more preferably 1 to 10% by mass.
  • the adhesive composition does not contain the tackifier (E).
  • the content of the tackifier (E) contained in the adhesive composition is preferably more than 0 parts by mass to 80 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the polyolefin resin (A). It is more than 30 parts by mass, more preferably 1 to 20 parts by mass. Further, when it is desired to suppress outgassing as much as possible, the content of the tackifier (E) is preferably as small as possible with respect to 100 parts by mass of the polyolefin resin (A), and is 0 parts by mass. Is more preferable. On the other hand, when the content of the tackifier (E) in the adhesive composition is small, the adhesive force a between the glass plate and the curable adhesive layer tends to decrease.
  • the above formula (1) can be satisfied by adjusting the adhesive force b between the gas barrier film and the protection film to a lower value. Further, by increasing the content of the tackifier (E) in the adhesive composition within a range satisfying the required outgas generation suppressing performance, the adhesive force a between the glass plate and the curable adhesive layer can be reduced. By adjusting the value to a value higher than the adhesive force b, the above formula (1) can be satisfied.
  • tackifier (E) examples include rosin resins such as polymerized rosin, polymerized rosin ester, and rosin derivative; terpene resins such as polyterpene resin, aromatic modified terpene resin and hydride thereof, and terpene phenol resin; Indene resin; petroleum resin such as aliphatic petroleum resin, aromatic petroleum resin and hydride thereof, aliphatic / aromatic copolymer petroleum resin; styrene or substituted styrene polymer; ⁇ -methylstyrene homopolymer resin , A copolymer of ⁇ -methylstyrene and styrene, a copolymer of styrene monomer and aliphatic monomer, a copolymer of styrene monomer and ⁇ -methylstyrene and aliphatic monomer, and styrene monomer Styrene resins such as homopolymers, copolymers of
  • tackifiers (E) can be used alone or in combination of two or more.
  • a styrene resin is preferable, and a copolymer of a styrene monomer and an aliphatic monomer is more preferable.
  • the softening point of the tackifier (E) further improves the shape retention of the formed adhesive layer, and enables the cured adhesive layer to exhibit excellent adhesiveness even in a high-temperature environment. Therefore, the temperature is preferably 80 ° C. or higher, more preferably 85 to 170 ° C., and still more preferably 90 to 150 ° C.
  • a softening point means the value measured based on JISK5902. When two or more kinds of tackifiers (E) are used, the weighted average of the softening points of the plurality of tackifiers preferably falls within the above range.
  • the adhesive composition may contain other additives other than the components (A) to (E) as long as the effects of the present invention are not significantly impaired.
  • Other additives are appropriately selected according to the intended use, and include, for example, ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, and the like. Additives. These additives can be used alone or in combination of two or more. In addition, even when the adhesive layer is not curable, the pressure-sensitive adhesive composition may contain these additives.
  • the adhesive composition may further contain a diluting solvent from the viewpoint of improving the moldability of the adhesive layer.
  • the diluting solvent can be appropriately selected from organic solvents, and specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; .
  • the pressure-sensitive adhesive composition may contain a diluting solvent.
  • the adhesive layer constituting the gas barrier laminate of the present invention is not particularly limited, and can be appropriately formed by using a known method or the like.
  • the adhesive layer is preferably formed from the above-described adhesive composition.
  • the above-mentioned adhesive composition is applied on the release-treated surface of the above-mentioned release sheet to form a coating film, and the coating film is dried to form an adhesive layer.
  • the adhesive layer is a curable adhesive layer
  • the heat treatment by the heat applied when drying the coating film is a curable adhesive layer. It is not included in the curing treatment of the adhesive layer.
  • Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • As the drying conditions for drying the coating film for example, it is preferable to carry out a drying treatment at usually 80 to 130 ° C., preferably 90 to 110 ° C. for 30 seconds to 5 minutes.
  • the gas barrier laminate of the present invention has a gas barrier film.
  • the gas barrier film is laminated on the adhesive layer.
  • an excellent gas barrier property having a high effect of preventing transmission of gases such as oxygen and water vapor can be exhibited.
  • a protection film is laminated on a gas barrier film, and the gas barrier film is protected by the protection film. Therefore, in addition to the storage and transport until use of the gas barrier laminate, the process of manufacturing the sealed body by sealing the object to be sealed with the gas barrier laminate, and processing and transport of the sealed body In the process, it is possible to prevent the gas barrier film from being damaged or cracked.
  • the gas barrier film included in the gas barrier laminate preferably has at least a base layer and has a gas barrier function.
  • a film having a base material layer and a gas barrier layer is given.
  • an embodiment having the following layer configuration is given.
  • -Base layer / gas barrier layer In the above-described embodiment of the "base layer / gas barrier layer", in order to increase the adhesion between the base layer and the gas barrier layer, the base layer and the gas barrier You may have an anchor coat layer between the layers.
  • the gas barrier film of the gas barrier laminate is a single-layer resin film or the like in which the base layer itself has a gas barrier function, and the base layer also has a function as a gas barrier layer. Is also good.
  • the gas barrier layer is disposed at a position closer to the adhesive layer than to the base material layer as in the following embodiment.
  • -Base layer / gas barrier layer / adhesive layer Since no base layer is interposed between the gas barrier layer and the adhesive layer, the performance of the gas barrier laminate to block water vapor is further improved.
  • the protection film is laminated on the base layer of the gas barrier film. Since a resin film is used for the base layer as described later, the adhesion between the protect film and the base layer is likely to be increased.
  • the gas barrier laminate of the present invention is adjusted so as to satisfy the relationship of the above formula (1). Therefore, when the protection film is peeled off, a gap is formed between the object to be sealed and the adhesive layer. Does not occur.
  • the gas barrier film of the gas barrier laminate has a water vapor permeability of preferably 0.1 g / m 2 / day or less in an environment of a temperature of 40 ° C. and 90% RH (relative humidity). more preferably 0.05g / m 2 / day, more preferably not more than 0.005g / m 2 / day.
  • the water vapor transmission rate of the gas barrier film is 0.1 g / m 2 / day or less, the use of the gas barrier laminate facilitates effective suppression of deterioration of the object to be sealed.
  • the water vapor transmission rate in an environment of a temperature of 40 ° C. and 90% RH (relative humidity) preferably has the same value as described above.
  • water vapor permeability of a gas barrier film means the value measured using the gas permeability measuring device (product name "AQUATRAN2" manufactured by mocon), but other general-purpose The measured value using the water vapor transmission rate measuring device shows the same value.
  • the gas barrier film of the gas barrier laminate preferably has optical transparency.
  • the total light transmittance measured according to JIS K7136: 2000 is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.
  • the b * value in the L * a * b * display color system, measured according to JIS K7136: 2000 is preferably 2 or less, more preferably 1.5 or less, and further preferably 1 or less. It is.
  • gas barrier film used for the gas barrier laminate of one embodiment of the present invention a gas barrier film having a laminated structure in which a substrate layer and a gas barrier layer are laminated will be described in detail as an example.
  • a resin film containing a resin component is preferable.
  • the resin component polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin-based Examples include polymers, cycloolefin-based copolymers, aromatic polymers, and polyurethane-based polymers.
  • polycarbonate, a cycloolefin-based polymer, and a cycloolefin-based copolymer are preferable from the viewpoint of obtaining a gas barrier film having high transparency and being optically isotropic.
  • these resins can be used individually by 1 type or in combination of 2 or more types.
  • the base layer may be a laminate of two or more resin films.
  • a resin film having optical isotropy is a more preferable resin film as a constituent material of a gas barrier film when a light-emitting element such as an organic EL element is used for a display application, but has poor flexibility and is brittle, so that it may be damaged during handling. There is a disadvantage that cracks easily occur.
  • a gas barrier film having poor flexibility and a brittle resin film such as polycarbonate, cycloolefin-based polymer, and cycloolefin-based copolymer is used. Is protected by the protection film, so that it is possible to prevent the gas barrier film from being damaged or cracked at the time of handling, and it is possible to suppress the occurrence of defects such as bright spots caused by the scratches or cracks on the display. Therefore, the yield can be improved in a display manufacturing process using a light emitting element such as an organic EL element.
  • the thickness of the substrate layer of the gas barrier film is not particularly limited, and is preferably 0.5 to 500 ⁇ m, more preferably 1 to 200 ⁇ m, and further preferably 5 to 100 ⁇ m.
  • a protection film is laminated on the gas barrier film. Therefore, even when the base material layer is thin, the thickness of the gas barrier laminate can be ensured by the protection film, so that the handleability of the gas barrier laminate can be sufficiently ensured. Therefore, the thickness of the base material layer may be 30 ⁇ m or less, which generally makes it difficult to ensure handling properties. Therefore, the thickness of the base layer included in the gas barrier laminate of one embodiment of the present invention may be 1 to 30 ⁇ m, 1 to 25 ⁇ m, or 1 to 20 ⁇ m.
  • the gas barrier layer of the gas barrier film can reduce the thickness of the gas barrier film and has excellent gas barrier properties, an inorganic film, and a polymer containing a polymer compound and subjected to a modification treatment
  • the layer is preferable, and more preferably the polymer layer.
  • the gas barrier layer can have high flexibility and excellent durability against bending of the gas barrier film.
  • polymer compound contained in the polymer layer for example, a polyorganosiloxane, a silicon-containing polymer compound such as a polysilazane-based compound, polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin,
  • a silicon-containing polymer compound such as a polysilazane-based compound, polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin
  • the polymer compound contained in the polymer layer is preferably a silicon-containing polymer compound, and more preferably a polysilazane-based compound.
  • the number average molecular weight of the polysilazane compound is preferably from 100 to 50,000.
  • the polysilazane-based compound is a polymer having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule, and specifically, a polymer having a repeating unit represented by the following general formula (I) It is preferred that
  • n represents the number of repeating units, and represents an integer of 1 or more.
  • Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted Represents an aryl group or an alkylsilyl group having a group.
  • Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
  • the polymer compound contained in the gas barrier layer may be an inorganic polysilazane in which Rx, Ry, and Rz in the general formula (I) are all hydrogen atoms, and at least one of Rx, Ry, and Rz is hydrogen.
  • Organic polysilazane which is a group other than an atom may be used.
  • polysilazane-based compound one kind can be used alone, or two or more kinds can be used in combination. Further, as the polysilazane-based compound, a modified polysilazane can be used, and a commercially available product can also be used.
  • the polymer layer may further contain other components in addition to the above-described polymer compound as long as the effects of the present invention are not impaired.
  • Other components include, for example, curing agents, other polymers, antioxidants, light stabilizers, flame retardants, and the like. These can be used alone or in combination of two or more.
  • the content of the polymer compound in the polymer layer is preferably 50 to 100 with respect to the total amount (100% by mass) of the components in the polymer layer from the viewpoint of obtaining a gas barrier layer having more excellent gas barrier properties. %, More preferably 70 to 100% by mass, even more preferably 80 to 100% by mass.
  • the thickness of the polymer layer included in the gas barrier film is preferably 50 to 500 nm, more preferably 50 to 300 nm, and further preferably 50 to 200 nm.
  • a gas barrier laminate having a sufficient gas barrier property can be obtained even if the thickness of the polymer layer is on the order of nanometers.
  • a method of forming a polymer layer for example, a solution for forming a polymer layer containing at least one kind of polymer compound, other components as required, and a solvent, etc., a spin coater, a knife coater, a gravure coater or the like
  • a coating film is formed by coating using a known device, and the coating film is dried to form the coating film.
  • Examples of the treatment for modifying the polymer layer include an ion implantation treatment, a plasma treatment, an ultraviolet irradiation treatment, and a heat treatment. These processes can be performed alone or in combination of two or more.
  • the ion implantation treatment is a method of modifying the polymer layer by injecting ions into the polymer layer, as described later.
  • Plasma treatment is a method in which a polymer layer is exposed to plasma to modify the polymer layer.
  • plasma processing can be performed according to the method described in JP-A-2012-106421.
  • the ultraviolet irradiation treatment is a method of irradiating the polymer layer with ultraviolet light to modify the polymer layer.
  • the ultraviolet ray modification treatment can be performed according to the method described in JP-A-2013-226575.
  • ion-implantation is used as a modification treatment of the polymer layer from the viewpoint that the polymer layer can be efficiently reformed to the inside without roughening the surface and a gas barrier layer having more excellent gas barrier properties can be formed. Processing is preferred.
  • the ions implanted into the polymer layer during the ion implantation treatment include, for example, ions of a rare gas such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, and fluorine.
  • a rare gas such as argon, helium, neon, krypton, and xenon
  • fluorocarbon hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, and fluorine.
  • alkane gas such as methane and ethane
  • alkene gas such as ethylene and propylene
  • alkadiene gas such as pentadiene and butadiene
  • alkyne gas such as acetylene Ion
  • aromatic hydrocarbon gas such as benzene and toluene
  • cycloalkane gas such as cyclopropane
  • cycloalkene gas such as cyclopentene
  • metal ion ion of organosilicon compound
  • ions of a rare gas such as argon, helium, neon, krypton, and xenon are preferred from the viewpoint that ions can be more easily implanted and a gas barrier layer having particularly excellent gas barrier properties is obtained.
  • Argon ions are more preferred.
  • the method for implanting ions is not particularly limited. For example, a method of irradiating ions (ion beam) accelerated by an electric field, a method of injecting ions in plasma (ions of plasma generation gas), and the like can be mentioned.
  • the method of implanting ions is preferred.
  • the method of implanting ions in the plasma is, for example, to generate plasma in an atmosphere containing a plasma generating gas and apply a negative high-voltage pulse to a layer into which the ions are implanted, so that ions (positive ions) in the plasma are generated. Can be implanted into the surface of the layer into which ions are implanted.
  • Examples of the inorganic film used as the gas barrier layer include a film formed by vapor-phase film formation of an inorganic compound or a metal.
  • Raw materials for the inorganic compound film include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; inorganic carbides; Sulfide; inorganic oxynitride such as silicon oxynitride; inorganic oxycarbide; inorganic oxynitride; inorganic oxynitride carbide.
  • Materials for the metal film include aluminum, magnesium, zinc, and tin.
  • an inorganic film made of an inorganic oxide, an inorganic nitride or a metal is preferable, and from the viewpoint of transparency, an inorganic film made of an inorganic oxide or an inorganic nitride is preferable. Is preferred. Further, the inorganic film may be a single layer or a multilayer.
  • the thickness of the inorganic film is preferably from 10 to 2,000 nm, more preferably from 20 to 1,000 nm, more preferably from 30 to 500 nm, and still more preferably from 40 to 200 nm, from the viewpoint of gas barrier properties and handleability.
  • a vapor deposition method for forming an inorganic film As a vapor deposition method for forming an inorganic film, a PVD (physical vapor deposition) method such as a vacuum deposition method, a sputtering method, or an ion plating method, and a CVD method such as a thermal CVD method, a plasma CVD method, and a light CVD method are used. Method (chemical vapor deposition method).
  • an anchor coat layer may be provided between the substrate layer and the gas barrier layer from the viewpoint of further improving the adhesion between the substrate layer and the gas barrier layer.
  • An example of the anchor coat layer is a layer obtained by curing a composition containing an ultraviolet curable compound.
  • the composition containing the ultraviolet curable compound may contain an inorganic filler such as silica particles.
  • the thickness of the anchor coat layer is preferably from 0.1 to 10 ⁇ m, more preferably from 0.5 to 5 ⁇ m.
  • the gas barrier laminate of the present invention has a protection film.
  • the protection film is laminated on the gas barrier film to protect the gas barrier film.
  • the protection film is peeled at a desired timing, such as when the protection of the gas barrier film becomes unnecessary or when the gas barrier film needs to be exposed, there is a gap between the sealed object and the adhesive layer. Does not occur, and penetration of oxygen, moisture and the like is prevented. In addition, the appearance is also prevented from becoming poor.
  • the protection film of the gas barrier laminate has at least a protection layer.
  • the form of the protection film may be a single layer of the protection layer, but is preferably a laminated structure of the protection layer and the pressure-sensitive adhesive layer. With the laminated structure of the protection layer and the pressure-sensitive adhesive layer, the adhesive strength of the protection film is adjusted, so that the gas barrier laminate satisfying the above formula (1) can be easily obtained.
  • the gas barrier laminate of the present invention can have good handleability of the gas barrier laminate while having the base layer of the gas barrier film thin by having the protection film.
  • the total thickness of the protective film and the base layer of the gas barrier film is preferably 40 to 500 ⁇ m, more preferably 40 to 200 ⁇ m, and further preferably 50 to 150 ⁇ m.
  • a protective film having a laminated structure in which a protective layer and an adhesive layer are laminated will be described in detail as an example of the protective film used for the gas barrier laminate of one embodiment of the present invention.
  • a resin film containing a resin component is preferable.
  • the resin component include those having high impact resistance among the resin components listed as the base layer of the gas barrier film.
  • examples of such a resin component include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, and aromatic resin.
  • the polymer include a polymer and a polyurethane-based polymer.
  • these resins can be used individually by 1 type or in combination of 2 or more types.
  • a film in which these are colored may be used. By coloring, the presence or absence of the protect film can be easily determined, and the interface between the gas barrier film and the protect film can be easily recognized, which is convenient when the protect film is peeled off.
  • the thickness of the protection layer of the protection film may be sufficient if it protects the gas barrier film, and is preferably 1 to 500 ⁇ m, more preferably 5 to 200 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the ratio of the thickness of the protection layer of the protection film to the thickness of the base layer of the gas barrier film is determined by reducing the thickness of the base layer and the gas barrier laminate. From the viewpoint of improving the handleability, it is preferably from 1 to 5, more preferably from 1.2 to 4.5, and still more preferably from 1.5 to 4.
  • the pressure-sensitive adhesive layer of the protection film is a layer that is laminated on one surface of the protection layer and is used for bonding the protection layer and the gas barrier film.
  • the adhesive strength b between the gas barrier film and the protection film is preferably adjusted to be low.
  • the adhesive strength b between the gas barrier film and the protection film can be adjusted low by reducing the adhesiveness of the pressure-sensitive adhesive layer of the protection film. Examples of a method for lowering the adhesiveness of the pressure-sensitive adhesive layer of the protection film include reducing the thickness of the pressure-sensitive adhesive layer, changing the type of the pressure-sensitive adhesive layer, and the like.
  • the adhesive layer included in the gas barrier laminate of the present invention must be provided with characteristics necessary for sealing an object to be sealed. Therefore, rather than changing the adhesive force a by adjusting the type and amount of the raw material of the adhesive composition for forming the adhesive layer, the pressure-sensitive adhesive layer having only to control the sticking property to the gas barrier film may be used. It is easier to change the adhesive force b by adjusting the adhesiveness of the above.
  • the thickness of the pressure-sensitive adhesive layer is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.5 ⁇ m to 40 ⁇ m, and still more preferably 1 ⁇ m to 25 ⁇ m, from the viewpoint of reducing the adhesiveness of the pressure-sensitive adhesive layer.
  • the type of the pressure-sensitive adhesive layer can be changed by selecting a resin which is a polymer contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer will be described in consideration of selection of a resin as a polymer.
  • the pressure-sensitive adhesive composition that is a material for forming the pressure-sensitive adhesive layer contains a resin (X) that is a polymer.
  • the resin (X) may have tackiness itself or may not have tackiness.
  • a tackifier described below is added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition exhibits tackiness. Is also good.
  • components other than the resin (X) contained in the pressure-sensitive adhesive composition can be appropriately adjusted as needed.
  • the adhesive composition may further contain at least one selected from the group consisting of a tackifier and a crosslinking agent, In addition to these, one or more selected from the group consisting of a diluting solvent and an adhesive additive used for a general adhesive may be contained.
  • the weight average molecular weight (Mw) of the resin (X) is preferably 10,000 or more, more preferably 10,000 to 2,000,000, and further preferably 20,000 to 1.5,000,000.
  • the resin (X) contained in the pressure-sensitive adhesive composition include an acrylic resin, a urethane resin, an olefin resin, an acrylic urethane resin, and a polyester resin. These resins (X) can be used alone or in combination of two or more.
  • the resin (X) is a copolymer having two or more types of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer may be used.
  • the resin (X) is made of acrylic resin. Resins and olefin resins are preferred, and acrylic resins are more preferred.
  • the content of the resin (X) in the pressure-sensitive adhesive composition is preferably 30 to 99.99% by weight, more preferably 40 to 99.95% by weight based on the total amount (100% by weight) of the active ingredients of the pressure-sensitive adhesive composition. %, More preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, and still more preferably 60 to 99.50% by mass.
  • an acrylic resin and an olefin resin which are preferable as the resin (X) in one embodiment of the present invention will be described.
  • the pressure-sensitive adhesive composition contains an acrylic resin.
  • the content ratio of the acrylic resin in the resin (X) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass in the total amount (100% by mass) of the resin (X) contained in the pressure-sensitive adhesive composition. %, More preferably 70 to 100% by mass, even more preferably 85 to 100% by mass.
  • acrylic resin examples include a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a (meth) acrylate having a cyclic structure. Polymers containing structural units derived therefrom are exemplified.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1.5 million, more preferably 130,000 to 1.3 million.
  • an acrylic polymer (A0) having a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) is preferable.
  • An acrylic copolymer (A1) having a structural unit (a2) derived from a functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) together with the unit (a1) is more preferable.
  • the number of carbon atoms in the alkyl group of the monomer (a1 ′) is preferably 1 to 24, and more preferably 1 to 12, from the viewpoint of making it easier to adjust the adhesive strength as the adhesive layer becomes thinner.
  • the alkyl group of the monomer (a1 ′) may be a straight-chain alkyl group or a branched-chain alkyl group.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl ( (Meth) acrylate, stearyl (meth) acrylate and the like.
  • methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferred, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferred.
  • One of these monomers (a1 ′) can be used alone, or two or more can be used in combination. Among them, the monomer (a1 ′) is preferably used in combination with butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
  • the mass ratio [butyl (meth) acrylate / 2-ethylhexyl (meth) acrylate] is preferably from 1/9 from the viewpoint of easily adjusting the adhesive strength b between the gas barrier film and the protection film to be low. It is 5/5, more preferably 1/9 to 4/6, and still more preferably 1/9 to 3/7.
  • the content of the structural unit (a1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass in all the structural units (100% by mass) of the acrylic polymer (A0) or the acrylic copolymer (A1). It is 99.9% by mass, more preferably 70 to 99.5% by mass, even more preferably 80 to 99.0% by mass.
  • the functional group of the monomer (a2 ′) reacts with a crosslinking agent that may be contained in the pressure-sensitive adhesive composition described below and refers to a functional group that can be a crosslinking starting point or a functional group having a crosslinking promoting effect, such as a hydroxyl group, Examples include a carboxy group, an amino group, and an epoxy group. That is, examples of the monomer (a2 ′) include a hydroxyl-containing monomer, a carboxy-containing monomer, an amino-containing monomer, and an epoxy-containing monomer. One of these monomers (a2 ′) can be used alone, or two or more can be used in combination. As the monomer (a2 ′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth)
  • hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate
  • unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; and ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid, and anhydrides thereof.
  • the monomer (a2 ′) 2-hydroxyethyl (meth) acrylate is preferable.
  • One of these monomers (a2 ′) can be used alone, or two or more can be used in combination.
  • the content of the structural unit (a2) is preferably from 0.1 to 40% by mass, more preferably from 0.3 to 30% by mass, based on all the structural units (100% by mass) of the acrylic copolymer (A1). More preferably, it is 0.5 to 20% by mass, and still more preferably 0.7 to 10% by mass. As the content of the structural unit (a2) serving as a crosslinking starting point increases, the adhesive strength b between the gas barrier film and the protection film tends to decrease.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the content of the structural units (a1) and (a2) is preferably 70 to 100% in all the structural units (100% by mass) of the acrylic copolymer (A1). %, More preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass.
  • Examples of the monomer (a3 ′) include olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate; Has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
  • olefins such as ethylene, propylene and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, isoprene and
  • (Meth) acrylate styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmol Phosphorus, N- vinylpyrrolidone and the like.
  • One of these monomers (a3 ′) can be used alone, or two or more can be used in combination.
  • As the monomer (a3 ′) vinyl acetate is preferred.
  • the olefin-based resin that can be used as the resin (X) is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene and propylene.
  • the olefin-based resin can be used alone or in combination of two or more.
  • olefin resins include, for example, polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other ⁇ - Copolymer with olefin, copolymer with propylene and other ⁇ -olefin, copolymer with ethylene and propylene with other ⁇ -olefin, copolymer with ethylene and other ethylenically unsaturated monomer And a copolymer (ethylene-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, ethylene-vinyl alcohol copolymer, etc.) and the like.
  • polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene
  • polypropylene copolymers of
  • an ethylene-vinyl acetate copolymer which is a copolymer of ethylene and another ethylenically unsaturated monomer
  • the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth) acrylate, and vinyl alcohol.
  • the olefin-based resin may be a rubber-based resin.
  • the rubber-based resin that can be used as the resin (X) include a polyisobutylene-based resin.
  • the polyisobutylene-based resin (hereinafter, also referred to as “PIB-based resin”) is not particularly limited as long as it has a polyisobutylene skeleton in at least one of the main chain and the side chain.
  • the number average molecular weight (Mn) of the PIB resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, further preferably 50,000 to 800,000, and still more preferably 70,000 to 600,000.
  • PIB resin examples include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and a copolymer of these. Brominated or chlorinated halogenated butyl rubber and the like can be mentioned. Among these, a copolymer of isobutylene and isoprene is preferred.
  • the structural unit composed of isobutylene is contained most in all the structural units.
  • the content of the structural unit composed of isobutylene is preferably from 80 to 100% by mole, more preferably from 90 to 100% by mole, and still more preferably from 95 to 100% by mole in all the structural units (100% by mole) of the PIB resin. is there.
  • These PIB resins can be used alone or in combination of two or more.
  • a PIB-based resin When a PIB-based resin is used, it is preferable to use a rubber-based resin capable of performing a cross-linking reaction, such as polyisoprene rubber having a carboxylic acid-based functional group.
  • the pressure-sensitive adhesive composition comprises a resin having the above-mentioned functional group (X ) Together with a crosslinking agent.
  • the crosslinking agent reacts with a functional group of the resin (X) to crosslink the resins.
  • the adhesive strength b between the gas barrier film and the protection film can be adjusted depending on the degree of crosslinking between the resins.
  • crosslinking agent examples include isocyanate-based crosslinking agents such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and adducts thereof; ethylene glycol glycidyl ether, 1,3-bis (N, N-diglycidyl-amino) Epoxy crosslinkers such as methyl) cyclohexane; aziridine crosslinkers such as hexa [1- (2-methyl) -aziridinyl] trifosphatriazine; chelate crosslinkers such as aluminum chelates; and the like.
  • These crosslinking agents can be used alone or in combination of two or more.
  • an isocyanate-based crosslinking agent is preferred from the viewpoint of easily adjusting the adhesive strength to a low level as the pressure-sensitive adhesive layer becomes thinner and from the viewpoint of easy availability.
  • the content of the cross-linking agent is appropriately adjusted depending on the number of functional groups of the resin (X). For example, 100 parts by mass of the resin (X) having the above-described functional group such as the acrylic copolymer or the like The amount is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 4 parts by mass.
  • the content of the cross-linking agent is large and the cross-linking density in the pressure-sensitive adhesive layer is high, the adhesive strength b between the gas barrier film and the protection film tends to be low.
  • the pressure-sensitive adhesive composition may further contain a tackifier together with the resin (X).
  • the same tackifier as the above-mentioned tackifier (E) can be used.
  • the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, still more preferably 0.1 to 50% by mass, based on the total amount of the pressure-sensitive adhesive composition. More preferably, it is 0.5 to 45% by mass, and still more preferably 1.0 to 40% by mass.
  • the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive additive used for a general pressure-sensitive adhesive other than the aforementioned tackifier and crosslinking agent, as long as the effects of the present invention are not impaired. May be.
  • the adhesive additive include an antioxidant, a softener (plasticizer), a rust preventive, a retarder, a catalyst, an ultraviolet absorber, a reaction accelerator, a reaction inhibitor, and the like.
  • these additives for adhesives can be used individually by 1 type or in combination of 2 or more types.
  • each pressure-sensitive adhesive additive is independently preferably 0.0001 to 20 parts by mass, more preferably 10001 parts by mass, based on 100 parts by mass of resin (X). Is 0.001 to 10 parts by mass.
  • the pressure-sensitive adhesive composition may contain water or an organic solvent as a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.
  • the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, tert-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane And the like.
  • these dilution solvents can be used individually by 1 type or in combination of 2 or more types.
  • the concentration of the active ingredient in the pressure-sensitive adhesive composition is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 60% by mass. %, More preferably 25 to 45% by mass, even more preferably 30 to 45% by mass.
  • release sheet a conventionally known release sheet can be used.
  • a material having a release layer that has been subjected to a release treatment with a release agent on a release sheet substrate may be used.
  • the release sheet substrate include paper substrates such as glassine paper, coated paper and woodfree paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene terephthalate resin, polybutylene terephthalate resin And a plastic film formed from polyethylene naphthalate resin, polypropylene resin, polyethylene resin and the like. These can be used alone or in combination of two or more. Further, the base material for a release sheet may be a laminate in which two or more of these are laminated.
  • the release agent examples include a rubber-based elastomer such as a silicone-based resin, an olefin-based resin, an isoprene-based resin, and a butadiene-based resin, a long-chain alkyl-based resin, an alkyd-based resin, and a fluorine-based resin. These can be used alone or in combination of two or more.
  • a rubber-based elastomer such as a silicone-based resin, an olefin-based resin, an isoprene-based resin, and a butadiene-based resin, a long-chain alkyl-based resin, an alkyd-based resin, and a fluorine-based resin.
  • the method for producing the gas barrier laminate is not particularly limited.
  • a gas barrier film is attached to the surface of the adhesive layer on which the release sheet is not provided, and the gas barrier film and the adhesive layer of the protection film are attached to each other to form a gas barrier film. It is possible to produce a functional laminate.
  • the protection film is a single protection layer, the gas barrier laminate can be manufactured by laminating the protection layer and the gas barrier film.
  • a protective layer can be laminated on a gas barrier film due to the self-adhesion of the protective film.
  • the sealed body seals the object to be sealed by bonding the exposed surface of the adhesive layer and the object to be sealed to cover the object to be sealed.
  • Examples of the object to be sealed include electronic devices such as an organic EL device, an organic EL display device, a liquid crystal display device, and a solar cell device.
  • the object to be sealed may be mounted on a substrate such as a transparent substrate.
  • the curable adhesive layer of the gas barrier laminate has a surface on the object to be sealed and a substrate surface around the object to be sealed. Affixed to cover.
  • the transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. In addition, a material having high blocking performance for preventing water vapor or gas entering from the outside of the element and having excellent solvent resistance and weather resistance is preferable.
  • transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetylcellulose, brominated phenoxy, aramids, polyimides, Transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins;
  • the thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance of blocking the inside and outside of the element.
  • the method for manufacturing the sealed body is not particularly limited.
  • a sealed body is obtained by covering at least the surface of the object to be sealed with the adhesive layer of the gas barrier laminate.
  • the adhesive layer of the gas barrier laminate is a curable adhesive layer
  • the adhesive layer of the gas barrier laminate is cured by performing a curing treatment such as heating or energy beam irradiation. Adhesion with the surface of the sealed object can be further improved.
  • the step of peeling and removing the protection film from the gas barrier laminate is a step of manufacturing a sealed body by sealing an object to be sealed with the gas barrier laminate, and a process of processing and transporting the sealed body. Any of them may be used.
  • the method for manufacturing a sealed body preferably includes the following steps (1) and (2) in this order.
  • Step (1) a step of attaching the gas barrier laminate of the present invention to an object to be sealed with the adhesive layer as a bonding surface.
  • Step (2) a step of peeling the protection film from the gas barrier laminate.
  • the protective film is peeled from the gas barrier laminate, and the step of removing is performed before or after the curing of the adhesive layer.
  • the adhesive layer is cured by heating, from the viewpoint of preventing the failure due to the change in the properties and the shape of the protective layer and the pressure-sensitive adhesive layer of the protective film due to the heat at the time of curing the adhesive layer, the protective film has a gas barrier property.
  • the step of peeling and removing from the laminate is preferably before the adhesive layer is cured.
  • the protective film is formed of a gas barrier property.
  • the step of peeling and removing from the laminate is preferably before the adhesive layer is cured. That is, in one embodiment of the present invention, the method for manufacturing a sealed body preferably includes the following steps (1) to (3) in this order. Step (1): A step of attaching the gas barrier laminate of the present invention to an object to be sealed with the curable adhesive layer as a bonding surface. Step (2): Peeling the protection film from the gas barrier laminate.
  • Step / Step (3) Step of Curing the Curable Adhesive Layer
  • the curing treatment in step (3) may be heating or energy beam irradiation.
  • the adhesive force a between the glass plate and the curable adhesive layer and the adhesive force b between the gas barrier film and the protection film satisfy the above formula (1). Therefore, even before the adhesive layer is cured, the protection film can be peeled off without generating a gap between the object to be sealed and the adhesive layer.
  • the bonding conditions when bonding the adhesive layer of the gas barrier laminate with the object to be sealed are not particularly limited.
  • the temperature at the time of sticking is, for example, 10 to 60 ° C, preferably 20 to 45 ° C. This bonding process may be performed while applying pressure.
  • the adhesive layer included in the gas barrier laminate is a thermosetting adhesive layer
  • the curing conditions for curing the thermosetting adhesive layer are not particularly limited.
  • the heating temperature is usually from 80 to 200 ° C. (preferably from 90 to 150 ° C.), and the heating time is usually from 30 minutes to 12 hours (preferably). Is 1 to 6 hours).
  • the curing conditions for curing the energy ray-curable adhesive layer are not particularly limited.
  • the adhesive layer of the gas barrier laminate is an energy ray-curable adhesive layer
  • the curing conditions for curing the energy ray-curable adhesive layer are not particularly limited.
  • Thickness of anchor coat layer The thickness was measured using a film thickness measurement device (manufactured by Filmetrics Co., Ltd., product name “F20”).
  • Thickness of gas barrier layer The thickness was measured using a spectroscopic ellipsometer (manufactured by JA Woolam Japan KK, product name "M-2000”).
  • (3) Measurement of the thickness of each layer other than the anchor coat layer and the gas barrier layer Using a constant-pressure thickness measuring instrument manufactured by Teklock Co., Ltd. (model number: “PG-02J”, standard: conforming to JIS K6783, Z1702, Z1709) Measured.
  • Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the modified polyolefin resin (A1) used as the polyolefin resin (A) as the raw material of the curable adhesive layer and the polyfunctional epoxy compound (B2) used as the curable component (B) Weight average molecular weight (Mw), the weight average molecular weight (Mw) of the acrylic resin that is the raw material of the pressure-sensitive adhesive layer of the protective film, and the number average molecular weight (Mn) of the PIB resin are values measured by the following methods. It is.
  • Weight average molecular weight (Mw) of polyfunctional epoxy compound (B2) Using a gel permeation chromatograph (GPC) apparatus described above, the weight average of the standard polystyrene corresponding to the retention time of the peak top having the largest area among the plurality of observed peaks was measured under the above conditions. The value was converted to a molecular weight.
  • gas barrier laminate A gas barrier film, a curable adhesive layer, and a protect film described below were prepared, and these were laminated to produce 18 types of gas barrier laminates 1 to 18.
  • PET50A4100 Polyethylene terephthalate (PET50A4100, manufactured by Toray Industries, Inc., thickness: 50 ⁇ m) is used as a base layer, and one side of the base layer (smooth surface that is not subjected to easy adhesion treatment) is applied with ultraviolet (UV) light.
  • a composition containing a curable resin and reactive silica product name “Opster Z7530” manufactured by JSR Corporation) was applied using a Meyer bar to form a coating film, and the coating film was dried at 70 ° C. for 1 minute.
  • UV irradiation conditions ⁇ UV lamp: High pressure mercury lamp ⁇ Line speed: 20 m / min ⁇ Integrated light amount: 120 mJ / cm 2 ⁇ Illuminance: 200 mW / cm 2 ⁇ Lamp height: 104mm
  • a coating material containing perhydropolysilazane as a main component (manufactured by Clariant Japan Co., Ltd., trade name “Aquamica NL110-20”) is applied to the surface of the anchor coat layer by spin coating, and heated at 120 ° C. for 1 minute, A polysilazane layer containing perhydropolysilazane was formed. The thickness of the polysilazane layer was 200 nm.
  • argon (Ar) was plasma ion-implanted on the surface of the polysilazane layer to form a gas barrier layer, thereby producing a gas barrier film 1 having the following laminated structure.
  • (Laminated structure of gas barrier film 1) ⁇ Base layer / Anchor coat layer / Gas barrier layer
  • thermosetting adhesive layers 1 to 3 were formed as adhesive layers.
  • thermosetting adhesive layer 1 100 parts by mass of polyolefin resin (A), 27 parts by mass of curable component (B), 0.1 parts by mass of silane coupling agent (C), curing catalyst (D) 0.6 part by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition 1 having a solid content concentration of 20% by mass.
  • the polyolefin resin (A) used for preparing the adhesive composition 1, the thermosetting component (B-1) used as the curable component (B), the silane coupling agent (C), and the curing catalyst (D ) Are shown below.
  • the prepared adhesive composition 1 was applied on a release-treated surface of a release sheet (trade name: “SP-PET381031”, manufactured by Lintec Corporation), and the obtained coating film was heated at 100 ° C. for 2 minutes to obtain a thickness. Formed a thermosetting adhesive layer 1 having a thickness of 10 ⁇ m.
  • thermosetting adhesive layer 2 In “(2-1) Formation of thermosetting adhesive layer 1”, the thermosetting component (B-1) is shown below.
  • the adhesive composition 2 was prepared by changing to the thermosetting component (B-2), and the thermosetting adhesive layer 2 was formed.
  • thermosetting adhesive layer 3 100 parts by mass of polyolefin resin (A), 90 parts by mass of curable component (B), 0.1 parts by mass of silane coupling agent (C), curing catalyst (D) 1.2 parts by mass and 50 parts by mass of a tackifier (E) were dissolved in methyl ethyl ketone to prepare an adhesive composition 3 having a solid content concentration of 28% by mass.
  • the polyolefin resin (A), the silane coupling agent (C), and the curing catalyst (D) were the same as those used in “(2-1) Formation of thermosetting adhesive layer 1” above.
  • the curable component (B) was the thermosetting component (B-2) used in the above “(2-2) Formation of thermosetting adhesive layer 2”.
  • thermosetting adhesive layer 3 was formed in the same manner as in “(2-1) Formation of thermosetting adhesive layer 1” described above.
  • a pressure-sensitive adhesive composition having a solid concentration of 37% by mass.
  • the pressure-sensitive adhesive composition was knife-coated on a release surface of a release sheet (manufactured by Lintec Corporation, product name "SP-PET381031," thickness: 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film with a silicone release agent. Coating was performed with a coater to form a coating film. The coating film was heated at 90 ° C. for 1 minute to form a 20 ⁇ m-thick pressure-sensitive adhesive layer.
  • a laminate comprising the pressure-sensitive adhesive layer and the release sheet was obtained.
  • the pressure-sensitive adhesive layer of the laminate is bonded to one side of a polyethylene terephthalate film (manufactured by Toray Advanced Materials Korea, product name “XD571S”, tensile modulus at 23 ° C .: 3.9 GPa, thickness: 38 ⁇ m).
  • a protected film 2 having the following laminated structure was produced. (Structure of the protection film 2) -Release sheet / adhesive layer (thickness: 20 ⁇ m, acrylic resin) / protect layer (thickness: 38 ⁇ m, polyethylene terephthalate film)
  • a protect film 4 was prepared in the same manner as in the above “(2) Protect film 2”, except that the thickness of the pressure-sensitive adhesive layer was adjusted to 2 ⁇ m. (Structure of the protection film 4) ⁇ Release sheet / pressure-sensitive adhesive layer (thickness: 2 ⁇ m, PIB resin) / protect layer (thickness: 38 ⁇ m, polyethylene terephthalate film)
  • a soda lime glass plate was prepared by peeling a release sheet of a gas barrier laminate cut to a width of 50 mm and a length of 20 mm, and using a thermosetting adhesive layer as a bonding surface. was laminated with a gas barrier laminate.
  • the lamination was performed using a laminator equipped with rollers (roll type multi-laminator manufactured by Japan Office Laminator Co., Ltd.) under the conditions of a temperature of 23 ° C., a pressure of 0.2 MPa, and a speed of 2.0 m / min. After lamination, 50% R.F. H.
  • thermosetting adhesive layer of the gas barrier laminate was adhered to a soda lime glass plate via a double-sided tape and measured again, and the adhesive strength b was measured. It was measured.
  • Table 1 shows the following. As in Examples 1 to 15, the gas-barrier laminate having a> b does not show any lifting and has a good appearance. On the other hand, as in Comparative Examples 1 to 3, it is found that the gas-barrier laminates in which a ⁇ b satisfy floating conditions and have poor appearance.

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  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un stratifié faisant barrière aux gaz ayant une structure en couches qui comprend une couche adhésive durcissable, un film faisant barrière aux gaz, et un film protecteur qui ont été disposés dans cet ordre. Dans les cas où le stratifié faisant barrière aux gaz est appliqué à une plaque de verre par pression du stratifié faisant barrière aux gaz contre la plaque de verre, à l'aide de la surface de la couche adhésive durcissable en tant que surface de liaison, avec un rouleau dans les conditions suivantes (alpha) puis décollée dans les conditions suivantes (beta) et dans d'autres conditions selon la Norme JIS Z0237: 2000 pour mesurer la force adhésive a entre la plaque de verre et la couche adhésive durcissable et la force adhésive b entre le film faisant barrière aux gaz et le film protecteur, alors les forces adhésives a et b satisfont la relation (1). (1) : a>b Conditions (alpha): température, 23 °C; pression, 0,2 MPa; et vitesse, 0,2 m/Min Conditions (beta) : après l'application, le stratifié sur la plaque de verre est laissé à reposer pendant 24 heures dans un environnement à 23 °C et avec une humidité relative de 50 % puis décollé à une vitesse de pelage de 300 mm/min.
PCT/JP2019/038313 2018-09-28 2019-09-27 Stratifié faisant barrière aux gaz WO2020067488A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020217008351A KR20210068018A (ko) 2018-09-28 2019-09-27 가스 배리어성 적층체
JP2020549468A JP7356442B2 (ja) 2018-09-28 2019-09-27 ガスバリア性積層体
CN201980062627.0A CN112752813B (zh) 2018-09-28 2019-09-27 阻气性层叠体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018185803 2018-09-28
JP2018-185803 2018-09-28

Publications (1)

Publication Number Publication Date
WO2020067488A1 true WO2020067488A1 (fr) 2020-04-02

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Country Link
JP (1) JP7356442B2 (fr)
KR (1) KR20210068018A (fr)
CN (1) CN112752813B (fr)
TW (1) TWI805854B (fr)
WO (1) WO2020067488A1 (fr)

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TWI811636B (zh) * 2020-03-31 2023-08-11 日商東洋紡股份有限公司 附有保護膜之無機基板/工程塑膠薄膜積層體、積層體之堆疊、積層體的保管方法、及積層體的運輸方法

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WO2013018602A1 (fr) * 2011-08-03 2013-02-07 リンテック株式会社 Feuille adhésive dotée de propriétés de barrière aux gaz ainsi que procédé de fabrication de celle-ci, et élément électronique ainsi qu'élément optique
JP2016089097A (ja) * 2014-11-07 2016-05-23 リンテック株式会社 フィルム状封止材、封止シートおよび電子デバイス
WO2016152558A1 (fr) * 2015-03-26 2016-09-29 富士フイルム株式会社 Film fonctionnel, et procédé de fabrication d'un film fonctionnel
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CN115464960A (zh) * 2022-07-27 2022-12-13 华东理工大学 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用

Also Published As

Publication number Publication date
JPWO2020067488A1 (ja) 2021-09-24
JP7356442B2 (ja) 2023-10-04
TW202030286A (zh) 2020-08-16
TWI805854B (zh) 2023-06-21
KR20210068018A (ko) 2021-06-08
CN112752813B (zh) 2023-02-28
CN112752813A (zh) 2021-05-04

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