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WO2018180962A1 - Film formant une barrière aux gaz et objet scellé de manière étanche - Google Patents

Film formant une barrière aux gaz et objet scellé de manière étanche Download PDF

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Publication number
WO2018180962A1
WO2018180962A1 PCT/JP2018/011633 JP2018011633W WO2018180962A1 WO 2018180962 A1 WO2018180962 A1 WO 2018180962A1 JP 2018011633 W JP2018011633 W JP 2018011633W WO 2018180962 A1 WO2018180962 A1 WO 2018180962A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas barrier
layer
barrier film
group
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/011633
Other languages
English (en)
Japanese (ja)
Inventor
智史 永縄
健太 西嶋
健寛 大橋
達矢 泉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Priority to CN201880017227.3A priority Critical patent/CN110392721A/zh
Priority to KR1020197025889A priority patent/KR102496772B1/ko
Priority to JP2019509697A priority patent/JP7158377B2/ja
Publication of WO2018180962A1 publication Critical patent/WO2018180962A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

  • the present invention relates to a gas barrier film and a sealing body in which an object to be sealed is sealed with the gas barrier film.
  • organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
  • the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity tend to deteriorate with time.
  • the problem of deterioration in performance over time is a problem that generally applies to electronic members and optical members that are attracting attention in recent years. As this cause, it is thought that oxygen, moisture, etc. permeate the inside of the electronic member or the optical member, causing the performance deterioration.
  • several methods have been proposed in which an electronic member, an optical member, or the like, which becomes an object to be sealed, is sealed with a gas barrier sealing material having a layer structure.
  • Patent Document 1 discloses a gas barrier pressure-sensitive adhesive sheet having a layer structure of release sheet / protective layer / gas barrier layer / adhesive layer / release sheet as a sealing material.
  • the invention of such a gas barrier pressure-sensitive adhesive sheet is based on the idea of providing a transfer laminate having a gas barrier layer (paragraph 0004 of Patent Document 1). That is, in the case of a laminate for transfer, the pressure-sensitive adhesive layer is bonded to the object to be sealed, and then the release sheet is removed, so that the release sheet is the support until the gas barrier member is applied to the object to be sealed. Since the protective layer does not need to have a function as a support, the range of selection of the material for the protective layer is widened.
  • Patent Document 1 discloses an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a polyurethane as a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer.
  • Type adhesives and silicone type adhesives are described.
  • Patent Document 2 discloses a gas barrier film having a layer structure of a cured resin layer / gas barrier layer / adhesive layer as a sealing material.
  • the invention according to Patent Document 2 also discloses a form in which a process sheet is laminated on a cured resin layer (see paragraph 0138 of Patent Document 2).
  • the gas barrier film is a transfer laminate as in Patent Document 1.
  • the gas barrier film using the cured resin layer of the invention according to Patent Document 2 has excellent heat resistance, solvent resistance, interlayer adhesion, and gas barrier properties, and has a low birefringence and excellent optical isotropy.
  • Patent Document 2 describes an acrylic, silicone, rubber-based adhesive or pressure-sensitive adhesive as a material for forming the adhesive layer.
  • An object of the present invention is to provide a gas barrier film that is held in the above and excellent in sealing performance with respect to an object to be sealed, and to provide a sealed body in which the object to be sealed is sealed with the gas barrier film.
  • the present inventor has formed an adhesive layer from an adhesive composition containing a polyolefin-based resin (A) and a thermosetting component (B).
  • A polyolefin-based resin
  • B thermosetting component
  • a gas barrier film according to [1] wherein the polyolefin resin (A) includes a modified polyolefin resin (A1).
  • the thermosetting component (B) includes a thermosetting epoxy resin (B1).
  • the method includes a step of adhering an adhesive layer of the gas barrier film according to any one of claims 1 to 10 to an object to be sealed, and a step of peeling the release sheet from the gas barrier film. Manufacturing method of sealing body.
  • the initial performance that the object to be sealed had for a long period of time is suitably maintained, and the sealing performance for the object to be sealed is improved. While providing an excellent gas barrier film, it is possible to provide a sealed body in which an object to be sealed is sealed with the gas barrier film.
  • the gas barrier film of the present invention has a laminate formed by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive layer in this order, and the adhesive layer is composed of a polyolefin resin (A) and thermosetting. It is the layer formed from the adhesive composition containing a sex component (B).
  • the “gas barrier property” refers to a characteristic that prevents permeation of gases such as oxygen and water vapor.
  • the gas barrier film of the present invention is not particularly limited as long as it is constituted by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive layer in this order, but the adhesive layer is formed on the gas barrier layer. It may be laminated directly, or may be laminated on the gas barrier layer via an adhesion improving layer.
  • first release sheet and the second release sheet may be the same or different.
  • the aspect of the layer configuration described above represents a state before the gas barrier film is used as a sealing material.
  • the second release sheet is usually peeled and removed, and the exposed adhesive layer The surface and the object to be sealed are bonded to obtain a sealed body.
  • the first release sheet is usually peeled and removed to expose the resin layer to have the layer configuration shown below. be able to. -Underlayer / Gas barrier layer / Adhesive layer-Underlayer / Gas barrier layer / Adhesion improving layer / Adhesive layer Even if the gas barrier film of the present invention has no substrate, the first release sheet is peeled and removed. In the meantime, it functions as a support or protective member for the gas barrier film.
  • the laminate of the present invention is constituted by laminating a release sheet, an underlayer, a gas barrier layer, and an adhesive layer in this order, and the adhesive layer is composed of a polyolefin resin (A) and a thermosetting component (B). It is formed from the containing adhesive composition.
  • the water vapor permeability of the laminate constituting the gas barrier film of the present invention is preferably 5.0 g / m 2 / day or less, more preferably 0.5 g / m 2 / day or less, and even more preferably 5 ⁇ 10 ⁇ 2. (G / m 2 / day) or less, more preferably 5 ⁇ 10 ⁇ 3 (g / m 2 / day) or less.
  • the “water vapor transmission rate” refers to a value measured in a high temperature and high humidity environment at 40 ° C. and a relative humidity of 90% using a water vapor transmission rate measuring device. A more specific measurement method will be described later. Based on the method of the embodiment.
  • the first release sheet is peeled and removed. Usually, the water vapor transmission rate of the release sheet is compared with the water vapor transmission rate of the gas barrier layer.
  • the water vapor permeability of the laminate measured with the first release sheet remaining is the gas barrier performance of the film-like body formed on the object to be sealed by removing the first release sheet from the laminate. Is considered to be reflected. Therefore, the water vapor permeability of the gas barrier film in the present invention is a numerical value measured with the first release sheet left in order to maintain the self-supporting property of the gas barrier film, as shown in the examples described later.
  • the present inventors have used a gas barrier film having a normal adhesive layer as a sealing material, and a sealing body formed by sealing an object to be sealed with the sealing material as a test for high temperature and high humidity.
  • a gas barrier film having a normal adhesive layer as a sealing material
  • a sealing body formed by sealing an object to be sealed with the sealing material as a test for high temperature and high humidity.
  • the present inventors have studied a material for forming an adhesive layer having excellent adhesive strength with little decrease in the adhesiveness of the adhesive surface between the adhesive layer of the sealing material and the object to be sealed over a long period of time. went. As a result of repeated studies, the present inventors have formed an adhesive layer from an adhesive composition containing a polyolefin-based resin (A) and a thermosetting component (B). It has been found that excellent adhesiveness is maintained on the adhesive surface between the adhesive layer of the stopper and the object to be sealed.
  • A polyolefin-based resin
  • B thermosetting component
  • 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 5 to 80 ⁇ m.
  • the thickness of the said adhesive bond layer exists in the said range, when using a gas barrier film as a sealing material, it becomes easy to use suitably.
  • the adhesive layer of the present invention is formed from an adhesive composition containing a polyolefin resin (A) and a thermosetting component (B).
  • A polyolefin resin
  • B thermosetting component
  • the water vapor barrier property of the adhesive layer is increased, the sealing performance can be improved, and an excellent adhesive strength can be obtained on the adhesive surface between the adhesive layer of the sealing material and the object to be sealed.
  • Excellent adhesiveness is maintained for a long time on the adhesive surface between the adhesive layer of the sealing material and the object to be sealed. Therefore, the gas barrier film excellent in the sealing performance with respect to a to-be-sealed object is suitably hold
  • each component contained in the adhesive composition suitable as a material for forming the adhesive layer will be described.
  • the adhesive composition of the present invention contains a polyolefin resin (A).
  • a polyolefin resin (A) refers to a polymer having a repeating unit derived from an olefin monomer.
  • the olefinic monomer ⁇ -olefins having 2 to 8 carbon atoms are preferable, and ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1-pentene, and 1-hexene are particularly preferable.
  • the polyolefin resin may have two or more types of ⁇ -olefin-derived units.
  • the polyolefin resin may be a polymer composed only of repeating units derived from olefinic monomers, or a single unit copolymerizable with repeating units derived from olefinic monomers and olefinic monomers. It may be a polymer composed of repeating units derived from a monomer. Examples of the monomer copolymerizable with the olefin monomer include vinyl acetate, (meth) acrylic acid ester, and styrene.
  • 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, and polypropylene (PP ), Ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, Examples thereof include polyisobutylene and polyisoprene.
  • VLDPE very low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • Ethylene-propylene copolymer olefin elastomer
  • TPO olefin elastomer
  • EVA ethylene-vinyl acetate copolymer
  • the modified polyolefin resin (A1) is included as the polyolefin resin (A).
  • the adhesive layer is further excellent in adhesive strength.
  • the “modified polyolefin resin (A1)” means that the polyolefin resin (A) as a precursor reacts with the modifier, and the functional group of the modifier is on the side of the polyolefin resin (A) as the main chain. It refers to a polymer introduced as a chain.
  • the modifier may have two or more types of functional groups in the molecule.
  • Examples of the functional group that the modifier has and can be introduced as a side chain into the polyolefin resin (A) as the 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, phosphone group, nitro group, urethane group, A halogen atom, alkoxysilyl, etc. are mentioned.
  • a carboxyl group a group derived from a carboxylic acid anhydride, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate, and an alkoxysilyl group are preferable. Origin groups are preferred.
  • modified polyolefin resin examples include acid-modified polyolefin resins and silane-modified polyolefin resins. Among these, acid-modified polyolefin resin is preferable from the viewpoint of high reactivity with the thermosetting component (B).
  • acid-modified polyolefin resin means that a polyolefin resin (A) as a precursor reacts with a compound having an acid group, and an acid group is introduced as a side chain into the polyolefin resin (A) as a main chain. It refers to the polymer made.
  • a known side chain introduction method can be employed as a method and conditions for introducing the acid group of the compound having an acid group into the polyolefin resin (A) as the main chain as a side chain.
  • the compound having an acid group is not particularly limited as long as it can be introduced as a side chain into the polyolefin-based resin (A) as a main chain, and preferably includes unsaturated carboxylic acid and its anhydride.
  • unsaturated carboxylic acid and its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride And aconitic acid, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like.
  • unsaturated carboxylic acids and anhydrides thereof can be used alone or in combination of two or more.
  • maleic anhydride is preferable because an adhesive composition that is superior in adhesive strength can be easily obtained.
  • a commercially available product may be used as the acid-modified polyolefin resin.
  • Examples of commercially available acid-modified polyolefin resins include Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistor (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), and orevac (registered trademark) (Made by ARKEMA), Modic (registered trademark) (made by Mitsubishi Chemical Corporation), and the like.
  • the compounding amount of the compound having an acid group to be reacted with the polyolefin resin (A) as a precursor is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin (A) as a precursor.
  • the amount is more preferably 0.2 to 3 parts by mass, still more preferably 0.2 to 1.0 part by mass.
  • the adhesive composition is more excellent in adhesive strength.
  • silane-modified polyolefin resin means that the polyolefin resin (A) as a precursor reacts with a compound having a silane group, and the silane group is introduced as a side chain into the polyolefin resin (A) as a main chain. It refers to the polymer made.
  • a known side chain introduction method can be employed as a method and conditions for introducing the silane group of the compound having a silane group as a side chain into the polyolefin resin (A) serving as the main chain.
  • the compound having a silane group is not particularly limited as long as it can be introduced as a side chain into the polyolefin resin (A) serving as the main chain, and an unsaturated silane compound is preferable.
  • an unsaturated silane compound a vinyl silane compound is preferable.
  • These unsaturated silane compounds can be used individually by 1 type or in combination of 2 or more types.
  • silane-modified polyolefin resin examples include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers. Among them, silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, silane-modified linear A silane-modified polyethylene resin such as a low-density polyethylene is preferred.
  • silane-modified polyolefin resin A commercially available product can also be used as the silane-modified polyolefin resin.
  • silane-modified polyolefin resins include, for example, Rinklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation).
  • Rinklon low-density polyethylene-based Rinklon, linear low-density polyethylene, and the like.
  • the linkron of the system, the linkron of the ultra-low density polyethylene system, and the linkron of the ethylene-vinyl acetate copolymer system are preferable.
  • the compounding amount of the compound having a silane group to be reacted with the polyolefin resin (A) as a precursor is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin (A) as a precursor.
  • the amount is more preferably 0.3 to 7 parts by mass, still more preferably 0.5 to 5 parts by mass.
  • the adhesive composition containing the resulting silane-modified polyolefin resin is more excellent in adhesive strength.
  • the weight average molecular weight (Mw) of the polyolefin resin (A) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 25,000 to 250,000. More preferably, it is 30,000 to 150,000.
  • the weight average molecular weight (Mw) is in the above range, the shape of the sheet formed from the adhesive composition even when the content of the polyolefin resin (A) in the adhesive composition is large. It becomes easy to maintain.
  • the “weight average molecular weight (Mw)” refers to a value obtained by conversion to standard polyethylene using gel permeation chromatography using tetrahydrofuran as a solvent.
  • the polyolefin resin (A) may be composed only of the modified polyolefin resin (A1), or may be composed of the modified polyolefin resin (A1) and an unmodified polyolefin resin.
  • the content of the modified polyolefin resin (A1) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the polyolefin resin (A). Is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the adhesive composition is more excellent in adhesive strength.
  • the content of the polyolefin resin (A) is preferably 30 to 95% by mass, more preferably 45 to 90% by mass, and still more preferably based on the total amount (100% by mass) of the active ingredients of the adhesive composition described above. Is 50 to 85% by mass.
  • the “active component of the adhesive composition” refers to a component excluding the solvent contained in the adhesive composition.
  • thermosetting component (B) refers to a component that forms a network structure and is cured in an insoluble and infusible state when heated.
  • thermosetting component (B) a thermosetting epoxy resin, a melamine resin, a urea resin, a maleimide resin etc. are mentioned, for example. It is preferable that a thermosetting epoxy resin (B1) is included as the thermosetting component (B).
  • thermosetting epoxy resin (B1)” refers to an epoxy compound that forms a network structure and cures in an insoluble and infusible state when heated.
  • a polyfunctional epoxy resin (B2) is included as the above-described thermosetting epoxy resin (B1).
  • the “polyfunctional epoxy resin (B2)” refers to a compound having at least two epoxy groups in the molecule.
  • the multifunctional epoxy resin (B2) has two epoxy groups in the molecule because excellent adhesive strength is more easily obtained on the adhesive surface between the adhesive layer of the sealing material and the object to be sealed.
  • a bifunctional epoxy resin is preferred.
  • 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 type epoxy resins (for example, phenol / novolak type epoxy resins, cresol / novolak type epoxy resins, brominated phenol / novolak type epoxy resins); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F di Alicyclic epoxy compounds such as glycidyl ether and hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hex 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 decanediglycidyl ether; and the like.
  • These bifunctional epoxy resins can be used singly or in combination
  • the content of the thermosetting component (B) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, more preferably 5 to 40% by mass, based on the total amount (100% by mass) of the active ingredients of the adhesive composition described above.
  • the content is preferably 10 to 30% by mass.
  • the “active component of the adhesive composition” refers to a component excluding the solvent contained in the adhesive composition.
  • the content of the thermosetting component (B) in the adhesive composition is preferably 5 to 110 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin (A). .
  • An adhesive layer formed from an adhesive composition in which the content of the thermosetting component (B) is within this range is more excellent in water vapor barrier properties.
  • the adhesive composition of the present invention preferably further contains a curing catalyst (C) from the viewpoint of easily obtaining an adhesive layer having higher adhesive strength.
  • the “curing catalyst (C)” refers to a catalyst for curing the thermosetting component (B).
  • an imidazole curing catalyst is preferable from the viewpoint of suitably proceeding the curing of the thermosetting component (B).
  • the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
  • These imidazole-based curing catalysts can be used alone or in combination of two or more. Of these imidazole-based curing catalysts, 2-ethyl-4-methylimidazole is preferable.
  • the content of the curing catalyst (C) to be contained in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the thermosetting component (B). Part.
  • the adhesive layer has excellent adhesiveness even at high temperatures.
  • the adhesive composition of the present invention may further contain a silane coupling agent (D).
  • a silane coupling agent (D) refers to an organosilicon compound having two or more different reactive groups in the molecule.
  • silane coupling agent (D) an organosilicon compound having at least one alkoxysilyl group in the molecule is preferable from the viewpoint of obtaining excellent adhesive strength.
  • silane coupling agents include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2 A silicon compound having an epoxy structure such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane; 3-aminopropyltrimethoxysilane; Amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl)
  • the content of the silane coupling agent (D) to be contained in the adhesive composition is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 with respect to 100 parts by mass of the polyolefin resin (A). 1.0 parts by mass.
  • the content of the silane coupling agent (D) is within the above range, even when exposed to a high temperature and high humidity environment for a long time, the adhesive layer of the sealing material and the object to be sealed are adhered. Excellent adhesion on the surface is easily maintained.
  • the adhesive composition is in the form of a solution by adding a solvent from the viewpoint of easily adjusting the adhesive composition to properties suitable for application when the adhesive layer is formed by application.
  • the solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane, n-hexane, and aliphatic hydrocarbon solvents such as n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; Among these, ketone solvents are preferable, and dimethyl ethyl ketone is particularly preferable.
  • the amount of the solvent used for the preparation of the adhesive composition is such that the solid content is preferably 8 to 48% by mass, more preferably 8 to 38% by mass, and still more preferably 8 to 28% by mass. Good.
  • the adhesive composition includes: It may further contain other components as long as the curing of the present invention is not impaired.
  • other components include ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, and tackifiers.
  • the gas barrier film of the present invention has a base layer, it is possible to suppress damage and deterioration of the gas barrier layer and to efficiently peel and remove the release sheet.
  • the underlayer is preferably laminated directly on the release sheet. The underlayer is interposed between the release sheet and the gas barrier layer.
  • the thickness of the underlayer is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
  • the thickness of the underlayer is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
  • the thickness of the underlayer is in the above range, it is easy to suppress damage and deterioration of the gas barrier layer and to easily peel and remove the release sheet efficiently.
  • the underlying layer is as thin as about 0.1 to 10 ⁇ m, it is easy to adjust the overall thickness of the gas barrier film to a small range, which is suitable for applications that require miniaturization of electronic devices such as organic EL elements. It is.
  • the gas barrier film is composed of a base material and a gas barrier layer, if the base material has such a thin thickness, it may be difficult to handle the gas barrier film.
  • the release sheet is present on the side opposite to the side on which the gas barrier layer is laminated, the problem of handleability is solved. And since a peeling sheet is normally removed after applying a gas barrier film to a to-be-sealed thing, the member derived from the gas barrier film which remains in a sealing body can be made thin.
  • the thickness of the base layer may be preferably 1 to 20 ⁇ m depending on the application, and in that case, the thickness of the base layer is more preferably 3 to 15 ⁇ m. .
  • the maximum cross-sectional height (Rt) of the roughness curve on the surface of the underlayer on the side of the underlayer that is in contact with the release sheet or the surface of the underlayer on the side opposite to the side that is in contact with the release sheet is preferably 1 to
  • the thickness is 300 nm, more preferably 1 to 200 nm, still more preferably 2 to 150 nm.
  • the maximum cross-sectional height (Rt) of the underlayer can be measured by observing the surface of the underlayer using an optical interference microscope. For example, when the base layer is formed on the release sheet in the gas barrier film manufacturing process, the exposed surface of the base layer can be a measurement target.
  • the release sheet can be easily peeled and removed efficiently while suitably protecting the gas barrier layer.
  • the said maximum cross-sectional height (Rt) can be made the said range by adjusting the average particle diameter and content of the inorganic filler mentioned later.
  • the underlayer of the present invention is preferably formed from an underlayer composition containing an energy ray curable component. Moreover, it is preferable that the composition for base layers contains the thermoplastic resin. Thereby, while making it easy to suppress damage and deterioration of a gas barrier layer, it can make it easy to peel and remove a peeling sheet efficiently.
  • each component contained in the composition for base layers suitable as a formation material of a base layer is described.
  • thermoplastic resin refers to a resin having a property of being melted or softened by heating and solidified when cooled.
  • thermoplastic resin examples include a resin having an aromatic ring structure and a resin having a ring structure such as an alicyclic structure, and a resin having an aromatic ring structure is preferable.
  • a resin having an aromatic ring structure for example, a polysulfone resin, a polyarylate resin, a polycarbonate resin, and an alicyclic hydrocarbon resin are preferable, and among them, a polysulfone resin is preferable.
  • the polysulfone resin may be a modified polysulfone resin.
  • the “polysulfone resin” refers to a resin made of a polymer compound having a sulfone group (—SO 2 —) in the main chain.
  • polysulfone resin examples include resins made of a polymer compound having a repeating unit represented by the following (a) to (h).
  • polysulfone resin examples include polyethersulfone resin and polysulfone resin are preferable, and among them, polysulfone resin is more preferable.
  • the glass transition temperature (Tg) of the thermoplastic resin is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher.
  • the “glass transition temperature (Tg)” means tan ⁇ (loss elastic modulus / loss) obtained by viscoelasticity measurement (frequency 11 Hz, temperature increase rate 3 ° C./minute, measurement in the tensile mode in the range of 0 to 250 ° C.). It refers to the temperature at the maximum point of storage modulus.
  • Tg glass transition temperature
  • the weight average molecular weight (Mw) of the thermoplastic resin is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, more preferably 500,000 to 2,000,000.
  • the molecular weight distribution (Mw / Mn) of the thermoplastic resin is preferably 1.0 to 5.0, more preferably 2.0 to 4.5.
  • “weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)” refer to values in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • the content of the thermoplastic resin is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 50% with respect to the total amount (100% by mass) of the active ingredients of the above-described underlayer composition. -70% by mass.
  • the “effective component of the composition for the underlayer” refers to a component excluding the solvent contained in the composition for the underlayer.
  • the gas barrier film having high transparency and low birefringence and high optical isotropy can be obtained by forming the underlayer from the underlayer composition containing the energy ray-curable component.
  • the optical anisotropy is high and the light extraction property when applied to a display or the like is inferior.
  • substrates with high optical isotropy such as cycloolefin polymers, but they are difficult to handle and it may be difficult to improve production suitability.
  • the underlayer By forming the underlayer from the underlayer composition containing the energy ray-curable component, it is possible to easily obtain a gas barrier film having high optical isotropy.
  • the composition for an underlayer also has an advantage that an underlayer excellent in solvent resistance can be easily obtained by containing an energy ray-curable component.
  • the energy ray curable component refers to a resin that is turned into a cured product when a curing reaction is initiated by irradiation or heating with an energy ray such as an electron beam or ultraviolet ray.
  • the energy ray curable component is usually a mixture containing a polymerizable compound as a main component.
  • the polymerizable compound is a compound having an energy ray polymerizable functional group. Examples of the energy ray polymerizable functional group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyl group, an allyl group, and a styryl group.
  • Examples of the polymerizable compound include a (meth) acrylate derivative, and specific examples of the (meth) acrylate derivative include, for example, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propoxy Ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 9,9-bis And [4- (2-acryloyloxyethoxy) phenyl] fluorene.
  • specific examples of the (meth) acrylate derivative include, for example, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propoxy Ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth
  • the molecular weight of the (meth) acrylate derivative is usually 3000 or less, preferably 200 to 2000, more preferably 200 to 1000.
  • the energy ray curable component may contain an oligomer as the polymerizable compound.
  • the oligomer include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyol acrylate oligomers, and the like.
  • the energy ray curable component may contain a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.
  • the energy ray curable component a component that is cured by ultraviolet irradiation (ultraviolet curable component) is preferable.
  • an ultraviolet curable component By using an ultraviolet curable component, a layer made of a cured product of an energy ray curable component can be efficiently formed.
  • the polymerization initiator is preferably a photopolymerization initiator, specifically, an alkylphenone photopolymerization initiator, a phosphorus photopolymerization initiator, an oxime ester photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone system.
  • a photopolymerization initiator is preferred, and among them, a phosphorus photopolymerization initiator is more preferred.
  • Examples of phosphorus photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and ethyl (2,4,6-trimethylbenzoyl). ) -Phenylphosphinate, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.
  • the content of the polymerization initiator contained in the energy ray curable component is preferably 0.5 to 6.5 parts by mass, more preferably 0.5 to 5.5 parts per 100 parts by mass of the polymerizable compound described above. Part by mass, more preferably 0.5 to 4.5 parts by mass.
  • the content of the energy ray-curable component is preferably 30 to 90% by mass, more preferably 50 to 70% by mass with respect to the total amount (100% by mass) of the active ingredients of the above-described underlayer composition.
  • the “effective component of the composition for the underlayer” refers to a component excluding the solvent contained in the composition for the underlayer.
  • the composition for underlayer may contain the inorganic filler.
  • inorganic substances constituting the inorganic filler include metal oxides such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide; And metal fluorides such as magnesium fluoride and sodium fluoride.
  • the surface of the inorganic filler may be modified with an organic compound.
  • the average particle size of the inorganic filler is not particularly limited, but is preferably 5 to 100 nm. If the average particle size of the inorganic filler is too small, it may be difficult to sufficiently improve the peelability of the release film. On the other hand, when the average particle size of the inorganic filler is in such a small range, it is easy to maintain high gas barrier properties of the gas barrier layer formed on the underlayer.
  • the average particle size of the inorganic filler can be measured by a dynamic light scattering method using a particle size distribution measuring device.
  • the content of the inorganic filler is preferably 10 to 70% by mass and more preferably 50 to 70% by mass with respect to the total amount (100% by mass) of the active ingredients of the above-described composition for the underlayer.
  • the “effective component of the composition for the underlayer” refers to a component excluding the solvent contained in the composition for the underlayer.
  • the underlayer composition used in one embodiment of the present invention contains a thermoplastic resin, the energy beam curable component contains a polymerizable compound and a polymerization initiator, and the underlayer composition does not contain an inorganic filler.
  • the total content of the thermoplastic resin, the polymerizable compound, and the polymerization initiator is preferably 70 to 100% by mass, more preferably based on the total amount (% by mass) of the active ingredients of the above-described underlayer composition. Is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the “effective component of the composition for the underlayer” refers to a component excluding the solvent contained in the composition for the underlayer.
  • the underlayer composition is in the form of a solution by adding a solvent from the viewpoint of easily adjusting the underlayer composition to properties suitable for application in the step of forming the underlayer by coating.
  • the solvent include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane Halogenated hydrocarbon solvents such as monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ethyl acetate, And ester solvents such as butyl acetate; cellosolv solvents such as butyl acetate;
  • the amount of the solvent used for the preparation of the composition for the underlayer is such that the solid content concentration of the thermoplastic resin is preferably 5 to 45% by mass, more preferably 5 to 35% by mass, and further preferably 5 to 25% by mass. What is necessary is just to use it.
  • the underlayer composition may further contain other components as long as the effects of the present invention are not impaired.
  • other components include a plasticizer, an antioxidant, and an ultraviolet absorber.
  • peeling sheet A conventionally well-known thing can be used for the peeling sheet (1st peeling sheet) laminated
  • a conventionally well-known thing can be utilized as a peeling film.
  • the release sheet substrate include paper substrates such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene terephthalate resin, polybutylene terephthalate resin, Examples thereof include plastic films such as polyethylene naphthalate resin, polypropylene resin, and polyethylene resin.
  • release agent examples include silicone elastomers, olefin resins, isoprene resins, rubber elastomers such as butadiene resins, long chain alkyl resins, alkyd resins, fluorine resins, and the like.
  • silicone elastomers examples include silicone elastomers, olefin resins, isoprene resins, rubber elastomers such as butadiene resins, long chain alkyl resins, alkyd resins, fluorine resins, and the like.
  • the two release films of the first release sheet and the second release sheet may be the same or different.
  • the second release sheet preferably has a release layer from the viewpoint of improving the peelability from the adhesive layer.
  • the thickness of the release sheet is preferably 10 to 300 ⁇ m, more preferably 20 to 125 ⁇ m, and still more preferably 30 to 100 ⁇ m.
  • the gas barrier film of the present invention can exhibit excellent gas barrier properties that are highly effective in preventing permeation of gases such as oxygen and water vapor.
  • the gas barrier layer is interposed between the base layer and the adhesive layer.
  • the gas barrier layer is a single layer, a gas barrier property satisfying a certain level can be obtained, but the effect of the gas barrier property can be enhanced by laminating two or more gas barrier layers.
  • Two or more gas barrier layers may have the same thickness or different thicknesses.
  • the thickness of one gas barrier layer is usually in the range of 20 nm to 50 ⁇ m, preferably 30 nm to 1 ⁇ m, more preferably 40 nm to 500 nm.
  • a gas barrier film having a gas barrier property satisfying a certain level with a high effect of preventing permeation of gases such as oxygen and water vapor can be easily obtained.
  • each gas barrier layer is preferably a layer formed from the same composition. Thereby, interlayer adhesion between two or more gas barrier layers can be improved.
  • the gas barrier layer As a preferred embodiment of the gas barrier layer, (i) a gas barrier layer made of an inorganic vapor deposition film, (ii) a gas barrier layer containing a gas barrier resin, and (iii) a layer containing a polymer compound (hereinafter also referred to as “polymer layer”). )) Surface modified gas barrier layer [in this case, the gas barrier layer means not only a modified region but also a “polymer layer including a modified region”].
  • the gas barrier layer at least one selected from the group consisting of Among these, as a more preferable embodiment of the gas barrier layer, at least one selected from the group consisting of (i) a gas barrier layer made of an inorganic vapor-deposited film and (iii) a gas barrier layer whose surface of the polymer layer is modified. It is a seed.
  • the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
  • the raw material for the vapor-deposited film of the inorganic compound includes inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride Inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides; Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin. These inorganic compounds and metal vapor-deposited film materials can be used singly or in combination of two or more.
  • the inorganic vapor deposition film is preferably an inorganic vapor deposition film using at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and metals as a raw material from the viewpoint of gas barrier properties.
  • an inorganic vapor deposition film using at least one selected from the group consisting of inorganic oxides and inorganic nitrides as a raw material is more preferable.
  • the inorganic vapor deposition film may be a single layer or a multilayer.
  • the thickness of the inorganic vapor deposition film is preferably 1 to 2,000 nm, more preferably 3 to 1,000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm, from the viewpoints of gas barrier properties and handling properties. .
  • the method for forming the inorganic vapor deposition film is not particularly limited, and a known method can be adopted.
  • Examples of the method for forming the inorganic vapor deposition film include PVD methods such as vacuum vapor deposition, sputtering, and ion plating; CVD methods such as thermal CVD, plasma CVD, and photo CVD; atomic layer deposition (ALD) Law);
  • Gas barrier layer containing gas barrier resin examples include polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polychloro Examples thereof include resins that are difficult to permeate gases such as oxygen and water vapor such as trifluoroethylene.
  • the thickness of the gas barrier layer containing the gas barrier resin is preferably 1 to 2,000 nm, more preferably 3 to 1,000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm from the viewpoint of gas barrier properties. is there.
  • Examples of a method for forming a gas barrier layer containing a gas barrier resin include a method in which a solution containing a gas barrier resin is applied on a release film or a substrate, and the obtained coating film is appropriately dried.
  • the coating method of the solution containing the gas barrier resin is not particularly limited, and known coating methods such as a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. A method is mentioned.
  • As a drying method of a coating film well-known drying methods, such as hot air drying, hot roll drying, and infrared irradiation, are mentioned.
  • the polymer compound used is a silicon-containing polymer compound, polyimide, polyamide, polyamideimide. , Polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, alicyclic hydrocarbon resin, aromatic polymer, etc. Can be mentioned. These polymer compounds can be used alone or in combination of two or more.
  • 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 a curing agent, an anti-aging agent, a light stabilizer, and a flame retardant.
  • the content of the polymer compound is preferably 50% by mass or more, more preferably 70% by mass or more with respect to the total amount (100% by mass) of the active ingredients of the polymer layer composition.
  • the “effective component of the polymer layer composition” refers to a component excluding the solvent contained in the polymer layer composition.
  • the thickness of the polymer layer is not particularly limited, but is preferably 20 nm to 50 ⁇ m, more preferably 30 nm to 1 ⁇ m, and still more preferably 40 nm to 500 nm.
  • the polymer layer is formed, for example, by applying a solution obtained by dissolving or dispersing a polymer compound in an organic solvent onto a release film or a substrate layer by a known coating method, and drying the obtained coating film. be able to.
  • organic solvent examples include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane, n-hexane, n -An aliphatic hydrocarbon solvent such as heptane; an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane; These organic solvents can be used individually by 1 type or in combination of 2 or more types.
  • aromatic hydrocarbon solvents such as benzene and toluene
  • ester solvents such as ethyl acetate and butyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • n-pentane n-hexane
  • the coating method of the liquid in which the polymer compound is dissolved or dispersed in the organic solvent is not particularly limited, and the bar coating method, spin coating method, dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife
  • the coating method include a die coating method, a screen printing method, a spray coating method, and a gravure offset method.
  • Examples of the method for drying the coating film for forming the polymer layer include known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
  • the heating temperature is preferably 80 to 150 ° C., and the heating time is usually several tens of seconds to several tens of minutes.
  • examples of the method for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
  • the ion implantation treatment is a method of injecting accelerated ions into the polymer layer to modify the polymer layer.
  • the plasma treatment is a method for modifying the polymer layer by exposing the polymer layer to plasma.
  • plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
  • the ultraviolet irradiation treatment is a method for modifying the polymer layer by irradiating the polymer layer with ultraviolet rays.
  • the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
  • silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. Among these, a polysilazane compound is preferable.
  • the polysilazane compound is a compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule.
  • a compound having a repeating unit represented by the following general formula (1) is preferable.
  • n represents a repeating unit 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, or unsubstituted Alternatively, it represents a non-hydrolyzable group such as an aryl group having a substituent or an alkylsilyl group.
  • alkyl group of the unsubstituted or substituted alkyl group examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
  • alkyl groups having 1 to 10 carbon atoms such as -pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
  • Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the alkenyl group of an unsubstituted or substituted alkenyl group include, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. ⁇ 10 alkenyl groups.
  • examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxy group; a thiol group
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • a hydroxy group such as a thiol group
  • An epoxy group a glycidoxy group; a (meth) acryloyloxy group; an unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
  • the description of “(meth) acryloyl” means “acryloyl” and / or “methacryloyl”.
  • the description of “(meth) acryl” means “acryl” and / or “methacryl”.
  • aryl group of the unsubstituted or substituted aryl group examples include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a methoxy group An alkoxy group having 1 to 6 carbon atoms such as ethoxy group, nitro group, cyano group, hydroxy group, thiol group, epoxy group, glycidoxy group, (meth) acryloyloxy group, phenyl group, 4-methylphenyl group, 4- An unsubstituted or substituted aryl group such as a chlorophenyl group; and the like.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-tert-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl 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.
  • Examples of the polysilazane compound having a repeating unit represented by the general formula (1) include inorganic polysilazanes in which Rx, Ry, and Rz are all hydrogen atoms, and organic polysilazanes in which at least one of Rx, Ry, and Rz is not a hydrogen atom. It may be.
  • a modified polysilazane compound can also be used as the polysilazane compound.
  • the modified polysilazane include, for example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, and JP-A-2-175726.
  • JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333 Examples thereof include those described in JP-A-5-345826 and JP-A-4-63833.
  • Rx, Ry, and Rz in the general formula (1) are all hydrogen atoms. Hydropolysilazane is preferred.
  • the polysilazane compound a commercially available product as a glass coating material or the like can be used as it is.
  • the polysilazane compounds may be used alone or in combination of two or more.
  • the number average molecular weight (Mn) of the polysilazane compound is not particularly limited, but a compound having a molecular weight of 100 to 50,000 can be preferably used.
  • the number average molecular weight (Mn) can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography.
  • ions implanted into the polymer layer ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .; methane, ethane Ions of alkane gases such as ethylene and propylene; ions of alkadiene gases such as pentadiene and butadiene; ions of alkyne gases such as acetylene; aromatics such as benzene and toluene Examples include hydrocarbon gas ions; cycloalkane gas ions such as cyclopropane; cycloalkene gas ions such as cyclopentene; metal ions; organosilicon compound ions; These ions may be used alone or in combination of two or more. Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more flu
  • Examples of the method for implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like.
  • the latter method of plasma ion implantation (plasma ion implantation method) is preferable because the target gas barrier layer can be easily formed.
  • plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer to thereby remove ions (positive ions) in the plasma. It can be performed by injecting into the surface portion of the polymer layer. More specifically, the plasma ion implantation method can be carried out by a method described in WO2010 / 107018 pamphlet or the like.
  • the amount of ions implanted can be determined as appropriate according to the purpose of use of the gas barrier film (necessary gas barrier properties, transparency, etc.), etc.
  • the thickness of the region into which ions are implanted by ion implantation depends on the type of ions. It can be controlled by the injection conditions such as applied voltage and processing time, and may be adjusted according to the thickness of the polymer layer and the purpose of use of the gas barrier film, but is preferably 10 to 400 nm.
  • the ion implantation can be confirmed by performing an elemental analysis measurement in the vicinity of 10 nm from the surface of the polysilazane layer using X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the gas barrier layer may be a single layer or a multilayer. For example, you may use together (i) the gas barrier layer which consists of an inorganic vapor deposition film, and (iii) the gas barrier layer where the surface of the polymer layer is modified.
  • the layer adjacent to the adhesion improving layer is preferably a gas barrier layer made of an inorganic vapor deposition film.
  • the gas barrier film of the present invention is not particularly limited as long as it is constituted by laminating an underlayer, a gas barrier layer, and an adhesive layer in this order, but the adhesive layer is interposed via an adhesion improving layer.
  • the gas barrier layer may be laminated on the gas barrier layer.
  • the gas barrier film of the present invention has an adhesion improving layer, whereby the adhesion between the gas barrier layer and the adhesive layer can be improved.
  • the thickness of the adhesion improving layer is preferably 700 nm or less, more preferably 50 to 700 nm, still more preferably 100 to 500 nm, and still more preferably 150 to 400 nm.
  • the thickness of the adhesion improving layer is within the above range, the effect of improving the adhesion between the gas barrier layer and the adhesive layer can be suitably exhibited.
  • the adhesion improving layer is preferably a layer containing an organic substance. Specifically, a layer containing a polyester resin; a layer containing an acrylic resin; a layer made of a cured product of a curable composition containing an energy ray-curable compound such as a polyfunctional acrylate compound or a polyfunctional urethane acrylate compound; A layer made of a cured product of a curable composition containing a thermosetting resin such as a curable epoxy resin or a melamine resin.
  • the adhesion improving layer is preferably a layer made of a cured product of a curable composition containing a thermosetting epoxy resin.
  • thermosetting epoxy resin is a compound having at least two epoxy groups in the molecule (hereinafter also referred to as “polyfunctional epoxy compound”).
  • thermosetting epoxy resins that can be used in the adhesion improving layer include epoxy resins having a glycidylamino group derived from metaxylylenediamine, and glycidylamino groups derived from 1,3-bis (aminomethyl) cyclohexane.
  • thermosetting epoxy resins an epoxy resin containing an aromatic ring in the molecule is preferable. These thermosetting epoxy resins may be used alone or in combination of two or more.
  • the content of the thermosetting epoxy resin in the curable composition is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the total solid content of the curable composition.
  • the “solid content of the curable composition” refers to a component excluding the solvent contained in the curable composition.
  • the curable composition preferably contains a polyfunctional amine compound. Since the curable composition containing a polyfunctional amine compound proceeds more efficiently, the adhesion improving layer can be efficiently formed.
  • polyfunctional amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, diaminodiphenylmethane, and metaphenylenediamine. It is done. These polyfunctional amine compounds may be used alone or in combination of two or more.
  • the content of the polyfunctional amine compound in the curable composition is preferably 25 to 80% by mass, more preferably 35 to 75% by mass, based on the total solid content of the curable composition.
  • the curable composition may contain a silane coupling agent.
  • a silane coupling agent When the curable composition contains a silane coupling agent, an adhesion improving layer that is more excellent in adhesion with the gas barrier layer can be formed.
  • silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltriethoxysilane.
  • Aminosilane coupling agents such as 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycid Epoxy silane coupling agents such as xyloxymethyldimethoxysilane; 3-mercaptopropyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane; JP 2000-239447 A, JP 2001-40037 A, etc. Polymeric silane coupling agent; and the like. These silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.005 parts by mass with respect to 100 parts by mass of the thermosetting epoxy resin. 01 to 3 parts by mass.
  • the curable composition may contain a solvent.
  • Solvents include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, mono Halogenated hydrocarbon solvents such as chlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ethyl acetate, butyl acetate Ester solvent such as ethyl cellosolve; ether solvent such as 1,3-dioxolane; and the like. These solvents may be used alone or in combination of two or more.
  • the content of the solvent in the curable composition is not particularly limited, but is preferably 85 to 99% by mass, more preferably 90 to 97% by mass, based on the total amount of the curable composition.
  • the curable composition may contain various additives as long as the effects of the present invention are not hindered.
  • the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to adjust content of these additives suitably according to the objective.
  • the curable composition can be prepared by appropriately mixing and stirring the thermosetting epoxy resin and, if necessary, other components according to a conventional method.
  • the adhesion improving layer is formed by, for example, applying a resin composition for forming an adhesion improving layer such as a curable composition on the gas barrier layer according to a conventional method, and curing or drying the obtained coating film.
  • a coating method a normal wet coating method can be used.
  • the heating temperature is preferably 70 to 180 ° C, more preferably 80 to 150 ° C.
  • the heating time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes.
  • the polyolefin resin (A) contained in the adhesive layer is a modified polyolefin resin (A1) and the gas barrier layer contains a polysilazane compound and is a layer formed by a modification treatment
  • the agent layer is preferably laminated directly on the gas barrier layer.
  • the adhesive layer containing the polyolefin resin (A) tends to be difficult to adhere, but when the polyolefin resin (A) contains the modified polyolefin resin (A1), In order to show good adhesion to the gas barrier layer as described above, it can be a means for omitting the adhesion improving layer.
  • the sealing body of the present invention is sealed with the object to be sealed using the gas barrier film of the present invention as a sealing material, and defects due to defects such as delamination and / or intrusion of water vapor or the like occur. It will be difficult. Therefore, the sealing body can be suitably used in applications that require the performance of the sealed object to be maintained over a long period of time. That is, excellent adhesiveness is maintained on the adhesive surface between the sealing material adhesive layer and the object to be sealed, and the initial performance of the object to be sealed can be suitably maintained.
  • the object to be sealed include at least one selected from the group consisting of organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements, and solar cell elements. .
  • the manufacturing method of the sealing body of this invention is not specifically limited, The process of adhering the adhesive bond layer which a gas barrier film has to a to-be-sealed object, and the process of peeling a peeling sheet from the gas barrier film of this invention. It is preferable to provide.
  • the gas barrier film of the present invention used as a sealing material has the following mode, the second release sheet is first peeled off. Next, the surface of the exposed adhesive layer and the surface of the object to be sealed are overlapped, pressurized as necessary, heated under desired heating conditions to cure the adhesive layer, and the object to be sealed is sealed. A sealed body is obtained which is sealed with a gas barrier film serving as a stopper.
  • First release sheet / undercoat layer / gas barrier layer / adhesive layer / second release sheet Normally, the first release sheet is peeled off after forming the surface of the adhesive layer and the object to be sealed. It is.
  • the removal of the first release sheet may be performed before or after the step of heating the gas barrier film.
  • the first release sheet is supported by the gas barrier film until the first release sheet is peeled and removed. Since it functions as a body, the gas barrier film is prevented from being broken or deformed, and is easy to handle.
  • Example 1 [Production of gas barrier film]
  • 40 parts of tricyclodecane dimethanol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., ADCP
  • an energy ray-curable component and bis (2,4,6-trimethylbenzoyl)-
  • phenylphosphine oxide manufactured by BASF, “Irgacure 819” was added and mixed to prepare an underlayer composition.
  • PET polyethylene terephthalate
  • PET50A-4100 thickness 50 ⁇ m
  • the obtained coating film was heated at 120 degreeC for 1 minute, the coating film was dried, and the 100-nm-thick polysilazane type compound layer was formed on the said base layer. Further, a plasma ion implantation apparatus (RF power source: “RF56000” manufactured by JEOL Ltd., high voltage pulse power source: “PV-3-HSHV-0835” manufactured by Kurita Seisakusho Co., Ltd.) is applied to the surface of the polysilazane compound layer formed as described above. Then, under the conditions shown below, a modification treatment by plasma ion implantation was performed to form a first gas barrier layer.
  • RF power source “RF56000” manufactured by JEOL Ltd.
  • high voltage pulse power source “PV-3-HSHV-0835” manufactured by Kurita Seisakusho Co., Ltd.
  • thermosetting component (B) 25 parts of polyfunctional epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., “YX8034”, hydrogenated bisphenol A diglycidyl ether), and as curing catalyst (C), imidazole
  • a system curing catalyst Shikoku Kasei Co., Ltd., “Curazole 2E4MZ”, 2-ethyl-4-methylimidazole
  • the adhesive composition prepared above is applied on the release-treated surface of a polyethylene terephthalate (PET) film (“SP-PET382150” manufactured by Lintec Corporation) so that the thickness after drying becomes 25 ⁇ m. It was applied with a knife coater to form a coating film. By heating this coating film at 100 ° C. for 2 minutes, the coating film was dried, and an adhesive layer having a thickness of 25 ⁇ m was formed on the second release sheet. Next, a peel-treated surface of a polyethylene terephthalate (PET) film (manufactured by Lintec Corporation, “SP-PET 381031”) was laminated as a third release sheet and laminated on the adhesive layer.
  • PET polyethylene terephthalate
  • the polyethylene terephthalate (PET) film used as the third release sheet was peeled off. Then, the surface of the exposed adhesive layer and the surface of the second gas barrier layer formed above are overlapped and heated to 60 ° C. using a heat laminator, whereby the second release sheet is applied to the adhesive layer. In the remaining state, an adhesive layer having a thickness of 25 ⁇ m is formed on the second gas barrier layer, and the first release sheet / underlayer / first gas barrier layer (with modification) / second gas barrier layer ( A gas barrier film of Example 1 having a layer structure of (modified) / adhesive layer / second release sheet was produced.
  • PET polyethylene terephthalate
  • ITO film An indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30 ⁇ / ⁇ ) was formed on the surface of the glass substrate by sputtering, and then the anode was formed by solvent cleaning and UV / ozone treatment. .
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (made by Luminescence Technology) is used as a light emitting layer forming material.
  • Al aluminum (manufactured by High Purity Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, and glass substrate / anode / light emitting layer / cathode
  • An organic EL device having the layer structure was prepared.
  • the degree of vacuum when sequentially depositing the light emitting layer forming material on the anode (ITO film) was set to 1 ⁇ 10 ⁇ 4 Pa or less.
  • the second release sheet was peeled and removed from the gas barrier film produced in Example 1 described above to expose the surface of the adhesive layer of the gas barrier film serving as a sealing material.
  • the surface of the exposed adhesive layer and the surface of the organic EL element to be sealed to be manufactured are overlapped and heated to 60 ° C. using a heat laminator in a nitrogen atmosphere.
  • the surface of the layer and the surface of the organic EL element to be sealed are bonded while being pressurized, and the organic EL element to be sealed is sealed with a gas barrier film serving as a sealing material.
  • the sealing body was produced.
  • the adhesive body was hardened by heating the sealing body produced above at 100 degreeC for 2 hours, and the sealing body of Example 1 was produced.
  • Comparative Example 1 In the step of forming the adhesive layer of Example 1, a rubber-based adhesive (“Exxon Butyl 268”, manufactured by Nippon Butyl Co., Ltd., number average molecular weight: 260,000, copolymer of isobutylene and isoprene, content of isoprene: 1 0.7 mol%) 100 parts and 20 parts of tackifier (manufactured by Nippon Zeon Co., Ltd., “Quinton A100”) were dissolved in toluene, and an adhesive composition was prepared so that the solid content concentration was 20%. Except for the above, a gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1. Further, in the production of the sealing body of Example 1, a sealing body of Comparative Example 1 was produced in the same manner as in Example 1 except that the adhesive layer was not cured.
  • a rubber-based adhesive (“Exxon Butyl 268”, manufactured by Nippon Butyl Co., Ltd., number average molecular weight: 260,000
  • Example 2 Evaluation of sealing performance for objects to be sealed
  • the first release sheet is peeled and removed from each sealing body produced in Example 1 and Comparative Example 1 described above, and the surface of the base layer of the gas barrier film is exposed. This was used as a measurement sample.
  • the sample for measurement was left in a high-temperature and high-humidity environment of 40 ° C. and 90% relative humidity for 100 hours, then the organic EL element was activated, the area of the non-emission point (dark spot) was measured, The ratio (%) of the area of the non-light emitting portion to the initial light emitting area (100%) was calculated.
  • the adhesive layer was formed from an adhesive composition containing a rubber-based adhesive and a tackifier.
  • the adhesiveness between the adhesive layer of the sealing material and the object to be sealed is not maintained, and the gas barrier film of Comparative Example 1 is sealed against the object to be sealed. It turned out to be inferior in performance.
  • the adhesive layer was formed from an adhesive composition containing a polyolefin resin (A) and a thermosetting component (B), Even when the sealing body of Example 1 is exposed to a high temperature and high humidity environment for a long time, excellent adhesion is maintained on the adhesive surface between the adhesive layer of the sealing material and the object to be sealed. It was found that this gas barrier film was excellent in sealing performance against an object to be sealed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)

Abstract

La présente invention concerne un film formant une barrière aux gaz, qui comprend un produit feuilleté obtenu par la superposition d'une feuille antiadhésive, d'une sous-couche, d'une couche formant une barrière aux gaz et d'une couche adhésive, dans cet ordre, la couche adhésive étant une couche formée à partir d'une composition adhésive comprenant une résine à base de polyoléfine (A) et un constituant thermodurcissable (B).
PCT/JP2018/011633 2017-03-30 2018-03-23 Film formant une barrière aux gaz et objet scellé de manière étanche Ceased WO2018180962A1 (fr)

Priority Applications (3)

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CN201880017227.3A CN110392721A (zh) 2017-03-30 2018-03-23 阻气性膜以及密封体
KR1020197025889A KR102496772B1 (ko) 2017-03-30 2018-03-23 가스 배리어성 필름, 및 봉지체
JP2019509697A JP7158377B2 (ja) 2017-03-30 2018-03-23 ガスバリア性フィルム、及び封止体

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JPPCT/JP2017/020347 2017-05-31
PCT/JP2017/020347 WO2018179458A1 (fr) 2017-03-30 2017-05-31 Stratifié formant barrière aux gaz, et élément d'étanchéité

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WO2020138206A1 (fr) * 2018-12-27 2020-07-02 リンテック株式会社 Stratifié doté de propriétés barrière au gaz
WO2020138207A1 (fr) * 2018-12-27 2020-07-02 リンテック株式会社 Stratifié doté de propriétés barrière au gaz

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TWI772392B (zh) 2022-08-01
KR102496772B1 (ko) 2023-02-06
WO2018179458A1 (fr) 2018-10-04
CN110392721A (zh) 2019-10-29
JP7158377B2 (ja) 2022-10-21
KR20190130565A (ko) 2019-11-22
TW201840415A (zh) 2018-11-16
JPWO2018179458A1 (ja) 2020-02-06

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