WO2018181192A1 - Adhesive composition, sealing sheet and sealed body - Google Patents

Adhesive composition, sealing sheet and sealed body Download PDF

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Publication number
WO2018181192A1
WO2018181192A1 PCT/JP2018/012164 JP2018012164W WO2018181192A1 WO 2018181192 A1 WO2018181192 A1 WO 2018181192A1 JP 2018012164 W JP2018012164 W JP 2018012164W WO 2018181192 A1 WO2018181192 A1 WO 2018181192A1
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WIPO (PCT)
Prior art keywords
component
pressure
sensitive adhesive
adhesive composition
group
Prior art date
Application number
PCT/JP2018/012164
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French (fr)
Japanese (ja)
Inventor
枝保 前谷
健太 西嶋
幹広 樫尾
Original Assignee
リンテック株式会社
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Priority to JP2019509814A priority Critical patent/JP7100622B2/en
Publication of WO2018181192A1 publication Critical patent/WO2018181192A1/en

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J121/00—Adhesives based on unspecified rubbers
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition in which adhesive strength does not decrease even when placed under high-humidity conditions, a sealing sheet having a pressure-sensitive adhesive layer formed using this pressure-sensitive adhesive composition, and an article to be sealed
  • the present invention relates to a sealing body that is sealed with a sealing sheet.
  • 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 are likely to deteriorate with time.
  • As a cause of the problem of the deterioration of the light emission characteristics it has been considered that oxygen, moisture or the like enters the inside of the organic EL element and degrades the electrode or the organic layer. For this reason, in order to solve this problem, it has been proposed to use an adhesive sheet excellent in moisture barrier properties as a sealing material.
  • an adhesive sheet is used for the purpose of bonding an optical member.
  • a moisture barrier property is used.
  • an adhesive sheet that is excellent in resistance.
  • Patent Document 1 describes a pressure-sensitive adhesive sheet containing a rubber-based resin as a main component and having specific pressure-sensitive adhesive characteristics.
  • the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having a low water vapor transmission rate, has sufficient adhesive strength even when wet heat has passed (when placed in a high humidity environment), and is yellow when wet heat has passed. It is described that the pressure-sensitive adhesive sheet preferably contains a silane coupling agent in addition to the rubber-based resin because the deformation is suppressed and these characteristics are easily exhibited.
  • Patent Document 1 As described in Patent Document 1, by using a pressure-sensitive adhesive composition containing a rubber-based resin as a main component, a pressure-sensitive adhesive sheet having excellent moisture barrier properties tends to be obtained.
  • a pressure-sensitive adhesive composition containing a rubber-based resin as a main component and containing a silane coupling agent the pressure-sensitive adhesive force decreases after being placed under high humidity conditions. I knew there was something to do. And it turned out that the sealing sheet which has an adhesive layer formed using such an adhesive composition tends to generate
  • the present invention was made for the purpose of solving these problems, and was formed using a pressure-sensitive adhesive composition in which the adhesive strength does not decrease even under high-humidity conditions, and this pressure-sensitive adhesive composition. It aims at providing the sealing body which has a sealing sheet which has an adhesive layer, and a to-be-sealed material is sealed with the said sealing sheet.
  • the adhesive strength of the pressure-sensitive adhesive composition does not decrease means that the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition does not decrease.
  • characteristics relating to the pressure-sensitive adhesive layer may be described as characteristics of the pressure-sensitive adhesive composition.
  • component rubber-based resin
  • component curable resin
  • component allophanate-based crosslinking agent
  • B The pressure-sensitive adhesive composition according to [1] or [2], further comprising the following component (B).
  • (B) Component Tackifier
  • a sealing film comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film, A sealing sheet in which the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition according to any one of [1] to [12].
  • the gas barrier film is a metal foil, a resin film, or thin film glass.
  • the pressure-sensitive adhesive layer has a thickness of 1 to 50 ⁇ m.
  • the sealed body according to [17], wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.
  • the adhesive composition by which adhesive force does not fall even if it puts on high humidity conditions the sealing sheet which has an adhesive layer formed using this adhesive composition, and a to-be-sealed thing Is provided with a sealing body sealed with the sealing sheet.
  • Adhesive composition contains the following (A) component, (C) component, and (D) component.
  • the pressure-sensitive adhesive composition of the present invention contains a rubber-based resin as the component (A).
  • the pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties by containing a rubber-based resin.
  • rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate-butadiene copolymer Examples thereof include urethane, rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene-propylene-nonconjugated diene terpolymer. It is done. These rubber resins
  • the polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers.
  • the polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.
  • Examples of the other monomer include isoprene, n-butene, butadiene, and styrene. Other monomers may be used alone or in combination of two or more.
  • isobutylene resin is a copolymer
  • isobutylene is the maximum amount of monomer as a main component in the raw material monomer.
  • the polyisobutylene-based resin is excellent in moisture barrier property, so that the monomer component is a homopolymer consisting only of isobutylene, and the isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as monomer components ( Butyl rubber) is preferred.
  • the isobutylene-based resin is excellent in moisture barrier property, so that the monomer component is a homopolymer consisting only of isobutylene, and the isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as monomer components ( Butyl rubber) is preferred.
  • the content of the structural unit composed of isobutylene that does not leave a polymerizable double bond in the main chain and side chain is preferably 80 to 99% by mass, more preferably 90 to 99%, based on all the structural units of the polyisobutylene resin. % By mass, more preferably 95 to 99% by mass.
  • the polyisobutylene resin can be obtained, for example, by a method of polymerizing a monomer component such as isobutylene in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
  • a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
  • the mass average molecular weight (Mw) of the rubber-based resin is preferably 10,000 to 3,000,000, more preferably 20,000 to 1,000,000.
  • the mass average molecular weight (Mw) can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC).
  • the pressure-sensitive adhesive composition of the present invention contains a curable resin as the component (C). Since the pressure-sensitive adhesive composition of the present invention contains a curable resin, the pressure-sensitive adhesive force is hardly lowered even under high humidity conditions.
  • the curable resin refers to a polymer having two or more functional groups capable of reacting with the allophanate-based crosslinking agent as component (D). Such functional groups include hydroxyl groups.
  • curable resin examples include polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polydiene polyols, hydrogenated polydiene polyols, and polymers having hydroxyl groups at both ends, such as silicones having hydroxyl groups at both ends. Can be mentioned.
  • a curable resin can be used individually by 1 type or in combination of 2 or more types.
  • a polydiene polyol or a hydrogenated polydiene polyol is preferable because a pressure-sensitive adhesive composition that does not easily lower the adhesive strength even when placed under a high humidity condition is easily obtained.
  • the polydiene polyol include polybutadiene polyol and polyisoprene polyol.
  • the hydrogenated polydiene polyol include hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol.
  • polydiene polyol and hydrogenated polydiene polyol can be used as the polydiene polyol and hydrogenated polydiene polyol.
  • commercially available products include NISSO PB G-1000, G-2000, G-3000 manufactured by Nippon Soda Co., Ltd., Poly bd R-15HT, R-45HT manufactured by Idemitsu Kosan Co., Ltd., Krasol LBH2000 manufactured by Cray Valley, LBH-P2000, LBH3000, LBH-P3000 (polybutadiene polyol), NISSO PB GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., Polytail H manufactured by Mitsubishi Chemical Corporation, Krasol manufactured by Cray Valley HLBH-P2000, HLBH-P3000 (hydrogenated polybutadiene polyol), Poly ip (polyisoprene polyol) manufactured by Idemitsu Kosan Co., Ltd., Epaul (hydrogenated poly
  • the mass average molecular weight (Mw) of the curable resin is preferably 1,000 to 5,000, more preferably 1,000 to 4,000. When the mass average molecular weight (Mw) of the curable resin is within the above range, an adhesive composition that is superior in adhesive strength can be obtained.
  • the content of the curable resin is not particularly limited, but is usually 1 to 50 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of component (A).
  • the content of the curable resin is 1 part by mass or more with respect to 100 parts by mass of the component (A)
  • an adhesive layer that excels in adhesive strength can be efficiently formed, and the content is 50 parts by mass or less. Thereby, the fall of the cohesion force of an adhesive layer can be avoided.
  • the pressure-sensitive adhesive composition of the present invention contains an allophanate-based crosslinking agent as the component (D).
  • the allophanate-based crosslinking agent can form a crosslinked structure with the component (C), and the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention containing these components has a cohesive force. It is high, and even when it is placed under high humidity conditions, the adhesive strength is difficult to decrease.
  • the allophanate-based crosslinking agent is a modified polyisocyanate and has an allophanate bond (hereinafter referred to as “allophanate-modified polyisocyanate”).
  • the allophanate-modified polyisocyanate can be obtained, for example, by reacting a polyisocyanate compound with a monool compound and / or a polyol compound in the presence of an allophanate-forming catalyst.
  • the allophanatization catalyst for example, a known catalyst such as a metal salt of carboxylic acid can be appropriately selected and used.
  • the polyisocyanate compound is a compound having at least two isocyanate groups in the molecule.
  • Examples of the polyisocyanate compound include aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.
  • Aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI).
  • MDI 4,4′-diphenylmethane diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4,4 ′, 4 ′′ -triisocyanate, 1,3,5-triisocyanate
  • Aromatic triisocyanates such as benzene and 2,4,6-triisocyanate toluene; aromatic tetraisocyanates such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate; and the like.
  • araliphatic polyisocyanate examples include 1,3- or 1,4-xylylene diisocyanate (XDI) or a mixture thereof, ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4- And araliphatic diisocyanates such as bis (1-isocyanate-1-methylethyl) benzene (TMXDI) or mixtures thereof; and araliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene; and the like.
  • XDI 1,3- or 1,4-xylylene diisocyanate
  • TMXDI 1,3- or 1,4-
  • araliphatic diisocyanates such as bis (1-isocyanate-1-methylethyl) benzene (TMXDI) or mixtures thereof
  • araliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene;
  • alicyclic polyisocyanates examples include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 4, 4′-methylenebis (cyclohexyl isocyanate) (H 12 MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (H 6 XDI) or mixtures thereof; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane, 2- (3-isocyanate pro ) -2,5-di (isocyanatemethyl) -bicyclo (2.2.1) heptane
  • Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate; lysine ester triisocyanate, 1,4,8-triisocyanate Octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane ali
  • polyisocyanate compound aliphatic polyisocyanate is preferable and hexamethylene diisocyanate is more preferable.
  • a polyisocyanate compound can be used individually by 1 type or in combination of 2 or more types.
  • Monool compounds include aliphatic monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol; alicyclic monoalcohols such as cyclopentanol and dimethylcyclohexanol; and aromatic fats such as benzyl alcohol Group monoalcohols; phenols such as phenol and cresol; and the like.
  • polyol compound examples include ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, diethylene glycol, Propylene glycol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bis Diol compounds such as hydroxyethylene terephthalate; glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6 Triol compounds such as hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) -3-butanol;
  • the content of the allophanate-based crosslinking agent is not particularly limited, but is usually 1 to 70 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of component (A).
  • the content of the allophanate-based crosslinking agent is 1 part by mass or more with respect to 100 parts by mass of the component (A)
  • a crosslinked structure can be sufficiently formed, and the adhesive is 70 parts by mass or less. A decrease in the cohesive strength of the agent layer can be avoided.
  • the pressure-sensitive adhesive composition of the present invention preferably contains a tackifier as the component (B) in addition to the components (A), (C) and (D).
  • a tackifier By containing a tackifier, the pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties and has high adhesive strength.
  • the tackifier is not particularly limited as long as it improves the adhesive strength of the pressure-sensitive adhesive layer, and a known one can be used.
  • Tackifiers include alicyclic petroleum resins, aliphatic petroleum resins, terpene resins, ester resins, coumarone-indene resins, rosin resins, epoxy resins, phenol resins, acrylic resins, butyral resins, olefin resins, Examples thereof include chlorinated olefin resins, vinyl acetate resins, modified resins thereof, and hydrogenated resins.
  • an aliphatic petroleum resin is preferable because it is easy to obtain a pressure-sensitive adhesive composition having excellent moisture barrier properties and high adhesive strength.
  • a tackifier can be used individually by 1 type or in combination of 2 or more types.
  • commercially available products can be used as they are as tackifiers.
  • commercially available products include aliphatic petroleum resins such as Escolets 1000 Series (Exxon Chemical Co., Ltd.), Quinton A, B, R, CX Series (Zeon Japan Co., Ltd.); Alcon P, M Series (Arakawa Chemical Co., Ltd.) ), ESCOREZ series (manufactured by Exxon Chemical), EASTOTAC series (manufactured by Eastman Chemical), ILARV series (manufactured by Idemitsu Kosan Co., Ltd.); ), Clearon P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by Hercules), etc .; Foal series (manufactured by Hercules), Pencel A series, ester gum, super ester, pine crystal Ester resins such as Arakawa Chemical Industries, etc .;
  • the mass average molecular weight (Mw) of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000.
  • the softening point of the tackifier is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, still more preferably 70 to 130 ° C.
  • the content of the tackifier is not particularly limited, but is usually 1 to 50 parts by mass, preferably 5 to 45 parts by mass with respect to 100 parts by mass of component (A).
  • the content of the tackifier is 1 part by mass or more with respect to 100 parts by mass of the component (A)
  • an adhesive layer that excels in adhesive strength can be efficiently formed, and the content is 50 parts by mass or less. Thereby, the fall of the cohesion force of an adhesive layer can be avoided.
  • the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent as the component (E) in addition to the components (A), (C), (D), and (B) as required. preferable.
  • a silane coupling agent when the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent, the pressure-sensitive adhesive force at room temperature and in a high temperature and high humidity environment tends to be further improved.
  • a known silane coupling agent can be used as the silane coupling agent, and is not particularly limited. Among these, a silane compound represented by the following formula (1) is preferable.
  • R 1 represents an alkylene group having 3 or more carbon atoms
  • R 2 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • R 3 represents an alkyl group having 1 to 4 carbon atoms.
  • Z represents a group containing a reactive group
  • n is 0 or 1.
  • the alkylene group represented by R 1 has 3 or more carbon atoms, preferably 3 to 20, and more preferably 4 to 15. When the carbon number of the alkylene group is 3 or more, the crosslinking reaction is more likely to occur.
  • Examples of the alkylene group represented by R 1 include trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and the like.
  • the monovalent hydrocarbon group represented by R 2 has 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4.
  • Examples of the monovalent hydrocarbon group represented by R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, and n-pentyl group.
  • the alkyl group represented by R 3 has 1 to 4, preferably 1 to 3, more preferably 1 or 2, carbon atoms.
  • Examples of the alkyl group represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and t-butyl group.
  • the reactive group contained in Z is not particularly limited as long as it can contribute to the crosslinking reaction.
  • an epoxy group or an amino group is preferable.
  • Z containing an epoxy group include an epoxy group, a glycidyl group, and an epoxycyclohexyl group.
  • Z containing an amino group include an amino group, a 2-aminoethylamino group, and a phenylamino group.
  • silane coupling agent represented by the formula (1) examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2 -Aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 8- (aminoethylamino) octyltrimethoxysilane, etc.
  • a silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the silane coupling agent is preferably 0.01 to 7 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.1 to 5 parts by mass.
  • a pressure-sensitive adhesive composition having a silane coupling agent content within this range tends to have excellent adhesive force even at high temperatures.
  • components other than the components (A) to (D) and the silane coupling agent contained in the pressure-sensitive adhesive composition of the present invention include solvents and various additives.
  • Solvents 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- And aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; These solvents can be used alone or in combination of two or more. The amount of the solvent used can be appropriately determined in consideration of coating properties and the like.
  • additives such as an ultraviolet absorber, an antistatic agent, a light stabilizer, an antioxidant, a resin stabilizer, a filler, a pigment, an extender, and a softening agent. These can be used alone or in combination of two or more. When the adhesive composition of this invention contains these additives, the content can be suitably determined according to the objective.
  • the pressure-sensitive adhesive composition of the present invention can be prepared by appropriately mixing and stirring predetermined components according to a conventional method.
  • the pressure-sensitive adhesive composition of the present invention is excellent in adhesive strength.
  • the adhesive strength is not easily lowered even when the adhesive is placed under high-humidity conditions.
  • the x value calculated by the following formula is preferably 1.0 or more.
  • A represents an adhesive strength obtained by performing a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%
  • B represents a condition of the test piece at a temperature of 60 ° C. and a relative humidity of 90%. For 168 hours, and then allowed to stand for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, followed by a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%.
  • A is not particularly limited, but is usually 2 to 25 N / 25 mm, preferably 2 to 20 N / 25 mm.
  • B is not particularly limited, but is usually 5 to 35 N / 25 mm, preferably 5 to 30 N / 25 mm.
  • Specimens for these 180 ° peel tests can be prepared according to the method described in the examples.
  • the pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties and adhesive strength, the pressure-sensitive adhesive composition of the present invention is suitably used when forming a sealing material.
  • sealing sheet of this invention is the following sealing sheet ((alpha)) or sealing sheet ((beta)).
  • Sealing sheet ( ⁇ ) a sealing sheet comprising two release films and an adhesive layer sandwiched between these release films, wherein the adhesive layer uses the adhesive composition of the present invention.
  • the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition of the present invention.
  • the release film constituting the sealing sheet ( ⁇ ) functions as a support in the production process of the sealing sheet ( ⁇ ), and protects the adhesive layer until the sealing sheet ( ⁇ ) is used. Functions as a sheet.
  • a conventionally well-known thing can be utilized as a peeling film.
  • the substrate for the release film 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.
  • the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the two release films in the sealing sheet ( ⁇ ) may be the same or different, but the two release films preferably have different release forces.
  • the peel strengths of the two release films are different, problems are less likely to occur when the sealing sheet is used. That is, the process of peeling a peeling film first can be performed more efficiently by making the peeling force of two peeling films differ.
  • the thickness of the pressure-sensitive adhesive layer of the sealing sheet ( ⁇ ) is not particularly limited, but is usually 1 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
  • the pressure-sensitive adhesive layer having a thickness in the above range is suitably used as a sealing material.
  • the manufacturing method of a sealing sheet ((alpha)) is not specifically limited.
  • the sealing sheet ( ⁇ ) can be manufactured using a casting method.
  • the sealing sheet ( ⁇ ) is produced by a casting method, by using a known method, the pressure-sensitive adhesive composition of the present invention is applied to the release-treated surface of the release film, and the obtained coating film is dried.
  • a sealing sheet ( ⁇ ) can be obtained by producing a pressure-sensitive adhesive layer with a release film and then stacking another release film on the pressure-sensitive adhesive layer.
  • Examples of the method for applying the pressure-sensitive adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the drying conditions for drying the coating film include, for example, 80 to 150 ° C. for 30 seconds to 5 minutes. After the drying treatment, the pressure-sensitive adhesive layer may be cured by allowing it to stand still for about one week. By curing the pressure-sensitive adhesive layer, a crosslinked structure can be sufficiently formed.
  • the gas barrier film which comprises a sealing sheet ((beta)) will not be specifically limited if it is a film which has a moisture barrier property.
  • gas barrier film examples include those having a gas barrier layer on the base material layer directly or via other layers such as a primer layer.
  • the base material layer constituting the gas barrier laminate of the present invention is not particularly limited as long as it is excellent in transparency and can carry a gas barrier layer or the like.
  • Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, cycloolefin polymer And aromatic polymers.
  • the resin film 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 determine suitably content of these additives according to the objective.
  • the resin film can be obtained by preparing a resin composition containing a resin component and optionally various additives, and molding the resin composition into a film.
  • the molding method is not particularly limited, and a known method such as a casting method or a melt extrusion method can be used.
  • the thickness of the base material layer is not particularly limited, and may be determined according to the purpose of the gas barrier laminate.
  • the thickness of the base material layer is usually 0.5 to 500 ⁇ m, preferably 1 to 100 ⁇ m.
  • the gas barrier layer constituting the gas barrier film is a layer having characteristics (gas barrier properties) for suppressing permeation of gases such as oxygen and water vapor.
  • This gas barrier layer is laminated on one surface (A) of the base material layer directly or via another layer.
  • the thickness of the gas barrier layer is usually 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm.
  • the gas barrier layer includes a gas barrier layer made of metal foil, a gas barrier layer made of thin glass, a gas barrier layer made of a gas barrier resin, a gas barrier layer made of an inorganic film, and a gas barrier layer in which the surface of the polymer layer is modified [in this case
  • the gas barrier layer does not mean only the modified region, but means “a layer including the modified region”.
  • Etc. are mentioned.
  • a gas barrier layer made of an inorganic film and a gas burr layer formed by modifying the surface of the polymer layer are preferable.
  • Metal foil is a thin stretch of metal.
  • metal foil such as aluminum, nickel, stainless steel, iron, copper, titanium, is mentioned.
  • the metal foil may be a single layer or a laminate in which layers made of the same material or layers made of different materials are laminated.
  • Examples of the material of the thin film glass include multi-component oxide glasses such as alkali-free glass, borosilicate glass, and aluminosilicate glass.
  • polyvinyl alcohol As a gas barrier resin, polyvinyl alcohol, or a partially saponified product thereof, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, and the like are hardly permeable to oxygen, water vapor, and the like. Resin.
  • the inorganic film examples include an inorganic compound and a metal deposited film.
  • 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 Inorganic sulfides
  • inorganic oxynitrides such as silicon oxynitride
  • the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
  • an inorganic vapor-deposited film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable from the viewpoint of gas barrier properties, and further, an inorganic material using an inorganic oxide or inorganic nitride as a raw material from the viewpoint of transparency.
  • a vapor deposition film is preferred.
  • a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method or an ion plating method
  • a CVD method such as a thermal CVD (chemical vapor deposition) method, a plasma CVD method or a photo CVD method is used. Law.
  • the thickness of the inorganic film varies depending on the inorganic compound and metal used, but is preferably in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm from the viewpoint of gas barrier properties and handling properties.
  • examples of the polymer used for forming the polymer layer include silicon-containing polymer compounds.
  • silicon-containing polymer compounds examples include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. And polysilazane compounds are more preferred.
  • the polysilazane compound is a compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the formula (1)
  • the compound which has a repeating unit represented by these is preferable.
  • the number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably 100 to 50,000.
  • n represents an arbitrary natural number.
  • 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, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group;
  • alkyl group of the unsubstituted or substituted alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-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.
  • alkenyl group of an unsubstituted or substituted alkenyl group examples include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like having 2 to 2 carbon atoms. 10 alkenyl groups are mentioned.
  • substituents for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
  • halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
  • hydroxyl group such as hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
  • An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
  • 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.
  • substituent of the aryl group examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc.
  • alkylsilyl group examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.
  • Rx, Ry, and Rz a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.
  • Examples of the polysilazane compound having a repeating unit represented by the 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 Kaihei 5-345826 and JP-A-4-63833.
  • the polysilazane compound perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
  • a polysilazane compound a commercially available product as a glass coating material or the like can be used as it is.
  • the polysilazane compounds can be used alone or in combination of two or more.
  • the polymer layer may contain other components as long as the object of the present invention is not impaired.
  • other components include a curing agent, an anti-aging agent, a light stabilizer, and a flame retardant.
  • the content of the silicon-containing polymer compound in the polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more because a gas barrier layer having better gas barrier properties can be formed.
  • the thickness of the polymer layer is not particularly limited, but is usually in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm.
  • the polymer layer is, for example, a coating film obtained by applying a solution obtained by dissolving or dispersing a silicon-containing polymer compound in an organic solvent directly or via another layer by a known coating method. Can be formed by drying.
  • 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 solvents can be used alone or in combination of two or more.
  • 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
  • Coating methods include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, and gravure offset. Law.
  • Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
  • the heating temperature is usually 80 to 150 ° C.
  • 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.
  • 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, etc.
  • rare gases such as argon, helium, neon, krypton, and xenon
  • fluorocarbon hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .
  • Ion of alkane gases such as ethylene and propylene
  • Ions of alkadiene gases such as pentadiene and butadiene
  • Ions of alkyne gases such as acetylene
  • Aromatic carbonization such as benzene and toluene
  • Examples include ions of hydrogen-based gases; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; ions of metals; ions of organosilicon compounds. These ions can be used alone or in combination of two or more.
  • ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily implanted and a gas barrier layer having better gas barrier properties can be formed.
  • the ion implantation amount can be appropriately determined according to the purpose of use of the gas barrier laminate (necessary gas barrier properties, transparency, etc.).
  • Examples of the method of 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. Of these, the latter method of injecting ions in plasma (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 thickness of the region into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, and processing time, and is determined according to the thickness of the polymer layer and the purpose of use of the laminate. Usually, it is 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 polymer layer using X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the gas barrier film preferably has a water vapor transmission rate of 0.1 g / m 2 / day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90% (hereinafter abbreviated as “90% RH”). It is more preferable that it is 0.05 g / m 2 / day or less, and it is more preferable that it is 0.005 g / m 2 / day or less.
  • the gas barrier film has a water vapor permeability of 0.1 g / m 2 / day or less in an environment of 40 ° C. and 90% RH, so that oxygen or oxygen can be contained inside the organic EL element or the like formed on the transparent substrate. It is possible to effectively suppress the penetration of moisture and the like and the deterioration of the electrode and the organic layer.
  • the transmittance of water vapor and the like of the gas barrier film can be measured using a known gas permeability measuring device.
  • the primer layer is not particularly limited, and a known layer can be used.
  • the primer layer etc. which were described in WO2012 / 039387, WO2013 / 147090 etc. are mentioned.
  • the manufacturing method of a sealing sheet ((beta)) is not specifically limited.
  • the sealing sheet ( ⁇ ) can be manufactured by replacing one of the release films with a gas barrier film.
  • the sealing sheet ((beta)) is manufactured by peeling the one peeling film and sticking the exposed adhesive layer and a gas-barrier film. You can also.
  • the sealing sheet ( ⁇ ) has two release films having different release forces, it is preferable to release the release film having the smaller release force from the viewpoint of handleability.
  • the pressure-sensitive adhesive layer of the sealing sheet of the present invention is excellent in adhesive strength and moisture barrier properties. For this reason, the deterioration can be efficiently suppressed by sealing an organic EL element using the sealing sheet of this invention.
  • the sealing body of the present invention is such that an object to be sealed is sealed using the sealing sheet of the present invention.
  • the sealed object is sealed using the sealing sheet of the present invention means that the release film constituting the sealing sheet of the present invention is removed to expose the pressure-sensitive adhesive layer. It means that a layer is brought into close contact with an object to be sealed to cover the object to be sealed.
  • the sealing body of the present invention includes, for example, a transparent substrate, an element (an object to be sealed) formed on the transparent substrate, and a sealing material for sealing the element. The said sealing material is what is the adhesive layer of the sealing sheet of this invention.
  • 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 a high blocking performance for blocking moisture and gas to enter 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, acetyl cellulose, brominated phenoxy, aramids, polyimides, Examples thereof include transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins, and the gas barrier film described above.
  • the thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance for blocking the inside and outside of the element.
  • Examples of the objects to be sealed include organic EL elements, organic EL display elements, liquid crystal display elements, solar cell elements, and the like.
  • the manufacturing method of the sealing body of the present invention is not particularly limited.
  • the pressure-sensitive adhesive layer of the sealing sheet of the present invention is stuck on the object to be sealed, and the pressure-sensitive adhesive layer of the sealing sheet and the object to be sealed are adhered.
  • the sealing body of the present invention is formed by sealing an object to be sealed with the sealing sheet of the present invention. Therefore, in the sealed body of the present invention, the performance of the object to be sealed is maintained for a long time.
  • the primer layer forming solution was applied onto a 50 ⁇ m thick polyethylene terephthalate film (hereinafter referred to as “PET film”) (Toyobo Co., Ltd., Cosmo Shine A-4300). By drying, a primer layer having a thickness of 1 ⁇ m was formed.
  • a coating agent mainly composed of perhydropolysilazane (“AZNN110-20” manufactured by Merck Performance Materials Co., Ltd.) is applied on the primer layer, and the obtained coating film is heated at 120 ° C. for 2 minutes. A polysilazane layer having a thickness of 200 nm was formed.
  • plasma ion implantation was performed on the polysilazane layer under the following conditions using a plasma ion implantation apparatus to modify the surface of the polysilazane layer to obtain a gas barrier film.
  • the water vapor transmission rate of this gas barrier film was 0.02 g / m 2 / day.
  • Plasma generation gas Argon gas flow rate: 100 sccm Duty ratio: 0.5% Repeat frequency: 1000Hz Applied voltage: -10kV RF output: 1000W RF power supply: (frequency) 13.56 MHz, (applied power) 1000 W Chamber internal pressure: 0.2 Pa Pulse width: 5 ⁇ sec Processing time (ion implantation time): 5 minutes Conveying speed: 0.2 m / min
  • Rubber-based resin (1) butyl rubber, mass average molecular weight (Mw): 34,000, manufactured by JSR Corporation, trade name: JSR BUTYL268
  • Rubber-based resin (2) butyl rubber, mass average molecular weight (Mw): 28,000, manufactured by JSR Corporation, trade name: JSR BUTYL365 Tackifier
  • (1) Aliphatic petroleum resin, manufactured by Nippon Zeon Co., Ltd., trade name: Quinton A-100 Curable resin (1): hydrogenated polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol HLBH-P2000 Curable resin (2): Polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol LBH-P2000 Crosslinking agent (1): Allophanate-modified hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc., trade name: Takenate D-178NL Crosslinking agent (2): pen
  • Example 1 80 parts of rubber-based resin (1), 20 parts of rubber-based resin (2), 20 parts of tackifier (1), 15 parts of curable resin (1), 5 parts of cross-linking agent (1), and silane coupling agent (1) 0.1 part was dissolved in toluene to prepare an adhesive composition (1) having a solid content concentration of 17%.
  • This pressure-sensitive adhesive composition (1) was applied onto the release-treated surface of a release film (product name: SP-PET382150, manufactured by Lintec Corporation), and the obtained coating film was dried at 100 ° C. for 1 minute, and the thickness was 20 ⁇ m.
  • a release sheet (1) was obtained by pasting the release-treated surface of another release film (trade name: SP-PET381031 manufactured by Lintec Corporation) on the adhesive layer.
  • Examples 2 to 8, Comparative Example 1 A sealing sheet was prepared in the same manner as in Example 1 except that pressure-sensitive adhesive compositions (2) to (9) were prepared by changing to the compositions shown in Table 1 and these pressure-sensitive adhesive compositions were used. (2) to (9) were obtained.
  • test (b) As a peel test (b), the test piece was allowed to stand for 168 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, and then for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. A 180 ° peel test was conducted under the conditions of 50 ° C. and 50% relative humidity. In this peeling test, the test was performed according to the method for measuring adhesive strength described in JIS Z0237: 2000 except for the test conditions described above.
  • An organic EL element having a glass substrate on which an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50 ⁇ / ⁇ ) was formed as an anode was produced by the following method.
  • ITO indium tin oxide
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidine) made by Luminescence Technology
  • Tris (8- Hydroxy-quinolinate) aluminum manufactured by Luminescence Technology
  • lithium fluoride (LiF) manufactured by High-Purity Chemical Laboratory
  • Al aluminum
  • the cathode was formed by vapor-depositing 100 nm at a rate of 0.1 nm / min to obtain an organic EL device.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • One release film of the sealing sheet obtained in Example or Comparative Example was peeled off, and the exposed pressure-sensitive adhesive layer was stacked on the gas barrier film obtained in Production Example 1, and these were attached using a roll laminator. .
  • the other release film is peeled off, and the exposed adhesive layer is stacked so as to cover the organic EL element formed on the glass substrate, and these are attached using a roll laminator,
  • a sealed bottom emission type electronic device was obtained. This electronic device is allowed to stand for 250 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%, and then the organic EL element is activated to observe the presence or absence of dark spots (non-light emitting portions). The area ratio was calculated.
  • Table 1 shows the following.
  • the sealing sheets (1) to (8) of Examples 1 to 8 show better adhesive strength after standing under high humidity conditions, and are excellent in sealing properties.
  • the sealing sheet (9) of Comparative Example 1 has a small adhesive force, and when placed in a high humidity condition, the adhesive force is greatly reduced. And the sealing sheet (9) is inferior to sealing performance.

Abstract

The present invention relates to: an adhesive composition which contains a rubber-based resin (component (A)), a curable resin (component (C)) and an allophanate-based crosslinking agent (component (D)); a sealing sheet which comprises an adhesive layer that is formed using this adhesive composition; and a sealed body which is obtained by sealing an object to be sealed with use of this sealing sheet. The present invention provides: an adhesive composition which does not decrease in the adhesive force even under high humidity conditions; a sealing sheet which comprises an adhesive layer that is formed using this adhesive composition; and a sealed body which is obtained by sealing an object to be sealed with use of this sealing sheet.

Description

粘着剤組成物、封止シート、及び封止体Adhesive composition, sealing sheet, and sealing body
　本発明は、高湿条件下に置かれても粘着力が低下しない粘着剤組成物、この粘着剤組成物を用いて形成された粘着剤層を有する封止シート、及び被封止物が前記封止シートで封止されてなる封止体に関する。 The present invention relates to a pressure-sensitive adhesive composition in which adhesive strength does not decrease even when placed under high-humidity conditions, a sealing sheet having a pressure-sensitive adhesive layer formed using this pressure-sensitive adhesive composition, and an article to be sealed The present invention relates to a sealing body that is sealed with a sealing sheet.
　近年、有機ＥＬ素子は、低電圧直流駆動による高輝度発光が可能な発光素子として注目されている。
　しかし、有機ＥＬ素子には、時間の経過とともに、発光輝度、発光効率、発光均一性等の発光特性が低下し易いという問題があった。
　この発光特性の低下の問題の原因として、酸素や水分等が有機ＥＬ素子の内部に浸入し、電極や有機層を劣化させることが考えられてきた。このため、この問題を解決するために、水分遮断性に優れる粘着シートを封止材として用いることが提案されてきた。 In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
However, the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to deteriorate with time.
As a cause of the problem of the deterioration of the light emission characteristics, it has been considered that oxygen, moisture or the like enters the inside of the organic EL element and degrades the electrode or the organic layer. For this reason, in order to solve this problem, it has been proposed to use an adhesive sheet excellent in moisture barrier properties as a sealing material.
　また、液晶ディスプレイ（ＬＣＤ）やタッチパネル等の表示装置を製造する際は、光学部材を貼り合せる目的で粘着シートが用いられるが、近年、光学部材の機械的劣化を抑制するために、水分遮断性に優れる粘着シートが求められている。 Moreover, when manufacturing a display device such as a liquid crystal display (LCD) or a touch panel, an adhesive sheet is used for the purpose of bonding an optical member. Recently, in order to suppress mechanical deterioration of the optical member, a moisture barrier property is used. There is a demand for an adhesive sheet that is excellent in resistance.
　このような特性を有する粘着シートとして、特許文献１には、ゴム系樹脂を主成分とする粘着シートであって、特定の粘着特性等を有するものが記載されている。
　この文献には、その粘着シートが水蒸気透過度の低い粘着シートであって、湿熱経過時（高湿度環境下に置かれた場合）においても十分な粘着力を有し、かつ湿熱経過時の黄変が抑制されたものであることや、これらの特性を発現し易いことから、粘着シートは、ゴム系樹脂に加えてシランカップリング剤を含有するものが好ましいこと等が記載されている。 As a pressure-sensitive adhesive sheet having such characteristics, Patent Document 1 describes a pressure-sensitive adhesive sheet containing a rubber-based resin as a main component and having specific pressure-sensitive adhesive characteristics.
In this document, the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having a low water vapor transmission rate, has sufficient adhesive strength even when wet heat has passed (when placed in a high humidity environment), and is yellow when wet heat has passed. It is described that the pressure-sensitive adhesive sheet preferably contains a silane coupling agent in addition to the rubber-based resin because the deformation is suppressed and these characteristics are easily exhibited.
特開２０１６－５３１５７号公報JP 2016-53157 A
　特許文献１に記載されるように、ゴム系樹脂を主成分とする粘着剤組成物を用いることで、水分遮断性に優れる粘着シートが得られる傾向がある。
　しかしながら、本発明者の検討によれば、ゴム系樹脂を主成分とし、かつ、シランカップリング剤を含有する粘着剤組成物であっても、高湿条件下に置かれた後に粘着力が低下するものがあることが分かった。そして、そのような粘着剤組成物を用いて形成された粘着剤層を有する封止シートは、高湿条件下に置かれたときに膨れや浮きが発生し易いことも分かった。 As described in Patent Document 1, by using a pressure-sensitive adhesive composition containing a rubber-based resin as a main component, a pressure-sensitive adhesive sheet having excellent moisture barrier properties tends to be obtained.
However, according to the study of the present inventor, even if it is a pressure-sensitive adhesive composition containing a rubber-based resin as a main component and containing a silane coupling agent, the pressure-sensitive adhesive force decreases after being placed under high humidity conditions. I knew there was something to do. And it turned out that the sealing sheet which has an adhesive layer formed using such an adhesive composition tends to generate | occur | produce a swelling and a float, when it puts on high-humidity conditions.
　本発明は、これらの問題を解決することを目的としてなされたものであり、高湿条件下に置かれても粘着力が低下しない粘着剤組成物、この粘着剤組成物を用いて形成された粘着剤層を有する封止シート、及び被封止物が前記封止シートで封止されてなる封止体を提供することを目的とする。
　なお、本発明において、「粘着剤組成物の粘着力が低下しない」とは、その粘着剤組成物を用いて形成された粘着剤層の粘着力が低下しないことを意味する。また、同様に、本明細書においては、粘着剤層に関する特性を、粘着剤組成物の特性として記載することがある。 The present invention was made for the purpose of solving these problems, and was formed using a pressure-sensitive adhesive composition in which the adhesive strength does not decrease even under high-humidity conditions, and this pressure-sensitive adhesive composition. It aims at providing the sealing body which has a sealing sheet which has an adhesive layer, and a to-be-sealed material is sealed with the said sealing sheet.
In the present invention, “the adhesive strength of the pressure-sensitive adhesive composition does not decrease” means that the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition does not decrease. Similarly, in the present specification, characteristics relating to the pressure-sensitive adhesive layer may be described as characteristics of the pressure-sensitive adhesive composition.
　本発明者らは上記課題を解決すべく鋭意検討した結果、ゴム系樹脂と特定の添加剤を含有する粘着剤組成物は、高湿条件下に置かれても粘着力が低下しないものであることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a pressure-sensitive adhesive composition containing a rubber-based resin and a specific additive does not decrease in adhesive strength even when placed under high humidity conditions. As a result, the present invention has been completed.
　かくして本発明によれば、下記〔１〕～〔１２〕の粘着剤組成物、〔１３〕～〔１６〕の封止シート、及び〔１７〕、〔１８〕の封止体、が提供される。

〔１〕下記の（Ａ）成分、（Ｃ）成分、及び（Ｄ）成分を含有する粘着剤組成物。
（Ａ）成分：ゴム系樹脂
（Ｃ）成分：硬化性樹脂
（Ｄ）成分：アロファネート系架橋剤
〔２〕前記（Ａ）成分が、ブチルゴムである、〔１〕に記載の粘着剤組成物。
〔３〕さらに、下記の（Ｂ）成分を含有する、〔１〕又は〔２〕に記載の粘着剤組成物。
（Ｂ）成分：粘着付与剤
〔４〕前記（Ｂ）成分が、脂肪族系石油樹脂である、〔３〕に記載の粘着剤組成物。
〔５〕前記（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対して１～５０質量部である、〔３〕又は〔４〕に記載の粘着剤組成物。
〔６〕前記（Ｃ）成分が、両末端に水酸基を有する重合体である、〔１〕～〔５〕のいずれかに記載の粘着剤組成物。
〔７〕前記（Ｃ）成分の含有量が、（Ａ）成分１００質量部に対して１～５０質量部である、〔１〕～〔６〕のいずれかに記載の粘着剤組成物。
〔８〕前記（Ｄ）成分が、アロファネート変性ヘキサメチレンジイソシアネートである、〔１〕～〔７〕のいずれかに記載の粘着剤組成物。
〔９〕前記（Ｄ）成分の含有量が、（Ａ）成分１００質量部に対して１～７０質量部である、〔１〕～〔８〕のいずれかに記載の粘着剤組成物。
〔１０〕さらに、下記の（Ｅ）成分を含有する、〔１〕～〔９〕のいずれかに記載の粘着剤組成物。
（Ｅ）成分：シランカップリング剤
〔１１〕前記（Ｅ）成分が、下記式（１）で示される化合物である、〔１０〕に記載の粘着剤組成物。 Thus, according to the present invention, there are provided the following pressure-sensitive adhesive compositions [1] to [12], sealing sheets [13] to [16], and sealing bodies [17] and [18]. .

[1] A pressure-sensitive adhesive composition containing the following component (A), component (C), and component (D).
(A) component: rubber-based resin (C) component: curable resin (D) component: allophanate-based crosslinking agent [2] The pressure-sensitive adhesive composition according to [1], wherein the component (A) is butyl rubber.
[3] The pressure-sensitive adhesive composition according to [1] or [2], further comprising the following component (B).
(B) Component: Tackifier [4] The pressure-sensitive adhesive composition according to [3], wherein the component (B) is an aliphatic petroleum resin.
[5] The pressure-sensitive adhesive composition according to [3] or [4], wherein the content of the component (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the component (C) is a polymer having hydroxyl groups at both ends.
[7] The pressure-sensitive adhesive composition according to any one of [1] to [6], wherein the content of the component (C) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
[8] The pressure-sensitive adhesive composition according to any one of [1] to [7], wherein the component (D) is allophanate-modified hexamethylene diisocyanate.
[9] The pressure-sensitive adhesive composition according to any one of [1] to [8], wherein the content of the component (D) is 1 to 70 parts by mass with respect to 100 parts by mass of the component (A).
[10] The pressure-sensitive adhesive composition according to any one of [1] to [9], further comprising the following component (E):
(E) Component: Silane coupling agent [11] The pressure-sensitive adhesive composition according to [10], wherein the component (E) is a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（Ｒ１は炭素数３以上のアルキレン基を表し、Ｒ２は炭素数１～１０の１価の炭化水素基を表し、Ｒ３は炭素数１～４のアルキル基を表す。Ｚは反応性基を含有する基を表し、ｎは０又は１である。）
〔１２〕前記（Ｅ）成分の含有量が、前記（Ａ）成分１００質量部に対して０．０１～７質量部である、〔１０〕又は〔１１〕に記載の粘着剤組成物。
〔１３〕２枚の剥離フィルムと、これらの剥離フィルムに挟持された粘着剤層とからなる封止シートであって、
　前記粘着剤層が、〔１〕～〔１２〕のいずれかに記載の粘着剤組成物を用いて形成されたものである封止シート。
〔１４〕剥離フィルム、ガスバリア性フィルム、及び、前記剥離フィルムとガスバリア性フィルムに挟持された粘着剤層からなる封止シートであって、
　前記粘着剤層が、〔１〕～〔１２〕のいずれかに記載の粘着剤組成物を用いて形成されたものである封止シート。
〔１５〕前記ガスバリア性フィルムが、金属箔、樹脂製フィルム、又は薄膜ガラスである〔１４〕に記載の封止シート。
〔１６〕粘着剤層の厚みが１～５０μｍである、〔１３〕～〔１５〕のいずれかに記載の封止シート。
〔１７〕被封止物が、〔１３〕～〔１６〕のいずれかに記載の封止シートを用いて封止されてなる封止体。
〔１８〕前記被封止物が、有機ＥＬ素子、有機ＥＬディスプレイ素子、液晶ディスプレイ素子、又は太陽電池素子である、〔１７〕に記載の封止体。 (R 1 represents an alkylene group having 3 or more carbon atoms, R 2 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 represents an alkyl group having 1 to 4 carbon atoms, and Z represents reactivity. Represents a group containing a group, and n is 0 or 1.)
[12] The pressure-sensitive adhesive composition according to [10] or [11], wherein the content of the component (E) is 0.01 to 7 parts by mass with respect to 100 parts by mass of the component (A).
[13] A sealing sheet comprising two release films and an adhesive layer sandwiched between these release films,
A sealing sheet in which the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition according to any one of [1] to [12].
[14] A sealing film comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film,
A sealing sheet in which the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition according to any one of [1] to [12].
[15] The sealing sheet according to [14], wherein the gas barrier film is a metal foil, a resin film, or thin film glass.
[16] The sealing sheet according to any one of [13] to [15], wherein the pressure-sensitive adhesive layer has a thickness of 1 to 50 μm.
[17] A sealed body obtained by sealing an object to be sealed using the sealing sheet according to any one of [13] to [16].
[18] The sealed body according to [17], wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.
　本発明によれば、高湿条件下に置かれても粘着力が低下しない粘着剤組成物、この粘着剤組成物を用いて形成された粘着剤層を有する封止シート、及び被封止物が前記封止シートで封止されてなる封止体が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition by which adhesive force does not fall even if it puts on high humidity conditions, the sealing sheet which has an adhesive layer formed using this adhesive composition, and a to-be-sealed thing Is provided with a sealing body sealed with the sealing sheet.
　以下、本発明を、１）粘着剤組成物、２）封止シート、及び、３）封止体、に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by dividing it into 1) an adhesive composition, 2) a sealing sheet, and 3) a sealing body.
１）粘着剤組成物
　本発明の粘着剤組成物は、下記の（Ａ）成分、（Ｃ）成分、及び（Ｄ）成分を含有するものである。
（Ａ）成分：ゴム系樹脂
（Ｃ）成分：硬化性樹脂
（Ｄ）成分：アロファネート系架橋剤 1) Adhesive composition The adhesive composition of this invention contains the following (A) component, (C) component, and (D) component.
(A) component: rubber-based resin (C) component: curable resin (D) component: allophanate-based crosslinking agent
〔（Ａ）成分：ゴム系樹脂〕
　本発明の粘着剤組成物は、（Ａ）成分としてゴム系樹脂を含有する。
　本発明の粘着剤組成物は、ゴム系樹脂を含有することで、水分遮断性に優れたものとなる。 [(A) component: rubber-based resin]
The pressure-sensitive adhesive composition of the present invention contains a rubber-based resin as the component (A).
The pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties by containing a rubber-based resin.
　ゴム系樹脂としては、例えば、天然ゴム、天然ゴムに（メタ）アクリル酸アルキルエステル、スチレンおよび（メタ）アクリロニトリルから選ばれる１種又は２種以上の単量体をグラフト重合させた変性天然ゴム、ポリイソブチレン系樹脂、ブタジエンゴム、クロロプレンゴム、イソプレンゴム、スチレン－ブタジエン共重合体（ＳＢＲ）、スチレン－イソプレン共重合体、アクリロニトリル－ブタジエンの共重合体（ニトリルゴム）、メタクリル酸メチル－ブタジエン共重合体、ウレタンゴム、スチレン－１，３－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、エチレン－プロピレン－非共役ジエン三元共重合体等が挙げられる。これらのゴム系樹脂は１種を単独で、あるいは２種以上を組み合わせて用いることができる。これらの中でも、ゴム系樹脂としては、ポリイソブチレン系樹脂を含むものが好ましい。 Examples of rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate-butadiene copolymer Examples thereof include urethane, rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene-propylene-nonconjugated diene terpolymer. It is done. These rubber resins can be used alone or in combination of two or more. Among these, as the rubber resin, those containing a polyisobutylene resin are preferable.
　ポリイソブチレン系樹脂は、モノマー成分としてイソブチレンを含む重合体（共重合体の概念を含む）をいい、モノマー成分がイソブチレンのみからなる単独重合体であってもよいし、モノマー成分としてイソブチレンと他のモノマーを重合して得られる共重合体であってもよい。ポリイソブチレン系樹脂は、一部を臭素化又は塩素化したハロゲン化ポリイソブチレン系樹脂であってもよく、一部を水酸基、カルボキシル基等の官能基で置換したものであってもよい。 The polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers. The polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.
　上記他のモノマーとしては、例えば、イソプレン、ｎ－ブテン、ブタジエン、スチレン等が挙げられる。他のモノマーは単独で又は２種以上を併用して用いてもよい。なお、ポリイソブチレン系樹脂が共重合体である場合は、原料モノマー中、イソブチレンは主成分として最大量のモノマーである。 Examples of the other monomer include isoprene, n-butene, butadiene, and styrene. Other monomers may be used alone or in combination of two or more. When the polyisobutylene resin is a copolymer, isobutylene is the maximum amount of monomer as a main component in the raw material monomer.
　上記の中でも、ポリイソブチレン系樹脂は、水分遮断性に優れるという点から、モノマー成分がイソブチレンのみからなる単独重合体、モノマー成分としてイソブチレンとイソプレンとを重合して得られるイソブチレン－イソプレン共重合体（ブチルゴム）であることが好ましい。
  これらの中でも、形成される粘着剤層の耐久性及び耐候性を向上させる観点から、重合した際に密な分子構造を有し、主鎖及び側鎖に重合性二重結合を残さないイソブチレンからなる構成単位を多く含むものが好ましい。 Among these, the polyisobutylene-based resin is excellent in moisture barrier property, so that the monomer component is a homopolymer consisting only of isobutylene, and the isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as monomer components ( Butyl rubber) is preferred.
Among these, from the viewpoint of improving the durability and weather resistance of the formed pressure-sensitive adhesive layer, from isobutylene that has a dense molecular structure when polymerized and does not leave a polymerizable double bond in the main chain and side chain What contains many structural units which become is preferable.
  主鎖及び側鎖に重合性二重結合を残さないイソブチレンからなる構成単位の含有量は、ポリイソブチレン系樹脂の全構成単位に対して、好ましくは８０～９９質量％、より好ましくは９０～９９質量％、更に好ましくは９５～９９質量％である。 The content of the structural unit composed of isobutylene that does not leave a polymerizable double bond in the main chain and side chain is preferably 80 to 99% by mass, more preferably 90 to 99%, based on all the structural units of the polyisobutylene resin. % By mass, more preferably 95 to 99% by mass.
  ポリイソブチレン系樹脂は、例えば、塩化アルミニウム、三フッ化ホウ素等のルイス酸触媒の存在下で、イソブチレン等のモノマー成分を重合する方法等により得ることができる。 The polyisobutylene resin can be obtained, for example, by a method of polymerizing a monomer component such as isobutylene in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
　ゴム系樹脂の質量平均分子量（Ｍｗ）は、好ましくは１０，０００～３，０００，０００、より好ましくは２０，０００～１，０００，０００である。
　本発明において、質量平均分子量（Ｍｗ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を行い、標準ポリスチレン換算値として求めることができる。 The mass average molecular weight (Mw) of the rubber-based resin is preferably 10,000 to 3,000,000, more preferably 20,000 to 1,000,000.
In the present invention, the mass average molecular weight (Mw) can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC).
〔（Ｃ）成分：硬化性樹脂〕
　本発明の粘着剤組成物は、（Ｃ）成分として、硬化性樹脂を含有する。
　本発明の粘着剤組成物は、硬化性樹脂を含有することで、高湿条件下に置かれても粘着力が低下し難いものとなる。
　硬化性樹脂とは、（Ｄ）成分のアロファネート系架橋剤と反応し得る官能基を２以上有する重合体をいう。かかる官能基としては、水酸基が挙げられる。 [(C) component: curable resin]
The pressure-sensitive adhesive composition of the present invention contains a curable resin as the component (C).
Since the pressure-sensitive adhesive composition of the present invention contains a curable resin, the pressure-sensitive adhesive force is hardly lowered even under high humidity conditions.
The curable resin refers to a polymer having two or more functional groups capable of reacting with the allophanate-based crosslinking agent as component (D). Such functional groups include hydroxyl groups.
　硬化性樹脂としては、ポリカーボネートポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリラクトンポリオール、ポリジエンポリオール、水素化ポリジエンポリオール、両末端に水酸基を有するポリシリコーン等の、両末端に水酸基を有する重合体が挙げられる。
　硬化性樹脂は、１種を単独で、あるいは２種以上を組み合わせて用いることができる。 Examples of the curable resin include polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polydiene polyols, hydrogenated polydiene polyols, and polymers having hydroxyl groups at both ends, such as silicones having hydroxyl groups at both ends. Can be mentioned.
A curable resin can be used individually by 1 type or in combination of 2 or more types.
　これらの中でも、高湿条件下に置かれても粘着力が低下し難い粘着剤組成物が得られ易いことから、ポリジエンポリオール又は水素化ポリジエンポリオールが好ましい。
　ポリジエンポリオールとしては、ポリブタジエンポリオール、ポリイソプレンポリオール等が挙げられる。
　水素化ポリジエンポリオールとしては、水素化ポリブタジエンポリオール、水素化ポリイソプレンポリオール等が挙げられる。 Among these, a polydiene polyol or a hydrogenated polydiene polyol is preferable because a pressure-sensitive adhesive composition that does not easily lower the adhesive strength even when placed under a high humidity condition is easily obtained.
Examples of the polydiene polyol include polybutadiene polyol and polyisoprene polyol.
Examples of the hydrogenated polydiene polyol include hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol.
　ポリジエンポリオールや水素化ポリジエンポリオールとしては、市販品を使用することができる。
　かかる市販品としては、日本曹達株式会社製のＮＩＳＳＯ　ＰＢ　Ｇ－１０００、Ｇ－２０００、Ｇ－３０００、出光興産株式会社製のＰｏｌｙ　ｂｄ　Ｒ－１５ＨＴ，Ｒ－４５ＨＴ、Ｃｒａｙ　Ｖａｌｌｅｙ社製のＫｒａｓｏｌ　ＬＢＨ２０００、ＬＢＨ－Ｐ２０００、ＬＢＨ３０００、ＬＢＨ－Ｐ３０００（以上ポリブタジエンポリオール）、日本曹達株式会社製のＮＩＳＳＯ　ＰＢ　ＧＩ－１０００、ＧＩ－２０００、ＧＩ－３０００、三菱化学株式会社製のポリテールＨ、Ｃｒａｙ　Ｖａｌｌｅｙ社製のＫｒａｓｏｌ　ＨＬＢＨ－Ｐ２０００、ＨＬＢＨ－Ｐ３０００（以上水素化ポリブタジエンポリオール）、出光興産株式会社製のＰｏｌｙ　ｉｐ（ポリイソプレンポリオール）、出光興産株式会社製のエポール（水素化ポリイソプレンポリオール）等が挙げられる。 Commercially available products can be used as the polydiene polyol and hydrogenated polydiene polyol.
Examples of such commercially available products include NISSO PB G-1000, G-2000, G-3000 manufactured by Nippon Soda Co., Ltd., Poly bd R-15HT, R-45HT manufactured by Idemitsu Kosan Co., Ltd., Krasol LBH2000 manufactured by Cray Valley, LBH-P2000, LBH3000, LBH-P3000 (polybutadiene polyol), NISSO PB GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., Polytail H manufactured by Mitsubishi Chemical Corporation, Krasol manufactured by Cray Valley HLBH-P2000, HLBH-P3000 (hydrogenated polybutadiene polyol), Poly ip (polyisoprene polyol) manufactured by Idemitsu Kosan Co., Ltd., Epaul (hydrogenated polyisoprene polyol manufactured by Idemitsu Kosan Co., Ltd.) Etc. The.
　硬化性樹脂の質量平均分子量（Ｍｗ）は、好ましくは１，０００～５，０００、より好ましくは１，０００～４，０００である。硬化性樹脂の質量平均分子量（Ｍｗ）が上記範囲内であることで、粘着力により優れる粘着剤組成物が得られる。 The mass average molecular weight (Mw) of the curable resin is preferably 1,000 to 5,000, more preferably 1,000 to 4,000. When the mass average molecular weight (Mw) of the curable resin is within the above range, an adhesive composition that is superior in adhesive strength can be obtained.
　硬化性樹脂の含有量は、特に限定されないが、（Ａ）成分１００質量部に対して、通常１～５０質量部、好ましくは５～４０質量部である。
　硬化性樹脂の含有量が、（Ａ）成分１００質量部に対して、１質量部以上であることで、粘着力により優れる粘着剤層を効率よく形成することができ、５０質量部以下であることで、粘着剤層の凝集力の低下を避けることができる。 The content of the curable resin is not particularly limited, but is usually 1 to 50 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of component (A).
When the content of the curable resin is 1 part by mass or more with respect to 100 parts by mass of the component (A), an adhesive layer that excels in adhesive strength can be efficiently formed, and the content is 50 parts by mass or less. Thereby, the fall of the cohesion force of an adhesive layer can be avoided.
〔（Ｄ）成分：アロファネート系架橋剤〕
　本発明の粘着剤組成物は、（Ｄ）成分として、アロファネート系架橋剤を含有する。
　アロファネート系架橋剤は（Ｃ）成分との間で架橋構造を形成し得るものであり、これらの成分を含有する本発明の粘着剤組成物を用いて得られた粘着剤層は、凝集力が高く、高湿条件下に置かれても粘着力が低下し難いものである。
　アロファネート系架橋剤は、ポリイソシアネートの変性体であって、アロファネート結合を有するもの（以下、「アロファネート変性ポリイソシアネート」という）である。
　アロファネート変性ポリイソシアネートは、例えば、アロファネート化触媒の存在下、ポリイソシアネート化合物と、モノオール化合物及び／又はポリオール化合物とを反応させることにより得ることができる。 [Component (D): Allophanate Crosslinking Agent]
The pressure-sensitive adhesive composition of the present invention contains an allophanate-based crosslinking agent as the component (D).
The allophanate-based crosslinking agent can form a crosslinked structure with the component (C), and the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention containing these components has a cohesive force. It is high, and even when it is placed under high humidity conditions, the adhesive strength is difficult to decrease.
The allophanate-based crosslinking agent is a modified polyisocyanate and has an allophanate bond (hereinafter referred to as “allophanate-modified polyisocyanate”).
The allophanate-modified polyisocyanate can be obtained, for example, by reacting a polyisocyanate compound with a monool compound and / or a polyol compound in the presence of an allophanate-forming catalyst.
　アロファネート化触媒としては、例えば、カルボン酸の金属塩等の公知の触媒から適宜選択して用いることができる。 As the allophanatization catalyst, for example, a known catalyst such as a metal salt of carboxylic acid can be appropriately selected and used.
　ポリイソシアネート化合物は、分子内に少なくとも２つのイソシアネート基を有する化合物である。ポリイソシアネート化合物としては、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネート、脂環族ポリイソシアネート、脂肪族ポリイソシアネート等が挙げられる。 The polyisocyanate compound is a compound having at least two isocyanate groups in the molecule. Examples of the polyisocyanate compound include aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.
　芳香族ポリイソシアネートとしては、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、１，５－ナフタレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、２，４－若しくは２，６－トリレンジイソシアネート（ＴＤＩ）又はこれらの混合物、４，４’－トルイジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート；トリフェニルメタン－４，４’，４’’－トリイソシアネート、１，３，５－トリイソシアネートベンゼン、２，４，６－トリイソシアネートトルエン等の芳香族トリイソシアネート；４，４’－ジフェニルメタン－２，２’，５，５’－テトライソシアネート等の芳香族テトライソシアネート；等が挙げられる。 Aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI). Or mixtures thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanate Aromatic triisocyanates such as benzene and 2,4,6-triisocyanate toluene; aromatic tetraisocyanates such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate; and the like.
　芳香脂肪族ポリイソシアネートとしては、１，３－若しくは１，４－キシリレンジイソシアネート（ＸＤＩ）又はこれらの混合物、ω，ω’－ジイソシアネート－１，４－ジエチルベンゼン、１，３－若しくは１，４－ビス（１－イソシアネート－１－メチルエチル）ベンゼン（ＴＭＸＤＩ）又はこれらの混合物等の芳香脂肪族ジイソシアネート；１，３，５－トリイソシアネートメチルベンゼン等の芳香脂肪族トリイソシアネート；等が挙げられる。 Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate (XDI) or a mixture thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4- And araliphatic diisocyanates such as bis (1-isocyanate-1-methylethyl) benzene (TMXDI) or mixtures thereof; and araliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene; and the like.
　脂環族ポリイソシアネートとしては、１，３－シクロペンタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート、３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（ＩＰＤＩ）、４，４’－メチレンビス（シクロヘキシルイソシアネート）（Ｈ１２ＭＤＩ）、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、１，３－若しくは１，４－ビス（イソシアネートメチル）シクロヘキサン（Ｈ６ＸＤＩ）又はこれらの混合物等の脂環族ジイソシアネート；１，３，５－トリイソシアネートシクロヘキサン、１，３，５－トリメチルイソシアネートシクロヘキサン、２－（３－イソシアネートプロピル）－２，５－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、２－（３－イソシアネートプロピル）－２，６－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、３－（３－イソシアネートプロピル）－２，５－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアネートエチル）－２－イソシアネートメチル－３－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン、６－（２－イソシアネートエチル）－２－イソシアネートメチル－３－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアネートエチル）－２－イソシアネートメチル－２－（３－イソシアネートプロピル）－ビシクロ（２．２．１）－ヘプタン、６－（２－イソシアネートエチル）－２－イソシアネートメチル－２－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン等の脂環族トリイソシアネート；等が挙げられる。 Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 4, 4′-methylenebis (cyclohexyl isocyanate) (H 12 MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (H 6 XDI) or mixtures thereof; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane, 2- (3-isocyanate pro ) -2,5-di (isocyanatemethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatemethyl) -bicyclo (2.2.1) Heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3- Isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- ( 2-Isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, and the like;
　脂肪族ポリイソシアネートとしては、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、２，４，４－又は２，２，４－トリメチルヘキサメチレンジイソシアネート、２，６－ジイソシアネートメチルカプロエート等の脂肪族ジイソシアネート；リジンエステルトリイソシアネート、１，４，８－トリイソシアネートオクタン、１，６，１１－トリイソシアネートウンデカン、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－トリイソシアネートヘキサン、２，５，７－トリメチル－１，８－ジイソシアネート－５－イソシアネートメチルオクタン等の脂肪族トリイソシアネート；等が挙げられる。 Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate; lysine ester triisocyanate, 1,4,8-triisocyanate Octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane aliphatic triisocyanate; and the like.
　これらの中でも、ポリイソシアネート化合物としては、脂肪族ポリイソシアネートが好ましく、ヘキサメチレンジイソシアネートがより好ましい。
　ポリイソシアネート化合物は、１種を単独で、あるいは２種以上を組み合わせて用いることができる。 Among these, as a polyisocyanate compound, aliphatic polyisocyanate is preferable and hexamethylene diisocyanate is more preferable.
A polyisocyanate compound can be used individually by 1 type or in combination of 2 or more types.
　モノオール化合物としては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、オクタノール等の脂肪族モノアルコール類；シクロペンタノール、ジメチルシクロヘキサノール等の脂環族モノアルコール類；ベンジルアルコール等の芳香脂肪族モノアルコール類；フェノール、クレゾール等のフェノール類；等が挙げられる。 Monool compounds include aliphatic monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol; alicyclic monoalcohols such as cyclopentanol and dimethylcyclohexanol; and aromatic fats such as benzyl alcohol Group monoalcohols; phenols such as phenol and cresol; and the like.
　ポリオール化合物としては、エチレングリコール、プロパンジオール、１，４－ブチレングリコール、１，３－ブチレングリコール、１，２－ブチレングリコール、１，６－ヘキサンジオール、ネオペンチルグリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、シクロヘキサンジメタノール、ビスフェノールＡ、水素化ビスフェノールＡ、１，４－ジヒドロキシ－２－ブテン、２，６－ジメチル－１－オクテン－３，８－ジオール、ビスヒドロキシエトキシベンゼン、キシレングリコール、ビスヒドロキシエチレンテレフタレート等のジオール化合物；グリセリン、２－メチル－２－ヒドロキシメチル－１，３－プロパンジオール、２，４－ジヒドロキシ－３－ヒドロキシメチルペンタン、１，２，６－ヘキサントリオール、１，１，１－トリス（ヒドロキシメチル）プロパン、２，２－ビス（ヒドロキシメチル）－３－ブタノール等のトリオール化合物；テトラメチロールメタン、Ｄ－ソルビトール、キシリトール、Ｄ－マンニトール等の水酸基を４個以上有するポリオール；等が挙げられる。 Examples of the polyol compound include ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, diethylene glycol, Propylene glycol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bis Diol compounds such as hydroxyethylene terephthalate; glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6 Triol compounds such as hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) -3-butanol; hydroxyl groups such as tetramethylolmethane, D-sorbitol, xylitol, D-mannitol A polyol having 4 or more of.
　アロファネート系架橋剤の含有量は、特に限定されないが、（Ａ）成分１００質量部に対して、通常１～７０質量部、好ましくは５～６０質量部である。
　アロファネート系架橋剤の含有量が、（Ａ）成分１００質量部に対して、１質量部以上であることで、架橋構造を十分に形成することができ、７０質量部以下であることで、粘着剤層の凝集力の低下を避けることができる。 The content of the allophanate-based crosslinking agent is not particularly limited, but is usually 1 to 70 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of component (A).
When the content of the allophanate-based crosslinking agent is 1 part by mass or more with respect to 100 parts by mass of the component (A), a crosslinked structure can be sufficiently formed, and the adhesive is 70 parts by mass or less. A decrease in the cohesive strength of the agent layer can be avoided.
　本発明の粘着剤組成物は、前記（Ａ）成分、（Ｃ）成分及び（Ｄ）成分に加えて、（Ｂ）成分として粘着付与剤を含有することが好ましい。
　本発明の粘着剤組成物は、粘着付与剤を含有することで、水分遮断性により優れ、かつ、粘着力が高いものとなる。 The pressure-sensitive adhesive composition of the present invention preferably contains a tackifier as the component (B) in addition to the components (A), (C) and (D).
By containing a tackifier, the pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties and has high adhesive strength.
　粘着付与剤としては、粘着剤層の粘着力を向上させるものであれば特に限定されず、公知のものを用いることができる。粘着付与剤としては、脂環族系石油樹脂、脂肪族系石油樹脂、テルペン樹脂、エステル系樹脂、クマロン－インデン樹脂、ロジン系樹脂、エポキシ樹脂、フェノール樹脂、アクリル樹脂、ブチラール樹脂、オレフィン樹脂、塩素化オレフィン樹脂、酢酸ビニル樹脂、及びこれらの変性樹脂又は水素添加された樹脂等が挙げられる。
　これらの中でも、水分遮断性により優れ、かつ、粘着力が高い粘着剤組成物が得られ易いことから、脂肪族系石油樹脂が好ましい。
　粘着付与剤は、１種を単独で、あるいは２種以上を組み合わせて用いることができる。 The tackifier is not particularly limited as long as it improves the adhesive strength of the pressure-sensitive adhesive layer, and a known one can be used. Tackifiers include alicyclic petroleum resins, aliphatic petroleum resins, terpene resins, ester resins, coumarone-indene resins, rosin resins, epoxy resins, phenol resins, acrylic resins, butyral resins, olefin resins, Examples thereof include chlorinated olefin resins, vinyl acetate resins, modified resins thereof, and hydrogenated resins.
Among these, an aliphatic petroleum resin is preferable because it is easy to obtain a pressure-sensitive adhesive composition having excellent moisture barrier properties and high adhesive strength.
A tackifier can be used individually by 1 type or in combination of 2 or more types.
　粘着付与剤として、市販品をそのまま使用することもできる。例えば、市販品としては、エスコレッツ１０００シリーズ（エクソン化学社製）、クイントンＡ、Ｂ、Ｒ、ＣＸシリーズ（日本ゼオン社製）等の脂肪族系石油樹脂；アルコンＰ、Ｍシリーズ（荒川化学社製）、ＥＳＣＯＲＥＺシリーズ（エクソン・ケミカル社製）、ＥＡＳＴＯＴＡＣシリーズ（イーストマン・ケミカル社製）、ＩＭＡＲＶシリーズ（出光興産社製）等の脂環族系石油樹脂；ＹＳレジンＰ、Ａシリーズ（安原油脂社製）、クリアロンＰシリーズ（ヤスハラ・ケミカル製）、ピコライトＡ、Ｃシリーズ（ハーキュレス社製）等のテルペン系樹脂；フォーラルシリーズ（ハーキュレス社製）、ペンセルＡシリーズ、エステルガム、スーパー・エステル、パインクリスタル（荒川化学工業社製）等のエステル系樹脂；等が挙げられる。 Commercially available products can be used as they are as tackifiers. For example, commercially available products include aliphatic petroleum resins such as Escolets 1000 Series (Exxon Chemical Co., Ltd.), Quinton A, B, R, CX Series (Zeon Japan Co., Ltd.); Alcon P, M Series (Arakawa Chemical Co., Ltd.) ), ESCOREZ series (manufactured by Exxon Chemical), EASTOTAC series (manufactured by Eastman Chemical), ILARV series (manufactured by Idemitsu Kosan Co., Ltd.); ), Clearon P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by Hercules), etc .; Foal series (manufactured by Hercules), Pencel A series, ester gum, super ester, pine crystal Ester resins such as Arakawa Chemical Industries, etc .;
　粘着付与剤の質量平均分子量（Ｍｗ）は、好ましくは、１００～１０，０００、より好ましくは５００～５，０００である。
　粘着付与剤の軟化点は、好ましくは、５０～１６０℃、より好ましくは６０～１４０℃、さらに好ましくは７０～１３０℃である。 The mass average molecular weight (Mw) of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000.
The softening point of the tackifier is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, still more preferably 70 to 130 ° C.
　粘着付与剤の含有量は、特に限定されないが、（Ａ）成分１００質量部に対して、通常１～５０質量部、好ましくは５～４５質量部である。
　粘着付与剤の含有量が、（Ａ）成分１００質量部に対して、１質量部以上であることで、粘着力により優れる粘着剤層を効率よく形成することができ、５０質量部以下であることで、粘着剤層の凝集力の低下を避けることができる。 The content of the tackifier is not particularly limited, but is usually 1 to 50 parts by mass, preferably 5 to 45 parts by mass with respect to 100 parts by mass of component (A).
When the content of the tackifier is 1 part by mass or more with respect to 100 parts by mass of the component (A), an adhesive layer that excels in adhesive strength can be efficiently formed, and the content is 50 parts by mass or less. Thereby, the fall of the cohesion force of an adhesive layer can be avoided.
〔その他の成分〕
　本発明の粘着剤組成物は、前記（Ａ）、（Ｃ）成分、（Ｄ）成分、及び、所望により（Ｂ）成分に加えて、（Ｅ）成分としてシランカップリング剤を含有するものが好ましい。
　本発明の粘着剤組成物は、シランカップリング剤を含有することで、常温及び高温高湿環境下における粘着力がさらに向上する傾向がある。 [Other ingredients]
The pressure-sensitive adhesive composition of the present invention contains a silane coupling agent as the component (E) in addition to the components (A), (C), (D), and (B) as required. preferable.
When the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent, the pressure-sensitive adhesive force at room temperature and in a high temperature and high humidity environment tends to be further improved.
　シランカップリング剤としては、公知のシランカップリング剤を用いることができ、特に限定されない。なかでも、下記式（１）で示されるシラン化合物が好ましい。 A known silane coupling agent can be used as the silane coupling agent, and is not particularly limited. Among these, a silane compound represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（１）中、Ｒ１は炭素数３以上のアルキレン基を表し、Ｒ２は炭素数１～１０の１価の炭化水素基を表し、Ｒ３は炭素数１～４のアルキル基を表す。Ｚは反応性基を含有する基を表し、ｎは０又は１である。 In formula (1), R 1 represents an alkylene group having 3 or more carbon atoms, R 2 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms. . Z represents a group containing a reactive group, and n is 0 or 1.
　Ｒ１で表されるアルキレン基の炭素数は、３以上であり、３～２０が好ましく、４～１５がより好ましい。
　アルキレン基の炭素数が３以上であることで、架橋反応がより起こり易くなる。
　Ｒ１で表されるアルキレン基としては、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基等が挙げられる。 The alkylene group represented by R 1 has 3 or more carbon atoms, preferably 3 to 20, and more preferably 4 to 15.
When the carbon number of the alkylene group is 3 or more, the crosslinking reaction is more likely to occur.
Examples of the alkylene group represented by R 1 include trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and the like.
　Ｒ２で表される１価の炭化水素基の炭素数は、１～１０であり、１～６が好ましく、１～４がより好ましい。
　Ｒ２で表される１価の炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等のアルキル基；ビニル基、１－プロペニル基、２－プロペニル基、イソプロペニル基、３－ブテニル基、４－ペンテニル基、５－ヘキセニル基等のアルケニル基；エチニル基、プロパルギル基、ブチニル基等のアルキニル基；フェニル基、１－ナフチル基、２－ナフチル基等のアリール基；等が挙げられる。 The monovalent hydrocarbon group represented by R 2 has 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4.
Examples of the monovalent hydrocarbon group represented by R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, and n-pentyl group. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3- Alkenyl groups such as butenyl group, 4-pentenyl group and 5-hexenyl group; alkynyl groups such as ethynyl group, propargyl group and butynyl group; aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group; It is done.
　Ｒ３で表されるアルキル基の炭素数は、１～４であり、１～３が好ましく、１又は２がより好ましい。
　Ｒ３で表されるアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔ－ブチル基が挙げられる。 The alkyl group represented by R 3 has 1 to 4, preferably 1 to 3, more preferably 1 or 2, carbon atoms.
Examples of the alkyl group represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and t-butyl group.
　Ｚに含まれる反応性基は、架橋反応に寄与し得る基であれば特に限定されない。
　反応性基としては、エポキシ基又はアミノ基が好ましい。
　エポキシ基を含有するＺとしては、エポキシ基、グリシジル基、エポキシシクロヘキシル基等が挙げられる。
　アミノ基を含有するＺとしては、アミノ基、２－アミノエチルアミノ基、フェニルアミノ基等が挙げられる。 The reactive group contained in Z is not particularly limited as long as it can contribute to the crosslinking reaction.
As the reactive group, an epoxy group or an amino group is preferable.
Examples of Z containing an epoxy group include an epoxy group, a glycidyl group, and an epoxycyclohexyl group.
Examples of Z containing an amino group include an amino group, a 2-aminoethylamino group, and a phenylamino group.
　式（１）で示されるシランカップリング剤としては、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、８－グリシドキシオクチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－（２－アミノエチルアミノ）プロピルメチルジメトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（フェニルアミノ）プロピルトリメトキシシラン、８－（アミノエチルアミノ）オクチルトリメトキシシラン等が挙げられる。 Examples of the silane coupling agent represented by the formula (1) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2 -Aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 8- (aminoethylamino) octyltrimethoxysilane, etc. .
　シランカップリング剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
　本発明の粘着剤組成物がシランカップリング剤を含有するとき、シランカップリング剤の含有量は、前記（Ａ）成分１００質量部に対して、好ましくは０．０１～７質量部、より好ましくは０．１～５質量部である。
　シランカップリング剤の含有量がこの範囲内にある粘着剤組成物は高温時においても優れた粘着力を有する傾向がある。 A silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
When the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.01 to 7 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.1 to 5 parts by mass.
A pressure-sensitive adhesive composition having a silane coupling agent content within this range tends to have excellent adhesive force even at high temperatures.
　本発明の粘着剤組成物に含まれる、（Ａ）～（Ｄ）成分やシランカップリング剤以外の成分としては、溶媒、各種添加剤が挙げられる。 Examples of components other than the components (A) to (D) and the silane coupling agent contained in the pressure-sensitive adhesive composition of the present invention include solvents and various additives.
　溶媒としては、ベンゼン、トルエンなどの芳香族炭化水素系溶媒；酢酸エチル、酢酸ブチルなどのエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタンなどの脂肪族炭化水素系溶媒；シクロペンタン、シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素系溶媒；等が挙げられる。
　これらの溶媒は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
　溶媒の使用量は、塗工性等を考慮して適宜決定することができる。 Solvents 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- And aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane;
These solvents can be used alone or in combination of two or more.
The amount of the solvent used can be appropriately determined in consideration of coating properties and the like.
　添加剤としては、紫外線吸収剤、帯電防止剤、光安定剤、酸化防止剤、樹脂安定剤、充填剤、顔料、増量剤、軟化剤等の添加剤が挙げられる。
　これらは１種単独で、あるいは２種以上を組み合わせて用いることができる。
　本発明の粘着剤組成物がこれらの添加剤を含有する場合、その含有量は、目的に合わせて適宜決定することができる。 Examples of the additive include additives such as an ultraviolet absorber, an antistatic agent, a light stabilizer, an antioxidant, a resin stabilizer, a filler, a pigment, an extender, and a softening agent.
These can be used alone or in combination of two or more.
When the adhesive composition of this invention contains these additives, the content can be suitably determined according to the objective.
　本発明の粘着剤組成物は、所定の成分を、常法に従って適宜混合・攪拌することにより調製することができる。 The pressure-sensitive adhesive composition of the present invention can be prepared by appropriately mixing and stirring predetermined components according to a conventional method.
　本発明の粘着剤組成物は、粘着力に優れるものである。特に、粘着後、高湿条件下に置かれた場合であっても、粘着力の低下が生じにくいという特徴を有する。
　例えば、本発明の粘着剤組成物を用いて得られた試験片について１８０°剥離試験を行ったときに、下記式で算出されるｘ値が１．０以上であることが好ましい。 The pressure-sensitive adhesive composition of the present invention is excellent in adhesive strength. In particular, the adhesive strength is not easily lowered even when the adhesive is placed under high-humidity conditions.
For example, when a 180 ° peel test is performed on a test piece obtained using the pressure-sensitive adhesive composition of the present invention, the x value calculated by the following formula is preferably 1.0 or more.
Figure JPOXMLDOC01-appb-M000004
Figure JPOXMLDOC01-appb-M000004
　式中、Ａは、温度２３℃、相対湿度５０％の条件下で１８０°剥離試験を行って得られた粘着力を表し、Ｂは、試験片を温度６０℃、相対湿度９０％の条件下に１６８時間、次いで、温度２３℃、相対湿度５０％の条件下に２４時間静置させた後に、温度２３℃、相対湿度５０％条件下で１８０°剥離試験を行って得られた粘着力を表す。 In the formula, A represents an adhesive strength obtained by performing a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and B represents a condition of the test piece at a temperature of 60 ° C. and a relative humidity of 90%. For 168 hours, and then allowed to stand for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, followed by a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. To express.
　Ａの値は特に限定されないが、通常、２～２５Ｎ／２５ｍｍ、好ましくは２～２０Ｎ／２５ｍｍである。
　Ｂの値は特に限定されないが、通常、５～３５Ｎ／２５ｍｍ、好ましくは５～３０Ｎ／２５ｍｍである。 The value of A is not particularly limited, but is usually 2 to 25 N / 25 mm, preferably 2 to 20 N / 25 mm.
The value of B is not particularly limited, but is usually 5 to 35 N / 25 mm, preferably 5 to 30 N / 25 mm.
　これらの１８０°剥離試験の試験片は、実施例に記載の方法に従って調製することができる。 Specimens for these 180 ° peel tests can be prepared according to the method described in the examples.
　本発明の粘着剤組成物は、水分遮断性及び粘着力に優れるため、本発明の粘着剤組成物は、封止材を形成する際に好適に用いられる。 Since the pressure-sensitive adhesive composition of the present invention is excellent in moisture barrier properties and adhesive strength, the pressure-sensitive adhesive composition of the present invention is suitably used when forming a sealing material.
２）封止シート
　本発明の封止シートは、下記の封止シート（α）又は封止シート（β）である。
封止シート（α）：２枚の剥離フィルムと、これらの剥離フィルムに挟持された粘着剤層とからなる封止シートであって、前記粘着剤層が、本発明の粘着剤組成物を用いて形成されたものであることを特徴とするもの
封止シート（β）：剥離フィルムと、ガスバリア性フィルムと、前記剥離フィルムと前記ガスバリア性フィルムに挟持された粘着剤層とからなる封止シートであって、前記粘着剤層が、本発明の粘着剤組成物を用いて形成されたものであることを特徴とするもの
　なお、これらの封止シートは使用前の状態を表したものであり、本発明の封止シートを使用する際は、通常、剥離フィルムは剥離除去される。 2) Sealing sheet The sealing sheet of this invention is the following sealing sheet ((alpha)) or sealing sheet ((beta)).
Sealing sheet (α): a sealing sheet comprising two release films and an adhesive layer sandwiched between these release films, wherein the adhesive layer uses the adhesive composition of the present invention. A sealing sheet (β): a sealing sheet comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film The pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition of the present invention. These sealing sheets represent a state before use. When using the sealing sheet of the present invention, the release film is usually peeled off.
　封止シート（α）を構成する剥離フィルムは、封止シート（α）の製造工程においては支持体として機能するとともに、封止シート（α）を使用するまでの間は、粘着剤層の保護シートとして機能する。 The release film constituting the sealing sheet (α) functions as a support in the production process of the sealing sheet (α), and protects the adhesive layer until the sealing sheet (α) is used. Functions as a sheet.
　剥離フィルムとしては、従来公知のものを利用することができる。例えば、剥離フィルム用の基材上に、剥離剤により剥離処理された剥離層を有するものが挙げられる。
　剥離フィルム用の基材としては、グラシン紙、コート紙、上質紙等の紙基材；これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙；ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリプロピレン樹脂、ポリエチレン樹脂等のプラスチックフィルム；等が挙げられる。
　剥離剤としては、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。 A conventionally well-known thing can be utilized as a peeling film. For example, what has the peeling layer by which the peeling process was carried out with the release agent on the base material for peeling films is mentioned.
As the substrate for the release film, 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.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
　封止シート（α）における２枚の剥離フィルムは同一であっても、異なっていてもよいが、２枚の剥離フィルムは異なる剥離力を有するものが好ましい。２枚の剥離フィルムの剥離力が異なることで、封止シートの使用時に問題が発生し難くなる。すなわち、２枚の剥離フィルムの剥離力を異なるようにすることで、最初に剥離フィルムを剥離する工程をより効率よく行うことができる。 The two release films in the sealing sheet (α) may be the same or different, but the two release films preferably have different release forces. When the peel strengths of the two release films are different, problems are less likely to occur when the sealing sheet is used. That is, the process of peeling a peeling film first can be performed more efficiently by making the peeling force of two peeling films differ.
　封止シート（α）の粘着剤層の厚みは特に限定されないが、通常、１～５０μｍであり、好ましくは５～３０μｍである。
　厚みが上記範囲内にある粘着剤層は、封止材として好適に用いられる。 The thickness of the pressure-sensitive adhesive layer of the sealing sheet (α) is not particularly limited, but is usually 1 to 50 μm, preferably 5 to 30 μm.
The pressure-sensitive adhesive layer having a thickness in the above range is suitably used as a sealing material.
　封止シート（α）の製造方法は特に限定されない。例えば、キャスト法を用いて、封止シート（α）を製造することができる。
　封止シート（α）をキャスト法により製造する場合、公知の方法を用いて、本発明の粘着剤組成物を剥離フィルムの剥離処理面に塗工し、得られた塗膜を乾燥することで、剥離フィルム付粘着剤層を製造し、次いで、もう１枚の剥離フィルムを粘着剤層上に重ねることで、封止シート（α）を得ることができる。 The manufacturing method of a sealing sheet ((alpha)) is not specifically limited. For example, the sealing sheet (α) can be manufactured using a casting method.
When the sealing sheet (α) is produced by a casting method, by using a known method, the pressure-sensitive adhesive composition of the present invention is applied to the release-treated surface of the release film, and the obtained coating film is dried. A sealing sheet (α) can be obtained by producing a pressure-sensitive adhesive layer with a release film and then stacking another release film on the pressure-sensitive adhesive layer.
　粘着剤組成物を塗工する方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等が挙げられる。
　塗膜を乾燥するときの乾燥条件としては、例えば８０～１５０℃で３０秒～５分間が挙げられる。
　乾燥処理を行った後、そのまま１週間程度静置し、粘着剤層を養生させてもよい。粘着剤層を養生させることで、架橋構造を十分に形成することができる。 Examples of the method for applying the pressure-sensitive adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
The drying conditions for drying the coating film include, for example, 80 to 150 ° C. for 30 seconds to 5 minutes.
After the drying treatment, the pressure-sensitive adhesive layer may be cured by allowing it to stand still for about one week. By curing the pressure-sensitive adhesive layer, a crosslinked structure can be sufficiently formed.
　封止シート（β）を構成する剥離フィルムと粘着剤層は、それぞれ、封止シート（α）を構成する剥離フィルムと粘着剤層として示したものと同様のものが挙げられる。
　封止シート（β）を構成するガスバリア性フィルムは、水分遮断性を有するフィルムであれば特に限定されない。 Examples of the release film and the pressure-sensitive adhesive layer constituting the sealing sheet (β) are the same as those shown as the release film and the pressure-sensitive adhesive layer constituting the sealing sheet (α), respectively.
The gas barrier film which comprises a sealing sheet ((beta)) will not be specifically limited if it is a film which has a moisture barrier property.
　ガスバリア性フィルムとしては、基材層上に、直接又はプライマー層等のその他の層を介して、ガスバリア層を有するものが挙げられる。 Examples of the gas barrier film include those having a gas barrier layer on the base material layer directly or via other layers such as a primer layer.
〔基材層〕
　本発明のガスバリア性積層体を構成する基材層は、透明性に優れ、かつ、ガスバリア層等を担持し得るものであれば特に制限されない。 [Base material layer]
The base material layer constituting the gas barrier laminate of the present invention is not particularly limited as long as it is excellent in transparency and can carry a gas barrier layer or the like.
　基材層としては、通常、樹脂フィルムが用いられる。
　樹脂フィルムの樹脂成分としては、ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリオレフィン、ポリエステル、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、アクリル系樹脂、シクロオレフィン系ポリマー、芳香族系重合体等が挙げられる。 As the base material layer, a resin film is usually used.
Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, cycloolefin polymer And aromatic polymers.
　前記樹脂フィルムは、本発明の効果を妨げない範囲において各種添加剤を含有していてもよい。添加剤としては、紫外線吸収剤、帯電防止剤、安定剤、酸化防止剤、可塑剤、滑剤、着色顔料等が挙げられる。これらの添加剤の含有量は、目的に合わせて適宜決定すればよい。 The resin film may contain various additives as long as the effects of the present invention are not hindered. Examples of 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 determine suitably content of these additives according to the objective.
　樹脂フィルムは、樹脂成分及び所望により各種添加剤を含む樹脂組成物を調製し、これをフィルム状に成形することにより得ることができる。成形方法は特に限定されず、キャスト法や溶融押出法等の公知の方法を利用することができる。 The resin film can be obtained by preparing a resin composition containing a resin component and optionally various additives, and molding the resin composition into a film. The molding method is not particularly limited, and a known method such as a casting method or a melt extrusion method can be used.
　基材層の厚みは特に限定されず、ガスバリア性積層体の目的に合わせて決定すればよい。基材層の厚みは、通常、０．５～５００μｍ、好ましくは１～１００μｍである。 The thickness of the base material layer is not particularly limited, and may be determined according to the purpose of the gas barrier laminate. The thickness of the base material layer is usually 0.5 to 500 μm, preferably 1 to 100 μm.
　ガスバリア性フィルムの構成するガスバリア層は、酸素や水蒸気等のガスの透過を抑制する特性（ガスバリア性）を有する層である。このガスバリア層は、前記基材層の一方の面（Ａ）上に、直接又はその他の層を介して積層されてなるものである。 The gas barrier layer constituting the gas barrier film is a layer having characteristics (gas barrier properties) for suppressing permeation of gases such as oxygen and water vapor. This gas barrier layer is laminated on one surface (A) of the base material layer directly or via another layer.
　ガスバリア層の厚みは、通常、１～２０００ｎｍ、より好ましくは３～１０００ｎｍ、より好ましくは５～５００ｎｍである。 The thickness of the gas barrier layer is usually 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm.
　ガスバリア層としては、金属箔からなるガスバリア層、薄膜ガラスからなるガスバリア層、ガスバリア性樹脂からなるガスバリア層、無機膜からなるガスバリア層、高分子層の表面が改質されてなるガスバリ層〔この場合、ガスバリア層とは、改質された領域のみを意味するのではなく、「改質された領域を含む層」を意味する。〕等が挙げられる。
　これらの中でも、ガスバリア性、透明性、生産性等の観点から、無機膜からなるガスバリア層、高分子層の表面が改質されてなるガスバリ層が好ましい。 The gas barrier layer includes a gas barrier layer made of metal foil, a gas barrier layer made of thin glass, a gas barrier layer made of a gas barrier resin, a gas barrier layer made of an inorganic film, and a gas barrier layer in which the surface of the polymer layer is modified [in this case The gas barrier layer does not mean only the modified region, but means “a layer including the modified region”. ] Etc. are mentioned.
Among these, from the viewpoint of gas barrier properties, transparency, productivity, etc., a gas barrier layer made of an inorganic film and a gas burr layer formed by modifying the surface of the polymer layer are preferable.
　金属箔は、金属を薄く伸ばしたものである。金属箔としては、アルミニウム、ニッケル、ステンレス、鉄、銅、チタン等の金属箔が挙げられる。
　金属箔は、単層であってもよく、同一材料から成る層または異なる材料から成る層を積層させた積層体であってもよい。 Metal foil is a thin stretch of metal. As metal foil, metal foil, such as aluminum, nickel, stainless steel, iron, copper, titanium, is mentioned.
The metal foil may be a single layer or a laminate in which layers made of the same material or layers made of different materials are laminated.
　薄膜ガラスの材質としては、無アルカリガラス、硼珪酸ガラス、アルミノシリケートガラス等の多成分系酸化物ガラス等が挙げられる。 Examples of the material of the thin film glass include multi-component oxide glasses such as alkali-free glass, borosilicate glass, and aluminosilicate glass.
　ガスバリア性樹脂としては、ポリビニルアルコール、又はその部分ケン化物、エチレン－ビニルアルコール共重合体、ポリアクリロニトリル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリクロロトリフルオロエチレン等の、酸素や水蒸気等を透過しにくい樹脂が挙げられる。 As a gas barrier resin, polyvinyl alcohol, or a partially saponified product thereof, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, and the like are hardly permeable to oxygen, water vapor, and the like. Resin.
　無機膜としては、無機化合物や金属の蒸着膜が挙げられる。
　無機化合物の蒸着膜の原料としては、酸化珪素、酸化アルミニウム、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ等の無機酸化物；窒化ケイ素、窒化アルミニウム、窒化チタン等の無機窒化物；無機炭化物；無機硫化物；酸化窒化ケイ素等の無機酸化窒化物；無機酸化炭化物；無機窒化炭化物；無機酸化窒化炭化物等が挙げられる。
　金属の蒸着膜の原料としては、アルミニウム、マグネシウム、亜鉛、及びスズ等が挙げられる。
　これらは１種単独で、あるいは２種以上を組み合わせて用いることができる。
　これらの中では、ガスバリア性の観点から、無機酸化物、無機窒化物又は金属を原料とする無機蒸着膜が好ましく、さらに、透明性の観点から、無機酸化物又は無機窒化物を原料とする無機蒸着膜が好ましい。 Examples of the inorganic film include an inorganic compound and a metal deposited film.
As the raw material for the vapor-deposited film of the inorganic compound, 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; Inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides and the like.
Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
These can be used alone or in combination of two or more.
Among these, an inorganic vapor-deposited film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable from the viewpoint of gas barrier properties, and further, an inorganic material using an inorganic oxide or inorganic nitride as a raw material from the viewpoint of transparency. A vapor deposition film is preferred.
　無機膜を形成する方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法等のＰＶＤ（物理的蒸着）法や、熱ＣＶＤ（化学的蒸着）法、プラズマＣＶＤ法、光ＣＶＤ法等のＣＶＤ法が挙げられる。 As a method for forming the inorganic film, a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method or an ion plating method, a CVD method such as a thermal CVD (chemical vapor deposition) method, a plasma CVD method or a photo CVD method is used. Law.
　無機膜の厚みは、使用する無機化合物や金属によっても異なるが、ガスバリア性と取り扱い性の観点から、好ましくは１～２０００ｎｍ、より好ましくは３～１０００ｎｍ、より好ましくは５～５００ｎｍの範囲である。 The thickness of the inorganic film varies depending on the inorganic compound and metal used, but is preferably in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm from the viewpoint of gas barrier properties and handling properties.
　高分子層の表面が改質されてなるガスバリア層において、高分子層の形成に用いる高分子としては、ケイ素含有高分子化合物が挙げられる、 In the gas barrier layer formed by modifying the surface of the polymer layer, examples of the polymer used for forming the polymer layer include silicon-containing polymer compounds.
　ケイ素含有高分子化合物としては、ポリシラザン系化合物、ポリカルボシラン系化合物、ポリシラン系化合物、ポリオルガノシロキサン系化合物、ポリ（ジシラニレンフェニレン）系化合物、及びポリ（ジシラニレンエチニレン）系化合物等が挙げられ、ポリシラザン系化合物がより好ましい。 Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. And polysilazane compounds are more preferred.
　ポリシラザン系化合物は、分子内に－Ｓｉ－Ｎ－結合（シラザン結合）を含む繰り返し単位を有する化合物である。具体的には、式（１） The polysilazane compound is a compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the formula (1)
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
で表される繰り返し単位を有する化合物が好ましい。また、用いるポリシラザン系化合物の数平均分子量は、特に限定されないが、１００～５０，０００であるのが好ましい。 The compound which has a repeating unit represented by these is preferable. The number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably 100 to 50,000.
　前記式（１）中、ｎは任意の自然数を表す。Ｒｘ、Ｒｙ、Ｒｚは、それぞれ独立して、水素原子、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基又はアルキルシリル基等の非加水分解性基を表す。 In the formula (1), n represents an arbitrary natural number. 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, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group;
　前記無置換若しくは置換基を有するアルキル基のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－へキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～１０のアルキル基が挙げられる。 Examples of the alkyl group of the unsubstituted or substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
　無置換若しくは置換基を有するシクロアルキル基のシクロアルキル基としては、例えば、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロへプチル基等の炭素数３～１０のシクロアルキル基が挙げられる。 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.
　無置換若しくは置換基を有するアルケニル基のアルケニル基としては、例えば、ビニル基、１－プロペニル基、２－プロペニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基等の炭素数２～１０のアルケニル基が挙げられる。 Examples of the alkenyl group of an unsubstituted or substituted alkenyl group include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like having 2 to 2 carbon atoms. 10 alkenyl groups are mentioned.
　前記アルキル基、シクロアルキル基及びアルケニル基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシル基；チオール基；エポキシ基；グリシドキシ基；（メタ）アクリロイルオキシ基；フェニル基、４－メチルフェニル基、４－クロロフェニル基等の無置換若しくは置換基を有するアリール基；等が挙げられる。 Examples of the substituent for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
　無置換又は置換基を有するアリール基のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基等の炭素数６～１５のアリール基が挙げられる。 Examples of the aryl group of the unsubstituted or substituted aryl group include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
　前記アリール基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基等の炭素数１～６のアルキル基；メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基；ニトロ基；シアノ基；ヒドロキシル基；チオール基；エポキシ基；グリシドキシ基；（メタ）アクリロイルオキシ基；フェニル基、４－メチルフェニル基、４－クロロフェニル基等の無置換若しくは置換基を有するアリール基；等が挙げられる。 Examples of the substituent of the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc. An aryl group having a substituent; and the like.
　アルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、トリイソプロピルシリル基、トリｔ-ブチルシリル基、メチルジエチルシリル基、ジメチルシリル基、ジエチルシリル基、メチルシリル基、エチルシリル基等が挙げられる。 Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.
　これらの中でも、Ｒｘ、Ｒｙ、Ｒｚとしては、水素原子、炭素数１～６のアルキル基、又はフェニル基が好ましく、水素原子が特に好ましい。 Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.
　前記式（１）で表される繰り返し単位を有するポリシラザン系化合物としては、Ｒｘ、Ｒｙ、Ｒｚが全て水素原子である無機ポリシラザン、Ｒｘ、Ｒｙ、Ｒｚの少なくとも１つが水素原子ではない有機ポリシラザンのいずれであってもよい。 Examples of the polysilazane compound having a repeating unit represented by the 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.
　また、本発明においては、ポリシラザン系化合物として、ポリシラザン変性物を用いることもできる。ポリシラザン変性物としては、例えば、特開昭６２－１９５０２４号公報、特開平２－８４４３７号公報、特開昭６３－８１１２２号公報、特開平１－１３８１０８号公報等、特開平２－１７５７２６号公報、特開平５－２３８８２７号公報、特開平５－２３８８２７号公報、特開平６－１２２８５２号公報、特開平６－３０６３２９号公報、特開平６－２９９１１８号公報、特開平９－３１３３３号公報、特開平５－３４５８２６号公報、特開平４－６３８３３号公報等に記載されているものが挙げられる。
　これらの中でも、ポリシラザン系化合物としては、入手容易性、及び優れたガスバリア性を有するイオン注入層を形成できる観点から、Ｒｘ、Ｒｙ、Ｒｚが全て水素原子であるペルヒドロポリシラザンが好ましい。
　また、ポリシラザン系化合物としては、ガラスコーティング材等として市販されている市販品をそのまま使用することもできる。
　ポリシラザン系化合物は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 In the present invention, a modified polysilazane compound can also be used as the polysilazane compound. Examples of 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 Kaihei 5-345826 and JP-A-4-63833.
Among these, as the polysilazane compound, perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
Moreover, as a polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.
The polysilazane compounds can be used alone or in combination of two or more.
　高分子層は、ケイ素含有高分子化合物の他に、本発明の目的を阻害しない範囲で他の成分を含有してもよい。他の成分としては、硬化剤、老化防止剤、光安定剤、難燃剤等が挙げられる。
　高分子層中のケイ素含有高分子化合物の含有量は、よりガスバリア性に優れるガスバリア層を形成し得ることから、５０質量％以上が好ましく、７０質量％以上がより好ましい。 In addition to the silicon-containing polymer compound, the polymer layer may contain other components as long as the object of the present invention is not impaired. Examples of other components include a curing agent, an anti-aging agent, a light stabilizer, and a flame retardant.
The content of the silicon-containing polymer compound in the polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more because a gas barrier layer having better gas barrier properties can be formed.
　高分子層の厚みは、特に制限されないが、通常１～２０００ｎｍ、より好ましくは３～１０００ｎｍ、より好ましくは５～５００ｎｍの範囲である。 The thickness of the polymer layer is not particularly limited, but is usually in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, and more preferably 5 to 500 nm.
　高分子層は、例えば、ケイ素含有高分子化合物を有機溶剤に溶解又は分散した液を、公知の塗布方法によって、直接又はその他の層を介して基材層上に塗布し、得られた塗膜を乾燥することにより形成することができる。 The polymer layer is, for example, a coating film obtained by applying a solution obtained by dissolving or dispersing a silicon-containing polymer compound in an organic solvent directly or via another layer by a known coating method. Can be formed by drying.
　有機溶剤としては、ベンゼン、トルエンなどの芳香族炭化水素系溶媒；酢酸エチル、酢酸ブチルなどのエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタンなどの脂肪族炭化水素系溶媒；シクロペンタン、シクロヘキサンなどの脂環式炭化水素系溶媒；等が挙げられる。
　これらの溶媒は、１種単独で、あるいは２種以上を組み合わせて用いることができる。　 Examples of the organic 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, n -An aliphatic hydrocarbon solvent such as heptane; an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane;
These solvents can be used alone or in combination of two or more.
　塗布方法としては、バーコート法、スピンコート法、ディッピング法、ロールコート法、グラビアコート法、ナイフコート法、エアナイフコート法、ロールナイフコート法、ダイコート法、スクリーン印刷法、スプレーコート法、グラビアオフセット法等が挙げられる。 Coating methods include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, and gravure offset. Law.
　塗膜の乾燥方法としては、熱風乾燥、熱ロール乾燥、赤外線照射等、従来公知の乾燥方法が挙げられる。加熱温度は、通常、８０～１５０℃であり、加熱時間は、通常、数十秒から数十分である。 Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation. The heating temperature is usually 80 to 150 ° C., and the heating time is usually several tens of seconds to several tens of minutes.
　高分子層の表面を改質する方法としては、イオン注入処理、プラズマ処理、紫外線照射処理、熱処理等が挙げられる。
　イオン注入処理は、後述するように、加速させたイオンを高分子層に注入して、高分子層を改質する方法である。
　プラズマ処理は、高分子層をプラズマ中に晒して、高分子層を改質する方法である。例えば、特開２０１２－１０６４２１号公報に記載の方法に従って、プラズマ処理を行うことができる。
　紫外線照射処理は、高分子層に紫外線を照射して高分子層を改質する方法である。例えば、特開２０１３－２２６７５７号公報に記載の方法に従って、紫外線改質処理を行うことができる。 Examples of the method for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
As will be described later, 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. For example, 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. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
　高分子層に注入するイオンとしては、アルゴン、ヘリウム、ネオン、クリプトン、キセノン等の希ガスのイオン；フルオロカーボン、水素、窒素、酸素、二酸化炭素、塩素、フッ素、硫黄等のイオン；メタン、エタン等のアルカン系ガス類のイオン；エチレン、プロピレン等のアルケン系ガス類のイオン；ペンタジエン、ブタジエン等のアルカジエン系ガス類のイオン；アセチレン等のアルキン系ガス類のイオン；ベンゼン、トルエン等の芳香族炭化水素系ガス類のイオン；シクロプロパン等のシクロアルカン系ガス類のイオン；シクロペンテン等のシクロアルケン系ガス類のイオン；金属のイオン；有機ケイ素化合物のイオン；等が挙げられる。
　これらのイオンは１種単独で、あるいは２種以上を組み合わせて用いることができる。
　これらの中でも、より簡便にイオンを注入することができ、より優れたガスバリア性を有するガスバリア層を形成し得ることから、アルゴン、ヘリウム、ネオン、クリプトン、キセノン等の希ガスのイオンが好ましい。 As 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, etc. Ion of alkane gases such as ethylene and propylene; Ions of alkadiene gases such as pentadiene and butadiene; Ions of alkyne gases such as acetylene; Aromatic carbonization such as benzene and toluene Examples include ions of hydrogen-based gases; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; ions of metals; ions of organosilicon compounds.
These ions can 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 easily implanted and a gas barrier layer having better gas barrier properties can be formed.
　イオンの注入量は、ガスバリア性積層体の使用目的（必要なガスバリア性、透明性等）等に合わせて適宜決定することができる。 The ion implantation amount can be appropriately determined according to the purpose of use of the gas barrier laminate (necessary gas barrier properties, transparency, etc.).
　イオンを注入する方法としては、電界により加速されたイオン（イオンビーム）を照射する方法、プラズマ中のイオンを注入する方法等が挙げられる。なかでも、簡便に目的のガスバリア層を形成できることから、後者のプラズマ中のイオンを注入する方法（プラズマイオン注入法）が好ましい。 Examples of the method of 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. Of these, the latter method of injecting ions in plasma (plasma ion implantation method) is preferable because the target gas barrier layer can be easily formed.
　プラズマイオン注入法は、例えば、希ガス等のプラズマ生成ガスを含む雰囲気下でプラズマを発生させ、高分子層に負の高電圧パルスを印加することにより、該プラズマ中のイオン（陽イオン）を、高分子層の表面部に注入して行うことができる。プラズマイオン注入法は、より具体的には、ＷＯ２０１０／１０７０１８号パンフレット等に記載された方法により実施することができる。 In the plasma ion implantation method, for example, 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.
　イオン注入により、イオンが注入される領域の厚みは、イオンの種類や印加電圧、処理時間等の注入条件により制御することができ、高分子層の厚みや積層体の使用目的等に応じて決定すればよいが、通常、１０～４００ｎｍである。 By ion implantation, the thickness of the region into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, and processing time, and is determined according to the thickness of the polymer layer and the purpose of use of the laminate. Usually, it is 10 to 400 nm.
　イオンが注入されたことは、Ｘ線光電子分光分析（ＸＰＳ）を用いて高分子層の表面から１０ｎｍ付近の元素分析測定を行うことによって確認することができる。 The ion implantation can be confirmed by performing an elemental analysis measurement in the vicinity of 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).
　ガスバリア性フィルムは、温度４０℃、相対湿度９０％（以下、「９０％ＲＨ」と略記する。）の環境下における水蒸気透過率が０．１ｇ／ｍ２／ｄａｙ以下であることが好ましく、０．０５ｇ／ｍ２／ｄａｙ以下であることがより好ましく、０．００５ｇ／ｍ２／ｄａｙ以下であることがさらに好ましい。
　ガスバリア性フィルムの温度４０℃、９０％ＲＨの環境下における水蒸気透過率が０．１ｇ／ｍ２／ｄａｙ以下であることで、透明基板上に形成された有機ＥＬ素子等の素子内部に酸素や水分等が浸入し、電極や有機層が劣化することを効果的に抑制することができる。
　ガスバリア性フィルムの水蒸気等の透過率は、公知のガス透過率測定装置を使用して測定することができる。 The gas barrier film preferably has a water vapor transmission rate of 0.1 g / m 2 / day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90% (hereinafter abbreviated as “90% RH”). It is more preferable that it is 0.05 g / m 2 / day or less, and it is more preferable that it is 0.005 g / m 2 / day or less.
The gas barrier film has a water vapor permeability of 0.1 g / m 2 / day or less in an environment of 40 ° C. and 90% RH, so that oxygen or oxygen can be contained inside the organic EL element or the like formed on the transparent substrate. It is possible to effectively suppress the penetration of moisture and the like and the deterioration of the electrode and the organic layer.
The transmittance of water vapor and the like of the gas barrier film can be measured using a known gas permeability measuring device.
　プライマー層としては特に限定されず、公知のものが使用できる。例えば、WO２０１２／０３９３８７号、WO２０１３／１４７０９０号等に記載されたプライマー層等が挙げられる。 The primer layer is not particularly limited, and a known layer can be used. For example, the primer layer etc. which were described in WO2012 / 039387, WO2013 / 147090 etc. are mentioned.
　封止シート（β）の製造方法は特に限定されない。例えば、先に説明した封止シート（α）の製造方法において、剥離フィルムの１枚をガスバリア性フィルムに置き換えることで封止シート（β）を製造することができる。
　また、封止シート（α）を製造した後、その１枚の剥離フィルムを剥離し、露出した粘着剤層とガスバリア性フィルムとを貼着することにより、封止シート（β）を製造することもできる。この場合、封止シート(α)が、異なる剥離力を有する２枚の剥離フィルムを有する場合には、取扱い性の観点から、剥離力の小さい方の剥離フィルムを剥離するのが好ましい。 The manufacturing method of a sealing sheet ((beta)) is not specifically limited. For example, in the manufacturing method of the sealing sheet (α) described above, the sealing sheet (β) can be manufactured by replacing one of the release films with a gas barrier film.
Moreover, after manufacturing a sealing sheet ((alpha)), the sealing sheet ((beta)) is manufactured by peeling the one peeling film and sticking the exposed adhesive layer and a gas-barrier film. You can also. In this case, when the sealing sheet (α) has two release films having different release forces, it is preferable to release the release film having the smaller release force from the viewpoint of handleability.
　本発明の封止シートの粘着剤層は、粘着力及び水分遮断性に優れる。このため、本発明の封止シートを用いて有機ＥＬ素子を封止することで、その劣化を効率よく抑えることができる。 The pressure-sensitive adhesive layer of the sealing sheet of the present invention is excellent in adhesive strength and moisture barrier properties. For this reason, the deterioration can be efficiently suppressed by sealing an organic EL element using the sealing sheet of this invention.
３）封止体
　本発明の封止体は、被封止物が、本発明の封止シートを用いて封止されてなるものである。
　「被封止物が、本発明の封止シートを用いて封止されてなる」とは、本発明の封止シートを構成する剥離フィルムを除去して粘着剤層を露出させ、その粘着剤層を被封止物に密着させて、被封止物を覆うことをいう。
　本発明の封止体としては、例えば、透明基板と、該透明基板上に形成された素子（被封止物）と、該素子を封止するための封止材とを備えるものであって、前記封止材が、本発明の封止シートの粘着剤層であるものが挙げられる。 3) Sealing body The sealing body of the present invention is such that an object to be sealed is sealed using the sealing sheet of the present invention.
“The sealed object is sealed using the sealing sheet of the present invention” means that the release film constituting the sealing sheet of the present invention is removed to expose the pressure-sensitive adhesive layer. It means that a layer is brought into close contact with an object to be sealed to cover the object to be sealed.
The sealing body of the present invention includes, for example, a transparent substrate, an element (an object to be sealed) formed on the transparent substrate, and a sealing material for sealing the element. The said sealing material is what is the adhesive layer of the sealing sheet of this invention.
　透明基板は、特に限定されるものではなく、種々の基板材料を用いることができる。特に可視光の透過率が高い基板材料を用いることが好ましい。また、素子外部から浸入しようとする水分やガスを阻止する遮断性能が高く、耐溶剤性や耐候性に優れている材料が好ましい。具体的には、石英やガラスなどの透明無機材料；ポリエチレンテレフタラート、ポリエチレンナフタラート、ポリカーボネート、ポリスチレン、ポリエチレン、ポリプロピレン、ポリフェニレンスルフィド、ポリフッ化ビニリデン、アセチルセルロース、ブロム化フェノキシ、アラミド類、ポリイミド類、ポリスチレン類、ポリアリレート類、ポリスルホン類、ポリオレフィン類などの透明プラスチック、前述したガスバリア性フィルム；が挙げられる。
　透明基板の厚みは特に制限されず、光の透過率や、素子内外を遮断する性能を勘案して、適宜選択することができる。 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 a high blocking performance for blocking moisture and gas to enter from the outside of the element and having excellent solvent resistance and weather resistance is preferable. Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, Examples thereof include transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins, and the gas barrier film described above.
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance for blocking the inside and outside of the element.
　被封止物としては、有機ＥＬ素子、有機ＥＬディスプレイ素子、液晶ディスプレイ素子、太陽電池素子等が挙げられる。 Examples of the objects to be sealed include organic EL elements, organic EL display elements, liquid crystal display elements, solar cell elements, and the like.
　本発明の封止体の製造方法は特に限定されない。例えば、本発明の封止シートの粘着剤層を被封止物上に重ねて貼着することにより、封止シートの粘着剤層と被封止物を粘着させる。 The manufacturing method of the sealing body of the present invention is not particularly limited. For example, the pressure-sensitive adhesive layer of the sealing sheet of the present invention is stuck on the object to be sealed, and the pressure-sensitive adhesive layer of the sealing sheet and the object to be sealed are adhered.
　本発明の封止体は、被封止物が、本発明の封止シートで封止されてなるものである。
　したがって、本発明の封止体においては、長期にわたって被封止物の性能が維持される。 The sealing body of the present invention is formed by sealing an object to be sealed with the sealing sheet of the present invention.
Therefore, in the sealed body of the present invention, the performance of the object to be sealed is maintained for a long time.
　以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は、以下の実施例になんら限定されるものではない。
　各例中の部及び％は、特に断りのない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.
〔製造例１〕
　（メタ）アクリレート系電離放射線硬化型化合物として、ジペンタエリスリトールヘキサアクリレート（新中村化学社製、商品名：Ａ－ＤＰＨ）２０部をメチルイソブチルケトン１００部に溶解させた後、光重合開始剤（ＢＡＳＦ社製、商品名：Ｉｒｇａｃｕｒｅ１２７）を、プライマー層形成用溶液の固形分１００部に対して、その量が３部になるように添加してプライマー層形成用溶液を調製した。
　次いで、厚みが５０μｍのポリエチレンテレフタレートフィルム（以下、「ＰＥＴフィルム」という。）（東洋紡社製、コスモシャインＡ－４３００）上に、上記のプライマー層形成用溶液を塗布し、得られた塗膜を乾燥させることで、厚み１μｍのプライマー層を形成した。
　次いで、このプライマー層上にペルヒドロポリシラザンを主成分とするコーティング剤（メルクパフォーマンスマテリアルズ社製、「ＡＺＮＮ１１０－２０」）を塗布し、得られた塗膜を１２０℃で２分間加熱することにより、厚み２００ｎｍのポリシラザン層を形成した。
　次いで、このポリシラザン層に、プラズマイオン注入装置を用いて、下記条件にてプラズマイオン注入を行い、ポリシラザン層の表面を改質し、ガスバリア性フィルムを得た。
　このガスバリア性フィルムの水蒸気透過率は、０．０２ｇ／ｍ２／ｄａｙであった。 [Production Example 1]
As a (meth) acrylate ionizing radiation curable compound, 20 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) was dissolved in 100 parts of methyl isobutyl ketone, and then a photopolymerization initiator ( A primer layer forming solution was prepared by adding BASF, trade name: Irgacure 127) to 100 parts of the solid content of the primer layer forming solution so that the amount thereof was 3 parts.
Next, the primer layer forming solution was applied onto a 50 μm thick polyethylene terephthalate film (hereinafter referred to as “PET film”) (Toyobo Co., Ltd., Cosmo Shine A-4300). By drying, a primer layer having a thickness of 1 μm was formed.
Next, a coating agent mainly composed of perhydropolysilazane (“AZNN110-20” manufactured by Merck Performance Materials Co., Ltd.) is applied on the primer layer, and the obtained coating film is heated at 120 ° C. for 2 minutes. A polysilazane layer having a thickness of 200 nm was formed.
Next, plasma ion implantation was performed on the polysilazane layer under the following conditions using a plasma ion implantation apparatus to modify the surface of the polysilazane layer to obtain a gas barrier film.
The water vapor transmission rate of this gas barrier film was 0.02 g / m 2 / day.
［プラズマイオン注入の処理条件］
プラズマ生成ガス：アルゴン
ガス流量：１００ｓｃｃｍ
Ｄｕｔｙ比：０．５％
繰り返し周波数：１０００Ｈｚ
印加電圧：－１０ｋＶ
ＲＦ出力：１０００Ｗ
ＲＦ電源：（周波数）１３．５６ＭＨｚ、（印加電力）１０００Ｗ
チャンバー内圧：０．２Ｐａ
パルス幅：５μｓｅｃ
処理時間（イオン注入時間）：５分間
搬送速度：０．２ｍ／ｍｉｎ [Processing conditions for plasma ion implantation]
Plasma generation gas: Argon gas flow rate: 100 sccm
Duty ratio: 0.5%
Repeat frequency: 1000Hz
Applied voltage: -10kV
RF output: 1000W
RF power supply: (frequency) 13.56 MHz, (applied power) 1000 W
Chamber internal pressure: 0.2 Pa
Pulse width: 5μsec
Processing time (ion implantation time): 5 minutes Conveying speed: 0.2 m / min
〔実施例又は比較例で用いた化合物〕
　実施例又は比較例においては、以下の化合物を使用した。
ゴム系樹脂（１）：ブチルゴム、質量平均分子量（Ｍｗ）：３４，０００、ＪＳＲ株式会社製、商品名：ＪＳＲ　ＢＵＴＹＬ２６８
ゴム系樹脂（２）：ブチルゴム、質量平均分子量（Ｍｗ）：２８，０００、ＪＳＲ株式会社製、商品名：ＪＳＲ　ＢＵＴＹＬ３６５
粘着付与剤（１）：脂肪族系石油樹脂、日本ゼオン株式会社製、商品名：クイントンＡ－１００
硬化性樹脂（１）：水素化ポリブタジエンポリオール、Ｃｒａｙ　Ｖａｌｌｅｙ社製、商品名：Ｋｒａｓｏｌ　ＨＬＢＨ－Ｐ２０００
硬化性樹脂（２）：ポリブタジエンポリオール、Ｃｒａｙ　Ｖａｌｌｅｙ社製、商品名：Ｋｒａｓｏｌ　ＬＢＨ－Ｐ２０００
架橋剤（１）：アロファネート変性ヘキサメチレンジイソシアネート、三井化学株式会社製、商品名：タケネートＤ－１７８ＮＬ
架橋剤（２）：ペンタメチレンジイソシアネート系ポリイソシアネート、三井化学株式会社製、商品名：スタビオ　Ｄ－３７０Ｎ
シランカップリング剤（１）：８－（アミノエチルアミノ）オクチルトリメトキシシラン、信越化学工業株式会社製、商品名：ＫＢＭ６８０３
シランカップリング剤（２）：３－グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社製、商品名：ＫＢＭ４０３
シランカップリング剤（３）：８－グリシドキシオクチルトリメトキシシラン、信越化学工業株式会社製、商品名：ＫＢＭ４８０３ [Compounds used in Examples or Comparative Examples]
In the examples or comparative examples, the following compounds were used.
Rubber-based resin (1): butyl rubber, mass average molecular weight (Mw): 34,000, manufactured by JSR Corporation, trade name: JSR BUTYL268
Rubber-based resin (2): butyl rubber, mass average molecular weight (Mw): 28,000, manufactured by JSR Corporation, trade name: JSR BUTYL365
Tackifier (1): Aliphatic petroleum resin, manufactured by Nippon Zeon Co., Ltd., trade name: Quinton A-100
Curable resin (1): hydrogenated polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol HLBH-P2000
Curable resin (2): Polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol LBH-P2000
Crosslinking agent (1): Allophanate-modified hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc., trade name: Takenate D-178NL
Crosslinking agent (2): pentamethylene diisocyanate polyisocyanate, manufactured by Mitsui Chemicals, Inc., trade name: STAVIO D-370N
Silane coupling agent (1): 8- (aminoethylamino) octyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM6803
Silane coupling agent (2): 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403
Silane coupling agent (3): 8-glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM4803
〔実施例１〕
　ゴム系樹脂（１）８０部、ゴム系樹脂（２）２０部、粘着付与剤（１）２０部、硬化性樹脂（１）１５部、架橋剤（１）５部、及び、シランカップリング剤（１）０．１部をトルエンに溶解し、固形分濃度１７％の粘着剤組成物（１）を調製した。
　この粘着剤組成物（１）を剥離フィルム（リンテック社製、商品名：ＳＰ－ＰＥＴ３８２１５０）の剥離処理面上に塗工し、得られた塗膜を１００℃で１分間乾燥し、厚みが２０μｍの粘着剤層を形成し、その上に、もう１枚の剥離フィルム（リンテック社製、商品名：ＳＰ－ＰＥＴ３８１０３１）の剥離処理面を貼り合わせて封止シート（１）を得た。 [Example 1]
80 parts of rubber-based resin (1), 20 parts of rubber-based resin (2), 20 parts of tackifier (1), 15 parts of curable resin (1), 5 parts of cross-linking agent (1), and silane coupling agent (1) 0.1 part was dissolved in toluene to prepare an adhesive composition (1) having a solid content concentration of 17%.
This pressure-sensitive adhesive composition (1) was applied onto the release-treated surface of a release film (product name: SP-PET382150, manufactured by Lintec Corporation), and the obtained coating film was dried at 100 ° C. for 1 minute, and the thickness was 20 μm. A release sheet (1) was obtained by pasting the release-treated surface of another release film (trade name: SP-PET381031 manufactured by Lintec Corporation) on the adhesive layer.
〔実施例２～８、比較例１〕
　第１表に記載の組成に変更して粘着剤組成物（２）～（９）を調製し、これらの粘着剤組成物を使用したこと以外は、実施例１と同様にして、封止シート（２）～（９）を得た。 [Examples 2 to 8, Comparative Example 1]
A sealing sheet was prepared in the same manner as in Example 1 except that pressure-sensitive adhesive compositions (2) to (9) were prepared by changing to the compositions shown in Table 1 and these pressure-sensitive adhesive compositions were used. (2) to (9) were obtained.
　実施例１～８、比較例１で得た封止シート（１）～（９）について、以下の試験を行った。なお、試験は、封止シートを作成後、２３℃相対湿度５０％環境下で、７日間養生した後に行った。
〔粘着力測定〕
　幅が２５ｍｍの封止シートの剥離フィルムを１枚剥がして露出させた粘着剤層を、製造例１で得られたガスバリア性フィルムに重ねた。次いで、もう１枚の剥離フィルムを剥がして露出させた粘着剤層を無アルカリガラスに重ね、圧着ロールで圧着させることにより、試験片を得た。
　剥離試験（ａ）として、試験片を、温度２３℃、相対湿度５０％の条件下で１８０°剥離試験を行った。
　剥離試験（ｂ）として、試験片を、温度６０℃、相対湿度９０％の条件下に１６８時間、次いで、温度２３℃、相対湿度５０％の条件下に２４時間静置させた後に、温度２３℃、相対湿度５０％条件下で１８０°剥離試験を行った。
　この剥離試験において、上述した試験条件以外は、ＪＩＳ　Ｚ０２３７：２０００に記載の粘着力の測定方法に準じて行った。 The following tests were performed on the sealing sheets (1) to (9) obtained in Examples 1 to 8 and Comparative Example 1. The test was carried out after the sealing sheet was prepared and then cured for 7 days in an environment of 23 ° C. and 50% relative humidity.
(Adhesion measurement)
The pressure-sensitive adhesive layer exposed by peeling off one release film of the sealing sheet having a width of 25 mm was overlaid on the gas barrier film obtained in Production Example 1. Then, another test piece was obtained by peeling the other release film and exposing the pressure-sensitive adhesive layer on non-alkali glass and press-bonding it with a press roll.
As a peel test (a), the test piece was subjected to a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%.
As a peel test (b), the test piece was allowed to stand for 168 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, and then for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. A 180 ° peel test was conducted under the conditions of 50 ° C. and 50% relative humidity.
In this peeling test, the test was performed according to the method for measuring adhesive strength described in JIS Z0237: 2000 except for the test conditions described above.
〔ブリスター性評価〕
　１辺１２５ｍｍの正方形状の封止シートの剥離フィルムを１枚剥がして露出させた粘着剤層を、製造例１で得られたガスバリア性フィルムに重ねた。次いで、もう１枚の剥離フィルムを剥がして露出させた粘着剤層を無アルカリガラスに重ね、ロールラミネーターを用いてこれらを貼着した。その後、加熱加圧オーブン（リンテック社製、型番：ＲＡＤ－９１００）にて、温度５０℃、圧力０．５ＭＰａ条件下で２０分処理することで試験片を得た。この試験片を、恒温恒湿器（エスペック社製、型番：ＰＬ－２ＫＴ）に入れ、温度８５℃、相対湿度８５％の環境下に７２時間静置した後、目視観察を行い、以下の基準によりブリスター性を評価した。
○：膨れの発生個数が５個未満
×：膨れの発生個数が５個以上 [Blister evaluation]
The pressure-sensitive adhesive layer, which was exposed by peeling off one release film of a square-shaped sealing sheet having a side of 125 mm, was superimposed on the gas barrier film obtained in Production Example 1. Next, another pressure-sensitive adhesive layer was peeled and exposed, and the pressure-sensitive adhesive layer was stacked on an alkali-free glass, and these were stuck using a roll laminator. Thereafter, a test piece was obtained by treatment in a heating and pressurizing oven (manufactured by Lintec Corporation, model number: RAD-9100) at a temperature of 50 ° C. and a pressure of 0.5 MPa for 20 minutes. This test piece was placed in a thermo-hygrostat (Model number: PL-2KT, manufactured by ESPEC Corp.), allowed to stand in an environment at a temperature of 85 ° C. and a relative humidity of 85% for 72 hours, and then visually observed. Was used to evaluate blister properties.
○: Number of blisters generated is less than 5 ×: Number of blisters generated is 5 or more
〔有機ＥＬ素子の評価試験〕
　酸化インジウムスズ（ＩＴＯ）膜（厚み：１００ｎｍ、シート抵抗：５０Ω／□）が成膜されたガラス基板を陽極として有する有機ＥＬ素子を、以下の方法により作製した。
　まず、前記ガラス基板のＩＴＯ膜上に、Ｎ，Ｎ’－ビス（ナフタレン－１－イル）－Ｎ，Ｎ’－ビス（フェニル）－ベンジジン）（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を５０ｎｍ、トリス（８－ヒドロキシ－キノリネート）アルミニウム（Ｌｕｍｉｎｅｓｃｅｎｃｅ　Ｔｅｃｈｎｏｌｏｇｙ社製）を５０ｎｍ、０．１～０．２ｎｍ／分の速度で順次蒸着させ、発光層を形成した。
　得られた発光層上に、電子注入材料として、フッ化リチウム（ＬｉＦ）（高純度化学研究所社製）を０．１ｎｍ／分の速度で４ｎｍ、次いでアルミニウム（Ａｌ）（高純度化学研究所社製）を０．１ｎｍ／分の速度で１００ｎｍ蒸着させて陰極を形成し、有機ＥＬ素子を得た。
　なお、蒸着時の真空度は、全て１×１０－４Ｐａ以下であった。 [Evaluation test of organic EL elements]
An organic EL element having a glass substrate on which an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50Ω / □) was formed as an anode was produced by the following method.
First, on the ITO film of the glass substrate, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidine) (made by Luminescence Technology) 50 nm, Tris (8- Hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) was sequentially deposited at a rate of 50 nm and a rate of 0.1 to 0.2 nm / min to form a light emitting layer.
On the obtained light emitting layer, as an electron injection material, lithium fluoride (LiF) (manufactured by High-Purity Chemical Laboratory) is 4 nm at a rate of 0.1 nm / min, and then aluminum (Al) (high-purity chemical laboratory) The cathode was formed by vapor-depositing 100 nm at a rate of 0.1 nm / min to obtain an organic EL device.
The degree of vacuum at the time of vapor deposition was 1 × 10 −4 Pa or less.
　実施例又は比較例で得た封止シートの剥離フィルムを１枚剥がし、露出した粘着剤層を、製造例１で得られたガスバリア性フィルム上に重ね、ロールラミネーターを用いてこれらを貼着した。次いで、もう１枚の剥離フィルムを剥離し、露出した粘着剤層を、ガラス基板上に形成された有機ＥＬ素子を覆うように重ね、ロールラミネーターを用いてこれらを貼着し、有機ＥＬ素子が封止されたボトムエミッション型の電子デバイスを得た。
　この電子デバイスを、温度６０℃、相対湿度９０％の環境下に２５０時間静置させた後、有機ＥＬ素子を起動させ、ダークスポット（非発光箇所）の有無を観察し、全体に対するダークスポットの面積の割合を算出した。 One release film of the sealing sheet obtained in Example or Comparative Example was peeled off, and the exposed pressure-sensitive adhesive layer was stacked on the gas barrier film obtained in Production Example 1, and these were attached using a roll laminator. . Next, the other release film is peeled off, and the exposed adhesive layer is stacked so as to cover the organic EL element formed on the glass substrate, and these are attached using a roll laminator, A sealed bottom emission type electronic device was obtained.
This electronic device is allowed to stand for 250 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%, and then the organic EL element is activated to observe the presence or absence of dark spots (non-light emitting portions). The area ratio was calculated.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　第１表から以下のことがわかる。
　実施例１～８の封止シート（１）～（８）は、高湿条件静置後においてより優れた粘着力を示し、また、封止性に優れている。
　一方、比較例１の封止シート（９）は、粘着力が小さく、また、高湿条件に置くと、粘着力が大きく低下する。そして、封止シート（９）は、封止性に劣っている。 Table 1 shows the following.
The sealing sheets (1) to (8) of Examples 1 to 8 show better adhesive strength after standing under high humidity conditions, and are excellent in sealing properties.
On the other hand, the sealing sheet (9) of Comparative Example 1 has a small adhesive force, and when placed in a high humidity condition, the adhesive force is greatly reduced. And the sealing sheet (9) is inferior to sealing performance.

Claims (18)

  1. 　下記の（Ａ）成分、（Ｃ）成分、及び（Ｄ）成分を含有する粘着剤組成物。
    （Ａ）成分：ゴム系樹脂
    （Ｃ）成分：硬化性樹脂
    （Ｄ）成分：アロファネート系架橋剤     The adhesive composition containing the following (A) component, (C) component, and (D) component.
    (A) component: rubber-based resin (C) component: curable resin (D) component: allophanate-based crosslinking agent
  2. 　前記（Ａ）成分が、ブチルゴムである、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the component (A) is butyl rubber.
  3. 　さらに、下記の（Ｂ）成分を含有する、請求項１又は２に記載の粘着剤組成物。
    （Ｂ）成分：粘着付与剤     Furthermore, the adhesive composition of Claim 1 or 2 containing the following (B) component.
    (B) component: Tackifier
  4. 　前記（Ｂ）成分が、脂肪族系石油樹脂である、請求項３に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 3, wherein the component (B) is an aliphatic petroleum resin.
  5. 　前記（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対して１～５０質量部である、請求項３又は４に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 3 or 4, wherein the content of the component (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  6. 　前記（Ｃ）成分が、両末端に水酸基を有する重合体である、請求項１～５のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the component (C) is a polymer having hydroxyl groups at both ends.
  7. 　前記（Ｃ）成分の含有量が、（Ａ）成分１００質量部に対して１～５０質量部である、請求項１～６のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the content of the component (C) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  8. 　前記（Ｄ）成分が、アロファネート変性ヘキサメチレンジイソシアネートである、請求項１～７のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the component (D) is allophanate-modified hexamethylene diisocyanate.
  9. 　前記（Ｄ）成分の含有量が、（Ａ）成分１００質量部に対して１～７０質量部である、請求項１～８のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 8, wherein the content of the component (D) is 1 to 70 parts by mass with respect to 100 parts by mass of the component (A).
  10. 　さらに、下記の（Ｅ）成分を含有する、請求項１～９のいずれかに記載の粘着剤組成物。
    （Ｅ）成分：シランカップリング剤     The pressure-sensitive adhesive composition according to any one of claims 1 to 9, further comprising the following component (E):
    (E) component: Silane coupling agent
  11. 　前記（Ｅ）成分が、下記式（１）で示される化合物である、請求項１０に記載の粘着剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     （Ｒ１は炭素数３以上のアルキレン基を表し、Ｒ２は炭素数１～１０の１価の炭化水素基を表し、Ｒ３は炭素数１～４のアルキル基を表す。Ｚは反応性基を含有する基を表し、ｎは０又は１である。）     The pressure-sensitive adhesive composition according to claim 10, wherein the component (E) is a compound represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (R 1 represents an alkylene group having 3 or more carbon atoms, R 2 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 represents an alkyl group having 1 to 4 carbon atoms, and Z represents reactivity. Represents a group containing a group, and n is 0 or 1.)
  12. 　前記（Ｅ）成分の含有量が、前記（Ａ）成分１００質量部に対して０．０１～７質量部である、請求項１０又は１１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 10 or 11, wherein the content of the component (E) is 0.01 to 7 parts by mass with respect to 100 parts by mass of the component (A).
  13. 　２枚の剥離フィルムと、これらの剥離フィルムに挟持された粘着剤層とからなる封止シートであって、
    　前記粘着剤層が、請求項１～１２のいずれかに記載の粘着剤組成物を用いて形成されたものである封止シート。     A sealing sheet composed of two release films and an adhesive layer sandwiched between these release films,
    A sealing sheet, wherein the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition according to any one of claims 1 to 12.
  14. 　剥離フィルム、ガスバリア性フィルム、及び、前記剥離フィルムとガスバリア性フィルムに挟持された粘着剤層からなる封止シートであって、
    　前記粘着剤層が、請求項１～１２のいずれかに記載の粘着剤組成物を用いて形成されたものである封止シート。     A release film, a gas barrier film, and a sealing sheet comprising an adhesive layer sandwiched between the release film and the gas barrier film,
    A sealing sheet, wherein the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition according to any one of claims 1 to 12.
  15. 　前記ガスバリア性フィルムが、金属箔、樹脂製フィルム、又は薄膜ガラスである請求項１４に記載の封止シート。 The sealing sheet according to claim 14, wherein the gas barrier film is a metal foil, a resin film, or a thin film glass.
  16. 　粘着剤層の厚みが１～５０μｍである、請求項１３～１５のいずれかに記載の封止シート。 The sealing sheet according to any one of claims 13 to 15, wherein the pressure-sensitive adhesive layer has a thickness of 1 to 50 µm.
  17. 　被封止物が、請求項１３～１６のいずれかに記載の封止シートを用いて封止されてなる封止体。 A sealed body obtained by sealing an object to be sealed using the sealing sheet according to any one of claims 13 to 16.
  18. 　前記被封止物が、有機ＥＬ素子、有機ＥＬディスプレイ素子、液晶ディスプレイ素子、又は太陽電池素子である、請求項１７に記載の封止体。 The sealing body according to claim 17, wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.
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CN111218240A (en) * 2020-03-27 2020-06-02 山东双圆密封科技有限公司 Dynamic cross-linking type hot-melt butyl self-adhesive sealant and preparation method thereof

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