TWI753008B - Gas barrier layered body and sealing body - Google Patents

Gas barrier layered body and sealing body Download PDF

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TWI753008B
TWI753008B TW106130606A TW106130606A TWI753008B TW I753008 B TWI753008 B TW I753008B TW 106130606 A TW106130606 A TW 106130606A TW 106130606 A TW106130606 A TW 106130606A TW I753008 B TWI753008 B TW I753008B
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gas barrier
layered product
adhesive layer
layer
adhesive composition
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TW201815561A (en
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西嶋健太
長谷川樹
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日商琳得科股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1339Gaskets; Spacers; Sealing of cells
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/04Semiconductor 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
    • H01L31/042PV modules or arrays of single PV cells
    • H01L31/048Encapsulation of modules
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • H05B33/04Sealing arrangements, e.g. against humidity
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/842Containers
    • H10K50/8426Peripheral sealing arrangements, e.g. adhesives, sealants
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electromagnetism (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)
  • Photovoltaic Devices (AREA)

Abstract

本發明提供一種氣體障壁性層合體,其具有使含高分子化合物且施以改質處理的氣體障壁層與接著劑層直接層合的構成。本發明之氣體障壁性層合體所具有之接著劑層之形成材料的接著劑組成物至少含有多官能環氧化合物(B)且進而含有聚烯烴系樹脂(A),而且由該接著劑組成物所形成之特定薄片狀物的水蒸氣透過率係調整為200g/m2 /day以下。藉此,本發明之氣體障壁性層合體由於經由接著劑層之水分朝被密封物浸入的抑制效果高而具有優異之層間密著性,故可成為被密封物劣化之抑制效果高的密封材。The present invention provides a gas barrier layered product having a configuration in which a gas barrier layer containing a polymer compound and subjected to a modification treatment and an adhesive layer are directly laminated. The adhesive composition of the material for forming the adhesive layer of the gas barrier layered product of the present invention contains at least the polyfunctional epoxy compound (B) and further contains the polyolefin-based resin (A), and is composed of the adhesive composition. The water vapor transmission rate of the formed specific flakes is adjusted to be 200 g/m 2 /day or less. Thereby, the gas barrier layered product of the present invention has a high effect of suppressing the penetration of moisture into the object to be sealed via the adhesive layer, and has excellent interlayer adhesion, so that it can be a sealing material with a high effect of suppressing the deterioration of the object to be sealed. .

Description

氣體障壁性層合體、及密封體Gas barrier layered body and sealing body

[0001] 本發明有關氣體障壁性層合體及將被密封體以該氣體障壁性層合體密封而成之密封體。[0001] The present invention relates to a gas barrier layered body and a sealing body obtained by sealing a to-be-sealed body with the gas barrier layered body.

[0002] 近幾年來,液晶顯示器或電致發光(EL)顯示器等之顯示器為了實現薄型化、輕量化、可撓化等,作為具有電極之基板,係代替玻璃板而使用具有氣體障壁性之氣體障壁性薄膜。   又,藉由於氣體障壁性薄膜上層合其他層,亦開發具有新的功能之薄膜。   例如,專利文獻1中記載於附氣體障壁層之基材(氣體障壁性薄膜)之氣體障壁層上形成黏著劑層之黏著薄片。於專利文獻1中,記載使用該黏著薄片,而可效率良好地密封有機EL元件等之主旨。 [先前技術文獻] [專利文獻]   [0003] [專利文獻1] WO2012/032907號In recent years, in order to achieve thinning, weight reduction, flexibility, etc. of displays such as liquid crystal displays and electroluminescence (EL) displays, as substrates with electrodes, instead of glass plates, gas barrier properties have been used. Gas barrier film. In addition, by laminating other layers on the gas barrier film, films with new functions are also developed. For example, Patent Document 1 describes an adhesive sheet in which an adhesive layer is formed on the gas barrier layer of the gas barrier layer-attached substrate (gas barrier film). In Patent Document 1, it is described that an organic EL element or the like can be efficiently sealed by using this adhesive sheet. [Prior Art Document] [Patent Document] [0003] [Patent Document 1] WO2012/032907

[發明欲解決之課題]   [0004] 一般,於氣體障壁性薄膜具有之氣體障壁層上直接層合含有樹脂之樹脂層而構成時,由於氣體障壁層與樹脂之親和性低,故有氣體障壁層與樹脂之層間密著性產生問題之情況。尤其使用含高分子化合物且施以改質處理的氣體障壁層時,該氣體障壁層與樹脂之層間密著性多數情況較差。   [0005] 另一方面,專利文獻1中,並未針對氣體障壁層與樹脂之層間密著性進行檢討。使用如專利文獻1記載之黏著薄片密封有機EL元件時,氣體障壁層與樹脂之層間密著性低時,因水分等自兩層間浸入,而容易產生有機EL元件之發光特性降低。   又,用以密封有機EL元件所用之密封材,不僅對於氣體障壁層要求抑制水分浸入之特性,對於接著劑層(黏著劑層)亦要求該特性。   [0006] 本發明係鑑於上述情況而完成者,目的在於提供經由接著劑層之水分朝被密封物浸入的抑制效果高而具有優異之層間密著性之氣體障壁性層合體及將被密封體以該氣體障壁性層合體密封而成之密封體。 [用以解決課題之手段]   [0007] 本發明人等發現於與含高分子化合物且施以改質處理的氣體障壁層直接層合之接著劑層的形成材料的接著劑組成物中,至少含有多官能環氧化合物並且於該接著劑組成物中進而含有特定樹脂,而且將由該接著劑組成物形成之特定薄片狀物之水蒸氣透過率調整為特定值以下,可解決上述課題,因而完成本發明。   [0008] 亦即,本發明係有關下述[1]~[11]。   [1] 一種氣體障壁性層合體,其特徵係具有含高分子化合物且施以改質處理的氣體障壁層、與由含有聚烯烴樹脂(A)及多官能環氧化合物(B)的接著劑組成物形成的接著劑層,   且具有前述氣體障壁層與前述接著劑層直接層合的構成。   [2] 如上述[1]記載之氣體障壁性層合體,其中,成分(A)含有改性聚烯烴樹脂(A1)。   [3] 如上述[2]記載之氣體障壁性層合體,其中,成分(A1)為酸改性聚烯烴樹脂。   [4] 如上述[1]~[3]中任一項記載之氣體障壁性層合體,其中,前述接著劑層的80℃之儲存彈性率G’為0.3MPa以下。   [5] 如上述[1]~[4]中任一項記載之氣體障壁性層合體,其中,成分(A)的含量相對於前述接著劑組成物的有效成分之全量而言,為5~ 90質量%。   [6] 如上述[1]~[5]中任一項記載之氣體障壁性層合體,其中,成分(B)的含量相對於前述接著劑組成物所含有的成分(A) 100質量份而言,為5~200質量份。   [7] 如上述[1]~[6]中任一項記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有黏著賦予劑(C)。   [8] 如上述[1]~[7]中任一項記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有咪唑系硬化觸媒(D)。   [9] 如上述[1]~[8]中任一項記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有矽烷偶合劑(E)。   [10] 一種氣體障壁性層合體,其特徵係具有含高分子化合物且施以改質處理的氣體障壁層、與由含有多官能環氧化合物(B)且符合下述要件(I)的接著劑組成物形成的接著劑層,   且具有前述氣體障壁層與前述接著劑層直接層合的構成,   .要件(I):由前述接著劑組成物形成的厚度50μm的薄片狀物的水蒸氣透過率為200g/m2 /day以下。   [11] 一種密封體,其特徵係將有機EL元件、有機EL顯示器元件、液晶顯示器元件、或太陽能電池元件以上述[1]~[10]中任一項記載之氣體障壁性層合體進行密封而成。 [發明效果]   [0009] 本發明之氣體障壁性層合體由於經由接著劑層之水分朝被密封物浸入的抑制效果高而具有優異之層間密著性,故可成為被密封物劣化之抑制效果高的密封材。[Problems to be Solved by the Invention] [0004] Generally, when a resin layer containing a resin is directly laminated on a gas barrier layer of a gas barrier film, the gas barrier layer has a low affinity with the resin, resulting in a gas barrier. A situation where the adhesion between the layers and the resin is problematic. In particular, when a modified gas barrier layer containing a polymer compound is used, the interlayer adhesion between the gas barrier layer and the resin is often poor. [0005] On the other hand, Patent Document 1 does not examine the interlayer adhesion between the gas barrier layer and the resin. When the organic EL element is sealed with the adhesive sheet described in Patent Document 1, when the interlayer adhesion between the gas barrier layer and the resin is low, moisture or the like penetrates from between the two layers, and the luminescent properties of the organic EL element are likely to deteriorate. In addition, the sealing material used for sealing the organic EL element is required not only for the gas barrier layer but also for the property of suppressing the intrusion of water, but also for the adhesive layer (adhesive layer). The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a gas barrier layered product and a to-be-sealed body that have a high effect of suppressing the intrusion of moisture into the object to be sealed through the adhesive layer and have excellent interlayer adhesion. A sealed body sealed with the gas barrier layered body. [MEANS TO SOLVE THE PROBLEM] [0007] The present inventors discovered that in the adhesive composition of the adhesive layer-forming material directly laminated with the modified gas barrier layer containing the polymer compound, at least The above-mentioned problems can be solved by containing a polyfunctional epoxy compound, further containing a specific resin in the adhesive composition, and adjusting the water vapor transmission rate of a specific sheet formed from the adhesive composition to a specific value or less. this invention. [0008] That is, the present invention relates to the following [1] to [11]. [1] A gas barrier layered product comprising a gas barrier layer containing a polymer compound and subjected to modification treatment, and an adhesive comprising a polyolefin resin (A) and a polyfunctional epoxy compound (B) The adhesive layer formed from the composition has a structure in which the gas barrier layer and the adhesive layer are directly laminated. [2] The gas barrier layered product according to the above [1], wherein the component (A) contains a modified polyolefin resin (A1). [3] The gas barrier layered product according to the above [2], wherein the component (A1) is an acid-modified polyolefin resin. [4] The gas barrier layered product according to any one of the above [1] to [3], wherein the storage elastic modulus G' of the adhesive layer at 80°C is 0.3 MPa or less. [5] The gas barrier layered body according to any one of the above [1] to [4], wherein the content of the component (A) is 5 to 5 with respect to the total amount of the active ingredients in the adhesive composition. 90% by mass. [6] The gas barrier layered body according to any one of the above [1] to [5], wherein the content of the component (B) is 100 parts by mass of the component (A) contained in the adhesive composition. In other words, it is 5 to 200 parts by mass. [7] The gas barrier layered product according to any one of the above [1] to [6], wherein the adhesive composition further contains an adhesion-imparting agent (C). [8] The gas barrier layered product according to any one of the above [1] to [7], wherein the adhesive composition further contains an imidazole-based curing catalyst (D). [9] The gas barrier layered body according to any one of the above [1] to [8], wherein the adhesive composition further contains a silane coupling agent (E). [10] A gas barrier layered product comprising a gas barrier layer containing a polymer compound and subjected to modification treatment, and a gas barrier layer containing a polyfunctional epoxy compound (B) and meeting the following requirements (I) The adhesive layer formed by the agent composition, and has the structure in which the gas barrier layer and the adhesive layer are directly laminated,. Requirement (I): The water vapor transmission rate of the sheet-like object having a thickness of 50 μm formed from the adhesive composition is 200 g/m 2 /day or less. [11] A sealing body characterized by sealing an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas barrier layered body according to any one of the above [1] to [10] made. [Effects of the Invention] [0009] The gas barrier layered product of the present invention has a high effect of suppressing the penetration of moisture into the object to be sealed via the adhesive layer, and has excellent interlayer adhesion, so it can be an effect of suppressing deterioration of the object to be sealed High sealing material.

[0010] 本說明書中,針對較佳數值範圍(例如含量等之範圍),而階段性記載之下限值及上限值可分別獨立組合。例如由「較好為10~90,更好為30~60」之記載,亦可將「較好的下限值(10)」與「更好的上限值(60)」組合,而成為「10~60」。   [0011] [氣體障壁性層合體之構成]   本發明之氣體障壁性層合體具有使含高分子化合物且施以改質處理的氣體障壁層與由接著劑組成物形成之接著劑層,且具有前述氣體障壁層與前述接著劑層直接層合的構成。   因此,本發明之第1實施形態之氣體障壁性層合體(1)(以下亦稱為「本發明之氣體障壁性層合體(1)」)中,前述接著劑層係由含有聚烯烴樹脂(A)及多官能環氧化合物(B)的接著劑組成物形成者。   又,本發明之第2實施形態之氣體障壁性層合體(2)(以下亦稱為「本發明之氣體障壁性層合體(2)」)中,前述接著劑層係由含有多官能環氧化合物(B)且滿足下述要件(I)的接著劑組成物形成者。   .要件(I):由前述接著劑組成物形成的厚度50μm的薄片狀物的水蒸氣透過率為200g/m2 /day以下。   又,本說明書中,將「本發明之氣體障壁性層合體(1)」與「本發明之氣體障壁性層合體(2)」彙總記載為「本發明之氣體障壁性層合體」。   [0012] 本發明之氣體障壁性層合體亦可具有氣體障壁層及接著劑層以外之層,例如亦可具有基材層或剝離薄膜,舉例為例如具有以下之層構成之態樣。   .(i)依順序層合基材層/氣體障壁層/接著劑層/剝離薄膜而成之層合體。   .(ii)依順序層合剝離薄膜/氣體障壁層/接著劑層/剝離薄膜而成之層合體。   [0013] 上述(i)之態樣中,為了提高基材層與氣體障壁層之密著性,亦可如下述(iii)之態樣般,於基材層與氣體障壁層之間具有底塗層。   .(iii)依順序層合基材層/底塗層/氣體障壁層/接著劑層/剝離薄膜而成之層合體。   [0014] 上述(ii)之態樣中,2片剝離薄膜可為相同亦可互為不同,較好為具有相互不同剝離力者。   又,上述(i)~(iii)之態樣係表示氣體障壁性層合體使用前之狀態者,使用時,通常將剝離薄膜剝離去除。   [0015] 此處,本發明之氣體障壁性層合體(1)具有之接著劑層由於含有多官能環氧化合物(B)且進而含有聚烯烴系樹脂(A),故可將該接著劑層之水蒸氣透過率調整為較低,可抑制經由接著劑層之水分朝被密封物之侵入。   又,本發明之氣體障壁性層合體(1)具有含高分子化合物且施以改質處理的氣體障壁層,經由本發明人等經檢討而了解僅由聚烯烴系樹脂(A)形成之接著劑層與該氣體障壁層之層間密著性差。   因此,由本發明人等積極檢討之結果,發現藉由由含有聚烯烴系樹脂(A)且含有多官能環氧化合物(B)之接著劑組成物形成之接著劑層,可提高與具有含高分子化合物且施以改質處理的氣體障壁層之層間密著性。   本發明之氣體障壁性層合體係由該見解而完成者,由於水蒸氣透過率低,可抑制經由接著劑之水分朝被密封物之侵入且具有優異之層間密著性,故而可成為被密封物劣化之抑制效果高的密封材。   [0016] 另一方面,本發明之氣體障壁性層合體(2)係適當調整接著劑層的形成材料之接著劑組成物的成分種類或含量,而調整為滿足上述要件(I)規定之厚度50μm的薄片狀物的水蒸氣透過率為200g/m2 /day以下者。   又,氣體障壁性層合體(2)具有之接著劑層之形成材料的接著劑組成物,若至少含有多官能環氧化合物(B)且滿足上述要件(I),則亦可含有聚烯烴系樹脂(A)以外之樹脂成分。   [0017] 本發明之氣體障壁性層合體(2)中,以上述要件(I)規定之厚度50μm的薄片狀物的水蒸氣透過率為200g/m2 /day以下,但較好為150 g/m2 /day以下,更好為100g/m2 /day以下。   藉由使該薄片狀物之水蒸氣透過率為200g/m2 /day以下,可抑制水分朝形成於透明基板上之有機EL元件等之被密封物內部之浸入,可有效地抑制電極或有機層劣化。   又,本說明書中,水蒸氣透過率意指藉由實施例記載之方法測定之值。   且,本發明之氣體障壁性層合體(2)具有之接著劑層與上述要件(I)所規定之薄片狀物係形成材料的接著劑組成物為相同,且前述薄片狀物規定為厚度係50μm,但前述接著劑層厚度不限制於50μm,而可根據用途適當設定。   [0018] 此處,本發明之氣體障壁性層合體(1)及(2)具有之接著劑層厚度係根據用途適當設定,但較好為2~50μm,更好為5~40μm,又更好為10~30μm。   [0019] 本發明之氣體障壁性層合體(1)及(2)具有之接著劑層的80℃之儲存彈性率G’較好為0.3MPa以下,更好為0.2MPa以下,又更好為0.1 MPa以下,再更好為0.09MPa以下。   藉由使接著劑層的80℃之儲存彈性率G’為0.3MPa以下,本發明之氣體障壁性層合體可成為凹凸追隨性優異、被密封物劣化之抑制效果高之密封材。   又,基於處理性之觀點,接著劑層的80℃之儲存彈性率G’通常為0.001MPa以上,較好為0.005MPa以上,更好為0.01MPa以上。   又,本說明書中,接著劑層之儲存彈性率G’意指藉由實施例中記載之方法測定之值。   [0020] 本發明之氣體障壁性層合體(1)及(2)具有之接著劑層較好具有熱硬化性。此等接著劑層於硬化後,接著強度極優異。   使接著劑層熱硬化時之條件並未特別限定,但加熱溫度通常為80~200℃(較好90~150℃),加熱時間通常為30分鐘~12小時(較好1~6小時)。   [0021] 本發明之氣體障壁性層合體(1)具有之接著劑層的形成材料之接著劑組成物,在不損及本發明效果之範圍內,亦可含有成分(A)及(B)以外之其他成分。   作為此等成分,該接著劑組成物較好進而含有選自黏著賦予劑(C)、咪唑系硬化觸媒(D)以及矽烷偶合劑(E)之至少一種,進而更好含有成分(C)、(D)及(E)。   [0022] 又,本發明之氣體障壁性層合體(2)具有之接著劑層的形成材料之接著劑組成物,若調製為滿足上述要件(I),則亦可含有成分(B)以外之其他成分,亦可與成分(B)一起含有聚烯烴系樹脂(A),亦可進而含有選自上述成分(C)~(E)之一種以上。   [0023] 本發明之氣體障壁性層合體(1)及(2)具有之接著劑層的形成材料之接著劑組成物,作為成分(A)及(B)之合計含量,相對於該接著劑組成物的有效成分之全量(100質量%),較好為30質量%以上,更好50質量%以上,又更好60質量%以上,再更好65質量%以上,特佳為70質量%以上,且通常為100質量%以下,較好為99.9質量%以下。   [0024] 本發明之氣體障壁性層合體(1)及(2)具有之接著劑層的形成材料之接著劑組成物,作為成分(A)、(B)、(C)、(D)及(E)之合計含量,相對於該接著劑組成物的有效成分之全量(100質量%),較好為60~100質量%,更好70~100質量%,又更好80~100質量%,再更好90~100質量%。   又,本說明書中,所謂接著劑組成物之有效成分係指接著劑組成物中所含之與物性無關之稀釋溶劑除外之成分。   以下,針對本發明之氣體障壁性層合體(1)及(2)具有之接著劑層的形成材料之接著劑組成物所含之各成分加以詳述。   [0025] <成分(A):聚烯烴系樹脂>   藉由使成為接著劑層的形成材料之接著劑組成物中含有聚烯烴系樹脂(A),可降低所形成之接著劑層之水蒸氣透過率,可有效地抑制經由接著劑層之水分朝被密封物之浸入。   [0026] 本發明中,所謂聚烯烴樹脂係指具有源自烯烴系單體之重複單位之聚合物。   本發明中,該聚烯烴樹脂可為僅由源自烯烴系單體之重複單位構成之聚合物,亦可為與源自烯烴系單體之重複單位一起具有源自烯烴系單體以外之單體之重複單位的共聚物。   [0027] 作為上述烯烴系單體,較好為碳數2~8之α-烯烴,更好為乙烯、丙烯、1-丁烯、異丁烯、或1-己烯,更好為乙烯或丙烯。   作為烯烴單體以外之單體舉例為例如乙酸乙烯酯、(甲基)丙烯酸酯、苯乙烯等。   [0028] 作為具體之聚烯烴樹脂舉例為例如超低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、直鏈狀低密度聚乙烯、聚丙烯(PP)、乙烯-丙烯共聚物、烯烴系彈性體(TPO)、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、聚異丁烯、聚異戊二烯等。   又,本說明書中,所謂「(甲基)丙烯酸」表示「丙烯酸」與「甲基丙烯酸」兩者,其他類似用語亦相同。   又,聚烯烴系樹脂(A)可單獨使用,亦可併用2種以上。   [0029] 又,本發明一態樣中,成分(A)較好含改性聚烯烴系樹脂(A1)。   含有改性聚烯烴系樹脂(A1)之接著劑組成物係接著強度優異並且可容易形成膜厚較薄之接著劑層。   [0030] 成分(A)亦可併用改性聚烯烴系樹脂(A1)與非改性聚烯烴系樹脂,亦可僅由改性聚烯烴系樹脂(A1)構成。   基於接著強度優異並且可容易形成膜厚較薄之接著劑層之接著劑組成物之觀點,成分(A1)之含有比例,相對於接著劑組成物所含之成分(A)之全量(100質量%)而言,較好為50~100質量%,更好為65~100質量%,又更好為80~100質量%,再更好為90~100質量%。   [0031] 本發明中,所謂改性聚烯烴系樹脂係使用具有官能基之改性劑對作為前驅物之上述聚烯烴樹脂施以改性處理而得之具有官能基之聚烯烴樹脂。   聚烯烴系樹脂之改性處理所用之改性劑只要於分子內具有官能基亦即有助於後述交聯反應之基的化合物即可。   作為官能基舉例為羧基、源自羧酸酐之基(-CO-O-CO-)、羧酸酯基、羥基、環氧基、醯胺基、銨基、腈基、胺基、醯亞胺基、異氰酸酯基、乙醯基、硫醇基、醚基、硫醚基、磺基、磷酸基、硝基、胺基甲酸酯基、鹵原子等。   該等中,較好為羧基、源自羧酸酐之基、羧酸酯基、羥基、銨基、胺基、醯亞胺基或異氰酸酯基,更好為源自羧酸酐之基或烷氧基矽烷基,更好為源自羧酸酐之基。   所使用之改性劑亦可為分子內具有2種以上官能基之化合物。   [0032] 作為改性聚烯烴系樹脂(A1),基於成為接著強度優異,並且水蒸氣透過率低、容易形成氣體障壁性高的接著劑層之接著劑組成物之觀點,較好為酸改性聚烯烴系樹脂或矽烷改性聚烯烴系樹脂,更好為酸改性聚烯烴系樹脂。   [0033] 本發明中,所謂酸改性聚烯烴系樹脂係指藉由改性劑之具有官能基之酸對聚烯烴樹脂進行接枝改性者。例如使聚烯烴樹脂與不飽和羧酸及/或不飽和羧酸之酸酐反應,而導入羧基及/或源自羧酸酐之基(接枝改性)者。   [0034] 與聚烯烴樹脂反應之不飽和羧酸及不飽和羧酸酐舉例為例如馬來酸、富馬酸、依康酸、檸康酸、戊烯二酸、四氫苯二甲酸、烏頭酸、馬來酸酐、依康酸酐、戊烯二酸酐、檸康酸酐、烏頭酸酐、降冰片烯二羧酸酐、四氫苯二甲酸酐等。   該等可單獨使用或併用2種以上。   該等中,基於成為接著強度優異,並且水蒸氣透過率低、容易形成氣體障壁性高的接著劑層之接著劑組成物之觀點,較好為馬來酸酐。   [0035] 與聚烯烴樹脂反應之不飽和羧酸及/或不飽和羧酸酐之摻合量,基於成為接著強度優異,並且水蒸氣透過率低、容易形成氣體障壁性高的接著劑層之接著劑組成物之觀點,相對於改性前之聚烯烴樹脂100質量份而言,較好為0.1~5質量份,更好為0.2~3質量份,又更好為0.2~1.0質量份。   [0036] 本發明中,酸改性聚烯烴系樹脂亦可使用市售品。   作為市售品之酸改性聚烯烴系樹脂舉例為例如ADOMER(註冊商標)(三井化學股份有限公司製)、UNISTOLE(註冊商標)(三井化學股份有限公司製)、BondyRam(Polyram公司製)、orevac(註冊商標)(ARKEMA公司製)、MODIC(註冊商標)(三菱化學股份有限公司製)等。   [0037] 又,本發明中,所謂矽烷改性聚烯烴系樹脂係指以改性劑的不飽和矽烷化合物對聚烯烴樹脂進行接枝改性者。亦即,矽烷改性聚烯烴系樹脂具有於主鏈的聚烯烴樹脂上接枝共聚合有側鏈的不飽和矽烷化合物之構造。   [0038] 作為與聚烯烴樹脂反應之不飽和矽烷化合物較好為乙烯基矽烷化合物,舉例為例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三丙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯基三丁氧基矽烷、乙烯基三戊氧基矽烷、乙烯基三苯氧基矽烷、乙烯基三苄氧基矽烷、乙烯基三亞甲二氧基矽烷、乙烯基三伸乙二氧基矽烷、乙烯基丙醯氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三羧基矽烷等。   該等不飽和矽烷化合物可單獨使用亦可併用2種以上。   又,將不飽和矽烷化合物接枝聚合於主鏈的聚烯烴樹脂時之條件只要採用習知之接枝聚合常用方法即可。   [0039] 與聚烯烴樹脂反應之不飽和矽烷化合物之摻合量,基於成為接著強度優異,並且水蒸氣透過率低、容易形成氣體障壁性高的接著劑層之接著劑組成物之觀點,相對於改性前之聚烯烴樹之100質量份而言,較好為0.1~10質量份,更好為0.3~7質量份,又更好為0.5~5質量份。   [0040] 作為具體之矽烷改性聚烯烴系樹脂舉例為例如矽烷改性聚乙烯樹脂及矽烷改性乙烯-乙酸乙烯酯共聚物,較好為矽烷改性低密度聚乙烯、矽烷改性超低密度聚乙烯、矽烷改性直鏈狀低密度聚乙烯等之矽烷改性聚乙烯樹脂。   [0041] 本發明中,矽烷改性聚烯烴系樹脂亦可使用市售品。   作為市售品之矽烷改性聚烯烴系樹脂舉例為例如LINKLON(註冊商標)(三菱化學股份有限公司製)等,但較好為低密度聚乙烯系之LINKLON、直鏈狀低密度聚乙烯系之LINKLON、超低密度聚乙烯系之LINKLON及乙烯-乙酸乙烯酯共聚物系之LINKLON。   [0042] 聚烯烴系樹脂(A)之重量平均分子量(Mw),基於成為接著強度優異,並且水蒸氣透過率低、容易形成氣體障壁性高的接著劑層之接著劑組成物之觀點,以及基於形成為薄片狀時,可維持其形狀之形狀維持性良好之接著劑組成物之觀點,較好為10,000~2,000,000,更好為20,000~1500,000,又更好為25,000~250,000,再更好為30,000~150,000。   藉由使聚烯烴系樹脂(A)之重量平均分子量(Mw)於上述範圍,即使接著劑組成物中之聚烯烴系樹脂(A)之含量多時,由該接著劑組成物形成之薄片形狀之維持變容易。   [0043] 又,本說明書中,重量平均分子量(Mw)係使用四氫呋喃作為溶劑,藉凝膠滲透層析(GPC)法測定之標準聚苯乙烯換算之值,具體係基於實施例中記載之方法測定之值。以下亦同。   [0044] 又,聚烯烴系樹脂(A),基於形成為薄片狀時,可維持其形狀之形狀維持性良好之接著劑組成物之觀點,較好於常溫(25℃)為固體。   [0045] 成分(A)之含量,相對於前述接著劑組成物的有效成分之全量(100質量%)而言,較好為5~90質量%,更好為15~80質量%,又更好為23~70質量%,再更好為30~60質量%。   [0046] <成分(B):多官能環氧化合物>   成為接著劑層之形成材料的接著劑組成物含有多官能環氧化合物(B)。   藉由含有多官能環氧化合物(B),可使形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性良好。   又,多官能環氧化合物(B)可單獨使用亦可併用2種以上。   [0047] 本發明中,所謂多官能環氧化合物係指分子內至少具有2個以上環氧基之化合物。   作為成分(B),基於使形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性更提高之觀點,較好為具有2個環氧基之2官能環氧化合物。   [0048] 作為2官能環氧化合物,舉例為雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、溴化雙酚A二縮水甘油醚、溴化雙酚F二縮水甘油醚、溴化雙酚S二縮水甘油醚、酚醛清漆型環氧樹脂(例如酚.酚醛清漆型環氧樹脂、甲酚.酚醛清漆型環氧樹脂、溴化酚.酚醛清漆型環氧樹脂)等之芳香族環氧化合物;氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、氫化雙酚S二縮水甘油醚等之脂環式環氧化合物;季戊四醇聚縮水甘油醚、1,6-己二醇二縮水甘油醚、六氫苯二甲酸二縮水甘油酯、新戊二醇二縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、2,2-雙(3-縮水甘油基-4-縮水甘油氧基苯基)丙烷、二羥甲基三環癸烷二縮水甘油醚等之脂肪族環氧化合物。   該等中,多官能環氧化合物(B)較好為選自多官能脂環式環氧化合物及多官能脂肪族環氧化合物之1種以上。   [0049] 多官能環氧化合物(B)之重量平均分子量(Mw),基於使形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性更提高之觀點,較好為200~5000,更好為300~4500,又更好為500~4000,再更好為600~3500。   [0050] 多官能環氧化合物之環氧當量較好為100~500g/eq,更好為120~400g/eq,又更好為150~ 300g/eq。   [0051] 成分(B)之含量,相對於前述接著劑組成物所含有的成分(A) 100質量份而言,基於使形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性更提高之觀點,較好為5質量份以上,更好為10質量份以上,又更好為20質量份以上,再者,基於將形成之接著劑層的80℃之儲存彈性率G’調整為較低,成為凹凸追隨性良好之氣體障壁性層合體之觀點,更好為30質量份以上,又更好為50質量份以上,再更好為65質量份以上。   且,基於容易形成接著強度優異之接著劑層之觀點,成分(B)之含量,相對前述接著劑組成物所含成分(A)100質量份而言,較好為200質量份以下,更好為180質量份以下,又更好為150質量份以下,再更好為120質量份以下。   [0052] <成分(C):黏著賦予劑>   接著劑組成物,基於使形成之接著劑層之形狀維持性更良好之觀點,較好進而含有黏著賦予劑(C)。   [0053] 作為黏著賦予劑(C)舉例為聚合松脂、聚合松脂酯、松脂衍生物等之松脂系樹脂;聚萜烯樹脂、芳香族改性萜烯樹脂及其氫化物、萜烯酚樹脂等之萜烯系樹脂;香豆酮.茚樹脂;脂肪族石油系樹脂、芳香族系石油樹脂及其氫化物、脂肪族/芳香族共聚物石油樹脂等之石油樹脂;苯乙烯或取代苯乙烯聚合物;α-甲基苯乙烯均聚合系樹脂、α-甲基苯乙烯與苯乙烯之共聚物、苯乙烯系單體與脂肪族系單體之共聚物、苯乙烯系單體與α-甲基苯乙烯及脂肪族系單體之共聚物、由苯乙烯系單體所成之均聚物、苯乙烯系單體與芳香族單體之共聚物等之苯乙烯系樹脂等。   該等黏著賦予劑(C)可單獨使用,亦可併用2種以上。   該等中,作為成分(C),較好為苯乙烯系樹脂,更好為苯乙烯系單體與脂肪族系單體之共聚物。   [0054] 黏著賦予劑(C)之軟化點,基於使形成之接著劑層之形狀維持性及接著強度更提高之觀點,較好為80℃以上,更好為85~170℃,又更好為90~150℃。   又,本說明書中,軟化點意指依據JIS K 5902測定之值。   使用2種以上之複數黏著賦予劑時,該等複數之黏著賦予劑之軟化點之加權平均較好屬於上述範圍。   [0055] 成分(C)之含量,基於使形成之接著劑層之形狀維持性更提高之觀點,相對於成分(A) 100質量份而言,較好為1~200質量份,更好為10~150質量份,又更好為15~100質量份,再更好為20~80質量份。   [0056] <成分(D):咪唑系硬化觸媒>   接著劑組成物,基於成為高溫環境下之接著強度更提高之接著劑層之觀點,較好進而含有咪唑系硬化觸媒(D)。   [0057] 作為咪唑系硬化觸媒(D),舉例為2-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑等。   該等咪唑系硬化觸媒(D)可單獨使用,亦可併用2種以上。   該等中,作為成分(D),較好為2-乙基-4-甲基咪唑。   [0058] 成分(D)之含量,基於成為高溫環境下之接著強度更提高之接著劑層之觀點,相對於成分(A) 100質量份而言,較好為0.1~10質量份,更好為0.2~5質量份,又更好為0.3~2.5質量份。   [0059] <成分(E):矽烷偶合劑>   接著劑組成物,基於容易形成在常溫及高溫環境下之任一者均具有優異接著強度之接著劑層之觀點,較好進而含有矽烷偶合劑(E)。   又,接著劑組成物含有矽烷偶合劑時,形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性更提高。   [0060] 作為矽烷偶合劑(E),基於上述觀點,較好係分子內具有至少1個烷氧基矽烷基之有機矽化合物。   作為具體之矽烷偶合劑(E),舉例為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷等之含聚合性不飽和基之矽化合物;3-縮水甘油氧基丙基三甲氧基矽烷、縮水甘油氧基辛基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷等之具有環氧基構造之矽化合物;3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等之含胺基之矽化合物;3-氯丙基三甲氧基矽烷;3-異氰酸酯基丙基三乙氧基矽烷等。   該等矽烷偶合劑(E)可單獨使用,亦可併用2種以上。   [0061] 成分(E)之含量,基於容易形成在常溫及高溫環境下之任一者均具有優異接著強度之接著劑層之觀點及使形成之接著劑層與含高分子化合物且施以改質處理的氣體障壁層之層間密著性更提高之觀點,相對於成分(A) 100質量份而言,較好為0.01~10質量份,更好為0.02~5質量份,又更好為0.05~2質量份。   [0062] <其他添加劑>   接著劑組成物在不損及本發明效果之範圍,亦可含有上述成分(A)~(E)以外之其他添加劑。   作為其他添加劑,可根據用途適當選擇,但舉例為例如紫外線吸收劑、抗靜電劑、光安定劑、抗氧化劑、樹脂安定劑、填充劑、顏料、增量劑、軟化劑等之添加劑。   該等添加劑可單獨使用,亦可併用2種以上。   [0063] 又,接著劑組成物,基於成形性良好之觀點,亦可進而含有稀釋溶劑。   作為稀釋溶劑可自有機溶劑中適當選擇,但具體而言,舉例為苯、甲苯等之芳香族烴系溶劑;乙酸乙酯、乙酸丁酯等之酯系溶劑;丙酮、甲基乙基酮、甲基異丁基酮等之酮系溶劑;正戊烷、正己烷、正庚烷等之脂肪族烴系溶劑;環戊烷、環己烷、甲基環己烷等之脂環式烴系溶劑等。   該等溶劑可單獨使用,亦可併用2種以上。   又,溶劑含量可考慮塗佈性等而適當設定。   [0064] <接著劑層之形成方法>   作為接著劑層之形成方法,舉例為例如於剝離薄膜之剝離處理面上塗佈接著劑組成物形成塗膜,使該塗膜乾燥形成接著劑層之方法。   作為接著劑組成物之塗佈方法舉例為例如旋轉塗佈法、噴霧塗佈法、棒塗佈法、刮刀塗佈法、輥塗佈法、刮板塗佈法、模嘴塗佈法、凹版塗佈法等。   又,基於塗佈性良好之觀點,較好為於接著劑組成物中添加上述稀釋溶劑作成溶液形態。   作為使塗膜乾燥時之乾燥條件較好例如於80~150℃施以30秒~5分鐘之乾燥處理。   [0065] [氣體障壁層]   本發明之氣體障壁性層合體具有之氣體障壁層係含高分子化合物且施以改質處理之層。該氣體障壁層由於具有優異氣體障壁性且柔軟性優異,故可成為對彎曲之耐性亦優異之氣體障壁性層合體。   該氣體障壁層之厚度較好為50~300nm,更好為50~200nm。   本發明之氣體障壁性層合體具有之氣體障壁層即使厚度為奈米等級,亦具有充分之氣體障壁性。   [0066] 作為氣體障壁層所含之高分子化合物舉例為例如聚有機矽氧烷、聚矽氮烷系化合物等之含矽高分子化合物,聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚苯醚、聚醚酮、聚醚醚酮、聚烯烴、聚酯、聚碳酸酯、聚碸、聚醚碸、聚苯硫醚、聚芳酸酯、丙烯酸系樹脂、環烯烴系聚合物、芳香族系聚合物等。   該等高分子化合物可單獨使用,亦可併用2種以上。   該等中,基於成為具有優異氣體障壁性之氣體障壁性層合體之觀點,作為氣體障壁層中所含之高分子化合物,較好為含矽高分子化合物,更好為聚矽氮烷系化合物。   聚矽氮烷系化合物之數平均分子量較好為100~ 50,000。   [0067] 聚矽氮烷系化合物係具有分子內含-Si-N-鍵(矽氮鍵)之重複單位的聚合物,具體而言係具有以下述通式(1)表示之重複單位之聚合物。

Figure 02_image001
[0068] 上述通式(1)中,n表示重複單位數,且表示1以上之整數。   Rx、Ry、Rz分別獨立表示氫原子、無取代或具有取代基之烷基、無取代或具有取代基之環烷基、無取代或具有取代基之烯基、無取代或具有取代基之芳基或烷基矽烷基。   該等中,作為Rx、Ry、Rz,較好為氫原子、碳數1~6之烷基或苯基,更好為氫原子。   又,作為氣體障壁層中所含之高分子化合物可為前述通式(1)中之Rx、Ry、Rz全部為氫原子之無機聚矽但烷,亦可為Rx、Ry、Rz之至少一個為氫原子以外之基之有機聚矽氮烷。   [0069] 聚矽氮烷化合物可單獨使用,亦可併用2種以上。   又,作為聚矽氮烷化合物,亦可使用聚矽氮烷改性物,且亦可使用市售品。   [0070] 氣體障壁層除了上述高分子化合物以外,在不損及本發明效果之範圍內,亦可進而含有其他成分。   作為其他成分舉例為例如硬化劑、其他高分子、抗老化劑、光安定劑、難燃劑等。   氣體障壁層中之高分子化合物含量,基於成為具有更優異氣體障壁性之氣體障壁層之觀點,相對於該氣體障壁層中之成分全量(100質量%),較好為50~100質量%,更好70~100質量%,又更好為80~100質量%。   [0071] 作為氣體障壁層之形成方法,舉例為例如將含有高分子化合物之至少一種、根據期望之其他成分及溶劑等之氣體障壁層形成用溶液,以旋轉塗佈器、刮刀塗佈器、凹版塗佈器等之習知裝置塗佈形成塗膜,使該塗膜乾燥而形成之方法。   [0072] 作為氣體障壁層之改質方法,較好為離子注入處理、電漿處理、放射線照射處理、熱處理等,使高分子層之結合構造變化之處理。該等處理可單獨使用1種,亦可組合2種以上進行。   離子注入處理係如後述於氣體障壁層中注入離子而使氣體障壁層改質之方法。   電漿處理係將氣體障壁層暴露於電漿中而使氣體障壁層改質之方法。例如可依據日本特開2012-106421號公報中記載之方法進行電漿處理。   放射線照射處理係對氣體障壁層照射放射線而使氣體障壁層改質之方法。放射線較好為使高分子層之結合構造變化之效果高的短波長者,較好使用紫外線,尤其是真空紫外光。例如可依據日本特開2013-226757號公報中記載之方法,進行真空紫外光改質處理。   該等中,基於不使氣體障壁層表面粗糙,效率良好地改質至內部,可形成氣體障壁性優異之氣體障壁層之觀點,作為氣體障壁層之改質處理較好為離子注入處理。   [0073] 離子注入處理時,作為注入於氣體障壁層之離子舉例為例如氬、氦、氖、氪、氙等之稀有氣體之離子;氟碳、氫、氮、氧、二氧化碳、氯、氟、硫等之離子;甲烷、乙烷等之烷系氣體類之離子;乙烯、丙烯等之烯系氣體類之離子;戊二烯、丁二烯等之烷二烯系氣體類之離子;乙炔等之炔系氣體類之離子;苯、甲苯等之芳香族烴系氣體類之離子;環丙烷等之環烷系氣體類之離子;環戊烯等之環烯系氣體類之離子;金屬離子;有機矽化合物之離子;等。   該等離子可單獨使用,亦可併用2種以上。   該等中,基於可更簡便注入離子,獲得具有特別優異氣體障壁性之氣體障壁層之觀點,較好為氬、氦、氖、氪、氙等之稀有氣體之離子,更好為氬離子。   [0074] 作為注入離子之方法並未特別限定。舉例為例如照射藉由電場加速之離子(離子束)之方法、注入電漿中之離子(電漿生成氣體之離子)之方法等,注入電漿中之離子之方法(以下有時稱為「電漿離子注入法」)可簡便地獲得氣體障壁層故而較佳。   電漿離子注入法可藉由例如於含電將生成氣體之環境下發生電漿,對注入離子之層施加負的高電壓脈衝,而使該電漿中之離子(陽離子)注入欲注入離子之層的表面部而進行。   [0075] [基材層]   作為本發明之氣體障壁性層合體具有之基材層舉例為例如金屬箔、樹脂薄膜、薄膜玻璃等,較好為樹脂薄膜。   作為構成樹脂薄膜之樹脂成分舉例為例如聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚苯醚、聚醚酮、聚醚醚酮、聚烯烴、聚酯、聚碳酸酯、聚碸、聚醚碸、聚苯硫醚、聚芳酸酯、丙烯酸系樹脂、環烯烴系聚合物、芳香族系聚合物、聚胺基甲酸酯系聚合物等。   該等樹脂成分可單獨使用,亦可併用2種以上。   [0076] 基材層以樹脂薄膜構成時,基於提高與層合於樹脂薄膜上之層之密著性之觀點,較好對樹脂薄膜表面藉由氧化法或凹凸化法等施以易接著處理。   作為氧化法舉例例如電暈放電法、電漿放電處理、鉻酸處理(溼式)、熱風處理、臭氧及紫外線照射處理等,作為凹凸化法舉例為例如噴沙法、溶劑處理法等。   [0077] 基材層厚度並未特別限制,基於處理容易性之觀點,較好為0.5~ 500μm,更好為1~200μm,又更好為5~100μm。   [0078] [底塗層]   本發明之氣體障壁性層合體中,基於更提高基材層與氣體障壁層之密著性之觀點,作為易接著處理手段之一,亦可於基材層與氣體障壁層之間設置底塗層。   作為前述底塗層,舉例為例如使含紫外線硬化性化合物之組成物硬化之層。該含紫外線硬化性化合物之組成物亦可含有氧化矽粒子等之無機填充材。   前述底塗層厚度較好為0.1~10μm,更好為0.5~5μm。   [0079] [剝離薄膜]   作為本發明之氣體障壁性層合體具有之剝離薄膜可利用以往習知者,舉例為例如於剝離薄膜用基材上具有藉由剝離劑進行剝離處理之剝離層者。   作為剝離薄膜用基材舉例為例如玻璃紙、銅版紙、上等紙等之紙基材;於該等紙基材上層合聚乙烯等之熱塑性樹脂之層合紙;由聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚萘二甲酸乙二酯樹脂、聚丙烯樹脂、聚乙烯樹脂等形成之塑膠薄膜;等。   作為剝離劑舉例為例如矽氧系樹脂、烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等之橡膠系彈性體、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂等。   [0080] [密封體]   本發明之密封體係被密封物以本發明之氣體障壁性層合體密封而成者。   作為本發明之密封體係例如具備透明基板與形成於該透明基板上之元件(被密封物)及用以密封該元件之密封材的氣體障壁性層合體者。   [0081] 透明基板並未特別限制,可使用各種基板材料。尤其較好使用可見光之透過率高的基板材料。且較好為阻止會自元件外部浸入之水分或氣體之遮斷性高、耐溶劑性或耐候性優異之材料。   具體而言舉例為石英或玻璃等之透明無機材料;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚苯乙烯、聚乙烯、聚丙烯、聚苯硫醚、聚偏氟化乙烯、乙醯基纖維素、溴化苯氧、芳醯胺類、聚醯亞胺類、聚苯乙烯類、聚芳酸酯類、聚碸類、聚烯烴類等之透明塑膠;前述之氣體障壁性薄膜。   透明基板厚度並未特別限制,可考慮光之透過氯、或遮斷元件內外之性能而適當選擇。   [0082] 作為被密封物舉例為有機EL元件、有機EL顯示器元件、液晶顯示器元件、太陽能電池元件等。   亦即,本發明之密封體較好為以本發明之氣體障壁性層合體密封有機EL元件、有機EL顯示器元件、液晶顯示器元件、或太陽能電池元件者。   [0083] 本發明之密封體之製造方法並未特別限制。例如將本發明之氣體障壁性層合體具有之接著劑層重疊於被密封物上後,藉由加熱而使該接著劑層與被密封物接著。   其次,藉由使該接著劑層硬化,可製造本發明之密封體。   [0084] 使氣體障壁性層合體與被密封物接著時之接著條件並未特別限制。接著溫度為例如23~100℃,較好為40~80℃。該接著處理可邊加壓邊進行。使接著劑層硬化時之硬化條件可利用先前說明之條件。 [實施例]   [0085] 以下列舉實施例更詳細說明本發明。但,本發明並非限定於以下實施例者。   又,改性聚烯烴系樹脂、丙烯酸系樹脂及多官能環氧化合物之重量平均分子量(Mw)係藉由以下方法測定之值。 <改性聚烯烴系樹脂及丙烯酸系樹脂之重量平均分子量(Mw)>   改性聚烯烴系樹脂之重量平均分子量(Mw)及丙烯酸系樹脂之重量平均分子量(Mw)係採用使用凝膠滲透層析(GPC)裝置(TOSOH股份有限公司製,製品名「HLC-8320」)於下述條件下測定,並換算為標準聚苯乙烯之重量平均分子量之值。 (測定條件)   .測定試料:樣品濃度1質量%之四氫呋喃溶液   .管柱:「TSK gel Super HM-H」2根與「TSK gel Super H2000」1根(均為TOSOH股份有限公司製)依序連結者   .管柱溫度:40℃   .展開溶劑:四氫呋喃四氫呋喃   .流速:0.60mL/min <多官能環氧化合物之重量平均分子量(Mw)>   多官能環氧化合物之重量平均分子量(Mw)係使用上述凝膠滲透層析(GPC)裝置,於下述條件下測定,自複數觀察到之波峰中,換算為與面積最大者之峰頂之保持時間對應之標準聚苯乙烯之重量平均分子量者。   [0086] 實施例1~2、比較例1~2 (1)接著劑組成物之調製   將下述所示各成分以表1記載之摻合量(有效成分比)進行添加,以甲基乙基酮稀釋,於實施例1~2及比較例1中,分別調製有效成分濃度30質量%之接著劑組成物,於比較例2中,調製有效成分濃度35質量%之接著劑組成物。   使用之各成分細節如以下。   .改性聚烯烴系樹脂:三井化學股份有限公司製,製品名「UNISTOLE H-200」,酸改性α-烯烴聚合物,於25℃下為固體,重量平均分子量(Mw)=52,000。   .丙烯酸系樹脂:丙烯酸丁酯(BA)及丙烯酸(AAc)之共聚物,BA/AAc=90/10,於25℃下為固體,重量平均分子量(Mw)=65萬。   .多官能環氧化合物:共榮社化學股份有限公司製,製品名「EPOLIGHT 4000」,氫化雙酚A二縮水甘油醚,於25℃下為液體,環氧當量=215~245g/eq,重量平均分子量(Mw)=800。   .黏著賦予劑:三井化學股份有限公司製,製品名「FTR6100」,苯乙烯系單體與脂肪族系單體之共聚物,軟化點=95℃。   .咪唑系硬化觸媒:四國化成工業股份有限公司製,製品名「CURAZOLE 2E4MZ」,2-乙基-4-甲基咪唑。   .矽烷偶合劑:信越化學工業股份有限公司製,製品名「KBM-4803」,縮水甘油氧基辛基三甲氧基矽烷。   [0087] (2)接著劑層之形成   於剝離薄膜(LINTEK股份有限公司製,製品名「SP-PET 382150」)之剝離處理面上,塗佈所調製之接著劑組成物形成塗膜,使該塗膜於100℃乾燥2分鐘,形成厚12μm之接著劑層。   且,另外如與上述同樣製作於剝離薄膜上形成厚50μm之接著劑層之層合體作為接著劑層之水蒸氣透過率之測定用。   [0088] (3)氣體障壁層之形成   於兩面經施以易接著處理之厚50μm之聚對苯二甲酸乙二酯(PET)薄膜(東洋紡股份有限公司製,製品名「PET50A4300」)上,使用線棒塗佈紫外線硬化型丙烯酸酯樹脂組成物(JSR股份有限公司製,製品名「OPSTAR Z7530」)形成塗膜,使該塗膜於70℃乾燥1分鐘。接著,使用無電極UV燈系統(HERAEUS股份有限公司製),以照度250 mW/cm2 、光量170mJ/cm2 照射紫外線,使該塗膜硬化,形成厚1000 nm之底塗層。   接著,於形成之前述底塗層上,使用旋轉塗佈器(MIKASA股份有限公司製,製品名「MS-A200」),以旋轉數3000rpm、旋轉時間30秒塗佈以全氫聚矽氮烷為主成分之固體成分濃度10質量%之塗佈劑(MERCK PERFORMANCE MATERIALS公司製,製品名「AKUAMIKA NL110-20」,溶劑:二甲苯),形成塗膜。接著使該塗膜於120℃乾燥2分鐘,於前述底塗層上形成厚150nm之由聚矽氮烷構成之聚矽氮烷層。   其次,對所形成之前述聚矽氮烷表面,使用電漿離子注入裝置以下述條件,藉由電漿離子注入法實施改質處理,形成厚150nm之氣體障壁層。 (電漿離子注入之處理條件)   .腔室內壓:0.2Pa   .電漿產生器體:氬   .氣體流量:100sccm   .RF輸出:1000W   .RF頻率:1000Hz   .RF脈衝寬:50μ秒   .RF延遲:25n秒   .DC電壓:-6kV   .DC頻率:1000Hz   .DC脈衝寬:5μ秒   .DC延遲:50μ秒   .佔空比:0.5%   .處理時間:200秒   又,於形成之氣體障壁層上,與上述同樣,進而重複3次形成厚150nm之氣體障壁層之形成,獲得具有層合4層之厚150nm之氣體障壁層所成之厚600nm之氣體障壁層之氣體障壁性薄膜。   [0089] (4)氣體障壁性層合體之製作   將上述(2)形成之厚12μm之接著劑層表面與上述(3)製作之氣體障壁性薄膜之厚600nm之氣體障壁層表面,使用熱層合機,於60℃貼合,製作氣體障壁性層合體。   [0090] 使用實施例及比較例所得之上述接著劑層及氣體障壁性層合體,進行以下之物性值之測定及評價。該等結果示於表1。   [0091] [接著劑層之水蒸氣透過率]   自實施例及比較例所製作之由剝離薄膜與厚50μm之接著劑層所成之層合體去除該剝離薄膜,僅前述接著劑層者作為試驗樣品,使用氣體透過率測定裝置(mocon公司製,製品名「PERMATRAN」),測定接著劑層之水蒸氣透過率。   [0092] [接著劑層之儲存彈性率G’]   實施例及比較例所形成之接著劑層複數層重疊,使用熱層合機,於60℃加熱壓縮,獲得厚1mm之接著劑層之多層體。   將該接著劑層之多層體作為試驗樣品,使用黏彈性測定裝置(Anton Paar公司製,製品名「Physica MCR301」),於頻率1Hz之條件下,測定於溫度範圍23~150℃下之硬化前之前述接著劑層之多層體之儲存彈性率G’。所測定之80℃下之儲存彈性率G’之值示於表1。   [0093] [層間密著性評價]   將實施例及比較例製作之氣體障壁性層合體切成長25mm×寬300mm之大小,去除剝離薄膜,將露出之接著劑層表面貼附於玻璃板,使用熱層合機,於60℃壓著,製作試驗樣品。接著將該試驗樣品於100℃加熱2小時,使接著劑層硬化後,於23℃靜置24小時。   進而,於溫度85℃、85%RH(相對溼度)之環境下靜置168小時後,以剝離角度180°之條件,將氣體障壁性層合體自玻璃板剝離時,確認接著劑層有無轉黏於玻璃板,藉以下基準,評價氣體障壁層與接著劑層之層間密著性。   A:未確認到接著劑層轉黏於玻璃板。   F:確認到接著劑層轉黏於玻璃板。   [0094] [凹凸追隨性評價]   於玻璃基板上,靜置厚10μm之聚對苯二甲酸乙二酯之小片作為擬裝置。接著,將實施例及比較例製作之氣體障壁性層合體之剝離薄膜去除,使露出之接著劑層完全覆蓋玻璃基板上之擬裝置之方式,層合於玻璃基板及擬裝置上,使用熱層合機於80℃密封,其次於80℃、0.5MPa實施20分鐘之加壓處理。此外,於100℃之環境下加熱2小時,使接著劑層硬化。   使用光學顯微鏡,俯視觀察擬裝置與硬化後之接著劑層之交界部分,如以下,藉由擬裝置與接著劑層之間有無存在間隙,而評價氣體障壁性層合體之凹凸追隨性。   A:擬裝置與接著劑層之間無間隙,故凹凸追隨性良好。   F:擬裝置與接著劑層之間確認到間隙,故凹凸追隨性差。   [0095]
Figure 02_image003
[0096] 實施例1及2製作之氣體障壁性層合體所具有之接著劑層由於與氣體障壁層之層間密著性優異且水蒸氣透過率低,故可說是抑制經由接著劑層之水分浸入至被密封體之效果優異的密封材。   另一方面,比較例1製作之氣體障壁性層合體,成為接著劑層與氣體障壁層之層間密著性差之結果。   且,比較例2製作之氣體障壁性層合體所具有之接著劑層之水蒸氣透過率為非常高的值。因此,比較例2中,未實施其他試驗即結束。[0010] In this specification, for the preferred numerical range (such as the range of content, etc.), the lower limit value and the upper limit value can be independently combined in the phased records. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", "a better lower limit value (10)" and "a better upper limit value (60)" may be combined to form "10~60". [Configuration of Gas Barrier Layered Product] The gas barrier layered product of the present invention includes a gas barrier layer containing a polymer compound and subjected to modification treatment, and an adhesive layer formed from an adhesive composition, and has A structure in which the gas barrier layer and the adhesive layer are directly laminated. Therefore, in the gas barrier layered product (1) according to the first embodiment of the present invention (hereinafter also referred to as "the gas barrier layered product (1) of the present invention"), the adhesive layer is made of a polyolefin resin ( A) and the form of the adhesive composition of the polyfunctional epoxy compound (B). Furthermore, in the gas barrier layered product (2) according to the second embodiment of the present invention (hereinafter also referred to as "the gas barrier layered product (2) of the present invention"), the adhesive layer is composed of a polyfunctional epoxy resin A compound (B) that satisfies the following requirement (I) in the form of an adhesive composition. . Requirement (I): The water vapor transmission rate of the sheet-like object having a thickness of 50 μm formed from the adhesive composition is 200 g/m 2 /day or less. In addition, in this specification, "the gas barrier layered product (1) of the present invention" and "the gas barrier layered product (2) of the present invention" are collectively described as "the gas barrier layered product of the present invention". [0012] The gas barrier layered product of the present invention may have layers other than the gas barrier layer and the adhesive layer, for example, may have a substrate layer or a release film, for example, a state having the following layer configuration. . (i) A laminate formed by laminating a base material layer/gas barrier layer/adhesive layer/release film in this order. . (ii) A laminate formed by laminating release film/gas barrier layer/adhesive layer/release film in this order. In the aspect (i) above, in order to improve the adhesion between the substrate layer and the gas barrier layer, as in the aspect (iii) below, there may be a bottom layer between the substrate layer and the gas barrier layer. coating. . (iii) A laminate formed by laminating a base layer/undercoat layer/gas barrier layer/adhesive layer/release film in this order. [0014] In the aspect of the above (ii), the two peeling films may be the same or different from each other, preferably those with mutually different peeling forces. In addition, the above-mentioned aspects (i) to (iii) represent the state before the gas barrier layered product is used, and the release film is usually peeled off and removed during use. Here, the adhesive layer of the gas barrier layered product (1) of the present invention contains the polyfunctional epoxy compound (B) and further contains the polyolefin-based resin (A), so the adhesive layer can be The water vapor transmission rate is adjusted to be low, and the intrusion of water through the adhesive layer into the object to be sealed can be suppressed. Moreover, the gas barrier layered product (1) of the present invention has a gas barrier layer containing a polymer compound and subjected to a modification treatment, and the inventors of the present invention have examined and found that the adhesive is formed only from the polyolefin-based resin (A). The interlayer adhesion between the agent layer and the gas barrier layer is poor. Therefore, as a result of active review by the present inventors, it was found that the adhesive layer formed by the adhesive composition containing the polyolefin-based resin (A) and containing the polyfunctional epoxy compound (B) can improve and have high content of the adhesive. The interlayer adhesion between the molecular compound and the modified gas barrier layer. The gas-barrier lamination system of the present invention has been completed based on this knowledge. Since the water vapor transmission rate is low, the intrusion of moisture into the object to be sealed through the adhesive can be suppressed, and it has excellent interlayer adhesion, so it can be sealed A sealing material with a high effect of suppressing physical deterioration. On the other hand, in the gas barrier layered product (2) of the present invention, the type or content of the components of the adhesive composition of the material for forming the adhesive layer is appropriately adjusted to satisfy the thickness specified in the above-mentioned requirement (1). The water vapor transmission rate of 50 μm flakes is 200 g/m 2 /day or less. In addition, the adhesive composition of the material for forming the adhesive layer included in the gas barrier layered body (2) may contain a polyolefin-based adhesive as long as it contains at least a polyfunctional epoxy compound (B) and satisfies the above-mentioned requirement (I). Resin components other than resin (A). In the gas barrier layered product (2) of the present invention, the water vapor transmission rate of the sheet having a thickness of 50 μm defined in the above-mentioned requirement (1) is 200 g/m 2 /day or less, but preferably 150 g /m 2 /day or less, more preferably 100 g/m 2 /day or less. By setting the water vapor transmission rate of the sheet to be 200 g/m 2 /day or less, the penetration of moisture into the inside of the sealed object such as the organic EL element formed on the transparent substrate can be suppressed, and the electrodes or organic EL elements can be effectively suppressed. layer degradation. In addition, in this specification, the water vapor transmission rate means the value measured by the method described in an Example. Furthermore, the adhesive layer of the gas barrier layered product (2) of the present invention has the same adhesive composition as that of the sheet-like material-forming material specified in the above-mentioned requirement (1), and the sheet-like material is defined as a thickness-based material. 50 μm, but the thickness of the adhesive layer is not limited to 50 μm, and can be appropriately set according to the application. Here, the thickness of the adhesive layer of the gas barrier layered bodies (1) and (2) of the present invention is appropriately set according to the application, but is preferably 2 to 50 μm, more preferably 5 to 40 μm, and more Preferably, it is 10 to 30 μm. [0019] The gas barrier layered bodies (1) and (2) of the present invention have an adhesive layer having a storage elastic modulus G' at 80°C of preferably 0.3 MPa or less, more preferably 0.2 MPa or less, still more preferably 0.1 MPa or less, more preferably 0.09 MPa or less. By setting the storage elastic modulus G' at 80°C of the adhesive layer to be 0.3 MPa or less, the gas barrier layered product of the present invention can be used as a sealing material which is excellent in conformability to irregularities and has a high effect of suppressing deterioration of the object to be sealed. Moreover, from the viewpoint of handleability, the storage elastic modulus G' of the adhesive layer at 80°C is usually 0.001 MPa or more, preferably 0.005 MPa or more, more preferably 0.01 MPa or more. In addition, in this specification, the storage elastic modulus G' of an adhesive layer means the value measured by the method as described in an Example. [0020] The adhesive layers possessed by the gas barrier layered bodies (1) and (2) of the present invention preferably have thermosetting properties. These adhesive layers are extremely excellent in adhesive strength after hardening. The conditions for thermosetting the adhesive layer are not particularly limited, but the heating temperature is usually 80 to 200°C (preferably 90 to 150°C), and the heating time is usually 30 minutes to 12 hours (preferably 1 to 6 hours). The adhesive composition of the adhesive layer forming material included in the gas barrier layered product (1) of the present invention may contain the components (A) and (B) within the range that does not impair the effects of the present invention. other ingredients. As these components, the adhesive composition preferably further contains at least one selected from the group consisting of an adhesion imparting agent (C), an imidazole-based hardening catalyst (D), and a silane coupling agent (E), and more preferably contains a component (C) , (D) and (E). In addition, the adhesive composition of the adhesive layer forming material included in the gas barrier layered product (2) of the present invention may contain components other than component (B) if it is prepared so as to satisfy the above-mentioned requirement (1). Other components may contain the polyolefin resin (A) together with the component (B), and may further contain one or more selected from the above-mentioned components (C) to (E). The adhesive composition of the adhesive layer-forming material contained in the gas barrier laminates (1) and (2) of the present invention is the total content of the components (A) and (B) relative to the adhesive. The total amount (100% by mass) of the active ingredients of the composition is preferably at least 30% by mass, more preferably at least 50% by mass, still more preferably at least 60% by mass, still more preferably at least 65% by mass, and particularly preferably at least 70% by mass or more, and usually 100 mass % or less, preferably 99.9 mass % or less. The adhesive composition of the adhesive layer forming material of the gas barrier layered products (1) and (2) of the present invention is used as components (A), (B), (C), (D) and The total content of (E) is preferably 60 to 100 mass %, more preferably 70 to 100 mass %, and still more preferably 80 to 100 mass % with respect to the total amount (100 mass %) of the active ingredients in the adhesive composition. , and even better 90~100% by mass. In addition, in this specification, the active ingredient of an adhesive composition means the component excluding the diluent solvent which is not related to a physical property contained in an adhesive composition. Hereinafter, each component contained in the adhesive composition of the material for forming the adhesive layer included in the gas barrier layered bodies (1) and (2) of the present invention will be described in detail. <Component (A): Polyolefin-based resin> By including the polyolefin-based resin (A) in the adhesive composition serving as a material for forming the adhesive layer, the water vapor in the formed adhesive layer can be reduced The transmittance can effectively suppress the penetration of moisture through the adhesive layer into the object to be sealed. In the present invention, the so-called polyolefin resin refers to a polymer having repeating units derived from olefin-based monomers. In the present invention, the polyolefin resin may be a polymer composed of only repeating units derived from an olefin-based monomer, or may have a monomer other than an olefin-based monomer together with the repeating units derived from the olefin-based monomer. A copolymer of repeating units. [0027] The olefin-based monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, more preferably ethylene or propylene. Examples of monomers other than olefin monomers include vinyl acetate, (meth)acrylate, and styrene. Example as concrete polyolefin resin is for example ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density Polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(methyl) Acrylate copolymer, polyisobutylene, polyisoprene, etc. In addition, in this specification, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same. Moreover, a polyolefin resin (A) may be used individually, and may use 2 or more types together. Also, in one aspect of the present invention, component (A) preferably contains modified polyolefin-based resin (A1). The adhesive composition containing the modified polyolefin-based resin (A1) is excellent in adhesive strength and can easily form an adhesive layer with a thin film thickness. Component (A) may use modified polyolefin-based resin (A1) in combination with non-modified polyolefin-based resin, or may be composed of modified polyolefin-based resin (A1). From the viewpoint of an adhesive composition that is excellent in adhesive strength and can easily form an adhesive layer with a thin film thickness, the content ratio of the component (A1) is based on the total amount of the component (A) contained in the adhesive composition (100 mass %), it is preferably 50 to 100 mass %, more preferably 65 to 100 mass %, still more preferably 80 to 100 mass %, still more preferably 90 to 100 mass %. In the present invention, the so-called modified polyolefin resin is a polyolefin resin having a functional group obtained by subjecting the above-mentioned polyolefin resin as a precursor to a modification treatment using a modifier having a functional group. The modifier used for the modification treatment of the polyolefin resin may be a compound having a functional group in the molecule, that is, a group contributing to the crosslinking reaction described later. Examples of the functional group include a carboxyl group, a group derived from a carboxylic acid anhydride (-CO-O-CO-), a carboxylate group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, and an imide group. group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfo group, phosphoric acid group, nitro group, urethane group, halogen atom and the like. Among these, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylate ester group, a hydroxyl group, an ammonium group, an amine group, an imide group or an isocyanate group are preferred, and a group derived from a carboxylic acid anhydride or an alkoxy group is more preferred The silyl group is more preferably a group derived from a carboxylic acid anhydride. The modifier used may be a compound having two or more functional groups in the molecule. The modified polyolefin-based resin (A1) is preferably an acid-modified resin from the viewpoint of being an adhesive composition having excellent adhesive strength, low water vapor transmission rate, and easy formation of an adhesive layer with high gas barrier properties. It is an acid-modified polyolefin-based resin or a silane-modified polyolefin-based resin, more preferably an acid-modified polyolefin-based resin. In the present invention, the so-called acid-modified polyolefin resin refers to the graft-modified polyolefin resin by the acid having a functional group of the modifier. For example, a polyolefin resin is reacted with an unsaturated carboxylic acid and/or an acid anhydride of an unsaturated carboxylic acid to introduce a carboxyl group and/or a group derived from a carboxylic acid anhydride (graft modification). The unsaturated carboxylic acid and unsaturated carboxylic acid anhydride reacted with polyolefin resin are exemplified as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid , maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. These can be used alone or in combination of two or more. Among these, maleic anhydride is preferred from the viewpoint of being an adhesive composition that is excellent in adhesive strength, has a low water vapor transmission rate, and can easily form an adhesive layer with high gas barrier properties. The blending amount of the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride reacted with the polyolefin resin is excellent in adhesive strength, low in water vapor transmission rate, and easy to form an adhesive layer with high gas barrier properties. From the viewpoint of the agent composition, it is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 1.0 parts by mass relative to 100 parts by mass of the polyolefin resin before modification. In the present invention, the acid-modified polyolefin-based resin may also use a commercially available product. Examples of commercially available acid-modified polyolefin-based resins include ADOMER (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), BondyRam (manufactured by Polyram Corporation), orevac (registered trademark) (manufactured by ARKEMA Corporation), MODIC (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like. Also, in the present invention, the so-called silane-modified polyolefin-based resin refers to a graft-modified polyolefin resin with an unsaturated silane compound of a modifier. That is, the silane-modified polyolefin resin has a structure in which the unsaturated silane compound of the side chain is graft-copolymerized on the polyolefin resin of the main chain. As the unsaturated silane compound reacted with the polyolefin resin is preferably a vinylsilane compound, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyl Triisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyl Triethylenedioxysilane, vinylpropoxysilane, vinyltriacetoxysilane, vinyltricarboxysilane, etc. These unsaturated silane compounds may be used alone or in combination of two or more. In addition, the conditions at the time of graft-polymerizing the unsaturated silane compound to the polyolefin resin of the main chain may be carried out by a conventional method for graft-polymerization. The blending amount of the unsaturated silane compound to be reacted with the polyolefin resin is relatively high from the viewpoint of being an adhesive composition having excellent adhesive strength, low water vapor transmission rate, and easy formation of an adhesive layer with high gas barrier properties. With respect to 100 parts by mass of the polyolefin tree before modification, it is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 5 parts by mass. Examples of specific silane-modified polyolefin resins are, for example, silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers, preferably silane-modified low-density polyethylene and silane-modified ultra-low density polyethylene. Silane-modified polyethylene resins such as density polyethylene and silane-modified linear low-density polyethylene. [0041] In the present invention, the silane-modified polyolefin-based resin may also be a commercially available product. Examples of commercially available silane-modified polyolefin-based resins include, for example, LINKLON (registered trademark) (manufactured by Mitsubishi Chemical Co., Ltd.), etc., but preferably LINKLON of low-density polyethylene-based, linear low-density polyethylene-based resins LINKLON of ultra-low density polyethylene and LINKLON of ethylene-vinyl acetate copolymer. The weight-average molecular weight (Mw) of the polyolefin-based resin (A) is based on the viewpoint of an adhesive composition having excellent adhesive strength, low water vapor transmission rate, and easy formation of an adhesive layer with high gas barrier properties, and From the viewpoint of an adhesive composition with good shape retention that can maintain its shape when formed into a sheet shape, it is preferably 10,000 to 2,000,000, more preferably 20,000 to 1500,000, still more preferably 25,000 to 250,000, and still more A good range is 30,000~150,000. By making the weight-average molecular weight (Mw) of the polyolefin-based resin (A) within the above-mentioned range, even when the content of the polyolefin-based resin (A) in the adhesive composition is large, the sheet-like shape of the adhesive composition can be formed. Maintenance becomes easier. Again, in this specification, the weight-average molecular weight (Mw) system uses tetrahydrofuran as solvent, the value of the standard polystyrene conversion that measures by gel permeation chromatography (GPC) method, specifically is based on the method recorded in the embodiment measured value. The same applies below. In addition, the polyolefin-based resin (A) is preferably solid at room temperature (25° C.) from the viewpoint of an adhesive composition with good shape retention that can maintain its shape when formed into a sheet shape. The content of component (A) is preferably 5 to 90 mass %, more preferably 15 to 80 mass %, relative to the total amount (100 mass %) of the active ingredients of the aforementioned adhesive composition. Preferably it is 23-70 mass %, More preferably, it is 30-60 mass %. <Component (B): Polyfunctional Epoxy Compound> The adhesive composition serving as a material for forming an adhesive layer contains a polyfunctional epoxy compound (B). By containing the polyfunctional epoxy compound (B), the adhesive layer to be formed and the gas barrier layer containing the polymer compound and subjected to the modification treatment can have good interlayer adhesion. In addition, the polyfunctional epoxy compound (B) may be used alone or in combination of two or more. In the present invention, the so-called polyfunctional epoxy compound refers to a compound having at least two or more epoxy groups in the molecule. The component (B) is preferably a bifunctional having two epoxy groups from the viewpoint of further improving the interlayer adhesion between the adhesive layer formed and the gas barrier layer containing the polymer compound and subjected to the modification treatment epoxy compound. As bifunctional epoxy compound, exemplified by bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolak-type epoxy resins (e.g. phenol. novolak-type epoxy resin, cresol. novolak-type epoxy resin, brominated phenol. novolak-type epoxy resin Aromatic epoxy compounds such as epoxy resins); alicyclic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, etc.; pentaerythritol polyglycidyl Glyceryl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalate diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis( Aliphatic epoxy compounds such as 3-glycidyl-4-glycidyloxyphenyl) propane, dimethylol tricyclodecane diglycidyl ether, etc. Among these, the polyfunctional epoxy compound (B) is preferably at least one selected from the group consisting of polyfunctional alicyclic epoxy compounds and polyfunctional aliphatic epoxy compounds. The weight average molecular weight (Mw) of the polyfunctional epoxy compound (B) is based on the viewpoint of further improving the interlayer adhesion between the adhesive layer formed and the gas barrier layer containing the polymer compound and subjected to modification treatment , preferably 200 to 5000, more preferably 300 to 4500, still more preferably 500 to 4000, still more preferably 600 to 3500. The epoxy equivalent of polyfunctional epoxy compound is preferably 100~500g/eq, more preferably 120~400g/eq, more preferably 150~300g/eq. The content of component (B), relative to 100 parts by mass of component (A) contained in the adhesive composition, is based on the adhesive layer to be formed and the gas containing the polymer compound and subjected to modification treatment. From the viewpoint of further improving the interlayer adhesion between the barrier layers, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and further, based on 80° C. of the adhesive layer to be formed The storage elastic modulus G' is adjusted to be low, and from the viewpoint of becoming a gas barrier layered product with good unevenness followability, it is more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 65 parts by mass or more . Furthermore, from the viewpoint of easily forming an adhesive layer with excellent adhesive strength, the content of the component (B) is preferably 200 parts by mass or less, more preferably 100 parts by mass of the component (A) contained in the adhesive composition. It is 180 mass parts or less, More preferably, it is 150 mass parts or less, More preferably, it is 120 mass parts or less. <Component (C): Adhesion-imparting agent> The adhesive composition preferably further contains an adhesion-imparting agent (C) from the viewpoint of making the shape retention of the formed adhesive layer more favorable. Examples of the tack-imparting agent (C) are rosin-based resins such as polymerized rosin, polymerized rosin esters, and rosin derivatives; polyterpene resins, aromatic modified terpene resins and their hydrogenated products, terpene phenol resins, etc. The terpene resin; coumarone. Indene resins; aliphatic petroleum resins, aromatic petroleum resins and their hydrides, petroleum resins such as aliphatic/aromatic copolymer petroleum resins; styrene or substituted styrene polymers; α-methylstyrene homopolymerization resins, copolymers of α-methylstyrene and styrene, copolymers of styrene monomers and aliphatic monomers, between styrene monomers and α-methylstyrene and aliphatic monomers Styrene resins such as copolymers, homopolymers of styrene monomers, copolymers of styrene monomers and aromatic monomers, etc. These adhesion-imparting agents (C) may be used alone or in combination of two or more. Among these, the component (C) is preferably a styrene-based resin, more preferably a copolymer of a styrene-based monomer and an aliphatic monomer. The softening point of the adhesion-imparting agent (C) is preferably 80° C. or higher, more preferably 85 to 170° C., more preferably from the viewpoint of further improving the shape retention and adhesive strength of the adhesive layer to be formed. 90~150℃. In addition, in this specification, a softening point means the value measured based on JISK5902. When two or more kinds of plural adhesion-imparting agents are used, the weighted average of the softening points of the plural adhesion-imparting agents preferably falls within the above-mentioned range. The content of the component (C) is preferably from 1 to 200 parts by mass, more preferably 1 to 200 parts by mass relative to 100 parts by mass of the component (A), from the viewpoint of further improving the shape retention of the adhesive layer to be formed. 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, still more preferably 20 to 80 parts by mass. <Component (D): Imidazole-based hardening catalyst> The adhesive composition preferably further contains an imidazole-based hardening catalyst (D) from the viewpoint of becoming an adhesive layer with a higher bonding strength in a high temperature environment. As the imidazole-based hardening catalyst (D), 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4- Methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. These imidazole-based hardening catalysts (D) may be used alone or in combination of two or more. Among these, as the component (D), 2-ethyl-4-methylimidazole is preferred. The content of the component (D) is preferably from 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A), and more It is 0.2-5 mass parts, More preferably, it is 0.3-2.5 mass parts. <Component (E): Silane Coupling Agent> The adhesive composition preferably further contains a silane coupling agent from the viewpoint of being easy to form an adhesive layer having excellent adhesive strength in both normal temperature and high temperature environments (E). In addition, when the adhesive composition contains a silane coupling agent, the interlayer adhesion between the formed adhesive layer and the modified gas barrier layer containing the polymer compound is further improved. The silane coupling agent (E) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule from the above viewpoint. Specific examples of the silane coupling agent (E) include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloyloxypropyltrimethoxysilane. ; 3-glycidyloxypropyltrimethoxysilane, glycidyloxyoctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Silicon compounds of structure; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane and other amine-containing silicon compounds; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane, etc. These silane coupling agents (E) may be used alone or in combination of two or more. The content of the component (E) is based on the viewpoint that it is easy to form an adhesive layer with excellent adhesive strength in any one of normal temperature and high temperature environment, and the formed adhesive layer and the polymer compound are modified. From the viewpoint of further improving the interlayer adhesion between the mass-treated gas barrier layers, relative to 100 parts by mass of the component (A), it is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and still more preferably 0.01 to 10 parts by mass. 0.05 to 2 parts by mass. <Other additives> The adhesive composition may contain other additives other than the above-mentioned components (A) to (E) within the range that does not impair the effect of the present invention. The other additives can be appropriately selected according to the application, and examples thereof include additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, and the like. These additives may be used alone or in combination of two or more. In addition, the adhesive composition may further contain a diluting solvent from the viewpoint of good formability. The dilution solvent can be appropriately selected from organic solvents, but specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, Ketone-based solvents such as methyl isobutyl ketone; aliphatic hydrocarbon-based solvents such as n-pentane, n-hexane, n-heptane, etc.; alicyclic hydrocarbon-based solvents such as cyclopentane, cyclohexane, and methylcyclohexane solvent, etc. These solvents may be used alone or in combination of two or more. In addition, the solvent content can be appropriately set in consideration of coatability and the like. <Method of Forming Adhesive Layer> As a method of forming the adhesive layer, for example, coating the adhesive composition on the release-treated surface of the release film to form a coating film, and drying the coating film to form the adhesive layer. method. Examples of the coating method of the adhesive composition include spin coating, spray coating, bar coating, blade coating, roll coating, blade coating, die coating, and gravure coating. coating method, etc. Moreover, from the viewpoint of good coatability, it is preferable to add the above-mentioned diluting solvent to the adhesive composition to form a solution. As a drying condition at the time of drying a coating film, it is preferable to perform a drying process for 30 seconds - 5 minutes at 80-150 degreeC, for example. [Gas Barrier Layer] The gas barrier layer of the gas barrier layered product of the present invention is a layer containing a polymer compound and subjected to modification treatment. Since this gas barrier layer has excellent gas barrier properties and flexibility, it can be a gas barrier property laminate that is also excellent in resistance to bending. The thickness of the gas barrier layer is preferably 50 to 300 nm, more preferably 50 to 200 nm. The gas barrier layer of the gas barrier layered product of the present invention has sufficient gas barrier properties even if the thickness is on the nanometer scale. Examples of the polymer compound contained in the gas barrier layer include silicon-containing polymer compounds such as polyorganosiloxane, polysilazane-based compounds, polyimide, polyamide, and polyamide amide. Amines, polyphenylene ethers, polyetherketones, polyetheretherketones, polyolefins, polyesters, polycarbonates, polysulfites, polyethersines, polyphenylene sulfides, polyarylates, acrylic resins, cycloolefin polymers compounds, aromatic polymers, etc. These polymer compounds may be used alone or in combination of two or more. Among these, the polymer compound contained in the gas barrier layer is preferably a silicon-containing polymer compound, more preferably a polysilazane-based compound, from the viewpoint of obtaining a gas barrier layered product having excellent gas barrier properties. . The number average molecular weight of the polysilazane-based compound is preferably from 100 to 50,000. The polysilazane-based compound is a polymer having a repeating unit containing a -Si-N- bond (silicon-nitrogen bond) in the molecule, specifically a polymer having a repeating unit represented by the following general formula (1) thing.
Figure 02_image001
In the above-mentioned general formula (1), n represents the number of repeating units, and represents an integer of 1 or more. Rx, Ry, and Rz independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, and an unsubstituted or substituted aryl group group or alkylsilyl group. Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferably a hydrogen atom. In addition, the polymer compound contained in the gas barrier layer may be an inorganic polysiloxane in which all of Rx, Ry, and Rz in the general formula (1) are hydrogen atoms, or may be at least one of Rx, Ry, and Rz. Organopolysilazane with a base other than hydrogen atom. [0069] The polysilazane compound may be used alone or in combination of two or more. Moreover, as a polysilazane compound, a polysilazane modification|denaturation thing can also be used, and a commercial item can also be used. [0070] In addition to the above-mentioned polymer compound, the gas barrier layer may further contain other components within a range that does not impair the effects of the present invention. Examples of other components include hardeners, other polymers, antiaging agents, light stabilizers, flame retardants, and the like. The content of the polymer compound in the gas barrier layer is preferably 50 to 100% by mass relative to the total amount (100% by mass) of the components in the gas barrier layer from the viewpoint of becoming a gas barrier layer having more excellent gas barrier properties, More preferably, it is 70 to 100 mass %, and still more preferably, it is 80 to 100 mass %. As a method for forming the gas barrier layer, for example, a solution for forming a gas barrier layer containing at least one of the polymer compounds, other components and solvents as desired, and the like, is exemplified by a spin coater, a blade coater, A method in which a conventional device such as a gravure coater coats and forms a coating film, and then dries the coating film. [0072] As the modification method of the gas barrier layer, treatment for changing the bonding structure of the polymer layer, such as ion implantation treatment, plasma treatment, radiation treatment, and heat treatment, is preferred. These treatments may be used alone or in combination of two or more. The ion implantation treatment is a method of modifying the gas barrier layer by implanting ions into the gas barrier layer as described later. Plasma treatment is a method of modifying the gas barrier layer by exposing the gas barrier layer to plasma. For example, the plasma treatment can be performed according to the method described in Japanese Patent Laid-Open No. 2012-106421. The radiation irradiation treatment is a method of modifying the gas barrier layer by irradiating the gas barrier layer with radiation. The radiation is preferably a short wavelength with a high effect of changing the bonding structure of the polymer layer, and ultraviolet rays, especially vacuum ultraviolet rays, are preferably used. For example, the vacuum ultraviolet light modification treatment can be performed according to the method described in Japanese Patent Laid-Open No. 2013-226757. Among these, the modification treatment of the gas barrier layer is preferably an ion implantation treatment from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed without roughening the surface of the gas barrier layer and efficiently reforming the gas barrier layer inside. During the ion implantation process, the ions implanted in the gas barrier layer are exemplified as ions of rare gases such as argon, helium, neon, krypton, xenon, etc.; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, Ions such as sulfur; ions of alkane-based gases such as methane and ethane; ions of alkene-based gases such as ethylene and propylene; ions of alkane-based gases such as pentadiene and butadiene; acetylene, etc. Ions of alkyne-based gases; ions of aromatic hydrocarbon-based gases such as benzene and toluene; ions of naphthenic-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; metal ions; Ions of organosilicon compounds; etc. These plasmas may be used alone or in combination of two or more. Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred, and argon ions are more preferred, from the viewpoint that ions can be implanted more easily and a gas barrier layer having particularly excellent gas barrier properties can be obtained. [0074] The method of implanting ions is not particularly limited. Examples include, for example, a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions into plasma (ions of plasma-generating gas), and the like, and a method of implanting ions into plasma (hereinafter sometimes referred to as "" The plasma ion implantation method") is preferred because the gas barrier layer can be easily obtained. Plasma ion implantation can, for example, generate a plasma in an environment containing a gas that will generate electricity, and apply a negative high-voltage pulse to the ion-implanted layer, so that ions (cations) in the plasma are implanted into the ions to be implanted. on the surface of the layer. [Substrate layer] Examples of the substrate layer included in the gas barrier layered product of the present invention include, for example, metal foil, resin film, thin film glass, and the like, preferably a resin film. Examples of the resin component constituting the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polyamide Silica, polyether ash, polyphenylene sulfide, polyarylates, acrylic resins, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like. These resin components may be used alone or in combination of two or more. When the base material layer is composed of a resin film, from the viewpoint of improving the adhesion with the layer laminated on the resin film, it is preferable to apply an easy-bonding treatment to the surface of the resin film by an oxidation method or a concavo-convex method. . Examples of the oxidation method include corona discharge method, plasma discharge treatment, chromic acid treatment (wet treatment), hot air treatment, ozone and ultraviolet irradiation treatment, and the like. [0077] The thickness of the base material layer is not particularly limited, but from the viewpoint of ease of handling, it is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, still more preferably 5 to 100 μm. [Undercoat layer] In the gas barrier layered product of the present invention, from the viewpoint of further improving the adhesion between the base material layer and the gas barrier layer, as one of the easy-adhesion treatment means, the base material layer and the gas barrier layer can also be used. An undercoat layer is provided between the gas barrier layers. As said undercoat layer, the layer which hardens the composition containing an ultraviolet curable compound, for example. The composition containing the ultraviolet curable compound may contain inorganic fillers such as silicon oxide particles. The thickness of the aforementioned undercoat layer is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm. [Release film] As the release film of the gas barrier layered product of the present invention, a conventionally known release film can be used, for example, a release layer having a release layer subjected to release treatment with a release agent on the base material for release film is exemplified. Examples of substrates for release films include paper substrates such as cellophane, coated paper, high-quality paper, etc.; laminated paper laminated with thermoplastic resins such as polyethylene on these paper substrates; polyethylene terephthalate Plastic films formed from ester resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc.; etc. Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, butadiene-based resins, etc., long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins. . [Sealed body] The sealing system of the present invention is sealed with the gas barrier laminate of the present invention. The sealing system of the present invention includes, for example, a transparent substrate, an element (an object to be sealed) formed on the transparent substrate, and a gas barrier layered body of a sealing material for sealing the element. [0081] The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material with high transmittance of visible light. In addition, it is preferably a material that has high barrier properties against moisture or gas that may penetrate from the outside of the element, and is excellent in solvent resistance or weather resistance. Specifically, it is exemplified by transparent inorganic materials such as quartz or glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, Transparent plastics of polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramides, polyimides, polystyrenes, polyarylates, polysaccharides, polyolefins, etc. ; The aforementioned gas barrier film. The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmission through chlorine or the performance of blocking the inside and outside of the element. [0082] Examples of the object to be sealed include organic EL elements, organic EL display elements, liquid crystal display elements, solar cell elements, and the like. That is, it is preferable that the sealing body of this invention seals an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas barrier layered body of this invention. [0083] The manufacturing method of the sealing body of the present invention is not particularly limited. For example, after stacking the adhesive layer which the gas barrier layered product of the present invention has on the object to be sealed, the adhesive layer and the object to be sealed are bonded by heating. Next, by hardening the adhesive layer, the sealing body of the present invention can be produced. [0084] The bonding conditions when bonding the gas barrier layered body and the object to be sealed are not particularly limited. The subsequent temperature is, for example, 23 to 100°C, preferably 40 to 80°C. This subsequent treatment can be performed under pressure. As the curing conditions when the adhesive layer is cured, the conditions described above can be used. [Examples] [0085] The present invention will be described in more detail with reference to examples below. However, the present invention is not limited to the following examples. In addition, the weight average molecular weight (Mw) of a modified polyolefin resin, an acrylic resin, and a polyfunctional epoxy compound is the value measured by the following method. <The weight-average molecular weight (Mw) of the modified polyolefin-based resin and acrylic resin> The weight-average molecular weight (Mw) of the modified polyolefin-based resin and the weight-average molecular weight (Mw) of the acrylic resin are based on the use of a gel permeation layer. The analysis (GPC) apparatus (manufactured by TOSOH Co., Ltd., product name "HLC-8320") was used to measure under the following conditions, and it was converted into a value of the weight average molecular weight of standard polystyrene. (measurement conditions). Measurement sample: tetrahydrofuran solution with a sample concentration of 1% by mass. Column: 2 pieces of "TSK gel Super HM-H" and 1 piece of "TSK gel Super H2000" (both manufactured by TOSOH Co., Ltd.) are connected in sequence. Column temperature: 40 ℃. Developing solvent: tetrahydrofuran tetrahydrofuran. Flow rate: 0.60 mL/min <The weight average molecular weight (Mw) of the polyfunctional epoxy compound> The weight average molecular weight (Mw) of the polyfunctional epoxy compound was measured using the above gel permeation chromatography (GPC) apparatus under the following conditions In the measurement, it is converted into the weight average molecular weight of standard polystyrene corresponding to the retention time of the peak top of the largest area among the peaks observed in plural. Examples 1 to 2 and Comparative Examples 1 to 2 (1) Preparation of Adhesive Composition The base ketone was diluted, and in Examples 1 to 2 and Comparative Example 1, adhesive compositions with an active ingredient concentration of 30% by mass were prepared, respectively, and in Comparative Example 2, an adhesive composition with an active ingredient concentration of 35% by mass was prepared. Details of each ingredient used are as follows. . Modified polyolefin resin: manufactured by Mitsui Chemicals Co., Ltd., product name "UNISTOLE H-200", acid-modified α-olefin polymer, solid at 25°C, weight average molecular weight (Mw)=52,000. . Acrylic resin: copolymer of butyl acrylate (BA) and acrylic acid (AAc), BA/AAc=90/10, solid at 25°C, weight average molecular weight (Mw)=650,000. . Polyfunctional epoxy compound: manufactured by Kyoeisha Chemical Co., Ltd., product name "EPOLIGHT 4000", hydrogenated bisphenol A diglycidyl ether, liquid at 25°C, epoxy equivalent = 215~245g/eq, weight average Molecular weight (Mw)=800. . Adhesion imparting agent: manufactured by Mitsui Chemicals Co., Ltd., product name "FTR6100", copolymer of styrene monomer and aliphatic monomer, softening point = 95°C. . Imidazole-based hardening catalyst: Shikoku Chemical Industry Co., Ltd., product name "CURAZOLE 2E4MZ", 2-ethyl-4-methylimidazole. . Silane coupling agent: Shin-Etsu Chemical Co., Ltd., product name "KBM-4803", glycidyloxyoctyltrimethoxysilane. (2) Formation of the adhesive layer on the peel-treated surface of the release film (manufactured by LINTEK Co., Ltd., product name "SP-PET 382150"), apply the prepared adhesive composition to form a coating film, so that The coating film was dried at 100° C. for 2 minutes to form an adhesive layer with a thickness of 12 μm. In addition, a laminate in which an adhesive layer with a thickness of 50 μm was formed on the release film was produced in the same manner as described above, and was used for the measurement of the water vapor transmission rate of the adhesive layer. (3) The formation of the gas barrier layer on both sides of a polyethylene terephthalate (PET) film with a thickness of 50 μm (manufactured by Toyobo Co., Ltd., product name "PET50A4300"), which is subjected to an easy-bonding treatment, An ultraviolet curable acrylate resin composition (manufactured by JSR Co., Ltd., product name "OPSTAR Z7530") was applied using a wire bar to form a coating film, and the coating film was dried at 70° C. for 1 minute. Next, using an electrodeless UV lamp system (manufactured by HERAEUS Co., Ltd.), ultraviolet rays were irradiated with an illuminance of 250 mW/cm 2 and a light intensity of 170 mJ/cm 2 to harden the coating film to form an undercoat layer with a thickness of 1000 nm. Next, on the formed undercoat layer, a spin coater (manufactured by MIKASA Co., Ltd., product name "MS-A200") was applied with perhydropolysilazane at a rotation speed of 3000 rpm and a rotation time of 30 seconds. A coating agent (manufactured by MERCK PERFORMANCE MATERIALS, product name "AKUAMIKA NL110-20", solvent: xylene) having a solid content concentration of 10% by mass as the main component was used to form a coating film. Then, the coating film was dried at 120° C. for 2 minutes to form a polysilazane layer made of polysilazane with a thickness of 150 nm on the undercoat layer. Next, the surface of the formed polysilazane was modified by plasma ion implantation using a plasma ion implantation apparatus under the following conditions to form a gas barrier layer with a thickness of 150 nm. (Processing conditions for plasma ion implantation). Chamber pressure: 0.2Pa. Plasma generator body: Argon. Gas flow: 100sccm. RF output: 1000W. RF frequency: 1000Hz. RF pulse width: 50μsec. RF delay: 25n seconds. DC voltage: -6kV. DC frequency: 1000Hz. DC pulse width: 5μsec. DC delay: 50μsec. Duty cycle: 0.5%. Processing time: 200 seconds. On the formed gas barrier layer, in the same manner as described above, the formation of a gas barrier layer with a thickness of 150 nm was repeated three times to obtain a gas barrier layer with a thickness of 150 nm in which four layers were laminated. Gas barrier thin film of 600nm gas barrier layer. (4) Preparation of gas barrier layered product The surface of the adhesive layer with a thickness of 12 μm formed in the above (2) and the surface of the gas barrier layer with a thickness of 600 nm of the gas barrier film produced in the above (3), using a thermal layer A bonding machine was used, and they were bonded together at 60° C. to produce a gas barrier layered product. [0090] The following physical property values were measured and evaluated using the above-mentioned adhesive layer and gas barrier layered product obtained in Examples and Comparative Examples. These results are shown in Table 1. [Water Vapor Transmission Rate of Adhesive Layer] The peeling film was removed from the laminate made of the peeling film and the adhesive layer with a thickness of 50 μm produced in Examples and Comparative Examples, and only the aforementioned adhesive layer was used as a test For the sample, the water vapor transmission rate of the adhesive layer was measured using a gas transmission rate measuring device (manufactured by mocon, product name "PERMATRAN"). [Storage Elastic Modulus G' of Adhesive Layer] The adhesive layers formed in Examples and Comparative Examples were overlapped in multiple layers, heated and compressed at 60° C. using a thermal laminator to obtain a multi-layer adhesive layer with a thickness of 1 mm. body. The multilayer body of the adhesive layer was used as a test sample, and a viscoelasticity measuring device (manufactured by Anton Paar Co., Ltd., product name "Physica MCR301") was used. The storage elastic modulus G' of the multilayer body of the aforementioned adhesive layer. The values of the measured storage elastic modulus G' at 80°C are shown in Table 1. [Interlayer Adhesion Evaluation] The gas barrier laminates produced in Examples and Comparative Examples were cut into a size of 25 mm in length × 300 mm in width, the release film was removed, and the surface of the exposed adhesive layer was adhered to a glass plate, using The thermal laminator was pressed at 60°C to prepare a test sample. Next, the test sample was heated at 100° C. for 2 hours to harden the adhesive layer, and then left to stand at 23° C. for 24 hours. Furthermore, after standing for 168 hours in an environment with a temperature of 85° C. and 85% RH (relative humidity), the gas barrier layered product was peeled off from the glass plate at a peeling angle of 180°, and it was confirmed whether the adhesive layer was turned off or not. On the glass plate, the interlayer adhesion between the gas barrier layer and the adhesive layer was evaluated based on the following criteria. A: It was not confirmed that the adhesive layer was transferred to the glass plate. F: It was confirmed that the adhesive layer was transferred to the glass plate. [Evaluation of Concavity and Concavity Followability] On a glass substrate, a small piece of polyethylene terephthalate having a thickness of 10 μm was left standing as a pseudo device. Next, the peeling films of the gas barrier laminates produced in the examples and comparative examples were removed, and the exposed adhesive layer was laminated on the glass substrate and the pseudo device in such a way that the exposed adhesive layer completely covered the pseudo device on the glass substrate, and a thermal layer was used. The machine was sealed at 80°C, followed by pressure treatment at 80°C and 0.5MPa for 20 minutes. In addition, the adhesive layer was hardened by heating in an environment of 100° C. for 2 hours. Using an optical microscope, the interface between the pseudo-device and the adhesive layer after curing was observed from above, and the unevenness followability of the gas barrier layered product was evaluated by the presence or absence of a gap between the pseudo-device and the adhesive layer as follows. A: There is no gap between the pseudo device and the adhesive layer, so the unevenness followability is good. F: A gap was observed between the pseudo device and the adhesive layer, so the unevenness followability was poor. [0095]
Figure 02_image003
The adhesive layer possessed by the gas barrier layered products produced in Examples 1 and 2 has excellent interlayer adhesion with the gas barrier layer and low water vapor transmission rate, so it can be said that the water through the adhesive layer is suppressed. A sealing material with excellent immersion effect on the body to be sealed. On the other hand, the gas barrier layered product produced in Comparative Example 1 had poor interlayer adhesion between the adhesive layer and the gas barrier layer. In addition, the water vapor transmission rate of the adhesive layer included in the gas barrier layered product produced in Comparative Example 2 was a very high value. Therefore, in the comparative example 2, it was completed without performing another test.

Claims (11)

一種氣體障壁性層合體,其特徵係具有含高分子化合物且施以改質處理的氣體障壁層、與由含有聚烯烴樹脂(A)及多官能環氧化合物(B)的接著劑組成物形成的接著劑層,前述多官能環氧化合物(B)係選自多官能脂環式環氧化合物及多官能脂肪族環氧化合物之1種以上,且具有前述氣體障壁層與前述接著劑層直接層合的構成。 A gas barrier layered product comprising a gas barrier layer containing a polymer compound and subjected to a modification treatment, and an adhesive composition comprising a polyolefin resin (A) and a polyfunctional epoxy compound (B). The adhesive layer, the polyfunctional epoxy compound (B) is one or more selected from polyfunctional alicyclic epoxy compounds and polyfunctional aliphatic epoxy compounds, and has the gas barrier layer and the adhesive layer directly. Laminated composition. 如請求項1記載之氣體障壁性層合體,其中,成分(A)含有改性聚烯烴樹脂(A1)。 The gas barrier layered product according to claim 1, wherein the component (A) contains a modified polyolefin resin (A1). 如請求項2記載之氣體障壁性層合體,其中,成分(A1)為酸改性聚烯烴樹脂。 The gas barrier layered product according to claim 2, wherein the component (A1) is an acid-modified polyolefin resin. 如請求項1或2記載之氣體障壁性層合體,其中,前述接著劑層的80℃之儲存彈性率G’為0.3MPa以下。 The gas barrier layered product according to claim 1 or 2, wherein the storage elastic modulus G' of the adhesive layer at 80°C is 0.3 MPa or less. 如請求項1或2記載之氣體障壁性層合體,其中,成分(A)的含量相對於前述接著劑組成物的有效成分之全量而言,為5~90質量%。 The gas barrier layered product according to claim 1 or 2, wherein the content of the component (A) is 5 to 90% by mass with respect to the total amount of the active ingredients in the adhesive composition. 如請求項1或2記載之氣體障壁性層合體,其中,成分(B)的含量相對於前述接著劑組成物所含有的成分(A)100質量份而言,為5~200質量份。 The gas barrier layered product according to claim 1 or 2, wherein the content of the component (B) is 5 to 200 parts by mass relative to 100 parts by mass of the component (A) contained in the adhesive composition. 如請求項1或2記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有黏著賦予劑(C)。 The gas barrier layered product according to claim 1 or 2, wherein the adhesive composition further contains an adhesion-imparting agent (C). 如請求項1或2記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有咪唑系硬化觸媒(D)。 The gas barrier layered product according to claim 1 or 2, wherein the adhesive composition further contains an imidazole-based curing catalyst (D). 如請求項1或2記載之氣體障壁性層合體,其中,前述接著劑組成物進一步含有矽烷偶合劑(E)。 The gas barrier layered product according to claim 1 or 2, wherein the adhesive composition further contains a silane coupling agent (E). 一種氣體障壁性層合體,其特徵係具有含高分子化合物且施以改質處理的氣體障壁層、與由含有多官能環氧化合物(B)且符合下述要件(I)的接著劑組成物形成的接著劑層,前述多官能環氧化合物(B)係選自多官能脂環式環氧化合物及多官能脂肪族環氧化合物之1種以上,且具有前述氣體障壁層與前述接著劑層直接層合的構成,‧要件(I):由前述接著劑組成物形成的厚度50μm的薄片狀物的水蒸氣透過率為200g/m2/day以下。 A gas barrier layered product, characterized by having a gas barrier layer containing a polymer compound and subjected to modification treatment, and an adhesive composition containing a polyfunctional epoxy compound (B) and meeting the following requirements (I) In the formed adhesive layer, the polyfunctional epoxy compound (B) is one or more selected from polyfunctional alicyclic epoxy compounds and polyfunctional aliphatic epoxy compounds, and has the gas barrier layer and the adhesive layer The structure of direct lamination, Requirement (I): The water vapor transmission rate of the sheet-like object with a thickness of 50 μm formed from the adhesive composition is 200 g/m 2 /day or less. 一種密封體,其特徵係將有機EL元件、有機EL顯示器元件、液晶顯示器元件、或太陽能電池元件以請求項1~10中任一項記載之氣體障壁性層合體進行密封而成。 A sealing body characterized by sealing an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas barrier layered body according to any one of claims 1 to 10.
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