TW202327868A - Multilayer structure and method for producing same, protective sheet for electronic device using said multilayer structure, and electronic device - Google Patents

Multilayer structure and method for producing same, protective sheet for electronic device using said multilayer structure, and electronic device Download PDF

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TW202327868A
TW202327868A TW111138188A TW111138188A TW202327868A TW 202327868 A TW202327868 A TW 202327868A TW 111138188 A TW111138188 A TW 111138188A TW 111138188 A TW111138188 A TW 111138188A TW 202327868 A TW202327868 A TW 202327868A
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layer
multilayer structure
substrate
coating
acid
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久詰修平
尾下竜也
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日商可樂麗股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

Provided are: a multilayer structure having high barrier properties and clarity and a method for producing the same; a protective sheet for an electronic device using the multilayer structure; and an electronic device. This multilayer structure includes a substrate (X) and a layer (Y). The layer (Y) contains a reaction product (D) of a metal oxide (A) that includes aluminum atoms, and an inorganic phosphorous compound (BI). The substrate (X) and the layer (Y) are contiguous. The image clarity of the multilayer structure with an optical comb width of 0.25 mm when measured according to ISO17221:2014 is 90% or more.

Description

多層構造體及其製造方法，以及使用其之電子裝置的保護薄片及電子裝置Multilayer structure, manufacturing method thereof, protective sheet for electronic device using same, and electronic device

本發明關於一種阻氣性及水蒸氣阻隔性高，且鮮明度高的多層構造體及其製造方法、以及使用其之電子裝置的保護薄片及電子裝置。The present invention relates to a multilayer structure with high gas barrier properties and water vapor barrier properties and high clarity, its manufacturing method, a protective sheet for electronic devices using the same, and electronic devices.

具備太陽電池或顯示裝置之電子機器等之電子裝置，係需要保護表面的透光性保護構件。作為該保護構件，例如有使用一種在厚玻璃板、樹脂基材上具備阻隔層的阻隔性(氧阻隔性及水蒸氣阻隔性)優異之保護薄片等的情況。Electronic devices such as electronic equipment equipped with solar cells or display devices require a light-transmitting protective member that protects the surface. As the protective member, for example, a protective sheet having a barrier layer on a thick glass plate or a resin substrate and having excellent barrier properties (oxygen barrier properties and water vapor barrier properties) may be used.

作為前述阻隔性優異的保護薄片，專利文獻中1中記載一種具備保護薄片之電子裝置，該保護薄片包含多層構造體，其為在基材(X)上塗佈含有鋁的化合物與磷化合物之塗佈液，接著進行乾燥及熱處理而設置含有反應生成物之層(Y)，前述反應生成物之平均粒徑為5~70nm，該保護薄片係阻氣性及水蒸氣阻隔性優異，即使於溫濕試驗後也能維持性能。 [先前技術文獻] [專利文獻] As the aforementioned protective sheet excellent in barrier properties, Patent Document 1 describes an electronic device provided with a protective sheet comprising a multilayer structure obtained by coating a compound containing aluminum and a phosphorus compound on a substrate (X). The coating solution is then dried and heat-treated to form a layer (Y) containing the reaction product. The average particle size of the reaction product is 5-70 nm. This protective sheet has excellent gas barrier properties and water vapor barrier properties. Maintains performance even after temperature and humidity tests. [Prior Art Literature] [Patent Document]

[專利文獻1]國際公開第2016/103720號[Patent Document 1] International Publication No. 2016/103720

[發明所欲解決的課題][Problems to be Solved by the Invention]

近年來，於電子裝置等之保護薄片(多層構造體)，有要求更高水準的鮮明度之情況，於前述以往的電子裝置所用的多層構造體中，有鮮明度不充分之情況。前述以往的電子裝置所用的多層構造體之高阻隔性係有用作為電子裝置等的保護薄片，要求維持著那樣的性能之具有高鮮明度的多層構造體。本發明者們為了實現鮮明度高的多層構造體，使用圖像清晰度高的基材作為基材(X)，進行反覆的檢討，但高鮮明度之實現為困難。本發明者們專心致力地檢討，結果發現在形成層(Y)時塗佈的塗佈液之塗佈速度與所得的多層構造體之鮮明度係有關聯，終於實現本發明。In recent years, protective sheets (multilayer structures) of electronic devices and the like have been required to have a higher level of sharpness, and the above-mentioned conventional multilayer structures used for electronic devices may not have sufficient sharpness. The high barrier properties of the multilayer structures used in the aforementioned conventional electronic devices are useful as protective sheets for electronic devices, etc., and a multilayer structure with high clarity maintaining such performance is required. In order to realize a multilayer structure with high definition, the present inventors have repeatedly examined using a substrate with high image definition as the substrate (X), but it has been difficult to realize high definition. As a result of intensive investigations, the present inventors found that the coating speed of the coating liquid applied when forming the layer (Y) is related to the clarity of the obtained multilayer structure, and finally achieved the present invention.

本發明是基於如以下的情事而完成者，其目的在於提供一種具有高的阻隔性及鮮明度之多層構造體及其製造方法、以及使用其之電子裝置的保護薄片及電子裝置。 [解決課題的手段] The present invention is based on the following circumstances, and an object of the present invention is to provide a multilayer structure having high barrier properties and clarity, a method for producing the same, a protective sheet for electronic devices using the same, and an electronic device. [means to solve the problem]

依據本發明，前述目的可藉由提供以下各項來達成： [1]一種多層構造體，其係具備基材(X)及層(Y)之多層構造體，層(Y)包含含有鋁原子的金屬氧化物(A)(以下，亦僅簡稱「金屬氧化物(A)」)與無機磷化合物(BI)之反應生成物(D)，基材(X)與層(Y)係鄰接，依據ISO17221：2014測定的光梳寬度0.25mm之前述多層構造體的圖像清晰度為90%以上。 [2]如[1]之多層構造體，其依據JIS K7105：1981測定的霧度值為3%以下。 [3]如[1]或[2]之多層構造體，其依據ISO15106-5：2015測定的40℃、90%RH下之水蒸氣透過率為1×10 -2g/m 2・day以下。 [4]如[1]~[3]中任一項之多層構造體，其中基材(X)在210℃下加熱1分鐘時的MD方向之熱收縮率為2.90%以下。 [5]如[1]~[4]中任一項之多層構造體，其中依據ISO17221：2014測定的光梳寬度0.25mm之基材(X)的圖像清晰度為90%以上。 [6]如[1]~[5]中任一項之多層構造體，其中基材(X)具有表面層。 [7]如[1]~[6]中任一項之多層構造體，其具有基材(X)與層(Y)直接積層之構成。 [8]如[1]~[6]中任一項之多層構造體，其具有基材(X)與層(Y)隔著接著層(I)積層之構成。 [9]如[1]~[8]之多層構造體，其中具備在基材(X)之兩面分別配置的層(Y)。 [10]一種多層構造體之製造方法，其包含：在基材(X)的至少一面側，塗佈包含含有鋁原子的金屬氧化物(A)、無機磷化合物(BI)及溶劑之塗佈液(S)，去除前述溶劑而形成層(Y)的前驅物層之步驟(I)；及，熱處理層(Y)的前驅物層而形成層(Y)之步驟(II)；步驟(I)的塗佈液(S)之塗佈速度係塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下，依據ISO17221：2014測定的在光梳寬度0.25mm所得之多層構造體的圖像清晰度為90%以上。 [11]一種電子裝置的保護薄片，其包含如[1]~[9]中任一項之多層構造體。 [12]如[11]的保護薄片，其係保護光電轉換裝置、資訊顯示裝置或照明裝置的表面之保護薄片。 [13]一種電子裝置，其具有如[11]或[12]之保護薄片。 [發明的效果] According to the present invention, the aforementioned objects can be achieved by providing the following items: [1] A multilayer structure comprising a base material (X) and a layer (Y), wherein the layer (Y) includes aluminum atoms The reaction product (D) of the metal oxide (A) (hereinafter referred to simply as "metal oxide (A)") and the inorganic phosphorus compound (BI), the substrate (X) and the layer (Y) are adjacent, The image definition of the aforementioned multilayer structure with a comb width of 0.25 mm measured in accordance with ISO17221:2014 is 90% or more. [2] The multilayer structure according to [1], wherein the haze value measured in accordance with JIS K7105:1981 is 3% or less. [3] The multilayer structure according to [1] or [2], which has a water vapor transmission rate of 1×10 -2 g/m 2 ·day or less at 40°C and 90%RH measured in accordance with ISO15106-5:2015 . [4] The multilayer structure according to any one of [1] to [3], wherein the heat shrinkage rate in the MD direction of the substrate (X) when heated at 210° C. for 1 minute is 2.90% or less. [5] The multilayer structure according to any one of [1] to [4], wherein the image resolution of the substrate (X) with a comb width of 0.25 mm measured in accordance with ISO17221:2014 is 90% or more. [6] The multilayer structure according to any one of [1] to [5], wherein the substrate (X) has a surface layer. [7] The multilayer structure according to any one of [1] to [6], which has a structure in which the substrate (X) and the layer (Y) are directly laminated. [8] The multilayer structure according to any one of [1] to [6], which has a structure in which a substrate (X) and a layer (Y) are laminated via an adhesive layer (I). [9] The multilayer structure according to [1] to [8], which includes layers (Y) respectively arranged on both surfaces of the substrate (X). [10] A method for producing a multilayer structure, comprising: coating a metal oxide (A) containing an aluminum atom, an inorganic phosphorus compound (BI), and a solvent on at least one side of a substrate (X) Liquid (S), the step (I) of removing the aforementioned solvent to form the precursor layer of the layer (Y); and the step (II) of forming the layer (Y) by heat-treating the precursor layer of the layer (Y); step (I ) of the coating solution (S), the coating speed is 0.03 cm/s to 2.5 cm/s per 1 cm of the coating width, and the image of the multilayer structure measured in accordance with ISO17221:2014 at a comb width of 0.25 mm The clarity is above 90%. [11] A protective sheet for an electronic device, comprising the multilayer structure according to any one of [1] to [9]. [12] The protective sheet according to [11], which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device or a lighting device. [13] An electronic device having the protective sheet according to [11] or [12]. [Effect of the invention]

依據本發明，可提供一種具有高的阻隔性及鮮明度之多層構造體及其製造方法、以及使用其之電子裝置的保護薄片及電子裝置。According to the present invention, it is possible to provide a multilayer structure having high barrier properties and clarity, a method for producing the same, a protective sheet for electronic devices using the same, and electronic devices.

[實施發明的形態][Mode of Carrying Out the Invention]

本說明書中，「阻隔性」主要意指氧阻隔性及水蒸氣阻隔性之兩者，「阻氣性」主要意指氧阻隔性。又，「鮮明度」係透過本發明之多層構造體所觀看的影像之鮮明度的評價，如實施例記載，藉由以目視確認透過本發明之多層構造體所觀看的影像時之視覺辨認性來判斷。In this specification, "barrier property" mainly means both of oxygen barrier property and water vapor barrier property, and "gas barrier property" mainly means oxygen barrier property. In addition, "sharpness" is an evaluation of the sharpness of images viewed through the multilayer structure of the present invention. As described in Examples, the visibility of images viewed through the multilayer structure of the present invention is visually confirmed. to judge.

[多層構造體] 本發明之多層構造體係具備基材(X)及層(Y)之多層構造體，層(Y)包含金屬氧化物(A)與無機磷化合物(BI)之反應生成物(D)，基材(X)與層(Y)係鄰接，依據ISO17221：2014測定的光梳寬度0.25mm之該多層構造體的圖像清晰度為90%以上。 [Multilayer structure] The multilayer structure system of the present invention has a multilayer structure comprising a substrate (X) and a layer (Y), the layer (Y) includes a reaction product (D) of a metal oxide (A) and an inorganic phosphorus compound (BI), and the substrate (X) is adjacent to the layer (Y), and the image resolution of the multilayer structure with a comb width of 0.25 mm measured in accordance with ISO17221:2014 is 90% or more.

本說明書中所謂「鄰接」，就是意指以非常接近狀態被積層，具體而言意指直接積層或隔著接著層等其他層(例如厚度為10μm以下的接著層)被積層。於基材(X)與層(Y)鄰接之構成中，基材(X)與層(Y)之距離可為0μm以上10μm以下，也可為0μm以上1μm以下，也可為0μm以上0.1μm以下，也可為0μm以上0.03μm以下。又，例如具有數個基材(X)時，只要其內之1層的基材(X)與層(Y)鄰接即可，其他基材(X)可與層(Y)不鄰接。同樣地，具有數個層(Y)時，只要其內之1層的層(Y)與基材(X)鄰接即可，其他層(Y)可與基材(X)不鄰接。亦即，只要至少1組的基材(X)與層(Y)鄰接即可。The term "adjacent" in this specification means to be laminated in a very close state, and specifically means to be laminated directly or via another layer such as an adhesive layer (for example, an adhesive layer with a thickness of 10 μm or less). In the structure in which the substrate (X) and the layer (Y) are adjacent, the distance between the substrate (X) and the layer (Y) may be 0 μm to 10 μm, may be 0 μm to 1 μm, or may be 0 μm to 0.1 μm Below, it may be not less than 0 μm and not more than 0.03 μm. Also, for example, when there are several substrates (X), it is only necessary that the substrate (X) of one layer is adjacent to the layer (Y), and the other substrates (X) may not be adjacent to the layer (Y). Likewise, when there are several layers (Y), it is only necessary that one layer (Y) is adjacent to the substrate (X), and the other layers (Y) may not be adjacent to the substrate (X). That is, at least one set of substrates (X) should just be adjacent to the layer (Y).

本發明之多層構造體由於圖像清晰度為90%以上，故例如作為電子裝置的保護薄片使用時，鮮明度優異。本發明之多層構造體的圖像清晰度較佳為91%以上，更佳為92%以上，尤佳為93%以上，亦有尤更佳為94%以上或95%以上之情況。本發明之多層構造體的圖像清晰度可為100%以下，也可為99%、98%、97%或96%以下。Since the image resolution of the multilayer structure of the present invention is 90% or more, it is excellent in sharpness when used as a protective sheet of an electronic device, for example. The image definition of the multilayer structure of the present invention is preferably 91% or higher, more preferably 92% or higher, especially preferably 93% or higher, and even more preferably 94% or higher or 95% or higher. The image clarity of the multilayer structure of the present invention may be 100% or less, or 99%, 98%, 97% or 96% or less.

使本發明之多層構造體的圖像清晰度成為90%以上之手法的詳細係如後述，但特別重要的是使用圖像清晰度高的基材(X)，及以後述塗佈液(S)之塗佈速度係塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下進行塗佈。此處，所謂「塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下」，就是按照塗佈寬度的長度，改變塗佈速度之條件，例如塗佈寬度為10cm時(以10cm的寬度進行塗佈時)，意指塗佈速度為0.3cm/s以上25cm/s以下。對基材(X)的一面全面，在與基材(X)的寬度呈垂直的方向中一次塗佈時，塗佈寬度等於基材(X)的寬度。尚且，取決於藉由塗佈等所設置的層(Y)之平滑性等，亦有相較於基材(X)的圖像清晰度，多層構造體的圖像清晰度成為更高值之情況。The details of the method for making the image resolution of the multilayer structure of the present invention 90% or more are described later, but it is particularly important to use a substrate (X) with high image resolution and a coating solution (S) to be described later. ) at a coating speed of 0.03 cm/s to 2.5 cm/s per 1 cm of coating width. Here, the so-called "coating width of 0.03 cm/s to 2.5 cm/s per 1 cm" refers to the condition of changing the coating speed according to the length of the coating width. For example, when the coating width is 10 cm (with a width of 10 cm When performing coating), it means that the coating speed is not less than 0.3 cm/s and not more than 25 cm/s. When one coat is applied to the entire surface of the substrate (X) in a direction perpendicular to the width of the substrate (X), the coating width is equal to the width of the substrate (X). Also, depending on the smoothness of the layer (Y) provided by coating or the like, there are cases where the image clarity of the multilayer structure becomes a higher value than the image clarity of the base material (X). Condition.

本說明書中，所謂「厚度」，就是意指任意5處的測定值之平均值(平均厚度)。In this specification, "thickness" means the average value (average thickness) of measured values at five arbitrary places.

[基材(X)] 基材(X)之材質係沒有特別的限定，但從具有高圖像清晰度之觀點來看，較佳為包含熱塑性樹脂。基材(X)之形態係沒有特別的限制，但較佳為薄膜或薄片等之層狀。作為基材(X)，較佳為包含熱塑性樹脂薄膜或積層有無機蒸鍍層(X’)之熱塑性樹脂薄膜，更佳為包含熱塑性樹脂薄膜，尤佳為熱塑性樹脂薄膜。 [Substrate (X)] The material of the substrate (X) is not particularly limited, but preferably includes a thermoplastic resin from the viewpoint of having high image definition. The form of the substrate (X) is not particularly limited, but is preferably a layered film or sheet. The substrate (X) preferably includes a thermoplastic resin film or a thermoplastic resin film laminated with an inorganic vapor-deposited layer (X'), more preferably includes a thermoplastic resin film, and is especially preferably a thermoplastic resin film.

作為基材(X)所用的熱塑性樹脂，例如可舉出聚乙烯、聚丙烯等之聚烯烴系樹脂；聚對苯二甲酸乙二酯(PET)、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸丁二酯或此等的共聚物等之聚酯系樹脂；尼龍-6、尼龍-66、尼龍-12等之聚醯胺系樹脂；聚乙烯醇、乙烯-乙烯醇共聚物等之含羥基的聚合物；聚苯乙烯；聚(甲基)丙烯酸酯；聚丙烯腈；聚乙酸乙烯酯；聚碳酸酯；聚芳酯；再生纖維素；聚醯亞胺；聚醚醯亞胺；聚碸；聚醚碸；聚醚醚酮；離子聚合物樹脂等。作為基材(X)所用的熱塑性樹脂，較佳為選自由聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、尼龍-6及尼龍-66所成之群組的至少1種，從圖像清晰度優異之觀點來看，更佳為聚對苯二甲酸乙二酯。Examples of the thermoplastic resin used for the substrate (X) include polyolefin-based resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene 2,6-naphthalate Polyester resins such as polybutylene terephthalate or their copolymers; polyamide resins such as nylon-6, nylon-66, nylon-12, etc.; polyvinyl alcohol, ethylene-vinyl alcohol copolymer Hydroxyl-containing polymers; polystyrene; poly(meth)acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetheramide Imine; Polymer; Polyether ketone; Polyetheretherketone; Ionic polymer resin, etc. The thermoplastic resin used as the substrate (X) is preferably at least one selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66. From the viewpoint of excellent image definition, polyethylene terephthalate is more preferable.

基材(X)係為了賦予易滑性或防黏連性，較佳為包含無機微粒子或有機微粒子。從提高基材(X)的圖像清晰度之觀點來看，包含無機微粒子或有機微粒子時，較佳為在後述表面層中包含該等。亦即，從圖像清晰度之觀點來看，於基材(X)之表面層以外的部分，有較佳的情況為不含無機微粒子或有機微粒子。作為無機微粒子，例如可使用金、銀、銅、鉑、鈀、錸、釩、鋨、鈷、鐵、鋅、釕、鐠、鉻、鎳、鋁、錫、鋅、鈦、鉭、鋯、銻、銦、釔、鑭等之金屬、氧化鋅、氧化鈦、氧化銫、氧化銻、氧化錫、銦・錫氧化物、氧化釔、氧化鑭、氧化鋯、氧化鋁、氧化矽等之金屬氧化物、氟化鋰、氟化鎂、氟化鋁、冰晶石等之金屬氟化物、磷酸鈣等之金屬磷酸鹽、碳酸鈣等之碳酸鹽、硫酸鋇等之硫酸鹽、其他滑石及高嶺土等。作為有機微粒子，除了聚矽氧系化合物、交聯苯乙烯或交聯丙烯酸、交聯三聚氰胺等之交聯微粒子之外，還可使用對於構成基材(X)的熱塑性樹脂不相溶，但微分散而形成海島構造的熱塑性樹脂作為微粒子。所用的微粒子(無機微粒子及有機微粒子)之平均粒徑較佳為0.001~5μm。The substrate (X) preferably contains inorganic fine particles or organic fine particles in order to impart slipperiness or anti-blocking properties. From the viewpoint of improving the image definition of the substrate (X), when inorganic fine particles or organic fine particles are contained, it is preferable to contain them in the surface layer described later. That is, from the viewpoint of image clarity, it may be preferable that the portion other than the surface layer of the substrate (X) does not contain inorganic fine particles or organic fine particles. As the inorganic fine particles, for example, gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, chromium, chromium, nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, and antimony can be used. , metals such as indium, yttrium, and lanthanum, metal oxides such as zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, lanthanum oxide, zirconium oxide, aluminum oxide, and silicon oxide , lithium fluoride, magnesium fluoride, aluminum fluoride, metal fluorides such as cryolite, metal phosphates such as calcium phosphate, carbonates such as calcium carbonate, sulfates such as barium sulfate, other talc and kaolin, etc. As the organic microparticles, in addition to crosslinked microparticles such as polysiloxane compounds, crosslinked styrene or crosslinked acrylic acid, crosslinked melamine, etc., it is also possible to use microparticles that are incompatible with the thermoplastic resin constituting the substrate (X), but slightly The thermoplastic resin dispersed to form the sea-island structure serves as fine particles. The average particle diameter of the microparticles (inorganic microparticles and organic microparticles) used is preferably 0.001-5 μm.

使用前述熱塑性樹脂薄膜作為基材(X)時，基材(X)可為延伸薄膜，也可為無延伸薄膜。從所得之多層構造體的加工適應性(印刷或層合等)優異來看，較佳為延伸薄膜，尤其雙軸延伸薄膜。雙軸延伸薄膜可為以同時雙軸延伸法、逐次雙軸延伸法及管狀延伸法之任一方法所製造的雙軸延伸薄膜。When the aforementioned thermoplastic resin film is used as the substrate (X), the substrate (X) may be a stretched film or an unstretched film. From the standpoint of excellent processing suitability (printing, lamination, etc.) of the resulting multilayer structure, stretched films, especially biaxially stretched films are preferred. The biaxially stretched film may be a biaxially stretched film manufactured by any method of simultaneous biaxial stretching, sequential biaxial stretching, and tubular stretching.

基材(X)之每1層的厚度較佳為5μm以上200μm以下，更佳為7μm以上150μm以下，尤佳為10μm以上100μm以下。若基材(X)之每1層的厚度為5μm以上，則有機械強度及加工性優異之傾向。又，若基材(X)之每1層的厚度為200μm以下，則有所得之多層構造體的柔軟性優異之傾向。The thickness per layer of the substrate (X) is preferably from 5 μm to 200 μm, more preferably from 7 μm to 150 μm, particularly preferably from 10 μm to 100 μm. When the thickness per layer of the base material (X) is 5 μm or more, it tends to be excellent in mechanical strength and processability. Moreover, when the thickness per one layer of a base material (X) is 200 micrometers or less, there exists a tendency for the flexibility of the obtained multilayer structure to be excellent.

基材(X)較佳為具有高的圖像清晰度。依據ISO17221：2014測定的光梳寬度0.25mm之基材(X)的圖像清晰度較佳為90%以上，更佳為91%以上，尤佳為92%以上。基材(X)的圖像清晰度，從製造成本之觀點來看，可為99%以下，也可為97%以下，也可為96%以下，也可為95%以下。若基材(X)的圖像清晰度為90%以上，則容易將所得之多層構造體的圖像清晰度調整至90%以上。The substrate (X) preferably has high image definition. The image definition of the substrate (X) with a comb width of 0.25mm measured according to ISO17221:2014 is preferably at least 90%, more preferably at least 91%, and especially preferably at least 92%. The image clarity of the substrate (X) may be 99% or less, 97% or less, 96% or less, or 95% or less from the viewpoint of production cost. When the image clarity of the substrate (X) is 90% or more, it is easy to adjust the image clarity of the obtained multilayer structure to 90% or more.

作為將基材(X)的圖像清晰度調整至90%以上之手段，可舉出在後述表面層以外之層中不含添加劑(熱塑性樹脂以外的成分)或即使含有也為少量，設置後述之表面層。As a means of adjusting the image clarity of the base material (X) to 90% or more, there are no additives (components other than thermoplastic resins) in layers other than the surface layer described later, or even a small amount of additives (components other than thermoplastic resins) are included. the surface layer.

從為了賦予各種功能且提高基材(X)的圖像清晰度之觀點來看，基材(X)較佳為具備表面層。表面層為設於基材(X)之表面的層，可設於基材(X)之單面，也可設於兩面。基材(X)可具有樹脂基材層與在此樹脂基材層之一面或兩面上所積層的表面層。樹脂基材層係在作為基材(X)所用的熱塑性樹脂，可為前述熱塑性樹脂之層。樹脂基材層可為PET層。於樹脂基材層與表面層之間，亦可存在無機蒸鍍層(X’)等之其他層。樹脂基材層與表面層較佳為直接積層。表面層為以樹脂作為主成分時，亦樹脂基材層與表面層可藉由構成各層的組成之差異等而區別。From the viewpoint of imparting various functions and improving the image clarity of the base material (X), the base material (X) preferably has a surface layer. The surface layer is a layer provided on the surface of the substrate (X), and may be provided on one or both surfaces of the substrate (X). The substrate (X) may have a resin substrate layer and a surface layer laminated on one or both surfaces of the resin substrate layer. The resin substrate layer is based on the thermoplastic resin used as the substrate (X), and may be a layer of the aforementioned thermoplastic resin. The resin base layer may be a PET layer. Between the resin base material layer and the surface layer, other layers such as an inorganic vapor-deposited layer (X') may exist. The resin base layer and the surface layer are preferably directly laminated. When the surface layer is made of resin as a main component, the resin base layer and the surface layer can also be distinguished by the difference in the composition of each layer.

表面層只要對樹脂基材層等具有接著性即可，並沒有特別的限定，較佳為以熱塑性樹脂作為主成分。此處，所謂「作為主成分」，就是意指含量超過50質量%。作為前述熱塑性樹脂，可適宜使用聚酯系樹脂、聚碳酸酯系樹脂、環氧系樹脂、醇酸系樹脂、丙烯酸系樹脂、尿素系樹脂、胺基甲酸酯系樹脂等。又，亦可組合不同2種以上的熱塑性樹脂例如聚酯系樹脂與胺基甲酸酯系樹脂、聚酯系樹脂與丙烯酸系樹脂、或胺基甲酸酯系樹脂與丙烯酸系樹脂等而使用。其中，較佳為選自由聚酯系樹脂、丙烯酸系樹脂及胺基甲酸酯系樹脂所成之群組的至少1種，更佳為聚酯系樹脂。The surface layer is not particularly limited as long as it has adhesiveness to the resin base material layer and the like, but preferably has a thermoplastic resin as the main component. Here, "as a main component" means that the content exceeds 50% by mass. As the thermoplastic resin, polyester resins, polycarbonate resins, epoxy resins, alkyd resins, acrylic resins, urea resins, urethane resins, and the like can be suitably used. Also, two or more different thermoplastic resins such as polyester resin and urethane resin, polyester resin and acrylic resin, or urethane resin and acrylic resin may be used in combination. . Among them, at least one selected from the group consisting of polyester resins, acrylic resins, and urethane resins is preferred, and polyester resins are more preferred.

表面層包含各種的交聯劑者，從耐熱接著性之提升，同時能顯著提高耐濕接著性之觀點來看為較佳的情況。特別地，作為表面層之主成分，使用聚酯系樹脂、胺基甲酸酯系樹脂或丙烯酸系樹脂，將交聯性官能基共聚合於前述樹脂時，較佳為進一步包含交聯劑。構成表面層的熱塑性樹脂與交聯劑可以任意之比率混合而使用，相對於熱塑性樹脂100質量份，交聯劑為0.2~20質量份者係在接著性提升之點上較宜，更佳為0.5~15質量份，尤佳為1~10質量份。It is preferable that the surface layer contains various cross-linking agents from the standpoint of improving the heat-resistant adhesiveness and remarkably improving the moisture-resistant adhesiveness at the same time. In particular, when a polyester-based resin, a urethane-based resin, or an acrylic resin is used as the main component of the surface layer, and a cross-linkable functional group is copolymerized in the resin, it is preferable to further include a cross-linking agent. The thermoplastic resin and the cross-linking agent constituting the surface layer can be mixed and used at any ratio. With respect to 100 parts by mass of the thermoplastic resin, 0.2 to 20 parts by mass of the cross-linking agent is more suitable for improving adhesion, more preferably 0.5-15 parts by mass, preferably 1-10 parts by mass.

表面層係為了賦予易滑性或防黏連性，可包含前述無機微粒子或有機微粒子。The surface layer may contain the aforementioned inorganic fine particles or organic fine particles in order to impart slipperiness or anti-blocking properties.

基材(X)在210℃下加熱1分鐘時的MD方向之熱收縮率，從更提高水蒸氣阻隔性及圖像清晰度之觀點來看，較佳為2.90%以下，更佳為2.80%以下。基材(X)的前述MD方向之熱收縮率可為0.5%以上，但從更提高水蒸氣阻隔性之觀點來看，2.10%以上為較佳的情況。此基材(X)之熱收縮率可為作為多層構造體的原料使用的基材(X)(形成後述層(Y)之前的基材(X))之熱收縮率。The heat shrinkage rate in the MD direction of the substrate (X) when heated at 210°C for 1 minute is preferably 2.90% or less, more preferably 2.80% from the viewpoint of further improving water vapor barrier properties and image clarity the following. The thermal shrinkage rate in the MD direction of the substrate (X) may be 0.5% or more, but it is preferably 2.10% or more from the viewpoint of further improving the water vapor barrier property. The thermal shrinkage rate of the base material (X) may be the thermal shrinkage rate of the base material (X) used as a raw material of the multilayer structure (the base material (X) before the layer (Y) described later is formed).

作為基材(X)，可使用市售品。作為圖像清晰度高的市售品，例如可舉出東麗股份有限公司製Lumirror (註冊商標)U403、U483、A48、XW731C、HYOSUNG公司製RH210、三菱化學股份有限公司製Diafoil(註冊商標)T600、東洋紡股份有限公司製Cosmoshine(註冊商標)A4160、SRF、東洋紡酯(註冊商標)薄膜HPE等。此等可在兩面或單面具有表面層。A commercially available item can be used as a base material (X). Commercially available products with high image resolution include, for example, Lumirror (registered trademark) U403, U483, A48, XW731C manufactured by Toray Co., Ltd., RH210 manufactured by HYOSUNG Corporation, and Diafoil (registered trademark) manufactured by Mitsubishi Chemical Corporation. T600, Toyobo Co., Ltd. Cosmoshine (registered trademark) A4160, SRF, Toyobo Ester (registered trademark) film HPE, etc. These may have surface layers on both sides or on one side.

基材(X)係從後述塗佈液(S)的塗佈性之觀點及所得之多層構造體的阻隔性之觀點來看，較佳為被施予表面處理。表面處理可以眾所周知之方法進行，例如可舉出UV臭氧處理、高濃度臭氧水處理、準分子臭氧處理、電暈處理、氧電漿處理或AP電漿處理等。The substrate (X) is preferably surface-treated from the viewpoint of coating properties of the coating solution (S) described later and the barrier properties of the obtained multilayer structure. Surface treatment can be carried out by well-known methods, such as UV ozone treatment, high-concentration ozone water treatment, excimer ozone treatment, corona treatment, oxygen plasma treatment, or AP plasma treatment.

積層有作為基材(X)使用的無機蒸鍍層(X’)之熱塑性樹脂薄膜，通常為具有對氧或水蒸氣的阻隔性之薄膜，為具有透明性之薄膜。作為基材(X)，使用在一面上積層有無機蒸鍍層(X’)之熱塑性樹脂薄膜時，後述的層(Y)係積層於無機蒸鍍層(X’)側。作為積層有無機蒸鍍層(X’)的熱塑性樹脂薄膜所用的熱塑性樹脂薄膜，可使用作為上述基材(X)所例示的熱塑性樹脂薄膜。無機蒸鍍層(X’)可藉由蒸鍍無機物而形成。作為無機物，可舉出金屬氧化物(例如氧化矽、氧化鋁)、金屬氮化物(例如氮化矽)或金屬氮氧化物(例如氧氮化矽)等。其中，以氧化鋁、氧化矽、氧化鎂或氮化矽形成的無機蒸鍍層(X’)，從透明性優異之觀點來看較宜。尚且，基材(X)從圖像清晰度之觀點來看，不含無機蒸鍍層(X’)者亦為較佳的情況。The thermoplastic resin film laminated with the inorganic vapor-deposited layer (X') used as the substrate (X) is usually a film having barrier properties to oxygen or water vapor, and a film having transparency. When a thermoplastic resin film with an inorganic vapor-deposited layer (X') laminated on one side is used as the substrate (X), the layer (Y) described later is laminated on the inorganic vapor-deposited layer (X') side. As the thermoplastic resin film used for the thermoplastic resin film on which the inorganic vapor-deposited layer (X') is laminated, the thermoplastic resin film exemplified as the base material (X) above can be used. The inorganic vapor-deposited layer (X') can be formed by vapor-depositing an inorganic substance. Examples of inorganic substances include metal oxides (such as silicon oxide and aluminum oxide), metal nitrides (such as silicon nitride), metal oxynitrides (such as silicon oxynitride), and the like. Among them, the inorganic vapor-deposited layer (X') formed of alumina, silicon oxide, magnesium oxide, or silicon nitride is preferable from the viewpoint of excellent transparency. Furthermore, it is preferable that the base material (X) does not contain the inorganic vapor-deposited layer (X') from the viewpoint of image clarity.

無機蒸鍍層(X’)之形成方法係沒有特別的限定，可舉出真空蒸鍍法(例如電阻加熱蒸鍍、電子束蒸鍍、分子線磊晶法等)、濺鍍法或離子鍍法等之物理氣相成長法；熱化學氣相成長法(例如觸媒化學氣相成長法)、光化學氣相成長法、電漿化學氣相成長法(例如電容耦合電漿、感應耦合電漿、表面波電漿、電子迴旋共振、雙靶磁控、原子層沉積法等)、有機金屬氣相成長法等之化學氣相成長法。The formation method of the inorganic vapor deposition layer (X') is not particularly limited, and vacuum evaporation methods (such as resistance heating evaporation, electron beam evaporation, molecular wire epitaxy, etc.), sputtering methods, or ion plating methods can be mentioned. Physical vapor growth method; thermal chemical vapor growth method (such as catalytic chemical vapor phase growth method), photochemical vapor phase growth method, plasma chemical vapor phase growth method (such as capacitively coupled plasma, inductively coupled plasma , surface wave plasma, electron cyclotron resonance, double-target magnetron, atomic layer deposition, etc.), organometallic vapor phase growth and other chemical vapor phase growth methods.

無機蒸鍍層(X’)之厚度係隨著構成無機蒸鍍層的成分之種類而不同，但較佳為0.002~0.5μm，更佳為0.005~0.2μm，尤佳為0.01~0.1μm。只要在此範圍內選擇多層構造體的阻隔性或機械物性變良好之厚度即可。若無機蒸鍍層(X’)之厚度為0.002μm以上，則有無機蒸鍍層(X’)對氧或水蒸氣的阻隔性變良好之傾向。又，若無機蒸鍍層(X’)之厚度為0.5μm以下，則有維持無機蒸鍍層(X’)的彎曲後之阻隔性的傾向。The thickness of the inorganic vapor-deposited layer (X') varies depending on the type of components constituting the inorganic vapor-deposited layer, but is preferably 0.002-0.5 μm, more preferably 0.005-0.2 μm, and most preferably 0.01-0.1 μm. What is necessary is just to select the thickness which becomes favorable barrier property and mechanical physical property of a multilayer structure within this range. When the thickness of the inorganic vapor-deposited layer (X') is 0.002 µm or more, the barrier properties of the inorganic vapor-deposited layer (X') to oxygen or water vapor tend to be good. In addition, when the thickness of the inorganic vapor-deposited layer (X') is 0.5 µm or less, the barrier property after bending of the inorganic vapor-deposited layer (X') tends to be maintained.

作為基材(X)，可單獨使用1種的基材，也可組合2種以上的基材而使用。具有複數層的基材(X)時，各自的基材(X)可相同或相異。基材(X)之層數可為1層，也可為2層以上。基材(X)之層數例如為1層以上3層以下，較佳為1層以上2層以下，更佳為1層。As the base material (X), one type of base material may be used alone, or two or more types of base materials may be used in combination. When having the base material (X) of several layers, each base material (X) may be the same or different. The number of layers of the substrate (X) may be one layer, or two or more layers. The number of layers of the substrate (X) is, for example, 1 to 3 layers, preferably 1 to 2 layers, more preferably 1 layer.

[層(Y)] 層(Y)包含金屬氧化物(A)與無機磷化合物(BI)之反應生成物(D)。於本發明之多層構造體中，層(Y)由於作為阻隔層發揮功能，故本發明之多層構造體藉由具備層(Y)，而有阻隔性變良好之傾向。又，以適當的手法形成層(Y)，可使多層構造體的圖像清晰度成為90%以上。 [Layer (Y)] The layer (Y) contains the reaction product (D) of the metal oxide (A) and the inorganic phosphorus compound (BI). In the multilayer structure of the present invention, since the layer (Y) functions as a barrier layer, the multilayer structure of the present invention tends to have better barrier properties by including the layer (Y). In addition, by forming the layer (Y) in an appropriate manner, the image clarity of the multilayer structure can be made 90% or more.

(含有鋁原子的金屬氧化物(A)) 構成金屬氧化物(A)的金屬原子(亦將彼等總稱為「金屬原子(M)」)，通常為選自屬於週期表的第2~14族之金屬原子的至少1種金屬原子，至少包含鋁原子。金屬原子(M)較佳為鋁原子，但亦可包含鋁原子與其以外的金屬原子。尚且，作為金屬氧化物(A)，可混合2種以上的金屬氧化物(A)而使用。作為鋁原子以外的金屬原子，例如可舉出鎂、鈣等之週期表第2族的金屬；鋅等之週期表第12族的金屬；週期表第13屬的金屬；矽等之週期表第14族的金屬；鈦、鋯等之過渡金屬等。尚且，矽會有被分類於半金屬之情況，但本說明書中將矽視為包含於金屬者。作為與鋁可併用的金屬原子(M)，從操作性或所得之多層構造體的阻氣性優異之觀點來看，較佳為選自由鈦及鋯所成之群組的至少1種。 (Metal oxide (A) containing aluminum atoms) The metal atoms constituting the metal oxide (A) (also collectively referred to as "metal atoms (M)") are usually at least one metal atom selected from metal atoms belonging to Groups 2 to 14 of the periodic table, and at least Contains aluminum atoms. The metal atom (M) is preferably an aluminum atom, but may also include an aluminum atom and other metal atoms. Furthermore, as the metal oxide (A), two or more metal oxides (A) may be mixed and used. Examples of metal atoms other than aluminum atoms include metals of group 2 of the periodic table such as magnesium and calcium; metals of group 12 of the periodic table such as zinc; metals of genus 13 of the periodic table; metals of group 13 of the periodic table such as silicon; Metals of group 14; transition metals such as titanium and zirconium, etc. Also, silicon may be classified as a semi-metal, but in this specification, silicon is considered to be included in a metal. The metal atom (M) that can be used together with aluminum is preferably at least one selected from the group consisting of titanium and zirconium from the viewpoint of excellent handling properties and gas barrier properties of the obtained multilayer structure.

鋁原子佔金屬原子(M)之比例較佳為50莫耳%以上，更佳為70莫耳%以上，尤佳為90莫耳%以上，也可為95莫耳%以上或實質上僅由鋁原子所構成。於金屬氧化物(A)之例中，包含藉由液相合成法、氣相合成法、固體粉碎法等之方法所製造的金屬氧化物。The ratio of aluminum atoms to metal atoms (M) is preferably at least 50 mol%, more preferably at least 70 mol%, especially preferably at least 90 mol%, may also be at least 95 mol%, or substantially only consists of composed of aluminum atoms. Examples of the metal oxide (A) include metal oxides produced by methods such as a liquid phase synthesis method, a gas phase synthesis method, and a solid pulverization method.

(含有能水解的特性基鍵結了的金屬原子(M)之化合物(E)) 金屬氧化物(A)可為含有能水解的特性基鍵結了的金屬原子(M)之化合物(E)(以下亦簡稱「化合物(E)」)的水解縮合物。作為該特性基，例如可舉出鹵素原子、NO 3、可具有取代基之碳數1~9的烷氧基、可具有取代基之碳數6~9的芳氧基、可具有取代基之碳數2~9的醯氧基、可具有取代基之碳數3~9的烯氧基、可具有取代基之碳數5~15的β-二酮基或可具有取代基之具有碳數1~9的醯基的二醯基甲基等。可將化合物(E)的水解縮合物實質上視為金屬氧化物(A)。因此，本說明書中，有將化合物(E)的水解縮合物稱為「金屬氧化物(A)」之情況。亦即，本說明書中，「金屬氧化物(A)」可改稱為「化合物(E)的水解縮合物」，另外可將「化合物(E)的水解縮合物」改稱為「金屬氧化物(A)」。 (Compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group) The metal oxide (A) may be a compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group (hereinafter also referred to as "compound (E)") hydrolytic condensate. Examples of the characteristic group include a halogen atom, NO 3 , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, an aryloxy group having 6 to 9 carbon atoms which may have a substituent, and an alkoxy group which may have a substituent Acyloxy with 2 to 9 carbons, alkenyloxy with 3 to 9 carbons that may have a substituent, β-diketone with 5 to 15 carbons that may have a substituent, or a carbon number that may have a substituent 1~9 acyl group, diacylmethyl group, etc. The hydrolytic condensate of compound (E) can be regarded as metal oxide (A) substantially. Therefore, in this specification, the hydrolytic condensate of compound (E) may be referred to as "metal oxide (A)". That is, in this specification, "metal oxide (A)" may be changed to "hydrolytic condensate of compound (E)", and "hydrolytic condensate of compound (E)" may be changed to "metal oxide (A)".

從與無機磷化合物(BI)之反應的控制變容易，所得之多層構造體的阻氣性來看，化合物(E)較佳為包含後述含有鋁原子的化合物(Ea)。It is preferable that the compound (E) contains the compound (Ea) containing an aluminum atom mentioned later from the viewpoint of easy control of the reaction with the inorganic phosphorus compound (BI) and the gas barrier property of the obtained multilayer structure.

作為化合物(Ea)，例如可舉出氯化鋁、硝酸鋁、乙酸鋁、參(2,4-戊二酮根)鋁、三甲氧基鋁、三乙氧基鋁、三正丙氧基鋁、三異丙氧基鋁、三正丁氧基鋁、三第二丁氧基鋁、三第三丁氧基鋁等，其中較佳為三異丙氧基鋁及三第二丁氧基鋁。作為化合物(E)，亦可併用2種以上的化合物(Ea)。Examples of the compound (Ea) include aluminum chloride, aluminum nitrate, aluminum acetate, ginseng(2,4-pentanedionato)aluminum, trimethoxyaluminum, triethoxyaluminum, and tri-n-propoxyaluminum , triisopropoxy aluminum, tri-n-butoxy aluminum, tri-second butoxy aluminum, tri-tertiary butoxy aluminum, etc., among which triisopropoxy aluminum and tri-second butoxy aluminum . As the compound (E), two or more compounds (Ea) may be used in combination.

又，化合物(E)可包含含有鋁以外的金屬原子(M)之化合物(Eb)。作為化合物(Eb)，例如可舉出四(2,4-戊二酮根)鈦、四甲氧基鈦、四乙氧基鈦、四異丙氧基鈦、四正丁氧基鈦、四(2-乙基己氧基)鈦等之鈦化合物；四(2,4-戊二酮根)鋯、四正丙氧基鋯、四正丁氧基鋯等之鋯化合物等。此等可單獨1種使用，也可併用2種以上的化合物(Eb)。In addition, the compound (E) may include a compound (Eb) containing a metal atom (M) other than aluminum. Examples of the compound (Eb) include tetrakis (2,4-pentanedionato)titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra Titanium compounds such as (2-ethylhexyloxy)titanium; zirconium compounds such as tetrakis(2,4-pentanedionato)zirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, etc. These may be used individually by 1 type, and may use 2 or more types of compounds (Eb) together.

化合物(Ea)佔化合物(E)之比例係沒有特別的限定，例如較佳為80莫耳%以上，更佳為90莫耳%以上，尤佳為95莫耳%以上，亦可為100莫耳%。The ratio of compound (Ea) to compound (E) is not particularly limited, for example, it is preferably 80 mol% or more, more preferably 90 mol% or more, especially preferably 95 mol% or more, or 100 mol% Ear%.

藉由化合物(E)被水解，化合物(E)所具有之能水解的特性基之至少一部分被轉換成羥基。再者，藉由其水解物縮合，可形成金屬原子(M)透過氧原子(O)鍵結的化合物。若重複該縮合，則形成實質上可被視為金屬氧化物的化合物。尚且，在以這樣的方式形成的金屬氧化物(A)之表面，通常存在羥基。When the compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic groups of the compound (E) is converted into a hydroxyl group. Furthermore, by condensation of its hydrolyzate, a compound in which a metal atom (M) is bonded through an oxygen atom (O) can be formed. When this condensation is repeated, a compound that can be regarded as a metal oxide is formed substantially. Also, on the surface of the metal oxide (A) formed in this way, hydroxyl groups usually exist.

本說明書中，將[僅鍵結於金屬原子(M)的氧原子(O)之莫耳數]/[金屬原子(M)之莫耳數]之比為0.8以上的化合物視為包含於金屬氧化物(A)中者。此處，僅鍵結於金屬原子(M)的氧原子(O)為以M-O-M表示的結構中之氧原子(O)，如以M-O-H表示的結構中之氧原子(O)般，鍵結於金屬原子(M)與氫原子(H)的氧原子係被排除在外。金屬氧化物(A)中的前述比較佳為0.9以上，更佳為1.0以上，尤佳為1.1以上。該比之上限係沒有特別的限定，但將金屬原子(M)的原子價設為n時，通常以n/2表示。In this specification, a compound whose ratio of [the number of moles of oxygen atoms (O) bonded only to metal atoms (M)]/[the number of moles of metal atoms (M)] is 0.8 or more is considered to be contained in the metal Those in oxide (A). Here, the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by M-O-M, and like the oxygen atom (O) in the structure represented by M-O-H, it is bonded to Oxygen atom systems of metal atoms (M) and hydrogen atoms (H) are excluded. The aforementioned ratio in the metal oxide (A) is preferably at least 0.9, more preferably at least 1.0, and most preferably at least 1.1. The upper limit of this ratio is not particularly limited, but when the valence of the metal atom (M) is n, it is usually represented by n/2.

為了發生前述水解縮合，重要的是化合物(E)具有能水解的特性基。彼等之基未鍵結時，由於水解縮合反應不發生或極緩慢，故目的之金屬氧化物(A)的調製會變困難。In order for the aforementioned hydrolytic condensation to occur, it is important that the compound (E) has a hydrolyzable characteristic group. When these groups are not bonded, since the hydrolytic condensation reaction does not occur or is extremely slow, preparation of the target metal oxide (A) becomes difficult.

化合物(E)之水解縮合物，例如可藉由眾所周知的溶膠凝膠法所用之手段，由特定原料來製造。於該原料中，可使用選自由化合物(E)、化合物(E)的部分水解物、化合物(E)的完全水解物、化合物(E)部分水解縮合而成的化合物及化合物(E)的完全水解物的一部分縮合而成的化合物所成之群組的至少1種。The hydrolysis-condensation product of compound (E) can be produced from specific raw materials by the means used for the well-known sol-gel method, for example. In this raw material, a compound selected from compound (E), a partial hydrolyzate of compound (E), a complete hydrolyzate of compound (E), a compound formed by partial hydrolysis and condensation of compound (E) and a complete hydrolyzate of compound (E) can be used. At least one of the group consisting of compounds formed by condensation of a part of the hydrolyzate.

尚且，於與後述無機磷化合物(BI)含有物(包含無機磷化合物(BI)或無機磷化合物(BI)之組成物)之混合中所供應的金屬氧化物(A)，較佳為實質上不含磷原子。Furthermore, it is preferable that the metal oxide (A) supplied during mixing with the inorganic phosphorus compound (BI)-containing substance (composition containing the inorganic phosphorus compound (BI) or the inorganic phosphorus compound (BI)) described later is substantially Does not contain phosphorus atoms.

(無機磷化合物(BI)) 無機磷化合物(BI)含有與金屬氧化物(A)能反應的部位，典型上含有數個該部位，宜含有2~20個。於該部位中，包含與在金屬氧化物(A)之表面上存在的官能基(例如羥基)能縮合反應的部位，例如可舉出直接鍵結於磷原子的鹵素原子、直接鍵結於磷原子的氧原子等。金屬氧化物(A)之表面上存在的官能基(例如羥基)通常鍵結於構成金屬氧化物(A)的金屬原子(M)。 (Inorganic phosphorus compound (BI)) The inorganic phosphorus compound (BI) contains a site capable of reacting with the metal oxide (A), typically several of these sites, preferably 2 to 20 sites. This site includes a site capable of condensation reaction with a functional group (such as a hydroxyl group) present on the surface of the metal oxide (A), for example, a halogen atom directly bonded to a phosphorus atom, a halogen atom directly bonded to a phosphorus atom, Atoms of oxygen atoms, etc. A functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).

作為無機磷化合物(BI)，例如可舉出磷酸、二磷酸、三磷酸、4分子以上的磷酸縮合而成的聚磷酸、亞磷酸、膦酸、亞膦酸、次膦酸、次亞膦酸等之磷的含氧酸及此等之鹽(例如磷酸鈉)、以及此等之衍生物(例如鹵化物(例如磷醯氯)、脫水物(例如五氧化二磷))等。無機磷化合物(BI)可單獨使用1種，也可併用2種以上。其中，從後述塗佈液(S)的安定性及所得之多層構造體的阻氣性提升之觀點來看，較佳為單獨使用磷酸，或併用磷酸與其以外的無機磷化合物。併用磷酸與其以外的無機磷化合物時，無機磷化合物(BI)的50莫耳%以上較佳為磷酸。Examples of inorganic phosphorus compounds (BI) include phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid obtained by condensation of four or more molecules of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, and phosphinic acid. Phosphorous oxyacids and their salts (such as sodium phosphate), and their derivatives (such as halides (such as phosphoryl chloride), dehydrates (such as phosphorus pentoxide)) and the like. The inorganic phosphorus compound (BI) may be used alone or in combination of two or more. Among them, it is preferable to use phosphoric acid alone or to use phosphoric acid and other inorganic phosphorus compounds in combination from the viewpoint of the stability of the coating liquid (S) described later and the improvement of the gas barrier properties of the obtained multilayer structure. When phosphoric acid and other inorganic phosphorus compounds are used in combination, phosphoric acid is preferably 50 mol% or more of the inorganic phosphorus compound (BI).

(反應生成物(D)) 反應生成物(D)可藉由金屬氧化物(A)與無機磷化合物(BI)之反應來獲得。金屬氧化物(A)與無機磷化合物(BI)進一步與其他化合物反應而生成的化合物亦被包含反應生成物(D)中。 (Reaction product (D)) The reaction product (D) can be obtained by reaction of a metal oxide (A) and an inorganic phosphorus compound (BI). The compound produced by further reacting the metal oxide (A) and the inorganic phosphorus compound (BI) with another compound is also included in the reaction product (D).

於層(Y)的紅外線吸收光譜中，800~1400cm -1的區域之最大吸收波數較佳在1080~1130cm -1之範圍。例如，於金屬氧化物(A)與無機磷化合物(BI)反應而成為反應生成物(D)之過程中，源自金屬氧化物(A)的金屬原子(M)與源自無機磷化合物(BI)的磷原子(P)係透過氧原子(O)形成以M-O-P表示的鍵結。結果，於反應生成物(D)的紅外線吸收光譜之中，出現了源自該鍵結的特性吸收帶。在1080 ~1130cm -1的區域看到基於M-O-P的鍵結之特性吸收帶時，所得之多層構造體係展現優異的阻氣性。特別地，該特性吸收帶係在一般看到源自各種原子與氧原子的鍵結之吸收的800~1400cm -1的區域中為最強吸收時，所得之多層構造體係展現更加優異的阻氣性。 In the infrared absorption spectrum of layer (Y), the maximum absorption wavenumber in the region of 800-1400 cm -1 is preferably in the range of 1080-1130 cm -1 . For example, in the process that the metal oxide (A) reacts with the inorganic phosphorus compound (BI) to become the reaction product (D), the metal atom (M) derived from the metal oxide (A) and the metal atom (M) derived from the inorganic phosphorus compound ( The phosphorus atom (P) of BI) passes through the oxygen atom (O) to form a bond represented by MOP. As a result, a characteristic absorption band derived from this bond appears in the infrared absorption spectrum of the reaction product (D). When the characteristic absorption band based on MOP bonding is seen in the region of 1080 ~ 1130 cm -1 , the resulting multilayer structure system exhibits excellent gas barrier properties. In particular, when this characteristic absorption band is the strongest absorption in the region of 800 to 1400 cm -1 where absorption originating from bonding of various atoms and oxygen atoms is generally seen, the resulting multilayer structure system exhibits more excellent gas barrier properties .

相對於其，將化合物(E)或金屬鹽等之金屬化合物與無機磷化合物(BI)預先混合後使其水解縮合時，可得到源自金屬化合物的金屬原子與源自無機磷化合物(BI)的磷原子大致均勻混合反應而成的複合體。於該情況下，在紅外線吸收光譜中，800~1400cm -1的區域中之最大吸收波數會脫離1080~1130cm -1之範圍。 On the other hand, when compound (E) or a metal compound such as a metal salt and an inorganic phosphorus compound (BI) are mixed in advance and then hydrolyzed and condensed, a metal atom derived from the metal compound and a metal atom derived from the inorganic phosphorus compound (BI) can be obtained. Phosphorus atoms are roughly evenly mixed and reacted to form a complex. In this case, in the infrared absorption spectrum, the maximum absorption wavenumber in the region of 800 to 1400 cm −1 deviates from the range of 1080 to 1130 cm −1 .

於層(Y)的紅外線吸收光譜中，800~1400cm -1的區域之最大吸收帶的半高寬，從所得之多層構造體的阻氣性之觀點來看，較佳為200cm -1以下，更佳為150cm -1以下，尤佳為100cm -1以下，特佳為50cm -1以下。 In the infrared absorption spectrum of the layer (Y), the full width at half maximum of the maximum absorption band in the region of 800 to 1400 cm -1 is preferably 200 cm -1 or less from the viewpoint of the gas barrier properties of the obtained multilayer structure, More preferably, it is not more than 150 cm -1 , especially preferably not more than 100 cm -1 , and most preferably not more than 50 cm -1 .

層(Y)的紅外線吸收光譜，可藉由使用傅立葉轉換紅外線分光光度計(PerkinElmer股份有限公司製的Spectrum One)，以800~1400cm -1作為測定區域，以衰減全反射法進行測定。惟，以前述方法無法測定時，可藉由反射吸收法、外部反射法、衰減全反射法等之反射測定，將層(Y)由多層構造體刮下，以石蠟糊法、錠劑法等之穿透測定的方法進行測定，但不受該等所限定。 The infrared absorption spectrum of the layer (Y) can be measured by an attenuated total reflection method using a Fourier transform infrared spectrophotometer (Spectrum One manufactured by PerkinElmer Co., Ltd.) with a measurement region of 800 to 1400 cm −1 . However, when it is impossible to measure by the above-mentioned methods, it can be measured by reflection absorption method, external reflection method, attenuated total reflection method, etc., by scraping off the layer (Y) from the multilayer structure, and using paraffin paste method, lozenge method, etc. The method of the penetration measurement is carried out, but it is not limited thereto.

又，層(Y)亦可部分地包含未參與反應的金屬氧化物(A)及/或無機磷化合物(BI)。Moreover, the layer (Y) may partially contain the metal oxide (A) and/or the inorganic phosphorus compound (BI) which did not participate in the reaction.

層(Y)中，源自金屬氧化物(A)的金屬原子與源自無機磷化合物(BI)的磷原子之莫耳比，較佳在[源自金屬氧化物(A)的金屬原子]：[源自無機磷化合物(BI)的磷原子]=1.0：1.0~3.6：1.0之範圍，更佳在1.1：1.0~3.0：1.0之範圍。於此範圍內時，得到優異的阻氣性能。層(Y)中的該莫耳比可藉由用於形成層(Y)的塗佈液(S)中之金屬氧化物(A)與無機磷化合物(BI)之混合比率來調整。層(Y)中的該莫耳比通常與塗佈液(S)中的比相同。In the layer (Y), the molar ratio of the metal atoms derived from the metal oxide (A) to the phosphorus atoms derived from the inorganic phosphorus compound (BI) is preferably [the metal atoms derived from the metal oxide (A)] : [Phosphorus atom derived from inorganic phosphorus compound (BI)]=1.0:1.0~3.6:1.0, more preferably 1.1:1.0~3.0:1.0. When it is within this range, excellent gas barrier performance is obtained. The molar ratio in the layer (Y) can be adjusted by the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (BI) in the coating liquid (S) used to form the layer (Y). This molar ratio in layer (Y) is usually the same as that in coating liquid (S).

層(Y)之厚度(多層構造體具有2層以上的層(Y)時，為各層(Y)之厚度的合計)較佳為0.05~4.0μm，更佳為0.1~2.0μm。藉由減薄層(Y)，可壓低印刷、層合等之加工時的多層構造體之尺寸變化。又，由於多層構造體的柔軟性增加，故亦可使其力學特性接近基材本身的力學特性。從阻氣性之觀點來看，層(Y)每1層的厚度較佳為0.05μm以上，更佳為0.1μm以上。層(Y)每1層的厚度較佳為2.0μm以下，更佳為1.0μm以下。層(Y)之厚度可藉由層(Y)之形成時所用的後述塗佈液(S)之濃度或其塗佈方法來控制。層(Y)之厚度可藉由以掃描式電子顯微鏡或穿透型電子顯微鏡觀察多層構造體剖面而測定。The thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is preferably 0.05 to 4.0 μm, more preferably 0.1 to 2.0 μm. By reducing the thickness of the layer (Y), the dimensional change of the multilayer structure during processing such as printing and lamination can be suppressed. In addition, since the flexibility of the multilayer structure is increased, the mechanical properties can be approached to those of the base material itself. From the viewpoint of gas barrier properties, the thickness per layer (Y) is preferably at least 0.05 μm, more preferably at least 0.1 μm. The thickness per layer (Y) is preferably at most 2.0 μm, more preferably at most 1.0 μm. The thickness of the layer (Y) can be controlled by the concentration of the coating liquid (S) described later used in the formation of the layer (Y) or its coating method. The thickness of the layer (Y) can be measured by observing the cross section of the multilayer structure with a scanning electron microscope or a transmission electron microscope.

層(Y)之層數可為1層，也可為2層以上。藉由具有2層以上的層(Y)，有阻隔性提升之傾向。層(Y)之層數亦可為2層。具有2層以上的層(Y)時，較佳為在各基材(X)之兩面上分別配置層(Y)。具有2層以上的層(Y)時，其積層方法係沒有特別的限定，可直接配置於基材(X)之單面或兩面，也可使用後述接著層(I)來貼合含有層(Y)的多層構造體。The number of layers of a layer (Y) may be 1 layer, and may be 2 or more layers. There exists a tendency for barrier property to improve by having 2 or more layers (Y). The number of layers of the layer (Y) may be 2 layers. When there are two or more layers (Y), it is preferable to arrange the layers (Y) on both surfaces of each substrate (X). When there are two or more layers (Y), the lamination method is not particularly limited, and it can be directly arranged on one or both sides of the substrate (X), and the layer containing ( Y) multilayer structure.

層(Y)係除了上述成分(金屬氧化物(A)、無機磷化合物(BI)及此等的反應生成物(D))之外，還可進一步包含其他成分。作為層(Y)可含有的其他成分，例如可舉出具有選自由羰基、羥基、羧基、羧酸酐基及羧基的鹽所成之群組的至少一種官能基之聚合物(F)(以下亦簡稱「聚合物(F)」)、有機磷化合物(BO)、含交聯劑的樹脂組成物(V)、碳酸鹽、鹽酸鹽、硝酸鹽、碳酸氫鹽、硫酸鹽、硫酸氫鹽、硼酸鹽等之無機酸金屬鹽、草酸鹽、乙酸鹽、酒石酸鹽、硬脂酸鹽等之有機酸金屬鹽、環戊二烯基金屬錯合物(例如二茂鈦)、氰基金屬錯合物(例如普魯士藍)等之金屬錯合物、層狀黏土化合物、交聯劑、聚合物(F)以外的高分子化合物、可塑劑、抗氧化劑、紫外線吸收劑、難燃劑等。多層構造體中之層(Y)中的前述其他成分之含有率較佳為50質量%以下，更佳為20質量%以下，尤佳為10質量%以下，特佳為5質量%以下，亦可為4質量%以下、3質量%以下、2質量%以下、1質量%以下或0質量%(不含其他成分)。本發明之多層構造體，從具有更高的鮮明度之觀點來看，其他成分之含量宜少。The layer (Y) may further contain other components in addition to the above-mentioned components (the metal oxide (A), the inorganic phosphorus compound (BI), and the reaction product (D) thereof). As other components that the layer (Y) may contain, for example, a polymer (F) (hereinafter also referred to as "Polymer (F)" for short), organophosphorus compound (BO), resin composition (V) containing crosslinking agent, carbonate, hydrochloride, nitrate, bicarbonate, sulfate, bisulfate, Metal salts of inorganic acids such as borates, metal salts of organic acids such as oxalates, acetates, tartrates, stearates, etc., cyclopentadienyl metal complexes (such as titanocenes), cyano metal complexes metal complexes such as Prussian blue compounds, layered clay compounds, crosslinking agents, polymer compounds other than polymer (F), plasticizers, antioxidants, ultraviolet absorbers, flame retardants, etc. The content of the aforementioned other components in the layer (Y) in the multilayer structure is preferably at most 50% by mass, more preferably at most 20% by mass, particularly preferably at most 10% by mass, particularly preferably at most 5% by mass, and also preferably at most 5% by mass. It may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0% by mass (excluding other components). The multilayer structure of the present invention preferably has less content of other components from the viewpoint of higher clarity.

(聚合物(F)) 聚合物(F)具有選自由羰基、羥基、羧基、羧酸酐基及羧基的鹽所成之群組的至少一種官能基。聚合物(F)較佳為具有選自由羥基及羧基所成之群組的至少1種官能基之聚合物。 (polymer (F)) The polymer (F) has at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group. The polymer (F) is preferably a polymer having at least one functional group selected from the group consisting of a hydroxyl group and a carboxyl group.

作為聚合物(F)，可舉出聚乙二醇；聚乙烯醇、含有1~50莫耳%的碳數4以下的α-烯烴單元之改質聚乙烯醇、聚乙烯縮醛(聚乙烯縮丁醛等)等之聚乙烯醇系聚合物；纖維素、澱粉等之多糖類；聚(甲基)丙烯酸羥乙酯、聚(甲基)丙烯酸、乙烯-丙烯酸共聚物等之(甲基)丙烯酸系聚合物；乙烯-馬來酸酐共聚物的水解物、苯乙烯-馬來酸酐共聚物的水解物、異丁烯-馬來酸酐交替共聚物的水解物等之馬來酸系聚合物等。其中，較佳為聚乙二醇或聚乙烯醇系聚合物。Examples of the polymer (F) include polyethylene glycol; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of α-olefin units having 4 or less carbon atoms, and polyvinyl acetal (polyvinyl acetal). polyvinyl alcohol-based polymers such as butyral, etc.); polysaccharides such as cellulose and starch; poly(meth)hydroxyethyl acrylate, poly(meth)acrylic acid, ethylene-acrylic acid copolymers ) acrylic polymer; maleic acid polymers such as hydrolyzate of ethylene-maleic anhydride copolymer, hydrolyzate of styrene-maleic anhydride copolymer, hydrolyzate of isobutylene-maleic anhydride alternating copolymer, etc. Among them, polyethylene glycol or polyvinyl alcohol-based polymers are preferred.

聚合物(F)可為具有聚合性基的單體之均聚物，也可為2種以上的單體之共聚物，亦可為具有選自由羰基、羥基、羧基、羧酸酐基及羧基的鹽所成之群組的至少一種官能基的單體與不具有該基的單體之共聚物。尚且，作為聚合物(F)，亦可混合2種以上的聚合物(F)而使用。The polymer (F) may be a homopolymer of a monomer having a polymerizable group, or a copolymer of two or more monomers, or may have a compound selected from carbonyl, hydroxyl, carboxyl, carboxylic anhydride, and carboxyl groups. A copolymer of a monomer having at least one functional group and a monomer having no such group. Moreover, as a polymer (F), you may mix and use 2 or more types of polymer (F).

聚合物(F)之分子量係沒有特別的限制，但為了得到具有更優異的阻氣性及機械強度之多層構造體，聚合物(F)之重量平均分子量較佳為5000以上，更佳為8000以上，尤佳為10000以上。聚合物(F)之重量平均分子量之上限係沒有特別的限定，例如為1500000以下。The molecular weight of the polymer (F) is not particularly limited, but in order to obtain a multilayer structure with more excellent gas barrier properties and mechanical strength, the weight average molecular weight of the polymer (F) is preferably 5000 or more, more preferably 8000 Above, preferably above 10,000. The upper limit of the weight average molecular weight of polymer (F) is not specifically limited, For example, it is 1,500,000 or less.

從保持多層構造體的外觀良好之觀點來看，層(Y)中的聚合物(F)之含量，以層(Y)的質量為基準，較佳為未達50質量%，更佳為20質量%以下，尤佳為10質量%以下，亦可為0質量%。聚合物(F)可與層(Y)中的成分反應，也可不反應。From the viewpoint of maintaining a good appearance of the multilayer structure, the content of the polymer (F) in the layer (Y) is preferably less than 50% by mass, more preferably 20% by mass, based on the mass of the layer (Y). Mass % or less, preferably 10 mass % or less, may be 0 mass %. Polymer (F) may or may not react with the ingredients in layer (Y).

(有機磷化合物(BO)) 有機磷化合物(BO)較佳為具有數個磷原子的聚合物(BOa)或後述有機磷化合物(BOb)。 (organophosphorus compounds (BO)) The organophosphorus compound (BO) is preferably a polymer (BOa) having several phosphorus atoms or an organophosphorus compound (BOb) described later.

(具有數個磷原子的聚合物(BOa)) 作為聚合物(BOa)所具有之含磷原子的官能基，例如可舉出磷酸基、亞磷酸基、膦酸基、亞膦酸基、次膦酸基、次亞膦酸基及由此等所衍生的官能基(例如鹽、(部分)酯化合物、鹵化物(例如氯化物)、脫水物)等，其中較佳為磷酸基及膦酸基，更佳為膦酸基。 (Polymer with several phosphorus atoms (BOa)) Examples of the phosphorus atom-containing functional groups of the polymer (BOa) include phosphoric acid groups, phosphorous acid groups, phosphonic acid groups, phosphinic acid groups, phosphinic acid groups, phosphinic acid groups, and the like. Among the derivatized functional groups (such as salts, (partial) ester compounds, halides (such as chlorides), dehydrates), etc., phosphoric acid groups and phosphonic acid groups are preferred, and phosphonic acid groups are more preferred.

作為聚合物(BOa)，例如可舉出丙烯酸6-[(2-膦醯基乙醯基)氧基]己酯、甲基丙烯酸2-膦醯氧基乙酯、甲基丙烯酸膦醯基甲酯、甲基丙烯酸11-膦醯基十一烷基酯、甲基丙烯酸1,1-二膦醯基乙酯等之(甲基)丙烯酸膦醯基酯類的聚合物；乙烯基膦酸、2-丙烯-1-膦酸、4-乙烯基苄基膦酸、4-乙烯基苯膦酸等之乙烯基膦酸類的聚合物；乙烯基次膦酸、4-乙烯基苄基次膦酸等之乙烯基次膦酸類的聚合物；磷酸化澱粉等。聚合物(BOa)可為具有至少1種含磷原子的官能基之單體的均聚物，也可為2種以上的單體的共聚物。又，作為聚合物(BOa)，亦可併用2種以上的由單一單體所形成的聚合物。其中，較佳為(甲基)丙烯酸膦醯酯類的聚合物及乙烯基膦酸類的聚合物，更佳為乙烯基膦酸類的聚合物，尤佳為聚乙烯基膦酸。另外，聚合物(BOa)亦可藉由將乙烯基膦酸鹵化物或乙烯基膦酸酯等之乙烯基膦酸衍生物單獨或共聚合後，進行水解而得。Examples of the polymer (BOa) include 6-[(2-phosphonylacetyl)oxy]hexyl acrylate, 2-phosphonyloxyethyl methacrylate, phosphonylmethyl methacrylate, and Polymers of (meth)phosphonyl esters such as 11-phosphonyl undecyl methacrylate, 1,1-diphosphonyl ethyl methacrylate, etc.; vinylphosphonic acid, Polymers of vinylphosphonic acids such as 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic acid; vinylphosphinic acid, 4-vinylbenzylphosphinic acid Polymers of vinyl phosphinic acid; phosphorylated starch, etc. The polymer (BOa) may be a homopolymer of a monomer having at least one phosphorus atom-containing functional group, or may be a copolymer of two or more monomers. Moreover, as a polymer (BOa), the polymer which consists of 2 or more types of single monomers can also be used together. Among them, polymers of phosphonyl (meth)acrylate and polymers of vinylphosphonic acid are preferred, polymers of vinylphosphonic acid are more preferred, and polyvinylphosphonic acid is especially preferred. In addition, the polymer (BOa) can also be obtained by hydrolyzing vinylphosphonic acid derivatives such as vinylphosphonic acid halides and vinylphosphonic acid esters alone or copolymerized.

又，聚合物(BOa)可為具有至少1種含磷原子的官能基的單體與其他乙烯基單體之共聚物。作為可與具有含磷原子的官能基的單體進行共聚合之其他乙烯基單體，例如可舉出(甲基)丙烯酸、(甲基)丙烯酸酯類、丙烯腈、甲基丙烯腈、苯乙烯、核取代苯乙烯類、烷基乙烯醚類、烷基乙烯酯類、全氟烷基乙烯醚類、全氟烷基乙烯酯類、馬來酸、馬來酸酐、富馬酸、伊康酸、馬來醯亞胺、苯基馬來醯亞胺等，其中較佳為(甲基)丙烯酸酯類、丙烯腈、苯乙烯、馬來醯亞胺及苯基馬來醯亞胺。Also, the polymer (BOa) may be a copolymer of a monomer having at least one phosphorus atom-containing functional group and another vinyl monomer. Examples of other vinyl monomers that can be copolymerized with monomers having phosphorus atom-containing functional groups include (meth)acrylic acid, (meth)acrylates, acrylonitrile, methacrylonitrile, benzene Ethylene, nuclear substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, Icon acid, maleimide, phenylmaleimide, and the like, among which (meth)acrylates, acrylonitrile, styrene, maleimide, and phenylmaleimide are preferred.

為了得到具有優異的耐彎曲性之多層構造體，源自具有含磷原子的官能基的單體之構成單元佔聚合物(BOa)的全部結構單元之比例較佳為10莫耳%以上，更佳為40莫耳%以上，尤佳為70莫耳%以上，特佳為90莫耳%以上，亦可為100莫耳%。In order to obtain a multilayer structure having excellent bending resistance, the proportion of the structural units derived from monomers having functional groups containing phosphorus atoms to the total structural units of the polymer (BOa) is preferably 10 mol% or more, more preferably Preferably it is more than 40 mol%, especially preferably more than 70 mol%, especially preferably more than 90 mol%, and may be 100 mol%.

聚合物(BOa)的分子量係沒有特別的限制，但數量平均分子量較佳在1000~100000之範圍。若數量平均分子量在該範圍，則可以高水準兼顧本發明之多層構造體的耐彎曲性之改善效果及使用後述塗佈液(S)時塗佈液(S)的黏度安定性。The molecular weight of the polymer (BOa) is not particularly limited, but the number average molecular weight is preferably in the range of 1,000-100,000. When the number average molecular weight is within this range, the effect of improving the bending resistance of the multilayer structure of the present invention and the viscosity stability of the coating solution (S) when using the coating solution (S) described later can be achieved at a high level.

於多層構造體的層(Y)中，包含聚合物(BOa)時，層(Y)中的聚合物(BOa)的質量WBOa相對於無機磷化合物(BI)的質量WBI之比WBOa/WBI，較佳為滿足0.01/99.99≦WBOa/WBI＜6.00/94.00之關係，從阻隔性能優異之點來看，較佳為滿足0.10/99.90≦WBOa/WBI＜4.50/95.50之關係，更佳為滿足0.20/99.80≦WBOa/WBI＜4.00/ 96.00之關係，特佳為滿足0.50/99.50≦WBOa/WBI＜3.50/96.50之關係。亦即，相對於WBOa為0.01以上且未達6.00的微量，WBI以多於94.00且在99.99以下的大量使用為佳。尚且，即使為在層(Y)中無機磷化合物(BI)及/或有機磷化合物(BOa)進行反應之情況，也將構成反應生成物(D)的無機磷化合物(BI)及/或有機磷化合物(BOa)的部分視為無機磷化合物(BI)及/或有機磷化合物(BOa)。於此情況下，將反應生成物(D)之形成時所用的無機磷化合物(BI)及/或有機磷化合物(BOa)的質量(反應前的無機磷化合物(BI)及/或有機磷化合物(BOa)的質量)包含於層(Y)中的無機磷化合物(BI)及/或有機磷化合物(BOa)的質量中。In the layer (Y) of the multilayer structure, when the polymer (BOa) is included, the ratio WBOa/WBI of the mass WBOa of the polymer (BOa) in the layer (Y) to the mass WBI of the inorganic phosphorus compound (BI), It is preferable to satisfy the relationship of 0.01/99.99≦WBOa/WBI<6.00/94.00. From the point of view of excellent barrier performance, it is preferable to satisfy the relationship of 0.10/99.90≦WBOa/WBI<4.50/95.50, and more preferably to satisfy 0.20 /99.80≦WBOa/WBI<4.00/96.00, particularly preferably 0.50/99.50≦WBOa/WBI<3.50/96.50. That is, it is preferable to use a large amount of WBI more than 94.00 and 99.99 or less with respect to a trace amount of WBOa of 0.01 or more and less than 6.00. Moreover, even in the case where the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) react in the layer (Y), the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) constituting the reaction product (D) The part of the phosphorus compound (BOa) is regarded as an inorganic phosphorus compound (BI) and/or an organic phosphorus compound (BOa). In this case, the mass of the inorganic phosphorus compound (BI) and/or organic phosphorus compound (BOa) used in the formation of the reaction product (D) (inorganic phosphorus compound (BI) and/or organic phosphorus compound before the reaction (mass of BOa)) is included in the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) in the layer (Y).

(有機磷化合物(BOb)) 有機磷化合物(BOb)中，透過碳數3以上20以下的伸烷基鏈或聚氧伸烷基鏈，至少1個羥基鍵結了的磷原子與極性基係鍵結。與金屬氧化物(A)、無機磷化合物(BI)及彼等的反應生成物(D)比較下，有機磷化合物(BOb)係表面自由能低，在層(Y)之前驅物形成過程中偏析於表面側。結果，有本發明之多層構造體的耐彎曲性或與層(Y)直接積層的層之接著性提升之情況。 (organophosphorus compounds (BOb)) In the organophosphorus compound (BOb), a phosphorus atom to which at least one hydroxyl group is bonded is bonded to a polar group through an alkylene chain or polyoxyalkylene chain having 3 to 20 carbon atoms. Compared with metal oxides (A), inorganic phosphorus compounds (BI) and their reaction products (D), organic phosphorus compounds (BOb) have low surface free energy, and during the formation of layer (Y) precursors Segregates on the surface side. As a result, the bending resistance of the multilayer structure of the present invention or the adhesiveness of the layer directly laminated with the layer (Y) may be improved.

作為有機磷化合物(BOb)，例如可舉出3-羥丙基膦酸、4-羥丁基膦酸、5-羥戊基膦酸、6-羥己基膦酸、7-羥庚基膦酸、8-羥辛基膦酸、9-羥壬基膦酸、10-羥癸基膦酸、11-羥基十一基膦酸、12-羥基十二基膦酸、13-羥基十三基膦酸、14-羥基十四基膦酸、15-羥基十五基膦酸、16-羥基十六基膦酸、17-羥基十七基膦酸、18-羥基十八基膦酸、19-羥基十九基膦酸、20-羥基二十基膦酸、3-羥丙基二氫磷酸酯、4-羥丁基二氫磷酸酯、5-羥戊基二氫磷酸酯、6-羥己基二氫磷酸酯、7-羥庚基二氫磷酸酯、8-羥辛基二氫磷酸酯、9-羥壬基二氫磷酸酯、10-羥癸基二氫磷酸酯、11-羥基十一基二氫磷酸酯、12-羥癸基二氫磷酸酯、13-羥基十三基二氫磷酸酯、14-羥基十四基二氫磷酸酯、15-羥基十五基二氫磷酸酯、16-羥基十六基二氫磷酸酯、17-羥基十七基二氫磷酸酯、18-羥基十八基二氫磷酸酯、19-羥基十九基二氫磷酸酯、20-羥基二十基二氫磷酸酯、3-羧丙基膦酸、4-羧丁基膦酸、5-羧戊基膦酸、6-羧己基膦酸、7-羧庚基膦酸、8-羧辛基膦酸、9-羧壬基膦酸、10-羧癸基膦酸、11-羧基十一基膦酸、12-羧基十二基膦酸、13-羧基十三基膦酸、14-羧基十四基膦酸、15-羧基十五基膦酸、16-羧基十六基膦酸、17-羧基十七基膦酸、18-羧基十八基膦酸、19-羧基十九基膦酸、20-羧基二十基膦酸等。此等可單獨使用1種，也可併用2種以上。Examples of organic phosphorus compounds (BOb) include 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, and 7-hydroxyheptylphosphonic acid. , 8-hydroxyoctylphosphonic acid, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxytridecylphosphine Acid, 14-hydroxytetradecylphosphonic acid, 15-hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxy Nonadecylphosphonic acid, 20-hydroxyeicosylphosphonic acid, 3-hydroxypropyl dihydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-hydroxypentyl dihydrogen phosphate, 6-hydroxyhexyl dihydrogen phosphate Hydrogen phosphate, 7-hydroxyheptyl dihydrogen phosphate, 8-hydroxyoctyl dihydrogen phosphate, 9-hydroxynonyl dihydrogen phosphate, 10-hydroxydecyl dihydrogen phosphate, 11-hydroxyundecyl dihydrogen phosphate Dihydrogen phosphate, 12-hydroxydecyl dihydrogen phosphate, 13-hydroxytridecyl dihydrogen phosphate, 14-hydroxytetradecyl dihydrogen phosphate, 15-hydroxypentadecyl dihydrogen phosphate, 16- Hydroxyhexadecyl dihydrogen phosphate, 17-hydroxyheptadecyl dihydrogen phosphate, 18-hydroxyoctadecyl dihydrogen phosphate, 19-hydroxynonadecyl dihydrogen phosphate, 20-hydroxyeicosyl dihydrogen phosphate Phosphate, 3-carboxypropylphosphonic acid, 4-carboxybutylphosphonic acid, 5-carboxypentylphosphonic acid, 6-carboxyhexylphosphonic acid, 7-carboxyheptylphosphonic acid, 8-carboxyoctylphosphonic acid, 9-Carboxynonylphosphonic acid, 10-carboxydecylphosphonic acid, 11-carboxyundecylphosphonic acid, 12-carboxydodecylphosphonic acid, 13-carboxytridecylphosphonic acid, 14-carboxytetradecylphosphonic acid Acid, 15-carboxypentadecylphosphonic acid, 16-carboxyhexadecylphosphonic acid, 17-carboxyheptadecylphosphonic acid, 18-carboxyoctadecylphosphonic acid, 19-carboxynonadecylphosphonic acid, 20-carboxy Eicosylphosphonic acid, etc. These may be used individually by 1 type, and may use 2 or more types together.

於多層構造體之層(Y)中，包含有機磷化合物(BOb)時，層(Y)中的有機磷化合物(BOb)的莫耳數MBob與無機磷化合物(BI)的莫耳數MBI之比MBob/MBI，較佳為滿足1.0×10 -4≦MBOb/MBI≦2.0×10 -2之關係，更佳為滿足3.5×10 -4≦MBOb/MBI≦1.0×10 -2之關係，尤佳為滿足5.0×10 -4≦MBOb/MBI≦6.0×10 -3之關係。 When the layer (Y) of the multilayer structure contains an organic phosphorus compound (BOb), the difference between the molar number MBob of the organic phosphorus compound (BOb) in the layer (Y) and the molar number MBI of the inorganic phosphorus compound (BI) Compared with MBob/MBI, it is better to satisfy the relationship of 1.0×10 -4 ≦MBOb/MBI≦2.0×10 -2 , more preferably to satisfy the relationship of 3.5×10 -4 ≦MBOb/MBI≦1.0×10 -2 , especially It is preferable to satisfy the relationship of 5.0×10 -4 ≦MBOb/MBI≦6.0×10 -3 .

層(Y)包含有機磷化合物(BOb)時，藉由X射線光電子分光分析法(XPS法)測定的多層構造體之層(Y)之與基材(X)未相接之側的表面起到5nm為止的範圍中的碳原子相對於鋁原子之原子數比(C/Al比)較佳在0.1~15.0之範圍，更佳在0.3~10.0之範圍，特佳在0.5~5.0之範圍。由於層(Y)表面的C/Al比在前述範圍，有層(Y)與鄰接的層之接著性提升之情況。When the layer (Y) contains an organophosphorus compound (BOb), from the surface of the layer (Y) of the multilayer structure that is not in contact with the substrate (X) measured by X-ray photoelectron spectroscopy (XPS method) The atomic number ratio of carbon atoms to aluminum atoms (C/Al ratio) in the range up to 5 nm is preferably in the range of 0.1 to 15.0, more preferably in the range of 0.3 to 10.0, and particularly preferably in the range of 0.5 to 5.0. Since the C/Al ratio on the surface of the layer (Y) is in the aforementioned range, the adhesiveness between the layer (Y) and the adjacent layer may be improved.

(含交聯劑的樹脂組成物(V)) 層(Y)由於包含含交聯劑的樹脂組成物(V)，有耐彎曲性變良好之情況。含交聯劑的樹脂組成物(V)係由含羥基的樹脂及交聯劑所構成。作為前述含羥基的樹脂，可舉出含羥基的環氧樹脂、含羥基的聚酯樹脂、含羥基的(甲基)丙烯酸樹脂、含羥基的聚胺基甲酸酯樹脂、乙烯醇系樹脂、多糖類等，其中較佳為包含乙烯醇系樹脂或多糖類，更佳為包含乙烯醇系樹脂，尤佳為包含聚乙烯醇樹脂。作為前述交聯劑，宜使用具有環氧丙基的矽化合物、有機鈦化合物或有機鋯化合物。前述含羥基的樹脂與前述交聯劑之質量比(含羥基的樹脂/交聯劑)較佳為2.0以上200以下，更佳為9.0以上60以下。 (Resin composition (V) containing a crosslinking agent) Since the layer (Y) contains the resin composition (V) containing a crosslinking agent, bending resistance may become favorable. The crosslinking agent-containing resin composition (V) is composed of a hydroxyl group-containing resin and a crosslinking agent. Examples of the hydroxyl-containing resin include hydroxyl-containing epoxy resins, hydroxyl-containing polyester resins, hydroxyl-containing (meth)acrylic resins, hydroxyl-containing polyurethane resins, vinyl alcohol-based resins, Among them, polysaccharides and the like preferably contain vinyl alcohol-based resins or polysaccharides, more preferably contain vinyl alcohol-based resins, and particularly preferably contain polyvinyl alcohol resins. As the aforementioned crosslinking agent, a silicon compound having a glycidyl group, an organotitanium compound or an organozirconium compound is preferably used. The mass ratio of the hydroxyl-containing resin to the cross-linking agent (hydroxyl-containing resin/cross-linking agent) is preferably from 2.0 to 200, more preferably from 9.0 to 60.

[層(W)] 本發明之多層構造體中，包含選自由聚合物(F)、有機磷化合物(BO)及含交聯劑的樹脂組成物(V)所成之群組的至少1種之層(W)，係可直接積層於層(Y)之與基材(X)相反側的面上。由於多層構造體具備層(W)，有耐彎曲性提升，或與後述接著層(I’)的密著性提升之情況。從多層構造體的鮮明度之觀點來看，有不含層(W)者為較佳的情況。 [Layer (W)] In the multilayer structure of the present invention, a layer (W) comprising at least one kind selected from the group consisting of a polymer (F), an organophosphorus compound (BO) and a crosslinking agent-containing resin composition (V), It can be directly laminated on the surface of the layer (Y) opposite to the substrate (X). Since the multilayer structure includes the layer (W), the bending resistance may be improved, or the adhesion with the adhesive layer (I') described later may be improved. From the viewpoint of the clarity of the multilayer structure, it may be preferable not to have a layer (W).

本發明之多層構造體具備層(W)時，層(W)較佳為與層(Y)直接積層。層(W)可含有的聚合物(F)、有機磷化合物(BO)及含交聯劑的樹脂組成物(V)之合適的態樣係如上述。When the multilayer structure of the present invention has a layer (W), it is preferable that the layer (W) is directly laminated with the layer (Y). Suitable aspects of the polymer (F), organophosphorus compound (BO) and crosslinking agent-containing resin composition (V) that the layer (W) may contain are as described above.

層(W)可進一步包含其他成分，例如可舉出碳酸鹽、鹽酸鹽、硝酸鹽、碳酸氫鹽、硫酸鹽、硫酸氫鹽、硼酸鹽等之無機酸金屬鹽、草酸鹽、乙酸鹽、酒石酸鹽、硬脂酸鹽等之有機酸金屬鹽、環戊二烯基金屬錯合物(例如二茂鈦)、氰基金屬錯合物(例如普魯士藍)等之金屬錯合物、層狀黏土化合物、交聯劑、聚合物(BOa)及聚合物(F)以外的高分子化合物、可塑劑、抗氧化劑、紫外線吸收劑、難燃劑等。層(W)中的前述其他成分之含有率較佳為20質量%以下，更佳為10質量%以下，尤佳為5質量%以下，亦可為2質量%以下，也可為1質量%以下，也可為0質量%(不含其他成分)。The layer (W) may further contain other components, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, borates, oxalates, acetates , metal salts of organic acids such as tartrates, stearates, etc., metal complexes such as cyclopentadienyl complexes (such as titanocene), cyanometallic complexes (such as Prussian blue), etc. clay compound, crosslinking agent, polymer compound other than polymer (BOa) and polymer (F), plasticizer, antioxidant, ultraviolet absorber, flame retardant, etc. The content of the aforementioned other components in the layer (W) is preferably at most 20% by mass, more preferably at most 10% by mass, even more preferably at most 5% by mass, may be at most 2% by mass, or may be at most 1% by mass. Below, 0 mass % (excluding other components) may be sufficient.

本發明之多層構造體具備層(W)時，從本發明之多層構造體的耐彎曲性變更良好之觀點來看，其厚度較佳為0.005μm以上。層(W)之厚度的上限係沒有特別的限定，但1.0μm以上時耐彎曲性的改善效果達到飽和，因此將層(W)之厚度的上限定設為1.0μm，此係在經濟上較宜。When the multilayer structure of the present invention has a layer (W), its thickness is preferably 0.005 μm or more from the viewpoint of improving the bending resistance of the multilayer structure of the present invention. The upper limit of the thickness of the layer (W) is not particularly limited, but the effect of improving the bending resistance is saturated when it is more than 1.0 μm, so it is more economical to set the upper limit of the thickness of the layer (W) to 1.0 μm. should.

[接著層(I)] 本發明之多層構造體可在基材(X)與層(Y)之間具備接著層(I)。由於具備接著層(I)，有能提高基材(X)與層(Y)之間的接著性之情況。特別地，於基材(X)具有表面層之情況中，較佳為在表面層與層(Y)之間設置接著層(I)，更佳為在將表面層進行表面處理後，設置接著層(I)。 [adhesion layer (I)] The multilayer structure of the present invention may include an adhesive layer (I) between the substrate (X) and the layer (Y). By providing the adhesive layer (I), the adhesiveness between the base material (X) and the layer (Y) may be improved. In particular, in the case where the base material (X) has a surface layer, it is preferable to provide an adhesive layer (I) between the surface layer and the layer (Y), more preferably after the surface layer is subjected to surface treatment, an adhesive layer (I) is provided. Layer (I).

作為構成接著層(I)的接著劑，只要具有基材(X)與層(Y)的接著性，則沒有特別的限定，但可舉出聚胺基甲酸酯系接著劑、聚酯系接著劑等。藉由在此等接著劑中添加眾所周知的矽烷偶合劑等之少量的添加劑，有能進一步提高接著性之情況。作為矽烷偶合劑，例如可舉出具有異氰酸酯基、環氧基、胺基、脲基、巰基等反應性基的矽烷偶合劑。The adhesive constituting the adhesive layer (I) is not particularly limited as long as it has adhesiveness between the substrate (X) and the layer (Y), but examples include polyurethane-based adhesives, polyester-based Adhesives, etc. By adding a small amount of additives such as well-known silane coupling agents to these adhesives, the adhesiveness may be further improved. As a silane coupling agent, the silane coupling agent which has reactive groups, such as an isocyanate group, an epoxy group, an amine group, a urea group, a mercapto group, is mentioned, for example.

作為聚胺基甲酸酯系接著劑，可使用眾所周知者，但較佳為使用將聚異氰酸酯成分與多元醇成分混合並使其反應的2液型聚胺基甲酸酯系接著劑。作為2液型聚胺基甲酸酯系接著劑，可使用市售品，例如可舉出三井化學股份有限公司製的Takelac(註冊商標)、Takenate(註冊商標)等。As the polyurethane adhesive, well-known ones can be used, but it is preferable to use a two-component polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted. As a two-component type polyurethane adhesive agent, a commercial item can be used, for example, Takelac (registered trademark) and Takenate (registered trademark) by Mitsui Chemicals Co., Ltd., etc. are mentioned.

作為聚酯系接著劑，可使用眾所周知者，作為市售品，例如可舉出Elitel(註冊商標)KT-0507、KT-8701、KT-8803、KT-9204、KA-5034、KA-3556、KA-1449、KA-5071S、KZA-1449S(以上為UNITIKA股份有限公司製)、Vylonal(註冊商標)MD-1200、Vylonal MD-1480 (以上為東洋紡績股份有限公司製)、Pesresin A124GP、Pesresin A684G(高松油脂股份有限公司製)等。藉由對聚酯系接著劑添加乙烯醇系樹脂，尤其是聚乙烯醇，有更提高接著性之情況。同時使用乙烯醇系樹脂與聚酯系樹脂時，其質量比(乙烯醇系樹脂/聚酯系樹脂)為1/99以上50/50以下者，從一邊維持良好的接著性，一邊顯示更高的剝離強度之觀點來看較宜。聚酯系樹脂，從與乙烯醇系樹脂的親和性之觀點來看，較佳為具有羧基的聚酯系樹脂。又，作為接著劑使用時，聚酯系樹脂較佳為水性分散體。由於聚酯系樹脂為水性分散體，有與聚乙烯醇系樹脂的親和性變更良好之傾向。As the polyester-based adhesive, well-known ones can be used, and examples of commercial products include Elitel (registered trademark) KT-0507, KT-8701, KT-8803, KT-9204, KA-5034, KA-3556, KA-1449, KA-5071S, KZA-1449S (manufactured by UNITIKA Co., Ltd. above), Vylonal (registered trademark) MD-1200, Vylonal MD-1480 (manufactured by Toyobo Co., Ltd. above), Pesresin A124GP, Pesresin A684G (manufactured by Takamatsu Oil Co., Ltd.), etc. By adding vinyl alcohol-based resins, especially polyvinyl alcohol, to polyester-based adhesives, the adhesiveness may be further improved. When vinyl alcohol-based resin and polyester-based resin are used at the same time, the mass ratio (vinyl alcohol-based resin/polyester-based resin) of 1/99 to 50/50 shows higher adhesiveness while maintaining good adhesion. It is preferable from the viewpoint of the peel strength. The polyester-based resin is preferably a polyester-based resin having a carboxyl group from the viewpoint of affinity with vinyl alcohol-based resins. Also, when used as an adhesive, the polyester-based resin is preferably an aqueous dispersion. Since the polyester-based resin is an aqueous dispersion, there is a tendency that the affinity change with the polyvinyl alcohol-based resin is improved.

接著層(I)之每1層的厚度較佳為0.001~10.0 μm，更佳為0.003~5.0μm，尤佳為0.005~1.0μm，尤更佳為0.007~0.1μm，特佳為0.01~0.03μm。The thickness of each layer of the subsequent layer (I) is preferably 0.001~10.0 μm, more preferably 0.003~5.0 μm, especially preferably 0.005~1.0 μm, still more preferably 0.007~0.1 μm, especially preferably 0.01~0.03 μm μm.

[其他層(J)] 本發明之多層構造體係為了提高各式各樣的特性(例如熱封性、阻隔性、力學物性)，可包含基材(X)、層(Y)、層(W)及接著層(I)以外的其他層(J)。如此的本發明之多層構造體例如可藉由在基材(X)上將層(Y)(視需要隔著接著層(I))積層，進一步將該其他層(J)直接或隔著後述接著層(I’)進行接著或形成而製造。作為其他層(J)，例如可舉出油墨層、聚烯烴層、乙烯-乙烯醇共聚物樹脂層等之熱塑性樹脂層等，但不受該等所限定。 [Other layers (J)] In order to improve various properties (such as heat-sealing properties, barrier properties, and mechanical properties), the multi-layer structure system of the present invention may include a substrate (X), a layer (Y), a layer (W) and an adhesive layer (I) Other layers than (J). Such a multilayer structure of the present invention can be, for example, laminated on the substrate (X) with the layer (Y) (if necessary via the adhesive layer (I)), and further directly or via the other layer (J) described later. The bonding layer (I') is manufactured by bonding or forming it. Examples of other layers (J) include thermoplastic resin layers such as ink layers, polyolefin layers, and ethylene-vinyl alcohol copolymer resin layers, but are not limited thereto.

本發明之多層構造體包含油墨層時，作為油墨層，例如可舉出將在溶劑中分散有含有顏料(例如二氧化鈦)的聚胺基甲酸酯樹脂之液體進行乾燥而得之皮膜，但亦可為將不含顏料的聚胺基甲酸酯樹脂、以其他樹脂作為主劑的油墨或電子電路配線形成用阻劑進行乾燥而得之皮膜。作為油墨層的塗佈方法，除了凹版印刷法之外，還可舉出線棒、旋塗、模塗等各種的塗佈方法。油墨層之厚度較佳為0.5~10.0μm，更佳為1.0~4.0μm。When the multilayer structure of the present invention includes an ink layer, the ink layer includes, for example, a film obtained by drying a liquid in which a polyurethane resin containing a pigment (for example, titanium dioxide) is dispersed in a solvent. It can be a film obtained by drying a pigment-free polyurethane resin, an ink based on other resins, or a resist for forming electronic circuit wiring. As the coating method of the ink layer, various coating methods such as wire bar, spin coating, and die coating can be mentioned besides the gravure printing method. The thickness of the ink layer is preferably 0.5-10.0 μm, more preferably 1.0-4.0 μm.

藉由將本發明之多層構造體的最表面層設為聚烯烴層，可將熱封性賦予至多層構造體，或提高多層構造體的力學特性。從熱封性或力學特性的提升等之觀點來看，聚烯烴較佳為聚丙烯或聚乙烯。又，為了提高多層構造體的力學特性，較佳為積層選自由聚酯所成的薄膜、聚醯胺所成的薄膜及含羥基的聚合物所成的薄膜所成之群組的至少1個薄膜。從力學特性的提升之觀點來看，聚酯較佳為聚對苯二甲酸乙二酯，聚醯胺較佳為尼龍-6，含羥基的聚合物較佳為乙烯-乙烯醇共聚物。By making the outermost layer of the multilayer structure of the present invention a polyolefin layer, it is possible to impart heat sealability to the multilayer structure, or to improve the mechanical properties of the multilayer structure. The polyolefin is preferably polypropylene or polyethylene from the viewpoint of improvement of heat sealability and mechanical properties. In addition, in order to improve the mechanical properties of the multilayer structure, it is preferable to laminate at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and a film made of a hydroxyl-containing polymer. film. From the viewpoint of improving the mechanical properties, the polyester is preferably polyethylene terephthalate, the polyamide is preferably nylon-6, and the hydroxyl-containing polymer is preferably ethylene-vinyl alcohol copolymer.

其他層(J)可為藉由擠出塗佈層合而形成的層。本發明可使用的擠出塗佈層合法係沒有特別的限定，可使用眾所周知的方法。於典型的擠出塗佈層合法中，藉由將經熔融熱塑性樹脂送到T字模，將從T字模的扁平狹縫所取出的熱塑性樹脂進行冷卻，而製造層合薄膜。The other layer (J) may be a layer formed by extrusion coating lamination. The extrusion coating lamination method usable in the present invention is not particularly limited, and a known method can be used. In a typical extrusion coating lamination method, a laminated film is produced by feeding molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from the flat slit of the T-die.

作為其他的擠出塗佈層合法，可舉出三明治層合法、串聯層合法等。三明治層合法係將經熔融的熱塑性樹脂擠出至一方的基材，從另一個解捲機(捲出機)供給第2基材，使其貼合而製作積層體之方法。串聯層合法為連接2台的單層合機，一次製作5層構成的積層體之方法。As another extrusion coating lamination method, a sandwich lamination method, a tandem lamination method, etc. are mentioned. The sandwich lamination method is a method in which molten thermoplastic resin is extruded to one base material, and the second base material is supplied from another unwinder (unwinder), and bonded together to produce a laminated body. The series lamination method is a method of connecting two single-layer lamination machines to produce a laminated body consisting of five layers at a time.

[接著層(I’)] 於本發明之多層構造體中，有使用接著層(I’)而能提高與其他構件(例如其他層(J)等)的接著性之情況。接著層(I)可由接著性樹脂構成。構成接著層(I’)的接著劑係可使用作為構成接著層(I)的接著劑所例示者。作為提高與前述其他構件的接著性之接著性樹脂，較佳為將聚異氰酸酯成分與多元醇成分混合並使其反應的2液反應型聚胺基甲酸酯系接著劑。又，藉由在錨塗劑或接著劑中，添加眾所周知的矽烷偶合劑等少量的添加劑，有能進一步提高接著性之情況。作為矽烷偶合劑，例如可舉出具有異氰酸酯基、環氧基、胺基、脲基、巰基等反應性基之矽烷偶合劑，但不受該等所限定。藉由與其他構件之接著，於對本發明之多層構造體施予印刷或層合等加工時，更有效地抑制阻氣性或外觀的變差，再者，有能提高使用本發明之多層構造體的保護薄片及電子裝置等之落下強度的情況。 [The next layer (I')] In the multilayer structure of the present invention, the adhesive layer (I') may be used to improve the adhesiveness with other members (for example, another layer (J), etc.). The adhesive layer (I) may consist of an adhesive resin. As the adhesive constituting the adhesive layer (I'), those exemplified as the adhesive constituting the adhesive layer (I) can be used. As an adhesive resin that improves the adhesiveness with the above-mentioned other members, a two-component reactive polyurethane-based adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. In addition, by adding a small amount of additives such as well-known silane coupling agents to the anchor coating agent or the adhesive agent, the adhesiveness may be further improved. As a silane coupling agent, the silane coupling agent which has reactive groups, such as an isocyanate group, an epoxy group, an amine group, a urea group, a mercapto group, is mentioned, for example, However, It is not limited to these. By bonding with other components, when the multilayer structure of the present invention is subjected to processing such as printing or lamination, the deterioration of gas barrier properties or appearance can be more effectively suppressed, and furthermore, it is possible to improve the use of the multilayer structure of the present invention. The drop strength of body protective sheets and electronic devices, etc.

[多層構造體之構成等] 於本發明之多層構造體中，至少一組的基材(X)及層(Y)係鄰接而被積層。基材(X)與層(Y)可直接積層，也可隔著接著層(I)積層，但於基材(X)具有表面層，且具備與表面層對向的層(Y)之情況，基材(X)與層(Y)較佳為隔著接著層(I)積層，於基材(X)不具有表面層之情況，基材(X)與層(Y)較佳為被直接積層。 [Constitution of multi-layer structures, etc.] In the multilayer structure of the present invention, at least one set of base material (X) and layer (Y) is adjacently laminated. Substrate (X) and layer (Y) may be laminated directly or laminated via adhesive layer (I), but in the case of substrate (X) having a surface layer and layer (Y) facing the surface layer , the substrate (X) and the layer (Y) are preferably laminated with the adhesive layer (I) interposed therebetween, and in the case where the substrate (X) does not have a surface layer, the substrate (X) and the layer (Y) are preferably covered direct lamination.

以下顯示本發明之多層構造體的構成例，但本發明之多層構造體不受此等所限定。各自的具體例亦可為複數組合之構成。此處，所謂「/」，就是意指隔著接著層或直接積層。 (1)層(Y)/基材(X) (2)層(Y)/基材(X)/層(Y) (3)基材(X)/層(Y)/層(Y)/基材(X) (4)層(Y)/基材(X)/基材(X)/層(Y) (5)層(Y)/基材(X)/層(Y)/基材(X) (6)層(Y)/基材(X)/層(Y)/基材(X)/層(Y) 於上述例示中，基材(X)較佳為包含PET層。又，亦可進一步具有其他層(J)，具有其他層(J)時，其他層(J)可隔著接著層(I’)積層於層(Y)或基材(X)等。多層構造體可僅由基材層(X)及層(Y)所構成，也可僅由基材層(X)、層(Y)及接著層(I)所構成。 The configuration examples of the multilayer structure of the present invention are shown below, but the multilayer structure of the present invention is not limited thereto. The specific examples of each may be configured in plural combinations. Here, the so-called "/" means that the layer is separated or directly laminated. (1) Layer (Y)/Substrate (X) (2) Layer (Y)/Substrate (X)/Layer (Y) (3) Substrate (X)/layer (Y)/layer (Y)/substrate (X) (4) Layer (Y)/Substrate (X)/Substrate (X)/Layer (Y) (5) Layer (Y)/Substrate (X)/Layer (Y)/Substrate (X) (6) Layer (Y)/Substrate (X)/Layer (Y)/Substrate (X)/Layer (Y) In the above examples, the substrate (X) preferably includes a PET layer. In addition, another layer (J) may be further provided, and when the other layer (J) is provided, the other layer (J) may be laminated on the layer (Y) or the substrate (X) via the adhesive layer (I'). The multilayer structure may consist only of the base layer (X) and layer (Y), or may consist of only the base layer (X), layer (Y) and adhesive layer (I).

依據JIS K7105：1981測定的本發明之多層構造體的霧度值較佳為3%以下，更佳為2.5%以下，尤佳為2.0%以下。藉由霧度值為前述上限以下，多層構造體的鮮明度更提高。本發明之多層構造體的霧度值可為0.1%以上，也可為0.5%以上。多層構造體的霧度值係可藉由基材(X)之種類及厚度、層(Y)之厚度等來調整。The haze value of the multilayer structure of the present invention measured in accordance with JIS K7105:1981 is preferably 3% or less, more preferably 2.5% or less, especially preferably 2.0% or less. When the haze value is not more than the above upper limit, the clarity of the multilayer structure is further improved. The haze value of the multilayer structure of the present invention may be 0.1% or more, and may be 0.5% or more. The haze value of the multilayer structure can be adjusted by the type and thickness of the substrate (X), the thickness of the layer (Y), and the like.

依據ISO15106-5：2015測定的40℃、90%RH下的本發明之多層構造體的水蒸氣透過率較佳為1×10 -2g/m 2・day以下，更佳為5.0×10 -3g/m 2・day以下，尤佳3.0 ×10 -3g/m 2・day以下。本發明之多層構造體的水蒸氣透過率可為1.0×10 -5g/m 2・day以上，也可為1.0×10 -4g/m 2・day以上。多層構造體的水蒸氣透過率係可藉由基材(X)之種類及厚度、層(Y)之厚度等來調整。 The water vapor transmission rate of the multilayer structure of the present invention at 40°C and 90% RH measured in accordance with ISO15106-5:2015 is preferably 1×10 -2 g/m 2 ·day or less, more preferably 5.0×10 - Below 3 g/m 2 ·day, preferably below 3.0 ×10 -3 g/m 2 ·day. The water vapor transmission rate of the multilayer structure of the present invention may be 1.0×10 -5 g/m 2 ·day or higher, and may be 1.0×10 -4 g/m 2 ·day or higher. The water vapor transmission rate of the multilayer structure can be adjusted by the type and thickness of the substrate (X), the thickness of the layer (Y), and the like.

[多層構造體之製造方法] 針對本發明之多層構造體說明的事項由於可適用於本發明之製造方法，因此有將重複的說明省略之情況。又，針對本發明之製造方法說明的事項係可適用於本發明之多層構造體。 [Manufacturing method of multilayer structure] Since the matters described for the multilayer structure of the present invention are applicable to the production method of the present invention, repeated descriptions may be omitted. Moreover, the matter demonstrated about the manufacturing method of this invention is applicable to the multilayer structure of this invention.

作為本發明之多層構造體之製造方法，例如可舉出一種製造方法，其包含：將包含金屬氧化物(A)、無機磷化合物(BI)與溶劑之塗佈液(S)塗佈於基材(X)的至少一面側，去除前述溶劑而形成層(Y)的前驅物層之步驟(I)；及，熱處理層(Y)的前驅物層而形成層(Y)之步驟(II)；步驟(I)的塗佈液(S)之塗佈速度係塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下。製造包含有機磷化合物(BO)或聚合物(F)之多層構造體時，在用於步驟(I)的塗佈液(S)中可含有有機磷化合物(BO)或聚合物(F)，形成包含有機磷化合物(BO)或聚合物(F)之層(Y)，藉由準備包含有機磷化合物(BO)或聚合物(F)之塗佈液(T)，在步驟(I)所得的層(Y)之前驅物層表面或在步驟(II)所得的層(Y)表面塗佈塗佈液(T)之步驟(III)，可使有機磷化合物(BO)或聚合物(F)含浸至層(Y)，亦可在層(Y)上設置層(W)。尚且，於基材(X)與層(Y)之間設置接著層(I)時，該製造方法可在步驟(I)之前包含在基材(X)上設置接著層(I)之步驟。As a method for producing the multilayer structure of the present invention, for example, a production method including: coating a coating liquid (S) containing a metal oxide (A), an inorganic phosphorus compound (BI) and a solvent on a base At least one side of the material (X), removing the aforementioned solvent to form the step (I) of the precursor layer of the layer (Y); and, heat-treating the precursor layer of the layer (Y) to form the step (II) of the layer (Y) ; The coating speed of the coating solution (S) of step (I) is that every 1 cm of the coating width is 0.03 cm/s or more and 2.5 cm/s or less. When producing a multilayer structure comprising an organophosphorus compound (BO) or a polymer (F), the coating liquid (S) used in the step (I) may contain an organophosphorus compound (BO) or a polymer (F), Forming a layer (Y) comprising an organophosphorus compound (BO) or a polymer (F), obtained in step (I) by preparing a coating solution (T) comprising an organophosphorus compound (BO) or a polymer (F) The surface of the precursor layer of the layer (Y) or the step (III) of coating the coating liquid (T) on the surface of the layer (Y) obtained in the step (II) can make the organic phosphorus compound (BO) or the polymer (F ) is impregnated to the layer (Y), and the layer (W) may also be provided on the layer (Y). Furthermore, when the adhesive layer (I) is provided between the substrate (X) and the layer (Y), the production method may include the step of providing the adhesive layer (I) on the substrate (X) before the step (I).

[步驟(I)] 於步驟(I)中，以塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下之速度，將包含金屬氧化物(A)、無機磷化合物(BI)與溶劑之塗佈液(S)塗佈於基材(X)的至少一面側後，去除溶劑，形成層(Y)的前驅物層。塗佈液(S)之塗佈通常係藉由在基材(X)的至少一面上，直接或隔著接著層(I)，塗佈塗佈液(S)而進行。亦即，對設有接著層(I)的基材(X)，可在接著層(I)上塗佈塗佈液(S)。塗佈液(S)之塗佈速度，從所得之多層構造體的圖像清晰度變良好之觀點來看，較佳塗佈寬度每1cm為2.4cm/s以下，更佳為2.0cm/s以下。又，塗佈液(S)之塗佈速度，從所得之多層構造體的圖像清晰度、生產性及塗佈的安定性之觀點來看，較佳塗佈寬度每1cm為0.05cm/s以上，更佳為0.2cm/s以上。 [Step (I)] In step (I), the coating liquid (S) comprising metal oxide (A), inorganic phosphorus compound (BI) and solvent is applied at a speed of 0.03 cm/s to 2.5 cm/s per 1 cm of coating width. ) is applied to at least one side of the substrate (X), and then the solvent is removed to form a precursor layer of the layer (Y). Coating of the coating solution (S) is usually performed by coating the coating solution (S) directly or via the adhesive layer (I) on at least one side of the substrate (X). That is, with respect to the base material (X) provided with the adhesive layer (I), the coating liquid (S) can be apply|coated on the adhesive layer (I). The coating speed of the coating liquid (S) is preferably 2.4 cm/s or less per 1 cm of coating width, more preferably 2.0 cm/s from the viewpoint of improving the image clarity of the obtained multilayer structure the following. In addition, the coating speed of the coating solution (S) is preferably 0.05 cm/s per 1 cm of coating width from the viewpoint of image clarity, productivity, and coating stability of the obtained multilayer structure. above, more preferably above 0.2 cm/s.

藉由塗佈液(S)之塗佈速度，所得之多層構造體的圖像清晰度升高的理由雖然未明，但推測塗佈速度為基材(X)的寬度每1cm超過2.5cm/s時，形成用目視難以確認之程度的塗佈條紋。另一方面，若塗佈速度係寬度每1cm未達0.03cm/s，則塗佈於基材的塗佈液(S)係有被基材排斥之傾向，推測變無法適當地構築層(Y)。又，於塗佈液(S)之塗佈中，為了達成本發明之效果，重要的是將相對於塗佈寬度而言的塗佈速度控制在前述範圍。其理由雖然未明，但認為與塗佈寬度成比例，在基材(X)上所塗佈的塗佈液(S)之對寬度方向的均平範圍變廣，故塗佈後的均平性係變化。The reason why the image clarity of the obtained multilayer structure is improved by the coating speed of the coating solution (S) is unknown, but it is estimated that the coating speed exceeds 2.5 cm/s per 1 cm of the width of the substrate (X) In this case, coating streaks to the extent that it is difficult to recognize visually are formed. On the other hand, if the coating speed is less than 0.03 cm/s per 1 cm width, the coating liquid (S) applied to the substrate tends to be repelled by the substrate, and it is presumed that the layer (Y ). In addition, in the coating of the coating liquid (S), in order to achieve the effect of the present invention, it is important to control the coating speed with respect to the coating width within the aforementioned range. Although the reason is not clear, it is considered that the average range of the coating solution (S) coated on the substrate (X) with respect to the width direction becomes wider in proportion to the coating width, so the uniformity after coating system changes.

塗佈液(S)係可藉由混合金屬氧化物(A)、無機磷化合物(BI)及溶劑而獲得。作為調整塗佈液(S)之具體手段，可舉出混合金屬氧化物(A)的分散液與含有無機磷化合物(BI)的溶液之方法；於金屬氧化物(A)的分散液中添加無機磷化合物(BI)，進行混合之方法等。此等混合時之溫度較佳為50℃以下，更佳為30℃以下，尤佳為20℃以下。塗佈液(S)可包含其他化合物(例如有機磷化合物(BO)或聚合物(F))，視需要可包含選自由乙酸、鹽酸、硝酸、三氟乙酸及三氯乙酸所成之群組的至少1種酸化合物(Q)。The coating solution (S) can be obtained by mixing a metal oxide (A), an inorganic phosphorus compound (BI) and a solvent. Specific means for adjusting the coating liquid (S) include the method of mixing the dispersion liquid of the metal oxide (A) and the solution containing the inorganic phosphorus compound (BI); adding Inorganic phosphorus compound (BI), method of mixing, etc. The temperature at the time of such mixing is preferably below 50°C, more preferably below 30°C, especially preferably below 20°C. The coating solution (S) may contain other compounds (such as organophosphorus compounds (BO) or polymers (F)), and optionally may contain compounds selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid and trichloroacetic acid at least one acid compound (Q).

金屬氧化物(A)之分散液可藉由例如依照眾所周知的溶膠凝膠法所採用之手法，例如混合化合物(E)、水及視需要的酸觸媒或有機溶劑，將化合物(E)縮合或水解縮合而調製。藉由將化合物(E)縮合或水解縮合而得到金屬氧化物(A)的分散液時，視需要亦可對於所得之分散液，進行特定的處理(前述酸化合物(Q)之存在下的解膠等)。金屬氧化物(A)的分散液之調製時所使用的溶劑係沒有特別的限定，但較佳為甲醇、乙醇、異丙醇等之醇類；水；或此等的混合溶劑。The dispersion of metal oxide (A) can be condensed by compound (E) by, for example, following the well-known sol-gel method, such as mixing compound (E), water and, if necessary, an acid catalyst or an organic solvent. Or hydrolytic condensation and modulation. When the dispersion of the metal oxide (A) is obtained by condensing or hydrolyzing the compound (E), the obtained dispersion may be subjected to a specific treatment (decomposition in the presence of the aforementioned acid compound (Q)) if necessary. glue, etc.). The solvent used for preparing the dispersion of the metal oxide (A) is not particularly limited, but alcohols such as methanol, ethanol, and isopropanol; water; or mixed solvents of these are preferred.

作為含有無機磷化合物(BI)之溶液中使用的溶劑，只要按照無機磷化合物(BI)之種類來適宜選擇即可，較佳為包含水。只要不妨礙無機磷化合物(BI)之溶解，則溶劑亦可包含有機溶劑(例如甲醇等之醇類)。As a solvent used for the solution containing an inorganic phosphorus compound (BI), what is necessary is just to select suitably according to the kind of inorganic phosphorus compound (BI), and it is preferable to contain water. As long as the dissolution of the inorganic phosphorus compound (BI) is not hindered, the solvent may also include an organic solvent (for example, alcohols such as methanol).

塗佈液(S)的固體成分濃度，從該塗佈液的保存安定性及對基材(X)的塗佈性之觀點來看，較佳為1~20質量%，更佳為2~15質量%，尤佳為3~10質量%。前述固體成分濃度例如可將塗佈液(S)之溶劑餾去後殘存的固體成分之質量除以供處理的塗佈液(S)之質量而算出。The solid content concentration of the coating solution (S) is preferably from 1 to 20% by mass, more preferably from 2 to 20% by mass, from the viewpoint of the storage stability of the coating solution and the applicability to the substrate (X). 15% by mass, preferably 3-10% by mass. The solid content concentration can be calculated, for example, by dividing the mass of solid content remaining after distilling off the solvent of the coating liquid (S) by the mass of the coating liquid (S) to be processed.

塗佈液(S)為以布魯克菲爾德(Brookfield)型旋轉黏度計(SB型黏度計：轉子No.3、轉速60rpm)測定之黏度，在塗佈時的溫度下，較佳為3000mPa・s以下，更佳為2500mPa・s以下，尤佳為2000mPa・s以下。藉由該黏度為3000mPa・s以下，塗佈液(S)的均平性提升，可得到外觀更優異的多層構造體。又，塗佈液(S)的黏度較佳為50mPa・s以上，更佳為100mPa・s以上，尤佳為200mPa・s以上。The coating liquid (S) is the viscosity measured by a Brookfield rotational viscometer (SB viscometer: rotor No.3, rotating speed 60rpm), and it is preferably below 3000mPa·s at the coating temperature , more preferably below 2500mPa·s, most preferably below 2000mPa·s. When the viscosity is 3000 mPa·s or less, the levelness of the coating solution (S) is improved, and a multilayer structure with a better appearance can be obtained. Also, the viscosity of the coating solution (S) is preferably at least 50 mPa·s, more preferably at least 100 mPa·s, and most preferably at least 200 mPa·s.

於塗佈液(S)中，鋁原子與磷原子之莫耳比，較佳為鋁原子：磷原子=1.0：1.0~3.6：1.0之範圍，更佳在1.1：1.0~3.0：1.0之範圍，特佳在1.11：1.00~1.50：1.00之範圍。鋁原子與磷原子之莫耳比係可進行塗佈液(S)的乾固物之螢光X射線分析而算出。In the coating solution (S), the molar ratio of aluminum atoms to phosphorus atoms is preferably in the range of aluminum atoms:phosphorus atoms=1.0:1.0~3.6:1.0, more preferably in the range of 1.1:1.0~3.0:1.0 , especially in the range of 1.11:1.00~1.50:1.00. The molar ratio of aluminum atoms and phosphorus atoms can be calculated by performing fluorescent X-ray analysis of the dry solid of the coating liquid (S).

塗佈液(S)之塗佈方法係沒有特別的限定，可採用眾所周知的方法。作為塗佈方法，例如可舉出輥塗法、凹版塗佈法、網版印刷法、反向塗佈法、吻塗法、模塗法、計量棒塗法、箱式刮刀併用塗佈法、棒塗法等。The coating method of the coating solution (S) is not particularly limited, and a well-known method can be employed. Examples of coating methods include roll coating, gravure coating, screen printing, reverse coating, kiss coating, die coating, metered bar coating, box blade coating, Stick coating, etc.

塗佈塗佈液(S)後的溶劑之去除方法(乾燥處理)係沒有特別的限制，可採用眾所周知的乾燥方法。作為乾燥方法，例如可舉出熱風乾燥法、熱輥接觸法、紅外線加熱法、微波加熱法等。The solvent removal method (drying treatment) after coating the coating liquid (S) is not particularly limited, and a known drying method can be used. As a drying method, a hot-air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, etc. are mentioned, for example.

乾燥溫度較佳為低於基材(X)的流動起始溫度。塗佈液(S)之塗佈後的乾燥溫度例如可為60℃以上180℃以下左右，較佳為60℃以上且未達140℃，更佳為70℃以上且未達130℃，特佳為80℃以上且未達120℃。乾燥時間係沒有特別的限定，但較佳為1秒以上且未達1小時，更佳為5秒以上且未達15分鐘，尤佳為5秒以上且未達300秒。特別地，乾燥溫度為100℃以上時(例如100~140℃)，乾燥時間較佳為1秒以上且未達4分鐘，更佳為5秒以上且未達4分鐘，尤佳為5秒以上且未達3分鐘。乾燥溫度低於100℃時(例如60~99℃)，乾燥時間較佳為3分鐘以上且未達1小時，更佳為6分鐘以上且未達30分鐘，尤佳為8分鐘以上且未達25分鐘。若塗佈液(S)的乾燥處理條件在前述範圍，則有得到具有更良好的阻氣性之多層構造體之傾向。經過上述乾燥，溶劑被去除，而形成層(Y)的前驅物層。The drying temperature is preferably lower than the flow initiation temperature of the substrate (X). The drying temperature of the coating liquid (S) after coating can be, for example, about 60°C to 180°C, preferably 60°C to less than 140°C, more preferably 70°C to less than 130°C, particularly preferably Above 80°C and below 120°C. The drying time is not particularly limited, but is preferably from 1 second to less than 1 hour, more preferably from 5 seconds to less than 15 minutes, and particularly preferably from 5 seconds to less than 300 seconds. In particular, when the drying temperature is above 100°C (for example, 100 to 140°C), the drying time is preferably at least 1 second and less than 4 minutes, more preferably at least 5 seconds and less than 4 minutes, and most preferably at least 5 seconds And less than 3 minutes. When the drying temperature is lower than 100°C (for example, 60-99°C), the drying time is preferably more than 3 minutes and less than 1 hour, more preferably more than 6 minutes and less than 30 minutes, and especially preferably more than 8 minutes and less than 1 hour. 25 minutes. When the drying treatment conditions of the coating liquid (S) are within the aforementioned ranges, there is a tendency to obtain a multilayer structure having better gas barrier properties. Through the above-mentioned drying, the solvent is removed to form a precursor layer of the layer (Y).

在基材(X)兩面積層層(Y)時，例如將塗佈液(S)塗佈於基材(X)的一面側後，藉由去除溶劑，而形成第1層(第1層(Y)的前驅物層)，接著將塗佈液(S)塗佈於基材(X)的另一面側後，藉由去除溶劑，而形成第2層(第2層(Y)的前驅物層)。塗佈於各面的塗佈液(S)之組成可相同或相異。When the base material (X) is laminated with layers (Y), for example, after coating the coating solution (S) on one side of the base material (X), the solvent is removed to form the first layer (the first layer ( Y) precursor layer), and then apply the coating solution (S) on the other side of the substrate (X), and then remove the solvent to form the second layer (the precursor of the second layer (Y) layer). The composition of the coating liquid (S) coated on each surface may be the same or different.

[步驟(II)] 於步驟(II)中，熱處理步驟(I)所形成的層(Y)的前驅物層而形成層(Y)。於步驟(II)中，進行反應生成物(D)生成的反應。為了使該反應充分地進行，熱處理的溫度較佳為140℃以上，更佳為170℃以上，尤佳為180℃以上，特佳為190℃以上。若熱處理溫度低，則得到充分的反應率所花費的時間變長，成為生產性降低之原因。熱處理的溫度係隨著基材(X)的種類等而不同，例如將由聚醯胺系樹脂所成的熱塑性樹脂薄膜使用作為基材(X)時，熱處理的溫度較佳為270℃以下。又，將由聚酯系樹脂所成的熱塑性樹脂薄膜使用作為基材(X)時，熱處理的溫度較佳為240℃以下。熱處理可在空氣環境下、氮氣環境下、氬氣環境下等實施。熱處理時間較佳為1秒~1小時，更佳為1秒~15分鐘，尤佳為5~300秒。 [Step (II)] In the step (II), the layer (Y) is formed by heat-treating the precursor layer of the layer (Y) formed in the step (I). In the step (II), the reaction to form the reaction product (D) is performed. In order to fully proceed the reaction, the heat treatment temperature is preferably 140°C or higher, more preferably 170°C or higher, particularly preferably 180°C or higher, and particularly preferably 190°C or higher. When the heat treatment temperature is low, it takes a long time to obtain a sufficient reaction rate, which causes a decrease in productivity. The heat treatment temperature varies depending on the type of substrate (X). For example, when a thermoplastic resin film made of polyamide resin is used as the substrate (X), the heat treatment temperature is preferably 270° C. or lower. Moreover, when using the thermoplastic resin film which consists of polyester resin as a base material (X), it is preferable that the temperature of heat treatment is 240 degreeC or less. The heat treatment can be performed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like. The heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes, and most preferably 5 to 300 seconds.

步驟(II)較佳為包含第1熱處理步驟(II-1)與第2熱處理步驟(II-2)。以2階段以上進行熱處理時，第2階段熱處理(以下，第2熱處理)的溫度較佳為高於第1階段熱處理(以下，第1熱處理)的溫度，更佳為比第1熱處理的溫度高15℃以上，尤佳為高20℃以上，特佳為高30℃以上。Step (II) preferably includes the first heat treatment step (II-1) and the second heat treatment step (II-2). When heat treatment is performed in two or more stages, the temperature of the second stage heat treatment (hereinafter, the second heat treatment) is preferably higher than the temperature of the first stage heat treatment (hereinafter, the first heat treatment), and more preferably higher than the temperature of the first heat treatment Above 15°C, preferably above 20°C, particularly preferably above 30°C.

又，步驟(II)的熱處理溫度(2階段以上的熱處理時為第1熱處理溫度)，從得到具有良好特性的多層構造體之點來看，較佳為高於步驟(I)的乾燥溫度，更佳為高30℃以上，尤佳為高50℃以上，尤更佳為高55℃以上，特佳為高60℃以上。Also, the heat treatment temperature in the step (II) (the first heat treatment temperature in the case of two or more heat treatments) is preferably higher than the drying temperature in the step (I) from the viewpoint of obtaining a multilayer structure with good properties, More preferably, it is higher than 30°C, especially preferably higher than 50°C, even more preferably higher than 55°C, particularly preferably higher than 60°C.

以2階段以上進行步驟(II)的熱處理時，第1熱處理的溫度較佳為140℃以上且未達200℃，而且第2熱處理的溫度較佳為180℃以上270℃以下，第2熱處理的溫度較佳為高於第1熱處理溫度，更佳為高15℃以上，尤佳為高25℃以上。特別地，熱處理溫度為200℃以上時，熱處理時間較佳為0.1秒~10分鐘，更佳為0.5秒~15分鐘，尤佳為1秒~3分鐘。熱處理溫度低於200℃時，熱處理時間較佳為1秒~15分鐘，更佳為5秒~10分鐘，尤佳為10秒~5分鐘。When the heat treatment of step (II) is performed in two or more stages, the temperature of the first heat treatment is preferably not less than 140°C and not higher than 200°C, and the temperature of the second heat treatment is preferably not less than 180°C and not more than 270°C. The temperature is preferably higher than the first heat treatment temperature, more preferably higher than 15°C, especially preferably higher than 25°C. In particular, when the heat treatment temperature is above 200° C., the heat treatment time is preferably 0.1 second to 10 minutes, more preferably 0.5 second to 15 minutes, and most preferably 1 second to 3 minutes. When the heat treatment temperature is lower than 200° C., the heat treatment time is preferably 1 second to 15 minutes, more preferably 5 seconds to 10 minutes, and most preferably 10 seconds to 5 minutes.

[步驟(III)] 於本發明之多層構造體之製造方法中，使用有機磷化合物(BO)、聚合物(F)及/或其他成分時，可具有：將藉由混合有機磷化合物(BO)、聚合物(F)及/或其他成分以及溶劑而得之塗佈液(T)，塗佈於步驟(I)所得之層(Y)的前驅物層、步驟(II)所得之層(Y)或步驟(II-1)後之層(Y)的前驅物層上，經過乾燥處理之步驟(III)。於步驟(II-1)之後進行步驟(III)時，較佳為在步驟(III)的乾燥處理後進行步驟(II-2)。於步驟(III)中，可增加塗佈液(T)的塗佈量，在層(Y)上形成層(W)。 [Step (III)] In the manufacturing method of the multilayer structure of the present invention, when using the organophosphorus compound (BO), the polymer (F) and/or other components, it may have: by mixing the organophosphorus compound (BO), the polymer (F ) and/or other components and the coating solution (T) obtained from the solvent, coated on the precursor layer of the layer (Y) obtained in the step (I), the layer (Y) obtained in the step (II) or the layer (Y) obtained in the step (II) -1) Step (III) of drying treatment on the precursor layer of the subsequent layer (Y). When step (III) is carried out after step (II-1), it is preferable to carry out step (II-2) after the drying treatment of step (III). In the step (III), the coating amount of the coating solution (T) may be increased to form the layer (W) on the layer (Y).

塗佈液(T)所用的溶劑，只要按照有機磷化合物(BO)、聚合物(F)及/或其他成分之種類來適宜選擇即可，但較佳為甲醇、乙醇、異丙醇等之醇類；水；或彼等的混合溶劑。The solvent used for the coating solution (T) may be appropriately selected according to the type of the organophosphorus compound (BO), the polymer (F) and/or other components, but methanol, ethanol, isopropanol, etc. are preferred. Alcohols; water; or their mixed solvents.

塗佈液(T)中的固體成分濃度，從溶液的保存安定性或塗佈性之觀點來看，較佳為0.01~60質量%，更佳為0.1~50質量%，尤佳為0.2~40質量%。固體成分濃度係可藉由與塗佈液(S)有關的記載之方法同樣之方法來求出。The solid content concentration in the coating solution (T) is preferably from 0.01 to 60% by mass, more preferably from 0.1 to 50% by mass, and most preferably from 0.2 to 40% by mass. Solid content concentration can be calculated|required by the method similar to the method of description concerning coating liquid (S).

與塗佈液(S)之塗佈同樣地，塗佈塗佈液(T)之方法係沒有特別的限定，可採用眾所周知的方法。Like the coating of the coating liquid (S), the method of coating the coating liquid (T) is not particularly limited, and a well-known method can be employed.

步驟(III)中的塗佈液(T)塗佈後之溶劑的去除方法(乾燥處理)之條件，可採用與步驟(I)中的塗佈液(S)塗佈後的乾燥處理條件同樣之方法。The conditions of the solvent removal method (drying treatment) after coating the coating solution (T) in step (III) can be the same as the drying treatment conditions after coating the coating solution (S) in step (I) method.

[步驟(IV)] 本發明之多層構造體之製造方法係在進行步驟(I)之前，可包含在基材(X)上視需要地施予表面處理後，設置接著層(I)之步驟。更適宜地，該製造方法可包含將包含PVA系樹脂、聚酯系樹脂及溶劑之塗佈液(R)塗佈於基材(X)上後，去除溶劑而形成接著層(I)之步驟(IV)。 [Step (IV)] The method for producing a multilayer structure of the present invention may include the step of providing an adhesive layer (I) after optionally surface-treating the substrate (X) before performing the step (I). More preferably, the production method may include the step of forming the adhesive layer (I) by removing the solvent after coating the coating liquid (R) comprising PVA-based resin, polyester-based resin and solvent on the substrate (X) (IV).

作為得到塗佈液(R)之手段，例如可直接混合PVA系樹脂、聚酯系樹脂及溶劑，也可混合包含PVA系樹脂的溶液或分散液與包含聚酯系樹脂的溶液或分散液。其中，從溶液的均勻性之觀點來看，較佳為混合PVA系樹脂的水溶液與聚酯系樹脂的分散液，得到塗佈液(R)。As means for obtaining the coating liquid (R), for example, PVA-based resin, polyester-based resin, and solvent may be mixed directly, or a solution or dispersion containing PVA-based resin and a solution or dispersion containing polyester-based resin may be mixed. Among them, it is preferable to mix an aqueous solution of a PVA-based resin and a dispersion liquid of a polyester-based resin to obtain a coating liquid (R) from the viewpoint of uniformity of the solution.

作為用於塗佈液(R)的溶劑，並沒有特別的限定，較佳為以水作為主成分，也可只有水。又，作為以水作為主成分之情況中使用他溶劑，較宜使用、甲醇、乙醇、異丙醇等之醇類。Although it does not specifically limit as a solvent used for a coating liquid (R), It is preferable to use water as a main component, and only water may be sufficient. In addition, as another solvent used in the case where water is used as the main component, alcohols such as methanol, ethanol, and isopropanol are preferably used.

塗佈液(R)的固體成分濃度，從該塗佈液的保存安定性及對基材(X)的塗佈性之觀點來看，較佳為0.01~10質量%。前述固體成分濃度例如可將塗佈液(R)之溶劑餾去後殘存的固體成分之質量除以供處理的塗佈液(R)之質量而算出。The solid content concentration of the coating liquid (R) is preferably 0.01 to 10% by mass from the viewpoint of storage stability of the coating liquid and applicability to the substrate (X). The solid content concentration can be calculated, for example, by dividing the mass of solid content remaining after distilling off the solvent of the coating liquid (R) by the mass of the coating liquid (R) to be processed.

塗佈液(R)之塗佈係沒有特別的限定，可採用眾所周知的方法。作為塗佈方法，例如可舉出澆鑄法、浸漬法、輥塗法、凹版塗佈法、網版印刷法、反向塗佈法、噴霧塗佈法、吻塗法、模塗法、計量棒塗法、箱式刮刀併用塗佈法、簾幕塗佈法、棒塗法等。The coating system of the coating liquid (R) is not particularly limited, and a well-known method can be employed. Examples of coating methods include casting, dipping, roll coating, gravure coating, screen printing, reverse coating, spray coating, kiss coating, die coating, and metering rods. Coating method, box blade combined coating method, curtain coating method, rod coating method, etc.

在基材(X)上塗佈後的塗佈液(R)之溶劑的去除方法係沒有特別的限制，可採用眾所周知的乾燥方法。作為乾燥方法，例如可舉出熱風乾燥法、熱輥接觸法、紅外線加熱法、微波加熱法等。The method of removing the solvent of the coating solution (R) coated on the substrate (X) is not particularly limited, and a known drying method can be used. As a drying method, a hot-air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, etc. are mentioned, for example.

[電子裝置的保護薄片及電子裝置] 使用本發明之多層構造體的電子裝置，係具備電子裝置本體與保護電子裝置本體之表面的保護薄片。本發明之電子裝置的保護薄片包含本發明之多層構造體。本發明之電子裝置的保護薄片可僅由本發明之多層構造體所構成，也可藉由本發明之多層構造體與其他構件而構成。本發明之電子裝置的保護薄片具有高的阻隔性及鮮明度。因此，藉由使用本發明的保護薄片，可得到即使在嚴酷的環境下也劣化少，穿透的影像之鮮明度高的電子裝置。例如，使用於電子紙用基板薄膜時，可適用作為容易受到水分影響之電子紙的油墨之保護材。 [Protective sheet for electronic device and electronic device] An electronic device using the multilayer structure of the present invention includes an electronic device body and a protective sheet for protecting the surface of the electronic device body. The protective sheet of the electronic device of the present invention includes the multilayer structure of the present invention. The protective sheet of the electronic device of the present invention may be composed only of the multilayer structure of the present invention, or may be composed of the multilayer structure of the present invention and other components. The protective sheet of the electronic device of the present invention has high barrier properties and clarity. Therefore, by using the protective sheet of the present invention, it is possible to obtain an electronic device with little deterioration even in a severe environment and high clarity of a transparent image. For example, when used as a substrate film for electronic paper, it can be applied as a protective material for ink of electronic paper that is easily affected by moisture.

本發明之電子裝置可為光電轉換裝置、資訊顯示裝置或照明裝置。於光電轉換裝置之例中，包含各種的太陽能電池及其他光電轉換裝置。於資訊顯示裝置之例中，包含液晶顯示器、有機EL顯示器、電漿顯示器、電子紙及其他資訊顯示裝置。於照明裝置之例中，包含LED照明、有機EL照明及其他照明裝置。The electronic device of the present invention can be a photoelectric conversion device, an information display device or a lighting device. Examples of photoelectric conversion devices include various solar cells and other photoelectric conversion devices. Examples of information display devices include liquid crystal displays, organic EL displays, plasma displays, electronic paper and other information display devices. Examples of lighting devices include LED lighting, organic EL lighting, and other lighting devices.

本發明之電子裝置可特佳地使用作為包含光學元件的裝置。作為光學元件，可按照本發明之電子裝置的用途來適宜選擇。此處，本發明中的光學元件為具有光學功能者，該光學功能例如可舉出資訊顯示功能、發光功能等。使用具有資訊顯示功能者作為前述光學元件時，本發明之電子裝置可作為資訊顯示裝置使用，使用具有發光功能者作為光學元件時，本發明之電子裝置可作為發光裝置(照明裝置)使用。The electronic device of the present invention can be used particularly preferably as a device including an optical element. As an optical element, it can select suitably according to the use of the electronic device of this invention. Here, the optical element in the present invention has an optical function, and the optical function includes, for example, an information display function, a light emitting function, and the like. When using an information display function as the aforementioned optical element, the electronic device of the present invention can be used as an information display device, and when using a light emitting function as an optical element, the electronic device of the present invention can be used as a light emitting device (illumination device).

作為具有前述資訊顯示功能的光學元件，例如可舉出液晶顯示裝置所用的液晶胞、有機EL顯示裝置所用的有機EL元件及電子紙裝置所用的電子紙用元件(粒子移動型、液晶型、電化學型等)等。此處，藉由使用液晶胞作為前述光學元件，本發明之光學裝置成為液晶顯示裝置，藉由使用有機EL元件而成為有機EL顯示裝置，更藉由使用電子紙用元件而成為電子紙裝置。Examples of optical elements having the aforementioned information display function include liquid crystal cells used in liquid crystal display devices, organic EL elements used in organic EL display devices, and electronic paper elements used in electronic paper devices (particle movement type, liquid crystal type, electrochemical study type, etc.), etc. Here, the optical device of the present invention becomes a liquid crystal display device by using a liquid crystal cell as the optical element, an organic EL display device by using an organic EL element, and an electronic paper device by using an electronic paper element.

作為前述液晶胞、有機EL元件及電子紙用元件，並沒別有特別的限定，但一般可使用眾所周知的元件。The liquid crystal cell, the organic EL element, and the element for electronic paper are not particularly limited, but generally known elements can be used.

本發明之多層構造體亦可作為LCD用基板薄膜、有機EL用基板薄膜、電子紙用基板薄膜等被稱為基板薄膜的薄膜使用。於該情況下，多層構造體兼任基板與保護薄片。又，保護薄片的保護對象之電子裝置係不限定於前述例示，例如亦可為IC標籤、光通訊用裝置、燃料電池等。The multilayer structure of the present invention can also be used as a film called a substrate film such as a substrate film for LCD, a substrate film for organic EL, and a substrate film for electronic paper. In this case, the multilayer structure serves both as a substrate and a protective sheet. In addition, the electronic device to be protected by the protective sheet is not limited to the aforementioned examples, and may be, for example, an IC tag, an optical communication device, a fuel cell, or the like.

本發明之電子裝置的保護薄片可包含配置於多層構造體之一表面的表面保護層。作為表面保護層，較佳為由透明性高、不易損傷的樹脂所構成之層。又，如太陽電池般會在室外利用的裝置之保護薄片中的表面保護層，較佳為由耐候性(例如耐光性)高的樹脂所構成。又，於保護必須透光的面之情況中，較佳為透光性高的表面保護層。作為表面保護層(表面保護薄膜)之材料，例如可舉出丙烯酸樹脂、聚碳酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、三乙醯纖維素、環烯烴聚合物、乙烯-四氟乙烯共聚物(ETFE)、聚四氟乙烯、四氟乙烯-全氯烷氧基共聚物、四氟乙烯-六氟丙烯共聚物、2-乙烯-四氟乙烯共聚物、聚三氟氯乙烯、聚偏二氟乙烯、聚氟乙烯等。The protective sheet of the electronic device of the present invention may include a surface protective layer disposed on one surface of the multilayer structure. As a surface protection layer, it is preferable that it is a layer which consists of resin with high transparency and is hard to damage. Also, the surface protective layer in the protective sheet of a device used outdoors such as a solar cell is preferably made of a resin with high weather resistance (for example, light resistance). Moreover, when protecting the surface which must transmit light, it is preferable that it is a surface protection layer with high light transmittance. Examples of materials for the surface protection layer (surface protection film) include acrylic resins, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, and cycloolefin polymers. , ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene, tetrafluoroethylene-perchloroalkoxy copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, 2-ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene Chlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, etc.

為了提高表面保護層的耐久性，亦可在表面保護層中添加各種的添加劑(例如紫外線吸收劑)。耐候性高的表面保護層之較佳一例為添加有紫外線吸收劑的丙烯酸樹脂層。作為紫外線吸收劑，例如可舉出苯并***系、二苯甲酮系、水楊酸酯系、氰基丙烯酸酯系、鎳系、三𠯤系的紫外線吸收劑，但不受該等所限定。又，亦可併用其他安定劑、光安定劑、抗氧化劑等。In order to improve the durability of the surface protection layer, various additives (such as ultraviolet absorbers) can also be added to the surface protection layer. A preferable example of the surface protection layer having high weather resistance is an acrylic resin layer to which an ultraviolet absorber is added. Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and trisulfone-based ultraviolet absorbers, but are not restricted by these. limited. Moreover, other stabilizers, light stabilizers, antioxidants, etc. can also be used together.

再者，為了提高表面保護層的耐久性，較佳為在表面上施予硬塗層等之耐候性的塗層。塗層的種類沒有特別的限定，可使用眾所周知的材料。Furthermore, in order to improve the durability of the surface protection layer, it is preferable to give a weather-resistant coating such as a hard coat layer on the surface. The type of coating is not particularly limited, and well-known materials can be used.

保護薄片之構成係沒有特別的限定，例如可適宜使用如下述的構成。 (1)多層構造體 (2)多層構造體/接著層/聚對苯二甲酸乙二酯 (3)多層構造體/接著層/三乙醯纖維素 (4)多層構造體/接著層/丙烯酸樹脂 (5)多層構造體/接著層/聚碳酸酯 (6)多層構造體/接著層/環烯烴聚合物 (7)多層構造體/接著層/ETFE 尚且，使本發明之多層構造體與其他材料積層時，為了保護多層構造體，較佳為以其他材料成為外側之方式配置。 [實施例] The structure of the protective sheet is not particularly limited, and for example, the following structures can be suitably used. (1) Multilayer structure (2) Multilayer structure/adhesive layer/polyethylene terephthalate (3) Multilayer structure/adhesion layer/triacetyl cellulose (4) Multilayer structure/adhesive layer/acrylic resin (5) Multilayer structure/adhesive layer/polycarbonate (6) Multilayer structure/adhesive layer/cycloolefin polymer (7) Multilayer structure/adhesive layer/ETFE Furthermore, when laminating the multilayer structure of the present invention with other materials, it is preferable to arrange the other materials on the outside in order to protect the multilayer structure. [Example]

接著，舉出實施例來更具體地說明本發明，惟本發明完全不受此等實施例所限定，在本發明技術思想之範圍內，由具有該領域中通常知識的人可作出許多的變形。以下的實施例及比較例中的分析及評估係如以下地進行。Next, the present invention is described in more detail by giving examples, but the present invention is not limited by these examples at all, and within the scope of the technical thought of the present invention, many deformations can be made by those who have common knowledge in this field . Analysis and evaluation in the following examples and comparative examples were performed as follows.

＜實施例及比較例所使用的材料＞ ・PET23-A：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)U403」(商品名)，在兩面具備表面層，厚度23μm、圖像清晰度94%、MD方向熱收縮率2.16% ・PET23-B：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)XW731C」(商品名)，在單面具備表面層，厚度23μm、圖像清晰度93%、MD方向熱收縮率2.79% ・PET23-C：雙軸延伸聚對苯二甲酸乙二酯薄膜；HYOSUNG公司製，「RH210」(商品名)，在兩面具備表面層，厚度23μm、圖像清晰度94%、MD方向熱收縮率2.70% ・PET23-D：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)S105」(商品名)，厚度23μm、圖像清晰度83%、MD方向熱收縮率3.00% ・PET38：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)U483」(商品名)，在兩面具備表面層，厚度38μm、圖像清晰度94%、MD方向熱收縮率2.05% ・PET50：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)U403」(商品名)，在兩面具備表面層，厚度50μm、圖像清晰度94%、MD方向熱收縮率2.04% ・PET75：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)U483」(商品名)，在兩面具備表面層，厚度75μm、圖像清晰度93%、MD方向熱收縮率2.08% ・PET12：雙軸延伸聚對苯二甲酸乙二酯薄膜；東麗股份有限公司製，「Lumirror(商標)P60」(商品名)，厚度12μm、圖像清晰度82%、MD方向熱收縮率3.12% 前述材料的圖像清晰度及MD方向熱收縮率係依照後述評價方法(5)圖像清晰度及(2)MD方向熱收縮率中記載之方法進行測定。 <Materials used in Examples and Comparative Examples> ・PET23-A: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) U403" (trade name), with surface layers on both sides, thickness 23 μm, image clarity 94%, MD direction heat shrinkage rate 2.16% ・PET23-B: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) XW731C" (trade name), with a surface layer on one side, 23 μm thick, clear image 93% heat shrinkage rate in MD direction 2.79% ・PET23-C: Biaxially stretched polyethylene terephthalate film; manufactured by HYOSUNG Co., Ltd., "RH210" (trade name), with surface layers on both sides, thickness 23 μm, image clarity 94%, heat shrinkable in MD direction Rate 2.70% ・PET23-D: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) S105" (trade name), thickness 23 μm, image resolution 83%, MD direction heat Shrinkage 3.00% ・PET38: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) U483" (trade name), with surface layers on both sides, thickness 38 μm, image clarity 94% , MD direction heat shrinkage rate 2.05% ・PET50: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) U403" (trade name), with surface layers on both sides, thickness 50 μm, image clarity 94% , MD direction heat shrinkage rate 2.04% ・PET75: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) U483" (trade name), with surface layers on both sides, thickness 75 μm, image clarity 93% , MD direction heat shrinkage rate 2.08% ・PET12: Biaxially stretched polyethylene terephthalate film; manufactured by Toray Co., Ltd., "Lumirror (trademark) P60" (trade name), thickness 12 μm, image resolution 82%, heat shrinkage rate in MD direction 3.12% The image clarity and MD direction heat shrinkage of the aforementioned materials were measured in accordance with the methods described in the evaluation method (5) Image clarity and (2) MD direction heat shrinkage described later.

＜評價方法＞ (1)紅外線吸收光譜的最大吸收波數(Imax)之測定 對於實施例及比較例所得之多層構造體的層(Y)，使用傅立葉轉換紅外線分光光度計，以衰減全反射法進行測定，算出800~1400cm -1的區域中之最大吸收波數(Imax)。測定條件係如以下。 裝置：PerkinElmer股份有限公司製Spectrum One 測定模式：衰減全反射法 測定區域：800~1400cm -1 <Evaluation method> (1) Measurement of the maximum absorption wavenumber (Imax) of the infrared absorption spectrum For the layer (Y) of the multilayer structure obtained in the examples and comparative examples, the attenuated total reflection method was used using a Fourier transform infrared spectrophotometer The measurement was performed, and the maximum absorption wavenumber (Imax) in the region of 800 to 1400 cm -1 was calculated. The measurement conditions are as follows. Device: Spectrum One manufactured by PerkinElmer Co., Ltd. Measuring mode: Attenuated total reflection method Measuring area: 800~1400cm -1

(2)MD方向收縮率 從實施例及比較例所用的基材(X)切出12cm×12cm，在其中央部以1方格為約1cm(MD方向)×1cm(TD方向)之方式畫出6cm×6cm(36方格)的格子，製作測定樣品，以游標卡尺測定平行於MD方向的各方格之長度。接著，將前述測定樣品在210℃的乾燥機內靜置3分鐘，取出後再度以游標卡尺測定平行於MD方向的各方格之長度。算出在乾燥機內靜置前後的平行於MD方向的各方格之長度的收縮率，將此等平均值當作MD方向的收縮率。 (2) Shrinkage rate in MD direction Cut out 12cm x 12cm from the base material (X) used in the examples and comparative examples, and draw a 6cm x 6cm (36 square grid) grid, make a measurement sample, and measure the length of each grid parallel to the MD direction with a vernier caliper. Next, the aforementioned measurement sample was left to stand in a dryer at 210° C. for 3 minutes, and after taking it out, the length of each square parallel to the MD direction was measured again with a vernier caliper. The shrinkage rate of the length of each square parallel to the MD direction before and after standing in the dryer was calculated, and these average values were regarded as the shrinkage rate in the MD direction.

(3)厚度 使用聚焦離子束(FIB)切削實施例及比較例所得到之多層構造體，製作剖面觀察用的切片。以碳膠帶將所製作的切片固定於試樣台座，以加速電壓30kV進行鉑離子濺鍍30秒。使用電場發射型穿透式電子顯微鏡觀察多層構造體的剖面，算出各層之厚度及多層構造體之厚度。測定條件係如以下。又，厚度為5處的測定值之平均。 裝置：日本電子股份有限公司製JEM-2100F 加速電壓：200kV 倍率：250,000倍 (3) Thickness The multilayer structures obtained in Examples and Comparative Examples were cut using a focused ion beam (FIB) to prepare slices for cross-sectional observation. The prepared slice was fixed to the sample stand with carbon tape, and platinum ion sputtering was performed for 30 seconds at an accelerating voltage of 30 kV. The cross-section of the multilayer structure was observed using an electric field emission type transmission electron microscope, and the thickness of each layer and the thickness of the multilayer structure were calculated. The measurement conditions are as follows. In addition, thickness is the average of the measured value of 5 places. Device: JEM-2100F manufactured by JEOL Ltd. Acceleration voltage: 200kV Magnification: 250,000 times

(4)水蒸氣透過度 將實施例及比較例所得之多層構造體安裝於水蒸氣透過量測定裝置，依據ISO15106-5：2015，藉由差壓法測定水蒸氣透過度。測定條件係如以下。水蒸氣透過度愈低，判定為水蒸氣阻隔性愈良好。 裝置：TECHNOLOX公司製DELTAPERM 溫度：40℃ 水蒸氣供給側的濕度：90%RH (4) Water vapor permeability The multilayer structures obtained in Examples and Comparative Examples were installed in a water vapor transmission rate measuring device, and the water vapor transmission rate was measured by the differential pressure method according to ISO15106-5:2015. The measurement conditions are as follows. The lower the water vapor permeability, the better the water vapor barrier property. Device: DELTAPERM manufactured by TECHNOLOX Temperature: 40°C Humidity on the water vapor supply side: 90%RH

(5)圖像清晰度 將實施例及比較例所用之基材(X)或實施例及比較例所得之多層構造體安裝於圖像清晰度測定裝置，依據ISO17221：2014測定圖像清晰度。測定條件係如下述，將5次測定的平均值當作測定值。 裝置：SUGA試驗機股份有限公司製圖像清晰度測定器IC-T 光梳寬度：0.25mm (5) Image clarity The substrate (X) used in Examples and Comparative Examples or the multilayer structures obtained in Examples and Comparative Examples were installed in an image clarity measuring device, and the image clarity was measured in accordance with ISO17221:2014. The measurement conditions are as follows, and the average value of five measurements is regarded as a measurement value. Device: Image Sharpness Meter IC-T manufactured by SUGA Testing Instrument Co., Ltd. Optical comb width: 0.25mm

(6)霧度 將實施例及比較例所得之多層構造體安裝於霧度計HR-100(股份有限公司村上色彩技術研究所製)，依據JIS K7105：1981測定霧度。測定係進行5次，將平均值當作測定值。 (6) Haze The multilayer structures obtained in Examples and Comparative Examples were mounted on a haze meter HR-100 (manufactured by Murakami Color Technology Laboratory Co., Ltd.), and the haze was measured in accordance with JIS K7105:1981. The measurement was performed 5 times, and the average value was regarded as a measured value.

(7)鮮明度 在任意的影像顯示裝置之表面上，將實施例及比較例所得之電子裝置用保護薄片以層合的材料側成為表面之方式載置，評價是否鮮明地看到影像顯示裝置所顯示的文字。將文字被鮮明地顯示者當作A，將文字的端部稍微暈開者當作B，將全體看起來朦朧者當作C，以10人的評審員分別進行評價，將佔多數的評價當作鮮明度的評價。尚且，佔最多數的評價為數個時，一併記載數個評價。 (7) Sharpness On the surface of an arbitrary image display device, the protective sheets for electronic devices obtained in Examples and Comparative Examples were placed so that the laminated material side became the surface, and whether the characters displayed on the image display device were clearly visible was evaluated. The case where the characters are clearly displayed is regarded as A, the case where the ends of the characters are slightly blurred is regarded as B, and the case where the overall appearance is blurred is regarded as C, and each evaluation is performed by 10 judges, and the majority of the evaluations are regarded as Evaluate clarity. In addition, when there are several evaluations which account for the most, several evaluations are collectively described.

(8)透氧度 從實施例及比較例所得之多層構造體切出10mm× 10mm。將所切出的多層構造體安裝於透氧量測定裝置，藉由等壓法測定透氧度。測定條件係如以下。 裝置：MOCON公司製OX-TRAN2/21 溫度：20℃ 氧供給側之濕度：85%RH 載體氣體側之濕度：85%RH 載體氣體流量：10mL/分鐘 氧壓：1.0atm 載體氣體壓力：1.0atm (8) Oxygen permeability 10 mm x 10 mm were cut out from the multilayer structures obtained in Examples and Comparative Examples. The cut-out multilayer structure was installed in an oxygen permeability measuring device, and the oxygen permeability was measured by the isobaric method. The measurement conditions are as follows. Device: OX-TRAN2/21 manufactured by MOCON Corporation Temperature: 20°C Humidity on oxygen supply side: 85%RH Humidity on carrier gas side: 85%RH Carrier gas flow: 10mL/min Oxygen pressure: 1.0atm Carrier gas pressure: 1.0atm

＜塗佈液(S-1)之製造例＞ 將蒸餾水230質量份邊攪拌邊升溫至70℃。在該蒸餾水中費1小時滴下三異丙氧基鋁88質量份，使液溫徐徐上升至95℃，藉由使所產生的異丙醇餾出而進行水解縮合。於所得之液體中添加60質量%的硝酸水溶液4.0質量份，在95℃下攪拌3小時，而使水解縮合物的粒子之凝聚體解膠。然後，將該液體濃縮至固體成分濃度以氧化鋁換算成為10質量%，得到溶液。對於如此所得之溶液22.50質量份，添加蒸餾水54.29質量份及甲醇18.80質量份，攪拌至均勻，而得到分散液。接著，於將液溫維持在15℃的狀態下，邊攪拌分散液邊滴下85質量%的磷酸水溶液4.41質量份。再者，滴加甲醇溶液18.80質量份，在15℃下繼續攪拌直到黏度成為1,500mPa・s為止，得到目的之塗佈液(S-1)。該塗佈液(S-1)中，鋁原子與磷原子之莫耳比為鋁原子：磷原子=1.15：1.00。 <Manufacturing example of coating solution (S-1)> 230 mass parts of distilled water were heated up to 70 degreeC, stirring. In this distilled water, 88 parts by mass of aluminum triisopropoxide was dropped over 1 hour, the liquid temperature was gradually raised to 95° C., and hydrolytic condensation was performed by distilling off generated isopropanol. 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added to the obtained liquid, and stirred at 95° C. for 3 hours to degullify the aggregates of the particles of the hydrolysis-condensation product. Then, this liquid was concentrated until the solid content concentration became 10 mass % in conversion of alumina, and the solution was obtained. Thus, 54.29 mass parts of distilled water and 18.80 mass parts of methanol were added to 22.50 mass parts of solutions obtained in this way, and it stirred until it became uniform, and obtained the dispersion liquid. Next, while the liquid temperature was maintained at 15° C., 4.41 parts by mass of an 85 mass % phosphoric acid aqueous solution was dropped while stirring the dispersion. Furthermore, 18.80 parts by mass of the methanol solution was added dropwise, and stirring was continued at 15° C. until the viscosity became 1,500 mPa·s to obtain the intended coating liquid (S-1). In this coating solution (S-1), the molar ratio of aluminum atoms and phosphorus atoms is aluminum atom:phosphorus atom=1.15:1.00.

＜塗佈液(R-1)之製造例＞ 混合PVA「Kuraray Poval(註冊商標)48-80」4.8質量份與水95.2質量份，在室溫下攪拌5小時而溶解「Kuraray Poval(註冊商標)48-80」，得到PVA水溶液。接著，混合聚酯系水分散體「Elitel(註冊商標)KA-5071S」(UNITIKA股份有限公司製)0.8質量份、前述PVA水溶液1.2質量份、水68.1質量份、甲醇29.9質量份，攪拌1小時而得到塗佈液(R-1)。 <Manufacturing example of coating solution (R-1)> 4.8 parts by mass of PVA "Kuraray Poval (registered trademark) 48-80" and 95.2 parts by mass of water were mixed and stirred at room temperature for 5 hours to dissolve "Kuraray Poval (registered trademark) 48-80" to obtain a PVA aqueous solution. Next, 0.8 parts by mass of polyester-based aqueous dispersion "Elitel (registered trademark) KA-5071S" (manufactured by UNITIKA Co., Ltd.), 1.2 parts by mass of the aforementioned PVA aqueous solution, 68.1 parts by mass of water, and 29.9 parts by mass of methanol were mixed and stirred for 1 hour. Thus, a coating liquid (R-1) was obtained.

＜實施例1＞ 使用PET23-A(寬度21cm)作為基材(X-1)。使用春日電機股份有限公司製電暈處理裝置TEC-4AC，以130W・min/m 2的強度，對基材的一面進行表面處理。在表面處理後的基材之一面上，以乾燥後的厚度成為10nm之方式，使用棒塗機塗佈塗佈液(R-1)。使塗佈後的基材在140℃下乾燥1分鐘，在基材的一面上形成接著層(I-1)。在形成有接著層(I-1)的基材之一面上，以乾燥後的厚度成為0.4μm之方式，使用棒塗機，於塗佈速度為12.6cm/s(塗佈寬度每1cm的塗佈速度為0.6cm/s)之條件下塗佈塗佈液(S-1)。將塗佈後的基材在120℃下乾燥3分鐘後，在180℃下熱處理1分鐘，而在基材上形成層(Y-1)的前驅物層。接著，在另一面上亦藉由同樣的方法進行表面處理後，形成接著層(I-1)及層(Y-1)的前驅物層。將所得之形成有層(Y-1)的前驅物層之薄膜在210℃下進行1分鐘的熱處理，得到層(Y-1)(0.4μm)/接著層(I-1)(10nm)/基材(X-1)(23μm)/接著層(I-1)(10nm)/層(Y-1)(0.4μm)之多層構造體。對於所得之多層構造體的層(Y-1)及多層構造體，依照前述評價方法(1)、(3)、(4)、(5)、(6)及(8)中記載之方法進行評價。表1中顯示結果。 <Example 1> PET23-A (21 cm in width) was used as a base material (X-1). Surface treatment was performed on one side of the substrate with a corona treatment device TEC-4AC manufactured by Kasuga Electric Co., Ltd. at an intensity of 130W・min/ m2 . The coating liquid (R-1) was applied using a bar coater to one surface of the surface-treated base material so that the thickness after drying would be 10 nm. The applied substrate was dried at 140° C. for 1 minute to form an adhesive layer (I-1) on one side of the substrate. On one side of the base material on which the adhesive layer (I-1) is formed, the thickness after drying becomes 0.4 μm, using a bar coater, at a coating speed of 12.6 cm/s (coating width per 1 cm) The coating liquid (S-1) was applied under the condition that the cloth speed was 0.6 cm/s). The coated substrate was dried at 120° C. for 3 minutes, and then heat-treated at 180° C. for 1 minute to form a layer (Y-1) precursor layer on the substrate. Next, after performing surface treatment by the same method on the other surface, a precursor layer adhering to layer (I-1) and layer (Y-1) was formed. The resulting thin film of the precursor layer formed with layer (Y-1) was heat-treated at 210° C. for 1 minute to obtain layer (Y-1) (0.4 μm)/adjacent layer (I-1) (10 nm)/ Multilayer structure of substrate (X-1) (23 μm)/adhesion layer (I-1) (10 nm)/layer (Y-1) (0.4 μm). Layer (Y-1) of the obtained multilayer structure and the multilayer structure were evaluated according to the methods described in the aforementioned evaluation methods (1), (3), (4), (5), (6) and (8) evaluate. The results are shown in Table 1.

準備6片所得之多層構造體，在各自的一面上藉由2液型聚胺基甲酸酯系接著劑(三井化學股份有限公司製的「Takelac(註冊商標)A-1102」與三井化學股份有限公司製的「Takenate(註冊商標)A-3070」)形成接著層，藉由在該接著層上分別層合下述所示的材料而製作6種類的電子裝置的保護薄片。對於所得之各電子裝置的保護薄片，依照前述評價方法(7)中記載之方法，進行鮮明度的評價。表1中顯示結果。尚且，表1之鮮明度1至鮮明度6各自意指與下述1.至6.的材料進行層合了的電子裝置的保護薄片之評價。 1.Lumirror(商標)U403(東麗股份有限公司製，厚度50μm) 2.CosmoshineSRF(商標)(東洋紡股份有限公司製，厚度80μm) 3.三乙醯纖維素(TAC)薄膜(KONICA MINOLTA公司製，厚度80μm) 4.OXIS(商標)PMMA(大倉工業股份有限公司製，厚度40μm) 5.聚碳酸酯薄膜Pureace(商標)(帝人股份有限公司製，厚度70μm) 6.Zeonor薄膜(商標)(日本ZEON股份有限公司製，厚度70μm) Six sheets of the obtained multilayer structure were prepared, and each surface was covered with a two-component polyurethane-based adhesive ("Takelac (registered trademark) A-1102" manufactured by Mitsui Chemicals Co., Ltd. and Mitsui Chemicals Co., Ltd. "Takenate (registered trademark) A-3070" manufactured by Co., Ltd.) formed an adhesive layer, and the protective sheets of six types of electronic devices were produced by laminating the materials shown below on the adhesive layer. The obtained protective sheets for each electronic device were evaluated for sharpness according to the method described in the evaluation method (7) above. The results are shown in Table 1. In addition, each of clarity 1 to clarity 6 in Table 1 means the evaluation of the protective sheet of an electronic device laminated with the following 1. to 6. materials. 1. Lumirror (trademark) U403 (manufactured by Toray Co., Ltd., thickness 50 μm) 2. Cosmoshine SRF (trademark) (manufactured by Toyobo Co., Ltd., thickness 80 μm) 3. Triacetyl cellulose (TAC) film (manufactured by KONICA MINOLTA, thickness 80 μm) 4. OXIS (trademark) PMMA (manufactured by Okura Industries Co., Ltd., thickness 40 μm) 5. Polycarbonate film Pureace (trademark) (manufactured by Teijin Co., Ltd., thickness 70 μm) 6. Zeonor film (trademark) (manufactured by Japan ZEON Co., Ltd., thickness 70 μm)

＜實施例2＞ 除了使用PET23-B代替實施例1所用的PET23-A，在不具備表面層的面上不設置接著層(I-1)以外，以與實施例1同樣之方法製作多層構造體及電子裝置的保護薄片並評價。表1中顯示結果。 <Example 2> Except that PET23-B was used instead of PET23-A used in Example 1, and the adhesive layer (I-1) was not provided on the surface that did not have the surface layer, the multilayer structure and the electronic device were produced in the same manner as in Example 1. Protect the flakes and evaluate. The results are shown in Table 1.

＜實施例3~6、比較例1＞ 除了使用表1中記載的基材(X)代替實施例1所用的PET23-A以外，以與實施例1同樣之方法製作多層構造體及電子裝置的保護薄片並評價。表1中顯示結果。 <Examples 3~6, Comparative Example 1> Except having used the base material (X) described in Table 1 instead of PET23-A used in Example 1, it carried out similarly to Example 1, produced and evaluated the protective sheet of a multilayer structure and an electronic device. The results are shown in Table 1.

＜實施例7＞ 除了對實施例1所用的PET23-A之一面不施予表面處理，且不設置接著層(I-1)及層(Y-1)，製作層(Y-1)(0.4μm)/接著層(I-1)(10nm)/(表面處理面)基材(X-1)(23μm)(非表面處理面)的多層構造體以外，與實施例1同樣地製作多層構造體及電子裝置的保護薄片並評價。表1中顯示結果。 <Example 7> Except that no surface treatment is applied to one side of the PET23-A used in Example 1, and the adhesive layer (I-1) and layer (Y-1) are not provided, the layer (Y-1) (0.4 μm)/adhesive layer is produced (I-1) (10nm)/(surface-treated surface) substrate (X-1) (23 μm) (non-surface-treated surface) multilayer structure, in the same manner as in Example 1, a multilayer structure and an electronic device were produced. Protect the flakes and evaluate. The results are shown in Table 1.

＜實施例8~10、比較例2、比較例3＞ 除了將實施例1的塗佈液(S)之塗佈速度變更為表1中記載以外，以與實施例1同樣之方法製作多層構造體及電子裝置的保護薄片並評價。表1中顯示結果。尚且，於比較例3之多層構造體中，在基材所塗佈的塗佈液(S)係被基材排斥，由於無法均勻地構築層(Y)，故不進行前述評價方法(4)、(5)、(6)及(8)之各評價。 <Examples 8~10, Comparative Example 2, Comparative Example 3> Except for changing the coating speed of the coating solution (S) in Example 1 to that described in Table 1, a multilayer structure and a protective sheet for an electronic device were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. Also, in the multilayer structure of Comparative Example 3, the coating liquid (S) coated on the substrate was repelled by the substrate, and the layer (Y) could not be constructed uniformly, so the aforementioned evaluation method (4) was not performed. , (5), (6) and (8) each evaluation.

＜比較例4＞ 除了使用PET12代替實施例1所用之PET23-A，將塗佈液(S)之塗佈速度變更為表1中記載以外，以與實施例1同樣之方法製作多層構造體及電子裝置的保護薄片並評價。表1中顯示結果。 ＜Comparative example 4＞ A protective sheet for a multilayer structure and an electronic device was produced in the same manner as in Example 1, except that PET12 was used instead of PET23-A used in Example 1, and the coating speed of the coating solution (S) was changed to that shown in Table 1. and evaluate. The results are shown in Table 1.

如表1所示，可知實施例1~10之多層構造體具有高的阻隔性及鮮明度。又，由實施例1、8~10及比較例2、3之比較等可知，用於形成層(Y)的塗佈液(S)之塗佈速度係大幅影響所得之多層構造體的圖像清晰度。As shown in Table 1, it can be seen that the multilayer structures of Examples 1 to 10 have high barrier properties and clarity. Also, from the comparison of Examples 1, 8 to 10 and Comparative Examples 2 and 3, it can be seen that the coating speed of the coating solution (S) used to form the layer (Y) greatly affects the image of the obtained multilayer structure. clarity.

Claims (13)

一種多層構造體，其係具備基材(X)及層(Y)之多層構造體， 層(Y)包含含有鋁原子的金屬氧化物(A)與無機磷化合物(BI)之反應生成物(D)， 基材(X)與層(Y)係鄰接， 依據ISO17221：2014測定的光梳寬度0.25mm之前述多層構造體的圖像清晰度為90%以上。 A multilayer structure, which is a multilayer structure with a substrate (X) and a layer (Y), The layer (Y) contains the reaction product (D) of the metal oxide (A) containing aluminum atoms and the inorganic phosphorus compound (BI), The substrate (X) is adjacent to the layer (Y), The image definition of the aforementioned multilayer structure with a comb width of 0.25 mm measured in accordance with ISO17221:2014 is 90% or more. 如請求項1之多層構造體，其依據JIS K7105：1981測定的霧度值為3%以下。In the multilayer structure according to claim 1, the haze value measured in accordance with JIS K7105:1981 is 3% or less. 如請求項1或2之多層構造體，其依據ISO15106-5：2015測定的40℃、90%RH下之水蒸氣透過率為1×10 -2g/m 2・day以下。 The multilayer structure of claim 1 or 2, which has a water vapor transmission rate of 1×10 -2 g/m 2 ·day or less at 40°C and 90%RH measured in accordance with ISO15106-5:2015. 如請求項1~3中任一項之多層構造體，其中基材(X)在210℃下加熱1分鐘時的MD方向之熱收縮率為2.90%以下。The multilayer structure according to any one of claims 1 to 3, wherein the heat shrinkage rate in the MD direction of the substrate (X) when heated at 210° C. for 1 minute is 2.90% or less. 如請求項1~4中任一項之多層構造體，其中依據ISO17221：2014測定的光梳寬度0.25mm之基材(X)的圖像清晰度為90%以上。The multilayer structure according to any one of Claims 1 to 4, wherein the image definition of the substrate (X) with a comb width of 0.25 mm measured according to ISO17221:2014 is 90% or more. 如請求項1~5中任一項之多層構造體，其中基材(X)具有表面層。The multilayer structure according to any one of claims 1 to 5, wherein the substrate (X) has a surface layer. 如請求項1~6中任一項之多層構造體，其具有基材(X)與層(Y)直接積層之構成。The multilayer structure according to any one of Claims 1 to 6, which has a structure in which the substrate (X) and the layer (Y) are directly laminated. 如請求項1~6中任一項之多層構造體，其具有基材(X)與層(Y)隔著接著層(I)積層之構成。The multilayer structure according to any one of Claims 1 to 6, which has a structure in which the substrate (X) and the layer (Y) are laminated via an adhesive layer (I). 如請求項1~8之多層構造體，其中具備在基材(X)之兩面分別配置的層(Y)。The multilayer structure according to Claims 1 to 8, wherein the layers (Y) are respectively arranged on both sides of the substrate (X). 一種多層構造體之製造方法，其包含： 在基材(X)的至少一面側，塗佈包含含有鋁原子的金屬氧化物(A)、無機磷化合物(BI)及溶劑之塗佈液(S)，去除前述溶劑而形成層(Y)的前驅物層之步驟(I)；及 熱處理層(Y)的前驅物層而形成層(Y)之步驟(II)； 步驟(I)的塗佈液(S)之塗佈速度係塗佈寬度每1cm為0.03cm/s以上2.5cm/s以下， 依據ISO17221：2014測定的在光梳寬度0.25mm所得之多層構造體的圖像清晰度為90%以上。 A method of manufacturing a multilayer structure, comprising: On at least one side of the substrate (X), apply a coating solution (S) containing a metal oxide (A) containing aluminum atoms, an inorganic phosphorus compound (BI) and a solvent, and remove the solvent to form a layer (Y) step (I) of the precursor layer; and Step (II) of forming layer (Y) by heat treating the precursor layer of layer (Y); The coating speed of the coating solution (S) in step (I) is that the coating width per 1 cm is more than 0.03 cm/s and less than 2.5 cm/s, According to ISO17221:2014, the image definition of the multi-layer structure obtained at an optical comb width of 0.25 mm is above 90%. 一種電子裝置的保護薄片，其包含如請求項1~9中任一項之多層構造體。A protective sheet for an electronic device, comprising the multilayer structure according to any one of Claims 1-9. 如請求項11之保護薄片，其係保護光電轉換裝置、資訊顯示裝置或照明裝置的表面之保護薄片。The protection sheet according to claim 11 is a protection sheet for protecting the surface of a photoelectric conversion device, an information display device or a lighting device. 一種電子裝置，其具有如請求項11或12之保護薄片。An electronic device having the protective sheet as claimed in claim 11 or 12.
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