TW201231263A - Method for manufacturing laminate - Google Patents

Method for manufacturing laminate Download PDF

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Publication number
TW201231263A
TW201231263A TW100119853A TW100119853A TW201231263A TW 201231263 A TW201231263 A TW 201231263A TW 100119853 A TW100119853 A TW 100119853A TW 100119853 A TW100119853 A TW 100119853A TW 201231263 A TW201231263 A TW 201231263A
Authority
TW
Taiwan
Prior art keywords
resin composition
curable resin
sealing portion
substrate
width
Prior art date
Application number
TW100119853A
Other languages
Chinese (zh)
Inventor
Yasunori Ito
Tateo Baba
Yu Nojiri
Satoshi Niiyama
Hiroshige Ito
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of TW201231263A publication Critical patent/TW201231263A/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10706—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being photo-polymerized
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10972—Degassing during the lamination
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Landscapes

  • Engineering & Computer Science (AREA)
  • Quality & Reliability (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)

Abstract

Disclosed is a method for manufacturing a laminate wherein: a seal section is formed by applying a second curable resin composition on the peripheral section of a substrate; the viscosity of the second curable resin composition during the step from when a first curable resin composition is supplied to when a laminate precursor is placed in a second atmospheric pressure is 800-5000 Pas; after the laminate precursor has been placed in the second atmospheric pressure the width of the seal section is 0.8-3.0mm and the height/width ratio of the cross section of the seal section is 0.05-1; the first curable resin composition is sandwiched between a pair of substrates under reduced atmospheric pressure; and the ratio (H/h) of the height (H) of the seal section when sealed, and the height (h) of the seal section after the laminate precursor has been placed in the second atmospheric pressure is 1.05-2.5.

Description

201231263 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種包括一對基板、以及存在於該一對基 板間之硬化性樹脂組合物之硬化物之層的積層體之製造方 法。 利用本發明之方法製造之積層體適於夾層玻璃、光學接 合有前面板之圖像顯示裝置，更具體而言光學接合有前面 板之液晶顯示裝置（LCD，Liquid Crystal Display)、有機 EL或無機EL等EL(電致發光，Electroluminescence)顯示裝 置、電漿顯示裝置、電子油墨型圖像顯示裝置等平板顯示 器（FPD，Flat Panel Display)、光學接合有保護板之薄層太 陽電池元件、觸控面板之保護板等用途。 【先前技術】 經由接著層使一對玻璃基板一體化而成之夾層玻璃因破 損之玻璃碎片附著於膜上而不飛散，故可用作汽車之擋風 玻璃，又，因難以貫通而強度優異，故可用作建築物之窗 玻璃（安全玻璃、防盜玻璃）（參照專利文獻1、2)。 又’就防止液晶面板之破損及防止光反射之觀點而言， 已知有將於透明保護板與液晶面板之偏光板之間封入透明 之中間膜而成的前面板設置於前面之液晶顯示裝置（表照 專利文獻3)。 又，已知有如下太陽電池模組，其包括於成為受光面之 透明正面材料與背面材料之間利用樹脂等密封材料加以密 封之太陽電池元件（參照專利文獻4)。 156745.doc -4- 201231263 如此，包括一對基板、以及存在於該一對基板間之硬化 性樹脂組合物之硬化物之層的積層體於各種技術領域均有 需要。 此種積層體之製造方法提出有多種方案，但專利文獻 1、2所記載之方法就使用之基板之種類無限定、夾持於基 板間成為中間層之硬化性樹脂組合物之種類的自由度大、 可有效地利用用以形成中間層之資源、生產性優異、環境 負荷小之方面而言較優異。 於該方法中，於一基板上之周邊部形成用以封入硬化性 樹脂組合物之密封部後’對基板上之密封部所包圍之區域 供給硬化性樹脂組合物。繼而，於減壓環境下於一基板上 疊加另一基板，藉此將硬化性樹脂組合物夹持於一對基板 間並密封。 繼而’將失持並密封有硬化性樹脂組合物之一對基板置 於高於上述減壓環境之壓力環境下（例如大氣壓下）^藉由 環境壓力之上升，而將一對透明基板彼此向密接之方向擠 壓，同時殘留於密閉之空間内之氣泡的體積對應於該環境 之差壓而縮減，因此硬化性樹脂組合物於由一對基板與密 封σ卩所密閉之达、閉空間中的減壓空間内流動，從而密閉空 間整體由硬化性樹脂組合物均勻地填充。其後，藉由使硬 化性樹脂組合物硬化而獲得積層體。 [先前技術文獻] [專利文獻] [專利文獻1]國際公開第2008/081838號公報 156745.doc 201231263 [專利文獻2]國際公開第2009/016943號公報 [專利文獻3]曰本專利特開2009-205065號公報 [專利文獻4]曰本專利特開平u-87743號公報 【發明内容】 [發明所欲解決之問題] 如上所述，專利文獻1、2所記載之積層體之製造方法係 藉由於在減壓環境下將硬化性樹脂組合物夾持於一對透明 基板間並密封後，置於高於上述減壓環境之環境壓力下 (例如大氣壓下），而形成由硬化性樹脂組合物均勻填充密 閉空間整體之狀態後，藉由使硬化性樹脂組合物硬化而獲 得積層體，但若於使硬化性樹脂組合物硬化時，於該硬化 性樹脂組合物中存在氣泡，則於使該硬化性樹脂組合物硬 化之樹脂層中會殘留氣泡。若適合積層體之用途之基準值 以上之大小的氣泡殘留於樹脂層中，則成為積層體之氣泡 缺陷’因此成為問題。 於專利文獻1、2所記載之積層體之製造方法中，若夾持 於透明基板間之硬化性樹脂組合物之厚度不均勻，則有積 層體變形之虞，因此成為問題。 於平板顯示器（FPD)之前面板、薄層太陽電池元件、觸 控面板之保護板等用途中，要求製造更大型之積層體，用 以製造積層體之透明基板就輕量化之觀點而言亦要求使用 厚度更小之玻璃基板，但於使用厚度較小之玻璃基板製造 大型積層體時，若夾持於玻璃基板間之硬化性樹脂組合物 之厚度不均勻，則於玻璃基板上產生變形，從而導致積層 156745.doc -6 · 201231263 體變形，因此成為問題。 又，於為用作平板顯示器(FPD)之前面板之積層體之产 形時，若爽持於透明基板間之硬化性樹脂組合物之厚度^ 均勻’則有使該硬化性樹脂組合物硬化之樹脂層亦存：厚 度之不均勻、產生光學應變等問題之虞。 ，於為平板顯示器（FPD)之前面板之情形時， 器之有效顯示區域之外周部與面板之外周部間的區：(: —域中形成有密封部)之寬度較小，用以形成密封部之 硬化性樹脂組合物於有效顯示區域側伸出，則於圖像上產 生變形1而要求縮小密封部之寬度而不使用以形成密封 部之硬化性樹馳合物於有效顯示區域側伸出，即不使用 以=成密封部之硬化性樹脂組合物自密封部向内侧伸出。 曰在封部之而度必需具有與夾持於透明基板間之樹脂層之 2對應之特定高度’因此要求密封部形成為寬度相對於 ”度較小之形狀，即使密封部之剖面形狀之高度，寬度 之比較大。 本發明之目的在於為解決上述先前技術之問題而提供一 種可製造滿足τ述⑴〜⑷之積㈣之龍之方法。 (1) 無氣泡缺陷之積層體 (2) 樹脂層之厚度均勻之積層體 ()密封4之寬度較小且該密封部之剖面形狀之高度，寬 度之比較大的積層體 ()抑制用以形成密封部之硬化性樹脂組合物自密封部 向内側伸出之積層體 156745.doc 201231263 [解決問題之技術手段] 為達成上述目的，本發明提供一種積層體之製造方法， 其係準備至少一個為透明基板之兩個基板，於上述一基板 上之周邊部形成用以封入第1硬化性樹脂組合物之密封 ’對上述密封部所包圍之區域供給上述第1硬化性樹脂 組合物，於減壓環境下在上述第丨硬化性樹脂組合物上疊 加另一基板，於一對基板間夾持上述第丨硬化性樹脂組合 物並被封，而獲得積層前驅物，將該積層前驅物置於環境 壓力n於上述減壓環境之第2壓力環境下，於該第2壓力環 境下使上述第1硬化性樹脂組合物硬化者，且 上述密封部藉由於上述一基板上之周邊部塗佈第2硬化 性樹脂組合物而形成， 自供給上述第1硬化性樹脂組合物時至將上述積層前驅 物置於上述第2壓力環境下為止之階段的上述第2硬化性樹 脂組合物之黏度為8〇〇〜5〇〇〇 Pa.s， 將上述積層前驅物置於上述第2壓力環境下之後的上述 进封部之寬度為0.8〜3 mm，且卜、+、》+* ϋ 上·上述密封部之剖面形狀之高 度/寬度之比為0.05〜1， 於上述減壓環境下在一對|„ + ， 了卷'板間夾持第1硬化性樹脂組 合物並密封時的上述密封部之古 @ 4 度（Η)與將上述積層前驅 物置於上述第2壓力環境下之你^ 衣兄下之後的上述密封部之高度（h)之 比（H/h)為 1.05〜2.5。 於本發明之積層體之製造方法中 性樹脂組合物於塗佈 較佳為上述第2硬化 時之黏度為1〇〜75〇 pa,s 156745.doc 201231263 . 於本發明之積層體之製造方法中，較佳為於對上述密封 部所包圍之區域供給上述第丨硬化性樹脂組合物前使上述 第2硬化性樹脂組合物半硬化。 於本發明之積層體之製造方法中，可於在上述第2壓力 環境下使上述第1硬化性樹脂組合物硬化時，使上述第2硬 化性樹脂組合物硬化，亦可於將上述積層前驅物置於上述 第2壓力環境下之後使上述第丨硬化性樹脂組合物硬化前， 使上述第2硬化性樹脂組合物硬化。 於本發明之積層體之製造方法中，較佳為以所形成之密 封部之角部附近的上述第2硬化性樹脂組合物之塗佈寬度 與其他塗佈寬度相比變細之方式，在上述一基板上之周邊 部塗佈第2硬化性樹脂組合物。 於本發明之積層體之製造方法中，更佳為以塗佈上述第 2硬化性樹脂組合物時之密封部之角部内緣側的位置較上 述積層前驅物之密封部之角部内緣側的位置更靠近基板之 外緣側之方式，於上述—基板上之周邊部塗佈第2硬化性 樹脂組合物。 於本發明之積層體之製造方法中’較佳為上述—對基板 中之至少一者為厚度〇丨〜3 mm之玻璃基板。 於本發明之積層體之製造方法中’較佳為上述第i硬化 性樹脂組合物之黏度為〇 2〜5〇 pa,s。 於本發明之積層體之製造方法中，較佳為存在於由上述 對基板與上述密封部密封之區域内的第i硬化性樹脂組 合物之層之厚度為30〜3〇〇〇 μιη。 156745.doc 201231263 [發明之效果] 本發明之積層體之製造方法由於可製造密封部之剖面形 狀之高度/寬度之比較大且密封部之寬度較小的積層體， 故而適於製造要求使密封部所包圍之區域較大之用作Fpd 之前面板的積層體。 本發明之積層體之製造方法由於可形成於使硬化性樹脂 組合物硬化時在該硬化性樹脂組合物中不存在與該積層體 之用途對應之基準值以上之大小的氣泡之狀態，故而可製 造不存在氣泡缺陷之高品質的積層體。 本發明之積層體之製造方法由於可使夾持於透明基板間 之硬化性樹脂組合物之厚度均勻，故而於將所製造之積層 體用作FPD之前面板之情形時，不產生光學應變等問題。 又，由於可使夾持於透明基板間之硬化性樹脂組合物之 厚度均勻，故而即便於使用厚度為0.^3 mm之薄板玻璃作 為透明基板之情形時，積層體亦不變形。 【實施方式】 以下，參照圖式對本發明之積層體之製造方法進行說 明。 於本發明之積層體之製造方法中，在一對基板中之一基 板上之周邊部形成用以封入第丨硬化性樹脂組合物之密封 部。圖1係基板之平面圖，表示於基板1〇上之周邊部形成 有密封部20之狀態。 [基板] 於本發明之積層體之製造方法中’如下所述較佳為使用 156745.doc -10· 201231263 光硬化性樹脂組合物作為硬化性樹脂組合物，因此於一對 基板中至少一者為透明基板。於此情形時，於一對基板中 可僅一者為透明基板’另一者為不透明基板，亦可兩個基 板均為透明基板。此處，使一者為透明基板、另一者為不 透明基板之情形時，可於透明基板之周邊部形成密封部， 亦可於不透明基板之周邊部形成密封部。 再者，亦可於透明基板之周邊部設置黑框等印刷部。 透明基板只要為透明，即具有可見光透過性之基板，則 無特別限疋。作為透明基板之具體例’可例示玻璃基板及 透明樹脂基板。該等之中’就具有透明性、耐光性、低雙 折射性、高平面精度、耐表面損傷性、高機械強度之方面 而言，較佳為玻璃基板。 作為玻璃基板之材料，除納約玻璃以外，亦可列舉鐵成 分更低且藍色更淺之高透過玻璃（白板）、蝴石夕玻璃等。 作為透明樹脂基板之材料，可列舉透明性較高之樹脂材 料（聚碳酸酯、聚甲基丙烯酸甲酯等）。 又’透明基板只要至少具有可見光透過性，則可為以使 光散射或折射為目的而對基板表面實施微細之凹凸加工 者，或者亦可為對基板表面實施遮光印刷者。 又’亦可使用貼合有複數片透明基板者或貼合有光學膜 等之透明基板作為一體之透明基板。 又，包括透明基板作為構成要素之一部分的構造體亦可 用作透明基板。作為此種包括透明基板作為構成要素之一 部分的構造體之具體例，可列舉：液晶顯示裝置（LCD， 156745.doc •11- 201231263[Technical Field] The present invention relates to a method for producing a laminate comprising a pair of substrates and a layer of a cured product of a curable resin composition existing between the pair of substrates. The laminate manufactured by the method of the present invention is suitable for a laminated glass, an image display device optically bonded to a front panel, and more specifically, a liquid crystal display device (LCD), an organic EL or an inorganic device optically bonded to a front panel. Flat panel display (FPD, Flat Panel Display) such as EL (electroluminescence) display device, plasma display device, electronic ink type image display device, thin solar cell component optically bonded with protective plate, and touch The protection board of the panel and the like. [Prior Art] The laminated glass in which a pair of glass substrates are integrated via an adhesive layer is adhered to the film without scattering, so that it can be used as a windshield of an automobile, and is excellent in strength because it is difficult to penetrate. Therefore, it can be used as a window glass (safety glass, anti-theft glass) of a building (refer to Patent Documents 1 and 2). Further, from the viewpoint of preventing damage of the liquid crystal panel and preventing light reflection, a liquid crystal display device in which a front panel in which a transparent intermediate film is sealed between a transparent protective plate and a polarizing plate of a liquid crystal panel is provided is provided. (Refer to Patent Document 3). Further, a solar cell module in which a solar cell element is sealed between a transparent front material and a back material which are light-receiving surfaces by a sealing material such as a resin is known (see Patent Document 4). 156745.doc -4- 201231263 Thus, a laminate including a pair of substrates and a layer of a cured product of the curable resin composition existing between the pair of substrates is required in various technical fields. There are various proposals for the method for producing such a laminate. However, the types of substrates used in the methods described in Patent Documents 1 and 2 are not limited, and the degree of freedom of the type of the curable resin composition which is sandwiched between the substrates is an intermediate layer. It is large and can be effectively utilized in terms of resources for forming an intermediate layer, excellent productivity, and small environmental load. In this method, a sealing portion for sealing the curable resin composition is formed in a peripheral portion of a substrate, and a curable resin composition is supplied to a region surrounded by the sealing portion on the substrate. Then, another substrate is superposed on one substrate in a reduced pressure environment, whereby the curable resin composition is sandwiched between the pair of substrates and sealed. Then, 'one of the hardened resin compositions will be lost and sealed, and the substrate is placed under a pressure environment higher than the above-mentioned reduced pressure environment (for example, under atmospheric pressure), and a pair of transparent substrates are moved toward each other by an increase in environmental pressure. The volume of the bubbles remaining in the sealed space is reduced in accordance with the difference pressure of the environment, so that the curable resin composition is sealed in the closed space and the closed space by the pair of substrates and the seal σ The inside of the decompression space flows, so that the entire sealed space is uniformly filled with the curable resin composition. Thereafter, the layered body is obtained by curing the hard resin composition. [PRIOR ART DOCUMENT] [Patent Document 1] [Public Document 1] International Publication No. 2008/081838 No. 156745.doc 201231263 [Patent Document 2] International Publication No. 2009/016943 [Patent Document 3] [Problem to be Solved by the Invention] As described above, the manufacturing method of the laminated body described in Patent Documents 1 and 2 is based on the above. After the curable resin composition is sandwiched between a pair of transparent substrates in a reduced pressure environment and sealed, and placed under an ambient pressure (for example, at atmospheric pressure) higher than the above-described reduced pressure environment, a curable resin composition is formed. After uniformly filling the entire sealed space, the cured resin composition is cured to obtain a laminate. However, when the curable resin composition is cured, bubbles are present in the curable resin composition. Air bubbles remain in the resin layer in which the curable resin composition is cured. When the bubble having a size larger than the reference value of the use of the laminated body remains in the resin layer, the bubble defect of the laminated body is a problem. In the method for producing a laminate according to Patent Documents 1 and 2, when the thickness of the curable resin composition sandwiched between the transparent substrates is not uniform, the laminate is deformed, which is a problem. In applications such as flat panel display (FPD) front panels, thin-film solar cell components, and touch panel protection boards, it is required to manufacture a larger laminated body, and a transparent substrate for manufacturing a laminated body is also required from the viewpoint of weight reduction. When a glass substrate having a smaller thickness is used, when a large-sized laminated body is produced using a glass substrate having a small thickness, if the thickness of the curable resin composition sandwiched between the glass substrates is not uniform, deformation occurs on the glass substrate. This causes the buildup of 156745.doc -6 · 201231263 body deformation, so it becomes a problem. Moreover, when it is used for the formation of a laminate of a front panel of a flat panel display (FPD), if the thickness of the curable resin composition between the transparent substrates is uniform, the curable resin composition is hardened. The resin layer also exists: the problem of uneven thickness, optical strain, and the like. In the case of a front panel of a flat panel display (FPD), the area between the outer periphery of the effective display area of the device and the outer periphery of the panel: (: - a seal formed in the domain) has a small width for forming a seal When the curable resin composition of the portion protrudes on the side of the effective display region, deformation 1 is caused on the image, and it is required to reduce the width of the sealing portion without using the curable tree compound forming the sealing portion to extend sideways in the effective display region. The cured resin composition which is not used as the sealing portion is protruded inward from the sealing portion. The thickness of the sealing portion must have a specific height corresponding to the resin layer 2 sandwiched between the transparent substrates. Therefore, the sealing portion is required to be formed in a shape having a smaller width than the degree, even if the height of the sectional shape of the sealing portion is high. The purpose of the present invention is to provide a method for manufacturing a dragon that satisfies the product (4) of (1) to (4) in order to solve the problems of the prior art described above. (1) Laminated body without bubble defects (2) Resin The laminate having a uniform thickness of the layer () has a small width and a height of the cross-sectional shape of the sealing portion, and the laminate having a relatively large width suppresses the curable resin composition for forming the sealing portion from the sealing portion. The laminated body of the inner side is extended 156745.doc 201231263 [Technical means for solving the problem] In order to achieve the above object, the present invention provides a method of manufacturing a laminated body, which is to prepare at least one substrate which is a transparent substrate on the above substrate The peripheral portion is formed with a seal for enclosing the first curable resin composition. The first curable resin composition is supplied to the region surrounded by the sealing portion, and is decompressed. In the environment, another substrate is superposed on the first enamel-curable resin composition, and the ruthenium resin composition is sandwiched between a pair of substrates and sealed to obtain a laminated precursor, and the laminated precursor is placed under ambient pressure. n in the second pressure environment of the reduced pressure environment, the first curable resin composition is cured in the second pressure environment, and the sealing portion is coated with the second hardening by the peripheral portion on the one substrate The viscosity of the second curable resin composition at the stage from when the first curable resin composition is supplied to when the laminated precursor is placed in the second pressure environment is 8 〇〇 〜 5〇〇〇Pa.s, the width of the sealing portion after the laminated precursor is placed in the second pressure environment is 0.8 to 3 mm, and the cross section of the sealing portion is on the surface of the sealing portion The ratio of the height/width of the shape is 0.05 to 1, and the sealing portion is held when the first curable resin composition is sandwiched between the pair of sheets in the above-mentioned reduced pressure environment and sealed. Degree (Η) and the above layer The ratio (H/h) of the height (h) of the above-mentioned sealing portion after the precursor is placed under the above-mentioned second pressure environment is 1.05 to 2.5. In the method for producing a laminate of the present invention, the neutral resin composition preferably has a viscosity of 1 〇 to 75 〇pa, s 156745.doc 201231263 when the second curing is applied. The method for producing the laminate of the present invention. In the above, it is preferred that the second curable resin composition is semi-cured before the second curable resin composition is supplied to the region surrounded by the sealing portion. In the method for producing a laminate according to the present invention, when the first curable resin composition is cured in the second pressure environment, the second curable resin composition may be cured, or the laminate precursor may be used. After the object is placed in the second pressure environment, the second curable resin composition is cured before the second curable resin composition is cured. In the method for producing a laminate according to the present invention, it is preferable that the coating width of the second curable resin composition in the vicinity of the corner portion of the formed sealing portion is thinner than the other coating width. The second curable resin composition is applied to the peripheral portion of the substrate. In the method for producing a laminate according to the present invention, it is more preferable that the position of the inner edge side of the corner portion of the sealing portion when the second curable resin composition is applied is higher than the inner edge side of the corner portion of the sealing portion of the laminated precursor. The second curable resin composition is applied to the peripheral portion of the substrate as described above so as to be closer to the outer edge side of the substrate. In the method for producing a laminate according to the present invention, it is preferable that at least one of the above-mentioned substrates is a glass substrate having a thickness of 〇丨 3 mm. In the method for producing a laminate according to the present invention, it is preferred that the viscosity of the ith curable resin composition is 〇 2 to 5 〇 pa, s. In the method for producing a laminate according to the present invention, it is preferable that the thickness of the layer of the i-th curable resin composition in the region sealed by the counter substrate and the sealing portion is 30 to 3 μm. 156745.doc 201231263 [Effects of the Invention] The method for producing a laminated body according to the present invention is capable of producing a laminated body having a relatively large height/width of a cross-sectional shape of a sealing portion and a small width of a sealing portion, and is therefore suitable for manufacturing requirements. The larger area enclosed by the department is used as a laminate of the front panel of the Fpd. In the method for producing a layered product of the present invention, when the curable resin composition is cured, the curable resin composition does not have a state of a bubble equal to or greater than a reference value corresponding to the use of the layered product. A high-quality laminate that does not have bubble defects is produced. In the method for producing a laminate according to the present invention, since the thickness of the curable resin composition sandwiched between the transparent substrates can be made uniform, when the laminated body to be produced is used as a front panel of the FPD, no problem such as optical strain occurs. . Further, since the thickness of the curable resin composition sandwiched between the transparent substrates can be made uniform, even when a thin plate glass having a thickness of 0.3 mm is used as the transparent substrate, the laminated body is not deformed. [Embodiment] Hereinafter, a method for producing a laminated body of the present invention will be described with reference to the drawings. In the method for producing a laminate according to the present invention, a sealing portion for enclosing the second curable resin composition is formed on a peripheral portion of one of the pair of substrates. Fig. 1 is a plan view showing a state in which a sealing portion 20 is formed on a peripheral portion of a substrate 1A. [Substrate] In the method for producing a laminate according to the present invention, it is preferable to use a 156745.doc -10·201231263 photocurable resin composition as a curable resin composition as described below, and thus at least one of a pair of substrates It is a transparent substrate. In this case, only one of the pair of substrates may be a transparent substrate. The other is an opaque substrate, and both of the substrates may be transparent substrates. Here, when one is a transparent substrate and the other is an opaque substrate, a sealing portion may be formed in a peripheral portion of the transparent substrate, or a sealing portion may be formed in a peripheral portion of the opaque substrate. Further, a printing portion such as a black frame may be provided on the peripheral portion of the transparent substrate. The transparent substrate is not particularly limited as long as it is transparent, that is, a substrate having visible light transmittance. As a specific example of the transparent substrate, a glass substrate and a transparent resin substrate can be exemplified. Among these, a glass substrate is preferred in terms of transparency, light resistance, low birefringence, high planar precision, surface damage resistance, and high mechanical strength. As the material of the glass substrate, in addition to the nano-glass, a high-transmission glass (whiteboard) or a butterfly glass, which has a lower iron component and a lighter blue color, may be used. The material of the transparent resin substrate is a resin material (polycarbonate, polymethyl methacrylate or the like) having high transparency. Further, the transparent substrate may have a fine unevenness on the surface of the substrate for the purpose of scattering or refracting light, or may be a light-shielding print on the surface of the substrate. Further, a transparent substrate in which a plurality of transparent substrates are bonded or a transparent substrate to which an optical film is bonded may be used as a single transparent substrate. Further, a structure including a transparent substrate as a part of a constituent element can also be used as a transparent substrate. Specific examples of the structure including such a transparent substrate as a constituent element include a liquid crystal display device (LCD, 156745.doc • 11-201231263)

Liquid Crystal Display)、有機EL或無機EL等EL(電致發光） 顯示裝置、電漿顯示裝置、電子油墨型圖像顯示裝置等平 板顯示器（FPD)、薄層太陽電池元件、觸控面板等。 於使一對基板中之一者為不透明基板之情形時，作為不 透明基板之具體例，可列舉：不鏽鋼等金屬材料製基板、 陶瓷材料製基板、藉由使吸收可見光之填充劑分散於基板 中而遮光之樹脂基板等。 再者’於使一對基板兩者均為透明基板之情形時，一對 透明基板可由同一材料形成，亦可由不同材料形成。即， 可一對透明基板均為玻璃基板或透明樹脂基板，亦可一對 透明基板中之一者為玻璃基板’另一者為透明樹脂基板。 基板之厚度並無特別限定，於透明基板之情形時，就機 械強度、透明性之方面而言，玻璃基板之情形時的厚度通 常為〇_1〜6 mm，透明樹脂基板之情形時的厚度通常為 0.1〜3 mm。於使用藉由本發明之方法製造之積層體作為 FPD之前面板之情形時，較佳為使用厚度為〇〗〜3爪爪之玻 璃基板，更佳為使用厚度為0.4—丨5 mm之玻璃基板。 另一方面，於不透明基板之情形時，就機械強度、薄型 輕量化之方面而言’厚度通常為〇 4〜4 mm。 再者，一對基板之厚度彼此可相同，亦可不同。 為提昇基板之表面，更具體而言於周邊部形成密封部之 側之表面與該密封部之界面接著力，亦可實施表面處理。 此處，表面處料僅對基板之周邊㈣施，亦可對基板之 表面整體實施。 156745.doc -12· 201231263 可列舉利用矽烷偶合劑對基板之 作為表面處理之方法 表面進行處理之方法等 [密封部] 密封。p係為封入供給於該密封部所包圍之區域、其後於 2壓環境下夾持於-對基板間並密封的&amp;硬化性樹脂組 °物而°又置’因此其具有於本發明之積層體之製造過程中 供、。於a密封部所包圍之區域之第】硬化性樹脂組合物未 漏出之程度以上的界面接著力。 ;X下述工序貫施真空積層時，藉由密封部具有黏 性而使其高度一定程度上減少，藉此一方面防止第i硬化 I·生樹月曰組合物之漏出，另—方面防止夾持於—對基板間之 第1硬化性樹脂組合物之層的厚度變得不均勾，故而要求 該密封為高黏度。 於本發明之積層體之製造方法中，藉由以使高黏度之硬 化[生樹月日、.且Q物於—基板之周邊部成為特^線寬及高度之 方式使m器等塗佈第2硬化性樹脂組合物而形成具有 上述性能之密封部。 由本發明之方法製造之積層體於以τ述工序解除減壓環 境後的密封部之寬度為〇.8〜3 _，該密封部之剖面形狀之 南度/寬度之比為0.05〜1，於塗佈第2硬化性樹脂組合物時 必需留意以下方面。 ⑴塗佈後之第2硬化性樹脂組合物因其㈣以其高度降 低、線寬增大之方式經時變化，故必需留意以於以下述工 序實施真空積層時密封部成為特定寬度及高度之方式設定 156745.doc -13· 201231263 塗佈時之第2硬化性樹脂組合物之線寬及高度之方面。 (2)於本發明之積層體之製造方法中，以於以下述工序 解除減壓環境時密封部之高度稍微減少之方式設定實施真 空積層時之密封部的高度（H)與解除減壓環境後之密封部 的向度（h)之比（H/h)。藉此，解除減壓環境後之密封部與 · 實施真空積層時之密封部相比，其高度降低、寬度增大。 因此，必需留意以於以下述工序解除減壓環境後密封部成 為特定寬度及高度之方式設定實施真空積層時之密封部的 寬度及高度之方面。 第2硬化性樹脂組合物至少自供給第丨硬化性樹脂組合物 時至以下述工序解除減壓環境為止之階段的黏度（以下， 於本說明書中存在稱為「塗佈後之第2硬化性樹脂組合物 之黏度」之情況）為800〜5000 Pa*s。再者，要求塗佈後之 第2硬化性樹脂組合物之黏度為上述範圍之理由如下所 述。 然而’若第2硬化性樹脂組合物於塗佈時之黏度為上述 範圍即800~5000 pa.s，則存在難以以成為特定寬度及高度 之方式塗佈該第2硬化性樹脂組合物之情況。 如上所述，由本發明之方法製造之積層體於以下述工序 . 解除減壓環境後之密封部的寬度為0.8〜3 mm。於使用分注 器等塗佈第2硬化性樹脂組合物之情形時，如上所述，其 形狀以其高度降低、線寬增大之方式經時變化。因此，為 將解除減壓環境後之密封部之寬度設為0.8〜3 mm而使塗佈 時之第2硬化性樹脂組合物之線寬小於上述密封部之寬度 156745.doc • 14- 201231263 且儘量縮短塗佈第2硬化性樹脂組合物所需要之時間。 然而，為了使高黏度之第2硬化性樹脂組合物自分注器 等之較細之喷嘴以較快之流速喷出，必需於高壓下喷出， 因此存在難以以工業規模塗佈之情況。 又，於使用分注器等塗佈高黏度之硬化性樹脂組合物 時，由於自分注器噴嘴之頂端開始喷出之前產生延遲，故 而難以控制塗佈時之硬化性樹脂組合物之線寬。 但是，若塗佈時之硬化性樹脂組合物之黏度過低，則塗 佈後之硬化性樹脂組合物的經時之形狀變化變得顯著，故 而存在於實施真空積料難以將密封部設為特定寬度及高 度之情況。 又 π» 因此’於本發明之積層體之製造方法中，較佳為將第2 硬化性樹脂組合物之塗佈時之黏度設為10〜750 pa.s。 若塗佈時之第2硬化性樹脂組合物之黏度為上述範圍， 則硬化性樹脂組合物之塗佈性優異且塗佈後之硬化性樹脂 組合物的經時之形狀變化並不顯著。 於本發明之積層體之製造方法中，更佳為塗佈時之第2 硬化性樹脂組合物之黏度為 30〜600 pa.s 〇 ::’於可藉由選擇所用之塗佈機構、塗佈條件等而消 二上佈上迷高黏度之硬化性樹脂組合物時的問題之情形 Η 2直接以上述塗佈狀黏度範圍塗㈣2硬化性樹 月曰組合物。 為了將第2硬化性樹 Pa«s、將塗佈後之第 於本發明之積層體之製造方法中， 月曰組合物之塗佈時之黏度設為10〜750 156745.doc -15· 201231263 2硬化性樹脂組合物之黏度設為800〜5000 pa.s，只要選擇 常溫下之黏度為800~5000 Pa*s之硬化性樹脂组合物作為第 2硬化性樹脂組合物並於加熱第2硬化性樹脂組合物而將黏 度設為1 0〜750 Pa，S之狀態下塗佈該第2硬化性樹脂組合物 即可。於塗佈後’第2硬化性樹脂組合物之黏度伴隨於第2 硬化性樹脂組合物之溫度下降而上升，上述所定義之塗佈 後之第2硬化性樹脂組合物之黏度成為8〇〇〜5〇〇〇 pa.s。再 者’於本說明書中，「常溫」係指「25»c」。 此處，為保持一對基板彼此之間隔’亦可將特定粒徑之 間隙粒子調配於第2硬化性樹脂組合物中。 再者，作為第2硬化性樹脂組合物，較佳為使用下述光 硬化性樹脂組合物，即常溫下之黏度滿足上述塗佈後之黏 度範圍（800〜5〇〇〇 pa.s)者。 於藉由塗佈第2硬化性樹脂組合物而形成密封部時，必 需留意以下方面。 、 用以形成密封部之第2硬化性樹脂組合物如上所述，由 於塗佈後之第2硬化性樹脂組合物黏度較高，&amp;而與供终 ;饴封所包圍之區域之第1硬化性樹脂組合物相比，资 :後之經時之形狀變化極少。心，於在所形成之密封部 產生部分缺損、或 X在封4之冕度部分減小之細化之悴 難以利用經時之形狀變化而解除該等缺陷。 &quot; 再者’於'&quot;JT# 处第2硬化性樹脂組合物之塗佈形雖 例中，使密封Ar 孕父佳 封部之寬度):密之附近之塗佈寬度(即 h、在封部之其他塗佈寬度相比變細，但為抑 156745.doc 201231263 制用以形成密封部之硬化性樹脂組合物自 密封部向内側伸 出，此處所述之密封部之部分細化不包括使密封部之角部 附近之塗佈寬度細化之操作。 於在所形成之密封部產生部分缺損或細化之情形時，因 於以下述工序實施真空積層冑、或實施真空積層時，供终 於密封部所包圍之區域之第1硬化性樹脂組合物向較該： 封部更外側伸出’故需要伸出之部分之去除等追加步驟， 因此不理想。 又，因供給於密封部所包圍 合物向較該密封部更外侧伸出 之新穎性之虞。 之區域之第1硬化性樹脂組 ，故有損害所製造之積層體 又’於在所形成之密封部產生部分缺損或細化之情形 時，因於以下述工序實施減壓環境之解除時，在由一對基 板與密封部密閉之空間内侵人氣體，故有於存在於密閉空 間内之第1硬化性樹脂組合物中產生較大氣泡之虞。卫 人π”成密封部時，於塗佈之起始及終止點部分』 生硬化性樹脂組合物重疊之情形時’難以藉由經時之形乐 變化而解除。因此，於以下述工序實施真空積層時，因落 封:之厚度變得部分性不均句，故有於存在於由—對基余 與密封部密閉之空間内的第i硬化性樹脂組合物中產生車: 大之氣泡之虞。又’因產生重疊之部分之密封部之寬度車: 大，故有損害所製造之積層體之新穎性之虞。 因此，於藉由塗佈第2硬化性樹脂纟且合物而形成密封名 時，較佳為對塗佈第2硬化性樹脂組合物後有無部分之在 156745.doc -17- 201231263 損、細化、重疊等缺陷進行檢査。其中，根據缺陷之大 小，亦存在不產生上述問題之情況，因此較佳為對有無超 過預先決定之所容許之範圍之大小的缺陷進行檢査。 再者’作為可谷許之缺陷基準，已知以下之基準。但 是’可容許之缺陷之基準並無限定，可視需要適當選擇。 (基準例） 於滿足以下之基準之情形時’於積層體之製造上無問 題》 缺損：以塗佈線方向之長度計缺損部分之長度未達〇 5 mm、或未達塗佈高度之70°/〇中之較小者。 細化：相對於基準塗佈宽度，塗佈寬度未達8〇%之部分 之長度（塗佈線方向之長度）未達連續10 。 重疊：塗佈線方向之長度之重疊未達5 mm。 缺陷之檢査方法並無特別限定。作為具體例，例如可列 舉：以目視檢查塗佈後之硬化性樹脂組合物有無缺陷之方 法、藉由圖像處理確認塗佈後之硬化性樹脂組合物有無缺 陷之方法。 於在缺陷檢査中未發現超過基準值之缺陷之情形時，以 下述工序對基板上之密封部所包圍之區域供給硬化性樹脂 組合物。 另一方面’於在缺陷檢査十發現超過基準值之缺陷之情 形時’只要於在存在缺陷之部位塗佈第2硬化性樹脂組合 物而修補缺陷後，以下述工序對基板上之密封部所包圍之 區域供給硬化性樹脂組合物即可。於此情形時，亦可於修 156745.doc -18_ 201231263 補缺陷後，再次實施缺陷檢査。 又，於缺陷之修補在成本上不適合之情形時，亦可不對 於缺陷檢査中發現超過基準值之缺陷者進行修補而將其廢 棄0 再者，於使第2硬化性樹脂組合物半硬化之情形時，較 佳為於使第2硬化樹脂組合物半硬化前，進行上述密封部 之缺陷檢査及缺陷之修補。 繼而，對基板上之密封部所包圍之區域供給第丨硬化性 樹脂組合物。 第1硬化性樹脂組合物之供給量係於以下述工序將第^^硬 化性樹脂組合物夾持於一對基板間並密封時，預先設為利 用第1硬化性樹脂組合物僅填充由一對基板與密封部密閉 之空間的量。此時’可預先考慮由第i硬化性樹脂組合物 之硬化收縮引起之體積減少而決定第i硬化性樹脂組合物 之供給量》 ，於以下述工序將第i 於本發明之積層體之製造方法中 硬化性樹脂組合物夾持於一對基板間並密封時，存在於由 -對基板與密封部密封之空間内的約硬化性樹脂組合物 之層之厚度較佳為30〜3000 μπ!。其原因在於：第i硬化性 樹脂組合物之層為了不僅賦予作為—對基㈣之接著劑之 功能而且賦予使該層具有機械強度或衝擊吸收性之功能而 必需為上述厚度，另一方面因通常以開口構件或顯示構件 為代表要求有薄型輕量化而不必要地增厚之情況欠佳。 於以下述卫序將第1硬化性樹脂組合物夾持於-對基板 156745.doc 201231263 間並密封時，存在於卜對基板與密封部密封之空間内之 第1硬化性樹脂組合物之層的厚度更佳為1〇〇〜16〇〇 ，更 佳為200〜_㈣。尤其是若為液晶用途，則第i硬化性樹 脂組合物之層之厚度更佳為1〇〇〜_ μιη，更佳為·〜彻 μηι 〇 作為第1硬化性樹脂組合物之供給方法可列舉：以上 述工序將形成有密封部之基板水平放置，利用分注器等供 給機構以點狀或線狀供給之方法。 &quot; 於本發明之製造方法中’可使用與預先於形成之積層體 之間隙中注人硬化性樹脂之先前之方法（例如日本專利特 開昭57-165411號公報、日本專利特開·_339〇88號公報 所圮載之方法）相比相對高黏度之硬化性樹脂組合物作為 第1硬化性樹脂組合物。藉此，可謀求使第“更化性樹脂組 合物硬化時之硬化收縮的降低、及硬化後之樹脂層之機械 強度的提昇。 第1硬化性樹脂組合物因黏度為0 2〜50 Pa.s，於工業上 製造、移送、塗佈大量硬化性樹脂組合物之步驟中易操 作，故較佳。 再者，此處所述之第1硬化性樹脂組合物之黏度係指實 施本發明之積層體之製造方法時之溫度區域的黏度，尤其 係指對密封部所包圍之區域供給硬化性樹脂組合物後、以 下述工序實施真空積層前之溫度區域的黏度。例如，於在 常溫下實施該等工序之情形時，其係常溫下之硬化性樹脂 組合物之黏度。 156745.doc -20· 201231263 第1硬化性樹脂組合物更佳為黏度為^20 Pa，s。 作為滿足上述黏度之第1硬化性樹脂組合物，可使用包 含以下所述之高分子量之硬化性化合物（寡聚物等）的硬化 性樹脂組合物。 高分子量之硬化性化合物因可減少硬化性樹脂組合物中 之化學鍵之數，故使硬化性樹脂組合物硬化時之硬化收縮 減小’又’可降低硬化後之樹脂層之殘留應力且可提昇機 械強度。另一方面’高分子量之硬化性化合物大多黏性較 高。因此，就確保硬化後之樹脂層之機械強度且抑制氣泡 之殘留之方面而言，較佳為於高分子量之硬化性化合物中 溶解分子量更小之硬化性單體而調整黏度。但是，藉由使 用分子量較小之硬化性單體，雖然硬化性樹脂組合物之黏 度下降’但存在由使硬化性樹脂組合物硬化時之硬化收縮 引起的殘留應力較大’又硬化後之樹脂層的機械強度下降 之情況。 使用之硬化性樹脂組合物較佳為光硬化性樹脂組合物。 光硬化性樹脂組合物與熱硬化性樹脂組合物相比，係藉由 較夕之熱此以較短時間硬化。因此，於本發明中，藉由使 用光硬化性樹脂組合物而減小製造積層體時之環境負荷。 又，因可花費數分鐘至數十分鐘左右使光硬化性樹脂级合 物實質上硬化’故積層體之生產效率較高。 所謂光硬化性樹脂組合物，係指由光之作用引起硬化反 應而形成樹脂層之材料。作為光硬化性樹脂組合物，例如 可列舉下述者，可於硬化後之樹脂層之硬度未變得過高之 156745.doc -21 - 201231263 範圍内使用》 •包含具有加成聚合性不飽和基之化合物與光聚合起始 劑之組合物》 •以不飽和基與硫氫基之莫耳數大致相等之比例包含具 有1〜6個不飽和基之多烯化合物（異氰脲酸三烯丙酿等）與 具有1〜6個之硫氫基之聚硫醇化合物（三乙二醇二硫醇）^ 包含光聚合起始劑的組合物。 •包含具有2個以上環氧基之環氧化合物與光陽離子產生 劑的Μ合物。 作為光硬化性樹脂組合物，就硬化速度較快、硬化後之 樹脂層之透明性較高之方面而言，更佳為包含具有選自丙 烯酿氧基及甲基丙烯醯氧基中之基（以下’記作（甲基）丙稀 醯氧基）之化合物中之至少丨種與光聚合起始劑者。 作為具有（甲基）丙烯醯氧基之化合物（以下，亦記作（甲 基）丙烯酸醋系化合物），較佳為平均i分子中具有丨〜6個（甲 基）丙烯醯氧基之化合物，就硬化後之樹脂層不會變得過 硬之方面而言，尤佳為平均丨分子中具有〗〜3個（甲基）丙烯 醯氧基之化合物。 作為（甲基）丙烯酸酯系化合物，就硬化後之樹脂層之耐 光性之方面而言，較佳為儘可能不含芳香環之脂肪族或脂 環式化合物。 又，作為（甲基）丙烯酸酯系化合物，就提昇與基板之界 面接著力之方面而言，更佳為具有羥基之化合物。具有羥 基之（甲基）丙烯酸酯系化合物之含量於全部（曱基）丙烯酸 156745.doc -22- 201231263 酯系化合物中較佳為1 5質量％以上，更佳為20質量％以 上。另一方面，具有羥基之化合物於硬化後之樹脂層之彈 性模數易升高，尤其是於使用具有羥基之（曱基）丙烯酸酉旨 之情形時’有根據積層體之用途而硬化後之樹脂層變得過 硬之虞。例如’於用於平板顯示器（FpD)之前面板之情形 時’由於硬化後之樹脂層較佳為低彈性模數，故而具有羥 基之（曱基）丙烯酸酯之含量較佳為4〇質量％以下，更佳為 3 0質量％以下。 又’如玻璃基板與聚碳酸酯等樹脂基板之積層般不同材 料製基板彼此之積層可於不同之表面能量之基板表面使用 顯示低彈性模數之黏著樣態的樹脂層而使樹脂層對任—基 板均可適當地表現密接力。 另方面，於積層較薄之玻璃基板與較厚之玻璃基板之 情形時，亦可藉由設置高彈性模數且〇1麵以下之較薄之 樹脂層而提高積層體的機械強度，於此情形時，亦可將具 有羥基之（曱基）丙烯酸酯之含量設為6〇質量％以上。 (曱基）丙烯酸酯系化合物可為相對低分子之化合物（以 下°己作（曱基）丙烯酸酯系單體），亦可為具有重複單位之 相對高分子量之化合物（以下’記作（甲基）丙嫦酸醋系寡聚 物）。 作為（甲基）丙稀酸醋系化合物，可列舉：包含（甲基）丙 烯酸醋系單體中之1種以上者、包含（甲基）丙稀酸r日系募聚 之1種以上者、包含（甲基）丙稀酸醋系單體中之^種以 上與(甲基)丙稀酸醋系寡聚物中u種以上者較佳為包含 156745.doc •23- 201231263 丙烯酸酯系寡聚物中之1種以上者、3戈包含丙烯酸S旨系寡 聚物中之1種以上與（甲基）丙烯酸酯系單體中之1種以上 者。為提高與基板之密接性，尤佳為平均每1分子中具有 1.8〜4個包含丙稀冑氧基與曱|丙稀醯氧纟中之一者或兩 者之硬化性官能基的胺基甲gU旨系寡聚物、含有具有經基 數為1個或2個且碳數為3〜8之羥烷基之曱基丙烯酸羥烷基 酯的硬化性樹脂組合物。 又，於積層體之用途為平板顯示器（FpD)之前面板之情 形時，較佳為硬化後之樹脂層為更低彈性模數而使硬化過 程之樹脂之收縮等不對平板顯示器（FPD)的顯示性能造成 不良影響。因此，較佳為含有平均每！分子中具有18〜4個 包含（曱基）丙烯醯氧基之硬化性官能基之募聚物、具有羥 基數為1個或2個且碳數為3〜8之羥烷基之甲基丙烯酸羥烷 基酯、不具有羥基之（甲基）丙烯酸酯系單體中之丨種以上的 硬化性樹脂組合物。進而，更佳為不具有羥基之（甲基）丙 烯酸酯系單體之總量與上述具有羥基之（甲基）丙稀酸酯系 單體之含量相比，以質量比計大致相等或更大。又，亦可 使用具有羥基為1個且碳數為12〜22之羥烷基之（甲基）丙烯 酸羥烷基酯代替不具有羥基之（甲基）丙稀酸酯系單體。 作為（曱基）丙烯酸酯系單體，若考慮將硬化性樹脂組合 物置於減壓裝置内之減壓環境下，則較佳為具有可充分抑 制揮發性之程度之低蒸汽壓的化合物。於硬化性樹脂組合 物含有不具有經基之（甲基）丙婦酸醋系單體之情形時，可 使用碳數為8〜22之（甲基）丙烯酸烷基酯、相對低分子量之 156745.doc -24· 201231263 聚乙二醇或聚丙二醇等聚趟二醇之單（甲基）丙烯酸酯或二 (甲基）丙烯酸酯等，較佳為碳數為8〜22之甲基丙稀酸烷基 酯0 作為（尹基）丙稀酸酯系寡聚物，較佳為包括具有2個以 上之重複單位之鍵（聚胺基甲酸S旨鏈、聚醋鍵、聚鍵鏈、 聚碳酸酯鏈等）與（甲基）丙烯醯氧基之分子構造的基）丙 烯酸酯系寡聚物。 作為該（甲基）丙烯酸S旨系寡聚物，例如可列舉：稱為胺 基甲酸酯（曱基）丙烯酸酯寡聚物的具有胺基曱酸酯鍵（通常 進而包含聚酯鏈與聚醚鏈）與2個以上之（甲基）丙烯醯氧基 之（甲基）丙烯酸酯系寡聚物。胺基甲酸酯（曱基）丙烯酸酯 由於可藉由胺基甲酸酯鏈之分子設計而大幅度調整硬化後 之樹脂層之機械性能或與基板之密接性等，故而更佳。 作為第1硬化性樹脂組合物之（曱基）丙烯酸酯系寡聚物 之數量平均分子量較佳為1〇〇〇〜1〇〇〇〇〇，更佳為1〇〇〇〇 〜70000。若數量平均分子量小於1000，則有硬化後之樹脂 層之交聯密度升高而損害樹脂層之柔軟性之虞。又，若數 量平均分子量大於100000，則有未硬化之硬化性樹脂組合 物之黏度變得過大之虞。於（曱基）丙烯酸酯系寡聚物之黏 度過N之情形時’較佳為與（曱基）丙烯酸酯系單體併用而 降低硬化性樹脂組合物整體之黏度。 另方面’於用作用以形成密封部之第2硬化性樹脂組 〇物之It形時’因易將常溫下之黏度調整至上述塗佈時之 黏度fe®、或上述塗佈後之黏度範圍，故較佳為包含具有 156745.doc •25- 201231263 硬化性基且數量平均分子量為30000〜100000之硬化性寡聚 物中之1種以上、與具有硬化性基且為（甲基）丙烯酸醋系之 單體中之1種以上，且單體之比例於寡聚物與單體之合計 (100質量％)中為15〜50質量％。 (甲基）丙烯酸酯系券聚物更佳為可於硬化過程中提高反 應性之丙烯酸酯系寡聚物。 作為光聚合起始劑，可列舉：苯乙酮系、縮酮系、安息 香或安息香醚系、氧化膦系、二苯甲酮系、硫雜蒽酮系、 酿系等光聚合起始劑’較佳為苯乙酮系或氧化膦系光聚合 起始劑。於藉由短波長之可見光進行硬化之情形時，就光 聚合起始劑之吸收波段而言更佳為氧化膦系光聚合起始 劑。藉由併用吸收波段不同之2種以上之光聚合起始劑， 可進而加快硬化時間，用以形成密封部之第2硬化性樹脂 組合物可提高表.面硬化性，因此更佳。 藉由使第1硬化性樹脂組合物所使用之光聚合起始劑與 第2硬化性樹脂組合物所使用之光聚合起始劑的光吸收波 長不同，可促進由來自積層前驅物之侧面之光照射引起的 第2硬化性樹脂組合物之硬化。於此情形時，第丨硬化性樹 脂組合物所使用之光聚合起始劑吸收更長波長之光。 作為光陽離子產生劑，可列舉鏽鹽系化合物等。 光硬化性樹脂組合物亦可視需要包含聚合抑制劑、光硬 化促進劑、鏈轉移劑、光穩定劑（紫外線吸收劑、自由基 捕獲劑等）、抗氧化劑、難燃劑、接著性改善劑（矽烷偶合 劑等）、顏料、染料等各種添加劑，較佳為包含聚合抑制 156745.doc -26- 201231263 劑、光穩疋劑。尤其是藉由以較聚合起始劑少之量包含聚 合抑制劑，可改善光硬化性樹脂組合物之穩定性，亦可調 整硬化後之樹脂層之分子量。 但是，根據積層體之用途，包含有妨礙光線透過硬化後 之樹脂層之虞的添加劑之情況欠佳。若舉出一例，則於積 層體之用途為平板顯示器（FPD)之前面板或薄層太陽電池 元件之情形時，由於前者係來自形成顯示圖像之平板顯示 器（FPD)之出射光或反射光透過硬化後之樹脂層、後者係 太陽光透過硬化後之樹脂層，故而包含有妨礙該等光線之 透過之虞的添加劑之情況欠佳。例如，紫外線吸收劑有吸 收透過樹脂層之太陽光的紫外線成分而降低入射至薄層太 陽電池70件上之光的量、或者對平板顯示器（FpD)之顯示 圖像之色調造成不良影響之虞。但是，另一方面太陽光^斤 透過之樹脂層要求有耐光性、尤其是對紫外線等短波長之 光的耐久性。因此，於包含紫外線吸收劑等之情形時，較 佳為適當調整其吸收特性、調配量等。 又，為提高與基板之密接性’調整硬化後之樹脂層之彈 性模數’較佳為包含鍵轉移劑、尤佳為分子内具有硫氮基 之鏈轉移劑。較佳之硫氫繫鏈轉移劑之一例為正十二烷基 硫醇。 几土 作為聚合抑制劑，可列舉：對苯二酚系（2,5_二_第三丁 基對苯二紛等）、冑苯二盼系（對帛三丁基鄰苯二紛等）、惹 醌系、酚噻嗪系、羥基曱笨系等聚合抑制劑。 心 作為光穩定劑，可列舉··紫外線吸收劑（苯并三唑系、 156745.doc •27- 201231263 二笨曱酮系、水楊酸酯（salicylate)系等）、自由基捕獲劑 (受阻胺系）等。 作為抗氧化劑，可列舉磷系、硫系化合物。 作為光聚合起始劑及各種添加劑，因光硬化性樹脂組合 物置於減壓環境下，故較佳為分子量較大、減壓下之蒸汽 壓較小之化合物。 繼而，於減壓環境下，在以上述工序供給於密封部所包 圍之區域之第1硬化性樹脂組合物上疊加另一基板。為達 成上述目的，只要於一基板之表面中的以上述工序供給第 1硬化性樹脂組合物側之表面朝向另一基板側之狀態下疊 加一對基板與另一基板即可。藉此獲得於一對基板間夾持 第1硬化性樹脂組合物並密封之積層體前驅物。 以下，於本說明書中，存在將於減壓環境下在供給於密 封部所包圍之區域的第1硬化性樹脂組合物上疊加另一基 板之工序僅稱為「真空積層j之情況。 於本發明之積層體之製造方法中，於實施真空積層時， 必需留意以下方面。 圖2係表示於將牛頓流體夾持於一對基板間之狀態下以 負重F進行加壓時之壓力分佈的示意圖。此處，於將牛頓 流體之半彳空設為R時’自牛頓流體中心之距離為r之位置的 壓力P由下述式所表示。 P=2xF/”R2x(R2_r2)/R2 因此’牛頓流體之中心部之壓力P成為2F/〇R2)，牛頓流 體之外緣部之壓力p成為〇。 156745.doc -28- 201231263 於實施真空積層時，夾持於—對基板1〇a、1〇b間之第i 硬化性树月曰組合物3 0係作為牛頓流體而發揮作用，因此第 1硬化性樹脂組合物30產生如圖2所示之壓力分佈。並且， 產生此種壓力分佈之結果有夾持於基板1〇a、i〇b間之第1 硬化性樹脂組合物30之厚度變得不均勻之虞。 若根據磨力分佈’夾持於基板1 、1 〇b間之第1硬化性 樹脂組合物30之厚度變得不均勻，則有產生以下問題之 虞。 於使用厚度較小之玻璃基板例如厚度為3 mm以下之玻 璃基板作為夾持第1硬化性樹脂組合物3〇之基板丨〇a、1 〇b 之情形時，有因玻璃之變形而導致積層體變形之虞。 又’於為用作平板顯示器（FPD)之前面板之積層體之情 形時’若夹持於透明基板間之硬化性樹脂組合物的厚度不 均勻，則有使該硬化性樹脂組合物硬化之樹脂層亦存在厚 度之不均勻、產生光學應變等問題之虞。 此處，產生圖2所示之壓力分佈之原因在於：第1硬化性 樹脂組合物作為牛頓流體而發揮作用且藉由加壓而向外側 擴展。因此’若可藉由形成於基板之周邊部之密封部而防 止第1硬化性樹脂組合物向外侧擴展，則可抑制第1硬化性 樹脂組合物所產生之壓力分佈。 但是’為藉由密封部而防止第1硬化性樹脂組合物向外 側擴展’構成密封部之第2硬化性樹脂組合物於自供給第1 硬化性樹脂組合物時直至以下述工序解除減壓環境期間具 有足夠咼之黏度變得較為重要。具體而言，上述所定義之 156745.doc •29· 201231263 塗佈後之第2硬化性樹脂組合物之黏度為刪〜测μ。 若塗佈冑之第2硬化性接十脂組合物之黏度滿足上述範 圍’則可抑制於實施以積層日夺夾持於一對基板間之第】 硬化性樹脂組合物所產生的壓力分佈，可防止第丨硬化性 樹脂組合物之厚度變得不均勻。 於本發月之積層體之製造方法中，塗饰後之第2硬化性 樹脂組合物之黏度較佳為1000〜5000 Pa.s。 如上所述，於藉由選擇使用之塗佈機構、塗佈條件等而 消除塗佈咼黏度之硬化性樹脂組合物時之問題之情形時， 可直接以上述塗佈後之黏度範圍（8〇〇〜5〇〇〇 Pa,s)塗佈第2 硬化性樹脂組合物。 然而’於此種情形時，選擇黏度較低者作為第2硬化性 樹脂組合物。具體而言’選擇25°c下之黏度範圍為 800〜3000 Pa，s左右者。 於選擇上述黏度較低者作為第2硬化性樹脂組合物之情 形時，較佳為於塗佈第2硬化性樹脂組合物後、供給第1硬 化性樹脂組合物前，使第2硬化性樹脂組合物半硬化，而 提高該第2硬化性樹脂組合物之黏度。 於本說明書中，所謂半硬化，係指藉由進行硬化反應而 提昇第2硬化性樹脂組合物之黏度，但可進一步進行硬化 反應之狀態。作為半硬化之基準，可使用膠體率。於使用 包含下述（甲基）丙烯酸酯系化合物之光硬化性樹脂組合物 且常溫下之黏度為800〜3000 Pa.s者作為第2硬化性樹脂組 合物之情形時，較佳為半硬化時之膠體率成為1〇〜80%。 156745.doc 30· 201231263 又’作為藉由半硬化之黏度上升之基準，亦可使用塗佈 第2硬化性樹脂組合物後之塗佈線寬之擴展。於使用包含 下述（甲基）丙烯酸酯系化合物之光硬化性樹脂組合物且常 溫下之黏度為800〜3000 Pa.s者作為第2硬化性樹脂組合物 之情形時’自塗佈60秒後起120秒鐘的塗佈線寬之擴展較 佳為與未半硬化者相比成為60%以下。 又，作為藉由半硬化之黏度上升之基準，亦可使用動態 黏彈性測定中之彈性項成分G'(儲存彈性模數）。於使用常 溫下之黏度為800〜3000 Pa*s者之情形時，半硬化後之儲存 彈性模數較佳為成為半硬化前之儲存彈性模數之5倍以 上。又，半硬化後之儲存彈性模數較佳為1χ1〇4〜5χΐ〇4 Pa ° 於使第2硬化性樹脂組合物半硬化之情形時，可一面塗 佈第2硬化性樹脂組合物一面使所塗佈之第2硬化性樹脂組 合物半硬化，亦可於第2硬化性樹脂組合物之塗佈完成後 使所塗佈之第2硬化性樹脂組合物半硬化。 又，於本發明之積層體之製造方法中，以實施真空積層 時之密封部之高度（H)與解除減壓環境後之密封部之高度 (h)之比（H/h;以下，於本說明書中稱為「密封部之高2 = ' 少率」)成為以5〜2.5之方式設定實施真空積層時之密：部 的高度。 ° 由於構成密封部之第2硬化性樹脂組合物具有—定程产 之黏性’故而於實施真空積層後，密封部 又 T丨乏间度一定程度 上減少。然而，必需留意如下方面：解除減壓環境後之存 156745.doc •31· 201231263 在於第1硬化性樹脂組合物中之氣泡的合計體積（解除減虔 % i兄之殘留氣泡的合計體積），即於解除減壓環境後，存 在於由一對基板與密封部密閉之空間内之第丨硬化性樹脂 組合物中所存在的氣泡之合計體積係由下述式所表示。 (解除減壓環境之殘留氣泡之合計體積）==(實施真空積層 後之密封部《高度《減少量）x(密封部所包圍《區域之面 積）x(由實施真空積層時與解除減壓環境後之壓力差所引 起之氣泡之縮減率） 此處，有解除減壓環境後之殘留氣泡之合計體積越大， 於解除減壓環境後之第1硬化性樹脂組合物中殘留越大之 氣泡的傾向。若於解除減壓環境後之第丨硬化性樹脂組合 物中殘留較大之氣泡’則該氣泡消失前需要較長時間，製 造積層體時之良率下降。又’若於使第!硬化性樹脂組合 物硬化時’在第1硬化性樹脂組合物中存在氣泡則於使 第1硬化性樹脂組合物硬化之樹脂層中殘留氣泡。若與積 層體之用途對應之基準值以上之大小的氣泡殘留於樹脂層 中’則成為積層體之氣泡缺陷，因此成為問題。 可認為：若減小實施真空積層後之密封部之高度的減少 量，則解除減壓環境後之殘留氣泡之合計體積減少、解除 減壓環境後之殘留於第1硬化性樹脂組合物中之氣泡亦進 而減小，故而於積層體之製造上較佳。 然而’若實施真空積層後之密封部之高度之減少量過 小’則有於真空積層時第1硬化性樹脂組合物自密封部向 外側漏出之虞。 156745.doc -32- 201231263 上述密封部之高度減少率亦可謂相同。即，可認為：若 減小密封部之高度減少率，則解除減壓環境後之殘留氣泡 之合計體積減少，解除減壓環境後之殘留於第&quot;更化性樹 &amp;組合物中之氣泡亦進而減小，故而於積層體之製造上較 佳。 然而’若密封部之高度減少率過小’則有於真空積層時 第1硬化性樹脂組合物自密封部向外側漏出之虞。 若密封部之高度減少率為上述範圍，則解除減壓環境後 之殘留氣泡之合計體積減少，解除減壓環境後之殘留於第 1硬化性樹脂組合物中之氣泡亦進而減小，因此於積層體 之製造上較佳，且於真空積層時第丄硬化性樹脂組合物不 自密封部向外側漏出。 可5忍為於密封部之高度減少率大於2.5之情形時，殘留 耽/包之合s十體積增大，於解除減壓環境後之第丄硬化性樹 脂組合物中殘留較大之氣泡，因此於積層體之製造上欠 佳。 圖3(a)、3(b)、3(c)及3⑷係表示實施真空積層時與解除 • 減壓環境後之積層前驅物（於一對基板l〇a、l〇b間夾持硬 化性樹知組合物30並密封而成之積層體前驅物）之狀態的 示’“圖® 3(a) (b)係表示密封部20之高度減少率大於2_5 之隋开/(6t/t 6)時的積層體前驅物之狀態之冑，圖3⑷係表 不實轭真空積層後之積層體前驅物之狀態之圖，圖3⑻係 表示解除減壓環境後之積層體前驅物之狀態之圖。圖 3(c)、（d)係表不密封部2〇之高度減少率於ι 〇5〜2·5之範圍 156745.doc -33- 201231263 内之情形（1.5t/t=1.5)時的積層體前驅物之狀態之圖，圖 3(c)係表示貫施真空積層後之積層體前驅物之狀態之圖， 圖3(d)係表不解除減壓環境後之積層體前驅物之狀態之 圖。 圖3(b)係於解除減壓環境後之第！硬化性樹脂組合物3〇 中殘留較大之氣泡1 〇〇，相對於此圖3 (d)係解除減壓環境後 之殘留於第1硬化性樹脂組合物3 〇中之氣泡2〇〇均較小而未 殘留較大之氣泡。 另一方面，於密封部20之高度減少率小於1〇5之情形 時，有於真空積層時第i硬化性樹脂組合物3〇自密封部2〇 向外側漏出之虞。 於本發明之積層體之製造方法中，較佳為以密封部之高 度減少率成為1.05〜1.8之方式設定。 根據上述觀點可明確：於實施真空積層後，密封部之高 度一疋程度上減少。此時，密封部之寬度增加。於本發明 之積層體之製造方法中，於在一基板之周邊部塗佈第2硬 化性樹脂組合物時’必需留意由實施真空積層引起之密封 部之形狀變化。 圖4(a)、4(b)係表示由實施真空積層引起之密封部之形 狀變化的示意圖，表示形成於基板上之密封部中之角部之 一。此處，圖4(a)表示實施真空積層前之狀態，圖4(b)表 示實施真空積層後之狀態。再者，於圖4(b)中以單點虛線 (dashed line)表示真空積層前之密封部之形狀。 作為密封部整體之共同點，實施真空積層後與實施真空 156745.doc -34- 201231263 積層前相比密封部之官亦# Α ^ ^ ^ ^ 之寬度增加。於塗佈第2硬化性樹脂組 物時#慮此種费封部之寬度之增加而設定第2硬化性 樹脂組合物之線寬。 進而根據圖4(a)、4(b)之比較可明確：藉由密封部之 形狀變化而顯用以形成密封部之硬化性樹脂組合物向角 部之内側伸出。即，相對於圖4⑷所示之實施真空積層前 之密封部之形狀，圖4(b)所示之實施真空積層後之密封部 係成為用以形成密封部之硬化性樹脂組合物向角部之内側 伸出的狀態。 如上所述，於為FPD之前面板之情形，由於若用以形成 密封部之硬化性樹脂組合物向有效顯示區域側伸出，則有 圖像產生變形之虞’故而要求用以形成密封部之硬化性樹 脂組合物不向有效顯示區域側伸出，即用以形成密封部之 硬化性樹脂組合物未自密封部向内側伸出，因此圖4(a)、 4(b)所示之由實施真空積層引起的密封部之形狀變化成為 問題。 本發明之積層體之製造方法係以用以形成密封部之硬化 性樹脂組合物於實施真空積層後不自密封部之角部向内側 伸出之方式塗佈第2硬化性樹脂組合物。 圖5(a)、5(b)係用以對本發明之積層體之製造方法申的 第2硬化性樹脂組合物之塗佈形態之較佳例進行說明之 圖’與圖4⑷、4(b)同樣，圖5⑷表示實施真空積層前之狀 態’圖5(b)表示實施真空積層後之狀態。於圖5⑷中，以 虛線表示使用分注器等塗佈機構塗佈第2硬化性樹脂組合 156745.doc -35· 201231263 物時之塗佈機構之路徑。又’於圖5⑻中。。 示真空積層前之密封部之形狀。 早點虛線表 於圖5(a)中，角部附近之塗佈寬度(即 之寬度）盥密^h# 杓附近之密封部 又广、密封。P之其他塗佈寬度相比變細 示，於實施真空積層後可防止用以形成 圖5(b)所 脂組合物自密封部之角部向内側伸出。。之硬化性樹 :本：明之積層體之製造方法中，如圓5(心所示，使密 角部附近之第2硬化性樹脂組合物之塗佈寬产與宋 封部之其他塗佈寬度相比變細，藉此於實施 抑制用以形成密封部之硬化性樹脂組合物自敎 向内側伸出。 | &lt;月4 、於圖5(a)中，除密封部之角部附近之塗佈寬度(即角部附 近之密封部之寬度）與密封部之其他塗佈寬度相比變細以 外塗佈時之密封部之角部内緣側亦位於較圖5(b)所示之 實施真工積層後之密封部之角部的内緣側更靠近基板之外 緣側。 本發明之積層體之製造方法仙除使密封部之肖部附近 之塗佈寬度與密封部之其他塗佈寬度相比變細以外，塗佈 時之推封冑之角部内緣側亦位於車交實施真空積層後之密封 P之角。卩的内緣側更靠近基板之外緣側之方式，塗佈第2 硬化f生树月曰組合物’於實施真空積層後，可抑制用以形成 氹封部之硬化性樹脂組合物自密封部之角部向内側伸出， 因此較佳。 圖6(a)、6(b)係用以對本發明之積層體之製造方法中的 156745.doc -36- 201231263 第2硬化性樹脂組合物之塗佈形態之另一較佳例進行說明 之圖’圖6(a)表示實施真空積層前之狀態，圖6(b)表示實 施真空積層後之狀態。於圖6(a)中，以虛線表示使用分注 器等塗佈機構塗佈第2硬化性樹脂組合物時之塗佈機構的 路在。又，於圖6(b)中，以單點虛線表示真空積層前之密 封部之形狀。 於圖6(a)_，下述方面與圖5(a)相同。 •密封部之角部附近之塗佈寬度（即角部附近之密封部之 寬度）與密封部之其他塗佈寬度相比變細之方面。 •塗佈時之密封部之角部内緣側位於較實施真空積層後 之密封部之角部的内緣側更靠近基板之外緣侧之方面。 其結果與圖5(b)相同，於圖6(b)中，於實施真空積層後 可防止用以形成密封部之硬化性樹脂組合物自密封部之角 部向内側伸出。 ” 方面，關於圖中以虛線表示之塗佈機構之路徑， ^(a)與圖5⑷不同。即，圖$⑷係塗佈機構之路徑朝向密 角。卩而形成直線路徑，相對於此圖6(叻係塗佈機構 =彳密封部之角㈣’形成朝向基板之外緣侧之 曲線路徑。 於可二佈機構之路控如圖6⑷所示設為曲線路徑之情況廷 短塗二t分注器等之嗔嘴之移動而進行塗佈，故而就可絲 组塗佈時間、及 而 …、為停止硬化性樹脂組合物自噴嘴噴技 ^控㈣佈量之方“言較佳。Liquid crystal display), EL (electroluminescence) such as organic EL or inorganic EL, flat panel display (FPD) such as plasma display device, electronic ink type image display device, thin-film solar cell element, touch panel, and the like. In the case where one of the pair of substrates is an opaque substrate, a specific example of the opaque substrate is a substrate made of a metal material such as stainless steel or a substrate made of a ceramic material, and a filler which absorbs visible light is dispersed in the substrate. A light-shielding resin substrate or the like. Further, in the case where both of the pair of substrates are transparent substrates, the pair of transparent substrates may be formed of the same material or may be formed of different materials. That is, the pair of transparent substrates may be a glass substrate or a transparent resin substrate, or one of the pair of transparent substrates may be a glass substrate. The other is a transparent resin substrate. The thickness of the substrate is not particularly limited. In the case of a transparent substrate, the thickness of the glass substrate is usually 〇_1 to 6 mm in terms of mechanical strength and transparency, and the thickness in the case of a transparent resin substrate. Usually 0. 1 to 3 mm. When the laminate manufactured by the method of the present invention is used as the front panel of the FPD, it is preferable to use a glass substrate having a thickness of 〇 〜 3 claws, and more preferably a thickness of 0. 4—丨5 mm glass substrate. On the other hand, in the case of an opaque substrate, the thickness is usually 〇 4 to 4 mm in terms of mechanical strength and thinness and weight reduction. Furthermore, the thickness of the pair of substrates may be the same or different. In order to raise the surface of the substrate, more specifically, the interface forming force between the surface on the side where the sealing portion is formed on the peripheral portion and the sealing portion, a surface treatment may be performed. Here, the surface material is applied only to the periphery (four) of the substrate, and may be applied to the entire surface of the substrate. 156745. Doc -12· 201231263 A method of treating a surface of a substrate with a decane coupling agent, a method of treating the surface, etc. [Sealing portion] Sealing. p is a &amp; curable resin group which is supplied to the region surrounded by the sealing portion and then sandwiched between the pair of substrates and sealed in a two-pressure environment, and is further set to be in the present invention. In the manufacturing process of the laminated body, it is supplied. The interfacial adhesion force is greater than or equal to the extent that the curable resin composition does not leak out in the region surrounded by the sealing portion. When the vacuum layer is applied in the following step, the height of the sealing portion is reduced to a certain extent by the viscosity of the sealing portion, thereby preventing the leakage of the i-hardening I. The thickness of the layer of the first curable resin composition sandwiched between the substrates becomes uneven, so that the seal is required to have a high viscosity. In the manufacturing method of the laminate of the present invention, by hardening the high viscosity [the tree, the day. Further, the Q-like material is applied to the second curable resin composition by means of a device or the like to form a sealing portion having the above-described properties. The width of the sealing portion after the decompression environment is released by the method of the present invention by the method of the present invention is 〇. 8~3 _, the ratio of the south/width of the cross-sectional shape of the sealing portion is 0. 05 to 1, when applying the second curable resin composition, it is necessary to pay attention to the following points. (1) The second curable resin composition after application is changed in time (4) because the height thereof is lowered and the line width is increased. Therefore, it is necessary to pay attention to the fact that the sealing portion has a specific width and height when the vacuum lamination is performed in the following steps. Mode setting 156745. Doc -13· 201231263 The aspect of the line width and height of the second curable resin composition at the time of coating. (2) In the method for producing a laminate according to the present invention, the height (H) of the sealing portion and the decompression environment at the time of performing vacuum lamination are set such that the height of the sealing portion is slightly reduced when the decompression environment is released in the following step. The ratio (H/h) of the degree of orientation (h) of the rear seal portion. As a result, the sealing portion after the decompression environment is released has a lower height and a larger width than the sealing portion when the vacuum lamination is performed. Therefore, it is necessary to note that the width and height of the sealing portion when performing vacuum lamination are set such that the sealing portion has a specific width and height after the pressure reducing environment is released by the following steps. The viscosity of the second curable resin composition at least from the time of supplying the ninth curable resin composition to the time of releasing the reduced pressure environment by the following steps (hereinafter, there is a second sclerosing property after application in the present specification) The viscosity of the resin composition is 800 to 5000 Pa*s. In addition, the reason why the viscosity of the second curable resin composition after application is required to be in the above range is as follows. However, the viscosity of the second curable resin composition at the time of coating is in the above range of 800 to 5000 pa. s, there is a case where it is difficult to apply the second curable resin composition to a specific width and height. As described above, the laminate produced by the method of the present invention is in the following procedure.  The width of the sealing portion after the decompression environment is released is 0. 8 to 3 mm. When the second curable resin composition is applied by using a dispenser or the like, as described above, the shape thereof changes with time as the height thereof decreases and the line width increases. Therefore, the width of the sealing portion after the decompression environment is released is set to 0. 8 to 3 mm, and the line width of the second curable resin composition at the time of coating is smaller than the width of the above-mentioned sealing portion 156745. Doc • 14-201231263 and minimize the time required to apply the second curable resin composition. However, in order to allow the second curable resin composition having a high viscosity to be ejected from a fine nozzle such as a dispenser at a relatively high flow rate, it is necessary to eject at a high pressure, so that it is difficult to apply it on an industrial scale. Further, when a high-viscosity curable resin composition is applied by using a dispenser or the like, a delay occurs before the discharge from the tip end of the dispenser nozzle is started, so that it is difficult to control the line width of the curable resin composition at the time of application. However, when the viscosity of the curable resin composition at the time of application is too low, the shape change of the curable resin composition after application becomes remarkable, and it is difficult to set the sealing portion in the vacuum deposition. The case of a specific width and height. Further, π» Therefore, in the method for producing a laminate of the present invention, it is preferred that the viscosity of the second curable resin composition is from 10 to 750 pa. s. When the viscosity of the second curable resin composition at the time of application is in the above range, the coating property of the curable resin composition is excellent, and the shape change over time of the curable resin composition after application is not remarkable. In the method for producing a laminate according to the present invention, it is more preferred that the viscosity of the second curable resin composition at the time of coating is 30 to 600 pa. s 〇:: 'In the case where the coating mechanism used, the coating conditions, etc., can be used to eliminate the problem of the high-viscosity curable resin composition on the cloth Η 2 directly in the above-mentioned coating-like viscosity range Coated (four) 2 sclerosing tree sorghum composition. In order to apply the second curable tree Pa«s to the method for producing the laminate according to the present invention, the viscosity of the composition of the mooncake composition is set to 10 to 750 156745. Doc -15· 201231263 2 The viscosity of the curable resin composition is set to 800~5000 pa. s, the curable resin composition having a viscosity of 800 to 5,000 Pa*s at room temperature is selected as the second curable resin composition, and the viscosity is set to 10 to 750 Pa when the second curable resin composition is heated. The second curable resin composition may be applied in the state of S. After the application, the viscosity of the second curable resin composition increases as the temperature of the second curable resin composition decreases, and the viscosity of the second curable resin composition after the application as defined above becomes 8〇〇. ~5〇〇〇pa. s. In the present specification, "normal temperature" means "25»c". Here, in order to keep the distance between the pair of substrates, the interstitial particles having a specific particle diameter may be blended in the second curable resin composition. Further, as the second curable resin composition, it is preferred to use the photocurable resin composition described below, that is, the viscosity at normal temperature satisfies the viscosity range after the above coating (800 to 5 〇〇〇 pa. s). When the sealing portion is formed by applying the second curable resin composition, it is necessary to pay attention to the following points. As described above, the second curable resin composition for forming the sealing portion has a higher viscosity due to the coating of the second curable resin composition, and the first portion of the region surrounded by the seal. Compared with the curable resin composition, there is little change in shape over time. The core, in the case where a partial defect is formed in the formed seal portion, or X is reduced in the thickness of the seal portion 4, it is difficult to release the defects by the shape change over time. &quot; Further, in the case of the coating form of the second curable resin composition at 'J'<JT#, the width of the sealing portion of the sealant Ar: The other coating width of the seal is thinner, but it is 156745. Doc 201231263 The curable resin composition for forming the sealing portion protrudes inward from the sealing portion, and the partial refinement of the sealing portion described herein does not include the operation of refining the coating width in the vicinity of the corner portion of the sealing portion. . In the case where a partial defect or a thinning occurs in the formed sealing portion, the first curable resin composition in the region surrounded by the finally sealed portion is formed by vacuum lamination or by vacuum lamination in the following step. This is not preferable because the sealing portion is extended more outwardly, so that an additional step such as removal of the protruding portion is required. Further, the envelope which is supplied to the sealing portion protrudes outward from the sealing portion. In the case of the first curable resin group in the region, when the laminated body produced is damaged, and the partial portion is broken or refined in the formed sealing portion, when the decompression environment is released in the following steps, In the space where the pair of the substrate and the sealing portion are sealed, the gas is invaded, so that a large bubble is generated in the first curable resin composition existing in the sealed space. When the π" seal portion is formed, when the green curable resin composition is overlapped at the start and end points of the coating, it is difficult to be released by the change in shape over time. Therefore, the following steps are performed. In the case of vacuum lamination, the thickness of the encapsulation is partially uneven, so that the car is generated in the i-th hardening resin composition in the space sealed by the base and the sealing portion: In addition, the width of the seal portion due to the overlap is large, so it is detrimental to the novelty of the laminated body produced. Therefore, by applying the second curable resin bismuth compound When forming a seal name, it is preferred to have a portion after coating the second curable resin composition at 156745. Doc -17- 201231263 Check for defects such as loss, refinement, and overlap. Among them, depending on the size of the defect, there is a case where the above problem does not occur. Therefore, it is preferable to check whether or not there is a defect exceeding the allowable range of the predetermined value. Furthermore, the following criteria are known as the basis of the defects of the company. However, the basis for the allowable defects is not limited and may be appropriately selected as needed. (Reference example) When there is a case where the following criteria are satisfied, 'there is no problem in the manufacture of the laminated body.' Defect: The length of the defective portion in the direction of the coating line is less than mm5 mm, or less than 70% of the coating height. The smaller of ° / 〇. Refining: The length of the portion where the coating width is less than 8 % (the length of the coating line direction) is less than 10 consecutively with respect to the reference coating width. Overlap: The overlap of the length of the coating line is less than 5 mm. The inspection method of the defect is not particularly limited. As a specific example, a method of visually inspecting the presence or absence of defects of the curable resin composition after application, and a method of confirming the presence or absence of the curable resin composition after application by image processing can be mentioned. When a defect exceeding the reference value is not found in the defect inspection, the curable resin composition is supplied to the region surrounded by the sealing portion on the substrate by the following procedure. On the other hand, when the defect inspection 10 is found to exceed the defect of the reference value, the sealing portion on the substrate is applied to the substrate by applying the second curable resin composition to the portion where the defect is present and repairing the defect. The curable resin composition may be supplied to the surrounding region. In this case, you can also repair 156745. Doc -18_ 201231263 After the defect is fixed, the defect check is performed again. In addition, when the repair of the defect is not suitable for the cost, the defect which is found to be more than the reference value in the defect inspection may be discarded, and the second curable resin composition may be semi-hardened. In the case where the second cured resin composition is semi-cured, it is preferable to perform defect inspection and repair of defects in the sealing portion. Then, the second crucible resin composition is supplied to the region surrounded by the sealing portion on the substrate. When the amount of the first curable resin composition is sandwiched between a pair of substrates and sealed in the following step, the first curable resin composition is filled only by the first curing resin composition. The amount of space in which the substrate and the sealing portion are sealed. In this case, the amount of supply of the i-th curable resin composition can be determined in consideration of the decrease in volume due to the hardening shrinkage of the i-th curable resin composition, and the production of the laminate of the present invention can be carried out in the following steps. In the method, when the curable resin composition is sandwiched between a pair of substrates and sealed, the thickness of the layer of the curable resin composition present in the space sealed by the counter substrate and the sealing portion is preferably 30 to 3000 μπ! . The reason for this is that the layer of the i-th hardening resin composition is required to have the function of not only imparting a function as an adhesive for the base (four) but also imparting mechanical strength or impact absorption to the layer. It is generally preferable that the opening member or the display member is required to be thin and lightweight and unnecessarily thickened. The first curable resin composition is held on the counter substrate 156745 in the following order. When the sealing is performed between the docs 201231263, the thickness of the layer of the first curable resin composition which is present in the space sealed by the substrate and the sealing portion is preferably from 1 〇〇 to 16 Å, more preferably from 200 Å to _ (4). In particular, in the case of liquid crystal use, the thickness of the layer of the i-th hardening resin composition is more preferably 1 〇〇 to _ ηηη, more preferably 〜 〜 μ η η 〇 〇 〇 〇 〇 彻 彻 η 〇 〇 〇 〇 〇 〇 彻 彻 彻 彻: The method in which the substrate on which the sealing portion is formed is horizontally placed in the above-described steps, and is supplied in a dot shape or a line shape by a supply mechanism such as a dispenser. &quot; In the manufacturing method of the present invention, 'the prior method of injecting a curable resin into the gap between the laminates formed in advance (for example, Japanese Patent Laid-Open No. Sho 57-165411, Japanese Patent Laid-Open No. 339) The method described in the publication No. 88 is a first curable resin composition as compared with a relatively high-viscosity curable resin composition. Thereby, it is possible to improve the hardening shrinkage at the time of curing of the tempering resin composition and the mechanical strength of the resin layer after curing. The first curable resin composition has a viscosity of 0 2 to 50 Pa. s is preferable because it is easy to handle in the steps of industrially producing, transferring, and coating a large amount of the curable resin composition. In addition, the viscosity of the first curable resin composition as used herein refers to the viscosity in the temperature region when the method for producing the laminate of the present invention is carried out, and particularly refers to the supply of the curable resin combination to the region surrounded by the sealing portion. After the object, the viscosity in the temperature region before the vacuum lamination was carried out in the following procedure. For example, in the case where these steps are carried out at normal temperature, it is the viscosity of the curable resin composition at normal temperature. 156745. Doc -20· 201231263 The first curable resin composition preferably has a viscosity of ^20 Pa,s. As the first curable resin composition which satisfies the above viscosity, a curable resin composition containing a high molecular weight curable compound (oligomer or the like) described below can be used. Since the high molecular weight curable compound can reduce the number of chemical bonds in the curable resin composition, the hardening shrinkage when the curable resin composition is cured is reduced, and the residual stress of the resin layer after hardening can be lowered and can be improved. Mechanical strength. On the other hand, the high molecular weight curable compound is mostly highly viscous. Therefore, in order to secure the mechanical strength of the resin layer after hardening and to suppress the residual of the bubbles, it is preferred to dissolve the curable monomer having a smaller molecular weight in the high molecular weight curable compound to adjust the viscosity. However, by using a curable monomer having a small molecular weight, the viscosity of the curable resin composition is lowered, but there is a resin having a large residual stress caused by hardening shrinkage when the curable resin composition is cured, and the resin is hardened. The mechanical strength of the layer is degraded. The curable resin composition to be used is preferably a photocurable resin composition. The photocurable resin composition is hardened in a shorter period of time by the heat of the day than the thermosetting resin composition. Therefore, in the present invention, the environmental load at the time of manufacturing the laminated body is reduced by using the photocurable resin composition. Further, since the photocurable resin grade can be substantially hardened in a few minutes to several tens of minutes, the production efficiency of the laminate is high. The photocurable resin composition refers to a material which forms a resin layer by a hardening reaction caused by the action of light. Examples of the photocurable resin composition include, for example, those in which the hardness of the resin layer after curing is not excessively high. Doc -21 - 201231263 Intra-range use · Composition containing a compound having an addition polymerizable unsaturated group and a photopolymerization initiator>> A ratio containing an unsaturated group and a molar number of sulfhydryl groups substantially 1 to 6 unsaturated polyalkylene compounds (trienyl isocyanurate, etc.) and a polythiol compound having 1 to 6 sulfhydryl groups (triethylene glycol dithiol) ^ including photopolymerization A composition of the starter. • A composition comprising an epoxy compound having two or more epoxy groups and a photocationic generator. The photocurable resin composition preferably contains a group selected from the group consisting of an acryloxy group and a methacryloxy group in terms of a high curing rate and a high transparency of the resin layer after curing. (hereinafter, at least one of the compounds referred to as (meth) acryloxy) and a photopolymerization initiator. The compound having a (meth) propylene fluorenyloxy group (hereinafter also referred to as a (meth)acrylic vinegar-based compound) is preferably a compound having an average of i to 6 (meth) acryloxy groups in the i molecule. Further, in terms of the hardened resin layer not becoming too hard, a compound having 〜3 (meth) propylene fluorenyloxy groups in the average oxime molecule is particularly preferable. The (meth) acrylate-based compound is preferably an aliphatic or alicyclic compound which does not contain an aromatic ring as much as possible in terms of light resistance of the resin layer after curing. Further, as the (meth) acrylate-based compound, a compound having a hydroxyl group is more preferable from the viewpoint of enhancing the adhesion to the interface of the substrate. The content of the (meth) acrylate compound having a hydroxyl group is in the total (mercapto) acrylic acid 156745. Doc -22-201231263 The ester compound is preferably 15% by mass or more, more preferably 20% by mass or more. On the other hand, the modulus of elasticity of the resin having a hydroxyl group after hardening tends to increase, especially when a (hydroxy) acrylate having a hydroxyl group is used, which is hardened according to the use of the laminate. The resin layer becomes too hard. For example, 'in the case of a front panel for a flat panel display (FpD)', since the resin layer after hardening preferably has a low modulus of elasticity, the content of the (fluorenyl) acrylate having a hydroxyl group is preferably 4% by mass or less. More preferably, it is 30% by mass or less. Further, if a laminate of a substrate made of a glass substrate and a resin substrate such as polycarbonate is laminated, a resin layer exhibiting a low elastic modulus can be used for the surface of the substrate having different surface energies to make the resin layer - The substrate can properly express the adhesion. On the other hand, in the case of laminating a thin glass substrate and a thick glass substrate, it is also possible to improve the mechanical strength of the laminated body by providing a thin resin layer having a high elastic modulus and less than one surface. In some cases, the content of the (fluorenyl) acrylate having a hydroxyl group may be 6% by mass or more. The (fluorenyl) acrylate-based compound may be a relatively low molecular compound (hereinafter referred to as a "mercapto" acrylate monomer), or a compound having a relatively high molecular weight of a repeating unit (hereinafter referred to as "A Base) propionate vinegar oligomers). The (meth)acrylic acid vinegar-based compound may be one or more selected from the group consisting of (meth)acrylic acid-based monomers, and one or more types containing (meth)acrylic acid r. Preferably, the (meth)acrylic acid vinegar-based monomer and the (meth)acrylic acid vinegar-based oligomer are more than 156,745. Doc. 23-201231263 One or more of the acrylate-based oligomers and one or more of the (meth)acrylate-based monomers, including one or more of the acrylic acid-based oligomers. In order to improve the adhesion to the substrate, it is particularly preferable to have an average of one molecule per molecule. 8 to 4 amino-based gU-based oligomers comprising a sclerosing oxy group and one or both of the sulfonium oxyhydroxides, having a base number of 1 or 2 A curable resin composition of a hydroxyalkyl methacrylate having a carbon number of 3 to 8 and a hydroxyalkyl group. Moreover, in the case where the use of the laminated body is a front panel of a flat panel display (FpD), it is preferable that the resin layer after hardening has a lower elastic modulus and the shrinkage of the resin in the hardening process is not displayed on the flat panel display (FPD). Performance has an adverse effect. Therefore, it is better to have an average per! a polymer having 18 to 4 sclerosing functional groups containing a (fluorenyl) acryloxy group in the molecule, and a methacrylic acid having 1 or 2 hydroxyalkyl groups having a carbon number of 3 to 8 A curable resin composition containing at least one of a hydroxyalkyl ester and a (meth) acrylate monomer having no hydroxyl group. Further, it is more preferable that the total amount of the (meth) acrylate monomer having no hydroxyl group is substantially equal to or more than the mass ratio of the above-mentioned (meth) acrylate monomer having a hydroxyl group. Big. Further, a (meth)acrylic acid hydroxyalkyl group having one hydroxyl group and a carbon number of 12 to 22 hydroxyalkyl groups may be used instead of the (meth) acrylate monomer having no hydroxyl group. When the (mercapto) acrylate monomer is placed under a reduced pressure in a pressure reducing device, it is preferred to have a low vapor pressure which can sufficiently suppress the degree of volatility. When the curable resin composition contains a (meth) propylene vinegar-based monomer having no trans group, an alkyl (meth) acrylate having a carbon number of 8 to 22 and a relatively low molecular weight of 156745 can be used. . Doc -24· 201231263 Mono(meth)acrylate or di(meth)acrylate of polydecanediol such as polyethylene glycol or polypropylene glycol, preferably methacrylic acid having a carbon number of 8 to 22 The alkyl ester 0 is preferably a (yinyl) acrylate-based oligomer, and preferably includes a bond having two or more repeating units (polyaminocarboxylic acid S chain, polyacetic acid bond, poly bond chain, polycarbonate) A acrylate-based oligomer having a molecular structure of a (meth) propylene oxime group, such as an ester chain. Examples of the (meth)acrylic acid S-based oligomer include, for example, a urethane oxime ester acrylate having an amino phthalate bond (generally further comprising a polyester chain and (Polyether chain) and (meth)acrylate-based oligomer of two or more (meth)acryloxy groups. Urethane (mercapto) acrylate is more preferable because the molecular properties of the urethane chain can be greatly adjusted by adjusting the mechanical properties of the cured resin layer or the adhesion to the substrate. The number average molecular weight of the (fluorenyl) acrylate-based oligomer as the first curable resin composition is preferably from 1 Torr to 1 Torr, more preferably from 1 Torr to 70,000. If the number average molecular weight is less than 1,000, the crosslinking density of the cured resin layer is increased to impair the flexibility of the resin layer. Further, when the number average molecular weight is more than 100,000, the viscosity of the uncured curable resin composition becomes excessively large. When the viscosity of the (fluorenyl) acrylate-based oligomer exceeds N, it is preferable to use it in combination with a (fluorenyl) acrylate-based monomer to lower the viscosity of the entire curable resin composition. On the other hand, when it is used as the It shape for forming the second curable resin group of the sealing portion, it is easy to adjust the viscosity at normal temperature to the viscosity at the time of coating, or the viscosity range after the coating. Therefore, it is preferable to include 156745. Doc • 25-201231263 One or more of the curable group having a number average molecular weight of 30,000 to 100,000 and one or more of the monomers having a curable group and being a (meth)acrylic acid vinegar The ratio of the monomer is 15 to 50% by mass in the total of the oligomer (100% by mass). The (meth) acrylate-based conjugate is more preferably an acrylate-based oligomer which can improve the reactivity during the curing process. Examples of the photopolymerization initiator include acetophenone-based, ketal-based, benzoin or benzoin-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and photopolymerization initiators such as brewing systems. An acetophenone-based or phosphine oxide-based photopolymerization initiator is preferred. In the case of hardening by a short-wavelength visible light, a phosphine oxide-based photopolymerization initiator is more preferable in terms of an absorption band of the photopolymerization initiator. By using two or more kinds of photopolymerization initiators having different absorption bands in combination, the curing time can be further accelerated, and the second curable resin composition for forming the sealing portion can be improved. The surface is hardenable and therefore better. When the photopolymerization initiator used in the first curable resin composition and the photopolymerization initiator used in the second curable resin composition have different light absorption wavelengths, the surface from the laminated precursor can be promoted. The curing of the second curable resin composition by light irradiation. In this case, the photopolymerization initiator used in the second sclerosing resin composition absorbs light of a longer wavelength. Examples of the photocation generating agent include a rust salt compound. The photocurable resin composition may optionally contain a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and an adhesion improver ( Various additives such as decane coupling agent, pigment, dye, etc., preferably contain polymerization inhibition 156,745. Doc -26- 201231263 Agent, light stabilizer. In particular, by including a polymerization inhibitor in a smaller amount than the polymerization initiator, the stability of the photocurable resin composition can be improved, and the molecular weight of the resin layer after curing can be adjusted. However, depending on the use of the laminate, it is not preferable to include an additive which hinders light from passing through the hardened resin layer. As an example, when the use of the laminate is in the case of a flat panel display (FPD) front panel or a thin-film solar cell element, the former is transmitted from the emitted light or reflected light from the flat panel display (FPD) forming the display image. The hardened resin layer and the latter are those in which the sunlight passes through the cured resin layer. Therefore, it is not preferable to include an additive which hinders the transmission of such light. For example, the ultraviolet absorber has an ultraviolet component that absorbs sunlight passing through the resin layer to reduce the amount of light incident on the thin solar cell 70, or adversely affects the color tone of the display image of the flat panel display (FpD). . However, on the other hand, the resin layer through which the sunlight passes is required to have light resistance, particularly durability against short-wavelength light such as ultraviolet rays. Therefore, in the case of including an ultraviolet absorber or the like, it is preferred to appropriately adjust the absorption characteristics, the blending amount, and the like. Further, in order to improve the adhesion to the substrate, the elastic modulus of the resin layer after the curing is adjusted is preferably a bond transfer agent, and particularly preferably a chain transfer agent having a sulfur-nitrogen group in the molecule. One example of a preferred sulphur-hydrogen chain transfer agent is n-dodecyl mercaptan. As a polymerization inhibitor, several kinds of soils include hydroquinone (2,5-di-t-butyl-p-phenylene), and indole-benzene (p-butylene phthalate). Polymerization inhibitors such as lanthanum, phenothiazine, and hydroxy oxime. Heart As a light stabilizer, a UV absorber (benzotriazole system, 156745. Doc •27- 201231263 Diclofenac, salicylate, etc., radical scavenger (hindered amine). Examples of the antioxidant include a phosphorus-based or sulfur-based compound. As the photopolymerization initiator and various additives, since the photocurable resin composition is placed under a reduced pressure atmosphere, a compound having a large molecular weight and a small vapor pressure under reduced pressure is preferred. Then, the other substrate is superposed on the first curable resin composition in the region surrounded by the sealing portion in the above-described step in a reduced pressure environment. In order to achieve the above object, a pair of substrates and another substrate may be stacked in a state in which the surface of the first curable resin composition side is supplied to the other substrate side in the above-described step on the surface of one substrate. Thereby, a laminated body precursor in which the first curable resin composition is sandwiched between a pair of substrates and sealed is obtained. In the present invention, the step of superimposing another substrate on the first curable resin composition in the region surrounded by the sealing portion in a reduced pressure environment is simply referred to as "vacuum layering j". In the method for producing a laminate according to the invention, it is necessary to pay attention to the following aspects when performing vacuum lamination. Fig. 2 is a schematic view showing a pressure distribution when a Newtonian fluid is sandwiched between a pair of substrates and pressurized with a load F. Here, when the half-empty of the Newtonian fluid is set to R, the pressure P at the position where the distance from the center of the Newtonian fluid is r is expressed by the following formula: P = 2xF / "R2x (R2_r2) / R2 Therefore ' The pressure P at the center of the Newtonian fluid is 2F/〇R2), and the pressure p at the outer edge of the Newtonian fluid becomes 〇. 156745. Doc -28-201231263 When the vacuum lamination is performed, the i-th hardening tree sap composition 30 sandwiched between the substrates 1A and 1b functions as a Newtonian fluid, so the first hardening property The resin composition 30 produces a pressure distribution as shown in FIG. In addition, as a result of such a pressure distribution, the thickness of the first curable resin composition 30 sandwiched between the substrates 1a and ib is uneven. When the thickness of the first curable resin composition 30 sandwiched between the substrates 1 and 1b is uneven depending on the friction distribution, the following problems occur. When a glass substrate having a small thickness, for example, a glass substrate having a thickness of 3 mm or less is used as the substrate 丨〇a or 1 〇b for sandwiching the first curable resin composition 3, the laminate is caused by deformation of the glass. The deformation of the body. In the case of using a laminate of a front panel of a flat panel display (FPD), when the thickness of the curable resin composition sandwiched between the transparent substrates is not uniform, there is a resin which hardens the curable resin composition. The layer also has problems such as uneven thickness and optical strain. Here, the reason why the pressure distribution shown in Fig. 2 is generated is that the first curable resin composition acts as a Newtonian fluid and expands outward by pressurization. Therefore, if the first curable resin composition is prevented from spreading outward by the sealing portion formed in the peripheral portion of the substrate, the pressure distribution generated by the first curable resin composition can be suppressed. In the second curable resin composition constituting the sealing portion, the second curable resin composition constituting the sealing portion is released from the time when the first curable resin composition is supplied until the decompression environment is removed in the following steps. It is more important to have a sufficient viscosity during the period. Specifically, the above defined 156745. Doc •29· 201231263 The viscosity of the second curable resin composition after coating is 〜μ measured μ. When the viscosity of the second curable decoctate composition of the coated crucible satisfies the above range, it is possible to suppress the pressure distribution generated by the first curable resin composition sandwiched between the pair of substrates by the lamination. The thickness of the ninth curable resin composition can be prevented from becoming uneven. In the manufacturing method of the laminate of the present month, the viscosity of the second curable resin composition after the coating is preferably 1000 to 5000 Pa. s. As described above, when the problem of the application of the coating mechanism, the coating conditions, and the like to eliminate the problem of applying the curable resin composition of the crucible is as described above, the viscosity range after the above coating can be directly used (8〇). 〇~5〇〇〇Pa, s) The second curable resin composition was applied. However, in such a case, the lower viscosity is selected as the second curable resin composition. Specifically, the viscosity at 25 ° C is selected to be in the range of 800 to 3000 Pa, s or so. When the second curable resin composition is selected as the second curable resin composition, it is preferred to apply the second curable resin composition and apply the second curable resin composition before the first curable resin composition. The composition is semi-hardened to increase the viscosity of the second curable resin composition. In the present specification, the term "semi-hardening" refers to a state in which the viscosity of the second curable resin composition is increased by performing a curing reaction, but the curing reaction can be further performed. As a benchmark for semi-hardening, a colloidal rate can be used. The photocurable resin composition containing the following (meth) acrylate-based compound is used and the viscosity at room temperature is 800 to 3000 Pa. In the case of the second curable resin composition, the colloidal ratio at the time of semi-hardening is preferably from 1 to 80%. 156745. Doc 30·201231263 Further, as a standard for increasing the viscosity of the semi-hardening, an extension of the coating line width after the application of the second curable resin composition can be used. The photocurable resin composition containing the following (meth) acrylate-based compound is used, and the viscosity at room temperature is 800 to 3000 Pa. In the case of the second curable resin composition, the spread of the coating line width for 120 seconds from the application of 60 seconds after the application is preferably 60% or less compared with the case of the non-semi-hardened. Further, as a criterion for increasing the viscosity by semi-hardening, the elastic term component G' (storage elastic modulus) in the dynamic viscoelasticity measurement can also be used. When the viscosity at room temperature is 800 to 3000 Pa*s, the storage elastic modulus after the semi-hardening is preferably more than 5 times the storage elastic modulus before the semi-hardening. Further, the storage elastic modulus after the semi-hardening is preferably 1χ1〇4 to 5χΐ〇4 Pa °. When the second curable resin composition is semi-cured, the second curable resin composition can be applied while being coated. The applied second curable resin composition is semi-cured, and the applied second curable resin composition may be semi-cured after the application of the second curable resin composition is completed. Further, in the method for producing a laminate according to the present invention, the ratio (H) of the height (H) of the sealing portion when the vacuum layer is laminated and the height (h) of the sealing portion after the pressure reduction environment is released (H/h; In this specification, it is called "the height of the seal 2 = 'low rate") becomes 5~2. The method of 5 sets the density at the time of vacuum lamination: the height of the part. ° Since the second curable resin composition constituting the sealing portion has a viscosity which is produced in a predetermined range, the thickness of the sealing portion is reduced to some extent after the vacuum lamination is performed. However, it is necessary to pay attention to the following aspects: after the decompression environment is removed, 156745. Doc 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 The total volume of the bubbles present in the second hardenable resin composition in the sealed space is represented by the following formula. (Total volume of residual air bubbles in the decompression environment) == (The sealing portion "height "reduction amount" x after the vacuum lamination is performed (the area of the area surrounded by the sealing portion) x (when the vacuum lamination is performed and the decompression is released) The reduction ratio of the bubble caused by the pressure difference after the environment) The larger the total volume of the residual bubbles after the decompression environment is removed, the larger the residual amount in the first curable resin composition after the decompression environment is released. The tendency of bubbles. If a large bubble remains in the first hardenable resin composition after the decompression environment is released, it takes a long time before the bubble disappears, and the yield when the laminated body is produced is lowered. In the case where the first curable resin composition is present in the first curable resin composition, air bubbles remain in the resin layer in which the first curable resin composition is cured. If bubbles of a size equal to or larger than the reference value corresponding to the use of the laminate are left in the resin layer, the bubble defects of the laminate are caused, which is a problem. When the amount of reduction in the height of the sealing portion after the vacuum lamination is reduced, the total volume of the residual bubbles after the decompression environment is released is reduced, and the remaining in the first curable resin composition is released after the decompression environment is released. The bubbles are further reduced, so that it is preferable to manufacture the laminated body. However, when the amount of reduction in the height of the sealing portion after the vacuum lamination is too small, the first curable resin composition leaks to the outside from the sealing portion at the time of vacuum lamination. 156745. Doc -32- 201231263 The height reduction rate of the above seals can be the same. In other words, it is considered that when the height reduction rate of the sealing portion is reduced, the total volume of residual bubbles after the decompression environment is released is reduced, and the decompression environment is released and remains in the &quot;transformer tree &amp;composition; The bubbles are further reduced, so that it is preferable to manufacture the laminated body. However, when the height reduction rate of the sealing portion is too small, the first curable resin composition leaks outward from the sealing portion at the time of vacuum lamination. When the height reduction rate of the sealing portion is in the above range, the total volume of the residual bubbles after the decompression environment is released is reduced, and the bubbles remaining in the first curable resin composition after the decompression environment is released are further reduced. The laminate is preferably produced, and the second crucible resin composition does not leak to the outside from the sealing portion at the time of vacuum lamination. Can bear 5 for the height reduction rate of the seal is greater than 2. In the case of 5, the residual 耽/package s has a ten-volume increase, and a large bubble remains in the sclerosing resin composition after the decompression environment is released, so that the production of the laminate is not preferable. 3(a), 3(b), 3(c), and 3(4) show laminated precursors after vacuum lamination and release/decompression environments (clamping between a pair of substrates l〇a, l〇b) The state of the state in which the composition 30 is sealed and sealed is shown in Fig. 3(a)(b) shows that the height reduction rate of the sealing portion 20 is greater than 2_5 / (6t/t) 6) The state of the precursor of the laminated body at the time, FIG. 3 (4) shows the state of the precursor of the laminated body after the solid yoke vacuum layer is laminated, and FIG. 3 (8) shows the state of the precursor of the laminated body after the decompression environment is released. Fig. 3(c), (d) shows the height reduction rate of the non-sealing portion 2〇 in the range of ι 〇5~2·5 156745. Doc -33- The situation within 201231263 (1. 5t/t=1. 5) The state of the precursor of the laminated body at the time, FIG. 3(c) is a view showing the state of the precursor of the laminated body after the vacuum layer is applied, and FIG. 3(d) is a layer showing the state after the pressure-reducing environment is not released. A diagram of the state of the precursor of the body. Figure 3 (b) is the first after the decompression environment is released! In the curable resin composition, the large bubbles 1 remain in the crucible, and the bubbles remaining in the first curable resin composition 3 after the decompression environment is released are shown in Fig. 3(d). Smaller without leaving large bubbles. On the other hand, when the height reduction rate of the sealing portion 20 is less than 1〇5, the i-th curable resin composition 3〇 leaks from the sealing portion 2〇 to the outside when the vacuum is laminated. In the method for producing a laminate of the present invention, it is preferable that the height reduction rate of the sealing portion becomes 1. 05~1. 8 way setting. From the above point of view, it is clear that the height of the sealing portion is reduced to a certain extent after the vacuum lamination is carried out. At this time, the width of the sealing portion increases. In the method for producing a laminate according to the present invention, when the second curable resin composition is applied to the peripheral portion of a substrate, it is necessary to pay attention to the shape change of the sealing portion caused by the vacuum lamination. Figs. 4(a) and 4(b) are views showing changes in the shape of the sealing portion caused by the vacuum lamination, and showing one of the corner portions formed in the sealing portion on the substrate. Here, Fig. 4(a) shows a state before the vacuum lamination is performed, and Fig. 4(b) shows a state after the vacuum lamination is performed. Further, in Fig. 4 (b), the shape of the sealing portion before the vacuum lamination is indicated by a dashed line. As a common point of the entire sealing portion, vacuum lamination is carried out and vacuum is implemented 156745. Doc -34- 201231263 Before the laminate, the width of the seal is also increased by #Α ^ ^ ^ ^. When the second curable resin composition is applied, the line width of the second curable resin composition is set in consideration of the increase in the width of the seal portion. Further, as is clear from the comparison of Figs. 4(a) and 4(b), the curable resin composition for forming the sealing portion by the change in the shape of the sealing portion protrudes toward the inner side of the corner portion. In other words, with respect to the shape of the sealing portion before the vacuum lamination shown in Fig. 4 (4), the sealing portion after the vacuum lamination shown in Fig. 4 (b) is a corner portion of the curable resin composition for forming the sealing portion. The state in which the inside is extended. As described above, in the case of the front panel of the FPD, since the curable resin composition for forming the sealing portion protrudes toward the effective display region side, the image is deformed. Therefore, it is required to form the sealing portion. The curable resin composition does not protrude toward the effective display region side, that is, the curable resin composition for forming the sealing portion does not protrude inward from the sealing portion, and therefore, as shown in FIGS. 4(a) and 4(b) The shape change of the sealing portion caused by the vacuum lamination is a problem. In the method for producing a laminate according to the present invention, the curable resin composition for forming the sealing portion is applied to the second curable resin composition so as not to protrude inward from the corner portion of the sealing portion after the vacuum lamination is performed. 5(a) and 5(b) are views for explaining a preferred embodiment of the coating form of the second curable resin composition according to the method for producing a laminate of the present invention, and Figs. 4(4) and 4(b). Similarly, Fig. 5 (4) shows the state before the vacuum lamination is performed. Fig. 5 (b) shows the state after the vacuum lamination is performed. In Fig. 5 (4), the second curable resin composition 156745 is coated with a coating mechanism such as a dispenser. Doc -35· 201231263 The path of the coating mechanism at the time of the object. Also in Figure 5 (8). . The shape of the sealing portion before the vacuum lamination is shown. The dotted line is shown in Fig. 5(a), and the coating width (i.e., the width) near the corner portion is wide and sealed in the vicinity of the sealing portion. The other coating width of P is finer than that, and after the vacuum lamination is performed, it is possible to prevent the fat composition of Fig. 5(b) from projecting inward from the corner portion of the sealing portion. . The curable tree: In the manufacturing method of the laminated body of the present invention, as shown in the circle 5, the coating of the second curable resin composition in the vicinity of the dense corner portion is widened and the other coating width of the seal portion is obtained. In comparison with the thinning, the curable resin composition for suppressing the formation of the sealing portion is prevented from projecting inward from the crucible. &lt;Month 4, in FIG. 5(a), the coating width in the vicinity of the corner portion of the sealing portion (that is, the width of the sealing portion in the vicinity of the corner portion) is thinner than the other coating width of the sealing portion. The inner edge side of the corner portion of the sealing portion is also located closer to the outer edge side of the substrate than the inner edge side of the corner portion of the sealing portion after the real laminated layer shown in Fig. 5(b). In the method for producing a laminate according to the present invention, the coating width in the vicinity of the ridge portion of the sealing portion is made thinner than the other coating width of the sealing portion, and the inner edge side of the corner portion of the squeezing squeegee at the time of application is also located in the vehicle. The angle of the seal P after the vacuum lamination is carried out. The coating of the second hardened f-tree sorghum composition is applied to the outer edge side of the substrate so as to be self-sealing after the vacuum lamination is performed to form the curable resin composition for forming the dam seal portion. It is preferable that the corner portion of the portion protrudes inward. 6(a) and 6(b) illustrate another preferred embodiment of the coating form of the second curable resin composition of 156745.doc-36-201231263 in the method for producing a laminate of the present invention. Fig. 6(a) shows a state before the vacuum lamination is performed, and Fig. 6(b) shows a state after the vacuum lamination is performed. In Fig. 6(a), the path of the coating mechanism when the second curable resin composition is applied by a coating means such as a dispenser is shown by a broken line. Further, in Fig. 6(b), the shape of the sealing portion before the vacuum lamination is indicated by a single dotted line. In Fig. 6(a)_, the following aspects are the same as Fig. 5(a). • The coating width in the vicinity of the corner portion of the sealing portion (i.e., the width of the sealing portion in the vicinity of the corner portion) is thinner than the other coating width of the sealing portion. • The inner edge side of the corner portion of the sealing portion at the time of coating is located closer to the outer edge side of the substrate than the inner edge side of the corner portion of the sealing portion after the vacuum lamination is performed. As a result, in the same manner as in Fig. 5(b), in Fig. 6(b), after the vacuum lamination is performed, the curable resin composition for forming the sealing portion can be prevented from projecting inward from the corner portion of the sealing portion. In the aspect, the path of the coating mechanism indicated by a broken line in the figure, ^(a) is different from that of Fig. 5 (4). That is, the path of the coating mechanism (Fig. $(4) is oriented toward the dense angle. 6 (叻 coating mechanism = angle of the sealing part (4) 'forms a curved path toward the outer edge side of the substrate. The road control of the second and second cloth mechanism is set as a curved path as shown in Fig. 6 (4). It is preferable to apply the coating time of the nozzle, etc., so that the coating time of the silk group can be adjusted, and the amount of the coating of the curable resin composition from the nozzle is controlled.

方面，將塗佈機構之路徑如圖5(a)所示設為直線S 156745.doc -37· 201231263 徑之情況就可完全地將分注it等之喷嘴之移動路徑設為直 角之方面而言較佳。 於實施圖5(a)、圖6⑷所示之第2硬化性樹脂組合物之塗 佈形態之較佳例時，必需留意以下方面。 使在封部之角部附近之塗佈寬度(即角部附近之密封部 之寬度）與密封部之其他塗佈宽度相比細多少？ 使塗佈時之密封部之角部内緣側位於較實施真空積層 後之密封部之角部的内緣側更靠近基板之外緣側多少距 關於該等方面，例如只要實施以下所示之工序即可。 圖7⑷係表示於以固定之塗佈寬度塗佈^硬化性樹脂自 :物之情形時的實施真空積層後之密封部之形狀的示清 ^係與圖4(b)相同之圖。於圖7⑷中，以單點虛線表开 真：積層前之密封部之形狀。又，於圖7⑷中，以虛㈣ 丁貫施真工積層後之密封部之角部附近之理想形狀。 户；：（a)中，較理想為如虛線所示於實施真空積層後之 在封用以形成密封部之硬化性樹脂組合物未向角部内 。：而’於以固定之塗佈寬度塗佈第2硬化性樹脂 為：物之情形時’實施真空積層後之密封部如實線所示成 狀熊。形成在封之硬化性樹脂組合物向角部内側伸出之 形狀 '7(&gt;)中，於以斜線表示之2個部分形成為同 A &amp;為同—面積）之情形時，實施真空積層後之密 °P向角部之内側伸出之部分的寬度C，等於圖7⑷中之c， 156745.doc -38- 201231263 此成為C，=(B部2。此處’ A為實施Μ積層前之第2硬化 性樹脂組合物之塗佈寬度，Β為實施真空積層後之第2硬化 性樹脂組合物之塗佈寬度（即密封部之寬度）。 繼而，於圖7(a)中以斜線表 1又崢刀之面積X可按照以 下之工序求出。 圖7⑻係以圖7(a)之角部外緣側之斜線表示之部分的周 邊之部分擴大圖。此處’與以斜線表示之部分鄰接之扇形 之徑r可藉由下述式而求出。In the case where the path of the coating mechanism is as shown in Fig. 5(a), the path of the nozzle S is equal to the straight line S 156745.doc -37·201231263, and the movement path of the nozzle such as the dispensing unit can be completely set to a right angle. Better words. In the preferred embodiment of the coating form of the second curable resin composition shown in Figs. 5(a) and 6(4), it is necessary to pay attention to the following points. Is the coating width in the vicinity of the corner portion of the seal (i.e., the width of the seal portion near the corner portion) as small as the other coat width of the seal portion? The inner edge side of the corner portion of the sealing portion at the time of application is located closer to the outer edge side of the substrate than the inner edge side of the corner portion of the sealing portion after the vacuum lamination, and for example, the following steps are performed. Just fine. Fig. 7 (4) is a view similar to Fig. 4 (b) showing the shape of the sealing portion after the vacuum lamination is applied to the case where the curable resin is applied in a fixed coating width. In Fig. 7 (4), the opening is shown by a single dotted line: the shape of the sealing portion before the lamination. Further, in Fig. 7 (4), the ideal shape in the vicinity of the corner portion of the sealing portion after the artificial layer is applied by the virtual (four). In the case of (a), it is preferable that the curable resin composition for sealing the portion to be formed after the vacuum lamination is applied as shown by the broken line is not in the corner portion. In the case where the second curable resin is applied in a fixed coating width, the sealing portion after the vacuum lamination is formed as a solid bear. In the case of forming a shape '7 (&gt;) in which the curable resin composition of the seal protrudes toward the inner side of the corner portion, when two portions indicated by oblique lines are formed to have the same area as A &amp; The width C of the portion where the dense layer PP protrudes toward the inner side of the corner portion is equal to c in Fig. 7(4), 156745.doc -38 - 201231263 This becomes C, = (B part 2. Here 'A is the implementation Μ The coating width of the second curable resin composition before lamination is 涂布 is the coating width of the second curable resin composition after vacuum lamination (that is, the width of the sealing portion). Then, in Fig. 7(a) The area X of the slanting table 1 and the boring tool can be obtained by the following steps. Fig. 7 (8) is an enlarged view of a portion of the periphery of the portion indicated by the oblique line on the outer edge side of the corner portion of Fig. 7 (a). The diameter r of the fan-shaped portion adjacent to the oblique line can be obtained by the following formula.

r=l/-/2xr + C =2/(2-V2)xC 因此，以斜線表示之部分之面積χ可藉由下述式 出。 Χ=Γ2-π/4χτ2 =(1-π/4)χΓ2 =(1-π/4)χ{2/(2--/2)}2χ〇2 =2.5xC2 繼而’根據第2硬化栂讲，人 更化丨生树脂組合物之塗佈形態之較佳 例’將表示塗佈第2硬化性槲，人a 树曰組合物之情形時之實施真 空積層後之密封部之开彡站沾-A 具 狀的不意圖示於圖8。圖8係與圖 6(b)相同之圖，於圖8中， 早點虛線表示真空積層前之密 封部之形狀。又，於阁 ^ 、 ，以虛線表示實施真空積層後 之密封部之角部附近之理想形狀。 積廣後 此處’為抑制密封部6 心“ &quot;向角部内側伸出，只要使圖8中以 斜線表示之2個部分ψ ，角邻内側之斜線部分的面積較角 156745.doc •39- 201231263r=l/-/2xr + C = 2/(2-V2)xC Therefore, the area 部分 of the portion indicated by oblique lines can be expressed by the following formula. Χ=Γ2-π/4χτ2 =(1-π/4)χΓ2 =(1-π/4)χ{2/(2--/2)}2χ〇2 =2.5xC2 and then 'based on the second hardened 栂A preferred example of the coating form of the humanized resin composition is to indicate that the second sclerosing sputum, the human a sapling composition is applied, and the sealing portion of the sealing portion after vacuum lamination is applied The -A figure is not shown in Figure 8. Fig. 8 is a view similar to Fig. 6(b), and in Fig. 8, an early dotted line indicates the shape of the sealing portion before the vacuum lamination. Further, in the cabinet, the ideal shape in the vicinity of the corner portion of the sealing portion after the vacuum lamination is performed is indicated by a broken line. After the accumulation, here, in order to suppress the inner side of the sealing portion 6 &quot; to the inner side of the corner, as long as the two parts are indicated by oblique lines in Fig. 8, the area of the oblique line on the inner side of the corner is smaller than the angle 156745.doc • 39- 201231263

部外側之斜線部分之面積大即可。因此，只要以滿足下述 式所示之關係之方式設定於密封部之角部附近且使第2硬 化性樹脂組合物之塗佈寬度變細之部分的距離（即，於角 部附近且使密封部之寬度變細之部分的距離）D、及密封部 之角邻附近之第2硬化性樹脂組合物之塗佈寬度的最小值 (即，角部附近之密封部之寬度的最小值）£即可。 1/2xDx(A-E)&gt;1/2xX D&gt;X/(A-E) D&gt; 1/(Α-Ε)χ(1-π/4)χ (2/(2-V2)}2xC2 〇&gt;(1-π/4)χ{2/(2-ν2)}2χΐ/4χ(Β-Α)2/(Α-Ε) D&gt;0.63x(B-A)2/(a_E)...式⑴ 但是’若於密封部之角部附近且使第2硬化性樹脂組合 物之塗佈寬度變細之部分的距離(即，於角部附近且使密 封部之寬度變細之部分的距離 丨刀的距離）D過大，則於實施真空積層 月1J或實施真空積層時，有供仏於玄μ加^二 ，仏、，。於抢封部所包圍之區域之第 1硬化性樹脂組合物自密封 &lt;見度變細之部分向該密封 部的外側伸出之盧。又，於存Α ^ …邱… 又於實施減屬環境之解除時，有氣The area of the diagonal portion on the outer side of the portion may be large. Therefore, the distance in the vicinity of the corner portion of the sealing portion and the portion where the coating width of the second curable resin composition is reduced (that is, in the vicinity of the corner portion and the like) is set so as to satisfy the relationship shown by the following formula. The distance D between the portion where the width of the sealing portion is tapered, and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner of the sealing portion (that is, the minimum value of the width of the sealing portion in the vicinity of the corner portion) £ can be. 1/2xDx(AE)&gt;1/2xX D&gt;X/(AE) D&gt; 1/(Α-Ε)χ(1-π/4)χ(2/(2-V2)}2xC2 〇&gt;( 1-π/4)χ{2/(2-ν2)}2χΐ/4χ(Β-Α)2/(Α-Ε) D&gt;0.63x(BA)2/(a_E)...(1) But ' The distance between the portion where the coating width of the second curable resin composition is narrowed in the vicinity of the corner portion of the sealing portion (that is, the distance from the portion near the corner portion and the width of the sealing portion is reduced) When the D is too large, the first hardening resin composition in the region surrounded by the seal portion is self-sealing when the vacuum laminate layer 1J or the vacuum laminate layer is applied. The part that has become thinner is extended to the outside of the sealing part. Also, Yu Cunzhen ^...Qi... In the implementation of the reduction of the environment, there is gas

體自外部Υ冗入由_科篇 Jtc tfe + A 對基板與密封部密閉之空間内之 因此’於密封部之备 m, 〇 且使第2硬化性樹脂組合物 之塗佈寬度變細之部分的距離 m ί ^ Λ Ρ於角邛附近且使密封 β之寬度變細之部分的距離 佔盔机盔c 往馮°又為】5 mm以下，更 佳為5又為5_以下，更佳為設以下。 基於上述觀點，將於密 樹脂組合物之塗佈寬度變細之部二=且使第2硬化性 刀的距離（即，於角部附 156745.doc 201231263 近且使岔封部之寬度變細之部分的距離）D、及密封部之角 部附近之第2硬化性樹脂組合物之塗佈寬度的最小值（即， 角部附近之密封部之寬度的最小值）E之設定之一例示於以 下〇 ， (參考例1) 於參考例1中，使用以與下述實施例（例4)所記載之光硬 化性樹脂組合物（第2·)相同之工序製作者作為第2硬化性樹 脂組合物。使用旋轉黏度計（RE-85U(東機產業公司製造）) 測定25°C下之黏度，結果約為950 Pa.s。 使用分注器於長度800 、寬度500 mm、厚度3 mm之 鈉鈣玻璃製基板（以下，稱為基板A)之中央部48〇χ6〇〇爪爪 之區域的外周部塗佈第2硬化性樹脂組合物而形成密封 部。 此處，分注器係使用具有内徑為丨〇6 之喷嘴者，將 基板A與喷嘴頂端之間隔設為〇 8 mm，密封部之直線部分 係以6.6 mg/cm之喷出量塗佈第2硬化性樹脂組合物。此 處’假設實施真空積層前之第2硬化性樹脂組合物之塗佈 寬度A 〇·9 mm，實施真空積層後之密封部之寬度B = 1 5 mm，圖 8 中之00.3 mm。 、又，密封部之角部附近係藉由調節喷嘴之移動速度而以 成為以圖8之單點虛線表示之形狀之方式塗佈第2硬化性樹 脂組合物。 此處’以於密封部之角部附近且使第2硬化性樹脂組合 物之塗佈寬度變細之部分的距離(即，於角部附近且使密 156745.doc •41· 201231263 封部之寬度變細之部分的距離）D、及密封部之角部附近之 第2硬化性樹脂組合物之塗佈寬度的最小值（即，角部附近 之密封部之寬度的最小值）E滿足上述式（丨）之關係之方式嗖 定。設定之D、E如以下所示。 D : 3 mm E · 0.3 mm 於第2硬化性樹脂組合物之塗佈完成6〇秒後藉由紫外 線（UV，ultraviolet)照射而使第2硬化性樹脂組合物半硬 化。紫外線照射係使用基板A之表面之365 nm之照度為2 mW/cm2的UV曝光機，於該uv曝光機中，花費3〇秒鐘自基 板A之單面進行UV照射。 再者，求出以與上述相同之條件實施uv照射之第2硬化 性樹脂組合物的膠體率作為半硬化之基準，結果約為 55%。再者，第2硬化性樹脂組合物之膠體率係以與下述 實施例（例4)相同之工序求出。 又’則疋自塗佈第2硬化性樹脂組合物6 〇秒後起12 〇秒鐘 之第2硬化性樹脂組合物之塗佈線寬的擴展作為利用半硬 化之黏度上升之基準，並與未進行半硬化者比較，結果該 擴展為50%。 繼而，於密封部所包圍之區域，以間隔均等之方式，花 費約ίο秒鐘，使用分注器分散滴加1536滴117 g之第i硬化 性樹脂組合物。 再者，使用以與下述實施例（例〗）所記載之樹脂層形成 用光硬化性樹脂組合物相同之工序製作者作為第丨硬化性 I56745.doc •42· 201231263 樹脂組合物。使用旋轉黏度計（RE-85U)測定25。(：下之黏 度’結果約為1.7 Pa.s。 於分散滴加第1硬化性樹脂組合物後，於壓力為丨〇以之 減壓容器内，以硬化性樹脂組合物介於基板間之方式對基 板A疊加相同形狀且相同厚度之鈉鈣玻璃板（稱為基板 B)(真空積層）。 以目視確認實施真空積層後之密封部之形狀，結果未產 生向角部之内側之伸出。 (參考例2) 於參考例2中，於密封部之角部附近且使第2硬化性樹脂 ’且0物之塗佈寬度變細之部分的距離（即，於角部附近且 使密封部之寬度變細之部分的距離）D、及密封部之角部附 近之第2硬化性樹脂組合物之塗佈寬度的最小值（即，角部 附近之迳封部之寬度的最小值）E按照以下所示之方式設 定，除此以外實施與參考例1相同之工序。 〇&quot; D : 3 mm E . 0.6 mm 上述D、E滿足上述式（1)之關係。 乂目視確„忍實施真空積層後之密封部之形狀’結果 生向角部之内側之伸出。 (參考例3) 考j中第2硬化性樹脂組合物以固定之塗 形成密封部（即，夫佶玄私如 ^ 佈寬度 未使被封。p之角部附近之塗佈寬In the space where the substrate and the sealing portion are sealed, the body is externally entangled, so that it is prepared in the sealing portion, and the coating width of the second curable resin composition is made thinner. The distance of the part m ί ^ Λ Ρ 邛 邛 且 且 且 且 且 且 且 且 占 占 占 占 占 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔 盔Jia is set below. From the above viewpoint, the coating width of the dense resin composition is reduced to 2 and the distance of the second curable knife is made (that is, the corner portion is attached to 156745.doc 201231263 and the width of the sealing portion is made thinner. An example of the setting of the distance D of the portion) and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion (that is, the minimum value of the width of the sealing portion in the vicinity of the corner portion) E (Reference Example 1) In the reference example 1, the same procedure as that of the photocurable resin composition (2nd) described in the following Example (Example 4) was used as the second curability. Resin composition. The viscosity at 25 ° C was measured using a rotary viscometer (RE-85U (manufactured by Toki Sangyo Co., Ltd.)), and it was about 950 Pa.s. Applying the second hardenability to the outer peripheral portion of the region of the central portion 48〇χ6〇〇 claw of the soda lime glass substrate (hereinafter referred to as substrate A) having a length of 800, a width of 500 mm, and a thickness of 3 mm using a dispenser The resin composition forms a sealing portion. Here, the dispenser uses a nozzle having an inner diameter of 丨〇6, the interval between the substrate A and the nozzle tip is set to 〇8 mm, and the straight portion of the sealing portion is coated at a discharge amount of 6.6 mg/cm. The second curable resin composition. Here, it is assumed that the coating width A 〇·9 mm of the second curable resin composition before the vacuum lamination is performed, and the width B = 15 mm of the sealing portion after the vacuum lamination is performed, and 00.3 mm in Fig. 8 . Further, in the vicinity of the corner portion of the sealing portion, the second curable resin composition is applied so as to have a shape indicated by a dotted line in Fig. 8 by adjusting the moving speed of the nozzle. Here, the distance from the vicinity of the corner portion of the sealing portion and the application width of the second curable resin composition is reduced (that is, in the vicinity of the corner portion and the sealing portion is 156745.doc •41·201231263 The distance D of the portion where the width is narrowed, and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion (that is, the minimum value of the width of the sealing portion in the vicinity of the corner portion) E satisfy the above The relationship between the formula (丨) is determined. The set D and E are as follows. D: 3 mm E · 0.3 mm After the coating of the second curable resin composition is completed for 6 seconds, the second curable resin composition is semi-hardened by ultraviolet (ultraviolet) irradiation. The ultraviolet irradiation was performed using a UV exposure machine having an illuminance of 2 mW/cm 2 at 365 nm on the surface of the substrate A, and in the uv exposure machine, it took 3 seconds to perform UV irradiation from one side of the substrate A. In addition, the colloidal ratio of the second curable resin composition subjected to uv irradiation under the same conditions as above was determined as a standard of semi-hardening, and it was about 55%. In addition, the colloidal ratio of the second curable resin composition was determined in the same manner as in the following Example (Example 4). In addition, the expansion of the coating line width of the second curable resin composition from the application of the second curable resin composition 6 after 12 seconds from the second curing period is used as a reference for increasing the viscosity by semi-curing, and The comparison was made without semi-hardening, and the expansion was 50%. Then, in the region surrounded by the sealing portion, 1536 drops of 117 g of the i-th hardening resin composition were dispersed and dropped using a dispenser for about 0.25 seconds. In addition, the same procedure as that of the photocurable resin composition for forming a resin layer described in the following Examples (Examples) was used as the second curing property I56745.doc • 42·201231263 resin composition. 25 was measured using a rotational viscometer (RE-85U). The viscosity of the lower layer was about 1.7 Pa.s. After the first curable resin composition was added dropwise, the pressure-sensitive resin was placed in a vacuum vessel, and the curable resin composition was interposed between the substrates. In a manner, a soda lime glass plate of the same shape and the same thickness (referred to as a substrate B) was superposed on the substrate A (vacuum laminate). The shape of the sealing portion after the vacuum lamination was visually confirmed, and as a result, no protrusion to the inner side of the corner portion was produced. (Reference Example 2) In Reference Example 2, the distance between the second curable resin 'and the coating width of the zero material in the vicinity of the corner portion of the sealing portion (that is, near the corner portion and sealing) The distance D of the portion where the width of the portion is narrowed, and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion (that is, the minimum value of the width of the sealing portion in the vicinity of the corner portion) E is set as follows, and the same steps as in Reference Example 1 are carried out. 〇 &quot; D : 3 mm E . 0.6 mm The above D and E satisfy the relationship of the above formula (1). The shape of the seal after the vacuum lamination is carried out. (Reference Example 3) The second curable resin composition in Test J is formed by a fixed coating to form a sealing portion (i.e., the width of the fabric is not sealed. The coating near the corner of p) Cloth width

細），除此以外實施與參考㈣目同之工序。 I 156745.doc -43· 201231263 、目視確實施真空積層後之密封部之形狀，結果未產 生向角部之内側之較大之伸出。 (參考例4) 於參考例4中，於密封部之角部附近且使第2硬化性樹脂 組°物之塗佈寬度變細之部分的距離（即，於角部附近且 使在封部之寬度變細之部分的距離、及密封部之角部附 近之第2硬化性樹脂組合物之塗佈寬度的最小值(即，角部 附近之也封之寬度的最小值）£按照以下所示之方式設 定，除此以外實施與參考例1相同之工序。 又 D : 0.5 mm E ： 0.6 mm 上述D、E不滿足上述式⑴之關係。 以目視球認實施真空積層後之密封部之形狀，結果產生 向角部之内側之伸出。 (參考例5) 於參考例5中，於密封部之角部附近且使第2硬化性樹脂 組合物之塗佈寬度變細之部分的距離（即，於角部附近且 使密封部之寬度變細之部分的距離)D、及密封部之角部附 近之第2硬化性樹脂組合物之塗佈寬度的最小值（即，’ 附近之饴封部之寬度的最小值）]6係按照以下所示之方八 疋’除此以外實施與參考例1相同之工序。 D : 20 mm E · 0.3 mm 上述D、E滿足上述式（1)之關係。 J56745.doc •44· 201231263Fine), except the same as the reference (4). I 156745.doc -43· 201231263 The shape of the sealing portion after vacuum lamination was visually confirmed, and as a result, a large protrusion to the inner side of the corner portion was not produced. (Reference Example 4) In Reference Example 4, the distance between the corner portion of the sealing portion and the portion where the coating width of the second curable resin group is narrowed (that is, in the vicinity of the corner portion and in the sealing portion) The distance between the portion where the width is reduced and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion (that is, the minimum value of the width of the seal near the corner portion) are as follows. In the other manners, the same procedure as in Reference Example 1 was carried out. D: 0.5 mm E : 0.6 mm The above D and E did not satisfy the relationship of the above formula (1). The sealing portion after vacuum lamination was visually recognized. In the case of the reference example 5, the distance from the corner portion of the sealing portion to the portion where the coating width of the second curable resin composition is narrowed is obtained. (that is, the distance between the portion where the width of the sealing portion is narrowed in the vicinity of the corner portion) D and the minimum value of the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion (that is, 'near' The minimum width of the 饴 seal is based on the following: 'Embodiment except that the same procedure as in Reference Example 1 D:. 20 mm E · 0.3 mm above D, E satisfies the relationship of formula (1) of J56745.doc • 44 · 201231263.

以目視確認實拍；亩_ # Q 真二積層後之密封部之形狀，結果未產 生向角部之内側之伸出。 然而，於實施直办&amp; a μ . .. 二積層後’確Srtii第1硬化性樹脂組合物 自密封部之寬度變細之部分伸出。 再者’將以密封部之角部附近之第2硬化性樹脂組合物 之塗佈寬度與密封部之其他塗佈寬度相比變細之方式塗佈 第2硬化性樹脂組合物之工序示於以下。 :本發明之積層體之製造方法中，必需使密封部之高度 固定H必需使第2硬化性樹脂組合物之塗佈高度固 定。 於第2硬化性樹脂組合物之塗佈高度固定之情形時，第2 硬化性樹脂組合物之塗佈量之變化與第2硬化性樹脂組合 物的塗佈寬度直接相關。此處’若改變第2硬化性樹脂组 合物自分注器等噴出機構中之喷出量，則第2硬化性樹脂 組合物之塗佈量變化，藉此可改變第2硬化性樹脂組合物 之塗佈寬度。因此’藉由使密封部之角部附近之第2硬化 性樹脂組合物的噴出量較密封部之其他塗佈寬度彡，可使 密封部之角部附近之塗佈寬度較密封部t其他塗佈寬度 細。 又，於第2硬化性樹脂組合物自分注器等噴出機構中之 喷出量固定之情形時，若改變噴出機構之移動速度，則第 2硬化性樹脂組合物之塗佈量變化，因此藉此可改變第2硬 化性樹脂組合物之塗佈寬度。因&amp;，藉由使喷出機構於密 封部之角部附近之移動速度較密封部之其他塗佈寬度快， 156745.doc •45· 201231263 可使第2硬化性樹脂組合物於进封部之角部附近之塗佈寬 度較密封部之其他塗佈寬度細。 於本發明之積層體之製造方法中，真空積層可按照以下 之工序貫施。以下’於本說明書中’在一對基板中將表面 上形成密封部及第1硬化性樹脂組合物之層之側的基板稱 為一基板，將表面上未形成該等之側的基板稱為另一基 板。 將一基板放入減壓裝置中，以第1硬化性樹脂組合物之 面朝上之方式於減壓裝置内之固定支撐盤上水平放置該基 板。 於減壓裝置内之上部設置可於上下方向移動之移動支樓 機構’於移動支撐機構上安裝另一基板。此處，於在另一 基板之表面上形成有薄膜系太陽電池元件之情形時，使形 成有薄膜系太陽電池元件之側的表面朝下β又，於積層體 之用途為平板顯示器（FPD)之情形時，使位於製品之更外 側之面朝下。又，於在另一基板之表面設置抗反射層之情 形時’使未形成抗反射層之側之表面朝.下。 另一基板位於一基板之上方且不與第丨硬化性樹脂組合 物接觸之位置。即，使一基板之表面上之第丨硬化性樹脂 組合物與另一基板不接觸而相對向。 再者，將可於上下方向移動之移動支撐機構設置於減壓 裝置内之下部，亦可於移動支撐機構上設置一基板。於此 情形時，另一基板係安裝於減壓裝置内之上部所設置之固 定支撐盤上，使一基板與另一基板相對向。 156745.doc -46- 201231263 又，亦可利用設置於減壓裝置内之上下 π切文得機 構支撐一基板及另一基板兩者 於將-基板及另-基板配置於特定位置後，使減壓裝置 之内部減壓而形成特定之減壓環境。若有可能，則亦可於 減壓操作過程中或形成特定之減壓環境後，於減壓裝置内 將一基板及另一基板配置於特定位置。 於減壓裝置之内部成為特定之減壓環境後，使由移動支 標機構所支撐之另-基板向下方移動，於一基板之表面上 之第1硬化性樹脂組合物上疊加另一基板。 藉由疊加而於由一基板之表面、另一基板之下表面及密 封部所包圍之空間内密封第i硬化性樹脂組合物。 於曼加時’藉由另一基板之自重、來自移動支標機構之 擠昼等而擴展第！硬化性樹脂組合物，從而於上述空間内 充滿第1硬化性樹脂組合物。 疊加時之減壓環境之環境壓力為1〇〇〇 pa以下，較佳為 Pa以上》若減璧環境之環境壓力過低，則有對硬化性 樹脂組合物所含之各成分(硬化性化合物、光聚合起始 劑、聚合抑制劑、光穩定劑等）造成不良影響之虞。例 如，若減愿環境之環境愿力過低，則有各成分氣化之虞， =存在為提供減壓環境而耗費時間之情況。減塵環境之環 楗壓力更佳為1〜100Pa，更佳為3〜3〇Pa。 繼而，將藉由真空積層而獲得之積層體前驅物置於環境 屋力較實施真空積層之減㈣境之環境愿力高之第2壓力 環境下(例如大氣麼下)(以下，於本說明書中，存在將該工 156745.doc 201231263 序稱為「減壓環境之解除」之情況）。藉由因減壓環境之 解除引起的環境壓力上升而使一對基板彼此向密接之方向 擠壓，同時殘留於第1硬化性樹脂組合物層中之氣泡之體 積對應於該環境壓力之差壓而縮減，藉此由一對基板與密 封部所密閉之密閉空間整體由第i硬化性樹脂組合物 填充。 二 此處，第2壓力環境較佳為較實施真空積層之減壓環境 之環境壓力高50 kPa，通常為80420 kPa。第2壓力環境可 為大氣壓環境，亦可為更高之壓力。就可於無需特殊之設 備之條件下進行第1硬化性樹脂組合物之硬化等操作之方 面而言，最佳為大氣壓環境。 自疊加一基板與另一基板時直至解除減壓環境為止之時 間並無特別限定，可與密封第丨硬化性樹脂組合物後立即 解除減壓環境，亦可於密封第1硬化性樹脂組合物後維持 減壓狀態特定時間。但是，於此情形時，所維持之減壓狀 態無法降低疊加時之環境壓力。藉由將減壓狀態維持特定 時間第1硬化性樹脂組合物於密閉空間内流動而使一基 板與另-基板間之間隔變得均句；藉由減壓環境之解除， 即便置於較實施真空積層之減壓環境更高之第2壓力環境 下，亦易維持密封狀態。維持減壓狀態之時間可為數小時 以上之較長時間，就生產效率之方面而言較佳為10分鐘以 内’更佳為1分鐘以内。 將積層體前驅物保持於較減壓環境高之第2壓力環境下 時間並無特別限定。將積層體前驅物自減壓裝置中取出 156745.doc •48- 201231263 、轉移至硬化裝置中，於使開始硬化前之製程在大氣壓環 境行之情形時，該製程所需之時間成為保持於第2壓 力環境下之時間。因此，於在置於大氣壓環境下時於密閉 工間内之硬化性樹脂組合物層中已不存在空隙之情形時， 或於在该製程期間硬化性樹脂組合物層中之空隙消失之情 形時，可立即使硬化性樹脂組合物硬化◎於在空隙消失前 需要時間之情形時，將積層體前驅物保持於第2壓力環境 下直至空隙消失。又，即便保持於第2壓力環境下之時間 延長，通常亦不產生故障，因此就製程上之其他必要性而 5 ’亦可將保持於第2壓力環境下之時間延長。 保持於第2壓力環境下之時間可為丨日以上之較長時間， 就生產效率之方面而言，較佳為6小時以内，更佳為丨小時 以内，就進而提高生產效率之方面而言，尤佳為1〇分鐘以 内。 繼而，藉由使密閉空間内之第丨硬化性樹脂組合物硬化 而製造包括一對基板、以及存在於該一對基板間之第1硬 化性樹脂組合物之硬化物之層的積層體。 此處’構成密封部之第2硬化性樹脂組合物可於使密閉 空間内之第1硬化性樹脂組合物硬化時同時硬化，於將積 層前驅物於第2壓力環境下保持較長時間之情形時，為防 止雄閉空間内之第1硬化性樹脂組合物漏出，較佳為於將 積層前驅物置於第2盤力環境下時’預先使構成密封部之 第2硬化性樹脂組合物硬化。其原因如下所述。 如上所述’塗佈後之第2硬化性樹脂組合物具有足夠高 156745.doc -49- 201231263 之黏度’為達成上述密封部之高度減少率，於實施真空積 層時及解除減壓環境時，需要具有一定程度之黏性。 另一方面，於將藉由本發明之方法而製造之積層體用作 FPD之前面板之情形時，為獲得圖像顯示面，要求密封部 形成為寬度相對於其高度較小之形狀，即使密封部之剖面 形狀之高度/寬度之比較大。 然而’由於對於來自橫方向之負重，此種形狀之密封部 變得脆弱’故而於將積層前驅物於第2壓力環境下保持較 長時間之情形時，有密閉空間内之第1硬化性樹脂組合物 漏出之虞。 於將積層前驅物置於第2壓力環境下時，若預先形成使 構成密封部之第2硬化性樹脂組合物硬化而不具有黏性之 狀態，則對於來自橫方向之負重，密封部具有充分之強 度故而即便於將積層前驅物於第2壓力環境下保持較長 時間之情形時，密閉空間内之第！硬化性樹脂组合物亦不 漏出。 於本發明之方法中，將積層前驅物置於第2壓力環境下 後的密封部之寬度為〇 8〜3 〇 mm，且該密封部之剖面形狀 之咼度/寬度之比為〇 05H。 於本發明之方法中，將積層前驅物置於第2壓力環境下 後的密封部之寬度為12〜2 mm，且該密封部之剖面形狀之 高度/寬度之比較佳為〇 .1 〜0.4。 使第1、第2硬化性樹脂組合物硬化之手段係對應於該等 硬化性樹脂組合物之種類而使用熱硬化或光硬化任一者。 156745.doc -50· 201231263 但是，如上所述，使用之硬化性樹脂組合物較佳為光硬化 性樹脂組合物。 於為光硬化性樹脂組合物之情形時，例如自光源（紫外 線燈、高壓水銀燈等）照射紫外線或短波長之可見光而使 該光硬化性樹脂組合物硬化，藉此製造包括—對基板、以 及存在於該一對基板間之第i硬化性樹脂組合物之硬化物 之層的積層體。 光係自-對基板中透明基板之側照射。於兩者均為透明 基板之情形時，可自兩侧照射。 於所製造之積層體為平板顯示器（FPD)之 板顔示器使用透過㈣示元件之情料，可 進行動作而獲得透光性，於未進行動作之狀態下，不具有 透光性者較多’故而自成為保護板之透明基板照射使光硬 化性樹脂組合物硬化之光H面，於使用在該平板顯 示器未進行動作時表現透明狀態之透過·散射型顯示元件 之凊$時，亦可利用來自顯示元件側之光。 作為光，較佳為紫外線或450 nm以下之可見光。尤其是 於在透明基板上設置抗反射層且抗反射層或用以形成抗反 射層之樹脂膜不透過紫外線之情形時，必需利用可見光進 行硬化》 藉由本發明之製造方法而獲得之積層體適用於薄層太陽 電池凡件或圖像顯示裝置等。作為薄層太陽電池元件之具 體例’可列舉：薄膜矽太陽電池元件、黃銅礦系或CdTe系 等化合物半導體太陽電池元件等。另-方面，作為圖像顯 156745.doc •51- 201231263 示裝置之具體例’可列舉：&amp;晶顯示裝置(LCD)、有機EL 或無機EL等EL(電致發光）顯示裝置、電漿顯示裝置 '電子 油墨型圖像顯示裝置等平板顯示器（FPD)。 於為薄層太陽電池元件之情形時，可僅於構成積層體之 對基板中之-基板上形成薄層太陽電池元件，亦可於兩 基板上形成薄層太陽電池元件。 [實施例] 以下，基於實施例更具體地說明本發明。但本發明並不 限定於此。再者，例丨、例3、例4、例5、例8、例1〇為實 施例’其他例為比較例。 (例1) 於例1中，按照以下工序製備第2硬化性樹脂組合物。 將利用環氧乙烷使分子末端改性之2官能聚丙二醇（由羥 值算出之數量平均分子量：4〇〇〇)與六亞甲基二異氰酸酯 以6比7之莫耳比混合，繼而利用丙烯酸異冰片酯（大阪有 機化學工業公司製造，ΙΒχΑ)加以稀釋後，於錫化物觸媒 之存在下使其反應而獲得預聚物，於該預聚物中以大致1 比2之莫耳比添加丙烯酸2_羥基乙酯使其反應，藉此獲得 以30質里〇/〇之丙浠酸異冰片酯稀釋之丙烯酸胺基甲酸酯寡 聚物（以下記作UC-1)溶液。ucji硬化性基數為2，數量 平均分子量約為55000。UC-1溶液於60°C下之黏度約為580The actual shot was confirmed by visual inspection; the shape of the seal portion after the accumulation of the layer of _# Q was not caused to the inside of the corner portion. However, after the implementation of the direct operation &amp; a μ . . . two layers, it is confirmed that the Srtii first curable resin composition protrudes from the portion where the width of the sealing portion is thinned. In addition, the step of applying the second curable resin composition so that the coating width of the second curable resin composition in the vicinity of the corner portion of the sealing portion is thinner than the other coating width of the sealing portion is shown in the following. In the method for producing a laminate according to the present invention, it is necessary to fix the height of the sealing portion, and it is necessary to fix the coating height of the second curable resin composition. When the coating height of the second curable resin composition is fixed, the change in the coating amount of the second curable resin composition is directly related to the coating width of the second curable resin composition. Here, when the amount of the second curable resin composition is ejected from a discharge mechanism such as a dispenser, the amount of the second curable resin composition is changed, whereby the second curable resin composition can be changed. Coating width. Therefore, by making the discharge amount of the second curable resin composition in the vicinity of the corner portion of the sealing portion smaller than the other coating width of the sealing portion, the coating width in the vicinity of the corner portion of the sealing portion can be made thinner than the sealing portion t. The cloth width is fine. In the case where the discharge amount of the second curable resin composition is increased from the discharge mechanism such as the dispenser, when the moving speed of the discharge mechanism is changed, the coating amount of the second curable resin composition changes. This can change the coating width of the second curable resin composition. By &amp;, the moving speed of the discharge mechanism in the vicinity of the corner portion of the sealing portion is faster than the other coating width of the sealing portion, 156745.doc •45·201231263 The second curable resin composition can be placed in the sealing portion The coating width near the corner portion is thinner than the other coating width of the sealing portion. In the method for producing a laminate according to the present invention, the vacuum laminate can be applied in the following steps. In the following description, the substrate on the side where the sealing portion and the layer of the first curable resin composition are formed on the pair of substrates is referred to as a substrate, and the substrate on the surface on which the side is not formed is referred to as a substrate. Another substrate. A substrate is placed in a decompression device, and the substrate is placed horizontally on the fixed support disk in the decompression device with the first curable resin composition facing upward. A moving branch mechanism that is movable in the up and down direction is disposed in the upper portion of the pressure reducing device, and another substrate is mounted on the moving support mechanism. Here, in the case where a thin film solar cell element is formed on the surface of another substrate, the surface on the side on which the thin film solar cell element is formed faces downward β, and the use in the laminated body is a flat panel display (FPD). In this case, the face on the outer side of the article is placed face down. Further, when the antireflection layer is provided on the surface of the other substrate, the surface on the side where the antireflection layer is not formed is faced downward. The other substrate is located above a substrate and is not in contact with the second hard curable resin composition. That is, the tantalum-curable resin composition on the surface of one substrate is opposed to the other substrate without being in contact with each other. Further, a moving support mechanism movable in the up and down direction is disposed in the lower portion of the decompression device, and a substrate may be disposed on the moving support mechanism. In this case, the other substrate is mounted on a fixed support disk provided on the upper portion of the pressure reducing device so that one substrate faces the other substrate. 156745.doc -46- 201231263 Further, the substrate and the other substrate may be supported by a mechanism provided in the decompression device, and the substrate and the other substrate may be disposed at a specific position. The interior of the pressure device is decompressed to form a specific reduced pressure environment. If possible, a substrate and another substrate may be placed in a specific position in the decompression device during a decompression operation or after a specific reduced pressure environment is formed. After the inside of the decompression device becomes a specific decompression environment, the other substrate supported by the moving labeling mechanism is moved downward, and the other substrate is superposed on the first curable resin composition on the surface of one substrate. The i-th hardening resin composition is sealed in a space surrounded by the surface of one substrate, the lower surface of the other substrate, and the sealing portion by superposition. At Manga's expansion by the weight of another substrate, the squeezing from a mobile branching mechanism, etc.! The curable resin composition is filled in the space to fill the first curable resin composition. The environmental pressure of the decompression environment at the time of superposition is 1 〇〇〇pa or less, preferably Pa or more. If the environmental pressure of the environment is too low, there are components (hardening compounds) contained in the curable resin composition. , photopolymerization initiators, polymerization inhibitors, light stabilizers, etc.) cause adverse effects. For example, if the environment of the environment for reducing the willingness is too low, there will be a problem of gasification of each component. = There is a time-consuming situation for providing a decompression environment. The ring of the dust-reducing environment is preferably 1 to 100 Pa, more preferably 3 to 3 Pa. Then, the laminated body precursor obtained by the vacuum lamination is placed in the second pressure environment (for example, the atmosphere) where the environmental power is higher than the environment in which the vacuum layer is reduced (for example, in the atmosphere) (hereinafter, in the present specification) There is a case where the 156745.doc 201231263 is referred to as "the release of the decompression environment". By pressing the pair of substrates in a direction in which the pressure is increased due to an increase in the environmental pressure due to the release of the reduced pressure environment, the volume of the bubbles remaining in the first curable resin composition layer corresponds to the difference in pressure of the ambient pressure. By the reduction, the entire sealed space in which the pair of substrates and the sealing portion are sealed is filled with the i-th curable resin composition. Second, the second pressure environment is preferably 50 kPa higher than the ambient pressure of the reduced pressure environment in which the vacuum buildup is performed, and is usually 80,420 kPa. The second pressure environment can be an atmospheric pressure environment or a higher pressure. It is preferable to carry out an operation such as hardening of the first curable resin composition without special equipment, and it is preferably an atmospheric pressure environment. The time from the time when the one substrate and the other substrate are superposed until the pressure-reducing environment is released is not particularly limited, and the pressure-reducing environment can be released immediately after the sealing of the second curing resin composition, and the first curable resin composition can be sealed. After the decompression state is maintained for a specific time. However, in this case, the maintained decompression state cannot reduce the environmental stress at the time of superposition. By maintaining the reduced pressure state for a predetermined period of time, the first curable resin composition flows in the sealed space, thereby making the interval between one substrate and the other substrate uniform; by the release of the reduced pressure environment, even if it is placed In the second pressure environment where the vacuum layer has a higher pressure reducing environment, it is also easy to maintain the sealed state. The time for maintaining the reduced pressure state may be a long time of several hours or more, and it is preferably within 10 minutes in terms of production efficiency, and more preferably within 1 minute. The time during which the laminated body precursor is maintained in the second pressure environment higher than the reduced pressure environment is not particularly limited. The laminated body precursor is taken out from the decompression device 156745.doc •48- 201231263, and transferred to the hardening device. When the process before the hardening starts is performed in an atmospheric environment, the time required for the process becomes the same. 2 Time under pressure environment. Therefore, when there is no void in the curable resin composition layer in the closed working chamber when placed under an atmospheric pressure environment, or when the void in the curable resin composition layer disappears during the process, The curable resin composition can be immediately cured. When the time is required before the void disappears, the laminate precursor is held in the second pressure environment until the void disappears. Further, even if the time remaining in the second pressure environment is prolonged, no malfunction is usually caused. Therefore, the time required to maintain the second pressure environment can be extended for other necessity in the process. The time to be maintained in the second pressure environment may be longer than the next day, and in terms of production efficiency, it is preferably within 6 hours, more preferably within a few hours, thereby improving productivity. , especially for less than 1 minute. Then, a layered body including a pair of substrates and a layer of a cured product of the first hard resin composition existing between the pair of substrates is produced by curing the ninth curable resin composition in the sealed space. Here, the second curable resin composition constituting the sealing portion can be simultaneously hardened when the first curable resin composition in the sealed space is cured, and the laminated precursor can be kept in the second pressure environment for a long period of time. In order to prevent leakage of the first curable resin composition in the male closed space, it is preferable to cure the second curable resin composition constituting the sealing portion in advance when the laminated precursor is placed in the second disk force environment. The reason is as follows. As described above, the 'viscosity of the second curable resin composition after coating is sufficiently high 156745.doc -49 - 201231263' to achieve the height reduction rate of the sealing portion, when vacuum lamination is performed, and when the decompression environment is released, Need to have a certain degree of stickiness. On the other hand, in the case where the laminated body manufactured by the method of the present invention is used as a front panel of the FPD, in order to obtain an image display surface, it is required that the sealing portion be formed into a shape having a smaller width with respect to its height even if the sealing portion The height/width of the cross-sectional shape is relatively large. However, when the seal portion of such a shape becomes weak with respect to the load from the lateral direction, when the laminated precursor is held in the second pressure environment for a long period of time, the first curable resin in the sealed space is present. The composition leaked out. When the laminated precursor is placed in the second pressure environment, if the second curable resin composition constituting the sealing portion is cured in a state in which it is not viscous, the sealing portion is sufficient for the load from the lateral direction. Intensity, even if the laminated precursor is kept in the second pressure environment for a long time, the first in the confined space! The curable resin composition also does not leak. In the method of the present invention, the width of the sealing portion after the laminated precursor is placed in the second pressure environment is 〇 8 to 3 〇 mm, and the ratio of the width/width of the cross-sectional shape of the sealing portion is 〇 05H. In the method of the present invention, the width of the sealing portion after the laminated precursor is placed in the second pressure environment is 12 to 2 mm, and the height/width of the cross-sectional shape of the sealing portion is preferably 〇1 to 0.4. The means for curing the first and second curable resin compositions is either thermosetting or photocuring depending on the type of the curable resin composition. 156745.doc -50· 201231263 However, as described above, the curable resin composition to be used is preferably a photocurable resin composition. In the case of a photocurable resin composition, for example, a light source (ultraviolet lamp, high pressure mercury lamp, or the like) is irradiated with ultraviolet light or short-wavelength visible light to harden the photocurable resin composition, thereby manufacturing a substrate including the pair, and A layered body of a layer of a cured product of the i-th curable resin composition between the pair of substrates. The light system is irradiated from the side of the transparent substrate in the substrate. When both are transparent substrates, they can be illuminated from both sides. In the case where the laminated body manufactured by the flat panel display (FPD) is used as a display device, the device can be operated to obtain light transmittance, and in the case where the operation is not performed, the light transmittance is not improved. In many cases, the transparent substrate which serves as the protective sheet is irradiated with the light H surface which cures the photocurable resin composition, and when the translucent/scattering type display element which exhibits a transparent state when the flat panel display is not operated is used, Light from the side of the display element can be utilized. As the light, ultraviolet light or visible light of 450 nm or less is preferable. In particular, when an antireflection layer is provided on a transparent substrate and the antireflection layer or the resin film for forming the antireflection layer does not transmit ultraviolet rays, it is necessary to use visible light for hardening. The laminate obtained by the production method of the present invention is suitable. For thin-film solar cells or image display devices. Examples of the thin-film solar cell element include a compound semiconductor solar cell element such as a thin film germanium solar cell element, a chalcopyrite system, or a CdTe system. On the other hand, as a specific example of the image display device 156745.doc • 51-201231263, an EL (electroluminescence) display device such as a crystal display device (LCD), an organic EL or an inorganic EL, or a plasma can be cited. A flat panel display (FPD) such as an electronic ink type image display device. In the case of a thin-film solar cell element, a thin-film solar cell element may be formed only on the substrate in the pair of substrates constituting the laminate, and a thin-film solar cell element may be formed on both substrates. [Examples] Hereinafter, the present invention will be more specifically described based on examples. However, the present invention is not limited to this. Further, Examples, Examples 3, 4, 5, 8 and 1 are examples. Other examples are comparative examples. (Example 1) In Example 1, the second curable resin composition was prepared in the following procedure. The bifunctional polypropylene glycol (the number average molecular weight calculated from the hydroxyl value: 4 Å) modified with ethylene oxide at the molecular end is mixed with hexamethylene diisocyanate at a molar ratio of 6 to 7, and then utilized. Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) is diluted, and then reacted in the presence of a tin catalyst to obtain a prepolymer having a molar ratio of approximately 1 to 2 in the prepolymer. The reaction was carried out by adding 2-hydroxyethyl acrylate to obtain a solution of an urethane urethane oligomer (hereinafter referred to as UC-1) diluted with 30 mg of yttrium/anthracene acetonate. The ucji has a hardening base of 2 and a number average molecular weight of about 55,000. The viscosity of UC-1 solution at 60 ° C is about 580

Pa.s。 將90質量份之UC-1溶液及10質量份之甲基丙烯酸2_羥基 丁醋（共榮社化學公司製造，LIGHTESTER HOB)均勻地混 156745.doc -52- 201231263 合而獲得混合物。將1 〇〇質量份之該混合物、1質量份之1 -羥基-環己基-苯基-酮（光聚合起始劑’汽巴精化公司製 造，IRGACURE 184)、0.1質量份之雙（2,4,6-三曱基笨曱醯 基）-苯基氧化膦（光聚合起始劑’汽巴精化公司製造’ IRGACURE 819)、0.04質量份之2,5-二-第三丁基對苯二酚 (聚合抑制劑）、及0.3質量份之紫外線吸收劑（汽巴精化公 司製造，TINUVIN 109)均勻地混合，而獲得光硬化性樹脂 組合物（第2)。 將光硬化性樹脂組合物（第2)放入容器中，並於開放狀 態下置於減壓裝置内，將減壓裝置内減壓至約20 Pa並保 持1 〇分鐘，藉此進行脫泡處理。對光硬化性樹脂組合物 (第2)於25°C下之黏度進行測定，結果約為1400 Pa.s。 STEP1 準備長度500 mm、寬度800 mm、厚度3 mm之納妈玻璃 製基板（以下稱為基板A)，使用分注器於該基板之塗佈硬 化性樹脂組合物之面之中央部之480x600 mm之區域的外 周部塗佈光硬化性樹脂組合物（第2)而形成密封部。 此處’分注器係使用具有内徑為1 mm之喷嘴者，將基 板A與喷嘴頂端之間隔設為〇8 mm，以〇84 之喷出 量、2 m/min之喷嘴移動速度進行光硬化性樹脂組合物（第 2)之塗佈。 STEP2 於由STEP 1中形成之密封部所包圍之區域_，以間隔均 等之方式’花費約U)秒鐘’使用分注器分散滴加1536滴以 156745.doc -53- 201231263 下述工序製備之光硬化性樹脂組合物（第1)121 g(以形成於 密封部所包圍之區域之光硬化性樹脂組合物（第1)之層的厚 度計’相當於0.4 mm)。 [光硬化性樹脂組合物（第1)之製備] 將利用環氧乙烷使分子末端改性之2官能基聚丙二醇（由 羥值算出之數量平均分子量：4000)與異佛爾酮二異氰酸 酯以4比5之莫耳比混合並於錫化物觸媒之存在下、在7 〇 下進行反應而獲得預聚物，於該預聚物中以大致1比2之莫 耳比添加丙烯酸2-羥基乙酯並於7〇°C下進行反應，藉此獲 得丙烯酸胺基甲酸酯寡聚物（以下記作UA-1)。UA-1硬化性 基數為2’數量平均分子量約為24000，25 °C下之黏度約為 830 Pa*s。 40質量份之UA-1、20質量份之甲基丙烯酸2-羥基丁酯 (共榮社化學公司製造，LIGHTESTER HOB)、40質量份之 甲基丙烯酸正十二烷基酯均勻混合，使〇 3質量份之雙 (2,4,6-三甲基苯甲醯基）_苯基氧化膦（光聚合起始劑，汽巴 精化公司製造’ IRGACURE 819)、0_04質量份之2,5-二-第 三丁基對苯二酚（聚合抑制劑，東京化成公司製造）、〇·5質 量份之正十二烷基硫醇（鏈轉移劑，花王公司製造、 THIOKALCOL 20)、0.3質量份之紫外線吸收劑（汽巴精化 公司製造，TINUVIN 109)於1〇〇質量份之上述混合物中均 勻溶解，而獲得光硬化性樹脂組合物（第丨）。 將上述光硬化性樹脂組合物（第丨）放入容器中並於開放 狀態下置於減壓裝置内，將減壓裝置内減壓至約20 Pa並 156745.doc •54- 201231263 保持ι〇分鐘，藉此進行脫泡處理。對光硬化性樹脂組合物 (第1)於25 c下之黏度進行測定，結果約為丨7 Pa,s。 STEP3 於分散滴加光硬化性樹脂組合物（第丨）後，於壓力為Μ Pa之減壓容器内，以硬化性樹脂組合物介於基板間之方 式，對於基板A疊加將於與光硬化性樹脂組合物（第〇接觸 之面具有自身黏著性之厚度為〇·〇75爪爪之隔離膜（T〇hceli〇 公司製造，PURETECT VLH_9)貼合於板面上的相同形狀 且相同厚度的鈉鈣玻璃板（以下稱為基板B)，藉此實施真 空積層後，藉由將減壓容器内之壓力恢復至大氣壓而解除 減壓環境，其後立即自基板B之面方向以該基板B表面之 365 nm之照度成為2 mW/cm2之方式照射紫外線1〇分鐘， 而使光硬化性樹脂組合物（第1、第2)硬化。 STEP4 於僅將基板B自隔離膜剝離後，將隔離膜自樹脂層剝 離’藉由KEYENCE公司製造之雷射位移計LK_G8〇對存在 於基板A上之樹脂層更具體而言存在於密封部所包圍之區 域中之樹脂層之厚度的偏差進行測定。 其結果’樹脂層之厚度之偏差約為0 05 mm，為無產生 光學應變等問題之虞的水平。 (例2) 於例2中，除不實施STEP 1之方面以外實施與例1相同之 工序。 以與例1相同之工序對樹脂層之厚度之偏差進行測定， 156745.doc -55- 201231263 結果樹脂層之厚度之偏差約為〇·1 mm，為有產生光學應變 等問題之虞的水平。 (例3) 於例3中，準備長度1 〇〇 mrn、寬度100 mm、厚度3 mm 之鈉鈣玻璃製基板（以下稱為基板C)，使用分注器於基板C 之中央部75 X 75 mm之區域之外周部塗佈光硬化性樹脂組 合物（第2)而形成密封部。 此處’分注器係使用具有内徑為1 ·〇6 mm之喷嘴者，將 基板C與喷嘴頂端之間隔設為mm，以8.8 mg/cm之喷出 量進行光硬化性樹脂組合物（第2)之塗佈。 對在封部之寬度之經時變化進行測定，即便於自形成密 封部起經過300秒後’密封部之寬度亦未超過2111111。 以與上述相同之工序於該基板亡上形成密封部後，於密 封部所包圍之區域，以間隔均等之方式，使用分注器分散 滴加光硬化性樹脂組合物（第ιμ92.3 g(以形成於密封部所 包圍之區域的光硬化性樹脂組合物（第丨）之層的厚度計相當 於 0.4 mm)。 於分散滴加光硬化性樹脂組合物（第1}後，在壓力為ι〇 Pa之減壓容器内’以硬化性樹脂組合物介於基板間之方 式，對基板C疊加相同形&amp;且相同厚度之納弼玻璃板（以下 稱為基板D)，藉此實施真空積層&amp;，藉由將減遷容器内之 壓力恢復至大氣壓而解除減壓環境。 於解除減壓環境後，以目視對存在於密封部所包圍之區 域的樹脂層進行確認，結果於樹脂層中未見空隙。 156745.doc •56- 201231263 又，將解除減壓環境後之積層體傾斜約2〇。之角度並保 持’對基板D自積層體滑落7,5 mm之時間進行測量，結果 約為60秒’為於實線之使用上無問題之保持力。因此，可 〜為存在於&amp;封部所包圍之區域之樹脂層之厚度的偏差為 與例1相同之程度。 (例4) 於例4中’使用25 C下之黏度為950 Pa.s之光硬化性樹脂 組合物（第2')。 按照以下之工序製備光硬化性樹脂組合物（第2，）。 將用以製備光硬化性樹脂組合物（第2)的86質量份之丙 烯酸胺基甲酸@旨募聚物溶液（uc_imi4f量份之曱基丙稀 酸2-羥基丁酯（共榮社化學公司製造，ughtester h〇b) 均勻混合而獲得混合物。將1〇〇質量份之該混合物、3質量 伤之1輕基-環己基-苯基__(光聚合起始劑，汽巴精化公 司製造，IRGACURE 184)、〇.1質量份之雙（2,4,6-三曱基苯 甲醯基)-苯基氧化膦(光聚合起始劑，汽巴精化公司製造， IRGACURE 819)均勻混合而獲得光硬化性樹脂組合物（第 2丨）。 將光硬化性樹脂組合物（第21)放入容器中並於開放狀態 下置於減壓裝置内，將減壓裝置内減壓至約2〇 pa並保持 10分鐘，藉此進行脫泡處理。對光硬化性樹脂組合物（第 21)於25C下之黏度進行測定，結果約為95〇pa,s。 以與例3相同之工序實施光硬化性樹脂組合物（第2ι)之塗 佈°藉由於塗佈完成6〇秒後利用紫外線（uv)照射使光硬化 156745.doc •57- 201231263 性樹脂組合物（第2，)半硬化而形成密封部。紫外線照射係 使用基板表面之365 nm之照度為2 mW/cm2的υν·光機， 於該υν曝光機中’花費30秒鐘自基板之單面進行uV照 射。 再者，求出於與上述相js)之條件下實施υν照射之光硬 化性樹脂組合物（第2，)之膠體率作為半硬化之基準，結果 約為55%，未進行半硬化之光硬化性樹脂組合物（第2,)之膠 體率為5。/。以下。膠體率係選取〇4 g經半硬化之光硬化性 樹脂組合物（第2·)，於100 mL之曱苯中在25t：下浸潰以小 時後，滤出甲$，於UHTC下使殘留固形物成分乾燥 時，對乾燥質量進行測定並根據下式而算出。 膠體率（％)=浸潰後之乾燥質量（g)/0 4(g)xl()〇。 又，測定自塗佈60秒後起120秒鐘之塗佈線寬之擴展作 為由半硬化引起之減的上升基準，與未進行半硬化者相 比’結果其擴展約為50%。 自UV照射完成90秒後起測定密封部之寬度之經時變 化，即便UV照射完成300秒後，密封部之寬度亦未超過2 mm ° 於以與上述相同之工序於該基板C上形成密封部後，在 密封部所包圍之區域，以間隔均等之方式，使用分注器分 散滴加光硬化性樹脂組合物（第υ約2 3 g(以形成於密封部 所包圍之區域之光硬化性樹脂組合物（第υ之層的厚度計相 當於0.4 mm)。 於分散滴加光硬化性樹脂組合物（第”後，於壓力1〇 &amp; I56745.doc -58· 201231263 之減壓容器内，以硬化性樹脂組合物介於基板間之方式， 對基板c積層相同形狀且相同厚度之鈉鈣玻璃板（以下稱為 基板D)，藉此實施真空積層後，藉由將減壓容器内之壓力 恢復至大氣壓而解除減壓環境。 於解除減壓環境後，以目視確認存在於密封部所包圍之 區域之樹脂層’結果於樹脂層中未見空隙。 又，將解除減壓環境後之積層體傾斜約2〇。之角度並保 持，對基板D滑落7.5 mm之時間進行測量，結果約為6〇 秒，為於實線之使用上無問題之保持力。因此，可認為存 在於密封部所包圍之區域之樹脂層之厚度的偏差為與例丄 相同之程度。 (例5) 於例5中，藉由於塗佈光硬化性樹脂組合物（第後立即 進行紫外線照射而使光硬化性樹脂組合物（第2,)半硬化， 於本例中，使用基板表面之365 nm之照度為4500 mW/cm2 的uv曝光機，對塗佈光硬化性樹脂組合物（第2)之部位分 別聚光照射紫外線10秒鐘。測定自塗佈6〇秒後起12〇秒鐘 之塗佈線寬之擴展作為由半硬化引起之黏度上升之基準， 並與未半硬化者進行比較，結果該擴展為5〇%以下。 自UV照射完成9〇秒後起測定密封部之寬度之經時變 化，即便UV照射完成3〇〇秒後，密封部之寬度亦未超過2 (例6) 於例6中’使用25°C下之黏度為660 Pa*s的光硬化性樹脂 156745.doc -59· 201231263 組合物（第2&quot;)，除此以外實施與例2相同之工序而於基板上 形成密封部。 按照以下之工序製備光硬化性樹脂組合物（第2”）。 用以製備光硬化性樹脂組合物（第2)的81質量份之丙稀 酸胺基甲酸酯寡聚物溶液（UC-1)及19質量份之甲基丙烯酸 2_羥基丁酯（共榮社化學公司製造，LIGHTESTER HOB)均 勻混合而獲得混合物》將1 00質量份之該混合物、3質量份 之1-羥基-環己基-苯基-酮（光聚合起始劑，汽巴精化公司 製造，IRGACURE 184)、0.1質量份之雙（2,4,6-三曱基苯曱 醯基）-苯基氧化膦（光聚合起始劑，汽巴精化公司製造， IRGACURE 819)均勻混合’而獲得光硬化性樹脂組合物 (第 2&quot;)。 將光硬化性樹脂組合物（第2&quot;)放入容器中並於開放狀態 下置於減壓裝置内，將減壓裝置内減壓至約20 Pa並保持 1 〇分鐘’藉此實施脫泡處理。測定光硬化性樹脂組合物 (第2&quot;)於25°C下之黏度，結果約為660 Pa*s。 測定密封部之寬度之經時變化，即便自形成密封部起 300秒後’密封部之寬度亦未超過2 mm。 以與例3相同之工序實施光硬化性樹脂組合物（第1)之分 散滴加、真空積層、及減壓環境之解除。 於解除減壓環境後，以目視確認存在於密封部所包圍之 區域之樹脂層，結果於樹脂層中未見空隙。 將解除減壓環境後之積層體傾斜約2〇。之角度並保持， 測定基板D滑落7.5 mm之時間，結果約為5〇秒，為於實線 156745.doc •60- 201231263 之使用上不充分之保持力。因此，可認為存在於密封部所 包圍之區域之樹脂層之厚度的偏差為與例2相同之程度。 (例7) 於例7中’使用25°C下之黏度為460 Pa.s之光硬化性樹脂 組合物（第2&quot;’），除此以外實施與例2相同之工序而於基板上 形成密封部。 按照以下之工序製備光硬化性樹脂組合物（第2&quot;,)。 將用以製備光硬化性樹脂組合物（第2)的8〇質量份之丙 烯酸胺基曱酸酯寡聚物溶液（UC4)及2〇質量份之甲基丙婦 酸羥基丁酯（共榮社化學公司製造，lightester η〇β) 均勻混合而獲得混合物。將1〇〇質量份之該混合物、3質量 伤之1 -羥基-環己基-苯基-酮（光聚合起始劑，汽巴精化公 司製造，IRGACURE 184)、〇· 1質量份之雙（2,4,6-三甲基笨 甲醯基）-苯基氧化膦（光聚合起始劑，汽巴精化公司製造， IRGACURE 819)均勻混合，而獲得光硬化性樹脂組合物 (第 2，，，）。 將光硬化性樹脂組合物（第2&quot;,)放入容器中並於開放狀態 下置於減壓裝置内，將減壓裝置内減壓至約20 Pa並保持 1〇分鐘，藉此進行脫泡處理。測定光硬化性樹脂組合物 (第2’&quot;)於25°C下之黏度，結果約為46〇 pa.s。 自光硬化性樹脂組合物（第2,)之塗佈完成9 〇秒後起測定 狁封邛之寬度之經時變化，結果於塗佈完成3〇〇秒後之時 刻密封部之寬度約成為2.3 mm。 以與例3相同之工序實施光硬化性樹脂組合物（第1)之分 156745.doc 201231263 散滴加、真空積層、及減壓環境之解除。 於解除減壓環境後，以目視確認存在於密封部所包圍之 區域的樹脂層，結果於樹脂層中未見空隙。 (例8) 於例8中，準備長度1〇〇 mm、寬度1〇〇 mm、厚度3 之鈉鈣玻璃製基板（以下稱為基板E)，使用分注器於基板E 之中央部50x50 mm之區域的外周部塗佈光硬化性樹脂組 合物（第2)而形成密封部。 此處，为/主器係使用具有内徑為1 ·〇6 mm之喷嘴者，將 基板E與喷嘴頂端之間隔設為〇8 mm，以66 mg/cm之喷出 量進行光硬化性樹脂組合物（第2)之塗佈。 以與上述相同之工序於該基板E上形成密封部後，於密 封部所包圍之區域，以間隔均等之方式’使用分注器分散 滴加光硬化性樹脂組合物（第丨广約]」g(以形成於密封部所 包圍之區域之光硬化性樹脂組合物（第1}之層的厚度計相當 於 0.4 mm)。 於分散滴加光硬化性樹脂組合物（第丨）後，於壓力為1〇 Pa之減壓容器内，以硬化性樹脂組合物介於基板間之方 式，對基板E疊加相同形狀且相同厚度之鈉鈣玻璃板（以下 稱為基板F),藉此實施真空積層後，藉由將減壓容器内之 壓力恢復至大氣壓而解除減壓環境。 於將減壓容器内之壓力恢復至大氣壓後，立即於以基板 E、F成為水平之方式配置積層前驅物之狀態下，自該基板 E、F之端面方向，使用基板E、F之端面之395 nm之照度 156745.doc •62- 201231263 為 50 mW/cm2 的 uv-led(製造者名稱：Integration khnology ’機種名稱：LEDZero Pincure)照射紫外線， 藉此使光硬化性樹脂組合物（第2)。 以基板E、F成為水平之方式放置uv照射後之積層前驅 ’纟。果即便放置丨日後’密封部亦未受光硬化性樹脂組 合物（第1)侵蝕而保持密封狀態。 (例9) 於將減壓谷器内之壓力恢復至大氣壓後不藉由uv照射 使光硬化性樹脂組合物（第2)硬化，除此以外實施與例8相 同之工序。 以基板E、F成為水平之方式放置將減壓容器内之壓力恢 復至大氣壓後之積層前驅物，並於放置約3〇分鐘後之時刻 進行確認，結果確認密封部受光硬化性樹脂組合物（第〖）侵 蝕而損害密封狀態，光硬化性樹脂組合物（第丨）自該密封部 漏出。 (例 10) 準備長度610 mm、寬度610 mm、厚度3 mm之鈉鈣玻璃 製之基板（以下稱為基板G)，使用分注器沿著自基板g之端 面5 mm之内側加熱塗佈（45。(：）光硬化性樹脂組合物（第2”&quot;) 而形成密封部。 此處，光硬化性樹脂組合物（第2&quot;&quot;)於25〇c下之黏度為 12〇0 Pa，s ’係按照以下之工序製備。 將用以製備光硬化性樹脂組合物（第2)的88質量份之丙 烯酸胺基甲酸酯寡聚物溶液（UC-1)及12質量份之曱基丙烯 156745.doc • 63 - 201231263 酸2_經基丁酯（共榮社化學公司製造，LIGHTESTEr HOB) 均句混合而獲得混合物。將丨00質量份之該混合物、3質量 份之1-羥基-環己基-苯基·酮（光聚合起始劑，汽巴精化公 司製造，IRGACURE 184)、〇·ι質量份之雙（2,4,6-三甲基苯 甲醯基）-苯基氧化膦（光聚合起始劑，汽巴精化公司製造， IRGACURE 819)均勻混合’而獲得光硬化性樹脂組合物 (第 2，。 將光硬化性樹脂組合物（第2&quot;，，)放入容器中並於開放狀態 下置於減壓裝置内，將減壓裝置内減壓至約2〇 pa並保持 10分鐘，藉此進行脫泡處理。測定光硬化性樹脂組合物 (第2&quot;&quot;)於25 c下之黏度’結果約為1200 Pa«s。 又’为/主器係使用具有内徑為1 〇6 mm之喷嘴者，將基 板E與喷嘴頂端之間隔設為〇 8 mm，以〇 u cc(6 6 之喷出量進行光硬化性樹脂組合物（第2”&quot;)之塗佈。再者， 加熱塗佈時之光硬化性樹脂組合物（第2&quot;&quot;)之黏度為2〇〇 Pa.s。 繼而，於密封部所包圍之區域，以間隔均等（滴加間 距：15 mm)之方式並以塗佈後之光硬化性樹脂組合物（第 1)之層厚成為0.4 mm之方式使用分注器分散滴加光硬化性 樹脂組合物（第1)。 於分散滴加光硬化性樹脂組合物（第丨）後，於壓力為1 〇 Pa之減壓容器内，以硬化性樹脂組合物介於基板間之方式 對基板G疊加相同形狀且相同厚度之鈉鈣玻璃板（以下稱為 基板H)，藉此實施真空積層後，藉由將減壓容器内之壓力 I56745.doc -64- 201231263 恢復至大氣壓而解除減壓環境。 此處’貫施真空積層時之密封部之高度、及解除減壓環 境後之密封部之高度分別如下所述。 實施真空積層時之密封部之高度：0.8 mm 解除減壓環境後之密封部之高度：0.4 mm 因此，密封部之高度減少率為0.8/0.4=2。 對自解除減壓環境起10分鐘後之積層前驅物，以目視確 認於硬化性樹脂組合物（第丨）之層上有無投影面積直徑為$ 〇 μιη以上之空隙。 其結果’未見投影面積直徑為5 〇 μχη以上之空隙。 (例 11) 藉由改變來自喷嘴之光硬化性樹脂組合物（第2 '，·，）而將實 施真卫積層時之密封部之高度設為2 ·丨mm，除此以外實施 與例10相同之工序。 达、封部之高度減少率為2 1/〇 4 = 5 25。 對自解除減壓環境起1〇分鐘後之積層前驅物，以目視確 認於硬化性樹脂組合物（第1)之層上有無投影面積直徑為5〇 μιη以上之空隙。 、。果存在160個投影面積直徑為5〇 μιη以上之空卩审。 (例 12) ?、 又自喷嘴之光硬化性樹脂組合物（第2&quot;&quot;)而將 施真空積層時之密# 封。卩的间度玟為0.4 mm，除此以外實施 與例10相同之工序。 4封部之高度減少率為Q屬4=ι。 156745.doc -65. 201231263 確認於解除減壓環境後之積層前驅物中，光硬化性樹脂 組合物（第1)自密封部漏出。 又參照特定之實施態樣對本發明進行了詳細地說明， 但業者明白可於不脫離本發明之範圍與精神之條件下加入 各種修正或變更。 本申明案係基於2010年6月7日申請之日本專利申請案 2010-129718者，其内容作為參照編入於此。 【圖式簡單說明】 圖1係基板之平面圖，即表示於基板上之周邊部形成有 密封部之狀態之圖。 圖2係表示於將牛頓流體夾持於一對基板間之狀態下以 負重F進行加壓時之壓力分佈的示意圖。 圖3(a)、3(b)、3(c)及3(d)係表示實施真空積層後與解除 減壓環境後之積層前驅物之狀態之示意圖。圖3(甸及3(b) 係表示於實施真空積層後之密封部之高度的減少量大於 2.5之情形時積層體前驅物之狀態之圖，圖3(句係表示實施 真空積層後之狀態之圖，圖3(b)係表示解除減壓環境後之 狀態之圖。圖3(c)及3(d)係表示於實施真空積層後之密封 部之高度的減少量於1.05〜2.5之範圍内之情形時積層體前 驅物之狀態之圖，圖3(c)係表示實施真空積層後之狀態之 圖’圖3(d)係表示解除減壓環境後之狀態之圖。 圖4(a)及4(b)係表示由真空積層之實施引起的密封部之 形狀變化之示意圖’圖4(a)表示實施真空積層前之狀態， 圖4(b)表示實施真空積層後之狀態。 156745.doc • 66 · 201231263 圖5 (a)及（b)係用以對本發明之積層體之製造方法中的第 2硬化性樹脂組合物之塗佈形態之較佳例進行說明的圖， 圖5(a)表示實施真空積層前之狀態，圖5(b)表示實施真空 積層後之狀態。 圖6(a)及（b)係用以對本發明之積層體之製造方法中的第 2硬化性樹脂組合物之塗佈形態之另一較佳例進行說明的 圖，圖6(a)表不實施真空積層前之狀態，圖6(b)表示實施 真空積層後之狀態。 圖7(a)係表示於以固定塗佈寬度塗佈第2硬化性樹脂組合 物之情形時實施真空積層後之密封部之形狀的示意圖，圖 7(b)係密封部之角部之部分擴大圖。 圖8係表示根據第2硬化性樹脂組合物之塗佈形態之較佳 例而塗佈第2硬化性樹脂組合物之情形時之實施真空積層 後之密封部之形狀的示意圖。 【主要元件符號說明】 10、l〇a、l〇b 基板 20 密封部 30 第1硬化性樹脂組合物層 100、200 氣泡 . A 實施真空積詹前之第2硬化性樹脂組 合物之塗佈寬度 B 實施真空積層後之第2硬化性樹脂組 合物之塗佈寬度 C、a 實施真空積層後之密封部向角部之内 156745.doc -67· 201231263 側伸出之部分的寬度 D 於角部附近且使密封部之寬度變細之 部分的距離 E 角部附近之密封部之寬度的最小值 R 牛頓流體之半徑 r 自牛頓流體中心之距離 t、1.5t、6t 密封部20之高度 156745.doc -68-Pa.s. 90 parts by mass of the UC-1 solution and 10 parts by mass of 2-hydroxybutyric acid methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHTESTER HOB) were uniformly mixed to obtain a mixture of 156745.doc -52 - 201231263. 1 part by mass of the mixture, 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator "Ciba Specialty Chemicals Co., Ltd., IRGACURE 184", 0.1 part by mass of double (2) , 4,6-tridecyl adenyl)-phenylphosphine oxide (photopolymerization initiator "Ciba" manufactured by Ciba Specialty Chemicals Co., Ltd." IRGACURE 819), 0.04 parts by mass of 2,5-di-t-butyl Hydroquinone (polymerization inhibitor) and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) were uniformly mixed to obtain a photocurable resin composition (No. 2). The photocurable resin composition (second) was placed in a container, placed in a decompression device in an open state, and decompressed to a pressure of about 20 Pa in the decompression device for 1 Torr. deal with. The viscosity of the photocurable resin composition (2nd) at 25 ° C was measured and found to be about 1400 Pa.s. STEP1 A Naoma glass substrate (hereinafter referred to as a substrate A) having a length of 500 mm, a width of 800 mm, and a thickness of 3 mm is prepared, and a dispenser is used to apply 480 x 600 mm at the center of the surface of the substrate to which the curable resin composition is applied. The outer peripheral portion of the region is coated with a photocurable resin composition (second) to form a sealed portion. Here, the 'dispenser' uses a nozzle having an inner diameter of 1 mm, and the interval between the substrate A and the nozzle tip is set to 〇8 mm, and the light is ejected at a jet velocity of 〇84 and a nozzle moving speed of 2 m/min. Coating of the curable resin composition (second). STEP2 is in the area _ surrounded by the seal formed in STEP 1, 'expends about U) seconds in a uniform interval. 'Distribution 1536 drops are dispensed using a dispenser to 156745.doc -53- 201231263 The photocurable resin composition (first) 121 g (the thickness of the layer of the photocurable resin composition (first) formed in the region surrounded by the sealing portion is equivalent to 0.4 mm). [Preparation of Photocurable Resin Composition (No. 1)] 2-functional polypropylene glycol (number average molecular weight calculated from a hydroxyl value: 4000) and isophorone diisocyanate modified with ethylene oxide The prepolymer is obtained by mixing at a molar ratio of 4 to 5 and reacting at 7 Torr in the presence of a tin catalyst, and adding acrylic acid 2 in the prepolymer at a molar ratio of approximately 1 to 2. The hydroxyethyl ester was reacted at 7 ° C to obtain an urethane acrylate oligomer (hereinafter referred to as UA-1). The UA-1 has a hardening base of 2' number average molecular weight of about 24,000 and a viscosity of about 830 Pa*s at 25 °C. 40 parts by mass of UA-1, 20 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHTESTER HOB), and 40 parts by mass of n-dodecyl methacrylate are uniformly mixed to make 〇 3 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd. ' IRGACURE 819), 0-04 parts by mass, 2,5 -Di-t-butyl hydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), 5 parts by mass of n-dodecyl mercaptan (chain transfer agent, manufactured by Kao Corporation, THIOKALCOL 20), 0.3 mass A UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) was uniformly dissolved in 1 part by mass of the above mixture to obtain a photocurable resin composition (No.). The photocurable resin composition (the third layer) is placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device is reduced to about 20 Pa and 156745.doc • 54 - 201231263 In minutes, the defoaming treatment is performed. The viscosity of the photocurable resin composition (No. 1) at 25 c was measured and found to be about Pa7 Pa,s. STEP3, after dispersing the dropwise addition of the photocurable resin composition (the third layer), in a vacuum vessel having a pressure of Μ Pa, the curable resin composition is interposed between the substrates, and the substrate A is superimposed and photohardened. The resin composition (the separator having the self-adhesiveness of the second contact surface is a separator of the 〇·〇75 claw (manufactured by T〇hceli Co., Ltd., PURETECT VLH_9) is attached to the same shape and the same thickness on the plate surface. The soda lime glass plate (hereinafter referred to as the substrate B) is subjected to vacuum lamination, and then the pressure in the decompression vessel is returned to atmospheric pressure to release the decompression environment, and immediately thereafter, the substrate B is directed from the direction of the substrate B. The 365 nm illuminance of the surface is 2 mW/cm2, and the ultraviolet curable resin composition (first and second) is cured by irradiation for about 1 minute. STEP4 is isolated after only the substrate B is peeled off from the separator. The film was peeled off from the resin layer. The deviation of the thickness of the resin layer present in the region surrounded by the sealing portion was measured by a laser displacement meter LK_G8 manufactured by KEYENCE. Its knot The deviation of the thickness of the resin layer is about 0 mm, which is a level which does not cause problems such as optical strain. (Example 2) In Example 2, the same steps as in Example 1 were carried out except that STEP 1 was not carried out. The deviation of the thickness of the resin layer was measured in the same manner as in Example 1, and the deviation of the thickness of the resin layer was 〇·1 mm, which was a level at which optical strain and the like were caused. (Example 3) In Example 3, a soda lime glass substrate (hereinafter referred to as a substrate C) having a length of 1 〇〇mrn, a width of 100 mm, and a thickness of 3 mm was prepared, and a dispenser was used in the central portion 75 X 75 of the substrate C. The photocurable resin composition (second) is applied to the peripheral portion of the mm region to form a sealing portion. Here, the 'dispenser is a nozzle having an inner diameter of 1 · 〇 6 mm, and the substrate C and the nozzle tip are used. The interval was set to mm, and the photocurable resin composition (second) was applied at a discharge amount of 8.8 mg/cm. The change in the width of the seal portion was measured, even from the formation of the seal portion. After 300 seconds, the width of the seal does not exceed 2111111. It is the same as above. After the sealing portion is formed on the substrate, the photocurable resin composition is dispersed and dropped using a dispenser in a region surrounded by the sealing portion (to be formed in the sealing portion). The thickness of the layer of the photocurable resin composition (the third layer) in the region enclosed is 0.4 mm). After the dispersion of the photocurable resin composition (first), the pressure is ι Pa In the pressure vessel, a vacuum glass layer (hereinafter referred to as a substrate D) of the same shape & and the same thickness is superimposed on the substrate C so that the curable resin composition is interposed between the substrates, thereby performing vacuum lamination & The reduced pressure environment is released by restoring the pressure in the reduced vessel to atmospheric pressure. After the pressure reduction environment was released, the resin layer existing in the region surrounded by the sealing portion was visually confirmed, and as a result, no void was observed in the resin layer. 156745.doc •56- 201231263 In addition, the layered body after releasing the decompression environment is tilted by about 2 〇. From the angle of view, the measurement was carried out for the time when the substrate D was slipped by 7, 5 mm from the laminated body, and the result was about 60 seconds, which was a problem-free retention force in the use of the solid line. Therefore, the variation in the thickness of the resin layer which is present in the region surrounded by the & seal portion is the same as in Example 1. (Example 4) In Example 4, a photocurable resin composition (2') having a viscosity of 950 Pa.s at 25 C was used. The photocurable resin composition (No. 2) was prepared according to the following procedure. 86 parts by mass of an acrylamide-based methacrylic acid solution for the preparation of the photocurable resin composition (second) (u_imi4f parts of mercaptopropionic acid 2-hydroxybutyl ester (Kyoeisha Chemical Co., Ltd.) Manufacture, ughtester h〇b) uniformly mixed to obtain a mixture. 1 〇〇 part by mass of this mixture, 3 mass of 1 light base-cyclohexyl-phenyl _ (photopolymerization initiator, Ciba Specialty Chemicals Co., Ltd. Manufactured, IRGACURE 184), 质量.1 parts by mass of bis(2,4,6-trimercaptobenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819) The photocurable resin composition (No. 2) is obtained by uniformly mixing. The photocurable resin composition (21st) is placed in a container and placed in a decompression device in an open state to decompress the inside of the decompression device. The defoaming treatment was carried out until the temperature was maintained at about 2 〇pa for 10 minutes. The viscosity of the photocurable resin composition (21) at 25 C was measured and found to be about 95 Åpa, s. The step of applying the photocurable resin composition (the second layer) is carried out by ultraviolet (uv) irradiation after 6 seconds of coating completion. Photohardening 156745.doc •57- 201231263 The resin composition (2nd) is semi-hardened to form a sealed portion. The ultraviolet irradiation is performed using a 365ν·光机 having an illuminance of 2 mW/cm 2 at 365 nm on the surface of the substrate. In the υν exposure machine, it took 30 seconds to perform uV irradiation from one side of the substrate. Further, the colloidal rate of the photocurable resin composition (second,) which was subjected to υν irradiation under the conditions of the above-mentioned phase js) was determined. As a result of the semi-hardening, the result was about 55%, and the colloidal ratio of the photocurable resin composition (second) which was not semi-hardened was 5. /. the following. The colloidal rate was selected from 〇4 g of a semi-hardened photocurable resin composition (2nd), and after being immersed in 100 mL of toluene at 25 t: for one hour, the residue was filtered off and the residue was left under UHTC. When the solid content component was dried, the dry mass was measured and calculated according to the following formula. Colloid rate (%) = dry mass after dipping (g) / 0 4 (g) xl () 〇. Further, the extension of the coating line width for 120 seconds from the application of 60 seconds after the coating was measured as a rise criterion by the semi-hardening, and the expansion was about 50% as compared with the case where the semi-hardening was not performed. The change in the width of the sealing portion was measured 90 seconds after the completion of the UV irradiation, and even after the UV irradiation was completed for 300 seconds, the width of the sealing portion did not exceed 2 mm ° to form a seal on the substrate C in the same manner as described above. After the portion, the photocurable resin composition is dispersed and dropped using a dispenser in a region surrounded by the sealing portion (the second light is about 2 g (the photo hardening is formed in the region surrounded by the sealing portion). The resin composition (the thickness of the layer of the second layer corresponds to 0.4 mm). After the dispersion of the photocurable resin composition (the first), the pressure vessel at a pressure of 1 〇 & I56745.doc -58· 201231263 In the inside, a soda lime glass plate (hereinafter referred to as a substrate D) having the same shape and the same thickness is laminated on the substrate c so that the curable resin composition is interposed between the substrates, thereby performing vacuum lamination and then decompressing the container. After the pressure is restored to the atmospheric pressure, the decompression environment is released. After the pressure reduction environment is released, the resin layer present in the region surrounded by the sealing portion is visually confirmed. As a result, no void is observed in the resin layer. After product The layer body is inclined by about 2 〇. The angle is maintained and measured when the substrate D is slid down by 7.5 mm, and the result is about 6 sec., which is a problem-free retention force for use in the solid line. Therefore, it can be considered that it exists in the seal. The variation of the thickness of the resin layer in the region surrounded by the portion is the same as that of the example. (Example 5) In Example 5, the photocurable resin composition was applied (the photocuring was performed immediately after ultraviolet irradiation) The resin composition (second) is semi-cured. In this example, a uv exposure machine having an illuminance of 365 nm on the surface of the substrate of 4,500 mW/cm 2 is used to apply a portion of the photocurable resin composition (second). Each of the ultraviolet rays was irradiated with light for 10 seconds, and the spread of the coating line width measured 12 seconds after the coating for 6 seconds was measured as a reference for the viscosity increase caused by the semi-hardening, and compared with those who were not semi-hardened. The expansion is 5% or less. The change in the width of the sealing portion is measured after 9 seconds from the completion of the UV irradiation, and the width of the sealing portion does not exceed 2 even after the UV irradiation is completed for 3 seconds (Example 6). Example 6 'Using light hardening at 625 Pa*s at 25 ° C In the same manner as in Example 2, a sealing portion was formed on the substrate in the same manner as in Example 2, except that the composition (2nd) was prepared. The photocurable resin composition (second) was prepared by the following procedure. 81 parts by mass of an acrylic urethane oligomer solution (UC-1) and 19 parts by mass of 2-hydroxybutyl methacrylate for preparing a photocurable resin composition (second) LIGHTESTER HOB) is uniformly mixed to obtain a mixture. 100 parts by mass of this mixture, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, Cibafin) Manufactured by the company, IRGACURE 184), 0.1 parts by mass of bis(2,4,6-trimercaptophenyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819) The photocurable resin composition (No. 2 &quot;) was obtained by uniformly mixing '. The photocurable resin composition (2nd &quot;) was placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device was reduced to about 20 Pa for 1 〇 minutes to thereby perform defoaming. deal with. The viscosity of the photocurable resin composition (2nd &quot;) at 25 ° C was measured and found to be about 660 Pa*s. The change in the width of the sealing portion was measured over time, even after 300 seconds from the formation of the sealing portion, the width of the sealing portion did not exceed 2 mm. In the same procedure as in Example 3, the dispersion of the photocurable resin composition (No. 1), the vacuum lamination, and the release of the reduced pressure atmosphere were carried out. After the pressure reduction environment was released, the resin layer existing in the region surrounded by the sealing portion was visually confirmed, and as a result, no void was observed in the resin layer. The layered body after the decompression environment is released is inclined by about 2 。. The angle is maintained and the time for the substrate D to fall by 7.5 mm is measured, and the result is about 5 sec., which is an insufficient retention force in the use of the solid line 156745.doc • 60-201231263. Therefore, it is considered that the variation in the thickness of the resin layer existing in the region surrounded by the sealing portion is the same as in Example 2. (Example 7) In Example 7, except that the photocurable resin composition (2nd &quot; Sealing section. The photocurable resin composition (2nd &quot;,) was prepared according to the following procedures. 8 parts by mass of an acrylamide phthalate oligomer solution (UC4) for preparing a photocurable resin composition (second) and 2 parts by mass of methyl propyl acetophenate hydroxybutyl ester Manufactured by the company, lightester η〇β) is uniformly mixed to obtain a mixture. 1 part by mass of this mixture, 3 mass of 1 -hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 184), 〇·1 part by mass (2,4,6-trimethyl beryllyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) was uniformly mixed to obtain a photocurable resin composition (No. 2,,,). The photocurable resin composition (2nd &quot;) is placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device is reduced to about 20 Pa for 1 minute, thereby performing the removal. Bubble treatment. The viscosity of the photocurable resin composition (2'&quot; at 25 ° C was measured and found to be about 46 〇 pa.s. After the coating of the photocurable resin composition (second) was completed, the change in the width of the crucible was measured after 9 seconds. As a result, the width of the sealing portion became approximately 3 seconds after the coating was completed. 2.3 mm. In the same procedure as in Example 3, the photocurable resin composition (No. 1) was subjected to 156745.doc 201231263. The dropping, the vacuum lamination, and the release of the reduced pressure environment were carried out. After the pressure-reducing environment was released, the resin layer existing in the region surrounded by the sealing portion was visually confirmed, and as a result, no void was observed in the resin layer. (Example 8) In Example 8, a soda lime glass substrate (hereinafter referred to as a substrate E) having a length of 1 mm, a width of 1 mm, and a thickness of 3 was prepared, and a dispenser was used in the central portion of the substrate E 50 x 50 mm. The outer peripheral portion of the region is coated with a photocurable resin composition (second) to form a sealed portion. Here, for the main unit, a nozzle having an inner diameter of 1 · 〇 6 mm is used, and the distance between the substrate E and the nozzle tip is set to 〇 8 mm, and the photocurable resin is discharged at a discharge amount of 66 mg/cm. Coating of the composition (2nd). After the sealing portion is formed on the substrate E in the same manner as described above, the photocurable resin composition is dispersed and dispensed using a dispenser in a region surrounded by the sealing portion in a uniform manner ("Division"] g (equivalent to 0.4 mm in thickness of the layer of the first layer formed in the region surrounded by the sealing portion). After the dropwise addition of the photocurable resin composition (the third layer), In a vacuum vessel having a pressure of 1 〇Pa, a soda lime glass plate of the same shape and the same thickness (hereinafter referred to as a substrate F) is superposed on the substrate E so that the curable resin composition is interposed between the substrates, thereby performing vacuum After the lamination, the pressure in the decompression vessel is returned to the atmospheric pressure to release the decompression environment. After the pressure in the decompression vessel is returned to the atmospheric pressure, the laminated precursor is placed on the substrate E and F immediately. In the state of the end faces of the substrates E and F, the illuminance at 395 nm of the end faces of the substrates E and F is 156745.doc • 62-201231263 is a uv-led of 50 mW/cm 2 (manufacturer name: Integration khnology 'model) Name: LEDZero Pincure is irradiated with ultraviolet light to form a photocurable resin composition (second). The laminated precursors after UV irradiation are placed so that the substrates E and F are horizontal. The skin is not photohardened even after being placed for a few days. The resin composition (first) is eroded and kept in a sealed state. (Example 9) After the pressure in the vacuum depressor is returned to atmospheric pressure, the photocurable resin composition (second) is not cured by uv irradiation. In addition, the same steps as in Example 8 were carried out. The laminated precursors in which the pressure in the reduced pressure vessel was returned to atmospheric pressure were placed so that the substrates E and F were horizontal, and the laminate was confirmed after being left for about 3 minutes. It is confirmed that the sealing portion is eroded by the photocurable resin composition (the first) to impair the sealed state, and the photocurable resin composition (the third) leaks from the sealing portion. (Example 10) Preparation length 610 mm, width 610 mm, thickness 3 A substrate made of soda-lime-lime glass (hereinafter referred to as a substrate G) was heated and applied along the inner side of the end surface of the substrate g by 5 mm using a dispenser (45. (:) photocurable resin composition (second) &quot;) Here, the photocurable resin composition (2nd &quot;&quot;) has a viscosity of 12 〇 0 Pa at 25 ° C, and s ' is prepared according to the following procedure. It is used to prepare a photocurable resin combination. (2nd part) 88 parts by mass of urethane urethane oligomer solution (UC-1) and 12 parts by mass of mercapto propylene 156745.doc • 63 - 201231263 Acid 2_by butyl butyl ester LIGHTESTEr HOB) was mixed to obtain a mixture. 00 parts by mass of this mixture, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (photopolymerization initiator, Ciba refined) Manufactured by the company, IRGACURE 184), ι·1 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819 ) uniformly mixed ' to obtain a photocurable resin composition (second.). The photocurable resin composition (2nd &quot;,) is placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device is reduced to about 2 〇pa and held for 10 minutes. Defoaming treatment. The viscosity of the photocurable resin composition (2&quot;&quot; at 25 c was measured to be about 1200 Pa «s. In the case of using a nozzle having an inner diameter of 1 〇 6 mm for the main unit, the distance between the substrate E and the nozzle tip is set to 〇8 mm, and the photocurable resin is 〇u cc (6 6 discharge amount). Coating of the composition (2nd &quot;). Further, the viscosity of the photocurable resin composition (2&quot;&quot;) at the time of heat application is 2 〇〇Pa.s. The area surrounded by the dispersion is added by means of a dispenser, in such a manner that the interval is uniform (dropping pitch: 15 mm) and the layer thickness of the photocurable resin composition (the first layer) after coating is 0.4 mm. Resin composition (first). After the dispersion of the photocurable resin composition (the third layer), the curable resin composition is interposed between the substrates in a pressure-reducing container having a pressure of 1 〇Pa. The substrate G is superposed with a soda lime glass plate of the same shape and the same thickness (hereinafter referred to as a substrate H), and after vacuum lamination is performed, the pressure in the decompression container is restored to atmospheric pressure by the pressure I56745.doc -64 - 201231263 Pressure environment. Here, the height of the seal at the time of vacuum lamination, and the decompression ring The heights of the sealing portions are as follows. The height of the sealing portion when vacuum lamination is performed: 0.8 mm The height of the sealing portion after releasing the decompression environment: 0.4 mm Therefore, the height reduction rate of the sealing portion is 0.8/0.4=2 The laminated precursors which were removed from the decompressed environment for 10 minutes were visually confirmed to have a void having a projected area diameter of $ 〇μηη or more on the layer of the curable resin composition (the third layer). The void having an area diameter of 5 〇μχη or more (Example 11) The height of the sealing portion when the true-lasting laminate is applied is changed by changing the photocurable resin composition (2', ·) from the nozzle. In the same manner as in Example 10, the height reduction rate of the seals and the seals was 2 1 / 〇 4 = 5 25 . The laminated precursors after 1 minute from the decompression environment were visually observed. It is confirmed whether or not there is a void having a projected area diameter of 5 μm or more on the layer of the curable resin composition (No. 1). There are 160 empty areas with a projected area diameter of 5 μm or more. (Example 12) Light hardening tree from the nozzle In the case of the fat composition (2&quot;&quot;), the density of the laminate was applied. The interval 卩 of the crucible was 0.4 mm, and the same procedure as in Example 10 was carried out. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the detailed description, it is understood that various modifications and changes can be made without departing from the scope and spirit of the invention. The present application is based on Japanese Patent Application No. 2010-129718, filed on Jun. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a state in which a sealing portion is formed on a peripheral portion of a substrate. Fig. 2 is a schematic view showing a pressure distribution when a Newtonian fluid is sandwiched between a pair of substrates and pressurized with a load F. Figs. 3(a), 3(b), 3(c) and 3(d) are views showing the state of the laminated precursor after the vacuum lamination is performed and after the decompression environment is released. Fig. 3 (Dian and 3(b) are diagrams showing the state of the precursor of the laminated body when the reduction amount of the height of the sealing portion after the vacuum lamination is more than 2.5, and Fig. 3 (the sentence system indicates the state after the vacuum lamination is performed) Fig. 3(b) is a view showing a state in which the decompression environment is released. Fig. 3(c) and Fig. 3(d) show the reduction in height of the sealing portion after vacuum lamination is performed at 1.05 to 2.5. In the case of the range, the state of the precursor of the laminated body is shown in Fig. 3(c), which is a diagram showing the state after the vacuum lamination is performed. Fig. 3(d) is a view showing the state after the decompression environment is released. A) and 4(b) show a schematic view of the shape change of the sealing portion caused by the implementation of the vacuum laminate. Fig. 4(a) shows the state before the vacuum lamination is performed, and Fig. 4(b) shows the state after the vacuum lamination is performed. 156745.doc • 66 · 201231263 FIG. 5 (a) and (b) are views for explaining a preferred embodiment of a coating form of a second curable resin composition in the method for producing a laminate of the present invention. 5(a) shows the state before the vacuum lamination is performed, and Fig. 5(b) shows the state after the vacuum lamination is performed. Fig. 6(a) and (b) Another preferred embodiment of the coating form of the second curable resin composition in the method for producing a laminate of the present invention is shown in FIG. 6(a), and the state before the vacuum lamination is performed, FIG. 6 (b) shows a state after the vacuum lamination is performed. Fig. 7(a) is a view showing the shape of the sealing portion after vacuum lamination is applied when the second curable resin composition is applied at a fixed coating width, and Fig. 7 (b) A partial enlarged view of the corner portion of the sealing portion. Fig. 8 shows a vacuum when the second curable resin composition is applied according to a preferred embodiment of the coating form of the second curable resin composition. Schematic diagram of the shape of the sealing portion after lamination. [Description of main component symbols] 10. l〇a, l〇b Substrate 20 Sealing portion 30 First curable resin composition layer 100, 200 Bubble. A Coating width B of the second curable resin composition The coating width C and a of the second curable resin composition after vacuum lamination are performed. The sealing portion after vacuum lamination is applied to the corner portion. 156745.doc -67· 201231263 The width of the side protruding portion is at the corner The distance from the portion where the width of the sealing portion is thinned. The minimum value of the width of the sealing portion near the corner portion. R The radius of the Newtonian fluid r The distance from the Newtonian fluid center, t, 1.5t, 6t The height of the sealing portion 20 is 156,745. Doc -68-

Claims (1)

201231263 七、申請專利範圍： 1. 一種積層體之製造方沐， 万法其準備至少一者為透明基板之 兩片基板， 於上述一基板上之周邊都 η逭》丨浴成用u封入第丨硬化性樹 脂組合物之密封部， 對上述密封部所包圍之區域供給上述第！硬化性樹脂 組合物， 於減壓環境下在上述第1硬化性樹脂組合物上疊加另 -基板’於-對基板間夾持上述第i硬化性樹脂組合物 並密封’而獲得積層前驅物， 將該積層前驅物置於環境壓力高於上述減廢環境之第 2壓力環境下，於該第2壓力環境下使上述第丨硬化性樹 脂組合物硬化；且 上述密封部係藉由於上述一基板上之周邊部塗佈第2 硬化性樹脂組合物而形成， _ 自供給上述弟1硬化性樹脂組合物時起至將上述積層 前驅物置於上述第2壓力環境下為止之階段的上述第2硬 化性樹脂組合物之黏度為800〜5〇〇〇 Pa.s， 將上述積層前驅物置於上述第2壓力環境下之後的上 述密封部之寬度為0.8〜3.0 mm ’且上述密封部之剖面形 狀之高度/寬度之比為0.05〜1， 於上述減壓環境下在一對基板間夾持第I硬化性樹脂 組合物並密封時的上述密封部之高度（H)與將上述積層前 驅物置於上述第2壓力環境下之後的上述密封部之高度 156745.doc 201231263 (h)之比（H/h)為 1.05〜2.5。 2. 如請求項丨之積層體之製造方法，其中上述第2硬化性樹 脂組合物時之塗佈時之黏度為1〇〜75〇 Pa,s。 3. 如請求項〗或2之積層體之製造方法，其中於對上述密封 部所包圍之區域供給上述第丨硬化性樹脂組合物前，使 上述第2硬化性樹脂組合物半硬化。 4. 如請求項丨至3中任一項之積層體之製造方法，其中於在 上述第2壓力環境下使上述第i硬〖性樹脂組合物硬化 時，使上述第2硬化性樹脂組合物硬化。 5. 如請求項1至3中任一項之積層體之製造方法，其中於將 上述積層前驅物置於上述第2壓力環境下之後且在使 上述第1硬化性樹脂組合物硬化之前，使上述第2硬化性 樹脂組合物硬化。 6. 如凊求項1至5中任-項之積層體之製造方法，其中以在 所形成之^6、封部之角部附近，上述第2硬化性樹脂組合 ^之塗佈寬度與其他塗佈寬度相比變細之方式，於上述 -基板上之周邊部塗佈第2硬化性樹脂組合物。 口項6之積層體之製造方法，其中以使塗佈上述 2知組合物時之密封部之角部内緣侧的位置彰 述積層則驅物之逾★ 在封之角部之内緣側的位置更靠切 板之外緣側之方4 £ y 式’於上述一基板上之周邊部塗佈 硬化性樹脂組合物。 8. 如請求項1至7 _ 述一對基板中， 任—項之積層體之製造方法，其中於上 至^、一者為厚度0.1〜3 mm之玻璃基板。 156745.doc 201231263 9. 如請求項丨至8中任一項之積層 中上述 中存在 的第1 第1硬化性樹脂組合物之黏度為製造方法’： ’ υ.2〜5〇 Pa.s。 10. 如請求項1至9中任一項之積層 β遐之製造方法，」 於由上述一對基板與上述密封邱 切27 #所密封之區域 硬化性樹脂組合物之層的厚度為30〜3〇〇〇 μπ1。 156745.doc201231263 VII. Patent application scope: 1. The manufacturing method of a laminated body, Wanfa prepares at least one of the two substrates of the transparent substrate, and the periphery of the above substrate is η逭The sealing portion of the sturdy resin composition is supplied to the region surrounded by the sealing portion. In the curable resin composition, a layered precursor is obtained by laminating the above-mentioned i-th curable resin composition between the substrate and the substrate on the first curable resin composition under a reduced pressure atmosphere, and sealing the mixture. The laminated precursor is placed in a second pressure environment having an ambient pressure higher than the waste reducing environment, and the second crucible resin composition is cured in the second pressure environment; and the sealing portion is formed on the substrate The second curable resin composition is applied to the peripheral portion, and the second curable property is obtained from the time when the above-described first hard curable resin composition is supplied to the step of placing the laminated precursor in the second pressure environment. The viscosity of the resin composition is 800 to 5 ÅPa.s, and the width of the sealing portion after the laminated precursor is placed in the second pressure environment is 0.8 to 3.0 mm' and the height of the cross-sectional shape of the sealing portion The ratio of the width (H) of the sealing portion when the first curable resin composition is sandwiched between the pair of substrates and sealed in the reduced pressure environment, and the ratio of the width is 0.05 to 1. Was placed over the front drive 156745.doc 201231263 (h) of the height of the seal portion after the above-described second pressure environment (H / h) is 1.05~2.5. 2. The method for producing a laminate according to the above aspect, wherein the viscosity of the second curable resin composition when applied is 1 〇 to 75 Å Pa, s. 3. The method for producing a laminate according to claim 2, wherein the second curable resin composition is semi-cured before the supply of the second curable resin composition to the region surrounded by the sealing portion. 4. The method for producing a laminate according to any one of the preceding claims, wherein the second curable resin composition is cured when the first hard resin composition is cured in the second pressure environment hardening. 5. The method for producing a laminated body according to any one of claims 1 to 3, wherein, after the laminated precursor is placed in the second pressure environment, and before the first curable resin composition is cured, The second curable resin composition is cured. 6. The method for producing a laminate according to any one of the items 1 to 5, wherein, in the vicinity of the formed corner portion of the sealing portion, the coating width of the second curable resin composition is different from The second curable resin composition is applied to the peripheral portion of the substrate described above in such a manner that the coating width is thinner. In the method for producing a laminate according to the above-mentioned item 6, the position of the inner edge side of the corner portion of the sealing portion when the above-mentioned composition is applied is described as a layer of the insulator, and the outer edge of the corner portion of the sealing portion is The position is further on the outer edge side of the cutting plate. 4 £ y The 'curable resin composition is applied to the peripheral portion of the above substrate. 8. The method for producing a laminated body according to any one of the first to seventh embodiments, wherein the substrate is a glass substrate having a thickness of 0.1 to 3 mm. 156745.doc 201231263 9. The viscosity of the first first curable resin composition present in the above-mentioned layer of any one of the items of item 8 to 8 is a manufacturing method ': ' υ. 2 to 5 〇 Pa.s. 10. The method for producing a layered β遐 according to any one of claims 1 to 9, wherein the thickness of the layer of the region-hardenable resin composition sealed by the pair of substrates and the sealing layer 27# is 30~ 3〇〇〇μπ1. 156745.doc
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WO2011155396A1 (en) 2011-12-15

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