TW201124354A - Process for producing laminate - Google Patents

Process for producing laminate Download PDF

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Publication number
TW201124354A
TW201124354A TW099138127A TW99138127A TW201124354A TW 201124354 A TW201124354 A TW 201124354A TW 099138127 A TW099138127 A TW 099138127A TW 99138127 A TW99138127 A TW 99138127A TW 201124354 A TW201124354 A TW 201124354A
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TW
Taiwan
Prior art keywords
resin composition
curable resin
substrates
substrate
sealing portion
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Application number
TW099138127A
Other languages
Chinese (zh)
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TWI429608B (en
Inventor
Hiroshige Ito
Yasunori Ito
Yu Nojiri
Tateo Baba
Satoshi Niiyama
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Asahi Glass Co Ltd
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Publication of TW201124354A publication Critical patent/TW201124354A/en
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Publication of TWI429608B publication Critical patent/TWI429608B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B29C65/54—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive between pre-assembled parts
    • B29C65/542—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive between pre-assembled parts by injection
    • 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
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1858—Handling of layers or the laminate using vacuum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • 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)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Sealing Material Composition (AREA)
  • Electroluminescent Light Sources (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

A novel process is provided for producing a laminate by curing a hardening resin held and enclosed between a pair of base plates, the process enabling shortening of the time for filling uniformly the hardening resin composition into the entire of the enclosed space. In the process for producing the laminate by curing a hardening resin held and enclosed between a pair of base plates, the layer of the hardening resin composition placed in the enclosed space satisfies the following conditions: (1) the circle-equivalent diameter of the projection geometry of the pores present in the hardening resin composition layer is less than or equal to 10 mm, (2) the circle-equivalent diameter of the projection geometry of the non-pore portion in the hardening resin composition layer is less than or equal to 40 mm, and (3) the layer of the hardening resin composition and the pores present in the hardening resin composition layer come in contact alternately with the enclosing seal member.

Description

201124354 六、發明說明： 【發明所屬之^技彳軒領域】 發明領域 本發明係關於積層體的製造方法，該積層體具備有一 對基板、以及存在於該一對基板間的硬化性樹脂組成物之 硬化物層。 依,¾本發明方法所製得的積層體，適用為諸如爽層玻 璃、影像顯示裝置的前面板，更具體而言，適用於諸如液 晶顯不裝置(LCD)、有機EL或無機EL之類的EL(電激發光) 顯不裝置、電漿顯示裝置、電子墨水型影像顯示裝置之類 的平面顯示器（FPD)之前面板，以及諸如薄層太陽電池裝 置、觸控面板的保護板等用途。 C先前技冬恃;| 發明背景 經由接著層將一對玻璃基板形成一體化的夾層玻璃， 因為遭破損的玻璃破片會附著於薄膜上而不會有飛散情 形’因而被使用為汽車的防風玻璃，又，因為較難貫穿且 強度優異，因而被使用為建物的窗玻璃（安全玻璃、防盜玻 璃)(參照專利文獻1、2)。 再者’就從防止液晶面板破損、及防止光反射的觀點， 已知有將前面板設置於該液晶面板前面的液晶顯示裝置， 該前面板係在透明保護板與偏光板間封入透明中間膜者 (參照專利文獻3)。 再者’已知有具太陽電池裝置的太陽電池模組，該太 201124354 〶電池裝置係在成為受光面的透明表面材與背面材間，利 用樹脂等密封材料進行密封者(參照專利文獻4)。 ,^此’具有—對基板、及存在於該-對基板間的硬化 ’、且成物之硬化物層的積層體，在各種技術領域中有 存在的需求。 此積層體的製造方法有多數提案，專利文獻卜2所記 載的方法並未限㈣使輯㈣赫，挾躲基板間而成 為中間層的硬化性樹脂組成物種類自由度大，能有效利用 用以升ν成中間層的資源，就生產性優異、環境負荷小的觀 點係屬優異。 此方法係在其中一基板上的周邊部形成用以封住硬化 性樹脂組成物的密封部，之後再對基板上由密封部所包圍 的區域供應硬化性樹脂組成物。接著，在減壓環境下，藉 由在其中一基板上重疊另一基板，以在一對基板間挾持硬 化性樹脂組成物並加以密封。 接著’將挾持著硬化性樹脂組成物且已密封的一對基 板，放置在高於前述減壓環境的壓力環境下（例如大氣壓 下）。藉由環境壓力的上升，朝一對透明基板彼此密接的方 向按壓，同時因為殘留在密閉空間内的空隙體積會配合環 境的差壓而縮減，因而硬化性樹脂組成物會流入由一對基 板與密封部所密閉的密閉空間中之減壓空間内，致使密閉 空間整體被硬化性樹脂組成物均勻填充。然後，藉由使硬 化性樹脂組成物硬化來獲得積層體。 先行技術文獻 4 201124354 專利文獻 專利文獻1 :國際公開W02008/081838號公報 專利文獻2 :國際公開W02009/016943號公報 專利文獻3 :日本專利特開2〇〇9_2〇5065號公報 專利文獻4 :曰本專利特開平11 -87743號公報 C發明内容：！ 發明概要 發明欲解決之課題 如上所述，專利文獻卜2所記載之積層體的製造方法’ 係在減壓環境下，於一對透明基板間挾持硬化性樹脂組成 物，經密封後再藉由放置在高於前述減壓環境的壓力環境 下（例如大氣壓下），以呈現密閉空間整體被硬化性樹脂組成 物均勻填充的狀態。但是’依照所使用之硬化性樹脂組成 物的黏度、存在於密封空間中之硬化性樹脂組成物的層 厚’會有較難呈現密閉空間整體被硬化性樹脂組成物均勻 填充狀態的情況。 即’當所使用之硬化性樹脂組成物的黏度較高時(例如 硬化性樹脂組成物黏度達0.2Pa· s以上之情況）、以及存在 於密封空間之硬化性樹脂組成物的層厚較大時（例如硬化 性樹脂組成物的層厚達30μιη以上之情況），將挟持著硬化性 樹脂組成物並經密封的一對基板，放置在古 '仕巧於前述減壓環 境的壓力環境下(例如大氣壓下），之後為縮減 間中的空隙，其所需時間會有增加的可能性。因 工 呈現密閉空間整體被硬化性樹脂組成物均勻填充2狀^此 201124354 便需要較長時間。 本發明係為解決上述習知技術的問題點而完成，其目 的在於提供：在使被挾持於一對基板間且經密閉的硬化性 樹脂組成物硬化以製造積層體的方法中，能縮翅為使密閉 空間整體被硬化性樹脂組成物均句填充的所需時間之新穎 方法。 用以欲解決課題之手段 為達成上述目的，本發明積層體的製造方法係包含有 下述步驟： 準備2片基板； 在其中一基板上的周邊部形成密封部，該密封部係用 以封住硬化性樹脂組成物者； 對其中一基板上由前述密封部所包圍的區域，供應硬 化性樹脂組成物； 於減壓環境下’在前述被供應的硬化性樹脂組成物上 重疊另一基板，以在一對基板間挾持硬化性樹脂組成物並 加以密封；及 將挾持著硬化性樹脂組成物的一對基板，放置在高於 前述減壓環境的第2壓力環境下，於該第2壓力環境下使硬 化性樹脂組成物硬化以製造積層體，該積層體的製造方法 之特徵在於： 控制供應至基板上之前述硬化性樹脂組成物的塗佈狀 態、以及在前述硬化性樹脂組成物上重疊另一基板的時 期，以在將前述另一基板重疊於其中一基板上之時，存在 6 201124354 於由前述密封部所包圍區域中的硬化性樹脂組成物層可滿 足下述（1)〜（3); (1)存在於前述硬化性樹脂組成物層中之空隙，其投影 形狀的等值 BJ 直徑(—lent drde diameter)IVe 為 1〇_ 以下； (2)前述硬化性樹脂組成物層中未存在有空隙之部分， 其投影1狀的等值圓直徑〇_障為4〇_以下； 、（）】述更化H；^脂組成物層和存在於前述硬化性樹脂 組成物層中之空陴，六 *、又互地與前述密封部呈相接觸之狀態。 述所明「可滿足（1)〜(3)」係指可滿足（1)、（2) 及(3)所記載要件中任—項。 發月積層體的製造方法巾，較㈣在料—對基板 中至少一片為透明基板。 本發明積層體的製 J方法中，前述硬化性樹脂組成物 的黏度係0.2〜5〇pa .。 义本發明積層體的製造方法巾，存在於由前述—對基板 /'1述岔封α卩所街封的空間内之硬化性樹脂組成物層的厚 度’係30〜30〇〇μηι。 3明積層H的製造方法中，前述㈣部係使用黏度 a s的第2硬化性樹脂組成物而形成者。 本心月積層體的製造方法中，較佳係前述減壓環境為 0.1〜lOOOPa的壓力辱产 私月積層體的製造方法，較佳係前述第2環境的壓力 較前述減壓環境的壓力“5GkPa以上 。另外，相對於該第 201124354 2壓力環境，在朝由密封部所包圍區域供應的前述樹脂膜形 成用硬化性樹脂組成物上，重疊另一基板並在減壓下進行 密封的減壓環境，相當於第1壓力環境。 本發明積層體的製造方法中，較佳係對其中一基板上 由前述密封部所包圍區域進行硬化性樹脂組成物供應，係 指對由前述密封部所包圍區域分散滴下硬化性樹脂組成 物。 此情況，較佳係藉由在使前述硬化性樹脂組成物分散 滴下之際，藉由使前述其中一基板、與分散滴下時所使用 喷嘴進行相對性擺動，而滴下的硬化性樹脂組成物之等值 圓直徑強制性擴大，俾使在由前述密封部所包圍區域中存 在的硬化性樹脂組成物之等值圓直徑呈均勻。 本發明積層體的製造方法中，對其中一基板上供應前 述硬化性樹脂組成物，以在對其中一基板上由前述密封所 包圍區域供應前述硬化性樹脂組成物時，使前述硬化性樹 月曰組成物呈滿足下述(4)〜(9)的振動曲線； (4) 相對於振動曲線前進方向，在垂直方向依一定的週 期(X)與振幅(Y)重複位移； (5) 相鄰接之振動曲線的位移係相互呈反相位； (6) 將開始供應時的振動曲線粗細度設為!!^!^!!)時，前 述週期(x)(mm)、及前述振幅(Y)(mm)係滿足下式： 2.1xm^X^ i〇xm (2.1xm)/2^Y^(1〇xm)/2 (7) 將開始供應時的振動曲線粗細度設為m(mm)時’振 8 201124354 動曲線與密封部間之最短距離d(s_r)(mm)係滿足下式： d(s.r)^ 2.5xm (8) 將開始供應時的振動曲線粗細度設為m(mm)時，相 鄰接之振動曲線間的最短距離d(r_r)(mm)係滿足下式： d(r.r)^ 5xm (9) 當E=2Y-2m時，該E(mm)係滿足下式： (Y+d(r.r))/10^E^Y+d(r.r) 另外，上述所謂「滿足(4)〜（9)」係指可滿足(4)至（9) 所記載要件中任一項。 再者，本發明積層體的製造方法中，對其中一基板上 供應前述硬化性樹脂組成物，以在對其中一基板上由前述 密封所包圍區域進行供應時，前述硬化性樹脂組成物之可 滿足下述（10)〜（14)的振動曲線和與該振動曲線朝同一方 向前進的直線相鄰接； (10) 相對於振動曲線前進方向，在垂直方向依一定的週 期（X)與振幅(Y)重複位移； (11) 將開始供應時的振動曲線粗細度設為m(mm)時，前 述週期（X)(mm)、及前述振幅(Y)(mm)係滿足下式： 2.1xm^ 10xm (2.1xm)/2^ Y^(10xm)/2 (12) 當振動曲線位於密封部附近，且將開始供應時的振 動曲線粗細度設為m(mm)時，該振動曲線與密封部間之最 短距離d(w)(mm)係滿足下式： d(s.r)^ 2.5xm 9 201124354 (13) 將開始供應時的振動曲線粗細度設為m(mm) 時，相鄰接之振動曲線與直線間之最短距離d(r-r)(mm)係 滿足下式： d(r.r)^ 2.5xm (14) 當E=2Y-2m時，該E(mm)係滿足下式： (Y+d(r.r))/20^E^(Y+d(r.r))/2 另外，上述所謂「滿足（10)〜（14)」係指可滿足（10)至 (14)所記載要件中任一項。 再者，上述本發明積層體的製造方法中，較佳係從硬 化性樹脂組成物完成對其中一基板上由前述密封部所包圍 區域的滴下開始，直到積層為止的時間係30〜1800秒。 發明效果 根據本發明積層體的製造方法，可縮短製造積層體過 程中所實施之利用硬化性樹脂組成物均勻填充由一對基板 與密封部所密閉的空間整體所需要的時間，並可提高積層 體的生產性。 圖式簡單說明 第1圖係基板的平面圖，在基板上的周邊部形成密封部 狀態。 第2圖係基板的平面圖，在基板由密封部所包圍的部分 中形成硬化性樹脂組成物層的狀態。 第3(a)〜（c)圖係對基板由密封部所包圍區域點狀分散 滴下之硬化性樹脂組成物的經時變化圖。 第4(a)〜（d)圖係硬化性樹脂組成物在第3(a)圖所示狀 10 201124354 態時施行真空積層的情況下，硬化性樹脂組成物在真空積 層時及解除減壓環境後的狀態圖。 第5⑷〜⑷圖係硬化性樹脂組成物在第3(b)圖所示狀 態時施行真空積層的情況下’硬化性樹脂組成物在真空積 層時及解除減壓環境後的狀態圖。 第6⑷〜⑷圖係硬化性樹脂組成物在第3⑷圖所示狀 態時施行真空積層的情況下，硬化性樹脂組成物在真空積 層時及解除減壓環境後的狀態圖。 第7(a)〜(e)圖係對基板由密封部所包圍區域點狀分散 滴下之硬化性樹脂組成物的經時變化圖。 第8圖係使用單點噴嘴，對基板由密封部所包圍區域分 ' 散滴下硬化性樹脂組成物的順序圖。 • 第9圖係使用多點喷嘴’對基板由密封部所包圍區域分 散滴下硬化性樹脂組成物的順序圖。 第10圖係使用多點噴嘴，對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第11圖係使用多點喷嘴，對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第12圖係使用多點喷嘴，對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第13圖係滴下後的經過時間t(sec)與硬化性樹脂組成 物的等值圓直徑d(mm)間之關係圖。 第14圖係滴下後的經過時間t、硬化性樹脂組成物的等 值圓直徑d及存在於硬化性樹脂组成物層中之空隙的等值 11 201124354 圓直徑Dpore間之關係圖。 第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第16圖相當於第15圖之部分放大圖，係顯示振動曲線 3〇a、30b形狀的經時變化。 第17圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第18圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第19圖係將硬化性樹脂組成物呈線狀塗佈時的較佳给 佈形態圖。 & 第20圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 ' 第21圖係將硬化性樹脂組成物呈線狀塗佈時的較佳条 佈形態圖。 & 第2 2圖係將硬化性樹脂組成物呈線狀塗佈時的較佳汾 佈形態圖。 & 第2 3圖係將硬化軸驗減呈線狀塗料的較佳塗 佈形態圖。 第2 4圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 C實方包方式】 用以實施發明之形態 以下’參照圖式針對本發明積層體的製造方法進行說 12 201124354 明。 本發明積層體的製造方法中，一對基板中，於其中一 基板上的周邊部形成密封部，該密封部係用以封住硬化性 樹脂組成物者。第1圖係基板的平面圖，顯禾在基板10上的 周邊部形成密封部20之狀態。 [基板] 本發明積層體的製造方法中，如後所述，因為密封部 形成用硬化性樹脂組成物較佳係使用光硬化性樹脂組成 物’因而一對基板中’最好至少有丨個係屬於透明基板。此 時，一對基板中，可僅係其中一者為透明基板而另一者為 不透明基板’亦可二片基板均為透明基板。此處，當其中 一者係透明基板而另一者係不透明基板時，可在透明基板 的周邊部形成密封部，亦可在不透明基板的周邊部形成密 封部。 另外’透明基板在屬於透明，即具可見光穿透性之基 板的前提下’其餘則無特別的限定。透明基板的具體例可 如玻璃基板及透明樹脂基板。該等之中，就從具透明性、 耐光性、低雙折射性、高平面精度、耐表面刮傷性、及高 機械強度的觀點’較佳為玻璃基板。 玻璃基板的材料除鈉辦玻璃之外，尚可例如鐵分更低 且偏藍之較小的高穿透玻璃（白板）、硼矽酸玻璃等。 透明樹脂基板的材料可如透明性較高的樹脂材料（聚 碳酸酯、聚曱基丙稀酸甲酷等）。 再者’透明基板在至少具有可見光穿透性的前提下， 13 201124354 亦可係諸如在使光進行散射或折敎目的下對基板表面施 行細u凹凸加工者、或對基板表面施行遮光印刷者。 再者，亦可使用由透明基板複數片貼合而成者、或將 貼合有光學薄膜等的透明基板當作-體的透明基板來使用 者。 再者，含有將透明基板當作構成要件其中一部分的構 造體亦可使用為透明基板。此種含有將透明基板當作構成 要件其中一部分的構造體具體例可如：液晶顯示裝置 (LCD)、有機EL或無機EL之類的Ε£(電激發光)顯示裝置、 電聚顯示裝置、電子墨水型影像顯示裝置之賴平面顯示 器（FPD)、薄層太陽電池裝置、觸控面板等。 “ 當一對基板中，其中一者為不透明基板時，不透明基 板的具體例可如.不銹鋼等金屬材料製基板、陶瓷材料製 基板、或藉由使可吸收可見光之填充劑分散於基板中而進 行遮光的樹脂基板等。 另外，當一對基板的雙方均為透明基板時，該—訝透 明基板可由相同材料形成，亦可由不同材料形成。即，— 對透明基板的雙方可均為玻璃基板或透明樹脂基板，亦可 一對透明基板中，其中一者為玻璃基板而另一者為透明樹 脂基板。 基板的厚度並無特別的限定，係透明基板的情況時， 就從機械強度、透明性的觀點，玻璃基板時通常較佳為 6mm。特別係要求厚度較薄之透明積層體的情況，玻璃基 板的厚度較佳為0.3〜l_5mm、更佳為〇.3〜1mm。又，透明 14 201124354 樹脂板時的厚度通常係0.1 〜3mm。 另—方面’不透明基板的情況，就從機械強度、薄型 輕量化的觀點，通常係0.8〜4mm。 另外，一對基板的厚度可相互相同、亦可為不同。 基板的表面，更具體而言，係在周邊部有形成密封部 J的表面，為升與該密封部間之界面接著力亦可施行 表面處理。此處，表面處理可僅對基板的周緣部實施，亦 可對基板的表面全體實施。 表面處理的方法係有將基板的表面利用矽烷偶合劑施 行處理的方法等。 [密封部] 因為係在對基板上由該密封部所包圍區域供應的硬化 性樹脂組成物予以擋止’之後於減壓環境下將被挾持於一 對基板間並密封的硬化性樹脂組成物予以封住之目的下來 S又置畨封部，因而在本發明積層體的製造過程中，要求對 該密封部所包_域供應的硬化性賴組成物具有不會發 生漏出程度以上的界面接著力，且要求在本發明積層體的 製U過私巾要有能維持形狀程度的堅固度。 滿足，種要求的密封部係在其中一基板的周邊部設置 表面”接著劏或黏著劑的密封構件便可形成。 此種在、封構件的具 •預先在表面設置 長條體（雙面膠帶等）。 體例係有如下述者。 黏著劑層或接著劑層的帶狀或棒狀 在其中-基板表面的周緣部形成接著劑層或黏著劑 15 201124354 層，並於其上貼附長條體者。 ^ •使用硬化性樹脂組成物以在其中一基板表面的周緣 部1用印刷或點轉方式形成壩狀密封前驅體，使硬化 樹月曰組成物進行硬化後，再於該表面上形成接著劑層或 黏著劑層者。 再者，將當作第2硬化性樹脂組成物的高黏度硬化性樹 月曰、及成物，使用分配器或模具塗佈機在其中一基板的周邊 部塗佈成既定厚度便可形成滿足上述要求的密封部。以 下’本說明書中’為形成密封部而使用的硬化性樹脂組成 物亦稱「第2硬化性樹脂組成物」。 此處，第2硬化性樹脂組成物在後述的順序中，可在使 被挾持於一對基板間並經密封的硬化性樹脂組成物硬化 時，亦同時進行硬化，亦可在使已密封的硬化性樹脂組成 物進行硬化前便硬化。另外，本發明積層體的製造方法的 構成要件之一，係包括有：「在其中一基板上的周邊部上形 成密封部，該密封部係用以封住硬化性樹脂組成物者」，此 處的「密封部」包含硬化前的密封前驅體，其係為形成密 封部而在其中一基板表面的周緣部，將硬化性樹脂組成物 形成壩狀者。 第2硬化性樹脂組成物係就從在對由密封部所包圍區 域供應硬化性樹脂組成物時，具有能封住該樹脂膜形成用 硬化性樹脂組成物的強度、當依照後述順序實施真空積層 與解除減壓環境時，能配合存在於由一對基板與密封部所 密封的空間内之硬化性樹脂組成物層的厚度而使該密封部 16 201124354 變形、以及當依照後述順序實施真空積層及解除減壓環境 時’密封部具有能承受大氣壓之強度的觀點，點度較佳為 200〜3000Pa · s、更佳為5〇〇〜2〇〇〇Pa · s。 此處，為能保持-對基板彼此間的間隔，亦可在第a硬 化性樹脂組成物中摻入既定粒徑的間隔粒子。 另外’第2硬化性樹脂組成物錢述㈣硬化性樹脂組 成物，較佳係使用滿足上述黏度者。 為使對由該密封部所包圍區域供應的硬化性樹脂組成 物不會漏出，密封部最好形成較由該密封部所包圍區域供 應的硬化性樹脂組成物所構成之層（以下，在本說明金中， 有簡稱「硬化性樹脂組成物層」的情況）的既定厚度多出若 • +厚度之狀態。例如較佳為硬化性樹脂組成物層既定厚度 的1.1倍以上且2倍以下。 再者’密封部的寬度係依照硬化性樹脂組成物層的厚 度而有所差異，較佳為0.5〜5mm、〇_5〜3mm程度。 當藉由前述黏度的第2硬化性樹脂組成物之塗佈而形 成密封部時，S為在密封部形成時所使用的第2硬化性樹脂 組成物係屬於高黏度，因而諸如對由密封部所包圍區域供 應的硬化性樹脂組成物，在塗佈後其形狀並不會有經時變 化。所以，所形成的密封部有發生部分性缺損、或密封部 的寬度有部分性變細的細化情況，而該等缺點不會經時消 除。因而’當所形成之密封部有發生部分性缺損或細化的 情況，在依照後述順序實施真空積層前、或者在實施真空 積層時’對由密封部所包圍區域供應的硬化性樹脂植成物 17 201124354 會滲出到較該密封部更靠外側處，因而在存在於由一對其 板與密封部所密閉的空間内之硬化性樹脂組成物中會有= 現較大空隙的可能性。又，對由密封部所包圍區域供應的 硬化性樹脂組成物滲出到較該密封部更靠外側處，便會有 損及所製造之積層體式樣性的可能性。 再者，當所形成的密封部有發生部分性缺損或細化的 情況，在依照後述順序實施減壓環境解除時，氣體會侵入 由一對基板與密封部所密閉的空間内，而導致存在於密閉 空間内的硬化性樹脂組成物有出現較大空隙的可能性。 再者，形成密封部之際，在塗佈的始終點部分發生硬 化性樹脂組成物重疊的情況不會經時消除，因而當依照後 述順序實施真空積層之際，密封部的厚度成為部分性不均 勻情形，導致在存在於由一對基板與密封部所密閉空間内 的硬化性樹脂組成物有出現較大空隙的可能性。又，因發 生重疊部分的密封部寬度會變大，導致會有損及所製造之 積層體式樣性的可能性。 所以，藉由塗佈第2硬化性樹脂組成物而形成密封部 時，為能不致發生前述的問題，最好在塗佈第2硬化性樹脂 組成物後，便檢查有無發生諸如部分性缺損、細化、重疊 之類的缺點。但，因為依照缺點的大小，亦有不會發生上 述問題的情況，因此最好檢查有無超過預定容許範圍大小 的缺點。 檢查方法有藉由影像處理來確認經塗佈後的硬化性樹 脂組成物中所存在之缺點的尺寸之方法。 18 201124354 其次，將硬化性樹脂組成物供應給基板上由密封部所 包圍的區域。 硬化性樹脂組成物的供應量預先設定為當依照後述順. 序在一對基板間挾持硬化性樹脂組成物並加以密封時，由 一對基板與密封部所密閉的空間剛好會被硬化性樹脂組成 物填充的量。此時’可預先考慮因硬化性樹脂組成物的硬 化收縮造成體積減少的情形之後，才決定硬化性樹脂組成 物的供應量。 本發明積層體的製造方法中，當依照後述順序在一對 基板間挾持硬化性樹脂組成物並加以密封時，存在於由_ 對基板與密封部所密封的空間内之硬化性樹脂組成物層的 厚度最好為30〜3000μηι。理由係為使硬化性樹脂組成物層 不僅具有當作一對基板間之接著劑的功能，且具有能對該 層賦予機械強度的功能’因而需要厚度，另一方面，一般 諸如開口構件或顯示構件要求為薄型輕量化，因而最好不 要無端增厚。 當依照後述順序在一對基板間挾持硬化性樹脂組成物 並加以密封時，在由一對基板與密封部所密封的空間内存 在之硬化性樹脂組成物層的厚度更佳係3〇〜8〇〇叫^、特佳 係100〜40〇μιη。又’依照情況，會有硬化性樹脂組 厚度越薄越佳的情況，此情況，硬化性樹餘成物層的厚 度較佳係30〜4〇〇μηι、更佳係100〜2〇〇μπι、特佳係1㈨〜 160μηι。 硬化性樹脂組成物的供應方法如將依照上述順序形成 19 201124354 岔封部的基板平放’再利用諸如分配器等供應機構呈點狀 或線狀滴下而進行供應者。另外，相關硬化性樹脂組成物 的具體供應順序容後呈述。 本發明的製造方法，相較於在預先形成的積層體間隙 注入硬化性樹脂的習知方法（例如日本專利特開昭 57-165411號公報、特開2001-339088號公報所記載的方法， 組合於本說明書中）’可使用較高黏度的硬化性樹脂組成 物。藉此，可使硬化性樹脂組成物硬化時降低硬化收縮、 及提升硬化後的樹脂層的機械強度。 所使用的樹脂膜形成用硬化性樹脂組成物之黏度，就 從在工業性製造、移送、塗佈大量硬化性樹脂組成物的步 驟中較容易處置之觀點，較佳係0.2〜50Pa . s。 另外，此處所謂「樹脂膜形成用硬化性樹脂組成物的 黏度」，係指在本發明積層體的製造方法實施時之溫度區域 中的黏度，特別係在將硬化性樹脂組成物供應給由密封部 所包圍區域中之後，再依照後述順序實施至真空積層的溫 度區域中之黏度。例如當依常溫實施該等順序時，即為常 溫下的硬化性樹脂組成物黏度。所以，雖依照實施該等順 序時的溫度而有所差異，但不管何種情況均在5〜80°C溫度 範圍内。關於此點，上述密封部形成時所使用的第2硬化性 樹脂組成物之黏度亦同。 所使用硬化性樹脂組成物的黏度較佳係1〜2〇Pa . s、 更佳係5〜20Pa。 滿足上述黏度的硬化性樹脂組成物，係可使用含有如 20 201124354 下述高分子量硬化性化合物(寡聚物等）的硬化性樹脂組成物。 因為高分子量的硬化性化合物可減少硬化性樹脂組成 物中化學鍵結的數量，因而使硬化性樹脂組成物硬化時的 硬化收縮情形會變小，且會提升硬化後的樹脂層的機械強 度。另一方面，高分子量的硬化性化合物大多係屬於高黏 性。因而，就從可確保硬化後的樹脂層的機械強度並抑制 氣泡殘存的觀點，最好利用在高分子量硬化性化合物中溶 解分子量較小的硬化性單體來調整黏度。可是，藉由使用 分子量較小的硬化性單體，硬化性樹脂組成物的黏度雖會 降低，但卻使硬化性樹脂組成物硬化時的硬化收縮情形變 大，且機械強度容易降低。 所使用的硬化性樹脂組成物最好係光硬化性樹脂組成 物。光硬化性樹脂組成物相較於熱硬化性樹脂組成物，可 利用較少的熱能並在短時間内硬化。所以，本發明藉由使 用光硬化性樹脂組成物，便可降低製造積層體時的環境負 荷。又，因為利用數份至數十份程度的光硬化性樹脂組成 物便可實質的硬化，因而積層體的生產效率較高。 所謂「光硬化性樹脂組成物」係指利用光的作用進行 硬化而形成樹脂層的材料。光硬化性樹脂組成物係可舉例 如下述物，可在硬化後的樹脂層的硬度不會過高之範圍内 使用。 •含有加成聚合性不飽和基之化合物與光聚合起始劑 的组成物。 •依不飽和基與硫醇基的莫耳數大約相等的比例含有 21 201124354 具1〜6個不飽和基的聚烯烴化合物（三聚異氰酸三烯丙酯 等）與具1〜6個硫醇基的聚硫醇化合物（三乙二醇二硫醇）， 且含光聚合起始劑的組成物。 •含有具2個以上環氧基之環氧化合物與光陽離子產生 劑的組成物。 光硬化性樹脂組成物就從硬化速度較快速、硬化後的 樹脂層透明性較高之觀點，更佳係含有具有選自由丙稀醯 氧基及曱基丙烯醯氧基所構成群組中之1種以上的基（以下 稱「（甲基）丙烯醯氧基」）之化合物的至少1種與光聚合起始 劑。 具（甲基）丙烯醯氧基的化合物（以下亦稱「（曱基）丙烯酸 酯系化合物」），較佳係每1分子具有1〜6個（甲基）丙烯醯氧 基的化合物，就從硬化後的樹脂層不會變為過硬的觀點， 更佳為每1分子具有1〜3個（甲基）丙烯醯氧基的化合物。 (甲基）丙烯酸酯系化合物就從硬化後的樹脂層的耐光 性而言，最好係盡可能未含芳香環的脂肪族或脂環式化 合物。 再者，（甲基）丙烯酸酯系化合物就從提升在與基板間之 界面接著力的觀點，更佳為具羥基的化合物。在（甲基）丙烯 酸醋系化合物總量中，具經基的（曱基）丙稀酸S旨系化合物的 含量較佳為25質量％以上、更佳為40質量％以上。另一方 面，具羥基的化合物容易導致硬化後的樹脂層彈性係數變 得過高，特別係使用具羥基的（甲基）丙烯酸酯時，依照積層 體的用途會有硬化後的樹脂層變得過硬的可能性。例如使 22 201124354 用於平面顯示器（FPD)的前面板時，因為硬化後的樹脂層最 好係屬於低彈性係數，因而在（甲基）丙烯酸酯系化合物總量 中’具經基的（甲基）丙烯酸酯含量較佳在4〇質量。/〇以下、更 佳在3〇質量％以下。 再者’譬如玻璃基板與聚碳酸酯等樹脂基板的積層之 異種材料製基板彼此間的積層，於不同表面能量的基板表 面’為能使樹脂層對任一基板均能顯現出適當密接力，可 使用呈低彈性係數之黏著態樣的樹脂層。 另一方面’當將較薄玻璃基板與較厚玻璃基板進行積 層時，藉由設置高彈性係數且薄至〇 lmm以下的樹脂層， 亦可提南積層體的機械強度，且此時亦可將㈣基的（甲基) 丙烯酸酯含量設為60質量％以上。 (甲基)丙烯酸S旨系化合物可為較低分子量的化合物（以 下稱6烯1系單體」），亦可為具重複單元的較高分子 里化。物(以下稱「（甲基)丙稀酸醋系寡聚物」）。 (甲基)丙烯S鳴系化合物係可舉例如：由^種以上（甲基） 丙烯酸I系單體構成者、由1種以增基)丙物旨系寡聚 物構成者、由1種Μ上（甲基）丙稀酸脂系單體與i種以上（甲 幻丙烯義系寡聚物構成者，較佳為由i種以上丙稀酸醋 系募承物構成者、或由〖種以上丙稀酸I系寡聚物與1種以 上（甲基)丙雜旨系單體構成者。在提高與基板間之密接性 的的下£佳為3有胺甲酸酉旨系寡聚物（其係由丙婦酿氧 基與曱基丙烯醢孔基其中—者或雙方構成的硬化性官能 基在母1刀子中平均具有】8〜4個）、與甲基兩稀酸經烧基 23 201124354 醋（其係具有髮基數1個或2個且碳數3〜8的羥烷基）的硬化 性樹脂組成物。 再者’當積層體用途係平面顯示器（FPD)的前面板時， 為使硬化過私的樹脂收縮等不會對平面顯示器（FpD)的顯 不性能造成不良影響’較佳係硬化後的樹脂層屬於更低彈 性係數。因而’較佳係含有寡聚物（其每1分子中平均具有 1.8〜4個由（曱基）丙稀醢氧基構成的硬化性官能基）、經烷 基甲基丙稀酸si(其具有經基個或2個且碳數3〜8的經 烧基）、以及1種以上未含羥基的（曱基）丙烯酸酯系單體之硬 化性樹脂組成物。且’未具有經基的（曱基)丙稀酸自旨系單體 、’、《 s里，較佳係依質量比計多於上述具羥基的（甲基）丙烯酸 ^系早體含量。又’亦可取代未具經基的（曱基）丙烯酸醋系 單體’改為使用具有經基1個且碳數12〜22之經烧基的經烧 基（甲基）丙烯酸酯羥基。 (甲基）丙稀酸酯系單體係若考慮光硬化性樹脂組成物 t被放置於減㈣置内的減壓環境下，最好為具有能充分 抑制揮發性程度之低蒸氣壓的化合物 。當硬化性樹脂組成 物含有未具羥基的（曱基）丙烯酸酯系單體時，可使用諸如： 石厌數8〜22的（甲基）丙烯酸烷基酯、較低分子量的聚乙二醇 或歙丙二醇等聚醚二醇的單（曱基）丙烯酸酯、或二（甲基）丙 稀酸S旨等’較佳為碳數8〜22的曱基丙烯酸烷基酯。 (甲基）丙烯酸酯系寡聚物較佳係具有含2個以上重複單 元的鏈（聚胺甲酸酯鏈、聚酯鏈、聚醚鏈、聚碳酸酯鏈等）、 與（甲基）丙烯醯氧基之分子構造的（曱基）丙烯酸酯系寡聚 24 201124354 物。該（甲基）丙烯酸酯系寡聚物係有如通稱「胺曱酸酯丙烯 酸酯寡聚物」之具胺曱酸酯鍵結（通常更進一步包括聚酯 鏈、聚醚鏈）' 與2個以上（甲基）丙烯醯氧基的（甲基）丙烯酸 酯系寡聚物。胺曱酸酯丙烯酸酯寡聚物係因為依照胺甲酸 酯鏈的分子設計，可對硬化後的樹脂層的機械性能、及在 與基板間之密接性等進行廣範圍調整，因而屬更佳。 (曱基）丙烯酸酯系寡聚物的數平均分子量較佳係丨〇〇〇 〜100000、更佳係10000〜70000。若數平均分子量小於 1000 ’則會提高硬化後的樹脂層的交聯密度，導致有損及 秘月曰層柔軟性的可能性。反之’若數平均分子量大於 100000，則會有未硬化的硬化性樹驗成物黏度變得過大 的可能性。當（甲基）丙烯酸酯系寡聚物的黏度過高時，最好 併用（甲基）㈣酸料單體，俾使整體硬化性樹脂組成物的 黏度降低。 另方面’當使用為密封部形成時所使用之第2硬化性 樹脂組成物的情況， 3000Pa · s範圍内，： 為能較容易將黏度調整為上述200〜 s乾圍内’最好含有具硬化性基且數平均分子量[Technical Field] The present invention relates to a method for producing a laminated body comprising a pair of substrates and a curable resin composition existing between the pair of substrates The hardened layer. The laminate produced by the method of the present invention is suitable for use as a front panel such as a refreshing glass, an image display device, and more particularly, for example, a liquid crystal display (LCD), an organic EL or an inorganic EL. EL (Electrically Excited Light) Display, front panel of a flat panel display (FPD) such as a plasma display device, an electronic ink type image display device, and a protective plate such as a thin-film solar cell device or a touch panel. C BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION A pair of glass substrates are formed into an integrated laminated glass via an adhesive layer, because the damaged glass fragments adhere to the film without scattering, and thus are used as windshields for automobiles. Further, since it is difficult to penetrate and has excellent strength, it is used as a window glass (safety glass, anti-theft glass) of a building (see 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 is provided on the front surface of the liquid crystal panel is known, and the front panel is sealed with a transparent interlayer film between the transparent protective plate and the polarizing plate. (refer to Patent Document 3). In addition, a solar cell module having a solar cell device is known, and the 201124354 〒 battery device is sealed between a transparent surface material and a back surface material that are light-receiving surfaces, and sealed with a sealing material such as resin (see Patent Document 4). . There is a need in various technical fields for a laminate having a pair of substrates and hardening between the pair of substrates and a cured layer of the resultant. There are many proposals for the production method of the laminated body, and the method described in Patent Document 2 is not limited to (4). The type of the curable resin composition which becomes the intermediate layer between the substrates and the substrate is not limited, and can be effectively utilized. The resource of the intermediate layer is excellent in terms of productivity and small environmental load. In this method, a sealing portion for sealing a curable resin composition is formed on a peripheral portion of one of the substrates, and then a curable resin composition is supplied to a region surrounded by the sealing portion on the substrate. Next, the other substrate is superposed on one of the substrates in a reduced pressure environment to hold and seal the hard resin composition between the pair of substrates. Next, a pair of substrates which are held by the curable resin composition and sealed are placed under a pressure environment higher than the above-described reduced pressure environment (e.g., at atmospheric pressure). When the environmental pressure rises, the pair of transparent substrates are pressed in the direction in which they are in close contact with each other, and since the void volume remaining in the sealed space is reduced in accordance with the environmental differential pressure, the curable resin composition flows into the pair of substrates and is sealed. In the decompression space in the sealed space in which the portion is sealed, the entire sealed space is uniformly filled with the curable resin composition. Then, a laminate is obtained by hardening the hard resin composition. For example, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2, No. Hei. No. Hei. No. Hei. Patent Application Laid-Open No. Hei 11-87743 C. SUMMARY OF THE INVENTION: SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION As described above, the method for producing a laminated body described in Patent Document 2 is a method in which a curable resin composition is held between a pair of transparent substrates in a reduced pressure environment, and sealed by a method. It is placed in a pressure environment higher than the above-described reduced pressure environment (for example, at atmospheric pressure) to exhibit a state in which the entire sealed space is uniformly filled with the curable resin composition. However, it is difficult to exhibit a uniform filling state of the curable resin composition in the entire sealed space, depending on the viscosity of the curable resin composition to be used and the layer thickness of the curable resin composition present in the sealed space. That is, when the viscosity of the curable resin composition used is high (for example, the viscosity of the curable resin composition is 0. When the layer thickness of the curable resin composition existing in the sealed space is large (for example, when the layer thickness of the curable resin composition is 30 μm or more), the curable resin composition is held. The sealed pair of substrates are placed under the pressure environment of the above-mentioned decompression environment (for example, at atmospheric pressure), and then the space between the spaces is reduced, and the required time is increased. Due to the fact that the entire closed space is uniformly filled with the curable resin composition, it takes a long time. 201124354 takes a long time. The present invention has been made to solve the problems of the above-described conventional techniques, and an object thereof is to provide a method for producing a laminate by curing a sealed curable resin composition held between a pair of substrates to form a laminate. A novel method for the time required for the entire sealed space to be uniformly filled with a curable resin composition. Means for Solving the Problem In order to achieve the above object, the method for manufacturing a laminated body according to the present invention comprises the steps of: preparing two substrates; forming a sealing portion on a peripheral portion of one of the substrates, the sealing portion being used for sealing a curable resin composition; a curable resin composition is supplied to a region surrounded by the sealing portion on one of the substrates; and another substrate is superposed on the supplied curable resin composition under a reduced pressure atmosphere And holding a curable resin composition between a pair of substrates and sealing the same; and placing a pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, in the second The curable resin composition is cured in a pressure environment to produce a laminate, and the method for producing the laminate is characterized in that the coated state of the curable resin composition supplied onto the substrate is controlled, and the curable resin composition is When the other substrate is overlapped on the other substrate, when the other substrate is superposed on one of the substrates, there is 6 201124354 in the foregoing sealing portion The curable resin composition layer in the surrounding region satisfies the following (1) to (3); (1) the voids present in the curable resin composition layer, and the equivalent BJ diameter of the projected shape (-lent drde) (diameter) IVe is 1 〇 _ or less; (2) a portion where the void is not present in the curable resin composition layer, and the equivalent circular diameter 〇 障 of the projection 1 shape is 4 〇 _ or less; The H composition layer and the voids present in the curable resin composition layer are in a state of being in contact with the sealing portion. It is to be noted that "satisfiable (1) to (3)" means that any of the items described in (1), (2), and (3) can be satisfied. The method of manufacturing the monthly laminate is more than (4) at least one of the substrate-to-substrate is a transparent substrate. In the method for producing a laminate according to the present invention, the viscosity of the curable resin composition is 0. 2~5〇pa. . The method for producing a laminated body according to the present invention is in the thickness of the curable resin composition layer in the space sealed by the above-mentioned substrate / '1', and is 30 to 30 μm. In the method for producing the laminate H, the portion (4) is formed using a second curable resin composition having a viscosity a s. In the manufacturing method of the core layer laminate, it is preferred that the pressure reducing environment is 0. It is preferable that the pressure of the second environment is higher than the pressure of the pressure-reduced environment by a pressure of 5 GkPa or more, and the pressure environment is sealed toward the pressure of the 201124354 2 In the curable resin composition for forming a resin film which is supplied in the region, the pressure-reducing environment in which the other substrate is superposed and sealed under reduced pressure corresponds to the first pressure environment. In the method for producing a laminate according to the present invention, Preferably, the curable resin composition is supplied to a region surrounded by the sealing portion on one of the substrates, and the curable resin composition is dispersed and dispersed in a region surrounded by the sealing portion. When the curable resin composition is dispersed and dropped, the equivalent circle diameter of the curable resin composition dropped by the one of the substrates and the nozzle used for the dispersion dripping is forcibly expanded, and 俾The equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion is made uniform. The manufacturer of the laminate of the present invention In the case where the curable resin composition is supplied onto one of the substrates to supply the curable resin composition to the region surrounded by the seal on one of the substrates, the curable dendrimer composition satisfies the following (4) The vibration curve of ~(9); (4) The displacement in the vertical direction according to the direction of the vibration curve (X) and the amplitude (Y) in the vertical direction; (5) The displacement of the adjacent vibration curve (6) When the thickness of the vibration curve at the start of supply is set to !!^!^!!), the period (x) (mm) and the amplitude (Y) (mm) are Satisfy the following formula: 2. 1xm^X^ i〇xm (2. 1xm)/2^Y^(1〇xm)/2 (7) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d (s_r) between the dynamic curve and the seal is used. (mm) is satisfied with the following formula: d(s. r)^ 2. 5xm (8) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d(r_r)(mm) between the adjacent vibration curves satisfies the following formula: d(r. r)^ 5xm (9) When E=2Y-2m, the E(mm) system satisfies the following formula: (Y+d(r. r))/10^E^Y+d(r. r) The above-mentioned "satisfaction (4) to (9)" means that any one of the requirements described in (4) to (9) can be satisfied. Further, in the method for producing a laminate according to the present invention, the curable resin composition is supplied to one of the substrates to supply the region surrounded by the seal on one of the substrates, and the curable resin composition may be used. The vibration curve satisfying the following (10) to (14) and the straight line advancing in the same direction as the vibration curve are adjacent to each other; (10) A certain period (X) and amplitude in the vertical direction with respect to the direction of advancement of the vibration curve (Y) Repeat displacement; (11) When the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) satisfy the following formula: 2 . 1xm^ 10xm (2. 1xm)/2^ Y^(10xm)/2 (12) When the vibration curve is located near the seal and the thickness of the vibration curve at the start of supply is m (mm), the vibration curve is the shortest between the seals The distance d(w)(mm) satisfies the following formula: d(s. r)^ 2. 5xm 9 201124354 (13) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d(rr) (mm) between the adjacent vibration curve and the line satisfies the following formula: d(r) . r)^ 2. 5xm (14) When E=2Y-2m, the E(mm) system satisfies the following formula: (Y+d(r. r)) / 20 ^ E ^ (Y + d (r. r))/2 In addition, the above-mentioned "satisfaction (10) to (14)" means that any one of the requirements described in (10) to (14) can be satisfied. Further, in the method for producing a laminate according to the present invention, it is preferable that the time from the start of the dropping of the region surrounded by the sealing portion on one of the substrates to the hardening resin composition is 30 to 1800 seconds. According to the method for producing a laminated body of the present invention, it is possible to shorten the time required for uniformly filling the entire space sealed by the pair of substrates and the sealing portion by the curable resin composition, which is carried out during the production of the laminated body, and to improve the lamination. Productivity. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of a substrate. Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion of the substrate surrounded by the sealing portion. Figs. 3(a) to 3(c) are diagrams showing temporal changes of the curable resin composition in which the substrate is dispersed in a dot shape by a region surrounded by the sealing portion. When the vacuum-curable resin composition of the fourth (a) to (d) figure is subjected to vacuum lamination in the state of 10201124354 shown in Fig. 3(a), the curable resin composition is decompressed during vacuum lamination. State diagram after the environment. In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(b) to (4), the state in which the curable resin composition is laminated in a vacuum state and after the decompression environment is released. In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(4) to (4), the state of the curable resin composition after vacuum lamination and after the decompression environment is released. The seventh (a) to (e) drawings are time-dependent changes of the curable resin composition in which the substrate is dispersed in a dot shape by a region surrounded by the sealing portion. Fig. 8 is a sequence diagram in which a substrate is surrounded by a sealing portion by a single-point nozzle, and the composition of the curable resin is dispersed. • Fig. 9 is a sequence diagram in which a multi-point nozzle is used to dispense a curable resin composition from a region surrounded by a sealing portion. Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse and drop a curable resin composition on a substrate surrounded by a sealing portion. Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a composition of a curable resin in a region surrounded by a sealing portion. Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a composition of a curable resin in a region surrounded by a sealing portion. Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable resin composition. Fig. 14 is a graph showing the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalent value of the voids present in the curable resin composition layer. 11 201124354 Relationship between the circle diameters Dpore. Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 16 corresponds to a partially enlarged view of Fig. 15, showing temporal changes in the shape of the vibration curves 3〇a, 30b. Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 19 is a view showing a preferred form of the coating when the curable resin composition is applied in a line shape. &20; Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 21 is a view showing a preferred strip form when the curable resin composition is applied in a line shape. <Fig. 2 is a view showing a preferred woven form when the curable resin composition is applied in a line. &2; Figure 2 is a diagram showing the preferred coating pattern of the hardened shaft as a linear coating. Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. C. The method of the invention is as follows. The following is a description of the method for producing the laminated body of the present invention with reference to the drawings. In the method for producing a laminate according to the present invention, in a pair of substrates, a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is used to seal the curable resin composition. Fig. 1 is a plan view showing a state in which a sealing portion 20 is formed on a peripheral portion of the substrate 10 in a plan view. [Substrate] In the method for producing a layered product of the present invention, it is preferable that at least one of the pair of substrates is used because the curable resin composition for forming a sealing portion is preferably a photocurable resin composition. It belongs to a transparent substrate. In this case, only one of the pair of substrates may be a transparent substrate and the other may be an opaque substrate. Alternatively, both of the substrates may be transparent substrates. Here, when one of them is a transparent substrate and the other is an opaque substrate, a sealing portion may be formed at a peripheral portion of the transparent substrate, or a sealing portion may be formed at a peripheral portion of the opaque substrate. Further, the 'transparent substrate' is not particularly limited as long as it is transparent, i.e., a substrate having visible light transmittance. Specific examples of the transparent substrate may be, for example, a glass substrate and a transparent resin substrate. Among these, a glass substrate is preferred from the viewpoints of transparency, light resistance, low birefringence, high planar precision, surface scratch resistance, and high mechanical strength. In addition to the sodium glass, the material of the glass substrate is, for example, a high-through glass (white plate) or a borosilicate glass having a lower iron content and a smaller blue color. The material of the transparent resin substrate can be, for example, a resin material having high transparency (polycarbonate, polyacrylic acid, etc.). Furthermore, the transparent substrate can be subjected to at least visible light transmittance, and 13 201124354 can also be used to perform fine-grain processing on the surface of the substrate for scattering or folding of light, or to perform light-shielding on the surface of the substrate. . Further, it is also possible to use a transparent substrate in which a plurality of transparent substrates are bonded together or a transparent substrate to which an optical film or the like is bonded as a body. Further, a structure including a transparent substrate as a part of constituent elements may be used as a transparent substrate. Such a structure including the transparent substrate as a part of the constituent elements may be, for example, a liquid crystal display device (LCD), an organic EL or an inorganic EL, or an electropolymer display device. The electronic ink type image display device is a flat panel display (FPD), a thin layer solar cell device, a touch panel, and the like. "When a pair of substrates, one of which is an opaque substrate, a specific example of an opaque substrate can be as follows. A substrate made of a metal material such as stainless steel, a substrate made of a ceramic material, or a resin substrate which is shielded by dispersing a filler capable of absorbing visible light in a substrate. Further, when both of the pair of substrates are transparent substrates, the substrate may be formed of the same material or may be formed of a different material. That is, both of the transparent substrates may be a glass substrate or a transparent resin substrate, and one of the pair of transparent substrates may be a glass substrate and the other may be a transparent resin substrate. The thickness of the substrate is not particularly limited, and in the case of a transparent substrate, the glass substrate is usually preferably 6 mm from the viewpoint of mechanical strength and transparency. In particular, in the case where a transparent laminated body having a small thickness is required, the thickness of the glass substrate is preferably 0. 3~l_5mm, more preferably 〇. 3 to 1 mm. Also, the thickness of the transparent 14 201124354 resin sheet is usually 0. 1 ~ 3mm. On the other hand, in the case of an opaque substrate, it is usually from the viewpoint of mechanical strength and thinness and weight reduction. 8~4mm. Further, the thickness of the pair of substrates may be the same or different. The surface of the substrate, more specifically, the surface on which the sealing portion J is formed in the peripheral portion, may be subjected to a surface treatment for the interfacial adhesion between the rising portion and the sealing portion. Here, the surface treatment may be performed only on the peripheral portion of the substrate, or may be performed on the entire surface of the substrate. The surface treatment method is a method in which the surface of the substrate is treated with a decane coupling agent or the like. [Seal portion] A curable resin composition that is held between a pair of substrates and sealed in a reduced pressure environment after the curable resin composition supplied from the region surrounded by the sealing portion is blocked on the substrate In the manufacturing process of the laminated body of the present invention, it is required to have an interface in which the hardenable composition supplied to the sealing portion does not leak more than the sealing target. It is required to have a firmness to maintain the shape of the laminated body in the laminated body of the present invention. The sealing portion that satisfies the requirements is provided on the peripheral portion of one of the substrates. The sealing member may be formed by a sealing member of the adhesive or the adhesive. The member of the sealing member is provided with a long strip on the surface (double-sided tape) The system is as follows: The strip or rod of the adhesive layer or the adhesive layer is formed in the periphery of the surface of the substrate to form an adhesive layer or an adhesive 15 201124354 layer, and a strip is attached thereto ^. • Using a curable resin composition to form a dam-shaped sealing precursor on the peripheral portion 1 of one of the substrate surfaces by printing or spot-turning, hardening the hardened tree scorpion composition, and then on the surface The adhesive layer or the adhesive layer is formed. Further, a high-viscosity curable tree sputum and a product which are used as the second curable resin composition are used, and a dispenser or a die coater is used in the periphery of one of the substrates. The sealing portion that satisfies the above requirements can be formed by applying a predetermined thickness. The following description of the curable resin composition used to form the sealing portion is also referred to as a "second curable resin composition". Here, in the order of the second curable resin composition described later, when the curable resin composition held between the pair of substrates and sealed is cured, the second curable resin composition may be cured at the same time, or may be sealed. The curable resin composition is hardened before being hardened. Further, one of the constituent elements of the method for producing a laminated body according to the present invention includes: "a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is for sealing a curable resin composition". The "sealing portion" at the position includes a sealing precursor before curing, which is a peripheral portion of the surface of one of the substrates on which the sealing portion is formed, and the curable resin composition is formed into a dam shape. When the curable resin composition is supplied to the region surrounded by the sealing portion, the second curable resin composition has a strength capable of sealing the curable resin composition for forming the resin film, and performs vacuum lamination in the order described later. When the pressure-reducing environment is released, the sealing portion 16 201124354 can be deformed by the thickness of the curable resin composition layer existing in the space sealed by the pair of substrates and the sealing portion, and vacuum lamination can be performed in the order described later. When the pressure-reducing environment is released, the sealing portion has a strength capable of withstanding atmospheric pressure, and the dot is preferably 200 to 3000 Pa·s, more preferably 5 to 2 〇〇〇Pa·s. Here, spacer particles having a predetermined particle diameter may be incorporated into the first hard resin composition in order to maintain the distance between the substrates. Further, the second curable resin composition (4) curable resin composition is preferably one which satisfies the above viscosity. In order to prevent the curable resin composition supplied to the region surrounded by the sealing portion from leaking, the sealing portion preferably forms a layer composed of a curable resin composition supplied from a region surrounded by the sealing portion (hereinafter, In the case of gold, there is a case where the thickness of the "thickness resin composition layer" is abbreviated to a certain thickness. For example, it is preferable that the curable resin composition layer has a predetermined thickness of 1. 1 time or more and 2 times or less. Further, the width of the sealing portion varies depending on the thickness of the curable resin composition layer, and is preferably 0. 5 to 5 mm, 〇 _ 5 to 3 mm. When the sealing portion is formed by application of the second curable resin composition having the viscosity, S is a high-viscosity resin composition used in the formation of the sealing portion, and thus is such as a pair of sealing portions. The shape of the curable resin composition supplied in the surrounding area does not change with time after coating. Therefore, the formed seal portion has a partial defect, or the width of the seal portion is partially thinned, and these defects are not eliminated over time. Therefore, when there is a partial defect or refinement of the formed sealing portion, the curable resin planting material supplied to the region surrounded by the sealing portion is performed before the vacuum lamination is performed in the order described later, or when the vacuum lamination is performed. 17 201124354 will bleed out to the outside of the sealing portion, and thus there is a possibility that there is a large gap in the curable resin composition existing in a space sealed by the plate and the sealing portion. Further, when the curable resin composition supplied from the region surrounded by the sealing portion oozes to the outside of the sealing portion, the laminated body pattern to be produced may be damaged. Further, when the formed sealing portion is partially defective or refining, when the decompression environment is released in the order described later, the gas enters the space sealed by the pair of the substrate and the sealing portion, resulting in the presence of the gas. The curable resin composition in a sealed space has a possibility of occurrence of a large void. In addition, when the sealing portion is formed, the case where the curable resin composition overlaps at the point where the coating is applied is not eliminated over time. Therefore, when the vacuum lamination is performed in the order described later, the thickness of the sealing portion becomes partial. In a uniform case, there is a possibility that a large gap occurs in the curable resin composition existing in the sealed space between the pair of substrates and the sealing portion. Further, the width of the sealing portion due to the overlapping portion is increased, which may impair the quality of the laminated body to be produced. Therefore, when the sealing portion is formed by applying the second curable resin composition, it is preferable that the second curable resin composition is applied, and then it is preferable to cause partial defects such as partial defects, after the second curable resin composition is applied. Shortcomings such as refinement and overlap. However, since the above problem does not occur depending on the size of the defect, it is preferable to check whether or not there is a disadvantage that the predetermined allowable range is exceeded. The inspection method is a method of confirming the size of the defects existing in the coated curable resin composition by image processing. 18 201124354 Next, the curable resin composition is supplied to a region on the substrate surrounded by the sealing portion. The supply amount of the curable resin composition is set in advance as follows.  When the curable resin composition is held between the pair of substrates and sealed, the space sealed by the pair of substrates and the sealing portion is filled with the curable resin composition. At this time, the supply amount of the curable resin composition is determined only after the volume reduction due to the hardening shrinkage of the curable resin composition is considered. In the method for producing a layered product of the present invention, when the curable resin composition is sandwiched between a pair of substrates and sealed in the order described later, the layer of the curable resin is present in the space sealed by the substrate and the sealing portion. The thickness is preferably from 30 to 3000 μm. The reason is that the curable resin composition layer not only functions as an adhesive between a pair of substrates, but also has a function of imparting mechanical strength to the layer. Thus, a thickness is required, and on the other hand, generally, such as an opening member or a display The component requirements are thin and lightweight, so it is best not to increase the thickness without any reason. When the curable resin composition is sandwiched between a pair of substrates and sealed in the order described later, the thickness of the curable resin composition layer existing in the space sealed by the pair of substrates and the sealing portion is more preferably 3 〇 8 8 〇〇叫^, 特佳系100~40〇μιη. Further, depending on the case, the thickness of the curable resin group may be as thin as possible. In this case, the thickness of the curable tree residue layer is preferably 30 to 4 〇〇 μηι, more preferably 100 to 2 〇〇 μπι. , especially good 1 (nine) ~ 160μηι. The method of supplying the curable resin composition is such that the substrate which is formed in accordance with the above-described procedure is laid flat and then supplied by a supply mechanism such as a dispenser in a dot shape or a linear shape. Further, the specific supply sequence of the relevant curable resin composition is described later. In the production method of the present invention, a method of injecting a curable resin into a gap of a laminate formed in advance (for example, a method described in JP-A-57-165411, JP-A-2001-339088, In the present specification, 'a higher viscosity curable resin composition can be used. Thereby, when the curable resin composition is cured, the hardening shrinkage can be lowered, and the mechanical strength of the resin layer after curing can be improved. The viscosity of the curable resin composition for forming a resin film to be used is preferably from the viewpoint of easy handling in the steps of industrial production, transfer, and application of a large amount of the curable resin composition. 2~50Pa.  s. In addition, the term "viscosity of the curable resin composition for forming a resin film" as used herein means the viscosity in the temperature region at the time of carrying out the method for producing the layered product of the present invention, in particular, the supply of the curable resin composition to After the region surrounded by the sealing portion, the viscosity in the temperature region of the vacuum laminate is carried out in the order described later. For example, when the order is carried out at normal temperature, it is the viscosity of the curable resin composition at normal temperature. Therefore, although it differs depending on the temperature at which the order is carried out, it is in the range of 5 to 80 °C in any case. In this regard, the viscosity of the second curable resin composition used in the formation of the sealing portion is also the same. The viscosity of the curable resin composition used is preferably 1 to 2 Å Pa.  s, better system 5~20Pa. As the curable resin composition satisfying the above viscosity, a curable resin composition containing a high molecular weight curable compound (oligomer or the like) as described in JP 201124354 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 at the time of hardening the curable resin composition becomes small, and the mechanical strength of the resin layer after hardening is enhanced. On the other hand, high molecular weight curable compounds are mostly highly viscous. Therefore, from the viewpoint of ensuring the mechanical strength of the resin layer after curing and suppressing the remaining of the bubbles, it is preferable to adjust the viscosity by dissolving the curable monomer having a small molecular weight in the high molecular weight curable compound. However, the viscosity of the curable resin composition is lowered by using a curable monomer having a small molecular weight, but the curing shrinkage at the time of curing the curable resin composition is increased, and the mechanical strength is liable to lower. The curable resin composition to be used is preferably a photocurable resin composition. The photocurable resin composition can be hardened in a short time by using less heat energy than the thermosetting resin composition. Therefore, in the present invention, by using the photocurable resin composition, the environmental load at the time of manufacturing the laminate can be reduced. Further, since the photocurable resin composition is used in an amount of several to several tens of parts, it can be substantially cured, so that the production efficiency of the laminated body is high. The "photocurable resin composition" refers to a material which is cured by the action of light to form a resin layer. The photocurable resin composition can be, for example, the following, and can be used in a range in which the hardness of the resin layer after curing is not excessively high. A composition containing a compound having an addition polymerizable unsaturated group and a photopolymerization initiator. • The ratio of the unsaturated group to the molar number of the thiol group is approximately 21 201124354 Polyolefin compound having 1 to 6 unsaturated groups (triallyl isocyanate, etc.) and having 1 to 6 A thiol group polythiol compound (triethylene glycol dithiol) and a composition containing a photopolymerization initiator. • A composition containing an epoxy compound having two or more epoxy groups and a photocationic generator. The photocurable resin composition preferably has a group selected from the group consisting of acryloxy group and mercapto propylene oxy group, from the viewpoint that the curing rate is relatively fast and the transparency of the resin layer after curing is high. At least one of a compound of one or more kinds of groups (hereinafter referred to as "(meth)acryloxy") and a photopolymerization initiator. A compound having a (meth) acryloxy group (hereinafter also referred to as "(fluorenyl) acrylate compound") is preferably a compound having 1 to 6 (meth) acryloxy groups per molecule. From the viewpoint that the resin layer after hardening does not become excessively hard, it is more preferably a compound having 1 to 3 (meth) acryloxy groups per molecule. The (meth) acrylate-based compound is preferably an aliphatic or alicyclic compound which does not contain an aromatic ring as much as possible from the light resistance of the resin layer after curing. Further, the (meth) acrylate-based compound is more preferably a compound having a hydroxyl group from the viewpoint of enhancing the adhesion at the interface with the substrate. The content of the (meth)acrylic acid S-based compound in the total amount of the (meth)acrylic acid-based compound is preferably 25% by mass or more, and more preferably 40% by mass or more. On the other hand, a compound having a hydroxyl group tends to cause an excessively high modulus of elasticity of the resin layer after curing, and in particular, when a (meth)acrylate having a hydroxyl group is used, the resin layer after hardening becomes used depending on the use of the laminate. The possibility of being strong. For example, when 22 201124354 is used for the front panel of a flat panel display (FPD), since the hardened resin layer is preferably a low modulus of elasticity, it has a base in the total amount of the (meth) acrylate compound (A) The acrylate content is preferably 4 Å by mass. /〇 The following, more preferably 3 〇 mass% or less. In addition, for example, a laminate of a substrate made of a different material such as a glass substrate and a resin substrate such as polycarbonate may be laminated on the surface of the substrate having different surface energies so that the resin layer can exhibit a proper adhesion to any of the substrates. A resin layer having an adhesive state of a low modulus of elasticity can be used. On the other hand, when a thinner glass substrate is laminated with a thicker glass substrate, the mechanical strength of the south laminate can also be improved by providing a resin layer having a high modulus of elasticity and being as thin as 〇1 mm or less. The (meth) acrylate content of the (tetra) group is set to 60% by mass or more. The (meth)acrylic acid S-based compound may be a lower molecular weight compound (hereinafter referred to as a 6-olefin 1-based monomer) or may be a higher molecular crystallization with a repeating unit. (hereinafter referred to as "(meth)acrylic acid vinegar oligomer"). The (meth) propylene S-based compound may be, for example, one composed of one or more (meth)acrylic acid I-based monomers, one composed of one type of propylene-based methacrylates, and one type. The above-mentioned (meth) acrylate monomer is composed of one or more kinds of (methicone methacrylate oligomers), preferably one or more types of acrylic acid vinegar-based constituents, or Any of the above-mentioned acrylic acid I-based oligomers and one or more (meth)acrylic monomers. The adhesion between the substrate and the substrate is improved. The product (which has an average of 8 to 4 in the mother 1 knives from the sulfonate oxy group and the fluorenyl propylene porphyrin group), and the methyl diacid acid is burned. Base 23 201124354 vinegar (which is a hydroxyalkyl group having one or two bases and having a carbon number of 3 to 8). Further, when the laminate is used as a front panel of a flat panel display (FPD) In order to shrink the hardened resin, etc., it will not adversely affect the display performance of the flat panel display (FpD). Coefficients. Thus' preferred system containing oligomer (which have per molecule an average of 1. 8 to 4 sclerosing functional groups composed of (fluorenyl) acryloxy), alkyl methacrylic acid si (having a base or two and a carbon number of 3 to 8) And a curable resin composition of one or more kinds of (nonyl) acrylate-based monomers having no hydroxyl group. Further, the amount of the (meth)acrylic acid-based precursor having no trans-group (indenyl)-acrylic acid-based monomer, ', and s, is preferably more than the above-mentioned hydroxyl group-containing (meth)acrylic acid. Further, it is also possible to use a mercapto (meth) acrylate hydroxyl group having a mercapto group having one via group and having a carbon number of 12 to 22 instead of the (fluorenyl) acrylate vinegar monomer having no mercapto group. When the (meth) acrylate-based single system is placed under a reduced pressure environment in which the photocurable resin composition t is placed in the reduced (four) position, it is preferably a compound having a low vapor pressure capable of sufficiently suppressing the degree of volatility. . When the curable resin composition contains a (hydroxyl) acrylate monomer having no hydroxyl group, an alkyl (meth) acrylate such as an anthrax 8 to 22, a polyethylene glycol having a lower molecular weight can be used. Or a mono(indenyl) acrylate of a polyether diol such as propylene glycol or a di(meth)acrylic acid S or the like is preferably an alkyl methacrylate having a carbon number of 8 to 22. The (meth) acrylate-based oligomer preferably has a chain having two or more repeating units (polyurethane chain, polyester chain, polyether chain, polycarbonate chain, etc.), and (meth) (Mercapto) acrylate oligomer 24 of the molecular structure of propylene methoxy group 201124354. The (meth) acrylate-based oligomer has an amine phthalate bond (generally further including a polyester chain or a polyether chain) as generally referred to as an "amine phthalate acrylate oligomer" and two A (meth) acrylate-based oligomer of the above (meth) acryloxy group. The amine phthalate acrylate oligomer is preferable because it can adjust the mechanical properties of the cured resin layer and the adhesion to the substrate in a wide range according to the molecular design of the urethane chain. . The number average molecular weight of the (fluorenyl) acrylate-based oligomer is preferably from 10,000 to 100,000, more preferably from 10,000 to 70,000. If the number average molecular weight is less than 1000 Å, the crosslinking density of the resin layer after curing is increased, which may impair the flexibility of the secret layer. On the other hand, if the average molecular weight is more than 100,000, there is a possibility that the viscosity of the unhardened curable tree is too large. When the viscosity of the (meth) acrylate-based oligomer is too high, it is preferable to use a (meth) (tetra) acid monomer alone to reduce the viscosity of the entire curable resin composition. On the other hand, when the second curable resin composition used for forming the sealing portion is used, in the range of 3,000 Pa·s, it is preferable to adjust the viscosity to the above-mentioned 200 to s dry circumference. Hardenable group and number average molecular weight

性的丙稀酸酯系寡聚物。Sexual acrylate oligomers.

姻或苯偶姻系、氧化膦系、 苯乙_系、酮縮醇系、笨偶 二苯基i§!系、噻噸酮系、醌 25 201124354 系等光聚合起始劑，較佳為 住马本乙_系或氧 始劑。當利用短波長可見 膦糸“。起 劑的吸收波長帶來看，更佳為時，/讀光聚合起始 為氣化鱗糸光聚合起始劑。藉 由併用吸收波長帶不同的2α(始劑藉 — 乂上先聚合起始劑，便可縮短 硬=間1、封部形成時所仙之第2硬化性樹脂組成物能 提尚表面硬化性，因而屬更佳。 光陽離子產㈣可例如鏽«、化合物等。 硬化性樹脂組成物係視必要亦可含有諸 劑、光硬化促_、鏈轉移劑、光安定劑（科線吸收劑、 自由基捕獲劑等)、抗氧化劑、難燃化劑、接著性提升劑(矽 烧偶。劑等）、顏料、染料等各種添加劑，較佳係含有聚合 終止劑、光蚊劑。特㈣聚合終止劑含有少於聚合起始 劑的量，便可改善硬化性樹脂組成物的安定性，亦可調整 硬化後的樹脂層的分子量。 但，依照積層體的用途，最好避免含有會妨礙硬化後 樹脂層之光線穿透可能性的添加劑。若舉一例，當積層體 用途係平面顯示器（FPD)的前面板、薄層太陽電池裝置的情 況，因為前者係來自形成顯示影像的平面顯示器（FPD)的射 出光與反射光、後者係太陽光會穿透硬化後樹脂層，因而 最好避免含有會妨礙該等光線穿透可能性的添加劑。例如 紫外線吸收劑便會吸收穿透樹脂層的太陽光的紫外線成 分，導致入射於薄層太陽電池裝置中的光量降低、或對平 面顯示器（FPD)的顯示影像色調造成不良影響之可能性。但 是，另一方面，對太陽光可穿透的樹脂層要求耐光性，特 26 201124354 別係對短波長光的耐 收：情况:較佳係適當調整其_性:= >的彈w：r :提w與基板間之密接性、及調整硬化後樹脂 «=劑較佳係含有鏈轉移劑，更佳係分子内具硫 =終止劑係可舉例如:氣卿二第三丁基氮酿 _:::=:基兒茶叫 二定劑係可舉例如:紫外線吸收劑(笨并三嗤系、二 %水楊酸酿系等）、自由基捕獲劑（受阻胺系）等。 =劑係可舉例如填系、硫系的化合物。 =聚σ起始劑及各種添加劑因為硬化性樹脂組成物會 t減壓環境下，因此最好係分子量較大、減壓下的 蒸氣壓較小之化合物。 其次’在減壓環境下，依照上述順序對基板上由密封 部所包圍區域供應的硬化性樹脂組成物上重疊另一基板。 為達成此步驟，只要在其中—基板的表面中，依上述順序 供應有硬化性樹脂組成物之—側的表面朝向另—基板的狀 態下’使-對基板與另-基板重疊便可。藉此在—對基板 間挾持硬化性樹脂組成物並加以密封。 以下，在本5兒明書中有將於減壓環境下，在對由密封 部所包JS區域供應的硬化_ 成物上重疊另—基板的 順序簡稱為「真空積層」之情況。 本發明積層體的製造方法中，存在於其中__基板之由 27 201124354 密封部所包®區域巾的硬化輯脂組成物層，係在滿足下 述（1)〜(3)的狀態下施行真空積層。 (1) 存在於前述硬化性樹脂組成物層中之空隙，其投影 形狀的等值圓直徑〇]3(^為1〇111„1以下。 (2) 硬化性樹脂組成物層中未存在有空隙之部分其投 影形狀的等值圓直徑Dn〇n-p〇re為40mm以下。 (3) 刖述硬化性樹脂組成物層和與存在於前述硬化性樹 脂組成物層中之空隙，交互地與前述密封部呈相接觸之狀 態。 第2圖係基板的平面圖，在該基板1〇的周邊部形成卢圭 部20，在由該密封部20所包圍的部分中形成硬化性樹浐系 成物層30。在該硬化性樹脂組成物層3〇中均勻存在*隙曰 本發明製造方法中’存在於密封部所包圍區域中 化性樹脂組成物層在滿足上述（1)〜（3)的狀態下施彳-真 積層之理由，說明如下。 二 如上述，本發明製造方法中，當對基板之由密封部戶斤 包圍區域供應硬化性樹脂組成物時，在已形成密封部的武 板呈平放的狀態下，利用分配器等供應機構，將硬化吐^ 脂組成物呈點狀或線狀供應。當供應機構係使用八 μ 刀配器 時’供應硬化性樹脂組成物的喷嘴形態並無特別的限< 可使用例如第8圖所示的單點喷嘴1〇〇 ’如第9〜u圖所示的 多點喷嘴(分支喷嘴）101、102、103 ’如第17圖所示的多零 噴嘴（分支噴嘴）104中任一者。第Π圖中，為形成複數的振 動曲線30b，而使用多點喷嘴（分支喷嘴）104，但為形成^條 28 201124354 粗細度較大的振動曲線，亦可使用多點喷嘴（分支喷嘴）。 又，亦可在如第9〜11圖所示的多點喷嘴（分支喷嘴）101、 102、103，或如第17圖所示的多點喷嘴（分支喷嘴）104前端 安裝狹縫喷嘴。上述所謂「單點喷嘴」係指將硬化性樹脂 組成物滴下於基板上的硬化性樹脂組成物供應機構（分配 器）的前端喷嘴由一個構成者；所謂「多點喷嘴」係指將硬 化性樹脂組成物滴下於基板上的硬化性樹脂組成物供應機 構(分配器）的前端喷嘴由複數個構成者；又所謂「分支喷嘴」 係指將硬化性樹脂組成物滴下於基板上的硬化性樹脂組成 物供應機構（分配器）之前端部分支為複數喷嘴者。 第3 (a)〜（c)圖係對基板由密封部所包圍區域點狀分散 滴下的硬化性樹脂組成物之經時變化圖。 第3 (a)圖係剛將硬化性樹脂組成物從硬化性樹脂組成 物供應機構（分配器）前端的單點喷嘴點狀分散滴下後的狀 態圖，在基板10由密封部20所包圍區域中，硬化性樹脂組 成物30呈點狀分散。 硬化性樹脂組成物隨時間經過會有其形狀崩壞的情 況，藉由呈點狀分散的硬化性樹脂組成物彼此間相接觸， 便如第3(b)圖所示，經由在内部形成空隙40的狀態，由密封 部20所包圍區域將呈面狀擴展。 然後，若再經過時間，空隙40便會消滅，而如第3(c) 圖所示，在由密封部20所包圍區域中，硬化性樹脂組成物 30呈均勻存在狀態。 本案發明者等發現當施行真空積層時，分散滴下在由 29 201124354 密封部所包圍區域中的硬化性樹脂組成物，存在於第3(a) 〜⑷圖中任-狀態中，而此時的硬化性樹脂組成物狀態會 對後續硬化性樹脂組成物層的狀態造成影響更具體而言 係將實施真空積層後的積層體（即在—對基板間挾持硬化 性樹脂組成物層並加以密封的積層體），放置在高於減廢環 境的壓力環境下之狀態時，會對硬化性樹脂組成物層中有 無空隙造成影響。本案發明者等發現特別係就該積層體放 置在高於減壓環境的壓力環境之狀態下空隙會消失的觀 點，相較於第3(e)圖的狀態之下，乍看雖較佳於第3⑼圖， 但並非如此，而是如第3_，最好在有存在某特定尺寸* 隙的狀態下實施真空積層之事。 二 一雖後有^述，經真空積層實施後的積層體被放置於較 經實施真空積層過的減壓環境更高之壓力環境下（例如大 氣壓下。本說明書中，實施真空積層的減壓環境的下—步 驟，即高於前述減壓環境之壓力環境下，與上述減壓# 相比，稱為「第2壓力環境下」）(以下，本說明書中，^ 該:序稱「解除減壓環境」的情況)。藉由解除 造成的環境壓力上升，朝一對基板彼此間相密接的方向按 甲同時殘留在硬化性樹脂組成物層中的 «境的轉而縮減，藉此由-對基板與密封部所 在閉空間整體便利用硬化性樹脂組成物而被均勻填充。另 外’前述真空積層實施後的積層體係由2片基體及密封部= ^封:樹脂層形成用硬化性樹驗成物呈尚未硬化狀能 者’此便是所謂的「積層體前驅體」，本說明書中，亦有將 30 201124354 包括樹脂層形成用硬化性樹脂組成物尚未硬化的積層狀態 物、及樹脂層形成用組成物已呈硬化狀態物在内稱為「積 層體」。 然而，根據施行真空積層時硬化性樹脂組成物的狀 態，並無法充分發揮因解除減壓環境所造成的上述作用， 在減壓環境解除後的硬化性樹脂組成物層中會有空隙殘 存。關於此點，參照第4〜6圖進行說明。 第4(a)〜（d)圖係硬化性樹脂組成物在第3(a)圖所示狀 態時施行真空積層的情況下，真空積層時及解除減壓環境 後的硬化性樹脂組成物狀態圖，第4(a)圖相當於第3(a)圖。 但，省略在基板周邊部形成的密封部。針對此點，在第4(b) 〜(d)圖及後示的第5,6圖中亦同。第4(b)圖係真空積層實施 時的硬化性樹脂組成物狀態圖，第4(c)、（d)圖係減壓環境 解除後的硬化性樹脂組成物狀態圖，顯示減壓環境解除後 的硬化性樹脂組成物狀態之經時變化。 如第4(a)圖所示’當硬化性樹脂組成物3〇在基板1〇上點 狀分散的狀態下實施真空積層時，如第4(b)圖所示，藉由呈 點狀分散的硬化性樹脂組成物3 〇彼此間相接觸，該硬化性 樹脂組成物便在基板10上呈面狀擴展。但，在面上擴展的 硬化性樹脂組成物30之層中，除呈均勻分散的小空隙4〇之 外，尚有無規則存在的大空隙41。 如第4(c)、（d)圖所示，減壓環境解除後，存在於硬化 性樹脂組成物30之層中的空隙40,41會經時地縮小，但無規 則存在的大空隙41卻不會消除而係殘存於該層中的狀態。 31 201124354 空隙殘存的狀態不僅只有第4〜6圖所記載之狀態而已，尚 有各種狀態。 第5(a)〜（d)圖係當在硬化性樹脂組成物呈第3(b)圖所 示狀態下施行真空積層時’真空積層時及減壓環境後的硬 化性樹脂組成物狀態圖，第5(a)圖係圖中的硬化性樹脂組成 物與空隙間之關係多少有些差異，但相當於第3(b)圖。第5(b) 圖係真空積層實施時的硬化性樹脂組成物狀態圖，第5(c)、 (d)圖係減壓環境解除後的硬化性樹脂組成物狀態圖，經減 壓環境解除後的硬化性樹脂組成物狀態之經時變化。 如第5(a)圖所示，在存在於硬化性樹脂組成物3〇之層中 之空隙40均較小，且空隙40彼此間的間距為較小狀態下， 依均勻存在於該層中的狀態實施真空積層時，便如第5(b) 圖所示，在真空積層實施前後，硬化性樹脂組成物狀態並 未有如何的變化’但如第5(c)圖所示，藉由解除減壓環境， 存在於硬化性樹脂組成物30之層中的空隙40會縮小，然 後，如第5(d)圖所示，存在於層中的空隙會消除。 第6(a)〜（d)圖係硬化性樹脂組成物在第3(c)圖所示狀 態時施行真空積層的情況下，真空積層時及減壓環境解除 後的硬化性樹脂組成物狀態圖，第6(a)圖係相當於第3(c) 圖。第6(b)圖係真空積層實施時的硬化性樹脂組成物狀態 圖’第6(c)、（d)圖係減壓環境解除後的硬化性樹脂組成物 狀態圖，減壓環境解除後的硬化性樹脂組成物狀態之經時 變化。 如第6(a)圖所示，當基板1〇上的硬化性樹脂組成物3〇 32 201124354 並未开v成空隙而呈均勻存在之狀態下實施真空積層時便 如第6(b)圖所示，藉由實施真空積層而沿硬化性樹脂組成物 3〇之層的外緣形成大空隙41。此種大空隙41係如第6(c)、（d) 圖所示，減壓環境解除後雖會經時的縮小，但呈未消除而 殘存於該層中的狀態。 本發明的製造方法中，使用黏度為〇 2〜5〇Pa · s的較高 黏度樹脂膜形成用硬化性樹脂組成物，且形成在由密封部 所包圍區域中的硬化性樹脂組成物層厚度亦達3 〇 μπι以上 之相對來說較厚狀態，因此在減壓環境解除後的硬化性樹 脂組成物層中容易有殘存空隙的傾向。所以，針對此現象， 在滿足上述（〗）〜(3)的狀態下實施真空積層，對不致在減壓 锿境解除後的硬化性樹脂組成物層令殘存空隙來說係屬重 要。 若硬化性樹脂組成物層滿足上述（1)〜（3)，包含與密封 部20間之界面的硬化性樹脂組成物3〇之層全體，在存在於 硬化性樹脂組成物30之層中的空隙40均較小，且空隙4〇彼 此間的間距為較小的狀態下’呈均勻存在於該層中的狀 態。所以’藉由實施真空積層，然後解除減壓環境，便可 使存在於硬化性樹脂組成物30之層中的空隙縮小並消除。 上述（1)、（2)中，所謂「存在於硬化性樹脂组成物層中 之空隙的投影形狀」及「硬化性樹脂組成物層中未存在有 空隙之部分的投影形狀」，係指空隙對硬化性樹脂組成物層 表面的投影形狀、及未存在空隙的部分對該層表面的投影 形狀。以下’本說明書中，將空隙投影形狀的等值圓直徑， 33 201124354 間稱「空隙的等值圓直徑」，將未存在空隙部分的投影形狀 之專值圓直徑，簡稱「未存在空隙部分的等值圓直徑」。 *另外，上述（1)係指存在於硬化性樹脂組成物層中的所 有=隙，其投影形狀的等值圓直徑〇1_在10随以下。又， 上=(2)係指存在於硬化性樹脂組成物層中的所有未存在空 隙p刀’其投影形狀的等值圓直徑〇晒_障在40咖以下。 第2圖係使用硬化性樹脂組成物供應機構（分配器）的單 ..、占嗔嘴’將硬化性樹脂组成物呈點狀滴下於基板上之後的 硬化性樹脂組成物狀態圖，同圖中，0晒__係指「未存在 空隙部分的等值圓直徑」’ Dpore係指「空隙的等值圓 徑」。 再者’第15圖係使用硬化性樹脂組成物供應機構(分配 益）的列狀多點喷嘴…邊使多时嘴進行擺動，—邊將硬 化性樹脂組成物呈線狀滴下於基板上之後的硬化性樹脂組 成物狀態圖，同圖中，Dn(jnpt)re係指「未存在空隙部分的等 值圓直徑」，Dp()re係指「空隙的等值圓直徑」。另外，上述 所謂「等值圓」並不僅侷限於圓形狀，廣泛涵蓋其中一部 分為圓形、橢圓形、曲面形狀的各種形狀。當非為圓形狀 時，該形狀之等值圓直徑係指其長軸、短軸中，長軸與短 軸的平均直徑。 當硬化性樹脂組成物層未滿足上述(1)的情況，因為在 硬化性樹脂組成物30之層中存在有較大空隙，因此即便實 施真空積層，然後再解除減壓環境，仍無法使存在於硬化 性樹脂組成物的層中之空隙消除，而呈在該層中仍殘存空 34 201124354 隙的狀態。 本發明製造方法中，存在於硬化性樹脂組成物層中的 空隙二其投影形狀的等值圓直徑D_較佳係3 _以下。 «硬化性樹脂組成物層未滿足上述⑺的情況因為存 在於硬化性樹脂組成物觀層巾的空隙做關之間距較 f =/或因為空隙4G在該層中呈不均勻存在因而即便實 積y二、:後再解除減壓環境，仍無法使在硬化性樹 月曰組成物層中存在的空隙消除，而呈在該層中仍殘存空隙 的狀態。 介本^明製造方法中，硬化性樹脂組成物層中未存在有 空隙之部分’其投影形狀的等值圓直徑〇_較佳係^ _ 以下。 +當硬化性樹脂組成物層未滿足上述_情況時，硬化 組成物層經常與密封部呈接觸狀態、或空隙經常與 1 封部呈接觸狀態。前者的情況，如使用第6⑷〜⑷圖進 丁兒月藉由實施真空積層，沿硬化性樹脂組成物之層 卜彖形成大工隙41。此種大空隙並無法利用減壓環境的 解除而肩除現在該層中仍殘存空隙的狀態。後者的情 况在實知真空積層時，沿硬化性樹脂組成物層之外緣存 工隙®此即便貫施真空積層’然後再解除減壓環 仍無法使存在於硬化性樹脂組成物層中的空隙消除， 而呈現在該層中仍殘存空隙的狀態。 >本發明製造方法中，為在滿足上述⑴〜⑺的狀態下實 施真空積層’只要依以下順序實施如使用分配器將硬化性 35 201124354 樹脂組成物分散滴下的順序便可。 在基板由密封部所包圍區域中呈點狀分散滴下的硬化 性樹脂組成物，係從分散滴下後經過時間t，其狀態便如第 7(a)〜（e)圖所示進行變化。此處，第7(a)圖係剛將硬化性 樹脂組成物30分散滴下於基板1〇由密封部20所包圍區域後 (即t=〇)的狀態圖’而在由該密封部20所包圍區域中，硬化 性樹脂組成物3 0呈點狀分散。然後’藉由呈點狀分散的硬 化性樹脂組成物30彼此間相接觸，便如第7(b)圖所示，硬化 性樹脂組成物30在由密封部20所包圍區域中擴展為面狀， 在從分散滴下起經過時間t,的時點於硬化性樹脂組成物3 〇 層中形成空隙40。然後，空隙40係經時的變小，在從分散 滴下起經過時間h的時點，如第7(c)圖所示，該空隙4〇的等 值圓直徑0,呈滿足上述（1)的狀態，即成為Dp<)re=10mm。然 後，空隙40再更進一步經時的變小，在從分散滴下起經過 時間h的時點，如第7(d)，（e)圖所示’空隙40將消除。時間 k係依照基板的大小而有所差異’但較佳為3〇〜18〇〇秒、50 〜1000秒程度。 當使用具有配合硬化性樹脂組成物滴下部位數量之喷 嘴的分配器，將硬化性樹脂組成物對既定區域統括滴下 時’只要在依下式所示之時間t範圍内實施減壓積層便可。 但’依照基板的尺寸’並無法實現統括滴下硬化性樹 脂組成物，如第8圖所示，一邊使喷嘴100在基板1〇由密封 部20所包圍區域上進行移動，一邊滴下硬化性樹脂組成物 36 201124354 3〇 °此情況’從滴下開始起至滴下結束為止發生時間差的 結果’依照施行滴下的時期，硬化性樹脂組成物的形狀會 變為不同m果會有存在於硬化‘_驗成物30之層 中的空隙4G，其等值®直徑rw變為不均勻的問題。 當取代第8®細單點喷嘴⑽，改為㈣如第9、_ 所示之多點喷嘴(分支喷嘴）1〇卜1〇2時，因為從滴下開始起 至滴下結束所需_會雜，目而可緩和上述問題，但並 無法完全解決問題。 所以，如第8〜1〇圖所示，當在基板1〇由密封部加所包 圍區域上，一邊使喷嘴1〇〇、1〇卜1〇2進行移動一邊滴下 硬化性樹脂組成物3〇時，在由密封部2〇所包圍的全區域 中，必需注意要滿足上述（1)〜（3)。具體而言，必需在從最 初滴下起h以内且從最後滴下起以上的時間内實施真空 積層。為此便必需將滴下條件設定成從滴下開始起至滴下 結束的所需時間ts為滿足下式： ts < ⑴士） “在基板由·封部所包圍區域上，一邊使喷嘴進行移 動’ 一邊滴下硬化性樹脂組成物時所發生的上述問題，藉 由配合滴下時期，強制性改變所滴下的硬化性樹脂組成物 的形狀’更具體而言’強制性擴展硬化性樹脂組成物的投 影形狀的等值圓直徑（以下在本說明書簡稱「硬化性樹脂組 成物的等值圓直徑」），便可解決上述問題。 如第11圖所示’當在基板10由密封部2〇所包圍區域 上，一邊使多點噴嘴（分支噴嘴）1〇3進行移動，一邊滴下硬 37 201124354 化性樹脂組成物3G時，依照進行滴下的時期，硬化性樹脂 組成物的形狀可呈不同的狀態。當著眼於硬化性樹脂組成 物的等值圓直徑時，在較早階段滴下的硬化性樹脂組成 物，相較於在較晚階段訂的硬化性樹脂組成物，等值圓 直控會變大。因為基板1G係具有各種大小，因此就準備能 滴下於基板整面的喷嘴而言，在成本面上較為_，因而 多數情況係使用多點喷嘴。 相對於此藉由強制性擴展在較晚階段滴下的硬化性 樹脂組成物之等值圓直徑，便可縮小因滴下時_造成的 硬化性樹脂組成物之等值圓直徑的差，更甚者亦可使已滴 下的硬化性樹脂組成物的等值圓直徑呈均勻。第12圖中， 藉由強制性擴展在較晚階段滴下的硬化性樹脂組成物之等 值圓直徑，便可使存在於基板10由密封部2〇所包圍區域中 的硬化性樹脂組成物30之等值圓直徑均勻。 強制性擴展已滴下的硬化性樹脂組成物之等值圓直徑 的方法，如第12圖中箭頭所示，藉由使基板1〇與多點喷嘴 (分支喷嘴）1〇3進行相對性擺動，而強制性擴展硬化性樹脂 組成物的等值圓直徑之方法。此情況，亦可使基板1〇進行 擺動，亦可使多點噴嘴（分支噴嘴）103進行擺動。又，藉由 使滴下後的硬化性樹脂組成物接觸到諸如授拌子等任何突 起物’亦可強制性擴展硬化性樹脂組成物的等值圓直徑。 已滴下的硬化性樹脂組成物之等值圓直徑要擴展為何 種程度，只要依循以下的想法後再實施便可。 第13圖係當滴下某硬化性樹脂組成物時，在所滴下的 38 201124354 時點（即t=o)硬化性樹脂組成物之等值圓直徑為d〇時，滴下 後的經過時間t(sec)與該硬化性樹脂組成物的等值圓直徑 d(mm)間之關係圖。如該圖所示，在從開始滴下起經過時間 ta、tb、tn時所滴下之硬化性樹脂組成物’藉由分別將該硬 化性樹脂組成物的等值圓直徑擴展為da、db、dn，便可使滴 下完成時的硬化性樹脂組成物之等值圓直徑呈均勻。 本案發明者等經實驗性確認到滴下後的經過時間1與 該硬化性樹脂組成物的等值圓直徑d的增量(d-dO)之間，成 立下式關係： d-d〇=a xt1/2 式中，α:係依照硬化性樹脂組成物的黏性、基板表面 對硬化性樹脂組成物的濕潤性、已滴下的各個硬化性樹脂 組成物的體積而決定之係數。 根據該式，藉由將所滴下的硬化性樹脂組成物之等值 圓直徑設為何種程度擴展，便可使滴下完成時的硬化性樹 脂組成物之等值圓直徑呈均勻。另外，藉由使基板1〇與噴 嘴103進行相對性擺動，當擴展已滴下的硬化性樹脂組成物 之等值圓直徑時，只要將擺動的振幅s設為依上式所求得之 等值圓直徑d的增量(d-d〇)便可。 滴下後的經過時間t、硬化性樹脂組成物的等值圓直徑 d、及存在於硬化性樹脂組成物層中之空隙的等值圓直徑a photopolymerization initiator such as a benzoin system, a phosphine oxide system, a phenethyl ketone system, a keto ketal system, a styrene diphenyl i§! system, a thioxanthone system, or a hydrazine 25 201124354 system, preferably Live in the horse 乙 _ or oxygen initiator. When using a short-wavelength visible phosphine 糸 ". The absorption wavelength of the initiator is brought about, more preferably, / read photopolymerization starts with a gasified squama photopolymerization initiator. By using a combination of different absorption bands 2α ( The first agent can be shortened by the first polymerization initiator, and the second hardening resin composition which is formed when the seal is formed can improve the surface hardenability, and thus is preferable. Photocation production (4) For example, rust «, a compound, etc. The curable resin composition may contain various agents, photohardening _, chain transfer agent, light stabilizer (ketone absorber, radical scavenger, etc.), antioxidant, if necessary. Various additives such as a flame retardant, an adhesion promoter (such as a sputum sputum agent), a pigment, and a dye, preferably contain a polymerization terminator and a light mosquito. The (4) polymerization terminator contains less than a polymerization initiator. The amount can improve the stability of the curable resin composition, and can also adjust the molecular weight of the resin layer after hardening. However, according to the use of the laminate, it is preferable to avoid the possibility of impeding light penetration of the resin layer after curing. Additive, if one example, when The use of the layer is the front panel of a flat panel display (FPD), and the case of a thin-film solar cell device, because the former is from the emitted light and reflected light of a flat panel display (FPD) forming a display image, and the latter is penetrated and hardened by sunlight. The resin layer, and thus it is preferable to avoid the inclusion of an additive which hinders the possibility of such light penetration. For example, the ultraviolet absorber absorbs the ultraviolet component of the sunlight penetrating the resin layer, resulting in a decrease in the amount of light incident on the thin-film solar cell device. Or the possibility of adversely affecting the color tone of the display image of a flat panel display (FPD). However, on the other hand, the resin layer that is transparent to sunlight is required to have light resistance, and the special resistance to short-wavelength light is : Situation: It is better to adjust the _ sex: = > bomb w: r: to improve the adhesion between w and the substrate, and to adjust the resin after the hardening «= agent preferably contains chain transfer agent, better system molecule The sulfur-containing terminator can be exemplified by the following: qiqing two third butyl nitrogen brewing _:::=: the base tea is called a two-component agent, for example, an ultraviolet absorber (stupid and triterpenoid, two%) Salicylic acid, etc.) The base trapping agent (hindered amine type) or the like. The agent is, for example, a compound or a sulfur-based compound. The polysulfonate-based initiator and various additives are preferred because the curable resin composition is in a reduced pressure environment. A compound having a large molecular weight and a small vapor pressure under reduced pressure. Next, in the reduced pressure environment, the other substrate is superposed on the curable resin composition supplied from the region surrounded by the sealing portion on the substrate in the above-described order. To achieve this step, it is only necessary to overlap the substrate with the other substrate in the surface of the substrate in which the surface of the substrate is supplied with the curable resin composition in the above-described order toward the other substrate. The curable resin composition is held between the substrates and sealed. Hereinafter, in the book of 5, there is a superposition of the hardening_substance supplied to the JS region enclosed by the sealing portion in a reduced pressure environment. - The order of the substrates is simply referred to as "vacuum buildup". In the method for producing a laminate of the present invention, the layer of the hardened grease composition of the region towel which is covered by the seal portion of the 27 201124354 is disposed in a state satisfying the following (1) to (3). Vacuum layering. (1) The voids present in the curable resin composition layer have an equivalence circle diameter 〇]3 of the projected shape (^ is 1 〇 111 „1 or less. (2) There is no presence in the curable resin composition layer. The part of the void has a contour circle diameter Dn〇np〇re of 40 mm or less in the projected shape. (3) The hardenable resin composition layer and the void existing in the curable resin composition layer are alternately described above. The sealing portion is in a state of being in contact with each other. Fig. 2 is a plan view of the substrate, the Lugui portion 20 is formed at a peripheral portion of the substrate 1A, and a curable tree layer is formed in a portion surrounded by the sealing portion 20. 30. The layer of the curable resin composition layer 3 is uniformly present in the present invention. In the manufacturing method of the present invention, the layer of the chemical resin composition present in the region surrounded by the sealing portion satisfies the above (1) to (3). The reason for the lower layer-true layer is as follows. As described above, in the manufacturing method of the present invention, when the curable resin composition is supplied to the substrate surrounded by the sealing portion, the slab having the sealing portion is formed. In a flat state, using a dispenser or the like In the mechanism, the hardened sputum composition is supplied in a dot shape or a line. When the supply mechanism uses an eight μ knife adapter, there is no particular limitation on the nozzle shape for supplying the curable resin composition. For example, Fig. 8 can be used. The illustrated single-point nozzle 1'' is a multi-nozzle (branch nozzle) 101, 102, 103' as shown in Fig. 9 to u', as shown in Fig. 17 of any of the multiple zero nozzles (branch nozzles) 104. In the figure, a multi-point nozzle (branch nozzle) 104 is used to form a plurality of vibration curves 30b, but a multi-point nozzle (branch nozzle) may be used to form a vibration curve having a large thickness of 201124354. Further, a slit nozzle may be attached to the multi-point nozzle (branch nozzle) 101, 102, 103 as shown in Figs. 9 to 11 or the multi-point nozzle (branching nozzle) 104 as shown in Fig. 17 In the above-mentioned "single-point nozzle", the front end nozzle of the curable resin composition supply means (dispenser) which drops the curable resin composition on the substrate is composed of one; the "multi-point nozzle" means hardening. The resin composition is dropped on the substrate The front end nozzle of the curable resin composition supply means (dispenser) is composed of a plurality of members; the "branch nozzle" is a curable resin composition supply mechanism (dispenser) which drops the curable resin composition onto the substrate. The front end portion is a plurality of nozzles. Fig. 3 (a) to (c) are diagrams showing the temporal change of the curable resin composition in which the substrate is dotted and dispersed in a region surrounded by the sealing portion. Fig. 3 (a) A state in which the curable resin composition is dropped from a single-point nozzle at the tip end of the curable resin composition supply means (dispenser), and is formed of a curable resin in a region surrounded by the sealing portion 20 of the substrate 10. The material 30 is dispersed in a dot shape. When the curable resin composition collapses over time, the curable resin composition dispersed in a dot shape is in contact with each other, as shown in Fig. 3(b). It is shown that the region surrounded by the sealing portion 20 expands in a planar shape via the state in which the void 40 is formed inside. Then, if the time elapses, the void 40 is destroyed, and as shown in Fig. 3(c), the curable resin composition 30 is uniformly present in the region surrounded by the sealing portion 20. The inventors of the present invention found that when the vacuum laminate is applied, the curable resin composition which is dispersed and dropped in the region surrounded by the sealing portion of 29 201124354 exists in the state of the third (a) to (4), and at this time The state of the curable resin composition affects the state of the subsequent curable resin composition layer. More specifically, the laminated body after vacuum lamination is performed (that is, the curable resin composition layer is sandwiched between the substrates and sealed) When the laminate is placed under a pressure environment higher than the waste reduction environment, it affects the presence or absence of voids in the curable resin composition layer. The inventors of the present invention have found that the voids disappear in a state in which the laminate is placed in a pressure environment higher than a reduced pressure environment, and it is preferable to look at the state in the third (e) diagram. Fig. 3(9), but not the case, but as the 3rd, it is preferable to carry out the vacuum lamination in the presence of a certain size* gap. Although it is described later, the laminated body after the vacuum lamination is placed in a higher pressure environment than the vacuum-decompressed environment (for example, atmospheric pressure). In this specification, the vacuum layer is decompressed. The next step of the environment, that is, the pressure environment higher than the decompression environment, is referred to as "the second pressure environment" compared with the above-mentioned decompression # (hereinafter, in the present specification, ^: the prologue is "released" The situation of the decompression environment"). By the increase in the environmental pressure caused by the release, the direction in which the pair of substrates are in close contact with each other is reduced in the direction in which the nail remains in the layer of the curable resin composition, whereby the closed space in which the substrate and the sealing portion are located is The whole is conveniently filled with a curable resin composition. In addition, the laminated system after the implementation of the vacuum lamination is composed of two substrates and a sealing portion = ^: the cured layer for forming a resin layer is not yet cured." This is a so-called "layer precursor". In the present specification, the term "layered body" is also referred to as a layered state in which the resin layer-forming curable resin composition is not cured, and the resin layer-forming composition is in a cured state. However, depending on the state of the composition of the curable resin when the vacuum layer is applied, the above-described action due to the release of the reduced pressure environment is not sufficiently exhibited, and voids remain in the curable resin composition layer after the pressure reduction environment is released. This point will be described with reference to Figs. 4 to 6. In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(a), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in the fourth (a) to (d). Fig. 4(a) corresponds to Fig. 3(a). However, the sealing portion formed at the peripheral portion of the substrate is omitted. This point is also the same in Figures 4(b) to (d) and in Figures 5 and 6 which will be shown later. 4(b) is a state diagram of a curable resin composition when vacuum lamination is performed, and 4(c) and (d) are diagrams showing a state of a curable resin composition after the decompression environment is released, showing that the decompression environment is released. The state of the subsequent curable resin composition changes over time. When the vacuum layering is performed in a state in which the curable resin composition 3〇 is dispersed in a dot shape on the substrate 1 as shown in Fig. 4(a), as shown in Fig. 4(b), it is dispersed in a dot shape. The curable resin composition 3 is in contact with each other, and the curable resin composition spreads in a planar shape on the substrate 10. However, in the layer of the curable resin composition 30 which spreads on the surface, in addition to the uniformly dispersed small voids 4, there are irregular voids 41 which are irregularly present. As shown in the fourth (c) and (d), after the pressure reduction environment is released, the voids 40, 41 existing in the layer of the curable resin composition 30 are reduced over time, but the large gaps 41 are irregularly present. It does not eliminate and remains in the state of the layer. 31 201124354 The state in which the void remains is not only the state described in the fourth to sixth figures, but also various states. 5(a) to (d) are diagrams showing the state of the curable resin composition when vacuum lamination is performed in a state where the curable resin composition is in the state shown in Fig. 3(b). The relationship between the curable resin composition in the figure (5) and the void is somewhat different, but corresponds to the third (b) diagram. Fig. 5(b) is a state diagram of the curable resin composition at the time of vacuum lamination, and the fifth (c) and (d) are diagrams showing the state of the curable resin after the decompression environment is released, and are released by a reduced pressure environment. The state of the subsequent curable resin composition changes over time. As shown in Fig. 5(a), the voids 40 present in the layer of the curable resin composition 3〇 are small, and the gaps 40 are relatively small in the state, and are uniformly present in the layer. When vacuum lamination is carried out, as shown in Fig. 5(b), the state of the curable resin composition does not change before and after the vacuum lamination is carried out, but as shown in Fig. 5(c), When the reduced pressure environment is released, the voids 40 existing in the layer of the curable resin composition 30 are reduced, and then, as shown in Fig. 5(d), the voids existing in the layer are eliminated. In the case where the vacuum-based resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in the sixth (a) to (d). Fig. 6(a) is equivalent to Fig. 3(c). Fig. 6(b) is a diagram showing the state of the curable resin composition in the case of the vacuum lamination. The sixth (c) and (d) are diagrams showing the state of the curable resin after the decompression environment is removed. The state of the curable resin composition changes over time. As shown in Fig. 6(a), when the hardened resin composition 3〇32 201124354 on the substrate 1 is not uniformly opened, the vacuum layer is uniformly formed as shown in Fig. 6(b). As shown, a large void 41 is formed along the outer edge of the layer of the curable resin composition 3〇 by performing vacuum lamination. As shown in the sixth (c) and (d), the large gap 41 is in a state in which it is reduced in time after the release of the reduced pressure environment, but remains in the layer without being eliminated. In the production method of the present invention, a curable resin composition for forming a high-viscosity resin film having a viscosity of 〇2 to 5 〇Pa·s is used, and a thickness of the curable resin composition layer formed in a region surrounded by the sealing portion is used. In the case of a relatively thick state of 3 〇μπι or more, the curable resin composition layer after the pressure reduction environment is released tends to have a void. Therefore, in this case, it is important to carry out the vacuum lamination in a state in which the above (J) to (3) are satisfied, and it is important for the curable resin composition layer which is not removed in the decompression environment to cause residual voids. When the curable resin composition layer satisfies the above (1) to (3), the entire layer of the curable resin composition 3〇 including the interface with the sealing portion 20 is present in the layer of the curable resin composition 30. The gaps 40 are all small, and the gaps 4 〇 are in a state where the distance between them is small, and the state is uniformly present in the layer. Therefore, by performing vacuum lamination and then releasing the decompression environment, the voids existing in the layer of the curable resin composition 30 can be reduced and eliminated. In the above (1) and (2), the "projection shape of the voids present in the curable resin composition layer" and the "projection shape of the portion where the voids are not present in the curable resin composition layer" means voids. The projected shape of the surface of the curable resin composition layer and the projected shape of the portion where the void is not present on the surface of the layer. In the following description, the equivalence circle diameter of the void projection shape is referred to as "the equivalent circle diameter of the void" between 33 201124354, and the diameter of the circle of the projection shape in which the void portion is not present is simply referred to as "there is no void portion. Equivalent circle diameter". In addition, the above (1) means all the gaps present in the curable resin composition layer, and the equivalence circle diameter 〇1_ of the projection shape is 10 or less. Further, the upper = (2) means that all of the voids present in the curable resin composition layer have the equivalent circle diameter of the projected shape of the blade knives of 40 coffee or less. Fig. 2 is a view showing a state of a curable resin composition in which a curable resin composition is supplied to a substrate in a punctiform manner using a curable resin composition supply means (dispenser). Medium, 0 drying __ means "equal diameter of the void portion" "Dpore" means "equal diameter of the void". In the case of the column-shaped multi-nozzle of the curable resin composition supply mechanism (distribution benefit), the multi-layer nozzle is oscillated while the curable resin composition is dropped onto the substrate in a line shape. In the figure of the curable resin composition, in the figure, Dn (jnpt) re means "the diameter of the equivalence circle where no void portion exists", and Dp () re means "the diameter of the equivalence circle of the void". Further, the above-mentioned "equivalent circle" is not limited to a circular shape, and covers a wide variety of shapes including a circular shape, an elliptical shape, and a curved shape. When it is not a circular shape, the equivalent circle diameter of the shape refers to the average diameter of the major axis, the minor axis, and the major axis and the minor axis. When the curable resin composition layer does not satisfy the above (1), since a large void exists in the layer of the curable resin composition 30, even if vacuum lamination is performed and then the decompression environment is released, the existence cannot be made. The voids in the layer of the curable resin composition are eliminated, and the state in which the gaps remain in the layer remains. In the production method of the present invention, the equivalence circle diameter D_ of the projection shape of the voids 2 present in the curable resin composition layer is preferably 3 or less. «The hardening resin composition layer does not satisfy the above (7) because the gap existing in the gap of the curable resin composition is smaller than f = / or because the void 4G is uneven in the layer, even the actual product Y2: After the decompression environment is released, the void existing in the sclerosing tree sap composition layer cannot be eliminated, and the void remains in the layer. In the manufacturing method of the present invention, the portion of the curable resin composition layer where no void exists is formed, and the equivalent circular diameter 〇 of the projected shape is preferably _ or less. + When the curable resin composition layer does not satisfy the above-described condition, the hardened composition layer is often in contact with the sealing portion, or the void is often in contact with the one portion. In the former case, by performing vacuum lamination using the sixth (4) to (4) drawing, a large gap 41 is formed along the layer of the curable resin composition. Such a large gap cannot be removed by the release of the reduced pressure environment, and the state in which the void remains in the layer is now removed. In the case of the latter, when the vacuum lamination is known, the work gap is applied along the outer edge of the curable resin composition layer, and even if the vacuum lamination is applied, then the decompression ring is released, and the residual resin composition layer cannot be present in the layer of the curable resin composition. The voids are eliminated, and a state in which voids remain in the layer is present. In the production method of the present invention, in order to carry out the vacuum lamination in a state in which the above (1) to (7) are satisfied, the order of dispersing the curable composition of the curable 35 201124354 resin by using a dispenser may be carried out in the following order. The curable resin composition which is dispersed in a dot shape in a region surrounded by the sealing portion in the substrate is subjected to a time t from the dispersion and the state is changed as shown in Figs. 7(a) to 6(e). Here, in the seventh (a) diagram, the curable resin composition 30 is dispersed and dropped on the substrate 1 after the region surrounded by the sealing portion 20 (that is, t = 〇), and the sealing portion 20 is used. In the surrounding region, the curable resin composition 30 is dispersed in a dot shape. Then, the curable resin composition 30 which is dispersed in a dot shape is in contact with each other, and as shown in Fig. 7(b), the curable resin composition 30 is expanded into a planar shape in a region surrounded by the sealing portion 20. The gap 40 is formed in the layer 3 of the curable resin composition at a time t from the dispersion of the dispersion. Then, the void 40 becomes smaller as time passes, and the time point h elapsed from the dispersion dripping, as shown in Fig. 7(c), the equivalence circle diameter 0 of the void 4〇 satisfies the above (1). State, that is, become Dp<)re=10mm. Then, the gap 40 is further reduced over time, and the gap 40 is eliminated as shown in Figs. 7(d) and (e) at the time h elapsed from the dispersion dripping. The time k varies depending on the size of the substrate, but is preferably about 3 〇 18 〇〇 sec, 50 〜 1000 sec. When a dispenser having a nozzle having a number of dropping portions of the curable resin composition is used, when the curable resin composition is dropped onto a predetermined region, the pressure-reducing layer may be applied in the range of time t shown by the following formula. However, it is not possible to realize a dripping curable resin composition in accordance with the size of the substrate. As shown in Fig. 8, the nozzle 100 is formed by dropping a curable resin while moving the nozzle 100 on the region surrounded by the sealing portion 20. Article 36 201124354 3〇°In this case, the result of the time difference from the start of the dripping to the end of the dripping, the shape of the curable resin composition will be different depending on the period of the dripping, and the fruit will be present in the hardening. The gap 4G in the layer of the object 30 has a problem that the equivalent value ® diameter rw becomes uneven. When replacing the 8th fine point nozzle (10), it is changed to (4) When the multi-point nozzle (branch nozzle) shown in ninth, _1 is 1〇2, it is necessary to be mixed from the start of dripping to the end of dripping. The above problem can be alleviated, but it cannot be completely solved. Therefore, as shown in the eighth to the first drawings, the curable resin composition is dropped while the nozzles 1 and 2 are moved while the substrate 1 is surrounded by the sealing portion. At the time, in the entire area surrounded by the sealing portion 2, it is necessary to pay attention to satisfying the above (1) to (3). Specifically, it is necessary to carry out vacuum lamination in a time period from the initial dropping of h and from the last dropping. For this reason, it is necessary to set the dropping condition so that the required time ts from the start of the dropping to the end of the dropping is satisfied by the following formula: ts < (1) ± "Moving the nozzle while the substrate is surrounded by the sealing portion" When the above-mentioned problem occurs when the curable resin composition is dropped, the shape of the hardened resin composition to be dropped is forcibly changed by the dropwise addition period, and more specifically, the projected shape of the curable resin composition is forcibly expanded. The equivalent circle diameter (hereinafter referred to as "equivalent circle diameter of the curable resin composition" in the present specification) can solve the above problem. As shown in Fig. 11, when the multi-point nozzle (branch nozzle) 1〇3 is moved while the substrate 10 is surrounded by the sealing portion 2〇, the hard 37 201124354 resin composition 3G is dropped. The shape of the curable resin composition may be in a different state during the dropping. When focusing on the equivalent circle diameter of the curable resin composition, the hardening resin composition dropped at an earlier stage becomes larger than the hardening resin composition set at a later stage. . Since the substrate 1G has various sizes, it is preferable to use a multi-point nozzle in order to prepare a nozzle that can be dropped on the entire surface of the substrate on the cost side. In contrast, by forcibly expanding the equivalence circle diameter of the curable resin composition which is dropped at a later stage, the difference in the equivalence circle diameter of the curable resin composition due to dropping can be reduced, and even worse. It is also possible to make the equivalence circle diameter of the dripped curable resin composition uniform. In Fig. 12, the curable resin composition 30 present in the region surrounded by the sealing portion 2 is formed by forcibly expanding the equivalence circle diameter of the curable resin composition which is dropped at a later stage. The equivalent circle has a uniform diameter. A method of forcibly expanding the equivalence circle diameter of the hardened resin composition that has been dropped, as shown by an arrow in FIG. 12, by relatively oscillating the substrate 1〇 with the multi-point nozzle (branching nozzle) 1〇3, A method of forcibly expanding the equivalence circle diameter of the curable resin composition. In this case, the substrate 1A can be oscillated or the multi-point nozzle (branch nozzle) 103 can be swung. Further, it is also possible to forcibly expand the equivalence circle diameter of the curable resin composition by bringing the curable resin composition after the dropping into contact with any protrusions such as a stir-feeding material. The extent to which the equivalence circle diameter of the hardened resin composition that has been dropped has to be expanded can be carried out by following the following ideas. Figure 13 is a graph showing the elapsed time t (sec) after dropping a 38 ° 24 24 24 24 24 24 24 24 24 24 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 A graph showing the relationship between the equivalent circle diameter d (mm) of the curable resin composition. As shown in the figure, the curable resin composition dripped when the elapsed time ta, tb, and tn from the start of the dripping is expanded by the equivalence circle diameter of the curable resin composition to da, db, dn The equivalence circle diameter of the curable resin composition at the time of completion of the dropping can be made uniform. The inventors of the present invention experimentally confirmed that the elapsed time 1 after the dropping and the increment (d-dO) of the equivalence circle diameter d of the curable resin composition establish the following relationship: dd〇=a xt1/ In the formula, α is a coefficient determined by the viscosity of the curable resin composition, the wettability of the surface of the substrate to the curable resin composition, and the volume of each of the curable resin compositions that have been dropped. According to this formula, by expanding the diameter of the equivalence circle of the hardened resin composition to be dropped, the equivalence circle diameter of the curable resin composition at the time of completion of the dropping can be made uniform. Further, when the substrate 1〇 and the nozzle 103 are relatively oscillated, when the equi-circular diameter of the hardened resin composition that has been dropped is expanded, the amplitude s of the wobble is set to the equivalent value obtained by the above formula. The increment of the diameter d (dd〇) can be. Elapsed time t after dropping, equivalent circle diameter d of the curable resin composition, and equivalent circle diameter of voids present in the curable resin composition layer

Dp〇re 間之關係將進一步敛述。 第I4圖係滴下後的經過時m、硬化性樹脂紅成物的等 值圓直徑d、及存在於硬化性樹脂組成物層巾之空隙的等值 39 201124354The relationship between Dp〇re will be further clarified. The first graph is the equivalent m diameter d after the dropping, the equivalent circle diameter d of the curable resin red product, and the equivalent value of the void existing in the curable resin composition layer sheet.

圓直彳二Dp〇re間之關係圖。由圖中得知，隨著滴下後的經過 時間t之增加，硬化性樹脂組成物的等值圓直徑d亦會增 加’而空隙的等值圓直徑D pore 則會減少。圖形中的t|、t2及 t3係與第7圖同義。即，在從分散滴下起經過時間^時，在 硬化性樹脂組成物3 0的層中形成空隙4 〇，在經過時間12時， 二隙4〇的等值圓直徑DpQre=1〇mm，在經過時間“時空隙 40會消除。 依如上述，當統括滴下硬化性樹脂組成物時，只要在 依下式所示之時間t内實施減壓積層便可。 根據第14圖的圖形，實施減壓積層時，若硬化性樹脂 組成物的等值圓直徑d、及空隙的等值圓直徑Dp〇re分別在以 下範圍内便可。 d2^d^d3 ^3 = Dpore = 〇2 S在基板由达、封部所包圍區域上，一邊使喷嘴進行移 動，一邊滴下硬化性樹脂組成物時，藉由使基板與噴嘴進 行相對性擺動，且將已滴下的硬化性樹脂組成物的等值圓 直徑，配合其滴下的時期進行適當擴展，便可使滴下結束 時的硬化性樹脂組成物之等值圓直徑呈均勻。此處，將第i 次滴下與第X次滴下間之時間差設為Tq、第丨次滴下的硬化 性樹脂組成物因經過時間TV,而造成的等值圓直徑擴展設 為ΔΑ-,、第X次的擺動振幅設為，若將第X次的擺動振 幅3;<設為SfAdy的話，在滴下結束時便可使硬化性樹脂組 40 201124354 成物的等值圓直徑呈均勻。 此處，就縮短從開始滴下起至實施真空積層的時間之 觀點’最好在剛要實施真空積層前便使所有硬化性樹脂組 成物的等值圓直徑成為屯。為能達成此情形，當最後滴下 的硬化性樹脂組成物之等值圓直徑設為士時，最好將屯與 的差分(drdf)當作振幅從第丨次滴下開始進行擺動。此時， 第η次的擺動振幅Sng Sn=Adx.|+(d2_df)。 使用分配器將硬化性樹脂組成物呈線狀塗佈的情況， 亦是當實施真空積層之際，存在於基板由密封部所包圍區 域中的硬化性樹脂組成物層必需滿足上述（丨）〜（3)。 本發明的製造方法中’為能在滿足上述〜(3)的狀態 下實施真空積層，只要依以下順序實施如將硬化性樹脂組 成物呈線狀塗佈的順序便可。 第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第15圖中，硬化性樹脂組成物的塗佈圖案形成振動曲 線30a，30b，該振動曲線30a，30b係相對於硬化性樹脂組 成物供應機構（分配器）的列狀多點噴嘴進行方向（第15圖的 情況，為基板10的長邊方向），在垂直方向（第15圖的情況， 為基板10的短邊方向）依一定的週期X及振幅γ進行重複位 移者。該振動曲線係具有藉由使基板與噴嘴進行相對性擺 動而將硬化性樹脂組成物施行塗佈而在基板上獲得之硬化 性樹脂組成物的帶狀既定週期與振幅之圖案塗膜。藉由將 硬化性樹脂組成物施行塗佈成為振動曲線3〇a、3〇b，便可 201124354 使基板10由密封部20所包圍區域中的較小空隙仙呈均句分 散的狀態。此處應注意之處，如使用第16圖進行的後述^ 振動曲線30a，30b的形成時期' 與空隙4〇的形成時期通常 並未一致，藉由振動曲線30a、30b的形狀進行經時性變化， 便會形成空隙40。此處’當硬化性樹月旨組成物呈線狀塗佈 時，塗佈的方法最好係僅從基板的長邊或短邊中任一方向 進行塗佈。從基板的長邊與短邊二方向進行塗佈因為會 發生已塗佈的硬化性樹脂組成物重疊、樹脂厚度出現較厚 部分與較薄部分的情況，因而最好避免。又，在重疊部分 中會有捲人氣泡的可祕，結果容易導致最終製品中發: 氣泡殘留情形，因而最好避免。 另外，為使由密封部20所包圍區域中的較小空隙4〇呈 均勻分散狀態’由第15圖中得知，相互鄰接振動曲線3如、 30b的位移必需相互成為反相位。 此處，就從基板10由密封部20所包圍區域中的較小空 隙40呈均勻分散狀態的觀點，當將開始供應時的振動曲線 30a之粗細度設為叫⑺叫時，週期x(mm)與振幅Y(mm)最好 分別滿足下式： 2.1xm^X^l〇Xm (2.1xm)/2^Y^(i〇xm)/2 更佳係週期χ及振幅γ滿足下式： 3xm^x^6xm (3xm)/2^Y^(6xm)/2 另外，上述說明中’利用與振動曲線3〇a的粗細度間之 42 201124354 關係，對週期X及振幅γ的較佳範圍進行說明，與振動曲線 3〇b的粗細度間之關係亦同。針對此點，下述d 較佳範圍亦同。 l(s-r>、d(r_r)的 再者，當實施真空積層之際，因為必需 即硬化性樹餘成物層中未存在空隙之部分，其投影(j狀 的等值圓直徑Dn〇np〇re必需在4〇mm以下，因而週期錄好在 mmu下、更佳在丨5麵以下。又振幅γ較佳在麵以 下、更佳在7.5mm以下。 再者’就沿密封部20不致產生較大空隙的觀點，振動 曲線3 0 a與密封部2 〇間之最短距離d ($ f)最好滿足下式： d(s-r)^ 2.5xm 此時’就與密封部20的各部位間之關係，要求振動曲 與密封部2〇間之最短距離d㈣滿足上式。即圖中上側 的密封部20與振動曲線3〇a間之最短距離、圖中下側的密封 部辦振動曲線鳩間之最短距離，要求圖中左側或圖中右 的在封#20、與振動曲線3〇a或振動曲線鳩間之最短距 離全部滿足上式。 振動曲線30a與㈣部2〇間之最短距離d㈣，更佳係滿 足下式： d(S.r)^ 0.5xm 振動曲線30a與密封部2〇間之最短距離d㈣的下限值並 無特別的限定，振動曲線他與密封部20相接亦可。但，若 縣曲線3〇a與密料2作疊，因為财該料的硬化性樹 成物層厚度會變大’因而最好振動曲線30a與密封部20 43 201124354 不要重疊。 再者，就使振動曲線30a、30b間不會產生較大空隙的 -觀點’最好相鄰接的振動曲線30a、30b的最短距離d(r-r)滿足 下式： d(r.r)^ 5xm 此情況，振動曲線30a、30b中’與開始供應時的粗細 度m間之關係最好能滿足上式。 相鄰接的振動曲線30a、30b的最短距離d(r_r)更佳係滿 足下式： d(r-r) ^ m 相鄰接的振動曲線3 0a、3 Ob的最短距離d(r_r)下限值並無 特別的限定，相鄰接的振動曲線3〇a、30b相接亦可。但， 若振動曲線30a、30b重疊，因為僅有該部分的硬化性樹脂 組成物層厚度會變大，因而最好振動曲線3〇a、30b不要 重疊。 第16圖係相當於第15圖之部分放大圖的圖示。其中， 為能圖示振動曲線30a、30b形狀的經時變化，便以擴大相 鄰接振動曲線30a、30b之間隔的狀態表示。第16圖振動曲 線30a、30b係如虛線所示，其粗細度會經時的擴大，導致 相鄰接的振動曲線30a、30b相接而形成空隙40。 另外，在形成相鄰接之振動曲線30a、30b時，振動曲 線30a、30b相接的情況下，便會在形成振動曲線3〇a、30b 的時點形成空隙40。 此處’所形成之空隙40的直徑E(mm)，更具體而言， 44 201124354 係在振動曲線3〇a、30b的振幅γ方向上之空隙4〇的直徑e(即 等值圓直徑），其依下式所示： E=2Y-2m 在實施真空積層0夺，最好空隙40的直徑E滿足下式，即 呈滿足上述（1)〜（3)的狀態，更具體係滿足上述⑴及⑺ 的狀態。 (Y+d㈣)/10SE$Y+d(叫 另外，上述係以振動曲線3〇a、幾的振中|γ及粗細^ 呈相等之情況為前提來記載。當振動曲線3〇a、通的振幅The relationship between the two straight lines and the Dp〇re. As is apparent from the figure, as the elapsed time t after the dropping increases, the equivalence circle diameter d of the curable resin composition also increases, and the equivalence circle diameter D pore of the void decreases. The t|, t2, and t3 in the graph are synonymous with the seventh graph. That is, when the elapsed time from the dispersion dripping, the void 4 形成 is formed in the layer of the curable resin composition 30, and the elapsed circle diameter DpQre = 1 〇 mm of the two-gap 4 在 at the elapse of time 12, When the elapsed time "time gap 40 is eliminated. As described above, when the curable resin composition is dripped, the pressure reduction layer can be carried out at time t shown by the following formula. When the layer is laminated, the equivalence circle diameter d of the curable resin composition and the equivalence circle diameter Dp〇re of the voids are respectively within the following ranges: d2^d^d3 ^3 = Dpore = 〇2 S on the substrate When the curable resin composition is dropped while the nozzle is moved, the substrate and the nozzle are relatively oscillated, and the equimolar circle of the hardened resin composition that has been dropped is formed by the movement of the nozzle. When the diameter is appropriately expanded in accordance with the period of the dropping, the diameter of the equivalence circle of the curable resin composition at the end of the dropping can be made uniform. Here, the time difference between the i-th drop and the X-th drop is set to Tq. , the first step of the hardening resin The equivalence circle diameter expansion due to the elapse of time TV is set to ΔΑ-, and the X-th swing amplitude is set to be the X-th swing amplitude 3; <SfAdy is ended at the end of the drop At this time, the equivalence circle diameter of the curable resin group 40 201124354 is uniform. Here, the viewpoint of shortening the time from the start of the dripping to the time of performing the vacuum lamination is made, and it is preferable to make all the vacuum layer just before the vacuum lamination is performed. The equivalence circle diameter of the curable resin composition is 屯. In order to achieve this, when the equivalence circle diameter of the last-dried curable resin composition is set to ±, it is preferable to treat the difference (drdf) of 屯The amplitude is swung from the third drop. At this time, the n-th swing amplitude Sng Sn=Adx.|+(d2_df). When the curable resin composition is applied linearly using a dispenser, it is also When the vacuum layering is performed, the curable resin composition layer existing in the region surrounded by the sealing portion of the substrate must satisfy the above (丨) to (3). In the manufacturing method of the present invention, 'the above-mentioned (3) can be satisfied. Carrying out vacuum lamination in the state of The order of applying the curable resin composition in a linear form may be sequentially performed. Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. The coating pattern of the resin composition forms vibration curves 30a, 30b which are oriented with respect to the column-shaped multi-nozzle of the curable resin composition supply means (dispenser) (in the case of Fig. 15, In the longitudinal direction of the substrate 10, in the vertical direction (the short-side direction of the substrate 10 in the case of FIG. 15), the displacement is repeatedly performed according to a predetermined period X and an amplitude γ. The vibration curve has a substrate by The nozzle is subjected to relative oscillation, and the curable resin composition is applied to apply a pattern of a predetermined period and amplitude of the curable resin composition obtained on the substrate. By applying the curable resin composition to the vibration curves 3a, 3b, it is possible to make the substrate 10 into a state in which the smaller gaps in the region surrounded by the sealing portion 20 are uniformly dispersed. It should be noted here that the formation period of the vibration curve 30a, 30b, which is described later using Fig. 16, is not consistent with the formation period of the gap 4〇, and the shape of the vibration curves 30a, 30b is temporally formed. When it changes, a gap 40 is formed. Here, when the curable tree composition is applied linearly, the coating method is preferably applied only from either the long side or the short side of the substrate. It is preferable to apply the coating from the long side and the short side of the substrate in such a manner that the applied curable resin composition overlaps and the resin thickness is thicker and thinner. Further, in the overlapping portion, there is a secret of the bubble of the person, and as a result, it is easy to cause the hair in the final product to be present, and it is preferable to avoid it. Further, in order to make the small gaps 4〇 in the region surrounded by the sealing portion 20 uniformly dispersed, it is understood from Fig. 15 that the displacements of the mutually adjacent vibration curves 3, 30b must be opposite to each other. Here, from the viewpoint that the small gap 40 in the region surrounded by the sealing portion 20 of the substrate 10 is uniformly dispersed, when the thickness of the vibration curve 30a at the time of starting supply is set to be called (7), the period x (mm) And the amplitude Y (mm) preferably satisfies the following formula: 2.1xm^X^l〇Xm (2.1xm)/2^Y^(i〇xm)/2 The better period χ and the amplitude γ satisfy the following formula: 3xm^x^6xm (3xm)/2^Y^(6xm)/2 In addition, in the above description, 'the best range for the period X and the amplitude γ is obtained by using the relationship between the thickness and the thickness of the vibration curve 3〇a 42 201124354. The relationship between the thickness and the thickness of the vibration curve 3〇b is also the same. For this point, the following preferred range of d is also the same. l (s-r>, d(r_r), when the vacuum layer is applied, since it is necessary that the portion of the layer of the curable tree is not present, the projection (j-shaped equivalent circle diameter Dn) 〇np〇re must be below 4〇mm, so the cycle is recorded under mmu, more preferably below 丨5. The amplitude γ is preferably below the surface, more preferably below 7.5mm. 20, the viewpoint of not causing a large gap, the shortest distance d ($f) between the vibration curve 30 a and the sealing portion 2 preferably satisfies the following formula: d(sr)^2.5xm at this time 'with the sealing portion 20 The relationship between the parts is required to satisfy the above formula by the shortest distance d (4) between the vibrating piece and the sealing portion 2, that is, the shortest distance between the upper sealing portion 20 and the vibration curve 3〇a in the figure, and the sealing portion on the lower side in the figure. The shortest distance between the vibration curve turns, the shortest distance between the seal #20, the vibration curve 3〇a or the vibration curve 左侧 on the left side or the right side of the figure is required to satisfy the above formula. The shortest between the vibration curve 30a and the (four) part 2〇 The distance d (four), better system satisfies the following formula: d (Sr) ^ 0.5xm The shortest distance d between the vibration curve 30a and the sealing portion 2 (4) The lower limit value is not particularly limited, and the vibration curve may be in contact with the sealing portion 20. However, if the county curve 3〇a is overlapped with the dense material 2, the thickness of the hardened tree layer of the material may change. Therefore, it is preferable that the vibration curve 30a and the sealing portion 20 43 201124354 do not overlap. Further, the viewpoints of the vibration curves 30a, 30b which do not cause a large gap between the vibration curves 30a, 30b are preferably the adjacent vibration curves 30a, 30b. The shortest distance d(rr) satisfies the following formula: d(rr)^ 5xm In this case, the relationship between the thickness of the vibration curves 30a, 30b and the thickness m at the start of supply is preferably satisfied by the above equation. The shortest distance d(r_r) of 30a and 30b is more preferably satisfying the following formula: d(rr) ^ m The lower limit of the shortest distance d(r_r) of the adjacent vibration curve 3 0a, 3 Ob is not particularly limited, The adjacent vibration curves 3a and 30b may be connected to each other. However, if the vibration curves 30a and 30b are overlapped, since only the thickness of the portion of the curable resin composition layer becomes large, the vibration curve is preferably 3〇. a, 30b do not overlap. Fig. 16 is a diagram corresponding to a partial enlarged view of Fig. 15. The temporal change of the shape of the moving curves 30a and 30b is expressed by expanding the interval between the adjacent vibration curves 30a and 30b. The vibration curves 30a and 30b of the sixteenth figure are indicated by broken lines, and the thickness thereof is expanded with time. The adjacent vibration curves 30a, 30b are brought into contact to form the gap 40. In addition, when the adjacent vibration curves 30a, 30b are formed, when the vibration curves 30a, 30b are connected, the vibration curve is formed. A gap 40 is formed at the time point of 3〇a, 30b. Here, the diameter E (mm) of the gap 40 formed, more specifically, 44 201124354 is the diameter e (i.e., the equivalent circle diameter) of the gap 4 在 in the amplitude γ direction of the vibration curves 3〇a, 30b. It is expressed by the following formula: E=2Y-2m In the implementation of the vacuum lamination 0, it is preferable that the diameter E of the void 40 satisfies the following formula, that is, the state satisfying the above (1) to (3), and the system satisfies the above. The status of (1) and (7). (Y+d(4))/10SE$Y+d (In addition, the above-mentioned system is described on the premise that the vibration curve 3〇a, the number of vibrations |γ, and the thickness ^ are equal. When the vibration curve is 3〇a, pass Amplitude

Ya、Yb及粗細度ma、mb係不同時，空隙4〇的直徑E便依下 式所示： E=Ya+Yb-(ma+mb) (Ya+Yb+2d(r.r))/20 ^ E ^ (Ya+Yb+2d(r.r))/2 再者，就從較容易工業性高速且曲線狀塗佈、以及由 使密封部所包圍區域中的硬化性樹脂組成物與空隙間之比 率為適g的觀點，開始供應時的振動曲線粗細度m較佳係1 〜40mm、更佳係3〜15mm。 為能將硬化性樹脂組成物塗佈呈既定振動曲線3〇还、 30b ’便如第17圖所示，使用在圖中χ軸、任一方向上均 可進行移動的喷嘴（多點喷嘴（包括分支喷嘴))1〇4塗佈硬化 性樹脂組成物塗佈。 如在將硬化性樹脂組成物呈點狀分散滴下的情況所說 明，滴下後的硬化性樹脂組成物會經時性擴展，導致其等 值圓直徑變大。當將硬化性樹脂組成物呈線狀塗佈時亦會 45 201124354 引發同樣的現象’振動曲線30a、30b的粗細度會絰時性變 粗。 因而，最好如第18，19圖所示，將形成振動曲綠3〇a時 的塗佈方向（第18圖中箭頭所示）、及形成與該振動曲線3〇a 相鄰接之振動曲線30b時的塗佈方向（第19圖中箭頭所示）設 為相反方向，理由係如第20圖所示，可使存在於由密封部 20所包圍區域中的空隙40大小呈均勻化。 再者，第15〜20圖係振動曲線3加與3〇15的振幅γ為相同 之例子’但亦可如第21圖所示，振動曲線3〇a’與振動曲線 30b’的振幅Y為不同。 再者，第15〜21圖中，相鄰接之硬化性樹脂組成物層 的圖案均形成振動曲線，但亦可如第22圖所示，相鄰接之 硬化性樹脂組成物層的圖案中，僅有其中一者為振動曲線 30a”，而另一者則為直線3〇c。 但，此情況下，最靠近密封部2〇必需非直線3〇c而必需 是振動曲線30a”。 再者，振動曲線30a”的週期χ及振幅γ，依照與開始供 應時的振動曲線粗細度m間之關係，最好滿足上述條件。 再者，振動曲線30a”與密封部2〇間之最短距離d(w),依 照與開始供應時的振動曲線粗細度m間之關係，最好滿足上 述條件。 再者，相鄰接之振動曲線3〇a”與直線30c間之最短距離 d(r-〇，依照與開始供應時的振動曲線粗細度m間之關係，最 好滿足有關相鄰接之振動曲線間之最短距離d(rr)所記載 46 201124354 的條件。 再者’利用相鄰接之振動曲線30a”與直線3〇(：的相接而 形成之空隙E(mrn) ’更具體而δ ’係在振動曲線3〇a”的振幅 Y方向上之空隙的直徑E(即等值圓直徑），其最好滿足下式： (Y+d(r.r))/20 ^ E ^ (Y+d(r.r))/2 再者，第15〜22圖中，在基板1〇的長邊方向上形成硬 化性樹脂組成物之層的圖案，但亦可如第23圖所示，在基 板10的短邊方向上形成硬化性樹脂組成物之層的圖案 (30e、30f)。 再者，第15〜23圖中，硬化性樹脂組成物層的圖案係 形成振動曲線’但亦可如第24圖所示，係在一定週期X設有 寬幅部位31的直線30f、30g。此情況亦適用將硬化性樹脂 組成物塗佈呈振動曲線3 0a、30b時所記載的條件。但，寬 幅部位31的最大寬度係滿足關於振動曲線所記載的振幅γ 之條件。 本發明積層體的製造方法中，真空積層可依照以下順 序實施。以下，本5兒明書中，一對基板中，將表面上有形 成密封部及硬化性樹脂組成物層之側的基板稱為「其中一 基板」’將表面上並無形成該等之側的基板稱為「另—基 板」。 將其中一基板放入減壓裝置中，在減壓裝置内的固定 支撐盤上將該基板平放成硬化性樹脂組成物層之面朝上狀 態。 在減壓裝置内的上部設有可朝上下方向移動的移動支 47 201124354 樓機構，在移動支撐機構安裝有另一基板。此處，當在另 一基板表面上形成薄膜系太陽電池裝置時，便將形成有薄 膜系太％電池裝置之側的表面朝下。又，當積層體的用途 係平面顯示器（FPD)時，便將顯示影像之側的表面朝下。 又，當在另一基板的表面設有抗反射層時，便將沒有形成 抗反射層之側的表面朝下。 另一基板放置於其中一基板上方且係未接觸到硬化性 樹脂組成物層的位置處。即，不使其中一基板上的硬化性 樹脂組成物層與另一基板相接觸而是呈相對向。 另外，亦可將能朝上下方向移動的移動支撐機構設置 於減壓裝置内的下部，並在移動支撐機構的上方放置其中 一基板。此時，另一基板係安裝於減壓裝置内的上部所設 置的固定支撐盤上，並使其中一基板與另一基板相對向。 再者，亦可使其中一基板與另一基板二者，由設置在 減壓裝置内的上下的移動支撐機構來支撐。 將其中一基板及另一基板配置於既定位置後，便將減 壓裝置的内部予以減壓而形成既定的減壓環境。若可能的 話’亦可在減壓操作中或形成既定減壓環境後，在減壓裝 置内使其中一基板及另一基板位於既定位置處。 在減壓裝置的内部形成既定減壓環境後，將由移動支 撐機構所支撐的另一基板朝下方移動，並使另一基板重營 於其中一基板上的硬化性樹脂組成物層上方。 藉由重疊’在其中一基板的表面、另一基板的下面、 以及由密封部所包圍的空間内密封著硬化性樹贿組成 48 201124354 物。 當重疊之際’利用另一基板的本身重量、來自移動支 樓機構的按壓等’硬化性樹脂組成物會被擠壓擴散，俾使 上述空間内充滿硬化性樹脂組成物，然後藉由解除減壓環 境’便形成無空隙的硬化性樹脂組成物層。 重疊時的減壓環境係l〇〇〇pa以下、較佳為〇.lpa以上。 若減壓環境過度低壓’便會有對硬化性樹脂組成物中所含 的各成分(硬化性化合物、光聚合起始劑、聚合終止劑、光 女定劑等）造成不良影響之可能性。例如若減壓環境過度低 壓，各成分便會有氣化的可能性，且為提供減壓環境而頗 耗費時間。減壓環境的壓力更佳係i〜1〇〇Pa。特佳係3〜 30Pa。 從使其中一基板與另一基板相重疊的時點起至解除減 壓環境為止的時間，並無特別的限定，可在硬化性樹脂組 成物Φ封後，便馬上解除減壓環境，亦可在硬化性樹脂組 成物密封後，仍將減壓狀態_在既定時間。藉由將減壓 狀態維持在既定時間，硬化性樹脂組成物便會在密閉空間 内進行抓動’俾使其中一基板與另一基板間的間隔能均 勻，即便藉由解除減壓環境，而被放置於較實施真空積層 時的減壓環境更高之第2壓力環境下，仍可輕易地維持密封 狀態。維持減壓狀態的時間係可為數小時以上的長時間， ’從生產政率的觀點’較佳在卜丨、時以内、更佳在分鐘 以内。 接著，若藉由解除減壓環境，而將挾持著硬化性樹脂 49 201124354 組成物的一對基板放置於較減壓環境更高的第2壓力環境 下，則藉由環境壓力的上升，其中一基板與另—基板便會 朝相抢接的方向按壓，因而硬化性樹脂組成物會在密閉空 門内進行流動，俾使被閉空間整體被硬化性樹脂組成物均 勻地真充，升> 成沒有空隙的硬化性樹脂組成物層。 此處’和壓力環境的壓力最好較實施真空積層的減壓 環境高出徽Pa以上。第2壓力環境的壓力通常最好為隱〜 120kPa。第2壓力環境可為大氣壓環境、亦可為較此更高的 壓力。就從硬化性樹脂組成物的硬化等操作能在不需要特 別設備的情況下便可實叙_，最佳為大氣壓環境。 在上述第2壓力環境下，利用其中一基板與另—基板的 按歷而進行之密接積層步驟，係可在執行上述^積層的 減壓裝置中，解除減壓裝置之減壓室的減壓，將該減壓室 調整為崎〜^㈣的壓力（例如大氣壓），再於該壓力環境 下化仃使前述飽旨層形成用硬化丨續餘成物進行硬化的 處理’或者亦可從施行真空積層的減壓裝置移往其他的化 處理農置’並將該硬化處理裝置内輕為嫩〜12啊的壓 力/再於該壓力環境下施行使前述樹脂層形仙硬化性樹 脂組成物進行硬化的處理。 將挾持著硬化性樹脂組成物的—對基板保持在較減壓 ¥境更高的第2壓力環境下之時間並無特別的限定。將挟持 者硬化性樹频成物的-對基板，從減壓裝 =理裝置中且截至開始進行硬化的製程均= 執行時’該製程所需要的時間便成為保持於第壎 50 201124354 力環境下的時間。所以，當放置於大氣壓環境下時，密閉 空間内的硬化性樹脂組成物層中已不存在空隙的情況、或 者在該製程期間硬化性樹脂組成物層中的空隙便已消失的 情況，可馬上使硬化性樹脂組成物硬化。當截至空隙消失 為止尚需要時間時，截至空隙消失為止前將挾持著硬化性 樹脂組成物的一對基板保持於第2壓力環境下。又，因為即 便拉長在第2壓力環境下保持的時間，通常仍不會造成阻 礙，因而就從製程上的其他必要性，亦可拉長在第2壓力環 境下的保持時間。 在第2壓力環境下的保持時間可為1日以上的長時間， 但就從生產效率的觀點，較佳在6小時以内、更佳在1小時 以内’就從更加提高生產效率的觀點，特佳在1〇分鐘以内。 接著’藉由使密閉空間内的硬化性樹脂組成物進行硬 化，便製得具有一對基板、與存在於該一對基板間的硬化 性樹脂組成物之硬化物層的積層體。 使硬化性樹脂組成物硬化的手段，係配合熱硬化性樹 脂組成物的種類而任意使用熱硬化或光硬化。但，如上述， 所使用的硬化性樹脂組成物較佳係光硬化性樹脂組成物。 光硬化性樹脂組成物的情況，例如從光源（紫外線燈、 高壓水銀燈等）照射紫外線或短波長可見光，藉由使密閉空 間内的硬化性樹脂組成物進行硬化，便製得具有—對基 板、與存在於該一對基板間的硬化性樹脂組成物之硬化物 層的積層體。 光從一對基板中的透明基板側進行照射。當雙方均為 51 201124354 透明基板的情況，亦可從二側進行照射。 當所製造的積層體係平面顯示器（FPD)的情況、以及當 該平面顯示_使用穿透型顯示裝置的情況，雖藉由使該 裝置產生動作便可獲得透光性，但因為大多屬於在未產生 動作的狀態下便不具透紐者，因而便從成為保護板的透 明基板照射會使硬化性樹脂組成物硬化的光。另一方面， 田忒平面顯不器係使用非動作時便呈透明狀態的穿透散 射型顯示裝置時，亦可彻來自顯示裝置側的光。 光較佳係紫外線或450nm以下的可見光4寺別係在透明 基板上設有抗反射層，而抗反射層或形成抗反射層時所使 用的秘月曰薄膜係紫外線不會穿透的情況，便必需利用可見 光進行硬化。 依照本發明製造方法所獲得的積層體，頗適用於薄層 太陽電池裝置或影像顯示裝置等。薄層太陽電池裝置的具 體例，係可舉例如：薄膜矽太陽電池裝置、黃銅礦系或cdTe 系等化合物半導體太陽電池裝置等等。另一方面，影像顯 不裝置的具體例係可舉例如：液晶顯示裝置(LCD)、有機EL 與無機EL之類的EL(電激發光）顯示裝置、電漿顯示裝置、 以及電子墨水型影像顯示裝置之類的平面顯示器（FPD)。 薄層太陽電池裝置的情況係構成積層體的一對基板 中’可僅在其中一基板上形成薄層太陽電池裝置，亦可在 雙方基板上均有形成薄層太陽電池裝置。 實施例 以下’根據實施例針對本發明進行更具體的說明。但， 52 201124354 本發月並不僅偏限於此。另外，例1、例7、例8、例1 〇、例 15係屬於實_ ’其他的例子則屬於比較例。 (例1) (搶封部形成用光硬化性樹脂組成物） 將分子末端經環氧乙烷改質過的雙官能基的聚丙二醇 (依羥值计算出的數平均分子量：4000)、與六亞甲二異氰酸 酯，依6比7的莫耳比進行混合，接著利用甲基丙烯酸異莰 酯（大阪有機化學工業公司製、ΙΒχΑ)進行稀釋後於在錫 化合物的觸媒存在下進行反應而獲得之預聚物中，依約丨比 2的莫耳比添加丙烯酸_2_羥乙酯並使其反應，藉此獲得經3〇 質量曱基丙烯酸異莰酯稀釋過的胺甲酸酯丙烯酸酯寡聚 物（以下稱「UC-1」）溶液。UC-1的硬化性基數係2，數平均 分子量約55000。UC-1溶液在60°C下的黏度約580Pa · s。 將90質量份的UC-1溶液、及10質量份的曱基丙烯酸_2-羥丁酯（共榮社化學公司製、LIGHTESTERHOB)均勻混合 而獲得混合物。將100質量份的該混合物、1質量份的丨_羥 基-¾己基-苯基-酮（光聚合起始劑，Ciba Specialty Chemicals公司製、IRGACURE 184)、0.1 質量份的雙(2,4,6-二曱基本曱酸基）-苯基氧化鱗（光聚合起始劑，Ciba Specialty Chemicals公司製、IRGACURE 819)、0·04質量份 的2,5-二第三丁基氫醌（聚合終止劑）、及0.3質量份的紫外線 吸收劑(Ciba Specialty Chemicals公司製、TINUVIN 109)均 勻混合，便獲得密封部形成用光硬化性樹脂組成物X。 在將密封部形成用光硬化性樹脂組成物X放入容器且 53 201124354 呈開放狀態下設置於減壓裝置内，將減壓裝置内減壓至約 20Pa並保持1〇分鐘，藉此施行脫泡處理 。經測定密封部形 成用光硬化性樹脂組成物χ (即第2硬化性樹脂組成物）在 25°C下的黏度，結果約14〇〇Pa · 8。 沿長1100mm、寬90〇mm、厚2min的鈉鈣玻璃製基板（以 下稱「基板A」。相當於本發明的其中一基板)距外周部靠内 側5mm位置’塗佈上述密封部形成用光硬化性樹脂組成物 X，便形成厚度1mm的密封部。 (樹脂層形成用光硬化性樹脂組成物） 將1莫耳的雙官能基的聚丙二醇(依羥值計算出的數平 均分子量：2000)、1莫耳的分子末端經環氧乙烷改質過的 雙g flb基的聚丙二醇（依經值計算出的數量平均分子量： 4000)、及1莫耳的乙二醇均勻混合，獲得多元醇混合物。 將該多元醇混合物、與異佛爾酮二異氰酸酯依5比6的莫耳 比進行混合，以在錫化合物觸媒存在下進行而獲得預聚 物’在該預聚物中依約1比2的莫耳比添加丙烯酸_2_羥乙酿 並使其反應’便獲得胺曱酸酯丙烯酸酯寡聚物（以下稱 「UA-2」）°UA-2的硬化性基數係2，數平均分子量約19000， 25°C下的黏度約1300Pa · s。 將60質量份的UA-2、及40質量份的甲基丙烯酸-2-羥丁 酯（共榮社化學公司製、LIGHT ESTER HOB)均勻混合，並 在100質量份的該混合物中，均勻溶解0.2質量份的雙(2,4,6-三甲基苯甲醯基）-苯基氧化膦（光聚合起始劑，Ciba Specialty Chemicals公司製、IRGACURE 819)、〇_〇4質量份 54 201124354 的2,5-二第三丁基氫醌（聚合終止劑）、以及ο.〗質量份的紫外 線吸收劑（Ciba Specialty Chemicals 公司製、TINUVIN 109)，便獲得樹脂層形成用光硬化性樹脂組成物γ。 在將上述樹脂層形成用光硬化性樹脂組成物γ放入容 器且呈開放狀態下設置於減壓裝置内，將減壓裝置内減壓 至約20Pa並保持10分鐘，藉此施行脫泡處理。經測定樹脂 層形成用光硬化性樹脂組成物Y在25。(：下的黏度，結果約 14Pa · s。 其次，使用如下述的多點喷嘴式分配器，在由密封部 所包圍的區域中，將上述樹脂層形成用光硬化性樹脂組成 物Y依以下條件分散滴下。 (分散滴下的條件） •滴下的間距：15mm。 •硬化性樹脂組成物層的厚度：〇 8mm(滴下量：〇 18cc/ 點）。 •滴下頭：在長邊方向上排列3台使用8x8=64點的多點 噴嘴（分支噴嘴)者。 •滴下時間：滴下節拍3.3secx24點=79.2sec。 將硬化性樹脂組成物呈點狀分散滴下後的基板A，載置 於減壓裝置的真空處理室内升降裝置下側的下平板之上 面。將與基板A所使用者為相同形狀且相同厚度的鈉鈣玻璃 板(稱「基板B」。相當於本發明的另一基板），靜電吸附於 升降裝置上側的上平板之下面。 接著’將真空處理室形成密封狀態，並施行排氣直到 55 201124354 處理至内成為15Pa為止。然後，利用真空處理室内的升降 裝置使上下的平板相靠近，便使基板A與基板B積層。在 此，從硬化性樹脂組成物完成滴下起至積層為止的時間係 12〇sec。然後’將真空處理室内返回於大氣壓。 其次，利用升降裝置使上下的平板相遠離，並吸附於 上側的上平板之吸附塾上，再使域板A與基板B構成的積 層體(稱「積層體C」）從上側的上平板剝離。 然後，將積層體C保持水平並靜置約10分鐘後，再從基 板B表面側依目視確認硬化性樹脂組成物層巾有無空隙。結 果如下表所示。 另外’表中的符號意義分別如下： 〇：在由密封部所包圍區域中並無存在直徑1〇〇叫以 上的空隙。 △.在由在、封部所包圍區域中存在直徑丨⑼叫^以上的 空隙個數係1〜30個/m2。 X:在由密封部所包圍區域中存在直經卿叫以上的空 隙個數係31個/m2以上。 其次，從積層體C的面方向均勻地由高壓水銀燈照射紫 外線，而使硬化性樹脂組成物硬化，藉此獲触層玻璃狀 的積層體(稱「積層體D」）。 (例2) 除使用25°C下的黏度為4Pa · 3之樹脂層形成用光硬化 性樹脂組成物以外，其餘均實施與例丨同樣的順序。 (例3) 56 201124354 除使用25°C下的黏度為IPa · s之樹脂層形成用光硬化 性樹脂組成物以外，其餘均實施與例1同樣的順序。 (例4) 除將滴下間距設為30mm之以外，其餘均實施與例3同 樣的順序。 (例5) 將基板尺寸設為長1300mm、寬1100mm、厚2mm，並 將滴下點數設為40點，且將滴下時間設為132sec(滴下節拍 3.3secx40點）以外，其餘均實施與例1同樣的順序。 (例6) 除將從完成滴下起至積層為止的時間設為70sec以 外，其餘均實施與例5同樣的順序。 (例7) 除藉由將在樹脂層形成用光硬化性樹脂組成物滴下 時，使滴下頭（噴嘴）依下示條件進行擺動而滴下的該硬化性 樹脂組成物之等值圓直徑進行強制性擴展，而使存在於由 密封部所包圍區域中的該硬化性樹脂組成物之等值圓直徑 呈均勻以外，其餘均實施與例6同樣的順序。 (滴下時擺動條件） •第1〜24點：無擺動 .第25〜27點：擺動振幅0.5mm •第28〜32點：擺動振幅1.0mm .第33〜40點：擺動振幅1.5mm [表1] 57 201124354 基板尺寸 (mmxnm) 滴下 時間 (sec) 樹脂 黏度 (Pa · s) 滴下 間距 (mm) 滴下 點數 (點） 擺動 消下完成〜 積層（sec) 空隙 例1 1100x900 79.2 14 15 24 無 120 〇 例2 1100x900 79.2 4 15 24 無 120 Δ 例3 1100x900 79.2 1 15 24 無 120 X 例4 1100x900 79.2 1 30 24 無 120 Δ 例5 1300x1100 132 14 15 40 無 120 X 例6 1300x1100 132 r 14 「15 40 無 70 Δ 例7 1300x1100 132 14 15 40 有 70 〇 例1中，在經靜置ίο分鐘後的積層體之硬化性樹脂組成 物層中，並無存在〇_-(5。^達1〇(^111以上的空隙。由此結果 得知，當實施真空積層之際，存在於基板A由密封部所包圍 區域中的硬化性樹脂組成物層呈滿足上述的狀態。 另一方面’使用硬化性樹脂組成物黏度低於例1的例 2，在經靜置1〇分鐘後的積層體之硬化性樹脂組成物層中， 空隙個數係1〜30個/m、結果，因為經分散滴下後的硬化 性樹脂組成物會更快速擴展，因而判斷當實施真空積層之 際’部分會如第7(e)圖所示，形成空隙已消除狀態。 使用硬化性樹脂組成物黏度低於例2的例3 ,在經靜置 1 〇刀釦後的積層體之硬化性樹脂組成物層中，空隙個數係 31個/m。由此結果得知，因為經分散滴下後的硬化性樹脂 組成物會更快速擴展，因而呈第7(e)圖所示狀態的部分會更 增加。 使用與例3相同的硬化性樹脂組成物，但擴大滴下間距 的例4，在M靜置1G分鐘後的積層體之硬化性樹脂組成物層 中’空隙個數係1〜30個/m2。由此結果得知，藉由所分散 滴下的硬化性樹脂組成物彼此間之間隔擴大，相較於例3之 58 201124354 下’呈第7⑷圖所示狀^部分會減少。 基板尺寸大於例1的例卜在經靜置10分鐘後的積層體 之硬化性樹驗成物層巾，空隙個數仙個以上。由此 結果得知’滴下職私㈣果，因為滴下㈣（即開始滴 下起至滴下完成為止所需要的時間）增加，因而當實施直空 積層時’有部分會呈第7(e)圖所示空隙已消除狀態。 相對於例5，縮短從滴下完成起至積層為止之時間的例 6 ’在經靜置1〇分鐘後的積層體之硬化性樹脂組成物層中， 空隙個數係1〜3G個W。由此結果得知，雖未生成有第7(e) 圖所不狀態的部分，但卻有生成如第7(b)圖所示Dp〇re大於 10mm的部分。 相對於例6 ’在硬化性樹脂組成物滴下時使滴下頭擺動 的例7，經靜置1 〇分鐘後的積層體之硬化性樹脂組成物層 中，並無存在直徑達ΙΟΟμηι以上的空隙。由此結果得知， 藉由滴下頭的擺動而分散滴下的硬化性樹脂組成物之等值 圓直徑會擴大，在滴下完成時的硬化性樹脂組成物之等值 圓直徑呈均勻。由此結果得知，實施真空積層之際，存在 於基板Α由岔封部所包圍區域中的硬化性樹脂組成物層，呈 滿足上述（1)〜（3)的狀態。 (例8) 依照與例1同樣的順序，在基板A上形成厚度lmm的密 封部。但，基板A係使用長1110mm、寬970mm、厚2mm的 鈉鈣玻璃製基板，沿該基板外周部距内側4mm的位置形成 密封部。另外，在密封部形成時，使用與例丨相同的密封部 59 201124354 形成用光硬化性樹脂組成物x。 其次’在密封部所包圍區域中’將硬化性樹脂組成物 塗佈成如第15圖所示的振動曲線3〇a、30b。硬化性樹脂組 成物係使用與例1的樹脂層形成用光硬化性樹脂組成物γ相 同者。但，使用25°C下的黏度為2Pa . s之硬化性樹脂組成 物。塗佈條件係如下。 (塗佈條件） •振動曲線：正弦曲線 •週期X : 20mm •振幅Y : 10mm •剛塗佈後的振動曲線粗細度m : 6mm 振動曲線的厚度係设定成在真空積層時，硬化性樹脂 組成物層的厚度與例1的厚度相同之狀態。就此點，例9〜 例15亦同。 •振動曲線與密封部間之最短距離d(w) : 0mm •相鄰接之振動曲線彼此間的最短距離d卜0 : 〇mm •塗佈裝置：具定量泵16分支頭的塗佈裝置、使用3台 (依2〇xl6x3=960mm寬度施行塗佈） 由下式所求得在振動曲線的振幅Y方向上的空隙直徑 E係 8mm 〇 E=2Y-2m 經硬化性樹脂組成物塗佈後，便實施與例1同樣的順 序。但’從滴下完成起至積層為止的時間係設為50sec。 (例9) 60 201124354 除將滴下完成起至積層為止的時間設為25sec之外，其 餘均實施與例8同樣的順序。 (例 10) 除將振動曲線與密封部間之最短距離d(s_r)設為 1 ·5mm，並將相鄰接之振動曲線彼此間的最短距離d(r…設為 3mm之外，其餘均實施與例8同樣的順序。 振動曲線的振幅Y方向上的空隙直徑E係2 m m。 (例 11) 除將剛塗佈後的振動曲線粗細度m設為3 mm之外，其 餘均實施與例10同樣的順序。此處，振動曲線的振幅Y方向 上的空隙直徑E係8mm。 (例 12) 除將剛塗佈後的振動曲線粗細度m設為9mm之外，其 餘均實施與例10同樣的順序。 振動曲線的振幅Y方向上的空隙直徑E係-4mm。此處， 空隙直徑E成為負值乙事，係表示在形成空隙時，相鄰接之 振動曲線彼此間有發生重疊情形。 (例 13) 除將振動曲線的週期X設為15mm，並將振幅Y設為 7.5mm之外，其餘均實施與例10同樣的順序。 振動曲線的振幅Y方向上的空隙直徑E係-3mm。 (例 14) 除將振動曲線的週期X設為25mm，並將振幅Y設為 12.5mm之外，其餘均實施與例10同樣的順序。 61 201124354 振動曲線的振幅Y方向上的空隙直徑£係7mm。 (例 15) 除將滴下完成起至積層為止的時間設為50sec之外，其 餘均實施與例14同樣的順序。 [表2] 基板 尺寸 (mmxmm) 樹脂 黏度 (Pa · s) m (mm) X (mm) Y (mm) (¾ to (Y+d(r-r)) (mm) E (mm) Y+d(,r) 塗佈完成 〜積層 (sec) 空隙 例8 1110x970 2 6 20 10 0 0 8 10 50 —ο— 例9 1110x970 2 6 20 10 0 0 8 10 25 Δ 例10 1110x970 2 6 20 10 3 1.5 1.3 2 13 25 〇 例11 1110x970 2 3 20 10 3 1.5 1.3 8 13 25 Δ 例12 1110x970 2 9 20 10 3 1.5 1.3 -4 13 25 —1 X 例13 1110x970 2 6 15 7.5 3 1.5 1.05 -3 10.5 25 X 例14 1110x970 2 6 25 12.5 3 1.5 1.55 7 15.5 25 △ 例15 1110x970 2 6 25 12.5 3 1.5 1.55 7 15.5 50 — ~0~ 例8中’在靜置10分鐘後的積層體之硬化性樹脂組成物 層中，並無存在直徑達ΙΟΟμπι以上的空隙。由此結果得知， 當實施真空積層之際’存在於基板Α由密封部所包圍區域中 的硬化性樹脂組成物層，呈滿足上述（丨）〜。）的狀態。 另一方面，從滴下完成起至積層為止的時間較例8短的 例9 ’在經靜置1〇分鐘後的積層體之硬化性樹脂組成物層 中’空隙個數係1〜30個/m2。由此結果得知，如第7(b)圖所 示有生成Dp()re大於l〇mm的部分。 62 201124354 例10中，在經靜置10分鐘後的積層體之硬化性樹脂組 成物層中，並無存在直徑達1 ΟΟμηι以上的空隙。由此結果 得知，當實施真空積層之際，存在於基板Α由密封部所包 圍區域中的硬化性樹脂組成物層，呈滿足上述（1)〜（3)的 狀態。 相對於例10,將剛塗佈後的振動曲線粗細度m設為較細 的例11，在經靜置10分鐘後的積層體之硬化性樹脂組成物 層中，空隙個數係1〜30個/m2。由此結果得知，當實施真 空積層之際，如第7(b)圖所示有生成DpQre大於10mm的部 分。 相對於例10，將剛塗佈後的振動曲線粗細度m設為較粗 的例12，在經靜置10分鐘後的積層體之硬化性樹脂組成物 層中，空隙個數達31個/m2以上。例12中，因為振動曲線的 振幅(Y)方向上的空隙直徑E係-4mm，因而判斷在形成空隙 時，相鄰接之振動曲線彼此間有發生重疊的情形。由此結 果得知，當實施真空積層之際，有部分如第7(e)圖所示的空 隙已為消除狀態。 相對於例10，縮小振動曲線之週期X與振幅Y的例13， 在經靜置10分鐘後的積層體之硬化性樹脂組成物層中，空 隙個數達31個/m2以上。例13中，因為振動曲線的振幅Y方 向上的空隙直徑E係-3mm，因而判斷在形成空隙時，相鄰 接之振動曲線彼此間有發生重疊的情形。由此結果得知， 當實施真空積層之際，有部分如第7(e)圖所示的空隙已為消 除狀態。 63 201124354 相對於例10，放大振動曲線之週期χ與振幅γ的例14，在 經邊置1 〇分鐘後的積層體之硬化性樹脂組成物層中，空隙 個數係1〜30個/m2。由此結果得知，當實施真空積層之際， 如第7(b)圖所示有生成Dpore大於l〇mrr^部分。 相對於例14，拉長從滴下完成起至積層為止的時間之 例15，在經靜置1〇分鐘後的積層體之硬化性樹脂組成物層 中，並無存在直徑達1〇〇μη:ι以上的空隙。由此結果得知， 藉由更縮小Dp()re’當實施真空積層之際，存在於基板六由密 封部所包圍區域中的硬化性樹脂組成物層，呈滿足上述（1) 〜(3)的狀態。 產業上之可利用性 根據本發明積層體的製造方法，可縮短在製造積廣體 的過程中所實施之將由一對基板與密封部所密閉的空間整 體’利用硬化性樹脂組成物均勻填充的所需時間，牌<提 升積層體的生產性。 另外2GG9年11月5日所提出巾請的日本專利申請案 2009-253984號的說明書、巾請專利範圍、圖式及摘要之全 部内容均0於本案中，並融人為本發明的揭示。 【圖式> 簡明】 第1圖係基板的平面圖，在基板上的周邊部形成密封部 狀態。 第2圖係基板的平面圖，在基板由密封部所包園的部分 中形成硬化性樹脂組成物層的狀態。 第3⑷〜⑷圖係對基板之由密封部所包圍區威點狀分 64 201124354 散滴下之硬化性樹脂組成物的經時變化圖。 第4⑷〜（d)圖係硬化性樹脂組成物在第3⑷圖所示狀 態時施行真空積層的情況下，硬化性樹脂組成物在真空積 層時及解除減壓環境後的狀態圖。 a第5⑷〜⑷圖係硬化性樹脂組成物在第3 (b)圖所示狀 態時施行真空積層的情況下，硬化性樹脂喊物在真空積 層時及解除減壓環境後的狀態圖。 第6 (a)〜（d)圖係硬化性樹脂組成物在第3 (c)圖所示狀 態時施行真空制㈣況下，硬化脂組成物在真空積 層時及解除減壓環境後的狀態圖。 第7(a)〜(e)圖係對基板之由密封部戶斤包圍區域點狀分 散滴下之硬化性樹脂組成物的經時變化圖。 第8圖係使用單點噴嘴’對基板由密封部所包圍區域分 散滴下硬化性樹脂組成物的順序圖。 第9圖係使用多點噴嘴，對基板由密封部所包圍區域分 散滴下硬化性樹脂組成物的順序圖。 第10圖係使用多點噴嘴，對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第11圖係使用多點喷嘴，對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第12圖係使用多點噴嘴’對基板由密封部所包圍區域 分散滴下硬化性樹脂組成物的順序圖。 第13圖係滴下後的經過時間t(sec)、與硬化性樹' 物的等值圓直徑d(mm)間之關係圖。 65 201124354 第14圖係滴下後的經過時間t、硬化性樹脂組成物的等 值圓直仏d、及所存在硬化性樹脂組成物層中之空隙的等值 圓直役Dp〇re間之關係圖0 第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 i 第16圖係相當於第15圖之部分放大圖，顯示振動曲線 30a、30b形狀的經時變化。 第17圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第18圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第19圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖》 第2 0圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第21圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第22圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖8 第23圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 第2 4圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗 佈形態圖。 66 201124354 【主要元件符號說明】 10.. .基板 20.. .密封部 30.. .硬化性樹脂組成物 30…硬化性樹脂組成物層 30a、30a’、30a”、30b、30b’、30d、30e···振動曲線 30c、30f、30g·.·直線 31.. .寬幅部位 40、41…空隙 100、 101、102、103、104···喷嘴 101、 102、103、104···多點噴嘴(分支喷嘴）When Ya, Yb and the thickness ma and mb are different, the diameter E of the gap 4〇 is expressed as follows: E=Ya+Yb-(ma+mb) (Ya+Yb+2d(rr))/20 ^ E ^ (Ya + Yb + 2d (rr)) / 2, the ratio between the curable resin composition and the void in the region which is relatively easy to industrially high-speed and curved, and in the region surrounded by the sealing portion From the viewpoint of the g, the thickness m of the vibration curve at the time of starting supply is preferably 1 to 40 mm, more preferably 3 to 15 mm. In order to apply the curable resin composition to a predetermined vibration curve 3〇, 30b', as shown in Fig. 17, use a nozzle that can move in either direction or in any direction in the figure (multi-point nozzle (including Branch nozzle)) 1〇4 coating curable resin composition coating. In the case where the curable resin composition is dispersed in a dot-like manner, the curable resin composition after the dropping is spread over time, resulting in an increase in the diameter of the equivalent circle. When the curable resin composition is applied in a line shape, the same phenomenon is caused by the occurrence of the phenomenon. The thickness of the vibration curves 30a and 30b becomes thicker. Therefore, as shown in Figs. 18 and 19, it is preferable to form a coating direction when the vibrating green 3〇a is formed (indicated by an arrow in Fig. 18), and to form a vibration adjacent to the vibration curve 3〇a. The application direction (indicated by an arrow in FIG. 19) at the time of the curve 30b is set to the opposite direction. The reason is that as shown in FIG. 20, the size of the void 40 existing in the region surrounded by the sealing portion 20 can be made uniform. Further, the vibration curves 3 of the 15th to 20th drawings are the same as the amplitude γ of 3〇15, but as shown in Fig. 21, the amplitude Y of the vibration curve 3〇a' and the vibration curve 30b' is different. Further, in the figures 15 to 21, the patterns of the adjacent curable resin composition layers each form a vibration curve, but as shown in Fig. 22, the patterns of the adjacent curable resin composition layers may be Only one of them is the vibration curve 30a", and the other is the straight line 3〇c. However, in this case, the closest to the sealing portion 2〇 must be a non-linear line 3〇c and must be the vibration curve 30a”. Further, the period χ and the amplitude γ of the vibration curve 30a" preferably satisfy the above conditions in accordance with the relationship between the thickness m of the vibration curve at the start of supply. Further, the shortest between the vibration curve 30a" and the sealing portion 2 The distance d(w) preferably satisfies the above conditions in accordance with the relationship between the thickness m of the vibration curve at the time of starting supply. Furthermore, the shortest distance d between the adjacent vibration curves 3〇a” and the straight line 30c (r-〇, according to the relationship between the thickness m and the thickness m of the vibration curve at the start of supply, preferably satisfies the vibration of the adjacent connection. The shortest distance between the curves d(rr) is the condition of 46 201124354. Further, 'the vibration curve 30a adjacent to each other is formed by the gap E(mrn) formed by the line 3〇(: 'The diameter E (i.e., the equivalent circle diameter) of the gap in the amplitude Y direction of the vibration curve 3〇a, which preferably satisfies the following formula: (Y+d(rr))/20 ^ E ^ (Y+ d(rr))/2 Further, in the drawings 15 to 22, a pattern of a layer of a curable resin composition is formed in the longitudinal direction of the substrate 1〇, but as shown in FIG. 23, on the substrate 10 In the short-side direction, the pattern (30e, 30f) of the layer of the curable resin composition is formed. Further, in the figures 15 to 23, the pattern of the curable resin composition layer forms a vibration curve 'but may be as shown in the 24th As shown in the figure, the straight lines 30f and 30g of the wide portion 31 are provided in a certain period X. This case is also applicable to applying the curable resin composition to the vibration curves 30a, 30b. The maximum width of the wide portion 31 satisfies the condition of the amplitude γ described in the vibration curve. In the method for producing a laminate according to the present invention, the vacuum laminate can be carried out in the following order. In the pair of substrates, a substrate having a side on which a seal portion and a curable resin composition layer are formed on the surface is referred to as "one of the substrates", and a substrate on the surface where the sides are not formed is referred to as "another - Substrate. One of the substrates is placed in a decompression device, and the substrate is placed flat on the fixed support disk in the decompression device so that the surface of the curable resin composition layer faces upward. There is a moving branch 47 201124354 floor mechanism, and another substrate is mounted on the moving support mechanism. Here, when a thin film system solar cell device is formed on the surface of the other substrate, a thin film system is formed. The side of the side of the battery device faces downward. Also, when the use of the laminate is a flat panel display (FPD), the surface on the side where the image is displayed faces downward. Also, when on the surface of the other substrate When the antireflection layer is provided, the surface on which the side of the antireflection layer is not formed faces downward. The other substrate is placed on one of the substrates and is not in contact with the layer of the curable resin composition. The curable resin composition layer on the substrate is in contact with the other substrate but is opposed to each other. Further, a movable supporting mechanism movable in the vertical direction may be provided in a lower portion of the decompression device, and in the moving support mechanism One of the substrates is placed on top of the substrate. At this time, another substrate is mounted on the fixed support disk provided on the upper portion of the decompression device, and one of the substrates is opposed to the other substrate. Both the substrate and the other substrate are supported by upper and lower moving support mechanisms provided in the decompression device. After one of the substrates and the other substrate are placed at a predetermined position, the inside of the pressure reducing device is decompressed to form a predetermined reduced pressure environment. If possible, one of the substrates and the other substrate may be placed at a predetermined position in the decompression device after the decompression operation or the formation of the predetermined decompression environment. After a predetermined decompression environment is formed inside the decompression device, the other substrate supported by the moving support mechanism is moved downward, and the other substrate is resuspended above the hard resin composition layer on one of the substrates. The sclerosing bribe is sealed by overlapping 'covering the surface of one of the substrates, the underside of the other substrate, and the space surrounded by the sealing portion. When overlapping, the 'curing resin composition by the weight of the other substrate, the pressing from the moving branch mechanism, etc.' will be squeezed and diffused, so that the space is filled with the curable resin composition, and then the reduction is made. The pressing environment 'forms a layer of a curable resin composition without voids. The pressure-reducing environment at the time of overlap is l〇〇〇pa or less, preferably 〇.lpa or more. If the pressure-reduced environment is excessively low-pressure, there is a possibility that the components (curing compound, photopolymerization initiator, polymerization terminator, photo-setting agent, etc.) contained in the curable resin composition may be adversely affected. For example, if the decompression environment is excessively low, the components may be vaporized, and it takes time to provide a reduced pressure environment. The pressure in the reduced pressure environment is better i~1〇〇Pa. Tejia is 3~30Pa. The time from when the one substrate overlaps the other substrate to when the pressure-reducing environment is released is not particularly limited, and the pressure-reducing environment can be immediately released after the curable resin composition is sealed. After the curable resin composition is sealed, the reduced pressure state is still _ at a predetermined time. By maintaining the reduced pressure state for a predetermined period of time, the curable resin composition is gripped in the sealed space, so that the interval between one of the substrates and the other substrate can be made uniform even by releasing the decompression environment. The sealed state can be easily maintained in the second pressure environment which is placed in a higher pressure reducing environment than when the vacuum laminate is applied. The time for maintaining the decompressed state may be a long time of several hours or more, and 'from the viewpoint of production ruling' is preferably within a period of time, more preferably within minutes, more preferably within minutes. Then, by releasing the decompression environment and placing the pair of substrates holding the composition of the curable resin 49 201124354 in a second pressure environment higher than the reduced pressure environment, one of the environmental pressures rises. When the substrate and the other substrate are pressed in the direction in which the substrate is in contact with each other, the curable resin composition flows in the sealed empty door, and the entire closed space is uniformly charged by the curable resin composition, and is increased. A layer of a curable resin composition having no voids. Here, the pressure in the pressure environment is preferably higher than that in the vacuum decompression environment in which the vacuum laminate is applied. The pressure in the second pressure environment is usually preferably as low as 120 kPa. The second pressure environment can be an atmospheric pressure environment or a higher pressure. The operation from the hardening of the curable resin composition can be realized without special equipment, and is preferably an atmospheric pressure environment. In the second pressure environment, a step of laminating and laminating one of the substrates and the other substrate is used to release the decompression chamber of the decompression device in the decompression device that performs the above-described layering Adjusting the decompression chamber to a pressure of (5) (for example, atmospheric pressure), and then purifying the crucible in the pressure environment to form a hardened crucible to form a hardened residue, or may be performed from The vacuum-decomposed pressure-reducing device is moved to another chemical treatment facility, and the pressure in the hardening treatment device is lightly reduced to 12 degrees, and the resin layer-shaped hardening resin composition is applied in the pressure environment. Hardening treatment. The time during which the substrate is held in the second pressure environment in which the substrate is held at a higher pressure than the reduced pressure is not particularly limited. The process of curing the sclerosing tree of the holder, the substrate, the process from the decompression device, and the hardening process until the start = the time required for the process is maintained at 壎50 201124354 force environment The time below. Therefore, when it is placed in an atmospheric pressure environment, there is no gap in the curable resin composition layer in the sealed space, or the void in the curable resin composition layer disappears during the process. The curable resin composition is cured. When it takes time until the void disappears, the pair of substrates holding the curable resin composition are held in the second pressure environment until the void disappears. Further, since the length of time held in the second pressure environment is easily elongated, it usually does not cause a hindrance, and thus the holding time in the second pressure environment can be lengthened from other necessity in the process. The holding time in the second pressure environment may be a long time of one day or more, but from the viewpoint of production efficiency, it is preferably within 6 hours, more preferably within 1 hour, from the viewpoint of further improving production efficiency. Good within 1 minute. Then, by hardening the curable resin composition in the sealed space, a laminate having a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates is obtained. The means for curing the curable resin composition is arbitrarily used for thermal curing or photocuring in combination with the type of the thermosetting resin composition. 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, and the curable resin composition in the sealed space is cured to obtain a substrate, A laminate of a cured layer of a curable resin composition existing between the pair of substrates. Light is irradiated from the side of the transparent substrate in the pair of substrates. When both sides are 51 201124354 transparent substrates, they can also be irradiated from both sides. In the case of the laminated system flat panel display (FPD) manufactured and the case where the flat display _ uses a transmissive display device, although the light transmission property can be obtained by causing the device to generate an action, since most of them belong to In the state in which the operation is performed, there is no translucent member, and thus the transparent substrate serving as the protective sheet is irradiated with light that hardens the curable resin composition. On the other hand, when the 忒 忒 显 显 使用 使用 使用 使用 使用 使用 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Preferably, the light is ultraviolet light or visible light of 450 nm or less, and an anti-reflection layer is provided on the transparent substrate, and the anti-reflection layer or the secret film of the secret film used in forming the anti-reflection layer does not penetrate. It is necessary to use visible light for hardening. The laminate obtained by the production method of the present invention is suitable for use in a thin-film solar cell device or an image display device. Specific examples of the thin-film solar battery device include, for example, a thin film germanium solar cell device, a compound semiconductor solar cell device such as a chalcopyrite system or a cdTe system, and the like. On the other hand, specific examples of the video display device include, for example, a liquid crystal display device (LCD), an EL (electroluminescence) display device such as an organic EL and an inorganic EL, a plasma display device, and an electronic ink type image. A flat panel display (FPD) such as a display device. In the case of a thin-film solar cell device, a thin-film solar cell device can be formed only on one of the substrates, and a thin-film solar cell device can be formed on both of the substrates. EXAMPLES Hereinafter, the present invention will be more specifically described based on examples. However, 52 201124354 This month is not limited to this. Further, the examples 1, the example 7, the example 8, the example 1 and the example 15 belong to the real example, and the other examples belong to the comparative example. (Example 1) (Photocurable resin composition for forming a seal portion) A difunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from a hydroxyl value: 4000), and Hexamethylene diisocyanate is mixed with a molar ratio of 6 to 7 and then diluted with isodecyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and then reacted in the presence of a catalyst of a tin compound. In the obtained prepolymer, 2-hydroxyethyl acrylate was added and reacted in a molar ratio of about 1 to about 2, thereby obtaining a urethane acrylic acid diluted with 3 Å by mass of isodecyl decyl acrylate. A solution of an ester oligomer (hereinafter referred to as "UC-1"). The hardening base of UC-1 is 2, and the number average molecular weight is about 55,000. The viscosity of the UC-1 solution at 60 ° C is about 580 Pa · s. 90 parts by mass of the UC-1 solution and 10 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHTESTERHOB) were uniformly mixed to obtain a mixture. 100 parts by mass of the mixture, 1 part by mass of hydrazine-hydroxy-3⁄4 hexyl-phenyl-ketone (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 184), 0.1 part by mass of bis (2, 4, 6-diindole basic decanoic acid)-phenyl oxidized scale (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 0. 04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization) The terminator) 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 X for forming a seal portion. The photocurable resin composition X for sealing portion formation is placed in a container, and 53 201124354 is placed in a decompression device in an open state, and the inside of the decompression device is decompressed to about 20 Pa for 1 minute, thereby performing the removal. Bubble treatment. The viscosity of the photocurable resin composition χ (i.e., the second curable resin composition) at 25 ° C was determined to be about 14 〇〇 Pa · 8 . A soda-lime glass substrate (hereinafter referred to as "substrate A", which corresponds to one of the substrates of the present invention) having a length of 1100 mm, a width of 90 mm, and a thickness of 2 min is applied to the sealing portion forming light at a position 5 mm inside from the outer peripheral portion. The curable resin composition X forms a sealing portion having a thickness of 1 mm. (Photocurable resin composition for resin layer formation) 1 mol of difunctional polypropylene glycol (number average molecular weight calculated based on hydroxyl value: 2000), 1 mol of molecular end modified with ethylene oxide The double g flb-based polypropylene glycol (the number average molecular weight calculated by the value: 4000) and the 1 molar alcohol were uniformly mixed to obtain a polyol mixture. Mixing the polyol mixture with isophorone diisocyanate at a molar ratio of 5 to 6 to obtain a prepolymer in the presence of a tin compound catalyst, which is about 1 to 2 in the prepolymer. Mohr is added to the acrylic acid 2_hydroxyethyl and reacted to obtain 'the amine phthalate acrylate oligomer (hereinafter referred to as "UA-2"). The hardening base of the UA-2 is 2, the number average The molecular weight is about 19,000, and the viscosity at 25 ° C is about 1300 Pa · s. 60 parts by mass of UA-2 and 40 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB) were uniformly mixed, and uniformly dissolved in 100 parts by mass of the mixture. 0.2 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 〇_〇 4 parts by mass 54 201124354 2,5-di-t-butylhydroquinone (polymerization terminator), and ο. parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals, TINUVIN 109), to obtain a photocurable resin for resin layer formation γ. The resin layer-forming photocurable resin composition γ is placed in a container and placed in a decompression device in an open state, and the inside of the decompression device is depressurized to about 20 Pa for 10 minutes, thereby performing defoaming treatment. . The photocurable resin composition Y for forming a resin layer was measured at 25. (The viscosity of the lower layer is about 14 Pa·s. The following is a multi-point nozzle type dispenser as described below. The resin layer forming photocurable resin composition Y is in the region surrounded by the sealing portion. Conditions are dispersed and dropped. (Dispersion dropping conditions) • Dropping pitch: 15 mm • Thickness of the curable resin composition layer: 〇8 mm (dropping amount: 〇18 cc/dot) • Dropping head: Arranging in the long side direction 3 A multi-point nozzle (branching nozzle) of 8x8=64 points is used for the table. • Drip time: 3.3sec x 24 dots = 79.2 sec. The substrate A after the dropping of the curable resin composition in a dot shape is placed under reduced pressure. The vacuum processing of the apparatus is performed on the upper surface of the lower flat plate on the lower side of the indoor lifting device. A soda lime glass plate having the same shape and the same thickness as the user of the substrate A (referred to as "substrate B". Corresponding to another substrate of the present invention), The static electricity is adsorbed on the lower surface of the upper plate on the upper side of the lifting device. Next, 'the vacuum processing chamber is sealed, and the exhaust gas is exhausted until 55 201124354 is processed to become 15 Pa. Then, the vacuum processing chamber is used. The lifting device brings the upper and lower flat plates closer together, and the substrate A and the substrate B are laminated. Here, the time from the completion of the deposition of the curable resin composition to the lamination is 12 sec. Then, the vacuum processing chamber is returned to the atmospheric pressure. Next, the upper and lower flat plates are separated from each other by the lifting device, and are adsorbed on the upper suction plate of the upper plate, and the laminated body composed of the domain plate A and the substrate B (referred to as "layered body C") is lifted from the upper plate. Then, the layered body C was kept horizontal and left to stand for about 10 minutes, and then the surface of the substrate B was visually observed to have a void in the layer of the curable resin composition. The results are shown in the following table. The following are as follows: 〇: There is no void with a diameter of 1 〇〇 or more in the area surrounded by the seal. △. The number of voids in the area surrounded by the seal and the seal 丨 (9) is more than 1 〜30/m2. X: The number of voids in the region surrounded by the seal portion is 31/m2 or more. Next, the ultraviolet light is uniformly irradiated from the surface of the laminate C by a high-pressure mercury lamp. Further, the curable resin composition is cured to obtain a layered glass-like layered body (referred to as "layered body D"). (Example 2) A resin layer having a viscosity of 4 Pa·3 at 25 ° C is used. Other than the photocurable resin composition, the same procedure as in the example is carried out. (Example 3) 56 201124354 Except that the photocurable resin composition for forming a resin layer of IPa · s at a viscosity of 25 ° C is used, The same procedure as in Example 1 was carried out. (Example 4) The same procedure as in Example 3 was carried out except that the dropping pitch was 30 mm. (Example 5) The substrate size was 1300 mm long, 1100 mm wide, and 2 mm thick. The same procedure as in Example 1 was carried out except that the number of dropping points was set to 40 points, and the dropping time was set to 132 sec (dropping the beat of 3.3 sec x 40 points). (Example 6) The same procedure as in Example 5 was carried out except that the time from the completion of the dropping to the lamination was 70 sec. (Example 7) When the resin layer forming photocurable resin composition is dropped, the dropping head (nozzle) is swayed under the conditions shown below, and the equivalent circle diameter of the curable resin composition is forced. The same procedure as in Example 6 was carried out except that the equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion was uniform. (Wobble condition when dropping) • 1st to 24th points: no swing. 25th to 27th point: swing amplitude 0.5mm • 28th to 32nd point: swing amplitude 1.0mm. 33rd to 40th point: swing amplitude 1.5mm [Table 1] 57 201124354 Substrate size (mmxnm) Drip time (sec) Resin viscosity (Pa · s) Drip pitch (mm) Drop point (dot) Wobble elimination completed ~ Laminated layer (sec) Void example 1 1100x900 79.2 14 15 24 None 120 Example 2 1100x900 79.2 4 15 24 No 120 Δ Example 3 1100x900 79.2 1 15 24 No 120 X Example 4 1100x900 79.2 1 30 24 No 120 Δ Example 5 1300x1100 132 14 15 40 No 120 X Example 6 1300x1100 132 r 14 "15 40 without 70 Δ Example 7 1300x1100 132 14 15 40 There are 70 cases. In the hardened resin composition layer of the laminate after standing for ίο minutes, there is no 〇_-(5.^达一〇) (a gap of (111) or more. As a result, when the vacuum layering is performed, the curable resin composition layer existing in the region surrounded by the sealing portion of the substrate A satisfies the above-described state. The resin composition has a viscosity lower than that of Example 2 of Example 1, and is allowed to stand for 1 minute. In the hardened resin composition layer of the laminate, the number of voids is 1 to 30/m, and as a result, since the curable resin composition after dispersion and dropping is more rapidly expanded, it is judged that when vacuum lamination is carried out' Part of the formation of the voids is eliminated as shown in Fig. 7(e). The viscosity of the composition using the curable resin is lower than that of the example 3 of Example 2, and the composition of the hardened resin of the laminate after standing 1 boring is used. In the layer, the number of the voids is 31/m. As a result, it is understood that since the curable resin composition after dispersion and dropping is more rapidly expanded, the portion shown in the state shown in Fig. 7(e) is more In the case of using the same curable resin composition as in Example 3, the number of voids was 1 to 30 in the hardened resin composition layer of the laminate after M was allowed to stand for 1 G minutes. M2. From this result, it is found that the interval between the hardened resin compositions dispersed and dispersed is increased, and the portion shown in Fig. 7(4) is reduced as compared with the case of Fig. 3, 2011. Example 1 of the laminate after standing for 10 minutes The sclerosing tree test layer towel, the number of gaps is more than a few cents. From this result, it is known that 'the dropping of the private (four) fruit, because the dropping (four) (that is, the time required from the start of dripping until the completion of the drip) increases, so when implemented When there is a straight space layer, there is a part where the gap shown in Figure 7(e) is eliminated. With respect to Example 5, the number of voids in the cured resin composition layer of the laminate after standing for 1 minute from the completion of the dropwise addition to the time of lamination was 1 to 3 G W. As a result, it was found that although the portion in the state of the seventh (e) is not formed, the portion in which Dp 〇re is larger than 10 mm as shown in Fig. 7(b) is generated. In the case of the example 7 in which the dropping head was swung when the curable resin composition was dropped, the voids having a diameter of ΙΟΟμηι or more were not present in the curable resin composition layer of the laminate after standing for 1 minute. As a result, it is found that the equivalent circle diameter of the curable resin composition dispersed and dropped by the swing of the dropping head is enlarged, and the equivalence circle diameter of the curable resin composition at the time of completion of the dropping is uniform. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate , is present, and the above (1) to (3) are satisfied. (Example 8) A sealing portion having a thickness of 1 mm was formed on the substrate A in the same manner as in Example 1. However, the substrate A was made of a soda lime glass substrate having a length of 1110 mm, a width of 970 mm, and a thickness of 2 mm, and a sealing portion was formed at a position 4 mm from the inner side of the outer peripheral portion of the substrate. Further, when the sealing portion is formed, the photocurable resin composition x is formed using the same sealing portion 59 201124354 as the example. Next, the curable resin composition is applied to the vibration curves 3a and 30b as shown in Fig. 15 in the region surrounded by the sealing portion. The curable resin composition was the same as the photocurable resin composition γ for forming a resin layer of Example 1. However, a curable resin composition having a viscosity at 25 ° C of 2 Pa·s was used. The coating conditions are as follows. (Coating conditions) • Vibration curve: sinusoidal curve • Cycle X: 20 mm • Amplitude Y: 10 mm • Vibration curve thickness immediately after coating m: 6 mm The thickness of the vibration curve is set to be a hardening resin when vacuum laminating The thickness of the composition layer was the same as the thickness of Example 1. At this point, the same applies to Example 9 to Example 15. • The shortest distance between the vibration curve and the seal d(w): 0mm • The shortest distance between adjacent vibration curves d 0 : 〇mm • Coating device: coating device with branching pump 16 branch head, Three sets (applied by 2〇xl6x3=960mm width) The void diameter E in the amplitude Y direction of the vibration curve was obtained by the following formula: 8mm 〇E=2Y-2m After being coated with the curable resin composition Then, the same procedure as in Example 1 was carried out. However, the time from the completion of the dropping to the lamination is set to 50 sec. (Example 9) 60 201124354 The same procedure as in Example 8 was carried out except that the time from the completion of the dropping to the lamination was 25 sec. (Example 10) Except that the shortest distance d (s_r) between the vibration curve and the sealing portion is set to 1 · 5 mm, and the shortest distance d (r... is set to 3 mm between the adjacent vibration curves, the rest are The same procedure as in Example 8 was carried out. The gap diameter E in the amplitude Y direction of the vibration curve was 2 mm. (Example 11) Except that the thickness m of the vibration curve immediately after application was set to 3 mm, In the same procedure as in Example 10. Here, the gap diameter E in the amplitude Y direction of the vibration curve is 8 mm. (Example 12) Except that the thickness m of the vibration curve immediately after application is set to 9 mm, The same order is given in Fig. 10. The gap diameter E in the Y direction of the vibration curve is -4 mm. Here, the gap diameter E becomes a negative value, which means that when the gap is formed, the adjacent vibration curves overlap each other. (Example 13) The same procedure as in Example 10 was carried out except that the period X of the vibration curve was set to 15 mm and the amplitude Y was set to 7.5 mm. The gap diameter E in the amplitude Y direction of the vibration curve was -3mm. (Example 14) Except that the period X of the vibration curve is set to 25 mm, and the amplitude Y is set to 12.5. The same procedure as in Example 10 was carried out except for mm. 61 201124354 The amplitude of the gap in the Y direction of the vibration curve is 7 mm. (Example 15) The time from the completion of the dropping to the lamination is 50 sec. The rest were carried out in the same order as in Example 14. [Table 2] Substrate size (mmxmm) Resin viscosity (Pa · s) m (mm) X (mm) Y (mm) (3⁄4 to (Y+d(rr)) ( Mm) E (mm) Y+d(,r) Coating completed~Laminated layer (sec) Void Example 8 1110x970 2 6 20 10 0 0 8 10 50 —ο— Example 9 1110x970 2 6 20 10 0 0 8 10 25 Δ Example 10 1110x970 2 6 20 10 3 1.5 1.3 2 13 25 Example 11 1110x970 2 3 20 10 3 1.5 1.3 8 13 25 Δ Example 12 1110x970 2 9 20 10 3 1.5 1.3 -4 13 25 —1 X Example 13 1110x970 2 6 15 7.5 3 1.5 1.05 -3 10.5 25 X Example 14 1110x970 2 6 25 12.5 3 1.5 1.55 7 15.5 25 △ Example 15 1110x970 2 6 25 12.5 3 1.5 1.55 7 15.5 50 — ~0~ Example 8 'Standing for 10 minutes In the curable resin composition layer of the subsequent laminate, voids having a diameter of ΙΟΟμπι or more are not present. As a result, it was found that the layer of the curable resin which is present in the region surrounded by the sealing portion of the substrate 之 when the vacuum layer is formed satisfies the above (丨). )status. On the other hand, in the case of the hardened resin composition layer of the laminate after being left to stand for 1 minute from the completion of the dropping to the time of laminating, the number of the gaps was 1 to 30/ M2. From this result, it is found that a portion in which Dp()re is larger than l〇mm is generated as shown in Fig. 7(b). In the case of the curable resin composition layer of the laminate after standing for 10 minutes, there is no void having a diameter of 1 ΟΟμηι or more. As a result, when the vacuum layer is formed, the layer of the curable resin which is present in the region surrounded by the sealing portion of the substrate 呈 is in a state satisfying the above (1) to (3). With respect to Example 10, the thickness of the vibration curve immediately after application was set to be finer in Example 11, and in the layer of the curable resin composition of the laminate after standing for 10 minutes, the number of voids was 1 to 30. /m2. From this result, it is found that when the vacuum layer is implemented, as shown in Fig. 7(b), a portion where DpQre is larger than 10 mm is generated. With respect to Example 10, the thickness m of the vibration curve immediately after application was set to be thicker, and in the case of the curable resin composition layer of the laminate after standing for 10 minutes, the number of voids was 31/ M2 or more. In the example 12, since the gap diameter E in the amplitude (Y) direction of the vibration curve is -4 mm, it is judged that the adjacent vibration curves overlap each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, a portion as shown in Fig. 7(e) was in a canceled state. With respect to Example 10, in the example 13 in which the period X and the amplitude Y of the vibration curve were reduced, the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 31/m2 or more. In Example 13, since the gap diameter E in the amplitude Y direction of the vibration curve is -3 mm, it is judged that the adjacent vibration curves overlap each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, the void as shown in Fig. 7(e) was partially removed. 63 201124354 With respect to Example 10, in Example 14, in which the period χ and the amplitude γ of the vibration curve were enlarged, the number of voids was 1 to 30/m2 in the layer of the curable resin composition of the laminate after being placed for 1 minute. . From this result, it is found that when vacuum lamination is performed, as shown in Fig. 7(b), a portion where Dpore is larger than l〇mrr^ is generated. With respect to Example 14, in the case of elongating the time from the completion of the dropping to the lamination, in the curable resin composition layer of the laminate after standing for 1 minute, there was no diameter of 1 μμη: ι above the gap. As a result, it is found that the hardening resin composition layer in the region surrounded by the sealing portion of the substrate 6 is satisfied by the above (1) to (3) when the vacuum layer is formed by the reduction of Dp()re'. )status. INDUSTRIAL APPLICABILITY According to the method for producing a laminated body of the present invention, it is possible to shorten the space in which a pair of substrates and a sealing portion are sealed in the process of manufacturing an integrated body, which is uniformly filled with a curable resin composition. Time required, card <Improve the productivity of the laminate. In addition, the specification, the scope of the patent, the drawings and the abstract of the Japanese Patent Application No. 2009-253984 filed on November 5, 1989, are all incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of a substrate. Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion where a substrate is surrounded by a sealing portion. The third (4) to (4) diagrams are diagrams showing the temporal change of the hardened resin composition under the scattered droplets on the substrate surrounded by the sealing portion. In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(4) to (d), the state of the curable resin composition at the time of vacuum lamination and after the decompression environment is released. (a) The state in which the curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3 (b), and the state of the curable resin is in the case of vacuum lamination and after the decompression environment is released. 6(a) to (d) are the state in which the curable resin composition is subjected to vacuum (4) in the state shown in Fig. 3(c), and the cured grease composition is in a state of vacuum lamination and after the decompression environment is released. Figure. The seventh (a) to (e) diagrams are time-dependent changes of the curable resin composition in which the substrate is dotted and dotted by the sealing portion. Fig. 8 is a sequence diagram in which a hard-pointing resin composition is dispersed and dropped on a substrate surrounded by a sealing portion using a single-point nozzle. Fig. 9 is a sequence diagram in which a multi-point nozzle is used to dispense a curable resin composition from a region surrounded by a sealing portion. Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse and drop a curable resin composition on a substrate surrounded by a sealing portion. Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a composition of a curable resin in a region surrounded by a sealing portion. Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a composition of a curable resin in a region surrounded by a sealing portion. Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable tree. 65 201124354 Fig. 14 is the relationship between the elapsed time t after dropping, the equivalence of the curable resin composition, and the equivalence of the gaps in the curable resin composition layer Dp〇re Fig. 0 Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. i Fig. 16 is a partial enlarged view corresponding to Fig. 15, showing temporal changes in the shape of the vibration curves 30a, 30b. Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 19 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 21 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 22 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 8 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape. 66 201124354 [Description of main component symbols] 10.. Substrate 20: Sealing part 30.. Curable resin composition 30: Curable resin composition layers 30a, 30a', 30a", 30b, 30b', 30d 30e···Vibration curve 30c, 30f, 30g···Line 31.. Wide area 40, 41...Voids 100, 101, 102, 103, 104···Nozzles 101, 102, 103, 104·· ·Multi-point nozzle (branch nozzle)

Dpc)re...存在於前述硬化性樹脂組成物層中之空隙，其投影形狀的 等值圓直徑 D__p()re…硬化性樹脂組成物之層中未存在有空隙之部分，其投影 形狀的等值圓直徑 E...空隙的直徑m、ma、mb...粗細度 X. ..週期 Y、 Ya、Yb...振幅 67Dpc)re... a void existing in the layer of the curable resin composition, the equivalence circle diameter of the projected shape D__p()re...the portion of the layer of the curable resin composition where no void exists, and the projected shape thereof Equivalent circle diameter E...Void diameter m, ma, mb...thickness X. .. period Y, Ya, Yb...amplitude 67

Claims (1)

201124354 七、申請專利範圍： 1. 一種積層體的製造方法，係包含有下述步驟： 準備2片基板； 在其中一基板上的周邊部形成密封部，該密封部係 用以封住硬化性樹脂組成物者； 對其中一基板上由前述密封部所包圍的區域，供應 硬化性樹脂組成物； 於減壓環境下，在前述被供應的硬化性樹脂組成物 上重疊另一基板，以在一對基板間挾持硬化性樹脂組成 物並加以密封；及 將挾持著硬化性樹脂組成物的一對基板，放置在高 於前述減壓環境的第2壓力環境下，於該第2壓力環境下 使硬化性樹脂組成物硬化以製造積層體，該積層體的製 造方法之特徵在於： 控制供應至基板上之前述硬化性樹脂組成物的塗佈 狀態、以及在前述硬化性樹脂組成物上重疊另一基板的 時期，以在將前述另一基板重疊於其中一基板上之時， 存在於由前述密封部所包圍區域中的硬化性樹脂組成物 層可滿足下述（1)〜 (1) 存在於前述硬化性樹脂組成物層中之空隙，其投 影形狀的等值圓直徑（equivalent circle diameter)Dpore 為 1 〇mm以下； (2) 前述硬化性樹脂組成物層中未存在有空隙之部 分’其投影形狀的等值圓直徑Dncnp()re為4〇mm以下； 68 201124354 (3)前述硬化性樹脂組成物層和存在於前述硬化性 樹脂組成物層中之空隙，交互地與前述密封部呈相接觸 之狀態。 2. 如申請專利範圍第1項之積層體的製造方法，其中在前 述2片基板中至少一片係透明基板。 3. 如申請專利範圍第1或2項之積層體的製造方法，其中前 述硬化性樹脂組成物的黏度係0.2〜50Pa · s。 4. 如申請專利範圍第1至3項中任一項之積層體的製造方 法，其中存在於由前述一對基板與前述密封部所密封的 空間内之硬化性樹脂組成物層的厚度，係30〜3000μηι。 5. 如申請專利範圍第1至4項中任一項之積層體的製造方 法，其中前述密封部係使用黏度200〜3000Pa . s的第2 硬化性樹脂組成物而形成者。 6. 如申請專利範圍第1至5項中任一項之積層體的製造方 法，其中前述減壓環境係0.1〜lOOOPa的壓力環境。 7. 如申請專利範圍第1至6項中任一項之積層體的製造方 法，其中前述第2環境的壓力較前述減壓環境的壓力高 出50kPa以上。 8. 如申請專利範圍第1至7項中任一項之積層體的製造方 法，其中對其中一基板上由前述密封部所包圍區域進行 硬化性樹脂組成物供應，係指對由前述密封部所包圍區 域分散滴下硬化性樹脂組成物。 9. 如申請專利範圍第8項之積層體的製造方法，其中對其 中一基板上分散滴下前述硬化性樹脂組成物時，使前述 69 201124354 其中一基板、與分散滴下時所使用的喷嘴進行相對性擺 動，而強制性地擴大已滴下之硬化性樹脂組成物的等值 圓直役，藉以使存在於由前述密封部所包圍區域中之硬 化性樹脂組成物的等值圓直徑呈均勻。 10.如申請專利範圍第1至7項中任一項之積層體的製造方 法’其中對其中一基板上供應前述硬化性樹脂組成物， 以在對其中一基板上由前述密封所包圍區域供應前述 硬化性樹脂組成物時，使前述硬化性樹脂組成物呈滿足 下述(4)〜（9)的振動曲線； (4) 相對於振動曲線前進方向，在垂直方向依一定的 週期（X)與振幅(γ)重複位移； (5) 相鄰接之振動曲線的位移係相互呈反相位； (6) 將開始供應時的振動曲線粗細度設為m(mm) 時’則述週期(X)(mm)、及前述振幅(Y)(mm)係滿足下式： 2-!xm^X^ l〇xm (2.1xm)/2^Y^(10xm)/2 (7) 將開始供應時的振動曲線粗細度設為m(mm) 每振動曲線與密封部間之最短距離d(s.r)(mni)係滿足 下式： d(s-r)S 2.5xm (8) 將開始供應時的振動曲線粗細度設為m(mm) 夺’相鄰接之振動曲線間的最短距離d(r r)(mm)係滿足 下式： d(r-r)S 5xm 70 201124354 (9) 當E=2Y-2m時，該E(mm)係滿足下式： (Y+d㈣)/10SESY+d« 11.如申請專利範圍第1至7項中任一項之積層體的製造方 法，其中對其中一基板上供應前述硬化性樹脂組成物， 以在對其中一基板上由前述密封所包圍區域進行供應 時，前述硬化性樹脂組成物之可滿足下述（10)〜（14)的 振動曲線和與該振動曲線朝同一方向前進的直線相鄰 接； (10) 相對於振動曲線前進方向，在垂直方向依一定 的週期（X)與振幅(Y)重複位移； (11) 將開始供應時的振動曲線粗細度設為m(mm) 時，前述週期（X)(mm)、及前述振幅(Y)(mm)係滿足下式： 2.1xm^ 10xm (2.1xm)/2^ Y^(10xm)/2 (12) 當振動曲線位於密封部附近，且將開始供應時 的振動曲線粗細度設為m(mm)時，該振動曲線與密封部 間之最短距離d(s_r)(mm)係滿足下式： d(s.r)^ 2.5xm (13) 將開始供應時的振動曲線粗細度設為m(mm) 時，相鄰接之振動曲線與直線間之最短距離d(r_0(mm)係 滿足下式： d(r.r)^ 2.5xm (14) 當E=2Y-2m時，該E(mm)係滿足下式： (Y+d㈣)/20SES(Y+d㈣)/2。 71 201124354 12.如申請專利範圍第1至11項中任一項之積層體的製造方 法，其中從硬化性樹脂組成物完成對其中一基板上由前 述密封部所包圍區域的滴下開始，直到積層為止的時間 係30〜1800秒。 72201124354 VII. Patent application scope: 1. A method for manufacturing a laminated body, comprising the steps of: preparing two substrates; forming a sealing portion on a peripheral portion of one of the substrates, the sealing portion sealing the hardenability a resin composition; a curable resin composition is supplied to a region surrounded by the sealing portion on one of the substrates; and another substrate is superposed on the supplied curable resin composition under a reduced pressure environment to Holding and curing a curable resin composition between a pair of substrates; and placing a pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, in the second pressure environment The curable resin composition is cured to produce a laminate, and the method for producing the laminate is characterized in that the coated state of the curable resin composition supplied onto the substrate is controlled, and the curable resin composition is superposed on the laminate. a period of a substrate present in a region surrounded by the sealing portion when the other substrate is superposed on one of the substrates The curable resin composition layer satisfies the following (1) to (1) voids present in the curable resin composition layer, and the projected circle has an equivalent circle diameter Dpore of 1 〇 mm or less. (2) The portion of the curable resin composition layer where no void exists, and the equivalent circular diameter Dncnp()re of the projected shape is 4 mm or less; 68 201124354 (3) The aforementioned curable resin composition layer and The voids present in the curable resin composition layer are in a state of being in contact with the sealing portion alternately. 2. The method of manufacturing a laminate according to the first aspect of the invention, wherein at least one of the two substrates described above is a transparent substrate. 3. The method for producing a laminate according to the first or second aspect of the invention, wherein the viscosity of the curable resin composition is 0.2 to 50 Pa·s. 4. The method for producing a laminated body according to any one of the first to third aspects of the present invention, wherein the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is 30~3000μηι. 5. The method for producing a laminate according to any one of claims 1 to 4, wherein the sealing portion is formed using a second curable resin composition having a viscosity of 200 to 3000 Pa.s. 6. The method of producing a laminate according to any one of claims 1 to 5, wherein the reduced pressure environment is a pressure environment of 0.1 to 100 OPa. 7. The method for producing a laminate according to any one of claims 1 to 6, wherein the pressure in the second environment is higher than the pressure in the reduced pressure environment by 50 kPa or more. 8. The method for producing a laminate according to any one of claims 1 to 7, wherein the supply of the curable resin composition to the region surrounded by the sealing portion on one of the substrates is referred to as the sealing portion. The curable resin composition was dispersed and dropped in the surrounding area. 9. The method for producing a laminate according to the eighth aspect of the invention, wherein, in the case where the curable resin composition is dispersedly dropped on one of the substrates, one of the substrates of the above-mentioned 69 201124354 is opposed to the nozzle used when the dispersion is dropped. The oscillating motion is forcibly expanding the equivalence of the hardened resin composition that has been dropped, so that the equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion is uniform. 10. The method for producing a laminate according to any one of claims 1 to 7, wherein the hardenable resin composition is supplied to one of the substrates to supply a region surrounded by the seal on one of the substrates. In the case of the curable resin composition, the curable resin composition has a vibration curve satisfying the following (4) to (9); (4) a predetermined period (X) in the vertical direction with respect to the direction of the vibration curve. Repeat displacement with amplitude (γ); (5) The displacements of the adjacent vibration curves are opposite to each other; (6) When the thickness of the vibration curve at the start of supply is m (mm), the period is described ( X) (mm), and the aforementioned amplitude (Y) (mm) satisfy the following formula: 2-!xm^X^ l〇xm (2.1xm)/2^Y^(10xm)/2 (7) The thickness of the vibration curve is m (mm). The shortest distance d(sr)(mni) between each vibration curve and the seal meets the following formula: d(sr)S 2.5xm (8) Vibration at the start of supply The curve thickness is set to m (mm). The shortest distance d(rr) (mm) between the adjacent vibration curves is satisfied by the following formula: d(rr)S 5xm 70 201124354 (9) When E=2Y-2m Time, The E (mm) system satisfies the following formula: (Y+d(4))/10SESY+d« 11. The method for manufacturing a laminate according to any one of claims 1 to 7, wherein the foregoing is supplied to one of the substrates When the curable resin composition is supplied to a region surrounded by the seal on one of the substrates, the curable resin composition satisfies the vibration curves of (10) to (14) below and the vibration curve Straight lines advancing in the same direction are adjacent to each other; (10) Repeating the displacement in the vertical direction with a certain period (X) and amplitude (Y) with respect to the direction of advancement of the vibration curve; (11) Setting the thickness of the vibration curve at the start of supply In the case of m (mm), the aforementioned period (X) (mm) and the aforementioned amplitude (Y) (mm) satisfy the following formula: 2.1xm^10xm (2.1xm)/2^ Y^(10xm)/2 (12) When the vibration curve is located near the seal portion and the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d(s_r) (mm) between the vibration curve and the seal portion satisfies the following formula: d (sr)^ 2.5xm (13) When the thickness of the vibration curve at the start of supply is m (mm), the shortest between the adjacent vibration curve and the line From d(r_0(mm), the following formula is satisfied: d(rr)^ 2.5xm (14) When E=2Y-2m, the E(mm) system satisfies the following formula: (Y+d(4))/20SES(Y+ The method for producing a laminated body according to any one of claims 1 to 11, wherein the hardenable resin composition is completed from a region surrounded by the aforementioned sealing portion on one of the substrates. The time from the start of the dripping until the lamination is 30 to 1800 seconds. 72
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