201133058 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種藉由保護板而保護液晶面板之液晶顯 示裝置之製造方法。 【先前技術】 作為液晶顯示裝置，已知將由-對偏光板夾持液晶單元 之液晶面板、及保護液晶面板之保護板介隔樹脂層而貼合 者。液晶面板通常係藉由於液晶單元之兩面上以黏著劑貼 附偏光板而獲得。此時，必需使一對偏光板之偏光轴精度 良好地對準。然而，柔軟的膜狀之偏光板難以操作，於偏 光板貼附時難以進行偏光軸之微調整❶而且，若貼附後一 對偏光板之偏光軸未對準，則無法重新貼附偏光板，從而 成為不良品。 因此，提出以下方案：將2塊偏光板中位於保護板側之 偏光板預先貼附於保護板而非液晶面板上，在即將貼合僅 於與保護板側為相反側之表面上貼附有偏光板之液晶面 板、與於液晶面板側之表面上貼附有偏光板之保護板之 前，使作為相較柔軟的膜狀偏光板自身更容易操作之剛直 . 構件之液晶面板與保護板進行相對移動，進行偏光軸之微 . 調整（專利文獻1之段落[0086]等）。 而且’作為液晶面板與保護板之貼合方法，提出有以下 方法：於液晶面板表面之周緣之四邊設置框體，於由框體 包圍之區域中流入有液狀之光硬化性樹脂後，於其上重聂 保護板（專利文獻〗之段落[〇〇58]等）。而且，為了使液晶= 154270.doc 201133058 板與保護板之間不殘留有氣泡，將框體之一邊之上半部八 形成為多孔質構件，使多孔質構件吸收氣泡。 刀 然而’該方法中存在以下問題：即便框體之多孔質構件 附近之氣泡被充分吸收、去除，但其以外之部位之氣泡亦 難以去除。 先行技術文獻 專利文獻 專利文獻1:曰本專利特開2〇〇9_75217號公報 【發明内容】 發明所欲解決之問題 本發明提供一種液晶顯示裝置之製造方法，其可將一對 偏光機構之偏光軸所成之較佳角度容易對準，且由保護板 與液晶面板所夹持之樹脂層中之氣泡之殘留受到充分抑 制。 解決問題之技術手段 本發明之液晶顯示裝置之製造方法之特徵在於，其係製 造如下液晶顯示裝置之方法，該液晶顯示裝置包含：於透 明面材之表面設置有第1偏光機構之保護板；於液晶單元 之表面設置有第2偏光機構之液晶面板；由保護板與液晶 面板夾持之樹脂層；及包圍樹脂層之周圍之密封部；第1 偏光機構位於透明面材與樹脂層之間，第2偏光機構位於 液晶單元之與樹脂層側為相反侧之表面，該液晶顯示裝置 之製造方法包括下述步驟（al)〜(dl)或下述步驟（a2)〜(d2)。 (al)於液晶面板之與第2偏光機構側為相反側之表面之周 154270.doc 201133058 組合物而形成 緣部，塗佈液狀之密封部形成用硬化性樹脂 未硬化之密封部； (b 1)對由未硬化之穷a π ，。卩所包圍之區域供給液狀之樹脂 層形成用硬化性樹脂組合物； (Cl)於1〇0以以下之減壓環境下，於樹脂層形成用硬化 性樹脂組合物上，以使第1偏光機構成為樹脂層形成用硬 化性樹脂組合物側之方式重疊保護板，由保護板、液晶面 板、及未硬化之密封部而獲得使包含樹脂層形成用硬化性 樹脂組合物之未硬化之樹脂層得以密封之積層物的步 驟；及 (dl)將積層物放置在5〇 kpa以上之壓力環境下之狀態 下，使未硬化之密封部及未硬化之樹脂層硬化。 (a2)於保。蒦板之第1偏光機構側之表面之周緣部，塗佈液 狀之密封部形成用硬化性樹脂組合物而形成未硬化之密封 部； (b2)對由未硬化之密封部所包圍之區域供給液狀之樹脂 層形成用硬化性樹脂組合物； (c2)於1 〇〇 pa以下之減壓環境下’於樹脂層形成用硬化 性樹脂組合物上’以使第2偏光機構成為與樹脂層形成用 硬化性樹脂組合物側為相反側之方式重疊液晶面板，由保 護板、液晶面板、及未硬化之密封部而獲得使包含樹脂層 形成用硬化性樹脂組合物之未硬化之樹脂層得以密封之積 層物的步驟；及 (d2)將積層物放置在50 kPa以上之壓力環境下之狀態 154270.doc 201133058 下，使未硬化之密封部及未硬化之樹脂層硬化。 上述步驟（cl)及步驟（c2)中，較佳為以使第1偏光機構及 第2偏光機構之偏光軸所成之角度符合液晶單元之設計之 方式，調整保護板及液晶面板之位置。 發明之效果 根據本發明之液晶顯示裝置之製造方法，可將一對偏光 機構之偏光軸所成之較佳角度容易對準，且由保護板與液 晶面板所夾持之樹脂層中之氣泡之殘留受到充分抑制。 【實施方式】 於本說明書中，「透明」係指具有透光性，「（甲基）丙稀 酸酯」係指丙烯酸酯或甲基丙烯酸酯。 <液晶顯示裝置> 圖1係表示本發明中之液晶顯示裝置之一例的剖面圖， 圖2係平面圖。 液晶顯示裝置1具有：保護板丨0、液晶面板2〇、由保護 板10與液晶面板20夾持之樹脂層4〇、及包圍樹脂層4〇之周 圍之密封部50。 液晶顯示裝置1之形狀通常為矩形。 關於液晶顯示裝置1之大小，由於本發明之製造方法特 別適合於較大面積之液晶顯示裝置之製造，故於電視接收 機之情形時，宜為0.5 mx〇.4 m以上，特佳為0.7 mx〇.4 m 以上。液晶顯示裝置之大小之上限較多由顯示面板之大小 而決定。另外，過大的液晶顯示裝置於設置等方面之操作 容易變得困難。由於該等之制約，液晶顯示裝置丨之大 154270.doc -6 · 201133058 之上限通常為2·5 mxl.5 m左右。 保護板10及液晶面板20之尺寸亦可大致相等，但由於與 收納有液晶顯示裝置1之框體之關係，故較多情形時保護 板10比液晶面板20大一圈。另外，相反，亦可根據框體之 • 構造而使保護板1 〇比液晶面板2 0稍小。 _ [保護板] 保護板10係設置於液晶面板20之圖像顯示側並保護液晶 面板20者。 保護板10具有：透明面材12 ;形成於透明面材12之樹脂 層40側之表面之周緣部的遮光印刷部14 ;及設置於透明面 材12之樹脂層40側之表面的第1偏光機構丨6。 保護板10與僅透明面材、或者與包含有於周緣部設置有 遮光印刷部之透明面材之先前的保護板不同，於保護板1〇 之表面設置有第1偏光機構1 6，於本發明中，將此種附帶 偏光機構之保護板亦簡單稱為保護板。 (透明面材） 作為透明面材12，可舉出玻璃板或透明樹脂板，自對來 自液晶面板2 0之出射光或反射光之透明性較高之觀點而言 自不必說，而且自具有耐光性、低複折射性、高平面精 度、表面耐受傷性、高機械強度之觀點而言，亦為玻璃板 最佳。自用以使光硬化性樹脂組合物硬化之光充分穿透之 觀點而言，亦為玻璃板較佳。 作為玻璃板之材料，可舉出鈉鈣玻璃等之玻璃材料，更 佳為鐵質更低、青度較少的高穿透玻璃（白板玻璃）。為了 154270.doc 201133058 ，: 提高安全性亦可使用強化玻璃。特別於要求較薄的透明面 材之情形時，可使用藉由化學強化法而獲得之強化玻璃。 例如，於透明面材之厚度為丨5 mm以下之情形時若使用 藉由化學強化法製造之強化玻璃，則可改善機械強度，故 較佳》 作為透明樹脂板之材料，可舉出透明性較高的樹脂材料 (聚碳酸脂、聚曱基丙浠酸曱酯等）。 於透明面材12之第1偏光機構16側之表面上，為了提高 與第1偏光機構16之界面接著力，亦可實施表面處理。作 為表面處理之方法，可舉出以矽烷偶合劑對透明面材12之 表面進行處理之方法、及經由火焰燃燒器（flame burner)之 氧化焰而形成氧化矽之薄膜之處理等。 於透明面材12之與第1偏光機構ι6側為相反側之表面 上，為了提高圖像之對比度亦可設置抗反射層❶抗反射層 係可藉由於透明面材12之表面直接形成無機薄膜之方法、 及將設置有抗反射層之透明樹脂膜黏貼於透明面材丨2上之 方法而設置。 又，根據目的，亦可使透明面材12之一部分或全體著 色，或者將透明面材12之一部分表面或整個表面形成磨砂 玻璃狀而使光散射’或者於透明面材12之一部分表面或整 個表面上形成微細之凹凸等而使穿透光折射或反射。又， 亦可將著色膜、光散射膜、光折射膜、光反射膜等黏貼於 透明面材12之一部分表面或整個表面上。 關於透明面材12之厚度，自機械強度、透明性之觀點而 154270.doc 201133058 。，於玻璃板之情形時，通常為0.5〜25 mm。對於室内使 用之電視接收機、PC(pers〇nal c〇mputer，個人電腦）用顯 示器等之用途方面’自液晶顯示裝置之輕量化之觀點而 5 ’較佳為1〜6 mm，對於室外設置之公共顯示用途方 面，較佳為3〜20 mm。於透明樹脂板之情形時，較佳為 2~10 mm。 (遮光印刷部） 遮光印刷部14係為了使液晶面板2〇之圖像顯示區域以外 無法自保護板10側目視確認而將連接於液晶面板2〇之配線 構件等隱藏者。遮光印刷部14可設置於透明面材12之樹脂 層40側或其相反側，於降低遮光印刷部14與圖像顯示區域 之視差之方面，較佳為將其設置於透明面材12之樹脂層4〇 側。於透明面材12為玻璃板之情形時，若遮光印刷部14使 用包含黑色顏料之陶瓷印刷則遮光性高，故而較佳。又， 亦可於設置於透明面材12之樹脂層40側之第}偏光機構16 之樹脂層40側、或其背面設置遮光印刷部。當第i偏光機 構16係藉由樹脂膜而提供之情形時，包含黑色顏料或黑色 染料之有機系油墨之印刷可降低印刷部形成之溫度，故而 較佳。 (第1偏光機構） 第1偏光機構16係由包含具有偏光功能之偏光子之構件 而構成。 第1偏光機構16係可藉由將偏光板以黏著劑黏貼於透明 面材12之表面之方法、由透明面材12與保護膜夾持膜狀之 I54270.doc 201133058 吸收型偏光子並將該等貼合之方法等而設置。 作為偏光板，可舉出於膜狀之吸收型偏光子之兩面上貼 合有一對保護膜之吸收型偏光板、於透明基材之表面形成 有由複數個金屬細線平行排列而成之線柵型偏光子的線柵 型偏光板等。 作為膜狀之吸收型偏光子，可舉出使碘等之二色性色素 定向於聚乙烯醇（以下，記作PVA)等之樹脂膜中者。 作為保護膜，可舉出三乙醯纖維素（以下，記作TAC)膜 等。 [液晶面板] 液晶面板20具有：液晶單元22 ;可撓性印刷配線板24， 其連接於液晶單元22 ’搭載有使液晶單元22動作之驅動 IC(integrated circuit ’積體電路）；及第2偏光機構26，其 設置於液晶單元22之與樹脂層40側為相反側之表面。 液晶面板20與於液晶單元之兩面設置有偏光板之先前之 液晶面板不同，僅於與保護板1 〇側為相反側之表面上設置 有偏光板·#之第2偏光機構26，但本發明中，將此種僅單 面附帶偏光機構之液晶面板亦簡單稱為液晶面板。 (液晶單元） 液晶單元22係將設置有彩色濾光片之透明面材3 2與設置 有TFT(thin film transistor，薄膜電晶體）之透明面材34介 隔液晶層36而貼合者。 於液晶單元22之樹脂層40側之表面上，為了提高樹脂層 4〇及密封部5〇之界面接著力，亦可實施表面處理。表面處 154270.doc •10· 201133058 理既可僅對表面之周緣部實施，亦可對整個表面實施。作 為表面處理之方法，可舉出以可低溫加工之接著用底漆 (primer)等進行處理之方法等。 關於液晶單兀22之厚度，於藉由TFT而動作之液晶單元 之情形時，通常為0.4〜4 mm。 (第2偏光機構） 第2偏光機構26係由包含具有偏光功能之偏光子之構件 而構成。 第2偏光機構26係可藉由將偏光板以黏著劑黏貼於液晶 單元22之表面之方法等而設置。 作為偏光板，可舉出上述吸收型偏光板、線柵型偏光板 等。 [樹脂層] 樹脂層40係使下述液狀之樹脂層形成用硬化性樹脂組合 物硬化而成之層。於液晶顯示裝置丨中，較佳為硬化後之 樹脂之彈性模數變低的樹脂層形成用硬化性樹脂組合物。 若樹脂之彈性模數較大，則存在有於樹脂硬化時由硬化收 縮等而產生之應力對液晶面板2G之顯示性能造成惡劣影響 之虞。 樹脂層40之厚度較佳為〇.〇3〜2 mm，更佳為〇丨〜^ mm。若樹脂層之厚度為〇·〇3 mm以上則樹脂層4〇可有效 緩衝來自保護板10側之外力之衝擊等而保護液晶面板2〇。 又’於本發明之製造方法中1便於保護板1〇與液晶面板 2〇之間混入有超過樹脂層40之厚度之異物，樹脂層仙之厚 154270.doc 201133058 度亦不會發生較大變化，對透光性能之影響較少。若樹脂 層40之厚度為2mm以下，則樹脂層4〇中難以殘留有氣泡， 而且液晶顯示裝置1之全體之厚度不會無用地變厚。 作為調整樹脂層40之厚度之方法，可舉出對下述未硬化 之密封部之厚度進行調節，並且對由未硬化之密封部包圍 之區域所供給之液狀之樹脂層形成用硬化性樹脂組合物之 供給量進行調節的方法。 [密封部] 密封部50係塗佈下述液狀之密封部形成用硬化性樹脂組 合物並使其硬化而成者。液晶面板20之圖像顯示區域之外 側之區域比較狹窄’故密封部50之寬度宜較窄。密封部5〇 之寬度較佳為0_5〜2 mm，更佳為0.8〜1.6 mm。 <液晶顯示裝置之製造方法> 本發明之液晶顯示裝置之製造方法係包括下述步驟 (al)〜(dl)之方法（α)，或包括下述步驟（a2)〜(d2)之方法 ⑻。 (方法⑷） (a 1)於液晶面板之與第2偏光機構側相反側之表面之周緣 部’塗佈液狀之密封部形成用硬化性樹脂組合物而形成未 硬化之密封部； (bl)對由未硬化之密封部所包圍之區域供給液狀之樹脂 層形成用硬化性樹脂組合物； (cl)於100 Pa以下之減壓環境下，於樹脂層形成用硬化 性樹脂組合物上，以使第1偏光機構成為樹脂層形成用硬 154270.doc -12- 201133058 化性樹脂組合物側之方式重疊保護板，由保護板、液晶面 板、及未硬化之密封部而獲得使包含樹脂層形成用硬化性 樹脂組合物之未硬化之樹脂層得以密封之積層物的步 驟；及 (dl)將積層物放置在50 kPa以上之壓力環境下之狀態 下’使未硬化之密封部及未硬化之樹脂層硬化。 (方法（P)) (a2)於保護板之第1偏光機構側之表面之周緣部，塗佈液 狀之密封部形成用硬化性樹脂組合物而形成未硬化之密封 部； (b2)對由未硬化之密封部所包圍之區域供給液狀之樹脂 層形成用硬化性樹脂組合物； (C2)於1〇〇 Pa以下之減壓環境下，於樹脂層形成用硬化 性樹脂組合物上，以使第2偏光機構成為與樹脂層形成用 硬化性樹脂組合物側為相反側之方式重疊液晶面板，由保 護板、液晶面板、及未硬化之密封部而獲得使包含樹脂層 形成用硬化性樹脂組合物之未硬化之樹脂層得以密封之積 層物的步驟；及 (d2)將積層物放置在5〇 kpa以上之壓力環境下之狀態 下，使未硬化之密封部及未硬化之樹脂層硬化。 方法（〇〇與方法（β)皆係於減壓環境下於保護板與液晶面 板之間封入有液狀之樹脂層形成用硬化性樹脂組合物，於 大氣壓環境下等之較高壓力環境下使所封入之樹脂層形成 用硬化性樹脂組合物硬化而形成樹脂層的方法。減壓下之 154270.doc 201133058 樹月θ層形成用硬化性樹脂組合物之封入並非係於保護板與 液Β曰面板之間隙狹窄且面積大的空間内注入樹脂層形成用 硬化性樹脂之方法’而是對保護板及液晶面板中之一方之 構件之大致整個面供給樹脂層形成用硬化性樹脂組合物， 其後重叠另一方之構件’於保護板與液晶面板之間封入樹 脂層形成用硬化性樹脂組合物的方法。 藉由減壓下之液狀之樹脂層形成用硬化性樹脂組合物之 封入及大氣壓下之樹脂層形成用硬化性樹脂組合物之硬 化而製造透明積層體之製造方法之一例已公知。例如，於 國際公開第2008/81838號小冊子、國際公開第2〇〇9/16943 號小冊子中記載有透明積層體之製造方法及該製造方法所 使用之硬化性樹脂組合物，其等被併入本說明書中。 以下，以方法（α)為例來說明本發明之液晶顯示裝置之 製k方法。再者，方法（β)僅係將方法（α)中之液晶面板換 成保護板’僅將方法⑷中之保護板換成液晶面板，除此 以外為完全相同之方法，故省略方法（ρ)之說明。 (步驟（a 1)) 首先，於液晶面板之與第2偏光機構側為相反側之表面 之周緣部，塗佈液狀之密封部形成用硬化性樹脂組合物而 形成未硬化之密封部。 塗佈係使用印刷機、點膠機等而進行。 於未硬化之密封部中，於下述步驟（cl)中，需要有不會 自未硬化之密封部與液晶面板之界面、及未硬化之密封部 與保護板之界面漏出液狀之樹脂形成用硬化性樹脂組合物 154270.doc •14- 201133058 :程度以上的界面接著力、以及可維持形狀之程度之堅固 Γ。因此’對於未硬化之密封部，録為使㈣度較高的 :封部形成用硬化性樹脂組合物。又’為了保持液晶面板 護板之間隔，亦可將特定之粒子徑之間隔粒子調配於 迸封部形成用硬化性樹脂組合物中。 密封部形成用硬化性樹脂組合物之黏度較佳為綱〜麵 ’更佳為_〜25GG Pa.s，進而更佳為〗麵〜謂BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a liquid crystal display device for protecting a liquid crystal panel by a protective sheet. [Prior Art] As a liquid crystal display device, it is known that a liquid crystal panel in which a liquid crystal cell is sandwiched between a pair of polarizing plates and a protective plate that protects the liquid crystal panel are laminated with a resin layer. The liquid crystal panel is usually obtained by attaching a polarizing plate with an adhesive on both sides of the liquid crystal cell. At this time, it is necessary to accurately align the polarization axes of the pair of polarizing plates. However, the soft film-shaped polarizing plate is difficult to handle, and it is difficult to perform fine adjustment of the polarizing axis when the polarizing plate is attached. Further, if the polarizing axes of the pair of polarizing plates are misaligned after attachment, the polarizing plate cannot be reattached. And thus become a defective product. Therefore, the following solution is proposed: the polarizing plate on the side of the protective plate of the two polarizing plates is attached to the protective plate in advance instead of the liquid crystal panel, and the surface to be bonded only on the opposite side to the side of the protective plate is attached. Before the liquid crystal panel of the polarizing plate and the protective plate to which the polarizing plate is attached on the surface on the side of the liquid crystal panel, the film-shaped polarizing plate itself which is softer is easier to operate. The liquid crystal panel of the member is opposite to the protective plate. Move, perform the slight adjustment of the polarization axis (paragraph [0086] of Patent Document 1, etc.). Further, as a method of bonding a liquid crystal panel and a protective plate, there is proposed a method in which a frame body is provided on four sides of a periphery of a surface of a liquid crystal panel, and a liquid photocurable resin is poured into a region surrounded by the frame body. The upper part of the Nie protection board (patent literature section [〇〇58], etc.). Further, in order to prevent air bubbles from remaining between the liquid crystal = 154270.doc 201133058 plate and the protective plate, the upper half of the frame body is formed into a porous member, and the porous member absorbs air bubbles. Knife However, in this method, there is a problem that even if bubbles in the vicinity of the porous member of the casing are sufficiently absorbed and removed, bubbles other than the bubbles are hard to remove. [Problem to be Solved by the Invention] The present invention provides a method of manufacturing a liquid crystal display device which can polarize a pair of polarizing mechanisms. The preferred angle formed by the shaft is easily aligned, and the residual of the bubbles in the resin layer sandwiched between the protective sheet and the liquid crystal panel is sufficiently suppressed. Solution to Problem A method of manufacturing a liquid crystal display device of the present invention is characterized in that it is a method of manufacturing a liquid crystal display device comprising: a protective plate provided with a first polarizing mechanism on a surface of a transparent surface material; a liquid crystal panel provided with a second polarizing mechanism on a surface of the liquid crystal cell; a resin layer sandwiched between the protective plate and the liquid crystal panel; and a sealing portion surrounding the periphery of the resin layer; the first polarizing mechanism is located between the transparent surface material and the resin layer The second polarizing means is located on the surface opposite to the resin layer side of the liquid crystal cell, and the manufacturing method of the liquid crystal display device includes the following steps (al) to (dl) or the following steps (a2) to (d2). (al) forming a rim on the surface of the surface of the liquid crystal panel opposite to the side of the second polarizing means 154270.doc 201133058, and applying a sealing portion for forming a liquid-like sealing portion to be cured without curing the curable resin; b 1) For a π that is not hardened. The curable resin composition for forming a liquid resin layer is supplied to the region surrounded by the crucible; (Cl) is applied to the curable resin composition for forming a resin layer in a reduced pressure atmosphere of 1 Torr or less to make the first The protective layer is superimposed on the side of the curable resin composition for forming a resin layer, and the uncured resin containing the curable resin composition for forming a resin layer is obtained from the protective sheet, the liquid crystal panel, and the uncured seal portion. a step of sealing the layered layer; and (dl) placing the laminate in a pressure environment of 5 〇 kpa or more to harden the uncured seal portion and the uncured resin layer. (a2) Yu Bao. A peripheral portion of the surface of the first polarizing means side of the fascia is coated with a curable resin composition for forming a liquid seal portion to form an uncured seal portion; (b2) an area surrounded by an uncured seal portion (c2) 'on the curable resin composition for forming a resin layer' in a reduced pressure environment of 1 〇〇pa or less to make the second polarizing means and resin The liquid crystal panel is stacked so that the side of the layer forming curable resin composition is on the opposite side, and the uncured resin layer containing the curable resin composition for forming a resin layer is obtained from the protective sheet, the liquid crystal panel, and the uncured seal portion. a step of sealing the laminate; and (d2) placing the laminate under a pressure of 50 kPa or more in a state of 154270.doc 201133058 to harden the uncured seal portion and the uncured resin layer. In the above steps (cl) and (c2), it is preferable to adjust the positions of the protective plate and the liquid crystal panel such that the angle formed by the polarization axes of the first polarizing means and the second polarizing means conforms to the design of the liquid crystal cell. Advantageous Effects of Invention According to the method of manufacturing a liquid crystal display device of the present invention, the preferred angle formed by the polarization axes of the pair of polarizing means can be easily aligned, and the bubbles in the resin layer sandwiched between the protective plate and the liquid crystal panel The residue is sufficiently suppressed. [Embodiment] In the present specification, "transparent" means light transmissive, and "(meth) acrylate" means acrylate or methacrylate. <Liquid Crystal Display Device> Fig. 1 is a cross-sectional view showing an example of a liquid crystal display device of the present invention, and Fig. 2 is a plan view. The liquid crystal display device 1 includes a protective plate 丨0, a liquid crystal panel 2A, a resin layer 4A sandwiched between the protective plate 10 and the liquid crystal panel 20, and a sealing portion 50 surrounding the resin layer 4A. The shape of the liquid crystal display device 1 is generally rectangular. Regarding the size of the liquid crystal display device 1, since the manufacturing method of the present invention is particularly suitable for the manufacture of a liquid crystal display device having a large area, in the case of a television receiver, it is preferably 0.5 mx 〇.4 m or more, and particularly preferably 0.7. Mx〇.4 m or more. The upper limit of the size of the liquid crystal display device is often determined by the size of the display panel. In addition, the operation of an excessively large liquid crystal display device in terms of setting and the like is apt to become difficult. Due to these constraints, the upper limit of the liquid crystal display device is generally about 5.2 m.sup.5. The protective plate 10 and the liquid crystal panel 20 may have substantially the same size. However, since the protective plate 10 has a relationship with the casing in which the liquid crystal display device 1 is housed, the protective plate 10 is often slightly larger than the liquid crystal panel 20. On the contrary, the protective plate 1 〇 may be slightly smaller than the liquid crystal panel 20 according to the structure of the casing. _ [Protection plate] The protection plate 10 is provided on the image display side of the liquid crystal panel 20 and protects the liquid crystal panel 20. The protective sheet 10 has a transparent surface material 12, a light-shielding printing portion 14 formed on a peripheral portion of the surface of the transparent surface material 12 on the resin layer 40 side, and a first polarized light provided on the surface of the transparent surface material 12 on the resin layer 40 side. Organization 丨 6. The protective plate 10 is different from the conventional protective plate including only the transparent surface material or the transparent surface material provided with the light-shielding printing portion on the peripheral edge portion, and the first polarizing mechanism 16 is provided on the surface of the protective plate 1〇. In the invention, such a protective plate with a polarizing mechanism is also simply referred to as a protective plate. (Transparent surface material) The transparent surface material 12 is a glass plate or a transparent resin plate, and it is self-evident from the viewpoint of high transparency of emitted light or reflected light from the liquid crystal panel 20, and Glass plate is also the best in terms of light resistance, low complex refractive index, high planar precision, surface damage resistance, and high mechanical strength. From the viewpoint of sufficiently penetrating the light for hardening the photocurable resin composition, it is also preferably a glass plate. The material of the glass plate may, for example, be a glass material such as soda lime glass, and more preferably a high penetration glass (white plate glass) having lower iron content and less greenness. For 154270.doc 201133058, tempered glass can also be used to improve safety. In particular, in the case where a thin transparent surface material is required, a tempered glass obtained by a chemical strengthening method can be used. For example, when the thickness of the transparent surface material is 丨5 mm or less, if the tempered glass produced by the chemical strengthening method is used, the mechanical strength can be improved, and therefore, as a material of the transparent resin sheet, transparency can be cited. Higher resin materials (polycarbonate, decyl phthalate, etc.). On the surface of the first surface of the transparent surface material 12 on the side of the first polarizing means 16, a surface treatment may be performed in order to increase the adhesion to the interface between the first polarizing means 16. As a method of surface treatment, a method of treating the surface of the transparent surface material 12 with a decane coupling agent, and a treatment for forming a film of cerium oxide via an oxidizing flame of a flame burner may be mentioned. On the surface of the transparent surface material 12 opposite to the side of the first polarizing means ι6, an antireflection layer may be provided for the purpose of improving the contrast of the image. The antireflection layer may be formed by directly forming an inorganic film on the surface of the transparent surface material 12. The method and the method of adhering the transparent resin film provided with the antireflection layer to the transparent surface material 丨2 are provided. Further, depending on the purpose, a part or the whole of the transparent surface material 12 may be colored, or a part of the surface or the entire surface of the transparent surface material 12 may be formed into a frosted glass shape to scatter light or be a part or the whole of the transparent surface material 12. Fine irregularities or the like are formed on the surface to refract or reflect the transmitted light. Further, a colored film, a light-scattering film, a light-refractive film, a light-reflecting film, or the like may be adhered to one surface or the entire surface of the transparent surface material 12. Regarding the thickness of the transparent face material 12, from the viewpoint of mechanical strength and transparency, 154270.doc 201133058. In the case of a glass plate, it is usually 0.5 to 25 mm. For the use of TV receivers for indoor use, displays for PCs (PCs), etc. 'From the viewpoint of weight reduction of liquid crystal display devices, 5' is preferably 1 to 6 mm, for outdoor setting For public display use, it is preferably 3 to 20 mm. In the case of a transparent resin sheet, it is preferably 2 to 10 mm. (Light-shielding printing unit) The light-shielding printing unit 14 is a hidden member that is connected to the wiring member of the liquid crystal panel 2, such that the liquid crystal panel 2 is not visually recognized from the protection panel 10 side. The light-shielding printing portion 14 may be disposed on the resin layer 40 side of the transparent surface material 12 or on the opposite side thereof, and is preferably provided in the resin of the transparent surface material 12 in terms of reducing the parallax between the light-shielding printing portion 14 and the image display region. Layer 4 〇 side. In the case where the transparent surface material 12 is a glass plate, it is preferable that the light-shielding printing portion 14 uses ceramic printing containing a black pigment to have high light-shielding property. Further, a light-shielding printing portion may be provided on the resin layer 40 side of the first polarizing mechanism 16 on the resin layer 40 side of the transparent surface material 12 or on the back surface thereof. When the i-th polarizing mechanism 16 is provided by a resin film, printing of an organic ink containing a black pigment or a black dye can lower the temperature at which the printing portion is formed, which is preferable. (First Polarizing Mechanism) The first polarizing mechanism 16 is constituted by a member including a polarizer having a polarizing function. The first polarizing mechanism 16 is capable of sandwiching a polarizing plate with an adhesive on the surface of the transparent surface material 12, and sandwiching the film-like I54270.doc 201133058 absorbing type photon by the transparent surface material 12 and the protective film and Set by the method of fitting, etc. The polarizing plate may be an absorption type polarizing plate in which a pair of protective films are bonded to both surfaces of a film-shaped absorbing polarizer, and a wire grid formed by arranging a plurality of metal thin wires in parallel on the surface of the transparent substrate A type of polarizer wire grid type polarizer or the like. The film-shaped absorbing type photo-polarizer is a resin film such as urethane (hereinafter referred to as PVA). The protective film may, for example, be a triacetyl cellulose (hereinafter referred to as TAC) film. [Liquid Crystal Panel] The liquid crystal panel 20 includes a liquid crystal cell 22, and a flexible printed wiring board 24 to which a driving IC (integrated circuit 'integrated circuit) for operating the liquid crystal cell 22 is mounted, and a second The polarizing mechanism 26 is provided on the surface of the liquid crystal cell 22 on the side opposite to the resin layer 40 side. Unlike the previous liquid crystal panel in which the polarizing plate is provided on both surfaces of the liquid crystal cell, the liquid crystal panel 20 is provided with the second polarizing means 26 of the polarizing plate # on the surface opposite to the side of the protective plate 1. However, the present invention In the above, the liquid crystal panel with only one side of the polarizing mechanism is also simply referred to as a liquid crystal panel. (Liquid Crystal Cell) The liquid crystal cell 22 is formed by interposing a transparent surface material 3 2 provided with a color filter and a transparent surface material 34 provided with a TFT (thin film transistor) through the liquid crystal layer 36. On the surface of the resin layer 40 side of the liquid crystal cell 22, in order to increase the interfacial adhesion force between the resin layer 4 and the sealing portion 5, a surface treatment may be performed. The surface is 154270.doc •10· 201133058 It can be applied only to the peripheral part of the surface or to the entire surface. As a method of surface treatment, a method of treating with a primer which can be processed at a low temperature and the like can be mentioned. The thickness of the liquid crystal cell 22 is usually 0.4 to 4 mm in the case of a liquid crystal cell which is operated by a TFT. (Second polarizing means) The second polarizing means 26 is constituted by a member including a polarizer having a polarizing function. The second polarizing means 26 can be provided by a method of adhering a polarizing plate to the surface of the liquid crystal cell 22 with an adhesive. Examples of the polarizing plate include the above-described absorption type polarizing plate and wire grid type polarizing plate. [Resin layer] The resin layer 40 is a layer obtained by curing the curable resin composition for forming a liquid resin layer described below. In the liquid crystal display device, a curable resin composition for forming a resin layer having a low modulus of elasticity of the resin after curing is preferred. When the modulus of elasticity of the resin is large, there is a problem that the stress generated by hardening or the like during curing of the resin adversely affects the display performance of the liquid crystal panel 2G. The thickness of the resin layer 40 is preferably 〇.〇3 to 2 mm, more preferably 〇丨~^ mm. When the thickness of the resin layer is 〇·〇 3 mm or more, the resin layer 4 〇 can effectively cushion the impact of the force from the side of the protective sheet 10 and the like to protect the liquid crystal panel 2 . Further, in the manufacturing method of the present invention, a foreign matter exceeding the thickness of the resin layer 40 is mixed between the protective sheet 1 and the liquid crystal panel 2, and the thickness of the resin layer is not changed greatly by 154270.doc 201133058 degrees. It has less effect on light transmission performance. When the thickness of the resin layer 40 is 2 mm or less, bubbles are less likely to remain in the resin layer 4, and the thickness of the entire liquid crystal display device 1 is not increased unnecessarily. The method of adjusting the thickness of the resin layer 40 is a curable resin for forming a liquid resin layer which is adjusted to the thickness of the uncured seal portion and which is supplied to the region surrounded by the uncured seal portion. A method of adjusting the amount of supply of the composition. [Sealing portion] The sealing portion 50 is obtained by applying and curing a curable resin composition for forming a liquid sealing portion. The area on the outer side of the image display area of the liquid crystal panel 20 is relatively narrow. Therefore, the width of the sealing portion 50 is preferably narrow. The width of the sealing portion 5〇 is preferably 0_5 to 2 mm, more preferably 0.8 to 1.6 mm. <Manufacturing Method of Liquid Crystal Display Device> The method of manufacturing the liquid crystal display device of the present invention includes the following steps (a1) to (d1), or includes the following steps (a2) to (d2) Method (8). (Method (4)) (a) forming a uncured seal portion by applying a curable resin composition for forming a liquid seal portion to a peripheral portion of a surface of the liquid crystal panel opposite to the second polarizing means side; a curable resin composition for forming a liquid resin layer is supplied to a region surrounded by the unhardened sealing portion; (cl) is applied to the curable resin composition for forming a resin layer in a reduced pressure environment of 100 Pa or less In the first polarizing means, the protective layer is superimposed on the side of the resin layer forming hard 154270.doc -12-201133058-based resin composition, and the resin is obtained by a protective plate, a liquid crystal panel, and an unhardened sealing portion. a step of forming a laminate in which the uncured resin layer of the curable resin composition is sealed; and (dl) placing the laminate in a pressure environment of 50 kPa or more to make the unhardened seal portion and The hardened resin layer is hardened. (Method (P)) (a2) Applying a curable resin composition for forming a liquid sealing portion to a peripheral portion of the surface of the first polarizing means side of the protective sheet to form an unhardened sealing portion; (b2) The curable resin composition for forming a liquid resin layer is supplied from a region surrounded by the unhardened sealing portion; (C2) is applied to the curable resin composition for forming a resin layer in a reduced pressure environment of 1 〇〇Pa or less. In the second polarizing means, the liquid crystal panel is placed so as to be opposite to the side of the curable resin composition for forming a resin layer, and the protective layer, the liquid crystal panel, and the unhardened sealing portion are obtained to cure the resin layer. a step of sealing the laminate of the uncured resin layer of the resin composition; and (d2) placing the laminate under a pressure environment of 5 〇 kpa or more to make the uncured seal portion and the uncured resin Layer hardening. (The method and the method (β) are a curable resin composition for forming a liquid resin layer between a protective plate and a liquid crystal panel in a reduced pressure environment, and are subjected to a high pressure environment such as an atmospheric pressure atmosphere. A method of forming a resin layer by curing the resin composition for forming a resin layer to be sealed, and forming a resin layer under reduced pressure. 154270.doc 201133058 The sealing of the curable resin composition for forming a tree θ layer is not attached to a protective sheet and liquid helium. In the method of injecting a curable resin for forming a resin layer into a space having a narrow gap and a large area of the slab, the resin layer forming curable resin composition is supplied to substantially the entire surface of one of the protective plate and the liquid crystal panel. Then, a method of encapsulating the curable resin composition for forming a resin layer between the protective sheet and the liquid crystal panel is superposed on the other member. The sealing of the curable resin composition for forming a liquid resin layer under reduced pressure and An example of a method for producing a transparent laminate by curing a curable resin composition for forming a resin layer under atmospheric pressure is known. For example, it is disclosed internationally. The method for producing a transparent laminate and the curable resin composition used in the method of the present invention are described in the above-mentioned publications, and the like. The method (α) is taken as an example to describe the method for manufacturing the liquid crystal display device of the present invention. Furthermore, the method (β) only replaces the liquid crystal panel in the method (α) with a protective plate 'only the protection in the method (4) The method of replacing the panel with the liquid crystal panel is completely the same, and the description of the method (ρ) is omitted. (Step (a 1)) First, the periphery of the surface opposite to the side of the second polarizing means of the liquid crystal panel The uncured sealing portion is formed by applying a curable resin composition for forming a liquid-like sealing portion. The coating is performed using a printing machine, a dispenser, or the like. In the unhardened sealing portion, the following steps are performed. In (cl), there is a need for a resin-forming curable resin composition that does not leak from the interface between the unsealed sealing portion and the liquid crystal panel, and the interface between the unhardened sealing portion and the protective sheet. 154270.doc • 14- 201133058 : degree The upper interface has a strong adhesive force and a degree of shape that can maintain the shape. Therefore, 'the uncured seal portion is recorded with a high degree of (four) degree: a curable resin composition for forming a seal portion. The spacer particles of the specific particle diameter may be blended in the curable resin composition for forming a seal portion. The viscosity of the curable resin composition for forming a seal portion is preferably from the surface to the surface. _~25GG Pa.s, and thus better for the face ~
Pw。若黏度為500⑹以上，則可較長時間地維持未硬 化之密封部之形狀’可充分維持未硬化之密封部之高度。 若黏度為侧Pa.s以下，則可藉由塗佈而形成未硬化之密 封部。 被封部形成用硬化性樹脂組合物之黏度係於25^時使用 E型黏度計測定。 密封部形成用硬化性樹脂組合物既可為光硬化性樹脂組 合物，亦可為熱硬化性樹脂組合物。作為密封部形成用硬 化性樹脂組合物，自可於低溫下硬化、且硬化速度較快之 觀點而言，較佳為含有硬化性化合物及光聚合起始劑（ci) 之光硬化性樹脂組合物。又，硬化無需較高之溫度，故由 咼溫導致之液晶面板損傷之虞亦較少。 作為密封部形成用光硬化性樹脂組合物，自容易將黏度 調整為上述範圍内之觀點而言，作為上述硬化性化合物， 較佳為含有具有硬化性基且數量平均分子量為3〇 〇〇〇〜 100,000之寡聚體（A)之1種以上、及具有硬化性基且分子量 為125〜600之單體（B)之1種以上，並且單體（B)於寡聚體（A) 15 154270.doc 201133058 與單體（B)之共計（丨00 wt%)中之比例為丨5〜5〇 wt%。 寡聚體（A)之數量平均分子量為3〇 〇〇〇〜ι〇〇 〇〇〇，較佳為 4M〇〇，_ ’更佳為50，_〜65，_。若寡聚體㈧之數 量平均分子量為該範圍，則容易將密封部形成用光硬化性 樹脂組合物之黏度調整為上述範圍。 寡聚體（A)之數量平均分子量係藉由Gp(：(gel chr〇matography，凝膠滲透色譜法）測定而獲得之聚苯乙烯 換算之數量平均分子量。再者，於Gpc測定中，當出現未 反應之低分子量成分（單體等）之峰值之情形時，將該峰值 除外而求出數量平均分子量。 作為寡聚體（A)之硬化性基，可舉出加成聚合性之不飽 和基（丙烯醯氧基、甲基丙烯醯氧基等）、不飽和基與硫氫 基之組合等，自硬化速度較快之觀點及獲得透明性較高之 密封部之觀點而言，較佳為選自丙烯醯氧基及甲基丙烯醯 氧基中之基。又，較高分子量之寡聚體中之硬化性基 相較於較低分子量之單體（B)中之硬化性基之反應性更容 易’隻低，故先增進單體（B)之硬化而導致組合物全體之黏 性急遽變高，從而存在有硬化反應成為不均質之虞。為了 減小兩者之硬化性基之反應性之差而獲得均質的密封部， 更佳為將寡聚體（A)之硬化性基形成為反應性較高之丙烯 醯氧基，將單體（B)之硬化性基形成為反應性較低之甲基 丙稀醯氧基。 作為寡聚體（A) ’自密封部形成用光硬化性樹脂組合物 之硬化性、密封部之機械特性之觀點而言，較佳為每】分 154270.doc •16- 201133058 子平均含有1.8〜4個硬化性基者。 作為寡聚體（A)，可舉出具有氨酯鍵之氨酯寡聚體、聚 氧化亞烷基多元醇（polyOXyalkylene p〇iy〇ls)之聚（甲基）丙 烯酸酯、及聚酯多元醇之聚（甲基）丙烯酸酯等，自可根據 氨酯鏈之分子設計等而大幅調整硬化後之樹脂之機械特 性、與液晶面板或保護板之密著性等之觀點而言，較佳為 氨酯寡聚體（A1)。 數1平均分子量為3〇,〇〇〇〜1〇〇,〇〇〇之氨酯寡聚體（八1)由 於成為高黏度，故以通常之方法難以合成，即便已合成亦 難以與單體（B)混合。因此，於本發明中較佳為，以下述 之合成方法合成氨酯募聚體（A1)之後，將所獲得之生成物 維持原樣直接用作密封部形成用光硬化性樹脂組合物，或 者將所獲得之生成物進而以下述單體（B)(單體（B 1 )、單體 (B3)等）稀釋後用作密封部形成用光硬化性樹脂組合物。 氨酯寡聚體（A1)之合成方法： "亥方法為.作為稀釋劑，於下述單體（B)之1種即不具有 與異氰酸酯基反應之基之單體（B1)存在的情況下，使多元 醇與聚異氰酸酯發生反應而獲得具有異氰酸酯基之預聚物 之後’使該預聚物之異氰酸酯基與具有與異氰酸酯基反應 之基及硬化性基之單體（B2)發生反應。 作為多元醇、聚異氰酸酯，可舉出公知之化合物，例 如’於國際公開第2009/016943號小冊子中記載之作為氨 醋系寡聚體（a)之原料之多元醇（i)、二異氰酸酯（ii)等，其 4被併入本說明書中。 154270.doc -17- 201133058 作為不具有與異氰酸酯基反應之基之單體（B1)，可舉出 具有碳數8〜22之烷基之（甲基）丙烯酸烷酯（（甲基）丙烯酸正 十一烷酯、（甲基）丙烯酸正十八烷酯、（甲基）丙烯酸正二 十二烷酯等）、具有脂環式烴基之（甲基）丙烯酸酯（（甲基）丙 烯I異冰片酯、（曱基）丙烯酸金剛院酯等）。 作為具有與異氰酸酯基反應之基及硬化性基之單體 (Β2)，可舉出具有活性氫（羥基、胺基等）及硬化性基之單 體，具體而言’可舉出具有碳數2〜6之羥烷基之（甲基）丙 烯酸羥烷醋（（甲基）丙烯酸2_羥基甲酯、（甲基）丙烯酸2_羥 基丙酯、（甲基）丙烯酸2-羥基丁酯、（曱基）丙烯酸4•羥基丁 Θ曰等）等，較佳為具有碳數2〜4之羥烷基之丙烯酸羥烷酯。 單體（Β)之分子量為125〜600，較佳為14〇〜4〇〇，更佳為 150〜350。若單體（Β)之分子量為125以上，則藉由下述減 壓積層方法而製造液晶顯示裝置時單體（Β)之揮發受到抑 制。若單體（Β)之分子量為60〇以下，則可提高單體（Β)相對 於高分子量之寡聚體（Α)之溶解性，可適當進行作為密封 形成用光硬化性樹脂組合物之黏度調整。 作為單體（Β)之硬化性基，可舉出加成聚合性之不飽和 基（丙烯醯氧基、甲基丙烯醯氧基等）、不飽和基與硫氫基 之組合等，自硬化速度較快之觀點及獲得透明性較高之密 封部之觀點而言，較佳為選自丙烯醯氧基及甲基丙烯醯氧 基中之基。又，較低分子量之單體（Β)中之硬化性基相較 於較高分子量之募聚體（Α)中之硬化性基之反應性更容易 變高，故先增進單體（Β)之硬化而導致組合物全體之黏性 154270.doc -18- 201133058 急遽變南從而存在有硬化反應成為不均質之虞。為了獲得 均質的密封部，更佳為將單體（B)之硬化性基形成為反應 性較低之甲基丙烯醯氧基，將寡聚體（A)之硬化性基形成 為反應性較高之丙烯醯氧基。 作為單體（B)，自密封部形成用光硬化性樹脂組合物之 硬化〖生、後封部之機械特性之觀點而言，較佳為每1分子 含有1〜3個硬化性基者。 在、封邛形成用光硬化性樹脂組合物中，亦可含有上述氨 西曰寡聚體（A1)之合成方法中用作稀釋劑之單體（B1)作為單 體（B)。又’亦可含有上述氨酯募聚體（A1)之合成方法中 所使用之未反應之單體（B2)作為單體。 關於單體（B)，自液晶面板或保護板與密封部之密著性 或者下述各種添加劑之溶解性之觀點而言，較佳為包含具 有羥基之單體（B3)。 作為具有經基之單體（B3)，較佳為具有羥基數丨〜2、碳 數3 8之沒烧基之甲基丙烯酸羥酯（曱基丙烯酸2_羥丙酯' 甲基丙稀酸2-經丁酿、曱基丙烯酸4_羥丁酯、甲基丙烯酸 6 I己g曰等），特佳為曱基丙稀酸經丁酯。 關於單體（B)之比例，於寡聚體（A)與單體之共計（1〇〇 wt/ο)中為15〜5〇 wt%，較佳為2〇〜45 wt〇/〇，更佳為25〜4〇Pw. When the viscosity is 500 (6) or more, the shape of the unhardened seal portion can be maintained for a long period of time. The height of the unhardened seal portion can be sufficiently maintained. If the viscosity is less than the side Pa.s, an uncured seal can be formed by coating. The viscosity of the curable resin composition for forming a seal was measured at 25 ° using an E-type viscometer. The curable resin composition for forming a sealing portion may be a photocurable resin composition or a thermosetting resin composition. The curable resin composition for forming a sealing portion is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator (ci) from the viewpoint of being hardenable at a low temperature and having a high curing rate. Things. Moreover, the hardening does not require a higher temperature, so the damage of the liquid crystal panel caused by the temperature is less. The photocurable resin composition for forming a sealing portion preferably contains a curable group and a number average molecular weight of 3 Å as the curable compound from the viewpoint of easily adjusting the viscosity to the above range. 1 or more of the oligomers (A) of 100,000 or more, and 1 or more types of the monomer (B) having a curable group and having a molecular weight of 125 to 600, and the monomer (B) is in the oligomer (A) 15 154270.doc 201133058 The ratio of the total amount of monomer (B) (丨00 wt%) is 丨5~5〇wt%. The number average molecular weight of the oligomer (A) is 3 〇 〇〇 to ι〇〇 〇〇〇, preferably 4 M 〇〇, _ ' more preferably 50, _ to 65, _. When the number average molecular weight of the oligomer (h) is within this range, the viscosity of the photocurable resin composition for sealing a portion is easily adjusted to the above range. The number average molecular weight of the oligomer (A) is a polystyrene-converted number average molecular weight obtained by Gp (: (gel chr〇 matography)). Further, in the Gpc measurement, when When a peak of an unreacted low molecular weight component (monomer or the like) is present, the number average molecular weight is determined by excluding the peak. The curable group of the oligomer (A) may be an additive polymerization property. A saturated group (acryloxy group, methacryloxy group, etc.), a combination of an unsaturated group and a sulfhydryl group, etc., from the viewpoint of a faster curing speed and a viewpoint of obtaining a sealing portion having high transparency Preferably, it is selected from the group consisting of an acryloxy group and a methacryloxy group. Further, the hardening group in the higher molecular weight oligomer is harder than the lower molecular weight monomer (B). The reactivity is easier to 'only low', so the hardening of the monomer (B) is first promoted, and the viscosity of the entire composition is rapidly increased, so that the hardening reaction becomes inhomogeneous. In order to reduce the hardenability of the two. A homogeneous seal is obtained by the difference in reactivity More preferably, the curable group of the oligomer (A) is formed into a highly reactive propylene oxime group, and the curable group of the monomer (B) is formed into a less reactive methyl propylene oxy group. From the viewpoint of the curability of the photocurable resin composition for self-sealing portion formation and the mechanical properties of the sealing portion, the oligomer (A) is preferably 154270.doc •16-201133058 1.8 to 4 hardening bases. As the oligomer (A), a urethane oligomer having a urethane bond or a polyoxyalkylene polyol (polyOXyalkylene p〇iy〇ls) may be mentioned. The acrylate and the poly(meth) acrylate of the polyester polyol, etc., can greatly adjust the mechanical properties of the cured resin according to the molecular design of the urethane chain, and the adhesion to the liquid crystal panel or the protective sheet. From the viewpoint of properties, etc., it is preferably a urethane oligomer (A1). The average molecular weight of number 1 is 3 〇, 〇〇〇~1 〇〇, and the urethane oligomer of 〇〇〇 (8) becomes High viscosity, so it is difficult to synthesize in the usual way, even if it is synthesized, it is difficult to mix with monomer (B). Therefore, in this In the invention, it is preferred that the urethane polymer (A1) is synthesized by the following synthesis method, and the obtained product is used as it is as a photocurable resin composition for forming a sealing portion, or the obtained product is used as it is. Further, it is diluted with the following monomer (B) (monomer (B1), monomer (B3), etc.) and used as a photocurable resin composition for forming a seal portion. Synthesis method of urethane oligomer (A1): "Hai method is used as a diluent to react a polyol with a polyisocyanate in the presence of a monomer (B1) which does not have a group reactive with an isocyanate group After obtaining the prepolymer having an isocyanate group, the isocyanate group of the prepolymer is reacted with the monomer (B2) having a group reactive with an isocyanate group and a curable group. The polyhydric alcohol and the polyisocyanate may, for example, be a known compound, for example, a polyol (i) or a diisocyanate which is a raw material of the aminoacetic acid oligomer (a) described in the pamphlet of International Publication No. 2009/016943 ( Ii) etc., 4 of which is incorporated in the specification. 154270.doc -17- 201133058 As the monomer (B1) having no reaction with an isocyanate group, an alkyl (meth)acrylate having a carbon number of 8 to 22 ((meth)acrylic acid) is exemplified. Undecyl ester, n-octadecyl (meth)acrylate, n-docosyl (meth)acrylate, etc., (meth) acrylate ((meth) acrylate I) having an alicyclic hydrocarbon group Borneol ester, (indenyl) acrylic acid, etc.). Examples of the monomer (Β2) having a group reactive with an isocyanate group and a curable group include a monomer having an active hydrogen (hydroxyl group, an amine group, etc.) and a curable group, and specifically, 'having a carbon number 2 to 6 hydroxyalkyl (meth) hydroxy methacrylate (2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (fluorenyl) 4, hydroxybutanyl, etc., etc., preferably a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms. The monomer (Β) has a molecular weight of from 125 to 600, preferably from 14 to 4, more preferably from 150 to 350. When the molecular weight of the monomer (Β) is 125 or more, the volatilization of the monomer (?) is suppressed when the liquid crystal display device is produced by the following pressure reduction lamination method. When the molecular weight of the monomer (Β) is 60 Å or less, the solubility of the monomer (Β) with respect to the high molecular weight oligomer (Α) can be improved, and the photocurable resin composition for sealing formation can be suitably used. Viscosity adjustment. Examples of the curable group of the monomer (Β) include an addition polymerizable unsaturated group (such as a propylene oxy group or a methacryloxy group), a combination of an unsaturated group and a sulfhydryl group, and self-hardening. From the viewpoint of a faster speed and a viewpoint of obtaining a sealing portion having high transparency, a group selected from the group consisting of an acryloxy group and a methacryloxy group is preferable. Moreover, the reactivity of the hardening group in the lower molecular weight monomer (Β) is more likely to be higher than the reactivity of the hardening group in the higher molecular weight polymer (Α), so the monomer (Β) is first promoted. The hardening results in the viscosity of the entire composition 154270.doc -18- 201133058 The urgency changes to the south and there is a hardening reaction to become heterogeneous. In order to obtain a homogeneous sealing portion, it is more preferable to form the curable group of the monomer (B) into a less reactive methacryloxy group, and to form the curable group of the oligomer (A) to be more reactive. High propylene oxime. The monomer (B) is preferably one to three hardening groups per molecule from the viewpoint of the hardening of the photocurable resin composition for forming a self-sealing portion and the mechanical properties of the post-sealing portion. In the photocurable resin composition for sealing formation, the monomer (B1) used as a diluent in the synthesis method of the above ampicillin oligomer (A1) may be contained as a monomer (B). Further, the unreacted monomer (B2) used in the synthesis method of the above urethane polymer (A1) may be contained as a monomer. The monomer (B) preferably contains a monomer (B3) having a hydroxyl group from the viewpoint of the adhesion of the liquid crystal panel or the protective sheet to the sealing portion or the solubility of various additives described below. As the monomer having a trans group (B3), it is preferably a hydroxy methacrylate having a hydroxyl group of 丨 〜2 and a carbon number of 38 (2-hydroxypropyl methacrylate) methacrylic acid 2-butyl, 4-hydroxybutyl methacrylate, 6 I hexyl methacrylate, etc., particularly preferably butyl acrylate. The ratio of the monomer (B) is 15 to 5 % by weight, preferably 2 to 45 wt / 〇, in the total of the oligomer (A) and the monomer (1 〇〇 wt / ο), More preferably 25~4〇
Wt% °右單體之比例為15 wt%以上，則密封部形成用光 M H >物之硬化性、液晶面板錢護板與密封部 之密著性成為良好。若單體⑻之比例為50 wt%以下，則 +易將密封部形成用光硬化性樹脂組合物之黏度調整為 154270.doc •19- 201133058 500 Pa*s以上。 作為光聚合起始劑（Cl) ’可舉出苯乙酮系、縮_系、安 息香或安息香醚系、氧化膦系、二笨曱酮系、硫雜蒽嗣 系、醌系等之光聚合起始劑，較佳為苯乙酮系、縮嗣系、 安息香醚系之光聚合起始劑。於藉由短波長之可見光進行 硬化之情形時，自吸收波長域之觀點而言，更佳為氧化鱗 系之光聚合起始劑。藉由併用吸收波長域不同之2種以上 之光聚合起始劑（C1 )，可進一步加快硬化時間，且可提高 密封部之表面硬化性。又，於不阻礙與未硬化之密封部鄰 接之部分之樹脂層形成用光硬化性樹脂組合物之硬化的範 圍内’亦可併用下述光聚合起始劑（C2)。於併用之情形 時’自效率良好且有效地進行硬化之觀點而言，聚合起始 劑（c 1)與聚合起始劑（C2)之比例較佳為20 : 1〜5 : 1。 光聚合起始劑（C1)之量（於含有光聚合起始劑（C2)之情形 時為（C1)與（C2)之共計量）相對於寡聚體與單體之共 計100重量份，較佳為0.01〜10重量份，更佳為〇5重量 份。 本發明之密封部形成用光硬化性樹脂組合物視需要，亦 可含有聚合抑制劑、光硬化促進劑、鏈轉移劑、光穩定劑 (紫外線吸收劑、自由基捕獲劑等）、抗氧化劑、難燃劑、 接著性提昇劑（矽烷偶合劑等）、顏料、染料等之各種添加 劑，較佳為含有聚合抑制劑、光穩定劑。尤其，由於含有 相較聚合起始劑更少量之聚合抑制劑，故可改善密封部形 成用光硬化性樹脂組合物之穩定性，亦可調整硬化後之樹 154270.doc •20· 201133058 脂層之分子量。 」乍為聚合抑制劑’可舉出對苯二酚系(2,5_二·叔丁基對 笨二盼等）、鄰苯二㈣（p何基兒㈣等）、請系、吩 噻嗪系、羥基甲苯系等之聚合抑制劑。 —作為光穩定劑’可舉出紫外線吸收劑（苯并三嗤系、二 苯曱酮系、水揚酸系等）、自由基捕獲劑（受阻胺系）等。 作為抗氧化劑，可舉出磷系、硫系之化合物。 各種添加劑之共計量相對於寡聚體與單體之共計 1 〇〇重量份’較佳為1〇重量份以下，更佳為5重量份以下。 (步驟（bl)) 於步驟（al)之後，對由未硬化之密封部所包圍之區域供 給液狀之樹脂層形成用硬化性樹脂組合物。 樹脂層形成用硬化性樹脂組合物之供給量預先設定為如 下之分量：使由未硬化之密封部、液晶面板及保護板所形 成之空間可藉由樹脂層形成用硬化性樹脂組合物而填充， 且使液晶面板與保護板之間成為特定之間隔（即，使樹脂 層成為特定之厚度）。此時，較佳為預先考慮藉由樹脂層 形成用硬化性樹脂組合物之硬化收縮而導致的體積減少。 因此，該分量較佳為使樹脂層形成用硬化性樹脂組合物之 厚度相較樹脂層之特定厚度少許厚的量。 作為供給方法，可舉出以下方法：將液晶面板平放，藉 由點膠機、擠壓式塗佈機等之供給機構而以點狀、線狀或 面狀進行供給。 树脂層形成用硬化性樹脂組合物之黏度較佳為〇 〇5〜5〇 154270.doc •21 · 201133058When the ratio of the Wt%° to the right monomer is 15% by weight or more, the sealing portion forming light M H > the hardenability of the material and the adhesion between the liquid crystal panel and the sealing portion are good. When the ratio of the monomer (8) is 50% by weight or less, the viscosity of the photocurable resin composition for sealing portion formation is easily adjusted to 154270.doc • 19 to 201133058 500 Pa*s or more. Examples of the photopolymerization initiator (Cl) include photopolymerization of acetophenone-based, condensed-based, benzoin or benzoin ether, phosphine oxide, diclofenac, thioindene, and lanthanide. The initiator is preferably an acetophenone-based, condensed or benzoin-based photopolymerization initiator. In the case of hardening by visible light having a short wavelength, from the viewpoint of the absorption wavelength region, a photopolymerization initiator which is an oxidized squama is more preferable. By using two or more kinds of photopolymerization initiators (C1) having different absorption wavelength ranges in combination, the hardening time can be further accelerated, and the surface hardenability of the sealing portion can be improved. Further, the following photopolymerization initiator (C2) may be used in combination in the range of curing of the photocurable resin composition for forming a resin layer which does not inhibit the portion adjacent to the uncured seal portion. In the case of the combination, the ratio of the polymerization initiator (c 1) to the polymerization initiator (C2) is preferably from 20:1 to 5:1 from the viewpoint of efficient and effective hardening. The amount of the photopolymerization initiator (C1) (co-measurement of (C1) and (C2) in the case of containing the photopolymerization initiator (C2)) relative to 100 parts by weight of the total of the oligomer and the monomer, It is preferably 0.01 to 10 parts by weight, more preferably 5 parts by weight. The photocurable resin composition for forming a seal portion of the present invention may contain a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, or the like, if necessary. Various additives such as a flame retardant, a further enhancer (such as a decane coupling agent), a pigment, and a dye preferably contain a polymerization inhibitor and a light stabilizer. In particular, since a polymerization inhibitor having a smaller amount than the polymerization initiator is contained, the stability of the photocurable resin composition for forming a seal portion can be improved, and the hardened tree can be adjusted. 154270.doc •20·201133058 Lipid layer The molecular weight.乍 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合A polymerization inhibitor such as a azine or a hydroxytoluene. The light stabilizers include ultraviolet absorbers (such as benzotriazine, benzophenone, and salicylic acid) and radical scavengers (hindered amines). Examples of the antioxidant include phosphorus-based and sulfur-based compounds. The total amount of the various additives is preferably 1 part by weight or less, more preferably 5 parts by weight or less based on the total amount of the oligomer and the monomer. (Step (b1)) After the step (al), a curable resin composition for forming a liquid resin layer is supplied to a region surrounded by the unhardened sealing portion. The supply amount of the curable resin composition for forming a resin layer is set in advance such that the space formed by the uncured seal portion, the liquid crystal panel, and the protective sheet can be filled with the curable resin composition for forming a resin layer. Further, a specific interval is formed between the liquid crystal panel and the protective plate (that is, the resin layer is made to have a specific thickness). In this case, it is preferable to reduce the volume reduction caused by the hardening shrinkage of the curable resin composition for forming a resin layer in advance. Therefore, the component is preferably such that the thickness of the curable resin composition for forming a resin layer is slightly thicker than the specific thickness of the resin layer. The supply method is a method in which the liquid crystal panel is laid flat and supplied in a dot shape, a line shape or a surface shape by a supply mechanism such as a dispenser or a squeeze coater. The viscosity of the curable resin composition for forming a resin layer is preferably 〇 〇 5 to 5 〇 154270.doc • 21 · 201133058
Pa.s，更佳為1〜20 Pa*s。若黏度為0.05 pa.s以上，則可抑 制下述單體（B1)之比例’從而樹脂層之物性下降受到抑 制。又’由於低沸點之成分變少，故對於下述減壓積層方 法較為適合。若黏度為50 Pa，s以下，則樹脂層中難以殘留 有氣泡。 樹脂層形成用硬化性樹脂組合物之黏度係於25。〇時使用 E型黏度計測定。 樹脂層形成用硬化性樹脂組合物既可為光硬化性樹脂組 合物’亦可為熱硬化性樹脂組合物。作為樹脂層形成用硬 化性樹脂組合物’自可於低溫下硬化、且硬化速度較快之 觀點而言，較佳為含有硬化性化合物及光聚合起始劑（C2) 之光硬化性樹脂組合物。又’硬化無需較高之溫度，故由 高溫導致之液晶面板損傷之虞亦較少。 作為樹脂層形成用光硬化性樹脂組合物，自容易將黏度 調整為上述範圍之觀點而言，作為上述硬化性化合物，較 佳為含有具有硬化性基且數量平均分子量為1〇〇〇〜1〇〇〇〇〇 之募聚體（A’）之1種以上、及具有硬化性基且分子量為 125〜600之單體（B，）之1種以上，並且單體（Β·)於寡聚體（Α·) 與單體（Β')之共計（1〇〇 wt0/〇)中之比例為40〜80 wt0/〇。 寡聚體（A')之數量平均分子量為1，〇〇〇〜1 〇〇,〇〇〇，較佳為 ΙΟ’ΟΟΟ〜70,000 ^若寡聚體（A1)之數量平均分子量為該範 圍’則容易將樹脂層形成用光硬化性樹脂組合物之黏度調 整為上述範圍。 寡聚體（A·)之數量平均分子量係藉由ope測定而獲之聚 I54270.doc •22- 201133058 苯乙烯換算之數量平均分子量。再者，於Gpc測定令，當 出現未反應之低分子量成分（單體等）之峰值之情形時將 该峰值除外而求出數量平均分子量。 作為寡聚體(A，)之硬化性基’可舉出加成聚合性之不飽 ♦基（丙婦酿氧基、甲基丙婦醯氧基等）、不飽和基與硫氮 基之組合等，自硬化速度較快之觀點及獲得透明性較高之Pa.s, more preferably 1 to 20 Pa*s. When the viscosity is 0.05 Pa.s or more, the ratio of the following monomer (B1) can be suppressed, and the deterioration of the physical properties of the resin layer can be suppressed. Further, since the component having a low boiling point is small, it is suitable for the following pressure reduction laminate method. When the viscosity is 50 Pa or less, bubbles are hard to remain in the resin layer. The viscosity of the curable resin composition for forming a resin layer is 25 . When measured, use an E-type viscometer. The curable resin composition for forming a resin layer may be a photocurable resin composition or a thermosetting resin composition. The curable resin composition for forming a resin layer is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator (C2) from the viewpoint of being hardenable at a low temperature and having a high curing rate. Things. Moreover, the hardening does not require a higher temperature, so the damage of the liquid crystal panel caused by the high temperature is less. The photocurable resin composition for forming a resin layer preferably contains a curable group and has a number average molecular weight of 1 〇〇〇 1 1 from the viewpoint of easily adjusting the viscosity to the above range. One or more kinds of the monomer (B') having a curable group and having a molecular weight of 125 to 600, and the monomer (Β·) is oligo The ratio of the total amount of the polymer (Α·) to the monomer (Β') (1〇〇wt0/〇) is 40 to 80 wt0/〇. The number average molecular weight of the oligomer (A') is 1, 〇〇〇~1 〇〇, 〇〇〇, preferably ΙΟ'ΟΟΟ~70,000 ^ If the number average molecular weight of the oligomer (A1) is in the range ' The viscosity of the resin layer-forming photocurable resin composition is easily adjusted to the above range. The number average molecular weight of the oligomer (A·) is obtained by the measurement of ope. I54270.doc • 22- 201133058 The number average molecular weight in terms of styrene. Further, in the case of the Gpc measurement order, when the peak of the unreacted low molecular weight component (monomer or the like) occurs, the peak value is excluded to obtain the number average molecular weight. Examples of the curable group of the oligomer (A) include an addition polymerizable unsaturated group (such as a glycosylated oxy group, a methyl acetophenoxy group, etc.), an unsaturated group and a sulfur-nitrogen group. Combination, etc., self-hardening speed and high transparency
樹脂層之觀點而言，軔# &A 叙佳為選自丙烯醯氧基及甲基丙烯醯 氧基中之基。X ’較高分子量之寡聚體⑽中之硬化性基 相較於較低分子量之單體（B,)中之硬化性基之反應性更容 易變低，：先增進單體(B，)之硬化而導致組合物全體之黏 ^遽^，k而存在有硬化反應成為不均質之虞。為了 獲得均質的樹脂層’更佳為將寡聚體(Α，)之硬化性基形成 =反應性較高之丙㈣氧基，將單體㈣之硬㈣基形成 為反應性較低之甲基氧基。 乍為寡聚體(Α )’自樹脂層形成用光硬化性樹脂組合物 更化眭樹月曰層之機械特性之觀點而言，較佳為每1分 子平均含有1.8〜4個硬化性基。 作為寡聚體（Α’）’可舉出具有氛醋鍵之氣醋寡聚體、聚 氧i化亞燒基多元醇之甲 聚（曱基）丙烯酸酯、聚酯多元醇之聚 ㈣酸S|等’自可根據氨賴之分子設計等而大幅 化後之樹脂之機械特性、與液晶面板或保護板之密 觀點而言’較佳為氨醋寡聚體。 關於寡聚體(A，)之比例，於寡聚體⑷與 (1〇° 154270.doc -23. 201133058 寡聚體（A’）之比例為20 wt%以上，則樹脂層之耐熱性成為 良好。若养聚體（A’）之比例為6〇 wt%以下，則樹脂層形成 用光硬化性樹脂組合物之硬化性、液晶面板或保護板與樹 脂層之密著性成為良好。 單體（6)之分子量為125〜6〇〇，較佳為14〇〜4〇〇。若單體 (B )之分子量為125以上，則藉由下述減壓積層方法而製造 顯示裝置時單體之揮發受到抑制。若單體（Βι)之分子量為 600以下，則液晶面板或保護板與樹脂層之密著性成為良 好0 作為單體（B，）之硬化性基，可舉出加成聚合性之不飽和 基（丙烯酿氧基、甲基丙烯酿氧基等）、不飽和基與硫氮基 之組合等’自硬化速度較快之觀點及獲得透明性較高之樹 月曰層之觀點而5，較佳為選自丙烯醯氧基及甲基丙烯醯氧 基中之基。又，較低分子量之單體（Β·)中之硬化性基相較 於較高分子量之寡聚體（Α.)甲之硬化性基之反應性更容易 隻同故先增進單體（Β’）之硬化而導致組合物全體之黏性 ^遽變高，從而存在有硬化反應成為不均f之虞。為了獲 得均質的樹脂層，更佳為將單體(B，)之硬化性基形成為反 應性較低之甲基丙烯醯氧基，將寡聚體（A,)之硬化性基形 成為反應性較高之丙稀醯氧基。 作為單體(B’)，自樹脂層形成用光硬化性樹脂組合物之 硬化性、樹脂層之機械特性之觀點而言，較佳為每1分子 含有1〜3個硬化性基。 作為單體（B’）’自液晶面板或保護板與樹脂層之密著性 154270.doc •24- 201133058 之觀點而言，較佳為包含具有羥基之單體（B3)。 作為具有經基之單體（Β3)，可舉出與密封部形成用光硬 化性樹脂組合物中之單體（Β3)為相同者，特佳為甲基丙稀 酸2-羥丁酯。 • 關於單體(Β3)之比例’於募聚體(Α’)與單體(Β，)之共計 (100 wt%)中，較佳為15〜7〇 wt% ’更佳為2〇〜5〇 若 單體（B3)之比例為15 wt%以上，則樹脂層形成用光硬化性 树月曰組口物之硬化性、液晶面板或保護板與樹脂層之密著 性成為良好。 關於單體（B’），自樹脂層之機械特性之觀點而言，較佳 為包含下述單體（B4)。 單體（B4):具有碳數8〜22之烷基之烷基甲基丙烯酸酯。 作為單體（B4) ’可舉出甲基丙稀酸正十二烧基醋、甲基 丙烯I正十八烷基酯、曱基丙烯酸正二十二烷基酯等，較 佳為甲基丙烯酸正十二烷基酯、甲基丙烯酸正十八烷基 醋。 關於單體（B4)之比例，於寡聚體（A，）與單體（B,)之共計 (100 wt%)中，較佳為5〜5〇 wt%，更佳為15〜4〇糾〇/。。若單 體（B4)之比例為5 wt%以上，則樹脂層之柔軟性成為良 好。 光水&起始劑（C2)係具有存在於相較上述光聚合起始劑 (ci)之吸收波長域（λ1)更長波長側之吸收波長域（λ2)者。 光聚合起始劑（C2)既可為僅具有吸收波長域（λ2)者，亦可 為具有與吸收波長域（λΐ)重複之吸收波長域（λ1，）及吸收波 154270.doc -25- 201133058 長域（λ2)者。 作為光聚合起始劑(C2)’可舉出苯乙酮系、縮酮系、安 息香或安息香喊系、氧化鱗系、二苯甲酮系、硫雜蒽_ 系、醌系等之光聚合起始劑，較佳為氧化膦系、硫雜蒽輞 系之光聚合起始劑’於光聚合反應後抑制著色之方面而言 特佳為氧化膦系。 ° 作為光聚合起始劑（C2)，冑當選擇該等光聚合起始劑中 相對於光聚合起始劑（C1)而具有„及收波長域⑽而使用。 關於光聚合起始劑（C2)之量，相對於寡聚體（Αι)與單體 (Β，）之共計100重量份，較佳為〇〇1〜1〇重量份，更佳為 〇. 1〜2.5重量份。 樹脂層形成用光硬化性樹脂組合物視需要，亦可含有聚 合抑制劑、光硬化促進劑、鏈轉移劑、光穩定劑(紫外線 吸收劑、自由基捕獲劑等)、抗氧化劑、難燃劑、接著性 提昇劑（石夕烷偶合劑等）、顏料、染料等之各種添加劑，較 佳為含有聚合抑制劑、光穩定劑。尤其，由於含有相較聚 合起始劑更少量之聚合抑制劑，故可改善樹脂層形成用光 硬化性樹脂組合物之穩定性，亦可調整硬化後之樹脂層之 分子量。 (步驟（cl)) 於步驟（bl)之後，將被供給有樹脂層形成用硬化性樹脂 組合物之液晶面板放入減壓裝置中，於減壓裝置内之固^ 支持盤上，以使樹脂層形成用硬化性樹脂組合物朝向上方 之方式平放液晶面板。 154270.doc -26- 201133058 在設置於減壓裝置内之上部之於上下方向可移動之移動 支持機構上’以使第1偏光機構朝向下方之方式安裝保護 板。 保護板被保持於液晶面板之上方且與樹脂層形成用硬化 性樹脂組合物不接觸的位置上。即，使液晶面板之表面之 樹月曰層形成用硬化性樹脂組合物與保護板不接觸而相對 向0 又，將液晶面板之安裝位置及保護板之安裝位置調整成 使第1偏光機構及第2偏光機構之偏光軸所成之角度符合液 晶單元之設計。例如’於非通電時液晶單元中之液晶相對 於液晶單元之透明面材大致成垂直方向的液晶單元中，第 1偏光機構及第2偏光機構之偏光軸所成之角度約為9〇。。 再者，亦可將於上下方向可移動之移動支持機構設置於 減壓裝置内之下部，於移動支持機構上放置被供給有樹脂 層形成用硬化性樹脂組合物之液晶面板。於該情形時，將 保護板女裝於設置於減壓裝置内之上部之固定支持盤上， 使液晶面板與保護板相對向。又，亦可由設置於減壓裝置 之上下之移動支持機構來支持液晶面板及保護板之兩 方。 將液晶面板及保護板配置於特定之位置後，將減壓裝置 之内部減壓而成為特定之減壓環境。若可能，亦可於減壓 刼作中或成為特定之減壓環境後，於減壓裝置内使液晶面 板及保護板位於特定之位置。 減壓裝置之内部成為特定之減壓環境後，將由移動支持 154270.doc •27· 201133058 機構而支持之保護板向下方移動，於液晶面板之表面之樹 脂層形成用硬化性樹脂組合物上疊合第2面材。 藉由疊合而將樹脂層形成用硬化性樹脂組合物密封於由 液晶面板之表面、保護板之表面、及未硬化之密封部所包 圍之空間内。 於疊合時，由於保護板之自重、來自移動支持機構之擠 屋4 ’而將樹脂層形成用硬化性樹脂組合物壓散開，於上 述空間内充滿樹脂層形成用光硬化性樹脂組合物而形成未 硬化之樹脂層。其後，於步驟中曝露於較高壓力環境 時’成為氣泡較少或無氣泡之未硬化之樹脂層。 疊合時之減壓環境為100 Pa以下，較佳為1〇 Pa以上。若 減壓環境為過度低壓，則存在有對樹脂層形成用硬化性樹 脂組合物中所含之各成分（硬化性化合物、光聚合起始 劑、聚合抑制劑、光穩定劑等）造成惡劣影響之虞。例 如’若減壓環境為過度低Μ，則存在有各成分氣化之虞， 又，為了提供減壓環境而需花費時間。減壓環境之壓力更 佳為15〜40 Pa。 自液晶面板與保護板疊合之時間點起直至解除減壓環 為止之時間無特別限定’既可於樹脂層形成用硬化性樹 組合物密封後，立即解除減壓環境，亦可於樹脂層形成 硬化性樹脂组合物密封後，將減壓狀態維持特定時間。由 於將減壓狀態維持特定時間，故樹脂層形成用硬化性樹脂 組合物於密閉空間内流動而使液晶面板與保護板之間的間 隔成為均句’即便提高環境壓力亦容易維持密封狀態。減 154270.doc -28- 201133058 壓狀態之維持時間亦可為數小時以上之較長時間，但自生 產效率之觀點而言，較佳為i小時以内，更佳為1〇分鐘以 内。 於本發明之製造方法中，塗佈黏度較高之密封部形成用 硬化性樹脂組合物而形成未硬化之密封部之情形時可將 步驟（C)所獲得之積層物中之未硬化之樹脂層之厚度形成為 3 0 μιη〜3 mm之較厚的厚度。 (步驟（dl)) 於步驟（c 1)中解除減壓環境後，將積層物放置於環境壓 力為50 kPa以上之壓力環境下。 將積層物放置於50 kPa以上之壓力環境下之後，藉由上 升之壓力而使其朝液晶面板與保護板密著之方向受到擠 壓，故而若積層物内之密閉空間中存在有氣泡，則氣泡中 會流動有未硬化之樹脂層，從而整個密閉空間藉由未硬化 之樹脂層而被均勻填充。 壓力環境通常為80 k〜120 kPa»壓力環境既可為大氣壓 環境，亦可為相較其更高的壓力。無需特別之設備即可進 行未硬化之樹脂層之硬化等之操作，因此大氣壓環境為最 佳。 自將積層物放置於50 kPa以上之壓力環境下之時間點起 直至未硬化之樹脂層開始硬化為止的時間（以下，記作高 壓保持時間)並無特別限定。當於大氣壓環境下執行將： 層物自減«置中取出並移動至硬化裝置而開始硬化為止 的製程之情形時，該製程所需之時間成為高壓保持時間。 154270.doc -29- 201133058 因此，在放置於大氣壓環境下之時間點於積層物之密閉空 間内已不存在氣泡之情形時、或於該製程期間氣泡消失: 情形時，可使未硬化之樹脂層立即硬化。於直至氣泡消失 為止需要花費時間之情形時，將積層物保持於5〇 kb以上 之α力％梃下直至氣泡消失為止。又，即便高壓保持時間 變長，通常亦不會發生故障，因此自製程上之其他必要性 考慮亦可延m㈣時間。高壓保持時間亦可^天以 上之較長時間，但自生產效率之兹 、 ㈢玍座双手之靦點而言，較佳為6小時 以内’更佳為1小時以内，$而自提高生產效率之觀點而 言，特佳為10分以内。 其次’藉由使未硬化之樹脂層硬化而形成有將液晶面板 與保護板加以接合之樹脂層，製造液晶顯示裝置。此時， 未硬化之密封部既可與未硬化之樹脂層同時硬化，亦可於 未硬化之樹脂層硬化之前預先使未硬化之密封部硬化。 於未硬化之樹脂層及未硬化之密封部包含光硬化性組合 Μ㈣㈣Μ使其硬化8例如’自光源（紫外線 燈、高麗水銀燈、UV-LED(Ultravi〇let Hght emitting diode，紫外發光二極體）等）照射紫外線或短波長之可見 光’而使光硬化性樹脂組合物硬化。 此時’於積層物之液晶面板及保護板中，自具有透光性 之保護板之側對未硬化之樹脂層照射光，又，自積層物之 側方對由遮光印刷部及液晶面板所夾持之未硬化之密封部 及未硬化之樹脂層照射光。 液晶面板及保s隻板中’液晶面板多為於不動作之狀態下 154270.doc •30· 201133058 不具有透光性者，因此自保護板之側通過由遮光印刷部包 圍之透光部而照射光。 ,若於保6蔓板之周緣部言免置有遮光印刷冑，且於由遮 光印刷部與液晶面板所夾持之區域中存在未硬化之密封部 及未硬化之樹脂層，則僅由來自保護板之透光部之光無法 充刀硬化。因此，自積層物之側方照射光。 作為光，較佳為紫外線或45 〇 nm以下之可見光。尤其， 於保遵板上設置有抗反射層，且抗反射層或者形成有抗反 射：之透明樹脂膜或上述抗反射膜與透明面材間所設置之 黏著層等未穿透紫外線之情形時，必需藉由可見光而進行 硬化。 作為來自積層物之側方之光照射之光源，亦可使用來自 保遵板之側之光照射所使用之光源，❻自適合於對光源之 配置空間及特定部錢行效率良好的光照射之觀點而言， 使用1外線或發出450⑽以下之可見光之LED為較佳。 、光係既可於來自㈣板之側之照射之後自積層物之側方 進行照射，亦可於來自積層物之側方之照射之後自保護板 ^側進行照射，亦可自保護板之側及積層物之側方同時進 行照射。A 了進一步促進遮光印刷部中之未硬化之密封部 及未硬化之樹脂層的硬化，較佳為先自積層物之侧方進行 照射’再與積層物之側方同時地自保護板之側進行昭射。 於本發明之製造方法中，由於下述之理由，較佳為：作 為樹知層形成用光硬化性樹脂組合物+所含之光聚合起始 劑（C2)，使用具有存在於相較密封部形成用光硬化性樹脂 154270.doc •31 - 201133058 組合物中所含之光聚合起始劑（Cl)之吸收波長域（λΐ)更長 波長側之吸收波長域（λ2)的光聚合起始劑，而且，作為自 積層物之側方照射之光，使用包含吸收波長域（λΐ)内之波 長之光及吸收波長域（λ2)内之波長之光的光。 理由： 由遮光印刷部及液晶面板所夾持之未硬化之密封部之寬 度為0.5〜2 mm、且由遮光印刷部及液晶面板所夾持之未硬 化之樹脂層之寬度為1〜1 〇 mm的情形，即未硬化之樹脂層 之厚度大於0.03〜2 mm的情形較多。因此，自側方照射之 光難以到達遮光印刷部與透光部之邊界部分之未硬化的樹 脂層。 於該狀況下’作為未硬化之密封部之光聚合起始劑及未 硬化之樹脂層之光聚合起始劑’若使用具有完全相同吸收 波長域者’則自側方照射之光之大部分會被未硬化之密封 部之光聚合起始劑吸收，硬化所必要之光並未充分到達未 硬化之樹脂層，從而無法充分進行硬化。若遮光印刷部之 未硬化之樹脂層之硬化不充分，則於遮光印刷部與透光部 之邊界之部分上，硬化不充分之樹脂層形成用光硬化性樹 脂組合物或未硬化之樹脂層形成用光硬化性樹脂組合物會 隨時間推移而擴散，由於透光部之充分硬化後之樹脂層、 與硬化不充分之部分之折射率的略微差異，故於遮光印刷 部與透光部之邊界之部分，穿透光會產生光學畸變，從而 有晝質下降之虞。 另一方面’作為未硬化之樹脂層之光聚合起始劑， 154270.doc •32- 201133058 使用具有存在於相較未硬化之密封部之光聚合起始劑（c j) 之吸收波長域（λΐ)更長波長側之吸收波長域（λ2)的光聚合 起始劑（C2) ’而且’作為自積層物之側方照射之光，使用 吸收波長域（九1)内之波長之光及吸收波長域（人2)内之波長 之光之兩方。因此，未被未硬化之密封部之光聚合起始劑 (C1)所吸收之吸收波長域（λ2)内之波長的光會充分到達由 遮光印刷部及液晶面板所夾持之未硬化之樹脂層，藉由具 有吸收波長域（λ2)之光聚合起始劑（C2)可充分進行未硬化 之樹脂層之硬化。 此時’既可同時照射來自具有至少一部分與吸收波長域 (λΐ)重複之發光波長域之光源的光、及具有至少一部分與 吸收波長域（λ2)重複之發光波長域之光源的光，亦可分別 照射。又，亦可照射來自具有至少一部分與吸收波長域 (λΐ)及吸收波長域（λ2)之兩方重複之發光波長域之光源的 光。 [具體例] 以下’以方法（(X)之情形為例’使用圖式來具體說明圖1 之液晶顯示裝置之製造方法。 (步驟（al)) 如圖3及圖4所示，沿液晶面板2〇之與第2偏光機構26側 為相反側之表面之周緣部，藉由點膠機（圖示略）等塗佈密 封部形成用光硬化性樹脂組合物而形成未硬化之密封部。 於液晶面板20之外周部，設置有傳達用以使液晶面板2〇 動作之電氣信號之可撓性印刷配線板24等的配線構件。於 154270.doc -33- 201133058 本發明之製造方法中，於保持液晶面板2〇及保護板10時會 使配線構件之配置容易’故較佳為將液晶面板2〇配置於下 側。 (步驟（bl)) 其次’如圖5及圖6所示’對由液晶面板20之未硬化之密 封部52所包圍之矩形狀之區域42供給樹脂層形成用光硬化 性樹脂組合物44。樹脂層形成用光硬化性樹脂組合物44之 供給量預先設定為如下之分量：使由未硬化之密封部5 2、 液晶面板20及保護板1 〇(參照圖7)所密閉之空間可藉由樹脂 層形成用光硬化性樹脂組合物44而填充。 樹脂層形成用光硬化性樹脂組合物44之供給如圖5及圖6 所示，藉由以下方法而實施：將液晶面板2〇平放於下定盤 66上’藉由於水平方向移動之點膠機6〇而將樹脂層形成用 光硬化性樹脂組合物44以線狀、帶狀或點狀進行供給。 點膠機60係藉由包含一對進給螺桿62及與進給螺桿62正 交之進給螺桿64之公知的水平移動機構而於區域42之整個 範圍内可水平移動。再者’亦可代替點膠機6〇而使用擠壓 式塗佈機。 (步驟（cl)) 其次，如圖7所示，將液晶面板20與保護板1〇搬入至減 壓裝置70内。於減壓裝置70内之上部，配置有具有複數個 吸附墊72之上定盤74 ’於下部設置有下定盤76。上定盤74 藉由氣缸78而於上下方向上可移動。 保護板10中，將第1偏光機構16朝下安裝於吸附塾72 154270.doc • 34· 201133058 上。液晶面板20中’將樹脂層形成用光硬化性樹脂組合物 44朝上固定於下定盤76上。 其次，藉由真空泵80而吸引減壓裝置7〇内之空氣。當減 壓裝置70内之環境壓力到達例如〗5〜4〇 pa之減壓環境之 後，於藉由上定盤74之吸附墊72而吸附保持有保護板丨〇之 狀態下，使氣缸78朝向於下方等待之液晶面板2〇而動作並 下降。然後，將液晶面板2〇與保護板〗〇介隔未硬化之密封 部52而疊合，由保s蒦板1〇、液晶面板及未硬化之密封部 52而構成使包含樹脂層形成用光硬化性樹脂組合物之未 硬化之樹脂層得以密封的積層物，並於減壓環境下將該積 層物保持特定時間。 再者’液晶面板20相對於下定盤76之安裝位置、吸附墊 72之個數、保護板丨〇相對於上定盤74之安裝位置等係根據 液晶面板20及保護板1〇之尺寸、形狀等而適當調整。又， 將液晶面板20之安裝位置及保護板1〇之安裝位置調整成使 第1偏光機構16及第2偏光機構26之偏光軸所成之角度符合 液晶單元之設計。例如，於非通電時液晶單元中之液晶相 對於液晶單元之透明面材大致成垂直方向之液晶單元中， 第1偏光機構及第2偏光機構之偏光軸所成之角度約為 90°。此時，使用靜電吸盤作為吸附墊，採用曰本專利特 願2008-206124所附之說明書（併入至本說明書）中記載之靜 電吸盤保持方法，藉此可將玻璃基板穩定地保持於減壓環 境下。 (步驟（dl)) 】54270.doc •35- 201133058 其次，使減壓裝置70之内部成為例如大氣壓後，自減壓 裝置70中取出積層物。將積層物放置於大氣壓環境下之 後，積層物之液晶面板20之側之表面與保護板1 〇之侧之表 面藉由大氣壓而受到擠壓，密閉空間内之樹脂層形成用光 硬化性樹脂組合物44於液晶面板20與保護板10上被加壓。 由於該壓力而使密閉空間内之未硬化之樹脂層流動，整個 密閉空間藉由未硬化之樹脂層而被均勻填充。即便上述整 個密閉空間藉由未硬化之樹脂層而填充之後，只要有微小 的位置調整便可使保護板10之位置相對於液晶面板20而移 動，藉此亦可調整第1偏光機構16及第2偏光機構26之偏光 軸所成之角度。 其次’如圖8所示’自積層物之側方對由遮光印刷部14 及液晶面板20所夾持之未硬化之密封部52及未硬化之樹脂 層46照射光（紫外線）至積層物之全周，且自保護板1〇之側 通過透光部1 8而對未硬化之樹脂層46照射光（紫外線），使 積層物内部之未硬化之密封部52及未硬化之樹脂層46硬 化，藉此製造液晶顯示裝置1。 以上’以方法（α)之情形為例具體說明了本發明之液晶 顯示裝置之製造方法，對於方法（β)之情形亦可以相同之方 法製造液晶顯示裝置。 (作用效果） 以上說明之本發明之液晶顯示裝置之製造方法中，將2 個偏光機構中位於保護板側之偏光機構預先貼附於保護板 而非液晶面板上，故可於剛要將液晶面板與保護板疊合之 154270.doc -36- 201133058 前’使液晶面板與保護板相對移動，對2個偏光機構之偏 光軸進行微調整。因此，可將2個偏光機構之偏光軸所成 之較佳角度容易對準。 又’根據以上說明之本發明之液晶顯示裝置之製造方 法，可不使樹脂層中產生氣泡地製造較大面積之液晶顯示 裝置。假設即便於減壓下於密封之未硬化之樹脂層中殘存 有氣泡，亦會於硬化前之較高壓力環境下對已密封之未硬 化之樹脂層施加該壓力，從而該氣泡之體積減少，氣泡容 易消失。例如，認為於1〇〇 Pa下密封之未硬化之樹脂層中 之氣泡中之氣體的體積為丨00 kpa下的i/iooo。氣體亦會溶 解於未硬化之樹脂層中，故微小體積之氣泡中之氣體會快 速溶解於未硬化之樹脂層中而消失。 又，即便對密封後之未硬化之樹脂層施加大氣壓等之壓 力，由於液狀之樹脂層形成用硬化性樹脂組合物為流動性 之組合物，故該壓力均勻分佈於液晶面板之表面，與未硬 化之樹脂層相接觸之液晶面板之表面之一部分並未被施加 有更夕之應力，故液晶面板損傷之虞較少。 又，因樹脂層形成用硬化性樹脂組合物之硬化而產生的 樹脂層與液晶面板及保護板之界面接著力高於因熱熔著性 樹脂之熔著而產生的界面接著力。而1，對流動性之樹脂 層形成用硬化性樹脂組合物進行加壓而使其密著於液晶面 板及保護板之表面，並於該狀態下使其硬化，故可獲得更 间的界面接著力，並且可取得相對於液晶面板及保護板之 表面之均勻的接$，局部界面接著力變低之情形較少。因 154270.doc •37· 201133058 此’於樹脂層之表面產生剝離之虞較低，而且水分或腐蝕 性氣體自界面接著力不充分之部分進入之虞亦較少。 又，與於液晶面板及保護板之間之狭窄且面積大的空間 中注入流動性之樹脂層形成用硬化性樹脂組合物的方法 (注入法）相比後，氣泡之產生較少且可於短時間内填充樹 脂層形成用硬化性樹脂組合物。而且，樹脂層形成用硬化 性樹脂組合物之黏度之制約較少，可容易填充高黏度之樹 脂層形成用硬化性樹脂組合物。因此，可使用能提高樹脂 層之強度的含有較高分子量之硬化性化合物之高黏度的樹 脂層形成用硬化性樹脂組合物。 又’作為未硬化之樹脂層之光聚合起始劑（C2)，使用具 有存在於相較未硬化之密封部之光聚合起始劑（c丨）之吸收 波長域（λΐ)更長波長側之吸收波長域（λ2)的光聚合起始劑 (C2) ’而且’作為自積層物之側方照射之光，使用吸收波 長域（λ 1)内之波長之光及吸收波長域（人2)内之波長之光之 兩方’因此未被未硬化之密封部之光聚合起始劑（c丨）所吸 收之吸收波長域（λ2)内之波長的光會充分到達由遮光印刷 部與液晶面板所夾持之未硬化之樹脂層，藉由具有吸收波 長域（λ2)之光聚合起始劑（C2)，可充分進行未硬化之樹脂 層之硬化。 實施例 以下，表示為了確認本發明之有效性而實施之例。例1 為實施例，例2為比較例。 (數量平均分子量） 154270.doc •38· 201133058 寡聚體之數量平均分子量係使用GPC裝置（t〇s〇h公司 製，HLC-8020)而求出。 (黏度） 光硬化性樹脂組合物之黏度係使用E型黏度計（東機產業 公司製，RE-85U)而測定。 (霧度值） 霧度值係使用東洋精機製作所製之Haze guard π，並藉 由以ASTMD1 003為基準之測定而求出。 [例1] (液晶面板） 準備液晶面板A，其係於非通電時將液晶定向於相對於 液晶單元之透明面材而大致垂直之方向上，於長度712 麵、寬度412 _、厚度約2咖之液日日日單元之僅—面上， 以使偏光轴與液晶單元之短邊平行之方式而黏貼吸收型偏 光板圖像顯不ϋ域之長度為696 _，寬度為别以爪。 (保護板） :長度794 mm、寬度479 mm、厚度3爪爪之鈉鈣玻璃板 之方之表面之周緣部，以使透光部成為長度_麵、寬 之方式藉由含有黑色顏料之陶瓷印刷而形成額緣 狀之遮光印刷部。 、以使PVA膜中定向有峨之膜狀之吸收型偏光子之 偏光軸與保護板之具 r 長邊平订’且與形成有鈉鈣玻璃板之遮 光印刷部之側$车 '^面相接觸的方式，由鈉鈣玻璃板與TAC 膜夾持吸收型偏光子，並將該等貼合。 154270.doc -39- 201133058 其次，於鈉鈣玻璃板之與吸收型偏光子側為相反側之整 個表面上，於附保護膜之狀態下黏貼抗反射膜（日本油脂 公司製’ ReaLookx4001)，製作保護板b。 (密封部形成用光硬化性樹脂組合物） 將分子末端由環氧乙烧改質後之2官能聚丙二醇（由經基 價計算出的數量平均分子量：4000)、與二異氰酸己二酯 以6比7之莫耳比加以混合，其次以異冰片基丙烯酸酯（大 阪有機化學工業公司製，IBXA)稀釋後，於存在有錫化合 物之觸媒之情形下以70eC進行反應而獲得之預聚物中，以 約1比2之莫耳比添加2-丙烯酸羥乙酯並以7〇°c進行反應， 藉此獲得30 wt%之由異冰片基丙烯酸酯稀釋而成之氨酯丙 烯酸酯寡聚體（以下，記作UC-1)溶液。UC-1之硬化性基數 為2 ’數量平均分子量約為55〇〇〇。UC-1溶液於60°C時之黏 度約 580 Pa，s。 將UC-1溶液90重量份及甲基丙烯酸2_羥丁酯（共榮社化 學公司製，Lightester HOB)1〇重量份加以均勻混合而獲得 混合物。將該混合物1〇〇重量份、卜羥基_環己基苯基酮（光From the viewpoint of the resin layer, 轫# &A is preferably a group selected from the group consisting of an acryloxy group and a methacryloxy group. The reactivity of the hardening group in the X' higher molecular weight oligomer (10) is lower than that of the hardening group in the lower molecular weight monomer (B,): first, the monomer (B,) is promoted. The hardening causes the entire composition to be viscous, and there is a tendency for the hardening reaction to become inhomogeneous. In order to obtain a homogeneous resin layer, it is more preferable to form a hardening group of the oligomer (Α,) into a highly reactive C (tetra)oxy group, and to form a hard (tetra) group of the monomer (4) into a less reactive group. Baseoxy. From the viewpoint of improving the mechanical properties of the eucalyptus layer, it is preferable to contain an average of 1.8 to 4 curable groups per one molecule from the viewpoint of improving the mechanical properties of the eucalyptus layer. Examples of the oligomer (Α')' include a vinegar oligomer having an acetal bond, a poly(i-alkylene) acrylate of a polyoxyalkylene-based polyol, and a poly(tetra) acid of a polyester polyol. S|etc. 'preferably, the mechanical properties of the resin which can be enlarged according to the molecular design of ammonia, and the viewpoint of the liquid crystal panel or the protective sheet are preferably a vinegar oligomer. Regarding the ratio of the oligomer (A,), when the ratio of the oligomer (4) to (1〇° 154270.doc -23. 201133058 oligomer (A') is 20 wt% or more, the heat resistance of the resin layer becomes When the ratio of the polymer (A') is 6 〇wt% or less, the curability of the resin layer-forming photocurable resin composition and the adhesion between the liquid crystal panel or the protective sheet and the resin layer are good. The molecular weight of the body (6) is 125 to 6 Å, preferably 14 Å to 4 Å. When the molecular weight of the monomer (B) is 125 or more, the display device is manufactured by the following pressure reduction lamination method. When the molecular weight of the monomer (Βι) is 600 or less, the adhesion between the liquid crystal panel or the protective sheet and the resin layer is good. 0 The curable group of the monomer (B) is exemplified. a polymerizable unsaturated group (acrylic oxy group, methacryloxy group, etc.), a combination of an unsaturated group and a sulphur nitrogen group, etc., a viewpoint of a faster self-hardening rate and a tree having a higher transparency. From the viewpoint of the layer, 5 is preferably a group selected from the group consisting of an acryloxy group and a methacryloxy group. Further, a lower score The reactivity of the hardening group in the monomer (Β·) is easier to react with the hardening group of the higher molecular weight oligomer (Α.), and only the monomer (Β') is promoted first. The hardening causes the viscosity of the entire composition to become high, so that the hardening reaction becomes uneven. In order to obtain a homogeneous resin layer, it is more preferable to form a hardening group of the monomer (B,) into a reaction. A methacryloxy group having a low degree of methacryloxy group, and a curable group of the oligomer (A) is formed into a highly reactive acryloyloxy group. As a monomer (B'), light is formed from the resin layer. From the viewpoint of the curability of the curable resin composition and the mechanical properties of the resin layer, it is preferred to contain 1 to 3 curable groups per molecule. As the monomer (B')' from the liquid crystal panel or the protective sheet and the resin From the viewpoint of the adhesion of the layer 154270.doc • 24-201133058, it is preferred to include a monomer having a hydroxyl group (B3). As a monomer having a radical (Β3), light for forming a portion with a sealing portion is exemplified. The monomer (Β3) in the curable resin composition is the same, particularly preferably 2-hydroxybutyl methacrylate. The ratio of (Β3) is preferably 15 to 7〇wt% in the total amount (100 wt%) of the polymer (Α') and the monomer (Β), and is preferably 2〇~5〇 When the ratio of the body (B3) is 15% by weight or more, the curability of the photocurable sapphire component for resin layer formation, and the adhesion between the liquid crystal panel or the protective sheet and the resin layer are good. ') From the viewpoint of mechanical properties of the resin layer, it is preferred to contain the following monomer (B4): Monomer (B4): an alkyl methacrylate having an alkyl group having 8 to 22 carbon atoms. The monomer (B4) 'is methacrylic acid n-dodecyl vinegar, methacrylic acid I n-octadecyl ester, n-docosyl decyl acrylate, etc., preferably methacrylic acid N-dodecyl ester, n-octadecyl methacrylate. The ratio of the monomer (B4) is preferably 5 to 5 % by weight, more preferably 15 to 4 %, based on the total of the oligomer (A,) and the monomer (B,) (100 wt%). Correction /. . When the ratio of the monomer (B4) is 5% by weight or more, the flexibility of the resin layer is good. The photo-water & starter (C2) has an absorption wavelength range (λ2) which is present on the longer wavelength side than the absorption wavelength range (λ1) of the above photopolymerization initiator (ci). The photopolymerization initiator (C2) may be either an absorption wavelength domain (λ2) alone or an absorption wavelength domain (λ1,) and an absorption wave 154270.doc -25- which are repeated with the absorption wavelength domain (λΐ). 201133058 Long-term (λ2). Examples of the photopolymerization initiator (C2) include photopolymerization of an acetophenone-based, ketal-based, benzoin or benzoin-based system, an oxidized squama system, a benzophenone-based system, a thioxanthene-based system, and an anthraquinone system. The initiator, preferably a phosphine oxide-based or thiastene-based photopolymerization initiator, is particularly preferably a phosphine oxide system in terms of suppressing coloration after photopolymerization. ° As a photopolymerization initiator (C2), it is used in the photopolymerization initiator to have a wavelength range (10) with respect to the photopolymerization initiator (C1). The amount of C2) is preferably 〇〇1 to 1 〇 by weight, more preferably 〇. 1 to 2.5 parts by weight, based on 100 parts by weight of the total of the oligomer (Αι) and the monomer (Β). The layer-forming photocurable resin composition may contain a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and, if necessary, Further, various additives such as a color enhancer (such as an oxetane coupling agent), a pigment, and a dye preferably contain a polymerization inhibitor and a light stabilizer. In particular, since a polymerization inhibitor having a smaller amount than the polymerization initiator is contained, Therefore, the stability of the photocurable resin composition for forming a resin layer can be improved, and the molecular weight of the resin layer after curing can be adjusted. (Step (cl)) After the step (b1), the resin layer is hardened. The liquid crystal panel of the resin composition is placed under reduced pressure The liquid crystal panel is placed flat on the fixing plate in the pressure reducing device so that the resin layer forming curable resin composition faces upward. 154270.doc -26- 201133058 is disposed in the pressure reducing device In the movement support mechanism that is movable in the up-and-down direction, the protective plate is attached so that the first polarizing means faces downward. The protective plate is held above the liquid crystal panel and does not contact the curable resin composition for forming a resin layer. In the position of the liquid crystal panel, the curable resin composition for forming a layer of the liquid crystal panel and the protective sheet are not in contact with each other, and the mounting position of the liquid crystal panel and the mounting position of the protective sheet are adjusted to be the first. The angle formed by the polarizing axis of the polarizing mechanism and the second polarizing mechanism conforms to the design of the liquid crystal cell. For example, in the liquid crystal cell in which the liquid crystal in the liquid crystal cell is substantially perpendicular to the transparent surface material of the liquid crystal cell in the case of non-energization, the first The angle between the polarizing mechanism of the polarizing mechanism and the second polarizing mechanism is about 9 〇. Further, the moving support mechanism that can be moved in the up and down direction can be set. A liquid crystal panel to which a curable resin composition for forming a resin layer is supplied is placed on a lower portion of the inside of the decompression device, and in this case, the protective plate is attached to the upper portion of the decompression device. Supporting the disk, the liquid crystal panel and the protection plate are opposed to each other. Further, the liquid crystal panel and the protection plate can be supported by the mobile support mechanism disposed above and below the pressure reducing device. The liquid crystal panel and the protection plate are disposed at a specific position. After that, the inside of the decompression device is decompressed to a specific decompression environment. If possible, the liquid crystal panel and the protective plate may be placed in the decompression device after decompression or a specific decompression environment. When the inside of the decompression device is a specific decompression environment, the protective sheet supported by the mobile support 154270.doc •27·201133058 mechanism is moved downward, and the resin layer on the surface of the liquid crystal panel is formed with a curable resin. A second facestock is superposed on the composition. The resin layer-forming curable resin composition is sealed in a space surrounded by the surface of the liquid crystal panel, the surface of the protective sheet, and the unhardened sealing portion by lamination. At the time of the superposition, the resin layer forming curable resin composition is dispersed by the self-weight of the protective sheet and the squeezing chamber 4' of the mobile supporting mechanism, and the resin layer-forming photocurable resin composition is filled in the space. An uncured resin layer is formed. Thereafter, when exposed to a higher pressure environment in the step, it becomes an uncured resin layer having less or no bubbles. The pressure reducing environment at the time of lamination is 100 Pa or less, preferably 1 〇 Pa or more. When the pressure-reducing environment is excessively low, the components (curing compound, photopolymerization initiator, polymerization inhibitor, light stabilizer, etc.) contained in the curable resin composition for forming a resin layer may be adversely affected. After that. For example, if the decompression environment is excessively low, there is a possibility that the components are vaporized, and it takes time to provide a reduced pressure environment. The pressure in the reduced pressure environment is preferably 15 to 40 Pa. The time from the time when the liquid crystal panel and the protective sheet are overlapped until the pressure-reduction ring is released is not particularly limited. The pressure-reducing environment can be released immediately after the resin layer forming curable tree composition is sealed, or the resin layer can be removed. After the formation of the curable resin composition is sealed, the reduced pressure state is maintained for a specific period of time. When the pressure-reduced state is maintained for a specific period of time, the resin layer-forming curable resin composition flows in the sealed space, and the interval between the liquid crystal panel and the protective sheet is made uniform. It is easy to maintain the sealed state even if the environmental pressure is increased. Subtraction 154270.doc -28- 201133058 The holding time of the pressure state may be a long time of several hours or more, but from the viewpoint of productivity, it is preferably within one hour, more preferably within one minute. In the production method of the present invention, when the curable resin composition for forming a seal portion having a high viscosity is applied to form an uncured seal portion, the uncured resin in the laminate obtained in the step (C) can be used. The thickness of the layer is formed to a thick thickness of 30 μm to 3 mm. (Step (dl)) After the pressure-reducing environment is released in the step (c1), the laminate is placed under a pressure environment having an ambient pressure of 50 kPa or more. After placing the laminate in a pressure environment of 50 kPa or more, the pressure is raised in the direction in which the liquid crystal panel and the protective sheet are adhered by the rising pressure. Therefore, if bubbles are present in the sealed space in the laminate, An uncured resin layer flows in the bubbles, so that the entire sealed space is uniformly filled by the uncured resin layer. The pressure environment is usually 80 k~120 kPa»pressure environment can be either atmospheric or higher pressure. The atmospheric pressure environment is optimal because it is possible to perform hardening of the unhardened resin layer without special equipment. The time from when the laminate is placed in a pressure environment of 50 kPa or more until the unhardened resin layer starts to harden (hereinafter referred to as high pressure holding time) is not particularly limited. When the pressure is applied to the atmosphere, the time required for the process becomes the high pressure holding time when the layer is self-reduced and the process is taken out and moved to the hardening device to start hardening. 154270.doc -29- 201133058 Therefore, when there is no air bubble in the closed space of the laminate under the atmospheric pressure environment, or during the process, the bubble disappears: In the case, the uncured resin can be made. The layer hardens immediately. When it takes time until the bubble disappears, the laminate is held at a force of 5 kb or more until the bubble disappears. Moreover, even if the high-voltage holding time becomes long, failure usually does not occur, so other necessity considerations in the self-made process can be extended by m (four) time. The high-pressure holding time can also be longer than the above, but since the production efficiency, (3) the position of the two-handed seat, it is preferably within 6 hours, preferably within 1 hour, and the production efficiency is increased. From the point of view, the special is less than 10 points. Next, a resin layer in which a liquid crystal panel and a protective sheet are bonded is formed by curing an uncured resin layer to produce a liquid crystal display device. At this time, the unhardened sealing portion may be simultaneously hardened with the uncured resin layer, or the uncured seal portion may be previously hardened before the uncured resin layer is cured. The uncured resin layer and the uncured seal portion comprise a photocurable composite Μ(4)(4), which is hardened 8 such as a self-light source (ultraviolet lamp, Koryo mercury lamp, UV-LED (Ultravi〇let Hght emitting diode)) The photocurable resin composition is cured by irradiating ultraviolet rays or short-wavelength visible light. At this time, in the liquid crystal panel and the protective sheet of the laminate, the uncured resin layer is irradiated with light from the side of the protective sheet having light transmissivity, and the side of the laminate is covered by the light-shielding portion and the liquid crystal panel. The uncured seal portion and the uncured resin layer are irradiated with light. In the liquid crystal panel and the s panel, the liquid crystal panel is mostly in a state of no operation. 154270.doc •30·201133058 It is not translucent, so the side of the protective plate passes through the light-transmitting portion surrounded by the light-shielding printing portion. Irradiation light. If there is a blackout printing enamel on the periphery of the vine plate, and there is an uncured seal and an uncured resin layer in the region sandwiched by the opaque printing portion and the liquid crystal panel, only protection is provided. The light in the light-transmitting part of the board cannot be hardened by the knife. Therefore, light is irradiated from the side of the laminate. As the light, it is preferably ultraviolet light or visible light of 45 〇 nm or less. In particular, when an anti-reflection layer is provided on the security plate, and the anti-reflection layer or the transparent resin film formed with the anti-reflection film or the adhesive layer provided between the anti-reflection film and the transparent surface material does not penetrate the ultraviolet ray, It is necessary to harden by visible light. As a light source for illuminating the light from the side of the laminate, a light source used for illuminating the light from the side of the compliant panel may be used, and it is suitable for the viewpoint of the arrangement space of the light source and the light irradiation of the specific portion. In other words, it is preferable to use an external line or an LED that emits visible light of 450 (10) or less. The light system may be irradiated from the side of the laminate after the irradiation from the side of the (four) plate, or may be irradiated from the side of the protective plate after the irradiation from the side of the laminate, or may be from the side of the protective plate. The side of the laminate is simultaneously irradiated. A. Further, the curing of the uncured seal portion and the uncured resin layer in the light-shielding printing portion is further promoted, and it is preferred to irradiate the side of the laminate first and then to the side of the laminate from the side of the protective sheet. Carry out the Zhao shooting. In the production method of the present invention, it is preferred to use the photopolymerization initiator (C2) contained in the photocurable resin composition for forming a known layer for the reason described below. Photo-curing resin for forming a part 154270.doc •31 - 201133058 Photopolymerization of the absorption wavelength range (λ2) of the longer wavelength side of the absorption wavelength range (λΐ) of the photopolymerization initiator (Cl) contained in the composition As the starting agent, as the light irradiated from the side of the laminate, light containing light of a wavelength within a wavelength range (λΐ) and light of a wavelength within a wavelength range (λ2) are used. Reason: The width of the uncured seal portion held by the light-shielding portion and the liquid crystal panel is 0.5 to 2 mm, and the width of the uncured resin layer sandwiched by the light-shielding portion and the liquid crystal panel is 1 to 1 〇 In the case of mm, the thickness of the unhardened resin layer is more than 0.03 to 2 mm. Therefore, it is difficult for the light irradiated from the side to reach the uncured resin layer at the boundary portion between the light-shielding portion and the light-transmitting portion. In this case, 'the photopolymerization initiator as the uncured seal portion and the photopolymerization initiator of the uncured resin layer', if most of the light having the same absorption wavelength is used, then most of the light irradiated from the side is irradiated. It is absorbed by the photopolymerization initiator of the uncured seal portion, and the light necessary for hardening does not sufficiently reach the uncured resin layer, so that the hardening cannot be sufficiently performed. When the hardening of the uncured resin layer of the light-shielding printing portion is insufficient, the resin layer forming photocurable resin composition or the uncured resin layer is insufficiently hardened at the boundary between the light-shielding portion and the light-transmitting portion. The photocurable resin composition for forming diffuses over time, and the resin layer which is sufficiently cured in the light transmitting portion has a slight difference in refractive index from the portion where the curing is insufficient, so that the light-shielding portion and the light-transmitting portion are In the part of the boundary, the transmitted light will cause optical distortion, which will lead to the decline of the enamel. On the other hand 'photopolymerization initiator as an uncured resin layer, 154270.doc • 32- 201133058 using an absorption wavelength domain (λΐ) having a photopolymerization initiator (cj) present in the uncured seal The photopolymerization initiator (C2) of the absorption wavelength range (λ2) on the longer wavelength side is 'and' is used as the light irradiated from the side of the laminate, and uses light of the wavelength in the absorption wavelength range (nine 1) and absorption. Both of the wavelengths of light in the wavelength domain (human 2). Therefore, the light of the wavelength in the absorption wavelength range (λ2) which is not absorbed by the photopolymerization initiator (C1) of the uncured seal portion sufficiently reaches the uncured resin which is sandwiched by the light-shielding printing portion and the liquid crystal panel. In the layer, the hardening of the uncured resin layer can be sufficiently performed by the photopolymerization initiator (C2) having the absorption wavelength domain (λ2). At this time, it is possible to simultaneously illuminate light from a light source having at least a part of the light-emitting wavelength range repeated with the absorption wavelength domain (λΐ), and light having a light source having at least a part of the light-emitting wavelength range repeated with the absorption wavelength domain (λ2). Can be irradiated separately. Further, light from a light source having at least a part of an emission wavelength range overlapping with both the absorption wavelength range (λΐ) and the absorption wavelength range (λ2) may be irradiated. [Specific Example] Hereinafter, the method of manufacturing the liquid crystal display device of Fig. 1 will be specifically described using the method (the case of (X) as an example]. (Step (al)) As shown in Fig. 3 and Fig. 4, along the liquid crystal The peripheral portion of the surface of the panel 2 on the side opposite to the second polarizing means 26 is formed by applying a photocurable resin composition for forming a sealing portion by a dispenser (not shown) or the like to form an uncured seal portion. A wiring member for transmitting a flexible printed wiring board 24 or the like for transmitting an electrical signal for operating the liquid crystal panel 2 is provided on the outer peripheral portion of the liquid crystal panel 20. In the manufacturing method of the present invention, 154270.doc-33-201133058 When the liquid crystal panel 2 and the protective sheet 10 are held, the arrangement of the wiring members is facilitated. Therefore, it is preferable to arrange the liquid crystal panel 2〇 on the lower side (step (bl)) Next, as shown in FIGS. 5 and 6 The resin layer forming photocurable resin composition 44 is supplied to the rectangular region 42 surrounded by the unhardened sealing portion 52 of the liquid crystal panel 20. The supply amount of the resin layer forming photocurable resin composition 44 is set in advance. For the following components: to make the seal from uncured The liquid crystal panel 20 and the protective sheet 1 〇 (see FIG. 7) are sealed by the resin layer forming photocurable resin composition 44. The resin layer forming photocurable resin composition 44 is filled. As shown in FIGS. 5 and 6, the liquid crystal panel 2 is placed flat on the lower fixed plate 66. The photo-curing property of the resin layer is formed by the dispensing machine 6〇 which is moved in the horizontal direction. The resin composition 44 is supplied in a line shape, a belt shape or a dot shape. The dispenser 60 is a known horizontal movement mechanism including a pair of feed screw 62 and a feed screw 64 orthogonal to the feed screw 62. It can be horizontally moved over the entire range of the region 42. Further, a squeeze coater can be used instead of the dispenser 6 (step (cl)) Next, as shown in Fig. 7, the liquid crystal panel 20 is The protective plate 1 is carried into the decompression device 70. The upper portion of the decompression device 70 is provided with a plurality of adsorption pads 72 above the fixed plate 74'. The lower plate 76 is provided at the lower portion. The upper plate 74 is closed by the cylinder. 78 is movable in the up and down direction. In the protective plate 10, the first polarizing mechanism 16 faces downward In the liquid crystal panel 20, the resin layer forming photocurable resin composition 44 is fixed upward to the lower fixed plate 76. Next, the vacuum pump 80 is used to attract the pressure. After the ambient pressure in the decompression device 70 reaches a decompression environment of, for example, 5 to 4 〇pa, the protective plate is adsorbed and held by the adsorption pad 72 of the upper plate 74. In the state, the air cylinder 78 is moved toward the liquid crystal panel 2 that is waiting downward, and then lowered. Then, the liquid crystal panel 2 is overlapped with the protective plate 〇 by the unhardened sealing portion 52, and the slab 1 is secured. The laminate, the liquid crystal panel, and the uncured seal portion 52 constitute a laminate in which the uncured resin layer including the photocurable resin composition for forming a resin layer is sealed, and the laminate is held for a specific time under a reduced pressure atmosphere. . Furthermore, the mounting position of the liquid crystal panel 20 with respect to the lower fixed plate 76, the number of the adsorption pads 72, the mounting position of the protective plate 丨〇 relative to the upper fixed plate 74, and the like are based on the size and shape of the liquid crystal panel 20 and the protective plate 1 Wait and adjust accordingly. Further, the mounting position of the liquid crystal panel 20 and the mounting position of the protective plate 1 are adjusted so that the angle formed by the polarization axes of the first polarizing means 16 and the second polarizing means 26 conforms to the design of the liquid crystal cell. For example, in the liquid crystal cell in which the liquid crystal in the liquid crystal cell is substantially perpendicular to the transparent surface material of the liquid crystal cell at the time of non-energization, the angle formed by the polarization axes of the first polarizing means and the second polarizing means is about 90°. In this case, an electrostatic chuck is used as the adsorption pad, and the electrostatic chuck holding method described in the specification attached to Japanese Patent Application No. 2008-206124 (incorporating this specification) is used, whereby the glass substrate can be stably maintained under reduced pressure. in environment. (Step (dl)) 54270.doc • 35-201133058 Next, after the inside of the decompression device 70 is at, for example, atmospheric pressure, the laminate is taken out from the decompression device 70. After the laminate is placed in an atmospheric pressure environment, the surface on the side of the liquid crystal panel 20 of the laminate and the surface on the side of the protective sheet 1 are pressed by atmospheric pressure, and the resin layer for forming a resin layer in the sealed space is combined with a photocurable resin. The object 44 is pressurized on the liquid crystal panel 20 and the protective sheet 10. Due to this pressure, the uncured resin layer in the sealed space flows, and the entire sealed space is uniformly filled by the uncured resin layer. Even after the entire sealed space is filled with the uncured resin layer, the position of the protective plate 10 can be moved relative to the liquid crystal panel 20 with a slight positional adjustment, whereby the first polarizing mechanism 16 and the first 2 The angle formed by the polarization axis of the polarizing mechanism 26. Next, as shown in Fig. 8, the uncured seal portion 52 and the uncured resin layer 46 sandwiched between the light-shielding portion 14 and the liquid crystal panel 20 are irradiated with light (ultraviolet rays) to the laminate. The uncured resin layer 46 is irradiated with light (ultraviolet rays) through the light transmitting portion 18 from the side of the protective sheet 1 全, and the uncured seal portion 52 and the uncured resin layer 46 in the laminate are hardened. Thereby, the liquid crystal display device 1 is manufactured. The above is a description of the method of manufacturing the liquid crystal display device of the present invention by taking the case of the method (α) as an example. In the case of the method (β), the liquid crystal display device can be manufactured in the same manner. (Effects) In the method for manufacturing a liquid crystal display device of the present invention described above, the polarizing means on the side of the protective plate of the two polarizing means is attached to the protective plate in advance instead of the liquid crystal panel, so that the liquid crystal can be just used. The panel is overlapped with the protective plate. 154270.doc -36- 201133058 Front 'The LCD panel and the protection plate are moved relative to each other, and the polarization axes of the two polarizing mechanisms are finely adjusted. Therefore, the preferred angles formed by the polarization axes of the two polarizing mechanisms can be easily aligned. Further, according to the method for producing a liquid crystal display device of the present invention described above, it is possible to manufacture a liquid crystal display device having a large area without generating bubbles in the resin layer. It is assumed that even if bubbles remain in the sealed uncured resin layer under reduced pressure, the pressure is applied to the sealed uncured resin layer under a higher pressure environment before hardening, so that the volume of the bubbles is reduced. The bubbles are easy to disappear. For example, the volume of gas in the bubble in the uncured resin layer sealed at 1 〇〇 Pa is considered to be i/iooo at 丨00 kpa. The gas also dissolves in the uncured resin layer, so that the gas in the minute volume of the bubble dissolves quickly in the uncured resin layer and disappears. In addition, even if a pressure of atmospheric pressure or the like is applied to the uncured resin layer after sealing, the liquid resin layer-forming curable resin composition is a fluid composition, and the pressure is uniformly distributed on the surface of the liquid crystal panel. A portion of the surface of the liquid crystal panel in contact with the unhardened resin layer is not subjected to the stress of the other day, so that the liquid crystal panel is less damaged. In addition, the interface adhesion force between the resin layer and the liquid crystal panel and the protective sheet due to the curing of the curable resin composition for forming a resin layer is higher than the interfacial adhesion force due to the fusion of the heat-fusible resin. 1. The pressure-sensitive resin layer-forming curable resin composition is pressed against the surface of the liquid crystal panel and the protective sheet, and is cured in this state, so that a further interface can be obtained. Force, and a uniform connection with respect to the surface of the liquid crystal panel and the protective plate can be obtained, and the local interface has a lower bonding force. Because 154270.doc •37·201133058, the peeling of the surface of the resin layer is low, and the moisture or corrosive gas enters less than the insufficient adhesion of the interface. In addition, after the method of injecting the curable resin composition for forming a resin layer into a space having a narrow space between the liquid crystal panel and the protective sheet (injection method), the generation of bubbles is small and can be performed. The curable resin composition for forming a resin layer is filled in a short time. Further, the curable resin composition for forming a resin layer has less restriction on the viscosity, and can easily be filled with a curable resin composition for forming a resin layer having a high viscosity. Therefore, a curable resin composition for forming a resin layer having a high viscosity and having a high molecular weight curable compound which can increase the strength of the resin layer can be used. Further, as the photopolymerization initiator (C2) of the uncured resin layer, the longer wavelength side of the absorption wavelength domain (λΐ) having the photopolymerization initiator (c丨) present in the uncured seal portion is used. The photopolymerization initiator (C2) of the absorption wavelength range (λ2) is 'and' is used as the light irradiated from the side of the laminate, and uses the wavelength of the absorption wavelength range (λ 1) and the absorption wavelength range (human 2 The light in the wavelength range (λ2) absorbed by the photopolymerization initiator (c丨) of the unhardened sealing portion is sufficiently reached by the light-shielding printing portion and The uncured resin layer held by the liquid crystal panel can sufficiently harden the uncured resin layer by the photopolymerization initiator (C2) having the absorption wavelength range (λ2). EXAMPLES Hereinafter, examples for carrying out the effectiveness of the present invention will be described. Example 1 is an example, and Example 2 is a comparative example. (Quantum average molecular weight) 154270.doc • 38· 201133058 The number average molecular weight of the oligomer was determined by using a GPC apparatus (HLC-8020, manufactured by T〇s〇h Co., Ltd.). (Viscosity) The viscosity of the photocurable resin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U). (Haze value) The Haze guard π manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and was determined by measurement based on ASTM D1 003. [Example 1] (Liquid Crystal Panel) A liquid crystal panel A was prepared which was oriented to be oriented substantially perpendicular to the transparent surface material of the liquid crystal cell when not energized, at a length of 712, a width of 412 Å, and a thickness of about 2 On the surface of the day-to-day unit of the coffee liquid, the length of the image of the absorptive polarizing plate is 696 _, and the width is not the claw, so that the polarizing axis is parallel to the short side of the liquid crystal cell. (protection plate): the peripheral portion of the surface of the soda-lime glass plate having a length of 794 mm, a width of 479 mm, and a thickness of 3 claws, so that the light-transmitting portion becomes a length-face and a width by a ceramic containing a black pigment Printing forms a opaque printed portion. In order to make the polarizing axis of the absorbing film-shaped absorbing polarizer in the PVA film and the protective plate have the long side of the protective plate, and the side of the opaque printing portion on which the soda lime glass plate is formed is formed. In the manner of contact, the absorption type polarizer is sandwiched between a soda lime glass plate and a TAC film, and these are bonded. 154270.doc -39- 201133058 Next, on the entire surface of the soda-lime glass plate opposite to the absorption-type polarizer side, an anti-reflection film (ReaLookx4001 manufactured by Nippon Oil Co., Ltd.) was attached to the surface with a protective film. Protection board b. (Photocurable resin composition for sealing portion formation) 2-functional polypropylene glycol (number average molecular weight calculated from base price: 4000) modified with ethylene ethoxide at the molecular end, and diisocyanate The ester was mixed at a molar ratio of 6 to 7, and then diluted with isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and then reacted at 70 eC in the presence of a catalyst of a tin compound. In the prepolymer, 2-hydroxyethyl acrylate was added at a molar ratio of about 1 to 2 and reacted at 7 ° C to obtain 30 wt% of a urethane acrylic acid diluted with isobornyl 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 Å. The viscosity of the UC-1 solution at 60 ° C is about 580 Pa, s. 90 parts by weight of UC-1 solution and 2-hydroxybutyl methacrylate (Lightester HOB, manufactured by Kyoeisha Chemical Co., Ltd.) were uniformly mixed to obtain a mixture. 1 part by weight of the mixture, hydroxy-cyclohexyl phenyl ketone (light
聚合起始劑 ’ Ciba Specialty Chemicals公司製，IRGACURE 184)0.9重量份、雙（2,4,6_三甲基笨）曱醯基氧化笨基膦（光 聚合起始劑’ Ciba Specialty Chemicals公司製， IRGACURE 819)0.1重量份、及25_二·叔丁基對苯二酚（聚 合抑制劑）0.04重量份加以均勻混合，獲得密封部形成用光 硬化性樹脂組合物〇 將密封部形成用光硬化性樹脂組合物（：放入容器中並維 154270.doc •40· 201133058 持原樣地於開放狀態下設置於減壓裝置内，將減壓裝置内 減壓至約20 Pa並保持1 〇分鐘以進行脫泡處理。測定密封 部形成用光硬化性樹脂組合物C於25。(：時之黏度，約為 1400 Pa*s。 . (樹脂層形成用光硬化性樹脂組合物） 將分子末端由環氧乙烷改質後之2官能聚丙二醇（由經基 價計算出的數量平均分子量：4000)、與異佛爾酮二異氰 酸自旨以4比5之莫耳比加以混合，於存在有錫化合物之觸媒 之情形下以70°C進行反應而獲得之預聚物中，以約1比2之 莫耳比添加2-丙烯酸羥乙酯並以70。〇進行反應，藉此獲得 氨S旨丙稀酸S旨券聚體（以下，記作UA-2)。UA-2之硬化性基 數為2’數量平均分子量約為24000，25。(：時之黏度約為 830 Pa.s。 將UA-2之40重量份、曱基丙烯酸2-羥丁酯（共榮社化學 公司製’ Lightester HOB)24重量份、及曱基丙烯酸正十二 烷基酯之36重量份均勻混合，於該混合物1 〇〇重量份中， 使雙（2,4,6-三曱基苯）曱醯基氧化苯基膦（光聚合起始劑，Polymerization initiator "IRGACURE 184", manufactured by Ciba Specialty Chemicals Co., Ltd., 0.9 parts by weight, bis(2,4,6-trimethyl phenyl) fluorenyl phenylphosphine (photopolymerization initiator - manufactured by Ciba Specialty Chemicals Co., Ltd.) , IRGACURE 819) 0.1 parts by weight and 0.04 parts by weight of 25-di-tert-butyl hydroquinone (polymerization inhibitor) are uniformly mixed to obtain a photocurable resin composition for forming a sealing portion, and a light for forming a sealing portion is formed. The curable resin composition (: placed in a container and dimensioned 154270.doc • 40· 201133058 is placed in the decompression device as it is in the open state, and the pressure in the decompression device is reduced to about 20 Pa for 1 〇 minutes. The defoaming treatment was carried out, and the photocurable resin composition C for sealing portion formation was measured at 25. (The viscosity at the time of the film was about 1400 Pa*s. (The photocurable resin composition for resin layer formation) The bifunctional polypropylene glycol modified by ethylene oxide (the number average molecular weight calculated from the base price: 4000) is mixed with the isophorone diisocyanate at a molar ratio of 4 to 5, In the presence of a catalyst for tin compounds In the prepolymer obtained by the reaction at 70 ° C, 2-hydroxyethyl acrylate was added at a molar ratio of about 1 to 2 and reacted at 70 Torr, thereby obtaining an ammonia S-supply acid S coupon. Polymer (hereinafter, referred to as UA-2). The hardening base of UA-2 is 2'. The number average molecular weight is about 24000, 25. (: viscosity at time is about 830 Pa.s. 40 weight of UA-2. 24 parts by weight of 2-hydroxybutyl methacrylate ("Lightester HOB" manufactured by Kyoeisha Chemical Co., Ltd.) and 36 parts by weight of n-dodecyl methacrylate are uniformly mixed, and 1 part by weight of the mixture is used. a bis(2,4,6-trimercaptophenyl) fluorenyl phenylphosphine (photopolymerization initiator,
Ciba Specialty Chemicals公司製，IRGACURE 819)0.2重量 • 份、2,5-二-叔丁基對苯二酚（聚合抑制劑）〇·〇4重量份、ι，4- • 雙（3-巯基丁醯氧基）丁烷（鏈轉移劑，昭和電工公司製，Made by Ciba Specialty Chemicals, IRGACURE 819) 0.2 parts by weight, 2,5-di-tert-butyl hydroquinone (polymerization inhibitor) 〇·〇 4 parts by weight, ι,4- • bis(3-mercaptobutyl)醯oxy)butane (chain transfer agent, manufactured by Showa Denko,
Karenz MT BD-1)1重量份、及紫外線吸收劑（ciba Specialty Chemicals公司製，TINUVIN 109)0.3重量均勻溶 解，獲得樹脂層形成用光硬化性樹脂組合物D。 IRGACURE 819於相較IRGACURE 184之吸收波長域（約 154270.doc -41 - 201133058 380 nm以下）更長波長側亦具有吸收波長域（約44〇 下）。 將樹脂層形成用光硬化性樹脂組合物D放入容器中並維 持原樣地於開放狀態下設置於減壓裝置内，將減壓裝置内 減壓至約20 Pa並保持10分鐘以進行脫泡處理。測定樹脂 層形成用光硬化性樹脂組合物D於25。(：時之黏度，為i 7 Pa.s 〇 (步驟（al)) 於液晶面板A之與偏光板側為相反側之表面（亦即，未形 成有偏光板之面）、且遍及圖像顯示區域之外側之約5 mm 之位置的全周，以寬度約1 mm、塗佈厚度約〇 6爪⑺之方 式藉由點膠機而塗佈密封部形成用光硬化性樹脂組合物 c，形成未硬化之密封部。 (步驟（bl)) 於液晶面板A之圖像顯示區域之外周所塗佈的未硬化之 密封部之内側之區域上，使用點膠機將樹脂層形成用光硬 化性樹脂組合物D供給至複數個部位，以使總質量成為丨25 g 0 於供給樹脂層形成用光硬化性樹脂組合物D之期間，未 硬化之密封部之形狀得以維持。 (步驟（cl)) 將液晶面板A以使樹脂層形成用光硬化性樹脂組合物d 朝上之方式平置於設置有-對定盤之升降裝置之減 内之下定盤的上表面。 】5427ad〇c -42· 201133058 將保護板B保持為：使吸收型偏光子側之表面與液晶面 板A相對向，於減壓裝置内之升降裝置之上定盤之下表面 使用靜電吸盤’使自上表面觀察時保護板B之無遮光印刷 部之透光部與液晶面板A之圖像顯示區域具有約ι麵之邊 緣而成為相同位置’且於垂直方向上與液晶面板A之距離 成為30 mm此時，配置成使液晶面板A之偏光板及保護 板B之吸收型偏光子之偏光軸彼此正交。 將減壓裝置形成為密封狀態並進行排氣，直至減壓裝置 内之壓力成為約10 Pa為止。於減壓裝置内之升降裝置中 使上下之定盤接近，介隔樹脂層形成用光硬化性樹脂組合 物D而對液晶面板a與保護板8以2 kpa之壓力進行壓接， 並保持1分鐘。將靜電吸盤除電並使其自上定盤離開保護 板B，以約15秒而使減壓裝置内還原成大氣壓由液晶面 板A、保護板B、及未硬化之密封部而獲得使包含樹脂層 形成用光硬化性樹脂組合物D之未硬化之樹脂層得以密封 的積層物E。 積層物E中未硬化之密封部之形狀維持於大致初期之狀 態。 (步驟（dl)) 對積層物E之設置於液晶面板a之周緣部之未硬化之密 封部（密封部形成用光硬化性樹脂組合物C)，自積層物e之 側方’使用將紫外線LED配置成線狀之紫外線光源 (Spectrum Illumination公司製 LL146-395)，遍及未硬化之 密封部之全周而照射約10分鐘的光，使未硬化之密封部硬 154270.doc -43- 201133058 化。以照度什（OAK製作所公司製，uv_M〇2，受光器ο% 42)測定照射光之強度，約為5 mW/em2。使未硬化之密封 部硬化後，將積層物E水平保持並靜置約1〇分鐘。 自積層物E之保護板B側之面，均勻照射來自化學燈之 紫外線及450 nm以下之可見光，使未硬化之樹脂層（樹脂 層形成用光硬化性樹脂組合物D)硬化，形成樹脂層，獲得 液晶顯不裝置F。對於液晶顯示裝置F而言，儘管無需於以 先别之注入法進行製造時所需之氣泡去除之步驟，但未確 認到樹脂層中殘留之氣泡等之缺陷。又，亦未確認到來自 密封部之樹脂層形成用光硬化性樹脂組合物之漏出等之缺 陷。另外’樹脂層之厚度成為目標厚度（約〇 4 mm) ° 為了觀察保護板B之遮光印刷部下之樹脂層形成用光硬 化性樹脂組合物〇之硬化狀態，自硬化後之密封部插入長 度35 mm、寬度5 mm、厚度〇 25 mm之不鏽鋼板，與密封 部鄰接之遮光印刷部下之樹脂層並不流動，樹脂層形成用 光硬化性樹脂組合物D得以充分硬化。 代替液晶面板A ’使用大致相同尺寸之玻璃板而同樣地 製作透明積層體’測定無印刷遮光部之部分之霧度值為 1%以下，為透明度較高之良品。 將液晶顯示裝置F放入液晶電視接收機之框體中，再連 接配線並接入電源，獲得顯示對比度較高的圖像。即便用 手指強力按壓圖像顯示面，圖像亦不會紊亂，保護板B效 率良好地保護液晶面板A。 [例2] 154270.doc -44 - 201133058 於液晶面板A之周緣部，黏貼厚度0.5 mm、寬度2爪爪之 雙面膠帶，僅殘留〗邊之雙面膠帶之脫模膜’剝掉表面之 脫模膜。於保護板B上重疊液晶面板A，並以3邊之雙面膠 帶貼合。 於殘留有脫模膜之1邊之雙面膠帶與保護板B之間，藉由 起子撬開2 mm左右，自該部分注入155 §的樹脂層形成用 光硬化性樹脂組合物D，但液晶面板八與保護板B間之空間 之下部殘留有氣泡，故無法將樹脂層形成用光硬化性樹脂 組合物D密實地注入至該空間中。 本發明參照特定之實施態樣進行了詳細說明，但本領域 技術人員明白，於不脫離本發明之精神及範疇内可實施各 種變更或修正。 本申請案係基於2010年2月18日提出申請之日本專利申 請2010-033702者，其内容作為參照而被併入於此。 產業上之可利用性 根據本發明，可消除製造藉由保護板而保護液晶面板之 液晶顯示裝置時之問題點。 【圖式簡單說明】 圖1係表不藉由保護板保護液晶面板之液晶顯示裝置之 一例的剖面圖； 圖2係圖1之液晶顯示裝置之平面圖； 圖3係表示步驟（al)之狀況之一例的平面圖； 圖4係表示步驟（al)之狀況之一例的剖面圖； 圖5係表示步驟（bl)之狀況之一例的平面圖； 154270.doc •45- 201133058 圖6係表示步驟（bl)之狀況之一例的 °1』面圖； 圖7係表示步驟（c 1)之狀況之一例的 ’ °】面圖；及 圖8係表示步驟（dl)之狀況之一例的剖面 【主要元件符號說明】 ° 1 液晶顯示裝置 10 保護板 12 透明面材 14 遮光印刷部 16 第1偏光機構 18 透光部 20 液晶面板 22 液晶單元 24 印刷配線板 26 第2偏光機構 32、34 透明面材 36 液晶層 40 樹脂層 42 由密封部包圍之區域 44 樹脂層形成用光硬化性樹脂組合物 46 未硬化之樹脂層 50 密封部 52 未硬化之密封部 60 點膠機 62 > 64 進給螺桿 154270.doc •46- 201133058 66 70 72 74 76 78 80 下定盤 減壓裝置 吸附墊 上定盤 下定盤 氣缸 真空泵 154270.doc •47-1 part by weight of the Karenz MT BD-1) and a UV absorber (TINUVIN 109, manufactured by Ciba Specialty Chemicals Co., Ltd.) were uniformly dissolved in 0.3 weight to obtain a photocurable resin composition D for forming a resin layer. IRGACURE 819 also has an absorption wavelength domain (approximately 44 〇) on the longer wavelength side of the absorption wavelength region of IRGACURE 184 (approximately 154270.doc -41 - 201133058 380 nm). The resin layer-forming photocurable resin composition D was placed in a container and kept in a decompression device as it is in an open state, and the inside of the decompression device was depressurized to about 20 Pa for 10 minutes to perform defoaming. deal with. The photocurable resin composition D for forming a resin layer was measured at 25. (: viscosity at the time, i 7 Pa.s 〇 (step (al)) on the opposite side of the liquid crystal panel A from the side of the polarizing plate (that is, the surface on which the polarizing plate is not formed), and throughout the image The photocurable resin composition c for sealing portion formation is applied by a dispenser to the entire circumference at a position of about 5 mm on the outer side of the display region by a thickness of about 1 mm and a coating thickness of about 6 claws (7). Forming an uncured seal. (Step (b1)) The resin layer is formed by photohardening using a dispenser on the inner side of the unhardened seal applied to the periphery of the image display area of the liquid crystal panel A. The resin composition D is supplied to a plurality of portions so that the total mass is 丨25 g 0 during the supply of the resin layer-forming photocurable resin composition D, and the shape of the unhardened sealing portion is maintained. )) The liquid crystal panel A is placed on the upper surface of the lower plate of the lowering device provided with the lifting device of the pairing plate so that the resin layer forming photocurable resin composition d faces upward. 】5427ad〇c - 42· 201133058 Keep the protection board B as: the table of the absorption type polarizer side The surface is opposite to the liquid crystal panel A, and the surface of the lower surface of the lifting device is used on the lower surface of the lifting device in the decompression device to make the light-transmitting portion of the protective plate B without the light-shielding printing portion and the liquid crystal panel A when viewed from the upper surface. The image display area has an edge of about ι surface and becomes the same position ' and the distance from the liquid crystal panel A in the vertical direction is 30 mm. At this time, the absorbing type photon of the polarizing plate of the liquid crystal panel A and the protective plate B are arranged. The polarizing axes are orthogonal to each other. The decompression device is sealed and exhausted until the pressure in the decompression device becomes about 10 Pa. In the lifting device in the decompression device, the upper and lower plates are brought close to each other. The resin layer forming photocurable resin composition D was pressure-bonded to the liquid crystal panel a and the protective plate 8 at a pressure of 2 kPa, and held for 1 minute. The electrostatic chuck was removed and the protective plate was removed from the upper plate. The uncured resin layer containing the photocurable resin composition D for forming a resin layer is obtained by the liquid crystal panel A, the protective sheet B, and the uncured seal portion by reducing the pressure in the pressure reducing device to atmospheric pressure in about 15 seconds. The shape of the unsealed seal portion in the laminate E is maintained at a substantially initial state. (Step (dl)) The unhardened seal portion of the laminate E provided on the peripheral portion of the liquid crystal panel a (Photocurable resin composition C for sealing portion formation), an ultraviolet light source (LL146-395 manufactured by Spectrum Illumination Co., Ltd.) in which the ultraviolet light LED is arranged in a line shape is used from the side of the laminated material e, and is spread over the unhardened sealing portion. The light was irradiated for about 10 minutes throughout the week, and the uncured seal portion was hardened 154270.doc -43- 201133058. The intensity of the illuminating light was measured by illuminating (made by OAK Co., Ltd., uv_M〇2, light receiver ο% 42) , about 5 mW/em2. After the uncured seal is hardened, the layer E is held horizontally and allowed to stand for about 1 minute. The ultraviolet ray from the chemical lamp and the visible light of 450 nm or less are uniformly irradiated from the surface of the protective sheet B on the side of the protective layer E, and the uncured resin layer (photocurable resin composition D for resin layer formation) is cured to form a resin layer. , the liquid crystal display device F is obtained. In the liquid crystal display device F, although the step of removing the bubbles required for the production by the prior injection method is not required, the defects such as bubbles remaining in the resin layer are not confirmed. In addition, defects such as leakage of the photocurable resin composition for forming a resin layer from the sealing portion have not been observed. In addition, the thickness of the resin layer is the target thickness (about mm4 mm). In order to observe the hardened state of the resin layer forming photocurable resin composition under the light-shielding portion of the protective sheet B, the sealing portion is inserted into the length 35 after hardening. In the stainless steel plate having a mm, a width of 5 mm, and a thickness of 〇25 mm, the resin layer under the light-shielding printing portion adjacent to the sealing portion does not flow, and the resin layer-forming photocurable resin composition D is sufficiently cured. In the same manner as the liquid crystal panel A', a transparent laminated body was produced in the same manner as the glass plate of the same size. The haze value of the portion where the non-printing light-shielding portion was measured was 1% or less, which was a good transparency. The liquid crystal display device F is placed in the casing of the liquid crystal television receiver, and the wiring is connected and connected to the power source to obtain an image with a high display contrast. Even if the image display surface is strongly pressed with a finger, the image is not disturbed, and the protective sheet B protects the liquid crystal panel A with good efficiency. [Example 2] 154270.doc -44 - 201133058 On the peripheral edge of the liquid crystal panel A, a double-sided tape with a thickness of 0.5 mm and a width of 2 claws is adhered, and only the release film of the double-sided tape remaining on the side is peeled off. Release film. The liquid crystal panel A is overlapped on the protective sheet B, and is bonded by a double-sided tape of three sides. A photocurable resin composition D is formed by injecting a resin layer of 155 § from the portion between the double-sided tape and the protective sheet B on the side where the release film is left, by a slit of about 2 mm, but the liquid crystal panel is formed. Since air bubbles remain in the lower portion of the space between the protective plate B and the protective sheet B, the resin layer forming photocurable resin composition D cannot be densely injected into the space. The present invention has been described in detail with reference to the specific embodiments thereof. The present application is based on Japanese Patent Application No. 2010-033702, filed on Feb. Industrial Applicability According to the present invention, it is possible to eliminate the problem of manufacturing a liquid crystal display device for protecting a liquid crystal panel by a protective sheet. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a liquid crystal display device which does not protect a liquid crystal panel by a protective plate; Fig. 2 is a plan view of the liquid crystal display device of Fig. 1; Fig. 3 is a view showing the state of the step (al) Fig. 4 is a cross-sectional view showing an example of the condition of the step (al); Fig. 5 is a plan view showing an example of the condition of the step (bl); 154270.doc • 45- 201133058 Fig. 6 shows the step (bl FIG. 7 is a '°' surface view showing an example of the condition of the step (c 1); and FIG. 8 is a cross section showing an example of the condition of the step (d1). DESCRIPTION OF REFERENCE NUMERALS 1 liquid crystal display device 10 protective plate 12 transparent surface material 14 light-shielding printing portion 16 first polarizing mechanism 18 light transmitting portion 20 liquid crystal panel 22 liquid crystal cell 24 printed wiring board 26 second polarizing mechanism 32, 34 transparent surface material 36 Liquid crystal layer 40 Resin layer 42 region 44 surrounded by sealing portion Resin layer forming photocurable resin composition 46 Unhardened resin layer 50 Sealing portion 52 Unhardened sealing portion 60 Dispenser 62 > 64 Screw 154270.doc •46- 201133058 66 70 72 74 76 78 80 Lowering plate Pressure reducing device Adsorption pad Upper plate Lower plate Cylinder Vacuum pump 154270.doc •47-