TW201124783A - Method for manufacturing liquid crystal display device - Google Patents

Method for manufacturing liquid crystal display device Download PDF

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Publication number
TW201124783A
TW201124783A TW099133457A TW99133457A TW201124783A TW 201124783 A TW201124783 A TW 201124783A TW 099133457 A TW099133457 A TW 099133457A TW 99133457 A TW99133457 A TW 99133457A TW 201124783 A TW201124783 A TW 201124783A
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TW
Taiwan
Prior art keywords
wavelength
liquid crystal
light
sealant
crystal material
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TW099133457A
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Chinese (zh)
Inventor
Shinshi Yamaguchi
Hiroshige Hata
Sayu Shioya
Kazuaki Yano
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Sekisui Chemical Co Ltd
Ushio Electric Inc
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Application filed by Sekisui Chemical Co Ltd, Ushio Electric Inc filed Critical Sekisui Chemical Co Ltd
Publication of TW201124783A publication Critical patent/TW201124783A/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13775—Polymer-stabilized liquid crystal layers

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Liquid Crystal (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)

Abstract

Disclosed is a method for manufacturing, with low cost and high efficiency, a liquid crystal display device having almost no liquid crystal contamination. The method has: a step (1) wherein a frame-shaped sealing agent layer is formed on one substrate using a photo-curable sealing agent containing a curable resin and a photopolymerization initiator; a step (2) wherein a liquid crystal material containing a polymerizable material and a photopolymerization initiator is dropped to a region surrounded by the sealing agent layer; a step (3) wherein said substrate and the other substrate are bonded to each other with the sealing agent therebetween, and the sealing agent is photocured by radiating light having a wavelength that photocures the sealing agent to the bonded substrates; a step (4) wherein the liquid crystal material is photopolymerized by radiating light having a wavelength that photopolymerizes the liquid crystal material. The wavelength of the light that photocures the sealing agent is further on the long wavelength side than the wavelength of the light that photopolymerizes the liquid crystal material, and the light having the wavelength that photocures the sealing agent in the step (3) is radiated by means of a light radiation apparatus having an LED element and a filter. The LED element has an emission peak wavelength in a wavelength region wherein the sealing agent is photocured, and is outside of the wavelength region wherein the liquid crystal material is photopolymerized. The filter cuts, among the light radiated from the LED element, the light, which is in a region further on the short wavelength side than the emission peak wavelength and overlaps the wavelength that photopolymerizes the liquid crystal material.

Description

201124783 六、發明說明： 【發明所屬之技術領域】 無液 本發明係關於一種可以低成本且高效率製造幾乎 晶污染之液晶顯示裝置的液晶顯示裝置之製造方法。 【先前技術】 近年來，對於液晶顯示面板，為了提高對比度或改善 響應速度，正開發藉由聚合物結構控制液晶分子之配向； 向的PSA(Polymer Sustained AHgnment)方式代替單元内部 开》成之阻隔壁結構（rib structure) 〇 PSA方式之液晶顯示面板之製造製程係向單元内注入 a有光聚合性成分之液晶材料，一面對所注入之液晶材料 施加電壓一面照射紫外線，藉此於單元内形成聚合物結 構。作為使液晶材料留存於液晶顯示面板之方法之一的液 晶滴下法’係藉由於構成單元之—塊透光性基板之表面塗 佈光硬化性密封劑’形成框狀之密封劑層，於由該一塊透 光性基板之表面之密封劑層所包圍之區域中塗佈含有單體 之液晶材料後，於重疊有另一塊透光性基板之狀態下，利 .4示面板之貼合裝置對密封劑層照射光，使該密封劑硬 化而將2塊透光性基板貼合。其後，藉由對液晶材料所含 有之單體照射紫外線而形成聚合物結構，而形成注入有液 晶材料之單元。 使用此種3有單體之液晶材料，利用可見光使密封劑 硬化，其後利用紫外線使液晶硬化而構成單元的方法，亦 201124783 通用於藍相方式。 顯示面板之貼合裝置，例如可使用專利文獻1所揭示 之具有如下部分的光照射裝置：放射光硬化型密封劑之吸 光波長區域之光的燈（作為用以對密封劑層照射光之光 源）、與遮蔽短波長側之光之濾光片。用於此種光照射裝置 之燈，一般為金屬鹵化物燈。然而，若利用使用有金屬鹵 化物燈之先前之一般光照射裝置來製造PSA方式或藍相方 式之液晶顯示面板，則有發生顯示不均之不良情況的問題。 專利文獻1.日本特開2003 — 149647號公報 【發明内容】 本發明之目的在於提供一種可以低成本且高效率製造 幾乎無液晶污染之液晶顯示裝置之液晶顯示裝置之製造方 法。 本發明係一種液晶顯示裝置之製造方法，其係具有如 y v驟者.步驟丨.使用含有硬化性樹脂與光聚合起始劑之 光硬化性密封劑於一塊基板上形成框狀之密封劑層；步驟 j將含有聚合性材料與光聚合起始劑之液晶材料滴加於由 該密封劑層包圍之區域；步驟3:藉由上述密封劑將上述一 六土板與3 &基板貼合，對該已貼合之基板照射使上述 二封劑光硬化之波長的&，而使上述密封劑光硬化；及步 :姑钮二射使上述液晶材料光聚合之波長的&，而使上述液 相# 2光聚〇，並且，使上述密封劑光硬化之光的波長， 乂；使上述液晶材料光聚合之光的波長，位於更長波長 201124783 側，於上述步驟3中使密封劑光硬化之波長之光係由具有 元件與/慮光片之光照射裝置照射，上述led元件於使 上述密封劑光硬化之波長的區域内之除使上述液晶材料光 聚合之波長的區$以外之區域具有發光峰值波《，並且， 该峰值之半值寬度為3Gnm以下，而上述遽光片則會過滤掉 自上述LED元件照射之光中位於較上述發光峰值波長更短 波長側且與使上述液晶材料光聚合之波長重複之區域之 光。 以下對本發明進行詳細說明。 本發明人等首先針對於利用使用有金屬鹵化物燈之一 般光照射裝置來製造PSA方式之液晶顯示面板時會發生顯 八不句之不良情況的原因進行了研究。結果查明原因為： 金屬鹵化物燈顯不出2〇〇〜6〇〇 nm之較廣範圍之寬發光光 —般而言，光硬化性密封劑之感光波長為2〇〇〜45〇打爪 左右，使液晶材料光聚合之波長亦因所使用之反應性單體 而異而為200〜400 nm左右。因此，若為了使密封劑硬化 而利用金屬函化物燈進行照射，則液晶材料之一部分同時 發生硬化，此情況被認為係導致顯示不均之原因。 為了防止此種液晶材料之部分硬化，可利用具有介電 體多層膜之濾光片等遮蔽使液晶材料硬化之短波長側之 光’僅照射長波長側之光而使密封劑硬化。然而，具有介 電體多層膜之濾光片有時其入射角依賴性明顯，會因為光 之入射角度不同而無法充分遮蔽目標波長區域之光。因 6 201124783 此，為了確實地防止液晶材料之部分硬化，而使用遮蔽至 相對長波長側為止之光的渡光片。然@，若使用此種遮蔽 較寬波長區域之光的濾光片，則自金屬_化物燈照射之光 之大。卩分會被遮蔽，光之利用效率會極度降低。實際上對 密封劑照射之光的照射量較低，且僅為長波長區域之光。 由於此種低照射量且長波長之光無法使密封劑充分硬化， 因此於密封劑完全硬化前密封劑成分會溶析至液晶令，弓丨 起液晶污染而導致顯示不均。為了轉保對密封劑之光之照 射量’若將金屬齒化物燈之照射強度設定為極高，則濾光 =無法充分遮蔽之短波長側之光之照射量亦增大，因而變 得無法防止液晶材料之部分硬化。 如此，即使利用使用有金屬齒化物燈之一般光照射裝 :=製w PSA方式之液晶顯示面板，亦會發生液晶材料之 P刀硬化或由密封劑之硬化不良引起之液晶污染中之任 一情況，而導致發生顯示不均之不良情況。 又’金屬函化物燈於節能方面亦存在問題。由於金屬 鹵化物燈自開始κ5、去 用始點凴至達到穩定點亮狀態為止需要相當時 間（即難以瞬時點亮），因此於光照射裝置中，係#由設置快 機構☆連續點亮燈之狀態下，藉由快門機構之快門開 閉而於需要時對昭射斜金 、、、射對象物照射光。因此，儘管實際利用 時間極短，但不復 — 進订連續照射’能量效率較低。並且， 方存在快門機構中 降低的問題。 了動零件易導致故障’裝置之可靠性 使用利用較使液晶材 針對上述情況，本發明者發現 201124783 料光聚合之光之波長更長波長側之光進行硬化之密封劑， 且使用具有「於使密封劑光硬化之波長之區域内之除使液 b曰材料光聚合之波長之區域以外之區域具有發光峰值波 長，且該發光峰值之半值寬度較窄」之LED元件及「㈣ 掉位於較LED元件之發光峰值波長更短波長側且與使液晶 材料光聚合之波長重複之區域之光」之滤光片之裝置以 作為用以照射使該密封劑硬化之光之光照射裝置，藉此可 以低成本且高效率製造幾乎無液晶污染之液晶顯示裝置， 從而完成本發明。 LED元件與金屬齒化物燈相比具有發光波長極為清晰 之優異特徵。將用以過濾位於較LED元件之發光峰值波長 更短波長側且與使液晶材料光聚合之波長重複之區域之光 的濾光片’與此種具有清晰發光峰之LED元件結合藉此 可確實地防止由液晶材料之部分硬化引起之顯示不均之發 並且可使大σρ分投入之光不受遮蔽，高效率地獲得利 用而到達密封劑，因此可確實地使密封劑硬化，亦可確實 地防止由液晶污染引起之顯示不均之發生。 進而Φ於LED元件自開始點亮至達到穩定點亮狀態 :時間極短’亦即可瞬時點冑，因此無需如金屬齒化物燈 般直點7^，節旎性優異。亦無需設置複雜之快門機構， 可獲得較高之可靠性。 於本發明之液晶顯示裝置之製造方法中，首先進行使 用含有硬化性樹脂與光聚合起始劑之光硬化性密封劑於一 塊基板上形成框狀之密封劑層之步驟1。 8 201124783 上述密封劑係下述利用較使液晶材料光聚合之光之波 長更長波長側之光進行硬化者。 上述密封劑含有硬化性樹脂與光聚合起始劑。 上述硬化性樹脂，較佳為具有（甲基）丙稀酸基與環氧 土藉由八有此種g旎基，所獲得之密封劑可經過光硬化、 熱硬化之二階段硬化。 _又，於上述硬化性樹脂中，於具有（甲基）丙烯酸基與環 氧基之清形時，銥氧基相對於（甲基）丙烯酸基與環氧基之合 計量的比率之較佳上限為4G莫耳^上述環氧基之比率 超過40莫耳％，則對液晶之溶解性提高，有時會產生導致 面板產生不均之污染。更佳上限為3〇莫耳％。 此種硬化性樹脂並無特別限定，例如可列舉：藉由使（甲 基）丙烯酸與具有羥基之化合物反應而獲得之酯化合物藉 由使（曱基）丙稀酸與環氧化合物反應而獲得之環氧（曱基）丙 烯酸酯、藉由使異氰酸酯與具有羥基之（甲基）丙烯酸衍生物 反應而獲得之（甲基）丙烯酸胺曱酸酯等。 上述藉由使（曱基）丙烯酸與具有羥基之化合物反應而 獲得之酯化合物並無特別限定，單官能者，例如可列舉、甲 基）丙烯酸2-羥乙酯、（曱基）丙烯酸2_羥丙酯、（曱基）丙烯 酸4-羥丁酯、（曱基）丙烯酸2_羥丁酯、（甲基）丙烯酸異丁酯、 (甲基）丙烯酸三級丁酯、（甲基）丙烯酸異辛酯、（曱基）丙烯 酸月桂醋、（曱基）丙烯酸硬脂酯、（曱基）丙烯酸異茨醋、（甲 基）丙烯酸環己酯、（曱基）丙烯酸2-曱氧基乙酯、曱氧基乙 二醇（甲基）丙烯酸酯、（曱基）丙烯酸2-乙氧基乙酯、（甲基） 201124783 丙烯酸四氫糠酯、（甲基）丙烯酸苄酯、乙基卡必醇（曱基）丙 烯酸酯、（曱基）丙烯酸笨氧基乙酯、苯氧基二乙二醇（甲基） 丙烯酸酯、苯氧基聚乙二醇（甲基）丙烯酸酯、甲氧基聚乙二 醇（甲基）丙烯酸酯、（甲基）丙烯酸2,2,2-三氟乙酯、（曱基） 丙烯酸2,2,3,3-四氟丙酯、（甲基）丙烯酸iH，1H，5H_八氟戊 酯、（甲基）丙烯醯亞胺、（曱基）丙烯酸甲酯、（曱基）丙烯酸 乙酯、（曱基）丙烯酸正丁酯、（甲基）丙烯酸丙酯、（曱基）丙 烯酸正丁酯、（曱基）丙烯酸環己酯、（甲基）丙烯酸2_乙基己 酯、（曱基）丙烯酸正辛酯、（甲基）丙烯酸異壬酯、（曱基）丙 烯酸異肉豆蔻酯、（甲基）丙烯酸2-丁氧基乙酯、（甲基）丙烯 酸2-苯氧基乙酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯酸 異癸酯、（曱基）丙烯酸二乙胺乙酯、（甲基）丙烯酸二曱胺乙 S曰、琥珀酸2-(甲基）丙缚醯氧基乙酯、六氫鄰苯二曱酸2·(甲 基）丙烯醯氧基乙酯、鄰苯二甲酸2-羥基丙酯2-(甲基）丙稀 醯氧基乙酯、（曱基）丙烯酸縮水甘油酯、磷酸2-(曱基）丙稀 醯氧基乙酯等。 。 又’上述藉由使（甲基）丙烯酸與具有羥基之化合物反應 而獲得之酯化合物中’ 2官能者並無特別限定，例如可列 舉.1,4-丁二醇二（甲基）丙浠酸酯、ι，3_ 丁二醇二（甲基）丙稀 酸顆、1，6-己二醇二（曱基）丙烯酸酯、19-壬二醇二（甲基） 丙烯酸酯、1，1〇_癸二醇二（曱基）丙烯酸酯、2_正丁基_2·乙 基-1，3-丙二醇二（曱基）丙烯酸酯、二丙二醇二（曱基）丙烯酸 酉旨、三丙二醇二（甲基）丙烯酸酯、聚丙二醇（甲基）丙烯酸酯、 乙二醇二（甲基）丙烯酸酯 '二乙二醇二（曱基）丙烯酸酯 '四 201124783 乙二醇二（曱基）丙烯酸酯、聚乙二醇二（曱基）丙烯酸酯、環 氧丙烷加成雙酚A二（曱基）丙烯酸酯、環氧乙烷加成雙酚A 二（甲基）丙烯酸酯、環氧乙烷加成雙酚F二（曱基）丙烯酸 酯、二羥甲基二環戊二烯二（甲基）丙烯酸酯、1,3-丁二醇二 (曱基）丙烯酸酯、新戊二醇二（曱基）丙烯酸酯、環氧乙烷改 質異三聚氰酸二（甲基）丙烯酸酯、（曱基）丙烯酸2-羥基 -3-(甲基）丙烯醯氧基丙酯、碳酸酯二醇二（甲基）丙烯酸酯、 聚醚二醇二（甲基）丙烯赛酯、聚酯二醇二（曱基）丙烯酸酯、 聚己内酯二醇二（曱基）丙烯酸酯、聚丁二烯二醇二（甲基）丙 烯酸酯等。 又，上述藉由使（曱基）丙烯酸與具有羥基之化合物反應 而獲得之酯化合物中，3官能以上者並無特別限定，例如可 列舉：新戊四醇三（曱基）丙烯酸酯、三經甲基丙烧三（曱基） 丙烯酸酯、環氧丙烷加成三羥甲基丙烷三（甲基）丙烯酸酯、 環氧乙烧加成二經曱基丙院三（甲基）丙稀酸酿、己内酷改質 一羥曱基丙烧二（曱基烯酸酯、環氧乙烧加成異三聚氰酸 三（曱基）丙烯酸酯、二新戊四醇五（曱基）丙烯酸酯、二新戊 四醇六（曱基）丙烯酸酯、二（三羥曱基丙烷）四（曱基）丙烯酸 醋 '新戊四醇四（甲基）丙烯酸醋、甘油三（曱基）丙烯酸醋、 環氧丙烷加成甘油三(甲基)丙烯酸酿、磷酸三(甲基)丙稀醯 氧基乙3旨等。 上述藉由使（曱基）丙烯酸與環氧化合物反應而獲得之 環氧（甲基）丙烯酸醋並無特別限定，例如可列舉：按照常規 方法於驗性觸媒之存在下藉由作摄 卜精由使％氧樹脂與（甲基）丙烯酸 11 201124783 反應而獲得者等β 作為用以合成上述環氧（尹基）丙稀酸醋之原料的環氧 化t物並無特別限^，可列舉：雙粉Α型環氧樹腊、雙紛F 型核氧樹脂、雙酚S型環氧樹脂、2,2._二烯丙基雙酚A型 !氧樹脂、氫化雙龄型環氧樹月旨、環氧丙烧加成雙酚A型 衣氧樹月曰、間本二齡型環氧樹脂、聯苯型環氧樹脂、硫化 物型環氧樹脂、㈣環氧樹脂、二環戊二烯型環氧樹脂、 秦型環氧樹脂、苯紛酴駿清漆型環氧樹脂、鄰甲㈣盤清 漆5L衣氧樹月曰、一 ％戊二烯齡酸清g型環氧樹月旨、聯苯酚 酸清漆型環氧樹脂、萘紛祕清漆型環氧樹脂、縮水甘油 胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧 樹脂、縮水甘油酯化合物、雙酚A型環硫樹脂等。义 上述雙酚A型環氧樹脂中之市售樹脂，例如可列舉： Epikote 828EL、Epikote 1〇〇4 (均由 Japan Ep〇xy Resins 公 司製造）、Epiclon EXA-850CRP ( DIC 公司製造）等。 上述雙酚F型環氧樹脂中之市售樹脂，例如可列舉： Epikote 806、Epikote 4004 (均由 Japan Ep〇xy 公司 製造）、Epiclon EXA-830CRP ( DIC 公司製造）等。 上述雙盼S型環氧樹脂中之市售樹脂，例如可列舉： Epiclon EXA-1514 ( DIC 公司製造）等。 上述2，2’ -一烯丙基雙盼A型環氧樹脂中之市售樹p， 例如可列舉：RE-8 1 0ΝΜ (曰本化藥公司製造）等。 上述氫化雙酴型環氧樹脂中之市售樹脂，* θ w /j日，例如可列 舉：Epiclon EXA-7015 ( DIC 公司製造）等。 12 201124783 上述環氧丙烷加成雙酚A型環氧樹脂中之市售樹脂， 例如可列舉：EP_4000S ( ADEKA公司製造）等。 .上述間苯二酚型環氧樹脂中之市售樹脂，例如可列 舉：EX-201 ( Nagase chemtex 公司製造）等。 上述聯苯型環氧檢脂中之市售樹脂，例如可列舉. Epikote YX_4000H ( Japan Ep〇xy Resins 公司製造）等牛。 上述硫化物型環氧樹脂中之市售樹脂，例如可列舉： YSLV-50TE (東都化成公司製造）等。 上述醚型環氧樹脂中之市售樹脂’例如可列舉： YSLV-80DE (東都化成公司製造）等。 上述二環戊二烯型環氧樹脂中之市售樹脂，例如可列 舉：EP-4088S ( ADEKA公司製造）等。 上述萘型環氧樹脂，例如可列舉：Epicl〇n 、BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a liquid crystal display device which can produce an almost crystal-contaminated liquid crystal display device at low cost and high efficiency. [Prior Art] In recent years, in order to improve the contrast or improve the response speed of liquid crystal display panels, the alignment of liquid crystal molecules by polymer structure is being developed; the PSA (Polymer Sustained AHgnment) method is used instead of the internal opening of the unit. Rib structure The manufacturing process of the liquid crystal display panel of the PSA type is to inject a liquid crystal material having a photopolymerizable component into the cell, and irradiate the ultraviolet light while applying a voltage to the injected liquid crystal material, thereby being in the cell. A polymer structure is formed. The liquid crystal dropping method as one of the methods for retaining the liquid crystal material on the liquid crystal display panel is formed by applying a photocurable sealant to the surface of the light-transmissive substrate constituting the unit to form a frame-shaped sealant layer. After the liquid crystal material containing the monomer is applied to the region surrounded by the sealant layer on the surface of the one translucent substrate, and the other translucent substrate is overlapped, the bonding device of the panel is shown in FIG. The sealant layer is irradiated with light, and the sealant is cured to bond the two light-transmitting substrates. Thereafter, a polymer structure is formed by irradiating ultraviolet rays to the monomer contained in the liquid crystal material to form a unit into which the liquid crystal material is injected. The use of such a liquid crystal material having three monomers, a method of curing the sealant by visible light, and then curing the liquid crystal by ultraviolet rays to form a unit is also commonly used in the blue phase method. For the bonding device of the display panel, for example, a light irradiation device having a portion of the light in the light absorption wavelength region of the radiation-curable sealant (as a light source for irradiating the sealant layer with light) can be used as disclosed in Patent Document 1. ), and a filter that shields light on the short wavelength side. A lamp for such a light irradiation device is generally a metal halide lamp. However, when a PSA method or a blue phase liquid crystal display panel is manufactured by a conventional general light irradiation device using a metal halide lamp, there is a problem that display unevenness occurs. SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a liquid crystal display device which can produce a liquid crystal display device which is almost free of liquid crystal contamination at low cost and high efficiency. The present invention relates to a method for producing a liquid crystal display device, which has a sealant layer formed on a substrate by using a photocurable sealant containing a curable resin and a photopolymerization initiator. Step j: adding a liquid crystal material containing a polymerizable material and a photopolymerization initiator to a region surrounded by the sealant layer; Step 3: bonding the above-mentioned six soil plates to the 3 & substrate by the above-mentioned sealant And irradiating the bonded substrate with the wavelength of the photocuring of the two sealing agents to lightly cure the sealing agent; and: stepping on the wavelength of the photopolymerization of the liquid crystal material; The liquid phase #2 is condensed, and the wavelength of the light which hardens the sealing agent is ,; the wavelength of the light which is photopolymerized by the liquid crystal material is located on the side of the longer wavelength 201124783, and is sealed in the above step 3. The light of the wavelength of the photohardening is irradiated by a light irradiation device having a device and a light-receiving device, and the region of the wavelength at which the above-mentioned LED element is photohardened in the region where the sealing agent is photohardened is a region of a wavelength at which the liquid crystal material is photopolymerized. other than The region has an emission peak wave ", and the half value width of the peak is 3 Gnm or less, and the calender sheet filters out light from the LED element to be shorter than the wavelength of the emission peak wavelength and The light of the region in which the wavelength of the liquid crystal material is photopolymerized is repeated. The invention is described in detail below. The inventors of the present invention have first studied the cause of the occurrence of a problem in which a PSA-type liquid crystal display panel is manufactured by using a general-purpose light irradiation device using a metal halide lamp. The results were ascertained as follows: The metal halide lamp does not show a wide range of broad illuminating light of 2 〇〇 to 6 〇〇 nm. Generally, the photohardenable sealing agent has a photosensitive wavelength of 2 〇〇 to 45 〇. The wavelength at which the liquid crystal material is photopolymerized around the claw is also about 200 to 400 nm depending on the reactive monomer to be used. Therefore, if the metallization material is irradiated by the metal halide lamp in order to harden the sealant, it is considered that the liquid crystal material hardens at the same time, which is considered to cause display unevenness. In order to prevent partial hardening of such a liquid crystal material, the light on the short-wavelength side which shields the liquid crystal material by a filter having a dielectric multilayer film or the like can be irradiated only by light on the long-wavelength side to cure the sealant. However, the filter having the dielectric multilayer film sometimes has a large incident angle dependency, and the light of the target wavelength region cannot be sufficiently shielded due to the difference in the incident angle of light. In order to reliably prevent partial hardening of the liquid crystal material, a light-draining sheet that shields light to the relatively long wavelength side is used. However, if such a filter for shielding light of a wide wavelength region is used, the light irradiated from the metal-chemical lamp is large. The sputum will be obscured and the efficiency of light utilization will be extremely reduced. In fact, the amount of light that is irradiated to the sealant is low and is only light in the long wavelength region. Since such a low-intensity and long-wavelength light does not sufficiently cure the sealant, the sealant component is eluted to the liquid crystal before the sealant is completely cured, causing liquid crystal contamination and uneven display. In order to transfer the amount of light to the sealant, if the irradiation intensity of the metal toothed lamp is set to be extremely high, the amount of light that is not sufficiently shielded on the short-wavelength side is also increased, so that it becomes impossible. Prevent partial hardening of the liquid crystal material. In this way, even if a liquid crystal display panel using a general-purpose light irradiation device using a metal toothed lamp is used, the liquid crystal display panel of the liquid crystal material may be cured by P-knife hardening of the liquid crystal material or liquid crystal contamination caused by poor curing of the sealant. The situation leads to a bad situation of uneven display. Also, metal-fossil lamps have problems in terms of energy conservation. Since the metal halide lamp needs a considerable time (i.e., it is difficult to instantaneously illuminate) from the start of κ5 to the start of the steady state, so in the light irradiation device, the system is continuously lighted by the setting mechanism ☆ In this state, the shutter is opened and closed by the shutter mechanism, and the incident object is irradiated with light when necessary. Therefore, although the actual utilization time is extremely short, it is no longer - the continuous irradiation is inefficient. Also, there is a problem in the shutter mechanism that is lowered. The moving parts are prone to failures. The reliability of the device is used. In view of the above situation, the inventors have found that the sealing agent of the light of the longer wavelength side of the light of the photopolymerization light of 201124783 is hardened. The region outside the region where the wavelength of the liquid b曰 material is photopolymerized in the region where the sealant is photohardened has an emission peak wavelength, and the half value width of the luminescence peak is narrow, and the LED element and "(4) are located at A device for filtering a light having a shorter wavelength on the wavelength side than the wavelength of the LED element and repeating the wavelength of photopolymerization of the liquid crystal material is used as a light irradiation device for irradiating light that hardens the sealant. This makes it possible to manufacture a liquid crystal display device which is almost free of liquid crystal contamination at a low cost and high efficiency, thereby completing the present invention. The LED element has an excellent characteristic that the emission wavelength is extremely clear compared to the metal toothed lamp. The filter 'for filtering the light of the region on the shorter wavelength side of the luminescence peak wavelength of the LED element and repeating the wavelength of photopolymerization of the liquid crystal material is combined with the LED element having the clear luminescence peak, thereby reliably It is possible to prevent the display unevenness caused by the partial hardening of the liquid crystal material and to prevent the large σρ-divided light from being shielded, and to efficiently obtain the light to reach the sealant, so that the sealant can be surely hardened or surely Prevents display unevenness caused by liquid crystal contamination. Further, Φ is excellent in thrift property when the LED element is turned on until it reaches a steady lighting state: the time is extremely short, so that it can be instantaneously clicked, so that it is not required to be straight like a metal toothed lamp. There is no need to set up a complex shutter mechanism for higher reliability. In the method for producing a liquid crystal display device of the present invention, first, a step 1 of forming a frame-shaped sealant layer on a single substrate using a photocurable sealant containing a curable resin and a photopolymerization initiator is carried out. 8 201124783 The above-mentioned sealant is cured by light having a wavelength longer than the wavelength of light which is photopolymerized by the liquid crystal material. The above sealant contains a curable resin and a photopolymerization initiator. The curable resin preferably has a (meth)acrylic acid group and an epoxy earth having eight such a mercapto group, and the obtained encapsulant can be subjected to two-stage hardening by photohardening and thermosetting. Further, in the above curable resin, in the case of having a clear form of a (meth)acryl group and an epoxy group, a ratio of a decyloxy group to a total amount of a (meth)acrylic group and an epoxy group is preferred. When the ratio of the above epoxy group exceeds 40 mol%, the solubility in the liquid crystal is improved, and contamination of the panel may be uneven. A better upper limit is 3 〇 mol%. The curable resin is not particularly limited, and for example, an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group can be obtained by reacting (mercapto)acrylic acid with an epoxy compound. Epoxy (mercapto) acrylate, (meth)acrylic acid amine phthalate obtained by reacting an isocyanate with a hydroxyl group-containing (meth)acrylic acid derivative. The ester compound obtained by reacting (fluorenyl)acrylic acid with a compound having a hydroxyl group is not particularly limited, and examples of the monofunctional one include 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid 2_. Hydroxypropyl ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, (meth) acrylate Isooctyl ester, (mercapto) acrylic laurel vinegar, (stearyl) stearyl acrylate, (mercapto) isopropyl ketone, (cyclo) (meth) acrylate, 2- methoxy (meth) acrylate Ester, decyloxyethylene (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (methyl) 201124783 tetrahydrofurfuryl acrylate, benzyl (meth) acrylate, ethyl card Alcohol (mercapto) acrylate, (meth)acrylic acid, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, ( Mercapto) 2,2,3,3-tetrafluoropropyl acrylate, iH, (H), 1H, 5H-octafluoropentyl ester, (meth) acrylimide, methyl (meth) acrylate, (fluorenyl) ethyl acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate 2 _ Ethylhexyl ester, n-octyl (meth) acrylate, isodecyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, (methyl) 2-phenoxyethyl acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylamine ethyl (meth)acrylate, diamine A (S) Bismuth, 2-(methyl)propenyloxyethyl succinate, hexahydrophthalic acid 2·(methyl)propenyloxyethyl ester, 2-hydroxypropyl phthalate 2-( Methyl) acryloxyethyl ester, glycidyl (mercapto) acrylate, 2-(indenyl) propylene methoxyethyl phosphate, and the like. . Further, the above-mentioned '2-functionality of the ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group is not particularly limited, and for example, 1,4-butanediol di(methyl)propene is exemplified. Acid ester, iota, 3-butanediol di(meth)acrylic acid, 1,6-hexanediol di(indenyl)acrylate, 19-decanediol di(meth)acrylate, 1,1 〇_癸diol bis(indenyl) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol bis(indenyl) acrylate, dipropylene glycol bis(indenyl) acrylate, tripropylene glycol Di(meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di(meth) acrylate 'diethylene glycol bis(indenyl) acrylate 'four 201124783 ethylene glycol bis(indenyl) Acrylate, polyethylene glycol bis(indenyl) acrylate, propylene oxide addition bisphenol A bis(indenyl) acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, epoxy Ethane addition bisphenol F bis(indenyl) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate, 1,3-butylene glycol di(曱) Acrylate, neopentyl glycol bis(indenyl) acrylate, ethylene oxide modified di(meth) acrylate, (hydroxy) (hydroxy) (hydroxy) (hydroxy) (hydroxy) (meth) acrylate Propylene methoxypropyl ester, carbonate diol di(meth) acrylate, polyether diol di(meth) propylene acrylate, polyester diol di(decyl) acrylate, polycaprolactone diol Di(indenyl)acrylate, polybutadienediol di(meth)acrylate, and the like. Further, among the ester compounds obtained by reacting (mercapto)acrylic acid with a compound having a hydroxyl group, the trifunctional or higher functional group is not particularly limited, and examples thereof include pentaerythritol tris(decyl)acrylate and tris(3). Addition of trimethyl (decyl) acrylate to propylene oxide, addition of trimethylolpropane tri(meth) acrylate to propylene oxide, addition of triacetin to tris(methyl) propylene Sour brewing, hexene cool modified hydroxy thiol propyl bromide (decyl enoate, epoxy bake addition of iso-cyanuric acid tris(decyl) acrylate, dipentaerythritol five (fluorenyl) Acrylate, dipentaerythritol hexa(meth) acrylate, bis(trihydroxydecylpropane) tetrakis(mercapto) acrylate vinegar, neopentyl alcohol tetrakis(meth)acrylate vinegar, glycerol Acrylic vinegar, propylene oxide addition glycerol tri(meth)acrylic acid, tris(methyl) propyl methoxy ethoxylate 3, etc. The above is obtained by reacting (hydrazino)acrylic acid with an epoxy compound The epoxy (meth) acrylate vinegar is not particularly limited, and for example, it can be exemplified by a conventional method. In the presence of a catalyst, by the reaction of % oxygen resin with (meth)acrylic acid 11 201124783, β is used as an epoxidation material for synthesizing the above-mentioned epoxy (Yinji) acrylic acid vinegar. There are no special restrictions on t, and there are listed: double powder type epoxy tree wax, double F type nuclear oxygen resin, bisphenol S type epoxy resin, 2,2._diallyl bisphenol A type! Oxygen resin, hydrogenated double-aged epoxy tree, propylene-acrylic acid addition bisphenol A-type oxy-alkali, bismuth epoxy resin, biphenyl type epoxy resin, sulfide-type epoxy Resin, (4) Epoxy Resin, Dicyclopentadiene Epoxy Resin, Qin Epoxy Resin, Benzene Junqing Enamel Epoxy Resin, Neighbor A (4) Disk Varnish 5L Oxygen Tree, 1% Pentadiene Acid-clear g-type epoxy tree, biphenolic acid varnish type epoxy resin, naphthalene varnish type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type Epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin, etc. The commercially available resin in the above bisphenol A type epoxy resin is exemplified by, for example, Epikote 828EL, Epikote 1〇〇4 (both manufactured by Japan Ep〇xy Resins Co., Ltd.), Epiclon EXA-850CRP (manufactured by DIC Corporation), etc. Commercially available resins among the above bisphenol F-type epoxy resins include, for example, Epikote 806, Epikote 4004 (both manufactured by Japan Ep〇xy Co., Ltd.), Epiclon EXA-830CRP (manufactured by DIC Corporation), etc. Commercially available resins in the above-mentioned double-presence S-type epoxy resin include, for example, Epiclon EXA-1514 (DIC The company's commercially available tree p in the 2,2'-monoallyl A-type epoxy resin may, for example, be RE-8 10 0 (manufactured by Sakamoto Chemical Co., Ltd.). The commercially available resin in the hydrogenated bismuth-type epoxy resin, * θ w /j, may be, for example, Epiclon EXA-7015 (manufactured by DIC Corporation). 12 201124783 The commercially available resin in the propylene oxide addition bisphenol A type epoxy resin is exemplified by EP_4000S (manufactured by ADEKA Co., Ltd.). The commercially available resin in the above resorcinol type epoxy resin may, for example, be EX-201 (manufactured by Nagase Chemtex Co., Ltd.). The commercially available resin in the above-mentioned biphenyl type epoxy resin is, for example, a cow such as Epikote YX_4000H (manufactured by Japan Ep〇xy Resins Co., Ltd.). Examples of the commercially available resin in the above-mentioned sulfide-type epoxy resin include YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.). For example, YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.), etc., may be mentioned as a commercially available resin in the above-mentioned ether type epoxy resin. The commercially available resin in the above-mentioned dicyclopentadiene type epoxy resin may, for example, be EP-4088S (manufactured by ADEKA Co., Ltd.). Examples of the above naphthalene type epoxy resin include Epicli〇,

Epiclon EXA-4700 (均由DIC公司製造）等。 上述苯酚酚醛清漆型環氧樹脂中之市售樹脂，例如可 列舉：Epiclon N-770 ( DIC公司製造）等。 上述鄰曱酚酚醛清漆型環氧樹脂中之市售樹脂，例如 可列舉：Epiclon N-670-EXP-S ( DIC 公司製造）等。 上述二環戊二烯酚醛清漆型環氧樹脂中之市售樹脂， 例如可列舉：Epiclon HP7200 ( DIC公司製造）等。 上述聯苯酚酸清漆型環氧樹脂中之市售樹脂，例如可 列舉：NC-3000P (曰本化藥公司製造）等。 上述萘酚酚醛清漆型環氧樹脂中之市售樹脂，例如可 列舉：ESN-165S (東都化成公司製造）等。 13 201124783 上述縮水甘油胺型環氧樹脂中之市售樹脂，例如可列 舉：Epikote 630 ( japan Epoxy Resins 公司製造）、Epicl〇n 430 ( DIC公司製造）、TETRAD-X (三菱瓦斯化學公司製 造）等。 上述烷基多元醇型環氧樹脂中之市售樹脂，例如可列 舉：ZX-1542 (東都化成公司製造）、Epicl〇n 726 ( DIC公 司製造）、Epolight 80MFA(共榮社化學公司製造）、 EX-6 11 ( Nagase chemtex 公司製造）等。 上述橡膠改質型環氧樹脂中之市售樹脂，例如可列 舉：YR-450 ' YR-207 (均由東都化成公司製造）、Ep〇lead PB ( Daicel化學公司製造）等。 上述縮水甘油酯化合物中之市售化合物，例如可列 舉.Denacol EX-147 ( Nagase chemtex 公司製造）等。 上述雙盼A型環硫樹脂中之市售樹脂，例如可列舉：Epiclon EXA-4700 (both manufactured by DIC) and others. The commercially available resin in the phenol novolac type epoxy resin is, for example, Epiclon N-770 (manufactured by DIC Corporation). The commercially available resin in the above-mentioned o-phenol novolak-type epoxy resin is, for example, Epiclon N-670-EXP-S (manufactured by DIC Corporation). The commercially available resin in the above-mentioned dicyclopentadiene novolac type epoxy resin is, for example, Epiclon HP7200 (manufactured by DIC Corporation). The commercially available resin in the above-mentioned biphenolic acid varnish-type epoxy resin is, for example, NC-3000P (manufactured by Sakamoto Chemical Co., Ltd.). The commercially available resin in the naphthol novolac type epoxy resin is, for example, ESN-165S (manufactured by Tohto Kasei Co., Ltd.). 13 201124783 The commercially available resin in the above glycidylamine type epoxy resin, for example, Epikote 630 (manufactured by japan Epoxy Resins), Epicl〇n 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Wait. The commercially available resin in the above-mentioned alkyl polyol type epoxy resin, for example, ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epicl〇n 726 (manufactured by DIC Corporation), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), EX-6 11 (manufactured by Nagase Chemex), etc. The commercially available resin in the rubber-modified epoxy resin may, for example, be YR-450 'YR-207 (all manufactured by Tohto Kasei Co., Ltd.), Ep〇lead PB (manufactured by Daicel Chemical Co., Ltd.), or the like. The commercially available compound among the glycidyl ester compounds may, for example, be Denacol EX-147 (manufactured by Nagase Chemtex Co., Ltd.) or the like. The commercially available resin in the above-mentioned double-prospective A-type episulfide resin may, for example, be:

Epikote YL-7000 ( Japan Epoxy Resins 公司製造）等。 上述環氧樹脂中之其他市售樹脂，例如可列舉： YDC-1312、YSLV-80XY、YSLV_90CR (均由東都化成公司 製造）、XAC4151(旭化成公司製造）、Epik〇te 1〇31、Epik()te 1032(均由 Japan Epoxy Resins 公司製造）、ΕχΑ 7ΐ2〇( dic 公司製造）、TEPIC (日產化學公司製造）等。 上述藉由使（甲基）丙烯酸與環氧化合物反應而獲得之 環氧（曱基）丙烯酸醋，具體而言，例如可藉由如下方式獲 得：一面送入空氣一面將間苯二酚型環氧樹脂（Εχ2〇ι、 Nagase chemtex公司製造）360重量份、作為聚合抑制劑之 201124783 對曱氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、 及丙烯酸2 10重量份於90°C下回流攪拌，並反應5小時。 又，上述環氧（甲基）丙烯酸酯之市售品，例如可列舉：Epikote YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.). Other commercially available resins among the above-mentioned epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV_90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), Epik〇te 1〇31, Epik (). Te 1032 (both manufactured by Japan Epoxy Resins Co., Ltd.), ΕχΑ 7ΐ2〇 (manufactured by dic Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like. The above-mentioned epoxy (mercapto) acrylic vinegar obtained by reacting (meth)acrylic acid with an epoxy compound can be obtained, for example, by, for example, resorcinol-type ring while being supplied with air. 360 parts by weight of an oxygen resin (manufactured by Nagase Chemtek Co., Ltd.), 2,024 parts by weight of 201124783 as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of acrylic acid. The mixture was stirred under reflux at 90 ° C and reacted for 5 hours. Further, examples of the commercially available epoxy (meth) acrylate include, for example:

Ebecryl 860、Ebecryl 3200、Ebecryl 3201、Ebecryl 3412、 Ebecryl 3600、Ebecryl 3700、Ebecryl 3701、Ebecryl 3702、 Ebecryl 3703 、 Ebecryl 3800 、 Ebecryl 6040 、 Ebecryl RDX63 182 (均由 Daicel-Cytec 公司製造），EA-1010、 EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020 (均由 新中村化學工業公司製造），Epoxy Ester M-600A、EpoxyEbecryl 860, Ebecryl 3200, Ebecryl 3201, Ebecryl 3412, Ebecryl 3600, Ebecryl 3700, Ebecryl 3701, Ebecryl 3702, Ebecryl 3703, Ebecryl 3800, Ebecryl 6040, Ebecryl RDX63 182 (all manufactured by Daicel-Cytec), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy

Ester 40EM、Epoxy Ester 70PA、Epoxy Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester 1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA (均由共榮社化學公司製 造），Denacol Acrylate DA-141、Denacol Acrylate DA-314、 Denacol Acrylate DA-911 (均由 Nagase chemtex 公司製造） 等。 上述藉由使異氰酸酯與使具有羥基之（甲基）丙烯酸衍 生物反應而獲得之（甲基）丙烯酸胺曱酸酯，例如可藉由如下 方式獲得：於觸媒量之錫系化合物之存在下，相對於具有2 個異氰酸酯基之化合物i當量，使具有羥基之（曱基）丙烯酸 衍生物2當量與其反應。 上述藉由使異氱酸酯與具有羥基之（曱基）丙烯酸衍生 物反應而獲;f寸之（曱基）丙稀酸胺甲酸酯之原料的異氰酸酯 並無特別限定，例如可列舉：異佛酮二異氰酸酯、2,4_曱苯 15 201124783 二異氰酸酯、2,6-甲苯二異氣酸酯、六亞甲基二異氣酸酯、 三曱基六亞甲基二異氰酸酯、二苯基曱烷-4,4，-二異氰酸酯 (MDI)、氫化MDI、聚合MDI、1，5-萘二異氰酸酯、降获 烷二異氰酸酯、聯曱苯胺二異氰酸酯、苯二亞甲基二異氣 酸酯（XDI)、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷 二異氰酸酿、三（異氰酸苯醋基）硫代填酸醋、四甲基二甲苯 二異氰酸酯、1,6,10-十一烷三異氰酸酯等。 又’上述藉由使異氰酸酯與具有羥基之（曱基）丙烯酸衍 生物反應而獲得之（曱基）丙晞酸胺甲酸g旨之原料的異氣酸 醋並無特別限定，例如亦可使用：藉由乙二醇、甘油、山 梨糖醇、三羥曱基丙烷、（聚）丙二醇、碳酸酯二醇、聚趟二 醇 '聚酯二醇、聚己内酯二醇等多元醇與過量之異氰酸酯 之反應所獲得之經鏈延長之異氰酸酯化合物。 上述藉由使異氰酸酯與具有羥基之（甲基）丙烯酸衍4 物反應而獲得之（甲基）丙烯酸胺甲酸酯之原料的具有羥連 之（甲基）丙烯酸衍生物並無特別限定.，例如可列舉：（甲美 丙烯酸2-羥乙酯、(甲基)丙烯酸2·羥丙酯、(子基)丙烯酸4 發丁醋、（甲基）丙烯酸2-羥丁酯等市售品戎 a c* 一醇、丙二 二:1，3-丙二醇、i，3_丁二醇、M_丁二醇、聚乙二醇等二 凡醇類之單(甲基)丙烯酸酯’三羥甲基乙烷、三羥甲美内 油等三元醇類之單（甲基）丙烯酸酿或二（甲―基）丙利 酉曰，雙酚A改質環氧丙烯酸酯等環氧丙烯酸酯等。 上述（甲基）丙稀酸胺甲酸酯之市售ρ ， M-U00、Μ_1200、Μ·121〇 ' 心：:東=可列舉： 甶東亞合成公司製 16 201124783 造）；Ebecryl 230、Ebecryl 270、Ebecryl 4858、Ebecryl 8402、 Ebecryl 8804、Ebecryl 8803、Ebecryl 8807、Ebecryl 9260、 Ebecryl 1290、Ebecryl 5129、Ebecryl 4842、Ebecryl 210、 Ebecryl 4827、Ebecryl 6700、Ebecryl 220、Ebecryl 2220 (均 由 Daicel-Cytec 公司製造）；Art Resin UN-9000H、Art Resin UN-9000A、Art Resin UN-7100、Art Resin UN-1255、Art Resin UN-330、Art Resin UN-3320HB、Art Resin UN-1200TPK、Art Resin SH-500B (均由根上工業公司製 造）；U-122P、U-108A、U-340P、U-4HA、U-6HA、U-324A、 U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、U-2HA、 U-2PHA、UA-4100、UA-7100、UA-4200、UA-4400、 UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、 U-340A、U-108、U-6H、UA-4000 (均由新中村化學工業公 司製造）；AH-600、AT-600、UA-306H、AI-600、UA-101T、 UA-101I、UA-306T、UA-306I 等。 關於上述具有（甲基）丙烯酸基之樹脂，就抑制對液晶造 成之不良影響方面而言，較佳為具有-0H基、-NH-基、-NH2 基等氫鍵性單元者，就合成之容易性等方面而言，特佳為 環氧（曱基）丙稀酸酯。 又，關於上述具有（曱基）丙烯酸基之樹脂，就反應性之 高低程度而言，較佳為分子中具有2〜3個（曱基）丙烯酸基 者。Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (both by Kyoei Chemical Co., Ltd.) Manufactured, Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemtex), and the like. The above (meth)acrylic acid amine phthalate obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group can be obtained, for example, by the presence of a catalyst amount of a tin-based compound. 2 equivalents of the (indenyl)acrylic acid derivative having a hydroxyl group are reacted with respect to the compound i equivalent having 2 isocyanate groups. The isocyanate obtained by reacting an isophthalic acid ester with a (mercapto)acrylic acid derivative having a hydroxyl group; the isocyanate of the raw material of the (indenyl) acrylic acid urethane is not particularly limited, and examples thereof include, for example, Isophorone diisocyanate, 2,4-nonylbenzene 15 201124783 Diisocyanate, 2,6-toluene diisophthalate, hexamethylene diisophthalate, trimethyl hexamethylene diisocyanate, diphenyl Cyclodecane-4,4,-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, reduced alkane diisocyanate, decyl aniline diisocyanate, benzodiamidylene diisophthalic acid Ester (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane diisocyanate, tris(phenylisocyanate) thioacetate, tetramethylxylene diisocyanate, 1,6 , 10-undecane triisocyanate, and the like. Further, the above-mentioned isogastric acid vinegar obtained by reacting an isocyanate with a (mercapto) acrylic acid amide having a hydroxyl group (mercapto) acrylic acid derivative is not particularly limited, and for example, it is also possible to use: By polyols such as ethylene glycol, glycerin, sorbitol, trihydroxydecylpropane, (poly)propylene glycol, carbonate diol, polydecanediol 'polyester diol, polycaprolactone diol, etc. A chain extended isocyanate compound obtained by the reaction of an isocyanate. The (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the (meth)acrylic acid urethane obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group is not particularly limited. For example, commercially available products such as 2-methyl acrylate, 2-hydroxypropyl (meth)acrylate, 4-butyl acetonate, and 2-hydroxybutyl (meth)acrylate may be mentioned. Ac* monool, propylene dichloride: 1,3-propanediol, i, 3-butanediol, M-butanediol, polyethylene glycol, etc. Mono- (meth)acrylic or tris(methyl)propanol, trisphenol A modified epoxy acrylate, etc., such as ethane or trishydroxyl oil The above-mentioned (meth)acrylic acid urethane is commercially available as ρ, M-U00, Μ_1200, Μ·121〇' heart:: East = can be listed as: 甶 East Asia Synthetic Company made 16 201124783); Ebecryl 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402, Ebecryl 8804, Ebecryl 8803, Ebecryl 8807, Ebecryl 9260, Ebecryl 1290, Ebecryl 5129, Ebecryl 4842 Ebecryl 210, Ebecryl 4827, Ebecryl 6700, Ebecryl 220, Ebecryl 2220 (both manufactured by Daicel-Cytec); Art Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Gensei Industrial Co., Ltd.); U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA- 340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); AH- 600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, etc. The resin having a (meth)acrylic group is preferably a hydrogen bond unit having an -OH group, a -NH- group or a -NH 2 group in terms of suppressing adverse effects on the liquid crystal. Epoxy (mercapto) acrylate is particularly preferred in terms of ease of use and the like. Further, the resin having a (fluorenyl) acrylate group preferably has 2 to 3 (fluorenyl) acrylate groups in the molecule in terms of the degree of reactivity.

上述用於密封劑之光聚合起始劑於曱醇或乙腈溶劑中 所測得之對405 nm之波長的吸光係數之較佳下限為50 mL 17 201124783 /g · cm。若上述對405 nm之波長的吸光係數未達5〇 mL / g · cm，則存在密封劑之硬化變得不充分，導致液晶污染 之情形。上述吸光係數之更佳下限為7〇 mL/ g · cm。 上述吸光係數存在數值越高則反應性越高之傾向，因 此其並無特別上限。 上述用於密封劑之光聚合起始劑較佳為：將曱醇或乙 腈吟劑中之濃度設為01重量％時的吸光波長區域與較下述 LED 7C #之發光波長區域中之由遽光片㊣滤掉《波長區域 更長波長側的發光波長區域具有50%以上之重疊。藉由使 用此種光聚合起始劑’可高效率地使密封劑層硬化。 上述用於密封劑之光聚合起始劑較佳為不會因U 〇。^ 以下溫度之加熱而產生自由I。若上述用於密封劑之光聚 合起始劑會因13(rc以下溫度之加熱而產生自由基，則存在 ;製&液曰曰顯不裝置時生成光聚合起始劑之分解物，引起 液晶污染之情形。 - 述用於搶封劑之光聚合起始劑車交佳為吸光波長 ----丁人丨工π 7D ?汉焚匪ΐ 波長側端未達45〇 nm。若上述用於密封劑之光聚合* =吸收波長450 nmw上之光，則存在於黃色燈下亦發j 反應’密封劑之操作性變差之情形。 ㉛用於⑧封劑之光聚合起始#|，例如可適當$ 化入私本甲：系化合物、苯乙酮系化合物、醯基氧化膦， ::，二茂鈦系化合物、肪醋系化合物、安息香驗“ :本偶酿、硫雜葱酮等。該等光聚合起始劑可單獨々 用，亦可併用2種以上。 18 201124783 又’作為上述光聚合起始劑中之市售者，例如可列舉： Irgacure 379 ' Irgacure 819 ' Irgacure OXEOl > Irgacure OXE02、Irgacure 907、Darocur TPO、ITX (以上均由 CibaThe preferred lower limit of the absorption coefficient of the photopolymerization initiator for the sealant in the decyl alcohol or acetonitrile solvent to the wavelength of 405 nm is 50 mL 17 201124783 /g · cm. If the above-mentioned absorption coefficient for the wavelength of 405 nm is less than 5 〇 mL / g · cm, the hardening of the sealant may become insufficient, resulting in liquid crystal contamination. A lower limit of the above absorption coefficient is 7 〇 mL / g · cm. The higher the value of the above-mentioned light absorption coefficient, the higher the reactivity tends to be, and therefore there is no particular upper limit. The photopolymerization initiator for the sealant is preferably a light-absorbing wavelength region when the concentration in the decyl alcohol or acetonitrile oxime is 01% by weight and a light-emitting wavelength region of the LED 7C # described below. The light sheet is filtering out "the wavelength region of the longer wavelength side of the wavelength region has an overlap of 50% or more. The sealant layer can be hardened efficiently by using such a photopolymerization initiator. The above photopolymerization initiator for the sealant is preferably not caused by U 〇. ^ The heating of the following temperatures produces a free I. If the photopolymerization initiator used for the sealant is generated by the heating of 13 (the temperature below rc, it exists; when the product is formed, the decomposition product of the photopolymerization initiator is generated, causing The case of liquid crystal contamination. - The photopolymerization initiator used for the sealant is the light absorption wavelength----Ding Renjian π 7D? Han incineration The wavelength side end is less than 45〇nm. Photopolymerization for sealant* = absorption of light at a wavelength of 450 nmw, which is also present under a yellow lamp. The reaction of the sealant is deteriorated. 31 Photopolymerization start for 8 sealants# |, for example, can be appropriately converted into a private one: a compound, an acetophenone-based compound, a fluorenylphosphine oxide, ::, a titanocene compound, a fatty vinegar compound, a benzoin test ": this brewed, thia The photopolymerization initiator may be used alone or in combination of two or more. 18 201124783 Further, as a commercially available one of the above photopolymerization initiators, for example, Irgacure 379 'Irgacure 819 ' Irgacure OXEOl > Irgacure OXE02, Irgacure 907, Darocur TPO, ITX (all above by Ciba

Japan公司製造）等。再者，於併用2種以上之光聚合起始 劑之情形時，例如可考慮併用Irgacure 907與Ιτχ等。 作為上述用於密封劑之光聚合起始劑之含量並無特別 限定，較佳下限為〇 2重量％，較佳上限為丨〇重量％。若上 述用於密封劑之光聚合起始劑之含量未達〇2重量％，則存 在硬化不充分之情形，若超過1〇重量％，則存在產生液晶 亏柒或對基板之附著力降低之情形。上述用於密封劑之 光聚合起始劑之含量之更佳下限為丨〇重量％，更佳上限為 5 · 0重量％。 於上述硬化性樹脂含有具有環氧基之樹脂之情形時， 較佳為上述密封劑更含有熱硬化劑。上述熱硬化劑並無特 別限之例如可列舉：有機酸醯肼、咪唑衍生物、胺化合 多酚系化合物、酸酐等。其中，固體有機酸醯肼較適 用。 上述固體有機酸醯肼並無特別限定’例如可列舉：癸 -义一醯肼、間苯二甲酸二醯肼、己二酸二醯肼等，作為 售者例如可列舉：Amicure VDH、Amicure UDH (均由 jinomoto Fine_Techn〇公司製造）、adh (大塚化學公司 製造）等。 且上述密封劑亦可含有矽烷偶合劑。上述矽烷偶合劑主 為提阿上述在、封劑與基板之黏接性的黏接助劑之 19 201124783 功能。 ^ 上述矽烷偶合劑雖無特別限定，但由於以下所列者之 提高與基板之黏接性之效果優異，且可藉由與硬化性㈣ 化學鍵結㈣止其流出至液晶材料中，因此可適當地使 用，例如：r-甲基丙烯醯氧基丙基三甲氧基石夕⑦、卜胺基 丙基三甲氧基矽烷、r省丙基三甲氧基矽烷、卜縮水甘油 氧基丙基三甲氧基錢、r•異氰酸自旨基丙基三甲氧基㈣ (r-⑽yanat〇propyltrimethoxysilane)等。該等㈣偶合劑 可單獨使用’亦可併用2種以上。 為了藉由應力分散效果而改善黏接性、線性膨脹係 數，上述密封劑亦可含有填充劑。 上述填充劑並無特別限定，例如可列舉：滑石' 石棉、 石夕土、石夕藻土、膨潤石、膨潤土、碳酸舞、碳酸鎂、氧化 =豕脫石：矽藻土、氧化鋅、氧化鐵、氧化鎂、氧化錫、 氫氧化鎂 '氫氧化鋁 '玻璃硃' 氮化矽、硫酸鋇' 夕㈣、㈣雲母活性白土、氮化料無機填充劑， 粒子、聚胺甲酸酷微粒子、乙稀基聚合物微粒子、 丙烯馱系聚合物微粒子等有機填充劑。 利用E型黏度計 度上限為6〇 、C下測疋上述密封劑而獲得的黏 心L生不。且若盈上述密封劑之黏度超過60萬 元件。上述藉由滴下法製造液晶顯示 45萬mPa· s。 下限為10 “Pa· s，較佳上限為 lJ疋上述密封劑之黏度之E型黏度計並無特別 20 201124783 限定，例如可列舉：Brookfi ld公 』製造之「DV-ΙΙΙ」等。 1k上述密封劑之方法並無特 τ乃』I民疋，可列舉將上沭 硬化性樹脂、上述光聚合起始劑、 之 久矾需要摻合之上述埶 硬化劑、上述石夕烧偶合劑等之特定量藉由先前公知之方: 加以混合之方法等。此時，為了去除所含有之離子性雜質， 亦可使其與離子吸附性固體接觸。 於本發明之液晶顯示裝置之製 I迈方法中，其次進行將 含有聚合性材料與光聚合起始劑 芯谢劁之液晶材料滴加於由上述 畨封劑層包圍之區域的步驟2。 上述液晶材料含有聚合性材料與光聚合起始劑。 此種液晶材料，例如可使用：曰本特開2〇〇3_3〇772〇 號公報、曰本特開，9_1〇4119號公報、曰本特開 2009-132718號公報中所揭示之材料。 於本發明之液晶顯示裝置之製造方法中，其次進行藉 由上述密封劑將上述-塊基板與另—塊基板貼合，對該^ 貼合之基板照射使上述密封劑光硬化之波長之光，而使上 述密封劑光硬化之步驟3。 上述步，驟3巾照射之光之照身士量雖亦取決於上述密封 劑之種，，但405 _之波長之累計光量之較佳下限為i 〇〇 mJ/ cm，較佳上限為5〇〇〇 mj/ 。若上述累計光量未達 則存在上述密封劑無法充分硬化污染液晶 導致員示不均之情形，若超過5000 mJ/ cm2 ,則存在部 刀液日日材料發生聚合，導致顯示不均之情形。上述累計光 量之更佳下限為l000 mJ//cm2,更佳上限為3〇〇〇mj/cm2。 21 201124783 上述步驟3中使密封劑光硬化之波長之光係'由具有 LED το件與濾光片之光照射裝置照射。 上述LED元件係選用於使上述密封劑光硬化之波長的 區域内之除使上述液晶材料光聚合之波長的區域以外之區 域具有發光峰值波長者。 丨 若上述發光峰值波長處於使上述密封劑光硬化之波長 之區域外，則無法使上述密封劑充分硬化。若上述發光峰 值波長處於使上述液晶材料光聚合之波長之區域内，則無 法使上述密封劑充分硬化，或因濾光片未能完全遮斷之光 導致上述液晶材料發生光聚合。 上述LED元件之發光峰之半值寬度較佳為3〇 以 下。若上述半值寬度超過3〇 nm，則存在光之利用效率降 低，或因濾光片未能完全遮斷之光導致上述液晶材料發生 光聚合之情形。上述半值寬度並無特別下限，越窄越佳， 貫質之下限為1〇 nm左右。 關於上述LED元件，例如可使用銦（In )系LED元件 或含有鋁（A1)之氮化鎵（GaN)系LED元件等先前公知 之LED元件。關於上述LED元件之發光峰，藉由調整led 中之In、A1、GaN之組成比，可獲得具有自2〇〇 nm至紅外 區之發光峰值波長的LED元件。只要自該等led元件中選 用於使上述密封劑光硬化之波長的區域内之除使上述液晶 材料光聚合之波長的區域以外之區域具有發光峰值波長、 並且發光峰之半值寬度較窄之LED元件即可，具體而言例 如選用具有3 60〜420 nm之發光峰值波長且發光峰之半值 22 201124783 見度為30 ητη以下之LED元件即可。 上述具有360〜420 nm之發光峰值波長且發光峰之半 值寬度為1〇〜30⑽之LED元件可使用市售者於無適當 之市售品之情形時，亦可使用特訂品。 田 上述濾光片係用以過濾掉自上述LED元件照射之光中 位於較上述發光峰值波長更短波長側且與使上述液晶材料 光聚合之波長重複之區域之光。更具體而t，係選用截止 波長（透光率成為50%之波長）為較上述LED元件之發光 峰值波長更短波長側且較與使上述液晶材料光聚合之波長 重複之區域更長波長側的遽光片。其中，宜採用可冑38〇麵 以下之光之穿透率為〇的濾光片。 圖5係示意性表示於本發明之液晶顯示裝置之製造方 法中上述LED元件之發光光譜與上述濾光片之分光特性之 關係的曲線圖。 如圖5示意性所示，上述LED元件係具有曲線⑴所 不之發光光譜者，上述濾光片，係具有曲線（F )所示之分 光特性者，亦即，係過濾掉LED元件照射之光中位於較lED 疋件之發光峰值波長更短波長側且與使液晶材料2光聚合 之波長重複之區域之光（圖5中之斜線部分之光）者。 若使用具有上述LED元件與濾光片之光照射裝置，由 於經由「過濾掉位於較上述發光峰值波長更短波長側且與 使上述液晶材料光聚合之波長重複的區域之光」之濾光片 ’系射來自發光光譜之波長區域較窄之LED元件之光，因此 照射之光之波長分佈極产。因此，根據使上述密封劑光硬 23 201124783 化之波長之區域及使上述该a 又上地/夜晶材料光聚合之波 擇LED元件，可在不使 & £成選 m 曰材#令之光聚合性成分進行聚 合反應之情形下，以較苒也 订取 化。 較r"之先利用效率使上述密封劑層硬 述光截止特性者則無特別限 層臈者。 ’但於無適當之市售品之情 上述濾光片只要為具有上 疋，例如可利用具有介電體多 上述遽光片可使用市售者 形時，亦可使用特訂品。 又’上述光照射裝置敍祛A 立 _ 衣亙敉佳為於任意面上配置有複數個 LED元件與遽光片者。上述井昭私括™ a* , . 述尤照射裝置#由具有此種構成， 可根據密封劑層之形態選擇具有可點亮之led元件與濾光 片之光照射部（以下亦稱為光源區段），且可選擇性地對 密封劑層照射光。因此，可獲得更高之能量效率且不再需 要為了選擇性地對上述密封劑層照射光而設置光罩，因此 可降低製造成本。X，於上述光源區段中之一個㈣元件 發生劣化時，藉由提高其他LED元件之照射強度，可使光 源區段整體照射穩定光量之光。 進而上述光照射裝置具有收納上述LED元件而成之 LED封裝，且亦可於該LED封裝上設置上述濾光片。上述 光照射裝置藉由具有此種構成，而不再需要設置大面積之 遽光片’因此可降低濾光片之成本並提高生產性。 於本發明之液晶顯示裝置之製造方法中，其次進行照 射使液晶材料光聚合之波長之光，而使上述液晶材料光聚 合之步驟4。 24 201124783 再者’於照射使上述液晶材料光聚合之波長之光之過 程中，藉由施加電壓，可控制液晶分子之初期形成角度。 以下’使用圖對本發明之液晶顯示裝置之製造方法進 行說明。 圖1係表不具有上述光照射裝置之顯示面板之貼合裝 置之一例之構成概略的說明圖。於上述顯示面板之貼合裝 置（以下簡稱為「貼合裝置」）中，於基台丨丨上，經由支 持台12設置有載置處理對象物之載置台1〇，於該載置台 10之上方配置有上述光照射裝置15。 上述貼合裝置之處理對象物丨係於2塊透光性基板4 之間形成液晶材料2與以圍繞該液晶材料2周圍之方式將 其包圍之密封劑層3而成者。該例中之處理對象物丨係用 以製造合計4塊顯示面板者，於該處理對象物丨中如圖2 所不，形成有彼此存在一定間隔而縱橫排列之4塊液晶材 料2與分別包圍一塊液晶材料2之4個密封劑層3。 光照射褒置15如圖3所示，係於適宜之支持體（省略 圖式）上以縱橫排列之方式配置複數個光源區段而構成。 於各個光源區段20中，如圖4所示，於同一矩形基板 21之表面配置有複數個LED元件25，於各個該等LED元 件25之表面’以包覆該LED元件25之方式設置有濾光片 30 〇 又’於基板21之表面之周圍部，配置有内面為光反射 面之矩形之筒狀之導光構件26,於該基板21之背面，設置 有將LED兀件25所散發之熱量散去的散熱用鰭片27。 25 201124783 個 各個光源區段20之LED元件25 之數量例如為5〜16 於上述光照射裝置15中，於所有光源區段2〇中使 根據處理對象4勿1中之密封劑層3之形狀而選擇之光源區 段20運作’而使來自該光源區段2〇中之㈣元件25的光 經由濾光片30自導光構件26之光出射部28出射，並照射 至貼合裝置之載置台H)上配置之處理對象物i中之密封劑 層3，藉此使密封劑層3硬化。 圖6係表示上述光照射裝置之另一例中之光源區段之 構成的說明圖。 於該光源區段20中，於同一矩形基板21之表面配置 有複數個LED封裝35，於該基板21之表面之周圍部配置 有内面為光反射面之矩形之筒狀之導光射％，於該基板 21之背面設置有將㈣封裝乃散發之熱兩散去之散熱用 鰭片27。 各個封裝35如圖7所示’具有中央形成有矩形之 凹部37的封裝基板36,該封裝基板％之凹部37内 LED元件25，且設置有封堵該封裝基板％之凹部 狀之滤光Θ 30。又，28係導光構件26之光Made by Japan company). Further, when two or more kinds of photopolymerization initiators are used in combination, for example, Irgacure 907, Ιτχ, or the like can be used in combination. The content of the photopolymerization initiator used as the sealant is not particularly limited, and a preferred lower limit is 〇 2% by weight, and a preferred upper limit is 丨〇 by weight. When the content of the photopolymerization initiator for the sealant is less than 2% by weight, the curing may be insufficient. If it exceeds 1% by weight, the liquid crystal may be insufficient or the adhesion to the substrate may be lowered. situation. A more preferred lower limit of the content of the photopolymerization initiator for the sealant is 丨〇% by weight, and more preferably 5% by weight. In the case where the curable resin contains a resin having an epoxy group, it is preferred that the sealant further contains a thermosetting agent. The thermosetting agent is not particularly limited, and examples thereof include an organic acid hydrazine, an imidazole derivative, an aminated polyphenol compound, and an acid anhydride. Among them, solid organic acid strontium is more suitable. The solid organic acid hydrazine is not particularly limited, and examples thereof include hydrazine-isoindole, diammonium isophthalate, and diammonium adipate. Examples of the product include Amicure VDH and Amicure UDH. (all manufactured by Jinomoto Fine_Techn Co., Ltd.), adh (manufactured by Otsuka Chemical Co., Ltd.), etc. Further, the above sealant may also contain a decane coupling agent. The above-mentioned decane coupling agent is mainly a bonding aid of the above-mentioned adhesion between the sealing agent and the substrate. ^ The above-mentioned decane coupling agent is not particularly limited, but is excellent in the effect of improving the adhesion to the substrate as listed below, and can be discharged into the liquid crystal material by chemical bonding with the curable (4) chemical bonding, thereby being suitable. For use, for example: r-methacryloxypropyltrimethoxyxanthine 7, aminopropyltrimethoxydecane, r-propyltrimethoxydecane, glycidoxypropyltrimethoxy Money, r•isocyanate, propyltrimethoxysilane, etc. (r-(10)yanat〇propyltrimethoxysilane). These (4) coupling agents may be used singly or in combination of two or more. In order to improve the adhesion and the coefficient of linear expansion by the stress dispersion effect, the above sealant may also contain a filler. The filler is not particularly limited, and examples thereof include talc's asbestos, Shishi soil, Shishizao soil, bentonite, bentonite, carbonated dance, magnesium carbonate, oxidation = strontium: diatomaceous earth, zinc oxide, and oxidation. Iron, Magnesium Oxide, Tin Oxide, Magnesium Hydroxide 'Aluminum Hydroxide' Glass Zhu's Tantalum Nitride, Barium Sulfate's (4), (4) Mica Activated White Clay, Nitride Inorganic Filler, Particles, Polyurethane Cool Microparticles, B An organic filler such as a dilute base polymer microparticle or an acrylonitrile-based polymer microparticle. The viscous heart L obtained by measuring the above-mentioned sealant under the upper limit of the E-type viscosity is 6 〇 and C. And if the above sealant has a viscosity of more than 600,000 components. The above liquid crystal display was produced by a dropping method of 450,000 mPa·s. The lower limit is 10 "Pa·s, and the preferred upper limit is lJ. The viscosity of the above-mentioned sealant is not limited to the specific type of 201124783, and examples thereof include "DV-ΙΙΙ" manufactured by Brookfild. The method of the above-mentioned sealing agent is not particularly high, and the above-mentioned enamel curing agent, the above-mentioned photopolymerization initiator, and the above-mentioned cerium hardening agent which are required to be blended, and the above-mentioned stone smelting coupling agent are exemplified. The specific amount is equal to the previously known method: a method of mixing, and the like. At this time, in order to remove the ionic impurities contained, it may be brought into contact with the ion-adsorbing solid. In the method for producing a liquid crystal display device of the present invention, a step 2 of dropping a liquid crystal material containing a polymerizable material and a photopolymerization initiator core into a region surrounded by the above-mentioned enamel sealant layer is carried out. The above liquid crystal material contains a polymerizable material and a photopolymerization initiator. For the liquid crystal material, for example, the materials disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2009-132718. In the method of manufacturing a liquid crystal display device of the present invention, the above-mentioned block substrate and the other substrate are bonded together by the above-mentioned sealant, and the substrate to be bonded is irradiated with light having a wavelength at which the sealant is photohardened. And step 3 of photohardening the above sealant. In the above steps, the amount of light to be irradiated by the towel is also dependent on the above-mentioned sealant species, but the preferred lower limit of the cumulative light amount of the wavelength of 405 _ is i 〇〇 mJ / cm, and the upper limit is preferably 5 〇〇〇mj/. If the amount of accumulated light is not reached, the above-mentioned sealant may not be sufficiently hardened to contaminate the liquid crystal, resulting in unevenness of the member. If it exceeds 5000 mJ/cm2, the material of the knife-day liquid may be polymerized, resulting in uneven display. A more preferable lower limit of the above cumulative light amount is l000 mJ/cm 2 , and a more preferable upper limit is 3 〇〇〇 mj/cm 2 . 21 201124783 The light system of the wavelength at which the sealant is photohardened in the above step 3 is irradiated by a light irradiation device having LEDs and filters. The LED element is selected to have an emission peak wavelength in a region other than a region in which the wavelength of the liquid crystal material is photopolymerized in a region where the sealing agent is photohardened.丨 If the above-mentioned luminescence peak wavelength is outside the region where the sealing agent is photohardened, the above-mentioned sealant cannot be sufficiently cured. When the wavelength of the luminescence peak is in a region where the wavelength of the liquid crystal material is photopolymerized, the above-mentioned liquid crystal material cannot be sufficiently cured by the above-mentioned liquid crystal material due to insufficient curing of the above-mentioned sealing agent or light which is not completely blocked by the filter. The half value width of the luminescence peak of the above LED element is preferably 3 Å or less. If the half value width exceeds 3 〇 nm, there is a case where the light use efficiency is lowered or the liquid crystal material is photopolymerized due to the light which is not completely blocked by the filter. There is no particular lower limit for the above-mentioned half-value width, and the narrower the better, the lower limit of the quality is about 1 〇 nm. As the LED element, for example, a conventionally known LED element such as an indium (In) type LED element or a gallium nitride (GaN) type LED element containing aluminum (A1) can be used. With respect to the luminescence peak of the above LED element, an LED element having an emission peak wavelength from 2 〇〇 nm to the infrared region can be obtained by adjusting the composition ratio of In, A1, and GaN in the LED. An LED having a light-emitting peak wavelength and a half-value width of a light-emitting peak in a region other than a region in which the wavelength of the liquid crystal material is photopolymerized in a region in which the above-mentioned liquid crystal material is photopolymerized is selected from the above-mentioned LED elements. The element may be, for example, an LED element having an emission peak wavelength of 3 60 to 420 nm and a half value 22 201124783 of 30 ητη or less. The above-mentioned LED element having an emission peak wavelength of 360 to 420 nm and a half-value width of the luminescence peak of 1 〇 to 30 (10) can be used in the case where a commercially available product is not commercially available, and a special product can be used. The filter is configured to filter out light from a region irradiated by the LED element at a wavelength shorter than the wavelength of the emission peak and overlapping with a wavelength at which the liquid crystal material is photopolymerized. More specifically, t is a wavelength at which the cutoff wavelength (wavelength at which the light transmittance is 50%) is shorter than the wavelength of the light-emitting peak of the LED element and is longer than the region where the wavelength of the liquid crystal material is photopolymerized. The twilight film. Among them, it is preferable to use a filter having a light transmittance of 〇 below 38 〇. Fig. 5 is a graph schematically showing the relationship between the light emission spectrum of the LED element and the spectral characteristics of the filter in the method of manufacturing a liquid crystal display device of the present invention. As schematically shown in Fig. 5, the LED element has an emission spectrum which is not shown by the curve (1), and the filter has a spectral characteristic as shown by the curve (F), that is, the LED element is filtered. The light in the region of the light having a shorter wavelength side than the emission peak wavelength of the lED element and which is a region where the wavelength of the liquid crystal material 2 is photopolymerized (the light of the oblique portion in Fig. 5). When a light irradiation device having the LED element and the filter is used, a filter that filters out light in a region that is shorter than the wavelength of the light emission peak and repeats the wavelength of photopolymerization of the liquid crystal material is used. 'The light from the LED elements having a narrow wavelength region from the luminescence spectrum is emitted, so the wavelength distribution of the illuminating light is extremely high. Therefore, according to the wavelength region in which the above-mentioned sealant hardening 23 201124783 is formed, and the wave-selective LED element which photopolymerizes the a-upper/infrared crystal material described above, it is possible to prevent the & £ from being selected as the m-coffin. In the case where the photopolymerizable component is subjected to a polymerization reaction, it is also prepared in a relatively fine manner. The efficiency of the above-mentioned sealant layer is more limited than that of the r" However, in the case where the above-mentioned filter is not available, the above-mentioned filter may be a commercially available one, for example, a commercially available one may be used. Further, the light-emitting device described above is a plurality of LED elements and a light-receiving sheet disposed on any surface. The above-mentioned well-in-laws include a light-emitting portion (hereinafter also referred to as a light source) having a illuminable LED element and a filter according to the form of the sealant layer. Section) and selectively illuminating the sealant layer. Therefore, higher energy efficiency can be obtained and it is no longer necessary to provide a photomask in order to selectively irradiate the above-mentioned sealant layer with light, so that the manufacturing cost can be reduced. X, when one of the (4) elements of the light source section is deteriorated, by increasing the irradiation intensity of the other LED elements, the entire light source section can be irradiated with light of a stable amount of light. Further, the light irradiation device may include an LED package in which the LED element is housed, and the filter may be provided on the LED package. By having such a configuration, the above-described light irradiation device eliminates the need to provide a large-area calender sheet', thereby reducing the cost of the filter and improving productivity. In the method for producing a liquid crystal display device of the present invention, the step 4 of irradiating the liquid crystal material with light at a wavelength of the liquid crystal material is irradiated. 24 201124783 Further, in the process of irradiating light of a wavelength at which the liquid crystal material is photopolymerized, an initial angle of formation of liquid crystal molecules can be controlled by applying a voltage. The method of manufacturing the liquid crystal display device of the present invention will be described below using the drawings. Fig. 1 is an explanatory view showing a schematic configuration of an example of a bonding apparatus of a display panel which does not have the above-described light irradiation device. In the above-described display panel bonding apparatus (hereinafter simply referred to as "bonding apparatus"), the mounting table 12 on which the processing object is placed is placed on the base station via the support table 12, and the mounting table 10 is placed on the mounting table 10. The above-described light irradiation device 15 is disposed above. The object to be treated of the bonding apparatus is formed by forming a liquid crystal material 2 between the two light-transmitting substrates 4 and a sealant layer 3 surrounding the liquid crystal material 2 so as to surround the liquid crystal material 2. The object to be processed in this example is used to manufacture a total of four display panels. In the object to be processed, as shown in FIG. 2, four liquid crystal materials 2 which are vertically and horizontally arranged at a certain interval are formed and surrounded. A layer of sealant 3 of a liquid crystal material 2. As shown in Fig. 3, the light irradiation means 15 is constructed by arranging a plurality of light source sections in a vertical and horizontal arrangement on a suitable support (omitted from the drawing). In each of the light source sections 20, as shown in FIG. 4, a plurality of LED elements 25 are disposed on the surface of the same rectangular substrate 21, and the surface of each of the LED elements 25 is disposed to cover the LED elements 25. The filter 30 and the peripheral portion of the surface of the substrate 21 are disposed with a rectangular tubular light guiding member 26 whose inner surface is a light reflecting surface, and the LED element 25 is disposed on the back surface of the substrate 21. The heat dissipation fins 27 are dissipated by the heat. 25 201124783 The number of the LED elements 25 of the respective light source sections 20 is, for example, 5 to 16 in the light irradiation device 15, and the shape of the sealant layer 3 according to the processing object 4 is made in all the light source sections 2? The selected light source section 20 operates to emit light from the (four) element 25 of the light source section 2 through the filter 30 from the light exit portion 28 of the light guiding member 26 and to illuminate the bonding device. The sealant layer 3 in the object to be processed i disposed on the H) is placed, whereby the sealant layer 3 is cured. Fig. 6 is an explanatory view showing a configuration of a light source section in another example of the light irradiation device. In the light source section 20, a plurality of LED packages 35 are disposed on the surface of the same rectangular substrate 21, and a rectangular cylindrical light guide % having a light reflecting surface on the inner surface is disposed on a peripheral portion of the surface of the substrate 21. On the back surface of the substrate 21, fins 27 for dissipating heat which dissipate heat from the (four) package are provided. Each of the packages 35 has a package substrate 36 having a rectangular recess 37 formed therein, an LED element 25 in the recess 37 of the package substrate, and a filter having a recessed portion that blocks the package substrate. 30. Moreover, the light of the 28-type light guiding member 26

元件25及濾光片30之特性與圖4 &quot;斤示之光 之LED元件及濾光片相同。 又T 上述光照射裝置如下所示可實施..各種變更。 ⑴於圖4所示之光源區段2〇中，遽光 圖8所示，為具有透鏡功能之半球狀者。 亦可如 26 201124783 入 央位置設置如圖9所示於導光構件26之筒孔内之中 r F〜光片30的構成，來代替將濾光片30設 置於各個LED元件25上。 26之筒孔内之頂端 LED封裝35中所 •為具有透鏡功能 &lt;叩，邳可如圖9所i 側位置配置積分器透鏡29 (2)於圖6所示之光源區段20中 設置之濾光片30亦可如圖1〇(a)所示 之半球狀者。 〇封裝35亦可如圖10 (b)所示，於板狀之濾 先片30之表面設置透鏡31。 ，根據本發明，可提供一種可以低成本且高效率製造幾 乎液/亏染之液晶顯示裝置的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尤其適用力PS a方 式或藍相方式之液晶顯示裝置之製造。 【實施方式】 以下提出實施例對本發明進而詳細地進行說明，但本 發明並不僅限定於該等實施例。 〈硬化性樹脂之合成〉 (雙酚A型環氧丙烯酸酯之合成） 將雙紛A型環氧樹脂（DIC公司製造，「EpieiQn EXA-850CRP」）17〇 g溶解於甲苯500 mL，向該溶液中添 加三苯基膦0.1 g，製成均勻溶液。於回流攪拌下用2小時 將丙烯酸72 g滴入所獲得之溶液後，進而回流攪拌8小時。 3 27 201124783 其次，藉由去除甲苯，獲得將所有環氧基轉化為丙烯 醯基之雙酚A型環氧丙烯酸酯。 (部分丙烯酸酯化雙酚F型環氧樹脂之合成） 將雙酚F型環氧樹脂（DIC公司製造，「Epicl EXA-830CRP」）156g溶解於曱苯5〇〇mL，向該溶液中Z 加三苯基膦(M g，製成均勻溶液。於回流攪拌下用2小： 將丙烯酸72 g滴人至所獲得之溶液後，進而回流授摔 時。 '‘ 其次’藉由去除甲苯’獲得5G莫耳％之環氧基與丙歸 酸反應而成之部分丙烯酸酯化雙酚F型環氧樹脂。 再者，改質率係藉由如下方法進行測定：:所獲得之 部分丙烯酸醋化雙紛F型環氧樹脂溶解於鹽酸-二口号院容 液後，使用KOH對環氧基所消耗之鹽酸量進行滴定。’令 (部分丙烯酸酯化醚型環氧樹脂之合成） 將謎型環氧樹脂（東都化成公司叙造〇，「yslv獅e」） 164 g溶解於甲苯500 mL，向 ^ ^ ，合及中添加三苯基膦0.1 g， 液：於回流攪拌下用2小時將丙稀酸72 g滴入 所獲彳于之溶液後，進而回流攪拌8小時。 &amp;其次’藉由去㈣苯，獲得5q莫耳％之環氧基與丙稀 酉文反應而成之部分丙烯酸酯化醚型環氡樹浐 再者’改質率係藉由如下方法 部分丙烯酸醋㈣型環氧樹脂溶解於T鹽二二 後，使用刪對環氧基所消耗之鹽酸量進㈣定。 28 201124783 (實施例1 ) (密封劑之製作） 播合作為硬化性樹脂之合成之雙酚A型環氧丙烯酸酯 100重量份及合成之部分丙稀酸酯化雙盼F型環氧樹脂i〇〇 重量份、作為光聚合起始劑之雙（2，4,6-三甲基笨曱醯基）苯 基氧化膦（Cibajapan公司製造，「irgacure8l9」，於曱 醇溶劑中測得之對405 nm之波長的吸光係數為899 ml/g • cm) 3重量份、作為矽烷偶合劑之τ _甲基丙烯醯氧基丙 基二甲氧基矽烷（Shin-Etsu Silicones公司製造，κβμ·5〇3) 3重量份、熱硬化劑（+jin〇moto Fine_Techn〇公司製造， mi cure VDH」）32重量份及作為填充劑之球狀石夕土 (Admatechs公司製造，r S0_C1」）4〇重量份，藉由行星 式攪拌裝置（Thinky公司製造，「除泡練太郎」）進行攪 拌後，利用陶瓷三輥使其均勻混合而獲得密封劑。 (液晶顯示面板之製作） 、利用分注器將所獲得之密封劑以描繪成長方形框之方 式塗佈於一塊附有配向膜及透明電極之基板上。其次，滴 入液晶材料，將另一塊基板貼合後，使用具有LED元件（發 光峰值波長為385 nm，發光峰之半值寬度為u nm)與濾 光片（ 380 nm以下之光之穿透率為〇)之光照射裝置，、= 該已貼合之基板之密封劑部，照射基於4〇5nm之波長之累 計光量為3000 mJ/cm2的土 杜—Α 、 。 n 的先，使密封劑光硬化，其後於12〇 °C下使其熱硬化1小時。 其次 一面對基板間施加電壓一 面照射紫外線，使液 29 201124783 晶材料配向而製成液晶顯示面板。 (實施例2) 除了將光聚合起始劑變更為2-(二甲胺基）-2-[(4-甲基 笨基）曱基]-l-[4-(4-嗎琳基）笨基]·ΐ-丁酮（ciba Japan公司 製造’ 「Irgacure 379」，於曱醇溶劑中測得之對405 nm之 波長的吸光係數為280 ml/ g · cin ) 3重量份以外，藉由與 實施例1相同之方式獲得密封劑及液晶顯示面板。 (實施例3) 除了將光聚合起始劑變更為丨_[4_(苯硫基）苯基]_丨，2_辛 二酮2-(0-苯曱醯肟）（Ciba Japan公司製造，「Irgacure OXEO1」，於乙腈溶劑中測得之對4〇5 nm之波長的吸光係 數為102 ml/g· cm) 3重量份以外，藉由與實施例i相同 之方式獲得密封劑及液晶顯示面板。 (實施例4) 除了將光聚合起始劑變更為2,4,6-三甲基苯甲醯基二 苯基氧化膦（Ciba Japan公司製造，「Darocur TPO」，於 乙腈溶劑中測得之對405 mn之波長的吸光係數為i 65 ml/ g · cm ) 3重量份以外，藉由與實施例i相同之方式獲得密 封劑及液晶顯示面板。 (實施例5) 除了將光聚合起始劑之摻合量變更為i重量份以外， 藉由與實施例4相同之方式獲得密封劑及液晶顯示面板。 (實施例6) 除了將光聚合起始劑之摻合量變更為9重量份以外， 30 201124783 藉由與實施例4相同 (實施例7) 之方式獲得密封劑及液晶顯示面板 〇 t除了將硬化性樹脂變更為合成之雙紛A型環氧丙稀酸 酉曰100重量份、合成之部分丙稀酸S旨化雙紛F型環氧樹脂 5〇重罝份、及合成之部分丙烯酸酯化醚型環氧樹脂兄重量 份以外’藉由與實施例&quot;目同之方式獲得密封劑及液晶顯 示面板。 (比較例1 ) 藉由與實施例1相同之方式獲得密封劑。又，除了使 用金屬-化物燈作為照射光源’且照射基於4〇5nm之波長 的累計光量為3000 mJ/cm2之光以外，藉由與實施例&quot;目 同之方式獲得液晶顯示面板。 (比較例2) 藉由與實施例1相同之方式獲得密封劑。又，除了使 用金屬-化物燈作為照射光源，且照射基於4〇5細之波長 的累汁光量為500 mj/ cm2之光以外，藉由與實施例2相同 之方式獲付液晶顯示面板。 (比較例3) 藉由與實施例2相同之方式獲得密封劑。又，除了使 用金屬齒化物燈作為照射光源以外，藉由與實施例2相同 方式獲传液晶顯示面板。 (比較例4) 藉由與實施例3相同之方式獲得密封劑。又，除了使 金屬齒化物燈作為照射光源以外，藉由與實施例3相同 31 201124783 之方式獲得液晶顯示面板。 (比較例5) 藉由與實施例4相同之方式獲得密封劑。又，除了使 用金屬函化物燈作為照射光源以外’藉由與實施例4相同 之方式獲得液晶顯示面板。 (比較例6) 除了將光聚合起始劑變更為2,2-二曱氧基-12-二苯基 乙烧-1-_((^匕3】3卩&amp;11公司製造，「11§3(：1^651」，於甲 醇溶劑中測得之對405 nm之波長之吸光係數未達1 mi/ g • cm ) 3重量份，且使用金屬鹵化物燈作為照射光源以外， 藉由與實施例1相同之方式獲得密封劑及液晶顯示面板。 (比較例7 ) 除了將光聚合起始劑變更為1-[4-(2-羥基乙氧基）苯 基]-2-經基-2-甲基-1-丙烧-1-酮（cib a Japan公司製造， 「IrgaCure 2959」，於甲醇溶劑中測得之對4〇5 nm之波長 的吸光係數未達Itni/g.cm) 3重量份，且使用金屬函化 物燈作為照射光源以外，藉由與實施例丨相同之方式獲得 密封劑及液晶顯示面板。 (比較例8) 藉由與實施例5相同之方式獲得密封劑。又，除了使 用金屬鹵化物燈作為照射光源以外，藉由與實施例5'相同 之方式獲得液晶顯示面板。 (比較例9) 藉由與實施例6相同之方式獲得密封劑。又，除了使 32 201124783 用金屬il化物燈作為照射光源以外，藉由與實施例6相同 之方式獲得液晶顯示面板。 (比較例1 〇 ) 藉由與實施例7相同之方式獲得密封劑…除了使 用金屬函化物燈作為照射光源以外，藉由與實施例7相同 之方式獲知液晶顯示面板。 〈評價〉 針對實施例及比較例所獲得之液晶顯示面板進行以下 之評價。將結果示於表1及表2。 (1 )顯示不均（液晶配向紊亂） 針對所獲得之液晶顯示面板（樣品數5個）’藉由目 視確認剛製成液晶顯示面板後之密封劑附近之液晶配向紊 亂。配向蒼就係藉由顯示部之色彩不均來判斷，根據色彩 不均之程度’作出以下4個等級之評價：將無色彩不均之 情形設為「◎」’將存在少許色彩不均之情形設為「〇」， 將存在色彩不均之情形設為「△」，#色彩相#不均之情 形設為「X」。又，針對照射光而使密封劑硬化時具有液晶 保濩光罩之情形與無液晶保護光罩之情形進行評價。 (2 )光之利用效率 將所獲得之密封劑lg溶解於f醇或乙腈1()虹而萃取 起始劑’利用分光光度計測定該萃取液，由所得社果 起始劑之吸收波長區域，將其作為使用波長區域。另一方 面’利用UV光譜儀測定光源之發光波長區域，將其作為發 光波長區域。由所獲得之使用波長區域及發光波長區域之 33 201124783 值，求出使用波長區域/發光波長區域。根據以下基準評 價光之利用效率。 〇：使用波長區域/發光波長區;域為50%以上 X:使用波長區域/發光波長區★未達50% [表1] 费施i歹丨 1 2 3 4 5 6 7 密封劑組成 (重量份） 硬化性 樹脂 雙酚A型環氧丙烯酸酯 (丙烯醯基化率100%) 100 100 100 100 100 100 100 部分丙烯酸酯化雙酚F型環氧樹脂 (丙烯醯基化率50%) 100 100 100 100 100 100 50 部分丙烯酸酯化醚型環氧樹脂 (丙烯醯基化率50%) 50 光聚合 起始劑 Irgacure 819 丨 (與發光波長區域之重疊為100%) 3 - Irgacure 379 (與發光波長區域之重疊為100%) - 3 - - - - - Irgacure OXE01 (與發光波長區域之重疊為100%) - - 3 - - - - Darocur TPO (與發光波長區域之重疊為100%) - - - 3 1 9 3 Irgacure 651 (與發光波長區域之重疊為20%) - Irgacure 2959 (與發光波長區域之重疊為〇%) - KBM-503 3 3 3 3 3 3 3 熱硬化劑 VDH 32 32 32 32 32 32 32 填充劑 SO-C1 40 40 40 40 40 40 40 密封用硬嫌 (使用：〇） 金屬鹵化物燈+ 400 nm CutFilter LED+ 400 nm CutFilte 〇 〇 〇 〇 〇 〇 〇 評價 顯示稍 無液晶保護光罩 Δ 〇 〇 〇 〇 〇 〇 有液晶保護光罩 〇 ◎ ◎ ◎ ◎ ◎ ◎ 光^j用 效率 使用波長區域/發光波長區域 (50%以上：〇，未達50% : X ) ◎ ◎ ◎ ◎ ◎ ◎ ◎ 34 201124783 [表2]The characteristics of the element 25 and the filter 30 are the same as those of the LED elements and filters of Fig. 4 &quot; Further, the above-described light irradiation device can be implemented as follows. (1) In the light source section 2A shown in Fig. 4, as shown in Fig. 8, the hemispherical shape having a lens function is shown. Instead of arranging the filter 30 on each of the LED elements 25, a configuration of r F to light 30 in the cylindrical hole of the light guiding member 26 as shown in Fig. 9 may be provided at the center position of 26 201124783. In the top LED package 35 of the 26-hole, it is provided with a lens function &lt; 叩, 邳, the integrator lens 29 (2) can be arranged in the light source section 20 shown in FIG. The filter 30 may also be a hemispherical shape as shown in Fig. 1(a). Alternatively, as shown in Fig. 10 (b), the package 35 may be provided with a lens 31 on the surface of the plate-shaped filter sheet 30. According to the present invention, it is possible to provide a method for manufacturing a liquid crystal display device which can manufacture an almost liquid/loss dyed liquid crystal display device at low cost and high efficiency. The method for manufacturing a liquid crystal display device of the present invention is particularly applicable to a PS a mode or a blue phase mode. The manufacture of liquid crystal display devices. [Embodiment] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the embodiments. <Synthesis of Curable Resin> (Synthesis of Bisphenol A Type Epoxy Acrylate) 17 〇g of a double-type A-type epoxy resin ("EpieiQn EXA-850CRP" manufactured by DIC Corporation) was dissolved in 500 mL of toluene. 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. 72 g of acrylic acid was added dropwise to the obtained solution under reflux for 2 hours, and further stirred under reflux for 8 hours. 3 27 201124783 Next, by removing toluene, a bisphenol A type epoxy acrylate which converts all epoxy groups to propylene groups is obtained. (Synthesis of a partially acrylated bisphenol F-type epoxy resin) 156 g of a bisphenol F-type epoxy resin ("Epicl EXA-830CRP", manufactured by DIC Corporation) was dissolved in 5 〇〇mL of toluene, and Z was added to the solution. Add triphenylphosphine (M g, make a homogeneous solution. Use 2 small under reflux and stir: 72 g of acrylic acid is dripped into the obtained solution, and then return to reflux. ''Second' by removing toluene' A partially acrylated bisphenol F-type epoxy resin obtained by reacting 5 G mol% of an epoxy group with a propionic acid is obtained. Further, the modification rate is determined by the following method: a part of the obtained acrylic vinegar After the double-type F-type epoxy resin is dissolved in the hydrochloric acid-two slogan volume, the amount of hydrochloric acid consumed by the epoxy group is titrated with KOH. 'Or (the synthesis of partially acrylated ether epoxy resin) Type epoxy resin (Dongdu Chemical Co., Ltd., "yslv Lion e") 164 g dissolved in 500 mL of toluene, adding 0.1 g of triphenylphosphine to ^^, combined with, and liquid: 2 hours under reflux with stirring 72 g of acrylic acid was added dropwise to the obtained solution, and further stirred under reflux for 8 hours. By 'removing (tetra)benzene, a part of the acrylated ether-type anthraquinone which is obtained by reacting 5q mol% of an epoxy group with acrylonitrile is further modified by a method of partially acrylating vinegar by the following method After the (4) type epoxy resin is dissolved in the T salt 22, the amount of hydrochloric acid consumed by the epoxy group is added to (4). 28 201124783 (Example 1) (Preparation of sealant) The sock cooperation is the synthesis of the curable resin. 100 parts by weight of bisphenol A type epoxy acrylate and a part of the synthesized acrylated double-prepared F type epoxy resin i 〇〇 by weight, as a photopolymerization initiator double (2,4,6-trimethyl) Phenylphosphine oxide (manufactured by Cibajapan, "irgacure8l9", measured at 405 nm wavelength in sterol solvent, 899 ml/g • cm) 3 parts by weight as a decane couple Mixture τ _methacryloxypropyl dimethoxy decane (manufactured by Shin-Etsu Silicones Co., Ltd., κβμ·5〇3) 3 parts by weight, heat hardener (manufactured by Jinjin Motomoto Fine_Techn Co., Ltd., mi cure VDH") 32 parts by weight and spherical shoal as a filler (Admatechs, r S0_C1 ") 4 parts by weight, stirred by a planetary stirring device ("Thinky", manufactured by Thinky Co., Ltd.), and then uniformly mixed with three ceramic rolls to obtain a sealant. (Production of liquid crystal display panel) The obtained sealant is applied to a substrate having an alignment film and a transparent electrode by drawing into a rectangular frame by a dispenser. Secondly, the liquid crystal material is dropped, and the other substrate is bonded, and the LED is used. A light-emitting device with a component (luminescence peak wavelength of 385 nm, half-value width of the luminescence peak is u nm) and a filter (light transmittance of 380 nm or less), = sealing of the bonded substrate In the agent portion, the organic light amount based on the wavelength of 4〇5 nm is 3,000 mJ/cm 2 . First, the sealant was photohardened and then thermally cured at 12 ° C for 1 hour. Next, a liquid crystal display panel is formed by irradiating ultraviolet rays on the surface of the substrate to apply a voltage to the liquid crystal. (Example 2) except that the photopolymerization initiator was changed to 2-(dimethylamino)-2-[(4-methylphenyl)indenyl]-l-[4-(4-morphinyl) Stupid base]·ΐ-butanone ("Irgacure 379" manufactured by ciba Japan), which has an absorbance coefficient of 280 ml/g · cin ) at a wavelength of 405 nm measured in a decyl alcohol solvent, by 3 parts by weight A sealant and a liquid crystal display panel were obtained in the same manner as in Example 1. (Example 3) The photopolymerization initiator was changed to 丨_[4_(phenylthio)phenyl]-anthracene, 2-dioctane-2-(0-benzoquinone) (manufactured by Ciba Japan Co., Ltd.) Sealant and liquid crystal display were obtained in the same manner as in Example i except that "Irgacure OXEO1" was measured in an acetonitrile solvent to have an absorption coefficient of a wavelength of 4 〇 5 nm of 102 ml/g·cm) of 3 parts by weight. panel. (Example 4) The photopolymerization initiator was changed to 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (Darocur TPO, manufactured by Ciba Japan Co., Ltd., in acetonitrile solvent). A sealant and a liquid crystal display panel were obtained in the same manner as in Example i except that the light absorption coefficient of the wavelength of 405 mn was i 65 ml/g·cm 3 parts by weight. (Example 5) A sealant and a liquid crystal display panel were obtained in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator was changed to i parts by weight. (Example 6) A sealing agent and a liquid crystal display panel were obtained in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator was changed to 9 parts by weight, in addition to the same as in Example 4 (Example 7). The curable resin is changed to 100 parts by weight of the synthesized A-type bismuth acrylate, and the synthesized part of the acrylic acid S is a double-type F-type epoxy resin 5 〇 heavy 罝, and a part of the acrylate synthesized. A sealant and a liquid crystal display panel were obtained by the same method as in the example of the ether-type epoxy resin. (Comparative Example 1) A sealant was obtained in the same manner as in Example 1. Further, a liquid crystal display panel was obtained in the same manner as in the Example except that a metal-chemical lamp was used as the irradiation light source ′ and the light having an integrated light amount of 3,000 mJ/cm 2 based on a wavelength of 4 〇 5 nm was irradiated. (Comparative Example 2) A sealant was obtained in the same manner as in Example 1. Further, a liquid crystal display panel was obtained in the same manner as in Example 2 except that a metal-chemical lamp was used as the irradiation light source and light having a light amount of 500 mj/cm 2 based on a wavelength of 4 〇 5 was irradiated. (Comparative Example 3) A sealant was obtained in the same manner as in Example 2. Further, a liquid crystal display panel was obtained in the same manner as in Example 2 except that a metal toothed lamp was used as the irradiation light source. (Comparative Example 4) A sealant was obtained in the same manner as in Example 3. Further, a liquid crystal display panel was obtained in the same manner as in Example 3 except that the metal toothed lamp was used as the irradiation light source. (Comparative Example 5) A sealant was obtained in the same manner as in Example 4. Further, a liquid crystal display panel was obtained in the same manner as in Example 4 except that a metal complex lamp was used as the irradiation light source. (Comparative Example 6) The photopolymerization initiator was changed to 2,2-dimethoxyoxy-12-diphenylethene-1-((^^3)3卩&amp;11 company, "11 §3(:1^651), which has an absorption coefficient of less than 1 mi/g•cm) of 3 kHz at a wavelength of 405 nm measured in a methanol solvent, and using a metal halide lamp as an illumination source, A sealant and a liquid crystal display panel were obtained in the same manner as in Example 1. (Comparative Example 7) except that the photopolymerization initiator was changed to 1-[4-(2-hydroxyethoxy)phenyl]-2-yl group -2-Methyl-1-propen-1-one (manufactured by Cib a Japan, "IrgaCure 2959", the absorbance of the wavelength of 4〇5 nm measured in methanol solvent is less than Itni/g.cm A sealant and a liquid crystal display panel were obtained in the same manner as in Example 3 except that 3 parts by weight and a metal halide lamp was used as the light source. (Comparative Example 8) A sealant was obtained in the same manner as in Example 5. Further, a liquid crystal display panel was obtained in the same manner as in Example 5' except that a metal halide lamp was used as the irradiation light source. (Comparative Example 9) The same as in Example 6. In the same manner as in Example 6, a liquid crystal display panel was obtained in the same manner as in Example 6 except that a metal ilicide lamp was used as the illumination source of 32 201124783. (Comparative Example 1 〇) By the same manner as in Example 7. A liquid crystal display panel was obtained in the same manner as in Example 7 except that a metal halide lamp was used as the light source. <Evaluation> The following evaluations were performed on the liquid crystal display panels obtained in the examples and the comparative examples. The results are shown in Tables 1 and 2. (1) Display unevenness (liquid crystal alignment disorder) The liquid crystal display panel (the number of samples 5) obtained was visually confirmed by the visual inspection of the vicinity of the sealant immediately after the liquid crystal display panel was fabricated. The alignment of the liquid crystal is disordered. The alignment is determined by the uneven color of the display portion, and the following four levels are evaluated according to the degree of color unevenness: the case of no color unevenness is set to "◎" and there will be a little In the case of uneven color, it is set to "〇", and the case where color unevenness is present is set to "△", and the case where #色相# is uneven is set to "X". When the light is applied to cure the sealant, the liquid crystal protection mask is used and the liquid crystal protection mask is not evaluated. (2) Light utilization efficiency The obtained sealant lg is dissolved in f alcohol or acetonitrile 1 () rainbow The extraction initiator' is measured by a spectrophotometer, and the absorption wavelength region of the obtained fruit starter is used as the wavelength region to be used. On the other hand, the wavelength of the light source is measured by a UV spectrometer. As the light-emitting wavelength region, the use wavelength region/light-emitting wavelength region is obtained from the obtained use wavelength region and the light-emitting wavelength region 33 201124783 value. The efficiency of light utilization is evaluated based on the following criteria. 〇: Use wavelength region/light-emitting wavelength region; domain is 50% or more X: use wavelength region/light-emitting wavelength region ★ less than 50% [Table 1] Fei Shi i歹丨1 2 3 4 5 6 7 Sealant composition (weight Parts) Curable resin bisphenol A epoxy acrylate (100% acrylonitrile) 100 100 100 100 100 100 100 Partially acrylated bisphenol F epoxy resin (propylene oximation rate 50%) 100 100 100 100 100 100 50 Partially acrylated ether epoxy resin (50% acrylonitrile) 50 Photopolymerization initiator Irgacure 819 丨 (100% overlap with emission wavelength region) 3 - Irgacure 379 (with The overlap of the emission wavelength region is 100%) - 3 - - - - - Irgacure OXE01 (100% overlap with the emission wavelength region) - - 3 - - - - Darocur TPO (overlap with the emission wavelength region is 100%) - - - 3 1 9 3 Irgacure 651 (20% overlap with the emission wavelength region) - Irgacure 2959 (with 发光% overlap with the emission wavelength region) - KBM-503 3 3 3 3 3 3 3 Thermal hardener VDH 32 32 32 32 32 32 32 Filler SO-C1 40 40 40 40 40 40 40 Sealing hard (use: 〇) metal Halide lamp + 400 nm CutFilter LED+ 400 nm CutFilte 〇〇〇〇〇〇〇Evaluation shows no liquid crystal protection mask Δ 液晶With liquid crystal protection 〇 ◎ ◎ ◎ ◎ ◎ ◎ Light efficiency Use wavelength region/light-emitting wavelength region (50% or more: 〇, less than 50%: X) ◎ ◎ ◎ ◎ ◎ ◎ ◎ 34 201124783 [Table 2]

比較例 1 2 3 4 5 6 7 8 9 10 密封劑組成 (重量份） 硬化性 樹脂 雙酚A型環氧丙烯酸酯 (丙烯醯基化率100%) 100 100 100 100 100 100 100 100 100 100 部分丙烯酸酯化雙酚 F型環氧樹脂 (丙烯醯基化率50%) 100 100 100 100 100 100 100 100 100 50 部分丙烯酸酯化醚型 環氧樹脂 (丙烯酿基化率50%) 50 光聚合 起始劑 Irgacure 819 (與發光波長區域之重 疊為100%) 3 3 - Irgacure 379 (與發光波長區域之重 疊為100%) - - 3 Irgacure OXE01 (與發光波長區域之重 疊為100%) - - - 3 - - - - - - Darocur TPO (與發光波長區域之重 疊為100%) - - - - 3 - - 1 9 3 Irgacure 651 (與發光波長區域之重 疊為20%) - - - - - 3 - - - - Irgacure 2959 (與發光波長區域之重 疊為0%) - - - - - - 3 - - - 矽烷 偶合劑 KBM-503 3 3 3 3 3 3 3 3 3 3 触· VDH 32 32 32 32 32 32 32 32 32 32 填充劑 SO-C1 40 40 40 40 40 40 40 40 40 40 密封用硬舰 (賴：〇） 金屬鹵化物燈+ 400 nm CutFilte 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 LED+ 400 nm CutFilte 評價 顯示稍 無液晶保護光罩 X X Δ Δ Δ X X X X Δ 有液晶保護光罩 X X Δ Δ Δ X X X X Δ 光之利用 效率 使用波長區域/發光波 長區域 (50%以上：〇，未達 50% ： X ) X X X X X X X X X X 35 201124783 [產業上之可利用性] 利用本發明，可接徂 J抆供一種可以低成本且高效率製 乎無液晶污染之液Bgg_壯印 及B日颁不裝置的液晶顯示裝置之製造方 【圖式簡單說明】 系表示具有光照射裝置之顯示面板之貼合裝置之 一例的構成概略之說明圖。 圖2係表示顯示面板之貼合裝置之處理對象物 圖。 圖3係表示光照射裝置之一例之構成的平面圖。 圖4係表示光照射裝置中之光源區段之構成的說叫 圖5係不意性表示led元件之發光光譜與渡光片之分 光特性之關係的曲線圖。 圖6係表示光照射裝置之另一例中之光源區段之構成 的說明圖。 圖7係表示光源區段中之LED封裝之構成的說明圖。 圖8係表示光源區段之變形例之主要部之構成的說明 圖。 圖9係表示光源區段之另一變形例之構成的說明圖。 圖1 〇係表示LED封裝之變形例之構成的說明圖。 【主要元件符號說明】 1 處理對象物 36 201124783 2 液晶材料 3 密封劑層 4 透光性基板 10 載置台 11 基台 12 支持台 15 光照射裝置 20 光源區段 21 基板 25 LED元件 26 導光構件 27 散熱用鰭片 28 光出射部 29 積分器透鏡 30 濾、光片 31 透鏡 35 LED封裝 36 封裝基板 37 凹部 37Comparative Example 1 2 3 4 5 6 7 8 9 10 Sealant Composition (Parts by Weight) Curable Resin Bisphenol A Type Epoxy Acrylate (100% Ethacrylic Acid) 100 100 100 100 100 100 100 100 100 100 Part Acrylate bisphenol F type epoxy resin (propylene oximation rate 50%) 100 100 100 100 100 100 100 100 100 50 Partially acrylated ether epoxy resin (propylene enrichment rate 50%) 50 Photopolymerization The initiator Irgacure 819 (100% overlap with the emission wavelength region) 3 3 - Irgacure 379 (100% overlap with the emission wavelength region) - - 3 Irgacure OXE01 (overlap with the emission wavelength region is 100%) - - - 3 - - - - - - Darocur TPO (100% overlap with the emission wavelength region) - - - - 3 - - 1 9 3 Irgacure 651 (over 20% overlap with the emission wavelength region) - - - - - 3 - - - - Irgacure 2959 (0% overlap with the emission wavelength region) - - - - - - 3 - - - Decane coupling agent KBM-503 3 3 3 3 3 3 3 3 3 3 Touch · VDH 32 32 32 32 32 32 32 32 32 32 Filler SO-C1 40 40 40 40 40 40 40 40 40 40 Sealed hard ship (Lai: 〇) Metal halide lamp + 400 nm CutFilte 〇〇〇〇〇〇〇〇〇〇LED+ 400 nm CutFilte Evaluation shows slightly no liquid crystal protection reticle XX Δ Δ Δ XXXX Δ With liquid crystal protection reticle XX Δ Δ Δ XXXX Δ Light utilization efficiency using wavelength area / Light-emitting wavelength region (50% or more: 〇, less than 50%: X) XXXXXXXXXX 35 201124783 [Industrial Applicability] With the present invention, it is possible to provide a low-cost and high-efficiency liquid-free pollution. (Brief Description of the Drawings) A description of the configuration of an example of a bonding apparatus having a display panel having a light irradiation device. Fig. 2 is a view showing a processing object of a bonding apparatus of a display panel. Fig. 3 is a plan view showing a configuration of an example of a light irradiation device. Fig. 4 is a view showing the configuration of a light source section in the light irradiation device. Fig. 5 is a graph showing the relationship between the light emission spectrum of the LED element and the spectral characteristics of the light-passing sheet. Fig. 6 is an explanatory view showing the configuration of a light source section in another example of the light irradiation device. Fig. 7 is an explanatory view showing the configuration of an LED package in a light source section. Fig. 8 is an explanatory view showing a configuration of a main part of a modification of the light source section. Fig. 9 is an explanatory view showing a configuration of another modification of the light source section. Fig. 1 is an explanatory view showing a configuration of a modification of the LED package. [Description of main components] 1 Processing object 36 201124783 2 Liquid crystal material 3 Sealant layer 4 Translucent substrate 10 Stage 11 Substrate 12 Support stage 15 Light irradiation device 20 Light source section 21 Substrate 25 LED element 26 Light guide member 27 Heat sink fin 28 Light exit portion 29 Integrator lens 30 Filter, light sheet 31 Lens 35 LED package 36 Package substrate 37 Concave portion 37

Claims (1)

201124783 七、申凊專利範圍： .1.-種液晶顯示裝置之製造方法，其係具有如下步驟 者.步驟1:使用含有硬化性樹脂與光聚合起始劑之光硬化 性密封劑於一塊基板上形成框狀之密封劑層，·步驟2··將含 有聚合性材料與光聚合起始劑之液晶材料滴加於由該密封 劑層包圍之區域；步驟3 :藉由該密封劑將該—塊基板與另 一塊基板貼合’對該已貼合之基板照射使該密封劑光硬化 之波長之光，而使該密封劑光硬化；及步驟4:照射使該液 晶材料光聚合之波長之光’而使該液晶材料光聚合，其特 徵在於： 使該密封劑光硬化之光的波長，相較於使該液晶材料 光聚合之光的波長，位於更長波長側， 於該步驟3中使密封劑光硬化之波長之光係由具有 LED元件與濾光片之光照射裝置照射，該led元件於使該 抢封劑光硬化之波長的區域内之除使該液晶材料光聚合之 波長的區域以外之區域具有發光峰值波長，而該濾光片則 會過濾掉自該LED元件照射之光中位於較該發光峰值波長 更紐波長側且與使該液晶材料光聚合之波長重複之區域之 光。 2. 如申請專利範圍第1項之液晶顯示裝置之製造方 法’其中’ LED元件之發光峰值波長之半值寬度為3〇 nm 以下。 3. 如申請專利範圍第1或2項之液晶顯示裝置之製造方 法，其中，具有LED元件與濾光片之光照射裴置，係於任 38 201124783 意面上配置有递叙〃m τ ，復數個LED元件與濾光片者。 申專利範圍第1、2或3項之液晶顯示裝置之製 造方法，其中， 、 用於社、封劑之光聚合起始劑，於甲醇或乙 腈冷劑中所測得之對4()5⑽之波長的吸光係數為 g · cm以上。 5’如申請專利範圍第卜2、3或4項之液晶顯示裝置之 製造方法，其中，用於密封劑之光聚合起始劑係下述者： 將曱醇或乙腈溶劑中之濃度設為〇丨重量％時的吸光波長區 域與較LED元件之發光波長區域中由滤光片過渡掉之波長 區域更長波長側的發光波長區域具有5〇%以上之重疊。 6_如申請專利範圍第丨、2、3、…項之液晶：示裝 置之製造方法，其中，用於密封劑之光聚合起始劑不會因 130°C以下溫度之加熱而產生自由基’且其吸光波長區域之 長波長側端未連450 nm ° 八、圖式： (如次頁） 39201124783 VII. Application scope of the invention: .1. A method for manufacturing a liquid crystal display device, which has the following steps. Step 1: using a photocurable sealant containing a curable resin and a photopolymerization initiator on a substrate Forming a frame-shaped sealant layer thereon, Step 2: adding a liquid crystal material containing a polymerizable material and a photopolymerization initiator to a region surrounded by the sealant layer; Step 3: using the sealant - the block substrate is bonded to the other substrate 'the substrate to be bonded is irradiated with light of a wavelength that hardens the sealant to lightly cure the sealant; and step 4: irradiating the wavelength of photopolymerization of the liquid crystal material Light-polymerizing the liquid crystal material, wherein the wavelength of the light that hardens the sealant is on the longer wavelength side than the wavelength of the light that causes the liquid crystal material to photopolymerize, in step 3 The light of the wavelength at which the sealant is photohardened is irradiated by a light irradiation device having an LED element and a filter, and the LED element is photopolymerized in a region of a wavelength at which the sealant is photohardened. wave The area outside the area has an emission peak wavelength, and the filter filters out the area of the light irradiated from the LED element which is located on the side of the wavelength of the emission peak and repeats the wavelength of photopolymerization of the liquid crystal material. Light. 2. The method of manufacturing a liquid crystal display device of claim 1, wherein the half-value width of the luminescence peak wavelength of the LED element is 3 〇 nm or less. 3. The method of manufacturing a liquid crystal display device according to claim 1 or 2, wherein the light-emitting device having the LED element and the filter is disposed on the surface of any 38 201124783 with a reciting 〃m τ , A plurality of LED elements and filters. The method for manufacturing a liquid crystal display device according to the first, second or third aspect of the invention, wherein, the photopolymerization initiator for the sealant is used in a methanol or acetonitrile refrigerant to measure 4() 5(10) The absorption coefficient of the wavelength is g·cm or more. 5' The method for producing a liquid crystal display device according to claim 2, 3 or 4, wherein the photopolymerization initiator for the sealant is: the concentration in the decyl alcohol or acetonitrile solvent is set to The light-absorbing wavelength region at the weight % of 〇丨 has an overlap with the light-emitting wavelength region on the longer wavelength side than the wavelength region in which the filter is shifted from the light-emitting wavelength region of the LED element, and has an overlap of 5 % or more. 6_ For example, in the liquid crystal of the application scope of the second, third, third, ..., the manufacturing method of the device, wherein the photopolymerization initiator for the sealant does not generate free radicals due to heating at temperatures below 130 ° C 'And the long-wavelength side of the absorption wavelength region is not connected to 450 nm °. Eight, the pattern: (such as the next page) 39
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