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TW200813630A - Photosensitive composition, photosensitive resin transferring film, method of produing photo spacer, substrate for liquid crystal display device, and liquid crystal display device - Google Patents

Photosensitive composition, photosensitive resin transferring film, method of produing photo spacer, substrate for liquid crystal display device, and liquid crystal display device Download PDF

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Publication number
TW200813630A
TW200813630A TW096126854A TW96126854A TW200813630A TW 200813630 A TW200813630 A TW 200813630A TW 096126854 A TW096126854 A TW 096126854A TW 96126854 A TW96126854 A TW 96126854A TW 200813630 A TW200813630 A TW 200813630A
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TW
Taiwan
Prior art keywords
group
liquid crystal
crystal display
display device
photosensitive
Prior art date
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TW096126854A
Other languages
Chinese (zh)
Inventor
Shinichi Yoshinari
Hidenori Gotoh
Kazuhiro Fujimaki
Kousaku Yoshimura
Kyohei Mochizuki
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Fujifilm Corp
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Publication of TW200813630A publication Critical patent/TW200813630A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a photosensitive composition comprising at least a resin (A) including a group having a branched and/or alicyclic structure in a side chain, a group having an acidic group in a side chain, and a group having an ethylene unsaturated group in a side chain; a polymerizable compound (B); and a photopolymerization initiator (C). The present invention also provides a photosensitive resin transferring film using the photosensitive composition; a method of producing a photo spacer using the photosensitive composition or the photosensitive resin transferring film; a substrate for a liquid crystal display device provided with the photo spacer; and a liquid crystal display device provided with the substrate for a liquid crystal display device. The present invention provides a photosensitive composition, a photosensitive resin transferring film, and a method of producing a photo spacer using the same, that exhibit a high degree of deformation resilience and are able to reduce unevenness of display in liquid crystal display devices, as well as a substrate for a liquid crystal display device and a liquid crystal display device that can prevent uneven displays and display high quality images.

Description

200813630 九、發明說明： 【發明所屬之技術領域】 本發明關於適用於製作構成顯示裝置（其液晶胞的液晶 胞厚之變動容易成爲顯示不均）的間隙子之感光性組成物’ 感光性樹脂轉印薄膜，光間隙子的製法，具備由該方法所 製作的光間隙子之液晶顯示裝置用基板，及液晶顯示裝置 〇 【先前技術】 向來，廣泛利用液晶顯示裝置於顯示高畫質影像的顯 示裝置。液晶顯示裝置一般係在一對基板間配置可以藉由 指定的配向而顯示影像的液晶層’將該基板間隔即液晶層 的厚度維持均一係爲決定畫質的要素之一。因此，爲了保 持液晶層的厚度於恒定，配設間隙子。該基板之間的厚度 一般係稱爲「液晶胞厚」。液晶胞厚通常表示上述液晶層 的厚度，換言之，表示用於施加電場於顯示區域的液晶的 2片電極間之距離。 間隙子在以往係藉由散佈珠粒而形成，但近年來變成 使用感光性組成物，藉由微影術來形成位置精度高的間隙 子。如此使用感光性組成物所形的間隙子係被稱爲光間隙 子。 使用感光性組成物，經由圖案化、鹼顯像、及烘烤所 製作的光間隙子，其間隙點的壓縮強度弱，於形成面板時 -6- 200813630 ，塑性變形有變大的傾向。於高畫質的影像顯示中，要求 不能發生以下問題：因其使得液晶層的厚度變成比設計値 還小等’而不能保持均一性的問題，或發生影像不均的問 題。又’於液晶顯示裝置的高精度化方面，不發生感光性 組成物的鹼顯像殘渣係亦重要的。 與上述有關聯，作爲用於將液晶層的厚度（液晶胞厚）保 持恒定之間隙子形成技術，有揭示間隙子形成用的聚烯丙 基之樹脂（例如參照特開2003-2 07787號公報）= 又’有揭示製造容易且儲存安定性優異的光間隙子用 之感光性組成物（例如參照特開2005-62620號公報）。 再者’也有揭示耐冷熱衝撃性優異的組成物（例如参照 特開2002-28 73 54號公報）。 【發明內容】 發明所欲解決的問顆 本來，於液晶胞所用的光間隙子中，要求高的變形回 復性。爲了實現此，藉由提高單體等的交聯反應率，而可 將變形回復率提高某一程度，但是該提高效果有變成達到 頂點的傾向，而要求進一步的改善。 本發明係鑒於上述者，以提供：具有高度的變形回復 性、能消除液晶顯示裝置的顯示不均之感光性組成物，感 光性樹脂轉印薄膜，使用此等的光間隙子之製法，防止顯 示不均且能顯示高畫質影像的液晶顯示裝置用基板，及液 200813630 晶顯示裝置當作目的，以達成該目的當作課題。 解決問題的手段 本發明得到以下知識：於使用一種樹脂，其含有在側 鏈具有分枝及/或脂環構造的基、在側鏈具有酸性基的基、 及在側鏈具有乙烯性不飽和基的基，則顯著提高變形回復 性，特別有效於改善顯示不均，以該知識爲基礎而達成者 〇 芾於達成上述課題的具體ΐ段係如下。 &lt; 1 &gt; 一種感光性組成物，其特徵爲至少包含：樹脂（Α) ，其含有在側鏈具有分枝及/或脂環構造的基、在側鏈具有 酸性基的基、及在側鏈具有乙烯性不飽和基的基；聚合性 化合物（Β);光聚合引發劑（C)。 &lt; 2 &gt;如&lt; 1 &gt;記載的感光性組成物，其中上述樹脂（Α) 的玻璃轉移溫度（Tg)係40〜180 °C，而且重量平均分子量 係 10,000〜100,000° &lt; 3 &gt;如&lt; 1 &gt;或&lt; 2 &gt;記載的感光性組成物，其中上述 聚合性化合物（B)對樹脂（A)的質量比率（（B)/(A))係0.5〜2 〇 &lt; 4 &gt;如&lt; 1 &gt;〜&lt; 3 &gt;中任1項記載的感光性組成物， 其中更含有微粒子（D)。 &lt; 5 &gt;如&lt; 4 &gt;記載的感光性組成物’其中上述微粒子 (D)的平均粒徑係5〜50nm，而且對於&lt; 4 &gt;記載的感光性 200813630 組成物中之總固體成分而言，質量比率係5〜50質量％。 &lt;6&gt;如&lt;4〉或&lt;5&gt;記載的感光性組成物，其中上述 微粒子（D)係膠態矽石。 &lt; 7 &gt; —種感光性樹脂轉印薄膜，其係在假支持體上至 少具有感光性樹脂層的感光性樹脂轉印薄膜，其特徵爲該 感光性樹脂層係使用如&lt; 1 &gt;〜&lt; 6 &gt;中任1項記載的感光 性組成物所形成。 &lt; 8 &gt;知&lt; 7 &gt;記載的感光性樹脂轉印薄膜，其中在上 述感光性樹脂層與上述假支持體之間，設有隔氧層及/或熱 塑性樹脂層。 &lt;9&gt; 一種光間隙子之製法，其特徵爲具有使用如&lt;1 &gt;〜&lt; 8 &gt;中任1項記載的感光性組成物，藉由塗布以在 支持體上形成慼光性樹脂層的步驟。 &lt; 1 0 &gt; —種光間隙子之製法，其特徵爲具有使用如&lt; 7 &gt;或&lt; 8 &gt;記載的感光性樹脂轉印薄膜，藉由加熱及/或加 壓來轉印感光性樹脂層，在支持體上形成感光性樹脂層的 步驟。 &lt; 1 1 &gt; 一種液晶顯示裝置用基板，其特徵爲具備由如 &lt; 9 &gt;或&lt; 1 0 &gt;記載的光間隙子之製法所製造的光間隙子 〇 &lt;12&gt; —種液晶顯示裝置，其特徵爲具備如&lt;11&gt;記 載的液晶顯示裝置用基板。 200813630 發明的效果 依照本發明，可提供具有高度的變形回復性、能消除 液晶顯示裝置的顯示不均之感光性組成物，感光性樹脂轉 印薄膜，使用此等的光間隙子之製法，防止顯示不均且可 顯示高畫質影像的液晶顯示裝置用基板，及液晶顯示裝置 【實施方式】 實施發明的最形態 以下詳細說明本發明的感光性組成物、光間隙子的製 法、液晶顯示裝置用基板、及液晶顯示裝置。 &lt;感光性組成物及光間隙子的製法&gt; 本發明的感光性組成物至少含有：樹脂（Α)，其含有在 側鏈具有分枝及/或脂環構造的基、在側鏈具有酸性基的基 、及在側鏈具有乙烯性不飽和基的基；聚合性化合物（Β); 光聚合引發劑（C)。由本發明的感光性組成物所製造的光間 隙子係具有高度的變形回復性，故可以消除顯示裝置的顯 示不均。 又，本發明的光間隙子之製法係用於製造液晶顯示裝 置的光間隙子之方法，該液晶顯示裝置具備至少2片支持 體、在上述支持體間所設置的液晶、施加電場於上述液晶 的2片電極、及用於管制上述支持體間的液晶胞厚之光間 隙子，該方法具有在上述2片支持體的一者之上，形成含 -10- 200813630 本發明的感光性組成物之感光性樹脂層的層形成步驟。 依照本發明的光間隙子之製法，可容易地製造具有高 度的變形回復性之光間隙子。 以下’說明本發明的光間隙子之製法，該說明亦陳述 本發明的感光性組成物之細節。 [層形成步驟] 本發明中的層形成步驟係在支持體上形成含本發明的 感光性組成物之感光性樹脂層（以下亦僅稱「感光性樹脂組 成物層」）的步驟。 該感光性樹脂層係經由後述的製造步驟，構成變形回 復性良好的能均勻保持液晶胞厚的光間隙子。藉由使用該 光間隙子，在因爲液晶胞厚的變動而容易發生顯示不均的 顯示裝置中，特別有效於消除影像中的顯示不均。 作爲在支持體上形成感光性樹脂層的方法，可合適地 舉出：（a)藉由眾所周知的塗布法來塗布含本發明的感光性 組成物之溶液的方法，及（b)藉由使用感光性樹脂轉印薄膜 的轉印法來積層之方法。以下，就各個作說明。 (a)塗布法 感光性組成物的塗布係可藉由眾所周知的塗布法，例 如旋塗法、簾幕塗布法、狹縫塗布法、浸塗法、空氣刀塗 布法、輥塗法、線桿塗布法、凹槽輥塗布法、或美國專利 第268 1 294號說明書中所記載的使用料斗的擠壓塗布法等 -11- 200813630 來進行。其中，較佳爲特開 2004-8985 1號公報、特開 2004- 1 7043號公報、特開 2003 - 1 70098號公報、特開 2003 - 1 64787號公報、特開 2003 - 1 0767號公報、特開 2002-79 1 63號公報、特開200 1 -3 1 0 1 47號公報等中所記載 的縫型噴嘴或狹縫塗布機的方法。 (b)轉印法 於轉印的情況，使用感光性樹脂轉印薄膜，將假支持 體上所形成之膜狀的感光性樹脂層，藉由經如熱及/或加壓 的輥或平板進行壓黏或加熱壓黏，而貼合於支持體面，然 後藉由剝離假支持體，而將感光性樹脂組成物層轉印到支 持體上。具體地，作爲例子可以舉出特開平7-110575號公 報、特開平11-77942號公報、特開2000-334836號公報、 特開2002- 1 48 794號公報中記載的積層機及積層方法。從 低異物的觀點來看，較佳爲使用特開平7- 1 1 05 75號公報中 記載的方法。 於形成感光性樹脂層的情況，亦可在感光性樹脂層與 假支持體之間，更設置隔氧層（以下亦稱「隔氧膜」或「中 間層」）。藉此可提高曝光感度。又，爲了提高轉印性，亦 可設置具有緩衝性的熱塑性樹脂層。 作爲構成該感光性轉印薄膜的假支持體、隔氧層、熱 塑性樹脂層、其它層或該感光性轉印薄膜的製作方法，可 舉出特開2006-23696號公報的段落編號[0024]〜[003 0]中 -12- 200813630 所記載的構成、製作方法。 於（a)塗布法、（b )轉印法一起塗布形成感光性樹脂層時 ，其層厚較佳爲〇·5〜10·0μιη，更佳爲1〜6μιη。層厚若在 上述範圍內，則在製造時於塗布形成之際，可防止針孔的 發生，可不需要長時間來進行未曝光部的顯像去除。 作爲用於形成感光性樹脂層的支持體，例如可舉出透 明基板（例如玻璃基板或塑膠基板）、附透明導電膜（例如 ΪΤΟ膜）的基板、附彩色濾光片的基板（亦稱爲彩色濾光片 基板）、附驅動元件（例如薄膜電晶體[TFT])的驅動基板等 。作爲支持體的厚度’ 一般較佳爲700〜1200μηι。 〜感光性組成物〜 接著，說明感光性組成物。 感光性組成物係至少含有：含有在側鏈具有分枝及/或 脂環構造的基、在側鏈具有酸性基的基、及在側鏈具有乙 烯性不飽和基的基之樹脂（Α)(以下亦僅稱「樹脂（Α)」）、 聚合性化合物（Β)、光聚合引發劑（C)。又，視需要，可以 使用著色劑或界面活性劑等的其它成分來構成。 上述感光性組成物用在光間隙子係特佳的。 一樹脂（A ) — 樹脂（A)係由含有在側鏈具有分枝及/或脂環構造的基： X(X莫耳％)、具有酸性基的基：Y(y莫耳％)、及具有乙烯 性不飽和基的基：Z (z莫耳％)所成。視需要地，亦可具有 -13- 200813630 其它基（L)(l旲耳％)。又，在樹脂中的—個基中，χ、γ 及Ζ可複數地組合。 一在側鏈具有分枝及/或脂環構造的基：X一 兹說明上述「在側鏈具有分枝及/或脂環構造的基」。 首先，作爲具有分枝的基，可舉出碳原子數3〜12個 的分枝狀之烷基，例如可舉出異丙基、異丁基、第二丁基 、第三丁基、異戊基、新戊基、2 -甲基丁基、異己基、2-乙基己基' 2-甲基己基、異戊基、第三戊基、r辛基、第 三辛基等。於此等之中，較佳爲異丙基、第二丁基、第三 丁基、異戊基等，更佳爲異丙基、第二丁基、第三丁基等 〇 作爲在側鏈具有脂環構造的基，可舉出碳原子數5〜20 個的脂環式烴基，例如可舉出、環戊基、環己基、環庚基 、環辛基、原冰片基、異冰片基、金剛烷基、三環癸基等 。於此等之中，較佳爲環己基、原冰片基、異冰片基、金 剛烷基、三環癸基等，更佳爲環己基、原冰片基、異冰片 基等。 作爲含有上述在側鏈具有分枝及/或脂環構造的基之單 體，可舉出苯乙烯類、（甲基）丙烯酸酯類、乙烯醚類、乙 烯酯類、（甲基）丙烯醯胺類等，較佳爲（甲基）丙烯酸酯類 、乙烯酯類、（甲基）丙烯醯胺類，更佳爲（甲基）丙烯酸酯 類0 -14- 200813630 作爲含有上述在側鏈具有分枝構造的基之單體的具體 例子，可舉出（甲基）丙烯酸異丙酯、（甲基）丙烯酸異丁酯 、（甲基）丙烯酸第二丁酯、（甲基）丙烯酸第三丁酯、（甲基） 丙烯酸異戊酯、（甲基）丙烯酸第三戊酯、（甲基）丙烯酸第 二-異-戊酯、（甲基）丙烯酸2-辛酯、（甲基）丙烯酸3-辛酯 、（甲基）丙烯酸第三辛酯等，其中較佳爲（甲基）丙烯酸異 丙酯、（甲基）丙烯酸異丁酯、甲基丙烯酸第三丁酯等，更 佳爲手基汚烯酸異丙酯、甲基丙烯酸第三丁酯等。 其次，作爲含有上述在側鏈具有脂環構造的基之單體 的具體例子，係具有碳原子數5〜20個的脂環式烴基之（甲 基）丙烯酸酯。作爲具體例子，可舉出（甲基）丙烯酸（雙環 [2.2.1]庚基-2)酯、（甲基）丙烯酸-1-金剛烷酯、（甲基）丙烯 酸-2-金剛烷酯、（甲基）丙烯酸-3-甲基-1-金剛烷酯、（甲基） 丙烯酸-3,5-二甲基-1-金剛烷酯、（甲基）丙烯酸-3-乙基金剛 烷酯、（甲基）丙烯酸-3-甲基-5-乙基-1-金剛烷酯 '(甲基）丙 烯酸-3，5,8 -三乙基-1-金剛烷酯、（甲基）丙烯酸-3，5·二甲 基-8-乙基-1-金剛烷酯、（甲基）丙烯酸-2-甲基-2-金剛烷酯 、（甲基）丙烯酸-2-乙基-2_金剛烷酯、（甲基）丙烯酸-3-羥 基-1-金剛烷酯、（甲基）丙烯酸八氫-4,7-亞甲基茚-5-基酯、 (甲基）丙烯酸八氫-4,7-亞甲基茚-1-基甲酯、（甲基）丙烯酸-1-蓋酯、（甲基）丙烯酸三環癸酯、（甲基）丙烯酸-3-羥基-2,6,6-三甲基·雙環[3·1·1]庚酯、（甲基）丙烯酸-3,7,7-三甲 -15 - 200813630 基-4-羥基-雙環[4·1·0]庚酯、（甲基）丙烯酸（原）冰片酯、（ 甲基）丙烯酸異冰片酯、（甲基）丙烯酸蔚酯、（甲基）丙烯酸-2,2,5-三甲基環己酯、（甲基）丙烯酸環己酯等。於此等（甲 基）丙烯酸酯之中，較佳爲（甲基）丙烯酸環己酯、（甲基）丙 烯酸（原）冰片酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸-1-金剛烷酯、（甲基）丙烯酸-2-金剛烷酯、（甲基）丙烯酸-2-甲基-2-金剛烷酯、（甲基）丙烯酸-2-乙基-2-金剛烷酯、（甲 一基）丙烯酸-3-羥基-1-金剛烷酯、（甲基）丙烯酸葑酯、（甲基） 丙烯酸1-蓋酯、（甲基）丙烯酸三環癸酯等，特佳爲（甲基） 丙烯酸環己酯、（甲基）丙烯酸（原）冰片酯、（甲基）丙烯酸異 冰片酯、（甲基）丙烯酸-2-金剛烷酯。 再者’作爲更含有上述在側鏈具有脂環構造的基之單 體的具體例子，可舉出下述通式（1)或（2)所表示的化合物 。此處’於通式（1)、（2)中，X表示1或2，R表示氫或甲 基。❿及n各自獨立地表示0〜15。於通式（1)、（2) ψ，較 佳爲X-1或2，m = 0〜8，η = 0〜4,更佳爲m=l〜4、η = 0〜 2 °作爲通式（1)或（2)所表示的化合物之較佳具體例子，可 舉出下述化合物D-1〜D-5、Τ-1〜Τ-8。 -16- 200813630[Technical Field] The present invention relates to a photosensitive composition which is suitable for use in the production of a spacer which constitutes a display device (the variation of the liquid crystal cell thickness of the liquid crystal cell is likely to be uneven). Transfer film, method for producing optical spacers, substrate for liquid crystal display device having optical spacers produced by the method, and liquid crystal display device 先前 [Prior Art] Conventionally, a liquid crystal display device is widely used for displaying high-quality images. Display device. The liquid crystal display device generally has a liquid crystal layer in which a video can be displayed by a predetermined alignment between the pair of substrates. The substrate thickness, that is, the thickness of the liquid crystal layer is uniformly maintained as one of the elements for determining the image quality. Therefore, in order to keep the thickness of the liquid crystal layer constant, a spacer is provided. The thickness between the substrates is generally referred to as "liquid crystal cell thickness". The cell thickness of the liquid crystal generally indicates the thickness of the liquid crystal layer, in other words, the distance between the two electrodes for applying an electric field to the liquid crystal in the display region. In the past, the spacer was formed by scattering beads, but in recent years, a photosensitive composition has been used, and a spacer having high positional accuracy has been formed by lithography. The spacers formed by using the photosensitive composition in this manner are referred to as optical spacers. With the use of the photosensitive composition, the optical spacer produced by patterning, alkali development, and baking has a weak compressive strength at the gap, and tends to have a large plastic deformation at the time of forming the panel -6-200813630. In the high-quality image display, it is required that the following problem cannot be caused: the thickness of the liquid crystal layer becomes smaller than the design 等, and the problem of uniformity cannot be maintained, or image unevenness occurs. Further, in terms of high precision of the liquid crystal display device, it is also important that the alkali developing residue system of the photosensitive composition does not occur. In connection with the above, as a technique for forming a spacer for keeping the thickness of the liquid crystal layer (liquid crystal cell thickness) constant, there is a resin for revealing a polyallyl group for forming a spacer (for example, see JP-A-2003-2 07787 In addition, there is a photosensitive composition for optical spacers which is easy to manufacture and has excellent storage stability (for example, see JP-A-2005-62620). Further, there is a composition which exhibits excellent cold and heat resistance (for example, see JP-A-2002-28 73 54). SUMMARY OF THE INVENTION Problems to be Solved by the Invention Originally, in the optical spacer used for a liquid crystal cell, high deformation reproducibility is required. In order to achieve this, the deformation recovery ratio can be increased to some extent by increasing the crosslinking reaction rate of the monomer or the like. However, the improvement effect tends to reach the apex, and further improvement is required. In view of the above, the present invention provides a photosensitive composition which has high deformation recovery property and can eliminate display unevenness of a liquid crystal display device, and a photosensitive resin transfer film can be prevented by using the optical spacer method. A substrate for a liquid crystal display device that displays uneven images and can display high-quality images, and a liquid crystal display device of 200813630 are intended for the purpose of achieving the object. Means for Solving the Problems The present invention has the following knowledge: a resin containing a group having a branching and/or alicyclic structure in a side chain, a group having an acidic group in a side chain, and an ethylenic unsaturated group in a side chain. The basis of the base significantly improves the deformation recovery property, and is particularly effective for improving the display unevenness. The specific steps based on the knowledge to achieve the above problems are as follows. &lt; 1 &gt; A photosensitive composition characterized by comprising at least a resin having a group having a branching and/or alicyclic structure in a side chain, a group having an acidic group in a side chain, and The side chain has a group having an ethylenically unsaturated group; a polymerizable compound (Β); and a photopolymerization initiator (C). The photosensitive composition of the above-mentioned resin (Α) has a glass transition temperature (Tg) of 40 to 180 ° C and a weight average molecular weight of 10,000 to 100,000 ° &lt; 3 &gt; The photosensitive composition of the above-mentioned polymerizable compound (B) to the resin (A) ((B)/(A)) is 0.5 to 2, in the photosensitive composition according to the above-mentioned <1>. The photosensitive composition according to any one of the above-mentioned items, wherein the photosensitive composition further contains fine particles (D). &lt; 5 &gt; The photosensitive composition described in <4> wherein the average particle diameter of the fine particles (D) is 5 to 50 nm, and the total amount of the photosensitive composition of 200813630 described in &lt;4 &gt; In terms of solid content, the mass ratio is 5 to 50% by mass. The photosensitive composition according to <4> or <5>, wherein the fine particles (D) are colloidal vermiculite. &lt;7&gt; A photosensitive resin transfer film which is a photosensitive resin transfer film having at least a photosensitive resin layer on a dummy support, characterized in that the photosensitive resin layer is used as &lt;1 &gt The photosensitive composition according to any one of the above-mentioned items. The photosensitive resin transfer film of the above-mentioned photosensitive resin layer and the dummy support are provided with an oxygen barrier layer and/or a thermoplastic resin layer. &lt;9&gt; A method for producing a photo-gap, characterized in that it has a photosensitive composition as described in any one of &lt;1&gt; to &lt;8&gt;, and is coated to form a light on a support. The step of the resin layer. &lt; 1 0 &gt; - A method for producing a photo-gap, characterized in that it has a photosensitive resin transfer film as described in &lt;7 &gt; or &lt;8&gt;, and is heated and/or pressurized A step of printing a photosensitive resin layer to form a photosensitive resin layer on a support. &lt; 1 1 &gt; A substrate for a liquid crystal display device, characterized in that it comprises an optical spacer 〇&lt;12&gt; manufactured by a method of optical spacers as described in &lt;9&gt; or &lt;10&gt; A liquid crystal display device comprising the substrate for a liquid crystal display device according to <11>. According to the present invention, it is possible to provide a photosensitive composition having high deformation recovery property and capable of eliminating display unevenness of a liquid crystal display device, and a photosensitive resin transfer film, which can be prevented by using the optical spacers. A substrate for a liquid crystal display device that displays uneven image quality and a liquid crystal display device. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a photosensitive composition, a method for producing a photo spacer, and a liquid crystal display device of the present invention will be described in detail. A substrate and a liquid crystal display device are used. &lt;Preparation method of photosensitive composition and optical spacer&gt; The photosensitive composition of the present invention contains at least a resin having a branch having a branching and/or an alicyclic structure in a side chain and having a side chain a group having an acidic group and a group having an ethylenically unsaturated group in a side chain; a polymerizable compound (Β); and a photopolymerization initiator (C). The optical gap sub-system manufactured by the photosensitive composition of the present invention has high deformation recovery property, so that display unevenness of the display device can be eliminated. Further, the method for producing an optical spacer of the present invention is a method for producing a photo spacer for a liquid crystal display device comprising at least two support members, liquid crystal provided between the support members, and an electric field applied to the liquid crystal The two electrodes and the optical spacer for controlling the liquid crystal cell thickness between the supports, the method comprising forming the photosensitive composition of the present invention containing -10-200813630 on one of the two support bodies A layer forming step of the photosensitive resin layer. According to the method of manufacturing the optical spacer of the present invention, the optical spacer having high deformation recovery property can be easily manufactured. The following describes the preparation of the optical spacer of the present invention, and the description also states the details of the photosensitive composition of the present invention. [Layer forming step] The layer forming step in the present invention is a step of forming a photosensitive resin layer (hereinafter also referred to as "photosensitive resin composition layer") containing the photosensitive composition of the present invention on a support. This photosensitive resin layer constitutes a light spacer which is excellent in deformation reproducibility and can uniformly maintain the liquid crystal cell thickness through a manufacturing step to be described later. By using the optical spacer, it is particularly effective in eliminating display unevenness in the image in a display device in which display unevenness is likely to occur due to fluctuations in liquid crystal cell thickness. As a method of forming the photosensitive resin layer on the support, (a) a method of applying a solution containing the photosensitive composition of the present invention by a well-known coating method, and (b) by using A method of laminating a photosensitive resin transfer film by a transfer method. Hereinafter, each will be explained. (a) Coating method The coating method of the photosensitive composition can be applied by a well-known coating method such as a spin coating method, a curtain coating method, a slit coating method, a dip coating method, an air knife coating method, a roll coating method, or a wire rod. The coating method, the gravure coating method, or the extrusion coating method using a hopper described in the specification of U.S. Patent No. 2,681,294, etc., is carried out in the manner of -11-200813630. Among them, JP-A-2004-8985, JP-A-2004- 1 7043, JP-A-2003-17098, JP-A-2003-16078, JP-A-2003-107767, A method of a slit nozzle or a slit coater described in Japanese Laid-Open Patent Publication No. JP-A No. 2002-79 No. (b) Transfer method In the case of transfer, a photosensitive resin transfer film is formed using a photosensitive resin, and a film-like photosensitive resin layer formed on a dummy support is passed through a roller or a plate such as heat and/or pressure. The pressure-sensitive adhesive or heat-pressing is applied to the support surface, and then the photosensitive resin composition layer is transferred onto the support by peeling off the dummy support. Specifically, the laminating machine and the laminating method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. From the viewpoint of low foreign matter, the method described in JP-A-7-10575 is preferably used. In the case of forming the photosensitive resin layer, an oxygen barrier layer (hereinafter also referred to as "oxygen barrier film" or "intermediate layer") may be further provided between the photosensitive resin layer and the dummy support. Thereby, the exposure sensitivity can be improved. Further, in order to improve the transfer property, a cushioning thermoplastic resin layer may be provided. As a dummy support, an oxygen barrier layer, a thermoplastic resin layer, another layer, or a method for producing the photosensitive transfer film, which constitute the photosensitive transfer film, a paragraph number [0024] of JP-A-2006-23696 is mentioned. ~ [0030] -12-200813630 The composition and production method described. When the photosensitive resin layer is applied together with the (a) coating method and the (b) transfer method, the layer thickness thereof is preferably 〇 5 to 10 · 0 μηη, more preferably 1 to 6 μηη. When the layer thickness is within the above range, pinholes can be prevented from occurring at the time of coating formation at the time of production, and development of the unexposed portion can be prevented from being removed for a long period of time. Examples of the support for forming the photosensitive resin layer include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, a ruthenium film), and a substrate with a color filter (also referred to as a substrate). A color filter substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. The thickness ' as a support is generally preferably from 700 to 1200 μm. ~Photosensitive Composition ~ Next, a photosensitive composition will be described. The photosensitive composition contains at least a group having a branch having a branching and/or an alicyclic structure in a side chain, a group having an acidic group in a side chain, and a resin having a group having an ethylenically unsaturated group in a side chain. (hereinafter, it is also called "resin (")"), a polymerizable compound (Β), and a photoinitiator (C). Further, it may be formed using other components such as a coloring agent or a surfactant, as needed. The above photosensitive composition is particularly excellent for use in an optical gap sub-system. Resin (A) - Resin (A) is a group having a branching and/or alicyclic structure in a side chain: X (X mole %), a group having an acidic group: Y (y mole %), And a group having an ethylenically unsaturated group: Z (z mole %). Optionally, it may have -13-200813630 other base (L) (% 旲%). Further, in the group of the resin, χ, γ and Ζ may be combined in plural. A group having a branching and/or alicyclic structure in a side chain: X is the above-mentioned "base having a branching and/or alicyclic structure in a side chain". First, as the group having a branch, a branched alkyl group having 3 to 12 carbon atoms is exemplified, and examples thereof include an isopropyl group, an isobutyl group, a second butyl group, a third butyl group, and an isobutyl group. Amyl, neopentyl, 2-methylbutyl, isohexyl, 2-ethylhexyl '2-methylhexyl, isopentyl, tert-pentyl, roctyl, trioctyl and the like. Among these, an isopropyl group, a second butyl group, a tert-butyl group, an isopentyl group or the like is preferred, and an isopropyl group, a second butyl group, a third butyl group or the like is preferably used as the side chain. Examples of the group having an alicyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an borneol group, and an isobornyl group. , adamantyl, tricyclic fluorenyl and the like. Among these, a cyclohexyl group, an borneol group, an isobornyl group, an adamantyl group, a tricyclodecyl group or the like is preferable, and a cyclohexyl group, an original borneol group, an isobornyl group or the like is more preferable. Examples of the monomer containing the above-mentioned group having a branching and/or alicyclic structure in a side chain include styrenes, (meth)acrylates, vinyl ethers, vinyl esters, and (meth)acryl oxime. The amines and the like are preferably (meth) acrylates, vinyl esters, (meth) acrylamides, more preferably (meth) acrylates 0 - 14 - 200813630 as having the above-mentioned side chain Specific examples of the monomer of the branched structure include isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, third amyl (meth)acrylate, second-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, (meth)acrylic acid 3-octyl ester, (meth)acrylic acid trioctyl ester, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl methacrylate, etc. are preferred, more preferably Isopropyl methacrylate, butyl methacrylate, and the like. Next, as a specific example of the monomer having the above-mentioned group having an alicyclic structure in the side chain, it is a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples thereof include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylic acid-1-adamantyl ester, and (meth)acrylic acid-2-adamantyl ester. 3-methyl-1-adamantyl (meth)acrylate,-3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate , (meth)acrylic acid 3-methyl-5-ethyl-1-adamantyl ester '(meth)acrylic acid-3,5,8-triethyl-1-adamantyl ester, (meth)acrylic acid -3,5· dimethyl-8-ethyl-1-adamantyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2_(meth)acrylate Adamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methylene fluoren-5-yl (meth) acrylate, octahydro (meth) acrylate 4,7-methyleneinden-1-ylmethyl ester, (meth)acrylic acid-1-capped ester, tricyclodecyl (meth)acrylate, (hydroxy)-3-hydroxy-2,6, 6-trimethyl-bicyclo[3·1·1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-15 - 200813630 keto-4-hydroxy-bicyclo[4·1·0]heptyl ester ,(Methacrylate Original) borneol ester, isobornyl (meth)acrylate, methacrylate, (meth)acrylic acid-2,2,5-trimethylcyclohexyl ester, cyclohexyl (meth)acrylate, etc. . Among these (meth) acrylates, cyclohexyl (meth)acrylate, borneol (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid are preferred. 1-adamantyl ester, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantane (meth)acrylate Ester, 3-methyl-1-adamantyl (meth) acrylate, decyl (meth) acrylate, 1-caprate (meth) acrylate, tricyclodecyl (meth) acrylate, etc. It is cyclohexyl (meth)acrylate, (meth)acrylic acid (former) borneol ester, isobornyl (meth)acrylate, and 2-adamantyl (meth)acrylate. Further, as a specific example of the monomer further containing the above-mentioned group having an alicyclic structure in the side chain, a compound represented by the following formula (1) or (2) can be given. Here, in the formulae (1) and (2), X represents 1 or 2, and R represents hydrogen or a methyl group. ❿ and n each independently represent 0 to 15. In the formula (1), (2) ψ, preferably X-1 or 2, m = 0 to 8, η = 0 to 4, more preferably m = 1 to 4, η = 0 to 2 ° as a pass Preferable specific examples of the compound represented by the formula (1) or (2) include the following compounds D-1 to D-5 and Τ-1 to Τ-8. -16- 200813630

〇^CmH2mOn)-C-?=CH2 通式（1)〇^CmH2mOn)-C-?=CH2 General formula (1)

R &lt;^30-〇-(CmH2m〇n)-C-C=CH2 通式（2) H2c=0—C-〇-CH2CH2-〇-^J^^ H2C=CH-C-〇-q^0&gt; D— 3 D- 1 CH3 H2〇=C—C&quot;&quot;0~CH2〇H2—〇 ~R &lt;^30-〇-(CmH2m〇n)-CC=CH2 General formula (2) H2c=0—C-〇-CH2CH2-〇-^J^^ H2C=CH-C-〇-q^0&gt; D— 3 D- 1 CH3 H2〇=C—C&quot;&quot;0~CH2〇H2—〇 ~

H2C=CH-g-〇-^Q D- 4 D- 2 H2O 印 i. D— 5 -17- 200813630H2C=CH-g-〇-^Q D- 4 D- 2 H2O India i. D— 5 -17- 200813630

Τ-4 Τ-8 含有上述在側鏈具有脂環構造的基之單體係可使用適 宜製造者，也可使用市售品。 作爲上述市售品，可舉出日立化成工業（股）製：FA-5 1 1 A、FA-5 12A(S)、FA-5 1 2M、FA-5 1 3 A、FA-513M、 TCPD-A、TCPD-M、H-TCPD-A、H-TCPD-M、TOE-A、 T Ο E - Μ、H - T Ο E - A、H - T Ο E - M等。於此等之中，從顯像性 優異、變形回復率優異之點來看，較佳爲 FA-5 12 A(S)、 5 12M。 一在側鏈具有酸性基的基：Y — 作爲上述酸性基，並沒有特別的限制，可以從眾所周 -18 - 200813630 知者之中適宜地選擇，例如可舉出羧基、磺酸基、磺醯月安 基、磷酸基、酚性羥基等。於此等之中，從顯像性及硬化 膜的耐水性優異之點來看，較佳爲羧基、酚性羥基。 作爲上述在側鏈具有酸性基的基之單體，並沒有特別 的限制，可舉出苯乙烯類、（甲基）丙烯酸酯類、乙烯醚類 、乙烯酯類、（甲基）丙烯醯胺類等，較佳爲（甲基）丙烯酸 酯類、乙烯酯類、（甲基）丙烯醯胺類，更佳爲（甲基）丙烯 酸酯類。 作爲上述在側鏈具有酸性基的基之單體的具體例子， 可以從眾所周知者之中適宜地選擇，例如可舉出（甲基）丙 烯酸、乙烯基苯甲酸、馬來酸、馬來酸單烷酯、富馬酸、 伊康酸、巴豆酸、肉桂酸、山梨酸、α-氰基肉桂酸、丙烯 酸二聚物、具羥基的單體與環狀酸酐的加成反應物、ω-羧 基-聚己內酯單（甲基）丙烯酸酯等。此等係可使用適宜製造 者，也可使用市售品。 作爲上述具羥基的單體與環狀酸酐的加成反應物所用 之具羥基的單體，例如可舉出（甲基）丙烯酸2-羥乙酯等。 作爲上述環狀酸酐，例如可舉出馬來酸酐、富馬酸酐、環 己烷二羧酸酐等。 作爲上述市售品，可舉出東亞合成化學工業（股）製： Aronix M-53 00、Aronix M-5400、Aronix M-5 500、Aronix M-5 600、新中村化學工業（股）製：NK酯 CB-1、NK酯 -19- 200813630 CBX-l、共榮社油脂化學工業（股）製；hoa-MP、HOA-MS 、大阪有機化學工業（股）製：Vi sco at #2100等。於此等 之中，從顯像性優異、低成本之點來看，較佳爲（甲基）丙 烯酸等。 一在側鏈具有乙烯性不飽和基的基：Z — 作爲上述「在側鏈的乙烯性不飽和基」，並沒有特別 的限制，作爲乙烯性不飽和基，較佳係（甲基）丙烯醯基。 又，乙烯性不飽积基與單體的連結，只要是酯基、醯胺基 、胺甲醯基等的2價連結基即可，並沒有特別的限制。作 爲在側鏈導入乙烯性不飽和基的方法，可以從眾所周知者 之中適宜地選擇，例如可舉出在具有酸性基的基附加具有 環氧基的（甲基）丙烯酸酯之方法，在具有羥基的基附加具 有異氰酸基的（甲基）丙烯酸酯之方法，在具有異氰酸基的 基附加具有羥基的（甲基）丙烯酸酯之方法等。 其中，在具有酸性基的重複單位附加具有環氧基的（甲 基）丙烯酸酯之方法係最容易製造，在低成本方面係較佳的 〇 作爲上述具有乙烯性不飽和結合及環氧基的（甲基）丙烯 酸酯，只要具有此等即可，而沒有特別的限制，例如較佳 爲下述構造式（1)所表示的化合物及下述構造式（2)所表示 的化合物。 -20- 200813630 R1 =(_〇 構造式⑴ J/ \ 1 0 L-v {曰是，於上述構造式（1)中’ R1表不氣原子或甲基。L1 表示有機基。Τ-4 Τ-8 A single system containing the above-mentioned group having an alicyclic structure in a side chain can be suitably used, and a commercially available product can also be used. As the above-mentioned commercial products, Hitachi Chemical Co., Ltd. can be used: FA-5 1 1 A, FA-5 12A (S), FA-5 1 2M, FA-5 1 3 A, FA-513M, TCPD. -A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, T Ο E - Μ, H - T Ο E - A, H - T Ο E - M, etc. Among these, FA-5 12 A(S) and 5 12M are preferable from the viewpoint of excellent developability and excellent deformation recovery. A group having an acidic group in the side chain: Y - is not particularly limited as the above-mentioned acidic group, and can be suitably selected from the public, -18 - 200813630, and examples thereof include a carboxyl group, a sulfonic acid group, and a sulfonate.醯月安基, phosphate group, phenolic hydroxyl group, etc. Among these, a carboxyl group or a phenolic hydroxyl group is preferred from the viewpoint of excellent development properties and water resistance of the cured film. The monomer having a group having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth)acrylates, vinyl ethers, vinyl esters, and (meth)acrylamide. The class or the like is preferably a (meth) acrylate, a vinyl ester or a (meth) acrylamide, more preferably a (meth) acrylate. Specific examples of the monomer having a group having an acidic group in the side chain can be appropriately selected from among those skilled in the art, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, maleic acid, and maleic acid. Addition reaction of alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxyl group - Polycaprolactone mono (meth) acrylate or the like. These may be either a suitable manufacturer or a commercially available product. The hydroxyl group-containing monomer used for the addition reaction of the hydroxyl group-containing monomer and the cyclic acid anhydride may, for example, be 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, fumaric anhydride, and cyclohexanedicarboxylic anhydride. As the above-mentioned commercial products, the East Asian Synthetic Chemical Industry Co., Ltd. system: Aronix M-53 00, Aronix M-5400, Aronix M-5 500, Aronix M-5 600, and New Nakamura Chemical Industry Co., Ltd.: NK ester CB-1, NK ester-19- 200813630 CBX-l, Kyoeisha Oil Chemical Industry Co., Ltd.; hoa-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.: Vi sco at #2100, etc. . Among these, (meth)acrylic acid or the like is preferred from the viewpoint of excellent developability and low cost. A group having an ethylenically unsaturated group in the side chain: Z - is not particularly limited as the above-mentioned "ethylenically unsaturated group in the side chain", and is preferably an ethylenically unsaturated group, preferably a (meth) propylene group.醯基. Further, the connection between the ethylenic unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, a mercapto group or an amine formazan group. The method of introducing an ethylenically unsaturated group into the side chain can be suitably selected from the well-known ones, and for example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group can be mentioned. A method of adding a (meth) acrylate having an isocyanate group to a group of a hydroxyl group, a method of adding a (meth) acrylate having a hydroxyl group to a group having an isocyanate group, and the like. Among them, a method in which a (meth) acrylate having an epoxy group is added to a repeating unit having an acidic group is most easily produced, and a hydrazine which is preferable at a low cost is used as the above-mentioned ethylenically unsaturated bond and epoxy group. The (meth) acrylate is not particularly limited as long as it has such a compound, and is preferably a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2). -20- 200813630 R1 = (_〇 Structural Formula (1) J / \ 1 0 L-v {曰 is, in the above structural formula (1), R1 represents no gas atom or methyl group. L1 represents an organic group.

構造式(2) 但是，於上述構造式（2)中’ R2表示氫原子或甲基。L2 表示有機基。W表不4〜7員環的脂肪族烴基。 於上述構造式（1)所表示的化合物及構造式（2)所表示的 化合物之中，構造式（1)所表示的化合物係優於構造式（2) () 。於上述構造式（1)及（2)中，L1及L2各自獨立更佳係碳數 1〜4的伸烷基者。 作爲上述構造式（1)所表示的化合物或構造式（2)所表示 的化合物，並沒有特別的限制，例如可舉出以下的例示化 合物（1)〜（1 〇)。 -21- 200813630Structural Formula (2) However, in the above structural formula (2), R 2 represents a hydrogen atom or a methyl group. L2 represents an organic group. The W table does not have an aliphatic hydrocarbon group of 4 to 7 membered rings. Among the compounds represented by the above structural formula (1) and the compounds represented by the structural formula (2), the compound represented by the structural formula (1) is superior to the structural formula (2) (). In the above structural formulae (1) and (2), L1 and L2 are each independently preferably an alkyl group having 1 to 4 carbon atoms. The compound represented by the above structural formula (1) or the compound represented by the structural formula (2) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (1). -21- 200813630

⑹ ⑺ ⑻ ⑼ Ό ’⑽ 一其它基：L 一 別的限制， 作爲具有上述其它基（L)的單體，並沒有特 -22- 200813630 例如可舉出不具有分枝及/或脂環構造的（甲基）丙烯酸酯、 苯乙烯、乙烯醚、具二元酸酐基、乙烯酯基、烴烯基等的 單體等。 作爲上述乙烯醚基，並沒有特別的限制，例如可舉出 丁基乙烯醚基等。 作爲上述二元酸酐基，並沒有特別的限制，例如可舉 出馬來酸酐基、伊康酸酐基等。 作爲上述乙烯酯基，益沒有特別的限制，倒可舉出 醋酸乙烯酯基等。 作爲上述烴烯基，並沒有特別的限制，例如可舉出丁 二烯基、異戊二烯基等。 於上述樹脂（A)中，具有其它基（L)的單體之含有率，以 莫耳組成比計較佳係0〜30莫耳％，更佳係〇〜20莫耳％。 作爲樹脂（A)的具體例子，例如可舉出下述化合物構造 P-1〜P-35所表示的化合物。 -23- 200813630(6) (7) (8) (9) Ό '(10) One other group: L is a limitation, and as a monomer having the above other group (L), there is no specific -22-200813630, for example, without branching and/or alicyclic structure (meth) acrylate, styrene, vinyl ether, a monomer having a dibasic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group, or the like. The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group. The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an Ikonic anhydride group. The vinyl ester group is not particularly limited, and examples thereof include a vinyl acetate group and the like. The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butylene group and a prenyl group. In the above resin (A), the content of the monomer having another group (L) is preferably from 0 to 30 mol%, more preferably from -20 mol%, based on the molar composition ratio. Specific examples of the resin (A) include the compounds represented by the following compound structures P-1 to P-35. -23- 200813630

COOHCOOH

COOH 〇 OH I x:y:z=45:20:35COOH 〇 OH I x:y:z=45:20:35

人 000^^0^^ OH I 〇 P-2Person 000^^0^^ OH I 〇 P-2

x:y:z=40:20:40x:y:z=40:20:40

coo^^ HCT^^Sd 〇 P-4Coo^^ HCT^^Sd 〇 P-4

x·y·z=40·30·30 P-5x·y·z=40·30·30 P-5

x:y:z=45:20:35x:y:z=45:20:35

C〇〇^^ 一 ΜHcr^^cr x:y:z=40:20:40C〇〇^^ One ΜHcr^^cr x:y:z=40:20:40

-24- 200813630-24- 200813630

x:y:z=30:25:45x:y:z=30:25:45

P-11 x:y:z=40:25:35P-11 x:y:z=40:25:35

c〇〇X^)c〇〇X^)

P-12 x:y:z=30:30:40 -25 200813630 coo,P-12 x:y:z=30:30:40 -25 200813630 coo,

L· coo^ ___?P{L· coo^ ___?P{

\^C〇〇H 0oo^co〇X^ 0\^C〇〇H 0oo^co〇X^ 0

HO P-13 x:y:z=45:15:40 coo,HO P-13 x:y:z=45:15:40 coo,

[_ C〇〇H[_ C〇〇H

P-14 x:y:z=35:30:35 〇P-14 x:y:z=35:30:35 〇

COOv C〇〇HCOOv C〇〇H

OH I P-15 x:y:z=45:30:25 coo, uOH I P-15 x:y:z=45:30:25 coo, u

C〇〇HC〇〇H

P-16 x:y:z=45:20:35 coo.P-16 x:y:z=45:20:35 coo.

y COOHy COOH

P-17 x:y:z=45:25:30 -26 200813630P-17 x:y:z=45:25:30 -26 200813630

ffz l OH I P-18 x*y*. ζ^Ο^δ^δFfz l OH I P-18 x*y*. ζ^Ο^δ^δ

P—20P-20

x:y:z=40:30:30 〇 &quot;&quot;P-21x:y:z=40:30:30 〇 &quot;&quot;P-21

coo^y^o^Y OH I χ.β y.*z=45：20：35Coo^y^o^Y OH I χ.β y.*z=45:20:35

x：y：z=40：20：40 27- 200813630x:y:z=40:20:40 27- 200813630

COOHCOOH

H X COO^Y^O^N^ OH I P—24 x:y:z=44:16:40H X COO^Y^O^N^ OH I P—24 x:y:z=44:16:40

C〇0、^^ C〇〇Me COOH P - 25 OH 丨 x:l:y:z二46:2:20:32 ΌC〇0,^^ C〇〇Me COOH P - 25 OH 丨 x:l:y:z二46:2:20:32 Ό

π COOMe COOH COO^Y^O&quot;%^ p_26 OH 1 x:l:y:z=45·5:2:19:33. coo u Όπ COOMe COOH COO^Y^O&quot;%^ p_26 OH 1 x:l:y:z=45·5:2:19:33. coo u Ό

•Ί COOH•ΊCOOH

Hicoo^^o^N^ P-27 OH 丨 x：y：z=48：22：30Hicoo^^o^N^ P-27 OH 丨 x:y:z=48:22:30

x COOx COO

fv COOHFv COOH

οοο^γ^ο OH 〇Οοο^γ^ο OH 〇

P-28 x:y:z=51. 5:18.5:30 28- 200813630P-28 x:y:z=51. 5:18.5:30 28- 200813630

coon〇Coon〇

C〇〇HC〇〇H

^ l OH I P-29^ l OH I P-29

COOnoCOOno

y C〇〇Hy C〇〇H

x:y:z=45:25:35 Ox:y:z=45:25:35 O

OH I P-30 COO ch2ch2-qOH I P-30 COO ch2ch2-q

y C〇〇Hy C〇〇H

x:y:z=41:24:35 O oh ' P-31x:y:z=41:24:35 O oh ' P-31

x:y:z=39:26:35 ux:y:z=39:26:35 u

〇〇

OH I P - 32 x:y:z=35:30:35OH I P - 32 x:y:z=35:30:35

OO

oh I P-33 x:y:z=42:28:30 29- 200813630Oh I P-33 x:y:z=42:28:30 29- 200813630

coo 0H2CH2 - ΟCoo 0H2CH2 - Ο

ffz l OH I P-34 x: y ·· z=37 ·· 28:35Ffz l OH I P-34 x: y ·· z=37 ·· 28:35

COOCOO

OO

y COOH CH2CH2 - oy COOH CH2CH2 - o

OH I P-35 χ·γ·z=39'26*35 —樹脂（A)的製法一 上述樹脂（A)係由單體的（共）聚合反應步驟及導入乙烯 性不飽和基的步驟之二階段步驟來製作。 首先’（共）聚合反應係由各種單體的（共）聚合反應來作 ’並沒有特別的限制，可從眾所周知者之中適宜地選擇。 例如’就聚合的活性種而言，可適宜選擇自由基聚合、陽 離子聚合、陰離子聚合、配位聚合等。於此等之中，從合 成容易、低成本之點來看，較佳爲自由基聚合。又，聚合 方法亦沒有特別的限制，可從眾所周知者之中適宜地選擇 。例如可適宜選擇整體聚合法、懸浮聚合法、乳化聚合法 、溶液聚合法等。於此等之中，更佳爲溶液聚合法。 一分子量一 適合作爲樹脂（A)的上述共聚物的重量平均分子量，較 -30- 200813630 佳係1 0，0 ο 〇〜1 〇萬，更佳係1 2，〇 〇 〇〜6萬，特佳係 15,000〜4.5萬。重量平均分子量若在上述範圍內，從共聚 物的製造適合性、顯像性之點來看係較宜的。又’在難以 由於熔融黏度的降低而使得所形成的形狀崩塌之點、以及 難以變交聯不良之點、顯像沒有間隙子形狀的殘渣之點係 較宜的。 -玻璃轉移溫度- 樹脂（Α)的合適玻璃轉移溫度（Tg)，較佳係40〜180Τ： ，更佳係45〜140°C，特佳係50〜130°C。玻璃轉移溫度 (Tg)若在上述較佳範圍內，則可得到具有良好顯像性、力 學強度之光間隙子。 一酸價一 樹脂（A)的合適酸價，雖然較佳的範圍係隨著分子構造 而變動，但一般較佳爲 20mgKOH/g 以上，更佳爲 50mgKOH/g以上，特佳爲 70〜130mgKOH/g。酸價若在上 述較佳範圍內內，則可得到具有良好顯像性、力學強度的 光間隙子。 上述樹脂（A)的玻璃轉移溫度（Tg)係40〜180°C，且重 量平均分子量係1 0,000〜1〇〇,〇〇〇，此從可得到具有良好顯 像性、力學強度的光間隙子之點來看係較宜的。 再者，上述樹脂（A)的較佳例子係爲較佳的上述分子量 、較佳的上述玻璃轉移溫度（Tg)、及較佳的上述酸價之各 -31- 200813630 自更佳組合。 本發明中的樹脂（A)係至少具有X(x莫耳％)的上述在側 鏈具有分枝及/或脂環構造的基、Y(y莫耳％)的具有酸性基 的基、及Z(z莫耳％)的具有乙烯性不飽和基的基之各自不 同的共聚合單位之3元共聚合以上的共聚物，此從變形回 復率、顯像殘渣、網狀物的觀點來看係較宜的。具體地， 較佳爲使構成上述X、Y、Z的各個單體以至少丨個所成的 共聚物Λ 上述樹脂（A)的上述各成分之共聚合組成比係考慮玻璃 轉移溫度和酸價來決定，不能一槪言之，但「在側鏈具有 分枝及/或脂環構造的基」較佳係1 0〜7 0莫耳％，更佳係 1 5〜6 5莫耳％，特佳係2 0〜6 0莫耳％。在側鏈具有分枝及 /或脂環構造的基的共聚合組成比若在上述範圍內，則可得 到良好的顯像性，而且影像部的顯像液耐性亦良好。 又’ 「在側鏈具有酸性基的基」的共聚合組成比較佳 係5〜7 0莫耳。/。，更佳係丨〇〜6 〇莫耳％，特佳係2 〇〜5 〇莫 耳％ °在側鏈具有酸性基的基之共聚合組成比若在上述範 圍內，則可得到良好的硬化性、顯像性。 另外’ 「在側鏈具有乙烯性不飽和基的基」的共聚合 組成比較佳係1〇〜7〇莫耳％，更佳係2〇〜7〇莫耳％，特佳 係3 0〜70莫耳％。在側鏈具有乙烯性不飽和基的基之共聚 合組成比若在上述範圍內，則顔料分散性優異，而且顯像 -32- 200813630 性及硬化性亦良好。 上述樹脂（A)的含量，對於上述感光性組成物總固體成 分而言，較佳係5〜70質量％，更佳係10〜50質量％。樹 脂（A)係可含有後述之樹脂（A)以外的樹脂，但較佳爲僅由 樹脂（A)所構成。 —樹脂（A)以外的樹脂― 作爲可與上述樹脂（A)倂用的樹脂（A)以外之樹脂，較佳 爲對鹼性水溶液顯示膨潤性的化合钧，更佳爲對鹼性水溶 液爲可溶性的化合物。 作爲對鹼性水溶液顯示膨潤性或溶解性的樹脂，例如 可合適地舉出具有酸性基者，具體地較佳爲在環氧化合物 導入有乙烯性不飽和雙鍵和酸性基的化合物（環氧丙烯酸酯 化合物）、在側鏈具有（甲基）丙烯醯基及酸性基的乙烯系共 聚物、環氧丙烯酸酯化合物與在側鏈具有（甲基）丙烯醯基 及酸性基的乙烯系共聚物之混合物、馬來醯胺酸系共聚物 等。 作爲上述酸性基，並沒有特別的限制，可按照目的來 適宜選擇，例如可舉出羧基、磺酸基、磷酸基等，於此等 之中，從原料的取得性等觀點來看，較佳可舉出羧基。 一樹脂（A)與樹脂（A)以外的樹脂之比率一 與上述樹脂（A)可倂用的樹脂之合計含量，對於上述感 光性組成物總固體成分而言，較佳爲5〜70質量％，更隹 -33- 200813630 爲1 0〜5 0質量％。該固體成分含量若低於5質量％，則後 述的感光層之膜強度容易變弱，該感光層的表面之膠黏性 會惡化，若超過70質量％，則曝光感度會降低。再者，上 述含量表示固體成分含量。 一聚合性化合物（Β)、光聚合引發劑（C)、其它成分一 於本發明中，作爲聚合性化合物（Β)、光聚合引發劑（C) 、其它成分，可以合適地採用眾所周知的構成組成物的成 分，作爲如此的成分，例如可舉出特聞2006-23 696號公報 的段落編號[〇〇1〇]〜[0 020]中記載的成分、或特開2006-64921號公報的段落編號[0027]〜[0053]中記載的成分。 就與上述樹脂（Α)的關係而言，聚合性化合物（Β)對樹脂 (Α)的質量比率（（Β)/(Α)比）較佳係0.5〜2.0，更佳係0.6〜 1.4，特佳係0.7〜1.2。（Β)/(Α)比若在上述較佳範圍內，則 可得到具有良好顯像性、力學強度之光間隙子。 上述光聚合引發劑（C)的含量，對於樹脂（Α)而言，較佳 係0 · 1〜2 0質量％，更佳係0.5〜1 0質量％。 一微粒子（D) — 於上述感光性組成物中，較佳爲添加微粒子。作爲上 述微粒子（D)，並沒有特別的限制，可按照目的作適宜選擇 ，例如較佳爲特開2003 -3 0263 9號公報[003 5 ]〜[〇〇41]中記 載的體質顔料，其中從得到具有良好顯像性、力學強度的 光間隙子之觀點來看，較佳爲膠態矽石。 -34- 200813630 上述微粒子（D)的平均粒徑，從得到具有高的 之光間隙子的觀點來看，較佳爲5〜50nm，更隹 40nm，特佳爲15〜30nm。 又，上述微粒子（D)的含量，從得到具有高的 之光間隙子的觀點來看，對於本發明的感光性組 總固體成分而言，質量比率較佳係5〜5 0質量％ 10〜40質量％，特佳係15〜30質量％。 [圖案化步驟] 本發明中的圖案化步驟，係將支持體上所形 性樹脂層作曝光及顯像而圖案化。作爲圖案化步 例子，可舉出特開2006_6492 1號公報的段落編顯 [0077]中所記載的形成例、或特開2006 — 23 696 段落編號[0040]〜[005 1 ]中所記載的步驟等當作 的合適例。 &lt;液晶顯示裝置用基板&gt; 本發明的液晶顯示裝置用基板係具備由上述 光間隙子之製法所得的光間隙子。光間隙子較佳 體上所形成的黑色矩陣等顯示用遮光部之上或在 驅動元件上形成。又，於黑色矩陣等的顯示用 TFT等的驅動元件與光間隙子之間，亦可存在有 透明導電層（透明電極）或聚醯亞胺等的液晶配向S 例如，於光間隙子設置在顯示用遮光部或驅 力學強度 i爲1 0〜 力學強度 成物中的 ，更佳係 成的感光 驟的具體 i [007 1]〜 號公報的 本發明中 本發明的 係在支持 TFT等的 遮光部或 ITO等的 莫。 動元件之 -35- 200813630 上時，可藉由在該支持體上覆蓋預先配設的顯示用遮光部（ 黑色矩陣等）或驅動元件，例如將感光性樹脂轉印薄膜的感 光性樹脂層積層在支持體面，作剝離轉印而形成感光性樹 脂層後，對其施予曝光、顯像、加熱處理等，以形成光間 隙子，而製作本發明的液晶顯示裝置用基板。 於本發明的液晶顯示裝置用基板中，更可視需要設置 紅色（R)、藍色（B)、綠色（G)的3色等之著色畫素。 &lt;液晶顯不兀件&gt; 可設置上述本發明的液晶顯示裝置用基板，以構成液 晶顯示元件。作爲液晶顯示元件的1個例子，可舉出在至 少一者爲透光性的一對支持體（含本發明的液晶顯示裝置用 基板）之間，至少具備液晶層與液晶驅動手段（含單純矩陣 驅動方式及主動矩陣驅動方式）者。 於該情況下，本發明的液晶顯示裝置用基板，係可構 成具有複數的RGB畫素群且構成該畫素群的各畫素互相被 黑色矩陣或離隔的彩色濾光片基板。於該彩色濾光片基板 中，可設置高度均一且變形回復性優異的光間隙子。因此 ，具備該彩色濾光片基板的液晶顯示元件，係可抑制彩色 濾光片基板與對向基板之間液晶胞間隙不均（液晶胞厚變動） 的發生，可有效地防止色不均等的顯示不均之發生。由此 所製作的液晶顯示元件係可顯示鮮明的影像。 又，作爲液晶顯示元件的其它態樣，有在至少一者爲 -36- 200813630 透光性的一對支持體（含本發明的液晶顯示裝置用基板）之 間，至少具備液晶層及液晶驅動手段，上述液晶驅動手段 具有主動元件（例如TFT)，而且在一對基板間藉由高度均 一且變形回復性優異的光間隙子來控制指定寬度所構成者 〇 於該情況下，本發明的液晶顯示裝置用基板，係可構 成具有複數的RGB畫素群且構成該畫素群的各畫素互相被 黑色矩陣或離隔的彩色濾光片基板。 作爲本發明中所可使用的液晶，可舉出向列液晶、膽 固醇型液晶、層列液晶、鐵電液晶。 又，上述彩色濾光片基板的上述畫素群，可由互相呈 現不同色的2色之畫素所構成，也可由3色的畫素、4色 以上的畫素所構成。例如於3色的情況，由紅（R)、綠（G) 及藍（B)的3個色相所構成。於配置RGB 3色的畫素群時 ，較佳爲馬賽克型、三角型等的配置，於配置4色以上的 畫素群時，可爲任何配置。彩色濾光片基板的製作，例如 可在形成2色以上的畫素群後，形成如前述的黑色矩陣， 相反地，亦可在形成黑色矩陣後，形成畫素群。關於RGB 畫素的形成，可參考特開2004-347831號公報等。 &lt;液晶顯示裝置&gt; 本發明的液晶顯示裝置，係設置上述液晶顯示裝置用 基板而構成者。又，本發明的液晶顯示裝置，係設置上述 -37- 200813630 液晶顯示元件而構成者。即，如前述地，以本發明的光間 隙子之製法所製作的光間隙子，將互相面對面而對向配置 的一對基板間控制在指定的寬度，在所控制的間隙中封入 液晶材料（將封入部位稱爲液晶層）而構成，使液晶層的厚 度（液晶胞厚）被保持在所欲的均一厚。 作爲液晶顯示裝置的液晶顯示模式，可合適地舉出 STN型、TN型、GH型、ECB型、鐵電性液晶、反鐵電性 液晶、VA型、IPS型、OCB型、ASM型、其它各種者。 其中’於本發明的液晶顯示裝置中，從最有效地達成本發 明的效果之觀點來看，希望容易由於液晶胞的液晶胞厚之 變動而發生顯示不均的顯示模式，較佳係液晶胞厚爲2〜 4μπι的VA型顯示模式、IPS型顯示模式、OCB型顯示模 式所構成者。 作爲本發明的液晶顯示裝置之基本構成態樣，可舉出 (a)薄膜電晶體（TFT)等的驅動元件與畫素電極（導電層）所排 列形成的驅動側基板，與具備對向電極（導電層）的對向基 板’隔著光間隙子作對向配置，在其間隙部封入液晶材料 而構成者，（b)具備驅動基板與對向電極（導電層）的對向基 板，隔著光間隙子作對向配置，在其間隙部封入液晶材料 而構成者等，本發明的液晶顯示裝置可合適地使用於各種 液晶顯示機器。 關於液晶顯示裝置，例如在「次世代液晶顯示器技術（ -38- 200813630 內田龍男編集，工業調査會，1994年發行）」中有記載。 於本發明的液晶顯示裝置中，除了具備本發明的液晶顯示 元件以外，並沒有特別的限制，例如可構成上述「次世代 液晶顯示技術」中所記載的各種方式之液晶顯示裝置。其 中，特別有效於構成彩色TFT方式的液晶顯示裝置。關於 彩色TFT方式的液晶顯示裝置，例如在「彩色TFT液晶顯 示器（共立出版（股），1 996年發行）」中有記載。 本發明的液晶顯不裝置，除了具備前述本發明的液晶 顯不兀件以外，一般使用電極基板、偏光薄膜、位相差薄 膜、背光、間隙子·視野角補償薄膜、抗反射薄膜、光擴 散薄膜、防眩薄膜等各式各樣的構件所構成者。此等構件 例如記載於「’ 9 4液晶顯示器周邊材料·化學品的市場（島 健太郎（股）CMC，1 994年發行）」、「2003液晶關聯市場 的現狀與將來展望（下卷）（表良吉（股）富士 Chi mera總硏， 2003等發行）」中。 [實施例] 以下藉由實施例來更具體說明本發明，只要不超越本 發明的主旨，則不受以下的實施例所限定。再者，只要沒 有特別預先指明，則「％」及「份」係質量基準。 下述合成例1中顯示上述化合物構造P-1所表示的樹 脂（A)之合成。 (合成例1) -39- 200813630 於反應容器中，預先添加8.57份的1-甲氧基-2-丙醇 (DAICEL化學工業（股）製），升溫到90°C，將由6.27份的 甲基丙烯酸異丙酯（當作具有在側鏈具有分枝及/或脂環構 造的基X之單體）、5 · 1 5份的甲基丙烯酸（當作具有在側鏈 具有酸性基的基Y之單體）、1份的偶氮系聚合引發劑（和 光純藥公司製的V-601)、及8.57份的1-甲氧基-2-丙醇所 成的混合溶液，在氮氣氛下，於90 °C的反應容器中，費2 小時滴下=滴下後使反應4小時，得到丙烯酸樹脂溶液。 其次，於上述丙烯酸樹脂溶液中，添加0.025份的氫醌 單甲基醚及0.084份的溴化四乙銨後，費2小時滴下5.41 份的甲基丙烯酸縮水甘油酯（當作具有在側鏈具有乙烯性不 飽和基的基Z之單體）。滴下後，邊吹入空氣邊在90艺使 反應4小時後，藉由添加溶劑（MMPGAC)以使固體成分濃 度成爲45 %來調製，而得到由具有不飽和基的上述化合物 P-1所表示之X: y: z爲45莫耳％: 20莫耳％: 35莫耳％ 的樹脂溶液。 再者，上述化合物P-1所表示的樹脂之分子量Mw，係 表不重量平均分子量’作爲上述分子量的測定方法，使用 凝膠滲透層析儀（GPC)來測定。 接著，下述合成例2〜合成例22及合成例24〜合成例 32中顯示上述化合物構造Ρ-2、Ρ-3、Ρ-7、Ρ-8、ρ_ι〇、p_ 12〜P-15及P-24〜P-35所表示的樹脂之合成。 -40- 200813630 (合成例2) 如以下地進行上述化合物構造P-2所表示的 成。 就上述化合物構造P-2所表示的樹脂而言， 述化合物構造P - 2中的X : y : z成爲4 0莫耳％ : :35莫耳％的方式，將甲基丙烯酸第三丁酯、甲 、及甲基丙烯酸縮水甘油酯的各自添加量作變更 ' 外，藉由與合咸倒1同樣的方法來合成，丽得到 飽和基的上述化合物構造P-2所表示的樹脂溶液&lt; (合成例3) 如以下地進行上述化合物構造P-3所表示的 成例3。 就上述化合物構造P-3所表示的樹脂而言， 述化合物構造P-3中的X : y : z成爲40莫耳％ : , :40莫耳％的方式，將甲基丙烯酸異丁酯、甲基 及甲基丙烯酸縮水甘油酯的各自添加量作變更及 ，藉由與合成例1同樣的方法來合成，而得到由 和基的上述化合物構造P-3所表示的樹脂溶液。 (合成例4) 如以下地進行上述化合物構造P-7所表示的 成例4。 就上述P-7所表不的樹脂而言，除了以上述 樹脂之合 除了以上 2 5莫耳％ 基丙烯酸 及使用以 由目右不 I—^ &quot;N I W I 樹脂之合 除了以上 2 0莫耳％ 丙烯酸、 使用以外 f具有不飽 ί樹脂之合 ;化合物構 -41- 200813630 造P-7中的x : y : z成爲40莫耳％ : 25莫耳％ ·· 35莫耳％ 的方式，將甲基丙烯酸異丙酯、甲基丙烯酸、及賽克若馬 (CYCLOMER)M-200(DAICEL化學工業（股）製）的各自添加 量作變更及使用以外，藉由與合成例1同樣的方法來合成 ，而得到由具有不飽和基的上述化合物構造P-7所表示的 樹脂溶液。 (合成例5) 如以下地進行上述化合锪搆造P-8所表示的樹脂之合 成例5。就上述P-8所表示的樹脂而言，除了以上述化合 物構造P-8中的X: y: z成爲35莫耳％: 30莫耳°/〇: 35莫 耳％的方式，將甲基丙烯酸第三丁酯、甲基丙烯酸、及賽 克若馬（CYCLOMER)A-200(DAICEL化學工業（股）製）的各 自添加量作變更及使用以外，藉由與合成例1同樣的方法 來合成，而得到由具有不飽和基的上述化合物構造P - 8所 表示的樹脂溶液。 (合成例6) 如以下地進行上述化合物構造P -1 0所表示的樹脂之合 成例6。 就上述P -1 0所表示的樹脂而言，除了以上述化合物構 造P-10中的X: y: z成爲30莫耳％: 30莫耳％: 40莫耳 %的方式，將甲基丙烯酸環己酯、甲基丙烯酸、及甲基丙 烯酸縮水甘油酯的各自添加量作變更及使用以外，藉由與 -42- 200813630 合成例1同樣的方法來合成’而得到由具有不飽和基的上 述化合物構造p -10所表示的樹脂溶液。 (合成例7) 如以下地進行上述化合物構造P -1 2所表不的樹肖曰之口 成例7。 就上述P-1 2所表示的樹脂而言’除了以上述化合物構 造P-12中的X: y: z成爲30莫耳％: 30莫耳％·· 40旲耳 二一％的方式，將甲基丙烯酸環己酯、甲基丙烯酸、及賽克若 馬（CYCLOMER)A-200(DAICEL化學工業（股）製）的各自添 加量作變更及使用以外，藉由與合成例1同樣的方法來合 成，而得到由具有不飽和基的上述化合物構造p-12所表示 的樹脂溶液。 (合成例8 ) 如以下地進行上述化合物構造P-13所表示的樹脂之合 () 成例8。 就上述P - 1 3所表示的樹脂而言，除了以上述化合物構 造P - 1 3中的X : y : z成爲4 5莫耳％ ·· 1 5莫耳％ : 4 0莫耳 %的方式，將甲基丙烯酸異冰片酯、丙烯酸二聚物、及賽 克若馬（CYCLOMER)M-200(DAICEL化學工業（股）製）的各 自添加量作變更及使用以外，藉由與合成例1同樣的方法 來合成，而得到由具有不飽和基的上述化合物構造P · 1 3所 表示的樹脂溶液。 •43- 200813630 (合成例9) 如以下地進行上述化合物構造P-14所表示的樹脂之，合 成例9。 就上述P-14所表示的樹脂而言，除了以上述化合物構 造P -1 4中的X : y ·· z成爲3 5莫耳％ : 3 0莫耳％ : 3 5莫耳 %的方式，將甲基丙烯酸異冰片酯、甲基丙烯酸、及賽克 若馬（CYCLOMER)A-200(DAICEL化學工業（股）製）的各自 添加量作變更及使用以外，藉由與合成例1同樣的方法來 合成，而得到由具有不飽和基的上述化合物構造P-1 4所表 示的樹脂溶液。； (合成例10) 如以下地進行上述化合物構造P-15所表示的樹脂之合 成例1 〇。 就上述P-15所表示的樹脂而言，除了以上述化合物構 造P-15中的X: y: z成爲45莫耳％: 3〇莫耳％: 25莫耳 %的方式，將甲基丙烯酸原冰片酯、甲基丙烯酸、及甲基 丙烯酸縮水甘油酯的各自添加量作變更及使用以外’藉由 與合成例1同樣的方法來合成，而得到由具有不飽和基的 上述化合物構造P· 1 5所表示的樹脂溶液。 (合成例11〜14) 於上述合成例2中，將合成例2所用的成分之添加量 調整爲表2中所記載的固體成分酸價、Mw，而得到由具有 -44- 200813630 不飽和基的上述化合物構造P-2所表示的樹脂溶液。 (合成例15〜17) 於上述合成例1中，將合成例1所用的成分之添加量 調整爲表2中所記載的固體成分酸價、Mw，而得到由具有 不飽和基的上述化合物構造P-1所表示的樹脂溶液。 (合成例1 8) 如以下地進行上述化合物構造P-24所表示的樹脂之合 成冽1 8。 就上述P-24所表示的樹脂而言，除了以上述化合物構 造P-24中的X: y·· z成爲44莫耳％: 16莫耳％·· 40莫耳 %的方式，將甲基丙烯酸環己酯、甲基丙烯酸、及甲基丙 烯酸縮水甘油酯的各自添加量作變更及使用以外，藉由與 合成例1同樣的方法來合成，而得到由具有不飽和基的上 述化合物構造P-24所表示的樹脂溶液。 (合成例19) 如以下地進行上述化合物構造P-25所表示的樹脂之合 成例1 9。 就上述P-25所表示的樹脂言，除了以上述化合物構造 P -1 8中的X ·· 1 ·· y ·· z成爲4 6莫耳％ ·· 2莫耳％ ·_ 2 0莫耳％ :32莫耳％的方式，將甲基丙烯酸環己酯、當作具有其它 基L的單體之甲基丙烯酸甲酯、甲基丙烯酸、及甲基丙烯 酸縮水甘油酯的各自添加量作變更及使用以外，藉由與合 -45- 200813630 成例1同樣的方法來合成’而得到由具有不飽和基的上述 化合物構造P - 2 5所表示的樹脂溶液。 (合成例20) 如以下地進行上述化合物構造p -2 6所表示的樹脂之合 成例20。 就上述p -2 6所表示的樹脂’除了以上述化合物構造p -2 6中的X : 1 : y : z成爲4 5.5莫耳°/“ 2莫耳°/❶：1 9莫耳％ ：3 3 .5莫耳％的方式，將甲基丙烯酸環己酯、當作具有其 它基L的單體之甲基丙烯酸甲酯、甲基丙烯酸、及甲基丙 烯酸縮水甘油酯的各自添加量作變更及使用以外，藉由與 合成例1同樣的方法來合成’而得到由具有不飽和基的上 述化合物構造P-26所表示的樹脂溶液。 (合成例21) 如以下地進行上述化合物構造P - 2 7所表示的樹脂之合 成例21。 就上述P-27所表示的樹脂而言，除了以上述化合物構 造P-27中的X ·· y ·· z成爲48莫耳％ : 22莫耳％ : 30莫耳 %的方式，將甲基丙烯酸環己酯、甲基丙烯酸、及甲基丙 烯酸縮水甘油酯的各自添加量作變更及使用以外’藉由與 合成例1同樣的方法來合成，而得到由具有不飽和基的上 述化合物構造P-27所表示的樹脂溶液。 (合成例22) 46- 200813630 如以下地進行上述化合物構造P-28所表示的樹脂之合 成例22。 就上述P-28所表示的樹脂，除了以上述化合物構造P-2 8中的X : y ·· z成爲5 1 . 5莫耳％ : 1 8.5莫耳。/。·· 3 0莫耳％ 的方式，將甲基丙烯酸環己酯、甲基丙烯酸、及甲基丙烯 酸縮水甘油酯的各自添加量作變更及使用以外，藉由與合 成例1同樣的方法來合成，而得到由具有不飽和基的上述 化合物構造P-28所表示的樹脂溶液。 (合成例23):鹼可溶樹脂（20)的調製 於反應容器中，預先添加25克1-甲氧基-2-丙醇和25 克1-甲氧基-2-丙基醋酸酯的混合溶劑，升溫到90°C，將 32.1克苯乙烯、36.5克甲基丙烯酸、6.73克偶氮系聚合引 發劑（和光純藥社製的V-601)、25克1-甲氧基-2-丙醇、及 25克1-甲氧基-2-丙基醋酸酯的混合溶液，在氮氣氛下， 於9 0 °C的反應容器中，費2小時滴下。滴下後使反應4小 時，得到丙烯酸樹脂溶液。 其次，於上述丙烯酸樹脂溶液中，添加0.5克氫醌單甲 基醚及0 · 0 1 5克溴化四乙銨後後，費2小時滴下3 1 · 3克甲 基丙烯酸縮水甘油酯。滴下後，邊吹入空氣邊在9(TC使反 應4小時，得到鹼可溶樹脂（20)溶液。該鹼可溶樹脂（2〇) 溶液中的固體成分係50%。 (合成例24) -47- 200813630 如以下地進行上述化合物構造P-25所表示的樹脂之合 成。 於合成例1 9中，除了調整引發劑量及反應溫度外，藉 由同樣的方法來合成，以得到由具有不飽和基的上述化合 物構造P-25所表示的樹脂溶液。 (合成例25〜31) 如以下地進行上述化合物構造P - 2 9〜P - 3 5所表示的樹 口匕一V 八OH I P-35 χ·γ·z=39'26*35—Preparation of Resin (A) The above resin (A) is a (co)polymerization step of a monomer and a step of introducing an ethylenically unsaturated group. Two-stage steps to make. First, the (co)polymerization reaction is carried out by (co)polymerization of various monomers, and is not particularly limited, and can be suitably selected from among those skilled in the art. For example, in terms of the active species to be polymerized, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, and the like can be suitably selected. Among these, from the viewpoint of ease of synthesis and low cost, radical polymerization is preferred. Further, the polymerization method is not particularly limited, and can be suitably selected from among those skilled in the art. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like can be suitably selected. Among these, a solution polymerization method is more preferred. The weight average molecular weight of the above copolymer having a molecular weight of one suitable as the resin (A) is more than -30-200813630, 10,0 ο 〇1 to 10,000, and more preferably 1 2, 〇〇〇~60,000. The best is 15,000~4.5 million. When the weight average molecular weight is within the above range, it is preferred from the viewpoint of the suitability and development of the copolymer. Further, it is preferable that the shape where the formed shape is collapsed due to the decrease in the melt viscosity, and the point where it is difficult to change the cross-linking failure, and the residue having no gap sub-shape is developed. - Glass transition temperature - a suitable glass transition temperature (Tg) of the resin (Α), preferably 40 to 180 Å: more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the above preferred range, a light gap having good developing power and mechanical strength can be obtained. The preferred acid value of the monovalent acid-resin (A), although the preferred range varies depending on the molecular structure, is generally preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more, and particularly preferably 70 to 130 mgKOH. /g. When the acid value is within the above preferred range, an optical spacer having good developing power and mechanical strength can be obtained. The glass transition temperature (Tg) of the above resin (A) is 40 to 180 ° C, and the weight average molecular weight is 10,000 〜1 〇〇, 〇〇〇, thereby obtaining an optical gap having good developing power and mechanical strength. It is more appropriate to look at the point of the child. Further, a preferred example of the above resin (A) is preferably a combination of a preferred molecular weight, a preferred glass transition temperature (Tg), and a preferred acid value of -31 to 200813630. The resin (A) in the present invention has at least X (x mole %) of the above-mentioned group having a branching and/or alicyclic structure in the side chain, Y (y mole %) having an acidic group, and Z (z mol %) of a copolymer having an ethylenically unsaturated group, which is a ternary copolymer of three or more copolymerized units, from the viewpoint of deformation recovery ratio, development residue, and network It is more suitable. Specifically, it is preferred that the copolymers constituting at least one of the above-mentioned X, Y, and Z monomers are copolymerized. The copolymerization ratio of the above components of the resin (A) is considered to be the glass transition temperature and the acid value. It is decided that it cannot be said in a nutshell, but "the base having a branching and/or alicyclic structure in the side chain" is preferably 10 to 70 mole %, more preferably 1 5 to 6 5 mole %, Good system 2 0~6 0 mol%. When the copolymerization ratio of the group having a branching and/or alicyclic structure in the side chain is within the above range, good developability can be obtained, and the image forming liquid resistance of the image portion is also good. Further, the copolymerization composition of "the group having an acidic group in the side chain" is preferably 5 to 70 moles. /. , more preferably 丨〇 6 6 6 6 6 , , , , , , , , , , , ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° Sexual and visual. In addition, the copolymerization composition of 'the group having an ethylenically unsaturated group in the side chain' is better than 1% to 7〇%, more preferably 2〇~7〇%, and particularly preferably 3 0~70 Moer%. When the copolymer composition ratio of the group having an ethylenically unsaturated group in the side chain is within the above range, the pigment dispersibility is excellent, and the development and the hardenability of the image are also good. The content of the resin (A) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, based on the total solid content of the photosensitive composition. The resin (A) may contain a resin other than the resin (A) to be described later, but it is preferably composed only of the resin (A). - Resin other than the resin (A) - The resin other than the resin (A) which can be used for the resin (A) is preferably a hydrazine compound which exhibits swelling property to an alkaline aqueous solution, and more preferably an alkaline aqueous solution. Soluble compound. The resin which exhibits swelling property or solubility in an alkaline aqueous solution is, for example, a compound having an acidic group, and particularly preferably a compound having an ethylenically unsaturated double bond and an acidic group introduced into the epoxy compound (epoxy) Acrylate compound), an ethylene-based copolymer having a (meth)acrylonyl group and an acidic group in a side chain, an epoxy acrylate compound, and an ethylene-based copolymer having a (meth)acrylonyl group and an acidic group in a side chain A mixture, a maleic acid copolymer or the like. The acidic group is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among them, from the viewpoint of availability of raw materials and the like, it is preferred. A carboxyl group is mentioned. The ratio of the ratio of the resin (A) to the resin other than the resin (A) to the total amount of the resin which can be used for the resin (A) is preferably 5 to 70 by mass based on the total solid content of the photosensitive composition. %, more 隹-33- 200813630 is 1 0~50 0% by mass. When the content of the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the adhesiveness of the surface of the photosensitive layer is deteriorated. When the content exceeds 70% by mass, the exposure sensitivity is lowered. Further, the above content represents the solid content. In the present invention, a polymerizable compound (Β), a photopolymerization initiator (C), and other components may be suitably used as a polymerizable compound (Β), a photopolymerization initiator (C), and other components. As a component of the composition, for example, the components described in paragraphs [〇〇1〇] to [0 020] of the Japanese Patent Publication No. 2006-23696, or the publication of JP-A-2006-64921 The components described in paragraphs [0027] to [0053]. The mass ratio ((Β) / (Α) ratio) of the polymerizable compound (Β) to the resin (Α) is preferably 0.5 to 2.0, more preferably 0.6 to 1.4, in relation to the above resin (Α). Very good 0.7 to 1.2. When the (Β)/(Α) ratio is within the above preferred range, an optical spacer having good developing power and mechanical strength can be obtained. The content of the photopolymerization initiator (C) is preferably from 0.1 to 2% by mass, more preferably from 0.5 to 10% by mass, based on the resin. A fine particle (D) - In the above photosensitive composition, fine particles are preferably added. The fine particles (D) are not particularly limited and may be appropriately selected according to the purpose, and are, for example, the extender pigments described in JP-A-2003-03902, [0035] to [41], wherein From the viewpoint of obtaining a light gap having good developing power and mechanical strength, colloidal vermiculite is preferred. The average particle diameter of the fine particles (D) is preferably 5 to 50 nm, more preferably 40 nm, and particularly preferably 15 to 30 nm from the viewpoint of obtaining a high optical spacer. Further, the content of the fine particles (D) is preferably from 5 to 50% by mass in terms of the total solid content of the photosensitive group of the present invention from the viewpoint of obtaining a high optical spacer. 40% by mass, particularly preferably 15 to 30% by mass. [Patterning Step] The patterning step in the present invention is to pattern and shape the resin layer on the support by exposure and development. Examples of the patterning step include the formation examples described in the paragraph [0077] of JP-A-2006-6492, and the paragraphs [0040] to [0051] of JP-A-2006-23 696. A suitable example of the steps and the like. &lt;Substrate for Liquid Crystal Display Device&gt; The substrate for a liquid crystal display device of the present invention includes a photo spacer obtained by the method for producing the optical spacer. The optical spacer is preferably formed on the display shading portion or the like on the driving element. Further, a liquid crystal alignment S such as a transparent conductive layer (transparent electrode) or a polyimide may be present between the driving element such as a display TFT such as a black matrix and the optical spacer, for example, in the optical spacer. In the present invention, the light-shielding portion or the mechanical strength i of the display is 10 to the mechanical strength, and the light-sensitive portion is more preferably incorporated in the present invention. Shading or ITO or the like. When the movable element is -35-200813630, the light-shielding portion (black matrix or the like) or the driving element which is disposed in advance on the support can be covered, for example, a photosensitive resin layer of the photosensitive resin transfer film can be laminated. After the photosensitive resin layer is formed by peeling and transferring on the support surface, exposure, development, heat treatment, or the like is applied to form a photo spacer, and the substrate for a liquid crystal display device of the present invention is produced. In the substrate for a liquid crystal display device of the present invention, it is more desirable to provide coloring elements such as three colors of red (R), blue (B), and green (G). &lt;Liquid crystal display device&gt; The substrate for a liquid crystal display device of the present invention described above can be provided to constitute a liquid crystal display element. An example of the liquid crystal display device includes at least one of a pair of light-transmitting supports (including the substrate for a liquid crystal display device of the present invention), and at least a liquid crystal layer and a liquid crystal driving means (including simple Matrix drive mode and active matrix drive mode). In this case, the substrate for a liquid crystal display device of the present invention can constitute a color filter substrate having a plurality of RGB pixel groups and each of the pixels constituting the pixel group being black matrixed or separated from each other. In the color filter substrate, an optical spacer having a uniform height and excellent deformation recovery property can be provided. Therefore, the liquid crystal display element including the color filter substrate can suppress the occurrence of uneven liquid crystal cell gap (change in liquid crystal cell thickness) between the color filter substrate and the counter substrate, and can effectively prevent color unevenness. The occurrence of unevenness is shown. The liquid crystal display element thus produced can display a sharp image. Further, as another aspect of the liquid crystal display device, at least one of the pair of supports having a light transmittance of -36 to 200813630 (including the substrate for a liquid crystal display device of the present invention) includes at least a liquid crystal layer and a liquid crystal drive. In the above, the liquid crystal driving means has an active element (for example, a TFT), and the optical gap between the pair of substrates is controlled by a light spacer having a high degree of uniformity and excellent deformation recovery property, and the liquid crystal of the present invention is used in this case. The display device substrate can constitute a color filter substrate having a plurality of RGB pixel groups and each of the pixels constituting the pixel group being black matrixed or separated from each other. The liquid crystal which can be used in the present invention includes nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal. Further, the pixel group of the color filter substrate may be composed of two color pixels which exhibit different colors, and may be composed of three color pixels or four or more pixels. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When RGB three-color pixel groups are arranged, it is preferably a mosaic type or a triangular type, and any arrangement of four or more pixel groups can be used. In the production of the color filter substrate, for example, a black matrix as described above may be formed after forming a pixel group of two or more colors, and conversely, a pixel group may be formed after forming a black matrix. For the formation of RGB pixels, Japanese Patent Laid-Open Publication No. 2004-347831 and the like can be referred to. &lt;Liquid Crystal Display Device&gt; The liquid crystal display device of the present invention is configured by providing the above-described substrate for a liquid crystal display device. Further, the liquid crystal display device of the present invention is constructed by providing the above -37-200813630 liquid crystal display element. In other words, as described above, the optical spacers produced by the method of manufacturing the optical spacer of the present invention are controlled to have a predetermined width between the pair of substrates which face each other and face each other, and the liquid crystal material is sealed in the controlled gap ( The sealed portion is referred to as a liquid crystal layer, and the thickness (liquid crystal cell thickness) of the liquid crystal layer is maintained to be as uniform as desired. Examples of the liquid crystal display mode of the liquid crystal display device include an STN type, a TN type, a GH type, an ECB type, a ferroelectric liquid crystal, an antiferroelectric liquid crystal, a VA type, an IPS type, an OCB type, an ASM type, and the like. Various. In the liquid crystal display device of the present invention, from the viewpoint of most effectively achieving the effects of the present invention, it is desirable to display a display mode in which display unevenness is likely to occur due to fluctuations in the liquid crystal cell thickness of the liquid crystal cell. It is composed of a VA type display mode, an IPS type display mode, and an OCB type display mode having a thickness of 2 to 4 μm. The basic configuration of the liquid crystal display device of the present invention includes (a) a driving side substrate in which a driving element such as a thin film transistor (TFT) and a pixel electrode (conductive layer) are arranged, and a counter electrode. The opposite substrate of the (conductive layer) is disposed opposite to each other with the optical gap interposed therebetween, and the liquid crystal material is sealed in the gap portion, and (b) the counter substrate having the driving substrate and the counter electrode (conductive layer) is interposed. The liquid crystal display device of the present invention can be suitably used for various liquid crystal display devices, in which the optical spacers are disposed opposite to each other and the liquid crystal material is sealed in the gap portion. The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (-38-200813630, Uchida Natsuo, Industrial Survey, Issued in 1994)". The liquid crystal display device of the present invention is not particularly limited, and may be, for example, a liquid crystal display device of various types described in the above-mentioned "second-generation liquid crystal display technology". Among them, it is particularly effective for a liquid crystal display device constituting a color TFT system. The liquid crystal display device of the color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". In the liquid crystal display device of the present invention, in addition to the liquid crystal display device of the present invention, an electrode substrate, a polarizing film, a phase difference film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, and a light diffusing film are generally used. And various components such as anti-glare film. These components are described, for example, in "The Market for Materials and Chemicals in Liquid Crystal Display (Minami Kentaro Co., Ltd., CMC, issued in 1994)", "The current status and future prospects of the liquid crystal related market in 2003 (volume)" Liang Ji (share) Fuji Chi mera, 2003, 2003, etc.). [Examples] Hereinafter, the present invention will be more specifically described by the examples, and the present invention is not limited by the following examples. Furthermore, "%" and "parts" are quality benchmarks as long as they are not specified in advance. The synthesis of the resin (A) represented by the above-mentioned compound structure P-1 is shown in the following Synthesis Example 1. (Synthesis Example 1) -39- 200813630 Into a reaction vessel, 8.57 parts of 1-methoxy-2-propanol (manufactured by DAICEL Chemical Industry Co., Ltd.) was added in advance, and the temperature was raised to 90 ° C, which was 6.27 parts. Isopropyl acrylate (as a monomer having a group X having a branching and/or alicyclic structure in a side chain), 5 · 15 parts of methacrylic acid (as having a group having an acidic group in a side chain) a mixed solution of 1 part of an azo polymerization initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) and 8.57 parts of 1-methoxy-2-propanol in a nitrogen atmosphere Next, in a reaction vessel at 90 ° C, it took 2 hours to drip = after the dropwise addition, the reaction was allowed to proceed for 4 hours to obtain an acrylic resin solution. Next, after adding 0.025 parts of hydroquinone monomethyl ether and 0.084 parts of tetraethylammonium bromide to the above acrylic resin solution, 5.41 parts of glycidyl methacrylate was dropped in 2 hours (as having a side chain) a monomer having a group Z of an ethylenically unsaturated group). After the dropwise addition, the reaction was carried out for 4 hours while blowing air, and then a solvent (MMPGAC) was added to prepare a solid content of 45% to obtain a compound P-1 having an unsaturated group. X: y: z is 45 mol%: 20 mol%: 35 mol% of the resin solution. Further, the molecular weight Mw of the resin represented by the above compound P-1 is expressed by a gel permeation chromatography (GPC) as a method for measuring the molecular weight as described above. Next, in the following Synthesis Example 2 to Synthesis Example 22 and Synthesis Example 24 to Synthesis Example 32, the above-mentioned compound structures Ρ-2, Ρ-3, Ρ-7, Ρ-8, ρ_ι〇, p_ 12 to P-15 and Synthesis of resin represented by P-24 to P-35. -40-200813630 (Synthesis Example 2) The formation of the above-mentioned compound structure P-2 was carried out as follows. With respect to the resin represented by the above-mentioned compound structure P-2, the compound in the structure P: 2 is X: y: z is 40% by mole: : 35 mol%, and the third butyl methacrylate is used. And the amount of each added to the glycidyl methacrylate and the glycidyl methacrylate were changed, and the resin solution represented by the above-mentioned compound structure P-2 obtained by the saturation of the salt was synthesized. (Synthesis Example 3) Example 3 shown by the above-mentioned compound structure P-3 was carried out as follows. With respect to the resin represented by the above-mentioned compound structure P-3, in the compound structure P-3, X: y: z is 40 mol% : , : 40 mol %, isobutyl methacrylate, The amount of each of the methyl group and the glycidyl methacrylate added was changed, and the mixture was synthesized in the same manner as in Synthesis Example 1 to obtain a resin solution represented by the above-mentioned compound structure P-3. (Synthesis Example 4) Example 4 shown by the above-mentioned compound structure P-7 was carried out as follows. In the case of the resin represented by the above P-7, in addition to the above resin, the above 2 5 mole % of the acrylic acid is used and the use of the NIWI resin is removed from the above 2 0 moles. % Acrylic acid, other than the use of f, which is not saturated with the resin; compound structure -41-200813630, x: y: z in the P-7 is 40 mol%: 25 mol% · · 35 mol %, In the same manner as in Synthesis Example 1, except that the respective amounts of isopropyl methacrylate, methacrylic acid, and CYCLOMER M-200 (manufactured by DAICEL Chemical Industry Co., Ltd.) were changed and used. The method was synthesized to obtain a resin solution represented by P-7 from the above compound having an unsaturated group. (Synthesis Example 5) The following is a synthesis example 5 of the resin represented by the above-mentioned compound structure P-8. With respect to the resin represented by the above P-8, in addition to the above compound, X: y: z in P-8 is 35 mol %: 30 mol / 〇: 35 mol %, methyl group In the same manner as in Synthesis Example 1, except that the respective amounts of addition of butyl acrylate, methacrylic acid, and CYCLOMER A-200 (manufactured by DAICEL Chemical Industry Co., Ltd.) were changed and used. Synthesis was carried out to obtain a resin solution represented by P-8 from the above compound having an unsaturated group. (Synthesis Example 6) The synthesis example 6 of the resin represented by the above-mentioned compound structure P -10 was carried out as follows. With respect to the resin represented by the above P -1 0 , methacrylic acid is used in such a manner that X: y: z in the structure P-10 of the above compound is 30 mol %: 30 mol %: 40 mol % The above-mentioned addition amounts of cyclohexyl ester, methacrylic acid, and glycidyl methacrylate were changed and used, and the same method as in Synthesis Example 1 of -42-200813630 was used to obtain 'the above-mentioned unsaturated group. The compound was constructed as a resin solution represented by p-10. (Synthesis Example 7) As shown in the following, the structure of the tree structure shown by the above-mentioned compound structure P -1 2 was carried out as an example 7. With respect to the resin represented by the above P-1 2, except that X: y: z in the structure P-12 of the above compound is 30 mol%: 30 mol%·40 旲 ear%, The same method as in Synthesis Example 1 except that the respective amounts of cyclohexyl methacrylate, methacrylic acid, and CYCLOMER A-200 (manufactured by DAICEL Chemical Industry Co., Ltd.) were changed and used. To synthesize, a resin solution represented by p-12 was synthesized from the above compound having an unsaturated group. (Synthesis Example 8) The combination of the resins represented by the above-mentioned compound structure P-13 was carried out as follows. With respect to the resin represented by the above P - 13 , in addition to the above compound, X: y : z in P - 1 3 is 4 5 mol % · · 1 5 mol % : 4 0 mol % In addition to the modification and use of the respective addition amounts of isobornyl methacrylate, acrylic acid dimer, and CYCLOMER M-200 (manufactured by DAICEL Chemical Industry Co., Ltd.), The same method was used for the synthesis, and a resin solution represented by P·13 was obtained from the above compound having an unsaturated group. • 43-200813630 (Synthesis Example 9) The resin represented by the above-mentioned compound structure P-14 was used as follows, and the synthesis example 9 was carried out. With respect to the resin represented by the above P-14, in addition to the above compound, X: y ·· z in P -1 4 is 3 5 mol % : 3 0 mol % : 3 5 mol %, The same amounts as those of Synthesis Example 1 were used except that the respective amounts of isobornyl methacrylate, methacrylic acid, and CYCLOMER A-200 (manufactured by DAICEL Chemical Industry Co., Ltd.) were changed and used. The method was synthesized to obtain a resin solution represented by P-1 4 from the above compound having an unsaturated group. (Synthesis Example 10) The synthesis example 1 of the resin represented by the above-mentioned compound structure P-15 was carried out as follows. With respect to the resin represented by the above P-15, in addition to the above compound, X: y: z in P-15 is 45 mol%: 3 mol% %: 25 mol%, methacrylic acid is used. The addition amount of each of the original borneol ester, methacrylic acid, and glycidyl methacrylate was changed by the same method as in Synthesis Example 1 to obtain a structure of the above compound having an unsaturated group. The resin solution represented by 15 . (Synthesis Examples 11 to 14) In the above Synthesis Example 2, the amount of the component used in Synthesis Example 2 was adjusted to the solid content acid value and Mw described in Table 2, and the unsaturated group having -44-200813630 was obtained. The above compound constitutes a resin solution represented by P-2. (Synthesis Examples 15 to 17) In the above Synthesis Example 1, the amount of the component used in Synthesis Example 1 was adjusted to the solid content acid value and Mw described in Table 2 to obtain the structure of the above compound having an unsaturated group. The resin solution represented by P-1. (Synthesis Example 18) The synthesis of the resin represented by the above-mentioned compound structure P-24 was carried out as follows. With respect to the resin represented by the above P-24, in addition to the above compound, X: y·· z in P-24 is 44 mol%: 16 mol%·40 mol%, methyl group is used. The respective addition amounts of cyclohexyl acrylate, methacrylic acid, and glycidyl methacrylate were changed and used, and the same procedure as in Synthesis Example 1 was carried out to obtain a structure P derived from the above compound having an unsaturated group. A resin solution represented by -24. (Synthesis Example 19) A synthesis example of the resin represented by the above-mentioned compound structure P-25 was carried out as follows. With respect to the resin represented by the above P-25, in addition to the above compound, X ·· 1 ·· y ·· z in P -1 8 is 4 6 mol % ·· 2 mol % ·_ 2 0 mol %: 32% by mole, the respective addition amounts of cyclohexyl methacrylate and methyl methacrylate, methacrylic acid, and glycidyl methacrylate which are monomers having other groups L are changed. And the synthesis was carried out in the same manner as in Example 1 of the combination of -45-200813630 to obtain a resin solution represented by P - 25 from the above-mentioned compound having an unsaturated group. (Synthesis Example 20) A synthesis example 20 of the resin represented by the above-mentioned compound structure p -26 was carried out as follows. The resin represented by the above p -2 6 'except that X: 1 : y : z in the p - 2 6 structure of the above compound becomes 4 5.5 mol / 2 mol / ❶: 19 mol % : 3 3 .5 % by mole, the respective addition amounts of cyclohexyl methacrylate, methyl methacrylate, methacrylic acid, and glycidyl methacrylate, which are monomers having other groups L, are used. In the same manner as in Synthesis Example 1, the resin solution represented by the above-mentioned compound structure P-26 having an unsaturated group was obtained. (Synthesis Example 21) The above-mentioned compound structure P was carried out as follows. - Synthesis Example 21 of the resin represented by the above-mentioned 7-7. In the resin represented by the above P-27, in addition to the above compound, X ·· y ·· z in P-27 is 48% by mole: 22 moles In the method of %: 30 mol%, the respective amounts of cyclohexyl methacrylate, methacrylic acid, and glycidyl methacrylate were changed and used, and synthesized by the same method as in Synthesis Example 1. And obtaining a resin solution represented by P-27 from the above compound having an unsaturated group (Synthesis Example 22) 46-200813630 The synthesis example 22 of the resin represented by the above-mentioned compound structure P-28 was carried out as follows. The resin represented by the above P-28 except the X in the structure of the above compound P-2 : y ·· z becomes 5 1.5 m% % : 1 8.5 mol. /.·· 3 0 mol % of the way, cyclohexyl methacrylate, methacrylic acid, and glycidyl methacrylate The resin solution represented by the structure P-28 of the above-mentioned compound having an unsaturated group was obtained by the same method as in Synthesis Example 1 except that the amount of each addition was changed and used. (Synthesis Example 23): alkali The solvent (20) was prepared in a reaction vessel, and a mixed solvent of 25 g of 1-methoxy-2-propanol and 25 g of 1-methoxy-2-propyl acetate was added in advance, and the temperature was raised to 90 ° C. 32.1 g of styrene, 36.5 g of methacrylic acid, 6.73 g of an azo polymerization initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.), 25 g of 1-methoxy-2-propanol, and 25 g of 1- A mixed solution of methoxy-2-propyl acetate was dropped in a reaction vessel at 90 ° C for 2 hours under a nitrogen atmosphere. After the dropping, the reaction was made 4 small. Then, an acrylic resin solution is obtained. Next, after adding 0.5 g of hydroquinone monomethyl ether and 0. 015 g of tetraethylammonium bromide to the above acrylic resin solution, 3 1 · 3 g of methyl group is dropped for 2 hours. After the dropwise addition, the reaction was carried out for 4 hours while blowing air at 9 (TC) to obtain a solution of the alkali-soluble resin (20). The solid content of the alkali-soluble resin (2 Å) solution was 50%. (Synthesis Example 24) -47-200813630 The synthesis of the resin represented by the above-mentioned compound structure P-25 was carried out as follows. In Synthesis Example 9, except that the initiator amount and the reaction temperature were adjusted, it was synthesized by the same method to obtain a resin solution represented by P-25 of the above compound having an unsaturated group. (Synthesis Examples 25 to 31) The above-described compound structure P - 2 9 to P - 3 5 was expressed as follows:

Jfe L 口 W U 就上述化合物構造P-29〜P-35所表示的樹脂而言，除 了以上述化合物構造P_29〜P-35中的X: y: z成爲表3中 所記載的莫耳％之方式，將表3的X單位中所記載的各化 合物、甲基丙烯酸、及甲基丙烯酸縮水甘油酯的添加量作 變更以外，藉由與合成例1同樣的方法來合成，而得到由 具有不飽和基的上述化合物構造P-29〜P-35所表示的樹脂 溶液。 (合成例32) 如以下地進行上述化合物構造P-2 1所表示的樹脂之合 成。 就上述P - 2 1所表示的樹脂而言，除了以上述化合物構 造P-21中的X: y: z成爲45莫耳％: 20莫耳％: 35莫耳 %的方式，將ADMA(甲基丙烯酸2-金剛烷酯）、甲基丙烯 酸、及甲基丙烯酸縮水甘油酯的添加量作變更以外，藉由 -48- 200813630 與合成例1同樣的方法來合成，而得到由具有不飽和基的 上述化合物構造p -21所表示的樹脂溶液。 (實施例1):轉印法 -間隙子用感光性轉印薄膜的製作一 於厚度75μηι的聚對酞酸乙二酯薄膜假支持體（PET假 支持體）之上，塗布由下述處方A所成的熱塑性樹脂層用 塗布液，使乾燥而形成乾燥層厚1 5 · 0 μηι的熱塑性樹脂層 [熱塑性樹脂層用塗布液的處方Α] •甲基甲基丙烯酸酯/丙烯酸2-乙基己酯/甲基丙烯酸苄酯/ 甲基丙烯酸共聚物 …25.0份 ( = 55/11·7/4·5/28·8[莫耳比]，質量平均分子量90,000) •苯乙烯/丙烯酸共聚物 …58.4份 ( = 63/3 7 [莫耳比]，質量平均分子量8,000)In the resin represented by the above-mentioned compound structure P-29 to P-35, X: y: z in the structure P_29 to P-35 of the above-mentioned compound becomes the % of the moles shown in Table 3 In the same manner as in the synthesis example 1, except that the amount of each compound described in the X unit of Table 3, methacrylic acid, and glycidyl methacrylate was changed, the synthesis was carried out in the same manner as in Synthesis Example 1. The above compound of a saturated group was used to construct a resin solution represented by P-29 to P-35. (Synthesis Example 32) The synthesis of the resin represented by the above-mentioned compound structure P-2 1 was carried out as follows. With respect to the resin represented by the above P - 2 1, in addition to the above compound, X: y: z in P-21 is 45 mol%: 20 mol%: 35 mol%, ADMA (A The amount of addition of 2-adamantyl acrylate, methacrylic acid, and glycidyl methacrylate was changed by the same method as in Synthesis Example 1 except that the amount of the unsaturated group was changed by -48-200813630. The above compound constitutes a resin solution represented by p-21. (Example 1): Preparation of a transfer method - a photosensitive transfer film for a spacer - A polyethylene terephthalate film dummy support (PET dummy support) having a thickness of 75 μm was coated with the following prescription A coating liquid for a thermoplastic resin layer formed by A is dried to form a thermoplastic resin layer having a dry layer thickness of 10.5 μm [Prescription of a coating liquid for a thermoplastic resin layer] • Methyl methacrylate/acrylic acid 2-B Benzyl ester / benzyl methacrylate / methacrylic acid copolymer... 25.0 parts ( = 55/11·7/4·5/28·8 [mole ratio], mass average molecular weight 90,000) • Styrene/acrylic acid copolymerization 58.4 parts (= 63/3 7 [mole ratio], mass average molecular weight 8,000)

• 2,2-雙[4-(甲基丙醯氧基聚乙氧基）苯基]丙烷 …3 9.0份 •界面活性劑1(含有下述構造物1) …10.0份 •甲醇 …9 0.0份 • 1-甲氧基-2-丙醇 …51.0份 •甲基乙基酮 …700份 其次，於所形成的熱塑性樹脂層上，塗布由下述處方Β 所成的中間層用塗布液，使乾燥而積層乾燥層厚1 . 5 μιη的 -49- 200813630 中間層。 *界面活性劑1的組成 •下述構造物1 …30% 70%• 2,2-bis[4-(methylpropoxypolyethoxy)phenyl]propane...3 9.0 parts • Surfactant 1 (containing the following structure 1) ... 10.0 parts • Methanol...9 0.0 • 1-methoxy-2-propanol...51.0 parts •methyl ethyl ketone...700 parts Next, a coating liquid for an intermediate layer prepared by the following formulation is applied onto the formed thermoplastic resin layer. Dry the layer and dry the layer thickness of 1. 5 μιη -49- 200813630 intermediate layer. *Composition of surfactant 1 • The following structures 1 ... 30% 70%

_(CH2H)y— 〇-〇 0(EO)7H •甲基乙基酮 構造物1 -(CH2-&lt;pH)4〇- -(CH^H)^ 0==€ &lt;p〇)7h OCHgCHgCnF2η+ι_(CH2H)y—〇-〇0(EO)7H •Methyl ethyl ketone structure 1 -(CH2-&lt;pH)4〇- -(CH^H)^ 0==€ &lt;p〇) 7h OCHgCHgCnF2η+ι

(n = 6，x = 5 5，y = 5，M w = 3 3 9 4 0，M w / Μ n = 2.5 5 PO:環氧丙烷，EO:環氧乙烷） [中間層用塗布液的處方B] •聚乙烯醇 …3.22份 (PVA-205，皂化率80%，（股）可樂麗製） •聚乙烯吡咯啶酮 …1.49份 (PVP K-30，ISP ·日本株式會社製） •甲醇 …42.3份 •蒸餾水 …5 24份 接著，於所形成的中間層上’更塗布由下述表1所示 處方1所成的感光性樹脂組成物層用塗布液’使乾燥而積 層乾燥層厚4 · 1 μιη的感光性樹脂組成物層。 如以上地作，構成PET假支持體/熱塑性樹脂層/中間 層/感光性樹脂組成物層的積層構造（3層的合計層厚爲 1 1.6 μ m )。然後，於感光性樹脂組成物層的表面’更加熱· -50- 200813630 加壓以黏貼當作覆蓋膜的厚度1 2 μιη之聚丙烯製薄膜’得 到間隙子用感光性轉印薄膜（1 )。 -彩色濾光片基板的製作- 藉由特開2005-3 86 1號公報的段落編號[0084]〜[0095] 中所記載的方法，製作具有黑色矩陣、R畫素、G畫素、Β 畫素的彩色濾光片。接著，在彩色濾光片基板的R畫素、 G畫素、及B畫素以及黑色矩陣之上，藉由濺鍍更形成 IΤ Ο (銦錫氧化伤）的透明電極w -光間隙子的製作- 剝離所得到的間隙子用感光性轉印薄膜（1 )之覆蓋膜’ 將所露出的感光性樹脂組成物層之表面重疊在上述所製作 的濺度形成有ITO膜的彩色濾光片基板之ITO膜上，使用 積層機LamicII型[(股）日立儀器製]，在線壓lOON/cm、 1 3 0°C的加壓·加熱條件下，以2m/分鐘的輸送速度作貼合 。然後，將PET假支持體，在與熱塑性樹脂層的界面作剝 離去除，以將感光性樹脂組成物層同時轉印到熱塑性樹脂 層及中間層（層形成步驟）。 其次，使用具有超高壓水銀燈的近接型曝光機（日立高 科技電子工程（股）製），使光罩（具有影像圖案的石英曝光 光罩）、與以該光罩和熱塑性樹脂層呈面對面的方式所配置 的彩色濾光片基板，成大略平行的垂直豎立之狀態，以光 罩面與接於感光性樹脂組成物層的中間層之側的表面之間 -51- 200813630 的距離爲 100 μπι，通過光罩，從熱塑性樹脂層側以 90mJ/cm2的曝光量作近接曝光。 然後，將三乙醇胺系顯像液（含有30%三乙醇胺，商品 名：T-PD2(富士軟片（股）製）經純水所12倍稀釋（以1份的 T-PD2與11份的純水之比例所混合）的液），在30°C於 0.04MPa的扁平噴嘴壓力下噴淋顯像50秒，去除熱塑性樹 脂層和中間層。接著，對該玻璃基板的上面，噴吹空氣以 除液後；藉囱嘖淋器來嘖灑純水10秒：以作純水嘖琳洗 淨，噴吹空氣以減少基板上的液體積留。 接著，使用碳酸鈉系顯像液（含有0.38莫耳/升的碳酸 氫鈉、0.47莫耳/升的碳酸鈉、5%的二丁基萘磺酸鈉、陰 離子界面活性劑、消泡劑、及安定劑；商品名：T-CD1 (富 士軟片（股）製）經純水所1 〇倍稀釋的液），在29 °C、 0.1 5 MP a的錐型噴嘴壓力下噴淋顯像3 0秒，得到間隙子的 圖像。 然後，使用洗淨劑（含有磷酸鹽·矽酸鹽•非離子界面 活性劑·消泡劑•安定劑，商品名：T-SD3(富士軟片（股） 製））經純水所10倍稀釋的液，藉由噴淋器，在33 °C、 0.02MPa的錐型噴嘴壓力下噴灑20秒，進行所形成的圖像 之周邊的殘渣去除，得到所欲的間隙子圖案。 接著，對設有間隙子圖案的彩色濾光片基板，在23 0 °C 下進行3 0分鐘的加熱處理（熱處理步驟），以製作光間隙子 -52- 200813630 所得到的間隙子圖案係直徑24μηι、平均高度3·6μπι的 圓柱狀。再者，平均高度係對所得到的1 〇 〇 〇個間隙子， 使用三次元表面構造解析顯微鏡（製造商：ZYG〇 Corporation，型式：New View 5022)，測定自 ITO 的透明 電極形成面起的最高間隙子之最高位置（n = 20)。 &lt;液晶顯示裝置的製作&gt; 另行’準備玻璃基板當作對岗基板，在上述所得到的 彩色濾光片基板之透明電極上及對向基板上，分別施予 PVA模式用的圖案化，在其上更設置由聚醯亞胺所成的配 向膜。 然後，在相當於環繞彩色濾光片之畫素群的周圍所設 置的黑色矩陣之外框的位置，以分配器方式來塗布紫外線 硬化樹脂的密封劑，滴下PVA模式用液晶，與對向基板貼 合後，對貼合後的基板照射UV後，作熱處理以使密封劑 硬化。於如此所得到的液晶胞之兩面，黏貼（股）SANRITZ 製的偏光板HLC2-2518。 接著，使用當作紅色（R)LED的FR1 1 12H (STANLEY電 氣（股）製的晶片型LED)、當作綠色（G)LED的DG1112H (STANLEY電氣（股）製的晶片型 LED)、當作藍色（B)LED 的DB 1 1 1 2 H (STANLEY電氣（股）製的晶片型L E D )，構成 側光方式的背光，配置在上述設有偏光板的液晶胞之背面 -53- 200813630 側，以成爲液晶顯示裝置。 (實施例2〜21、30〜37、比較例1、2) 除了於實施例1中，將樹脂（A)由合成例1所得到的化 合物構造P-1變更爲表2或表3中所記載的合成例2〜17 、25〜32所得到的化合物構造P-1〜P-15、P-21、P-29〜 P-35，將感光性樹脂組成物層用塗布液的處方1變更爲表 1中所記載的處方1〜7以外，藉由與實施例1同樣的方法 來製作光間隙子和液晶顯示裝置~所得到的間隙子圖案係 直徑24μηι、平均高度3.6μιη的圓柱狀。 表1中所記載的碳黑分散液1之組成係如下述。 •碳黑（商品名：Nipex35，Degussa日本（股）製）13.1% •分散劑（下述化合物1 ) 0.65% •聚合物（甲基丙烯酸苄酯/甲基丙烯酸=72/28莫耳比的無 規共聚合物，分子量3.7萬） 6.72% •丙二醇單甲基醚醋酸酯 79.53 %(n = 6, x = 5 5, y = 5, M w = 3 3 9 4 0, M w / Μ n = 2.5 5 PO: propylene oxide, EO: ethylene oxide) [coating solution for intermediate layer Prescription B] • Polyvinyl alcohol...3.22 parts (PVA-205, saponification rate 80%, made by Kuraray) • Polyvinylpyrrolidone... 1.49 parts (PVP K-30, ISP, Japan) • Methanol...42.3 parts•Distilled water...5 24 parts Next, the coating liquid for the photosensitive resin composition layer formed by the prescription 1 shown in Table 1 below was applied to the formed intermediate layer to dry and dry. A photosensitive resin composition layer having a layer thickness of 4 · 1 μm. As described above, the laminated structure of the PET dummy support/thermoplastic resin layer/intermediate layer/photosensitive resin composition layer (the total layer thickness of the three layers was 1 1.6 μm). Then, the surface of the photosensitive resin composition layer is heated to -50-200813630 to adhere to a polypropylene film having a thickness of 12 μm as a cover film to obtain a photosensitive transfer film for a spacer (1). . - Production of a color filter substrate - A black matrix, an R pixel, a G pixel, and a Β are produced by the method described in paragraphs [0084] to [0095] of JP-A-2005-3 86 1 A color filter for pixels. Next, on the R pixel, the G pixel, the B pixel, and the black matrix of the color filter substrate, a transparent electrode w-optical spacer of IΤ Ο (indium tin oxide damage) is formed by sputtering. Production - peeling of the obtained barrier film for photosensitive transfer film (1) - The surface of the exposed photosensitive resin composition layer is superposed on the above-described color filter in which the ITO film is formed The ITO film of the substrate was bonded at a conveying speed of 2 m/min under a pressurization/heating condition of a linear pressure of 10 O/cm and 130 ° C using a laminator type Lamic II type (manufactured by Hitachi Instruments Co., Ltd.). Then, the PET dummy support is peeled off at the interface with the thermoplastic resin layer to simultaneously transfer the photosensitive resin composition layer to the thermoplastic resin layer and the intermediate layer (layer formation step). Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp, a photomask (a quartz exposure mask having an image pattern) is faced to face the mask and the thermoplastic resin layer. The color filter substrate disposed in a manner of being substantially parallel and vertically erected with a distance of -51-200813630 between the surface of the mask surface and the side of the intermediate layer of the photosensitive resin composition layer is 100 μm The proximity exposure was performed from the side of the thermoplastic resin layer by an exposure amount of 90 mJ/cm 2 through a photomask. Then, triethanolamine-based imaging solution (containing 30% triethanolamine, trade name: T-PD2 (made by Fujifilm)) was diluted 12 times with pure water (1 part of T-PD2 and 11 parts of pure) The liquid in which the ratio of water was mixed) was spray-developed at 30 ° C under a flat nozzle pressure of 0.04 MPa for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. Next, the upper surface of the glass substrate is sprayed with air to remove the liquid; the pure water is sprinkled by the chimney shower for 10 seconds: it is washed as pure water, and air is blown to reduce the liquid volume on the substrate. . Next, a sodium carbonate-based developing solution (containing 0.38 mol/liter of sodium hydrogencarbonate, 0.47 mol/liter of sodium carbonate, 5% of sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, And stabilizer; trade name: T-CD1 (Fuji film (manufactured by Fujifilm)) diluted with 1 纯 pure water), sprayed at 29 ° C, 0.1 5 MP a cone nozzle pressure 3 0 seconds, an image of the gap is obtained. Then, using a detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, stabilizer, trade name: T-SD3 (Fuji film)), diluted 10 times with pure water. The liquid was sprayed by a cone sprayer at a pressure of a cone nozzle of 33 ° C and 0.02 MPa for 20 seconds to remove the residue around the formed image to obtain a desired gap sub-pattern. Next, the color filter substrate provided with the spacer sub-pattern is subjected to a heat treatment (heat treatment step) at 30 ° C for 30 minutes to prepare a spacer pattern diameter obtained by the optical spacer -52-200813630. 24μηι, a columnar shape with an average height of 3·6μπι. Furthermore, the average height was measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYG〇 Corporation, type: New View 5022) for one of the obtained gaps, and the measurement was made from the transparent electrode forming surface of ITO. The highest position of the highest gap (n = 20). &lt;Production of Liquid Crystal Display Device&gt; In addition, the glass substrate is prepared as a counter substrate, and the pattern for the PVA mode is applied to the transparent electrode and the counter substrate of the obtained color filter substrate, respectively. An alignment film made of polyimine is further disposed thereon. Then, the sealant of the ultraviolet curable resin is applied in a dispenser manner at a position corresponding to the outer frame of the black matrix provided around the pixel group surrounding the color filter, and the liquid crystal for PVA mode is dropped, and the counter substrate After the bonding, the bonded substrate is irradiated with UV, and then heat-treated to harden the sealing agent. On both sides of the thus obtained liquid crystal cell, a polarizing plate HLC2-2518 made of SANRITZ was adhered. Next, FR1 1 12H (a wafer-type LED manufactured by STANLEY Electric Co., Ltd.) which is a red (R) LED, and DG1112H (a wafer-type LED manufactured by STANLEY Electric Co., Ltd.) which is a green (G) LED are used. DB 1 1 1 2 H (a wafer type LED manufactured by STANLEY Electric Co., Ltd.) which is a blue (B) LED, and constitutes a backlight of a side light type, and is disposed on the back surface of the liquid crystal cell provided with the polarizing plate - 53 - 200813630 Side to become a liquid crystal display device. (Examples 2 to 21, 30 to 37, and Comparative Examples 1 and 2) In the first embodiment, the compound structure P-1 obtained by the resin (A) in Synthesis Example 1 was changed to the one shown in Table 2 or Table 3. The compound structures P-1 to P-15, P-21, and P-29 to P-35 obtained in the synthesis examples 2 to 17 and 25 to 32 are described, and the formulation 1 of the coating liquid for a photosensitive resin composition layer is changed. In the same manner as in Example 1, except that the prescriptions 1 to 7 described in Table 1, the optical spacers and the liquid crystal display device were obtained in a columnar shape having a gap sub-pattern diameter of 24 μm and an average height of 3.6 μm. The composition of the carbon black dispersion 1 described in Table 1 is as follows. • Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.) 13.1% • Dispersant (Compound 1 below) 0.65% • Polymer (benzyl methacrylate/methacrylic acid = 72/28 molar ratio) Random copolymer, molecular weight 37,000) 6.72% • Propylene glycol monomethyl ether acetate 79.53 %

N(C2H5)2 化合物1 使用日機裝公司製Nanotrac UPA-EX150，測定該碳黑 -54- 200813630 分散液1的粒徑’結果數平均粒徑爲20nm ° (實施例22):塗布法 一光間隙子的製作（液體光阻法）- 於上述所製作的濺鍍形成有ITO膜的彩色濾光片基板 之ITO膜上，藉由具有縫狀噴嘴的玻璃基板用塗布機MH-1 6 00 (FAS亞洲公司製），塗布由上述表1中所示處方的感 光性樹脂組成物層用塗布液。接著，使用真空乾燥機 VCD(東京應化公司製），歷30秒而使溶劑的一部分被乾燥 ，使塗布膜喪失流動性後，在1 20°C預烘烤3分鐘，形成 膜厚4·0 μηι的感光性樹脂組成物層（層形成步驟）。 接著’藉由與實施例1同樣的圖案化步驟及熱處理步 驟’在彩色濾光片基板上製作光間隙子。但是，曝光量爲 3 00m：T/cm2，ΚΟΗ系顯像液的顯像爲在23°C、60秒。所得 到的間隙子圖案係直徑24 μιη、平均高度3 · 6 μ m的圓柱狀 〇 光間隙子的製作後，使用該彩色濾光片基板，與實施 例1同樣地作，以製作本發明的PVA模式液晶顯示裝置。 -55- 200813630 【I嗽】 1處方7 I 比較例2 〇〇 CN 〇〇 &lt;Ν r-H 寸· | 0.42 | o o o 18.4 0.227 0.0036 0.032 2.05 處方6 比較例1 wo | 0.42 I o On o 1 9.17 ο 0.23 0.0036 0.03 2.04 處方5 實施例21 ο Ο cn ο o 1 32.! 1 (N 〇&lt; 15.8 o ο 0.23 1 0.0036 1 0.032 2.04 處方4 實施例20 00 &lt;Ν 〇\ &lt;Ν 寸· 0.42： _1 o 寸· Γ·Η 11.9 o ο 1 0.35 1_ 0.0055 0.032 2.05 處方3 實施例19 00 CN Os (Ν — Η Γ 0-42 _] o 12.7 14.3 o ο 丨 0.316 0.005 0.032 2.05 處方2 實施例18 艺 r-H 寸· ί—Η | Ό.42 I o 24.2 o ο 0.152 I 0.0024 1 0.032 2.05 處方1 il 1, ν〇 (Ν 〇〇 (Ν r-H — r-H 0.42 o S 20.5 o ο 0.227 0.0036 0.032 2.05 i 感光性樹脂組成物層用塗布液 | I 1-甲氧基-2-丙基醋酸酯 甲基乙基酮 卜 蛾 S贫 ffi- ，田 ^ M ..A gH es 鬆m 翁· ΦΦ ·· 騮ffi mm Solspass 20000 碳黑分散液1 1 Φ v〇 餾 裝§ *K .. i题 s氍 跡w 11 r f « g嫲 Q ffi- s 链 ® &lt;π 1ES If $迭 0s ^ &lt; ssg &lt;§ &lt;Π w w I 齡一 am v〇 f τ i|B| 裝Φ fe兪 B- M 經5 裝1 κ宕 « a fr ΛΛ φ 應 l^QC Μ Ci m 薆 锲 鎏 稍 祕 hJ » 9IH ^ 1 21 T ±m Β- 賴 氫醌單甲基醚 窗 i Η * 思 讲 m K ύ 観忒 fe ^ &amp; 乾各顯 s i i H νΦ C/3 蠢， 1键 Φ_Μ : Μ 丨 91? 200813630 【(N嗽】 評價 顯示 不均 &lt; c &lt; &lt; &lt; &lt; &lt; m &lt; &lt; &lt; &lt; PQ &lt; 網狀 物 cn cn τ—H 寸 寸 m m m 寸 cn m m cn &lt;N m m m m m m m m m m m m &lt;N T-^ m 顯像 性 寸 寸 对 寸 寸 寸 寸 寸 寸 寸 CN (N (N 變形回 復率 (%) 寸 寸 ·〇 寸 &lt;N (N (N m 寸 寸 寸 1辑 &amp; S 轉印 s s s s s s s s 轉印 s s s s s s £ S s s s s s s s s 微粒子(D) 平均 粒徑 (nm) JO IT) JO jn jn JO JO m Urrfll ss 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 1膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 〇 ο JO o O o o 〇 o 〇 jn o JQ Ο JO o jn O vn d jn d am N m o m ^T) m o 〇 o cn *T) (N m m cn m m CN 宕 (N 沄 沄 JO 沄 (N &lt;N &lt;N &lt;N — 〇 O o O O o 〇 〇 O 〇 〇 〇 o O O X «ο o o o in cn JO m o 〇 o o »Tj X:單位 甲基丙烯酸異丙酯 甲基丙烯酸第三丁酯 甲基丙烯酸異丁酯 甲基丙麵異丙酯 甲基丙烯酸第三丁酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸異冰片酯 甲基丙烯酸異冰片酯 甲基丙烯酸原冰片酯 甲基丙烯酸第三丁酯 甲基丙烯酸第三丁酯 甲基丙烯酸第三丁酯 甲基丙烯酸第三丁酯 甲基丙烯酸異丙酯 Μ 酸價 mgKO H/g rn s 00 vo s ο 1—4 ο m ss OS 00 〇〇 00 s 重暈平 均分子 量 10000 1 15000 13000 11000 11000 18000 10000 13000 [ 14000 10000 5000 19000 90000 110000 9000 玻璃轉 移溫度 CC) § rn g &lt;Ν (Ν Ό in 00 S f-Ή ο τ-Η VO (N 化合物 構造 ώ &lt;N cL cn pi pL 00 pL Ο PL, 04 pL m r«H pi pL di (N (N pL (N pi (N pin pL 合成例 Τ-Η m 寸 &lt;Τ) ν〇 r&gt; 00 ON ο (N ΓΠ ίο 實施例1 實施例2 1 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 丨^丨 200813630N(C2H5)2 Compound 1 was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle diameter of the carbon black-54-200813630 dispersion 1 was measured. The number average particle diameter was 20 nm (Example 22): Coating method 1 Preparation of optical spacer (liquid photoresist method) - On the ITO film of the color filter substrate on which the ITO film is formed by sputtering as described above, the coating machine for glass substrate MH-1 6 having a slit nozzle is used. 00 (manufactured by FAS Asia Co., Ltd.), a coating liquid for a photosensitive resin composition layer prescribed in the above Table 1 was applied. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.), a part of the solvent was dried for 30 seconds, and the coating film was lost in fluidity, and then prebaked at 1200 ° C for 3 minutes to form a film thickness of 4. A photosensitive resin composition layer of 0 μm (layer formation step). Then, a light spacer was formed on the color filter substrate by the same patterning step and heat treatment step as in the first embodiment. However, the exposure amount was 300 m:T/cm2, and the development of the lanthanide developing solution was at 23 ° C for 60 seconds. The obtained spacer sub-pattern was prepared by forming a cylindrical calender spacer having a diameter of 24 μm and an average height of 3 · 6 μm, and using the color filter substrate in the same manner as in the first embodiment to fabricate the present invention. PVA mode liquid crystal display device. -55- 200813630 [I嗽] 1 Prescription 7 I Comparative Example 2 〇〇CN 〇〇&lt;Ν rH inch· | 0.42 | ooo 18.4 0.227 0.0036 0.032 2.05 Prescription 6 Comparative Example 1 wo | 0.42 I o On o 1 9.17 ο 0.23 0.0036 0.03 2.04 Prescription 5 Example 21 ο Ο cn ο o 1 32.! 1 (N 〇&lt; 15.8 o ο 0.23 1 0.0036 1 0.032 2.04 Prescription 4 Example 20 00 &lt;Ν 〇\ &lt;Ν inch · 0.42 : _1 o inch · Γ · Η 11.9 o ο 1 0.35 1_ 0.0055 0.032 2.05 prescription 3 Example 19 00 CN Os (Ν - Η Γ 0-42 _] o 12.7 14.3 o ο 丨 0.316 0.005 0.032 2.05 Prescription 2 Example 18艺rH inch · ί—Η | Ό.42 I o 24.2 o ο 0.152 I 0.0024 1 0.032 2.05 Prescription 1 il 1, ν〇(Ν H(Ν rH — rH 0.42 o S 20.5 o ο 0.227 0.0036 0.032 2.05 i Coating liquid for a resin composition layer | I 1-methoxy-2-propyl acetate methyl ethyl ketone moth S poor ffi- , Tian ^ M ..A gH es 松 m 翁 · ΦΦ ·· 骝Ffi mm Solspass 20000 carbon black dispersion 1 1 Φ v〇 distillation § *K .. i title s trace w 11 rf « g嫲Q ffi- s chain® &lt;π 1ES If $叠0s ^ &lt; ssg &lt ;§ &lt;Π Ww I age one am v〇f τ i|B| loaded Φ fe兪B- M via 5 loaded 1 κ宕« a fr ΛΛ φ should l^QC Μ Ci m 薆锲鎏 slightly secret hJ » 9IH ^ 1 21 T ±m Β- lysine monomethyl ether window i Η * think m K ύ 観忒fe ^ &amp; dry each sii H νΦ C/3 stupid, 1 key Φ_Μ : Μ 丨91? 200813630 [(N嗽】 Evaluation shows unevenness &lt; c &lt;&lt;&lt;&lt;&lt; m &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; N T-^ m imaging inch inch inch inch inch inch inch inch CN (N (N deformation recovery rate (%) inch inch inch inch inch &lt;N (N (N m inch inch inch 1 &amp; S transfer sssssssss transfer ssssss £ S ssssssss microparticles (D) average particle size (nm) JO IT) JO jn jn JO JO m Urrfll ss colloidal vermiculite colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal state Meteorite 1 colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal colloidal 〇 JO JO o O oo 〇o 〇jn o JQ Ο JO o jn O vn d jn d am N mom ^T) mo 〇o cn *T) (N mm cn mm CN 宕(N 沄沄JO 沄(N &lt;N &lt;N &lt;N — 〇O o OO o 〇〇O 〇〇〇o OOX «ο ooo in cn JO mo 〇oo »Tj X: unit isopropyl methacrylate methacrylic acid tert-butyl ester isobutyl methacrylate methyl isopropyl isopropyl methyl Dibutyl acrylate methacrylate cyclohexyl methacrylate cyclohexyl methacrylate isobornyl methacrylate isobornyl methacrylate borneol ester methacrylic acid tert-butyl methacrylate tert-butyl ester Third butyl acrylate methacrylate third butyl methacrylate isopropyl acid mg acid price mgKO H / g rn s 00 vo s ο 1 - 4 ο m ss OS 00 〇〇 00 s heavy halo average molecular weight 10000 1 15000 13000 11000 11000 18000 10000 13000 [ 14000 10000 5000 19000 90000 110000 9000 Glass Transfer Temperature CC) § rn g &lt; Ν (Ν Ό in 00 S f-Ή ο τ-Η VO (N compound structure ώ &lt;N cL cn Pi pL 00 pL Ο PL, 04 pL mr«H pi pL di (N (N pL (N pi (N pin pL synthesis example Τ- m inch &lt;Τ) ν〇r&gt; 00 ON ο (N ΓΠ ίο Embodiment 1 Embodiment 2 1 Embodiment 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Embodiment 12 Embodiment 13 Embodiment 14 Example 15 丨^丨200813630

&lt; PQ &lt; &lt; &lt; &lt; CQ &lt; &lt; C &lt; &lt; C &lt; 〇 U CN cn m m m f-H 1 (N m m cn 寸 m m m cn CN (N m m m 1 m cn m m m m m m CN 寸 ro 寸 in 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 … »n «〇 «η &lt;〇 in τ—Η 轉印 轉印 S tt 轉印 轉印 轉印 塗布 &amp; S 轉印 轉印 轉印 轉印 轉印 轉印 轉印 轉印 yn »〇 in 12 in *Τ) &lt;〇 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 碳黑 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 膠態矽石 0.75 0.75 in (N 0.75 On 〇 Os d ON 〇 OS 〇 Os d ON 〇 Os d 0.75 0.75 m cn o ο Ο 〇 〇 &lt;N m 33.5 &lt;N m (N 1 m (N 沄 2 CN (N 18.5 宕 1 jr&gt; 〇 O o ο Ο 〇 〇 〇 (N (N 1 1 (N &lt;N 1 1 45.5 51.5 1 &lt;N m 甲基丙烯酸異丙酯 甲基丙烯酸異丙酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 甲基丙烯酸環己酯 1 (苯乙嫌） r^4 ο 〇 〇 〇 T-H 〇 1-H VO S S 5〇 ο 14000 12000 18000 18000 18000 18000 18000 13000 12000 13000 13000 13000 30000 30000 36000 12000 Eo ο S S S VO 2 m 00 νο pL pin P-10 P-10 P-10 P-10 1 P-10 P-24 P-25 P-26 P-27 1 P-28 P-25 P-25 1 v〇 VO VO VO v〇 00 Os 1 m &lt;Ν 實施例16 實施例17 實施例18 | 實施例19 實施例20 實施例21 實施例22 實施例23 實施例24 實施例25 實施例26 實施例27 實施例匙 實施例22 比較例1* 比較例2 ^4n^s0009e$PM %wMo(N/%wMooo=瀣褰K稍&amp;/餵^褰瀣线1£稍&amp;:*。聊X迄輕恶«rai^e彦靼() •oovo· 200813630 【e漱】 評價 lv 鷗 &lt; &lt; &lt; &lt; &lt; C &lt;d &lt; 網狀物 m m cn cn m ΓΛ cn m 積層適 合性 m m m cn CO m m m 顯像性 m cn m m m m cn m 變形回 復率 (%) &lt;n tn in tn 轉印 轉印 轉印 轉印 「獅 轉印 轉印 轉印 微粒子(D) 平均 粒徑! (nm) vn 12 12 »Ti jn 駿 i1ml1 W 膠態矽石 膠態矽石 膠態矽石 膠態矽石 in 鍛 醮 膠態矽石 膠態矽石 膠態矽石 1 JO ο JQ d ο d JQ Ο ο JQ d d 樹脂(A) N *Τί m cn in cn m m 4/Ί m ^Τ) &lt;Ν 艺 vo (N 沄 oo CN Ό (N X Ο T-H On m m P； On cn nmL X 寸 Q CO Q ▼-H Q S ν〇 寸 oo ADM A 酸價 (mgKOH /g) T-H m T—&lt; &lt;N 00 ON ΓΛ v〇 H 卜 Os s $ 韋暈平 均分子 里 15000 15000 15000 11000 11000 11000 11000 13000 玻璃轉移 溫度(°c) ο Os o ^&quot;4 r-H r-H CN (N f-H ΓΛ g H 化合物 構造 Ον CN cL pL T-H rn Oh (N rn pI m cL rn T-H (N pL 合成例 &lt;Ν CN oo &lt;N O &lt;N (N m 實施例30 實施例31 實施例32 實施例33 實施例34 實施例35 實施例36 實施例37 二餾遯匿領-&lt;Ν瀣繫 K_Bl·: vwav)^(^)雜 Hls^iLmKw}學鬆4n^s5&gt;螂：χ 丨6ς_ 200813630 (實施例23〜28) ··直徑小的平均高度高之間隙子的例 ' 於行動式機器等的小型液晶顯示裝置中，〜般畫素 係小的，且使用TN型的液晶模式。因此，大多要求間 隙子的直徑小且高度更高者。但是，直徑小、高度高 的間隙子，在製程中有一部分脫落的情況。 對應於該要求，作爲更適合的例子，於本實施例中 ，除了將樹脂（A)由合成例1所得到的化合物構造Ρ-；ι 變更爲合成洌18〜22质得到的化合锪構造P-24〜P_2 8 ，將感光性樹脂組成物層用塗布液的處方1變更爲表4 中所記載的處方8〜1 3以外，藉由與實施例1同樣的 方法來作成光間隙子。但是，T-CD1係使用經純水所5 倍稀釋者。所得到的間隙子圖案係直徑1 5 μιη、平均高 度4.7 μιη的圓柱狀。製程中沒有見到脫落。又，於本 實施例中，增加膠態矽石的比例，提高間隙子的厚度 精度。 (實施例29) 除了調整實施例28中的感光性樹脂組成物層用塗 布液之塗布量，所得到的間隙子圖案變更爲直徑1 5 μιη 、平均高度4.7 μιη的圓柱狀以外，與實施例2 8同樣地 進行。 -60- 200813630 【寸漱】 處方13 實施例28、29 (Ν (Ν Ό C&lt;l 0.22 〇 〇 〇 〇 〇 0.27 0.042 00 iri 處方12 實施例27 VO VO (N 0.22 r«H 〇 〇 〇 〇 〇 0.27 0.042 00 處方11 實施例26 CN v〇 Ό (N 0.22 〇 〇 〇 〇 〇 0.27 C.042 oo wri _1〇 實施例25 (N VO v〇 CN 0.22 〇 〇 〇 〇 〇 r 1 0.27 0.042 oo … 處方9 實施例24 (N (N VO VO &lt;N 0.22 〇 〇 〇 〇 〇 0.27 0.042 oo tn 處方8 實施例23 (S 04 VO VO (N 0.22 〇 〇 〇 〇 〇 0.27 0.042 00 感光性樹脂組成物層用塗布液 1-甲氧基-2-丙基醋酸酯 甲基乙基酮 膠態矽石分散物(與表l同樣） Solspass 20000 DPHA液(與表1同樣） 樹脂(A)的溶液(合成例18) 樹月旨(A)的溶液(合成例19) 樹月旨㈧的溶液(合成例20) 樹月旨(A)的溶液(合成例21) 樹脂(A)的溶液(合成例22) 樹月旨(A)的溶液(合成例24) |1 J if 111 W EEl· ί « 界面活性劑1(與表1同樣） 撇 H 爸 i議 § ® 冏£ m§ φ_® :赵齡 _ 19丨 200813630 [評價] 一變形回復率一 對各個光間隙子，藉由微小硬度計（DUH-W201，（股）島 津製作所製），如以下地進行測定，作評價。測定係採用 5 0μιηφ的圓錘台壓頭，於直徑24μιη的光間隙子時，最大荷 重爲50mN、保持時間爲5秒，藉由負荷-除荷試驗法來進 行，於直徑1 5 μπι的光間隙子時，最大荷重爲2 1 mN、保持 時間爲5秒，同樣地進行。由此測定値藉由下式來求得變 ί 形回復率[%]，依照下述基準作評價。測定係在22±1°C、 5 0%RH的環境下進行。 變形回復率（％) =(荷重所致的變形量[μιη]/荷重解除後的 回復量[μιη])χ100 &lt;評價基準&gt; 5 :變形回復率爲90%以上。 4 :變形回復率爲87%以上且低於90%。 3 :變形回復率爲85%以上且低於87%。 I j 2 :變形回復率爲80%以上且低於85%。 1 :變形回復率爲75 %以上且低於80%。 〇:變形回復率爲低於75%。 一顯像性一 於上述「一光間隙子的製作-」中，在近接型曝光後 ，藉由與各實施例的顯像條件同樣的方法來顯像，對所形 成的光間隙子周邊部分進行SEM觀察，確認周邊有沒有殘 渣殘留。 -62- 200813630 〈評價基準〉 5 :完全沒有見到殘渣。 4 :在圖案周邊見到若干殘渣。 3 :在圖案周邊見到殘渣。 2:在圖案周邊及圖案附近的基板上見到殘渣。 1 :基板上處處可確認有殘渣。 -積層適合性 &lt; 積層泡 &gt; 評價- 於在彩色濾光片基板上已轉印感光性樹脂轉印薄膜的 ^ ' 狀態下，剝離假支持體後，用光學顯微鏡來觀察積層狀態 ，觀察有無積層泡（積層時捲入空氣而發生的氣泡）。 &lt;評價基準&gt; 3 :完全沒有積層泡。 2 :積層泡係在圖案形成地方以外發生。 1 :積層泡係發生在圖案形成部。 一網狀物一 於45 °C /7 5 %RH環境下放置24小時後，使用顯微鏡來&lt; PQ &lt;&lt;&lt;&lt; CQ &lt;&lt; C &lt;&lt; C &lt; 〇U CN cn mmm fH 1 (N mm cn inch mmm cn CN (N mmm 1 m cn mmmmmm CN inch ro inch) In inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch Printing transfer yn »〇in 12 in *Τ) &lt;〇 colloidal gangue colloidal gangue colloidal gangue colloidal gangue colloidal gangue carbon black colloidal gangue colloidal gangue colloidal gangue State gangue colloidal gangue colloidal gangue colloidal gangue colloidal gangue colloidal gangue colloidal gangue 0.75 0.75 in (N 0.75 On 〇Os d ON 〇OS 〇Os d ON 〇Os d 0.75 0.75 m Cn o ο Ο 〇〇&lt;N m 33.5 &lt;N m (N 1 m (N 52 CN (N 18.5 宕1 jr&gt; 〇O o ο Ο 〇〇〇(N (N 1 1 (N &lt; N 1 1 45.5 51.5 1 &lt;N m isopropyl methacrylate isopropyl methacrylate methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate Acid cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate cyclohexyl methacrylate ring Hexyl ester 1 (Phenol B) r^4 ο 〇〇〇TH 〇1-H VO SS 5〇ο 14000 12000 18000 18000 18000 18000 18000 13000 12000 13000 13000 13000 30000 30000 36000 12000 Eo ο SSS VO 2 m 00 νο pL Pin P-10 P-10 P-10 P-10 1 P-10 P-24 P-25 P-26 P-27 1 P-28 P-25 P-25 1 v〇VO VO VO v〇00 Os 1 m &lt;Ν Example 16 Example 17 Example 18 | Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example Example Example 22 Comparative Example 1 * Comparative Example 2 ^4n^s0009e$PM %wMo(N/%wMooo=瀣褰KSlightly &/feeding 褰瀣 line 1 £ slightly &:*. Chat X is ignorant «rai^e 靼 靼 () •oovo· 200813630 [e漱] evaluation lv gull &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; Laminated suitability mmm cn CO mmm developability m cn mmmm cn m deformation recovery rate (%) &lt;n tn in tn transfer transfer transfer transfer "lion transfer transfer transfer microparticles (D) average particle size (nm) vn 12 12 »Ti jn 骏i1ml1 W Colloidal gangue colloidal gangue colloidal gangue colloidal gangue in forging 醮 colloidal gangue colloidal gangue colloidal gangue 1 JO ο JQ d ο d JQ Ο ο JQ dd Resin (A) N *Τί m cn in cn mm 4/Ί m ^Τ) &lt;Ν vo vo (N 沄oo CN Ό (NX Ο TH On mm P; On cn nmL X inch Q CO Q ▼-HQS ν〇 inch oo ADM A acid value (mgKOH /g) TH m T—&lt;&lt;N 00 ON ΓΛ v〇H 卜 Os s $ Weihal average numerator 15000 15000 15000 11000 11000 11000 11000 13000 Glass transition temperature (°c) ο Os o ^&quot;4 rH rH CN (N fH ΓΛ g H compound structure Ον CN cL pL TH rn Oh (N rn pI m cL rn TH (N pL synthesis example &lt;Ν CN oo &lt;NO &lt;N ( N m Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Distillation collar - &lt; Ν瀣K_Bl·: vwav)^(^) Miscellaneous Hls^iLmKw }Songsong 4n^s5&gt;螂:χ 丨6ς_ 200813630 (Examples 23 to 28) ·Examples of spacers with a small average height and a small height in a small liquid crystal display device such as a mobile device It is small and uses a TN type liquid crystal mode. Therefore, the diameter of the spacer is required to be small and the height is higher. However, the spacer having a small diameter and a high height may be partially peeled off during the process. As a more suitable example, in the present embodiment, in addition to the compound (A) obtained from the synthesis example 1, the structure Ρ-; ι is changed to the synthetic 洌 18 to 22 to obtain the compound 锪 structure P-24~ In the same manner as in Example 1, except that the prescription 1 of the coating liquid for a photosensitive resin composition layer was changed to the prescriptions 8 to 13 described in Table 4, a light spacer was produced. However, T-CD1 was diluted 5 times with pure water. The resulting gap sub-pattern was a cylindrical shape having a diameter of 1 5 μηη and an average height of 4.7 μηη. No shedding was seen in the process. Further, in the present embodiment, the proportion of the colloidal vermiculite is increased to increase the thickness precision of the spacer. (Example 29) The coating amount of the coating liquid for a photosensitive resin composition layer in Example 28 was adjusted, and the obtained gap sub-pattern was changed to a cylindrical shape having a diameter of 15 μm and an average height of 4.7 μm, and examples. 2 8 is carried out in the same manner. -60- 200813630 [Inch 漱] Prescription 13 Example 28, 29 (Ν (Ν Ό C&lt;l 0.22 〇〇〇〇〇0.27 0.042 00 iri prescription 12 Example 27 VO VO (N 0.22 r«H 〇〇〇〇 〇0.27 0.042 00 Prescription 11 Example 26 CN v〇Ό (N 0.22 〇〇〇〇〇0.27 C.042 oo wri _1〇Example 25 (N VO v〇CN 0.22 〇〇〇〇〇r 1 0.27 0.042 oo ... Prescription 9 Example 24 (N (N VO VO &lt; N 0.22 〇〇〇〇〇 0.27 0.042 oo tn prescription 8 Example 23 (S 04 VO VO (N 0.22 〇〇〇〇〇 0.27 0.042 00 photosensitive resin composition) Layer coating solution 1-methoxy-2-propyl acetate methyl ethyl ketone colloidal vermiculite dispersion (same as in Table 1) Solspass 20000 DPHA solution (same as in Table 1) Solvent (A) solution ( Synthesis Example 18) Solution of the formula (A) (Synthesis Example 19) Solution of the formula (8) (Synthesis Example 20) Solution of the formula (A) (Synthesis Example 21) Solution of the resin (A) (Synthesis Example) 22) Solution of Tree Moon (A) (Synthesis Example 24) |1 J if 111 W EEl· ί « Surfactant 1 (same as Table 1) 撇H Daddy § ® 冏 £ m§ φ_® : Zhao Age _ 19 200813630 [Evaluation] A pair of optical gaps, which are measured by the microhardness tester (DUH-W201, manufactured by Shimadzu Corporation), are evaluated as follows. The measurement system uses a round hammer of 50 μm ηφ. The head pressure head has a maximum load of 50 mN and a holding time of 5 seconds in a diameter of 24 μm, and is carried out by a load-load-removal test method. When the optical gap of a diameter of 15 μm is used, the maximum load is 2 1 mN and a holding time of 5 seconds were carried out in the same manner. From this measurement, the recovery rate [%] was determined by the following formula and evaluated according to the following criteria. The measurement was performed at 22 ± 1 ° C, 5 In the environment of 0% RH, the deformation recovery rate (%) = (the amount of deformation due to the load [μιη] / the amount of recovery after the load is removed [μιη]) χ 100 &lt; evaluation criteria &gt; 5 : deformation recovery rate is 90 %: The deformation recovery rate is 87% or more and less than 90%. 3 : The deformation recovery rate is 85% or more and less than 87%. I j 2 : The deformation recovery rate is 80% or more and less than 85%. 1: The deformation recovery rate is 75% or more and less than 80%. 〇: The deformation recovery rate is less than 75%. In the above-mentioned "production of a photo spacer", after the proximity type exposure, the image is developed in the same manner as the development conditions of the respective embodiments, and the peripheral portion of the formed optical spacer is formed. The SEM observation was carried out to confirm whether or not there was residue remaining in the periphery. -62- 200813630 <Evaluation Criteria> 5 : No residue was seen at all. 4: Several residues were seen around the pattern. 3: See the residue around the pattern. 2: Residues were observed on the periphery of the pattern and on the substrate near the pattern. 1 : Residues can be confirmed everywhere on the substrate. - Multilayer suitability &lt;Laminating foam&gt; Evaluation - After peeling off the dummy support in the state where the photosensitive resin transfer film was transferred on the color filter substrate, the laminated state was observed with an optical microscope, and observation was observed. Whether there are laminar bubbles (bubbles that occur when air is trapped when laminating). &lt;Evaluation Criteria&gt; 3: There was no stratified bubble at all. 2: The laminated bubble system occurs outside the pattern forming place. 1: The laminated bubble system occurs in the pattern forming portion. A mesh is placed in a 45 ° C / 7 5 % RH environment for 24 hours, using a microscope

ί I V 觀察感光性樹脂轉印薄膜的表面，依照下述基準藉由目視 來進行評價。 〈評價基準〉 / 4 :完全沒有看到細小的「皺紋」等之發生。 3 :稍微看到細小的「皺紋」等之發生，但是爲實用上可 能使用的程度。 2 :少許看到細小的「皺紋」等的發生。 1 :看到相當多的細小「皴紋」等之發生。 -63- 200813630 一顯τκ不均一 對各個液晶顯示裝置，輸入灰色的測試訊號時，目視 及藉由放大鏡來觀察灰色顯示，依照下述評價基準來評估 有無顯示不均的發生。 &lt;評價基準&gt; A :完全沒有看到顯示不均。 B :稍微看到顯示不均。 C:顯著看到顯示不均。 -64-ί I V The surface of the photosensitive resin transfer film was observed and evaluated by visual observation according to the following criteria. <Evaluation Criteria> / 4 : No small "wrinkles" occurred at all. 3 : Slightly see the occurrence of small "wrinkles", etc., but it is practically usable. 2: A little bit of seeing the occurrence of small "wrinkles". 1 : I saw quite a few tiny "skull lines" and so on. -63- 200813630 One display τκ unevenness For each liquid crystal display device, when a gray test signal is input, the gray display is visually observed and viewed by a magnifying glass, and the occurrence of display unevenness is evaluated according to the following evaluation criteria. &lt;Evaluation Criteria&gt; A: No display unevenness was observed at all. B: I saw a slight unevenness. C: Significantly see uneven display. -64-

Claims (1)

200813630 十、申請專利範圍： 1 · 一種感光性組成物，其特徵爲至少包含：樹脂（A)，其含 有在側鏈具有分枝及/或脂環構造的基、在側鏈具有酸性 基的基、及在側鏈具有乙烯性不飽和基的基；聚合性化 合物（B);光聚合引發劑（C)。 2 ·如申請專利範圍第1項之感光性組成物，其中上述樹脂 (A)的玻璃轉移溫度（Tg)係40〜180°C，而且重量平均分 # 子量係 10,000 〜1 00,000。 3 ·如申請夢利範圍第1項之感光性里成物，其中上述聚合 性化合物（B)對樹脂（A)的質量比率（（B)/(A))係0.5〜2。 4·如申請專利範圍第1項之感光性組成物，其中更含有微 粒子（D)。 5 ·如申請專利範圍第4項之感光性組成物，其中上述微粒 子（D)的平均粒徑係5〜50nm，而且對於如申請專利範圍 第4項之感光性組成物中的總固體成分而言，質量比率 係5〜50質量％。 6. 如申請專利範圍第4項之感光性組成物，其中上述微粒 子（D)係膠態矽石。 7. —種感光性樹脂轉印薄膜，其係在假支持體上至少具有 感光性樹脂層的感光性樹脂轉印薄膜’其特徵爲該感光 性樹脂層係使用如申請專利範圍第1至6項中任一項之 感光性組成物所形成。 8. 如申請專利範圍第7項之感光性樹脂轉印薄膜，其中在 上述感光性樹脂層與上述假支持體之間，設有隔氧層及/ -65- 200813630 或熱塑性樹脂層。 9. 一種光間隙子之製法，其特徵爲具有使用如申請專利範 圍第1項之感光性組成物，藉由塗布以在支持體上形成 感光性樹脂層的步驟。 10. —種光間隙子之製法，其特徵爲具有使用如申請專利範 圍第7項之感光性樹脂轉印薄膜，藉由加熱及/或加壓 來轉印感光性樹脂層，在支持體上形成感光性樹脂層的 步驟。 / , 1 1. 一種液晶顯示裝置用基板’其特徵爲具備由如申請專利 範圍第9項之光間隙子之製法所製造的光間隙子。 1 2. —種液晶顯示裝置，其特徵爲具備如申請專利範圍第 11項之液晶顯示裝置用基板。 •66- 200813630 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明: 〇 j\\\ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：200813630 X. Patent application scope: 1 . A photosensitive composition characterized by comprising at least a resin (A) containing a group having a branching and/or alicyclic structure in a side chain and an acidic group in a side chain. a group having a group having an ethylenically unsaturated group in the side chain; a polymerizable compound (B); and a photopolymerization initiator (C). 2. The photosensitive composition of claim 1, wherein the resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C and a weight average of 10,000 to 10,000,000. 3. The photosensitive composition according to the first item of the invention, wherein the mass ratio ((B)/(A)) of the polymerizable compound (B) to the resin (A) is 0.5 to 2. 4. The photosensitive composition of claim 1, wherein the microparticle (D) is further contained. 5. The photosensitive composition of claim 4, wherein the fine particles (D) have an average particle diameter of 5 to 50 nm, and are the total solid content in the photosensitive composition as in the fourth aspect of the patent application. In other words, the mass ratio is 5 to 50% by mass. 6. The photosensitive composition of claim 4, wherein the microparticles (D) are colloidal vermiculite. 7. A photosensitive resin transfer film which is a photosensitive resin transfer film having at least a photosensitive resin layer on a dummy support, which is characterized in that the photosensitive resin layer is used as in Patent Application Nos. 1 to 6 The photosensitive composition of any one of the items is formed. 8. The photosensitive resin transfer film of claim 7, wherein an oxygen barrier layer and/or -65-200813630 or a thermoplastic resin layer are provided between the photosensitive resin layer and the dummy support. A method of producing a photonic spacer, which comprises the step of applying a photosensitive composition as in the first aspect of the patent application, by coating to form a photosensitive resin layer on a support. 10. A method for producing a photo-gap, characterized in that it has a photosensitive resin transfer film as in claim 7 of the patent application, and the photosensitive resin layer is transferred by heating and/or pressurization on the support. A step of forming a photosensitive resin layer. / 1, 1 1. A substrate for a liquid crystal display device, which is characterized by comprising a photo spacer manufactured by the method of manufacturing the optical spacer of the ninth aspect of the patent application. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 11 of the patent application. •66- 200813630 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 j\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW096126854A 2006-07-26 2007-07-24 Photosensitive composition, photosensitive resin transferring film, method of produing photo spacer, substrate for liquid crystal display device, and liquid crystal display device TW200813630A (en)

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