TWI336815B - Spacer for display panels, radiation sensitive resin composition and liquid crystal display device - Google Patents

Spacer for display panels, radiation sensitive resin composition and liquid crystal display device Download PDF

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Publication number
TWI336815B
TWI336815B TW093116718A TW93116718A TWI336815B TW I336815 B TWI336815 B TW I336815B TW 093116718 A TW093116718 A TW 093116718A TW 93116718 A TW93116718 A TW 93116718A TW I336815 B TWI336815 B TW I336815B
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TW
Taiwan
Prior art keywords
spacer
weight
liquid crystal
meth
ether
Prior art date
Application number
TW093116718A
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Chinese (zh)
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TW200510936A (en
Inventor
Daigo Ichinohe
Tomohiro Uetsuhara
Toshihiro Nishio
Michinori Nishikawa
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Jsr Corp
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Publication of TW200510936A publication Critical patent/TW200510936A/en
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Publication of TWI336815B publication Critical patent/TWI336815B/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

1336815 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於供顯示面板用之間隔物，感射線樹脂組 成物以及液晶顯示裝置，更確定地說，其係關於供液晶顯 示面板、觸摸面板等使用的顯示面板用之間隔物，用於形 成該間隔物之感射線樹脂組成物，及含該間隔物之液晶顯 示裝置。1336815 (1) Technical Field of the Invention The present invention relates to a spacer for a display panel, a radiation sensitive resin composition, and a liquid crystal display device, and more specifically, to a liquid crystal display panel, A spacer for a display panel used for a touch panel or the like, a radiation sensitive resin composition for forming the spacer, and a liquid crystal display device including the spacer.

【先前技術】 迄今，間隔物粒子例如具有預先決定直徑的玻璃珠或 塑膠粒曾經用在液晶顯示面板使兩個基板之間的間隙寬度 保持固定，但是，因爲間隔物粒子是隨意噴灑在基板上， 當其存在於有效畫像區域時，其成像或散射入射光，因而 降低液晶顯示面板之對比。[Prior Art] Heretofore, spacer particles such as glass beads or plastic pellets having a predetermined diameter have been used in a liquid crystal display panel to keep the gap width between the two substrates fixed, but since the spacer particles are randomly sprayed on the substrate When it exists in the effective image area, it images or scatters incident light, thereby reducing the contrast of the liquid crystal display panel.

因此，間隔物是經由光石印形成，在此技術中，在基 板上塗覆光敏性樹脂，經由預先決定的光罩暴露至紫外光 並顯影而形成點狀或條狀的間隔物，根據此技術，間隔物 可以在有效畫像區域以外的區域形成且當噴灑間隔物粒子 所發生的上述問題可以解決，而且，因爲室間隙可經由此 項技藝中的光敏性樹脂塗覆厚度控制，間隙寬度之控制很 容易且可得到高精確性。 液晶顯示面板基板之間的間隙寬度是在常溫下經由基 板之間的間隔物保持在定値，因此基板之間的液晶層厚度 保持固定，但是當在液晶顯示面板生產過程於液晶注射及 -5- (2) (2)1336815 密封後的退火步驟及高溫上架測試供評估液晶顯示面板之 信賴度時，液晶顯示面板放在高溫下，塡入基板之間的液 晶會熱膨脹且經由膨脹壓力使得間隙寬度改變，基板因而 變形且液晶層之厚度變成部份不均勻，因此，顯示對比變 成不均勻且顯示品質惡化，特別是有大基板面積之大型液 晶顯示面板，經由液晶熱膨脹造成的基板變形容易明顯， 因爲用於電視之液晶顯示面板變得尺寸越來越大，經由液 晶熱膨脹造成的不均勻顯示對比變成一個需要解決的嚴重 問題。 已經有多種提議用於降低經由液晶熱膨脹造成的不均 勻顯示對比。 JP-A 8-15708 (在本文中使用的名詞、JP—A"係指 ”未經檢查公告的日本專利申請案〃）揭示一種利用多種 不同直徑及彈性的球形間隔物之方法，關於用於組裝顯示 面板之製程情形，JP-A 2002-4904 1揭示一種控制球形間 隔物散射密度之方法，JP-A 200 1 - 1 47437揭示柱式間隔物 之安排。 但是，當液晶顯示面板是在高溫下從水平方向傾斜時 ，因爲球形間隔物粒子不會黏附在基板的表面，粒子在液 晶層中移動且不均勻分布，因而造成不均勻顯示，柱式間 隔物安排之規格說明限制面板之設計自由度，其因爲液晶 顯示面板之設計在未來將變成越來越廣泛而不建議。 【發明內容】 -6- (3) (3)1336815 本發明之目的是提供一種用於顯示面板之間隔物’其 具有特定的線性熱膨脹係數，可在常溫及高溫下使基板間 隙寬度保持固定，且不受溫度變化影響可以一直保有極佳 的顯示品質’一種用於形成此間隔物之感射線樹脂組成物 及含此間隔物之液晶顯示裝置。 本發明之其他目的及優點從下列說明將變得更明顯。 根據本發明之第一點’本發明之上述目的及優點是一 種用於顯示面板之間隔物，其具有高於2 〇 X 1 〇 - 4 / t及 8,0xl(T 4/ °C或更低之線性熱膨脹係數。 根據本發明之第二點，本發明之上述目的及優點是一 種a [A]—種（al)不飽和的翔酸及/或不飽和的竣酸酐 及（a2)成份（al)除外之不飽和的化合物之共聚物、 [B]—種多官能基不飽和的單體及[c]—種感射線的聚合作 用引發劑之感射線樹脂組成物，其中感射線樹脂組成物之 固化膜具有高於2,0xI0_4/t：及、(^㈧^/乞或更低之 線性熱膨脹係數且此感射線樹脂組成物用於形成在申§靑專 利範圍第1項說明之用於顯示面板之間隔物。 根據本發明之第三點’本發明之上述目的及優點是含 用於本發明顯示面板的間隔物之液晶顯示裝置。 【實施方式】 較佳具體實施例之詳細說明 以下將詳細說明本發明。 (4) (4)1336815 用於顯示面板之間隔物 本發明顯示面板的間隔物之線性熱膨脹係數是高於 2.0><10~4/°(：及8.(^10_4/：1(：或更低，較宜是（3.0至 8.0) xl(T4/°C，更宜是（4.0 至 8.0) xl〇-4/t：，特 別較宜是（5.0 至 8.0) xlO—4 / °C。 本發明顯示面板的間隔物可以在常溫及高溫下使基板 間隙寬度保持固定，且不受溫度變化影響可以一直保有極 佳的顯示品質，且可以合適用在液晶顯示面板、觸摸面板 等，當其線性熱膨脹係數落在上述範圍時，不受限於其形 狀及位置以及面板之設計自由度。 感射線樹脂組成物 用於形成本發明顯示面板的間隔物之材料沒有特別的 限制’只要間隔物具有上述之線性熱膨脹係數及需要的強 度、表面硬度、耐熱性及耐化學性，且可形成具有預先決 定的形狀之間隔物，較佳的材料是含[A ] —種（a 1 )不飽 和的羧酸及/或不飽和的羧酸酐（以下稱爲、酸不飽和的 化合物（a】）〃）及（a 2 )成份（a 1 )除外之不飽和的化 合物（以下稱爲％其他不飽和的化合物（a2 ) 〃 ）之共聚 物（以下稱爲，共聚物[A]〃 ）、[B]—種多官能基不飽和 的單體及[C ] 一種感射線的聚合作用引發劑之感射線樹脂 '組成物’從其所得之固化膜具有高於2.OXI〇-4/t及8.0 X 1 4/ °c或更低之線性熱膨脹係數。 (5) (5)1336815 -共聚物[A] - 用於共聚物[A]之酸不飽和的化合物（al )的實例包 括不飽和的單羧酸例如（甲基）丙烯酸及科洛酸（ corotonic acid );不飽和的二羧酸例如馬來酸、富馬酸、 檸康酸、中康酸及衣康酸；及這些不飽和的二羧酸之酸酐 〇 這些不飽和的化合物（a 1 )中，從共聚合反應性及容 易取得之觀點，較宜是丙烯酸、甲基丙烯酸及馬來酸酐。 上述酸不飽和的化合物（a 1 )可以單獨或二或多種混 合使用。 用於共聚物[A]之其他不飽和的化合物（a2 )的實例 包括（甲基）丙烯酸烷酯例如（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯 酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁 酯、（甲基）丙烯酸第二丁酯及（甲基）丙烯酸第三丁酯 ;脂環族（甲基）丙烯酸酯例如（甲基）丙烯酸環戊酯、 (甲基）丙烯酸環己酯、（甲基）丙烯酸2-甲基環己酯 、（甲基）丙烯酸三環[5.2.1.02·6]十一碳—8 —酯、（甲 基）丙烯酸2 -二環戊氧基乙酯及（甲基）丙烯酸異冰片 酯；（甲基）丙烯酸芳酯例如（甲基）丙烯酸苯酯及（甲 基）丙烯酸苄酯：（甲基）丙烯酸羥基烷酯例如（甲基） 丙烯酸2-羥基乙酯及（甲基）丙烯酸2 -羥基丙酯；含 環氧基的（甲基）丙烯酸酯例如（甲基）丙烯酸縮水甘油 酯、（甲基）丙烯酸3，4 —環氧基丁酯、（甲基）丙燃 -9- (6) (6)1336815 酸6’ 7 -環氧基庚酯、（甲基）丙烯酸2，3-環氧基環 戊酯及（甲基）丙烯酸3，4-環氧基環己酯；不飽和的 二羧酸二酯類例如馬來酸二乙酯、富馬酸二乙酯及衣康酸 二乙酯；不飽和的亞醯胺化合物例如N -苯基馬來醯亞胺 、N_苄基馬來醯亞胺及N -環己基馬來醯亞胺；乙烯基 氰化物例如（甲基）丙烯腈' α -氯丙烯腈及乙烯叉二腈 :不飽和的醯胺化合物例如（甲基）丙烯醯胺及Ν，Ν _ 二甲基（甲基）丙烯醯胺：芳族乙烯基化合物例如苯乙烯 ' α —甲基苯乙烯、間一甲基苯乙烯、對一甲基苯乙烯、 乙烯基甲苯及對-甲氧基苯乙烯；茚衍生物例如茚及1 _ 甲基茚：共軛的二烯化合物例如1，3 -丁二烯、異戊間 二烯及2，3_二甲基_1，3_ 丁二烯；及氯乙烯、偏氯 乙烯及醋酸乙烯酯。 這些其他不飽和的化合物（a2 )中，從共聚合反應性 之觀點，較宜是（甲基）丙烯酸烷酯例如（甲基）丙烯酸 正丁酯、脂環族（甲基）丙烯酸酯例如（甲基）丙烯酸三 環[5.2.1.02·6]十一碳一 8—酯、（甲基）丙烯酸芳酯例如 (甲基）丙烯酸苄酯、含環氧基的（甲基）丙烯酸酯例如 (甲基）丙烯酸縮水甘油酯、苯乙烯及1，3 — 丁二烯。 上述其他不飽和的化合物（a2 )可以單獨或二或多種 混合使用。 衍生自共聚物[A]中的酸不飽和的化合物（a 1 )之重 複出現單元含量較宜是5至50重量％，特別較宜是10至 40重量％，當重複出現單元含量是低於5重量％時，間 -10- (7) (7)1336815 隔物之耐熱性、耐化學性及表面硬度將惡化且當含量大於 5 0重量％時，組成物之儲存安定性可能降低。 共聚物[A]以聚苯乙烯爲基準之重量平均分子量（以 下稱爲)較宜是2,000至5 00,000’更宜是5,000 至100,000，當共聚物[A]之Mw低於2,000時’耐熱性及 表面硬度可能下降且當Mw是局於500,000時’顯力 可能惡化。 在本發明中，共聚物[A]可以單獨或二或多種混合使 用。 共聚物[A]可以在聚合引發劑存在下’在溶劑中經由 酸不飽和的化合物（a ])與其他不飽和的化合物（a2 )聚 合而生產。 用於生產共聚物[A]之溶劑實例包括醇類例如甲醇及 乙醇；醚類例如四氫呋喃及二哼烷；乙二醇醚類例如乙二 醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚及乙二醇單丁 醚；乙二醇烷基醚醋酸酯例如乙二醇甲基醚醋酸酯 '乙二 醇乙基醚醋酸酯、乙二醇正丙基醚醋酸酯及乙二醇正丁基 醚醋酸酯；二甘醇醚類例如二甘醇單甲醚、二甘醇單乙醚 、二甘醇二甲醚、二甘醇二乙醚及二甘醇乙醚甲醚：二甘 醇烷基醚醋酸酯例如二甘醇甲醚醋酸酯、二甘醇乙醚醋酸 酯、二甘醇正丙醚醋酸酯及二甘醇正丁醚醋酸酯；丙二醇 醚類例如丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚 、丙二醇單正丁醚；丙二醇烷基醚醋酸酯例如丙二醇甲醚 醋酸酯、丙二醇乙醚醋酸酯、丙二醇正丙醚醋酸酯及丙二 -11 - (8) (8)1336815 醇正丁醚醋酸酯；丙二醇烷基醚丙酸酯例如丙二醇甲基醚 丙酸酯 '丙二醇乙基醚丙酸酯、丙二醇正丙基醚丙酸酯及 丙二醇正丁基醚丙酸酯：芳族烴類例如甲苯及二甲苯：酮 類例如甲基乙基酮、環己酮、4_羥基_4 一甲基_2-戊 酮及甲基異戊基酮；及其他酯類例如醋酸甲酯、醋酸乙酯 、醋酸正丙酯、醋酸正丁酯、羥基醋酸甲酯、羥基醋酸乙 酯、羥基醋酸正丙酯、羥基醋酸正丁酯、甲氧基醋酸甲酯 、甲氧基醋酸乙酯、甲氧基醋酸正丙酯、甲氧基醋酸正丁 酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸正丙 酯、乙氧基醋酸正丁酯、正丙氧基醋酸甲酯、正丙氧基醋 酸乙酯、正丙氧基醋酸正丙酯、正丙氧基醋酸正丁酯、正 丁氧基醋酸甲酯、正丁氧基醋酸乙酯、正丁氧基醋酸正丙 酯、正丁氧基醋酸正丁酯、乳酸甲酯、乳彎乙酯、乳酸正 丙酯、乳酸正丁酯、3-羥基丙酸甲酯、3 -羥基丙酸乙酯 、3 -羥基丙酸正丙酯、3 -羥基丙酸正丁酯、2_甲氧基 丙酸甲酯、2-甲氧基丙酸乙酯、2 -甲氧基丙酸正丙酯、 2 -甲氧基丙酸正丁酯、2 —乙氧基丙酸甲酯、2_乙氧基 丙酸乙酯、2_乙氧基丙酸正丙酯、2_乙氧基丙酸正丁酯 、2 -正丙氧基丙酸甲酯、2 -正丙氧基丙酸乙酯、2 —正 丙氧基丙酸正丙酯、2-正丙氧基丙酸正丁酯、2 -正丁氧 基丙酸甲酯、2—正丁氧基丙酸乙酯、2—正丁氧基丙酸正 丙酯、2_正丁氧基丙酸正丁酯、3—甲氧基丙酸甲酯、3 —甲氧基丙酸乙酯、3—甲氧基丙酸正丙酯、3—甲氧基丙 酸正丁酯、3 -乙氧基丙酸甲酯、3_乙氧基丙酸乙酯、3 -12- (12) (12)1336815 一 [c ]感射線聚合引發劑一 感射線聚合引發劑回應射線而產生可以引發多官能基 不飽和的單體[B ]聚合之活性物種。 感射線聚合引發劑較宜是感射線游離基聚合引發劑。 上述感射線游離基聚合引發劑之實例包括α -二酮類 例如苄基及二乙烯基；偶姻類例如苯偶姻；偶姻醚類例如 偶姻甲醚、偶姻乙醚及偶姻異丙醚；二苯甲酮類例如噻噸 酮、2，4 -二乙基噻噸酮、噻噸酮-4—磺酸、二苯甲酮 、4，4，—雙（二甲胺基）二苯甲酮及4，4<-雙（二 乙胺基）二苯甲酮；乙醯苯類例如乙醯苯、對-二甲胺基 乙醯苯、4— (α ，α / —二甲氧基乙醯氧基）乙醯苯、2 ’ 2 - _二甲氧基_2_苯基乙醯苯' 對一甲氧基乙醯苯、 2_甲基—2-嗎福啉基一1_ (4 一甲硫基苯基）—1—丙 酮及2-苄基一2-二甲胺基一 1 一 （4_嗎福啉基苯基） —丁一 1 一酮；醌類例如蒽醌及1，4 一萘醌：鹵素化合物 例如苯甲醯甲基氯、三溴甲基苯基碾及參（三氯甲基）-s_三畊；醯基膦氧化物例如2，4，6_三甲基苯並二苯 基膦氧化物、雙（2，6_二甲氧基苯甲醯基）一 2，4，4 一三甲基戊基膦氧化物及雙（2，4，6-三甲基苯甲醯基 )苯基膦氧化物；及過氧化物例如二第三丁基過氧化物。 感射線游離基聚合引發劑之商業化供應的產品包括 IRGACURE-1 24、149、184、3 69、5 00、65 1、819、907 、1 000、1 700' 1 800、1 8 5 0 及 29 5 9，及 Darocur-1 1 1 6 ' 1173、 1 6 6 4、2 9 5 9 及 4 0 4 3 ( Ciba Specialty Chemicals -16- (13) (13)1336815Therefore, the spacer is formed by photolithography, in which a photosensitive resin is coated on the substrate, exposed to ultraviolet light through a predetermined mask, and developed to form a dot or strip spacer, according to this technique, The spacer may be formed in an area other than the effective image area and the above-described problem that occurs when the spacer particles are sprayed can be solved, and since the chamber gap can be controlled by the photosensitive resin coating thickness in the art, the gap width is controlled very much. Easy and high accuracy. The gap width between the liquid crystal display panel substrates is kept at a constant temperature through the spacers between the substrates, so the thickness of the liquid crystal layer between the substrates remains fixed, but when liquid crystal injection and liquid crystal display panel production process (2) (2) 1336815 Annealing step after sealing and high-temperature rack test For evaluating the reliability of the liquid crystal display panel, the liquid crystal display panel is placed at a high temperature, and the liquid crystal between the substrates is thermally expanded and the gap width is increased via the expansion pressure. The substrate is thus deformed and the thickness of the liquid crystal layer becomes partially uneven. Therefore, the display contrast becomes uneven and the display quality deteriorates. In particular, a large liquid crystal display panel having a large substrate area is easily deformed by the substrate due to thermal expansion of the liquid crystal. Since the liquid crystal display panel for televisions becomes larger and larger, uneven display contrast caused by thermal expansion of the liquid crystal becomes a serious problem to be solved. A variety of proposals have been made to reduce uneven display contrast caused by thermal expansion of the liquid crystal. JP-A 8-15708 (a noun, JP-A" as used herein refers to a Japanese patent application filed by the unexamined publication), discloses a method of using a plurality of spherical spacers of different diameters and elasticity, with respect to A process for assembling a display panel, JP-A 2002-4904 1 discloses a method of controlling the scattering density of a spherical spacer, and the arrangement of the column spacers is disclosed in JP-A 200 1 - 1 47437. However, when the liquid crystal display panel is at a high temperature When tilting from the horizontal direction, since the spherical spacer particles do not adhere to the surface of the substrate, the particles move in the liquid crystal layer and are unevenly distributed, thereby causing uneven display, and the specification of the column spacer arrangement limits the design freedom of the panel. Degree, because the design of the liquid crystal display panel will become more and more extensive in the future, it is not recommended. [Abstract] -6- (3) (3) 1336815 The object of the present invention is to provide a spacer for a display panel' It has a specific linear thermal expansion coefficient, which can keep the gap width of the substrate constant at normal temperature and high temperature, and can maintain excellent performance regardless of temperature change. A sensible ray resin composition for forming the spacer and a liquid crystal display device comprising the spacer. Other objects and advantages of the present invention will become more apparent from the following description. The above objects and advantages of the present invention are a spacer for a display panel having a linear thermal expansion coefficient higher than 2 〇X 1 〇 - 4 / t and 8,0xl (T 4 / ° C or lower. According to a second aspect of the invention, the above objects and advantages of the present invention are a (A)- (a)-unsaturated acid and/or unsaturated phthalic anhydride and (a2) component (al) except for unsaturated a radiation-sensitive resin composition of a copolymer of a compound, [B] a polyfunctional unsaturated monomer, and [c] a radiation-inducing initiator, wherein the cured film of the radiation-sensitive resin composition has higher 2,0xI0_4/t: and (^(8)^/乞 or lower linear thermal expansion coefficient and the radiation-sensitive resin composition is used to form a spacer for a display panel described in the first aspect of the patent application. According to a third aspect of the present invention, the above objects and advantages of the present invention A liquid crystal display device including a spacer for a display panel of the present invention. [Embodiment] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail. (4) (4) 1336815 Spacer for display panel The present invention The linear thermal expansion coefficient of the spacer of the display panel is higher than 2.0 < 10~4/° (: and 8. (^10_4/:1 (or lower, preferably (3.0 to 8.0) xl (T4) / ° C, more preferably (4.0 to 8.0) xl 〇 -4 / t:, particularly preferably (5.0 to 8.0) x lO - 4 / ° C. The spacer of the display panel of the present invention can be made at normal temperature and high temperature The gap width of the substrate is kept constant, and the display quality is always maintained without being affected by the temperature change, and can be suitably used in a liquid crystal display panel, a touch panel, etc., and when the linear thermal expansion coefficient falls within the above range, it is not limited thereto. Shape and position and design freedom of the panel. The material of the radiation sensitive resin composition for forming the spacer of the display panel of the present invention is not particularly limited as long as the spacer has the above-mentioned linear thermal expansion coefficient and required strength, surface hardness, heat resistance and chemical resistance, and can be formed with A spacer of a predetermined shape, preferably a material containing [A]-(a1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (hereinafter referred to as acid-unsaturated compound (a)) 〃) and (a 2 ) a copolymer of an unsaturated compound other than the component (a 1 ) (hereinafter referred to as % other unsaturated compound (a2 ) 〃 ) (hereinafter referred to as copolymer [A] 〃 ), [ B] - a polyfunctional unsaturated monomer and [C ] a radiation-sensitive polymerization initiator of a radiation-sensitive resin composition having a cured film having a higher than 2.OXI〇-4/t and Linear thermal expansion coefficient of 8.0 X 1 4/ °c or lower. (5) (5) 1336815 - Copolymer [A] - Examples of the acid-unsaturated compound (al ) used for the copolymer [A] include unsaturated monocarboxylic acids such as (meth)acrylic acid and clophonic acid ( Corotonic acid ); unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these unsaturated dicarboxylic acids 〇 these unsaturated compounds (a 1 Among them, acrylic acid, methacrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity and easy availability. The above acid-unsaturated compound (a 1 ) may be used singly or in combination of two or more. Examples of the other unsaturated compound (a2) used for the copolymer [A] include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. Ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate and tert-butyl (meth)acrylate; Ring family (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo(methyl) acrylate [5.2. 1.02·6] eleven carbon-8 ester, 2-dicyclopentyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; aryl (meth)acrylate such as benzene (meth)acrylate Esters and benzyl (meth)acrylate: hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; epoxy-containing (methyl) Acrylates such as glycidyl (meth)acrylate, 3,4-epoxy (meth)acrylate Butyl ester, (meth)propanol-9-(6) (6)1336815 acid 6' 7-epoxyheptyl ester, 2,3-epoxycyclopentyl (meth)acrylate and (methyl) 3,4-Epoxycyclohexyl acrylate; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; unsaturated sulfoxide compounds For example, N-phenylmaleimide, N-benzylmaleimide and N-cyclohexylmaleimide; vinyl cyanide such as (meth)acrylonitrile 'α-chloroacrylonitrile and ethylene A phthalonitrile compound: an unsaturated guanamine compound such as (meth) acrylamide and hydrazine, Ν dimethyl dimethyl methacrylate: an aromatic vinyl compound such as styrene 'α-methyl styrene, M-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; anthracene derivatives such as anthracene and 1 -methylindole: conjugated diene compounds such as 1,3 - Diene, isoprene and 2,3-dimethyl-1,3-butadiene; and vinyl chloride, vinylidene chloride and vinyl acetate. Among these other unsaturated compounds (a2), from the viewpoint of copolymerization reactivity, an alkyl (meth)acrylate such as n-butyl (meth)acrylate or an alicyclic (meth)acrylate such as Methyl)acrylic acid tricyclo[5.2.1.02·6]undecyl 8-octyl ester, (meth)acrylic acid aryl ester such as benzyl (meth) acrylate, epoxy group-containing (meth) acrylate such as Glycidyl methacrylate, styrene and 1,3-butadiene. The above other unsaturated compound (a2) may be used singly or in combination of two or more. The content of the recurring unit derived from the acid-unsaturated compound (a 1 ) derived from the copolymer [A] is preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight, when the repeating unit content is lower than At 5% by weight, the heat resistance, chemical resistance and surface hardness of the inter--10-(7)(7)1336815 separator will deteriorate and when the content is more than 50% by weight, the storage stability of the composition may be lowered. The weight average molecular weight (hereinafter referred to as) of the copolymer [A] based on polystyrene is preferably 2,000 to 50,000,000', more preferably 5,000 to 100,000, and when the Mw of the copolymer [A] is less than 2,000, heat resistance. And the surface hardness may decrease and the apparent force may deteriorate when Mw is at 500,000. In the present invention, the copolymer [A] may be used singly or in combination of two or more. The copolymer [A] can be produced by polymerizing in the solvent via the acid-unsaturated compound (a) with other unsaturated compound (a2) in the presence of a polymerization initiator. Examples of the solvent used for the production of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Mono-n-propyl ether and ethylene glycol monobutyl ether; ethylene glycol alkyl ether acetate such as ethylene glycol methyl ether acetate 'ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate and ethylene Alcohol n-butyl ether acetate; diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglyme, diethylene glycol diethyl ether and diethylene glycol diethyl ether methyl ether: diethylene glycol alkane Ethyl ether acetate such as diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol n-propyl ether acetate and diethylene glycol n-butyl ether acetate; propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol n-propyl ether acetate and propylene di-l- (8) (8) 1336815 Ether acetate; propylene glycol alkyl ether propionate such as propylene glycol methyl ether Acid esters propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate and propylene glycol n-butyl ether propionate: aromatic hydrocarbons such as toluene and xylene: ketones such as methyl ethyl ketone, cyclohexyl Ketone, 4-hydroxy-4-methyl-1-pentanone and methyl isoamyl ketone; and other esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate , ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, ethoxy Methyl acetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propoxyacetic acid Propyl ester, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, n-butyl n-butoxyacetate, methyl lactate, Ethyl acetate, n-propyl lactate, n-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate n-Butyl 3-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate , 2 - methyl ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, 2-n-propoxypropane Methyl ester, 2-n-propoxy propionate ethyl ester, 2-n-propoxy propionate n-propyl ester, 2-n-propoxy propionate n-butyl ester, 2-n-butoxypropionate methyl ester, 2-N-butylbutoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-12 - (12) (12) 1336815 A [c] ray-initiating polymerization-inductive ray polymerization initiator responds to radiation to produce an active species of monomer [B] which can initiate polyfunctional unsaturation. The radiation ray polymerization initiator is preferably a radiation sensitive radical polymerization initiator. Examples of the above-mentioned radiation-sensitive radical polymerization initiator include α-diketones such as benzyl and divinyl; acyms such as benzoin; aceton ethers such as acetoin, acetophenone and isopropyl Ether; benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4,-bis(dimethylamino)di Benzophenone and 4,4<-bis(diethylamino)benzophenone; acetophenones such as acetophenone, p-dimethylaminobenzidine, 4-(α,α/-dimethyl Oxyethoxy ethoxy) acetophenone, 2 ' 2 - dimethyloxy 2 phenyl acetophenone Benzyl p-methoxymethoxy phenyl benzene, 2-methyl-2- phenanthroline 1-(4-methylthiophenyl)-1-propanone and 2-benzyl-2-dimethylamino-1-indanyl 4-(norfosylphenyl)-butan-1-one; hydrazines such as hydrazine And 1,4-naphthoquinone: halogen compounds such as benzamidine methyl chloride, tribromomethylphenyl milling and ginseng (trichloromethyl)-s_three tillage; mercaptophosphine oxides such as 2, 4, 6_Trimethylbenzodiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4 Trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide; and a peroxide such as di-tert-butyl peroxide. Commercially available products of radiation-sensitive radical polymerization initiators include IRGACURE-1 24, 149, 184, 3 69, 5 00, 65 1, 819, 907, 1 000, 1 700' 1 800, 1 8 5 0 and 29 5 9, and Darocur-1 1 1 6 ' 1173, 1 6 6 4, 2 9 5 9 and 4 0 4 3 (Ciba Specialty Chemicals -16- (13) (13) 1336815

Co., Ltd. ) 、KA Y ARAD - DETX、- MBP、- DMBI、一Co., Ltd. ), KA Y ARAD - DETX, - MBP, - DMBI, one

EPA 及-OA ( Nippon Kayaku Co·，Ltd. ) 、LUCIRIN TPOEPA and -OA (Nippon Kayaku Co., Ltd.), LUCIRIN TPO

(BASF Co., Ltd.) 、VICURE-1 0 及 55 ( STAUFFER Co., Ltd.) ' TRIGGNALP1 ( AKZO Co., Ltd. ) 、SANDORAY(BASF Co., Ltd.), VICURE-1 0 and 55 (STAUFFER Co., Ltd.) ' TRIGGNALP1 ( AKZO Co., Ltd. ) , SANDORAY

1000 ( SANDOZ AG) 、DEAP ( APJOHN Co., Ltd.)及 QU ANTACURE — PDO 、 - ITX 及-EPD ( WARD BLEKINSOP Co., Ltd.)。 這些感射線游離基聚合引發劑可以單獨或二或多種混 合使用。 具有高敏性且幾乎不會被空氣中所含的氧氣減活化之 感射線樹脂組成物可以得自經由使用至少一種射線敏化劑 結合上述感射線游離基聚合引發劑。 至於本發明感射線樹脂組成物各成份之含量’多官能 基單體[B]之量較宜是10至〗50重量份，更宜是20至 1 2 0重量份，以共聚物[A ]之1 0 0重量份爲基準，且感射 線聚合引發劑[C]之量較宜是1至40重量份’更宜是3至 35重量份，以共聚物[A]之100重量份爲基準。 當多官能基單體[B ]之量是小於】〇重量份時’很難形 成厚度均勻的膜且當量大於150重量份時’對基板之黏附 可能下降，當感射線聚合引發劑[C]之量是小於1重量份 時，耐熱性、表面硬度及耐化學性可能惡化且當量大於 4 0重量份時，透明度可能下降。 -其他添加物 -17- (14) 1336815 本發明感射線樹脂組成物可含有限 表面活性劑及助黏著劑，而不會損害本 上述表面活性劑是用於改進塗覆性 上述表面活性劑是較宜是氟基質的 基質的表面活性劑。 氟基質的表面活性劑較宜是在其任 及側鏈含氟烷基或氟伸烷基之化合物， 劑實例包括1，1，2，2 -四氟丙基（ 辛基）醚 '己基（1，1，2，2—四氟辛 二（1，〗，2，2 -四氟辛基）醚、六Z ，2-四氟辛基）醚 '八丙二醇二（1， 基）醚 '六丙二醇二（1，1，2，2—四 十二烷基磺酸鈉、1，1，2，2，8，8， 氟十二烷、1，1，2，2，3，3 -六氟癸 鈉、氟烷基磷酸鈉、氟烷基碳酸鈉、氟 二甘油肆（氟烷基聚氧乙烯醚）、氟烷 甜菜鹼、氟烷基聚氧乙烯醚、全氟烷基 基烷氧基酯及氟基質的烷基酯類。 氟基質的表面活性劑之商業化供應 1 000 及 1100 ( BM CHEMIE Co., F142D、 F172 ' F173、 F178、 F183、 F1 (Dainippon Ink and Chemicals, Inc. 1 7 0 C、171、4 3 0 及 431 ( Sumitomo Surflon S — 112、 113、 131' 141、 145 的其他添加劑例如 發明之目的。 〇 表面活性劑或矽酮 何一個末端、主鏈 氟基質的表面活性 1 ’ 1，2，2 —四氟 基）醚、八乙二醇 丨二醇二（1，1，2 1，2，2 —四氟辛 氟辛基）醚、全氟 9，9，I 0，1 〇 ——(- 烷、氟烷基苯磺酸 烷基聚氧乙烯醚、 基破化鞍、氟院基 聚氧乙醇、全氟烷 的產品包括B Μ -Ltd. ) ' Megafac 91 、 F471 及 F476 )、Florade FC — 3 M Limited )、 及 382 及 Surflon -18- (15) (15)1336815 SC- 101、102、103 ' 104、105 及 106 ( Asahi Glass Co., Ltd. ) 、F Top EF301、3 03 及 3 52 ( Shin Akita Kasei Co.,1000 (SANDOZ AG), DEAP (APJOHN Co., Ltd.) and QU ANTACURE — PDO, - ITX and -EPD ( WARD BLEKINSOP Co., Ltd.). These radiation-sensitive radical polymerization initiators may be used singly or in combination of two or more. The radiation sensitive resin composition having high sensitivity and hardly being deactivated by oxygen contained in the air may be obtained by combining the above-described radiation-based radical polymerization initiator by using at least one radiation sensitizer. The content of the component of the radiation sensitive resin composition of the present invention, the content of the polyfunctional monomer [B] is preferably from 10 to 50 parts by weight, more preferably from 20 to 120 parts by weight, based on the copolymer [A]. The amount of the radiation ray polymerization initiator [C] is preferably from 1 to 40 parts by weight, more preferably from 3 to 35 parts by weight, based on 100 parts by weight of the copolymer [A]. . When the amount of the polyfunctional monomer [B] is less than 〇 by weight, it is difficult to form a film having a uniform thickness and the equivalent weight is more than 150 parts by weight, the adhesion to the substrate may decrease, when the radiation polymerization initiator [C] When the amount is less than 1 part by weight, heat resistance, surface hardness, and chemical resistance may be deteriorated, and when the equivalent weight is more than 40 parts by weight, transparency may be lowered. -Other Additives-17- (14) 1336815 The radiation sensitive resin composition of the present invention may contain a surfactant-restricting agent and an adhesion promoter without impairing the above surfactants for improving coatability. A surfactant which is preferably a matrix of a fluorine matrix. The fluorine-based surfactant is preferably a compound having a fluorine-containing alkyl group or a fluorine-extended alkyl group in the side chain, and examples of the agent include 1,1,2,2-tetrafluoropropyl(octyl)ether 'hexyl ( 1,1,2,2-tetrafluorooctanedi(1,], 2,2-tetrafluorooctyl)ether, hexa-Z,2-tetrafluorooctyl)ether octapropanediol bis(1,yl)ether Hexapropylene glycol bis (sodium 1,1,2,2-tetradecyl sulfonate, 1,1,2,2,8,8, fluorododecane, 1,1,2,2,3,3 - Sodium hexafluoroantimonate, sodium fluoroalkylphosphate, sodium fluoroalkyl carbonate, fluorodiglyceride (fluoroalkyl ethoxylate), fluoroalkane betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkylalkyl Alkyl esters of oxyesters and fluorine bases. Commercial supply of surfactants based on fluorine matrix 1 000 and 1100 (BM CHEMIE Co., F142D, F172 'F173, F178, F183, F1 (Dainippon Ink and Chemicals, Inc 1 7 0 C C, 171, 4 3 0 and 431 (Sumitomo Surflon S - 112, 113, 131' 141, 145 other additives such as the purpose of the invention. 〇 surfactant or fluorenone one end, main chain fluorine matrix Surface activity 1 ' 1,2,2 -tetrafluoro)ether, octaethylene glycol decanediol di(1,1,2 1,2,2-tetrafluorooctylfluorooctyl)ether, perfluoro 9,9,I 0,1 〇——(- Alkane, fluoroalkyl benzene sulfonyl polyoxyethylene ether, lysine saddle, fluorine-based polyoxyethanol, perfluoroalkane products including B Μ -Ltd. ) ' Megafac 91 , F471 and F476), Florade FC — 3 M Limited ), and 382 and Surflon -18- (15) (15) 1336815 SC-101, 102, 103 '104, 105 and 106 (Asahi Glass Co., Ltd.) , F Top EF301, 3 03 and 3 52 ( Shin Akita Kasei Co.,

Ltd.)及 Futargent FT- 100、110、140A ' 150、250、 251、300、310 及 400S 及 Futargent FTX— 251 及 2 18( Neos Co., Ltd.)。 上述矽酮基質的表面活性劑之商業化供應的產品包括 Toray Silicone DC3PA、DC7PA、SH11PA、SH21PA、 SH28PA ' SH29PA、SH30PA、SH- 190 ' SH- 193、SZ -603 2、S F — 8 4 2 8、DC — 57 及 DC — 190 ( Toray Dow Corning Silicone Co ., Ltd.)及 T S F - 4 3 0 0、4 4 0 0、4 4 4 5 、4446、445 2 及 4 4 6 0 ( GE Toshiba Silicone Co·, Ltd.) o 其他表面活性劑包括非離子性表面活性劑包括聚氧乙 烯烷基醚類例如聚氧乙烯月桂基醚、聚氧乙烯硬脂醯基醚 及聚氧乙烯油基醚；聚氧乙烯芳基醚類例如聚氧乙烯-正 辛基苯基醚及聚氧乙烯-正壬基苯基醚：及聚氧乙烯二烷 基酯類例如聚氧乙烯二月桂酸酯及聚氧乙烯二硬脂酸酯； 及KP341有機矽氧烷聚合物（Shin-Etsu Chemical Co., Ltd.)及 Poly flow No. 57 及 No. 95 (甲基）丙烯酸一基 質的共聚物（Kyoeisha Kagaku Co·, Ltd.)。 這些表面活性劑可以單獨或二或多種混合使用❶ 表面活性劑之量較宜是5重量份或更少，更宜是2重 量份或更少’以共聚物[A]之100重量份爲基準，當表面 活性劑之量大於5重量份時，膜在應用時可能會粗糙化。 -19- (16) (16)1336815 上述助黏著劑是用於改善對基板之黏附。 助黏著劑較宜是含官能基之矽烷偶合劑，具體地說是 含官能基例如羧基、甲基丙烯醯基、異氰酸酯基或環氧基 之矽烷偶合劑，助黏著劑實例包括三甲氧基矽烷基苯甲酸 、r -甲基丙烯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧 基矽烷、乙烯基三甲氧基矽烷、r -異氰酸酯基丙基三乙 氧基矽烷、7 -甘油氧基丙基三甲氧基矽烷及/5- (3, 4-環氧基環己基）乙基三甲氧基矽烷。 這些助黏著劑可以單獨或二或多種混合使用。 助黏著劑之量較宜是20重量份或更少，更宜是15重 量份或更少，以共聚物[A ]之1 0 0重量份爲基準，當助黏 著劑之量大於2 0重量份時，耐熱性可能會下降。 在本發明感射線樹脂組成物中，共聚物[A]、多官能 基單體[B]、感射線聚合引發劑[C]及其他添加劑及這些成 份之量是經適當地選擇，使從其所得的固化膜之線性熱膨 脹係數變成高於2.0><1〇-4/°(：及8.0)<1〇-4/。(：或更低， 較宜（3.0 至 8.0) ΧΙΟ—4 / t，更宜（4.0 至 8.0) xlO 一 4 / °C，特別較宜（5 · 0 至 8.0 ) X 1 0 - 4 /。(：。 感射線樹脂組成物之製備 本發明感射線樹脂組成物較宜經由混合上述共聚物 [A]、多官能基單體[B]、感射線聚合引發劑[C]及視需要 選用的其他添加劑混合並將這些成份溶解在合適的溶劑中 ，製備成組成物溶液。 -20- (17) 1336815 用於製備上述組成物溶液之上述溶劑較宜是溶解這些 成份且不會與這些成份反應。 該溶劑實例是相同於製備上述共聚物[A]所使用的溶 劑名單。 這些溶劑中，從與各成份之溶解度、反應性及形成塗 覆膜的容易性之觀點，較宜是乙二醇烷基醚醋酸酯、二乙 二醇醚類' 丙二醇烷基醚醋酸酯及其他酯類。Ltd.) and Futargent FT-100, 110, 140A '150, 250, 251, 300, 310 and 400S and Futargent FTX- 251 and 2 18 ( Neos Co., Ltd.). Commercially available products of the above-mentioned anthrone matrix surfactants include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA 'SH29PA, SH30PA, SH-190 'SH-193, SZ-603 2, SF — 8 4 2 8 , DC — 57 and DC — 190 ( Toray Dow Corning Silicone Co ., Ltd.) and TSF - 4 3 0 0, 4 4 0 0, 4 4 4 5 , 4446, 445 2 and 4 4 6 0 ( GE Toshiba Silicone Co·, Ltd.) o Other surfactants include nonionic surfactants including polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-decylphenyl ether: and polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxygen Ethylene distearate; and KP341 organooxane polymer (Shin-Etsu Chemical Co., Ltd.) and Poly flow No. 57 and No. 95 (meth)acrylic acid-matrix copolymer (Kyoeisha Kagaku Co ·, Ltd.). These surfactants may be used singly or in combination of two or more kinds. The amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant is more than 5 parts by weight, the film may be roughened when applied. -19- (16) (16) 1336815 The above adhesion promoter is used to improve the adhesion to the substrate. The adhesion promoter is preferably a functional group-containing decane coupling agent, specifically a decane coupling agent containing a functional group such as a carboxyl group, a methacryl oxime group, an isocyanate group or an epoxy group, and examples of the adhesion promoter include trimethoxy decane. Benzoic acid, r-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, r-isocyanatepropyltriethoxydecane, 7-glyceroloxy Propyltrimethoxydecane and /5-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. These adhesion promoters may be used singly or in combination of two or more. The amount of the adhesion promoter is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the copolymer [A], when the amount of the adhesion promoter is more than 20% by weight. Heat resistance may decrease at the time of serving. In the radiation sensitive resin composition of the present invention, the copolymer [A], the polyfunctional monomer [B], the radiation ray polymerization initiator [C], and other additives and the amounts of these components are appropriately selected so as to be The linear thermal expansion coefficient of the obtained cured film became higher than 2.0 <1〇-4/° (: and 8.0) <1〇-4/. (: or lower, more suitable (3.0 to 8.0) ΧΙΟ -4 / t, more suitable (4.0 to 8.0) xlO - 4 / °C, especially suitable (5 · 0 to 8.0) X 1 0 - 4 /. (: Preparation of the radiation sensitive resin composition The radiation sensitive resin composition of the present invention is preferably selected by mixing the above copolymer [A], the polyfunctional monomer [B], the radiation polymerization initiator [C], and optionally The other additives are mixed and dissolved in a suitable solvent to prepare a composition solution. -20- (17) 1336815 The above solvent for preparing the above composition solution is preferably dissolved in these components and does not react with these components. The solvent example is the same as the solvent used in the preparation of the above copolymer [A]. Among these solvents, ethylene glycol is preferred from the viewpoints of solubility to various components, reactivity, and ease of formation of a coating film. Alkyl ether acetate, diethylene glycol ether 'propylene glycol alkyl ether acetate and other esters.

上述溶劑可以單獨或二或多種混合使用。 尚沸點溶劑可以結合上述溶劑使用。The above solvents may be used singly or in combination of two or more. The boiling point solvent can be used in combination with the above solvent.

高沸點溶劑實例包括N -甲基甲醯胺、N，N -二甲 基甲醯胺、N —甲基甲醯替苯胺、n_甲基乙醯胺、N，N 一二甲基乙醯胺、N —甲基吡咯酮、二甲亞碩、苄基乙基 醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、I 一辛醇、1 一壬醇、苄醇 '乙酸苄酯 '苯甲酸乙酯、草酸 二乙酯、馬來酸二乙酯、r 一 丁內酯、碳酸乙酯、碳酸丙 酯及纖維素醋酸苯酯。 上述高沸點溶劑可以單獨或二或多種混合使用。 根據上述製備的組成物溶液在使用前是用開口直徑是 約0 · 2至0 · 5微米之多孔濾紙過濾。 形成顯示面板用的間隔物之方法 以下提供從本發明感射線樹脂組成物形成本發明顯示 面板用的間隔物之方法。 上述組成物溶液先施加至基板表面形成塗覆膜。 -21 - (18) (18)1336815 組成物溶液可經由合適的方法施加，例如噴霧、滾軸 塗覆、旋轉塗覆、棒塗覆或墨水噴射塗覆。 隨後，經由預烘烤此塗膜將溶劑蒸發而得到無流動性 的膜。 根據各成份種類及量而不同之預烘烤情形通常是溫度 爲60至1 2〇°C且時間是1 0至600秒。 然後將膜透過預定圖案之光罩暴露照射並用顯影劑顯 影而去除不要的部份。 用於暴露之照射是可見光、紫外光、遠紫外光、電子 照射、X -光等，較宜是波長爲190至450毫微米之紫外 光。 暴露量較宜是〗〇〇至20,000焦耳/平方米，更宜是 1 50至1 〇,〇〇〇焦耳/平方米。 顯影劑可以是無機鹼之鹼性水溶液例如氫氧化鈉、氫 氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉或氨水；一級胺例如 乙胺或正丙胺；二級胺例如二乙胺或二正丙胺；三級胺例 如三乙胺、甲基二乙基胺或N -甲基吡咯酮；醇胺例如二 甲基乙醇胺或三乙醇胺；四級銨鹽例如四甲基氫氧化銨、 四乙基氫氧化銨或膽鹼；或環胺例如吡咯、六氫吡啶、1 ’8 —二氮雜二環[5·4·0]-7 -十一碳烯或1，5 -二氮雜 二環[4.3.0] - 5 —壬烯。 上述鹼性水溶液可含合適量的水溶性有機溶劑例如甲 醇或乙醇及表面活性劑。 顯影較宜在常溫下進行30至1 80秒。 -22- (19) (19)1336815 顯影可以是攪煉顯影、浸漬或噴霧。 顯影後，用流水淸洗進行3 0至90秒，然後用壓縮空 氣或壓縮氮氣噴霧去除水，以便得到有預定圖案之膜。 隨後，用加熱器例如加熱板或烤爐在1 50至250°C加 熱此膜，例如在加熱板上5至30分鐘且在烤爐中30至 90分鐘而固化，因而得到有預定形狀之間隔物。 實例 下列實例之目的是提供用於進一步說明本發明，不能 以任何方式作爲其限制。 合成實例1 將4重量份之2，—偶氮雙異丁腈（AIBN )及20 重量份之二乙二醇乙基甲基醚注射至配備攪拌器之燒瓶內 ，再將5重量份之1 ’ 3-丁二烯、18重量份之甲基丙烯 酸、40重量份之甲基丙烯酸苄酯及37重量份之甲基丙烯 酸正丁酯注射至燒瓶內’燒瓶內部用氮氣取代，將這些物 質溫和攪拌，且反應溶液之溫度上升至80 °C，維持在此 點經5小時後進一步至1 0 〇 C而持續反應經1小時，隨後 ，使反應溶液之溫度降低至室溫而得到含共聚物[A ]之聚 合物溶液（固體含量=30.0重量％ )，此共聚物之Mw是 27,000，此共聚物命名爲共聚物（A— 1)。 合成實例2 -23- (20) (20)1336815 將4重量份之2’2> -偶氮雙異丁腈（AIBN )及 200重量份之二乙二醇乙基甲基醚注射至配備攪拌器之燒 瓶內，再將5重量份之1，3-丁二烯、5重量份之苯乙烯 、：18重量份之甲基丙烯酸、40重量份之甲基丙烯酸甘油 酯及32重量份之甲基丙烯酸三環[5.2. 1.02’6】癸—8—酯注 射至燒瓶內，燒瓶內部用氮氣取代，將這些物質溫和攪拌 ，且反應溶液之溫度上升至8 0 °C，維持在此點經5小時 後進一步至1 〇 0 °C而持續反應經1小時，隨後，使反應溶 液之溫度降低至室溫而得到含共聚物[A]之聚合物溶液（ 固體含量= 29.8重量％)，此共聚物之Mw是26,000，此 共聚物命名爲共聚物（A - 2) » 實例1 (1 )製備組成物溶液 將1〇〇重量份（固體含量）作爲成份[A]之共聚物（A -1 ) 、80 重量份之 KAYARAD DPHA ( Nippon KayakuExamples of high boiling solvents include N-methylformamide, N,N-dimethylformamide, N-methylformamidine, n-methylacetamide, N,N-dimethylethoxime Amine, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, I monooctanol, 1-nonanol, benzyl alcohol 'Benzyl acetate' ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethyl carbonate, propyl carbonate and cellulose acetate phenyl ester. The above high boiling point solvents may be used singly or in combination of two or more. The composition solution prepared as described above was filtered using a porous filter paper having an opening diameter of about 0 · 2 to 0.5 μm before use. Method of Forming Spacer for Display Panel The following provides a method of forming a spacer for the display panel of the present invention from the radiation sensitive resin composition of the present invention. The above composition solution is first applied to the surface of the substrate to form a coating film. -21 - (18) (18) 1336815 The composition solution can be applied by a suitable method such as spraying, roller coating, spin coating, bar coating or ink jet coating. Subsequently, the solvent was evaporated by prebaking this coating film to obtain a film having no fluidity. The prebaking conditions which vary depending on the type and amount of each component are usually 60 to 12 ° C and the time is 10 to 600 seconds. The film is then exposed to light through a reticle of a predetermined pattern and developed with a developer to remove unwanted portions. The exposure for exposure is visible light, ultraviolet light, far ultraviolet light, electron irradiation, X-ray, etc., and is preferably ultraviolet light having a wavelength of 190 to 450 nm. The exposure is preferably 〇〇 to 20,000 joules per square meter, more preferably 1 50 to 1 〇, 〇〇〇 joules per square meter. The developer may be an aqueous alkaline solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or aqueous ammonia; a primary amine such as ethylamine or n-propylamine; a secondary amine such as diethylamine or Di-n-propylamine; tertiary amine such as triethylamine, methyldiethylamine or N-methylpyrrolidone; alcoholamine such as dimethylethanolamine or triethanolamine; quaternary ammonium salt such as tetramethylammonium hydroxide, four Ethyl ammonium hydroxide or choline; or a cyclic amine such as pyrrole, hexahydropyridine, 1 '8-diazabicyclo[5·4·0]-7-undecene or 1,5-diaza Bicyclo [4.3.0] - 5 - decene. The above aqueous alkaline solution may contain a suitable amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant. Development is preferably carried out at room temperature for 30 to 180 seconds. -22- (19) (19) 1336815 Development can be scouring, dipping or spraying. After development, it is rinsed with running water for 30 to 90 seconds, and then water is removed by spraying with compressed air or compressed nitrogen to obtain a film having a predetermined pattern. Subsequently, the film is heated at 150 to 250 ° C by a heater such as a hot plate or an oven, for example, on a hot plate for 5 to 30 minutes and in an oven for 30 to 90 minutes, thereby obtaining a predetermined shape interval. Things. EXAMPLES The following examples are provided to further illustrate the invention and are not intended to be limiting in any way. Synthesis Example 1 4 parts by weight of 2, azobisisobutyronitrile (AIBN) and 20 parts by weight of diethylene glycol ethyl methyl ether were injected into a flask equipped with a stirrer, and then 5 parts by weight ' 3-butadiene, 18 parts by weight of methacrylic acid, 40 parts by weight of benzyl methacrylate and 37 parts by weight of n-butyl methacrylate were injected into the flask. The inside of the flask was replaced with nitrogen to make these materials mild. Stirring, and the temperature of the reaction solution was raised to 80 ° C, and maintained at this point for 5 hours and further to 10 ° C for 1 hour, and then the temperature of the reaction solution was lowered to room temperature to obtain a copolymer. The polymer solution of [A] (solid content = 30.0% by weight), the Mw of this copolymer was 27,000, and this copolymer was named copolymer (A-1). Synthesis Example 2 -23- (20) (20) 1336815 4 parts by weight of 2'2>-azobisisobutyronitrile (AIBN) and 200 parts by weight of diethylene glycol ethyl methyl ether were injected to be stirred In a flask, 5 parts by weight of 1,3-butadiene, 5 parts by weight of styrene, 18 parts by weight of methacrylic acid, 40 parts by weight of glyceryl methacrylate, and 32 parts by weight of A The tricyclo[5.1.02'6]癸-8-ester was injected into the flask, and the inside of the flask was replaced with nitrogen. The materials were gently stirred, and the temperature of the reaction solution was raised to 80 ° C, and maintained at this point. After 5 hours, the reaction was further continued to 1 Torr °C for 1 hour, and then the temperature of the reaction solution was lowered to room temperature to obtain a polymer solution (solid content = 29.8% by weight) containing the copolymer [A]. The Mw of the copolymer was 26,000, and the copolymer was named as copolymer (A-2). Example 1 (1) Preparation of a composition solution 1 part by weight (solid content) of a copolymer of the component [A] (A - 1 ) , 80 parts by weight of KAYARAD DPHA ( Nippon Kayaku

Co., Ltd.)及 20 重量份作爲成份[B]之 R — 1302 ( Dai-ichi Kogyo Seiyaku Co., Ltd.)及 25 重量份作爲成份[C]之 2 — 苄基一 2 -二甲胺基一 1— (4 —嗎福啉基苯基）—丁一 1 — 酮（Ciba Specialty Chemicals Co·, Ltd.之 Irgacure 3 69 ) 溶解在丙二醇單甲基醚醋酸酯至固體含量是35重量％並 將所得的溶液經由開口直徑是0.2微米之微孔濾紙過濾而 製備組成物溶液。 -24- (21) (21)1336815 (2 )形成間隔物圖案 將上述組成物溶液用旋轉器施加至玻璃基板並在8 〇 °C之加熱板上預烘烤3分鐘而形成塗膜。 然後將塗膜暴露在空氣中，經由有預定圖案之光罩（ 10微米Χίο微米）在波長是365毫微米下用強度是1〇〇 瓦/平方米之紫外光照射3 0秒，隨後，在2 51用四甲基 氫氧化銨之0.2重量％水溶液將塗膜顯影1分鐘用純水淸 洗1分鐘，去除不要的部份而得到間隔物圖案（殘留物） ’將此間隔物圖案在220 °C之烤爐中加熱60分鐘，固化 而得到高度是5微米之間隔物圖案。 (3 )測量線性熱膨脹係數 將上述組成物溶液用旋轉器施加至玻璃基板並在8 〇 °C之加熱板上預烘烤3分鐘而形成塗膜。 然後將塗膜暴露在空氣中，經由有預定圖案之光罩（ 微米xl〇微米）在波長是365毫微米下用強度是1〇〇 瓦/平方米之紫外光照射30秒，隨後，在25 °C用四甲基 氫氧化銨之〇 · 2重量％水溶液將塗膜顯影1分鐘用純水淸 洗〗分鐘，將此間隔物圖案在2 2 0 °C之烤爐中加熱6 〇分 鐘，固化而得到用於量測之膜。 此膜在各測量溫度之厚度變化是經由配備溫度上升速 率是2.5 °C /分鐘之溫度變化器且測量溫度範圍是2〇至 180°C 之橢圓計（Mizojiri Kogaku Kogyosho Co·, Ltd.之 DVA - 3 6LH )測量且對各溫度繪圖而得到從其線性近似 -25- (22) (22)1336815 値之傾度ε ’因而從下式得到線性熱膨脹係數α，T代表 膜之最初厚度。 a = ξ. / Τ 傳統間隔物材料之線性熱膨脹係數是2 · Ο χ 1 〇 - 4 / 或更低’高於此値之線性熱膨脹係數可以說是高，測量結 果列在表1。 (4 )間隔物強度之評估 在上述（2 )所得的間隔物圖案之強度是在2 5卞之測 里溫度下用微擠壓測g式機（Shimadzu Corporation之 MCTM— 200)評估’在固定速率（2.65毫牛頓/秒）經 由直徑是5 0微米之扁平成穴器將負重施加至間隔物並測 量間隔物裂開或斷裂時之斷裂負重及斷裂扭曲（在斷裂時 之擠壓位移除以間隔物高度所得之値並以％表示），評估 結果列在表1。 (5 )耐熱擠壓性之評估 在上述（2 )所得的間隔物圖案之耐熱擠壓性是用微 擠壓測試機（Shimadzu Corporation 之 MCTM - 200)評估 ，在固定速率（0.28毫牛頓/秒）經由直徑是50微米之 扁平成穴器將負重施加至在1 60 °C加熱之間隔物且當間隔 物擠壓〇.75微米後移除，從下式得到其恢復因子。 恢復因子（％ )=( 0.75—殘留變形）xi 〇〇/ 0.75 當恢復因子是90 %或更高時，耐熱擠壓性可以說是 -26- (23) 1336815 滿意，評估結果列在表1。 (6 )熱尺寸安定性之評估 在上述（2 )所得的間隔物圖案在2 5 0 °C之烤爐中加 熱60分鐘’測量其膜厚度在加熱前後的尺寸變化率，當 熱尺寸安定性之値是5 %或更低時，熱尺寸安定性可以說 是滿意，評估結果列在表1。Co., Ltd.) and 20 parts by weight of R-1302 (Dai-ichi Kogyo Seiyaku Co., Ltd.) as component [B] and 25 parts by weight as component [C] 2 - benzyl- 2 -dimethyl Amino-1,4-(4-norpolinylphenyl)-butyl-1-ketone (Irgacure 3 69 from Ciba Specialty Chemicals Co., Ltd.) is dissolved in propylene glycol monomethyl ether acetate to a solid content of 35 weight % The resulting solution was filtered through a microporous filter paper having an opening diameter of 0.2 μm to prepare a composition solution. -24- (21) (21) 1336815 (2) Formation of spacer pattern The above composition solution was applied to a glass substrate by a spinner and prebaked on a hot plate at 8 ° C for 3 minutes to form a coating film. The coating film is then exposed to air and irradiated with ultraviolet light having a intensity of 1 watt/m 2 for 30 seconds at a wavelength of 365 nm via a mask having a predetermined pattern (10 μm Χίο μm), followed by 2 51 The coating film was developed with a 0.2% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute, rinsed with pure water for 1 minute, and the unnecessary portion was removed to obtain a spacer pattern (residue) 'This spacer pattern was 220. The oven was heated in a °C oven for 60 minutes and cured to obtain a spacer pattern having a height of 5 μm. (3) Measurement of Linear Thermal Expansion Coefficient The above composition solution was applied to a glass substrate by a spinner and prebaked on a hot plate at 8 ° C for 3 minutes to form a coating film. The coating film is then exposed to air and irradiated with ultraviolet light having a intensity of 1 watt/m 2 for 30 seconds at a wavelength of 365 nm via a mask having a predetermined pattern (micron x 10 μm), followed by 25 °C, the coating film was developed with tetramethylammonium hydroxide in 2% by weight aqueous solution for 1 minute, rinsed with pure water for 1 minute, and the spacer pattern was heated in an oven at 2200 ° C for 6 minutes. Curing to obtain a film for measurement. The thickness variation of the film at each measured temperature is via an ellipsometer equipped with a temperature changer with a temperature rise rate of 2.5 ° C /min and a temperature range of 2 〇 to 180 ° C (DVA of Mizojiri Kogaku Kogyosho Co., Ltd.) - 3 6LH ) Measured and plotted for each temperature to obtain a linear approximation ε from its linear approximation -25 - (22) (22) 1336815 因而 ', thus obtaining a linear thermal expansion coefficient α from the following equation, where T represents the initial thickness of the film. a = ξ. / Τ The linear thermal expansion coefficient of the conventional spacer material is 2 · Ο χ 1 〇 - 4 / or lower. The linear thermal expansion coefficient higher than this 可以 can be said to be high, and the measurement results are listed in Table 1. (4) Evaluation of spacer strength The strength of the spacer pattern obtained in the above (2) was evaluated by micro-extrusion g-type machine (MCTM-200 of Shimadzu Corporation) at a temperature of 25 Torr. Rate (2.65 millinewtons per second) The load was applied to the spacer via a flat hole crater with a diameter of 50 microns and the fracture weight and fracture distortion at the time of cracking or fracture of the spacer were measured (the crush position was removed at the time of the break) The results obtained by the height of the spacer are expressed in %), and the evaluation results are shown in Table 1. (5) Evaluation of heat-resistant extrusion property The heat-resistant extrusion property of the spacer pattern obtained in the above (2) was evaluated by a micro-extrusion tester (MCTM-200 of Shimadzu Corporation) at a fixed rate (0.28 mN/s). The load was applied to the spacer heated at 1600 ° C via a flat hole boringer having a diameter of 50 μm and removed after the spacer was pressed 〇 75 μm, and its recovery factor was obtained from the following formula. Recovery factor (%) = (0.75 - residual deformation) xi 〇〇 / 0.75 When the recovery factor is 90% or higher, the hot extrusion resistance can be said to be -26- (23) 1336815 Satisfactory, the evaluation results are listed in Table 1. . (6) Evaluation of thermal dimensional stability The spacer pattern obtained in the above (2) was heated in an oven at 250 ° C for 60 minutes to measure the dimensional change rate of the film thickness before and after heating, when the thermal dimensional stability was After the 5% is 5% or lower, the thermal dimensional stability can be said to be satisfactory, and the evaluation results are listed in Table 1.

實例2 除了 70 重量份之 KAYARAD DPHA(Nippon Kayaku Co·，Ltd.)及 30 重量份之 R — 1302 (Dai-ichi Kogyo Seiyaku Co·，Ltd.)作爲成份[B]使用外，相同於實例l之 方法製備並評估組成物溶液，評估結果列在表1。 實例3Example 2 The same as Example 1 except that 70 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.) and 30 parts by weight of R - 1302 (Dai-ichi Kogyo Seiyaku Co., Ltd.) were used as the component [B]. The composition solution was prepared and evaluated, and the evaluation results are shown in Table 1. Example 3

除了共聚物（A - 2 )作爲成份[A ]使用外，相同於實 例1之方法製備並評估組成物溶液，評估結果列在表1。 比較實例1 除了共聚物（A — 2 )作爲成份[A]且100重量份之 KAYARAD DPHA ( Nippon Kayaku Co·, Ltd.)作爲成份 [B]使用外，相同於實例1之方法製備並評估組成物溶液 ’評估結果列在表1。 -27-The composition solution was prepared and evaluated in the same manner as in Example 1 except that the copolymer (A-2) was used as the component [A], and the evaluation results are shown in Table 1. Comparative Example 1 The composition was prepared and evaluated in the same manner as in Example 1 except that the copolymer (A-2) was used as the component [A] and 100 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.) was used as the component [B]. The results of the solution 'evaluation are listed in Table 1. -27-

Claims (1)

13368,15 - 一~一―) I公告本） 、一·》»^~·· , — Ι·—-- 拾、申請專利範圍 否$研日修正本 第9 3 1 1 6 7 1 8號專利申請案 中文申請專利範圍修正本 民國99年4月14日修正 1 ·—種供顯示面板用之間隔物，其線性熱膨脹係數 係介於2.0xlCT4/°C (不包括此端値）及8·〇χι〇-4/ι (包括 此端値）之間，且其係形成自感射線樹脂組成物，該組成 物包含[A]—種（al )與（a2 )之共聚物：（ai )不飽和 的羧酸及/或不飽和的羧酸酐，與（a2)係除了成份（al )以外之不飽和的化合物、[B]多官能基不飽和的單體及 [C]感射線的聚合作用引發劑’其中該成份[b]的含量以 1〇〇重量份之該成份[a]爲基準是10至15〇重量份，且該 成份[B]含有以該化合物[B]的總量爲基準之1 〇至5〇重量 %之具有胺基甲酸酯鍵之多官能基（甲基）丙嫌酸酯。 2. —種液晶顯示裝置，其包含申請專利範圍第丨項供 顯示面板用之間隔物》13368,15 - 一~一―) I Announcement), 一··»^~··, — Ι·—-- Pick up, apply for patent scope No $ 研日修正本第9 3 1 1 6 7 1 8 Patent application Chinese patent application scope revision Amendment of the Republic of China on April 14, 1999 1 · A spacer for display panels with a linear thermal expansion coefficient of 2.0xlCT4/°C (excluding this end) and 8 〇χι〇-4/ι (including this end 値), and which forms a self-inductive ray resin composition comprising [A]-copolymer of (al) and (a2): (ai An unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) an unsaturated compound other than the component (al), [B] a polyfunctional unsaturated monomer, and [C] radiation-sensitive The polymerization initiator' wherein the content of the component [b] is 10 to 15 parts by weight based on 1 part by weight of the component [a], and the component [B] contains the total of the compound [B] A polyfunctional (meth)propionic acid ester having a urethane bond in an amount of from 1 Torr to 5% by weight based on the amount. 2. A liquid crystal display device comprising a spacer for a display panel in the scope of the patent application 》
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