TW200401002A - Resin composition and protective film - Google Patents

Resin composition and protective film Download PDF

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Publication number
TW200401002A
TW200401002A TW092112983A TW92112983A TW200401002A TW 200401002 A TW200401002 A TW 200401002A TW 092112983 A TW092112983 A TW 092112983A TW 92112983 A TW92112983 A TW 92112983A TW 200401002 A TW200401002 A TW 200401002A
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TW
Taiwan
Prior art keywords
protective film
weight
copolymer
component
acid
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TW092112983A
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Chinese (zh)
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TWI286563B (en
Inventor
Umaba Atsushi
Taniwa Kazuaki
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Jsr Corp
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Priority claimed from JP2002213816A external-priority patent/JP3797288B2/en
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Publication of TWI286563B publication Critical patent/TWI286563B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds

Abstract

A resin composition comprises (A) a copolymer of an epoxy-containing unsaturated compound and an unsaturated compound of a different alkenic series; (B) a reaction product of a hydroxy-containing epoxy resin and an alkoxysilane; and (C) a cationic polymeric compound different from the components (A) and (B). The resin composition can form an optical device protective film having high planarity, surface hardness, excellent thermal resistance, pressure withstanding, acid resistance, alkaline resistance, anti-sputtering, etc.

Description

200401002 (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關固化性樹脂組成物，形成保護膜的方法， 以及保護膜。詳言之，有關作爲形成用於液晶顯示器元件 (LCD)用濾色器及電荷耦合元件（CCD)用濾色器等的保護 膜之用的材料很適用的固化性樹脂組成物，使用其組成物 的保護膜之形成方法，以及由其組成物所形成的保護膜。 【先前技術】 LCD或CCD等之放射性裝置，在其製造過程中將實施 使用溶劑、酸或鹼溶液等的顯示元件之浸漬處理。又藉由 濺鍍（sputtering)以形成配線電極層時，元件表面將被局部 性曝露在高溫中。因而，爲防止被此等處理而元件劣化或 受損起見，在來採用在表面設置由對此等處理具有耐性的 薄膜而成的保護膜之作法。 如此的保護膜必須是具有··對待形成該保護膜的基體 或下層以及對將形成在保護膜上的層具有高密貼性者，膜 本身爲平滑且強韌者，具有透明性者，耐熱性及耐光性高 且長期不會引起著色、變黃、白化等之變質者，耐水性、 抗溶劑性、抗酸性及抗鹼性優異者等之各種物性。爲形成 能符合此等種種物性的保護膜用之材料而言，周知有在日 本專利特開平5-78453號公報中所揭示的含有具有縮水甘 油基的聚合物的熱固化性組成物。 又，如將此等保護膜使用爲彩色液晶顯示器裝置或電 0〇74 -5- (2) (2)200401002 荷耦合元件之濾色器時，一般需要可使底子基板上所形成 的因濾色器所引起的高低差加以平坦的條件。 再者，在彩色液晶顯示裝置，例如STN(Super Twisted Nematic ’ 超扭轉向列）方式或 TFT(Thin Film Transister，薄膜電晶體）方式之彩色液晶顯示元件方面， 爲均句保持液晶層之單兀間隙（c e 11 g a p )起見，一般採用 在保護膜上散佈熔珠狀之間隔物之後將面板（panel)貼合之 方式。然後’將密封材加以熱壓接以進行液晶單元之密封 ，惟由於當時所施加的熱及壓力，會出現熔珠所存在的部 份之保護膜凹陷的現象，而引起單元間隙混亂的問題。 特別是當製造S T N方式之彩色液晶顯示元件時，必須 嚴格實施濾色器與相對向基板間的張貼之精密度，而對保 護膜則需要具有極高度的高低差之平坦化性能及耐熱耐壓 性能。 又’近年來’亦在採用藉由濺鍍而在濾色器之保護膜 上進行配線電極（銦錫氧化物，I T 0 )之成膜，並使用強酸 或強鹼等將I T 0加以濺鍍的方式。由此，保護膜會在濺鍍 時表面被局部性曝露在高溫中，或經過種種藥品處理。因 因此，保護膜亦需要能抗耐此等處理，以及爲防止在藥品 處理時ITO將從保護膜上剝離起見，尙需要具有與配線電 極間的密貼性。 在如此的保護膜之形成上，如能使用具有可以簡單方 法即可形成硬度優異的保護膜的優點的熱固化性組成物， 則甚爲方便’惟目則爲止尙未被開發一種能形成既能符合 -6 - (3) (3)200401002 透明性等作爲保護膜的一般性的必備性能，又能符合如上 述的各種性能的保護膜，且作爲組成物的儲存安定性優異 的材料。 【發明內容】 本發明係鑑於上述情形所開發者。 本發明之目在於提供一種即使表面之平坦性較差的基 板而言，仍能在該基體上形成平坦性較高的固化膜，並且 適合用於爲形成表面硬度高，耐熱耐壓性、抗酸性、抗鹼 性、抗濺鍍性等的各種耐性優異的光學裝置用保護膜的樹 脂組成物。 本發明之其他目的在於提供使用本發明之上述組成物 的保護膜之形成方法。 本發明之再其他目的在於提供由上述組成物所形成的 保護膜。 本發明之再其他目的及優點，可由下述說明即明瞭。 如依本發明’則本發明之上述目的及優點，第一，可 由一種樹脂組成物達成，其特徵爲：含有 [A](al)含有環氧基之不飽和化合物，和（a2)與（al)成 份不相同的稀烴系不飽和化合物之共聚物（以下簡稱共聚 物[A]。） [B ] (b 1 )含有趨基之環氧樹脂與（b 2 )烷氧基矽烷的反應 物，以及 [C]與[A]成份及[B]成份不相同的陽離子聚合性化合 (4) (4) 200401002 物。 如依本發明，則本發明之上述目的及優點，第二，可 由一種樹脂組成物達成，其特徵爲：含有 [E] (el)不飽和羧酸及/或不飽和羧酸酐，（e2)含有環 氧基之不飽和化合物以及（e3)與（el)成份及（e2)成份不相 同的烯烴系不飽和化合物之共聚物（以下，簡稱共聚物[E] 。） [B](bl)含有羥基之環氧樹脂與（b2)烷氧基矽烷的反應 物，以及 [F] 與[B]成份及[E]成份不相同的陽離子聚合性化合物 〇 如依本發明，則本發明之上述目的及優點，第三，可 由一種保護膜之形成方法所達成，而其特徵爲： 將上述[A ]成份、[B ]成份、[C ]成份以及[B ]固化劑加 以混合’將其混合物塗佈在基板上，接著，藉由熱及/或 放射線而加以處理。 又’如依本發明’則本發明之上述目的及優點，第四 ’可由一種保護膜之形成方法所達成，而其特徵爲： 將上述[E]成份、[B]成份、[F]成份以及[G]因熱及/或 放射線而將產生酸的化合物加以混合，並將其混合物塗佈 在基板上’接著’藉由熱及/或放射線加以處理。 再者，如依本發明，則本發明之上述目的及優點，第 五，可由從本發明之上述樹脂組成物所形成的保護膜所達 成。 * 8 - (5) (5)200401002 發曰月之最佳實施形態 以下，就本發明加以詳述。首先，就本發明之樹脂組 成物加以說明。 共聚物[A] 本發明中所使用的共聚物[A]，係 (a)含有環氧基之不飽和化合物，和（a2)與（al)成份 不相同的烯烴系不飽和化合物之共聚物。 修 上述al)含有環氧基之不飽和化合物，係在一分子中 持有環氧基及聚合性碳-碳雙鍵的化合物。具體而言，可 例舉：丙烯酸縮水甘油酸、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、 α-正丁基丙烯酸縮水甘油酯、丙烯酸-3，4-環氧基丁酯 、甲基丙烯酸-3，4 -環氧基丁酯、丙烯酸-6，7 -環氧基庚 酯、甲基丙烯酸-6，7-環氧基庚酯、α-乙基丙烯酸-6’ 7-環氧基庚酯 '鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮 鲁 水甘油醚、對乙烯基苄基縮水甘油醚等。 此中，從共聚合反應性及能提高所製得的保護膜之耐 熱性、硬度的觀點來看，較佳爲使用甲基丙烯酸縮水甘油 酯、甲基丙烯酸-6，7 -環氧基庚酯、鄰乙稀基苄基縮水甘 油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油 醚等。此等（a 1)含有環氧基之不飽和化合物’可以單獨或/ 及或組合2種以上使用。 上述與（a2)(al)成份不相同的烯烴系不飽和化合物’ -9- (6) (6)200401002 不具有環氧基而持有聚合性碳-碳雙鍵的化合物。具體而 言’可例舉：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙 烯酸正丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酬 等之甲基丙烯酸烷酯； 丙烯酸甲酯、丙烯酸異丙酯等之丙烯酸烷酯； 環己基甲基丙烯酸酯、2-甲基環己基甲基丙烯酸酯、 甲基丙烯酸環己酯、甲基丙烯酸三環[5.2.1.02,6]癸-8-基（ 在該技術領域中，作爲慣用名而稱爲甲基丙烯酸二環戊烷 酯）、二環戊烷氧基乙基甲基丙烯酸酯、異冰片基甲基丙 烯酸酯等之甲基丙烯酸環狀烷酯； 環己基丙烯酸酯、2-甲基環己基丙烯酸酯、丙烯酸環 己酯 '丙烯酸三環[5.2.1.02,6]癸-8-基（在該技術領域中， 作爲慣用名而稱爲丙烯酸二環戊烷酯）、二環戊烷氧乙基 丙烯酸酯、異冰片基丙烯酸酯等之丙烯酸環狀烷酯； 苯基甲基丙烯酸酯、苄基甲基丙烯酸酯等之甲基丙烯 酸芳酯；苯基丙烯酸酯、苄基丙烯酸酯等之丙烯酸芳酯；馬 來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等之二羧酸酯 5 茚、1 -甲茚等之茚衍生物； 苯基馬來醯亞胺、苄基馬來醯亞胺、環己基馬來醯亞 胺、N-琥珀醯亞胺基-3-馬來醯亞胺安息香酸酯、N-琥珀 醯亞胺基-4-馬來醯亞胺丁酸酯、N_琥珀醯亞胺基-6-馬來 醯亞胺己酸酯、N-琥珀醯亞胺基-3 -馬來醯亞胺丙酸酯、 N-(9-吖啶基）馬來醯亞胺等之二羧醯亞胺衍生物；2-羥乙 (7) (7)200401002 基甲基丙烯酸酯、2-羥丙基甲基丙烯酸酯等之羥烷基酯； 以及 苯乙烯、α -甲基苯乙烯、間甲基苯乙烯、對甲基苯 乙烯、乙烯基甲苯、對乙氧基苯乙烯、丙烯腈、甲基丙烯 腈、氯化乙烯、二氯亞乙烯、丙烯醯胺 '甲基丙烯醯胺、 乙酸乙烯酯、1，3 -丁二烯、異戊二烯、2，3·二甲基-1， 3-丁二烯等。 此中，從共聚反應性及所製得的保護膜之耐熱性的觀 點來看，較佳爲苯乙烯、第三丁基甲基丙烯酸酯、甲基丙 烯酸二環戊烷酯、對甲氧基苯乙烯、2-甲基環己基丙烯酸 酯、1，3 -丁二烯、苯基馬來醯亞胺、環己基馬來醯亞胺 等。此等化合物（a2)，可以單獨或組合使用。 共聚物[A]之具體例而言，可例舉： 苯乙烯/縮水甘油基甲基丙烯酸酯共聚物、 苯乙烯/縮水甘油基丙烯酸酯共聚物、 甲基丙烯酸三環[5.2.1.02’6]癸烷-8-基酯/縮水甘油基 甲基丙烯酸酯共聚物、 甲基丙烯酸三環[5.2.1 ·02’6]癸烷-8-基酯/縮水甘油基 丙烯酸酯共聚物、 苯乙烯/環己基馬來醯亞胺/縮水甘油基甲基丙烯酸酯 共聚物、 苯乙烯/苯基馬來醯亞胺/縮水甘油基甲基丙烯酸酯共 聚物、 苯乙烯/甲基丙烯酸三環[5.2.1.〇2’6]癸烷-8-基酯/縮水 -11 - 200401002 ⑹ 甘油基甲基丙烯酸酯共聚物、 苯乙烯/甲基丙烯酸-6，7_環氧基庚酯共聚合物、 甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯/甲基丙烯酸-6，7 -環氧基庚酯共聚物、 苯乙烯/環己基馬來醯亞胺/甲基丙烯酸-6，7-環氧基 庚酯共聚物。 其中’較佳者可舉：苯乙烯/縮水甘油基甲基丙烯酸 酯共聚物、甲基丙烯酸三環[5.2.1.02,6]癸烷-8 -基酯/縮水 甘油基甲基丙烯酸酯共聚物、苯乙烯/環己基馬來醯亞胺/ 縮水甘油基甲基丙烯酸酯共聚物、苯乙烯/甲基丙烯酸三 環[5.2.1 ·〇2’6]癸烷-8-基酯/縮水甘油基甲基丙烯酸酯共聚 物等。 共聚物[Α]可以單獨或2種以上一起使用。 共聚物[Α]，係對每共聚物[Α]ι 00重量份，從化合物 (al)所衍生的組成單元含有較佳爲1至90重量份，更佳爲 40至90重量份。 共聚物[A]，係聚乙烯換算重量平均分子量（以下，簡 稱「Mw」。）在較佳爲3,000至100,000，更佳爲3,000至 50,000 ' 特佳爲 3,000戋 20,000者。 共聚物[A]，可將上述（al)含有環氧基之不飽和化合 物及（a2)烯烴系不飽和化合物，在適當的溶媒及聚合起始 劑之存在下’藉由例如自由基聚合而加以合成。 共聚物[A]之合成時可使用的溶媒而言，可例舉： 200401002 Ο) 四氫呋喃等之醚類； 乙二醇-甲醚、乙二醇-乙醚等之乙二醇醚類； 甲基溶纖素乙酸酯、乙基溶纖素乙酸酯等之乙二醇烷 基醚乙酸酯類； 二乙醇一甲醚、二乙二醇一乙醚、二乙二醇二甲醚、 二乙醇二乙醚、二乙二醇乙基甲基醚等之二乙二醇類； 丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙二醇丁醚 等之丙二醇一烷醚類； 丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙醚 乙酸酯、丙二醇丁醚乙酸酯等之丙二醇烷醚乙酸酯類； 丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚 丙酸酯、丙二醇丁醚丙酸酯等之丙二醇烷醚丙烯酸類； 甲苯、二甲苯等之芳香族烴類； 甲基乙基甲酮、環己酮、4-羥基-4-甲基-2-戊酮、甲 基異戊基甲酮等之酮等；以及 乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基 丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸 乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳 酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲 酯、3 -羥基丙酸乙酯、3 -羥基丙酸丙酯、3 -羥基丙酸丁酉旨 、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙 酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸 甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁 酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯 -13- (10) (10)200401002 、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、 丁氧基乙酸丙酯、丁氧基乙酸丁酯、2_甲氧基丙酸甲酯、 2 -甲氧基丙酸乙酯、2 -甲氧基丙酸丙酯、2 -甲氧基丙酸丁 酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2_乙氧基丙 酸丙酯、2 -乙氧基丙酸丁酯、2 -丁氧基丙酸甲酯、2 -丁氧 基丙酸乙酯' 2 -丁氧基丙酸丙酯、2 -丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、3 -甲氧基丙酸丙酯 ' 3 -甲氧基丙酸丁酯、3 -乙氧基丙酸甲酯' 3 -乙氧基丙酸 乙酯、3 -乙氧基丙酸丙酯、3 -乙氧基丙酸丁酯、3 -丙氧基 丙酸甲酯' 3 -丙氧基丙酸乙酯' 3 -丙氧基丙酸丙醋、3 -丙 氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、 3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等之酯類。 溶媒可以單獨或2種以上一起使用。 此中，較佳爲二乙二醇類、丙二醇烷基乙酸酯類，特 佳爲乙二醇乙基甲基醚、丙二醇甲醚乙酸酯、丙二醇乙醚 乙酸酯。 共聚物[A]之製造時可使用的起始劑而言’可使用一 般作爲自由基聚合起始劑而周知者，可例舉：2 ’ 2 偶 氮異丁腈、2，2，-偶氮雙（2,4 -二甲基戊腈）、2’ 2 / -偶 氮雙（4-甲氧基-二甲基戊腈）等之偶氮化合物；過氧化苯甲 醯、過氧化月桂醯、過氧化第三丁基三甲基乙酸醋、工’ 1 一-雙（過氧化第三丁基）環己烷等之有機過氧化物；以及過 氧化氫。如作爲自由基聚合起始劑而使用過氧化物時’則 可將過氧化物與還原劑一起作用而作爲氧化還原（red〇X)型 (11) (11)200401002 起始劑。 [B](bl)含有羥基之環氧樹脂與（b2)烷氧基矽烷間的反應生 成物 本發明中所使用的[B ]成份，係（b 1)含有羥基之環氧 樹脂與（b 2)烷氧基矽烷間的反應生成物。 (bl)含有經基之環氧樹脂而言’可例舉：雙酚型環氧 樹脂、淸漆型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘 油胺型環氧樹脂、線形脂肪族環氧樹脂及脂環式環氧樹脂 ，以及雙1女型環氧樹脂等。此中，較佳爲使用雙酣型環氧 樹脂及淸漆型環氧樹脂。 上述雙酚型環氧樹脂’可由雙酚類與表氯醇或甲 基表氯醇等之鹵化環氧化物間的反應而製得。 上述雙酚類而言’可例舉：酚或2, 6_二鹵化苯與甲 醛、乙醛、丙嗣、甲基苯基酮、環己酮、二苯基嗣等之醛 類或酮類間的反應生成物、及二羥基苯基硫化物之因過氧 酸而生成的氧化生成物’以及氫醌互相間之醚化反應生成 物等。在此等雙酮型環氧樹脂之中，特別是作爲雙酚，使 用雙酚A、雙酚S、雙酚F或此等之氫添加物所製得的雙酚 型環氧樹脂最廣被採用而最佳。 又，雙酚型環氧樹脂，具有能與後述的（b2)烷氧基矽 烷反應的羥基。惟構成雙酚型環氧樹脂的所有分子不需要 都具有該羥基，而祗要是作爲雙酚型環氧樹脂全體而具有 羥基即可。例如，雙酚A型環氧樹脂可以下述式表示， (12)200401002 ch2chch200401002 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a curable resin composition, a method for forming a protective film, and a protective film. Specifically, a curable resin composition is suitably used as a material for forming a protective film for a color filter for a liquid crystal display element (LCD) and a color filter for a charge-coupled element (CCD), and the composition is used. A method for forming a protective film for an object, and a protective film formed from a composition thereof. [Prior art] In the manufacturing process of a radioactive device such as an LCD or a CCD, a display element such as a solvent, an acid or an alkali solution is immersed during the manufacturing process. When the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to a high temperature. Therefore, in order to prevent the elements from being deteriorated or damaged by these processes, a method of providing a protective film made of a thin film having resistance to these processes has been adopted on the surface. Such a protective film must have a base body or a lower layer to be formed with the protective film and a layer having high adhesion to the layer to be formed on the protective film. The film itself is smooth and strong, transparent, and heat resistant. And those who have high light resistance and do not cause coloration, yellowing, whitening and other deterioration for a long time, and various physical properties such as water resistance, solvent resistance, acid resistance and alkali resistance. In order to form a material for a protective film that can meet these various physical properties, a thermosetting composition containing a polymer having a glycidyl group, which is disclosed in Japanese Patent Laid-Open No. 5-78453, is known. In addition, if these protective films are used as color liquid crystal display devices or electrical filters of 0074 -5- (2) (2) 200401002 with a coupling element, it is generally necessary to make the factor filter formed on the base substrate. The level difference caused by the color device gives a flat condition. Furthermore, in terms of color liquid crystal display devices, such as STN (Super Twisted Nematic ') or TFT (Thin Film Transister) method, color liquid crystal display elements are uniform units that maintain the liquid crystal layer. For the gap (ce 11 gap), generally, a method is adopted in which a bead-shaped spacer is spread on a protective film and a panel is attached. Then, the sealing material is thermocompression-bonded to seal the liquid crystal cell. However, due to the heat and pressure applied at that time, a phenomenon in which the protective film of the molten beads exists is depressed, which causes a problem that the cell gap is disordered. Especially when manufacturing STN-type color liquid crystal display elements, it is necessary to strictly implement the precision between the color filter and the opposing surface, and the protective film needs to have a very high level of flatness and heat resistance and pressure resistance. performance. In recent years, it has also been used to form wiring electrodes (indium tin oxide, IT 0) on the protective film of color filters by sputtering, and IT 0 is sputtered using a strong acid or alkali. The way. As a result, the surface of the protective film is locally exposed to high temperatures during sputtering, or subjected to various chemical treatments. Therefore, the protective film also needs to be resistant to such treatments, and in order to prevent the ITO from peeling off from the protective film during drug processing, it is necessary to have adhesion to the wiring electrodes. In the formation of such a protective film, it is very convenient to use a thermosetting composition that has the advantage that a protective film with excellent hardness can be formed by a simple method. It can meet the general necessary properties of -6-(3) (3) 200401002 as a protective film, and also can meet the various properties of the protective film as described above, and is a material with excellent storage stability of the composition. SUMMARY OF THE INVENTION The present invention has been developed in view of the above circumstances. An object of the present invention is to provide a substrate having a low flatness on the surface, which can still form a cured film with high flatness on the substrate, and is suitable for forming a high surface hardness, heat and pressure resistance, and acid resistance. Resin composition of a protective film for an optical device which is excellent in various resistances such as alkali resistance, sputtering resistance, and the like. Another object of the present invention is to provide a method for forming a protective film using the composition of the present invention. Still another object of the present invention is to provide a protective film formed from the above composition. Still other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above-mentioned objects and advantages of the present invention are firstly achieved by a resin composition, which is characterized in that it contains [A] (al) an unsaturated compound containing an epoxy group, and (a2) and ( al) Copolymers of dilute hydrocarbon-based unsaturated compounds with different compositions (hereinafter referred to as copolymer [A].) [B] (b 1) Reaction of tacky epoxy resin with (b 2) alkoxysilane (4) (4) 200401002 substances, and cationically polymerizable compounds whose [C] and [A] and [B] components are different. According to the present invention, the above-mentioned objects and advantages of the present invention can be achieved by a resin composition, which is characterized by containing [E] (el) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (e2) Copolymers of unsaturated compounds containing epoxy groups and olefin-based unsaturated compounds having different components (e3) from (el) and (e2) (hereinafter referred to as copolymer [E].) [B] (bl) A reaction product of a hydroxyl-containing epoxy resin and (b2) an alkoxysilane, and a cationically polymerizable compound having a component [F] different from the component [B] and the component [E]. According to the present invention, the above-mentioned of the present invention The purpose and advantages, third, can be achieved by a method for forming a protective film, which is characterized by: mixing the above-mentioned [A] component, [B] component, [C] component, and [B] curing agent 'to mix the mixture It is coated on a substrate and then processed by heat and / or radiation. And 'as according to the present invention', the above-mentioned objects and advantages of the present invention, the fourth 'can be achieved by a method for forming a protective film, and is characterized in that the above-mentioned [E] component, [B] component, [F] component And [G] The acid-generating compound is mixed by heat and / or radiation, and the mixture is coated on a substrate and then 'treated' by heat and / or radiation. Furthermore, according to the present invention, the above-mentioned objects and advantages of the present invention are fifthly achieved by a protective film formed from the above-mentioned resin composition of the present invention. * 8-(5) (5) 200401002 The best embodiment of the month is described in detail below. First, the resin composition of the present invention will be described. Copolymer [A] The copolymer [A] used in the present invention is a copolymer of (a) an unsaturated compound containing an epoxy group, and (a2) an olefinic unsaturated compound having a different component from (al) . The above al) unsaturated compound containing an epoxy group is a compound having an epoxy group and a polymerizable carbon-carbon double bond in one molecule. Specific examples include: glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and acrylic acid. -3,4-epoxybutyl ester, -3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate Α-ethylacrylic acid-6 '7-epoxyheptyl' o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Among these, from the viewpoints of copolymerization reactivity and heat resistance and hardness of the protective film to be produced, it is preferable to use glycidyl methacrylate and -6,7-epoxyheptyl methacrylate. Esters, o-ethylene benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like. These (a 1) epoxy group-containing unsaturated compounds' can be used singly or / and in combination of two or more kinds. The above-mentioned olefin-based unsaturated compound having a component different from (a2) (al) '-9- (6) (6) 200401002 does not have an epoxy group and has a polymerizable carbon-carbon double bond. Specifically, 'can be exemplified: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, third butyl methacrylate, and the like; Alkyl acrylates such as methyl acrylate, isopropyl acrylate, etc .; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, cyclohexyl methacrylate, tricyclic methacrylate [5.2.1.02,6 ] Dec-8-yl (known in the technical field as dicyclopentyl methacrylate), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, etc. Cyclic alkyl methacrylate; cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, cyclohexyl acrylate 'acrylic tricyclo [5.2.1.02,6] dec-8-yl (in the technical field, Common names are dicyclopentane acrylate), dicyclopentane oxyethyl acrylate, isobornyl acrylate and other cyclic alkyl acrylates; phenyl methacrylate, benzyl methacrylate Aryl methacrylate; phenyl acrylate, benzyl acrylate Aryl acrylate, etc .; dicarboxylic acid esters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. 5 indene, 1-indane derivatives, etc .; phenyl malein Imine, benzylmaleimide, cyclohexylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleate Succinimide butyrate, N-succinimide imino-6-maleimide hexanoate, N-succinimide imino-3 -maleimide propionate, N- (9- Acridinyl) Maleimidine imine and other dicarboximide derivatives; 2-hydroxyethyl (7) (7) 200401002-based methacrylate, 2-hydroxypropyl methacrylate, etc. Esters; and styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-ethoxystyrene, acrylonitrile, methacrylonitrile, ethylene chloride, dichloride Vinylidene, acrylamide 'methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3 · dimethyl-1,3-butadiene, and the like. Among these, from the viewpoints of copolymerization reactivity and heat resistance of the produced protective film, styrene, third butyl methacrylate, dicyclopentane methacrylate, and p-methoxystyrene are preferable. , 2-methylcyclohexyl acrylate, 1,3-butadiene, phenylmaleimide, cyclohexylmaleimide, and the like. These compounds (a2) can be used alone or in combination. Specific examples of the copolymer [A] include styrene / glycidyl methacrylate copolymer, styrene / glycidyl acrylate copolymer, and tricyclic methacrylate [5.2.1.02'6 ] Decane-8-yl ester / glycidyl methacrylate copolymer, tricyclic methacrylate [5.2.1.02'6] decane-8-yl ester / glycidyl acrylate copolymer, benzene Ethylene / cyclohexylmaleimide / glycidyl methacrylate copolymer, styrene / phenylmaleimide / glycidyl methacrylate copolymer, styrene / methacrylic tricycle [ 5.2.1.〇2'6] decane-8-yl ester / glycid-11-200401002 ⑹ Glyceryl methacrylate copolymer, styrene / methacrylic acid-6,7-epoxyheptyl copolymer Compound, tricyclo [5.2.1.02,6] decane-8-yl methacrylate / -6,7-epoxyheptyl methacrylate copolymer, styrene / cyclohexylmaleimide / formyl Acrylic acid-6,7-epoxyheptyl copolymer. Among them, the preferred ones are: styrene / glycidyl methacrylate copolymer, tricyclo [5.2.1.02,6] decane-8-yl ester / glycidyl methacrylate copolymer Styrene / cyclohexylmaleimide / glycidyl methacrylate copolymer, styrene / cyclomethacrylic tricyclic [5.2.1.〇2'6] decane-8-yl ester / glycidyl Methacrylate copolymers and the like. The copolymer [A] may be used alone or in combination of two or more kinds. The copolymer [A] is preferably from 1 to 90 parts by weight, and more preferably from 40 to 90 parts by weight per 100 parts by weight of the copolymer [A]. The copolymer [A] is a polyethylene-based weight average molecular weight (hereinafter, referred to as "Mw") preferably from 3,000 to 100,000, more preferably from 3,000 to 50,000 ', and particularly preferably from 3,000 to 20,000. In the copolymer [A], the above-mentioned (al) unsaturated compound containing an epoxy group and (a2) an olefin-based unsaturated compound can be obtained by, for example, radical polymerization in the presence of a suitable solvent and a polymerization initiator. To synthesize. Examples of solvents that can be used in the synthesis of the copolymer [A] include: 200401002 0) ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol-methyl ether and ethylene glycol-ether; methyl Ethylene glycol alkyl ether acetates such as lysocellulose acetate, ethyl lysocellulose acetate; diethanol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethanol Diethylene glycols such as diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, and other propylene glycol monoalkyl ethers; propylene glycol methyl ether acetate, propylene glycol Propylene glycol alkyl ether acetates such as diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether Propylene glycol alkyl ether acrylics such as propionate; Aromatic hydrocarbons such as toluene and xylene; Methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isopropyl Ketones such as amyl ketone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate , Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 -Methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate-13- (10) (10) 200401002, butyl propoxyacetate Ester, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-propyl methoxypropionate, 2-butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-butyl ethoxypropionate, methyl 2-butoxypropionate, 2- Ethyl butoxypropionate '2-propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Propyl methoxypropionate '3-Methoxypropionate, Methyl 3-ethoxypropionate' 3 -Ethoxypropionate, 3 -Ethoxypropionate, 3- Butyl ethoxypropionate, methyl 3-propoxypropionate '3-ethyl propoxypropionate' 3-propoxypropionate acetic acid, 3-propoxypropionate butyl ester, 3- Esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like. The solvent may be used alone or in combination of two or more kinds. Among these, diethylene glycols and propylene glycol alkyl acetates are preferred, and ethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate are particularly preferred. As for the initiator that can be used in the production of the copolymer [A], it is known that it can be generally used as a radical polymerization initiator, and can be exemplified by 2 '2 azoisobutyronitrile, 2, 2, and- Azo compounds (2,4-dimethylvaleronitrile), 2 '2 / -azobis (4-methoxy-dimethylvaleronitrile) and other azo compounds; benzamidine peroxide, lauryl peroxide醯, organic peroxides such as tertiary butyl trimethyl acetate, iso- 1-bis (tertiary butyl peroxide) cyclohexane; and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, the peroxide can be used together with a reducing agent as a redox (redox) type (11) (11) 200401002 initiator. [B] (bl) Reaction product between a hydroxyl-containing epoxy resin and (b2) an alkoxysilane. The component [B] used in the present invention is (b 1) a hydroxyl-containing epoxy resin and (b 2) A reaction product between alkoxysilanes. (bl) For epoxy resins containing warp-based groups, examples include: bisphenol epoxy resin, lacquer epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, linear aliphatic Epoxy resin and alicyclic epoxy resin, and double 1 female epoxy resin. Among these, a double-type epoxy resin and a lacquer-type epoxy resin are preferably used. The above-mentioned bisphenol type epoxy resin 'can be produced by a reaction between bisphenols and a halogenated epoxide such as epichlorohydrin or methyl epichlorohydrin. The above bisphenols can be exemplified by phenols or 2, 6-dihalogenated benzenes and aldehydes or ketones such as formaldehyde, acetaldehyde, propionium, methylphenyl ketone, cyclohexanone, diphenylfluorene and the like. Reaction products, and oxidation products of dihydroxyphenyl sulfide produced by peroxyacids, and etherification reaction products of hydroquinone. Among these bisketone epoxy resins, especially as bisphenols, bisphenol-type epoxy resins prepared by using bisphenol A, bisphenol S, bisphenol F, or these hydrogen additives are most widely used. Adopt it best. The bisphenol-type epoxy resin has a hydroxyl group capable of reacting with the (b2) alkoxysilane described later. However, it is not necessary that all molecules constituting the bisphenol type epoxy resin have the hydroxyl group, and it is sufficient if the bisphenol type epoxy resin as a whole has a hydroxyl group. For example, bisphenol A epoxy resin can be expressed by the following formula: (12) 200401002 ch2chch

0-CH2CHCH2 OH0-CH2CHCH2 OH

O丨 (3H2CHCH2 O …⑴ (式中，m爲0以上之整數’而111之平均重複單元數爲 0.1至 34)。 惟祗要是含有m爲1以上者’則可含有相當多的m爲0 者 ° 此等雙酚型環氧樹脂，可例如使與磷化合物反應’而 作爲磷改性雙酚型環氧樹脂使用。 上述淸漆型環氧樹脂，可由例如對酚淸漆型樹脂、甲 酚淸漆型樹脂，使鹵化環氧化物進行反應而製得。 上述縮水甘油酯型環氧樹脂，可由使例如酞酸等的多 元酸類與表氯醇進行反應而製得。 上述縮水甘油基胺型環氧樹脂，可由使例如二胺基二 苯基甲烷、異三聚氰酸等之多元胺類與表氯醇進行反應而 製得。 上述線形脂肪族環氧樹脂及脂環式環氧樹脂，可由使 用過乙酸等之過氧酸處理例如烯烴類而製得。 上述雙酚型環氧樹脂，可由使例如酚類與表氯醇進行 反應而製得。 0〇as -16- (13) (13)200401002 (b 1 )含有羥基之環氧樹脂之環氧當量之較佳値，係視 (bl)含有羥基之環氧樹脂之構造而異。可按照用途而適宜 選擇使用。通常，如使用環氧當量過份小的（bl)成份時， 則由於作成保護膜時可能會成爲與基板間的密貼性差的情 形之故，（b 1)成份之環氧當量較佳爲作成1 80以上。 另一方面，如使用環氧當量過份大的（bl)成份時，則 由於在與後述的（b2)烷氧基矽烷間的反應時可能會凝膠化 的情形之故，（bl)成份之環氧當量較佳爲作成5,000以下。 更佳的環氧當量爲200至4 00。 又，上述（b2)烷氧基矽烷而言，一般可使用溶膠-凝 膠法中所使用者。可例示 例如，以式：RSSMOI^h.p (式中，P表示〇或1之整數。R1表示可持有與碳原子直 結的官能基的碳數1至6之烷基、碳數1至6之芳基或碳數2 至6之不飽和脂肪族殘餘基，R2表示氫原子或碳數1至6之 烷基，存在有複數個R2可爲各相同或不相同。）表示的化 合物，或此等之部份縮合物等。就R1的上述官能基而言， 可例舉：乙烯基、锍基、環氧基、縮水甘油氧基等。 又，「部份縮合物」，係指將上述式所表示的烷氧基 矽烷中之烷氧基之一部份加以縮合而製得者之意。如此的 部份縮合物，可由將上述烷氧基矽烷在酸或鹼與水的存在 之下進行加水分解而製得。 如此的（b2)烷氧基矽烷之具體例而言，可舉：如四甲 氧基矽烷、四乙氧基矽烷、四丙氧基矽烷' 四異丙氧基矽 -17- (14) 200401002 烷、四丁氧基矽烷之四烷氧基矽烷類；甲基三甲氧基矽烷 、甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三丁氧基 矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷 '正丙基三 甲氧基矽烷 '正丙基三乙氧基矽烷、異丙基三甲氧基矽烷 、異丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三 乙氧基矽烷、3 -縮水甘油氧基丙基三甲氧基矽烷、3 -縮水 甘油氧基丙基三乙氧基矽烷、3-SfL基丙基三甲氧基矽烷、 3-巯基丙基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙 氧基矽烷、3，4-環氧基環己基乙基三甲氧基矽烷、3，4-環 氧基環己基乙基三乙氧基矽烷之三烷氧基矽烷類；或此等 之部份縮合物等。 此中，較佳爲可以下述（2): ch3oO 丨 (3H2CHCH2 O… ⑴ (where m is an integer of 0 or more and the average number of repeating units of 111 is 0.1 to 34). However, if it contains m or more, it may contain a considerable amount of m as 0 ° These bisphenol-type epoxy resins can be used, for example, as a phosphorus-modified bisphenol-type epoxy resin by reacting with a phosphorus compound. The above-mentioned lacquer-type epoxy resin can be made of, for example, p-phenol-lacquer-type resin, The phenol lacquer type resin is prepared by reacting a halogenated epoxide. The glycidyl ester type epoxy resin can be prepared by reacting a polyacid such as phthalic acid with epichlorohydrin. The glycidylamine Type epoxy resin, which can be produced by reacting polyamines such as diaminodiphenylmethane, isotricyanic acid, and epichlorohydrin. The above-mentioned linear aliphatic epoxy resin and alicyclic epoxy resin It can be obtained by treating peroxy acids such as peracetic acid with peracetic acid, etc. The above bisphenol type epoxy resin can be made by reacting, for example, phenols with epichlorohydrin. 0〇as -16- (13) (13) 200401002 (b 1) The best choice depends on the structure of (bl) epoxy resin containing hydroxyl groups. It can be appropriately selected and used according to the application. Generally, if the epoxy equivalent is too small (bl), it will be protected due to its protection. The film may have poor adhesion to the substrate, so the epoxy equivalent of the component (b 1) is preferably 1 80 or more. On the other hand, if the epoxy equivalent is excessively large (bl) In the case of a component, since it may gel when reacting with the (b2) alkoxysilane described later, the epoxy equivalent of the (bl) component is preferably made 5,000 or less. The equivalent weight is 200 to 400. In addition, as for the (b2) alkoxysilane, generally used by the sol-gel method. An example is, for example, the formula: RSSMOI ^ hp (where P represents 0). Or an integer of 1. R1 represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms or an unsaturated aliphatic residue having 2 to 6 carbon atoms, which can hold a functional group directly bonded to a carbon atom, R2 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R2 may be the same or different.) Or these partial condensates, etc. As far as the above functional groups of R1 are mentioned, vinyl, fluorenyl, epoxy, glycidyloxy, etc. Also, "partial condensates" are It is the meaning obtained by condensing a part of the alkoxy group in the alkoxysilane represented by the above formula. Such a partial condensate can be obtained by combining the above alkoxysilane with an acid or a base and water. It is prepared by hydrolyzing in the presence of. Specific examples of such (b2) alkoxysilanes include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropyl Siloxy-17- (14) 200401002 Alkane, tetrabutoxysilane, tetraalkoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane 'n-propyltrimethoxysilane' n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltrimethoxysilane Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-SfLpropylpropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Trisilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, trialkoxysilanes; or partial condensation of these Things. Among them, preferably the following (2): ch3o

Ί r3 I ，一och3 -n 〇CH3 …(2)Ί r3 I, a och3 -n 〇CH3… (2)

(式中，R3爲甲氧基或碳數1至6之烷基，而η爲1以上 之整數，η之平均重複單元數爲1至7)。 表示的四甲氧基矽烷或者烷基三甲氧基矽烷之部份縮合物 〇 該四甲氧基矽烷或烷基三甲氧基矽烷之部份縮合物之 -18 - (15) (15)200401002 數平均分子量較佳爲260至2,000程度者’更佳爲260至890 程度者。該四甲氧基砂院或院基二甲氧基砂院之部份縮合 物，由於在與（bl)成份間的反應中’與甲烷一起，未反應 之（b 2 )成份會蒸發而不會流出系外之故’反應操作上亦較 佳。又，由於在如此的部份縮合物中並不持有如所對應的 單體所持有的毒性之故，從此方面來看’亦很合適。 在前述式（2)中，平均重複單元數之値（η)較佳爲11以 下，更佳爲7以下。如此値超過1 1時，則由於溶解性變差 ，而變成對（b 1)含有羥基之環氧樹脂及有機溶劑中不溶化 之故，有與（b 1 )含有羥基之環氧樹脂間的反應性會低落的 傾向。 [B]成份，可由前述（bl)含有羥基之環氧樹脂與（b2)烷 氧基矽烷間的脫醇縮合反應而製得。（bl)含有羥基之環氧 樹脂與（b2)烷氧基矽烷之使用比例，如抵要是烷氧基能實 質上會殘留在所得的[B]成份中的比例，則並不特別限制 ，惟較佳爲將（b2)烷氧基矽烷之矽換算重量/(b 1 )含有羥基 之環氧樹脂之重量（重量比）作成0.01至3之範圍。 但，如（bl)含有羥基之環氧樹脂係環氧當量400程度 以上之高分子量樹脂時，則由於因脫醇反應之進行而會引 起溶液之高粘度化或凝膠化之故，作成如下述之方式即可 避免如此的不合適的情況。 ①較佳爲按（bl)含有羥基之環氧樹脂之羥基當量，或 (b2)烷氧基矽烷之任一方能較多之方式調整前述當量比爲 1以下以上或1以上之方式。特佳爲將前述當量比爲0 · 8以 ‘.·％ Λ n a(In the formula, R3 is a methoxy group or an alkyl group having 1 to 6 carbon atoms, η is an integer of 1 or more, and the average number of repeating units of η is 1 to 7). Partial condensate of tetramethoxysilane or alkyltrimethoxysilane represented by -18-(15) (15) 200401002 number of partial condensate of tetramethoxysilane or alkyltrimethoxysilane The average molecular weight is preferably about 260 to 2,000, and more preferably about 260 to 890. Part of the condensate of the tetramethoxy sand courtyard or the courtyard-based dimethoxy sand courtyard, because of the reaction with the (bl) component, together with methane, the unreacted (b 2) component will evaporate without Because it will flow out of the system, the reaction operation is also better. In addition, since such a partial condensate does not have the toxicity as the corresponding monomer holds, it is also suitable from this point of view. In the aforementioned formula (2), 値 (η) of the average number of repeating units is preferably 11 or less, and more preferably 7 or less. If it exceeds 11 in this way, it will become insoluble in (b 1) hydroxyl-containing epoxy resins and organic solvents due to poor solubility, and will react with (b 1) epoxy resins containing hydroxyl groups. Sexual tendency to decline. The component [B] can be prepared by the dealcoholization condensation reaction between the aforementioned (bl) hydroxyl-containing epoxy resin and (b2) alkoxysilane. (Bl) The use ratio of the epoxy resin containing a hydroxyl group and (b2) an alkoxysilane is not particularly limited if the ratio of the alkoxy group to be substantially remained in the obtained [B] component, but It is preferred that the silicon-based weight of (b2) alkoxysilane / (b1) the weight (weight ratio) of the epoxy resin containing a hydroxyl group be in the range of 0.01 to 3. However, if (bl) an epoxy resin containing a hydroxyl group is a high molecular weight resin having an epoxy equivalent of about 400 or more, the solution will have high viscosity or gelation due to the progress of dealcoholization reaction. The way described can avoid such inappropriate situations. ① It is preferred to adjust the aforementioned equivalence ratio to be 1 or more or 1 in such a way that (bl) the hydroxyl equivalent of an epoxy resin containing a hydroxyl group, or (b2) an alkoxysilane. It is particularly preferable that the aforementioned equivalent ratio is 0 · 8 to ‘. ·% Λ n a

DOOO -19- (16) (16)200401002 下或1.2以下之方式。尤其是較佳爲調整爲1.2以上。 ②藉由使脫醇反應在反應中途即停止等之方法，以防 止高粘度化、凝膠法。可採用例如’在逐漸高粘度化時將 反應系改成回流系以調整來自反應系的甲醇之餾除量，或 冷卻反應系以終止反應之方法等。 上述[B]成份之製造，可由例如飼給前述各成份，在 餾除因加熱而所生成的醇之下進行脫醇縮合反應而實施。 反應溫度較佳爲150至130 °C ，更佳爲70至110 °C，而反應 時間較佳爲1至1 5小時。此反應，爲防止（b 2)院氧基5夕垸 本身之聚縮合反應起見，較佳爲在實質上無水條件下實施 。又，此反應’爲短縮反應時間起見，亦能在（bl)含有羥 基之環氧樹脂不蒸發的範圍，在減壓下實施。 又’在進行上述脫醇縮合反應時，爲促進反應起見， 可使用在來周知之觸媒中不會使環氧乙烷環（oxirane ring) 開環者。該觸媒而言，可例舉：如鋰、鈉、鉀、、铯 、鎂、耗、鋇、總、鋅、銘、軚、姑、鍺、錫、鉛、銻、 砷、鈽、鎘、錳的金屬；此等金屬之氧化物、有機酸鹽、 鹵化物、烷氧化物等。此中，特佳爲有機錫、有機酸錫， 具體上，二丁基錫月桂酸酯、辛酸錫等。 又，上述反應亦可在溶劑中實施。溶劑祗要是能溶解 (bl)含有羥基之環氧樹脂及（b2)烷氧基矽烷，且不會與此 等反應的有機溶劑’則並不特別限定，如此的有機溶劑而 言’可例舉：二甲基甲醯胺、二甲基乙醯胺、四氫呋喃、 甲基乙基甲酮等之非質子性極性溶媒。 -20- (17) (17)200401002 適合作爲含有烷氧基之矽烷改性環氧樹脂使用的市售 品，可舉：荒川化學工業（股）製，商品名：孔甫色朗丑- 101、 E-102、 E-201、 E-202' E-211、 E-212等。 此中，荒川化學工學工業（股）製’商品名：孔甫色朗 E-20 1，E-202，E-212，由於所製得的保護膜能具有高的 表面硬度之故，較佳。 [C〗與[A]成份及[B]成份不相同的陽離子聚合性化合物 本發明中所使用的[C]與[A]成份及[B]成份不相同的 陽離子聚合性化合物而言，可例舉：在分子內具有氧雜環 丁烷基、3，4-環氧基環己基或環氧基2個以上的化合物。 如此的[C]陽離子聚合性化合物之具體例而言，可例 舉如下述者。 在分子內具有上述氧雜環丁烷基2個以上的化合物而 言，可例舉：3，7-雙（-氧雜環丁烷基）-5-氧雜-壬烷、3， -(1，3-(2-亞甲基）丙烷二基雙（甲醛）雙（3-甲基氧雜環 丁烷）、1，4-雙[(3-甲基-3-氧雜環丁烷基甲氧基）甲基]苯 、1，2-雙[(3-甲基-3-氧雜環丁烷基甲氧基）甲基]乙烷、1 ，3-雙[(3-甲基-3-氧雜環丁烷基甲氧基）甲基]丙烷、乙二 醇雙（3-甲基-3-氧雜環丁烷基甲基）醚、二環戊基雙[3-甲 基-3-氧雜環丁烷基甲基]醚、三乙二醇雙（3-甲基-3-氧雜 環丁烷基甲基）醚、四乙二醇雙（3-甲基-3-氧雜環丁烷基甲 基）醚、三環癸烷二基二亞甲基雙（3-乙基-3-氧雜環丁烷基 甲基）醚、三羥甲基丙烷參（3-甲基-3-氧雜環丁烷基甲基） -21 - (18) (18)200401002 醚、].，4-雙（3-乙基-3-氧雜環丁烷基甲氧基）丁烷、1 ’ 6_ 雙（3-乙基-3-氧雜環丁烷基甲氧基）己烷、異戊四醇參（3_ 乙基-3-氧雜環丁烷基甲基）醚、異戊四醇肆（3_乙基氧 雜環丁烷基甲基）醚、聚乙二醇雙（3 -乙基-3 —氧雜環丁院基 甲基）醚、二異戊四醇陸（3-乙基-3-氧雜環丁烷基甲基）醚 、二異戊四醇伍（3-乙基-3-氧雜環丁烷基甲基）醚、二異戊 四醇肆（3 -乙基-3 -氧雜環丁烷基甲基）醚、二異戊四醇陸 (3 -乙基-氧雜環丁烷基甲基）醚與己內酯間的反應生成物、 二異戊四醇伍（3 -乙基-3-氧雜環丁烷基甲基）醚與己內酯間 的反應生成物、雙三羥甲基丙烷肆（3-乙基-3 —氧雜環丁院 基甲基）醚、雙酚A雙（3_乙基-3-氧雜環丁烷基甲基）醚與環 氧乙烷間的反應物 '雙酚A雙（3_乙基-3-氧雜環丁院基甲 基）醚與環氧丙烷間的反應物、加氫雙酚六雙（3 —乙基-3·氧 雜環丁烷基甲基）醚與環氧乙烷間的反應生成物' 加氫雙 酚A雙（3-乙基-3-氧雜環丁烷基甲基）醚與環氧丙烷間的反 應生成物、雙酚F雙（3 -乙基-3-氧雜環丁烷基甲基）醚與環 氧乙烷間之反應生成物等。 在分子內具有3，4 -環氧基環己基2個以上的化合物而 言，可例舉：3，4 -環氧基環己基甲基-3> ’ -環氧基 環己羧酸酯、2-(3，I環氧基環己基-5，5-螺-3’ 4-環氧 基）環己烷-間二哼烷、雙（3 ’ 4-環氧基環己基甲基）己二酸 酯、雙（3，4_環氧基-6-甲基環己基甲基）己二酸酯、3’ 4-環氧基_6_甲基環己基-3，，4，-環氧基-6< -甲基環己烷 羧酸酯、亞甲基雙（3’ 4-環氧基環己烷）、二環戊二烯二 -22 ~ (19) (19)200401002 環氧化物、乙二醇之二（3，4-環氧基環己基甲基）醚、亞 甲基雙（3，4 -環氧基環己烷羧酸酯）、內酯改性3 ’ 4 -環氧 基環己基甲基-3 β ，4 / -環氧基環己烷羧酸酯等。 在分子內具有上述環氧基2個以上的化合物而言，可 例舉：如雙酚Α二縮水甘油基醚、雙酚F二縮水甘油基醚 、雙酚S二縮水甘油基醚、加氫雙酚A二縮水甘油基醚、 加氫雙酚F二縮水甘油基醚、加氫雙酚AD二縮水甘油基醚 、溴化雙酚A二縮水甘油基醚、溴化雙酚F二縮水甘油基 醚、溴化雙酚S二縮水甘油基醚的各種雙酚化合物之二縮 水甘油基醚類； 如1，4 -丁二醇二縮水甘油基醚、1，6 -己二醇二縮水 甘油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘 油基醚、聚乙二醇二縮水甘油基醚、聚丙二醇二縮水甘油 基醚的多元醇之聚縮水甘油基醚類； 可由對乙二醇、丙二醇、甘油等之脂肪族多元醇中附 加1種或2種以上之環氧化物而製得的聚醚聚醇之聚縮水甘 油基醚類； 酚淸漆型環氧樹脂； 甲酚淸漆型環氧樹脂； 聚酚型環氧樹脂； 脂肪族長鏈二元酸之二縮水甘油基醚類； 咼級脂肪酸之縮水甘油基酯類； 環氧化大豆油、環氧化亞麻仁油等。 具有上述環氧基2個以上的化合物之市售品而言’可 -23- (20) (20)200401002 例舉··作爲雙酚A型環氧樹脂之埃比可將1〇〇1、同1〇〇2、 同 1003、同 1004、同 1007、同 1〇〇9、同 1〇1〇、同 828(以上 均爲油化雪爾愛博克斯（股）製）等； 作爲雙酚F型環氧樹脂之埃比可將8 〇 7 (油化雪爾愛博 克斯（股）製）等； 作爲酚淸漆型環氧樹脂之埃比可特152、同154、同 15 7S65(以上均爲油化雪爾愛博克斯（股）製）、EPPN201、 同202(以上均爲日本化藥（股）製）； 作爲甲酚淸漆型環氧樹脂之EOCN102、同103S、同 104S ' 1020、1025、1027(以上均爲日本化藥（股）製），埃 比可特180S75(油化雪爾愛博克斯（股）製）等； 作爲聚酚型環氧樹脂之埃比可特1032H60、同XY-4000(以上均爲油化雪爾愛博克斯（股）製）等； 作爲環狀脂肪族環氧樹脂之CY-175、同177、同179 、阿拉爾代特CY-182、同192、同184(以上奇巴.特殊化 學品（股）製），ERL-4234、同 4299、同 4221' 同 4206(以上 均爲U.C.C.社製）、蕭代茵596(昭和電工（股）製）、埃比科 隆200、同400(以上，大日本油墨（股）製、埃比可特871、 同872(以上均爲油化雪爾愛博克斯（股）製）、EP-5661、同 5662(以上，色拉尼斯塗覆（股）製）等； 作爲脂肪族聚縮水甘油基醚之埃博萊特100MF(共榮 社化學（股）製），埃比歐爾TMP(日本油脂（股）製）等。 上述之陽離子聚合性化合物’可以單獨1種，或組合2 種以上使用。 -24- (21) (21)200401002 此等[c ]陽離子聚合性化合物之中，較佳者可舉：酚 淸漆型環氧樹脂、聚酚型環氧樹脂。 [D ]固化劑 在本發明之組成物中所使用的[D ]固化劑而言，可例 舉：多元羧酸、多元羧酸酐，以及不飽和多元羧酸酐與烯 烴系不飽和化合物間之共聚物。 上述多元羧酸而言，較佳爲脂肪酸多元羧酸、脂環族 φ 多元羧酸以及芳香族多元羧酸。可例舉：如琥珀酸、戊二 酸、己二酸、丁烷四羧酸、馬來酸、衣康酸之脂肪族多元 羧酸；如六氫酞酸、1 ’ 2-環己烷二羧酸、1，2，4_環己烷 三羧酸、環戊烷四羧酸之脂環族多元羧酸；酞酸、異酞酸 、對酞酸、偏苯三甲酸、均苯四甲酸、1，2，5，8 -萘四 羧酸之芳香族多元羧酸。此中，從固化性組成物之反應性 ，所形成的固化膜之耐熱性等之觀點來看，特佳爲芳香族 多元羧酸。 _ 上述多元羧酸酐而言，較佳爲脂肪族二羧酸酐、脂環 族多元羧酸二酐、芳香族多元羧酸酐及含有酯之酸酐。可 例舉：如衣康酸酐、琥珀酸酐、檸康酸酐、十二碳烯琥珀 酸酐、均丙三甲酸酐、馬來酸酐 '六氫酞酸酐、甲基四氫 酞酸酐、海明酸酐之脂肪族二羧酸酐，如1 ’ 2 ’ 3 ’ 4 - 丁 烷四羧酸酐、環戊烷四羧酸二酐之脂環族多元羧酸二酐； 如酞酸酐、均苯四甲酸酐 '偏苯三甲酸酐、二苯基酮四羧 酸酐之芳香族多元羧酸酐；如乙二醇雙偏苯三甲酸醋酐、 -25- (22) (22)200401002 甘油參偏苯三甲酸酯酐之含有酯之酸酐。此中，由於芳香 族多元羧酸酐，尤其是偏苯三甲酸酐可製得耐熱性較高的 固化膜之故，特佳。 爲合成上述不飽和多元羧酸酐與烯烴系不飽和化合物 的共聚物所使用的不飽和多元羧酸酐而言，可例舉：如衣 康酸酐 '檸康酸酐、馬來酸酐、順式1，2，3，4-四氫酞 酸酐之不飽和多元羧酸酐之至少1種以上。 又，爲合成不飽和多元羧酸酐與烯烴系不飽和化合物 的共聚物所使用的烯烴系不飽和化合物而言，可例舉：如 苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯、甲基甲基丙烯 酸酯、第三丁基甲基丙烯酸酯、甲基丙烯酸三環 [5.2.1.02 = 6]癸烷-8-基酯、2-甲基環己基丙烯酸酯、苯基馬 來醯亞胺、環己基馬來醯亞胺之烯烴系不飽和化合物之至 少1種以上。 對不飽和多元羧酸酐與烯烴系不飽和化合物的共聚物 每100重量份之不飽和多元羧酸酐之共聚比例’較佳爲1至 80重量份，更佳爲1〇至60重量份。由於使用如此的共聚物 ，即可製得平坦化性優異的保護膜。 不飽和多元羧酸酐與烯烴系不飽和化合物的共聚物之 較佳例而言，可舉：無水馬來酸共聚物/苯乙烯、檸康酸 酐/甲基丙烯酸三環[5.2.1 ·02’6]癸烷-8-基酯共聚物等。 又，上述不飽和多元羧酸酐與烯烴系不飽和化合物的 共聚物之聚苯乙烯換算重量平均分子量’較佳爲500至 50,000，更佳爲500至1〇,000。由於使用如此分子量範圍 -26- (23) (23)200401002 之共聚物’即可製得平坦化性優異的保護膜。 共聚物[E] 本發明中所使用的共聚物[E ]，係（e 1)不飽和羧酸酐及 /或不飽和羧酸酐，（e 2)含有環氧基之不飽和化合物’以及 (e3)與（el)成份和（e2)成份不相同的烯烴系不飽和化合物 之共聚物。 共聚物[E]，對共聚物[E]每100重量份，含有從化合 物（e 1)所衍生的組成單元，較佳爲5至4 0重量份，特佳爲 10至30重量份。在此組成單元在5重量份以下的共聚物有 耐熱性、抗藥品性、表面硬度會降低的傾向，另一方面， 在組成單元超過40重量份的共聚物，則儲存安定性可能會 低落。 上述（e 1 )不飽和羧酸及/或不飽和羧酸酐而言，可例舉 :丙烯酸、甲基丙烯酸、巴豆酸等之單羧酸；馬來酸、富 馬酸、檸康酸、中康酸、衣康酸等之二羧酸；以及此等二 羧酸之無水物。此中，由於共聚反應性、耐熱性以及容易 取得，較佳爲使用丙烯酸、甲基丙烯酸、馬來酸酐等。此 等化合物（e 1)’可以單獨或組合使用。 共聚物[E]，對共聚物[E]每100重量份，含有從化合 物（e 2)所衍生的組成單兀，較佳爲1 0至7 0重量份，特佳爲 20至60重量份。如此組成單元在1〇重量份以下時，則所得 的保護膜有耐熱性’表面硬度會降低的傾向’而另一方面 ，如超過7 0重量份時’則有含有如此共聚物的組成物之儲 -27- (24) (24)200401002 存安定性會低落的傾向。 (e2)含有環氧基之不飽和化合物而言，可使用與作爲 前述共聚物[A]所用的化合物（al)所例示者同樣者。 共聚物[E]，對共聚物[E]每1〇〇重量份，含有從化合 物（e3)所衍生的組成單元，較佳爲1〇至70重量份，特佳爲 2 0至5 0重量份。如此組成單元在1 0重量份以下時，則含有 此共聚物的組成物之儲存安定性會降低的傾向，而另一方 面，如超過70重量份時，則有所得的保護膜之耐熱性、表 面硬度會降低的傾向。 (e3)除（el)及（e2)以外之烯烴系不飽和化合物，可使 用與作爲前述共聚物[A]所用的化合物（a2)所例示者相同 者。 本發明所使用的共聚物[E]之具體例而言，可例舉： 苯乙烯/甲基丙烯酸三環[5.2.1.02’6]癸烷-8-基酯/甲基 丙烯酸縮水甘油酯共聚物， 苯乙烯/丙烯酸/丙烯酸三環[5.2.1.02’6]癸烷-8-基酯/丙 烯酸縮水甘油酯共聚物， 苯乙烯/甲基丙烯酸/苯基馬來醯亞胺/甲基丙烯酸縮水 甘油酯共聚物， 苯乙烯/丙烯酸/苯基馬來醯亞胺/丙烯酸縮水甘油酯共 聚物， 苯乙烯/甲基丙烯酸/環己基馬來醯亞胺/甲基丙烯酸縮 水甘油酯共聚物， 丁二烯/苯乙烯/甲基丙烯酸/甲基丙烯酸三環 -28- (25) (25)200401002 [5.2.1 ·〇2’6]癸烷-8-基酯/甲基丙烯酸縮水甘油酯共聚物， 丁二烯/甲基丙烯酸/甲基丙烯酸三環[5.2.1.02’6]癸院. 8 -基酯/甲基丙烯酸縮水甘油酯共聚物， 苯乙烯/甲基丙烯酸三環[5.2.1.02’6]癸烷-8-基酯/甲基 丙烯酸-6，7-環氧基庚基酯共聚物。 苯乙烯/丙烯酸/馬來酸酐/甲基丙烯酸-6，7-環氧基庚 基酯共聚物， 第三丁基甲基丙烯酸酯/丙烯酸/馬來酸酐/甲基丙烯酸 酯-6，7-環氧基庚基共聚物， 苯乙烯/甲基丙烯酸/甲基丙烯酸甲酯/甲基丙烯酸縮水 甘油酯共聚物， 對甲氧基苯乙烯/甲基丙烯酸/環己基丙烯酸酯/甲基丙 烯酸縮水甘油酯共聚物等。 其中較佳者可舉：苯乙烯/甲基丙烯酸/甲基丙烯酸三 環[5.2.1.02’6]癸烷-8-基酯/甲基丙烯酸縮水甘油酯共聚物 苯乙烯/甲基丙烯酸/苯基馬來醯亞胺/甲基丙烯酸縮水 甘油酯共聚物， 苯乙烯/甲基丙烯酸/環己基馬來醯亞胺/甲基丙烯酸縮 水甘油酯共聚物、丁二烯/苯乙烯/甲基丙烯酸/甲基丙烯酸 三環[5.2.1.02’6]癸烷-8·基酯/甲基丙烯酸縮水甘油酯共聚 物， 丁二烯/甲基丙烯酸/甲基丙烯酸三環[5.2.l.o2,6]癸烷· 8-基酯/甲基丙烯酸縮水甘油酯共聚物。 -29- (26) (26)200401002 共聚物[E]，係聚苯乙烯換算重量平均分子量在較佳 爲 3,000 至 1〇〇,〇〇〇，更佳爲 3,000 至 50,〇〇〇’ 特佳爲 3,000 至2 0,000。使用持有此範圍之分子量的共聚物’則可製^ 平坦化性優異的保護膜。 共聚物[E]，可在適當的溶媒及聚合起始劑之存在下 ，將上述（el)不飽和羧酸及/或不飽和羧酸酐’（e2)含有環 氧基之不飽和化合物，以及（e3)與（el)成份和（e2)成份不 相同的烯烴系不飽和化合物，藉由例如自由基聚合而合成 〇 可使用爲共聚物[E]之合成的溶媒及聚合起始劑而言 ，可使用與作爲前述之共聚物[A ]之製造時所使用的溶媒 及聚合起始劑所例示者相同者。 [F]與[B]成份和[E]成份不相同的陽離子聚合性化合物 本發明中所使用的[F]與[B]成份和[E]成份不相同的陽 離子聚合性化合物而言，可使用與作爲前述之[C]成份所 舉者相同者。 [G]因熱及/或放射線而將產生酸的化合物 本發明中所使用的[G ]成份，係放射線引發酸產生劑 或熱引發酸產生劑。 放射線引發酸產生劑而言，可例舉：二芳基碘鐵鹽類 、三芳基銃鹽類、二芳基鱗鹽類等，並且很適用。又，熱 引發酸產生劑而言，可例舉：锍鹽類（前述之三芳基锍鹽 -30- (27) (27)200401002 類則除外），苯并噻唑鎰鹽類、銨鹽類、銹鹽類等，此中 ，銃鹽類（前述之三芳基銃鹽類則除外）、苯并噻唑鏺很適 用。 上述二芳基碘鏺鹽類而言，可例舉：二苯基碘鎰四氟 硼酸鹽、二苯基碘鏺六氟磷酸鹽、二苯基碘鎗六氟砷酸鹽 、二苯基碘鏺三氟甲烷磺酸鹽、二苯基碘鏡三氟乙酸鹽、 二苯基對甲苯磺酸鹽、4-甲氧基苯基苯基碘鐵四氟硼酸鹽 、4 -甲氧基苯基苯基碘鏺六氟磺酸鹽、4 -甲氧基苯基苯基 φ 碘鐵六氟砷酸鹽、4 -甲氧基苯基苯基碘鏺三氟甲烷磺酸鹽 、4-甲氧基苯基苯基碘鏠三氟乙酸鹽、4-甲氧基苯基苯基 碘鏺三氟乙酸鹽、4 -甲氧基苯基苯基碘鏺對甲苯磺酸鹽、 雙（4-第三丁基苯基）碘鐵四氟硼酸鹽、雙（4-第三丁基苯基 )碘鎗六氟砷酸鹽、雙（4-第三丁基苯基）碘鏺三氟甲烷磺酸 鹽、雙（4-第三丁基苯基）碘鐺三氟乙酸鹽、雙（4-第三丁基 苯基）碘鏺對甲苯磺酸鹽等。此中，二苯基碘鏺六氟磺酸 鹽很適用。 _ 上述三芳基銃鹽類而言，可例舉：三苯基銃四氟硼酸 鹽、三苯基銃六氟磷酸鹽、三苯基銃六氟砷酸鹽、三苯基 毓三氟甲烷磺酸鹽、三苯基銃三氟乙酸鹽、三苯基銃對甲 苯磺酸鹽、4-甲氧苯基二苯基銃四氟硼酸鹽、4-甲氧基苯 基二苯基銃六氟磷酸鹽、4-甲氧基苯基二苯基銃六氟砷酸 鹽、4 -甲氧基苯基二苯基銃三氟甲烷磺酸鹽、4 -甲氧基苯 基二苯基銃三氟乙酸鹽、4 -甲氧基苯基二苯基銃對甲苯磺 酸鹽、4-苯基苯硫基二苯基四氟硼酸鹽、4-苯基苯硫基二 -31 - (28) (28)200401002 苯基六氟磷酸鹽、4-苯基苯硫基二苯基六氟砷酸鹽、4-苯 ~ 基苯硫基二苯基三氟甲烷磺酸鹽、4-苯基苯硫基二苯基三 -氟乙酸鹽、4-苯基苯硫基二苯基對甲苯磺酸鹽等。此中， 三苯基銃三氟甲烷磺酸鹽很適用。 上述二芳基鱗鹽類而言，可舉：（1-6-77 -茴香素）（？？ -環戊二烯基）鐵六氟磷酸鹽等。 作爲引發放射線酸發生劑很適用的酸產生劑而言，可 舉：作爲二芳基碘鎗鹽類之聯合碳化鈣社製，商品名： 鲁 UVI-6950 ' UVI-6970、UVI-6974、UVI-6990、綠色化學（ 股）製，商品名：MPI-103' BBI-103等。 又，作爲三芳基锍鹽類，可舉：旭電化工業（股）製， 商品名：阿德卡歐布多瑪SP-150、SP-151、SP-170、SP-171、日本曹達（股）製，商品名：（：1-248 1、<：1-2624、（：1-263 9、CI-20 64、綠色化學（股）製，商品名：DTS-102、 DTS-103 ' NAT-103、NDS-103、TPS-103、MDS-103、莎 多瑪社製，商品名：CD-1010、CD-1011、CD-1012 等。 · 又，作爲二芳基錢鹽類而言，可舉：奇巴特殊化學品 (股）製，商品名：伊爾加求亞261，日本化藥（股）製，商品 名：PCI-061T、PCI-062T、PCI-020T、PCI-022T等。 此中，聯合碳化鈣社製，商品名：UVI-6970、UVI-6974、UVI-6990、旭電化工業（股）製，商品名··阿德卡歐 布多瑪SP-170、SP-171、莎多瑪社製，商品名：CD-1012 、綠色化學（股）製，商品名：MPI-103，由於所得的保護 膜具有高的表面硬度之故，較佳。 -32- (29) (29)200401002 上述熱引發酸產生劑之中，銃鹽類（前述之三芳基銃 鹽類則除外）之具體例而言，可舉：4 -乙醯氧基苯基二甲 基銃六氟銻酸鹽、4 -乙醯氧基苯基二甲基銃六氟砷酸鹽、 二甲基-4-(苄氧基羰氧基）苯基銃六氟銻酸鹽、二甲基_4 —( 苯醯氧基）苯基锍六氟銻酸鹽、二甲基- 4- (苯醯氧基）苯基 銃六氟砷酸鹽、二甲基-3-氯代-4-乙醯氧基苯基毓六氟銻 酸鹽等之烷基銃鹽； 苄基-4-羥基苯基甲基銃六氟銻酸鹽、苄基-4-羥基苯 基甲基銃六氟磷酸鹽、4-乙醯氧基苯基苄基甲基銃六氟銻 酸鹽、苄基-4-甲氧基苯基甲基銃六氟銻酸鹽、苄基-2-甲 基-4-羥基苯基甲基銃六氟銻酸鹽、苄基-3-氯代-4-羥基苯 基甲基銃六氟砷酸鹽、4-甲氧基苄基-4-羥基苯基甲基銃 六氟磷酸鹽等之苄基銃鹽； 二苄基-4-羥基苯基銃六氟銻酸鹽、二苄基-4-羥基苯 基銃六氟磷酸鹽、4-乙醯氧基苯基二苄基銃六氟銻酸鹽、 二苄基-4-甲氧基苯基鏑六氟銻酸鹽、二苄基-3-氯代-4-羥 基苯基銃六氟砷酸鹽、二苄基-3-甲基-4 -羥基-5 -第三丁基 苯基銃六氟銻酸鹽、苄基-4-甲氧基苄基-4-羥基苯基銃六 氟磷酸鹽等之二苄基銃鹽； 對氯代苄基-4-羥基苯基甲基銃六氟銻酸鹽、對硝基 苄基-4-羥基苯基甲基銃六氟銻酸鹽、對氯代苄基-4-羥基 苯基甲基銃六氟磷酸鹽、對硝基苄基-3-甲基-4-羥基苯基 甲基銃六氟銻酸鹽、3，5-二氯代苄基-4-羥基苯基甲基銃 六氟銻酸鹽、鄰氯代苄基-3-氯代-4-羥基苯基甲基銃六氟 -33- (30) (30)200401002 銻酸鹽等之取代苄基銃鹽等。 此中較適用者爲：4-乙醯氧基苯基二甲基毓六氟砷酸 鹽、苄基-4-羥基苯基甲基锍六氟銻酸鹽、4-乙醯氧基苯 基苄基甲基銃六氟銻酸鹽、二苄基-4-羥基苯基銃六氟鋪 酸鹽、乙醯氧基苯基二苄基鏑六氟銻酸鹽等。 上述苯并噻唑鐵鹽類而言，可例舉：3 -苄基苯并噻哩 鑰六氟銻酸鹽、3 -苄基苯并噻唑鐵六氟磷酸鹽、3- +基苯 并噻唑鎗四氟硼酸鹽、3-(對甲氧基苄基）苯并噻唑鏺六氟 銻酸鹽' 3 -苄基-2-甲硫基苯并噻唑鎗六氟銻酸鹽、3_卡 基-5 -氯代苯并噻唑鎗六氟銻酸鹽等之苄基苯并噻唑鎗鹽 〇 此中，3 -苄基苯并噻哇鎰六氟銻酸鹽等較適用。 作爲熱引發酸產生劑很適用的酸產生劑，例如作爲烷 基毓鹽，可取得：旭電化工業（股）製，商品名：阿德卡歐 布頓cp-66、cp-77等之市售品。 又，作爲苄基疏鹽，可舉：三新化學工業（股）製，商 品名：SI-60、 SI-80、 SI-100、 SI-110、 SI-145、 SI-150、 SI-80L、SI-100L、SI-110L。 此中，由於所得的保護膜具有筒的表面硬度之故’較 佳爲 SI-80、 si-100、 SI-110。 組成物 其次，就本發明之組成物加以說明。 本發明之組成物可由將各成份較佳爲均勻溶解或分散 -34- (31) 200401002 在後述的適當的溶媒中而調製。 本發明之組成物之實施狀態，可舉如下之各種情形。 ① 以前述之共聚物[A]、[B]以及[C]成份爲必須成份 ，而視情況，含有後述的任意添加成份的組成物（以下， 簡稱「第1組成物」。）。 ② 除上述第1組成物之各成份之外，尙含有[D]固化劑 的組成物。 ③ 以共聚物[E]、[B]成份以及[F]成份爲必須成份，而 視情況，含有後述的任意添加成份的組成物（以下，簡稱 「第2組成物」。）。 ④ 除上述第2組成物之各成份之外，尙含有「G」成 份的組成物（以下，簡稱「第3組成物。」。） 第1組成物中的各成份之調配比例，係如下之方式者 〇 [B]成份，係按對共聚物[A]100重量份，較佳爲3至 2〇〇重量份，更佳爲5至100重量份，特佳爲10至50重量份 之量使用。如此値在3重量份以下，則所得的保護膜之硬 度可能會不足，而另一方面，如此値超過200重量份，則 在塗膜之形成過程中可能會產生困難。 第1組成物中所含有的[C]成份，係按對共聚物[A] 100 重量份較佳爲3至100重量份，更佳爲5至50重量份之量使 用。如在此範圍之使用量使用，則可製得具有足夠強度的 保護膜 上述第1組成物，係長期安定性優異者。 -35- (32) (32)200401002 上述第1組成物，係在使用時再添加[D]固化劑之後， 可依後述的方法形成保護膜。如此方式所形成的保護膜， 除能滿足密貼性、表面硬度、透明性、耐熱性、耐光性、 抗溶劑性等的要求之外，在施加有熱的狀態下仍不會因荷 重而凹陷且優於使底子基板上所形成的濾色器之高低差平 坦化的性能。 可在第1組成物中再添加的[D ]固化劑，較佳爲在經溶 解在適當的溶媒中的狀態下使用。溶液中之[D ]固化劑之 濃度較佳爲5至50重量％，更佳爲10至40重量％。在此可 使用的溶媒，係可使用與作爲在前述之共聚物[B]之製造 中使用的溶媒所例示者相同者。固化劑之添加量，係對共 聚物[A]每100重量％，較佳爲20至60重量份’更佳爲20至 50重量份。如在此範圍之使用量使用，則組成物可顯示良 好的固化特性，而不致於影響所得的保護膜之各種物性。 在第1組成物中再添加有[D]固化劑的組成物’較佳爲 通常在2 4小時以內供給使用。 上述第2組成物中的各成份之調配比例’係如下所示 〇 [B]成份’係按對共聚物[E] 100重量份’較佳爲3至 300重量份，更佳爲5至1〇〇重量份’特佳爲1〇至50重量份 之量使用。如此値在3重量份以下’則所得的保護膜之硬 度可能會不足，而另一方面’如此値超過2 5 0重量份，則 在塗膜之形成過程中可能會發生困難。 第2組成物中所含有的[F]成份’係按對共聚物[E] 100 -36- (33) (33)200401002 重量份，較佳爲3至100重量份’更佳爲5至50重量份之量 使用。如在此範圍之使用量使用，則可製得足夠硬度之保 護膜。 上述第2組成物中可再含有[G]因熱及/或放射線而將 產生酸的化合物以作成第3組成物。 第3組成物中所含有的[G ]成份之量’係對共聚物[E ] 每100重量份，較佳爲20重量份以下，更佳爲〇.〇5至20重 量份，特佳爲0.1至1 〇重量份。如在此圍之使用量使用 ，則組成物可顯示良好的固化特性，而不致於影響所得的 保護膜之各種物性。 上述第2或第3組成物，可依後述的方法形成保護膜。 如此方式所形成的保護膜除能滿足密貼性、表面硬度、透 明性、耐熱性、耐光性、抗溶劑性等的要求之外，在施加 有熱的狀態下仍不會因荷重而凹陷且優於使底子基板上所 形成的濾色器之高低差平坦化的性能。 任意添加成份 本發明之組成物可爲上述的種種狀態，惟視需要，不 影響本發明之目的之範圍內可含有上述以外之其他成份。 如此的其他成份而言，可例舉：表面活化劑、粘接助劑等 〇 上述表面活化劑’係爲提升組成物之塗佈性而所添加 者。 如此的表面活性劑而言’可例舉：氟系表面活性劑； -37- (34) (34)200401002 矽酮系表面活性劑；聚環氧乙烷烷基醚類、聚環氧乙烯芳 基醚類、聚環氧乙烷二烷基酯類等之非離子系表面活性劑 等。 聚環氧乙烷烷基醚類而言，可例舉：聚環氧乙烷月桂 基醚、聚環氧乙烷硬脂基醚、聚環氧乙烷油烯基醚等。聚 環氧乙烷芳基醚類而言，可例舉：聚環氧乙烷辛基苯基醚 '聚環氧乙烷壬基苯基醚。又，聚環氧乙烷二烷基酯類而 言，可例舉：聚環氧乙烷二月桂酸酯、聚環氧乙烷二硬脂 酸酯等。 如此的表面活性劑，例如可以氟系表面活性劑而取得 :BMCHIMIE社製，商品名：BM- 1000、BM-1100、大日本 油墨化學工業（股）社製，商品名：墨加滑克F142D、同 F172、同F173、同F-183、住友蘇利埃姆（股）社製，商品名 :浮樂拉土FC-135、同 FC-170C、同 FC-430、同 FC-431、 旭硝子（股）社製，商品名：撒弗隆s -1 1 2、同S -1 13、同S -131 、同 S-141 、同 S-145 、同 S-382 、同 SC-101 、同 SC-102 、同 SC-103、同 SC-104、同 SC-105、同 SC-106等； 可以矽酮系表面活性劑而取得：東麗矽酮（股）社製， 商品名：SH-28PA、SH-190、SH-193、SZ-603 2、SF-8428 、DC-5 7、DC-190，信越化學工業（股）社製，商品名： KP341，新秋田化成（股）社製，商品名：埃佛特補EF301、 同 EF303 ' 石 EF352等； 可以其他表面活性劑而取得：共榮社化學（股）社製 ，商品名：（甲基）丙烯酸系共聚物坡里佛羅NO.57、同 (35) (35)200401002 NO. 9 0等之市售品。 此等表面活性劑之添加量，在對上述第1組成物添加 時’係對共聚物[A ]每1 0 0重量份，或在對上述第2組成物 添加時’則對共聚物[E]每1 00重量份，按較佳爲5重量份 以下’更佳爲2重量份以下使用。如表面活性劑之量超過5 重量份時，可能在塗佈過程中容易發生塗膜之膜粗糙化。 上述粘接助劑，係爲提升所形成的保護膜與基板間的 密貼性而添加者。 如此的粘接助劑而言，可例舉：羧基、甲基丙烯醯基 、異氰酸酯基、環氧基等之反應性取代基的官能基矽烷偶 合劑很適用。具體而言，可舉：三甲氧基甲矽烷基安息香 酸、τ -甲基丙烯醯氧丙基三甲氧基矽烷、乙烯基三乙醯 氧基矽烷、乙烯基三甲氧基矽烷、r-異氰酸酯丙基三乙 氧基砂院、7·縮水甘油興基丙基二由氧基砂院、-(3， 4-環氧基環己基）乙基三甲氧基矽烷等。 如此的粘接助劑’在對上述第1組成物添加時，係對 共聚物[A ]每1 〇 〇重量份’或在對上述第2組成物添加時， 則對共聚物[E]每100重量份’按較佳爲30重量份以下，更 佳爲25重量部以下之量使用。如粘接助劑超過30重量份時 ，可能所得的保護膜之耐熱性會成爲不足的情形。 溶媒 本發明之組成物，可由將各成份均勻溶解或分散在較 佳爲適當的溶媒中而調製。可使用的溶媒，係使用能溶解 -39- (36) (36)200401002 或分散組成物之各成份，而不會與各成份反應者。 如此的溶媒，可使用與作爲在製造前述之共聚物[A] 時所使用的溶媒而例示者相同者。溶媒之使用量，係本發 明之組成物每1 0 0重量份之全固體成份之含量能成爲較佳 爲1至50重量份，更佳爲5至40重量份的量。 又，可與前述之溶媒一起，倂用高沸點溶媒，可倂用 的高沸點溶媒而言，可例舉：N-甲基甲醯胺、N，N-二甲 基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺' N，N-二甲 基乙醯胺、N-甲基吡咯烷酮、二甲基亞硕、苄基乙醚、二 己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、 1 -壬醇、苄醇、乙酸苄酯、安息香酸乙酯、草酸二乙酯、 馬來酸二乙酯、r-丁內酯、碳酸乙烯酯、碳酸丙烯酯、 苯基溶纖素乙酸酯等。 倂用高沸點溶媒時之使用量，係對全溶媒量100重量 份，較佳爲90重量份以下，更佳爲80重量份以下。 如上述方式所調製的組成物，亦可在使用較佳爲孔徑 0.2至3.0 μιη，更佳爲孔徑0.2至0.5 μιη程度之米利波亞過 濾器（Millipore filter)加以濾別後，供爲使用。 保護膜之形成 其次，就使用本發明之組成物以形成本發明之保護膜 的方法加以說明。 如本發明之組成物係上述第1組成物，第2組成物或作 爲[G]成份而含有熱引發酸產生劑的第3組成物時，則將該 -40- (37) (37)200401002 組成物塗佈在基板表面，藉由預焙（prebake)以去除溶媒並 作成塗膜後，加以加熱處理即可形成作爲目的之保護膜。 可作爲上述基板而使用者，有例如玻璃、石英、矽、 樹脂等之基板。樹脂而言，可例舉：如聚對苯二甲酸乙二 醇酯、聚對苯二甲酸丁二醇酯、聚醚硕、聚碳酸酯、聚醯 亞胺、以及環狀烯烴之開環聚合物和其氫添加物的樹脂。 塗佈方法而言，可採用例如噴霧法、輥塗法、旋轉塗 佈法、鑲條塗佈法、噴墨法等適當方法。 上述預焙之條件而言，視各成份之種類或調配比例而 有所不同，惟可採用例如在7 0至9 0 °C下1至1 5分間程度之 條件。 塗膜形成後之加熱處理，可使用加熱板或烤爐等適當 的加熱裝置實施。處理溫度較佳爲1 5 0至2 5 0 r程度，如作 爲加熱裝置而使用加熱板時較佳爲採用5至30分鐘，使用 烤爐時則較佳爲採用30至90分鐘之處理時間。 另一方面，如本發明之組成物係作爲[G ]成份而含有 放射線引發酸產生劑的第3組成物時，則將該組成物塗佈 在基板表面上並藉由預焙以去除溶媒並作成塗膜之後，實 施放射線照射處光（曝光處理），即可形成作爲目的物之保 護膜。需要時，亦可再在曝光處理後實施加熱處理。 此時’與上述同樣方式在基板上形成塗膜。 在上述放射線之照射處理時可使用的放射線而言，可 例舉：可視光線' 紫外線、遠紫外線、電子線、X光線等 。此中’特佳爲含有190至450nm之波長之光的紫外線。 -41 - (38) (38)200401002 曝光量較佳爲100至20,00(H/m2，更佳爲ι〇0至 1 0,000J/m2，特佳爲 100至 5,000J/m2，。 如此方式所形成的保護膜之膜厚，較佳爲0.1至8 μηι ，更佳爲0.1至6 μ m，特佳爲0 · 1至4 μ m。在此，如本發明之 保護膜將形成在具有濾色器之局低差的基板上時，則上述 膜厚，係指從濾色器之最上部的厚度之意。 本發明之保護膜，如下述實施例即可明瞭，除能滿足 密貼性、表面硬度、透明性、耐熱性、耐光性、抗溶劑性 等的要求之外，在施加有熱的狀態下仍不會因荷重而凹陷 ，並且可適用爲使底子基板上所形成的濾色器之高低差平 坦化的性能優異的光學裝置用保護膜。 【實施方式】 以下，將記述合成例、實施例以更具體說明本發明， 惟本發明並不被下述之實施例所限定。 共聚物[A ]之製造 以下’將本發明中所使用的共聚物[A ]之製造例記述 在合成例1及2。 合成例1 在具備有冷卻管、攪拌機的燒瓶中飼裝2，2 -—偶氮 二異丁腈ό重量份、2 ’ 4-二苯基甲基-卜戊烯6重量份以 及丙二醇一甲醚乙酸酯200重量份。接著，飼裝縮水甘油 -42 - (39) (39)200401002 基甲基丙烯酸酯80重量份及苯乙烯20重量份並進行氮氣置 換後，緩慢開始攪拌。使溶液溫度上升至，並保持此 ~ 溫度4小時，製得含有共聚物（A-1)的聚合物溶液。所得的 聚合物溶液之固體成份濃度爲33.0重量％。又，共聚物（A-1)之重量平均分子量（Mw)爲8,00 0。 合成例2 在具備有冷卻管、攪拌機的燒瓶中飼裝2，2 > -偶氮 φ 二異丁腈6重量份、2，4-二苯基-4-甲基-1-戊烯1〇.〇重量份 以及丙二醇一甲醚乙酸酯200重量份。接著，飼裝縮水甘 油基甲基丙烯酸酯50重量份及甲基丙烯酸三環[5.2.1.02,6] 癸烷-8-基酯50重量份並進行氮氣置換後，緩慢開始攪拌 。使溶液溫度上升至95 °C，並保持此溫度4小時，製得含 有共聚物（A - 2)的聚合物溶液。所得的聚合物溶液之固體 成份濃度爲33.0重量％。又，共聚物（A-2)之重量平均分子 量（Mw)爲 6,000。 泰 共聚物[E]之製造 以下’將本發明中所使用的共聚物[E]之製造例記述 在合成例3及4。 合成例3 在具備有冷卻管、攪拌機的燒瓶中飼裝2，2 —-偶氮 (2，4 -二甲基戊腈）5重量份、二乙二醇甲基乙基醚2〇〇重量 -43 · (40) (40)200401002 份。接著，飼裝苯乙烯25重量份，甲基丙烯酸20重量份’ 甲基丙烯酸縮水甘油酯45重量份以及甲基丙烯酸三環 [5.2.1.02·6]癸烷-8-基酯10重量份並進行氮氣置換後，緩慢 開始攪拌。使溶液溫度上升至7 0 °C，並保持此溫度5小時 ，製得含有共聚物（E-1)的聚合物溶液。所得的聚合物溶 液之固體成份濃度爲33.0重量％。又，共聚物（E-1)之重量 平均分子量（Mw)爲6,000。 合成例4 在具備有冷卻管、攪拌機的燒瓶中飼裝2，2 z -偶氮 (2，4-二甲基戊腈）5重量份、二乙二醇甲基乙基醚200重量 份。接著，飼裝苯乙烯18重量份，甲基丙烯酸20重量份， 甲基丙烯酸縮水甘油酯40重量份以及環己基馬來醯亞胺22 重量份並進行氮氣置換後，緩慢開始攪拌。使溶液溫度上 升至70°C，並保持此溫度5小時，製得含有共聚物（E-2)的 聚合物溶液。所得的聚合物溶液之固體成份濃度爲3 3.0重 量％。又’共聚物（E-2)之重量平均分子量（Mw)爲1 2,000。 第1組成物之調製及評估 實施例1 在上述合成例1所得的含有聚合物（A -1)的溶液（相當於 共聚物（A-l)lOO重量份（固體成份）的量）中，添加作爲[b]成 份之「孔甫色朗E-202」（商品名，荒川光學工業（股）製 )20.0重量份’作爲[C]成份之雙酚A淸漆型環氧樹脂「埃比 -44 - (41) (41)200401002 可特157s65」（商品名，油化雪爾愛博克斯（股）製10.0重量 份，作爲粘接助劑之r -縮水甘油氧丙基三甲氧基矽烷1 5 重量份，以及作爲表面活性劑之SH28PA(東麗矽嗣（股）製 0.1重量份，再按固體成份能成爲20%之方式添加丙二醇一 甲基醚乙酸酯後，使用孔徑0.5 μιη之米利波亞過濾器過濾 以調製第1組成物。 保護膜之形成 對上述方式所調製的組成物中，添加作爲[D]成份而 將偏苯三甲酸酐35重量份溶解在乙二醇甲基乙基醚65重量 份中者，以調製保護膜形成用組成物。在此所調製的組成 份係無色透明者。 使用旋塗機將上述組成物塗佈在S1 Ch浸漬玻璃基板上 後，在加熱板上在8 0 °C下預焙5分鐘以形成塗膜，再在烤 爐中在230°C下加熱處理60分鐘以形成膜厚2.0μιη之保護膜 保護膜之評估 ①透明性之評估 訧具有如上述方式所形成的保護膜的基板，使用分光 光度計（1 50-20型雙射束（日立製作所（股）製））以測定4〇〇至 800nm之穿透率。表1中表示400至800nm之穿透率之最小値 。如此値在9 5 %以上時’即可認爲該保護膜之透明性良好 -45- (42) (42)200401002 ② 耐熱尺寸安定性之評估 就具有如上述方式所形成的保護膜的基板，在烤爐中 在25 0。(：下加熱1小時’並測定加熱前後之膜厚。表1中表 示彳衣下述式所算出的耐熱尺寸安定性。如此値在9 5 %以上 時’即可認爲耐熱尺寸安定性良好。 耐熱尺寸安定性=(加熱後之膜厚）/加熱前之膜厚x1〇〇(%) ③ 耐熱變色性之評估 就具有如上述方式所形成的保護膜的基板，在烤爐中 在2 5 0 °C下加熱1小時，並按與上述①同樣方式測定加熱前 後之透明性。表1中表示依下述式所算出的抗熱變色性。 抗熱變色性=加熱前之穿透率（％)-加熱後之穿透率（％) ④ 表面硬度之測定 就具有如上述方式所形成的保護膜的基板，依照jIS K5400- 1 990之8.4.1鉛筆刮傷試驗，測定保護膜之表面硬度 。表1中表示此値。如此値爲4 Η或較硬時，則可認爲表面 硬度良好。 ⑤ 動態顯微硬度之測定 就具有如上述方式所形成的保護膜的基板，使用島津 動態顯微硬度計DuH-201(島津製作所（股）製），依照稜角 _ 46 - (43) (43)200401002 11 5 °三角壓頭（赫爾科必知型）之押痕試驗’按荷重： O.lgf、速度：〇.〇145gf/秒，保持時間：5秒鐘’溫度：23 t：及140°C之測定條件，測定保護膜之動態顯微硬度。表1 中表示其結果。 ⑥ 密貼性之評估 就具有如上述方式所形成的保護膜的基板，實施壓力 鍋試驗（120°C，濕度100%，4小時）之後，依照〗IS K-5400-1 9 9 0之8.5.3附著性方格子粘膠帶法評估保護膜之密貼性（ 對SiCh(二氧化矽）的密貼性）。表1中表示100個方格子中所 留下的方格子之數。 又，作爲對Cr(鉻）的密貼性之評估，除不用Si〇2浸漬 基板而使用Cr基板之外，其餘則按與上述者同樣方式以形 成膜厚2.0μπι之保護膜，並依上述之方格子粘膠帶法同樣 加以評估。表1中表示其結果。 ⑦ 平坦化性之評估 在Si〇2浸漬玻璃基板上，使用旋塗器塗佈顔料系色光 阻（商品 名「JCRRED689」、「JCR GEEN 706」、「 CR8 200B」、以上均爲傑伊埃斯愛爾（股）製，在加熱板上 在90 °C，預焙150秒鐘以形成塗膜。然後，介由既定之圖 型遮罩（pattern mask)而使用曝光機Canon(佳能）PLA501F( 佳能（股）製，將ghi線（波長436nm、405nm、365nm之強度 比=2.7 : 2.5 : 4.8)按i線換算以2,00 0J/m2之曝光量照射， -47- (44) (44)200401002 並使用0.05%氫氧化鉀水溶液加以顯像，使用超純水進行 漂洗60秒鐘後，再在烤爐中在230°C加熱處理30分鐘以形 成紅、綠以及藍之3色帶狀濾色器（條紋寬度ΙΟΟμηι)。 將此形成有濾色器的基板表面之凹凸，使用表面粗糙 計「α -斯貼補」（商品名：添可爾社製）測定的結果，爲 Ι.Ομιη。在此，按測定長度2,000μηι，測定範圍2,000μιη， 角，測定點數η = 5之條件進行測定。亦即，將測定方向作 成紅、綠、藍方向之帶狀線（stripe line)短軸方向及紅· 紅、綠·綠、藍•藍之同一色之帶狀線長軸方向之2方向 ，並就各方向按n = 5加以測定（合計之η數爲10)。 在此上面，使用旋塗機塗佈上述保護膜形成用組成物 之後，在加熱板上在90°C下預焙5分鐘，再在烤爐中在230 °C加熱處理60分鐘以形成從濾色器之上面的膜厚爲2.Ομιη 之保護膜。 就如上述方式所形成的在濾色器上具有基板，使用接 觸式膜厚測定裝置（2 -斯貼補（添可爾日本（股）製），測定保 護膜表面之凹凸。在此，按測定長度2,000μιη，測定範圍 2,000μπι角，測定點數η = 5之條件進行測定。亦即，將測定 方向作成紅、綠、藍方向之帶狀線短線方向及紅•紅、綠 、•綠、藍•藍之同一色之同一色帶狀線長軸方向之2方 向’並就各方向按η = 5加以測定（合計之η數爲10)。表1中 表示每次測定的最高部與最底部之高低差（nm)之1〇次平均 値，如此値爲300nm以下時，則可認爲平坦化性良好。 (45) (45)200401002 實施例2至7及比較例1，2 將組成物之各成份之種類及量作成如表1所記載之方 式’並除不用丙二醇一甲基醚乙酸酯而使用表1所記載之 溶媒以配合表I所記載之固體成份濃度以外，其餘則按與 實施例1同樣方式調製組成物。 對其組成物，作爲[D ]成份而添加使偏苯三甲酸酐3 5 重量份溶解在二乙二醇甲基乙基醚65重量份中者，以調製 保護膜形成用組成物。將在此所調製的組成物之外觀，在 表1中表示。 使用如上述方式所調製的保護膜形成用組成物，按與 實施例1同樣方式形成保護膜，並加以評估。其結果如表1 所示。 在此，表1中各成份之添加量係重量份，而表中之「--」表示未添加有所相當之成份之意。 另外，[B]成份、[C]成份、溶媒之簡稱係分別表示如 下所述者。 B-1 :矽烷改性環氧樹脂「孔甫色朗E-202」（商品名 ，荒川化學工業（股）製） B-2 :矽烷改性環氧樹脂「孔甫色朗E-201」（商品名 ，荒川化學工業（股）製） B-3 :矽烷改性環氧樹脂「孔甫色朗E-101」（商品名 ，荒川化學工業（股）製） B-4 :矽烷改性環氧樹脂「孔甫色朗E-2 1 2」（商品名 ,荒川化學工業（股）製） -49 - (46) (46)200401002 C-l :雙酚A淸漆型環氧樹脂（油化雪爾愛博克斯（股） 製，商品名：埃比可特157S65) C-2 :雙酚A型環氧樹脂（油化雪爾愛博克斯（股）製， 商品名：埃比可特828) S-1:丙二醇一甲基乙基乙酸酯 S-2:二乙二醇一甲基乙基乙酸酯DOOO -19- (16) (16) 200401002 or less than 1.2. In particular, it is preferably adjusted to 1.2 or more. (2) The method such as stopping the dealcoholization reaction in the middle of the reaction to prevent the increase in viscosity and the gel method. For example, a method of changing the reaction system to a reflux system to adjust the distilling amount of methanol from the reaction system when the viscosity is gradually increased, or cooling the reaction system to stop the reaction, and the like can be used. The production of the above-mentioned component [B] can be carried out, for example, by feeding the aforementioned components and distilling off the alcohol produced by heating to perform a dealcoholization condensation reaction. The reaction temperature is preferably 150 to 130 ° C, more preferably 70 to 110 ° C, and the reaction time is preferably 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent (b 2) the polycondensation reaction of the oxo group. In addition, this reaction 'can be carried out under a reduced pressure in a range where the epoxy resin containing a hydroxyl group does not evaporate in order to shorten the reaction time. When the above-mentioned dealcoholization reaction is carried out, in order to promote the reaction, a catalyst known in the art that does not cause ring opening of an oxirane ring can be used. The catalyst can be exemplified by: lithium, sodium, potassium, cesium, magnesium, consumption, barium, total, zinc, Ming, thorium, cobalt, germanium, tin, lead, antimony, arsenic, thallium, cadmium, Metals of manganese; oxides, organic acid salts, halides, alkoxides, etc. of these metals. Among them, particularly preferred are organic tin and organic acid tin, specifically, dibutyltin laurate, tin octoate and the like. The above reaction may be carried out in a solvent. The solvent 祗 is not particularly limited as long as it can dissolve (bl) an epoxy resin containing a hydroxyl group and (b2) an alkoxysilane, and will not react therewith. Such an organic solvent can be exemplified. : Aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, etc. -20- (17) (17) 200401002 A commercially available product suitable for use as an alkoxy-containing silane-modified epoxy resin. Examples include: Arakawa Chemical Industry Co., Ltd., trade name: Kongfu Serangu-101 , E-102, E-201, E-202 'E-211, E-212, etc. Among them, Arakawa Chemical Engineering Industry Co., Ltd. 'trade name: Kongfusera E-20 1, E-202, E-212, because the protective film produced can have a high surface hardness, good. [C] Cationic polymerizable compound different from [A] component and [B] component The cationically polymerizable compound different from [C] and [A] component and [B] component used in the present invention may be Examples: Compounds having two or more oxetanyl groups, 3,4-epoxycyclohexyl groups, or epoxy groups in the molecule. Specific examples of such a [C] cationically polymerizable compound include the following. Examples of the compound having two or more oxetanyl groups in the molecule include 3,7-bis (-oxetanyl) -5-oxo-nonane, and 3,-( 1,3- (2-methylene) propanediylbis (formaldehyde) bis (3-methyloxetane), 1,4-bis [(3-methyl-3-oxetane Methoxy) methyl] benzene, 1,2-bis [(3-methyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-methyl Methyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-methyl-3-oxetanylmethyl) ether, dicyclopentylbis [3- Methyl-3-oxetanylmethyl] ether, triethylene glycol bis (3-methyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-methyl -3-oxetanylmethyl) ether, tricyclodecanediyldimethylene bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane (3-methyl-3-oxetanylmethyl) -21-(18) (18) 200401002 ether,]., 4-bis (3-ethyl-3-oxetanylmethyl) Oxy) butane, 1 '6_bis (3-ethyl-3-oxetanylmethoxy) hexane, isopentaerythritol (3 _ Ethyl-3-oxetanylmethyl) ether, isopentaerythritol (3-ethyloxetanemethyl) ether, polyethylene glycol bis (3-ethyl-3 —Oxetanylmethyl) ether, diisopentaerythritol (3-ethyl-3-oxetanylmethyl) ether, diisopentaerythritol (3-ethyl-3 -Oxetanylmethyl) ether, diisopentaerythritol (3-ethyl-3 -oxetanylmethyl) ether, diisopentaerythritol (3-ethyl-oxyl) Reaction product between heterocyclobutanemethyl) ether and caprolactone, reaction between diisopentaerythritol (3-ethyl-3-oxetanylmethyl) ether and caprolactone Product, bistrimethylolpropane (3-ethyl-3 -oxetanylmethyl) ether, bisphenol A bis (3-ethyl-3-oxetanylmethyl) Reactant between ether and ethylene oxide 'Resin between bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether and propylene oxide, hydrogenated bisphenol hexabis (3 —Ethyl-3 · oxetanylmethyl) ether and reaction product between ethylene oxide 'Hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) Ether and propylene oxide Reaction product, reaction product between bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether and ethylene oxide, etc. It has 3,4-epoxy group in the molecule For compounds having two or more cyclohexyl groups, 3,4-epoxycyclohexylmethyl-3 > '-epoxycyclohexylcarboxylate, 2- (3, I epoxycyclohexyl -5,5-spiro-3 '4-epoxy) cyclohexane-m-dioxane, bis (3' 4-epoxycyclohexylmethyl) adipate, bis (3,4_cyclo Oxy-6-methylcyclohexylmethyl) adipate, 3 '4-epoxy-6_methylcyclohexyl-3,4, -epoxy-6 <-methylcyclohexane carboxylate, methylene bis (3 '4-epoxy cyclohexane), dicyclopentadiene di-22 ~ (19) (19) 200401002 epoxide, ethyl Diol (3,4-epoxycyclohexylmethyl) ether, methylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3 '4-epoxy Cyclohexylmethyl-3β, 4 / -epoxycyclohexane carboxylate and the like. Examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenation. Bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether Ethers, brominated bisphenol S diglycidyl ether diglycidyl ethers of various bisphenol compounds; such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Polyglycidyl ethers of polyols based on polyethers, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyalcohols prepared by adding one or more epoxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; phenolic epoxy resins; Cresol lacquer type epoxy resin; Polyphenol type epoxy resin; Aliphatic long chain dibasic acid Glycidyl ether; glycidyl 咼 glyceryl esters of fatty acid; epoxidized soybean oil, epoxidized linseed oil and the like. As for a commercially available product having two or more of the above-mentioned epoxy groups, "May-23- (20) (20) 200401002" is exemplified as ... Same as 002, same as 1003, same as 1004, same as 1007, same as 109, same as 010, same as 828 (the above are all made by Petrochemical Shire Aikesi), etc .; as bisphenol For E-type epoxy resins, Ebb can be 807 (made by Shire Aikebox Co., Ltd.), etc .; Epicot 152, same as 154, and 15 7S65 ( The above are all made by Shire Aikex (stock), EPPN201, and 202 (the above are all made by Nippon Kayakusho (stock)); EOCN102, same as 103S, and 104S as cresol lacquer type epoxy resin '' 1020, 1025, 1027 (the above are manufactured by Nippon Kayaku Co., Ltd.), Epicot 180S75 (Oilized by Shire Aikex Co., Ltd.), etc .; Epicco as a polyphenol epoxy resin Special 1032H60, the same XY-4000 (the above are all made of oil-based Shier Aikesi (shares)), etc .; CY-175, 177, 179, Alardet CY- 182, same as 192, 184 (above Chiba. Special Chemicals (stock) system), ERL-4234, same 4299, same 4221 'and 4206 (above all are produced by UCC), Xiao Daiyin 596 (showa Denko (stock) system), Ebikolon 200, the same as 400 (above, Dainippon Ink (stock) system, Epicort 871, the same as 872 (the above are all made by Petrochemical Shire Aikesi (stock)), EP-5661, the same as 5662 (above, salad Nice Coated (made by Co., Ltd.), etc .; Ebolite 100MF (made by Kyoeisha Chemical Co., Ltd.) as an aliphatic polyglycidyl ether, TMP (made by Nippon Oil & Fats Co., Ltd.), etc. The cationically polymerizable compound can be used alone or in combination of two or more. -24- (21) (21) 200401002 Among these [c] cationically polymerizable compounds, the preferred one is phenol lacquer type [D] curing agent [D] curing agent used in the composition of the present invention can be exemplified by polycarboxylic acids, polycarboxylic anhydrides, and unsaturated polycarboxylic acids. A copolymer between a carboxylic anhydride and an olefin-based unsaturated compound. As for the polyvalent carboxylic acid, it is preferably a fatty acid Carboxylic acids, alicyclic φ polycarboxylic acids, and aromatic polycarboxylic acids. Examples include aliphatic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid. Polycarboxylic acids; such as alicyclic polycarboxylic acids of hexahydrophthalic acid, 1 '2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid; phthalic acid , Isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, aromatic polycarboxylic acids of 1,2,5,8-naphthalenetetracarboxylic acid. Among these, from the viewpoints of the reactivity of the curable composition and the heat resistance of the formed cured film, an aromatic polycarboxylic acid is particularly preferred. _ As for the said polycarboxylic acid anhydride, an aliphatic dicarboxylic acid anhydride, an alicyclic polycarboxylic acid dianhydride, an aromatic polycarboxylic acid anhydride, and the acid anhydride containing an ester are preferable. Examples include: fatty acids such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, trimellitic anhydride, maleic anhydride 'hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and heming anhydride Dicarboxylic anhydrides, such as alicyclic polycarboxylic dianhydrides of 1 '2' 3 '4 -butanetetracarboxylic anhydride and cyclopentanetetracarboxylic dianhydride; such as phthalic anhydride, pyromellitic anhydride' trimellitic acid Aromatic polycarboxylic anhydrides of acid anhydrides and diphenylketone tetracarboxylic anhydrides; such as ethylene glycol bistrimellitic acid acetic anhydride, -25- (22) (22) 200401002 glycerol-trimellitic anhydride-containing esters Acid anhydride. Among these, an aromatic polycarboxylic acid anhydride, especially trimellitic anhydride, is particularly preferable because a cured film having high heat resistance can be obtained. Examples of the unsaturated polycarboxylic acid anhydrides used to synthesize the copolymer of the unsaturated polycarboxylic acid anhydride and an olefin-based unsaturated compound include, for example, itaconic anhydride, citraconic anhydride, maleic anhydride, and cis 1,2. 3,4-tetrahydrophthalic anhydride, at least one type of unsaturated polycarboxylic anhydride. Examples of the olefin-based unsaturated compound used to synthesize a copolymer of an unsaturated polycarboxylic anhydride and an olefin-based unsaturated compound include styrene, p-methylstyrene, p-methoxystyrene, Methyl methacrylate, third butyl methacrylate, tricyclo [5.2.1.02 = 6] decane-8-yl ester, 2-methylcyclohexyl acrylate, phenylmaleimide At least one or more olefinic unsaturated compounds of cyclohexylmaleimide. The copolymerization ratio of the copolymer of unsaturated polycarboxylic acid anhydride and olefin-based unsaturated compound per 100 parts by weight of unsaturated polycarboxylic acid anhydride is preferably 1 to 80 parts by weight, and more preferably 10 to 60 parts by weight. By using such a copolymer, a protective film having excellent planarity can be obtained. Preferred examples of the copolymer of an unsaturated polycarboxylic acid anhydride and an olefinic unsaturated compound include: anhydrous maleic acid copolymer / styrene, citraconic anhydride / methacrylic acid tricyclic [5.2.1 · 02 ' 6] Decane-8-yl ester copolymer and the like. The polystyrene-equivalent weight average molecular weight 'of the copolymer of the unsaturated polycarboxylic acid anhydride and the olefin-based unsaturated compound is preferably 500 to 50,000, and more preferably 500 to 10,000. Since such a copolymer 'having a molecular weight range of -26 to (23) (23) 200401002' can be used, a protective film having excellent planarity can be obtained. Copolymer [E] The copolymer [E] used in the present invention is (e 1) an unsaturated carboxylic acid anhydride and / or an unsaturated carboxylic acid anhydride, (e 2) an unsaturated compound containing an epoxy group ', and (e3 ) A copolymer of an olefinic unsaturated compound different from the (el) component and the (e2) component. The copolymer [E], for each 100 parts by weight of the copolymer [E], contains the constituent unit derived from the compound (e 1), preferably 5 to 40 parts by weight, particularly preferably 10 to 30 parts by weight. Here, a copolymer having a composition unit of 5 parts by weight or less tends to decrease heat resistance, chemical resistance, and surface hardness. On the other hand, a copolymer having a composition unit of more than 40 parts by weight may have low storage stability. As for the (e 1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, medium Dicarboxylic acids such as fumaric acid, itaconic acid, and the like; and anhydrous form of these dicarboxylic acids. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of copolymerization reactivity, heat resistance, and easy availability. These compounds (e 1) 'can be used alone or in combination. The copolymer [E] contains the composition unit derived from the compound (e 2) per 100 parts by weight of the copolymer [E], preferably 10 to 70 parts by weight, particularly preferably 20 to 60 parts by weight . When the composition unit is 10 parts by weight or less, the resulting protective film has a heat resistance that tends to decrease the surface hardness. On the other hand, when it exceeds 70 parts by weight, the composition contains such a copolymer. Chu-27- (24) (24) 200401002 The tendency of stability to decline. (e2) As the unsaturated compound containing an epoxy group, the same as those exemplified for the compound (al) used as the copolymer [A] can be used. The copolymer [E] contains the constituent unit derived from the compound (e3) per 100 parts by weight of the copolymer [E], preferably 10 to 70 parts by weight, and particularly preferably 20 to 50 parts by weight Serving. When the composition unit is 10 parts by weight or less, the storage stability of the composition containing the copolymer tends to decrease. On the other hand, when it exceeds 70 parts by weight, the heat resistance of the obtained protective film, The surface hardness tends to decrease. (e3) The olefin-based unsaturated compounds other than (el) and (e2) may be the same as those exemplified for the compound (a2) used as the copolymer [A]. Specific examples of the copolymer [E] used in the present invention include: styrene / triacrylic acid [5.2.1.02'6] decane-8-yl ester / glycidyl methacrylate copolymerization Polymer, styrene / acrylic acid / acrylic acid tricyclic [5.2.1.02'6] decane-8-yl ester / glycidyl acrylate copolymer, styrene / methacrylic acid / phenylmaleimide / methacrylic acid Glycidyl ester copolymer, styrene / acrylic acid / phenylmaleimide / glycidyl acrylate copolymer, styrene / methacrylic acid / cyclohexylmaleimide / glycidyl methacrylate copolymer, Butadiene / styrene / methacrylic acid / tricyclic methacrylate-28- (25) (25) 200401002 [5.2.1.〇2'6] decane-8-yl ester / glycidyl methacrylate Copolymer, butadiene / methacrylic acid / methacrylic acid tricyclic [5.2.1.02'6] decane. 8-yl ester / glycidyl methacrylate copolymer, styrene / methacrylic acid tricyclic [5.2 .1.02'6] decane-8-yl ester / -6,7-epoxyheptyl methacrylate copolymer. Copolymer of styrene / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl ester, tertiary butyl methacrylate / acrylic acid / maleic anhydride / methacrylic acid ester-6,7-epoxy Heptyl copolymer, styrene / methacrylic acid / methyl methacrylate / glycidyl methacrylate copolymer, p-methoxystyrene / methacrylic acid / cyclohexyl acrylate / glycidyl methacrylate Copolymers, etc. Preferred among them are: styrene / methacrylic acid / triacrylic acid [5.2.1.02'6] decane-8-yl ester / glycidyl methacrylate copolymer styrene / methacrylic acid / benzene Co-maleimide / glycidyl methacrylate copolymer, styrene / methacrylic acid / cyclohexylmaleimide / glycidyl methacrylate copolymer, butadiene / styrene / methacrylic acid copolymer /Tricyclomethacrylate[5.2.1.02'6]decane-8·yl ester / glycidyl methacrylate copolymer, butadiene / methacrylic acid / methacrylic acid tricyclic [5.2.l.o2, 6] Decane 8-yl ester / glycidyl methacrylate copolymer. -29- (26) (26) 200401002 Copolymer [E], polystyrene-equivalent weight-average molecular weight is preferably 3,000 to 100,000, more preferably 3,000 to 50,000. It is preferably 3,000 to 20,000. When a copolymer having a molecular weight within this range is used, a protective film having excellent planarity can be produced. The copolymer [E] can be an unsaturated compound containing the (el) unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride '(e2) containing an epoxy group in the presence of a suitable solvent and a polymerization initiator, and (E3) An olefin-based unsaturated compound different from the (el) component and the (e2) component can be synthesized by, for example, radical polymerization. A synthetic solvent and a polymerization initiator for the copolymer [E] can be used. The same as those exemplified for the solvent and polymerization initiator used in the production of the aforementioned copolymer [A] can be used. [F] Cationic polymerizable compound different from [B] component and [E] component The cationically polymerizable compound different from [F] and [B] component and [E] component used in the present invention may be Use the same as those mentioned as the [C] component mentioned above. [G] Compound that will generate acid due to heat and / or radiation The component [G] used in the present invention is a radiation-induced acid generator or a thermally-induced acid generator. As the radiation-initiating acid generator, diaryl iron iodide salts, triarylsulfonium salts, diaryl scale salts, and the like can be exemplified, and are very applicable. In addition, as the thermally-induced acid generator, sulfonium salts (except the aforementioned triarylsulfonium salts-30- (27) (27) 200401002), benzothiazole sulfonium salts, ammonium salts, Rust salts and the like. Among them, sulfonium salts (except the aforementioned triarylsulfonium salts) and benzothiazole sulfonium are very suitable. Examples of the diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, and diphenyliodine.鏺 Trifluoromethanesulfonate, diphenyliodine trifluoroacetate, diphenylp-toluenesulfonate, 4-methoxyphenylphenyliodide iron tetrafluoroborate, 4-methoxyphenyl Phenyliodonium hexafluorosulfonate, 4-methoxyphenylphenyl φ iron iodide hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxy Phenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium p-toluenesulfonate, bis (4-th Tributylphenyl) iron iron tetrafluoroborate, bis (4-thirdbutylphenyl) iodine gun hexafluoroarsenate, bis (4-thirdbutylphenyl) iodine trifluoromethanesulfonic acid Salt, bis (4-tert-butylphenyl) iodotrifluoroacetate, bis (4-tert-butylphenyl) iodohydrazone p-toluenesulfonate and the like. Among them, diphenyliodonium hexafluorosulfonate is suitable. _ For the above triarylphosphonium salts, there may be mentioned: triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluoroarsenate, triphenylphosphonium trifluoromethanesulfonate Acid salt, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluoride Phosphate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium Fluoroacetate, 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate, 4-phenylphenylthiodiphenyltetrafluoroborate, 4-phenylphenylthiodi-31-(28) (28) 200401002 Phenylhexafluorophosphate, 4-phenylphenylthiodiphenylhexafluoroarsenate, 4-phenyl ~ phenylphenylthiodiphenyltrifluoromethanesulfonate, 4-phenylbenzene Thiodiphenyl tri-fluoroacetate, 4-phenylphenylthiodiphenyl p-toluenesulfonate, and the like. Among them, triphenylsulfonium trifluoromethanesulfonate is suitable. As for the above diaryl scale salts, (1-6-77 -anisin) (?? -cyclopentadienyl) iron hexafluorophosphate and the like can be mentioned. As an acid generator which is very suitable for generating a radioacid generator, it can be made as a joint calcium carbide company of diaryl iodogun salts, trade name: Lu UVI-6950 'UVI-6970, UVI-6974, UVI -6990, green chemical (stock) system, trade name: MPI-103 'BBI-103, etc. In addition, as the triarylsulfonium salts, there can be mentioned: Asahi Denka Kogyo Co., Ltd., trade names: Adka Obuduo SP-150, SP-151, SP-170, SP-171, Soda Japan (stock ) System, trade name: (: 1-248 1, <: 1-2624, (: 1-263 9, CI-20 64, green chemical (stock) system, trade name: DTS-102, DTS-103 'NAT-103, NDS-103, TPS-103, MDS -103, manufactured by Shaduosha, trade name: CD-1010, CD-1011, CD-1012, etc. · As for diary aryl salts, for example: Chiba Specialty Chemicals (stock) system , Trade name: Ilgaya 261, Japan Chemicals (stock) system, trade name: PCI-061T, PCI-062T, PCI-020T, PCI-022T, etc. Here, the joint calcium carbide company, trade name : UVI-6970, UVI-6974, UVI-6990, manufactured by Asahi Denka Kogyo Co., Ltd., trade name · Adka Obudo 瑪 SP-170, SP-171, manufactured by Sado 瑪, trade name: CD -1012, green chemical (stock) system, trade name: MPI-103, because the resulting protective film has high surface hardness, it is preferred. -32- (29) (29) 200401002 Among the specific examples of sulfonium salts (except for the aforementioned triarylsulfonium salts), there may be mentioned: 4-ethylacetoxyphenyldimethylfluorene hexafluoroantimonate, 4-ethylacetoxybenzene Dimethyl phosphonium hexafluoroarsenate, dimethyl-4- (benzyloxy Carbonyloxy) phenylfluorene hexafluoroantimonate, dimethyl-4 — (phenylfluorenyloxy) phenyl fluorene hexafluoroantimonate, dimethyl-4- (phenylfluorenyloxy) phenylfluorene Alkyl sulfonium salts of hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenyl hexafluoroantimonate; benzyl-4-hydroxyphenylmethyl fluorinated antimony Acid salt, benzyl-4-hydroxyphenylmethylfluorene hexafluorophosphate, 4-ethoxyfluorenylbenzylmethylfluorene hexafluoroantimonate, benzyl-4-methoxyphenylmethyl Phenylhexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl, hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl, hexafluoroarsenate , 4-methoxybenzyl-4-hydroxyphenylmethyl hexafluorophosphate and other benzyl sulfonium salts; dibenzyl-4-hydroxyphenyl hexafluoroantimonate, dibenzyl-4- Hydroxyphenylphosphonium hexafluorophosphate, 4-Ethyloxyphenyldibenzylhexafluoroantimonate, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4 -hydroxy-5 -third butylphenylphosphonium hexafluoroantimonate, benzyl-4-methyl Oxybenzyl-4-hydroxyphenylfluorene Dibenzylphosphonium salt of phosphate, etc .; p-chlorobenzyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate, P-chlorobenzyl-4-hydroxyphenylmethylfluorene hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate, 3,5-dichloro Benzyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylfluorene hexafluoro-33- (30) (30) 200401002 antimony Substituted benzylphosphonium salts and the like. Among the more suitable ones are: 4-ethoxyloxyphenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-ethoxyloxyphenyl Benzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoropropionate, ethynyloxyphenyldibenzylsulfonium hexafluoroantimonate, and the like. For the above-mentioned benzothiazole iron salts, there may be mentioned: 3-benzylbenzothiazole hexafluoroantimonate, 3-benzylbenzothiazole iron hexafluorophosphate, and 3- + benzobenzothiazole gun Tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazole, hexafluoroantimonate '3-benzyl-2-methylthiobenzothiazole, hexafluoroantimonate, 3-carbyl- 5-Benzylbenzothiazole hexafluoroantimonate and other benzylbenzothiazole pentoxide. Among these, 3-benzylbenzothiazole hexafluoroantimonate and the like are more suitable. An acid generator that is very suitable as a thermally-induced acid generator, for example, as an alkyl salt, available from: Asahi Denka Kogyo Co., Ltd., trade name: Adka Obdon cp-66, cp-77, etc. Sale. In addition, as the benzyl sparse salt, there may be mentioned: Sanxin Chemical Industry Co., Ltd., trade names: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L , SI-100L, SI-110L. Among these, SI-80, si-100, and SI-110 are more preferable because the obtained protective film has the surface hardness of the cylinder. Composition Next, the composition of the present invention will be described. The composition of the present invention can be prepared by dissolving or dispersing each component uniformly -34- (31) 200401002 in a suitable solvent described later. The state of implementation of the composition of the present invention can be exemplified in the following various cases. ① The above-mentioned copolymers [A], [B], and [C] are essential components, and, as the case may be, a composition containing an optional added component described below (hereinafter, referred to as "the first composition"). ② In addition to the above components of the first composition, 尙 a composition containing a [D] curing agent. ③ A composition containing the copolymers [E], [B], and [F] as essential components, and optionally a component to be described later (hereinafter, referred to as "the second component"). ④ In addition to the above components of the second composition, 尙 a composition containing a "G" component (hereinafter referred to as "the third composition.") The mixing ratio of each component in the first composition is as follows The component [B] is based on 100 parts by weight of the copolymer [A], preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, and particularly preferably 10 to 50 parts by weight. use. If it is less than 3 parts by weight, the hardness of the resulting protective film may be insufficient. On the other hand, if it is more than 200 parts by weight, difficulties may occur in the formation of the coating film. The [C] component contained in the first composition is used in an amount of preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. If it is used in an amount within this range, a protective film having sufficient strength can be obtained. The above-mentioned first composition is excellent in long-term stability. -35- (32) (32) 200401002 The above-mentioned first composition is formed by adding a [D] curing agent during use, and then forming a protective film according to the method described later. The protective film formed in this way can meet the requirements of adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., and will not sag due to load when heat is applied. And it is better than flattening the level difference of the color filters formed on the base substrate. The [D] curing agent which can be further added to the first composition is preferably used in a state of being dissolved in an appropriate solvent. The concentration of the [D] curing agent in the solution is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. The solvent usable here is the same as that exemplified as the solvent used in the production of the aforementioned copolymer [B]. The addition amount of the curing agent is preferably 20 to 60 parts by weight per 100% by weight of the copolymer [A], more preferably 20 to 50 parts by weight. If it is used in an amount within this range, the composition can exhibit good curing characteristics without affecting various physical properties of the resulting protective film. The composition 'to which the [D] curing agent is further added to the first composition is preferably supplied and used usually within 24 hours. The blending ratio of each component in the above-mentioned second composition is shown below. [B] The component is 100 parts by weight of the copolymer [E], preferably 3 to 300 parts by weight, and more preferably 5 to 1 〇part by weight is particularly preferably used in an amount of 10 to 50 parts by weight. If it is less than 3 parts by weight, the hardness of the protective film obtained may be insufficient. On the other hand, if it is more than 250 parts by weight, difficulties may occur in the formation of the coating film. [F] component 'contained in the second composition is based on the copolymer [E] 100 -36- (33) (33) 200401002 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 to 50 Use in parts by weight. If used in this range, a protective film with sufficient hardness can be obtained. The second composition may further contain [G] a compound which generates an acid due to heat and / or radiation to form a third composition. The amount of the [G] component contained in the third composition is based on 100 parts by weight of the copolymer [E], preferably 20 parts by weight or less, more preferably 0.05 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight. If used in this amount, the composition can exhibit good curing characteristics without affecting the various physical properties of the resulting protective film. The second or third composition can be formed into a protective film by a method described later. In addition to meeting the requirements of adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., the protective film formed in this way will not sag due to load under the state of heat and Better than flattening the level difference of the color filters formed on the base substrate. Arbitrarily added ingredients The composition of the present invention can be in various states as described above, but may contain other ingredients than the above as long as it does not affect the purpose of the present invention. Examples of such other components include a surface active agent and an adhesion assistant. The surface active agent 'is added to improve the coating property of the composition. Such surfactants include, for example, fluorine-based surfactants; -37- (34) (34) 200401002 silicone-based surfactants; polyethylene oxide alkyl ethers, and polyethylene oxide aromatics. Non-ionic surfactants such as alkyl ethers and polyethylene oxide dialkyl esters. Examples of the polyethylene oxide alkyl ethers include polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether. As the polyethylene oxide aryl ethers, there may be mentioned: polyethylene oxide octylphenyl ether 'polyethylene oxide nonylphenyl ether. Examples of the polyethylene oxide dialkyl esters include polyethylene oxide dilaurate, polyethylene oxide distearate, and the like. Such a surfactant can be obtained, for example, from a fluorine-based surfactant: BMCHIMIE, trade names: BM-1000, BM-1100, Dainippon Ink Chemical Industry Co., Ltd., trade name: Mokako F142D , Same as F172, same as F173, same as F-183, Sumitomo Suliem Co., Ltd., trade name: Flora FC-135, same FC-170C, same FC-430, same FC-431, Asahi Glass (Stock) social system, trade name: Safuron s -1 1 2, same as S -1 13, same as S-131, same as S-141, same as S-145, same as S-382, same as SC-101, same as SC-102, same as SC-103, same as SC-104, same as SC-105, same as SC-106, etc .; can be obtained with silicone-based surfactants: made by Toray Silicone Corporation, trade name: SH- 28PA, SH-190, SH-193, SZ-603 2, SF-8428, DC-5 7, DC-190, Shin-Etsu Chemical Industry Co., Ltd., trade name: KP341, Shin Akita Chemical Co., Ltd. , Trade name: Evert special supplement EF301, same as EF303 'stone EF352, etc .; can be obtained by other surfactants: made by Kyoeisha Chemical Co., Ltd., trade name: (meth) acrylic copolymer, Polifo NO.57, same as (35) ( 35) 200401002 NO. 9 0 and other commercial products. The amount of these surfactants added to the first composition is "per 100 parts by weight of the copolymer [A], or when added to the second composition", the copolymer [E ] It is preferably used in an amount of 5 parts by weight or less per 100 parts by weight, and more preferably 2 parts by weight or less. If the amount of the surfactant exceeds 5 parts by weight, the film roughening of the coating film may easily occur during the coating process. The above-mentioned adhesion assistant is added to improve the adhesion between the formed protective film and the substrate. As such an adhesive auxiliary agent, a functional silane coupling agent such as a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group is suitably used. Specific examples include: trimethoxysilyl benzoic acid, τ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, r-isocyanate-propyl Base triethoxy sand garden, 7 · glycidyl propyl dioxane sand garden,-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like. When such an adhesion promoter is added to the first composition, it is added to the copolymer [A] per 1,000 parts by weight, or when it is added to the second composition, it is added to the copolymer [E]. 100 parts by weight 'is used in an amount of preferably 30 parts by weight or less, and more preferably 25 parts by weight or less. When the adhesion aid exceeds 30 parts by weight, the heat resistance of the obtained protective film may be insufficient. Solvent The composition of the present invention can be prepared by uniformly dissolving or dispersing each component in a suitable solvent. Usable solvents are those which can dissolve the ingredients of -39- (36) (36) 200401002 or disperse the composition without reacting with the ingredients. Such a solvent can be the same as that exemplified as the solvent used in the production of the aforementioned copolymer [A]. The used amount of the solvent is an amount of preferably 1 to 50 parts by weight and more preferably 5 to 40 parts by weight per 100 parts by weight of the total solid content of the composition of the present invention. In addition, a high boiling point solvent can be used together with the aforementioned solvent, and high boiling point solvents that can be used include, for example, N-methylformamide, N, N-dimethylformamide, and N- Methylformanilide, N-methylacetamide 'N, N-dimethylacetamide, N-methylpyrrolidone, dimethylasco, benzyl ether, dihexyl ether, acetone acetone, isopropyl Furone, hexanoic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, carbonic acid Vinyl ester, propylene carbonate, phenylcellosolve acetate, and the like. The amount used when a high boiling point solvent is used is 100 parts by weight of the total solvent amount, preferably 90 parts by weight or less, and more preferably 80 parts by weight or less. The composition prepared in the above manner can also be used after being filtered using a Millipore filter having a pore size of preferably 0.2 to 3.0 μm, more preferably a pore size of 0.2 to 0.5 μm. Formation of Protective Film Next, a method for forming the protective film of the present invention using the composition of the present invention will be described. If the composition of the present invention is the first composition, the second composition, or the third composition containing a thermal-initiating acid generator as the [G] component, the -40- (37) (37) 200401002 The composition is coated on the surface of a substrate, a solvent is removed by prebake, a coating film is formed, and then a heat treatment is performed to form a protective film for the purpose. As a user of the substrate, there are substrates such as glass, quartz, silicon, and resin. For resins, examples include: ring-opening polymerization of polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, polyimide, and cyclic olefins Resins and their hydrogen additives. As the coating method, suitable methods such as a spray method, a roll coating method, a spin coating method, a bead coating method, and an inkjet method can be adopted. The conditions for the pre-baking described above differ depending on the type of each component or the blending ratio, but conditions such as 1 to 15 minutes at 70 to 90 ° C can be used. The heat treatment after the coating film is formed can be performed using a suitable heating device such as a hot plate or an oven. The treatment temperature is preferably in the range of 150 to 250 r. If a heating plate is used as a heating device, it is preferably 5 to 30 minutes. When an oven is used, a treatment time of 30 to 90 minutes is preferable. On the other hand, when the composition of the present invention is a third composition containing a radiation-inducing acid generator as the [G] component, the composition is coated on the surface of a substrate and the solvent is removed by pre-baking and After the coating film has been formed, light is irradiated (exposure treatment) to form a protective film as a target. If necessary, a heat treatment may be performed after the exposure treatment. In this case, a coating film is formed on the substrate in the same manner as described above. Examples of the radiation that can be used in the above radiation irradiation treatment include visible light rays, ultraviolet rays, extreme ultraviolet rays, electron rays, and X-rays. Among these, particularly preferred is ultraviolet rays containing light having a wavelength of 190 to 450 nm. -41-(38) (38) 200401002 The exposure is preferably 100 to 20,00 (H / m2, more preferably ι0 to 10,000J / m2, and particularly preferably 100 to 5,000J / m2. The film thickness of the protective film formed by the method is preferably 0.1 to 8 μηι, more preferably 0.1 to 6 μm, and particularly preferably 0.1 to 4 μm. Here, the protective film according to the present invention will be formed on When the color filter has a low-level substrate, the above-mentioned film thickness refers to the thickness from the uppermost part of the color filter. The protective film of the present invention can be understood as shown in the following examples, except that it can meet the dense In addition to the requirements of adhesiveness, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., it will not sag due to load when heat is applied, and it can be used to form the substrate on the substrate. [Protective film for an optical device] excellent in performance of level difference leveling of a color filter. [Embodiments] Hereinafter, the present invention will be described more specifically by describing synthesis examples and examples, but the present invention is not limited to the following examples. Production of Copolymer [A] The following describes production examples of the copolymer [A] used in the present invention. Examples 1 and 2. Synthesis Example 1 A flask equipped with a cooling tube and a stirrer was fed with 2,2--azobisisobutyronitrile, and 2 '4-diphenylmethyl-papene by weight. Parts and 200 parts by weight of propylene glycol monomethyl ether acetate. Then, 80% by weight of glycidyl-42-(39) (39) 200401002 methacrylate and 20 parts by weight of styrene were fed, and then nitrogen was substituted, and then slowly Start stirring. Raise the solution temperature to this temperature for 4 hours to prepare a polymer solution containing copolymer (A-1). The solid content concentration of the obtained polymer solution is 33.0% by weight. In addition, the copolymer The weight-average molecular weight (Mw) of (A-1) was 8,000. Synthesis Example 2 A flask equipped with a cooling tube and a stirrer was fed with 2, 2 >-6 parts by weight of azoφdiisobutyronitrile, 10.0 parts by weight of 2,4-diphenyl-4-methyl-1-pentene and 200 parts by weight of propylene glycol monomethyl ether acetate. Next, 50 parts by weight of glycidyl methacrylate and After 50 parts by weight of tricyclo [5.2.1.02,6] decane-8-yl methacrylate was replaced with nitrogen, stirring was started slowly. The temperature of the solution was increased. The temperature was raised to 95 ° C, and the temperature was maintained for 4 hours to prepare a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 33.0% by weight. The copolymer (A-2 ) Has a weight average molecular weight (Mw) of 6,000. Production of the Thai copolymer [E] The following will describe production examples of the copolymer [E] used in the present invention in Synthesis Examples 3 and 4. Synthesis Example 3 The cooling tube and the flask of the stirrer were fed with 5 parts by weight of 2,2-azo (2,4-dimethylvaleronitrile), and diethylene glycol methyl ethyl ether 2000-43-(40) (40) 200401002 copies. Next, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 10 parts by weight of tricyclo [5.2.1.02 · 6] decane-8-yl ester were fed. After nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to prepare a polymer solution containing the copolymer (E-1). The solid content concentration of the obtained polymer solution was 33.0% by weight. The weight average molecular weight (Mw) of the copolymer (E-1) was 6,000. Synthesis Example 4 A flask equipped with a cooling tube and a stirrer was fed with 5 parts by weight of 2,2 z-azo (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether. Next, 18 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 22 parts by weight of cyclohexylmaleimide were fed, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to prepare a polymer solution containing the copolymer (E-2). The solid content concentration of the obtained polymer solution was 3 3.0% by weight. The weight average molecular weight (Mw) of the copolymer (E-2) was 12,000. Preparation and Evaluation Example 1 of the First Composition Example 1 was added to the polymer (A-1) -containing solution (amount corresponding to 100 parts by weight (solid content) of the copolymer (Al)) obtained in the above Synthesis Example 1 as [b] 20.0 parts by weight of "Kung Fu Serang E-202" (trade name, manufactured by Arakawa Optical Industries, Ltd.) 'as a [C] component, bisphenol A lacquer-type epoxy resin "Eb-44 -(41) (41) 200401002 Kate 157s65 "(trade name, 10.0 parts by weight of oil-based Shier Aikesi Co., Ltd.), as r-glycidyloxypropyltrimethoxysilane 1 5 Parts by weight, and SH28PA (0.1 parts by weight of Toray Silicon Dioxide Co., Ltd.) as a surfactant, and after adding propylene glycol monomethyl ether acetate so that the solid content can be 20%, use Millipore with a pore size of 0.5 μm Filtered by a boar filter to prepare the first composition. Formation of a protective film To the composition prepared as described above, 35 parts by weight of trimellitic anhydride was added as a component [D] and dissolved in ethylene glycol methylethyl. Among the 65 parts by weight of ether, a composition for forming a protective film is prepared. The composition is colorless and transparent. After the above composition is coated on a S1 Ch immersed glass substrate using a spin coater, it is prebaked on a hot plate at 80 ° C for 5 minutes to form a coating film, and then placed in an oven. Heat treatment at 230 ° C for 60 minutes to form a protective film with a thickness of 2.0 μm. Evaluation of the protective film ① Evaluation of the transparency 的 A substrate with a protective film formed as described above, using a spectrophotometer (1 50-20 type double Beam (made by Hitachi, Ltd.)) to measure the transmittance from 400 to 800 nm. Table 1 shows the minimum transmittance from 400 to 800 nm. In this way, it can be recognized when it is more than 95%. For the good transparency of this protective film -45- (42) (42) 200401002 ② Evaluation of heat resistance dimensional stability The substrate with the protective film formed as described above was heated in an oven at 250 °. (: Under heating 1 hour 'and measured the film thickness before and after heating. Table 1 shows the heat-resistant dimensional stability calculated by the following formula. When it is more than 95%, the heat-resistant dimensional stability is considered good. Heat-resistant dimensional stability Property = (film thickness after heating) / film thickness before heating x 100 (%) For evaluation of heat discoloration resistance, the substrate having the protective film formed as described above was heated in an oven at 250 ° C for 1 hour, and the transparency before and after heating was measured in the same manner as in ① above. Table 1 It shows the thermal discoloration resistance calculated according to the following formula: Thermal discoloration resistance = transmittance before heating (%)-transmittance after heating (%) ④ The measurement of the surface hardness has the form as described above. For the substrate of the protective film, the surface hardness of the protective film was measured according to jIS K5400-1990, 8.4.1 pencil scratch test. This is shown in Table 1. When it is 4 4 or harder, the surface hardness is considered good. ⑤ Measurement of dynamic microhardness: For substrates with a protective film formed as described above, use the Shimadzu Dynamic Microhardness Tester DuH-201 (manufactured by Shimadzu Corporation) in accordance with the angle _ 46-(43) (43) 200401002 11 5 ° Triangular Indenter (Herco must know type) scoring test 'by load: O.lgf, speed: 0.015gf / sec, holding time: 5 seconds' temperature: 23 t: and 140 The measurement conditions at ° C are used to determine the dynamic microhardness of the protective film. The results are shown in Table 1. ⑥ Evaluation of adhesiveness After a substrate with a protective film formed as described above is subjected to a pressure cooker test (120 ° C, humidity 100%, 4 hours), it is in accordance with 〖IS K-5400-1 9 9 0 of 8.5. 3 Adhesive square grid adhesive tape method to evaluate the adhesiveness of the protective film (adhesiveness to SiCh (silicon dioxide)). Table 1 shows the number of squares left in the 100 squares. In addition, as an evaluation of the adhesion of Cr (chrome), a protective film having a thickness of 2.0 μm was formed in the same manner as the above except that a Cr substrate was not used to impregnate the substrate with SiO2, and the above was used. The square grid adhesive tape method was also evaluated. The results are shown in Table 1.评估 Evaluation of flatness on a SiO2 immersed glass substrate, using a spin coater to apply a pigment-based color photoresist (trade names "JCRRED689", "JCR GEEN 706", "CR8 200B", all of which are Jay Eis Manufactured by Air (strand), pre-baked on a hot plate at 90 ° C for 150 seconds to form a coating film. Then, an exposure machine Canon PLA501F (is used through a predetermined pattern mask. Canon (stock) system, ghi line (wavelength 436nm, 405nm, 365nm intensity ratio = 2.7: 2.5: 4.8) according to i-line conversion with an exposure of 2,00 0J / m2, -47- (44) (44 ) 200401002 and developed with 0.05% potassium hydroxide aqueous solution, rinsed with ultrapure water for 60 seconds, and then heat-treated in an oven at 230 ° C for 30 minutes to form red, green and blue three-color ribbons Color filter (stripe width 100 μm). The unevenness on the surface of the substrate on which the color filter was formed was measured using a surface roughness meter "α-Stone Patch" (trade name: manufactured by Timcore Corporation) and was 1.0 μm Here, according to the measurement length of 2,000 μηι, the measurement range of 2,000 μιη, the angle, the number of measurement points η = 5 That is, the measurement direction is the short axis direction of the strip line in the red, green, and blue directions, and the long axis of the strip line of the same color of red, red, green, green, blue, and blue. Two directions, and each direction was measured by n = 5 (the total number of η is 10). After the above, the composition for forming a protective film was applied using a spin coater, and then heated at 90 ° on a hot plate. Pre-baked at 5 ° C for 5 minutes, and then heat-treated in an oven at 230 ° C for 60 minutes to form a protective film with a thickness of 2.0 μm from the top of the color filter. The color filter was formed in the same manner as above. There is a substrate on the substrate, and a contact-type film thickness measuring device (2-Styrol (manufactured by Timcore Japan) is used to measure the unevenness on the surface of the protective film. Here, the measurement length is 2,000 μm, the measurement range is 2,000 μm, and the angle is measured. The measurement is performed under the condition that the number of points is η = 5. That is, the measurement direction is made into a strip line of the red, green, and blue directions, and the short-line direction and the same color band shape of the same color of red, red, green, green, and blue. 2 directions of the long axis direction of the line and measure η = 5 for each direction ( The total number of η is 10). Table 1 shows the average ten times of the difference in height (nm) between the highest part and the bottom part of each measurement. If the mean value is 300 nm or less, the flatness is considered to be good. (45) (45) 200401002 Examples 2 to 7 and Comparative Examples 1, 2 The types and amounts of the components of the composition were made as described in Table 1 and used without using propylene glycol monomethyl ether acetate The solvent described in Table 1 was prepared in the same manner as in Example 1 except that the solid content concentration described in Table I was matched. To this composition, a component in which 35 parts by weight of trimellitic anhydride was dissolved in 65 parts by weight of diethylene glycol methyl ethyl ether was added as a component [D] to prepare a composition for forming a protective film. The appearance of the composition prepared here is shown in Table 1. Using the composition for forming a protective film prepared as described above, a protective film was formed in the same manner as in Example 1 and evaluated. The results are shown in Table 1. Here, the added amount of each component in Table 1 is part by weight, and "-" in the table means that no equivalent component is added. In addition, the abbreviations of the [B] component, the [C] component, and the solvent represent the following, respectively. B-1: Silane-modified epoxy resin "Kongfuserang E-202" (trade name, manufactured by Arakawa Chemical Industries, Ltd.) B-2: Silane-modified epoxy resin "Kongfuserang E-201" (Brand name, manufactured by Arakawa Chemical Industry Co., Ltd.) B-3: Silane-modified epoxy resin "Kung Fu Serang E-101" (brand name, manufactured by Arakawa Chemical Industry Co., Ltd.) B-4: Silane modified Epoxy Resin "Kung Fu Serang E-2 1 2" (trade name, manufactured by Arakawa Chemical Industries, Ltd.) -49-(46) (46) 200401002 Cl: Bisphenol A lacquer-type epoxy resin (oil-based Sherborn Box (trade name), trade name: Epicot 157S65) C-2: Bisphenol A type epoxy resin (Oilized Sherlock Boxer trade, trade name: Epicote) 828) S-1: Propylene glycol monomethyl ethyl acetate S-2: Diethylene glycol monomethyl ethyl acetate

-50- 200401002-50- 200401002

一.^ 比較例 CM 1 100 1 1 1 1 in 1 CM ώ 無色透明 00 ⑦ 00 σ> CO 工 寸 卜 CM 卜 τ— 100 o CM 195 T— 100 1 1 1 1 1 LO 1 ώ 無色透明 CD CD σ) σ> CO X ο CM CO τ— 100 o 210 實施例 卜 1 100 1 1 1 s 1 LO t— OJ ώ 無色透明 σ) σ> ⑦ 05 CO 工 CD CO CO CM 100 100 200 CO 100 1 1 j 1 s o Ύ— 1 ώ 無色透明 ⑦ σ» σ> σ> CO X CD T— CO 00 C\i 100 100 190 1〇 1 〇 1 Ο LO » ! 〇 i ώ 無色透明 CD Ο) σ> σ> CO 工 CO CM CO oi 100 100 195 寸 1 100 S I 1 1 1 LO t— CM ώ 無色透明 σ> Ο) ⑦ CO 工 CD 〇 CO c5 o T— 100 180 CO 100 1 1 1 ο m 1 1 o T— ώ 無色透明 σ> σ> σ> σ> CO X CD CvJ CO cvi 100 100 I 200 CsJ 100 1 1 s 1 1 ID 1 C\J ώ 無色透明 σ> ⑦ σ> Ο) CO 工 CD 寸 CO σ> CM 100 100 I 200 T— 100 1 〇 CM 1 1 1 〇 1 ώ 無色透明 σ> Ο) Ο) CO X ΙΟ σ> CM ir> CM 100 | 100 I 190 A-2 ώ CM ώ B-3 I B-4 t— ό C-2 溶媒 固體成份(％) j |[D]成份添加後之外觀 透明性(％) 1耐熱尺寸安定性(％) 抗熱變色性(％) , 鉛筆硬度 23°c P o T— Si〇2 ό 平坦化能(nm) 共聚物 [A] [Β滅份 [c]成份 動態顯微 硬度 密貼性 -51 - (48) (48)200401002 第2組成物之調製及評估 實施例8 對作爲[E]成份而含有上述合成例3所得的共聚物（E-1) 的溶液（相當於共聚物（E-l)lOO重量份（固體成份）的量）中 ，混合作爲[B ]成份之矽烷改性環氧樹脂「孔甫色朗E - 2 0 2 」商品名，荒川化學工業（股）製）20.0重量份，作爲[F]成 份之雙酚A淸漆型環氧樹脂（油化雪爾愛博克斯（股）製，商 品名：埃比可特1 5 7 S 6 5 ) 1 0 · 0重量份，以及作爲表面活性 劑之SH-28PA(東麗矽酮（股）製）〇.1重量份，按固體成份濃 度能成爲20.0重量份之方式添加丙二醇一甲基醚乙酸酯之 後，使用孔徑0.5 μπι之米利波亞過濾器過濾以調製第2組成 物。 在此所調製的組成物之外觀，爲無色透明者。 保護膜之形成及評估 將如上述方式所調製的組成物，使用旋塗器塗佈在 S i Ο 2浸漬玻璃基板上後，在加熱板上在8 0 °C下預焙5分鐘 以形成塗膜，再在烤爐中在2 3 0 °C下加熱處理6 0分鐘以形 成保護膜。 又，在按與實施例1所記載之方法同樣方式形成有濾 色器的基板上，按與上述方法形成保護膜。 使用具有此等保護膜的基板，與實施例1同樣方式實 施評估。表2中表示其結果。 -52- (49) (49)200401002 實施例9、1 0以及比較例3、4 將組成物之各成份之種類及量作成與表2中所記載者 同樣方式’除不用丙一 _ —甲基酸乙酸酯而使用表2中記 載之溶媒以外’其餘則按與實施例8同樣方式調製組成物 〇 將在此所調製的組成物外觀，表示在表2中。 使用如上述方式所調製的組成物，按與實施例8同樣 方式形成保護膜並加以評估。表2中表示其結果。 第3組成物之調製及評估 實施例Π 對作爲[E ]成份而含有上述合成例4所得的共聚物（E - 2 ) 的溶液（相當於共聚物（E -1 ) 1 0 0重量份（固體成份）的量）中 ，混合作爲[B]成份之矽烷改性環氧樹脂「孔甫色朗E-202 」（商品名’荒川化學工業（股）製）20.0重量份，作爲[F]成 份之三羥甲基丙烷參（3-甲基-3-氧雜環丁烷基甲基）醚15.0 重量份，作爲[G]成份之苄基-2-甲基-4-羥基苯基锍六氟銻 酸酯2重量份，以及作爲表面活性劑之S Η - 2 8 P A (東麗矽酮（ 股）製）0.1重量份，按固體成份濃度能成爲20.0重量％之方 式添加乙二醇二甲基醚之後，使用孔徑〇.5μιη之米利波亞 過濾器過濾以調製第3組成物。 將在此所調製的組成物之外觀，表示在表2中。 使用如上述方式所調製的組成物，按與實施例8同樣 -53- (50) (50)200401002 方式形成保護膜並加以評估。表2中表示其結果。 實施例1 2 除將組成物之各成份之種類及量作成與表2中所記載 者同樣方式者以外，其餘則按與同樣方式以調製組成物。 將在此所調製的組成物外觀，表示在表2中。 將上述組成物溶液，使用旋塗器塗佈在Si 〇2浸漬玻璃 基板上後，在加熱板上在80°C上預焙5分鐘以形成塗膜。 接著，對所形成的塗膜，使用曝光機Canon(佳能 )P L A 5 0 1 F (佳能（股）製），將 g h i 線（波長 4 3 6 n m、4 0 5 n m、 365nm之強度比=2.7 : 2.5 : 4.8)按1線換算以2,OOOJ/m2之曝 光量照射。再在烤爐中在230 °C下加熱60分鐘，以形成保 護膜。 又，在按與實施例1所記載之方法形成有濾色器的基 板上，與上述方式同樣實施塗佈、預焙、曝光以及加熱之 各過程以形成保護膜。 使用具有此等保護膜的基板’按與實施例6同樣方式 加以評估。表2中表示評估結果。 實施例1 3 除在實施例1 2中將曝光量改變爲30(U/ni2以外其餘則 作成同樣方式，獲得如表2所示結果。 在此，表2中，各成份之添加量係重量份’而表中之 「-」表示未添加有所相當的成份之意。 又，[B ]成份、[F ]成份、[G ]成份’以及溶媒之簡稱’ -54- (51) (51)200401002 分別表示如下所示者。 B-1 ··矽烷改性環氧樹脂「孔甫色朗E-202」（商品名 ，荒川化學工業（股）製） B - 2 :矽烷改性環氧樹脂「孔甫色朗E - 2 0 1」（商品名 ，荒川化學工業（股）製） B-3 :矽烷改性環氧樹脂「孔甫色朗E-101」（商品名 ，荒川化學工業（股）製） F-1 ··雙酚A淸漆型環氧樹脂（油化雪爾愛博克斯（股） φ 製，商品名：埃比可特1 5 7 S 6 5 ) F-2 :三羥甲基丙烷參（3-甲基-3-氧雜環丁烷基甲基） 醚 G-1:苄基-2-甲基-4-羥基苯基甲基锍六氟銻酸酯 G-2:三苯基銃三氟甲烷磺酸酯 S-3 :丙二醇一甲基醚乙酸醋 S-4:二乙二醇二甲基酸 痲 -55- 200401002I. ^ Comparative example CM 1 100 1 1 1 1 in 1 CM colorless and transparent 00 ⑦ 00 σ > CO CM inch CM τ— 100 o CM 195 T— 100 1 1 1 1 1 LO 1 free colorless transparent CD CD σ) σ > CO X ο CM CO τ— 100 o 210 Example 1 1 100 1 1 1 s 1 LO t— OJ (colorless and transparent σ) σ > ⑦ 05 CO Engineering CD CO CO CM 100 100 200 CO 100 1 1 j 1 so Ύ— 1 FREE colorless and transparent ⑦ »σ > σ > CO X CD T— CO 00 C \ i 100 100 190 1〇1 〇1 〇 LO»! 〇i FREE colorless and transparent CD 〇) σ > σ > CO Engineering CO CM CO oi 100 100 195 inch 1 100 SI 1 1 1 LO t— CM colorless and transparent σ > 〇) ⑦ CO engineering CD 〇CO c5 o T— 100 180 CO 100 1 1 1 ο m 1 1 o T — FREE colorless transparent σ > σ > σ > σ > CO X CD CvJ CO cvi 100 100 I 200 CsJ 100 1 1 s 1 1 ID 1 C \ J FREE colorless transparent σ > ⑦ σ > 〇) CO engineering CD inch CO σ > CM 100 100 I 200 T— 100 1 〇CM 1 1 1 〇1 free colorless σ > 〇) 〇) CO X ΙΟ σ > CM ir > CM 100 | 100 I 190 A-2 free CM free B-3 I B-4 t— ό C-2 Solvent solids ( ) j | [D] Appearance transparency (%) after addition of components 1 Heat resistance dimensional stability (%) Thermal discoloration resistance (%), pencil hardness 23 ° c P o T— Si〇2 ⑥ flattening energy (nm ) Copolymer [A] [B] [c] Component Dynamic Micro Hardness Adhesiveness -51-(48) (48) 200401002 Preparation and Evaluation of the Second Composition Example 8 Contained as [E] component In the solution of the copolymer (E-1) obtained in the above Synthesis Example 3 (equivalent to 100 parts by weight of the copolymer (El) (solid content)), the silane-modified epoxy resin as the component [B] was mixed. "Fu Serang E-2 0 2" "Brand name, 20.0 parts by weight of Arakawa Chemical Industry Co., Ltd.", bisphenol A lacquer-type epoxy resin (Oilized Shire Abox) System, trade name: Epicot 1 5 7 S 6 5) 1 0 · 0 parts by weight, and SH-28PA (made by Toray Silicone Co., Ltd.) as a surfactant, 0.1 parts by weight, based on solids After the propylene glycol monomethyl ether acetate was added so that the component concentration could be 20.0 parts by weight, it was filtered using a Millipore filter with a pore size of 0.5 μm to prepare a second composition. The appearance of the composition prepared here is colorless and transparent. Formation and Evaluation of the Protective Film The composition prepared as described above was applied on a Si 02-impregnated glass substrate using a spin coater, and pre-baked at 80 ° C for 5 minutes on a hot plate to form a coating. Film, and then heat-treated in an oven at 230 ° C for 60 minutes to form a protective film. A protective film was formed on the substrate on which the color filters were formed in the same manner as in the method described in Example 1. Using a substrate having such a protective film, evaluation was performed in the same manner as in Example 1. The results are shown in Table 2. -52- (49) (49) 200401002 Examples 9, 10 and Comparative Examples 3 and 4 The types and amounts of each component of the composition were made in the same manner as described in Table 2 'except without the use of C1 — —A The composition was prepared in the same manner as in Example 8 except that the solvent described in Table 2 was used except for the acetic acid acetate. The appearance of the composition prepared here is shown in Table 2. Using the composition prepared as described above, a protective film was formed and evaluated in the same manner as in Example 8. The results are shown in Table 2. Example 3 for Preparation and Evaluation of the Third Composition To a solution containing the copolymer (E-2) obtained in the above Synthesis Example 4 as the [E] component (corresponding to the copolymer (E -1)) 100 parts by weight ( (Solid content), 20.0 parts by weight of a silane-modified epoxy resin "Confuserang E-202" (trade name: Arakawa Chemical Industry Co., Ltd.), which is a component [B], is [F] 15.0 parts by weight of trimethylolpropane ginseng (3-methyl-3-oxetanylmethyl) ether as the benzyl-2-methyl-4-hydroxyphenyl hydrazone as the [G] component 2 parts by weight of hexafluoroantimonate, and 0.1 part by weight of S Η-2 8 PA (manufactured by Toray Silicone Co., Ltd.) as a surfactant, and ethylene glycol is added so that the solid content concentration becomes 20.0% by weight After the dimethyl ether, it was filtered using a Millipore filter having a pore size of 0.5 μm to prepare a third composition. The appearance of the composition prepared here is shown in Table 2. Using the composition prepared as described above, a protective film was formed and evaluated in the same manner as in Example 8 -53- (50) (50) 200401002. The results are shown in Table 2. Example 1 2 A composition was prepared in the same manner except that the types and amounts of the components of the composition were prepared in the same manner as described in Table 2. The external appearance of the composition prepared here is shown in Table 2. The composition solution was applied on a SiO 2 impregnated glass substrate using a spin coater, and then prebaked on a hot plate at 80 ° C. for 5 minutes to form a coating film. Next, using the exposure machine Canon PLA 5 0 1 F (manufactured by Canon Inc.), the intensity ratio of the ghi line (wavelength 4 3 6 nm, 40 5 nm, 365 nm = 2.7) : 2.5: 4.8) It is irradiated with an exposure of 2,000J / m2 on a 1-line basis. It was then heated in an oven at 230 ° C for 60 minutes to form a protective film. In addition, on the substrate on which the color filters were formed in the same manner as described in Example 1, the processes of coating, prebaking, exposure, and heating were performed in the same manner as described above to form a protective film. Evaluation was performed in the same manner as in Example 6 using the substrate 'having such a protective film. Table 2 shows the evaluation results. Example 1 3 Except that the exposure amount was changed to 30 (U / ni2) in Example 12 and the same manner was performed, and the results shown in Table 2 were obtained. Here, in Table 2, the added amount of each component is weight "'" In the table means that some equivalent ingredients have not been added. Also, [B] ingredient, [F] ingredient, [G] ingredient' and the abbreviation of solvent '-54- (51) (51 ) 200401002 Represents the following: B-1 ··· Silane-modified epoxy resin "Kong Fusele E-202" (trade name, manufactured by Arakawa Chemical Industry Co., Ltd.) B-2: Silane-modified epoxy resin Resin "Kung Fu Serang E-2 0 1" (trade name, manufactured by Arakawa Chemical Industries, Ltd.) B-3: Silane-modified epoxy resin "Kung Fu Serang E-101" (trade name, Arakawa Chemical Industries) (Manufactured by the company) F-1 ·· Bisphenol A lacquer-type epoxy resin (manufactured by Shire Approx (stock) φ, trade name: Epicot 1 5 7 S 6 5) F-2 : Trimethylolpropane (3-methyl-3-oxetanylmethyl) ether G-1: benzyl-2-methyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate G-2: Triphenylsulfonium trifluoromethanesulfonate S-3: Propylene glycol monomethyl Vinegar ether acetate S-4: diethylene glycol dimethacrylate acid Ma -55-200401002

(\|嗽 比較例 1 寸 1 .......................................1.....0.Q.................................... i 1 1 LO i 1 1 ώ ο OJ 無色透明 00 Ο) CD σ> C\J 工 00 CM ο τ— 100 o T— I 210 I CO 100 1 I i 1 Ο 1 1 1 CO ώ ο eg 無色透明 CD σ> CD σ) CM 工 ⑦ C\J CM CM 100 o 210 實施例 CO T— 100 i I § 1 LO 1 1 C\J Z ο CM 無色透明 CD Ο) Ο) φ CM 工 LO 〇 CO LO CM loo I 100 | 200 I CM T— 100 1 1 Ο ΙΟ 1 tn 1 1 OJ Z 〇 C\J 無色透明 CD σ» φ σ> CM 工 CD σ CO ir> CM ίο。 I 100 | 200 I τ— 1 Γιοο 1 o CM 1 1 1 in CM I CO ώ ο C\J 無色透明 σ> 03 σ> (M X CM CO 卜 CNJ 〇 T— 100 | 200 I 〇 1 100 1 1 ο LO 1 LO 1 < Z ο C\J 無色透明 σ> Ο) CM 工 CD CTl CM ID C\J 100 I 丨 100 I 205 05 1 I ....1001 1 s 1 1 i 1 CO ώ 無色透明 σ> Ο) σ> σ> CM 工 1〇 T— CO CD CM [100 I 100 220 00 100 1 1 1 o 1 1 1 CO ώ 無色透明 Ο) σ> σ> Ο) CM 工 CD 寸 CO O) CM 100 100 I__ 210 I UJ CM LLJ ώ CM ώ Β-3 T— uL c\i li ό G-2 溶媒 固體成份(％) 所調製的組成物之外觀 1透明性(％) ι 耐熱尺寸安定性(％) 抗熱變色性(％) 鉛筆硬度 23°c CJ c o τ— Si〇2 ό |平坦化能(nm) I 共聚物[E] 同成份 [F]成份 [G]成份 動態顯微硬度 密貼性 -56- (53) (53)200401002 如上所述，如使用本發明，則可製得除能滿足作爲保 護膜而在來即需要具備的各種特性’具體而言’密貼性、 表面硬度、透明性、耐熱尺寸安定性、抗熱變色性、抗賤 鍍性之外’在施加有熱的狀態下仍不會因荷重而凹陷，並 且可適用爲使底子基板上所形成的濾色器之高低差平坦化 的性能優異的光學裝置用保護膜形成材料的組成物，以及 由此所形成的保護膜。(\ | Comparative example 1 inch 1 ........................ 1. ..0.Q .............. i 1 1 LO i 1 1 ώ ο OJ Colorless and transparent 00 Ο) CD σ > C \ J 工 00 CM ο τ— 100 o T— I 210 I CO 100 1 I i 1 Ο 1 1 1 CO Royalty Free ο eg Colorless and transparent CD σ > CD σ) CM Industrial C \ J CM CM 100 o 210 Example CO T-100 i I § 1 LO 1 1 C \ JZ ο CM Colorless and transparent CD 〇) 〇) φ CM Industrial LO 〇CO LO CM loo I 100 | 200 I CM T— 100 1 1 Ο ΙΟ 1 tn 1 1 OJ Z 〇C \ J colorless and transparent CD σ »φ σ > CM engineering CD σ CO ir & CM ο. I 100 | 200 I τ— 1 Γιοο 1 o CM 1 1 1 in CM I CO ο ο C \ J colorless and transparent σ > 03 σ > (MX CM CO bu CNJ 〇T— 100 | 200 I 〇1 100 1 1 ο LO 1 LO 1 < Z ο C \ J colorless and transparentσ > 〇) CM CDCDl CM ID C \ J 100 I 丨 100 I 205 05 1 I .... 1001 1 s 1 1 i 1 CO σ > Ο) σ > σ > CM Engineering 1〇T— CO CD CM [100 I 100 220 00 100 1 1 1 o 1 1 1 CO free colorless and transparent 0) σ > σ > 〇) CM Engineering CD inch CO O) CM 100 100 I__ 210 I UJ CM LLJ FREE CM FREE B-3 T— uL c \ i li ό G-2 Solvent solid content (%) Modified composition appearance 1 Transparency (%) ι Heat-resistant dimensional stability (%) Thermal discoloration resistance (%) Pencil hardness 23 ° c CJ co τ—Si〇2 ό | Planarization energy (nm) I Copolymer [E] Same component [F] Component [G] Component Dynamic microhardness Adhesiveness -56- (53) (53) 200401002 As described above, if the present invention is used, various properties can be obtained that can satisfy the various characteristics that need to be provided as a protective film. Surface hardness, transparency, heat resistance, dimensional stability, resistance In addition to discoloration and resistance to low-level plating, it can be applied to an optical device that has excellent performance in flattening the level difference of a color filter formed on a base substrate without being dented by a load even when heat is applied. The composition of the material is formed using a protective film, and the protective film formed thereby.

-57--57-

Claims (1)

(1) (1)200401002 拾、申請專利範圍 1. 一種樹脂組成物，其特徵爲：含有 [A] (al)含有環氧基之不飽和化合物，和（a2)與（al)成 份不相同的烯烴系不飽和化合物之共聚物’ [B] (bl)含有羥基之環氧樹脂與（b2)烷氧基矽烷的反應 物，以及 [C] 與[A]成份及[B]成份不相同的陽離子聚合性化合 物。 鲁 2. 如申請專利範圍第1項所記載之樹脂組成物，其中 再含有[D ]硬化劑。 3. —種樹脂組成物，其特徵爲：含有 [E] (el)不飽和羧酸及/或不飽和羧酸酐，（e2)含有環 氧基之不飽和化合物，以及（e3)與（el)成份及（e 2)成份不 相同的烯烴系不飽和化合物之共聚物， [B](bl)含有羥基之環氧樹脂與（b2)烷氧基矽烷的反應 物’以及 [F] 與[B]成份及[E]成份不相同的陽離子聚合性化合物 〇 4 _如申請專利範圍第3項所記載之樹脂組成物，其中 再含有因熱及/或放射線而產生酸的化合物。 5 . —種保護膜之形成方法’其特徵爲：將申請專利範 圍第1項所記載之[A]成份、[B]成份、[C]成份以及[〇]固化 劑加以混合，並將其混合物塗佈在基板上，接著，藉由熱 及/或放射線加以處理。 -58 - (2) (2)200401002 6. —種保護膜之形成方法，其特徵爲：將申請專利範 圍第3項所記載之[E]成份、[B]成份、[F]成份以及[G]因熱 及/或放射線而將產生酸的化合物加以混合，並將其混合 物塗佈在基板上，接著，藉由熱及/或放射線而加以處理 7 . —種保護膜，係由申請專利範圍第2項之第4項之任 項所記載之樹脂組成物所形成者。(1) (1) 200401002, application for patent scope 1. A resin composition characterized by containing [A] (al) unsaturated compounds containing epoxy groups, and (a2) and (al) components are not the same Copolymer of olefinic unsaturated compounds' [B] (bl) A reaction product of a hydroxyl-containing epoxy resin and (b2) an alkoxysilane, and the components [C] are different from the components [A] and [B] Cationically polymerizable compound. Lu 2. The resin composition as described in item 1 of the scope of patent application, which further contains a [D] hardener. 3. A resin composition characterized by containing [E] (el) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (e2) an unsaturated compound containing an epoxy group, and (e3) and (el ) And (e 2) copolymers of olefinic unsaturated compounds having different components, [B] (bl) a reactant of a hydroxyl-containing epoxy resin and (b2) an alkoxysilane, and [F] and [ B] and cationically polymerizable compounds having different components [E]. The resin composition as described in item 3 of the scope of patent application, which further contains a compound that generates an acid due to heat and / or radiation. 5. —Method for forming a protective film ', characterized in that: [A] component, [B] component, [C] component and [〇] curing agent described in item 1 of the scope of patent application are mixed and mixed The mixture is coated on a substrate and then processed by heat and / or radiation. -58-(2) (2) 200401002 6. A method for forming a protective film, characterized in that the [E] component, [B] component, [F] component and [ G] Compounds that generate acid due to heat and / or radiation are mixed, and the mixture is coated on a substrate, and then processed by heat and / or radiation 7. A protective film, which is applied for by a patent Formed by the resin composition described in any one of the second item in the second item in the range. -59- 200401002 柒、（一）本案指定代表圖爲：無 (二)本代表圖之元件代表符號簡單說明：無-59- 200401002 柒 、 (1) The designated representative figure in this case is: None (II) The representative symbols of the components in this representative figure are simply explained: None 捌、本案若有化學式時，請揭示最能顯示發明特徵之化學式：無捌 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 4—4—
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