TW200835744A - Curable resin composition, process for forming a color filter protective film and color filter protective film - Google Patents

Curable resin composition, process for forming a color filter protective film and color filter protective film Download PDF

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TW200835744A
TW200835744A TW096142237A TW96142237A TW200835744A TW 200835744 A TW200835744 A TW 200835744A TW 096142237 A TW096142237 A TW 096142237A TW 96142237 A TW96142237 A TW 96142237A TW 200835744 A TW200835744 A TW 200835744A
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acrylate
meth
methyl
weight
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TW096142237A
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Chinese (zh)
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Masayasu Fujioka
Junji Yoshizawa
Jiro Ueda
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Jsr Corp
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    • 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
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

To provide a composition forming a cured film of high surface smoothness even on a substrate of lower surface smoothness, and applicable preferably to form an optical device protective film having high transparency and surface hardness, and excellent resistance such as heat and pressure resistance, acid resistance, alkali resistance and sputter resistance, as well as having good storage stability as the composition. This curable resin composition comprises a copolymer composed of a polymerization unit derived from a polymerizable unsaturated compound having at least one structure selected from the group consisting of a carboxylic acid acetal ester structure, a carboxylic acid ketal ester structure, a carboxylic acid 1-alkyl cycloalkyl ester structure and a carboxylic acid t-butyl ester structure, a polymerization unit derived from a polymerizable unsaturated compound having an oxetanyl group, and a polymerization unit derived from a polymerizable unsaturated compound excepting the two polymerization units.

Description

200835744 九、發明說明 【發明所屬之技術領域】 本發明係關於硬化性樹脂組成物、其組成物所成的彩 色濾光片之保護膜的方法及該保護膜。更詳細爲作爲形成 使用於液晶顯示元件（LCD )用彩色濾光片及電荷結合元 件（CCD )用彩色濾光片的保護膜的材料之較佳組成物' 使其組成物的保護膜之形成方法以及自該組成物所形成之 保護膜。 【先前技術】 LCD或C CD等放射線裝置於該製造步驟中，進行藉 由溶劑、酸或鹼溶液等之顯示元件的浸漬處理，且藉由濺 射形成配線電極層時，元件表面上局部地暴露於高溫下。 因此，欲防止如此處理所造成的元件劣化或損傷，對於這 些處理，必須將具有耐性之薄膜所成的保護膜設置於元件 表面上。 如此保護膜係爲，對於必須形成該保護膜之基體或下 層、且於保護膜上所形成之層的密著性被要求必須爲較高 者、膜本身被要求爲平滑且強靭者、被要求爲具有透明性 者、耐熱性及耐光性被要求較高者、經過長期間被要求亦 不會產生著色、黃變、白化等變質者、耐水性、耐溶劑性 、耐酸性及耐鹼性被要求爲優良者等性能。作爲使用於形 成可滿足彼等特性的保護膜之材料，例如已知有含具有縮 水甘油基的聚合物之熱硬化性組成物（特開平5 - 7 8 4 5 3號 200835744 公報及特開20(Π-9 1 732號公報參照）。 又，將如此保護膜作爲彩色液晶顯不裝置或電荷結合 元件之彩色濾光片的保護膜使用時，一般要求於底基板上 所形成的彩色濾光片所產生的段差必須可平坦化。 且’彩色液晶顯不裝置中，例如STN ( Super Twisted Nematic)方式或 TFT (Thin Film Transi ster )方式之彩 色液晶顯示元件中，欲將液晶層之晶胞間隙保持於均一狀 態下，將珠子狀的間隔物散佈於保護膜下再貼合面板。其 後藉由熱壓著封閉材而密封液晶胞，此時的熱或壓力會使 珠子存在部分之保護膜成凹陷現象，使得晶胞間隙雜亂而 成爲問題。 特別於製造STN方式的彩色液晶顯示元件時，彩色 濾光片與對向基板之貼合精度必須於極嚴密下進行，保護 膜被要求必須具有極高度段差之平坦化性能及耐熱耐壓性 能。 又，近年來藉由濺射於彩色濾光片之保護膜上進行配 線電極（銦錫氧化物：ITO、或銦鋅氧化物：IZO )的成 膜，另外強酸或強鹼等形成ITO或IZO之圖型的方式亦 被採用。藉此’彩色濾光片保護膜於濺射時其表面局部暴 露於高溫中’並經由數種藥品處理。因此，對於這些處理 對抗、及藥品處理時ITO或IZO不會自保護膜上剝落的 與配線電極之密著性亦被要求。 如此保護膜之形成因具有可由簡易方法形成硬度優良 的保護膜之優點，故可方便使用熱硬化性組成物，作爲可 -6 - 200835744 表現如上述各特性之保護膜樹脂組成物，具有形成強固交 聯之反應性佳的交聯基或觸媒，故有著組成物本身的保存 期間非常短之問題，其處理上非常困難。即，組成物的塗 佈性能本身不僅會經時性地惡化，且塗佈機的頻繁性維護 ^ 、洗淨等成爲必要步驟，於操作上亦爲繁雜。 ~ 滿足作爲透明性等保護膜之一般被要求的性能下，可 簡易地形成滿足上述各性能的保護膜，且作爲組成物之保 φ 存安定性優良的材料係爲未知的技術。 又，特開平4-218561號公報中雖揭示塗料、墨水、 接著劑、成形品所使用的含有潛在化羧基化合物之熱硬化 性組成物，對於彩色濾光片之保護膜則完全未揭示。。 【發明內容】 本發明係爲基於如上述情事所得者，其目的爲，提供 即使爲表面平坦性較低的基體，該基體上可形成平坦性高 •) 之硬化膜，且可適用於形成透明性及表面硬度高、耐熱耐 壓性、耐酸性、耐鹼性、耐濺射性等各種耐性優良的光裝 置用保護膜，且作爲組成物之保存安定性優良的組成物， ^ 使用上述組成物之保護膜的形成方法、及藉由上述組成物 • 所形成之保護膜。 本發明的另一其他目的及利點可由以下說明得知。 所謂本發明之上述目的，第一藉由含有（a-1 )來自 具有至少1種選自羧酸的縮醛酯結構、羧酸的酮縮醇酯結 構' 羧酸的1-烷基環烷基酯結構及羧酸的t-丁基酯結構所 200835744 成群之結構的聚合性不飽和化合物之聚合單位、（a-2 ) 來自具有氧雜環丁烷基之聚合性不飽和化合物的聚合單位 及（a-3 )來自上述（a-l ) 、（ a-2 )的聚合單位以外的聚 合性不飽和化合物之聚合單位所成的共聚合物（以下稱爲 ~ 共聚合物（A ))爲特徴的硬化性樹脂組成物而達成。 ^ 本發明的上述目的，第二藉由以共聚合物（A )的凝 膠滲透層析儀所測定之聚苯乙烯換算數平均分子量爲 φ ^ 1，〇〇〇〜5〇,〇〇〇的範圍之上述硬化性樹脂組成物而達成。 本發明的上述目的，第三藉由彩色濾光片之保護膜形 成用之上述硬化性樹脂組成物而達成。 本發明的上述目的，第四藉由含有將上述硬化性樹脂 組成物塗佈於基板上形成塗膜的步驟、及於該塗膜以放射 線照射之步驟者爲特徴之彩色濾光片的保護膜形成方法而 達成。 本發明的上述目的，第五藉由將上述硬化性樹脂組成 # ) 物塗佈於基板上形成塗膜之步驟、及加熱該塗膜之步驟者 爲特徴的彩色濾光片之保護膜的形成方法而達成。 本發明的上述目的，第六藉由由上述硬化性樹脂組成 ‘ 物所形成的彩色濾光片之保護膜而達成。 實施發明的最佳形態 以下對本發明之樹脂組成物的各成分做說明。 硬化性樹脂組成物 200835744 本發明的硬化性樹脂組成物爲含有（a-1 )來自具有 至少1種選自羧酸的縮醛酯結構、羧酸的酮縮醇酯結構、 羧酸的1 -烷基環烷基酯結構及羧酸的t-丁基酯結構所成群 之結構的聚合性不飽和化合物之聚合單位、（a-2 )來自 具有氧雜環丁烷基之聚合性不飽和化合物的聚合單位、及 (a-3 )來自上述（a-1 ) 、（ a-2)的聚合單位以外之聚合 性不飽和化合物的聚合單位所成之共聚合物（A )。該共 聚合物（A )較佳爲以凝膠滲透層析儀測定之聚苯乙烯換 算數平均分子量爲1，000〜50,000之範圍。 作爲聚合性不飽和化合物（a · 1 )，僅具有竣酸的縮 醛酯結構、羧酸的酮縮醇酯結構、羧酸的1 -烷基環烷基 酯結構及羧酸的t-丁基酯結構者即可，並無特別限定。羧 酸的縮醛酯結構可由下述式（1 )表示。 *-C——Ο——CH—Ο-Rh (1)[Technical Field] The present invention relates to a method for protecting a protective film of a color filter formed of a curable resin composition and a composition thereof, and a protective film. More specifically, it is a preferable composition of 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-bonding element (CCD), and a protective film is formed. A method and a protective film formed from the composition. [Prior Art] In the manufacturing step, a radiation device such as an LCD or a C CD performs immersion treatment by a display element such as a solvent, an acid or an alkali solution, and when a wiring electrode layer is formed by sputtering, the surface of the element is partially Exposure to high temperatures. Therefore, in order to prevent deterioration or damage of components caused by such treatment, it is necessary for these treatments to provide a protective film made of a film having resistance on the surface of the member. Such a protective film is required to have a higher adhesion to a substrate or a lower layer in which the protective film must be formed and a layer formed on the protective film, and the film itself is required to be smooth and strong, and is required to be required. For those who have transparency, heat resistance and light resistance are required, and they are required to be colored, yellowed, whitened, etc., water resistance, solvent resistance, acid resistance and alkali resistance after being used for a long period of time. Requirements are excellent and other performance. As a material for forming a protective film that satisfies the characteristics thereof, for example, a thermosetting composition containing a polymer having a glycidyl group is known (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. (Refer to Π-9 1 732). When such a protective film is used as a protective film for a color liquid crystal display device or a color filter of a charge-bonding element, color filter formed on the base substrate is generally required. The step difference generated by the sheet must be flattenable. And in the color liquid crystal display device, for example, in the STN (Super Twisted Nematic) mode or the TFT (Thin Film Transister) color liquid crystal display device, the cell of the liquid crystal layer is to be used. The gap is kept in a uniform state, and the bead-shaped spacer is spread under the protective film and then attached to the panel. Thereafter, the liquid crystal cell is sealed by heat pressing the sealing material, and the heat or pressure at this time causes partial protection of the bead. The film is dented, which makes the cell gap disorder a problem. Especially when manufacturing the STN type color liquid crystal display device, the bonding precision between the color filter and the opposite substrate must be The protective film is required to have a flatness of a high degree of difference and a heat and pressure resistance. In recent years, a wiring electrode (indium tin oxide: ITO) is deposited on a protective film by sputtering on a color filter. Or indium zinc oxide: IZO), and a pattern of ITO or IZO formed by strong acid or strong alkali, etc., whereby the color filter protective film is partially exposed to the surface during sputtering. In the high temperature, it is treated by several kinds of drugs. Therefore, the adhesion of the ITO or IZO to the wiring electrode which is not peeled off from the protective film during the treatment and the treatment of the drug is also required. Since the thermosetting composition can be easily formed by a simple method, it is convenient to use a thermosetting composition, and it is a protective film resin composition which exhibits the above characteristics as the above-mentioned, and has excellent reactivity for forming strong cross-linking. Cross-linking group or catalyst, so there is a problem that the composition itself is very short during storage, and it is very difficult to handle. That is, the coating performance of the composition itself is not only time-dependent. The deterioration of the coater and the frequent maintenance of the coater, washing, etc. are necessary steps, and the operation is also complicated. ~ The performance that satisfies the above properties can be easily formed by satisfying the generally required performance as a protective film such as transparency. The protective film is a material which is excellent in stability and stability as a composition. The material contained in the paint, the ink, the adhesive, and the molded article is disclosed in Japanese Laid-Open Patent Publication No. Hei-4-218561. The thermosetting composition of the carboxy compound is not disclosed at all for the protective film of the color filter. [Invention] The present invention is based on the above-mentioned circumstances, and its object is to provide even low surface flatness. The base material can form a cured film having high flatness and high hardness, and can be suitably used for forming various kinds of excellent resistances such as transparency, surface hardness, heat resistance and pressure resistance, acid resistance, alkali resistance, and sputtering resistance. A protective film for an optical device, and a composition excellent in storage stability of the composition, a method for forming a protective film using the above composition, and a composition comprising the above composition The protective film formed. Still other objects and advantages of the present invention will be apparent from the following description. The above object of the present invention is first, by containing (a-1) a 1-alkylcycloalkane derived from a ketal ester structure carboxylic acid having at least one acetal ester structure selected from carboxylic acids, a carboxylic acid The structure of a base ester and the t-butyl ester structure of a carboxylic acid. 200835744 A polymerization unit of a polymerizable unsaturated compound having a structure of a group, (a-2) polymerization of a polymerizable unsaturated compound having an oxetanyl group The unit (a-3) is a copolymer (hereinafter referred to as "copolymer (A))) derived from a polymerization unit of a polymerizable unsaturated compound other than the polymerization unit of the above (al) or (a-2). It is achieved by a special curable resin composition. ^ The above object of the present invention, the second average molecular weight by polystyrene conversion measured by a gel permeation chromatograph of the copolymer (A) is φ ^ 1, 〇〇〇 〜 5 〇, 〇〇〇 Achieved in the above range of the curable resin composition. The above object of the present invention is achieved by the formation of the above-mentioned curable resin composition for a protective film of a color filter. According to a fourth aspect of the present invention, there is provided a protective film comprising a step of forming a coating film by applying the curable resin composition onto a substrate, and a color filter comprising the step of irradiating the coating film with radiation. The method of formation is achieved. According to the above object of the present invention, the fifth step of forming the coating film by applying the curable resin composition on the substrate, and forming the protective film of the color filter which is the step of heating the coating film The method is achieved. According to the above object of the present invention, the sixth object is achieved by the protective film of the color filter formed of the curable resin. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the resin composition of the present invention will be described. Curable resin composition 200835744 The curable resin composition of the present invention contains (a-1) a ketal ester structure having at least one carboxylic acid-containing acetal ester structure, a carboxylic acid, and a carboxylic acid. a polymerization unit of a polymerizable unsaturated compound having a structure in which an alkylcycloalkyl ester structure and a t-butyl ester structure of a carboxylic acid are grouped, and (a-2) is derived from a polymerizable unsaturated group having an oxetanyl group. A polymerization unit of the compound and (a-3) a copolymer (A) derived from a polymerization unit of a polymerizable unsaturated compound other than the polymerization unit of the above (a-1) and (a-2). The copolymer (A) is preferably in the range of 1,000 to 50,000 in terms of a polystyrene conversion average molecular weight measured by a gel permeation chromatography. The polymerizable unsaturated compound (a · 1 ) has only an acetal structure of citric acid, a ketal structure of a carboxylic acid, a 1-alkylcycloalkyl structure of a carboxylic acid, and a t-butyl group of a carboxylic acid. The base ester structure is not particularly limited. The acetal structure of the carboxylic acid can be represented by the following formula (1). *-C——Ο——CH—Ο-Rh (1)

II I 〇 R! 〔式（1)中，R!彼此獨立表示碳數1〜20之烷基、碳數 3〜20之脂環式基或碳數6〜20之芳香族烴基、或各Rl 彼此結合形成環。又，（* )表示結合鍵。〕 作爲與羧基結合形成羧酸的縮醛酯結構之基（前述式 (1 )中的-OCH ( Ri ) OR!)，例如可舉出！—甲氧基乙 氧基、1 一乙氧基乙氧基、1— η—丙氧基乙氧基、1 一 i — 丙氧基乙氧基、1 一 η-丁氧基乙氧基、1— i 一丁氧基乙氧 基、1— sec— 丁氧基乙氧基、1 一 t — 丁氧基乙氧基、1一 -9- 200835744 環戊氧基乙氧基、1-環己氧基乙氧基、1 一降冰片氧基乙 氧基、1 —冰片氧基乙氧基、1 一苯氧基乙氧基、1 一 （1 一 萘氧基）乙氧基、1-苯甲氧基乙氧基、1 一苯乙氧基乙氧 基、（環己基）（甲氧基）甲氧基、（環己基）（乙氧基 )甲氧基、（環己基）（η—丙氧基）甲氧基、（環己基 )(i 一丙氧基）甲氧基、（環己基）（環己氧基）甲氧 基、（環己基）（苯氧基）甲氧基、（環己基）（苯甲氧 基）甲氧基、（苯基）（甲氧基）甲氧基、（苯基）（乙 氧基）甲氧基、（苯基）（η-丙氧基）甲氧基、（苯基 )(i_丙氧基）甲氧基、（苯基）（環己氧基）甲氧基 、（苯基）（苯氧基）甲氧基、（苯基）（苯甲氧基）甲1 氧基、（苯甲基）（甲氧基）甲氧基、（苯甲基）（乙氧 基）甲氧基、（苯甲基）（η—丙氧基）甲氧基、（苯甲 基）（i 一丙氧基）甲氧基、（苯甲基）（環己氧基）甲 氧基、（苯甲基）（苯氧基）甲氧基、（苯甲基）（苯甲 氧基）甲氧基、2—四氫呋喃氧基、2-四氫舭喃氧基等。 其中較佳者可舉出1 -乙氧基乙氧基、1 一環己氧基 乙氧基、2—四氫吡喃氧基、1一 η —丙氧基乙氧基、2—四 氫呋喃氧基。 羧酸的酮縮醇酯結構可由下述式（2 )表示。 r2 I 氺 —C— I I —C— I I 〇 I r2 〔式（2 )中，R2彼此獨立表示碳數1〜20之烷基、碳數 -10- 200835744 3〜20之脂環式基或碳數6〜20之芳香族烴基，（* )表 示結合鍵。〕 作爲與羧基結合形成羧酸的酮縮醇酯結構之基（前述 式（2 )中的-OC(R2)2OR2 )，例如可舉出1 —甲基一1 — 甲氧基乙氧基、1—甲基一 1—乙氧基乙氧基、1—甲基一 1 ' 一 η—丙氧基乙氧基、1 一甲基一 l—i一丙氧基乙氧基、1 —甲基一 1— η — 丁氧基乙氧基、1—甲基—1 一 i一丁氧基 φ 乙氧基、1—甲基一1— sec — 丁氧基乙氧基、1—甲基一1 一 t 一丁氧基乙氧基、1 一甲基—1 一環戊氧基乙氧基、1 一 甲基一 1 一環己氧基乙氧基、1 一甲基一 1 一降冰片氧基乙 氧基、1—甲基一 1—冰片氧基乙氧基、1 一甲基一1—苯氧 基乙氧基、1 一甲基—1 一（1 一萘氧基）乙氧基、1 一甲基 —1—苯甲氧基乙氧基、1—甲基—1 一苯乙氧基乙氧基、1 —環己基一1—甲氧基乙氧基、1一環己基一 1—乙氧基乙 氧基、1—環己基一 1 一 η-丙氧基乙氧基、1—環己基一1 # ) — i 一丙氧基乙氧基、1 一環己基一 1 一環己氧基乙氧基、1 —環己基—1-苯氧基乙氧基、1 一環己基一1 一苯甲氧基 乙氧基、1 一苯基—1—甲氧基乙氧基、1 一苯基—1—乙氧 基乙氧基、1—苯基一1— η —丙氧基乙氧基、1—苯基一1 - —i —丙氧基乙氧基、1—苯基一1—環己氧基乙氧基、1 — 苯基一 1 一苯氧基乙氧基、1 一苯基一 1 一苯甲氧基乙氧基 、：1—苯甲基一 1 一甲氧基乙氧基、1—苯甲基一 1—乙氧基 乙氧基、1 一苯甲基—1 一 η—丙氧基乙氧基、1 一苯甲基一 1 一 i一丙氧基乙氧基、1 一苯甲基一 1 一環己氧基乙氧基、 -11 - 200835744 1 一苯甲基一 1 一苯氧基乙氧基、1 一苯甲基一1—苯甲氧基 乙氧基、2— (2-甲基—四氫呋喃）氧基、2— (2 —甲基 —四氫吡喃）氧基、1 一甲氧基一環戊氧基、1 一甲氧基一 環己氧基等。 其中作爲較佳者可舉出1 -甲基一 1 -甲氧基乙氧基 、1 一甲基一 1—環己氧基乙氧基。 作爲與羧基結合形成羧酸的1 -烷基環烷基酯結構之 基，例如作爲較佳者可舉出1 -甲基環丙基、1 -甲基環 丁基、1 一甲基環戊基、1 一甲基環己基、1 一甲基環庚基 、1—甲基環辛基、1 一甲基環壬基、1 一甲基環癸基、1 一 乙基環丙基、1—乙基環丁基、1-乙基環戊基、1—乙基 環己基、1 -乙基環庚基、1 一乙基環辛基、1 一乙基環壬 基、1—乙基環癸基、1一（異）丙基環丙基、1—(異） 丙基環丁基、1一（異）丙基環戊基、1一（異）丙基環己 基、1一（異）丙基環庚基、1一（異）丙基環羊基、1一 (異）丙基環壬基、1一（異）丙基環癸基、1一（異）丁 基環丙基、1一（異）丁基環丁基、1一（異）丁基環戊基 、1—(異）丁基環己基、1 一 （異）丁基環庚基、1 一 （ 異）丁基環辛基、1一（異）丁基環壬基、1一（異）丁基 環癸基、1一（異）戊基環丙基、1一（異）戊基環丁基、 1 一 （異）戊基環戊基、1 一（異）戊基環己基、1 一（異 )戊基環庚基、1 一（異）戊基環辛基、1 一（異）戊基環 壬基、1一（異）戊基環癸基、1一（異）己基環丙基、1 —(異）己基環丁基、1 一（異）己基環戊基、1一（異） -12- 200835744 己基環己基、1 一（異）己基環庚基、1 一（異）己基環辛 基、1一 （異）己基環壬基、1一 （異）己基環癸基、1 一 (異）庚基環丙基、1一（異）庚基環丁基、1一（異）庚 基環戊基、1 一（異）庚基環己基、1 一（異）庚基環庚基 、1 一 （異）庚基環辛基、1 一 （異）庚基環壬基、1 一 （ 異）庚基環癸基、1 一（異）辛基環丙基、1 一（異）半基 環丁基、1 一（異）辛基環戊基、1一（異）辛基環己基、 φ) 1-(異）辛基環庚基、1-(異）辛基環辛基、1-(異 )辛基環壬基及1 一（異）辛基環癸基。 作爲具有上述縮醛酯或酮縮醇酯結構之聚合性不飽和 化合物，例如可舉出（甲基）丙烯酸酯化合物。作爲（甲f 基）丙烯酸酯化合物之具體例，例如可舉出1-乙氧基乙 基（甲基）丙燒酸酯、四氫一 2H—卩比喃一 2—基（甲基） 丙烯酸酯、1 一（環己氧基）乙基（甲基）丙烯酸酯、1 一 (2—甲基丙氧基）乙基（甲基）丙烯酸酯、1— (1，1 一 ® )二甲基一乙氧基）乙基（甲基）丙烯酸酯等。 作爲賦予聚合單位（a-1)之聚合性不飽和化合物， 其中以具有羧酸的縮醛酯或酮縮醇酯結構之（甲基）丙烯 " 酸酯化合物及t-丁基（甲基）丙烯酸酯爲佳，特佳爲1 ' 一乙氧基乙基甲基丙烯酸酯、四氫一 2H—吡喃一2—基甲 基丙烯酸酯、1 一（環己氧基）乙基甲基丙烯酸酯、1 一（ 2 —甲基丙氧基）乙基甲基丙嫌酸酯、；[一’（1，1一二甲基 一乙氧基）乙基甲基丙烯酸酯、t-丁基甲基丙烯酸酯。 作爲具有上述1 一烷基環烷基酯結構之（甲基）丙烯 -13- 200835744 酸醋化合物的具體例，可舉出1 -甲基環丙基（甲基）丙 烯酸酯、1 -甲基環丁基（甲基）丙烯酸酯、1 一甲基環戊 基（甲基）丙稀酸酯、1 一甲基環己基（甲基）丙燦酸酯 、1 一甲基環庚基（甲基）丙烯酸酯、1一甲基環辛基（甲 基）丙烯酸酯、1 一甲基環壬基（甲基）丙烯酸酯、1一甲 基環癸基（甲基）丙烯酸酯、1一乙基環丙基（甲基）丙 烯酸酯、1 一乙基環丁基（甲基）丙烯酸酯、1 一乙基環戊 基（甲基）丙烯酸酯、1一乙基環己基（甲基）丙烯酸酯 、1一乙基環庚基（甲基）丙烯酸酯、1 一乙基環辛基（甲 基）丙烯酸酯、1 一乙基環壬基（甲基）丙烯酸酯、1 —乙 基環癸基（甲基）丙烯酸酯、1一 （異）丙基環丙基（甲 基）丙烯酸酯、1一（異）丙基環丁基（甲基）丙烯酸酯 、1 一（異）丙基環戊基（甲基）丙烯酸酯、1 一（異）丙 基環己基（甲基）丙烯酸酯、1一 （異）丙基環庚基（甲 基）丙烯酸酯、1一（異）丙基環辛基（甲基）丙烯酸酯 、：I一（異）丙基環壬基（甲基）丙烯酸酯、1一（異）丙 基環癸基（甲基）丙烯酸酯、1一 （異）丁基環丙基（甲 基）丙烯酸酯、1一（異）丁基環丁基（甲基）丙烯酸酯 、1一（異）丁基環戊基（甲基）丙烯酸酯、1一（異）丁 基環己基（甲基）丙烯酸酯、1 一 （異）丁基環庚基（甲 基）丙烯酸酯、1-（異）丁基環辛基（甲基）丙烯酸酯 、1一（異）一丁基環壬基（甲基）丙烯酸酯、1一（異） 丁基環癸基（甲基）丙燒酸酯、1 一（異）戊基環丙基（ 甲基）丙烯酸酯、1 -（異）戊基環丁基（甲基）丙烯酸 -14- 200835744 酯、1一 （異）戊基環戊基（甲基）丙烯酸酯' 1 一 （異） 戊基環己基（甲基）丙烯酸酯、1 一（異）戊基環庚基（ 甲基）丙烯酸酯、1 一（異）戊基環辛基（甲基）丙烯酸 酯、1一 （異）戊基環壬基（甲基）丙烯酸酯、1一 （異） 戊基環癸基（甲基）丙烯酸酯、1 一（異）己基環丙基（ ^ 甲基）丙烯酸酯、1 一（異）己基環丁基（甲基）丙烯酸 酯、1 一 （異）己基環己基（甲基）丙烯酸酯、1—(異） • } 己基環庚基（甲基）丙烯酸酯、1 一（異）己基環辛基（ 甲基）丙烯酸酯、1 一（異）己基環壬基（甲基）丙烯酸 酯、1一 （異）己基環癸基（甲基）丙烯酸酯、1一 （異） 庚基環丙基（甲基）丙烯酸酯、1 -（異）庚基環丁基（ 甲基）丙烯酸酯、1 一（異）庚基環戊基（甲基）丙烯酸 酯、1 一 （異）庚基環己基（甲基）丙烯酸酯、1 一 （異） 庚基環庚基（甲基）丙烯酸酯、1 一（異）庚基環辛基（ 甲基）丙烯酸酯、1 一（異）庚基環壬基（甲基）丙烯酸 ® ) 酯、1一（異）庚基環癸基（甲基）丙烯酸酯、1一 （異） 辛基環丙基（甲基）丙烯酸酯、1 一（異）辛基環丁基（ 甲基）丙烯酸酯、1一（異）辛基環戊基（甲基）丙烯酸 ‘ 酯、1一 （異）辛基環己基（甲基）丙烯酸酯、1一 （異） 辛基環庚基（甲基）丙烯酸酯、1一（異）辛基環辛基（ 甲基）丙烯酸酯、1 一（異）辛基環壬基（甲基）丙烯酸 酯、1 一（異）辛基環癸基（甲基）丙烯酸酯等。 其中使用1—乙基環戊基（甲基）丙烯酸酯、1 一乙 基環己基（甲基）丙烯酸酯、1 一 （異）丙基環戊基（甲 -15- 200835744 基）丙烯酸酯、1 -（異）丙基環己基（甲基）丙烯酸酯 、1 一（異）丁基環戊基（甲基）丙烯酸酯、1—(異）丁 基環己基（甲基）丙烯酸酯爲佳，更佳爲1-乙基環戊基 (甲基）丙烯酸酯、1—乙基環己基（甲基）丙烯酸酯， 特佳爲1 一乙基環戊基（甲基）丙烯酸酯、1—乙基環己 基（甲基）丙烯酸酯。這些由共聚合反應性及所得之保護 膜耐熱性、組成物溶液之保存安定性提高的觀點來看爲佳 〇 賦予這些聚合單位（a-1 )之聚合性不飽和化合物可 單獨或組合下使用。 賦予聚合單位（a-2 )之聚合性不飽和化合物爲具有 氧雜環丁烷基之聚合性不飽和化合物，例如可舉出3 -（ 甲基丙烯醯氧基甲基）氧雜環丁烷、3 -（甲基丙烯醯氧 基甲基）一 3 —乙基氧雜環丁烷、3—(甲基丙烯醯氧基甲 基）〜2—甲基氧雜環丁烷、3—（甲基丙烯醯氧基甲基） 一 2—三氟甲基氧雜環丁烷、3一（甲基丙烯醯氧基甲基） 一 五氟乙基氧雜環丁烷、3—（甲基丙烯醯氧基甲基） 一 2〜苯基氧雜環丁烷、3-（甲基丙烯醯氧基甲基）一 2 ’ 2〜二氟氧雜環丁烷、3 — （甲基丙烯醯氧基甲基）一 2,2,4—三氟氧雜環丁烷、3—（甲基丙烯醯氧基甲基）一 2，2,4,4 一四氟氧雜環丁烷、3—（甲基丙烯醯氧基乙基） 氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-3—乙基氧雜 環丁烷、2—乙基- 3-（甲基丙烯醯氧基乙基）氧雜環丁 院、（甲基丙烯醯氧基乙基）一 2—三氟甲基氧雜環丁 -16 - 200835744 烷、3-(甲基丙烯醯氧基乙基）- 2-五氟乙基氧雜環丁 垸、3-（甲基丙稀醯氧基乙基）一 2 -苯基氧雜環丁院、 2，2 -二氟一 3 -（甲基丙烯醯氧基乙基）氧雜環丁烷、3 一（甲基丙烯醯氧基乙基）一 2,2,4一三氟氧雜環丁烷、3 一（甲基丙烯醯氧基乙基）一 2,2,4，4 一四氟氧雜環丁烷等 甲基丙烯酸酯； 3-（丙烯醯氧基甲基）氧雜環丁烷、3—(丙烯醯氧 基甲基）一 3-乙基氧雜環丁院、3—(丙烯醯氧基甲基） 〜2—甲基氧雜環丁烷、3 - （丙烯醯氧基甲基）一 2一三 氟甲基氧雜環丁烷、3-（丙烯醯氧基甲基）一 2一五氟乙. 基氧雜環丁烷、3-（丙烯醯氧基甲基）- 2—苯基氧雜環 丁烷、3—(丙烯醯氧基甲基）一2,2 -二氟氧雜環丁烷、 3〜（丙烯醯氧基甲基）—2,2,4一三氟氧雜環丁烷、3 — (丙烯醯氧基甲基）一 2,2,4,4 —四氟氧雜環丁烷、3 一 （ 朽稀醯氧基乙基）氧雜環丁院、3 -（丙烯醯氧基乙基） 〜3—乙基氧雜環丁烷、2 -乙基一 3 - （丙烯醯氧基乙基 )氧雜環丁烷、3-（丙烯醯氧基乙基）一 2—三氟甲基氧 雜環丁烷、3-（丙烯醯氧基乙基）- 2-五氟乙基氧雜環 丁烷、3-(丙烯醯氧基乙基）—2-苯基氧雜環丁烷、 2，2 —二氟—3 -（丙烯醯氧基乙基）氧雜環丁烷、3—( 汽烯醯氧基乙基）-2,2,4 -三氟氧雜環丁烷、3 - （丙烯 醯氧基乙基）- 2,2,4,4-四氟氧雜環丁烷等丙烯酸酯； 2—（甲基丙烯醯氧基甲基）氧雜環丁烷、2一甲基一 2〜（甲基丙烯醯氧基甲基）氧雜環丁烷、3 一甲基一 2 一 -17- 200835744 (甲基丙烯醯氧基甲基）氧雜環丁烷、4一甲基一 2— （甲 基丙烯醯氧基甲基）氧雜環丁烷、2- （甲基丙烯醯氧基 甲基）一 2—三氟甲基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 3—三氟甲基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 4一三氟甲基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 2-五氟乙基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 3-五氟乙基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 4一五氟乙基氧雜環丁烷、2—（甲基丙烯醯氧基 甲基）一 2-苯基氧雜環丁烷、2—（甲基丙烯醯氧基甲基 )一 3-苯基氧雜環丁烷、2-（甲基丙烯醯氧基甲基 4 -苯基氧雜環丁烷、2,3 -二氟一 2- （甲基丙烯醯氧基 甲基）氧雜環丁烷、2,4 一二氟一 2-（甲基丙烯醯氧基甲 基）氧雜環丁垸、3,3 -二氟一 2—(甲基丙燃酸氧基甲基 )氧雜環丁烷、3,4 一二氟一 2-（甲基丙烯醯氧基甲基） 氧雜環丁烷、4,4 一二氟一 2-（甲基丙烯醯氧基甲基）氧 雜環丁烷、2—(甲基丙烯醯氧基甲基）一 3,3,4一三氟氧 雜環丁烷、2-（甲基丙烯醯氧基甲基）一 3,4,4 一三氟氧 雜環丁烷、2—（甲基丙烯醯氧基甲基）一 3,3,4,4 一四氟 氧雜環丁烷、2-（甲基丙烯醯氧基乙基）氧雜環丁烷、2 一（2 —（2—甲基氧雜環丁烷基））乙基甲基丙烯酸酯、 2 一 （2 -（3 -甲基氧雜環丁烷基））乙基甲基丙烯酸酯 、2— （甲基丙烯醯氧基乙基）一 2—甲基氧雜環丁烷、2 一（甲基丙烯醯氧基乙基）—4一甲基氧雜環丁烷、2—（ 甲基丙烯醯氧基乙基）一 2 —三氟甲基氧雜環丁烷、2-( -18- 200835744 甲基丙烯醯氧基乙基）一 3—三氟甲基氧雜環丁烷、2一 （ 甲基丙_醯氧基乙基）一 4一三氟甲基氧雜環丁院、2一（ 甲基丙烯醯氧基乙基）一 2—五氟乙基氧雜環丁丨兀、2一 （ 甲基丙烯醯氧基乙基）一 3-五氟乙基氧雜環丁院、2一（ 甲基丙烯醯氧基乙基）一 4一五氟乙基氧雜環丁院、2一（ ' 甲基丙烯醯氧基乙基）一 2—苯基氧雜環丁烷、2— （甲基 丙烯醯氧基乙基）一 3-苯基氧雜環丁烷、2— （甲基丙燒 • 醯氧基乙基）—4一苯基氧雜環丁烷、2,3 —二氟一2- （ 甲基丙嫌醯氧基乙基）氧雜環丁院、2,4 一一黑一 2— （甲 基丙烯醯氧基乙基）氧雜環丁烷、3,3 —二氟一 2—(甲基 丙烯醯氧基乙基）氧雜環丁烷、3,4 一二氟一 2— （甲基丙 烯醯氧基乙基）氧雜環丁烷、4,4 一二氟一 2— （甲基丙儲 醯氧基乙基）氧雜環丁烷、2_ (甲基丙烯醯氧基乙基） 一 3，3,4 一三氯氧雜環丁院、2—（甲基丙條釀黑基乙基） 一 3，4,4 一三氟氧雜環丁院、2-（甲基丙嫌醯氧基乙基） • ) — 3,3,4,4-四氟氧雜環丁烷等甲基丙烯酸酯； 2— （丙嫌醯氧基甲基）氧雜環丁院、2—甲基一 2 — (丙烯醯氧基甲基）氧雜環丁烷、3 —甲基一 2—（丙烯醯 ‘ 氧基甲基）氧雜環丁烷、4 —甲基一 2-（丙烯醯氧基甲基 - )氧雜環丁烷、2—（丙烯醯氧基甲基）一 2—三氟甲基氧 雜環丁烷、2-（丙烯醯氧基甲基）- 3—三氟甲基氧雜環 丁烷、2-（丙烯醯氧基甲基）一 4一三氟甲基氧雜環丁烷 、2—(丙烯醯氧基甲基）一 2 —五氟乙基氧雜環丁烷、2 一（丙烯醯氧基甲基）一 3-五氟乙基氧雜環丁烷、2-（ -19 - 200835744 丙烯醢氧基甲基）- 4-五氟乙基氧雜環丁烷、2—(丙烯 醯氧基甲基）一 2—苯基氧雜環丁烷、2— （丙烯醯氧基甲 基）一 3 -苯基氧雜環丁烷、2—（丙烯醯氧基甲基）一 4 一苯基氧雜環丁烷、2,3 -二氟一 2-（丙烯醯氧基甲基） 氧雜環丁烷、2,4 一二氟一 2- （丙烯醯氧基甲基）氧雜環 丁烷、3,3 -二氟一 2-（丙烯醯氧基甲基）氧雜環丁烷、 3，4 一二氟—2- （丙烯醯氧基甲基）氧雜環丁烷、4,4 一 二氟一 2-（丙烯醯氧基甲基）氧雜環丁烷、2-（丙烯醯 氧基甲基）-3,3，4 一三氟氧雜環丁烷、2-（丙烯醯氧基 甲基）一 3,4，4 一三氟氧雜環丁烷、2—(丙烯醯氧基甲基 )——3,3,4,4 一四氟氧雜環丁烷、2- （丙烯醯氧基乙基） 氧雜環丁烷、2-（2-（2-甲基氧雜環丁烷基））乙基 甲基丙烯酸酯、2—（2 —（3 -甲基氧雜環丁烷基））乙 基甲基丙烯酸酯、2—（丙烯醯氧基乙基）一 2—甲基氧雜 環丁烷、2-（丙烯醯氧基乙基）一 4一甲基氧雜環丁烷、 2— （丙烯醯氧基乙基）—2 —三氟甲基氧雜環丁烷、2-(丙烯醯氧基乙基）一 3-三氟甲基氧雜環丁烷、2—（丙 烯醯氧基乙基）一 4一三氟甲基氧雜環丁烷、2-（丙烯醯 氧基乙基）- 2-五氟乙基氧雜環丁烷、2-（丙烯醯氧基 乙基）一 3-五氟乙基氧雜環丁烷、2—（丙烯醯氧基乙基 )一 4一五氟乙基氧雜環丁烷、2-（丙烯醯氧基乙基）一 2-苯基氧雜環丁烷、2-（丙烯醯氧基乙基）一 3 —苯基 氧雜環丁烷、2-（丙烯醯氧基乙基）一 4一苯基氧雜環丁 烷、2,3 -二氟一 2- （丙烯醯氧基乙基）氧雜環丁烷、 -20- 200835744 2，4 一二氟一 2 - （丙烯醯氧基乙基）氧雜環丁烷、3,3 — 二氟一 2- （丙烯醯氧基乙基）氧雜環丁烷、3,4 一二氟一 2- （丙烯醯氧基乙基）氧雜環丁烷、4,4 一二氟—2- （ 丙烯醯氧基乙基）氧雜環丁烷、2-（丙烯醯氧基乙基） 一 3，3,4 一三氟氧雜環丁烷、2 - （丙烯醯氧基乙基）— - 3，4,4 一三氟氧雜環丁烷、2 — （丙烯醯氧基乙基）一 3,3,4,4 一四氟氧雜環丁烷等丙烯酸酯。 馨 其中3-（甲基丙烯醯氧基乙基）氧雜環丁烷、3 — (丙烯醯氧基乙基）氧雜環丁烷、3- （甲基丙烯醯氧基 甲基）一2-三氟甲基氧雜環丁烷、3—(甲基丙烯醯氧基 甲基）_2-苯基氧雜環丁烷、2—（甲基丙烯醯氧基甲基 )氧雜環丁烷、2-（甲基丙烯醯氧基甲基）一 4一三氟甲 基氧雜環丁烷等由共聚合反應性及所得之保護膜的平坦性 、提高保存安定性之觀點來看爲佳。 賦予這些聚合單位（a-2 )之聚合性不飽和化合物可 ® )單獨或組合下使用。 硬化性樹脂組成物爲含有來自聚合單位（a-1 )、( a-2 )以外之聚合性不飽和化合物的聚合單位（a_3 )。作 ' 爲賦予聚合單位（a-3 )之聚合性不飽和化合物，例如可 ' 舉出含有環氧乙烷基之聚合性不飽和化合物、（甲基）丙 烯酸烷基酯（但除t-丁基（甲基）丙烯酸酯之外）、（甲 基）丙烯酸環狀烷基酯、（甲基）丙烯酸芳基酯、不飽和 二羧酸二酯、雙環不飽和化合物、馬來醯亞胺化合物、不 飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、 -21 - 200835744 不飽和二羧酸、不飽和二羧酸酐、其他不飽和化合物。II I 〇R! [In the formula (1), R! independently represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, or each R1 Combine with each other to form a ring. Also, (*) indicates a bond. As a group which forms a acetal ester structure of a carboxylic acid in combination with a carboxyl group (-OCH ( Ri ) OR! in the above formula (1)), for example, it can be mentioned! - methoxyethoxy, 1-ethoxyethoxy, 1-n-propoxyethoxy, 1-i-propoxyethoxy, 1-n-butoxyethoxy, 1-i-butoxyethoxy, 1-sec-butoxyethoxy, 1-t-butoxyethoxy, 1-9-200835744 cyclopentyloxyethoxy, 1-ring Hexyloxyethoxy, 1 -norbornyloxyethoxy, 1 -borneaoxyethoxy, 1 -phenoxyethoxy, 1 -(1 -naphthyloxy)ethoxy, 1- Benzyloxyethoxy, 1-phenylethoxyethoxy, (cyclohexyl)(methoxy)methoxy, (cyclohexyl)(ethoxy)methoxy, (cyclohexyl)(η —propoxy)methoxy, (cyclohexyl)(i-propoxy)methoxy, (cyclohexyl)(cyclohexyloxy)methoxy, (cyclohexyl)(phenoxy)methoxy (cyclohexyl)(benzyloxy)methoxy, (phenyl)(methoxy)methoxy, (phenyl)(ethoxy)methoxy, (phenyl)(η-propoxy Methoxy, (phenyl)(i-propoxy)methoxy, (phenyl)(cyclohexyloxy)methoxy , (phenyl)(phenoxy)methoxy, (phenyl)(benzyloxy)methyloxy, (benzyl)(methoxy)methoxy, (benzyl)(B Oxy) methoxy, (benzyl) (η-propoxy) methoxy, (benzyl) (i-propoxy) methoxy, (benzyl) (cyclohexyloxy) Methoxy, (benzyl)(phenoxy)methoxy, (benzyl)(benzyloxy)methoxy, 2-tetrahydrofuranyloxy, 2-tetrahydrofurfuryloxy, and the like. Preferred among them are 1-ethoxyethoxy, 1-cyclohexyloxyethoxy, 2-tetrahydropyranyloxy, 1-n-propoxyethoxy, 2-tetrahydrofuranoxy . The ketal ester structure of the carboxylic acid can be represented by the following formula (2). R2 I 氺—C— II —C— II 〇I r2 [In the formula (2), R 2 independently of each other represents an alkyl group having 1 to 20 carbon atoms, a carbon number of -10 to 200835744 3 to 20 alicyclic group or carbon An aromatic hydrocarbon group of 6 to 20, (*) represents a bond. The group of the ketal ester structure which forms a carboxylic acid in combination with a carboxyl group (-OC(R2)2OR2 in the above formula (2)) is, for example, 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy, 1-methyl-1'-n-propoxyethoxy, 1-methyl-l-i-propoxyethoxy, 1-methyl 1,1-butoxyethoxy, 1-methyl-1, i-butoxy ethoxy, 1-methyl-1,4-sec-butoxyethoxy, 1-methyl 1-1 -1 -butoxyethoxy, 1 -methyl-1 -cyclopentyloxyethoxy, 1 -methyl- 1 -cyclohexyloxyethoxy, 1 -methyl-1 -norbornyloxy Ethyloxy, 1-methyl-l-borneooxyethoxy, 1-methyl-1-phenoxyethoxy, 1-methyl-1(1-naphthyloxy)ethoxy , 1-methyl-1-benzyloxyethoxy, 1-methyl-1-phenylethoxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-cyclohexyl-1 —ethoxyethoxy, 1-cyclohexyl-1—n-propoxyethoxy, 1-cyclohexyl-1# — — i-prop Oxyethoxyethoxy, 1-cyclohexyl-1-cyclohexyloxyethoxy, 1-cyclohexyl-1-phenoxyethoxy, 1-cyclohexyl-1-phenylmethoxyethoxy, 1-benzene 1-methoxyethoxy, 1-phenyl-1-ethoxyethoxy, 1-phenyl-1-methoxy-ethoxyoxy, 1-phenyl- 1 --i —propoxyethoxy, 1-phenyl-1-cyclohexyloxyethoxy, 1-phenyl-1-monophenoxyethoxy, 1-phenyl-1-benzomethoxyethoxy Base: 1-benzyl-monomethoxypropion, 1-benzyl-1-methoxyethoxy, 1-benzyl--1-n-propoxyethoxy, 1 monobenzyl- 1 -i-propoxyethoxy, 1 -benzylmethyl- 1 -cyclohexyloxyethoxy, -11 - 200835744 1 monobenzyl- 1 -phenoxyethoxy 1, 1-benzyl-mono-benzyloxyethoxy, 2-(2-methyl-tetrahydrofuran)oxy, 2-(2-methyl-tetrahydropyran)oxy, 1-methoxy A mono-cyclopentyloxy group, a 1-methoxy-cyclohexyloxy group, and the like. Among them, preferred are 1-methyl-1-methoxyethoxy and 1-methyl-1-cyclohexyloxyethoxy. As a group of a 1-alkylcycloalkyl ester structure which forms a carboxylic acid in combination with a carboxyl group, for example, 1-methylcyclopropyl, 1-methylcyclobutyl, 1-methylcyclopentane is preferable. 1, 1-methylcyclohexyl, 1-methylcycloheptyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclodecyl, 1-ethylcyclopropyl, 1 —Ethylcyclobutyl, 1-ethylcyclopentyl, 1-ethylcyclohexyl, 1-ethylcycloheptyl, 1-ethylcyclooctyl, 1-ethylcyclodecyl, 1-ethyl Cyclodecyl, 1-(iso)propylcyclopropyl, 1-(iso)propylcyclobutyl, 1-monopropylidenecyclopentyl, 1-monopropylidenecyclohexyl, 1 ( Isopropylcycloheptyl, 1-(iso)propylcyclopentyl, 1-monopropylidene fluorenyl, 1-monopropylidene fluorenyl, 1 (iso)butylcyclopropane 1, 1-(iso)butylcyclobutyl, 1-(iso)butylcyclopentyl, 1-(iso)butylcyclohexyl, 1-(iso)butylcycloheptyl, 1 (iso) Butylcyclooctyl, 1-(iso)butylcyclodecyl, 1-monoisobutylcyclodecyl, 1-monoisopentylcyclopropyl, 1 Iso)pentylcyclobutyl, 1 (iso)pentylcyclopentyl, 1 (iso)pentylcyclohexyl, 1 (iso)pentylcycloheptyl, 1 (iso)pentylcyclooctyl , 1 (iso)pentylcyclodecyl, 1 (iso)pentylcyclodecyl, 1 -(iso)hexylcyclopropyl, 1 -(iso)hexylcyclobutyl, 1 (iso)hexyl ring Pentyl, 1 (iso) -12- 200835744 hexylcyclohexyl, 1 (iso)hexylcycloheptyl, 1 (iso)hexylcyclooctyl, 1 -(iso)hexylcyclodecyl, 1 (different) Hexylcyclodecyl, 1 (iso)heptylcyclopropyl, 1 (iso)heptylcyclobutyl, 1 (iso)heptylcyclopentyl, 1 (iso)heptylcyclohexyl, 1 Mono(iso)heptylcycloheptyl, 1 (iso)heptylcyclooctyl, 1 (iso)heptylcyclodecyl, 1 (iso)heptylcyclodecyl, 1 (iso)octyl Cyclopropyl, 1 (iso)halylcyclobutyl, 1 (iso)octylcyclopentyl, 1 (iso)octylcyclohexyl, φ) 1-(iso)octylcycloheptyl, 1 -(iso)octylcyclooctyl, 1-(iso)octylcyclodecyl and 1(iso)octylcyclodecyl. The polymerizable unsaturated compound having the above acetal ester or ketal ester structure may, for example, be a (meth) acrylate compound. Specific examples of the (meth) acrylate compound include 1-ethoxyethyl (meth) propionate, and tetrahydro-2H-fluorenyl-2-phenyl (meth) acrylate. Ester, 1-(cyclohexyloxy)ethyl (meth) acrylate, 1-(2-methylpropoxy)ethyl (meth) acrylate, 1-(1,1-®) dimethyl Ethyl ethoxy) ethyl (meth) acrylate and the like. As the polymerizable unsaturated compound to which the polymerization unit (a-1) is imparted, a (meth) propylene " acid ester compound having a acetal ester or a ketal ester structure of a carboxylic acid and t-butyl (methyl group) Acrylate is preferred, especially 1 '-ethoxyethyl methacrylate, tetrahydro-2H-pyran-2-yl methacrylate, 1-(cyclohexyloxy)ethylmethyl Acrylate, 1-(2-methylpropoxy)ethylmethylpropionate, [1-(1,1-dimethyl-ethoxy)ethyl methacrylate, t-butyl Acrylate. Specific examples of the (meth)acryl-13-200835744 acid vinegar compound having the above monoalkylcycloalkyl ester structure include 1-methylcyclopropyl (meth) acrylate and 1-methyl group. Cyclobutyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (methyl) acrylate, 1-methylcycloheptyl (A) Acrylate, 1-methylcyclooctyl (meth) acrylate, 1-methylcyclodecyl (meth) acrylate, 1-methylcyclodecyl (meth) acrylate, 1-B Cyclopropyl (meth) acrylate, 1-ethylcyclobutyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate Ester, 1-ethylcycloheptyl (meth) acrylate, 1-ethylcyclooctyl (meth) acrylate, 1-ethylcyclodecyl (meth) acrylate, 1-ethyl fluorene Base (meth) acrylate, 1-(iso)propylcyclopropyl (meth) acrylate, 1-monopropyl butyl butyl (meth) acrylate, 1 (different) ) propylcyclopentyl (meth) acrylate, mono (iso)propylcyclohexyl (meth) acrylate, mono (iso) propyl cycloheptyl (meth) acrylate, 1 (different) Propylcyclooctyl (meth) acrylate, I-(iso)propylcyclodecyl (meth) acrylate, mono-(isopropyl)cyclodecyl (meth) acrylate, 1 (Isobutyl butyl propyl (meth) acrylate, mono-isobutyl butyl butyl (meth) acrylate, mono (iso) butyl cyclopentyl (meth) acrylate, 1 Mono(isobutyl)cyclohexyl (meth) acrylate, mono(iso)butylcycloheptyl (meth) acrylate, 1-(iso)butylcyclooctyl (meth) acrylate, 1 Mono (iso)-butylcyclodecyl (meth) acrylate, mono-(iso)butylcyclodecyl (meth)propionate, 1 (iso)pentylcyclopropyl (methyl) Acrylate, 1-(iso)pentylcyclobutyl(meth)acrylate-14-200835744 ester, mono-(iso)pentylcyclopentyl (meth) acrylate ' 1 mono(iso)pentylcyclohexyl (A Acrylate, 1 (iso)pentylcycloheptyl (meth) acrylate, 1 (iso)pentylcyclooctyl (meth) acrylate, 1 (iso)pentyl fluorenyl (A) Acrylate, 1 (iso)pentylcyclodecyl (meth) acrylate, 1 (iso)hexylcyclopropyl (^-methyl) acrylate, 1 (iso)hexylcyclobutyl (A) Acrylate, 1-(iso)hexylcyclohexyl (meth) acrylate, 1-(iso) • } hexylcycloheptyl (meth) acrylate, 1-(iso)hexylcyclooctyl (methyl) Acrylate, 1-(iso)hexylcyclodecyl (meth) acrylate, mono-(iso)hexylcyclodecyl (meth) acrylate, mono-(iso)heptylcyclopropyl (methyl) Acrylate, 1-(iso)heptylcyclobutyl(meth)acrylate, 1-(iso)heptylcyclopentyl (meth)acrylate, 1-(iso)heptylcyclohexyl (methyl) Acrylate, 1 (iso)heptylcycloheptyl (meth) acrylate, 1 (iso)heptylcyclooctyl (meth) acrylate, 1 ( Heptylcyclodecyl (meth)acrylic acid®) ester, mono-(iso)heptylcyclodecyl (meth) acrylate, mono(iso)octylcyclopropyl (meth) acrylate, 1 Mono(iso)octylcyclobutyl(meth)acrylate, mono(iso)octylcyclopentyl (meth)acrylic acid ester, mono-(iso)octylcyclohexyl (meth) acrylate, 1-(iso)octylcycloheptyl (meth) acrylate, mono(iso)octylcyclooctyl (meth) acrylate, mono(iso)octylcyclodecyl (meth) acrylate , 1 (iso)octylcyclodecyl (meth) acrylate, and the like. Wherein 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-(iso)propylcyclopentyl (methyl-15-200835744) acrylate, 1-(Isopropyl)cyclohexyl (meth) acrylate, 1-(iso)butylcyclopentyl (meth) acrylate, 1-(iso)butylcyclohexyl (meth) acrylate is preferred More preferably, it is 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, particularly preferably 1-ethylcyclopentyl (meth) acrylate, 1- Ethylcyclohexyl (meth) acrylate. These polymerizable unsaturated compounds which are imparted to these polymerization units (a-1) can be used singly or in combination from the viewpoints of the copolymerization reactivity and the heat resistance of the obtained protective film and the storage stability of the composition solution. . The polymerizable unsaturated compound to which the polymerization unit (a-2) is added is a polymerizable unsaturated compound having an oxetanyl group, and examples thereof include 3-(methacryloxymethyl)oxetane. , 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)~2-methyloxetane, 3-—( Methyl propylene methoxymethyl) 2- 2-trifluoromethyl oxetane, 3-(methacryloxymethyl) pentafluoroethyl oxetane, 3-(methyl Propylene methoxymethyl) 1-2 phenyl oxetane, 3-(methacryloxymethyl)-2'2-difluorooxetane, 3-(methacryl oxime) Oxymethyl) 2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4 tetrafluorooxetane, 3 —(methacryloxyethyl) oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methyl Propylene oxiranyl ethyl) oxetane, (methacryloxyethyl) 2-trifluoro Methyl oxetane-16 - 200835744 alkane, 3-(methacryloxyethyl)-2-pentafluoroethyl oxetane, 3-(methyl propyl methoxyethyl) 2-Phenyloxetan, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2 , 2,4-trifluorooxetane, 3-(methacryloxyethyl)-2,2,4,4 tetrafluorooxetane, etc.; 3-( Propylene methoxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(propyleneoxymethyl)~2-methyloxy Heterocyclic butane, 3-(propenyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2,5-fluoropentyl. Alkanes, 3-(acryloxymethyl)-2-phenyloxetane, 3-(propylene methoxymethyl)-2,2-difluorooxetane, 3~(propylene醯oxymethyl)-2,2,4-trifluorooxetane, 3-(propylene methoxymethyl)-2,2,4,4-tetrafluorooxetane, 3 ( Dilute oxyethyl) oxetane, 3-(propenyloxyethyl)~3-ethyloxetane, 2-ethyl-3-(propenyloxyethyl)oxy Heterocyclic butane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(acryloxyethyl)-2-pentafluoroethyloxetane , 3-(propylene oxiranyloxy)-2-phenyloxetane, 2,2-difluoro-3-(propenyloxyethyl)oxetane, 3-(hydrogen) Acrylates such as methoxyethyl)-2,2,4-trifluorooxetane, 3-(propenyloxyethyl)-2,2,4,4-tetrafluorooxetane ; 2-(methacryloxymethyl)oxetane, 2-methyl-2-(methacryloxymethyl)oxetane, 3-methyl-2-one- 17- 200835744 (methacryloxymethyl) oxetane, 4-methyl-2-(methacryloxymethyl)oxetane, 2-(methacryloxyl) Methyl)- 2-trifluoromethyloxetane, 2-(methacryloxymethyl)-trifluoromethyloxetane, 2-—( Methyl propylene methoxymethyl) 4-tetrafluoromethyl oxetane, 2-(methacryloxymethyl)- 2-pentafluoroethyl oxetane, 2-—( Methyl propylene methoxymethyl) 1,3-pentafluoroethyl oxetane, 2-(methacryloxymethyl)-tetrafluoropentayl oxetane, 2-—( Methyl propylene methoxymethyl) 2-phenyl oxetane, 2-(methacryloxymethyl)- 3-phenyloxetane, 2-(methacryl oxime Oxymethylmethyl 4-phenyloxetane, 2,3-difluoro-2-(methacryloxymethyl)oxetane, 2,4-difluoro- 2-(A Acryloxymethyl)oxetanium, 3,3-difluoro-2-(methylpropionateoxymethyl)oxetane, 3,4-difluoro- 2-( Methyl propylene methoxymethyl) oxetane, 4,4 difluoro-2-(methacryloxymethyl)oxetane, 2-(methacryloxyloxy) a 3,3,4-trifluorooxetane, 2-(methacryloxymethyl)-3,4,4-trifluorooxetane, 2-(methyl propyl)醯oxymethyl)-3,3,4,4 tetrafluorooxetane, 2-(methacryloxyethyl)oxetane, 2 (2 - (2-) Oxetanealkyl))ethyl methacrylate, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2-(methacryloxyloxy) Ethyl)-2-methyloxetane, 2-(methacryloxyethyl)-4-methyloxetane, 2-(methacryloxyethyl) 2-trifluoromethyloxetane, 2-( -18-200835744 methacryloxyethyl)-trifluoromethyloxetane, 2-(methylpropane-oxime) Ethyl ethyl) 4-tetrafluoromethyl oxetane, 2-(methacryloxyethyl)-2-pentafluoroethyl oxetane, 2-(methacryl oxime) Oxyethyl)-3-pentafluoroethyl oxetan, 2-(methacryloxyethyl)-tetrafluoropropanol, 2-('methacrylate Oxyloxyethyl)-2-phenyloxetane, 2-(methacryloxyethyl)-3-phenyloxy Heterocyclobutane, 2-(methylpropanone • oxiranyloxy)-4-phenyloxetane, 2,3-difluoro-2-(methylpropionyloxyethyl) Oxime, 2,4, one black, 2-(methacryloxyethyl)oxetane, 3,3-difluoro-2-(methacryloxyethyl) Oxetane, 3,4-difluoro-2-(methacryloxyethyl)oxetane, 4,4-difluoro-2-(methylpropanyloxyethyl) Oxetane, 2_(methacryloxyethyl)-3,3,4-trichlorooxetine, 2-(methylpropane black ethyl)-3,4 , 4-trifluorooxetine, 2-(methylpropionyloxyethyl) • ) — 3,3,4,4-tetrafluorooxetane and other methacrylates; (Anodic oxymethyl) oxetan, 2-methyl-2-(propylene methoxymethyl) oxetane, 3-methyl-2-(propylene 醯' oxy- Oxycyclobutane, 4-methyl- 2-(propylene methoxymethyl-) oxetane, 2-(propylene methoxymethyl)-2-trifluoromethyl Oxetane, 2-(propylene methoxymethyl)-3-trifluoromethyloxetane, 2-(propylene methoxymethyl)-tetrafluoromethyl oxetane Alkane, 2-(propenyloxymethyl)-2-pentafluoroethyloxetane, 2-(propenyloxymethyl)-3-pentafluoroethyloxetane, 2- ( -19 - 200835744 propylene methoxymethyl) 4-pentafluoroethyl oxetane, 2-(propylene methoxymethyl)-2-phenyl oxetane, 2- (propylene醯oxymethyl)-3-phenyloxetane, 2-(propenyloxymethyl)-tetraphenyloxybutane, 2,3-difluoro-2-propene Oxymethyl) oxetane, 2,4 difluoro-2-(propenyloxymethyl)oxetane, 3,3-difluoro-2-propyryloxymethyl Oxetane, 3,4-difluoro-2-(propenyloxymethyl)oxetane, 4,4-difluoro-2-(propyleneoxymethyl)oxyheterocycle Butane, 2-(acryloxymethyl)-3,3,4-trifluorooxetane, 2-(acryloxymethyl)-3,4,4-trifluoro Heterocyclobutane, 2-(propylene methoxymethyl)-3,3,4,4 tetrafluorooxetane, 2-(propylene oxiranyloxy) oxetane, 2 -(2-(2-methyloxetanyl))ethyl methacrylate, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2 —(Propyleneoxyethyl)-2-methyloxetane, 2-(acryloxyethyl)-4-methyloxetane, 2-(propyleneoxyoxyethyl) - 2 - trifluoromethyl oxetane, 2-(acryloxyethyl)-trifluoromethyl oxetane, 2-(propylene oxiranyloxy) 4-41 Trifluoromethyloxetane, 2-(acryloxyethyl)-2-pentafluoroethyloxetane, 2-(acryloxyethyl)-1-pentafluoroethyl Oxetane, 2-(propylene methoxyethyl)-4,5pentafluoroethyl oxetane, 2-(acryloxyethyl)-2-phenyloxetane, 2-(Propyloxyethyl)-3-phenyloxybutane, 2-(acryloxyethyl)-tetraphenyloxybutane, 2,3 -di Fluor-2-(propenyloxyethyl)oxetane, -20- 200835744 2,4 difluoro-2-(propenyloxyethyl)oxetane, 3,3 - 2 Fluor-2-(propenyloxyethyl)oxetane, 3,4-difluoro-2-(propenyloxyethyl)oxetane, 4,4-difluoro-2- (propylene oxyethyl) oxetane, 2-(acryloxyethyl)-3,3,4-trifluorooxetane, 2-(propyleneoxyethyl)- - an acrylate such as 3,4,4-trifluorooxetane, 2-(acryloxyethyl)- 3,3,4,4-tetrafluorooxetane.馨 wherein 3-(methacryloxyethyl)oxetane, 3-(propyleneoxyethyl)oxetane, 3-(methacryloxymethyl)-2 -trifluoromethyloxetane, 3-(methacryloxymethyl)_2-phenyloxetane, 2-(methacryloxymethyl)oxetane 2-(methacryloxymethyl)tetrafluoromethyloxetane is preferred from the viewpoints of copolymerization reactivity, flatness of the obtained protective film, and improvement in storage stability. . The polymerizable unsaturated compound imparted to these polymerization units (a-2) can be used singly or in combination. The curable resin composition is a polymerization unit (a-3) containing a polymerizable unsaturated compound other than the polymerization units (a-1) and (a-2). The polymerizable unsaturated compound which is a polymerizable unit (a-3), for example, may be a polymerizable unsaturated compound containing an oxiranyl group or an alkyl (meth)acrylate (but except t-butyl) Other than (meth) acrylate), cyclic alkyl (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, -21 - 200835744 unsaturated dicarboxylic acid, unsaturated dicarboxylic anhydride, and other unsaturated compound.

作爲含有環氧乙烷基之聚合性不飽和化合物，例如可 舉出丙烯酸縮水甘油基、甲基丙烯酸縮水甘油基、^ -乙 基丙烯酸縮水甘油基、α - η -丙基丙烯酸縮水甘油基、 α - η -丁基丙烯酸縮水甘油基、丙烯酸一 3，4 -環氧基丁 基、甲基丙烯酸一 3,4 —環氧基丁基、丙烯酸一 6,7-環氧 基庚基、甲基丙烯酸- 6，7 —環氧基庚基、α -乙基丙烯 酸一 6,7 -環氧基庚基、〇 -乙烯苯甲基縮水甘油基醚、m 一乙烯苯甲基縮水甘油基醚、p —乙烯苯甲基縮水甘油基 醚等； 作爲（甲基）丙烯酸院基酯，例如可舉出羥基甲基（ 甲基）丙烯酸酯、2—羥基乙基（甲基）丙烯酸酯、3—羥 基丙基（甲基）丙烯酸酯、4 一羥基丁基（甲基）丙烯酸 酯、二乙二醇單（甲基）丙烯酸酯、2，3 一二羥基丙基（ 甲基）丙燒酸酯、2—甲基丙烯氧基乙基縮水甘油、4一羥 基苯基（甲基）丙烯酸酯、甲基（甲基）丙烯酸酯、乙基 (甲基）丙烯酸酯、η-丁基（甲基）丙烯酸酯、sec — 丁 基（甲基）两烯酸酯、2-乙基己基（甲基）丙烯酸酯、 異癸基（甲基）丙烯酸酯、η—月桂基（甲基）丙烯酸酯 、十一纟兀基（甲基）丙烯酸酯、η -硬脂醯（甲基）丙烯 酉文酯1一 丁氧基（甲基）丙烯酸酯、1 一二甲基（異）丙 基（甲基）丙烯酸酯、；！ 一二甲基（異）丁基（甲基）丙 燒酸醋1 一 一甲基（異）辛基（甲基）丙烯酸酯、1 一甲 基一1 一乙基乙基（甲基）丙烯酸酯、1一甲基一 1 一乙基 -22- 200835744 (異）丙基（甲基）丙烯酸酯、1 一甲基一 1 一乙基（異） 丁基（甲基）丙烯酸酯、1一甲基一 1 一乙基（異）辛基丙 烯酸酯、1 一 一乙基（異）丙基（甲基）丙烯酸酯、1 一二 乙基（異）丁基（甲基）丙烯酸酯、1 一二乙基（異）辛 基（甲基）丙烯酸酯等； " 作爲（甲基）丙烯酸環狀烷基酯，例如可舉出環己基 (甲基）丙烯酸酯、2—甲基環己基（甲基）丙烯酸酯、 φ 三環〔5.2.1.〇2,6〕癸烷一 8-基（甲基）丙烯酸酯、三環 〔5.2.1.0，〕癸；I：兀一 8-基氧基乙基（甲基）丙嫌酸酯、 異冰片（甲基）丙烯酸酯、1 一甲基環丙烷（甲基）丙烯 酸酯、1 一甲基環丁烷（甲基）丙烯酸酯、1—甲基環戊基 (甲基）丙烯酸酯、1 一甲基環己基（甲基）丙烯酸酯、1 一甲基環庚烷（甲基）丙烯酸酯、1 一甲基環辛烷（甲基 )丙烯酸酯、1—甲基環壬烷（甲基）丙烯酸酯、1 一乙基 環癸烷（甲基）丙烯酸酯、1 -乙基環丙烷（甲基）丙烯 ® J 酸酯、1 一乙基環丁烷（甲基）丙烯酸酯、1—乙基環戊基 (甲基）丙烯酸酯、1—乙基環己基（甲基）丙烯酸酯、1 一乙基環庚烷（甲基）丙烯酸酯、1-乙基環辛烷（甲基 ' )丙烯酸酯、1 一乙基環壬烷（甲基）丙烯酸酯、1一乙基 - 環癸烷（甲基）丙烯酸酯、1 一（異）丙基環丙烷（甲基 )丙烯酸酯、1一（異）丙基環丁院（甲基）丙儲酸酯、1 一（異）丙基環戊基（甲基）丙烯酸酯、1 一 （異）丙基 環己基（甲基）丙烯酸酯、1一 （異）丙基環庚烷（甲基 )丙烯酸酯、1一（異）丙基環辛烷（甲基）丙烯酸酯、1 -23- 200835744 一（異）丙基環壬烷（甲基）丙烯酸酯、1一 （異）丙基 環癸烷（甲基）丙烯酸酯、1一（異）丁基環丙烷（甲基 )丙烯酸酯、1一（異）丁基環丁烷（甲基）丙烯酸酯' 1 一（異）丁基環戊基（甲基）丙烯酸酯、1一 （異）丁基 環己基（甲基）丙烯酸酯、1一（異）丁基環庚烷（甲基 ' )丙烯酸酯、1一（異）丁基環辛烷（甲基）丙烯酸酯' 1 一（異）丁基環壬烷（甲基）丙烯酸酯、1一 （異）丁基 • 環癸基（甲基）丙烯酸酯、1一（異）戊基環丙基（甲基 )丙烯酸酯、1 一（異）戊基環丁基（甲基）丙烯酸酯、1 一（異）戊基環戊基（甲基）丙烯酸酯、1一 （異）戊基 環己基（甲基）丙烯酸酯、1一 （異）戊基環庚基（甲基 )丙烯酸酯、1一（異）戊基環辛基（甲基）丙烯酸酯、1 一（異）戊基環壬基（甲基）丙烯酸酯、1一 （異）戊基 環癸基（甲基）丙烯酸酯、1一（異）己基環丙基（甲基 )丙烯酸酯、1一（異）己基環丁基（甲基）丙烯酸酯、1 ® ) 一 （異）己基環己基（甲基）丙烯酸酯、1—(異）己基 環庚基（甲基）丙烯酸酯、1一（異）己基環辛基（甲基 )丙烯酸酯、1一（異）己基環壬基（甲基）丙烯酸酯、1 ' 一（異）己基環癸基（甲基）丙烯酸酯、1一 （異）庚基 ~ 環丙基（甲基）丙烯酸酯、1一（異）庚基環丁基（甲基 )丙烯酸酯、1一（異）庚基環庚基（甲基）丙烯酸酯、1 一（異）庚基環庚基（甲基）丙烯酸酯、1一 （異）庚基 環庚基（甲基）丙烯酸酯、1一（異）庚基環辛基（甲基 )丙烯酸酯、1一（異）庚基環壬基（甲基）丙烯酸酯、1 24 - 200835744 一（異）庚基環癸基（甲基）丙烯酸酯、1 一 （異）辛基 環丙基（甲基）丙烯酸酯、1 一 （異）辛基環丁基（甲基 )丙烯酸酯、1 一（異）辛基環辛基（甲基）丙烯酸酯、1 一（異）辛基環辛基（甲基）丙烯酸酯、1 一（異）辛基 環庚基（甲基）丙烯酸酯、1 一 （異）辛基環辛基（甲基 )丙細酸醋、1一（異）羊基環壬基（甲基）丙嫌酸醋、1 一（異）辛基環癸基（甲基）丙烯酸酯、2-乙基三環〔 3.3.1.13’7〕癸烷—2—基一（甲基）丙烯酸酯、2一甲基三 環〔3.3.1.13’7〕癸烷一 2—基一（甲基）丙烯酸酯、1 一乙 基三環〔3 · 3 · 1 · 13，7〕癸烷一 1 一基一（甲基）丙烯酸酯、；i 一乙基三環〔3·3·1·13,7〕癸烷一 1 一基一（甲基）丙烯酸 酯、3—羥基三環〔3.3.1.13,7〕癸烷一 i —基一（甲基）丙 烯酸酯等； (甲基）丙烯酸環狀烷基酯之烷基部可爲內脂結構、. 內醯胺結構、縮醛結構，作爲其例子可舉出2 —乙基- r 一丁內脂一 2—基一（甲基）丙烯酸酯、2 一甲基_ r 一丁 內脂一 2—基一（甲基）丙烯酸酯、2一乙基一 ？，一丁內脂 _ 3 —基—（甲基）丙烯酸酯、2一甲基—r 一 丁內脂—3 一基一（甲基）丙烯酸酯、2—乙基一^ —丁內脂一 4一基 -(甲基）丙烯酸酯、2—甲基一/ 一丁內脂一 4一基一（ 甲基）丙烯酸酯、2 —乙基一 3 一戊內脂—2—基一（甲基 )丙烯酸酯、2 —甲基一 5 —戊內脂一 2—基一（甲基）丙 燏酸酯、2 —乙基一（5 —戊內脂一 3 —基一（甲基）丙烯酸 酯、2 —甲基一 0 —戊內脂一 3—基一（甲基）丙烯酸酯、 -25- 200835744 2 —乙基一（5 —戊內脂一 4一基一（甲基）丙烯酸酯、2 — 甲基一 δ —戊內脂—4 一基一（甲基）丙烯酸酯、2_乙基 —(5 —戊內脂一 5 —基一（甲基）丙烯酸酯、2—甲基一 δ 一戊內脂一 5 —基一（甲基）丙烯酸酯之內脂： 如2—乙基一 7 - 丁內醯胺一 2-基一（甲基）丙烯 • 酸酯、2 -甲基一 7 — 丁內醯胺一 2-基一（甲基）丙烯酸 酯、2 —乙基一 r 一丁內醯胺一 3—基一（甲基）丙烯酸酯 鲁 、2 —甲基—T — 丁內醯胺—3-基—（甲基）丙儲酸酯、 2 —乙基一 r — 丁內醯胺一 4一基一（甲基）丙烯酸酯' 2 一甲基一 γ — 丁內醯胺—4 一基一（甲基）丙烯酸酯、2 — 乙基一 δ —戊內醯胺一 2 —基一（甲基）丙烯酸酯、2—甲 基一 5 —戊內醯胺一 2-基一（甲基）丙烯酸酯、2 一乙基 一 5 —戊內醯胺一3—基一（甲基）丙j：希酸酯、2—甲基一 5 —戊內醯胺一 3—基一（甲基）丙烯酸酯、2 —乙基一 5 一戊內醯胺一 4一基一（甲基）丙烯酸酯、2 —甲基一 5 — # « 戊內醯胺一 4 —基_(甲基）丙烯酸酯、2 —乙基一 δ —戊 內醯胺一 5—基一（甲基）丙烯酸酯、2—甲基一 —戊內 醯胺一 5 -基一（甲基）丙烯酸酯之內醯胺等； • 作爲（甲基）丙烯酸芳基酯，例如可舉出苯基甲基丙 - 烯酸酯、苯甲基甲基丙烯酸酯等； 作爲不飽和二羧酸二酯，例如可舉出馬來酸二乙酯、 富馬酸二乙基、衣康酸二乙基等； 作爲雙環不飽和化合物’例如可舉出雙環〔2.2.1〕 庚一2 —烯、5 —甲基雙環〔2.2·!〕庚一2—烯、5 —乙基 -26- 200835744 雙環〔2.2.1〕庚一 2 —烯、5 —甲氧基雙環〔2.2.1〕庚一 2 一烯、5 —乙氧基雙環〔2.2.1〕庚一 2—烯、5,6 —二甲氧 基雙環〔2.2.1〕庚_2 —丨希、5,6 — 一·乙氧基雙環〔2.2.1 〕庚一 2-烯、5— (2,一羥基乙基）雙環〔2.2.1〕庚一 2 一烯、5，6— 二羥基雙環〔2.2.1〕庚一 2-烯、5,6 - 二（ 羥基甲基）雙環〔2 · 2 · 1〕庚一 2 —烯、5，6 —二（2 ’ 一羥基 乙基）雙環〔2.2.1〕庚一 2—烯、5—羥基一5 —甲基雙環 〔2 · 2 · 1〕庚一 2 -烯、5 —羥基—5 —乙基雙環〔2.2 · 1〕庚 一 2—烯、5 一羥基甲基—5 —甲基雙環〔2.2.1〕庚一2 — 烯等； 作爲馬來醯亞胺化合物，例如可舉出苯基馬來醯亞胺 、環己基馬來醯亞胺、苯甲基馬來醯亞胺、N —琥珀醯胺 基一 3 -馬來醯亞胺苯甲酸酯、N-琥珀醯胺基一 4一馬來 醯亞胺丁酸酯、N -琥珀醯胺基- 6 -馬來醯亞胺己酸酯 、N-琥珀醯胺基—3一馬來醯亞胺丙酸酯、N- （9一吖 啶基）馬來醯亞胺等； 作爲不飽和芳香族化合物，例如可舉出苯乙烯、α -甲基苯乙烯、甲基苯乙烯、ρ 一甲基苯乙烯、乙烯甲 苯、P-甲氧基苯乙烯等； 作爲共軛二烯系化合物，例如可舉出1，3 -丁二烯、 異戊二烯、2，3—二甲基一 1，3 — 丁二烯等； 作爲不飽和單羧酸，例如可舉出丙烯酸、甲基丙烯酸 、巴豆酸等； 作爲不飽和二羧酸，例如可舉出馬來酸、富馬酸、檸 -27- 200835744 康酸、中康酸、衣康酸等； 作爲不飽和二羧酸酐，例如可舉出上述不飽和二竣酸 的各無水物； 作爲其他不飽和化合物’例如可舉出丙嫌腈、甲基丙 …烯腈、氯化乙烯、氯化亞乙烯、丙烯醯胺、甲基丙儲醯胺 - 、乙酸乙烯酯等。 彼等中甲基丙烯酸縮水甘油基、苯乙嫌、三環〔 φ 5.2.1·02,6〕癸烷一 8—基甲基丙烯酸酯、P —甲氧基苯乙烯 、2 —甲基環己基丙烯酸酯、1，3 — 丁二烯、雙環〔2.2.1〕 庚一 2 —烯、Ν-環己基馬來醯亞胺、甲基丙烯酸、〗一乙 基環戊基甲基丙燒酸酯、2 -甲基一 2-丙儲酸等由共聚合 反應性、耐熱性等觀點來看爲佳。 賦予這些聚合單位（a-3 )之聚合性不飽和化合物可 單獨或組合下使用。 共聚合物（A )以凝膠滲透層析儀（溶出溶劑四氫呋 # ) 喃）測定之聚苯乙烯換算數平均分子量（以下稱爲「Mu 」。）較佳爲1，〇〇〇以上，更佳爲1，000〜50,000，更佳 爲 2，500〜25,000，特佳爲 2,5 00〜15,000。Μη若未達 ' 時，會有組成物之塗佈性會不充分、或所形成之保 , 護膜的耐熱性會不足之情況，另一方面若Μη超過50,000 時，平坦化性能會有不充分的情況。 又’共聚合物（A )以凝膠滲透層析儀（溶出溶劑四 氫呋喃）測定之重量平均分子量（以下稱爲「Mw」）較 佳爲2，0 0 〇以上，更佳爲2，0 0 0〜1 0 0，0 0 0，更佳爲4，〇 0 0 -28- 200835744 〜5 0，0 0 0，特佳爲5，0 0 0〜3 0，0 0 0。Μ w若比2，0 0 0小時， 會有組成物之塗佈性不充分、或所形成之保護膜的耐熱性 不足之情況，另一方面，Mw若超過1 00,000時，會有平 坦化能不足的情況。 且，共聚合物（A)的分子量分佈（Mw/Mn )較佳爲 — 5 · 0以下，更佳爲3.0以下。 共聚合物（A )的較佳情況爲含有結構單位（a-1 )爲 φ 5〜90重量％，結構單位（a-2 )爲5〜90重量％及結構單 位（a-3 )爲5〜90重量％，更佳爲結構單位（a-Ι )爲5 〜60重量％，結構單位（a-2 )爲20〜90重量％及結構單 位（a - 3 )爲5〜6 0重量％，最佳爲結構單位（a -1 )爲5 〜50重量％，結構單位（a-2)爲30〜90重量％及結構單 位（a-3 )爲5〜50重量％。此範圍之含有量中，可實現 良好平坦性、保存安定性及耐熱性。 如此共聚合物（A )爲，將賦予結構單位（a-1 )、( # ) a-2 )及（a-3 )之聚合性不飽和化合物於適當溶劑及適當 聚合啓始劑的存在下，可藉由公知方法，例如藉由自由基 聚合而合成。 ‘ 作爲共聚合物（A )之較佳具體例，例如可舉出苯乙 * 烯/四氫一 2 Η -吡喃一 2 -基（甲基）丙烯酸酯/甲基丙 烯酸縮水甘油基/3 -甲基一 3 - （甲基）丙烯醯氧基（ acroyloxy )甲基氧雜環丁烷共聚合物、苯乙烯/四氫— 2H—吡喃一 2 —基（甲基）丙烯酸酯/ 3—甲基一 3— （甲 基）丙燒醯氧基（acroyloxy)甲基氧雜環丁烷共聚合物 -29- 200835744 苯乙烯/四氫—2H_吡喃一 2 —基（甲基）丙烯酸酯 /N-環己基馬來醯亞胺/ 3 —甲基一 3 — （甲基）丙j：希醯 氧基（acroyloxy )甲基氧雜環丁烷共聚合物、苯乙烯/ 四氫一 2H—吡喃一 2—基（甲基）丙烯酸酯/1，3 — 丁二烯 /3 —甲基—3—(曱基）丙儲醯氧基（acroyloxy)甲基 氧雜環丁烷共聚合物、苯乙烯/四氫一 2H—吡喃一 2-基 (甲基）丙烯酸酯/甲基丙烯酸三環〔5.2.1· 〇2,6〕癸烷一 8 —基/3 —甲基一3—(甲基）丙燒醯氧基（acroyloxy) 甲基氧雜環丁烷共聚合物、苯乙烯/四氫一 2H—吡喃一 2 一基（甲基）丙烯酸酯/甲基丙烯酸/ 3 —甲基一 3 —（甲 基）丙烯醯氧基（&(：1*(^1〇\7)甲基氧雜環丁院共聚合物 苯乙烯/四氫一 2H-吡喃一 2—基（甲基）丙烯酸酯 /甲基丙烯酸縮水甘油基/ 3 —乙基一 3—（甲基）丙烯醯 氧基（acroyloxy )甲基氧雜環丁烷共聚合物、苯乙烯/ 四氫一 2H —吡喃一 2 —基（甲基）丙烯酸酯/ 3—乙基一3 一（甲基）丙烯醯氧基（acroyloxy)甲基氧雜環丁烷共 聚合物、苯乙烯/四氫一 2H—吡喃一 2—基（甲基）丙烯 酸酯/ N—環己基馬來醯亞胺/ 3 —乙基一 3 — （甲基）丙 烯醯氧基（acroyloxy )甲基氧雜環丁烷共聚合物、苯乙 烯/四氫一 2H —吡喃—2 —基（甲基）丙烯酸酯/ u— 丁 二嫌/3 —乙基—3—(甲基）两嫌醯氧基（acroyloxy) 甲基氧雜環丁烷共聚合物、苯乙烯/四氫一 2H—吡喃—2 -30- 200835744 一基（甲基）丙烯酸酯/甲基丙烯酸三環〔5.2.1. 02,6〕癸 烷一 8 —基/ 3 -乙基一 3 — （甲基）丙烯醯氧基（ aero y 1 oxy )甲基氧雜環丁烷共聚合物、苯乙烯/四氫一 2H—吡喃一 2 —基（甲基）丙烯酸酯/甲基丙烯酸/ 3 — 乙基一3—(甲基）丙烯醯氧基（acroyloxy)甲基氧雜環 ^ 丁烷共聚合物、苯乙烯/1 一 （環己氧基）乙基（甲基） 丙烯酸酯/甲基丙烯酸縮水甘油基/ 3—甲基一 3— （甲基 Φ )丙烯醯氧基（acroyloxy )甲基氧雜環丁烷共聚合物、 苯乙烯/1 一（環己氧基）乙基（甲基）丙烯酸酯/ 3-甲 基一3—(甲基）丙燃醯氧基（acroyloxy)甲基氧雜環丁 烷共聚合物、苯乙烯/1 一（環己氧基）乙基（甲基）丙 烯酸酯/ N—環己基馬來醯亞胺/ 3 -甲基一 3 — （甲基） 丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙烯/1 一（環 己氧基）乙基（甲基）丙烯酸酯/1，3 — 丁二烯/ 3 —甲基 - 3 - （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯 ) 乙燃/1 一（環己氧基）乙基（甲基）丙嫌酸醋/甲基丙 烯酸三環〔5.2.1.02,6〕癸烷一 8 —基/3 一甲基一 3一 （甲 基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙靖/ ；!一 * (環己氧基）乙基（甲基）丙烯酸酯/甲基丙嫌酸/ 3 — • 甲基- 3-（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物 、苯乙烯/1一 （環己氧基）乙基（甲基）丙烯酸酯/甲 基丙烯酸縮水甘油基/ 3 —乙基一 3 -（甲基）丙烯驢氧基 甲基氧雜環丁烷共聚合物、苯乙烯/1 - （環己氧基）乙 基（甲基）丙烯酸酯/ 3 —乙基一 3—（甲基）丙燒醯氧基 -31 - 200835744 甲基氧雜環丁烷共聚合物、苯乙烯71一（環己氧基）乙 基（甲基）丙Μ酸酯/ N-環己基馬來醋亞胺—乙基 - 3- （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯 乙烯/1—(環己氧基）乙基（甲基）丙烯酸酯/;1，3 一丁 一烯/ 3乙基一 3—（甲基）丙烯醯氧基甲基氧雜環丁烷 共聚合物、Examples of the polymerizable unsaturated compound containing an oxirane group include glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, and α-η-propyl acrylate glycidyl. Α-η-butyl acrylate glycidyl, acrylic 3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxyheptyl, A Acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, fluorene-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether And p-vinylbenzyl glycidyl ether; and examples of the (meth)acrylic acid esters include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 3 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3 dihydroxypropyl (methyl) propionate Ester, 2-methyl propylene oxyethyl glycidol, 4-hydroxyphenyl (meth) acrylate , methyl (meth) acrylate, ethyl (meth) acrylate, η-butyl (meth) acrylate, sec - butyl (methyl) enoate, 2-ethylhexyl (A Acrylate, isodecyl (meth) acrylate, η-lauryl (meth) acrylate, undecyl (meth) acrylate, η - stearin (meth) acrylate Ester 1 -butoxy (meth) acrylate, 1 dimethyl (iso) propyl (meth) acrylate, ; Monomethyl(iso)butyl(methyl)propoxylate vinegar 1 monomethyl(iso)octyl (meth) acrylate, 1 methyl mono-1-ethylethyl (meth) acrylate Ester, 1-methyl-l-ethyl-22-200835744 (iso)propyl (meth) acrylate, 1-methyl-monoethyl (iso)butyl (meth) acrylate, 1 Methyl-1-ethyl(iso)octyl acrylate, monoethyl (iso)propyl (meth) acrylate, mono-di(iso)butyl (meth) acrylate, 1 Monoethyl (iso)octyl (meth) acrylate, etc.; " As the cyclic alkyl (meth) acrylate, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, φ tricyclo [5.2.1. 〇 2, 6] decane 8-octyl (meth) acrylate, tricyclo [5.2.1.0,] oxime; I: 兀 8-yl Oxyethyl (meth) propionate, isobornyl (meth) acrylate, 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) acrylate, 1 —methylcyclopenta (Meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1- Methylcyclodecane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclopropane (meth) propylene® J acid ester, 1-ethylcyclobutane (1 ethylcyclobutane) Methyl) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (meth) acrylate, 1-B Cyclooctane (methyl') acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethyl-cyclodecane (meth) acrylate, 1-(iso)propylcyclopropane (Meth) acrylate, 1-(iso)propylcyclobutyl (meth)propionate, 1 (iso)propylcyclopentyl (meth) acrylate, 1 (iso)propyl Cyclohexyl (meth) acrylate, mono (iso) propyl cycloheptane (meth) acrylate, 1- (iso) propyl cyclooctane (meth) acrylate, 1 -23- 200835744 one ( different Propylcyclodecane (meth) acrylate, 1-(iso)propylcyclodecane (meth) acrylate, mono-isobutylcyclopropane (meth) acrylate, 1 (iso) Butylcyclobutane (meth) acrylate ' 1 mono(isobutyl)cyclopentyl (meth) acrylate, mono-isobutyl cyclohexyl (meth) acrylate, 1 (iso) Butylcycloheptane (methyl') acrylate, mono-(iso)butylcyclooctane (meth) acrylate ' 1 mono(iso)butylcyclodecane (meth) acrylate, 1 ( Isobutyl butyl cyclomethic acid (meth) acrylate, mono (iso)pentyl cyclopropyl (meth) acrylate, mono (iso) amyl cyclobutyl (meth) acrylate, 1 Mono(iso)pentylcyclopentyl (meth) acrylate, mono-(iso)pentylcyclohexyl (meth) acrylate, mono-(iso)pentylcycloheptyl (meth) acrylate, 1 Mono(iso)pentylcyclooctyl (meth) acrylate, mono(iso)pentylcyclodecyl (meth) acrylate, mono-(iso)pentylcyclodecyl (meth) acrylate, 1 a Iso)hexylcyclopropyl (meth) acrylate, 1-(iso)hexylcyclobutyl (meth) acrylate, 1 ® ) mono(iso)hexylcyclohexyl (meth) acrylate, 1-(iso) Hexylcycloheptyl (meth) acrylate, mono-(iso)hexylcyclooctyl (meth) acrylate, mono-(iso)hexylcyclodecyl (meth) acrylate, 1 'one (di) Hexylcyclodecyl (meth) acrylate, mono (iso)heptyl ~ cyclopropyl (meth) acrylate, mono (iso)heptylcyclobutyl (meth) acrylate, 1 (different) Heptylcycloheptyl (meth) acrylate, 1-(iso)heptylcycloheptyl (meth) acrylate, mono-(iso)heptylcycloheptyl (meth) acrylate, 1 ( Isoheptylcyclooctyl (meth) acrylate, 1-(iso)heptylcyclodecyl (meth) acrylate, 1 24 - 200835744 mono (iso)heptylcyclodecyl (meth) acrylate , 1 (iso)octylcyclopropyl (meth) acrylate, 1 (iso)octylcyclobutyl (meth) acrylate, 1 (iso)octylcyclooctyl (methyl) Acrylate, 1 (iso)octylcyclooctyl (meth) acrylate, 1 (iso)octylcycloheptyl (meth) acrylate, 1 (iso)octylcyclooctyl (A) Base) Acetate vinegar, 1 (iso) arginylcyclodecyl (methyl) propyl vinegar, 1 (iso)octylcyclodecyl (meth) acrylate, 2-ethyltricyclo[ 3.3.1.13'7]decane-2-yl-(meth)acrylate, 2-methyltricyclo[3.3.1.13'7]decane-2-yl-(meth)acrylate, 1-B Tricyclo[3 · 3 · 1 · 13,7] decane-l-yl-mono(meth)acrylate; i-ethyltricyclo[3·3·1·13,7]decane-1 Mono-(meth)acrylate, 3-hydroxytricyclo[3.3.1.13,7]decane-i-yl-(meth)acrylate, etc.; alkyl moiety of cyclic alkyl (meth)acrylate It may be a lactone structure, an intrinsic amine structure or an acetal structure, and as an example thereof, 2-ethyl-r-butyrolactone-2-alkyl-(meth)acrylate, 2-methyl-r-r Butyl lactone 2-yl-(meth) acrylate, 2-ethyl ? , butyl lactone _ 3 - yl - (meth) acrylate, 2 - methyl - r - butyl lactone - 3 - yl mono (meth) acrylate, 2-ethyl phthalate - butyl lactone 4-yl-(meth) acrylate, 2-methyl-/butyrolactone-tetramethyl-(meth)acrylate, 2-ethyl-1,3-pentalactone-2-yl-(A) Acrylate, 2-methyl-5-pentalactone-2-phenyl-propionate, 2-ethyl-(5-pentalactone-3-yl-(meth)acrylic acid Ester, 2-methyl-O-pentalactone-3-yl-(meth)acrylate, -25- 200835744 2 -ethyl-(5-pentalactone-4-1-yl-(meth)acrylate , 2 - methyl-δ-pental lactone-4-yl-(meth)acrylate, 2-ethyl-(5-pentalactone-5-yl-(meth)acrylate, 2-methyl a δ-p-lactone-5-yl-(meth) acrylate lactone: such as 2-ethyl-7-butylidene-2-yl-(meth) propylene ester, 2-A Base one 7 - butane phthalamide 2-yl mono (meth) acrylate, 2-ethyl-r-butyrolactam-3-yl-(meth)acrylate Lu, 2-methyl-T-butylidene-3-yl-(methyl)propionate, 2 —Ethyl-r-butylidene-1,4-yl-mono(meth)acrylate' 2 monomethyl-γ-butylidene-4-yl-mono(meth)acrylate, 2-ethyl-ethyl δ-Pentamylamine 2-yl-(meth)acrylate, 2-methyl-5-pentalamine- 2-yl-(meth)acrylate, 2-ethyl-5-pentene Indoleamine 3-yl-(meth)propanyl j: oxalate, 2-methyl-5-pentalinamide-3-yl-(meth)acrylate, 2-ethyl-5-pentene Indoleamine 4-yl-mono(meth)acrylate, 2-methyl-5-# « valeroinyl 4-yl-(meth) acrylate, 2-ethyl-δ-valeroinamide a 5-methyl-(meth) acrylate, 2-methyl-pentalinamide-5-yl-(meth) acrylate, decylamine, etc.; • as an aryl (meth) acrylate, For example, phenylmethyl propenoate, benzyl group Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate; and examples of the bicyclic unsaturated compound are exemplified. Bicyclo[2.2.1] Glycid-2-ene, 5-methylbicyclo[2.2·!]gly-2-ene, 5-ethyl-6-200835744 Bicyclo[2.2.1]gly-2-ene, 5 — Methoxybicyclo[2.2.1]heptane-2-ene, 5-ethoxybicyclo[2.2.1]heptane-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2丨希,5,6 —1·ethoxybicyclo[2.2.1]heptan-2-ene, 5-(2,1-hydroxyethyl)bicyclo[2.2.1]heptane-2-ene, 5,6- Dihydroxybicyclo[2.2.1]heptyl-2-ene, 5,6-di(hydroxymethyl)bicyclo[2 ·2 ·1]heptan-2-ene, 5,6-di(2'-hydroxyethyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo[2 · 2 · 1] hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2 · 1]g 2-alkenyl, 5-hydroxymethyl- 5-methylbicyclo[2.2.1]gly- 2-ene; as a horse Examples of the quinone imine compound include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinylamino-3-maleimide benzene. Acid ester, N-succinylamine, 4-maleimide butyrate, N-succinylamino-6-maleimide caproate, N-succinylamine-3醯iminopropionate, N-(9-acridinyl)maleimide, etc. Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, methylstyrene, and ρ. Methylstyrene, vinyl toluene, P-methoxystyrene, etc.; as the conjugated diene compound, for example, 1,3-butadiene, isoprene, 2,3-dimethyl 1. 1,3-butadiene or the like; examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid; and examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, and lemon. -27- 200835744 Kang acid, mesaconic acid, itaconic acid, etc.; as the unsaturated dicarboxylic anhydride, for example, each anhydrate of the above unsaturated dicarboxylic acid; as other unsaturated It was' too nitriles and examples thereof include malonic, ... methylpropionitrile acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylic reservoir Amides -, and vinyl acetate. Among them, glycidyl methacrylate, benzene, tricyclo[ φ 5.2.1·02,6]decane-8 methacrylate, P-methoxystyrene, 2-methyl ring Hexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, fluorene-cyclohexylmaleimide, methacrylic acid, monoethylcyclopentylmethylpropanoic acid The ester, 2-methyl-2-hydrogen storage acid, and the like are preferred from the viewpoints of copolymerization reactivity, heat resistance, and the like. The polymerizable unsaturated compound to which these polymerization units (a-3) are imparted can be used singly or in combination. The polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mu") measured by a gel permeation chromatography (dissolved solvent tetrahydrofuran #) is preferably 1, more than 〇〇〇 More preferably, it is 1,000 to 50,000, more preferably 2,500 to 25,000, and particularly preferably 2, 5 to 00 to 15,000. If Μη does not reach ', the coating property of the composition may be insufficient, or the formation may be insufficient, and the heat resistance of the film may be insufficient. On the other hand, if Μη exceeds 50,000, the flattening performance may not be Full case. Further, the weight average molecular weight (hereinafter referred to as "Mw") measured by the gel permeation chromatography (dissolved solvent tetrahydrofuran) of the copolymer (A) is preferably 2,0 0 or more, more preferably 2,0 0. 0 to 1 0 0, 0 0 0, more preferably 4, 〇 0 0 -28- 200835744 ~ 5 0, 0 0 0, particularly preferably 5, 0 0 0 to 3 0, 0 0 0. When Μ w is less than 2,0 0, the coating property of the composition is insufficient, or the heat resistance of the formed protective film is insufficient. On the other hand, if Mw exceeds 100,000, flattening occurs. Insufficient situation. Further, the molecular weight distribution (Mw/Mn) of the copolymer (A) is preferably -5 · 0 or less, more preferably 3.0 or less. The copolymer (A) preferably has a structural unit (a-1) of φ 5 to 90% by weight, a structural unit (a-2) of 5 to 90% by weight, and a structural unit (a-3) of 5 ～90% by weight, more preferably 5 to 60% by weight of the structural unit (a-Ι), 20 to 90% by weight of the structural unit (a-2) and 5 to 60% by weight of the structural unit (a - 3 ) Preferably, the structural unit (a-1) is 5 to 50% by weight, the structural unit (a-2) is 30 to 90% by weight, and the structural unit (a-3) is 5 to 50% by weight. Among the contents of this range, good flatness, storage stability, and heat resistance can be achieved. Thus, the copolymer (A) is a polymerizable unsaturated compound which imparts structural units (a-1), (#) a-2) and (a-3) in the presence of a suitable solvent and a suitable polymerization initiator. It can be synthesized by a known method, for example, by radical polymerization. As a preferable specific example of the copolymer (A), for example, phenethyl ene/tetrahydro-2 Η-pyran-2-yl (meth) acrylate/glycidyl methacrylate/3 is exemplified. -methyl-3-(meth)acryloxyl (acroyloxy)methyloxetane copolymer, styrene/tetrahydro-2H-pyran-2-yl acrylate / 3 —Methyl 3-(methyl)propanoxy acroyloxymethyloxetane copolymer -29- 200835744 Styrene/tetrahydro-2H-pyran-2-yl (methyl) Acrylate/N-cyclohexylmaleimide/3-methyl-1,3-(methyl)propene j: acroyloxymethyloxetane copolymer, styrene/tetrahydrogen a 2H-pyran-2-yl (meth) acrylate / 1,3 - butadiene / 3-methyl-3-(indenyl) propyl acroyloxy methyl oxetane Copolymer, styrene/tetrahydro-2H-pyran-2-yl (meth) acrylate/trimethyl methacrylate [5.2.1· 〇2,6] decane-8-yl/3-A A 3-(methyl)propanoxy acroyloxy Oxycyclobutane copolymer, styrene/tetrahydro-2H-pyran-2-yl (meth) acrylate/methacrylic acid/3-methyl-3-(methyl) propylene oxy group (&(:1*(^1〇\7)methyloxetan compound copolymer styrene/tetrahydro-2H-pyran-2-yl (meth) acrylate/methacrylic acid glycidol /3 -ethyl-3-(meth)acryloxy acroyloxymethyloxetane copolymer, styrene / tetrahydro-2H-pyran-2-yl (meth)acrylic acid Ester / 3-ethyl-1,3-(meth)acryloxy acroyloxymethyloxetane copolymer, styrene/tetrahydro-2H-pyran-2-yl (meth)acrylic acid Ester / N-cyclohexylmaleimide / 3 - ethyl - 3 - (meth) propylene alkoxy (acroyloxy ) methyl oxetane copolymer, styrene / tetrahydro - 2H - pyr —-2-yl (meth) acrylate / u - butyl succinyl / 3 - ethyl - 3 - (methyl) sulphonic acid (acroyloxy) methyl oxetane copolymer, styrene /tetrahydro-2H-pyran-2 - 30- 200835744 mono-(meth)acrylate/trimethyl methacrylate [5.2.1. 02,6]decane-8-yl/3-ethyl-3-(methyl)propenyloxy (aero y 1 oxy )methyloxetane copolymer, styrene/tetrahydro-2H-pyran-2-yl acrylate/methacrylic acid / 3 - ethyl 3-(methyl) Acroyloxy methyl oxo-butane copolymer, styrene / 1 mono(cyclohexyloxy)ethyl (meth) acrylate / glycidyl methacrylate / 3 - A A 3-(methyl Φ ) acryloxy acroyloxy methyl oxetane copolymer, styrene / 1 - (cyclohexyloxy) ethyl (meth) acrylate / 3-methyl A 3-(methyl)propane oxy-oxylated acroyloxymethyl oxetane copolymer, styrene / 1 -(cyclohexyloxy)ethyl (meth) acrylate / N-ring Hexylmaleimide / 3-methyl-3-(meth) propylene methoxymethyl oxetane copolymer, styrene / 1 mono(cyclohexyloxy)ethyl (methyl) Acrylate / 1,3 - Ding / 3 -Methyl- 3 - (meth) propylene methoxymethyl oxetane copolymer, benzene) Ethylene / 1 mono(cyclohexyloxy)ethyl (methyl) propylene vinegar /Tricyclo[meth] methacrylate [5.2.1.02,6]decane-8-yl/3 monomethyl-3-mono(methyl)propenyloxymethyloxetane copolymer, phenethyl jing/ ;**(cyclohexyloxy)ethyl(meth)acrylate/methylpropionic acid/3 — • methyl-3-(methyl)propenyloxymethyloxetane copolymerization , styrene / 1-mono(cyclohexyloxy)ethyl (meth) acrylate / glycidyl methacrylate / 3-ethyl 3-(methyl) propylene methoxymethyl oxetane Alkane copolymer, styrene/1-(cyclohexyloxy)ethyl(meth)acrylate/3-ethyl-3-(methyl)propanoximeoxy-31 - 200835744 methyloxyheterocycle Butane copolymer, styrene 71-(cyclohexyloxy)ethyl(methyl)propionate / N-cyclohexylmaleacetamide-ethyl-3-(methyl)propenyloxy Methyl oxetane copolymer, styrene / 1-(cyclohexyloxy) Ethyl (meth) acrylate /; 1,3 monobutene / 3 ethyl - 3 - (meth) propylene methoxymethyl oxetane copolymer,

本乙烯/1 一（環己氧基）乙基（甲基）丙烯酸酯/ 甲基丙烯酸三環〔5H0U〕癸烷_8 一基/3—乙基一 3 -（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙烯 /1 一 （環己氧基）乙基（甲基）丙烯酸酯/甲基丙烯酸 /3—乙基〜（甲基）丙烯醯氧基甲基氧雜環丁烷共聚 合物、本乙烯/ t 一丁基甲基丙烯酸酯/甲基丙烯酸縮水 甘油基/ 3〜甲基—3一（甲基）丙烯醯氧基甲基氧雜環丁 烷共聚合物、苯乙烯/ t 一丁基甲基丙烯酸酯/ 3一甲基一 3- （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙 燃/ ί 一丁基甲基丙烯酸酯/ N-環己基馬來醯亞胺/ 3 -甲基一 3-(甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物 、苯乙；H/t〜丁基甲基丙烯酸酯/1，3 一 丁二烯/ 3 一甲 基- 3—(甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、 丁基甲基丙烯酸酯/甲基丙烯酸三環〔 5·2·1·0’〕癸烷—8 —基/ 3—甲基一 3— （甲基）丙烯醯 氧基甲基氧雜環丁烷共聚合物、 苯乙燦/t 一丁基甲基丙烯酸酯/甲基丙烯酸/ 3 一甲 基一 3 一（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、 -32- 200835744 苯乙烯/t 一丁基甲基丙烯酸酯/甲基丙烯酸縮水甘油基 /3—乙基一 3—（甲基）丙烯醯氧基甲基氧雜環丁烷共聚 合物、苯乙烯/ t 一丁基甲基丙烯酸酯/ 3 —乙基一 3 - （ 甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙烯/ t 一丁基甲基丙烯酸酯/ N-環己基馬來醯亞胺/ 3 -乙基 - 3- （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯 乙烯/ t 一丁基甲基丙烯酸酯/ ；[，3 — 丁二烯/ 3 —乙基一 3 -（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯乙烯 /t — 丁基甲基丙烯酸酯/甲基丙烯酸三環〔5.2.〗.〇2,6〕 癸烷—8-基/ 3—乙基一 3—(甲基）丙烯醯氧基甲基氧 雜環丁烷共聚合物、 苯乙嫌/ t 一丁基甲基丙烯酸酯/甲基丙烯酸/ 3一乙 基- 3 —（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、 苯乙烯/1 -乙基環戊基甲基丙烯酸酯/甲基丙烯酸縮水 甘油基/ 3 -甲基〜3一（甲基）丙烯醯氧基甲基氧雜環丁 烷共聚合物、苯乙烯/1 -乙基環戊基甲基丙烯酸酯/ 3 -甲基- 3 -（甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物 、苯乙烯/1 一乙基環戊基甲基丙烯酸酯/ N 一環己基馬 來醯亞胺/ 3-甲基一 3一（甲基）丙烯醯氧基甲基氧雜環 丁烷共聚合物、苯乙烯/1 一乙基環戊基甲基丙烯酸酯/ 1，3 — 丁二烯/ 3〜甲基—3 — （甲基）丙烯醯氧基甲基氧 雜環丁烷共聚合物、苯乙烯/1 -乙基環戊基甲基丙烯酸 酯/甲基丙烯酸三環〔5·2·1·02,6〕癸烷一 8—基/ 3-甲基 一 3— （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、苯 -33- 200835744 乙_/1 一乙基環戊基甲基丙烯酸酯/甲基丙烯酸/ 3 一甲 基- 3 — （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、 苯乙烯/1 -乙基環戊基甲基丙烯酸酯/甲基丙烯酸縮水 甘油基/ 3 -乙基一 3〜（甲基）丙烯醯氧基甲基氧雜環丁 院共聚合物、苯乙烯/1 一乙基環戊基甲基丙烯酸酯/ 3 一 乙基- 3 - （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物 、苯乙嫌/1 一乙基環戊基甲基丙烯酸酯/ N 一環己基馬 來釀亞胺/ 3 -乙基〜3一（甲基）丙烯醯氧基甲基氧雜環 丁院共聚合物、苯乙烯/1 一乙基環戊基甲基丙烯酸酯/ ，3 — 丁二烯 乙基- 3 — （甲基）丙烯醯氧基甲基氧 雜環丁；I：完共聚合物、苯乙烯/1 一乙基環戊基甲基丙烯酸 酯/甲基丙嫌酸三環〔5.21〇2,6〕癸烷一 8 一基/3 —乙基 - 3 - （甲基）丙嫌醯氧基甲基氧雜環丁烷共聚合物、苯 乙嫌/1 一乙基環戊基甲基丙烯酸酯/甲基丙烯酸/ 3 一乙 基_3 - （甲基）丙烯醯氧基甲基氧雜環丁烷共聚合物、 苯Z 1 -乙基環戊基甲基丙烯酸酯/甲基丙烯酸縮水 甘 '油S/3 -（甲基）丙烯醯氧基乙基氧雜環丁烷共聚合 物、苯乙燃/1 一乙基環戊基甲基丙烯酸酯/ 3 一（甲基） 丙嫌醯氧基乙基氧雜環丁烷共聚合物、苯乙烯/1 一乙基 環戊基甲基丙嫌酸酯/ N-環己基馬來醯亞胺/ 3 — （甲 基）丙烯醯氧基乙基氧雜環丁烷共聚合物、苯乙烯/i — 乙基環戊基甲基丙烯酸酯/1，3 — 丁二烯/ 3 -（甲基）丙 烯醯氧基乙基氧雜環丁烷共聚合物、苯乙烯/1 -乙基環 戊基甲基丙烯酸酯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷一 -34- 200835744 8—基/ 3 -（甲基）丙烯醯氧基乙基氧雜環丁烷共聚合物 、苯乙烯/1 一乙基環戊基甲基丙烯酸酯/甲基丙烯酸/ 3 -（甲基）丙烯醯氧基乙基氧雜環丁烷共聚合物、苯乙烯 /1 -乙基環戊基甲基丙烯酸酯/甲基丙烯酸縮水甘油基 /3 -（甲基）丙烯醯氧基乙基氧雜環丁烷共聚合物、苯 乙烯/1 -乙基環戊基甲基丙烯酸酯/3- （甲基）丙烯醯 氧基乙基氧雜環丁烷共聚合物、苯乙烯/1 -乙基環戊基 甲基丙烯酸酯/ N-環己基馬來醯亞胺/ 3 - （甲基）丙 烯醯氧基乙基氧雜環丁烷共聚合物、苯乙烯/1 一乙基環 戊基甲基丙嫌酸酯/1，3 — 丁二嫌/ 3 - （甲基）丙嫌醯氧 基乙基氧雜環丁烷共聚合物、苯乙烯/1 -乙基環戊基甲 基丙烯酸酯/甲基丙烯酸三環〔5.2.1 · 02，6〕癸烷一 8 —基 /3 -（甲基）丙烯醯氧基乙基氧雜環丁烷共聚合物、苯 乙烯/1 一乙基環戊基甲基丙烯酸酯/甲基丙烯酸/ 3 — （ 甲基）丙烯醯氧基乙基氧雜環丁烷共聚合物等。 本發明的硬化性樹脂組成物除上述共聚合物（A )以 外，亦可含有其他成分。作爲相關其他成分，例如可舉出 接著助劑（B )、陽離子聚合性化合物（C )、界面活性 劑（D )、多官能丙烯酸酯單體（E )、感熱性酸產生劑 (F )等。 接著助劑（B ) 上述接著助劑（B )係爲提高所形成之保護膜與基板 的密著性而添加。 -35- 200835744 作爲如此接著助劑（B )，例如可使用具有反應性取 代基之官能性矽烷偶合劑。作爲上述反應性取代基，例如 可舉出羧基、甲基丙烯醯基、異氰酸酯基、環氧基等。 作爲接著助劑（B )之具體例，例如可舉出三甲氧基 甲石夕院基安息香酸、7 -甲基丙烯氧基丙基三甲氧基矽烷 、乙烯三乙酸矽烷、乙烯三甲氧基矽烷、7 一異氰酸酯丙 基三乙氧基矽烷、7 一環氧丙氧基丙基三甲氧基矽烷、7 -環氧丙氧基丙基三乙氧基矽烷、^一 （3,4一環氧基環 己基）乙基二甲氧基砂院等。 如此接著助劑（B )對共聚合物（a ) 1 0 0重、量份中， 較佳爲使用3 0重量份以下，更佳爲使用2 5重量份以下的 量。接著助劑（B )的量若超過30重量份時，所得之保護 膜的耐熱性會有不充分的情況。 陽離子聚合性化合物（C) 上述陽離子聚合性化合物（C )係爲提高所形成之保 護膜的ITO蝕刻耐性時而添加。陽離子聚合性化合物（C )爲分子内具有2個以上之環氧乙烷基或氧雜環丁烷基的 化合物。作爲上述分子内具有2個以上之環氧乙烷基或氧 雜環丁烷基的化合物，例如可舉出分子内具有2個以上的 環氧基之化合物、或具有3，4-環氧基環己基之化合物。 作爲上述分子内具有2個以上之環氧基的化合物，例 如可舉出雙酚A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、氫化雙酚A二縮水甘油基 -36- 200835744 醚、氫化雙酚F二縮水甘油基醚、氫化雙酚AD二縮水甘 油基醚、臭素化雙酚A二縮水甘油基醚、臭素化雙酚f 二縮水甘油基醚、臭素化雙酚S二縮水甘油基醚等雙酚化 合物之二縮水甘油基醚； 1，4 一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 醚等多元醇之聚縮水甘油基醚； 藉由乙二醇、丙二醇、甘油等脂肪族多元醇中加成1 種或2種以上的環氧化物所得之聚醚多元醇之聚縮水甘油 基醚；酚漆用酚醛型環氧基樹脂；甲酚漆用酚醛型環氧基 樹脂；聚酚型環氧基樹脂；脂肪族長鏈二鹽基酸之二縮水 甘油基酯；高級脂肪酸之縮水甘油基酯；環氧基化大豆油 、環氧基化亞麻仁油等。 作爲上述分子内具有2個以上的環氧基之化合物的販 賣品，例如作爲雙酚A型環氧基樹脂可使用Epikote 1001 、同 1002 、同 1003 、同 1004 、同 1007 、同 1009 、同 1010、同828(以上，日本環氧樹脂（股）製）等； 作爲雙酚F型環氧基樹脂可使用Epikote 8 07 (日本 環氧樹脂（股）製）等； 作爲酚漆用酚醛型環氧基樹脂可使用Epikote 152、 同154、同157S65(以上，日本環氧樹脂（股）製）、 EPPN201、同202(以上，日本化藥（股）製）等； 作爲甲酚漆用酚醛型環氧基樹脂可使用 E0CN 102、 -37- 200835744 同 103S、同 104S、 1020、 1025、 1027(以上，日本化藥 (股）製）、Epikote 180S75 (日本環氧樹脂（股）製） 等； 作爲聚酚型環氧基樹脂可使用 Epikote 1 03 2H60、同 XY-40 00 (以上，日本環氧樹脂（股）製）等； 作爲環狀脂肪族環氧基樹脂可使用CY-175、同177 、同 179、araldat CY-182、同 192、184 (以上，Ciba Specialty Chemicals Inc 公司製）、ERL-4234、4299、 4221、4206(以上，U.C.C 公司製）、Shodyne509(昭和 電工（股）製）、EPICLON200、同 400 (以上，大日本 墨水（股）製）、Epikote 871、同872 (以上，曰本環氧 樹脂（股）製）、ED-5 66 1、同 5 662 (以上，Calanese 塗 佈公司製）等； 作爲脂肪族聚縮水甘油基醚可使用EPOLIGHT100MF (共榮社化學（股）製）、epiol TMP (日本油脂（股） 製）等。 作爲上述分子内具有2個以上之3，4 一環氧基環己基 的化合物，例如可舉出3，4 一環氧基環己基甲基一3’，4’ -環 氧基環己烷羧酸酯、2-（3，4 一環氧基環己基一 5，5 -螺 —3，4 一環氧基）環己烷一間一二噁烷、雙（3,4 一環氧基 環己基甲基）己二酸酯、雙（3，4 一環氧基一 6 —甲基環己 基甲基）己二酸酯、3,4一環氧基一 6 —甲基環己基一3’，4’ 一環氧基—6’ 一甲基環己烷羧酸酯、伸甲基雙（3,4 一環 氧基環己烷）、二環戊二烯二環氧化物、乙二醇的二（ -38- 200835744 3，4 一環氧基環己基甲基）醚、伸乙基雙（3,4 一環氧基環 己烷羧酸酯）、內脂變性3,4一環氧基環己基甲基一 3’，4’ -環氧基環己烷羧酸酯等。 這些陽離子聚合性化合物（c )中，以酣漆用酣醒型 環氧基樹脂及聚酚型環氧基樹脂爲佳° 本發明的樹脂組成物中陽離子聚合性化合物（C )之 使用量爲共聚合物（A) 100重量份中，較佳爲3〜200重 量份，更佳爲5〜100重量份，特佳爲1〇〜50重量份。陽 離子聚合性化合物（C )的使用量若比200重量份多時， 組成物之塗佈性會產生問題，另一方面若未達3重量份時 ，所得之保護膜的硬度會有不足之情況。 界面活性劑（D ) 上述界面活性劑（D )係爲提高本發明之樹脂組成物 的塗佈性能而添加。 作爲如此界面活性劑（D )，例如可舉出氟界面活性 劑、聚矽氧界面活性劑、非離子界面活性劑、其他界面活 性劑。 作爲上述氟界面活性劑，例如可舉出BM CHEMIE公 司製 商品名：BM-1000、BM-1100、大日本墨水化學工 業（股）製商品名：MegafakF142D、同 F172、同 F173 、同 F183、同 R_08、住友 3M (股）製 商品名： FrolardFC-135、同 FC-170C、同 FC-43 0、同 FC-431、( 股）Neos 製商品名：Ftergent 250、同 251、同 222F、 -39- 200835744 FTX-21 8、旭硝子（股）製商品名：SerflonS-1 12、同S-113、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等販賣品。 作爲上述聚矽氧界面活性劑，例如可舉出 Toray · dowcorning·聚矽氧（股）製商品名：SH-28PA、SH-190 、SH-193 、 SZ-603 2 、 SF-842 8 、 DC-57 、 DC-190 、Ethylene/1(cyclohexyloxy)ethyl(meth)acrylate/tricyclo[5H0U]decane_8-yl/3-ethyl-3-(methyl)propenyloxy Methyl oxetane copolymer, styrene / 1 mono(cyclohexyloxy)ethyl (meth) acrylate / methacrylic acid / 3-ethyl ~ (meth) propylene methoxymethyl Oxetane copolymer, this ethylene/t-butyl methacrylate/glycidyl methacrylate/3~methyl-3(meth)acryloxymethyloxybutane copolymerization , styrene / t monobutyl methacrylate / 3 monomethyl - 3 - (meth) propylene methoxy methyl oxetane copolymer, phenyl ethane / butyl mono methacrylate / N -cyclohexylmaleimide / 3-methyl-3-(meth)propenyloxymethyloxetane copolymer, phenethyl; H/t~butyl methacrylate/1,3 Butadiene / 3 monomethyl 3-(meth) propylene methoxymethyl oxetane copolymer, butyl methacrylate / methacrylic acid tricyclo [5·2·1·0'癸 — - 8 — / 3-methyl-3-(meth)propenyloxymethyloxetane copolymer, phenethylcan/t-butyl methacrylate/methacrylic acid / 3 monomethyl one 3 one ( Methyl) propylene methoxymethyl oxetane copolymer, -32- 200835744 styrene / t monobutyl methacrylate / glycidyl methacrylate / 3-ethyl 3-(methyl) Propylene methoxymethyl oxetane copolymer, styrene / t monobutyl methacrylate / 3-ethyl 3-(3-methyl) propylene methoxymethyl oxetane copolymer , styrene / t monobutyl methacrylate / N-cyclohexylmaleimide / 3-ethyl-3-(meth) propylene methoxymethyl oxetane copolymer, styrene / T-butyl methacrylate / ; [, 3 - butadiene / 3-ethyl 3-(methyl) propylene methoxymethyl oxetane copolymer, styrene / t - butyl methacrylate Ester/trimethyl methacrylate [5.2.]. 〇2,6] decane-8-yl/3-ethyl-3-(methyl)propenyloxymethyloxetane copolymer, Benzene/t-butyl-butyl methacrylate/methacrylic acid/3-ethyl-3-(methyl)propenyloxymethyloxetane copolymer, styrene/1-ethylcyclopentane Methyl methacrylate / glycidyl methacrylate / 3-methyl~3-(meth) propylene methoxymethyl oxetane copolymer, styrene / 1-ethylcyclopentyl Acrylate / 3-methyl-3-(meth)propenyloxymethyloxetane copolymer, styrene/1 ethylcyclopentyl methacrylate / N-cyclohexylmalay醯imino/3-methyl-3-mono(methyl)propenyloxymethyloxetane copolymer, styrene/1 ethylethylcyclopentyl methacrylate / 1,3 - Diene / 3~methyl-3(meth)propenyloxymethyloxetane copolymer, styrene/1-ethylcyclopentyl methacrylate/methacrylic acid tricyclo[ 5·2·1·02,6]decane-8-yl/3-methyl-3-(meth)propenyloxymethyloxetane copolymer, benzene-33- 200835744 B /1 monoethylcyclopentyl methacrylate / methyl Acrylic acid / 3 monomethyl-3 - (meth) propylene methoxymethyl oxetane copolymer, styrene / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate / 3-ethyl-1,3-(methyl)propenyloxymethyloxetan compound copolymer, styrene/1 ethylethylcyclopentyl methacrylate / 3 monoethyl- 3 - (A Base) propylene methoxymethyl oxetane copolymer, phenethyl ethene / 1 ethylcyclopentyl methacrylate / N cyclohexylmaleimine / 3-ethyl ~ 3 a ( Methyl) propylene methoxymethyl oxetane copolymer, styrene / 1 monoethylcyclopentyl methacrylate / , 3 - butadiene ethyl - 3 - (meth) propylene oxime Oxymethyloxetane; I: complete copolypolymer, styrene / 1 monoethylcyclopentyl methacrylate / methyl propyl sulphonate tricyclo [5.21 〇 2, 6] decane -8 //3-ethyl-3-(methyl)-propyl decyloxymethyloxetane copolymer, phenylethyl/1 ethylcyclopentyl methacrylate/methacrylic acid / 3 Monoethyl-3-(methyl)propene oxime Methyl oxetane copolymer, Benzene Z 1 -ethylcyclopentyl methacrylate / glycidyl methacrylate oil S/3 -(meth) propylene oxiranyl ethyl oxetane Alkane copolymer, phenethyl ketone / 1 monoethylcyclopentyl methacrylate / 3 mono(methyl) propyl decyloxyethyl oxetane copolymer, styrene / 1 monoethyl Cyclopentylmethylpropane acrylate / N-cyclohexylmaleimide / 3 - (meth) propylene oxiranoxy oxetane copolymer, styrene / i - ethyl cyclopentane Methyl methacrylate / 1,3 - butadiene / 3 - (meth) propylene oxiranoxy oxetane copolymer, styrene / 1-ethylcyclopentyl methacrylate / Tricyclo[meth] acrylate [5.2.1.02,6] decane-34-200835744 8-based / 3-(meth) propylene oxiranoxy oxetane copolymer, styrene / 1 - B Cyclopentyl methacrylate / methacrylic acid / 3-(meth) propylene oxiranoxy oxetane copolymer, styrene / 1-ethylcyclopentyl methacrylate / A Glycidyl acrylate/3-(methyl) Ethylideneoxyethyloxetane copolymer, styrene/1-ethylcyclopentyl methacrylate/3-(meth)propenyloxyethyloxetane copolymer , styrene/1-ethylcyclopentyl methacrylate/N-cyclohexylmaleimide/3-(meth)acryloxyethyl oxetane copolymer, styrene/ 1 monoethylcyclopentylmethylpropane acrylate /1,3 - butyl bismuth / 3 - (methyl) propyl decyloxyethyl oxetane copolymer, styrene / 1-B Cyclopentyl methacrylate/tricyclo[5.2.1 · 02,6]decane-8-yl/3-(meth)propenyloxyethyloxetane copolymer , styrene / 1 monoethylcyclopentyl methacrylate / methacrylic acid / 3 - (methyl) propylene oxiranoxy oxetane copolymer, and the like. The curable resin composition of the present invention may contain other components in addition to the above-mentioned copolymer (A). Examples of other related components include a secondary auxiliary agent (B), a cationically polymerizable compound (C), a surfactant (D), a polyfunctional acrylate monomer (E), and a heat-sensitive acid generator (F). . Next, the auxiliary agent (B) is added in order to improve the adhesion between the formed protective film and the substrate. -35- 200835744 As such a further auxiliary (B), for example, a functional decane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples of the subsequent auxiliary agent (B) include trimethoxymethionine-based benzoic acid, 7-methacryloxypropyltrimethoxydecane, ethylene triacetate, and ethylene trimethoxydecane. , 7-isocyanate propyl triethoxy decane, 7-glycidoxypropyltrimethoxydecane, 7-glycidoxypropyltriethoxydecane, ^1 (3,4-epoxy) Base cyclohexyl) ethyl dimethoxy sand pot and the like. Thus, the auxiliary agent (B) is preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of the copolymer (a). When the amount of the auxiliary (B) exceeds 30 parts by weight, the heat resistance of the obtained protective film may be insufficient. Cationic Polymerizable Compound (C) The above cationically polymerizable compound (C) is added in order to improve the ITO etching resistance of the formed protective film. The cationically polymerizable compound (C) is a compound having two or more oxirane groups or oxetane groups in the molecule. Examples of the compound having two or more oxirane groups or oxetanyl groups in the molecule include a compound having two or more epoxy groups in the molecule or a 3,4-epoxy group. a cyclohexyl compound. 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 hydrogenated bisphenol A. Diglycidyl-36- 200835744 Ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, succinylated bisphenol A diglycidyl ether, odorated bisphenol f diglycidyl a diglycidyl ether of a bisphenol compound such as an ether or a flavonoid bisphenol S diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin a polyglycidyl ether of a polyhydric alcohol such as triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; a polyglycidyl ether of a polyether polyol obtained by adding one or more kinds of epoxides to an aliphatic polyol such as propylene glycol or glycerin; a phenolic epoxy resin for phenol paint; and a phenol type for cresol paint Epoxy resin; polyphenol type epoxy resin; aliphatic length Di-hydroglyceryl ester of a chain dibasic acid; glycidyl ester of a higher fatty acid; epoxidized soybean oil, epoxylated linseed oil, and the like. As a commercial product having a compound having two or more epoxy groups in the molecule, for example, Epikote 1001, 1002, 1003, 1004, 1007, 1009, and 1010 can be used as the bisphenol A epoxy resin. 828 (above, Japan Epoxy Resin Co., Ltd.), etc.; as a bisphenol F-type epoxy resin, Epikote 8 07 (made by Nippon Epoxy Resin Co., Ltd.) or the like; phenolic ring for phenol paint As the oxyresin, Epikote 152, 154, 157S65 (above, manufactured by Nippon Epoxy Resin Co., Ltd.), EPPN201, and 202 (above, manufactured by Nippon Kayaku Co., Ltd.) can be used; As the epoxy resin, E0CN 102, -37-200835744, 103S, 104S, 1020, 1025, 1027 (above, Nippon Chemical Co., Ltd.), Epikote 180S75 (made by Nippon Epoxy Co., Ltd.), and the like can be used; As the polyphenol type epoxy resin, Epikote 1 03 2H60, the same XY-40 00 (above, manufactured by Nippon Epoxy Resin Co., Ltd.), or the like can be used; as the cyclic aliphatic epoxy resin, CY-175 can be used. 177, with 179, araldat CY-182, with 192, 184 (to , manufactured by Ciba Specialty Chemicals Inc., ERL-4234, 4299, 4221, 4206 (above, UCC), Shodyne 509 (made by Showa Denko), EPICLON200, and 400 (above, Dainippon Ink) ), Epikote 871, the same as 872 (above, 曰本 epoxy resin (manufactured by 曰), ED-5 66 1, the same 5 662 (above, manufactured by Calanese Coating Co., Ltd.); as an aliphatic polyglycidyl ether EPOLIGHT 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), epiol TMP (manufactured by Nippon Oil & Fats Co., Ltd.), and the like are used. Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. Acid ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-di-dioxane, bis(3,4-epoxy ring) Hexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl- 3' , 4'-epoxy- 6'-methylcyclohexanecarboxylate, methyl bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol Two (-38-200835744 3,4-epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), lactone-denatured 3,4-epoxy A cyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate or the like. In the cationically polymerizable compound (c), the oxime-type epoxy resin and the polyphenol-type epoxy resin are preferably used for the enamel paint. The amount of the cationically polymerizable compound (C) used in the resin composition of the present invention is The 100 parts by weight of the copolymer (A) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 1 to 50 parts by weight. When the amount of the cationically polymerizable compound (C) is more than 200 parts by weight, the coating property of the composition may cause a problem. On the other hand, if it is less than 3 parts by weight, the hardness of the obtained protective film may be insufficient. . Surfactant (D) The above surfactant (D) is added to improve the coating properties of the resin composition of the present invention. Examples of the surfactant (D) include a fluorine surfactant, a polyoxyn surfactant, a nonionic surfactant, and other surfactants. For example, the BM CHEMIE company's trade name: BM-1000, BM-1100, Dainippon Ink Chemical Industry Co., Ltd., trade name: Megafak F142D, F172, F173, F183, and the same R_08, Sumitomo 3M (share) system name: FrolardFC-135, with FC-170C, with FC-43 0, with FC-431, (stock) Neos product name: Ftergent 250, same 251, same 222F, -39 - 200835744 FTX-21 8. Asahi Glass Co., Ltd. Product Name: SerflonS-1 12, Same as S-113, Same S-131, Same S-141, Same S-145, Same S-382, Same as SC-101 ' Same as SC-102, same SC-103, same SC-104, same SC-105, and SC-106. Examples of the polyfluorene surfactant include trade names of Toray Dow Corning Co., Ltd., trade names: SH-28PA, SH-190, SH-193, SZ-603 2 , SF-842 8 , DC. -57, DC-190,

PAINTAD19、FZ-2101、同 77、同 2118、L-7001、L-7002 、：B YK-Chemie·日本（股）製、Byk-3 00、同 3 06、同 310 、同335、同341、同344'同370、信越化學工業（股） 製商品名：KP341、新秋田化成（股）製商品名： FTopEF301、同 EF303、同 EF352 等販賣品。 作爲上述非離子界面活性劑，例如可舉出聚環氧乙院 烷基醚、聚環氧乙烷芳基醚、聚環氧乙烷二烷基酯等。 作爲上述聚環氧乙烷烷基醚，例如可舉出聚環氧乙院 月桂基醚、聚環氧乙烷硬脂醯醚、聚環氧乙烷油醚等，作 爲聚環氧乙院芳基醚’例如可舉出聚環氧乙垸辛基苯基醚 、聚環氧乙垸壬基苯基醚，作爲聚環氧乙垸二院基醋，例 如可舉出聚環氧乙院一月桂酸酯、聚環氧乙院二硬脂酸酯 等。 作爲上述的其他界面活性劑，可舉出共榮社化學（股 )製商品名：（甲基）丙烯酸系共聚合物P〇lyfr〇N〇.57 、同 No.90 等。 1 0 0 這些界面活性劑（D )之添加量爲共聚合物（a ) -40- 200835744 重量份下，較佳爲5重量份以下，更佳爲2重量份以下。 界面活性劑的量若超過5重量份時，於塗佈步驟中容易產 生塗膜之膜粗糙。 ' 多官能丙烯酸酯單體（E) " 本發明的樹脂組成物係以表現保護膜之修改（剝膜） 特性爲目的而可添加多官能丙烯酸酯單體。 馨作爲多官能丙烯酸酯單體（E )，以不損害作爲保護 膜之硬度下以3官能以上之丙烯酸酯單體爲佳。 例如可舉出三丙烯醯氧基季戊四醇琥珀酸{別名：3 一丙烯醯氧基一 2，2-雙丙烯醯氧基甲基一丙基}酯}、 二丙烯醯氧基季戊四醇琥珀酸{別名：3-丙烯醯氧基一 2 -丙烯醯氧基甲基-丙基丨酯}、五丙烯醯氧基二季戊四 醇琥珀酸{別名：〔3 — ( 3 -丙烯醯氧基一 2,2 —雙一丙 烯醯氧基甲基一丙基）一 2,2—雙一丙烯醯氧基甲基一丙 9 } 基〕酯}、四丙烯醯氧基二季戊四醇琥珀酸{別名：[3 一（3 -丙烯醯氧基一 2,2—雙一丙烯醯氧基甲基一丙基） - 2—丙烯醯氧基甲基-丙基〕酯}、三丙烯醯氧基乙基 ' 三聚異氰酸{別名：參（丙烯氧基乙基）三聚異氰酸酯} • 、二季戊四醇六丙烯酸酯（DPHA )、季戊四醇Η丙烯酸 酯、三羥甲基丙烷三丙烯酸酯、參丙烯醯氧基乙基磷@自 三羥甲基丙烷ΕΟ加成三丙烯酸酯、季戊四醇四丙纟希酸酯 等。 其中以提高硬度之目的下，使用五丙烯醯氧基二^$ -41 - 200835744 四醇琥珀酸{別名：〔3— (3 —丙烯醯氧基一 2,2—雙— 丙烯醯氧基甲基一丙基）- 2,2—雙一丙烯醯氧基甲基— 丙基丨酯、簡稱：PADPS }、二季戊四醇六丙烯酸酯（ DPHA )、三丙烯醯氧基乙基三聚異氰酸{別名：參（丙 烯氧基乙基）三聚異氰酸酯}爲佳，使用五丙烯醯氧基二 季戊四醇琥珀酸{別名：〔3 — （ 3 -丙烯醯氧基—2,2 — 雙一丙烯醯氧基甲基一丙基）一 2,2-雙一丙烯醯氧基甲 基—丙基}酯，簡稱：PADPS丨爲最佳。 多官能丙烯酸酯單體（E )之添加量對於共聚合物（ A ) 100重量份而言，較佳爲150重量份以下，更佳爲 120重量份以下。超過150重量份時，與基板之密著力會 降低故不佳。這些可單獨或混合2種以上使用。 感熱性酸產生劑（F ) 本發明的組成物中可添加感熱性酸產生劑（F )。作 爲感熱性酸產生劑（F )，可舉出鎏鹽、苯並噻11坐_鹽、 銨鹽、鳞鹽等，這些中以鎏鹽類、苯並噻唑鐵鹽類爲保護 膜具有較高表面硬度而較佳。 感熱性酸產生劑（F )之添加量對於共聚合物（A ) 1 0 0重量份而言，較佳爲3 0重量份以下’更佳爲2 0重量 份以下。超過30重量份時’硬度會大幅度降低。這些可 單獨或混合2種以上使用。 溶劑 -42- 200835744 本發明的樹脂組成物較佳可由將上述的各成分均勻地 溶解或分散於適當溶劑中而調製。作爲所使用之溶劑，以 可溶解或分散組成物之各成分，且與各成分不會產生反應 者爲佳。 作爲如此溶劑，可舉出醇、醚、乙二醇醚、乙二醇烷 • 基醚乙酸酯、二乙二醇單烷基醚、二乙二醇二烷基醚、丙 二醇單烷基醚、丙二醇烷基醚乙酸酯、丙二醇烷基醚丙酸 φ 酯、芳香族烴、酮、酯等。 作爲這些具體例，例如以醇可舉出甲醇、乙醇、苯甲 醇等； 以醚可舉出四氫呋喃等； 作爲乙二醇醚，可舉出乙二醇單甲醚、乙二醇單乙醚 等； 作爲可舉出乙二醇烷基醚乙酸酯，可舉出甲基溶纖劑 乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁基醚乙酸酯、二 ® )乙二醇單乙醚乙酸酯等； 作爲二乙二醇單烷基醚，可舉出二乙二醇單甲醚、二 乙二醇單乙醚等； • 作爲二乙二醇二烷基醚，可舉出二乙二醇二甲基醚、 - 二乙二醇二乙基醚、二乙二醇乙基甲基醚等； 作爲丙二醇單烷基醚，可舉出丙二醇甲基醚、丙二醇 乙基醚、丙二醇丙基醚、丙二醇丁基醚等； 作爲丙二醇烷基醚乙酸酯，可舉出丙二醇甲基醚乙酸 酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、丙二醇 -43 - 200835744 丁基醚乙酸酯等； 作爲丙二醇烷基醚丙酸酯可舉出丙二醇甲基醚丙酸酯 、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁 基醚丙酸酯等； " 作爲芳香族烴可舉出甲苯、二甲苯等； • 作爲酮可舉出甲基乙基酮、環己酮、4一羥基一 4 一甲 基一 2—戊酮、甲基異戊酮等； φ 作爲酯可舉出乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸 丁酯、乙酸環己基、2—羥基丙酸乙基、2—羥基一 2-甲 基丙酸甲基、2 -羥基一 2 -甲基丙酸乙基、羥基乙酸甲醋 、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲基、乳酸乙基、 乳酸丙基 '乳酸丁基、3 -羥基丙酸甲基、3 —羥基丙酸乙 基、3-羥基丙酸丙基、3-羥基丙酸丁基、2—羥基—3_ 甲基丁烷酸甲基、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、两氧基乙 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—甲氧基丙酸甲基、2 一甲氧基 . 丙酸乙基、2-甲氧基丙酸丙基、2-甲氧基丙酸丁基、2 一乙氧基丙酸甲基、2 —乙氧基丙酸乙基、2—乙氧基丙酸 丙基、2-乙氧基丙酸丁基、2— 丁氧基丙酸甲基、2 一丁 氧基丙酸乙基、2- 丁氧基丙酸丙基、2-丁氧基丙酸丁基 、3 —甲氧基丙酸甲基、3 —甲氧基丙酸乙基、3 —甲氧基 -44- 200835744 丙酸丙基、3-甲氧基丙酸丁基、3—乙氧基丙酸甲基、3 -乙氧基丙酸乙基、3—乙氧基丙酸丙基、3 —乙氧基丙酸 丁基、3-丙氧基丙酸甲基、3 -丙氧基丙酸乙基、3 —丙 氧基丙酸丙基、3-丙氧基丙酸丁基、3- 丁氧基丙酸甲基 、3- 丁氧基丙酸乙基、3 - 丁氧基丙酸丙基、3 一 丁氧其 丙酸丁基等。 其中以醇、二乙二醇、丙二醇烷基乙酸酯、乙二醇院 基醚乙酸酯、二乙二醇二烷基醚爲佳，特別爲苯甲基醇、 二乙二醇乙基甲基醚、丙二醇甲基醚乙酸酯、丙二醇乙基 醚乙酸酯、二乙二醇二甲基醚、乙二醇單丁基醚乙酸酯、 二乙二醇單乙醚乙酸酯、二乙二醇二乙基醚、3 —甲氧基 丙酸甲基、3-乙氧基丙酸甲基、3 —甲氧基丙酸乙基爲佳 〇 作爲溶劑之使用量，對於本發明組成物中的全固體成 分（溶劑量除以含有溶劑之組成物的總量所得値）之含有 量較佳爲1〜50重量％，更佳爲5〜40重量％之範圍。 前述溶劑可並用高沸點溶劑。作爲其中可並用的高沸 點溶劑，例如可舉出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、二甲基亞礪、苯甲基乙基醚、 二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1 -辛 醇、1 一壬醇、乙酸苯甲酯、安息香酸乙酯、草酸二乙酯 、馬來酸二乙酯、^一 丁內脂、碳酸乙烯酯、碳酸丙烯酯 、苯基溶纖劑乙酸酯等。 -45- 200835744 作爲並用高沸點溶劑時的使用量，對於全溶 較佳爲90重量％以下，更佳爲80重量％以下。 如上述所調製之組成物，使用較佳爲孔徑〇. #m，更佳爲孔徑0.2〜0.5//m程度的millipore 過濾後使用。 彩色濾光片之保護膜的形成 其次，對於作爲使用本發明的組成物之彩色 保護膜之形成方法做說明。 將本發明的樹脂組成物溶液塗佈於基板表面 煅燒後除去溶劑而形成塗膜後，經加熱處理後可 目的之彩色濾光片的保護膜。 作爲可爲上述基板使用者，例如可使用玻璃 矽、樹脂等基板。作爲樹脂，例如可舉出聚對苯 二醇酯、聚對苯二甲酸丁二醇酯、聚醚颯、聚碳 亞胺、以及環狀烯烴之開環聚合物及如該氫化物 作爲塗佈方法，例如可採用噴霧法、輥塗佈 佈法、棒塗佈法、墨點噴射法等適宜方法，特別 動塗佈法、無轉動塗佈、狹縫模頭塗佈法進行塗 作爲上述預煅燒之條件，雖依各成分種類或 等而相異，但例如可採用7 0〜9 0 °C下1〜1 5分 條件。作爲塗膜厚度，較佳爲0.1 5〜8.5 μ m 〇·15〜6.5#m，特佳爲0.15〜4.5//m。且，此所 厚度爲除去溶劑後的厚度而言。 劑量而言 2 〜3.0 過濾器等 濾光片的 上，經預 形成作爲 、石英、 二甲酸乙 酸酯、聚 之樹脂。 、轉動塗 可使用轉 佈爲佳。 配合比率 鐘程度之 ，更佳爲 謂的塗膜 -46- 200835744 塗膜形成後之加熱處理可藉由加熱板或無塵烤箱等適 宜加熱裝置實施。作爲處理溫度以150〜2 5〇t程度爲佳 ’加熱時間於使用加熱板之情況時可採用5〜3 0分鐘，使 用烤箱之情況爲可採用3 0〜90分鐘之處理時間。 又’於樹脂組成物使用感放射線性酸產生劑時，將該 * 樹脂組成物塗佈於基板表面，經預煅燒使溶劑除去並做成 塗fe後’施予放射線照射處理（曝光處理）而形成目的之 # , 保護膜。視所需可於曝光處理後再進行加熱處理。 作爲上述放射線之照射處理中可使用的放射線，可舉 出可見光線、紫外線、遠紫外線、電子線、X線等，其中 以含有190〜450 nm之波長光的紫外線爲佳。 曝光量較佳爲 100〜20,000J/m2，更佳爲 150〜 1 0,000J/m2 ° 放射線照射後可再進行任意加熱處理。作爲此時的加 熱溫度，以1 5 0〜2 5 0 °C程度爲佳，作爲加熱裝置例如可 ® ) 使用加熱板、無塵烤箱等適宜裝置。加熱時間於使用加熱 板的情況可採用5〜3 0分鐘，使用烤箱的情況可採用3 〇 〜90分鐘之處理時間。 - 彩色濾光片之保護膜 如此所形成之保護膜中，該膜厚較佳爲〇. 1〜8 # m， 更佳爲〇·1〜6//m’最佳爲〇.；[〜4#m。且，本發明的保 護膜形成於具有彩色濾光片之段差的基板上時，上述膜厚 爲自彩色濾光片的最上部的厚度。 -47- 200835744 本發明的保護膜由如下述實施例得知，滿足密著 表面硬度、透明性、耐熱性、耐鹼性等的同時，即使 狀態的荷重亦不會造成凹陷，又具有優良的使底基板 形成之彩色濾光片的段差平坦化之性能，而適合作爲 置用保護膜使用。 如以上，本發明爲提供一種即使爲表面平坦性低 體，該基體上可形成平坦性極高的硬化膜，且，適用 成透明性及表面硬度高、耐熱耐壓性、耐酸性、耐鹼 耐濺射性等各種耐性亦優良的光裝置用保護膜上，且 組成物而言爲保存安定性亦優良的樹脂組成物，使用 脂組成物的保護膜之形成方法、及藉由上述組成物所 之保護膜。 【實施方式】 實施例 以下記載合成例、實施例，對本發明做更具體說 但本發明並未限定於以下實施例。 (共）聚合物之製造 合成例1 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙 —二甲基戊腈5重量份及二乙二醇乙基甲基醚200重 。繼續再裝入四氫一 2H-吡喃一 2—基甲基丙烯酸圈 重量份、苯乙烯20重量份、3一（甲基丙烯醯氧基乙 性、 經熱 上所 光裝 的基 於形 性、 作爲 該樹 形成 明， -2,4 量份 | 20 基） -48- 200835744 氧雜環丁烷40重量份及N-環己基馬來醯亞胺20重量份 ’以氮氣取代後開始緩緩攪拌。將溶液溫度上升至70 °C ’將該溫度保持7小時後得到含有共聚合物〔A-1〕之聚 合物溶液。所得之聚合物溶液的固體成分濃度爲3 3 · 〇重 量％。聚合物的數平均分子量爲4,300 (數平均分子量爲 • 使用GPC (凝膠滲透色層法）HLC-8020 (東索（股）製 )進行測定後之聚苯乙烯換算分子量。以下相同。）。 合成例2 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入四氫一 2H—吡喃一 2-基甲基丙烯酸酯20 重量份、苯乙烯20重量份、3—（甲基丙烯醯氧基乙基） 氧雜環丁烷40重量份及甲基丙烯酸三環〔5.2.1.02,6〕癸 烷一 8 -基20重量份，以氮氣取代後開始緩緩攪拌。將溶 ^ i 液溫度上升至70Ϊ：，將該溫度保持7小時後得到含有共 聚合物〔A-2〕之聚合物溶液。所得之聚合物溶液的固體 成分濃度爲32.8重量％。聚合物的數平均分子量爲4,300 合成例3 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入四氫一 2H-吡喃一 2-基甲基丙烯酸酯20 -49- 200835744 重量份、苯乙烯20重量份、3-（丙烯醯氧基乙基）氧雜 環丁烷40重量份及n-環己基馬來醯亞胺20重量份，以 氮氣取代後開始緩緩攪拌。將溶液溫度上升至70它，將 該溫度保持7小時後得到含有共聚合物〔A-3〕之聚合物 溶液。所得之聚合物溶液的固體成分濃度爲3 2.9重量％ • 。聚合物的數平均分子量爲4,200。 籲、合成例4 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼li再裝入四氫一 2H —卩比喃一 2-基甲基丙燒酸酯20 重重份、苯乙嫌20重量份、3—（丙稀醯氧基乙基）氧雜 環丁烷40重量份及甲基丙烯酸三環〔5·2·1.〇2,6〕癸院一 8 -基20重量份，以氮氣取代後開始緩緩攪拌。將溶液溫 度上升至7 0 °C，將該溫度保持7小時後得到含有共聚合 ® i 物〔A —4〕之聚合物溶液。所得之聚合物溶液的固體成分 濃度爲32.9重量％。聚合物的數平均分子量爲4，4 00。 合成例5 ~ 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2，4 一一甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入1一（環己氧基）乙基甲基丙烯酸酯20重 量份、苯乙烯20重量份、3—（甲基丙烯醯氧基乙基）氧 雜環丁烷40重量份及N -環己基馬來醯亞胺20重量份， -50- 200835744 以氮氣取代後開始緩緩攪拌。將溶液溫度上升至70 °C， 將該溫度保持7小時後得到含有共聚合物〔A-5〕之聚合 物溶液。所得之聚合物溶液的固體成分濃度爲3 3.0重量 %。聚合物的數平均分子量爲4,300。 合成例6 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入1 -（環己氧基）乙基甲基丙烯酸酯20重 量份、苯乙烯20重量份、3 -（甲基丙烯醯氧基乙基）氧 雜環丁烷40重量份及甲基丙烯酸三環〔5.2.1.02，6〕癸烷 一 8 -基20重量份，以氮氣取代後開始緩緩攪拌。將溶液 溫度上升至7 0 °C，將該溫度保持7小時後得到含有共聚 合物〔A-6〕之聚合物溶液。所得之聚合物溶液的固體成 分濃度爲32.7重量％。聚合物的數平均分子量爲4,4〇〇。 合成例7 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚2〇〇重量份 。繼續再裝入1 -（環己氧基）乙基甲基丙嫌酸酯20重 量份、苯乙烯20重量份、3—（丙烯醯氧基乙基）氧雜環 丁烷40重量份及N -環己基馬來醯亞胺20重量份，以氮 氣取代後開始緩緩攪拌。將溶液溫度上升至7 0 °C，將該 溫度保持7小時後得到含有共聚合物〔A-7〕之聚合物溶 -51 - 200835744 液。所得之聚合物溶液的固體成分濃度爲3 3.2重量％。 聚合物的數平均分子量爲4,2〇〇。 合成例8 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙- 2,4 • —二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入1一（環己氧基）乙基甲基丙烯酸酯20重 Φ > 量份、苯乙烯20重量份、3—(丙烯醯氧基乙基）氧雜環 丁烷40重量份及甲基丙烯酸三環〔5.2.1〇2,6〕癸烷一 8一 基2〇重量份，以氮氣取代後開始緩緩攪拌。將溶液溫度 上升至7 0 °C，將該溫度保持7小時後得到含有共聚合物 〔A -8〕之聚合物溶液。所得之聚合物溶液的固體成分濃 度爲33.0重量％。聚合物的數平均分子量爲4,200。 合成例9 ® ) 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙- 2，4 —二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼繪再裝入四氫一 2H —眼喃—2 —基甲基丙燃酸酯25 重量份、苯乙烯25重量份及3一（甲基丙烯醯氧基乙基 - )氧雜環丁烷5 0重量份，以氮氣取代後開始緩緩攪拌。 將溶液溫度上升至70 °C，將該溫度保持7小時後得到含 有共聚合物〔A-9〕之聚合物溶液。所得之聚合物溶液的 固體成分濃度爲3 2 · 6重量％。聚合物的數平均分子量爲 452 00 -52- 200835744 合成例1 ο 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙- 2,4 -二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入1 -乙基環戊基甲基丙烯酸酯20重量份、 苯乙烯20重量份、3-（甲基丙烯醯氧基乙基）氧雜環丁 烷40重量份及Ν-環己基馬來醯亞胺20重量份，以氮氣 取代後開始緩緩攪拌。將溶液溫度上升至70 °C，將該溫 度保持7小時後得到含有共聚合物〔A-1 〇〕之聚合物溶液 。所得之聚合物溶液的固體成分濃度爲3 3.0重量％。聚 合物的數平均分子量爲4,300。 比較合成例1 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入甲基丙烯酸20重量份、苯乙烯20重量份、 N-環己基馬來醯亞胺20重量份及甲基丙烯酸縮水甘油 基40重量份，以氮氣取代後開始緩緩攪拌。將溶液溫度 上升至7 0 °C，將該溫度保持7小時後得到含有共聚合物 〔a-1〕之聚合物溶液。所得之聚合物溶液的固體成分濃 度爲33.0重量％。聚合物的數平均分子量爲4，4〇〇。 比較合成例2 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 -53- 200835744 一二甲基戊腈5重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入四氫一 2H-吡喃一 2—基甲基丙烯酸酯20 重量份、苯乙烯20重量份、N-環己基馬來醯亞胺20重 量份及甲基丙烯酸縮水甘油基4 0重量份，以氮氣取代後 開始緩緩攪拌。將溶液溫度上升至70 °C，將該溫度保持7 • 小時後得到含有共聚合物〔a-2〕之聚合物溶液。所得之 聚合物溶液的固體成分濃度爲3 3 · 1重量％。聚合物的數 φ . 平均分子量爲4，2 00。 比較合成例3 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 —二甲基戊腈5重量份及二乙二醇乙基甲基醚2〇〇重量份 。繼續再裝入甲基丙烯酸20重量份、苯乙烯2〇重量份、 甲基丙烯酸三環〔5·2 ·1.02,6〕癸烷一 8一基2〇重量份及3 -（甲基丙烯醯氧基乙基）氧雜環丁烷4〇重量份，以氮 馨）氣取代後開始緩緩攪拌。將溶液溫度上升至7 0 °C，將該 溫度保持7小時後得到含有共聚合物〔& _ 3〕之聚合物溶 液。所得之聚合物溶液的固體成分濃度爲3 2.9重量％。 • 聚合物的數平均分子量爲4,400。 比較合成例4 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙一 2,4 —二甲基戊腈2重量份及二乙二醇乙基甲基醚200重量份 。繼續再裝入四氫一 2H —吡喃〜2 一基甲基丙烯酸酯25 -54- 200835744 重量份、苯乙烯25重量份及3一 （甲基丙烯醯氧基乙基 )氧雜環丁烷5 0重量份’以氮氣取代後開始緩緩攪拌。 將溶液溫度上升至70 °C，將該溫度保持7小時後得到含 有共聚合物〔a-4〕之聚合物溶液。所得之聚合物溶液的 固體成分濃度爲32.5重量％。聚合物的數平均分子量爲 6 1，000 ° 比較合成例5 於具備冷却管與攪拌機之燒瓶中，裝入偶氮雙- 2,4 —二甲基戊腈10重量份及二乙二醇乙基甲基醚200重量 份。繼續再裝入四氫— 2H—吡喃—2—基甲基丙烯酸酯25 重量份、苯乙烯25重量份及3—（甲基丙烯醯氧基乙基 )氧雜環丁烷50重量份，以氮氣取代後開始緩緩攪拌。 將溶液溫度上升至70 °C，將該溫度保持7小時後得到含 有共聚合物〔a_ 5〕之聚合物溶液。所得之聚合物溶液的 固體成分濃度爲32.5重量％。聚合物的數平均分子量爲 8 00 ° 樹脂組成物的調製及評估 實施例1 含有上述合成例1所得之共聚合物（A-1 )之溶液（ 相當於共聚合物（A-1) 100重量份（固體成分）之量） 中加入（B-l) τ 一環氧丙氧基丙基三甲氧基矽烷15.0重 量份、（D-1 )作爲界面活性劑之SH-28PA ( Toray · -55- 200835744 dowcorning·聚矽氧（股）製）0.1重量份、（E-1)二季 戊四醇六丙烯酸酯（日本化藥（股）製 商品名： KAYARAD DPHA) 50重量份，再使固體成分濃度成爲20 重量％下添加8對2比率的丙二醇單甲醚乙酸酯（S-1) 及二乙二醇乙基甲基醚（S-2 )後，以孔徑0.5 // m之 m i 11 i ρ 〇 r e過濾器進行濾過調製出樹脂組成物。 使用轉動子將上述組成物塗佈於S i 02浸漬玻璃基板 上後，以加熱板上進行80°C、5分鐘預煅燒後形成塗膜， 再於烤箱中23 0 °C下進行60分鐘加熱處理形成膜厚2.0 // m之保護膜。 保護膜之評估 (1 )透明性之評估 對於具有如上述所形成之保護膜的基板，使用分光光 度計（1 50-20型雙光束（日立製作所（股）製）），測 定 400〜800nm之透過率。400〜800nm的透過率最小値 如表1所示。該値若爲95 %以上時，表示保護膜之透明 性爲良好。 (2 )耐熱尺寸安定性之評估 具有如上述所形成之保護膜的基板，於烤箱中25 0 °C 下1小時的條件下進行加熱，測定加熱前後之膜厚。依據 下述式所算出之耐熱尺寸安定性如表1表示。此値若爲 95%以上時，表示耐熱尺寸安定性爲良好。 -56- 200835744 耐熱尺寸安定性=(加熱後之膜厚）/(加熱前之膜厚 )χ100(%) (3 )耐鹼性之評估 具有如上述所形成之保護膜的基板於3 0 °C ，5 % N a Ο Η中浸漬3 0 m i η後，於加熱板除去水分，其後測定膜 厚。依據下述式所算出之耐鹼性如表1表示。該値若爲 9 5 %以上時，表示耐鹼性爲良好。 耐鹼性=(水分除去後之膜厚）/(浸漬前之膜厚）x 1 00(%) (4 )耐熱變色性之評估 對於具有如上述所形成的保護膜之基板，烤箱中以 25 0°C加熱1小時，將加熱前後之透明性以與上述（1 )之 同樣下進行測定。依據下述式所算出之耐熱變色性如表1 表示。該値若爲5 %以下時，表示耐熱變色性良好。 耐熱變色性=加熱前之透過率-加熱後之透過率（％) (5 )表面硬度之測定 對於具有如上述所形成的保護膜之基板，藉由 JIS K-5 400- 1 99 0之8.4.1鉛筆牽引試驗測定出保護膜表面 硬度。該値如表1表示。該値若爲4H或比此硬時，表示 表面硬度良好。 (6)動態微小硬度之測定 -57 - 200835744 對於具有如上述所形成的保護膜之基板，使用島津動 態微小硬度計DUH-201 ((股）島津製作所製），藉由稜 角115°三角壓子（helocobitch型）之壓入試驗，將保護 膜的動態微小硬度以荷重：O.lgf、速度：0.0145gf/sec.、 保持時間：5sec.、溫度爲23°C及140°C之測定條件下進 行測定。結果如表1所示。 (7 )密著性之評估 對於使用與具有如上述所形成之保護膜的基板（Si02 浸漬玻璃）的相同方法所作成的Glass Wefer、OA10，進 行壓力鍋試驗（Pressure Cooker Test)試驗（120 °C、濕 度 100%、4 小時）後，藉由 JIS K-5400- 1 990 的 8.5.3 附 著性方格表法評估保護膜之密著性。方格子1 〇〇個中剩下 的方格子數如表1所示。 (8 )保存安定性之評估 實施例1所調製的保護膜形成用之樹脂組成物中的黏 度，使用東京計器（股）製 ELD型黏度計進行測定。其 後，將該組成物靜置於25°C下，每天測定於25°C之溶液 黏度。以調製後馬上測得知黏度作爲基準求得5 %增黏所 需的日數，此日數如表1所示。該日數若爲20日以上時 ，表示保存安定性良好。 (9 )平坦化性之評估 -58- 200835744 於Glass Wefer基板上將顔料系彩色光阻（商品名「 JCR RED 689」、「JCR GREEN 706」、「CR 8200B」、 以上SR (股）製）使用轉動子進行塗佈，於加熱板上 進行90 °C、150秒間預煅燒後形成塗膜。其後，介著所定 圖型光罩，使用曝光機Canon PLA501F(Canon (股）製 ’ ）將 ghi 線（波長 436nm、405nm、3 65 nm 的強度比=2.7 :2.5 : 4.8 )以i線換算下爲2,000J/m2的曝光量進行照 • X 射’使用0.05%氫氧化鉀水溶液進行顯像，以超純水進行 60秒輕洗後，再於烤箱中進行23 0°C之30分鐘加熱處理 ’形成紅、綠、及藍之3色條紋狀彩色濾光片（條紋寬. 10 0// m )。 將形成該彩色濾光片之基板表面的凹凸，以表面粗度 計「a - s t e p」（商品名：T e n c ο 1日本（股）製）進行測 定後得到1 m。但其以測定長度2,000 // m，測定範圍 2,000 // m角、測定點數η = 5下進行測定。即，將測定方 Φ ) 向成爲紅、綠、藍方向之條紋線路短軸方向及紅•紅、綠 •綠、藍·藍之同一色的條紋線路長軸方向之2方向，對 於各方向進行η = 5測定（合計η數爲1 0 )。 ^ 此上將上述保護膜形成用組成物以轉動子進行塗佈後 - ，加熱板上進行90°C、5分鐘預煅燒後形成塗膜，再於烤 箱中進行230 °C之60分鐘加熱處理，形成自彩色濾光片 上面之膜厚爲2.0 // m的保護膜。但，其中所謂的膜厚表 示自基板上所形成之彩色濾光片的最上面之厚度。 對於如上述所形成之彩色濾光片上具有保護膜的基板 -59- 200835744 ，於接觸式膜厚測定裝置a -step ( Tencol日本（股）製 )測定保護膜之表面凹凸。但，其爲測定長度2，0 0 0 // m ，測定範圍2,000 // m角，測定點數n = 5下進行測定。即 ，使測定方向成爲紅、綠、藍方向之條紋線路短軸方向及 紅•紅、綠•綠、藍·藍之同一色的條紋線路長軸方向之 2方向，對於各方向進行η二5測定（合計η數爲1 0 )。 每次測定之最高部與最底部的高低差（nm )之1 0次平均 値如表1所示。此値若爲3 00nm以下時，表示平坦化性 良好。 實施例2〜1 0及比較例1〜5 組成物的各成分之種類及量如表1所記載’與實施例 1相同下調製出樹脂組成物。 使用如上述所調製之保護膜形成用樹脂組成物’與實 施例1相同下形成保護膜並進行評估。結果如表1所示。 -60- 200835744PAINTAD19, FZ-2101, same 77, same 2118, L-7001, L-7002, :B YK-Chemie·Japan (share) system, Byk-3 00, same 3 06, same 310, same 335, same 341, Same as 344' 370, Shin-Etsu Chemical Industry Co., Ltd. Product name: KP341, New Akita Chemicals Co., Ltd. Product name: FTopEF301, EF303, EF352 and other sales. The nonionic surfactant may, for example, be a polyepoxyalkylene ether, a polyethylene oxide aryl ether or a polyethylene oxide dialkyl ester. Examples of the polyethylene oxide alkyl ethers include polyepoxyether lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, and the like. Examples of the ether can be, for example, polyethylene oxide octyl phenyl ether or polyethylene oxide phenyl ether, and polyethylene epoxide aldehyde vinegar. Lauric acid ester, polyepoxyethylene distearate, and the like. The other surfactants mentioned above include the trade name of Kyoeisha Chemical Co., Ltd.: (meth)acrylic copolymer P〇lyfr〇N〇.57, the same as No. 90, and the like. The amount of the surfactant (D) to be added is from 5 to 10 parts by weight, more preferably 2 parts by weight or less, based on the total amount of the copolymer (a) -40 to 200835744 parts by weight. When the amount of the surfactant exceeds 5 parts by weight, the film of the coating film is likely to be rough in the coating step. 'Polyfunctional acrylate monomer (E) " The resin composition of the present invention can be added with a polyfunctional acrylate monomer for the purpose of expressing the modification (peeling) property of the protective film. As the polyfunctional acrylate monomer (E), sensitization is preferably a trifunctional or higher acrylate monomer which does not impair the hardness as a protective film. For example, tripropenyloxypentaerythritol succinic acid {alias: 3-propenyloxy- 2,2-bispropenyloxymethyl-propyl} ester), dipropylene decyloxypentaerythritol succinic acid {alias : 3-propenyloxy 2- 2 -propenyloxymethyl-propyl decyl ester}, penta propylene oxy dipentaerythritol succinic acid {alias: [3 - ( 3 - propylene oxyl 2, 2 - Bis-acryloyloxymethyl-propyl)- 2,2-bis-propenyloxymethyl-propyl-9}yl]ester}, tetrapropenyloxydipentaerythritol succinic acid {alias: [3 one ( 3-propenyloxy- 2,2-di-propylene methoxymethyl-propyl)-2-propenyloxymethyl-propyl], tripropylene methoxyethyl 'trimer Cyanic acid {alias: ginseng (propyleneoxyethyl) trimer isocyanate} • dipentaerythritol hexaacrylate (DPHA), pentaerythritol oxime acrylate, trimethylolpropane triacrylate, propylene propylene oxide ethyl phosphate @Addition of trimethylolpropane oxime to triacrylate, pentaerythritol tetrapropionate and the like. Among them, for the purpose of improving the hardness, the use of penta propylene oxy group II - 41 - 200835744 tetraol succinic acid {alias: [3 - (3 - propylene oxyl-2,2-bis- propylene oxy group A) Propyl-propyl)- 2,2-di-bis-acryloxymethyl-propyl decyl ester, abbreviated as: PADPS }, dipentaerythritol hexaacrylate (DPHA), tripropylene methoxyethyl isocyanuric acid {alias: ginseng(propyleneoxyethyl)trimeric isocyanate} is preferred, using penta propylene oxydipentaerythritol succinic acid {alias: [3 - (3 - propylene oxy- 2, 2 - bis-acrylonitrile) Oxymethylmethyl-propyl)- 2,2-bis-propylene methoxymethyl-propyl} ester, abbreviated as: PADPS 丨 is the best. The amount of the polyfunctional acrylate monomer (E) to be added is preferably 150 parts by weight or less, more preferably 120 parts by weight or less, based on 100 parts by weight of the copolymer (A). When the amount is more than 150 parts by weight, the adhesion to the substrate is lowered, which is not preferable. These can be used individually or in mixture of 2 or more types. Heat-sensitive acid generator (F) A heat-sensitive acid generator (F) can be added to the composition of the present invention. Examples of the thermosensitive acid generator (F) include an onium salt, a benzothiazide 11 salt, an ammonium salt, a scale salt, and the like, and among these, a phosphonium salt and a benzothiazole iron salt are used as a protective film. The surface hardness is preferred. The amount of the heat-sensitive acid generator (F) to be added is preferably 30 parts by weight or less or more preferably 20 parts by weight or less based on 100 parts by weight of the copolymer (A). When it exceeds 30 parts by weight, the hardness is greatly lowered. These can be used alone or in combination of two or more. Solvent - 42 - 200835744 The resin composition of the present invention is preferably prepared by uniformly dissolving or dispersing the above components in a suitable solvent. As the solvent to be used, it is preferred that the components of the composition are dissolved or dispersed, and that no reaction occurs with each component. Examples of such a solvent include alcohol, ether, glycol ether, ethylene glycol alkane ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, and propylene glycol monoalkyl ether. , propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionic acid φ ester, aromatic hydrocarbon, ketone, ester, and the like. Examples of the specific examples of the alcohol include methanol, ethanol, and benzyl alcohol; and examples of the ether include tetrahydrofuran; and examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and di®) Glycol monoethyl ether acetate; etc.; as the diethylene glycol monoalkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.; Examples thereof include diethylene glycol dimethyl ether, -diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as the propylene glycol monoalkyl ether, propylene glycol methyl ether and propylene glycol ethyl group are mentioned. Ether, propylene glycol propyl ether, propylene glycol butyl ether, etc.; as propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol -43 - 200835744 Butyl ether acetate, etc.; as propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, C Alcohol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; " as an aromatic hydrocarbon, toluene, xylene, etc.; Ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, etc.; φ as the ester may, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetic acid Cyclohexyl, 2-hydroxypropionic acid ethyl, 2-hydroxy-2-methylpropionic acid methyl, 2-hydroxy-2-ethylpropionic acid ethyl, glycolic acid methyl vinegar, ethyl hydroxyacetate, hydroxyacetic acid Ester, methyl lactate, ethyl lactate, lactic acid propyl 'lactide butyl, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid ethyl, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid butyl, 2-Hydroxy-3_methylbutanoic acid methyl, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy ® ; ethyl acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxy propyl acetate, Butyl oxyacetate, methyl butoxyacetate, ethyl butoxyacetate, 'propyl propyloxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methoxyl . Propionic acid ethyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxy Propyl propyl, 2-ethoxypropionic acid butyl, 2-butoxypropionic acid methyl, 2-butoxypropionic acid ethyl, 2-butoxypropionic acid propyl, 2-butoxy Butyl propyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy-44-200835744 propionic acid propyl, 3-methoxypropionic acid butyl, 3-ethoxypropyl propionate methyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid propyl, 3-ethoxypropionic acid butyl, 3-propoxypropionic acid methyl, 3-propoxypropionic acid ethyl, 3-propoxypropionic acid propyl, 3-propoxypropionic acid butyl, 3-butoxypropionic acid methyl, 3-butoxypropionic acid ethyl, 3-butoxypropionic acid propyl, 3-butoxypropionic acid butyl, and the like. Among them, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol ether acetate, diethylene glycol dialkyl ether, especially benzyl alcohol, diethylene glycol ethyl Methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol diethyl ether, 3-methoxypropionic acid methyl, 3-ethoxypropionic acid methyl, 3-methoxypropionic acid ethyl is used as a solvent, for the present invention The content of the total solid content (the amount of the solvent divided by the total amount of the solvent-containing composition) in the composition is preferably from 1 to 50% by weight, more preferably from 5 to 40% by weight. The above solvent may be used in combination with a high boiling point solvent. Examples of the high boiling point solvent which can be used in combination include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, and N. N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octyl alcohol 1, 1-sterol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, monobutyl lactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate Wait. -45- 200835744 The amount of use in the case of using a high boiling point solvent in combination is preferably 90% by weight or less, and more preferably 80% by weight or less for total dissolution. The composition prepared as described above is preferably filtered using a millipore having a pore diameter of 〇. #m, more preferably 0.2 to 0.5/m. Formation of Protective Film of Color Filter Next, a method of forming a color protective film using the composition of the present invention will be described. The resin composition solution of the present invention is applied onto the surface of the substrate, and after calcination, the solvent is removed to form a coating film, and then the protective film of the desired color filter is obtained by heat treatment. As the substrate user, for example, a substrate such as glass crucible or resin can be used. Examples of the resin include a polyparaphenylene glycol ester, a polybutylene terephthalate, a polyether fluorene, a polycarbimine, and a ring-opening polymer of a cyclic olefin, and a coating such as the hydride. The method can be applied, for example, by a spray method, a roll coating method, a bar coating method, an ink jet method, or the like, a special dynamic coating method, a non-rotation coating method, or a slit die coating method. The conditions for calcination vary depending on the type of each component or the like, but for example, conditions of 1 to 15 minutes at 70 to 90 ° C can be employed. The coating film thickness is preferably 0.15 to 8.5 μm 〇15 to 6.5 #m, particularly preferably 0.15 to 4.5/m. Further, the thickness is the thickness after solvent removal. For the dose, 2 to 3.0 filters, etc., are pre-formed as quartz, dicarboxylic acid acetate, and poly resin. Rotating coating can be used to transfer. The blending ratio is preferably a coating film -46- 200835744 The heat treatment after the formation of the coating film can be carried out by a suitable heating device such as a hot plate or a dust-free oven. The treatment temperature is preferably from 150 to 2 5 Torr. The heating time may be 5 to 30 minutes in the case of using a hot plate, and the treatment time may be 30 to 90 minutes in the case of using an oven. Further, when a radiation-sensitive acid generator is used for the resin composition, the *resin composition is applied onto the surface of the substrate, and the solvent is removed by pre-baking to form a coating, and then radiation irradiation treatment (exposure treatment) is applied. Form the purpose of #, protective film. The heat treatment may be performed after the exposure treatment as needed. Examples of the radiation that can be used in the irradiation treatment of the radiation include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Among them, ultraviolet light having a wavelength of 190 to 450 nm is preferable. The exposure amount is preferably from 100 to 20,000 J/m2, more preferably from 150 to 10,000 J/m2. Further heat treatment may be performed after the irradiation. As the heating temperature at this time, it is preferably about 150 to 250 ° C, and as a heating means, for example, a suitable device such as a hot plate or a dust-free oven can be used. The heating time can be 5 to 30 minutes for the use of the heating plate, and 3 to 90 minutes for the oven. - In the protective film formed by the protective film of the color filter, the film thickness is preferably 〇. 1~8 # m, more preferably 〇·1~6//m' is optimally 〇.; 4#m. Further, when the protective film of the present invention is formed on a substrate having a step of a color filter, the film thickness is the thickness of the uppermost portion of the color filter. -47- 200835744 The protective film of the present invention is known from the following examples, and satisfies the surface hardness, transparency, heat resistance, alkali resistance, etc., and does not cause dents even in the state load, and has excellent It is suitable for use as a protective film for the purpose of flattening the step of the color filter formed on the base substrate. As described above, the present invention provides a cured film having extremely high flatness even on a surface having a low surface flatness, and is suitable for transparency, surface hardness, heat resistance, pressure resistance, acid resistance, and alkali resistance. a protective film for an optical device which is excellent in various resistances such as a sputtering resistance, and a resin composition excellent in storage stability, a method for forming a protective film using a fat composition, and a composition using the above composition The protective film. [Embodiment] EXAMPLES Hereinafter, the synthesis examples and examples will be described, and the present invention will be more specifically described. However, the present invention is not limited to the following examples. Production of (co)polymer Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-dimethylvaleronitrile and 200 parts of diethylene glycol ethyl methyl ether were charged. Continue to refill the weight fraction of tetrahydro-2H-pyran-2-yl methacrylate, 20 parts by weight of styrene, 3 (methacryloxy ethoxylate), photo-based based on heat , as the tree formed, -2,4 parts | 20 base) -48- 200835744 40 parts by weight of oxetane and 20 parts by weight of N-cyclohexylmaleimine Stir. The temperature of the solution was raised to 70 ° C. This temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-1]. The solid content concentration of the obtained polymer solution was 3 3 · 〇 by weight. The number average molecular weight of the polymer was 4,300 (the number average molecular weight was • the molecular weight in terms of polystyrene after measurement by GPC (gel permeation chromatography) HLC-8020 (manufactured by Tosoh Corporation). The same applies hereinafter.). Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. 20 parts by weight of tetrahydro-2H-pyranyl 2-yl methacrylate, 20 parts by weight of styrene, 40 parts by weight of 3-(methacryloxyethyl)oxetane and further 20 parts by weight of tricyclo[5.2.1.02,6]decane-8-yl methacrylate was gradually stirred with nitrogen. The temperature of the solution was raised to 70 Torr: and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 32.8% by weight. The number average molecular weight of the polymer was 4,300. Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and diethylene glycol ethyl methyl ether 200 were charged. Parts by weight. Continue to charge tetrahydro-2H-pyran-2-yl methacrylate 20 -49- 200835744 parts by weight, styrene 20 parts by weight, 3-(acryloxyethyl) oxetane 40 weight A part by weight and 20 parts by weight of n-cyclohexylmaleimide were gradually stirred with nitrogen. The temperature of the solution was raised to 70, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-3]. The obtained polymer solution had a solid concentration of 32.9 wt%. The polymer had a number average molecular weight of 4,200. In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylacetonitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were placed. After refilling with tetrahydro-2H-indole-20-ylmethylpropionate 20 parts by weight, benzene and 200 parts by weight, 3-(isopropyloxyethyl)oxetane 40 parts by weight and 20 parts by weight of bismuth methacrylate [5·2·1.〇2,6] 癸院-8-base, after stirring with nitrogen, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymerized product i [A-4]. The obtained polymer solution had a solid content concentration of 32.9% by weight. The number average molecular weight of the polymer was 4,400. Synthesis Example 5 - In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis- 2,4-monomethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. 20 parts by weight of 1-(cyclohexyloxy)ethyl methacrylate, 20 parts by weight of styrene, 40 parts by weight of 3-(methacryloxyethyl)oxetane and N are further added. - 20 parts by weight of cyclohexylmaleimine, -50-200835744 After stirring with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-5]. The obtained polymer solution had a solid content concentration of 3 3.0% by weight. The polymer had a number average molecular weight of 4,300. Synthesis Example 6 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. 20 parts by weight of 1-(cyclohexyloxy)ethyl methacrylate, 20 parts by weight of styrene, 40 parts by weight of 3-(methacryloxyethyl)oxetane and A 20 parts by weight of a tricyclo[5.2.1.02,6]decane-8-yl group of acrylic acid, and after stirring with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-6]. The resulting polymer solution had a solid component concentration of 32.7 wt%. The number average molecular weight of the polymer was 4,4 Torr. Synthesis Example 7 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 2 parts by weight of diethylene glycol ethyl methyl ether were charged. 20 parts by weight of 1-(cyclohexyloxy)ethylmethylpropionate, 20 parts by weight of styrene, 40 parts by weight of 3-(acryloxyethyl)oxetane and N 20 parts by weight of cyclohexylmaleimide, which was slowly stirred after being replaced with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer-solvent-51 - 200835744 solution containing the copolymer [A-7]. The solid content concentration of the obtained polymer solution was 33.6% by weight. The number average molecular weight of the polymer was 4,2 Torr. Synthesis Example 8 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Continue to charge 1 -(cyclohexyloxy)ethyl methacrylate 20 wt Φ > parts by weight, 20 parts by weight of styrene, 40 parts by weight of 3-(acryloxyethyl) oxetane And trimethyl methacrylate [5.2.1 〇 2,6] decane -8 yl 2 〇 parts by weight, after stirring with nitrogen, began to slowly stir. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-8]. The solid content of the obtained polymer solution was 33.0% by weight. The polymer had a number average molecular weight of 4,200. Synthesis Example 9 ® ) In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Subsequent loading of 25 parts by weight of tetrahydro-2H-anthracene-2-methylpropionate, 25 parts by weight of styrene and 3-(methacryloxyethyl) oxetane 50 parts by weight, after stirring with nitrogen, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-9]. The obtained polymer solution had a solid content concentration of 3 2 · 6 wt%. The number average molecular weight of the polymer is 452 00 -52 - 200835744. Synthesis Example 1 ο In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and diethylene glycol were charged. 200 parts by weight of ethyl methyl ether. 20 parts by weight of 1-ethylcyclopentyl methacrylate, 20 parts by weight of styrene, 40 parts by weight of 3-(methacryloxyethyl)oxetane and fluorene-cyclohexyl group were further charged. 20 parts by weight of maleimide, which was replaced with nitrogen, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [A-1 〇]. The obtained polymer solution had a solid content concentration of 3 3.0% by weight. The polymer had a number average molecular weight of 4,300. Comparative Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylacetonitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Further, 20 parts by weight of methacrylic acid, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, and 40 parts by weight of glycidyl methacrylate were further charged, and after stirring with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [a-1]. The solid content of the obtained polymer solution was 33.0% by weight. The number average molecular weight of the polymer was 4,4 Torr. Comparative Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis- 2,4-53-200835744-dimethylacetonitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Further, 20 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, and glycidyl methacrylate 40 are further charged. The parts by weight were gradually stirred after being replaced with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [a-2]. The obtained polymer solution had a solid content concentration of 3 3 · 1% by weight. The number of polymers φ . The average molecular weight is 4,200. Comparative Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of azobis-2,4-dimethylvaleronitrile and 2 parts by weight of diethylene glycol ethyl methyl ether were charged. 20 parts by weight of methacrylic acid, 2 parts by weight of styrene, 3 parts by weight of tricyclo [5·2 · 1.02, 6] decane, 8 yl groups, and 3 - (methacryl oxime) The oxyethyl)oxetane 4 parts by weight, after being replaced with a nitrogen gas, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [& _ 3]. The solid content concentration of the obtained polymer solution was 32.9 wt%. • The polymer has a number average molecular weight of 4,400. Comparative Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of azobis-2,4-dimethylvaleronitrile and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Further loading of tetrahydro-2H-pyran~2-yl methacrylate 25-54-200835744 parts by weight, 25 parts by weight of styrene and 3-(methacryloxyethyl)oxetane After 50 parts by weight of 'substituting with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [a-4]. The obtained polymer solution had a solid content concentration of 32.5% by weight. The number average molecular weight of the polymer was 61,000 °. Comparative Synthesis Example 5 In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of azobis-2,4-dimethylvaleronitrile and diethylene glycol B were charged. 200 parts by weight of methyl ether. Further, 25 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 25 parts by weight of styrene, and 50 parts by weight of 3-(methacryloxyethyl)oxetane are further charged. Stirring was started after replacing with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 7 hours to obtain a polymer solution containing the copolymer [a-5]. The obtained polymer solution had a solid content concentration of 32.5% by weight. The number average molecular weight of the polymer was 800 °. Modulation and evaluation of the resin composition Example 1 The solution containing the copolymer (A-1) obtained in the above Synthesis Example 1 (corresponding to the copolymer (A-1) 100 weight (Bl) τ-glycidoxypropyltrimethoxydecane 15.0 parts by weight, (D-1) as a surfactant SH-28PA (Toray · -55- 200835744) Dowcorning·polyoxyl (manufactured by the company) 0.1 parts by weight, (E-1) dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 50 parts by weight, and the solid content concentration is 20 weight After adding 8 to 2 ratios of propylene glycol monomethyl ether acetate (S-1) and diethylene glycol ethyl methyl ether (S-2), the ratio of 0.5 μm to mi 11 i ρ 〇re The filter was filtered to prepare a resin composition. The composition was applied onto a Si02-impregnated glass substrate using a rotor, and then pre-calcined at 80 ° C for 5 minutes on a hot plate to form a coating film, which was then heated in an oven at 230 ° C for 60 minutes. A protective film having a film thickness of 2.0 // m was formed. Evaluation of Protective Film (1) Evaluation of Transparency For the substrate having the protective film formed as described above, a spectrophotometer (1 50-20 type double beam (manufactured by Hitachi, Ltd.)) was used, and 400 to 800 nm was measured. Transmittance. The transmittance at 400 to 800 nm is the smallest as shown in Table 1. When the enthalpy is 95% or more, the transparency of the protective film is good. (2) Evaluation of heat-resistant dimensional stability The substrate having the protective film formed as described above was heated in an oven at 25 ° C for 1 hour, and the film thickness before and after heating was measured. The heat resistance dimensional stability calculated according to the following formula is shown in Table 1. If the enthalpy is 95% or more, it means that the heat resistance dimensional stability is good. -56- 200835744 Heat-resistant dimensional stability = (film thickness after heating) / (film thickness before heating) χ 100 (%) (3) Evaluation of alkali resistance The substrate having the protective film formed as described above at 30 ° After immersing 3 0 mi η in C, 5 % N a Η ,, water was removed from the hot plate, and then the film thickness was measured. The alkali resistance calculated according to the following formula is shown in Table 1. If the enthalpy is 95% or more, the alkali resistance is good. Alkali resistance = (film thickness after moisture removal) / (film thickness before immersion) x 1 00 (%) (4) Evaluation of heat discoloration resistance For a substrate having a protective film formed as described above, 25 in an oven The mixture was heated at 0 ° C for 1 hour, and the transparency before and after heating was measured in the same manner as in the above (1). The heat-resistant discoloration property calculated according to the following formula is shown in Table 1. When the enthalpy is 5% or less, the heat discoloration resistance is good. Heat-resistant discoloration = transmittance before heating - transmittance after heating (%) (5) Measurement of surface hardness For a substrate having a protective film formed as described above, by 8.4 of JIS K-5 400- 1 99 0 .1 Pencil Traction Test Determines the surface hardness of the protective film. This is shown in Table 1. If the crucible is 4H or harder than this, it means that the surface hardness is good. (6) Measurement of dynamic microhardness -57 - 200835744 For the substrate having the protective film formed as described above, a Shimadzu dynamic micro hardness tester DUH-201 (manufactured by Shimadzu Corporation) was used, and a triangular angle of 115° was used. (helocobitch type) of the indentation test, the protective film to a load dynamic micro hardness: O.lgf, speed:. 0.0145gf / sec, hold time:. 5sec, and the measuring temperature was 23 ° C 140 ° C under conditions of The measurement was carried out. The results are shown in Table 1. (7) Evaluation of Adhesion The Glass Wefer, OA10, which was made in the same manner as the substrate (SiO 2 impregnated glass) having the protective film formed as described above, was subjected to a Pressure Cooker Test (120 ° C). After the humidity was 100%, 4 hours, the adhesion of the protective film was evaluated by the 8.5.3 adhesion grid method of JIS K-5400- 1 990. The number of squares remaining in the square lattice 1 is shown in Table 1. (8) Evaluation of storage stability The viscosity of the resin composition for forming a protective film prepared in Example 1 was measured using an ELD type viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the composition was allowed to stand at 25 ° C, and the solution viscosity at 25 ° C was measured every day. The number of days required for 5% adhesion is determined by measuring the viscosity as a reference immediately after the modulation. The number of days is shown in Table 1. If the number of days is 20 days or longer, it indicates that the storage stability is good. (9) Evaluation of flatness -58- 200835744 Painted color resists on the Glass Wefer substrate (trade name "JCR RED 689", "JCR GREEN 706", "CR 8200B", above SR (share)) Coating was carried out using a rotor, and pre-calcination was carried out at 90 ° C for 150 seconds on a hot plate to form a coating film. Then, using the exposure lens Canon PLA501F (manufactured by Canon), the ghi line (intensity ratio of wavelengths of 436 nm, 405 nm, and 3 65 nm = 2.7:2.5:4.8) was converted into i-line. Under the exposure of 2,000 J/m2, X-ray was developed with 0.05% potassium hydroxide aqueous solution, lightly washed with ultrapure water for 60 seconds, and then heated in the oven for 30 minutes at 30 °C for 30 minutes. Processing 'three-color striped color filters forming red, green, and blue (strip width. 10 0// m ). The unevenness of the surface of the substrate on which the color filter was formed was measured by the surface roughness "a - s t e p" (trade name: T e n c ο 1 manufactured by Japan Co., Ltd.) to obtain 1 m. However, it was measured at a measurement length of 2,000 // m, a measurement range of 2,000 // m, and a measurement number of η = 5. In other words, the measurement direction Φ) is in the direction of the short axis direction of the stripe line in the red, green, and blue directions, and the direction of the long axis direction of the stripe line of the same color of red, green, green, blue, and blue, and is performed in each direction. η = 5 (total η number is 10). ^ After the above protective film forming composition is coated with a rotor, the hot plate is pre-calcined at 90 ° C for 5 minutes to form a coating film, which is then heated in an oven at 230 ° C for 60 minutes. A protective film having a film thickness of 2.0 // m formed on the color filter is formed. However, the so-called film thickness is expressed as the uppermost thickness of the color filter formed on the substrate. In the contact-type film thickness measuring apparatus a-step (manufactured by Tencol Japan Co., Ltd.), the surface unevenness of the protective film was measured on the substrate-59-200835744 having the protective film on the color filter formed as described above. However, it is measured at a measurement length of 2,0 0 0 // m, a measurement range of 2,000 // m, and a measurement number of n = 5. In other words, the measurement direction is the direction of the short-axis direction of the stripe line in the red, green, and blue directions, and the direction of the long-axis direction of the stripe line of the same color of red, green, green, blue, and blue, and η 2 is performed for each direction. The measurement was performed (the total number of η was 10). The average of the height difference (nm) of the highest part and the bottom part of each measurement is 10 times as shown in Table 1. When the enthalpy is 300 00 nm or less, the flatness is good. Examples 2 to 10 and Comparative Examples 1 to 5 The types and amounts of the respective components of the composition are as shown in Table 1. The resin composition was prepared in the same manner as in Example 1. A protective film was formed using the resin composition for forming a protective film prepared as described above in the same manner as in Example 1 and evaluated. The results are shown in Table 1. -60- 200835744

實施例 ο 雇 1 I 雇 I 1 1 1 1 Ο τ— If) 1 ϊ τ- Ο 1 1 1 s σ> 1 i i 1 1 1 1 1 Ο ο χ— i 1 1 1 1 1 in 1 g χ- Ο 1 I 1 s 00 1 1 1 瞻 ϊ 1 1 Ο τ— 1 I 1 1 1 I 1 l〇 1 1 τ- Ο 1 1 I s 卜 1 1 1 1 1 1 ο ο τ— 1 1 κ 1 1 1 1 1 in T— S I 1 1 1 ^r- d s CD 1 1 1 1 1 Ο ν 1 i 1 ϊ 1 1 1 1 1 LO 1 s 1 1 τ- Ο 1 § LO I 1 1 1 ο τ— 1 1 I 1 I I 1 1 麵 I in 1 s 1 i 1 CNJ d § 1 1 1 Ο Τ— 1 1 « I 1 1 1 1 1 1 1 l〇 1 s 1 τ- Ο 1 1 s CO 1 1 o T— I 1 1 1 1 1 1 1 1 1 1 i in T— 〇 CNJ I 1 I CNI ο I o LO r- CM ! 〇 T— 1 1 1 1 I 1 1 1 雇 1 1 1 1 LO 1 1 麵 1 T— d s τ— T— 〇 1 1 1 1 1 雇 1 I 1 1 1 1 1 I IT) 1 藝 τ- Ο 1 1 1 s CNI o Cf o 3: g jl 工 Ο χ H ή Έ d) X 〇 LJJ § o 0 3: δ Έ 〇 Q 01 工 H ή Έ ώ X 〇 LJJ O ω § 0 04 δ 1 11 I 工 ο 0： X 卜 ή ① X 〇 LU έ ω Csl δ ο 1 Έ Ο Q DL 工 Η Έ ώ X 〇 UJ C0 % § ο εϋ ο 3: δ jT 工 工 ο ή ώ X Ο UJ 2 ω § ο ο 3: ο CNJ Έ ο Q ίϋ 工 Ο ή Έ 1 ① X 〇 UJ 2 ω § ο CVJ δ 5： 邑 Ίί 1 工 ο m 工 ο ή ① X Ο LLJ 2 C0 § ο ο 3： ο CN "ίΓ Ο Q m 1 ο Έ X LLJ 2 CO ίο S ί5 1Γ CL 工 Η ή Έ ώ X ο UJ σ) § ο ο 5 ο eg Τ 工 Ο αΐ ο UJ ή Έ ω X 〇 UJ C0 ω S § ο ο 茇 ο CM τ X ο ο ω 1 § ο 3: ο οα 1Γ I X ο οΐ 工 卜 ύ ϋ ω OJ ο ο 3： (1 Ο Q ώ X 〇 UJ ω ίο g ΙΟ ίο CM DL X Η ή ώ X 〇 υϋ 会 ω Gr o lO l〇 CNI^ IT Ο χ H ύ Έ ώ X O LLJ 2 00 T -環氧丙氧基丙基三甲氧基砂烷 ΈΡ828 EP154 SH-28PA 寸 A ω FTX-218 PAINTAD19 DPHA SI-300 I < (N < m < 寸 < < < 卜 < 00 <： ΟΝ < ο 1—^ < τ-Η ά CN ά ΓΛ ά cd cd τ-Η PQ ό (N ό 1 Q (Ν Q m Q 寸 Q r-H ώ t-H ώ 麟A ¢1( < |(B戚分] (Q成分 (D减分 |(E戚分| |(F)成分| -61- 200835744Example ο Employment 1 I Employment I 1 1 1 1 Ο τ— If) 1 ϊ τ- Ο 1 1 1 s σ> 1 ii 1 1 1 1 1 Ο ο χ — i 1 1 1 1 1 in 1 g χ- Ο 1 I 1 s 00 1 1 1 ϊ 1 1 Ο τ— 1 I 1 1 1 I 1 l〇1 1 τ- Ο 1 1 I s 1 1 1 1 1 1 ο ο τ— 1 1 κ 1 1 1 1 1 in T— SI 1 1 1 ^r- ds CD 1 1 1 1 1 Ο ν 1 i 1 ϊ 1 1 1 1 1 LO 1 s 1 1 τ- Ο 1 § LO I 1 1 1 ο τ— 1 1 I 1 II 1 1 face I in 1 s 1 i 1 CNJ d § 1 1 1 Ο Τ — 1 1 « I 1 1 1 1 1 1 1 l〇1 s 1 τ- Ο 1 1 s CO 1 1 o T — I 1 1 1 1 1 1 1 1 1 1 i in T— 〇CNJ I 1 I CNI ο I o LO r- CM ! 〇T— 1 1 1 1 I 1 1 1 Employment 1 1 1 1 LO 1 1 1 T— ds τ— T— 〇1 1 1 1 1 Employment 1 I 1 1 1 1 1 I IT) 1 Art τ- Ο 1 1 1 s CNI o Cf o 3: g jl Industrial χ H ή Έ d) X 〇LJJ § o 0 3: δ Έ 〇Q 01 H ή ώ ώ X 〇LJJ O ω § 0 04 δ 1 11 I ο 0: X ή 1 X 〇LU έ ω Csl δ ο 1 Έ Ο Q DL Έ ώ X 〇 UJ C0 % § ο εϋ ο 3: δ jT 工 ο ή Ο X Ο UJ 2 ω § ο ο 3: ο CNJ Έ ο Q ϋ Ο ή Έ 1 1 X 〇 UJ 2 ω § ο CVJ δ 5: 邑Ίί 1 work ο m ο ή 1 X Ο LLJ 2 C0 § ο ο 3: ο CN " Γ Ο Q m 1 ο Έ X LLJ 2 CO ίο S ί5 1Γ CL Η Έ ώ ώ X ο UJ σ) § ο ο 5 ο eg Τ Ο αΐ ο UJ ή Έ ω X 〇 UJ C0 ω S § ο ο 茇 CM τ X ο ο ω 1 § ο 3: ο οα 1Γ IX ο ο ΐ ύ ω ω ω OJ ο ο 3: (1 Ο Q ώ X 〇 UJ ω ίο g ΙΟ ίο CM DL X Η ή ώ X 〇υϋ ω Gr o lO l〇CNI^ IT Ο χ H ύ Έ ώ XO LLJ 2 00 T-glycidoxypropyltrimethoxysane ΈΡ 828 EP154 SH-28PA inch A ω FTX-218 PAINTAD19 DPHA SI-300 I < (N < m &lt ; inch <<<< 00 <: ΟΝ < ο 1—^ < τ-Η ά CN ά ΓΛ ά cd cd τ-Η PQ ό (N ό 1 Q (Ν Q m Q inch Q rH ώ tH ώ A A ¢ 1 ( < | (B 戚 points) (Q component (D minus points | (E 戚 points | | (F) ingredients | -61- 200835744

(ilH 漱 實施例 ο τ— S-1/S-2 =8/2 I 4300 I CO CN σ> σ> 00 σ> σ> CO 工 CNJ 100 100 30日以上 130 ⑦ S-1/S-2 =8/2 4200 寸 csi 00 σ> σ> σ> σ> σ> 00 工 卜 〇 CD CO 100 100 30日以上 170 00 S-1/S-2 =8/2 o CNJ 4200 CO c\i CO σ> CD Ο) 〇> σ> CO X 1〇 CN1 CO CM 100 100 30日以上 150 卜 S-1/S-2 =8/2 I 4200 I CO c\i 00 σ> CD CO 工 卜 T— (D CO 100 100 30日以上 170 CD S-1/S-2 =8/2 4400 CM c\i 00 σ> σ> σ> CO 工 卜 〇 in CO 100 100 30日以上 170 LO S-1/S-2 =8/2 4300 CN csi σ> σ> 00 σ> σ) CO 工 寸 CVJ in CsJ 100 100 30日以上 160 寸 S-1/S-2 =8/2 4400 CO c\i 00 σ> σ> σ> σ> CO 工 卜 CO CO 100 100 30日以上 170 CO S-1/S-2 =8/2 4200 CO csi σ> σ> 00 σ> σ> σ) CO 工 1〇 T- 00 00 CM 100 100 30日以上 160 CNJ S-1/S-2 =8/2 I 4400 I CM csi σ> σ> 00 σ> σ) ο CO 工 1〇 CNI CO 00 CNJ 100 100 30日以上 150 τ— S-1/S-2 =8/2 4300 CO c\i 00 σ> 卜 σ> σ> σ> 00 I 寸 CD CM 100 100 30日以上 140 溶劑 固體成分濃度(重量 %) 共聚合物(A)Mn 共聚合物(A)Mw/Mn 透明性(％) I耐熱尺寸安定性(％) ι 耐鹼性(％) 耐熱變色性 铅筆硬度 23 °C 140°c Glass Wefer OAIO 保存安定性(曰） @25 °C 平坦化性(nm) 動態微小 硬度 密著性 -62- 200835744 表ι(續)(ilH 漱 embodiment ο τ - S-1 / S-2 = 8 / 2 I 4300 I CO CN σ > σ > 00 σ > σ > CO Gong CNJ 100 100 30 days or more 130 7 S-1/S-2 =8/2 4200 inch csi 00 σ>σ>σ>σ>σ> 00 work 〇 CD CO 100 100 30 days or more 170 00 S-1/S-2 = 8/2 o CNJ 4200 CO c\i CO σ> CD Ο) 〇>σ> CO X 1〇CN1 CO CM 100 100 30 days or more 150 s S-1/S-2 = 8/2 I 4200 I CO c\i 00 σ> CD CO — (D CO 100 100 30 days or more 170 CD S-1/S-2 = 8/2 4400 CM c\i 00 σ>σ>σ> CO work in CO 100 100 30 days or more 170 LO S-1 /S-2 =8/2 4300 CN csi σ>σ> 00 σ> σ) CO inch CVJ in CsJ 100 100 30 days or more 160 inch S-1/S-2 = 8/2 4400 CO c\i 00 σ>σ>σ>σ> CO workbench CO CO 100 100 30 days or more 170 CO S-1/S-2 = 8/2 4200 CO csi σ>σ> 00 σ>σ> σ) CO work 1〇T - 00 00 CM 100 100 30 days or more 160 CNJ S-1/S-2 =8/2 I 4400 I CM csi σ>σ> 00 σ> σ) ο CO 1 〇 CNI CO 00 CNJ 100 100 30 days or more 150 τ — S-1/S-2 = 8/2 4300 CO c\i 00 σ>卜σ>σ>σ> 00 I inch CD CM 100 100 30 days or more 140 Solvent solid content concentration (% by weight) Copolymer (A) Mn Copolymer (A) Mw/Mn Transparency (%) I Heat-resistant dimensional stability (%) ι Alkali resistance (%) Heat-resistant discoloration pencil hardness 23 °C 140 °C Glass Wefer OAIO Preservation stability (曰) @25 °C Flatness (nm) Dynamic micro hardness adhesion-62- 200835744 Table ι (continued)

比較例 1 2 3 4 5 共聚合物 (A) A-1 - - - - - A-2 - - - - - A-3 - - - - - A-4 - - - - - A-5 - - - - - A-6 - - - - - A-7 - - - - - A-8 - - - - - A-9 - - - - - A-10 - - - - - a-1 100 - - - - a-2 - 100 - - - a-3 - - 100 - - a-4 - - - 100 - a-5 - - - - 100 (B)成分 B-l 15 15 15 15 15 (C)成分 C-l - - - 20 20 C-2 - - - - - (D诚分 D-l 0.1 0.1 0.1 - - D-2 - - - - - D-3 - - - - - D-4 - - - 0.1 0.1 (E)成分 E-l 50 50 50 50 50 (F戚分 F-i 1 1 1 溶劑 S-l/S-2 二 8/2 S-l/S-2 二 8/2 S-l/S-2 =8/2 S-l/S-2 =8/2 S-l/S-2 =8/2 固體成分濃度(重量％) 20 20 20 20 20 共聚合物(A)Mn 4400 4200 4400 61000 800 共聚合物(A)Mw/Mn 2.3 2.2 2.3 2.2 2.3 透明性(％) 98 98 98 99 99 耐熱尺寸安定性(％) 99 98 96 98 94 耐鹼性(％) 98 99 98 99 99 耐熱變色性 3 3 3 3 6 鉛筆硬度 5H 5H 5H 5H 5H 動態微小硬 度 23 °C 31 30 31 31 31 140°C 28 26 27 26 26 密著性 Glass Wefer 100 100 100 100 100 OA10 100 100 100 100 100 保存安定性(日） @25〇C 7曰 20曰 14日 30日以上 30日以上 平坦化能㈣ 350 280 320 370 150 -63- 200835744 且，於表1中，共聚合物（A)之St表示苯乙烯、3-EOxe-MA表示3-(甲基丙烯醯氧基乙基）氧雜環丁烷、 M-THP表示四氫- 2H-吡喃-2-基甲基丙烯酸酯、CHMI表示 N -環己基馬來醯亞胺、DCM表示甲基丙烯酸三環〔 5·2·1·02 ’ 6〕癸烷-8-基、3-EOxe-A表示3-(丙烯醯氧基 乙基）氧雜環丁烷、M-CHE表示1-(環己氧基）乙基甲 基丙烯酸酯、M-ECP表示卜乙基環戊基甲基丙烯酸酯、 GMA表示甲基丙烯酸縮水甘油基、MA表示甲基丙烯酸。 又’接著助劑（B )、添加劑（C )、界面活性劑（D )及溶劑（S )各如以下者。 B-1: 7-環氧丙氧基丙基三甲氧基矽烷 C-1 :雙酚A漆用酚醛型環氧基樹脂（日本環氧樹脂 (股）製商品名：EP 82 8 ) C-2 :漆用酚醛型環氧基樹脂（日本環氧樹脂（股） 製商品名：EP154 ) D-1:聚砂氧系界面活性劑（Toray· dowcorning·聚 矽氧（股）製商品名：SH-28PA) D-2 :聚矽氧系界面活性劑（Βγκ-Chemie·日本（股 )製商品名：Byk-344) D-3 :氟系界面活性劑（（股）Neos製商品名： Ftergent FTX-2 1 8 ) D ·4 :聚砍氧系界面活性劑（T 〇 r a y · d 〇 w c 〇 r n i n g ·聚石夕 氧（股）製商品名：PAINT ADI 9 ) E_l:二季戊四醇六丙烯酸酯（日本化藥（股）製商 -64- 200835744 品名：KAYARAD DPHA ) F-l:三苯基鎏三氟甲磺酸酯（三新化學（股）製SI- 300 ) S-1 :丙二醇單甲醚乙酸酯 S-2 :二乙二醇乙基甲基醚 -65-Comparative Example 1 2 3 4 5 Copolymer (A) A-1 - - - - - A-2 - - - - - A-3 - - - - - A-4 - - - - - A-5 - - - - - A-6 - - - - - A-7 - - - - - A-8 - - - - - A-9 - - - - - A-10 - - - - - a-1 100 - - - - a-2 - 100 - - - a-3 - - 100 - - a-4 - - - 100 - a-5 - - - - 100 (B) Ingredient Bl 15 15 15 15 15 (C) Component Cl - - - 20 20 C-2 - - - - - (D Cheng Dl 0.1 0.1 0.1 - - D-2 - - - - - D-3 - - - - - D-4 - - - 0.1 0.1 (E) Component El 50 50 50 50 50 (F戚Fi 1 1 1 Solvent Sl/S-2 2 8/2 Sl/S-2 2 8/2 Sl/S-2 =8/2 Sl/S-2 =8/2 Sl/S-2 = 8/2 Solid content concentration (% by weight) 20 20 20 20 20 Copolymer (A) Mn 4400 4200 4400 61000 800 Copolymer (A) Mw/Mn 2.3 2.2 2.3 2.2 2.3 Transparency ( %) 98 98 98 99 99 Heat resistance dimensional stability (%) 99 98 96 98 94 Alkali resistance (%) 98 99 98 99 99 Heat resistance discoloration 3 3 3 3 6 Pencil hardness 5H 5H 5H 5H 5H Dynamic micro hardness 23 ° C 31 30 31 31 31 140°C 28 26 27 26 26 Adhesion Glass Wefer 100 100 100 100 100 OA10 100 100 100 100 100 Preservation stability (Day) @25〇C 7曰20曰14日30日以上30日平化化(四) 350 280 320 370 150 -63- 200835744 Also, in Table 1, the copolymer of the copolymer (A) represents styrene 3-EOxe-MA represents 3-(methacryloxyethyl)oxetane, M-THP represents tetrahydro-2H-pyran-2-ylmethacrylate, and CHMI represents N-ring Hexylmaleimine, DCM means tricyclo[5.2·1·02 '6]decane-8-yl, 3-EOxe-A represents 3-(acryloxyethyl)oxa Cyclobutane, M-CHE means 1-(cyclohexyloxy)ethyl methacrylate, M-ECP means bethyl cyclopentyl methacrylate, GMA means glycidyl methacrylate, MA means methacrylic acid . Further, the auxiliary agent (B), the additive (C), the surfactant (D) and the solvent (S) are each as follows. B-1: 7-glycidoxypropyltrimethoxydecane C-1: phenolic epoxy resin for bisphenol A paint (trade name: EP 82 8 manufactured by Japan Epoxy Resin Co., Ltd.) C- 2: phenolic epoxy resin for lacquer (trade name: EP154, manufactured by Nippon Epoxy Resin Co., Ltd.) D-1: Polysilicate surfactant (Toray·dowcorning·Polyoxime) SH-28PA) D-2: Polyoxo-based surfactant (trade name: Byk-344, manufactured by Βγκ-Chemie·Japan) D-3: Fluorine-based surfactant (trade name: Neos) Ftergent FTX-2 1 8 ) D ·4 : Polyoxonated surfactant (T 〇ray · d 〇wc 〇rning · Ju Shi Xi Oxygen Co., Ltd. trade name: PAINT ADI 9 ) E_l: dipentaerythritol hexaacrylate Ester (Nippon Chemical Co., Ltd. -64-200835744 Product Name: KAYARAD DPHA) Fl: Triphenylsulfonium trifluoromethanesulfonate (SI-300, Sanshin Chemical Co., Ltd.) S-1: Propylene glycol monomethyl Ether acetate S-2: diethylene glycol ethyl methyl ether-65-

Claims (1)

200835744 十、申請專利範圍 1 · 一種硬化性樹脂組成物，其特徵爲含有（A ) ( a- 1 )來自具有至少1種選自羧酸的縮醛酯結構、羧酸的酮 縮醇酯結構、羧酸的1-烷基環烷基酯結構及羧酸的t-丁基 酯結構所成群之結構的聚合性不飽和化合物之聚合單位、200835744 X. Patent Application No. 1 A curable resin composition characterized in that (A) (a-1) is derived from a ketal structure having at least one acetal ester structure selected from a carboxylic acid and a carboxylic acid a polymerization unit of a polymerizable unsaturated compound having a structure in which a 1-alkylcycloalkyl ester structure of a carboxylic acid and a t-butyl ester structure of a carboxylic acid are grouped (a-2 )來自具有氧雜環丁烷基之聚合性不飽和化合物的 聚合單位、（a-3 )來自含有至少1種選自含有環氧乙烷 基之聚合性不飽和化合物、（甲基）丙烯酸烷基酯、（甲 基）丙烯酸環狀烷基酯、（甲基）丙烯酸芳基酯、不飽和 二羧酸二酯、雙環不飽和化合物、馬來醯亞胺化合物、不 飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、 不飽和二羧酸、及不飽和二羧酸酐所成群所成之上述（a-1 ) 、（ a-2 )聚合單位以外的聚合性不飽和化合物之聚合 單位所成共聚合物、以及溶劑。 2 ·如申請專利範圍第1項之硬化性樹脂組成物，其 中共聚合物的凝膠滲透層析儀所測定之聚苯乙烯換算數平 均分子量爲1，〇〇〇〜50,000的範圍。 3. 如申請專利範圍第1項或第2項之硬化性樹脂組 成物，其爲使用於彩色濾光片之保護膜形成上。 4. 一種彩色濾光片之保護膜的形成方法，其特徵爲 含有將如申請專利範圍第1項至第3項中任一項之硬化性 樹脂組成物塗佈於基板上形成塗膜之步驟、及於該塗膜以 放射線照射之步驟。 5. 一種彩色濾光片之保護膜的形成方法，其特徵爲 -66 - 200835744 含有將如申請專利範圍第1項至第3項中任一項之硬化性 樹脂組成物塗佈於基板上形成塗膜之步驟、及加熱該塗膜 之步驟。 6. 一種彩色濾光片之保護膜，其特徵爲以如申請專 利範圍第4項獲第5項之方法所形成。 -67- 200835744 七 無 ·· 明 說 單 簡 號 符 表 為代 圖件 表元 代之 定圖 指表 :案代 圖本本 表' ， 代 定一二 .b曰 無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無(a-2) a polymerization unit derived from a polymerizable unsaturated compound having an oxetanyl group, (a-3) derived from a polymerizable unsaturated compound containing at least one selected from the group consisting of an oxirane group, Alkyl acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic a group other than the above (a-1) and (a-2) polymerization units formed by a group of a compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated dicarboxylic anhydride A copolymer formed by a polymerization unit of a polymerizable unsaturated compound, and a solvent. (2) The curable resin composition according to the first aspect of the patent application, wherein the average molecular weight of the polystyrene converted by the gel permeation chromatograph of the conjugated polymer is 1, 〇〇〇 50,000 to 50,000. 3. The curable resin composition of claim 1 or 2, which is used for the formation of a protective film for a color filter. A method of forming a protective film for a color filter, comprising the step of applying a curable resin composition according to any one of claims 1 to 3 to a substrate to form a coating film. And a step of irradiating the coating film with radiation. A method of forming a protective film for a color filter, characterized in that -66 - 200835744 comprises applying a curable resin composition according to any one of claims 1 to 3 on a substrate. a step of coating the film and a step of heating the coating film. A protective film for a color filter, which is characterized by the method of item 5 of item 4 of the patent application. -67- 200835744 七无·· 明说单单单符表 is the map of the generation of the map table on behalf of the map: the representative of the map of this table', the set of one or two. b曰 no eight, if there is a chemical formula in this case, Please reveal the chemical formula that best shows the characteristics of the invention: none
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CN101186740B (en) 2011-05-25
KR101442241B1 (en) 2014-09-19
JP2008144124A (en) 2008-06-26
CN101186740A (en) 2008-05-28

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