[go: up one dir, main page]

TW200806701A - Resin composition, protective film of color filter, and method for forming the same - Google Patents

Resin composition, protective film of color filter, and method for forming the same Download PDF

Info

Publication number
TW200806701A
TW200806701A TW096113230A TW96113230A TW200806701A TW 200806701 A TW200806701 A TW 200806701A TW 096113230 A TW096113230 A TW 096113230A TW 96113230 A TW96113230 A TW 96113230A TW 200806701 A TW200806701 A TW 200806701A
Authority
TW
Taiwan
Prior art keywords
acrylate
meth
weight
protective film
copolymer
Prior art date
Application number
TW096113230A
Other languages
Chinese (zh)
Other versions
TWI411623B (en
Inventor
Jiro Ueda
Hiroshi Shiho
Junji Yoshizawa
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200806701A publication Critical patent/TW200806701A/en
Application granted granted Critical
Publication of TWI411623B publication Critical patent/TWI411623B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133519—Overcoatings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a resin composition which is capable of forming a cured film having high flatness even on a substrate having low surface flatness, is suitably used for forming a protective film for an optical device having high transparency and surface hardness and excellent in various resistances such as heat and pressure resistances, acid and alkali resistances and sputtering resistance, and excels in storage stability as a composition, a method for forming a protective film from the composition and the protective film. The curable resin composition comprises a high-molecular-weight body (A) having at least one structure selected from the group consisting of acetal ester structures of carboxylic acid, ketal ester structures of carboxylic acid, 1-alkylcycloalkyl ester structures of carboxylic acid and t-butyl ester structures of carboxylic acid, and an alkoxysilyl structure.

Description

200806701 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關硬性性樹脂組成物，由該組成物形成保 護膜之方法及保護膜。更詳細爲，有關適用爲形成液晶顯 示元件（LCD )用彩色濾光片及電荷結合元件（c CD )用 彩色濾光片所使用之保護膜材料的硬化性樹脂組成物，使 . 用該組成物形成保護膜之方法，及由該組成物形成的保護200806701 (1) Description of the Invention [Technical Field] The present invention relates to a hard resin composition, a method of forming a protective film from the composition, and a protective film. More specifically, the composition is a curable resin composition suitable for forming a protective film material for a color filter for a liquid crystal display element (LCD) and a color filter for a charge-carrying element (c CD). Method of forming a protective film, and protection formed by the composition

【先前技術】 LCD及C CD等放射線裝置於製造過程中需進行溶劑、 酸或鹼溶液等浸漬顯示元件之處理，又，以濺射法形成配 線電極層時局部性表面會曝露於高溫下。爲了防止該類處 理破害或損傷元件’因此元件表面設置對該處理具有耐性 之薄膜所形成的保護膜。 該類保護膜被要求具有，對所有形成該保護膜之基體 、底層及形成於保護膜上之層具有高密合性、膜本身具有 平滑及強靭性、具有透明性、具有高耐熱性及耐光性、長 期間不會有著色、變黃、白化等變質情形，及具有優良耐 水性、耐溶劑性、耐酸性及耐鹼性等之性能。已知形成符 合此等諸特性之保護膜用的材料如，含有具環氧丙基聚合 物之熱硬化性組成物（參考特開平5 -7 8 45 3號公報及特開 2 0 0 1 - 9 1 7 3 2 號公報）。 又，以該類保護膜作爲彩色液晶顯示裝置、電荷結合 -5^ 200806701 (2) 元件之彩色濾光片保護膜用時，一般要求該形成於底部基 板上之彩色濾光片可使段差平坦化。 另外彩色液晶顯示裝置，例如STN ( Super Twisted Nematic)方式或 TFT( Thin Film Transis ter)方式之彩色[Prior Art] A radiation device such as an LCD or a C CD needs to be treated with a solvent, an acid or an alkali solution, etc. during the manufacturing process, and a localized surface is exposed to a high temperature when a wiring electrode layer is formed by a sputtering method. In order to prevent such treatment from damaging or damaging the element, the surface of the element is provided with a protective film formed of a film resistant to the treatment. Such a protective film is required to have high adhesion to all of the substrate, the underlayer and the layer formed on the protective film, the film itself has smoothness and toughness, transparency, high heat resistance and light resistance. In the long period of time, there will be no deterioration of coloring, yellowing, whitening, etc., and it has excellent water resistance, solvent resistance, acid resistance and alkali resistance. It is known that a material for forming a protective film conforming to such characteristics, for example, contains a thermosetting composition having a epoxy propyl polymer (refer to Japanese Laid-Open Patent Publication No. Hei 5-7-8 45 3 and JP-A-200- 9 1 7 3 2). Moreover, when such a protective film is used as a color liquid crystal display device or a color filter protective film of a charge-bonding device, it is generally required that the color filter formed on the base substrate can flatten the step. Chemical. In addition, a color liquid crystal display device such as an STN (Super Twisted Nematic) method or a TFT (Thin Film Transis ter) method

L 液晶顯示元件爲了使液晶層保持均勻的晶粒間距，係貼合 保護膜上散布管狀調距器之板物。其後熱壓合密封劑以密 封液晶單元，但此時之熱及壓力會造成存在管子部分的保 護膜凹陷現象，而使晶粒間距混亂之問題。 特別是製造STN方式之彩色液晶顯示元件時，需極嚴 格要求彩色濾光片與對向基板之貼合精準度，因此要求保 護膜具有高度段差平坦化性能及耐熱耐壓性能。 又，近年來也採用以濺射法於彩色濾光片之保護膜上 形成配線電極（銦錫氧化物：ITO )膜後，以強酸或強鹼 等製圖於ITO之方式。因此彩色濾光片保護膜於濺射時會 使局部表面曝露於高溫下，及經歷各種藥品處理。故要求 具有對此等處理之耐性，及藥品處理時ITO不會由保護膜 剝離般對配線電極之密合性。 形成該類保護膜時使用優點爲，可以簡易方式形成硬 度優良之保護膜的熱硬化性組成物雖可降低成本，但爲了 使保護膜樹脂組成物具有上述般諸特性需具有，可形成強 固交聯之良好反應性的交聯基或觸媒。因此會有組成物本 身之架構壽命非常短的問題，而不易控制。即，組成物之 塗佈性能本身除了會經時惡化外，塗佈機頻繁維修、洗淨 等必要操作也煩雜。 -6- 200806701 (3) 目前尙無可簡易形成透明性等保護膜用一般所要求之 性能均能符合上述諸性能的保護膜，及具有組成物用優良 保存安定性之材料。 又，特開平4-2 1 8 56 1號公報雖揭示塗料、油墨、接著 劑、成形品所使用含有潛在化羧基化合物之熱硬化性組成 物，但未揭示任何有關彩色濾光片之保護膜。 【發明內容】 發明之揭示 基於上述事情，因此本發明之目的爲提供適用於形成 ，既使表面平坦性較低之基體也可形成平坦性高之硬化膜 ，且具有高透明性、高表面硬度及優良耐熱耐壓性、耐酸 性、耐鹼性、耐濺污性及各種耐性的光裝置用保護膜，具 有優良組成物用保存安定性之組成物，使用該組成物形成 保護膜之方法及由該組成物形成之保護膜。 本發明之其他目的及優點可由後述說明得知。 本發明之上述目的可由第一特徵爲，含有具有羧酸之 縮醛酯構造、羧酸之縮酮酯構造、羧酸之1 -烷基環烷基 酯構造及羧酸之t - 丁基酯構造群中所選出至少一種之構 造與烷氧基矽烷基構造的高分子量物（A )，及有機溶劑 之硬化性樹脂組成物達成。 本發明之上述目的可由第二特徵爲，含有將本發明之 硬化性樹脂組成物塗佈於基板上以形成塗膜之步驟，及以 放射線照射該塗膜之步驟的彩色濾光片之保護膜的形成方 200806701 (4) 法達成。 本發明之上述目的可由第三特徵爲，含有將本發明之 硬化性樹脂組成物塗佈於基板上以形成塗膜之步驟，及將 該塗膜加熱之步驟的彩色濾光片之保護膜的形成方法達成 〇 本發明之上述目的可由第四特徵，以上述本發明之形 成方法由上述硬化性樹脂組成物形成的彩色濾光片之保護 膜達成。 實施發明之最佳形態 下面將說明本發明之樹脂組成物的各成份。 高分子量物（A ) 本發明所使用之高分子量物（A )爲’具有羧酸之纖 醛酯構造、羧酸之縮酮酯構造、羧酸之1 一烷基環烷基酯 構造及羧酸之t- 丁基酯構造群中所選出至少一種之構造 與烷氧基矽烷基構造。 鍵結醯基形成羧酸之縮醛酯構造的基如，1 -甲氧基 乙氧基、1 一乙氧基乙氧基、1 一 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 一 sec — 丁氧基乙氧基、1— t—丁氧基乙氧基、1 一環戊氧基乙氧基、1-環己氧基乙興基、1一降坎氧基乙 氧基、1一冰片氧基乙氧基、1—苯氧基乙氧基、1— (1 一 萘氧基）乙氧基、1一节氧基乙氧基、1 一苯乙氧基、（環 -8- 200806701 (5) 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）（苄氧基）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 一丙氧基 ^ .)甲氧基、（苯基）（環己氧基）甲氧基、（苯基）（苯 φ 氧基）甲氧基、（苯基）（苄氧基）甲氧基、（苄基）（ 甲氧基）甲氧基、（苄基）（乙氧基）甲氧基、（苄基） (η —丙氧基）甲氧基、（苄基）（i 一丙氧基）甲氧基、 (苄基）（環己氧基）甲氧基、（苄基）（苯氧基）甲氧 基、（苄基）（苄氧基）甲氧基、2-四氫呋喃氧基、2 — 四氫吡喃氧基等。 其中較佳爲，1 一乙氧基乙氧基、1—環己氧基乙氧基: 、2 —四氫卩比喃氧基、1一 η—丙氧基乙氧基。 • 鍵結羧基形成羧酸之縮酮酯構造的基如，1一甲基- 甲氧基乙氧基、1 一甲基—1一乙氧基乙氧基、1 一甲基一 1 ^ — η—丙氧基乙氧基、1—甲基—：[一 i 一丙氧基乙氧基、1 —甲基一 1— η — 丁氧基乙氧基'1 一甲基一l—i一丁氧基 乙氧基、1—甲基—Ι-sec— 丁氧基乙氧基、1—甲基一1 一 t 一丁氧基乙氧基、1—甲基一 1 一環戊氧基乙氧基、1 — 甲基—1 一環己氧基乙氧基、1 一甲基一 1 一降坎氧基乙氧 基'1 一甲基一 1 一冰片氧基乙氧基、1 一甲基_1_苯氧基 乙氧基、1 一甲基—1 一 （1 一萘氧基）乙氧基、〗一甲基— -9- 200806701 (6) 1 一千氧基乙氧基、1 一甲基一1 一苯乙氧基乙氧基、1 一環 己基一 1 一甲氧基乙氧基、1 一環己基一 1 一乙氧基乙氧基 、1—環己基—1— η —丙氧基乙氧基、1—環己基一 1 一 i — 丙氧基乙氧基、1 一環己基一 1 一環己氧基乙氧基、1 一環 己基一 1 一苯氧基乙氧基、1 一環己基一 1 一苄氧基乙氧基 、1 一苯基—1 一甲氧基乙氧基、1 一苯基一 1 一乙氧基乙氧 ★ 基' 1—苯基一 l—n —丙氧基乙氧基、1—苯基—l—i一丙 氧基乙氧基、1 一苯基—1—環己氧基乙氧基、1 一苯基一 1 一苯氧基乙氧基、1一苯基一 1 一苄氧基乙氧基、1 一苄基 _1一甲氧基乙氧基、1_苄基一 1 一乙氧基乙氧基、1一苄 基—1— η —丙氧基乙氧基、1—节基—1— i —丙氧基乙氧 基、1 一苄基—1—環己氧基乙氧基、1—苄基—1—苯氧基 乙氧基、1—苄基一 1 一苄氧基乙氧基、2— （2—甲基一四 氫呋喃基）氧基、2-（2-甲基一四氫吡喃基）氧基、1 一甲氧基一環戊氧基、1 一甲氧基一環己氧基等。 其中較佳爲，1 一甲基—1—甲氧基乙氧基、1—甲基 —1—環己氧基乙氧基。 ^ 鍵結羧基形成羧酸之1 -烷基環烷基酯構造的基較佳 如，1一甲基環丙基、1 一甲基環丁基、1 一甲基環戊基、1 _甲基環己基、1 一甲基環庚基、1 一甲基環辛基、1—甲 基環壬基、1 一甲基環癸基、1—乙基環丙基、1—乙基環 丁基、1 一乙基環戊基、1 一乙基環己基、1 一乙基環庚基 '1—乙基環辛基'1—乙基環己基、1—乙基環癸基、1 — (異）丙基環丙基、〗一（異）丙基環丁基、1 一（異）丙 -10- 200806701 (7) 基環戊基、1-(異）丙基環己基、1一（異）丙基環庚基 、1 一（異）丙基環辛基、1—(異）丙基環己基、1一（ 異）丙基環癸基、1一（異）丁基環丙基、〗一（異）丁基 環丁基、1一（異）丁基環戊基、1一（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 Φ 一（異）戊基環己基、1—(異）戊基環庚基、1—(異） 戊基環辛基、1一（異）戊基環壬基、1—(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）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—(異）己基環癸基、1一（異）庚基環丙基、1—( 異）庚基環丁基、1一（異）庚基環戊基、1—(異）庚基 環己基、1一（異）庚基環庚基、〗—（異）庚基環辛基、 Φ 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）辛基環丁基、1一（異）辛基環 w 戊基、1 一 （異）辛基環己基、1 一（異）辛基環庚基、1 一（異）辛基環辛基、1 一（異）辛基環壬基及1 一（異） 辛基環癸基。 高分子量物（A )以凝膠滲透色譜法（溶出溶劑四氫 呋喃）測定之聚苯乙烯換算重量平均分子量（以下稱爲^ Mw」）較佳爲2,000以上，更佳爲2,000至〗00,000，特佳 爲3,000至50,000。1^〜未達2,000時會使組成物之塗佈性不 -11 - 200806701 (8) 足，或所形成之保護膜的耐熱性不足。又Mw超過1 00,000 時會使平坦化性能不足。 又，高分子量物（A )以凝膠滲透色譜法（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 「Μη」）較佳爲15〇〇〇以上，又以1，〇〇〇至50,000爲佳，更 佳爲 2,000 至 25,000，特佳爲 4,5 00至 20,000。Mil小於 1，000 ^ 時會使組成物之塗佈性不足，或所形成之保護膜的耐熱性 φ 不足。又Μη超過50,000時會使平坦化性能不足。 另外高分子量物（Α)之分子量分布（Mw/Mn )較佳 爲5.0以下，更佳爲3.0以下。 高分子量物（A )符合上述條件下並無特別限制，例 如可爲（al)具有羧酸之縮醛酯構造、羧酸之縮酮酯構造 、羧酸之1 -烷基環烷基酯構造或羧酸之t 一丁基酯構造的 不飽和化合物（以下稱爲「單體（a 1 )」），（a2 )具善. 烷氧基矽烷基構造之不飽和化合物（以下稱爲「單體（ φ )」），及必要時使用的（a3 )具有環氧基之不飽和化合 物（以下稱爲「單體（a3 )」），及必要時使用的（a4 ) ‘ （a 1 ) 、（ a2 )與（a3 )以外之烯烴系不飽和化合物（以 下稱爲「單體（a4 )」）的共聚物（以下稱爲「共聚物（ A )」）。 單體（a 1 )如，具有羧酸之縮醛酯構造或羧酸之縮酮 酯構造的降莰烯化合物，及具有羧酸之縮醛、縮酮或1 -烷基環烷基酯構造的（甲基）丙烯酸酯化合物、t -丁基 (甲基）丙烯酸酯。 -12 - 200806701 (9) 上述具有縮醛酯構造或縮酮酯構造之降莰烯化合物的 具體例如，2,3 -二一四氫吡喃—2 -基氧基羰基一 5 -降 莰烯、 2，3—二一三甲基矽烷氧基羰基一 5-降莰烯、 2.3 —二一三乙基矽烷氧基羰基一 5 -降莰烯、 2，3 —二一 t 一丁基二甲基矽烷氧基羰基一 5 -降莰烯、 2，3—二—三甲基甲鍺烷氧基羰基一 5—降莰烯、In order to maintain a uniform crystal grain pitch of the liquid crystal layer, the L liquid crystal display element is attached to the protective film to spread the plate of the tubular distiller. Thereafter, the sealant is thermocompression-sealed to seal the liquid crystal cell, but the heat and pressure at this time cause a problem that the protective film is recessed in the tube portion and the grain pitch is disordered. In particular, when manufacturing a color liquid crystal display element of the STN type, the precision of bonding the color filter to the counter substrate is extremely strict, and therefore the protective film is required to have a flatness flatness and heat resistance. Further, in recent years, a wiring electrode (indium tin oxide: ITO) film is formed on a protective film of a color filter by a sputtering method, and a pattern of ITO is applied with a strong acid or a strong alkali. Therefore, the color filter protective film exposes the partial surface to a high temperature during sputtering and undergoes various drug treatments. Therefore, it is required to have resistance to such treatment, and the adhesion of the ITO to the wiring electrode without peeling off the protective film during the treatment of the drug. When forming such a protective film, it is advantageous in that a thermosetting composition which can form a protective film having a high hardness in a simple manner can reduce the cost, but in order to have the above-mentioned characteristics of the protective film resin composition, it is possible to form a strong solid. A well-reacted cross-linking group or catalyst. Therefore, there is a problem that the life of the composition itself is very short and it is not easy to control. That is, in addition to the deterioration of the coating performance of the composition itself, the necessary operations such as frequent maintenance and washing of the coater are also troublesome. -6- 200806701 (3) At present, there is no protective film that can be easily formed into a protective film such as transparency, which can meet the above-mentioned properties, and a material having excellent storage stability for the composition. Japanese Patent Publication No. 4-2 1 8 56 1 discloses a thermosetting composition containing a latent carboxyl compound for use in paints, inks, adhesives, and molded articles, but does not disclose any protective film for color filters. . SUMMARY OF THE INVENTION The present invention has been made in view of the above, and it is therefore an object of the present invention to provide a cured film which is suitable for formation and which has a high flatness even in a substrate having a low surface flatness, and which has high transparency and high surface hardness. And a protective film for an optical device excellent in heat resistance, pressure resistance, acid resistance, alkali resistance, splash resistance and various resistances, a composition having excellent stability for storage stability, and a method for forming a protective film using the composition A protective film formed from the composition. Other objects and advantages of the invention will be apparent from the description which follows. The above object of the present invention may be characterized in that it comprises a acetal structure having a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a t-butyl ester of a carboxylic acid. At least one structure selected from the structural group is obtained by a high molecular weight substance (A) having an alkoxyalkylene structure and a curable resin composition of an organic solvent. The above object of the present invention is to provide a protective film of a color filter comprising the step of applying the curable resin composition of the present invention to a substrate to form a coating film, and irradiating the coating film with radiation. The formation of the party is 200806701 (4). The above object of the present invention is to provide a protective film of a color filter comprising the step of applying the curable resin composition of the present invention to a substrate to form a coating film, and heating the coating film. Formation Method Achieved The above object of the present invention can be attained by the fourth aspect of the present invention, which is achieved by the protective film of the color filter formed of the curable resin composition described above. BEST MODE FOR CARRYING OUT THE INVENTION The components of the resin composition of the present invention will be described below. High molecular weight substance (A) The high molecular weight substance (A) used in the present invention is a structure having a carboxylic acid chiral ester structure, a carboxylic acid ketal ester structure, a carboxylic acid monoalkylcycloalkyl ester structure, and a carboxy group. At least one of the configurations selected from the acid t-butyl ester structural group is alkoxyalkylene structure. The bond thiol group forms a acetal ester of a carboxylic acid such as 1-methoxyethoxy, 1-ethoxyethoxy, 1-n-propoxyethoxy, 1-i-propyl Oxyethoxyethoxy, 1-n-butoxyethoxy, 1-n-butoxyethoxy, 1-sec-butoxyethoxy, 1-t-butoxyethoxy, 1 cyclopentyloxyethoxy, 1-cyclohexyloxyethyl, 1-norkanoxyethoxy, 1-monobornyloxyethoxy, 1-phenoxyethoxy, 1- ( 1 1-naphthyloxy)ethoxy, 1 oxyethoxy, 1 phenylethoxy, (cyclo-8- 200806701 (5) hexyl) (methoxy)methoxy, (cyclohexyl) (ethoxy)methoxy, (cyclohexyl)(η-propoxy)methoxy, (cyclohexyl)(i-propoxy)methoxy, (cyclohexyl)(cyclohexyloxy)methyl Oxyl, (cyclohexyl)(phenoxy)methoxy, (cyclohexyl)(benzyloxy)methoxy, (phenyl)(methoxy)methoxy, (phenyl)(ethoxy) ) methoxy, (phenyl)(η-propoxy)methoxy, (phenyl) (i-propoxy^.) Oxyl, (phenyl)(cyclohexyloxy)methoxy, (phenyl)(phenylφoxy)methoxy, (phenyl)(benzyloxy)methoxy, (benzyl) (A) Oxy) methoxy, (benzyl) (ethoxy) methoxy, (benzyl) (η-propoxy) methoxy, (benzyl) (i-propoxy) methoxy, (benzyl)(cyclohexyloxy)methoxy, (benzyl)(phenoxy)methoxy, (benzyl)(benzyloxy)methoxy, 2-tetrahydrofuranyloxy, 2-tetrahydro Pyryloxy and the like. Among them, preferred are 1-ethoxyethoxy, 1-cyclohexyloxyethoxy: 2-tetrahydroindole oxycarbonyl, and 1-n-propoxyethoxy. • A group in which a carboxyl group is bonded to form a ketal ester of a carboxylic acid, such as 1-methyl-methoxyethoxy, 1-methyl-1-ethoxyethoxy, 1-methyl- 1^- Η-propoxyethoxy, 1-methyl-:[i-propoxyethoxy, 1-methyl-1,4-n-butoxyethoxy]1-methyl-l-i Monobutoxyethoxy, 1-methyl-hydrazine-sec-butoxyethoxy, 1-methyl-l-t-butoxyethoxy, 1-methyl-1,4-pentyloxy Ethoxy, 1-methyl-1 1-cyclohexyloxyethoxy, 1-methyl-l-norkanoxyethoxy '1 monomethyl-1 borneoloxyethoxy, 1 A 1,1-phenoxyethoxy, 1-methyl-1,1-(1-naphthyloxy)ethoxy, dimethyl--9-200806701 (6) 1 1-methoxyethoxy, 1 monomethyl-1-phenylethoxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-cyclohexyl-1-η Propoxyethoxy, 1-cyclohexyl-1, i-propoxyethoxy, 1 cyclohexyl-1 cyclohexyloxyethoxy , 1-cyclohexyl-1-monophenoxyethoxy, 1-cyclohexyl-1-benzyloxyethoxy, 1-phenyl-1-methoxyethoxy, 1-phenyl-1-methoxy Ethyloxyl group - 1 -phenyl-l-n-propoxyethoxy, 1-phenyl-l-i-propoxyethoxy, 1-phenyl-1-cyclohexyloxy Oxyl, 1-phenyl-1-monophenoxyethoxy, 1-phenyl-1-benzyloxyethoxy, 1-benzyl-1-methoxyethoxy, 1-benzyl 1-Ethoxyethoxy, 1-benzyl-1-n-propoxyethoxy, 1-n-l-1-i-propoxyethoxy, 1-benzyl- 1-cyclohexyl Oxyethoxyethoxy, 1-benzyl-1-phenoxyethoxy, 1-benzyl-1-benzyloxyethoxy, 2-(2-methyltetrahydrofuranyl)oxy, 2- (2-Methyltetrahydropyranyl)oxy, 1-methoxy-cyclopentyloxy, 1-methoxy-cyclohexyloxy and the like. Among them, preferred is 1-methyl-1-methoxyethoxy, 1-methyl-1-cyclohexyloxyethoxy. ^ A group in which a carboxyl group is bonded to a 1-alkylcycloalkyl ester of a carboxylic acid is preferably, for example, 1-methylcyclopropyl, 1-methylcyclobutyl, 1-methylcyclopentyl, 1 -A Cyclohexyl, 1-methylcycloheptyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclodecyl, 1-ethylcyclopropyl, 1-ethylcyclobutane 1, 1-ethylcyclopentyl, 1-ethylcyclohexyl, 1-ethylcycloheptyl '1-ethylcyclooctyl '1-ethylcyclohexyl, 1-ethylcyclodecyl, 1 — (Isopropyl)cyclopropyl, isopropyl (iso)propylcyclobutyl, 1 (iso)propen-10- 200806701 (7) Cyclopentyl, 1-(iso)propylcyclohexyl, 1 (Isopropyl)cycloheptyl, 1-(iso)propylcyclooctyl, 1-(iso)propylcyclohexyl, 1-monopropylidenethiol, 1-monoisobutylcyclopropane , (I) (iso)butylcyclobutyl, 1-(iso)butylcyclopentyl, 1-monoisobutylcyclohexyl, 1-monoisobutylcycloheptyl, 1 (iso) Butylcyclooctyl, 1 -(iso)butylcyclodecyl, 1 (iso)butylcyclodecyl, 1 (iso)pentylcyclopropyl, 1 (different) Butylcyclobutyl, 1-monoisopentylcyclopentyl, 1 Φ-(iso)pentylcyclohexyl, 1-(iso)pentylcycloheptyl, 1-(iso)pentylcyclooctyl, 1-(iso)pentylcyclodecyl, 1-(iso)pentylcyclodecyl, 1-(iso)hexylcyclopropyl, 1-(iso)hexylcyclobutyl, 1-(iso)hexylcyclopentyl 1, 1 (iso)hexylcyclohexyl, 1 -(iso)hexylcycloheptyl, 1 -(iso)hexylcyclooctyl, 1 -(iso)hexylcyclodecyl, 1-(iso)hexylcyclodecyl , 1-(iso)heptylcyclopropyl, 1-(iso)heptylcyclobutyl, 1-(iso)heptylcyclopentyl, 1-(iso)heptylcyclohexyl, 1-mono(iso)g Base ring heptyl, 〖-(iso)heptylcyclooctyl, Φ 1 -(iso)heptylcyclodecyl, 1 -(iso)heptylcyclodecyl, 1 -(iso^)octylcyclopropyl , 1 (iso)octylcyclobutyl, 1 (iso)octyl ring w pentyl, 1 (iso)octylcyclohexyl, 1 (iso)octylcycloheptyl, 1 (iso) Octylcyclooctyl, 1 (iso)octylcyclodecyl and 1 (iso)octylcyclodecyl. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (extraction solvent tetrahydrofuran) of the high molecular weight substance (A) is preferably 2,000 or more, more preferably 2,000 to 00,000, and particularly preferably It is 3,000 to 50,000. When the amount is less than 2,000, the coating property of the composition is not -11 - 200806701 (8) The heat resistance of the formed film or the formed protective film is insufficient. If the Mw exceeds 100,000, the flattening performance will be insufficient. In addition, the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Μη") measured by gel permeation chromatography (dissolved solvent tetrahydrofuran) of the high molecular weight substance (A) is preferably 15 Å or more and 1 Å. 〇〇 to 50,000 is preferred, preferably 2,000 to 25,000, and particularly preferably 4,500 to 20,000. When Mil is less than 1,000 ^, the coating property of the composition is insufficient, or the heat resistance φ of the formed protective film is insufficient. Further, when Μη exceeds 50,000, the flattening performance is insufficient. Further, the molecular weight distribution (Mw/Mn) of the high molecular weight substance (M) is preferably 5.0 or less, more preferably 3.0 or less. The high molecular weight substance (A) is not particularly limited as long as it satisfies the above conditions, and may be, for example, (al) a acetal structure having a carboxylic acid, a ketal ester structure of a carboxylic acid, or a 1-alkylcycloalkyl ester structure of a carboxylic acid. Or an unsaturated compound of a t-butyl ester of a carboxylic acid (hereinafter referred to as "monomer (a 1 )"), (a2) is a good. Alkoxyalkylene structure of an unsaturated compound (hereinafter referred to as "single" ( φ )"), and if necessary, (a3) an unsaturated compound having an epoxy group (hereinafter referred to as "monomer (a3)"), and if necessary, (a4) ' (a 1 ), (a2) a copolymer of an olefin-based unsaturated compound other than (a3) (hereinafter referred to as "monomer (a4)") (hereinafter referred to as "copolymer (A)"). The monomer (a 1 ), for example, a norbornene compound having a acetal structure of a carboxylic acid or a ketal ester structure of a carboxylic acid, and an acetal, ketal or 1-alkylcycloalkyl ester structure having a carboxylic acid (meth) acrylate compound, t-butyl (meth) acrylate. -12 - 200806701 (9) Specifically, for example, 2,3-ditetrahydropyran-2-yloxycarbonyl-5-norbornene having a decylene structure or a ketal ester structure , 2,3-di-trimethyl-decyloxycarbonyl- 5-decene, 2.3-di-triethyl-decyloxycarbonyl-5-northene, 2,3-di-t-butyl Methyl nonyloxycarbonyl 5-non-decene, 2,3-di-trimethylformyloxycarbonyl-5-norbornene,

2，3 —二一三乙基甲鍺烷氧基羰基一 5 —降莰烯、 2.3— 二一 t 一丁基二甲基甲鍺烷氧基羰基一 5—降莰烯、 2.3— 一 t — 丁氧基擬基一 5—降茨烯、 2，3—二一苄氧基羰基一 5-降莰烯、 2.3 —二一四氫呋喃—2 —基氧基羰基一 5—降莰烯、 2.3 —二一四氫卩比喃一 2 -基氧基鑛基一 5 —降莰嫌、 2.3 —二一環丁氧基羰基一 5-降莰烯、 2.3— _環戊氧基鑛基一 5-降茨燦、 2.3 —二—環己氧基羰基—5_降莰烯、 2，3-二—環庚氧基羰基—5 —降茨燏、 2.3 — _1—甲氧基乙氧基鑛基一5-降茨矯、 2.3— 一 — 1 一 ί一丁氧基乙氧基羰基一 5 —降莰烯、 2.3— 二—1 一苄氧基乙氧基羰基一 5 —降莰烯、 2.3 —二一（環己基）（乙氧基）甲氧基羰基一 5 —降莰烯 2,3 —二一 1 一甲基一 1—甲氧基乙氧基羰基—5 —降莰烯、 2，3 —二—1 一甲基一 1— i — 丁氧基乙氧基羰基一 5 -降莰 -13- 200806701 (10) 烯、 2，3—二一（苄基）（乙氧基）甲氧基羰基一 5—降莰烯等 y 上述具有縮醛酯或縮酮酯構造之（甲基）丙烯酸酯化合物 的具體例如，1一乙氧基乙基（甲基）丙燃酸酯、四氫— 2H—卩比喃一 2 —基（甲基）丙燒酸醋、1 一 （環己氧基） 乙基（甲基）丙燒酸醋、1一（2—甲基丙氧基）乙基（甲 Φ 基）丙烯酸酯、卜（U 一二甲基〜乙氧基）乙基（甲基 )丙烯酸酯、1 一（環己氧基）乙基（甲基）丙烯酸酯等 〇 上述具有1 -烷基環烷基酯構造之（甲基）丙烯酸酯 化合物的具體例如， 1 一甲基環丙基（甲基）丙嫌酸酯、1 一甲基環丁基（甲基 )丙烯酸酯、1 —甲基環戊基（甲基）丙烯酸酯、丨一甲基 環己基（甲基）丙烯酸酯、1 -甲基環庚基（甲基）丙烯 • 酸酯、1 —甲基環辛基（甲基）丙烯酸酯、丨一甲基環壬基 (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）丙烯酸醋、〗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、〗一乙基 ^己基（甲基）丙烯酸酯、〗—乙基環庚基（甲基）丙烯 酸醋、1—乙基環辛基（甲基）丙烯酸酯、1 一乙基環壬基 (甲基）丙烯酸酯、】一乙基環癸基（甲基）丙烯酸酯、！ 一（異）丙基環丙基（甲基）丙烯酸酯、^一 （異）丙基 丁基（甲基）丙烯酸酯、〗一（異）丙基環戊基（甲基 -14- 200806701 (11) )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、1 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、〗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 Φ 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）丁基環壬基（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 φ )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、〗一（異）己基環己基（甲基 )丙烯酸酯、1一（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、I - （異）庚基環戊基（甲基 -15- 200806701 (12) )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- （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-(異）辛基環壬基（甲基 )丙烯酸酯、1-(異）辛基環癸基（甲基）丙烯酸酯等 〇 其中較佳爲’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（ 甲基）丙烯酸酯、1 一（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 一（異） ® 丁基環己基（甲基）丙烯酸酯，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、〗一乙基環己基（ 甲基）丙烯酸酯。又就提升共聚合反應性及所得保護膜之 耐熱性、組成物溶液之保存安定性觀點，又以使用該物爲 佳。 其中較佳爲，具有羧酸之縮醛酯或縮酮酯構造的（甲 基）丙烯酸酯化合物及t -丁基（甲基）丙烯酸酯，特佳 爲1—乙氧基乙基甲基丙細酸醋、四氨一 2H—卩比喃一 2 — -16- 200806701 (13) 基甲基丙烯酸酯、1 _ (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 一 （U1 —二 甲基一乙氧基）乙基甲基丙烯酸酯、丨一（環己氧基）乙 基甲基丙烯酸酯、t 一丁基甲基丙烯酸酯。 此等單體（al)可單獨或組合使用。 單體（)如，3 -(甲基）丙烯氧基丙基三氯矽烷 、3—（甲基）丙烯氧基丙基三甲氧基矽烷、3一（甲基） 丙燃氧基丙基三乙氧基矽烷、3 - （甲基）丙烯氧基丙基 三一 η-丙氧基矽烷、3_ (甲基）丙烯氧基丙基三一 i 一 丙氧基矽烷、3-（甲基）丙烯氧基丙棊三- η- 丁氧基矽 院、3 - （甲基）丙烯氧基丙基三一 sec — 丁氧基矽烷、3 一（甲基）丙烯氧基丙基二甲氧基矽烷、3_ (甲基）丙 烯氧基丙基甲基二乙氧基矽烷、3 —(甲基）丙烯氧基丙 基甲基二氯矽烷等。 其中就提升共聚合反應性及所得保護膜或絕緣膜之密 合性、表面硬度觀點，又以使用3 —（甲基）丙烯氧基丙 基三甲氧基矽烷' 3 一（甲基）丙烯氧基丙基三乙氧基矽 院等爲佳 ° 此等單體（a2)可單獨或組合使用。 又任意成份之單體（a3 )如，丙烯酸環氧丙酯、甲基 丙烯酸環氧丙酯、α -乙基丙烯酸環氧丙酯、α — η-丙 基丙烯酸環氧丙酯、α - η - 丁基丙烯酸環氧丙酯、丙烯 酸一 3,4 一環氧丁酯、甲基丙烯酸一 3，4 一環氧丁酯、丙烯 酸一 6,7—環氧庚酯、甲基丙烯酸一 6,7 —環氧庚酯、α - -17- 200806701 (14) 乙基丙烯酸- 6,7—環氧庚酯、〇 一乙烯基苄基環氧丙醚、 m-乙烯基苄基環氧丙醚、ρ一乙烯基苄基環氧丙醚等。 其中就提升共聚合反應性及所得保護膜或絕緣膜之耐 熱性、表面硬度觀點，又以使用甲基丙烯酸環氧丙酯、甲 基丙嫌酸一 6，7-環氧庚醋、〇一乙燒基辛基環氧丙醚、m -乙烯基苄基環氧丙醚、P 一乙烯基苄基環氧丙醚等爲佳 * 〇 φ 此等單體（a3 )可單獨或組合使用。使用單體（a3 ) 所得之高分子量物（A )可具有來自單體（a3 )之環氧構 造。 同樣任意成份之單體（a4 )如，甲基丙烯酸烷基酯（ 但t -丁基甲基丙烯酸酯除外）、丙烯酸烷基酯（但t -丁 基丙烯酸酯）、甲基丙烯酸環狀烷基酯、丙烯酸環狀烷基: 酯、甲基丙烯酸芳基酯、丙烯酸芳基酯、不飽和二羧酸二 酯、二環不飽和化合物類、馬來醯亞胺化合物類、不飽和 φ 芳香族化合物、共軛二烯系化合物、不飽和一羧酸、不飽 和二羧酸、不飽和二羧酸酐、其他之不飽和化合物。 ' 此等具體例中甲基丙烯酸烷基酯（但t一丁基甲基丙 烯酸酯除外）如，羧基甲基甲基丙烯酸酯、2-經基乙基 甲基丙烯酸酯、3-羥基丙基甲基丙烯酸酯、4-經基丁基 甲基丙烯酸酯、二乙二醇—甲基丙烯酸酯、2,3 —二羥基 丙基甲基丙烯酸酯、2—甲基丙烯氧基乙基糖音、4一經基 苯基甲基丙烯酸酯、甲基甲基丙烯酸酯、乙基甲基丙嫌酸 醋、η—丁基甲基丙稀酸醋' sec— 丁基甲基丙烯酸酯、2 -18- 200806701 (15) 一乙基己基甲基丙烯酸酯、異癸基甲基丙烯酸酯、n 一月 桂基甲基丙烯酸酯、十三烷基甲基丙烯酸酯、η -硬脂醯 甲基丙烯酸酯等； 丙烯酸烷基酯（但t -丁基丙烯酸酯除外）如，甲基 丙烯酸酯、異丙基丙烯酸酯等；2,3-di-tert-triethylmethaneoxycarbonyl-5-northene, 2.3-di-t-butyldimethylmercaptooxycarbonyl-5-northene, 2.3-one t —butoxymethyl-5-norzene, 2,3-dibenzyloxycarbonyl-5-norbornene, 2.3-ditetrahydrofuran-2-yloxycarbonyl-5-norbornene, 2.3 - 1,4-hydroquinone than ketone-2-yloxy ortho-5-norborn, 2.3-di-cyclobutoxycarbonyl-5-northene, 2.3-cyclopentyloxy ortho- 5 - Descizhan, 2.3-di-cyclohexyloxycarbonyl-5_northene, 2,3-di-cycloheptyloxycarbonyl-5-norz, 2.3-_1-methoxyethoxylate Base one 5-norzyl, 2.3-1 -1 - methoxy-butoxyethoxycarbonyl - 5 - norbornene, 2.3 - 1-2 - benzyloxy ethoxycarbonyl - 5 - norbornene, 2.3 —Di-(cyclohexyl)(ethoxy)methoxycarbonyl-5-norbornene 2,3-di- 1-1-methyl-1-methoxyethoxycarbonyl-5-norbornene, 2,3 -di-1 monomethyl-1-i-butoxyethoxycarbonyl-5-莰-13- 200806701 (10) Alkene, 2,3-di-(benzyl)(ethoxy)methoxycarbonyl-5-northene, etc. y The above acetal ester or ketal ester structure (A) Specific examples of the acrylate compound are, for example, 1-ethoxyethyl (meth) propionate, tetrahydro-2H-indole-pyran-2-yl (meth)propanoic acid vinegar, 1 (ring) Hexyloxy) ethyl (meth) propyl sulphate, 1-(2-methylpropoxy)ethyl (meth) acrylate, b (U-dimethyl-ethoxy)ethyl Specific examples of the (meth) acrylate compound having a 1-alkylcycloalkyl ester structure, such as (meth) acrylate or mono-(cyclohexyloxy)ethyl (meth) acrylate, for example, 1 Methylcyclopropyl (meth)propionic acid ester, 1-methylcyclobutyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, fluorenylmethylcyclohexyl (A) Acrylate, 1-methylcycloheptyl (meth) propylene • acid ester, 1-methylcyclooctyl (meth) acrylate, fluorenylmethylcyclodecyl (meth) acrylate, 1 One Base ring fluorenyl (meth) acrylate, 1-ethylcyclopropyl (meth) acrylate, 1-ethylcyclobutyl (meth) acrylate, 1-ethylcyclopentyl (methyl) Acrylate, hexylethylhexyl (meth) acrylate, ethyl-ethylcycloheptyl (meth) acrylate, 1-ethylcyclooctyl (meth) acrylate, 1-ethyl oxime (Meth) acrylate, monoethylcyclodecyl (meth) acrylate,! Mono (iso)propylcyclopropyl (meth) acrylate, mono (iso) propyl butyl (meth) acrylate, mono (iso) propyl cyclopentyl (methyl-14- 200806701 ( 11)) acrylate, 1-(iso)propylcyclohexyl (meth) acrylate, 1-(iso)propylcycloheptyl (meth) acrylate, 1-(iso)propylcyclooctyl ( Methyl) acrylate, 1 (iso)propylcyclodecyl (meth) acrylate, 1 (iso)propylcyclodecyl (meth) acrylate, 1 (iso)butylcyclopropyl (Meth) acrylate, mono (iso)butylcyclobutyl (meth) acrylate, mono-(iso)butylcyclopentyl (methyl-) acrylate, mono-(iso)butyl ring Hexyl (meth) acrylate, 1 Φ mono(iso)butylcycloheptyl (meth) acrylate, 1-(iso)butylcyclooctyl (meth) acrylate, 1-mono(iso)butyl Cyclodecyl (meth) acrylate, mono (iso)butylcyclodecyl (meth) acrylate, mono (iso)pentyl cyclopropyl (meth) acrylate, 1 mono (iso) pentyl Cyclobutyl Methyl) acrylate, 1-(iso)pentylcyclopentyl (meth) acrylate, mono-(iso)pentylcyclohexyl (meth) acrylate, 1-(iso)pentylcycloheptyl ( Methyl) acrylate, 1 (iso)pentylcyclooctyl (meth) acrylate, 1 (iso)pentylcyclodecyl (methyl φ ) acrylate, 1 -(iso)pentyl ring oxime (meth) acrylate, '1-isohexylcyclopropyl (meth) acrylate, mono-(iso)hexylcyclobutyl (meth) acrylate, mono(iso)hexylcyclohexyl (Meth) acrylate, 1-(iso)hexylcycloheptyl (meth) acrylate, 1-(iso)hexylcyclooctyl (meth) acrylate, 1-(iso)hexylcyclodecyl (A) Acrylate, 1 (iso)hexylcyclodecyl (meth) acrylate, 1 (iso)heptylcyclopropyl (meth) acrylate, 1 (iso)heptylcyclobutyl (A) Acrylate, I - (iso)heptylcyclopentyl (methyl-15-200806701 (12)) acrylate, 1 (iso)heptylcyclohexyl (meth) acrylate 1 mono(iso)heptylcycloheptyl (meth) acrylate, mono (iso)heptylcyclooctyl (meth) acrylate, 1-(iso)heptylcyclodecyl (meth) acrylate , 1 (iso)heptylcyclodecyl (meth) acrylate, 1 (iso)octylcyclopropyl (meth) acrylate, 1 (iso)octylcyclobutyl (meth) acrylate Ester, 1-(iso)octylcyclopentyl (meth) acrylate, mono-(iso)octylcyclohexyl (meth) acrylate, 1 #-(iso)octylcycloheptyl (methyl) Acrylate, 1-(iso)octylcyclooctyl (meth) acrylate, 1-(iso)octylcyclodecyl (meth) acrylate, 1-(iso)octylcyclodecyl (methyl) Acrylates and the like are preferably -1 -ethylcyclopentyl (meth) acrylate, 1 -ethylcyclohexyl (meth) acrylate, 1 (iso)propylcyclopentyl (methyl) Acrylate, 1 (iso)propylcyclohexyl (meth)acrylic acid: ester, 1 (iso)butylcyclopentyl (meth) acrylate, 1 (iso) butylcyclohexyl (A) Propylene The acid ester is more preferably 1-ethylcyclopentyl (*methyl) acrylate, 1-ethylcyclohexyl (meth) acrylate, particularly preferably 1-ethylcyclopentyl (meth) acrylate. , 1-ethylcyclohexyl (meth) acrylate. Further, from the viewpoint of improving the copolymerization reactivity and the heat resistance of the obtained protective film and the preservation stability of the composition solution, it is preferred to use the material. Among them, preferred are (meth) acrylate compounds having a acetal or ketal ester structure of a carboxylic acid and t-butyl (meth) acrylate, particularly preferably 1-ethoxyethyl methyl propyl acrylate. Fine acid vinegar, tetraammonium 2H-indole ratio 2 - 16-200806701 (13) methacrylic acid ester, 1 _ (cyclohexyloxy) ethyl methacrylate, 1 (2-methyl group) Propyl)ethyl methacrylate, 1-(U1-dimethyl-ethoxy)ethyl methacrylate, decyl(cyclohexyloxy)ethyl methacrylate, t-butylmethyl Acrylate. These monomers (al) may be used singly or in combination. Monomer (), for example, 3-(meth)acryloxypropyltrichlorodecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propoxy oxypropyl three Ethoxy decane, 3-(meth)acryloxypropyl tris-n-propoxy decane, 3-(meth) acryloxypropyl tri-i-propoxy decane, 3-(methyl) Propylene oxypropionate tris-n-butoxy fluorene, 3 - (meth) acryloxypropyl tris sec - butoxy decane, 3 - (meth) propylene oxy propyl dimethoxy Decane, 3-(meth)acryloxypropylmethyldiethoxydecane, 3-(meth)acryloxypropylmethyldichlorodecane, and the like. Among them, the viewpoint of improving the copolymerization reactivity and the adhesion and surface hardness of the obtained protective film or insulating film, and using 3-(meth)acryloxypropyltrimethoxydecane ' 3 -(meth)acryloyloxy The propyl triethoxy oxime or the like is preferred. These monomers (a2) may be used singly or in combination. Further optional monomer (a3) such as glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate propyl acrylate, α-η-propyl propylene acrylate, α - η - Glycidyl butyl acrylate, 3,4 epoxide butyl acrylate, 3,4 epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, methacrylate 7 —Epoxyheptyl ester, α - -17- 200806701 (14) Ethyl acrylate - 6,7-epoxyheptyl ester, fluorene monovinylbenzyl epoxidized ether, m-vinylbenzyl epoxidized ether , ρ-vinylbenzyl epoxidized propyl ether and the like. Among them, the viewpoint of improving the copolymerization reactivity and the heat resistance and surface hardness of the obtained protective film or insulating film, and the use of glycidyl methacrylate, methyl propylene succinic acid, 6,7-epoxy vinegar, hydrazine Ethyl octyl epipyl ether, m-vinyl benzyl epoxidized propyl ether, P-vinyl benzyl epoxidized propyl ether, etc. are preferable. ** φ These monomers (a3) may be used singly or in combination. The high molecular weight substance (A) obtained by using the monomer (a3) may have an epoxy structure derived from the monomer (a3). The same optional monomer (a4) such as alkyl methacrylate (except t-butyl methacrylate), alkyl acrylate (but t-butyl acrylate), cyclic alkyl methacrylate Acrylic cyclic alkyl: ester, aryl methacrylate, aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleic imine compound, unsaturated φ aromatic compound A conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic anhydride, or another unsaturated compound. 'In these specific examples, alkyl methacrylate (except t-butyl methacrylate) such as carboxymethyl methacrylate, 2-carbylethyl methacrylate, 3-hydroxypropylmethyl Acrylate, 4-butylbutyl methacrylate, diethylene glycol-methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methylpropenyloxyethyl sugar, 4-monomethyl Phenyl methacrylate, methyl methacrylate, ethyl methyl propyl vinegar, η butyl methyl acrylate vine sec - butyl methacrylate, 2 -18- 200806701 (15) monoethyl Hexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, η-stearin methacrylate, etc.; alkyl acrylate (but t - other than butyl acrylate) such as methacrylate, isopropyl acrylate, etc.;

甲基丙烯酸環狀烷基酯如，環己基甲基丙烯酸酯、2 一甲基環己基甲基丙烯酸酯、三環[5·2·1·〇2,6]癸院一 8一 基甲基丙烯酸酯、三環[5.2.1.〇2,6]癸烷一8一基氧基乙基 甲基丙烯酸酯、異甲硼烷基甲基丙烯酸酯等； 丙矯酸运狀垸基醋如’環己基丙矯酸酯、2 -甲基環 己基丙烯酸酯、三環[5.2.1.02,6]癸烷—8 —基丙烯酸酯、 三環[5·2· 1 ·02,6]癸烷一 8 -基氧基乙基丙烯酸酯、異甲硼 烷基丙烯酸酯等； 甲基丙烯酸芳基酯如，苯基甲基丙燒酸酯、节基甲基 丙烯酸酯等； 丙烯酸芳基酯如，苯基丙烯酸酯、苄基丙烯酸醋等； 不飽和二羧酸二酯如’馬來酸二乙酯、富馬酸二乙酯 、衣康酸二乙酯等； 二環不飽和化合物如，二環[2·2·1]庚一 2—嫌、5〜甲 基二環[2.2.1]庚—2-烯、5 -乙基二環[2·2 ：[]庚一 2〜烯 、5 —甲氧基二環[2.2.1]庚一 2 —烯、5 一乙氧基二環 [2.2.1]庚一 2—烯、5,6—二甲氧基二環[2·21]庚一 2〜烯 、5，6 —二乙氧基二環[2.2.1]庚一 2 一烯、5 — ( 2,—經基 乙基）二環[2,2·1]庚一 2-烯、5,6-二羥基二環[221]庚 -19- 200806701 (16) —2—烯、5,6-二（羥基甲基）二環[2 ·2.1]庚一 2—烯、 5,6 —二（2’—羥基乙基）二環[2·2·1]庚—2—烯' 5-羥 基一5—甲基二環[2.2.1]庚一 2_烯、5—羥基一 5 -乙基二 環[2.2.1]庚一 2—烯、5 —羥基甲基一 5 —甲基二環[2.2.1] 庚一 2 —烯等； 馬來醯亞胺化合物如，苯基馬來醯亞胺、環己基馬來 • 醯亞胺、节基馬來醯亞胺、Ν -號拍醯酵亞胺基- 3 -馬 φ 來醯亞胺苯甲酸酯、Ν-琥珀醯酵亞胺基一 4-馬來醯亞 胺丁酸酯、Ν -琥珀醯酵亞胺基一 6 -馬來醯亞胺己酸酯 、Ν-琥珀醯酵亞胺基一 3-馬來醯亞胺丙酸酯'Ν- (9 -吖啶基）馬來醯亞胺等； 不飽和芳香族化合物如，苯乙烯、α —甲基苯乙烯、 m —甲基苯乙烯、ρ—甲基苯乙烯、乙烯基甲苯、ρ—甲氧 基苯乙烯等； 共軛二烯系化合物如，1，3 - 丁二烯、異戊二烯、2,3 _ —二甲基一1，3— 丁二烯等； 不飽和一羧酸如，丙烯酸、甲基丙烯酸、巴豆酸等； ' 不飽和二羧酸如，馬來酸、富馬酸、檸康酸、中康酸 '衣康酸等； 不飽和二羧酸酐如，上述不飽和二羧酸之各酐； 其他不飽和化合物如，丙烯腈、甲基丙烯腈、氯乙烯 、偏氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙酯等。 其中就共聚合反應性等觀點，較佳爲苯乙烯、三環 [5.2.1.02’6]癸院一 8-基甲基丙烯酸酯、ρ一甲氧基苯乙燒 -20 - 200806701 (17) 、2—甲基環己基丙烯酸酯、ι，3 一 丁二烯、二環[2·2·1]庚 —2 —燒等。 此等單體（a4 )可單獨或組合使用。 共聚物（A)中來自單體（a〗）之構造單位的含量較 佳爲5至60重量％，更佳爲1〇至50重量％。該範圍之含量 可實現良好平坦化性能及耐熱性。 ^ 共聚物（Α)中來自單體（a2)之構造單位的含量較 φ 佳爲至70重量％，更佳爲20至60重量％。該値未達10重 量％時會使所得保護膜之耐熱性、表面硬度不足。又該値 超過70重量％時會傾向降低樹脂組成物之保存安定性。 共聚物（A )中來自單體（a3 )之構造單位的含量較 佳爲〇·1至50重量％，更佳爲1至20重量％。該値未達0.1 重量％時會使所得保護膜之密合性、表面硬度不足。又該 値超過5 0重量％時會傾向降低樹脂組成物之保存安定性。 共聚物（A)中來自單體（a4)之構造單位的含量爲 φ ，100重量％減去上述來自單體（al ) 、（ a2 )及（a3 ) λ 之構造單位含量的量，但所使用之單體（a4 )爲不飽和一 ‘ 羧酸、不飽和二羧酸或不飽和二羧酸酐時，來自不飽和一 羧酸 '不飽和二羧酸及不飽和二羧酸酐之構造單位的合計 含量不得超過40重量％。超過40重量％時會損害所得組成 物之安定性，故以不超過該値爲佳。 共聚物（A)之具體例以單體組合表示時較佳如，苯 乙烯/四氫一 2H —吡喃—2 —基（甲基）丙烯酸酯/甲基 丙烯酸三環[5.2.1. 02,6]癸烷一 8 -酯/ 3 —甲基丙烯氧基丙 -21 - 200806701 (18) 基三甲氧基矽烷/甲基丙烯酸環氧丙酯共聚物、 苯乙烯/1 一 （環己氧基）乙基（甲基）丙烯酸醋/ 甲基丙烯酸三環[5.2.1.02’6]癸烷一 8一酯/ 3一甲基丙燒氧 基丙基三甲氧基矽烷/甲基丙烯酸環氧丙酯共聚物、 本乙烯/四氫一 211_啦喃一 2 —基（甲基）丙燒酸醋 /苯基馬來醯亞胺/ 3-甲基丙烯氧基丙基三甲氧基砂院 M /甲基丙烯酸環氧丙酯共聚物、 儀| 本乙靖/ 2,3 — 一 一四氫卩比喃—2—基氧基鑛基—5 — 降莰烯/甲基丙烯酸三環[5.2.1 ·02,6]癸烷一 8 一醋/ 3 —甲 基丙烯氧基丙基三甲氧基矽烷/甲基丙烯酸環氧丙酯共聚 物、 苯乙烯/1 一 （環己氧基）乙基（甲基）丙烯酸酯/ 環己基馬來醯亞胺/ 3-甲基丙烯氧基丙基三甲氧基砍院 /甲基丙烯酸環氧丙酯共聚物、 苯乙烯/四氫一 2Η—吡喃一 2 —基（甲基）丙烯酸酯 • /環己基馬來醯亞胺/ 3 -甲基丙烯氧基丙基三甲氧基矽 烷/甲基丙烯酸環氧丙酯共聚物、 ^ 苯乙烯/ 2，3 -二一四氫吡喃一 2 _基氧基羰基—5 一 降莰烯/環己基馬來醯亞胺/ 3—甲基丙烯氧基丙基三甲 氧基矽烷/甲基丙烯酸環氧丙酯共聚物、 丁二烯/苯乙烯/ 1 一 （環己氧基）乙基（甲基）丙 烯酸酯/甲基丙烯酸三環[5.2.1.02,6]癸烷一8—酯/ 3—甲 基丙烯氧基丙基三甲氧基矽烷/甲基丙烯酸環氧丙酯共聚 物、 -22- 200806701 (19) 丁二烯/四氫一 2H -吡喃—2 —基（甲基）丙烯酸酯 /甲基丙烯酸三環[5.2·1·02’6]癸院一 8 —酯/ 3-甲基丙嫌 氧基丙基二甲氧基砂院/甲基丙嫌酸環氧丙醋共聚物、 t 一丁基甲基丙燒酸酯/四氫一 2Η—卩比喃一 2—基（甲 基）丙燏酸酯/馬來酸酐/ 3 -丙烯氧基丙基三甲氧基砂 烷/甲基丙烯酸- 6,7-環氧庚酯共聚物、 - 苯乙烯/四氫一 2H —吡喃一 2 —基（甲基）丙烯酸酯 /甲基丙烯酸甲酯/ 3—甲基丙烯氧基丙基三甲氧基矽院 /甲基丙烯酸環氧丙酯共聚物、 p —甲氧基苯乙嫌/四氫一 2H—卩比喃一 2 —基（甲基 )丙烯酸酯/環己基丙烯酸酯/ 3 -甲基丙烯氧基丙基三 甲氧基矽烷/甲基丙烯酸環氧丙酯共聚物； t- 丁基甲基丙嫌酸醋/苯乙嫌/ 3-甲基丙稀氧基丙 基三甲氧基矽烷/甲基丙烯酸環氧丙酯/環己基馬來醯亞 胺共聚物、 φ 苯乙烯/ t- 丁基甲基丙烯酸酯/甲基丙烯酸三環 • [5.2.1. 02’6]癸烷一 8 —酯/ 3_甲基丙烯氧基丙基三乙氧基 - 矽烷/甲基丙烯酸一 6,7-環氧庚酯共聚物、 苯乙烯/t一丁基甲基丙烯酸酯/馬來酸酐/ 3—甲基 丙烯氧基丙基三乙氧基矽烷/甲基丙烯酸- 6,7 -環氧庚 酯共聚物、 苯乙烯/ t-丁基甲基丙烯酸酯/苯基馬來醯亞胺/ 3 一丙烯氧基丙基三甲氧基矽烷/丙烯酸環氧丙酯共聚物等 •23- 200806701 (20) 其中較佳爲， 苯乙燒/四氨一 2H —卩比喃一 2 /甲基丙烯酸三環[5.2·1· 02,6]癸烷 氧基丙基三甲氧基矽烷/甲基丙烯 苯乙希/四氫一2 Η —卩比喃一 2 /苯基馬來醯亞胺/ 3 -甲基丙烯 /甲基丙烯酸環氧丙酯共聚物、 苯乙烯/ 2,3 —二一四氫吡喃 降莰烯/甲基丙烯酸三環[5·2·1·02 基丙烯氧基丙基三甲氧基矽烷/甲 物、 苯乙烯/1—(環己氧基）乙 環己基馬來醯亞胺/ 3 -甲基丙烯 /甲基丙烯酸環氧丙酯共聚物、 苯乙烯/四氫一2Η —吡喃一 2 /環己基馬來醯亞胺/ 3 -甲基丙 烷/甲基丙烯酸環氧丙酯共聚物、 苯乙烯/ 2,3 —二一四氫吡喃 降莰烯/環己基馬來醯亞胺/甲基 丁二烯/苯乙烯/1 一（環己 烯酸酯/甲基丙烯酸三環[5.2.1.0 = 基丙烯氧基丙基三甲氧基矽烷/甲 物0 一基（甲基）丙烯酸酯 一 8—酯/ 3—甲基丙烯 酸環氧丙酯共聚物、 一基（甲基）丙烯酸酯 氧基丙基三甲氧基矽烷 一 2-基氧基幾基—5 -’6]癸烷—8 -酯/ 3 —甲 基丙烯酸環氧丙酯共聚 基（甲基）丙烯酸酯/ 氧基丙基三甲氧基矽烷 一基（甲基）丙烯酸酯 烯氧基丙基三甲氧基砂 一 2 -基氧基駿基一 5 — 丙烯酸環氧丙酯共聚物 氧基）乙基（甲基）丙 5’6]癸烷一8—酯/ 3〜甲 1基丙烯酸環氧丙酯共聚 -24 200806701 (21) 該類共聚物（A )可由，存在適當溶劑及適當聚合引 發劑下以已知方法’例如自由基聚合上述單體（a（ )及必要時使用之（a3 )及（a4 )而合成。 又，共聚物（A)較佳爲，不存在酸觸媒下以室溫至 1 〇〇 °C之溫度，將乙烯醚化合物或乙烯基硫醚化合物附加 於不飽和多價羧酸酐共聚合所得之前述共聚物中的酸酐基 - ，而得之共聚物。但該共聚物（A )又以不存在游離羧基 • ，或含量少，例如爲前述共聚物中酸醉基之20莫耳％以下 爲佳。 該類共聚物（A )如， (甲基）丙烯酸環氧丙酯/3 一 （甲基）丙燦氧基丙 基三甲氧基矽烷/馬來酸酐/ N-環己基馬來醒亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之乙基乙烯醚的共聚 物、 (甲基）丙烯酸環氧丙酯/ 3 一 （甲基）丙嫌氧基丙 φ 基三甲氧基矽烷/馬來酸酐/ N —環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之n 一丙基乙燒酸的共 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/ Ν 一環己基馬來釀亞胺/本 乙烯共聚物附加對酸酐基爲2倍莫耳之1 一丙基乙燒酸的共 聚物、 (甲基）丙烯酸環氧丙酯/ 3 一 （甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/Ν一環己基馬來醯亞胺/本 -25- 200806701 (22) 乙烯共聚物附加對酸酐基爲2倍莫耳之η —丁 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基 基三甲氧基矽烷/馬來酸酐/ Ν -環己基馬: 乙烯共聚物附加對酸酐基爲2倍莫耳之- i -共聚物、 . (甲基）丙烯酸環氧丙酯/ 3 — （甲基 φ 基三甲氧基矽烷/馬來酸酐/ N -環己基馬 乙烯共聚物附加對酸酐基爲2倍莫耳之t 一丁 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基 基三甲氧基矽烷/馬來酸酐/ N -環己基馬 乙烯共聚物附加對酸酐基爲2倍莫耳之3，4 一 喃的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 - （甲基 • 基三甲氧基矽烷/衣康酸酐/ N -環己基馬 乙烯共聚物附加對酸酐基爲2倍莫耳之乙基 ^ 物、 (甲基）丙烯酸環氧丙酯/ 3 - （甲基 基三甲氧基矽烷/衣康酸酐/ N-環己基馬 乙烯共聚物附加對酸酐基爲2倍莫耳之i 一丙 聚物、 (甲基）丙烯酸環氧丙酯/ 3〜（甲基 基三甲氧基矽烷/衣康酸酐/ N-環己基馬 基乙烯醚的共 )丙烯氧基丙 來醯亞胺/苯 丁基乙烯醚的 )丙烯氧基丙 來醯亞胺/苯 基乙烯醚的共 )丙烯氧基丙 來醯亞胺/苯 二氯一 2 Η — D比 )丙烯氧基丙 來醯亞胺/苯 乙烯醚的共聚 )丙烯氧基丙 來醯亞胺/苯 基乙烯醚的共 )丙烯氧基丙 來醯亞胺/苯 -26- 200806701 (23) 乙烯共聚物附加對酸酐基爲2倍莫耳之3,4 一二氫一 2H—毗 喃的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 —（甲基）丙烯氧基丙 基三甲氧基矽烷/檸康酸酐/ N-環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之乙基乙烯醚的共聚 物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/檸康酸酐/ N -環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之i -丙基乙烯醚的共 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/檸康酸酐/ N-環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之3，4一二氫一 2H—吡 喃的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 —（甲基）丙嫌氧基丙 基三甲氧基砂院/順一 1，2,3,4 一四氫酞酸酐/ N -環己基 馬來醯亞胺/苯乙烯共聚物附加對酸酐基爲2倍莫耳之乙 基乙烯醚的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/順一 1，2,3,4 一四氫酞酸酐/ N—環己基 馬來醯亞胺/苯乙烯共聚物附加對酸酐基爲2倍莫耳之i 一 丙基乙烯醚的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基砂院/順一 15 2，3，4 -四氫酞酸酐/ N -環己基 -27- 200806701 (24) 馬來醯亞胺/苯乙烯共聚物附加對酸酐基爲2倍莫耳之3，4 一二氫一 2H—吡喃的共聚物，及 此等共聚物附加取代各乙烯醚用之各自對應的硫醚之共聚 物等。 此等共聚物（A )中更佳爲， (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/ N—環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之乙基乙烯醚的共聚 物、 (甲基）丙烯酸環氧丙酯/ 3 —（甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/ N-環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之n -丙基乙烯醚的共 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基两 基三甲氧矽烷/馬來酸酐/ Ν -環己基馬來醯亞胺/苯乙 燒共聚物附加對酸酐基爲2倍莫耳之i 一丙基乙烯醚的共聚 物、 (甲基）丙烯酸環氧丙酯/ 3 —（甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/ N-環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之η —丁基乙烯醚的共 聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/馬來酸酐/ Ν—環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之3,4 一二氫一 2Η-吡 •28- 200806701 (25) 喃的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/衣康酸酐/ N -環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之乙基乙烯醚的共聚 物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 • 基三甲氧基矽烷/衣康酸酐/ N-環己基馬來醯亞胺/苯 φ 乙烯共聚物附加對酸酐基爲2倍莫耳之i -丙基乙烯醚的共 聚物、 (甲基）丙烯酸環氧丙酯/3 - （甲基）丙烯氧基丙 基三甲氧基矽烷/衣康酸酐/ N -環己基馬來醯亞胺/苯 乙烯共聚物附加對酸酐基爲2倍莫耳之3,4 —二氫一 2H-吡 喃的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基矽烷/衣康酸酐/ N -環己基馬來醯亞胺/苯 φ 乙烯共聚物附加對酸酐基爲2倍莫耳之3，4 一二氫一 2H -吡 ^ 喃的共聚物、 一 (甲基）丙烯酸環氧丙酯/ 3 — （甲基）丙烯氧基丙 基三甲氧基砂烷/順—1，2，3，4 一四氫酞酸酐/ N -環己基 馬來醯亞胺/苯乙烯共聚物附加對酸酐基爲2倍莫耳之乙 基乙烯醚的共聚物、 (甲基）丙烯酸環氧丙酯/ 3 一 （甲基）丙烯氧基丙 基三甲氧基矽烷/順一 H 3，4 一四氫酞酸酐/ N —環己基 馬來醯亞胺/苯乙烯共聚物附加對酸酐基爲2倍莫耳之丨一 -29- 200806701 (26) 丙基乙烯醚的共聚物等。 本發明之樹脂組成物係以上述高分子量物（A )爲必 須成份，但必要時可含有乙烯性不飽和化合物（B )以更 進一步提升平坦性。 乙烯性不飽和化合物（B ) 本發明所使用之乙焴性不飽和化合物（B )如，單官 能（甲基）丙烯酸酯、2官能（甲基）丙烯酸酯、3官能以 上（甲基）丙烯酸酯，同時具有（甲基）丙烯基及羧基之 化合物、胺基甲酸乙酯（甲基）丙烯酸酯、胺基甲酸乙酯 加成物及聚酯（甲基）丙烯酸酯等。其中又以同時具有（ 甲基）丙烯基及羧基之化合物爲佳。該化合物可爲，分子 內各自含有羧基及（甲基）丙烯基1個以上。 上述單官能（甲基）丙烯酸酯如，2一羥基乙基（甲 基）丙烯酸酯、卡必醇（甲基）丙烯酸酯、異甲硼烷基（ 甲基）丙烯酸酯、3—甲氧基丁基（甲基）丙烯酸酯、2一 (甲基）丙燦醯氧基乙基一 2-經基丙基酞酸酯等。其市 售品如’阿洛尼Μ -1 0 1、Μ _ 1 1 1、Μ -1 1 4 (以上爲東亞合成 (股）製）、KAYARAD TC-110S、TC-120S (以上爲日本 化藥（股）製）、比斯可1 5 8、23 1 1 (以上爲大阪有機化 學工業（股）製）。 上述2官能（甲基）丙烯酸酯如，乙二醇（甲基）丙 嫌酸酯、1，6 -己二醇二（甲基）丙烯酸酯、I，9 一己二醇 二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、四 -30- 200806701 (27) 乙二醇二（甲基）丙烯酸酯、雙苯氧基乙醇芴二丙烯酸酯 等。其市售品如，阿洛尼M-210、M-240、M6200 (以上爲 東亞合成（股）製）、KAYARAD HDDA、HX-220、 R-604 (以上爲日本化藥（股）製）、比斯可26〇、312、 3 3 5 HP (以上爲大阪有機化學工業（股）製）等。 上述3官能以上之（甲基）丙烯酸酯如，三羥甲基丙 • 烷三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、 φ 三（（甲基）丙烯醯氧基乙基）磷酸酯、季戊四醇四（甲 基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊 四醇六（甲基）丙烯酸酯等。其市售品如，阿洛尼Μ·3 09 、Μ-400、Μ-402、Μ-405 ' Μ-45 0、Μ-7100、Μ-8030 ' Μ_ 8060、Μ-1 3 1 0 ' Μ- 1 600 ' Μ- 1 960、Μ-8100、Μ-8530 ' Μ-8 5 60、Μ-905 0 (以上爲東亞合成（股）製）、KAYARAD ΤΜΡΑΤ、DPHA、DPCA-20、DPCA-30、DPCA-60、DPCA-120 (以上爲日本化藥（股）製）、比斯可295、3 00、360 • 、GPT、3ΡΑ、400 (以上爲大阪有機化學工業（股）製） * 等。 ~ 上述同時具有（甲基）丙烯基及羧基之化合物如，三 丙烯醯氧基季戊四醇琥珀酸{別名：3 -丙烯醯氧基- 2,2 -雙丙烯醯氧基甲基-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 -丙烯醯氧基甲基一丙 基）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 一雙一丙烯醯氧基甲基一丙基]酯}、四丙烯醯氧基二 -31 - 200806701 (28) 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）- 2-丙烯醯氧基甲基一丙基] 酯}等。 又’胺基甲酸乙酯（甲基）丙烯酸酯、胺基甲酸乙酯 加成物及聚酯（甲基）丙烯酸酯之市售品如，阿洛尼M _ 7100、Μ·8030、M-8060、M-1 310、M-1600、M-1 960、M- ♦ 8 1 00、Μ· 8 53 0、Μ-8 5 60、Μ_9〇5〇 (以上爲東亞合成（股 φ )製）。 又’例如以自由基反應法等使具有羧基之聚合性不飽 和化合物與具有經基之聚合性不飽和化合物聚合後，對該 羥基使具有異氰酸酯基及聚合性不飽和基的化合物進行胺 基甲酸乙酯化反應而得之物，可期待同不飽和化合物（Β )之效果。該具有羧基之聚合性不飽和化合物如，（甲基 )丙烯酸。具有羥基之聚合性化合物如，2 -羥基乙基（ 甲基）丙烯酸酯、4 -羥基丁基（甲基）丙烯酸酯等，具 φ 有異氰酸酯基及聚合性不飽和基之化合物如，（甲基）丙 烯醯氧基乙基異氰酸酯。 ^ 上述乙烯性不飽和化合物（Β )可單獨或2種以上一起 使用。 乙烯性不飽和化合物（Β )對共聚物（A ) 1 00重量份 較佳爲10至2 00重量份，更佳爲20至150重量份。未達10重 量份時會降低修正性及平坦性，又超過200重量份時會降 低基板密合性而不宜。A cyclic alkyl methacrylate such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5·2·1·〇2,6] 癸院一八一基methyl Acrylate, tricyclo[5.2.1.〇2,6]decane-8-oxyethyl methacrylate, isobornyl methacrylate, etc.; 'Cyclohexyl propyl orthoate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02,6]decane-8 acrylate, tricyclo[5·2·1 ·02,6]decane 8-octyloxyethyl acrylate, isobornyl acrylate, etc.; aryl methacrylate such as phenylmethyl propionate, benzyl methacrylate, etc.; aryl acrylate such as , phenyl acrylate, benzyl acrylate vinegar, etc.; unsaturated dicarboxylic acid diester such as 'diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; bicyclic unsaturated compounds such as Bicyclo[2·2·1]g- 2, suspected, 5~methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2·2 :[]hepta-2-ene 5-methoxybicyclo[2.2.1]gly-2-ene, 5-ethoxybicyclo[2.2.1]g 2-ene, 5,6-dimethoxybicyclo[2·21]heptane-2-ene, 5,6-diethoxybicyclo[2.2.1]heptane-2-ene, 5 — ( 2 ,-ylidylethyl)bicyclo[2,2·1]heptyl-2-ene, 5,6-dihydroxybicyclo[221]heptane-19- 200806701 (16) —2-ene, 5,6- Di(hydroxymethyl)bicyclo[2.2.1]gly-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2·2·1]hept-2-ene' 5-hydroxyl 5- 5-bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl Ring [2.2.1] Geng 2-Ethene, etc.; Maleidin compounds such as phenylmaleimide, cyclohexylmaleimide, benzylideneimine, Ν-number醯 亚 亚 - 3 3 3 3 3 3 3 3 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯Maleic acid hexanoate hexanoate, hydrazine-amber phthalate imine-3-maleimide propionate 'Ν-(9-acridinyl)maleimide, etc.; unsaturated aromatic compound For example, styrene, α-methylstyrene, m-methylbenzene Alkene, ρ-methylstyrene, vinyltoluene, ρ-methoxystyrene, etc.; conjugated diene compounds such as 1,3 -butadiene, isoprene, 2,3 _-dimethyl Base-1,3-butadiene, etc.; unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, etc.; 'unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, Zhongkang Acid 'itaconic acid, etc.; unsaturated dicarboxylic anhydrides such as the various anhydrides of the above unsaturated dicarboxylic acids; other unsaturated compounds such as acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, A Acrylamide, ethyl acetate, and the like. Among them, in terms of copolymerization reactivity, etc., styrene, tricyclo [5.2.1.02'6] brothel-8-yl methacrylate, ρ-methoxy phenyl bromide-20 - 200806701 (17) , 2-methylcyclohexyl acrylate, iota, butadiene, bicyclo[2·2·1]heptane-2, etc. These monomers (a4) may be used singly or in combination. The content of the structural unit derived from the monomer (a) in the copolymer (A) is preferably from 5 to 60% by weight, more preferably from 1 to 50% by weight. The content of this range can achieve good flattening performance and heat resistance. The content of the structural unit derived from the monomer (a2) in the copolymer (Α) is preferably from φ to 70% by weight, more preferably from 20 to 60% by weight. When the enthalpy is less than 10% by weight, the heat resistance and surface hardness of the obtained protective film are insufficient. Further, when the amount exceeds 70% by weight, the storage stability of the resin composition tends to decrease. The content of the structural unit derived from the monomer (a3) in the copolymer (A) is preferably from 1 to 50% by weight, more preferably from 1 to 20% by weight. When the ruthenium is less than 0.1% by weight, the adhesion and surface hardness of the obtained protective film are insufficient. Further, when the cerium exceeds 50% by weight, the storage stability of the resin composition tends to be lowered. The content of the structural unit derived from the monomer (a4) in the copolymer (A) is φ, 100% by weight minus the amount of the structural unit content derived from the monomers (al), (a2) and (a3) λ, but When the monomer (a4) used is an unsaturated-carboxylic acid, an unsaturated dicarboxylic acid or an unsaturated dicarboxylic anhydride, the structural unit derived from the unsaturated monocarboxylic acid 'unsaturated dicarboxylic acid and the unsaturated dicarboxylic anhydride The total content must not exceed 40% by weight. When the amount exceeds 40% by weight, the stability of the obtained composition is impaired, so that it is preferably not more than this. Specific examples of the copolymer (A) are preferably represented by a combination of monomers, such as styrene/tetrahydro-2H-pyran-2-yl (meth) acrylate/methacrylic acid tricyclic [5.2.1. 02 ,6]decane-8-ester/3-methylpropenyloxypropane-21 - 200806701 (18) bis-trimethoxydecane/glycidyl methacrylate copolymer, styrene/1 (cyclohexyloxy) Ethyl (meth) acrylate vinegar / trimethyl methacrylate [5.2.1.02'6] decane octaester / 3 methacryloxypropyltrimethoxy decane / methacrylic acid epoxy Propyl Ester Copolymer, Benzoethylene/Tetrahydro-211-Lauryl-2-(Methyl)-propionate/Vinyl Maleimide/3-Methylpropoxypropyltrimethoxy Sand M / Glycidyl methacrylate copolymer, instrument | Benyijing / 2,3 - one to four tetrahydrofuran than 2 -oxyl base -5 - norbornene / methacrylic acid tricyclic [ 5.2.1 ·02,6]decane-8 vinegar / 3 -methacryloxypropyltrimethoxydecane / styrene methacrylate copolymer, styrene / 1 -(cyclohexyloxy) Ethyl (meth) acrylate / cyclohexyl malayan Amine / 3-methacryloxypropyltrimethoxy chopping / glycidyl methacrylate copolymer, styrene / tetrahydro-2-indole-pyran-2-yl (meth) acrylate • / ring Hexylmalimine / 3-methylpropoxypropyltrimethoxydecane/glycidyl methacrylate copolymer, ^styrene / 2,3 -ditetrahydropyranyl-2 yloxy Carbonyl-5-5-decene/cyclohexylmaleimide/3-methylpropoxypropyltrimethoxydecane/glycidyl methacrylate copolymer, butadiene/styrene/1 (cyclohexyloxy)ethyl (meth) acrylate / tricyclo[meth] methacrylate [5.2.1.02,6]decane-8-ester / 3-methylpropoxypropyltrimethoxydecane / methyl Glycidyl acrylate copolymer, -22- 200806701 (19) Butadiene/tetrahydro-2H-pyran-2-yl (meth) acrylate/methacrylic acid tricyclo[5.2·1·02'6 ]癸院一8 — ester / 3-methylpropane oxypropyl dimethoxy sand yard / methyl propyl succinic acid propylene vinegar copolymer, t butyl methyl propionate / tetrahydro 2 Η —卩比喃一2-基(methyl)-propyl Phthalate/maleic anhydride/3-propoxypropyltrimethoxysane/methacrylic acid-6,7-epoxyheptyl ester copolymer, -styrene/tetrahydro-2H-pyranyl-2 (meth) acrylate / methyl methacrylate / 3-methyl propylene oxy propyl trimethoxy fluorene / propylene methacrylate copolymer, p - methoxy benzene / tetrahydrogen a 2H-fluorenyl-2-yl (meth) acrylate / cyclohexyl acrylate / 3-methyl propylene oxy propyl trimethoxy decane / glycidyl methacrylate copolymer; t-butyl methyl Acrylic acid vinegar / benzene bismuth / 3-methyl propyloxy propyl trimethoxy decane / glycidyl methacrylate / cyclohexyl maleimide copolymer, φ styrene / t-butyl methyl Acrylate / Tricyclomethacrylate • [5.2.1. 02'6] decane-8-ester / 3_methacryloxypropyl triethoxy-decane / methacrylic acid a 6,7-ring Oxyheptyl ester copolymer, styrene/t-butyl methacrylate/maleic anhydride/3-methylpropoxypropyltriethoxydecane/methacrylic acid-6,7-epoxyheptyl ester copolymer, Styrene / t- Butyl methacrylate/phenylmaleimide/3-propenyloxypropyltrimethoxydecane/glycidyl acrylate copolymer, etc. 23-200806701 (20) Among them, benzopyrene/four Ammonia-2H-indole-pyrene-2/methacrylic acid tricyclo[5.2·1·02,6]decyloxypropyltrimethoxydecane/methacryl phenethyl/tetrahydro-2 Η-卩 ratio一2/phenylmaleimide/3-methacryl/glycidyl methacrylate copolymer, styrene/2,3-ditetrahydropyranyl-decene/methacrylic acid tricyclic [5·2·1·02-propenyloxypropyltrimethoxydecane/methyl, styrene/1-(cyclohexyloxy)ethylcyclohexylmaleimide/3-methylpropene/methyl Glycidyl acrylate copolymer, styrene/tetrahydro-2-indole-pyranyl-2/cyclohexylmaleimide/3-methylpropane/glycidyl methacrylate copolymer, styrene/ 2, 3—Di-tetrahydropyran-decene/cyclohexylmaleimide/methylbutadiene/styrene/1 A (cyclohexenoate/methacrylic acid tricyclo[5.2.1.0 = propylene Oxypropyl trimethoxy decane / methyl 0 Methyl) acrylate 8-octyl ester / 3-glycidyl methacrylate copolymer, a group of (meth) acrylate oxypropyl trimethoxy decane - 2-yloxy group - 5 - ' 6] decane-8-ester/3-glycidyl methacrylate copolymer (meth) acrylate / oxypropyl trimethoxy decane-based (meth) acrylate methoxy propyl trimethoxy Base sand - 2 - oxy group - 5 - propylene acrylate copolymer oxy) ethyl (methyl) propyl 5 '6] decane - 8 - ester / 3 ~ methyl 1 acrylate acrylic Ester Copolymer-24 200806701 (21) The copolymer (A) can be obtained by a known method in the presence of a suitable solvent and a suitable polymerization initiator, for example, radical polymerization of the above monomer (a( ) and, if necessary, (a3) And (a4) and synthesized. Further, the copolymer (A) is preferably obtained by copolymerizing a vinyl ether compound or a vinyl sulfide compound with an unsaturated polyvalent carboxylic acid anhydride at a temperature of from room temperature to 1 ° C in the absence of an acid catalyst. The acid anhydride group in the aforementioned copolymer, and the resulting copolymer. However, the copolymer (A) is preferably in the absence of a free carboxyl group, or has a small content, and is preferably, for example, 20 mol% or less of the acid-toxic group in the copolymer. Such copolymers (A) are, for example, glycidyl (meth)acrylate/3-(methyl)propenyloxypropyltrimethoxydecane/maleic anhydride/N-cyclohexylmamarinamide/ The styrene copolymer is a copolymer of ethyl vinyl ether having an acid anhydride group of 2 times molar, glycidyl (meth)acrylate / 3 - (meth) propionyloxypropyl 1,3-trimethoxydecane / Maleic anhydride / N - cyclohexyl maleimide / styrene copolymer plus copolymer of 2-fold molar n-propyl ethane succinic acid anhydride, glycidyl (meth) acrylate / 3 — (Meth) propylene oxy propyl trimethoxy decane / maleic anhydride / Ν one cyclohexyl maleimide / the present ethylene copolymer plus the anhydride group is 2 times the molar of 1 propyl ethanoic acid Copolymer, glycidyl (meth)acrylate / 3 - (meth) propylene oxy propyl trimethoxy decane / maleic anhydride / hydrazine - cyclohexyl maleimide / this - 25 - 200806701 (22) The ethylene copolymer is added to the acid anhydride group of 2 times mole of η-butylene, (meth)acrylic acid propyl acrylate / 3 - (methyltrimethoxydecane / maleic anhydride) / Ν -cyclohexylma: ethylene copolymer added to the anhydride group is 2 times molar - i - copolymer, . (meth)acrylic acid propyl acrylate / 3 - (methyl φ trimethoxy decane / horse The anhydride/N-cyclohexylmethylene copolymer is added to the acid anhydride group of 2 times moles of t-butyl polymer, glycidyl (meth)acrylate / 3 - (methyltrimethoxydecane / Malay) Anhydride/N-cyclohexylmethylene copolymer with a copolymer of 2,4 moles of an acid anhydride group, a glycidyl (meth)acrylate / 3 - (methyl methoxytrimethoxydecane) /Itaconic anhydride / N -cyclohexylmethylene copolymer plus an ethyl acetate of 2 moles of anhydride, glycidyl (meth)acrylate / 3 - (methyltrimethoxydecane / clothing The anhydride/N-cyclohexylmethylene copolymer is added to the anhydride group of 2 times moles of i-polymer, (meth)acrylic acid propyl acrylate / 3~(methyltrimethoxydecane/Icon Anhydride/N-cyclohexyl-methylene vinyl ether co-) propylene oxy propylene imidate / phenyl butyl vinyl ether) propylene oxy propylene sulfide / phenyl vinyl ether) Alkenyloxypropionimine / phenyldichloro-2 Η - D ratio) copolymerization of propylene oxy propylene amide / styrene ether) propylene propylene propylene amide / phenyl vinyl ether) Propylene oxy propylene imidate / benzene-26- 200806701 (23) Ethylene copolymer with a copolymer of 2,4 dihydrogen-2H-pyrene having an acid anhydride group of 2 moles, (meth)acrylic acid Glycidylpropyl / 3-(meth)acryloxypropyltrimethoxydecane / citraconic anhydride / N-cyclohexylmaleimide / styrene copolymer with an anhydride group of 2 times Mo Copolymer of vinyl ether, glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/citraconic anhydride/N-cyclohexylmaleimide/styrene copolymerization a copolymer of 2-propyloleic i-propyl vinyl ether with an acid anhydride group, glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/citonic anhydride / N-cyclohexylmaleimide/styrene copolymer with a copolymer of 2,4 dihydrogen-2H-pyran having an acid anhydride group of 2 moles, (meth)acrylic acid propylene / 3 —(Methyl)propoxypropyltrimethoxy sands/cis-1,2,3,4 tetrahydrophthalic anhydride/N-cyclohexylmaleimide/styrene copolymer with anhydride a copolymer of 2-fold molar ethyl vinyl ether, glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/cis-1,2,3,4 Tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene copolymer plus copolymer of 2 gram of i propyl vinyl ether anhydride anhydride group, glycidyl (meth) acrylate / 3 — (Meth) propylene oxypropyl trimethoxy sand yard / cis-15 2,3,4 -tetrahydrophthalic anhydride / N-cyclohexyl-27- 200806701 (24) Maleimide / styrene copolymer Further, a copolymer of 3,4-dihydro-2H-pyran having an acid anhydride group of 2 mols is added, and a copolymer of these copolymers in which each of the corresponding thioethers for each vinyl ether is substituted is added. More preferably, in the copolymer (A), glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/maleic anhydride/N-cyclohexylmalayiya The amine/styrene copolymer is a copolymer of ethyl vinyl ether having an acid anhydride group of 2 times molar, glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane / Maleic anhydride / N-cyclohexylmaleimide / styrene copolymer plus copolymer of 2 - molar n - propyl vinyl ether anhydride anhydride group, glycidyl (meth)acrylate / 3 - (Meth)acryloxybisyltrimethoxyoxane/maleic anhydride/Ν-cyclohexylmaleimide/phenylethene copolymer plus copolymerization of an acid anhydride group of 2 times mole of i-propyl vinyl ether , glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/maleic anhydride/N-cyclohexylmaleimide/styrene copolymer with an anhydride group 2 times mole of η-butyl vinyl ether copolymer, (meth)acrylic acid propyl acrylate / 3 - (meth) propylene oxypropyl trimethoxy decane / The anhydride/ruthenium-cyclohexylmaleimide/styrene copolymer is added to the acid anhydride group of 2 times mole of 3,4 dihydrogen-2Η-pyrid. 28-200806701 (25) copolymer of butyl, Glycidyl methacrylate / 3 - (meth) propylene oxy propyl trimethoxy decane / itaconic anhydride / N - cyclohexyl maleimide / styrene copolymer plus 2 times the anhydride group Copolymer of ethyl vinyl ether of Moer, glycidyl (meth)acrylate / 3-(meth)acryloxypropyltrimethoxydecane/itaconic anhydride/N-cyclohexylmalazone Amine/benzene φ ethylene copolymer with a copolymer of 2-fold molar i-propyl vinyl ether anhydride, glycidyl (meth)acrylate/3-(meth)acryloxypropyltrimethoxy a decyl/itaconic anhydride/N-cyclohexylmaleimide/styrene copolymer with a copolymer of 2,4-dihydro-2H-pyran having an acid anhydride group of 2 moles, (meth) Glycidyl acrylate / 3 - (meth) propylene oxy propyl trimethoxy decane / itaconic anhydride / N - cyclohexyl maleimide / benzene φ ethylene copolymer with an additional anhydride group 2 times molar copolymer of 3,4 dihydrogen-2H-pyran, a glycyl propyl (meth)acrylate / 3 - (meth) propylene oxypropyl trimethoxy sulane / cis —1,2,3,4 tetrahydrophthalic anhydride/N-cyclohexylmaleimide/styrene copolymer plus copolymer of ethyl vinyl ether having an anhydride group of 2 times mol, (methyl) Glycidyl acrylate / 3 - (meth) propylene oxy propyl trimethoxy decane / cis H 3, 4 tetrahydrophthalic anhydride / N - cyclohexyl maleimide / styrene copolymer plus anhydride The base is 2 times the mole of 丨--29-200806701 (26) a copolymer of propyl vinyl ether and the like. The resin composition of the present invention contains the above-mentioned high molecular weight substance (A) as a necessary component, but may contain an ethylenically unsaturated compound (B) as necessary to further improve flatness. Ethylenically unsaturated compound (B) The ethylenically unsaturated compound (B) used in the present invention is, for example, a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a trifunctional or higher (meth) acrylate. The ester includes a compound of a (meth)acryl group and a carboxyl group, an ethyl urethane (meth) acrylate, an ethyl urethane adduct, a polyester (meth) acrylate, and the like. Among them, a compound having both a (meth)acryl group and a carboxyl group is preferred. The compound may have one or more carboxyl groups and (meth)acryl groups in the molecule. The above monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboryl (meth) acrylate, 3-methoxy Butyl (meth) acrylate, 2-(methyl) propyl decyloxyethyl 2- 2-propyl propyl phthalate, and the like. Its commercial products such as 'Alonian Μ -1 0 1 , Μ _ 1 1 1 , Μ -1 1 4 (above is East Asia Synthetic (stock) system), KAYARAD TC-110S, TC-120S (above is Japanese Pharmaceutical (stock) system, Biske 1 5 8 , 23 1 1 (above is Osaka Organic Chemical Industry Co., Ltd.). The above bifunctional (meth) acrylates such as ethylene glycol (meth) propylene sulphate, 1,6-hexane diol di(meth) acrylate, I, hexahexane diol di(meth) acrylate Ester, polypropylene glycol di(meth)acrylate, tetra-30-200806701 (27) ethylene glycol di(meth)acrylate, bisphenoxyethanol hydrazine diacrylate, and the like. Commercially available products such as Aloni M-210, M-240, M6200 (above are East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (the above are manufactured by Nippon Kayaku Co., Ltd.) , Biske 26, 312, 3 3 5 HP (above is Osaka Organic Chemical Industry Co., Ltd.). The above trifunctional or higher (meth) acrylate such as trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, φ tris((meth) propylene methoxyethyl Phosphate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. Its commercial products such as, Alonni · 3 09, Μ-400, Μ-402, Μ-405 'Μ-45 0, Μ-7100, Μ-8030 ' Μ _ 8060, Μ-1 3 1 0 ' Μ - 1 600 ' Μ - 1 960, Μ-8100, Μ-8530 ' Μ-8 5 60, Μ-905 0 (above is East Asia Synthetic (stock) system), KAYARAD ΤΜΡΑΤ, DPHA, DPCA-20, DPCA-30 , DPCA-60, DPCA-120 (above is Nippon Chemical Co., Ltd.), Bisko 295, 30,000, 360 • , GPT, 3ΡΑ, 400 (above is Osaka Organic Chemical Industry Co., Ltd.) * . ~ The above compound having both (meth) propylene group and carboxyl group, for example, tripropylene decyloxy pentaerythritol succinic acid {alias: 3-propenyloxy-2,2-bispropenyloxymethyl-propyl) ester }, Dipropylene decyloxy pentaerythritol succinic acid {alias: 3-propenyloxy 2- 2 -propenyloxymethyl monopropyl)}, penta propylene oxydipentaerythritol succinic acid {alias: [3 - (3-propenyloxy- 2,2-di-propylene methoxymethyl-propyl)- 2,2-bis-propylene oxymethyl-propyl] ester, tetrapropenyloxy 2 -31 - 200806701 (28) Pentaerythritol succinic acid {alias: [3 - (3-propenyloxy- 2,2-bis-propylene methoxymethyl-propyl)-2-propenyloxymethyl- Propyl] ester} and the like. Further, commercially available products of 'ethyl urethane (meth) acrylate, ethyl urethane adduct and polyester (meth) acrylate, for example, Aloni M _ 7100, Μ 8030, M- 8060, M-1 310, M-1600, M-1 960, M- ♦ 8 1 00, Μ· 8 53 0, Μ-8 5 60, Μ_9〇5〇 (above is East Asia Synthetic (Share φ) system) . Further, for example, a polymerizable unsaturated compound having a carboxyl group and a polymerizable unsaturated compound having a trans group are polymerized by a radical reaction method, and the compound having an isocyanate group and a polymerizable unsaturated group is subjected to an aminocarboxylic acid to the hydroxyl group. The effect of the same unsaturated compound (Β) can be expected from the ethyl esterification reaction. The polymerizable unsaturated compound having a carboxyl group is, for example, (meth)acrylic acid. a polymerizable compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate, or the like having a φ isocyanate group and a polymerizable unsaturated group. Base) propylene methoxyethyl isocyanate. The above ethylenically unsaturated compound (Β) may be used alone or in combination of two or more. The ethylenically unsaturated compound (Β) is preferably from 10 to 200 parts by weight, more preferably from 20 to 150 parts by weight, per 100 parts by weight of the copolymer (A). When the amount is less than 10 parts by weight, the correctness and flatness are lowered, and when it exceeds 200 parts by weight, the substrate adhesion is lowered.

本發明之硬化性樹脂組成物係以上述高分子量物（A -32- 200806701 (29) )爲必須成份，但必要時可含有上述乙烯性不飽和化合物 (B )，又可另含有環氧化合物（C )及/或感放射線性 酸發生劑（D )及/或感熱性酸發生劑（E )。 環氧化合物（C ) 必要時本發明可使用分子內具有2個以上環氧構造之 * 化合物（C )(但前述（A )成份除外）。使用環氧化合 φ 物時可解除所得保護膜之硬度不足情形。 該類環氧化合物（C )如，分子內具有2個以上環氧基 之化合物、分子內具有2個以上3，4 -環氧環己基之化合物 等。 上述分子內具有2個以上環氧基之化合物如，雙酚A 二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚 、氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、 氫化雙酚AD二縮水甘油醚、溴化雙酚A二縮水甘油醚、溴 • 化雙酚F二縮水甘油醚、溴化雙酚S二縮水甘油醚等雙酚化 * 合物之二縮水甘油醚； • 1，4 一丁二醇二縮水甘油醚、1，6 —己二醇二縮水甘油 醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、聚 乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚等多價醇之 聚縮水甘油醚； 11311 種 2 或 \1巨1 種 1 ·， 加醚 附油 醇甘 價水 多縮 族聚 肪之 脂醇； 等聚脂 油醚樹 甘聚氧 、 的環 醇得型 二而漆 丙物清 、 化醛 醇氧酚 二環酚 乙之苯 上 以 -33 - 200806701 (30) 甲酚酚醛清漆型環氧樹脂； 聚苯酚型環氧樹脂； 脂肪族長鏈二羧酸之二縮水甘油酯； 高級脂肪酸之縮水甘油酯； 環氧化大豆油、環氧化亞麻仁油等。 上述具有2個以上環氧基之化合物的市售品如，雙酚 ‘ A型環氧樹脂之耶皮可1001、 1002、 1003、 1004、 1007、 Φ 1009、1010、828 (以上爲日本環氧樹脂（股）製）等； 雙酚F型環氧樹脂之耶皮可807 (日本環氧樹脂（股） 製）等； 苯酚酚醛清漆型環氧樹脂之耶皮可152、154、157S65 (以上爲日本環氧樹脂（股）製、EPPN 201、202 (以上 爲曰本化藥（股）製）等； 甲酚酚醛清漆型環氧樹脂之EOCN 102、103S、104S 、1 020、1 025、1 027 (以上爲日本化藥（股）製）、耶皮 # 可1S0S75 (日本環氧樹脂（股）製）等； 癱 聚苯酚型環氧樹脂之耶皮可1032H60、XY-4000 (以 ’ 上爲日本環氧樹脂（股）製）等； 環狀脂肪族環氧樹脂之CY-175、177、179、艾拉爾 CY-182、192、184 (以上爲吉巴斯（股）製）、 ERL-4234、4299、4 2 2 1、4 2 0 6 (以上爲 U . C . C 公司製）、 修戴因5 09 (昭和電工（股）製）、耶皮克200、400 (以 上爲日本油墨（股）製）、耶皮可871、872 (以上爲日本 環氧樹脂（股）製）、ED_ 5 66 1、5 662 (以上爲歇拉尼公 -34- 200806701 (31) 司製）等； 脂肪族聚縮水甘油醚之耶波來1 0 0 M F (共榮社化學（ 股）製）、耶皮歐ΤΜΡ (日本油脂（股）製）等。 上述分子內具有2個以上3,4-環氧環己基之化合物如 ，3，4一環氧環己基甲基一 3’，4’一環氧環己烷羧酸酯、2-(3,4 —環氧環己基—5,5 -螺—3,4 一環氧基）環己烷一偏 • 一二噁烷、雙（3，4 一環氧環己基甲基）己二酸酯、雙（ φ 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 —環氧環己烷）、二環戊二烯二 環氧化物、乙二醇之二（3,4 —環氧環己基甲基）醚、伸 乙基雙（3，4 -環氧環己烷羧酸酯）、內酯改性3，4 一環氧 環己基甲基- 3 ’，4 ’ —環氧環己烷羧酸酯等。 該類環氧化合物（C)中又以苯酚酚醛清漆型環氧樹 脂及聚苯酚型環氧樹脂爲佳。 Φ 又，高分子量物（Α)之分子內雖具有2個以上環氧 ^ 構造，但就具有羧酸之縮醛酯基、縮酮酯基、1 一烷基環 ^ 烷基酯基及t -丁基酯基觀點，係不同於不具有羧酸之縮 醛酯基、縮酮酯基、1 -烷基環烷基酯基及t -丁基酯中任 何一種的環氧化合物（C )。 本發明之樹脂組成物中，環氧化合物（C )的使用量 對高分子量物（A)每1〇〇重量份較佳爲〇至200重量份， 更佳爲〇至100重量份，特佳爲〇至50重量份。環氧化合物 (C )之使用量多於200重量份時，會使組成物之塗佈性產 -35- 200806701 (32) 生問題。 感放射線性酸發生劑（D ) 感放射線性酸發生劑可爲，照射可視光線、紫外n、 遠紫外線、電子線、X線等放射線可發生酸之化合物。 該類感放射線性酸發生劑較佳如，二芳基碘鑰鹽、= ^ 芳基毓鹽、二芳基鳞鹽等。 φ 上述二芳基碘鏺鹽如，二苯基碘鐵四氟硼酸鹽、二苯 基碘鐵六氟膦酸鹽、二苯基碘鑰六氟砷酸鹽、二苯基碘錄 三氟甲烷磺酸鹽、二苯基碘鐵三氟乙酸鹽、二苯基碘錄〜 P -甲苯磺酸鹽、4 -甲氧基苯基苯基碘鐵四氟硼酸鹽、4 -甲氧基苯基苯基碘鑰六氟膦酸鹽、4一甲氧基苯基苯基 «銷六氟砷酸鹽、4 -甲氧基苯基苯基碘鑰三氟甲烷磺酸 鹽、4一甲氧基苯基苯基碘鏺三氟乙酸鹽、4一甲氧基苯其： 本基碘:鐵一 ρ-甲苯磺酸鹽、雙（4 一 tert— 丁基苯基）碘 • 鐵四氟硼酸鹽、雙（4 一 tert — 丁基苯基）碘鎗六氟砷酸鹽 、雙（4 一 tert -丁基苯基）碘銷三氟甲烷磺酸鹽、雙（4 一 tert 一丁基苯基）碘鐵三氟乙酸鹽、雙（4一 “η一丁基 本基）碘鑰- p-甲苯磺酸鹽等。其中較佳爲使用二苯其 碘鐵六氟膦酸鹽。 上述二芳基毓鹽如，二苯基銃四氟硼酸鹽、三苯基鏡 六氟膦酸鹽、三苯基毓六氟砷酸鹽、三苯基毓三氟甲院礦 酸鹽、三苯基毓三氟乙酸鹽、三苯基毓一 P 一甲苯擴酸鹽 、4-甲氧基苯基二苯基鏑四氟硼酸鹽'4一甲氧基苯基二 -36- 200806701 (33) 苯基毓六氟膦酸鹽、4 -甲氧基苯基二苯基毓六氟砷酸鹽 、4 —甲氧基苯基二苯基锍三氟甲烷磺酸鹽、4 一甲氧基苯 基毓三氟乙酸鹽、4-甲氧基苯基二苯基毓一 p一甲苯磺酸 鹽、4一苯基硫苯基二苯基四氟硼酸鹽、4-苯基硫苯基二 苯基六氟膦酸鹽' 4-苯基硫苯基二苯基六氟砷酸鹽、4-苯基硫苯基二苯基三氟甲烷磺酸鹽、4 -苯基硫苯基二苯 ^ 基三氟乙酸鹽、4 一苯基硫苯基二苯基一 p一甲苯磺酸鹽等 φ 。其中又以用三苯基锍三氟甲烷磺酸鹽爲佳。 上述一·方基鱗鹽如’ （1 一 6 - Tj 一枯嫌）(T} 一環戊 二烯基）鐵六氟膦酸鹽等。 適用爲感放射線性酸發生劑之酸發生劑的市售品如， 二烷基碘鐵鹽類之尤尼歐公司製商品名：UVI-6950、 UVI-6970、UVI-6974、UVI-6990、綠化學（股）製商品. 名：MPI-103、BBI-103 等。 又，三芳基毓鹽類如，旭電化工業（股）製商品名： _ 艾得考 SP-150、 SP-151、 SP-170、 SP-171、日本曹達（股 * )製商品名：CI - 2 4 8 1、CI - 2 6 2 4、CI - 2 6 3 9、C I - 2 0 6 4、綠 ‘ 化學（股）製商品名：DTS-102、DTS-103、NAT-103、 NDS-1 03、TPS-103、MDS-1 03、撒特曼公司製商品名： CD-1010、CD-1011、CD-1012 等。 又，二芳基鳞鹽如，吉巴斯公司製商品名：伊路凱 261、日本化藥（股）製商品名：PCI-061T、PCI-062T、 PCI-020T、PCI-02 2T等。 其中又以尤尼歐公司製商品名：UVI-6970、 -37- 200806701 (34) UV1-6974、UV1-6990、旭電化工業（股）製商品名：艾 得考SP-170、SP-17 1、撒特曼公司製商品名：CD-1012、 綠化學（股）製商品名：MPI-103所得之保護膜具有高表 面硬度爲佳。 本發明之硬化性樹脂組成物爲含有感放射線性酸發生 劑（D)之物時，其使用量對高分子量物（A) 100重量份 ’ 較佳爲〇.〇5至20重量份，更佳爲0.1至10重量份。使用量 φ 爲該範圍時可得具有充分硬度之保護膜。 感熱性酸發生劑（E ) 感熱性酸發生劑如，毓鹽（前述三芳基毓鹽除外）、 苯并噻唑鐵鹽、銨鹽、鱗鹽等，其中又以使用鏑鹽（前述 三芳基鏟鹽除外）、苯并噻唑鑰鹽爲佳。 上述毓鹽（前述三芳基毓鹽除外）之具體例如，4 一 乙醯苯基三甲基鏑六氟銻酸鹽、4-乙醯氧基苯基二甲基 • 鏑六氟砷酸鹽、二甲基- 4 -（节氧基鑛氧基）苯基鏑六 ¥ 氟銻酸鹽、二甲基一 4-（苯醯氧基）苯基毓六氟銻酸鹽 ^ 、二甲基一 4一（苯醯氧基）苯基锍六氟砷酸鹽、二甲基 -3-氯-4-乙醯氧基苯基毓六氟銻酸鹽爲烷基毓鹽；苄 基- 4一羥基苯基甲基毓六氟銻酸鹽、苄基一 4-羥基苯基 甲基鏡六氟磷酸鹽、4-乙醯氧基苯基苄基甲基毓六氟銻 酸鹽、苄基- 4-甲氧基苯基甲基锍六氟銻酸鹽、苄基- 2 一甲基一 4 一羥基苯基甲基毓六氟銻酸鹽、节基一 3 —氯一 4 一羥基苯基甲基毓六氟砷酸鹽、4一甲氧基苄基一 4-羥 -38- 200806701 (35) 基苯基甲基鏡六氟磷酸鹽等苄基毓鹽； 二苄基一 4 一羥基苯基毓六氟銻酸鹽、二苄基一 4 一羥 基苯基毓六氟磷酸鹽、4-乙醯氧基苯基二苄基毓六氟銻 酸鹽、二苄基一 4 一甲氧基苯基毓六氟銻酸鹽、二苄基一 3 一氯一 4 —羥基苯基毓六氟砷酸鹽、二苄基—3 -甲基一 4 一羥基一 5 - tert-丁基苯基毓六氟銻酸鹽、苄基一 4 一甲 - 氧基苄基- 4 -羥基苯基鏡六氟磷酸鹽等苄基毓鹽； φ P -氯苄基- 4 一羥基苯基甲基毓六氟銻酸鹽、p -硝 基苄基一 4-羥基苯基甲基鏡六氟銻酸鹽、p-氯苄基- 4 一羥基苯基甲基毓六氟磷酸鹽、P-硝基苄基- 3 —甲基一 4一羥基苯基甲基毓六氟銻酸鹽、3,5 —二氯苄基一 4 —羥 基苯基甲基毓六氟銻酸鹽、〇 -氯苄基一 3 -氯一 4 一羥基 苯基甲基锍六氟銻酸鹽等取代苄基毓鹽等。 其中又以使用4 -乙醯氧基苯基二甲基毓六氟砷酸鹽鹽 、苄基一 4-羥基苯基甲基鏡六氟銻酸鹽、4一乙醯氧基苯 • 基苄基甲基毓六氟銻酸鹽、二苄基- 4-羥基苯基毓六氟 ^ 銻酸鹽、4 -乙醯氧基苯基苄基毓六氟銻酸鹽等爲佳。 ^ 上述苯并噻唑鐵鹽如，3 -苄基苯并噻唑鍚六氟銻酸 鹽、3 —苄基苯并噻唑鑰六氟磷酸鹽、3 -苄基苯并噻唑鑰 四氟硼酸鹽、3 —（ p —甲氧基苄基）苯并噻唑鐵六氟銻酸 鹽、3 —苄基一 2—甲基噻唑鑰六氟銻酸鹽、3—苄基一 5 -氯苯并噻唑鑰六氟銻酸鹽等苄基苯并噻唑鐵鹽。 其中又以使用3 -苄基苯并噻唑鐺六氟銻酸鹽等。 適用爲感熱酸發生劑之酸發生劑的市售品如，烷基毓 •39- 200806701 (36)The curable resin composition of the present invention contains the above-mentioned high molecular weight substance (A-32-200806701 (29)) as an essential component, but may contain the above-mentioned ethylenically unsaturated compound (B) if necessary, and may further contain an epoxy compound. (C) and/or a sensory radioactive acid generator (D) and/or a thermosensitive acid generator (E). Epoxy compound (C) If necessary, the compound (C) having two or more epoxy structures in the molecule can be used in the present invention (except for the above (A) component). When the epoxidized φ substance is used, the insufficient hardness of the obtained protective film can be released. The epoxy compound (C) is a compound having two or more epoxy groups in the molecule, a compound having two or more 3,4-epoxycyclohexyl groups in the molecule, and the like. a compound having two or more epoxy groups in the above molecule, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol Bisphenolation of F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Diglycidyl ether; 1,1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, poly Polyglycidyl ether of polyvalent alcohol such as ethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; 11311 species 2 or \1 giant 1 species 1 ·, ether ether oleyl alcohol, valence water, polycondensation Alkyl alcohol; a phenolic phenolic varnish type ring; a phenolic phenolic varnish type ring; a phenolic phenolic varnish type ring; Oxygen resin; polyphenol type epoxy resin; diglycidyl ester of aliphatic long-chain dicarboxylic acid; Glycidyl esters of fatty acid; epoxidized soybean oil, epoxidized linseed oil and the like. Commercial products of the above compound having two or more epoxy groups, such as bisphenol 'A type epoxy resin, yuppie 1001, 1002, 1003, 1004, 1007, Φ 1009, 1010, 828 (above is Japanese epoxy Resin (manufactured by resin), etc.; bisphenol F-type epoxy resin, yuppie 807 (made by Nippon Epoxy Resin Co., Ltd.), etc.; phenol novolac type epoxy resin, yuppie 152, 154, 157S65 (above It is made of Japan Epoxy Resin Co., Ltd., EPPN 201, 202 (above is Sakamoto Chemical Co., Ltd.), etc.; EOCN 102, 103S, 104S, 1 020, 1 025 of cresol novolak type epoxy resin, 1 027 (The above is made by Nippon Kayaku Co., Ltd.), Yapi #1S0S75 (made by Nippon Epoxy Resin Co., Ltd.), etc. 瘫 Phenol type epoxy resin of Phi Phi 1032H60, XY-4000 (by ' The above is made of Japanese epoxy resin (share), etc.; CY-175, 177, 179 of cyclic aliphatic epoxy resin, CY-182, 192, 184 of Alar (manufactured by Gibbs Co., Ltd.) , ERL-4234, 4299, 4 2 2 1 , 4 2 0 6 (above is U. C. C company), Xiu Daiyin 5 09 (Showa Denko (share) system), Yepike 200, 400 (above is Japanese ink (share) system), yuppie 871, 872 (above is Japanese epoxy resin (share) system), ED_ 5 66 1, 5 662 (above is 歇拉尼公-34- 200806701 (31) Servicing), etc.; Yebolai 1 0 0 MF (made by Kyoeisha Chemical Co., Ltd.), Jeepou (made by Japanese Oils and Fats Co., Ltd.), etc. a compound having two or more 3,4-epoxycyclohexyl groups therein, such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, bis ( φ 3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl- 3',4'-epoxy- 6' Monomethylcyclohexanecarboxylate, methyl bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol (3,4-epoxycyclohexyl) Methyl)ether, exoethyl bis(3,4-epoxycyclohexanecarboxylate), lactone modification 3 4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, etc. The epoxy compound (C) is further composed of a phenol novolac type epoxy resin and a polyphenol type epoxy resin. Preferably, the high molecular weight substance (Α) has two or more epoxy structures in the molecule, but has an acetal ester group, a ketal ester group, and a monoalkylcycloalkyl ester of a carboxylic acid. The base and the t-butyl ester group are different from the epoxy compound having no acetal ester group, ketal ester group, 1-alkylcycloalkyl ester group and t-butyl ester of the carboxylic acid. (C). In the resin composition of the present invention, the epoxy compound (C) is preferably used in an amount of from 〇 to 200 parts by weight, more preferably from 〇 to 100 parts by weight, per 100 parts by weight of the high molecular weight substance (A). It is 50 parts by weight. When the epoxy compound (C) is used in an amount of more than 200 parts by weight, the coating property of the composition is caused to be problem-35-200806701 (32). The radiation-sensitive linear acid generator (D) The radiation-sensitive linear acid generator may be a compound which can generate an acid by radiation such as visible light, ultraviolet n, far ultraviolet light, electron beam or X-ray. The radiation-sensitive acid generator of this type is preferably, for example, a diaryl iodine salt, a = aryl sulfonium salt, a diaryl sulfonium salt or the like. φ The above diaryl iodonium salt, for example, diphenyl iodine iron tetrafluoroborate, diphenyl iodine iron hexafluorophosphonate, diphenyl iodine hexafluoroarsenate, diphenyl iodine trifluoromethane Sulfonic acid salt, diphenyliodop iron trifluoroacetate, diphenyl iodide ~ P-toluenesulfonate, 4-methoxyphenylphenyl iodide iron tetrafluoroborate, 4-methoxyphenyl Phenyl iodide hexafluorophosphonate, 4-methoxyphenylphenyl «pin hexafluoroarsenate, 4-methoxyphenylphenyl iodide trifluoromethanesulfonate, 4-methoxyl Phenylphenyliodonium trifluoroacetate, 4-methoxybenzene: Benzo iodide: iron-p-toluenesulfonate, bis(4-tert-butylphenyl)iodine•iron tetrafluoroborate , bis(4-tert-butylphenyl) iodine gun hexafluoroarsenate, bis(4-tert-butylphenyl)iodopin trifluoromethanesulfonate, bis(4-tert-butylphenyl) Iodine trifluoroacetate, bis(4-monoethylidene) iodine-p-toluenesulfonate, etc. Among them, diphenyl iridium iron hexafluorophosphonate is preferably used.毓 salt, such as diphenyl sulfonium tetrafluoroborate, triphenyl mirror Phosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoride ore, triphenylsulfonium trifluoroacetate, triphenylsulfonium-P-toluene acid ester, 4-methyl Oxyphenyl diphenyl sulfonium tetrafluoroborate '4-methoxyphenyl di-36- 200806701 (33) phenyl sulfonium hexafluorophosphonate, 4-methoxyphenyl diphenyl sulfonium hexafluoride Arsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium-p-toluene Sulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate 4-phenylthiophenyldiphenylhexafluoroarsenate , 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonic acid Salt, etc. φ. Among them, triphenylsulfonium trifluoromethanesulfonate is preferred. The above-mentioned one-square scale salt such as '(1-6-Tj) is a (T}-cyclopentadienyl) iron Hexafluorophosphonate, etc. Commercial products suitable as acid generators for radiation sensitive acid generators, for example, The product name of the product is UVI-6950, UVI-6970, UVI-6974, UVI-6990, and Green Chemical Co., Ltd.. Name: MPI-103, BBI-103, etc. In addition, triaryl sulfonium salts such as: Asahi Chemical Industry Co., Ltd. product name: _ Adeko SP-150, SP-151, SP-170, SP-171, Japan Soda (stock *) system name: CI - 2 4 8 1, CI - 2 6 2 4, CI - 2 6 3 9, CI - 2 0 6 4, Green 'Chemical (share) system name: DTS-102, DTS-103, NAT-103, NDS -1 03, TPS-103, MDS-1 03, and the product names of the Saturnman company: CD-1010, CD-1011, CD-1012, etc. Further, the diaryl scale salt is, for example, a product name of the company: Ilukai 261, a product of the Japanese chemical company (shares): PCI-061T, PCI-062T, PCI-020T, PCI-02 2T, and the like. Among them, the brand names of Unio Co., Ltd. are: UVI-6970, -37-200806701 (34) UV1-6974, UV1-6990, and Asahi Chemical Industry Co., Ltd. Trade name: Aidekau SP-170, SP-17 1. The product name of the product of the company: CD-1012, Green Chemical Co., Ltd. Product name: The protective film obtained by MPI-103 has a high surface hardness. When the curable resin composition of the present invention contains a radiation-sensitive acid generator (D), the amount thereof is preferably from 5 to 20 parts by weight, preferably from 5 to 20 parts by weight, based on 100 parts by weight of the high molecular weight substance (A). It is preferably from 0.1 to 10 parts by weight. When the amount of use φ is in this range, a protective film having sufficient hardness can be obtained. Heat-sensitive acid generator (E) A heat-sensitive acid generator such as a barium salt (excluding the aforementioned triarylsulfonium salt), a benzothiazole iron salt, an ammonium salt, a scale salt, etc., wherein a barium salt is used (the aforementioned triaryl spade) Except for salt), benzothiazole key salt is preferred. Specific examples of the above sulfonium salt (excluding the aforementioned triarylsulfonium salt) include 4-ethyl phenyl phenyl trimethyl sulfonium hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, Dimethyl-4-(n-oxyorthooxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzoxyloxy)phenylphosphonium hexafluoroantimonate^, dimethyl one 4-(phenoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate is an alkyl phosphonium salt; benzyl-4 Hydroxyphenylmethyl hydrazine hexafluoroantimonate, benzyl- 4-hydroxyphenylmethyl hexafluorophosphate, 4-ethoxycarbonylphenylbenzylmethyl hexafluoroantimonate, benzyl- 4-methoxyphenylmethyl sulfonium hexafluoroantimonate, benzyl-2 methyl mono-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl 3-chloro-4-hydroxyphenyl Methyl hydrazine hexafluoroarsenate, 4-methoxybenzyl- 4-hydroxy-38-200806701 (35) benzyl sulfonium salt such as phenylmethyl hexafluorophosphate; dibenzyl-4-hydroxyl Phenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethenyloxyphenyl Dibenzyl hexafluoroantimonate, dibenzyl-4-methoxy methoxy hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenyl hexafluoroarsenate, dibenzyl Benzyl such as 3-methyl-1,4-tetrahydroxy-5-tert-butylphenylphosphonium hexafluoroantimonate or benzyl-4-methyl-oxybenzyl-4-hydroxyphenyl mirror hexafluorophosphate Base salt; φ P -chlorobenzyl-4 tetrahydroxyphenylmethyl hexafluoroantimonate, p-nitrobenzyl- 4-hydroxyphenylmethyl hexafluoroantimonate, p-chlorobenzyl Benzyl 4-hydroxyphenylmethyl sulfonium hexafluorophosphate, P-nitrobenzyl-3-methoxy-5-hydroxyphenylmethyl hexafluoroantimonate, 3,5-dichlorobenzyl A substituted benzyl sulfonium salt such as 4-hydroxyphenylmethyl sulfonium hexafluoroantimonate or fluorenyl-chlorobenzyl- 3 -chloro-4-hydroxyphenylmethyl hexafluoroantimonate. Among them, 4-ethoxyphen phenyl dimethyl hexafluoroarsenate, benzyl- 4-hydroxyphenylmethyl hexafluoroantimonate, 4-glycidyl benzyl benzyl ester Methyl hydrazine hexafluoroantimonate, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-ethoxycarbonylphenylbenzyl hexafluoroantimonate or the like is preferred. ^ The above benzothiazole iron salt, such as 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazole hexafluorophosphate, 3-benzylbenzothiazole key tetrafluoroborate, 3 —( p —methoxybenzyl)benzothiazole iron hexafluoroantimonate, 3-benzyl-2-methylthiazole hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazole Benzylbenzothiazole iron salt such as fluoroantimonate. Among them, 3-benzylbenzothiazolium hexafluoroantimonate or the like is used. A commercial product suitable for use as an acid generator for a sensible acid generator, such as alkyl hydrazine • 39-200806701 (36)

鹽之旭電化工業（股）製商品名：艾得考CP-66、CP_77 ° 又，苄基毓鹽如，三新化學工業（股）製商品名： SI-6 0' SI-80' S1-100' SI-110' SI-145' SI-150' SI-80L 、SI-100L、SI-1 10L ° 其中又以SI-80、SI-100、SI-110所得之保護膜具有局 表面硬度爲佳。 • 本發明之樹脂組成物爲含有（E )感熱酸發生劑之物 φ 時，其使用量對高分子量物（A) 10 0重量份較佳爲〇·〇5至 2 0重量份，更佳爲〇 · 1至1 〇重量份。使用量爲該範圍時可 得具有充分硬度之保護膜。 其他成份 如上述，本發明之樹脂組成物係以高分子量物（A ) 爲必須成份，又必要時可含有乙烯性不飽和化合物（B) ，及另含有（C)環氧化合物及/或（D)感放射線性酸 • 發生劑及/或（E )感熱性酸發生劑，但必要時可含有其 他成份。該類其他成份如，（F )表面活性劑、（G )接 ^ 著助劑等。 表面活性劑（F ) 上述表面活性劑之添加目的爲，提升本發明之樹脂組 成物的塗佈性能。 該類表面活性劑如’氟系表面活性劑、聚矽氧烷系表 面活性劑、非離子系表面活性劑、其他表面活性劑。 -40- 200806701 (37) 上述氟系表面活性劑如，BM CHIMIE公司製商品名： BM- 1 000、BM-1100、大日本油墨化學工業（股）製商品 名：美佳發F〗4 2 D、F 1 7 2、F 1 7 3、F 1 8 3、住友3 Μ (股）製 商品名：佛洛拉 FC-135、FC-170C、FC-430、FC-431、旭 硝子（股）製商品名：撒佛隆S-112、S-113、S-131、 S-141、 S-145、 S-382、 SC-101、 SC-102、 SC-103、 ^ SC-104、 SC-105、 SC-106等市售品。 m 上述聚矽氧烷系表面活性劑如，東雷島（股）製商品 名：SH-28PA、SH-19 0、SH-193、SZ-6 032、SF-842 8、 DC-57、DC-190、住越化學工業（股）製商品名：ΚΡ34Ϊ 、新秋田化成（股）製商品名··耶佛特EF301、EF3 03、 EF35 2等巾售品。 上述非離子系表面活性劑如，聚環氧乙烷烷基醚、聚 環氧乙烷芳基醚、聚環氧乙烷二烷基酯等。 上述聚環氣乙烷烷基醚如，聚環氧乙烷月桂醚、聚環 φ 氧乙烷硬脂醚、聚環氧乙烷油醚等，聚環氧乙烷芳基醚如 ，聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚、聚環氧乙 • 烷二烷基酯如，聚環氧乙烷二月桂酸酯、聚環氧乙烷二硬 脂酸酯等。 上述其他表面活性劑如，共榮社化學（股）製商品名 ：(甲基）丙烯酸系共聚物聚流Ν〇.57、Ν〇·90等。 此等（F )表面活性劑之添加量對高分子量物（A ) 每1 0 0重量份較佳爲5重量份以下，更佳爲2重量份以下。 表面活性劑量超過5重量份時，塗佈步驟易產生塗膜雛摺 -41 - 200806701 (38) 接著助劑（G ) 上述（G )接著助劑之添加目的爲，提升所形成之保 S蒦膜與基板的密合性。 該類（G )接著助劑可使用，例如具有反應性取代基 * 之官能性矽烷偶合劑。上述反應性取代基如，羧基、甲基 φ 丙烯醯胺、異氰酸酯基、環氧基等。 (〇 )接著助劑之具體例如，三甲氧基矽烷基安息香 酸、7 —甲基丙烯氧基丙基三甲氧基矽烷 '乙烯基三乙醯 氧基矽烷、乙烯基三甲氧基矽烷、r 一異氰酸酯丙基三乙 氧基砂院、7 -環氧丙氧基丙基三甲氧基砂院、( 3，4 一環氧己基）乙基三甲氧基矽烷等。 該類（G)接著助劑之使用量對高分子量物（A)肇 10 0重量份較佳爲30重量份以下，更佳爲25重量份以下。 # ( G )接著助劑量超過30重量份時，會使所得保護膜之耐 熱性不足。 硬化性樹脂組成物 本發明之硬化性樹脂組成物係以上述高分子量物（A )爲必須成份，又必要時可含有乙烯性不飽和化合物（B )、環氧化合物（C )、感放射線性酸發生劑（D )、感 熱性酸發生劑（E )、表面活性劑（F )及接著助劑（G ) -42、 200806701 (39) 本發明之硬化性樹脂組成物較佳由，適當有 均勻分解或分散上述各成份調製而得。所使用之 爲，能溶解或分散組成物之各成份，且不會與各 之物。 該類溶劑如，醇、醚、二元醇醚、乙二醇烷 酯、二乙二醇一烷基醚、二乙二醇二烷基醚、丙 基醚、丙二醇烷基醚乙酸酯、丙二醇烷基醚丙酸 族烴、酮、酯等。 此等具體例如，甲醇、乙醇、苄醇等醇； 四氫呋喃等醚； 乙二醇一甲醚、乙二醇一乙醚等二元醇醚； 甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙 醚乙酸酯、二乙二醇一乙醚乙酸酯等乙二醇烷基 9 二乙二醇一甲醚、二乙二醇一乙醚等二乙二 醚； 二乙二醇二甲醚、二乙二醇二乙醚、二乙二 醚等二乙二醇二烷基醚； 丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙 等丙二醇一烷基醚； 丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙 乙酸酯 '丙二醇丁醚乙酸酯等丙二醇烷基醚乙酸 丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙 丙酸酯、丙二醇丁醚丙酸酯等丙二醇烷基醚丙酸 機溶劑中 溶劑較佳 成份反應 基醚乙酸 二醇一烷 醋、芳香 二醇一丁 醚乙酸酯 醇一院基 醇乙基甲 二醇丁醚 二醇丙醚 酯； 二醇丙醚 -43- 200806701 (40) 甲苯、二甲苯等芳香族烴； 甲基乙酮、環己酮、4一經基一4 一甲基一2 —戊酮、 甲基異戊酮等酮； 乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2一經 基丙酸乙酯、2-羥基一2—甲基丙酸甲酯、2一羥基一2 — 甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸 ^ 丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3 — ❿ 羥基丙酸甲酯、3—羥基丙酸乙酯、3 —羥基丙酸丙酯、3 —羥基丙酸丁酯、2—羥基一 3 —甲基丁酸甲酯、甲氧基乙 酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸 丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙 酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯 、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、 丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2· 一甲氧基丙酸甲酯、2—甲氧基丙酸乙酯、2—甲氧基丙酸 φ 丙酯、2—甲氧基丙酸丁酯、2—乙氧基丙酸甲酯、2-乙 m 氧基丙酸乙酯、2-乙氧基丙酸丙酯、2—乙氧基丙酸丁酯 ‘ 、2 — 丁氧基丙酸甲酯、2—丁氧基丙酸乙酯、2一 丁氧基 丙酸丙酯、2 -丁氧基丙酸丁酯、3 -甲氧基丙酸甲酯、3 一甲氧基丙酸乙酯、3—甲氧基丙酸丙酯'3 —甲氧基丙酸 丁酯、3 -乙氧基丙酸甲酯、3 —乙氧基丙酸乙酯、3一乙 氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯 、3-丙氧基丙酸乙酯、3 —丙氧基丙酸丙酯、3-丙氧基 丙酸丁醋、3 —丁氧基丙酸甲酯、3 -丁氧基丙酸乙醋、3 -44- 200806701 (41) -丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等酯。 其中較佳爲醇、二乙二醇、丙二醇烷基乙酸酯、乙二 醇烷基醚乙酸酯、二乙二醇二烷基醚，特佳爲苄醇、二乙 二醇乙基甲醚、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、 二乙二醇二甲醚、乙二醇一丁醚乙酸酯、二乙二醇一乙醚 乙酸酯、二乙二醇二乙醚。 ^ 溶劑使用量較佳爲，能使本發明組成物中之全固體成 φ 扮（甶含溶劑之組成物總量去除溶劑量的量）含量爲1至 50重量％，更佳爲5至40重量％之量。 前述溶劑可倂用高沸點溶劑。可倂用之高沸點溶劑如 ，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、Ν,Ν —二甲基乙醯胺、N —甲基吡咯 烷酮、二甲基亞颯、苄基乙醚、二己醚、丙酮基丙酮、異 佛爾酮、己酸、癸酸、1 -辛醇、1 一壬醇、乙酸苄酯、安 息香酸乙酯、草酸二乙酯、馬來酸二乙酯、r 一丁內酯、 • 碳酸乙烯、碳酸丙烯、苯基溶纖劑乙酸酯等。 倂用高沸點溶劑時其使用量對全溶劑量較佳爲90重量 ‘ ％以下，更佳爲80重量％以下。 上述調製所得之組成物可使用孔徑0.2至3·〇 μ m，較 佳爲孔徑0.2至0.5 # m之米利波阿濾器等過濾後供使用。 形成彩色濾光片之保護膜 下面將說明使用本發明之硬化性樹脂組成物形成彩色 濾光片之保護膜的方法 -45- 200806701 (42) 本發明之硬化性樹脂組成物爲含有上述高分子量物（ A )之必須成份，及必要時使用之乙烯性不飽和化合物（ B ) ’以及任意之環氧化合物（C )及/或表面活性劑（F )及/或接著助劑（G)之物時，或含有上述高分子量物 (A )及感熱性酸發生劑（Ε )，以及任意之環氧化合物 (C )、表面活性劑（F )及/或接著助劑（G )之物時， * 將該樹脂組成物塗佈於基板表面上，預烤以去除溶劑形成 φ 塗膜後加熱處理，可形成目的之彩色濾光片的保護膜。 上述基板可使用之物如，玻璃、石英、矽、樹脂等基 板。該樹脂如，聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁 二醇酯、聚酯颯、聚碳酸酯、聚醯亞胺、環氧烯烴之開環 聚合物及其氫添加物般樹脂。 塗佈方法可採用例如噴霧法、輥塗法、回轉塗佈法、 棒塗佈法、噴墨法等適當方法，特別適合使用旋塗機、噴 霧不旋塗佈機、狹縫模頭塗佈機塗佈。 9 上述預烤條件會因各成份之種類及添加比率等而異， ψ 較佳爲採用70至90 °C下1至15分鐘之條件。塗膜厚度較佳 爲0.15至8.5/zm，更佳爲0.15至6.5// m，特佳爲0.1 5至4.5 //m。又已理解該塗膜厚度爲去除溶劑後之厚度。 形成塗膜後之加熱處理可利用熱板、清潔烤箱等適當 加熱裝置實施。處理溫度較佳爲150至2 5(TC，使用熱板時 所採用之加熱時間可爲5至3 0分鐘，使用烤箱時可採用3 0 至90分鐘之處理時間。 又本發明之硬化性樹脂組成物爲含有上述高分子量物 -46 - 200806701 (43) (A )及感放射線性酸發生劑（D )，以及任意之環 合物（C )及/或表面活性劑（F )及/或接著助劑（ 之物時，將該樹脂組成物塗佈於基板表面上，預烤以 溶劑形成塗膜後進行放射線照射處理（曝光處理）， 成目的之保護膜。又必要時可於曝光處理後進行加熱 〇 # 此時所使用之基板，形成塗膜之方法可同上述。 ^ 厚度較佳爲〇 · 1 5至8 · 5 /i m，更佳爲0 : 1 5至6 s 5 /j m，特 0.1 5至4 · 5 // m。又已理解該塗膜厚度爲去除溶劑後之 〇 上述照射放射線處理所使用之放射線可爲可視光 紫外線、遠紫外線、電子線、X線等，但以含有波j 至4 5 0 nm之光線的紫外線爲佳。 曝光量較佳爲100至20,000：f/m2，較佳爲1 1 0,000J/m2。 ♦ 照射放射線後可另進行任意之加熱處理。此時之 攀 溫度較佳爲150至250°C，所使用之加熱裝置可爲熱板 潔烤箱等適當裝置。使用熱板時所採用之加熱時間1 至30分鐘，使用烤箱時可採用30至90分鐘之處理時間 彩色濾光片之保護膜 該類形成之保護膜的膜厚較佳爲0.1至8// m，更 0 · 1至6 // m，特佳爲〇. 1至4 // m。又本發明之保護膜 於具有彩色濾光片段差之基板上時，可理解該膜厚 氧化 G) 去除 可形 處理 塗膜 佳爲 厚度 線、 I 190 50至 加熱 、清 叮爲5 佳爲 形成 彩色 -47- 200806701 (44) 濾光片最上面算起之厚度。 由下述實施例得知，本發明之保護膜適用爲，可符合 密合性、表面硬度、透明性、耐熱性、耐光性、耐溶劑性 等條件，且加熱狀態下也不會因荷重而凹陷，又具有優良 的能使形成於底層基板上之彩色濾光片段差平坦化性能的 光裝置用保護膜。 ° 特別是面板製造步騾中，本發明之保護膜曝光於超過 φ 25(TC之加熱狀態下也能具有充分耐熱性，又270。(：下可保 證具有充分尺寸安定性。 因此本發明係提供，適用於形成既使於表面平坦性較 差之基體上，也可於該基體上形成平坦性高之硬化膜，且 可具有高透明性、高表面硬度及優良之耐熱電壓性、密合 性、耐酸性、耐鹼性、耐濺污性等各種耐性的光裝置用保 護膜，具有優良組成物用之保存安定性的樹脂組成物，使 用該樹脂組成物之保護膜的形成方法，及上述組成物所形 • 成之保護膜。 - 【實施方式】 實施例 下面將以合成例及實施例更具體說明本發明，但本發 明非限於下列實施例。 製造高分子量物（A) 合成例1 -48- 200806701 (45) 將2，2’ 一偶氮雙（2,4 一二甲基戊腈）2重量份、二乙 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯〗5重量份、1 一 （環己氧基）乙基甲 基丙烯酸酯20重量份、3-甲基丙烯氧基丙基三甲氧基矽 院10重量份、甲基丙烯酸環氧丙酯45重量份及甲基丙烯酸 三環[5·2·1.02,6]癸烷一 8—酯10重量份，氮取代後開始緩 一 緩攪拌。將溶液溫度升至70 °C後保持該溫度5小時，得含 A 共聚物（A-1 )之聚合物溶液。所得聚合物溶液之固體成 份濃度爲3 3重量％。又共聚物（a-之重量平均分子量 (Mw )、數平均分子量（Μη )及Mw/Mn如表1所示。 合成例2 將2,2 -偶氮雙（2,4 一二甲基戊腈）5重量份、二乙 1醇=S甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯1 5重量份、四氫一 2 Η —吡喃—2 -基 參 甲基丙嫌酸酯20重量份、3 —甲基丙烯氧基丙基三甲氧基 石夕院5重量份、甲基丙烯酸環氧丙酯4〇重量份及環己基馬 來酸亞胺2〇重量份’氮取代後開始緩緩攪拌。將溶液溫度 升至7〇°C後保持該溫度5小時，得含有共聚物（α-2 )之聚 合物彳谷 '液。所得聚合物溶液之固體成份濃度爲3 3重量％。 又共聚物（Α-2 )之Mw、Μη及Mw/Mn如表1所示。 合成例3 將2,2’一偶氮雙（2,4一二甲基戊腈）1〇重量份、二乙 -49- 200806701 (46) 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯1 5重量份、1 -(-環己氧基）乙基甲 基丙烯酸酯20重量份、3 -甲基丙烯氧基丙基三甲氧基矽 烷〗〇重量份、甲基丙烯酸環氧丙酯40重量份及環己基馬來 醯亞胺1 5重量份，氮取代後開始緩緩攪拌。將溶液溫度升 至70°C後保持該溫度5小時，得含有共聚物（A-3 )之聚合 . 物溶液，所得聚合物溶液之固體成份濃度爲32.7重量％。 m 又共聚物（A-3 )之Mw、Μη及Mw/Mn如表1所示。 合成例4 將2，2’ 一偶氮雙（2,4 一二甲基戊腈）5重量份、二乙 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯13重量份、1 一（環己氧基）乙基甲 基丙烯酸酯25重量份、3 -甲基丙烯氧基丙基三甲氧基磙 烷15重量份、甲基丙烯酸環氧丙酯30重量份及環己基馬來 # 醯亞胺1 7重量份’氮取代後開始緩緩攪拌。將溶液溫度升 至7 0 °C後保持該溫度5小時，得含有共聚物（A - 4 )之聚合 • 物溶液。所得聚合物溶液之固體成份濃度爲3 3重量％。又 共聚物（A-4)之Mw、Mn及Mw/Mn如表1所示。 合成例5 將2，2’ 一偶氮雙（2，4 一二甲基戊腈）8重量份、二乙 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯1 5重量份、t — 丁基甲酸丙烯酸酯2 〇 -50- 200806701 (47) 重量份、3—甲基丙烯氧基丙基三甲氧基矽烷5重量份、甲 基丙烯酸環氧丙酯4 0重量份及環己基馬來醯亞胺2 0重量份 ’氮取代後開始緩緩攪拌。將溶液溫度升至7(TC後保持該 溫度5小時，得含有共聚物（A-5 )之聚合物溶液。所得聚 合物溶液之固體成份濃度爲33重量％。又共聚物（A-5 ) 之Mw、Μη及Mw/Mn如表1所示。 φ 合成例6 將2,2’ 一偶氮雙（2,4 一二甲基戊腈）5重量份、二乙 二醇乙基甲醚200重量份放入備有冷卻管及攬拌機之燒瓶 中。其次放入苯乙烯18重量份、2，3 —二羧酸四氫吡喃一 2 -基氧基羰基- 5 -降莰烯20重量份、3—丙烯氧基丙基三 甲氧基矽烷10重量份、甲基丙烯酸環氧丙酯4〇重量份及環 己基馬來醯亞胺1 2重量份，氮取代後開始緩緩攪拌。將灌 液溫度升至7 0 °C後保持該溫度5小時，得含有共聚物（A - 6 ® )之聚合物溶液。所得聚合物溶液之固體成份濃度爲3 3重 量％。又共聚物（A-6)之Mw、Μη及Mw/Mn如表1所示。 合成例7 將2,2’ 一偶氮雙（2,4一二甲基戊腈）5重量份及二乙 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中，其次放入3 —丙烯氧基丙基三甲氧基矽烷5重量份、甲 基丙烯酸環氧丙酯4 5份、馬來酸酐；1 5份、n -環己基馬來 醯亞胺1 5份及苯乙烯20份，氮取代後開始緩緩攪拌。將反 -51 - 200806701 (48) 應溶液之溫度升至70。(：後保持該溫度5小時，再滴入i 一丙 基乙嫌醚3 〇份，其後攪拌同時反應2小時，得含有共聚物 (A-7 )之聚合物溶液。所得聚合物溶液之固體成份濃度 爲33.2重量％。又共聚物（A-7 )之Mw、Μη及Mw/Mn如表 1所示。 ^ 合成例8 • 將2，2’一偶氮雙（2,4 —二甲基戊腈）2重量份、二乙 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯15重量份、1 一乙基環戊基甲基丙烯 酸酯20重量份、3 —甲基丙嫌氧基丙基三甲氧基砂院10重 量份、甲基丙烯酸環氧丙酯4 5重量份及甲基丙烯酸三環 [5.2.1 ·02’6]癸烷一 8 -酯10重量份，氮取代後開始緩緩攪 拌。將溶液溫度升至7 0 Τ：後保持該溫度5小時，得含有共 聚物（Α- 8 )之聚合物溶液。所得聚合物溶液之固體成份 • 濃度爲33重量％。又共聚物（Α-8)之重量平均分子量（ M w )、數平均分子量（Μη)及Mw/Mn如表1所示。 比較合成例1 將2，2’一偶氮雙（2，4一二甲基戊腈）2重量份、二乙 二醇乙基甲醚2〇〇重量份放入備有冷卻管及攪拌機之燒瓶 中。其次放入苯乙烯25重量份、甲基丙烯酸20重量份、甲 基丙烯酸環氧丙酯45重量份及甲基丙烯酸三環[5.2.1 ·02’6] 癸烷- 8 -酯1 〇重量份，氮取代後開始緩緩攪拌。將溶液 •52- 200806701 (49) 溫度升至70 °C後保持該溫度5小時，得含有共聚物（A-1 ) 之聚合物溶液。所得聚合物溶液之固體成份濃度爲3 3重量 %。又共聚物（a-Ι)之Mw、Μη及Mw/Mn如表1所示。 比較合成例2 將2,2’ 一偶氮雙（2,4 —二甲基戊腈）20重量份、二乙 • 二醇乙基甲醚200重量份放入備有冷卻管及攪拌機之燒瓶 ❿ 中。其次放入苯乙烯25重量份、1—(環己氧基）乙基甲 基丙烯酸酯20重量份、甲基丙烯酸環氧丙酯45重量份及甲 基丙烯酸三環[5.2.1.02,6]癸烷—8 -酯10重量份，氮取代 後開始緩緩攪拌。將溶液溫度升至70 °C後保持該溫度5小 時’得含有共聚物（a- 2 )之聚合物溶液。所得聚合物溶 液之固體成份濃度爲32.8重量％。又共聚物（a_2 )之Mw 、Μη及Mw/Mn如表1所示。Yanzhixu Electrochemical Industry Co., Ltd. Product Name: Adeco CP-66, CP_77 ° Also, benzyl sulfonium salt, Sanshin Chemical Industry Co., Ltd. Trade name: SI-6 0' SI-80' S1 -100' SI-110' SI-145' SI-150' SI-80L, SI-100L, SI-1 10L ° The protective film obtained with SI-80, SI-100, SI-110 has a surface hardness It is better. • When the resin composition of the present invention is a substance φ containing (E) a sensible acid generator, the amount thereof is preferably from 10 to 20 parts by weight, more preferably from 10 to 20 parts by weight, per 100 parts by weight of the high molecular weight substance (A). It is 1 to 1 part by weight. When the amount used is in this range, a protective film having sufficient hardness can be obtained. Other Ingredients As described above, the resin composition of the present invention contains the high molecular weight (A) as an essential component, and if necessary, the ethylenically unsaturated compound (B), and further contains (C) an epoxy compound and/or ( D) Radiation-sensitive acid generators and/or (E) sensitizing acid generators, but may contain other ingredients if necessary. Such other components as (F) surfactant, (G), and the like. Surfactant (F) The above surfactant is added for the purpose of improving the coating properties of the resin composition of the present invention. Such surfactants are, for example, 'fluoro-based surfactants, polyoxyalkylene-based surfactants, nonionic surfactants, and other surfactants. -40- 200806701 (37) The above-mentioned fluorine-based surfactants, for example, are manufactured by BM CHIMIE Co., Ltd.: BM-1 000, BM-1100, Dainippon Ink Chemical Industry Co., Ltd. Trade name: Meijiafa F〗 4 2 D , F 1 7 2, F 1 7 3, F 1 8 3, Sumitomo 3 Μ (share) system name: Flora FC-135, FC-170C, FC-430, FC-431, Asahi Glass Co., Ltd. Product Name: Saffron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, ^ SC-104, SC-105 , SC-106 and other commercial products. m The above polyoxyalkylene-based surfactants, for example, manufactured by Toray Island Co., Ltd., trade names: SH-28PA, SH-19 0, SH-193, SZ-6 032, SF-842 8, DC-57, DC -190, Suohui Chemical Industry Co., Ltd. Product Name: ΚΡ34Ϊ, New Akita Chemicals Co., Ltd. Product Name··Yevte EF301, EF3 03, EF35 2 and other towel sales. The above nonionic surfactants are, for example, polyethylene oxide alkyl ether, polyethylene oxide aryl ether, polyethylene oxide dialkyl ester and the like. The above polycyclohexane ethylene ether such as polyethylene oxide lauryl ether, polycycloethylene oxide stearyl ether, polyethylene oxide oleyl ether, etc., polyethylene oxide aryl ether such as polycyclic ring Ethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, polyethylene oxide dialkyl ester such as polyethylene oxide dilaurate, polyethylene oxide distearate Wait. The above-mentioned other surfactants are, for example, trade names of Kyoeisha Chemical Co., Ltd.: (meth)acrylic copolymers, polycondensation Ν〇.57, Ν〇90, and the like. The amount of the (F) surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less per 100 parts by weight of the high molecular weight substance (A). When the surfactant amount exceeds 5 parts by weight, the coating step is liable to cause a film to be folded. -41 - 200806701 (38) Next, the auxiliary agent (G) is added to the above (G) and the auxiliary agent is added to enhance the formed protective layer. Adhesion of the film to the substrate. Such a (G) adjunct agent can be used, for example, a functional decane coupling agent having a reactive substituent*. The above reactive substituent is, for example, a carboxyl group, a methyl φ acrylamide, an isocyanate group or an epoxy group. (〇) specific examples of the auxiliary agent, for example, trimethoxydecyl benzoic acid, 7-methacryloxypropyltrimethoxydecane 'vinyl triethoxy decane, vinyl trimethoxy decane, r Isocyanate propyl triethoxy sand pot, 7-glycidoxypropyl trimethoxy sand pot, (3,4-epoxyhexyl) ethyl trimethoxy decane, and the like. The amount of the (G)-based auxiliary agent to be used is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of the high molecular weight substance (A). #(G) When the amount of the auxiliary agent exceeds 30 parts by weight, the heat resistance of the obtained protective film is insufficient. The curable resin composition of the present invention contains the above-mentioned high molecular weight substance (A) as an essential component, and may contain an ethylenically unsaturated compound (B), an epoxy compound (C), and a radiation-sensitive linearity as necessary. Acid generator (D), heat-sensitive acid generator (E), surfactant (F), and adhesion aid (G) -42, 200806701 (39) The curable resin composition of the present invention is preferably composed of It is obtained by uniformly decomposing or dispersing the above components. It is used to dissolve or disperse the components of the composition and does not interfere with each other. Such solvents are, for example, alcohols, ethers, glycol ethers, glycol alkyl esters, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propyl ethers, propylene glycol alkyl ether acetates, Propylene glycol alkyl ether propionic acid hydrocarbons, ketones, esters, and the like. These are, for example, alcohols such as methanol, ethanol, and benzyl alcohol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methyl cellosolve acetate and ethyl cellosolve. Ethylene glycol alkyl 9 diethylene glycol monomethyl ether such as acetate, diethyl ether acetate or diethylene glycol monoethyl ether acetate; diethylene glycol such as diethylene glycol monoethyl ether; diethylene glycol II Diethylene glycol dialkyl ether such as methyl ether, diethylene glycol diethyl ether or diethyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol and other propylene glycol monoalkyl ether; propylene glycol methyl ether acetate, Propylene glycol alkyl ether, propylene glycol ester, propylene glycol butyl ether acetate, propylene glycol alkyl ether acetate, propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propionate, propylene glycol butyl ether propionate, etc. Base ether propionic acid machine solvent, preferred component, reactive group, ether, acetic acid diol, monoalkyl vinegar, aromatic diol, monobutyl ether acetate, alcohol, ethyl methacrylate, butyl ether glycol propyl ether ester, diol Diethyl ether-43- 200806701 (40) Aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexyl a ketone such as 4-methyl-mono-2-pentanone or methyl isoamyl ketone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-propyl propylate, 2-hydroxyl Methyl 2-methylpropionate, ethyl 2-hydroxy-2-oxopropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate , butyl lactate, 3-hydrazone methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate Methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Propyl oxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, φ propyl 2-methoxypropionate, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethyloxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2 - butyl Methyl oxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, propyl 3-methoxypropionate butyl 3-methoxypropanoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-B Propyl oxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propane Butyl oxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-44-200806701 (41)-propylbutoxypropionate, 3-butoxypropane An ester such as butyl acrylate. Among them, preferred are alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether, particularly preferably benzyl alcohol, diethylene glycol ethyl methyl Ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether. The solvent is preferably used in an amount such that the total solid content in the composition of the present invention is φ (the amount of the solvent-containing composition is a total amount of the solvent removed) of from 1 to 50% by weight, more preferably from 5 to 40. The amount by weight%. The aforementioned solvent can be used with a high boiling point solvent. High-boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, hydrazine, hydrazine-dimethyl Ethyl amide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, citric acid, 1-octyl alcohol, 1-nonanol, Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, • ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. When the high-boiling solvent is used, the amount of the solvent used is preferably 90% by weight or less, more preferably 80% by weight or less. The composition obtained by the above-mentioned preparation can be used after being filtered using a pore size of 0.2 to 3 · 〇 μ m, preferably a Millipo filter having a pore diameter of 0.2 to 0.5 # m. Protective film forming a color filter, a method of forming a protective film of a color filter using the curable resin composition of the present invention - 45-200806701 (42) The curable resin composition of the present invention contains the above-mentioned high molecular weight The essential component of the substance (A), and if necessary, the ethylenically unsaturated compound (B)' and any epoxy compound (C) and/or surfactant (F) and/or the subsequent auxiliary agent (G) Or the above-mentioned high molecular weight (A) and sensible acid generator (Ε), and any of the epoxy compound (C), the surfactant (F) and/or the auxiliary agent (G) * The resin composition is applied onto the surface of the substrate, pre-baked to remove the solvent to form a φ coating film, and then heat-treated to form a protective film for the desired color filter. The substrate can be used, for example, a substrate such as glass, quartz, rhodium, or resin. The resin is, for example, polyethylene terephthalate, polybutylene terephthalate, polyester oxime, polycarbonate, polyimide, ring-opening polymer of epoxy olefin and hydrogen additive thereof General resin. The coating method may be, for example, a suitable method such as a spray method, a roll coating method, a rotary coating method, a bar coating method, or an inkjet method, and is particularly preferably a spin coater, a spray spin coater, or a slit die coating. Machine coating. 9 The above pre-bake conditions vary depending on the type of ingredients and the ratio of addition, etc. ψ It is preferably used at 70 to 90 °C for 1 to 15 minutes. The film thickness is preferably from 0.15 to 8.5/zm, more preferably from 0.15 to 6.5/m, and particularly preferably from 0.15 to 4.5 //m. It is also understood that the thickness of the coating film is the thickness after solvent removal. The heat treatment after the formation of the coating film can be carried out by a suitable heating means such as a hot plate or a cleaning oven. The treatment temperature is preferably from 150 to 25 (TC, the heating time used for the hot plate may be 5 to 30 minutes, and the oven may be used for a treatment time of 30 to 90 minutes. Further, the curable resin of the present invention. The composition contains the above high molecular weight compound -46 - 200806701 (43) (A) and a radioactive acid generator (D), and any cyclized compound (C) and / or surfactant (F) and / or Next, when the auxiliary agent is used, the resin composition is applied onto the surface of the substrate, pre-baked with a solvent to form a coating film, and then subjected to radiation irradiation treatment (exposure treatment) to form a protective film for the purpose. After heating, the substrate used at this time can be formed by the same method as above. ^ The thickness is preferably 〇·1 5 to 8 · 5 /im, more preferably 0: 1 5 to 6 s 5 /jm , 0.1 5 to 4 · 5 // m. It is understood that the thickness of the coating film is after removing the solvent. The radiation used for the above-mentioned radiation treatment may be visible ultraviolet light, far ultraviolet light, electronic light, X-ray, etc., but It is preferred to use ultraviolet rays having a wavelength of from j to 450 nm. The exposure amount is preferably 100. Up to 20,000: f/m2, preferably 1 1 0,000 J/m2 ♦ Any radiation treatment may be performed after the radiation is irradiated. The climbing temperature is preferably 150 to 250 ° C, and the heating device used may be Suitable equipment such as hot plate cleaning oven. The heating time used for hot plate is 1 to 30 minutes. When using oven, it can be used for 30 to 90 minutes. The protective film of color filter is the film thickness of the protective film. Preferably, it is 0.1 to 8//m, more preferably 0. 1 to 6 // m, particularly preferably 〇. 1 to 4 // m. Further, when the protective film of the present invention is applied to a substrate having a color filter segment difference, It can be understood that the film thickness oxidation G) removes the shapeable coating film as the thickness line, I 190 50 to heat, and the clearing is 5 to form the color -47-200806701 (44) The thickness of the filter is calculated from the top. It is understood from the following examples that the protective film of the present invention is suitable for conditions such as adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like, and does not cause load due to heating. The recess has excellent excellent color filter segments formed on the underlying substrate The protective film for the optical device of the performance. ° Especially in the panel manufacturing step, the protective film of the present invention is exposed to more than φ 25 (the TC can also have sufficient heat resistance in the heated state, and 270. (: can be guaranteed to have The present invention provides that it can be used to form a cured film having high flatness even on a substrate having poor surface flatness, and can have high transparency and high surface hardness. A protective film for an optical device having excellent heat resistance voltage resistance, adhesion, acid resistance, alkali resistance, and splash resistance, and a resin composition having excellent storage stability for a composition, and the resin composition is used. A method of forming a protective film and a protective film formed by the above composition. [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples. Production of High Molecular Weight (A) Synthesis Example 1 - 48 - 200806701 (45) 2 parts by weight of 2,2'-azobis(2,4-dimethylpentanenitrile), diethylene glycol ethyl methyl ether 200 Parts by weight are placed in a flask equipped with a cooling tube and a stirrer. Next, 5 parts by weight of styrene, 20 parts by weight of 1-(cyclohexyloxy)ethyl methacrylate, 10 parts by weight of 3-methylpropoxypropyltrimethoxy fluorene, and a methacrylic acid ring were placed. 45 parts by weight of oxypropyl ester and 10 parts by weight of tricyclo[5·2·1.02,6]decane-8-ester of methacrylic acid were mixed with nitrogen and then slowly stirred. After the temperature of the solution was raised to 70 ° C and the temperature was maintained for 5 hours, a polymer solution containing the A copolymer (A-1 ) was obtained. The resulting polymer solution had a solid component concentration of 33% by weight. Further, the copolymer (a-weight average molecular weight (Mw), number average molecular weight (?n), and Mw/Mn are shown in Table 1. Synthesis Example 2 2,2-azobis(2,4-dimethyl pentane) 5 parts by weight of nitrile), 200 parts by weight of diethyl ether = S methyl ether, placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of styrene, tetrahydro-2-pyrene-pyran-2 - 20 parts by weight of methyl propyl acrylate, 5 parts by weight of 3-methyl propylene oxy propyl trimethoxy sylvestre, 4 parts by weight of glycidyl methacrylate and cyclohexyl maleimide 2 After the nitrogen substitution, the stirring was started slowly. After the temperature of the solution was raised to 7 ° C, the temperature was maintained for 5 hours to obtain a polymer solution of the copolymer (α-2 ). The obtained polymer solution was obtained. The solid content concentration was 33% by weight. Further, the Mw, Μη and Mw/Mn of the copolymer (Α-2) are shown in Table 1. Synthesis Example 3 2,2'-azobis(2,4-dimethylene) 1 part by weight of valeronitrile, 2, 4-49-200806701 (46) 200 parts by weight of diol ethyl methyl ether was placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of styrene was placed, 1 -(-cyclohexyloxy 20 parts by weight of ethyl methacrylate, 3 parts by weight of 3-methacryloxypropyltrimethoxydecane, 40 parts by weight of glycidyl methacrylate and 15 parts by weight of cyclohexylmaleimide After the nitrogen substitution, the stirring was started slowly. After the temperature of the solution was raised to 70 ° C and the temperature was maintained for 5 hours, a polymerization solution containing the copolymer (A-3 ) was obtained, and the solid concentration of the obtained polymer solution was 32.7. M%, Μη and Mw/Mn of the copolymer (A-3) are shown in Table 1. Synthesis Example 4 2,2'-azobis(2,4-dimethylpentanenitrile) 5 Parts by weight and 200 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 13 parts by weight of styrene and 1 (cyclohexyloxy)ethyl methacrylate 25 were placed. Parts by weight, 15 parts by weight of 3-methoxypropoxypropyltrimethoxydecane, 30 parts by weight of glycidyl methacrylate, and 7 parts by weight of cyclohexylmaleimide The mixture was stirred slowly, and the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymerization solution containing the copolymer (A - 4 ). The solid content of the polymer solution was 33% by weight, and the Mw, Mn and Mw/Mn of the copolymer (A-4) are shown in Table 1. Synthesis Example 5 2,2'-azo double (2, 4 parts by weight of dimethyl valeronitrile, 200 parts by weight of diethylene glycol ethyl methyl ether, placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of styrene, t-butyl formate Acrylate 2 〇-50- 200806701 (47) parts by weight, 5 parts by weight of 3-methacryloxypropyltrimethoxydecane, 40 parts by weight of glycidyl methacrylate and cyclohexylmaleimide After 20 parts by weight of 'nitrogen substitution, the stirring was started slowly. The temperature of the solution was raised to 7 (the temperature was maintained for 5 hours after TC to obtain a polymer solution containing the copolymer (A-5). The solid content of the obtained polymer solution was 33% by weight. Further copolymer (A-5) Mw, Μη and Mw/Mn are shown in Table 1. φ Synthesis Example 6 5 parts by weight of 2,2'-azobis(2,4-dimethylpentanenitrile), diethylene glycol ethyl methyl ether 200 parts by weight was placed in a flask equipped with a cooling tube and a mixer. Next, 18 parts by weight of styrene, 2,3-dicarboxylic acid tetrahydropyran-2-yloxycarbonyl-5-norbornene was placed. 20 parts by weight, 10 parts by weight of 3-propoxypropyltrimethoxydecane, 4 parts by weight of glycidyl methacrylate and 12 parts by weight of cyclohexylmaleimide, and slowly stirred after nitrogen substitution After the temperature of the liquid was raised to 70 ° C and maintained at this temperature for 5 hours, a polymer solution containing the copolymer (A - 6 ® ) was obtained, and the solid concentration of the obtained polymer solution was 33% by weight. Mw, Μη and Mw/Mn of (A-6) are shown in Table 1. Synthesis Example 7 5 parts by weight of 2,2'-azobis(2,4-dimethylpentanenitrile) and diethylene glycol Ethyl methyl ether 200 weight The mixture was placed in a flask equipped with a cooling tube and a stirrer, followed by 5 parts by weight of 3-propoxypropyltrimethoxydecane, 45 parts of glycidyl methacrylate, maleic anhydride; 15 parts, 1 part of n-cyclohexylmaleimide and 20 parts of styrene, slowly stirring after nitrogen substitution. The temperature of the solution was raised to 70. (: after maintaining the temperature 5 In an hour, another 3 parts of i-propyl propyl ether was added dropwise, followed by stirring for 2 hours to obtain a polymer solution containing the copolymer (A-7). The solid content concentration of the obtained polymer solution was 33.2% by weight. Further, Mw, Μη and Mw/Mn of the copolymer (A-7) are shown in Table 1. ^ Synthesis Example 8: 2,2'-azobis(2,4-dimethylvaleronitrile) 2 weight 200 parts by weight of diethylene glycol ethyl methyl ether was placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of styrene and 20 parts by weight of 1-ethylcyclopentyl methacrylate were added. - 10 parts by weight of methyl propionate propyl trimethoxy sand, 45 parts by weight of glycidyl methacrylate and tricyclo [5.2.1 · 02' 6] decane methacrylate 10 parts by weight of 8-octyl ester, stirring was started slowly after nitrogen substitution. The temperature of the solution was raised to 70 Τ: after maintaining the temperature for 5 hours, a polymer solution containing the copolymer (Α-8) was obtained. The solid content of the solution was 33% by weight. The weight average molecular weight (M w ), number average molecular weight (Μη) and Mw/Mn of the copolymer (Α-8) are shown in Table 1. Comparative Synthesis Example 1 2 parts by weight of 2'-azobis(2,4-dimethylpentanenitrile) and 2 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and tricyclo [5.2.1 · 02'6] decane-8-ester 1 〇 weight of methacrylic acid. After the nitrogen substitution, the mixture began to stir slowly. After the temperature of the solution was raised to 70 ° C and the temperature was maintained for 5 hours, a polymer solution containing the copolymer (A-1 ) was obtained. The resulting polymer solution had a solid concentration of 33% by weight. Further, Mw, Μη and Mw/Mn of the copolymer (a-Ι) are shown in Table 1. Comparative Synthesis Example 2 20 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. ❿ Medium. Next, 25 parts by weight of styrene, 20 parts by weight of 1-(cyclohexyloxy)ethyl methacrylate, 45 parts by weight of glycidyl methacrylate, and tricyclomethacrylate [5.2.1.02,6] were placed. 10 parts by weight of decane-8-ester was gradually stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-2). The solid content of the obtained polymer solution was 32.8% by weight. Further, Mw, Μη and Mw/Mn of the copolymer (a_2) are shown in Table 1.

表1 合成例1 合成例2 合成例3 合成例4 合成例5 合成例6 合成例7 合成例8 Mw 18,000 7,500 3,800 14,000 9,000 14,000 15,000 17,500 Μη 9,000 4,500 2,000 6,000 5,000 7,000 6,000 8,500 Mw/Mn 2 2 2 2 2 2 3 2 共聚物 (A-1) (A-2 ) (A-3) (A-4) (Α·5) (Α-6) (Α-7) (Α-8 ) -53 - 200806701 (50) 表1 (續） 比較合成例1 比較合成例2 M w 2 0,000 80 0 Μη 9,000 500 M w / Μ η 2 2 共聚物 (a * 1) - (a-2) 調製及評估樹脂組成物 實施例1 加入上述合成例1所得含有共聚物（a- 1 )之溶液（相 當於共聚物（A-1) 100重量份（固體成份）之量）’及（ B)三丙烯醯氧基季戊四醇琥珀酸（TAPS) 50.0重量份， 及（F )表面活性劑SH-28PA (東雷島（股）製）〇.1重量 份及（G)接著助劑7 -環氧丙氧基丙基三甲氧基矽烷15 重量份，再加入丙二醇-甲基醚乙酸酯使固體成份濃度爲 20%後，使用孔徑0.5 # m之米利波阿濾器過濾調製樹脂組· 成物。調製所得之組成物爲無色透明。 .使用旋塗機將上述組成物塗佈於Si02浸漬玻璃基板上 ，熱板上以8 0 °C預烤5分鐘後形成塗膜，接著於烤箱中以 230 °C加熱處理60分鐘，形成膜厚2.0// m之保護膜。 評估保護膜 (1 )評估透明性 使用分光光度計（〗50_20型雙光束（日立製作所（股 )製）測定上述形成保護膜之基板的400至800nm透光率 。4 0 0至8 0 0 n m透光率之最小値如表2所示。該値爲9 5 %以 -54· 200806701 (51) 上時表示保護膜之透明性良好。 (2 )評估耐熱尺寸安定性 烤箱中各自以250°C下1小時之條件及270°C下1小時之 條件加熱上述形成保護膜之基板’並測定加熱前後之膜厚 。由下列式所算出之耐熱尺寸安定性如表2所示。該値爲 ， 95%以上時表示耐熱尺寸安定性良好。 着 耐熱尺寸安定性=(加熱後之膜厚）/(加熱前之膜厚 )xlOO ( % ) (3 )評估耐熱變色性 烤箱中以2 5 0 °C加熱上述形成保護膜之基板1小時，同 時上述（1 )測定加熱前後之透明性。由下列式算出之耐 熱變色性如表2所示。該値爲5%以下時表示耐熱變色性良 好。 φ 耐熱變色性=加熱前之透光率-加熱後之透光率（％ ) ¥ ( 4 )測定表面硬度 以JIS K-5 4 00- 1 9 90之8.4.1鉛筆抓搔試驗測定上述形 成保護膜之基板的保護膜表面硬度。該値如表2所示。又 該値爲4H或比其硬時表示表面硬度良好。 (5 )測定動態微小硬度 使用島津動態微小硬度計DUH-201 (島津製作所（股 -55- 200806701 (52) )製）以稜角1 1 5 °C三角壓頭（擊潰型）進行測定條件爲 測定荷重：o.lgf、速度：0.0145gf/sec、保持時間：5sec 、溫度2 3 °C及1 40 °C之壓入試驗以測定保護膜動態微小硬 度，結果如表2所示。 (6 )評估密合性Table 1 Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Mw 18,000 7,500 3,800 14,000 9,000 14,000 15,000 17,500 Μη 9,000 4,500 2,000 6,000 5,000 7,000 6,000 8,500 Mw/Mn 2 2 2 2 2 2 3 2 Copolymer (A-1) (A-2 ) (A-3) (A-4) (Α·5) (Α-6) (Α-7) (Α-8) -53 - 200806701 (50) Table 1 (continued) Comparative Synthesis Example 1 Comparative Synthesis Example 2 M w 2 0,000 80 0 Μη 9,000 500 M w / Μ η 2 2 Copolymer (a * 1) - (a-2) Preparation and Evaluation of Resin Composition Example 1 A solution containing the copolymer (a-1) obtained in the above Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer (A-1)) and (B) tripropylene oxime 50.0 parts by weight of base pentaerythritol succinic acid (TAPS), and (F) surfactant SH-28PA (manufactured by Toray Island) 1.1 parts by weight and (G) auxiliaries 7-epoxypropoxy propyl After 15 parts by weight of methoxymethoxysilane, propylene glycol-methyl ether acetate was added to have a solid concentration of 20%, and the resin group and the product were filtered using a Millipore filter having a pore size of 0.5 # m. The composition obtained by the preparation is colorless and transparent. The composition was applied onto a SiO 2 -impregnated glass substrate using a spin coater, and pre-baked at 80 ° C for 5 minutes on a hot plate to form a coating film, followed by heat treatment at 230 ° C for 60 minutes in an oven to form a film. Protective film with a thickness of 2.0//m. Evaluation of Protective Film (1) Evaluation of Transparency The transmittance of 400 to 800 nm of the above-mentioned substrate for forming a protective film was measured using a spectrophotometer (a 50_20 type double beam (manufactured by Hitachi, Ltd.). 4 0 0 to 800 nm The minimum light transmittance is shown in Table 2. The 値 is 95% to -54·200806701 (51), indicating that the transparency of the protective film is good. (2) Evaluating the heat-resistant dimensional stability of each oven at 250° The substrate "forming the protective film" was heated under the conditions of 1 hour under C and 1 hour at 270 ° C, and the film thickness before and after heating was measured. The heat resistance dimensional stability calculated by the following formula is shown in Table 2. When it is 95% or more, it indicates that the heat resistance dimensional stability is good. The heat resistance dimensional stability = (film thickness after heating) / (film thickness before heating) xlOO (%) (3) Evaluation of heat-resistant discoloration oven in 2 50 The substrate on which the protective film was formed was heated at ° C for 1 hour, and the transparency before and after heating was measured in the above (1). The heat-resistant discoloration property calculated by the following formula is shown in Table 2. When the 値 was 5% or less, the heat-resistant discoloration property was good. φ heat-resistant discoloration = transmittance before heating - after heating Rate (%) ¥ (4) Determination of surface hardness The surface hardness of the protective film of the substrate on which the protective film was formed was measured by the 8.4.1 pencil scratch test of JIS K-5 4 00- 1 9 90. In addition, when the crucible is 4H or harder than it, the surface hardness is good. (5) The dynamic micro hardness is measured using Shimadzu dynamic micro hardness tester DUH-201 (Shimadzu Corporation (share-55-200806701 (52))) with an angular angle of 1 The 1 5 °C triangular indenter (crush type) was measured by measuring the load: o.lgf, speed: 0.0145gf/sec, holding time: 5sec, temperature 2 3 °C and 1 40 °C. The dynamic hardness of the protective film was as shown in Table 2. (6) Evaluation of adhesion

* 對上述形成保護膜之基板進行壓力炊具試驗（1 2(TC φ 、濕度 100%、4小時）後，以 JIS K-5400- 1 990 之 8,5 J 附 著性棋盤貼合法評估保護膜之密合性（對Si〇2之密合性） 。棋格100個中殘留棋格數目如表2所示。 又，除了以Cr基板取代Si02浸漬玻璃基板外，其他同 上述形成膜厚2.0// m之保護膜後，同上述棋盤貼合法評估 對Cir之密合性，結果如表2所示。 (7 )評估平坦化性 # 使用旋塗機將顏料系彩色光阻劑（商品名 ▼ 「JCR RED 689」、「JCR GREEN 706」、「CR 8200B」 、以上爲]SR (股）製）塗佈於Si02浸漬玻璃基板上，熱 板上以9 0 °C預烤1 5 0秒後形成塗膜。其次介有一定圖罩使 用曝光機Canon PLA501F (佳能（股）製）以ghi線（波長 43 6nm、40 5nm、3 65nm之強度比= 2.7 : 2.5 : 4·8 )照射 i線 換算下2,000J/m2之曝光量，再以0.05%氫氧化鉀水溶液顯 像，以超純水漂洗60秒後，烤箱中以23 0 °C加熱處理30分 鐘’形成紅、綠及藍3色線條狀彩色濾光片（線幅1 〇 〇 μ m •56- 200806701 (53) 使用表面粗細計「α -分級」（商品名：丹可爾公司 製）測定形成該彩色濾光片之基板的表面凹凸程度，結果 爲1.0//m。測定條件爲，測定長2，000// m、測定範圍 2，0 0 0 // m角、測定點數η = 5。即，測定方向爲紅、綠、藍 方向之線條短軸方向及紅•紅、綠•綠、藍•藍同一色之 ’ 線條長軸方向，各自測定η=5 (合計η數爲1 〇 )。 φ 其次使用旋塗機塗佈上述形成保護膜用組成物，熱板 上以90°C預烤5分鐘後形成塗膜，再於烤箱中以23 0 °C加熱 處理60分鐘，可於彩色濾光片上面形成膜厚2.0// m之保護 膜。此時該膜厚係指，由形成於基板上之彩色濾光片最上 面算起之厚度。 使用接觸式膜厚測定裝置α -分級（日本丹可爾（股 )製）測定上述彩色濾光片上形成保護膜之基板的保、護膜 表面凹凸程度。又測定條件爲，測定長2，0 0 0 μ m、測定範 # 圍2,000 // m角、測定點數n = 5。即，測定方向爲紅、綠、 藍方向之線條短軸方向及紅•紅、綠•綠 '藍•藍同一色 - 之線條長軸方向，各自測定n = 5 (合計η數爲1 0 )。各測定 點之最高部及最底部的高低差（nm )之1 0次平均値如表2 所示。該値爲3 0 0nm以下時表示平坦化性良好。 (8 )評估保存安定性 使用東京計器（股）製ELD型黏度計測定實施例1調 製所得之形成保護膜用樹脂組成物（加入（D )感熱性酸 -57- 200806701 (54) 發生劑之物）的黏度。其後將該組成物靜置於25 °C下，每 日測定2 5 °C之溶液黏度。計算以調製後黏度爲基準下增黏 5%所需的日數，該日數如表2所示。該日數爲30以上時表 示保存安定性良好。 實施例2至7及比較例1、2 除了組成物之各成份種類及量如表2所示，以及使用 表2所示溶劑組成表2所示固體成份濃度外，其他同實施例 1調製樹脂組成物。 使用上述調製所得之形成保護膜用樹脂組成物，同實 施例1形成保護膜後評估，結果如表2所示。 調製及評估含有感熱性酸發生劑（E )之樹脂組成物 實施例8 加入上述合成例7所得含有共聚物（A - 7 )之溶液（相 當於共聚物（A-7 ) 100重量份之量），及（ρ )表面活性 劑SH-28PA (東雷島（股）製）0·1重量份及（G )接著助 劑r -環氧丙氧基丙基三甲氧基矽烷15重量份，再加入丙 二醇一甲醚乙酸酯使固體成份濃度爲20%。 將（E )感熱性酸發生劑苄基一 2 -甲基一 4 一羥基苯 基甲基毓六氟銻酸鹽1重量份溶解於二乙二醇乙基甲醚6 5 重量份而得之物加入上述所得組成物中，再以孔徑〇 . 5 // m 米利波阿濾器過濾調製樹脂組成物。調製所得之組成物爲 無色透明。 -58- 200806701 (55) 實施例9及比較例1、2 除了組成物之各成份種類及量如表2所示，以及使用 表2所示溶劑組成表2所示固體成份濃度外，其他同實施例 1調製樹脂組成物。 使用上述調製所得之形成保護膜用樹脂組成物，同實 ^ 施例1形成保護膜後評估，結果如表2所示。 實施例10至12 除了組成物之各成份種類及量如表2所示，且以狹縫 模頭塗佈機取代旋塗機外，其他同竇施例1調製樹脂組成 物及形成保護膜再評估，結果如表2所示。 -59- 200806701 (56)* After the pressure cooker test was carried out on the substrate on which the protective film was formed (1 2 (TC φ , humidity 100%, 4 hours), the protective film was evaluated by the 8,5 J adhesion checkerboard method of JIS K-5400-1 990. Adhesion (adhesion to Si〇2) The number of remaining chess pieces in the 100 pieces is shown in Table 2. In addition, the film thickness is 2.0/, as described above, except that the SiO2-impregnated glass substrate is replaced by a Cr substrate. After the protective film of /m, the adhesion to Cir was evaluated by the above-mentioned checkerboard method, and the results are shown in Table 2. (7) Evaluation of flatness# The pigment-based color resist was used by a spin coater (product name ▼ "JCR RED 689", "JCR GREEN 706", "CR 8200B", and above] SR (manufactured by SR) are applied to a SiO2-impregnated glass substrate, and pre-baked at 90 °C for 1500 seconds on a hot plate. A coating film is formed. Secondly, a certain mask is used to irradiate the i-line with an exposure machine Canon PLA501F (manufactured by Canon) to ghi line (intensity ratio of wavelengths of 4 6 nm, 40 5 nm, and 3 65 nm = 2.7 : 2.5 : 4·8 ). The exposure amount of 2,000 J/m2 was converted, and then developed with 0.05% potassium hydroxide aqueous solution, rinsed with ultrapure water for 60 seconds, and then ovend at 23 0 ° C heat treatment for 30 minutes' to form red, green and blue 3-color line color filters (line width 1 〇〇μ m •56- 200806701 (53) Surface roughness meter "α-grading" (trade name: Danke The surface roughness of the substrate on which the color filter was formed was measured and found to be 1.0/m. The measurement conditions were a measurement length of 2,000 / / m, a measurement range of 2, 0 0 0 / m angle, The number of measured points is η = 5. That is, the measurement direction is the short axis direction of the line in the red, green, and blue directions and the long axis direction of the line of the red, red, green, green, blue, and blue colors, and each is measured as η=5 ( The total number of η was 1 〇). φ Next, the composition for forming a protective film was applied by a spin coater, and the coating was pre-baked at 90 ° C for 5 minutes on a hot plate to form a coating film, which was then heated at 23 ° C in an oven. After 60 minutes of treatment, a protective film having a film thickness of 2.0/m can be formed on the color filter. At this time, the film thickness refers to the thickness of the color filter formed on the substrate. Membrane thickness measuring device α-classification (manufactured by Nippon Steel Co., Ltd.) for measuring a substrate on which a protective film is formed on the color filter The degree of unevenness of the surface of the film and the protective film is determined by measuring a length of 2,0 0 0 μm, a measurement range of 2,000 // m angle, and a measurement point of n = 5. That is, the measurement direction is red, green, and The direction of the short axis of the blue direction and the long axis direction of the lines of red, red, green, green, blue, and blue are measured by n = 5 (the total number of η is 1 0 ). The average of the height difference (nm) of the highest part and the bottom part of each measurement point is shown in Table 2. When the enthalpy is 300 nm or less, the flatness is good. (8) Evaluation of storage stability The resin composition for forming a protective film prepared by the preparation of Example 1 was measured using an ELD-type viscometer manufactured by Tokyo Keiki Co., Ltd. (addition of (D) thermosensitive acid-57-200806701 (54) generating agent Viscosity. Thereafter, the composition was allowed to stand at 25 ° C, and the viscosity of the solution at 25 ° C was measured every day. Calculate the number of days required to increase the viscosity by 5% based on the adjusted viscosity. The number of days is shown in Table 2. When the number of days is 30 or more, it indicates that the storage stability is good. Examples 2 to 7 and Comparative Examples 1 and 2 The same as Example 1 except that the composition and amount of each component of the composition are as shown in Table 2, and the solid content concentration shown in Table 2 of the solvent composition shown in Table 2 was used. Composition. Using the resin composition for forming a protective film obtained by the above-mentioned preparation, a protective film was formed in the same manner as in Example 1, and the results are shown in Table 2. Preparation and Evaluation of Resin Composition Containing Thermosensitive Acid Generating Agent (E) Example 8 A solution containing the copolymer (A-7) obtained in the above Synthesis Example 7 (corresponding to 100 parts by weight of the copolymer (A-7)) And (ρ) surfactant SH-28PA (manufactured by Toray Island Co., Ltd.) 0.1 part by weight and (G) 15 parts by weight of the auxiliary r-glycidoxypropyltrimethoxydecane, Further, propylene glycol monomethyl ether acetate was added to have a solid concentration of 20%. 1 part by weight of (E) a thermosensitive acid generator benzyl 2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate was dissolved in 6 5 parts by weight of diethylene glycol ethyl methyl ether. The composition was added to the above-obtained composition, and the resin composition was filtered by a pore size of 5. 5 // m. The composition obtained by the preparation is colorless and transparent. -58- 200806701 (55) Example 9 and Comparative Examples 1 and 2, except that the types and amounts of the components of the composition are as shown in Table 2, and the solid content concentrations shown in Table 2 of the solvent composition shown in Table 2 were used. Example 1 Modulation of a resin composition. Using the resin composition for forming a protective film obtained by the above-mentioned preparation, a protective film was formed in the same manner as in Example 1, and the results are shown in Table 2. Examples 10 to 12 Except that the types and amounts of the components of the composition are as shown in Table 2, and the spin coater was replaced by a slit die coater, the other sinus application example 1 modulated the resin composition and formed a protective film. Evaluation, the results are shown in Table 2. -59- 200806701 (56)

<n€ 實施例9 t-μ < 〇 CM ώ (N ό 1—1 1—^ ώ κη ^Η ώ 無色透明 OS ON ON v〇 ON m 寸 (N ΓΓ> 〇 o o o o ψ 'i 60日以上 實施例8 卜 < 〇 V 1 1 t 1 '! ώ (Ν GO 無色透明 ON ON ON ON 00 CTv m ffi 寸 ^-4 m o o o o § r—H 60日以上 實施例7 VO < 〇 I·1 i » V 1 1 1 1 Ψ t m 1 ON ON Os 00 a\ m 寸 沄 in (N o t—i o o irv ON T-H 60日以上1 實施例6 f—H < 〇 rn ώ Ο 1 1 1 1 m 1 On ON On ON 〇〇 ON m Ε 寸 ON (Ν <N 0 1 ί o n · i 60曰以上 實施例5 < Ο (Ν ώ ο m 1 1 1 1 m I CTs Os ON ON ON Ε 寸 <Ν m <N o 1 o r· < § T—4 60曰以上 實施例4 寸 < Ο (Ν PQ 宕 1 1 1 1 (N GO 1 〇\ Os Os oo c\ cn PC 寸 o o o 〇 1 ( 60日以上 實施例3 < Ο τ—i ώ ο yn t 1 1 1 Ύ—Κ xh 1 as Ch ON ON rn 寸 <N m 0 1 i 〇 f—! 〇 i—H 60曰以上 實施例2 (N < ο r—Η 寶\ ώ g 1 1 1 1 (N m 1 ON ON ON ON X 寸 荔 〇\ <M o r-H 〇 g 60日以上 實施例1 < ο τ-Η 1 m ο 1 I 1 1 m 1 ON ON OS ON m 寸 ON (Ν in Cs| o T—^ o o o 卜 60日以上 種類 量(重量份) 種類 量(重量份) 種類 量(重量份) 種類 量(重量份） 種類 h _ g 添加後(E)成份之外觀 透明性(％) 耐熱尺寸安定性(％)250 °C x 1小時 ο (Ν s 姻 — 癒χ _Ρ 耐熱變色性(％) 表面硬度 P m (N 140°C Si〇2 _^Hi 平坦化性(nm) 保存安定性(曰） _ Φ S 乙烯性不 飽和化合 物(B) 碱 (Ε)感熱性 酸發生劑 溶劑 m 链 m 画 動態微小 硬度 密合性 _ -60 - 200806701<n € Example 9 t-μ < 〇CM ώ (N ό 1—1 1—^ ώ κη ^Η ώ Colorless and transparent OS ON ON v〇ON m inch (N ΓΓ> 〇oooo ψ 'i 60 days The above embodiment 8 卜< 〇V 1 1 t 1 '! ώ (Ν GO colorless transparent ON ON ON ON 00 CTv m ffi inch ^-4 moooo § r-H 60 days or more embodiment 7 VO < 〇 I· 1 i » V 1 1 1 1 Ψ tm 1 ON ON Os 00 a\ m inch 沄 in (N ot—ioo irv ON TH 60 days or more 1 Example 6 f—H < 〇rn ώ Ο 1 1 1 1 m 1 On ON On ON 〇〇ON m Ε 寸 ON (Ν <N 0 1 ί on · i 60曰 or more Example 5 < Ο (Ν ώ ο m 1 1 1 1 m I CTs Os ON ON ON 寸 inch <Ν m <N o 1 or· < § T—4 60曰 or more Example 4 inch< Ο (Ν PQ 宕1 1 1 1 (N GO 1 〇\ Os Os oo c\ cn PC inch ooo 〇1 (60 days or more, embodiment 3 < Ο τ - i ώ ο yn t 1 1 1 Ύ - Κ xh 1 as Ch ON ON rn inch <N m 0 1 i 〇f—! 〇i—H 60曰The above embodiment 2 (N < ο r - 宝 \ \ 1 g 1 1 1 1 (N m 1 ON ON ON ON X inch 荔〇 \ <M o rH 〇g 60 days or more implementation 1 < ο τ-Η 1 m ο 1 I 1 1 m 1 ON ON OS ON m 寸 ON (Ν in Cs| o T—^ ooo 卜 60-odd type (weight parts) Type (weight parts) Amount (parts by weight) Type (parts by weight) Type h _ g Appearance transparency of (E) component after addition (%) Heat resistance dimensional stability (%) 250 °C x 1 hour ο (Ν s marriage - χ _ _ Ρ Heat discoloration (%) Surface hardness P m (N 140 °C Si〇2 _^Hi Flatness (nm) Storage stability (曰) _ Φ S Ethylene unsaturated compound (B) Alkali (Ε) sensible heat Acid generator solvent m chain m draw dynamic micro hardness adhesion _ -60 - 200806701

§(N« 比較例 (N ώ ο r—ί； r—1 ώ 〇 r-H1 ^^4 〇 ο 1—1 ▼—Η ώ r—Η r—ί ώ 無色透明 σ\ Os (N ON oo 寸 Ε m (Ν (N (N 〇 o in T—H 60曰以上 比較例1 Ο f I 1 1 1 ώ v—( t 00 無色透明 ON Os Os C\ m 寸 CM m oo o 480 10日以上 實施例12 A-l ο 1—Η cn ώ 〇 r-H ό ο r-H ώ rn ώ cn f—< 無色透明 ON ON OS Os oo Os m 寸 ο m (M O Ψ < o ί § 1—4 60日以上 實施例11 A-l Ο Τ-Η 1 I C-2 vry τ—ί ώ r1 Η ώ 無色透明 On ON ON ON G\ m 寸 (N m 卜 (N o r—H o 〇 m 60日以上 實施例10 < Ο ι—Ι r111 ^ ώ Ο t 1—( d Ο Τ—Η ώ rn (/} m 無色透明 On ON Os ON 00 〇\ m Ε 寸 o (N O 1—H o H g H 60日以上 種類 量(重量份） 種類 量(重量份） 種類 量(重量份) 種類 量(重量份） I 種類 固體成份濃度(重量％) 添加後(E)成份之外觀 透明性(％) 耐熱尺寸安定性(％)250°C x 1小時 耐熱尺寸安定性(％)270°c x 1小時 耐熱變色性(％) 表面硬度 23 °C 140°C Si〇2 平坦化性(nm) 保存安定性(曰） 高分子量物(A) 乙烯性不飽和化合 物(Β) (C)環氧化合物 (Ε)感熱性酸發生劑 I 1 溶劑 動態微小硬度 密合性 -61 * 200806701 (58) 又，表2中乙烯性不飽和化合物（B )、環氧化合物（ C )、感熱性酸發生劑（E )及溶劑的簡稱各自代表下列 之物。 B-1 :三丙烯醯氧基季戊四醇琥珀酸{別名：3-丙烯醯 氧基-2,2-雙丙烯醯氧基甲基-丙基}酯，簡稱TAPS} B-2:五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-丙烯醯氧基甲基-丙基）-2,2-雙-丙 烯醯氧基甲基-丙基]酯，簡稱PADPS} B-3 :二季戊四醇六丙烯酸酯 C-1 :雙酚A酚醛清漆型環氧樹脂（日本環氧樹脂（ 股）製，商品名：耶皮可157S65 ) C-2 :三羥甲基丙烷三（3-乙基-3-氧雜環丁烷基甲基 )醚 E-1:苄基-2-甲基-4-羥基苯基甲基鏑六氟銻酸鹽 S -1 :丙二醇一甲醚乙酸酯 S-2 :二乙二醇二甲醚 S-3 :二乙二醇乙基甲醚 調製及評估含有感放射線性酸發生劑（D )之樹脂組成物 實施例1 3 加入上述合成例1所得含有共聚物（A-1 )之溶液（相 當於共聚物（A-1 ) 100重量份（固體成份）之量）’及環 氧化合物（C )雙酚A酚醛清漆型環氧樹脂^耶皮可 157S65」（日本環氧樹脂（股）製）1〇·〇重量份、表面活 -62- 200806701 (59) 性劑（F ) S Η - 2 8 P A (東雷島（股）製）0 ·1重量份及接著 助劑（G) 7 •環氧丙氧基丙基三甲氧基砂院15重量份’再 加入二乙二醇二甲醚使固體成份濃度爲20 % ° 將感放射線性酸發生劑（D)三苯基毓三氟甲烷磺酸 鹽1重量份溶解於二乙二醇乙基甲醚65重量％而得之物加 入上述所得組成物中，再以孔徑〇·5 // πι之米利波阿濾器過 濾調製形成保護膜用樹脂組成物。調製所得之組成物爲無 色透明。 使用旋塗機將上述組成物塗佈於Si〇2浸漬玻璃基板上 ，熱板上以8(TC預烤5分鐘後形成塗膜。 其次使用曝光機Canon PLA501F (佳能（股）製）以 ghi 線（波長 43 6nm、405nm、365nm之強度比=2·7: 2.5 · 4.8)照射i線換算下爲2,00(H/m2之曝光量。其後於烤箱中 以23 0°C加熱.處理60分鐘，形成膜厚2.0 // m之保護膜。 評估保護膜 使用上述所形成具有保護膜之基板，同實施例1進行 (1 )評估透明性、（2 )評估耐熱尺寸安定性、（3 )評 估耐熱變色性、（4 )測定表面硬度、（5 )測定動態微小 硬度及（6 )評估密合性，結果如表3所示。 (7 )評估平坦化性 使用旋塗機將顏料系彩色光阻劑（商品名 「JCR RED689」、「JCR GREEN 706」、「CR 8200B」 -63- 200806701 (60) ，以上爲JSR (股）製）塗佈於Si 02浸漬玻璃基板上，熱 板上以90°C預烤150秒後形成塗膜。其次介有一定圖罩使 用曝光機Canon PLA501F (佳能（股）製）以ghi線（波長 4 3 6nm、405nm、3 65nm之強度比=2.7 : 2.5 : 4.8 )照射 i線 換算下爲2，000J/m2之曝光量後，使用0.05%氫氧化鉀水溶 液顯像，再以超純水漂洗60秒，接著於烤箱中以23 0 °C加 ‘ 熱處理3 0分鐘，形成紅、綠及藍3色線條狀彩色濾光片（ _ 線幅 1 ο 〇 /ζ Π1)。 使用表面粗細計「α -分級」（商品名：丹可爾公司 製）測定該形成彩色濾光片之表面凹凸程度，結果爲1 .〇 m。又，測定條件爲，測定長2,000 // m、測定範圍2,000 # m角、測定點數n = 5。即，測定方向爲紅、綠、藍方向 之線條短軸方向及紅•紅、綠•綠、藍·藍同一色之線條 長軸方向，各自測定n = 5 (合計η數爲1 0 )。 其次使用旋塗機塗佈上述形成保護膜用組成物，熱板 φ 上以80°C預烤5分鐘後形成塗膜。 ~ 接著使用曝光機Canon PLA501F (佳能（股）製）以 " ghi線（波長 436nm、405nm、365nm之強度比=2·7: 2.5: 4.8 )照射i線換算下爲2,000J/m2之曝光量後’烤箱中以 2 3 0 °C加熱處理6 0分鐘，形成膜厚2 · 0 // m之保護膜。此時 該膜厚係指，由形成於基板上之彩色濾光片最上面算起之 厚度。 使用接觸式膜厚測定裝置^ -分級（丹可爾日本（股 )製）測定上述形成彩色濾光片上具有保護膜之基板的保 •64- 200806701 (61) 護膜表面凹凸程度。又測定條件爲，測定長2,000 μ m、測 定範圍2,0〇〇 # m角、測定點數n = 5。即，測定方向爲紅' 綠、藍方向之線條短軸方向及紅•紅、綠•綠、藍•藍同 一色之線條長軸方向，各自測定n = 5 (合計η數爲1 0 )。各 測定點之最高部及最底部的高低差（nm )之1 0次平均値 如表3所示。該値爲300nm以下時表示平坦化性良好。 Φ φ (8)評估保存安定性 使用東京計器（股）製ELD型黏度計測定實施例〗3調 製所得之形成保護膜用樹脂組成物（添加（D )感放射線 性酸發生劑之物）25 °C之黏度。其次將該組成物靜置25 °C 下，每日測定溶液黏度，計算以調製後黏度爲基準時增黏 5 %所需日數，結果如表3所示。該臼數爲3 0曰以上時表示 保存安定性良好。 φ 實施例14、15、18及比較例3 ~ 除了組成物之各成份種類及量如表3所示，以及使用 ▲ 表3所示溶劑組成表3所示固體成份濃度外，其他同實施例 13調製樹脂組成物。 使用上述所得之形成保護膜用樹脂組成物同實施例1 3 形成保護膜再評估，結果如表3所示。 實施例〗6、1 7 除了組成物之各成份種類及量如表3所示，且以狹縫 -65- 200806701 (62) 模頭塗佈機取代旋塗機外，其他同實施例1 3調製樹脂組成 物、形成保護膜再評估，結果如表3所示。§(N«Comparative example (N ώ ο r—ί; r—1 ώ 〇r-H1 ^^4 〇ο 1—1 ▼—Η ώ r—Η r—ί ώ colorless transparent σ\ Os (N ON oo Inch Ε m (Ν (N (N 〇o in T-H 60曰 above Comparative Example 1 Ο f I 1 1 1 ώ v—( t 00 colorless transparent ON Os Os C\ m inch CM m oo o 480 10 days or more Embodiment 12 Al ο 1—Η cn ώ 〇rH ό ο rH ώ rn ώ cn f—< colorless transparent ON ON OS Os oo Os m inch ο m (MO Ψ < o ί § 1-4 60 days or more Example 11 Al Ο Τ-Η 1 I C-2 vry τ—ί ώ r1 Η ώ Colorless and transparent On ON ON ON G\ m inch (N m 卜 (N or—H o 〇m 60 days or more embodiment 10 < ι ι—Ι r111 ^ ώ Ο t 1—( d Ο Τ—Η rn rn (/} m colorless transparent On ON Os ON 00 〇\ m Ε inch o (NO 1—H o H g H 60 days or more (Parts by weight) Type (parts by weight) Type (parts by weight) Type (parts by weight) I Solid content concentration (% by weight) Appearance transparency (%) of the component after the addition (%) Heat resistance dimensional stability (%) ) 250 ° C x 1 hour heat resistance dimensional stability (%) 270 ° cx 1 hour heat discoloration (%) Surface hardness 23 °C 140 °C Si〇2 Flatness (nm) Storage stability (曰) High molecular weight (A) Ethylene unsaturated compound (Β) (C) Epoxy compound (Ε) sensible acid generation Agent I 1 Solvent dynamic micro-hardness adhesion -61 * 200806701 (58) Further, the abbreviation of ethylenically unsaturated compound (B), epoxy compound (C), sensible acid generator (E) and solvent in Table 2 Each represents the following: B-1: Tripropylene decyloxypentaerythritol succinic acid {alias: 3-propenyloxy-2,2-bispropenyloxymethyl-propyl} ester, referred to as TAPS} B- 2: penta propylene decyl dipentaerythritol succinic acid {alias: [3-( 3-propenyloxy-2,2-bis-propenyloxymethyl-propyl)-2,2-bis-acrylofluorene] Oxymethyl-propyl]ester, abbreviated as PADPS} B-3: dipentaerythritol hexaacrylate C-1: bisphenol A novolac type epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name: Yeppi 157S65) C-2: Trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether E-1: benzyl-2-methyl-4-hydroxyphenylmethyl Hexafluoroantimonate S-1: propylene glycol monomethyl ether acetate S-2: two Diethylene glycol dimethyl ether S-3: Diethylene glycol ethyl methyl ether Preparation and evaluation of resin composition containing radiation sensitive acid generator (D) Example 1 3 The copolymer containing the above Synthesis Example 1 was added (A- 1) solution (corresponding to the copolymer (A-1) 100 parts by weight (solid content)) and epoxy compound (C) bisphenol A novolac type epoxy resin ^Yelpi 157S65" (Japanese ring Oxygen resin (stock)) 1〇·〇 parts by weight, surface activity-62- 200806701 (59) Sex agent (F) S Η - 2 8 PA (manufactured by Toray Island) 0 · 1 part by weight and then Additive (G) 7 • Glycidoxypropyltrimethoxy sand yard 15 parts by weight 'add diethylene glycol dimethyl ether to make the solid concentration of 20% °. Radiation-sensitive acid generator (D) 1 part by weight of triphenylsulfonium trifluoromethanesulfonate is dissolved in 65% by weight of diethylene glycol ethyl methyl ether, and the obtained composition is added to the above-mentioned composition, and then it is a pore diameter of 5·5 // πι. The filter was filtered to prepare a resin composition for a protective film. The composition obtained by the preparation is colorless and transparent. The composition was applied onto a Si〇2-impregnated glass substrate using a spin coater, and a coating film was formed by pre-baking for 8 minutes on a hot plate for 8 minutes. Next, an exposure machine Canon PLA501F (manufactured by Canon) was used to ghi. The line (intensity ratio of wavelengths of 4 6 nm, 405 nm, and 365 nm = 2·7: 2.5 · 4.8) was 2,00 (H/m 2 exposure) under i-line conversion, and then heated at 23 ° C in an oven. After treating for 60 minutes, a protective film having a film thickness of 2.0 // m was formed. Evaluation of the protective film Using the substrate having the protective film formed as described above, (1) evaluation of transparency, (2) evaluation of heat-resistant dimensional stability, (1) 3) evaluation of heat discoloration resistance, (4) measurement of surface hardness, (5) measurement of dynamic micro hardness, and (6) evaluation of adhesion, and the results are shown in Table 3. (7) Evaluation of flatness using a spin coater to pigment Color resist (product name "JCR RED689", "JCR GREEN 706", "CR 8200B" -63-200806701 (60), the above is JSR (share)) coated on Si 02 impregnated glass substrate, heat The plate was pre-baked at 90 ° C for 150 seconds to form a coating film. Secondly, a certain mask was used to expose the lens Canon PLA501F (Canon ( In the case of the ghi line (intensity ratio of wavelength 436 nm, 405 nm, and 3 65 nm = 2.7:2.5:4.8), the exposure amount of 2,000 J/m2 in the i-line conversion is used, and then 0.05% potassium hydroxide aqueous solution is used. Image, rinse with ultrapure water for 60 seconds, then heat-treat at 30 °C for 30 minutes in the oven to form red, green and blue 3-color line color filters ( _ line 1 ο 〇 / ζ ) 1) The surface roughness of the color filter was measured by the surface roughness meter "α - classification" (trade name: manufactured by Dankel), and the result was 1. 〇m. Further, the measurement conditions were: 2,000 // m, measurement range 2,000 # m angle, number of measurement points n = 5. That is, the measurement direction is the short axis direction of the red, green, and blue directions and the red, green, green, blue, and blue colors The long axis direction of the line was measured for n = 5 (the total number of η was 10). Next, the composition for forming a protective film was applied by a spin coater, and the hot plate φ was prebaked at 80 ° C for 5 minutes to form a coating film. ~ Then use the exposure machine Canon PLA501F (manufactured by Canon) to > ghi line (wavelength of 436nm, 405nm, 365nm) =2·7: 2.5: 4.8) After exposure to 2,000 J/m2 in the i-line conversion, the oven was heated at 203 °C for 60 minutes to form a protective film with a film thickness of 2 · 0 // m. . In this case, the film thickness means the thickness of the uppermost color of the color filter formed on the substrate. The degree of unevenness of the surface of the protective film formed on the substrate having the protective film on the color filter was measured by a contact type film thickness measuring device-classification (manufactured by Dankel Japan Co., Ltd.). Further, the measurement conditions were as follows: measurement length: 2,000 μm, measurement range of 2, 0 〇〇 # m angle, and number of measurement points n = 5. That is, the measurement direction is the short axis direction of the line in the red 'green, blue direction, and the long axis direction of the line of red, red, green, green, blue, and blue, and each of them is measured as n = 5 (the total number of η is 1 0 ). The average of the height difference (nm) of the highest part and the bottom part of each measurement point is shown in Table 3. When the 値 is 300 nm or less, the flatness is good. Φ φ (8) Evaluation of storage stability The resin composition for forming a protective film (addition of (D) sensitizing radioactive acid generator) prepared by using the ELD-type viscometer manufactured by Tokyo Instruments Co., Ltd. was measured. Viscosity of °C. Next, the composition was allowed to stand at 25 ° C, and the viscosity of the solution was measured daily, and the number of days required to increase the viscosity by 5 % based on the viscosity after the preparation was calculated. The results are shown in Table 3. When the number of turns is 30 or more, the storage stability is good. φ Examples 14, 15, 18 and Comparative Example 3 ~ Except that the composition and amount of each component of the composition are as shown in Table 3, and the solid content concentration shown in Table 3 of the solvent composition shown in Table 3 is used, the same examples. 13 Modification of the resin composition. Using the resin composition for forming a protective film obtained above, a protective film was formed and evaluated in the same manner as in Example 13. The results are shown in Table 3. EXAMPLES 6, 6 In addition to the composition and amount of each component of the composition as shown in Table 3, and the slit coater was replaced by a slit-65-200806701 (62) die coater, the same as in the first embodiment. The resin composition was prepared and a protective film was formed and evaluated. The results are shown in Table 3.

-66- 200806701 (63)-66- 200806701 (63)

比較例3 ά ο f i 1 1 1 1 Q (N ώ Ο (Ν 無色透明 〇〇 Os 00 ON r—Η 〇\ cn 寸 (N cn 00 (Ν 〇〇 Ο 430 10曰 實施例18 〇〇 < 〇 r-H ώ 〇 1 I 1' 11 < Q ι 1 ζ/) 無色透明 ON Os On Os oo On m 寸 沄 v〇 CN ο r—Η ο ο t-H 60日以上 實施例Π τ—Η < o r—l B»3 瞧 1 D-1 1—Η <Ν ΟΟ 無色透明i Os ON G\ ON OO ON m 寸 m 卜 (Μ Ο ο ο s Τ—Η 60日以上 實施例16 Τ—Η < o ” _H B»2 I ό 〇 r*"H τ—Hi Q S-3/S-4=7/3 無色透明 ON ON ON 〇s OO ON 寸 m ο ι—Ι ο ο § Η 60日以上 實施例15 Α-7 o B-2 1 1 Η Q (Ν m 無色透明 ON ON On C\ ON m 寸 (Ν m 0C (Ν ο Τ-Η ο ο Ο r-^ 60日以上 實施例14 Α-2 〇 r—H ώ 〇 m 1 1 D-1 in r—< ζλ 無色透明 c\ ON Os Os m π 寸 (Ν m Ο ο ο ο ▼—Η 60日以上 實施例13 ^4 < o ώ 1 1 r*H Q r—1 (Ν ζλ 無色透明 os Os Os ON OO OS m 寸 产丨, rn (Ν ο r—ί ο 60日以上 種類 量(重量份） 種類 量(重量份) 種類 量(重量份） 種類 量(重量份） 種類 固體成份濃度(重量％) 添加後(C)成份之外觀 透明性(％) 耐熱尺寸安定性(％)250°c x 1小時 耐熱尺寸安定性(％)270°C x 1小時 耐熱變色性(％) 表面硬度 23 °C 140°C Si〇2 平坦化性(nm) 保存安定性(曰） 高分子量物(A) 乙烯性不飽和化合 物(Β) (C)環氧化合物 (D)感放射線性發 生劑 溶劑 動態微小硬度 密合性 1 -67- 200806701 (64) 又，表3中乙烯性不飽和化合物（B)、環氧化合物 (C )、感放射線性酸發生劑（D )及溶劑之簡稱各自代 表下列物。 B-1 :三丙烯醯氧基季戊四醇琥珀酸{別名：3_丙燃醯 氧基-2,2-雙丙烯醯氧基甲基-丙基）酯，簡稱：TAPS}. B-2 :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·丙烯醯氧基甲基-丙基）-2,2-雙-丙 烯醯氧基甲基-丙基]酯，簡稱：PADPS} B-3 :二季戊四醇六丙烯酸酯 C-2 ··三羥甲基丙烷三（3-乙基-3-氧雜環丁烷基甲基 )醚 D -1 :三苯基毓三氟甲烷磺酸鹽 S-1 :丙二醇一甲醚乙酸酯 S-2 :二乙二醇二甲醚 S-3 :二乙二醇乙基甲醚 S-4 :乙二醇一丁醚乙酸酯 -68-Comparative Example 3 ά ο fi 1 1 1 1 Q (N ώ Ο (Ν colorless transparent 〇〇 Os 00 ON r - Η 〇 cn inch (N cn 00 (Ν 430 430 10 曰 Example 18 〇〇 < 〇rH ώ 〇1 I 1' 11 < Q ι 1 ζ/) Colorless and transparent ON Os On Os oo On m 沄 沄v〇CN ο r—Η ο ο tH 60th or more embodiment Π τ—Η < or —l B»3 瞧1 D-1 1—Η <Ν ΟΟ colorless and transparent i Os ON G\ ON OO ON m inch m 卜 (Μ Ο ο ο s Τ Η Η 60 days or more Example 16 Τ—Η <; o ” _H B»2 I ό 〇r*"H τ—Hi Q S-3/S-4=7/3 colorless transparent ON ON ON 〇s OO ON inch m ο ι—Ι ο ο § Η 60 More than the above embodiment 15 Α-7 o B-2 1 1 Η Q (Ν m colorless transparent ON ON On C\ ON m inch (Ν m 0C (Ν ο Τ-Η ο ο Ο r-^ 60 days or more embodiment 14 Α-2 〇r-H ώ 〇m 1 1 D-1 in r—< ζλ colorless transparent c\ ON Os Os m π inch (Ν m Ο ο ο ο ▼—Η 60 days or more Example 13 ^4 < o ώ 1 1 r*HQ r—1 (Ν ζλ colorless transparent os Os Os ON OO OS m inch 丨, rn (Ν ο r—ί ο 60 days or more (weight parts) Type (parts by weight) Type (parts by weight) Type (parts by weight) Type of solid content (% by weight) Appearance transparency (%) after addition (C) Heat resistance dimensional stability (%) 250°cx 1 Hour heat resistance dimensional stability (%) 270 ° C x 1 hour heat discoloration (%) Surface hardness 23 ° C 140 ° C Si〇 2 Flatness (nm) Storage stability (曰) High molecular weight (A) Ethylene Unsaturated compound (Β) (C) Epoxy compound (D) Radiation-linear generator, solvent dynamic micro-hardness adhesion 1 -67- 200806701 (64) Further, the ethylenically unsaturated compound (B) in Table 3, The abbreviations of the epoxy compound (C), the radioactive acid generator (D) and the solvent each represent the following: B-1: tripropylene decyloxy pentaerythritol succinic acid {alias: 3_propanol oxime-2, 2-bisacryloxymethyl-propyl)ester, abbreviated as: TAPS}. B-2: penta propylene oxydipentaerythritol succinic acid {alias: [3_(3-acryloxyl-2,2- Bis-propylene methoxymethyl-propyl)-2,2-bis-acryloxymethyl-propyl]ester, abbreviation: PADPS} B-3: dipentaerythritol hexaacrylate C-2 Trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether D-1: triphenylsulfonium trifluoromethanesulfonate S-1: propylene glycol monomethyl ether acetate S-2: Diethylene glycol dimethyl ether S-3: Diethylene glycol ethyl methyl ether S-4: Ethylene glycol monobutyl ether acetate-68-

Claims (1)

200806701 (1) 十、申請專利範圍 1 · 一種硬化性樹脂組成物，其特徵爲含有，具有羧 酸之縮醛酯構造、羧酸之縮酮酯構造、羧酸之1 -烷基環 烷基酯構造及羧酸之t - 丁基酯構造群中所選出至少一種 的構造與院氧基砂院基構造之局分子量物（A)，以及有 機溶劑。 ^ 2 .如申請專利範圍第1項之硬化性樹脂組成物，其中 φ 高分子量物（A)爲，（al)具有羧酸之縮醛酯構造、羧 酸之縮酮酯構造、羧酸之1 -烷基環烷基酯構造或羧酸之t -丁基酯構造的不飽和化合物、（a2 )具有烷氧基矽烷基 構造之不飽和化合物，及必要時使用之（a3 )具有環氧基 之不飽和化合物，以及必要時使用之（a4 )上述（a 1 )、 (a2 )及（a3 )成份以外的烯烴系不飽和化合物之共聚物 〇 3·如申請專利範圍第1或2項之硬化性樹脂組成物， # 其中高分子量物（A )以凝膠滲透色譜法測定的聚苯乙烯 換算重量平均分子量爲2,000以上。 4 ·如申請專利範圍第1至3項中任何1項之硬化性樹脂 組成物，其中另含有至少具有羧基及（甲基）丙烯基之化 合物（B )。 5 ·如申請專利範圍第1至4項中任何1項之硬化性樹脂 組成物，其爲形成彩色濾光片之保護膜用。 6 · —種彩色濾光片之保護膜的形成方法，其特徵爲 ，包含將如申請專利範圍第5項之硬化性樹脂組成物塗佈 -69- 200806701 (2) 於基板上以形成塗膜之步驟，及以放射線照射該塗膜之步 驟。 7 · —種彩色濾光片之保護膜的形成方法，其特徵爲 ，包含將如申請專利範圍第5項之硬化性樹脂組成物塗佈 於基板上以形成塗膜之步驟，及將該塗膜加熱之步驟。 8 · —種彩色濾光片之保護膜，其特徵係以如申請專 • 利範圍第6或7項之方法形成。 200806701 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 Z-'N 定一二 b日 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200806701 (1) X. Patent Application No. 1 · A curable resin composition characterized by having a acetal structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, and a 1-alkylcycloalkyl group of a carboxylic acid The ester structure and the t-butyl ester structural group of the carboxylic acid are selected from at least one of the structure and the local molecular weight (A) of the alkoxy sand-based structure, and an organic solvent. ^2. The curable resin composition of claim 1, wherein the φ high molecular weight (A) is (al) having an acetal structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, or a carboxylic acid An unsaturated compound of a 1-alkylcycloalkyl ester structure or a t-butyl ester of a carboxylic acid, (a2) an unsaturated compound having an alkoxyalkylene structure, and if necessary, (a3) having an epoxy a base-unsaturated compound, and if necessary, (a4) a copolymer of an olefin-based unsaturated compound other than the above components (a1), (a2) and (a3) 〇3, as in claim 1 or 2 The curable resin composition, # wherein the high molecular weight substance (A) has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 2,000 or more. The curable resin composition according to any one of claims 1 to 3, which further comprises a compound (B) having at least a carboxyl group and a (meth)acryl group. The curable resin composition according to any one of claims 1 to 4, which is a protective film for forming a color filter. A method of forming a protective film for a color filter, comprising: coating a curable resin composition according to claim 5 of the patent application-69-200806701 (2) on 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, comprising the steps of: applying a curable resin composition according to claim 5 of the patent application to a substrate to form a coating film, and coating the coating film The step of film heating. 8 - A protective film for a color filter, which is characterized by the method of claim 6 or 7 of the application specification. 200806701 七无·· Ming said single simple number % character: #表为代图表表代的图图表: Case generation map, this table, generation Z-'N fixed one or two b, eight, if the case has a chemical formula Please reveal the chemical formula that best shows the characteristics of the invention: none
TW096113230A 2006-04-19 2007-04-14 A resin composition, a protective film of a color filter, and a method of forming the same TWI411623B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006115553 2006-04-19

Publications (2)

Publication Number Publication Date
TW200806701A true TW200806701A (en) 2008-02-01
TWI411623B TWI411623B (en) 2013-10-11

Family

ID=38817981

Family Applications (1)

Application Number Title Priority Date Filing Date
TW096113230A TWI411623B (en) 2006-04-19 2007-04-14 A resin composition, a protective film of a color filter, and a method of forming the same

Country Status (2)

Country Link
KR (1) KR20070103693A (en)
TW (1) TWI411623B (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101003871B1 (en) * 2003-03-10 2010-12-30 제이에스알 가부시끼가이샤 Resin composition, the protective film of a color filter, and its formation method

Also Published As

Publication number Publication date
KR20070103693A (en) 2007-10-24
TWI411623B (en) 2013-10-11

Similar Documents

Publication Publication Date Title
TWI317371B (en)
TWI467247B (en) A method for forming a hardening resin composition, a protective film and a protective film
KR100977962B1 (en) Curable resin composition, protective film, and its formation method
CN101165091A (en) Thermosetting resin composition, method of forming protective film for color filter and the protective film
JP2004051876A (en) Resin composition and protective film
TWI421268B (en) A method for forming a hardening resin composition, a protective film and a protective film
TWI385192B (en) A hardening resin composition, a protective film, and a method for forming the same
JP5187492B2 (en) Curable resin composition, protective film and method for forming protective film
TWI401272B (en) A resin composition, a method for forming a protective film of a color filter, and a color filter protective film
JP2004256754A (en) Resin composition, protective film and method of forming the same
JP3831947B2 (en) Resin composition, protective film for color filter and method for forming the same
TWI286563B (en) Resin composition and protective film
JP4577507B2 (en) Resin composition, protective film and method for forming protective film
CN101186740B (en) Hot curing resin composition and color filter protection film
CN101328298B (en) Copolymer, resin composition, overcoating film and process for forming the same
TW200808856A (en) Thermosetting resin composition, protective film and method for forming protective film
TWI396715B (en) Resin composition, protective film for color filter and method of forming same
TW200806701A (en) Resin composition, protective film of color filter, and method for forming the same
TW200427766A (en) Resin composition, protection film of color filter and its formation method
JP5003876B2 (en) Resin composition, protective film for color filter and method for forming the same
JP2006083248A (en) Curable resin composition, protective film and method for forming the same
JP2007126647A (en) Curable resin composition, method for forming protective film, and protective film