TWI409284B - A thermosetting resin composition, a protective film for a color filter, and a method for forming the same - Google Patents

A thermosetting resin composition, a protective film for a color filter, and a method for forming the same Download PDF

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TWI409284B
TWI409284B TW096101146A TW96101146A TWI409284B TW I409284 B TWI409284 B TW I409284B TW 096101146 A TW096101146 A TW 096101146A TW 96101146 A TW96101146 A TW 96101146A TW I409284 B TWI409284 B TW I409284B
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acrylate
meth
weight
resin composition
protective film
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TW096101146A
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TW200738772A (en
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Junji Yoshizawa
Hideki Yamauchi
Jiro Ueda
Yoshifumi Kato
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Jsr Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Abstract

Provided is a thermosetting resin composition, which is able to form cured films having high flatness on a substrate having low flatness, has high transparency and surface hardness and excellent various resistances, and is useful for protective films for optical devices. The thermosetting resin composition comprises (A) a copolymer of (a1) a polymerizable unsaturated compound having an oxyranyl group or oxetanyl group and (a2) other polymerizable unsaturated compound than the component (a1), (B) a compound having at least one carboxyl group and at least one (meth)acrylic group, and further (C) an adhesive aid consisting of a silane coupling agent having a reactive substituent.

Description

熱硬化性樹脂組成物、彩色濾光片之保護膜及其形成方法 Thermosetting resin composition, protective film for color filter, and method of forming same

本發明為有關熱硬化性樹脂組成物、由該組成物形成彩色濾光片之保護膜之方法，及彩色濾光片之保護膜之發明。更詳細言之，為有關形成液晶顯示元件(LCD)用彩色濾光片及電荷耦合耦合元件(CCD)用彩色濾光片所使用之保護膜之適當組成物，使用該組成物之保護膜的形成方法，與該組成物所形成之保護膜。 The present invention relates to a thermosetting resin composition, a method of forming a protective film for a color filter from the composition, and a protective film for a color filter. More specifically, the protective film of the composition is used as a suitable composition for forming a protective film for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled coupling element (CCD). A method of forming a protective film formed with the composition.

LCD或CCD等輻射線裝置，於其製造步驟中，多將其顯示元件於溶劑、酸或鹼溶液等中進行浸漬處理，又，以濺鍍方式形成電路電極層之際，將會使顯示元件表面局部地暴露於高溫中。 A radiation device such as an LCD or a CCD, in which a display element is immersed in a solvent, an acid or an alkali solution, etc., and a display electrode is formed by sputtering to form a circuit electrode layer. The surface is locally exposed to high temperatures.

因此，為防止因前述處理所造成之顯示元件劣化，或損傷，而於該顯示元件表面設置對前述處理具有耐性之薄膜所形成之保護膜。 Therefore, in order to prevent deterioration or damage of the display element due to the above-described processing, a protective film formed of a film resistant to the above treatment is provided on the surface of the display element.

前述保護膜，被要求應對於形成該保護膜之基體或下層、形成於保護膜上之層具有高度密著性，膜本身需具有平滑與強韌性，且具有透明性，具有高度之耐熱性及耐光性，即使經過長期間亦不會產生著色、黄變、白化等變質現象，且具有優良耐水性、耐溶劑性、及耐鹼性等性能。可形成滿足前述各種特性之保護膜的材料，已知例如含有具縮水甘油基之聚合物的熱硬化性組成物(參考特開平5- 78453號公報及特開2001-91732號公報)。 The protective film is required to have high adhesion to a substrate or a lower layer forming the protective film and a layer formed on the protective film, the film itself needs to have smoothness and toughness, and has transparency, high heat resistance and Light resistance, even after a long period of time, it does not cause deterioration such as coloring, yellowing, whitening, etc., and has excellent water resistance, solvent resistance, and alkali resistance. A material which can form a protective film which satisfies the aforementioned various characteristics, and is known, for example, a thermosetting composition containing a polymer having a glycidyl group (refer to Japanese Patent Laid-Open No. 5- Japanese Patent Publication No. 78453 and JP-A-2001-91732).

又，前述保護膜作為彩色液晶顯示裝置或電荷耦合元件的彩色濾光片之保護膜使用之情形，一般多要求其於底層基板上所形成之彩色濾光片所造成之高低段差應予平坦化之要求。 Further, when the protective film is used as a protective film for a color filter of a color liquid crystal display device or a charge coupled device, it is generally required that the height difference caused by the color filter formed on the underlying substrate should be flattened. Requirements.

此外，於彩色液晶顯示裝置，例如STN(Super Twisted Nematic)形式或TFT(Thin Film Transister)形式的彩色液晶顯示元件中，為使液晶層之胞間隔保持均勻狀態，多將顆粒狀之調距物散佈於保護膜上，再以面板進行貼合。其後，再使用密封材料以熱壓著方式，將液晶胞密封，但此時所加注之熱量與壓力，常會造成顆粒存在之部分的保護膜發生凹陷現象，而發生胞間隔不均勻等問題。 Further, in a color liquid crystal display device, for example, a color liquid crystal display device in the form of a STN (Super Twisted Nematic) or a TFT (Thin Film Transister), in order to maintain a uniform cell spacing of the liquid crystal layer, a granular spacer is often provided. Spread on the protective film and then attached to the panel. Thereafter, the liquid crystal cell is sealed by using a sealing material in a hot pressing manner, but the heat and pressure which are added at this time often cause a depression of the protective film in the portion where the particles are present, and uneven cell spacing occurs. .

特別是製造STN形式的的彩色液晶顯示元件之際，彩色濾光片與對向基板貼合之精度必須極嚴密地進行，因此對於保護膜則要求極高度之高低段差平坦化性能及耐熱耐壓性能。 In particular, in the case of manufacturing a color liquid crystal display element of the STN type, the precision of bonding the color filter to the counter substrate must be extremely tight. Therefore, the protective film requires extremely high and low step flatness and heat resistance. performance.

又，近年來，於TV用途等玻璃基板尺寸逐漸趨向大型化結果，使不良品之彩色濾光片再予以重製之方式，就經濟面觀之時為一極重要之特性之一。為使該彩色濾光片得以重製，保護膜則需要具有剝離(re-work；膜剝離)之特性。剝離特性，與耐鹼性具有平衡(trade-off)之關係，但目前仍未出現兼具有剝離性與耐鹼性之保護膜。 In addition, in recent years, the size of a glass substrate such as a TV application has gradually increased, and the color filter of a defective product has been reworked, which is one of the most important characteristics in terms of economical appearance. In order to reproduce the color filter, the protective film is required to have the characteristics of re-work (film peeling). The peeling property has a trade-off relationship with alkali resistance, but a protective film having both peeling property and alkali resistance has not yet appeared.

前述保護膜之形成，就可使用簡易方法形成具有優良 硬度之保護膜等優點，於方便上可使用熱硬化性樹脂組成物，但為產生上述各種特性之保護膜用樹脂組成物，其具有可形成強固交聯之交聯基或觸媒，因此，會產生組成物本身之保存期限非常短之問題，於處理上則形成非常繁雜之工作。即，組成物之塗佈性能本身除會產生經時的惡化以外，對塗佈機進行頻繁的維護、洗浄等必要操作上亦為煩雑之工作。 The formation of the aforementioned protective film can be formed by using a simple method. The thermosetting resin composition can be used for convenience, and a resin composition for a protective film which has various characteristics described above, which has a crosslinkable group or a catalyst which can form a strong crosslink, and therefore, There is a problem that the shelf life of the composition itself is very short, and it is very complicated in processing. In other words, in addition to the deterioration of the coating performance of the composition itself, it is also annoying to perform necessary operations such as frequent maintenance and washing of the coater.

但目前仍未出現一種可簡易地形成可滿足透明性等保護膜之一般性能要求以外，且可滿足上述各種性能之保護膜，且作為組成物時仍具有優良之保存安定性之材料。 However, there has not been a material which can easily form a protective film which satisfies the general performance requirements of a protective film such as transparency and which satisfies the above various properties, and which has excellent preservation stability as a composition.

又，特開平4-218561號公報中，雖揭示可使用於塗料、油墨、黏著劑、成形品之含有潛在化羧基化合物之熱硬化性組成物，但其對於彩色濾光片之保護膜則無任何記載。 Further, Japanese Laid-Open Patent Publication No. Hei-4-218561 discloses a thermosetting composition which can be used for a coating material, an ink, an adhesive or a molded article containing a latent carboxyl compound, but it does not have a protective film for a color filter. Any record.

本發明即為鑒於上述情事所提出之發明，其目的為，提供一種即使於低表面平坦性之基體，亦可於該基體上形成高平坦性之硬化膜，此外，具有高度透明性與高表面硬度，故極適用於形成具有優良之耐熱耐壓性、耐鹼性、剝離(re-work)性等各種耐性之光設備用保護膜，及，作為組成物時亦具有優良保存安定性之熱硬化性樹脂組成物，使用該組成物之保護膜的形成方法，及該組成物所形成之保護膜。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a cured film having high flatness on a substrate even in a substrate having low surface flatness, and further having high transparency and high surface. It is extremely suitable for forming a protective film for optical equipment having excellent heat and pressure resistance, alkali resistance, re-workability, and the like, and also has excellent heat retention stability as a composition. A curable resin composition, a method of forming a protective film of the composition, and a protective film formed of the composition.

本發明之其他目的及優點可由以下說明而了解。 Other objects and advantages of the invention will be apparent from the description which follows.

依本發明內容，本發明之上述目的及優點，第1為以含有(A)(a1)具有氧雜環丙烷基(oxiranyl)或氧雜環丁烷基(oxetanyl)之聚合性不飽和化合物及(a2)具有上述(a1)以外之聚合性不飽和化合物所得共聚物(以下亦稱為「(A)共聚物」)，及(B)具有1個以上之羧基及1個以上之(甲基)丙烯酸基之化合物(以下亦稱為「(B)化合物」)為特徵之熱硬化性樹脂組成物而達成。 According to the present invention, the above objects and advantages of the present invention, the first is to contain (A) (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (a2) a copolymer obtained by using the polymerizable unsaturated compound other than the above (a1) (hereinafter also referred to as "(A) copolymer"), and (B) having one or more carboxyl groups and one or more (methyl group) The acrylic group-based compound (hereinafter also referred to as "(B) compound") is a thermosetting resin composition characterized by the composition.

其中，構成(A)共聚物之(a1)成分與(a2)成分之比例，較佳為(a1)5~95重量%、(a2)95~5重量%〔其中，(a1)+(a2)=100重量%〕。 The ratio of the component (a1) to the component (a2) constituting the (A) copolymer is preferably (a1) 5 to 95% by weight, (a2) 95 to 5% by weight (where (a1) + (a2) ) = 100% by weight].

又，(B)化合物之添加量，較佳為相對於(A)共聚物100重量份為10~200重量份。 Further, the amount of the compound (B) to be added is preferably 10 to 200 parts by weight based on 100 parts by weight of the (A) copolymer.

本發明之熱硬化性樹脂組成物中，可再含有(C)具有反應性取代基之矽烷偶合劑所形成之黏著助劑，(C)黏著助劑之添加量，較佳為相對於(A)共聚物100重量份為3~40重量份。 The thermosetting resin composition of the present invention may further contain (C) an adhesion aid formed of a decane coupling agent having a reactive substituent, and (C) an addition amount of the adhesion aid, preferably relative to (A) The copolymer is used in an amount of 3 to 40 parts by weight based on 100 parts by weight.

又，本發明之熱硬化性樹脂組成物，可再含有(D)界面活性劑亦可，(D)界面活性劑之添加量，較佳為相對於(A)共聚物100重量份為0.01~1重量份。 Further, the thermosetting resin composition of the present invention may further contain (D) a surfactant, and (D) the amount of the surfactant added is preferably 0.01 to 100 parts by weight of the (A) copolymer. 1 part by weight.

本發明之熱硬化性樹脂組成物為適合用於形成彩色濾光片之保護膜。 The thermosetting resin composition of the present invention is a protective film suitable for forming a color filter.

又，依本發明之內容，本發明之上述目的及優點，第2為以於基板上，形成上述熱硬化性樹脂組成物之塗膜， 其次經由加熱處理等特徵之彩色濾光片之保護膜之形成方法所達成。 Further, according to the present invention, the above objects and advantages of the present invention are, in a second aspect, a coating film for forming the thermosetting resin composition on a substrate. Next, it is achieved by a method of forming a protective film of a color filter such as heat treatment.

最後，依本發明之內容，本發明之上述目的及優點，第3為以上述彩色濾光片之保護膜之形成方法所形成之彩色濾光片之保護膜之方式予以達成。 Finally, in accordance with the present invention, the above objects and advantages of the present invention are achieved in the third embodiment by the protective film of the color filter formed by the method for forming a protective film for a color filter.

以下，將對本發明之樹脂組成物的各成分作一說明。 Hereinafter, each component of the resin composition of the present invention will be described.

(A)共聚物 (A) copolymer

本發明之(A)共聚物，為含有(a1)具有氧雜環丙烷基或氧雜環丁烷基之聚合性不飽和化合物所產生之聚合單位，及(a2)上述(a1)之聚合單位以外之聚合性不飽和化合物所產生之聚合單位。 The (A) copolymer of the present invention is a polymerization unit produced by containing (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (a2) a polymerization unit of the above (a1) The polymerization unit produced by the polymerizable unsaturated compound other than the polymerization unit.

(A)共聚物中，(a1)聚合性不飽和化合物，並沒有特別限定為含有氧雜環丙烷基或氧雜環丁烷基及聚合性不飽和基。含有氧雜環丙烷基之聚合性不飽和化合物，例如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-n-丙基丙烯酸縮水甘油酯、α-n-丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧丁酯、甲基丙烯酸-3,4-環氧丁酯、丙烯酸-6,7-環氧庚酯、甲基丙烯酸-6,7-環氧庚酯、α-乙基丙烯酸-6,7-環氧庚酯、o-乙烯基苄基縮水甘油醚、m-乙烯基苄基縮水甘油醚、p-乙烯基苄基縮水甘油醚等。 In the (A) copolymer, the (a1) polymerizable unsaturated compound is not particularly limited to an oxiranyl group or an oxetane group and a polymerizable unsaturated group. A polymerizable unsaturated compound containing an oxirane group, such as glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, α-n- Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid-6,7- Epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. .

又，含有氧雜環丁烷基之聚合性不飽和化合物例如3-甲基-3-(甲基)丙烯醯氧甲基氧雜環丁烷、3-乙基-3-( 甲基)丙烯醯氧甲基氧雜環丁烷等。 Further, a polymerizable unsaturated compound containing an oxetanyl group such as 3-methyl-3-(meth)acryloyloxymethyloxetane or 3-ethyl-3-( Methyl) propylene oxime methyl oxetane and the like.

其中又以甲基丙烯酸縮水甘油酯、甲基丙烯酸-6,7-環氧庚酯、o-乙烯基苄基縮水甘油醚、m-乙烯基苄基縮水甘油醚、p-乙烯基苄基縮水甘油醚等，就提高共聚反應性及所得保護膜或絶縁膜之耐熱性、表面硬度等觀點而言為較佳者。 Among them, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl shrinkage Glycerol ether or the like is preferable from the viewpoint of improving copolymerization reactivity and heat resistance and surface hardness of the obtained protective film or the insulating film.

(A)共聚物，除(a1)以外，尚含有由(a2)上述(a1)以外之聚合性不飽和化合物所產生之聚合單位。(a2)聚合性不飽和化合物，例如，具有(甲基)丙烯酸烷酯、(甲基)丙烯酸環狀烷酯、(甲基)丙烯酸芳香酯、不飽和二羧酸二酯、二環不飽和化合物、馬來醯亞胺化合物、不飽和芳香族化合物、共軛二烯化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐、縮醛構造、縮酮構造之不飽和化合物等。 (A) The copolymer contains, in addition to (a1), a polymerization unit produced by (a2) a polymerizable unsaturated compound other than the above (a1). (a2) a polymerizable unsaturated compound, for example, having an alkyl (meth)acrylate, a cyclic alkyl (meth)acrylate, an aromatic (meth)acrylate, an unsaturated dicarboxylic acid diester, and a bicyclic unsaturated group. Compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic anhydride, acetal structure, ketal structure, unsaturated compound Wait.

前述(a2)聚合性不飽和化合物之具體例，例如，(甲基)丙烯酸烷酯如羥甲基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、3-羥丙基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、2,3-二羥丙基(甲基)丙烯酸酯、2-甲基丙烯醯氧乙基水楊酸酯、4-羥苯基(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、sec-丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、n-月桂基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯、n-硬脂基(甲基)丙 烯酸酯、t-丁氧基(甲基)丙烯酸酯、1-二甲基(異)丙基(甲基)丙烯酸酯、1-二甲基(異)丁基(甲基)丙烯酸酯、1-二甲基(異)辛基(甲基)丙烯酸酯、1-甲基-1-乙基(甲基)丙烯酸酯、1-甲基-1-乙基(異)丙基(甲基)丙烯酸酯、1-甲基-1-乙基(異)丁基(甲基)丙烯酸酯、1-甲基-1-乙基(異)辛基丙烯酸酯、1-二乙基(異)丙基(甲基)丙烯酸酯、1-二乙基(異)丁基(甲基)丙烯酸酯、1-二乙基(異)辛基(甲基)丙烯酸酯等；(甲基)丙烯酸環狀烷酯例如環己基環己基(甲基)丙烯酸酯、2-甲基環己基(甲基)丙烯酸酯、三環〔5.2.1.02,6〕癸烷-8-基(甲基)丙烯酸酯、三環〔5.2.1.02,6〕癸烷-8-基氧乙基(甲基)丙烯酸酯、異佛爾酮基(甲基)丙烯酸酯、1-甲基環丙烷(甲基)丙烯酸酯、1-甲基環丁烷(甲基)丙烯酸酯、1-甲基環戊烷(甲基)丙烯酸酯、1-甲基環己基(甲基)丙烯酸酯、1-甲基環庚烷(甲基)丙烯酸酯、1-甲基環辛烷(甲基)丙烯酸酯、1-甲基環壬烷(甲基)丙烯酸酯、1-乙基環癸烷(甲基)丙烯酸酯、1-乙基環丙烷(甲基)丙烯酸酯、1-乙基環丁烷(甲基)丙烯酸酯、1-乙基環戊烷(甲基)丙烯酸酯、1-乙基環己基(甲基)丙烯酸酯、1-乙基環庚烷(甲基)丙烯酸酯、1-乙基環辛烷(甲基)丙烯酸酯、1-乙基環壬烷(甲基)丙烯酸酯、1-乙基環癸烷(甲基)丙烯酸酯、1-(異)丙基環丙烷(甲基)丙烯酸酯、1-(異)丙基環丁烷(甲基)丙烯酸酯、1-(異)丙基環戊烷(甲基)丙烯酸酯、1-(異)丙 基環己基(甲基)丙烯酸酯、1-(異)丙基環庚烷(甲基)丙烯酸酯、1-(異)丙基環辛烷(甲基)丙烯酸酯、1-(異)丙基環壬烷(甲基)丙烯酸酯、1-(異)丙基環癸烷(甲基)丙烯酸酯、1-(異)丁基環丙烷(甲基)丙烯酸酯、1-(異)丁基環丁烷(甲基)丙烯酸酯、1-(異)丁基環戊烷(甲基)丙烯酸酯、1-(異)丁基環己基(甲基)丙烯酸酯、1-(異)丁基環庚烷(甲基)丙烯酸酯、1-(異)丁基環辛烷(甲基)丙烯酸酯、1-(異)丁基環壬烷(甲基)丙烯酸酯、1-(異)丁基環癸基(甲基)丙烯酸酯、1-(異)苄基戊基環丙烷基(甲基)丙烯酸酯、1-(異)戊基環丁烷基(甲基)丙烯酸酯、1-(異)戊基環戊基(甲基)丙烯酸酯、1-(異)戊基環己基(甲基)丙烯酸酯、1-(異)戊基環庚基(甲基)丙烯酸酯、1-(異)戊基環辛基(甲基)丙烯酸酯、1-(異)戊基環壬基(甲基)丙烯酸酯、1-(異)戊基環癸基(甲基)丙烯酸酯，1-(異)己基環丙烷基(甲基)丙烯酸酯、1-(異)己基環丁烷基(甲基)丙烯酸酯、1-(異)己基環己烷基(甲基)丙烯酸酯、1-(異)己基環庚烷基(甲基)丙烯酸酯、1-(異)己基環辛烷基(甲基)丙烯酸酯、1-(異)己基環壬烷基(甲基)丙烯酸酯、1-(異)己基環癸烷基(甲基)丙烯酸酯，1-(異)庚基環丙烷基(甲基)丙烯酸酯、1-(異)庚基環丁烷基(甲基)丙烯酸酯、1-(異)庚基環庚烷基 (甲基)丙烯酸酯、1-(異)庚基環己烷基(甲基)丙烯酸酯、1-(異)庚基環庚烷基(甲基)丙烯酸酯、1-(異)庚基環辛烷基(甲基)丙烯酸酯、1-(異)庚基環壬烷基(甲基)丙烯酸酯、1-(異)庚基環癸烷基(甲基)丙烯酸酯、1-(異)辛基環丙烷基(甲基)丙烯酸酯、1-(異)辛基環丁烷基(甲基)丙烯酸酯、1-(異)辛基環辛基(甲基)丙烯酸酯、1-(異)辛基環己基(甲基)丙烯酸酯、1-(異)辛基環庚烷基(甲基)丙烯酸酯、1-(異)辛基環辛烷基(甲基)丙烯酸酯、1-(異)辛基環壬烷基(甲基)丙烯酸酯、1-(異)辛基環癸烷基(甲基)丙烯酸酯、2-乙基三環〔3.3.1.13,7〕癸烷-2-基-(甲基)丙烯酸酯、2-甲基三環〔3.3.1.13,7〕癸烷-2-基-(甲基)丙烯酸酯、1-乙基三環〔3.3.1.13,7〕癸烷-1-基-(甲基)丙烯酸酯、1-乙基三環〔3.3.1.13,7〕癸烷-1-基-(甲基)丙烯酸酯、3-羥三環〔3.3.1.13,7〕癸烷-1-基-(甲基)丙烯酸酯等；其中，丙烯酸環狀烷酯之環狀烷基部，其亦可為具有例如內酯構造、內醯胺構造、縮醛構造等環狀構造等。例如，2-乙基-γ-丁內酯-2-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-2-基-(甲基)丙烯酸酯、2-乙基-γ-丁內酯-3-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-3-基-(甲基)丙烯酸酯、2-乙基-γ-丁內酯-4-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-2-基-(甲基)丙烯酸酯、2-甲基-δ-戊內酯-2-基-(甲 基)丙烯酸酯、2-乙基-δ-戊內酯-3-基-(甲基)丙烯酸酯、2-甲基-δ-戊內酯-3-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-4-基-(甲基)丙烯酸酯、2-甲基-δ-戊內酯-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-5-基-(甲基)丙烯酸酯、2-甲基-δ-戊內酯-5-基-(甲基)丙烯酸酯等內酯類：2-乙基-γ-丁內醯胺-2-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-2-基-(甲基)丙烯酸酯、2-乙基-γ-丁內醯胺-3-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-3-基-(甲基)丙烯酸酯、2-乙基-γ-丁內醯胺-4-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-2-基-(甲基)丙烯酸酯、2-甲基-6-戊內醯胺-2-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-3-基-(甲基)丙烯酸酯、2-甲基-6-戊內醯胺-3-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-4-基-(甲基)丙烯酸酯、2-甲基-δ-戊內醯胺-4-基-(甲基)丙烯酸酯、2-乙基-6-戊內醯胺-5-基-(甲基)丙烯酸酯、2-甲基-δ-戊內醯胺-5-基-(甲基)丙烯酸酯等內醯胺類；縮醛或縮酮構造，例如1-乙氧乙基(甲基)丙烯酸酯、四氫-2H-吡喃-2-基(甲基)丙烯酸酯、1-(環己基氧基)乙基(甲基)丙烯酸酯、1-(2-甲基丙氧基)乙基(甲基)丙烯酸酯、1-(1,1-二甲基-乙氧基)乙基(甲基)丙烯酸酯、1-(環己基氧基)乙基(甲基)丙烯酸酯等；(甲基)丙烯酸芳香酯，例如苯基甲基丙烯酸酯、苄 基甲基丙烯酸酯等；不飽和二羧酸二酯，例如馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等；二環不飽和化合物，例如二環〔2.2.1〕庚-2-烯、5-甲基二環〔2.2.1〕庚-2-烯、5-乙基二環〔2.2.1〕庚-2-烯、5-甲氧基二環〔2.2.1〕庚-2-烯、5-乙氧基二環〔2.2.1〕庚-2-烯、5,6-二甲氧基二環〔2.2.1〕庚-2-烯、5,6-二乙氧基二環〔2.2.1〕庚-2-烯、5-(2’-羥乙基)二環〔2.2.1〕庚-2-烯、5,6-二羥二環〔2.2.1〕庚-2-烯、5,6-二(羥甲基)二環〔2.2.1〕庚-2-烯、5,6-二(2’-羥乙基)二環〔2.2.1〕庚-2-烯、5-羥基-5-甲基二環〔2.2.1〕庚-2-烯、5-羥基-5-乙基二環〔2.2.1〕庚-2-烯、5-羥甲基-5-甲基二環〔2.2.1〕庚-2-烯等；馬來醯亞胺化合物，例如苯基馬來醯亞胺、環己基馬來醯亞胺、苄基馬來醯亞胺、N-琥珀酵醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-琥珀酵醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀酵醯亞胺基-6-馬來醯亞胺己酸酯、N-琥珀酵醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等；不飽和芳香族化合物，例如苯乙烯、α-甲基苯乙烯、m-甲基苯乙烯、p-甲基苯乙烯、乙烯基甲苯、p-甲氧基苯乙烯等；共軛二烯化合物，例如1,3-丁二烯、異丁烯、2,3-二甲基-1,3-丁二烯等； 不飽和單羧酸，例如丙烯酸、甲基丙烯酸、巴豆酸等；不飽和二羧酸，例如馬來酸、富馬酸、檬康酸、中康酸、衣康酸等；不飽和二羧酸酐，例如上述不飽和二羧酸之各酐；其他不飽和化合物，例如丙烯腈、甲基丙烯腈、氯化乙烯、氯化亞乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯等。 Specific examples of the above (a2) polymerizable unsaturated compound, for example, alkyl (meth)acrylate such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl group (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methyl Propylene oxiranyl salicylate, 4-hydroxyphenyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate , sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl ( Methyl) acrylate, n-stearyl (meth) acrylate, t-butoxy (meth) acrylate, 1-dimethyl(iso)propyl (meth) acrylate, 1-di Methyl (iso)butyl (meth) acrylate, 1-dimethyl (iso) octyl (meth) acrylate, 1-methyl-1-ethyl (meth) acrylate, 1-methyl 1-ethyl(iso)propyl (meth) acrylate, 1-methyl-1-ethyl (iso)butyl (meth) acrylate, 1-methyl-1-ethyl (iso) ) Octyl acrylate, 1-diethyl (isopropyl) (meth) acrylate, 1-diethyl (iso) butyl (meth) acrylate, 1-diethyl (iso) octyl ( Methyl) acrylate or the like; (meth)acrylic acid alkyl ester such as cyclohexylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2, 6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6 ]decane-8-yloxyethyl (meth) acrylate, isophorone (meth) acrylate Ester, 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) acrylate, 1-methylcyclopentane (meth) acrylate, 1-methylcyclohexyl ( Methyl) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1-methylcyclodecane (meth) acrylate, 1- Ethylcyclodecane (meth) acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentane (methyl) Acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (meth) acrylate, 1-ethylcyclooctane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-(iso)propylcyclopropane (meth) acrylate, 1-(iso) propyl Butane (meth) acrylate, 1-(iso)propylcyclopentane (meth) acrylate, 1-(iso)propylcyclohexyl (meth) acrylate, 1-(iso) propyl Cycloheptane (meth) acrylate, 1-(isopropyl)cyclooctane (meth) acrylate, 1-(iso)propylcyclodecane (meth) acrylate, 1-(iso) Propylcyclodecane (meth) acrylate, 1-(iso)butylcyclopropane (meth) acrylate, 1-(iso)butylcyclobutane (meth) acrylate, 1-(iso) Butylcyclopentane (meth) acrylate, 1-(iso)butylcyclohexyl (meth) acrylate, 1-(iso)butylcycloheptane (meth) acrylate, 1-(iso) Butyl cyclooctane (meth) acrylate, 1-(iso)butylcyclodecane (meth) acrylate, 1-(iso)butylcyclodecyl (meth) acrylate, 1-(iso) Benzylpentylcyclopropane (meth) acrylate, 1-(iso)pentylcyclobutane (meth) acrylate, 1-(iso)pentylcyclopentyl (meth) acrylate, 1-(iso)pentylcyclohexyl (meth) acrylate, 1-(iso) Cycloheptyl (meth) acrylate, 1-(iso)pentylcyclooctyl (meth) acrylate, 1-(iso)pentylcyclodecyl (meth) acrylate, 1-(iso) Pentylcyclodecyl (meth) acrylate, 1-(iso)hexylcyclopropane (meth) acrylate, 1-(iso)hexylcyclobutane (meth) acrylate, 1-(iso) Hexylcyclohexane (meth) acrylate, 1-(iso)hexylcycloheptyl (meth) acrylate, 1-(iso)hexylcyclooctyl (meth) acrylate, 1-(iso) Hexylcyclodecylalkyl (meth) acrylate, 1-(iso)hexylcyclodecyl (meth) acrylate, 1-(iso)heptylcyclopropane (meth) acrylate, 1-( Isoheptylcyclobutane (meth) acrylate, 1-(iso)heptylcycloheptyl (meth) acrylate, 1-(iso)heptylcyclohexane (meth) acrylate , 1-(iso)heptylcycloheptyl (meth) acrylate, 1-(iso)heptylcyclooctyl (meth) acrylate, 1-(iso)heptylcyclodecyl (A) Acrylate, 1-(iso)heptylcyclodecyl (meth) acrylate, 1-(iso)octylcyclopropane (meth) acrylate, 1-(iso)octylcyclobutane Base (meth) acrylate, 1-(iso) octyl Cyclooctyl (meth) acrylate, 1-(iso)octylcyclohexyl (meth) acrylate, 1-(iso)octylcycloheptyl (meth) acrylate, 1-(iso) octyl Cyclooctyl (meth) acrylate, 1-(iso)octylcyclodecyl (meth) acrylate, 1-(iso)octylcyclodecyl (meth) acrylate, 2- Ethyltricyclo[3.3.1.1 3,7 ]decane-2-yl-(meth)acrylate, 2-methyltricyclo[3.3.1.1 3,7 ]decane-2-yl-(methyl Acrylate, 1-ethyltricyclo[3.3.1.1 3,7 ]decane-1-yl-(meth)acrylate, 1-ethyltricyclo[3.3.1.1 3,7 ]nonane-1 -yl-(meth) acrylate, 3-hydroxytricyclo[3.3.1.1 3,7 ]decane-1-yl-(meth) acrylate, etc.; wherein the cyclic alkyl moiety of the cyclic alkyl acrylate Further, it may have a cyclic structure such as a lactone structure, an indoleamine structure, or an acetal structure. For example, 2-ethyl-γ-butyrolactone-2-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-2-yl-(meth) acrylate, 2-ethyl -γ-butyrolactone-3-yl-(meth)acrylate, 2-methyl-γ-butyrolactone-3-yl-(meth)acrylate, 2-ethyl-γ-butyrolactone 4-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-4-yl-(meth) acrylate, 2-ethyl-δ-valerolactone-2-yl-( Methyl) acrylate, 2-methyl-δ-valerolactone-2-yl-(meth) acrylate, 2-ethyl-δ-valerolide-3-yl-(meth) acrylate, 2-methyl-δ-valerolactone-3-yl-(meth) acrylate, 2-ethyl-δ-valerolactone-4-yl-(meth) acrylate, 2-methyl-δ -valerolide-4-yl-(meth) acrylate, 2-ethyl-δ-valerolactone-5-yl-(meth) acrylate, 2-methyl-δ-valerolactone-5 - lactones such as benzyl-(meth) acrylates: 2-ethyl-γ-butylidene-2-yl-(meth) acrylate, 2-methyl-γ-butylidene-2 -yl-(meth) acrylate, 2-ethyl-γ-butylidene-3-yl-(meth) acrylate, 2-methyl-γ-butylidene-3-yl-( Methyl) acrylate, 2-ethyl-γ-butylidene-4-yl-(meth)acrylic acid , 2-methyl-γ-butylidene-4-yl-(meth) acrylate, 2-ethyl-δ-pentalin-2-yl-(meth) acrylate, 2-methyl -6-valeroindol-2-yl-(meth) acrylate, 2-ethyl-δ-pentalin-3-yl-(meth) acrylate, 2-methyl-6- Valentin-3-yl-(meth) acrylate, 2-ethyl-δ-pentalin-4-yl-(meth) acrylate, 2-methyl-δ-valeroinamide 4-yl-(meth) acrylate, 2-ethyl-6-pentalinamide-5-yl-(meth) acrylate, 2-methyl-δ-valeroinamide-5-yl - an internal amide such as (meth) acrylate; an acetal or ketal structure such as 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate Ester, 1-(cyclohexyloxy)ethyl (meth) acrylate, 1-(2-methylpropoxy)ethyl (meth) acrylate, 1-(1,1-dimethyl- Ethoxy)ethyl (meth) acrylate, 1-(cyclohexyloxy)ethyl (meth) acrylate, etc.; (meth)acrylic acid aromatic esters, such as phenyl methacrylate, benzyl Acrylate or the like; unsaturated dicarboxylic acid diester, such as diethyl maleate, diethyl fumarate, itaconic acid Ester or the like; a bicyclic unsaturated compound such as bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1 ???hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxyl -5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; maleimide compound, for example Phenyl maleimide, cyclohexylmaleimide, benzyl maleimide, N-succinimide, imino-3-maleimide benzoate, N-amber Imino-4-maleimine butyrate, N-succinimide-6-maleimide caproate, N-succinimide-imido-3-malaya Amine propionate, N-(9-acridinyl) maleimide, etc. An unsaturated aromatic compound such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene or the like; a conjugated diene compound, For example, 1,3-butadiene, isobutylene, 2,3-dimethyl-1,3-butadiene, etc.; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; unsaturated dicarboxylic acid For example, maleic acid, fumaric acid, miconic acid, mesaconic acid, itaconic acid, etc.; unsaturated dicarboxylic anhydrides such as the various anhydrides of the above unsaturated dicarboxylic acids; other unsaturated compounds such as acrylonitrile, A Acrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, and the like.

其中又以苯乙烯、三環〔5.2.1.02,6〕癸烷-8-基甲基丙烯酸酯、p-甲氧基苯乙烯、2-甲基環己基丙烯酸酯、1,3-丁二烯、二環〔2.2.1〕庚-2-烯、N-環己基馬來醯亞胺、甲基丙烯酸、1-乙基環戊烷甲基丙烯酸酯、2-甲基-2-丙烯酸四氫-2H-吡喃-2-基酯等，就共聚合反應性、耐熱性等觀點而言為較佳。 Among them, styrene, tricyclo [5.2.1.0 2,6 ]decane-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butane Alkene, bicyclo[2.2.1]hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentane methacrylate, 2-methyl-2-acrylic acid Hydrogen-2H-pyran-2-yl ester or the like is preferred from the viewpoints of copolymerization reactivity, heat resistance and the like.

前述(a2)聚合性不飽和化合物可單獨或組合使用。 The aforementioned (a2) polymerizable unsaturated compound may be used singly or in combination.

(A)共聚物中，由聚合性不飽和化合物單體所得之構造單位，以單體換算時，較佳為含有(a1)5~95重量%及(a2)95~5重量%，又，更佳為含有(a1)20~95重量%及(a2)80~5重量%，最佳為含有(a1)30~90重量%及(a2)70~10重量%。於該範圍內之含量時，可實現良好之平坦化性能及耐熱性。 In the (A) copolymer, the structural unit obtained from the polymerizable unsaturated compound monomer preferably contains (a1) 5 to 95% by weight and (a2) 95 to 5% by weight in terms of a monomer. More preferably, it contains (a1) 20-95% by weight and (a2) 80-5 weight%, and it is preferable to contain (a1)30-90 weight% and (a2) 70-10 weight%. When the content is within this range, good planarization performance and heat resistance can be achieved.

(A)共聚物之較佳具體例，例如，苯乙烯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙 烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/1-乙基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/1-乙基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/1-乙基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/1-乙基環戊烷甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/1-乙基環戊烷甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N一苯基馬來醯亞胺/1-乙基環戊烷甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/1-甲基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/1-甲基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/1-甲基環己基甲基丙烯酸酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基 丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物等。 (A) Preferred examples of the copolymer, for example, styrene/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2,6 ]decane-8-yl ester/A Glycidyl acrylate copolymer, styrene/N-cyclohexylmaleimide/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/glycidyl methacrylate copolymerization , N-cyclohexylmaleimide/glycidyl methacrylate copolymer, N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclic [5.2 .1.0 2,6 〕decane-8-yl ester/methacrylic acid/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/methacrylic acid/glycidyl methacrylate Copolymer, styrene/N-phenylmaleimide/methacrylic acid/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2,6 ]nonane-8- Ester/1-ethylcyclohexyl methacrylate/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/1-ethylcyclohexyl Acrylate/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-ethylcyclohexyl methacrylate/glycidyl methacrylate copolymer, styrene/A Tricyclohexyl acrylate [5.2.1.0 2,6 ]decane-8-yl ester/1-ethylcyclopentane methacrylate/glycidyl methacrylate copolymer, styrene/N-cyclohexylmalay Yttrium imine/1-ethylcyclopentane methacrylate/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-ethylcyclopentane methacrylate/ Glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2,6 ]decane-8-yl ester/1-methylcyclohexyl methacrylate/glycidyl methacrylate Copolymer, styrene/N-cyclohexylmaleimide/1-methylcyclohexyl methacrylate/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1 -Methylcyclohexyl methacrylate/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2,6 ]decane-8-yl ester/tetrahydro-2H-pyran -2- base Ester/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/tetrahydro-2H-pyran-2-yl ester/glycidyl methacrylate copolymer, styrene/N -phenylmaleimide/tetrahydro-2H-pyran-2-yl ester/glycidyl methacrylate copolymer and the like.

(A)共聚物於使用凝膠滲透色層分析儀(溶出溶劑：四氫呋喃)測定所得之聚苯乙烯換算重量平均分子量(以下，亦稱為「Mw」)較佳為1,000~100,000，更佳為2,000~50,000，最佳為3,000~40,000。Mw未達1,000時，組成物之塗佈性會有不充分之情形，或所形成之保護膜之耐熱性會有不足之情形，又，Mw超過100,000時，其平坦化性能會有不充分之情形。 (A) The polystyrene-equivalent weight average molecular weight (hereinafter, also referred to as "Mw") measured by using a gel permeation chromatography analyzer (dissolving solvent: tetrahydrofuran) is preferably 1,000 to 100,000, more preferably 2,000~50,000, the best is 3,000~40,000. When the Mw is less than 1,000, the coating property of the composition may be insufficient, or the heat resistance of the formed protective film may be insufficient, and when the Mw exceeds 100,000, the flattening performance may be insufficient. situation.

又，(A)共聚物之分子量分布(Mw/Mn)，較佳為5.0以下，更佳為3.0以下。 Further, the molecular weight distribution (Mw/Mn) of the (A) copolymer is preferably 5.0 or less, more preferably 3.0 or less.

前述(A)共聚物，可將上述(a1)聚合性不飽和化合物，及(a2)上述(a1)以外之聚合性不飽和化合物，於適當溶劑及適當聚合起始劑之存在下，使用本身公知之方法，例如自由基聚合方法予以合成。 In the above (A) copolymer, the (a1) polymerizable unsaturated compound and (a2) the polymerizable unsaturated compound other than the above (a1) may be used in the presence of a suitable solvent and a suitable polymerization initiator. A known method, such as a free radical polymerization method, is used for the synthesis.

例如，上述自由基聚合中，將甲基丙烯酸縮水甘油酯等(a1)聚合性不飽和化合物5~95重量份，與苯乙烯等(a2)上述(a1)以外之聚合性不飽和化合物95~5重量份〔其中，(a1)+(a2)=100重量份〕，例如，於乙基溶纖素乙酸酯、丙二醇單甲基醚乙酸酯等溶劑100~400重量份中混合，再對單體成分之合計量100重量份，添加 0.5~15重量份之作為聚合起始劑之偶氮二異丁腈(AIBN)、2,2’-偶氮雙(2,4-二甲基戊腈)等自由基聚合起始劑，於70~100℃下進行3~10小時之聚合反應而製得。 For example, in the above-mentioned radical polymerization, 5 to 95 parts by weight of the (a1) polymerizable unsaturated compound such as glycidyl methacrylate, and styrene or the like (a2), the polymerizable unsaturated compound other than the above (a1) 95~ 5 parts by weight [wherein (a1) + (a2) = 100 parts by weight], for example, mixed in 100 to 400 parts by weight of a solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, and then 100 parts by weight of the total monomer components, added 0.5 to 15 parts by weight of a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator It is obtained by performing polymerization for 3 to 10 hours at 70 to 100 °C.

(B)具有1個以上之羧基及1個以上之(甲基)丙烯酸基之化合物 (B) a compound having one or more carboxyl groups and one or more (meth)acrylic groups

本發明所使用之(B)化合物，例如，三(甲基)丙烯醯氧基季戊四醇琥珀酸(別名：3-(甲基)丙烯醯基氧基-2,2-雙(甲基)丙烯醯基氧基甲基-丙基)酯)、五丙烯醯氧基季戊四醇琥珀酸(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)、二(甲基)丙烯醯氧基季戊四醇琥珀酸(別名：3-(甲基)丙烯醯基氧基-2-(甲基)丙烯醯基氧基甲基-丙基)酯)、五(甲基)丙烯醯氧基二季戊四醇琥珀酸(別名：〔3-(3-(甲基)丙烯醯氧基-2,2-雙-(甲基)丙烯醯氧基甲基-丙基)-2,2-雙-(甲基)丙烯醯氧基甲基-丙基〕酯)、四(甲基)丙烯醯氧基二季戊四醇琥珀酸(別名：〔3-(3-(甲基)丙烯醯氧基-2,2-雙-(甲基)丙烯醯氧基甲基-丙基)-2-(甲基)丙烯醯氧基甲基-丙基)酯)等。 The compound (B) used in the present invention, for example, tris(meth)propenyloxypentaerythritol succinic acid (alias: 3-(methyl)propenyloxy-2,2-bis(methyl)propene oxime氧基oxymethyl-propyl) ester, penta propylene methoxy pentaerythritol succinic acid (alias: (3-(3-propenyloxy-2,2-bis-acryloxymethyl-propyl)) -2,2-bis-acryloxymethyl-propyl) ester, abbreviated as: PADPS), di(methyl) propylene decyl pentaerythritol succinic acid (alias: 3-(methyl) propylene fluorenyl oxygen Benzyl-2-(methyl)propenyl methoxymethyl-propyl) pentoxide, penta(methyl) propylene decyl dipentaerythritol succinic acid (alias: [3-(3-(methyl) propylene oxime] Oxy-2,2-bis-(meth)acryloxymethyl-propyl)-2,2-bis-(methyl)propenyloxymethyl-propyl]), tetra (A) Acryl methoxy dipentaerythritol succinic acid (alias: [3-(3-(methyl) propylene oxime-2,2-bis-(methyl) propylene methoxymethyl-propyl)-2 -(Meth)acryloxymethyl-propyl) ester and the like.

又，(B)化合物，例如可將具有羧基之聚合性不飽和化合物及具有羥基之聚合性不飽和化合物，例如以自由基反應等進行聚合，該羥基亦可使用具有異氰酸酯基與聚 合性不飽和基之化合物經胺基甲酸酯化反應所得者。該情形亦可得到相同之効果。該具有羧基之聚合性不飽和化合物，例如(甲基)丙烯酸等，具有羥基之聚合性化合物例如2-羥乙基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯等，具有異氰酸酯基與聚合性不飽和基之化合物，例如(甲基)丙烯醯氧基乙基異氰酸酯等。 Further, the (B) compound may, for example, be a polymerizable unsaturated compound having a carboxyl group and a polymerizable unsaturated compound having a hydroxyl group, for example, by a radical reaction or the like, and the hydroxyl group may also have an isocyanate group and a poly The compound obtained by the urethanation reaction of the compound of the unsaturated group is obtained. This situation can also achieve the same effect. The polymerizable unsaturated compound having a carboxyl group, for example, a (meth)acrylic acid or the like, a polymerizable compound having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, A compound having an isocyanate group and a polymerizable unsaturated group, for example, (meth)acryloxyethyl isocyanate or the like.

(B)具有1個以上之羧基及1個以上之(甲基)丙烯酸基之化合物，相對於(A)共聚物100重量份而言，較佳為使用10~200重量份，更佳為使用20~150重量份。未達10重量份時，剝離性及平坦性會降低，又，超過200重量份時，因其與基板之密著性會降低，故為不佳。 (B) A compound having one or more carboxyl groups and one or more (meth)acrylic groups is preferably used in an amount of 10 to 200 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the (A) copolymer. 20 to 150 parts by weight. When it is less than 10 parts by weight, the peeling property and flatness are lowered, and when it exceeds 200 parts by weight, the adhesion to the substrate is lowered, which is not preferable.

(C)黏著助劑 (C) Adhesive additives

本發明之熱硬化性樹脂組成物中，於提昇所形成之保護膜與基板間之密著性等目的上可添加(C)黏著助劑。 In the thermosetting resin composition of the present invention, (C) an adhesion aid may be added for the purpose of improving the adhesion between the protective film formed and the substrate.

前述(C)黏著助劑，例如，可使用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，例如，羧基、甲基丙烯醯基基、異氰酸酯基、環氧基等。 As the (C) adhesion aid, for example, a functional decane coupling agent having a reactive substituent can be used. The above reactive substituent is, for example, a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group.

(C)黏著助劑之具體例，例如，三甲氧基矽烷基苯甲酸、γ-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、γ-異氰酸酯基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。 (C) Specific examples of the adhesion promoter, for example, trimethoxydecyl benzoic acid, γ-methyl propyloxypropyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-Isocyanatepropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, β-(3,4-epoxy Cyclohexyl)ethyltrimethoxydecane, and the like.

前述(C)黏著助劑，對(A)共聚物100重量份，較佳為使用3~40重量份，更佳為使用4~20重量份之量。(C)黏著助劑之量超過40重量份時，所得之保護膜會有耐熱性不充分之情形，未達3重量份時，則會有未能得到充分之密著性等問題。 The (C) adhesion aid is preferably used in an amount of from 3 to 40 parts by weight, more preferably from 4 to 20 parts by weight, per 100 parts by weight of the (A) copolymer. (C) When the amount of the adhesion aid exceeds 40 parts by weight, the obtained protective film may have insufficient heat resistance, and if it is less than 3 parts by weight, there may be a problem that sufficient adhesion is not obtained.

(D)界面活性劑 (D) surfactant

本發明之熱硬化性樹脂組成物中，為提昇本發明之樹脂組成物的塗佈性能時，可添加(D)界面活性劑。 In the thermosetting resin composition of the present invention, in order to improve the coating performance of the resin composition of the present invention, (D) a surfactant may be added.

前述界面活性劑，例如氟系界面活性劑、聚矽氧系界面活性劑、質子系界面活性劑、其他界面活性劑等。 The surfactant is, for example, a fluorine-based surfactant, a polyoxyn-based surfactant, a proton-based surfactant, or another surfactant.

上述氟系界面活性劑，例如，BM CHIMIE公司製商品名：BM-1000、BM-1100、大日本油墨學工業(股)製 商品名：美格發F142D、同F172、同F173、同F183、住友3M(股)製 商品名：普拉特FC-135、同FC-170C、同FC-430、同FC-431、(股)彩虹公司製 商品名：富達喜250、同251、同222F、FTX-218、旭硝子(股)製 商品名：S-112、同S-113、同S-131、同S-141，同S-145、同S-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106等市售品等。 The fluorine-based surfactant is, for example, a product name of BM CHIMIE Co., Ltd.: BM-1000, BM-1100, and Dainippon Ink Industrial Co., Ltd., trade name: Megfa F142D, F172, F173, F183, Sumitomo 3M (share) system name: Pratt FC-135, with FC-170C, with FC-430, with FC-431, (share) Rainbow company product name: Fidelity 250, with 251, with 222F , FTX-218, Asahi Glass (stock) system name: S-112, with S-113, with S-131, with S-141, with S-145, with S-382, with SC-101, with SC- 102, the same as SC-103, the same SC-104, the same SC-105, the same as SC-106 and other commercial products.

上述聚矽氧聚矽氧系界面活性劑，例如，東麗．道康寧．聚矽氧(股)製 商品名：SH-28PA、SH-190、SH-193、SZ-6032、SF-8428、DC-57、DC-190、PAINTAD19、FZ-2101、同77、同2118、L-7001、L-7002、大化學． 日本(股)製、Byk-300、同306、同310、同335、同341、同344、同370、信越化學工業(股)製 商品名：KP341、新秋田化成(股)製 商品名：艾伯特EF301、同EF303、同EF352等市售品等。 The above polyfluorene-polyoxy-based surfactant, for example, Toray. Dow Corning. Polyoxymethylene (stock) system name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, the same 77, the same 2118, L-7001, L-7002, Dachemistry. Japanese (share) system, Byk-300, 306, 310, 335, 341, 344, 370, Shin-Etsu Chemical Co., Ltd. Albert EF301, EF303, and EF352 and other commercial products.

上述質子系界面活性劑，例如，聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯二烷酯等。 The proton-based surfactant is, for example, a polyoxyethylene alkyl ether, a polyoxyethylene aryl ether, a polyoxyethylene dialkyl ester or the like.

上述聚氧乙烯烷基醚，例如，聚氧乙烯月桂基醚、聚氧乙烯硬脂醯基醚、聚氧乙烯油基醚等。聚氧乙烯芳基醚，例如，聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等。聚氧乙烯二烷酯，例如，聚氧乙烯二月桂酯、聚氧乙烯二硬脂酯等。 The above polyoxyethylene alkyl ether is, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether or the like. Polyoxyethylene aryl ether, for example, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like. Polyoxyethylene dialkyl ester, for example, polyoxyethylene dilauryl ester, polyoxyethylene distearyl ester, and the like.

上述其他界面活性劑，例如共榮社化學(股)製 商品名：(甲基)丙烯酸系共聚物普利氟No.57、同No.90等。 The above-mentioned other surfactants are, for example, manufactured by Kyoeisha Chemical Co., Ltd., trade name: (meth)acrylic copolymer pril fluoride No. 57, the same as No. 90, and the like.

前述之(D)界面活性劑，相對於(A)共聚物100重量份，較佳為使用0.01~1重量份，更佳為使用0.05~0.4重量份。界面活性劑之量超過1重量份時，於塗佈步驟中塗膜將容易產生膜粗糙龜裂等情形。 The (D) surfactant is preferably used in an amount of 0.01 to 1 part by weight, more preferably 0.05 to 0.4 part by weight, based on 100 parts by weight of the (A) copolymer. When the amount of the surfactant exceeds 1 part by weight, the coating film may easily cause cracking of the film or the like in the coating step.

(E)多元羧酸酐 (E) polycarboxylic anhydride

本發明之熱硬化性樹脂組成物，就提昇耐熱性、耐鹼性等目的上，可添加多元羧酸酐。 In the thermosetting resin composition of the present invention, a polyvalent carboxylic anhydride can be added for the purpose of improving heat resistance and alkali resistance.

(E)多元羧酸酐，例如，衣康酸酐、琥珀酸酐、檬康酸酐、十二碳烯琥珀酸酐、丙三羧酸酐、馬來酸酐、六 氫苯二甲酸酐、甲基四氫苯二甲酸酐、原菠烯二羧酸酐等脂肪族二羧酸酐；1,2,3,4-丁烷四羧酸二酐、環戊烷四羧酸二酐等脂環族多元羧酸二酐；苯二甲酸酐、均苯四甲酸酐、偏苯三甲酸酐、二苯甲酮四羧酸酐等芳香族多元羧酸酐；乙二醇雙偏苯三酸酐、丙三醇三偏苯三酸酯酐等含酯基之酸酐等。其中，又以芳香族多元羧酸酐、特別是偏苯三酸酐，就可得到具有高耐熱性之硬化膜等觀點而為較佳。 (E) a polycarboxylic acid anhydride, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propylene tricarboxylic anhydride, maleic anhydride, six An aliphatic dicarboxylic anhydride such as hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride or raw porphyrin dicarboxylic anhydride; 1,2,3,4-butane tetracarboxylic dianhydride or cyclopentane tetracarboxylic acid An alicyclic polycarboxylic dianhydride such as dianhydride; an aromatic polycarboxylic anhydride such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride or benzophenone tetracarboxylic anhydride; ethylene glycol trimellitic anhydride, and C An acid anhydride-containing acid anhydride such as an alcohol trimellitate anhydride. Among them, an aromatic polycarboxylic acid anhydride, particularly trimellitic anhydride, is preferred because a cured film having high heat resistance can be obtained.

(F)硬化促進劑 (F) hardening accelerator

添加上述(E)多元羧酸酐之情形時，為促進硬化等目的上，可再添加(F)硬化促進劑。 When the above (E) polycarboxylic acid anhydride is added, (F) a hardening accelerator may be further added for the purpose of promoting curing or the like.

(F)硬化促進劑之具體例，如2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、2,4-二胺基-6-〔2’-甲基咪唑基-(1’)〕-乙基-S-三、2,4-二胺基-6-〔2’-十一烷基咪唑基-(1’)〕-乙基-S-三、2,4-二胺基-6-〔2’-乙基-4’-甲基咪唑基十一烷基咪唑基-(1’)〕-乙基-S-三、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基咪唑三聚異氰酸加成物、2,4-二胺基-6-〔2’-甲基咪唑基-(1’)〕-乙基-S-三三聚異氰酸加成物等。 (F) Specific examples of the hardening accelerator, such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[ 2'-methylimidazolyl-(1')]-ethyl-S-three 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-S-III 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolylundecylimidyl-(1')]-ethyl-S-III , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole trimer isocyanate adduct, 2,4 -diamino-6-[2'-methylimidazolyl-(1')]-ethyl-S-three A trimeric isocyanate adduct or the like.

(G)感熱性酸產生劑 (G) sensible acid generator

本發明之熱硬化性樹脂組成物，可添加(G)感熱性 酸產生劑。感熱性酸產生劑例如鋶鹽、苯並噻唑鎓鹽、銨鹽、鏻鹽等，其中又以鋶鹽、苯並噻唑鎓鹽為佳。 The thermosetting resin composition of the present invention may be added with (G) heat sensitivity Acid generator. A thermosensitive acid generator such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, a phosphonium salt or the like, among which a sulfonium salt and a benzothiazolium salt are preferred.

(G)感熱性酸產生劑之添加量，相對於(A)共聚物100重量份，較佳為添加30重量份以下，更佳為為添加20重量份以下。超過30重量份時，其硬度將會大幅降低。 (G) The amount of the heat-sensitive acid generator to be added is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the (A) copolymer. When it exceeds 30 parts by weight, the hardness thereof will be greatly lowered.

樹脂組成物之調製 Modification of resin composition

本發明之熱硬化性樹脂組成物，可將上述各成分，較佳為使其溶解或分散於適當的溶劑中之方式予以調製。較適合使用之溶劑為，可溶解或分散組成物之各成分，且不會與各成分發生反應者。 The thermosetting resin composition of the present invention can be prepared by dissolving or dispersing the above components in a suitable solvent. The solvent which is more suitably used is one which can dissolve or disperse the components of the composition and does not react with each component.

前述溶劑，例如醇、醚、二醇醚、乙二醇烷基醚乙酸酯、二乙二醇單烷基醚、二乙二醇二烷基醚、丙二醇單烷基醚、丙二醇烷基醚乙酸酯、丙二醇烷基醚丙酸酯、芳香族碳化氫、酮、酯等。 The aforementioned solvent, such as alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether Acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like.

其中之具體例，於醇時，例如甲醇、乙醇、苄醇等；醚，例如四氫呋喃等；二醇醚，例如乙二醇單甲基醚、乙二醇單乙基醚等；乙二醇烷基醚乙酸酯，例如甲基溶纖素乙酸酯、乙基溶纖素乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯等；二乙二醇單烷基醚，例如二乙二醇單甲基醚、二乙二醇單乙基醚等； 二乙二醇二烷基醚，例如二乙二醇二甲基醚、二乙二醇二乙酯醚、二乙二醇乙基甲基醚等；丙二醇單烷基醚，例如丙二醇甲基醚、丙二醇乙基醚、丙二醇丙基醚、丙二醇丁基醚等；丙二醇烷基醚乙酸酯，例如丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、丙二醇丁基醚乙酸酯等；丙二醇烷基醚丙酸酯，例如丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等；芳香族碳化氫，例如甲苯、二甲苯等；酮，例如甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、甲基異戊酮等；酯，例如乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥乙酸甲酯、羥乙酸乙酯、羥乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥丙酸甲酯、3-羥丙酸乙酯、3-羥丙酸丙酯、3-羥丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸 乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等。 Specific examples thereof include, in the case of an alcohol, methanol, ethanol, benzyl alcohol, etc.; ethers such as tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; Ethyl acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; Ethylene glycol monoalkyl ether, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.; Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether ether, diethylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether, such as propylene glycol methyl ether , propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, Propylene glycol butyl ether acetate; propylene glycol alkyl ether propionate, such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc. Aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, etc.; esters, for example Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate , propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxypropionic acid Methyl ester, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropionic acid Propyl ester, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxypropionic acid Butyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropionic acid Ethyl ester, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Propyl ester, butyl 3-butoxypropionate, and the like.

其中，又以醇、二乙二醇、丙二醇烷基乙酸酯、乙二醇烷基醚乙酸酯、二乙二醇二烷基醚為佳，其中，又以苄基醇、二乙二醇乙基甲基醚、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、二乙二醇二甲基醚、乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇二乙酯醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲酯、3-甲氧基丙酸乙酯為特佳。 Among them, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether is preferred, wherein benzyl alcohol, diethylene glycol Alcohol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol diethyl ether ether, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate are particularly preferred.

溶劑之使用量，以其於本發明之組成物中的全固體成分(由包含溶劑之組成物總量除以溶劑量所得之量)的含量，較佳為1~50重量%、更佳為5~40重量%之範圍。 The amount of the solvent to be used is preferably from 1 to 50% by weight, more preferably from 1 to 50% by weight, based on the total solid content (the amount obtained by dividing the total amount of the solvent-containing composition by the amount of the solvent) in the composition of the present invention. 5 to 40% by weight range.

與上述溶劑同時，可併用高沸點溶劑。其中所可併用之高沸點溶劑，例如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、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碸、苄基乙基醚、二己基 醚、丙酮基丙酮、異佛爾酮、己酸、辛酸酸、1-辛醇、1-壬醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯、碳酸丙烯、苯基溶纖素乙酸酯等。 At the same time as the above solvent, a high boiling point solvent can be used in combination. A high boiling point solvent which can be used in combination, such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl Ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ- Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

合併高沸點溶劑時之使用量，以相對於包含高沸點溶劑之全溶劑量，較佳為使用90重量%以下，更佳為使用80重量%以下。 The amount of the high-boiling solvent to be combined is preferably 90% by weight or less, and more preferably 80% by weight or less based on the total amount of the solvent containing the high-boiling solvent.

依上述方法調製所得之組成物，較佳為使用孔徑0.2~3.0μm、更佳為孔徑0.2~0.5μm左右之微孔過濾器過濾後再提供使用。 The composition obtained by the above method is preferably filtered using a micropore filter having a pore diameter of 0.2 to 3.0 μm, more preferably about 0.2 to 0.5 μm, and then used.

彩色濾光片之保護膜的形成 Formation of protective film of color filter

其次，將對使用本發明之樹脂組成物的彩色濾光片之保護膜之形成方法作一說明。 Next, a method of forming a protective film of a color filter using the resin composition of the present invention will be described.

將本發明之樹脂組成物溶液塗佈於基板表面，再進行欲燒焙處理以去除溶劑形成塗膜之際，再經加熱處理及可形成目的之彩色濾光片之保護膜。 The resin composition solution of the present invention is applied onto the surface of the substrate, and then subjected to a baking treatment to remove the solvent to form a coating film, and then subjected to heat treatment to form a protective film of the intended color filter.

可作為上述基板使用之物品，例如玻璃、石英、矽、樹脂等之基板。樹脂，例如聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚醚碸、聚碳酸酯、聚亞胺，及環狀烯烴之閉環聚合物及其氫添加物等樹脂。 An article that can be used as the substrate, for example, a substrate of glass, quartz, rhodium, or resin. Resins, such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and ring-shaped polymers of cyclic olefins and their hydrogen additives .

塗佈方法，例如可採用噴灑法、滾筒塗佈法、迴轉塗佈法、條狀塗佈法、油墨噴射法法等適當之方法等，其中，特別是使用旋轉塗佈法、無旋轉塗佈法、孔槽(slit-die )塗佈法等進行塗佈為佳。 The coating method may be, for example, a suitable method such as a spray method, a roll coating method, a rotary coating method, a strip coating method, or an ink jet method, and the like, in particular, a spin coating method or a spin coating method is used. Method, slot (slit-die Coating by a coating method or the like is preferred.

上述欲燒焙之條件，依各成分之種類或添加比例等而有所不同，例如可採用70~90℃、1~15分鐘左右之條件。塗膜之厚度，較佳為0.15~8.5μm、更佳為0.15~6.5μm、又最佳為0.15~4.5μm。又，此處所稱塗膜之厚度，係指去除溶劑後之厚度。 The conditions for the above-mentioned baking are different depending on the type of each component, the ratio of addition, and the like, and for example, it can be used at 70 to 90 ° C for about 1 to 15 minutes. The thickness of the coating film is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm, and most preferably 0.15 to 4.5 μm. Here, the thickness of the coating film referred to herein means the thickness after removing the solvent.

塗膜形成後之加熱處理，可使用熱壓板或乾淨之烤箱等適當的加熱裝置予以實施。處理溫度，例如以150~250℃左右為佳，加熱時間，於使用熱壓板之情形時，例如為5~30分鐘之間，於使用烤箱之情形時，例如採用30~90分鐘之間的處理時間等。 The heat treatment after the formation of the coating film can be carried out using a suitable heating device such as a hot press plate or a clean oven. The treatment temperature is preferably, for example, about 150 to 250 ° C, and the heating time is, for example, between 5 and 30 minutes in the case of using a hot plate, and between 30 and 90 minutes in the case of using an oven, for example. Processing time, etc.

又，樹脂組成物中使用輻射敏感性酸產生劑時，為將該樹脂組成物塗佈於基板表面，經預燒焙去除溶劑以形成塗膜之後，施以輻射線照射處理(曝光處理)後形成目的之保護膜。必要時，可於曝光處理後再進行加熱處理亦可。 Further, when a radiation-sensitive acid generator is used in the resin composition, the resin composition is applied onto the surface of the substrate, and the solvent is removed by pre-baking to form a coating film, and then subjected to radiation irradiation treatment (exposure treatment). A protective film for the purpose is formed. If necessary, heat treatment may be performed after the exposure treatment.

可使用於上述輻射線之照射處理中之輻射線，例如可為可見光線、紫外線、遠紫外線、電子線、X線等，又以含有190~450nm波長之光的紫外線為佳。 The radiation used in the irradiation treatment of the above-mentioned radiation may be, for example, visible light, ultraviolet light, far ultraviolet light, electron light, X-ray, or the like, and ultraviolet light having a wavelength of 190 to 450 nm is preferable.

曝光量，通常為100~20,000 J/m2,較佳為150~10,000 J/m2。 The amount of exposure is usually from 100 to 20,000 J/m 2 , preferably from 150 to 10,000 J/m 2 .

照射輻射線後，可再進行任意之加熱處理。此時之加熱溫度，以150~250℃左右為佳，加熱裝置例如可使用熱壓板或乾淨之烤箱等適當的加熱裝置。加熱時間，於使用 熱壓板時為5~30分鐘之間，於使用烤箱時，可採用30~90分鐘之間的處理時間等。 After the radiation is irradiated, any heat treatment may be performed. The heating temperature at this time is preferably about 150 to 250 ° C. For the heating device, for example, a suitable heating device such as a hot plate or a clean oven can be used. Heating time, for use The hot platen is between 5 and 30 minutes, and when using the oven, the processing time between 30 and 90 minutes can be used.

彩色濾光片之保護膜 Protective film for color filters

依前述方式形成之保護膜，其膜厚度較佳為0.1~8μm，更佳為0.1~6μm，最佳為0.1~4μm。又，本發明之保護膜形成於具有彩色濾光片段差之基板上時，上述之膜厚度，係指彩色濾光片之最上部起算之厚度。 The protective film formed in the above manner preferably has a film thickness of 0.1 to 8 μm, more preferably 0.1 to 6 μm, most preferably 0.1 to 4 μm. Further, when the protective film of the present invention is formed on a substrate having a color filter segment difference, the film thickness refers to the thickness of the uppermost portion of the color filter.

本發明之保護膜，可由下述實施例了解，除滿足密著性、表面硬度、透明性、耐熱性、耐光性、耐溶劑性等以外，即使於加熱狀態下荷重也不會產生凹陷，且具有可使形成於底層基板上之彩色濾光片之高低段差平坦化之優異性能的光裝置用保護膜。 The protective film of the present invention can be understood from the following examples, and in addition to the adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., even if the load is applied under heating, no depression occurs, and A protective film for an optical device having excellent performance in which the height difference of the color filter formed on the underlying substrate is flattened.

特別是，本發明之保護膜，於面板製造步驟中之需暴露於超過250℃之加熱過程中，即使於該情形下，亦具有充分耐性之耐熱性，即使於270℃下亦可保證具有充分之尺寸安定性。 In particular, the protective film of the present invention needs to be exposed to a heating process exceeding 250 ° C in the panel manufacturing step, and even in this case, has sufficient resistance to heat resistance, and is ensured to be sufficient even at 270 ° C. The dimensional stability.

如上所述般，本發明為提供一種可以形成即使於低表面平坦性之基體上，亦可於該基體上形成具有高度平坦性之硬化膜，此外，亦具有高度透明性及表面硬度、耐熱耐壓性、耐鹼性、剝離性等各種優良耐性之光裝置用保護膜所使用之具有優良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，及以上述組成物所形成之保護膜。 As described above, the present invention provides a cured film which can be formed on a substrate which has a high degree of flatness even on a substrate having low surface flatness, and also has high transparency, surface hardness, and heat resistance. a resin composition having excellent storage stability used for a protective film for light-sensitive devices of various excellent resistances such as pressure resistance, alkali resistance, and releasability, a method for forming a protective film using the resin composition, and a composition using the above composition A protective film is formed.

以下將以合成例、實施例對本發明作更具體之說明，但本發明並不受以下實施例所限定。 Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited by the following examples.

(A)共聚物之製造 (A) Manufacture of copolymer

合成例1 Synthesis Example 1

於具備冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮異丁腈5重量份、丙二醇單甲基醚乙酸酯200重量份。隨後加入甲基丙烯酸縮水甘油酯70重量份、苯乙烯30重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，並於該溫度下保持5小時後得含有共聚物(A-1)之聚合物溶液。所得聚合物溶液之固體成分濃度為33.1重量%。 Into a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azoisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Subsequently, 70 parts by weight of glycidyl methacrylate and 30 parts by weight of styrene were added, and after nitrogen substitution, stirring was gradually started. The temperature of the solution was raised to 70 ° C, and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 33.1% by weight.

合成例2 Synthesis Example 2

於具備冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮二異丁腈5重量份、丙二醇單甲基醚乙酸酯200重量份。隨後，加入(3-乙基-3-氧代乙基)甲基丙烯酸甲酯80重量份、苯乙烯20重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，並於此溫度下保持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分濃度為32.9重量%。 To a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 80 parts by weight of (3-ethyl-3-oxoethyl)methyl methacrylate and 20 parts by weight of styrene were added, and after nitrogen substitution, stirring was gradually started. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 32.9% by weight.

合成例3 Synthesis Example 3

於具備冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮雙(2,4-二甲基戊腈)5重量份、丙二醇單甲基醚乙酸酯200重量份。隨後，加入甲基丙烯酸縮水甘油酯40重量份、苯乙烯20重量份、及N-環己基馬來醯亞胺20重量份、甲基丙烯酸20重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，於此溫度下保持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分濃度為29.7重量%。 Into a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, and 20 parts by weight of methacrylic acid were added, and after stirring with nitrogen, stirring was gradually started. . The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-3). The solid content concentration of the obtained polymer solution was 29.7% by weight.

合成例4 Synthesis Example 4

於具備冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮雙(2,4-二甲基戊腈)5重量份、丙二醇單甲基醚乙酸酯200重量份。隨後，加入甲基丙烯酸縮水甘油酯40重量份、苯乙烯20重量份、及甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯20重量份、2-甲基-2-丙烯酸四氫-2H-吡喃-2-基酯20重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，於此溫度下保持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分濃度為30.1重量%。 To a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and 20 parts by weight of tricyclo [5.2.1.0 2,6 ]nonane-8-yl methacrylate, 2-methyl-2, were added. 20 parts by weight of tetrahydro-2H-pyran-2-yl acrylate, and after being substituted with nitrogen, stirring was gradually started. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-4). The solid content concentration of the obtained polymer solution was 30.1% by weight.

合成例5 Synthesis Example 5

於具備有冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮雙(2,4-二甲基戊腈)5重量份、丙二醇單甲基醚乙酸酯 200重量份。隨後，加入甲基丙烯酸縮水甘油酯40重量份、苯乙烯20重量份、及甲基丙烯酸三環〔5.2.1.02,6〕癸烷-8-基酯20重量份、1-乙基環戊烷甲基丙烯酸酯20重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，於此溫度下保持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分濃度為29.8重量%。 To a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and 20 parts by weight of tricyclo [5.2.1.0 2,6 ]nonane-8-yl methacrylate, 1-ethylcyclopentane After 20 parts by weight of the alkyl methacrylate, the mixture was gradually replaced with nitrogen, and stirring was gradually started. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-5). The solid content concentration of the obtained polymer solution was 29.8% by weight.

(B)成分之製造 (B) component manufacturing

合成例6 Synthesis Example 6

於具備有冷卻管、攪拌機之燒瓶中，加入2,2’-偶氮雙(2,4-二甲基戊腈)5重量份、丙二醇單甲基醚乙酸酯200重量份。隨後，加入苯乙烯20重量份、及甲基丙烯酸20重量份、2-羥乙基甲基丙烯酸酯60重量份，以氮取代後，緩緩開始進行攪拌。使溶液溫度上升至70℃，於此溫度下保持5小時。隨後，滴下甲基丙烯醯氧乙基異氰酸酯70重量份，以實施胺基甲酸酯化反應，得含有共聚物(B-3)之聚合物溶液。所得聚合物溶液之固體成分濃度為32.9重量%。 Into a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, and 60 parts by weight of 2-hydroxyethyl methacrylate were added, and after nitrogen substitution, stirring was gradually started. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours. Subsequently, 70 parts by weight of methacryloyloxyethyl isocyanate was dropped to carry out a urethanization reaction to obtain a polymer solution containing the copolymer (B-3). The solid content concentration of the obtained polymer solution was 32.9% by weight.

樹脂組成物之製作及評估 Production and evaluation of resin composition

實施例1 Example 1

加入含有上述合成例1所製得之共聚物(A-1)的溶液(相當於共聚物(A-1)100重量份(固體成分)之量 )，與(B)三丙烯醯氧基季戊四醇琥珀酸(TAPS)80.0重量份，與(C)γ-環氧丙氧基丙基三甲氧基矽烷5.0重量份、(D)界面活性劑之SH-28PA(東麗．道康寧．聚矽氧(股)製)0.1重量份，再加入重量比為8比2之比例的丙二醇單甲基醚乙酸酯(S-1)及二乙二醇乙基甲基醚(S-2)溶液使固體成分濃度達20重量%後，以孔徑0.5μm之微孔過濾器濾過以製作樹脂組成物。 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) 80.0 parts by weight of tripropylene decyloxypentaerythritol succinic acid (TAPS), and 5.0 parts by weight of (C) γ-glycidoxypropyltrimethoxydecane, (D) SH of the surfactant -28PA (Toray, Dow Corning, manufactured by Polyoxane), 0.1 parts by weight, and then added propylene glycol monomethyl ether acetate (S-1) and diethylene glycol B in a ratio of 8 to 2 by weight. The methyl ether (S-2) solution was allowed to have a solid content concentration of 20% by weight, and then filtered through a micropore filter having a pore size of 0.5 μm to prepare a resin composition.

使用旋轉塗佈器將上述組成物塗佈於醺塑SiO2之玻璃基板上後，於熱壓板上經80℃、5分鐘預燒焙後形成塗膜，再於烤箱中進行230℃、60分鐘之加熱處理，得膜厚度2.0μm之保護膜。 The composition was applied onto a glass substrate of SiO 2 by a spin coater, and then pre-baked on a hot plate at 80 ° C for 5 minutes to form a coating film, which was then subjected to 230 ° C, 60 in an oven. After a minute of heat treatment, a protective film having a film thickness of 2.0 μm was obtained.

保護膜之評估 Evaluation of protective film

(1)透明性之評估 (1) Evaluation of transparency

對具有依上述方法形成保護膜之基板，使用分光光度計(150-20型雙束(日立製作所(股)製))測定其400~800nm之透過率。400~800nm之透過率中，最小值係如表1所示。此數值為95%以上時，即可稱保護膜具有良好之透明性。 The substrate having the protective film formed by the above method was measured for a transmittance of 400 to 800 nm using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). Among the transmittances of 400 to 800 nm, the minimum values are shown in Table 1. When the value is 95% or more, the protective film can be said to have good transparency.

(2)耐熱性(耐熱尺寸安定性)之評估 (2) Evaluation of heat resistance (heat stability dimensional stability)

對具有依上述方法形成保護膜之基板，於烤箱中以250℃、1小時之條件下進行加熱，並測定加熱前後之膜厚度。依下述式所算出之耐熱尺寸安定性係如表1所示。此 數值為95%以上時，即可稱具有良好之耐熱尺寸安定性。 The substrate having the protective film formed by the above method was heated in an oven at 250 ° C for 1 hour, and the film thickness before and after heating was measured. The heat resistance dimensional stability calculated by the following formula is shown in Table 1. this When the value is 95% or more, it is said to have good heat-resistant dimensional stability.

耐熱尺寸安定性=〔(加熱後之膜厚度)/(加熱前之膜厚度)〕×100(%) Heat resistance dimensional stability = [(film thickness after heating) / (film thickness before heating)] × 100 (%)

(3)耐鹼性(耐鹼尺寸安定性)之評估 (3) Evaluation of alkali resistance (alkali stability)

對具有依上述方法形成保護膜之基板，將其浸漬於加溫至40℃之5%氫氧化鈉水溶液中30分鐘後，將其取出，以超純水洗浄，並於加溫至120℃之熱壓板上乾燥2分鐘，測定鹼浸漬前後之膜厚度。依下述式所算出之耐鹼尺寸安定性係如表1所示。 The substrate having the protective film formed by the above method was immersed in a 5% sodium hydroxide aqueous solution heated to 40 ° C for 30 minutes, and then taken out, washed with ultrapure water, and heated to 120 ° C. The plate was dried on a hot plate for 2 minutes, and the film thickness before and after alkali immersion was measured. The alkali resistance dimensional stability calculated by the following formula is shown in Table 1.

此數值為95%以上時，即可稱具有良好之耐鹼尺寸安定性。 When the value is 95% or more, it can be said to have good alkali stability.

耐鹼尺寸安定性=〔(鹼浸漬後之膜厚度)/(鹼浸漬前之膜厚度)〕×100(%) Alkali resistance dimensional stability = [(film thickness after alkali impregnation) / (film thickness before alkali impregnation)] × 100 (%)

(4)耐熱變色性之評估 (4) Evaluation of heat discoloration

對具有依上述方法形成保護膜之基板，於烤箱中以250℃加熱1小時，對加熱前後之透明性依上述(1)相同方法進行測定。依下述式所算出之耐熱變色性係如表1所示。此數值為5%以下時，即稱具有良好之耐熱變色性。 The substrate having the protective film formed by the above method was heated in an oven at 250 ° C for 1 hour, and the transparency before and after heating was measured in the same manner as in the above (1). The heat discoloration property calculated by the following formula is shown in Table 1. When the value is 5% or less, it is said to have good heat discoloration resistance.

耐熱變色性=加熱前之透過率-加熱後之透過率(%) Heat discoloration = transmittance before heating - transmittance after heating (%)

(5)表面硬度(鉛筆硬度)之測定 (5) Determination of surface hardness (pencil hardness)

對具有依上述方法形成保護膜之基板，依JIS K-5400-1990之8.4.1鉛筆劃割試驗以測定保護膜之表面硬度。此數值係如表1所示。該數值為3~4H或更硬時，則稱具有良好之表面硬度。 For the substrate having the protective film formed by the above method, the surface hardness of the protective film was measured in accordance with the 8.4.1 pencil dicing test of JIS K-5400-1990. This value is shown in Table 1. When the value is 3~4H or harder, it is said to have good surface hardness.

(6)動態微小硬度之測定 (6) Determination of dynamic micro hardness

對具有依上述方法形成保護膜之基板，使用島津動態微小硬度計DUH-201((股)島津製作所製)，以稜角115°三角錐體(Herchcovitch型)之擠壓試驗，將保護膜之動態微小硬度以荷重：0.1 gf、速度：0.0145gf/sec.、保持時間：5 sec.、溫度23℃及140℃之測定條件下進行測定。其結果係如表1所示。 For the substrate having the protective film formed by the above method, the Shimadzu dynamic micro hardness tester DUH-201 (manufactured by Shimadzu Corporation) was used to test the dynamics of the protective film by an extrusion test of an angular pyramid of 115° (Herchcovitch type). The microhardness was measured under the measurement conditions of a load of 0.1 gf, a speed of 0.0145 gf/sec., a holding time of 5 sec., and a temperature of 23 ° C and 140 ° C. The results are shown in Table 1.

(7)密著性之評估 (7) Evaluation of adhesion

對具有依上述方法形成保護膜之基板，於進行加壓鍋(pressure cooker)試驗(120℃、溼度100%、4小時)後，再以JIS K-5400-1990之8.5.3付著性棋盤孔膠布法評估其保護膜之密著性(對SiO2之密著性)。棋盤孔目100個中，所残留之棋盤孔數目係如表1所示。 For the substrate having the protective film formed by the above method, after performing a pressure cooker test (120 ° C, humidity of 100%, 4 hours), the magnetic board is also given as 8.5.3 of JIS K-5400-1990. The hole tape method was used to evaluate the adhesion of the protective film (adhesion to SiO 2 ). Among the 100 checker holes, the number of remaining checkerboard holes is shown in Table 1.

又，對Cr之密著性評估中，除將醺塑SiO2玻璃基板以Cr基板取代以外，其他皆依上述相同方法形成膜厚度2.0μm之保護膜，依上述之棋盤孔膠布法進行相同之評估 。其結果係如表1所示。 Further, in the adhesion evaluation of Cr, except that the SiO 2 glass substrate was replaced with a Cr substrate, a protective film having a film thickness of 2.0 μm was formed by the same method as described above, and the same method was carried out according to the checkerboard tape method described above. Evaluation. The results are shown in Table 1.

(8)平坦化性之評估 (8) Evaluation of flatness

於醺塑SiO2玻璃基板上，將顏料系彩色光阻(商品名「JCRRED 689」、「JCR GREEN 706」、「CR 8200B」，以上皆為JSR(股)製)使用旋轉塗佈器塗佈於其上，再於熱壓板上以90℃、150秒間進行預燒焙以形成塗膜。其後，介由特定之圖型光罩，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)以i線換算為2,000J/m2之曝光量進行照射後，以0.05%氫氧化鉀水溶液予以顯影，經超純水洗滌60秒後，再於烤箱中以230℃進行30分鐘加熱處理，形成紅、綠、及藍等3色之條紋狀彩色濾光片(條紋寬度100μm)。 On a SiO 2 glass substrate, a pigment-based color resist (trade name "JCRRED 689", "JCR GREEN 706", "CR 8200B", all of which is manufactured by JSR Co., Ltd.) was coated with a spin coater. On this, a pre-baking was carried out at 90 ° C for 150 seconds on a hot plate to form a coating film. Thereafter, a specific pattern mask was used, and the exposure machine Canon PLA501F (manufactured by Canon) was used to convert the i-line into 2,000 in ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7:2.5:4.8). After the exposure amount of J/m 2 was irradiated, it was developed with a 0.05% potassium hydroxide aqueous solution, washed with ultrapure water for 60 seconds, and then heat treated in an oven at 230 ° C for 30 minutes to form red, green, and blue. A three-color striped color filter (strip width 100 μm).

形成有該彩色濾光片之基板表面的凹凸，以表面粗度計「α-史貼普」(商品名：丹克爾公司製)測定結果，得知其為1.0μm。其係以測定長度2,000μm、測定範圍2,000μm四方、測定點數n=5下進行測定。即，將測定方向設定為紅、綠、藍方向之條紋直線的短軸方向及紅．紅、綠．綠、藍．藍之同色的條紋直線的長軸方向等2方向，並對各方向以n=5之條件進行測定(合計之n數為10)。 The unevenness of the surface of the substrate on which the color filter was formed was measured by a surface roughness of "α-Street" (trade name: manufactured by Dankel), and it was found to be 1.0 μm. The measurement was carried out by measuring a length of 2,000 μm, a measurement range of 2,000 μm, and a measurement number of n=5. That is, the measurement direction is set to the short-axis direction of the stripe line in the red, green, and blue directions and red. Red, green. Green blue. The long-axis direction of the stripe line of the same color of blue is in two directions, and the measurement is performed under the condition of n=5 in each direction (the total number of n is 10).

於其上方，將上述保護膜形成用組成物使用旋轉塗佈器塗佈後，於熱壓板上以90℃、5分鐘預燒焙而形成塗膜 ，再於烤箱中進行230℃、60分鐘之加熱處理，以於彩色濾光片之上面再形成膜厚度2.0μm之保護膜。其中，此處所稱之膜厚度，係指形成於基板上之彩色濾光片的最上面起算的厚度之意。 The protective film-forming composition was applied thereon by a spin coater, and then pre-baked at 90 ° C for 5 minutes on a hot plate to form a coating film. Then, heat treatment was carried out at 230 ° C for 60 minutes in an oven to form a protective film having a film thickness of 2.0 μm on the color filter. Here, the film thickness referred to herein means the thickness of the uppermost layer of the color filter formed on the substrate.

對依上述方法形成之於彩色濾光片上具有保護膜之基板，使用接觸式膜厚測定裝置「α-史貼普」(商品名：丹克爾公司製)測定保護膜之表面凹凸。其係以測定長度2,000μm、測定範圍2,000μm四方、測定點數n=5下測定者。即，將測定方向設定為紅、綠、藍方向之條紋直線的短軸方向及紅．紅、綠．綠、藍．藍之同色的條紋直線的長軸方向等2方向，並對各方向以n=5之條件進行測定(合計之n數為10)。 With respect to the substrate having the protective film formed on the color filter by the above method, the surface unevenness of the protective film was measured using a contact type film thickness measuring device "α-Shi Pu Pu" (trade name: manufactured by Dankel). This was measured by measuring a length of 2,000 μm, a measurement range of 2,000 μm, and a measurement number of n=5. That is, the measurement direction is set to the short-axis direction of the stripe line in the red, green, and blue directions and red. Red, green. Green blue. The long-axis direction of the stripe line of the same color of blue is in two directions, and the measurement is performed under the condition of n=5 in each direction (the total number of n is 10).

各測定之最高部與最底部之高低差(nm)之10次平均值係如表1所示。 The 10th average of the height difference (nm) between the highest part and the bottom part of each measurement is shown in Table 1.

此數值低於300nm以下時，即稱具有良好平坦性。 When the value is less than 300 nm, it is said to have good flatness.

(9)剝離性之評估 (9) Evaluation of peelability

於(8)所製作之彩色濾光片之上面形成膜厚度為2.0μm之保護膜。將彩色濾光片用剝離液(横浜油脂(股)製、Semi Clean DF-7)加溫至50℃，並將上述附有保護膜之彩色濾光片浸漬於其中。於10分鐘後及20分鐘後將基板取出，以海綿擦拭中使用純水予以洗浄，以目視方式觀察保護膜(包含顏料系彩色光阻)是否剝離。於10分鐘即可剝離者為「○」，於20分鐘使可剝離者為「△ 」、20分鐘亦不能剝離者則為「×」。剝離時間越短者，則判斷其具有良好剝離性。 A protective film having a film thickness of 2.0 μm was formed on the color filter prepared in (8). The color filter was heated to 50 ° C with a peeling liquid (manufactured by Yokohama Oil Co., Ltd., Semi Clean DF-7), and the above-mentioned color filter with a protective film was immersed therein. After 10 minutes and 20 minutes, the substrate was taken out, washed with pure water by sponge wiping, and the protective film (including the pigment-based color resist) was visually observed to be peeled off. The peeling can be "○" in 10 minutes, and the peelable person can be "△" in 20 minutes. If it is not peelable in 20 minutes, it is "X". The shorter the peeling time, the better the peelability is judged.

(10)保存安定性之評估 (10) Evaluation of preservation stability

對於依實施例1所製得之保護膜形成用之樹脂組成物的黏度，使用東京計器(股)製ELD型黏度計進行測定。其後，將該組成物於25℃下静置，並每日測定25℃下之溶液黏度。以調製後之黏度為基準，計算增黏5%增黏時所需要之日數，此日數係如表1所示。此日數為15日以上時，則稱其具有良好之保存安定性。 The viscosity of the resin composition for forming a protective film obtained in Example 1 was measured using an ELD type viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the composition was allowed to stand at 25 ° C, and the solution viscosity at 25 ° C was measured daily. Based on the viscosity after the modulation, the number of days required to increase the viscosity and increase the viscosity is calculated. The number of days is shown in Table 1. When the number of days is 15 days or more, it is said to have good preservation stability.

實施例2~22及比較例1~3 Examples 2 to 22 and Comparative Examples 1 to 3

組成物之各成分種類及量係如表1所記載般，除使用表1所記載之溶劑並配合表1記載之固體成分濃度以外，其他皆依實施例1相同方法製作樹脂組成物。 The composition and amount of each component of the composition were as follows. The resin composition was produced in the same manner as in Example 1 except that the solvent described in Table 1 was used and the solid content concentration shown in Table 1 was used.

使用依上述方法製作之保護膜形成用之樹脂組成物，依實施例1相同方法形成保護膜，並進行評估。其結果係如表1所示。 Using the resin composition for forming a protective film prepared by the above method, a protective film was formed in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

實施例23~31 Examples 23~31

組成物之各成分的種類及量係如表2所記載般，除使用表2所記載之溶劑，並配合表2記載之固體成分濃度以外，其他皆依實施例1相同方法製作樹脂組成物。 The type and amount of each component of the composition were as follows. The resin composition was produced in the same manner as in Example 1 except that the solvent described in Table 2 was used and the solid content concentration shown in Table 2 was used.

除使用孔槽(slit-die)塗佈法取代旋轉塗佈法以外， 其他皆依實施例1相同方法製作樹脂組成物，以形成保護膜，並進行評估。其結果係如表2所示。 In addition to using a slit-die coating method instead of a spin coating method, The resin composition was prepared in the same manner as in Example 1 to form a protective film and evaluated. The results are shown in Table 2.

又，表1及表2中，(B)具有1個以上之羧基及1個以上之丙烯酸基之化合物、(C)黏著助劑、(D)界面活性劑、(E)多元羧酸酐、(F)硬化促進劑、及(S)溶劑等之簡稱，分別為以下所述內容。 Further, in Tables 1 and 2, (B) a compound having one or more carboxyl groups and one or more acrylic groups, (C) an adhesion aid, (D) a surfactant, (E) a polycarboxylic acid anhydride, ( F) The abbreviations of the hardening accelerator, the (S) solvent, and the like are as follows.

B-1：三丙烯醯氧基季戊四醇琥珀酸(別名：3-丙烯醯基氧代-2,2-雙丙烯醯基氧代甲基-丙基)酯，簡稱：TAPS) B-1: tripropylene decyloxy pentaerythritol succinic acid (alias: 3-propenyl oxo oxo-2,2-bispropenyl methoxymethyl-propyl) ester, referred to as: 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-2: penta propylene decyl dipentaerythritol succinic acid (alias: [3-(3-propenyloxy-2,2-bis-acryloxymethyl-propyl)-2,2-bis- Propylene methoxymethyl-propyl) ester, abbreviation: PADPS)

C-1：γ-環氧丙氧基丙基三甲氧基矽烷 C-1: γ-glycidoxypropyltrimethoxydecane

D-1：聚矽氧系界面活性劑(東麗．道康寧．聚矽氧(股)製商品名：SH-28PA) D-1: Polyoxane surfactant (Dongli. Dow Corning. Polyethylene Oxide (stock) product name: SH-28PA)

D-2：聚矽氧系界面活性劑(大化學．日本(股)製、商品名：BYK-344)、 D-3：氟系界面活性劑((股)彩虹公司製、商品名：FTX-218)、 D-4：聚矽氧系界面活性劑(東麗．道康寧．聚矽氧(股)製、商品名：PAINTAD19)、 D-2: Polyoxane surfactant (Major Chemical Co., Ltd., trade name: BYK-344), D-3: a fluorine-based surfactant (manufactured by Rainbow Co., Ltd., trade name: FTX-218), D-4: polyfluorene-based surfactant (Dongli. Dow Corning. Polyoxyl (manufactured by the company), trade name: PAINTAD19),

E-1：偏苯三酸酐 E-1: trimellitic anhydride

F-1：2-苯基-4-甲基咪唑 F-1: 2-phenyl-4-methylimidazole

S-1：丙二醇單甲基醚乙酸酯 S-1: propylene glycol monomethyl ether acetate

S-2：二乙二醇乙基甲基醚 S-2: diethylene glycol ethyl methyl ether

S-3：3-甲氧基丙酸甲基 S-3: 3-methoxypropionic acid methyl

a-1：雙酚A酚醛清漆型環氧樹脂(日本環氧樹脂(股)製 商品名：艾碧康157S65、簡稱：EP157S65) A-1: bisphenol A novolak type epoxy resin (Japanese epoxy resin (stock) system name: Ai Bikang 157S65, abbreviation: EP157S65)

b-1：三丙烯醯氧基乙基三聚異氰酸(東亜合成(股)製，商品名：艾羅力M-315M) B-1: tripropylene methoxyethyl isomeric isocyanate (manufactured by Tosoh Chemical Co., Ltd., trade name: Eloline M-315M)

b-2：二季戊四醇六丙烯酸酯(日本化藥(股)製商品名：KAYARAD DPHA) B-2: dipentaerythritol hexaacrylate (product name: KAYARAD DPHA)

本發明之樹脂組成物，即使於低表面平坦性之基體，亦可於該基體上，形成具有高度平坦性之硬化膜，此外，亦具有高度透明性及表面硬度，且具有優良之耐熱耐壓性、耐鹼性、剝離性等各種耐性，而極適合作為液晶顯示元件(LCD)用彩色濾光片或電荷耦合元件(CCD)用彩色濾光片等之光裝置用保護膜。 The resin composition of the present invention can form a cured film having high flatness on the substrate even in a substrate having low surface flatness, and also has high transparency and surface hardness, and has excellent heat resistance and pressure resistance. A protective film for an optical device such as a color filter for a liquid crystal display element (LCD) or a color filter for a charge coupled device (CCD), which is suitable for various resistances such as properties, alkali resistance, and releasability.

Claims (9)

一種熱硬化性樹脂組成物，其特徵為，含有(A)(a1)具有氧雜環丙烷基(oxiranyl)或氧雜環丁烷基(oxetanyl)之聚合性不飽和化合物及(a2)上述(a1)以外之聚合性不飽和化合物之共聚物，及(B)具有1個以上之羧基及1個以上之(甲基)丙烯酸基之化合物；構成(A)共聚物之(a1)成分與(a2)成分之比例，以相對於(a1)成分與(a2)成分之合計重量為基準，(a1)成分為5~95重量%，(a2)成分為95~5重量%；且(a1)為由丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-n-丙基丙烯酸縮水甘油酯、α-n-丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧丁酯、甲基丙烯酸-3,4-環氧丁酯、丙烯酸-6,7-環氧庚酯、甲基丙烯酸-6,7-環氧庚酯、α-乙基丙烯酸-6,7-環氧庚酯、o-乙烯基苄基縮水甘油醚、m-乙烯基苄基縮水甘油醚、p-乙烯基苄基縮水甘油醚、3-甲基-3-(甲基)丙烯醯氧甲基氧雜環丁烷及3-乙基-3-(甲基)丙烯醯氧甲基氧雜環丁烷中選擇之1者以上；(a2)為由(甲基)丙烯酸烷酯、(甲基)丙烯酸環狀烷酯、(甲基)丙烯酸芳香酯、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、不飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐及具有縮醛構造或縮酮構造之不飽和化合物中選擇之1者以上。 A thermosetting resin composition comprising (A) (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group and (a2) the above ( a copolymer of a polymerizable unsaturated compound other than a1), and (B) a compound having one or more carboxyl groups and one or more (meth)acrylic groups; (a1) component and (a) copolymer (A) The ratio of the component a2) is 5 to 95% by weight based on the total weight of the component (a1) and the component (a2), and the component (a2) is 95 to 5% by weight; and (a1) It is composed of glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic-3,4 -butyl butyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6 , 7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3-(methyl) propylene Oxyxymethyloxetane and 3-ethyl One or more selected from the group consisting of -3-(meth)acryloyloxymethyloxetane; (a2) is an alkyl (meth)acrylate, a cyclic alkyl (meth)acrylate, (methyl) Acrylic acid aromatic ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleic imine compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated two One or more selected from the group consisting of a carboxylic acid, an unsaturated dicarboxylic anhydride, and an unsaturated compound having an acetal structure or a ketal structure. 如申請專利範圍第1項之熱硬化性樹脂組成物，其 中，(B)具有1個以上之羧基及1個以上之(甲基)丙烯酸基之化合物的添加量為，相對於(A)共聚物100重量份為10~200重量份。 A thermosetting resin composition as claimed in claim 1 of the patent scope, In the above, (B) the compound having one or more carboxyl groups and one or more (meth)acrylic groups is added in an amount of 10 to 200 parts by weight based on 100 parts by weight of the (A) copolymer. 如申請專利範圍第1或2項之熱硬化性樹脂組成物，其尚含有(C)由具有反應性取代基之矽烷偶合劑所形成之黏著助劑。 The thermosetting resin composition of claim 1 or 2 further comprising (C) an adhesion promoter formed of a decane coupling agent having a reactive substituent. 如申請專利範圍第3項之熱硬化性樹脂組成物，其中，(C)黏著助劑之添加量為’相對於(A)共聚物100重量份為3~40重量份。 The thermosetting resin composition of the third aspect of the invention, wherein the (C) adhesion aid is added in an amount of from 3 to 40 parts by weight based on 100 parts by weight of the (A) copolymer. 如申請專利範圍第1或2項之熱硬化性樹脂組成物，其尚含有(D)界面活性劑。 The thermosetting resin composition of claim 1 or 2, which further contains (D) a surfactant. 如申請專利範圍第5項之熱硬化性樹脂組成物，其中，(D)界面活性劑之添加量為，相對於(A)共聚物100重量份為0.01~1重量份。 The thermosetting resin composition of claim 5, wherein the (D) surfactant is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the (A) copolymer. 如申請專利範圍第1或2項之熱硬化性樹脂組成物，其係用於形成彩色濾光片之保護膜。 A thermosetting resin composition according to claim 1 or 2, which is used for forming a protective film of a color filter. 一種彩色濾光片之保護膜的形成方法，其特徵為，於基板上形成申請專利範圍第7項之熱硬化性樹脂組成物的塗膜，其次進行加熱處理所得者。 A method for forming a protective film for a color filter, which comprises forming a coating film of a thermosetting resin composition of claim 7 on a substrate, and secondarily performing heat treatment. 一種彩色濾光片之保護膜，其特徵為由申請專利範圍第8項之彩色濾光片之保護膜的形成方法所形成者。 A protective film for a color filter, which is characterized by the method for forming a protective film for a color filter of claim 8 of the patent application.
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