TWI422601B - Thermosetting resin composition - Google Patents

Thermosetting resin composition Download PDF

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TWI422601B
TWI422601B TW097141647A TW97141647A TWI422601B TW I422601 B TWI422601 B TW I422601B TW 097141647 A TW097141647 A TW 097141647A TW 97141647 A TW97141647 A TW 97141647A TW I422601 B TWI422601 B TW I422601B
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copolymer
meth
acrylate
acrylic acid
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TW200938555A (en
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Kazuo Takebe
Katsuharu Inoue
Kimiyuki Shirouchi
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Sumitomo Chemical Co
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

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  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

熱硬化性樹脂組成物Thermosetting resin composition

本發明係關於一種熱硬化性樹脂組成物。The present invention relates to a thermosetting resin composition.

液晶顯示裝置或固體攝像元件等裝置係使用在玻璃基板或矽晶圓等基材上形成著色畫素之彩色濾光基板，或形成驅動元件或配線之陣列基板等之構件。該等構件在製造步驟中浸漬於酸或鹼溶液中，在形成驅動元件或配線時，藉由濺鍍局部暴露於高溫之下等，而有遭受嚴苛處理之情況。因此，為了避免該等構件在製造步驟中受損，因此有在構件表面上設置保護膜之情況。A device such as a liquid crystal display device or a solid-state image sensor is a member that forms a color filter substrate on which a color pixel is formed on a substrate such as a glass substrate or a germanium wafer, or an array substrate on which a driver element or a wiring is formed. These members are immersed in an acid or alkali solution in the manufacturing step, and are subjected to severe treatment when the driving element or wiring is formed by partial exposure to high temperature by sputtering or the like. Therefore, in order to prevent the members from being damaged in the manufacturing steps, there is a case where a protective film is provided on the surface of the member.

該保護膜要求有可耐受上述嚴苛處理之特性，具體而言，在可形成圖型之程度下要求與基材或底層之密著性優異，且表面硬度高、透明性優異、耐溶劑性優異、耐熱性優異。The protective film is required to have the characteristics to withstand the above-mentioned severe treatment. Specifically, it is required to have excellent adhesion to the substrate or the underlayer to the extent that the pattern can be formed, and has high surface hardness, excellent transparency, and solvent resistance. Excellent in properties and excellent in heat resistance.

作為如此保護膜中可使用之熱硬化性樹脂組成物已知含有由以羧基及縮水甘油醚基為代表之具有環氧基之丙烯酸系共聚物組成之結合劑樹脂、具有乙烯性不飽和鍵之聚合性化合物及熱自由基產生化合物之熱硬化性組成物(專利文獻1)。A thermosetting resin composition which can be used in such a protective film is known to contain a binder resin composed of an acrylic copolymer having an epoxy group typified by a carboxyl group and a glycidyl ether group, and has an ethylenically unsaturated bond. A thermosetting composition of a polymerizable compound and a thermal radical generating compound (Patent Document 1).

[專利文獻1]特開2000-119472號公報　第2頁左欄第2行-第8行[Patent Document 1] JP-A-2000-119472, page 2, left column, second line - line 8

本發明之目的係提供一種可形成透明性、表面硬度優異之塗膜之熱硬化性樹脂組成物。An object of the present invention is to provide a thermosetting resin composition which can form a coating film having excellent transparency and surface hardness.

本發明者經檢討之結果發現本發明之熱硬化性樹脂組成物可解決上述問題。As a result of review, the inventors have found that the thermosetting resin composition of the present invention can solve the above problems.

亦即，本發明係提供下列[1]~[5]者。That is, the present invention provides the following [1] to [5].

[1]一種熱硬化性樹脂組成物，其特徵為含有結合劑樹脂(A)、熱硬化性化合物(B)及溶劑(C)，且不含光聚合起始劑，其中結合劑樹脂(A)為不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環式環氧基之單體(A2)共聚合而成之共聚物，或不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環式環氧基之單體(A2)以及與(A1)及(A2)不同且可與(A1)及(A2)共聚合之單體(A3)之共聚物。[1] A thermosetting resin composition comprising a binder resin (A), a thermosetting compound (B), and a solvent (C), and containing no photopolymerization initiator, wherein a binder resin (A) a copolymer obtained by copolymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1) with a monomer having an aliphatic polycyclic epoxy group (A2), or an unsaturated carboxylic acid and/or an unsaturated group The carboxylic anhydride (A1) is a monomer (A2) having an aliphatic polycyclic epoxy group and a monomer (A3) different from (A1) and (A2) and copolymerizable with (A1) and (A2). Copolymer.

[2]如[1]所述之熱硬化性樹脂組成物，其中具有脂肪族多環式環氧基之單體(A2)係選自由以式(I)表示之化合物及以式(II)表示之化合物組成之群組之至少一種化合物：[2] The thermosetting resin composition according to [1], wherein the monomer (A2) having an aliphatic polycyclic epoxy group is selected from the group consisting of the compound represented by the formula (I) and the formula (II) At least one compound representing a group consisting of:

[式(I)及式(II)中，R分別獨立表示氫原子或可經羥基取代之碳數1~4之烷基，[In the formulae (I) and (II), R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group,

X分別獨立表示單鍵或可含有雜原子之碳數1~6之伸烷基]。X each independently represents a single bond or an alkyl group having 1 to 6 carbon atoms which may contain a hetero atom.

[3]如[1]或[2]所述之熱硬化性樹脂組成物，其中該熱硬化性化合物(B)為含有不飽和雙鍵之化合物。[3] The thermosetting resin composition according to [1], wherein the thermosetting compound (B) is a compound containing an unsaturated double bond.

[4]一種塗膜，其特徵係使用[1]至[3]所述之熱硬化性樹脂組成物所形成。[4] A coating film comprising the thermosetting resin composition according to [1] to [3].

[5]一種顯示裝置，其特徵係包含[4]所述之塗膜。[5] A display device comprising the coating film according to [4].

以下詳細說明本發明。The invention is described in detail below.

本發明之熱硬化性樹脂組成物為含有結合劑樹脂(A)、熱硬化性化合物(B)及溶劑(C)，且不含光聚合起始劑之熱硬化性樹脂組成物。The thermosetting resin composition of the present invention is a thermosetting resin composition containing a binder resin (A), a thermosetting compound (B), and a solvent (C), and which does not contain a photopolymerization initiator.

該結合劑樹脂(A)為不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環式環氧基之單體(A2)共聚合而成之共聚物，或不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環式環氧基之單體(A2)以及與(A1)及(A2)不同且可與(A1)及(A2)共聚合之單體(A3)之共聚物。The binder resin (A) is a copolymer obtained by copolymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1) with a monomer having an aliphatic polycyclic epoxy group (A2), or an unsaturated carboxylic acid. The acid and/or unsaturated carboxylic anhydride (A1) is different from the monomer (A2) having an aliphatic polycyclic epoxy group and (A1) and (A2) and can be copolymerized with (A1) and (A2). Copolymer of monomer (A3).

至於上述不飽和羧酸及/或不飽和羧酸酐(A1)，具體而言為列舉為例如丙烯酸、甲基丙烯酸、巴豆酸等之不飽和單羧酸類；The unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (A1) is specifically, for example, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid;

馬來酸、富馬酸、檸康酸、中康酸、衣康酸等不飽和二羧酸類；Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;

及上述不飽和羧酸類之酸酐；And an acid anhydride of the above unsaturated carboxylic acid;

琥珀酸單[2-(甲基)丙烯醯氧基乙酯]、苯二甲酸單[2-(甲基)丙烯醯氧基乙酯]等二價以上之多價羧酸之不飽和單[(甲基)丙烯醯氧基烷]酯類；Unsaturated monovalent polyvalent carboxylic acid such as succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester] (methyl) propylene oxirane] esters;

如α-(羥基甲基)丙烯酸之同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。For example, an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)acrylic acid.

該等中，就共聚合反應性、對鹼性水溶液之溶解性而言較好使用丙烯酸、甲基丙烯酸、馬來酸酐等。該等可單獨使用亦可組合兩種以上使用。Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used in terms of copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used alone or in combination of two or more.

上述具有脂肪族多環式環氧基之單體(A2)為於脂肪族多環化合物之環狀中具有環氧基且具有不飽和鍵之化合物。該脂肪族多環化合物列舉為二環戊烷、三環癸烷等。The monomer (A2) having an aliphatic polycyclic epoxy group is a compound having an epoxy group in the cyclic group of the aliphatic polycyclic compound and having an unsaturated bond. The aliphatic polycyclic compound is exemplified by dicyclopentane, tricyclodecane, and the like.

具有脂肪族多環式環氧基之單體(A2)較好列舉為選自由以式(I)表示之化合物及以式(II)表示之化合物組成之群組之至少一種之化合物：The monomer (A2) having an aliphatic polycyclic epoxy group is preferably a compound selected from at least one selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II):

[式(I)及式(II)中，R分別獨立表示氫原子或可經羥基取代之碳數1~4之烷基，[In the formulae (I) and (II), R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group,

X分別獨立表示單鍵或可含有雜原子之碳數1~6之伸烷基]。X each independently represents a single bond or an alkyl group having 1 to 6 carbon atoms which may contain a hetero atom.

至於R具體而言列舉為氫原子、甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等烷基、羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基正丙基、2-羥基正丙基、3-羥基正丙基、1-羥基異丙基、2-羥基異丙基、1-羥基正丁基、2-羥基正丁基、3-羥基正丁基、4-羥基正丁基等含羥基之烷基。其中，較佳者列舉為氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基等。更好者列舉為氫原子、甲基。R is specifically listed as a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group or the like, an hydroxymethyl group, a 1-hydroxyethyl group. , 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxyisopropyl, 2-hydroxyisopropyl, 1-hydroxy-n-butyl, 2 a hydroxyl group-containing alkyl group such as hydroxy-n-butyl group, 3-hydroxy-n-butyl group or 4-hydroxy-n-butyl group. Among them, preferred are hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group and the like. More preferred are listed as hydrogen atoms and methyl groups.

至於X列舉為單鍵、亞甲基、伸乙基、伸丙基等伸烷基；氧基亞甲基、氧基伸乙基、氧基伸丙基、硫亞甲基、硫伸乙基、硫伸丙基、胺基亞甲基、胺基伸乙基、胺基伸丙基等含雜原子之伸烷基等。其中，較佳者為單鍵、亞甲基、伸乙基、氧基亞甲基、氧基伸乙基，更好為單鍵、氧基伸乙基。As for X, it is exemplified by a single bond, a methylene group, an ethyl group, a propyl group, an alkyl group, an oxymethylene group, an oxyethyl group, an oxypropyl group, a thiomethylene group, a sulfur-extended ethyl group, and a sulfur group. A propyl group, an aminomethylene group, an amine group ethyl group, an amine group propyl group and the like, and a hetero atom-containing alkyl group. Among them, preferred are a single bond, a methylene group, an ethylidene group, an oxymethylene group, an oxyethyl group, and more preferably a single bond or an oxyethyl group.

至於以式(I)表示之化合物列舉為以式(I-1)~式(I-15)表示之化合物等，較好為式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)、式(I-11)~式(I-15)，更好者列舉為式(I-1)、式(I-7)、式(I-9)、式(I-15)。The compound represented by the formula (I) is exemplified by the compound represented by the formula (I-1) to the formula (I-15), and preferably the formula (I-1), the formula (I-3), and the formula (I). -5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15), and more preferably, Formula (I-1), Formula (I-7) , formula (I-9), formula (I-15).

以式(II)表示之化合物列舉為以式(II-1)~式(II-15)表示之化合物等，較佳者列舉為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)、式(II-11)~式(II-15)，更佳者列舉為式(II-1)、式(II-7)、式(II-9)、式(II-15)。The compound represented by the formula (II) is exemplified by the compound represented by the formula (II-1) to the formula (II-15), and the preferred ones are the formula (II-1), the formula (II-3), and the formula (II). II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably listed as formula (II-1), formula (II-7) ), formula (II-9), formula (II-15).

選自由以式(I)表示之化合物及以式(II)表示之化合物組成之群組之至少一種化合物可分別單獨使用，另外，該等可以任意之比率混合。當混合時，其混合比率以莫耳比計，較好式(I)：式(II)為5:95~95:5，更好為10:90~90:10，又更好為20:80~80:20。At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination at any ratio. When mixing, the mixing ratio is in molar ratio, preferably (I): Formula (II) is 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20: 80~80:20.

上述之可與(A1)及(A2)共聚合之單體(A3)(但(A1)及(A2)除外)，舉例為例如下列者：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯等之(甲基)丙烯酸烷酯類；The above-mentioned monomer (A3) which can be copolymerized with (A1) and (A2) (except for (A1) and (A2)), for example, the following: methyl (meth)acrylate, (meth)acrylic acid a (meth)acrylic acid alkyl ester such as ethyl ester, n-butyl (meth)acrylate, second butyl (meth)acrylate or t-butyl (meth)acrylate;

丙烯酸甲酯、丙烯酸異丙酯等之丙烯酸烷酯類；An alkyl acrylate such as methyl acrylate or isopropyl acrylate;

(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6 ]癸-8-基酯(該技術領域中慣用之名稱為(甲基)丙烯酸二環戊烯酯)、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸異冰片酯等之(甲基)丙烯酸環狀烷酯類；Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]non-8-yl (meth)acrylate (used in the art) a (meth)acrylic acid cyclic alkyl ester such as dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate or isobornyl (meth)acrylate;

丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環[5.2.1.02,6 ]癸-8-基酯(該技術領域中慣用之名稱為丙烯酸二環戊烯酯)、丙烯酸二環戊氧基乙酯、丙烯酸異冰片酯等之丙烯酸環狀烷酯類；Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 2,6 ]non-8-yl ester (known in the art as dicyclopentenyl acrylate), acrylic acid a cyclic alkyl acrylate of cyclopentyloxyethyl ester or isobornyl acrylate;

(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等之(甲基)丙烯酸芳基酯類；An aryl (meth)acrylate such as phenyl (meth)acrylate or benzyl (meth)acrylate;

丙烯酸苯酯、丙烯酸苄酯等之丙烯酸芳基酯類；An aryl acrylate such as phenyl acrylate or benzyl acrylate;

馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等之二羧酸二酯；a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate;

(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等之羥基烷酯類；a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate;

雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羧基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯酸無水物(雙環庚烯二甲酸酐(himic acid anhydride))、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己基氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-二(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-二(環己基氧基羰基)雙環[2.2.1]庚-2-烯等之雙環不飽和化合物類；Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2 .1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6 -Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]g 2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[ 2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-enoic acid anhydrate (himic acid anhydride), 5-third Butoxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6- Bicyclic unsaturated compounds of bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene class;

N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺基-6-馬來醯亞胺己酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖丁啶基)馬來醯亞胺等二羰基醯亞胺衍生物類；N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-Amber succinimide-4-maleimide butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-malay a dicarbonyl quinone imine derivative such as quinone imine propionate or N-(9-azetidinyl)maleimide;

苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯、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、乙酸乙烯酯、1,3-丁二烯、異戊間二烯、2,3-二甲基-1,3-丁二烯、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-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧丁酯、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、鄰-乙烯基苄基縮水甘油醚、間-乙烯基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚等。Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride , acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, Glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid -3,4-epoxybutyl acrylate, acrylate-6,7-epoxyheptyl ester, methacrylic acid-6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, adjacent -vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

該等中，就共聚合反應性及對鹼性水溶液之溶解性之觀點而言，較好為苯乙烯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、雙環[2.2.1]庚-2-烯。Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N- are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution. Benzyl maleimide, bicyclo [2.2.1] hept-2-ene.

該等可單獨使用亦可組合兩種以上使用。These may be used alone or in combination of two or more.

本發明中使用之結合劑樹脂(A)為(A1)及(A2)共聚合獲得之共聚物，以及(A1)、(A2)及(A3)共聚合獲得之共聚物之至少一種，由各所導入之構成成份之比率，相對於構成上述共聚物之構成成份之合計莫耳數之莫耳分率計，以在下列範圍內較佳。The binder resin (A) used in the present invention is a copolymer obtained by copolymerization of (A1) and (A2), and at least one of copolymers obtained by copolymerization of (A1), (A2) and (A3), by each of The ratio of the constituent components to be introduced is preferably in the following range with respect to the molar fraction meter which constitutes the total number of moles of the constituent components of the above copolymer.

自(A1)導入之構成單位；2~55莫耳%The constituent unit imported from (A1); 2~55 mol%

自(A2)導入之構成單位；2~95莫耳%The constituent unit imported from (A2); 2~95 mol%

自(A3)導入之構成單位；0~65莫耳%The constituent unit imported from (A3); 0~65 mol%

另外，上述構成成分之比率更好在以下範圍內：In addition, the ratio of the above constituent components is better in the following range:

自(A1)導入之構成單位；5~45莫耳%The constituent unit imported from (A1); 5~45 mol%

自(A2)導入之構成單位；5~80莫耳%The constituent unit imported from (A2); 5~80 mol%

自(A3)導入之構成單位；0~60莫耳%The constituent unit imported from (A3); 0~60 mol%

上述構成比率在上述範圍內時，有儲存安定性、透明性、耐溶劑性、耐熱性、表面硬度均良好之傾向。When the composition ratio is within the above range, storage stability, transparency, solvent resistance, heat resistance, and surface hardness tend to be good.

該等共聚物列舉為(甲基)丙烯酸/式(I-1)之共聚物、(甲基)丙烯酸/式(I-2)之共聚物、(甲基)丙烯酸/式(I-3)之共聚物、(甲基)丙烯酸/式(I-4)之共聚物、(甲基)丙烯酸/式(I-5)之共聚物、(甲基)丙烯酸/式(I-6)之共聚物、(甲基)丙烯酸/式(I-7)之共聚物、(甲基)丙烯酸/式(I-8)之共聚物、(甲基)丙烯酸/式(I-9)之共聚物、(甲基)丙烯酸/式(I-10)之共聚物、(甲基)丙烯酸/式(I-11)之共聚物、(甲基)丙烯酸/式(I-12)之共聚物、(甲基)丙烯酸/式(I-13)之共聚物、(甲基)丙烯酸/式(I-14)之共聚物、(甲基)丙烯酸/式(I-15)之共聚物、(甲基)丙烯酸/式(II-1)之共聚物、(甲基)丙烯酸/式(II-2)之共聚物、(甲基)丙烯酸/式(II-3)之共聚物、(甲基)丙烯酸/式(II-4)之共聚物、(甲基)丙烯酸/式(II-5)之共聚物、(甲基)丙烯酸/式(II-6)之共聚物、(甲基)丙烯酸/式(II-7)之共聚物、(甲基)丙烯酸/式(II-8)之共聚物、(甲基)丙烯酸/式(II-9)之共聚物、(甲基)丙烯酸/式(II-10)之共聚物、(甲基)丙烯酸/式(II-11)之共聚物、(甲基)丙烯酸/式(II-12)之共聚物、(甲基)丙烯酸/式(II-13)之共聚物、(甲基)丙烯酸/式(II-14)之共聚物、(甲基)丙烯酸/式(II-15)之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)之共聚物、(甲基)丙烯酸/式(I-2)/式(II-2)之共聚物、(甲基)丙烯酸/式(I-3)/式(II-3)之共聚物、(甲基)丙烯酸/式(I-4)/式(II-4)之共聚物、(甲基)丙烯酸/式(I-5)/式(II-5)之共聚物、(甲基)丙烯酸/式(I-6)/式(II-6)之共聚物、(甲基)丙烯酸/式(I-7)/式(II-7)之共聚物、(甲基)丙烯酸/式(I-8)/式(II-8)之共聚物、(甲基)丙烯酸/式(I-9)/式(II-9)之共聚物、(甲基)丙烯酸/式(I-10)/式(II-10)之共聚物、(甲基)丙烯酸/式(I-11)/式(II-11)之共聚物、(甲基)丙烯酸/式(I-12)/式(II-12)之共聚物、(甲基)丙烯酸/式(I-13)/式(II-13)之共聚物、(甲基)丙烯酸/式(I-14)/式(II-14)之共聚物、(甲基)丙烯酸/式(I-15)/式(II-15)之共聚物、(甲基)丙烯酸/式(I-1)/式(I-7)之共聚物、(甲基)丙烯酸/式(I-1)/式(II-7)之共聚物、巴豆酸/式(I-1)之共聚物、巴豆酸/式(I-2)之共聚物、巴豆酸/式(I-3)之共聚物、巴豆酸/式(I-4)之共聚物、巴豆酸/式(I-5)之共聚物、巴豆酸/式(I-6)之共聚物、巴豆酸/式(I-7)之共聚物、巴豆酸/式(I-8)之共聚物、巴豆酸/式(I-9)之共聚物、巴豆酸/式(I-10)之共聚物、巴豆酸/式(I-11)之共聚物、巴豆酸/式(I-12)之共聚物、巴豆酸/式(I-13)之共聚物、巴豆酸/式(I-14)之共聚物、巴豆酸/式(I-15)之共聚物、巴豆酸/式(II-1)之共聚物、巴豆酸/式(II-2)之共聚物、巴豆酸/式(II-3)之共聚物、巴豆酸/式(II-4)之共聚物、巴豆酸/式(II-5)之共聚物、巴豆酸/式(II-6)之共聚物、巴豆酸/式(II-7)之共聚物、巴豆酸/式(II-8)之共聚物、巴豆酸/式(II-9)之共聚物、巴豆酸/式(II-10)之共聚物、巴豆酸/式(II-11)之共聚物、巴豆酸/式(II-12)之共聚物、巴豆酸/式(II-13)之共聚物、巴豆酸/式(II-14)之共聚物、巴豆酸/式(II-15)之共聚物、馬來酸/式(I-1)之共聚物、馬來酸/式(I-2)之共聚物、馬來酸/式(I-3)之共聚物、馬來酸/式(I-4)之共聚物、馬來酸/式(I-5)之共聚物、馬來酸/式(I-6)之共聚物、馬來酸/式(I-7)之共聚物、馬來酸/式(I-8)之共聚物、馬來酸/式(I-9)之共聚物、馬來酸/式(I-10)之共聚物、馬來酸/式(I-11)之共聚物、馬來酸/式(I-12)之共聚物、馬來酸/式(I-13)之共聚物、馬來酸/式(I-14)之共聚物、馬來酸/式(I-15)之共聚物、馬來酸/式(II-1)之共聚物、馬來酸/式(II-2)之共聚物、馬來酸/式(II-3)之共聚物、馬來酸/式(II-4)之共聚物、馬來酸/式(II-5)之共聚物、馬來酸/式(II-6)之共聚物、馬來酸/式(II-7)之共聚物、馬來酸/式(II-8)之共聚物、馬來酸/式(II-9)之共聚物、馬來酸/式(II-10)之共聚物、馬來酸/式(II-11)之共聚物、馬來酸/式(II-12)之共聚物、馬來酸/式(II-13)之共聚物、馬來酸/式(II-14)之共聚物、馬來酸/式(II-15)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-2)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-3)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-4)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-5)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-6)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-7)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-8)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-9)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-10)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-11)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-12)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-13)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-14)之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-15)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-2)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-3)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-4)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-5)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-6)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-7)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-8)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-9)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-10)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-11)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-12)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-13)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-14)之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-15)之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-2)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-3)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-4)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-5)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-6)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-7)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-8)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-9)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-10)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-11)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-12)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-13)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-14)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-15)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-2)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-3)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-4)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-5)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-6)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-7)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-8)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-9)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-10)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-11)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-12)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-13)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-14)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(II-15)/(甲基)丙烯酸甲酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/(甲基)丙烯酸二環戊烯酯之共聚物、巴豆酸/式(I-1)/(甲基)丙烯酸二環戊烯酯之共聚物、馬來酸/式(I-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸二環戊烯酯之共聚物、巴豆酸/式(II-1)/(甲基)丙烯酸二環戊烯酯之共聚物、馬來酸/式(II-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸二環戊烯酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/(甲基)丙烯酸苯酯之共聚物、巴豆酸/式(I-1)/(甲基)丙烯酸苯酯之共聚物、馬來酸/式(I-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸苯酯之共聚物、巴豆酸/式(II-1)/(甲基)丙烯酸苯酯之共聚物、馬來酸/式(II-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸苯酯之共聚物、(甲基)丙烯酸/式(I-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/式(II-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/馬來酸二乙酯之共聚物、巴豆酸/式(I-1)/馬來酸二乙酯之共聚物、馬來酸/式(I-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/馬來酸二乙酯之共聚物、巴豆酸/式(II-1)/馬來酸二乙酯之共聚物、馬來酸/式(II-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/馬來酸二乙酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/馬來酸二乙酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、巴豆酸/式(I-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、馬來酸/式(I-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸2-羥基乙酯之共聚物、巴豆酸/式(II-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、馬來酸/式(II-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/(甲基)丙烯酸2-羥基乙酯之共聚物、(甲基)丙烯酸/式(I-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/式(II-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/雙環[2.2.1]庚-2-烯之共聚物、巴豆酸/式(I-1)/雙環[2.2.1]庚-2-烯之共聚物、馬來酸/式(I-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/雙環[2.2.1]庚-2-烯之共聚物、巴豆酸/式(II-1)/雙環[2.2.1]庚-2-烯之共聚物、馬來酸/式(II-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/雙環[2.2.1]庚-2-烯之共聚物、(甲基)丙烯酸/式(I-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/式(II-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/N-環己基馬來醯亞胺之共聚物、巴豆酸/式(I-1)/N-環己基馬來醯亞胺之共聚物、馬來酸/式(I-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/N-環己基馬來醯亞胺之共聚物、巴豆酸/式(II-1)/N-環己基馬來醯亞胺之共聚物、馬來酸/式(II-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/N-環己基馬來醯亞胺之共聚物、(甲基)丙烯酸/式(I-1)/苯乙烯之共聚物、(甲基)丙烯酸/式(II-1)/苯乙烯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/苯乙烯之共聚物、巴豆酸/式(I-1)/苯乙烯之共聚物、馬來酸/式(I-1)/苯乙烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/苯乙烯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/苯乙烯之共聚物、巴豆酸/式(II-1)/苯乙烯之共聚物、馬來酸/式(II-1)/苯乙烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/苯乙烯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/苯乙烯之共聚物、(甲基)丙烯酸/式(I-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/式(II-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/式(I-1)/式(II-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、巴豆酸/式(I-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、馬來酸/式(I-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(I-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/式(I-1)/(甲基)丙烯酸甲酯/N-環己基馬來醯亞胺/苯乙烯之共聚物、巴豆酸/式(II-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、馬來酸/式(II-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/馬來酸酐/式(II-1)/N-環己基馬來醯亞胺/苯乙烯之共聚物、(甲基)丙烯酸/式(II-1)/(甲基)丙烯酸甲酯/N-環己基馬來醯亞胺/苯乙烯之共聚物等。These copolymers are exemplified by (meth)acrylic acid / copolymer of formula (I-1), (meth)acrylic acid / copolymer of formula (I-2), (meth)acrylic acid / formula (I-3) Copolymer, (meth)acrylic acid / copolymer of formula (I-4), (meth)acrylic acid / copolymer of formula (I-5), copolymerization of (meth)acrylic acid / formula (I-6) a copolymer of (meth)acrylic acid/formula (I-7), a copolymer of (meth)acrylic acid/formula (I-8), a copolymer of (meth)acrylic acid/formula (I-9), (Meth)acrylic acid / copolymer of formula (I-10), (meth)acrylic acid / copolymer of formula (I-11), (meth)acrylic acid / copolymer of formula (I-12), (A Acrylic acid / copolymer of formula (I-13), (meth)acrylic acid / copolymer of formula (I-14), (meth)acrylic acid / copolymer of formula (I-15), (methyl) Acrylic acid / copolymer of formula (II-1), (meth)acrylic acid / copolymer of formula (II-2), (meth)acrylic acid / copolymer of formula (II-3), (meth)acrylic acid / Copolymer of the formula (II-4), (meth)acrylic acid / copolymer of the formula (II-5), (meth)acrylic acid / copolymer of the formula (II-6), (meth)acrylic acid / formula ( II-7) copolymer, (meth)acrylic acid / copolymer of formula (II-8), (meth)acrylic acid / (II-9) copolymer, (meth)acrylic acid / copolymer of formula (II-10), (meth)acrylic acid / copolymer of formula (II-11), (meth)acrylic acid / formula (II -12) copolymer, (meth)acrylic acid / copolymer of formula (II-13), (meth)acrylic acid / copolymer of formula (II-14), (meth)acrylic acid / formula (II-15 Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1), (meth)acrylic acid / copolymer of formula (I-2) / formula (II-2) , (meth)acrylic acid / copolymer of formula (I-3) / formula (II-3), (meth)acrylic acid / copolymer of formula (I-4) / formula (II-4), (methyl Acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth)acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth)acrylic acid / (I-7) / copolymer of the formula (II-7), (meth)acrylic acid / copolymer of the formula (I-8) / formula (II-8), (meth)acrylic acid / formula (I-9 Copolymer of formula (II-9), (meth)acrylic acid / copolymer of formula (I-10) / formula (II-10), (meth)acrylic acid / formula (I-11) / formula ( Copolymer of II-11), (meth)acrylic acid / copolymer of formula (I-12) / formula (II-12), (meth)acrylic acid / formula (I-13) / formula (II-13) Copolymer, (meth)acrylic acid / copolymer of formula (I-14) / formula (II-14) , (meth)acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth)acrylic acid / copolymer of formula (I-1) / formula (I-7), (methyl Acrylic acid / copolymer of formula (I-1) / formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / formula Copolymer of (I-3), crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5), crotonic acid / copolymer of formula (I-6), crotonic acid a copolymer of the formula (I-7), a crotonic acid/copolymer of the formula (I-8), a crotonic acid/copolymer of the formula (I-9), a crotonic acid/copolymer of the formula (I-10), Crotonic acid / copolymer of formula (I-11), copolymer of crotonic acid / formula (I-12), copolymer of crotonic acid / formula (I-13), copolymerization of crotonic acid / formula (I-14) , crotonic acid / copolymer of formula (I-15), crotonic acid / copolymer of formula (II-1), crotonic acid / copolymer of formula (II-2), crotonic acid / formula (II-3) Copolymer, crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / formula (II- 7) copolymer, crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / copolymer of formula (II-10) Crotonic acid / copolymer of formula (II-11), copolymer of crotonic acid / formula (II-12), copolymer of crotonic acid / formula (II-13), copolymerization of crotonic acid / formula (II-14) , crotonic acid / copolymer of formula (II-15), copolymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2), maleic acid / formula (I -3) copolymer, maleic acid / copolymer of formula (I-4), copolymer of maleic acid / formula (I-5), copolymer of maleic acid / formula (I-6), horse Copolymer / copolymer of formula (I-7), copolymer of maleic acid / formula (I-8), copolymer of maleic acid / formula (I-9), maleic acid / formula (I-10) Copolymer, maleic acid / copolymer of formula (I-11), copolymer of maleic acid / formula (I-12), copolymer of maleic acid / formula (I-13), maleic acid / copolymer of formula (I-14), copolymer of maleic acid / formula (I-15), copolymer of maleic acid / formula (II-1), maleic acid / formula (II-2) Copolymer, maleic acid / copolymer of formula (II-3), copolymer of maleic acid / formula (II-4), copolymer of maleic acid / formula (II-5), maleic acid / formula Copolymer of (II-6), copolymer of maleic acid / formula (II-7), copolymer of maleic acid / formula (II-8), copolymer of maleic acid / formula (II-9) , maleic acid / formula (II- 10) copolymer, maleic acid / copolymer of formula (II-11), copolymer of maleic acid / formula (II-12), copolymer of maleic acid / formula (II-13), Malay Acid / copolymer of formula (II-14), copolymer of maleic acid / formula (II-15), copolymer of (meth)acrylic acid / maleic anhydride / formula (I-1), (methyl) Acrylic acid/maleic anhydride/copolymer of formula (I-2), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-3), (meth)acrylic acid/maleic anhydride/formula (I- 4) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-6), (methyl) Acrylic acid/maleic anhydride/copolymer of formula (I-7), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/formula (I- 9) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-11), (methyl) Acrylic acid/maleic anhydride/copolymer of formula (I-12), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-13), (meth)acrylic acid/maleic anhydride/formula (I- 14) Copolymer, (meth)acrylic acid / maleic anhydride / a total of (I-15) Polymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-2), (meth)acrylic acid/horse Toluene anhydride / copolymer of formula (II-3), (meth)acrylic acid / maleic anhydride / copolymer of formula (II-4), (meth)acrylic acid / maleic anhydride / formula (II-5) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-6), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-7), (meth)acrylic acid/horse Toluene anhydride / copolymer of formula (II-8), (meth)acrylic acid / maleic anhydride / copolymer of formula (II-9), (meth)acrylic acid / maleic anhydride / formula (II-10) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-11), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-12), (meth)acrylic acid/horse Toluene anhydride / copolymer of formula (II-13), (meth)acrylic acid / maleic anhydride / copolymer of formula (II-14), (meth)acrylic acid / maleic anhydride / formula (II-15) Copolymer, (meth)acrylic acid / copolymer of methyl (I-1) / methyl (meth)acrylate, copolymer of (meth)acrylic acid / methyl (I-2) / (meth) acrylate , (meth)acrylic acid / formula (I-3) / ( Copolymer of methyl acrylate, (meth)acrylic acid / copolymer of methyl (I-4) / methyl (meth) acrylate, (meth) acrylic / formula (I-5) / (methyl) Copolymer of methyl acrylate, copolymer of (meth)acrylic acid/methyl (I-6)/(meth)acrylate, (meth)acrylic acid/(I-7)/(meth)acrylic acid Copolymer of ester, (meth)acrylic acid / copolymer of methyl (I-8) / methyl (meth)acrylate, (meth)acrylic acid / methyl (I-9) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of formula (I-10) / methyl (meth) acrylate, copolymer of (meth) acrylate / methyl (I-11) / methyl (meth) acrylate a copolymer of (meth)acrylic acid/methyl (I-12)/(meth)acrylate, a copolymer of (meth)acrylic acid/methyl (I-13)/(meth)acrylate, ( Methyl)acrylic acid/copolymer of formula (I-14)/methyl (meth)acrylate, (meth)acrylic acid/copolymer of formula (I-15)/methyl (meth)acrylate, (methyl) Acrylic acid / copolymer of (II-1) / methyl (meth) acrylate, (meth) acrylate / copolymer of (II-2) / methyl (meth) acrylate, (meth) acrylic acid /Formula (II-3) / (meth)acrylic acid Copolymer of ester, (meth)acrylic acid / copolymer of methyl (II-4) / methyl (meth)acrylate, (meth)acrylic acid / methyl (II-5) / methyl (meth)acrylate Copolymer, (meth)acrylic acid / copolymer of methyl (II-6) / methyl (meth) acrylate, copolymer of (meth) acrylate / methyl (II-7) / methyl (meth) acrylate , (meth)acrylic acid / copolymer of methyl (II-8) / (meth) acrylate, (meth) acrylate / copolymer of methyl (II-9) / methyl (meth) acrylate, ( Methyl)acrylic acid/copolymer of formula (II-10)/methyl (meth)acrylate, (meth)acrylic acid/copolymer of formula (II-11)/methyl (meth)acrylate, (methyl) Acrylic acid / copolymer of (II-12) / methyl (meth) acrylate, (meth) acrylic / copolymer of (II-13) / methyl (meth) acrylate, (meth) acrylic acid / (II-14) / (meth) acrylate copolymer, (meth) acrylate / copolymer of (II-15) / methyl (meth) acrylate, (meth) acrylic / Copolymer of (I-1)/(di)pentyl (meth)acrylate, (meth)acrylic acid/copolymer of formula (II-1)/dicyclopentenyl (meth)acrylate, (methyl) Acrylic acid / formula (I-1) / formula (II- 1) / copolymer of dicyclopentenyl (meth) acrylate, copolymer of crotonic acid / dicyclopentenyl (I-1) / (meth) acrylate, maleic acid / formula (I-1 Copolymer of /(meth)acrylic acid dicyclopentenyl ester, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/dicyclopentenyl (meth)acrylate, (methyl) Acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / dicyclopentenyl (meth) acrylate, crotonic acid / dicyclopentanyl (II-1) / (meth) acrylate Copolymer of olefin ester, maleic acid / copolymer of formula (II-1) / dicyclopentenyl (meth) acrylate, (meth) acrylate / maleic anhydride / formula (II-1) / (A Copolymer of dicyclopentenyl acrylate, copolymer of (meth)acrylic acid/methyl (II-1)/methyl (meth)acrylate/dicyclopentenyl (meth)acrylate, (methyl) Acrylic / copolymer of (I-1) / phenyl (meth) acrylate, (meth) acrylic / copolymer of phenyl (II-1) / (meth) acrylate, (meth) acrylic acid / (I-1) / (II-1) / (meth) acrylate copolymer, crotonic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, maleic acid /Complex of formula (I-1) / (meth) acrylate , (meth)acrylic acid/maleic anhydride/copolymer of phenyl (I-1)/(meth)acrylate, (meth)acrylic acid/methyl (I-1)/(meth)acrylate Copolymer of phenyl (meth) acrylate, copolymer of crotonic acid / phenyl (II-1) / phenyl (meth) acrylate, maleic acid / benzene of formula (II-1) / (meth) acrylate Copolymer of ester, (meth)acrylic acid/maleic anhydride/copolymer of phenyl (II-1)/phenyl (meth)acrylate, (meth)acrylic acid/(II-1)/(methyl) Copolymer of methyl acrylate/phenyl (meth) acrylate, copolymer of (meth)acrylic acid / formula (I-1) / diethyl maleate, (meth)acrylic acid / formula (II-1) / copolymer of diethyl maleate, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / formula (I-1) / copolymer of diethyl maleate, copolymer of maleic acid / formula (I-1) / diethyl maleate, (meth)acrylic acid / maleic anhydride / formula (I-1) / horse Copolymer of diethyl carbonate, copolymer of (meth)acrylic acid/methyl (I-1)/methyl (meth)acrylate/diethyl maleate, crotonic acid/formula (II-1)/ Copolymer of diethyl maleate, maleic acid / formula (II-1) / maleic acid diethyl Copolymer of ester, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/diethyl maleate, (meth)acrylic acid/(II-1)/(meth)acrylic acid Copolymer of methyl ester / diethyl maleate, copolymer of (meth)acrylic acid / 2-hydroxyethyl (I-1) / (meth) acrylate, (meth) acrylic / formula (II- 1) / Copolymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth)acrylate a crotonic acid/copolymer of 2-hydroxyethyl (I-1)/(meth)acrylate, a copolymer of maleic acid/2-hydroxyethyl (I-1)/(meth)acrylate, (Meth)acrylic acid/maleic anhydride/copolymer of 2-hydroxyethyl (I-1)/(meth)acrylate, (meth)acrylic acid/(I-1)/(meth)acrylic acid Copolymer / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / formula (II-1) Copolymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/2-hydroxyethyl (meth)acrylate, (methyl) Acrylic acid / methyl (II-1) / (meth) acrylate / (methyl) Copolymer of 2-hydroxyethyl enoate, (meth)acrylic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (II-1 / Bicyclo [2.2.1] copolymer of hept-2-ene, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene , crotonic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/bicyclo[2.2.1]hept-2-ene, (meth)acrylic acid/formula (I-1)/(A) a copolymer of methyl acrylate/bicyclo[2.2.1]hept-2-ene, a copolymer of crotonic acid/formula (II-1)/bicyclo[2.2.1]hept-2-ene, maleic acid/ Copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / maleic anhydride / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, (meth)acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, (meth) acrylate / formula (I- 1) copolymer of /N-cyclohexylmaleimide, copolymer of (meth)acrylic acid/(II-1)/N-cyclohexylmaleimide, (meth)acrylic acid/form ( I-1) / formula (II-1) / N-cyclohexylmaleimide Copolymer, crotonic acid / copolymer of formula (I-1) / N-cyclohexyl maleimide, maleic acid / copolymer of formula (I-1) / N-cyclohexyl maleimide, (Meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/N-cyclohexylmaleimine, (meth)acrylic acid/methyl (I-1)/(meth)acrylate /N-cyclohexylmaleimide copolymer, crotonic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide, maleic acid / formula (II-1) / N- Copolymer of cyclohexylmaleimide, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/N-cyclohexylmaleimide, (meth)acrylic acid/form (II -1) / (meth) acrylate / N-cyclohexyl maleimide copolymer, (meth) acrylate / copolymer of formula (I-1) / styrene, (meth) acrylic acid / Copolymer of formula (II-1) / styrene, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / styrene, crotonic acid / formula (I-1) / benzene Copolymer of ethylene, copolymer of maleic acid / formula (I-1) / styrene, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1) / styrene, (meth)acrylic acid / (I-1) / (methyl) acrylate / styrene copolymer, Croton / copolymer of formula (II-1) / styrene, copolymer of maleic acid / formula (II-1) / styrene, (meth)acrylic acid / maleic anhydride / formula (II-1) / styrene Copolymer, (meth)acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / styrene, (meth) acrylate / formula (I-1) / N-cyclohexylmalay Copolymer of quinone imine/styrene, copolymer of (meth)acrylic acid/(II-1)/N-cyclohexylmaleimide/styrene, (meth)acrylic acid/form (I-1 Copolymer of formula (II-1)/N-cyclohexylmaleimide/styrene, crotonic acid/copolymer of formula (I-1)/N-cyclohexylmaleimide/styrene , maleic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth)acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexyl horse Copolymer of bismuth imine/styrene, copolymer of (meth)acrylic acid/methyl (I-1)/(meth)acrylate/N-cyclohexylmaleimide/styrene, crotonic acid Copolymer of formula (II-1)/N-cyclohexylmaleimide/styrene, maleic acid/copolymer of formula (II-1)/N-cyclohexylmaleimide/styrene , (meth)acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmalay Imide copolymer / styrene, the (meth) acrylic acid / the formula (II-1) / (meth) acrylate / N- cyclohexylmaleimide (PEI) / the styrene copolymer.

而且，作為表記之方法，上述(甲基)丙烯酸表示丙烯酸或甲基丙烯酸，(甲基)丙烯酸甲酯表示丙烯酸甲酯或甲基丙烯酸甲酯。Further, as a method of expression, the above (meth)acrylic acid means acrylic acid or methacrylic acid, and methyl (meth)acrylate means methyl acrylate or methyl methacrylate.

上述結合劑樹脂(A)可參考例如文獻「高分子合成之實驗法」(大津隆行著發行所(股)化學同人　第一版第一刷　1972年3月1日發行)中所述之方法及該文獻中所列之引用文獻製造。The above-mentioned binder resin (A) can be referred to, for example, the method described in the document "Experimental method for polymer synthesis" (the issue of the first edition of the first edition of the Otsuka Ryokan Chemical Co., Ltd., issued on March 1, 1972). The citations listed in this document are manufactured.

具體而言，將既定量之導入構成共聚物之單位(A1)、(A2)及(A3)之化合物、聚合起始劑及溶劑饋入反應容器，且以氮氣置換氧氣，在沒有氧之下藉由攪拌、加熱、保溫獲得聚合物。再者，所得共聚物可以反應後之溶液直接使用，亦可使用濃縮或稀釋之溶液，亦可以再沉澱等方法取出固體(粉體)者使用。Specifically, a compound which is quantitatively introduced into units (A1), (A2), and (A3) constituting the copolymer, a polymerization initiator, and a solvent are fed into the reaction vessel, and oxygen is replaced with nitrogen, without oxygen. The polymer is obtained by stirring, heating, and heat preservation. Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as reprecipitation.

上述之結合劑樹脂(A)換算成聚苯乙烯之重量平均分子量較好為3,000~100,000，更好為5,000~50,000。結合劑樹脂(A)之重量平均分子量在上述範圍時，有塗佈性變良好之傾向而較佳。The weight average molecular weight of the above binder resin (A) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the above range, the coating property tends to be good, which is preferable.

結合劑樹脂(A)之分子量分佈[重量平均分子量(Mw)/數平均分子量(Mn)]較好為1.1~6.0，更好為1.2~4.0。當分子量分佈在上述範圍內時由於具有優異顯像性之傾向而較佳。The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, it is preferred because of its tendency to have excellent developability.

本發明之熱硬化性樹脂組成物中使用之結合劑樹脂(A)之含有量，以相對於熱硬化性樹脂組成物中之固成份之質量分率計，較好為5~90質量%，更好為10~80質量%，又更好為20~70質量%。結合劑樹脂(A)之含有量在上述範圍內時，具有儲存安定性、透明性、耐溶劑性、耐熱性、表面硬度良好之傾向而較佳。The content of the binder resin (A) used in the thermosetting resin composition of the present invention is preferably from 5 to 90% by mass based on the mass fraction of the solid content in the thermosetting resin composition. More preferably, it is 10 to 80% by mass, and more preferably 20 to 70% by mass. When the content of the binder resin (A) is within the above range, storage stability, transparency, solvent resistance, heat resistance, and surface hardness tend to be good, and it is preferred.

本發明之熱硬化性樹脂組成物中所含熱硬化性化合物(B)為具有不飽和雙鍵之化合物，且可為2官能基單體、3官能基以上之多官能基單體。The thermosetting compound (B) contained in the thermosetting resin composition of the present invention is a compound having an unsaturated double bond, and may be a bifunctional monomer or a trifunctional or higher polyfunctional monomer.

2官能基單體之具體例列舉為1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯等。Specific examples of the bifunctional monomer are 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethyl Glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

3官能基以上之多官能基單體之具體例列舉為例如三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、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、季戊四醇三(甲基)丙烯酸酯與酸酐之反應產物、二季戊四醇五(甲基)丙烯酸酯與酸酐之反應產物、己內酯改質之季戊四醇四(甲基)丙烯酸酯、己內酯改質之二季戊四醇五(甲基)丙烯酸酯、己內酯改質之二季戊四醇六(甲基)丙烯酸酯、環氧乙烷改質之季戊四醇四(甲基)丙烯酸酯、環氧乙烷改質之二季戊四醇五(甲基)丙烯酸酯、環氧乙烷改質之二季戊四醇六(甲基)丙烯酸酯、環氧丙烷改質之季戊四醇四(甲基)丙烯酸酯、環氧丙烷改質之二季戊四醇五(甲基)丙烯酸酯、環氧丙烷改質之二季戊四醇六(甲基)丙烯酸酯等。其中，較好使用2官能基以上之多官能基單體。該等之光聚合性化合物(B)可單獨使用，亦可組合兩種以上使用。Specific examples of the polyfunctional monomer having a trifunctional or higher functional group are, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol-5. Reaction product of (meth) acrylate, dipentaerythritol hexa(meth) acrylate, pentaerythritol tri(meth) acrylate and an acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, caprolactone modification Pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, oxirane modified Pentaerythritol tetra(meth)acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa(meth) acrylate, propylene oxide modified pentaerythritol Tetrakis (meth) acrylate, propylene oxide modified dipentaerythritol penta (meth) acrylate, propylene oxide modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, a polyfunctional monomer having a bifunctional group or more is preferably used. These photopolymerizable compounds (B) may be used singly or in combination of two or more.

又，在不損及本發明效果之程度下亦可倂用單官能基單體。Further, a monofunctional monomer can also be used to the extent that the effects of the present invention are not impaired.

單官能基單體之具體例列舉為壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯啶酮等。另外，結合劑樹脂(A)之單體列舉有(A1)、(A2)及(A3)等。Specific examples of the monofunctional monomer are decyl phenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate , N-vinyl pyrrolidone and the like. Further, examples of the monomer of the binder resin (A) include (A1), (A2), and (A3).

熱硬化性化合物(B)之含有量，以相對於結合劑樹脂(A)及熱硬化性化合物(B)之合計量之質量分率計，較好為1~70質量%，更好為5~65質量%。熱硬化性化合物(B)之含有量在上述範圍內時，具有透明性、耐溶劑性、耐熱性、表面硬度、平坦性良好之傾向而較佳。The content of the thermosetting compound (B) is preferably from 1 to 70% by mass, more preferably from 5 to 70% by mass based on the total mass of the binder resin (A) and the thermosetting compound (B). ~65 mass%. When the content of the thermosetting compound (B) is within the above range, transparency, solvent resistance, heat resistance, surface hardness, and flatness tend to be good, and it is preferable.

本發明之熱硬化性樹脂組成物係包含溶劑(C)。至於上述溶劑(C)可使用熱硬化性樹脂組成物領域中使用之各種有機溶劑。其具體例列舉為如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚及乙二醇單丁基醚之乙二醇單烷基醚類；The thermosetting resin composition of the present invention contains a solvent (C). As the solvent (C), various organic solvents used in the field of thermosetting resin compositions can be used. Specific examples thereof are ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、二乙二醇乙基甲基醚之二乙二醇二烷基醚類；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether diethylene glycol Dialkyl ethers;

如二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丙基醚乙酸酯、二乙二醇單丁基醚乙酸酯之二乙二醇單烷基醚乙酸酯類；Such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate Ethylene glycol monoalkyl ether acetates;

如甲基溶纖素乙酸酯及乙基溶纖素乙酸酯之乙二醇烷基醚乙酸酯類；Such as methyl cellosolve acetate and ethyl cellosolve acetate ethylene glycol alkyl ether acetate;

如二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚及二丙二醇單丁基醚之二丙二醇單烷基醚類；Such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether dipropylene glycol monoalkyl ethers;

如二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇二丙基醚、二丙二醇二丁基醚、二丙二醇乙基甲基醚之二丙二醇二烷基醚類；Such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol ethyl methyl ether dipropylene glycol dialkyl ether;

如二丙二醇單甲基醚乙酸酯、二丙二醇單乙基醚乙酸酯、二丙二醇單丙基醚乙酸酯、二丙二醇單丁基醚乙酸酯之二丙二醇單烷基醚乙酸酯類；For example, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate dipropylene glycol monoalkyl ether acetate ;

如甲基溶纖素乙酸酯及乙基溶纖素乙酸酯之乙二醇烷基醚乙酸酯類；Such as methyl cellosolve acetate and ethyl cellosolve acetate ethylene glycol alkyl ether acetate;

如丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙酸甲氧基丁酯及乙酸甲氧基戊酯之烷二醇烷基醚乙酸酯類；Such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxy pentyl acetate alkyl alkane alkyl ether acetate class;

如苯、甲苯、二甲苯及均三甲苯之芳香族烴類；Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

如甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮、環戊酮及環己酮之酮類；Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone;

如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇及甘油之醇類；Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol;

如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯之酯類；Such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

如γ-丁內酯之環狀酯類等。Such as γ-butyrolactone cyclic esters and the like.

上述溶劑中，就塗佈性、乾燥性之觀點而言，較佳者舉例為上述溶劑中沸點在100℃~200℃之有機溶劑，更好舉例為烷二醇烷基醚乙酸酯類、酮類、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯之酯類，又更好為舉例為丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、環己酮、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯等。Among the above solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of from 100 ° C to 200 ° C in the above solvent is preferred, and alkanediol alkyl ether acetates and ketones are more preferably exemplified. Esters, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably exemplified by propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ring Hexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like.

該等溶劑(C)可分別單獨使用，亦可組合兩種以上使用。These solvents (C) may be used alone or in combination of two or more.

本發明之熱硬化性樹脂組成物中之溶劑(C)之含有量，以相對於熱硬化性樹脂組成物之質量分率計，通常為30~95質量%，較好為50~90質量%，更好為55~85質量%。溶劑(C)之含有量在上述範圍內時，以旋轉塗佈器、狹縫及旋轉塗佈器、狹縫塗佈器(亦稱為模嘴塗佈器、簾流塗佈器)、噴墨、輥塗佈器等塗佈裝置塗佈可預見到良好之塗佈性而較佳。The content of the solvent (C) in the thermosetting resin composition of the present invention is usually 30 to 95% by mass, preferably 50 to 90% by mass, based on the mass fraction of the thermosetting resin composition. More preferably, it is 55 to 85% by mass. When the content of the solvent (C) is within the above range, a spin coater, a slit and a spin coater, a slit coater (also referred to as a die coater, a curtain coater), and a spray It is preferred that the coating device such as an ink or a roll coater can predict good coatability.

本發明之熱硬化性樹脂組成物可進而有抗氧化劑(D)藉此進而有良好耐熱性之傾向。抗氧化劑(D)列舉為例如酚系抗氧化劑、硫系抗氧化劑、磷系抗氧化劑等。The thermosetting resin composition of the present invention may further have an antioxidant (D) and thus has a tendency to have good heat resistance. The antioxidant (D) is exemplified by, for example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like.

至於上述酚系抗氧化劑列舉為2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基芐基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯基丙烯酸酯、2,2’-亞甲基雙(6-第三丁基-4-甲基酚)、4,4’-亞丁基雙(6-第三丁基-3-甲基酚)、4,4’-硫基雙(3-甲基-6-第三丁基酚)、2,2’-硫基雙(4-甲基-6-第三丁基酚)、3,9-雙[2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烷(dioxaphosphepin)、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己烷二醇-雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2,4-雙-(正辛基硫基)-6-(4-羥基-3,5-二第三丁基苯胺基)-1,3,5-三嗪、季戊四醇基．肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、參-(3,5-二第三丁基-4-羥基苄基)-異脲氰酸酯、2,6-二第三丁基-4-甲基酚等。The above phenolic antioxidant is exemplified as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1 -(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate, 2,2'-methylene bis (6-third Butyl-4-methylphenol), 4,4'-butylene bis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(3-methyl-6- Tributylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-) Hydroxy-5-methylphenyl)propenyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,6-[3- (3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3 , 2] dioxaphosphepin, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1, 6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-( 4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol. [3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionate], gins-(3,5-di-t-butyl-4-hydroxybenzyl)-isourea cyanate Ester, 2,6-di-t-butyl-4-methylphenol, and the like.

上述硫系抗氧化劑列舉為二月桂基-3,3’-硫二丙酸酯、二(十四烷基)-3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、季戊四醇基-肆(3-月桂基硫丙酸酯)、2-巰基苯并咪唑、二月桂基-3,3'-硫二丙酸酯、二(十四烷基)-3,3'-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、季戊四醇基-肆(3-月桂基硫丙酸酯)等。The above sulfur-based antioxidants are exemplified by dilauryl-3,3'-thiodipropionate, di(tetradecyl)-3,3'-thiodipropionate, distearyl-3,3' -thiodipropionate, pentaerythritol-indole (3-lauryl thiopropionate), 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, di(tetradecyl) -3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol-anthracene (3-lauryl thiopropionate), and the like.

上述磷系抗氧化劑列舉為磷酸三苯酯、磷酸二苯酯異癸酯、磷酸苯酯二異癸酯、4,4’-亞丁基-雙(3-甲基-6-第三丁基苯基二(十三烷基))磷酸酯、磷酸十八烷酯、參(壬基苯基)磷酸酯、二磷酸二異癸酯季戊四醇酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(3,5-二第三丁基-4-羥基苄基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-去氧-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、參(2,4-二第三丁基苯基)磷酸酯、環狀新戊烷四基雙(2,4-二第三丁基苯基)磷酸酯、環狀新戊烷四基雙(2,6-二第三丁基苯基)磷酸酯、2,2-亞甲基雙(4,6-二第三丁基苯基)辛基磷酸酯、參(2,4-二第三丁基苯基)磷酸酯、肆(2,4-二第三丁基苯基)[1,1-聯苯]-4,4’-二基雙膦酸酯、雙[2,4-雙(1,1-二甲基乙基)-6-甲基苯基]乙基酯、膦酸、雙(2,4-二第三丁基苯基)季戊四醇二磷酸酯等。The above phosphorus-based antioxidants are exemplified by triphenyl phosphate, isophthalic acid diphenyl ester, diphenyl phenyl phosphate, 4,4'-butylene-bis(3-methyl-6-t-butylbenzene). Di(tridecyl) phosphate, octadecyl phosphate, decylphenyl phosphate, diisononyl diphosphate pentaerythritol, 9,10-dihydro-9-oxa-10 -phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 10-deoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, ginseng (2,4-di-t-butylphenyl)phosphate, cyclic Neopentane tetrakis(2,4-di-t-butylphenyl)phosphate, cyclic neopentyltetrakis(2,6-di-t-butylphenyl)phosphate, 2,2- Methylene bis(4,6-di-t-butylphenyl)octyl phosphate, bis(2,4-di-t-butylphenyl)phosphate, hydrazine (2,4-di-t-butyl) Phenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl] Ethyl ester, phosphonic acid, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphate, and the like.

該等抗氧化劑(D)可個別單獨使用，亦可組合兩種以上使用。These antioxidants (D) may be used singly or in combination of two or more.

本發明之熱硬化性樹脂組成物中所用抗氧化劑(D)之含有量，以相對於熱硬化性樹脂組成物中之固成份之質量分率計，較好為10質量%以下，更好為5質量%以下，又更好為3質量%以下。抗氧化劑(D)在上述質量分率內時，有耐熱性良好之傾向。The content of the antioxidant (D) used in the thermosetting resin composition of the present invention is preferably 10% by mass or less, more preferably 10% by mass or less, based on the mass fraction of the solid content in the thermosetting resin composition. 5 mass% or less, more preferably 3% by mass or less. When the antioxidant (D) is within the above mass fraction, the heat resistance tends to be good.

本發明之熱硬化性樹脂組成物不含光聚合起始劑。由於不含光聚合起始劑，因此可抑制所得塗膜之透過率之降低。The thermosetting resin composition of the present invention does not contain a photopolymerization initiator. Since the photopolymerization initiator is not contained, the decrease in the transmittance of the resulting coating film can be suppressed.

本發明之熱硬化性樹脂組成物中，可依據需要合倂使用充填劑、其他高分子化合物、顏料分散劑、密著促進劑、紫外線吸收劑、凝集劑、鏈轉移劑等添加劑(F)。In the thermosetting resin composition of the present invention, an additive (F) such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an ultraviolet absorber, a coagulant, or a chain transfer agent may be used as needed.

充填劑具體而言例示為玻璃、氧化矽、氧化鋁等。The filler is specifically exemplified by glass, cerium oxide, aluminum oxide, or the like.

其他高分子化合物之具體例可使用環氧樹脂、馬來醯亞胺樹脂等熱硬化性樹脂或聚乙烯基醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯、聚酯、聚胺基甲酸酯等熱可塑性樹脂等。Specific examples of the other polymer compound may be a thermosetting resin such as an epoxy resin or a maleimide resin, or a polyvinyl alcohol, a polyacrylic acid, a polyethylene glycol monoalkyl ether, a polyfluoroalkyl acrylate, or a poly A thermoplastic resin such as an ester or a polyurethane.

至於顏料分散劑可使用市售界面活性劑，列舉為例如矽氧系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性等界面活性劑等，且可個別單獨使用，亦可組合兩種以上使用。上述界面活性劑之例列舉為聚氧伸乙基烷基醚類、聚氧伸乙基烷基苯基醚類、聚乙二醇二酯類、山梨糖醇酐脂肪酸酯類、脂肪酸改質之聚酯類、三級胺改質之聚胺基甲酸酯類、聚伸乙基亞胺類等，此外又可舉例以商品名KP(信越化學工業(股)製造)、POLTFLOW(共榮化學(股)製造)、F TOP(TOHKEM PRODUCT公司製造)、MEGAFACK(大日本油墨化學工業(股)製造)、FLORID(住友3M(股)製造)、ASAHIGARD、SULFLONE(以上為旭硝子(股)製造)、SOLUSBASE(ZENECA(股)製造)、EFKA(EFKA化學公司製造)、PB821(味之素(股)製造)等。As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include an anthracene-based, a fluorine-based, an ester-based, a cationic-based, an anionic-based, nonionic-based, amphoteric surfactant, and the like, and can be used individually or separately. Use two or more combinations. Examples of the above surfactants are polyoxyethylene ethyl ethers, polyoxyethylene ethyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modifications. Polyesters, tertiary amine modified polyurethanes, polyethylenimines, etc., in addition to the trade name KP (Shin-Etsu Chemical Co., Ltd.), POLTFLOW (Common Chemicals ( (manufacturing), F TOP (manufactured by TOHKEM PRODUCT), MEGAFACK (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), FLORID (manufactured by Sumitomo 3M Co., Ltd.), ASAHIGARD, SULFLONE (above, manufactured by Asahi Glass Co., Ltd.) SOLUSBASE (manufactured by ZENECA), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

密著促進劑具體而言列舉為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。The adhesion promoter is specifically exemplified by vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-chloro Propylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

熱自由基產生劑具體而言列舉為2,2'-偶氮雙(2-甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)等。Specific examples of the thermal radical generating agent are 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and the like.

紫外線吸收劑具體而言列舉為2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并***、烷氧基二苯甲酮等。Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

另外凝集劑具體而言列舉為聚丙烯酸鈉等。Further, the aggregating agent is specifically exemplified by sodium polyacrylate or the like.

鏈轉移劑列舉為十二烷基硫醇、2,4-二苯基-4-甲基-1-戊烯等。The chain transfer agent is exemplified by dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.

本發明之熱硬化性樹脂組成物可例如塗佈於如下列之基材上之後，經加熱硬化形成硬化塗膜。首先，將該組成物塗佈於基板(通常為玻璃)或彩色濾光片基板或陣列基板上，藉由真空乾燥或預烘烤自塗佈之熱硬化性樹脂組成物層去除溶劑等揮發成份，獲得平滑之塗膜。此時之塗膜厚度為0.1~10μm。至於真空乾燥之條件為在50~300pa之真空度下1~60秒。預烘烤之條件為在5~150℃下5~180秒。The thermosetting resin composition of the present invention can be applied, for example, to a substrate such as the following, and then cured by heating to form a cured coating film. First, the composition is applied onto a substrate (usually glass) or a color filter substrate or an array substrate, and a volatile component such as a solvent is removed by vacuum drying or prebaking from the coated thermosetting resin composition layer. , to obtain a smooth coating film. The film thickness at this time is 0.1 to 10 μm. The conditions for vacuum drying are 1 to 60 seconds under a vacuum of 50 to 300 Pa. The prebaking conditions are 5 to 180 seconds at 5 to 150 °C.

使如此般獲得之塗膜在150~230℃下進行後烘烤10~120分鐘，藉此可形成硬化塗膜。The thus obtained coating film is post-baked at 150 to 230 ° C for 10 to 120 minutes, whereby a hardened coating film can be formed.

使用本發明之熱硬化性樹脂組成物，經歷上述各步驟，可在基板上或彩色濾光片上形成硬化塗膜。該硬化塗膜可使用作為液晶顯示裝置中之保護塗層(overcoat)。Using the thermosetting resin composition of the present invention, a hardened coating film can be formed on a substrate or a color filter by the above respective steps. The hard coat film can be used as an overcoat in a liquid crystal display device.

因此，藉由將如此般獲得之硬化塗膜組裝在液晶顯示裝置等顯示裝置上，可以高成品率製造優異品質之顯示裝置。Therefore, by assembling the hardened coating film thus obtained on a display device such as a liquid crystal display device, it is possible to manufacture a display device of excellent quality with high yield.

本發明之熱硬化性樹脂組成物在儲存時之黏度變化小，且可形成透明性、耐溶劑性、耐熱性、表面硬度優異之塗膜。The thermosetting resin composition of the present invention has a small change in viscosity during storage, and can form a coating film excellent in transparency, solvent resistance, heat resistance, and surface hardness.

本發明之熱硬化性樹脂組成物為形成構成彩色濾光片之一部份之透明膜之材料，例如適合形成面塗層(亦稱為保護膜)、絕緣膜、用以調和著色圖型之膜厚之塗層等之透明膜，自本發明之熱硬化性樹脂組成物形成之塗膜適用於彩色濾光片、具備有彩色濾光片之液晶顯示裝置。The thermosetting resin composition of the present invention is a material for forming a transparent film constituting a part of a color filter, and is, for example, suitable for forming a top coat (also referred to as a protective film), an insulating film, and a coloring pattern. A transparent film such as a film thickness coating or the like, and a coating film formed from the thermosetting resin composition of the present invention is applied to a color filter and a liquid crystal display device having a color filter.

實施例Example

以下，基於實施例詳細說明本發明，但本發明並不受該等實施例之限制自當不再贅言。Hereinafter, the present invention will be described in detail based on the examples, but the present invention is not limited by the examples.

又，實例中之表示含有量及使用量之%及份若無特別說明則為質量基準。Further, in the examples, the % and the parts indicating the content and the amount used are based on mass unless otherwise specified.

合成例1Synthesis Example 1

在配置回流冷卻器、滴加漏斗及攪拌機之1升燒瓶內，使氮氣以0.02升/分鐘流過作成氮氣氛圍中饋入200質量份之3-甲氧基-1-丁醇及105質量份之乙酸3-甲氧基丁酯，且攪拌下加熱至70℃。接著，使60質量份之甲基丙烯酸、240質量份之丙烯酸3,4-環氧基三環[5.2.1.02,6 ]癸酯(以莫耳比50:50混合以式(I-1)表示之化合物及以式(II-1)表示之化合物)溶解於140質量份之乙酸3-甲氧基丁酯中調配溶液，使用滴加漏斗，在4小時內將該溶解溶液滴加於在70℃下保溫之燒瓶內。另一方面，使用另一滴加漏斗，在4小時內將使30質量份之聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)溶解於225質量份之乙酸3-甲氧基丁酯中而成之溶液滴加於燒瓶內。聚合起始劑之溶液滴加結束後，在70℃下維持4小時，隨後冷卻至室溫，獲得固成份32.6質量%，酸價34.3mg-KOH/g之共聚物(樹脂Aa)之溶液。所得樹脂Aa之重量平均分子量(Mw)為13,400，分散度為2.50。In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was fed at 0.02 liter/min to feed 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass in a nitrogen atmosphere. 3-methoxybutyl acetate was heated to 70 ° C with stirring. Next, 60 parts by mass of methacrylic acid and 240 parts by mass of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate (mixed with a molar ratio of 50:50 to give the formula (I-1) The compound represented by the formula (II-1) is dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution is added dropwise to the solution within 4 hours using a dropping funnel. The flask was incubated at 70 ° C. On the other hand, using another dropping funnel, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of acetic acid in 4 hours. A solution of 3-methoxybutyl ester was added dropwise to the flask. After completion of the dropwise addition of the solution of the polymerization initiator, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 32.6% by mass and an acid value of 34.3 mg-KOH/g. The obtained resin Aa had a weight average molecular weight (Mw) of 13,400 and a degree of dispersion of 2.50.

合成例2Synthesis Example 2

在配置回流冷卻器、滴加漏斗及攪拌機之1升燒瓶內，使氮氣以0.02升/分鐘流過作成氮氣氛圍中饋入200質量份之3-甲氧基-1-丁醇及105質量份之乙酸3-甲氧基丁酯，且攪拌下加熱至70℃。接著，使55質量份之甲基丙烯酸、175質量份之丙烯酸3,4-環氧基三環[5.2.1.02,6 ]癸酯(以莫耳比50:50混合以式(I-1)表示之化合物及以式(II-1)表示之化合物)及70質量份之N-環己基馬來醯亞胺溶解於140質量份之乙酸3-甲氧基丁酯調製溶液，且使用滴加漏斗，在4小時內將該溶解溶液滴加於在70℃下保溫之燒瓶內。另一方面，使用另一滴加漏斗，在4小時內將使30質量份之聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)溶解於225質量份之乙酸3-甲氧基丁酯中而成之溶液滴加於燒瓶內。聚合起始劑之溶液滴加結束後，在70℃下維持4小時，隨後冷卻至室溫，獲得固成份32.6質量%，酸價34.2mg-KOH/g之共聚物(樹脂Ab)之溶液。所得樹脂Ab之重量平均分子量(Mw)為13,600，分散度為2.54。In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was fed at 0.02 liter/min to feed 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass in a nitrogen atmosphere. 3-methoxybutyl acetate was heated to 70 ° C with stirring. Next, 55 parts by mass of methacrylic acid and 175 parts by mass of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate (mixed with a molar ratio of 50:50 by the formula (I-1) a compound represented by the formula (II-1) and 70 parts by mass of N-cyclohexylmaleimide dissolved in 140 parts by mass of a 3-methoxybutyl acetate preparation solution, and using a drop A funnel was added, and the dissolved solution was added dropwise to the flask which was incubated at 70 ° C over 4 hours. On the other hand, using another dropping funnel, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of acetic acid in 4 hours. A solution of 3-methoxybutyl ester was added dropwise to the flask. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 32.6% by mass and an acid value of 34.2 mg-KOH/g. The obtained resin Ab had a weight average molecular weight (Mw) of 13,600 and a degree of dispersion of 2.54.

合成例3Synthesis Example 3

如特開平11-133600號公報之合成例1般，在配置冷卻管、攪拌機之燒瓶內饋入7質量份之2,2’-偶氮雙(2,4-二甲基戊腈)、200質量份之二乙二醇二甲基醚。接著饋入30質量份之苯乙烯、20質量份之甲基丙烯酸及50質量份之甲基丙烯酸縮水甘油酯且以氮氣置換後，開始緩慢攪拌。使溶液之溫度上升至70℃，在該溫度下維持5小時，獲得包含樹脂Ac之聚合物溶液。所得樹脂Ac換算成聚苯乙烯之重量平均分子量(Mw)為24,000。In the flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 were fed in the same manner as in Synthesis Example 1 of JP-A-11-133600. Parts by mass of diethylene glycol dimethyl ether. Next, 30 parts by mass of styrene, 20 parts by mass of methacrylic acid, and 50 parts by mass of glycidyl methacrylate were fed and replaced with nitrogen, and stirring was started slowly. 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 resin Ac. The weight average molecular weight (Mw) of the obtained resin Ac in terms of polystyrene was 24,000.

合成例4Synthesis Example 4

除將合成例1之丙烯酸3,4-環氧基三環[5.2.1.02,6 ]癸酯(以莫耳比50:50混合以式(I-1)表示之化合物及以式(II-1)表示之化合物)變更為甲基丙烯酸3,4-環氧基環己基甲酯以外，其餘如合成例1般進行操作，獲得黏度(23℃)120mPa‧s、固成份32.8質量%，酸價36.2mg-KOH/g之共聚物(樹脂Ad)之溶液。所得樹脂Ad之重量平均分子量(Mw)為13,900，分散度為2.55。In addition to the 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate of Synthesis Example 1, a compound represented by the formula (I-1) in a molar ratio of 50:50 and a formula (II) The compound represented by the formula (1) was changed to 3,4-epoxycyclohexylmethyl methacrylate, and the other procedure was carried out as in Synthesis Example 1 to obtain a viscosity (23 ° C) of 120 mPa·s and a solid content of 32.8% by mass. A solution of a copolymer (resin Ad) having an acid value of 36.2 mg-KOH/g. The obtained resin Ad had a weight average molecular weight (Mw) of 13,900 and a degree of dispersion of 2.55.

上述結合劑樹脂之重量平均分子量(Mw)及數平均分子量(Mn)之測定係使用GPC法，以下列條件進行。The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above binder resin were measured by the GPC method under the following conditions.

裝置；K2479(島津製作所(股)製造)Device; K2479 (made by Shimadzu Corporation)

管柱；SHIMADZU Shim-pack GPC-80MPipe string; SHIMADZU Shim-pack GPC-80M

管柱溫度；40℃Column temperature; 40 ° C

溶劑；THF(四氫呋喃)Solvent; THF (tetrahydrofuran)

流速；1.0mL/minFlow rate; 1.0mL/min

檢測器；RIDetector; RI

以上述獲得之換算成聚苯乙烯之重量平均分子量及數平均分子量之比作為分散度(Mw/Mn)。The ratio of the weight average molecular weight and the number average molecular weight converted into polystyrene obtained above was defined as the degree of dispersion (Mw/Mn).

實施例1Example 1

於184份含合成例1中獲得之樹脂Aa之樹脂溶液(換算成固成份60份)中混合40份之二季戊四醇六丙烯酸酯、0.8份之1,3,5-參(3,5-二第三丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮(汽巴‧日本股份有限公司製造之IRGANOX3114)及53份之丙二醇單甲基醚乙酸酯、20份之丙酸3-乙氧基乙酯、37份之3-甲氧基-1-丁醇及87份之乙酸3-甲氧基丁酯，獲得熱硬化性樹脂組成物1。Mixing 40 parts of dipentaerythritol hexaacrylate, 0.8 parts of 1,3,5-parameter (3,5-di) in 184 parts of the resin solution containing the resin Aa obtained in Synthesis Example 1 (converted into 60 parts by weight) Third butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (IRGANOX 3114 manufactured by Ciba Japan Co., Ltd.) and 53 parts of propylene glycol monomethyl ether acetate, 20 parts of 3-ethoxyethyl propionate, 37 parts of 3-methoxy-1-butanol and 87 parts of 3-methoxybutyl acetate A thermosetting resin composition 1 was obtained.

表1中，(-)表示未包含該成份。In Table 1, (-) indicates that the component is not included.

<儲存安定性><Storage Stability>

使熱硬化性樹脂組成物1在23℃下放置2週，且將經放置後之熱硬化性樹脂組成物之黏度除以放置前組成物之黏度之值以%表示。結果示於表2。The thermosetting resin composition 1 was allowed to stand at 23 ° C for 2 weeks, and the viscosity of the thermosetting resin composition after standing was divided by the value of the viscosity of the composition before standing in %. The results are shown in Table 2.

若黏度改變趨近100%，例如在100~103%之範圍，則為良好。If the viscosity changes to 100%, for example, in the range of 100 to 103%, it is good.

黏度；使用黏度計(VISCOMETER TV-30；東機產業(股)製造)，於23℃下測定。Viscosity; measured using a viscometer (VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.) at 23 °C.

<鉛筆硬度><pencil hardness>

依序以中性洗劑、水及醇洗淨2英吋見方之玻璃基板(Eagle 2000；康寧公司製造)並經乾燥。以旋轉塗佈將熱硬化性樹脂組成物塗佈於該玻璃基板上，在100℃下預烘烤3分鐘後，於220℃下進行後烘烤20分鐘。冷卻後，測定該硬化膜之膜厚為3.0μm。A 2 inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated) was washed with a neutral detergent, water and alcohol in that order and dried. The thermosetting resin composition was applied onto the glass substrate by spin coating, prebaked at 100 ° C for 3 minutes, and then post-baked at 220 ° C for 20 minutes. After cooling, the film thickness of the cured film was measured to be 3.0 μm.

對上述獲得之硬化塗膜，以JIS K5400為準測定鉛筆硬度。結果示於表2。數字愈大則硬度愈佳，以5H以上較佳。The pencil hardness of the hardened coating film obtained above was measured in accordance with JIS K5400. The results are shown in Table 2. The larger the number, the better the hardness, preferably 5H or more.

<透過率><transmittance rate>

使用膜厚測定裝置(DEKTAK3；日本真空技術(股)製造)測定使用熱硬化性樹脂組成物1，以與用以測定鉛筆硬度而製作之硬化塗膜相同之方法製作硬化膜使膜厚成為2.9~3.1μm。Using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), a thermosetting resin composition 1 was used, and a cured film was produced in the same manner as the cured coating film prepared for measuring pencil hardness to have a film thickness of 2.9. ~3.1μm.

接著，使用顯微分光測光裝置(OSP-SP200；OLYMPUS公司製造)，測定所得硬化膜在400nm下之透過率(%)，且換算成膜厚3.0μm時之換算透過率。結果示於表2。Next, the transmittance (%) of the obtained cured film at 400 nm was measured using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.), and converted into a converted transmittance at a film thickness of 3.0 μm. The results are shown in Table 2.

<耐溶劑性><Solvent resistance>

以與用以測定鉛筆硬度製作之硬化塗膜相同之方法製作之塗膜在30℃之N-甲基吡咯啶酮(以下，簡稱為NMP)中浸漬30分鐘，且測定浸漬後之膜厚及透過率，且以下式求得其變化。The coating film produced by the same method as the hardened coating film prepared for measuring the pencil hardness was immersed in N-methylpyrrolidone (hereinafter, abbreviated as NMP) at 30 ° C for 30 minutes, and the film thickness after immersion was measured. Transmittance, and the following formula finds its change.

膜厚變化(%)；(浸漬後之膜厚(μm)/浸漬前之膜厚(μm))×100Film thickness change (%); (film thickness after immersion (μm) / film thickness before immersion (μm)) × 100

透過率變化(%)；(浸漬後之透過率(%)/浸漬前之透過率(%))×100Transmittance change (%); (transmission rate after immersion (%) / transmittance before immersion (%)) × 100

當膜厚變化之值接近100%時，膜未溶解或膨潤而較佳。另外，當透過率變化值高者為未變色而較佳。When the value of the film thickness change is close to 100%, the film is preferably not dissolved or swollen. Further, it is preferable that the transmittance change value is high without discoloration.

密著性；使用市售切割刀，在於NMP中浸漬後之塗膜上形成100個每邊1mm之正方形。使用市售玻璃紙膠帶進行剝離試驗。求得[(未被剝離而殘留在基板上之正方形數目)/100]。[(未被剝離而殘留在基板上之正方形數目)/100]之數值越大，膜之密著性越優異而較佳。Adhesiveness; using a commercially available cutting blade, 100 squares of 1 mm per side were formed on the coating film after immersion in NMP. The peel test was carried out using a commercially available cellophane tape. Obtained [(the number of squares remaining on the substrate without being peeled off) / 100]. The larger the value of [(the number of squares remaining on the substrate without being peeled off) / 100], the more excellent the adhesion of the film is, and it is preferable.

耐熱性；以與用以測定鉛筆硬度製作硬化塗膜相同之方法製作之塗膜在240℃下於清潔烘箱中放置1小時，測定加熱前後之膜厚及透過率(測定波長；400nm)，且以下式其變化。結果示於表2。Heat resistance; a film prepared by the same method as that for producing a hardened coating film for measuring the hardness of a pencil was placed in a cleaning oven at 240 ° C for 1 hour, and the film thickness and transmittance (measuring wavelength; 400 nm) before and after heating were measured, and The following formula changes. The results are shown in Table 2.

膜厚變化(%)；(加熱後之膜厚(μm)/加熱前之膜厚(μm))×100Film thickness change (%); (film thickness after heating (μm) / film thickness before heating (μm)) × 100

透過率變化(%)；(加熱後之透過率(%)/加熱前之透過率(%))×100Transmittance change (%); (transmittance after heating (%) / transmittance before heating (%)) × 100

膜厚變化之值接近100%時，未因加熱而使膜分解等而較佳。另外，透過率變化之值高者膜未變色而較佳。When the value of the film thickness change is close to 100%, it is preferable that the film is not decomposed by heating or the like. Further, it is preferred that the film having a high value of transmittance change does not change color.

密著性；使用市售切割刀，在經耐熱性試驗之加熱後塗膜上形成100個每邊1mm之正方形。使用市售玻璃紙膠帶進行剝離試驗。求得[(未被剝離而殘留在基板上之正方形數目)/100]。[(未被剝離而殘留在基板上之正方形數目)/100]之數值越大，膜之密著性越優異而較佳。Adhesiveness: Using a commercially available cutting blade, 100 squares of 1 mm per side were formed on the coating film after heating by the heat resistance test. The peel test was carried out using a commercially available cellophane tape. Obtained [(the number of squares remaining on the substrate without being peeled off) / 100]. The larger the value of [(the number of squares remaining on the substrate without being peeled off) / 100], the more excellent the adhesion of the film is, and it is preferable.

實施例2Example 2

如表1中所示之組成獲得熱硬化性樹脂組成物2，且如熱硬化性樹脂組成物1般進行其評價。結果示於表2。The thermosetting resin composition 2 was obtained as the composition shown in Table 1, and the evaluation was performed as in the thermosetting resin composition 1. The results are shown in Table 2.

比較例1Comparative example 1

使成為表1中所示之組成，獲得熱硬化性樹脂組成物3，且如實施例1般測定儲存安定性，由於增黏故終止其評價。僅在儲存安定性試驗前進行鉛筆硬度。The composition shown in Table 1 was obtained, and the thermosetting resin composition 3 was obtained, and the storage stability was measured as in Example 1, and the evaluation was terminated due to the increase in viscosity. Pencil hardness was only performed before the storage stability test.

比較例2Comparative example 2

使成為表1中所示之組成，獲得熱硬化性樹脂組成物4，且如實施例1般測定儲存安定性，由於增黏故終止其評價。僅在儲存安定性試驗前進行鉛筆硬度。The composition shown in Table 1 was obtained, and the thermosetting resin composition 4 was obtained, and the storage stability was measured as in Example 1, and the evaluation was terminated due to the increase in viscosity. Pencil hardness was only performed before the storage stability test.

比較例3Comparative example 3

於實施例1中使用之熱硬化性樹脂組成物1中添加4份作為光聚合起始劑之B-CIM(保土谷化學工業(股)製造)、0.8份作為增感劑之異丙基呫噸酮、3份作為促進劑之PEMP(堺化學工業(股)製造)，獲得組成物5，如實施例1般進行其評價。結果示於表2。4 parts of B-CIM (manufactured by Hodogaya Chemical Industry Co., Ltd.) as a photopolymerization initiator, and 0.8 parts of isopropyl hydrazine as a sensitizer were added to the thermosetting resin composition 1 used in Example 1. Toluene ketone, 3 parts of PEMP (manufactured by Sigma Chemical Industry Co., Ltd.) as a promoter, and the composition 5 was obtained, and the evaluation was carried out as in Example 1. The results are shown in Table 2.

由表2中所示之實施例1~2之結果，可知含有具有特定構造之環氧基之結合劑樹脂之本發明熱硬化性樹脂組成物之儲存安定性優異，且若使用本發明之熱硬化性樹脂組成物，可形成透明性、耐溶劑性、耐熱性、表面硬度優異之塗膜。From the results of Examples 1 and 2 shown in Table 2, it is understood that the thermosetting resin composition of the present invention containing a binder resin having a specific structure is excellent in storage stability, and if the heat of the present invention is used, The curable resin composition can form a coating film excellent in transparency, solvent resistance, heat resistance, and surface hardness.

另一方面，比較例1及2中揭示之未含具有特定構造之環氧基之結合劑樹脂之熱硬化性樹脂組成物僅只能得到儲存安定性差之塗膜。另外，含有光聚合起始劑之比較例3之組成物僅只能得到透過率低，透明性差之膜。On the other hand, the thermosetting resin composition of the binder resin not containing the epoxy group having a specific structure disclosed in Comparative Examples 1 and 2 can only obtain a coating film having poor storage stability. Further, the composition of Comparative Example 3 containing a photopolymerization initiator only obtained a film having low transmittance and poor transparency.

產業上利用之可能性Industrial use possibility

本發明之熱硬化性樹脂組成物之儲存安定性優異，可形成透明性、耐溶劑性、耐熱性、表面硬度均優異之塗膜，用於絕緣膜、用以調和著色圖型之膜厚之塗層等而可用於顯示裝置用之透明膜之形成。The thermosetting resin composition of the present invention is excellent in storage stability, and can form a coating film excellent in transparency, solvent resistance, heat resistance, and surface hardness, and is used for an insulating film to adjust the film thickness of a coloring pattern. A coating or the like can be used for the formation of a transparent film for a display device.

Claims (4)

一種熱硬化性樹脂組成物，其特徵為含有結合劑樹脂(A)、熱硬化性化合物(B)及溶劑(C)，且不含光聚合起始劑；其中結合劑樹脂(A)為使不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環式環氧基之單體(A2)共聚合而成之共聚物，或不飽和羧酸及/或不飽和羧酸酐(A1)與具有脂肪族多環環氧基之單體(A2)，以及與(A1)及(A2)不同且可與(A1)及(A2)共聚合之單體(A3)之共聚物；熱硬化性化合物(B)為含有不飽和雙鍵之2官能單體或3官能以上之多官能單體化合物。 A thermosetting resin composition comprising a binder resin (A), a thermosetting compound (B), and a solvent (C), and does not contain a photopolymerization initiator; wherein the binder resin (A) is used Copolymerization of an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1) with a monomer having an aliphatic polycyclic epoxy group (A2), or an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1) a copolymer of a monomer (A2) having an aliphatic polycyclic epoxy group, and a monomer (A3) different from (A1) and (A2) and copolymerizable with (A1) and (A2) The thermosetting compound (B) is a bifunctional monomer having an unsaturated double bond or a polyfunctional monomer compound having three or more functional groups. 如申請專利範圍第1項之熱硬化性樹脂組成物，其中具有脂肪族多環式環氧基之單體(A2)係選自由以式(I)表示之化合物及以式(II)表示之化合物所組成之群組之至少一種化合物： 式(I)及式(II)中，R分別獨立表示氫原子或可經羥基取代之碳數1~4之烷基，X分別獨立表示單鍵或可含有雜原子之碳數1~6之伸烷基。The thermosetting resin composition of claim 1, wherein the monomer having an aliphatic polycyclic epoxy group (A2) is selected from the group consisting of the compound represented by the formula (I) and represented by the formula (II) At least one compound of the group consisting of: In the formulae (I) and (II), R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, and X each independently represents a single bond or may have a carbon number of 1 to 6 of a hetero atom. Alkyl. 一種塗膜，其特徵係使用申請專利範圍第1項或第2項之熱硬化性樹脂組成物所形成。 A coating film characterized by being formed using the thermosetting resin composition of the first or second aspect of the patent application. 一種顯示裝置，其特徵係包含申請專利範圍第3項之塗膜。 A display device characterized by comprising a coating film of the third application of the patent application.
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