TWI765948B

TWI765948B - Resin composition for liquid crystal display device, film and copolymer for liquid crystal display device

Info

Publication number: TWI765948B
Application number: TW106145528A
Authority: TW
Inventors: 河西裕
Original assignee: 日商住友化學股份有限公司
Priority date: 2016-12-27
Filing date: 2017-12-25
Publication date: 2022-06-01
Also published as: JP7105562B2; CN108241258B; CN108241258A; KR102443099B1; KR20180076331A; JP2018106172A; TW201833256A

Abstract

A resin composition for a liquid crystal display device, contains a resin (A), a solvent, and a leveling agent, the resin (A) is a copolymer containing a constituent unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a constituent unit (Ab) having an active methylene group or an active methine group, and not containing any constituent unit (Ac) derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

Description

液晶顯示裝置用樹脂組成物、液晶顯示裝置用膜及共聚合物 Resin composition for liquid crystal display device, film for liquid crystal display device, and copolymer

本發明係有關液晶顯示裝置用樹脂組成物、液晶顯示裝置用膜及共聚合物。 The present invention relates to a resin composition for a liquid crystal display device, a film for a liquid crystal display device, and a copolymer.

近年的液晶顯示裝置中，已在形成外塗層等膜方面使用樹脂組成物。日本特開2008-181087號公報記載之樹脂組成物係含有由甲基丙烯酸及3,4-環氧基三環[5.2.1.0^2.6]丙烯酸癸酯聚合而成之共聚合物的樹脂組成物。 In recent liquid crystal display devices, resin compositions have been used to form films such as overcoat layers. The resin composition described in Japanese Patent Laid-Open No. 2008-181087 is a resin composition containing a copolymer obtained by polymerizing methacrylic acid and 3,4-epoxytricyclo[ ^5.2.1.02.6 ]decyl acrylate.

即使在具有階差的基底或基板上形成液晶顯示裝置的外塗層時，也要求該外塗層是平整的。 Even when an overcoat layer of a liquid crystal display device is formed on a base or substrate having a step difference, the overcoat layer is required to be flat.

本發明的目的是提供即使在具有階差的基底或基板上形成，也可形成平整的膜之液晶顯示裝置用樹脂組成物、及適合作為該樹脂組成物的材料之共聚合物。 An object of the present invention is to provide a resin composition for liquid crystal display devices which can form a flat film even when formed on a base or substrate having a step difference, and a copolymer suitable as a material for the resin composition.

本發明係包含以下的發明。 The present invention includes the following inventions.

〔1〕一種液晶顯示裝置用樹脂組成物，係含有樹脂(A)、溶劑及整平劑，前述樹脂(A)係含有具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)而不含來自屬於不飽和羧酸及不飽和羧酸酐所組成之群組的化合物之構成單元(Ac)的共聚合物。 [1] A resin composition for a liquid crystal display device, comprising a resin (A), a solvent and a leveling agent, wherein the resin (A) comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and A copolymer having a constituent unit (Ab) of an active methylene group or an active methine group without a constituent unit (Ac) derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

〔2〕如〔1〕項所述之液晶顯示裝置用樹脂組成物，其中，前述樹脂(A)的酸價為0mg-KOH/g至5mg-KOH/g。 [2] The resin composition for a liquid crystal display device according to the item [1], wherein the acid value of the resin (A) is 0 mg-KOH/g to 5 mg-KOH/g.

〔3〕如〔1〕或〔2〕項所述之液晶顯示裝置用樹脂組成物，其中，前述樹脂(A)係由具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)形成之共聚合物。 [3] The resin composition for a liquid crystal display device according to the item [1] or [2], wherein the resin (A) is composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and A copolymer formed by a constituent unit (Ab) having an active methylene group or an active methine group.

〔4〕如〔1〕至〔3〕項中任一項所述之液晶顯示裝置用樹脂組成物，其中，前述構成單元(Aa)係由具有環氧乙烷基與乙烯性不飽和鍵的單體衍生而得之構成單元。 [4] The resin composition for a liquid crystal display device according to any one of [1] to [3], wherein the structural unit (Aa) is composed of a compound having an oxirane group and an ethylenically unsaturated bond A unit derived from a monomer.

〔5〕如〔1〕至〔4〕項中任一項所述之液晶顯示裝置用樹脂組成物，其中，前述構成單元(Aa)係式(Aa-1)或式(Aa-2)表示的構成單元。 [5] The resin composition for a liquid crystal display device according to any one of [1] to [4], wherein the structural unit (Aa) is represented by formula (Aa-1) or formula (Aa-2) constituent unit.

[式(Aa-1)及式(Aa-1)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。

[In formula (Aa-1) and formula (Aa-1), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^b1及X^b2係表示單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊--R^b3-NH-。 X ^b1 and X ^b2 represent a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *--R ^b3 -NH-.

R^b3係表示碳數1至6的烷二基。 R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

＊係表示與O的鍵結。] * indicates a bond with O. ]

〔6〕如〔1〕至〔5〕項中任一項所述之液晶顯示裝置用樹脂組成物，其中，整平劑是氟系界面活性劑。 [6] The resin composition for a liquid crystal display device according to any one of [1] to [5], wherein the leveling agent is a fluorine-based surfactant.

〔7〕一種液晶顯示裝置用膜，係由〔1〕至〔6〕項中任一項所述之液晶顯示裝置用樹脂組成物形成者。 [7] A film for a liquid crystal display device formed from the resin composition for a liquid crystal display device according to any one of [1] to [6].

〔8〕一種共聚合物，係含有具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)而不含來自屬於由不飽和羧酸及不飽和羧酸酐所組成之群組的化合物之構成單元(Ac)，前述構成單元(Aa)包含式(Aa-1)或式(Aa-2)表示的構成單元。 [8] A copolymer comprising a constituent unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a constituent unit (Ab) having an active methylene group or an active methine group, but not derived from The structural unit (Ac) of the compound of the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, the said structural unit (Aa) contains the structural unit represented by formula (Aa-1) or formula (Aa-2).

[式(Aa-1)及式(Aa-2)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。

[In formula (Aa-1) and formula (Aa-2), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^b1及X^b2係表示單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊-R^b3-NH-。 X ^b1 and X ^b2 represent a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-.

＊係表示與O的鍵結。] * indicates a bond with O. ]

若藉由本發明的液晶顯示裝置用樹脂組成物，因可減少基底或基板的階差，故即使在具有階差的基底或基板上也可形成平整的膜。 According to the resin composition for liquid crystal display devices of the present invention, since the level difference of the base or the substrate can be reduced, a flat film can be formed even on the base or the substrate having the level difference.

1‧‧‧玻璃基板 1‧‧‧glass substrate

2‧‧‧線與間隔圖案 2‧‧‧Line and Space Patterns

2a‧‧‧間隔 2a‧‧‧interval

2b‧‧‧線 2b‧‧‧line

3‧‧‧膜 3‧‧‧Film

第1圖係表示玻璃基板上經積層線圖案與膜之狀態的示意圖。 FIG. 1 is a schematic view showing a state in which a line pattern and a film are laminated on a glass substrate.

本說明書中，例示作為各成分的化合物如無特別的說明，可單獨使用或將數種組合使用。 In the present specification, the compounds exemplified as the respective components may be used alone or in combination of several unless otherwise specified.

[液晶顯示裝置用樹脂組成物] [Resin composition for liquid crystal display device]

以下，本發明的液晶顯示裝置用樹脂組成物也稱為「本發明的樹脂組成物」或「樹脂組成物」。 Hereinafter, the resin composition for liquid crystal display devices of the present invention is also referred to as "the resin composition of the present invention" or "resin composition".

本發明的樹脂組成物係含有樹脂(A)、溶劑(E)及整平劑(B)的樹脂組成物，樹脂(A)係含有具有碳數2至4的環狀醚結構的構成單元(以下，稱為構成單元(Aa)。)與具有活性亞甲基或活性次甲基的構成單元(以下，稱為構成單元(Ab)。)而不含有來自屬於由不飽和羧酸及不飽和羧酸酐所組成之群組的構成單元(以下，稱為構成單元(Ac)。)之共聚合物。本發明的樹脂組成物，因樹脂(A)含有構成單元(Aa)與構成單元(Ab)、而不含構成單元(Ac)，故可改善由樹脂組成物形成的膜之平整性。 The resin composition of the present invention is a resin composition containing a resin (A), a solvent (E), and a leveling agent (B), and the resin (A) contains a structural unit having a cyclic ether structure having 2 to 4 carbon atoms ( Hereinafter, it is referred to as a structural unit (Aa).) and a structural unit having an active methylene group or an active methine group (hereinafter, referred to as a structural unit (Ab).) do not contain components derived from unsaturated carboxylic acid and unsaturated A copolymer of a structural unit (hereinafter, referred to as a structural unit (Ac)) of the group consisting of a carboxylic acid anhydride. In the resin composition of the present invention, since the resin (A) contains the structural unit (Aa) and the structural unit (Ab), but does not contain the structural unit (Ac), the flatness of the film formed from the resin composition can be improved.

本發明的樹脂組成物係以含有聚合性化合物(C)為佳。含有聚合性化合物(C)時，係以含有聚合起始劑(D)為佳。同時，本發明的樹脂組成物也可含有其他的成分、抗氧化劑(F)、硬化劑(G)等。硬化劑(G)可例示如多元羧酸(G1)、咪唑化合物(G2)等。 The resin composition of the present invention preferably contains the polymerizable compound (C). When a polymerizable compound (C) is contained, it is preferable to contain a polymerization initiator (D). At the same time, the resin composition of the present invention may contain other components, antioxidants (F), hardeners (G), and the like. As a hardening|curing agent (G), a polyhydric carboxylic acid (G1), an imidazole compound (G2), etc. can be illustrated, for example.

<樹脂(A)> <Resin (A)>

樹脂(A)係具有硬化性的樹脂，並以熱硬化性樹脂為佳，而以於60℃以上的熱進行硬化之樹脂更佳。樹脂(A)係含有構成單元(Aa)與構成單元(Ab)而不含構成單元(Ac)的共聚合物。該共聚合物可進一步與構成單元(Aa)或構成單元(Ab)共聚合，且亦可具有來自構成單元(Aa)、(Ab)及(Ac)以外的化合物之構成單元(以下，稱為構成單元(Ad))。 The resin (A) is a curable resin, preferably a thermosetting resin, and more preferably a resin cured by heat at 60° C. or higher. Resin (A) is a copolymer which contains a structural unit (Aa) and a structural unit (Ab), and does not contain a structural unit (Ac). The copolymer may further copolymerize with the structural unit (Aa) or the structural unit (Ab), and may have structural units derived from compounds other than the structural units (Aa), (Ab) and (Ac) (hereinafter, referred to as Constituent unit (Ad)).

本說明中，「(甲基)丙烯酸」係指選自丙烯酸及甲基丙烯酸所組成之群組的至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等標示也具有相同之意。樹脂(A)含有構成單元(Aa)、構成單元(Ab)及構成單元(Ad)，可各別含有2種以上。 In this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Designations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning. The resin (A) contains a structural unit (Aa), a structural unit (Ab), and a structural unit (Ad), and each of two or more types may be contained.

〔1〕構成單元(Aa) [1] Constituent unit (Aa)

構成單元(Aa)係由碳數2至4的環狀醚結構(例如選自環氧乙烷環、氧雜環丁烷環及四氫呋喃環所組成之群組的至少1種)及具有乙烯性不飽和鍵的不飽和化合物衍生而得之構成單元。構成單元(Aa)可由該不飽和化合物聚合而得。構成單元(Aa)亦可藉由其他的構成單元(Aa’)與具有碳數2至4的環狀醚結構之化合物反應聚合而得。 The constituent unit (Aa) is composed of a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and has vinyl properties Units derived from unsaturated compounds with unsaturated bonds. The constituent unit (Aa) can be obtained by polymerizing the unsaturated compound. The structural unit (Aa) can also be obtained by reacting and polymerizing other structural units (Aa') with a compound having a cyclic ether structure having 2 to 4 carbon atoms.

衍生而得構成單元(Aa)的不飽和化合物可列舉：例如具有環氧乙烷基與乙烯性不飽和鍵的單體(以下，稱為單體(Aa1))、具有氧雜環丁烷基與乙烯性不飽和鍵的單體(以下，稱為單體(Aa2))、具有四氫呋喃基與乙烯性不飽和鍵的單體(以下，稱為單體(Aa3))。 The unsaturated compound derived from the structural unit (Aa) includes, for example, a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa1)), an oxetanyl group A monomer having an ethylenically unsaturated bond (hereinafter, referred to as a monomer (Aa2)), and a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter, referred to as a monomer (Aa3)).

單體(Aa1)可列舉：例如具有直鏈狀或分枝鏈狀的不飽和脂肪族烴基係環氧化之結構與乙烯性不飽和鍵的單體(以下，稱為單體(Aa1-1))、及具有不飽和脂環式烴基係環氧化的構造與乙烯性不飽和鍵之單體(以下，稱為單體(Aa1-2))。 The monomer (Aa1) includes, for example, a monomer having a linear or branched unsaturated aliphatic hydrocarbon-based epoxidized structure and an ethylenically unsaturated bond (hereinafter, referred to as monomer (Aa1-1)) ), and a monomer having an epoxidized structure of an unsaturated alicyclic hydrocarbon group and an ethylenically unsaturated bond (hereinafter, referred to as monomer (Aa1-2)).

單體(Aa1-1)可列舉(甲基)丙烯酸去水甘油酯、(甲基)丙烯酸β-甲基去水甘油酯、(甲基)丙烯酸β-乙基去水甘油酯、去水甘油基乙烯醚、鄰-乙烯基苯甲基去水甘油醚、間-乙烯基苯甲基去水甘油醚、對-乙烯基苯甲基去水甘油醚、α-甲基-鄰-乙烯基苯甲基去水甘油醚、α-甲基-間-乙烯基苯甲基去水甘油醚、α-甲基-對-乙烯基苯甲基去水甘油醚、2,3-雙(去水甘油基氧基甲基)苯乙烯、2,4-雙(去水甘油基氧基甲基)苯乙烯、2,5-雙(去水甘油基氧基甲基)苯乙烯、2,6-雙(去水甘油基氧基甲基)苯乙烯、2,3,4-參(去水甘油基氧基甲基)苯乙烯、2,3,5-參(去水甘油基氧基甲基)苯乙烯、2,3,6-參(去水甘油基氧基甲基)苯乙烯、3,4,5-參(去水甘油基氧基甲基)苯乙烯、2,4,6-參(去水甘油基氧基甲基)苯乙烯等。 Examples of the monomer (Aa1-1) include (meth)acrylate dehydrated glyceride, (meth)acrylate β-methyl dehydrated glyceride, (meth)acrylate β-ethyl dehydrated glyceride, and (meth)acrylate dehydrated glycerol Ethyl vinyl ether, o-vinylbenzyl anhydrous, m-vinylbenzyl anhydrous, p-vinylbenzyl anhydrous, alpha-methyl-o-vinylbenzene Methyl deglyceryl ether, α-methyl-m-vinylbenzyl anhydroglycerol, α-methyl-p-vinylbenzyl anhydroglycerol, 2,3-bis(dehydrated glycerol) oxymethyl)styrene, 2,4-bis(dehydroglyceryloxymethyl)styrene, 2,5-bis(dehydroglyceryloxymethyl)styrene, 2,6-bis (Dehydroglyceryloxymethyl)styrene, 2,3,4-paras(deglyceryloxymethyl)styrene, 2,3,5-paraffin(desglyceryloxymethyl) Styrene, 2,3,6-paraffin (dehydroglyceryloxymethyl) styrene, 3,4,5-paraffin (dehydroglyceryloxymethyl) styrene, 2,4,6-paraffin (Dehydroglyceryloxymethyl)styrene and the like.

單體(Aa1-2)可列舉乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如，CELLOXIDE 2000；(股)Daicel製造)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如，Cyclomer A 400；(股)Daicel製造)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如，Cyclomer M 100；(股)Daicel製造)、式(I)表示的化合物及式(II)表示的化合物等。 Examples of the monomer (Aa1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel), (methyl) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A 400; manufactured by (stock) Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M 100; ( Co., Ltd.) Daicel Co., Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[式(I)及式(II)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。 [In formula (I) and formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^b1及X^b2係相互獨立的表示單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊-R^b3-NH-。 X ^b1 and X ^b2 independently represent a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-.

＊係表示與O的鍵結。] * indicates a bond with O. ]

碳數1至4的烷基可列舉甲基、乙基、正-丙基、異丙基、正-丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.

氫原子經羥基取代的烷基可列舉羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1- Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R^b1及R^b2較佳可列舉氫原子、甲基、羥基甲基、1-羥基乙基及2-羥基乙基，更佳的可列舉氫原子及甲基。 Preferred examples of R ^b1 and R ^b2 include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

碳數1至6的烷二基可列舉亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl having 1 to 6 carbon atoms include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl, hexane-1,6-diyl, etc.

X^b1及X^b2較佳的可列舉單鍵、亞甲基、伸乙基、＊-CH₂-O-、＊-CH₂CH₂-O-，更佳的可列舉單鍵、＊-CH₂CH₂-O-。＊是表示與O的鍵結。 Preferred examples of X ^b1 and X ^b2 include single bond, methylene group, ethylidene group, *-CH ₂ -O-, *-CH ₂ CH ₂ -O-, and more preferred examples include single bond, *-CH _2CH2 - _O- . * is a bond with O.

式(I)表示的化合物可列舉式(I-1)至式(I-15)中任一式表示的化合物等。其中，以式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)至式(I-15)表示的化合物為佳，而以式(I-1)、式(I-7)、式(I-9)或式(I-15)表示的化合物更佳。 As the compound represented by the formula (I), the compound represented by any one of the formulae (I-1) to (I-15), and the like can be exemplified. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) ) is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

式(II)表示的化合物可列舉式(II-1)至式(II-15)中任一式表示的化合物等。其中，以式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)至式(II-15)表示的化合物為佳，而以式(II-1)、式(II-7)、式(II-9)或式(II-15)表示的化合物更佳。 As the compound represented by the formula (II), the compound represented by any one of the formulae (II-1) to (II-15), and the like can be exemplified. Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) ) is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

式(I)表示的化合物及式(II)表示的化合物，可分別單獨使用，也可用任意比率混合後使用。混合使用時，式(I)表示的化合物及式(II)表示的化合物之含有比率以莫耳為基準，較佳的是5：95至95：5，更佳的是10：90至90：10，又更佳的是20：80至80：20。例如，可使用以50：50之比例含有式(I-1)表示的化合物與式(II-1)表示的化合物之混合物(作為市售品，有商品名「E-DCPA」((股)Daicel製造))。 The compound represented by the formula (I) and the compound represented by the formula (II) may be used independently, respectively, or may be mixed in an arbitrary ratio and used. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is based on moles, preferably 5:95 to 95:5, more preferably 10:90 to 90: 10, and even better is 20:80 to 80:20. For example, a mixture (commercially available under the trade name "E-DCPA" ((stock) Manufactured by Daicel)).

單體(Aa2)係以具有氧雜環丁烷基與(甲基)丙烯醯氧基的單體更佳。單體(Aa2)可列舉3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 The monomer (Aa2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of the monomer (Aa2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl Alkyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-propenyloxymethyl oxetane, 3-methyl-3-methacryloyloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3- Ethyl-3-propenyloxyethyl oxetane, etc.

單體(Aa3)係以具有四氫呋喃基與(甲基)丙烯醯氧基的單體為佳。單體(Aa3)可列舉丙烯酸四氫呋喃酯(例如Viscoat V # 150，大阪有機化學工業(股)製造)。 The monomer (Aa3) is preferably a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. As the monomer (Aa3), tetrahydrofuran acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.

就使樹脂組成物的保存穩定性、獲得的膜之耐藥品性、耐熱性及機械強度傾向優異，並且可得優異的平整性而言，構成單元(Aa)是以由單體(Aa1)衍生的構成單元為佳，並以由單體(Aa1-2)衍生的構成單元更佳，而以式(Aa1-1)、式(Aa1-2)表示的構成單元又更佳。 The constituent unit (Aa) is derived from the monomer (Aa1) so that the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the obtained film tend to be excellent, and excellent flatness can be obtained. The structural unit of is preferable, and the structural unit derived from the monomer (Aa1-2) is more preferable, and the structural unit represented by the formula (Aa1-1) and the formula (Aa1-2) is even more preferable.

式(Aa1-1)表示的構成單元可由式(I)表示的化合物衍生而得，式(Aa1-2)表示的構成單元可由式(II)表示的化合物衍生而得。 The structural unit represented by the formula (Aa1-1) can be derived from the compound represented by the formula (I), and the structural unit represented by the formula (Aa1-2) can be derived from the compound represented by the formula (II).

[式(Aa1-1)及式(Aa1-2)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。 [In formula (Aa1-1) and formula (Aa1-2), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^b1及X^b2係表示相互獨立的單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊-R^b3-NH-。 X ^b1 and X ^b2 represent mutually independent single bonds, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-.

＊係表示與O的鍵結。] * indicates a bond with O. ]

〔2〕構成單元(Ab) [2] Constituent unit (Ab)

構成單元(Ab)係由具有活性亞甲基或活性次甲基的不飽和化合物衍生而得之構成單元。由具有活性亞甲基或活性次甲基的不飽和化合物衍生而得之構成單元係指由該不飽和化合物聚合而得的共聚合物中之該不飽和化合物的構成單元。該構成單元可藉由具有活性亞甲基或活性次甲基的不飽和化合物聚合而得。或也可使另外的構成單元(Ab’)與具有活性亞甲基或活性次甲基的化合物(Ab”)反應而得。 The constituent unit (Ab) is a constituent unit derived from an unsaturated compound having an active methylene group or an active methine group. The structural unit derived from an unsaturated compound having an active methylene group or an active methine group refers to the structural unit of the unsaturated compound in the copolymer obtained by polymerizing the unsaturated compound. This structural unit can be obtained by polymerizing an unsaturated compound having an active methylene group or an active methine group. Alternatively, it can be obtained by reacting another constituent unit (Ab') with a compound (Ab") having an active methylene group or an active methine group.

衍生而得構成單元(Ab)的不飽和化合物是以式(III)表示，具有活性次甲基的不飽和化合物可列舉式(IV)表示的化合物。 The unsaturated compound derived from the structural unit (Ab) is represented by the formula (III), and the unsaturated compound having an active methine group includes the compound represented by the formula (IV).

R¹¹-X-R¹²-R¹³-CH₂-R¹⁴ (III) R ¹¹ -XR ¹² -R ¹³ -CH ₂ -R ¹⁴ (III)

[式(III)及式(VI)中，R¹¹係表示氫原子或可含有雜原子的碳數1至24的烴基。 [In formula (III) and formula (VI), R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.

R¹²係表示單鍵或碳數1至20的二價烴基。 R ¹² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.

R¹³係表示式(1-1)至式(1-3)中任一式表示的二價之基。 R ¹³ represents a divalent group represented by any of the formulae (1-1) to (1-3).

R¹⁴係表示式(1-4)至式(1-7)中任一式表示的基。] R ¹⁴ represents a group represented by any of the formulae (1-4) to (1-7). ]

[R¹⁴係表示氫原子或可含有雜原子的碳數1至24之羥基。X係表示式(1-8)至式(1-10)中任一式表示的二價基。] [R ¹⁴ represents a hydrogen atom or a hydroxyl group having 1 to 24 carbon atoms which may contain a hetero atom. X represents a divalent group represented by any of the formulae (1-8) to (1-10). ]

R¹¹及R¹⁵係以可具有氧原子或氮原子的碳數1至8之烷基、可具有氧原子或氮原子的碳數3至10之環烷基、氫原子等為佳。 R ¹¹ and R ¹⁵ are preferably an alkyl group having 1 to 8 carbon atoms which may have an oxygen atom or a nitrogen atom, a cycloalkyl group having 3 to 10 carbon atoms which may have an oxygen atom or a nitrogen atom, a hydrogen atom or the like.

R¹¹及R¹⁵係相互獨立，以氫原子、甲基、乙基、丙基、丁基、己基、環己基、甲氧基、乙氧基、丙氧基、己氧基、環己氧基或式(1-11)至式(1-13)表示的基為佳，並以氫原子或甲基更佳。 R ¹¹ and R ¹⁵ are independent of each other, and are represented by hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexyloxy group, cyclohexyloxy group Or the groups represented by the formula (1-11) to the formula (1-13) are preferable, and a hydrogen atom or a methyl group is more preferable.

R¹²係以單鍵、碳數1至20(以碳數1至4為佳)的烷二基、碳數3至10的環烷二基為佳。R¹²係以單鍵、亞甲基、伸乙基、丙烷二基、丁烷二基、己烷二基、環己烷二基、辛烷二基、癸烷二基、十二烷二基、下述式表示的基(＊是表示鍵結。)為佳，並以單鍵、亞甲基、伸乙基更佳。 R ¹² is preferably a single bond, an alkanediyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms), or a cycloalkanediyl group having 3 to 10 carbon atoms. R ¹² is represented by a single bond, methylene, ethylidene, propanediyl, butanediyl, hexanediyl, cyclohexanediyl, octanediyl, decanediyl, dodecanediyl , The group represented by the following formula (* represents a bond.) is preferable, and a single bond, a methylene group, and an ethylidene group are more preferable.

式(III)表示的化合物，具體上可列舉以下的化合物等。 The compound represented by the formula (III) specifically includes the following compounds.

式(IV)表示的化合物可具體列舉以下的化合物等。 Specific examples of the compound represented by the formula (IV) include the following compounds.

式(III-1)至(III-7)、(III-16)、(IV-1)、(IV-2)及(IV-5)係R¹¹為甲基的化合物，同樣的，將R¹¹置換成氫原子的化合物，也可列舉作為式(III)表示的化合物或式(IV)表示的化合物。 Formulas (III-1) to (III-7), (III-16), (IV-1), (IV-2) and (IV-5) are compounds in which R ¹¹ is methyl. Similarly, R The compound in which ¹¹ is substituted with a hydrogen atom can also be exemplified as the compound represented by the formula (III) or the compound represented by the formula (IV).

構成單元(Ab)係以式(Ab-1)表示的構成單元為佳。 The structural unit (Ab) is preferably a structural unit represented by the formula (Ab-1).

[式(Ab-1)中，R³是表示氫原子或甲基，R⁴是表示氫原子或碳數1至6的烷基。] [In formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

衍生而得式(Ab-1)表示的構成單元之化合物可列舉：例如乙醯乙酸2-(甲基丙烯醯氧基)乙酯〔式(III-1)表示的化合物〕。 As a compound which derives the structural unit represented by formula (Ab-1), for example, 2-(methacryloyloxy)ethyl acetonitrile [compound represented by formula (III-1)] can be mentioned.

〔3〕構成單元(Ac) [3] Structural unit (Ac)

構成單元(Ac)係由屬於由不飽和羧酸及不飽和羧酸酐所組成之群組的化合物衍生而得之構成單元。屬於由不飽和羧酸及不飽和羧酸酐組成之群組的化合物可列舉：例如丙烯酸、甲基丙烯酸、巴豆酸、鄰-乙烯基苯甲酸、間-乙烯基苯甲酸、對-乙烯基苯甲酸等不飽和單羧酸；順丁烯二酸、反丁烯二酸、檸康酸、甲基反丁烯二酸(或中康酸)、衣康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸；甲基-5-降冰片烯-2,3-二羧酸、5-羧基二環[2.2.1]庚-2-烯、5,6-二羧基二環[2.2.1]庚-2-烯、5-羧基-5-甲基二環[2.2.1]庚-2-烯、5-羧基-5-乙基二環[2.2.1]庚-2-烯、5-羧基-6-甲基二環[2.2.1]庚-2-烯、5-羧基-6-乙基二環[2.2.1]庚-2-烯等含有羧基的二環不飽和化合物；順丁烯二酸酐、檸康酸酐、衣康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基二環[2.2.1]庚-2-烯酐等不飽和二羧酸酐；琥珀酸單〔2-(甲基)丙烯醯氧基乙基〕酯、鄰苯二甲酸單〔2-(甲基)丙烯醯氧基乙基〕酯等2價以上的多元羧酸之不飽和單〔(甲基)丙烯醯氧基烷基〕酯；α-(羥基甲基)丙烯酸等在同一分子中含有羥基及羧基之不飽和丙烯酸酯等。 The constitutional unit (Ac) is a constitutional unit derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Compounds belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include, for example, acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid Isounsaturated monocarboxylic acids; maleic acid, fumaric acid, citraconic acid, methyl fumaric acid (or mesaconic acid), itaconic acid, 3-vinylphthalic acid, 4-Vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1 ,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5 ,6-dicarboxybicyclo[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-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2- Bicyclic unsaturated compounds containing carboxyl groups such as alkene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5 ,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1 ] Unsaturated dicarboxylic anhydrides such as hept-2-ene anhydride; mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acrylooxyethyl phthalate] Unsaturated mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids with a valence of divalent or more, such as hydroxy] esters; unsaturated acrylic acids containing hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl)acrylic acid esters, etc.

〔4〕構成單元(Ad) [4] Structural unit (Ad)

衍生而得構成單元(Ad)的化合物可列舉：例如以下的化合物。 As a compound which derives the structural unit (Ad), the following compounds are mentioned, for example.

(甲基)丙烯酸甲酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(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[5.2.1.0^2.6]癸烷-8-基酯(在該技術領域中，通稱為「(甲基)丙烯酸二環戊基酯。同時，也稱為「(甲基)丙烯酸三環癸基酯。)、(甲基)丙烯酸三環[[5.2.1.0^2.6]癸烯-8-基酯(在該技術領域中，通稱為「(甲基)丙烯酸二環戊烯基酯。)、(甲基)丙烯酸二環戊烯氧基乙基酯、(甲基)丙烯酸異冰片基酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸丙炔酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯等含有羥基的(甲基)丙烯酸酯；順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙酯等二羧酸二酯；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-羥基二環[2.2.1]庚-2-烯、5-羥基甲基二環[2.2.1]庚-2-烯、5-(2’-羥基乙基)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、5,6-二羥基二環[2.2.1]庚-2-烯、5,6-二(羥基甲基)二環[2.2.1]庚-2-烯、5,6-二(羥基乙基)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-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-羥基甲基-5-甲基二環[2.2.1]庚-2-烯、5-第三丁氧基羰基二環[2.2.1]庚-2-烯、5-環己氧基羰基二環[2.2.1]庚-2-烯、5-苯氧基羰基二環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)二環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)二環[2.2.1]庚-2-烯等二環不飽和化合物；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺乙酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基亞胺衍生物；苯乙烯、α-甲基苯乙烯、鄰-乙烯基甲苯、間-乙烯基甲苯、對-乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯及2,3-二甲基-1,3-丁二烯等。 Methyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, ( Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[ ^5.2.1.02.6 ]decan-8-yl (meth)acrylate (In this technical field, it is commonly called "dicyclopentyl (meth)acrylate. At the same time, it is also called "tricyclodecyl (meth)acrylate.), (meth)acrylate tricyclo[[5.2 .1.0 ^2.6 ] Decen-8-yl ester (in this technical field, commonly known as "(meth)acrylic acid dicyclopentenyl ester.), (meth)acrylic acid dicyclopentenyloxyethyl ester, Isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate (meth)acrylates such as naphthyl acrylate and benzyl (meth)acrylate; (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate ) acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; 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- 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-bis( Hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-th Tributoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1 ]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2. 1] Bicyclic unsaturated compounds such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimide yl-6-cis-butene Dicarbonyl imine derivatives such as imide acetate, N-succinimidyl-3-maleimide propionate, N-(9-acridyl) maleimide, etc. compounds; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, paraffin Dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, etc.

就共聚合反應性及耐熱性而言，此等之中，係以苯乙烯、乙烯基甲苯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺及N-苯甲基順丁烯二醯亞胺為佳。 In terms of copolymerization reactivity and heat resistance, among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N- - Benzylmaleimide is preferred.

〔5〕各構成單元的比率 [5] Ratio of each constituent unit

樹脂(A)為以下的樹脂[K1]或[K2]。樹脂[K1]：由構成單元(Aa)及構成單元(Ab)構成的共聚合物；樹脂[K2]：由構成單元(Aa)、構成單元(Ab)及構成單元(Ad)構成的共聚合物。 The resin (A) is the following resin [K1] or [K2]. Resin [K1]: A copolymer composed of a structural unit (Aa) and a structural unit (Ab); Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ad) thing.

本發明的樹脂組成物係以含有樹脂[K1]為佳。 The resin composition of the present invention preferably contains resin [K1].

樹脂[K1]中，相對於構成樹脂[K1]的總構成單元，各構成單元的比率如下：構成單元(Aa)：5至95莫耳%、構成單元(Ab)：5至95莫耳%為佳，並以構成單元(Aa)：30至90莫耳%、構成單元(Ab)：10至70莫耳%更佳。 In the resin [K1], the ratios of the respective constituent units with respect to the total constituent units constituting the resin [K1] are as follows: constituent unit (Aa): 5 to 95 mol %, constituent unit (Ab): 5 to 95 mol % More preferably, the constituent unit (Aa): 30 to 90 mol %, and the constituent unit (Ab): 10 to 70 mol %.

構成樹脂[K1]的構成單元之比率以在上述的範圍內為佳，因可使樹脂組成物的保存穩定性、獲得的膜之耐藥品性、耐熱性及機械強度傾向優異，並且可得優異的平整性。 The ratio of the constituent units constituting the resin [K1] is preferably within the above-mentioned range, since the storage stability of the resin composition, the chemical resistance, heat resistance, and mechanical strength of the obtained film tend to be excellent, and excellent flatness.

樹脂[K1]可參照例如文獻「高分子合成的實驗法」(大津隆行著發行者：(股)化學同人第1版第1刷 1972年3月1日發行)所述之方法及參考該文獻所述之引用文獻而製造。 For resin [K1], for example, the method described in the document "Experimental Method for Polymer Synthesis" (Published by Takashi Otsu: (stock) Chemical Doujin 1st Edition No. 1 Issued on March 1, 1972) and reference to this document can be referred to. Manufactured from the cited references.

具體而言可列舉將設定量的構成單元(Aa) 及構成單元(Ab)、聚合起始劑及溶劑等放入反應容器中，藉由例如以氮氣替代氧氣而成為去氧環境，並一邊攪拌一邊加熱及保溫的方法。又，此處使用的聚合起始劑及溶劑等並無特別的限制，可使用該領域中通常使用者。聚合起始劑可列舉例如偶氮化合物(2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(苯甲醯基過氧化物等)；溶劑是只要可溶解各單體者即可可列舉樹脂組成物中使用的後述之溶劑等。 Specifically, a predetermined amount of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and the oxygen-deoxidized environment is replaced by nitrogen, for example, and stirring is performed. A method of heating and keeping warm. In addition, the polymerization initiator, solvent and the like used here are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides ( benzyl peroxide, etc.); the solvent is a solvent that can be used in the resin composition as long as it can dissolve each monomer, and the like can be mentioned later.

所得的樹脂可直接使用反應後的溶液，也可使用濃縮或稀釋的溶液，也可使用以再沉澱等方法作成固體(粉體)取出者。藉由使用本發明的樹脂組成物中使用之溶劑作為聚合溶劑，可將反應後的溶液直接使用在樹脂組成物的製造，故可簡化樹脂組成物的製造步驟。 As the obtained resin, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or one obtained as a solid (powder) by a method such as reprecipitation may be used. By using the solvent used in the resin composition of the present invention as a polymerization solvent, the solution after the reaction can be directly used in the production of the resin composition, so that the production steps of the resin composition can be simplified.

樹脂[K2]中，在構成樹脂[K2]的總構成單元中，各構成單元的比率係如下述：構成單元(Aa)：5至90莫耳%、構成單元(Ab)：5至90莫耳%、構成單元(Ad)：1至40莫耳為佳，並以構成單元(Aa)：17至80莫耳%、構成單元(Ab)：17至80莫耳%、構成單元(Ad)：3至35莫耳更佳。 In the resin [K2], among the total structural units constituting the resin [K2], the ratio of each structural unit is as follows: structural unit (Aa): 5 to 90 mol %, structural unit (Ab): 5 to 90 mol % Ear %, structural unit (Ad): 1 to 40 mol %, and structural unit (Aa): 17 to 80 mol %, structural unit (Ab): 17 to 80 mol %, structural unit (Ad) : 3 to 35 moles is better.

以構成樹脂[K2]的構成單元之比率為上述的範圍內為佳，因可使樹脂組成物的保存穩定性、獲得的膜之耐藥品性、耐熱性及機械強度優異，並且可得優異的平整性。樹脂[K2]可藉由與樹脂[K1]相同的方法製造。 It is preferable that the ratio of the constituent units constituting the resin [K2] be within the above-mentioned range, because the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the obtained film can be excellent, and excellent resin can be obtained. Flatness. Resin [K2] can be produced by the same method as resin [K1].

樹脂(A)的換算聚苯乙烯之重量平均分子量(Mw)係以3,000至100,000為佳，並以5,000至50,000更佳，而以5,000至20,000又更佳，而以5,000至10,000尤佳。樹脂(A)的重量平均分子量(Mw)為前述的範圍內，則可使樹脂組成物的塗布性變佳。 The polystyrene-converted weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 20,000, and still more preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the aforementioned range, the coatability of the resin composition can be improved.

樹脂(A)的分散度[重量平均分子量(Mw)/數平均分子量(Mn)]係以1.1至6.0為佳，並以1.2至4.0更佳。分散度為前述的範圍內，則獲得的膜之耐藥品性傾向優異。 The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the aforementioned range, the obtained film tends to be excellent in chemical resistance.

樹脂(A)的酸價係以0mg-KOH/g以上135mg-KOH/g以下為佳，並以0mg-KOH/g以上50mg-KOH/g以下更佳，而以0mg-KOH/g以上5mg-KOH/g以下又更佳，而以0mg-KOH/g尤佳。 The acid value of resin (A) is preferably 0 mg-KOH/g or more and 135 mg-KOH/g or less, more preferably 0 mg-KOH/g or more and 50 mg-KOH/g or less, and 0 mg-KOH/g or more and 5 mg -KOH/g or less is more preferable, and 0 mg-KOH/g is more preferable.

樹脂(A)的酸價為前述的範圍內，則獲得的膜與基板間的密合性傾向優異。 When the acid value of the resin (A) is within the above-mentioned range, the obtained film and the substrate tend to have excellent adhesion.

本說明書中，上述的酸價是換算為固形分的酸價，可藉由下述步驟求得。 In this specification, the above-mentioned acid value is an acid value converted into solid content, and can be obtained by the following procedure.

步驟：在1g樹脂溶液中加入70mL四氫呋喃[THF]及10mL蒸餾水，再加入酚酞溶液2至3滴，攪拌至均勻。用0.1N-NaOH水溶液滴定所得的樹脂溶液直至指示劑呈色。將滴定所需的0.1N-NaOH水溶液之量設為A(mL)。也同樣的用0.1N-NaOH水溶液滴定70mL THF、10mL蒸餾水及2至3滴酚酞溶液之混合液，將該混合液滴定中所需之0.1N-NaOH水溶液之量設為B(mL)。然後，藉由下式計算出樹脂的酸價。 Steps: Add 70 mL of tetrahydrofuran [THF] and 10 mL of distilled water to 1 g of resin solution, then add 2 to 3 drops of phenolphthalein solution, and stir until uniform. The resulting resin solution was titrated with 0.1N-NaOH aqueous solution until the indicator was colored. The amount of 0.1N-NaOH aqueous solution required for the titration was A (mL). Similarly, titrate a mixture of 70 mL of THF, 10 mL of distilled water and 2 to 3 drops of phenolphthalein solution with 0.1N-NaOH aqueous solution, and the amount of 0.1N-NaOH aqueous solution required for titration of the mixture is set as B (mL). Then, the acid value of the resin was calculated by the following formula.

酸價(mg-KOH/g)=[(A-B)×5.6×(樹脂溶液的樹脂濃度(%))]/100 Acid value (mg-KOH/g)=[(A-B)×5.6×(resin concentration of resin solution (%))]/100

相對於本發明的樹脂組成物之固形分，樹脂(A)的含有率係以20至100質量%為佳，並以25至100質量%更佳，而以30至100質量%又更佳。 The content of the resin (A) is preferably 20 to 100 mass %, more preferably 25 to 100 mass %, and still more preferably 30 to 100 mass % with respect to the solid content of the resin composition of the present invention.

樹脂(A)的含有率為前述的範圍內，則所得的膜之耐熱性傾向優異，且與基板間的密合性及耐藥品性傾向優異。此處，樹脂組成物的固形分係指自本發明的樹脂組成物之總量中去除溶劑(E)的含量後之量。 When the content of the resin (A) is within the above-mentioned range, the obtained film tends to be excellent in heat resistance, and tends to be excellent in adhesion and chemical resistance with the substrate. Here, the solid content of the resin composition means the amount excluding the content of the solvent (E) from the total amount of the resin composition of the present invention.

<整平劑(B)> <Leveler (B)>

整平劑(B)可列舉聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子的聚矽氧系界面活性劑等，並以氟系界面活性劑為佳。此等整平劑也可在側鏈具有聚合性基。 The leveling agent (B) includes polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having a fluorine atom, and fluorine-based surfactants are preferred. These levelers may have a polymerizable group in the side chain.

聚矽氧系界面活性劑可列舉分子內具有矽氧烷鍵的界面活性劑等。具體而言可列舉東麗(Toray)聚矽氧DC3PA、同樣SH7PA、同樣DC11PA、同樣SH21PA、同樣SH28PA、同樣SH29PA、同樣SH30PA、同樣SH8400(商品名，Toray Dow Corning(股)製造)、KP 321、KP 322、KP 323、KP 324、KP 326、KP 340、KP 341(信越化學工業(股)製造)、TSF 400、TSF 401、TSF 410、TSF 4300、TSF 4440、TSF 4445、TSF 4446、TSF 4452及TSF 4460(日本Momentive高性能材料有限責任合資公司製造)等。 The polysiloxane-based surfactant includes a surfactant having a siloxane bond in the molecule, and the like. Specifically, Toray polysiloxane DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.), KP 321 , KP 322, KP 323, KP 324, KP 326, KP 340, KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF 400, TSF 401, TSF 410, TSF 4300, TSF 4440, TSF 4445, TSF 4446, TSF 4452 and TSF 4460 (manufactured by Momentive High Performance Materials Co., Ltd., a joint venture in Japan), etc.

前述氟系界面活性劑可列舉分子內具有氟碳鏈的界面活性劑等。具體而言可列舉Fluorad(註冊商標))FC 430、同樣FC 431(住友3M(股)製造)；Megafac(註冊商標)F142D、同樣F171、同樣F172、同樣F173、同樣F177、同樣F183、同樣F554；同樣R30、同樣RS-718-K(DIC(股)製造)、F-Top(註冊商標)EF301、同樣EF303、同樣EF351、同樣EF352(三菱材料電子化成(股)製造)；Surflon(註冊商標)S381、同樣S382、同樣SC101、同樣SC105(旭硝子(股)製造)及E5844((股)大金精密化學品(Daikin Fine Chemicals)研究所製造)等。 As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Fluorad (registered trademark)) FC 430, the same FC 431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554 ; same R30, same RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, same EF303, same EF351, same EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) ) S381, the same S382, the same SC101, the same SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by (stock) Daikin Fine Chemicals Research Institute), etc.

前述具有氟原子的聚矽氧系界面活性劑可列舉分子內具有矽氧烷鍵及氟碳鏈的界面活性劑等。具體而言可列舉Megafac(註冊商標)R08、同樣BL20、同樣F475、同樣F477及同樣F443(DIC(股)製造)等。 Examples of the polysiloxane-based surfactant having a fluorine atom include those having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Corporation), etc. are mentioned.

相對於樹脂組成物的總量，整平劑(B)的含有率係以0.001質量%以上0.2質量%以下為佳，並以0.002質量%以上0.1質量%以下更佳，而以0.005質量%以上0.07質量%以下又更佳。整平劑(B)的含有率為前述的範圍內，則可更加改善膜之平整性。 The content of the leveling agent (B) is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.1 mass % or less, and 0.005 mass % or more with respect to the total amount of the resin composition. 0.07 mass % or less is still more preferable. When the content rate of the leveling agent (B) is within the aforementioned range, the leveling property of the film can be further improved.

<聚合性化合物(C)> <Polymerizable compound (C)>

聚合性化合物(C)係藉由熱或聚合起始劑(D)的作用而反應的單體，該單體可列舉具有乙烯性不飽和鍵的化合物，較佳可列舉(甲基)丙烯酸化合物，更佳的是具有選自丙烯醯基及甲基丙烯醯基所組成之群組的至少1種基之化合物。 The polymerizable compound (C) is a monomer reacted by heat or by the action of the polymerization initiator (D). Examples of the monomer include compounds having an ethylenically unsaturated bond, preferably (meth)acrylic compounds. , and more preferably a compound having at least one group selected from the group consisting of acrylyl and methacryloyl.

具有1個(甲基)丙烯醯基的(甲基)丙烯酸化合物可列舉(甲基)丙烯酸烷酯、(甲基)丙烯酸的苯氧化聚乙二醇酯、(甲基)丙烯酸的烷氧化聚乙二醇酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙基酯、(甲基)丙烯酸四氫呋喃基酯等。 Examples of the (meth)acrylic compound having one (meth)acryloyl group include alkyl (meth)acrylate, phenoxy polyethylene glycol ester of (meth)acrylic acid, and alkoxylated poly(meth)acrylic acid. Ethylene glycol ester, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acrylate Hydroxy-3-phenoxypropyl ester, tetrahydrofuryl (meth)acrylate, etc.

具有2個(甲基)丙烯醯基的(甲基)丙烯酸化合物可列舉1,3-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(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、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚、環氧化雙酚A二(甲基)丙烯酸酯、丙氧化新戊二醇二(甲基)丙烯酸酯、乙氧化新戊二醇二(甲基)丙烯酸酯、3-甲基戊二醇二(甲基)丙烯酸酯等。 Examples of the (meth)acrylic compound having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,3-butanediol (meth)acrylate. 6-Hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethyl Glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acrylooxyethyl) ether of bisphenol A, epoxidized bisphenol A Di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate Wait.

具有3個以上(甲基)丙烯醯基的(甲基)丙烯酸化合物可列舉三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、參(2-羥基乙基)新三聚氰酸酯三(甲基)丙烯酸酯、乙氧化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧化三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇四(甲基)丙烯酸酯、三新戊四醇五(甲基)丙烯酸酯、三新戊四醇六(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯與酸酐的反應物、二新戊四醇五(甲基)丙烯酸酯與酸酐的反應物、三新戊四醇七(甲基)丙烯酸酯與酸酐的反應物、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質新戊四醇三(甲基)丙烯酸酯、己內酯改質參(2-羥基乙基)新三聚氰酸酯三(甲基)丙烯酸酯、己內酯改質新戊四醇四(甲基)丙烯酸酯、己內酯改質二新戊四醇五(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯、己內酯改質三新戊四醇四(甲基)丙烯酸酯、己內酯改質三新戊四醇五(甲基)丙烯酸酯、己內酯改質三新戊四醇六(甲基)丙烯酸酯、己內酯改質三新戊四醇七(甲基)丙烯酸酯、己內酯改質三新戊四醇八(甲基)丙烯酸酯、己內酯改質新戊四醇三(甲基)丙烯酸酯與酸酐的反應物、己內酯改質二新戊四醇五(甲基)丙烯酸酯與酸酐的反應物、己內酯改質三新戊四醇七(甲基)丙烯酸酯與酸酐的反應物等。 Examples of the (meth)acrylic compound having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, gins(2-hydroxyl) Ethyl) neocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentyltetrakis Alcohol Tetra(meth)acrylate, Dipiveaerythritol Penta(meth)acrylate, Dipiveaerythritol Hex(meth)acrylate, Tripivalerythritol Tetra(meth)acrylate, Sanxin Pentaerythritol penta(meth)acrylate, Trinetaerythritol hexa(meth)acrylate, Trinetaerythritol hepta(meth)acrylate, Trinetaerythritol octa(meth)acrylate, The reaction product of neopentaerythritol tri(meth)acrylate and acid anhydride, the reaction product of dipeutaerythritol penta(meth)acrylate and acid anhydride, the reaction product of trinetaerythritol hepta(meth)acrylate and acid anhydride Reactants, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified neopentaerythritol tri(meth)acrylate, caprolactone-modified ginseng (2-hydroxyethyl) ) New cyanurate tri(meth)acrylate, caprolactone-modified neopentaerythritol tetra(meth)acrylate, caprolactone-modified dipivalerythritol penta(meth)acrylate, Caprolactone-modified dipivoerythritol hexa(meth)acrylate, caprolactone-modified trinepentaerythritol tetra(meth)acrylate, caprolactone-modified trinepentaerythritol penta(methyl)acrylate ) Acrylate, caprolactone-modified trinepentaerythritol hexa(meth)acrylate, caprolactone-modified trinepentaerythritol hepta(meth)acrylate, caprolactone-modified trinepentaerythritol Octa(meth)acrylate, caprolactone-modified neotaerythritol tri(meth)acrylate and acid anhydride reactant, caprolactone-modified dipivalerythritol penta(meth)acrylate and acid anhydride Reactant, caprolactone-modified trinepentaerythritol hepta(meth)acrylate and acid anhydride reactant, etc.

聚合性化合物(C)係以具有3個以上(甲基)丙烯醯基的(甲基)丙烯酸化合物為佳，並以二新戊四醇六(甲基)丙烯酸酯更佳。 The polymerizable compound (C) is preferably a (meth)acrylic compound having three or more (meth)acryloyl groups, and is more preferably dipivoerythritol hexa(meth)acrylate.

本發明的樹脂組成物含有聚合性化合物(C)時，相對於100質量份的樹脂(A)，該化合物(C)以20至80質量份為佳，並以25至70質量份更佳。聚合性化合物(C)的含量若為前述的範圍內，則可使獲得的膜之耐藥品性及機械強度傾向優異，且可獲得平整性。 When the resin composition of the present invention contains the polymerizable compound (C), the compound (C) is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass, relative to 100 parts by mass of the resin (A). When the content of the polymerizable compound (C) is within the aforementioned range, the obtained film tends to be excellent in chemical resistance and mechanical strength, and flatness can be obtained.

<聚合起始劑(D)> <Polymerization initiator (D)>

聚合起始劑(D)係藉由光或熱的作用而產生活性自由基、酸等，只要是可使聚合性化合物(C)開始聚合之化合物即無特別的限制，可使用已知的聚合起始劑。聚合起始劑(D)係以含有選自O-醯肟化合物、烷基苯酮化合物、三

化合物、醯基勝氧化物化合物及二咪唑化合物所組成之群組的至少1種之聚合起始劑為佳，並以含有O-醯肟化合物的聚合起始劑更佳。此等聚合起始劑傾向於高感度，且可見光域中的透過率高。 The polymerization initiator (D) generates active radicals, acids, etc. by the action of light or heat, and is not particularly limited as long as it is a compound that can start the polymerization of the polymerizable compound (C), and known polymerization can be used. starter. The polymerization initiator (D) is selected from the group consisting of O-hydroxyoxime compounds, alkyl phenone compounds,

At least one polymerization initiator from the group consisting of a compound, an acyl oxide compound and a diimidazole compound is preferred, and a polymerization initiator containing an O-oxime compound is more preferred. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

O-醯肟化合物係具有式(D1)表示的部份結構之化合物。以下，＊是表示鍵結。 The O-oxime compound is a compound having a partial structure represented by the formula (D1). Hereinafter, * denotes a bond.

O-醯肟化合物可列舉：例如N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊烷基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3- 基]-3-環戊基丙烷-1-酮-2-亞胺。也可使用Irgacure(註冊商標)OXE01、OXE02(以上，BASF公司製造)、N-1919((股)ADEKA製造)等市售品。 Examples of the O-oxime compound include N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1 -(4-Phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane -1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane- 1-Imine, N-Acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane Methoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Carboxylic)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methyl) benzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (the above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) can also be used.

烷基苯酮化合物係具有式(D2-1)表示的部份結構或式(D2-2)表示的部分結構之化合物。此等部分結構中，苯環可具有取代基。 The alkylphenone compound is a compound having a partial structure represented by formula (D2-1) or a partial structure represented by formula (D2-2). In these partial structures, the benzene ring may have a substituent.

具有式(D2-1)表示的部份結構之化合物可列舉：例如2-甲基-2-嗎啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎啉基苯基)-2-苯甲基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮。可使用Irgacure(註冊商標)369、907及379(以上，BASF公司製造)等市售品。同時，也可使用日本特表2002-544205號公報所述之具有產生鏈轉移的基之聚合起始劑。具有式(D2-2)表示的部份結構之化合物可列舉：例如2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-〔4-(2-羥基乙氧基)苯基〕丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮的寡聚物、α,α-二乙氧基苯乙酮、苯甲基二甲基縮酮。就感度而言，烷基苯酮化合物係以具有式(D2-2)表示的部份結構之化合物為佳。 Compounds having a partial structure represented by formula (D2-1) include, for example, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (the above, manufactured by BASF Corporation) can be used. At the same time, a polymerization initiator having a chain transfer-generating group described in Japanese Patent Application Laid-Open No. 2002-544205 can also be used. Compounds having a partial structure represented by formula (D2-2) include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxyacetophenone, benzyl dimethyl ketal. In terms of sensitivity, the alkyl phenone compound is preferably a compound having a partial structure represented by formula (D2-2).

三

化合物可列舉：例如2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(5-甲基呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(4-二乙基胺基-2-甲基苯基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(3,4-二甲氧基苯基)乙烯基〕-1,3,5-三

。 three

Examples of compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

.

醯基膦氧化物化合物可列舉2,4,6-三甲基苯甲醯基二苯基膦氧化物等。可使用Irgacure819(日本BASF(股)製造)等市售品。 As an acylphosphine oxide compound, 2,4,6- trimethylbenzyldiphenylphosphine oxide etc. are mentioned. Commercially available products such as Irgacure 819 (manufactured by Japan BASF Co., Ltd.) can be used.

二咪唑化合物可列舉：例如2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基二咪唑(參照日本特開平6-75372號公報、日本特開平6-75373號公報等。)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)二咪唑(參照日本特公昭48-38403號公報、日本特開昭62-174204號公報等。)、以碳烷氧基取代4,4’,5,5’-位的苯基之二咪唑化合物(參照日本特開平7-10913號公報等)。 As a diimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl) Phenyl)-4,4',5,5'-tetraphenyldiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxy) phenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)diimidazole, 2,2'-bis( 2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.). ), a diimidazole compound in which the phenyl group at the 4,4', 5,5'-position is substituted with a carbon alkoxy group (refer to Japanese Patent Laid-Open No. 7-10913, etc.).

另外，聚合起始劑(D)可列舉安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物；二苯甲酮、鄰-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫化物、3,3’,4,4’-四(第三丁基過氧羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物；9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、苯甲基、苯基乙醛酸甲酯、茂鈦化合物等。此等化合物，可與後述的聚合起始助劑(H)(尤其是胺)組合使用。 In addition, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzylbenzoate, 4 -Phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridine pyridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. These compounds can be used in combination with a polymerization initiator (H) (especially, an amine) to be described later.

又，酸產生劑也可使用作為聚合起始劑(D)。酸產生劑可列舉：例如4-羥基苯基二甲基硫鎓對-甲苯磺酸鹽、4-羥基苯基二甲基硫鎓六氟銻酸鹽、4-乙醯氧基苯基二甲基硫鎓對-甲苯磺酸鹽、4-乙醯氧基苯基/甲基/苯甲基硫鎓六氟銻酸鹽、三苯基硫鎓對-甲苯磺酸鹽、三苯基硫鎓六氟銻酸鹽、二苯基碘鎓對-甲苯磺酸鹽、二苯基碘鎓六氟銻酸鹽等鎓鹽、或硝基苯甲基甲苯磺酸鹽、安息香甲苯磺酸鹽。 Moreover, an acid generator can also be used as a polymerization initiator (D). Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylene. Sulfonium p-toluenesulfonate, 4-acetyloxyphenyl/methyl/benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium Onium salts such as hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltoluenesulfonate, and benzoin tosylate.

本發明的樹脂組成物含有聚合起始劑(D)時，相對於與樹脂(A)和聚合性化合物(C)的合計含量100質量份，聚合起始劑(D)之含量係以0.01至30質量份為佳，並以0.02至15質量份更佳，而以0.03至8質量份又更佳。聚合起始劑(D)的含量若為前述的範圍內，則所得圖案的可見光透過率傾向變高。 When the resin composition of the present invention contains the polymerization initiator (D), the content of the polymerization initiator (D) is 0.01 to 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (C). It is preferably 30 parts by mass, more preferably 0.02 to 15 parts by mass, and more preferably 0.03 to 8 parts by mass. When content of a polymerization initiator (D) is in the said range, the visible light transmittance of the obtained pattern tends to become high.

<聚合起始助劑(H)> <Polymerization Initiating Auxiliary (H)>

聚合起始助劑(H)可與聚合起始劑(D)一起使用，該聚合起始助劑(H)係為了促進因聚合起始劑(D)而開始聚合的聚合性化合物(C)之聚合而使用的化合物或增敏劑。 The polymerization initiator (H) can be used together with the polymerization initiator (D), and the polymerization initiator (H) is a polymerizable compound (C) for accelerating the initiation of polymerization by the polymerization initiator (D). Compounds or sensitizers used for polymerization.

聚合起始助劑(H)可列舉噻唑啉化合物、胺化合物、烷氧基蒽化合物、噻吨酮化合物、羧酸化合物等。 The polymerization initiator (H) includes thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

噻唑啉化合物可列舉式(H1-1)至式(H1-3)表示的化合物、日本特開2008-65319號公報所述之化合物等。 As a thiazoline compound, the compound represented by Formula (H1-1) - Formula (H1-3), the compound described in Unexamined-Japanese-Patent No. 2008-65319, etc. are mentioned.

胺化合物可列舉三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮(通稱米其勒酮(Michler's ketone))、4,4’-雙(二乙基胺基)二苯甲酮、4,4’-雙(乙基甲基胺基)二苯甲酮等，其中並以4,4’-雙(二乙基胺基)二苯甲酮為佳。也可使用EAB-F(保土谷化學工業(股)製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis (Dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl) methylamino) benzophenone and the like, among which 4,4'-bis(diethylamino) benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

烷氧基蒽化合物可列舉9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10- 二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10 - Diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

噻吨酮化合物可列舉2-異丙基噻吨酮、4-異丙基噻吨酮、2,4-二乙基噻吨酮、2,4-二氯噻吨酮、1-氯-4-丙氧基噻吨酮等。 Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxy thioxanthone, etc.

羧酸化合物可列舉苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯基硫基乙酸、二甲基苯基硫基乙酸、甲氧基苯基硫基乙酸、二甲氧基苯基硫基乙酸、氯苯基硫基乙酸、二氯苯基硫基乙酸、N-苯基甘氨酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘氨酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthalene glycine, naphthoxyacetic acid, etc.

本發明的樹脂組成物含有聚合起始助劑(H)時，相對於樹脂(A)與聚合性化合物(C)的合計含量100質量份，該聚合起始助劑(H)之含量係以0.1至30質量份為佳，並以0.2至10質量份更佳。聚合起始助劑(H)之量若為前述的範圍內，則傾向於以更高感度形成圖案。 When the resin composition of the present invention contains a polymerization initiator (H), the content of the polymerization initiator (H) is 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (C). 0.1 to 30 parts by mass is preferable, and 0.2 to 10 parts by mass is more preferable. When the amount of the polymerization initiation aid (H) is within the aforementioned range, a pattern tends to be formed with higher sensitivity.

<抗氧化劑(F)> <Antioxidant (F)>

抗氧化劑(F)可列舉酚系抗氧化劑、硫系抗氧化劑、磷系抗氧化劑、胺系抗氧化劑。其中，就使所得的膜著色較少而言，係以酚系抗氧化劑為佳。 The antioxidant (F) includes a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Among them, a phenolic antioxidant is preferable in terms of making the obtained film less colored.

酚系抗氧化劑可列舉：例如丙烯酸2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苯甲基)-4-甲基苯酯、丙烯酸2-[1-(2-羥基-3,5-二-第三-戊基苯基)乙基]-4,6-二-第三戊基苯酯、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、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’-硫代雙(2-第三丁基-5-甲基酚)、2,2’-硫代雙(6-第三丁基-4-甲基酚)、1,3,5-參(3,5-二-第三丁基-4-羥基苯甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、3,3’,3”,5,5’,5”-六-第三丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三-對-甲酚、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,6-二-第三丁基-4-甲基酚及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]二氧雜磷雜庚英(phosphepine)。前述酚系抗氧化劑也可使用市售品。市售的酚系抗氧化劑可列舉：例如Sumilizer(註冊商標)BHT、GM、GS、GP(以上，全是住友化學(股)製造)、Irganox(註冊商標)1010、1076、1330、3114(以上，全是BASF公司製造)。 Phenolic antioxidants include, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[ 1-(2-Hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl ester, 3,9-bis[2-{3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol) , 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), 1,3 ,5-Sham(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(both Trimethylol-2,4,6-triyl)tris-p-cresol, neotaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-Di-tert-butyl-4-methylphenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4, 8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine (phosphepine). Commercially available products can also be used as the aforementioned phenolic antioxidants. Commercially available Examples of phenolic antioxidants include: Sumilizer (registered trademark) BHT, GM, GS, GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all of which are above, all It is made by BASF Corporation).

硫系抗氧化劑可列舉：例如3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉荳蒄酯、3,3’-硫代二丙酸二硬脂酸酯、肆(3-月桂基硫代丙酸)新戊四醇酯。前述硫系抗氧化劑也可使用市售品。市售的硫系抗氧化劑可列舉：例如Sumilizer(註冊商標)TPL-R、TP-D(以上，全是住友化學(股)製造)。 Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristine 3,3'-thiodipropionate, and dihard 3,3'-thiodipropionate. Fatty acid ester, tetra(3-laurylthiopropionic acid) neopentaerythritol ester. A commercial item can also be used for the said sulfur-type antioxidant. Commercially available sulfur-based antioxidants include, for example, Sumilizer (registered trademark) TPL-R and TP-D (the above are all manufactured by Sumitomo Chemical Co., Ltd.).

磷系抗氧化劑可列舉：例如亞磷酸三辛酯、亞磷酸三月桂酯、亞磷酸十三烷酯、亞磷酸參(壬基苯基)酯、二亞磷酸二硬脂基新戊四醇酯、四(十三烷基)- 1,1,3-參(2-甲基-5-第三丁基-4-羥基苯基)丁烷二亞磷酸酯。前述磷系抗氧化劑也可使用市售品。市售的磷系抗氧化劑可列舉：例如Irgafos(註冊商標)168、12、38(以上，全是BASF公司製造)、Adekastab 329K、AdekastabPEP36(以上，全是(股)ADEKA製造)。 Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, gins(nonylphenyl) phosphite, and distearyl neopentaerythritol diphosphite. , tetrakis (tridecyl)-1,1,3-para(2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. A commercial item can also be used for the said phosphorus antioxidant. Commercially available phosphorus-based antioxidants include, for example, Irgafos (registered trademark) 168, 12, and 38 (all of which are manufactured by BASF), Adekastab 329K, and Adekastab PEP36 (all of which are manufactured by ADEKA).

胺系抗氧化劑可列舉：例如N,N’-二-第二丁基-對-伸苯二胺、N,N’-二-異丙基-對-伸苯二胺、N,N’-二環己基-對-伸苯二胺、N,N’-二苯基-對-伸苯二胺、N,N’-雙(2-萘基)-對-伸苯二胺。前述胺系抗氧化劑也可使用市售品。市售的胺系抗氧化劑可列舉：例如Sumilizer(註冊商標)BPA、BPA-M1、4ML(以上，全是住友化學(股)製造)。 Amine-based antioxidants include, for example, N,N'-di-2-butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, N,N'- Dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine. A commercial item can also be used for the said amine type antioxidant. Commercially available amine-based antioxidants include, for example, Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

本發明的樹脂組成物含有抗氧化劑(F)時，相對於樹脂(A)與聚合性化合物(C)的合計含量100質量部，抗氧化劑(F)的含量係以0.1質量份以上5質量份以下為佳，並以0.5質量份以上3質量份以下更佳。抗氧化劑(F)的含量若為前述的範圍內，則獲得的膜之耐熱性及鉛筆硬度傾向優良。 When the resin composition of the present invention contains the antioxidant (F), the content of the antioxidant (F) is 0.1 part by mass or more and 5 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). The content is preferably less than or equal to 0.5 parts by mass or more and less than or equal to 3 parts by mass. When the content of the antioxidant (F) is within the aforementioned range, the obtained film tends to be excellent in heat resistance and pencil hardness.

<多元羧酸(G1)> <Polycarboxylic acid (G1)>

多元羧酸(G1)係選自多元羧酸酐及多元羧酸所組成之群組的至少1種化合物。多元羧酸係指具有2個以上的羧基之化合物；多元羧酸酐係指多元羧酸的無水物。多元羧酸(G1)的分子量係以3,000以下為佳，並以1,000以下更佳。 The polyvalent carboxylic acid (G1) is at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. The polycarboxylic acid refers to a compound having two or more carboxyl groups; the polycarboxylic acid anhydride refers to the anhydrate of the polycarboxylic acid. The molecular weight of the polyvalent carboxylic acid (G1) is preferably 3,000 or less, and more preferably 1,000 or less.

前述的多元羧酸酐可列舉：例如順丁烯二酸酐、琥珀酸酐、戊二酸酐、檸康酸酐、衣康酸酐、2-十二烷基琥珀酸酐、2-(2-辛-3-烯基)琥珀酸酐、2-(2,4,6-三甲基壬-3-烯基)琥珀酸酐、丙三羧酸酐、1,2,3,4-丁烷四羧酸二酐等鏈狀多元羧酸酐；3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、4-甲基六氫鄰苯二甲酸酐、降冰片烯二羧酸酐、甲基二環[2.2.1]庚烷-2,3-二羧酸酐、二環[2.2.1]庚烷-2,3-二羧酸酐、二環[2.2.1]庚-5-烯-2,3-二羧酸酐、甲基二環[2.2.1]庚-5-烯-2,3-二羧酸酐、環戊烷四羧酸二酐等脂環式多元羧酸酐；鄰苯二甲酸酐、3-乙烯鄰苯二甲酸酐、4-乙烯鄰苯二甲酸酐、均苯四甲酸酐、偏苯三酸酐、二苯甲酮四羧酸二酐、3,3’,4,4’-二苯碸四羧酸二酐、乙二醇雙(脫水偏苯三酸酯(anhydrotrimellitate))、甘油參(脫水偏苯三酸酯)、甘油雙(脫水偏苯三酸酯)單乙酸酯、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧-3-呋喃基)萘[1,2-c]呋喃-1,3-二酮等芳香族多元羧酸酐。 The aforementioned polycarboxylic acid anhydrides include, for example, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-oct-3-enyl ) Chain polyvalent anhydride such as succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, glyceric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Carboxylic anhydrides; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Dicarboxylic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1] Heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3 - Alicyclic polycarboxylic acid anhydrides such as dicarboxylic acid anhydride and cyclopentanetetracarboxylic acid dianhydride; phthalic anhydride, 3-ethylene phthalic anhydride, 4-ethylene phthalic anhydride, pyromellitic anhydride , trimellitic anhydride, benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, ethylene glycol bis(anhydrotrimellitate), glycerol (anhydro trimellitate), glycerol bis (anhydro trimellitate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Aromatic polycarboxylic acid anhydrides such as pendant oxy-3-furyl)naphthalene[1,2-c]furan-1,3-dione.

也可使用Adekahadna(註冊商標)-EH-700(商品名(以下相同)，(股)ADEKA製造)、Rikasidd(註冊商標)-HH、同樣BT-W、同樣-TH、同樣-MH、同樣MH-700(新日本理化(股)製造)、Epikinia 126、同樣YH-306、同樣DX-126(油化Shell Epoxy(股)製造)等市售品。 Adekahadna (registered trademark)-EH-700 (trade name (hereinafter the same), manufactured by (stock) ADEKA), Rikasidd (registered trademark)-HH, same BT-W, same-TH, same-MH, same MH can also be used Commercial products such as -700 (manufactured by Nippon Rika Co., Ltd.), Epikinia 126, the same YH-306, and the same DX-126 (manufactured by Petrochemical Shell Epoxy Co., Ltd.).

前述的多元羧酸可列舉衍生而得鏈狀多元羧酸酐的鏈狀多元羧酸(例如草酸、丙二酸、己二酸、癸二酸、反丁烯二酸、酒石酸、檸檬酸等)；衍生而得脂環式多元羧酸酐的脂環式多元羧酸(例如環己烷二羧酸)；衍生而得芳香族多元羧酸酐的芳香族多元羧酸(例如間苯二甲酸、對苯二甲酸、1,4,5,8-萘四羧酸等)。 The aforementioned polybasic carboxylic acids can include chain polycarboxylic acids derived from chain polycarboxylic acid anhydrides (for example, oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, etc.); Alicyclic polycarboxylic acids (such as cyclohexanedicarboxylic acid) derived from alicyclic polycarboxylic acid anhydrides; aromatic polycarboxylic acids (such as isophthalic acid, terephthalic acid) derived from aromatic polycarboxylic acid anhydrides formic acid, 1,4,5,8-naphthalenetetracarboxylic acid, etc.).

其中，就使獲得的膜之耐熱性優異，尤其可見光域中的透明性不易降低而言，係以鏈狀多元羧酸酐、脂環式多元羧酸酐為佳，並以脂環式多元羧酸酐更佳。 Among them, chain polycarboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferable, and alicyclic polycarboxylic acid anhydrides are more preferable in terms of making the obtained film excellent in heat resistance, and in particular, the transparency in the visible light region is not easily reduced. good.

本發明的樹脂組成物含有多元羧酸(G1)時，相對於樹脂(A)和聚合性化合物(C)之合計含量100質量份，該多元羧酸(G1)係以1至30質量份為佳，並以2至20質量份更佳，而以2至15質量份又更佳。多元羧酸(G1)的含量若為前述的範圍內，則獲得的膜之耐熱性及密合性優異。 When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), the polyvalent carboxylic acid (G1) is 1 to 30 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). Preferably, it is 2 to 20 parts by mass, and it is still more preferably 2 to 15 parts by mass. If the content of the polyvalent carboxylic acid (G1) is within the aforementioned range, the obtained film will be excellent in heat resistance and adhesiveness.

<咪唑化合物(G2)> <Imidazole compound (G2)>

咪唑化合物(G2)係只要具有咪唑骨架的化合物即可，並無特別的限制，可列舉：例如已知作為環氧硬化劑的化合物。其中，並以式(G2-1)表示的化合物為佳。 The imidazole compound (G2) is not particularly limited as long as it has an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, the compound represented by the formula (G2-1) is preferable.

[式(2)中，R³¹係表示碳數1至20的烷基、苯基、苯甲基或碳數2至5的氰基烷基。 [In formula (2), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.

R³²至R³⁴係相互獨立的表示氫原子、鹵素原子、碳數 1至20的烷基、苯基、硝基或碳數1至20的醯基，該烷基及該苯基中所含的氫原子可用羥基取代。] R ³² to R ³⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group contained in the phenyl group The hydrogen atoms can be replaced by hydroxyl groups. ]

碳數1至20的烷基可列舉：例如甲基、乙基、丙基、異丁基、丁基、第三丁基、己基、庚基、辛基、壬基、癸基、十七烷基、十一烷基。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecanyl base, undecyl.

碳數2至5的氰基烷基可列舉：例如氰基甲基、氰基乙基、氰基丙基、氰基丁基、氰基戊基。 Examples of the cyanoalkyl group having 2 to 5 carbon atoms include cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, and cyanopentyl.

鹵素原子可列舉：例如氟原子、氯原子、溴原子。 As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

碳數1至20的醯基可列舉：例如甲醯基、乙醯基、丙醯基、異丁醯基、戊醯基、異戊醯基、新戊醯基、月桂醯基、肉荳蔻醯基、硬脂醯基。 Examples of the acyl group having 1 to 20 carbon atoms include methylyl, acetyl, propionyl, isobutyryl, pentamyl, isopentyl, neopentyl, lauryl, myristyl, Stearyl.

咪唑化合物(G2)可列舉：例如1-甲基咪唑、2-甲基咪唑、2-羥基甲基咪唑、2-甲基-4-羥基甲基咪唑、5-羥基甲基-4-甲基咪唑、2-乙基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、4-羥基甲基-2-苯基咪唑、2-苯基咪唑、2-苯基-羥基甲基咪唑、1-苯甲基-4-甲基咪唑、1-苯甲基-4-苯基咪唑、1-苯甲基-5-羥基甲基咪唑、2-(對-羥基苯基)咪唑、1-氰基甲基-2-甲基咪唑、1-(2-氰基乙基)-2-羥基甲基咪唑、2,4-二苯基咪唑、1-氰基甲基-2-十一烷基咪唑、1-氰基甲基-2-乙基-4-甲基咪唑、1-氰基甲基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑。其中並以1-苯甲基-4-苯基咪唑、2-乙基-4-甲基咪唑、1-(2-氰基乙基)-2-乙基-4- 甲基咪唑為佳。 The imidazole compound (G2) includes, for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, and 5-hydroxymethyl-4-methyl Imidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl- 2-phenylimidazole, 2-phenylimidazole, 2-phenyl-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl yl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1-(2-cyanoethyl)-2-hydroxymethylimidazole , 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl- 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

本發明的樹脂組成物含有咪唑化合物(G2)時，相對於樹脂(A)和聚合性化合物(C)之合計含量100質量份，該咪唑化合物(G2)的含量係以0.1質量份以上25質量份以下為佳，並以0.2質量份以上15質量份以下更佳，而以0.5質量份以上5質量份以下又更佳。咪唑化合物(G2)的含量若為前述的範圍時，則獲得的膜在可見光域中的透明性傾向優異。 When the resin composition of the present invention contains the imidazole compound (G2), the content of the imidazole compound (G2) is 0.1 part by mass or more and 25 mass parts relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). part is preferably not more than 0.2 parts by mass, more preferably not less than 0.2 parts by mass but not more than 15 parts by mass, and still more preferably not less than 0.5 parts by mass and not more than 5 parts by mass. When the content of the imidazole compound (G2) is within the aforementioned range, the obtained film tends to be excellent in transparency in the visible light region.

<溶劑(E)> <Solvent (E)>

本發明的樹脂組成物含有溶劑(E)。溶劑(E)可列舉樹脂組成物的領域中使用的各種有機溶劑，其具體例可列舉：如乙二醇單甲醚、乙二醇單***、乙二醇單丙醚及乙二醇單丁醚的乙二醇單烷醚；二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲醚、二乙二醇二丙醚、二乙二醇二丁醚等二乙二醇二烷醚；甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單***乙酸酯等乙二醇烷醚乙酸酯；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯等烷二醇烷醚乙酸酯；丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等丙二醇單烷醚；丙二醇二甲醚、丙二醇二***、丙二醇乙基甲醚、丙二醇二丙醚、丙二醇丙基甲醚、丙二醇乙基丙醚等丙二醇二烷醚；丙二醇甲醚丙酸酯、丙二醇***丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等丙二醇烷醚丙酸酯；甲氧基丁醇、乙氧基丁醇、丙氧基丁醇、丁氧基丁醇等丁二醇單烷醚；甲氧基丁基乙酸酯、乙氧基丁基乙酸酯、丙氧基丁基乙酸酯、丁氧基丁基乙酸酯等丁二醇單烷醚乙酸酯；甲氧基丁基丙酸酯、乙氧基丁基丙酸酯、丙氧基丁基丙酸酯、丁氧基丁基丙酸酯等丁二醇單烷醚丙酸酯；二丙二醇二甲醚、二丙二醇二***、二丙二醇甲基***等二丙二醇二烷醚；苯、甲苯、二甲苯、均三甲苯等芳香族烴；甲基乙基酮、丙酮、甲基戊基酮、甲基異丁酮、環己酮等酮；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等醇；乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、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-丁氧基丙酸丁酯等酯；四氫呋喃、吡喃等環狀醚；γ-丁內酯等環狀酯等。 The resin composition of this invention contains a solvent (E). The solvent (E) includes various organic solvents used in the field of resin compositions, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethylene glycol monoalkyl ether of ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc. Ethylene glycol dialkyl ethers; ethylene glycol alkyl ethers such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc. acid esters; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxyamyl acetate and other alkyl glycol alkyl ethers Ester; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl ether Methyl ether, propylene glycol ethyl propyl ether and other propylene glycol dialkyl ethers; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether propionates; Methoxy Butyl butanol, ethoxybutanol, propoxybutanol, butoxybutanol and other butanediol monoalkyl ethers; methoxybutyl acetate, ethoxybutyl acetate, propoxy Butylene glycol monoalkyl ether acetates such as butyl acetate and butoxybutyl acetate; methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionic acid Butylene glycol monoalkyl ether propionate such as ester, butoxybutyl propionate; dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether; benzene, toluene, xylene , aromatic hydrocarbons such as mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, Ethylene glycol, glycerin and other alcohols; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methyl propionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxyl Ethyl Propionate, Propionate 3-Hydroxypropionate, Butyl 3-Hydroxypropionate, Methyl 2-Hydroxy-3-Methylbutyrate, Methyl Methoxyacetate, Ethyl Methoxyacetate, Methoxyacetate propyl acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, propoxy acetate Ethyl acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 2-methoxyacetate methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate Propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate , butyl 3-propoxy propionate, methyl 3-propoxy propionate, ethyl 3-propoxy propionate, propyl 3-propoxy propionate, butyl 3-propoxy propionate , methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc.; cyclic tetrahydrofuran, pyran, etc. ethers; cyclic esters such as γ-butyrolactone, etc.

就塗布性、乾燥性而言，上述的溶劑之中，較佳的可列舉前述溶劑中的沸點為100至200℃之有機溶劑。沸點為100至200℃之有機溶劑，具體上可列舉：烷二醇烷醚乙酸酯、甲氧基丁醇及乙氧基丁醇等醇、環己酮等酮、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯等酯，較好的可列舉丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、環己酮、甲氧基丁醇、甲氧基丁基乙酸酯、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。此等溶劑(E)可分別單獨使用，或將2種以上混合使用。 Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200° C. in the above-mentioned solvents are preferably mentioned in terms of coating properties and drying properties. Organic solvents with a boiling point of 100 to 200°C, specifically: alkanediol alkyl ether acetate, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, 3-ethoxypropane Acid ethyl ester and methyl 3-methoxypropionate and other esters, preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl Ethyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These solvents (E) may be used alone or in combination of two or more.

相對於樹脂組成物的總量，本發明的樹脂組成物中之溶劑(E)的含有率係以60至95質量%為佳，並以70至95質量%更佳。換言之，本發明的樹脂組成物之固形分係以5至40質量%為佳，並以5至30質量%更佳。溶劑(E)的含有率若為前述的範圍，則塗布樹脂組成物而得之膜的平整性傾向高。 The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, relative to the total amount of the resin composition. In other words, the solid content of the resin composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content rate of the solvent (E) is in the above-mentioned range, the flatness of the film obtained by coating the resin composition tends to be high.

<其他的成分> <other ingredients>

本發明的樹脂組成物中，可視需要而含有充填劑、其他的高分子化合物、熱自由基產生劑、紫外線吸收劑、鏈轉移劑、密合促進劑等該技術領域中已知的添加劑。 The resin composition of the present invention may optionally contain additives known in the technical field such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, and adhesion promoters.

充填劑可列舉玻璃、氧化矽、氧化鋁等。 Glass, silica, alumina, etc. are mentioned as a filler.

其他的高分子化合物可列舉順丁烯二醯亞胺樹脂等熱硬化性樹脂或聚乙烯醇、聚丙烯酸、聚乙二醇單烷醚、聚氟烷基丙烯酸酯、聚酯、聚胺酯等熱可塑性樹脂等。 Other polymer compounds include thermosetting resins such as maleimide resins, and thermoplastics such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. resin, etc.

熱自由基產生劑可列舉2,2’-偶氮雙(2-甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)等。 The thermal radical generator includes 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like.

紫外線吸收劑可列舉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。 The ultraviolet absorber includes 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

鏈轉移劑可列舉十二烷基硫醇、2,4-二苯基-4-甲基-1-戊烯等。 The chain transfer agent includes dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

密合促進劑可列舉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、3-去水甘油氧基丙基三甲氧基矽烷、3-去水甘油氧基丙基甲基二甲氧基矽烷、3-去水甘油氧基丙基甲基二乙氧基矽烷、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-硫醇基丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、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-胺基丙基甲基二乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷等。 Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-dehydroglyceryloxypropyltrimethoxysilane, 3-Deglyceryloxypropylmethyldimethoxysilane, 3-Deglyceryloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane Oxysilane, 3-Hydrothiopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3 -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Ethoxysilane, etc.

又，本發明的樹脂組成物在充填於光路長1cm的石英小瓶中，利用分光光度計於測定波長400至700nm的條件下測定透射率時，其平均透射率是以70%以上為佳，並以80%以上更佳。 In addition, when the resin composition of the present invention is filled in a quartz vial with an optical path length of 1 cm, and the transmittance is measured by a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm, the average transmittance is preferably 70% or more, and More than 80% is better.

在使用本發明的樹脂組成物形成膜時，膜的平均透過率是以90%以上為佳，並以95%以上更佳。該平均透過率係對加熱硬化(100至250℃，5分鐘至3小時)後的厚度為2μm之膜，使用分光光度計於測定波長400至700nm的條件下測定時之平均值。藉此，即可提供可見光域中的透明性優異之膜。 When a film is formed using the resin composition of the present invention, the average transmittance of the film is preferably 90% or more, more preferably 95% or more. The average transmittance is an average value when measured with a spectrophotometer on a film having a thickness of 2 μm after heat curing (100 to 250° C., 5 minutes to 3 hours) at a measurement wavelength of 400 to 700 nm. Thereby, a film excellent in transparency in the visible light region can be provided.

<樹脂組成物的製造方法> <Manufacturing method of resin composition>

本發明的樹脂組成物可藉由已知的方法將樹脂(A)、整平劑(B)及溶劑(E)，以及視需要的聚合性化合物(C)、聚合起始劑(D)、聚合起始助劑(H)、抗氧化劑(F)、硬化劑(G)及其他的成分混合而製造。混合後較好以孔徑0.05至 1.0μm左右的過濾器過濾。 In the resin composition of the present invention, the resin (A), the leveling agent (B), the solvent (E), and optionally the polymerizable compound (C), the polymerization initiator (D), The polymerization initiator (H), antioxidant (F), hardener (G), and other components are mixed and produced. After mixing, it is preferably filtered through a filter having a pore size of about 0.05 to 1.0 µm.

<液晶顯示裝置用膜的製造方法> <The manufacturing method of the film for liquid crystal display devices>

本發明的液晶顯示裝置用膜下文也稱「本發明的膜」或「膜」。 The film for liquid crystal display devices of the present invention is hereinafter also referred to as "the film of the present invention" or "film".

本發明的膜，可藉由將本發明的樹脂組成物塗布在基板上，乾燥後進行加熱而製造。更具體而言，本發明的膜之製造方法係包含以下的步驟(1)至(3)。步驟(1)：將本發明的樹脂組成物塗布在基板的步驟、步驟(2)：將塗布後的樹脂組成物進行減壓乾燥及/或加熱乾燥而形成組成物層的步驟、步驟(3)：將組成物層加熱的步驟。 The film of this invention can be manufactured by apply|coating the resin composition of this invention on a board|substrate, drying, and heating. More specifically, the method for producing the film of the present invention includes the following steps (1) to (3). Step (1): the step of coating the resin composition of the present invention on the substrate, step (2): the step of drying the coated resin composition under reduced pressure and/or heating to form a composition layer, step (3) ): the step of heating the composition layer.

本發明的樹脂組成物含有聚合性化合物(C)及聚合起始劑(D)時，可藉由進行下述的步驟製造硬化膜。步驟(1)：將本發明的樹脂組成物塗布在基板的步驟、步驟(2)：將塗布後的樹脂組成物進行減壓乾燥及/或加熱乾燥而形成組成物層的步驟、步驟(2a)：將樹脂組成物層曝光的步驟、步驟(2b)：使曝光後的樹脂組成物層顯像之步驟、步驟(3a)：將顯像後的樹脂組成物層加熱之步驟。 When the resin composition of this invention contains a polymerizable compound (C) and a polymerization initiator (D), a cured film can be manufactured by carrying out the following procedure. Step (1): the step of coating the resin composition of the present invention on the substrate, step (2): the step of drying the coated resin composition under reduced pressure and/or heating to form a composition layer, step (2a) ): a step of exposing the resin composition layer, step (2b): a step of developing the exposed resin composition layer, step (3a): a step of heating the developed resin composition layer.

步驟(1)係將本發明的樹脂組成物塗布在基板的步驟。基板可列舉玻璃、金屬、塑膠等，也可在基板上形成彩色濾光片、絕緣膜、導電膜及/或驅動電路等。在基板上的塗布係以使用旋轉塗布機、細縫與旋轉塗布機、細縫塗布機、噴墨、滾塗機、浸塗機等塗布裝置進行為佳。在形成有彩色濾光片、絕緣膜、導電膜的基板上形成本發明的樹脂組成物時，係塗布在彩色濾光片、絕緣膜、導電膜等上。 Step (1) is a step of applying the resin composition of the present invention to a substrate. Examples of the substrate include glass, metal, plastic, etc., and a color filter, an insulating film, a conductive film, and/or a driving circuit, etc. may be formed on the substrate. The coating on the substrate is preferably carried out using a coating apparatus such as a spin coater, a slit and spin coater, a slit coater, an ink jet, a roll coater, and a dip coater. When the resin composition of the present invention is formed on the substrate on which the color filter, insulating film, and conductive film are formed, the resin composition is applied on the color filter, insulating film, conductive film, and the like.

步驟(2)係將塗布後的樹脂組成物減壓乾燥及/或加熱乾燥後形成樹脂組成物層的步驟。藉由進行該步驟去除樹脂組成物中的溶劑等揮發成分。減壓乾燥係以在50至150Pa的壓力下、20至25℃的溫度範圍進行為佳。在減壓乾燥之前或之後，也可進行加熱乾燥(預焙)。加熱乾燥通常是利用烘箱、加熱板等加熱裝置進行。加熱乾燥的溫度係以30至120℃為佳，並以50至110℃更佳。又，加熱時間係以10秒至60分鐘為佳，並以30秒至30分鐘更佳。 Step (2) is a step of forming a resin composition layer after drying the coated resin composition under reduced pressure and/or heating. Volatile components such as solvents in the resin composition are removed by performing this step. The vacuum drying system is preferably carried out under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. Before or after drying under reduced pressure, heat drying (prebaking) may also be performed. Heating drying is usually performed using a heating device such as an oven and a hot plate. The temperature for heating and drying is preferably 30 to 120°C, and more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

步驟(3)係將樹脂組成物層加熱的步驟(後焙)。加熱通常是利用烘箱、加熱板等加熱裝置進行。加熱溫度係以130至270℃為佳，並以150至260℃更佳，而以200至250℃又更佳。加熱溫度為200至250℃時，可防止膜中殘留不需要的溶劑。加熱時間係以1至120分鐘為佳，並以10至60分鐘更佳。 Step (3) is a step of heating the resin composition layer (post-baking). Heating is usually performed using a heating device such as an oven and a hot plate. The heating temperature is preferably 130 to 270°C, more preferably 150 to 260°C, and still more preferably 200 to 250°C. When the heating temperature is 200 to 250°C, unnecessary solvents can be prevented from remaining in the film. The heating time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

步驟(2a)係對經步驟(2)形成之樹脂組成物層進行曝光的步驟。曝光時使用的光源係以產生250至450nm波長之光的光源為佳。例如使用切割此波域的濾光片切割未達350nm的光，也可使用選擇取出此等波域之帶通濾光片(band pass filter)取出436nm附近、408nm附近、365nm附近的光。光源可列舉水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等。 The step (2a) is a step of exposing the resin composition layer formed in the step (2). The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter for cutting this wavelength range is used to cut light below 350 nm, and a band pass filter for selecting and extracting these wavelength ranges can also be used to extract light around 436 nm, around 408 nm, and around 365 nm. Examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

步驟(2b)係將曝光後的樹脂組成物層顯像之步驟。藉由使曝光後的樹脂組成物層與顯像液接觸，使樹脂組成物層的未曝光部份溶解在顯像液中而去除，即可在基板上形成具有圖案的樹脂組成物層。顯像液係以氫氧化鉀、碳酸氫鈉、碳酸鈉、四甲基氫氧化銨等鹼性化合物的水溶液為佳。此等鹼性化合物的水溶液之濃度係以0.01至10質量%為佳，並以0.03至5質量%更佳。此外，顯像液也可含有界面活性劑。顯像方法可以是槳法、浸漬法、噴霧法等的任一種方法。此外，顯像時可將基板以任意角度傾斜。顯像後係以水洗為佳。 Step (2b) is a step of developing the exposed resin composition layer. By contacting the exposed resin composition layer with the developer, the unexposed part of the resin composition layer is dissolved in the developer and removed, so that the patterned resin composition layer can be formed on the substrate. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method, and the like. In addition, the substrate can be tilted at any angle during development. It is better to wash with water after developing.

步驟(3a)係將顯像後的樹脂組成物層加熱之步驟。藉由進行與前述步驟(3)同樣的加熱，使具有圖案的組成物層硬化，即可在基板上形成具有圖案的膜。 Step (3a) is a step of heating the developed resin composition layer. The patterned film can be formed on the substrate by curing the patterned composition layer by heating in the same manner as in the aforementioned step (3).

由此而得的膜，因表面的平整性優異，故可供使用作為例如液晶顯示裝置、有機EL顯示裝置或電子紙使用的彩色濾光片基板、觸控面板的保護膜或外塗層。因此，可製造具備高品質膜之顯示裝置。表面具有凹凸著色圖案的彩色濾光片基板中，也可藉由以本發明的樹脂組成物形成外塗層，而改善表面的平整性。由本發明的樹脂組成物形成之外塗層的膜厚(被塗布面具有凹凸時，係自凸部表面之膜厚)係以0.5μm以上5μm以下為佳，並以0.5μm以上3μm以下更佳。被塗布面具有凹凸時，由本發明的樹脂組成物形成之外塗層的膜厚係以被塗布面的凹凸之高低差的30%以上為佳。由本發明的樹脂組成物獲得的外塗層，即使膜厚較薄也可改善表面的平整性。藉由使用本發明的樹脂組成物形成外塗層，可使外塗層表面的凹凸之高低差，成為被塗布面的凹凸之高低差的50%以下。 The film thus obtained is excellent in surface flatness, and thus can be used as a color filter substrate, a protective film or an overcoat layer for a touch panel, for example, in a liquid crystal display device, an organic EL display device, or electronic paper. Therefore, a display device with a high-quality film can be manufactured. In the color filter substrate having a concave-convex coloring pattern on the surface, the surface flatness can also be improved by forming an overcoat layer with the resin composition of the present invention. The film thickness of the overcoat layer formed from the resin composition of the present invention (when the surface to be coated has unevenness, the film thickness from the surface of the convex portion) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. . When the surface to be coated has irregularities, the film thickness of the overcoat layer formed from the resin composition of the present invention is preferably 30% or more of the difference in height of the irregularities on the surface to be coated. The overcoat layer obtained from the resin composition of the present invention can improve the flatness of the surface even if the film thickness is thin. By forming the overcoat layer using the resin composition of the present invention, the unevenness of the surface of the overcoat layer can be made to be 50% or less of the unevenness of the surface to be coated.

[共聚合物] [Copolymer]

本發明的共聚合物係含有構成單元(Aa)與構成單元(Ab)而不含構成單元(Ac)的樹脂(A)，構成單元(Aa)係包含上述式(Aa-1)或上述式(Aa-2)表示的構成單元。本發明的共聚合物可供使用作為彩色光阻(color resist)的外塗層等、液晶顯示裝置用樹脂組成物之材料。本發明的共聚合物中之構成單元(Aa)也可以是上述式(Aa-1)或上述式(Aa-2)表示的構成單元。 The copolymer of the present invention is a resin (A) which contains a structural unit (Aa) and a structural unit (Ab) but does not contain a structural unit (Ac), and the structural unit (Aa) contains the above formula (Aa-1) or the above formula The constituent unit represented by (Aa-2). The copolymer of the present invention can be used as a material of a resin composition for liquid crystal display devices, such as an overcoat layer of a color resist. The structural unit (Aa) in the copolymer of the present invention may be a structural unit represented by the above formula (Aa-1) or the above formula (Aa-2).

[實施例] [Example]

以下，藉由實施例更詳細說明本發明。例中的「%」及「份」如無特別的說明係表示質量%及質量份。 Hereinafter, the present invention will be described in more detail by way of examples. "%" and "part" in the example represent mass % and mass part unless otherwise specified.

[實施例1至5及比較例1] [Examples 1 to 5 and Comparative Example 1]

<樹脂組成物的調製> <Preparation of resin composition>

以表1所示之比例將樹脂(A)、聚合性化合物(C)、聚合起始劑(D)、硬化劑(G)及整平劑(B)混合，並以使固形分濃度成為表1所示濃度的方式與作為溶劑(E)的丙二醇單甲醚乙酸酯混合，獲得各樹脂組成物。表1中，各成分的份數係表示換算固形分的質量份。 Resin (A), polymerizable compound (C), polymerization initiator (D), hardener (G), and leveling agent (B) were mixed in the proportions shown in Table 1, and the solid content concentration was as shown in Table 1. 1 was mixed with propylene glycol monomethyl ether acetate as a solvent (E) to obtain each resin composition. In Table 1, the parts of each component represent parts by mass in terms of solid content.

表1中的各成分係如下述。 Each component in Table 1 is as follows.

樹脂(a1)：由合成例1獲得的樹脂、樹脂(a2)：由合成例2獲得的樹脂、聚合性化合物(c1)：二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股)製造)、聚合性化合物(c2)：乙二醇改質二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DP-3060；日本化藥(股)製造)、聚合起始劑(d1)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE01；BASF(股)製造)、多元羧酸(g1)：1,2,3,4-丁烷四羧酸(Rikasidd(註冊商標)BT-W；新日本理化(股)製造)、整平劑(b1)：Megafac(註冊商標)F554；DIC(股)製造)。 Resin (a1): Resin obtained by Synthesis Example 1, Resin (a2): Resin obtained by Synthesis Example 2, Polymerizable Compound (c1): Dipivalerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Japan Kayaku Co., Ltd.), polymerizable compound (c2): ethylene glycol-modified dipivoerythritol hexaacrylate (KAYARAD (registered trademark) DP-3060; Nippon Kayaku Co., Ltd. product), polymerization start Agent (d1): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Corporation) , polycarboxylic acid (g1): 1,2,3,4-butane tetracarboxylic acid (Rikasidd (registered trademark) BT-W; manufactured by Nippon Chemical Co., Ltd.), leveling agent (b1): Megafac (registered trademark) trademark) F554; manufactured by DIC (stock)).

(合成例1：樹脂(a1)) (Synthesis Example 1: Resin (a1))

將氮氣充分流入具備回流冷卻器、滴液漏斗及攪拌機的燒瓶內成為氮氣環境，加入二乙二醇乙基甲醚260份，一邊攪拌一邊加熱至85℃。其次，將式(III-1)表示之化合物77份、式(I-1)表示之化合物及式(II-1)表示的化合物之混合物(混合物中二種化合物之莫耳比是50：50)278份與二乙二醇乙基甲醚155份之混合液，以4小時滴入保溫在85℃中的燒瓶內。 Nitrogen gas was sufficiently poured into the flask equipped with a reflux cooler, a dropping funnel, and a stirrer to obtain a nitrogen atmosphere, 260 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 85°C while stirring. Next, 77 parts of the compound represented by the formula (III-1), a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (the molar ratio of the two compounds in the mixture is 50:50) ) 278 parts of mixed solution and 155 parts of diethylene glycol ethyl methyl ether were dropped into the flask which was kept at 85°C over 4 hours.

另一方面，將二乙二醇乙基甲醚208份中溶解有聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)23份之溶液以5小時滴入燒瓶內。聚合起始劑溶液滴加終了之後，保持在85℃中3小時，然後冷卻至室溫，獲得B型黏度(23℃)28mPas、固形分35.7%的共聚合物(樹脂(a1))之溶液。所得的樹脂(a1)之重量平均分子量(Mw)是6.3×10³、分散度(Mw/Mn)是1.80、換算固形分的酸價是0mg-KOH/g。樹脂(a1)具有下述的構成單元。 On the other hand, a solution in which 23 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 208 parts of diethylene glycol ethyl methyl ether was dropped over 5 hours. inside the flask. After the dropwise addition of the polymerization initiator solution, the solution was kept at 85°C for 3 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin (a1)) with a B-type viscosity (23°C) of 28 mPas and a solid content of 35.7%. . The weight average molecular weight (Mw) of the obtained resin (a1) was 6.3×10 ³ , the degree of dispersion (Mw/Mn) was 1.80, and the acid value in terms of solid content was 0 mg-KOH/g. The resin (a1) has the following structural units.

獲得的樹脂之重量平均分子量(Mw)及數平均分子量(Mn)之測定係利用GPC以下述的條件進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin was carried out by GPC under the following conditions.

裝置：HLC-8120GPC(東曹(Tosoh)(股)製造) Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

管柱：TSK-GELG2000HXL Column: TSK-GELG2000HXL

管柱溫度：40℃ Column temperature: 40℃

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

流速：1.0mL/分鐘 Flow rate: 1.0mL/min

被測液固形分濃度：0.001至0.01質量% Measured liquid and solid concentration: 0.001 to 0.01% by mass

注入量：50μL Injection volume: 50 μL

檢測器：RI Detector: RI

校正用標準物質：TSK標準聚苯乙烯(STANDARD POLYSTYRENE)F-40、F-4、F-288、A-2500、A-500(東曹(股)製造) Standard material for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

以上述所獲得的換算聚苯乙烯之重量平均分子量及數平均分子量之比(Mw/Mn)作為分散度。 The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight of the converted polystyrene obtained above was used as the degree of dispersion.

(合成例2：樹脂(a2)) (Synthesis Example 2: Resin (a2))

將氮氣充分流入具備回流冷卻器、滴液漏斗及攪拌機的燒瓶內作成氮氣環境，加入二乙二醇乙基甲醚140份，一邊攪拌一邊加熱至70℃。其次，使甲基丙烯酸40份、式(I-1)表示的單體及式(II-1)表示的單體之混合物(混合物中二種化合物之莫耳比是50：50)360份溶解在二乙二醇乙基甲醚190份中調製溶液，利用滴液泵將此溶液以4小時滴入保溫在70℃中的燒瓶內。 Nitrogen gas was sufficiently poured into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70°C while stirring. Next, 40 parts of methacrylic acid, 360 parts of a mixture of the monomer represented by the formula (I-1) and the monomer represented by the formula (II-1) (the molar ratio of the two compounds in the mixture is 50:50) were dissolved A solution was prepared in 190 parts of diethylene glycol ethyl methyl ether, and this solution was dropped into a flask that was kept at 70° C. by a drip pump over 4 hours.

另一方面，利用另外的滴液泵將二乙二醇乙基甲醚240份中溶解有聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30份之溶液，以5小時滴入燒瓶內。聚合起始劑溶液滴加終了之後，保持在70℃中4小時，然後冷卻至室溫，獲得固形分42%的共聚合物(樹脂(a2))之溶液。獲得的樹脂(a2)之重量平均分子量(Mw)是7,800、分散度(Mw/Mn)是2.0、換算固形分的酸價是61mg-KOH/g。樹脂(a2)具有下述的構成單元。 On the other hand, 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethyl methyl ether using a separate drip pump. The solution was dropped into the flask over 5 hours. After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin (a2)) having a solid content of 42%. The weight average molecular weight (Mw) of the obtained resin (a2) was 7,800, the degree of dispersion (Mw/Mn) was 2.0, and the acid value in terms of solid content was 61 mg-KOH/g. The resin (a2) has the following structural units.

(合成例3：樹脂(a3)) (Synthesis Example 3: Resin (a3))

合成例1中，除了使用式(III-1)表示的化合物136份、式(I-1)表示的化合物及式(II-1)表示的化合物之混合物(混合物中二種化合物之莫耳比是50：50)218份以外，以與合成例1相同的方法進行反應，獲得固形分26.2重量%、重量平均分子量(Mw)7,750、分散度1.8之樹脂(a3)。樹脂(a3)換算固形分的酸價為0mg-KOH/g。 In Synthesis Example 1, except that 136 parts of the compound represented by the formula (III-1), the mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (the molar ratio of the two compounds in the mixture) were used. 50:50) except 218 parts, it reacted by the same method as Synthesis Example 1, and obtained the resin (a3) of 26.2 weight% of solid content, weight average molecular weight (Mw) 7,750, and dispersion degree 1.8. The acid value of the resin (a3) in terms of solid content is 0 mg-KOH/g.

(合成例4：樹脂(a4)) (Synthesis Example 4: Resin (a4))

合成例1中，除了使用式(III-1)表示的化合物177份、式(I-1)表示的化合物及式(II-1)表示的化合物之混合物(混合物中二種化合物之莫耳比是50：50)177份以外，以與合成例1相同的方法進行反應，獲得固形分24.6重量%、重量平均分子量(Mw)7,960、分散度1.8之樹脂(a4)。樹脂(a4)換算固形分的酸價為0mg-KOH/g。 In Synthesis Example 1, except that 177 parts of the compound represented by the formula (III-1), the mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (the molar ratio of the two compounds in the mixture) were used. Except for 50:50) 177 parts, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain a resin (a4) having a solid content of 24.6% by weight, a weight average molecular weight (Mw) of 7,960 and a degree of dispersion of 1.8. The acid value of the resin (a4) in terms of solid content is 0 mg-KOH/g.

<評估用基板的製作> <Production of Evaluation Board>

依序用中性洗劑、水及異丙醇將2吋方形的玻璃基板(Eagle XG：康寧公司製造)洗淨後，使其乾燥。將市售的感光性樹脂組成物(商品名：Diebright(註冊商標))以後焙後的膜厚成為2.0μm之方式旋轉塗布在上述基板上。接著，在清潔烤箱中，以100℃預焙3分鐘形成組成物層。放冷後，使基板上的組成物層與石英玻璃製光罩的間隔成為100μm，使用曝光機(TME-150RSK；Topcon(股)製造，光源；超高壓水銀燈)於大氣壓下，以100mJ/cm²的曝光量(365nm基準)進行光照射。又，此光照射係使超高壓水銀燈發射的光通過光學濾光片(UV-313；旭科技玻璃(Technoglass)(股)製造)而進行。又，光罩係使用形成線寬20μm的1：1線與間隔圖案用之光罩。在23℃將光照射後的組成物層浸泡在含有0.12%非離子系界面活性劑與0.04%氫氧化鉀之水性顯像液中60秒使顯像，水洗後，在烤箱中以230℃進行15分鐘的後焙，製作形成有線寬20μm之線與間隔之圖案(分別具有10個線與間隔)的評估用基板。 A 2-inch square glass substrate (Eagle XG: manufactured by Corning Incorporated) was washed with a neutral detergent, water, and isopropyl alcohol in this order, and then dried. A commercially available photosensitive resin composition (trade name: Diebright (registered trademark)) was spin-coated on the above-mentioned substrate so that the film thickness after post-baking was 2.0 μm. Next, the composition layer was formed by prebaking at 100° C. for 3 minutes in a clean oven. After cooling, the distance between the composition layer on the substrate and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used under atmospheric pressure at 100 mJ/cm Light irradiation was performed at an exposure amount of ² (365 nm reference). In addition, this light irradiation was performed by making the light emitted from an ultra-high pressure mercury lamp pass through an optical filter (UV-313; manufactured by Technoglass Co., Ltd.). In addition, the photomask used for forming a 1:1 line and space pattern with a line width of 20 μm was used. The light-irradiated composition layer was immersed in an aqueous developing solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for 60 seconds at 23°C for development, washed with water, and then carried out in an oven at 230°C After post-baking for 15 minutes, a substrate for evaluation in which a pattern of lines and spaces with a line width of 20 μm (10 lines and spaces, respectively) was formed was produced.

<膜的製作(條件1)> <Production of Film (Condition 1)>

以使後焙後的膜厚(從評估用基板的線圖案表面計的膜厚)成為1.0μm的條件，藉由旋轉塗布機將實施例1至3、6至7及比較例1的各樹脂組成物塗布在前述評估用基板。然後，用減壓乾燥機(VCD微科技(Microtech)(股)製造)，以旋轉泵旋轉數1000rpm、增壓泵旋轉數700rpm、常溫25℃的條件，使其減壓乾燥至減壓度達到66Pa，在加熱板上以溫度100℃預焙3分鐘。放冷後，藉由在溫度230℃進行後焙30分鐘而形成膜。利用接觸式膜厚測定裝置(DEKTAK6M；(股)ULVAC製造)，以測定寬度500μm、測定速率10秒的條件，測定評估用基板上的膜之膜厚，獲得膜表面形狀的輪廓。 Each resin of Examples 1 to 3, 6 to 7, and Comparative Example 1 was coated by a spin coater under the condition that the film thickness after post-baking (film thickness measured from the surface of the line pattern of the evaluation substrate) was 1.0 μm. The composition was coated on the aforementioned evaluation substrate. Then, it was dried under reduced pressure until the degree of reduced pressure reached 66Pa, pre-baked at 100°C for 3 minutes on a hot plate. After standing to cool, a film was formed by post-baking at a temperature of 230°C for 30 minutes. Using a contact film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.), the film thickness of the film on the evaluation substrate was measured under the conditions of a measurement width of 500 μm and a measurement rate of 10 seconds, and the outline of the film surface shape was obtained.

又，由該輪廓計算出膜之膜厚的平均值，從評估用基板的線圖案表面計之膜厚的平均值是1.0μm。 Moreover, the average value of the film thickness of a film was calculated from this profile, and the average value of the film thickness measured from the line pattern surface of the substrate for evaluation was 1.0 μm.

<膜的製作(條件2)> <Production of Film (Condition 2)>

以使後焙後的膜厚(從評估用基板的線圖案表面計的膜厚)成為1.0μm的條件，藉由旋轉塗布機將實施例4、5的各樹脂組成物塗布在前述評估用基板上。然後，利用減壓乾燥機(VCD微科技(股)製造)，以旋轉泵旋轉數1000rpm、增壓泵旋轉數700rpm、常溫25℃的條件，使其減壓乾燥至減壓度達到66Pa，在加熱板上以溫度100℃預焙3分鐘。放冷後，利用曝光機(TME-150RSK；Topcon(股)製造，光源；超高壓水銀燈)，大氣壓下，以25mJ/cm²的曝光量(365nm基準)進行光照射。將光照射後的組成物層在23℃浸泡在含有0.12%非離子系界面活性劑與0.04%氫氧化鉀0.04%之水性顯像液中60秒顯像，水洗後，在烤箱中以230℃進行15分鐘的後焙而形成膜。利用接觸式膜厚測定裝置(DEKTAK6M；(股)ULVAC製造)，以測定寬度500μm、測定速率10秒的條件，測定評估用基板上的膜之膜厚，獲得膜表面形狀的輪廓。由該輪廓計算出膜之膜厚的平均值，從評估用基板的線圖案表面計之膜厚的平均值是1.0μm。 The resin compositions of Examples 4 and 5 were coated on the aforementioned substrate for evaluation by a spin coater under the condition that the film thickness after post-baking (the film thickness measured from the surface of the line pattern of the substrate for evaluation) was 1.0 μm. superior. Then, use a decompression dryer (manufactured by VCD Micro-Technology Co., Ltd.), with the rotation speed of the rotary pump at 1000 rpm, the rotation speed of the booster pump at 700 rpm, and the conditions of normal temperature 25 ° C, make it dry under reduced pressure until the decompression degree reaches 66 Pa, The hot plate was pre-baked at a temperature of 100°C for 3 minutes. After standing to cool, light irradiation was performed at an exposure amount (365 nm standard) of 25 mJ/cm ² under atmospheric pressure using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp). The composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% non-ionic surfactant and 0.04% potassium hydroxide 0.04% at 23°C for 60 seconds for development, and after washing with water, in an oven at 230°C A film was formed by post-baking for 15 minutes. Using a contact film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.), the film thickness of the film on the evaluation substrate was measured with a measurement width of 500 μm and a measurement rate of 10 seconds to obtain the outline of the film surface shape. The average value of the film thickness of the film was calculated from the profile, and the average value of the film thickness measured from the line pattern surface of the substrate for evaluation was 1.0 μm.

<平整性評估> <Flatness Evaluation>

對於前述評估用基板上形成之膜，利用觸針式膜厚計(商品名：DEKTAK3；日本真空(股)製)測定評估用基板的線與間隔圖案上形成之膜的表面輪廓。如第1圖所示之示意截面圖，測定基板1上的線與間隔圖案2(間隔2a、線2b)與膜3為已積層的狀態之最大膜厚與最小膜厚之差△(μm)，評估平整性。將測定結果表示於表1中。差△之值越小，形成之膜越平整。 For the film formed on the aforementioned evaluation substrate, the surface profile of the film formed on the line and space pattern of the evaluation substrate was measured using a stylus type film thickness meter (trade name: DEKTAK3; manufactured by Nippon Vacuum Co., Ltd.). As shown in the schematic cross-sectional view shown in FIG. 1, the difference Δ(μm) between the maximum film thickness and the minimum film thickness in the state where the line and space pattern 2 (space 2a, line 2b) and the film 3 on the substrate 1 are laminated is measured. , to evaluate flatness. The measurement results are shown in Table 1. The smaller the value of the difference Δ, the smoother the film formed.

藉由本發明的樹脂組成物，即使在具有階差的基底或基板上，也可形成平整之膜。因由該樹脂組成物獲得的膜之平整性優異，故可適用於顯示裝置等。 With the resin composition of the present invention, a flat film can be formed even on a base or a substrate having a level difference. Since the film obtained from this resin composition is excellent in flatness, it can be applied to a display device and the like.

由於本案之圖式僅為例舉之例不足以代表，故本案無指定代表圖。 Since the diagrams in this case are only examples and are not representative, there is no designated representative diagram in this case.

Claims

一種液晶顯示裝置用樹脂組成物，係含有樹脂(A)、溶劑及整平劑，前述樹脂(A)係含有具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)、而不含來自屬於由不飽和羧酸及不飽和羧酸酐所組成之群組的化合物之構成單元(Ac)的共聚合物，前述構成單元(Aa)包含式(Aa-1)或式(Aa-2)表示的構成單元；

式(Aa-1)及式(Aa-1)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代；X^b1及X^b2係表示單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊-R^b3-NH-；R^b3係表示碳數1至6的烷二基；＊係表示與O的鍵結前述構成單元(Ab)為式(Ab-1)表示的構成單元，

式(Ab-1)中，R³表示氫原子或甲基，R⁴表示氫原子或碳數1至6的烷基。 A resin composition for a liquid crystal display device, comprising a resin (A), a solvent and a leveling agent, wherein the resin (A) comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a reactive subunit (Aa). A copolymer of a structural unit (Ab) of a methyl group or an active methine group without a structural unit (Ac) from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, the aforementioned structural unit (Aa) contains a structural unit represented by formula (Aa-1) or formula (Aa-2);

In formula (Aa-1) and formula (Aa-1), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group can be substituted with a hydroxyl group; X ^b1 and X ^b2 represents a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-; R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms ; * represents the bond with O The aforementioned structural unit (Ab) is a structural unit represented by the formula (Ab-1),

In formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

如申請專利範圍第1項所述之液晶顯示裝置用樹脂組成物，其中，前述樹脂(A)的酸價為0mg-KOH/g至5mg-KOH/g。 The resin composition for a liquid crystal display device according to claim 1, wherein the acid value of the resin (A) is 0 mg-KOH/g to 5 mg-KOH/g.

如申請專利範圍第1或2項所述之液晶顯示裝置用樹脂組成物，其中，前述樹脂(A)係由具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)形成之共聚合物。 The resin composition for a liquid crystal display device according to claim 1 or 2, wherein the resin (A) is composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a reactive subunit (Aa). A copolymer formed by the structural unit (Ab) of methyl group or active methine group.

如申請專利範圍第1或2項所述之液晶顯示裝置用樹脂組成物，其中，整平劑是氟系界面活性劑。 The resin composition for liquid crystal display devices according to claim 1 or 2, wherein the leveling agent is a fluorine-based surfactant.

一種液晶顯示裝置用膜，係由申請專利範圍第1至4項中任一項所述之液晶顯示裝置用樹脂組成物形成者。 A film for a liquid crystal display device formed from the resin composition for a liquid crystal display device described in any one of claims 1 to 4 of the patent application.

一種共聚合物，係含有具有碳數2至4的環狀醚結構之構成單元(Aa)與具有活性亞甲基或活性次甲基的構成單元(Ab)而不含來自屬於由不飽和羧酸及不飽和羧酸酐所組成之群組的化合物之構成單元(Ac)，前述構成單元(Aa)包含式(Aa-1)或式(Aa-2)表示的構成單元；

式(Aa-1)及式(Aa-2)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代；X^b1及X^b2係表示單鍵、＊-R^b3-、＊-R^b3-O-、＊-R^b3-S-或＊-R^b3-NH-；R^b3係表示碳數1至6的烷二基；＊係表示與O的鍵結前述構成單元(Ab)為式(Ab-1)表示的構成單元，

式(Ab-1)中，R³表示氫原子或甲基，R⁴表示氫原子或碳數1至6的烷基。 A copolymer containing a constituent unit (Aa) having a cyclic ether structure with a carbon number of 2 to 4 and a constituent unit (Ab) having an active methylene group or an active methine group, but not derived from an unsaturated carboxyl group. The constituent unit (Ac) of the compound of the group consisting of acid and unsaturated carboxylic acid anhydride, the aforementioned constituent unit (Aa) comprises the constituent unit represented by formula (Aa-1) or formula (Aa-2);

In formula (Aa-1) and formula (Aa-2), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group can be substituted with a hydroxyl group; X ^b1 and X ^b2 represents a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-; R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms ; * represents the bond with O The aforementioned structural unit (Ab) is a structural unit represented by the formula (Ab-1),