TWI636087B - Curable composition, method for manufacturing cured film, cured film and display device - Google Patents

Curable composition, method for manufacturing cured film, cured film and display device Download PDF

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TWI636087B
TWI636087B TW103139839A TW103139839A TWI636087B TW I636087 B TWI636087 B TW I636087B TW 103139839 A TW103139839 A TW 103139839A TW 103139839 A TW103139839 A TW 103139839A TW I636087 B TWI636087 B TW I636087B
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group
compound
curable composition
cured film
acrylate
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TW201522474A (en
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山健太
米澤裕之
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富士軟片股份有限公司
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
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    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer

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Abstract

本發明的硬化性組成物含有：(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂、(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外)、(C)烷氧基矽烷化合物、(D)有機溶劑、以及(E)平均粒徑為1nm~200nm的無機粒子及/或平均粒徑為1nm~200nm的聚合物粒子，且無機粒子及聚合物粒子的平均空隙率小於10%，平均空隙率為200個所述粒子的由電子顯微鏡所得的粒子的剖面圖像的空隙部分與粒子剖面之面積比的算術平均值，並且使所述硬化性組成物硬化而成的膜的依據JIS-K-7136所測定的全光線透射率為90%以上。 The curable composition of the present invention contains (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group, and (J) a compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000 (wherein (A) a compound corresponding to the component (I), (C) an alkoxydecane compound, (D) an organic solvent, and (E) inorganic particles having an average particle diameter of 1 nm to 200 nm and/or an average particle diameter of 1 nm. 200 nm polymer particles, and the average porosity of the inorganic particles and the polymer particles is less than 10%, and the average void ratio is 200. The area ratio of the void portion of the cross-sectional image of the particles obtained by the electron microscope to the particle cross-section of the particles The arithmetic mean value and the film obtained by hardening the curable composition have a total light transmittance of 90% or more as measured according to JIS-K-7136.

Description

硬化性組成物、硬化膜的製造方法、硬化膜及顯示 裝置 Curing composition, method for producing cured film, cured film, and display Device

本發明是有關於一種硬化性組成物、硬化膜的製造方法、硬化膜、以及使用硬化膜的有機電致發光(Electroluminescence，EL)顯示裝置及液晶顯示裝置。 The present invention relates to a curable composition, a method for producing a cured film, a cured film, and an organic electroluminescence (EL) display device and a liquid crystal display device using the cured film.

液晶顯示裝置、有機EL顯示裝置等平板顯示器(flat panel display)被廣泛使用。最近，於該些顯示器的製造步驟中，就減少對基板或電路等的損傷、節能化等觀點而言，必須實現製造步驟中的各種硬化膜的加熱溫度的低溫化。 A flat panel display such as a liquid crystal display device or an organic EL display device is widely used. Recently, in the manufacturing steps of these displays, it is necessary to reduce the heating temperature of various cured films in the manufacturing process from the viewpoint of reducing damage to the substrate or the circuit, energy saving, and the like.

作為此種硬化性組成物，例如於專利文獻1中揭示有一種熱硬化性樹脂組成物，其特徵在於：其是將不飽和羧酸及/或不飽和羧酸酐、含環氧基的自由基聚合性化合物、與單烯烴系不飽和化合物的共聚物溶解於有機溶劑中而成。 As such a curable composition, for example, Patent Document 1 discloses a thermosetting resin composition characterized in that it is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride or an epoxy group-containing radical. The polymerizable compound and a copolymer of a monoolefin-based unsaturated compound are dissolved in an organic solvent.

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平6-157716號公報 [Patent Document 1] Japanese Patent Laid-Open No. 6-157716

然而，專利文獻1所記載的硬化性組成物的加熱溫度必須為200℃以上，若於低溫(例如180℃以下、進而150℃以下)下進行加熱，則無法獲得充分的硬度。 However, the heating temperature of the curable composition described in Patent Document 1 must be 200° C. or more, and if it is heated at a low temperature (for example, 180° C. or lower and further 150° C. or lower), sufficient hardness cannot be obtained.

本發明的目的在於解決所述課題，且其目的在於提供一種即便於低溫下加熱亦可獲得高硬度的硬化性組成物。進而，本發明的目的在於提供一種使用所述硬化性組成物的硬化膜的製造方法及硬化膜、以及使用硬化膜的有機EL顯示裝置及液晶顯示裝置。 An object of the present invention is to solve the above problems, and an object thereof is to provide a curable composition which can obtain high hardness even when heated at a low temperature. Further, an object of the present invention is to provide a method for producing a cured film using the curable composition, a cured film, and an organic EL display device and a liquid crystal display device using the cured film.

本申請案發明者根據所述狀況進行了研究，結果藉由下述手段<1>、較佳為藉由手段<2>~手段<12>而解決了所述課題。 The inventors of the present application have conducted research based on the above-described situation, and as a result, the above problem has been solved by the following means <1>, preferably by means <2> to means <12>.

<1>一種硬化性組成物，含有：(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂、(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中，將相當於(I)成分的化合物除外)、(C)烷氧基矽烷化合物、(D)有機溶劑、以及(E)平均粒徑為1nm~200nm的無機粒子及/或平均粒徑為1nm~200nm的聚合物粒子，且無機粒子及聚合物粒子的平均空 隙率小於10%，所述平均空隙率為200個所述粒子的由電子顯微鏡所得的粒子的剖面圖像的空隙部分與粒子剖面之面積比的算術平均值，並且使硬化性組成物硬化而成的膜的依據日本工業標準(Japanese Industrial Standard，JIS)-K-7136所測定的全光線透射率為90%以上。 <1> A curable composition comprising: (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group; and (J) a compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000 (excluding the compound corresponding to the component (I)), (C) an alkoxydecane compound, (D) an organic solvent, and (E) inorganic particles having an average particle diameter of 1 nm to 200 nm and/or an average particle diameter It is a polymer particle of 1 nm to 200 nm, and the average particle of the inorganic particle and the polymer particle The gap ratio is less than 10%, and the average void ratio is an arithmetic mean of the ratio of the area of the void portion of the cross-sectional image of the particles obtained by the electron microscope to the particle cross-section of the particles of 200 particles, and the hardenable composition is hardened. The total light transmittance of the obtained film measured according to Japanese Industrial Standard (JIS)-K-7136 was 90% or more.

<2>如<1>所記載的硬化性組成物，更含有(F)交聯劑。 <2> The curable composition according to <1>, further comprising (F) a crosslinking agent.

<3>如<2>所記載的硬化性組成物，其中(F)交聯劑包含封端異氰酸酯(blocked isocyanate)化合物。 <3> The curable composition according to <2>, wherein the (F) crosslinking agent comprises a blocked isocyanate compound.

<4>如<2>或<3>所記載的硬化性組成物，其中(F)交聯劑包含多官能巰基化合物。 <4> The curable composition according to <2> or <3> wherein the (F) crosslinking agent comprises a polyfunctional mercapto compound.

<5>如<1>至<4>中任一項所記載的硬化性組成物，其中硬化性組成物的固體成分濃度為20質量%~40質量%。 The curable composition according to any one of <1> to <4>, wherein the solid content concentration of the curable composition is 20% by mass to 40% by mass.

<6>一種硬化膜的製造方法，其特徵在於包括：(1)將如<1>至<5>中任一項所記載的硬化性組成物塗佈於基板上的步驟；(2)自所塗佈的硬化性組成物中去除溶劑的步驟；以及(3)進行熱硬化的步驟。 <6> A method for producing a cured film, comprising: (1) a step of applying the curable composition according to any one of <1> to <5> on a substrate; (2) a step of removing the solvent from the applied curable composition; and (3) a step of performing thermal hardening.

<7>如<6>所記載的硬化膜的製造方法，其中(3)步驟中的熱硬化溫度為150℃以下。 <7> The method for producing a cured film according to <6>, wherein the heat curing temperature in the step (3) is 150 ° C or lower.

<8>如<6>或<7>所記載的硬化膜的製造方法，其中於(2)去除溶劑的步驟後、(3)進行熱硬化的步驟前，包括進行全面曝光的步驟。 <8> The method for producing a cured film according to <6> or <7>, wherein the step of performing total exposure is performed after the step of (2) removing the solvent and (3) performing the step of thermally curing.

<9>一種硬化膜，其是使如<1>至<5>中任一項所記載的硬化性組成物硬化而成。 <9> A cured film obtained by curing the curable composition according to any one of <1> to <5>.

<10>如<9>所記載的硬化膜，其為保護膜。 <10> The cured film according to <9>, which is a protective film.

<11>如<9>或<10>所記載的硬化膜，其中依據JIS5600所測定的負重750g時的鉛筆硬度為2H以上。 <11> The cured film according to <9> or <10>, wherein the pencil hardness at a load of 750 g measured in accordance with JIS 5600 is 2H or more.

<12>一種有機EL顯示裝置或液晶顯示裝置，具有如<9>至<11>中任一項所記載的硬化膜。 <12> An organic EL display device or a liquid crystal display device, comprising the cured film according to any one of <9> to <11>.

藉由本發明，可提供一種即便於低溫下加熱亦可獲得高硬度的硬化性組成物。進而，可提供一種使用所述硬化性組成物的硬化膜的製造方法及硬化膜、以及使用硬化膜的有機EL顯示裝置及液晶顯示裝置。 According to the present invention, it is possible to provide a curable composition which can obtain high hardness even when heated at a low temperature. Further, a method for producing a cured film using the curable composition, a cured film, and an organic EL display device and a liquid crystal display device using the cured film can be provided.

1、16‧‧‧TFT(薄膜電晶體) 1,16‧‧‧TFT (thin film transistor)

2‧‧‧配線 2‧‧‧Wiring

3、8‧‧‧絕緣膜 3,8‧‧‧Insulation film

4‧‧‧平坦化膜 4‧‧‧Flat film

5‧‧‧第一電極 5‧‧‧First electrode

6、14、15‧‧‧玻璃基板 6, 14, 15‧ ‧ glass substrate

7、18‧‧‧接觸孔 7, 18‧‧‧ contact holes

10‧‧‧液晶顯示裝置 10‧‧‧Liquid crystal display device

12‧‧‧背光單元 12‧‧‧Backlight unit

17‧‧‧硬化膜 17‧‧‧ hardened film

19‧‧‧ITO透明電極 19‧‧‧ITO transparent electrode

20‧‧‧液晶 20‧‧‧LCD

22、122‧‧‧彩色濾光片 22, 122‧‧‧ color filters

110‧‧‧畫素基板 110‧‧‧ pixel substrate

111、127‧‧‧偏光板 111, 127‧‧‧ polarizing plate

112、123‧‧‧透明基板 112, 123‧‧‧ Transparent substrate

113‧‧‧共通電極 113‧‧‧Common electrode

114‧‧‧絕緣層 114‧‧‧Insulation

115‧‧‧畫素電極 115‧‧‧ pixel electrodes

116、121‧‧‧配向膜 116, 121‧‧‧ alignment film

120‧‧‧對向基板 120‧‧‧ opposite substrate

124‧‧‧相位差膜 124‧‧‧ phase difference film

126‧‧‧接著層 126‧‧‧Next layer

130‧‧‧感測器部 130‧‧‧Sensor Department

140‧‧‧液晶層 140‧‧‧Liquid layer

圖1表示有機EL顯示裝置的一例的構成概念圖，且表示底部發光(bottom emission)型的有機EL顯示裝置中的基板的示意性剖面圖，具有平坦化膜4。 1 is a conceptual view showing an example of an organic EL display device, and is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4.

圖2表示液晶顯示裝置的一例的構成概念圖，且表示液晶顯示裝置中的主動式矩陣基板的示意性剖面圖，具有作為層間絕緣膜的硬化膜17。 2 is a conceptual view showing an example of a liquid crystal display device, and shows a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device, and has a cured film 17 as an interlayer insulating film.

圖3表示具有觸控面板功能的液晶顯示裝置的一例的構成概念圖。 FIG. 3 is a conceptual view showing an example of a liquid crystal display device having a touch panel function.

以下，對本發明的內容加以詳細說明。以下記載的構成要件的說明有時是根據本發明的具代表性的實施態樣來進行，但本發明不限定於此種實施態樣。另外，本申請案說明書中，所謂「~」是以包含其前後所記載的數值作為下限值及上限值的含意而使用。另外，本發明中所謂有機EL元件，是指有機電致發光元件。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be carried out in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, in the specification of the present application, "~" is used to include the numerical values described before and after the lower limit value and the upper limit value. Further, the term "organic EL element" as used in the present invention means an organic electroluminescence element.

於本說明書中的基團(原子團)的表述中，未記載經取代及未經取代的表述包含不具有取代基的基團，並且亦包含具有取代基的基團。例如所謂「烷基」，不僅包含不具有取代基的烷基(未經取代的烷基)，而且亦包含具有取代基的烷基(經取代的烷基)。再者，本說明書中，「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯，「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸，「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基。 In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime.

本發明中所謂固體成分，是指25℃下的固體成分。 The solid component in the present invention means a solid component at 25 °C.

於本說明書中，重量平均分子量及數量平均分子量是以由凝膠滲透層析法(Gel Permeation Chromatography，GPC)測定所得的聚苯乙烯換算值而定義。本說明書中，重量平均分子量(Mw)及數量平均分子量(Mn)例如可藉由以下方式求出：使用HLC-8220(東曹(股)製造)，使用TSKgel Super AWM-H(東曹(股)製造，6.0mm ID×15.0cm)作為管柱，使用10mmol/L的溴化鋰N-甲基吡咯啶酮(N-methyl pyrrolidinone，NMP)溶液 作為溶離液。 In the present specification, the weight average molecular weight and the number average molecular weight are defined by polystyrene equivalent values obtained by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (Dongcao) ), manufactured as 6.0mm ID × 15.0cm) as a column, using 10mmol/L lithium bromide N-methylpyrrolidone (NMP) solution As a solution.

本發明的組成物含有：(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂、(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中，將相當於(I)成分的化合物除外)、(C)烷氧基矽烷化合物、(D)有機溶劑、以及(E)平均粒徑為1nm~200nm的無機粒子及/或平均粒徑為1nm~200nm的聚合物粒子，且所述無機粒子及聚合物粒子的平均空隙率小於10%，所述平均空隙率為200個所述粒子的由電子顯微鏡所得的剖面圖像的空隙部分與粒子剖面之面積比的算術平均值，並且所述硬化性組成物的特徵在於：使所述硬化性組成物硬化而成的膜的依據JIS-K-7136所測定的全光線透射率為90%以上。 The composition of the present invention contains: (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group, and (J) a compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000 (wherein (C) alkoxydecane compound, (D) an organic solvent, and (E) inorganic particles having an average particle diameter of 1 nm to 200 nm and/or an average particle diameter of 1 nm to 200 nm Polymer particles, wherein the inorganic particles and the polymer particles have an average void ratio of less than 10%, and the average void ratio is a void portion of the cross-sectional image obtained by an electron microscope of 200 particles and an area of the particle cross-section The averaging average of the ratio, and the curable composition is characterized in that the film obtained by curing the curable composition has a total light transmittance of 90% or more as measured according to JIS-K-7136.

藉由設定為此種構成，可於低溫下硬化，且可獲得硬度高的硬化膜。本發明的硬化性組成物亦可更含有交聯劑或界面活性劑等其他成分。 By setting it as such a structure, it can harden at low temperature, and can obtain the hardened film of high hardness. The curable composition of the present invention may further contain other components such as a crosslinking agent or a surfactant.

<(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂> <(I) Acrylic resin having an epoxy group and/or styrene resin having an epoxy group>

本發明的硬化性組成物含有具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂(以下有時稱為「具有環氧基的丙烯酸系樹脂等」)。本發明中所謂丙烯酸系樹脂，是指丙烯酸酯及/或甲基丙烯酸酯的聚合物，亦可與其他自由基聚合性單體進行共聚合。所謂具有環氧基的苯乙烯系樹脂，含有源自苯乙烯的重複單元，亦可含有其他自由基聚合性單體。另外，本說明書中，關於 含有源自(甲基)丙烯酸酯的重複單元及源自苯乙烯的重複單元兩者的樹脂，將源自(甲基)丙烯酸酯的重複單元的莫耳比高的樹脂稱為丙烯酸系樹脂，將源自苯乙烯的重複單元的莫耳比高的樹脂稱為苯乙烯系樹脂。 The curable composition of the present invention contains an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group (hereinafter sometimes referred to as "acrylic resin having an epoxy group" or the like). The acrylic resin in the present invention means a polymer of an acrylate and/or a methacrylate, and may be copolymerized with another radical polymerizable monomer. The styrene-based resin having an epoxy group contains a repeating unit derived from styrene, and may contain another radical polymerizable monomer. In addition, in this manual, about A resin containing both a repeating unit derived from (meth) acrylate and a repeating unit derived from styrene, and a resin having a high molar ratio derived from a repeating unit of (meth) acrylate is referred to as an acrylic resin. A resin having a high molar ratio of a repeating unit derived from styrene is referred to as a styrene resin.

具有環氧基的丙烯酸系樹脂中的源自(甲基)丙烯酸酯的重複單元較佳為70mol%(莫耳百分比)以上，更佳為90mol%以上，進而佳為95mol%以上。上限並無特別限定，亦可為100mol%。 The repeating unit derived from (meth) acrylate in the epoxy resin having an epoxy group is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. The upper limit is not particularly limited and may be 100 mol%.

具有環氧基的苯乙烯系樹脂中的源自苯乙烯的重複單元較佳為70mol%以上，更佳為90mol%以上，進而佳為95mol%以上。上限並無特別限定，亦可為100mol%。 The repeating unit derived from styrene in the styrene resin having an epoxy group is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. The upper limit is not particularly limited and may be 100 mol%.

<<具有環氧基的重複單元>> <<Repeating unit with epoxy group>>

本發明的具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂含有具有環氧基的重複單元。具有環氧基的重複單元較佳為源自具有環氧基的(甲基)丙烯酸酯的重複單元或源自具有環氧基的苯乙烯的重複單元。 The epoxy group-containing acrylic resin and/or the epoxy group-containing styrene resin of the present invention contain a repeating unit having an epoxy group. The repeating unit having an epoxy group is preferably a repeating unit derived from a (meth) acrylate having an epoxy group or a repeating unit derived from styrene having an epoxy group.

(I)具有環氧基的丙烯酸系樹脂等中，具有環氧基的重複單元的含有率較佳為10mol%~90mol%，更佳為20mol%~80mol%，尤佳為30mol%~80mol%。 (I) In the acrylic resin having an epoxy group, the content of the repeating unit having an epoxy group is preferably from 10 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, still more preferably from 30 mol% to 80 mol%. .

本發明中所用的具有環氧基的丙烯酸系樹脂等較佳為含有下述式(3)~式(5)的任一個所表示的重複單元。進而，亦可含有源自其他自由基聚合性單體的重複單元。 The epoxy group-containing acrylic resin or the like used in the present invention preferably contains a repeating unit represented by any one of the following formulas (3) to (5). Further, it may contain a repeating unit derived from another radical polymerizable monomer.

[化1] [Chemical 1]

(式(3)~式(5)中，R1表示氫原子、甲基或鹵素原子，R2、R3、R4、R5、R6、R7、R8及R9分別表示氫原子或烷基。n為1~10的整數) (In the formulae (3) to (5), R 1 represents a hydrogen atom, a methyl group or a halogen atom, and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each represent hydrogen. Atom or alkyl. n is an integer from 1 to 10)

R1較佳為氫原子或甲基，更佳為甲基。 R 1 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

R2、R3、R4、R5、R6、R7、R8及R9分別較佳為氫原子或甲基，更佳為氫原子。 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

若對用於形成具有環氧基的重複單元的自由基聚合性單體加以具體例示，則可列舉：丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧丁酯、甲基丙烯酸-3,4-環氧丁酯、丙烯酸-4,5-環氧戊酯、甲基丙烯酸-4,5-環氧戊酯、丙烯酸-6,7-環氧庚酯、甲基丙烯酸-6,7-環氧庚酯等(甲基)丙烯酸酯類；鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基鄰乙烯基苄基縮水甘油醚、α-甲基間乙烯基苄基縮水甘油醚、α-甲基對乙烯基苄基縮水甘油醚等乙烯基苄基縮水甘 油醚類；鄰乙烯基苯基縮水甘油醚、間乙烯基苯基縮水甘油醚、對乙烯基苯基縮水甘油醚等乙烯基苯基縮水甘油醚類；丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯。該些單體中，較佳為丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、對乙烯基苯基縮水甘油醚、丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯，尤佳為丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯。該些單體可單獨使用或組合使用兩種以上。 Specific examples of the radical polymerizable monomer for forming a repeating unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and 3,4-butylbutyl acrylate. 3-,4-epoxybutyl methacrylate, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, -6,7-epoxyheptyl acrylate, methyl (meth) acrylates such as -6,7-epoxyheptyl acrylate; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl Vinylbenzyl glycidyl ether, α-methyl-vinylvinyl benzyl glycidyl ether, α-methyl-vinyl vinyl glycidyl ether, etc. Oleic ethers; vinyl vinyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether; 3,4-epoxycyclohexyl acrylate Methyl ester, 3,4-epoxycyclohexylmethyl methacrylate. Among these monomers, glycidyl acrylate, glycidyl methacrylate, p-vinylphenyl glycidyl ether, 3,4-epoxycyclohexyl methyl acrylate, methacrylic acid-3, 4 are preferred. Epoxycyclohexylmethyl ester, more preferably glycidyl acrylate or glycidyl methacrylate. These monomers may be used alone or in combination of two or more.

<<其他自由基聚合性單體>> <<Other free radical polymerizable monomers>>

本發明的具有環氧基的丙烯酸系樹脂等亦可含有具有環氧基的重複單元以外的重複單元。其他重複單元只要可與所述式(3)~式(5)的任一個所表示的自由基聚合性單體進行共聚合，則並無特別限制。具體例可列舉源自以下單體的重複單元：苯乙烯、第三丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、α-甲基-乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯腈等。 The epoxy group-containing acrylic resin or the like of the present invention may contain a repeating unit other than the repeating unit having an epoxy group. The other repeating unit is not particularly limited as long as it can be copolymerized with the radical polymerizable monomer represented by any one of the above formulas (3) to (5). Specific examples include repeating units derived from the following monomers: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, α-A Ethyl ethoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, A Methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, methacrylic acid Butyl ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, Isobornyl methacrylate, acrylonitrile, and the like.

該些單體可單獨使用或組合使用兩種以上。 These monomers may be used alone or in combination of two or more.

於含有其他重複單元的情形時，於(I)具有環氧基的丙烯酸系樹脂等中，其他重複單元較佳為50mol%以下，更佳為30mol%以下。下限值較佳為5mol%以上，更佳為10mol%以上。 In the case of the (I) acrylic resin having an epoxy group, the other repeating unit is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 5 mol% or more, more preferably 10 mol% or more.

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂的重量平均分子量以苯乙烯換算計，較佳為1,000~200,000、更佳為2,000~50,000的範圍。 The weight average molecular weight of the (I) epoxy group-containing acrylic resin and/or epoxy group-containing styrene resin is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of styrene.

關於本發明的硬化性組成物中的(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂的含量，就硬化膜硬度的觀點而言，於組成物的固體成分100質量份中，所述含量較佳為20質量份~80質量份，更佳為25質量份~70質量份，進而佳為29質量份~60質量份。 In the curable composition of the present invention, the content of the (I) epoxy group-containing acrylic resin and/or the epoxy group-containing styrene resin is solid in the composition from the viewpoint of the hardness of the cured film. The content is preferably 20 parts by mass to 80 parts by mass, more preferably 25 parts by mass to 70 parts by mass, and still more preferably 29 parts by mass to 60 parts by mass, per 100 parts by mass of the component.

另外，本發明的硬化性組成物較佳為以固體成分的20質量%~80質量%而含有(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂，更佳為含有25質量%~70質量%，進而佳為含有29質量%~60質量%。 In addition, the curable composition of the present invention preferably contains (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group, in an amount of 20% by mass to 80% by mass of the solid component. The content is preferably from 25% by mass to 70% by mass, and more preferably from 29% by mass to 60% by mass.

(I)具有環氧基的丙烯酸系樹脂等可僅使用一種，亦可混合使用兩種以上。於調配兩種以上的情形時，較佳為合計量為所述範圍。本發明中，較佳為至少含有具有環氧基的丙烯酸系樹脂。 (I) The acrylic resin having an epoxy group may be used alone or in combination of two or more. In the case of blending two or more types, it is preferred that the total amount is the above range. In the present invention, it is preferred to contain at least an acrylic resin having an epoxy group.

<(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中，將相當於(I)成分的化合物除外)> <(J) A compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000 (excluding a compound corresponding to the component (I))>

本發明的硬化性組成物含有(J)具有羧基的重量平均分子量為1000~50,000的化合物。其中，(J)具有羧基的重量平均分子 量為1000~50,000的化合物並非相當於所述(I)具有環氧基的丙烯酸系樹脂的化合物。 The curable composition of the present invention contains (J) a compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000. Wherein (J) a weight average molecule having a carboxyl group The compound having an amount of from 1,000 to 50,000 is not a compound corresponding to the (I) acrylic resin having an epoxy group.

具有羧基的重量平均分子量為1000~50,000的化合物可使用公知的化合物。其中，較佳為丙烯酸系樹脂。 As the compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000, a known compound can be used. Among them, an acrylic resin is preferred.

具有羧基的重量平均分子量為1000~50,000的化合物較佳為含有式(1)~式(4)的任一個所表示的重複單元及具有羧酸基的重複單元的樹脂，更佳為丙烯酸系樹脂。 The compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000 is preferably a resin containing a repeating unit represented by any one of the formulae (1) to (4) and a repeating unit having a carboxylic acid group, more preferably an acrylic resin. .

(式(1)~式(4)中，X1、X2、X3、X4及X5分別表示氫原子或一價有機基，W1、W2、W3及W4分別表示-O-或-NH-，R分別表示氫原子或一價有機基，R'分別表示分支或直鏈伸烷基，Y1、Y2、Y3及Y4分別表示二價連結基，Z1、Z2、Z3及Z4分別表示氫原子或一價有機基，n、m、p及q分別獨立地為3~500的整數， j及k分別獨立地為2~8的整數) (In the formulae (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each represent a hydrogen atom or a monovalent organic group, and W 1 , W 2 , W 3 and W 4 respectively represent - O- or -NH-, R represents a hydrogen atom or a monovalent organic group, respectively, R' represents a branched or linear alkyl group, respectively, and Y 1 , Y 2 , Y 3 and Y 4 each represent a divalent linking group, Z 1 , Z 2 , Z 3 and Z 4 respectively represent a hydrogen atom or a monovalent organic group, and n, m, p and q are each independently an integer of 3 to 500, and j and k are each independently an integer of 2 to 8)

X1、X2、X3、X4及X5分別較佳為氫原子或烷基，更佳為氫原子或甲基。 X 1 , X 2 , X 3 , X 4 and X 5 are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

W1、W2、W3及W4分別表示-O-或-NH-，較佳為-O-。 W 1 , W 2 , W 3 and W 4 each represent -O- or -NH-, preferably -O-.

(J)具有羧基的重量平均分子量為1000~50,000的化合物中的式(1)~式(4)的任一個所表示的重複單元的含有率較佳為10mol%~90mol%，更佳為20mol%~80mol%，進而更佳為30mol%~80mol%，尤佳為30mol%~70mol%。 (J) The content of the repeating unit represented by any one of the formulae (1) to (4) in the compound having a weight average molecular weight of the carboxyl group of from 1,000 to 50,000 is preferably from 10 mol% to 90 mol%, more preferably 20 mol%. % to 80 mol%, more preferably 30 mol% to 80 mol%, and particularly preferably 30 mol% to 70 mol%.

式(1)~式(4)的任一個所表示的重複單元可僅含有一種，亦可含有兩種以上。於含有兩種以上的情形時，其合計量成為所述範圍。 The repeating unit represented by any one of the formulas (1) to (4) may be contained alone or in combination of two or more. When two or more cases are contained, the total amount thereof becomes the above range.

具有羧酸基的重複單元較佳為丙烯酸、甲基丙烯酸。(J)具有羧基的重量平均分子量為1000~50,000的化合物中的具有羧酸基的重複單元的含有率較佳為所有重複單元的10mol%~90mol%，更佳為20mol%~80mol%，進而更佳為30mol%~80mol%，尤佳為30mol%~70mol%。具有羧酸基的重複單元可僅含有一種，亦可含有兩種以上。於含有兩種以上的情形時，其合計量成為所述範圍。 The repeating unit having a carboxylic acid group is preferably acrylic acid or methacrylic acid. (J) The content of the repeating unit having a carboxylic acid group in the compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 is preferably from 10 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, based on all repeating units. More preferably, it is 30 mol% - 80 mol%, and especially preferably 30 mol% - 70 mol%. The repeating unit having a carboxylic acid group may be contained alone or in combination of two or more. When two or more cases are contained, the total amount thereof becomes the above range.

進而，(J)具有羧基的重量平均分子量為1000~50,000的化合物亦可含有其他公知的重複單元。 Further, (J) a compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000 may contain other known repeating units.

其他重複單元只要可與式(1)~式(4)的任一個共聚合，則並無特別限制。具體例可列舉源自以下單體的重複單元：苯乙 烯、第三丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、α-甲基-乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯腈等。 The other repeating unit is not particularly limited as long as it can be copolymerized with any of the formulae (1) to (4). Specific examples include repeating units derived from the following monomers: phenylethyl Alkene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, α-methyl-ethoxylated styrene, methoxystyrene , ethoxystyrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, N-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxypropyl ester, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, and the like.

(J)具有羧基的重量平均分子量為1000~50,000的化合物中的其他重複單元較佳為0mol%~50mol%的範圍，更佳為10mol%~30mol%的範圍。其他重複單元可僅含有一種，亦可含有兩種以上。於含有兩種以上的情形時，其合計量成為所述範圍。 (J) The other repeating unit in the compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 is preferably in the range of from 0 mol% to 50 mol%, more preferably in the range of from 10 mol% to 30 mol%. Other repeating units may be contained alone or in combination of two or more. When two or more cases are contained, the total amount thereof becomes the above range.

(J)具有羧基的重量平均分子量為1000~50,000的化合物亦可使用式(5)所表示的化合物。 (J) A compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000 can also be used as the compound represented by the formula (5).

(式(5)中，R3表示(m+n)價的連結基，R4及R5分別表示單鍵或二價連結基，A2表示含有羧基的一價有機基，n個A2及R4可分別相同亦可不同，m表示0~8，n表示2~9，m+n為3~ 10，P2表示高分子骨架，m個P2及R5可分別相同亦可不同) (In the formula (5), R 3 represents a (m+n)-valent linking group, R 4 and R 5 each represent a single bond or a divalent linking group, and A 2 represents a monovalent organic group having a carboxyl group, and n A 2 And R 4 may be the same or different, m represents 0-8, n represents 2-9, m+n is 3-10, P 2 represents a polymer skeleton, and m P 2 and R 5 may be the same or different )

所述式(5)中，R4及R5分別獨立地表示單鍵或二價連結基。存在n個的R4可分別相同亦可不同。另外，存在m個的R5可分別相同亦可不同。 In the formula (5), R 4 and R 5 each independently represent a single bond or a divalent linking group. There may be n or more R 4 which may be the same or different. Further, there may be m or more R 5 which may be the same or different.

R4及R5的二價連結基包含由1個~100個的碳原子、0個~10個的氮原子、0個~50個的氧原子、1個~200個的氫原子及0個~20個的硫原子所形成的基團，可未經取代，亦可更具有取代基。 The divalent linking group of R 4 and R 5 includes one to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 The group formed by ~20 sulfur atoms may be unsubstituted or may have a substituent.

所述二價連結基可列舉下述結構單元或將所述結構單元組合而構成的基團作為具體例。 The divalent linking group may be exemplified by the following structural unit or a group formed by combining the structural units.

R4及R5分別獨立地較佳為單鍵或由1個~50個的碳原子、0個~8個的氮原子、0個~25個的氧原子、1個~100個的氫原子及0個~10個的硫原子所形成的二價連結基，更佳為單鍵或由1個~30個的碳原子、0個~6個的氮原子、0個~15個的氧 原子、1個~50個的氫原子及0個~7個的硫原子所形成的二價連結基，尤佳為單鍵或由1個~10個的碳原子、0個~5個的氮原子、0個~10個的氧原子、1個~30個的氫原子及0個~5個的硫原子所形成的二價連結基。 R 4 and R 5 are each independently preferably a single bond or from 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, and 1 to 100 hydrogen atoms. And a divalent linking group formed by 0 to 10 sulfur atoms, more preferably a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms a divalent linking group formed by one to 50 hydrogen atoms and 0 to 7 sulfur atoms, particularly preferably a single bond or a carbon atom of 1 to 10, and 0 to 5 nitrogen atoms. a divalent linking group formed by 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.

所述中，於二價連結基具有取代基的情形時，所述取代基例如可列舉：甲基、乙基等碳數1~20的烷基，苯基、萘基等碳數6~16的芳基，羥基，胺基，羧基，磺醯胺基，N-磺醯基醯胺基，乙醯氧基等碳數1~6的醯氧基，甲氧基、乙氧基等碳數1~6的烷氧基，氯原子、溴原子等鹵素原子，甲氧基羰基、乙氧基羰基、環己氧基羰基等碳數2~7的烷氧基羰基，氰基，第三丁基碳酸酯基等碳酸酯基等。 In the case where the divalent linking group has a substituent, the substituent may, for example, be an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, or a carbon number of 6 to 16 such as a phenyl group or a naphthyl group. Carbon group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amine group, carboxyl group, sulfonylamino group, N-sulfonylguanidino group, ethoxycarbonyl group, etc., carbon number such as methoxy group and ethoxy group Alkoxy group of 1 to 6, a halogen atom such as a chlorine atom or a bromine atom; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a cyano group; A carbonate group such as a carbonate group or the like.

所述式(5)中，R3表示(m+n)價的連結基。m+n滿足3~10。 In the formula (5), R 3 represents a (m+n)-valent linking group. m+n satisfies 3~10.

所述R3所表示的(m+n)價的連結基包含由1個~60個的碳原子、0個~10個的氮原子、0個~50個的氧原子、1個~100個的氫原子及0個~20個的硫原子所形成的基團，可未經取代，亦可更具有取代基。 The (m+n)-valent linking group represented by R 3 includes one to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 The hydrogen atom and the group of 0 to 20 sulfur atoms may be unsubstituted or substituted.

所述(m+n)價的連結基可列舉下述結構單元或將所述結構單元組合而構成的基團(亦可形成環結構)作為具體例。 The (m+n)-valent linking group may be exemplified by the following structural unit or a group formed by combining the structural units (which may also form a ring structure).

[化5] [Chemical 5]

(m+n)價的連結基較佳為由1個~60個的碳原子、0個~10個的氮原子、0個~40個的氧原子、1個~120個的氫原子及0個~10個的硫原子所形成的基團，更佳為由1個~50個的碳原子、0個~10個的氮原子、0個~30個的氧原子、1個~100個的氫原子及0個~7個的硫原子所形成的基團，尤佳為由1個~40個的碳原子、0個~8個的氮原子、0個~20個的氧原子、1個~80個的氫原子及0個~5個的硫原子所形成的基團。 The (m+n) valent linking group is preferably one to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0. The group formed by ~10 sulfur atoms is more preferably one to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, and 1 to 100 A group formed by a hydrogen atom and 0 to 7 sulfur atoms is preferably one to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, and 1 ring. a group of ~80 hydrogen atoms and 0 to 5 sulfur atoms.

所述中，於(m+n)價的連結基具有取代基的情形時，所述取代基例如可列舉：甲基、乙基等碳數1~20的烷基，苯基、萘基等碳數6~16的芳基，羥基，胺基，羧基，磺醯胺基，N-磺醯基醯胺基，乙醯氧基等碳數1~6的醯氧基，甲氧基、乙氧基等碳數1~6的烷氧基，氯原子、溴原子等鹵素原子，甲氧基羰基、乙氧基羰基、環己氧基羰基等碳數2~7的烷氧基羰基，氰基，第三丁基碳酸酯基等碳酸酯基等。 In the case where the (m+n)-valent linking group has a substituent, the substituent may, for example, be an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, or a phenyl group or a naphthyl group. a aryl group having 6 to 16 carbon atoms, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylguanidino group, an ethoxy group, a methoxy group having 1 to 6 carbon atoms, a methoxy group, and a ethoxy group. Alkoxy group having 1 to 6 carbon atoms such as an oxy group; a halogen atom such as a chlorine atom or a bromine atom; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; A carbonate group such as a tributyl carbonate group or the like.

以下示出所述R3所表示的(m+n)價的連結基的具體例 [具體例(1)~具體例(17)]。其中，本發明不限制於該些具體例。 Specific examples are shown below [specific examples (1) - Specific Example (17)] of the R (m + n) valent linking group represented by the three. However, the invention is not limited to the specific examples.

[化7] [Chemistry 7]

所述具體例中，就原料的獲取性、合成的容易程度、於各種溶劑中的溶解性的觀點而言，最佳的(m+n)價的連結基為下述基團。 In the specific examples, the optimum (m+n)-valent linking group is the following group from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

所述式(5)中，m表示0~8。m較佳為0.5~5，更佳為0.5~4，尤佳為0.5~3。 In the formula (5), m represents 0 to 8. m is preferably from 0.5 to 5, more preferably from 0.5 to 4, and particularly preferably from 0.5 to 3.

另外，所述式(5)中，n表示2~9。n較佳為2~8，更佳為2~7，尤佳為3~6。 Further, in the formula (5), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

另外，式(5)中的P2表示高分子骨架，可根據目的等自公知的聚合物等中選擇。於式(5)中存在m個的P2可分別相同亦可不同。 In addition, P 2 in the formula (5) represents a polymer skeleton, and can be selected from known polymers and the like according to the purpose and the like. The number of P 2 present in the formula (5) may be the same or different.

聚合物中，為了構成高分子骨架，較佳為選自由乙烯系單體的聚合物或共聚物、酯系聚合物、醚系聚合物、胺基甲酸酯系聚合物、醯胺系聚合物、環氧系聚合物、矽酮系聚合物、及該等的改質物或共聚物[例如包含聚醚/聚胺基甲酸酯共聚物、聚醚/乙烯系單體的聚合物的共聚物等(可為無規共聚物、嵌段共聚物、接枝共聚物的任一種)]所組成的組群中的至少一種，更佳為選自由乙烯系單體的聚合物或共聚物、酯系聚合物、醚系聚合物、胺基甲酸酯系聚合物、及該等的改質物或共聚物所組成的組群中的至少一種，進而佳為乙烯系單體的聚合物或共聚物，尤佳為丙烯酸系樹脂((甲基)丙烯酸系單體的聚合物或共聚物)。 In the polymer, in order to form a polymer skeleton, a polymer or copolymer selected from a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, and a guanamine polymer are preferable. , an epoxy-based polymer, an anthrone-based polymer, and a modified or copolymer thereof (for example, a copolymer comprising a polyether/polyurethane copolymer, a polyether/vinyl monomer) At least one of the groups consisting of (any of a random copolymer, a block copolymer, and a graft copolymer), more preferably selected from the group consisting of polymers or copolymers of vinyl monomers, esters a polymer, an ether polymer, a urethane polymer, and at least one of the group consisting of the modified or copolymer, and more preferably a polymer or copolymer of a vinyl monomer More preferably, it is an acrylic resin (polymer or copolymer of a (meth)acrylic monomer).

本發明中，所述P2的高分子骨架較佳為具有至少一種酸基。 In the present invention, the polymer skeleton of P 2 preferably has at least one acid group.

具有構成所述高分子骨架的酸基的聚合物例如可列舉：具有酸基的聚醯胺-胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚胺基甲酸酯、改質聚酯、改質聚(甲基)丙烯酸酯、(甲基)丙 烯酸系共聚物、萘磺酸福馬林縮合物、及聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺、烷醇胺、顏料衍生物等。該等中，較佳為(甲基)丙烯酸共聚物。 Examples of the polymer having an acid group constituting the polymer skeleton include a polyamine-amine having an acid group and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, and a modified polyamine group. Acid ester, modified polyester, modified poly(meth) acrylate, (methyl) propyl An olefinic copolymer, a naphthalenesulfonic acid famarin condensate, a polyoxyethylene alkyl phosphate, a polyoxyethylene alkylamine, an alkanolamine, a pigment derivative, and the like. Among these, a (meth)acrylic copolymer is preferred.

於高分子骨架中導入酸基的方法並無特別限制，可採用藉由具有酸基的乙烯系單體來進行導入的方法、藉由利用交聯性側鏈加成酸基來進行導入的方法等，就容易控制酸基的導入量的方面、合成的成本的方面而言，較佳為以下形態：如後述般，高分子骨架是含有源自具有酸基的乙烯系單體的構成單元而構成，藉此導入酸基。 The method of introducing an acid group into the polymer skeleton is not particularly limited, and a method of introducing the vinyl monomer having an acid group and introducing the acid group by using a crosslinkable side chain may be employed. In terms of the amount of introduction of the acid group and the cost of the synthesis, it is preferred that the polymer skeleton contains a constituent unit derived from a vinyl monomer having an acid group, as will be described later. The composition is thereby introduced into an acid group.

此處，所謂「酸基」，可列舉羧基、磺酸基、磷酸基、酚性羥基，較佳為羧基。 Here, the "acid group" may, for example, be a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group, and is preferably a carboxyl group.

所述乙烯系單體並無特別限制，例如較佳為(甲基)丙烯酸酯類、丁烯酸酯類、乙烯酯類、馬來酸二酯類、富馬酸二酯類、衣康酸二酯類、(甲基)丙烯醯胺類、苯乙烯類、乙烯醚類、乙烯酮類、烯烴類、馬來醯亞胺類、(甲基)丙烯腈、具有酸基的乙烯系單體等。 The vinyl monomer is not particularly limited, and is preferably, for example, a (meth) acrylate, a butenoate, a vinyl ester, a maleic acid diester, a fumaric acid diester, or itaconic acid. Diesters, (meth) acrylamides, styrenes, vinyl ethers, ketenes, olefins, maleimides, (meth)acrylonitrile, vinyl monomers having acid groups Wait.

以下，對該些乙烯系單體的較佳例加以說明。 Hereinafter, preferred examples of the vinyl monomers will be described.

(甲基)丙烯酸酯類的例子可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙 烯酸第三辛酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸乙醯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸3-苯氧基-2-羥基丙酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸2-苯基乙烯酯、(甲基)丙烯酸1-丙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-烯丙氧基乙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二乙二醇單甲醚、(甲基)丙烯酸二乙二醇單***、(甲基)丙烯酸三乙二醇單甲醚、(甲基)丙烯酸三乙二醇單***、(甲基)丙烯酸聚乙二醇單甲醚、(甲基)丙烯酸聚乙二醇單***、(甲基)丙烯酸β-苯氧基乙氧基乙酯、(甲基)丙烯酸壬基苯氧基聚乙二醇酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸三溴苯氧基乙酯、(甲基)丙烯酸γ-丁內酯-2-基酯等。 Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, Tertiary butyl cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) propyl Third octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, (methyl) ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl ethyl ester, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-(meth)acrylate Hydroxypropyl ester, 2-chloroethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinyl (meth)acrylate, (A) 2-phenylvinyl acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate Ester, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, (A) Base) triethylene glycol monoethyl acrylate, polyethylene glycol monomethyl ether (meth) acrylate, (methyl) Polyethylene glycol monoethyl acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate , dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, (methyl) Dicyclopentyl acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, γ-butyrolactone-2-yl (meth)acrylate, and the like.

丁烯酸酯類的例子可列舉丁烯酸丁酯及丁烯酸己酯等。 Examples of the butenoate esters include butyl butenoate and hexyl butenoate.

乙烯酯類的例子可列舉：乙酸乙烯酯、氯乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、甲氧基乙酸乙烯酯及苯甲酸乙烯酯等。 Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

馬來酸二酯類的例子可列舉：馬來酸二甲酯、馬來酸二乙酯 及馬來酸二丁酯等。 Examples of the maleic acid diesters include dimethyl maleate and diethyl maleate. And dibutyl maleate and the like.

富馬酸二酯類的例子可列舉：富馬酸二甲酯、富馬酸二乙酯及富馬酸二丁酯等。 Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

衣康酸二酯類的例子可列舉：衣康酸二甲酯、衣康酸二乙酯及衣康酸二丁酯等。 Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(甲基)丙烯醯胺類可列舉：(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-硝基苯基丙烯醯胺、N-乙基-N-苯基丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮丙烯醯胺、N-羥甲基丙烯醯胺、N-羥基乙基丙烯醯胺、乙烯基(甲基)丙烯醯胺、N,N-二烯丙基(甲基)丙烯醯胺、N-烯丙基(甲基)丙烯醯胺等。 Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl (methyl). Acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl ( Methyl) acrylamide, N-(2-methoxyethyl)(methyl) acrylamide, N,N-dimethyl(meth) decylamine, N,N-diethyl (A Base acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) propylene Guanamine, (meth) propylene decyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N - diallyl (meth) acrylamide, N-allyl (meth) acrylamide, and the like.

苯乙烯類的例子可列舉：苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、氯甲基苯乙烯、經可藉由酸性物質而脫保護的基團(例如第三丁氧基羰基(t-Boc)等)保護的羥基苯乙烯、乙烯基苯甲酸甲酯及α-甲基苯乙烯等。 Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, groups deprotected by acidic materials (eg A hydroxystyrene, a methyl benzoate, an α-methyl styrene or the like protected by a third butoxycarbonyl group (t-Boc) or the like.

乙烯醚類的例子可列舉：甲基乙烯醚、乙基乙烯醚、2- 氯乙基乙烯醚、羥乙基乙烯醚、丙基乙烯醚、丁基乙烯醚、己基乙烯醚、辛基乙烯醚、甲氧基乙基乙烯醚及苯基乙烯醚等。 Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and 2- Chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxy ethyl vinyl ether, and phenyl vinyl ether.

乙烯酮類的例子可列舉：甲基乙烯酮、乙基乙烯酮、丙基乙烯酮、苯基乙烯酮等。 Examples of the ketenes include methyl ketene, ethyl ketene, propyl ketene, and phenyl ketene.

烯烴類的例子可列舉：乙烯、丙烯、異丁烯、丁二烯、異戊二烯等。 Examples of the olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

馬來醯亞胺類的例子可列舉：馬來醯亞胺、丁基馬來醯亞胺、環己基馬來醯亞胺、苯基馬來醯亞胺等。 Examples of the maleidinide include maleic imine, butyl maleimide, cyclohexylmaleimide, and phenylmaleimide.

亦可使用(甲基)丙烯腈、經乙烯基取代的雜環式基(例如乙烯基吡啶、N-乙烯基吡咯啶酮、乙烯基咔唑等)、N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基咪唑、乙烯基己內酯等。 It is also possible to use (meth)acrylonitrile, a vinyl-substituted heterocyclic group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N- Vinyl acetamide, N-vinylimidazole, vinyl caprolactone, and the like.

除了所述化合物以外，例如亦可使用具有胺基甲酸酯基、脲基、磺醯胺基、酚基、醯亞胺基等官能基的乙烯系單體。此種具有胺基甲酸酯基或脲基的單體例如可利用異氰酸酯基與羥基或胺基的加成反應來適當合成。具體而言，可藉由以下反應來適當合成：含異氰酸酯基的單體與含有1個羥基的化合物、或者含有1個一級胺基或二級胺基的化合物的加成反應，或含羥基的單體、或者含一級胺基或二級胺基的單體與單異氰酸酯的加成反應等。 In addition to the above compounds, for example, a vinyl monomer having a functional group such as a urethane group, a urea group, a sulfonylamino group, a phenol group or a quinone group can also be used. Such a monomer having a urethane group or a ureido group can be appropriately synthesized, for example, by an addition reaction of an isocyanate group with a hydroxyl group or an amine group. Specifically, it can be suitably synthesized by an addition reaction of an isocyanate group-containing monomer with a compound having one hydroxyl group or a compound containing one primary or secondary amine group, or a hydroxyl group-containing compound. Addition reaction of a monomer or a monomer containing a primary or secondary amine group with a monoisocyanate.

繼而，對為了於高分子骨架P2中導入酸基而使用的具有酸基的乙烯系單體加以說明。 Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P 2 will be described.

所述具有酸基的乙烯系單體的例子可列舉具有羧基的乙烯系 單體或具有磺酸基的乙烯系單體。 Examples of the vinyl group having an acid group include a vinyl group having a carboxyl group. A monomer or a vinyl monomer having a sulfonic acid group.

具有羧基的乙烯系單體可列舉：(甲基)丙烯酸、乙烯基苯甲酸、馬來酸、馬來酸單烷基酯、富馬酸、衣康酸、丁烯酸、肉桂酸、丙烯酸二聚物等。另外，亦可利用(甲基)丙烯酸-2-羥乙酯等具有羥基的單體與馬來酸酐或鄰苯二甲酸酐、環己烷二羧酸酐般的環狀酸酐的加成反應物，ω-羧基聚己內酯單(甲基)丙烯酸酯等。另外，亦可使用馬來酸酐、衣康酸酐、檸康酸酐等含酸酐的單體作為羧基的前驅物。再者，該等中，就共聚合性或成本、溶解性等的觀點而言，尤佳為(甲基)丙烯酸。 Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid. Polymer, etc. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic acid anhydride such as maleic anhydride or phthalic anhydride or cyclohexane dicarboxylic anhydride may be used. Ω-carboxypolycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of a carboxyl group. Further, among these, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

另外，具有磺酸基的乙烯系單體可列舉2-丙烯醯胺-2-甲基丙磺酸等，具有磷酸基的乙烯系單體可列舉磷酸單(2-丙烯醯氧基乙基酯)、磷酸單(1-甲基-2-丙烯醯氧基乙基酯)等。 Further, examples of the vinyl monomer having a sulfonic acid group include 2-propenylamine-2-methylpropanesulfonic acid and the like, and the vinyl monomer having a phosphoric acid group is exemplified by mono(2-propenyloxyethyl phosphate). ), mono(1-methyl-2-propenyloxyethyl phosphate), and the like.

進而，亦可利用含有酚性羥基的乙烯系單體或含有磺醯胺基的乙烯系單體等作為具有酸基的乙烯系單體。 Further, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonylamino group may be used as the vinyl monomer having an acid group.

於高分子骨架P2含有源自含酸基的乙烯系單體的單體單元的情形時，關於源自含酸基的乙烯系單體的單體單元於高分子骨架中的含量，以質量換算計，相對於高分子骨架總體，較佳為3質量%~40質量%，更佳為5質量%~20質量%的範圍。 In the case where the polymer skeleton P 2 contains a monomer unit derived from an acid group-containing vinyl monomer, the content of the monomer unit derived from the acid group-containing vinyl monomer in the polymer skeleton is determined by mass. The conversion amount is preferably from 3% by mass to 40% by mass, and more preferably from 5% by mass to 20% by mass based on the total mass of the polymer skeleton.

成分J中的酸基的含量是根據成分J所具有的酸值而適當決定。成分J的酸值較佳為20mgKOH/g~300mgKOH/g，更佳為50mgKOH/g~250mgKOH/g，尤佳為50mgKOH/g~210mgKOH/g。若酸值為20mgKOH/g以上，則可充分獲得感光性樹 脂組成物的鹼顯影性，若酸值為300mgKOH/g以下，則顯影穩定性或膜薄化性優異。 The content of the acid group in the component J is appropriately determined depending on the acid value of the component J. The acid value of the component J is preferably from 20 mgKOH/g to 300 mgKOH/g, more preferably from 50 mgKOH/g to 250 mgKOH/g, still more preferably from 50 mgKOH/g to 210 mgKOH/g. If the acid value is 20 mgKOH/g or more, the photosensitive tree can be sufficiently obtained. The alkali developability of the fat composition is excellent in development stability or film thinning property when the acid value is 300 mgKOH/g or less.

(J)具有羧基的重量平均分子量為1000~50,000的化合物的市售品可例示莊克麗(Joncryl)67(巴斯夫(BASF)公司製造)。 (J) A commercially available product having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000 is exemplified by Joncryl 67 (manufactured by BASF Corporation).

(J)具有羧基的重量平均分子量為1000~50,000的化合物除了所述以外，可例示日本專利特開2013-83698號公報的段落編號0019~段落編號0032中所記載的含羧酸的樹脂，將該些內容併入至本申請案說明書中。 (J) The carboxylic acid-containing resin described in Paragraph No. 0019 to Paragraph No. 0032 of JP-A-2013-83698, which is a compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000, will be exemplified. This content is incorporated into the specification of the present application.

(J)具有羧基的重量平均分子量為1000~50,000的化合物的重量平均分子量較佳為2000~20,000，更佳為3,000~50,000的範圍。 (J) The weight average molecular weight of the compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 is preferably from 2,000 to 20,000, more preferably from 3,000 to 50,000.

本發明的硬化性組成物中，相對於組成物的固體成分100質量份，較佳為以10質量份~60質量份的比例而含有(J)具有羧基的重量平均分子量為1000~50,000的化合物，更佳為以15質量份~50質量份的比例而含有(J)具有羧基的重量平均分子量為1000~50,000的化合物，進而佳為以20質量份~45質量份的比例而含有(J)具有羧基的重量平均分子量為1000~50,000的化合物。 In the curable composition of the present invention, it is preferable to contain (J) a compound having a weight average molecular weight of 1,000 to 50,000 having a carboxyl group in a ratio of 10 parts by mass to 60 parts by mass based on 100 parts by mass of the solid content of the composition. More preferably, (J) a compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000, more preferably from 20 parts by mass to 45 parts by mass, in a ratio of from 15 parts by mass to 50 parts by mass (J) A compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000.

本發明的硬化性組成物可僅含有一種(J)具有羧基的重量平均分子量為1000~50,000的化合物，亦可含有兩種以上。於含有兩種以上的情形時，較佳為合計量成為所述範圍。 The curable composition of the present invention may contain only one (J) compound having a carboxyl group and having a weight average molecular weight of 1,000 to 50,000, or may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<(C)烷氧基矽烷化合物> <(C) alkoxydecane compound>

本發明的硬化性組成物含有烷氧基矽烷化合物。若使用烷氧基矽烷化合物，則可提高由本發明的硬化性組成物所形成的膜與基板的密接性。本發明的硬化性組成物中可使用的烷氧基矽烷化合物較佳為使基材、例如矽、氧化矽、氮化矽等矽化合物、金、銅、鉬、鈦、鋁等金屬與絕緣膜的密接性提高的化合物。具體而言，公知的矽烷偶合劑等亦有效。較佳為具有乙烯性不飽和鍵的矽烷偶合劑。 The curable composition of the present invention contains an alkoxydecane compound. When an alkoxy decane compound is used, the adhesiveness of the film formed by the curable composition of this invention, and a board|substrate can be improved. The alkoxydecane compound which can be used in the curable composition of the present invention is preferably a substrate, a ruthenium compound such as ruthenium, iridium oxide or ruthenium nitride, or a metal such as gold, copper, molybdenum, titanium or aluminum, and an insulating film. A compound with improved adhesion. Specifically, a known decane coupling agent or the like is also effective. A decane coupling agent having an ethylenically unsaturated bond is preferred.

矽烷偶合劑例如可列舉：γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三烷氧基矽烷、γ-縮水甘油氧基丙基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-巰基丙基三烷氧基矽烷、β-(3,4-環氧環己基)乙基三烷氧基矽烷、乙烯基三烷氧基矽烷。該些化合物中，更佳為γ-甲基丙烯醯氧基丙基三烷氧基矽烷或γ-丙烯醯氧基丙基三烷氧基矽烷或乙烯基三烷氧基矽烷、γ-縮水甘油氧基丙基三烷氧基矽烷。該些化合物可單獨使用一種或組合使用兩種以上。 Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl dialkoxy decane, γ-chloropropyl trialkoxy decane And γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, these compounds are γ-methacryloxypropyltrialkoxydecane or γ-acryloxypropyltrialkoxydecane or vinyltrialkoxydecane, γ-glycidol. Oxypropyl propyl alkoxy decane. These compounds may be used alone or in combination of two or more.

市售品可例示信越化學公司製造的KBM-403或KBM-5103。 Commercially available products are KBM-403 or KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

相對於總固體成分的合計量100質量份，本發明的硬化性組成物中的烷氧基矽烷化合物的含量較佳為0.1質量份~30質量份，更佳為2質量份~20質量份，進而佳為2質量份~15質量份。烷氧基矽烷化合物可僅為一種，亦可含有兩種以上。於含有 兩種以上的情形時，較佳為合計量成為所述範圍。 The content of the alkoxydecane compound in the curable composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 2 parts by mass to 20 parts by mass, per 100 parts by mass of the total solid content. Further preferably, it is 2 parts by mass to 15 parts by mass. The alkoxydecane compound may be used alone or in combination of two or more. Containing In the case of two or more types, it is preferred that the total amount is within the above range.

<(D)溶劑> <(D) Solvent>

本發明的硬化性組成物含有溶劑。本發明的硬化性組成物較佳為以將作為必需成分的成分A及成分B、成分C與後述的任意成分溶解於溶劑中的溶液的形式而製備。 The curable composition of the present invention contains a solvent. The curable composition of the present invention is preferably prepared in the form of a solution in which the component A, the component B, and the component C, which are essential components, and an optional component described later are dissolved in a solvent.

本發明的硬化性組成物中使用的溶劑可使用公知的溶劑，可例示：乙二醇單烷基醚類、乙二醇二烷基醚類、乙二醇單烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇二烷基醚類、丙二醇單烷基醚乙酸酯類、二乙二醇二烷基醚類、二乙二醇單烷基醚乙酸酯類、二丙二醇單烷基醚類、丁二醇二乙酸酯類、二丙二醇二烷基醚類、二丙二醇單烷基醚乙酸酯類、酯類、酮類、醯胺類、內酯類等。該些溶劑的具體例可參照日本專利特開2009-098616號公報的段落0062。具體可例示丙二醇單甲醚乙酸酯或甲基乙基二甘醇。 A known solvent can be used as the solvent to be used in the curable composition of the present invention, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol. Monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers Examples, butanediol diacetate, dipropylene glycol dialkyl ether, dipropylene glycol monoalkyl ether acetate, esters, ketones, guanamines, lactones, and the like. Specific examples of such solvents can be referred to paragraph 0062 of Japanese Patent Laid-Open Publication No. 2009-098616. Specifically, propylene glycol monomethyl ether acetate or methyl ethyl diethylene glycol can be exemplified.

就塗佈性的觀點而言，溶劑的沸點較佳為100℃~300℃，更佳為120℃~250℃。 The boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C from the viewpoint of coatability.

本發明中可使用的溶劑可單獨使用一種或併用兩種以上。亦較佳為併用沸點不同的溶劑。 The solvent which can be used in the invention may be used alone or in combination of two or more. It is also preferred to use a solvent having a different boiling point.

就調整為適於塗佈的黏度的觀點而言，相對於固體成分100質量份，本發明的硬化性組成物中的溶劑的含量較佳為100質量份~3,000質量份，更佳為200質量份~2,000質量份，進而佳為250質量份~1,000質量份。 From the viewpoint of adjusting the viscosity suitable for coating, the content of the solvent in the curable composition of the present invention is preferably from 100 parts by mass to 3,000 parts by mass, more preferably 200% by mass based on 100 parts by mass of the solid content. It is preferably 2,000 parts by mass, and more preferably from 250 parts by mass to 1,000 parts by mass.

硬化性組成物的固體成分濃度較佳為3質量%~50質量%，更佳為20質量%~40質量%。 The solid content concentration of the curable composition is preferably from 3% by mass to 50% by mass, more preferably from 20% by mass to 40% by mass.

硬化性組成物的黏度較佳為1mPa．s~200mPa．s，更佳為2mPa．s~100mPa．s，最佳為3mPa．s~80mPa．s。黏度例如較佳為使用東機產業(股)公司製造的RE-80L型旋轉黏度計於25℃±0.2℃下進行測定。關於測定時的轉速，於黏度小於5mPa．s的情況下較佳為以100rpm的轉速進行測定，於黏度為5mPa．s以上且小於10mPa．s的情況下較佳為以50rpm的轉速進行測定，於黏度為10mPa．s以上且小於30mPa．s的情況下較佳為以20rpm的轉速進行測定，於黏度為30mPa．s以上的情況下較佳為以10rpm的轉速進行測定。 The viscosity of the curable composition is preferably 1 mPa. s~200mPa. s, more preferably 2mPa. s~100mPa. s, the best is 3mPa. s~80mPa. s. The viscosity is preferably measured by using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. at 25 ° C ± 0.2 ° C. Regarding the rotational speed at the time of measurement, the viscosity is less than 5 mPa. In the case of s, it is preferably measured at a rotation speed of 100 rpm, and the viscosity is 5 mPa. Above s and less than 10mPa. In the case of s, it is preferably measured at a rotational speed of 50 rpm, and the viscosity is 10 mPa. Above s and less than 30mPa. In the case of s, it is preferably measured at a rotation speed of 20 rpm, and the viscosity is 30 mPa. In the case of s or more, it is preferably measured at a number of revolutions of 10 rpm.

<(E)平均粒徑為1nm~200nm的無機粒子及/或平均粒徑為1nm~200nm的聚合物粒子> <(E) Inorganic particles having an average particle diameter of 1 nm to 200 nm and/or polymer particles having an average particle diameter of 1 nm to 200 nm >

本發明的硬化性組成物含有平均粒徑為1nm~200nm的無機粒子及/或平均粒徑為1nm~200nm的聚合物粒子。藉由含有此種粒子，硬化膜的硬度變得更優異。 The curable composition of the present invention contains inorganic particles having an average particle diameter of 1 nm to 200 nm and/or polymer particles having an average particle diameter of 1 nm to 200 nm. By containing such particles, the hardness of the cured film becomes more excellent.

就硬化膜的硬度的觀點而言，粒子的空隙率較佳為小於10%，更佳為小於3%，最佳為並無空隙。此處所謂空隙，是指觀察粒子的剖面時可見的成為粒子內部的孔的部分。粒子的空隙率為200個粒子的由電子顯微鏡所得的粒子的剖面圖像的空隙部分與粒子剖面之面積比的算術平均值。 From the viewpoint of the hardness of the cured film, the void ratio of the particles is preferably less than 10%, more preferably less than 3%, and most preferably no void. The term "void" as used herein refers to a portion of a hole that is visible inside a particle when the cross section of the particle is observed. The void ratio of the particles is an arithmetic mean of the ratio of the area of the void portion of the cross-sectional image of the particles obtained by the electron microscope to the area of the particle cross section of 200 particles.

就硬化膜的硬度、透明性的觀點而言，粒徑為1nm~200 nm，較佳為5nm~100nm，進而佳為5nm~50nm。粒徑是指藉由電子顯微鏡來測定任意200個粒子的粒徑而求出的其算術平均值。另外，於粒子的形狀並非球形的情形時，將最長邊設定為直徑。 From the viewpoint of hardness and transparency of the cured film, the particle diameter is from 1 nm to 200. The nm is preferably 5 nm to 100 nm, and more preferably 5 nm to 50 nm. The particle diameter refers to an arithmetic mean value obtained by measuring the particle diameter of an arbitrary 200 particles by an electron microscope. Further, when the shape of the particles is not spherical, the longest side is set to the diameter.

<<無機粒子>> <<Inorganic particles>>

就粒子的穩定性、硬化膜的硬度、透明性、折射率調整性的觀點而言，無機粒子可列舉金屬、金屬氧化物、雲母的粒子等。 The inorganic particles include metals, metal oxides, and mica particles, from the viewpoints of the stability of the particles, the hardness of the cured film, the transparency, and the refractive index adjustability.

金屬粒子可應用過渡金屬元素、典型金屬元素的任一種，例如較佳為應用可廣泛地用於各種用途中的屬於元素週期表第VIII族的鐵、鈷、鎳、釕、銠、鈀、鋨、銥、鉑，或屬於元素週期表第IB族的銅、銀、金等。其中，較佳為導電性優異的金、銀、鉑、鈀、銅、鎳，更佳為銅、銀、鎳。另外，該些元素不限於一種，亦可將兩種以上組合，亦可為合金。 The metal particles may be any of a transition metal element and a typical metal element, and for example, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium belonging to Group VIII of the periodic table which can be widely used in various applications is preferably used. , bismuth, platinum, or copper, silver, gold, etc. belonging to Group IB of the Periodic Table of the Elements. Among them, gold, silver, platinum, palladium, copper, and nickel which are excellent in conductivity are preferable, and copper, silver, and nickel are more preferable. Further, the elements are not limited to one type, and may be used in combination of two or more types.

金屬氧化物粒子較佳為含有矽(Si)、鈹(Be)、鎂(Mg)、鈣(Ca)、鍶(Sr)、鋇(Ba)、鈧(Sc)、釔(Y)、鑭(La)、鈰(Ce)、釓(Gd)、鋱(Tb)、鏑(Dy)、鐿(Yb)、鑥(Lu)、鈦(Ti)、鋯(Zr)、鉿(Hf)、鈮(Nb)、鉬(Mo)、鎢(W)、鋅(Zn)、硼(B)、鋁(Al)、鍺(Ge)、錫(Sn)、鉛(Pb)、銻(Sb)、鉍(Bi)、碲(Te)等原子的氧化物粒子，更佳為氧化矽、氧化鈦、鈦複合氧化物、氧化鋅、氧化鋯、銦/錫氧化物、銻/錫氧化物，進而佳為氧化矽、氧化鈦、鈦複合氧化物、氧化鋯。 The metal oxide particles preferably contain bismuth (Si), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), strontium (Sc), strontium (Y), strontium ( La), cerium (Ce), yttrium (Gd), yttrium (Tb), yttrium (Dy), yttrium (Yb), lanthanum (Lu), titanium (Ti), zirconium (Zr), yttrium (Hf), yttrium ( Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), aluminum (Al), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), antimony ( Oxide particles of atoms such as Bi) and cerium (Te), more preferably cerium oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin oxide, antimony/tin oxide, and preferably oxidation. Antimony, titanium oxide, titanium composite oxide, zirconia.

天然雲母(以下簡稱為雲母)為造岩礦物的重要一族， 為形成積層結構、具備解理性(各層間容易剝離的特徵)的礦物的總稱。雲母為形成以下結構的2：1型黏土礦物：於3原子的矽(Si)與1原子的鋁(Al)的氧化物所形成的4個四面體結構間，夾持有2個或3個金屬氧化物/氫氧化物所構成的八面體結構。由於4面體的1/4經取代為Al，故將四面體-八面體-四面體作為1個單元而構成的雲母各層的層間具有負電荷，而形成以下結構：於層間，於6個四面體所形成的6員環的中心，以12配位的形態而取入有一價陽離子(cation)。 Natural mica (hereinafter referred to as mica) is an important family of rock-forming minerals. A general term for minerals that have a laminated structure and have cleavage properties (features that are easily peeled off between layers). Mica is a 2:1 type clay mineral having the following structure: 2 or 3 sandwiched between four tetrahedral structures of 3 atomic yttrium (Si) and 1 atom of aluminum (Al) oxide. An octahedral structure composed of a metal oxide/hydroxide. Since 1/4 of the tetrahedron is substituted with Al, the layers of the mica layers composed of the tetrahedral-octahedral-tetrahedron as one unit have a negative charge, and the following structure is formed: between the layers, at 6 The center of the 6-membered ring formed by the tetrahedron takes a cation in the form of a 12-coordinate.

另外，雲母可人工合成。以與天然雲母的結晶結構相同的方式含有OH的合成雲母必須於加壓下將原料混合物熔融，但天然雲母結晶中的OH經氟取代的氟雲母可於常壓下熔融而合成，故工業上合成的雲母大部分為氟雲母，所謂合成雲母通常是指此種氟雲母。例如，合成雲母中亦良好地調配至化粧品中的合成鉀金雲母[理論式：KMg3(AlSi3O10)F2]為具有將天然金雲母[理論式：KMg3(AlSi3O10)(OH)2]的OH取代為F而成的結構的合成氟金雲母。 In addition, mica can be artificially synthesized. Synthetic mica containing OH in the same manner as the crystal structure of natural mica must melt the raw material mixture under pressure, but the fluorine-mica-substituted fluoromica in the natural mica crystal can be synthesized by melting under normal pressure, so industrially Most of the synthesized mica is fluoromica, and so-called synthetic mica usually refers to such fluoromica. For example, synthetic potassium phlogopite, which is also well formulated in synthetic mica [theoretical: KMg 3 (AlSi 3 O 10 )F 2 ], has natural phlogopite [theoretical: KMg 3 (AlSi 3 O 10 ) Synthetic fluorophlogopite having a structure in which OH is substituted with F of (OH) 2 ].

市售品可例示：PMA-ST(日產化學公司製造)、MIBK-ST-L(日產化學公司製造)、TTO-51(石原產業公司製造)、銀奈米粒子(安達新產業公司製造)等。 Commercially available products include PMA-ST (manufactured by Nissan Chemical Co., Ltd.), MIBK-ST-L (manufactured by Nissan Chemical Co., Ltd.), TTO-51 (manufactured by Ishihara Sangyo Co., Ltd.), and silver nanoparticles (manufactured by Anda New Industries Co., Ltd.). .

<<聚合物無機粒子>> <<Polymer inorganic particles>>

聚合物粒子的材料可列舉：聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、 聚碸、聚碳酸酯、聚醯胺等線性聚合物；使二乙烯基苯、己三烯(hexatriene)、二乙烯基醚、二乙烯基碸、二烯丙基甲醇、伸烷基二丙烯酸酯、寡聚或聚伸烷基二醇二丙烯酸酯、寡聚或聚伸烷基二醇二甲基丙烯酸酯、伸烷基三丙烯酸酯、伸烷基四丙烯酸酯、伸烷基三甲基丙烯酸酯、伸烷基四甲基丙烯酸酯、伸烷基雙丙烯醯胺、伸烷基雙甲基丙烯醯胺、兩末端丙烯酸改質聚丁二烯寡聚物等進行均聚合或與其他聚合性單體進行聚合所得的網狀聚合物；使苯酚甲醛樹脂、三聚氰胺甲醛樹脂、苯并胍胺甲醛樹脂、脲甲醛樹脂等熱硬化性樹脂、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、三甲氧基矽烷基苯乙烯、乙烯基三甲氧基矽烷等含矽烷的單體進行均聚合或與其他聚合性單體進行共聚合所得的樹脂等。就膜強度的觀點而言，較佳為聚合物交聯粒子。 Examples of the material of the polymer particles include polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyethylene terephthalate, and polybutylene terephthalate. Linear polymer such as polyfluorene, polycarbonate, polyamine; divinylbenzene, hexatriene, divinyl ether, divinyl fluorene, diallyl methanol, alkyl diacrylate , oligomeric or polyalkylene glycol diacrylate, oligomeric or polyalkylene glycol dimethacrylate, alkylene triacrylate, alkylene tetraacrylate, alkyltrimethacrylate Ester, alkylene tetramethacrylate, alkyl bis decylamine, alkyl bis methacrylamide, two-terminal acrylic modified polybutadiene oligomer, etc. for homopolymerization or other polymerization a network polymer obtained by polymerizing a monomer; a thermosetting resin such as a phenol formaldehyde resin, a melamine formaldehyde resin, a benzoguanamine formaldehyde resin, a urea formaldehyde resin, or the like, γ-(meth)acryloxypropyltrimethoxy A decane-containing monomer such as a decane, a trimethoxydecyl styrene or a vinyltrimethoxy decane is a resin obtained by homopolymerization or copolymerization with another polymerizable monomer. From the viewpoint of film strength, polymer crosslinked particles are preferred.

市售品可例示凱米斯諾(Chemisnow)MP-1451(綜研化學公司製造)。 Commercially available products can be exemplified by Chemisnow MP-1451 (manufactured by Amika Chemical Co., Ltd.).

本發明中，粒子亦能以分散液的形式而供使用，所述分散液是藉由在適當的分散劑及溶劑中使用球磨機、棒磨機等混合裝置進行混合、分散而製備。 In the present invention, the particles can also be used in the form of a dispersion prepared by mixing and dispersing a suitable dispersant and a solvent using a mixing device such as a ball mill or a rod mill.

關於該些粒子的含量，就硬度的觀點而言，相對於固體成分100質量份，所述含量較佳為1質量份~80質量份，更佳為1質量份~50質量份，進而佳為10質量份~40質量份。 The content of the particles is preferably from 1 part by mass to 80 parts by mass, more preferably from 1 part by mass to 50 parts by mass, based on 100 parts by mass of the solid component, and more preferably from 1 part by mass to 50 parts by mass. 10 parts by mass to 40 parts by mass.

該些粒子可僅含有一種，亦可含有兩種以上。於含有兩種以上的情形時，較佳為合計量成為所述範圍。 These particles may be contained alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

<(F)交聯劑> <(F) Crosslinker>

本發明的硬化性組成物中，視需要可添加交聯劑。 A crosslinking agent may be added to the curable composition of the present invention as needed.

交聯劑可列舉：具有乙烯性不飽和鍵的聚合性單體、於分子內具有2個以上的環氧基及/或氧雜環丁基的化合物(其中，將相當於(I)成分的化合物除外)、含烷氧基甲基或羥甲基的交聯劑、封端異氰酸酯系化合物、多官能巰基化合物(較佳為脂肪族多官能巰基化合物)、公知的環氧硬化劑(其中，將相當於(I)成分的化合物除外)等。藉由添加交聯劑，可使硬化膜成為牢固的膜。 Examples of the crosslinking agent include a polymerizable monomer having an ethylenically unsaturated bond and a compound having two or more epoxy groups and/or oxetanyl groups in the molecule (wherein the component (I) is equivalent. a compound other than a compound), an alkoxymethyl group or a methylol group-containing crosslinking agent, a blocked isocyanate compound, a polyfunctional mercapto compound (preferably an aliphatic polyfunctional mercapto compound), and a known epoxy hardener (wherein Except for the compound corresponding to the component (I)). By adding a crosslinking agent, the cured film can be made into a strong film.

<<具有乙烯性不飽和鍵的聚合性單體>> <<Polymerizable monomer having ethylenic unsaturated bond>>

本發明的硬化性組成物亦可含有具有乙烯性不飽和鍵的聚合性單體。具有乙烯性不飽和鍵的聚合性單體較佳為(甲基)丙烯酸酯，更佳為多官能(甲基)丙烯酸酯，進而佳為3官能~6官能的(甲基)丙烯酸酯。 The curable composition of the present invention may also contain a polymerizable monomer having an ethylenically unsaturated bond. The polymerizable monomer having an ethylenically unsaturated bond is preferably a (meth) acrylate, more preferably a polyfunctional (meth) acrylate, and further preferably a trifunctional to hexafunctional (meth) acrylate.

具體可列舉：季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三((甲基)丙烯醯氧基乙基)異氰脲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯EO改質體、二季戊四醇六(甲基)丙烯酸酯EO改質體等。 Specific examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((meth)acryl oxime). Oxyethyl)isocyanurate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate EO modified body, dipentaerythritol hexa(meth)acrylate EO modified body Wait.

<<於分子內具有2個以上的環氧基及/或氧雜環丁基的化合物(其中，將相當於(I)成分的化合物除外)>> <<A compound having two or more epoxy groups and/or oxetanyl groups in the molecule (except for compounds corresponding to the component (I))>>

於分子內具有2個以上的環氧基的化合物的具體例可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹 脂、甲酚酚醛清漆型環氧樹脂、脂肪族環氧樹脂等。 Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy tree. Lipid, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like.

該些化合物可作為市售品而獲取。例如雙酚A型環氧樹脂為JER827、JER828、JER834、JER1001、JER1002、JER1003、JER1055、JER1007、JER1009、JER1010(以上為日本環氧樹脂(Japan Epoxy Resin)(股)製造)，艾比克隆(EPICLON)860、艾比克隆(EPICLON)1050、艾比克隆(EPICLON)1051、艾比克隆(EPICLON)1055(以上為迪愛生(DIC)(股)製造)等；雙酚F型環氧樹脂為JER806、JER807、JER4004、JER4005、JER4007、JER4010(以上為日本環氧樹脂(Japan Epoxy Resin)(股)製造)、艾比克隆(EPICLON)830、艾比克隆(EPICLON)835(以上為迪愛生(DIC)(股)製造)，LCE-21、RE-602S(以上為日本化藥(股)製造)等；苯酚酚醛清漆型環氧樹脂為JER152、JER154、JER157S70、JER157S65(以上為日本環氧樹脂(Japan Epoxy Resin)(股)製造)，艾比克隆(EPICLON)N-740、艾比克隆(EPICLON)N-770、艾比克隆(EPICLON)N-775(以上為迪愛生(DIC)(股)製造)等；甲酚酚醛清漆型環氧樹脂為艾比克隆(EPICLON)N-660、艾比克隆(EPICLON)N-665、艾比克隆(EPICLON)N-670、艾比克隆(EPICLON)N-673、艾比克隆(EPICLON)N-680、艾比克隆(EPICLON)N-690、艾比克隆(EPICLON)N-695(以上為迪愛生(DIC)(股)製造)，EOCN-1020(以上為日本化藥(股)製造)等；脂肪族環氧樹脂為艾迪科樹脂(ADEKA RESIN)EP-4080S、 艾迪科樹脂(ADEKA RESIN)EP-4085S、艾迪科樹脂(ADEKA RESIN)EP-4088S(以上為艾迪科(ADEKA)(股)製造)、賽羅西德(Celloxide)2021P、賽羅西德(Celloxide)2081、賽羅西德(Celloxide)2083、賽羅西德(Celloxide)2085、EHPE3150、艾波利得(EPOLEAD)PB 3600、艾波利得(EPOLEAD)PB 4700(以上為大賽璐(Daicel)化學工業(股)製造)等。除此以外，亦可列舉：艾迪科樹脂(ADEKA RESIN)EP-4000S、艾迪科樹脂(ADEKA RESIN)EP-4003S、艾迪科樹脂(ADEKA RESIN)EP-4010S、艾迪科樹脂(ADEKA RESIN)EP-4011S(以上為艾迪科(ADEKA)(股)製造)，NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上為艾迪科(ADEKA)(股)製造)等。該些樹脂可單獨使用一種或組合使用兩種以上。 These compounds are available as commercial products. For example, bisphenol A type epoxy resin is JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above is made by Japan Epoxy Resin), Abby clone ( EPICLON) 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, DIC), etc.; bisphenol F epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above is made by Japan Epoxy Resin), Apiclon (EPICLON) 830, Epiclon 835 (above is Di Aisheng ( DIC) (manufactured by DIC), LCE-21, RE-602S (the above is manufactured by Nippon Chemical Co., Ltd.), etc.; phenol novolac type epoxy resin is JER152, JER154, JER157S70, JER157S65 (above is Japanese epoxy resin) (Japan Epoxy Resin) (manufacturer), Abilon (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (above is Di Aisheng (DIC) ))); cresol novolac type epoxy resin is Epiclon N-660, Epiclon N-665, Abby clone (EPICL) ON) N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above is Di Aisheng) (DIC) (manufactured by the company), EOCN-1020 (above is manufactured by Nippon Chemical Co., Ltd.); aliphatic epoxy resin is ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA), Celloxide 2021P, Cyrusi Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above is Daicel) ) Chemical industry (stock) manufacturing). In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN)EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is Edico ( ADEKA) (manufacturing) and so on. These resins may be used alone or in combination of two or more.

具有氧雜環丁基的化合物的具體例可使用：亞龍氧雜環丁烷(Aron Oxetane)OXT-121、亞龍氧雜環丁烷(Aron Oxetane)OXT-221、亞龍氧雜環丁烷(Aron Oxetane)OX-SQ、亞龍氧雜環丁烷(Aron Oxetane)PNOX(以上為東亞合成(股)製造)。另外，含有氧雜環丁基的化合物較佳為單獨使用或與含有環氧基的化合物混合使用。 Specific examples of the compound having an oxetanyl group can be used: Aron Oxetane OXT-121, Aron Oxetane OXT-221, and argon oxetane Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.). Further, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

<<封端異氰酸酯化合物>> <<Capping isocyanate compound>>

本發明的硬化性組成物亦可含有封端異氰酸酯化合物。封端異氰酸酯化合物只要為具有封端異氰酸酯基的化合物，則並無特別限制，就硬化性的觀點而言，較佳為於一分子內具有2個以上 的封端異氰酸酯基的化合物。上限並無特別限定，較佳為6個以下。 The curable composition of the present invention may also contain a blocked isocyanate compound. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, and from the viewpoint of curability, it is preferably two or more in one molecule. A blocked isocyanate-based compound. The upper limit is not particularly limited, but is preferably 6 or less.

另外，封端異氰酸酯系化合物的骨架並無特別限定，只要於一分子中具有2個異氰酸酯基，則可為任意骨架，可為脂肪族、脂環族或芳香族的聚異氰酸酯，例如可較佳地使用：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、異佛爾酮二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,3-三亞甲基二異氰酸酯、1,4-四亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、1,9-九亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烷二異氰酸酯、2,2'-二乙基醚二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、鄰二甲苯二異氰酸酯、間二甲苯二異氰酸酯、對二甲苯二異氰酸酯、亞甲基雙(環己基異氰酸酯)、環己烷-1,3-二亞甲基二異氰酸酯、環己烷-1,4-二亞甲基二異氰酸酯、1,5-萘二異氰酸酯、對苯二異氰酸酯、3,3'-亞甲基二甲苯-4,4'-二異氰酸酯、4,4'-二苯基醚二異氰酸酯、四氯苯二異氰酸酯、降冰片烷二異氰酸酯、氫化1,3-伸二甲苯(xylylene)二異氰酸酯、氫化1,4-二甲苯二異氰酸酯等異氰酸酯化合物，及由該些化合物所衍生的預聚物型的骨架的化合物。該些化合物中，尤佳為甲苯二異氰酸酯(TDI)或二苯基甲烷二異氰酸酯(MDI)、六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)。 Further, the skeleton of the blocked isocyanate-based compound is not particularly limited, and may have any skeleton, and may be an aliphatic, alicyclic or aromatic polyisocyanate, as long as it has two isocyanate groups in one molecule, and for example, it is preferably used. Use: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4 -tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate 1,10-Decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene Diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-di Methyl diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'- Isocyanate compounds such as phenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylene diisocyanate, and the like A compound of the derived prepolymer type skeleton. Among these compounds, toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

本發明的組成物中的封端異氰酸酯系化合物的母結構可列舉：縮二脲型、異氰脲酸酯型、加合物型、二官能預聚物型 等。 The parent structure of the blocked isocyanate compound in the composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a difunctional prepolymer type. Wait.

形成所述封端異氰酸酯化合物的封端結構的封端劑可列舉：肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物、硫醇化合物、咪唑系化合物、醯亞胺系化合物等。該些化合物中，尤佳為選自肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物中的封端劑。 Examples of the terminal blocking agent for forming the terminal blocking structure of the blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole. A compound, a quinone imine compound, or the like. Among these compounds, a blocking agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

本發明的組成物中可使用的封端異氰酸酯化合物可作為市售品而獲取，例如可較佳地使用：克羅奈特(Coronate)AP stable M、克羅奈特(Coronate)2503、克羅奈特(Coronate)2515、克羅奈特(Coronate)2507、克羅奈特(Coronate)2513、克羅奈特(Coronate)2555、米利奧奈特(Millionate)MS-50(以上為日本聚胺酯工業(股)製造)，塔克奈特(Takenate)B-830、塔克奈特(Takenate)B-815N、塔克奈特(Takenate)B-820NSU、塔克奈特(Takenate)B-842N、塔克奈特(Takenate)B-846N、塔克奈特(Takenate)B-870N、塔克奈特(Takenate)B-874N、塔克奈特(Takenate)B-882N(以上為三井化學(股)製造)，多耐德(Duranate)17B-60P、多耐德(Duranate)17B-60PX、多耐德(Duranate)17B-60P、多耐德(Duranate)TPA-B80X、多耐德(Duranate)TPA-B80E、多耐德(Duranate)MF-B60X、多耐德(Duranate)MF-B60B、多耐德(Duranate)MF-K60X、多耐德(Duranate)MF-K60B、多耐德(Duranate)E402-B80B、多耐德 (Duranate)SBN-70D、多耐德(Duranate)SBB-70P、多耐德(Duranate)K6000(以上為旭化成化學(Asahi Kasei Chemicals)(股)製造)，德斯莫(Desmodule)BL1100、德斯莫(Desmodule)BL1265 MPA/X、德斯莫(Desmodule)BL3575/1、德斯莫(Desmodule)BL3272MPA、德斯莫(Desmodule)BL3370MPA、德斯莫(Desmodule)BL3475BA/SN、德斯莫(Desmodule)BL5375MPA、德斯莫(Desmodule)VPLS2078/2、德斯莫(Desmodule)BL4265SN、德斯莫(Desmodule)PL340、德斯莫(Desmodule)PL350、蘇米度(Sumidule)BL3175(以上為住化拜耳胺酯(股)製造)等。 The blocked isocyanate compound which can be used in the composition of the present invention can be obtained as a commercial product, and for example, Coronate AP stable M, Coronate 2503, Crowe can be preferably used. Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555, Millionate MS-50 (above for the Japanese polyurethane industry) (Stock) manufacturing), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N, Takenate B-846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above is Mitsui Chemicals) ) Manufacturing), Duranate 17B-60P, Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Duranate E402-B80B, Dornard (Duranate) SBN-70D, Duranate SBB-70P, Duranate K6000 (above made by Asahi Kasei Chemicals), Desmodule BL1100, Dess Desmodule BL1265 MPA/X, Desmodule BL3575/1, Desmodule BL3272MPA, Desmodule BL3370MPA, Desmodule BL3475BA/SN, Desmodule ) BL5375MPA, Desmodule VPLS2078/2, Desmodule BL4265SN, Desmodule PL340, Desmodule PL350, Sumidule BL3175 (above is Bayer Bayer) Amine ester (manufactured by the company) and the like.

<<多官能巰基化合物>> <<Multifunctional thiol compound>>

本發明的硬化性組成物亦可含有多官能巰基化合物。多官能巰基化合物只要為具有2個以上的巰基的化合物，則並無特別限制，較佳為具有2個~6個巰基的化合物，更佳為具有2個~4個巰基的化合物。多官能巰基化合物較佳為脂肪族多官能巰基化合物。脂肪族多官能巰基化合物的較佳例可例示：包含脂肪族烴基與-O-、-C(=O)-的組合的化合物，且脂肪族烴基的至少2個氫原子經巰基取代的化合物。 The curable composition of the present invention may also contain a polyfunctional mercapto compound. The polyfunctional fluorenyl compound is not particularly limited as long as it is a compound having two or more fluorenyl groups, and is preferably a compound having two to six fluorenyl groups, more preferably a compound having two to four fluorenyl groups. The polyfunctional mercapto compound is preferably an aliphatic polyfunctional mercapto compound. Preferable examples of the aliphatic polyfunctional mercapto compound include a compound containing a combination of an aliphatic hydrocarbon group and -O-, -C(=O)-, and a compound in which at least two hydrogen atoms of the aliphatic hydrocarbon group are substituted with a mercapto group.

脂肪族多官能巰基化合物可列舉：季戊四醇四(3-巰基丁酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷等。市售品例如可列舉：卡蘭茨(Karenz)MT-PE-1、卡蘭茨(Karenz)MT-BD-1、卡蘭茨(Karenz)MT-NR-1(昭和電工公司製造)等。 Examples of the aliphatic polyfunctional fluorenyl compound include pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy)butane, and the like. Commercially available products include, for example, Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1 (manufactured by Showa Denko Co., Ltd.), and the like.

<<環氧硬化劑>> <<Epoxy hardener>>

環氧硬化劑可列舉：脂肪族胺或芳香族胺等胺類、脂肪族酸酐或芳香族酸酐等酸酐類。 Examples of the epoxy curing agent include amines such as aliphatic amines and aromatic amines, and acid anhydrides such as aliphatic acid anhydrides and aromatic acid anhydrides.

<<其他交聯劑>> <<Other crosslinkers>>

含烷氧基甲基或羥甲基的交聯劑等其他交聯劑亦可使用公知者，具體可列舉日本專利特開2011-221494號公報的段落編號0187~段落編號0199所記載的交聯劑，將該些內容併入至本申請案說明書中。 Other cross-linking agents, such as a crosslinking agent containing an alkoxymethyl group or a hydroxymethyl group, may be used, and the cross-linking as described in Paragraph No. 0187 - Paragraph No. 0199 of JP-A-2011-221494 These are incorporated into the specification of the present application.

就可獲得優異的硬化膜的硬度的觀點而言，相對於固體成分100質量份，交聯劑的添加量較佳為0質量份~50質量份，更佳為1質量份~30質量份，進而佳為1.5質量份~20質量份，尤佳為2質量份~10質量份。 The amount of the crosslinking agent added is preferably from 0 part by mass to 50 parts by mass, more preferably from 1 part by mass to 30 parts by mass, per 100 parts by mass of the solid component, from the viewpoint of obtaining the hardness of the cured film. Further, it is preferably from 1.5 parts by mass to 20 parts by mass, particularly preferably from 2 parts by mass to 10 parts by mass.

本發明的硬化性組成物可僅含有一種交聯劑，亦可含有兩種以上。於含有兩種以上的情形時，較佳為合計量成為所述範圍。 The curable composition of the present invention may contain only one type of crosslinking agent, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<(G)界面活性劑> <(G) surfactant]

本發明的硬化性組成物亦可含有界面活性劑。界面活性劑可使用陰離子系、陽離子系、非離子系或兩性的任一種，較佳的界面活性劑為非離子系界面活性劑。界面活性劑較佳為非離子系界面活性劑，更佳為氟系界面活性劑。 The curable composition of the present invention may also contain a surfactant. As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant may be used, and a preferred surfactant is a nonionic surfactant. The surfactant is preferably a nonionic surfactant, more preferably a fluorine surfactant.

本發明中可使用的界面活性劑例如可列舉：作為市售品的美佳法(Megafac)F142D、美佳法(Megafac)F172、美佳法(Megafac)F173、美佳法(Megafac)F176、美佳法(Megafac)F177、美佳 法(Megafac)F183、美佳法(Megafac)F479、美佳法(Megafac)F482、美佳法(Megafac)F554、美佳法(Megafac)F780、美佳法(Megafac)F781、美佳法(Megafac)F781-F、美佳法(Megafac)R30、美佳法(Megafac)R08、美佳法(Megafac)F-472SF、美佳法(Megafac)BL20、美佳法(Megafac)R-61、美佳法(Megafac)R-90(迪愛生(DIC)(股)製造)，弗洛德(Fluorad)FC-135、弗洛德(Fluorad)FC-170C、弗洛德(Fluorad)FC-430、弗洛德(Fluorad)FC-431、諾貝克(Novec)FC-4430(住友3M(股)製造)，旭嘉德(Asahi Guard)AG7105、旭嘉德(Asahi Guard)7000、旭嘉德(Asahi Guard)950、旭嘉德(Asahi Guard)7600、沙福隆(Surflon)S-112、沙福隆(Surflon)S-113、沙福隆(Surflon)S-131、沙福隆(Surflon)S-141、沙福隆(Surflon)S-145、沙福隆(Surflon)S-382、沙福隆(Surflon)SC-101、沙福隆(Surflon)SC-102、沙福隆(Surflon)SC-103、沙福隆(Surflon)SC-104、沙福隆(Surflon)SC-105、沙福隆(Surflon)SC-106(旭硝子(股)製造)，艾福拓(Eftop)EF351、艾福拓(Eftop)352、艾福拓(Eftop)801、艾福拓(Eftop)802(三菱材料電子化成(股)製造)，福吉特(Ftergent)250(尼奧斯(Neos)(股)製造)，KP(信越化學工業製造)，寶理弗洛(Ployflow)(共榮社化學製造)，艾福拓(Eftop)(捷慕柯(JEMCO)製造)，美佳法(Megafac)(大日本油墨化學工業製造)、弗洛德(Fluorad)(住友3M製造)，旭嘉德(Asahi Guard)、沙福隆(Surflon)(旭硝子製)，寶理佛斯(PolyFox) (歐諾瓦(OMNOVA)公司製造)等的各系列。 Examples of the surfactant which can be used in the present invention include Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Megafac which are commercially available products. ) F177, Meijia Method (Megafac) F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (Di Aisheng) (DIC) (manufactured by) (shares), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Connaught Novec FC-4430 (made by Sumitomo 3M), Asahi Guard AG7105, Asahi Guard 7000, Asahi Guard 950, Asahi Guard 7600, Shafu Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Suffolk Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Shafu Surflon SC-105, Surflon SC-106 (made by Asahi Glass), Eftop EF351, Efto p) 352, Eftop 801, Eftop 802 (Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (made by Neos), KP (Shin-Etsu Chemical Manufacturing), Ployflow (manufactured by Kyoeisha Chemical Co., Ltd.), Eftop (made by JEMCO), Megafac (made by Dainippon Ink Chemical Industry) ), Fluorad (made by Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), PolyFox Each series (manufactured by OMNOVA).

另外，界面活性劑可列舉以下共聚物作為較佳例，所述共聚物含有下述式(W)所表示的構成單元A及構成單元B，且以四氫呋喃作為溶劑而由凝膠滲透層析法所測定的聚苯乙烯換算的重量平均分子量(Mw)為1,000以上且10,000以下。 Further, as a surfactant, a copolymer comprising a constituent unit A represented by the following formula (W) and a constituent unit B, and a tetrahydrofuran as a solvent by gel permeation chromatography is used as a preferred example. The measured polystyrene-equivalent weight average molecular weight (Mw) is 1,000 or more and 10,000 or less.

式(W)中，R1及R3分別獨立地表示氫原子或甲基，R2表示碳數1以上且4以下的直鏈伸烷基，R4表示氫原子或碳數1以上且4以下的烷基，L表示碳數3以上且6以下的伸烷基，p及q為表示聚合比的質量百分率，p表示10質量%以上且80質量%以下的數值，q表示20質量%以上且90質量%以下的數值，r表示1以上且18以下的整數，n表示1以上且10以下的整數)所述L較佳為下述式(W-2)所表示的分支伸烷基。式(W-2)中的R5表示碳數1以上且4以下的烷基，就相溶性及對被塗佈面的濡濕性的方面而言，較佳為碳數1以上且3以下的烷基，更佳為碳數2或3的烷基。 In the formula (W), R 1 and R 3 each independently represent a hydrogen atom or a methyl group, R 2 represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R 4 represents a hydrogen atom or a carbon number of 1 or more and 4 In the following alkyl group, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more. And a numerical value of 90% by mass or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less. The L is preferably a branched alkyl group represented by the following formula (W-2). R 5 in the formula (W-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more and 3 or less in terms of compatibility and wettability to a surface to be coated. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms.

式(W)中的p與q之和(p+q)較佳為p+q=100、即100質量%。 The sum (p+q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.

所述共聚物的重量平均分子量(Mw)更佳為1,500以上且5,000以下。 The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

關於本發明的硬化性組成物中的界面活性劑的含量，於調配界面活性劑的情形時，相對於硬化性組成物的總固體成分100質量份，所述含量較佳為0.001質量份~5.0質量份，更佳為0.01質量份~2.0質量份。 The content of the surfactant in the curable composition of the present invention is preferably from 0.001 part by mass to 5.0 parts by mass based on 100 parts by mass of the total solid content of the curable composition in the case of formulating the surfactant. The mass part is more preferably 0.01 parts by mass to 2.0 parts by mass.

界面活性劑可僅含有一種，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The surfactant may be contained alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

<其他成分> <Other ingredients>

本發明的硬化性組成物中，視需要可添加塑化劑、聚合抑制劑、熱酸產生劑、酸增殖劑、抗氧化劑等其他成分。關於該些成分，例如可使用日本專利特開2009-98616號公報、日本專利特開2009-244801號公報中記載者及其他公知者。另外，亦可將「高分子添加劑的新展開(日刊工業報社(股))」所記載的各種紫外線吸收劑或金屬鈍化劑等添加至本發明的硬化性組成物中。 In the curable composition of the present invention, other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid proliferator, and an antioxidant may be added as needed. For the above-mentioned components, for example, those described in JP-A-2009-98616, JP-A-2009-244801, and other known persons can be used. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikko Kogyo Co., Ltd.)" can be added to the curable composition of the present invention.

本發明中，例示含有以下成分的組成物(較佳為以下成分以外的調配量為組成物的3質量%以下的組成物)作為具體的實施形態。 In the present invention, a composition containing the following components (preferably a composition other than the following components, which is a composition of 3% by mass or less of the composition) is exemplified as a specific embodiment.

<第1實施形態> <First embodiment>

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂、 (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group,

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑為1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

<第2實施形態> <Second embodiment>

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂 (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑為1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

(F)分子內具有2個以上的環氧基的化合物(其中將相當於(I)成分的化合物除外) (F) a compound having two or more epoxy groups in the molecule (except for a compound corresponding to the component (I))

<第3實施形態> <Third embodiment>

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂 (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑為1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

(F)封端異氰酸酯系化合物 (F) blocked isocyanate compound

<第4實施形態> <Fourth embodiment>

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂 (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑為1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

(F)多官能巰基化合物 (F) polyfunctional sulfhydryl compounds

<第5實施形態> <Fifth Embodiment>

(I)具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂、 (I) an acrylic resin having an epoxy group and/or a styrene resin having an epoxy group,

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑為1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

(F)於分子內具有2個以上的環氧基的化合物(其中將相當於(I)成分的化合物除外) (F) a compound having two or more epoxy groups in the molecule (except for a compound corresponding to the component (I))

(F)封端異氰酸酯系化合物 (F) blocked isocyanate compound

<第6實施形態> <Sixth embodiment>

(I)使下述式(3)所表示的化合物、(甲基)丙烯酸、與其他自由基聚合性單體進行共聚合而成的丙烯酸系樹脂 (I) Acrylic resin obtained by copolymerizing a compound represented by the following formula (3), (meth)acrylic acid, and another radical polymerizable monomer

(J)具有羧基的重量平均分子量為1000~50,000的化合物(其中將相當於(I)成分的化合物除外) (J) a compound having a carboxyl group having a weight average molecular weight of from 1,000 to 50,000 (excluding a compound equivalent to the component (I))

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

(D)有機溶劑 (D) organic solvent

(E)平均粒徑1nm~200nm的無機粒子 (E) inorganic particles having an average particle diameter of 1 nm to 200 nm

(F)封端異氰酸酯系化合物 (F) blocked isocyanate compound

[化11] [11]

(式(3)中，R1表示氫原子、甲基或鹵素原子，R2、R3及R4分別表示氫原子或烷基。n為1~10的整數) (In the formula (3), R 1 represents a hydrogen atom, a methyl group or a halogen atom, and R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group. n is an integer of 1 to 10)

<第7實施形態> <Seventh embodiment>

於所述第1實施形態~第6實施形態中，將(E)平均粒徑為1nm~200nm的無機粒子變更為平均粒徑為1nm~200nm的聚合物粒子的實施形態 In the first embodiment to the sixth embodiment, an embodiment in which (E) inorganic particles having an average particle diameter of 1 nm to 200 nm are changed to polymer particles having an average particle diameter of 1 nm to 200 nm are used.

<第8實施形態> <Eighth Embodiment>

於所述第1實施形態~第7實施形態中進一步調配有界面活性劑的實施形態 Embodiments in which a surfactant is further formulated in the first embodiment to the seventh embodiment

<本發明的硬化膜的製造方法> <Method for Producing Cured Film of the Present Invention>

本發明的硬化膜的製造方法較佳為包括以下的(1)~(3)的步驟。 The method for producing a cured film of the present invention preferably includes the following steps (1) to (3).

(1)將本發明的硬化性組成物塗佈於基板上的步驟，(2)自所塗佈的硬化性組成物中去除溶劑的步驟， (3)進行熱硬化的步驟。 (1) a step of applying the curable composition of the present invention onto a substrate, and (2) a step of removing a solvent from the applied curable composition, (3) A step of performing thermal hardening.

於(1)塗佈步驟中，較佳為將本發明的硬化性組成物塗佈於基板上而製成含有溶劑的濕潤膜。於將硬化性組成物塗佈於基板上之前，可進行鹼清洗或電漿清洗等基板的清洗。進而，可於基板清洗後利用六甲基二矽氮烷等對基板表面進行處理。藉由進行該處理，有硬化性組成物對基板的密接性提高的傾向。 In the (1) coating step, it is preferred to apply the curable composition of the present invention to a substrate to form a wet film containing a solvent. The substrate may be cleaned such as an alkali cleaning or a plasma cleaning before the curable composition is applied onto the substrate. Further, the surface of the substrate can be treated with hexamethyldiazane or the like after the substrate is cleaned. By performing this treatment, the adhesion of the curable composition to the substrate tends to be improved.

所述基板可列舉無機基板、樹脂、樹脂複合材料等。 Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.

無機基板例如可列舉：玻璃、石英、矽酮(silicone)、氮化矽及於此種基板上蒸鍍有鉬、鈦、鋁、銅等而成的複合基板。 Examples of the inorganic substrate include glass, quartz, silicone, tantalum nitride, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.

關於樹脂，可列舉以下樹脂：聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚苯乙烯、聚碳酸酯、聚碸、聚醚碸、聚芳酯、烯丙基二甘醇碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚苯并唑、聚苯硫醚、聚環烯烴、降冰片烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸系樹脂、環氧樹脂、矽酮樹脂、離聚物(ionomer)樹脂、氰酸酯樹脂、交聯富馬酸二酯、環狀聚烯烴、芳香族醚、馬來醯亞胺-烯烴、纖維素、環硫樹脂等合成樹脂。該些基板很少以所述形態直接使用，通常視最終產品的形態而形成有例如TFT元件般的多層積層結構。 Examples of the resin include the following resins: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, Polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzoxazole, polyphenyl sulphide Ether, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, anthrone resin, ionomer resin, cyanate resin, and A synthetic resin such as a bifuranic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide resin. These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a TFT element is usually formed depending on the form of the final product.

本發明的硬化性組成物對藉由濺鍍而製膜的金屬膜或金屬氧化物的密接良好，故基板較佳為含有藉由濺鍍而製膜的金屬膜。金屬較佳為鈦、銅、鋁、銦、錫、錳、鎳、鈷、鉬、鎢、 鉻、銀、釹及該些金屬的氧化物或合金，更佳為鉬、鈦、鋁、銅及該些金屬的合金。再者，金屬或金屬氧化物可種單獨使用一種，亦可併用多種。 Since the curable composition of the present invention has good adhesion to a metal film or a metal oxide formed by sputtering, the substrate preferably contains a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, Chromium, silver, ruthenium and oxides or alloys of such metals are more preferably molybdenum, titanium, aluminum, copper and alloys of such metals. Further, the metal or the metal oxide may be used singly or in combination of two or more.

對基板的塗佈方法並無特別限定，例如可使用：噴墨法、狹縫塗佈法、噴霧法、輥式塗佈法、旋轉塗佈法、流延塗佈法、狹縫及旋轉法等方法。 The method of applying the substrate is not particularly limited, and for example, an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit method, and a spin method can be used. And other methods.

於(2)去除溶劑的步驟中，藉由減壓(真空)及/或加熱等自所塗佈的所述膜中去除溶劑，於基板上形成乾燥塗膜。溶劑去除步驟的加熱條件較佳為於70℃~130℃下加熱30秒鐘~300秒鐘左右。 In the step (2) of removing the solvent, the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably from 70 ° C to 130 ° C for about 30 seconds to 300 seconds.

進而本發明中，就提高膜硬度的觀點而言，亦可於(2)去除溶劑的步驟後、(3)進行熱硬化的步驟前，包括進行全面曝光的步驟。於該情形時，較佳為利用水銀燈或發光二極體(Light Emitting Diode，LED)燈等來進行50mJ/cm2~3000mJ/cm2左右的能量曝光。 Further, in the present invention, from the viewpoint of improving the film hardness, the step of performing total exposure may be performed before (2) the step of removing the solvent and (3) the step of performing thermal curing. In this case, it is preferable to perform energy exposure of about 50 mJ/cm 2 to 3000 mJ/cm 2 by using a mercury lamp, a light emitting diode (LED) lamp or the like.

另外，為了形成圖案，亦可於(2)溶劑去除步驟後進行圖案曝光、顯影的步驟。圖案曝光的方法較佳為使用遮罩的方法、或利用雷射等的直接描畫等方法。 Further, in order to form a pattern, the step of pattern exposure and development may be performed after the (2) solvent removal step. The method of pattern exposure is preferably a method using a mask or a method such as direct drawing using a laser or the like.

於(3)進行熱硬化的步驟中，藉由加熱而形成硬化膜。加熱溫度較佳為180℃以下，更佳為150℃以下，進而佳為130℃以下。下限值較佳為80℃以上，更佳為90℃以上。 In the step of (3) performing thermal hardening, a cured film is formed by heating. The heating temperature is preferably 180 ° C or lower, more preferably 150 ° C or lower, and still more preferably 130 ° C or lower. The lower limit is preferably 80 ° C or higher, more preferably 90 ° C or higher.

加熱的方法並無特別限定，可使用公知的方法。例如可列舉 加熱板、烘箱、紅外線加熱器等。 The method of heating is not particularly limited, and a known method can be used. For example, Heating plate, oven, infrared heater, etc.

另外，關於加熱時間，加熱板的情況下較佳為1分鐘~30分鐘左右，除此以外的情況下較佳為20分鐘~120分鐘左右。於該範圍內，可不對基板、裝置造成損傷而進行硬化。 Further, in the case of the heating time, the heating plate is preferably about 1 minute to 30 minutes, and in other cases, it is preferably about 20 minutes to 120 minutes. Within this range, the substrate and the device can be hardened without being damaged.

<硬化膜> <hardened film>

本發明的硬化膜為使本發明的硬化性組成物硬化而獲得的硬化膜。本發明的硬化膜可將依據JIS-K-7136所測定的全光線透射率設定為90%以上，進而可設定為95%以上。本發明的硬化膜的厚度可根據用途而適當決定，例如可設定為0.5μm~3μm。 The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention. The cured film of the present invention can have a total light transmittance of 90% or more measured according to JIS-K-7136, and can be set to 95% or more. The thickness of the cured film of the present invention can be appropriately determined depending on the use, and can be, for example, 0.5 μm to 3 μm.

本發明的硬化膜可較佳地用作保護膜或層間絕緣膜。另外，本發明的硬化膜較佳為藉由本發明的硬化膜的形成方法所得的硬化膜。 The cured film of the present invention can be preferably used as a protective film or an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

藉由本發明的硬化性組成物，即便於低溫下硬化亦可獲得具有充分硬度的硬化膜。例如，可獲得依據JIS5600所測定的負重750g時的鉛筆硬度為2H以上的硬化膜。使用本發明的硬化性組成物而成的保護膜由於硬化膜物性優異，故於有機EL顯示裝置或液晶顯示裝置的用途中有用。 According to the curable composition of the present invention, a cured film having sufficient hardness can be obtained even if it is cured at a low temperature. For example, a cured film having a pencil hardness of 2H or more when a load of 750 g measured according to JIS 5600 can be obtained. The protective film obtained by using the curable composition of the present invention is excellent in physical properties of the cured film, and thus is useful for use in an organic EL display device or a liquid crystal display device.

本發明的硬化性組成物由於硬化性及硬化膜特性優異，故作為微機電系統(Micro-electromechanical Systems，MEMS)用元件的結構構件，將使用本發明的硬化性組成物而形成的抗蝕劑圖案作為隔離壁，或作為機械驅動零件的一部分組入而使用。此種MEMS用元件例如可列舉：表面聲波(Surface Acoustic Wave，SAW)濾波器、體聲波(Bulk Acoustic Wave，BAW)濾波器、陀螺儀感測器、顯示器用微快門(micro-shutter)、影像感測器、電子紙、噴墨頭、生物晶片、密封劑等零件。更具體的例子是例示於日本專利特表2007-522531號公報、日本專利特開2008-250200號公報、日本專利特開2009-263544號公報等中。 Since the curable composition of the present invention is excellent in curability and cured film properties, a resist formed using the curable composition of the present invention as a structural member of a device for a microelectromechanical system (MEMS) is used. The pattern is used as a partition or as part of a mechanically driven part. Examples of such MEMS components include surface acoustic waves (Surface Acoustic) Wave, SAW) Filters, Bulk Acoustic Wave (BAW) filters, gyroscope sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, Parts such as sealants. More specific examples are exemplified in Japanese Patent Laid-Open Publication No. 2007-522531, Japanese Patent Laid-Open No. Hei. No. 2008-250200, and Japanese Patent Laid-Open No. 2009-263544.

本發明的硬化性組成物由於平坦性或透明性優異，故例如亦可用於形成：日本專利特開2011-107476號公報的圖2所記載的岸堤層(16)及平坦化膜(57)、日本專利特開2010-9793號公報的圖4(a)所記載的隔離壁(12)及平坦化膜(102)、日本專利特開2010-27591號公報的圖10所記載的岸堤層(221)及第3層間絕緣膜(216b)、日本專利特開2009-128577號公報的圖4(a)所記載的第2層間絕緣膜(125)及第3層間絕緣膜(126)、日本專利特開2010-182638號公報的圖3所記載的平坦化膜(12)及畫素分離絕緣膜(14)等。除此以外，亦可較佳地用於：用以將液晶顯示裝置中的液晶層保持於一定厚度的間隔件，傳真機(facsimile)、電子影印機、固體攝像元件等的晶載彩色濾光片(on-chip filter)的成像光學系統或光纖連接器的微透鏡。 The curable composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming the bank layer (16) and the planarizing film (57) described in Fig. 2 of JP-A-2011-107476. The partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the bank layer described in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577, Japan The planarizing film (12) and the pixel separation insulating film (14) described in FIG. 3 of Japanese Laid-Open Patent Publication No. 2010-182638. In addition, it can also be preferably used for: spacers for holding a liquid crystal layer in a liquid crystal display device at a certain thickness, and crystal color filter for a facsimile, an electronic photocopier, a solid-state imaging device, and the like. An on-chip filter imaging optical system or microlens of a fiber optic connector.

<有機EL顯示裝置> <Organic EL display device>

本發明的有機EL顯示裝置的特徵在於具有本發明的硬化膜。 The organic EL display device of the present invention is characterized by having the cured film of the present invention.

本發明的有機EL顯示裝置除了具有使用所述本發明的硬化性組成物所形成的平坦化膜或層間絕緣膜以外，並無特別限制，可列舉採用各種結構的公知的各種有機EL顯示裝置或液晶顯示 裝置。 The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and various known organic EL display devices having various structures or LCD Device.

例如，本發明的有機EL顯示裝置所具有的薄膜電晶體(Thin-Film Transistor，TFT)的具體例可列舉：非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電氣特性優異，故可與該些TFT組合而較佳地使用。 Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

圖1為有機EL顯示裝置的一例的構成概念圖，且表示底部發光型的有機EL顯示裝置中的基板的示意性剖面圖，具有平坦化膜4。 1 is a conceptual view showing an example of an organic EL display device, and shows a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4.

於玻璃基板6上形成底部閘極型的TFT1，以覆蓋該TFT1的狀態而形成包含Si3N4的絕緣膜3。於絕緣膜3中形成此處省略圖示的接觸孔(contact hole)後，於絕緣膜3上形成經由該接觸孔而連接於TFT1的配線2(高度1.0μm)。配線2為用以將TFT1間連接、或將後續步驟中形成的有機EL元件與TFT1連接的配線。 A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si 3 N 4 is formed to cover the state of the TFT 1. After forming a contact hole (not shown) in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 is a wiring for connecting the TFTs 1 or connecting the organic EL element formed in the subsequent step to the TFT 1.

進而，為了使因形成配線2所致的凹凸平坦化，以填埋由配線2所致的凹凸的狀態於絕緣膜3上形成平坦化膜4。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled.

於平坦化膜4上形成底部發光型的有機EL元件。即，於平坦化膜4上經由接觸孔7連接於配線2而形成包含ITO的第一電極5。另外，第一電極5相當於有機EL元件的陽極。 A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is formed on the planarizing film 4 via the contact hole 7 and connected to the wiring 2. Further, the first electrode 5 corresponds to the anode of the organic EL element.

形成覆蓋第一電極5的邊緣的形狀的絕緣膜8，藉由設置該絕緣膜8，可防止第一電極5與此後的步驟中形成的第二電極之間的短路。 The insulating film 8 having a shape covering the edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

進而，於圖1中雖未圖示，但介隔所需的圖案遮罩來依序蒸 鍍設置電洞傳輸層、有機發光層、電子傳輸層，繼而於基板上方的整個面上形成包含Al的第二電極，使用密封用玻璃板及紫外線硬化型環氧樹脂進行貼合，由此加以密封，獲得對各有機EL元件連接用以驅動各有機EL元件的TFT1而成的主動式矩陣型的有機EL顯示裝置。 Further, although not shown in FIG. 1, the desired pattern mask is interposed to sequentially steam. A hole transport layer, an organic light-emitting layer, and an electron transport layer are plated, and then a second electrode containing Al is formed on the entire upper surface of the substrate, and is bonded by using a sealing glass plate and an ultraviolet curable epoxy resin. By sealing, an active matrix type organic EL display device in which the TFTs 1 for driving the respective organic EL elements are connected to the respective organic EL elements is obtained.

<液晶顯示裝置> <Liquid crystal display device>

本發明的液晶顯示裝置的特徵在於具有本發明的硬化膜。 The liquid crystal display device of the present invention is characterized by having the cured film of the present invention.

本發明的液晶顯示裝置除了具有使用所述本發明的硬化性組成物所形成的保護膜、平坦化膜或層間絕緣膜以外，並無特別限制，可列舉採用各種結構的公知的液晶顯示裝置。 The liquid crystal display device of the present invention is not particularly limited as long as it has a protective film, a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and a known liquid crystal display device having various configurations is exemplified.

例如，本發明的液晶顯示裝置所具有的薄膜電晶體(Thin-Film Transistor，TFT)的具體例可列舉：非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電氣特性優異，故可與該些TFT組合而較佳地使用。 Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

另外，本發明的液晶顯示裝置可採取的液晶驅動方式可列舉：扭轉向列(Twisted Nematic，TN)方式、垂直配向(Vertical Alignment，VA)方式、共面切換(In-Plane-Switching，IPS)方式、邊緣場切換(Fringe Field Switching，FFS)方式、光學補償彎曲(Optically Compensated Bend，OCB)方式等。 Further, examples of the liquid crystal driving method that can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (In-Plane-Switching, IPS). Mode, Fringe Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc.

關於面板構成，於彩色濾光片陣列(Color Filter on Array，COA)方式的液晶顯示裝置中亦可使用本發明的硬化膜，例如可用作日本專利特開2005-284291的有機絕緣膜(115)、或日本專利 特開2005-346054的有機絕緣膜(212)。另外，本發明的液晶顯示裝置可採取的液晶配向膜的具體的配向方式可列舉摩擦配向法、光配向法等。另外，亦可藉由日本專利特開2003-149647號公報或日本專利特開2011-257734號公報所記載的聚合物穩定配向(Polymer Sustained Alignment，PSA)技術來進行聚合物穩定配向。 The cured film of the present invention can also be used in a liquid crystal display device of a color filter on Array (COA) type, for example, as an organic insulating film (115) of Japanese Patent Laid-Open Publication No. 2005-284291. ), or Japanese patent An organic insulating film (212) of JP-A-2005-346054. Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention includes a rubbing alignment method, a photoalignment method, and the like. Further, the polymer stable alignment can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

另外，本發明的硬化性組成物及本發明的硬化膜不限定於所述用途，可用於各種用途。例如，除了平坦化膜或層間絕緣膜以外，亦可較佳地用於保護膜、或用以將液晶顯示裝置中的液晶層保持於一定厚度的間隔件、或於固體攝像元件中設置於彩色濾光片上的微透鏡等。 Further, the curable composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the interlayer insulating film, it may be preferably used for a protective film, a spacer for holding a liquid crystal layer in a liquid crystal display device at a certain thickness, or a color for a solid-state imaging device. Microlenses and the like on the filter.

圖2為表示主動式矩陣方式的液晶顯示裝置10的一例的概念性剖面圖。該液晶顯示裝置10為於背面上具有背光單元12的液晶面板，並且液晶面板中，配置有與貼附有偏光膜的2片玻璃基板14、玻璃基板15之間所配置的所有畫素相對應的TFT16的元件。對於形成於玻璃基板上的各元件，通過形成於硬化膜17中的接觸孔18而進行形成畫素電極的ITO透明電極19的配線。於ITO透明電極19上，設有液晶20的層及配置有黑色矩陣的紅色-綠色-藍色(Red Green Blue，RGB)彩色濾光片22。 FIG. 2 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed with all the pixels arranged between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached. The components of the TFT16. The wiring of the ITO transparent electrode 19 forming the pixel electrode is formed by the contact hole 18 formed in the cured film 17 for each element formed on the glass substrate. On the ITO transparent electrode 19, a layer of the liquid crystal 20 and a red-green-blue (RGB) color filter 22 in which a black matrix is disposed are provided.

背光的光源並無特別限定，可使用公知的光源。例如可列舉：白色LED、藍色/紅色/綠色等的多色LED、螢光燈(冷陰極管)、有機EL等。 The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue/red/green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.

另外，液晶顯示裝置可設定為三維(Three dimensions，3D)(立體視)型，亦可設定為觸控面板型。進而，亦可設定為可撓型，可用作日本專利特開2011-145686號公報所記載的第2層間絕緣膜(48)、或日本專利特開2009-258758號公報所記載的層間絕緣膜(520)。 Further, the liquid crystal display device can be set to a three-dimensional (3D) (stereoscopic) type, or can be set to a touch panel type. In addition, the second interlayer insulating film (48) described in JP-A-2011-145686 or the interlayer insulating film described in JP-A-2009-258758 can be used. (520).

觸控面板型可列舉：所謂單元內(in-cell)型(例如日本專利特表2012-517051的圖6)、所謂單元上(on-cell)型(例如日本專利特開2012-43394的圖14)、單片式玻璃觸控(One Glass Solution，OGS)型、單層電容式觸控(Touch On Lens，TOL)型、其他構成(例如日本專利特開2013-164871的圖6)。例如，本發明的硬化膜適合用於圖3中的各層之間的保護膜，另外，亦適合用於將觸控面板的檢測電極間隔開的層間絕緣膜。 The touch panel type is exemplified by an in-cell type (for example, FIG. 6 of Japanese Patent Laid-Open No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Laid-Open No. 2012-43394). 14), One Glass Solution (OGS) type, single-layer capacitive touch (Touch On Lens, TOL) type, and other configurations (for example, FIG. 6 of Japanese Patent Laid-Open Publication No. 2013-164871). For example, the cured film of the present invention is suitably used for the protective film between the layers in FIG. 3, and is also suitable for the interlayer insulating film which separates the detecting electrodes of the touch panel.

圖3中，110表示畫素基板，140表示液晶層，120表示對向基板，130表示感測器部。畫素基板110自圖3的下側起而依序具有偏光板111、透明基板112、共通電極113、絕緣層114、畫素電極115、配向膜116。對向基板120自圖3的下側起而依序具有配向膜121、彩色濾光片122、透明基板123。感測器部130分別具有相位差膜124、接著層126、偏光板127。另外，圖3中，125為感測器用檢測電極。本發明的硬化膜可用於畫素基板部分的絕緣層(114)(亦稱為層間絕緣膜)或各種保護膜(未圖示)、畫素基板部分的各種保護膜(未圖示)、感測器部分的各種保護膜(未圖示)等。 In Fig. 3, 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor portion. The pixel substrate 110 has a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in this order from the lower side of FIG. The counter substrate 120 has an alignment film 121, a color filter 122, and a transparent substrate 123 in this order from the lower side of FIG. The sensor unit 130 has a retardation film 124, an adhesion layer 126, and a polarizing plate 127, respectively. In addition, in Fig. 3, 125 is a detecting electrode for a sensor. The cured film of the present invention can be used for an insulating layer (114) (also referred to as an interlayer insulating film) of a pixel substrate portion, various protective films (not shown), various protective films (not shown) of a pixel substrate portion, and a feeling. Various protective films (not shown) of the detector portion, and the like.

進而，於靜態(static)驅動方式的液晶顯示裝置中，亦可藉由應用本發明而顯示設計性高的圖案。作為例子，可作為日本專利特開2001-125086號公報中記載般的聚合物網路型液晶的絕緣膜而應用本發明。 Further, in the liquid crystal display device of the static driving method, a design pattern can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.

[實施例] [Examples]

以下列舉實施例對本發明加以更具體說明。以下的實施例中所示的材料、使用量、比例、處理內容、處理順序等只要不偏離本發明的主旨，則可適當變更。因此，本發明的範圍不限定於以下所示的具體例。再者，只要無特別說明，則「份」、「%」為質量基準。 The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are the quality standards.

另外，使用以下簡稱。 In addition, the following abbreviation is used.

MATHF：甲基丙烯酸-2-四氫呋喃酯(合成品) MATHF: 2-tetrahydrofuran methacrylate (synthetic)

MAA：甲基丙烯酸(和光純藥工業公司製造) MAA: Methacrylic Acid (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65：2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥工業公司製造) V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

<具有環氧基的丙烯酸系樹脂及/或具有環氧基的苯乙烯系樹脂> <Acrylic resin having epoxy group and/or styrene resin having epoxy group>

I-1：亞如風(Arufon)UG-4000(東亞合成公司製造) I-1: Arufon UG-4000 (manufactured by East Asia Synthetic Co., Ltd.)

I-2：化合物2(合成品，參照下述) I-2: Compound 2 (synthetic product, see below)

<具有羧基的重量平均分子量為1000~50,000的化合物> <Compound having a weight average molecular weight of a carboxyl group of 1,000 to 50,000>

J-1：莊克麗(Joncryl)67(巴斯夫(BASF)公司製造)，Mw為12,500 J-1: Joncryl 67 (made by BASF), Mw is 12,500

J-2：化合物3(合成品，參照下述) J-2: Compound 3 (synthetic product, see below)

J-3：化合物4(合成品，參照下述) J-3: Compound 4 (synthetic product, see below)

<烷氧基矽烷化合物> <Alkoxydecane compound>

C-1：KBM-403(信越化學公司製造) C-1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

C-2：KBM-5103(信越化學公司製造) C-2: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<有機溶劑> <organic solvent>

D-1：丙二醇單甲醚乙酸酯(大賽璐(Daicel)公司製造) D-1: propylene glycol monomethyl ether acetate (manufactured by Daicel)

D-2：甲基乙基二甘醇(大賽璐(Daicel)公司製造) D-2: methylethyl diethylene glycol (manufactured by Daicel)

<無機粒子> <Inorganic Particles>

E-1：PMA-ST(日產化學公司製造)，二氧化矽微粒子，平均粒徑10nm~15nm E-1: PMA-ST (manufactured by Nissan Chemical Co., Ltd.), cerium oxide microparticles, with an average particle diameter of 10 nm to 15 nm

E-2：MIBK-ST-L(日產化學公司製造)，二氧化矽微粒子，平均粒徑40nm~50nm E-2: MIBK-ST-L (manufactured by Nissan Chemical Co., Ltd.), cerium oxide microparticles, average particle size 40 nm to 50 nm

E-3：TTO-51(石原產業公司製造)，氧化鈦，平均粒徑20nm E-3: TTO-51 (manufactured by Ishihara Sangyo Co., Ltd.), titanium oxide, average particle size 20 nm

E-4：銀奈米粒子(安達新產業公司製造)，平均粒徑200nm E-4: Silver nanoparticles (manufactured by Anda New Industries Co., Ltd.) with an average particle diameter of 200 nm

E-5：凱米斯諾(Chemisnow)MP-1451(綜研化學公司製造)，聚合物交聯粒子、平均粒徑100nm E-5: Chemisnow MP-1451 (manufactured by Amika Chemical Co., Ltd.), polymer crosslinked particles, average particle diameter 100 nm

<交聯劑> <crosslinker>

F-1：JER157S65(三菱化學公司製造)，於分子內具有2個以上的環氧基的化合物 F-1: JER157S65 (manufactured by Mitsubishi Chemical Corporation), a compound having two or more epoxy groups in the molecule

F-2：塔克奈特(Takenate)B870N(三井化學公司製造)，封端異氰酸酯化合物 F-2: Takenate B870N (manufactured by Mitsui Chemicals, Inc.), blocked isocyanate compound

F-3：卡蘭茨(Karenz)MT-PE-1(昭和電工公司製造)，官能基數為4的巰基化合物 F-3: Karenz MT-PE-1 (manufactured by Showa Denko Co., Ltd.), a mercapto compound having a functional group of 4

<界面活性劑> <Surfactant>

W-1：美佳法(Megafac)F554(迪愛生(DIC)公司製造)，氟系界面活性劑 W-1: Megafac F554 (manufactured by Di Aisheng (DIC) Co., Ltd.), fluorine-based surfactant

<化合物2的合成例> <Synthesis Example of Compound 2>

於具備冷凝管及攪拌機的燒瓶中，添加2,2'-偶氮雙-(2,4-二甲基戊腈)7質量份及二乙二醇乙基甲基醚200質量份。繼而，添加甲基丙烯酸12質量份(相當於聚合物中的19.5mol%)、甲基丙烯酸縮水甘油酯50質量份(相當於49.4mol%)、3-乙基(2-甲基丙烯醯氧基甲基)氧雜環丁烷8質量份(相當於6.0mol%)、N-環己基馬來醯亞胺10質量份(相當於7.9mol%)、甲基丙烯酸四氫糠基酯15質量份(相當於12.3mol%)、丙烯醯基嗎啉5質量份(相當於4.9mol%)及季戊四醇四(3-巰基丙酸酯)2質量份並進行氮氣置換後，緩緩開始攪拌。使溶液的溫度上升至70℃，於反應溶液溫度達到70℃的時刻開始聚合。其後，自聚合開始起經過30分鐘後將N-環己基馬來醯亞胺3質量份滴加至反應溶液中，1小時後將N-環己基馬來醯亞胺3質量份滴加至反應溶液中。其後，保持3小時，藉此獲得含有共聚物(I-2)的聚合物溶液。共聚物(I-2)的聚苯乙烯換算重量平均分子量(Mw)為9,000，分子量分佈(Mw/Mn)為2.0。 In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Then, 12 parts by mass of methacrylic acid (corresponding to 19.5 mol% in the polymer), 50 parts by mass of glycidyl methacrylate (corresponding to 49.4 mol%), and 3-ethyl (2-methylpropene oxime) were added. 8 parts by mass of methyl group) oxetane (corresponding to 6.0 mol%), 10 parts by mass of N-cyclohexylmaleimide (corresponding to 7.9 mol%), and tetrahydrofurfuryl methacrylate 15 mass After a part (corresponding to 12.3 mol%), 5 parts by mass of acryloylmorpholine (corresponding to 4.9 mol%), and 2 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate), and after nitrogen substitution, stirring was gradually started. The temperature of the solution was raised to 70 ° C, and polymerization was started at the time when the temperature of the reaction solution reached 70 °C. Thereafter, 3 parts by mass of N-cyclohexylmaleimide was added dropwise to the reaction solution after 30 minutes from the start of the polymerization, and after 1 hour, 3 parts by mass of N-cyclohexylmaleimide was added dropwise. In the reaction solution. Thereafter, it was kept for 3 hours, whereby a polymer solution containing the copolymer (I-2) was obtained. The copolymer (I-2) had a polystyrene-equivalent weight average molecular weight (Mw) of 9,000 and a molecular weight distribution (Mw/Mn) of 2.0.

<化合物3的合成例> <Synthesis Example of Compound 3>

<<MATHF的合成>> <<Synthesis of MATHF>>

將甲基丙烯酸(86g、1mol)冷卻至15℃，添加樟腦磺酸(4.6g、0.02mol)。於該溶液中滴加2-二氫呋喃(71g、1mol、1.0當量)。攪拌1小時後，添加飽和碳酸氫鈉(500mL)，利用乙酸乙酯(500mL)進行萃取，以硫酸鎂加以乾燥後，將不溶物過濾後於40℃以下減壓濃縮，將殘渣的黃色油狀物減壓蒸餾，以無色油狀物的形式獲得沸點(bp.)54℃~56℃/3.5mmHg餾分的甲基丙烯酸四氫-2H-呋喃-2-基酯(MATHF)125g(產率為80%)。 Methyl acrylate (86 g, 1 mol) was cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2-Dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate, and then filtered, and the insoluble materials were filtered and concentrated under reduced pressure at 40 ° C or less to give a yellow oily residue. Distillation under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C to 56 ° C / 3.5 mmHg as a colorless oil. 80%).

<<化合物3的合成>> <<Synthesis of Compound 3>>

於三口燒瓶中加入PGMEA(丙二醇單甲醚乙酸酯)(89g)，於氮氣環境下升溫至90℃。於該溶液中用2小時滴加使MAA(成為所有單體成分中的9.5mol%的量)、MATHF(成為所有單體成分中的43mol%的量)、MMA(相當於所有單體成分中的47.5mol%)、V-65(相對於所有單體成分的合計量100mol%而相當於4mol%)於室溫下溶解於PGMEA(89g)中而成的溶液。滴加結束後攪拌2小時，使反應結束。藉此獲得聚合物化合物3。再者，以溶劑以外的成分(稱為固體成分)的濃度成為40質量%的方式進行調整。Mw為15,000。 PGMEA (propylene glycol monomethyl ether acetate) (89 g) was placed in a three-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (to be 9.5 mol% of all monomer components), MATHF (to be 43 mol% of all monomer components), and MMA (corresponding to all monomer components) were added dropwise to the solution over 2 hours. A solution obtained by dissolving 46.5 mol%) and V-65 (100 mol% based on the total amount of all monomer components and corresponding to 4 mol%) in PGMEA (89 g) at room temperature. After the completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, the polymer compound 3 was obtained. In addition, the concentration of the component other than the solvent (referred to as a solid component) was adjusted to 40% by mass. Mw is 15,000.

<化合物4的合成例> <Synthesis Example of Compound 4>

依照日本專利第5036269號公報所記載的合成方法，合成下述結構式所表示的化合物4(J-3)。 According to the synthesis method described in Japanese Patent No. 5036269, the compound 4 (J-3) represented by the following structural formula is synthesized.

[化12] [化12]

<硬化性組成物的調和> <Reconciliation of hardening composition>

如下述表所記載般將各成分調配、攪拌而製成溶劑溶液，利用孔徑0.3μm的聚四氟乙烯製過濾器進行過濾，獲得本發明的硬化性組成物。除了固體成分濃度以外，下述表的各成分的單位為質量份。另外，有機溶劑以外表示固體成分換算的質量份。 Each component was prepared and stirred to prepare a solvent solution, and the mixture was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.3 μm to obtain a curable composition of the present invention. The unit of each component of the following table is a part by mass in addition to the solid content concentration. Further, the organic solvent means a part by mass in terms of solid content.

<鉛筆硬度的評價> <Evaluation of pencil hardness>

將所述調和的各組成物旋塗於玻璃基板上，於90℃下進行120秒鐘的預烘烤，獲得膜厚2.0μm的塗佈膜。繼而，藉由高壓水銀燈進行500mJ/cm2(i射線換算)的光照射，進而利用烘箱於120℃下烘烤60分鐘，藉此製成硬化膜。 Each of the blended compositions was spin-coated on a glass substrate, and prebaked at 90 ° C for 120 seconds to obtain a coating film having a film thickness of 2.0 μm. Then, it was irradiated with light of 500 mJ/cm 2 (i-ray conversion) by a high pressure mercury lamp, and further baked at 120 ° C for 60 minutes in an oven to prepare a cured film.

對所得的硬化膜利用依據JIS5600的方法(負重750g)進行鉛筆硬度試驗，評價膜強度。2H以上為實用範圍。 The obtained cured film was subjected to a pencil hardness test by a method according to JIS 5600 (weight: 750 g) to evaluate the film strength. 2H or more is a practical range.

<透射率的評價> <Evaluation of Transmittance>

將所調和的各組成物旋塗於玻璃基板上，於90℃下進行120秒鐘的預烘烤，獲得膜厚為2.0μm的塗佈膜。繼而，藉由高壓水 銀燈來進行500mJ/cm2(i射線換算)的光照射，進而利用烘箱於120℃下進行60分鐘烘烤，藉此製成硬化膜。 Each of the blended compositions was spin-coated on a glass substrate, and prebaked at 90 ° C for 120 seconds to obtain a coating film having a film thickness of 2.0 μm. Then, light irradiation of 500 mJ/cm 2 (i-ray conversion) was performed by a high pressure mercury lamp, and further baked at 120 ° C for 60 minutes in an oven to prepare a cured film.

對所得的硬化膜使用霧度計(haze meter)NDH7000(日本電色工業公司製造)來測定全光線透射率。全光線透射率90%以上為實用範圍。 The total light transmittance was measured using a haze meter NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) on the obtained cured film. A total light transmittance of 90% or more is a practical range.

如由所述表所表明，本發明的組成物即便於低溫下硬化亦具有高硬度。 As indicated by the above table, the composition of the present invention has high hardness even if it is hardened at a low temperature.

Claims (13)

一種硬化性組成物，含有：I：具有環氧基的丙烯酸系樹脂及具有環氧基的苯乙烯系樹脂的至少一種；J：具有羧基的重量平均分子量為1000~50,000的化合物，其中，將相當於所述I成分的化合物除外；C：烷氧基矽烷化合物；D：有機溶劑；以及E：平均粒徑為1nm~200nm的無機粒子及平均粒徑為1nm~200nm的聚合物粒子的至少一種；且所述無機粒子及聚合物粒子的平均空隙率小於10%，所述平均空隙率為200個所述粒子的由電子顯微鏡所得的粒子的剖面圖像的空隙部分與粒子剖面之面積比的算術平均值，並且使所述硬化性組成物硬化而成的膜的依據JIS-K-7136測得的全光線透射率為90%以上。 A curable composition comprising: at least one of an acrylic resin having an epoxy group and a styrene resin having an epoxy group; J: a compound having a weight average molecular weight of a carboxyl group of from 1,000 to 50,000, wherein Except for the compound of the I component; C: alkoxydecane compound; D: organic solvent; and E: at least inorganic particles having an average particle diameter of 1 nm to 200 nm and at least polymer particles having an average particle diameter of 1 nm to 200 nm And an average void ratio of the inorganic particles and the polymer particles is less than 10%, and the average void ratio is an area ratio of a void portion of the cross-sectional image of the particles obtained by an electron microscope of 200 particles to a particle cross-section The arithmetic mean value and the film obtained by hardening the curable composition have a total light transmittance of 90% or more as measured according to JIS-K-7136. 如申請專利範圍第1項所述的硬化性組成物，更含有F：交聯劑。 The curable composition according to claim 1, further comprising F: a crosslinking agent. 如申請專利範圍第2項所述的硬化性組成物，其中所述F：交聯劑包含封端異氰酸酯化合物。 The curable composition according to claim 2, wherein the F:crosslinking agent comprises a blocked isocyanate compound. 如申請專利範圍第2項或第3項所述的硬化性組成物，其中所述F：交聯劑包含多官能巰基化合物。 The sclerosing composition according to claim 2, wherein the F:crosslinking agent comprises a polyfunctional fluorenyl compound. 如申請專利範圍第1項至第3項中任一項所述的硬化性組成物，其中所述硬化性組成物的固體成分濃度為20質量%~40質 量%。 The curable composition according to any one of claims 1 to 3, wherein the hardening composition has a solid content concentration of 20% by mass to 40% the amount%. 一種硬化膜的製造方法，其特徵在於包括：將如申請專利範圍第1項至第5項中任一項所述的硬化性組成物塗佈於基板上的步驟；自所塗佈的硬化性組成物中去除溶劑的步驟；以及進行熱硬化的步驟。 A method for producing a cured film, comprising the step of applying a curable composition according to any one of claims 1 to 5 to a substrate; a step of removing the solvent in the composition; and a step of performing thermal hardening. 如申請專利範圍第6項所述的硬化膜的製造方法，其中所述進行熱硬化的步驟中的熱硬化溫度為150℃以下。 The method for producing a cured film according to the sixth aspect of the invention, wherein the heat hardening temperature in the step of performing thermal hardening is 150 ° C or lower. 如申請專利範圍第6項或第7項所述的硬化膜的形成方法，其中於所述去除溶劑的步驟後、所述進行熱硬化的步驟前，包括進行全面曝光的步驟。 The method for forming a cured film according to claim 6 or 7, wherein the step of removing the solvent and the step of performing the thermal hardening include a step of performing total exposure. 一種硬化膜，其是使如申請專利範圍第1項至第5項中任一項所述的硬化性組成物硬化而成。 A cured film obtained by curing the curable composition according to any one of claims 1 to 5. 如申請專利範圍第9項所述的硬化膜，其為保護膜。 The cured film according to claim 9, which is a protective film. 如申請專利範圍第9項或第10項所述的硬化膜，其中依據JIS5600測得的負重750g時的鉛筆硬度為2H以上。 The cured film according to claim 9 or 10, wherein the pencil hardness at a load of 750 g measured in accordance with JIS 5600 is 2H or more. 一種有機EL顯示裝置，具有如申請專利範圍第9項至第11項中任一項所述的硬化膜。 An organic EL display device having the cured film according to any one of the items 9 to 11. 一種液晶顯示裝置，具有如申請專利範圍第9項至第11項中任一項所述的硬化膜。 A liquid crystal display device having the cured film according to any one of the items 9 to 11.
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6913435B2 (en) * 2015-09-30 2021-08-04 日東電工株式会社 In-cell liquid crystal panel and liquid crystal display device
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JP7345107B2 (en) * 2019-04-15 2023-09-15 パナソニックＩｐマネジメント株式会社 photocurable composition
CN113939550B (en) * 2019-06-19 2024-05-03 住友电气工业株式会社 Resin composition, secondary coating material for optical fiber, and method for producing optical fiber

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201317331A (en) * 2011-07-22 2013-05-01 Nippon Kayaku Kk Liquid crystal sealant and liquid crystal display cell using same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200517436A (en) * 2003-10-09 2005-06-01 Nippon Kayaku Kk Resin composition for protective film
JP4617954B2 (en) * 2005-03-25 2011-01-26 日油株式会社 Resin composition for color filter protective film and color filter
KR100805688B1 (en) * 2005-09-15 2008-02-21 제일모직주식회사 Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same
JP4736679B2 (en) * 2005-09-29 2011-07-27 大日本印刷株式会社 Cured film for liquid crystal display
JP4802817B2 (en) * 2006-03-31 2011-10-26 大日本印刷株式会社 Photocurable resin composition for batch formation of different kinds of members
CN103214888A (en) * 2013-03-25 2013-07-24 佛山佛塑科技集团股份有限公司 Coating liquid for preparation of weather resistant optical grade hard coating film and corresponding hard coating film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201317331A (en) * 2011-07-22 2013-05-01 Nippon Kayaku Kk Liquid crystal sealant and liquid crystal display cell using same

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