TW201813982A - Curable composition and cured films thereof, display device comprising cured films capable of providing excellent film-forming property and low-temperature curing property - Google Patents

Curable composition and cured films thereof, display device comprising cured films capable of providing excellent film-forming property and low-temperature curing property Download PDF

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TW201813982A
TW201813982A TW106124946A TW106124946A TW201813982A TW 201813982 A TW201813982 A TW 201813982A TW 106124946 A TW106124946 A TW 106124946A TW 106124946 A TW106124946 A TW 106124946A TW 201813982 A TW201813982 A TW 201813982A
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curable composition
acrylate
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岡本優紀
目黒聡
堀田佑策
和田亜弥
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捷恩智股份有限公司
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Abstract

Disclosed is a curable composition, which comprises: a polymer (A) obtained by performing free radical polymerization of a raw material monomer containing trifunctional or higher functional (meth)acrylate (a1) in the presence of a chain transfer agent (a2); a photo-polymerization initiator (B); and a solvent (C). The curable composition of the present invention has excellent film-forming property and low-temperature curing property, and is capable of forming a cured film with high transparency.

Description

硬化性組成物及其硬化膜、包含硬化膜的顯示元件Curable composition and cured film thereof, and display element including cured film

本發明涉及一種能夠進行低溫硬化的硬化性組成物及其硬化膜、包含硬化膜的顯示元件。The present invention relates to a curable composition capable of performing low-temperature curing, a cured film thereof, and a display element including the cured film.

伴隨使用液晶顯示元件等的信息終端的急速的產品開發,不斷推進電子電路、顯示器、傳感器等在使用現有玻璃或金屬等無機材料的部位使用有機材料的產品的開發。With the rapid product development of information terminals using liquid crystal display elements, the development of products that use organic materials in areas such as existing glass or metal, such as electronic circuits, displays, and sensors, has been promoted.

使用有機材料的優點除可通過分子設計或合成條件容易調整各特性以外,還在於產品的輕量化或製程的改善。特別是,將現有的玻璃基材替代為有機材料基材,不僅有輕量化的優點,而且由於有機材料所具有的機械柔軟性,對柔性化的適合性高,並可應用輥對輥(roll to roll)等印刷方式,由此可期待製程的低成本化。另一方面,通過將現有的玻璃替代為有機材料來作為基材,產生基材的耐熱性降低的問題。The advantages of using organic materials are that, in addition to being easy to adjust each characteristic through molecular design or synthesis conditions, it also lies in the weight reduction of the product or the improvement of the manufacturing process. In particular, replacing the existing glass substrate with an organic material substrate not only has the advantage of being lightweight, but also because of the mechanical softness of organic materials, it is highly suitable for flexibility, and can be applied roll-to-roll. to roll) and other printing methods, which can reduce the cost of the manufacturing process. On the other hand, when a conventional glass is replaced with an organic material as a base material, a problem arises in that the heat resistance of the base material decreases.

推進以有機材料為基材的開發,而且在為了形成彩色濾光片保護膜、或者設於薄膜晶體管(Thin Film Transistor,TFT)與配向膜間或TFT與透明電極間的透明絕緣膜而使用硬化性樹脂組成物的情況下,為了防止伴隨對基材的熱過載的劣化,期望在低溫(比基材的玻璃化轉變點溫度低的溫度)下容易硬化、且與有機材料的適合性高的材料。又,就製程能量的減少的觀點而言,也要求硬化性樹脂的低溫下的硬化。Promote the development of organic materials as substrates, and use hardening in order to form a color filter protective film, or a transparent insulating film provided between a thin film transistor (TFT) and an alignment film, or between a TFT and a transparent electrode In the case of a flexible resin composition, in order to prevent deterioration due to thermal overload on the substrate, it is desirable that the resin is easily hardened at a low temperature (a temperature lower than the glass transition point of the substrate) and has high suitability for organic materials. material. In addition, from the viewpoint of reduction in process energy, curing at a low temperature of a curable resin is also required.

至今,進行了多種用以應對低溫硬化的研究,且提出可溶性聚合物的使用(參照專利文獻1)、硬化促進劑的使用(參照專利文獻2及專利文獻3)等,但在基礎聚合物合成的複雜度、樹脂組成物的保存穩定性方面存在問題。。To date, various studies have been conducted to deal with low-temperature hardening, and the use of soluble polymers (see Patent Document 1) and the use of hardening accelerators (see Patent Document 2 and Patent Document 3) have been proposed. There are problems in the complexity and storage stability of the resin composition. .

本發明提出一種克服所述課題、且聚合物合成容易、保存穩定性優異並能夠進行低溫硬化的樹脂組成物(參照專利文獻4)。然而,專利文獻4中記載的樹脂組成物的煆燒溫度的下限為140℃,無法用於耐熱溫度為120℃以下的聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)基板或三乙醯纖維素(Triacetyl cellulose,TAC)基板。 [現有技術文獻]The present invention proposes a resin composition that overcomes the above-mentioned problems, has easy polymer synthesis, excellent storage stability, and can be cured at low temperatures (see Patent Document 4). However, the lower limit of the firing temperature of the resin composition described in Patent Document 4 is 140 ° C, and it cannot be used for a polyethylene terephthalate (PET) substrate or triethylpyrene having a heat resistance of 120 ° C or lower. Cellulose (Triacetyl cellulose, TAC) substrate. [Prior Art Literature]

[專利文獻] [專利文獻1]日本專利特開2009-203414 [專利文獻2]國際公開2009/011304 [專利文獻3]日本專利特開2002-69311 [專利文獻4]日本專利特願2015-104566[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2009-203414 [Patent Literature 2] International Publication 2009/011304 [Patent Literature 3] Japanese Patent Laid-Open No. 2002-69311 [Patent Literature 4] Japanese Patent Laying-Open No. 2015-104566

[發明所要解決的問題] 本發明的目的在於提供一種成膜性、低溫硬化性、及硬化膜的透明性良好的硬化性組成物。 [解決問題的技術手段][Problems to be Solved by the Invention] An object of the present invention is to provide a curable composition having good film-forming properties, low-temperature curability, and transparency of a cured film. [Technical means to solve the problem]

本發明者等人發現,如下的硬化性組成物的成膜性、低溫硬化性良好,並形成透明性良好的硬化膜,所述硬化性組成物含有:聚合物(A),使包含三官能以上的(甲基)丙烯酸酯(a1)的原料單體在鏈轉移劑(a2)的存在下進行自由基聚合而獲得;光聚合起始劑(B);以及溶劑(C);基於該見解而完成了本發明。本發明包含以下的項。The present inventors have found that a hardening composition having a good film-forming property and low-temperature hardening property and forming a hardened film with good transparency, the hardening composition containing a polymer (A) and containing trifunctional The above (meth) acrylate (a1) raw material monomer is obtained by radical polymerization in the presence of a chain transfer agent (a2); a photopolymerization initiator (B); and a solvent (C); based on this knowledge The present invention has been completed. The present invention includes the following items.

[1] 一種硬化性組成物,其含有:聚合物(A),使包含三官能以上的(甲基)丙烯酸酯(a1)的原料單體在鏈轉移劑(a2)的存在下進行自由基聚合而獲得;光聚合起始劑(B);以及溶劑(C)。[1] A curable composition comprising a polymer (A), and a raw material monomer containing a trifunctional or higher (meth) acrylate (a1) is subjected to radicals in the presence of a chain transfer agent (a2) Obtained by polymerization; a photopolymerization initiator (B); and a solvent (C).

[2] 根據[1]項所述的硬化性組成物,其中鏈轉移劑(a2)為2,4-二苯基-4-甲基-1-戊烯。[2] The curable composition according to [1], wherein the chain transfer agent (a2) is 2,4-diphenyl-4-methyl-1-pentene.

[3] 根據[1]項所述的硬化性組成物,其中聚合物(A)的重量平均分子量為2,000~200,000。[3] The curable composition according to [1], wherein the weight average molecular weight of the polymer (A) is 2,000 to 200,000.

[4] 根據[1]項所述的硬化性組成物,其中光聚合起始劑(B)為選自α-胺基苯烷基酮系光聚合起始劑、醯基氧化膦系光聚合起始劑、肟酯系光聚合起始劑中的至少一種。[4] The curable composition according to [1], wherein the photopolymerization initiator (B) is selected from the group consisting of an α-aminobenzoyl ketone photopolymerization initiator and a fluorenyl phosphine oxide system photopolymerization. At least one of an initiator and an oxime ester-based photopolymerization initiator.

[5] 根據[1]項所述的硬化性組成物,其中溶劑(C)基於總溶劑的重量而含有50重量%以上的沸點為150℃以下的溶劑。[5] The curable composition according to [1], wherein the solvent (C) contains 50% by weight or more of a solvent having a boiling point of 150 ° C or less based on the weight of the total solvent.

[6] 一種硬化膜,其是使用根據[1]至[5]中任一項所述的硬化性組成物而獲得。[6] A cured film obtained using the curable composition according to any one of [1] to [5].

[7] 一種顯示元件,其包含根據[6]項所述的硬化膜。[7] A display element comprising the cured film according to [6].

[發明的效果] 本發明的硬化性組成物具有低溫硬化性,可用以形成彩色濾光片保護膜、設於TFT與配向膜間或TFT與透明電極間的透明絕緣膜等。[Effects of the Invention] The curable composition of the present invention has low-temperature curability and can be used to form a color filter protective film, a transparent insulating film provided between a TFT and an alignment film, or a TFT and a transparent electrode.

本說明書中,有時為了表示丙烯酸與甲基丙烯酸此兩者而表述為「(甲基)丙烯酸」。又,同樣地有時為了表示丙烯酸酯與甲基丙烯酸酯的一者或兩者而表述為「(甲基)丙烯酸酯」。In this specification, in order to show both acrylic acid and methacrylic acid, it may be expressed as "(meth) acrylic acid". In the same manner, in order to indicate one or both of acrylate and methacrylate, it may be expressed as "(meth) acrylate".

本說明書中,所謂「烷基」是直鏈或分支鏈的烷基,例子為甲基、乙基、丙基、正丁基、第三丁基、戊基、己基。In the present specification, the "alkyl group" is a linear or branched alkyl group, and examples thereof include methyl, ethyl, propyl, n-butyl, third butyl, pentyl, and hexyl.

<1.本發明的硬化性組成物> 本發明的硬化性組成物的特徵在於含有:聚合物(A),使包含三官能以上的(甲基)丙烯酸酯(a1)的原料單體在鏈轉移劑(a2)的存在下進行自由基聚合而獲得;光聚合起始劑(B);以及溶劑(C)。可通過根據目標特性,進一步視需要選擇添加其他添加劑並將這些均勻地混合溶解而獲得本發明的硬化性組成物。<1. The curable composition of the present invention> The curable composition of the present invention contains a polymer (A), and a raw material monomer containing a trifunctional or higher (meth) acrylate (a1) is chained. Obtained by radical polymerization in the presence of a transfer agent (a2); a photopolymerization initiator (B); and a solvent (C). The hardenable composition of the present invention can be obtained by further selecting other additives and mixing and dissolving these additives uniformly according to the target characteristics.

<1-1.三官能以上的(甲基)丙烯酸酯(a1)> 本發明中所使用的三官能以上的(甲基)丙烯酸酯(a1)只要在一分子內具有三個以上(甲基)丙烯酸酯,則並無特別限定。<1-1. Tri- or more-functional (meth) acrylate (a1)> The tri- or more-functional (meth) acrylate (a1) used in the present invention has three or more (meth) ) Acrylic acid ester is not particularly limited.

三官能以上的(甲基)丙烯酸酯(a1)的具體例為:三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧乙烷(Ethylene Oxide,EO)改性三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷(Propylene Oxide,PO)改性三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、丙三醇EO改性三(甲基)丙烯酸酯、丙三醇PO改性三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧化異氰脲酸三(甲基)丙烯酸酯、及ε-己內酯改性三-(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯等三官能的(甲基)丙烯酸酯;二-三羥甲基丙烷四(甲基)丙烯酸酯、環氧化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇烷氧基四(甲基)丙烯酸酯、及二甘油EO改性四丙烯酸酯等四官能的(甲基)丙烯酸酯;二季戊四醇五(甲基)丙烯酸酯等五官能的(甲基)丙烯酸酯;二季戊四醇六丙烯酸酯等六官能的(甲基)丙烯酸酯;以及具有羧基的多官能(甲基)丙烯酸酯。Specific examples of the trifunctional or higher (meth) acrylate (a1) are: trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide (EO) modified tri ( (Meth) acrylate, trimethylolpropane propylene oxide (PO) modified tri (meth) acrylate, glycerol tri (meth) acrylate, glycerol EO modified tri (methyl) Acrylate), glycerol PO modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, epoxidized isocyanurate tri (meth) acrylate, and ε-caprolactone modification Trifunctional (meth) acrylates such as tri- (2- (meth) acryloxyethyl) isocyanurate; di-trimethylolpropane tetra (meth) acrylate, pentaerythritol epoxidized Tetrafunctional (meth) acrylates such as tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, and diglycerol EO modified tetraacrylate; Pentaerythritol penta (meth) acrylate and other pentafunctional (meth) acrylates; dipentaerythritol hexaacrylate and other functional (meth) acrylates; And polyfunctional (meth) acrylates having a carboxyl group.

所述化合物中,就聚合物的製造容易度及聚合物的物性,例如製造時不會引起聚合物的析出的程度的溶解性的高低、或容易處理的聚合物溶液的黏度低的觀點而言,優選為二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯。Among these compounds, from the viewpoints of the ease of production of the polymer and the physical properties of the polymer, such as the level of solubility that does not cause precipitation of the polymer during production, or the low viscosity of a polymer solution that is easy to handle. , Preferably dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate.

三官能以上的(甲基)丙烯酸酯(a1)可使用下述般的市售品。As the trifunctional or higher (meth) acrylate (a1), commercially available products described below can be used.

作為三官能丙烯酸酯的三羥甲基丙烷三丙烯酸酯的市售品的具體例為:NK酯(NK Ester)TMPT(商品名,新中村工業股份有限公司)、TMPTA(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)、及亞羅尼斯(Aronix)M-309(商品名,東亞合成股份有限公司);三羥甲基丙烷EO改性三丙烯酸酯的市售品的具體例為:TMPEOTA(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)、亞羅尼斯(Aronix)M-350、亞羅尼斯(Aronix)M-360(均為商品名,東亞合成股份有限公司);三羥甲基丙烷PO改性三丙烯酸酯的市售品的具體例為:艾柏西路(EBECRYIL)135(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)、亞羅尼斯(Aronix)M-310、亞羅尼斯(Aronix)M-321(均為商品名,東亞合成股份有限公司);丙三醇PO改性三丙烯酸酯的市售品的具體例為OTA 480(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司);環氧化異氰脲酸三丙烯酸酯的市售品的具體例為NK酯(NK Ester)A-9300(商品名,新中村工業股份有限公司);ε-己內酯改性三-(2-丙烯醯氧基乙基)異氰脲酸酯的市售品的具體例為NK酯(NK Ester)A-9300-1CL(商品名,新中村工業股份有限公司)。Specific examples of commercially available products of trimethylolpropane triacrylate as trifunctional acrylate are: NK Ester (NK Ester) TMPT (trade name, Shin Nakamura Industry Co., Ltd.), TMPTA (trade name, Daiceleo) Daicel Allnex Co., Ltd.) and Aronix M-309 (trade name, East Asia Synthesis Co., Ltd.); specific examples of commercially available products of trimethylolpropane EO modified triacrylate For: TMPEOTA (trade name, Daicel Allnex Co., Ltd.), Aronix M-350, Aronix M-360 (all are trade names, East Asia Synthetic Co., Ltd. Company); Specific examples of commercially available products of trimethylolpropane PO modified triacrylate are: EBECRYIL 135 (trade name, Daicel Allnex Co., Ltd.), Asia Aronix M-310, Aronix M-321 (both trade names, East Asia Synthesis Co., Ltd.); specific examples of commercially available products of glycerol PO modified triacrylate are OTA 480 (Trade name, Celluloids Daicel Allnex) Co., Ltd.); a specific example of a commercially available product of epoxidized isocyanuric acid triacrylate is NK Ester A-9300 (trade name, Shin Nakamura Industry Co., Ltd.); A specific example of a commercially available product of ester-modified tri- (2-propenyloxyethyl) isocyanurate is NK Ester (NK Ester) A-9300-1CL (trade name, Shin Nakamura Industry Co., Ltd.) .

作為三官能甲基丙烯酸酯的三羥甲基丙烷三甲基丙烯酸酯的市售品的具體例為NK酯(NK Ester)TMPT(商品名,新中村工業股份有限公司)。A specific example of a commercially available product of trimethylolpropane trimethacrylate, which is a trifunctional methacrylate, is NK Ester TMPT (trade name, Shin Nakamura Industry Co., Ltd.).

作為四官能丙烯酸酯的二-三羥甲基丙烷四丙烯酸酯的市售品的具體例為:NK酯(NK Ester)AD-TMP(商品名,新中村工業股份有限公司)、艾柏西路(EBECRYIL)140、及艾柏西路(EBECRYIL)1142(均為商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)、亞羅尼斯(Aronix)M-408(商品名,東亞合成股份有限公司);環氧化季戊四醇四丙烯酸酯的市售品的具體例為NK酯(NK Ester)ATM-35E(商品名,新中村工業股份有限公司);季戊四醇四丙烯酸酯的市售品的具體例為NK酯(NK Ester)A-TMMT(商品名,新中村工業股份有限公司);季戊四醇烷氧基四丙烯酸酯的市售品的具體例為艾柏西路(EBECRYIL)40(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司);二甘油EO改性四丙烯酸酯的市售品的具體例為亞羅尼斯(Aronix)M-460(商品名,東亞合成股份有限公司)。Specific examples of commercially available products of di-trimethylolpropane tetraacrylate as a tetrafunctional acrylate are: NK Ester (NK Ester) AD-TMP (trade name, Shin Nakamura Industrial Co., Ltd.), Abbey Road (EBECRYIL) 140, and EBECRYIL 1142 (both trade names, Daicel Allnex Co., Ltd.), Aronix M-408 (trade name, East Asia Synthetic) Co., Ltd.); specific examples of commercially available products of epoxidized pentaerythritol tetraacrylate are NK ester (NK Ester) ATM-35E (trade name, Shin Nakamura Industry Co., Ltd.); specific examples of commercially available products of pentaerythritol tetraacrylate NK Ester (NK Ester) A-TMMT (trade name, Shin Nakamura Industrial Co., Ltd.); a specific example of a commercially available product of pentaerythritol alkoxytetraacrylate is EBECRYIL 40 (trade name, contest Daicel Allnex Co., Ltd.); A specific example of a commercially available product of diglycerol EO modified tetraacrylate is Aronix M-460 (trade name, East Asia Synthetic Co., Ltd.).

作為六官能丙烯酸酯的二季戊四醇六丙烯酸酯的市售品的具體例為:NK酯(NK Ester)A-DPH(商品名,新中村工業股份有限公司)、及DPHA(商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)。Specific examples of commercially available products of dipentaerythritol hexaacrylate as hexafunctional acrylates are: NK Ester (NK Ester) A-DPH (trade name, Shin Nakamura Industrial Co., Ltd.), and DPHA (trade name, Daiceleo) (Daicel Allnex).

具有羧基的多官能丙烯酸酯的市售品的具體例為亞羅尼斯(Aronix)M-510及亞羅尼斯(Aronix)M-520(均為商品名,東亞合成股份有限公司)。Specific examples of commercially available products of a polyfunctional acrylate having a carboxyl group are Aronix M-510 and Aronix M-520 (both are trade names of Toa Synthetic Co., Ltd.).

作為包含作為三官能丙烯酸酯的環氧化異氰脲酸三丙烯酸酯的混合物的環氧化異氰脲酸二丙烯酸酯及環氧化異氰脲酸三丙烯酸酯的混合物的市售品的具體例為亞羅尼斯(Aronix)M-313(30重量%~40重量%)及亞羅尼斯(Aronix)M-315(3重量%~13重量%)(均為商品名,東亞合成股份有限公司,括號內的含有率為混合物中的環氧化異氰脲酸二丙烯酸酯的含有率的目錄記載值)。A specific example of a commercially available product of a mixture of an epoxidized isocyanurate diacrylate and an epoxidized isocyanurate triacrylate that is a mixture of epoxidized isocyanurate triacrylate as a trifunctional acrylate is a Aronix M-313 (30% to 40% by weight) and Aronix M-315 (3% to 13% by weight) (both trade names, East Asia Synthesis Co., Ltd., brackets (The content rate is the catalog value of the content rate of the epoxidized isocyanurate diacrylate in the mixture).

作為三官能丙烯酸酯的季戊四醇三丙烯酸酯、及作為四官能丙烯酸酯的季戊四醇四丙烯酸酯的混合物的市售品的具體例為PETIA、PETRA、及PETA(均為商品名,大賽璐奧諾斯(Daicel Allnex)股份有限公司)、亞羅尼斯(Aronix)M-306(65重量%~70重量%)、亞羅尼斯(Aronix)M-305(55重量%~63重量%)、亞羅尼斯(Aronix)M-303(30重量%~60重量%)、亞羅尼斯(Aronix)M-452(25重量%~40重量%)、及亞羅尼斯(Aronix)M-450(未滿10重量%)(均為商品名,東亞合成股份有限公司,括號內的含有率為混合物中的季戊四醇三丙烯酸酯的含有率的目錄記載值)。Specific examples of commercially available products of pentaerythritol triacrylate as a trifunctional acrylate, and a mixture of pentaerythritol tetraacrylate as a tetrafunctional acrylate are PETIA, PETRA, and PETA (all are trade names, Daicel Onos ( Daicel Allnex Co., Ltd.), Aronix M-306 (65% to 70% by weight), Aronix M-305 (55% to 63% by weight), Aronix ( Aronix) M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight), and Aronix M-450 (less than 10% by weight) ) (Both are trade names, Toa Synthetic Co., Ltd., and the content rates in parentheses are the listed values of the content rates of pentaerythritol triacrylate in the mixture).

作為五官能丙烯酸酯的二季戊四醇五丙烯酸酯、及作為六官能丙烯酸酯的二季戊四醇六丙烯酸酯的混合物的市售品的具體例為亞羅尼斯(Aronix)M-403(50重量%~60重量%)、亞羅尼斯(Aronix)M-400(40重量%~50重量%)、亞羅尼斯(Aronix)M-402(30重量%~40重量%)、亞羅尼斯(Aronix)M-404(30重量%~40重量%)、亞羅尼斯(Aronix)M-406(25重量%~35重量%)、及亞羅尼斯(Aronix)M-405(10重量%~20重量%)(商品名,東亞合成股份有限公司,括號內的含有率為混合物中的季戊四醇五丙烯酸酯的含有率的目錄記載值)。A specific example of a commercially available product of a mixture of dipentaerythritol pentaacrylate as a pentafunctional acrylate and dipentaerythritol hexaacrylate as a hexafunctional acrylate is Aronix M-403 (50% to 60% by weight). %), Aronix M-400 (40% to 50% by weight), Aronix M-402 (30% to 40% by weight), Aronix M-404 (30% to 40% by weight), Aronix M-406 (25% to 35% by weight), and Aronix M-405 (10% to 20% by weight) (Products Name, East Asia Synthetic Co., Ltd., the content rate in parentheses is the catalog value of the content rate of pentaerythritol pentaacrylate in the mixture).

三官能以上的(甲基)丙烯酸酯(a1)可單獨使用,也可將兩種以上混合使用。根據本發明的方法,可在不將現有製造例中未報告的兩種以上的三官能以上的(甲基)丙烯酸酯凝膠化的情況下進行自由基聚合來製造分支聚合物。The trifunctional or higher (meth) acrylate (a1) may be used alone or as a mixture of two or more. According to the method of the present invention, a branched polymer can be produced by performing radical polymerization without gelling two or more trifunctional or higher (meth) acrylates not reported in the conventional manufacturing examples.

<1-2.鏈轉移劑(a2)> 本發明中使用的鏈轉移劑(a2)的具體例為硫代乙醇酸、巰基丙酸、2,4-二苯基-4-甲基-1-戊烯、川崎化成工業股份有限公司製造的庫諾克斯特(Quinoexter)QE-2014(商品名)、及川崎化成工業股份有限公司製造的庫諾克斯特(Quinoexter)QE-3124(商品名)。<1-2. Chain transfer agent (a2)> Specific examples of the chain transfer agent (a2) used in the present invention are thioglycolic acid, mercaptopropionic acid, and 2,4-diphenyl-4-methyl-1 -Pentene, Quinoexter QE-2014 (trade name) manufactured by Kawasaki Chemical Industry Co., Ltd., and Quinoexter QE-3124 (Products manufactured by Kawasaki Chemical Industry Co., Ltd.) name).

鏈轉移劑(a2)中,更優選為加成解裂型鏈轉移劑,加成解裂型鏈轉移劑中,就製造時的安全性及再現性的觀點而言,更優選為2,4-二苯基-4-甲基-1-戊烯。The chain transfer agent (a2) is more preferably an addition and cleavage type chain transfer agent, and the addition and cleavage type chain transfer agent is more preferably 2,4 from the viewpoints of safety and reproducibility during production. -Diphenyl-4-methyl-1-pentene.

鏈轉移劑(a2)可單獨使用,也可將兩種以上混合使用。The chain transfer agent (a2) may be used alone or as a mixture of two or more kinds.

<1-3.具有聚合性雙鍵的化合物(a3)> 在本發明的硬化性組成物中含有的聚合物(A)的原料單體中除三官能以上的(甲基)丙烯酸酯(a1)以外,可進而包含具有聚合性雙鍵的化合物(a3)。<1-3. Compound (a3) having a polymerizable double bond> The raw material monomer of the polymer (A) contained in the curable composition of the present invention is excluding a trifunctional (meth) acrylate (a1) ) And may further include a compound (a3) having a polymerizable double bond.

本發明中,具有聚合性雙鍵的化合物(a3)大致分為「具有烷氧基矽烷基及聚合性雙鍵的化合物」、「具有羧基及聚合性雙鍵的化合物」及「不具有烷氧基矽烷基及羧基而具有聚合性雙鍵的化合物」。In the present invention, the compound (a3) having a polymerizable double bond is roughly classified into "a compound having an alkoxysilyl group and a polymerizable double bond", "a compound having a carboxyl group and a polymerizable double bond", and "a compound having no alkoxy group" A silyl group and a carboxyl group and a polymerizable double bond. "

通過包含具有烷氧基矽烷基及聚合性雙鍵的化合物作為具有聚合性雙鍵的化合物(a3),具有提高使用本發明的硬化性組成物而形成的硬化膜與基底的密接性的效果。通過包含具有羧基及聚合性雙鍵的化合物,具有提高本發明的硬化性組成物的鹼溶解性的效果。The inclusion of a compound having an alkoxysilyl group and a polymerizable double bond as the compound (a3) having a polymerizable double bond has the effect of improving the adhesion between the cured film formed using the curable composition of the present invention and the substrate. By including a compound having a carboxyl group and a polymerizable double bond, there is an effect of improving the alkali solubility of the curable composition of the present invention.

又,通過包含不具有烷氧基矽烷基及羧基而具有聚合性雙鍵的化合物作為具有聚合性雙鍵的化合物(a3),具有使其他特性變化的效果。效果的例子為硬化膜的折射率控制效果。Moreover, when the compound (a3) which has a polymerizable double bond is contained without having an alkoxysilyl group and a carboxyl group, it has the effect of changing another characteristic. An example of the effect is the refractive index control effect of the cured film.

具有聚合性雙鍵的化合物(a3)可單獨使用,也可將兩種以上混合使用。The compound (a3) having a polymerizable double bond may be used alone or as a mixture of two or more kinds.

為了使聚合物(A)更強地表現出分支聚合物的性質,優選為在原料單體100質量%中,具有聚合性雙鍵的化合物(a3)的總量為0質量%~49.9質量%。In order to make the polymer (A) more strongly exhibit the properties of the branched polymer, it is preferable that the total amount of the compound (a3) having a polymerizable double bond in 100% by mass of the raw material monomer is 0% to 49.9% by mass. .

<1-3-1.具有烷氧基矽烷基及聚合性雙鍵的化合物> 本發明中可使用的具有烷氧基矽烷基及聚合性雙鍵的化合物為每一分子具有至少一個烷氧基矽烷基、且每一分子具有一個~兩個聚合性雙鍵的化合物。<1-3-1. Compound having an alkoxysilyl group and a polymerizable double bond> The compound having an alkoxysilyl group and a polymerizable double bond that can be used in the present invention has at least one alkoxy group per molecule A silane-based compound having one to two polymerizable double bonds per molecule.

具有烷氧基矽烷基及聚合性雙鍵的化合物的具體例為:(甲基)丙烯酸3-(三甲氧基矽烷基)丙酯及(甲基)丙烯酸3-(三乙氧基矽烷基)丙酯等具有烷氧基矽烷基的(甲基)丙烯酸酯;乙烯基三甲氧基矽烷及乙烯基三乙氧基矽烷等具有烷氧基矽烷基及乙烯基的化合物;以及對苯乙烯基三甲氧基矽烷及對苯乙烯基三乙氧基矽烷等具有烷氧基矽烷基及苯乙烯基的化合物。Specific examples of the compound having an alkoxysilyl group and a polymerizable double bond are 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (triethoxysilyl) (meth) acrylate. (Meth) acrylates having alkoxysilyl groups such as propyl esters; compounds having alkoxysilyl groups and vinyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane; and p-styryltrimethyl Compounds having an alkoxysilyl group and a styryl group, such as oxysilane and p-styryltriethoxysilane.

這些具有烷氧基矽烷基及聚合性雙鍵的化合物的具體例中,優選為容易獲取、且製成聚合物時的與光聚合起始劑(B)的相容性良好的甲基丙烯酸3-(三甲氧基矽烷基)丙酯及乙烯基三甲氧基矽烷,進而優選為甲基丙烯酸3-(三甲氧基矽烷基)丙酯。Among specific examples of these compounds having an alkoxysilyl group and a polymerizable double bond, methacrylic acid 3 which is easily available and has good compatibility with the photopolymerization initiator (B) when it is made into a polymer is preferred. -(Trimethoxysilyl) propyl and vinyltrimethoxysilane, and more preferably 3- (trimethoxysilyl) propyl methacrylate.

具有聚合性雙鍵的化合物(a3)內,具有烷氧基矽烷基及聚合性雙鍵的化合物可單獨使用,也可將兩種以上混合使用。Among the compounds (a3) having a polymerizable double bond, compounds having an alkoxysilyl group and a polymerizable double bond may be used alone, or two or more kinds may be used in combination.

為了使聚合物更強地表現出分支聚合物的性質、且表現出充分的密接性,優選為在原料單體100質量%中具有烷氧基矽烷基及聚合性雙鍵的化合物的總量為1質量%~30質量%。In order to make the polymer more strongly exhibit the properties of a branched polymer and exhibit sufficient adhesion, the total amount of the compound having an alkoxysilyl group and a polymerizable double bond in 100% by mass of the raw material monomer is preferably 1% to 30% by mass.

<1-3-2.具有羧基及聚合性雙鍵的化合物> 本發明中可使用的具有羧基及聚合性雙鍵的化合物為每一分子具有至少一個羧基、且每一分子具有一個~兩個聚合性雙鍵的化合物。<1-3-2. Compound having a carboxyl group and a polymerizable double bond> The compound having a carboxyl group and a polymerizable double bond that can be used in the present invention has at least one carboxyl group per molecule and one to two molecules per molecule. Polymeric double bond compound.

具有羧基及聚合性雙鍵的化合物的具體例為:(甲基)丙烯酸、及丁烯酸等不飽和單羧酸;馬來酸、富馬酸、檸康酸、中康酸及衣康酸等不飽和二羧酸;以及鄰苯二甲酸單羥基乙基(甲基)丙烯酸酯等具有羧基的(甲基)丙烯酸酯。Specific examples of the compound having a carboxyl group and a polymerizable double bond are: unsaturated monocarboxylic acids such as (meth) acrylic acid and butene acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid And other unsaturated dicarboxylic acids; and (meth) acrylates having a carboxyl group, such as phthalic acid monohydroxyethyl (meth) acrylate.

這些具有羧基及聚合性雙鍵的化合物的具體例中,優選為容易獲取、且製成聚合物時的與光聚合起始劑(B)的相容性良好的(甲基)丙烯酸及鄰苯二甲酸單羥基乙基(甲基)丙烯酸酯,進而優選為(甲基)丙烯酸。Among specific examples of these compounds having a carboxyl group and a polymerizable double bond, preferred are (meth) acrylic acid and orthobenzene, which are easily available and have good compatibility with the photopolymerization initiator (B) when they are made into polymers. The dihydroxy monohydroxyethyl (meth) acrylate is more preferably (meth) acrylic acid.

具有聚合性雙鍵的化合物(a3)內,具有羧基及聚合性雙鍵的化合物可單獨使用,也可將兩種以上混合使用。Among the compounds (a3) having a polymerizable double bond, the compounds having a carboxyl group and a polymerizable double bond may be used alone, or two or more kinds may be used in combination.

為了使聚合物(A)更強地表現出分支聚合物的性質、且表現出適度的鹼溶解性,優選為在原料單體100質量%中具有羧基及聚合性雙鍵的化合物的總量為5質量%~40質量%。若為該範圍,則容易形成曝光部與未曝光部的溶解速度差,硬化性組成物具有相對於鹼顯影的良好的圖案形成性。In order for the polymer (A) to exhibit the properties of the branched polymer more strongly and to exhibit a moderate alkali solubility, the total amount of the compound having a carboxyl group and a polymerizable double bond in 100% by mass of the raw material monomer is preferably 5 mass% to 40 mass%. If it is this range, a difference in the dissolution rate between the exposed portion and the unexposed portion is easily formed, and the curable composition has a good pattern forming property with respect to alkali development.

<1-3-3.不具有烷氧基矽烷基及羧基而具有聚合性雙鍵的化合物> 本發明中可使用的不具有烷氧基矽烷基及羧基而具有聚合性雙鍵的化合物為不具有烷氧基矽烷基及羧基、且每一分子具有一個~兩個聚合性雙鍵的化合物。<1-3-3. Compounds without polymerizable double bond without alkoxysilyl group and carboxyl group> Compounds without polymerizable double bond without alkoxysilyl group and carboxyl group which can be used in the present invention are A compound having an alkoxysilyl group and a carboxyl group and having one to two polymerizable double bonds per molecule.

不具有烷氧基矽烷基及羧基而具有聚合性雙鍵的化合物的具體例為:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、及(甲基)丙烯酸正丁酯等(甲基)丙烯酸烷基酯;(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、及(甲基)丙烯酸異冰片酯等(甲基)丙烯酸環狀烷基酯;(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、丁氧基二乙二醇(甲基)丙烯酸酯、及甲氧基聚乙二醇(甲基)丙烯酸酯等具有醚鍵的(甲基)丙烯酸酯;(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯等具有環狀醚的(甲基)丙烯酸酯;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、及(甲基)丙烯酸4-羥基丁酯等具有醇性羥基的(甲基)丙烯酸酯;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯氧基聚乙二醇(甲基)丙烯酸酯、及乙氧基化O-苯基苯酚(甲基)丙烯酸酯等甲基丙烯酸芳基酯;(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸-1,1,1,3,3,3-六氟異丙酯、(甲基)丙烯酸-2,2,3,3,4,4,4-七氟丁酯、(甲基)丙烯酸-2,2,3,3,3-五氟丙酯、(甲基)丙烯酸-2,2,3,4,4,4-六氟丁酯、(甲基)丙烯酸-2,2,2-三氟乙酯、及(甲基)丙烯酸-2,2,3,3-四氟丙酯等含氟(甲基)丙烯酸酯;N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺等N-取代馬來醯亞胺;苯乙烯、以及α-丁基-ω-(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷。Specific examples of the compound which does not have an alkoxysilyl group and a carboxyl group and has a polymerizable double bond are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) Alkyl (meth) acrylates such as isopropyl acrylate and n-butyl (meth) acrylate; cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, and iso (meth) acrylate Bornyl esters such as cyclic alkyl (meth) acrylates; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxydiethylene glycol (methyl ) (Meth) acrylates with ether linkages, such as acrylates and methoxypolyethylene glycol (meth) acrylates; glycidyl (meth) acrylate, (3-ethyloxy) (meth) acrylate (Meth) acrylates having cyclic ethers such as heterocyclobutane-3-yl) methyl ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (methyl) ) (Meth) acrylates with alcoholic hydroxyl groups such as 4-hydroxybutyl acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylic acid And aryl methacrylates such as ethoxylated O-phenylphenol (meth) acrylate; trifluoroethyl (meth) acrylate, -1,1,1,3,3 , 3-hexafluoroisopropyl ester, (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutyl ester, (meth) acrylic acid-2,2,3,3,3- Pentafluoropropyl ester, (meth) acrylic acid-2,2,3,4,4,4-hexafluorobutyl ester, (meth) acrylic acid 2, -2,2-trifluoroethyl ester, and (meth) Fluorinated (meth) acrylates such as acrylic acid-2,2,3,3-tetrafluoropropyl; N-substituted maleates such as N-phenylmaleimide and N-cyclohexylmaleimide Fluorene imine; styrene, and α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane.

<1-4.聚合物(A)的製造方法> 本發明的硬化性組成物中所含的聚合物(A)的製造方法優選為在鏈轉移劑(a2)的存在下,使用一個以上三官能以上的(甲基)丙烯酸酯(a1)的在溶液中的自由基聚合。聚合溫度只要為自所使用的聚合起始劑充分產生自由基的溫度,則並無特別限定,通常為50℃~140℃的範圍,就抑制凝膠化的觀點而言,理想為90℃以下。聚合時間也無特別限定,通常為1小時~24小時的範圍,就作業性的觀點而言,理想為8小時以下。又,該聚合可在加壓、減壓或大氣壓的任一壓力下進行。<1-4. Production method of polymer (A)> The production method of the polymer (A) contained in the curable composition of the present invention is preferably one or more of three in the presence of a chain transfer agent (a2). Radical polymerization of a functional (meth) acrylate (a1) or more in solution. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, and is usually in the range of 50 ° C to 140 ° C, and is preferably 90 ° C or lower from the viewpoint of suppressing gelation . The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours, and is preferably 8 hours or less from the viewpoint of workability. The polymerization can be performed under any pressure of increased pressure, reduced pressure, or atmospheric pressure.

所述聚合反應中使用的溶劑優選為可溶解所使用的三官能以上的(甲基)丙烯酸酯(a1)、與其併用的鏈轉移劑(a2)、視需要使用的具有聚合性雙鍵的化合物(a3)、及所獲得的聚合物(A)的溶劑。此種溶劑的具體例為甲醇、乙醇、1-丙醇、2-丙醇、丙二醇、甲基丙二醇、丙酮、甲基異丁基酮、2-丁酮、乙酸乙酯、乙酸丙酯、乙酸丁酯、四氫呋喃、乙腈、二噁烷、甲苯、二甲苯、環己酮、環戊酮、乙二醇單乙醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、二乙二醇二甲醚、二乙二醇乙基甲醚、二乙二醇單乙醚、二乙二醇丁基甲醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、N,N-二甲基甲醯胺、乙酸、及水。溶劑可為這些溶劑的一種,也可為這些溶劑的兩種以上的混合物。The solvent used in the polymerization reaction is preferably a trifunctional or higher-functional (meth) acrylate (a1), a chain transfer agent (a2) used in combination, and a compound having a polymerizable double bond, if necessary. (A3) and the solvent of the obtained polymer (A). Specific examples of such a solvent are methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methylpropanediol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, and acetic acid. Butyl ester, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethyl Methylformamide, acetic acid, and water. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

製造聚合物(A)時的溶劑的使用量只要在製造開始時成為均勻的溶液,則並無限定,為了抑制凝膠化,相對於製造時的投入總量,優選為40重量%~90重量%,更優選為60重量%~80重量%。The amount of the solvent used in the production of the polymer (A) is not limited as long as it becomes a homogeneous solution at the beginning of production. In order to suppress gelation, it is preferably 40% to 90% by weight relative to the total amount of input during production. %, More preferably 60% to 80% by weight.

製造聚合物(A)時使用的聚合起始劑可使用由於熱而產生自由基的化合物、偶氮雙異丁腈等偶氮系起始劑、或過氧化苯甲醯等過氧化物系起始劑。As the polymerization initiator used in the production of the polymer (A), a compound that generates a radical due to heat, an azo-based initiator such as azobisisobutyronitrile, or a peroxide-based compound such as benzoyl peroxide can be used. Starting agent.

熱自由基產生劑的具體例為:2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)(V-70;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙(2,4-二甲基戊腈)(V-65;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙(異丁腈)(V-60;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙(2-甲基丁腈)(V-59;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺](VF-096;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)(VAm-110;商品名,和光純藥工業股份有限公司)、2,2'-偶氮雙(異丁酸)二甲酯(V-601;商品名,和光純藥工業股份有限公司)、VPE-0201、VPE-0401、VPE-0601、VPS-1001(以上均為商品名,和光純藥工業股份有限公司)。Specific examples of the thermal radical generator are: 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70; trade name, Wako Pure Chemical Industries, Ltd. ), 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65; trade name, Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (isobutyronitrile) ) (V-60; trade name, Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2-methylbutyronitrile) (V-59; trade name, Wako Pure Chemical Industries, Ltd.) , 2,2'-azobis [N- (2-propenyl) -2-methylpropanamide] (VF-096; trade name, Wako Pure Chemical Industries, Ltd.), 2,2'-couple Azobis (N-butyl-2-methylpropanamide) (VAm-110; trade name, Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (isobutyric acid) dimethyl ( V-601; trade name, Wako Pure Chemical Industry Co., Ltd.), VPE-0201, VPE-0401, VPE-0601, VPS-1001 (the above are all trade names, Wako Pure Chemical Industries Co., Ltd.).

聚合物(A)的重量平均分子量優選為2,000~200,000,就抑制凝膠化的觀點而言,更優選為5,000~100,000。The weight average molecular weight of the polymer (A) is preferably 2,000 to 200,000, and from the viewpoint of suppressing gelation, it is more preferably 5,000 to 100,000.

本說明書中的重量平均分子量為利用膠體滲透層析(Gel Permeation Chromatography,GPC)法(管柱溫度:35℃,流速:1 mL/min)而求出的聚苯乙烯換算的值。可使用如下條件來測定重量平均分子量:標準的聚苯乙烯是使用分子量為645~285,300的聚苯乙烯(例如,安捷倫(Agilent)S-M2-10聚苯乙烯校準套裝(calibration kit)PL2010-0102(商品名,安捷倫科技(Agilent Technologies)股份有限公司)),管柱是使用PLgel MIXED-D(商品名,安捷倫科技(Agilent Technologies)股份有限公司),移動相是使用四氫呋喃(Tetrahydrofuran,THF)。此外,本說明書中的市售品的重量平均分子量為目錄記載值。The weight average molecular weight in this specification is a polystyrene-equivalent value calculated by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 mL / min). The following conditions can be used to determine the weight average molecular weight: Standard polystyrene uses polystyrene with a molecular weight of 645 to 285,300 (for example, Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (Trade name, Agilent Technologies Co., Ltd.), PLgel MIXED-D (trade name, Agilent Technologies Co., Ltd.) was used for the column, and tetrahydrofuran (THF) was used as the mobile phase. In addition, the weight average molecular weight of a commercial item in this specification is a value described in a catalog.

通過所述而獲得的聚合物(A)可以包含反應中使用的溶劑的溶液的狀態而用於本發明的硬化性組成物。該情況下的反應溶劑如後述般,優選為包含50重量%以上的沸點為150℃以下的溶劑。另外,當製備硬化性組成物時,在需要調整溶劑的組成比的情況下,可暫時將反應溶劑減壓餾去而溶解於新的組成的溶劑中來使用。The polymer (A) obtained as described above can be used in the curable composition of the present invention in the state of a solution of a solvent used in the reaction. The reaction solvent in this case is preferably a solvent having a boiling point of 150 ° C. or lower as 50% by weight or more, as described later. In addition, when preparing a hardenable composition, when it is necessary to adjust the composition ratio of the solvent, the reaction solvent can be temporarily distilled off under reduced pressure and dissolved in a solvent of a new composition for use.

就硬化性組成物的硬化性的觀點而言,通過所述而獲得的聚合物(A)優選為利用再沉澱法去除未反應物。作為利用再沉澱的純化方法,攪拌所獲得的聚合物溶液的3倍~10倍容量的無極性溶劑,向其中滴加聚合物溶液而使聚合物沉澱。在去除上清液後將沉澱物再次溶解於溶劑中,由此可進行純化。From the viewpoint of the sclerosis of the sclerosing composition, the polymer (A) obtained as described above is preferably removed by a reprecipitation method. As a purification method using reprecipitation, a non-polar solvent having a capacity of 3 to 10 times the obtained polymer solution is stirred, and the polymer solution is added dropwise to the polymer to precipitate the polymer. After the supernatant is removed, the precipitate can be purified by dissolving it in a solvent again.

所述再沉澱法中使用的無極性溶劑優選為己烷或庚烷。The non-polar solvent used in the reprecipitation method is preferably hexane or heptane.

<1-5.光聚合起始劑(B)> 本發明的硬化性組成物中所含有的光聚合起始劑只要為可引發含有聚合物(A)、光聚合起始劑(B)、及溶劑(C)的組成物的聚合者,則並無特別限定。<1-5. Photopolymerization initiator (B)> As long as the photopolymerization initiator contained in the curable composition of the present invention contains a polymer (A), a photopolymerization initiator (B), The polymer of the composition of the solvent and the solvent (C) is not particularly limited.

本發明的硬化性組成物中所含有的光聚合起始劑的具體例為:二苯甲酮、米其勒酮、4,4'-雙(二乙基胺基)二苯甲酮、氧雜蒽酮、硫雜蒽酮、異丙基氧雜蒽酮、2,4-二乙基硫雜蒽酮、2-乙基蒽醌、苯乙酮、2-羥基-2-甲基苯丙酮、2-羥基-2-甲基-4'-異丙基苯丙酮、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、樟腦醌、苯並蒽酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮(豔佳固(IRGACURE)907;商品名,日本巴斯夫(BASF Japan)股份有限公司)、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁酮-1(豔佳固(IRGACURE)369;商品名,日本巴斯夫(BASF Japan)股份有限公司)、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4,4'-二(第三丁基過氧化羰基)二苯甲酮、3,4,4'-三(第三丁基過氧化羰基)二苯甲酮、1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)(豔佳固(IRGACURE)OXE01;商品名,日本巴斯夫(BASF Japan)股份有限公司)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)(豔佳固(IRGACURE)OXE02;商品名,日本巴斯夫(BASF Japan)股份有限公司)、豔佳固(IRGACURE)OXE03(商品名,日本巴斯夫(BASF Japan)股份有限公司)、1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)(艾迪科亞庫魯茲(ADEKA ARKLS)NCI-930;商品名,艾迪科(ADEKA)股份有限公司)、艾迪科亞庫魯茲(ADEKA ARKLS)NCI-831(商品名,艾迪科(ADEKA)股份有限公司)、艾迪科奧托馬(ADEKA OPTOMER)N-1919(商品名,艾迪科(ADEKA)股份有限公司)、2,4,6-三甲基苯甲醯基二苯基氧化膦、2-(4'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(3',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(4'-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、4-[對-N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-均三嗪、1,3-雙(三氯甲基)-5-(2'-氯苯基)-均三嗪、1,3-雙(三氯甲基)-5-(4'-甲氧基苯基)-均三嗪、2-(對二甲基胺基苯乙烯基)苯並噁唑、2-(對二甲基胺基苯乙烯基)苯並噻唑、2-疏基苯並噻唑、3,3'-羰基雙(7-二乙基胺基香豆素)、2-(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二溴苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、3-(2-甲基-2-二甲基胺基丙醯基)哢唑、3,6-雙(2-甲基-2-嗎啉代丙醯基)-9-正十二烷基哢唑、1-羥基環己基苯基酮、及雙(η5 -2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦。Specific examples of the photopolymerization initiator contained in the curable composition of the present invention are: benzophenone, Michelin, 4,4'-bis (diethylamino) benzophenone, oxygen Hexanthone, thiaxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone , 2-hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyphenethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine Propane-1-one (IRGACURE) 907; trade name, BASF Japan Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1 (IRGACURE) 369; trade name, BASF Japan Co., Ltd., ethyl 4-dimethylaminobenzoate, 4-dimethylamino Isoamyl benzoate, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4,4'-tri (third butylperoxycarbonyl) benzophenone, 1, 2-Sin Ketone, 1- [4- (phenylthio) phenyl] -2- (O-benzylidene oxime) (IRGACURE) OXE01; trade name, BASF Japan Co., Ltd., Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime) (IRGACURE ) OXE02; trade name, BASF Japan Co., Ltd.), IRGACURE OXE03 (trade name, BASF Japan Co., Ltd.), 1,2-propanedione, 1- [ 4- [4- (2-Hydroxyethoxy) phenylthio] phenyl] -2- (O-acetylamoxime) (ADEKA ARKLS) NCI-930; trade name, ADEKA Co., Ltd.), ADEKA ARKLS NCI-831 (trade name, ADEKA Co., Ltd.), ADEKA OPTOMER N-1919 (trade name, ADEKA), 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -mesytriazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -mesytriazine , 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4, 6-bis (trichloromethyl) -mesytriazine, 2- (4'-pentoxystyryl) -4,6-bis (trichloromethyl) -mesytriazine, 4- [p-N , N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorobenzene ) -Mesytriazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -mesytriazine, 2- (p-dimethylaminostyryl) benzene Benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-sulfobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2 -(O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5'-tetra (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole,2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi Imidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl -2-dimethylaminopropylamido) oxazole, 3,6-bis (2-methyl-2-morpholinopropylamido) -9-n-dodecyloxazole, 1-hydroxy ring Jiji Ketone, and bis (η 5 -2,4- cyclopentadien-1-yl) - bis (2,6-difluoro-3- (lH-pyrrol-1-yl) - phenyl) titanium.

光聚合起始劑可單獨使用,也可將兩種以上混合使用。光聚合起始劑中,就硬化膜的透明性的觀點而言,優選為α-胺基苯烷基酮系、醯基氧化膦系、肟酯系光聚合起始劑。The photopolymerization initiator may be used alone or in combination of two or more. Among the photopolymerization initiators, from the viewpoint of the transparency of the cured film, an α-aminobenzoyl ketone system, a fluorenyl phosphine oxide system, and an oxime ester system photopolymerization initiator are preferred.

光聚合起始劑中,就硬化膜的透明性的觀點而言,更優選為1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)或1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)相對於光聚合起始劑的總重量而為20重量%以上。又,若為50重量%以上,則進而優選。光聚合起始劑可僅包含1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)或1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)。Among the photopolymerization initiators, from the viewpoint of the transparency of the cured film, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzyl) is more preferable. Fluorenyl oxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-ethylfluorenyl oxime), or 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidooxime) relative to the photopolymerization initiator The total weight is 20% by weight or more. Moreover, if it is 50 weight% or more, it is more preferable. The photopolymerization initiator may contain only 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzylideneoxime), ethyl ketone, 1- [9- Ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime) or 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidooxime).

<1-6.溶劑(C)> 本發明的硬化性組成物中所添加的溶劑優選為可溶解聚合物及其他添加劑的溶劑。可添加的溶劑的具體例為水、丙酮、甲基異丁基酮、甲醇、乙醇、1-丙醇、2-丙醇、丙二醇、2-丁酮、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸丁酯、乳酸乙酯、氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧基丙酸甲酯、3-氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯、四氫呋喃、乙腈、二噁烷、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、乙二醇單異丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、環己酮、環戊酮、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚、二乙二醇丁基甲醚、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇乙基甲醚、甲苯、二甲苯、γ-丁內酯、N,N-二甲基乙醯胺、及N,N-二甲基甲醯胺。這些化合物可單獨使用,也可將兩種以上組合使用。<1-6. Solvent (C)> The solvent added to the curable composition of the present invention is preferably a solvent capable of dissolving a polymer and other additives. Specific examples of solvents that can be added are water, acetone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, 2-butanone, ethyl acetate, propyl acetate, and butyl acetate. Ester, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -Methyloxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- Ethyl methyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, 2-oxo Ethyl butyrate, tetrahydrofuran, acetonitrile, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, Cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, toluene, xylene, γ-butyrolactone , N, N-dimethylacetamide, and N, N-dimethylformamide. These compounds may be used alone or in combination of two or more.

溶劑(C)優選為以在本發明的硬化性組成物中,固體成分的聚合物(A)、光聚合起始劑(B)及其他添加劑以總量計成為5重量%~90重量%的方式調配。The solvent (C) is preferably such that the polymer (A), the photopolymerization initiator (B), and other additives having a solid content in the curable composition of the present invention are 5 to 90% by weight based on the total amount. Way deployment.

優選為在本發明的硬化性組成物中所含的溶劑(C)100重量%中包含50重量%以上的沸點為150℃以下的溶劑。若設為此種溶劑組成,則減少硬化時的乾燥步驟負荷。It is preferable that 50% by weight or more of the solvent having a boiling point of 150 ° C or less is contained in 100% by weight of the solvent (C) contained in the curable composition of the present invention. With such a solvent composition, the load on the drying step during curing is reduced.

就減少本發明的硬化性组合物的乾燥步驟負荷的觀點及對人體的安全性的觀點而言,優選溶劑的例子為選自丙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、及乙酸丁酯中的至少一種。From the viewpoint of reducing the drying step load of the curable composition of the present invention and the viewpoint of safety to the human body, examples of preferred solvents are selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxy At least one of methyl propionate and butyl acetate.

<1-7.添加劑> 本發明的硬化性組成物也可含有添加劑。就使塗布均勻性、接著性、穩定性等本發明的硬化性組成物的特性提高的觀點而言,添加本發明的硬化性組成物中所任意添加的添加劑。添加劑的例子為聚合抑制劑,丙烯酸系、苯乙烯系、聚乙烯亞胺系或胺基甲酸酯系的高分子分散劑,陰離子系、陽離子系、非離子系或氟系的表面活性劑,矽酮樹脂系塗布性提高劑,矽烷偶聯劑等密接性提高劑,聚丙烯酸鈉等抗凝聚劑,環氧化合物、三聚氰胺化合物或雙疊氮化合物等熱交聯劑,受阻系苯酚等抗氧化劑,及咪唑系或多官能丙烯酸酯系的硬化促進劑。<1-7. Additives> The curable composition of the present invention may contain additives. The additives arbitrarily added to the curable composition of the present invention are added from the viewpoint of improving the properties of the curable composition of the present invention such as coating uniformity, adhesion, and stability. Examples of additives are polymerization inhibitors, acrylic, styrenic, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, Silicone resin-based coating improver, adhesion improver such as silane coupling agent, anti-agglomerating agent such as sodium polyacrylate, thermal cross-linking agent such as epoxy compound, melamine compound or diazide compound, and hindered antioxidant such as phenol , And imidazole-based or polyfunctional acrylate-based hardening accelerators.

<1-7-1.表面活性劑、塗布性提高劑> 本發明的硬化性組成物中也可添加表面活性劑、塗布性提高劑。表面活性劑、塗布性提高劑是用以使對基底基板的潤濕性、流平性、或塗布性提高者。本發明的硬化性組成物中所任意添加的表面活性劑、塗布性提高劑的具體例為:珀利弗洛(Polyflow)No.45、珀利弗洛(Polyflow)KL-245、珀利弗洛(Polyflow)No.75、珀利弗洛(Polyflow)No.90、珀利弗洛(Polyflow)No.95(以上均為商品名,共榮社化學工業股份有限公司);畢克(BYK)-300、畢克(BYK)-306、畢克(BYK)-310、畢克(BYK)-320、畢克(BYK)-330、畢克(BYK)-342、畢克(BYK)-346(以上均為商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司);KP-341、KP-358、KP-368、KF-96-50CS、KF-50-100CS(以上均為商品名,信越化學工業股份有限公司);沙福隆(Surflon)SC-101、沙福隆(Surflon)KH-40、沙福隆(Surflon)S611(以上均為商品名,AGC清美化學(AGC Seimi Chemical)股份有限公司);福傑特(Ftergent)222F、福傑特(Ftergent)208G、福傑特(Ftergent)251、福傑特(Ftergent)710FL、福傑特(Ftergent)710FM、福傑特(Ftergent)710FS、福傑特(Ftergent)601AD、福傑特(Ftergent)602A、福傑特(Ftergent)650A、FTX-218(以上均為商品名,尼歐斯(Neos)股份有限公司);艾福拓(EFTOP)EF-351、艾福拓(EFTOP)EF-352、艾福拓(EFTOP)EF-601、艾福拓(EFTOP)EF-801、艾福拓(EFTOP)EF-802(以上均為商品名,三菱材料(Mitsubishi Material)股份有限公司);美佳法(Megafac)F-171、美佳法(Megafac)F-177、美佳法(Megafac)F-410、美佳法(Megafac)F-430、美佳法(Megafac)F-444、美佳法(Megafac)F-472SF、美佳法(Megafac)F-475、美佳法(Megafac)F-477、美佳法(Megafac)F-552、美佳法(Megafac)F-553、美佳法(Megafac)F-554、美佳法(Megafac)F-555、美佳法(Megafac)F-556、美佳法(Megafac)F-558、美佳法(Megafac)R-30、美佳法(Megafac)R-94、美佳法(Megafac)RS-75、美佳法(Megafac)RS-72-K、美佳法(Megafac)RS-76-NS(以上均為商品名,迪愛生(DIC)股份有限公司);迪高特溫(TEGO Twin)4000、迪高特溫(TEGO Twin)4100、迪高弗洛(TEGO Flow)370、迪高格萊德(TEGO Glide)420、迪高格萊德(TEGO Glide)440、迪高格萊德(TEGO Glide)450、迪高拉德(TEGO Rad)2200N、迪高拉德(TEGO Rad)2250N(以上均為商品名,日本贏創德固賽(Evonik Degussa Japan)股份有限公司);氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚、聚氧乙烯月桂基醚、聚氧乙烯油烯基醚、聚氧乙烯十三烷基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、聚氧乙烯月桂基胺、山梨糖醇酐月桂酸酯、山梨糖醇酐棕櫚酸酯、山梨糖醇酐硬脂酸酯、山梨糖醇酐油酸酯、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐月桂酸酯、聚氧乙烯山梨糖醇酐棕櫚酸酯、聚氧乙烯山梨糖醇酐硬脂酸酯、聚氧乙烯山梨糖醇酐油酸酯、聚氧乙烯萘基醚、烷基苯磺酸鹽、及烷基二苯基醚二磺酸鹽。優選為將選自這些的至少一種用於添加劑中。<1-7-1. Surfactant and coatability improving agent> A surfactant and a coatability improving agent may be added to the curable composition of the present invention. The surfactant and the coating property improving agent are used to improve the wettability, leveling property, or coating property of the base substrate. Specific examples of the surfactant and the coating property improving agent arbitrarily added to the curable composition of the present invention are: Polyflow No. 45, Polyflow KL-245, Polyflux (Polyflow) No. 75, Polyflow (Polyflow) No. 90, Polyflow (Polyflow) No. 95 (the above are all trade names, Gongrongshe Chemical Industry Co., Ltd.); BYK ) -300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK- 346 (the above are the trade names, BYK-Chemie Japan Co., Ltd.); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are all Trade name, Shin-Etsu Chemical Industry Co., Ltd.); Surflon SC-101, Surflon KH-40, Surflon S611 (the above are all trade names, AGC Qingmei Chemical (AGC) Seimi Chemical Co., Ltd.); Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710F L, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (the above are all goods Name, Neos Corporation); Eftop (EFTOP) EF-351, Eftop (EFTOP) EF-352, Eftop (EFTOP) EF-601, Eftop (EFTOP) EF -801, Eftop (EFTOP) EF-802 (all above are trade names, Mitsubishi Material Co., Ltd.); Megafac F-171, Megafac F-177, Megafac (Megafac) F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F- 477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac ( Megafac F-558, Megafac R-30, Megafac R-94, Megafac RS-75, Megafac RS-7 2-K, Megafac RS-76-NS (all above are trade names, DIC Corporation); TEGO Twin 4000, TEGO Twin 4100 , TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Glide Rad) 2200N, TEGO Rad 2250N (all above are trade names, Evonik Degussa Japan Co., Ltd.); fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate , Fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt , Fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene hard Acid ester, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester , Polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthalene Ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. Preferably, at least one selected from these is used in the additive.

在這些表面活性劑、塗布性提高劑中,若添加選自氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽、美佳法(Megafac)R-08、美佳法(Megafac)R-30、美佳法(Megafac)F-477、美佳法(Megafac)F-556、及美佳法(Megafac)F-554等氟系表面活性劑,以及畢克(BYK)-306、畢克(BYK)-342、畢克(BYK)-344、畢克(BYK)-346、KP-341、KP-358、及KP-368等矽酮系塗布性提高劑中的至少一種,則就提高本發明的硬化性組成物的塗布均勻性的觀點而言優選。To these surfactants and coatability improving agents, if selected from the group consisting of fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, and fluoroalkyl beet Alkali, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, Megafac R-08, Mega Fluorine surfactants such as Megafac R-30, Megafac F-477, Megafac F-556, and Megafac F-554, and BYK-306 At least one of silicone coating improvers such as, BYK-342, BYK-344, BYK-346, KP-341, KP-358, and KP-368, From the viewpoint of improving the coating uniformity of the curable composition of the present invention, it is preferable.

本發明的硬化性組成物中的表面活性劑、塗布性提高劑的含量優選為分別相對於組成物的總體量而言為0.001重量%~0.1重量%。The content of the surfactant and the coatability improving agent in the curable composition of the present invention is preferably 0.001% to 0.1% by weight relative to the total amount of the composition.

<1-7-2.硬化促進劑> 本發明的硬化性組成物中也可添加硬化促進劑。硬化促進劑是用以促進硬化性組成物的硬化反應,使硬化膜的硬度、耐熱性、耐化學品性提高者。本發明的硬化性組成物中所任意添加的硬化促進劑的具體例為:三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷EO改性三(甲基)丙烯酸酯、三羥甲基丙烷PO改性三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、丙三醇EO改性三(甲基)丙烯酸酯、丙三醇PO改性三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧化異氰脲酸三(甲基)丙烯酸酯、ε-己內酯改性三-(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、環氧化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇烷氧基四(甲基)丙烯酸酯、二甘油EO改性四丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯、及具有羧基的多官能(甲基)丙烯酸酯等三官能以上的(甲基)丙烯酸酯、以及2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、及2,3-二氫-1H-吡咯並[1,2-a]苯並咪唑等咪唑化合物。三官能以上的(甲基)丙烯酸酯與作為本發明的聚合物(A)的原料的成分(a1)相通,可使用所述具體例中列舉的化合物。其中,可優選地使用亞羅尼斯(Aronix)M-510、亞羅尼斯(Aronix)M-520、亞羅尼斯(Aronix)M-450、亞羅尼斯(Aronix)M-403、亞羅尼斯(Aronix)M-402。<1-7-2. Hardening accelerator> A hardening accelerator may be added to the hardening composition of the present invention. The hardening accelerator is used to accelerate the hardening reaction of the hardenable composition and improve the hardness, heat resistance, and chemical resistance of the cured film. Specific examples of the hardening accelerator optionally added to the hardenable composition of the present invention are trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, and Methylolpropane PO modified tri (meth) acrylate, glycerol tri (meth) acrylate, glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (methyl) ) Acrylate, pentaerythritol tri (meth) acrylate, epoxidized isocyanurate tri (meth) acrylate, ε-caprolactone-modified tri- (2- (meth) acryloxyethyl) Isocyanurate, di-trimethylolpropane tetra (meth) acrylate, epoxidized pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (methyl) Acrylate, diglycerol EO modified tetraacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, and polyfunctional (meth) acrylic acid having a carboxyl group and more Esters, and 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro- 1H-pyrrolo [1,2-a] benzimidazole and other imidazole compounds. The trifunctional or higher (meth) acrylate is compatible with the component (a1) as a raw material of the polymer (A) of the present invention, and the compounds listed in the specific examples can be used. Among them, Aronix M-510, Aronix M-520, Aronix M-450, Aronix M-403, Aronix ( Aronix) M-402.

通過將所述硬化促進劑添加至本發明的硬化性組成物中,可迅速地形成硬化膜,進而可對硬化膜賦予耐溶劑性或耐擦傷性等機械強度。硬化促進劑可單獨使用,也可將兩種以上混合使用。By adding the hardening accelerator to the curable composition of the present invention, a cured film can be formed quickly, and further, mechanical strength such as solvent resistance and scratch resistance can be imparted to the cured film. The hardening accelerator may be used alone or in combination of two or more.

<1-7-3.密接性提高劑> 本發明的硬化性組成物中也可添加密接性提高劑。密接性提高劑用以使硬化性組成物與基板的密接性提高。本發明的硬化性組成物中所任意添加的密接性提高劑可適宜使用偶聯劑。密接性提高劑可為一種,也可為兩種以上。偶聯劑中可使用矽烷系、鋁系或鈦酸酯系的化合物。此種偶聯劑的具體例為:3-縮水甘油氧基丙基二甲基乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、乙醯烷氧基二異丙醇鋁、及四異丙基雙(二辛基亞磷酸鹽(phosphite))鈦酸酯。這些中,3-縮水甘油氧基丙基三甲氧基矽烷的使密接性提高的效果大,因此優選。<1-7-3. Adhesiveness improving agent> An adhesiveness improving agent may be added to the curable composition of the present invention. The adhesiveness improving agent is used to improve the adhesiveness between the curable composition and the substrate. A coupling agent can be suitably used as the adhesiveness improvement agent arbitrarily added to the curable composition of this invention. The adhesion improving agent may be one type, or two or more types. As the coupling agent, a silane-based, aluminum-based, or titanate-based compound can be used. Specific examples of such coupling agents are: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Trimethoxysilane, acetoalkoxy aluminum diisopropoxide, and tetraisopropylbis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving the adhesion.

<1-7-4.抗凝聚劑> 本發明的硬化性組成物中也可添加抗凝聚劑。抗凝聚劑可以與溶劑溶合而用以防止凝聚。本發明的硬化性組成物中所任意添加的抗凝聚劑的具體例為:迪斯帕畢克(DISPERBYK)-145、迪斯帕畢克(DISPERBYK)-161、迪斯帕畢克(DISPERBYK)-162、迪斯帕畢克(DISPERBYK)-163、迪斯帕畢克(DISPERBYK)-164、迪斯帕畢克(DISPERBYK)-182、迪斯帕畢克(DISPERBYK)-184、迪斯帕畢克(DISPERBYK)-185、迪斯帕畢克(DISPERBYK)-2163、迪斯帕畢克(DISPERBYK)-2164、畢克(BYK)-220S、迪斯帕畢克(DISPERBYK)-191、迪斯帕畢克(DISPERBYK)-199、迪斯帕畢克(DISPERBYK)-2015(均為商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司)、FTX-218、福傑特(Ftergent)710FM、福傑特(Ftergent)710FS(均為商品名,尼歐斯(Neos)股份有限公司)、弗洛倫(FLOWLEN)G-600、弗洛倫(FLOWLEN)G-700(均為商品名,共榮社化學工業股份有限公司)。<1-7-4. Anti-agglomerating agent> An anti-agglomerating agent may be added to the curable composition of the present invention. The anticoagulant can be fused with a solvent to prevent aggregation. Specific examples of the anticoagulant arbitrarily added to the hardening composition of the present invention are: DISPERBYK-145, DISPERBYK-161, DISPERBYK -162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-182, DISPERBYK-184, DISPAR DISPERBYK-185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DI DISPERBYK-199, DISPERBYK-2015 (both trade names, BYK-Chemie Japan Co., Ltd.), FTX-218, Ftergent ) 710FM, Ftergent 710FS (all are trade names, Neos Co., Ltd.), FLOWLEN G-600, FLOWLEN G-700 (all products Name, Gongrongshe Chemical Industry Co., Ltd.).

<1-7-5.抗氧化劑> 本發明的硬化性組成物中也可添加抗氧化劑。抗氧化劑可適宜使用受阻酚系、受阻胺系、磷系、及硫系化合物。抗氧化劑可單獨使用,也可將兩種以上混合使用。就耐候性的觀點而言,抗氧化劑優選為受阻酚系化合物的抗氧化劑。<1-7-5. Antioxidant> An antioxidant may be added to the curable composition of the present invention. As the antioxidant, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds can be suitably used. The antioxidant may be used alone or in combination of two or more. From the viewpoint of weather resistance, the antioxidant is preferably an antioxidant of a hindered phenol compound.

本發明的硬化性組成物中所任意添加的抗氧化劑可使用受阻胺系、受阻酚系等。抗氧化劑具體而言為:易璐佛斯(IRGAFOS)XP40、易璐佛斯(IRGAFOS)XP60、易璐諾斯(IRGANOX)1010、易璐諾斯(IRGANOX)1035、易璐諾斯(IRGANOX)1076、易璐諾斯(IRGANOX)1135、易璐諾斯(IRGANOX)1520L(均為商品名,日本巴斯夫(BASF Japan)股份有限公司)、艾迪科斯塔波(ADK STAB)AO-20、艾迪科斯塔波(ADK STAB)AO-30、艾迪科斯塔波(ADK STAB)AO-50、艾迪科斯塔波(ADK STAB)AO-60、艾迪科斯塔波(ADK STAB)AO-70、艾迪科斯塔波(ADK STAB)AO-80(商品名,艾迪科(ADEKA)股份有限公司)。就抑制本發明的硬化性組成物的變色的觀點而言,這些中更優選為易璐諾斯(IRGANOX)1010、艾迪科斯塔波(ADK STAB)AO-60。As the antioxidant optionally added to the curable composition of the present invention, a hindered amine system, a hindered phenol system, or the like can be used. Specifically, the antioxidants are: IRGAFOS XP40, IRGAFOS XP60, IRANOX 1010, IRANOX 1035, IRANOX 1076, IRGANOX 1135, IRGANOX 1520L (both trade names, BASF Japan), ADK STAB AO-20, AI ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 , ADK STAB AO-80 (trade name, ADEKA Co., Ltd.). From the viewpoint of suppressing discoloration of the hardenable composition of the present invention, among these, IRGANOX 1010 and ADK STAB AO-60 are more preferable.

<1-7-6.交聯劑> 就使耐熱性、耐化學品性、膜面內均勻性、可撓性、柔軟性、彈性提高的觀點而言,本發明的硬化性組成物可任意地添加交聯劑。<1-7-6. Crosslinking agent> From the viewpoint of improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity, the curable composition of the present invention can be arbitrarily selected. Add a cross-linking agent.

本發明的硬化性組成物中所任意添加的熱交聯劑的具體例為:jER807、jER815、jER825、jER827、jER828、jER190P及jER191P(均為商品名,三菱化學股份有限公司)、jER1004、jER1256、YX8000(均為商品名,三菱化學股份有限公司)、愛牢達(Araldite)CY177、愛牢達(Araldite)CY184(均為商品名,日本亨斯邁(Huntsman Japan)股份有限公司)、賽羅西德(Celloxide)2021P、EHPE-3150(均為商品名,大賽璐化學工業股份有限公司)、特克摩阿(Techmore)VG3101L(商品名,普林泰科(Printec)股份有限公司)、尼卡拉庫(NIKALAC)MW-30HM、尼卡拉庫(NIKALAC)MW-100LM、尼卡拉庫(NIKALAC)MW-270、尼卡拉庫(NIKALAC)MW-280、尼卡拉庫(NIKALAC)MW-290、尼卡拉庫(NIKALAC)MW-390、尼卡拉庫(NIKALAC)MW-750LM(均為商品名,三和化學股份有限公司)。Specific examples of the thermal crosslinking agent arbitrarily added to the curable composition of the present invention are: jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (all are trade names, Mitsubishi Chemical Corporation), jER1004, jER1256 , YX8000 (both trade names, Mitsubishi Chemical Corporation), Araldite CY177, Araldite CY184 (both trade names, Huntsman Japan Co., Ltd.), Sai Rosside (Celloxide) 2021P, EHPE-3150 (both trade names, Daicel Chemical Industry Co., Ltd.), Techmore VG3101L (trade name, Printec Co., Ltd.), NIKALAC MW-30HM, NIKALAC MW-100LM, NIKALAC MW-270, NIKALAC MW-280, NIKALAC MW-290, NIKALAC MW-390, NIKALAC MW-750LM (both trade names, Sanwa Chemical Co., Ltd.).

<1-7-8.光酸產生劑> 本發明的硬化性組成物為了表現出優異的解析性,可任意地添加光酸產生劑。光酸產生劑可列舉1,2-醌二疊氮化合物。<1-7-8. Photoacid generator> The curable composition of the present invention may optionally add a photoacid generator in order to exhibit excellent resolution. Examples of the photoacid generator include 1,2-quinonediazide compounds.

1,2-醌二疊氮化合物的具體例為:2,3,4-三羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,4-三羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯(例如,NT-200;商品名,東洋合成化學工業)、2,4,6-三羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,4,6-三羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯;2,2',4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,2',4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯、2,3,3',4-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,3',4-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯、2,3,4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯;雙(2,4-二羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,4-二羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、雙(對羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(對羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯;三(對羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、三(對羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、1,1,1-三(對羥基苯基)乙烷-1,2-萘醌二疊氮-4-磺酸酯、1,1,1-三(對羥基苯基)乙烷-1,2-萘醌二疊氮-5-磺酸酯;雙(2,3,4-三羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,3,4-三羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、2,2-雙(2,3,4-三羥基苯基)丙烷-1,2-萘醌二疊氮-4-磺酸酯、2,2-雙(2,3,4-三羥基苯基)丙烷-1,2-萘醌二疊氮-5-磺酸酯;1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷-1,2-萘醌二疊氮-4-磺酸酯、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷-1,2-萘醌二疊氮-5-磺酸酯、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚-1,2-萘醌二疊氮-4-磺酸酯、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚-1,2-萘醌二疊氮-5-磺酸酯;雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷-1,2-萘醌二疊氮-5-磺酸酯、3,3,3',3'-四甲基-1,1'-螺二茚-5,6,7,5',6',7'-己醇-1,2-萘醌二疊氮-4-磺酸酯、3,3,3',3'-四甲基-1,1'-螺二茚-5,6,7,5',6',7'-己醇-1,2-萘醌二疊氮-5-磺酸酯;2,2,4-三甲基-7,2',4'-三羥基黃烷-1,2-萘醌二疊氮-4-磺酸酯、及2,2,4-三甲基-7,2',4'-三羥基黃烷-1,2-萘醌二疊氮-5-磺酸酯。Specific examples of 1,2-quinonediazide compounds are: 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4-triazine Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate (eg, NT-200; trade name, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthalene Quinonediazide-5-sulfonate, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide 4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; bis (2,4-dihydroxyphenyl) Methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, bis (p- Hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate; tris ( Hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1 1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthalene Quinonediazide-5-sulfonate; bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide Aza-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-tris (2,5- Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate, 4,4 '-[1- [4- [1- [4- Hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4 '-[1- [4- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis (2,5-bis (Methyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3 ', 3'- Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3 , 3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-5- Sulfonate; 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane-1,2-naphthoquinonediazide-4-sulfonate, and 2,2,4- Trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate.

<1-8.硬化性組成物的保存> 本發明的硬化性組成物若在-30℃~25℃的範圍內遮光而保存,則組成物的經時穩定性變得良好而優選。更優選為在-10℃~20℃下保存。<1-8. Preservation of hardenable composition> The hardenable composition of the present invention is preferably stored in the range of -30 ° C to 25 ° C with light-shielding and preservation, as the stability of the composition over time is good. More preferably, it is stored at -10 ° C to 20 ° C.

<2.由硬化性組成物所得的硬化膜> 若將本發明的硬化性組成物塗布在基材表面,通過例如加熱等而將溶劑去除,則可形成塗膜。<2. A cured film obtained from a curable composition> A coating film can be formed by applying the curable composition of the present invention to the surface of a substrate and removing the solvent by, for example, heating.

本發明的硬化性組成物的塗布方法可利用旋塗法、輥塗法、浸漬法、狹縫塗布法、噴墨法、柔版印刷法及凹版印刷法等現有公知的方法而形成塗膜。The coating method of the curable composition of the present invention can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, a slit coating method, an inkjet method, a flexographic printing method, and a gravure printing method.

成膜時所使用的基材可列舉塑料、玻璃、帶有氟摻雜氧化錫(Fluorine-doped Tin Oxide,FTO)或氧化銦錫(Indium Tin Oxide,ITO)等透明電極的玻璃等基材。塑料的具體例可列舉聚碳酸酯、聚(甲基)丙烯酸酯、聚胺基甲酸酯、聚對苯二甲酸乙二酯、環烯烴、三乙醯纖維素。Examples of the substrate used in film formation include plastics, glass, glass with transparent electrodes such as Fluorine-doped Tin Oxide (FTO) or Indium Tin Oxide (ITO). Specific examples of the plastic include polycarbonate, poly (meth) acrylate, polyurethane, polyethylene terephthalate, cycloolefin, and triethyl cellulose.

該塗膜可利用加熱板、或烘箱等進行加熱(預烘烤)。加熱條件因各成分的種類及調配比例而異,通常為60℃~100℃、1分鐘~15分鐘。其後,為了使塗膜硬化,在80℃~140℃、優選為80℃~120℃下進行5分鐘~60分鐘的加熱處理(後烘烤),由此可獲得硬化膜。This coating film can be heated (pre-baked) using a hot plate or an oven. The heating conditions vary depending on the type of each component and the blending ratio, and are usually 60 ° C to 100 ° C, and 1 minute to 15 minutes. Thereafter, in order to harden the coating film, a heat treatment (post-baking) is performed at 80 ° C. to 140 ° C., preferably 80 ° C. to 120 ° C. for 5 minutes to 60 minutes, thereby obtaining a cured film.

本發明的硬化性組成物即使在使塗膜硬化的溫度為85℃~120℃的低溫下也可進行熱硬化而獲得硬化膜。因此,若對如塑料般的玻璃化轉變點低的基材應用本發明的硬化性組成物,則可並不引起基材的劣化、破損地獲得硬化膜。The curable composition of the present invention can be thermally cured even at a low temperature at which the coating film is cured at a low temperature of 85 ° C to 120 ° C to obtain a cured film. Therefore, when the curable composition of the present invention is applied to a substrate having a low glass transition point, such as plastic, a cured film can be obtained without causing degradation or damage to the substrate.

關於本發明的硬化性組成物,可對預烘烤後的塗膜照射紫外線。適當的是紫外線照射量以i射線計為5 mJ/cm2 ~1000 mJ/cm2 。經紫外線照射的硬化性組成物通過具有聚合性雙鍵的化合物的聚合而成為三維交聯體,膜硬化性提高。 [實施例]Regarding the curable composition of the present invention, ultraviolet rays can be irradiated to the coating film after the prebaking. It is suitable that the amount of ultraviolet irradiation is 5 mJ / cm 2 to 1000 mJ / cm 2 in terms of i-rays. The curable composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and the film hardenability is improved. [Example]

以下,通過實施例來對本發明進一步進行說明,但本發明並不受這些實施例的限定。以下表示本發明的硬化性組成物的評價方法。Hereinafter, the present invention is further described by examples, but the present invention is not limited by these examples. The evaluation method of the curable composition of this invention is shown below.

對於每種成分,記載聚合例、實施例、以及比較例中使用的化合物。For each component, compounds used in the polymerization examples, examples, and comparative examples are described.

三官能以上的(甲基)丙烯酸酯(a1): 亞羅尼斯(Aronix)M-402(商品名,東亞合成股份有限公司,以下略記為「M-402」) 鏈轉移劑(a2): 2,4-二苯基-4-甲基-1-戊烯(以下略記為「α-MSD」) 具有聚合性雙鍵的化合物(a3): 作為具有烷氧基矽烷基及聚合性雙鍵的化合物的甲基丙烯酸3-(三甲氧基矽烷基)丙酯(商品名,希拉艾斯(Sila-ace)S710,JNC股份有限公司,以下略記為「S710」) 作為具有羧基及聚合性雙鍵的化合物的甲基丙烯酸 聚合起始劑: V-65(商品名,和光純藥工業股份有限公司,以下略記為「V-65」) 聚合溶劑: 丙二醇單甲醚(以下略記為「PGME」) 光聚合起始劑(B): 豔佳固(IRGACURE)OXE01(商品名,日本巴斯夫(BASF Japan)股份有限公司,以下略記為「OXE01」) 豔佳固(IRGACURE)OXE02(商品名,日本巴斯夫(BASF Japan)股份有限公司,以下略記為「OXE02」) 艾迪科亞庫魯茲(ADEKA ARKLS)NCI-930(商品名,艾迪科(ADEKA)股份有限公司,以下略記為「NCI-930」) 稀釋溶劑: PGME 添加劑: 作為矽酮系表面活性劑的畢克(BYK)-342(商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司,以下略記為「畢克(BYK)-342」) 作為三官能丙烯酸酯的季戊四醇三丙烯酸酯及作為四官能丙烯酸酯的季戊四醇四丙烯酸酯的混合物即亞羅尼斯(Aronix)M-450(商品名,東亞合成股份有限公司,以下略記為「M-450」) 作為光酸產生劑的NT-200(商品名,東洋合成化學工業)。Trifunctional or higher (meth) acrylate (a1): Aronix M-402 (trade name, East Asia Synthetic Co., Ltd., hereinafter abbreviated as "M-402") Chain transfer agent (a2): 2 , 4-Diphenyl-4-methyl-1-pentene (hereinafter abbreviated as "α-MSD") Compound (a3) having a polymerizable double bond: As a compound having an alkoxysilyl group and a polymerizable double bond Compound 3- (trimethoxysilyl) propyl methacrylate (trade name, Sila-ace S710, JNC Corporation, hereinafter abbreviated as "S710") as having a carboxyl group and a polymerizable double bond Methacrylic acid polymerization initiator of the compound: V-65 (trade name, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "V-65") Polymerization solvent: propylene glycol monomethyl ether (hereinafter abbreviated as "PGME") Photopolymerization initiator (B): IRGACURE OXE01 (trade name, BASF Japan Co., Ltd., hereinafter referred to as "OXE01") IRGACURE OXE02 (trade name, BASF Japan) (BASF Japan) Co., Ltd. "OXE02") ADEKA ARKLS NCI-930 (trade name, ADEKA Co., Ltd., hereinafter abbreviated as "NCI-930") Diluent solvent: PGME additive: as silicon Ketone surfactant BYK-342 (trade name, BYK-Chemie Japan Co., Ltd., hereinafter referred to as "BYK-342") as a trifunctional acrylate A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as a tetrafunctional acrylate is Aronix M-450 (trade name, East Asia Synthetic Co., Ltd., hereinafter abbreviated as "M-450"). Agent NT-200 (trade name, Toyo Synthetic Chemical Industry).

[聚合例1] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 18.0 g、作為三官能以上的(甲基)丙烯酸酯(a1)的M-402 4.51 g、作為鏈轉移劑(a2)的α-MSD 0.90 g、作為聚合起始劑的V-65 0.23 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 1] In a four-necked flask equipped with a stirrer, 18.0 g of PGME as a polymerization solvent and M-402 as a trifunctional or higher (meth) acrylate (a1) were charged while bubbling with nitrogen. 4.51 g, α-MSD 0.90 g as a chain transfer agent (a2), and V-65 0.23 g as a polymerization initiator, stirred at 35 ° C. for 5 minutes to confirm the dissolution of the content, and took 15 minutes to rise to 80 ℃ so far. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A1)。對含聚合物的溶液(A1)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為11,800。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A1). A part of the polymer-containing solution (A1) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 11,800.

[聚合例2] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-402 6.51 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的S710 0.34 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱5小時而進行聚合。[Polymerization Example 2] In a four-necked flask equipped with a stirrer, 16.0 g of PGME as a polymerization solvent, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer were charged while bubbling with nitrogen. M-402 6.51 g, S710 0.34 g as a compound (a3) having a polymerizable double bond in the raw monomer, 1.37 g α-MSD as a chain transfer agent (a2), and V-65 0.34 g as a polymerization initiator After stirring at 35 ° C for 5 minutes to confirm the dissolution of the contents, it took 15 minutes to raise the temperature to 80 ° C. Then, it heated at 80 degreeC for 5 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A2)。對含聚合物的溶液(A2)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為12,600。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A2). A part of the polymer-containing solution (A2) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 12,600.

[聚合例3] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-402 4.80 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的甲基丙烯酸2.06 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 3] In a four-necked flask equipped with a stirrer, 16.0 g of PGME as a polymerization solvent, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer were charged while bubbling with nitrogen. M-402 4.80 g, 2.06 g of methacrylic acid as a compound (a3) having a polymerizable double bond in the raw material monomer, 1.37 g of α-MSD as a chain transfer agent (a2), and V-65 as a polymerization initiator 0.34 g, stirred at 35 ° C for 5 minutes to confirm the dissolution of the contents, and it took 15 minutes to raise the temperature to 80 ° C. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A3)。對含聚合物的溶液(A3)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為18,800。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A3). A part of the polymer-containing solution (A3) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 18,800.

[聚合例4] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-402 3.91 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的甲基丙烯酸2.13 g、S710 0.82 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 4] In a four-necked flask equipped with a stirrer, 16.0 g of PGME as a polymerization solvent, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer were charged while bubbling with nitrogen. M-402 3.91 g, 2.13 g of methacrylic acid as a compound (a3) having a polymerizable double bond in the raw material monomer, 0.82 g of S710, 1.37 g of α-MSD as a chain transfer agent (a2), and polymerization initiator V-65 0.34 g, stirred at 35 ° C for 5 minutes to confirm the dissolution of the contents, and then heated to 80 ° C in 15 minutes. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A4)。對含聚合物的溶液(A4)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為35,200。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A4). A part of the polymer-containing solution (A4) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 35,200.

[聚合例5] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-520 5.35 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的甲基丙烯酸1.51 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 5] In a four-necked flask equipped with a stirrer, 16.0 g of PGME as a polymerization solvent, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer were charged while bubbling with nitrogen. M-520 5.35 g, 1.51 g of methacrylic acid as a compound (a3) having a polymerizable double bond in the raw material monomer, 1.37 g of α-MSD as a chain transfer agent (a2), and V-65 as a polymerization initiator 0.34 g, stirred at 35 ° C for 5 minutes to confirm the dissolution of the contents, and it took 15 minutes to raise the temperature to 80 ° C. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A5)。對含聚合物的溶液(A5)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為23,600。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A5). A part of the polymer-containing solution (A5) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 23,600.

[聚合例6] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-402 4.11 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的甲基丙烯酸2.19 g、甲基丙烯酸丁酯0.55 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 6] In a four-necked flask equipped with a stirrer, 16.0 g of PGME as a polymerization solvent, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer were charged while bubbling with nitrogen. M-402 4.11 g, 2.19 g of methacrylic acid, 0.55 g of butyl methacrylate as a compound (a3) having a polymerizable double bond in the raw material monomer, 1.37 g of α-MSD as a chain transfer agent (a2), and 0.34 g of V-65 as a polymerization initiator was stirred at 35 ° C for 5 minutes to confirm the dissolution of the content, and the temperature was raised to 80 ° C in 15 minutes. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A6)。對含聚合物的溶液(A6)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為26,800。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A6). A part of the polymer-containing solution (A6) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 26,800.

[聚合例7] 在帶有攪拌器的四口燒瓶中,一面用氮氣起泡,一面投入作為聚合溶劑的PGME 16.0 g、作為原料單體內三官能以上的(甲基)丙烯酸酯(a1)的M-402 4.18 g、作為原料單體內具有聚合性雙鍵的化合物(a3)的甲基丙烯酸2.19 g、甲基丙烯酸2-羥基乙酯0.48 g、作為鏈轉移劑(a2)的α-MSD 1.37 g、作為聚合起始劑的V-65 0.34 g,在35℃下攪拌5分鐘而確認內容物的溶解後,花費15分鐘升溫至80℃為止。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 7] A four-necked flask equipped with a stirrer was charged with 16.0 g of PGME as a polymerization solvent while foaming with nitrogen, and tri- or higher-functional (meth) acrylate (a1) as a raw material monomer. M-402 4.18 g, 2.19 g of methacrylic acid as compound (a3) with polymerizable double bond in raw material monomer, 0.48 g of 2-hydroxyethyl methacrylate, α-MSD 1.37 as chain transfer agent (a2) g, V-65 0.34 g as a polymerization initiator, stirred at 35 ° C. for 5 minutes to confirm the dissolution of the contents, and then heated to 80 ° C. in 15 minutes. Then, it heated at 80 degreeC for 3 hours, and superposed | polymerized.

將聚合後的溶液冷卻至室溫而獲得含聚合物的溶液(A7)。對含聚合物的溶液(A7)的一部分進行取樣,通過GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,重量平均分子量為37,200。The polymerized solution was cooled to room temperature to obtain a polymer-containing solution (A7). A part of the polymer-containing solution (A7) was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 37,200.

[實施例1] 以表1所記載的比例(單位:g)將聚合例1中獲得的含聚合物的溶液(A1)、作為光聚合起始劑(B)的OXE01、作為添加劑的畢克(BYK)-342、及作為稀釋溶劑的PGME混合溶解,利用膜濾器(0.2 μm)進行過濾而獲得熱硬化性組成物。[Example 1] The polymer-containing solution (A1) obtained in Polymerization Example 1, OXE01 as a photopolymerization initiator (B), and Pike as an additive were used at the ratio (unit: g) described in Table 1. (BYK) -342 and PGME as a diluent are mixed and dissolved, and filtered with a membrane filter (0.2 μm) to obtain a thermosetting composition.

此外,該硬化性組成物中所含的溶劑的總量為含聚合物的溶液(A1)中所含的PGME及稀釋溶劑的PGME的總量,在該步驟中以固體成分濃度成為約20重量%的方式進行調整。實施例2~實施例13及比較例1、比較例2中也同樣。The total amount of the solvent contained in the curable composition is the total amount of PGME contained in the polymer-containing solution (A1) and the PGME of the diluent solvent. In this step, the solid content concentration becomes about 20 weight % Way to adjust. The same applies to Examples 2 to 13 and Comparative Examples 1 and 2.

以300 rpm歷時10秒鐘將硬化性組成物旋塗於玻璃基板上,在85℃的加熱板上預烘烤2分鐘。繼而,在空氣中,使用近接式曝光機TME-150PRC(商品名,拓普康(Topcon)股份有限公司)並進行曝光。曝光量是利用累計光量計UIT-102(商品名,牛尾(USHIO)股份有限公司)、光接收器UVD-365PD(商品名,牛尾(USHIO)股份有限公司)進行測定而設為100 mJ/cm2 。進而在85℃的加熱板上後烘烤30分鐘,獲得膜厚為3.0 μm的帶有85℃烘烤硬化膜的玻璃基板。除將後烘烤時的加熱板的溫度自85℃變更為140℃以外,進行同樣的步驟而獲得帶有140℃烘烤硬化膜的玻璃基板。The curable composition was spin-coated on a glass substrate at 300 rpm for 10 seconds, and pre-baked on a hot plate at 85 ° C for 2 minutes. Next, exposure was performed in the air using a proximity exposure machine TME-150PRC (trade name, Topcon Co., Ltd.). The exposure amount was measured using a cumulative light meter UIT-102 (trade name, USHIO) Co., Ltd. and a light receiver UVD-365PD (trade name, USHIO) Co., Ltd. and set to 100 mJ / cm 2 . Further, it was post-baked for 30 minutes on a hot plate at 85 ° C. to obtain a glass substrate with an 85 ° C. baked cured film having a film thickness of 3.0 μm. Except changing the temperature of the heating plate at the time of post-baking from 85 ° C to 140 ° C, the same procedure was performed to obtain a glass substrate with a 140 ° C baking cured film.

[成膜性的評價方法] 利用光學顯微鏡觀察所獲得的帶有85℃烘烤硬化膜的玻璃基板的基板端,測定自基板端至硬化膜端的距離、即在玻璃基板上不存在硬化膜的區域的寬度距離,並將測定值記載於表1中。但是,於無法觀察到在玻璃基板上不存在硬化膜的區域的情況下,記載為「無」。將自基板端至硬化膜端的距離未滿100 μm的情況評價為成膜性「○」,將自基板端至硬化膜端的距離為100 μm以上的情況評價為成膜性「×」,並將評價結果記載於表1中。[Evaluation method of film formation property] The substrate end of the obtained glass substrate with a baked cured film at 85 ° C was observed with an optical microscope, and the distance from the substrate end to the cured film end was measured, that is, the cured film was not present on the glass substrate. The width and distance of the area are shown in Table 1. However, when a region where a cured film does not exist on the glass substrate cannot be observed, it is described as "none". The case where the distance from the substrate end to the cured film end was less than 100 μm was evaluated as film formation property “○”, and the case where the distance from the substrate end to the cured film end was 100 μm or more was evaluated as film formation property “×”, and The evaluation results are shown in Table 1.

[低溫硬化性的評價方法] 將進行了膜厚測定的帶有85℃烘烤硬化膜的玻璃基板在保持為24℃的PGME中浸漬2分鐘。進行自PGME取出,通過鼓風去除PGME的浸漬試驗。其後,測定膜厚而算出浸漬殘膜率=(浸漬後膜厚/浸漬前膜厚)×100,並將算出值記載於表1中。進而,使用進行了膜厚測定的帶有140℃烘烤硬化膜的玻璃基板,進行同樣的浸漬試驗及浸漬殘膜率算出,並將算出值記載於表1中。將帶有85℃烘烤硬化膜的玻璃基板的浸漬殘膜率及帶有140℃烘烤硬化膜的玻璃基板的浸漬殘膜率均成為95%以上的情況評價為低溫硬化性「○」,將其他情況評價為低溫硬化性「×」,並將評價結果記載於表1中。[Evaluation method of low-temperature hardenability] A glass substrate with a baked cured film at 85 ° C subjected to film thickness measurement was immersed in PGME maintained at 24 ° C for 2 minutes. An immersion test was performed to take out the PGME and remove the PGME by blowing air. Thereafter, the film thickness was measured to calculate the immersion residual film ratio = (film thickness after immersion / film thickness before immersion) × 100, and the calculated values are shown in Table 1. Furthermore, the glass substrate with a 140 degreeC baking-hardened film which measured the film thickness was used, the same immersion test and the immersion residual film rate calculation were performed, and the calculated value is described in Table 1. The case where the dipped residual film rate of the glass substrate with the 85 ° C bake cured film and the dipped residual film rate of the glass substrate with the 140 ° C bake cured film both reached 95% or more was evaluated as low-temperature hardening "○", The other cases were evaluated as low-temperature curability "X", and the evaluation results are shown in Table 1.

[透明性的評價方法] 使用紫外可見近紅外分光光度計(商品名,V-670,日本分光股份有限公司),在紫外可見近紅外分光光度計的參考側設置無硬化膜的玻璃基板,在樣品側設置帶有85℃烘烤硬化膜的玻璃基板,由此測定僅85℃烘烤硬化膜在光的波長400 nm下的透光率,並將測定值記載於表1中。將透光率為95%以上的情況評價為透明性「○」,將透光率未滿95%的情況評價為透明性「×」,並將評價結果記載於表1中。[Evaluation method of transparency] A UV-visible near-infrared spectrophotometer (trade name, V-670, Japan Spectrophotometer Co., Ltd.) was used, and a glass substrate without a hardened film was set on the reference side of the ultraviolet-visible near-infrared spectrophotometer. A glass substrate with a baked cured film at 85 ° C was set on the sample side, and the light transmittance of the baked cured film at only 85 ° C at a wavelength of light of 400 nm was measured. The measured values are shown in Table 1. The case where the light transmittance was 95% or more was evaluated as transparency “○”, and the case where the light transmittance was less than 95% was evaluated as transparency “×”. The evaluation results are shown in Table 1.

[實施例2~實施例9及比較例1~比較例2] 依據實施例1的方法,以表1中所記載的比例(單位:g)將各成分混合溶解而獲得硬化性組成物。依據實施例1的方法,測定自基板端至硬化膜端的距離及透光率,並算出浸漬殘膜率且進行成膜性、低溫硬化性及透明性的評價。將這些結果記載於表1中。[Example 2 to Example 9 and Comparative Example 1 to Comparative Example 2] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) described in Table 1 to obtain a hardenable composition. In accordance with the method of Example 1, the distance from the substrate end to the cured film end and the light transmittance were measured, and the immersion residual film rate was calculated, and the film forming properties, low-temperature curing properties, and transparency were evaluated. These results are described in Table 1.

表1-1 Table 1-1

表1-2 Table 1-2

[密接性試驗(實施例6~實施例8、實施例10)] 對實施例6~實施例8的分別獲得的帶有85℃烘烤硬化膜的玻璃基板進行硬化膜的膠帶剝離的交叉切割試驗(JIS-K5600,ISO2409),計數殘存數。任一試驗結果均為分類0,因此將該硬化性組成物的密接性判斷為良好。[Adhesion Test (Examples 6 to 8 and Example 10)] Cross-cutting of the cured film tape peeling was performed on each of the glass substrates with a baked cured film at 85 ° C obtained in Examples 6 to 8 Test (JIS-K5600, ISO2409), counting the remaining number. Since any test result was classified as 0, the adhesiveness of this curable composition was judged to be good.

[圖案形成性試驗(實施例9~實施例13)] 以300 rpm歷時10秒鐘將硬化性組成物旋塗於玻璃基板上,在85℃的加熱板上預烘烤2分鐘。繼而,在空氣中隔著具有50 μm見方的正方形圖案的罩幕,使用近接式曝光機TME-150PRC(商品名,拓普康(Topcon)股份有限公司)進行曝光。曝光量是利用累計光量計UIT-102(商品名,牛尾(USHIO)股份有限公司)、光接收器UVD-365PD(商品名,牛尾(USHIO)股份有限公司)進行測定而設為100 mJ/cm2 。利用2.38重量%氫氧化四甲基銨水溶液對曝光後的塗膜進行60秒鐘的覆液顯影後,利用純水對塗膜清洗20秒鐘後,利用85℃的加熱板乾燥2分鐘。進而,在85℃的加熱板上後烘烤30分鐘後,使用光學顯微鏡進行觀察,結果確認到圖案寬為大約50 μm的點狀圖案,因此將該硬化性組成物的圖案形成性判斷為良好。[Pattern Formability Test (Examples 9 to 13)] The curable composition was spin-coated on a glass substrate at 300 rpm for 10 seconds, and pre-baked on a hot plate at 85 ° C for 2 minutes. Next, exposure was performed using a proximity exposure machine TME-150PRC (trade name, Topcon Co., Ltd.) through a mask having a square pattern of 50 μm square in the air. The exposure amount was measured using a cumulative light meter UIT-102 (trade name, USHIO) Co., Ltd. and a light receiver UVD-365PD (trade name, USHIO) Co., Ltd. and set to 100 mJ / cm 2 . After the exposed coating film was developed with a 2.38% by weight tetramethylammonium hydroxide aqueous solution for 60 seconds, the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 85 ° C. for 2 minutes. Furthermore, after post-baking for 30 minutes on a hot plate at 85 ° C., observation was performed using an optical microscope. As a result, a dot pattern having a pattern width of about 50 μm was confirmed. Therefore, the pattern formability of the curable composition was judged to be good .

由表1的結果所明確般,實施例1~實施例13的含有聚合物(A)、光聚合起始劑(B)及溶劑(C)的硬化性組成物的成膜性、低溫硬化性、及透明性優異。As is clear from the results in Table 1, the film-forming properties and low-temperature curing properties of the curable composition containing the polymer (A), the photopolymerization initiator (B), and the solvent (C) in Examples 1 to 13 are as follows. And excellent transparency.

比較例1的硬化性組成物不含有光聚合起始劑(B),在140℃的烘烤中進行硬化,但在85℃的烘烤下的硬化不充分,低溫硬化性不良。比較例2的硬化性組成物不含有聚合物(A),成膜性及透明性不良。The curable composition of Comparative Example 1 did not contain a photopolymerization initiator (B) and was cured during baking at 140 ° C. However, the curing was insufficient at 85 ° C and the low-temperature curability was poor. The curable composition of Comparative Example 2 did not contain the polymer (A), and had poor film-forming properties and transparency.

進而,由所述密接性試驗結果所明確般,在聚合物(A)的原料單體的一部分中使用具有烷氧基矽烷基及聚合性雙鍵的化合物的實施例6~實施例8及實施例10的硬化性組成物的密接性也優異。Furthermore, as is clear from the results of the adhesion test, Examples 6 to 8 and Examples in which a compound having an alkoxysilyl group and a polymerizable double bond was used as a part of the raw material monomer of the polymer (A) were implemented. The adhesiveness of the curable composition of Example 10 was also excellent.

進而,由所述圖案形成性試驗結果所明確般,在聚合物(A)的原料單體的一部分中使用具有羧基及聚合性雙鍵的化合物的實施例9~實施例13的硬化性組成物的圖案形成性也優異。 [產業上的可利用性]Furthermore, as is clear from the results of the pattern formation test, the curable compositions of Examples 9 to 13 in which a compound having a carboxyl group and a polymerizable double bond was used as a part of the raw material monomer of the polymer (A). It is also excellent in pattern formation. [Industrial availability]

本發明的硬化性組成物的成膜性、低溫硬化性、及硬化膜的透明性優異,使用本發明的硬化性組成物而獲得的硬化膜可用作彩色濾光片保護膜、或者設於TFT與配向膜間或TFT與透明電極間的透明絕緣膜等。低溫硬化性優異,因此特別是在以有機材料為基材的情況下有效。The curable composition of the present invention has excellent film-forming properties, low-temperature curability, and transparency of the cured film. The cured film obtained by using the curable composition of the present invention can be used as a color filter protective film or provided in A transparent insulating film between a TFT and an alignment film or between a TFT and a transparent electrode. Since it is excellent in low-temperature curability, it is effective especially when an organic material is used as a base material.

無。no.

no

Claims (7)

一種硬化性組成物,其特徵在於含有:聚合物(A),使包含三官能以上的(甲基)丙烯酸酯(a1)的原料單體在鏈轉移劑(a2)的存在下進行自由基聚合而獲得;光聚合起始劑(B);以及溶劑(C)。A hardenable composition comprising a polymer (A) and radical polymerization of a raw material monomer containing a trifunctional or higher (meth) acrylate (a1) in the presence of a chain transfer agent (a2) And obtained; a photopolymerization initiator (B); and a solvent (C). 如申請專利範圍第1項所述的硬化性組成物,其中,鏈轉移劑(a2)為2,4-二苯基-4-甲基-1-戊烯。The hardenable composition according to item 1 of the patent application scope, wherein the chain transfer agent (a2) is 2,4-diphenyl-4-methyl-1-pentene. 如申請專利範圍第1項所述的硬化性組成物,其中,聚合物(A)的重量平均分子量為2,000~200,000。The curable composition according to item 1 of the scope of patent application, wherein the weight average molecular weight of the polymer (A) is 2,000 to 200,000. 如申請專利範圍第1項所述的硬化性組成物,其中,光聚合起始劑(B)為選自α-胺基苯烷基酮系光聚合起始劑、醯基氧化膦系光聚合起始劑、肟酯系光聚合起始劑中的至少一種。The hardenable composition according to item 1 of the scope of the patent application, wherein the photopolymerization initiator (B) is selected from the group consisting of an α-aminobenzoyl ketone photopolymerization initiator and a fluorenyl phosphine oxide system photopolymerization. At least one of an initiator and an oxime ester-based photopolymerization initiator. 如申請專利範圍第1項所述的硬化性組成物,其中,溶劑(C)基於總溶劑的重量而含有50重量%以上的沸點為150℃以下的溶劑。The curable composition according to item 1 of the scope of patent application, wherein the solvent (C) contains 50% by weight or more of a solvent having a boiling point of 150 ° C or less based on the weight of the total solvent. 一種硬化膜,其特徵在於,使用如申請專利範圍第1項至第5項中任一項所述的硬化性組成物而獲得。A cured film obtained by using the curable composition according to any one of claims 1 to 5 of the patent application scope. 一種顯示元件,其特徵在於,包含如申請專利範圍第6項所述的硬化膜。A display element comprising a cured film according to item 6 of the patent application scope.
TW106124946A 2016-10-07 2017-07-25 Curable composition and cured films thereof, display device comprising cured films capable of providing excellent film-forming property and low-temperature curing property TW201813982A (en)

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