200940570 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種活性能量線硬化性樹脂。更詳而 言，係關於在被膜形成後，藉由曝光及稀鹼水溶液之顯影 即可容易地形成影像之感光性樹脂。特別是關於一種可用 於與電子設備相關之印刷電路板、LSI (大型積體電路）方 面、附隨於液晶之彩色濾光片、封止劑（sealing agent)等 之光阻印墨（resist ink)之黏結劑樹脂之活性能量線硬化 0 性樹脂。此外，也係關於該活性能量線硬化性樹脂之製造 方法。 【先前技術】 在印刷電路板方面，防焊阻劑樹脂（solder resist resin )係已廣泛被用作爲基板電路之永久保護被膜。先前欲在印 刷電路板上形成防焊阻劑時，則以網版印刷法（s c r e e n p r i n t i n g method )印刷熱硬化型之阻劑印墨，然後將轉印部加以熱硬 化或紫外線硬化所達成。然而，網版印刷法卻會在印刷時造 © 成例如溢流（bleeding)、滲漏（bleed-through)、下垂（sagging )之現象’結果導致其無法相對應於電路板之高密度化。因 此，爲解決此問題而開發出照相法（光阻（photoresist)等） 並已付諸實務應用化。照相法係一種透過經形成圖案之薄膜 而加以曝光顯影，以形成目的圖案之方法。 關於如上所述之照相法，先前一直在使用氯系溶劑等作 爲顯影液’但是近年來由於環境問題、節約資源、節約能源 、提高作業性等之理由，在各領域則有從溶劑顯影轉移至稀 鹼水溶液顯影之趨勢，而在印刷電路板加工領域方面，也已 200940570 演變成由溶劑顯影型轉移至稀鹸水溶液顯影型之光阻印墨。 對應於此等趨勢已有提案各種光阻印墨，例如，作爲印 墨感度與不黏（表乾：tack free )是平衡的光硬化性樹脂組成 物而揭述：一種具有可鍵結於不飽和基與羧基之間的二價之 基的化合物；一種包含經在由（甲基）丙烯酸及（甲基）丙 烯酸酯所獲得之共聚合物的一部份酸基加成含有環氧基之不 飽和化合物所獲得之改質共聚合物的硬化性樹脂（參閱發明 專利文獻1);或一種包含將經在1莫耳之（甲基）丙烯酸羥 0 基烷基酯加成少於1莫耳之比率的ε -己內酯單體所獲得之末 端羥基（甲基）丙烯酸酯加以酸酐改質所獲得之具有末端羧 基之單體組成物的光硬化性樹脂組成物；或一種包含經在（ 甲基）丙烯酸加成少於1莫耳之比率的ε-己內酯單體所獲得 之具有末端羧基之單體組成物的光硬化性樹脂組成物（參閱 發明專利文獻2)。 然而，近年來對於此等光硬化性樹脂材料之要求則趨向 於更嚴格。隨著電子零組件之高功能化、省電化、小型化， 〇 使得電路圖案已演變成更微細者，而對於光硬化性樹脂材料 則要求可正確地形成高精細圖案之優越的圖案形成性。另一 方面，伴隨圖案之微細化，卻已經顯現在曝光後光阻圖案（ resist pattern)容易崩潰之新問題。針對於此問題，雖然可採 取以光阻薄膜化使得圖案縱橫比（aspect ratio)減小之方法 ，但是在此情形下，耐蝕刻性之降低即將成問題。因此，藉 由提高光阻圖案本身的機械強度以抑制對於微細化之崩潰已 成爲必要措施。並且，視用途而定，對於光阻圖案要求之性 能係不僅是例如所謂的「硬度」的機械強度而已，有時候也 200940570 要求在施加荷重然後移除荷重後之形狀恢復力。亦即，對於 光硬化性樹脂材料，除了如前所述感度或不黏（表乾）等之 特性外，則更進一步要求必須具備優越的圖案形成性與因應 要求之圖案的機械特性。 已揭述於如前所述發明專利文獻之光硬化性樹脂組成物 ，雖然感度等之問題方面已獲得解決，但是目前對於此等之 圖案形成性、機械特性卻仍然並未獲得足夠的特性。 (發明專利文獻1 )日本發明專利特開第2000-256428號 © 公報 (發明專利文獻2 )日本發明專利特開第2002-220407號 公報 【發明内容】 〔所欲解決之技術問題〕 本發明係以提供一種具有優越的圖案形成性與圖案的機 械特性之活性能量線硬化性樹脂材料爲其目的。 〔解決問題之技術方法〕 ® 本發明之發明人等發現：藉由在由含有特定的碳數之直 鏈或分枝鏈狀之烷基之（甲基）丙烯酸酯、（甲基）丙烯酸 及其他之（甲基）丙烯酸酯所獲得之共聚合物的一部份酸基 加成含有環氧基之不飽和化合物，則可獲得具有良好的圖案 形成性與圖案的機械特性兩者並存之活性能量線硬化性樹脂 (改質共聚合物），因此達成本發明。 亦即，本發明係提供一種活性能量線硬化性樹脂，其係 由在共聚合物（A)的一部份酸基加成含有環氧基之不飽和化 合物（d)所獲得之改質共聚合物（B)所構成，其中共聚合 -6- 200940570 物（A)係由含有碳數爲5至18之直鏈或分枝鏈狀烷基之（ 甲基）丙烯酸酯（a)、（甲基）丙烯酸（b)、及未含有碳 數爲5至18之直鏈或分枝鏈狀烷基之（甲基）丙烯酸酯（c )所獲得。 並且，本發明係提供一種如前所述之活性能量線硬化性 樹脂，其中「含有碳數爲5至18之直鏈或分枝鏈狀烷基之（ 甲基）丙烯酸酯（a)」係含有分枝鏈狀烷基之（甲基）丙烯 酸酯。 〇 並且，本發明係提供一種如前所述之活性能量線硬化性 樹脂，其中「含有碳數爲5至18之直鏈或分枝鏈狀烷基之（ 甲基）丙烯酸酯（a)」係（甲基）丙烯酸異癸酯。 並且，本發明係提供一種如前所述之活性能量線硬化性 樹脂，其中「含有環氧基之不飽和化合物（d)」係（甲基） 丙烯酸3,4-環氧環己基甲酯。 並且，本發明係提供一種如前所述之活性能量線硬化性 樹脂，其係用作爲液狀阻劑（liquid resist )、乾膜（dry film ® )、液晶顯示器用彩色濾光片或黑色矩陣（black matrix)用 顔料阻劑（pigment resist)或塗布用保護膜之成份。 並且，本發明係提供一種如前所述之活性能量線硬化性 樹脂之製造方法，其特徵爲：在由含有碳數爲5至18之直鏈 或分枝鏈狀烷基之（甲基）丙烯酸酯（a)、（甲基）丙烯酸 (b)、及未含有碳數爲5至18之直鏈或分枝鏈狀烷基之（ 甲基）丙烯酸酯（c)所獲得之共聚合物（A)的一部份酸基 ’在觸媒之存在下，加成含有環氧基之不飽和化合物（d)以 獲得改質聚合物（B )。 200940570 〔發明之功效〕 本發明之活性能量線硬化性樹脂或使用它所構成之活性 能量線硬化性樹脂組成物，係在使用照相法形成之圖案中， 由於可顯現優越的圖案形成性且所獲得之圖案係具有優越的 機械特性，因此適合用作爲需要形成微細圖案之印刷電路板 用途等。 【實施方式】 〔本發明之最佳實施方式〕 〇 在下文中，則就本發明更詳細地加以說明。 本發明之活性能量線硬化性樹脂係以在共聚合物（A )的 一部份酸基加成含有環氧基之不飽和化合物（d)所獲得之改 質共聚合物（B)作爲必要之成份所構成，其中共聚合物（A )係由含有碳數爲5至18之直鏈或分枝鏈狀烷基之（甲基） 丙烯酸酯（a)(在下文中，有時候只稱爲（甲基）丙烯酸酯 (a))、（甲基）丙烯酸（b)、及未含有碳數爲5至18之 直鏈或分枝鏈狀烷基之（甲基）丙烯酸酯（c)(在下文中， 〇 有時候只稱爲（甲基）丙烯酸酯（C))所獲得》 如上所述「共聚合物（A)」係以（甲基）丙烯酸酯（a )、（甲基）丙烯酸（b)、及（甲基）丙烯酸酯（c)作爲 必要之單體成份所構成之共聚合物。 用作爲本發明之共聚合物（A)之單體成份之「（甲基） 丙烯酸酯（a)」係具有直鏈狀或分枝鏈狀之烷基之（甲基） 丙烯酸烷基酯，且可以下列通式來代表。 200940570200940570 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to an active energy ray-curable resin. More specifically, it relates to a photosensitive resin which can be easily formed into an image by exposure and development of a dilute aqueous alkali solution after the film is formed. In particular, it relates to a resistive ink (resist ink) which can be used for a printed circuit board, an LSI (large integrated circuit) related to an electronic device, a color filter attached to a liquid crystal, a sealing agent, or the like. ) The active energy ray-hardening 0 resin of the binder resin. Further, it relates to a method for producing the active energy ray-curable resin. [Prior Art] In terms of a printed circuit board, a solder resist resin has been widely used as a permanent protective film for a substrate circuit. When a solder resist is previously formed on a printed circuit board, a thermosetting resist ink is printed by a screen printing method, and then the transfer portion is thermally hardened or ultraviolet hardened. However, the screen printing method causes a phenomenon such as bleeding, bleed-through, and sagging during printing, which results in an inability to correspond to the high density of the board. Therefore, in order to solve this problem, a photographic method (photoresist, etc.) has been developed and put into practical application. Photographic method is a method of exposing and developing through a patterned film to form a desired pattern. In the photographic method as described above, a chlorine-based solvent or the like has been used as a developing solution. However, in recent years, it has been transferred from solvent development to various fields due to environmental problems, resource conservation, energy conservation, and workability. The development trend of dilute alkali aqueous solution, and in the field of printed circuit board processing, has also evolved into a photoresist printing ink that has been transferred from a solvent developing type to a dilute aqueous solution developing type. Various photoresist inks have been proposed corresponding to these trends, for example, as a photocurable resin composition in which the ink sensitivity and the non-sticky (tack free) are balanced: one has a bondable a divalent group of compounds between a saturated group and a carboxyl group; a part comprising an acid group containing an epoxy group in a copolymer obtained from (meth)acrylic acid and (meth)acrylic acid ester a curable resin of a modified copolymer obtained by an unsaturated compound (see Patent Document 1); or a composition comprising less than 1 mole of a hydroxyalkylalkyl (meth)acrylate obtained by adding 1 mole a photocurable resin composition having a terminal carboxyl group-containing monomer composition obtained by modifying an acid anhydride of a terminal hydroxyl group (meth) acrylate obtained by a ratio of an ε-caprolactone monomer; or a A photocurable resin composition having a monomer composition having a terminal carboxyl group obtained by adding an ε-caprolactone monomer having a ratio of (meth)acrylic acid of less than 1 mol (see Patent Document 2). However, the demand for such photocurable resin materials tends to be stricter in recent years. With the high functionality, power saving, and miniaturization of electronic components, the circuit pattern has evolved into a finer one, and the photocurable resin material is required to have a good pattern formation property of a high-definition pattern. On the other hand, with the miniaturization of the pattern, a new problem that the resist pattern is easily collapsed after exposure has appeared. In response to this problem, although a method of thinning the photoresist to reduce the aspect ratio of the pattern can be employed, in this case, the reduction in etching resistance is a problem. Therefore, it has become a necessary measure to suppress the collapse of the miniaturization by increasing the mechanical strength of the resist pattern itself. Further, depending on the application, the performance required for the photoresist pattern is not only the mechanical strength such as the so-called "hardness", but sometimes the 200940570 requires the shape restoring force after the load is applied and then the load is removed. In other words, in addition to the characteristics of the photocurable resin material as described above, such as sensitivity or non-stickiness (surface dryness), it is further required to have excellent pattern formability and mechanical characteristics of the pattern according to the requirements. The photocurable resin composition of the invention patent document as described above has been solved in terms of sensitivity and the like, but at present, sufficient characteristics have not been obtained for such pattern formation properties and mechanical properties. (Patent Document 1) Japanese Laid-Open Patent Publication No. 2000-256428 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2002-220407 [Draft of the Invention] [Technical Problem to be Solved] The present invention is It is an object of the invention to provide an active energy ray-curable resin material having excellent pattern formability and mechanical properties of a pattern. [Technical method for solving the problem] The inventors of the present invention found that (meth)acrylic acid (meth)acrylic acid and (meth)acrylic acid are contained in a linear or branched chain alkyl group having a specific carbon number. A part of the acid group of the copolymer obtained by the other (meth) acrylate is added to the epoxy group-containing unsaturated compound, and the activity of both the pattern forming property and the mechanical property of the pattern can be obtained. The energy ray-curable resin (modified copolymer) is thus obtained. That is, the present invention provides an active energy ray-curable resin which is obtained by adding an epoxy group-containing unsaturated compound (d) to a part of the acid group of the copolymer (A). Polymer (B) wherein copolymerization-6-200940570 (A) is a (meth) acrylate (a) containing a linear or branched chain alkyl group having 5 to 18 carbon atoms (a), Methyl)acrylic acid (b), and (meth)acrylate (c) which does not contain a linear or branched chain alkyl group having 5 to 18 carbon atoms. Further, the present invention provides an active energy ray-curable resin as described above, wherein "(meth)acrylate (a)" having a linear or branched chain alkyl group having 5 to 18 carbon atoms is used. A (meth) acrylate containing a branched chain alkyl group. Further, the present invention provides an active energy ray-curable resin as described above, wherein "(meth) acrylate (a) having a linear or branched chain alkyl group having 5 to 18 carbon atoms" Is isodecyl (meth)acrylate. Further, the present invention provides an active energy ray-curable resin as described above, wherein the "epoxy group-containing unsaturated compound (d)" is (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester. Further, the present invention provides an active energy ray-curable resin as described above, which is used as a liquid resist, a dry film ® , a color filter for a liquid crystal display or a black matrix. (black matrix) A pigment resist or a component of a protective film for coating. Further, the present invention provides a method for producing an active energy ray-curable resin as described above, which is characterized in that it is composed of a linear or branched chain alkyl group having a carbon number of 5 to 18 (methyl). Acrylate (a), (meth)acrylic acid (b), and a copolymer obtained from (meth) acrylate (c) which does not contain a linear or branched chain alkyl group having 5 to 18 carbon atoms A part of the acid group of (A) is added to the epoxy group-containing unsaturated compound (d) in the presence of a catalyst to obtain a modified polymer (B). 200940570 [Effect of the invention] The active energy ray-curable resin of the present invention or the active energy ray-curable resin composition using the same is used in a pattern formed by a photographic method, since excellent pattern formability can be exhibited and The obtained pattern has excellent mechanical properties and is therefore suitable for use as a printed circuit board or the like which requires a fine pattern to be formed. [Embodiment] [Best Embodiment of the Invention] 〇 Hereinafter, the present invention will be described in more detail. The active energy ray-curable resin of the present invention is required to be a modified copolymer (B) obtained by adding an epoxy group-containing unsaturated compound (d) to a part of the acid group of the copolymer (A). The composition of the copolymer (A) is a (meth) acrylate (a) containing a linear or branched chain alkyl group having a carbon number of 5 to 18 (hereinafter, sometimes only referred to as (Meth) acrylate (a)), (meth)acrylic acid (b), and (meth) acrylate (c) which does not contain a linear or branched chain alkyl group having 5 to 18 carbon atoms ( In the following, 〇 is sometimes only referred to as (meth) acrylate (C)). As described above, "copolymer (A)" is based on (meth) acrylate (a), (meth) acrylate. (b), and (meth) acrylate (c) as a copolymer of the necessary monomer components. The "(meth) acrylate (a)" used as a monomer component of the copolymer (A) of the present invention is an alkyl (meth) acrylate having a linear or branched chain alkyl group. And can be represented by the following formula. 200940570
H2C=〒， (1) COOR2 在上式（1)中，R1係代表氫和/或甲基；R2係較佳爲碳 數爲5至18(更佳爲7至18，進一步更佳爲10至15)之直 鏈狀烷基或分枝鏈狀烷基。此外，該烷基係由碳-碳鍵之骨架 所構成，且未含有具有環狀結構之烷基。其中，（甲基）丙 烯酸酯（a)較佳爲R2爲分枝鏈狀之烷基之含有分枝鏈狀烷基 0 之（甲基）丙烯酸酯。屬於此等者係包括：例如（甲基）丙 烯酸2-乙基己酯、（甲基）丙烯酸異癸酯等；其中，特佳爲 (甲基）丙烯酸異癸酯。此外，該烷基較佳爲僅由碳原子及 氫原子所構成之烷基，但是也可爲含有羥基之羥基烷基。 由於含有如上所述特定範圍的碳數之直鏈或分枝鏈狀之 烷基，（甲基）丙烯酸酯（a)會使共聚合物之結晶性崩潰， 而其功效係對於硬化物賦予變形恢復力。同時，具有調整共 聚合物之疏水性/親水性之作用，而其功效係改良與樹脂組成 〇 物之相溶性。若烷基係具有環狀結構時、或在骨架含有醚鍵 或酯鍵等時，則無法充分地獲得如上所述之功效。 本發明之共聚合物（A)之單體成份係更進一步使用（甲 基）丙烯酸（b)。此外，所謂的「（甲基）丙烯酸」係意謂 「丙烯酸和/或甲基丙烯酸」。該（甲基）丙烯酸（b)係可對 於共聚合物提供酸基，而其功效係可實現在稀鹼水溶液下之 顯影。其中，從能保持該樹脂之高玻璃轉移點及與組成物中 之其他成份之相溶性的觀點來考慮，則較佳爲甲基丙烯酸。 本發明之共聚合物（A)之單體成份係更進一步使用除了 200940570 (甲基）丙烯酸酯（a)以外之（甲基）丙烯酸酯（c)。在 本發明所使用的「（甲基）丙烯酸酯（c)」係包括_·例如， (甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯 酸丙酯、（甲基）丙烯酸正-丁酯等之含有碳數爲1至4之直 鏈狀烷基之（甲基）丙烯酸烷基酯，（甲基）丙烯酸金剛烷 酯、（甲基）丙烯酸降冰片酯等之含有環狀結構之（甲基） 丙烯酸烷基酯等的除了如前所述含有烷基之（甲基）丙烯酸 烷基酯（a)以外之（甲基）丙烯酸烷基酯類；（甲基）丙烯 〇 酸2-羥基乙酯、（甲基）丙烯酸羥基丙酯、（甲基）丙烯酸 羥基丁酯、（甲基）丙烯酸羥基金剛烷酯、（甲基）丙烯酸 羥基降冰片酯等之含有碳數爲1至4之直鏈狀烷基或環狀結 構的含有羥基之（甲基）丙烯酸酯類；經己內酯改質之（甲 基）丙烯酸2-羥基乙酯、（甲基）丙烯酸甲氧基二甘醇酯、 (甲基）丙烯酸乙氧基二甘醇酯、（甲基）丙烯酸異辛氧基 二甘醇酯、（甲基）丙烯酸苯氧基三甘醇酯、（甲基）丙烯 酸甲氧基三甘醇酯、聚（甲基）丙烯酸甲氧基乙二醇酯等之 Ο 「（甲基）丙烯酸酯類」等。在如上所述之中，較佳爲甲基 丙烯酸甲酯、甲基丙烯酸正-丁酯、甲基丙烯酸苯甲酯；特佳 爲甲基丙烯酸甲酯、甲基丙烯酸正-丁酯。此等係可單獨使用 或混合倂用。 該（甲基）丙烯酸酯（c)係具有將共聚合物之疏水性/ 親水性加以微調整之作用，而其功效係可改善與樹脂組成物 之相溶性。 此外，視需要也可含有其他之共聚合單體成份。其他之 共聚合單體成份係包括：例如，在分子中含有兩個以上之乙 -10- .200940570 烯基苯酚類或順丁烯二酸（馬來酸）等之羧基之單體。此等 係可單獨使用或混合使用。 本發明之共聚合物（A)係將如上所述（a)至（c)之成 份以傳統慣用的丙烯酸系共聚合物之聚合方法及聚合條件加 以聚合來製造。聚合方法或聚合條件雖然並無特殊的限制， 但疋從反應控制之合易性的觀點來考慮，則較佳爲溶液聚合 ，且較佳爲聚合溫度爲90至no °c、聚合時間爲6至1〇小時 〇 在本發明之共聚合物（A)中’（甲基）丙烯酸酯（3) 之單體混合比率，從賦予硬化物之變形恢復力的觀點來考慮 ’則較佳爲在共聚合物（A)中爲1〇至80莫耳％，更佳爲1〇 至50莫耳％。從賦予在稀鹼水溶液下之顯影性的觀點來考慮 ’則（甲基）丙烯酸（b)較佳爲1至50莫耳％。從調整共聚 合物（A)與其他成份之相溶性的觀點來考慮，則（甲基）丙 烯酸酯（c )較佳爲10至80莫耳％，更佳爲20至70莫耳％。 本發明之共聚合物（A)係在如上所述舉例中，（a)爲 甲基丙烯酸異癸酯、（b)爲甲基丙烯酸、（c)爲由甲基丙 烯酸甲酯和/或甲基丙烯酸正-丁酯之單體的組合所構成者，由 於會發揮特別優越的硬化物之變形恢復力、圖案形成性，因 此爲較佳。在如上所述之組合中之單體混合比率〔（a )/( b )/ (c)〕（莫耳％)較佳爲（15至30莫耳％) / (35至50 莫耳％) / ( 30至45莫耳％)，更佳爲（17至28莫耳％) / ( 38至49莫耳％ ) / (31至42莫耳％ )，進一步更佳爲（20至 25莫耳％ ) / ( 41至47莫耳％ ) / ( 32至37莫耳％ )。H2C=〒, (1) COOR2 In the above formula (1), R1 represents hydrogen and/or methyl; R2 preferably has a carbon number of 5 to 18 (more preferably 7 to 18, still more preferably 10). a linear alkyl group or a branched chain alkyl group of 15). Further, the alkyl group is composed of a skeleton of a carbon-carbon bond, and does not contain an alkyl group having a cyclic structure. Among them, the (meth) acrylate (a) is preferably a (meth) acrylate having a branched chain alkyl group in which R2 is a branched chain alkyl group. These include, for example, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and the like; among them, isodecyl (meth)acrylate is particularly preferred. Further, the alkyl group is preferably an alkyl group composed only of a carbon atom and a hydrogen atom, but may be a hydroxyalkyl group having a hydroxyl group. The (meth) acrylate (a) collapses the crystallinity of the copolymer due to the linear or branched chain alkyl group having a specific range of carbon numbers as described above, and the effect is to impart deformation to the cured product. Resilience. At the same time, it has the effect of adjusting the hydrophobicity/hydrophilicity of the copolymer, and its effect is to improve the compatibility with the resin composition. When the alkyl group has a cyclic structure or when the skeleton contains an ether bond or an ester bond, the above effects cannot be sufficiently obtained. The monomer component of the copolymer (A) of the present invention further uses (meth)acrylic acid (b). Further, the term "(meth)acrylic" means "acrylic acid and/or methacrylic acid". The (meth)acrylic acid (b) provides an acid group for the copolymer, and its efficacy enables development under a dilute aqueous alkali solution. Among them, methacrylic acid is preferred from the viewpoint of maintaining a high glass transition point of the resin and compatibility with other components in the composition. The monomer component of the copolymer (A) of the present invention is further used (meth) acrylate (c) other than 200940570 (meth) acrylate (a). The "(meth) acrylate (c)" used in the present invention includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (methyl) a (meth)acrylic acid alkyl ester containing a linear alkyl group having 1 to 4 carbon atoms such as n-butyl acrylate, an adamantyl (meth)acrylate, a norbornene (meth)acrylate, or the like. a (meth)acrylic acid alkyl ester having a cyclic structure, such as an alkyl (meth)acrylate other than the alkyl (meth)acrylate (a) as described above; Included as 2-hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, hydroxynorbornyl (meth) acrylate, etc. a linear alkyl group having 1 to 4 carbon atoms or a hydroxyl group-containing (meth) acrylate having a cyclic structure; 2-hydroxyethyl (meth) acrylate modified by caprolactone, (meth) Methoxydiglycol acrylate, ethoxydiglycol (meth)acrylate, (methyl) Isooctyl octaethoxylate, phenoxy triethylene glycol (meth)acrylate, methoxy triethylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate Etc. 「 "(Meth) acrylates" and the like. Among the above, methyl methacrylate, n-butyl methacrylate, and benzyl methacrylate are preferred; methyl methacrylate and n-butyl methacrylate are particularly preferred. These can be used alone or in combination. The (meth) acrylate (c) has a function of finely adjusting the hydrophobicity/hydrophilicity of the copolymer, and its effect is to improve the compatibility with the resin composition. In addition, other copolymerized monomer components may be contained as needed. Other copolymerized monomer components include, for example, monomers having two or more carboxyl groups in the molecule of B-.200940570 alkenylphenol or maleic acid (maleic acid). These can be used alone or in combination. The copolymer (A) of the present invention is produced by polymerizing the components (a) to (c) as described above by a conventional polymerization method and polymerization conditions of an acrylic copolymer. The polymerization method or the polymerization conditions are not particularly limited, but from the viewpoint of the ease of reaction control, solution polymerization is preferred, and the polymerization temperature is preferably 90 to no ° c and the polymerization time is 6 In the copolymer (A) of the present invention, the monomer mixing ratio of (meth) acrylate (3) is considered to be from the viewpoint of imparting a restoring force to the cured product. The copolymer (A) is from 1 to 80 mol%, more preferably from 1 to 50 mol%. From the viewpoint of imparting developability under a dilute aqueous alkali solution, the (meth)acrylic acid (b) is preferably from 1 to 50 mol%. The (meth) acrylate (c) is preferably from 10 to 80 mol%, more preferably from 20 to 70 mol%, from the viewpoint of adjusting the compatibility of the copolymer (A) with other components. The copolymer (A) of the present invention is exemplified above, (a) is isodecyl methacrylate, (b) is methacrylic acid, (c) is methyl methacrylate and/or The combination of the monomers of n-butyl acrylate and the like is preferable because it exhibits particularly excellent deformation restoring power and pattern formability of the cured product. The monomer mixing ratio [(a)/(b)/(c)] (mol%) in the combination as described above is preferably (15 to 30 mol%) / (35 to 50 mol%) / (30 to 45 mole%), more preferably (17 to 28 mole%) / (38 to 49 mole%) / (31 to 42 mole%), further better (20 to 25 moles) %) / (41 to 47 mol%) / (32 to 37 mol%).
本發明之共聚合物（A)之分子量，從調整共聚合物（A -11- 200940570 )與其他成份之相溶性的觀點來考慮，則較佳爲5,000至10,000 ，更佳爲5,000至8,000。 本發明之改質共聚合物（B)係在該共聚合物（A)的一 部份酸基加成含有環氧基之不飽和化合物（d)所獲得。 如上所述含有環氧基之不飽和化合物（d)係在一分子中 具有一個自由基聚合性之不飽和基與環氧基之化合物。該環 氧基係可爲含有用於構成環狀脂肪族骨架的兩個碳原子所形 成之所謂的「脂環式環氧基、或脂環族環氧基」。 〇 該「含有脂環式環氧基之不飽和化合物」係包括：例如 ，如下所述通式之化合物；其中，特佳爲（甲基）丙烯酸3,4-環氧環己基甲酯。The molecular weight of the copolymer (A) of the present invention is preferably from 5,000 to 10,000, more preferably from 5,000 to 8,000, from the viewpoint of adjusting the compatibility of the copolymer (A -11-200940570) with other components. The modified copolymer (B) of the present invention is obtained by adding an acid group-containing unsaturated compound (d) containing an epoxy group to a part of the copolymer (A). The epoxy group-containing unsaturated compound (d) as described above is a compound having a radical polymerizable unsaturated group and an epoxy group in one molecule. The epoxy group may be a so-called "alicyclic epoxy group or alicyclic epoxy group" which is formed by two carbon atoms constituting a cyclic aliphatic skeleton. The "alicyclic compound having an alicyclic epoxy group" includes, for example, a compound of the formula: wherein it is particularly preferably 3,4-epoxycyclohexylmethyl (meth)acrylate.
-12 200940570-12 200940570
此外，在如上所述通式中，R3係代表氫原子或甲基：r4 係代表碳數爲1至6之二價之脂肪族烴基。 此外，「含有脂環族環氧基之不飽和化合物」係包括： 例如，甲基丙烯酸縮水甘油酯、甲基丙烯酸甲基縮水甘油 酯、烯丙基縮水甘油基醚等。此等之含有環氧基之不飽和化 合物係可單獨使用或兩種以上倂用。 在本發明之改質共聚合物（B)中，相對於1公斤之改質 共聚合物（B)，含有環氧基之不飽和化合物（d)之加成量 較佳爲使用能使雙鍵量成爲0.9至3.3莫耳之量。若少於0.9 莫耳時，則有可能導致無法獲得足夠的硬化性，若多於3.3 莫耳時，則有可能導致儲存穩定性差之情況。 在本發明中，在共聚合物（A)加成含有環氧基之不飽和 化合物（d)時所使用的「觸媒」係包括：二甲基苯甲基胺、 三乙基胺、四甲基伸乙基二胺、三-正辛基胺等之「三級胺」 ’四甲基氯化銨、四甲基溴化銨、四丁基溴化銨等之四級銨 鹽，四甲基脲等之烷基脲，四甲基胍等之烷基狐，以環烷酸 鈷等所代表之金屬化合物、有機金屬錯合物，三苯基膦等之 -13- .200940570 膦系化合物及此等之鹽等，但是較佳爲以三苯基膦所代表之 三級膦。如上所述之觸媒係可單獨使用或混合使用。相對於 100重量份之含有環氧基之不飽和化合物（d)此等之觸媒較 佳爲使用0.01至10重量份，更佳爲0.1至5.0重量份，進一 步更佳爲使用0.5至3.0重量份。若少於0.01重量份時，則觸 媒功效低，但是不必加入超過10重量份之量。 此外，在共聚合物（A)加成含有環氧基之不飽和化合物 (d)時所使用的溶劑，只要其爲能溶解所使用的原料者時， 〇 則並無特殊的限制，可使用：例如，苯、甲苯、二甲苯等之 「芳香族烴類」；甲醇、乙醇、2-丙醇等之「醇類」；丙酮、 甲基乙基酮、甲基異丁基酮等之「酮類」：二乙基醚、二丁 基醚、二噁烷等之「醚類」：醋酸乙酯、醋酸異丁酯、一醋 酸乙二醇酯、一醋酸丙二醇酯、一醋酸二丙二醇酯等之「酯 類」；乙二醇一烷基醚類、二甘醇一烷基醚類、丙二醇一烷 基醚類、二丙二醇一烷基醚類、丁二醇一烷基醚類、乙二醇 二烷基醚類、二甘醇二甲基醚、二甘醇二乙基醚等之二甘醇 〇 二烷基醚類、醋酸乙二醇一烷基醚酯類、醋酸二甘醇一烷基 醚酯類；二甲基甲醯胺、二甲基乙醯胺等之「醯胺類」·，四 氯化碳、氯仿等之「鹵化烴」等。此等之溶劑係可單獨使用 或混合使用。加成含有環氧基之不飽和化合物（d)之條件係 並無特殊的限制，例如，可爲在50至120°C下爲約4至50小 時。 此外，雖然改質共聚合物（B)係較佳爲將如上所述（甲 基）丙烯酸酯（a)、（甲基）丙烯酸（b)、及（甲基）丙 烯酸酯（c)加以共聚合以製得共聚合物（A)後，加成含有 -14- 200940570 環氧基之不飽和化合物（d)之製造方法所獲得者，但是若最 終結構爲相同的聚合物時，則製造方法並無特殊的限制，也 可爲未經由如上所述之共聚合物（A)所製得之共聚合物。例 如，在僅由（甲基）丙烯酸（b)、及（甲基）丙烯酸酯（c )所構成之共聚合物之羧基，加成具有碳數爲5至18之直鏈 或分枝鏈狀之烷基鏈部份的環氧化合物（不飽和化合物除外 )與含有環氧基之不飽和化合物（d)兩者所獲得之化合物等 〇 〇 本發明之改質共聚合物（B)之酸價較佳爲10至120 ( KOH-mg/g)，更佳爲45至70 ( KOH-mg/g)。若酸價爲小於 10 ( KOH-mg/g)時，欲在稀鹼水溶液下移除未硬化膜則有困 難，若超過120 ( KOH-mg/g)時，則有可能發生硬化皮膜之 耐水性、電特性劣化之情況。 本發明之改質共聚合物（B)之重量平均分子量較佳爲 5,000至15,000，更佳爲5,000至10,000，進一步更佳爲5,000 至8,000。若重量平均分子量爲少於5,000時，則有可能導致 Ο 不黏（表乾）性能差之情況、曝光後的塗膜之耐濕性惡化， 使得在顯影時造成膜減少現象以致解析度大幅度地變差之情 況。此外，若重量平均分子量爲超過15，000時，則有可能導 致顯影性顯著地惡化之情況、或儲存穩定性變差之情況。 從本發明之活性能量線硬化性樹脂、稀釋單體和/或寡聚 物即可製得可溶於稀鹸水溶液之活性能量線硬化性樹脂組成 物。其中，欲獲得光硬化性之樹脂組成物時，則較佳爲進一 步添加光聚合引發劑。如上所述之活性能量線硬化性樹脂組 成物係以可見光、紅外線、紫外線、電子射線等之活性能量 -15- .200940570 線加以硬化；其中，較佳爲紫外線、電子射線。 如上所述之稀釋單體或寡聚物係包括：以（甲基）丙烯 酸酯化合物、苯乙烯等之乙烯基芳香族化合物、醯胺系不飽 和化合物等所代表之具有自由基聚合性雙鍵之化合物。代表 性的「（甲基）丙烯酸酯化合物」係可例示：（甲基）丙烯 酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲 基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己 酯等之「（甲基）丙烯酸烷基酯類」；（甲基）丙烯酸2-羥 〇 基乙酯、（甲基）丙烯酸羥基丙酯、（甲基）丙烯酸羥基丁 酯、經己內酯改質之（甲基）丙烯酸2-羥基乙酯等之「具有 羥基之（甲基）丙烯酸酯類」；（甲基）丙烯酸甲氧基二甘 醇酯、（甲基）丙烯酸乙氧基二甘醇酯、（甲基）丙烯酸異 辛氧基二甘醇酯、（甲基）丙烯酸苯氧基三甘醇酯、（甲基 )丙烯酸甲氧基三甘醇酯、聚（甲基）丙烯酸甲氧基乙二醇 #400酯等之「（甲基）丙烯酸酯類」；二（甲基）丙烯酸1，6-己二醇酯、二（甲基）丙烯酸新戊二醇酯等之「二官能（甲 〇 基）丙烯酸酯類」：三（甲基）丙烯酸三羥甲基丙烷酯等之 「三官能（甲基）丙烯酸酯類」等。此外，「聚合性預聚合 物（寡聚物）」係包括：例如，聚酯多元醇之（甲基）丙烯 酸酯類、聚醚多元醇之（甲基）丙烯酸酯類、經在聚環氧化 物與（甲基）丙烯酸之加成物及多元醇隔著聚異氰酸酯而導 入羥基（甲基）丙烯酸酯所獲得之樹脂等。 相對於100重量份之改質共聚合物（B)，如上所述之稀 釋單體及寡聚物之混合量較佳爲1至300重量份，更佳爲1 至100重量份。若稀釋單體及寡聚物之混合量爲超過300重 -16 - 200940570 量份時，則有可能圖案形成性降低之情況、或硬化後之圖案 的機械強度及變形恢復力降低之情況。 使用於如上所述之活性能量線硬化性樹脂組成物之「光 聚合引發劑」係包括：例如，二苯甲酮、苯乙酮、二苯乙二 酮（benzil)、苯甲基二甲基酮、苯偶姻、苯偶姻甲基醚、苯 偶姻乙基醚、苯偶姻異丙基醚、二甲氧基苯乙酮、二甲氧基 苯基苯乙酮、二乙氧基苯乙酮、二苯基二硫化物等。此等之 光聚合引發劑係可單獨或混合使用。此等之光聚合引發劑係 〇 可含有用於加強光吸收能量對於聚合引發游離基之轉換的增 效劑（synergist)，例如第三級胺。相對於1〇〇重量份之活性 能量線硬化性樹脂，光聚合引發劑之使用量較佳爲0.1至50 重量份，更佳爲1至20重量份。此外，若採取以電子射線照 射來硬化如上所述之活性能量線硬化性樹脂組成物時，則未 必需要添加光聚合引發劑。 如上所述之活性能量線硬化性樹脂組成物，從賦予吾所 欲之功能的觀點來考慮，則可進一步含有環氧化合物和/或環 〇 氧樹脂（脂環式環氧樹脂或共聚合型環氧樹脂等），將酚醛 清漆或雙酚系環氧樹脂以（甲基）丙烯酸加以酸改質後加成 酸酐所獲得之樹脂。可添加之「環氧化合物」係包括：例如 ，環氧化聚丁二烯、環氧化丁二烯-苯乙烯嵌段共聚合物等含 有不飽和基之環氧化樹脂，且可獲得之市售商品則係包括： DAICEL化學工業股份有限公司（DAICEL CHEMICAL INDUSTRIES，LTD.)製造之 EPOLEAD PB、ESBS 等。「S旨環 式環氧樹脂」係包括：例如，DAICEL化學工業股份有限公司 製造之CELLOXIDE 2021、EHPE ;三井化學股份有限公司（ -17- .200940570Further, in the above formula, R3 represents a hydrogen atom or a methyl group: the r4 system represents a divalent aliphatic hydrocarbon group having a carbon number of 1 to 6. Further, the "alicyclic compound having an alicyclic epoxy group" includes, for example, glycidyl methacrylate, methyl glycidyl methacrylate, allyl glycidyl ether and the like. These epoxy group-containing unsaturated compounds may be used singly or in combination of two or more. In the modified copolymer (B) of the present invention, the addition amount of the epoxy group-containing unsaturated compound (d) is preferably used in combination with 1 kg of the modified copolymer (B). The amount of the bond is from 0.9 to 3.3 moles. If it is less than 0.9 moles, it may result in insufficient hardenability, and if it is more than 3.3 moles, it may result in poor storage stability. In the present invention, the "catalyst" used in the addition of the epoxy group-containing unsaturated compound (d) to the copolymer (A) includes dimethylbenzylamine, triethylamine, and tetra a "tertiary amine" such as methyl ethyl diamine or tri-n-octylamine, and a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or tetrabutylammonium bromide, Alkyl urea such as methyl urea, alkyl fox such as tetramethyl hydrazine, metal compound represented by cobalt naphthenate or the like, organometallic complex, triphenylphosphine, etc.-13-.200940570 phosphine system The compound, such a salt or the like, but is preferably a tertiary phosphine represented by triphenylphosphine. The catalysts as described above may be used singly or in combination. The catalyst is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, still more preferably 0.5 to 3.0 parts by weight, per 100 parts by weight of the epoxy group-containing unsaturated compound (d). Share. If it is less than 0.01 part by weight, the catalytic effect is low, but it is not necessary to add more than 10 parts by weight. Further, the solvent used in the addition of the epoxy group-containing unsaturated compound (d) to the copolymer (A) is not particularly limited as long as it is a material which can be used for dissolving, and can be used. For example, "aromatic hydrocarbons" such as benzene, toluene, and xylene; "alcohols" such as methanol, ethanol, and 2-propanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc." Ketones: "ethers" such as diethyl ether, dibutyl ether, dioxane, etc.: ethyl acetate, isobutyl acetate, ethylene glycol monoacetate, monopropylene glycol acetate, dipropylene glycol monoacetate Such as "esters"; ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, butanediol monoalkyl ethers, B Diethylene glycol sulfonium dialkyl ethers such as diol dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monoalkyl ether esters, diethylene glycol acetate A monoalkyl ether ester; a "halamine" such as dimethylformamide or dimethylacetamide, or a "halogenated hydrocarbon" such as carbon tetrachloride or chloroform. These solvents may be used singly or in combination. The conditions for the addition of the epoxy group-containing unsaturated compound (d) are not particularly limited and, for example, may be from about 4 to 50 hours at 50 to 120 °C. Further, although the modified copolymer (B) is preferably a total of (meth) acrylate (a), (meth) acrylate (b), and (meth) acrylate (c) as described above. After the polymerization to obtain the copolymer (A), the method of producing the unsaturated compound (d) containing -14 to 200940570 epoxy group is obtained, but if the final structure is the same polymer, the production method There is no particular limitation, and it may also be a copolymer which is not obtained by the copolymer (A) as described above. For example, in the carboxyl group of the copolymer composed only of (meth)acrylic acid (b) and (meth) acrylate (c), the addition has a linear or branched chain having a carbon number of 5 to 18. The compound obtained by the epoxy compound of the alkyl chain moiety (excluding the unsaturated compound) and the epoxy group-containing unsaturated compound (d) is equivalent to the acid of the modified copolymer (B) of the present invention. The price is preferably from 10 to 120 (KOH-mg/g), more preferably from 45 to 70 (KOH-mg/g). If the acid value is less than 10 (KOH-mg/g), it is difficult to remove the uncured film under a dilute aqueous alkali solution. If it exceeds 120 (KOH-mg/g), the water resistance of the hardened film may occur. Deterioration of properties and electrical characteristics. The weight average molecular weight of the modified copolymer (B) of the present invention is preferably from 5,000 to 15,000, more preferably from 5,000 to 10,000, still more preferably from 5,000 to 8,000. When the weight average molecular weight is less than 5,000, there is a possibility that the non-sticky (dry surface) performance is poor, and the moisture resistance of the coating film after exposure is deteriorated, so that the film is reduced during development so that the resolution is large. The situation of poor ground. Further, when the weight average molecular weight is more than 15,000, the developability may be remarkably deteriorated or the storage stability may be deteriorated. From the active energy ray-curable resin, the diluted monomer and/or the oligomer of the present invention, an active energy ray-curable resin composition soluble in a dilute aqueous solution can be obtained. Among them, in order to obtain a photocurable resin composition, it is preferred to further add a photopolymerization initiator. The active energy ray-curable resin composition as described above is cured by an active energy -15 - 200940570 line of visible light, infrared rays, ultraviolet rays, electron beams or the like; among them, ultraviolet rays and electron rays are preferable. The dilute monomer or oligomer as described above includes a radical polymerizable double bond represented by a (meth) acrylate compound, a vinyl aromatic compound such as styrene, a guanamine-based unsaturated compound or the like. Compound. Representative examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. "(meth)acrylic acid alkyl esters such as pentyl acrylate or hexyl (meth) acrylate; 2-hydroxymethyl ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ( "hydroxy) hydroxybutyl acrylate, "hydroxy) (meth) acrylate such as 2-hydroxyethyl (meth) acrylate modified by caprolactone; methoxy bisglycol (meth) acrylate Alcohol ester, ethoxydiglycol (meth)acrylate, isooctyloxyethylene glycol (meth)acrylate, phenoxy triethylene glycol (meth)acrylate, methoxy (meth)acrylate "(meth)acrylates" such as triethylene glycol ester, poly(meth)acrylic acid methoxyglycol #400 ester, etc.; 1,6-hexanediol di(meth)acrylate, two ( "Difunctional (meth) acrylates such as methyl methacrylate neopentyl glycol ester: tris(methyl) Acrylate, trimethylolpropane triacrylate, etc. "trifunctional (meth) acrylate" and the like. Further, the "polymerizable prepolymer (oligomer)" includes, for example, a (meth) acrylate of a polyester polyol, a (meth) acrylate of a polyether polyol, and a polyepoxy resin. A resin obtained by introducing a hydroxyl group (meth) acrylate with an addition product of a compound and (meth)acrylic acid and a polyhydric alcohol via a polyisocyanate. The blending amount of the diluent monomer and the oligomer as described above is preferably from 1 to 300 parts by weight, more preferably from 1 to 100 parts by weight, per 100 parts by weight of the modified copolymer (B). When the amount of the diluted monomer and the oligomer is more than 300 parts by weight -16 to 200940570 parts, the pattern formability may be lowered or the mechanical strength and the deformation restoring force of the pattern after curing may be lowered. The "photopolymerization initiator" used in the active energy ray-curable resin composition as described above includes, for example, benzophenone, acetophenone, benzil, benzyldimethyl Ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxy Acetophenone, diphenyl disulfide, and the like. These photopolymerization initiators can be used singly or in combination. These photopolymerization initiators may contain a synergist for enhancing the conversion of the light-absorbing energy to the polymerization-initiated radical, such as a tertiary amine. The photopolymerization initiator is preferably used in an amount of from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per part by weight of the active energy ray-curable resin. Further, when the active energy ray-curable resin composition as described above is cured by electron beam irradiation, it is not necessary to add a photopolymerization initiator. The active energy ray-curable resin composition as described above may further contain an epoxy compound and/or a cyclodecyloxy resin (alicyclic epoxy resin or copolymerized type) from the viewpoint of imparting a desired function. An epoxy resin or the like, a resin obtained by adding an acid anhydride to a novolak or a bisphenol epoxy resin by acid modification with (meth)acrylic acid. The "epoxy compound" which may be added includes, for example, an epoxidized resin containing an unsaturated group such as an epoxidized polybutadiene, an epoxidized butadiene-styrene block copolymer, and a commercially available product. It includes: EPOLEAD PB, ESBS, etc. manufactured by DAICEL CHEMICAL INDUSTRIES, LTD. "S-ring epoxy resin" includes, for example, CELLOXIDE 2021, EHPE manufactured by DAICEL Chemical Industry Co., Ltd.; Mitsui Chemicals Co., Ltd. (-17-.200940570)
Mitsui Chemicals, Inc.)製造之 EPOMIC VG-3101 ;油化 Shell 環氧樹脂股份有限公司（Yuka Shell Epoxy Co.，Ltd.)製造之 E-1031S;二菱氣體化學股份有限公司（Mitsubishi Gas Chemical Co.，Inc.)製造之TETRAD-X、TETRAD-C :曰本曹達股份有限 公司（Nippon Soda Co·，Ltd.)製造之 EPB-13，EPB-27 等。「 共聚合型環氧樹脂j係包括：例如，甲基丙烯酸縮水甘油酯 與苯乙烯之共聚合物；屬於甲基丙烯酸縮水甘油酯、苯乙烯 及甲基丙烯酸甲酯之共聚合物的日本油脂股份有限公司（NOF ❹ CORPORATION )製造之CP-50M、CP-50S ;或甲基丙烯酸縮水 甘油酯與環己基順丁烯二醯亞胺等之共聚合物等。此外，「 酚醛清漆型環氧樹脂」係包括：例如，將苯酚、甲酚、鹵化 苯酚及烷基苯酚等之酚類與甲醛在酸性觸媒下進行反應所獲 得之酚醛清漆類與表氯醇和/或甲基表氯醇進行反應所獲得之 樹脂等；且可獲得之市售商品則係包括：日本化藥股份有限 公司（Nippon Kayaku Co.，Ltd.)製造之 EOCN-103、EOCN-104S 、EOCN-1020、EOCN-1027、EPPN-201、BREN-S ;陶氏化學公 〇 司（The Dow Chemical Company)製造之 DEN-431、DEN-439 ;大日本油墨化學股份有限公司（DIC Corporation )製造之 N-73、VH-4150等。「雙酚型環氧樹脂」係包括：例如，將雙 酚A、雙酚F、雙酚S及四溴雙酚A等之雙酚類與表氯醇進行 反應所獲得者，或將雙酚A之二縮水甘油基醚與如前所述雙 酚類之縮合物與表氯醇進行反應所獲得之樹脂等；且可獲得 之市售商品則係包括：油化Shell公司（Yuka Shell Co.，Ltd. )製造之Epikote 1004、Epikote 1002;陶氏化學公司製造之 DER-330、DER-3 37等。並且，其他之環氧樹脂則係包括：將 -18- 200940570 參苯酚甲烷、參甲酚甲烷等與表氯醇和/或甲基表氯醇進行反 應所獲得之樹脂，且可獲自日本化藥股份有限公司製造之 EPPN-501、EPPN-502 等。異三聚氰酸參（2,3-環氧基丙基） 酯、聯苯基二縮水甘油基醚等係可獲自市售商品者。此外， 在如上所述之環氧樹脂之中，經將酚醛清漆或雙酚系環氧樹 脂以（甲基）丙烯酸加以改質後加成酸酐所獲得之樹脂（經 酸改質之環氧樹脂）係可與本發明之硬化性樹脂倂用。 如上所述之環氧化合物、環氧樹脂、及經酸改質之環氧 〇 樹脂係可單獨使用或混合使用。相對於100重量份之改質共 聚合物（B)，此等之環氧化合物、環氧樹脂、及經酸改質之 環氧樹脂之總混合量較佳爲0至100重量份，更佳爲〇至80 重量份。若環氧化合物等之總混合量超過100重量份時，則 有可能圖案形成性降低之情況、或硬化後之圖案的機械強度 及變形恢復力降低之情況。 視需要可使用熱聚合抑制劑、界面活性劑、光吸收劑、 觸變性賦予劑、染料、顏料等作爲其他之添加劑。並且，也 〇 可混合熱塑性樹脂、熱硬化性樹脂等。 本發明之活性能量線硬化性樹脂及活性能量線硬化性樹 脂組成物係經使其在基材上被覆成薄膜並加以硬化，則可形 成硬化樹脂層。形成薄膜之方法係可使用噴霧式塗布 (spray coating)、刷式塗布（brush coating)、輕式塗布（roller coating )、簾幕式塗布（curtain coating )、電沉積式塗布（ electrodeposition coating)、靜電式塗布（electrostatic coating )等之方法。硬化雖然較佳爲在惰性氣體環境下進行，但是 在空氣環境下也可使其硬化。 -19- 200940570 本發明之活性能量線硬化性樹脂及活性能量線硬化性樹 脂組成物係可應用於例如：印墨、塑膠塗料、紙印刷、薄膜 塗布、家倶塗布等之各種塗布領域、FRP(纖維強化塑膠）、 襯裏（lining)、以及在電子設備領域中之絕緣清漆（insulation varnish)、絕緣片、積層板、印刷基板、液狀阻劑、乾膜、 阻劑印墨、液晶顯示器用彩色濾光片或黑色矩陣用顏料光阻 、或塗布用保護膜之成份、半導體封止劑等之許多產業領域 之應用上。 D 《實施例》 在下文中，則以實施例更具體地說明本發明，但是本發 明並不受限於此等實施例。 〔實施例1〕 在配備攪拌機、溫度計、回流冷卻管、滴液泵及氮氣導 入管之3公升之分離式燒瓶中飼入314克之二丙二醇一甲基 醚（曰本乳化劑股份有限公司（NIPPON NYUKAZAI CO·，LTD· )製造之「MFDG」），升溫至125°C後，以歷時4小時逐滴 〇 加入186克之甲基丙烯酸異癸酯、124克之甲基丙烯酸甲酯、 140克之甲基丙烯酸、25 2克之MFDG及36克之己酸三級-丁 基-過氧基-2-乙酯（日本油脂股份有限公司製造之「PERBUTYL 0」）。在逐滴加入30分鐘後追加13克之「PERBUTYL 0」 、94克之「MFDG」後，進行4.5小時之熟化以獲得共聚合物 (A-1 )。此外，甲基丙烯酸異癸酯/甲基丙烯酸/甲基丙烯酸 甲酯之比率（莫耳比）爲12.7/25.2/19.2。 其次，在共聚合物（A-1)溶液（固體成份量：499克） ，加入196克之丙烯酸3,4-環氧環己基甲酯（DAICEL化學工 -20- .200940570 業股份有限公司製造之「CYCLOMER A400」）、8克之三苯 基膦、1.5克之甲基氫酷、79克之「MFDG」，並在i〇〇°c下 進行反應約10小時。反應係在空氣/氮氣之混合環境下進行。 藉此則可獲得本發明之活性能量線硬化性樹脂（B-1)。 B-1係樹脂酸價（KOH mg/g) : 58、雙鍵當量（每1莫耳不飽 和基之樹脂克重量）：600、重量平均分子量：6,000者。 〔實施例2〕 在配備攪拌機、溫度計、回流冷卻管、滴液泵及氮氣導 〇 入管之3公升之分離式燒瓶中飼入314克之二丙二醇一甲基 醚（日本乳化劑股份有限公司製造之MFDG)，升溫至125 °C 後，以歷時4小時逐滴加入152克之甲基丙烯酸甲酯、222克 之甲基丙烯酸、252克之「MFDG」及30克之「PERBUTYL 0 」。在逐滴加入30分鐘後追加11克之「PERBUTYL 0」、94 克之「MFDG」後，進行4.5小時之熟化以獲得共聚合物（A_2 )° 其次，在共聚合物（A-2)之溶液中，加入341克之丙烯 〇 酸3,4-環氧環己基甲酯（DAICEL化學工業股份有限公司製造 之「CYCLOMER A400」）、3.4克之三苯基膦、1.5克之甲基 氫醌、47克之「MFDG」後，接著加入110克之長鏈烷基環氧 化物（DAICEL化學工業股份有限公司製造之「AOE X24」） 、7克之三苯基膦、47克之「MFDG」，並在110°C下進行反 應約15小時。反應係在空氣/氮氣之混合蟫境下進行。 藉此則可獲得本發明之活性能量線硬化性樹脂（B-2 )。 B-2係樹脂酸價（KOH mg/g) : 25、雙鍵當量：440、重量平 均分子量：1 3,000者。 -21- 200940570 〔比較例1〕EPOMIC VG-3101 manufactured by Mitsui Chemicals, Inc.; E-1031S manufactured by Yuka Shell Epoxy Co., Ltd.; Mitsubishi Gas Chemical Co., Ltd. .., TETRAD-X, TETRAD-C manufactured by Inc.: EPB-13, EPB-27, etc. manufactured by Nippon Soda Co., Ltd. "Copolymerized epoxy resin j includes, for example, a copolymer of glycidyl methacrylate and styrene; a Japanese fat belonging to a copolymer of glycidyl methacrylate, styrene and methyl methacrylate. CP-50M, CP-50S manufactured by NOF ❹ CORPORATION; or a copolymer of glycidyl methacrylate and cyclohexylmethyleneimine, etc. In addition, "novolak type epoxy" The resin includes, for example, a phenol novolak obtained by reacting a phenol such as phenol, cresol, a halogenated phenol or an alkylphenol with formaldehyde under an acidic catalyst with epichlorohydrin and/or methyl epichlorohydrin. The resin obtained by the reaction, etc.; and commercially available products include: EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027 manufactured by Nippon Kayaku Co., Ltd. , EPPN-201, BREN-S; DEN-431, DEN-439 manufactured by The Dow Chemical Company; N-73, VH- manufactured by DIC Corporation 4150 and so on. The "bisphenol type epoxy resin" includes, for example, a bisphenol A, a bisphenol F, a bisphenol S, and a bisphenol S such as tetrabromobisphenol A, which are obtained by reacting epichlorohydrin or bisphenol. A resin obtained by reacting a condensed product of A bis glycidyl ether with a bisphenol condensate as described above and epichlorohydrin; and commercially available products include: Oily Shell Co., Ltd. (Yuka Shell Co.) , Ltd.) manufactured by Epikote 1004, Epikote 1002; DER-330, DER-3 37, manufactured by The Dow Chemical Company. In addition, other epoxy resins include: a resin obtained by reacting -18-200940570 phenol phenol methane, cresyl methane, etc. with epichlorohydrin and/or methyl epichlorohydrin, and can be obtained from a Japanese chemical. EPPN-501, EPPN-502, etc. manufactured by the company. The isocyanuric acid ginseng (2,3-epoxypropyl) ester, biphenyl diglycidyl ether, and the like can be obtained from commercially available products. Further, among the epoxy resins described above, a resin obtained by modifying a novolac or a bisphenol epoxy resin with (meth)acrylic acid and then adding an acid anhydride (acid-modified epoxy resin) It can be used together with the curable resin of the present invention. The epoxy compound, the epoxy resin, and the acid-modified epoxy oxime resin as described above may be used singly or in combination. The total amount of the epoxy compound, the epoxy resin, and the acid-modified epoxy resin is preferably from 0 to 100 parts by weight, more preferably 100 parts by weight of the modified copolymer (B). It is 〇 to 80 parts by weight. When the total amount of the epoxy compound or the like is more than 100 parts by weight, the pattern formability may be lowered or the mechanical strength and the deformation restoring force of the pattern after curing may be lowered. A thermal polymerization inhibitor, a surfactant, a light absorber, a thixotropic imparting agent, a dye, a pigment, or the like can be used as other additives as needed. Further, a thermoplastic resin, a thermosetting resin, or the like may be mixed. The active energy ray-curable resin and the active energy ray-curable resin composition of the present invention can be formed into a film on a substrate and cured to form a cured resin layer. The method of forming the film may use spray coating, brush coating, roller coating, curtain coating, electrodeposition coating, static electricity. A method such as electrostatic coating. Although hardening is preferably carried out under an inert gas atmosphere, it can be hardened in an air environment. -19- 200940570 The active energy ray-curable resin and the active energy ray-curable resin composition of the present invention can be applied to various coating fields such as ink, plastic paint, paper printing, film coating, and home coating, and FRP. (fiber reinforced plastic), lining, and insulation varnish, insulating sheet, laminate, printed circuit board, liquid resist, dry film, resist ink, liquid crystal display It is used in many industrial fields such as color filters, pigment barriers for black matrices, components of protective films for coating, and semiconductor sealants. D. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. [Example 1] 314 g of dipropylene glycol monomethyl ether (Nippon Emulsifier Co., Ltd. (NIPPON) was fed into a 3 liter separation flask equipped with a stirrer, a thermometer, a reflux cooling tube, a drip pump, and a nitrogen introduction tube. "MFDG" manufactured by NYUKAZAI CO·, LTD.), after raising the temperature to 125 ° C, 186 g of isodecyl methacrylate, 124 g of methyl methacrylate, and 140 g of methyl group were added dropwise over 4 hours. Acrylic acid, 25 g of MFDG and 36 g of hexanoic acid tris-butyl-peroxy-2-ethyl acrylate ("PERBUTYL 0" manufactured by Nippon Oil & Fats Co., Ltd.). After adding 13 g of "PERBUTYL 0" and 94 g of "MFDG" after 30 minutes of dropwise addition, the mixture was aged for 4.5 hours to obtain a copolymer (A-1). Further, the ratio of the isodecyl methacrylate/methacrylic acid/methyl methacrylate (mol ratio) was 12.7/25.2/19.2. Next, in the copolymer (A-1) solution (solid content: 499 g), 196 g of 3,4-epoxycyclohexylmethyl acrylate (DAICEL Chemist -20-.200940570 Co., Ltd.) was added. "CYCLOMER A400"), 8 g of triphenylphosphine, 1.5 g of methyl hydrogen, 79 g of "MFDG", and reacted at i ° ° C for about 10 hours. The reaction was carried out in a mixed air/nitrogen atmosphere. Thereby, the active energy ray-curable resin (B-1) of the present invention can be obtained. B-1 resin acid value (KOH mg/g): 58. Double bond equivalent (per gram weight of resin per 1 mole of unsaturated): 600, weight average molecular weight: 6,000. [Example 2] 314 g of dipropylene glycol monomethyl ether was fed into a 3 liter seperate flask equipped with a stirrer, a thermometer, a reflux cooling tube, a drip pump, and a nitrogen gas-introducing tube (manufactured by Nippon Emulsifier Co., Ltd.) MFDG), after raising the temperature to 125 ° C, 152 g of methyl methacrylate, 222 g of methacrylic acid, 252 g of "MFDG" and 30 g of "PERBUTYL 0" were added dropwise over 4 hours. After adding 11 g of "PERBUTYL 0" and 94 g of "MFDG" after 30 minutes of dropwise addition, 4.5 hours of ripening was carried out to obtain a copolymer (A_2). Next, in a solution of the copolymer (A-2) 341 g of 3,4-epoxycyclohexylmethyl acrylate ("CYCLOMER A400" manufactured by DAICEL Chemical Industry Co., Ltd.), 3.4 g of triphenylphosphine, 1.5 g of methylhydroquinone, 47 g of "MFDG" Then, 110 g of a long-chain alkyl epoxide ("AOE X24" manufactured by DAICEL Chemical Industry Co., Ltd.), 7 g of triphenylphosphine, and 47 g of "MFDG" were added, and the reaction was carried out at 110 ° C. About 15 hours. The reaction was carried out under a mixture of air/nitrogen. Thereby, the active energy ray-curable resin (B-2) of the present invention can be obtained. B-2 resin acid value (KOH mg/g): 25, double bond equivalent: 440, weight average molecular weight: 1 3,000. -21- 200940570 [Comparative Example 1]
在配備攪拌機、溫度計、回流冷卻管、滴液泵及氮氣導 入管之3公升之分離式燒瓶中飼入375克之「MFDG」，升溫 至95°C後，以歷時3小時逐滴加入81克之甲基丙烯酸甲酯、 117克之丙烯酸、311克之聚一丙烯酸羧基-己內酯（東亞 合成股份有限公司（TOAGOSEI CO·，LTD.)製造之「ARONIX M5300」）、194 克之「MFDG」及 38 克之「PERBUTYLO」、 31 克之 2,2’ -偶氮雙（2-甲基 丁腈）（JAPAN FINECHEM 〇 COMPANY，INC.製造之「ΑΒΝ·Ε」）。然後，進行3小時之熟 化，最後則在11 0°C下熟化1小時以獲得共聚合物（Α-3 )。 其次，在共聚合物（A-3)之溶液中，加入346克之「 CYCLOMER A400」、6.9克之三苯基膦、1.5克之甲基氫醌、 76克之「MFDG」，並在100°C下進行反應約15小時。反應係 在空氣/氮氣之混合環境下進行。 藉此則可獲得活性能量線硬化性樹脂（B-3 ) » B-3係樹 脂酸價（KOH mg/g ) : 55、雙鍵當量：450、重量平均分子量 Ο : 8,500 者。 〔比較例2〕 使用市售之丙烯酸共聚合物樹脂（DAICEL化學工業股份 有限公司製造之「CYCLOMER P(ACA) 250」；由甲基丙烯 酸甲酯/甲基丙烯酸/「CYCLOMER A400」所獲得之共聚合物 、溶劑MFDG)作爲比較例2之活性能量線硬化性樹脂（B-4 )° 使用藉由如上所述實施例及比較例所獲得之活性能量線 硬化性樹脂（B-1 )至（B-4 )來製造活性能量線硬化性樹脂 -22- 200940570 組成物，且以如下所述之方法評估該組成物。評估結果如表1 所示。 (活性能量線硬化性樹脂組成物之製造） 將40重量份（固體成份）之藉由如上所述實施例1所獲 得之活性能量線硬化性樹脂溶液（B-1 )、80重量份之經己內 酯改質之六丙烯酸二新戊四醇酯（日本化藥股份有限公司製 造之「KAYARAD DCPA-120」）、15重量份之光聚合引發劑 (汽巴精化股份有限公司（Ciba Specialty Chemicals Co.，Ltd. D )製造之「INGACURE 3 69」）、8重量份之熱交聯劑（旭化 成工業股份有限公司（AsahiKasei Chemicals Corporation)製 造）製造之「Duranate E-402-B80T」）、及140重量份之作爲 溶劑的二甘醇二甲基醚加以混合，以獲得黏稠之活性能量線 硬化性樹脂組成物。 並且，分別使用（B-2)至（B-4)以取代（B-1)作爲活 性能量線硬化性樹脂溶液，並以與如上所述相同的方式製造 活性能量線硬化性樹脂組成物。 Ο ( 1) 圖案形成性 將藉由如上所述所獲得之各活性能量線硬化性樹脂組成 物（活性能量線聚合性樹脂組成物），以旋轉塗布法塗布在 玻璃基板（ 300 mm X 400 mm、厚度爲0.7 mm)上，然後在烘 箱中在100°C下乾燥2分鐘以獲得塗膜。在所獲得之塗膜，隔 著點矩陣圖型遮罩（dot pattern mask)照射200 mJ/cm2之紫外 線後，以0.04% KOH溶液顯影80秒鐘，然後以純水洗淨3 0 秒鐘以形成圖案。並且，施加220°C、1小時之烘烤處理。結 果所獲得之圖案底面積爲30"mx30；wm、高度爲4.6//m。並 -23- .200940570 以每1 mm2爲4個之密度形成此等形狀之點矩陣圖型（dot pattern )。圖案形成性係以電子顯微鏡觀察該阻劑圖案，而 以如下所述之基準進行評估： 〇： 從圖案上部觀察，輪廓明顯，且在表面也無凹凸 之感； △: 從圖案上部觀察，輪廓雖稍微模糊，但表面並無 凹凸之感； X: 從圖案上部觀察，輪廓模糊，且表面也有凹凸之 © 感。 (2) 機械特性（壓縮彈性模數） 對於藉由如上所述所獲得之點矩陣圖型，以1 0 mN/秒鐘 荷重施加速度加以壓縮，直至到達相當於初期高度（H。）的 85%之高度（)爲止。並假設以到達H，的時刻之荷重爲F 。爾後保持荷重F歷時5秒鐘，給予在一定荷重下之變形後 ，以10 mN/秒鐘荷重施加速度移除荷重，並觀察由於彈性恢 復的點矩陣圖型高度之恢復變形而加以相對比較。評估係以 Q 實施例2之試料爲基準，而以下式所計算得之壓縮彈性模數 (compression elastic modulus)之大小來實施（若壓縮彈性模 數爲與實施例2相同程度，則視爲「中」）。 E= F/ ( D X S ) E: 壓縮彈性模數（Pa); F: 荷重； D: 點矩陣圖型之高度變形率=(H〇— IL· ) /H。； S: 點矩陣圖型之截面積（m2)。 此外，若如上所述壓縮彈性模數分別爲大中小時，則通 -24- .200940570 常係將顯現如下所述之變形模式： 小： 相對於荷重而大幅度地變形，荷重一旦移除則立 刻恢復； 中： 相對於荷重而變形，荷重一旦移除則緩慢地恢復 t 大： 相對於荷重之變形雖小，但是最終則將破壞。 (3) 活性能量線硬化性樹脂組成物（活性能量線聚合性樹 脂組成物）之溶解狀態 〇 以目視觀察藉由如上所述所獲得之各活性能量線硬化性 樹脂組成物（活性能量線聚合性樹脂組成物）之溶解狀態， 若爲未觀測到不溶物且未發生相分離時，則視爲溶解狀態良 好，而發生相分離時，則判斷爲溶解狀態不良。 表1 活性能量線 硬化性樹脂 樹脂組成物之 溶解狀態 圖案 形成性 機械特性 (壓縮彈性模數） 實施例1 B-1 良好 〇 小 實施例2 B-2 m 〇 中 比較例1 B-3 稍微良好 Δ 小 比較例2 B-4 (CYCLOMERPACA250) 不良 X 大 由表1即可明白，藉由使用本發明之活性能量線硬化性 樹脂之樹脂組成物，則可使優越的圖案形成性與機械特性兩 者並存。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 • 25-In a 3 liter seperate flask equipped with a stirrer, a thermometer, a reflux cooling tube, a drip pump, and a nitrogen inlet tube, 375 g of "MFDG" was fed, and after heating to 95 ° C, 81 g of A was added dropwise over 3 hours. Methyl acrylate, 117 g of acrylic acid, 311 g of polycarboxylate carboxy-caprolactone ("ARONIX M5300" manufactured by TOAGOSEI CO., LTD.), 194 g of "MFDG" and 38 g of " PERBUTYLO", 31 g of 2,2'-azobis(2-methylbutyronitrile) ("AP· F" manufactured by JAPAN FINECHEM, INC., INC.). Then, ripening was carried out for 3 hours, and finally, it was aged at 110 ° C for 1 hour to obtain a copolymer (Α-3 ). Next, in the solution of the copolymer (A-3), 346 g of "CYCLOMER A400", 6.9 g of triphenylphosphine, 1.5 g of methylhydroquinone, and 76 g of "MFDG" were added and carried out at 100 ° C. The reaction was about 15 hours. The reaction was carried out in a mixed air/nitrogen atmosphere. Thereby, the active energy ray-curable resin (B-3) is obtained. » B-3-based resin acid value (KOH mg/g): 55, double bond equivalent: 450, weight average molecular weight Ο: 8,500. [Comparative Example 2] A commercially available acrylic copolymer resin ("CYCLOMER P (ACA) 250" manufactured by DAICEL Chemical Industry Co., Ltd.; and methyl methacrylate/methacrylic acid/"CYCLOMER A400" was used. Copolymer, solvent MFDG) as active energy ray-curable resin (B-4) of Comparative Example 2 The active energy ray-curable resin (B-1) obtained by the above examples and comparative examples was used. (B-4) An active energy ray-curable resin-22-200940570 composition was produced, and the composition was evaluated in the following manner. The evaluation results are shown in Table 1. (Production of active energy ray-curable resin composition) 40 parts by weight (solid content) of the active energy ray-curable resin solution (B-1) obtained in the above Example 1 and 80 parts by weight Caprolactone modified dipentaerythritol hexaacrylate ("KAYARAD DCPA-120" manufactured by Nippon Kayaku Co., Ltd.), 15 parts by weight of photopolymerization initiator (Ciba Specialty) "INGACURE 3 69" manufactured by Chemicals Co., Ltd. D), 8 parts by weight of a thermal crosslinking agent ("Duranate E-402-B80T" manufactured by Asahi Kasei Chemicals Corporation), And 140 parts by weight of diethylene glycol dimethyl ether as a solvent were mixed to obtain a viscous active energy ray-curable resin composition. Further, (B-2) to (B-4) were used instead of (B-1) as the active amount linear curable resin solution, and an active energy ray-curable resin composition was produced in the same manner as described above. Ο (1) Pattern formation property is applied to a glass substrate (300 mm X 400 mm by spin coating) by each active energy ray-curable resin composition (active energy ray-polymerizable resin composition) obtained as described above. The thickness was 0.7 mm), and then dried in an oven at 100 ° C for 2 minutes to obtain a coating film. After the obtained coating film was irradiated with ultraviolet rays of 200 mJ/cm 2 through a dot pattern mask, it was developed with a 0.04% KOH solution for 80 seconds, and then washed with pure water for 30 seconds. Form a pattern. Further, a baking treatment at 220 ° C for 1 hour was applied. The resulting pattern has a bottom area of 30"mx30; wm and a height of 4.6/m. And -23-.200940570 forms a dot pattern of these shapes at a density of 4 per 1 mm2. The pattern formation was observed by an electron microscope, and was evaluated on the basis of the following: 〇: The outline was observed from the upper portion of the pattern, and there was no unevenness on the surface; Δ: viewed from the upper portion of the pattern, the outline Although slightly blurred, there is no unevenness on the surface; X: Observed from the upper part of the pattern, the outline is blurred, and the surface also has a feeling of unevenness. (2) Mechanical properties (compression elastic modulus) With respect to the dot matrix pattern obtained as described above, compression is performed at a load application speed of 10 mN/sec until reaching an initial height (H.) 85 % height (). It is assumed that the load at the time of reaching H is F. After that, the load F was held for 5 seconds, and after being deformed under a certain load, the load was removed at a load rate of 10 mN/second, and the relative deformation was observed due to the recovery of the height of the point matrix of the elastic recovery. The evaluation is carried out based on the sample of the second embodiment and the magnitude of the compression elastic modulus calculated by the following formula (if the compression modulus is the same as in the second embodiment, it is regarded as " in"). E= F/ ( D X S ) E: Compressive elastic modulus (Pa); F: load; D: Height deformation rate of point matrix pattern = (H〇 - IL· ) /H. ; S: The cross-sectional area of the dot matrix pattern (m2). In addition, if the compression modulus is as large as medium as described above, then -24-.200940570 will usually show the deformation mode as follows: Small: Large deformation with respect to the load, once the load is removed Immediately recover; Medium: Deformed relative to the load, once the load is removed, slowly recovers t: The deformation relative to the load is small, but will eventually break. (3) The dissolved state of the active energy ray-curable resin composition (active energy ray-polymerizable resin composition) 〇 visually observed each active energy ray-curable resin composition obtained by the above (active energy ray polymerization) In the dissolved state of the resin composition, if no insoluble matter is observed and phase separation does not occur, the dissolution state is considered to be good, and when phase separation occurs, it is determined that the dissolution state is poor. Table 1 Dissolution state of active energy ray-curable resin resin composition Pattern forming mechanical properties (compression elastic modulus) Example 1 B-1 Good 实施 Small Example 2 B-2 m 比较 Comparative Example 1 B-3 Slightly Good Δ Small Comparative Example 2 B-4 (CYCLOMERPACA250) Poor X Large As can be understood from Table 1, by using the resin composition of the active energy ray-curable resin of the present invention, superior pattern formability and mechanical properties can be obtained. Both coexist. [Simple description of the diagram] None. [Main component symbol description] None. • 25-