TW202406945A

TW202406945A - Curable resin composition, insulating cured film and insulating cured film for touch panel that result from curing said composition, and touch panel

Info

Publication number: TW202406945A
Application number: TW112124443A
Authority: TW
Inventors: 大浦裕貴; 伊藤朱里
Original assignee: 日商大阪有機化學工業股份有限公司
Priority date: 2022-07-01
Filing date: 2023-06-30
Publication date: 2024-02-16
Also published as: WO2024005195A1

Abstract

A curable resin composition including: a heat-curable alkali-soluble resin (A1) that has an acid value of 55-100 mgKOH/g; a photocurable alkali-soluble resin (A2); a (meth)acrylic monomer (B) that has two polymerizable functional groups and a ring structure included between the two polymerizable functional groups; and a photopolymerization initiator (C), wherein the mass ratio [A:B] of the total quantity [A] of the heat-curable alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) and the total quantity [B] of the (meth)acrylic monomer (B) is 100:35-80.

Description

硬化性樹脂組合物、使該組合物硬化而成的絕緣性硬化膜及觸控面板用絕緣性硬化膜、以及觸控面板Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel

本發明是關於硬化性樹脂組合物以及使該組合物硬化而成的絕緣性硬化膜，例如關於對觸控面板等之中使用的絕緣性硬化膜用途（例如，絕緣膜用途、保護膜用途、平坦膜用途等）有用的硬化性樹脂組合物、以及使該組合物硬化而成的觸控面板用絕緣性硬化膜和具備該硬化膜的觸控面板。The present invention relates to a curable resin composition and an insulating cured film obtained by curing the composition. For example, it relates to applications of insulating cured films used in touch panels and the like (for example, insulating film applications, protective film applications, A curable resin composition useful for flat film applications, etc., an insulating cured film for a touch panel obtained by curing the composition, and a touch panel provided with the cured film.

近年來，伴隨電子設備的高功能化、多樣化、小型輕量化發展，在液晶等之顯示元件的前表面安裝透明觸控面板，通過該透明觸控面板進行顯示元件所顯示的文字、符號、圖樣等的視認、選擇，通過透明觸控面板的操作進行設備的各功能的切換的情況增加。In recent years, as electronic equipment has become more functional, diversified, smaller and lighter, a transparent touch panel is installed on the front surface of a display element such as a liquid crystal, and the characters, symbols, etc. displayed on the display element are displayed through the transparent touch panel. It is increasingly common to view and select patterns, etc., and to switch various functions of the device through the operation of the transparent touch panel.

觸控面板的檢測方式有電阻膜方式、電容方式、超聲波方式、光學方式等，近年來，電阻膜方式和電容方式正在普及。例如，電阻膜方式是由上部電極膜和下部電極玻璃的雙面構成所構成，通過用筆尖等從上部電極膜的上方施加壓力來按下開關而引起反應的方式。另外，電容方式是由表面的保護玻璃和傳感器玻璃構成，通過用手指觸摸表面的玻璃，使之發生靜電耦合而與裡面的玻璃產生電容差，根據該電容差來推斷出所觸摸的部位的方式。Touch panel detection methods include resistive film method, capacitive method, ultrasonic method, optical method, etc. In recent years, resistive film method and capacitive method are becoming popular. For example, the resistive film method is composed of a double-sided structure of an upper electrode film and a lower electrode glass, and a reaction is caused by pressing a switch by applying pressure from above the upper electrode film with a pen tip or the like. In addition, the capacitive method is composed of a surface protective glass and a sensor glass. By touching the surface glass with a finger, electrostatic coupling occurs and a capacitance difference is generated with the glass inside. The touched part is inferred based on the capacitance difference.

電容式觸控面板例如基板使用帶ITO膜的玻璃，為了防止接觸的位置的誤認，在層疊結構中設置了絕緣膜、保護膜。作為這樣的保護膜，使用了由高硬度的無機系的SiO ₂、SiN _x、透明樹脂等形成的保護膜、有機系的保護膜。另外，觸控面板在與液晶顯示裝置組合時，根據其設置部位，可以區分為外嵌（Out-Cell）結構、表嵌（On-Cell）結構、內嵌（In-Cell）結構。近年來可視性優異的表嵌結構、內嵌結構正成為主流。這些表嵌結構和內嵌結構中，觸控面板被裝入液晶面板內。進而，作為觸控面板的結構，已知有在絕緣膜的一面配置有X電極且在另一面配置有Y電極的雙面型、以及在同一平面上形成有X電極和Y電極的單面型。 For example, capacitive touch panels use glass with an ITO film as the substrate. In order to prevent misrecognition of the contact position, an insulating film and a protective film are provided in the laminated structure. As such a protective film, a protective film made of high-hardness inorganic SiO ₂ , SiN _x , transparent resin, etc., or an organic protective film is used. In addition, when a touch panel is combined with a liquid crystal display device, it can be classified into an Out-Cell structure, an On-Cell structure, and an In-Cell structure according to its installation location. In recent years, surface-embedded structures and embedded structures with excellent visibility have become mainstream. In these surface-embedded structures and embedded structures, the touch panel is built into the liquid crystal panel. Furthermore, as structures of the touch panel, there are known a double-sided type in which an X electrode is arranged on one side of an insulating film and a Y electrode on the other side, and a single-sided type in which the X electrode and the Y electrode are formed on the same plane. .

作為能夠應用於這樣的觸控面板的技術，例如，提出了一種與硬化膜有關的技術，該硬化膜使用特定的鹼溶性樹脂和光反應性單體，耐化學藥品性、顯影性和耐褶皺性優異（例如，參照專利文獻1）。〈現有技術文獻〉〈專利文獻〉 As a technology that can be applied to such a touch panel, for example, a technology related to a cured film that uses a specific alkali-soluble resin and a photoreactive monomer and has chemical resistance, development properties, and wrinkle resistance has been proposed. Excellent (for example, refer to Patent Document 1). 〈Existing technical documents〉〈Patent documents〉

專利文獻1：國際公開WO2020／251004號Patent Document 1: International Publication No. WO2020/251004

如上所述，為了形成觸控面板、液晶顯示裝置等之中使用的絕緣膜，多使用硬化性樹脂組合物。有時對這樣的絕緣膜實施圖案化，特別是出於將電極間導通等之目的，有時形成微細的貫通孔（所謂通孔）。As described above, curable resin compositions are often used in order to form insulating films used in touch panels, liquid crystal display devices, and the like. Such an insulating film may be patterned, and in particular, fine through holes (so-called through holes) may be formed for the purpose of electrically connecting electrodes.

為了形成微細的圖案，有利的是使用正型的硬化性樹脂組合物。但是，使用正型的硬化性樹脂組合物時，存在硬化物產生著色等之問題。In order to form a fine pattern, it is advantageous to use a positive curable resin composition. However, when a positive curable resin composition is used, there is a problem such as coloring of the cured product.

另一方面，為了避免硬化物的著色，也考慮了使用負型的硬化性樹脂組合物。但是，現有的負型的硬化性組合物難以以適當的形狀形成微細的圖案，特別是微細的通孔。因此，強烈期望開發出一種雖然為負型的硬化性樹脂組合物，但能夠形成微細的圖案的技術，特別是能夠形成微細且良好的形狀的通孔的技術（通孔加工性優異的技術）。On the other hand, in order to avoid coloring of the cured product, it is also considered to use a negative curable resin composition. However, it is difficult to form fine patterns, especially fine through holes, in appropriate shapes with conventional negative-type curable compositions. Therefore, there is a strong desire to develop a technology that can form a fine pattern although it is a negative-type curable resin composition, and in particular, a technology that can form a fine and well-shaped through hole (a technology with excellent through-hole processability) .

本發明為了解決上述的課題，其目的在於提供能夠一種形成微細的圖案、特別是通孔加工性優異的硬化性樹脂組合物、使該組合物硬化而成的絕緣性硬化膜和觸控面板用絕緣性硬化膜、以及具備該硬化膜的觸控面板。In order to solve the above-mentioned problems, an object of the present invention is to provide a curable resin composition capable of forming fine patterns, particularly excellent through-hole processability, and an insulating cured film obtained by curing the composition, and for a touch panel. An insulating cured film, and a touch panel provided with the cured film.

本發明人等為了解決上述課題進行了深入研究。其結果發現通過使用以特定的比率包含具有特定結構的共聚物和具有特定結構的單體的組合物，能夠實現上述的課題，至此完成了本發明。＜1＞一種硬化性樹脂組合物，包含：酸價為55～100mgKOH／g的熱硬化性鹼溶性樹脂（A1），光硬化性鹼溶性樹脂（A2），具有2個聚合性官能基和包含在上述2個聚合性官能基之間的環結構的（甲基）丙烯酸系單體（B），以及光聚合起始劑（C）；上述熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）的總量〔A〕與上述（甲基）丙烯酸系單體（B）的總量〔B〕的質量比〔A：B〕為100：35～80。＜2＞根據上述＜1＞所述的硬化性樹脂組合物，其中，上述熱硬化性鹼溶性樹脂（A1）具有酸基和環狀醚基。＜3＞根據上述＜1＞或＜2＞所述的硬化性樹脂組合物，其中，上述熱硬化性鹼溶性樹脂（A1）至少包含下述單元（a1-1）和（a1-2）。（單元（a1-1）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基。單元（a1-2）中，R ¹表示氫原子或甲基，R ³表示具有環狀醚結構且可包含氧原子的碳原子數3～15的直鏈型或分枝型脂肪族烴基）＜4＞根據上述＜3＞所述的硬化性樹脂組合物，其中，上述熱硬化性鹼溶性樹脂（A1）進一步包含下述單元（a1-3）。（式中，R ¹表示氫原子或甲基，R ⁴表示選自可包含氧原子的直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、及它們的組合中的至少1種）＜5＞根據上述＜1＞～上述＜4＞中任一項所述的硬化性樹脂組合物，其中，上述光硬化性鹼溶性樹脂（A2）的酸價為70mgKOH／g以下。＜6＞根據上述＜1＞～上述＜5＞中任一項所述的硬化性樹脂組合物，其中，上述光硬化性鹼溶性樹脂（A2）至少包含下述單元（a2-1）和（a2-2）。（單元（a2-1）中，R ¹各自獨立地表示氫原子或甲基，R ⁵表示可包含雜原子的直鏈型、分枝型或環狀的碳原子數2～15的脂肪族烴基。單元（a2-2）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基）＜7＞根據上述＜6＞所述的硬化性樹脂組合物，其中，上述光硬化性鹼溶性樹脂（A2）進一步包含下述單元（a2-3）。（式中，R ¹表示氫原子或甲基，R ⁴表示選自可包含氧原子的直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、及它們的組合中的至少1種）＜8＞根據上述＜1＞～上述＜7＞中任一項所述的硬化性樹脂組合物，其中，上述光硬化性鹼溶性樹脂（A2）的重量平均分子量為20000以下。＜9＞根據上述＜1＞～上述＜8＞中任一項所述的硬化性樹脂組合物，其中，上述熱硬化性鹼溶性樹脂（A1）和上述光硬化性鹼溶性樹脂（A2）中的至少一者具有環狀的基。＜10＞根據上述＜1＞～上述＜9＞中任一項所述的硬化性樹脂組合物，其中，上述（甲基）丙烯酸系單體（B）中的上述環結構為選自可包含氧原子的碳原子數6～26的脂肪族烴基、可包含氧原子的碳原子數6～26的芳香族烴以及它們的組合中的任一種。＜11＞根據上述＜1＞～上述＜10＞中任一項所述的硬化性樹脂組合物，其中，上述（甲基）丙烯酸系單體（B）中的上述2個聚合性官能基包含丙烯醯基。＜12＞根據上述＜1＞～上述＜11＞中任一項所述的硬化性樹脂組合物，其中，上述（甲基）丙烯酸系單體（B）為下述式（b1）表示的化合物。（式中，R ¹¹和R ¹²各自獨立地表示氫原子或甲基，Y ¹和Y ²各自獨立地表示單鍵、或者可包含氧原子的直鏈型或分枝型的碳原子數1～26的脂肪族烴基，X ¹¹表示具有環狀骨架的碳原子數6～26的脂肪族烴基或芳香族基，W ₁和W ₂各自獨立地表示O、N或S。＜13＞根據上述＜1＞～上述＜12＞中任一項所述的硬化性樹脂組合物，其為使用於形成絕緣膜的用途。＜14＞一種絕緣性硬化膜，其為由上述＜1＞～上述＜12＞中任一項所述的硬化性樹脂組合物硬化而成的。＜15＞一種觸控面板用絕緣性硬化膜，其為由上述＜1＞～上述＜12＞中任一項所述的硬化性樹脂組合物硬化而成的。＜16＞一種觸控面板，其為具備上述＜15＞所述的觸控面板用絕緣性硬化膜。 The present inventors conducted intensive research in order to solve the above-mentioned problems. As a result, they found that the above-mentioned subject can be achieved by using a composition containing a copolymer having a specific structure and a monomer having a specific structure in a specific ratio, and thus completed the present invention. <1> A curable resin composition, including: a thermosetting alkali-soluble resin (A1) with an acid value of 55 to 100 mgKOH/g, a photocurable alkali-soluble resin (A2), having 2 polymerizable functional groups and containing The (meth)acrylic monomer (B) with a ring structure between the two polymerizable functional groups, and the photopolymerization initiator (C); the above-mentioned thermosetting alkali-soluble resin (A1) and photocuring alkali The mass ratio [A:B] of the total amount [A] of the soluble resin (A2) and the total amount [B] of the (meth)acrylic monomer (B) is 100:35 to 80. <2> The curable resin composition according to the above <1>, wherein the thermosetting alkali-soluble resin (A1) has an acid group and a cyclic ether group. <3> The curable resin composition according to the above <1> or <2>, wherein the thermosetting alkali-soluble resin (A1) contains at least the following units (a1-1) and (a1-2). (In unit (a1-1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom. Unit ( In a1-2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents a linear or branched aliphatic hydrocarbon group with 3 to 15 carbon atoms that has a cyclic ether structure and may contain oxygen atoms) <4> The curable resin composition according to the above <3>, wherein the thermosetting alkali-soluble resin (A1) further contains the following unit (a1-3). (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, and At least one of their combinations) <5> The curable resin composition according to any one of the above <1> to the above <4>, wherein the acid value of the photocurable alkali-soluble resin (A2) It is 70mgKOH/g or less. <6> The curable resin composition according to any one of the above <1> to the above <5>, wherein the photocurable alkali-soluble resin (A2) contains at least the following units (a2-1) and ( a2-2). (In unit (a2-1), R ¹ each independently represents a hydrogen atom or a methyl group, and R ⁵ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms that may contain heteroatoms. .In the unit (a2-2), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom) <7 > The curable resin composition according to the above <6>, wherein the photocurable alkali-soluble resin (A2) further contains the following unit (a2-3). (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, and At least one of their combinations) <8> The curable resin composition according to any one of the above <1> to the above <7>, wherein the weight average of the photocurable alkali-soluble resin (A2) The molecular weight is below 20,000. <9> The curable resin composition according to any one of the above <1> to the above <8>, wherein the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) are At least one of has a cyclic group. <10> The curable resin composition according to any one of the above <1> to the above <9>, wherein the ring structure in the (meth)acrylic monomer (B) is selected from the group consisting of Any of an aliphatic hydrocarbon group having 6 to 26 carbon atoms that may contain an oxygen atom, an aromatic hydrocarbon group having 6 to 26 carbon atoms that may contain an oxygen atom, and a combination thereof. <11> The curable resin composition according to any one of the above <1> to the above <10>, wherein the two polymerizable functional groups in the (meth)acrylic monomer (B) include Acrylyl. <12> The curable resin composition according to any one of the above <1> to the above <11>, wherein the (meth)acrylic monomer (B) is a compound represented by the following formula (b1) . (In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a single bond, or a linear or branched carbon atom number of 1 to 1 that may include an oxygen atom. 26 aliphatic hydrocarbon group, X ¹¹ represents an aliphatic hydrocarbon group or aromatic group having a cyclic skeleton with 6 to 26 carbon atoms, and W ₁ and W ₂ each independently represent O, N or S. ＜13＞ According to the above ＜ 1> The curable resin composition according to any one of the above <12>, which is used for forming an insulating film. <14> An insulating cured film composed of the above <1> to the above <12 >The curable resin composition according to any one of the above is cured. <15> An insulating cured film for a touch panel, which is the insulating cured film according to any one of the above <1> to the above <12> A curable resin composition is cured. <16> A touch panel provided with the insulating cured film for a touch panel according to the above <15>.

根據本發明，能夠提供一種能夠形成微細的圖案、特別是通孔加工性優異的硬化性樹脂組合物，使該組合物硬化而成的絕緣性硬化膜和觸控面板用絕緣性硬化膜，以及具備該硬化膜的觸控面板。According to the present invention, it is possible to provide an insulating cured film and an insulating cured film for a touch panel obtained by curing a curable resin composition capable of forming a fine pattern and having particularly excellent through-hole processability, and A touch panel provided with the cured film.

以下，對用於實施本發明的方式（以下稱為「本實施方式」）進行詳細說明。但是，本發明並不限定於此，可以在不脫離其主旨的範圍內進行各種變形。Hereinafter, the mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist of the invention.

《硬化性樹脂組合物》本實施方式的硬化性樹脂組合物包含：酸價為55～100mgKOH／g的熱硬化性鹼溶性樹脂（A1），光硬化性鹼溶性樹脂（A2），具有2個聚合性官能基和包含在上述2個聚合性官能基之間的環結構的（甲基）丙烯酸系單體（B），以及光聚合起始劑（C）；上述熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）的總量〔A〕與上述（甲基）丙烯酸系單體（B）的總量〔B〕的質量比〔A：B〕為100：35～80。 "Cure resin composition" The curable resin composition of this embodiment contains a thermosetting alkali-soluble resin (A1) with an acid value of 55 to 100 mgKOH/g, a photocurable alkali-soluble resin (A2), and has two polymerizable functional groups and is included in The (meth)acrylic monomer (B) with a ring structure between the two polymerizable functional groups, and the photopolymerization initiator (C); the above-mentioned thermosetting alkali-soluble resin (A1) and photo-hardening alkali-soluble resin The mass ratio [A:B] of the total amount [A] of the resin (A2) and the total amount [B] of the (meth)acrylic monomer (B) is 100:35 to 80.

本實施方式的硬化性樹脂組合物能夠形成微細的圖案，特別是通孔的加工性優異，雖然為負型的組合物，但能夠以期望的尺寸形成充分開口至孔側面且孔截面形狀從曝光方向觀察為倒梯形的通孔。本實施方式的硬化性樹脂組合物能夠形成微細的圖案，特別是通孔加工性優異的理由尚不確定，首先，推測一個原因在於：由於本實施方式的硬化性樹脂組合物以特定的比例包含熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）與（甲基）丙烯酸系單體，因此製作通孔時的非潛像部（非曝光部）的顯影性優異，並且在潛像部（曝光部）對顯影液的耐性高。進而，推測由於本實施方式的硬化性樹脂組合物包含熱硬化性鹼溶性樹脂，因此通孔壁面不會因顯影後的後烘時的熱而坍塌，能夠保持孔截面形狀從曝光方向觀察為倒梯形。The curable resin composition of this embodiment can form fine patterns and is particularly excellent in processability of through-holes. Although it is a negative-type composition, it can form a sufficient opening to the side of the hole in a desired size and the cross-sectional shape of the hole changes from exposure to light. The through hole is an inverted trapezoid when viewed from the direction. The reason why the curable resin composition of the present embodiment can form fine patterns and is particularly excellent in through-hole processability is not yet certain. First, it is speculated that one reason is because the curable resin composition of the present embodiment contains the curable resin composition in a specific ratio. The thermosetting alkali-soluble resin (A1) and the photo-curing alkali-soluble resin (A2) are combined with (meth)acrylic monomers, so the developability of the non-latent image portion (non-exposed portion) when making through holes is excellent, and the The latent image portion (exposed portion) has high resistance to developer. Furthermore, it is speculated that since the curable resin composition of the present embodiment contains a thermosetting alkali-soluble resin, the wall surface of the through hole does not collapse due to the heat during post-baking after development, and the cross-sectional shape of the hole can be maintained to be inverted when viewed from the exposure direction. trapezoid.

＜鹼溶性樹脂（A）＞本實施方式的硬化性樹脂組合物包含熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）。熱硬化性鹼溶性樹脂（A1）與光硬化性鹼溶性樹脂（A2）為不同的化合物。對於「鹼溶性樹脂」，非硬化部對顯影液顯示溶解性，硬化部對顯影液顯示不溶性或難溶性。另外，從硬化物對顯影液的耐性（以下，簡稱為「對顯影液的耐性」）的觀點考慮，優選熱硬化性鹼溶性樹脂（A1）和上述光硬化性鹼溶性樹脂（A2）中的至少一者具有環狀的基。以下，有時將熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）分別稱為「鹼溶性樹脂（A1）」或「鹼溶性樹脂（A2）」。另外，有時將鹼溶性樹脂（A1）和（A2）統稱為「鹼溶性樹脂（A）」。本實施方式的硬化性樹脂組合物可以包含多個鹼溶性樹脂（A1）和（A2）。＜Alkali-soluble resin (A)＞ The curable resin composition of this embodiment contains a thermosetting alkali-soluble resin (A1) and a photocurable alkali-soluble resin (A2). The thermosetting alkali-soluble resin (A1) and the photo-curing alkali-soluble resin (A2) are different compounds. Regarding "alkali-soluble resin", the non-hardened part shows solubility to the developer, and the hardened part shows insolubility or poor solubility to the developer. In addition, from the viewpoint of the resistance of the cured product to the developer (hereinafter simply referred to as "resistance to the developer"), the thermosetting alkali-soluble resin (A1) and the above-mentioned photocurable alkali-soluble resin (A2) are preferred. At least one has a cyclic group. Hereinafter, the thermosetting alkali-soluble resin (A1) and the photo-curing alkali-soluble resin (A2) may be referred to as "alkali-soluble resin (A1)" or "alkali-soluble resin (A2)" respectively. In addition, alkali-soluble resins (A1) and (A2) may be collectively referred to as "alkali-soluble resin (A)". The curable resin composition of this embodiment may contain a plurality of alkali-soluble resins (A1) and (A2).

（熱硬化性鹼溶性樹脂（A1））鹼溶性樹脂（A1）是酸價為55～100mgKOH／g的熱硬化性鹼溶性樹脂。鹼溶性樹脂（A1）是具有熱反應性基且在70℃以上進行硬化的樹脂。作為上述熱反應性基，沒有特別限定，從低溫硬化性的方面考慮，例如，可舉出酸基（例如羧基、酸酐基、磺基、磷酸基）、環狀醚基、羥基、氨基、硫醇基、異氰酸酯基、矽烷醇基等。鹼溶性樹脂（A1）優選具有酸基和環狀醚基（例如環氧基、氧雜環丁烷基等）作為熱反應性基。熱硬化性鹼溶性樹脂（A1）的硬化進行的溫度根據熱反應性基的種類和數量而變動，從低溫硬化性和未曝光部的顯影性（未曝光部在顯影液中的溶解性）的觀點考慮，為70℃以上，優選為80℃～230℃，進一步優選為90℃～150℃。 (Thermosetting alkali-soluble resin (A1)) The alkali-soluble resin (A1) is a thermosetting alkali-soluble resin with an acid value of 55 to 100 mgKOH/g. The alkali-soluble resin (A1) has a thermally reactive group and hardens at 70° C. or higher. The thermally reactive group is not particularly limited. From the viewpoint of low-temperature curability, examples include acid groups (such as carboxyl groups, acid anhydride groups, sulfo groups, and phosphoric acid groups), cyclic ether groups, hydroxyl groups, amino groups, and sulfide groups. Alcohol group, isocyanate group, silanol group, etc. The alkali-soluble resin (A1) preferably has an acid group and a cyclic ether group (for example, an epoxy group, an oxetanyl group, etc.) as a thermally reactive group. The temperature at which the thermosetting alkali-soluble resin (A1) is cured varies depending on the type and amount of the thermoreactive group, ranging from the low-temperature curability and the developability of the unexposed portion (solubility of the unexposed portion in the developer) From a viewpoint, the temperature is 70°C or higher, preferably 80°C to 230°C, and more preferably 90°C to 150°C.

鹼溶性樹脂（A1）的酸價為55～100mgKOH／g，進一步優選為60～95mgKOH／g，進一步優選為70～90mgKOH／g。如果鹼溶性樹脂（A1）的酸價在55～100mgKOH／g的範圍內，則能夠抑制顯影不良的產生，且對顯影液（例如，四甲基氫氧化銨）的耐性高，能夠抑制過度顯影。另外，如果酸價小於55mgKOH／g，則顯影性有可能降低。作為鹼溶性樹脂的酸價，可以採用理論固體成分酸價值，可以如下算出。理論固體成分酸價值（mgKOH／g）＝［56.1（氫氧化鉀的分子量）×（鹼溶性樹脂（A1）中的含酸基單元的總量［g］）×1000］／［（鹼溶性樹脂（A1）的固體成分的總量［g］）×（含酸基單元的分子量）］ The acid value of the alkali-soluble resin (A1) is 55 to 100 mgKOH/g, more preferably 60 to 95 mgKOH/g, and even more preferably 70 to 90 mgKOH/g. If the acid value of the alkali-soluble resin (A1) is in the range of 55 to 100 mgKOH/g, the occurrence of poor development can be suppressed, and the resistance to a developer (for example, tetramethylammonium hydroxide) is high, and excessive development can be suppressed. . In addition, if the acid value is less than 55 mgKOH/g, the developability may decrease. As the acid value of the alkali-soluble resin, the theoretical solid content acid value can be used and can be calculated as follows. Theoretical solid content acid value (mgKOH/g) = [56.1 (molecular weight of potassium hydroxide) × (total amount of acid group-containing units in alkali-soluble resin (A1) [g]) × 1000] / [(alkali-soluble resin) Total amount of solid content of (A1) [g]) × (molecular weight of acid group-containing units)]

作為熱硬化性鹼溶性樹脂（A1），可以使用至少包含下述單元（a1-1）和（a1-2）的樹脂。熱硬化性鹼溶性樹脂（A1）可以為包含2種以上的下述同一構成單元（例如，2種單元（a1-2））的樹脂。As the thermosetting alkali-soluble resin (A1), a resin containing at least the following units (a1-1) and (a1-2) can be used. The thermosetting alkali-soluble resin (A1) may be a resin containing two or more types of the same structural unit described below (for example, two types of units (a1-2)).

（單元（a1-1）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基。單元（a1-2）中，R ¹表示氫原子或甲基，R ³表示具有環狀醚結構且可包含氧原子的碳原子數3～15的直鏈型或分枝型脂肪族烴基） (In unit (a1-1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom. Unit ( In a1-2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents a linear or branched aliphatic hydrocarbon group with 3 to 15 carbon atoms that has a cyclic ether structure and may contain oxygen atoms)

-單元（a1-1）- 單元（a1―1）為來自不飽和羧酸的單元。單元（a1-1）中，R ¹表示氫原子或甲基，從所得到的硬化物的耐熱性（是指硬化物的形狀不易因熱而變化。以下，簡稱為「耐熱性」）的方面考慮，優選甲基。另外，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基（二價鍵結基）。從耐熱性的觀點考慮，作為可包含氧原子的脂肪族烴基的碳原子數，優選為1～9。這些脂肪族烴基可以在結構中具有-O-結構（包含氧原子的結構：例如醚基（-O-）、酯基（-CO-O-）、酸酐基（-CO-O-CO-））。作為直鏈的脂肪族烴基，可舉出碳原子數1～15的伸烷基、可包含多個酯基、酸酐基（-CO-O-CO-）的碳原子數3～15的脂肪族烴基等。另外，作為環狀的脂肪族烴基，可舉出碳原子數3～15的伸環烷基、可包含多個酯基、酸酐基的碳原子數3～15的伸環烷基等。另外，X ¹可以為包含直鏈部分和環狀部分這兩者的脂肪族烴基。作為具有多個酯基、酸酐基的X ¹的例子，可舉出-CO-O-CH ₂-CH ₂-O-CO-CH ₂-CH ₂-、-CO-O-CH ₂-CH ₂-O-CO-環己基-等。 -Unit (a1-1)- Unit (a1-1) is a unit derived from unsaturated carboxylic acid. In the unit (a1-1), R ¹ represents a hydrogen atom or a methyl group, and the heat resistance of the obtained cured product (meaning that the shape of the cured product is not easily changed by heat. Hereinafter, simply referred to as "heat resistance") It is considered that methyl is preferred. In addition, X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group (bivalent bonding group) having 1 to 15 carbon atoms that may contain an oxygen atom. From the viewpoint of heat resistance, the number of carbon atoms of the aliphatic hydrocarbon group which may contain an oxygen atom is preferably 1 to 9. These aliphatic hydrocarbon groups can have an -O- structure in the structure (a structure containing oxygen atoms: such as ether group (-O-), ester group (-CO-O-), acid anhydride group (-CO-O-CO-) ). Examples of the linear aliphatic hydrocarbon group include an alkylene group having 1 to 15 carbon atoms, an aliphatic group having 3 to 15 carbon atoms that may contain a plurality of ester groups, and an acid anhydride group (-CO-O-CO-). Hydrocarbyl etc. Examples of the cyclic aliphatic hydrocarbon group include a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms that may contain a plurality of ester groups, and an acid anhydride group. In addition, X ¹ may be an aliphatic hydrocarbon group containing both a linear part and a cyclic part. Examples of X ¹ having a plurality of ester groups and acid anhydride groups include -CO-O-CH ₂ -CH ₂ -O-CO-CH ₂ -CH ₂ -, -CO-O-CH ₂ -CH ₂ -O-CO-cyclohexyl-etc.

作為單元（a1-1），例如，可舉出甲基丙烯酸（以下有時稱為「MAA」），丙烯酸、巴豆酸（反式）、馬來酸（順式）、富馬酸（反式）、檸康酸（順式）、中康酸（反式）、衣康酸、馬來酸酐、檸康酸酐、衣康酸酐、六氫鄰苯二甲酸-2-甲基丙烯醯氧基乙酯等。作為單元（a1-1）的優選的結構，可例示來自以下的化合物的單元。Examples of the unit (a1-1) include methacrylic acid (hereinafter sometimes referred to as "MAA"), acrylic acid, crotonic acid (trans form), maleic acid (cis form), and fumaric acid (trans form). ), citraconic acid (cis), mesaconic acid (trans), itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic acid-2-methacryloxyethane Ester etc. Preferable structures of the unit (a1-1) include units derived from the following compounds.

-單元（a1-2）- 單元（a1-2）為來自具有環狀醚結構的不飽和羧酸的單元。下述單元（a1-2）中，R ¹表示氫原子或甲基，R ³表示具有環狀醚結構且可包含氧原子的碳原子數3～15的直鏈型或分枝型脂肪族烴基。 - Unit (a1-2) - Unit (a1-2) is a unit derived from an unsaturated carboxylic acid having a cyclic ether structure. In the following unit (a1-2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms that has a cyclic ether structure and may contain oxygen atoms. .

單元（a1-2）中，R ¹表示氫原子或甲基，從耐熱性的方面考慮，優選甲基。另外，R ³表示具有環狀醚結構且可包含氧原子的碳原子數3～15的直鏈型或分枝型脂肪族烴基。在此，從顯影性的觀點考慮，具有環狀醚結構的直鏈型或分枝型脂肪族烴基的碳原子數優選為3～7。這些脂肪族烴基可以在結構中具有-O-結構（包含氧原子的結構：例如醚基（-O-）、酯基（-CO-O-）、酸酐基（-CO-O-CO-））。作為具有環狀醚結構的直鏈型或分枝型脂肪族烴基，可舉出在伸烷基（例如伸甲基）的末端鍵合有環狀醚結構的基等。作為單元（a1-2）的優選的結構，可例示來自以下的化合物的單元。 In the unit (a1-2), R ¹ represents a hydrogen atom or a methyl group, and from the viewpoint of heat resistance, a methyl group is preferred. In addition, R ³ represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms which has a cyclic ether structure and may contain an oxygen atom. Here, from the viewpoint of developability, the number of carbon atoms of the linear or branched aliphatic hydrocarbon group having a cyclic ether structure is preferably 3 to 7. These aliphatic hydrocarbon groups can have an -O- structure in the structure (a structure containing oxygen atoms: such as ether group (-O-), ester group (-CO-O-), acid anhydride group (-CO-O-CO-) ). Examples of the linear or branched aliphatic hydrocarbon group having a cyclic ether structure include a group in which a cyclic ether structure is bonded to the terminal end of an alkylene group (for example, a methyl methyl group). Preferable structures of the unit (a1-2) include units derived from the following compounds.

-單元（a1-3）- 作為熱硬化性鹼溶性樹脂（A1），從對顯影液的耐性的觀點考慮，可以使用除上述的單元（a1-1）和（a1-2）以外還包含下述單元（a1-3）的樹脂。單元（a1-3）為來自不飽和化合物的單元。 -Unit (a1-3)- As the thermosetting alkali-soluble resin (A1), from the viewpoint of resistance to a developer, one containing the following unit (a1-3) in addition to the above-mentioned units (a1-1) and (a1-2) can be used. resin. Unit (a1-3) is a unit derived from an unsaturated compound.

（式中，R ¹表示氫原子或甲基，R ⁴表示選自可包含氧原子的直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、及它們的組合中的至少1種） (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, and At least 1 of their combinations)

單元（a1-3）中，R ¹表示氫原子或甲基，從耐熱性的方面考慮，優選甲基。另外，R ⁴為直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、或者上述脂肪族烴與芳香族基的組合。在此，從對顯影液的耐性和顯影性的觀點考慮，上述脂肪族烴基的碳原子數優選為1～10。這些脂肪族烴基可以在結構中具有-O-結構（包含氧原子的結構：例如醚基（-O-）、酯基（-CO-O-）、酸酐基（-CO-O-CO-））。作為上述直鏈基、分枝型或環狀的脂肪族烴基，可舉出碳原子數1～20的直鏈型、分枝型或環狀的烷基，從對顯影液的耐性的方面考慮，優選甲基、正丙基、正丁基、正己基、環戊基、環己基、異冰片基、三環癸基、金剛烷基。另外，作為上述芳香族基，可舉出苯基、聯苯基、萘基、蒽基等，從硬化物的透明性的方面考慮，優選苯基。另外，作為碳原子數1～20的脂肪族烴基與芳香族基的組合，可舉出烷氧基苯基、烷基苯基、烷氧基萘基、烷基萘基、烷氧基蒽基、烷基蒽基等，從硬化物的透明性的方面考慮，優選烷氧基苯基、烷基苯基。作為單元（a1-3）的優選的結構，可例示來自以下的化合物的單元。 In the unit (a1-3), R ¹ represents a hydrogen atom or a methyl group, and from the viewpoint of heat resistance, a methyl group is preferred. In addition, R ⁴ is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, or a combination of the above-mentioned aliphatic hydrocarbon and aromatic group. Here, from the viewpoint of resistance to a developer and developability, the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 10. These aliphatic hydrocarbon groups can have an -O- structure in the structure (a structure containing oxygen atoms: such as ether group (-O-), ester group (-CO-O-), acid anhydride group (-CO-O-CO-) ). Examples of the linear, branched or cyclic aliphatic hydrocarbon group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, from the viewpoint of resistance to a developer. , preferably methyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl, isobornyl, tricyclodecyl, and adamantyl. Examples of the aromatic group include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, and the like, and a phenyl group is preferred from the viewpoint of transparency of the cured product. Examples of the combination of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic group include an alkoxyphenyl group, an alkylphenyl group, an alkoxynaphthyl group, an alkylnaphthyl group, and an alkoxyanthracenyl group. , alkylanthracenyl, etc., from the viewpoint of transparency of the cured product, alkoxyphenyl and alkylphenyl are preferred. Preferable structures of the unit (a1-3) include units derived from the following compounds.

-構成比- 從對顯影液的耐性和顯影性的觀點考慮，鹼溶性樹脂（A）中的單元（a1-1）、單元（a1-2）和單元（a1-3）的含有率（莫耳%）優選為（a1-1）／（a1-2）／（a1-3）＝10～50／10～70／0～70，進一步優選為15～40／15～60／15～65，特別優選為15～30／20～50／30～60。 -Composition ratio- From the viewpoint of resistance to a developer and developability, the content (mol %) of the unit (a1-1), the unit (a1-2), and the unit (a1-3) in the alkali-soluble resin (A) is preferred It is (a1-1)/(a1-2)/(a1-3)=10~50/10~70/0~70, more preferably 15~40/15~60/15~65, particularly preferably 15 ~30/20~50/30~60.

-其他構成單元- 鹼溶性樹脂（A1）可以包含不屬上述的單元（a1-1）～（a1-3）中的任一種的其他構成單元。作為其他構成單元，例如，可舉出1,3-雙（甲基丙烯醯氧基）-2-丙醇、2-甲基丙烯醯氧基乙基異氰酸酯、甲基丙烯酸2-羥基乙酯、N-環己基琥珀醯亞胺等。從對顯影液的耐性和顯影性的觀點考慮，上述鹼溶性樹脂（A1）中的其他構成單元的含有率（莫耳%）優選為0～35莫耳%，進一步優選為0～20莫耳%。 -Other structural units- The alkali-soluble resin (A1) may contain other structural units that do not belong to any one of the above-mentioned units (a1-1) to (a1-3). Examples of other structural units include 1,3-bis(methacryloxy)-2-propanol, 2-methacryloxyethyl isocyanate, 2-hydroxyethyl methacrylate, N-cyclohexylsuccinimide, etc. From the viewpoint of resistance to a developer and developability, the content (mol%) of other structural units in the alkali-soluble resin (A1) is preferably 0 to 35 mol%, and more preferably 0 to 20 mol%. %.

（分子量）從顯影性的觀點考慮，鹼溶性樹脂（A1）的重量平均分子量優選為3000～30000，進一步優選為4000～25000，特別優選為5000～20000。鹼溶性樹脂（A）的分子量測定可以通過凝膠滲透色譜（東曹株式會社製，型號：HLC-8120，管柱：G-5000HXL與G-3000HXL這兩個連接，檢測器：RI，流動相：四氫呋喃）進行。 (molecular weight) From the viewpoint of developability, the weight average molecular weight of the alkali-soluble resin (A1) is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and particularly preferably 5,000 to 20,000. The molecular weight of the alkali-soluble resin (A) can be measured by gel permeation chromatography (manufactured by Tosoh Corporation, model: HLC-8120, column: G-5000HXL and G-3000HXL, two connections, detector: RI, mobile phase : Tetrahydrofuran).

（玻璃化轉變溫度）從耐熱性、顯影性和低溫硬化性的觀點考慮，鹼溶性樹脂（A1）的玻璃化轉變溫度優選為0～300℃，進一步優選為30～250℃，特別優選為50～200℃。該玻璃化轉變溫度可以利用差示掃描熱量分析儀（DSC）測定。 (glass transition temperature) From the viewpoint of heat resistance, developability and low-temperature curability, the glass transition temperature of the alkali-soluble resin (A1) is preferably 0 to 300°C, more preferably 30 to 250°C, and particularly preferably 50 to 200°C. The glass transition temperature can be measured using a differential scanning calorimeter (DSC).

（環氧當量）從兼顧對顯影液的耐性與顯影性的觀點考慮，鹼溶性樹脂（A1）的環氧當量優選為200～1000，進一步優選為250～800，特別優選為300～600。該環氧當量例如可以依照JIS K7236（2001）而求出。 (epoxy equivalent) From the viewpoint of balancing resistance to a developer and developability, the epoxy equivalent of the alkali-soluble resin (A1) is preferably 200 to 1,000, more preferably 250 to 800, and particularly preferably 300 to 600. This epoxy equivalent can be calculated|required based on JIS K7236 (2001), for example.

（雙鍵當量）從耐熱性和反應性的觀點考慮，鹼溶性樹脂（A1）的雙鍵當量優選為150～2000，進一步優選為150～1500，特別優選為200～1000。該雙鍵當量例如可以通過「（每1mol的聚合物的質量）／（每1mol的烯鍵式不飽和基的數量）」而求出。 (double bond equivalent) From the viewpoint of heat resistance and reactivity, the double bond equivalent of the alkali-soluble resin (A1) is preferably 150 to 2000, more preferably 150 to 1500, and particularly preferably 200 to 1000. The double bond equivalent can be calculated, for example, by "(mass of polymer per 1 mol)/(number of ethylenically unsaturated groups per 1 mol)".

（具體例）作為鹼溶性樹脂（A1）的具體例，例如，可舉出以下的聚合物。 (Specific example) Specific examples of the alkali-soluble resin (A1) include the following polymers.

（光硬化性鹼溶性樹脂（A2））鹼溶性樹脂（A2）為利用來自光聚合起始劑（C）的自由基而進行硬化的樹脂。鹼溶性樹脂（A2）優選具有烯鍵式不飽和雙鍵作為與自由基反應的官能基。作為烯鍵式不飽和雙鍵，沒有特別限定，從所得到的硬化物的耐化學藥品性的方面考慮，例如，可舉出（甲基）丙烯醯基、乙烯基、烯丙基，優選（甲基）丙烯醯基。 (Photocurable alkali-soluble resin (A2)) The alkali-soluble resin (A2) is a resin that is cured using radicals derived from the photopolymerization initiator (C). The alkali-soluble resin (A2) preferably has an ethylenically unsaturated double bond as a functional group that reacts with radicals. The ethylenically unsaturated double bond is not particularly limited. From the viewpoint of chemical resistance of the obtained cured product, examples include (meth)acrylyl group, vinyl group, and allyl group, and preferably ( Meth)acrylyl.

作為光硬化性鹼溶性樹脂（A2），可以使用至少包含下述單元（a2-1）和（a2-2）的樹脂。光硬化性鹼溶性樹脂（A2）可以為包含2種以上的下述同一構成單元（例如，2種單元（a2-2））的樹脂。As the photocurable alkali-soluble resin (A2), a resin containing at least the following units (a2-1) and (a2-2) can be used. The photocurable alkali-soluble resin (A2) may be a resin containing two or more types of the same structural unit described below (for example, two types of units (a2-2)).

（單元（a2-1）中，R ¹各自獨立地表示氫原子或甲基，R ⁵表示可包含雜原子的直鏈型、分枝型或環狀的碳原子數2～15的脂肪族烴基。單元（a2-2）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基） (In unit (a2-1), R ¹ each independently represents a hydrogen atom or a methyl group, and R ⁵ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms that may contain heteroatoms. .In the unit (a2-2), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom)

-單元（a2-1）- 單元（a2-1）為來自具有（甲基）丙烯醯基的不飽和化合物的單元。單元（a2-1）中，R ¹各自獨立地表示氫原子或甲基，從耐熱性的方面考慮，優選甲基。另外，R ⁵表示可包含雜原子的直鏈型、分枝型或環狀的碳原子數2～15的脂肪族烴基（二價鍵結基）。從組合物的反應性的觀點考慮，作為可包含雜原子的脂肪族烴基的碳原子數，優選為3～10。這些脂肪族烴基可以在結構中具有-O-結構（包含氧原子的結構：例如-OH（羥基）、醚基（-O-）、酯基（-CO-O-）、酸酐基（-CO-O-CO-））、-S-結構等之包含硫原子的結構、-NH-結構等之包含氮原子的結構。作為直鏈或分支的脂肪族烴基，可舉出碳原子數2～15的伸烷基、可包含多個酯基、酸酐基（-CO-O-CO-）的碳原子數2～15的脂肪族烴基等。另外，作為環狀的脂肪族烴基，可舉出碳原子數3～15的伸環烷基、可包含多個酯基、酸酐基的碳原子數3～15的伸環烷基等。另外，R ⁵可以為包含直鏈部分和環狀部分這兩者的脂肪族烴基。作為具有雜原子的R ⁵的例子，可舉出-CH ₂-CH（OH）-CH ₂-、-CH ₂-CH ₂-O-CO-NH-CH ₂-CH ₂-O-、-CO-O-CH ₂-CH（OH）-CH ₂-O-、-CO-O-CH ₂-CH ₂-O-CO-NH-CH ₂-CH ₂-O-、-CO-O-CH ₂-CH ₂-CH ₂-CH ₂-O-CO-NH-CH ₂-CH ₂-O-等。 - Unit (a2-1) - The unit (a2-1) is a unit derived from an unsaturated compound having a (meth)acrylyl group. In the unit (a2-1), R ¹ each independently represents a hydrogen atom or a methyl group, and from the viewpoint of heat resistance, a methyl group is preferred. In addition, R ⁵ represents a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms (bivalent bonding group) which may contain a heteroatom. From the viewpoint of the reactivity of the composition, the number of carbon atoms of the aliphatic hydrocarbon group which may contain hetero atoms is preferably 3 to 10. These aliphatic hydrocarbon groups can have an -O- structure (a structure containing oxygen atoms) in the structure: for example -OH (hydroxyl), ether group (-O-), ester group (-CO-O-), acid anhydride group (-CO -O-CO-)), -S- structure, etc., structures containing sulfur atoms, -NH- structure, etc., structures containing nitrogen atoms. Examples of the linear or branched aliphatic hydrocarbon group include an alkylene group having 2 to 15 carbon atoms, an alkylene group having 2 to 15 carbon atoms which may contain a plurality of ester groups, and an acid anhydride group (-CO-O-CO-). Aliphatic hydrocarbon groups, etc. Examples of the cyclic aliphatic hydrocarbon group include a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms that may contain a plurality of ester groups, and an acid anhydride group. In addition, R ⁵ may be an aliphatic hydrocarbon group containing both a linear part and a cyclic part. Examples of R ⁵ having a hetero atom include -CH ₂ -CH(OH)-CH ₂ -, -CH ₂ -CH ₂ -O-CO-NH-CH ₂ -CH ₂ -O-, -CO -O-CH ₂ -CH(OH)-CH ₂ -O-, -CO-O-CH ₂ -CH ₂ -O-CO-NH-CH ₂ -CH ₂ -O-, -CO-O-CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-CO-NH-CH ₂ -CH ₂ -O-etc.

作為單元（a2-1）的優選的結構，可例示來自以下的化合物的單元。Preferable structures of the unit (a2-1) include units derived from the following compounds.

-單元（a2-2）- 單元（a2-2）為來自不飽和羧酸的單元，表示與上述的單元（a1-1）同樣的構成。單元（a2-2）中，R ¹、X ¹與單元（a1-1）中的R ¹、X ¹含義相同，優選的具體例也同樣。 -Unit (a2-2)- The unit (a2-2) is a unit derived from an unsaturated carboxylic acid, and represents the same structure as the above-mentioned unit (a1-1). In the unit (a2-2), R ¹ and X ¹ have the same meaning as R ¹ and X ¹ in the unit (a1-1), and the preferred specific examples are also the same.

-單元（a2-3）- 從對顯影液的耐性的觀點考慮，作為光硬化性鹼溶性樹脂（A2），可以使用除上述的單元（a2-1）和（a2-2）以外還包含下述單元（a2-3）的樹脂。 -Unit (a2-3)- From the viewpoint of resistance to a developer, as the photocurable alkali-soluble resin (A2), in addition to the above-mentioned units (a2-1) and (a2-2), it is possible to use one containing the following unit (a2-3) resin.

單元（a2-3）為來自不飽和化合物的單元，表示與上述的單元（a1-3）同樣的構成。單元（a2-3）中，R ¹、R ⁴與單元（a1-1）中的R ¹、R ⁴含義相同，優選的具體例也同樣。 The unit (a2-3) is a unit derived from an unsaturated compound and represents the same structure as the above-mentioned unit (a1-3). In the unit (a2-3), R ¹ and R ⁴ have the same meaning as R ¹ and R ⁴ in the unit (a1-1), and the preferred specific examples are also the same.

-構成比- 從兼顧對顯影液的耐性與顯影性的觀點考慮，鹼溶性樹脂（A2）中的單元（a2-1）、單元（a2-2）和單元（a2-3）的含有率（莫耳%）優選為（a2-1）／（a2-2）／（a2-3）＝10～70／1～50／0～70，進一步優選為15～60／5～40／0～60，特別優選為20～50／10～30／0～50。 -Composition ratio- From the viewpoint of balancing the resistance to the developer and the developability, the content rate (mol%) of the unit (a2-1), the unit (a2-2) and the unit (a2-3) in the alkali-soluble resin (A2) Preferably (a2-1)/(a2-2)/(a2-3)=10 to 70/1 to 50/0 to 70, more preferably 15 to 60/5 to 40/0 to 60, particularly preferably 20～50/10～30/0～50.

-其他構成單元- 鹼溶性樹脂（A2）可以包含不屬上述的單元（a2-1）～（a2-3）中的任一種的其他構成單元。作為其他構成單元，例如，可舉出甲基丙烯酸苄酯、2-甲基丙烯醯氧基乙基異氰酸酯、甲基丙烯酸2-羥基乙酯、N-環己基琥珀醯亞胺等。從兼顧對顯影液的耐性與顯影性的觀點考慮，上述鹼溶性樹脂（A2）中的其他構成單元的含有率（莫耳%）優選為0～30莫耳%，進一步優選為0～15莫耳%。 -Other structural units- The alkali-soluble resin (A2) may contain other structural units that do not belong to any one of the above-mentioned units (a2-1) to (a2-3). Examples of other structural units include benzyl methacrylate, 2-methacryloyloxyethyl isocyanate, 2-hydroxyethyl methacrylate, and N-cyclohexylsuccinimide. From the viewpoint of balancing resistance to a developer and developability, the content (mol %) of other structural units in the alkali-soluble resin (A2) is preferably 0 to 30 mol %, and more preferably 0 to 15 mol %. Ear%.

（分子量）從顯影性的觀點考慮，鹼溶性樹脂（A2）的重量平均分子量例如可以為20000以下，優選為500～20000，進一步優選為1000～15000，更優選為2000～10000。鹼溶性樹脂（A2）的分子量測定可以與鹼溶性樹脂（A1）同樣地進行。 (molecular weight) From the viewpoint of developability, the weight average molecular weight of the alkali-soluble resin (A2) may be, for example, 20,000 or less, preferably 500 to 20,000, more preferably 1,000 to 15,000, and more preferably 2,000 to 10,000. The molecular weight of the alkali-soluble resin (A2) can be measured in the same manner as the alkali-soluble resin (A1).

（酸價）從兼顧對顯影液的耐性與顯影性的觀點考慮，鹼溶性樹脂（A2）的酸價優選為70mgKOH／g以下，優選為10～60mgKOH／g以下，進一步優選為20～60mgKOH／g。作為鹼溶性樹脂的酸價，可以採用上述的理論固體成分酸價值。 (acid price) From the viewpoint of balancing resistance to a developer and developability, the acid value of the alkali-soluble resin (A2) is preferably 70 mgKOH/g or less, preferably 10 to 60 mgKOH/g or less, and further preferably 20 to 60 mgKOH/g. As the acid value of the alkali-soluble resin, the above-mentioned theoretical solid content acid value can be used.

（玻璃化轉變溫度）從耐熱性和顯影性的觀點考慮，鹼溶性樹脂（A2）的玻璃化轉變溫度優選為0～300℃，進一步優選為30～250℃，特別優選為50～200℃。該玻璃化轉變溫度可以利用差示掃描熱量分析儀（DSC）測定。 (glass transition temperature) From the viewpoint of heat resistance and developability, the glass transition temperature of the alkali-soluble resin (A2) is preferably 0 to 300°C, more preferably 30 to 250°C, and particularly preferably 50 to 200°C. The glass transition temperature can be measured using a differential scanning calorimeter (DSC).

（雙鍵當量）從反應性和顯影性的觀點考慮，鹼溶性樹脂（A2）的雙鍵當量優選為150～2000，進一步優選為150～1500，特別優選為200～1000。該雙鍵當量可以與鹼溶性樹脂（A1）同樣地求出。 (double bond equivalent) From the viewpoint of reactivity and developability, the double bond equivalent of the alkali-soluble resin (A2) is preferably 150 to 2000, more preferably 150 to 1500, and particularly preferably 200 to 1000. This double bond equivalent can be calculated|required similarly to alkali-soluble resin (A1).

（具體例）作為鹼溶性樹脂（A2）的具體例，例如，可舉出以下的聚合物。 (Specific example) Specific examples of the alkali-soluble resin (A2) include the following polymers.

（含量）本實施方式的硬化性樹脂組合物中的鹼溶性樹脂（A）的含量（鹼溶性樹脂（A1）和鹼溶性樹脂（A2）的總量）沒有特別限定，例如，從顯影性的觀點考慮，相對於組合物中的全部固體成分，優選為30～80質量%，進一步優選為40～70質量%，特別優選為45～65質量%。本說明書中「全部固體成分」是指樹脂組合物中的除溶劑以外的全部成分。 (content) The content of the alkali-soluble resin (A) in the curable resin composition of the present embodiment (the total amount of the alkali-soluble resin (A1) and the alkali-soluble resin (A2)) is not particularly limited. For example, from the viewpoint of developability, It is preferably 30 to 80 mass%, more preferably 40 to 70 mass%, and particularly preferably 45 to 65 mass% relative to the total solid content in the composition. In this specification, "total solid content" refers to all components in the resin composition except the solvent.

（鹼溶性樹脂（A1）與鹼溶性樹脂（A2）的組合）本實施方式的硬化性樹脂組合物中的鹼溶性樹脂（A1）與鹼溶性樹脂（A2）的質量比沒有特別限定，例如，從低溫硬化性的觀點考慮，質量比（A1）：（A2）優選為100：1～100，進一步優選為100：5～60，特別優選為100：10～50。 (Combination of alkali-soluble resin (A1) and alkali-soluble resin (A2)) The mass ratio of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of low-temperature curability, the mass ratio (A1): (A2) The ratio is preferably 100:1 to 100, more preferably 100:5 to 60, and particularly preferably 100:10 to 50.

＜其他聚合物＞本實施方式的硬化性樹脂組合物可以包含除鹼溶性樹脂（A）以外的其他聚合物。本實施方式的硬化性樹脂組合物中的其他聚合物的含量沒有特別限定，例如，從不會大幅阻礙硬化膜的耐化學藥品性等，得到包含其他聚合物所帶來的效果的觀點考慮，相對於鹼溶性樹脂（A）100質量份，優選為5～30質量份，進一步優選為10～20質量份。＜Other polymers＞ The curable resin composition of this embodiment may contain other polymers besides the alkali-soluble resin (A). The content of the other polymers in the curable resin composition of the present embodiment is not particularly limited. For example, the content of the other polymers in the curable resin composition of the present embodiment is not particularly hindered in terms of the chemical resistance of the cured film and the effects brought about by the inclusion of the other polymers are obtained. The amount is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A).

＜（甲基）丙烯酸系單體（B）＞（甲基）丙烯酸系單體（B）為具有2個聚合性官能基和包含在上述2個聚合性官能基之間的環構造的化合物，具有至少1個（甲基）丙烯醯基。本實施方式的硬化性樹脂組合物通過使用（甲基）丙烯酸系單體（B），能夠提高通孔加工性。＜(Meth)acrylic monomer (B)＞ The (meth)acrylic monomer (B) is a compound having two polymerizable functional groups and a ring structure contained between the two polymerizable functional groups, and has at least one (meth)acryl group. The curable resin composition of this embodiment can improve through-hole processability by using the (meth)acrylic monomer (B).

在此，「環結構」是指具有至少一個環狀骨架的結構，包含僅由環狀骨架構成的結構、及由環狀骨架和與環狀骨架鍵合的直鏈狀的結構等構成的結構。另外，「包含在2個聚合性官能基之間的環結構」是指2個聚合性官能基經由環結構鍵合，聚合性官能基可以直接鍵合於環狀骨架，也可以間接鍵合於環狀骨架。從對顯影液的耐性的觀點考慮，（甲基）丙烯酸系單體（B）的環結構可以為選自可包含氧原子的碳原子數6～26的脂肪族烴基、可包含氧原子的碳原子數6～26的芳香族烴、及它們的組合（例如，脂肪族烴與芳香族烴的組合、以及不同的脂肪族烴彼此的組合、不同的芳香族烴化合物等）中的任一種。作為環狀骨架的具體例，例如，可舉出芴骨架、環己烷骨架、雙酚A骨架、二環戊烷骨架、及它們的組合等。Here, the "ring structure" refers to a structure having at least one cyclic skeleton, and includes a structure composed only of a cyclic skeleton, a structure composed of a cyclic skeleton and a linear structure bonded to the cyclic skeleton, etc. . In addition, "a ring structure contained between two polymerizable functional groups" means that two polymerizable functional groups are bonded through a ring structure. The polymerizable functional group may be directly bonded to the cyclic skeleton or indirectly bonded to the cyclic skeleton. Ring skeleton. From the viewpoint of resistance to a developer, the ring structure of the (meth)acrylic monomer (B) may be selected from an aliphatic hydrocarbon group having 6 to 26 carbon atoms that may contain an oxygen atom, and a carbon group that may contain an oxygen atom. Any of aromatic hydrocarbons having 6 to 26 atoms, and combinations thereof (for example, combinations of aliphatic hydrocarbons and aromatic hydrocarbons, combinations of different aliphatic hydrocarbons, different aromatic hydrocarbon compounds, etc.). Specific examples of the cyclic skeleton include, for example, a fluorene skeleton, a cyclohexane skeleton, a bisphenol A skeleton, a dicyclopentane skeleton, and combinations thereof.

「聚合性官能基」為（甲基）丙烯醯基本身、包含1個（甲基）丙烯醯基的基或包含1個除（甲基）丙烯醯基以外的聚合性基的官能基。作為除（甲基）丙烯醯基以外的聚合性官能基，可舉出乙烯基、烯丙基、（甲基）丙烯醯胺基等。以下，稱為「包含（甲基）丙烯醯基的基」時，是指（甲基）丙烯醯基本身或包含1個（甲基）丙烯醯基的基。（甲基）丙烯酸系單體（B）優選2個聚合性官能基分別為包含（甲基）丙烯醯基的基，優選2個聚合性官能基中的至少一者為丙烯醯基。（甲基）丙烯酸系單體（B）中，聚合性官能基的數量為2個。如果聚合性官能基的數量超過2，則有時通孔加工性降低。另外，2個聚合性官能基的種類可以相同，也可以相互不同。The "polymerizable functional group" is a (meth)acrylyl group itself, a group containing one (meth)acrylyl group, or a functional group containing one polymerizable group other than a (meth)acrylyl group. Examples of the polymerizable functional group other than the (meth)acrylyl group include a vinyl group, an allyl group, a (meth)acrylamide group, and the like. Hereinafter, when referred to as "the group containing a (meth)acrylyl group", it refers to the (meth)acrylyl group itself or a group containing one (meth)acrylyl group. The (meth)acrylic monomer (B) preferably has two polymerizable functional groups each containing a (meth)acrylyl group, and preferably at least one of the two polymerizable functional groups is an acrylyl group. In the (meth)acrylic monomer (B), the number of polymerizable functional groups is two. If the number of polymerizable functional groups exceeds 2, through-hole processability may decrease. In addition, the types of the two polymerizable functional groups may be the same or different from each other.

作為（甲基）丙烯酸系單體（B），可以使用下述式（b1）表示的化合物。As the (meth)acrylic monomer (B), a compound represented by the following formula (b1) can be used.

（式中，R ¹¹和R ¹²各自獨立地表示氫原子或甲基，Y ¹和Y ²各自獨立地表示單鍵、或者可包含氧原子的直鏈型或分枝型的碳原子數1～26的脂肪族烴基，X ¹¹表示具有環狀骨架的碳原子數6～26的脂肪族烴基或芳香族基，W ₁和W ₂各自獨立地表示O、N或S） (In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a single bond, or a linear or branched carbon atom number of 1 to 1 that may include an oxygen atom. 26 aliphatic hydrocarbon group, X ¹¹ represents an aliphatic hydrocarbon group or aromatic group with 6 to 26 carbon atoms having a cyclic skeleton, W ₁ and W ₂ each independently represent O, N or S)

式（b1）中，R ¹¹和R ¹²各自獨立地表示氫原子或甲基，從曝光時組合物顯示良好的硬化性的（以下簡稱為「硬化性」）觀點考慮，優選氫原子。 Y ¹和Y ²各自獨立地表示單鍵、或者可包含氧原子的直鏈型或分枝型的碳原子數1～26的脂肪族烴基（二價鍵結基）。從硬化性的觀點考慮，作為脂肪族烴基的碳原子數，優選為1～20，進一步優選為1～12。作為直鏈型或分枝型的脂肪族烴基，可舉出碳原子數1～26的伸烷基，可舉出伸甲基、伸乙基、1-甲基伸乙基、1-甲基伸丙基、2-甲基伸丙基、1,1-二甲基伸乙基等。另外，作為包含氧原子的Y ¹和Y ²，例如，可舉出-O（C ₂H ₄O） _m-表示的基（m為1～13）等。作為Y ¹和Y ²，例如，優選伸甲基。 In the formula (b1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint that the composition exhibits good curing properties upon exposure (hereinafter referred to as “curing properties”). Y ¹ and Y ² each independently represent a single bond or a linear or branched aliphatic hydrocarbon group having 1 to 26 carbon atoms (bivalent bonding group) which may contain an oxygen atom. From the viewpoint of hardening properties, the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, and more preferably 1 to 12. Examples of the linear or branched aliphatic hydrocarbon group include an alkylene group having 1 to 26 carbon atoms, and examples include methylethylene group, ethylidene group, 1-methylethylidene group, and 1-methyl group. propylene group, 2-methyl propylene group, 1,1-dimethyl ethyl group, etc. Examples of Y ¹ and Y ² containing an oxygen atom include a group represented by -O(C ₂ H ₄ O) _m - (m is 1 to 13). As Y ¹ and Y ² , for example, methyl methylene is preferred.

X ¹¹表示具有環狀骨架的碳原子數6～26的脂肪族烴基或芳香族基（二價鍵結基）。從對顯影液的耐性的觀點考慮，作為X ¹¹的碳原子數，優選為6～26。作為具有上述環狀骨架的碳原子數6～26的脂肪族烴，可舉出由環己烷環、環癸烷環、三環癸烷環、金剛烷環、降冰片烷環或萘烷環構成的2價鍵結基，作為上述芳香族基，可舉出由苯環、萘環構成的2價鍵結基等。作為X ¹¹，優選包含選自上述的芴骨架、環己烷骨架、雙酚A骨架、二環戊烷骨架、及它們的組合中的至少1種的2價鍵結基。 X ¹¹ represents an aliphatic hydrocarbon group or aromatic group (bivalent bonding group) having 6 to 26 carbon atoms having a cyclic skeleton. From the viewpoint of resistance to a developer, the carbon number of X ¹¹ is preferably 6 to 26. Examples of the aliphatic hydrocarbon having 6 to 26 carbon atoms having the above-mentioned cyclic skeleton include a cyclohexane ring, a cyclodecane ring, a tricyclodecane ring, an adamantane ring, a norbornane ring, or a decalin ring. Examples of the divalent bonding group constituted by the aromatic group include a divalent bonding group composed of a benzene ring and a naphthalene ring. X ¹¹ preferably contains at least one divalent bonding group selected from the above-mentioned fluorene skeleton, cyclohexane skeleton, bisphenol A skeleton, dicyclopentane skeleton, and combinations thereof.

作為（甲基）丙烯酸系單體（B），沒有特別限定，可舉出以下的化合物。The (meth)acrylic monomer (B) is not particularly limited, and examples thereof include the following compounds.

從形成通孔時的顯影性的觀點考慮，本實施方式的硬化性樹脂組合物中的（甲基）丙烯酸系單體（B）的含量以熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）的總量〔A〕與（甲基）丙烯酸系單體（B）的總量〔B〕的質量比〔A：B〕成為100：35～80的方式進行設定。如果相對於熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）的總量〔A〕100質量份，（甲基）丙烯酸系單體（B）的總量〔B〕小於35，則有時形成通孔時的顯影性降低。從通孔加工性的觀點考慮，質量比〔A：B〕優選為100：40～75，進一步優選為100：45～70。另外，雖然沒有特別限定，但從兼顧對顯影液的耐性與顯影性的觀點考慮，鹼溶性樹脂（A1）和鹼溶性樹脂（A2）與（甲基）丙烯酸系單體（B）的組合例如可以為A1：A2：B＝100：5～40：35～110，可以為100：10～30：50～100。 From the viewpoint of developability when forming through holes, the content of the (meth)acrylic monomer (B) in the curable resin composition of the present embodiment is determined by the amount of the thermosetting alkali-soluble resin (A1) and the photocuring alkali. The mass ratio [A:B] of the total amount [A] of the soluble resin (A2) and the total amount [B] of the (meth)acrylic monomer (B) is set so that it becomes 100:35 to 80. If the total amount [B] of the (meth)acrylic monomer (B) is less than 35 parts per 100 parts by mass of the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) , the developability may be reduced when forming through holes. From the viewpoint of through-hole processability, the mass ratio [A:B] is preferably 100:40 to 75, and more preferably 100:45 to 70. In addition, although there is no particular limitation, from the viewpoint of balancing the resistance to the developer and the developability, the combination of the alkali-soluble resin (A1), the alkali-soluble resin (A2) and the (meth)acrylic monomer (B) may be, for example, It can be A1:A2:B=100:5～40:35～110, it can be 100:10～30:50～100.

另外，本實施方式的硬化性樹脂組合物可以包含除（甲基）丙烯酸系單體（B）以外的光反應性單體。作為其他光反應性單體，沒有特別限定，例如，可舉出在分子內具有3個以上的烯鍵式不飽和基的化合物。作為這樣的化合物的例子，例如，可舉出三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇六丙烯酸酯等。In addition, the curable resin composition of this embodiment may contain a photoreactive monomer other than the (meth)acrylic monomer (B). The other photoreactive monomer is not particularly limited, and examples thereof include compounds having three or more ethylenically unsaturated groups in the molecule. Examples of such compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like.

（雙鍵當量）從反應性和顯影性的觀點考慮，（甲基）丙烯酸系單體（B）的雙鍵當量優選為120～1000，進一步優選為120～800，特別優選為120～600。該雙鍵當量可以依照（（甲基）丙烯酸系單體（B）的分子量）/（（甲基）丙烯酸系單體（B）所具有的烯鍵式不飽和基的數量）而求出。 (double bond equivalent) From the viewpoint of reactivity and developability, the double bond equivalent of the (meth)acrylic monomer (B) is preferably 120 to 1,000, more preferably 120 to 800, and particularly preferably 120 to 600. This double bond equivalent can be calculated based on (the molecular weight of the (meth)acrylic monomer (B))/(the number of ethylenically unsaturated groups the (meth)acrylic monomer (B) has).

（LogP）從對顯影液的耐性和顯影性的觀點考慮，（甲基）丙烯酸系單體（B）的LogP優選為1～8，更優選為1.5～7，進一步優選為2～6，特別優選為2.5～6，最優選為3～5。該LogP可以依照OECD GUIDELINES FOR THE TESTING CHEMICALS Partition Coefficient（n-octanol／water），High Performance Liquid Chromatography（HPLC） Method 117（Adopted 13 April 2004），使用逆相管柱（C18）並通過HPLC（高壓效液相色譜儀）進行測定來確定。LogP已知的標準物質使用苄醇、苯甲醚、甲苯、丁苯。 (LogP) From the viewpoint of resistance to a developer and developability, the LogP of the (meth)acrylic monomer (B) is preferably 1 to 8, more preferably 1.5 to 7, still more preferably 2 to 6, and particularly preferably 2.5. ~6, most preferably 3-5. This LogP can be used in accordance with OECD GUIDELINES FOR THE TESTING CHEMICALS Partition Coefficient (n-octanol/water), High Performance Liquid Chromatography (HPLC) Method 117 (Adopted 13 April 2004), using a reverse-phase column (C18) and passing HPLC (high pressure efficiency). liquid chromatograph) to determine. Known standard materials for LogP include benzyl alcohol, anisole, toluene, and butylbenzene.

LogP的測定條件的例子如下。 ·裝置：Agilent Technology公司製的1200Series HPLC ·管柱：DiKMA公司製Inspire C18 5μm 150×4.6mm（粒徑5μm、內徑4.6mm、長度150mm） ·流動相：乙腈與0.5wt%磷酸水溶液的混合液｛混合比率55：45（體積比）｝ ·烘箱溫度：40℃ ·流速：1mL／min ·UV檢測波長：210nm Examples of measurement conditions for LogP are as follows. ·Device: 1200Series HPLC manufactured by Agilent Technology ·Column: Inspire C18 5μm 150×4.6mm made by DiKMA (particle size 5μm, inner diameter 4.6mm, length 150mm) ·Mobile phase: a mixture of acetonitrile and 0.5wt% phosphoric acid aqueous solution {mixing ratio 55:45 (volume ratio)} ·Oven temperature: 40℃ ·Flow rate: 1mL/min ·UV detection wavelength: 210nm

（光聚合起始劑（C））本實施方式的硬化性樹脂組合物為包含光聚合起始劑（C）的負型的硬化性樹脂組合物。光聚合起始劑是由各種活性光線、例如紫外線等活化而引發聚合的化合物。作為光聚合起始劑，例如，可舉出自由基光聚合起始劑、陽離子光聚合起始劑、陰離子光聚合起始劑。光聚合起始劑（C）沒有特別限定，例如，可以適當地使用通過紫外線到可見光線而產生使烯鍵式不飽和基聚合的自由基的光聚合起始劑。 (Photopolymerization initiator (C)) The curable resin composition of this embodiment is a negative curable resin composition containing a photopolymerization initiator (C). Photopolymerization initiators are compounds that are activated by various active rays, such as ultraviolet rays, to initiate polymerization. Examples of the photopolymerization initiator include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators. The photopolymerization initiator (C) is not particularly limited, and for example, a photopolymerization initiator that generates radicals that polymerize an ethylenically unsaturated group by ultraviolet to visible rays can be suitably used.

作為光聚合起始劑，沒有特別限定，例如，可舉出苯乙酮、2,2’-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基氨基苯丙酮、二氯苯乙酮、三氯苯乙酮、對叔丁基苯乙酮等之苯乙酮類；2-苄基-2-二甲基氨基-1-（4-嗎啉基苯基）-丁烷-1-酮、2-二甲基氨基-2-（4-甲基苄基）-1-（4-嗎啉-4-基-苯基）-丁烷-1-酮、2-甲基-1-（4-甲硫基苯基）-2-嗎啉基丙烷-1-酮等之α-氨基酮系光聚合起始劑；1-[4-（苯硫基）苯基]辛烷-1,2-二酮＝2-（O-苯甲醯肟）、1-〔9-乙基-6-（2-甲基苯甲醯基）-9H-哢唑-3-基〕乙酮1-（O-乙醯肟）、1-〔9-乙基-6-苯甲醯基-9.H.-哢唑-3-基〕-辛烷-1-酮肟-O-乙酸酯、1-〔9-乙基-6-（2-甲基苯甲醯基）-9.H.-哢唑-3-基〕-乙烷-1-酮肟-O-苯甲酸酯、1-〔9-正丁基-6-（2-乙基苯甲醯基）-9.H.-哢唑-3-基〕-乙烷-1-酮肟-O-苯甲酸酯、1-［9-乙基-6-（2-甲基-4-四氫呋喃基苯甲醯基）-9.H.-哢唑-3-基］乙酮-1-（O-乙醯肟）、1-〔9-乙基-6-（2-甲基-4-四氫吡喃基苯甲醯基）-9.H.-哢唑-3-基〕乙酮-1-（O-乙醯肟）、1-〔9-乙基-6-（2-甲基-5-四氫呋喃基苯甲醯基）-9.H.-哢唑-3-基〕乙酮-1-（O-乙醯肟）、1-〔9-乙基-6-｛2-甲基-4-（2,2-二甲基-1,3-二氧雜環戊基）甲氧基苯甲醯基｝-9.H.-哢唑-3-基〕乙酮-1-（O-乙醯肟）等之肟酯系光聚合起始劑；二苯甲酮、2-氯二苯甲酮、p,p’-雙二甲基氨基二苯甲酮等之二苯甲酮類；苯偶醯、苯偶姻、苯偶姻甲醚、苯偶姻異丙醚、苯偶姻異丁醚等之苯偶姻醚類；苯偶醯二甲基縮酮、噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等之硫化合物；2-乙基蒽醌、八甲基蒽醌、1,2-苯並蒽醌、2,3-二苯基蒽醌等之蒽醌類；2,4-三氯甲基-（4’-甲氧基苯基）-6-三嗪、2,4-三氯甲基-（4’-甲氧基萘基）-6-三嗪、2,4-三氯甲基-（胡椒基）-6-三嗪、2,4-三氯甲基-（4’-甲氧基苯乙烯基）-6-三嗪等之三嗪類；偶氮二異丁腈、過氧化苯甲醯、過氧化異丙苯等之有機過氧化物；2-巰基苯並咪唑、2-巰基苯並唑、2-巰基苯並噻唑等之硫醇化合物等。從兼顧對顯影液的耐性與顯影性的觀點考慮，作為光聚合起始劑（C），優選肟酯系光聚合起始劑。這些光聚合起始劑可以單獨使用其1種，也可以併用2種以上。The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone, 2,2'-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and dimethylacetophenone. Acetophenones such as chloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, etc.; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone Alk-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl α-aminoketone photopolymerization initiator such as -1-(4-methylthiophenyl)-2-morpholinylpropan-1-one; 1-[4-(phenylthio)phenyl] Octane-1,2-dione=2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-triazol-3-yl 〕Ethyl ketone 1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9.H.-oxazol-3-yl]-octane-1-one oxime-O -Acetate, 1-[9-ethyl-6-(2-methylbenzyl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzene Formate, 1-[9-n-butyl-6-(2-ethylbenzyl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzene Formate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzyl)-9.H.-trimazol-3-yl]ethanone-1-(O- Acetyl oxime), 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-triazol-3-yl]ethanone-1 -(O-acetyl oxime), 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9.H.-triazol-3-yl]ethanone- 1-(O-acetyl oxime), 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxy Oxime ester photopolymerization initiators such as benzoyl}-9.H.-triazol-3-yl]ethanone-1-(O-acetyl oxime); benzophenone, 2-chloro Benzophenones such as benzophenone and p,p'-bisdimethylaminobenzophenone; benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin Benzoin ethers such as indium isobutyl ether; benzodimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone , sulfur compounds such as 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, etc. ;2,4-Trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-Trichloromethyl-(4'-methoxynaphthyl)-6-triazine , 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, etc. ; Organic peroxides such as azobisisobutyronitrile, benzyl peroxide, cumene peroxide, etc.; Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Compounds etc. From the viewpoint of balancing resistance to a developer and developability, the photopolymerization initiator (C) is preferably an oxime ester-based photopolymerization initiator. One type of these photopolymerization initiators may be used alone, or two or more types may be used in combination.

本實施方式的硬化性樹脂組合物中的光聚合起始劑（C）的含量沒有特別限定，例如，從光反應性和保存穩定性的觀點考慮，將（甲基）丙烯酸系單體（B）、光反應性單體和光硬化性鹼溶性樹脂（A2）的合計設為100質量份時，優選為0.1～30質量份，進一步優選為1～20質量份，特別優選為2～15質量份。The content of the photopolymerization initiator (C) in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of photoreactivity and storage stability, the (meth)acrylic monomer (B) ), the photoreactive monomer and the photocurable alkali-soluble resin (A2) are preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 15 parts by mass when the total amount is 100 parts by mass .

＜硬化性樹脂組合物的製法＞本實施方式的硬化性樹脂組合物為包含鹼溶性樹脂（A）、（甲基）丙烯酸系單體（B）、光聚合起始劑（C）的負型的硬化性樹脂，此外，可以加入溶劑、聚合防止劑、矽烷耦合劑等並進行攪拌·混合而製備。 <How to prepare curable resin composition> The curable resin composition of this embodiment is a negative curable resin containing an alkali-soluble resin (A), a (meth)acrylic monomer (B), and a photopolymerization initiator (C). In addition, it may be added Solvent, polymerization inhibitor, silane coupling agent, etc. are stirred and mixed to prepare.

（溶劑）本實施方式中，溶劑可以根據期望的目的適當地選定公知的溶劑而使用。作為上述溶劑，例如，可舉出環己酮（anone）、環戊酮、二乙二醇甲***、乙醯丙酮、甲醇、乙醇、乙基溶纖劑、乙酸乙基溶纖劑、甲基溶纖劑、乙酸甲基溶纖劑、二甘醇二甲醚（diglyme）、環己酮（cyclohexanone）、乙苯、二甲苯、乙酸異戊酯、乙酸正戊酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***、丙二醇單***乙酸酯、二乙二醇、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單***、二乙二醇甲***（EDM）、二乙二醇單***乙酸酯、二乙二醇單丁醚、乙二醇單丁醚乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單甲醚乙酸酯、三乙二醇單***、三乙二醇單***乙酸酯、液體聚乙二醇、二丙二醇單甲醚、二丙二醇單甲醚乙酸酯、二丙二醇單***、二丙二醇單***乙酸酯、乳酸酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等。 (solvent) In this embodiment, a known solvent can be appropriately selected and used according to the desired purpose. Examples of the solvent include cyclohexanone (anone), cyclopentanone, diethylene glycol methyl ethyl ether, acetylacetone, methanol, ethanol, ethyl cellosolve, ethyl acetate cellosolve, methyl Cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n-amyl acetate, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol Ethylene glycol methyl ether (EDM), diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactate, methyl methoxypropionate, ethoxyethyl propionate, etc.

上述溶劑可以僅使用1種，也可以併用2種以上。另外，本實施方式的硬化性樹脂組合物中的溶劑的含量沒有特別限定，例如，從保存穩定性和塗覆性的觀點考慮，優選以全部固體成分（組合物中除溶劑以外的成分的總質量）濃度優選為1～40質量%、進一步優選為5～40質量%、特別優選為10～30質量%的方式使用溶劑。通過使固體成分比例為上述的範圍內，能夠使硬化性樹脂組合物的粘度適當，塗布於基材等形成膜時的塗覆性特別提高。 Only one type of the above solvent may be used, or two or more types may be used in combination. In addition, the content of the solvent in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of storage stability and coating properties, it is preferably the total solid content (the total of components other than the solvent in the composition) Mass) concentration is preferably 1 to 40 mass%, more preferably 5 to 40 mass%, and particularly preferably 10 to 30 mass%. By setting the solid content ratio within the above-mentioned range, the viscosity of the curable resin composition can be made appropriate, and the coatability when applying to a base material or the like to form a film is particularly improved.

（聚合防止劑）從抑制（甲基）丙烯酸系單體（B）等之聚合的觀點考慮，本實施方式的硬化性樹脂組合物可以包含聚合防止劑。另外，作為聚合防止劑，可以使用公知的紫外線吸收劑。 (polymerization inhibitor) The curable resin composition of this embodiment may contain a polymerization inhibitor from the viewpoint of inhibiting the polymerization of the (meth)acrylic monomer (B) and the like. In addition, as the polymerization inhibitor, a known ultraviolet absorber can be used.

作為聚合防止劑，例如，可舉出4-甲氧基苯酚、2,2’-伸甲基雙（4-乙基-6-叔丁基苯酚）、2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-N,N-二甲基氨基對甲酚、2,4-二甲基-6-叔丁基苯酚、4-叔丁基鄰苯二酚、4,4’-硫代-雙（3-甲基-6-叔丁基苯酚）、4,4’-伸丁基-雙（3-甲基-6-叔丁基苯酚）等之酚系化合物；4-羥基-2,2,6,6-四甲基呱啶-N-氧基、4-乙醯氨基-2,2,6,6-四甲基呱啶-N-氧基、4-苯甲醯氧基-2,2,6,6-四甲基呱啶-N-氧基、4-氧代-2,2,6,6-四甲基呱啶-N-氧基、2,2,6,6-四甲基呱啶-N-氧基等之N-氧基系化合物；對甲氧基苯酚（MEHQ）、對苯二酚、2,5-二叔丁基對苯二酚、2,6-二叔丁基對苯二酚、苯醌等之醌系化合物；氯化亞銅；二甲基二硫代氨基甲酸銅等之二烷基二硫代氨基甲酸銅；吩噻嗪、N,N’-二苯基對苯二胺、苯基-β-萘胺、N,N’-二-β-萘基對苯二胺、N-苯基-N’-異丙基對苯二胺等之氨基化合物；1,4-二羥基-2,2,6,6-四甲基呱啶、1-羥基-2,2,6,6-四甲基呱啶、4-羥基-2,2,6,6-四甲基呱啶等之羥基胺系化合物等。作為聚合防止劑，例如，可以適當地使用上述對甲氧基苯酚。作為聚合防止劑，它們可以單獨使用，也可以併用2種以上。Examples of the polymerization inhibitor include 4-methoxyphenol, 2,2'-methylbis(4-ethyl-6-tert-butylphenol), and 2,6-di-tert-butyl-4 -Methylphenol, 2,6-di-tert-butyl-N,N-dimethylamino-p-cresol, 2,4-dimethyl-6-tert-butylphenol, 4-tert-butylcatechol , 4,4'-Thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol) and other phenols Compounds; 4-hydroxy-2,2,6,6-tetramethylpyridin-N-oxy, 4-acetylamino-2,2,6,6-tetramethylpyridin-N-oxy , 4-benzyloxy-2,2,6,6-tetramethylpiridin-N-oxy, 4-oxo-2,2,6,6-tetramethylpiridin-N-oxy base, 2,2,6,6-tetramethylpyridine-N-oxy and other N-oxy compounds; p-methoxyphenol (MEHQ), hydroquinone, 2,5-di-tert-butyl Quinone compounds such as hydroxyhydroquinone, 2,6-di-tert-butylhydroquinone, benzoquinone, etc.; cuprous chloride; dialkyl dithioamino compounds such as copper dimethyldithiocarbamate. Copper formate; phenothiazine, N,N'-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N Amino compounds such as '-isopropyl-p-phenylenediamine; 1,4-dihydroxy-2,2,6,6-tetramethylpiridine, 1-hydroxy-2,2,6,6-tetramethyl Hydroxylamine compounds such as pyridine and 4-hydroxy-2,2,6,6-tetramethylpyridine, etc. As the polymerization inhibitor, for example, the above-mentioned p-methoxyphenol can be suitably used. As a polymerization inhibitor, these may be used individually or in combination of 2 or more types.

本實施方式的硬化性樹脂組合物中的聚合防止劑的量沒有特別限定，從通孔加工性的觀點考慮，相對於全部固體成分（組合物中除溶劑以外的成分的總質量），優選為0.1～0.6質量%，進一步優選為0.1～0.4質量%。The amount of the polymerization inhibitor in the curable resin composition of the present embodiment is not particularly limited, but from the viewpoint of through-hole processability, it is preferably 0 to 100% based on the total solid content (the total mass of components in the composition excluding the solvent). 0.1 to 0.6 mass%, more preferably 0.1 to 0.4 mass%.

（矽烷耦合劑）從提高基材與塗膜的密合性的觀點考慮，本實施方式的硬化性樹脂組合物可以使用矽烷耦合劑。另外，如果本實施方式的硬化性樹脂組合物中包含矽烷耦合劑，則能夠提高所得到的硬化物的絕緣性。 (silane coupling agent) From the viewpoint of improving the adhesion between the base material and the coating film, a silane coupling agent can be used in the curable resin composition of the present embodiment. In addition, if the curable resin composition of this embodiment contains a silane coupling agent, the insulation properties of the obtained cured product can be improved.

矽烷耦合劑的種類沒有特別限定，可以使用公知的矽烷耦合劑，例如，可以使用下述化合物。The type of silane coupling agent is not particularly limited, and known silane coupling agents can be used. For example, the following compounds can be used.

本實施方式的硬化性樹脂組合物中的矽烷耦合劑的量沒有特別限定，從提高與基板的密合性、絕緣性的觀點考慮，相對於鹼溶性樹脂（A）的總量100質量份，優選為1～40質量份，進一步優選為5～30質量份。The amount of the silane coupling agent in the curable resin composition of the present embodiment is not particularly limited. From the viewpoint of improving the adhesion to the substrate and the insulation properties, it is: It is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass.

此外，本實施方式的硬化性樹脂組合物也可以根據需要使用其他無機微粒、密合促進添加劑、表面活性劑、儲存安定劑、整平劑、光安定劑、抗氧化劑等之各種添加劑。作為這些添加劑的例子，例如，可舉出日本特開2012-215833號中記載的添加劑。In addition, the curable resin composition of this embodiment may also use various additives such as other inorganic fine particles, adhesion promoting additives, surfactants, storage stabilizers, leveling agents, light stabilizers, and antioxidants as necessary. Examples of these additives include those described in Japanese Patent Application Laid-Open No. 2012-215833.

《絕緣性硬化膜》本實施方式的硬化性樹脂組合物的用途沒有特別限定，可以用於形成絕緣膜的用途，例如，可以用作絕緣性硬化膜、特別是觸控面板用絕緣性硬化膜。觸控面板用絕緣性硬化膜可以通過如下操作而形成：使用旋塗等之旋轉塗布、模塗等之流延塗布、基於輥塗的塗布、基於輥轉印法的塗布等之各種賦予方法將硬化性樹脂組合物在玻璃基材、ITO、金屬膜、有機膜等之基材上形成塗膜，並使該塗膜硬化。 "Insulating hardened film" The use of the curable resin composition of this embodiment is not particularly limited, and it can be used for forming an insulating film. For example, it can be used as an insulating cured film, particularly an insulating cured film for touch panels. The insulating cured film for touch panels can be formed by various application methods such as spin coating such as spin coating, cast coating such as die coating, coating using a roller coating, and coating using a roller transfer method. The curable resin composition forms a coating film on a base material such as a glass base material, ITO, metal film, organic film, etc., and hardens the coating film.

具體而言，通過將硬化性樹脂組合物塗布在玻璃基板等之基材上，經由光罩照射光，顯影後，根據需要進行加熱處理，從而進行圖案加工，由此能夠形成本實施方式的硬化膜。Specifically, the cured resin composition of the present embodiment can be formed by applying the curable resin composition on a base material such as a glass substrate, irradiating light through a photomask, developing, and performing heat treatment as necessary to perform pattern processing. membrane.

絕緣性硬化膜在絕緣膜用途、保護膜用途、平坦膜用途等之任一用途中均可使用。使用本實施方式的硬化性樹脂組合物的絕緣性硬化膜可以特別適合使用來做為觸控面板用保護膜、觸控面板用絕緣膜。The insulating cured film can be used for any of applications such as insulating film applications, protective film applications, and flat film applications. The insulating cured film using the curable resin composition of this embodiment can be particularly suitably used as a protective film for touch panels and an insulating film for touch panels.

另外，本實施方式的絕緣性硬化膜不僅可以用於維持在觸控面板等之裝置內的作為所謂永久膜的用途，也可以用作在玻璃基板上將ITO膜進行圖案化時使用的抗蝕劑膜。In addition, the insulating cured film of this embodiment can be used not only as a so-called permanent film maintained in a device such as a touch panel, but also as a resist used when patterning an ITO film on a glass substrate. agent film.

（通孔）出於電極間的通電等之目的，可以在觸控面板的絕緣性硬化膜等之中使用的硬化膜設置具有期望尺寸的通孔。通孔是通過圖案化而形成的圖案的一個方式。如上所述，本實施方式的硬化性樹脂組合物雖然為負型的組合物，但通孔加工性優異，能夠形成充分開口至孔側面且孔截面形狀從曝光方向觀察為倒梯形的通孔，因此可以適合使用來做為帶通孔的硬化膜形成用組合物。 (through hole) For the purpose of electrical conduction between electrodes, etc., a through hole having a desired size may be provided in a cured film used for an insulating cured film or the like of a touch panel. Vias are a way of forming patterns through patterning. As described above, although the curable resin composition of this embodiment is a negative composition, it has excellent through-hole processability and can form a through-hole that is sufficiently open to the side of the hole and has a cross-sectional shape of an inverted trapezoid when viewed from the exposure direction. Therefore, it can be suitably used as a composition for forming a cured film with through holes.

對使用本實施方式的硬化性樹脂組合物製作帶通孔的硬化膜的方法沒有特別限定，可以適當地選定公知的通孔形成方法和硬化膜的製作方法。作為使用本實施方式的硬化性樹脂組合物製作帶通孔的硬化膜的方法的一個例子，可舉出包括如下步驟的方法：在基板上賦予本實施方式的硬化性樹脂組合物而形成塗膜的步驟（塗膜形成步驟），將上述塗膜經由通孔形成用光罩進行曝光的步驟（曝光步驟），用顯影液除去曝光後的上述塗膜的非曝光部的步驟（顯影步驟），以及將除去了非曝光部的上述塗膜加熱（例如，90～230℃，10～60分鐘）的步驟（後烘步驟）。在塗膜形成步驟與曝光步驟之間等，可以實施將塗膜加熱（例如，80～100℃，60～180秒）的步驟（預烘步驟）。本實施方式的硬化性樹脂組合物的非曝光部（非硬化部）的顯影性優異，並且曝光部（硬化部）的耐顯影液性能高。因此，能夠抑制過度顯影，並且能夠形成期望的微細的圖案。另外，由於除光硬化性樹脂（鹼溶性樹脂（A2））以外還包含熱硬化性樹脂（鹼溶性樹脂（A1）），因此在後烘步驟中通孔壁面不會坍塌而能夠維持孔截面形狀的推拔角(taper angle)。如此，如果使用本實施方式的硬化性樹脂組合物，則即便為具有小孔徑（例如直徑5μm以下的孔徑）的通孔，也能夠形成充分開口至孔側面且孔截面形狀從曝光方向觀察為倒梯形的通孔。 The method of producing a cured film with a through hole using the curable resin composition of this embodiment is not particularly limited, and a known through hole forming method and a cured film production method can be appropriately selected. An example of a method for producing a cured film with through holes using the curable resin composition of the present embodiment is a method including the step of applying the curable resin composition of the present embodiment to a substrate to form a coating film. the step of (coating film forming step), the step of exposing the above-mentioned coating film through a through-hole forming photomask (exposure step), the step of removing the non-exposed portion of the above-mentioned coating film after exposure with a developer (development step), and a step of heating (for example, 90 to 230°C, 10 to 60 minutes) the above-mentioned coating film with the non-exposed portion removed (post-baking step). Between the coating film formation step and the exposure step, etc., a step (prebaking step) of heating the coating film (eg, 80 to 100° C., 60 to 180 seconds) may be performed. The curable resin composition of this embodiment has excellent developability in the non-exposed portion (non-hardened portion), and has high developer resistance in the exposed portion (hardened portion). Therefore, excessive development can be suppressed and a desired fine pattern can be formed. In addition, since the thermosetting resin (alkali-soluble resin (A1)) is included in addition to the photocurable resin (alkali-soluble resin (A2)), the through-hole wall surface does not collapse during the post-baking step and the hole cross-sectional shape can be maintained. The taper angle of . In this way, if the curable resin composition of this embodiment is used, even if it is a through hole with a small pore diameter (for example, a pore diameter of 5 μm or less), it can be formed that is sufficiently open to the side of the hole and has a cross-sectional shape that is inverted when viewed from the exposure direction. Trapezoidal through hole.

帶通孔的硬化膜的厚度可以根據目的而適當地設定，例如，從反應性的觀點考慮，可以為0.2μm～10μm，進一步可以為0.5μm～5μm。另外，形成於帶通孔的硬化膜的通孔的孔徑可以根據目的而適當地設定，例如，從反應性和顯影性的觀點考慮，可以為100μm以下，進一步可以為10μm以下。應予說明，如圖3所示，形成於帶通孔的硬化膜的通孔的「孔徑」可以定義為從通孔底面起與10%的高度相當的高度的孔徑（圖3中的10%底面CD；有時也稱為「R ₁₀」）。硬化膜的膜厚〔T〕與開口徑〔R ₁₀〕（從通孔底面起與10%的高度相當的高度的孔徑（圖3中的10%底面CD）的比〔T：R ₁₀〕優選為1：10以下，進一步優選為1：1～4。 The thickness of the cured film with through holes can be appropriately set according to the purpose. For example, from the viewpoint of reactivity, it may be 0.2 μm to 10 μm, and further may be 0.5 μm to 5 μm. In addition, the pore diameter of the through hole formed in the cured film with through holes can be appropriately set according to the purpose. For example, from the viewpoint of reactivity and developability, it may be 100 μm or less, and further may be 10 μm or less. In addition, as shown in Figure 3, the "pore diameter" of the through hole formed in the cured film with the through hole can be defined as the hole diameter at a height equivalent to 10% of the height from the bottom surface of the through hole (10% in Figure 3 Bottom CD; sometimes called "R ₁₀ "). The ratio of the film thickness [T] of the cured film to the opening diameter [R ₁₀ ] (the hole diameter corresponding to 10% of the height from the bottom of the through hole (10% bottom CD in Figure 3)) is preferred [T: R ₁₀ ] The ratio is 1:10 or less, and more preferably 1:1 to 4.

另外，形成於帶通孔的硬化膜的通孔的開口尺寸沒有特別限定，對光罩尺寸（光罩的開口徑（直徑）；例如開口直徑為5μm））減去通孔的孔徑（R ₁₀；10%底面CD值）而得的值（絕對值）優選為1.5μm以下，進一步優選小於0.5μm。對於通孔的截面形狀的推拔角（圖3所示的直線A與直線B的交點的角度α（推拔角），在絕緣膜上層形成金屬配線時，希望金屬配線從絕緣膜上層到通孔底面不會斷線，優選小於90°，進一步優選為15～70°。 In addition, the opening size of the through hole formed in the cured film with a through hole is not particularly limited. The hole diameter of the through hole (R ₁₀ ; 10% bottom surface CD value) (absolute value) is preferably 1.5 μm or less, more preferably less than 0.5 μm. Regarding the push-out angle of the cross-sectional shape of the through hole (the angle α (pull-out angle) at the intersection of straight line A and straight line B shown in Figure 3), when forming metal wiring on the upper layer of the insulating film, it is desirable that the metal wiring extends from the upper layer of the insulating film to the through hole. The bottom surface of the hole does not break, and is preferably less than 90°, and more preferably 15 to 70°.

《觸控面板》如上所述，本實施方式的硬化性樹脂組合物和使用其的絕緣性硬化膜可以適合使用來做為觸控面板用絕緣膜。以下，有時將本實施方式的絕緣性硬化膜和觸控面板用絕緣膜簡單統稱為「本實施方式的硬化膜」。 "Touch Panel" As described above, the curable resin composition of this embodiment and the insulating cured film using the same can be suitably used as an insulating film for a touch panel. Hereinafter, the insulating cured film of this embodiment and the insulating film for touch panels may be simply collectively referred to as "the cured film of this embodiment."

本實施方式的觸控面板可以為電阻膜方式、電容方式、超聲波方式、光學方式中的任一種，優選為電容方式的觸控面板。電容式觸控面板例如基板使用帶ITO膜的玻璃，為了防止接觸的位置的誤認，在層疊結構中（例如電極間）設置絕緣膜、保護膜。本實施方式的觸控面板為電容式觸控面板時，本實施方式的觸控面板可以將本實施方式的硬化膜用於例如層疊結構中的絕緣膜、保護膜或這兩者。 The touch panel of this embodiment may be any one of a resistive film type, a capacitive type, an ultrasonic type, and an optical type, and is preferably a capacitive type touch panel. For example, capacitive touch panels use glass with an ITO film as the substrate. In order to prevent misrecognition of the contact position, an insulating film and a protective film are provided in the stacked structure (for example, between electrodes). When the touch panel of this embodiment is a capacitive touch panel, the cured film of this embodiment can be used in the touch panel of this embodiment, for example, as an insulating film, a protective film, or both in a laminated structure.

另外，觸控面板可以分為在絕緣膜的一面配置有X電極且在另一面配置有Y電極的雙面型結構、以及在同一平面上形成有X電極和Y電極的單面型結構。本實施方式的觸控面板可以為雙面型或單面型中的任一種結構，特別優選為單面型結構的觸控面板。單面型的觸控面板結構中，X電極與Y電極電分離。此時，根據電極的圖案，例如，可以區分為島型圖案、通孔型圖案等。例如，在島型圖案的情況下，另外，在單面的觸控面板結構中，經分離的電極彼此由例如被稱為跳線部的部件電連接。另外，電極跳線部使用了ITO膜等之透明電極，但例如在跳線部將經分離的Y電極彼此結合的情況下，為了保持與X電極的絕緣性，在跳線部的下方設置絕緣層。另外，通常，在配置於單面型的各電極上均勻地形成絕緣膜（保護膜）。因此，本實施方式的觸控面板為單面型的觸控面板結構時，本實施方式的觸控面板可以是例如將本實施方式的硬化膜用於被形成在電極上的絕緣膜、被形成於跳線部的下方的絕緣層、或這該兩者。 In addition, touch panels can be classified into a double-sided structure in which X electrodes are arranged on one side of an insulating film and Y electrodes are arranged on the other side, and a single-sided structure in which X electrodes and Y electrodes are formed on the same plane. The touch panel of this embodiment may have any structure of a double-sided type or a single-sided type, and a touch panel with a single-sided structure is particularly preferred. In a single-sided touch panel structure, the X electrode and the Y electrode are electrically separated. At this time, depending on the pattern of the electrode, it can be classified into, for example, an island pattern, a through hole pattern, and the like. For example, in the case of an island pattern or a single-sided touch panel structure, the separated electrodes are electrically connected to each other by a component called a jumper portion, for example. In addition, the electrode jumper part uses a transparent electrode such as an ITO film. However, for example, when the jumper part connects the separated Y electrodes to each other, insulating material is provided below the jumper part in order to maintain insulation from the X electrode. layer. In addition, usually, an insulating film (protective film) is formed uniformly on each electrode arranged in a single-sided type. Therefore, when the touch panel of this embodiment has a single-sided touch panel structure, the touch panel of this embodiment may be formed by using, for example, the cured film of this embodiment for an insulating film formed on an electrode. the insulation layer underneath the jumper part, or both.

進而，將觸控面板裝入液晶顯示裝置時，可以根據其設置部位而區分為外嵌結構、表嵌結構、內嵌結構。表嵌結構和內嵌結構中，觸控面板被裝入液晶面板內，外嵌結構中，觸控面板被裝在液晶面板的外側。表嵌結構中，在觀察方向側的偏振片與液晶層疊體（由一對基板玻璃和介設於其間的液晶層構成的層疊體）之間設置觸控面板。另外，內嵌結構中，液晶層疊體的液晶層具有觸控面板功能。本實施方式的觸控面板在任一種結構中均可應用，但優選被用於例如表嵌結構。Furthermore, when a touch panel is incorporated into a liquid crystal display device, it can be classified into an external embedded structure, a surface embedded structure, and an embedded structure according to its installation location. In the surface-mounted structure and the in-line structure, the touch panel is installed inside the LCD panel. In the external-embedded structure, the touch panel is installed on the outside of the LCD panel. In the surface-mounted structure, a touch panel is installed between a polarizing plate on the viewing direction side and a liquid crystal laminate (a laminate composed of a pair of substrate glasses and a liquid crystal layer interposed therebetween). In addition, in the in-cell structure, the liquid crystal layer of the liquid crystal laminate has a touch panel function. The touch panel of this embodiment can be used in any structure, but is preferably used in a surface-mounted structure, for example.

以下，使用圖對本實施方式的觸控面板的一個方式進行說明。圖1是表示本實施方式的觸控面板的一個方式的構成的俯視圖。如圖1所示，本實施方式的觸控面板為單面型觸控面板時，在玻璃基板10上形成ITO（氧化銦錫）電極（X1～X3、Y1～Y3）。Hereinafter, one embodiment of the touch panel of this embodiment will be described using drawings. FIG. 1 is a plan view showing the structure of one embodiment of the touch panel according to this embodiment. As shown in FIG. 1 , when the touch panel of this embodiment is a single-sided touch panel, ITO (indium tin oxide) electrodes (X1 to X3, Y1 to Y3) are formed on the glass substrate 10.

作為玻璃基板10的坯材，例如，沒有特別限定，例如，可以使用鈉鈣玻璃、低鹼硼矽玻璃、無鹼鋁硼矽酸鹽玻璃等的玻璃板。另外，可以使用由聚對苯二甲酸乙二醇酯（PET）、三乙酸纖維素（TAC）、聚甲基丙烯酸甲酯（PMMA）、聚碳酸酯（PC）等構成的塑料板、塑料膜代替玻璃基板。The material of the glass substrate 10 is not particularly limited. For example, a glass plate such as soda-lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, or the like can be used. In addition, plastic plates and plastic films made of polyethylene terephthalate (PET), triacetylcellulose (TAC), polymethylmethacrylate (PMMA), polycarbonate (PC), etc. can be used Instead of glass substrate.

ITO電極（X1～X3、Y1～Y3）為透明電極。本實施方式中使用了ITO作為透明電極的材料，但只要能夠配設於基板表面，就沒有特別限定，除ITO以外，例如，也可以使用ZnO（氧化鋅）等之無機導電材料，PEDOT／PSS（聚乙烯二氧噻吩／聚苯乙烯磺酸）、聚苯胺、聚吡咯等之有機導電材料。這些材料可以僅使用1種，也可以併用2種以上。應予說明，雖然在圖1和2中省略了記載，但在各電極和跳線部X12中，可以使用具有作為金屬配線的功能的金屬薄膜作為其下層或者代替透明電極。金屬薄膜可以使用Mo（鉬）、Al（鋁）、Ag（銀）、Pd（鈀）等金屬材料，優選使用Mo和Al中的任一者以上。 The ITO electrodes (X1~X3, Y1~Y3) are transparent electrodes. In this embodiment, ITO is used as the material of the transparent electrode, but it is not particularly limited as long as it can be disposed on the substrate surface. In addition to ITO, for example, inorganic conductive materials such as ZnO (zinc oxide), PEDOT/PSS, etc. can also be used. Organic conductive materials such as (polyethylenedioxythiophene/polystyrenesulfonic acid), polyaniline, polypyrrole, etc. Only one type of these materials may be used, or two or more types may be used in combination. Although description is omitted in FIGS. 1 and 2 , a metal thin film having a function as a metal wiring may be used as the underlying layer of each electrode and the jumper portion X12 or in place of the transparent electrode. As the metal thin film, metal materials such as Mo (molybdenum), Al (aluminum), Ag (silver), and Pd (palladium) can be used, and one or more of Mo and Al is preferably used.

如圖1所示，ITO電極X1～X3為在圖1中的箭頭P方向排列的電極，ITO電極X1～X3與鄰接的電極分離，但經由跳線部X12與在P方向鄰接的電極電連接。跳線部X12可以由ITO等之與透明電極同樣的材料形成。另外，在跳線部X12的厚度方向的下方，在與ITO電極Y的連接部之間介設有圖2所示的絕緣膜14。進而，為了使在P方向鄰接的電極電連接，在各跳線部X12的兩端設置有通孔20。另外，ITO電極Y1～Y3為在圖1中的箭頭Q方向排列的電極。ITO電極Y1～Y3經由利用ITO膜形成的連接部與在Q方向鄰接的電極連續耦合，在Q方向電連接。應予說明，通常ITO電極Y1～Y3在電極成型時與各連接部連續形成為一體。以下，將在P方向電連接的電極組稱為「X電極」，將在Q方向電連接的電極組稱為「Y電極」。如圖1所示，單面型觸控面板中，X電極沿P方向排列，Y電極沿Q方向排列。 As shown in Fig. 1 , ITO electrodes X1 to . The jumper portion X12 can be formed of the same material as the transparent electrode such as ITO. In addition, the insulating film 14 shown in FIG. 2 is interposed between the connection portion with the ITO electrode Y below the jumper portion X12 in the thickness direction. Furthermore, in order to electrically connect electrodes adjacent to each other in the P direction, through holes 20 are provided at both ends of each jumper portion X12. In addition, the ITO electrodes Y1 to Y3 are electrodes arranged in the direction of arrow Q in FIG. 1 . The ITO electrodes Y1 to Y3 are continuously coupled to the electrodes adjacent in the Q direction via a connection portion formed of an ITO film, and are electrically connected in the Q direction. In addition, the ITO electrodes Y1 to Y3 are usually formed continuously and integrally with each connecting portion during electrode molding. Hereinafter, the electrode group electrically connected in the P direction will be called "X electrode", and the electrode group electrically connected in the Q direction will be called "Y electrode". As shown in Figure 1, in a single-sided touch panel, the X electrodes are arranged along the P direction, and the Y electrodes are arranged along the Q direction.

接下來使用圖2對本實施方式的觸控面板的截面結構進行說明。圖2是圖1的AA截面圖。如圖2所示，在ITO電極X2與X3之間介設有絕緣膜14、以及ITO電極Y1和Y2的連接部Y12。ITO電極X2和X3如上所述由跳線部X12電連接。另外，在跳線部X12的厚度方向的下方，絕緣膜14的一部分延伸到與連接部Y12之間，保持跳線部X12與連接部Y12的絕緣性。另外，在絕緣膜14以及跳線部X12的厚度方向上側設置有絕緣性保護層16。Next, the cross-sectional structure of the touch panel of this embodiment will be described using FIG. 2 . Fig. 2 is a cross-sectional view taken along line AA in Fig. 1 . As shown in FIG. 2 , an insulating film 14 and a connecting portion Y12 of the ITO electrodes Y1 and Y2 are interposed between the ITO electrodes X2 and X3. The ITO electrodes X2 and X3 are electrically connected by the jumper portion X12 as described above. In addition, a part of the insulating film 14 extends downward in the thickness direction of the jumper portion X12 between the jumper portion X12 and the connection portion Y12 to maintain the insulation between the jumper portion X12 and the connection portion Y12. In addition, an insulating protective layer 16 is provided on the upper side in the thickness direction of the insulating film 14 and the jumper portion X12.

本實施方式中，絕緣膜14或絕緣性保護層16中的至少任一者使用本實施方式的硬化膜。但是，可以使用以往在絕緣膜或保護膜中使用的公知的材料形成任一另一者，但優選絕緣膜14和絕緣性保護層16這兩者為本實施方式的硬化膜。In this embodiment, the cured film of this embodiment is used for at least one of the insulating film 14 or the insulating protective layer 16 . However, the other can be formed using known materials conventionally used for the insulating film or the protective film. However, it is preferable that both the insulating film 14 and the insulating protective layer 16 be the cured films of this embodiment.

上述的觸控面板中，形成本實施方式的硬化膜的方法沒有特別限定，例如，可以通過噴塗、旋塗、狹縫式模塗、輥塗、棒塗等之塗布方法在下層（例如為針對絕緣膜14的玻璃基板10和ITO電極，或者為針對絕緣性保護層16的ITO電極等）上形成塗膜。此時，塗膜的乾燥膜厚沒有特別限定，例如，在絕緣性保護層16的情況下，優選為0.5～20μm，進一步優選為1.0～10μm。同樣地，在絕緣膜14的情況下，乾燥膜厚優選為0.2～10μm，進一步優選為0.5～5μm。另外，根據需要，塗膜可以通過以與塗膜接觸或非接觸狀態設置的具有規定圖案的光罩進行曝光。曝光時的光線的種類沒有特別限定，可舉出可見光線、紫外線、遠紅外線、電子束、X射線等，其中，優選紫外線。光線的照度沒有特別限定，在365nm處優選為5～150mW／cm ²，特別優選為5～35mW／cm ²。其後，根據需要浸漬在碳酸鈉、氫氧化鈉、氫氧化鉀等之水性鹼顯影液、或者四甲基氫氧化銨（TMAH）中，或者通過噴射等來噴霧顯影液而除去非硬化部，形成期望的圖案。進而，為了促進感光性組合物的聚合而使其硬化，可以分別根據需要實施加熱（後烘）。應予說明，在形成該硬化膜時，可以應用上述的通孔的形成方法。 In the above-mentioned touch panel, the method of forming the cured film of this embodiment is not particularly limited. For example, it can be applied to the lower layer (for example, for A coating film is formed on the glass substrate 10 of the insulating film 14 and the ITO electrode, or on the ITO electrode of the insulating protective layer 16 . At this time, the dry film thickness of the coating film is not particularly limited. For example, in the case of the insulating protective layer 16, it is preferably 0.5 to 20 μm, and more preferably 1.0 to 10 μm. Similarly, in the case of the insulating film 14, the dry film thickness is preferably 0.2 to 10 μm, more preferably 0.5 to 5 μm. In addition, if necessary, the coating film can be exposed through a photomask having a predetermined pattern that is placed in contact or non-contact with the coating film. The type of light used during exposure is not particularly limited, and examples thereof include visible rays, ultraviolet rays, far-infrared rays, electron beams, X-rays, and the like. Among these, ultraviolet rays are preferred. The illumination intensity of light is not particularly limited, but it is preferably 5 to 150 mW/cm ² at 365 nm, and particularly preferably 5 to 35 mW/cm ² . Thereafter, the non-hardened portion is removed by immersing it in an aqueous alkali developer such as sodium carbonate, sodium hydroxide, potassium hydroxide, or tetramethylammonium hydroxide (TMAH), or by spraying the developer by spraying or the like. form the desired pattern. Furthermore, in order to accelerate the polymerization of the photosensitive composition and harden it, heating (post-baking) can be performed as necessary. In addition, when forming this cured film, the above-mentioned formation method of a through hole can be applied.

進而，例如，形成跳線部X12時，首先，可以在玻璃基板10上形成經圖案化的X電極、Y電極，其後，在玻璃基板10和電極表面塗布硬化性樹脂組合物，使用能夠形成絕緣膜14、通孔20的光罩對硬化性樹脂組合物進行曝光、顯影。接下來，利用PVD等使跳線部X12的材料（ITO等）堆疊在絕緣膜14和通孔20上而形成導電層。其後，僅在形成跳線部X12的部位（例如圖2中的連接部Y12上的絕緣膜14）的導電層表面設置保護層，並實施蝕刻處理，由此能夠在連接部Y12上的絕緣膜14上形成跳線部X12。實施例 Furthermore, for example, when forming the jumper portion The insulating film 14 and the photomask of the through hole 20 are exposed and developed to the curable resin composition. Next, the material (ITO, etc.) of the jumper portion X12 is stacked on the insulating film 14 and the through hole 20 using PVD or the like to form a conductive layer. Thereafter, a protective layer is provided only on the surface of the conductive layer where the jumper portion A jumper portion X12 is formed on the film 14 . Example

以下，使用實施例和比較例對本發明進行更具體的說明。本發明不受以下的實施例任何限定。Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited by the following examples.

［實施例和比較例］按照下表所示的配合混合各成分，製備硬化性樹脂組合物。混合在室溫下進行，以不引發聚合反應的方式遮蔽紫外線而進行。 [Examples and Comparative Examples] Mix each component according to the formula shown in the table below to prepare a curable resin composition. The mixing is performed at room temperature, and the ultraviolet rays are shielded so as not to initiate a polymerization reaction.

[表1] ※　表中，「OXE-01」表示Irgacure OXE01（BASF JAPAN株式會社）。另外，表中針對各成分的數值表示相對於組合物整體（其中不包括溶劑）的質量份。 [Table 1] ※ In the table, "OXE-01" means Irgacure OXE01 (BASF JAPAN Co., Ltd.). In addition, the numerical value for each component in the table represents the mass part with respect to the whole composition (excluding the solvent).

上述表中各成分使用下表所示的物質。For each component in the above table, use the substances shown in the table below.

[表2] [Table 2]

[表3] [table 3]

[表4] [Table 4]

[表5] [table 5]

《評價》對上述得到的實施例和比較例的硬化性組合物進行各評價。將結果示於下表。 "Evaluation" Each of the curable compositions of the Examples and Comparative Examples obtained above was evaluated. The results are shown in the table below.

（Log P的測定） Log P的測定依照以下的測定條件，依照OECD GUIDELINES FOR THE TESTING CHEMICALS Partition Coefficient （n-octanol/water）， High Performance Liquid Chromatography（HPLC） Method 117（Adopted 13 April 2004），使用逆相管柱（C18）並通過HPLC（高效液相色譜）進行測定。Log P已知的標準物質使用苄醇、苯甲醚、甲苯、丁苯。［測定條件］ ·裝置：Agilent Technology公司製的1200Series HPLC ·管柱：DiKMA公司製Inspire C18　5μm　150×4.6mm （粒徑5μm、內徑4.6mm、長度150mm） ·流動相：乙腈與0.5wt%磷酸水溶液的混合液（混合比率55：45） ·烘箱溫度：40℃ ·流速：1mL／min ·UV檢測波長：210nm (Measurement of Log P) Log P was measured according to the following measurement conditions, in accordance with OECD GUIDELINES FOR THE TESTING CHEMICALS Partition Coefficient (n-octanol/water), High Performance Liquid Chromatography (HPLC) Method 117 (Adopted 13 April 2004), using a reverse-phase column (C18 ) and measured by HPLC (high performance liquid chromatography). Known standard materials for Log P include benzyl alcohol, anisole, toluene, and butylbenzene. [Measurement conditions] ·Device: 1200Series HPLC manufactured by Agilent Technology ·Column: Inspire C18 made by DiKMA | 5μm | 150×4.6mm (Particle size 5μm, inner diameter 4.6mm, length 150mm) ·Mobile phase: a mixture of acetonitrile and 0.5wt% phosphoric acid aqueous solution (mixing ratio 55:45) ·Oven temperature: 40℃ ·Flow rate: 1mL/min ·UV detection wavelength: 210nm

（通孔的形成）通過旋塗法在具有ITO膜的基板上塗布所得到的硬化性樹脂組合物，在90℃的加熱板上預烘90秒而形成塗膜。接下來，使用負片用的接觸孔圖案（孔間距100μm／孔徑5μm），以40mJ／cm ²照射超高壓汞燈的光（365nm處的照度：10mW／cm ²）。接下來，使用2.38%TMAH水溶液顯影30秒，在90℃加熱30分鐘，由此製作膜厚1.6μm的帶硬化膜的基板。 (Formation of Through Holes) The obtained curable resin composition was applied to a substrate having an ITO film by a spin coating method, and was prebaked on a hot plate at 90° C. for 90 seconds to form a coating film. Next, using the contact hole pattern for negative film (hole pitch: 100 μm/aperture diameter: 5 μm), light from an ultrahigh-pressure mercury lamp is irradiated at 40 mJ/cm ² (illuminance at 365 nm: 10 mW/cm ² ). Next, the substrate was developed using a 2.38% TMAH aqueous solution for 30 seconds and heated at 90° C. for 30 minutes to produce a substrate with a cured film having a film thickness of 1.6 μm.

利用激光顯微鏡（LASERTEC公司製，製品名：OPTELICSHYBRID）觀察所得到的帶硬化膜的基板的截面，依照以下的基準進行各評價。The cross section of the obtained substrate with a cured film was observed using a laser microscope (manufactured by LASERTEC, product name: OPTELICSHYBRID), and each evaluation was performed based on the following standards.

〔通孔的開口〕 A：通孔貫通至基底。 C：在孔底部確認到膜，未開口。 [Opening of through hole] A: The through hole penetrates to the base. C: The membrane was confirmed at the bottom of the hole, but no opening was found.

〔開口尺寸〕對於確認到開口的帶硬化膜的基板，算出從光罩尺寸減去通孔的孔徑（R ₁₀；10%底面CD值）而得的值（光罩尺寸（5μm）－R ₁₀（絕對值）），依照以下的基準進行評價。 A：小於0.5μm B：0.5μm以上且小於1.5μm C：1.5μm以上 [Opening size] For a substrate with a cured film where an opening is confirmed, calculate the value obtained by subtracting the diameter of the through hole (R ₁₀ ; 10% bottom surface CD value) from the mask size (mask size (5 μm) - R ₁₀ (absolute value)), evaluated based on the following criteria. A: Less than 0.5μm B: 0.5μm or more and less than 1.5μm C: 1.5μm or more

〔錐形〕利用掃描電子顯微鏡（日本電子株式會社製；型號：JSM-IT500）觀察所得到的帶硬化膜的基板的截面，測定圖3所示的直線A與直線B的交點的角度α（推拔角），依照下述基準進行評價。 A：推拔角小於90°。 C：推拔角為90°以上。〔Tapered〕 The cross section of the obtained substrate with the cured film was observed using a scanning electron microscope (manufactured by JEOL Ltd.; model: JSM-IT500), and the angle α (pull-out angle) at the intersection of straight line A and straight line B shown in Figure 3 was measured. , evaluated according to the following criteria. A: The push-out angle is less than 90°. C: The push-out angle is more than 90°.

[表6] [Table 6]

由得到的結果可知，未使用本實施方式的光硬化性鹼溶性樹脂（A2）的比較例1、未使用本實施方式的熱硬化性鹼溶性樹脂（A1）的比較例2雖然通孔開口，但開口尺寸小，加工性差。另外，未使用本實施方式的（甲基）丙烯酸系單體（B）的比較例3～6、熱硬化性鹼溶性樹脂（A1）和光硬化性鹼溶性樹脂（A2）的總量〔A〕與上述（甲基）丙烯酸系單體（B）的總量〔B〕的質量比〔A：B〕為100：30的比較例7、以及使用酸價小於55mgKOH／g的樹脂的比較例8的通孔均沒有貫通至基底。與此相對，使用本實施方式的硬化性組合物的實施例的通孔貫通，在開口尺寸、膜厚：開口徑比、錐形的任一評價中均為優異的結果。因此，可知實施例的硬化性組合物的通孔加工性優異，且能夠針對1.6μm左右的膜厚形成4μm左右的通孔。 From the obtained results, it can be seen that in Comparative Example 1, which does not use the photocurable alkali-soluble resin (A2) of this embodiment, and Comparative Example 2, which does not use the thermosetting alkali-soluble resin (A1) of this embodiment, although the through holes are opened, However, the opening size is small and the processability is poor. In addition, Comparative Examples 3 to 6 in which the (meth)acrylic monomer (B) of the present embodiment is not used, the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) Comparative Example 7 in which the mass ratio [A:B] to the total amount [B] of the (meth)acrylic monomer (B) is 100:30, and Comparative Example 8 using a resin with an acid value of less than 55 mgKOH/g. None of the through holes penetrate to the base. On the other hand, the through-hole penetration of the examples using the curable composition of this embodiment showed excellent results in all evaluations of opening size, film thickness:opening diameter ratio, and taper shape. Therefore, it was found that the curable compositions of Examples have excellent through-hole processability and can form through-holes of about 4 μm with a film thickness of about 1.6 μm.

10:玻璃基板 14:絕緣膜 16:絕緣性保護層 X1～X3、Y1～Y4:ITO電極 X12:跳線部 Y12:連接部 20:通孔 10:Glass substrate 14:Insulating film 16: Insulating protective layer X1～X3, Y1～Y4: ITO electrode X12: Jumper part Y12:Connection part 20:Through hole

圖1是表示本實施方式的觸控面板的一個方式的構成的俯視圖。圖2是圖1的AA截面圖。圖3是表示通孔的截面形狀的示意圖。 FIG. 1 is a plan view showing the structure of one embodiment of the touch panel according to this embodiment. Fig. 2 is a cross-sectional view taken along line AA in Fig. 1 . FIG. 3 is a schematic diagram showing the cross-sectional shape of a through hole.

無。without.

Claims

一種硬化性樹脂組合物，包含：酸價為55～100mgKOH／g的熱硬化性鹼溶性樹脂A1，光硬化性鹼溶性樹脂A2，具有2個聚合性官能基和包含在所述2個聚合性官能基之間的環結構的（甲基）丙烯酸系單體B，以及光聚合起始劑C；所述熱硬化性鹼溶性樹脂A1和光硬化性鹼溶性樹脂A2的總量A與所述（甲基）丙烯酸系單體B的總量B的質量比A：B為100：35～80。 A hardening resin composition containing: Thermosetting alkali-soluble resin A1 with an acid value of 55 to 100 mgKOH/g, Photohardening alkali-soluble resin A2, (meth)acrylic monomer B having two polymerizable functional groups and a ring structure contained between the two polymerizable functional groups, and Photopolymerization initiator C; The mass ratio A:B of the total amount A of the thermosetting alkali-soluble resin A1 and the photocurable alkali-soluble resin A2 and the total amount B of the (meth)acrylic monomer B is 100:35-80.

如請求項1所述的硬化性樹脂組合物，其中，所述熱硬化性鹼溶性樹脂A1具有酸基和環狀醚基。The curable resin composition according to claim 1, wherein the thermosetting alkali-soluble resin A1 has an acid group and a cyclic ether group.

如請求項1所述的硬化性樹脂組合物，其中，所述熱硬化性鹼溶性樹脂A1至少包含下述單元（a1-1）和（a1-2），單元（a1-1）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基，單元（a1-2）中，R ¹表示氫原子或甲基，R ³表示具有環狀醚結構且可包含氧原子的碳原子數3～15的直鏈型或分枝型脂肪族烴基。 The curable resin composition according to claim 1, wherein the thermosetting alkali-soluble resin A1 contains at least the following units (a1-1) and (a1-2), In unit (a1-1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom. Unit (a1) In -2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms that has a cyclic ether structure and may contain oxygen atoms.

如請求項3所述的硬化性樹脂組合物，其中，所述熱硬化性鹼溶性樹脂A1進一步包含下述單元（a1-3），式中，R ¹表示氫原子或甲基，R ⁴表示選自可包含氧原子的直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、及它們的組合中的至少1種。 The curable resin composition according to claim 3, wherein the thermosetting alkali-soluble resin A1 further contains the following unit (a1-3), In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, and the like, which may contain an oxygen atom. At least 1 of the combinations.

如請求項1所述的硬化性樹脂組合物，其中，所述光硬化性鹼溶性樹脂A2的酸價為70mgKOH／g以下。The curable resin composition according to claim 1, wherein the acid value of the photocurable alkali-soluble resin A2 is 70 mgKOH/g or less.

如請求項1所述的硬化性樹脂組合物，其中，所述光硬化性鹼溶性樹脂A2至少包含下述單元（a2-1）和（a2-2），單元（a2-1）中，R ¹各自獨立地表示氫原子或甲基，R ⁵表示可包含雜原子的直鏈型、分枝型或環狀的碳原子數2～15的脂肪族烴基，單元（a2-2）中，R ¹表示氫原子或甲基，X ¹表示單鍵、或者可包含氧原子的碳原子數1～15的直鏈型或環狀的脂肪族烴基。 The curable resin composition according to claim 1, wherein the photocurable alkali-soluble resin A2 at least contains the following units (a2-1) and (a2-2), In the unit (a2-1), R ¹ each independently represents a hydrogen atom or a methyl group, and R ⁵ represents a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms that may contain heteroatoms, In the unit (a2-2), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms that may contain an oxygen atom.

如請求項6所述的硬化性樹脂組合物，其中，所述光硬化性鹼溶性樹脂A2進一步包含下述單元（a2-3），式中，R ¹表示氫原子或甲基，R ⁴表示選自可包含氧原子的直鏈型、分枝型或環狀的碳原子數1～20的脂肪族烴基、芳香族基、及它們的組合中的至少1種。 The curable resin composition according to claim 6, wherein the photocurable alkali-soluble resin A2 further contains the following unit (a2-3), In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, and the like, which may contain an oxygen atom. At least 1 of the combinations.

如請求項1所述的硬化性樹脂組合物，其中，所述光硬化性鹼溶性樹脂A2的重量平均分子量為20000以下。The curable resin composition according to claim 1, wherein the weight average molecular weight of the photocurable alkali-soluble resin A2 is 20,000 or less.

如請求項1所述的硬化性樹脂組合物，其中，所述熱硬化性鹼溶性樹脂A1和所述光硬化性鹼溶性樹脂A2中的至少一者具有環狀的基。The curable resin composition according to claim 1, wherein at least one of the thermosetting alkali-soluble resin A1 and the photo-curing alkali-soluble resin A2 has a cyclic group.

如請求項1所述的硬化性樹脂組合物，其中，所述（甲基）丙烯酸系單體B中的所述環結構為選自可包含氧原子的碳原子數6～26的脂肪族烴基、可包含氧原子的碳原子數6～26的芳香族烴、及它們的組合中的任一種。The curable resin composition according to claim 1, wherein the ring structure in the (meth)acrylic monomer B is an aliphatic hydrocarbon group having 6 to 26 carbon atoms that may contain an oxygen atom. , aromatic hydrocarbons having 6 to 26 carbon atoms that may contain oxygen atoms, and any combination thereof.

如請求項1所述的硬化性樹脂組合物，其中，所述（甲基）丙烯酸系單體B中的所述2個聚合性官能基包含丙烯醯基。The curable resin composition according to claim 1, wherein the two polymerizable functional groups in the (meth)acrylic monomer B contain an acryl group.

如請求項1所述的硬化性樹脂組合物，其中，所述（甲基）丙烯酸系單體B為下述式（b1）表示的化合物，式中，R ¹¹和R ¹²各自獨立地表示氫原子或甲基，Y ¹和Y ²各自獨立地表示單鍵、或者可包含氧原子的直鏈型或分枝型的碳原子數1～26的脂肪族烴基，X ¹¹表示具有環狀骨架的碳原子數6～26的脂肪族烴基或芳香族基，W ₁和W ₂各自獨立地表示O、N或S。 The curable resin composition according to claim 1, wherein the (meth)acrylic monomer B is a compound represented by the following formula (b1), In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a single bond or a linear or branched carbon number of 1 to 26 that may include an oxygen atom. an aliphatic hydrocarbon group, X ¹¹ represents an aliphatic hydrocarbon group or aromatic group having a cyclic skeleton with 6 to 26 carbon atoms, and W ₁ and W ₂ each independently represent O, N or S.

如請求項1～12中任一項所述的硬化性樹脂組合物，其為使用於形成絕緣膜的用途。The curable resin composition according to any one of claims 1 to 12, which is used for forming an insulating film.

一種絕緣性硬化膜，其為由如請求項1～12中任一項所述的硬化性樹脂組合物硬化而成。An insulating cured film formed by curing the curable resin composition according to any one of claims 1 to 12.

一種觸控面板用絕緣性硬化膜，其為由如請求項1～12中任一項所述的硬化性樹脂組合物硬化而成。An insulating cured film for a touch panel, which is cured from the curable resin composition according to any one of claims 1 to 12.

一種觸控面板，其為具備如請求項15所述的觸控面板用絕緣性硬化膜。A touch panel provided with the insulating cured film for a touch panel according to claim 15.