TWI649339B - Curable resin composition, cured film for display element, method for forming cured film for display element, and display element - Google Patents

Curable resin composition, cured film for display element, method for forming cured film for display element, and display element Download PDF

Info

Publication number
TWI649339B
TWI649339B TW104107834A TW104107834A TWI649339B TW I649339 B TWI649339 B TW I649339B TW 104107834 A TW104107834 A TW 104107834A TW 104107834 A TW104107834 A TW 104107834A TW I649339 B TWI649339 B TW I649339B
Authority
TW
Taiwan
Prior art keywords
group
resin composition
curable resin
compound
examples
Prior art date
Application number
TW104107834A
Other languages
Chinese (zh)
Other versions
TW201534628A (en
Inventor
佐藤光央
Original Assignee
Jsr股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr股份有限公司 filed Critical Jsr股份有限公司
Publication of TW201534628A publication Critical patent/TW201534628A/en
Application granted granted Critical
Publication of TWI649339B publication Critical patent/TWI649339B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)

Abstract

本發明是一種含有聚合物及溶劑的硬化性樹脂組成物,所述聚合物具有下述式(1)所表示的結構單元、以及含羧基的結構單元。式(1)中,R1、R2及R3為氫原子或1價的烴基。R4為(a)(n+1)價的烴基、(b)在(a)烴基的碳-碳間含有選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、或(c)(a)烴基及(b)基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及烷氧基組成的群組中的至少1種取代而成的基。R5為單鍵或-COO-*。 The present invention is a curable resin composition containing a polymer and a solvent, the polymer having a structural unit represented by the following formula (1) and a structural unit containing a carboxyl group. In Formula (1), R 1 , R 2 and R 3 are a hydrogen atom or a monovalent hydrocarbon group. R 4 is (a) a (n + 1) -valent hydrocarbon group, and (b) the carbon-carbon between (a) a hydrocarbon group is selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO 2- At least one kind of group, or a part or all of the hydrogen atoms of (c) (a) hydrocarbon group and (b) group are selected from the group consisting of halogen atom, cyano, nitro, carboxyl, sulfinyl, thiol, and A group substituted with at least one of the alkoxy groups. R 5 is a single bond or -COO- *.

Description

硬化性樹脂組成物、顯示元件用硬化膜、顯示元件 用硬化膜的形成方法及顯示元件 Curable resin composition, cured film for display element, display element Method for forming cured film and display element

本發明涉及一種硬化性樹脂組成物、感放射線性樹脂組成物、顯示元件用硬化膜、該顯示元件用硬化膜的形成方法及顯示元件。 The present invention relates to a curable resin composition, a radiation-sensitive resin composition, a cured film for a display element, a method for forming the cured film for a display element, and a display element.

在液晶顯示元件、有機電致發光(electroluminescence,EL)等顯示元件中,設有如下硬化膜:用以保持配置為層狀的配線間的絕緣性的層間絕緣膜、用以抑制以觸摸面板(touch panel)為代表的電子零件的劣化或損傷的保護膜、用以將液晶層等設為固定膜厚的間隔件等。對於此種硬化膜除了要求對基板、透明導電膜、配線等的黏附性優異以外,也要求透明性優異。 A display element such as a liquid crystal display element or organic electroluminescence (EL) is provided with a hardened film: an interlayer insulating film for maintaining the insulation of the wiring rooms arranged in a layered manner; Touch panel) is a protective film for deterioration or damage of electronic components, and a spacer for fixing a liquid crystal layer or the like to a fixed film thickness. Such a cured film is required to have excellent adhesion to a substrate, a transparent conductive film, wiring, and the like, as well as excellent transparency.

所述硬化膜的形成中,就用以獲得所需圖案形狀的步驟數少且可獲得充分的平坦性的觀點而言,使用硬化性樹脂組成物。作為此種硬化性樹脂組成物,就可獲得高的表面硬度的方面 而言,已研究有含有在側鏈上具有乙烯性不飽和鍵的聚合物者,且作為所述聚合物已知有使含環氧基的不飽和化合物與具有羧基的聚合物進行反應而得者、使含有異氰酸酯基的不飽和化合物與具有羧基及羥基的聚合物進行反應而得者(參照日本專利特開平11-174464號公報及日本專利特開2002-20442號公報)。 In the formation of the cured film, a curable resin composition is used from the viewpoint that the number of steps for obtaining a desired pattern shape is small and sufficient flatness can be obtained. As such a curable resin composition, a high surface hardness can be obtained In terms of a polymer containing an ethylenically unsaturated bond in a side chain, a polymer obtained by reacting an unsaturated compound containing an epoxy group with a polymer having a carboxyl group has been known as the polymer. It is obtained by reacting an isocyanate group-containing unsaturated compound with a polymer having a carboxyl group and a hydroxyl group (see Japanese Patent Laid-Open No. 11-174464 and Japanese Patent Laid-Open No. 2002-20442).

其中,近來對於硬化膜的性能、特別是黏附性的要求進一步提高,所述現有的硬化性樹脂組成物無法滿足所述要求。此外,就工藝(process)穩定性的觀點而言,對所述現有的硬化性樹脂組成物也要求保存穩定性的改善。 Among them, recently, the requirements for the properties of the cured film, especially the adhesion, have been further increased, and the existing curable resin composition cannot meet the requirements. In addition, from the viewpoint of process stability, improvement of storage stability is also required for the conventional curable resin composition.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平11-174464號公報 [Patent Document 1] Japanese Patent Laid-Open No. 11-174464

[專利文獻2]日本專利特開2002-20442號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2002-20442

本發明是基於以上所述的情況而成,其目的在於提供一種可形成黏附性及透明性優異的硬化膜,且保存穩定性優異的硬化性樹脂組成物。 The present invention is based on the above-mentioned circumstances, and an object thereof is to provide a curable resin composition which can form a cured film having excellent adhesion and transparency and has excellent storage stability.

為了解決所述問題而成的發明為一種硬化性樹脂組成物,其含有聚合物(以下也稱為“[A]聚合物”)及溶劑(以下也 稱為“[B]溶劑”),所述聚合物具有下述式(1)所表示的結構單元(以下也稱為“結構單元(I)”)、以及含酸性基的結構單元(以下也稱為“結構單元(II)”)。 An invention made in order to solve the problems is a curable resin composition containing a polymer (hereinafter also referred to as "[A] polymer") and a solvent (hereinafter also referred to as "[A] polymer"). (Referred to as "[B] solvent"), the polymer has a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (I)") and an acidic group-containing structural unit (hereinafter also referred to as (Referred to as "structural unit (II)").

(式(1)中,R1、R2及R3分別獨立地為氫原子或碳數1~20的1價的烴基;R1、R2及R3中的2個以上可相互鍵結且與它們所鍵結的碳原子一起形成員環數3~20的環結構;R4為(a)碳數1~20的(n+1)價的烴基、(b)在(a)烴基的碳-碳間含有選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、或(c)(a)烴基及(b)基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及碳數1~12的烷氧基組成的群組中的至少1種取代而成的基;n為1~6的整數;n為2以上時,多個R1可相同也可不同,多個R2可相同也可不同,多個R3可相同也可不同;R5為單鍵或-COO-*;*表示與R4鍵結的部位;R6為氫原子、甲基或氟化甲基) (In formula (1), R 1 , R 2, and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; two or more of R 1 , R 2, and R 3 may be bonded to each other. And together with the carbon atoms to which they are bonded, form a ring structure with 3 to 20 member rings; R 4 is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) a hydrocarbon group in (a) The carbon-carbon group contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO 2- , or a group of (c) (a) a hydrocarbon group and (b) A group in which a part or all of the hydrogen atom is substituted with at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. ; N is an integer from 1 to 6; when n is 2 or more, multiple R 1 may be the same or different, multiple R 2 may be the same or different, multiple R 3 may be the same or different; R 5 is a single bond Or -COO- *; * indicates a site bonded to R 4 ; R 6 is a hydrogen atom, a methyl group, or a fluorinated methyl group)

為了解決所述問題而成的另一發明為一種作為層間絕緣膜、保護膜或間隔件的顯示元件用硬化膜,其由所述硬化性樹脂 組成物形成。 Another invention made in order to solve the problem is a cured film for a display element as an interlayer insulating film, a protective film, or a spacer, which is made of the curable resin The composition is formed.

為了解決所述問題而成的進而另一發明為一種顯示元件用硬化膜的形成方法,其包括:在基板上形成塗膜的步驟;對所述塗膜的至少一部分照射放射線的步驟;對所述經放射線照射的塗膜進行顯影的步驟;以及對所述經顯影的塗膜進行加熱的步驟,且由所述硬化性樹脂組成物來形成所述塗膜。 In order to solve the problem, still another invention is a method for forming a cured film for a display element, which includes a step of forming a coating film on a substrate; a step of irradiating at least a part of the coating film with radiation; The step of developing the coating film irradiated with radiation, and the step of heating the developed coating film, and forming the coating film from the curable resin composition.

為了解決所述問題而成的進而另一發明為一種顯示元件,其包括所述顯示元件用硬化膜。 Another invention made in order to solve the said problem is a display element including the said hardened film for display elements.

本發明的硬化性樹脂組成物可形成黏附性及透明性優異的硬化膜,且保存穩定性優異。本發明的顯示元件用硬化膜如上所述般由於黏附性及透明性優異,故可適宜地用作顯示元件的層間絕緣膜、保護膜、間隔件等。因此,這些可適宜地用於液晶裝置(device)等的顯示元件的製造工藝。 The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and has excellent storage stability. Since the cured film for display elements of the present invention is excellent in adhesiveness and transparency as described above, it can be suitably used as an interlayer insulating film, a protective film, a spacer, and the like of a display element. Therefore, these can be suitably used for the manufacturing process of a display element, such as a liquid crystal device.

<硬化性樹脂組成物> <Curable resin composition>

本發明的硬化性樹脂組成物含有[A]聚合物及[B]溶劑。所述硬化性組成物可含有[C]具有乙烯性不飽和鍵的聚合性化合物(以 下也稱為“[C]聚合性化合物”)、[D]自由基聚合起始劑、[E]酸產生劑、及/或[F]使包含選自由不飽和羧酸及不飽和羧酸酐組成的群組中的至少1種與含環氧基的不飽和化合物的單體進行共聚而成的聚合物(以下也稱為“[F]聚合物”)作為優選成分,也可在不損及本發明的效果的範圍內含有其他任意成分。 The curable resin composition of the present invention contains [A] a polymer and [B] a solvent. The curable composition may contain [C] a polymerizable compound having an ethylenically unsaturated bond (as Hereinafter also referred to as "[C] polymerizable compound"), [D] radical polymerization initiator, [E] acid generator, and / or [F] selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride As a preferred component, a polymer (hereinafter also referred to as a "[F] polymer") obtained by copolymerizing at least one of the group consisting of an epoxy-containing unsaturated compound monomer may be used without any damage. And other arbitrary components are included in the range of the effect of this invention.

所述硬化性樹脂組成物由於[A]聚合物的結構單元(I)的(甲基)丙烯醯基可利用加熱而進行聚合反應,因此可作為熱硬化性樹脂組成物發揮功能。另外,所述硬化性樹脂組成物如後述般藉由含有感放射線性的自由基聚合起始劑及/或感放射線性的酸產生劑,可作為感放射線性樹脂組成物發揮功能。放射線例如可列舉:可見光、紫外線、遠紫外線、X射線等電磁波;電子束、α射線等帶電粒子束等。 Since the (meth) acrylfluorenyl group of the structural unit (I) of the polymer of [A] polymer can be polymerized by heating, the curable resin composition can function as a thermosetting resin composition. The curable resin composition can function as a radiation-sensitive resin composition by containing a radiation-sensitive radical polymerization initiator and / or a radiation-sensitive acid generator as described later. Examples of the radiation include electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, and X-rays; charged particle beams such as electron beams and alpha rays; and the like.

以下對各成分進行說明。 Each component is explained below.

<[A]聚合物> <[A] polymer>

[A]聚合物是具有結構單元(I)與結構單元(II)的聚合物。[A]聚合物優選為除了具有所述結構單元以外,還具有為結構單元(I)及結構單元(II)以外的結構單元且不含有羥基、胺基及亞胺基的任一者的結構單元(III),也可在不損及本發明的效果的範圍內含有結構單元(I)~結構單元(III)以外的其他結構單元。[A]聚合物可含有1種或2種以上的各結構單元。 [A] The polymer is a polymer having a structural unit (I) and a structural unit (II). [A] The polymer preferably has a structure that is a structural unit other than the structural unit (I) and the structural unit (II) and does not contain any of a hydroxyl group, an amine group, and an imine group in addition to the structural unit. The unit (III) may contain other structural units other than the structural unit (I) to the structural unit (III) as long as the effect of the present invention is not impaired. [A] The polymer may contain one type or two or more types of each structural unit.

藉由含有[A]聚合物,所述硬化性樹脂組成物的硬化膜的黏附性及透明性優異,並且保存穩定性優異。另外,如後述般在 製成放射線硬化性樹脂組成物的情形時放射線感度優異。關於所述硬化性樹脂組成物藉由具有所述構成而取得所述效果的理由未必明確,但例如可如下般進行推測。即,[A]聚合物具有結構單元(I)作為在側鏈含有乙烯性不飽和鍵的結構單元。所述結構單元(I)與現有的硬化性樹脂組成物的情形不同,並不具有藉由羧基與環氧基的反應而生成的羥基、或藉由羥基與異氰酸酯基的反應而生成的亞胺基等。其結果認為:藉由例如在顯影步驟中抑制鹼性水溶液向圖案間的滲入等,來提高硬化膜的黏附性。另外,由[A]聚合物的結構單元(I)不具有羥基、亞胺基等,而認為是由這些基所引起的加熱時的變質得以抑制,從而硬化膜的透明性提高。進而認為,不會引起所述羥基、亞胺基等與結構單元(II)的羧基等的縮合等,故保存穩定性提高。在製成放射線硬化性樹脂組成物的情形時,認為因在乙烯性不飽和鍵等附近不具有羥基、亞胺基等,自由基或酸的活性變高,其結果為放射線感度進一步提高。 By containing the [A] polymer, the cured film of the curable resin composition is excellent in adhesion and transparency, and has excellent storage stability. In addition, as described later, In the case of a radiation-curable resin composition, the radiation sensitivity is excellent. The reason why the curable resin composition has the above-mentioned effect is not necessarily clear, but it can be estimated as follows, for example. That is, the [A] polymer has a structural unit (I) as a structural unit containing an ethylenically unsaturated bond in a side chain. The structural unit (I) is different from the case of the conventional curable resin composition, and does not have a hydroxyl group generated by a reaction of a carboxyl group and an epoxy group, or an imine formed by a reaction of a hydroxyl group and an isocyanate group. Base etc. As a result, it is considered that the adhesion of the cured film is improved by, for example, suppressing the penetration of the alkaline aqueous solution between the patterns in the development step. In addition, since the structural unit (I) of the [A] polymer does not have a hydroxyl group, an imine group, or the like, it is thought that deterioration due to heating caused by these groups is suppressed, and the transparency of the cured film is improved. Furthermore, it is thought that the above-mentioned hydroxyl group, imide group, and the like do not cause condensation and the like with the carboxyl group and the like of the structural unit (II), so that storage stability is improved. When a radiation-curable resin composition is produced, it is considered that since there is no hydroxyl group, imine group, etc. near the ethylenically unsaturated bond, the activity of radicals or acids is increased, and as a result, radiation sensitivity is further improved.

以下對各結構單元進行說明。 Each structural unit will be described below.

[結構單元(I)] [Construction unit (I)]

結構單元(I)由下述式(1)表示。 The structural unit (I) is represented by the following formula (1).

[化2] [Chemical 2]

所述式(1)中,R1、R2及R3分別獨立地為氫原子或碳數1~20的1價的烴基。R1、R2及R3中的2個以上可相互鍵結且與它們所鍵結的碳原子一起形成員環數3~20的環結構。R4為(a)碳數1~20的(n+1)價的烴基、(b)在(a)烴基的碳-碳間含有選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、或(c)(a)烴基及(b)基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及碳數1~12的烷氧基組成的群組中的至少1種取代而成的基。n為1~6的整數。n為2以上時,多個R1可相同也可不同,多個R2可相同也可不同,多個R3可相同也可不同。R5為單鍵或-COO-*。*表示與R4鍵結的部位。R6為氫原子、甲基或氟化甲基。 In the formula (1), R 1 , R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Two or more of R 1 , R 2, and R 3 may be bonded to each other and form a ring structure with 3 to 20 member rings together with the carbon atoms to which they are bonded. R 4 is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and (b) the carbon-carbon between (a) the hydrocarbon group is selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO 2 -At least one type of group in the group or a part or all of the hydrogen atoms of (c) (a) hydrocarbon group and (b) group are selected from the group consisting of halogen atom, cyano group, nitro group, carboxyl group, A group substituted with at least one of a group consisting of a sulfonic acid group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. n is an integer from 1 to 6. When n is 2 or more, a plurality of R 1 may be the same or different, a plurality of R 2 may be the same or different, and a plurality of R 3 may be the same or different. R 5 is a single bond or -COO- *. * Indicates a site to which R 4 is bonded. R 6 is a hydrogen atom, a methyl group or a fluorinated methyl group.

R1、R2及R3所表示的碳數1~20的1價的烴基例如可列舉:碳數1~20的1價的鏈狀烴基、碳數3~20的1價的脂環式烴基、碳數6~20的1價的芳香族烴基等。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 , R 2 and R 3 include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic group having 3 to 20 carbon atoms. A hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

1價的鏈狀烴基例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、叔丁基等烷基;乙烯基、丙烯基、丁烯基等烯基;乙炔基、丙炔基、丁炔基等炔基等。 Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and t-butyl; vinyl, propenyl, Alkenyl such as butenyl; alkynyl such as ethynyl, propynyl, butynyl and the like.

1價的脂環式烴基例如可列舉:環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、金剛烷基等環烷基;環丙烯基、環丁烯基、環戊烯基、環己烯基、環庚烯基、環辛烯基、降冰片烯基等環烯基等。 Examples of the monovalent alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl; cyclopropenyl, Cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, norbornenyl and other cycloalkenyl groups.

1價的芳香族烴基例如可列舉:苯基、甲苯基、二甲苯基、均三甲苯基、萘基、蒽基等芳基;苄基、苯乙基、萘基甲基、蒽基甲基等芳烷基等。 Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, and anthracenyl; benzyl, phenethyl, naphthylmethyl, and anthrylmethyl And so on.

R1、R2及R3中的2個以上相互鍵結且與它們所鍵結的碳原子一起形成的員環數3~20的環結構例如可列舉:環丙烯結構、環丁烯結構、環戊烯結構、環己烯結構、環辛烯結構、降冰片烯結構等環烯結構等。 Examples of the ring structure of R 1 , R 2 and R 3 having two or more member rings having 3 to 20 members bonded together with the carbon atom to which they are bonded include, for example, a cyclopropene structure, a cyclobutene structure, Cyclopentene structure, cyclohexene structure, cyclooctene structure, norbornene structure and other cycloolefin structures.

R1、R2及R3優選為氫原子、1價的鏈狀烴基,更優選為氫原子、烷基,進而優選為氫原子、甲基、乙基,特別優選為氫原子。 R 1 , R 2 and R 3 are preferably a hydrogen atom and a monovalent chain hydrocarbon group, more preferably a hydrogen atom and an alkyl group, still more preferably a hydrogen atom, a methyl group, and an ethyl group, and particularly preferably a hydrogen atom.

R4所表示的(a)碳數1~20的(n+1)價的烴基例如可列舉:自作為R1、R2及R3所表示的1價的烴基而例示的基中去除n個氫原子而成的基等。 Examples of the (a) (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R 4 include the group exemplified as the monovalent hydrocarbon group represented by R 1 , R 2, and R 3 . A hydrogen atom.

R4所表示的(b)在(a)烴基的碳-碳間含有氧原子的基例如可列舉:自作為R1、R2及R3而例示的烴基中的2個與氧原子鍵結而成的醚中去除(n+1)個氫原子而成的基等。 Examples of the (b) group containing an oxygen atom between the carbon and carbon of the (a) hydrocarbon group represented by R 4 include two of the hydrocarbon groups exemplified as R 1 , R 2, and R 3 bonded to an oxygen atom. The resulting ether is a group obtained by removing (n + 1) hydrogen atoms.

R4所表示的(b)在(a)烴基的碳-碳間含有硫原子的基例如可列舉:自作為R1、R2及R3而例示的烴基中的2個與硫原子 鍵結而成的硫醚中去除(n+1)個氫原子而成的基等。 Examples of (b) a group containing a sulfur atom between the carbon and carbon of the (a) hydrocarbon group represented by R 4 include two of the hydrocarbon groups exemplified as R 1 , R 2, and R 3 bonded to a sulfur atom. A group obtained by removing (n + 1) hydrogen atoms from the resulting thioether.

R4所表示的(b)在(a)烴基的碳-碳間含有-SO-的基例如可列舉:自作為R1、R2及R3而例示的烴基中的2個與-SO-的硫原子鍵結而成的亞碸化合物中去除(n+1)個氫原子而成的基等。 Examples of the (b) group containing -SO- between the carbon-carbon of (a) a hydrocarbon group represented by R 4 include two of the hydrocarbon groups exemplified as R 1 , R 2, and R 3 and -SO- A group obtained by removing an (n + 1) hydrogen atom from a fluorene compound in which a sulfur atom is bonded.

R4所表示的(b)在(a)烴基的碳-碳間含有-SO2-的基例如可列舉:自作為R1、R2及R3而例示的烴基中的2個與-SO2-的硫原子鍵結而成的碸化合物中去除(n+1)個氫原子而成的基等。 Examples of the (b) group containing -SO 2 -between the carbon and carbon of the (a) hydrocarbon group represented by R 4 include two of the hydrocarbon groups exemplified as R 1 , R 2, and R 3 and -SO. 2 - sulfur atom bonded sulfone compound obtained by removing (n + 1) hydrogen atoms from a group.

碳數1~12的烷氧基例如可列舉:甲氧基、乙氧基、丙氧基、丁氧基、戊氧基等。 Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy.

R4所表示的(c)基的鹵素原子例如可列舉:氟原子、氯原子、溴原子、碘原子等。亞磺酸基是指-SO2H。 Examples of the halogen atom of the (c) group represented by R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The sulfinic group refers to -SO 2 H.

R4優選為(a)烴基、(b)基,更優選為自烷烴、環烷烴、芳烴(arene)及環烷基烷基醚中去除(n+1)個氫原子而成的基,進而優選為自碳數2~6的烷烴、碳數3~15的環烷烴、碳數6~18的芳烴及碳數5~20的環烷基烷基醚中去除(n+1)個氫原子而成的基,特別優選為自乙烷基、環己烷、金剛烷、苯及金剛烷基乙基醚中去除(n+1)個氫原子而成的基。 R 4 is preferably (a) a hydrocarbon group and (b) group, more preferably a group obtained by removing (n + 1) hydrogen atoms from an alkane, a cycloalkane, an arene (arene), and a cycloalkylalkyl ether, and furthermore It is preferred to remove (n + 1) hydrogen atoms from alkanes having 2 to 6 carbon atoms, naphthenes having 3 to 15 carbon atoms, aromatics having 6 to 18 carbon atoms and cycloalkyl alkyl ethers having 5 to 20 carbon atoms. The formed group is particularly preferably a group obtained by removing (n + 1) hydrogen atoms from an ethane group, cyclohexane, adamantane, benzene, and adamantyl ethyl ether.

就提供結構單元(I)的單體的合成容易性的觀點而言,n優選為1~3的整數,更優選為1或2,就進一步提高硬化性及製成放射線硬化性樹脂組成物時的放射線感度的觀點而言,n進而優選為2。 From the viewpoint of providing ease of synthesis of the monomer of the structural unit (I), n is preferably an integer of 1 to 3, and more preferably 1 or 2. In order to further improve the hardenability and produce a radiation-curable resin composition, From the viewpoint of the radiation sensitivity, n is more preferably 2.

在R4為鏈狀烴基、脂環式烴基、在這些基的碳-碳間含有 選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、以及所述基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及碳數1~12的烷氧基組成的群組中的至少1種取代而成的基的情形時,R5優選為-COO-*。 R 4 is a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, -SO- and -SO 2 -between the carbon and carbon of these groups, And at least part of or all of the hydrogen atoms of the group are selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. In the case of one substituted group, R 5 is preferably -COO- *.

R6所表示的氟化甲基例如可列舉:氟甲基、二氟甲基、三氟甲基等。其中優選為三氟甲基。 Examples of the fluorinated methyl group represented by R 6 include fluoromethyl, difluoromethyl, and trifluoromethyl. Among these, trifluoromethyl is preferred.

就提供結構單元(I)的單體的共聚性的觀點而言,R6優選為甲基。 From the viewpoint of providing copolymerization of the monomer of the structural unit (I), R 6 is preferably a methyl group.

結構單元(I)例如可列舉:下述式(1-1)~式(1-12)所表示的結構單元(以下也稱為“結構單元(I-1)~結構單元(I-12)”)等。 The structural unit (I) can be exemplified by the structural units represented by the following formulae (1-1) to (1-12) (hereinafter also referred to as "structural units (I-1) to (I-12) ")Wait.

[化3] [Chemical 3]

所述式(1-1)~式(1-12)中,R6與所述式(1)同義。 In the formulae (1-1) to (1-12), R 6 is synonymous with the formula (1).

其中,優選為結構單元(I-1)~結構單元(I-7)。 Among these, the structural unit (I-1) to the structural unit (I-7) are preferred.

將結構單元(I)組入至[A]聚合物的方法並無特別限定, 例如可列舉如下方法等:如下述流程所示般,藉由使用下述式(i)所表示的單體的聚合,合成組入有下述式(1')所表示的結構單元(I')的聚合物,並使所述聚合物例如在三乙胺等鹼的存在下進行脫鹵化氫反應,由此生成乙烯性不飽和雙鍵,從而形成下述式(1)所表示的結構單元(I)。 The method for incorporating the structural unit (I) into the [A] polymer is not particularly limited, For example, as shown in the following scheme, a polymerization unit using a monomer represented by the following formula (i) is synthesized to incorporate a structural unit (I ') represented by the following formula (1'). ), And the polymer is subjected to a dehydrohalogenation reaction in the presence of a base such as triethylamine to generate an ethylenically unsaturated double bond, thereby forming a structural unit represented by the following formula (1) (I).

所述流程中,R1~R6及n與所述式(1)同義。X為鹵素原子。 In the scheme, R 1 to R 6 and n are synonymous with the formula (1). X is a halogen atom.

就提高脫鹵化氫反應的產率的觀點而言,X所表示的鹵素原子優選為氯原子、溴原子,更優選為氯原子。 From the viewpoint of improving the yield of the dehydrohalogenation reaction, the halogen atom represented by X is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

所述式(i)所表示的單體例如可藉由如下方式進行合成:使(甲基)丙烯酸2-羥基乙酯等具有(甲基)丙烯醯基及羥基的化合物與3-氯丙醯氯等β-鹵代-羧醯鹵在吡啶等鹼的存在下,在二氯甲 烷等溶劑中進行脫鹵化氫縮合反應。 The monomer represented by the formula (i) can be synthesized, for example, by using a compound having a (meth) acrylfluorenyl group and a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and 3-chloropropylammonium Β-halo-carboxamidines such as chlorine in the presence of bases such as pyridine, The dehydrohalogenation condensation reaction is performed in a solvent such as alkane.

所述結構單元(I)的含有比例以相對於[A]聚合物的合成中所使用的全部單體的投入比計,優選為5莫耳%~90莫耳%,更優選為10莫耳%~70莫耳%,進而優選為15莫耳%~40莫耳%。藉由將所述含有比例設為所述範圍,可進一步提高硬化膜的黏附性及透明性、保存穩定性、以及製成放射線硬化性樹脂組成物時的放射線感度。 The content ratio of the structural unit (I) is based on the input ratio of all monomers used in the synthesis of the [A] polymer, and is preferably 5 mol% to 90 mol%, and more preferably 10 mol. % To 70 mol%, more preferably 15 to 40 mol%. By setting the content ratio to the range, it is possible to further improve the adhesion and transparency of the cured film, storage stability, and radiation sensitivity when the radiation-curable resin composition is made.

[結構單元(II)] [Construction unit (II)]

結構單元(II)是含有酸性基的結構單元。酸性基可列舉羧基、酚性羥基、磺基、含有氟醇的基等,其中特別優選為羧基。藉由[A]聚合物具有結構單元(II),所述硬化性樹脂組成物可發揮鹼顯影性,從而作為鹼可溶性樹脂發揮功能。 The structural unit (II) is a structural unit containing an acidic group. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a fluoroalcohol-containing group. Among them, a carboxyl group is particularly preferred. When the [A] polymer has the structural unit (II), the curable resin composition can exhibit alkali developability and function as an alkali-soluble resin.

提供所述結構單元(II)的單體例如可列舉:不飽和單羧酸、不飽和二羧酸、多元羧酸的單[(甲基)丙烯醯基氧基烷基]酯、不飽和二羧酸的酐、在兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯、具有羧基的不飽和多環式化合物及其酐等。 Examples of the monomer providing the structural unit (II) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, poly [(meth) acrylfluorenyloxyalkyl] ester of polycarboxylic acid, and unsaturated dicarboxylic acid. An anhydride of a carboxylic acid, a mono (meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both ends, an unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

不飽和單羧酸例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸等。 Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and butenoic acid.

不飽和二羧酸例如可列舉:順丁烯二酸、反丁烯二酸、檸康酸、中康酸、衣康酸等。 Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.

多元羧酸的單[(甲基)丙烯醯基氧基烷基]酯例如可列舉:順丁烯二酸單[(甲基)丙烯醯基氧基乙基]酯、丁二酸單[2-(甲 基)丙烯醯基氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯基氧基乙基]酯等。 Examples of the mono [(meth) acrylfluorenyloxyalkyl] ester of a polycarboxylic acid include maleic acid mono [(meth) acrylfluorenyloxyethyl] ester, and succinic acid mono [2 -(A Propyl) acrylfluorenyloxyethyl] ester, phthalate mono [2- (meth) acrylfluorenyloxyethyl] ester, and the like.

不飽和二羧酸的酐例如可列舉:作為所述二羧酸而例示的化合物的酐等。 Examples of the anhydride of the unsaturated dicarboxylic acid include anhydrides of the compounds exemplified as the dicarboxylic acid.

在兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯例如可列舉:ω-羧基聚己內酯單(甲基)丙烯酸酯等。 Examples of the mono (meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxy polycaprolactone mono (meth) acrylate and the like.

具有羧基的不飽和多環式化合物及其酐例如可列舉:5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。 Examples of unsaturated polycyclic compounds having a carboxyl group and their anhydrides include 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2 .1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like.

另外,提供所述結構單元(II)的單體也可使用保護所述羧酸等的羧基而成的化合物。所述化合物中的被保護的羧基例如可列舉羧基的氫原子經-C(Ra)(Rb)(ORc)取代而成的基(Ra及Rb分別獨立地為氫原子或碳數1~20的1價的烴基。Rc為碳數1~20的1價的烴基)等。Ra、Rb及Rc所表示的碳數1~20的1價的烴基例如可列舉與作為所述R1、R2及R3而例示的1價的烴基同樣的基等。其中,Ra及Rc優選為烷基。Rb優選為氫原子。 Moreover, as a monomer which provides the said structural unit (II), you may use the compound which protected the carboxyl group, such as the said carboxylic acid. Examples of the protected carboxyl group in the compound include a group in which a hydrogen atom of a carboxyl group is substituted with -C (R a ) (R b ) (OR c ) (R a and R b are each independently a hydrogen atom or a carbon A monovalent hydrocarbon group having a number of 1 to 20. R c is a monovalent hydrocarbon group having a carbon number of 1 to 20) and the like. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R a , R b and R c include the same groups as the monovalent hydrocarbon group exemplified as the R 1 , R 2 and R 3 . Among them, R a and R c are preferably an alkyl group. R b is preferably a hydrogen atom.

保護所述羧酸等的羧基而成的化合物例如可列舉:(甲基)丙烯酸1-丁氧基乙酯、(甲基)丙烯酸1-乙氧基乙酯、(甲基)丙烯酸1-乙氧基丁酯等。 Examples of the compound obtained by protecting the carboxyl group such as the carboxylic acid include 1-butoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, and 1-ethyl (meth) acrylate Oxybutyl etc.

其中,就提供結構單元(II)的單體的共聚性及獲得容易 性、以及[A]聚合物對鹼性水溶液的溶解性的觀點而言,優選為不飽和單羧酸、保護不飽和單羧酸的羧基而成的化合物,更優選為甲基丙烯酸、甲基丙烯酸1-丁氧基乙酯。 Among them, the copolymerization of the monomers providing the structural unit (II) and the ease of obtaining From the viewpoint of the solubility and the solubility of the [A] polymer in an alkaline aqueous solution, an unsaturated monocarboxylic acid and a compound that protects the carboxyl group of the unsaturated monocarboxylic acid are preferred, and methacrylic acid and methyl are more preferred. 1-butoxyethyl acrylate.

所述結構單元(II)的含有比例以相對於[A]聚合物的合成中所使用的全部單體的投入比計,優選為5莫耳%~50莫耳%,更優選為10莫耳%~40莫耳%,進而優選為15莫耳%~35莫耳%。藉由將所述含有比例設為所述範圍,可將所述硬化性樹脂組成物的鹼顯影性設為更適當的性質。 The content ratio of the structural unit (II) is preferably 5 mol% to 50 mol%, and more preferably 10 mol, based on the input ratio of all monomers used in the synthesis of the [A] polymer. % To 40 mol%, more preferably 15 to 35 mol%. By setting the content ratio to the range, the alkali developability of the curable resin composition can be set to a more appropriate property.

[結構單元(III)] [Construction unit (III)]

結構單元(III)是結構單元(I)及結構單元(II)以外的結構單元且是不含有羥基、胺基及亞胺基的任一者的結構單元。藉由[A]聚合物具有結構單元(III),可進一步提高所述硬化性樹脂組成物的保存穩定性。 The structural unit (III) is a structural unit other than the structural unit (I) and the structural unit (II), and is a structural unit that does not contain any of a hydroxyl group, an amine group, and an imine group. When the [A] polymer has the structural unit (III), the storage stability of the curable resin composition can be further improved.

提供所述結構單元(III)的單體例如可列舉甲基丙烯酸烷基酯、甲基丙烯酸環烷基酯、丙烯酸烷基酯、丙烯酸環烷基酯、甲基丙烯酸芳香族酯、丙烯酸芳香族酯等,另外可列舉為以下化合物等且不具有羥基、胺基及亞胺基的任一者等:不飽和二羧酸二酯、雙環不飽和化合物、N-順丁烯二醯亞胺化合物、不飽和芳香族化合物、共軛二烯、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架或吡喃骨架的不飽和化合物、其他不飽和化合物等。 Examples of the monomer providing the structural unit (III) include alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aromatic methacrylate, and aromatic acrylic Examples of the ester include the following compounds and the like, which do not have any of a hydroxyl group, an amine group, and an imine group: unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, and N-maleimide diimide compounds , Unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton, other unsaturated compounds, and the like.

甲基丙烯酸烷基酯例如可列舉:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸第二丁酯、甲基丙 烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異癸酯、甲基丙烯酸正月桂基酯、甲基丙烯酸十三烷基酯、甲基丙烯酸正硬脂基酯等。 Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and methacrylic acid. Tert-butyl enoate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

甲基丙烯酸環烷基酯例如可列舉:甲基丙烯酸環己酯、甲基丙烯酸2-甲基環己酯、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基氧基乙酯、甲基丙烯酸異冰片基酯等。 Examples of the cycloalkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, Tricyclo [5.2.1.0 2,6 ] decane-8-yloxyethyl methacrylate, isobornyl methacrylate and the like.

丙烯酸烷基酯例如可列舉:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸第二丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸異癸酯、丙烯酸正月桂基酯、丙烯酸十三烷基酯、丙烯酸正硬脂基酯等。 Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-lauryl acrylate. , Tridecyl acrylate, n-stearyl acrylate, etc.

丙烯酸環烷基酯例如可列舉:丙烯酸環己酯、丙烯酸-2-甲基環己酯、丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、丙烯酸三環[5.2.1.02,6]癸烷-8-基氧基乙酯、丙烯酸異冰片基酯等。 Examples of the cycloalkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl acrylate, and tricyclic acrylate [5.2.1.0] 2,6 ] decane-8-yloxyethyl, isobornyl acrylate and the like.

甲基丙烯酸芳香族酯例如可列舉:甲基丙烯酸苯基酯、甲基丙烯酸萘基酯等甲基丙烯酸芳基酯;甲基丙烯酸苄基酯、甲基丙烯酸苯乙基酯等甲基丙烯酸芳烷基酯等。 Examples of aromatic methacrylic esters include aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate; aromatic methacrylates such as benzyl methacrylate and phenethyl methacrylate. Alkyl esters, etc.

丙烯酸芳香族酯例如可列舉:丙烯酸苯基酯、丙烯酸萘基酯等丙烯酸芳基酯;丙烯酸苄基酯、丙烯酸苯乙基酯等丙烯酸芳烷基酯等。 Examples of the acrylic aromatic esters include aryl acrylates such as phenyl acrylate and naphthyl acrylate; aralkyl acrylates such as benzyl acrylate and phenethyl acrylate; and the like.

不飽和二羧酸二酯例如可列舉:順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙酯等。 Examples of the unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

雙環不飽和化合物例如可列舉:雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-叔丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己基氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-二(叔丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-二(環己基氧基羰基)雙環[2.2.1]庚-2-烯等。 Examples of the bicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept-2- Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonylcarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] Hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc.

N-順丁烯二醯亞胺化合物例如可列舉:N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-(4-羥基苯基)順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等。 Examples of the N-cis-butene difluorene imine compound include N-phenyl-cis-butene difluorene imine, N-cyclohexyl-cis-butene difluorene imine, N-benzyl-cis butene difluorene, N- (4-hydroxyphenyl) cis-butenediamidoimide, N-succinimidylimido-3-cisbutenediamidoiminobenzoate, N-succinimidylimino-4-cis Butene difluorene imide butyrate, N-succinimide imino-6-cis butene diimide hexanoate, N-succinimide 3-maleimide dipropionate Esters, N- (9-acridyl) cis-butenediamidine, and the like.

不飽和芳香族化合物例如可列舉:苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯等。 Examples of the unsaturated aromatic compound include styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

共軛二烯例如可列舉:1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

具有四氫呋喃骨架的不飽和化合物例如可列舉:甲基丙烯酸四氫糠基酯、2-甲基丙烯醯基氧基-丙酸四氫糠基酯、3-(甲基)丙烯醯基氧基四氫呋喃-2-酮等。 Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacrylfluorenyloxy-propionate tetrahydrofurfuryl ester, and 3- (meth) acrylfluorenyloxytetrahydrofuran. -2-ketone, etc.

含有呋喃骨架的不飽和化合物例如可列舉:2-甲基-5-(3- 呋喃基)-1-戊烯-3-酮、(甲基)丙烯酸糠基酯、1-呋喃-2-丁基-3-烯-2-酮、1-呋喃-2-丁基-3-甲氧基-3-烯-2-酮、6-(2-呋喃基)-2-甲基-1-己烯-3-酮、6-呋喃-2-基-己-1-烯-3-酮、丙烯酸2-呋喃-2-基-1-甲基-乙基酯、6-(2-呋喃基)-6-甲基-1-庚烯-3-酮等。 Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5- (3- Furanyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3- Methoxy-3-en-2-one, 6- (2-furanyl) -2-methyl-1-hexene-3-one, 6-furan-2-yl-hex-1-ene-3 -Ketone, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furanyl) -6-methyl-1-hepten-3-one, and the like.

含有四氫吡喃骨架的不飽和化合物例如可列舉:甲基丙烯酸四氫吡喃-2-基甲酯、2,6-二甲基-8-(四氫吡喃-2-基氧基)辛-1-烯-3-酮、2-甲基丙烯酸四氫吡喃-2-基酯、1-(四氫吡喃-2-氧基)丁基-3-烯-2-酮等。 Examples of the unsaturated compound containing a tetrahydropyran skeleton include tetrahydropyran-2-yl methyl methacrylate and 2,6-dimethyl-8- (tetrahydropyran-2-yloxy). Oct-1-en-3-one, tetrahydropyran-2-yl 2-methacrylate, 1- (tetrahydropyran-2-oxy) butyl-3-en-2-one, and the like.

含有吡喃骨架的不飽和化合物例如可列舉:4-(1,4-二氧雜-5-氧代-6-庚烯基)-6-甲基-2-吡喃、4-(1,5-二氧雜-6-氧代-7-辛烯基)-6-甲基-2-吡喃等。 Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxo-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1, 5-dioxa-6-oxo-7-octenyl) -6-methyl-2-pyran and the like.

其他不飽和化合物例如可列舉:丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯等。 Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

其中,就提供結構單元(III)的單體的共聚性的觀點而言,優選為甲基丙烯酸烷基酯、不飽和芳香族化合物,更優選為甲基丙烯酸甲酯、苯乙烯。 Among these, from the viewpoint of providing copolymerization of the monomers of the structural unit (III), alkyl methacrylate and unsaturated aromatic compounds are preferred, and methyl methacrylate and styrene are more preferred.

所述結構單元(III)的含有比例以相對於[A]聚合物的合成中所使用的全部單體的投入比計,優選為0莫耳%~80莫耳%,更優選為20莫耳%~75莫耳%,進而優選為40莫耳%~70莫耳%。藉由將所述含有比例設為所述範圍,可進一步提高所述硬化性樹脂組成物的保存穩定性。 The content ratio of the structural unit (III) is based on the input ratio of all monomers used in the synthesis of the [A] polymer, and is preferably 0 mol% to 80 mol%, and more preferably 20 mol. % To 75 mol%, more preferably 40 to 70 mol%. By setting the content ratio to the range, the storage stability of the curable resin composition can be further improved.

[其他結構單元] [Other structural units]

其他結構單元例如可列舉含有羥基、胺基或亞胺基的結構單元等。其他結構單元的含有比例以相對於[A]聚合物的合成中所使用的全部單體的投入比計,優選為20莫耳%以下,更優選為5莫耳%以下,進而優選為0莫耳%。 Examples of the other structural unit include a structural unit containing a hydroxyl group, an amine group, or an imine group. The content ratio of the other structural units is preferably 20 mol% or less, more preferably 5 mol% or less, and still more preferably 0 mol, based on the input ratio of all monomers used in the synthesis of the [A] polymer. ear%.

相對於所述硬化性樹脂組成物的總固體成分,[A]聚合物的含有量優選為30質量%以上,更優選為35質量%~95質量%,進而優選為40質量%~70質量%。 The content of the [A] polymer is preferably 30% by mass or more, more preferably 35% by mass to 95% by mass, and still more preferably 40% by mass to 70% by mass with respect to the total solid content of the curable resin composition. .

<[A]聚合物的合成方法> <[A] Synthesis method of polymer>

[A]聚合物可如所述般藉由如下方式進行合成,例如在溶劑中使用自由基聚合起始劑,將如所述式(i)所表示的單體般在聚合反應後利用脫鹵化氫反應來提供結構單元(I)的單體、提供結構單元(II)的單體、視需要提供結構單元(III)的單體等聚合,使所得的聚合物進行脫鹵化氫反應而形成結構單元(I)。 [A] The polymer can be synthesized as described by, for example, using a radical polymerization initiator in a solvent, and dehalogenating the monomer as represented by the formula (i) after the polymerization reaction. Hydrogen reacts to polymerize the monomers that provide structural unit (I), monomers that provide structural unit (II), and monomers that provide structural unit (III) as needed, and polymerize the resulting polymer by dehydrohalogenation to form a structure Unit (I).

溶劑例如可列舉:醇、鏈狀醚、環狀醚、二醇醚、乙二醇烷基醚乙酸酯、二乙二醇烷基醚、丙二醇單烷基醚、丙二醇單烷基醚乙酸酯、丙二醇單烷基醚丙酸酯、芳香族烴、酮、其他酯等。 Examples of the solvent include alcohols, chain ethers, cyclic ethers, glycol ethers, glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Esters, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, other esters, and the like.

醇例如可列舉:甲醇、乙醇、苄醇、2-苯基乙基醇、3-苯基-1-丙醇等。 Examples of the alcohol include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol.

鏈狀醚例如可列舉:二乙醚、二丙醚、二丁醚、苯甲醚、二苯基醚等。 Examples of the chain ether include diethyl ether, dipropyl ether, dibutyl ether, anisole, and diphenyl ether.

環狀醚例如可列舉:四氫呋喃、四氫吡喃等。 Examples of the cyclic ether include tetrahydrofuran and tetrahydropyran.

二醇醚例如可列舉:乙二醇單甲醚、乙二醇單乙醚等。 Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

乙二醇烷基醚乙酸酯例如可列舉:甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙醚乙酸酯等。 Examples of the glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate. .

二乙二醇烷基醚例如可列舉:二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇乙基甲醚等。 Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether. .

丙二醇單烷基醚例如可列舉:丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚等。 Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

丙二醇單烷基醚乙酸酯例如可列舉:丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯等。 Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

丙二醇單烷基醚丙酸酯例如可列舉:丙二醇單甲醚丙酸酯、丙二醇單乙醚丙酸酯、丙二醇單丙醚丙酸酯、丙二醇單丁醚丙酸酯等。 Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like.

芳香族烴例如可列舉:甲苯、二甲苯等。 Examples of the aromatic hydrocarbon include toluene and xylene.

酮例如可列舉:甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮等。 Examples of the ketone include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

其他酯例如可列舉:乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、 3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等。 Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methyl Ethyl propionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, Ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate , Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, Ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2 -Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3 -Butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate , Methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate , Ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

溶劑優選為其他酯類,更優選為3-甲氧基丙酸甲酯。所述溶劑可使用1種或2種以上。 The solvent is preferably another ester, and more preferably methyl 3-methoxypropionate. These solvents can be used alone or in combination of two or more.

自由基聚合起始劑例如可列舉:2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)、4,4'-偶氮雙(4-氰基戊酸)、二甲基-2,2'-偶氮雙(2-甲基丙酸酯)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等。 Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), and 2,2'-azo Bis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis ( 2-methylpropionate), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and the like.

其中優選為2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基 戊腈)。 Among them, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethyl Valeronitrile).

相對於聚合中使用的單體的合計100莫耳,自由基聚合起始劑的使用量優選為1莫耳%~10莫耳%,更優選為2莫耳%~8莫耳%。自由基聚合起始劑可使用1種或2種以上。 The use amount of the radical polymerization initiator is preferably 1 mol% to 10 mol%, and more preferably 2 mol% to 8 mol% with respect to 100 mol of the monomers used in the polymerization in total. As the radical polymerization initiator, one kind or two or more kinds can be used.

在聚合反應中,為了調整分子量可使用分子量調整劑。分子量調整劑例如可列舉:氯仿、四溴化碳等鹵化烴類;正己基硫醇、正辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、硫代乙醇酸等硫醇類;硫化黃原酸二甲酯、二硫化黃原酸二異丙酯等黃原酸類;萜品油烯、α-甲基苯乙烯二聚物等。 In the polymerization reaction, a molecular weight modifier can be used in order to adjust the molecular weight. Examples of molecular weight regulators include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and thioglycolic acid. Thiols; xanthates such as dimethyl xanthate and diisopropyl xanthate; terpineolene and α -methylstyrene dimers.

分子量調整劑的使用量可根據所期望的[A]聚合物的分子量而適宜選擇,但相對於聚合中使用的單體的合計100莫耳%,優選為0.1莫耳%~10莫耳%,更優選為0.5莫耳%~5莫耳%。分子量調整劑可使用1種或2種以上。 The use amount of the molecular weight modifier can be appropriately selected according to the desired molecular weight of the [A] polymer, but is preferably 0.1 mol% to 10 mol% relative to the total of 100 mol% of the monomers used in the polymerization. More preferably, it is 0.5 to 5 mol%. The molecular weight adjuster can be used alone or in combination of two or more.

聚合溫度通常為0℃~150℃,優選為50℃~120℃。 聚合時間通常為10分鐘~20小時,優選為30分鐘~6小時。 The polymerization temperature is usually 0 ° C to 150 ° C, and preferably 50 ° C to 120 ° C. The polymerization time is usually 10 minutes to 20 hours, and preferably 30 minutes to 6 hours.

聚合反應後的脫鹵化氫反應中使用的溶劑可使用作為所述聚合中可使用的溶劑而例示的溶劑,優選為直接使用所述聚合中使用的溶劑。即,優選為在所述聚合反應液中添加鹼,並進行脫鹵化氫反應。 As the solvent used in the dehydrohalogenation reaction after the polymerization reaction, a solvent exemplified as a solvent usable in the polymerization can be used, and the solvent used in the polymerization is preferably used directly. That is, it is preferable to add a base to the polymerization reaction liquid and perform a dehydrohalogenation reaction.

脫鹵化氫反應中使用的鹼例如可列舉: 二乙胺、二丙胺、三甲胺、三乙胺、三丙胺、吡咯啶、呱啶、吡啶、三乙醇胺等胺類;氫氧化鈉、氫氧化鉀、氫氧化鈣等金屬氫氧化物;碳酸鈉、碳酸鉀、碳酸鈣等金屬碳酸鹽;碳酸氫鈉、碳酸氫鉀、碳酸氫鈣等金屬碳酸氫鹽;甲醇鈉、叔丁醇鉀等金屬醇鹽等。 Examples of the base used in the dehydrohalogenation reaction include: Diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, pyrrolidine, pyridine, pyridine, triethanolamine and other amines; sodium hydroxide, potassium hydroxide, calcium hydroxide and other metal hydroxides; sodium carbonate , Potassium carbonate, calcium carbonate and other metal carbonates; sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and other metal bicarbonates; sodium methoxide, potassium tert-butoxide and other metal alkoxides.

相對於脫離的鹵化氫1莫耳,脫鹵化氫反應中使用的鹼的量優選為1莫耳~10莫耳,更優選為1.5莫耳~7莫耳,進而優選為2莫耳~5莫耳。 The amount of the base used in the dehydrohalogenation reaction is preferably 1 mol to 10 mol, more preferably 1.5 mol to 7 mol, and still more preferably 2 mol to 5 mol, relative to 1 mol of the desorbed hydrogen halide. ear.

脫鹵化氫反應的溫度通常為0℃~150℃,優選為50℃~100℃。 The temperature of the dehydrohalogenation reaction is usually 0 ° C to 150 ° C, and preferably 50 ° C to 100 ° C.

脫鹵化氫反應的時間通常為10分鐘~20小時,優選為30分鐘~6小時。 The time of the dehydrohalogenation reaction is usually 10 minutes to 20 hours, and preferably 30 minutes to 6 hours.

[A]聚合物的聚苯乙烯換算重量平均分子量(Mw)優選為2,000~100,000,更優選為3,000~50,000,進而優選為5,000~20,000。藉由將[A]聚合物的Mw設為所述範圍,可進一步提高硬化膜的黏附性,另外可進一步提高製成放射線硬化性樹脂組成物時的放射線感度。 [A] The polystyrene-equivalent weight average molecular weight (Mw) of the polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 5,000 to 20,000. By setting the Mw of the [A] polymer to the above range, the adhesiveness of the cured film can be further improved, and the radiation sensitivity when the radiation-curable resin composition is made can be further improved.

[A]聚合物的分子量分布(Mw/Mn)優選為5.0以下,更優選為3.0以下。藉由將[A]聚合物的Mw/Mn設為所述上限以下,可使硬化膜的圖案形狀進一步良好。 [A] The molecular weight distribution (Mw / Mn) of the polymer is preferably 5.0 or less, and more preferably 3.0 or less. By setting the Mw / Mn of the [A] polymer to be equal to or lower than the upper limit, the pattern shape of the cured film can be further improved.

<[B]溶劑> <[B] Solvent>

[B]溶劑只要是均勻地溶解含有成分且不與含有成分反應的溶劑便可使用。[B]溶劑例如可列舉與作為合成[A]聚合物的聚合中使用的溶劑而例示的溶劑同樣的溶劑等。[B]溶劑可使用1種或2種以上。 [B] The solvent can be used as long as it dissolves the contained component uniformly and does not react with the contained component. Examples of the [B] solvent include the same solvents as those exemplified as the solvent used in the polymerization of the polymer [A], and the like. [B] One or more solvents can be used.

就溶解性、固體成分的分散性、所述硬化性樹脂組成物的塗佈性等觀點而言,[B]溶劑優選為丙二醇單甲醚、丙二醇單乙醚、乙酸乙二醇單甲醚酯、乙酸丙二醇單甲醚酯、乙酸丙二醇單乙醚酯、乙酸3-甲氧基丁酯、二乙二醇二甲醚、二乙二醇甲基乙醚、環己酮、2-庚酮、3-庚酮、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯、乳酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯,更優選為3-甲氧基丙酸甲酯、二乙二醇甲基乙醚、乙酸3-甲氧基丁酯。另外[B]溶劑也優選為既含有所述溶劑也含有高沸點溶劑。所述高沸點溶劑例如可列舉:苄基乙醚、二-正己醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、乙酸苄基酯、苯甲酸乙酯、乙二酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯、碳酸伸乙酯、碳酸伸丙酯、乙二醇單苯基醚乙酸酯等。 [B] The solvent is preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether ester, or the like from the viewpoints of solubility, dispersibility of solid content, and coatability of the curable resin composition. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptane Ketone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-pentyl formate , Isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, more preferably methyl 3-methoxypropionate, diethylene glycol Alcohol methyl ether, 3-methoxybutyl acetate. [B] The solvent also preferably contains both the solvent and the high-boiling-point solvent. Examples of the high boiling point solvent include benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, and ethyl benzoate. Esters, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

[B]溶劑的含有量並無特別限定,但就所述硬化性樹脂組成物的塗敷性、保存穩定性等觀點而言,優選為20質量%~90質量%,更優選為40質量%~80質量%。 [B] The content of the solvent is not particularly limited, but from the viewpoints of coatability and storage stability of the curable resin composition, it is preferably from 20% by mass to 90% by mass, and more preferably from 40% by mass. ~ 80% by mass.

<[C]聚合性化合物> <[C] polymerizable compound>

[C]聚合性化合物是具有乙烯性不飽和鍵的聚合性化合物。所述硬化性樹脂組成物藉由還含有[C]聚合性化合物,在形成負型圖案時可進一步提高硬化膜的黏附性,另外在形成正型圖案時可提高圖案形狀的熱穩定性。也可以藉由加熱使[C]聚合性化合物硬化,但藉由含有後述的[D]自由基聚合起始劑可更有效地使其硬化。 [C] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. The curable resin composition further contains a [C] polymerizable compound, which can further improve the adhesion of the cured film when forming a negative pattern, and can improve the thermal stability of the pattern shape when forming a positive pattern. The [C] polymerizable compound may be hardened by heating, but can be more effectively hardened by containing a [D] radical polymerization initiator described later.

含有乙烯性不飽和鍵的基例如可列舉:乙烯基、烯丙基、(甲基)丙烯醯基、苯乙烯基等。 Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, and a styryl group.

[C]聚合性化合物所具有的乙烯性不飽和鍵的個數可為1個也可為多個。就提高硬化膜的黏附性的觀點而言,乙烯性不飽和鍵的個數優選為2以上,更優選為3以上,就提高保存穩定性的觀點而言,乙烯性不飽和鍵的個數優選為10以下,更優選為6以下。 [C] The number of ethylenically unsaturated bonds in the polymerizable compound may be one or plural. From the viewpoint of improving the adhesion of the cured film, the number of ethylenically unsaturated bonds is preferably 2 or more, and more preferably 3 or more. From the viewpoint of improving storage stability, the number of ethylenically unsaturated bonds is preferred. It is 10 or less, and more preferably 6 or less.

[C]聚合性化合物例如可列舉:單官能丙烯酸酯、多官能丙烯酸酯、其他聚合性化合物等。 [C] Examples of the polymerizable compound include monofunctional acrylate, polyfunctional acrylate, and other polymerizable compounds.

單官能丙烯酸酯例如可列舉:ω-羧基聚己內酯單(甲基)丙烯酸酯、乙二醇單(甲基)丙烯酸酯等。 Examples of the monofunctional acrylate include ω-carboxy polycaprolactone mono (meth) acrylate, ethylene glycol mono (meth) acrylate, and the like.

多官能丙烯酸酯例如可列舉:乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、雙苯氧基乙 醇芴二(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、甲基丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基乙基)磷酸酯、環氧乙烷改性二季戊四醇六丙烯酸酯、丁二酸改性季戊四醇三丙烯酸酯、丁二酸改性二季戊四醇五丙烯酸酯、使具有直鏈伸烷基及脂環式結構且具有2個以上的異氰酸酯基的化合物與分子內具有1個以上的羥基且具有3個~5個(甲基)丙烯醯氧基的化合物進行反應而得的(甲基)丙烯酸胺基甲酸酯等多官能(甲基)丙烯酸酯化合物等。 Examples of the polyfunctional acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and Ethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxy Jiyi Alcohol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acrylic acid oxypropyl methacrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol seven (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (2- (meth) acryloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid Modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, and A polyfunctional (meth) acrylate compound such as a (meth) acrylic acid urethane obtained by reacting a compound having 3 to 5 (meth) acrylic fluorenyloxy groups.

其他聚合性化合物例如可列舉:(甲基)丙烯酸2-(2'-乙烯氧基乙氧基)乙酯等。 Examples of other polymerizable compounds include 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate.

[C]聚合性化合物的市售品例如可列舉:亞羅尼斯(Aronix)M-400、亞羅尼斯(Aronix)M-402、亞羅尼斯(Aronix)M-405、亞羅尼斯(Aronix)M-450、亞羅尼斯(Aronix)M-520、亞羅尼斯(Aronix)M-1310、亞羅尼斯(Aronix)M-1600、亞羅尼斯(Aronix)M-1960、亞羅尼斯(Aronix)M-7100、亞羅尼斯(Aronix)M-8030、亞羅尼斯(Aronix)M-8060、亞羅尼斯(Aronix)M-8100、亞羅尼斯(Aronix)M-8530、亞羅尼斯(Aronix)M-8560、亞羅尼斯(Aronix)M-9050、亞羅尼斯(Aronix)TO-756、亞羅尼斯(Aronix)TO-1450、亞羅尼斯(Aronix)TO-1382 (以上,東亞合成公司);卡亞拉德(KAYARAD)DPHA、卡亞拉德(KAYARAD)DPCA-20、卡亞拉德(KAYARAD)DPCA-30、卡亞拉德(KAYARAD)DPCA-60、卡亞拉德(KAYARAD)DPCA-120、卡亞拉德(KAYARAD)MAX-3510(以上,日本化藥公司);比斯克特(Viscoat)295、比斯克特(Viscoat)300、比斯克特(Viscoat)360、比斯克特(Viscoat)802、比斯克特(Viscoat)GPT、比斯克特(Viscoat)3PA、比斯克特(Viscoat)400(以上,大阪有機化學工業公司);作為丙烯酸胺基甲酸酯系化合物的新邊界R-1150(New Frontier R-1150)(第一工業製藥公司);卡亞拉德(KAYARAD)DPHA-40H、卡亞拉德(KAYARAD)DPEA-12、HUX-5000(以上,日本化藥公司);UN-9000H(根上工業公司);亞羅尼斯(Aronix)M-5300、亞羅尼斯(Aronix)M-5600、亞羅尼斯(Aronix)M-5700、亞羅尼斯(Aronix)M-210、亞羅尼斯(Aronix)M-220、亞羅尼斯(Aronix)M-240、亞羅尼斯(Aronix)M-270、亞羅尼斯(Aronix)M-6200、亞羅尼斯(Aronix)M-305、亞羅尼斯(Aronix)M-309、亞羅尼斯(Aronix)M-310、亞羅尼斯(Aronix)M-315(以上,東亞合成公司);卡亞拉德(KAYARAD)HDDA、卡亞拉德(KAYARAD)HX-220、卡亞拉德(KAYARAD)HX-620、卡亞拉德(KAYARAD) R-526、卡亞拉德(KAYARAD)R-167、卡亞拉德(KAYARAD)R-604、卡亞拉德(KAYARAD)R-684、卡亞拉德(KAYARAD)R-551、卡亞拉德(KAYARAD)R-712、UX-2201、UX-2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、MU-2100、MU-4001(以上,日本化藥公司);亞特樹脂(Art Resin)UN-9000PEP、亞特樹脂(Art Resin)UN-9200A、亞特樹脂(Art Resin)UN-7600、亞特樹脂(Art Resin)UN-333、亞特樹脂(Art Resin)UN-1003、亞特樹脂(Art Resin)UN-1255、亞特樹脂(Art Resin)UN-6060PTM、亞特樹脂(Art Resin)UN-6060P、亞特樹脂(Art Resin)SH-500B(以上,根上工業公司);比斯克特(Viscoat)260、比斯克特(Viscoat)312、比斯克特(Viscoat)335HP(以上,大阪有機化學工業公司)等。 [C] Examples of commercially available polymerizable compounds include: Aronix M-400, Aronix M-402, Aronix M-405, and Aronix M-450, Aronix M-520, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-756, Aronix TO-1450, Aronix TO-1382 (Above, East Asia Synthesis); KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above, Nippon Kayakusho); Viscoat 295, Viscoat 300, Biscott ( Viscoat 360, Viscoat 802, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, Osaka Organic Chemical Industry Co., Ltd.); as acrylic amino New frontier R-1150 (First Industrial Pharmaceutical Company) of ester compounds; KAYARAD DPHA-40H, KAYARAD DPEA-12, HUX-5000 (Above, Nippon Kayakusho); UN-9000H (Kanekami Corporation); Aronix M-5300, Aronix M-5600, Aronix M-5700, Yarrow Aronix M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Yarrow Aronix M-305, Aronix M-30 9. Aronix M-310, Aronix M-315 (above, East Asia Synthesis); KAYARAD HDDA, KAYARAD HX-220, card Kayarad HX-620, Kayarad R-526, Kayarad R-167, Kayarad R-604, Kayarad R-684, Kayarad R-551, Kaya KAYARAD R-712, UX-22201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU -4001 (above, Nippon Kayakusho); Art Resin UN-9000PEP, Art Resin UN-9200A, Art Resin UN-7600, Art Resin ) UN-333, Art Resin UN-1003, Art Resin UN-1255, Art Resin UN-6060PTM, Art Resin UN-6060P, Asia Special resin (Art Resin) SH-500B (above, Genjo Industrial Co.); Viscoat 260, Viscoat 312, Viscoat 335HP (above, Osaka Organic Chemical Industry Co., Ltd.) .

[C]聚合性化合物優選為多官能丙烯酸酯,更優選為二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、丁二酸改性季戊四醇三丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三季戊四醇七丙烯酸酯、三季戊四醇八丙烯酸酯、丁二酸改性二季戊四醇五丙烯酸酯。 [C] The polymerizable compound is preferably a polyfunctional acrylate, and more preferably dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, trimethylolpropane triacrylate, and tripentaerythritol seven Acrylate, tripentaerythritol octaacrylate, succinic acid modified dipentaerythritol pentaacrylate.

相對於[A]聚合物100質量份,[C]聚合性化合物的含有量優選為20質量份以上且200質量份以下,更優選為40質量份以上且160質量份以下。藉由將[C]聚合性化合物的含有量設為所述範圍,所述硬化性樹脂組成物可進一步提高所述形成負型圖案時的硬化膜的黏附性及形成正型圖案時的圖案形狀的熱穩定性。 The content of the [C] polymerizable compound with respect to 100 parts by mass of the [A] polymer is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 160 parts by mass or less. By setting the content of the [C] polymerizable compound to the range, the curable resin composition can further improve the adhesion of the cured film when the negative pattern is formed and the pattern shape when the positive pattern is formed. Thermal stability.

<[D]自由基聚合起始劑> <[D] radical polymerization initiator>

[D]自由基聚合起始劑是生成如下活性種的成分,所述活性種可引發具備聚合性的化合物的自由基聚合。所述硬化性樹脂組成物藉由含有[D]自由基聚合起始劑,可進一步提高硬化膜的黏附性。[D]自由基聚合起始劑例如可列舉:藉由加熱而分解並產生自由基的[D1]感熱性自由基聚合起始劑、藉由放射線的照射而產生自由基的[D2]感放射線性自由基聚合起始劑等。所述硬化性樹脂組成物中的[D]自由基聚合起始劑的含有形態可為後述般的低分子化合物的形態、作為[A]聚合物等的一部分而被組入的形態、所述兩者的形態。可含有1種或2種以上[D]自由基聚合起始劑。 [D] The radical polymerization initiator is a component that generates active species that can initiate radical polymerization of a polymerizable compound. When the curable resin composition contains a [D] radical polymerization initiator, the adhesion of the cured film can be further improved. Examples of the [D] radical polymerization initiator include: [D1] thermosensitive radical polymerization initiator which is decomposed by heating to generate radicals, and [D2] radiation which generates radicals by irradiation of radiation. Radical polymerization initiators, etc. The contained form of the [D] radical polymerization initiator in the curable resin composition may be a form of a low-molecular compound as described below, a form incorporated as part of the [A] polymer, and the like Both forms. It may contain 1 type or 2 or more types of [D] radical polymerization initiators.

[[D1]感熱性自由基聚合起始劑] [[D1] Thermosensitive radical polymerization initiator]

[D1]感熱性自由基聚合起始劑是藉由加熱而分解並產生自由基的化合物。所述硬化性樹脂組成物若含有[D1]感熱性自由基聚合起始劑,則可作為熱硬化性樹脂組成物發揮功能。 [D1] The thermosensitive radical polymerization initiator is a compound that is decomposed by heating and generates radicals. When the said curable resin composition contains a [D1] thermosensitive radical polymerization initiator, it can function as a thermosetting resin composition.

[D1]感熱性自由基聚合起始劑例如可列舉:偶氮雙異丁腈(azobisisobutyronitrile,AIBN)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮雙(2-環丙基丙腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、二甲基2,2'-偶氮雙異丁酸酯等偶氮系自由基起始劑;苯甲醯基過氧化物、叔丁基氫過氧化物、枯烯氫過氧化物等過氧化物系自由基起始劑等。 [D1] Thermosensitive radical polymerization initiators include, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylpentane) Nitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'- Azo radical initiators such as azobisisobutyrate; peroxide radical initiators such as benzamyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide.

[[D2]感放射線性自由基聚合起始劑] [[D2] Radiation-sensitive Radical Polymerization Initiator]

[D2]感放射線性自由基聚合起始劑是藉由放射線的照射而產 生自由基的化合物。所述硬化性樹脂組成物若含有[D2]感放射線性自由基聚合起始劑,則可作為放射線硬化性樹脂組成物發揮功能,且[A]聚合物、[C]聚合性化合物等利用產生的自由基進行聚合,由此發揮負型感放射線性特性。所述硬化性樹脂組成物藉由含有[D2]感放射線性自由基聚合起始劑,可進一步提高放射線感度。 [D2] Radiation-sensitive radical polymerization initiator is produced by irradiation of radiation Free radical generating compounds. If the curable resin composition contains a [D2] radiation-sensitive radical polymerization initiator, it can function as a radiation curable resin composition, and the [A] polymer, [C] polymerizable compound, etc. Polymerizes the free radicals, thereby exerting negative radiation-sensitive properties. By including the [D2] radiation-sensitive radical polymerization initiator in the curable resin composition, the radiation sensitivity can be further improved.

[D2]感放射線性自由基聚合起始劑例如可列舉O-醯基肟化合物、苯乙酮化合物、聯咪唑化合物、硫雜蒽酮化合物等。 [D2] The radiation-sensitive radical polymerization initiator includes, for example, an O-fluorenyl oxime compound, an acetophenone compound, a biimidazole compound, and a thia anthrone compound.

O-醯基肟化合物例如可列舉:1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、1,2-辛二酮1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)、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、乙酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基苯甲醯基)-9.H.-哢唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-4-四氫吡喃基苯甲醯基)-9.H.-哢唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-5-四氫呋喃基苯甲醯基)-9.H.-哢唑-3-基]-1-(O-乙醯基肟)、乙酮-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]-1-(O-乙醯基肟)等。 Examples of the O-fluorenyl oxime compound include 1- [4- (phenylthio) -2- (O-benzylidene oxime)], 1,2-octanedione 1- [4- (phenylthio ) -2- (O-benzylideneoxime)], ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1 -(O-ethylamidoxime), 1- [9-ethyl-6-benzylidene-9.H.-oxazol-3-yl] -octane-1-oneoxime-O-acetic acid Ester, 1- [9-ethyl-6- (2-methylbenzyl) -9.H.-oxazol-3-yl] -ethane-1-one oxime-O-benzoate , 1- [9-n-butyl-6- (2-ethylbenzylidene) -9.H.-oxazol-3-yl] -ethane-1-oneoxime-O-benzoate Ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzyl) -9.H.-oxazol-3-yl] -1- (O-acetamidine Oxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzyl) -9.H.-oxazol-3-yl] -1 -(O-ethylamidoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzyl) -9.H.-oxazol-3-yl ] -1- (O-acetylamoxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxa Cyclopentyl) methoxybenzylidene} -9.H.-oxazol-3-yl] -1- (O-acetamidooxime) and the like.

苯乙酮化合物例如可列舉:α-胺基酮化合物、α-羥基酮化合物等。 Examples of the acetophenone compound include an α -amino ketone compound and an α -hydroxy ketone compound.

α-胺基酮化合物例如可列舉:2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-二甲基胺基-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。 Examples of the α -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one and 2-dimethylamino- 2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) 2-morpholinylpropan-1-one and the like.

α-羥基酮化合物例如可列舉:1-苯基-2-羥基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯基酮。 Examples of the α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone.

聯咪唑化合物例如可列舉:2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑等,優選為2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc., preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

硫雜蒽酮化合物例如可列舉:硫雜蒽酮、2,4-二乙基硫雜蒽酮、2-異丙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮、2-氯硫雜蒽酮等。 Examples of the xanthone compound include xanthone, 2,4-diethylxanthone, 2-isopropylxanthone, 2,4-diisopropylxanthone, 2 -Chlorothanthone and the like.

其中,優選為O-醯基肟化合物、苯乙酮化合物、硫雜蒽酮化合物,更優選為O-醯基肟化合物、α-胺基酮化合物、硫雜蒽酮化合物,進而優選為乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)、2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮、2,4-二乙基硫雜蒽酮。 Among these, an O-fluorenyl oxime compound, an acetophenone compound, and a thia anthrone compound are preferable, an O-fluorenyl oxime compound, an α -amino ketone compound, and a thia anthrone compound are more preferable, and an ethyl ketone is more preferable -1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one, 2,4-diethylthiaxanthone.

相對於[A]聚合物100質量份,[D]自由基聚合起始劑的含有量優選為1質量份以上且40質量份以下,更優選為5質量份以上且30質量份以下。藉由將[D]自由基聚合起始劑的含有量設為 所述範圍,所述硬化性樹脂組成物可進一步提高硬化膜的黏附性,另外在為放射線硬化性樹脂組成物的情形時,可進而提高放射線感度。 The content of the [D] radical polymerization initiator relative to 100 parts by mass of the [A] polymer is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less. By setting the content of the [D] radical polymerization initiator to Within the above range, the curable resin composition can further improve the adhesion of the cured film, and in the case of a radiation curable resin composition, can further improve the radiation sensitivity.

<[E]酸產生劑> <[E] acid generator>

[E]酸產生劑是產生酸的化合物。所述產生的酸例如可列舉羧酸、磺酸等。所述硬化性樹脂組成物藉由含有[E]酸產生劑,可提高硬化膜的耐熱性、硬度等特性。[E]酸產生劑例如可列舉:藉由加熱而產生酸的[E1]感熱性酸產生劑、藉由放射線的照射而產生酸的[E2]感放射線性酸產生劑等。所述硬化性樹脂組成物中的[E]酸產生劑的含有形態可為後述般的低分子化合物的形態、作為[A]聚合物等的一部分而被組入的形態、所述兩者的形態。所述硬化性樹脂組成物可含有1種或2種以上的[E]酸產生劑。 [E] An acid generator is a compound that generates an acid. Examples of the generated acid include carboxylic acid and sulfonic acid. By including the [E] acid generator in the curable resin composition, properties such as heat resistance and hardness of the cured film can be improved. Examples of the [E] acid generator include a [E1] thermosensitive acid generator that generates an acid by heating, and a [E2] radiation-sensitive acid generator that generates an acid by irradiation of radiation. The content of the [E] acid generator in the curable resin composition may be a form of a low-molecular compound as described below, a form incorporated as a part of the [A] polymer, or the like. form. The said curable resin composition may contain 1 type or 2 or more types of [E] acid generator.

[[E1]感熱性酸產生劑] [[E1] Thermosensitive acid generator]

[E1]感熱性酸產生劑是藉由加熱而產生酸的化合物。所述硬化性樹脂組成物若含有[E1]感熱性酸產生劑,則可作為熱硬化性樹脂組成物發揮功能。 [E1] The thermosensitive acid generator is a compound that generates an acid by heating. When the said curable resin composition contains a [E1] thermosensitive acid generator, it can function as a thermosetting resin composition.

[E1]感熱性酸產生劑例如可列舉:鋶鹽、苯並噻唑鎓鹽、銨鹽、鏻鹽等鎓鹽等。[E1]感熱性酸產生劑化合物的具體例可列舉與作為日本專利特開2010-134442號公報中所記載的[E]成分而例示的化合物同樣的化合物。 [E1] Examples of the thermosensitive acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. [E1] Specific examples of the thermosensitive acid generator compound include the same compounds as those exemplified as the [E] component described in Japanese Patent Laid-Open No. 2010-134442.

[[E2]感放射線性酸產生劑] [[E2] Radioactive acid generator]

[E2]感放射線性酸產生劑是藉由放射線的照射而產生酸的化 合物。所述硬化性樹脂組成物若含有[E2]感放射線性酸產生劑,則可作為放射線硬化性樹脂組成物發揮功能。所述硬化性樹脂組成物藉由含有[E2]感放射線性酸產生劑,可進一步提高放射線感度。 [E2] A radiation-sensitive acid generator is an acid that is generated by radiation. 组合。 The compound. When the said curable resin composition contains a [E2] radiation-sensitive acid generator, it can function as a radiation-curable resin composition. By containing the [E2] radiation-sensitive acid generator, the curable resin composition can further improve radiation sensitivity.

[E2]酸產生劑例如可列舉:醌二疊氮化合物、肟磺酸酯化合物、鎓鹽、磺醯亞胺化合物、含鹵素的化合物、重氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物等。 [E2] Examples of the acid generator include quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfonylimine compounds, halogen-containing compounds, diazomethane compounds, sulfonium compounds, sulfonate compounds, and carboxylates. Ester compounds, etc.

醌二疊氮化合物藉由放射線的照射而產生羧酸。所述硬化性樹脂組成物藉由含有醌二疊氮化合物作為[E2]酸產生劑,則產生的羧酸提高放射線照射部分在鹼性顯影液中的溶解性,由此可發揮正型感放射線特性。 A quinonediazide compound generates a carboxylic acid by irradiation of radiation. When the curable resin composition contains a quinonediazide compound as an [E2] acid generator, the generated carboxylic acid improves the solubility of the radiation irradiated portion in the alkaline developer, thereby exhibiting positive radiation sensitivity. characteristic.

醌二疊氮化合物例如可使用酚性化合物或醇性化合物(以下也稱為“母核”)與1,2-萘醌二疊氮磺醯鹵的縮合物。 As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used.

母核例如可列舉:三羥基二苯甲酮、四羥基二苯甲酮、五羥基二苯甲酮、六羥基二苯甲酮、(多羥基苯基)烷烴、其他母核等。 Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

三羥基二苯甲酮例如可列舉:2,3,4-三羥基二苯甲酮、2,4,6-三羥基二苯甲酮等。 Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

四羥基二苯甲酮例如可列舉:2,2',4,4'-四羥基二苯甲酮、2,3,4,3'-四羥基二苯甲酮、2,3,4,4'-四羥基二苯甲酮、2,3,4,2'-四羥基-4'-甲基二苯甲酮、2,3,4,4'-四羥基-3'-甲氧基二苯甲酮等。 Examples of the tetrahydroxybenzophenone include: 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4 '-Tetrahydroxybenzophenone, 2,3,4,2'-Tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-Tetrahydroxy-3'-methoxydi Benzophenone and so on.

五羥基二苯甲酮例如可列舉:2,3,4,2',6'-五羥基二苯甲酮等。 Examples of the pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like.

六羥基二苯甲酮例如可列舉:2,4,6,3',4',5'-六羥基二苯甲酮、3,4,5,3',4',5'-六羥基二苯甲酮等。 Examples of hexahydroxybenzophenone include: 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxydione Benzophenone and so on.

(多羥基苯基)烷烴例如可列舉:雙(2,4-二羥基苯基)甲烷、雙(對羥基苯基)甲烷、三(對羥基苯基)甲烷、1,1,1-三(對羥基苯基)乙烷、雙(2,3,4-三羥基苯基)甲烷、2,2-雙(2,3,4-三羥基苯基)丙烷、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚、雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷、3,3,3',3'-四甲基-1,1'-螺二茚-5,6,7,5',6',7'-己醇、2,2,4-三甲基-7,2',4'-三羥基黃烷等。 Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris ( P-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] Phenyl] ethylene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1, 1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.

其他母核例如可列舉:2-甲基-2-(2,4-二羥基苯基)-4-(4-羥基苯基)-7-羥基色滿、1-[1-{3-(1-[4-羥基苯基]-1-甲基乙基)-4,6-二羥基苯基}-1-甲基乙基]-3-〔1-{3-(1-[4-羥基苯基]-1-甲基乙基)-4,6-二羥基苯基}-1-甲基乙基]苯、4,6-雙{1-(4-羥基苯基)-1-甲基乙基}-1,3-二羥基苯等。 Examples of other mother cores include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- ( 1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4- Hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1- Methylethyl} -1,3-dihydroxybenzene and the like.

所述母核中優選為2,3,4,4'-四羥基二苯甲酮、1,1,1-三(對羥基苯基)乙烷、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚。 The mother core is preferably 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol.

1,2-萘醌二疊氮磺醯鹵優選為1,2-萘醌二疊氮磺醯氯。1,2-萘醌二疊氮磺醯氯例如可列舉:1,2-萘醌二疊氮-4-磺醯氯、1,2-萘醌二疊氮-5-磺醯氯等。其中優選為1,2-萘醌二疊氮-5-磺醯氯。 The 1,2-naphthoquinonediazidesulfonium halide is preferably 1,2-naphthoquinonediazidesulfonyl chloride. Examples of the 1,2-naphthoquinonediazidesulfonyl chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferred.

醌二疊氮化合物的合成可藉由公知的縮合反應進行。在所述縮合反應中,相對於酚性化合物或醇性化合物中的OH基數, 可使用相當於優選為30莫耳%~85莫耳%、更優選為50莫耳%~70莫耳%的1,2-萘醌二疊氮磺醯鹵。 The synthesis of the quinonediazide compound can be performed by a known condensation reaction. In the condensation reaction, with respect to the number of OH groups in the phenolic compound or the alcoholic compound, The 1,2-naphthoquinonediazidesulfonium halide equivalent to preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% can be used.

另外,醌二疊氮化合物也可適宜地使用將剛才所例示的母核的酯鍵變更為醯胺鍵而成的1,2-萘醌二疊氮磺醯胺類,例如2,3,4-三胺基二苯甲酮-1,2-萘醌二疊氮-4-磺醯胺等。 In addition, as the quinonediazide compound, 1,2-naphthoquinonediazidesulfonamides obtained by changing the ester bond of the mother nucleus just exemplified to the amidine bond can be suitably used. For example, 2,3,4 -Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like.

在[E2]酸產生劑為醌二疊氮化合物以外的、例如肟磺酸酯化合物、鎓鹽、磺醯亞胺化合物、含鹵素的化合物、重氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物等的情形時,關於所述硬化性樹脂組成物,藉由產生的酸的作用而後述的[F]聚合物等進行反應並硬化,由此通常可發揮負型感放射線性特性。 The [E2] acid generator is other than a quinonediazide compound, for example, an oxime sulfonate compound, an onium salt, a sulfonylimide compound, a halogen-containing compound, a diazomethane compound, a sulfonium compound, a sulfonate compound, In the case of a carboxylic acid ester compound and the like, the above-mentioned curable resin composition can react with and harden the [F] polymer and the like described later by the action of an acid generated, and thus can generally exhibit negative radiation-sensitive properties. .

肟磺酸酯化合物例如可列舉:(5-丙基磺醯基氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-辛基磺醯基氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(樟腦磺醯基氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-對甲苯磺醯基氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-辛基磺醯基氧基亞胺基)-(4-甲氧基苯基)乙腈等。 Examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, and (5-octylsulfonyl) Oxyoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2 -Methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyl) Oxyimino)-(4-methoxyphenyl) acetonitrile and the like.

鎓鹽化合物例如可列舉:錪鹽、鋶鹽、鏻鹽、重氮鎓鹽、吡啶鎓鹽。優選的鎓鹽的具體例可列舉:二苯基錪三氟甲磺酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽、二苯基錪六氟磷酸鹽、二苯基錪四氟硼酸鹽、三苯基鋶三氟甲磺酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、4-叔丁基苯基.二苯基鋶三氟甲磺酸鹽、4-叔丁基苯基.二苯基鋶對甲苯磺酸鹽、4,7-二-正丁 氧基萘基四氫噻吩鎓三氟甲磺酸鹽、4-(苯硫基)苯基二苯基鋶三(五氟乙基)三氟磷酸鹽、4-(苯硫基)苯基二苯基鏻六氟磷酸鹽。 Examples of onium salt compounds include sulfonium salts, sulfonium salts, sulfonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include diphenylsulfonium triflate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, diphenylsulfonium hexafluorophosphate, Diphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl. Diphenylsulfonium triflate, 4-tert-butylphenyl. Diphenylphosphonium p-toluenesulfonate, 4,7-di-n-butyl Oxynaphthyl tetrahydrothienium trifluoromethanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldi Phenylphosphonium hexafluorophosphate.

N-磺醯基氧基醯亞胺化合物例如可列舉:N-(三氟甲基磺醯基氧基)琥珀醯亞胺、N-(三氟甲基磺醯基氧基)鄰苯二甲醯亞胺、N-(三氟甲基磺醯基氧基)二苯基順丁烯二醯亞胺、N-(三氟甲基磺醯基氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯基氧基)萘基醯亞胺。 Examples of the N-sulfonyloxyfluorenimine compound include N- (trifluoromethylsulfonyloxy) succinimine, N- (trifluoromethylsulfonyloxy) phthalimide Fluorenimine, N- (trifluoromethylsulfonyloxy) diphenylcis-butenedifluorenimine, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxyfluorenimine, N- (trifluoromethylsulfonyloxy) naphthylfluorenimine.

含鹵素的化合物例如可列舉:含鹵代烷基的烴化合物、含鹵代烷基的雜環式化合物。優選的含鹵素的化合物的具體例可列舉:1,10-二溴-正癸烷、1,1-雙(4-氯苯基)-2,2,2-三氯乙烷、苯基-雙(三氯甲基)-均三嗪、4-甲氧基苯基-雙(三氯甲基)-均三嗪、苯乙烯基-雙(三氯甲基)-均三嗪、萘基-雙(三氯甲基)-均三嗪等均三嗪衍生物。 Examples of the halogen-containing compound include a halogenated alkyl group-containing hydrocarbon compound and a halogenated alkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl- Bis (trichloromethyl) -mesytriazine, 4-methoxyphenyl-bis (trichloromethyl) -mesytriazine, styryl-bis (trichloromethyl) -mesytriazine, naphthyl -Bis (trichloromethyl) -mesytriazine derivatives and the like.

重氮甲烷化合物例如可列舉:雙(三氟甲基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(苯基磺醯基)重氮甲烷。 Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

碸化合物例如可列舉:β-酮碸化合物、β-磺醯基碸化合物及這些化合物的α-二偶氮化合物。優選的碸化合物的具體例可列舉:4-三苯甲醯甲基碸、均三甲苯基苯甲醯甲基碸、雙(苯甲醯甲基磺醯基)甲烷等。 Examples of the fluorene compound include a β -ketofluorene compound, a β -sulfonylfluorene compound, and an α -diazo compound of these compounds. Specific examples of the preferred sulfonium compound include 4-tribenzylfluorenylmethylfluorene, mesitylbenzylfluorenylmethylfluorene, bis (benzylfluorenylmethylsulfonyl) methane, and the like.

磺酸酯化合物例如可列舉:烷基磺酸酯類、鹵代烷基磺酸酯類、芳基磺酸酯類、亞胺基磺酸酯類。優選的磺酸酯化合物的具體例可列舉:安息香甲苯磺酸酯、鄰苯三酚三(三氟甲磺酸 酯)、鄰硝基苄基三氟甲磺酸酯、鄰硝基苄基對甲苯磺酸酯。 Examples of the sulfonate compound include alkylsulfonates, haloalkylsulfonates, arylsulfonates, and iminosulfonates. Specific examples of preferred sulfonate compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonic acid) Ester), o-nitrobenzyl triflate, o-nitrobenzyl p-toluenesulfonate.

羧酸酯化合物例如可列舉:羧酸鄰硝基苄基酯等。 Examples of the carboxylic acid ester compound include o-nitrobenzyl carboxylic acid ester and the like.

相對於[A]聚合物100質量份,[E]酸產生劑的含有量優選為5質量份以上且100質量份以下,更優選為10質量份以上且50質量份以下。藉由將[E]酸產生劑的含有量設為所述範圍,所述硬化性樹脂組成物可進一步提高硬化膜的黏附性,另外在為放射線硬化性樹脂組成物的情形時,可進而提高放射線感度。 The content of the [E] acid generator relative to 100 parts by mass of the [A] polymer is preferably 5 parts by mass or more and 100 parts by mass, and more preferably 10 parts by mass or more and 50 parts by mass or less. By setting the content of the [E] acid generator within the above range, the curable resin composition can further improve the adhesion of the cured film, and can further improve the radiation curable resin composition. Radiosensitivity.

<[F]聚合物> <[F] Polymer>

[F]聚合物是如下的聚合物:使含有選自由不飽和羧酸及不飽和羧酸酐組成的群組中的至少1種(以下也稱為“(F1)化合物”)、與含環氧基的不飽和化合物(以下也稱為“(F2)化合物”)的單體進行共聚而成。所述硬化性樹脂組成物藉由含有[F]聚合物,可進一步提高硬化膜的黏附性,且可提高耐溶劑性及硬度。也可藉由加熱使[F]聚合物硬化,但藉由含有[D]自由基聚合起始劑及/或[E]酸產生劑,可更有效地使其硬化。 [F] The polymer is a polymer containing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter also referred to as "(F1) compound"), and an epoxy-containing polymer A monomer of an unsaturated compound (hereinafter also referred to as a "(F2) compound") is copolymerized. By containing the [F] polymer in the curable resin composition, the adhesiveness of the cured film can be further improved, and the solvent resistance and hardness can be improved. The [F] polymer can be hardened by heating, but it can be more effectively hardened by containing a [D] radical polymerization initiator and / or an [E] acid generator.

在[F]聚合物的合成時,可使(F1)化合物及(F2)化合物以外的不飽和化合物(以下也稱為“(F3)化合物”)共聚。這些化合物可使用1種或2種以上。 In the synthesis of the [F] polymer, an unsaturated compound (hereinafter also referred to as a "(F3) compound") other than the (F1) compound and the (F2) compound can be copolymerized. These compounds can be used alone or in combination of two or more.

以下對各化合物進行說明。 Each compound will be described below.

[(F1)化合物] [(F1) Compound]

(F1)化合物是選自由不飽和羧酸及不飽和羧酸酐組成的群組中的至少1種。(F1)化合物可列舉:不飽和單羧酸、不飽和二 羧酸、不飽和二羧酸的酐、多元羧酸的單[(甲基)丙烯醯基氧基烷基]酯、在兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯、具有羧基的不飽和多環式化合物及其酐等。這些化合物可列舉與作為提供[A]聚合物的結構單元(II)的單體而例示的化合物同樣的化合物等。 The (F1) compound is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. (F1) Compounds include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids Carboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acrylfluorenyloxyalkyl] esters of polycarboxylic acids, mono (meth) acrylates of polymers having carboxyl and hydroxyl groups at both ends, Unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof. These compounds include the same compounds as those exemplified as the monomers that provide the structural unit (II) of the [A] polymer, and the like.

其中,就共聚反應性及獲得容易性、以及[F]聚合物對鹼性水溶液的溶解性的觀點而言,優選為單羧酸、二羧酸的酐,更優選為丙烯酸、甲基丙烯酸、順丁烯二酸酐,進而優選為甲基丙烯酸。 Among these, from the viewpoints of copolymerization reactivity and availability, and the solubility of the [F] polymer in an alkaline aqueous solution, preferred are monocarboxylic and dicarboxylic anhydrides, and more preferred are acrylic acid, methacrylic acid, Maleic anhydride is more preferably methacrylic acid.

源自所述(F1)化合物的結構單元的含有比例以相對於[F]聚合物的合成中使用的全部單體的投入比計,優選為1質量%~40質量%,更優選為2質量%~30質量%,進而優選為3質量%~20質量%。藉由將所述含有比例設為所述範圍,可使[F]聚合物對鹼性水溶液的溶解性最適化,可進一步提高所述硬化性樹脂組成物的顯影性。 The content ratio of the structural unit derived from the (F1) compound is preferably 1% to 40% by mass, and more preferably 2% by mass based on the input ratio of all monomers used in the synthesis of the [F] polymer. % To 30% by mass, and more preferably 3 to 20% by mass. By setting the content ratio to the range, the solubility of the [F] polymer in the alkaline aqueous solution can be optimized, and the developability of the curable resin composition can be further improved.

[(F2)化合物] [(F2) compound]

(F2)化合物是含環氧基的不飽和化合物。(F2)化合物具有自由基聚合性且通常既具有環氧基也具有乙烯性不飽和鍵。所述環氧基可列舉:氧雜環丙基(1,2-環氧結構)、氧雜環丁基(1,3-環氧結構)。 The (F2) compound is an epoxy-containing unsaturated compound. The (F2) compound has radical polymerizability and usually has both an epoxy group and an ethylenically unsaturated bond. Examples of the epoxy group include an oxetanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

具有氧雜環丙基的不飽和化合物例如可列舉:丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、 α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧基丁酯、甲基丙烯酸-3,4-環氧基丁酯、丙烯酸-6,7-環氧基庚酯、甲基丙烯酸-6,7-環氧基庚酯、α-乙基丙烯酸-6,7-環氧基庚酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、甲基丙烯酸3,4-環氧基環己酯等。 Examples of the unsaturated compound having an oxetanyl group include glycidyl acrylate, glycidyl methacrylate, α -ethyl acrylate, α -n-propyl acrylate, and α -n-butyl acrylate. Glycidyl acrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7 methacrylate -Epoxyheptyl, α -ethylhexyl-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like.

具有氧雜環丁基的不飽和化合物例如可列舉:3-(丙烯醯基氧基甲基)氧雜環丁烷、3-(丙烯醯基氧基甲基)-2-甲基氧雜環丁烷、3-(丙烯醯基氧基甲基)-3-乙基氧雜環丁烷、3-(丙烯醯基氧基甲基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯基氧基甲基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯基氧基甲基)-2-苯基氧雜環丁烷、3-(丙烯醯基氧基甲基)-2,2-二氟氧雜環丁烷、3-(丙烯醯基氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯基氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-丙烯醯基氧基乙基)氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2-乙基氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-3-乙基氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2-苯基氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-丙烯醯基氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的丙烯酸酯;3-(甲基丙烯醯基氧基甲基)氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2-甲基氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2-三氟甲基氧雜環丁烷、 3-(甲基丙烯醯基氧基甲基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2-苯基氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2,2-二氟氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯基氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2-乙基氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-3-乙基氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2-苯基氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-甲基丙烯醯基氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的甲基丙烯酸酯等。 Examples of the unsaturated compound having an oxetanyl group include 3- (propenyloxymethyl) oxetane and 3- (propenyloxymethyl) -2-methyloxane Butane, 3- (propenyloxymethyl) -3-ethyloxetane, 3- (propenyloxymethyl) -2-trifluoromethyloxetane, 3 -(Propenyloxymethyl) -2-pentafluoroethyloxetane, 3- (propenyloxymethyl) -2-phenyloxetane, 3- (propenefluorene Methoxymethyl) -2,2-difluorooxetane, 3- (propenyloxymethyl) -2,2,4-trifluorooxetane, 3- (propenefluorene) Ethoxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-propenyloxyethyl) oxetane, 3- (2-propenylfluorenyl) (Oxyethyl) -2-ethyloxetane, 3- (2-propenyloxyethyl) -3-ethyloxetane, 3- (2-propenyloxy) (Ethyl) -2-trifluoromethyloxetane, 3- (2-propenyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-propenyloxetyl (Oxyethyl) -2-phenyloxetane, 3- (2-propenyloxyethyl) -2,2-difluorooxetane, 3- (2-propenyloxetyl Oxyethyl Acryl) -2,2,4-trifluorooxetane, 3- (2-propenyloxyethyl) -2,2,4,4-tetrafluorooxetane, etc. ; 3- (methacrylfluorenyloxymethyl) oxetane, 3- (methacrylfluorenyloxymethyl) -2-methyloxetane, 3- (methacryl Fluorenyloxymethyl) -3-ethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-trifluoromethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-phenyloxetane, 3- (methacrylfluorenyloxymethyl) -2,2-difluorooxetane, 3- (methacrylfluorenyloxymethyl) -2,2,4-trifluorooxe Cyclobutane, 3- (methacrylfluorenyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacrylfluorenyloxyethyl) oxy Heterocyclobutane, 3- (2-methylpropenyloxyethyl) -2-ethyloxetane, 3- (2-methpropenyloxyethyl) -3-ethyl Oxetane, 3- (2-methacrylfluorenyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacrylfluorenyloxyethyl) 2-pentafluoroethyloxetane, 3- (2-methacrylfluorenyloxyethyl) -2-phenyloxetane, 3- (2-methacrylfluorenyloxy) Ethyl) -2,2-difluorooxetane, 3- (2-methylpropenyloxyethyl) -2,2,4-trifluorooxetane, 3- ( 2-methacrylfluorenyloxyethyl) -2,2,4,4-tetrafluorooxetane and other methacrylates.

其中,就共聚反應性及所述硬化性樹脂組成物的硬化性的提高的觀點而言,優選為甲基丙烯酸縮水甘油酯、甲基丙烯酸-6,7-環氧基庚酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、甲基丙烯酸3,4-環氧基環己酯,更優選為甲基丙烯酸縮水甘油酯、甲基丙烯酸3,4-環氧基環己酯。 Among these, from the viewpoint of improving the copolymerization reactivity and the curability of the curable resin composition, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, and o-vinyl group are preferred. Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, more preferably glycidyl methacrylate, methyl 3,4-epoxycyclohexyl acrylate.

源自所述(F2)化合物的結構單元的含有比例以相對於[F]聚合物的合成中使用的全部單體的投入比計,優選為5質量%~70質量%,更優選為10質量%~60質量%,進而優選為15質量%~50質量%。藉由將所述含有比例設為所述範圍,可進一步提 高硬化膜的耐溶劑性及硬度。 The content ratio of the structural unit derived from the (F2) compound is preferably 5% to 70% by mass, and more preferably 10% by mass based on the input ratio of all monomers used in the synthesis of the [F] polymer. % To 60% by mass, and more preferably 15% to 50% by mass. By setting the content ratio to the range, it is possible to further improve High solvent resistance and hardness.

[(F3)化合物] [(F3) Compound]

(F3)化合物是(F1)化合物及(F2)化合物以外的不飽和化合物。(F3)化合物只要是具有自由基聚合性的不飽和化合物則並無特別限定。(F3)化合物例如可列舉:甲基丙烯酸烷基酯、甲基丙烯酸環烷基酯、具有羥基的甲基丙烯酸酯、丙烯酸烷基酯、丙烯酸環烷基酯、具有羥基的丙烯酸酯、甲基丙烯酸芳香族酯、丙烯酸芳香族酯、不飽和二羧酸二酯、雙環不飽和化合物、N-順丁烯二醯亞胺化合物、不飽和芳香族化合物、共軛二烯、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架、吡喃骨架或下述式(2)所表示的骨架的不飽和化合物、下述式(3)所表示的含酚性羥基的不飽和化合物、具有水解性矽烷基的不飽和化合物、其他不飽和化合物等。 The (F3) compound is an unsaturated compound other than the (F1) compound and the (F2) compound. The (F3) compound is not particularly limited as long as it is a radically polymerizable unsaturated compound. Examples of the (F3) compound include alkyl methacrylate, cycloalkyl methacrylate, methacrylate having a hydroxyl group, alkyl acrylate, cycloalkyl acrylate, acrylate having a hydroxyl group, and methyl Aromatic acrylic acid, aromatic acrylic acid, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, N-cis butylene diimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan Unsaturated compounds having a skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the following formula (2), unsaturated compounds containing a phenolic hydroxyl group represented by the following formula (3), and hydrolyzable silane groups Unsaturated compounds, other unsaturated compounds, etc.

所述式(2)中,R7為氫原子或甲基。m為1以上的整數。 In the formula (2), R 7 is a hydrogen atom or a methyl group. m is an integer of 1 or more.

[化6] [Chemical 6]

所述式(3)中,R8為氫原子或碳數1~4的烷基。R9~R13分別獨立地為氫原子、羥基或碳數1~4的烷基。Y為單鍵、-COO-或-CONH-。p為0~3的整數。其中,R9~R13的至少1個為羥基。 In the formula (3), R 8 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 9 to R 13 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO-, or -CONH-. p is an integer from 0 to 3. Among them, at least one of R 9 to R 13 is a hydroxyl group.

甲基丙烯酸烷基酯、甲基丙烯酸環烷基酯、丙烯酸烷基酯、丙烯酸環烷基酯、甲基丙烯酸芳香族酯、丙烯酸芳香族酯、不飽和二羧酸二酯、雙環不飽和化合物、N-順丁烯二醯亞胺化合物、不飽和芳香族化合物、共軛二烯、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架或吡喃骨架的不飽和化合物、其他化合物例如可列舉與作為提供[A]聚合物的結構單元(III)的化合物而例示的化合物同樣的化合物等。 Alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aromatic methacrylate, aromatic acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound , N-cis-butene difluorene imine compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton or pyran skeleton, and other compounds include The same compounds as the compounds exemplified as the compound providing the structural unit (III) of the [A] polymer, and the like.

具有羥基的甲基丙烯酸酯例如可列舉:甲基丙烯酸羥基甲酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸3-羥基丙酯、甲基丙烯酸4-羥基丁酯、二乙二醇單甲基丙烯酸酯、甲基丙烯酸2,3-二羥基丙酯、2-甲基丙烯醯氧基乙基葡糖苷、甲基丙烯酸4-羥基苯基酯等。 Examples of the methacrylate having a hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and diethylene glycol monoester. Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glucoside, 4-hydroxyphenyl methacrylate, and the like.

具有羥基的丙烯酸酯例如可列舉:丙烯酸羥基甲酯、丙 烯酸2-羥基乙酯、丙烯酸3-羥基丙酯、丙烯酸4-羥基丁酯、二乙二醇單丙烯酸酯、丙烯酸2,3-二羥基丙酯、2-丙烯醯氧基乙基葡糖苷、丙烯酸4-羥基苯基酯等。 Examples of the acrylate having a hydroxyl group include hydroxymethyl acrylate, acrylic 2-hydroxyethyl enoate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, 2,3-dihydroxypropyl acrylate, 2-propenyloxyethyl glucoside , 4-hydroxyphenyl acrylate and the like.

含有所述式(2)所表示的骨架的不飽和化合物例如可列舉:聚乙二醇(n=2~10)單(甲基)丙烯酸酯、聚丙二醇(n=2~10)單(甲基)丙烯酸酯等。 Examples of unsaturated compounds containing a skeleton represented by the formula (2) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, and polypropylene glycol (n = 2 to 10) mono (methyl) Group) acrylate and the like.

所述式(3)所表示的含酚性羥基的不飽和化合物可列舉:根據Y與p的定義而由下述式(4)~式(8)表示的化合物等。 Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the formula (3) include compounds represented by the following formulae (4) to (8) based on the definitions of Y and p.

所述式(4)中,q為1~3的整數。R8~R13與所述式(3)同義。 In the formula (4), q is an integer of 1 to 3. R 8 to R 13 are synonymous with the formula (3).

[化8] [Chemical 8]

所述式(5)中,R8~R13與所述式(3)同義。 In the formula (5), R 8 to R 13 are synonymous with the formula (3).

所述式(6)中,r為1~3的整數。R8~R13與所述式(3)同義。 In the formula (6), r is an integer of 1 to 3. R 8 to R 13 are synonymous with the formula (3).

所述式(7)中,R8~R13與所述式(3)同義。 In the formula (7), R 8 to R 13 are synonymous with the formula (3).

[化11] [Chemical 11]

所述式(8)中,R8~R13與所述式(3)同義。 In the formula (8), R 8 to R 13 are synonymous with the formula (3).

具有水解性矽烷基的不飽和化合物例如可列舉:2-甲基丙烯醯氧基乙基三甲氧基矽烷、2-甲基丙烯醯氧基乙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三丙基矽烷、3-甲基丙烯醯氧基丙基三氯矽烷、4-甲基丙烯醯氧基丁基三甲氧基矽烷、4-甲基丙烯醯氧基丁基三乙氧基矽烷、2-丙烯醯氧基乙基三甲氧基矽烷、2-丙烯醯氧基乙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三丙基矽烷、3-丙烯醯氧基丙基三氯矽烷、4-丙烯醯氧基丁基三甲氧基矽烷、4-丙烯醯氧基丁基三乙氧基矽烷等。 Examples of the unsaturated compound having a hydrolyzable silane group include 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, and 3-methacrylfluorene Oxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropylsilane, 3-methacryloxypropyltripropyl Trichlorosilane, 4-methacryloxybutyltrimethoxysilane, 4-methacryloxybutyltriethoxysilane, 2-acryloxyethyltrimethoxysilane, 2- Propylene ethoxyethyltriethoxysilane, 3-propylene ethoxypropyltrimethoxysilane, 3-propylene ethoxypropyltriethoxysilane, 3-propylene ethoxypropyltripropyl Silane, 3-propenyloxypropyltrichlorosilane, 4-propenyloxybutyltrimethoxysilane, 4-propenyloxybutyltriethoxysilane, and the like.

其中,優選為甲基丙烯酸烷基酯、甲基丙烯酸環烷基酯、N-順丁烯二醯亞胺化合物、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架、吡喃骨架或所述式(2)所表示的骨架的不飽和化合物、所述式(3)所表示的含酚性羥基的不飽和化合物、不飽和芳香族化合物、丙烯酸環烷基酯、具有水解性矽烷基的不飽和化合物。其中,就共聚反應性及[F]聚合物對鹼性水溶液的溶解性的方面而言更優選為苯乙烯、甲基丙烯酸叔丁酯、甲基丙烯酸正月桂基酯、 甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、對甲氧基苯乙烯、丙烯酸2-甲基環己酯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、(甲基)丙烯酸四氫糠基酯、聚乙二醇(n=2~10)單(甲基)丙烯酸酯、3-(甲基)丙烯醯基氧基四氫呋喃-2-酮、(甲基)丙烯酸4-羥基苄基酯、(甲基)丙烯酸4-羥基苯基酯、鄰羥基苯乙烯、對羥基苯乙烯、α-甲基-對羥基苯乙烯,進而優選為α-甲基-對羥基苯乙烯、苯乙烯、甲基丙烯酸四氫糠基酯、N-環己基順丁烯二醯亞胺、甲基丙烯酸正月桂基酯、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、3-甲基丙烯醯氧基丙基三乙氧基矽烷。 Among them, an alkyl methacrylate, a cycloalkyl methacrylate, an N-cis butylene diimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, or the formula is preferable. Unsaturated compounds of the skeleton represented by (2), phenolic hydroxyl-containing unsaturated compounds represented by the formula (3), unsaturated aromatic compounds, cycloalkyl acrylates, and unsaturated hydrolysable silane groups Compound. Among them, styrene, tert-butyl methacrylate, n-lauryl methacrylate, and tricyclic methacrylate are more preferred in terms of copolymerization reactivity and the solubility of the [F] polymer in an alkaline aqueous solution. 5.2.1.0 2,6 ] Decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylcis butylene diimide, N-cyclohexylcis butene Diamidine, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 ~ 10) mono (meth) acrylate, 3- (meth) propenyloxytetrahydrofuran-2- Ketone, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, α -methyl-p-hydroxystyrene, more preferably α -Methyl-p-hydroxystyrene, styrene, tetrahydrofurfuryl methacrylate, N-cyclohexyl cis butene diamidine, n-lauryl methacrylate, tricyclic methacrylate [5.2.1.0 2,6 ] decane-8-yl ester, 3-methacryloxypropyltriethoxysilane.

源自所述(F3)化合物的結構單元的含有比例以相對於[F]聚合物的合成中使用的全部單體的投入比計,優選為10質量%~90質量%,更優選為30質量%~80質量%,進而優選為40質量%~65質量%。藉由將所述含有比例設為所述範圍,可進一步提高所述硬化性樹脂組成物的顯影性、及硬化膜的耐溶劑性。 The content ratio of the structural unit derived from the (F3) compound is preferably 10% to 90% by mass, and more preferably 30% by mass relative to the input ratio of all monomers used in the synthesis of the [F] polymer. % To 80% by mass, and more preferably 40% to 65% by mass. By setting the content ratio to the range, the developability of the curable resin composition and the solvent resistance of the cured film can be further improved.

<[F]聚合物的合成方法> <[F] Synthesis method of polymer>

[F]聚合物可藉由如下方式進行合成:與所述合成[A]聚合物的聚合同樣地、在溶劑中使用自由基聚合起始劑使所述(F1)化合物及(F2)化合物、以及視需要的(F3)化合物等進行聚合。 [F] The polymer can be synthesized by, as in the polymerization of the synthesized [A] polymer, using a radical polymerization initiator in a solvent to make the (F1) compound and (F2) compound, And (F3) compound etc., as needed, are polymerized.

[F]聚合物的Mw優選為2,000~100,000,更優選為3,000~50,000,進而優選為5,000~20,000。藉由將[F]聚合物的Mw設為所述範圍,所述硬化性樹脂組成物可進一步提高顯影性,另外在製成放射線硬化性樹脂組成物的情形時,可進一步提高放射線 感度。 [F] The Mw of the polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 20,000. By setting the Mw of the [F] polymer to the above range, the curable resin composition can further improve developability, and when the radiation curable resin composition is made, the radiation can be further improved. Sensitivity.

相對於[A]聚合物100質量份,[F]聚合物的含有量優選為10質量份以上且3,000質量份以下,更優選為50質量份以上且1,500質量份以下,進而優選為150質量份以上且800質量份以下。藉由將[F]聚合物的含有量設為所述範圍,所述硬化性樹脂組成物可進一步提高硬化膜的硬度。 The content of the [F] polymer is preferably 10 parts by mass or more and 3,000 parts by mass relative to 100 parts by mass of the [A] polymer, more preferably 50 parts by mass or more and 1,500 parts by mass or less, and still more preferably 150 parts by mass More than 800 parts by mass. By setting the content of the [F] polymer to the above range, the curable resin composition can further increase the hardness of the cured film.

<其他任意成分> <Other optional ingredients>

其他任意成分例如可列舉:環氧化合物、黏附助劑、金屬氧化物粒子、表面活性劑、硬化劑等。所述硬化性樹脂組成物可含有1種或2種以上的所述其他任意成分,也可含有1種或2種以上的各自的成分。 Examples of other optional components include epoxy compounds, adhesion aids, metal oxide particles, surfactants, and hardeners. The said curable resin composition may contain one or two or more of said other arbitrary components, and may contain one or two or more of each of them.

[環氧化合物] [Epoxy compound]

環氧化合物是具有環氧基的化合物(其中,相當於所述[F]聚合物的化合物除外)。所述硬化性樹脂組成物藉由含有環氧化合物,可進一步提高硬化膜的耐熱性、表面硬度及膜厚均勻性。 The epoxy compound is a compound having an epoxy group (except for compounds corresponding to the [F] polymer). The curable resin composition can further improve the heat resistance, surface hardness, and film thickness uniformity of the cured film by containing an epoxy compound.

環氧基例如可列舉氧雜環丙基、氧雜環丁基等。環氧化合物可具有1個或2個以上的環氧基。 Examples of the epoxy group include oxetanyl and oxetanyl. The epoxy compound may have one or two or more epoxy groups.

具有1個環氧基的化合物例如可列舉:(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基丁酯、α-乙基丙烯酸3,4-環氧基丁酯、(甲基)丙烯酸6,7-環氧基庚酯、α-乙基丙烯酸6.7-環氧基庚酯、鄰乙烯基苄基縮水甘油醚、間乙烯 基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、苯基縮水甘油醚、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基二乙氧基矽烷等。 Examples of the compound having one epoxy group include glycidyl (meth) acrylate, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl α -ethylacrylate, 6,7-epoxyheptyl (meth) acrylate, α -ethylacrylic acid 6.7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloxy Methyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, phenyl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyldiethoxysilane, and the like.

具有2個以上的環氧基的化合物例如可列舉:3,4-環氧基環己基甲基-3',4'-環氧基環己烷羧酸酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間二噁烷、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、3,4-環氧基-6-甲基環己基-3',4'-環氧基-6'-甲基環己烷羧酸酯、亞甲基雙(3,4-環氧基環己烷)、二環戊二烯二環氧化物、乙二醇的二(3,4-環氧基環己基甲基)醚、伸乙基雙(3,4-環氧基環己烷羧酸酯);雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、氫化雙酚AD二縮水甘油醚等雙酚型二縮水甘油醚類;1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、丙三醇三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚等多元醇的聚縮水甘油醚類;藉由在乙二醇、丙二醇、丙三醇等脂肪族多元醇上加成1種或2種以上的環氧烷而獲得的聚醚多元醇的聚縮水甘油醚類;苯酚酚醛清漆型環氧樹脂;甲酚酚醛清漆型環氧樹脂; 多酚型環氧樹脂;脂肪族長鏈二元酸的二縮水甘油酯類;高級脂肪酸的縮水甘油酯類;脂肪族聚縮水甘油醚類;環氧化大豆油、環氧化亞麻油等。 Examples of the compound having two or more epoxy groups include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, and 2- (3,4-cyclo Oxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3 , 4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-form Cyclohexanecarboxylic acid ester, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexyl) of ethylene glycol Methyl) ether, ethyl bis (3,4-epoxycyclohexanecarboxylate); bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenation Bisphenol-type diglycidyl ethers such as bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6 -Polyglycidyl polyol such as hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; phenol novolacs Epoxy resin; cresol novolac epoxy resin; Polyphenol epoxy resins; diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl esters of higher fatty acids; aliphatic polyglycidyl ethers; epoxidized soybean oil, epoxidized linseed oil, etc.

具有2個以上的環氧基的化合物的市售品例如可列舉:作為雙酚A酚醛清漆型環氧樹脂的愛皮考特(Epikote)1001、愛皮考特(Epikote)1002、愛皮考特(Epikote)1003、愛皮考特(Epikote)1004、愛皮考特(Epikote)1007、愛皮考特(Epikote)1009、愛皮考特(Epikote)1010、愛皮考特(Epikote)828(以上,日本環氧樹脂(Japan Epoxy Resins)公司)等;作為雙酚F型環氧樹脂的愛皮考特(Epikote)807(以上,日本環氧樹脂公司)等;作為苯酚酚醛清漆型環氧樹脂的愛皮考特(Epikote)152、愛皮考特(Epikote)154、愛皮考特(Epikote)157S65(以上,日本環氧樹脂公司),EPPN201、EPPN202(以上,日本化藥公司)等;作為甲酚酚醛清漆型環氧樹脂的EOCN102、EOCN103S、EOCN104S、1020、1025、1027(以上,日本化藥公司),愛皮考特(Epikote)180S75(日本環氧樹脂公司)等;作為多酚型環氧樹脂的愛皮考特(Epikote)1032H60、愛皮考特(Epikote)XY-4000(以上,日本環氧樹脂公司)等; 作為環狀脂肪族環氧樹脂的CY-175、CY-177、CY-179、艾勞達(Araldite)CY-182、艾勞達(Araldite)192、184(以上,汽巴精化(Ciba specialty chemicals)製造),ERL-4234、4299、4221、4206(以上,U.C.C公司),昭達因(Shodain)509(昭和電工公司),艾匹克隆(Epiclon)200、艾匹克隆(Epiclon)400(以上,迪愛生(DIC)公司),愛皮考特(Epikote)871、愛皮考特(Epikote)872(以上,日本環氧樹脂公司),ED-5661、ED-5662(以上,塞拉尼斯塗佈(Celanese Coating)公司)等;作為脂肪族聚縮水甘油醚的艾博萊特(Epolight)100MF(共榮社化學公司),愛皮奧魯(Epiol)TMP(日本油脂公司)等。 Commercially available products of compounds having two or more epoxy groups include, for example, Epikote 1001, Epikote 1002, and Epicote as bisphenol A novolac epoxy resins. Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (Above, Japan Epoxy Resins), etc .; Epikote 807 (above, Japan Epoxy Resins), etc. as bisphenol F type epoxy resin; etc., as phenol novolac type ring Epoxyte 152, Epikote 154, Epikote 157S65 (above, Japan Epoxy Resin), EPPN201, EPPN202 (above, Japan Chemical Co.) Etc .; as cresol novolac epoxy resin EOCN102, EOCN103S, EOCN104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Co., Ltd.), etc .; Epikote 1032H60, Epikote XY-4000 (above, Japanese epoxy resin) Fat company), etc .; Cycyclic aliphatic epoxy resins CY-175, CY-177, CY-179, Araldite CY-182, Araldite 192, 184 (above, Ciba specialty chemicals), ERL-4234, 4299, 4221, 4206 (above, UCC), Shodain 509 (Showa Denko), Epiclon 200, Epiclon 400 ( Above, DIC Corporation), Epikote 871, Epikote 872 (above, Japan Epoxy Resin Company), ED-5661, ED-5662 (above, Celanese (Celanese Coating Co.), etc .; Epolight 100MF (Kyoeisha Chemical Co., Ltd.) as an aliphatic polyglycidyl ether; Epiol TMP (Nippon Oil & Fats Co., Ltd.).

相對於[A]聚合物100質量份,環氧化合物的含有量優選為100質量份以下,更優選為75質量份以下,進而優選為50質量份以下。藉由將環氧化合物的含有量設為所述範圍,所述硬化性樹脂組成物可進而提高硬化膜的耐熱性、表面硬度及膜厚均勻性。 The content of the epoxy compound is preferably 100 parts by mass or less with respect to 100 parts by mass of the [A] polymer, more preferably 75 parts by mass or less, and still more preferably 50 parts by mass or less. By setting the content of the epoxy compound to the above range, the curable resin composition can further improve the heat resistance, surface hardness, and film thickness uniformity of the cured film.

[黏附助劑] [Adhesion aid]

黏附助劑用以進而提高由所述硬化性樹脂組成物所得的硬化膜與基板等的黏附性。此種黏附助劑優選為官能性矽烷偶合劑。官能性矽烷偶合劑例如可列舉:具有羧基、甲基丙烯醯基、異氰酸酯基、環氧基等反應性基的偶合劑等。此種官能性矽烷偶合劑例如可列舉:三甲氧基矽烷基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ- 異氰酸酯基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷等。 The adhesion auxiliary agent is used to further improve the adhesion between the cured film obtained from the curable resin composition and a substrate or the like. Such an adhesion promoter is preferably a functional silane coupling agent. Examples of the functional silane coupling agent include a coupling agent having a reactive group such as a carboxyl group, a methacryl group, an isocyanate group, and an epoxy group. Examples of such a functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

相對於[A]聚合物100質量份,黏附助劑的含有量優選為20質量份以下,更優選為10質量份以下。藉由將黏附助劑的含有量設為20質量份以下,可抑制顯影步驟中的顯影殘留的產生。 The content of the adhesion aid is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the [A] polymer. By setting the content of the adhesion aid to 20 parts by mass or less, it is possible to suppress generation of development residue in the development step.

[金屬氧化物粒子] [Metal oxide particles]

金屬氧化物粒子在由所述硬化性樹脂組成物形成絕緣膜的情形時,可維持所述絕緣膜的電絕緣性且可抑制相對介電常數的上升。所述金屬氧化物粒子也可出於如下目的等來使用,即,絕緣膜的折射率的控制、絕緣膜的透明性的控制、因緩和硬化收縮而導致的裂紋的抑制、絕緣膜表面硬度的提高。 When the metal oxide particles form an insulating film from the curable resin composition, the electrical insulating properties of the insulating film can be maintained, and an increase in the relative dielectric constant can be suppressed. The metal oxide particles can also be used for the following purposes: control of the refractive index of the insulating film, control of the transparency of the insulating film, suppression of cracks due to relaxation hardening shrinkage, and reduction of the surface hardness of the insulating film. improve.

金屬氧化物粒子例如為矽、鋁、鋯、鈦、鋅、銦、錫、銻、鍶、鋇、鈰、鉿的氧化物粒子。金屬氧化物粒子可為單一氧化物粒子也可為複合氧化物粒子。 The metal oxide particles are, for example, oxide particles of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, or thallium. The metal oxide particles may be single oxide particles or composite oxide particles.

單一氧化物可列舉:二氧化矽、氧化鋁、氧化鋯、二氧化鈦、氧化鈰等。 Examples of the single oxide include silicon dioxide, aluminum oxide, zirconia, titanium dioxide, and cerium oxide.

複合氧化物例如可列舉:鈦酸鋇、鈦酸鍶、氧化銻錫(antimony-tin oxide,ATO)、氧化銦錫(indium-tin oxide,ITO)、氧化銦鋅(indium-zinc oxide,IZO)等。 Examples of the composite oxide include barium titanate, strontium titanate, antimony-tin oxide (ATO), indium-tin oxide (ITO), and indium-zinc oxide (IZO). Wait.

其中,優選為矽、鋯、鈦、鋅、鋇的氧化物粒子,更優選為二氧化矽粒子、氧化鋯粒子、二氧化鈦粒子、鈦酸鋇(BaTiO3)。金屬氧化物粒子的市售品例如可使用希愛化成 (C.I.Kasei)公司的“納諾達克(Nanotec)(註冊商標)”等。 Among these, oxide particles of silicon, zirconium, titanium, zinc, and barium are preferable, and silicon dioxide particles, zirconia particles, titanium dioxide particles, and barium titanate (BaTiO 3 ) are more preferable. As a commercially available product of metal oxide particles, for example, "Nanotec (registered trademark)" of CIKasei Co., Ltd. can be used.

金屬氧化物粒子的形狀並無特別限定,可為球狀也可為不定形狀,另外也可為中空粒子、多孔質粒子、核.殼型粒子等。 The shape of the metal oxide particles is not particularly limited, and may be spherical or indefinite, and may also be hollow particles, porous particles, or nuclei. Shell-type particles, etc.

以利用動態光散射法求出的值計,金屬氧化物粒子的體積平均粒徑優選為5nm~200nm,更優選為5nm~100nm,進而優選為10nm~80nm。若金屬氧化物粒子的體積平均粒徑小於5nm,則有使用硬化性樹脂組成物而得的絕緣膜的硬度降低的擔憂、及無法顯現所謀求的相對介電常數的擔憂。另一方面,若體積平均粒徑超過200nm,則有絕緣膜的霧度變高而透過率降低的擔憂、及絕緣膜的平滑性惡化的擔憂。 The volume average particle diameter of the metal oxide particles is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and even more preferably 10 nm to 80 nm, as a value obtained by a dynamic light scattering method. When the volume average particle diameter of the metal oxide particles is less than 5 nm, there is a concern that the hardness of the insulating film obtained by using the curable resin composition may decrease, and that the required relative dielectric constant may not be developed. On the other hand, if the volume average particle diameter exceeds 200 nm, there is a concern that the haze of the insulating film increases and the transmittance decreases, and the smoothness of the insulating film may deteriorate.

相對於[A]聚合物100質量份,金屬氧化物粒子的含有量優選為0.01質量份以上且20質量份以下,更優選為1質量份以上且10質量份以下。若金屬氧化物粒子的含有量小於0.01質量份,則有無法將絕緣膜的相對介電常數控制於所需範圍內的擔憂。另一方面,若金屬氧化物粒子的調配量超過20質量份,則有塗佈性或膜的硬化性降低、且絕緣膜的霧度變高的擔憂。 The content of the metal oxide particles is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the [A] polymer, and more preferably 1 part by mass or more and 10 parts by mass or less. When the content of the metal oxide particles is less than 0.01 parts by mass, there is a concern that the relative dielectric constant of the insulating film cannot be controlled within a desired range. On the other hand, when the compounding quantity of a metal oxide particle exceeds 20 mass parts, there exists a possibility that coating property or film hardenability may fall, and the haze of an insulating film may become high.

[表面活性劑] [Surfactant]

表面活性劑是提高所述硬化性樹脂組成物的塗佈性的化合物。所述表面活性劑優選為氟系表面活性劑、矽酮系表面活性劑、非離子系表面活性劑。 The surfactant is a compound that improves the coatability of the curable resin composition. The surfactant is preferably a fluorine-based surfactant, a silicone-based surfactant, or a non-ionic surfactant.

氟系表面活性劑例如可列舉:1,1,2,2-四氟辛基(1,1,2,2-四氟丙基)醚、1,1,2,2-四氟辛基己基醚、八乙二醇二(1,1,2,2-四氟 丁基)醚、六乙二醇(1,1,2,2,3,3-六氟戊基)醚、八丙二醇二(1,1,2,2-四氟丁基)醚、六丙二醇二(1,1,2,2,3,3-六氟戊基)醚、全氟十二烷基磺酸鈉、1,1,2,2,8,8,9,9,10,10-十氟十二烷、1,1,2,2,3,3-六氟癸烷等,此外還可列舉:氟烷基苯磺酸鈉;氟烷基氧基伸乙基醚;氟烷基碘化銨、氟烷基聚氧化乙烯醚、全氟烷基聚氧化乙醇;全氟烷基烷氧基化物;氟系烷基酯等。 Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, and 1,1,2,2-tetrafluorooctylhexyl Ether, octaethylene glycol di (1,1,2,2-tetrafluoro Butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol Bis (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10 -Decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. In addition, there may be mentioned: sodium fluoroalkylbenzenesulfonate; fluoroalkyloxyethyl ether; fluoroalkyl Ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol; perfluoroalkyl alkoxylates; fluorine-based alkyl esters, etc.

氟系表面活性劑的市售品例如可列舉:“BM-1000”、“BM-1100”(以上,碧陌化學(BM Chemie)公司),“美佳法(Megafac)F142D”、“美佳法(Megafac)F172”、“美佳法(Megafac)F173”、“美佳法(Megafac)F183”、“美佳法(Megafac)F178”、“美佳法(Megafac)F191”、“美佳法(Megafac)F471”(以上,大日本油墨化學工業公司),“弗洛德(Fluorad)FC-170C”、“弗洛德(Fluorad)FC-171”、“弗洛德(Fluorad)FC-430”、“弗洛德(Fluorad)FC-431”(以上,住友3M公司),“沙福隆(Surflon)S-112”、“沙福隆(Surflon)S-113”、“沙福隆(Surflon)S-131”、“沙福隆(Surflon)S-141”、“沙福隆(Surflon)S-145”、“沙福隆(Surflon)S-382”、“沙福隆(Surflon)SC-101”、“沙福隆(Surflon)SC-102”、“沙福隆(Surflon)SC-103”、“沙福隆(Surflon)SC-104”、“沙福隆(Surflon)SC-105”、“沙福隆(Surflon)SC-106”(以上,旭硝子公司),“艾福拓(Eftop)EF301”、“艾福拓(Eftop)EF303”、“艾福拓(Eftop)EF352”(以上,新秋田化成公司) 等。 Examples of commercially available products of the fluorine-based surfactant include: "BM-1000", "BM-1100" (above, BM Chemie), "Megafac F142D", and "Megaf ( Megafac) F172 "," Megafac F173 "," Megafac F183 "," Megafac F178 "," Megafac F191 "," Megafac F471 "( Above, Dainippon Ink Chemical Industry Co., Ltd.), "Fluorad FC-170C", "Fluorad FC-171", "Fluorad FC-430", "Flod (Fluorad) FC-431 "(above, Sumitomo 3M)," Surflon S-112 "," Surflon S-113 "," Surflon S-131 " , "Surflon S-141", "Surflon S-145", "Surflon S-382", "Surflon SC-101", " "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Saflon (Surflon SC-106 "(above, Asahi Glass Co., Ltd.)," Eftop EF301 "," Aifu (Eftop) EF303 "," aifo extension (Eftop) EF352 "(above, new Akita Kasei Corporation) Wait.

矽酮系表面活性劑的市售品例如可列舉:“DC3PA”、”DC7PA”、“FS-1265”、“SF-8428”、“SH11PA”、“SH21PA”、“SH28PA”、“SH29PA”、“SH30PA”、“SH-190”、“SH-193”、“SZ-6032”(以上,東麗道康寧矽酮(toray dowcorning silicone)公司),“TSF-4440”、“TSF-4300”、“TSF-4445”、“TSF-4446”、“TSF-4460”、“TSF-4452”(以上,GE東芝矽酮公司)等。 Examples of commercially available silicone surfactants include "DC3PA", "DC7PA", "FS-1265", "SF-8428", "SH11PA", "SH21PA", "SH28PA", "SH29PA", "SH30PA", "SH-190", "SH-193", "SZ-6032" (above, toray dowcorning silicone company), "TSF-4440", "TSF-4300", " TSF-4445 "," TSF-4446 "," TSF-4460 "," TSF-4452 "(above, GE Toshiba Silicone Corporation), etc.

非離子系表面活性劑例如可列舉:聚氧化乙烯月桂基醚、聚氧化乙烯硬脂基醚、聚氧化乙烯油烯基醚等聚氧化乙烯烷基醚類;聚氧化乙烯辛基苯基醚、聚氧化乙烯壬基苯基醚等聚氧化乙烯芳基醚類;聚氧化乙烯二月桂酸酯、聚氧化乙烯二硬脂酸酯等聚氧化乙烯二烷基酯類;(甲基)丙烯酸系共聚物類等。 Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, Polyoxyethylene aryl ethers such as polyethylene oxide nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate; (meth) acrylic copolymer Category, etc.

非離子系表面活性劑的市售品可列舉:“波力弗洛(Polyflow)No.57”、“波力弗洛(Polyflow)No.95”(以上,共榮社化學公司)等。 Examples of commercially available nonionic surfactants include "Polyflow No. 57", "Polyflow No. 95" (above, Kyoeisha Chemical Co., Ltd.), and the like.

相對於[A]聚合物100質量份,表面活性劑的含有量優選為10質量份以下,更優選為5質量份以下,進而優選為3質量份以下。藉由將表面活性劑的含有量設為10質量份以下,可進一步 提高所述硬化性樹脂組成物的塗佈性。 The content of the surfactant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the surfactant to 10 parts by mass or less, The coating property of the curable resin composition is improved.

[硬化劑] [hardener]

硬化劑例如可使用日本專利特開2012-88459號公報中所記載的硬化劑。 As the hardener, for example, the hardener described in Japanese Patent Laid-Open No. 2012-88459 can be used.

<硬化性樹脂組成物的製備方法> <Preparation method of curable resin composition>

所述硬化性樹脂組成物可藉由如下方式製備:將[A]聚合物及[B]溶劑、視需要的[C]聚合性化合物、[D]自由基聚合起始劑、[E]酸產生劑、[F]聚合物及其他任意成分均勻地混合,優選為利用0.2μm左右的薄膜過濾器進行過濾。優選為將所述硬化性樹脂組成物溶解於適當的溶劑中而以溶液狀來使用。 The curable resin composition can be prepared by: [A] polymer and [B] solvent, [C] polymerizable compound as needed, [D] radical polymerization initiator, [E] acid The generator, the [F] polymer, and other optional components are uniformly mixed, and it is preferably filtered through a membrane filter of about 0.2 μm. The curable resin composition is preferably used in the form of a solution by dissolving in a suitable solvent.

所述硬化性樹脂組成物可形成黏附性及透明性優異的硬化膜,因此可適宜地用於例如作為層間絕緣膜、保護膜或間隔件的顯示元件用硬化膜的形成。 Since the said curable resin composition can form the hardened film excellent in adhesiveness and transparency, it can be used suitably for formation of the hardened film for display elements, for example as an interlayer insulation film, a protective film, or a spacer.

<顯示元件用硬化膜> <Cured film for display elements>

本發明的顯示元件用硬化膜由所述硬化性樹脂組成物形成。因所述顯示元件用硬化膜由所述硬化性樹脂組成物形成,故黏附性及透明性優異,例如可適宜地用於顯示元件的層間絕緣膜、保護膜、間隔件等。所述顯示元件用硬化膜的形成方法並無特別限定,但優選為應用如下所說明的顯示元件用硬化膜的形成方法。 The cured film for a display element of the present invention is formed of the curable resin composition. Since the cured film for a display element is formed of the curable resin composition, it has excellent adhesion and transparency, and can be suitably used for, for example, an interlayer insulating film, a protective film, a spacer, and the like of a display element. The method for forming the cured film for a display element is not particularly limited, but it is preferable to apply the method for forming a cured film for a display element described below.

<顯示元件用硬化膜的形成方法> <Method for Forming Cured Film for Display Elements>

本發明的顯示元件用硬化膜的形成方法具有:在基板上形成塗膜的步驟(以下也稱為“塗膜形成步驟”), 對塗膜的至少一部分照射放射線的步驟(以下也稱為“照射步驟”),對經放射線照射的塗膜進行顯影的步驟(以下也稱為“顯影步驟”),及對經顯影的塗膜進行加熱的步驟(以下也稱為“加熱步驟”)。所述形成方法中由所述硬化性樹脂組成物形成所述塗膜。所述硬化性樹脂組成物優選為藉由含有所述[D2]感放射線性自由基聚合起始劑及/或[E2]感放射線性酸產生劑等而得的放射線硬化性樹脂組成物。 The method for forming a cured film for a display element of the present invention includes a step of forming a coating film on a substrate (hereinafter also referred to as a "coating film forming step"), A step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "irradiation step"), a step of developing a coating film irradiated with radiation (hereinafter also referred to as "development step"), and a developed coating film A step of heating (hereinafter also referred to as a "heating step"). In the forming method, the coating film is formed from the curable resin composition. The curable resin composition is preferably a radiation curable resin composition obtained by containing the [D2] radiation-sensitive radical polymerization initiator and / or [E2] radiation-sensitive acid generator or the like.

[塗膜形成步驟] [Coating film formation step]

本步驟中,在基板表面塗佈所述硬化性樹脂組成物,且優選為藉由進行預烘烤(prebake)來去除溶劑而形成塗膜。本步驟中所使用的基板例如可列舉:玻璃基板、矽晶片、塑料基板、及在這些基板的表面形成有各種金屬的基板。塑料基板例如可列舉以聚對苯二甲酸乙二酯(Polyethylene Terephthalate,PET)、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚醯亞胺等塑料為主成分的基板等。 In this step, the surface of the substrate is coated with the curable resin composition, and a solvent is preferably removed by performing a prebake to form a coating film. Examples of the substrate used in this step include a glass substrate, a silicon wafer, a plastic substrate, and a substrate having various metals formed on the surface of these substrates. Examples of the plastic substrate include a substrate mainly composed of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether fluorene, polycarbonate, and polyimide. .

所述硬化性樹脂組成物的塗佈方法例如可採用噴霧法、輥塗法、旋轉塗佈法(旋塗(spin coat)法)、狹縫模塗佈法、棒塗佈法、噴墨法等適宜的方法。所述塗佈方法中優選為旋塗法、棒塗佈法、狹縫模塗佈法。預烘烤條件根據所述硬化性樹脂組成物的含有成分的種類、含有量等而不同,但例如可設為在60℃~120℃下進行30秒~10分鐘左右。所述塗膜的膜厚以預烘烤後的值計,優選為0.1μm~8μm,更優選為0.1μm~6μm,進而 優選為0.1μm~4μm。 The coating method of the curable resin composition may be, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method. And other suitable methods. The coating method is preferably a spin coating method, a bar coating method, or a slit die coating method. The pre-baking conditions differ depending on the type, content, and the like of the components contained in the curable resin composition, but they may be performed at 60 ° C. to 120 ° C. for about 30 seconds to 10 minutes, for example. The film thickness of the coating film is a value after pre-baking, preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and further It is preferably 0.1 μm to 4 μm.

[照射步驟] [Irradiation procedure]

本步驟中,對在所述塗膜形成步驟中形成的塗膜介隔具有規定圖案的遮罩照射放射線。此時的放射線例如可列舉:紫外線、遠紫外線、X射線、帶電粒子束等。 In this step, the coating film formed in the coating film forming step is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation at this time include ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

紫外線例如可列舉g射線(波長436nm)、i射線(波長365nm)等。遠紫外線例如可列舉KrF準分子雷射等。X射線例如可列舉同步加速器放射線等。帶電粒子束例如可列舉電子束等。這些放射線中優選為紫外線,紫外線中特別優選包含g射線及/或i射線的放射線。曝光量優選為30J/m2~1,500J/m2Examples of the ultraviolet rays include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). Examples of the far ultraviolet rays include KrF excimer lasers. Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among ultraviolet rays, radiations including g rays and / or i rays are particularly preferable. The exposure amount is preferably 30 J / m 2 to 1,500 J / m 2 .

[顯影步驟] [Developing steps]

本步驟中,可對在所述照射步驟中照射了放射線的塗膜進行顯影,來形成所期望的圖案。顯影處理中所使用的顯影液可使用鹼性水溶液。鹼例如可列舉:氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二乙基胺基乙醇、二-正丙基胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、吡咯、呱啶、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烷等。另外,顯影液可使用在所述鹼性水溶液中添加適量的甲醇、乙醇等水溶性有機溶劑或表面活性劑而成的水溶液、或者為了溶解由所述硬化性樹脂組成物形成的塗膜而含有少量各種有機溶劑的顯影液。進而,顯影方法例如可利用覆液法、浸漬(dipping)法、搖動浸漬法、 噴淋法等方法。顯影時間根據硬化性樹脂組成物的組成而不同,但例如可設為30秒~120秒。 In this step, a coating film irradiated with radiation in the irradiation step may be developed to form a desired pattern. As the developing solution used in the developing process, an alkaline aqueous solution can be used. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propylamine , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyridine, 1,8-diazabicyclo [5.4.0 ] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like. In addition, the developing solution may be an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution, or it may be contained for dissolving a coating film formed of the curable resin composition. A small amount of a developing solution of various organic solvents. Further, as the development method, for example, a liquid coating method, a dipping method, a shaking dipping method, or the like can be used. Spray method and other methods. The development time varies depending on the composition of the curable resin composition, but it can be set to, for example, 30 seconds to 120 seconds.

在顯影步驟之後,優選為進行如下處理:對經圖案化的塗膜進行利用流水清洗的淋洗處理,繼而全面地照射(後曝光)源自高壓水銀燈等的放射線,由此塗膜中殘存的[D2]感放射線性自由基聚合起始劑、[E2]感放射線性酸產生劑等分解。後曝光時的曝光量優選為2,000J/m2~5,000J/m2左右。 After the developing step, it is preferable to perform a process of subjecting the patterned coating film to a rinsing treatment using flowing water cleaning, and then comprehensively irradiating (post-exposure) radiation from a high-pressure mercury lamp or the like, so that the remaining in the coating film [D2] The radiation-sensitive radical polymerization initiator, [E2] the radiation-sensitive acid generator, and the like decompose. The exposure amount at the time of post exposure is preferably about 2,000 J / m 2 to 5,000 J / m 2 .

[加熱步驟] [Heating step]

本步驟中,使用對在所述顯影步驟中經顯影的塗膜進行煆燒的加熱板、烘箱等加熱裝置,對所述塗膜進行加熱(後烘烤處理),由此進行塗膜的硬化。另外,加熱溫度優選為100℃~300℃,更優選為120℃~280℃,進而優選為150℃~250℃。加熱時間根據加熱設備的種類而不同,優選為5分鐘~300分鐘,更優選為10分鐘~180分鐘,進而優選為20分鐘~120分鐘。 In this step, the coating film is heated (post-baking treatment) by using a heating device such as a hot plate or an oven for sintering the coating film developed in the developing step, thereby curing the coating film. . The heating temperature is preferably 100 ° C to 300 ° C, more preferably 120 ° C to 280 ° C, and even more preferably 150 ° C to 250 ° C. The heating time varies depending on the type of heating equipment, but is preferably 5 minutes to 300 minutes, more preferably 10 minutes to 180 minutes, and even more preferably 20 minutes to 120 minutes.

根據所述顯示元件用硬化膜的形成方法,是所述硬化性樹脂組成物利用感放射線性且藉由曝光、顯影及加熱來形成圖案的方法,因此可容易地形成黏附性及透明性優異的硬化膜圖案。 According to the method for forming a cured film for a display element, the curable resin composition is a method for forming a pattern by exposing radiation, developing, and heating by using a radiation-sensitive radiation. Therefore, an excellent adhesiveness and transparency can be easily formed. Hardened film pattern.

<顯示元件> <Display element>

本發明的顯示元件具備所述顯示元件用硬化膜。所述顯示元件可列舉液晶顯示元件、有機EL元件等。此種顯示元件具備硬化膜作為例如層間絕緣膜、保護膜、間隔件。 A display element of the present invention includes the cured film for a display element. Examples of the display element include a liquid crystal display element and an organic EL element. Such a display element includes a cured film as, for example, an interlayer insulating film, a protective film, and a spacer.

[實施例] [Example]

以下,基於實施例而具體地說明本發明,但本發明並不受這些實施例的限定。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

[Mw及Mn] [Mw and Mn]

以下的合成例中,藉由利用下述測定裝置及測定條件的凝膠滲透色譜法(Gel Permeation Chromatography,GPC)來測定[A]聚合物的Mw及Mw/Mn。 In the following synthesis examples, Mw and Mw / Mn of the [A] polymer were measured by Gel Permeation Chromatography (GPC) using the following measurement devices and measurement conditions.

測定裝置:昭和電工公司的“GPC-101” Measuring device: "GPC-101" by Showa Denko Corporation

測定條件: Measurement conditions:

GPC管柱:連結使用昭和電工公司的“GPC-KF-801”、“GPC-KF-802”、“GPC-KF-803”及“GPC-KF-804”。 GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804" used by Showa Denko Corporation.

流動相:四氫呋喃 Mobile phase: tetrahydrofuran

<化合物的合成> <Synthesis of Compound>

[合成例1](化合物(HC-1)的合成) [Synthesis Example 1] (Synthesis of Compound (HC-1))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯酸2-羥基乙酯65.1g(0.5mol)、吡啶59.3g(0.75mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯76.18g(0.6mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-1)所表示的化合物83.4g(產率76%)。 In a 5 L reactor equipped with a stirrer and a dropping funnel, 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate, 59.3 g (0.75 mol) of pyridine and 500 mL of dichloromethane were charged, and the reaction was carried out under nitrogen. The inside of the apparatus was cooled to 0 ° C, and 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 83.4 g of a compound represented by the following formula (HC-1) ( 76% yield).

[化12] [Chemical 12]

[合成例2](化合物(HC-2)的合成) [Synthesis Example 2] (Synthesis of Compound (HC-2))

在設置有攪拌機及滴加漏斗的5L反應器內,投入4-羥基-α-甲基苯乙烯67.1g(0.5mol)、吡啶59.3g(0.75mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯76.18g(0.6mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-2)所表示的化合物80.0g(產率71%)。 In a 5 L reactor equipped with a stirrer and a dropping funnel, 67.1 g (0.5 mol) of 4-hydroxy- α -methylstyrene, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane were charged. The inside of the reactor was cooled to 0 ° C, while 76.18 g (0.6 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 80.0 g of a compound represented by the following formula (HC-2) ( 71% yield).

[合成例3](化合物(HC-3)的合成) [Synthesis Example 3] (Synthesis of Compound (HC-3))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯酸2,3-二羥基丙酯80.1g(0.5mol)、吡啶118.7g(1.5mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯152.4g(1.2mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食 鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-3)所表示的化合物106.3g(產率62%)。 In a 5 L reactor equipped with a stirrer and a dropping funnel, 80.1 g (0.5 mol) of 2,3-dihydroxypropyl methacrylate, 118.7 g (1.5 mol) of pyridine, and 500 mL of dichloromethane were charged. While cooling the inside of the reactor to 0 ° C., 152.4 g (1.2 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C. with stirring for 2 hours. For the obtained reaction solution, an aqueous sodium hydrogen carbonate solution and a saturated food were used in this order. After washing with brine, the solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 106.3 g (yield 62%) of a compound represented by the following formula (HC-3).

[合成例4](化合物(HC-4)的合成) [Synthesis Example 4] (Synthesis of Compound (HC-4))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯酸(3,4-二羥基環己基)甲酯107.2g(0.5mol)、吡啶118.7g(1.5mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯152.4g(1.2mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-4)所表示的化合物125.5g(產率64%)。 In a 5 L reactor equipped with a stirrer and a dropping funnel, 107.2 g (0.5 mol) of methyl (3,4-dihydroxycyclohexyl) methacrylate, 118.7 g (1.5 mol) of pyridine and 500 mL of dichloromethane were charged. While cooling the inside of the reactor to 0 ° C. under nitrogen, 152.4 g (1.2 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C. with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 125.5 g of a compound represented by the following formula (HC-4) ( 64% yield).

[合成例5](化合物(HC-5)的合成) [Synthesis Example 5] (Synthesis of Compound (HC-5))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯 酸3-羥基-1-金剛烷基酯118.2g(0.5mol)、吡啶59.3g(0.75mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯76.18g(0.6mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-5)所表示的化合物117.2g(產率72%)。 In a 5L reactor equipped with a stirrer and a dropping funnel, methacrylic acid was charged. 118.2 g (0.5 mol) of 3-hydroxy-1-adamantyl acid, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane. The reactor was cooled to 0 ° C under nitrogen while the reactor was added dropwise. 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise, and the mixture was reacted at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 117.2 g of a compound represented by the following formula (HC-5) ( 72% yield).

[合成例6](化合物(HC-6)的合成) [Synthesis Example 6] (Synthesis of Compound (HC-6))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯酸3-(2-羥基乙氧基)-金剛烷基酯140.2g(0.5mol)、吡啶59.3g(0.75mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯76.18g(0.6mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-6)所表示的化合物128.5g(產率69%)。 In a 5L reactor equipped with a stirrer and a dropping funnel, 140.2 g (0.5 mol) of 3- (2-hydroxyethoxy) -adamantyl methacrylate, 59.3 g (0.75 mol) of pyridine, and dichloride were charged. In 500 mL of methane, 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel while cooling the inside of the reactor to 0 ° C. under nitrogen, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 128.5 g of a compound represented by the following formula (HC-6) ( Yield 69%).

[化17] [Chemical 17]

[合成例7](化合物(HC-7)的合成) [Synthesis Example 7] (Synthesis of Compound (HC-7))

在設置有攪拌機及滴加漏斗的5L反應器內,投入甲基丙烯酸4-羥基苯基酯89.1g(0.5mol)、吡啶59.3g(0.75mol)及二氯甲烷500mL,在氮氣下,一邊將反應器內冷卻至0℃,一邊自滴加漏斗滴加3-氯丙醯氯76.18g(0.6mol),然後在0℃、攪拌下反應2小時。對所得的反應液依次利用碳酸氫鈉水溶液及飽和食鹽水進行清洗後進行減壓濃縮,利用矽膠管柱色譜法進行純化,由此獲得下述式(HC-7)所表示的化合物105.1g(產率78%)。 In a 5L reactor equipped with a stirrer and a dropping funnel, 89.1 g (0.5 mol) of 4-hydroxyphenyl methacrylate, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane were charged. While the inside of the reactor was cooled to 0 ° C, 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel, and the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 105.1 g of a compound represented by the following formula (HC-7) ( Yield: 78%).

<[A]聚合物的合成> <[A] Synthesis of polymer>

[合成例8](聚合物(A-1)的合成) [Synthesis Example 8] (Synthesis of Polymer (A-1))

將所述合成的化合物(HC-1)36.6g(20莫耳%)、甲基丙烯酸17.8g(25莫耳%)及甲基丙烯酸甲酯45.6g(55莫耳%)溶解於140g的3-甲氧基丙酸甲酯中,添加2,2'-偶氮雙(2,4-二甲基戊腈)14.4g來製備單體溶液。繼而,對加入有60g的3-甲氧基丙酸 甲酯的500mL的三口燒瓶進行30分鐘氮氣沖洗後,一邊攪拌一邊加熱至70℃,利用滴加漏斗花2小時滴加所述製備的單體溶液。將滴加開始設為聚合反應的開始時間,實施4小時聚合反應。其後,將聚合反應液的溫度設為90℃,攪拌30分鐘。進而其後,將聚合反應液的溫度設為70℃,添加三乙胺77.9mL,保持70℃的溫度攪拌3小時。冷卻至室溫後,添加12N鹽酸水55.9mL,攪拌30分鐘後添加乙酸乙酯並進行分液。利用蒸餾水清洗有機相後,對回收的有機相進行濃縮並利用3-甲氧基丙酸甲酯(作為[B]溶劑的(B-1))進行稀釋,由此獲得含有40質量%聚合物(A-1)的聚合物溶液。聚合物(A-1)的Mw為7,000。 36.6 g (20 mole%) of the synthesized compound (HC-1), 17.8 g (25 mole%) of methacrylic acid, and 45.6 g (55 mole%) of methyl methacrylate were dissolved in 140 g of 3 To a methyl methoxypropionate, 14.4 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to prepare a monomer solution. Then, 60 g of 3-methoxypropionic acid was added. After the methyl ether 500 mL three-necked flask was purged with nitrogen for 30 minutes, it was heated to 70 ° C. while stirring, and the prepared monomer solution was added dropwise using a dropping funnel for 2 hours. The start of the dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was performed for 4 hours. After that, the temperature of the polymerization reaction liquid was set to 90 ° C. and stirred for 30 minutes. After that, the temperature of the polymerization reaction solution was set to 70 ° C, 77.9 mL of triethylamine was added, and the temperature was maintained at 70 ° C and stirred for 3 hours. After cooling to room temperature, 55.9 mL of 12N hydrochloric acid water was added, and after stirring for 30 minutes, ethyl acetate was added to carry out liquid separation. After the organic phase was washed with distilled water, the recovered organic phase was concentrated and diluted with methyl 3-methoxypropionate ((B-1) as a [B] solvent), thereby obtaining a polymer containing 40% by mass Polymer solution of (A-1). The Mw of the polymer (A-1) was 7,000.

[合成例9~合成例19] [Synthesis example 9 to synthesis example 19]

除了使用下述表1所示的種類及使用量的單體以外,與合成例8同樣地進行操作,合成各聚合物。將所合成的各聚合物的Mw及Mw/Mn一併示於表1中。此外,“-”表示並未使用符合條件的單體。合成例16及合成例19中,在使用保護羧基而成的甲基丙烯酸1-丁氧基乙酯作為提供結構單元(II)的化合物的情形時,在所得的[A]聚合物中,經脫保護而生成羧基。 Each polymer was synthesized in the same manner as in Synthesis Example 8 except that monomers of the kinds and amounts used in Table 1 below were used. The Mw and Mw / Mn of each synthesized polymer are shown in Table 1. In addition, "-" indicates that no eligible monomer was used. In Synthesis Example 16 and Synthesis Example 19, when 1-butoxyethyl methacrylate obtained by protecting a carboxyl group was used as a compound providing a structural unit (II), in the obtained [A] polymer, Deprotection to form a carboxyl group.

[合成例20](聚合物(a-1)的合成) [Synthesis Example 20] (Synthesis of polymer (a-1))

在具備冷卻管及攪拌機的燒瓶中,投入2,2'-偶氮雙(2,4-二甲基戊腈)7質量份及3-甲氧基丙酸甲酯(作為[B]溶劑的(B-1))200質量份。繼而,投入甲基丙烯酸40質量份及甲基丙烯酸甲酯60質量份並進行氮氣置換後,開始緩慢地攪拌。將聚合反應液的溫 度升溫至70℃,將所述溫度保持5小時後,添加甲基丙烯酸縮水甘油酯30質量份及四丁基溴化銨3質量份,進而在90℃下使其反應10小時,獲得含有40質量%聚合物(a-1)的聚合物溶液。聚合物(a-1)的Mw為10,000。 In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and methyl 3-methoxypropionate (as a solvent of [B] (B-1)) 200 parts by mass. Next, 40 parts by mass of methacrylic acid and 60 parts by mass of methyl methacrylate were introduced and replaced with nitrogen, and then, stirring was started slowly. The temperature of the polymerization reaction solution The temperature was raised to 70 ° C, and the temperature was maintained for 5 hours. Then, 30 parts by mass of glycidyl methacrylate and 3 parts by mass of tetrabutylammonium bromide were added, and further reacted at 90 ° C for 10 hours. A polymer solution of a mass% polymer (a-1). The Mw of the polymer (a-1) was 10,000.

[合成例21](聚合物(F-1)的合成) [Synthesis Example 21] (Synthesis of Polymer (F-1))

在具備冷卻管及攪拌機的燒瓶中,投入2,2'-偶氮雙(2,4-二甲基戊腈)8質量份及二乙二醇甲基乙醚(作為[B]溶劑的(B-2))220質量份,進而添加甲基丙烯酸13質量份、甲基丙烯酸縮水甘油酯40質量份、α-甲基-對羥基苯乙烯10質量份、苯乙烯10質量份、甲基丙烯酸四氫糠基酯12質量份、N-環己基順丁烯二醯亞胺15質量份及甲基丙烯酸正月桂基酯10質量份,進行氮氣置換後,緩慢地攪拌並將溶液的溫度上升至70℃,將所述溫度保持5小時並進行聚合,由此獲得含有聚合物(F-1)的溶液。所述溶液的固體成分濃度為31.9質量%。聚合物(F-1)的Mw為8,000,分子量分布(Mw/Mn)為2.3。 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ether ((B as a solvent of [B] -2)) 220 parts by mass, further added 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α -methyl-p-hydroxystyrene, 10 parts by mass of styrene, and four parts of methacrylic acid 12 parts by mass of hydrogen furfuryl ester, 15 parts by mass of N-cyclohexyl cis butylene diimide and 10 parts by mass of n-lauryl methacrylate. After nitrogen substitution, slowly stir and raise the temperature of the solution to 70 The temperature was maintained at 5 ° C. for 5 hours and polymerization was performed, thereby obtaining a solution containing a polymer (F-1). The solid content concentration of the solution was 31.9% by mass. The polymer (F-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[合成例22](聚合物(F-2)的合成) [Synthesis Example 22] (Synthesis of Polymer (F-2))

在具備冷卻管及攪拌機的燒瓶中,投入2,2'-偶氮雙異丁腈5質量份及乙酸3-甲氧基丁酯(作為[B]溶劑的(B-3))250質量份,進而添加甲基丙烯酸7質量份、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯18質量份、苯乙烯15質量份、3-甲基丙烯醯氧基丙基三乙氧基矽烷40質量份及甲基丙烯酸縮水甘油酯20質量份,進行氮氣置換後,緩慢地攪拌並將溶液的溫度上升至80℃,將所述溫度 保持5小時並進行聚合,由此獲得含有聚合物(F-2)的溶液。所述溶液的固體成分濃度為28.8質量%。所述聚合物(F-2)的Mw為12,000,分子量分布(Mw/Mn)為2.2。 In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate ((B-3) as the [B] solvent) were charged. 7 parts by mass of methacrylic acid, 18 parts by mass of tricyclo [5.2.1.0 2,6 ] decane-8-yl ester, 15 parts by mass of styrene, and 3-methacryloxypropyl After 40 parts by mass of triethoxysilane and 20 parts by mass of glycidyl methacrylate, after nitrogen substitution, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization. A solution containing the polymer (F-2) was obtained. The solid content concentration of the solution was 28.8% by mass. The polymer (F-2) had a Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.2.

[合成例23](聚合物(F-3)的合成) [Synthesis Example 23] (Synthesis of polymer (F-3))

在具備冷卻管及攪拌機的燒瓶中,投入2,2'-偶氮雙異丁腈5質量份及乙酸3-甲氧基丁酯250質量份,進而添加甲基丙烯酸7質量份、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯28質量份、苯乙烯25質量份及甲基丙烯酸縮水甘油酯40質量份,進行氮氣置換後,緩慢地攪拌並將溶液的溫度上升至80℃,將所述溫度保持5小時並進行聚合,由此獲得含有聚合物(F-3)的溶液。所述溶液的固體成分濃度為28.8質量%。所述聚合物(F-3)的Mw為10,000,分子量分布(Mw/Mn)為2.2。 In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and 7 parts by mass of methacrylic acid and methacrylic acid were further added. 28 parts by mass of tricyclo [5.2.1.0 2,6 ] decane-8-yl ester, 25 parts by mass of styrene, and 40 parts by mass of glycidyl methacrylate. After nitrogen substitution, the solution was slowly stirred and the temperature of the solution was increased. The temperature was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing the polymer (F-3). The solid content concentration of the solution was 28.8% by mass. The polymer (F-3) had an Mw of 10,000 and a molecular weight distribution (Mw / Mn) of 2.2.

[合成例24](聚合物(F-4)的合成) [Synthesis Example 24] (Synthesis of Polymer (F-4))

在具備冷卻管及攪拌機的燒瓶中,投入2,2'-偶氮雙異丁腈5質量份及乙酸3-甲氧基丁酯250質量份,進而添加甲基丙烯酸7質量份、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯28質量份、苯乙烯25質量份及甲基丙烯酸3,4-環氧基環己基甲酯40質量份,進行氮氣置換後,緩慢地攪拌並將溶液的溫度上升至80℃,將所述溫度保持5小時並進行聚合,由此獲得含有聚合物(F-4)的溶液。所述溶液的固體成分濃度為28.8質量%。所述聚合物(F-4)的Mw為11,000,分子量分布(Mw/Mn)為2.1。 In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and 7 parts by mass of methacrylic acid and methacrylic acid were further added. After 28 parts by mass of tricyclo [5.2.1.0 2,6 ] decane-8-yl ester, 25 parts by mass of styrene, and 40 parts by mass of 3,4-epoxycyclohexyl methyl methacrylate, after nitrogen substitution, The solution was slowly stirred and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing the polymer (F-4). The solid content concentration of the solution was 28.8% by mass. The polymer (F-4) had a Mw of 11,000 and a molecular weight distribution (Mw / Mn) of 2.1.

<硬化性樹脂組成物的製備> <Preparation of curable resin composition>

將硬化性樹脂組成物的製備中使用的[B]溶劑、[C]聚合性化合物、[D]自由基聚合起始劑及[E]酸產生劑示於以下。 The [B] solvent, [C] polymerizable compound, [D] radical polymerization initiator, and [E] acid generator used in the preparation of the curable resin composition are shown below.

[[B]溶劑] [[B] Solvent]

B-1:3-甲氧基丙酸甲酯 B-1: methyl 3-methoxypropionate

B-2:二乙二醇甲基乙醚 B-2: Diethylene glycol methyl ether

B-3:乙酸3-甲氧基丁酯 B-3: 3-methoxybutyl acetate

[[C]聚合性化合物] [[C] Polymerizable compound]

C-1:二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物(日本化藥公司的“卡亞拉德(KAYARAD)DPHA”) C-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA" of Nippon Kayaku Co., Ltd.)

C-2:丁二酸改性季戊四醇三丙烯酸酯(東亞合成公司的“亞羅尼斯(Aronix)TO-756”) C-2: Succinic acid-modified pentaerythritol triacrylate ("Aronix TO-756" of Toa Synthesis Corporation)

C-3:三羥甲基丙烷三丙烯酸酯 C-3: Trimethylolpropane triacrylate

C-4:三季戊四醇八丙烯酸酯與三季戊四醇七丙烯酸酯的混合物(大阪有機化學工業公司的“比斯克特(Viscoat)802”) C-4: Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate ("Viscoat 802" of Osaka Organic Chemical Industry Co., Ltd.)

C-5:丁二酸改性二季戊四醇五丙烯酸酯(東亞合成公司的“亞羅尼斯(Aronix)M-520”) C-5: Succinic acid-modified dipentaerythritol pentaacrylate ("Aronix M-520" of Toa Synthesis Corporation)

[[D]自由基聚合起始劑] [[D] radical polymerization initiator]

D-1:2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮(巴斯夫(BASF)公司的“艷佳固(Irgacure)907”) D-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one ("Irgacure 907" by BASF)

D-2:乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)(巴斯夫公司的“艷佳固(Irgacure)OXE02”) D-2: Ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime) (BASF Company's "Irgacure OXE02")

D-3:2,4-二乙基硫雜蒽酮 D-3: 2,4-Diethylthiaxanthone

[[E]酸產生劑] [[E] Acid generator]

E-1:4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚-1,2-萘醌二疊氮-5-磺酸酯 E-1: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinone di Azide-5-sulfonate

[實施例1] [Example 1]

將含有所述合成例8中合成的作為[A]聚合物的(A-1)100質量份與作為[B]溶劑的(B-1)150質量份的溶液、作為[B]溶劑的(B-1)200質量份、作為[C]聚合性化合物的(C-1)50質量份及作為[D]自由基聚合起始劑的(D-1)10質量份混合,利用孔徑0.2μm的薄膜過濾器進行過濾,由此製備硬化性樹脂組成物(J-1)。 A solution containing 100 parts by mass of (A-1) as the [A] polymer synthesized in the aforementioned Synthesis Example 8 and 150 parts by mass of (B-1) as the solvent of [B], and ( B-1) 200 parts by mass of (C-1) as a [C] polymerizable compound and 10 parts by mass of (D-1) as a [D] radical polymerization initiator were mixed, and a pore diameter of 0.2 μm was used. The thin-film filter was filtered to prepare a curable resin composition (J-1).

[實施例2~實施例25及比較例1~比較例3] [Example 2 to Example 25 and Comparative Example 1 to Comparative Example 3]

除了以含有下述表2及表3中所示的種類及含有量的各成分的方式混合各原料以外,與實施例1同樣地進行操作來製備硬化性樹脂組成物(J-2)~硬化性樹脂組成物(J-25)及硬化性樹脂組成物(CJ-1)~硬化性樹脂組成物(CJ-3)。表3中的“-”表示未使用符合條件的成分。 A curable resin composition (J-2) was prepared in the same manner as in Example 1 except that the raw materials were mixed so as to contain the respective components of the types and contents shown in Tables 2 and 3 below. Hardening resin composition (J-25) and hardening resin composition (CJ-1) to hardening resin composition (CJ-3). "-" In Table 3 indicates that no eligible component was used.

<評價> <Evaluation>

對於所述製備的硬化性樹脂組成物,依照下述方法評價硬化膜的黏附性及透明性、以及保存穩定性及放射線感度。 About the prepared curable resin composition, the adhesiveness and transparency of the cured film, storage stability, and radiation sensitivity were evaluated according to the following methods.

[硬化膜的黏附性] [Adhesiveness of hardened film]

硬化膜的黏附性是對硬化膜圖案在曝光延遲後進行評價。具體而言,首先,使用旋塗器在玻璃基板上塗佈硬化性樹脂組成物 後,在90℃下在加熱板上預烘烤2分鐘而形成膜厚3.0μm的塗膜。繼而,使用曝光機(佳能(Canon)公司的“MPA-600FA(ghi射線混合)”),介隔10μm的線與空間(1:1)圖案形成用遮罩,以700(J/m2)的曝光量進行曝光。其後,使用0.5質量%的四甲基氫氧化銨水溶液,在25℃下利用覆液法進行80秒的顯影。繼而,利用超純水進行1分鐘流水清洗,其後進行乾燥,從而在玻璃基板上形成圖案。利用光學顯微鏡觀察顯影後的基板,確認圖案剝離的有無。根據以下判斷基準評價圖案的黏附性。 The adhesiveness of the cured film was evaluated after the retardation of the cured film pattern. Specifically, first, a curable resin composition was applied to a glass substrate using a spin coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, using an exposure machine ("MPA-600FA (ghi-ray hybrid)" by Canon), a mask for pattern formation with a space of 10 μm between lines and space (1: 1) was used at 700 (J / m 2 ) Exposure. Thereafter, a 0.5% by mass tetramethylammonium hydroxide aqueous solution was used for development for 80 seconds at 25 ° C. by a liquid coating method. Subsequently, the glass was washed with flowing water for 1 minute with ultrapure water, and then dried to form a pattern on the glass substrate. The developed substrate was observed with an optical microscope, and the presence or absence of pattern peeling was confirmed. The adhesion of the pattern was evaluated according to the following judgment criteria.

幾乎未發現圖案剝離的情形:“○” Hardly found pattern peeling: "○"

略微發現圖案剝離的情形:“△” Slightly found pattern peeling: "△"

圖案發生剝離、基板上幾乎未殘留圖案的情形:“×” When the pattern is peeled off and there is almost no pattern left on the substrate: "×"

[硬化膜的透明性] [Transparency of hardened film]

在矽基板上,使用硬化性樹脂組成物形成厚度為3.0μm的塗膜。在潔淨烘箱中以220℃對所述矽基板加熱1小時而形成硬化膜。對所述硬化膜,使用分光光度計(日立製作所的“150-20型雙光束”)測定波長400nm時的透過率。將所述透過率(%)的值示於表2及表3中。關於透明性,在所述透過率為90%以上的情形時可評價為良好,在小於90%的情形時可評價為不良。 A coating film having a thickness of 3.0 μm was formed on a silicon substrate using a curable resin composition. The silicon substrate was heated at 220 ° C. for 1 hour in a clean oven to form a cured film. With respect to the cured film, a transmittance at a wavelength of 400 nm was measured using a spectrophotometer ("150-20 type dual beam" by Hitachi, Ltd.). The values of the transmittance (%) are shown in Tables 2 and 3. Regarding transparency, when the transmittance is 90% or more, it can be evaluated as good, and when it is less than 90%, it can be evaluated as poor.

[保存穩定性的評價] [Evaluation of storage stability]

將硬化性樹脂組成物在40℃的烘箱中放置1周。測定初期的黏度(1)與放置1周後的黏度(2),根據|黏度(2)-黏度(1)|×100/ 黏度(1)來算出黏度變化率(%)。|黏度(2)-黏度(1)|是指黏度(2)與黏度(1)的差的絕對值。將所述黏度變化率(%)的值示於表2及表3中。關於保存穩定性,在黏度變化率為5%以下的情形時可評價為良好,在超過5%的情形時可評價為不良。 The curable resin composition was left in an oven at 40 ° C for one week. Measure the initial viscosity (1) and the viscosity (2) after standing for 1 week, according to | viscosity (2)-viscosity (1) | × 100 / Viscosity (1) to calculate the viscosity change rate (%). | Viscosity (2)-Viscosity (1) | refers to the absolute value of the difference between viscosity (2) and viscosity (1). The values of the viscosity change rate (%) are shown in Tables 2 and 3. Regarding storage stability, a case where the viscosity change rate is 5% or less can be evaluated as good, and a case where it exceeds 5% can be evaluated as poor.

[放射線感度] [Radiation sensitivity]

使用旋塗器在玻璃基板上塗佈硬化性樹脂組成物後,在90℃下在加熱板上預烘烤2分鐘而形成膜厚3.0μm的塗膜。繼而,使用曝光機(佳能公司的“MPA-600FA(ghi射線混合)”),介隔具有10μm的線與空間(1:1)圖案的遮罩,且將曝光量設為變量而對塗膜照射放射線。其後,利用0.5質量%的四甲基氫氧化銨水溶液,在25℃下利用覆液法進行80秒的顯影。繼而,利用超純水進行1分鐘流水清洗,其後進行乾燥,由此在玻璃基板上形成圖案。此時,調查10μm的空間.圖案完全溶解所需要的曝光量。將所述曝光量(J/m2)的值示於表2及表3中。關於放射線感度,在所述曝光量為500(J/m2)以下的情形時可評價為良好。 After the curable resin composition was coated on a glass substrate using a spin coater, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, an exposure machine ("MPA-600FA (ghi-ray hybrid) from Canon") was used, and a mask having a line and space (1: 1) pattern of 10 μm was separated, and the exposure amount was set as a variable to coat the coating film. Expose radiation. Thereafter, development was performed for 80 seconds at 25 ° C. by a liquid coating method using a 0.5% by mass tetramethylammonium hydroxide aqueous solution. Then, the pattern was formed on a glass substrate by running-water washing with ultrapure water for 1 minute and then drying. At this time, investigate the space of 10 μm. The amount of exposure required to completely dissolve the pattern. The values of the exposure amount (J / m 2 ) are shown in Tables 2 and 3. The radiation sensitivity can be evaluated as good when the exposure amount is 500 (J / m 2 ) or less.

[表3] [table 3]

根據表2及表3的結果而明確:關於實施例的硬化性樹脂組成物,硬化膜的黏附性及透明性、保存穩定性、以及製成放射線硬化性樹脂組成物時的放射線感度優異。相對於此,比較例的硬化性樹脂組成物關於這些全部的性能均未獲得良好的結果。 From the results of Tables 2 and 3, it is clear that the curable resin composition of the examples has excellent adhesion and transparency of the cured film, storage stability, and excellent radiation sensitivity when the radiation-curable resin composition is formed. In contrast, the curable resin composition of the comparative example did not obtain good results with respect to all of these properties.

[產業上的可利用性] [Industrial availability]

本發明的硬化性樹脂組成物可形成黏附性及透明性優異的硬化膜,且保存穩定性優異。本發明的顯示元件用硬化膜由於黏附性及透明性優異,故可適宜地用作顯示元件的層間絕緣膜、保護膜、間隔件等。因此,這些可適宜地用於液晶裝置等顯示元件的製造工藝中。 The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and has excellent storage stability. Since the cured film for display elements of the present invention is excellent in adhesion and transparency, it can be suitably used as an interlayer insulating film, a protective film, a spacer, and the like of a display element. Therefore, these can be suitably used in the manufacturing process of a display element, such as a liquid crystal device.

Claims (11)

一種硬化性樹脂組成物,其含有聚合物及溶劑,所述聚合物具有下述式(1)所表示的結構單元、以及含酸性基的結構單元,式(1)中,R1、R2及R3分別獨立地為氫原子或碳數1~20的1價的烴基;R1、R2及R3中的2個以上可相互鍵結且與它們所鍵結的碳原子一起形成員環數3~20的環結構;R4為(a)碳數1~20的(n+1)價的烴基、(b)在(a)烴基的碳-碳間含有選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、或(c)(a)烴基及(b)基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及碳數1~12的烷氧基組成的群組中的至少1種取代而成的基;n為1~6的整數;n為2以上時,多個R1可相同也可不同,多個R2可相同也可不同,多個R3可相同也可不同;R5為-COO-*;*表示與R4鍵結的部位;R6為氫原子、甲基或氟化甲基;其中,當n為1時,R4為(d)碳數1~20的(n+1)價的環狀烴基、(e)在(d)環狀烴基的碳-碳間含有選自由氧原子、硫原子、-SO-及-SO2-組成的群組中的至少1種的基、(f)在碳數1~20的(n+1)價的鏈狀烴基的碳-碳間含有選自由硫原子、-SO-及-SO2-組成的群組中的至少1種的基、或(g)(d)環狀烴基、(e)基及(f)基所具有的氫原子的一部分或全部經選自由鹵素原子、氰基、硝基、羧基、亞磺酸基、巰基及碳數1~12的烷氧基組成的群組中的至少1種取代而成的基。A curable resin composition containing a polymer and a solvent, the polymer having a structural unit represented by the following formula (1) and a structural unit containing an acidic group, In formula (1), R 1 , R 2, and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; two or more of R 1 , R 2, and R 3 may be bonded to each other and Forms a ring structure with 3 to 20 member rings together with the carbon atoms to which they are bonded; R 4 is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) a (a) hydrocarbon group The carbon-to-carbon group contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO- and -SO 2- , or a hydrogen possessed by the (c) (a) hydrocarbon group and (b) group. Some or all of the atoms are substituted with at least one member selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms; n is an integer from 1 to 6; when n is 2 or more, multiple R 1 may be the same or different, multiple R 2 may be the same or different, multiple R 3 may be the same or different; R 5 is -COO- *; * Indicates a site bonded to R 4 ; R 6 is a hydrogen atom, a methyl group, or a fluorinated methyl group; wherein, when n is 1, R 4 is (d) (n + 1) having a carbon number of 1 to 20 ) Valent cyclic hydrocarbon group, (e) contains at least one selected from the group consisting of oxygen atom, sulfur atom, -SO- and -SO 2 -between carbons and carbons of (d) cyclic hydrocarbon group. (F) contains at least 1 selected from the group consisting of a sulfur atom, -SO- and -SO 2 -between the carbon-carbon of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms. Part of or all of the hydrogen atoms of (g) (d) cyclic hydrocarbon group, (e) group and (f) group are selected from halogen atom, cyano, nitro, carboxyl, and sulfinic acid. A group substituted with at least one of the group consisting of a group, a mercapto group and an alkoxy group having 1 to 12 carbon atoms. 如申請專利範圍第1項所述的硬化性樹脂組成物,其還含有:具有乙烯性不飽和鍵的聚合性化合物。The curable resin composition according to item 1 of the patent application scope, further comprising: a polymerizable compound having an ethylenically unsaturated bond. 如申請專利範圍第1項或第2項所述的硬化性樹脂組成物,其還含有:選自由自由基聚合起始劑及酸產生劑組成的群組中的至少1種。The curable resin composition according to claim 1 or claim 2, further comprising: at least one selected from the group consisting of a radical polymerization initiator and an acid generator. 如申請專利範圍第3項所述的硬化性樹脂組成物,其含有所述自由基聚合起始劑。The curable resin composition according to item 3 of the scope of patent application, which contains the radical polymerization initiator. 如申請專利範圍第4項所述的硬化性樹脂組成物,其中,所述自由基聚合起始劑為感放射線性。The curable resin composition according to item 4 of the scope of patent application, wherein the radical polymerization initiator is radiation-sensitive. 如申請專利範圍第3項所述的硬化性樹脂組成物,其含有所述酸產生劑。The curable resin composition according to item 3 of the scope of patent application, which contains the acid generator. 如申請專利範圍第6項所述的硬化性樹脂組成物,其中,所述酸產生劑為感放射線性。The curable resin composition according to item 6 of the scope of patent application, wherein the acid generator is radiation-sensitive. 如申請專利範圍第1項或第2項所述的硬化性樹脂組成物,其用於作為層間絕緣膜、保護膜或間隔件的顯示元件用硬化膜的形成。The curable resin composition according to item 1 or 2 of the scope of patent application, which is used for forming a cured film for a display element as an interlayer insulating film, a protective film, or a spacer. 一種顯示元件用硬化膜,其作為層間絕緣膜、保護膜或間隔件,且其是由如申請專利範圍第8項所述的硬化性樹脂組成物形成。A cured film for a display element, which serves as an interlayer insulating film, a protective film, or a spacer, and is formed of a curable resin composition as described in item 8 of the scope of patent application. 一種顯示元件用硬化膜的形成方法,其包括:在基板上形成塗膜的步驟;對所述塗膜的至少一部分照射放射線的步驟;對經所述放射線照射的塗膜進行顯影的步驟;以及對經所述顯影的塗膜進行加熱的步驟;且由如申請專利範圍第5項或第7項所述的硬化性樹脂組成物來形成所述塗膜。A method for forming a cured film for a display element, comprising: a step of forming a coating film on a substrate; a step of irradiating at least a portion of the coating film with radiation; a step of developing a coating film irradiated with the radiation; and A step of heating the developed coating film; and forming the coating film from a curable resin composition according to item 5 or 7 of the scope of patent application. 一種顯示元件,其包括:如申請專利範圍第9項所述的顯示元件用硬化膜。A display element includes the cured film for a display element according to item 9 of the scope of patent application.
TW104107834A 2014-03-13 2015-03-12 Curable resin composition, cured film for display element, method for forming cured film for display element, and display element TWI649339B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014050848A JP6390125B2 (en) 2014-03-13 2014-03-13 Curable resin composition, cured film for display element, method for forming the same, and display element
JP2014-050848 2014-03-13

Publications (2)

Publication Number Publication Date
TW201534628A TW201534628A (en) 2015-09-16
TWI649339B true TWI649339B (en) 2019-02-01

Family

ID=54083859

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104107834A TWI649339B (en) 2014-03-13 2015-03-12 Curable resin composition, cured film for display element, method for forming cured film for display element, and display element

Country Status (4)

Country Link
JP (1) JP6390125B2 (en)
KR (1) KR102252030B1 (en)
CN (1) CN104914668B (en)
TW (1) TWI649339B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102630893B1 (en) * 2015-11-25 2024-01-31 롬엔드하스전자재료코리아유한회사 Photosensitive resin composition and cured film prepared therefrom
JP6750213B2 (en) * 2015-12-08 2020-09-02 Jsr株式会社 Radiation-sensitive resin composition, method for forming cured film, cured film, semiconductor element and display element
KR102654731B1 (en) * 2017-09-28 2024-04-03 제이에스알 가부시끼가이샤 Radiation-sensitive resin composition and use thereof
JP7122819B2 (en) * 2017-12-06 2022-08-22 富士フイルム株式会社 Photosensitive composition, transfer film, cured film, touch panel and manufacturing method thereof
TWI795489B (en) * 2018-12-14 2023-03-11 奇美實業股份有限公司 Chemically amplified positive photosensitive resin composition and application thereof
JPWO2022259893A1 (en) 2021-06-07 2022-12-15
CN118541644A (en) * 2021-12-24 2024-08-23 富士胶片株式会社 Method for producing laminate having conductor pattern, photosensitive composition, and transfer film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005060531A (en) * 2003-08-12 2005-03-10 Fuji Photo Film Co Ltd Alkali-soluble polymer, method for producing the same, polymerizable composition containing the same and image-recording material using the same
CN1651512A (en) * 2004-02-02 2005-08-10 富士胶片株式会社 Polymerizable composition
JP2011022509A (en) * 2009-07-17 2011-02-03 Fujifilm Corp Positive photosensitive resin composition for organic insulating film, organic insulating film, organic el display device and liquid crystal display device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3951396B2 (en) 1997-12-12 2007-08-01 日立化成工業株式会社 Photosensitive film for resin spacer formation
KR100484444B1 (en) 2000-09-08 2005-04-22 엘지전자 주식회사 Method for controlling web fax service system with authorization function
JP2004117555A (en) * 2002-09-24 2004-04-15 Fuji Photo Film Co Ltd Photo or thermosetting composition
JP4119772B2 (en) * 2002-09-25 2008-07-16 富士フイルム株式会社 Image recording material
JP2006184521A (en) * 2004-12-27 2006-07-13 Sekisui Chem Co Ltd Photocurable resin composition
JP5344790B2 (en) * 2006-12-28 2013-11-20 富士フイルム株式会社 Curable composition, color filter and method for producing the same
JP2009098602A (en) * 2007-09-26 2009-05-07 Fujifilm Corp Negative resist composition and resist pattern forming method
JP5181613B2 (en) * 2007-10-17 2013-04-10 日油株式会社 Thermosetting resin composition for color filter and color filter
JP5313740B2 (en) * 2009-03-31 2013-10-09 東京応化工業株式会社 Photosensitive resin composition and liquid crystal panel
JP5505066B2 (en) * 2010-04-28 2014-05-28 Jsr株式会社 Radiation-sensitive resin composition, interlayer insulating film of display element, protective film and spacer, and method for forming them

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005060531A (en) * 2003-08-12 2005-03-10 Fuji Photo Film Co Ltd Alkali-soluble polymer, method for producing the same, polymerizable composition containing the same and image-recording material using the same
CN1651512A (en) * 2004-02-02 2005-08-10 富士胶片株式会社 Polymerizable composition
JP2011022509A (en) * 2009-07-17 2011-02-03 Fujifilm Corp Positive photosensitive resin composition for organic insulating film, organic insulating film, organic el display device and liquid crystal display device

Also Published As

Publication number Publication date
KR20150107639A (en) 2015-09-23
JP2015175923A (en) 2015-10-05
JP6390125B2 (en) 2018-09-19
CN104914668B (en) 2019-05-14
CN104914668A (en) 2015-09-16
KR102252030B1 (en) 2021-05-13
TW201534628A (en) 2015-09-16

Similar Documents

Publication Publication Date Title
TWI649339B (en) Curable resin composition, cured film for display element, method for forming cured film for display element, and display element
JP6750213B2 (en) Radiation-sensitive resin composition, method for forming cured film, cured film, semiconductor element and display element
WO2011046230A1 (en) Radiation-sensitive resin composition and method of forming interlayer dielectric
JP4905700B2 (en) Radiation-sensitive resin composition, interlayer insulating film, microlens and method for forming them
KR101421299B1 (en) Radiation-sensitive resin composition, interlayer insulation film and microlens, and process for producing them
TWI611266B (en) Negative-type radiation-radiating resin composition, cured film, method of forming the same, semiconductor element, and display element
JP2015069164A (en) Radiation-sensitive resin composition, insulation film of display element, method for forming the same, and display element
JP2007101762A (en) Radiation-sensitive resin composition and formation of interlayer insulation film and microlens
JP6939381B2 (en) Curable resin composition for interlayer insulating film, interlayer insulating film, display element, and method for forming interlayer insulating film
JP4677871B2 (en) Radiation sensitive resin composition and formation of interlayer insulating film and microlens
JP5177404B2 (en) Radiation-sensitive resin composition, interlayer insulating film and microlens and method for producing the same
JP4544370B2 (en) Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof
KR101289223B1 (en) Radiation Sensitive Resin Composition, and Formation of Interlayer Insulating Film and Microlens
JP2016160393A (en) Curable resin composition, cured film for display element, method for forming the same, and display element
JP2010085929A (en) Radiation-sensitive resin composition, and spacer for liquid crystal display element and method for manufacturing the spacer
JP4581810B2 (en) Radiation-sensitive resin composition for forming interlayer insulating film and radiation-sensitive composition for forming microlens
JP2007101759A (en) Radiation-sensitive resin composition, and formation of interlayer insulation film and microlens
JP2007128061A (en) Radiation-sensitive resin composition, method for forming interlayer insulation film and microlens, and interlayer insulation film and microlens
KR101744645B1 (en) Resin composition for forming cured film, the cured film and method for forming the same, and display device
KR20100109848A (en) Radiation-sensitive resin composition, interlayer insulating film and method for forming the same
JP2008175889A (en) Radiation-sensitive resin composition, interlayer insulating film and microlens, and method for producing those
JP6443021B2 (en) Radiation-sensitive resin composition, insulating film, method for forming the same, and display element
JP4581952B2 (en) Radiation sensitive resin composition and formation of interlayer insulating film and microlens
TWI394000B (en) Radiation sensitive resin composition, radiation sensitive dry film, interlayer dielectric film and a forming method thereof, and microlens and a forming method thereof
JP2015092233A (en) Radiation-sensitive resin composition, interlayer insulator for display element, method for forming the same and display element