JP7178986B2 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

Info

Publication number
JP7178986B2
JP7178986B2 JP2019506286A JP2019506286A JP7178986B2 JP 7178986 B2 JP7178986 B2 JP 7178986B2 JP 2019506286 A JP2019506286 A JP 2019506286A JP 2019506286 A JP2019506286 A JP 2019506286A JP 7178986 B2 JP7178986 B2 JP 7178986B2
Authority
JP
Japan
Prior art keywords
monomer unit
group
meth
resin composition
radically polymerizable
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
JP2019506286A
Other languages
Japanese (ja)
Other versions
JPWO2018169036A1 (en
Inventor
幸樹 椿
豊 星野
秀之 高野
大 杉山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Organic Chemicals Ind.,Ltd.
Original Assignee
Osaka Organic Chemicals Ind.,Ltd.
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 Osaka Organic Chemicals Ind.,Ltd. filed Critical Osaka Organic Chemicals Ind.,Ltd.
Publication of JPWO2018169036A1 publication Critical patent/JPWO2018169036A1/en
Application granted granted Critical
Publication of JP7178986B2 publication Critical patent/JP7178986B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Liquid Crystal (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Description

本発明は，（メタ）アクリル系樹脂組成物に関し，より詳しくは感光性樹脂組成物，特に，フォトスペーサー等に用いられる感光性樹脂組成物に関する。 TECHNICAL FIELD The present invention relates to a (meth)acrylic resin composition, and more particularly to a photosensitive resin composition, particularly to a photosensitive resin composition used for photospacers and the like.

液晶ディスプレイ（ＬＣＤ）等の表示装置において，絶縁膜，保護膜，液晶層を一定の厚みに保つためのスペーサー等の硬化膜として，複数の（メタ）アクリロイルオキシ基を含む構造単位とカルボキシル基を含む構造単位を有する重合体と，塩基性化合物を含有する硬化性樹脂組成物が知られている（特許文献１）。 In display devices such as liquid crystal displays (LCDs), structural units containing multiple (meth)acryloyloxy groups and carboxyl groups are used as cured films such as spacers to keep the thickness of the insulating film, protective film, and liquid crystal layer constant. A curable resin composition containing a basic compound and a polymer having a structural unit containing such a compound is known (Patent Document 1).

液晶ディスプレイ（ＬＣＤ）の製造において，液晶層の厚み（前後の配向膜の間のギャップ）が一定となるよう高度に制御することが求められ，その成否が画質の良否に直結する。このため，スペーサーが用いられ，近年では，カラーフィルター上等にカラム状のフォトスペーサー（ＰＳ）が形成されるようになっている。フォトスペーサーは，フォトリソグラフィーにより形成されることから，その作製材料として良好な感光性を有するレジスト必要である。同時に，作製工程の効率の点から，迅速な現像性，即ちレジストの露光後に，不要な部分が現像液によって迅速に除去できることが求められる。更には，ディスプレイ画面に対し指などにより外力がかかった場合，特にカラム状のフォトスペーサーに外力が集中するが，フォトスペーサーは，それにより幾らか圧縮された場合でも圧力の除去後には実質的な回復が可能であるよう，用いるレジストが優れた弾性回復率の硬化物を与えるものであることが重要である。 In the manufacture of a liquid crystal display (LCD), it is required to control the thickness of the liquid crystal layer (gap between the front and rear alignment layers) to be constant, and the success or failure of this control is directly linked to the quality of the image. Therefore, spacers are used, and in recent years, columnar photospacers (PS) have been formed on color filters and the like. Since the photospacer is formed by photolithography, a resist with good photosensitivity is required as a material for its fabrication. At the same time, from the viewpoint of the efficiency of the manufacturing process, rapid developability, that is, the ability to quickly remove unnecessary portions with a developer after exposure of the resist is required. Furthermore, when an external force is applied to the display screen by a finger or the like, the external force concentrates particularly on the column-shaped photospacers. It is important that the resist used gives a cured product with good elastic recovery so that recovery is possible.

特開２０１６－１６３９３号公報JP 2016-16393 A

本発明の目的は，活性エネルギー線に対する良好な感光性（硬化性）と，感光後の迅速な現像性を有し，且つ外力の負荷による変形に対して優れた弾性回復率を示す硬化物を与えるものである，活性エネルギー線硬化型の樹脂組成物を提供することである。 The object of the present invention is to provide a cured product that has good photosensitivity (curability) to active energy rays, rapid developability after photosensitivity, and excellent elastic recovery rate against deformation due to external force load. It is to provide an active energy ray-curable resin composition.

上記目的に沿って研究の結果，本発明者らは，複数の末端にラジカル重合性置換基を備えてなる分枝した側鎖を有するタイプのモノマーと，複数の末端にカルボキシル基とラジカル重合性置換基とを備えてなる分枝した側鎖を有するタイプのモノマーとを構成単位として含んでなる重合性樹脂と，多官能（メタ）アクリレート系モノマーとを含んでなる重合性樹脂組成物が，これを光硬化させるとき，優れた感光性を有し，感光後はアルカリ溶液への迅速な現像性を示し，得られる硬化物が優れた弾性回復率を有することを見出した。本発明は，当該発見に基づき，更に検討を重ねて完成させたものである。即ち，本発明は以下を提供する。 As a result of research in line with the above purpose, the present inventors have found a type of monomer having a branched side chain with radically polymerizable substituents at multiple ends, and a carboxyl group and radically polymerizable monomer at multiple ends. A polymerizable resin composition comprising a polymerizable resin comprising a monomer having a branched side chain with a substituent as a structural unit and a polyfunctional (meth)acrylate monomer, It has been found that when this is photocured, it exhibits excellent photosensitivity, exhibits rapid developability in an alkaline solution after exposure, and the resulting cured product has an excellent elastic recovery rate. The present invention has been completed through further studies based on this discovery. That is, the present invention provides the following.

１．各々がラジカル重合性置換基に終わる２～３個の末端を有する分枝した側鎖を備えたモノマー単位（１）と，カルボキシル基に終わる末端とラジカル重合性置換基に終わる末端とを有する２つに分枝した側鎖を備えたモノマー単位（２）と，又は更に，ラジカル重合性置換基で終わる１つの末端を有する側鎖を備えたモノマー単位（３）と，を構成要素として含んでなる重合性（メタ）アクリル系ポリマー（Ａ）と，多官能（メタ）アクリレート系モノマー（Ｂ）と光重合開始剤（Ｃ）を含んでなる，感光性樹脂組成物。
２．該重合性（メタ）アクリル系ポリマー（Ａ）において，該モノマー単位（１）における該ラジカル重合性置換基は，側鎖の一部をなす炭素数３～５個を含んでなる炭化水素鎖（Ｌ）上に置換しており，該モノマー単位（２）における該ラジカル重合性置換基は，側鎖の一部をなす炭素数３～５個を含んでなる炭化水素鎖（Ｍ）上に置換すると共に，該炭化水素鎖（Ｍ）上に基－ＯＣ(Ｏ)－Ｚ－を介して該カルボキシル基が結合しており，ここに該基の一部をなす基－Ｚ－は，炭素数２～７個からなる，飽和若しくは不飽和の鎖状若しくは環状の，炭化水素骨格又はベンゼン環を含んでなるものであり，且つ該モノマー単位（３）における該ラジカル重合性置換基が，側鎖の一部をなす炭素数３～５個を含んでなる炭化水素鎖上に置換しているものである，上記１の樹脂組成物。
３．該モノマー単位（２）における基－Ｚ－の２個の結合位置が，当該基を構成する炭素原子のうち互いに隣接する２個の炭素原子上に存在するものである，上記１又は２の樹脂組成物。
４．該ラジカル重合性置換基が，相互に独立して，（メタ）アクリロイルオキシ基である，上記１～３の何れかの樹脂組成物。
５．該モノマー単位（１）が，アクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ａ）と，メタクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ｂ）とからなるものである，上記１～４の何れかの樹脂組成物。
６．該重合性（メタ）アクリル系ポリマー（Ａ）を構成する該モノマー単位間のモル比が，モノマー単位（１）：モノマー単位（２）：モノマー単位（３）＝２０～８０：５～５０：０～３０である，上記１～５の何れかの樹脂組成物。
７．該重合性（メタ）アクリル系ポリマー（Ａ）が次の一般式：1. Monomeric units (1) with branched side chains each having 2-3 ends terminating in a radically polymerizable substituent and 2 having a terminal terminating in a carboxyl group and a terminal terminating in a radically polymerizable substituent comprising as building blocks a monomer unit (2) with a two-branched side chain, or additionally a monomer unit (3) with a single terminal side chain ending with a radically polymerizable substituent A photosensitive resin composition comprising a polymerizable (meth)acrylic polymer (A), a polyfunctional (meth)acrylate monomer (B), and a photopolymerization initiator (C).
2. In the polymerizable (meth)acrylic polymer (A), the radically polymerizable substituent in the monomer unit (1) is a hydrocarbon chain ( L), and the radically polymerizable substituent in the monomer unit (2) is substituted on the hydrocarbon chain (M) containing 3 to 5 carbon atoms forming part of the side chain At the same time, the carboxyl group is bonded to the hydrocarbon chain (M) via the group -OC(O)-Z-, and the group -Z- forming part of the group here has a carbon number 2 to 7 saturated or unsaturated chain or cyclic hydrocarbon skeletons or benzene rings, and the radically polymerizable substituent in the monomer unit (3) is a side chain The resin composition of 1 above, which is substituted on a hydrocarbon chain containing 3 to 5 carbon atoms forming a part of.
3. The resin according to 1 or 2 above, wherein the two bonding positions of the group -Z- in the monomer unit (2) are present on two adjacent carbon atoms among the carbon atoms constituting the group. Composition.
4. 4. The resin composition according to any one of 1 to 3 above, wherein the radically polymerizable substituents are (meth)acryloyloxy groups independently of each other.
5. The monomer unit (1) consists of a monomer unit (1a) having an acryloyloxy group as the radically polymerizable substituent and a monomer unit (1b) having a methacryloyloxy group as the radically polymerizable substituent. , the resin composition according to any one of 1 to 4 above.
6. The molar ratio between the monomer units constituting the polymerizable (meth)acrylic polymer (A) is monomer unit (1): monomer unit (2): monomer unit (3) = 20 to 80: 5 to 50: 5. The resin composition according to any one of 1 to 5 above, wherein the resin composition is 0 to 30.
7. The polymerizable (meth)acrylic polymer (A) has the following general formula:

Figure 0007178986000001
Figure 0007178986000001

〔式中，各Ｒ１は，独立して，水素原子又はメチル基を表し，Ｘ１，Ｘ２，Ｘ３及びＸ４は，それぞれ独立して，下記一般式（１）で示される置換基を表し，[Wherein, each R 1 independently represents a hydrogen atom or a methyl group, and X 1 , X 2 , X 3 and X 4 each independently represents a substituent represented by the following general formula (1) represents

Figure 0007178986000002
Figure 0007178986000002

（式中，Ｒ２は，水素原子又はメチル基を表し，「＊－」は単結合を表す。），
Ｒ３は，下記構造式で表される置換基の何れか表し，(Wherein, R 2 represents a hydrogen atom or a methyl group, and "*-" represents a single bond.),
R 3 represents any of the substituents represented by the following structural formulas,

Figure 0007178986000003
Figure 0007178986000003

ｌ，ｍ及びｎは，比ｌ：ｍ：ｎの形で各モノマー単位相互のモル比を表す。〕で示されるものである，上記１～５の何れかの樹脂組成物。
８．該重合性（メタ）アクリル系ポリマー（Ａ）において，比ｌ：ｍ：ｎ＝２０～８０：５～５０：０～３０である，上記７の樹脂組成物。
９．該重合性（メタ）アクリル系ポリマー（Ａ）の一般式中，次式：l, m and n represent the molar ratios of each monomer unit to each other in the form of the ratio l:m:n. ]. The resin composition according to any one of 1 to 5 above.
8. 8. The resin composition according to 7 above, wherein the ratio l:m:n is 20-80:5-50:0-30 in the polymerizable (meth)acrylic polymer (A).
9. In the general formula of the polymerizable (meth)acrylic polymer (A), the following formula:

Figure 0007178986000004
Figure 0007178986000004

で示されるモノマー単位（１）が，Ｘ１，Ｘ２共にアクリロイルオキシ基であるモノマー単位（１ａ）と，Ｘ１，Ｘ２共にメタクリロイルオキシ基であるモノマー単位（１ｂ）とを含んでなるものである，上記７又は８の樹脂組成物。
１０．該重合性（メタ）アクリル系ポリマー（Ａ）が，次式comprising a monomer unit (1a) in which both X 1 and X 2 are acryloyloxy groups, and a monomer unit (1b) in which both X 1 and X 2 are methacryloyloxy groups. The resin composition of 7 or 8 above.
10. The polymerizable (meth)acrylic polymer (A) has the following formula

Figure 0007178986000005
Figure 0007178986000005

Figure 0007178986000006
Figure 0007178986000006

Figure 0007178986000007
Figure 0007178986000007

の何れかで示されるものである，上記７～９の何れかの組成物。
１１．該多官能（メタ）アクリレート系モノマー（Ｂ）が，ジペンタエリスリトールヘキサアクリレート，ジペンタエリスリトールポリアクリレート，ペンタエリスリトールトリアクリレート，ペンタエリスリトールテトラアクリレート，エトキシ化ペンタエリスリトールテトラアクリレート，ジトリメチロールプロパンテトラアクリレート，トリメチロールプロパントリアクリレート，エトキシ化イソシアヌル酸トリアクリレート，及びε-カプロラクトン変性トリス－（２－アクリロキシエチル）イソシアヌレートからなる群より選ばれるものである，上記１～１０の何れかの樹脂組成物。10. The composition according to any one of 7 to 9 above, which is represented by any of
11. The polyfunctional (meth)acrylate monomer (B) includes dipentaerythritol hexaacrylate, dipentaerythritol polyacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, tri 11. The resin composition according to any one of 1 to 10 above, which is selected from the group consisting of methylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate.

１２．該重合性（メタ）アクリル系ポリマー（Ａ）が，該モノマー単位（１），（２），及び（３）の何れとも異なるモノマー単位（４）を更に含んでなるものである，上記１～５の何れかの樹脂組成物。
12. 1 to 1 above, wherein the polymerizable (meth)acrylic polymer (A) further comprises a monomer unit (4) different from any of the monomer units (1), (2), and (3); 5. Any resin composition.

本発明によれば，活性エネルギー線に対する良好な反応性（本発明において，包括的に「感光性」という。）を示して硬化し，感光後のアルカリ性現像液に対する迅速な現像性を有する樹脂組成物を得ることができる。また本発明の樹脂組成物は，外力の負荷による変形に対して優れた弾性回復率を示す硬化物を与えることができる。 According to the present invention, a resin composition that exhibits good reactivity to active energy rays (in the present invention, collectively referred to as "photosensitivity") and cures, and has rapid developability with an alkaline developer after exposure. can get things. Moreover, the resin composition of the present invention can provide a cured product exhibiting excellent elastic recovery against deformation due to external force.

本発明において，「活性エネルギー線」とは，紫外線，電子線，α線，β線，γ線等の電離放射線をいう。これらのうち，取扱いに便利なものとして，例えば紫外線が挙げられ，照射には高圧水銀灯，超高圧水銀灯を簡便に用いることができる。 In the present invention, the term "active energy ray" refers to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays are considered to be convenient for handling, and high-pressure mercury lamps and ultra-high-pressure mercury lamps can be used simply for irradiation.

本発明において，「（メタ）アクリル系」の語は，アクリル酸及びメタクリル酸に基づく化合物を，両者を区別することなく包括的に意味する。「（メタ）アクリレート」の語も同様である。 In the present invention, the term "(meth)acrylic" comprehensively means compounds based on acrylic acid and methacrylic acid without distinguishing between the two. The same applies to the term "(meth)acrylate".

本発明において，重合性（メタ）アクリル系ポリマー（Ａ）は，モノマー単位（１）及（２）を，又は更にモノマー単位（３）を含んでなり，それらのモノマー単位は，各々（メタ）アクリル系モノマー単位である。本発明において，各モノマー単位の構造について「側鎖」というときは，それらが共通して有する（メタ）アクリレート部分が付加重合してなる主鎖に対する側鎖を構成する部分をいう。 In the present invention, the polymerizable (meth)acrylic polymer (A) comprises monomer units (1) and (2), or further monomer units (3), each of which comprises (meth) It is an acrylic monomer unit. In the present invention, when the structure of each monomer unit is referred to as a "side chain", it means a portion constituting a side chain with respect to the main chain formed by addition polymerization of the (meth)acrylate portion that these monomer units have in common.

モノマー単位（１）は，各々がラジカル重合性置換基に終わる２～３個の末端を有する分枝した側鎖を備えている。それらラジカル重合性置換基は，好ましくは，炭化水素鎖（Ｌ）上にそれぞれ置換しており，当該炭化水素鎖（Ｌ）は，好ましくは基－ＣＯＯ－を介して，ポリマーの主鎖に結合している。当該炭化水素鎖（Ｌ）を構成する炭素数は好ましくは３～５個であり，より好ましくは３又は４個であり，特に好ましくは３個である。 Monomer unit (1) has a branched side chain with 2-3 ends each terminating in a radically polymerizable substituent. The radically polymerizable substituents are preferably each substituted on the hydrocarbon chain (L), and the hydrocarbon chain (L) is preferably attached to the main chain of the polymer via the group -COO-. is doing. The number of carbon atoms constituting the hydrocarbon chain (L) is preferably 3 to 5, more preferably 3 or 4, and particularly preferably 3.

モノマー単位（２）は，カルボキシル基に終わる末端とラジカル重合性置換基に終わる末端とを有する２つに分枝した側鎖を備えている。ここに，当該ラジカル重合性置換基は，好ましくは，炭化水素鎖（Ｍ）上に置換しており，当該炭化水素鎖（Ｍ）は，好ましくは基－ＣＯＯ－を介して，ポリマーの主鎖に結合している。当該炭化水素鎖（Ｍ）を構成する炭素の数は好ましくは３～５個であり，より好ましくは３又は４個であり，特に好ましくは３個である。他方，当該カルボキシル基は，当該炭化水素鎖（Ｍ）上に，基－ＯＣ(Ｏ)－Ｚ－を介して置換している。ここに，当該基の一部をなす基－Ｚ－は，炭素数２～７個からなり，飽和若しくは不飽和の鎖状若しくは環状の，炭化水素骨格又はベンゼン環を含んでなる。また，基－Ｚ－は，その２個の結合位置が，当該基を構成する炭素原子のうち互いに隣接する２個の炭素原子上に存在することが，より好ましい。また，モノマー単位（２）は，分子量が１０００未満であることが好ましい。 Monomeric unit (2) has a two-branched side chain with a terminal terminating in a carboxyl group and a terminal terminating in a radically polymerizable substituent. Here, the radically polymerizable substituent is preferably substituted on the hydrocarbon chain (M), and the hydrocarbon chain (M) is preferably attached to the main chain of the polymer via the group -COO- is bound to The number of carbon atoms constituting the hydrocarbon chain (M) is preferably 3-5, more preferably 3 or 4, and particularly preferably 3. On the other hand, the carboxyl group is substituted on the hydrocarbon chain (M) via the group -OC(O)-Z-. Here, the group -Z- forming part of the group has 2 to 7 carbon atoms and includes a saturated or unsaturated chain or cyclic hydrocarbon skeleton or benzene ring. Further, it is more preferable that the two bonding positions of the group -Z- are present on two carbon atoms adjacent to each other among the carbon atoms constituting the group. Moreover, the monomer unit (2) preferably has a molecular weight of less than 1,000.

モノマー単位（３）は，ラジカル重合性置換基で終わる１つの末端を有する側鎖を備えている。当該ラジカル重合性置換基は，好ましくは，炭化水素鎖（Ｎ）上に置換しており，当該炭化水素鎖（Ｎ）は，好ましくは基－ＣＯＯ－を介して，ポリマーの主鎖に結合している。当該炭化水素鎖（Ｎ）を構成する炭素の数は好ましくは３～５個であり，より好ましくは３又は４個であり，特に好ましくは３個である。 Monomer unit (3) has a side chain with one end that terminates in a radically polymerizable substituent. The radically polymerizable substituent is preferably substituted on the hydrocarbon chain (N), and the hydrocarbon chain (N) is preferably attached to the main chain of the polymer via the group -COO-. ing. The number of carbon atoms constituting the hydrocarbon chain (N) is preferably 3-5, more preferably 3 or 4, and particularly preferably 3.

モノマー単位（１）～（３）において，「ラジカル重合性置換基」は，好ましくは（メタ）アクリロイルオキシ基である。該モノマー単位（１）は，アクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ａ）と，メタクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ｂ）とからなるものであってもよい。 In the monomer units (1) to (3), the "radical polymerizable substituent" is preferably a (meth)acryloyloxy group. The monomer unit (1) consists of a monomer unit (1a) having an acryloyloxy group as the radically polymerizable substituent and a monomer unit (1b) having a methacryloyloxy group as the radically polymerizable substituent. may

該重合性（メタ）アクリル系ポリマー（Ａ）は，上記モノマー単位（３）を含まずに，モノマー単位（１）及び（２）で構成されていることができる。その場合，当該ポリマーにおけるモノマー単位（１）とモノマー単位（２）とのモル比に明確な限界はないが，一般に好ましくは，モノマー単位（１）：モノマー単位（２）＝２０～８０：５～５０であり，より好ましくは５０～７０：１０～３０である。 The polymerizable (meth)acrylic polymer (A) may be composed of monomer units (1) and (2) without containing the monomer unit (3). In that case, there is no definite limit to the molar ratio of monomer units (1) and monomer units (2) in the polymer, but generally preferably monomer unit (1):monomer unit (2) = 20 to 80:5 ~50, more preferably 50-70:10-30.

該重合性（メタ）アクリル系ポリマー（Ａ）が，モノマー単位（３）を含んで構成されている場合，モノマー単位（１）～（３）の相互のモル比に明確な限界はないが，一般に好ましくは，モノマー単位（１）：モノマー単位（２）：モノマー単位（３）＝２０～８０：５～５０：０～３０であり，より好ましくは５０～７０：１０～３０：０～１０である。 When the polymerizable (meth)acrylic polymer (A) contains the monomer unit (3), there is no clear limit to the mutual molar ratio of the monomer units (1) to (3), Generally preferably monomer unit (1): monomer unit (2): monomer unit (3) = 20-80: 5-50: 0-30, more preferably 50-70: 10-30: 0-10 is.

また，フォトスペーサの弾性回復率を高める観点からは，該重合性（メタ）アクリル系ポリマー（Ａ）は二重結合当量が１００～２７０のものであることが好ましい。ここで，「二重結合当量」とは，アクリロイル基１モルに対する樹脂組成物のグラム数をいう。また，「樹脂組成物のグラム数」とは，樹脂組成物の全体（但し，溶媒を除く）の質量を意味する。 From the viewpoint of increasing the elastic recovery rate of the photospacer, the polymerizable (meth)acrylic polymer (A) preferably has a double bond equivalent of 100-270. Here, "double bond equivalent" refers to the number of grams of the resin composition per 1 mol of acryloyl groups. Also, the term "the number of grams of the resin composition" means the mass of the entire resin composition (excluding the solvent).

なお，該重合性（メタ）アクリル系ポリマー（Ａ）は，本発明の目的に反しない限り，上記モノマー単位（１）～（３）以外の追加のモノマー単位を更に含んでいてもよい。そのような追加のモノマー単位は，例えば，所望により，本発明の感光性樹脂組成物のガラス転移点（Ｔｇ）や疎水性等の物性を調整する目的で利用できる。追加のモノマー単位「モノマー単位（４）」を含めたとき，該重合性（メタ）アクリル系ポリマー（Ａ）を構成する各モノマー単位のモル比に明確な限定はないが，一般に好ましくは，モノマー単位（１）：モノマー単位（２）：モノマー単位（３）：モノマー単位（４）＝２０～８０：５～５０：０～３０：０～４０であり，より好ましくは５０～７０：１０～３０：０～１０：０～３０である。 The polymerizable (meth)acrylic polymer (A) may further contain additional monomer units other than the monomer units (1) to (3) as long as it does not contradict the object of the present invention. Such additional monomer units can be used, if desired, for the purpose of adjusting physical properties such as the glass transition point (Tg) and hydrophobicity of the photosensitive resin composition of the present invention. When the additional monomer unit "monomer unit (4)" is included, there is no clear limitation on the molar ratio of each monomer unit constituting the polymerizable (meth)acrylic polymer (A), but generally preferably, the monomer Unit (1): Monomer unit (2): Monomer unit (3): Monomer unit (4) = 20-80:5-50:0-30:0-40, more preferably 50-70:10- 30:0-10:0-30.

上記追加のモノマー単位の例としては，重合性（メタ）アクリル系モノマーが挙げられるが，これに限定されない。また重合性（メタ）アクリル系モノマーの具体例としては，ジシクロペンテニルアクリレ－ト，ジシクロペンテニルオキシエチルアクリレ－ト，ジシクロペンタニルアクリレ－ト，ベンジルアクリレート，ノニルフェノキシポリエチレングリコールアクリレート，ノニルフェノキシポリエチレングリコールアクリレート，ノナンジオールジアクリレ－ト，ポリプロピレングリコールアクリレート，１，４－ブタンジオールジメタクリレート，ジシクロペンテニルオキシエチルメタクリレート，ジシクロペンタニルメタクリレート，ペンタメチルピペリジルメタクリレ－ト，テトラメチルピペリジルメタクリレート，メトキシポリエチレングリコールメタクリレート，ベンジルメタクリレート，ネオペンチルグリコールジメタクリレート，ポリエチレングリコールジメタクリレート等が挙げられるが，これらに限定されない。 Examples of the additional monomer units include, but are not limited to, polymerizable (meth)acrylic monomers. Specific examples of polymerizable (meth)acrylic monomers include dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, benzyl acrylate, nonylphenoxy polyethylene glycol acrylate. , nonylphenoxy polyethylene glycol acrylate, nonanediol diacrylate, polypropylene glycol acrylate, 1,4-butanediol dimethacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, pentamethylpiperidyl methacrylate, tetra Examples include, but are not limited to, methyl piperidyl methacrylate, methoxy polyethylene glycol methacrylate, benzyl methacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, and the like.

上記重合性（メタ）アクリル系ポリマー（Ａ）は，特に好ましくは次の一般式， The polymerizable (meth)acrylic polymer (A) is particularly preferably represented by the following general formula,

Figure 0007178986000008
Figure 0007178986000008

〔式中，各Ｒ１は，独立して，水素原子又はメチル基を表し，Ｘ１，Ｘ２，Ｘ３及びＸ４は，それぞれ独立して，下記一般式（１）で示される置換基を表し，[Wherein, each R 1 independently represents a hydrogen atom or a methyl group, and X 1 , X 2 , X 3 and X 4 each independently represents a substituent represented by the following general formula (1) represents

Figure 0007178986000009
Figure 0007178986000009

（式中，Ｒ２は，水素原子又はメチル基を表し，「＊－」は単結合を表す。），
Ｒ３は，下記構造式で表される置換基の何れか表し，(Wherein, R 2 represents a hydrogen atom or a methyl group, and "*-" represents a single bond.),
R 3 represents any of the substituents represented by the following structural formulas,

Figure 0007178986000010
Figure 0007178986000010

ｌ，ｍ及びｎは，ｌ：ｍ：ｎの形で各モノマー単位相互のモル比を表す。〕で示される。 l, m and n represent the molar ratios of each monomer unit to each other in the form l:m:n. ].

上記において，該重合性（メタ）アクリル系ポリマー（Ａ）の一般式中，次式 In the above, in the general formula of the polymerizable (meth)acrylic polymer (A), the following formula

Figure 0007178986000011
Figure 0007178986000011

で示されるモノマー単位（１）は，Ｘ１，Ｘ２共にアクリロイルオキシ基であるモノマー単位（１ａ）と，Ｘ１，Ｘ２共にメタクリロイルオキシ基であるモノマー単位（１ｂ）とを含んでなるものであってもよい。The monomer unit (1) represented by is composed of a monomer unit (1a) in which both X 1 and X 2 are acryloyloxy groups and a monomer unit (1b) in which both X 1 and X 2 are methacryloyloxy groups. may be

上記において，好ましくは，比ｌ：ｍ：ｎ＝２０～８０：５～５０：０～３０であり，より好ましくは５０～７０：１０～３０：０～１０である。 In the above, the ratio l:m:n is preferably 20-80:5-50:0-30, more preferably 50-70:10-30:0-10.

本発明の活性エネルギー線硬化型樹脂組成物の構成要素の１つである多官能（メタ）アクリレート系モノマー（Ｂ）の例としては，ジペンタエリスリトールヘキサアクリレート，ジペンタエリスリトールポリアクリレート，ペンタエリスリトールトリアクリレート，ペンタエリスリトールテトラアクリレート，エトキシ化ペンタエリスリトールテトラアクリレート，ジトリメチロールプロパンテトラアクリレート，トリメチロールプロパントリアクリレート，エトキシ化イソシアヌル酸トリアクリレート，及びε-カプロラクトン変性トリス－（２－アクリロキシエチル)イソシアヌレートが挙げられるが，これらに限定されない。これらのうち，ジペンタエリスリトールヘキサアクリレートは，特に好ましいものの１つである。本発明の樹脂組成物中，重合性（メタ）アクリル系ポリマー（Ａ）の固形分１００重量部に対し，多官能（メタ）アクリレート系モノマー（Ｂ）は，好ましくは５０～３５０重量部，より好ましくは８０～３００重量部，更に好ましく１００～２５０重量部が含有される。 Examples of the polyfunctional (meth)acrylate monomer (B), which is one of the components of the active energy ray-curable resin composition of the present invention, include dipentaerythritol hexaacrylate, dipentaerythritol polyacrylate, pentaerythritol tri acrylates, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate Examples include, but are not limited to: Of these, dipentaerythritol hexaacrylate is one of the most preferred. In the resin composition of the present invention, the polyfunctional (meth)acrylate monomer (B) is preferably 50 to 350 parts by weight, more than 100 parts by weight of the solid content of the polymerizable (meth)acrylic polymer (A). It is preferably contained in an amount of 80 to 300 parts by weight, more preferably 100 to 250 parts by weight.

本願発明において，ラジカル重合開始剤としては，慣用のものを適宜用いることができる。例として，光重合開始剤イルガキュア９０７，イルガキュア３７９，イルガキュア８１９，イルガキュアＯＸＥ－０１，イルガキュアＯＸＥ－０２等が挙げられるが，これに限定されない。 In the present invention, a commonly used radical polymerization initiator can be appropriately used. Examples include, but are not limited to, photopolymerization initiators Irgacure 907, Irgacure 379, Irgacure 819, Irgacure OXE-01, Irgacure OXE-02, and the like.

以下実施例を参照して本発明を更に詳細に説明するが，本発明がそれらの実施例に限定されることは意図しない。 The invention will be described in more detail below with reference to examples, but it is not intended that the invention be limited to those examples.

〔製造例１〕 アクリル樹脂（Ａ－１）（Ｘ：Ｙ＝８０：２０）の製造 [Production Example 1] Production of acrylic resin (A-1) (X:Y=80:20)

Figure 0007178986000012
Figure 0007178986000012

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，プロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２‘－アゾビス（２，４－ ジメチルバレロニトリル）８．７ｇを添加し，８０℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更に無水アクリル酸ｇ，アクリル酸１５ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート１７３ｇを添加し，７０℃で１２時間反応させた。その後，反応後の溶液に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－１）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は３７．４であった。ＧＰＣによる重量平均分子量（Ｍｗ）は２４，０００であった。100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 8.7 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
To the resulting solution were added acrylic anhydride (g), acrylic acid (15 g), tetrabutylammonium chloride (2 g), hydroquinone (0.3 g) and propylene glycol monomethyl ether acetate (173 g), and the mixture was reacted at 70° C. for 12 hours. After that, 14 g of succinic anhydride was added to the solution after the reaction and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-1).
The acid value of this acrylic resin in terms of solid content was 37.4. The weight average molecular weight (Mw) by GPC was 24,000.

〔製造例２〕 アクリル樹脂（Ａ－２）（Ｘ：Ｙ＝８０：２０）の製造 [Production Example 2] Production of acrylic resin (A-2) (X:Y=80:20)

Figure 0007178986000013
Figure 0007178986000013

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，プロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２‘－アゾビス（２，４－ジメチルバレロニトリル）８．７ｇを添加し，８０ ℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更に無水メタクリル酸８７ｇ，アクリル酸１５ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート１９０ｇを添加し，７０℃で１２時間反応させた。その後，溶液に更に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－２）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は３４．８であった。ＧＰＣによる重量平均分子量（Ｍｗ）は２１，０００であった。100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 8.7 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
87 g of methacrylic anhydride, 15 g of acrylic acid, 2 g of tetrabutylammonium chloride, 0.3 g of hydroquinone, and 190 g of propylene glycol monomethyl ether acetate were further added to the obtained solution and reacted at 70° C. for 12 hours. After that, 14 g of succinic anhydride was further added to the solution and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-2).
The acid value of this acrylic resin in terms of solid content was 34.8. The weight average molecular weight (Mw) by GPC was 21,000.

〔製造例３〕 アクリル樹脂（Ａ－３）の製造（Ｘ：Ｙ：Ｚ＝４０：４０：２０） [Production Example 3] Production of acrylic resin (A-3) (X: Y: Z = 40: 40: 20)

Figure 0007178986000014
Figure 0007178986000014

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，プロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２‘－アゾビス（２，４－ ジメチルバレロニトリル）８．７ｇを添加し，８０ ℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更に無水アクリル酸３５ｇ，無水メタクリル酸４３ｇ，アクリル酸１５ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート１８０ｇを添加し，７０℃で１２時間反応させた。その後，溶液に更に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－３）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は３６．２であった。ＧＰＣによる重量平均分子量（Ｍｗ）は２２，０００であった。100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 8.7 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
35 g of acrylic anhydride, 43 g of methacrylic anhydride, 15 g of acrylic acid, 2 g of tetrabutylammonium chloride, 0.3 g of hydroquinone, and 180 g of propylene glycol monomethyl ether acetate were further added to the obtained solution and reacted at 70° C. for 12 hours. . After that, 14 g of succinic anhydride was further added to the solution and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-3).
The acid value of this acrylic resin in terms of solid content was 36.2. The weight average molecular weight (Mw) by GPC was 22,000.

〔製造例４〕 アクリル樹脂（Ａ－４）（Ｘ：Ｙ＝８０：２０）の製造 [Production Example 4] Production of acrylic resin (A-4) (X:Y=80:20)

Figure 0007178986000015
Figure 0007178986000015

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，プロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２‘－アゾビス（２，４－ジメチルバレロニトリル）８．７ｇを添加し，８０ ℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更にアクリル酸５１ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート１１０ｇを添加し，１００℃で１２時間反応させた。その後，溶液に更に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－４）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は４６．２であった。ＧＰＣによる重量平均分子量（Ｍｗ）は１７，０００であった。100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 8.7 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
Further, 51 g of acrylic acid, 2 g of tetrabutylammonium chloride, 0.3 g of hydroquinone, and 110 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 12 hours. After that, 14 g of succinic anhydride was further added to the solution and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-4).
The acid value of this acrylic resin in terms of solid content was 46.2. The weight average molecular weight (Mw) by GPC was 17,000.

〔製造例５〕 アクリル樹脂（Ａ－５）（Ｘ：Ｙ＝８０：２０）の製造 [Production Example 5] Production of acrylic resin (A-5) (X:Y=80:20)

Figure 0007178986000016
Figure 0007178986000016

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，プロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２‘－アゾビス（２，４－ジメチルバレロニトリル）８．７ｇを添加し，８０ ℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更にアクリル酸５１ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート２４０ｇを添加し，１００℃で１２時間反応させた。反応後，カレンズＭＯＩ８７ｇを添加し，７０℃で１０時間反応させた。その後，溶液に更に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－５）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は３０．０であった。ＧＰＣによる重量平均分子量（Ｍｗ）は２８，０００であった。100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 8.7 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
Further, 51 g of acrylic acid, 2 g of tetrabutylammonium chloride, 0.3 g of hydroquinone, and 240 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 12 hours. After the reaction, 87 g of Karenz MOI was added and reacted at 70° C. for 10 hours. After that, 14 g of succinic anhydride was further added to the solution and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-5).
The acid value of this acrylic resin in terms of solid content was 30.0. The weight average molecular weight (Mw) by GPC was 28,000.

〔製造例６〕 アクリル樹脂（Ａ－６）の製造（Ｗ：Ｘ：Ｙ：Ｚ＝２０：５６：１６：８） [Production Example 6] Production of acrylic resin (A-6) (W: X: Y: Z = 20: 56: 16: 8)

Figure 0007178986000017
Figure 0007178986000017

加熱冷却・撹拌装置，還流冷却管，窒素導入管を備えたガラス製フラスコに，グリシジルメタクリレート１００ｇ，ジシクロペンタニルメタクリレート３９ｇ，プロピレングリコールモノメチルエーテルアセテート２０８ｇを仕込んだ。系内の気相部分を窒素で置換したのち，２，２’－アゾビス（２，４－ジメチルバレロニトリル）７．２ｇを添加し，８０℃に加熱し，同温度で８時間反応させた。
得られた溶液に，更に無水メタクリル酸７６ｇ，アクリル酸１５ｇ，テトラブチルアンモニウムクロライド２ｇ，ハイドロキノン０．３ｇ，プロピレングリコールモノメチルエーテルアセテート１６０ｇを添加し，７０℃で１２時間反応させた。その後，得られた溶液に無水コハク酸１４ｇを添加し，７０℃で６時間反応させ，目的の重合体（Ａ－６）の４０％溶液を得た。
このアクリル樹脂の固形分換算した酸価は３２．３であった。ＧＰＣによる重量平均分子量（Ｍｗ）は２５，０００であった。100 g of glycidyl methacrylate, 39 g of dicyclopentanyl methacrylate, and 208 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 7.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 80°C, and reacted at the same temperature for 8 hours.
76 g of methacrylic anhydride, 15 g of acrylic acid, 2 g of tetrabutylammonium chloride, 0.3 g of hydroquinone, and 160 g of propylene glycol monomethyl ether acetate were further added to the resulting solution and reacted at 70° C. for 12 hours. After that, 14 g of succinic anhydride was added to the resulting solution and reacted at 70° C. for 6 hours to obtain a 40% solution of the desired polymer (A-6).
The acid value of this acrylic resin in terms of solid content was 32.3. The weight average molecular weight (Mw) by GPC was 25,000.

〔実施例１～１４，比較例１～８〕
（１）フォトスペーサー用レジストの調製
表１に示した組成に従い，重合体（Ａ－１）３５．７ｇ，多官能アクリレート系モノマー（Ｂ）としてジペンタエリスリトールヘキサアクリレート(KAYARAD DPHA)（Ｂ－１）１４．３ｇ，光重合開始剤イルガキュア９０７（Ｃ－１）１．５ｇ，及びプロピレングリコールモノメチルエーテルアセテート４８．５ｇを遮光下で混合し，実施例１のフォトスペーサー用レジストを調製した。表中の実施例２～１４及び比較例１～８も同様に調製した。なお，表中のＢ－２は，ペンタエリスリトールトリアクリレート（大阪有機化学（株）製，製品名：ＰＥＴ３Ａ）である。[Examples 1 to 14, Comparative Examples 1 to 8]
(1) Preparation of photospacer resist According to the composition shown in Table 1, 35.7 g of polymer (A-1) and dipentaerythritol hexaacrylate (KAYARAD DPHA) (B-1) as polyfunctional acrylate monomer (B) ), 1.5 g of photopolymerization initiator Irgacure 907 (C-1), and 48.5 g of propylene glycol monomethyl ether acetate were mixed under light shielding conditions to prepare a photospacer resist of Example 1. Examples 2-14 and Comparative Examples 1-8 in the table were similarly prepared. B-2 in the table is pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Co., Ltd., product name: PET3A).

Figure 0007178986000018
Figure 0007178986000018

（２）フォトスペーサーの作製
１０ｃｍ×１０ｃｍ角のガラス基板上に，実施例及び比較例の各レジストをスピンコーターにより塗布し，乾燥し，乾燥膜厚３μｍの塗膜を形成した。この塗膜をホットプレート上で９０℃，２分間加熱した。得られた塗膜に対し複数の開口部を有するフォトスペーサー形成用のマスクを通して超高圧水銀灯の光を１００ｍＪ／ｃｍ２照射した（ｉ線換算で照度２０ｍＷ／ｃｍ２）。なお，マスクと基板の間隔（露光ギャップ）は１００μｍで露光した。その後０．３％Ｋ２ＣＯ３水溶液を用いてアルカリ現像した。水洗したのち，２３０℃で３０分間ポストベークを行い，膜厚３μｍのフォトスペーサーを作製した。なお，マスク開口径を調整することにより下底径７μｍを有するフォトスペーサーを作製した。(2) Fabrication of Photospacer Each resist of Examples and Comparative Examples was applied onto a 10 cm×10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 3 μm. This coating film was heated on a hot plate at 90° C. for 2 minutes. The resulting coating film was irradiated with 100 mJ/cm 2 of light from an ultra-high pressure mercury lamp through a photospacer-forming mask having a plurality of openings (i-line conversion illuminance: 20 mW/cm 2 ). The distance between the mask and the substrate (exposure gap) was set to 100 μm. After that, alkali development was carried out using a 0.3% K 2 CO 3 aqueous solution. After washing with water, post-baking was performed at 230° C. for 30 minutes to produce a photospacer with a film thickness of 3 μm. A photospacer having a bottom diameter of 7 μm was produced by adjusting the mask opening diameter.

（３）現像速度の測定
１０ｃｍ×１０ｃｍ角のガラス基板上にスピンコーターにより塗布し，乾燥し，乾燥膜厚３μｍの塗膜を形成した。この塗膜をホットプレート上で９０℃，２分間加熱した。０．３％Ｋ２ＣＯ３水溶液を用いて得られた塗膜をアルカリ現像し，基板上からレジスト残渣がなくなるまでの現像時間を測定した。結果を表２に示す。(3) Measurement of Development Speed A 10 cm×10 cm square glass substrate was coated with a spin coater and dried to form a coating film having a dry film thickness of 3 μm. This coating film was heated on a hot plate at 90° C. for 2 minutes. The coating film obtained was subjected to alkali development using a 0.3% K 2 CO 3 aqueous solution, and the development time until the resist residue disappeared from the substrate was measured. Table 2 shows the results.

（４）弾性回復率の測定
フォトスペーサーの弾性回復特性は，下記数式（１）で定義された一定の圧力がかかった時の「弾性回復率」によって評価することができる。弾性回復率（％）の値の高い方が弾性回復特性に優れる。
ガラス基板上に形成したフォトスペーサーのうち任意に選択した１個のフォトスペーサーに対し，微小硬度計（フィッシャーインストルメンツ社製；「フィッシャースコープＨ－ １００」）と断面が正方形の平面圧子（５０μｍ×５０μｍ）を用いて，荷重をかけたときと戻したときの変形量を測定した。この際に２ｍＮ／秒の負荷速度で，１０秒かけて２０ｍＮまで荷重をかけ，５秒間保持した。荷重がかかった状態でのフォトスペーサーの初期位置からの変形量を測定した。このときの変化量を総変形量Ｔ０（μｍ）とする。次に，２ｍＮ／秒の除荷速度で１０秒かけて荷重を０まで解除し，その状態で５秒間保持した。この時のフォトスペーサーの変形量を塑性変形量Ｔ１（μ ｍ）とする。
上記のようにして測定したＴ０とＴ１から，下記数式（１）を用いて弾性回復率を算出した。結果を表２に示す。
・弾性回復率（％）＝［（Ｔ０－Ｔ１）／Ｔ０］×１００ ・・・（１）(4) Measurement of elastic recovery rate The elastic recovery property of the photospacer can be evaluated by the "elastic recovery rate" when a constant pressure is applied, which is defined by the following formula (1). The higher the elastic recovery rate (%), the better the elastic recovery characteristics.
For one photospacer arbitrarily selected from the photospacers formed on the glass substrate, a micro hardness tester (manufactured by Fisher Instruments; "Fisherscope H-100") and a flat indenter with a square cross section (50 μm × 50 μm) was used to measure the amount of deformation when the load was applied and when the load was returned. At this time, the load was applied at a load rate of 2 mN/sec over 10 seconds up to 20 mN and held for 5 seconds. The amount of deformation from the initial position of the photospacer under load was measured. The amount of change at this time is assumed to be the total amount of deformation T0 (μm). Next, the load was released to 0 over 10 seconds at an unloading rate of 2 mN/sec, and this state was maintained for 5 seconds. The amount of deformation of the photospacer at this time is defined as the amount of plastic deformation T1 (μm).
From T0 and T1 measured as described above, the elastic recovery rate was calculated using the following formula (1). Table 2 shows the results.
・ Elastic recovery rate (%) = [(T0-T1) / T0] × 100 (1)

Figure 0007178986000019
Figure 0007178986000019

表２に見られるように，実施例のフォトレジストは現像完了まで８～１３秒であり，比較例の１５～６０秒に比べて，現像速度が顕著に速い。また実施例のフォトレジストでは，弾性回復率が，８０％以上のもの５例（全体の４２％），７５％～８０％未満のもの４例（全体の３３％），７０％～７５％未満のもの３例（全体の２５％）であるのに対し，比較例のフォトレジストでは，８０％以上のものはなく（全体の０％），７５％～８０％未満のもの１例（全体の１３％），７０％～７５％未満のもの２例（全体の２５％），６５％～７０％未満のもの４例（全体の５０％），６０％～６５％未満のもの１例（全体の１３％）であり，実施例のフォトレジストは比較例により全体として顕著に優れている。また比較例のレジストにおいて弾性回復率が７０以上を示したものは，現像速度が５０秒（比較例２），６０秒（比較例６），及び２０秒（比較例８）であり，とりわけ長い現像時間を要するものである。これらの結果は，実施例のレジストにより，現像の迅速性と優れた弾性回復率との両立が達成されていることを示している。 As can be seen in Table 2, the photoresists of the examples take 8 to 13 seconds to complete development, which is significantly faster than the 15 to 60 seconds of the comparative examples. In the photoresists of the examples, the elastic recovery rate was 80% or more in 5 cases (42% of the total), 75% to less than 80% in 4 cases (33% of the total), and 70% to less than 75%. 3 cases (25% of the total), whereas in the photoresist of the comparative example, there were no cases of 80% or more (0% of the total), and 1 case of 75% to less than 80% (of the total). 13%), 2 cases of 70% to less than 75% (25% of the total), 4 cases of 65% to less than 70% (50% of the total), 1 case of 60% to less than 65% (total 13% of the total), and the photoresists of the examples are significantly superior to the comparative examples as a whole. In addition, the resists of Comparative Examples that showed an elastic recovery rate of 70 or more had development speeds of 50 seconds (Comparative Example 2), 60 seconds (Comparative Example 6), and 20 seconds (Comparative Example 8), which were particularly long. Development time is required. These results indicate that the resists of the examples achieve both rapid development and excellent elastic recovery.

本発明は，活性エネルギー線に対する良好な感光性と，感光後のアルカリ性現像液に対する迅速な現像性と，外力の負荷による変形に対して優れた弾性回復率を示す硬化物を与えることができるものとして，有用である。 The present invention provides a cured product that exhibits good photosensitivity to active energy rays, rapid developability with an alkaline developer after exposure, and excellent elastic recovery against deformation due to external force. is useful as

Claims (12)

側鎖を備え，該側鎖は２つに分枝した末端の各々がラジカル重合性置換基に終わっており，該ラジカル重合性置換基のそれぞれは該側鎖の一部をなす炭素数３個の炭化水素鎖（Ｌ）上に置換しており，該炭化水素鎖（Ｌ）はポリマーの主鎖に基－Ｃ(Ｏ)Ｏ－を介して結合しているものである,（メタ）アクリル系モノマー単位（１）と，
側鎖を備え，該側鎖は２つに分枝した末端の一方がカルボキシル基に終わり，他方がラジカル重合性置換基に終わっており，該ラジカル重合性置換基は該側鎖の一部をなす炭素数３個の炭化水素鎖（Ｍ）上に置換し，該炭化水素鎖（Ｍ）はポリマーの主鎖に基－Ｃ(Ｏ)Ｏ－を介して結合しており，該カルボキシル基は該炭化水素鎖（Ｍ）上に基－ＯＣ(Ｏ)－Ｚ－を介して結合しているものであり，ここに該基の一部をなす基－Ｚ－は，炭素数２～７個からなる，飽和若しくは不飽和の鎖状若しくは環状の，炭化水素骨格又はベンゼン環を含んでなるものである，（メタ）アクリル系モノマー単位（２）と，又は更に
ラジカル重合性置換基で終わる１つの末端を有する側鎖を備えた（メタ）アクリル系モノマー単位（３）と，
を構成要素として含んでなり，かつ該ラジカル重合性置換基は相互に独立して（メタ）アクリロイルオキシ基である，重合性（メタ）アクリル系ポリマー（Ａ）と，
多官能（メタ）アクリレート系モノマー（Ｂ）と
光重合開始剤（Ｃ）を含んでなる，
感光性樹脂組成物。 a side chain having two branched ends each terminating in a radically polymerizable substituent, each of said radically polymerizable substituents having 3 carbon atoms forming part of said side chain; is substituted on one hydrocarbon chain (L), and the hydrocarbon chain (L) is attached to the main chain of the polymer through the group -C (O) O-, (meta) an acrylic monomer unit (1);
a side chain, one of the two branched ends of the side chain ends in a carboxyl group and the other ends in a radically polymerizable substituent , and the radically polymerizable substituent is one of the side chains. is substituted on a hydrocarbon chain (M) having 3 carbon atoms forming a part, the hydrocarbon chain (M) is bonded to the main chain of the polymer through a group -C (O) O-, and the carboxyl The group is bonded to the hydrocarbon chain (M) via the group -OC(O)-Z-, wherein the group -Z- forming part of the group has 2 to A (meth)acrylic monomer unit (2) consisting of 7 saturated or unsaturated linear or cyclic, hydrocarbon backbones or benzene rings , or further
a (meth)acrylic monomer unit (3) with a side chain having one end terminating with a radically polymerizable substituent;
as a component , and the radically polymerizable substituents are independently (meth)acryloyloxy groups, a polymerizable (meth)acrylic polymer (A);
With a polyfunctional (meth)acrylate monomer (B)
comprising a photoinitiator (C),
A photosensitive resin composition. モノマー単位（３）における該ラジカル重合性置換基が，側鎖の一部をなす炭素数３～５個を含んでなる炭化水素鎖上に置換しているものである，請求項１の樹脂組成物。 The resin composition according to claim 1, wherein the radically polymerizable substituent in the monomer unit (3) is substituted on a hydrocarbon chain containing 3 to 5 carbon atoms forming part of the side chain. thing. 該モノマー単位（２）における基－Ｚ－の２個の結合位置が，当該基を構成する炭素原子のうち互いに隣接する２個の炭素原子上に存在するものである，請求項１又は２の樹脂組成物。 The two bonding positions of the group -Z- in the monomer unit (2) are present on two carbon atoms adjacent to each other among the carbon atoms constituting the group. Resin composition. 該モノマー単位（１）が，アクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ａ）と，メタクリロイルオキシ基を該ラジカル重合性置換基として有するモノマー単位（１ｂ）とからなるものである，請求項１～３の何れかの樹脂組成物。 The monomer unit (1) consists of a monomer unit (1a) having an acryloyloxy group as the radically polymerizable substituent and a monomer unit (1b) having a methacryloyloxy group as the radically polymerizable substituent. , the resin composition according to any one of claims 1 to 3 . 該重合性（メタ）アクリル系ポリマー（Ａ）を構成する該モノマー単位間のモル比が，モノマー単位（１）：モノマー単位（２）：モノマー単位（３）＝２０～８０：５～５０：０～３０である，請求項１～４の何れかの樹脂組成物。 The molar ratio between the monomer units constituting the polymerizable (meth)acrylic polymer (A) is monomer unit (1): monomer unit (2): monomer unit (3) = 20 to 80: 5 to 50: The resin composition according to any one of claims 1 to 4 , which is 0 to 30. 該重合性（メタ）アクリル系ポリマー（Ａ）が次の一般式：
Figure 0007178986000020
〔式中，各Ｒ１は，独立して，水素原子又はメチル基を表し，Ｘ１，Ｘ２，Ｘ３及びＸ４は，それぞれ独立して，下記一般式（１）で示される置換基を表し，
Figure 0007178986000021
（式中，Ｒ２は，水素原子又はメチル基を表し，「＊－」は単結合を表す。），
Ｒ３は，下記構造式で表される置換基の何れかを表し，
Figure 0007178986000022
ｌ，ｍ及びｎは，比ｌ：ｍ：ｎの形で各モノマー単位相互のモル比を表す。〕で示されるものである，請求項１～４の何れかの樹脂組成物。 The polymerizable (meth)acrylic polymer (A) has the following general formula:
Figure 0007178986000020
[Wherein, each R 1 independently represents a hydrogen atom or a methyl group, and X 1 , X 2 , X 3 and X 4 each independently represents a substituent represented by the following general formula (1) represents
Figure 0007178986000021
(Wherein, R 2 represents a hydrogen atom or a methyl group, and "*-" represents a single bond.),
R 3 represents any of the substituents represented by the following structural formulas,
Figure 0007178986000022
l, m and n represent the molar ratios of each monomer unit to each other in the form of the ratio l:m:n. ], the resin composition according to any one of claims 1 to 4 . 該重合性（メタ）アクリル系ポリマー（Ａ）において，比ｌ：ｍ：ｎ＝２０～８０：５～５０：０～３０である，請求項６の樹脂組成物。 7. The resin composition according to claim 6 , wherein the polymerizable (meth)acrylic polymer (A) has a ratio l:m:n of 20-80:5-50:0-30. 該重合性（メタ）アクリル系ポリマー（Ａ）の一般式中，次式：
Figure 0007178986000023
で示されるモノマー単位（１）が，Ｘ１，Ｘ２共にアクリロイルオキシ基であるモノマー単位（１ａ）と，Ｘ１，Ｘ２共にメタクリロイルオキシ基であるモノマー単位（１ｂ）とを含んでなるものである，請求項６又は７の樹脂組成物。 In the general formula of the polymerizable (meth)acrylic polymer (A), the following formula:
Figure 0007178986000023
comprising a monomer unit (1a) in which both X 1 and X 2 are acryloyloxy groups, and a monomer unit (1b) in which both X 1 and X 2 are methacryloyloxy groups. The resin composition according to claim 6 or 7 , which is 該重合性（メタ）アクリル系ポリマー（Ａ）が，次式
Figure 0007178986000024
Figure 0007178986000025
Figure 0007178986000026
（式中，ｌ，ｍ及びｎは，比ｌ：ｍ：ｎの形で各モノマー単位相互のモル比を表し，比ｌ：ｍ：ｎ＝２０～８０：５～５０：０～３０である）の何れかで示されるものである，請求項６～８の何れかの樹脂組成物。 The polymerizable (meth)acrylic polymer (A) has the following formula
Figure 0007178986000024
Figure 0007178986000025
Figure 0007178986000026
(Wherein, l, m and n represent the molar ratio of each monomer unit to each other in the form of a ratio l:m:n, the ratio l:m:n = 20-80:5-50:0-30. ) , the resin composition according to any one of claims 6 to 8 . 該多官能（メタ）アクリレート系モノマー（Ｂ）が，ジペンタエリスリトールヘキサアクリレート，ジペンタエリスリトールポリアクリレート，ペンタエリスリトールトリアクリレート，ペンタエリスリトールテトラアクリレート，エトキシ化ペンタエリスリトールテトラアクリレート，ジトリメチロールプロパンテトラアクリレート，トリメチロールプロパントリアクリレート，エトキシ化イソシアヌル酸トリアクリレート，及びε-カプロラクトン変性トリス－（２－アクリロキシエチル）イソシアヌレートからなる群より選ばれるものである，請求項１～９の何れかの樹脂組成物。 The polyfunctional (meth)acrylate monomer (B) includes dipentaerythritol hexaacrylate, dipentaerythritol polyacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, tri The resin composition according to any one of claims 1 to 9 , which is selected from the group consisting of methylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate. . 該重合性（メタ）アクリル系ポリマー（Ａ）が，該モノマー単位（１），（２），及び（３）の何れとも異なるモノマー単位（４）を更に含んでなるものである，請求項１～４の何れかの樹脂組成物。 Claim 1, wherein the polymerizable (meth)acrylic polymer (A) further comprises a monomer unit (4) different from any of the monomer units (1), (2), and (3). 4. The resin composition according to any one of 1 to 4. 側鎖を備え，該側鎖は２つに分枝した末端の各々がラジカル重合性置換基に終わっており，該ラジカル重合性置換基のそれぞれは該側鎖の一部をなす炭素数３個の炭化水素鎖（Ｌ）上に置換しており，該炭化水素鎖（Ｌ）はポリマーの主鎖に基－Ｃ(Ｏ)Ｏ－を介して結合しているものである，（メタ）アクリル系モノマー単位（１）と，
側鎖を備え，該側鎖は２つに分枝した末端の一方がカルボキシル基に終わり，他方がラジカル重合性置換基に終わっており，該ラジカル重合性置換基は該側鎖の一部をなす炭素数３個の炭化水素鎖（Ｍ）上に置換し，該炭化水素鎖（Ｍ）はポリマーの主鎖に基－Ｃ(Ｏ)Ｏ－を介して結合しており，該カルボキシル基は該炭化水素鎖（Ｍ）上に基－ＯＣ(Ｏ)－Ｚ－を介して結合しているものであり，ここに該基の一部をなす基－Ｚ－は，炭素数２～７個からなる，飽和若しくは不飽和の鎖状若しくは環状の，炭化水素骨格又はベンゼン環を含んでなるものである，（メタ）アクリル系モノマー単位（２）と，又は更に，
ラジカル重合性置換基で終わる１つの末端を有する側鎖を備えた（メタ）アクリル系モノマー単位（３）と，
を構成要素として含んでなり，かつ該ラジカル重合性置換基は相互に独立して（メタ）アクリロイルオキシ基である，重合性（メタ）アクリル系ポリマー。
 a side chain having two branched ends each terminating in a radically polymerizable substituent, each of said radically polymerizable substituents having 3 carbon atoms forming part of said side chain; is substituted on one hydrocarbon chain (L), and the hydrocarbon chain (L) is bonded to the main chain of the polymer through the group -C (O) O-, (meta) an acrylic monomer unit (1);
a side chain, one of the two branched ends of the side chain ends in a carboxyl group and the other ends in a radically polymerizable substituent , and the radically polymerizable substituent is one of the side chains. is substituted on a hydrocarbon chain (M) having 3 carbon atoms forming a part, the hydrocarbon chain (M) is bonded to the main chain of the polymer through a group -C (O) O-, and the carboxyl The group is bonded to the hydrocarbon chain (M) via the group -OC(O)-Z-, wherein the group -Z- forming part of the group has 2 to A (meth)acrylic monomer unit (2) consisting of 7 saturated or unsaturated linear or cyclic, hydrocarbon skeletons or benzene rings , or further,
a (meth)acrylic monomer unit (3) with a side chain having one end terminating with a radically polymerizable substituent;
as constituent elements , and the radically polymerizable substituents are independently (meth)acryloyloxy groups .
JP2019506286A 2017-03-17 2018-03-16 Photosensitive resin composition Active JP7178986B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017052527 2017-03-17
JP2017052527 2017-03-17
PCT/JP2018/010400 WO2018169036A1 (en) 2017-03-17 2018-03-16 Photosensitive resin composition

Publications (2)

Publication Number Publication Date
JPWO2018169036A1 JPWO2018169036A1 (en) 2020-01-16
JP7178986B2 true JP7178986B2 (en) 2022-11-28

Family

ID=63523166

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2019506286A Active JP7178986B2 (en) 2017-03-17 2018-03-16 Photosensitive resin composition

Country Status (4)

Country Link
JP (1) JP7178986B2 (en)
CN (2) CN110419003B (en)
TW (1) TWI778031B (en)
WO (1) WO2018169036A1 (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08184961A (en) * 1994-11-02 1996-07-16 Toray Ind Inc Damping waterless planographic printing master plate
JP3543409B2 (en) * 1995-03-24 2004-07-14 大日本インキ化学工業株式会社 Active energy ray-curable epoxy acrylate resin composition
JP5058757B2 (en) * 2007-11-07 2012-10-24 太陽ホールディングス株式会社 Photocurable resin composition, cured product pattern thereof, and printed wiring board comprising the cured product pattern
JP5376793B2 (en) * 2007-11-07 2013-12-25 太陽ホールディングス株式会社 Photocurable resin composition, cured product pattern thereof, and printed wiring board comprising the cured product pattern
JP5107960B2 (en) * 2009-04-10 2012-12-26 太陽ホールディングス株式会社 Solder resist composition, dry film and printed wiring board using the same
JP2011144230A (en) * 2010-01-13 2011-07-28 Japan U-Pica Co Ltd Polyfunctional epoxy (meth)acrylate compound and photosensitive thermosetting resin composition comprising the compound, and cured product thereof
KR20150118582A (en) * 2013-02-12 2015-10-22 도레이 카부시키가이샤 Photosensitive resin composition, protective film or insulation film obtained by heat curing said composition, touch panel using said film, and production method for said touch panel
JP6495769B2 (en) * 2014-07-18 2019-04-03 株式会社日本触媒 Curable resin composition and use thereof
JP6324517B2 (en) * 2015-02-26 2018-05-16 Dic株式会社 Unsaturated group-containing alkali developable resin and solder resist resin material

Also Published As

Publication number Publication date
CN110419003A (en) 2019-11-05
CN110419003B (en) 2023-04-18
JPWO2018169036A1 (en) 2020-01-16
CN116640266A (en) 2023-08-25
TWI778031B (en) 2022-09-21
WO2018169036A1 (en) 2018-09-20
TW201841955A (en) 2018-12-01

Similar Documents

Publication Publication Date Title
JP4680867B2 (en) Photosensitive resin composition
JP5665615B2 (en) Photosensitive resin composition for color filter
JP6404557B2 (en) Curable resin composition
TW201300949A (en) Photosensitive Resin Composition For Forming Spacer, Spacer Manufactured By The Same For Display Device, And Display Device With The Spacer
JP2011248274A (en) Photosensitive resin composition
TWI665518B (en) Negative-type photosensitive resin composition, photo-curable pattern and image display device using the same
TWI676627B (en) Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern
JPWO2013115262A1 (en) Photosensitive resin composition, photosensitive element using the same, method for forming spacer, and spacer
JP6506732B2 (en) Negative photosensitive resin composition and photocurable pattern produced therefrom
TWI628195B (en) Multifunctional (meth) acrylate copolymer, curable resin composition, and cured product thereof
KR20230128119A (en) Alkali-soluble resin, photosensitive resin composition, cured product, and image display device
WO2017204079A1 (en) Photosensitive resin composition for forming black column spacer, black column spacer and image display device
JP6644565B2 (en) Photosensitive resin composition, photocurable pattern formed therefrom, and image display device having the same
JP7178986B2 (en) Photosensitive resin composition
JP2016143064A (en) Photosensitive resin composition, photocured pattern formed from photosensitive resin composition, and image display device including photocured pattern
JP2009096857A (en) Curable composition and its molded product
JP6694230B2 (en) Alkali-soluble resin and curable resin composition containing the same
KR20150011070A (en) A photosensitive resin composition for spacer and a spacer using the same
KR20140143951A (en) Photosensitive resin composition and spacer prepared therefrom
JP6854147B2 (en) Resin for photo spacers, resin composition for photo spacers, photo spacers and color filters
JP2009263546A (en) Curable resin composition, curable composition for image formation, and pillar spacer obtained by curing composition
JP2016060861A (en) Alkali-soluble resin and curable resin composition containing the same
JP2016199703A (en) Alkali-soluble resin and curable resin composition containing the same
JP6872918B2 (en) Polymers and their uses
JP2009096862A (en) Polymerizable compound and polymer

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210310

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20210310

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20220329

A601 Written request for extension of time

Free format text: JAPANESE INTERMEDIATE CODE: A601

Effective date: 20220524

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20220727

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20221114

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20221115

R150 Certificate of patent or registration of utility model

Ref document number: 7178986

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150