TWI385485B - A photosensitive resin composition, a display panel spacer, and a display panel - Google Patents

A photosensitive resin composition, a display panel spacer, and a display panel Download PDF

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TWI385485B
TWI385485B TW094138879A TW94138879A TWI385485B TW I385485 B TWI385485 B TW I385485B TW 094138879 A TW094138879 A TW 094138879A TW 94138879 A TW94138879 A TW 94138879A TW I385485 B TWI385485 B TW I385485B
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ethyl
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TW200634433A (en
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Daigo Ichinohe
Toshihiro Nishio
Hitoshi Hamaguchi
Tomoko Iwabuchi
Isamu Yonekura
Toru Kajita
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Jsr Corp
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    • 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
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)

Description

感光性樹脂組成物、顯示面板用間隔物及顯示面板Photosensitive resin composition, spacer for display panel, and display panel

本發明係關於感光性樹脂組成物、顯示面板用間隔物及顯示面板。更詳細而言，係關於形成液晶顯示面板或觸控面板等顯示面板用之間隔物之感光性樹脂組成物，由該感光性樹脂組成物所形成之顯示面板用間隔物及具備該間隔物所成顯示面板。The present invention relates to a photosensitive resin composition, a spacer for a display panel, and a display panel. More specifically, the photosensitive resin composition for forming a spacer for a display panel such as a liquid crystal display panel or a touch panel, the spacer for a display panel formed of the photosensitive resin composition, and the spacer Become a display panel.

以往液晶顯示面板為了使2片基板間之間隔(晶胞間隙)保持一定，而使用具有所定粒徑之玻璃珠、塑膠珠等之間隔物粒子。這些間隔物粒子在玻璃基板等透明基板上呈不規則散布，因此在像素形成區域含有間隔物粒子時，會產生間隔物粒子之映入現象或入射光散亂，液晶面板之對比降低之問題。Conventionally, in order to keep the interval (cell gap) between two substrates constant, the liquid crystal display panel uses spacer particles such as glass beads or plastic beads having a predetermined particle diameter. Since these spacer particles are irregularly dispersed on a transparent substrate such as a glass substrate, when the pixel formation region contains spacer particles, a phenomenon in which spacer particles are reflected or scattered incident light is generated, and the contrast of the liquid crystal panel is lowered.

因此，為了解決這些問題，而採用藉由光蝕刻來形成間隔物的方法。此方法係將感光性樹脂組成物塗佈於基板上，經由所定之光罩以紫外線曝光後進行顯像，形成點狀或條帶狀之間隔物者，因僅在像素形成區域以外之所定場所可形成間隔物，因此基本上解決如前述的問題。Therefore, in order to solve these problems, a method of forming a spacer by photo etching is employed. In this method, a photosensitive resin composition is applied onto a substrate, and after exposure to ultraviolet light through a predetermined mask, development is performed to form dots or strip-shaped spacers, which are only in a predetermined place other than the pixel formation region. Spacers can be formed, thus substantially solving the problems as described above.

實際之間隔物形成步驟，例如在彩色濾光片等所用之基板上藉由光蝕刻形成間隔物時，大多使用接近式曝光機。此接近式曝光機曝光時，光罩與塗佈感光性組成物之基板之間設置一定之間隙曝光，如光罩之圖案曝光較理想。但是前述間隙充滿空氣或氮氣，通過光罩之開口部(透明部)之光以該間隙部擴散，因此產生比光罩圖案之設計尺寸更寬曝光的問題。In the actual spacer forming step, for example, when a spacer is formed by photolithography on a substrate used for a color filter or the like, a proximity exposure machine is often used. When the proximity exposure machine is exposed, a certain gap is exposed between the photomask and the substrate on which the photosensitive composition is applied, and the pattern exposure of the photomask is ideal. However, the gap is filled with air or nitrogen, and the light passing through the opening (transparent portion) of the mask is diffused by the gap portion, so that there is a problem that the exposure is wider than the design size of the mask pattern.

為了解決這種問題，本申請人已於日本特開2001－261761號公報中揭示使用1,2－辛烷二酮－1－〔4－(苯硫基)苯基〕－2－(O－苯醯基肟)作為感光性組成物之光聚合引發劑，即使以接近式曝光也可忠實實現光罩圖案之設計尺寸，可形成強度、耐熱性等優異之顯示面板用間隔物。In order to solve such a problem, the present applicant has disclosed the use of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-) in JP-A-2001-261761. As a photopolymerization initiator of the photosensitive composition, the design of the mask pattern can be faithfully achieved by the proximity exposure, and a spacer for a display panel excellent in strength, heat resistance, and the like can be formed.

隨著液晶顯示面板之大型化，必須精確控制晶胞間隙，但是由間隔物用感光性組成物所形成之被膜與基板之密著性不足時，所形成之間隔物會偏離基板，結果精確保持晶胞間隙。液晶顯示面板係進行像素之高開口率化，結果可配置間隔物之黑色矩陣區域之面積漸漸縮小。因此即使在某程度可進入像素區域也不影響像素之色調，對於間隔物仍要求更高透明性。With the enlargement of the liquid crystal display panel, it is necessary to precisely control the cell gap, but when the adhesion between the film formed by the photosensitive composition of the spacer and the substrate is insufficient, the spacer formed is deviated from the substrate, and the result is accurately maintained. Cell gap. The liquid crystal display panel performs high aperture ratio of pixels, and as a result, the area of the black matrix region in which the spacers can be arranged is gradually reduced. Therefore, even if the pixel area can be entered to some extent without affecting the hue of the pixel, higher transparency is required for the spacer.

但是也包括特開2001－261761號公報所記載者，形成間隔物所用之感光性組成物在與基板之密著性及透明性方面仍不充分，需要開發兼具這些特性之感光性組成物。However, as described in Japanese Laid-Open Patent Publication No. 2001-261761, the photosensitive composition for forming a spacer is insufficient in adhesion to the substrate and transparency, and it is necessary to develop a photosensitive composition having these characteristics.

近年，因液晶顯示裝置之大面積化或提高生產性等，因此主玻璃基板也進行大型化。以往之基板尺寸(680×880mm)係基板尺寸小於光罩，因此可使用一次曝光方式。In recent years, the size of the liquid crystal display device has increased, and productivity has increased. In the conventional substrate size (680 × 880 mm), the substrate size is smaller than that of the mask, so that one exposure method can be used.

但是大型基板(例如1500×1800mm)幾乎無法製作與此基板相同之光罩尺寸，很難使用一次曝光方式。大型基板曝光方式提案使用階段曝光方式。但是階段曝光方式係對於基板進行數次曝光，每一次需要對準位置、階段移動之時間。階段曝光方式相較於一次曝光方式，可能會降低生產率。一次曝光方式可容許3000J/m2 之曝光感度，但是階段曝光方式則要求1500J/m2 以下之曝光感度。以往之材料很難要求以1500J/m2 以下之曝光量得到充分之間隔物形狀及膜厚。However, a large substrate (for example, 1500 × 1800 mm) is almost impossible to produce the same mask size as the substrate, and it is difficult to use the one-time exposure method. The large substrate exposure method proposal uses a stage exposure method. However, the stage exposure method is to perform several exposures on the substrate, each time requiring alignment time and phase shift time. The stage exposure method may reduce productivity compared to the one-shot method. A permissible exposure method 3000J / m 2 of exposure sensitivity, but the phase of the exposure method of claim 2 or less exposure sensitivity 1500J / m. In the conventional materials, it is difficult to obtain a sufficient spacer shape and film thickness at an exposure amount of 1500 J/m 2 or less.

關於間隔物形狀、膜厚之控制性之要求值，近年越來越嚴格，仍有形成間隔物時因製程變動產生形狀、膜厚之變動、組成物溶液之經時變化所產生之形狀、膜厚之安定性的問題。特別是1500J/m2 以下之曝光量範圍，仍有對於曝光量之間隔物形狀、膜厚之控制性的問題。The value of the controllability of the shape of the spacer and the thickness of the film has become more and more stringent in recent years, and there are still shapes and film thickness variations due to process variations in the formation of spacers, and shapes due to changes in the composition solution over time. The problem of thick stability. In particular, in the range of exposure amount of 1500 J/m 2 or less, there is still a problem of controllability of the shape of the spacer and the film thickness of the exposure amount.

近年液晶顯示面板製造用之感光性組成物，因保存期間，使用中因組成物中之成分結晶等產生雜質污染裝置等問題嚴重，因而期待降低這種問題之感光性組成物。In recent years, the photosensitive composition for producing a liquid crystal display panel has a problem that the device is contaminated by impurities such as crystals of components in the composition during use, and a photosensitive composition which is expected to reduce such a problem is expected.

〔發明之揭示〕[disclosure of invention]

本發明之課題係高感度，且可忠實實現光罩圖案之設計尺寸，且與基板之密著性優，在1500J/m2 以下之曝光量也可得到充分之間隔物形狀及膜厚，可形成強度、耐熱性優異，另外在低曝光區域之間隔物形狀及膜厚之抑制性優異，保存期間中，使用中不易產生異物，可形成製程安定性、經過時間之安定性優異之顯示面板用間隔物的感光性樹脂組成物，顯示面板用間隔物及顯示面板。The subject of the present invention is high sensitivity, and can faithfully realize the design size of the mask pattern, and has excellent adhesion to the substrate, and a sufficient spacer shape and film thickness can be obtained at an exposure amount of 1500 J/m 2 or less. It is excellent in formation strength and heat resistance, and is excellent in the shape of the spacer and the film thickness in the low-exposure region. In the storage period, foreign matter is less likely to be generated during use, and the display panel is excellent in process stability and stability over time. A photosensitive resin composition of a spacer, a spacer for a display panel, and a display panel.

依據本發明時，前述課題第一可藉由下述感光性樹脂組成物(以下稱為「感光性樹脂組成物(甲)」)來達成。According to the present invention, the first object can be achieved by the following photosensitive resin composition (hereinafter referred to as "photosensitive resin composition (A)").

一種感光性樹脂組成物，其特徵為含有：〔A〕(a1)乙烯性不飽和羧酸及/或乙烯性不飽和羧酸酐與(a2)其他乙烯性不飽和化合物之共聚物，〔B〕具有乙烯性不飽和鍵之聚合性化合物及〔C〕由下述式(1)或(2)表示之化合物所構成之光聚合引發劑， A photosensitive resin composition comprising: [A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and [C] a photopolymerization initiator composed of a compound represented by the following formula (1) or (2),

〔R1 表示碳數1~20之烷基、碳數3~8之環烷基或苯基，R2 與R3 分別為氫原子、碳數1~20之烷基、碳數3~8之環烷基、取代或未取代之苯基或碳數7~20之脂環基(但是碳數7~8之環烷基除外)，上述取代苯基之取代基為碳數1~6之烷基、碳數1~6之烷氧基、苯基或鹵原子，R4 為碳數4~20之含氧雜環基、碳數4~20之含氮雜環基或碳數4~20之含硫雜環基，R5 係表示氫、碳數1~12之烷基或碳數1~12之烷氧基，n為1~5之整數，m為0~5之整數，n＋m≦5， [R 1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3 to 8 a cycloalkyl group, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the above substituted phenyl group is a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, R 4 is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a carbon number of 4~ a sulfur-containing heterocyclic group of 20, R 5 represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, n + m ≦5,

R1 、R2 、R3 、R4 、R5 、m及n之定義係與上述相同，l為0~6之整數。The definitions of R 1 , R 2 , R 3 , R 4 , R 5 , m and n are the same as above, and l is an integer of 0-6.

依據本發明時，前述課題第二可藉由感光性樹脂組成物(甲)所形成之顯示面板用間隔物來達成。According to the invention, the second problem can be achieved by the spacer for a display panel formed by the photosensitive resin composition (A).

依據本發明時，前述課題第三可藉由具備前述顯示面板用間隔物所成之顯示面板來達成。According to the invention, the third problem can be achieved by providing the display panel formed by the spacer for the display panel.

以下詳細說明本發明。The invention is described in detail below.

感光性樹脂組成物(甲)－共聚物〔A〕－感光性樹脂組成物(甲)之〔A〕成分係由(a1)乙烯性不飽和羧酸及/或乙烯性不飽和羧酸酐與(a2)其他乙烯性不飽和化合物之共聚物(以下稱為「共聚物〔A〕」)所構成。Photosensitive resin composition (A)-copolymer [A] - The photosensitive resin composition (A) [A] is composed of (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and A2) A copolymer of another ethylenically unsaturated compound (hereinafter referred to as "copolymer [A]").

構成共聚物〔A〕之各成分中，(a1)乙烯性不飽和羧酸及/或乙烯性不飽和羧酸酐(以下這些統稱為「不飽和羧酸系單體(a1)」例如有丙烯酸、甲基丙烯酸、巴豆酸、2－甲基丙烯醯氧基乙基琥珀酸、2－甲基丙烯醯氧基乙基六氫鄰苯二甲酸之單羧酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、依康酸之二羧酸；前述二羧酸之酸酐等。Among the components constituting the copolymer [A], (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic acid anhydride (hereinafter collectively referred to as "unsaturated carboxylic acid monomer (a1)", for example, acrylic acid, Monocarboxylic acid of methacrylic acid, crotonic acid, 2-methylpropenyloxyethyl succinic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid; maleic acid, anti-butene a dicarboxylic acid of diacid, citraconic acid, mesaconic acid, and itaconic acid; an acid anhydride of the above dicarboxylic acid; and the like.

這些不飽和羧酸系單體(a1)中，從共聚反應性、共聚物對於鹼水溶液之溶解性及易於取得之觀點而言，較佳為丙烯酸、甲基丙烯酸、順丁烯二酸酐等。Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity, solubility of the copolymer to an aqueous alkali solution, and ease of availability.

在感光性樹脂組成物(甲)中，不飽和羧酸系單體(a1)可單獨使用或混合2種以上使用。In the photosensitive resin composition (A), the unsaturated carboxylic acid monomer (a1) may be used singly or in combination of two or more.

共聚物〔A〕中，來自不飽和羧酸系單體(a1)之重覆單元之含有比率較佳為5~50重量%，更佳為10~40重量%，特佳為15~30重量%。來自不飽和羧酸系單體(a1)之重覆單元之含有比率未達5重量%時，對於鹼水溶液之溶解性有降低之傾向，另外超過50重量%時，對於鹼水溶液之溶解性可能過大。In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. %. When the content ratio of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is less than 5% by weight, the solubility in the aqueous alkali solution tends to decrease, and when it exceeds 50% by weight, the solubility in the aqueous alkali solution may be is too big.

又，(a2)其他乙烯性不飽和化合物可使用含環氧基乙烯性不飽和化合物(以下稱為「含環氧基單體」)及不含環氧基之其他乙烯性不飽和化合物(以下僅稱「其他單體」)。這些可單獨或組合使用。含環氧基單體例如有丙烯酸環氧丙酯、丙烯酸2－甲基環氧丙酯、丙烯酸3,4－環氧基丁酯、丙烯酸6,7－環氧基庚酯、丙烯酸3,4－環氧基環己酯之丙烯酸環氧基烷酯；甲基丙烯酸環氧丙酯、甲基丙烯酸2－甲基環氧丙酯、甲基丙烯酸3,4－環氧基丁酯、甲基丙烯酸6,7－環氧基庚酯、甲基丙烯酸3,4－環氧基環己酯之甲基丙烯酸環氧基烷酯；α－乙基丙烯酸環氧丙酯、α－正丙基丙烯酸環氧丙酯、α－正丁基丙烯酸環氧丙酯、α－乙基丙烯酸6,7－乙氧基庚酯之α－烷基丙烯酸環氧基烷酯；鄰乙烯基苄基環氧丙基醚、間乙烯基苄基環氧丙基醚、對乙烯基苄基環氧丙基醚之環氧丙基醚。Further, (a2) other ethylenically unsaturated compound may be an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing monomer") and other ethylenically unsaturated compound not containing an epoxy group (hereinafter) Just called "other monomers"). These can be used singly or in combination. The epoxy group-containing monomer is, for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, acrylic acid 3,4. - epoxycycloalkyl acrylate of epoxy-cyclohexyl ester; glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, methyl 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl methacrylate, epoxy methacrylate, α-ethyl methacrylate, α-n-propyl acrylate Glycidyl acrylate, α-n-butyl acrylate propylene acrylate, α-alkyl acrylate epoxy methacrylate of α-ethyl acrylate 6,7-ethoxyheptyl ester; o-vinyl benzyl epoxide Epoxy ether, m-vinylbenzyl epoxy propyl ether, p-vinylbenzyl epoxy propyl ether epoxy propyl ether.

這些含環氧基單體中，從共聚反應性及間隔物之強度之觀點而言，較佳為甲基丙烯酸環氧丙酯、甲基丙烯酸2－甲基環氧丙酯、甲基丙烯酸6,7－環氧基庚酯、鄰乙烯基苄基環氧丙基醚、間乙烯基苄基環氧丙基醚、對乙烯基苄基環氧丙基醚。Among these epoxy group-containing monomers, from the viewpoints of copolymerization reactivity and strength of the spacer, glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 6 are preferable. , 7-epoxyheptyl ester, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether.

感光性樹脂組成物(甲)中，含環氧基單體可單獨使用或混合2種以上使用。In the photosensitive resin composition (A), the epoxy group-containing monomers may be used singly or in combination of two or more.

共聚物〔A〕中，來自含環氧基單體之重覆單元之含有比率較佳為10~70重量%，更佳為20~60重量%，特佳為30~50重量%。來自含環氧基單體之重覆單元之含有比率未達10重量%時，所得之間隔物之強度有降低的傾向，另外超過70重量%時，所得之共聚物之保存安定性有降低的傾向。In the copolymer [A], the content ratio of the repeating unit derived from the epoxy group-containing monomer is preferably from 10 to 70% by weight, more preferably from 20 to 60% by weight, particularly preferably from 30 to 50% by weight. When the content ratio of the repeating unit derived from the epoxy group-containing monomer is less than 10% by weight, the strength of the obtained spacer tends to decrease, and when it exceeds 70% by weight, the storage stability of the obtained copolymer is lowered. tendency.

(a3)乙烯性不飽和化合物之其他單體，例如有丙烯酸甲酯、丙烯酸異丙酯等之丙烯酸烷酯；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、甲基丙烯酸第三丁酯之甲基丙烯酸烷酯；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－酯、丙烯酸2－(三環〔5.2.1.02 , 6 〕癸烷－8－氧基)乙酯、丙烯酸異冰片酯之丙烯酸脂環酯；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、甲基丙烯酸2－(三環〔5.2.1.02 , 6 〕癸烷－8－氧基)乙酯、甲基丙烯酸異冰片酯之甲基丙烯酸脂環酯；丙烯酸苯酯、丙烯酸苄酯之丙烯酸之芳酯或芳烷酯；甲基丙烯酸苯酯、甲基丙烯酸苄酯之甲基丙烯酸芳酯或芳烷酯；順丁烯二酸二乙酯、反丁烯二酸二乙酯、依康酸二乙酯之二羧酸二烷酯；甲基丙烯酸2－羥基乙酯、甲基丙烯酸2－羥丙酯之甲基丙烯酸羥烷酯；甲基丙烯酸四氫糠酯、甲基丙烯酸四氫呋喃酯、甲基丙烯酸四氫哌喃－2－甲酯之含氧一原子之不飽和雜五及六員環甲基丙烯酸酯；苯乙烯、α－甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯之乙烯芳香族化合物；1,3－丁二烯、異戊二烯、2，3－二甲基－1,3－丁二烯之共軛二烯系化合物及丙烯腈、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、氯化乙烯、偏氯乙烯、乙酸乙烯等。(a3) other monomers of the ethylenically unsaturated compound, for example, alkyl acrylate such as methyl acrylate or isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl Dibutyl acrylate, alkyl methacrylate of butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 2 , 6 ] decane-8- Ester, 2-(tricyclo[5.2.1.0 2 , 6 ]decane-8-oxy)ethyl acrylate, acrylate cyclic ester of isobornyl acrylate; cyclohexyl methacrylate, 2-methyl methacrylate cyclohexyl methacrylate, tricyclo [5.2.1.0 2, 6] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 2, 6] decan-8-yloxy) acetate Esters, methacrylate alicyclic esters of isobornyl methacrylate; phenyl acrylate, aryl or aryl acrylate of benzyl acrylate; phenyl methacrylate, methacrylate methacrylate Or arylalkyl ester; diethyl maleate, diethyl fumarate, diethyl diconate dialkyl dicarboxylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate hydroxyalkyl methacrylate; tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate, tetrahydropyran-2-methacrylate Oxygen-containing monoatomic unsaturated penta- and six-membered ring methacrylates of esters; ethylene of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene Aromatic compound; conjugated diene compound of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and acrylonitrile, methacrylonitrile, propylene oxime Amine, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, and the like.

這些其他單體中，從共聚反應性及所得之共聚物對鹼水溶液之溶解性的觀點而言，較佳為丙烯酸2－甲基環己酯、甲基丙烯酸第三丁酯、甲基丙烯酸三環〔5.2.1.02 , 6 〕癸烷－8－酯、苯乙烯、對甲氧基苯乙烯、甲基丙烯酸四氫糠酯、1,3－丁二烯等。Among these other monomers, from the viewpoints of copolymerization reactivity and solubility of the obtained copolymer to an aqueous alkali solution, 2-methylcyclohexyl acrylate, tert-butyl methacrylate, and methacrylic acid are preferable. Ring [5.2.1.0 2 , 6 ] decane-8-ester, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene, and the like.

感光性樹脂組成物(甲)中，其他之單體可單獨使用或混合2種以上使用。In the photosensitive resin composition (A), the other monomers may be used singly or in combination of two or more.

共聚物〔A〕中，來自其他單體之重覆單元之含有比率，較佳為10~70重量%，更佳為20~50重量%，特佳為30~50重量%。來自其他單體之重覆單元之含有比率未達10重量%時，所得之共聚物之保存安定性有降低的傾向，而超過70重量%時，所得之共聚物對鹼水溶液之溶解性有降低的傾向。In the copolymer [A], the content ratio of the repeating unit derived from the other monomer is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight, particularly preferably from 30 to 50% by weight. When the content ratio of the repeating unit derived from another monomer is less than 10% by weight, the storage stability of the obtained copolymer tends to be lowered, and when it exceeds 70% by weight, the solubility of the obtained copolymer to the aqueous alkali solution is lowered. Propensity.

共聚物〔A〕係具有羧基及/或羧酸酐基與環氧基，對於鹼水溶液具有適度溶解性，同時，即使不併用特別的硬化劑藉由加熱也可容易硬化，含有該共聚物之感光性樹脂組成物(甲)在顯像時，不會產生顯像殘留及膜變薄，可容易形成設定圖型之間隔物。The copolymer [A] has a carboxyl group and/or a carboxylic acid anhydride group and an epoxy group, and has an appropriate solubility in an aqueous alkali solution, and can be easily cured by heating without using a special curing agent, and the photosensitive film containing the copolymer When the resin composition (A) is developed, no development residue or film thinning occurs, and a spacer of a pattern can be easily formed.

共聚物〔A〕可在適當溶劑及自由基聚合引發劑之存在下，使不飽和羧酸單體(a1)、含環氧基單體及/或其他單體(a2)藉由聚合製造。The copolymer [A] can be produced by polymerizing an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer, and/or another monomer (a2) in the presence of a suitable solvent and a radical polymerization initiator.

製造共聚物〔A〕所用之溶劑例如有醇、醚、乙二醇醚、乙二醇烷基醚乙酸酯、二乙二醇、二丙二醇、丙二醇單烷醚、丙二醇烷醚乙酸酯、丙二醇烷醚丙酸酯、芳香族烴、酮、酯等。The solvent used for the production of the copolymer [A] is, for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, Propylene glycol alkane propionate, aromatic hydrocarbon, ketone, ester, and the like.

這些具體例，其中醇有甲醇、乙醇、苄醇、2－苯基乙醇、3－苯基－1－丙醇等；醚例如有四氫呋喃等；乙二醇醚例如有乙二醇單甲醚、乙二醇單***等；乙二醇烷醚乙酸酯例如有甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單***乙酸酯等；二乙二醇例如有二乙二醇單甲醚、二乙二醇單***、二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲醚等；二丙二醇例如有二丙二醇單甲醚、二丙二醇單***、二丙二醇二甲醚、二丙二醇二***、二丙二醇乙基甲醚等；丙二醇單烷醚例如有丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等；丙二醇烷醚乙酸酯例如有丙二醇甲醚乙酸酯、丙二醇***乙酸酯、丙二醇丙醚乙酸酯、丙二醇丁醚乙酸酯等；丙二醇烷醚丙酸酯例如有丙二醇甲醚丙酸酯、丙二醇***丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等；芳香族烴例如有甲苯、二甲苯等；酮例如有甲基乙基酮、環己酮、4－羥基－4－甲基－2－戊酮等；酯例如有乙酸甲酯、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－丁氧基丙酸丁基等之酯。Specific examples thereof include methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, and the like; ethers such as tetrahydrofuran; and glycol ethers such as ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether Acetate, etc.; diethylene glycol, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. Dipropylene glycol is, for example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; Propionates such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol Ether propionate, propylene glycol butyl ether propionate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate , propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxide, butyl butoxyacetate, butyl butoxyacetate, 2- Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butyl Propyl oxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propane Methyl oxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butyl An ester of ethyl oxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate or the like.

這些中，較佳為乙二醇烷基醚乙酸酯、二乙二醇、二丙二醇、二丙二醇單烷醚、丙二醇烷醚乙酸酯，更佳為二乙二醇二甲醚、二乙二醇乙基甲醚、二丙二醇二甲醚、二丙二醇乙基甲醚、丙二醇甲醚、丙二醇甲醚乙酸酯。Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, dipropylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, more preferably diethylene glycol dimethyl ether, diethyl Glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate.

上述溶劑可單獨使用或混合2種以上使用。These solvents may be used singly or in combination of two or more.

上述聚合所用之自由基聚合引發劑，無特別限定，例如有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)之偶氮化合物；苯醯基過氧化物、月桂醯基過氧化物、第三丁基過氧三甲基乙酸酯、1，1－雙(第三丁基過氧)環己烷之有機過氧化物；過氧化氫等。自由基聚合引發劑使用過氧化物時，可與還原劑併用，作為氧化還原型引發劑。The radical polymerization initiator to be used in the above polymerization is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2 , 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2' - azo compound of azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzoguanidino peroxide , lauryl sulfhydryl peroxide, tert-butyl peroxytrimethyl acetate, organic peroxide of 1,1-bis(t-butylperoxy)cyclohexane; hydrogen peroxide and the like. When a peroxide is used as a radical polymerization initiator, it can be used together with a reducing agent as a redox type initiator.

這些自由基聚合引發劑可單獨使用或混合2種以上使用。These radical polymerization initiators can be used alone or in combination of two or more.

上述所得之共聚物〔A〕可為溶液狀態，直接供調製輻射敏感性樹脂組成物用，也可從溶液中分離，供調製輻射敏感性樹脂組成物用。The copolymer [A] obtained above may be in the form of a solution, and may be used as a composition for modulating a radiation-sensitive resin, or may be separated from a solution for modulating a composition of a radiation-sensitive resin.

共聚物〔A〕之凝膠滲透層析法(GPC)之聚苯乙烯換算重量平均分子量(以下稱為「Mw」)，較佳為2,000~100,000，更佳為5,000~50,000。Mw未達2,000時，所得之被膜之顯像性、殘膜率等會降低，且可能損及圖案形狀、耐熱性等，又超過100,000時，解像度降低，或可能影響圖案形狀。The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the gel permeation chromatography (GPC) of the copolymer [A] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the Mw is less than 2,000, the development of the obtained film, the residual film ratio, and the like may be lowered, and the shape, heat resistance, and the like may be impaired. When the Mw exceeds 100,000, the resolution is lowered or the pattern shape may be affected.

－聚合性化合物〔B〕－感光性樹脂組成物(甲)中之〔B〕成分係具有乙烯性不飽和鍵之聚合性化合物(以下稱為「聚合性化合物〔B〕」)。- Polymerizable Compound [B] - The component [B] in the photosensitive resin composition (A) is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as "polymerizable compound [B]").

聚合性化合物〔B〕無特別限定，但單官能、2官能或3官能以上(甲基)丙烯酸酯因聚合性良好，可提高所得之間隔物的強度，因此較佳。The polymerizable compound [B] is not particularly limited, but a monofunctional, bifunctional or trifunctional or higher (meth) acrylate is preferred because it has good polymerizability and can increase the strength of the resulting spacer.

單官能(甲基)丙烯酸酯例如有，2－羥乙基丙烯酸酯、2－羥乙基甲基丙烯酸酯、二乙二醇單***丙烯酸酯、二乙二醇單***甲基丙烯酸酯、異冰片基丙烯酸酯、異冰片基甲基丙烯酸酯、3－甲氧基丁基丙烯酸酯、3－甲氧基丁基甲基丙烯酸酯、2－丙烯醯氧基乙基－2－羥丙基鄰苯二甲酸酯、2－甲基丙烯醯氧基乙基－2－羥丙基鄰苯二甲酸酯等，又市售品例如有Aronix M－101、同M－111、同M－114(東亞合成(股)製)；KAYARAD TC－110S，同TC－120S(日本化藥(股)製)；Viscoat 158、同2311(大阪有機化學工業(股)製)等。Monofunctional (meth) acrylates are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, diethylene glycol monoethyl methacrylate, and Borne based acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-propenyloxyethyl-2-hydroxypropyl phthalate Formate, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate, etc., and commercially available products such as Aronix M-101, M-111, and M-114 (East Asia Synthetic (stock) system; KAYARAD TC-110S, same as TC-120S (Nippon Chemical Co., Ltd.); Viscoat 158, same 2311 (Osaka Organic Chemical Industry Co., Ltd.).

2官能基(甲基)丙烯酸酯例如有乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、丁二醇二丙烯酸酯、丁乙二醇二甲基丙烯酸酯、1,6－己二醇二丙烯酸酯、1,6－己二醇二甲基丙烯酸酯、1,9－壬二醇二丙烯酸酯、1,9－壬二醇二甲基丙烯酸酯、雙苯氧基乙醇芴二丙烯酸酯、雙苯氧基乙醇芴二甲基丙烯酸酯等，又市售品例如有Aronix M－210、同M－240、同M－6200(東亞合成(股)製)、KAYARAD HDDA、同HX－220、同R－604(日本化藥(股)製)、Viscoat 260、同312、同335HP(大阪有機化學工業(股)製)等。The bifunctional (meth) acrylates are, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, butanediol diacrylic acid. Ester, butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9 - decanediol dimethacrylate, bisphenoxyethanol hydrazine diacrylate, bisphenoxyethanol hydrazine dimethacrylate, etc., and commercially available products such as Aronix M-210, same M-240, same M-6200 (East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Chemical Co., Ltd.), Viscoat 260, 312, and 335HP (Osaka Organic Chemical Industry Co., Ltd.) System) and so on.

3官能以上之(甲基)丙烯酸酯例如有三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇三甲基丙烯酸酯、新戊四醇四丙烯酸酯、新戊四醇四甲基丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇五甲基丙烯酸酯、二新戊四醇六丙烯酸酯、二新戊四醇六甲基丙烯酸酯、三(2－丙烯醯基氧乙基)磷酸酯、三(2－甲基丙烯醯基氧乙基)磷酸酯等。The trifunctional or higher (meth) acrylate is, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, new Pentaerythritol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Alcohol hexamethacrylate, tris(2-propenyl methoxyethyl) phosphate, tris(2-methylpropenyl oxyethyl) phosphate, and the like.

特別是9官能以上之(甲基)丙烯酸酯係具有伸烷基直鏈及脂環構造，將含有2個以上異氰酸酯基之化合物與分子內含有1個以上羥基之3官能、4官能及5官能之(甲基)丙烯酸酯化合物產生反應所得之胺基甲酸乙酯丙烯酸酯化合物。In particular, the hexa-functional or higher (meth) acrylate has a linear alkyl chain and an alicyclic structure, and a compound containing two or more isocyanate groups and a trifunctional, tetrafunctional, and pentafunctional group having one or more hydroxyl groups in the molecule. The (meth) acrylate compound produces a urethane acrylate compound obtained by the reaction.

上述市售品例如有Aronix M－309、同M－400、同M－405、同M－450、同M－7100、同M－8030、同M－8060、同TO－1450(東亞合成(股)製)、KAYARAD TMPTA、同DPHA、同DPCA－20、同DPCA－30、同DPCA－60、同DPCA－120(日本化藥(股)製)、Viscoat 295、同300、同360、同GPT、同3PA、同400(大阪有機化學工業(股)製)等。9官能以上之多官能胺基甲酸乙酯丙烯酸酯之市售品，例如有New frontier R－1150(以上，第一工業製藥(股)製)、KAYARAD DPHA－40H(以上，日本化藥(股)製)等。The above-mentioned commercial products include, for example, Aronix M-309, the same M-400, the same M-405, the same M-450, the same M-7100, the same M-8030, the same M-8060, the same TO-1450 (East Asian synthesis) )), KAYARAD TMPTA, with DPHA, with DPCA-20, with DPCA-30, with DPCA-60, with DPCA-120 (Nippon Chemical Co., Ltd.), Viscoat 295, with 300, with 360, with GPT , the same as 3PA, the same 400 (Osaka Organic Chemical Industry Co., Ltd.) and so on. A commercial product of a polyfunctional urethane acrylate having a ninth or more functional group, for example, New Frontier R-1150 (above, manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (above, Nippon Kayaku Co., Ltd.) ))).

這些單官能、2官能或3官能以上之(甲基)丙烯酸酯中，以3官能以上之(甲基)丙烯酸酯較佳，特佳為三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇五丙烯酸酯及二新戊四醇六丙烯酸酯。Among these monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates, a trifunctional or higher (meth) acrylate is preferable, and particularly preferably trimethylolpropane triacrylate or neopentyl alcohol Acrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

上述單官能、2官能或3官能以上之(甲基)丙烯酸酯可單獨或組合2種以上使用。The above-mentioned monofunctional, bifunctional or trifunctional or higher functional (meth) acrylate may be used alone or in combination of two or more.

感光性樹脂組成物(甲)中，聚合性化合物〔B〕之使用量係對於共聚物〔A〕100重量份時，較佳為50~140重量份，更佳為60~120重量份。聚合性化合物〔B〕使用量未達50重量份時，顯像時可能會發生顯像殘留，另外超過140重量份時，所得之間隔物之硬度有降低的傾向。In the photosensitive resin composition (A), the amount of the polymerizable compound [B] used is preferably from 50 to 140 parts by weight, more preferably from 60 to 120 parts by weight, per 100 parts by weight of the copolymer [A]. When the amount of the polymerizable compound [B] is less than 50 parts by weight, development residue may occur during development, and when it exceeds 140 parts by weight, the hardness of the obtained spacer tends to decrease.

－光聚合引發劑〔C〕－感光性樹脂組成物(甲)之〔C〕成分係由O－醯基肟型光聚合引發劑所構成，特別是上述式(1)或(2)表示之化合物(以下稱為「光聚合引發劑〔C〕」)較佳。- Photopolymerization Initiator [C] - The component [C] of the photosensitive resin composition (A) is composed of an O-fluorenyl hydrazine type photopolymerization initiator, and is particularly represented by the above formula (1) or (2). A compound (hereinafter referred to as "photopolymerization initiator [C]") is preferred.

本發明之光聚合引發劑係指藉由可見光線、紫外線、遠紫外線、帶電粒子線、X射線等之曝光，可產生使聚合性化合物〔B〕之開始聚合之活性種的成分。The photopolymerization initiator of the present invention is a component which can cause an active species which polymerizes the start of the polymerizable compound [B] by exposure to visible light, ultraviolet rays, far ultraviolet rays, charged particle rays, X-rays or the like.

上述式(1)或(2)表示之「光聚合引發劑〔C〕」中，R1 表示碳數1~20之烷基、碳數3~8之環烷基或苯基，R2 與R3 分別表示氫原子、碳數1~20之烷基、碳數3~8之環烷基，取代或未取代之苯基或碳數7~20之脂環基(但是碳數7~8之環烷基除外)。上述取代苯基之取代基為碳數1~6之烷基、碳數1~6之烷氧基、苯基及鹵原子。此等取代基可為1~5個，R4 為碳數4~20之含氧雜環基、碳數4~20之含氮雜環基或碳數4~20之含硫雜環基。R5 係表示氫、碳數1~12之烷基或碳數1~12之烷氧基。n為1~5之整數，m為0~5之整數，n＋m≦5，l為0~6之整數。In the "photopolymerization initiator [C]" represented by the above formula (1) or (2), R 1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R 2 is R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (but a carbon number of 7 to 8) Except for the cycloalkyl group). The substituent of the above substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. These substituents may be 1 to 5, and R 4 is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms. R 5 represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. n is an integer from 1 to 5, m is an integer from 0 to 5, n + m ≦ 5, and l is an integer from 0 to 6.

式(1)或(2)之R1 之碳數1~20之烷基可為直鏈狀或支鏈狀之烷基，其具體例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基。碳數3~8之環烷基例如有環戊基、環己基等。The alkyl group having 1 to 20 carbon atoms of R 1 of the formula (1) or (2) may be a linear or branched alkyl group, and specific examples thereof are a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. , n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl. The cycloalkyl group having 3 to 8 carbon atoms is, for example, a cyclopentyl group or a cyclohexyl group.

R2 與R3 之碳數1~20之烷基可為直鏈狀或支鏈狀之烷基，其具體例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基。碳數3~8之環烷基例如有環戊基、環己基等。The alkyl group having 1 to 20 carbon atoms of R 2 and R 3 may be a linear or branched alkyl group, and specific examples thereof are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like. Dibutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl. The cycloalkyl group having 3 to 8 carbon atoms is, for example, a cyclopentyl group or a cyclohexyl group.

R2 與R3 之取代苯基之取代基之碳數1~6之烷基可為直鏈狀、支鏈狀或環狀之烷基，其具體例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、環戊基、環己基等。The alkyl group having 1 to 6 carbon atoms of the substituent of the substituted phenyl group of R 2 and R 3 may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like.

碳數1~6之烷氧基可為直鏈狀、支鏈狀或環狀之烷基，其具體例為甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基等。鹵原子例如有氟原子、氯原子等。The alkoxy group having 1 to 6 carbon atoms may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, third butoxy, and the like. The halogen atom is, for example, a fluorine atom or a chlorine atom.

碳數7~20之脂環基(但是碳數7~8之環烷基除外)，例如有雙環烷基、三環烷基、螺烷基、第三環烷基、含帖烯骨架之基、含金剛烷骨架之基等。An alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a third cycloalkyl group, and a group containing a fluorene skeleton. , the base of the adamantane skeleton, and the like.

R4 之碳數4~20之含氮雜環基、碳數4~20之含氧雜環基、碳數4~20之含硫雜環基，例如有四氫噻吩基、吖庚因基、二氫吖庚因基、二氧雜環戊烷基、三嗪基、氧雜硫雜基、噻唑基、氧雜二嗪基、二氧雜茚滿基、二硫雜萘基、呋喃基、苯硫基、吡咯基、噁唑基、異噁唑基、噻唑基、異噻唑基、吡唑基、呋咱基、吡喃基、吡啶基、噠嗪基、嘧啶基、吡嗪基、吡咯啉基、嗎啉基、哌嗪基、奎寧環基、吲哚基、異吲哚基、苯並呋喃基、苯並苯硫基、吲哚嗪基、色烯基、喹啉基、異喹啉基、嘌呤基、喹唑啉基、異喹唑啉基、酞嗪基、喋啶基、咔唑基、吖啶基、菲繞啉基、噻噸基、吩嗪基、吩噻嗪基、吩噁嗪基、吩噻噁基、噻蒽基、四氫呋喃基、四氫吡喃基等。其中較佳者為四氫呋喃基、四氫吡喃基等。a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms of R 4 , an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, for example, a tetrahydrothiophenyl group or an azepine group , dihydroazepine, dioxolane, triazinyl, oxathiazyl, thiazolyl, oxadiazinyl, dioxaindanyl, dithianaphthyl, furyl , phenylthio, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, Pyrrolinyl, morpholinyl, piperazinyl, quinuclidinyl, fluorenyl, isodecyl, benzofuranyl, benzophenylthio, pyridazinyl, chromenyl, quinolyl, Isoquinolyl, fluorenyl, quinazolinyl, isoquinazolinyl, pyridazinyl, acridinyl, oxazolyl, acridinyl, phenanthroline, thioxanthyl, phenazinyl, phenothiazine Azinyl, phenoxazinyl, phenothionyl, thioxyl, tetrahydrofuranyl, tetrahydropyranyl and the like. Preferred among them are tetrahydrofuranyl group, tetrahydropyranyl group and the like.

R5 之碳數1~12之烷基可為直鏈狀、支鏈狀或環狀之烷基，其具體例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、環戊基、環己基等。The alkyl group having 1 to 12 carbon atoms of R 5 may be a linear, branched or cyclic alkyl group, and specific examples thereof are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like. Dibutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl and the like.

碳數1~12之烷氧基可為直鏈狀、支鏈狀或環狀之烷基，其具體例為甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基、正戊氧基等。The alkoxy group having 1 to 12 carbon atoms may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, third butoxy, n-pentyloxy and the like.

R5 中，較佳者為甲基、乙基、正丙基、異丙基、正丁基、甲氧基、乙氧基。Preferred among R 5 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a methoxy group or an ethoxy group.

n為1較佳。m為0、1、2其中之一，更佳為1。l為0、1、2其中之一，更佳為1。It is preferable that n is 1. m is one of 0, 1, 2, and more preferably 1. l is one of 0, 1, 2, and more preferably 1.

化合物〔C〕之具體例為乙酮，1－〔9－乙基－6－(2－甲基－2－四氫呋喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－2－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－2－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－2－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－3－四氫呋喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－3－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯距)；乙酮，1－〔9－乙基－6－(2－甲基－3－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－3－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫呋喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-5-四氫吡喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-2-四氫呋喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-2-四氫吡喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-2-四氫呋喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-2-四氫吡喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-，1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-3-四氫呋喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-3-四氫吡喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-3-四氫呋喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-3-四氫吡喃基甲氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-4-四氫呋喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-4-四氫吡喃氧基苯醯基)-9.H.-咔唑-3-基〕-,1-(O-苯醯基乙醯肟)；乙酮，1-〔9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－(2，2－二甲基－1,3－二氧雜環戊基)甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)等。A specific example of the compound [C] is ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]- , 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxyphenyl)-9.H.-carbazole 3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranylmethoxyphenyl)--9. H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranylmethoxy) Benzo hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-3) -tetrahydrofuranyloxybenzoyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl Benzyl-3-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl- 6-(2-methyl-3-tetrahydrofuranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1- [9-ethyl-6-(2-methyl-3-tetrahydropyranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine)乙); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O -acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)--9.H.-carbazole 3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl) -9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranoxybenzene Mercapto)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetra Hydropyridyloxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2- Methyl-5-tetrahydro Furyl methoxyphenyl fluorenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2- Methyl-5-tetrahydropyranylmethoxybenzoinyl-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9- Ethyl-6-(2-methyl-2-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone , 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-benzene Ethyl ketone); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranylmethoxyphenyl)--9 .H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranyloxy) Benzoyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl -3-tetrahydropyranoxyphenyl fluorenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-B -6-(2-methyl-3-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-benzoinylhydrazine Ethylketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydropyranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinium); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyloxyphenyl)-9.H.-carbazole- 3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl) -9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran) Methoxy phenyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl 4--4-hydropyranylmethoxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-B -6-(2-methyl-5-tetrahydrofuranyloxyphenyl)-9.H.-oxazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[ 9-ethyl-6-(2-methyl-5-tetrahydropyranyloxyphenyl)-9.H.-oxazol-3-yl]-, 1-(O-acetyl); Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)--9.H.-carbazole-3- ]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl)--9.H .-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-(2,2-dimethyl) -1,3-dioxolyl)methoxybenzoinyl-9-H.-carbazol-3-yl]-, 1-(O-acetamidine) and the like.

其中較佳者為乙酮，1－〔9－乙基－6－(2－甲基－4－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；乙酮，1－〔9－乙基－6－(2－甲基－5－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)；及乙酮，1－〔9－乙基－6－(2－甲基－4－(2，2－二甲基－1,3－二氧雜環戊基)甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯肟)。Preferred among them are ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenylhydrazino)-9.H.-咔Zyrid-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)--9 .H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl) Oxyphenyl phenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); and ethyl ketone, 1-[9-ethyl-6-(2-methyl 4-(2,2-dimethyl-1,3-dioxolanyl)methoxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-醯肟)).

這些光聚合引發劑〔C〕這些可單獨一種或組合2種以上使用。These photoinitiators (C) may be used alone or in combination of two or more.

光聚合引發劑〔C〕也可併用上述式(1)以外之O－乙醯肟型光聚合引發劑(以下稱為「光聚合引發劑〔C－2〕」)。As the photopolymerization initiator [C], an O-acetonitrile type photopolymerization initiator other than the above formula (1) (hereinafter referred to as "photopolymerization initiator [C-2]") may be used in combination.

這些光聚合引發劑〔C－2〕之具體例為1,2－辛二酮－1－〔4－(苯硫基)苯基〕－2－(O－苯醯基肟)、1,2－丁二酮－1－〔4－(苯硫基)苯基〕－2－(O－苯醯基肟)、1,2－丁二酮－1－〔4－(苯硫基)苯基〕－2－(O－乙醯基肟)、1,2－辛二酮－1－〔4－(甲硫基)苯基〕－2－(O－苯醯基肟)、1,2－辛二酮－1－〔4－(苯硫基)苯基〕－2－(O－(4－甲基苯醯基肟))等。其中較佳者為1,2－辛二酮－1－〔4－(苯硫基)苯基〕－2－(O－苯醯基肟)。光聚合引發劑〔C－2〕可使用光聚合引發劑〔C〕之30重量%以下。Specific examples of the photopolymerization initiator [C-2] are 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoinhydrazino), 1,2 -butanedione-1-[4-(phenylthio)phenyl]-2-(O-phenylhydrazinyl), 1,2-butanedione-1-[4-(phenylthio)phenyl -2-(O-ethylindenyl), 1,2-octanedione-1-[4-(methylthio)phenyl]-2-(O-phenylhydrazinyl), 1,2- Octanedione-1-[4-(phenylthio)phenyl]-2-(O-(4-methylphenylhydrazinyl)) and the like. The preferred one is 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-phenylhydrazinyl). The photopolymerization initiator [C-2] can be used in an amount of 30% by weight or less based on the photopolymerization initiator [C].

使用這些光聚合引發劑〔C〕即使以1500J/m2 以下之曝光量也可得到具有充分感度、密著性之間隔物。By using these photopolymerization initiators [C], a spacer having sufficient sensitivity and adhesion can be obtained even at an exposure amount of 1500 J/m 2 or less.

感光性樹脂組成物(甲)中之光聚合引發劑〔C〕之使用量係對於聚合性化合物〔B〕100重量份時，較佳為1~20重量份，更佳為2~15重量份。光聚合引發劑〔C〕之使用量未達1重量份時，顯像時之殘膜率有下降的傾向，另外超過20重量份時，顯像時未曝光部對於鹼性顯像液之溶解性有降低的傾向。The amount of the photopolymerization initiator [C] used in the photosensitive resin composition (A) is preferably from 1 to 20 parts by weight, more preferably from 2 to 15 parts by weight, per 100 parts by weight of the polymerizable compound [B]. . When the amount of the photopolymerization initiator [C] used is less than 1 part by weight, the residual film ratio at the time of development tends to decrease, and when it exceeds 20 parts by weight, the unexposed portion is dissolved in the alkaline developing solution at the time of development. Sex has a tendency to decrease.

感光性樹脂組成物(甲)中，可併用光聚合引發劑〔C〕與至少一種O－乙醯肟型光聚合引發劑以外之其他光聚合引發劑。In the photosensitive resin composition (A), a photopolymerization initiator [C] and at least one photopolymerization initiator other than the O-acetonitrile type photopolymerization initiator may be used in combination.

上述其他光聚合引發劑例如有雙咪唑系化合物、苯偶因系化合物、乙醯苯系化合物、二苯甲酮系化合物、α－二酮系化合物、多核醌系化合物、呫噸酮系化合物、膦系化合物、三嗪系化合物等。其中較佳者為乙醯苯系化合物(以下有時稱為「(D)成分」)、雙咪唑系化合物(以下有時稱為「(E)成分」)。Examples of the other photopolymerization initiator include a bisimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a polynuclear oxime compound, and a xanthone compound. A phosphine compound, a triazine compound, or the like. Among them, an acetaminophen compound (hereinafter sometimes referred to as "(D) component)" or a bisimidazole compound (hereinafter sometimes referred to as "(E) component") is preferred.

(D)成分：乙醯苯系化合物乙醯苯系化合物例如有α－羥基酮系化合物、α－胺基酮系化合物、這些以外之化合物。(D) component: acetonitrile-based compound The acetaminophen-based compound may, for example, be an α-hydroxyketone compound or an α-amino ketone compound or a compound other than these.

α－羥基酮系化合物之具體例，例如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－羥基環己基苯基酮等。α－胺基酮系化合物之具體例，例如2－甲基－1－〔4－(甲硫基)苯基〕－2－嗎啉基丙烷－1－酮、2－苄基－2－二甲基胺基－1－(4－嗎啉基苯基)－丁酮－1、2－(4－甲基苄基)－2－二甲基胺基－1－(4－嗎啉基苯基)－丁酮－1等。這些以外之化合物之具體例，例如2,2－二甲氧基乙醯苯、2,2－二乙氧基乙醯苯、2,2－二甲氧基－2－苯基乙醯苯等。Specific examples of the α-hydroxyketone-based compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like. Specific examples of the α-aminoketone compound are, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylbenzene Base)-butanone-1 and the like. Specific examples of the compounds other than these include, for example, 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenylethyl benzene, and the like. .

這些乙醯苯系化合物可單獨使用或混合2種以上使用。These acetophenone-based compounds may be used singly or in combination of two or more.

使用這些乙醯苯系化合物可提高感度、間隔物形狀及壓縮強度。The use of these acetophenone compounds can improve the sensitivity, the shape of the spacer, and the compressive strength.

(E)成份：雙咪唑系化合物雙咪唑系化合物之具體例，例如2,2'－雙(2－氯苯基)－4,4',5,5'－四(4－乙氧基羰基苯基)－1,2'－雙咪唑，2,2'－雙(2－溴苯基)－4,4',5,5'－四(4－乙氧基羰基苯基)－1,2'－雙咪唑，2,2'－雙(2－氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑，2,2'－雙(2,4－二氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑，2,2'－雙(2,4,6－三氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑，2,2'－雙(2－溴苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑，2,2'－雙(2,4－二溴苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑，2,2'－雙(2,4,6－三溴苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑等。(E) component: specific examples of the biimidazole-based compound diimidazole-based compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonyl) Phenyl)-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1, 2'-bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-bisimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2 '-Bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

上述雙咪唑系化合物中，較佳者為2,2'－雙(2－氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑、2,2'－雙(2,4－二氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑、2,2'－雙(2,4,6－三氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑等，更佳為2,2'－雙(2,4－二氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑。Among the above bisimidazole compounds, preferred is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2 '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-three Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, etc., more preferably 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-Tetraphenyl-1,2'-bisimidazole.

上述雙咪唑系化合物可單獨使用或混合2種以上使用。These biimidazole-based compounds may be used singly or in combination of two or more.

使用這些雙咪唑系化合物可提高感度、解像度及密著性。The use of these biimidazole-based compounds improves sensitivity, resolution, and adhesion.

又，為了使雙咪唑化合物增感，可使用具有二烷基胺基之脂肪族或芳香族系化合物(以下有時稱為「增感劑〔E－2〕」)。Further, in order to sensitize the bisimidazole compound, an aliphatic or aromatic compound having a dialkylamine group (hereinafter sometimes referred to as "sensitizer [E-2]") may be used.

上述增感劑〔E－2〕之具體例，例如N－甲基二乙醇胺、4,4'－雙(二甲基胺基)二苯甲酮、4,4'－雙(二乙基胺基)二苯甲酮、對二甲基胺基苯甲酸乙酯、對二甲基胺基苯甲酸異戊酯等。這些增感劑中，較佳者為4,4'－雙(二乙基胺基)二苯甲酮。Specific examples of the above sensitizer [E-2], such as N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamine) Base) benzophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. Of these sensitizers, preferred is 4,4'-bis(diethylamino)benzophenone.

這些增感劑〔E－2〕可使用1種或2種以上。These sensitizers [E-2] may be used alone or in combination of two or more.

增感劑〔E－2〕之使用量係對於〔A〕100重量份時，較佳為0.1~50重量份，更佳為1~20重量份。The amount of the sensitizer [E-2] used is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of [A].

增感劑〔E－2〕之量未達0.1重量份時，所得之間隔物有膜變薄或圖案形狀不良的傾向，又，超過50重量份時，同樣地會有圖案形狀不良的傾向。When the amount of the sensitizer [E-2] is less than 0.1 part by weight, the obtained spacer tends to have a thin film or a poor pattern shape, and when it exceeds 50 parts by weight, the pattern shape tends to be poor.

使用雙咪唑化合物時，可使用提供氫之化合物的硫醇系化合物(以下有時稱為「硫醇系化合物〔E－3〕。雙咪唑化合物係因具有二烷基胺基之二苯甲酮系化合物產生增感，使雙咪唑化合物開裂產生咪唑自由基。此時，未產生高自由基聚合開始能，常形成倒圓錐形狀之不良形狀。此問題可在雙咪唑化合物與具有二烷基胺基之二苯甲酮系化合物之共存體系中添加硫醇系化合物〔E－3〕予以緩和。將硫醇化合物之氫自由基供給咪唑自由基，產生具有中性之咪唑基與聚合引發能較高之硫自由基的化合物。藉此可由倒圓錐形狀形成較佳之圓錐形狀。When a bisimidazole compound is used, a thiol compound which provides a hydrogen compound (hereinafter sometimes referred to as "thiol compound [E-3]) may be used. The diimidazole compound is a benzophenone having a dialkylamine group. The compound is sensitized to cause the imidazole compound to be cleaved to generate an imidazole radical. At this time, no high radical polymerization initiation energy is produced, and a poor shape of an inverted conical shape is often formed. This problem can be caused by a diimidazole compound and a dialkylamine. The addition of the thiol compound [E-3] to the coexistence system of the benzophenone compound is moderated. The hydrogen radical of the thiol compound is supplied to the imidazole radical to produce a neutral imidazole group and the polymerization initiation energy. A compound of high sulfur radicals whereby a preferred conical shape can be formed from an inverted conical shape.

上述硫醇系化合物〔E－3〕之使用比率係對於化合物〔C〕100重量份時，較佳為0.1~50重量份，更佳為1~20重量份。硫醇系化合物〔E－3〕之量未達0.1重量份時，所得之間隔物有膜變薄或圖案形狀不良的傾向，又，超過50重量份時，同樣地也有圖案形狀不良的傾向。The use ratio of the above-mentioned thiol compound [E-3] is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the compound [C]. When the amount of the thiol compound [E-3] is less than 0.1 part by weight, the obtained spacer tends to have a thin film or a poor pattern shape, and when it exceeds 50 parts by weight, the pattern shape tends to be poor.

其具體例為2－氫硫基苯并噻唑、2－氫硫基苯并噁唑、2－氫硫基苯并咪唑、2－氫硫基－5－甲氧基苯并噻唑、2－氫硫基－5－甲氧基苯并咪唑等之芳香族系硫醇、3－氫硫基丙酸、3－氫硫基丙酸甲酯、3－氫硫基丙酸乙酯、3－氫硫基丙酸辛酯等之脂肪族系單硫醇。2官能基以上之脂肪族硫醇例如3,6－二氧雜－1,8－辛二硫醇、季戊四醇四(氫硫基乙酸酯)、季戊四醇四(3－氫硫基丙酸酯)等。Specific examples thereof are 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-5-methoxybenzothiazole, 2-hydrogen An aromatic thiol such as thio-5-methoxybenzimidazole, 3-hydrothiopropionic acid, methyl 3-hydrothiopropionate, ethyl 3-hydrothiopropionate, 3-hydrogen An aliphatic monothiol such as octyl thiopropionate. An aliphatic thiol having 2 or more functional groups such as 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetrakis (hydrothioacetate), pentaerythritol tetrakis(3-hydrothiopropionate) Wait.

其他光聚合引發劑之使用比例係對於全光聚合引發劑100重量份時，較佳為100重量份以下，更佳為80重量份以下，特佳為60重量份以下。此時其他光聚合引發劑之使用比例超過100重量份時，有時會影響本發明之效果。The ratio of use of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, even more preferably 60 parts by weight or less, per 100 parts by weight of the all-photopolymerization initiator. In this case, when the ratio of use of the other photopolymerization initiator exceeds 100 parts by weight, the effects of the present invention may be affected.

－添加劑－在感光性樹脂組成物(甲)中，在不影響本發明之效果的範圍內，可因應需要使用上述成分以外之添加劑。- Additive - In the photosensitive resin composition (A), an additive other than the above components may be used as needed within a range that does not impair the effects of the present invention.

例如，為了提高塗佈性，可配合界面活性劑。該界面活性劑，可適度使用氟系界面活性劑及聚矽氧系界面活性劑。For example, in order to improve coatability, a surfactant may be blended. As the surfactant, a fluorine-based surfactant and a polyoxyn-based surfactant can be suitably used.

在氟系界面活性劑可使用末端、主鏈及側鏈之至少任一部位具有氟烷基或氟伸烷基之化合物。其具體例有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、氟烷基苯磺酸鈉、氟烷基膦酸鈉、氟烷基羧酸鈉、氟烷基聚氧乙烯醚、二甘油基四(氟烷基聚氧乙烯醚)、氟烷基碘化銨、氟烷基甜菜鹼、氟烷基聚氧乙烯醚、全氟烷基聚氧基乙醇、全氟烷基烷基化物、氟系烷基酯等。As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluorine-extended alkyl group in at least any one of a terminal, a main chain and a side chain can be used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octaethylene. Alcohol bis(1,1,2,2-tetrafluorobutyl)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, sodium fluoroalkylbenzenesulfonate, fluoroalkylphosphonic acid Sodium, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglyceryl tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene Ether, perfluoroalkylpolyoxyethanol, perfluoroalkylalkylate, fluoroalkyl ester, and the like.

又，這些市售品例如有BM－1000、BM－1100(以上，BMCHEMIE公司製)、Megafac F142D、同F172、同F173、同F183、同F178、同F191、同F471、同F476(以上，大日本油墨化學工業(股)製)、Fulorad FC－170C、FC－171、FC－430、FC－431(以上，住友3M(股)製)、Surflon S－112、同S－113、同S－131、同S－141、同S－145、同S－382、同SC－101、同SC－102、同SC－103、同SC－104、同SC－105、同SC－106(以上，旭硝子(股)製)、Ftop EF301、同303、同352(以上，新秋田化成(股)製)、Ftergent FT－100、同FT－110、同FT－140A、同FT－150、同FT－250、同FT－251、同FTX－251、同FTX－218、同FT－300、同FT－310、同FT－400S(以上，(股)Neos製)等。Further, these commercially available products include, for example, BM-1000, BM-1100 (above, BMCHEMIE), Megafac F142D, F172, F173, F183, F178, F191, F471, and F476 (above, large Japan Ink Chemical Industry Co., Ltd., Fulorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M (share) system), Surflon S-112, same S-113, same S- 131, with S-141, with S-145, with S-382, with SC-101, with SC-102, with SC-103, with SC-104, with SC-105, with SC-106 (above, Asahi Glass) (share) system), Ftop EF301, same 303, same 352 (above, new Akita Chemicals Co., Ltd.), Ftergent FT-100, same FT-110, same FT-140A, same FT-150, same FT-250 , with FT-251, with FTX-251, with FTX-218, with FT-300, with FT-310, with FT-400S (above, (share) Neos) and so on.

又，聚矽氧系界面活性劑例如Toray聚矽氧DC3PA、同DC7PA、同SH11PA、同SH21PA、同SH28PA、同SH29PA、同SH30PA、同SH－190、同SH－193、同SZ－6032、同SF－8428、同DC－57、同DC－190(以上，Toray．DowCorning．Silicone(股)製)、TSF－4440、TSF－4300、TSF－4445、TSF－4446、TSF－4460、TSF－4452(以上，GE東芝Silicone(股)製)等之商品名市售者。Further, the polyoxo-type surfactants such as Toray polyoxyl DC3PA, the same DC7PA, the same SH11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH-190, the same SH-193, the same SZ-6032, the same SF-8428, same DC-57, same DC-190 (above, Toray.DowCorning.Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (The above, GE Toshiba Silicone (share) system) and other commercial names.

又，前述以外之界面活性劑例如有聚氧乙烯月桂基醚、聚氧乙烯硬脂醯基烯丙基醚、聚氧乙烯油基醚之聚氧乙烯烷基醚；聚氧乙烯正辛基苯醚、聚氧乙烯正壬基苯醚之聚氧乙烯芳基醚；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯之聚氧乙烯二烷基酯等之非離子系界面活性劑或市售品之KP341(信越化學工業(股)製)、Polyflow No.57，95(共榮社油脂化學工業(股)製)等。Further, the surfactant other than the above is, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl allyl ether, polyoxyethylene alkyl ether of polyoxyethylene oleyl ether; polyoxyethylene n-octylbenzene Polyoxyethylene aryl ether of ether, polyoxyethylene n-decyl phenyl ether; nonionic surfactant such as polyoxyethylene dilaurate, polyoxyethylene dialkyl ester of polyoxyethylene distearate Or KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), etc., which are commercially available.

這些界面活性劑可單獨使用或混合2種以上使用。These surfactants can be used singly or in combination of two or more.

界面活性劑之配合量係對於共聚物〔A〕100重量份時，較佳為5重量份以下，更佳為2重量份以下。此時，界面活性劑之配合量超過5重量份時，在塗佈時容易產生膜粗糙的傾向。When the amount of the surfactant is 100 parts by weight based on the copolymer [A], it is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. At this time, when the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

又，為了提高與基體之密著性，可配合接著助劑。Further, in order to improve the adhesion to the substrate, a bonding aid may be blended.

該接著助劑較佳為官能性矽烷偶合劑，例如具有羧基、甲基丙烯醯基、異氰酸酯基、環氧基等反應性官能基之矽烷偶合劑。更具體例如有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－異氰酸酯丙基三乙氧基矽烷、γ－環氧丙基丙基三甲氧基矽烷、2－(3,4－環氧基環己基)乙基三甲氧基矽烷等。The adhesion aid is preferably a functional decane coupling agent such as a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. More specifically, for example, trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethyl Oxydecane, γ-glycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

這些接著助劑可單獨使用或混合2種以上使用。These adjunct agents may be used singly or in combination of two or more.

接著助劑之配合量係對於共聚物〔A〕100重量份時，較佳為20重量份以下，更佳為10重量份以下。接著助劑之配合量超過20重量份時，有容易產生顯像殘留的傾向。When the amount of the auxiliary agent is 100 parts by weight based on the copolymer [A], it is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. When the amount of the auxiliary agent exceeds 20 parts by weight, the development of the developer tends to be likely to occur.

可添加其他添加劑。為了提高保存安定性等而添加之添加劑，具體言例為硫、醌類、氫醌類、聚氧化合物、胺、硝基亞硝基化合物。其例有4－甲氧基苯酚、N－亞硝基－N－苯基羥基胺鋁等。這些係對於共聚物〔A〕100重量份時，較佳使用3.0重量份以下，更佳為0.001~0.5重量份。超過3.0重量份時，無法獲得充分感度，且圖案形狀變差。Other additives can be added. Additives added to improve stability, etc., are specifically sulfur, anthraquinone, hydroquinone, polyoxyl compound, amine, nitronitroso compound. Examples thereof include 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, per 100 parts by weight of the copolymer [A]. When it exceeds 3.0 parts by weight, sufficient sensitivity cannot be obtained and the pattern shape is deteriorated.

又，為了提高耐熱性，可添加N－(烷氧基甲基)甘脲化合物、N－(烷氧基甲基)三聚氰胺化合物及1分子中具有2官能以上之環氧基的化合物。上述N－(烷氧基甲基)甘脲化合物之具體例,N,N,N,N－四(甲氧基甲基)甘脲、N,N,N,N－四(乙氧基甲基)甘脲、N,N,N,N－四(正丙氧基甲基)甘脲、N,N,N,N－四(異丙氧基甲基)甘脲、N,N,N,N－四(正丁氧基甲基)甘脲、N,N,N,N－四(第三丁氧基甲基)甘脲等。這些中,特別理想為N,N,N,N－四(甲氧基甲基)甘脲。上述N－(烷氧基甲基)三聚氰胺化合物之具體例為N,N,N,N,N,N－六(甲氧基甲基)三聚氰胺、N,N,N,N,N,N－六(乙氧基甲基)三聚氰胺、N,N,N,N,N,N－六(正丙氧基甲基)三聚氰胺、N,N,N,N,N,N－六(異丙氧基甲基)三聚氰胺、N,N,N,N,N,N－六(正丁氧基甲基)三聚氰胺、N,N,N,N,N,N－六(第三丁氧基甲基)三聚氰胺等。這些當中,特別是N,N,N,N,N,N－六(甲氧基甲基)三聚氰胺較佳。這些之市售品例如有Nikalac N－2702，MW－30M(以上三和化學(股)製)等。Further, in order to improve heat resistance, a N-(alkoxymethyl)glycoluride compound, an N-(alkoxymethyl)melamine compound, and a compound having a bifunctional or higher functional group in one molecule may be added. Specific examples of the above N-(alkoxymethyl)glycoluric compound, N,N,N,N-tetrakis(methoxymethyl)glycoluril, N,N,N,N-tetra(ethoxymethyl) Glycoluril, N, N, N, N-tetrakis (n-propoxymethyl) glycoluril, N, N, N, N-tetrakis(isopropoxymethyl) glycoluril, N, N, N N-tetrakis(n-butoxymethyl) glycoluril, N,N,N,N-tetrakis(t-butoxymethyl)glycoluril and the like. Among these, N, N, N, N-tetrakis(methoxymethyl) glycoluril is particularly preferred. Specific examples of the above N-(alkoxymethyl)melamine compound are N,N,N,N,N,N-hexa(methoxymethyl)melamine, N,N,N,N,N,N- Hexa(ethoxymethyl)melamine, N,N,N,N,N,N-hexa(n-propoxymethyl)melamine, N,N,N,N,N,N-hexa(isopropoxy Methyl) melamine, N, N, N, N, N, N-hexa(n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) ) melamine and the like. Among these, especially N, N, N, N, N, N-hexa(methoxymethyl) melamine is preferred. Commercially available products of these are, for example, Nikalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

1分子中具有2官能以上環氧基之化合物例如有乙二醇二環氧丙基醚、二乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1，6－己二醇二環氧丙基醚、甘油二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、氫化雙酚A二環氧丙基醚、雙酚A二環氧丙基醚等。這些市售品之具體例有EPOLIGHT 40E、EPOLIGHT 100E、EPOLIGHT 200E、EPOLIGHT 70P、EPOLIGHT 200P、EPOLIGHT 400P、EPOLIGHT 40E、EPOLIGHT 1500NP、EPOLIGHT 1600、EPOLIGHT 80MF、EPOLIGHT 100MF、EPOLIGHT 4000、EPOLIGHT 3002(以上共榮社化學(股)製)等。這些可單獨或者組合2種以上使用。The compound having a bifunctional or higher epoxy group in one molecule is, for example, ethylene glycol diepoxypropyl ether, diethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxy Propyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol bicyclo Oxypropyl propyl ether, trimethylolpropane triepoxypropyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. Specific examples of these commercial products include EPOLIGHT 40E, EPOLIGHT 100E, EPOLIGHT 200E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 400P, EPOLIGHT 40E, EPOLIGHT 1500NP, EPOLIGHT 1600, EPOLIGHT 80MF, EPOLIGHT 100MF, EPOLIGHT 4000, EPOLIGHT 3002 (above Social chemistry (shares) system, etc. These can be used individually or in combination of 2 or more types.

組成物溶液感光性樹脂組成物(甲)在使用時，將共聚物〔A〕、聚合性化合物〔B〕、光聚合引發劑〔C〕聚合物等之構成成分溶解於適當溶劑中，形成組成物溶液來調製較佳。上述組成物溶液調製所用之溶劑係使用可均勻溶解構成感光性樹脂組成物(甲)之各成分，且不與各成分反應者。When the photosensitive resin composition (a) of the composition solution is used, the constituent components such as the copolymer [A], the polymerizable compound [B], and the photopolymerization initiator [C] polymer are dissolved in a suitable solvent to form a composition. The solution is preferably prepared. The solvent used for the preparation of the above-mentioned composition solution is used to uniformly dissolve the components constituting the photosensitive resin composition (A), and does not react with each component.

這種溶劑例如有製造上述共聚物〔A〕所用之溶劑所例示者。Such a solvent is exemplified, for example, as a solvent for producing the above copolymer [A].

這些溶劑中，從各成分之溶解性、與各成分之反應性、塗膜形成之容易性等觀點，較佳為使用醇、乙二醇醚、乙二醇烷基醚乙酸酯、酯及二乙二醇。其中較佳為苄基醇、2－苯基乙基醇、3－苯基－1－丙醇、乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇二乙基醚、二乙二醇乙基甲基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯。Among these solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester, and the like are preferably used from the viewpoints of solubility of each component, reactivity with each component, and ease of formation of a coating film. Diethylene glycol. Among them, preferred are benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and Ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, Ethyl ethoxypropionate.

上述溶劑為了提高膜厚面內之均勻性，可併用高沸點溶劑。可併用之高沸點溶劑例如有N－甲基甲醯胺、N,N－二甲基甲醯胺、N－甲醯苯胺、N－甲基乙醯胺、N,N－二甲基乙醯胺、N－甲基吡咯啶酮、二甲基亞碸、苄基乙基醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1－辛醇、1－壬醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ－丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基乙二醇***乙酸酯等。其中較佳者為N－甲基吡咯啶酮、γ－丁內酯、N,N－二甲基乙醯胺。In order to increase the uniformity in the film thickness plane, the above solvent may be used in combination with a high boiling point solvent. High-boiling solvents which can be used in combination are, for example, N-methylformamide, N,N-dimethylformamide, N-methylanilide, N-methylacetamide, N,N-dimethylacetamidine Amine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylethylene glycol ethyl ether acetate, and the like. Preferred among them are N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide.

上述調製之組成物溶液在必要時，可藉由孔徑例如0.2~0.5μm之millipore過濾器等過濾後，供使用。感光性樹脂組成物(甲)特別適用於形成液晶面板或觸控面板等顯示面板用間隔物的材料。The composition solution prepared as described above may be used after being filtered by a millipere filter having a pore diameter of, for example, 0.2 to 0.5 μm, if necessary. The photosensitive resin composition (A) is particularly suitable for forming a material for a spacer for a display panel such as a liquid crystal panel or a touch panel.

顯示面板用間隔物使用感光性樹脂組成物(甲)形成顯示面板用間隔物時，將組成物溶液塗佈於基板表面後，經過預烘烤除去溶劑，藉此形成塗膜。When a spacer for a display panel is formed using a photosensitive resin composition (A) for a spacer for a display panel, a composition solution is applied onto the surface of the substrate, and then the solvent is removed by prebaking to form a coating film.

組成物溶液之塗佈方法例如有噴灑法、輥塗佈法、旋轉塗佈法、縫隙模塗佈法、棒塗佈法、噴墨塗佈法等適當方法，特別理想為旋轉塗佈法、縫隙模塗佈法。The coating method of the composition solution is, for example, a suitable method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet coating method, and particularly preferably a spin coating method. Slot die coating method.

又，預烘烤之條件係因各構成成分之種類、配合比率等而異，例如70~90℃下，預烘烤1~15分鐘。Further, the prebaking conditions vary depending on the type of the constituent components, the blending ratio, and the like, and are, for example, pre-baked at 70 to 90 ° C for 1 to 15 minutes.

接著，經由所定之圖案光罩曝光於被預烘烤後之塗膜上，使之聚合後，以顯像液顯像，除去不要的部分形成圖案。Then, the film is exposed to the pre-baked coating film through a predetermined pattern mask, and after polymerization, the developing solution is developed to remove unnecessary portions to form a pattern.

使用於曝光之放射線可適度選擇可見光、紫外線、遠紫外線、帶電粒子線、X射線等，較佳為波長190~450nm之範圍的放射線。The radiation used for exposure may be appropriately selected from visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, etc., and is preferably a radiation having a wavelength in the range of 190 to 450 nm.

顯像方法例如有攪拌法、浸漬法、沖洗法等任一方法，顯像時間通常為30~180秒。The development method is, for example, a stirring method, a dipping method, a rinsing method, or the like, and the development time is usually 30 to 180 seconds.

該顯像液可使用例如氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨之無機鹼；乙胺、正丙胺之1級胺；二乙胺、二正丙胺之2級胺；三甲胺、甲基二乙胺、乙基二甲基胺、三乙胺之3級胺；二甲基乙醇胺、甲基二乙醇胺、三乙醇胺之3級烷醇胺；吡咯、哌啶、N－甲基哌啶、N－甲基吡咯啶、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－壬烯之脂環族3級胺；吡啶、三甲基吡啶、二甲基吡啶、喹啉之芳香族3級胺；氫氧化四甲銨、氫氧化四乙銨之4級銨鹽等之鹼性化合物之水溶液。The developing solution can use, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and an inorganic base of ammonia; ethylamine, a primary amine of n-propylamine; diethylamine, di-n-propylamine. Grade 2 amine; tertiary amine of trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine; octaethanolamine of methylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperazine Pyridine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]- 5-decene alicyclic tertiary amine; pyridine, trimethylpyridine, lutidine, quinoline aromatic tertiary amine; tetramethylammonium hydroxide, tetraethylammonium hydroxide 4-grade ammonium salt, etc. An aqueous solution of a basic compound.

又，上述鹼性化合物之水溶液中可添加適當量之甲醇、乙醇等之水溶性有機溶劑及/或界面活性劑。Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the aqueous solution of the basic compound.

顯像後，例如藉由流水洗淨等，例如30~90秒洗淨去除不要部後，吹入壓縮空氣或壓縮氮使之乾燥，可形所定之圖案。After the development, for example, by washing with running water, for example, after washing for 30 to 90 seconds, the unnecessary portion is removed, and compressed air or compressed nitrogen is blown and dried to form a predetermined pattern.

其後，此圖案藉由熱板、烘箱等加熱裝置，以所定溫度例如150~250℃，以所定時間，在熱板上例如5~30分鐘，烘箱中例如以30~90分鐘加熱處理，可得到目的之間隔物。Thereafter, the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C, for a predetermined time, for example, 5 to 30 minutes on a hot plate, for example, 30 to 90 minutes in an oven. Get the spacer for the purpose.

本發明之感光性樹脂組成物(甲)係高感度，且可忠實實現光罩圖案之設計尺寸，且與基板之密著性優，在1500J/m2 以下之曝光量可得到充分之間隔物形狀及膜厚，且強度、耐熱性優異，另外在低曝光區域之間隔物形狀及膜厚之抑制性優異，保存期間中，使用中不易產生異物。The photosensitive resin composition (A) of the present invention is highly sensitive, and can faithfully realize the design size of the mask pattern, and has excellent adhesion to the substrate, and a sufficient spacer can be obtained at an exposure amount of 1500 J/m 2 or less. The shape and the film thickness are excellent in strength and heat resistance, and are excellent in the shape of the spacer and the film thickness in the low-exposure region, and during the storage period, foreign matter is less likely to be generated during use.

實施例Example

以下，以實施例及比較例更具體說明本發明，但本發明不限於這些實施例。Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

合成例1Synthesis Example 1

將2,2'－偶氮雙(2,4－二甲基戊腈)5重量份、二乙二醇甲基乙基醚200重量份投入具備冷卻管、攪拌機之燒瓶中，接著添加甲基丙烯酸18重量份、甲基丙烯酸環氧丙酯40重量份、苯乙烯5重量份、甲基丙烯酸三環〔5.2.1.02 , 6 〕癸烷－8－基酯32重量份，進行氮取代後，再添加1,3－丁二烯5重量份，緩慢攪拌使溶液之溫度上升至70℃，此溫度保持5小時進行聚合，得到共聚物〔A－1〕之溶液。5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 18 parts by weight of acrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0 2 , 6 ]decane-8-yl methacrylate, after nitrogen substitution Further, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was gradually increased to 70 ° C while stirring, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-1].

此溶液之固形分濃度為33.0重量%，共聚物〔A－1〕之Mw為11,000。The solid content concentration of this solution was 33.0% by weight, and the Mw of the copolymer [A-1] was 11,000.

合成例2Synthesis Example 2

將2,2'－偶氮雙(2,4－二甲基戊腈)7重量份、二乙二醇甲基乙基醚200重量份投入具備冷卻管、攪拌機之燒瓶中，接著添加甲基丙烯酸15重量份、甲基丙烯酸環氧丙酯20重量份、甲基丙烯酸2－甲基環氧丙酯25重量份、苯乙烯5重量份、甲基丙烯酸三環〔5.2.1.02 , 6 〕癸烷－8－基酯20重量份、甲基丙烯酸四氫糠基酯10重量份，進行氮取代後，再添加1,3－丁二烯5重量份，緩慢攪拌使溶液之溫度上升至70℃，此溫度保持5小時進行聚合，得到共聚物〔A－2〕之溶液。7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 15 parts by weight of acrylic acid, 20 parts by weight of glycidyl methacrylate, 25 parts by weight of 2-methylglycidyl methacrylate, 5 parts by weight of styrene, tricyclomethacrylate [5.2.1.0 2 , 6 ] 20 parts by weight of decane-8-yl ester and 10 parts by weight of tetrahydrofurfuryl methacrylate, after nitrogen substitution, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was raised to 70 by stirring slowly. At ° C, the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-2].

此溶液之固形分濃度為33.4重量%，共聚物〔A－2〕之Mw為7,000。The solid content concentration of this solution was 33.4% by weight, and the Mw of the copolymer [A-2] was 7,000.

合成例3Synthesis Example 3

將2,2'－偶氮雙(2,4－二甲基戊腈)5重量份、二乙二醇甲基乙基醚250重量份投入具備冷卻管、攪拌機之燒瓶中，接著添加甲基丙烯酸10重量份、2－甲基丙烯醯氧基乙基琥珀酸30重量份、甲基丙烯酸正丁酯25重量份、苯甲基甲基丙烯酸酯30重量份，進行氮取代後，再添加1,3－丁二烯5重量份，緩慢攪拌使溶液之溫度上升至80℃，此溫度保持5小時進行聚合，得到固形分濃度28.0重量%之共聚物〔A－3〕之溶液。所得之共聚物〔A－3〕之Mw為9,000。5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 10 parts by weight of acrylic acid, 30 parts by weight of 2-methacryloxyethyl succinic acid, 25 parts by weight of n-butyl methacrylate, and 30 parts by weight of benzyl methacrylate, and after nitrogen substitution, 1 is added. 5 parts by weight of 3-butadiene was slowly stirred to raise the temperature of the solution to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-3] having a solid content of 28.0% by weight. The Mw of the obtained copolymer [A-3] was 9,000.

實施例1Example 1

組成物溶液之調製將共聚物〔A〕：以合成例1所得之共聚物〔A－1〕之溶液100重量份(固形份)、聚合性化合物〔B〕：KAYARAD DPHA(日本化藥(股)製)80重量份、光聚合引發劑〔C〕：乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)5重量份溶解於丙二醇單甲醚乙酸酯，使固形成份濃度成為35重量%後，以孔徑0.2 μ m之milipore過濾器過濾，調製組成物溶液(S－1)。Preparation of a solution solution: Copolymer [A]: 100 parts by weight of a solution of the copolymer [A-1] obtained in Synthesis Example 1 (solid content), polymerizable compound [B]: KAYARAD DPHA (Nippon Chemical Co., Ltd. )) 80 parts by weight, photopolymerization initiator [C]: ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)--9 5 parts by weight of H.-carbazol-3-yl]-, 1-(O-acetyl ketone oxime) was dissolved in propylene glycol monomethyl ether acetate to have a solid content of 35% by weight, and a pore diameter of 0.2. The milipore filter of μ m was filtered to prepare a composition solution (S-1).

(I)間隔物之形成使用旋轉器將上述組成物溶液塗佈於無鹼玻璃基板上後，以90℃於熱板上預烘烤3分鐘形成膜厚6.0μm之塗膜。(I) Formation of a spacer The above composition solution was applied onto an alkali-free glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a coating film having a film thickness of 6.0 μm.

經由殘留10μm方形之圖案光罩，曝光間隙為150μm，波長365nm之曝光強度為300W/m2 之紫外線在上述製得之塗膜上曝光。接著以氫氧化鉀0.05重量%水溶液以25℃、顯像60秒後，使用純水清洗1分鐘。再於烘箱中，以150℃加熱120分鐘，形成間隔物。Ultraviolet rays having an exposure gap of 150 μm and an exposure intensity of 300 W/m 2 having a wavelength of 365 nm were exposed on the above-prepared coating film via a pattern mask having a residual 10 μm square. Subsequently, the mixture was washed with pure water at a temperature of 25 ° C for 60 seconds in a 0.05 wt% aqueous solution of potassium hydroxide, and then washed with pure water for 1 minute. The mixture was further heated in an oven at 150 ° C for 120 minutes to form a spacer.

(II)解像度之評價在上述(1)所得之圖案中，顯像後之殘膜率(顯像後之膜厚/初期膜厚×100)為90%以上之感度之最小圖案尺寸來評價。圖案尺寸越小解像度越佳。結果如表2所示。(II) Evaluation of resolution In the pattern obtained in the above (1), the residual film ratio after development (thickness after development/initial film thickness × 100) was evaluated as the minimum pattern size of sensitivity of 90% or more. The smaller the pattern size, the better the resolution. The results are shown in Table 2.

(III)感度評價在上述(1)所得之圖案中，顯像後之殘膜率為90%以上之感度為1，500J/m2 以下時，表示感度良好。(III) Sensitivity evaluation In the pattern obtained in the above (1), when the residual film ratio after development is 90% or more and the sensitivity is 1,500 J/m 2 or less, the sensitivity is good.

(IV)圖案剖面形狀之評價以掃描型電子顯微鏡觀察上述(1)所得之圖案斷面形狀之結果，其形狀如第1圖所示相當於A~C之其中任一形狀。如A所示，圖案邊緣為圓錐型時，圖案形狀良好。如B所示，圖案邊緣形成垂直狀時，表示圖案形狀稍微良好。(IV) Evaluation of Pattern Cross-Section Shape The result of observing the cross-sectional shape of the pattern obtained in the above (1) by a scanning electron microscope was as shown in Fig. 1 and corresponds to any of A to C. As shown in A, when the pattern edge is a conical shape, the pattern shape is good. As shown by B, when the pattern edges are formed vertically, the pattern shape is slightly good.

又，如C所示，形成倒圓錐(斷面形狀之膜表面之邊比基板側之邊更長者，倒三角形狀)之形狀係在其後研磨步驟時，圖案剝離之可能性非常高，因此，這種形狀不佳。Further, as shown by C, the shape in which the inverted cone (the side of the film surface having the cross-sectional shape is longer than the side of the substrate side, and the inverted triangular shape) is formed is highly likely to be peeled off during the subsequent polishing step. This shape is not good.

(V)壓縮強度之評價使用微小壓縮試驗機(MCTM－200，(股)島津製作所製)評價上述(1)所得之間隔物之壓縮強度。藉由直徑50μm之平面壓頭，測定施加10mN之負荷之變形量(測定溫度：23℃)。此值在0.5以下時，壓縮強度良好。結果如表2所示。(V) Evaluation of Compressive Strength The compressive strength of the spacer obtained in the above (1) was evaluated using a micro compression tester (MCTM-200, manufactured by Shimadzu Corporation). The amount of deformation (measuring temperature: 23 ° C) at which a load of 10 mN was applied was measured by a flat head having a diameter of 50 μm. When the value is 0.5 or less, the compressive strength is good. The results are shown in Table 2.

(VI)研磨耐性之評價藉由液晶配向膜塗佈用印刷機將液晶配向劑之AL3046(JSR(股)製)塗佈於上述(1)所得之基板上，以180℃乾燥1小時，形成乾燥膜厚0.05μm之配向劑之塗膜。(VI) Evaluation of the polishing resistance The liquid crystal alignment agent AL3046 (manufactured by JSR) was applied onto the substrate obtained in the above (1), and dried at 180 ° C for 1 hour to form a liquid crystal alignment film coating printer. A coating film of an alignment agent having a film thickness of 0.05 μm was dried.

對於此塗膜藉由具有捲繞耐綸製之布之滾筒的研磨機，以滾筒之轉數500rpm、研磨台之移動速度1cm/秒進行研磨處理。此時之間隔物圖案之切削或剝離之有無如表2所示。This coating film was subjected to a grinding treatment by a grinding machine having a drum wound with a nylon fabric at a number of revolutions of the drum of 500 rpm and a moving speed of the polishing table of 1 cm/sec. The presence or absence of cutting or peeling of the spacer pattern at this time is as shown in Table 2.

(VII)密著性之評價除了不使用圖案光罩外，其他與上述(1)同樣地實施，形成密著性評價用之硬化膜，進行密著性試驗。試驗法係依據JIS K－5400(1900)8.5之附著性試驗中之8.5．2之棋盤格膠帶法。此際殘留棋盤格之數目如表2所示。(VII) Evaluation of Adhesiveness A cured film for adhesion evaluation was formed in the same manner as in the above (1) except that the pattern mask was not used, and the adhesion test was performed. The test method is based on the checkerboard tape method of 8.5.2 in the adhesion test of JIS K-5400 (1900) 8.5. The number of remaining checkerboards is shown in Table 2.

(VIII)保存安定性之評價調製組成物物後，以－15℃保存，與上述(III)感度評價相同，追蹤顯像後之殘膜率成為90%以上之必要曝光量之經時變化，測定對於保存3個月後之感度與剛調製後之感度的相對值。以光散射式粒子檢知器(KS－28B，Lion股份公司製)測定3個月後之溶液中之0.5 μ m以上之異物產生的情形。結果如表2所示。(VIII) Evaluation of Preservation Stability After modulating the composition, the composition was stored at -15 ° C, and the change in the necessary exposure amount after the development of the residual film ratio after the development was 90% or more was traced as in the above (III) sensitivity evaluation. The relative value of the sensitivity after storage for 3 months and the sensitivity after the preparation was measured. A light scattering type particle detector (KS-28B, manufactured by Lion Co., Ltd.) was used to measure the occurrence of foreign matter of 0.5 μm or more in the solution after 3 months. The results are shown in Table 2.

(IX)耐熱性之評價了未使用光罩外，其餘與間隔物之形成相同，形成硬化膜後，在240℃之烘箱中加熱60分鐘，測定加熱前後之膜厚，評價殘膜率(加熱後之膜厚×100/初期膜厚)。結果如表2所示。(IX) Heat resistance was evaluated except that the mask was not used, and the formation of the spacer was the same. After the cured film was formed, it was heated in an oven at 240 ° C for 60 minutes, and the film thickness before and after the heating was measured to evaluate the residual film rate (heating). After film thickness × 100 / initial film thickness). The results are shown in Table 2.

實施例2~12、比較例1~4Examples 2 to 12 and Comparative Examples 1 to 4

除了在實施例1中，〔A〕成分~〔E〕成分使用如表1之種類、量外，其他與實施例1相同，調製組成物溶液形成間隔物進行評價。〔B〕~〔E〕之添加量係對於共聚物〔A〕100重量份時之重量比。In the same manner as in Example 1, except that the components [A] to [E] in the first embodiment were used in the same manner as in Example 1, the composition solution was prepared to form a spacer and evaluated. The addition amount of [B] to [E] is a weight ratio of 100 parts by weight of the copolymer [A].

表1中，成分之簡稱係表示以下之化合物。In Table 1, the abbreviations of the ingredients mean the following compounds.

(B－1)：(KAYARAD DPHA(日本化藥(股)製)(B－2)：KAYARAD DPHA－40H(日本化藥(股)製)(B－3)：二乙二醇二丙烯酸酯(C－1)：乙酮，1－〔9－乙基－6－(2－甲基－4－四氫吡喃氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)(C－2)：乙酮，1－〔9－乙基－6－(2－甲基－4－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)(C－3)：乙酮，1－〔9－乙基－6－(2－甲基－5－四氫吡喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)(C－4)：乙酮，1－〔9－乙基－6－(2－甲基－5－四氫呋喃基甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)(C－5)：乙酮，1－〔9－乙基－6－〔2－甲基－4－(2，2－二甲基－1,3－二氧雜環戊基)甲氧基苯醯基)－9.H.－咔唑－3－基〕－,1－(O－乙醯基酮肟)(D－1)：2－甲基－1－〔4－(甲硫基)苯基〕－2－嗎啉基丙烷－1－酮(Ciba geigy chemicals公司製Irgacure 907)(D－2)：2－(4－甲基苄基)－2－二甲基胺基－1－(4－嗎啉基苯基)丁酮－1(Ciba geigy chemicals公司製Irgacure 306)(E－1)：2,2'－雙(2,4－二氯苯基)－4,4',5,5'－四苯基－1,2'－雙咪唑(E－2)：4,4'－雙(二乙基胺基)二苯甲酮(E－3)：2－氫硫基苯并噻唑表1中，－之記號表示未添加該成分。(B-1): (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (B-2): KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) (B-3): Diethylene glycol diacrylate (C-1): ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-acetylhydrazinone) (C-2): ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxyphenyl)- 9.H.-carbazol-3-yl]-, 1-(O-acetylhydrazinone) (C-3): ethyl ketone, 1-[9-ethyl-6-(2-methyl- 5-tetrahydropyranylmethoxyphenylhydrazino)-9.H.-carbazol-3-yl]-,1-(O-ethylmercapto oxime) (C-4): ethyl ketone, 1 -[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-ethenyl ketone肟)(C-5): Ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) A Oxyl phenyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetyl ketone oxime) (D-1): 2-methyl-1-[4-(A Thio)phenyl]-2-morpholinylpropane 1-ketone (Irgacure 907, manufactured by Ciba Geigy Chemical Co., Ltd.) (D-2): 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl) Keto-1 (Irgacure 306, manufactured by Ciba Geigy chemicals) (E-1): 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-bisimidazole (E-2): 4,4'-bis(diethylamino)benzophenone (E-3): 2-hydrothiobenzothiazole, in Table 1, the mark of - Indicates that the ingredient has not been added.

評價結果如表2所示。The evaluation results are shown in Table 2.

第1圖係例示圖案之斷面形狀圖。Fig. 1 is a cross-sectional view showing an example of a pattern.

Claims (3)

一種感光性樹脂組成物，其特徵為含有：〔A〕(a1)乙烯性不飽和羧酸及/或乙烯性不飽和羧酸酐與(a2)其他乙烯性不飽和化合物之共聚物，〔B〕具有乙烯性不飽和鍵之聚合性化合物及〔C〕由下述式(2)表示之化合物所構成之光聚合引發劑， 〔R1 係碳數1~20之烷基、碳數3~8之環烷基或苯基，R2 與R3 分別為氫原子、碳數1~20之烷基、碳數3~8之環烷基、取代或未取代之苯基或碳數7~20之脂環基(但碳數7~8之環烷基除外)，上述取代苯基之取代基為碳數1~6之烷基、碳數1~6之烷氧基、苯基或鹵原子，R4 為碳數4~20之含氧雜環基、碳數4~20之含氮雜環基或碳數4~20之含硫雜環基，R5 係氫、碳數1~12之烷基或碳數1~12之烷氧基，n為1~5之整數，m為0~5之整數，n+m≦5，1為0~6之整數。A photosensitive resin composition comprising: [A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and [C] a photopolymerization initiator composed of a compound represented by the following formula (2), [R 1 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group; and R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3 to 8; a cycloalkyl group, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the above substituted phenyl group is a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, R 4 is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a carbon number of 4~ a sulfur-containing heterocyclic group of 20, R 5 is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, n+ m ≦ 5, 1 is an integer from 0 to 6. 一種顯示面板用間隔物，其特徵係由申請專利範圍第1項之感光性樹脂組成物所形成。 A spacer for a display panel, which is characterized in that it is formed of a photosensitive resin composition of the first application of the patent scope. 一種顯示面板，其特徵係具備申請專利範圍第2項之顯示面板用間隔物所成。 A display panel comprising the spacer for a display panel according to item 2 of the patent application scope.
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