TW576950B - Photosensitive resin compound, spacer, forming material, colorfilter forming material and the liquid crystal display device - Google Patents

Photosensitive resin compound, spacer, forming material, colorfilter forming material and the liquid crystal display device Download PDF

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Publication number
TW576950B
TW576950B TW090124787A TW90124787A TW576950B TW 576950 B TW576950 B TW 576950B TW 090124787 A TW090124787 A TW 090124787A TW 90124787 A TW90124787 A TW 90124787A TW 576950 B TW576950 B TW 576950B
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Taiwan
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alkali
epoxy
photosensitive resin
item
scope
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TW090124787A
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Chinese (zh)
Inventor
Fumitaka Oizumi
Seiki Mitani
Eiji Watanabe
Setsuo Itami
Nobuyuki Otsuka
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Chisso Corp
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Priority claimed from JP2000397180A external-priority patent/JP2002196489A/en
Priority claimed from JP2000397181A external-priority patent/JP3705132B2/en
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Publication of TW576950B publication Critical patent/TW576950B/en

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • 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
    • G03F7/027—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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

A negative type photosensitive resin composition and a photosetting colored composition are provided. The photosensitive resin composition and the photosetting colored composition can be formed a polymer film having high sensitivity, excellent development characteristics with no development residue, resistance to alkali, and waterproofness. And a spacer, a color filter and a liquid crystal display device made from those compound are provided. The photosensitive resin compound includes: a polymer binder, an ethylenic-double-bond- containing compound, an organic peroxide having a benzophenone structure, a photosensitizer having a coumarin structure, wherein the polymer binder is alkali-soluable resin or a mixture of alkali-soluable resin and alkali-insoluble epoxy-group- containing vinyl polymer, the photosetting colored composition of this invention is a compound that the photosensitive resin composition having a colorants. In those compositions, the alkali-soluable resin in the polymer binder is 40-100 weight %, for the polymer binder, the ethylenic-double-bond- containing compound is 10-200 weight %, the organic peroxide having a benzophenone structure is 0.1-50 weight %, and the photosensitizer having a coumarin structure is 0.1-50 weight %, a full solid ingredient in the composition is 0.1-50 weight %. When the composition having the colorants, the colorants is 5-130 weight % for the amount to the polymer binder and the ethylenic-double-bond- containing compound.

Description

8310-pif2 玖、發明說明： 發明領域 本發明係關於感光性樹脂組成物、其作爲材料所形成之 液晶顯示元件用間隔件、濾色鏡以及液晶顯示元件。 習知技術 習知以來，液晶顯示器(LCD)的間隙（gap)控制技術，係在 兩塊基板之間，散佈例如是玻璃珠或是塑膠珠等的間隔件粒 子，且使用依此些粒子的大小控制液晶層厚度。但是，此種 方式具有下述的問題。 1) 間隔件配置於有效像素部內的場合，由於在間隔件粒子存在 的部位，像素無法顯示，使得對比以及開口率降低，亦使得 顯示成色降低。 2) 間隔件粒子的移動所造成的配向膜的損傷，間隔件粒子的凝 集、或是間隔件粒子周邊的配向異常所引起的顯示不佳。 3) 間隔件粒子徑的參差不齊容易造成間隙不整齊。 4) 間隔件粒子過小而造成面板強度降低。 更加的，此些問題隨著LCD大畫面化、高精細化(狹間隙化、 高解像度化)而變得更形顯著。 爲了解決此些的問題，提出了以微影的方式形成間隔件 的方式，依此方法的話，係在基板上塗佈感光性樹脂，並藉 由預定的罩幕照射紫外線後，而能夠顯影形成點狀或是條狀 的間隔件。依此方法能夠在有效像素部以外的場所形成間隔 件。更加的’依此方法的話，由於能夠控制感光性樹脂塗佈 於胞間隙的塗膜厚，而容易控制間隙的厚度。亦即是，能夠 提高間隙控制的精密度，以解決上述的問題。 8310-pif2 在LCD製程中，製備間隔件與硏磨(Rubbing)的配向膜的 方法，能夠使用下列3種的方法。 a·在配向膜塗佈之前形成間隔件，進行硏磨。 b·在配向膜塗佈之後形成間隔件，進行硏磨。 c.在硏磨的配向膜上形成間隔件。 以感光性樹脂形成的間隔件，爲了能夠使用a〜c全部的方法， 而必須具備下列的特性。 1) 形成間隔件的顯影步驟，爲了提高成品率，必須具備I·高感 度、II.顯影後無顯影殘渣(scum)。 2) 而且，所形成的間隔件： I·具備塗佈配向膜之前的洗淨步驟所需的耐鹼性、耐水性， II.具備配向膜所使用溶劑的耐溶劑性。 III·具備在配向膜的燒成步驟中，不產生熱變形的耐熱性。 IV·不產生硏磨所致的顯示不佳的高耐硏磨性。 V.必須不產生液晶配向不佳，且電壓保持率、殘留直流電流不 會降低。 而且，加入於前述間隔件形成材料中，使用此感光性樹 脂組成物中加入著色劑的光硬化性著色組成物，而能夠使用 同樣的微影步驟以製造濾色鏡。製造間隔件以及濾色鏡所使 用的光阻技術中，具聚合性不飽和基單體與感光劑的選擇相 當重要。習知以來，使用光聚合用的感光性光阻，由提昇液 晶顯示元件的技術而更高耐性、高精細度以及高感度化成爲 課題。 習知以來，具乙烯基等聚合性不飽和基單體或是寡聚物 在聚合、硬化時，在感光劑的光聚合引發劑與光增感劑的存 在下，採用照射光線的聚合方法。由於此種方法具有較其他 8310-pif2 方法快的硬化速度，能夠在低溫硬化等優點，而廣泛的應用 於塗料以及光阻等。由於硬化的速度是依存於光聚合引發劑 與光增感劑。因此開發了各種的光聚合引發劑與光增感劑。 光聚合引發劑例如是揭示於德國專利第1694149號的苯偶因 醚(benzoin ether)類，美國專利第404803號的乙醯苯衍生物。 而且此些之外，所知亦有烯丙基重氮鎗鹽或鹵化碳化氫等光 自由基引發劑。而且，所知亦有一種有機過氧化物作爲光聚 合引發劑使用，此些的聚合系亦作了相當多的硏究。 具體而言，美國專利第4171252號、4416826號以及 4752629號中，揭示了具特定t-丁基過氧酯的芳香族化合物。 更加的 Journal of Organic Chemistry 的第 44 卷第 4123 頁（1979 年）’或 Journal of Polymer Science Chemistry 的第 21 卷第 3129 頁（1983年），檢討了具有1〜2個4,4’-二(t-丁基過氧羰基)二 苯甲酮等的過氧酯等的二苯甲酮衍生物的合成與乙烯基單體 的聚合。但是，由於光聚合引發劑的吸收波長存在於短波長 側，通常製造面板所使用的超高壓水銀燈並不能提供足夠的 感度。因此，與光增感劑組合使用成爲必要而不可缺少。 在特公平4-10482號公報揭示了顯示特定結構之具二苯甲 酮基的多價過氧酯化合物與有機染料化合物所組成的光引發 劑組成物。而且，特公平4-66349號公報，揭示了含有：具乙 烯性不飽和聚合的化合物、具二苯甲酮基的多價過氧酯化合 物以及4,4’-雙（二烷基胺）二苯甲酮所形成的光聚合引發劑以 及含有此光聚合引發劑的高感度光聚合組成物。依此，提出 了種種的光增感劑’以與具二苯甲酮結構的有機過氧化物系 光聚合引發劑組合使用。但是，以往的光增感劑，由於在短 波長側U S 400)具有吸收區間，只有使用g線或是h線曝光（λ 8310-pif2 max = 435nm、405nm)並不能得到足夠的感度。 發明槪要 本發明的目的，係提供一種新規格的感光性樹脂組成物 以及光硬化性著色組成物，用以在藉由微影形成液晶顯示元 件的間隔件以及濾色鏡的時候。更加詳述而言，係能夠形成 具備以往的特性之外，對g線或是h線具高感度、具有無顯 影殘渣（scum)之優異顯影性、耐鹼性以及耐水性之高分子膜， 提供負光阻型的感光性樹脂組成物以及光硬化性著色組成 物。然後，此些組成物係適合作爲間隔件形成材料以及濾色 鏡形成材料，本發明的另一目的爲提供此樹脂組成物所形成 的間隔件、濾色鏡以及液晶顯示元件。 本發明者們對於包含：鹼可溶性樹脂、鹼不溶性的具環 氧基乙烯基聚合物、具乙烯性雙鍵化合物、具二苯甲酮結構 有機過氧化物，以及具香豆素結構光增感劑的感光性樹脂組 成物，作爲用以形成間隔件的材料進行硏究。然後，將使用 此組成物所形成的間隔件以光照射，特別是發現此組成物兼 具··以水銀燈的g線以及h線照射時具備高感度，且耐溶劑 性、耐熱性、以及硏磨耐性優良，不會產生液晶配向不佳， 且電壓保持率、殘留直流電流不會降低等特性。 更加的，含有：使用鹼可溶性樹脂、或是鹼可溶性樹脂 與驗不溶性的具環氧基乙烯基聚合物的混合物作爲高分子結 合劑，其與具乙烯性雙鍵化合物、具二苯甲酮結構有機過氧 化物(光聚合引發劑），具香豆素結構光增感劑以及著色劑的感 光性樹脂組成物，同樣以光照射，發現特別是在使用水銀燈 的g線以及h線照射時顯示出高感度，依此而完成本發明。 8310-pif2 亦即是，本發明的感光性樹脂組成物，其特徵爲具有下 述的構成。 (1) 含有：高分子結合劑、具乙烯性雙鍵化合物、具二苯甲酮 結構有機過氧化物以及具香豆素結構光增感劑的感光性樹脂 組成物， 此高分子結合劑係爲鹼可溶性樹脂、或是此鹼可溶性樹脂與 鹼不溶性的具環氧基乙烯基聚合物的混合物， 此高分子結合劑中的鹼可溶性樹脂的比例爲40〜100重量％ 左右，相對於此高分子結合劑，具乙烯性雙鍵化合物爲10〜200 重量％左右，具二苯甲酮結構有機過氧化物爲0.1〜50重量％ 左右，以及具香豆素結構光增感劑爲0.1〜50重量％左右’組 成物中全固形成份的含有量爲1〇〜50重量％左右。 (2) 於前述（1)項記載的感光性樹脂組成物，其中鹼可溶性樹脂’ 係爲至少一種不飽和羧酸單體與至少一種不飽和羧酸單體以 外之自由基聚合性單體聚合所得的共聚合物。 (3) 於前述(2)項記載的感光性樹脂組成物，其中不飽和竣酸單 體以外之自由基聚合性單體，係爲包含如式（1)所示化合物白勺 至少一種的自由基聚合性單體的混合物。8310-pif2 (1) Description of the invention: Field of the invention The present invention relates to a photosensitive resin composition, a spacer for a liquid crystal display element formed by using the photosensitive resin composition, a color filter, and a liquid crystal display element. Known technology Since the beginning, the gap control technology of the liquid crystal display (LCD) is between two substrates, where spacer particles such as glass beads or plastic beads are dispersed, and the particles based on these particles are used. The size controls the thickness of the liquid crystal layer. However, this method has the following problems. 1) When the spacer is arranged in the effective pixel portion, the pixels cannot be displayed in the part where the spacer particles are present, so that the contrast and the aperture ratio are reduced, and the display color is also reduced. 2) Damage to the alignment film caused by the movement of the spacer particles, agglomeration of the spacer particles, or poor display caused by an abnormal alignment around the spacer particles. 3) The uneven particle diameter of the spacer is likely to cause irregular gaps. 4) The spacer particles are too small, which reduces the panel strength. Furthermore, these problems become more and more significant with the enlargement of the LCD screen and high definition (narrow gap and high resolution). In order to solve these problems, a method of forming spacers in a lithographic manner has been proposed. In this method, a photosensitive resin is coated on a substrate, and ultraviolet rays are irradiated through a predetermined mask to form a developing film. Dot- or strip-shaped spacers. In this way, a spacer can be formed in a place other than the effective pixel portion. Further, according to this method, since the thickness of the coating film where the photosensitive resin is applied to the intercellular space can be controlled, it is easy to control the thickness of the gap. That is, the precision of the gap control can be improved to solve the above-mentioned problems. 8310-pif2 In the LCD manufacturing process, the following three methods can be used to prepare a spacer and a rubbing alignment film. a. A spacer is formed and the honing is performed before the alignment film is applied. b. A spacer is formed after application of the alignment film, and honing is performed. c. Forming a spacer on the honing alignment film. The spacer made of a photosensitive resin must have the following characteristics in order to be able to use all the methods a to c. 1) In the development step for forming the spacer, in order to improve the yield, it is necessary to have I · high sensitivity, and II. No development scum after development. 2) The formed spacer: I. It has the alkali resistance and water resistance required for the washing step before coating the alignment film, and II. It has the solvent resistance of the solvent used for the alignment film. III. It has heat resistance that does not cause thermal deformation during the firing step of the alignment film. IV. High abrasion resistance with poor display due to abrasion does not occur. V. Must not cause poor alignment of the liquid crystal, and the voltage retention and residual DC current will not decrease. Furthermore, by adding the photocurable coloring composition to which the coloring agent is added to the above-mentioned spacer-forming material, a color filter can be manufactured using the same lithography process. In the photoresist technology used in the manufacture of spacers and color filters, the choice of polymerizable unsaturated monomers and photosensitizers is important. Conventionally, the use of a photoresist for photopolymerization has improved the technology of liquid crystal display elements to achieve higher resistance, higher precision, and higher sensitivity. Conventionally, a polymerizable unsaturated monomer or oligomer having a vinyl group or the like has been subjected to a light irradiation polymerization method in the presence of a photopolymerization initiator and a photosensitizer in a photosensitizer during polymerization and curing. Because this method has faster hardening speed than other 8310-pif2 methods, and can be cured at low temperature, it is widely used in coatings and photoresists. The rate of hardening depends on the photopolymerization initiator and photosensitizer. Therefore, various photopolymerization initiators and photosensitizers have been developed. Photopolymerization initiators are benzoin ethers disclosed in German Patent No. 1694149, and acetophenone derivatives of U.S. Patent No. 404803, for example. In addition to these, photo-radical initiators such as allyl diazo gun salts and halogenated hydrocarbons are known. Moreover, it is known that an organic peroxide is used as a photopolymerization initiator, and a considerable amount of research has been conducted on these polymerization systems. Specifically, U.S. Patent Nos. 4,171,252, 4,416,826, and 4,752,629 disclose aromatic compounds having specific t-butylperoxy esters. More Journal of Organic Chemistry, Vol. 44, p. 4123 (1979) 'or Journal of Polymer Science Chemistry, Vol. 21, p. 3129 (1983), reviews with 1 ~ 2 4,4'-two ( Synthesis of benzophenone derivatives such as t-butylperoxycarbonyl) benzophenone and other peroxyesters and polymerization of vinyl monomers. However, since the absorption wavelength of the photopolymerization initiator exists on the short-wavelength side, the ultrahigh-pressure mercury lamp usually used for manufacturing a panel cannot provide sufficient sensitivity. Therefore, a combination with a photosensitizer is necessary and indispensable. Japanese Patent Publication No. 4-10482 discloses a photoinitiator composition composed of a benzophenone group-containing polyvalent peroxyester compound and an organic dye compound showing a specific structure. Furthermore, Japanese Patent Publication No. 4-66349 discloses a compound containing an ethylenically unsaturated polymerization compound, a polyvalent peroxyester compound having a benzophenone group, and 4,4'-bis (dialkylamine) diamine. A photopolymerization initiator formed by benzophenone and a high-sensitivity photopolymerization composition containing the photopolymerization initiator. Accordingly, various photosensitizers have been proposed for use in combination with an organic peroxide-based photopolymerization initiator having a benzophenone structure. However, conventional photosensitizers have an absorption range on the short wavelength side (U S 400). Therefore, sufficient sensitivity cannot be obtained only with g-line or h-line exposure (λ 8310-pif2 max = 435 nm, 405 nm). Summary of the Invention The object of the present invention is to provide a new type of photosensitive resin composition and a photocurable coloring composition for forming spacers and color filters of a liquid crystal display element by lithography. In more detail, it can form a polymer film with high sensitivity to g-line or h-line, excellent developability without development scum, alkali resistance, and water resistance in addition to the previous characteristics. Provides a negative photoresist type photosensitive resin composition and a photocurable coloring composition. Then, these compositions are suitable as a spacer-forming material and a color filter-forming material. Another object of the present invention is to provide a spacer, a color filter, and a liquid crystal display element formed of the resin composition. The inventors have: alkali-soluble resins, alkali-insoluble epoxy-based vinyl polymers, vinyl double-bond compounds, organic peroxides with benzophenone structure, and photosensitization with coumarin structure The photosensitive resin composition of the agent is investigated as a material for forming the spacer. Then, the spacer formed by using the composition was irradiated with light, and it was found that the composition had both high sensitivity when irradiated with the g-line and h-line of a mercury lamp, and had solvent resistance, heat resistance, and 硏It has excellent abrasion resistance, does not cause poor liquid crystal alignment, and does not reduce voltage retention and residual DC current. Furthermore, it contains: using an alkali-soluble resin or a mixture of an alkali-soluble resin and an insoluble epoxy-based vinyl polymer as a polymer binder, which is combined with an ethylenic double bond compound and a benzophenone structure. Organic peroxides (photopolymerization initiators), photosensitive resin compositions with coumarin-structured photosensitizers, and coloring agents are also irradiated with light, and it was found that they were particularly exhibited when using the g-line and h-line of a mercury lamp. With high sensitivity, the present invention has been completed. 8310-pif2, that is, the photosensitive resin composition of the present invention is characterized by having the following structure. (1) A photosensitive resin composition containing a polymer binder, an ethylenic double bond compound, an organic peroxide with a benzophenone structure, and a photosensitizer with a coumarin structure. The polymer binder is It is an alkali-soluble resin or a mixture of the alkali-soluble resin and an alkali-insoluble epoxy-based vinyl polymer. The proportion of the alkali-soluble resin in the polymer binder is about 40 to 100% by weight, which is relatively high. Molecular binding agent, about 10 ~ 200% by weight of compound with ethylenic double bond, about 0.1 ~ 50% by weight of organic peroxide with benzophenone structure, and 0.1 ~ 50 of photosensitizer with coumarin structure The content of the total solids in the composition is about 10 to 50% by weight. (2) The photosensitive resin composition according to the above item (1), wherein the alkali-soluble resin 'is a polymer of at least one unsaturated carboxylic acid monomer and a radical polymerizable monomer other than the at least one unsaturated carboxylic acid monomer. The resulting copolymer. (3) The photosensitive resin composition according to the above item (2), wherein the radical polymerizable monomer other than the unsaturated monomer is a free polymerizable monomer containing at least one compound represented by the formula (1) Of polymerizable monomers.

(式中R!爲Η或是甲基，1^2爲Η或是碳數1〜5的烷基’四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲0〜5的整數） (4)於前述（3)項記載的感光性樹脂組成物，其中在式（1)中’ n 爲1或是2，112爲Η。 576950 8310-pif2 (5) 於前述（1)項記載的感光性樹脂組成物，其中鹼不溶性的具 環氧基乙烯基聚合物，係由具環氧基自由基聚合性單體的單 獨聚合，兩種以上的具環氧基自由基聚合性單體的共聚合’ 或是至少一種具環氧基自由基聚合性單體與至少一種非不飽 和羧酸自由基聚合性單體且不具環氧基的化合物，共聚合所 得的聚合體。 (6) 於前述（1)項記載的感光性樹脂組成物，其中具二苯甲酮結 構有機過氧化物爲如式(2)所表示的化合物。(In the formula, R! Is fluorene or methyl, 1 ^ 2 is fluorene, or 2 to 4 positions of alkyl'tetrahydrofuran ring with 1 to 5 carbon atoms can also be bonded to carbon atoms, and η is an integer of 0 to 5) (4) The photosensitive resin composition according to the above item (3), wherein 'n is 1 or 2,112 in formula (1), and Η is Η. 576950 8310-pif2 (5) The photosensitive resin composition described in the above item (1), wherein the alkali-insoluble epoxy-based vinyl polymer is independently polymerized from an epoxy-based radical polymerizable monomer, Copolymerization of two or more epoxy radical polymerizable monomers' or at least one epoxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical polymerizable monomer without epoxy A compound obtained by copolymerizing a radical-based compound. (6) The photosensitive resin composition according to the above (1), wherein the organic peroxide having a benzophenone structure is a compound represented by the formula (2).

(式中，R3〜R6爲各別獨立的碳數1〜U的烷基，X!以及X2 爲各別獨立的或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與p 位置的碳原子的其中任一個結合。） (Ό於前述(6)項記載的感光性樹脂組成物，其中在式(2)中，χ 以及Χ2爲-〇-。 (8) 於前述（1)項記載的感光性樹脂組成物，其中具乙燦性雙鍵 化合物爲丙烯酸酯以及甲基丙烯酸酯。 (9) 於前述（1)項記載的感光性樹脂組成物，其中具乙燦性雙鍵 化合物爲3個以上的具乙烯性雙鍵化合物。 (1〇)於前述（1)項記載的感光性樹脂組成物，其特徵爲鹼可溶性 樹脂係爲至少一種不飽和羧酸單體與至少一種不飽和竣酸單 11 576950 B31〇-pif2 體以外之自由基聚合性單體聚合所得的共聚合物’此不飽和 羧酸單體以外之自由基聚合性單體，係爲包含如式（1)所示化 合物的至少一種的自由基聚合性單體的混合物，(In the formula, R3 to R6 are each independent alkyl groups having 1 to U carbon atoms, and X! And X2 are each independent or -NH-, benzophenone structure carbonyl groups, as opposed to those having a benzene ring. The carbon atom of the substituent may be individually bonded to any one of the carbon atoms at the p position.) (The photosensitive resin composition described in the above item (6), wherein in the formula (2), χ and χ2 It is -〇-. (8) The photosensitive resin composition according to the above (1), wherein the compound having an ethylenic double bond is an acrylate and a methacrylate. (9) The above-mentioned (1) A photosensitive resin composition in which the compound having an ethylenic double bond is three or more ethylenic double bond compounds. (10) The photosensitive resin composition according to the above item (1), characterized in that it is an alkali-soluble resin It is a copolymer obtained by polymerizing at least one unsaturated carboxylic acid monomer with at least one unsaturated carboxylic acid monomer 11 576950 B31〇-pif2 body. 'Free from this unsaturated carboxylic acid monomer Radical polymerizable monomer, which is a radical polymerization containing at least one kind of compound represented by formula (1) Sex monomer mixture,

⑴ (式中1爲Η或是甲基，R2爲Η或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲0〜5的整數） j、, 鹼不溶性的具環氧基乙烯基聚合物，係由具環氧基自由基聚 / 合性單體的單獨聚合，兩種以上的具環氧基自由基聚合性單· 體的共聚合，或是至少一種具環氧基自由基聚合性單體與至 少一種非不飽和羧酸自由基聚合性單體且不具環氧基的化合 物，共聚合所得的聚合體， 具二苯甲酮結構有機過氧化物爲如式P)所表示的化合物，⑴ (wherein 1 is Η or methyl, R2 is Η or alkyl having 1 to 5 carbons, and 2 to 4 positions of the tetrahydrofuran ring may also be bonded to a carbon atom, η is an integer of 0 to 5) j, , Alkali-insoluble epoxy-based vinyl polymer, which is polymerized separately from epoxy-based radical polymerizable / combinable monomers, and copolymerized with two or more epoxy-based radical polymerizable monomers, Or a compound obtained by copolymerizing at least one compound having an epoxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical polymerizable monomer without an epoxy group, and having an organic compound having a benzophenone structure. Peroxide is a compound represented by formula P),

(式中，R3〜R6爲各別獨立的碳數1〜13的烷基’ Χι以及 爲各別獨立的或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子’亦可以各別與P 位置的碳原子的其中任一個結合。） 然後，具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙稀酸酯。 12 576950 8310-pif2 (11) 前述（1)〜（10)項的其中任一項記載的感光性樹脂組成物作 爲材料所形成的塗膜。 (12) 前述（11)項記載的塗膜所形成的液晶顯示元件用間隔件。 (13) 前述（12)項記載的液晶顯示元件用間隔件，係由前述（11) 項記載的塗膜以微影步驟圖案化之後，熱硬化以形成。 (14) 具備前述（12)或是（13)項所記載的間隔件之液晶顯示元 件。 (15) 於前述第（1)項中加入著色劑的光硬化性著色組成物，其特 徵爲相對於高分子結合劑與具乙烯性雙鍵化合物的合計量， 著色劑含有5〜130重量％，組成物中全固形成份的含有量爲 10〜50重量％左右。 (16) 於前述（15)項記載的光硬化性著色組成物，其中鹼可溶性 樹脂，係爲至少一種不飽和羧酸單體與至少一種不飽和羧酸 單體以外之自由基聚合性單體聚合所得的共聚合物。 (17) 於前述（16)項記載的光硬化性著色組成物，其中不飽和羧 酸單體以外之自由基聚合性單體，係爲包含如式（1)所示化合 物的至少一種的自由基聚合性單體的混合物。 CH2=^1 {〇-CH2CH2CH2CH2CH2l+CM：H2-<( Ο ο n (1) (式中I爲Η或是甲基，1爲Η或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，11爲0〜5的整數） (18) 於前述（17)項記載的光硬化性著色組成物，其中在式（1) 中’ η爲1或是2 ’ R2爲Η。 (19) 於前述（15)項記載的光硬化性著色組成物，其中鹼不溶性 13 576950 8310-pif2 的具環氧基乙烯基聚合物，係由具環氧基自由基聚合性單體 的單獨聚合，兩種以上的具環氧基自由基聚合性單體的共聚 合，或是至少一種具環氧基自由基聚合性單體與至少一種非 不飽和羧酸自由基聚合性單體且不具環氧基的化合物，共聚 合所得的聚合體。 (20)於前述（15)項記載的光硬化性著色組成物，其中具二苯甲 酮結構有機過氧化物爲如式(2)所表示的化合物。 R3—Ο—0—0 R5—Χι—(In the formula, R3 to R6 are each independent alkyl groups having 1 to 13 carbon atoms, and are carbonyl groups each having an independent or -NH-, benzophenone structure, with respect to a substituent having a benzene ring. The carbon atom 'may be bonded to any one of the carbon atoms at the P position.) Then, the compound having an ethylenic double bond is an acrylate and a methacrylic acid ester. 12 576950 8310-pif2 (11) The coating film formed by using the photosensitive resin composition according to any one of the items (1) to (10) as a material. (12) The spacer for liquid crystal display elements formed by the coating film as described in said (11). (13) The spacer for a liquid crystal display element according to the item (12), which is formed by patterning the coating film according to the item (11) in a lithography step, and then thermosetting. (14) A liquid crystal display device provided with the spacer according to the item (12) or (13). (15) The photocurable coloring composition to which a colorant is added in the above item (1), wherein the colorant contains 5 to 130% by weight based on the total amount of the polymer binder and the compound having an ethylenic double bond. The total solid content of the composition is about 10-50% by weight. (16) The photocurable coloring composition according to the item (15), wherein the alkali-soluble resin is a radically polymerizable monomer other than at least one unsaturated carboxylic acid monomer and at least one unsaturated carboxylic acid monomer. The resulting copolymer was polymerized. (17) The photocurable coloring composition according to the above item (16), wherein the radical polymerizable monomer other than the unsaturated carboxylic acid monomer is a compound containing at least one kind of the compound represented by the formula (1). Of polymerizable monomers. CH2 = ^ 1 {〇-CH2CH2CH2CH2CH2l + CM: H2- < (Ο ο n (1) (where I is fluorene or methyl, 1 is fluorene or alkyl having 1 to 5 carbon atoms, tetrahydrofuran ring 2 to 4 positions may be bonded to a carbon atom, 11 is an integer of 0 to 5) (18) The photocurable coloring composition described in the above item (17), wherein 'η is 1 or 1 in the formula (1) 2 'R2 is fluorene. (19) The photocurable coloring composition described in the above item (15), wherein the alkali-insoluble 13 576950 8310-pif2 epoxy-based vinyl polymer is composed of epoxy-based radical Individual polymerization of polymerizable monomers, copolymerization of two or more epoxy radical polymerizable monomers, or at least one epoxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical A polymer obtained by polymerizing a compound having no polymerizable monomer and having no epoxy group. (20) The photocurable coloring composition according to the above item (15), wherein the organic peroxide having a benzophenone structure is such as Compound represented by formula (2): R3—0—0—0 R5—Χι—

⑺ (式中，R3〜R6爲各別獨立的碳數1〜13的烷基，Xi以及X2 爲各別獨立的-0-、- 〇-〇-或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與p 位置的碳原子的其中任一個結合。） - (21) 於前述（20)項記載的光硬化性著色組成物，其中在式（2) φ 中，Xi以及X2爲-0-。 (22) 於前述（15)項記載的光硬化性著色組成物，其中具乙烯性 雙鍵化合物爲丙烯酸酯以及甲基丙烯酸酯。 (23) 於前述（15)項記載的光硬化性著色組成物，其特徵爲鹼可 溶性樹脂係爲至少一種不飽和羧酸單體與至少一種不飽和羧 酸單體以外之自由基聚合性單體聚合所得的共聚合物，此不 飽和羧酸單體以外之自由基聚合性單體，係爲包含如式（1)所 示化合物的至少一種的自由基聚合性單體的混合物， 14 576950 8310-pif2⑺ (wherein R3 to R6 are each independently alkyl groups having 1 to 13 carbon atoms, Xi and X2 are each independently -0-, -〇-〇- or -NH-, benzophenone structure The carbonyl group may be bonded to any of the carbon atoms at the p position with respect to the carbon atom of the substituent having a benzene ring.)-(21) The photocurable coloring composition according to the item (20) , Where in the formula (2) φ, Xi and X2 are -0. (22) The photocurable coloring composition according to the item (15), wherein the ethylenic double bond compound is an acrylate or a methacrylate. (23) The photocurable coloring composition according to the above item (15), wherein the alkali-soluble resin is a radically polymerizable monomer other than at least one unsaturated carboxylic acid monomer and at least one unsaturated carboxylic acid monomer. The copolymer obtained by bulk polymerization, and the radical polymerizable monomer other than the unsaturated carboxylic acid monomer is a mixture of radical polymerizable monomers including at least one compound represented by formula (1), 14 576950 8310-pif2

CH2=C1 oCH2 = C1 o

0—CH2CH2CH2CH2CH2—0—CH2CH2CH2CH2CH2—

⑴ (式中心爲^!或是甲基，R2爲H或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲〇〜5的整數） 鹼不溶性的具環氧基乙烯基聚合物，係由具環氧基自由基聚 合性單體的單獨聚合，兩種以上的具環氧基自由基聚合性單 體的共聚合，或是至少一種具環氧基自由基聚合性單體與至 少一種非不飽和羧酸自由基聚合性單體且不具環氧基的化合 物，共聚合所得的聚合體， 具二苯甲酮結構有機過氧化物爲如式(2)所表示的化合物，⑴ (the center of the formula is ^! Or methyl, R2 is H or an alkyl group having 1 to 5 carbons, and the 2 to 4 positions of the tetrahydrofuran ring can also be bonded to a carbon atom, and η is an integer of 0 to 5) Epoxy-based vinyl polymer, which is polymerized by an epoxy-based radically polymerizable monomer alone, copolymerized with two or more epoxy-based radically polymerizable monomers, or at least one of which has a cyclic A polymer obtained by copolymerizing an oxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical polymerizable monomer and having no epoxy group, and the organic peroxide having a benzophenone structure has the formula: The compound represented by (2),

(式中’ R3〜R0爲各別獨立的碳數1〜13的院基，Χι以及& 爲各別獨立的或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與p 位置的碳原子的其中任一個結合。） 然後，具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙烯酸酯。 (24) 前述（15)〜（22)項的其中任一項記載的光硬化性著色物作 爲材料所形成的塗膜。 (25) 前述(24)項記載的塗膜所形成的液晶顯示元件用濾色鏡。 15 8310-pif2 (26) 前述（25)項記載的液晶顯示元件用濾色鏡，係由前述(24) 項記載的塗膜以微影步驟圖案化之後，熱硬化以形成。 (27) 具備前述（25)或是（26)項所記載的濾色鏡之液晶顯示元 件。 [發明的揭示1] <感光性樹脂組成物> 本發明的感光性樹脂組成物所使用的高分子結合劑，係 爲鹼可溶性樹脂或是此鹼可溶性樹脂與鹼不溶性的具環氧基 乙烯基聚合物的混合物。然後，鹼可溶性樹脂（以下爲了容易 區分起見附上記號[A]表示，依場合亦有僅以[A]表示的情形）， 係由至少一種不飽和羧酸單體與至少一種不飽和羧酸單體以 外之自由基聚合性單體聚合所得的共聚合物。尙且，在以下 的說明中，不飽和羧酸單體係以不飽和羧酸單體（a-Ι)、或僅 以（a-Ι)表示。 (a-Ι)例如是所舉的（甲基)丙烯酸、丁烯酸、甲叉丁二酸、 順丁烯二酸、反式丁烯二酸、順式甲基丁烯二酸以及甲基反 式丁烯二酸等。此些係單獨或是組合使用。尙且，上述的（甲 基)係表不包含附有接頭§吾「甲基」場合以及未附場合的兩方 面的化合物，以下亦相同。 本發明所使用的鹼可溶性樹脂[A]，爲了對鹼水溶液的溶 解性做適度的調整，以不飽和羧酸單體（a-Ι)與（a-Ι)以外的自 由基聚合性單體共聚合所得。[A]中的（a-Ι)之聚合成份的含有 量，係爲5〜40重量％，較佳爲10〜20重量％。（a-Ι)所得的 聚合成份，在[A]中未滿5重量％的話則不容易溶於水溶液中， 超過40重量％的話，對鹼水溶液的溶解度過大的話，顯影後 576950 8310-pif2 的皮膜有容易發生膜粗糙的傾向。亦即是，（a-1)以外的自由 基聚合性單體，係爲單獨聚合物的鹼不溶性的自由基聚合性 單體，或是必須含有此自由基聚合性單體的物件。尙且，單 獨聚合物的自由基聚合性單體，表示爲自由基聚合性單體(a-2) 或是僅表示爲（a-2)。 (a-2)例如是所舉的苯乙烯、甲基苯乙烯、乙烯基甲苯等 乙烯基化合物，（甲基)丙烯酸甲酯、（甲基)丙烯酸乙酯、（甲基) 丙烯酸丙酯、（甲基）丙烯酸丁酯、2-羥乙基（甲基）丙烯酸酯、 苄基（甲基)丙烯酸酯、丁烯酸乙酯、順丁烯二酸二乙酯等不飽 和羧酸烷醇，（甲基)丙烯醯胺、二甲基胺丙烯（甲基)丙烯醯胺、 N，N-二甲基（甲基）丙烯醯胺等的（甲基）丙烯醯胺類，環氧丙基 (甲基)丙烯酸酯、3,4-環氧基丁基（甲基)丙烯酸酯、2-甲基-3,4-環氧基環己基（甲基)丙烯酸酯等的具環氧基（甲基)丙烯酸酯，3-環己烯基甲基（甲基）丙烯酸酯、環戊烯基（甲基）丙烯酸酯、三 環[5·2·1_02,6]癸烯基（甲基)丙烯酸酯、2,2,6,6-四甲基哌啶基（甲 基）丙烯酸酯、Ν-甲基-2,2,6,6-四甲基哌啶基（甲基）丙烯酸酯等 的具脂環式基或複素環式基（甲基）丙烯酸酯等。然後，此些的 單品或是混合物能夠由市售品得到。 本發明較佳爲將式（1)所表示的自由基聚合性單體，作爲 不飽和羧酸單體（a-Ι)以外之自由基聚合性單體所用的成份。 在以下的說明中，式（1)所表示的自由基聚合性單體，表示爲 自由基聚合性單體(a-3)或是僅表示爲(a-3)。(In the formula, 'R3 ~ R0 are each independent carbon groups with 1 ~ 13 carbon atoms, and X and & are each independently or -NH-, benzophenone structure carbonyl group, compared with the benzene ring The carbon atom of the substituent may be bonded to any one of the carbon atoms at the p position.) Then, the compound having an ethylenic double bond is an acrylate and a methacrylate. (24) The coating film formed by using the photocurable coloring material according to any one of the items (15) to (22) as a material. (25) The color filter for liquid crystal display elements formed by the coating film as described in said (24). 15 8310-pif2 (26) The color filter for liquid crystal display elements according to the above item (25) is formed by patterning the coating film according to the above item (24) in a lithography step and then thermosetting it. (27) A liquid crystal display device having the color filter described in the item (25) or (26) above. [Disclosure of the Invention 1] < Photosensitive resin composition > The polymer binder used in the photosensitive resin composition of the present invention is an alkali-soluble resin or an epoxy group having an alkali-insolubility with the alkali-soluble resin and alkali. Mixture of vinyl polymers. Then, the alkali-soluble resin (herein indicated by a symbol [A] for easy identification, and occasionally only [A] may be used), is composed of at least one unsaturated carboxylic acid monomer and at least one unsaturated carboxylic acid A copolymer obtained by polymerizing a radical polymerizable monomer other than the monomer. In addition, in the following description, an unsaturated carboxylic acid monosystem is represented by an unsaturated carboxylic acid monomer (a-1) or only (a-1). (a-1) are, for example, the mentioned (meth) acrylic acid, butenoic acid, mesuccinic acid, maleic acid, trans butenedioic acid, cis methylbutenedioic acid, and methyl Trans-butenedioic acid and the like. These are used alone or in combination. In addition, the above (methyl) series does not include the compound in both the case where the linker is attached to the "methyl" and the case where it is not attached, and the same applies hereinafter. The alkali-soluble resin [A] used in the present invention uses a radically polymerizable monomer other than the unsaturated carboxylic acid monomers (a-1) and (a-1) in order to appropriately adjust the solubility of the alkaline aqueous solution. Copolymerization. The content of the polymerized component (a-1) in [A] is 5 to 40% by weight, and preferably 10 to 20% by weight. (A-1) The polymerization component obtained in [A] is less than 5% by weight and is not easily soluble in an aqueous solution. If it exceeds 40% by weight, if the solubility in an alkaline aqueous solution is too large, 576950 8310-pif2 after development The film tends to be rough. That is, the free-radically polymerizable monomer other than (a-1) is an alkali-insoluble radically polymerizable monomer of an individual polymer or an article which must contain the radically polymerizable monomer. In addition, a radical polymerizable monomer of a separate polymer is expressed as a radical polymerizable monomer (a-2) or only (a-2). (a-2) Examples are vinyl compounds such as styrene, methylstyrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Unsaturated carboxylic acid alkanols, such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethyl butenoate, and diethyl maleate (Meth) acrylamide, (meth) acrylamide, dimethylamine, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc., propylene oxide (Meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, etc. (Meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, cyclopentenyl (meth) acrylate, tricyclic [5 · 2 · 1_02,6] decenyl (methyl ) Acrylate, 2,2,6,6-tetramethylpiperidinyl (meth) acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl (meth) acrylate Etc. have alicyclic group or complex element cyclic group (meth) acrylate. Then, these single products or mixtures can be obtained from commercial products. In the present invention, the radical polymerizable monomer represented by the formula (1) is preferably used as a component for a radical polymerizable monomer other than the unsaturated carboxylic acid monomer (a-1). In the following description, the radical polymerizable monomer represented by the formula (1) is expressed as the radical polymerizable monomer (a-3) or only (a-3).

ch2=c-ch2 = c-

0 0-CH2CH2CH2CH2CH20 0-CH2CH2CH2CH2CH2

(1) 17 576950 8310-pif2 (式中1爲H或是甲基，112爲H或是碳數1〜5的烷基’四氫 · 呋喃環的2〜4位置亦可以與碳原子結合，η爲〇〜5的整數） (a-3)爲了用於提升顯影性，較佳η爲1或是2，I爲Η 的化合物。爲了提升顯影性，亦可以增加不飽和羧酸單體(a-1) 的使用量，以增加鹼可溶性樹脂組成物對鹼顯影液的可溶性。 但是在此場合的話，感光性樹脂組成物的安全溶劑的丙二醇 單甲基醚乙酸酯等的溶解度降低，顯影後會產生表面粗糙等 的特性降低。以使用（a-3)，能夠改善[A]的前述丙二醇單甲基 醚乙酸酯等的溶解性，而且能夠控制鹼顯像液對感光性塗膜 & 滲透性。因此在此場合，不飽和羧酸單體的使用量不會增加’ ， 能夠提升顯影性。爲了得到[A]在全單體中（a-3)的含量爲30重 量％以下。此含量在5重量％以下的場合，對於增加對鹼顯 像液的溶解性僅有一點效果。而且在30重量％以上的場合’ 溶解度過大而使得顯影後皮膜表面容易產生粗糙。尙且使用 (a-3)時，（a-Ι)與(a-3)的合計量爲單體中的1〇〜50重量％較佳， 更佳爲15〜45重量％。 本發明的感光性樹脂的第2成份的鹼不溶性的具環氧基 ~ 乙烯基聚合物，係爲具環氧基的自由基聚合性單體的單獨聚 # 合，具環氧基的自由基聚合性單體兩種以上的共聚合，或是 至少一種具環氧基的自由基聚合性單體與至少一種非不飽和 羧酸自由基聚合性單體且不含環氧基的化合物共聚合所得。 尙且，於下述說明中，鹼不溶性的具環氧基乙烯基聚合物， 附上記號[AIS]或是僅表示爲[AIS]。具環氧基的自由基聚合性 單體附上記號（a-4)或是僅表示爲（a-4)。然後，非不飽和羧酸 自由基聚合性單體的不含環氧基化合物附上記號（a-5)或是僅 表示爲(a-5)。 18 576950 8310-pif2 (a-4)例如是所舉的環氧丙基（甲基）丙烯酸酯、3,‘環氧基 丁基（甲基）丙烯酸酯、2-甲基-3,4-環氧基環己基（甲基）丙烯酸 酯等。此些爲單獨使用或是兩種以上組合使用。例如是 前述的所舉的(a-2)(其單獨聚合物爲鹼不溶性的自由基聚合物) 之中具環氧基的甲基丙烯酸酯以外的例子，或是式（1)所表示 的自由基聚合性單體（a-3)。然後，此些亦爲單獨使用或是兩 種以上組合使用。 鹼可溶性樹脂[A]以及鹼不溶性的具環氧基乙烯基聚合物 [AIS]，係以習知以來的已知方法聚合而得。聚合溶劑的話， 只要是在聚合反應中不具活性，在聚合條件下安定的化合物 就可使用。具體而言，例如是所舉的甲醇、乙醇、2-丙醇、乙 酸乙酯、乙酸丁酯、乙二醇單異丙醚、乙二醇單丁醚、乙基 乙氧乙氧基乙醇、丙二醇單甲醚、丙二醇單甲基醚乙酸酯、 乙二醇單丁基醚乙酸酯、甲基乙基酮、環己酮、二乙二醇二 甲醚、二乙二醇二乙醚、甲苯、二甲苯r -呋喃烷酮、N，N-二 甲基乙醯胺、四氫呋喃等其中以甲醇、乙酸乙酯、環己酮、 甲基乙基酮、丙二醇單甲基醚乙酸酯爲較佳。當然亦可以使 用兩種以上的混合溶劑。 聚合反應中，通常以反應液中單體濃度爲5〜5〇重量％， 同樣的聚合引發劑爲0.01〜5重量％，反應溫度50〜160°C， 反應時間3〜12小時進行。且爲了調整分子量，亦可以加入 锍基乙酸等的鍵轉移劑。聚合反應結束後，將反應液保持此 狀態，或將反應液投入大量的非溶劑中，將寡聚物或是未反 應單體，而使用形成沈澱並經乾燥的物質。將反應液投入大 量的非溶劑中精製的場合，使用甲醇與乙酸乙酯的混合液作 爲反應溶劑，非溶劑使用環己酮或是乙酸乙酯/環己酮混合液 19 576950 8310-pif2 的話其乾燥性良好爲較佳。 鹼可溶性樹脂[A]以及鹼不溶性的具環氧基乙烯基聚合物 [AIS]的其中任一，使用N，N二甲基甲醯胺作爲溶劑以GPC分 析，聚環氧乙烷換算重量平均分子量（Mw)較佳爲1000〜 100000，更佳爲2000〜30000。此平均分子量(Mw)不滿1000 則膜的強度弱，顯影時容易引起膜粗糙，圖案剝離。另一方 面，超過100000的話，顯影性或感度會下降，顯影後會殘留 殘渣。 本發明的感光性樹脂組成物的第3成份的具乙烯性雙鍵 化合物（以下附上記號[B]以表示，亦有僅以[B]的情形。），較 佳爲甲基丙烯酸酯，具體而言例如可爲所舉的甲基（甲基)丙烯 酸酯、乙基（甲基）丙烯酸酯、丁基（甲基）丙烯酸酯、2-乙基己 基（甲基）丙烯酸酯、苯基（甲基）丙烯酸酯、苄基（甲基）丙烯酸 酯、2-羥基乙基（甲基)丙烯酸酯、2-羥基丙基（甲基)丙烯酸酯、 2-羥基丁基（甲基）丙烯酸酯、環氧丙基（甲基）丙烯酸酯、3,4-環 氧基丁基（甲基）丙烯酸酯、2-甲基-3,4-環氧基環己基（甲基）丙 烯酸酯、ω-羧基聚己內酯單（甲基）丙烯酸酯、苯二酸單羥基 乙基（甲基）丙烯酸酯、2-羥基-3-苯氧基丙基（甲基）丙烯酸酯、 二環戊烯基（甲基）丙烯酸酯、二環戊烯基羥基乙基（甲基）丙烯 酸酯、三環[5·2·1·02,6]癸烯基（甲基）丙烯酸酯、2,2,6,6·四甲基 哌啶基（甲基）丙烯酸酯、Ν-甲基-2,2,6,6-四甲基哌啶基（甲基） 丙烯酸酯、1，4-丁二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基） 丙烯酸酯、乙二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯 酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸 酯、聚乙二醇二（甲基）丙烯酸酯、羥基三甲基乙酸新戊二醇二 (甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、環氧化三 20 576950 8310-pif2 羥甲基丙烷三（甲基）丙烯酸酯、三羥甲基丙烷四（甲基）丙烯酸 酯、季戊四醇二（甲基)丙烯酸酯、季戊四醇三（甲基)丙烯酸酯、 季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、 二季戊四醇六（甲基)丙烯酸酯、二環戊烯基二（甲基)丙烯酸酯、 環氧化氫化雙酚A二（甲基)丙烯酸酯、環氧化雙酚F二（甲基) 丙烯酸酯、環氧化氫化雙酚S二（甲基)丙烯酸酯、羥基丙基二 (甲基）丙烯酸酯、二乙二醇雙羥基丙基二（甲基）丙烯酸酯、單 羥基季戊四醇三（甲基)丙烯酸酯等。此些化合物可單獨或是組 合使用。 尙且，具乙烯性雙鍵化合物[B]，爲含有3個以上的雙鍵 之化合物更佳，由上述化合物中選取的話，例如可爲所舉的 三羥甲基丙烷四（甲基)丙烯酸酯、季戊四醇二（甲基)丙烯酸酯、 季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二 季戊四醇五（甲基）丙烯酸酯以及二季戊四醇六（甲基）丙烯酸酯 等。 本發明的感光性樹脂組成物的第4成份的具二苯甲酮結 構有機過氧化物（以下附上記號[C]以表示，亦有僅以[C]的情 形。），係作爲光聚合引發劑使用。其具體例例如是所舉的4,4’-二（t-丁基過氧羰基）二苯甲酮、3,3’-二（甲氧羰基）-4,4’-二（t-丁 基過氧羰基）二苯甲酮、4,4’-二（甲氧羰基)-3,3’-二（t-丁基過氧 羰基)二苯甲酮、3,4’-二（甲氧羰基)-4,3’-二（t-丁基過氧羰基）二 苯甲酮、3,4,4’-三（t-丁基過氧羰基）二苯甲酮、3,5,4’·三（t-丁 基過氧羰基）二苯甲酮、3,4,5-三（t-丁基過氧羰基）二苯甲酮、 3,4,3’-三(t-丁基過氧羰基)二苯甲酮、2,3,4-三（t-丁基過氧羰基） 二苯甲酮、3,5,3’-三（t-丁基過氧羰基）二苯甲酮、3,4,4’-三（t-戊基過氧幾基）二苯甲酮、3,4,4’-三（t-辛基過氧簾基）二苯甲 21 576950 8310-pif2 酮、3,4,4’-三(t·異丙苯基過氧羰基）二苯甲酮、4_甲基_2，，4，_二 (t-丁基過氧羰基）二苯甲酮、4-甲基_3’，4’-二（t-丁基過氧羰基) 二苯甲酮、3_甲基-2’，4’-二（t-丁基過氧羰基)二苯甲酮、2-甲基 -2’，4’-二（t-丁基過氧羰基）二苯甲酮、4-乙基-2’，4’-二（t_丁基過 氧羰基）二苯甲酮、3,3’，4,4’-四（^丁基過氧羰基）二苯甲酮、 3,3’，4,4’-四屮己基過氧羰基）二苯甲酮等。 而且，上述的具二苯甲酮結構有機過氧化物[C]亦可以與 其他的光聚合引發劑組合使用。其他的光聚合引發劑，例如 是所舉的2,2’-二甲氧基-1，2’-二苯乙烷_1_酮、1-羥基環己基苯 基醒、2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉代丙院-1-酮、2-节基 -2-一甲胺基-1-(4-嗎啉代苯基)-丁酮-1，2,4,6-三甲苯基二苯基氧 化鱗、2_(4_甲氧基-1-萘基)-4,6-雙（三氯甲基)-s-三連氮。 上述的具二苯甲酮結構有機過氧化物[C]的具體例中，較 佳作爲光聚合引發劑的化合物，例如是下述式(2)所表示的化 合物。(1) 17 576950 8310-pif2 (wherein 1 is H or methyl, 112 is H, or 2 to 4 positions of alkyl'tetrahydro · furan ring with 1 to 5 carbon atoms can also be bonded to carbon atoms, η is an integer of 0 to 5) (a-3) In order to improve developability, a compound in which η is 1 or 2 and I is Η is preferable. In order to improve the developability, the amount of the unsaturated carboxylic acid monomer (a-1) may be increased to increase the solubility of the alkali-soluble resin composition to the alkali developer. However, in this case, the solubility of propylene glycol monomethyl ether acetate or the like, which is a safe solvent for the photosensitive resin composition, is reduced, and characteristics such as surface roughness after development are reduced. By using (a-3), the solubility of the aforementioned propylene glycol monomethyl ether acetate and the like of [A] can be improved, and the permeability of the alkali developer to the photosensitive coating film & can be controlled. Therefore, in this case, the use amount of the unsaturated carboxylic acid monomer is not increased ', and the developability can be improved. In order to obtain [A], the content of (a-3) in the total monomer is 30% by weight or less. When the content is less than 5% by weight, it has only a small effect on increasing the solubility in an alkali developing solution. In the case of 30% by weight or more, the solubility is too large, and the surface of the film is likely to be rough after development.使用 When (a-3) is used, the total amount of (a-1) and (a-3) is preferably from 10 to 50% by weight, and more preferably from 15 to 45% by weight. The second component of the photosensitive resin of the present invention is an alkali-insoluble epoxy-containing vinyl polymer, which is an independent polymerization of a radically polymerizable monomer having an epoxy group, and a radical having an epoxy group. Copolymerization of two or more polymerizable monomers, or copolymerization of at least one radically polymerizable monomer having an epoxy group and at least one compound of an unsaturated carboxylic acid radically polymerizable monomer and containing no epoxy group Income. In addition, in the following description, an alkali-insoluble epoxy-based vinyl polymer is marked with [AIS] or simply expressed as [AIS]. The radically polymerizable monomer having an epoxy group is marked with (a-4) or is simply expressed as (a-4). Then, the epoxy-group-free compound of the unsaturated carboxylic acid radically polymerizable monomer is given a mark (a-5) or simply (a-5). 18 576950 8310-pif2 (a-4) is, for example, the mentioned epoxypropyl (meth) acrylate, 3, 'epoxy-butyl (meth) acrylate, 2-methyl-3,4- Epoxy cyclohexyl (meth) acrylate and the like. These are used alone or in combination of two or more. For example, it is an example other than the epoxy methacrylate among the aforementioned (a-2) (the individual polymer is an alkali-insoluble free radical polymer), or it is represented by formula (1) Radical polymerizable monomer (a-3). Then, these are used alone or in combination of two or more. The alkali-soluble resin [A] and the alkali-insoluble epoxy-based vinyl polymer [AIS] are obtained by polymerization by a conventionally known method. As the polymerization solvent, a compound which is stable under the polymerization conditions can be used as long as it is inactive in the polymerization reaction. Specifically, for example, methanol, ethanol, 2-propanol, ethyl acetate, butyl acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylethoxyethoxyethanol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, methyl ethyl ketone, cyclohexanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Toluene, xylene r-furananone, N, N-dimethylacetamide, tetrahydrofuran, etc. Among them, methanol, ethyl acetate, cyclohexanone, methyl ethyl ketone, propylene glycol monomethyl ether acetate are Better. Of course, two or more mixed solvents may be used. In the polymerization reaction, the monomer concentration in the reaction solution is usually 5 to 50% by weight, the same polymerization initiator is 0.01 to 5% by weight, the reaction temperature is 50 to 160 ° C, and the reaction time is 3 to 12 hours. In addition, in order to adjust the molecular weight, a bond transfer agent such as fluorenylacetate may be added. After the polymerization reaction is completed, the reaction solution is kept in this state, or the reaction solution is put into a large amount of a non-solvent, and an oligomer or an unreacted monomer is used, and a substance that forms a precipitate and is dried is used. When the reaction solution is purified by adding a large amount of non-solvent, a mixed solution of methanol and ethyl acetate is used as the reaction solvent, and cyclohexanone or an ethyl acetate / cyclohexanone mixed solution is used as the non-solvent 19 576950 8310-pif2. It is preferable that the drying property is good. Either alkali-soluble resin [A] or alkali-insoluble epoxy-based vinyl polymer [AIS], analyzed by GPC using N, N dimethylformamide as a solvent, and average weight in terms of polyethylene oxide The molecular weight (Mw) is preferably 1,000 to 100,000, and more preferably 2,000 to 30,000. When the average molecular weight (Mw) is less than 1,000, the strength of the film is weak, and the film is likely to be roughened and the pattern is peeled during development. On the other hand, if it exceeds 100,000, the developability or sensitivity will decrease, and residue will remain after development. The third component of the photosensitive resin composition of the present invention has an ethylenic double bond compound (hereinafter, it is indicated by the symbol [B], and there may be only [B].), Preferably methacrylate, Specifically, for example, there may be mentioned meth (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Ester, epoxypropyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, ω-carboxy polycaprolactone mono (meth) acrylate, phthalic acid monohydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentyl Alkenyl (meth) acrylate, dicyclopentenyl hydroxyethyl (meth) acrylate, tricyclic [5 · 2 · 1.02,6] decenyl (meth) acrylate, 2,2 , 6,6 · Tetramethylpiperidinyl (meth) acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, tris Methylolpropane tri (meth) acrylate, epoxidized tri 20 576950 8310-pif2 methylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, pentaerythritol di (methyl) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentenyl di (methyl Acrylate), epoxidized hydrogenated bisphenol A di (meth) acrylate, epoxidized bisphenol F di (meth) acrylate Epoxidized hydrogenated bisphenol S di (meth) acrylate, hydroxypropyl di (meth) acrylate, diethylene glycol bishydroxypropyl di (meth) acrylate, monohydroxypentaerythritol tri (methyl) Acrylate, etc. These compounds can be used alone or in combination.乙烯 Furthermore, the compound [B] having an ethylenic double bond is more preferably a compound containing three or more double bonds. When selected from the above compounds, for example, trimethylolpropane tetra (meth) acrylic acid may be mentioned. Esters, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. An organic peroxide having a benzophenone structure as the fourth component of the photosensitive resin composition of the present invention (hereinafter, the symbol [C] is attached, and sometimes only [C] is used.), Which is used as photopolymerization. Use of initiator. Specific examples are the 4,4'-bis (t-butylperoxycarbonyl) benzophenone and 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butyl) as examples. Peroxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (t-butylperoxycarbonyl) benzophenone, 3,4'-bis (methyl (Oxycarbonyl) -4,3'-bis (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tris (t-butylperoxycarbonyl) benzophenone, 3,5, 4 '· tris (t-butylperoxycarbonyl) benzophenone, 3,4,5-tris (t-butylperoxycarbonyl) benzophenone, 3,4,3'-tris (t- Butylperoxycarbonyl) benzophenone, 2,3,4-tris (t-butylperoxycarbonyl) benzophenone, 3,5,3'-tris (t-butylperoxycarbonyl) di Benzophenone, 3,4,4'-tris (t-pentylperoxoyl) benzophenone, 3,4,4'-tris (t-octylperoxycuryl) benzophene 21 576950 8310-pif2 ketone, 3,4,4'-tris (t.cumenylperoxycarbonyl) benzophenone, 4-methyl_2,, 4, _bis (t-butylperoxycarbonyl) Benzophenone, 4-methyl-3 ', 4'-bis (t-butylperoxycarbonyl) benzophenone, 3-methyl-2', 4'-bis (t-butylperoxy) (Carbonyl) dibenzoyl Ketone, 2-methyl-2 ', 4'-bis (t-butylperoxycarbonyl) benzophenone, 4-ethyl-2', 4'-bis (t_butylperoxycarbonyl) di Benzophenone, 3,3 ', 4,4'-tetrakis (^ butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetramethylhexylperoxycarbonyl) benzophenone, etc. . Further, the above-mentioned benzophenone structure-containing organic peroxide [C] may be used in combination with other photopolymerization initiators. Other photopolymerization initiators include, for example, 2,2'-dimethoxy-1,2'-diphenylethane_1_one, 1-hydroxycyclohexylphenyl, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-monomethylamino-1- (4-morpholinophenyl)- Butanone-1,2,4,6-trimethylphenyldiphenyl oxide scale, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -s-triad nitrogen. Among the specific examples of the organic peroxide [C] having a benzophenone structure described above, a compound that is more preferable as a photopolymerization initiator is, for example, a compound represented by the following formula (2).

(式中，R3〜R6爲各別獨立的碳數1〜13的烷基，Xi以及X2 爲各別獨立的或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與p 位置的碳原子的其中任一個結合。） 具體而言例如是所舉的3,3’-二（甲氧羰基）-4,4’-二（t-丁基過氧 羰基）二苯甲酮、4,4’-二（甲氧羰基）-3,3’-二（t-丁基過氧羰基）二 苯甲酮、3,4’-二（甲氧羰基)-4,3’-二（t-丁基過氧羰基）二苯甲酮 22 576950 8310-pif2(In the formula, R3 to R6 are each independent alkyl groups having 1 to 13 carbons, Xi and X2 are each independent or -NH-, benzophenone structure carbonyl groups, and are substituted with benzene rings. The carbon atom of the radical may be bonded to any one of the carbon atoms at the p position.) Specifically, for example, 3,3'-bis (methoxycarbonyl) -4,4'-bis (t -Butylperoxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (t-butylperoxycarbonyl) benzophenone, 3,4'-di (Methoxycarbonyl) -4,3'-bis (t-butylperoxycarbonyl) benzophenone 22 576950 8310-pif2

本發明的感光性樹脂組成物的第5成份的具香豆素結構 光增感劑（以下附上記號[D]以表示，亦有僅以[D]的情形。）的 具體例’例如可爲所舉的3_苯醯-5,7-二甲氧基香豆素、3-苯酿 -7-甲氧基香豆素、3-苯醯-6-甲氧基香豆素、3-苯醯-8-甲氧基 香豆素、7-甲氧基-3-(p-硝基苯醯)香豆素、3-苯醯香豆素、 硝基苯醯）香豆素、3-苯醯苯并[f]香豆素、3-乙醯基-7-甲氧基 香豆素、3-苯醯-6-溴基香豆素、3-苯醯-7-二甲胺基香豆素、 羧基香豆素、3-羧基-7-甲氧基香豆素等。此些可單獨或組合 使用。 本發明的感光性樹脂組成物的成份含有比例，相對於高 分子結合劑（鹼可溶性樹脂[A]以及此[A]與鹼不溶性的具環氧 基乙烯基聚合物[AIS]的混合物），具乙烯性雙鍵化合物巧]爲1〇 〜200重量％，較佳爲130〜150重量％，具二苯甲嗣結構有 機過氧化物[C]爲0.1〜50重量％，較佳爲1〜30重量％以及 具香豆素結構光增感劑[D]爲0.1〜50重量％，較佳爲0.5〜30 重量％。[C]與其他的光聚合引發劑並用的場合，相對於[C]， 其他的光聚合引發劑較佳爲使用1〇〜1〇〇重量部。 相對於高分子結合劑，具乙烯性雙鍵化合物[B]未滿1〇重 量％的話，感光性樹脂的光硬化則不充分’對顯影液的溶解 性增加而於顯影之後的塗膜表面產生膜粗糙。相對於高分子 結合劑，[B]超過200重量％的話，塗膜表面的黏性會變得過 大，硬化後所得的被覆膜會產生粗糙’於顯影後會殘留殘渣。 相對於高分子結合劑，具二苯甲酮結構有機過氧化物[C]的比 例未滿0.1重量％，[B]的架橋(硬化)反應不能充分的進行。相 對於高分子結合劑，[C]的比例超過50重量％的話，顯影性會 23 576950 8310-pif2 降低。相對於高分子結合劑，具香豆素結構光增感劑[D]的比 例未滿0.1重量％，對[C]的增感作用不充分而感度降低’顯 影後會產生膜粗糙。然後，相對於高分子結合劑，[D]的比例 超過50重量％的話，所得被覆膜的殘膜率降低。 高分子結合劑，係爲如前所述之鹼可溶性樹脂[A]以及此[A] 與鹼不溶性的具環氧基乙烯基聚合物[AIS]的混合物。高分子 結合劑中[AIS]佔的比例爲〇〜60重量％，較佳爲1〇〜4〇重量 %。[AIS]係用以賦予熱硬化後被覆膜耐鹼性以及耐熱性’上 述的比例未滿5重量％則此些物性可能會降低，但在鹼可溶 性樹脂製造時的共聚合單體係使用具環氧基自由基聚合性單 體，且前述的具乙烯性雙鍵化合物[B]係使用具環氧基化合物 的場合，亦可以僅使用鹼可溶性樹脂。 本發明的感光性樹脂組成物，在不損及本發明目的之範 圍，亦可以因應需要含有上述成分之外的其他成分。此些其 他成分，例如是所舉的偶合劑(表面處理劑）、界面活性劑等。 偶合劑係用以提升與基板的緊密接合性。對於上述感光性樹 脂組成物去除掉溶劑的殘餘成分(以下略稱爲「固形成份」）， 係使用10重量％以下的添加量。 偶合劑例如是使用矽烷、鋁系以及鈦酸酯系的化合物。 具體而言可爲所舉的3-環氧丙氧基丙基二甲基乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三甲氧 基矽烷、3-丙烯醯基丙基二甲基乙氧基矽烷、3_丙烯醯基丙基 甲基二乙氧基矽烷、3-丙烯醯基丙基三乙氧基矽烷、3-甲基丙 烯醯基丙基二甲基乙氧基矽烷、3-甲基丙烯醯基丙基甲基二乙 氧基矽烷、3-甲基丙烯醯基丙基三乙氧基矽烷、3-丙烯醯基丙 基二甲基甲氧基矽烷、3-丙烯醯基丙基甲基二甲氧基矽烷等的 24 576950 8310-pif2 矽烷系、乙醯烷氧基鋁二異丙酯等的鋁系，四異丙基雙（二辛 基磷酸酯)鈦酸酯等的鈦酸酯系。 界面活性劑係用於提升對下方基板的濕潤性、平坦化性、 塗佈性，相對於上述感光性樹脂組成物添加0.01〜1重量％。 界面活性劑例如是使用矽系界面活性劑、丙烯醯系界面活性 劑，氟素系界面活性劑等，能夠由各種的市售品獲得。 本發明的感光性樹脂組成物，通常係溶解於適當的溶劑 而以溶液狀態使用。此溶液係在溶劑中投入前述的高分子結 合劑完全溶解後，於此溶液中將具乙烯性雙鍵化合物[B]、具 二苯甲酮結構有機過氧化物[C]、具香豆素結構光增感劑[D]以 及因應需要的偶合劑、界面活性劑以預定的比例混合，將固 形成份的濃度調製爲10〜50重量％，其後將之攪拌完全溶解 以得本發明的感光性樹脂組成物。 此固形成份濃度，必須設定爲了要對基板表面進行圓滑 的塗佈、或是爲了調節塗膜厚度的輔助手段，高分子結合劑 的分子量大時、或是塗膜的厚度薄時，調整降低固形成份濃 度，而且高分子結合劑的分子量小時、或是塗膜的厚度厚時， 則調整提高固形成份濃度。 此時所使用的溶劑，可爲所舉的甲氧基二乙醇、乙氧基 乙醇、1-甲氧基-2-丙醇、甲基乙二醇乙醚、乙基乙二醇乙醚、 丁基乙二醇乙醚、二乙二醇單甲基醚、二乙二醇單乙基醚、 二乙二醇二甲基醚、甲基乙二醇乙醚乙酸酯、乙基乙二醇乙 醚乙酸酯、丙二醇甲基醚乙酸酯、乳酸乙酯、N-甲基-2-吡咯 烷酮、N，N-二甲基乙醯胺等，此些溶劑可單獨或是兩種以上 混合使用。 將如上所述之經調製的感光性樹脂組成物溶液，塗佈於 25 576950 8310-pif2 基板表面、加熱除去溶劑，而能夠形成塗膜。對基板表面塗 佈感光性樹脂組成物的方法，例如可使用所舉的旋轉塗佈(spin coat)法、滾筒塗佈(roll coat)法以及浸泡塗佈（dipping coat)法 等習知所已知的方法進行。其次，此塗膜置於熱墊板（Ή(η P1ate)、熱爐（〇ven)等力口熱（以下略記爲「預烤（prebake)」）。 預烤的條件依各成分的種類、混合比例而不同，通常爲在7〇 〜110°C，於熱墊板爲1〜5分鐘之間，於熱爐則爲5〜15分鐘 之間。 本發明的液晶顯示元件用間隔件，係將上述經預烤的塗 膜形成於液晶顯示元件用的電極基板上後，藉由已形成預定 圖案的光罩以紫外光照射後，以顯影液顯影去除不要的部份 而得。（對於間隔件的形成方法，在後述本發明的液晶顯示元 件的說明中會做更詳細的描述） 頒影液例如是使用所舉的碳酸鈉、氫氧化鈉氫氧化鉀等 的無機鹽類，或是四甲基銨氫氧化物、四乙基銨氫氧化物等 有機鹼水溶液。而且，於上述鹼液中亦能夠加入適當量的甲 醇、乙醇界面活性劑等。 顯^的方法可使用浸泡 '淋浴(Shower)、噴灑（Spray)等的 任意方法，顯影時間通常爲30〜24〇秒，顯影後以水淸洗、 乾燥而能夠形成圖案。其後，此圖案置於熱墊板、熱爐等加 熱（以下略記爲「事後烤(p〇stbake)」），進一步將未反應的具 乙烯性雙鍵化合物[B]架橋的同時，將溶劑完全除去，而能夠 得到預定的塗膜圖案。事後烤的條件依各成分的種類、混合 比例而不同，通常爲在180〜25(rc，於熱墊板爲5〜3〇分鐘 之間，於熱爐則爲30〜90分鐘之間。 本發明的液晶顯示元件，其特徵爲具有以前述本發明的 26 576950 8310-pif2 感光性樹脂組成物所形成的間隔件。其液晶顯示元件的製作 方法如下說明。 在已依次沈積有透明導電性電極（例如可爲所舉的銦錫氧 化物（ITO)、氧化錫（SnOx)等）與配向膜的基板的配向膜表面、 或是在已沈積有透明導電性電極的基板的電極表面上，塗佈 本發明的感光性樹脂組成物並使之乾燥，以形成目的厚度的 塗膜。其後，經由例如是具有5 /z mx 5 // m〜15 μ mx 15 // m 的格子狀透光部份圖案的光罩，以放射線照射，以顯影將放 射線非照射部份去除以進行固化，於液晶面板的開口部之外 的部份(例如是像素間），形成感光性樹脂的硬化膜亦即是成爲 格子狀的柱狀間隔件。 此間隔件的形狀並沒有特別的限制，由正上方所見的場 合’較佳爲正方形、長方形、圓形、橢圓形。爲長方形、橢 圓形的場合，長的方向較佳爲與硏磨方向垂直或是平行。而 且，由剖面觀之的場合爲正方形、長方形、梯形，特別是較 佳爲梯形。更加的梯形上方的角落亦可以圓化，梯形的下方 亦可以延伸有裙狀。在梯形的間隔件上塗佈配向膜，進行硏 磨處理時’特別有效於平均的塗佈配向膜或是平均的硏磨處 理。 基板可爲所舉的白板玻璃、藍板玻璃、矽膠塗佈藍板玻 璃等透明玻璃基板、聚碳酸酯、聚乙酯、丙烯醯樹脂、氯化 乙烯樹脂、芳香族聚醯胺樹脂、聚醯胺醯亞胺、聚醯亞胺樹 脂等的合成樹脂薄板、薄膜或是基板，鋁板、銅板、鎳板、 不銹鋼板等的金屬基板，其他的陶瓷板、具有光電變換元件 的半導體基板等。此些基板依照需要能夠進行矽烷偶合劑等 的藥品處理、電漿處理、離子電鍍、濺鍍、化學氣象沈積法、 27 576950 8310-pif2 真空蒸鑛等前處理。 對基板塗佈感光性樹脂組成物，能夠以旋轉塗佈法、滾 筒塗佈法、浸泡塗佈等習知所已知的方法。塗膜的乾燥例如 可對塗膜吹附過熱的空氣，或是將基板放置於過熱的熱墊板 上。乾燥風或熱墊板的加熱溫度爲30〜300°C，特別是較佳爲 50〜200°C。加熱時間較適合爲丨〜川分鐘，加熱溫度可保持 一定’亦可以階段性的上升。乾燥後的膜厚通常爲0.1〜10/z m，較佳爲1〜7# m。 形成間隙壁時使用的放射線，能夠使用可見光、紫外線、 深紫外光、電子線、X射線等。特別是較佳爲波長範圍19〇nm 〜450nm的放射線。放射線的照射能量，較佳爲1〜 1000mJ/cm2 〇 顯影液例如是使用所舉的碳酸鈉、氫氧化鈉氫氧化鉀等 的無機鹽類，或是四甲基銨氫氧化物、四乙基銨氫氧化物等 有機鹼水溶液。而且於上述鹼水溶液能夠添加適當量的甲醇、 乙醇、界面活性劑。顯影方法可採用浸泡、淋浴、噴灑等的 任意方法，顯影時間通常爲30〜240秒，顯影後以水淸洗、 乾燥而能夠形成圖案。 依此形成的間隔件可爲點狀亦可爲線狀。更加的，亦可 以於此樹脂塗膜中散佈、固定習知所使用的小珠。而且，感 光性樹脂組成物塗佈於玻璃基板上，僅於同樣的進行圖案化 的基板的周邊部殘留此組成物，於其上與其他基板相對向的 將液晶記憶胞組合、壓著、固化，而能夠將此組成物作爲密 封材以組合液晶元件。更加的，亦可以在此樹脂塗膜上進行 配向處理以形成膜。 液晶顯示元件的製作，係將如上所述之已形成的上下元 28 576950 8310-pif2 件基板的位置對準並壓著後，以熱處理將之組合後注入液晶， 將注入口密封。而且，亦可以在液晶元件基板散布液晶後， 將基板重合，使液晶不外漏的密封以製作液晶顯示元件。依 此，能夠在液晶顯示元件中，具有本發明的感光性樹脂組成 物所形成之具有優良耐液晶性的間隔件。 尙且，本發明的液晶表示元件所使用的液晶’亦即是液 晶化合物以及液晶組成物沒有特別的限制’可以使用任意的 液晶化合物以及液晶組成物° 本發明的液晶顯示元件所用的配向劑’如果具有規範液 晶分子的配向的物件的話，則沒有特別的限定’無機物或是 有機物皆可以。一般而言爲多使用聚醯亞胺系、聚醯胺的樹 脂，具體而言，具有如下式（3)或是式（4)所示結構的聚合單位 的樹脂爲較佳。A specific example of the fifth component of the photosensitive resin composition of the present invention is a coumarin-structured photosensitizer (hereinafter, the symbol [D] is attached, and the case may be [D] alone.) For example, 3-phenylhydrazone-5,7-dimethoxycoumarin, 3-benzene-7-methoxycoumarin, 3-phenyl-6-methoxycoumarin, 3 -Phenylhydrazone-8-methoxycoumarin, 7-methoxy-3- (p-nitrophenylhydrazone) coumarin, 3-phenylhydrazonecoumarin, nitrophenylhydrazone) coumarin, 3-Benzenebenzo [f] coumarin, 3-Ethyl-7-methoxycoumarin, 3-Benzene-6-bromocoumarin, 3-Benzene-7-dimethyl Aminocoumarin, carboxycoumarin, 3-carboxy-7-methoxycoumarin, and the like. These can be used individually or in combination. The content ratio of the components of the photosensitive resin composition of the present invention is relative to the polymer binder (the alkali-soluble resin [A] and the mixture of [A] and the alkali-insoluble epoxy-based vinyl polymer [AIS]), The compound having an ethylenic double bond is 10 to 200% by weight, preferably 130 to 150% by weight, and the organic peroxide [C] with a dibenzofluorene structure is 0.1 to 50% by weight, preferably 1 to 30% by weight and coumarin structure photosensitizer [D] is 0.1 to 50% by weight, preferably 0.5 to 30% by weight. When [C] is used in combination with other photopolymerization initiators, it is preferable to use 10 to 100 parts by weight of other photopolymerization initiators relative to [C]. Relative to the high-molecular binder, if the ethylenic double bond compound [B] is less than 10% by weight, the photocuring of the photosensitive resin is insufficient. The solubility in the developing solution is increased and the surface of the coating film after development is generated. The film is rough. When [B] is more than 200% by weight relative to the polymer binder, the viscosity of the coating film surface becomes too large, and the coating film obtained after curing is roughened. Residues remain after development. The ratio of the organic peroxide [C] having a benzophenone structure to the polymer binder is less than 0.1% by weight, and the bridging (hardening) reaction of [B] cannot proceed sufficiently. When the proportion of [C] exceeds 50% by weight relative to the polymer binder, the developability is lowered 23 576950 8310-pif2. The proportion of the coumarin structure light sensitizer [D] is less than 0.1% by weight relative to the polymer binder, and the sensitization effect on [C] is insufficient and the sensitivity is reduced ', resulting in film roughness. When the ratio of [D] to the polymer binder exceeds 50% by weight, the residual film rate of the obtained coating film decreases. The polymer binder is a mixture of the alkali-soluble resin [A] as described above and the [A] and an alkali-insoluble epoxy-based vinyl polymer [AIS]. The proportion of [AIS] in the polymer binder is 0 to 60% by weight, and preferably 10 to 40% by weight. [AIS] is used to impart alkali resistance and heat resistance to the coating film after heat curing. 'The above ratio may be less than 5% by weight. These physical properties may be reduced. However, it is used as a copolymerized single system in the manufacture of alkali-soluble resins. When an epoxy-based radically polymerizable monomer is used and the aforementioned ethylene-based double bond compound [B] is an epoxy-based compound, only an alkali-soluble resin may be used. The photosensitive resin composition of the present invention may contain other components in addition to the above-mentioned components, as long as the object of the present invention is not impaired. These other ingredients are, for example, the mentioned coupling agents (surface treatment agents), surfactants, and the like. The coupling agent is used to improve the close adhesion with the substrate. The residual amount of the solvent (hereinafter referred to as "solid content") from which the above-mentioned photosensitive resin composition is removed is used in an amount of 10% by weight or less. The coupling agent is, for example, a silane, aluminum-based, or titanate-based compound. Specifically, it may be 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-propenylpropyldimethylethoxysilane, 3-propenylpropylmethyldiethoxysilane, 3-propenylpropyltriethoxysilane, 3 -Methacrylfluorenylpropyldimethylethoxysilane, 3-methacrylfluorenylpropylmethyldiethoxysilane, 3-methacrylfluorenylpropyltriethoxysilane, 3- 24 576950 8310-pif2 Silane based, Acryloylpropyldimethylmethoxysilane, 3-propenylpropylmethyldimethoxysilane, etc. Titanate, such as tetraisopropylbis (dioctyl phosphate) titanate. The surfactant is used to improve the wettability, flatness, and coatability of the lower substrate, and is added in an amount of 0.01 to 1% by weight based on the photosensitive resin composition. The surfactant is, for example, a silicon-based surfactant, an acryl-based surfactant, or a fluorine-based surfactant, and can be obtained from various commercially available products. The photosensitive resin composition of the present invention is usually dissolved in an appropriate solvent and used in a solution state. This solution is prepared by dissolving the above-mentioned polymer binder in a solvent and completely dissolving it. In this solution, an ethylenic double bond compound [B], a benzophenone structure organic peroxide [C], and a coumarin The structured light sensitizer [D] and the coupling agent and the surfactant as required are mixed in a predetermined ratio, and the concentration of the solid component is adjusted to 10 to 50% by weight, which is then stirred and completely dissolved to obtain the photosensitivity of the present invention. Sexual resin composition. This solid content concentration must be set to facilitate smooth coating of the substrate surface or to assist in adjusting the thickness of the coating film. When the molecular weight of the polymer binder is large, or when the thickness of the coating film is thin, adjust to reduce the solid shape. When the component concentration is low and the molecular weight of the polymer binder is small or the thickness of the coating film is thick, the solid content concentration is adjusted to increase. The solvent used at this time may be the methoxydiethanol, ethoxyethanol, 1-methoxy-2-propanol, methyl glycol ether, ethyl glycol ether, butyl Glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, methyl glycol ether acetate, ethyl glycol ether acetate Esters, propylene glycol methyl ether acetate, ethyl lactate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, etc. These solvents can be used alone or in combination of two or more. The prepared photosensitive resin composition solution as described above is applied to the surface of a substrate of 25 576950 8310-pif2 and the solvent is removed by heating to form a coating film. As a method for applying a photosensitive resin composition to the surface of a substrate, for example, conventional spin coating methods, roll coating methods, and dipping coating methods can be used. Known method. Secondly, this coating film is placed on a hot pad (P (η P1ate), hot oven (〇ven), etc. (hereinafter referred to as "prebake"). The conditions for prebake depend on the type of each component, The mixing ratio varies, usually between 70 ° C and 110 ° C, between 1 and 5 minutes on a hot pad, and between 5 and 15 minutes on a hot plate. The spacer for a liquid crystal display element of the present invention is The pre-baked coating film is formed on an electrode substrate for a liquid crystal display element, and is irradiated with ultraviolet light through a photomask having a predetermined pattern, and then developed by a developing solution to remove unnecessary portions. (For the interval The method of forming the element will be described in more detail in the description of the liquid crystal display element of the present invention described later.) The filming solution is, for example, an inorganic salt such as sodium carbonate, sodium hydroxide, potassium hydroxide, or the like. Organic alkali aqueous solutions such as methyl ammonium hydroxide and tetraethylammonium hydroxide. In addition, an appropriate amount of methanol, ethanol surfactant, etc. can be added to the above-mentioned lye. The obvious method can use immersion 'shower ( Shower), Spray (Spray), etc. The filming time is usually 30 to 24 seconds. After development, the pattern can be washed with water and dried to form a pattern. Thereafter, the pattern is heated on a hot plate, a hot oven, etc. (hereinafter abbreviated as "post-bake") ”), While unreacting the unreacted ethylenic double bond compound [B], and completely removing the solvent, a predetermined coating film pattern can be obtained. Post-baking conditions vary depending on the type and mixing ratio of each component, It is usually between 180 and 25 (rc, between 5 and 30 minutes on the hot pad, and between 30 and 90 minutes on the hot plate. The liquid crystal display element of the present invention is characterized by having 26 576950 8310-pif2 A spacer made of a photosensitive resin composition. The manufacturing method of its liquid crystal display element is described below. Transparent conductive electrodes (such as indium tin oxide (ITO), Tin oxide (SnOx, etc.) and the alignment film surface of the substrate of the alignment film, or the electrode surface of the substrate on which the transparent conductive electrode has been deposited, is coated with the photosensitive resin composition of the present invention and dried to Forming purpose After that, it is irradiated with radiation through a photomask having a grid-like light-transmitting partial pattern of 5 / z mx 5 // m ~ 15 μmx 15 // m, for example, and the radiation is non-irradiated by development. Partially removed for curing, the hardened film of photosensitive resin is formed on the part other than the opening of the liquid crystal panel (for example, between pixels), that is, a columnar spacer made into a grid. The shape of this spacer is There is no particular limitation, when viewed from directly above, 'square, rectangle, circle, and oval are preferred. When rectangular or oval, the long direction is preferably perpendicular to or parallel to the honing direction. Also, When viewed from a cross section, it is square, rectangular, trapezoidal, and particularly preferably trapezoidal. The corners above the trapezoid can also be rounded, and the skirt can be extended below the trapezoid. When an alignment film is coated on a trapezoidal spacer and subjected to a honing process, it is particularly effective for applying an average alignment film or an average honing process. The substrate may be transparent glass substrates such as white board glass, blue plate glass, and silicone-coated blue plate glass, polycarbonate, polyethylene, acrylic resin, vinyl chloride resin, aromatic polyamide resin, and polyfluorene. Synthetic resin thin plates, films, or substrates such as amine imine and polyimide resins; metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; other ceramic plates; and semiconductor substrates having photoelectric conversion elements. These substrates can be used for chemical processing such as silane coupling agents, plasma processing, ion plating, sputtering, chemical weather deposition, 27 576950 8310-pif2 vacuum evaporation, etc. as required. The substrate may be coated with a photosensitive resin composition by a conventionally known method such as a spin coating method, a roll coating method, or a dip coating method. The drying of the coating film can be performed by, for example, blowing superheated air on the coating film, or placing the substrate on an overheated hot pad. The heating temperature of the drying wind or the hot pad is 30 to 300 ° C, and particularly preferably 50 to 200 ° C. The heating time is more preferably from 1 minute to 1 minute, and the heating temperature can be kept constant 'or it can be increased in stages. The film thickness after drying is usually 0.1 to 10 / z m, preferably 1 to 7 # m. The radiation used when forming the partition wall can be visible light, ultraviolet light, deep ultraviolet light, electron beam, X-ray, or the like. In particular, radiation having a wavelength range of 19 to 450 nm is preferred. The irradiation energy of radiation is preferably 1 to 1000 mJ / cm2. The developing solution is, for example, an inorganic salt such as sodium carbonate, sodium hydroxide, or potassium hydroxide, or tetramethylammonium hydroxide, tetraethyl, etc. Aqueous organic alkali such as ammonium hydroxide. Further, an appropriate amount of methanol, ethanol, and a surfactant can be added to the alkaline aqueous solution. The development method can be any method such as immersion, shower, spray, etc. The development time is usually 30 to 240 seconds. After development, it can be washed with water and dried to form a pattern. The spacers thus formed may be dot-shaped or linear. Furthermore, beads which are conventionally used may be dispersed and fixed in this resin coating film. In addition, the photosensitive resin composition is coated on a glass substrate, and the composition remains only on the peripheral portion of the same patterned substrate, and the liquid crystal memory cells are assembled, pressed, and cured facing the other substrate thereon , And this composition can be used as a sealing material to combine liquid crystal elements. Furthermore, an alignment treatment may be performed on the resin coating film to form a film. The liquid crystal display device is manufactured by aligning and pressing the formed upper and lower elements 28 576950 8310-pif2 substrates as described above, and then combining them by heat treatment to inject liquid crystals and sealing the injection port. In addition, after the liquid crystal element substrate is dispersed with liquid crystal, the substrates may be overlapped so that the liquid crystal is not leaked to form a liquid crystal display element. Accordingly, in the liquid crystal display element, a spacer having excellent liquid crystal resistance formed from the photosensitive resin composition of the present invention can be used. In addition, the liquid crystal used in the liquid crystal display element of the present invention, that is, the liquid crystal compound and the liquid crystal composition is not particularly limited. Any liquid crystal compound and liquid crystal composition can be used. Alignment agent used in the liquid crystal display element of the present invention. If there is an object that regulates the alignment of liquid crystal molecules, there is no particular limitation on whether it is an inorganic or organic substance. Generally, resins using polyfluorene-based or polyfluorene-based resins are used in many cases, and specifically, resins having a polymerization unit having a structure represented by the following formula (3) or formula (4) are preferred.

(式中，G爲二胺化合物的殘餘基，係爲具芳香族基的有機基 或是脂肪族基，Y爲四羧酸化合物的殘餘基’係爲脂肪族基、 芳香族基、脂環式基、縮合環式基、架橋瓌式基’或是含有2 29 576950 8310-pif2 種以上此些基的有機基。） 2價的有機基G的具體例，例如可爲下列式(G1)〜（G10)所舉 的基。(In the formula, G is a residual group of a diamine compound, which is an organic group having an aromatic group or an aliphatic group, and Y is a residual group of a tetracarboxylic acid compound, which is an aliphatic group, an aromatic group, and an alicyclic group. Formula group, condensed cyclic group, bridging hydrazone group, or an organic group containing 2 or more of these groups 2 29 576 950 8310-pif.) Specific examples of the divalent organic group G may be, for example, the following formula (G1) ~ (G10) The bases given.

(01)(01)

(式中，R8爲Η或是碳數1〜10的烷基，R9爲碳數1〜10的烷 基，η表不1〜3的整數，m表示1或是2) 4價的有機基Y的具體例，例如可爲下列式(Y1)〜（Y11) 所舉的基。 30 576950 8310-pif2(Wherein R8 is fluorene or an alkyl group having 1 to 10 carbon atoms, R9 is an alkyl group having 1 to 10 carbon atoms, η represents an integer of 1 to 3, and m represents 1 or 2) A tetravalent organic group Specific examples of Y may be, for example, the groups given by the following formulae (Y1) to (Y11). 30 576950 8310-pif2

(¥1)(¥ 1)

<Y4) m (Υ6) (Yf)< Y4) m (Υ6) (Yf)

(Υ8) (Υ5) >〇: (Ί9) (Υιό) κ (YU ) (式中，：^8爲Η或是碳數1〜10的院基，q表示0〜4的整 數，r表示0或是1) [發明的揭示2] <光硬化性著色組成物> 本發明的光硬化性著色組成物，係於前述的感光性樹脂 組成物加入著色劑的組成物。 於本發明中，能使用染料、無機顏料、有機顏料等的著 色劑。著色劑的具體例例如是偶氮基染量、蔥醌染料、三苯 甲基染料、聚甲炔染料、金屬錯鹽染料、雙偶氮染料、三偶 氮染料、硫化染料、靛類染料等合成染料或C.I.顏料黃12、13、 14、17、20、24、31、55、83、93、109、110、137、138、139、 150、153、154、166、168、173、180、185，C.I·顏料橘 36、 31 576950 8310-pif2 43、51、71，C.I·顏料紅 9、97、122、123、149、176、177、 180、215、254，C.I·顏料紫 19、23、29，C.I_顏料藍 15、15 : 3、15 : 6，C.I·顏料綠 7、36，C.I·顏料棕、28，c·;[•顏料黑 1、 7等有機顏料。由色純度、耐熱性、耐光性的觀點以有機顏料 較佳。更加的，由色純度與透過率的觀點以C.I.顏料紅177、 254，C.I·顏料黃 138、139、150、180、185，C.L顏料橘 71、 C.I·顏料綠36 ’ C.I.顏料藍15、15 : 6更佳。 本發明的著色劑的使用量，依所製造濾色鏡的顏色或濾 色鏡的使用目的具有相當大的差異，相對於高分子結合劑與 具乙烯性雙鍵化合物[B]的合計量，較佳爲5〜130重量％。其 使用量相對於高分子結合劑與[B]的合計量，未滿5重量％則 無法形成爲了達成所需色純度的膜厚，反之超過130重量％ 的話，於圖案邊緣則容易產生鋸齒狀等的不佳狀況。 本發明的光硬化性著色組成物，亦可以因應需要含有上 述成分之外的其他成分。使用偶合劑的場合，其添加比例係 相對於組成物中的著色劑所含固形成份爲10重量％以下。而 且，添加界面活性劑的場合，其添加比例係相對於組成物中 的著色劑所含固形成份爲0.01〜10重量％。 本發明的光硬化性著色組成物，係於本發明的感光性樹 脂組成物中加入著色劑的溶液或分散液，以增加或減少溶劑 的使用量以調整固形成份濃度至10〜50重量％，攪拌混合而 得。此固形成份濃度，必須設定對基板表面進行圓滑的塗佈、 或是爲了調節塗膜厚度用的輔助手段，高分子結合劑的分子 量大時、或是塗膜的厚度薄時，調整降低固形成份濃度，而 且高分子結合劑的分子量小時、或是塗膜的厚度厚時，則調 整提高固形成份濃度。尙且，在調製著色劑的溶液或分散液 32 576950 8310-pif2 所用的溶劑時，能夠由本發明的感光性樹脂組成物用的溶劑 選擇適當的使用。 將如上所述之經調製的光硬化性著色組成物，塗佈於基 板表面、加熱除去溶劑，而能夠形成塗膜。對基板表面塗佈 感光性樹脂組成物的方法，例如可使用所舉的旋轉塗佈法、 滾筒塗佈法以及浸泡塗佈法等習知所公知的方法進行。塗佈 後塗膜的乾燥，例如可對塗膜吹附過熱的空氣，或是將基板 放至於過熱的熱墊板上或是靜置於熱爐內加熱(以下略記爲「預 烤(Prebake)」）。預烤的條件依各成分的種類、混合比例而不 同，通常爲在30〜300°C，特別是較佳爲50〜200°C。加熱時 間較適合爲1〜30分鐘，加熱溫度可保持一定，亦可以階段 性的上升。乾燥後的膜厚通常爲0.1〜ΙΟ/zm，較佳爲〇.5〜5 μ m。 而且，在液晶顯示元件用基板的透明導電性電極（例如可 爲所舉的銦錫氧化物(ITO)、氧化錫（SnOx)等）上，或是已施以 配向處理的配向膜上面，上述的塗膜形成預定的厚度後，經 由例如是具有5//mx 5//m〜15/zmx 15/zm的格子狀透光部 份圖案的光罩，以放射線照射，以顯影將放射線非照射部份 去除以進行固化，作成描繪有必要圖案的濾色鏡。此時使用 的放射線，能夠使用可見光、紫外線、深紫外光、電子線、χ 射線等。特別是較佳爲波長範圍190nm〜450nm的放射線。放 射線的照射能量，較佳爲1〜l〇〇〇mJ/cm2。 顯影液例如是使用所舉的碳酸鈉、氫氧化鈉氫氧化鉀等 的無機鹽類，或是四甲基銨氫氧化物、四乙基銨氫氧化物等 有機鹼水溶液。而且於上述鹼水溶液能夠添加適當量的甲醇、 乙醇、界面活性劑。顯影方法可採用浸泡、淋浴、噴灑等的 33 576950 8310-pif2 任意方法，顯影時間通常爲30〜240秒，顯影後以水淸洗、 卓乙燥而哇夠形成圖案。其後，此圖案鹰於熱墊板、熱爐等加 熱（以下略記爲「事後烤(Postbake)」），進一步將未反應的具 乙烯性雙鍵化合物[B]架橋的同時，将溶劑完全除去，而能夠 得到預定的塗膜圖案。事後烤的條件依 各成分的種類、混合比例而不同，通常爲在18〇〜250°C， 於熱墊板爲5〜30分鐘之間，於熱爐則爲〜分鐘之間。 基板可爲所舉的白板玻璃、藍板ϊ皮璃、砂膠塗佈藍板玻 璃等透明玻璃基板、聚碳酸酯、聚乙_、丙儲醯樹脂、氯化 乙烯樹脂、芳香族聚醯胺樹脂、聚醯胺醯亞胺、聚醯亞胺樹 脂等的合成樹脂薄板、薄膜或是基板，錦板、銅板、鎳板、 不銹鋼板等的金屬基板，其他的陶瓷板、具有光電變換元件 的半導體基板等。此些基板依照需5能夠進行砂院偶合劑等 的藥品處理、電漿處理、離子電鍍、濺鍍、化學氣象沈積法、 真空蒸鍍等前處理。 [本發明的最佳實施例] 以下對h本發明的間隔件形成材料的實施例進行更詳細 的說明，然而本發明並非限定於此實施例。 (鹼可溶性樹脂[A]的調製） 實施例、比較例所使用的鹼可溶性樹脂[A-1]〜[A-3]如下 述所調製。 <[A-1]的調製〉 在裝設有攪拌機、冷卻管、氮氣導入管以及溫度計的可 分離式燒瓶中，加入作爲不飽和羧酸的甲基丙烯酸20g，作爲 其單獨聚合物係具鹼不溶性自由基聚合性單體(a_2)的苄基甲 34 576950 8310-pif 2 基丙烯酸酯130g以及2-羥基乙基甲基丙烯酸酯20g，作爲式（1) 的自由基聚合性單體（a-3)的5-四氫呋喃羥基碳基戊基丙烯酸 酯30g、作爲聚合引發劑的2,2’-偶氮二異丁腈lg、作爲鍊轉 移劑的锍基乙酸3g、作爲溶劑的甲醇167g以及乙酸乙酯 333g。於30分鐘之間以氮氣去除氧氣將燒瓶進行油浴，以保 持瓶內爲65°C而進行6小時聚合反應。其後在聚合液中加入 環己烷3000g以析出高分子，將上澄液以傾析除去後，於40 °(：真空乾燥20小時以得鹼可溶性樹脂[A-1]。所得的 聚乙烯氧撐換算重量平均分子量爲7000(請參照表1) <鹼可溶性樹脂[A-2]以及[A-3]的調製> 變更如表1所示的單體成份的比例，與鹼可溶樹脂[A-1] 相同的方法，而得到[A-2]以及[A-3]。所得的樹脂的分子量表 示於表1。 35 8310-pif2 表l A-1 A-2 A-3 (單體） (g) a-1 甲基丙烯酸 20 30 20 a-2 BMA 130 130 90 MMA — — 80 HEMA 20 20 10 a-3 FCPA 30 20 _ (聚合引發劑） (g) AIBN 1 1 1 (鍵轉移劑） (g) TGA 3 3 3 (溶劑） (g) 甲醇 167 167 167 乙酸乙酯 333 333 333 重量平均分子量 (Mw) 7000 7200 8300 576950 表1中的記號，各別表示下列化合物。 BMA :苄基甲基丙烯酸酯 MMA :甲基甲基丙烯酸酯 HEMA : 2-羥基乙基甲基丙烯酸酯 FCPA: 5-四氫呋喃羥基碳基戊基丙烯酸酯 AIBN : 2,2’-偶氮二異丁腈 TGA :酼基乙酸 (鹼不溶性的具環氧基乙烯聚合物[AIS]的調製） 實施例、比較例所用的鹼不溶性的具環氧基乙烯聚合物 36 576950 8310-pif2 [AIS-1]〜[AIS_4]如下述所調製。 <[AIS-1]的調製> 在裝設有攪拌機、冷卻管、氮氣導入管以及溫度計的可 分離式燒瓶中，加入作爲具環氧基自由基聚合性單體（a-4)的 環氧丙基甲基丙烯酸酯16〇g、作爲不含環氧基自由基聚合性 單體（a-5)的甲基甲基丙烯酸酯40g、作爲聚合引發劑的2,2’-偶氮二異丁腈8g、作爲溶劑的甲基乙基甲酮800g。於30分 鐘之間以氮氣去除氧氣將燒瓶進行油浴，以保持瓶內爲80°C 而進行6小時聚合反應。其後在聚合液中加入環己烷3〇〇〇g 以析出高分子，將上澄液以傾析除去後，於40°C真空乾燥20 小時以得[AIS-1]。[AIS-1]的聚乙烯氧撐換算重量平均分子量爲 61〇〇(請參照表2) <鹼不溶性的具環氧基乙烯聚合物[AIS-2]〜[AIS-4]的調製> 變更如表2所示的單體成份的比例，與鹼不溶性的具環 氧基乙烯聚合物[AIS-1]相同的方法，而得到[Ais_q〜[Af4]。 各別的分子量表示於表2。 37 8310-pif2 表2 AIS-1 AIS，2 AIS，3 AIS，4 (單體） (g) a-4 GMA 160 160 160 200 MMA 40 a-5 HEMA 40 TCDMA 40 (聚合引發劑) (g) AIBN 8 8 8 8 (溶劑） (g) MEK 800 800 800 800 重量平均分子量 （Mw) 6100 6100 7000 6200 576950 表2中的記號，各別表示下列化合物。 GMA :環氧丙基甲基丙烯酸酯 MMA :甲基甲基丙烯酸酯 HEMA : 2-羥基乙基甲基丙烯酸酯 TCDMA:三環[5.2.1.02,6]癸烯基甲基丙烯酸酯 AIBN : 2,2’-偶氮二異丁腈 MEK :曱基乙基甲酮 以下爲對感光性樹脂組成物的調製、其性能的評價、使 用其所製作的間隔件與液晶顯示元件以及對此些進行評價的 結果，以下述的實施例加以說明。 (感光性樹脂組成物的調製） 第1實施例 鹼可溶性樹脂[A_l]1.00g，鹼不溶性的具環氧基乙烯聚合 38 576950 8310-pif2 物[AIS_l]〇.15g，以及丙二醇單甲基醚乙酸酯2.5〇g混合溶解 後，將作爲具乙烯性雙鍵化合物[B]的二季戊四醇六丙烯酸酯 以及二季戊四醇五丙烯酸酯的混合物（東亞合成化學工業（株) 製「ARONIX M400」）0.6g、作爲具一苯甲酮結構有機過酸化 物[C](光聚合引發劑）的3,3’，4,4’-四〇丁基過氧羰基)二苯甲酮 的25重量％甲苯溶液0.24g、作爲具香豆素結構光增感劑[D] 的3-苯醯-7-二乙胺基香豆素以及作爲其他成份的砂系 界面活性劑（Byk-Chemie · JaPan(株）製「Byk_344」）0.003g 混 合，以調整固形成份濃度至39重量％的加入丙二醇單甲基醚 乙酸醋。宜後擾伴至得到均勻的溶液爲止’以孔徑爲m 的薄膜過濾器加以過濾後，而得到感光性樹脂組成物的溶液。 第2實施例〜第34實施例 除了以預定量加入表3〜表7所記載的各成份之外’與第 1實施例的進行相同，以得到各別的感光性樹脂組成物。 第1比較例〜第8比較例 取代具香豆素結構光增感劑[D]，使用具4,4’-雙（二烷基 胺)香豆素的光增感劑[D，]，各成份除了如表8所記載的加入 之外，以與第1實施例相同的調製感光性樹脂組成物溶液。 表3〜表8中記載的略稱的意義如下。 <1>具乙烯性雙鍵化合物[B] B-1 :二季戊四醇六丙烯酸酯以及二季戊四醇五丙嫌酸酯 的混合物(東亞合成化學工業(株)製「AR0NIXM4()()」） B_2 :三甲醇丙烷丙烯酸酯 39 8310-pif2 B_3 :季戊四醇三丙烯酸酯 B-4 :季戊四醇四丙烯酸酯 <2〉具二苯甲酮結構有機過酸化物[C](光聚合引發劑） C-1 : 3,3’，4,4’-四（t-丁基過氧羰基）二苯甲酮的25重量％ 甲苯溶液 匸-2:3,4,4’-三〇-丁基過氧羰基）二苯甲酮的25重量％甲 苯溶液 C-3 : 3,3’-二（甲氧羰基）-4,4’-二（t-丁基過氧羰基）二苯甲 酮的20重量％甲苯溶液 <3〉具香豆素結構光增感劑p] D-1 : 3_苯醯-7-二乙胺基香豆素 D-2 : 3-苯醯-7-甲氧基香豆素 D’ ： 4,4’-雙(二烷基胺)香豆素 <4>其他成份(界面活性劑） E-1 :砂系界面活性劑 Byk-Chemie· Japan(株)製「Byk_344」) <5>其他成份(偶合劑） F-1 ·· 3-甲基丙烯醯基丙基甲氧基矽烷。 尙且，表3〜表8的各成份的使用量’係以對鹼可溶性樹 脂[A]爲100的重量比表示’僅有[c]的値係以對固形成份的重 量比（％)。 576950 8310-pif2 表3 實施例編號 1 2 3 4 5 6 7 鹼可溶性樹脂[A] A-1 100 100 100 100 100 100 100 A-2 A-3 A-4 鹼不溶性的具環氧 基乙烯聚合物[AIS] AIS-1 15 15 15 15 AIS-2 15 AiS-3 15 AIS-4 15 具乙烯性雙鍵化合 物[B] B-l 60 60 60 60 60 60 60 B-2 B-3 B-4 具二苯甲酮結構有 機過酸化物[C] C-l 6 6 6 6 6 6 C-2 6 C-3 具香豆素結構光增 感劑[D] D-l 3 3 3 3 3 3 D-2 3 D， 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 6 41 576950 8310-pif2 表4 實施例編號 8 9 10 11 12 13 14 鹼可溶性樹脂[A] A-1 100 100 100 100 100 100 100 A-2 A-3 A-4 鹼不溶性的具環氧 AiS_l 15 15 15 15 15 15 15 基乙烯聚合物[AIS] AIS-2 AIS-3 Ais_4 具乙烯性雙鍵化合 B-l 60 30 30 30 30 30 30 物[B] B-2 30 30 30 30 B-3 30 B_4 30 具二苯甲酮結構有 C-l 6 6 6 6 機過酸化物[C] C-2 6 C-3 6 6 具香豆素結構光增 D-l 3 3 3 3 3 3 3 感劑[D] D-2 D， 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 6 42 576950 8310-pif2 表5 實施例編號 15 16 17 18 19 20 21 鹼可溶性樹脂[A] A-1 100 100 100 100 100 100 100 A-2 A-3 A-4 鹼不溶性的具環氧 基乙烯聚合物[AIS] AIS-1 15 15 15 15 15 15 15 AIS-2 AIS-3 AIS-4 具乙烯性雙鍵化合 物[B] B-l 30 30 100 100 B-2 30 30 60 B-3 60 B-4 60 具二苯甲酮結構有 機過酸化物[C] C-l 6 6 6 10 10 C-2 6 C-3 6 具香豆素結構光增 感劑[D] D-l 3 3 3 3 3 1 1 D-2 D， 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 6 6 6 6 6 10 43 576950 8310-pif2 表6 實施例編號 鹼可溶性樹脂[A] A-1 100 A-2 100 100 100 100 A-3 100 100 A-4 鹼不溶性的具環氧 AiS-l 20 22 15 基乙烯聚合物[AIS] AIS-2 22 15 AiS-3 22 AIS-4 17 具乙烯性雙鍵化合 B-l 60 60 60 60 60 60 60 物[B] B-2 B-3 B-4 具二苯甲酮結構有 C-l 6 6 6 6 6 6 6 機過酸化物[C] C-2 C-3 具香豆素結構光增 D-l 3 3 3 3 3 3 3 感劑[D] D-2 D, 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 44 576950 8310-pif2 表7 養 :施例編號 29 30 31 32 33 34 鹼可溶性樹脂[A] A-1 A-2 100 100 100 100 A-3 100 100 A-4 鹼不溶性的具環氧 基乙烯聚合物[AIS] AIS-1 15 15 15 15 AIS-2 AIS-3 15 AIS-4 13 具乙烯性雙鍵化合 物[B] B-l 60 60 30 30 30 30 B-2 30 30 B-3 30 B-4 具二苯甲酮結構有 機過酸化物[C] C-l 6 6 6 6 6 6 C-2 C-3 具香豆素結構光增 感劑[D] D-l 3 3 3 3 3 3 D-2 D， 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 6 45 576950 表8 8310-pif2 比較例編號 1 2 3 4 5 6 7 8 鹼可溶性樹脂[A] A-1 100 100 100 100 100 100 A-2 100 100 A-3 100 100 A-4 鹼不溶性的具環 氧基乙儲聚合物 [Ais] AIS-1 15 15 15 15 15 15 15 15 AIS-2 AIS-3 AIS-4 具乙烯性雙鍵化 合物[B] B-l 60 60 100 100 60 100 60 100 B-2 B-3 B-4 具二苯甲酮結構 有機過酸化物[C] C-l 6 6 10 10 6 10 6 10 C-2 C-3 具香豆素結構光 增感劑[D] D-l D-2 D, 3 3 1 1 3 1 3 1 界面活性劑 E-l 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 有機矽烷偶合劑 F-l 6 10 6 10 6 10 使用上述實施例以及比較例所得的感光性樹脂組成物， 形成塗膜、間隔件並評價其性能。其方法與結果如下所記載。 <間隔件的形成法(a)> 46 576950 8310-pif2 在玻璃基板/或是形成有ITO膜所構成之透明電極的玻璃 基板上，於其上乘載預定量的由實施例、比較例所得的感光 性樹脂組成物，並以9000rpm於15秒之間旋轉塗佈後，以熱 墊板進行於90°C、3分鐘的預烤以形成塗膜。其後，所得的 塗膜使用PLA-501F光罩對準器（Mask Aligne〇(CANON(株) 製），並介由以10/^nix 10/zm的透光部份形成格子狀圖案的 光罩而曝光。尙且，曝光係於大氣中，各別以⑴全線曝光（無 濾色鏡）、以及(ii)以g線與h線(使用HOYA(株)製i線切斷過 濾器(Cut Filter)，COLORED OPTICAL GLASS，GLASS TYPE L40, 2.5mm厚）進行。曝光量以累加光量計測定的同時，全線 的場合以i換算lOOmJ/cm2照射，g線與h線的場合以g線與 h線混合的能量100mJ/cm2的紫外線照射。曝光量的測定係使 用累加光量計UIT-102(USHIO(株）製）。受光器的話，於全線 的場合使用感度波長範圍330nm-390nm的受光器UVD-365PD(USHIO(株）製），g線與h線的場合使用感度波長範圍 33〇nm_490nm 的受光器 UVD_405PD(USHIO(株）製）。其次，使 用〇·〇5重量％氫氧化鉀，於23t以預定時間（30秒〜120秒） 進行顯影(淋浴顯影、淋浴壓〇.〇4MPa)後，以純水淋浴洗淨15 秒並乾燥。更加的於熱爐以200°C、30分鐘加熱固化，而在 基板上以10/zmx l〇//m柱狀的感光性樹脂組成物的硬化 膜’形成圖案化的格子狀圖案、厚度5//m的間隔件。 <間隔件的形成法(b)> 以lOOOrpm旋轉塗佈，塗佈厚度變更爲4.8// m之外，與 形成法(a)以相同的方法進行。 <間隔件的形成法(c)> 曝光以200 mj/cm2的紫外線照射之外，與形成法(a)以相 47 576950 8310-pif2 同的方法進行。 以上述所得的間隔件(塗膜），進行如下的物性調查。 <感度〉 上述所得的間隔件中，測定⑴顯影後的殘膜率((顯影後的 膜厚/預烤後的膜厚）χ 100)以及(ii)所得塗膜的殘膜率，以下述 的基準判定。 〇：殘膜率爲90%以上 X :殘膜率未滿90% <耐鹼性> 將上述所得附有4cmx 4cm主要圖案的玻璃基板，於5重 量％氫氧化鈉溶液以6(TC浸泡處理1〇分鐘後，以棋盤眼膠帶 法(JIS K5400，第8· 5. 2項，使用橫切導引1mm角X 1〇〇個) 進行密接性試驗，更加的，觀察浸泡處理前後的膜厚變化率， 以及用400倍的光學顯微鏡觀察塗膜表面的變化，以下面的 基準判定。 〇：以棋盤眼膠帶法無剝離，膜厚的變化率未滿5%，且處理 前後塗膜表面無變化。 X:上述之外的場合 <耐水性> 將上述所得附有4cmx 4cm主要圖案的玻璃基板，於超純 水中以80°C浸泡處理1小時後，更加的浸泡於超純水以8〇°C 進行1小時的超音波洗淨處理後，以棋盤眼膠帶法(JIS K5400, 第8. 5. 2項，使用橫切導引1mm角X 100個)進行密接性試驗， 更加的，觀察處理前後的膜厚變化率，以及用400倍的光學 顯微鏡觀察塗膜表面的變化，以下面的基準判定。 48 576950 8310-pif2 ◦:經由任何的處理，以棋盤眼膠帶法無剝離，膜厚的變化 率未滿5%，且處理前後塗膜表面無變化。 X:上述之外的場合 <耐熱性〉 將形成於基板的間隔件以240°C再加熱1小時後，測定再 加熱後的殘膜率（(再加熱後的膜厚/事後烤後的膜厚）x 1〇〇)， 以下面的基準判定。 〇：再加熱後的殘膜率爲95%以上 X :再加熱後的殘膜率未滿95% <耐溶劑性> 形成於基板的間隔件，於N-甲基-2-吡咯烷酮中施以25 °C、1小時的浸泡處理後，觀察處理前後的膜厚變化率，以及 用400倍的光學顯微鏡觀察塗膜表面的變化，以下面的基準 判定。 〇：膜厚的變化率未滿5%，且處理前後塗膜表面無變化。 X :膜厚的變化率在5%以上 使用實施例所得的感光性樹脂組成物形成的間隔件的評 價結果，表示於表9〜表11，而且使用比較例所得的感光性 樹脂組成物形成的間隔件的評價結果，表示於表12。 49 576950 8310-pif2 表9 感光性樹脂 塗膜(間隔件)的形成 塗月 莫澗隔件)物性 組成物 方法 曝光 感度 耐鹼性 耐水性 耐熱性 耐溶劑性 第1實施例 ⑻ 全線 〇 〇 〇 〇 〇 ⑻ gh線 〇 〇 〇 〇 〇 (b) 全線 〇 〇 〇 〇 〇 (b) gh線 〇 〇 〇 〇 〇 (c) 全線 〇 〇 〇 〇 〇 (c) gh線 〇 〇 〇 〇 〇 第2實施例 ⑻ 全線 〇 〇 〇 〇 〇 ⑷ gh線 〇 〇 〇 〇 〇 第3實施例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 〇 〇 〇 〇 〇 第4實施例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 〇 〇 〇 〇 〇 第5實施例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 〇 〇 〇 〇 〇 第6實施例 (a) 全線 〇 〇 〇 〇 〇 ⑻ gh線 〇 〇 〇 〇 〇 第7實施例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 〇 〇 〇 〇 〇 50 576950 表10 8310-pif2 感光性樹脂 塗膜(間隔件)的形成 塗fi 莫澗隔件)物性 組成物 方法 曝光 感度 耐鹼性 耐水性 耐熱性 耐溶劑性 第8實施例 ⑻ 全線 〇 〇 〇 〇 〇 ⑻ gh線 〇 〇 〇 〇 〇 第9實施例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 〇 〇 〇 〇 〇 第10實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第11實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第12實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第13實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第Η實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第15實施 (a) 全線 〇 〇 〇 〇 〇 例 ⑻ gh線 〇 〇 〇 〇 〇 第16實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第17實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第18實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 51 576950 8310-pif2 第19實施 ⑻ 全線 〇 〇 〇 〇 〇 例 ⑻ gh線 〇 〇 〇 〇 〇 第20實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第21實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 52 576950 8310-pif2 表11 感光性樹脂 塗膜(間隔件)的形成 塗月 莫澗隔件雌 組成物 方法 曝光 感度 耐鹼性 耐水丨生 耐熱性 耐溶劑性 第22實施 ⑻ 全線 〇 〇 〇 〇 〇 例 ⑻ gh線 〇 〇 〇 〇 〇 第23實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第24實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第25實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第26實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第27實施 (a) 全線 〇 〇 〇 〇 〇 例 ⑻ gh線 〇 〇 〇 〇 〇 第28實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第29實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第30實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第31實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 53 576950 8310-pif2 第32實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第33實施 ⑻ 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 第34實施 (a) 全線 〇 〇 〇 〇 〇 例 (a) gh線 〇 〇 〇 〇 〇 54 576950 表12 8310-pif2(Υ8) (Υ5) > 〇: (Ί9) (Υιό) κ (YU) (where: ^ 8 is Η or a radical with a carbon number of 1 to 10, q represents an integer of 0 to 4, and r represents 0 or 1) [Disclosure of Invention 2] < Photocurable coloring composition > The photocurable coloring composition of the present invention is a composition in which a colorant is added to the aforementioned photosensitive resin composition. In the present invention, coloring agents such as dyes, inorganic pigments, and organic pigments can be used. Specific examples of the colorant are, for example, azo-based dye amount, onion quinone dye, trityl dye, polymethine dye, metal salt dye, diazo dye, triazo dye, sulfur dye, indigo dye, etc. Synthetic Dye or CI Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 83, 93, 109, 110, 137, 138, 139, 150, 153, 154, 166, 168, 173, 180, 185, CI · Pigment Orange 36, 31 576950 8310-pif2 43, 51, 71, CI · Pigment Red 9, 97, 122, 123, 149, 176, 177, 180, 215, 254, CI · Pigment Violet 19, 23 , 29, C.I_Pigment Blue 15, 15: 3, 15: 6, CI · Pigment Green 7, 36, CI · Pigment Brown, 28, c ·; [• Pigment Black 1, 7 and other organic pigments. From the viewpoints of color purity, heat resistance, and light resistance, organic pigments are preferred. Furthermore, from the viewpoints of color purity and transmittance, CI Pigment Red 177, 254, CI · Pigment Yellow 138, 139, 150, 180, 185, CL Pigment Orange 71, CI · Pigment Green 36 'CI Pigment Blue 15, 15 : 6 is better. The amount of the colorant used in the present invention varies considerably depending on the color of the manufactured color filter or the purpose of the color filter, and is preferably 5 relative to the total amount of the polymer binder and the ethylenic double bond compound [B]. ~ 130% by weight. The amount used is relative to the total amount of the polymer binder and [B]. If it is less than 5% by weight, a film thickness to achieve the desired color purity cannot be formed. Conversely, if it exceeds 130% by weight, the edges of the pattern tend to be jagged. And other poor conditions. The photocurable coloring composition of the present invention may contain components other than the above-mentioned components as necessary. When a coupling agent is used, its addition ratio is 10% by weight or less based on the solid content of the coloring agent in the composition. When a surfactant is added, the addition ratio is 0.01 to 10% by weight based on the solid content of the coloring agent in the composition. The photocurable coloring composition of the present invention is a solution or dispersion in which a colorant is added to the photosensitive resin composition of the present invention to increase or decrease the amount of solvent used to adjust the solid content concentration to 10 to 50% by weight. Obtained by mixing. This solid content concentration must be set to smooth the substrate surface, or an auxiliary means to adjust the thickness of the coating film. When the molecular weight of the polymer binder is large, or when the thickness of the coating film is thin, adjust the solid content reduction. When the molecular weight of the polymer binder is small or the thickness of the coating film is thick, the solid content concentration is adjusted to increase. In addition, when preparing a solvent or dispersion for a colorant 32 576950 8310-pif2, the solvent used for the photosensitive resin composition of the present invention can be appropriately selected and used. The thus-prepared photocurable colored composition can be applied to the surface of a substrate, and the solvent can be removed by heating to form a coating film. The method for applying a photosensitive resin composition to the substrate surface can be performed using, for example, conventionally known methods such as a spin coating method, a roll coating method, and a dip coating method. After coating, the coating film can be dried. For example, the coating film can be blown with superheated air, or the substrate can be placed on an overheated hot pad or left to heat in a heating furnace (hereinafter abbreviated as "Prebake" "). The conditions for pre-baking vary depending on the type and mixing ratio of each ingredient, but it is usually 30 to 300 ° C, and particularly preferably 50 to 200 ° C. The heating time is preferably 1 to 30 minutes. The heating temperature can be kept constant or it can be increased in stages. The film thickness after drying is usually 0.1 to 10 / zm, preferably 0.5 to 5 μm. In addition, on a transparent conductive electrode (for example, indium tin oxide (ITO), tin oxide (SnOx), etc.) of a substrate for a liquid crystal display element, or on an alignment film that has been subjected to an alignment treatment, the above After the coating film is formed to a predetermined thickness, it is irradiated with radiation through a photomask having a grid-like light-transmitting partial pattern of 5 // mx 5 // m to 15 / zmx 15 / zm, for example, and non-irradiated with radiation for development. A part is removed for curing, and a color filter is drawn to draw the necessary pattern. As the radiation used at this time, visible light, ultraviolet light, deep ultraviolet light, electron rays, x-rays, and the like can be used. In particular, radiation having a wavelength range of 190 nm to 450 nm is preferable. The radiation irradiation energy is preferably 1 to 1000 mJ / cm2. The developing solution is, for example, an inorganic salt such as sodium carbonate, sodium hydroxide or potassium hydroxide, or an organic alkali aqueous solution such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, and a surfactant can be added to the alkaline aqueous solution. The development method can be any of 33 576950 8310-pif2, such as immersion, shower, spray, etc. The development time is usually 30 ~ 240 seconds. After development, it can be washed with water, dried and dried to form a pattern. Thereafter, the patterned eagle was heated on a hot pad, a hot furnace, etc. (hereinafter abbreviated as "Postbake") to bridge the unreacted ethylenic double bond compound [B] and completely remove the solvent. , And a predetermined coating film pattern can be obtained. The post-baking conditions vary depending on the type and mixing ratio of each component, usually between 180 ° C and 250 ° C, between 5 and 30 minutes on a hot pad, and between and ~ minutes on a hot stove. The substrate can be transparent glass substrates such as white board glass, blue plate glass, sand-coated blue plate glass, polycarbonate, polyethylene, acrylic resin, vinyl chloride resin, and aromatic polyamide. Sheets, films or substrates of synthetic resins such as resin, polyimide, polyimide resin, metal substrates such as brocade, copper, nickel, and stainless steel plates, other ceramic plates, and photoelectric conversion elements Semiconductor substrates, etc. These substrates can be subjected to pretreatments such as chemical processing of sand garden coupling agents, plasma processing, ion plating, sputtering, chemical weather deposition, and vacuum evaporation as required. [Best embodiment of the present invention] Hereinafter, the embodiment of the spacer-forming material of the present invention will be described in more detail, but the present invention is not limited to this embodiment. (Preparation of alkali-soluble resin [A]) The alkali-soluble resins [A-1] to [A-3] used in Examples and Comparative Examples were prepared as described below. < Preparation of [A-1]> In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 20 g of methacrylic acid as an unsaturated carboxylic acid was added as a separate polymer system. As the radical polymerizable monomer of formula (1), benzyl methyl 34 576950 8310-pif 2 acrylate 130 g and 20 g of 2-hydroxyethyl methacrylate of the base-insoluble radical polymerizable monomer (a_2) ( a-3) 30 g of 5-tetrahydrofuran hydroxycarbon pentyl acrylate, 2,2'-azobisisobutyronitrile lg as a polymerization initiator, 3 g of fluorenylacetic acid as a chain transfer agent, and 167 g of methanol as a solvent And 333 g of ethyl acetate. The flask was subjected to an oil bath by removing oxygen with nitrogen between 30 minutes, and the polymerization reaction was performed for 6 hours while keeping the inside of the flask at 65 ° C. Thereafter, 3000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant liquid was removed by decantation, and then dried at 40 ° (: vacuum for 20 hours to obtain an alkali-soluble resin [A-1]. Polyethylene obtained The weight average molecular weight of the oxygen-dioxide conversion is 7000 (please refer to Table 1) < Preparation of alkali-soluble resins [A-2] and [A-3] > Change the proportion of monomer components shown in Table 1 to The same method was used to dissolve the resin [A-1] to obtain [A-2] and [A-3]. The molecular weight of the obtained resin is shown in Table 1. 35 8310-pif2 Table 1 A-1 A-2 A-3 (Monomer) (g) a-1 methacrylic acid 20 30 20 a-2 BMA 130 130 90 MMA — — 80 HEMA 20 20 10 a-3 FCPA 30 20 _ (polymerization initiator) (g) AIBN 1 1 1 (Key Transfer Agent) (g) TGA 3 3 3 (solvent) (g) Methanol 167 167 167 Ethyl acetate 333 333 333 Weight average molecular weight (Mw) 7000 7200 8300 576950 The symbols in Table 1 each indicate the following compounds. BMA: benzyl methacrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate FCPA: 5-tetrahydrofuran hydroxy carbon pentyl acrylate AIBN: 2,2 '-Azobisisobutyronitrile TGA: fluorenylacetic acid (preparation of alkali-insoluble epoxy-based ethylene polymer [AIS]) Base-insoluble epoxy-based ethylene polymer used in Examples and Comparative Examples 36 576950 8310 -pif2 [AIS-1] ~ [AIS_4] are prepared as follows. < Preparation of [AIS-1] > In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, add as a 160 g of epoxypropylmethacrylate with epoxy radical polymerizable monomer (a-4), and methylmethyl as epoxy group-free polymerizable monomer (a-5) 40 g of acrylate, 8 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 800 g of methyl ethyl ketone as a solvent. The flask was subjected to an oil bath by removing oxygen with nitrogen in 30 minutes. The inside of the bottle was polymerized at 80 ° C for 6 hours. Thereafter, 3,000 g of cyclohexane was added to the polymerization solution to precipitate a polymer, and the supernatant liquid was removed by decantation, followed by vacuum drying at 40 ° C for 20 minutes. Hours to get [AIS-1]. The weight average molecular weight of polyethylene oxide of [AIS-1] is 6100 (see Table 2) < Alkali insoluble with Preparation of oxyethylene polymers [AIS-2] to [AIS-4]> The ratio of the monomer components shown in Table 2 is changed to be the same as the alkali-insoluble epoxy-based ethylene polymer [AIS-1] Method to get [Ais_q ~ [Af4]. The respective molecular weights are shown in Table 2. 37 8310-pif2 Table 2 AIS-1 AIS, 2 AIS, 3 AIS, 4 (monomer) (g) a-4 GMA 160 160 160 200 MMA 40 a-5 HEMA 40 TCDMA 40 (polymerization initiator) (g) AIBN 8 8 8 8 (solvent) (g) MEK 800 800 800 800 Weight average molecular weight (Mw) 6100 6100 7000 6200 576950 The symbols in Table 2 each indicate the following compounds. GMA: Glycidyl methacrylate MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate TCDMA: Tricyclic [5.2.1.02,6] decenyl methacrylate AIBN: 2 , 2'-Azobisisobutyronitrile MEK: fluorenyl ethyl ketone. The following are preparations of photosensitive resin compositions, evaluation of their performance, spacers and liquid crystal display elements made using them, and the following. The evaluation results are described in the following examples. (Preparation of photosensitive resin composition) 1.00 g of alkali-soluble resin [A_l], alkali-insoluble epoxy-ethylene polymer 38 576950 8310-pif2 [AIS_l] 0.15 g, and propylene glycol monomethyl ether in Example 1 After mixing and dissolving 2.50 g of acetate, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("ARONIX M400" manufactured by Toa Synthetic Chemical Industry Co., Ltd.) as an ethylenic double bond compound [B] was 0.6. g. 25% by weight toluene of 3,3 ', 4,4'-tetrabutylbutyloxycarbonyl) benzophenone as an organic peracid [C] (photopolymerization initiator) having a benzophenone structure 0.24 g of solution, 3-phenylhydrazone-7-diethylaminocoumarin as a coumarin structure photosensitizer [D], and a sand-based surfactant (Byk-Chemie · JaPan (strain) "Byk_344") 0.003g was mixed to adjust the solid content concentration to 39% by weight, and propylene glycol monomethyl ether acetate was added. It is preferable that the solution is filtered after it is filtered through a membrane filter having a pore size of m to obtain a solution of the photosensitive resin composition. Examples 2 to 34 were performed in the same manner as in Example 1 except that the components described in Tables 3 to 7 were added in predetermined amounts to obtain respective photosensitive resin compositions. The first comparative example to the eighth comparative example replaced the photosensitizer [D] with a coumarin structure, and used a photosensitizer [D,] with 4,4'-bis (dialkylamine) coumarin, Except that each component was added as described in Table 8, the photosensitive resin composition solution was prepared in the same manner as in the first example. The meanings of the abbreviations described in Tables 3 to 8 are as follows. < 1 > Compound with ethylenic double bond [B] B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentapropanoate ("ARONIXM4 () ()" manufactured by Toa Synthetic Chemical Industry Co., Ltd. B_2 : Trimethylolpropane acrylate 39 8310-pif2 B_3: pentaerythritol triacrylate B-4: pentaerythritol tetraacrylate < 2> organic peracid with benzophenone structure [C] (photopolymerization initiator) C-1 : 25% by weight toluene solution of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone 匸 -2: 3,4,4'-tris-butylperoxycarbonyl ) 25% by weight toluene solution of benzophenone C-3: 20% by weight of 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) benzophenone Toluene solution < 3> Photosensitizer with coumarin structure p] D-1: 3_phenylhydrazone-7-diethylaminocoumarin D-2: 3-phenylhydrazone-7-methoxy fragrant Dactin D ': 4,4'-bis (dialkylamine) coumarin < 4 > Other ingredients (surfactant) E-1: Sand-based surfactant Byk-Chemie · Japan Co., Ltd. " Byk_344 」) < 5 > Other ingredients (coupling agent) F-1 ·· 3-Methacrylfluorenylpropylmethoxysilane . In addition, the amount of each component used in Tables 3 to 8 is expressed as a weight ratio of 100 to alkali-soluble resin [A], and the ratio of only [c] is a weight ratio (%) to solid components. 576950 8310-pif2 Table 3 Example No. 1 2 3 4 5 6 7 Alkali-soluble resin [A] A-1 100 100 100 100 100 100 100 A-2 A-3 A-4 Alkali-insoluble polymer with epoxy-based ethylene [AIS] AIS-1 15 15 15 15 AIS-2 15 AiS-3 15 AIS-4 15 Compounds with ethylenic double bonds [B] Bl 60 60 60 60 60 60 60 B-2 B-3 B-4 Organic peracids of benzophenone structure [C] Cl 6 6 6 6 6 6 C-2 6 C-3 Photosensitizers with coumarin structure [D] Dl 3 3 3 3 3 3 D-2 3 D Surfactant El 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Organic silane coupling agent Fl 6 41 576950 8310-pif2 Table 4 Example No. 8 9 10 11 12 13 14 Alkali soluble resin [A] A-1 100 100 100 100 100 100 100 A-2 A-3 A-4 Alkali-insoluble epoxy AiS_l 15 15 15 15 15 15 15 Ethylene polymer [AIS] AIS-2 AIS-3 Ais_4 Ethylene double bond Bl 60 30 30 30 30 30 30 物 [B] B-2 30 30 30 30 B-3 30 B_4 30 with benzophenone Structure Cl 6 6 6 6 Organic peracid [C] C-2 6 C-3 6 6 With coumarin structure light increase Dl 3 3 3 3 3 3 3 sensitizer [D] D-2 D, interface activity Agent El 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Organic Silane Coupling Agent Fl 6 42 576950 8310-pif2 Table 5 Example No. 15 16 17 18 19 20 21 Alkali-soluble resin [A] A-1 100 100 100 100 100 100 100 A- 2 A-3 A-4 Alkali-insoluble vinyl polymer with epoxy group [AIS] AIS-1 15 15 15 15 15 15 15 15 AIS-2 AIS-3 AIS-4 compound with ethylenic double bond [B] Bl 30 30 100 100 B-2 30 30 60 B-3 60 B-4 60 Organic peracid with benzophenone structure [C] Cl 6 6 6 10 10 C-2 6 C-3 6 With coumarin structured light Sensitizer [D] Dl 3 3 3 3 3 1 1 D-2 D, Surfactant El 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Organic Silane Coupling Agent Fl 6 6 6 6 6 10 43 576950 8310-pif2 Table 6 Examples Number Alkali-soluble resin [A] A-1 100 A-2 100 100 100 100 A-3 100 100 A-4 Alkali-insoluble epoxy AiS-l 20 22 15 ethylene polymer [AIS] AIS-2 22 15 AiS-3 22 AIS-4 17 Ethylene double bond Bl 60 60 60 60 60 60 60 60 [B] B-2 B-3 B-4 with benzophenone structure with Cl 6 6 6 6 6 6 6 organic peracid [C] C-2 C-3 with coumarin structure light increase Dl 3 3 3 3 3 3 3 Sensitive [D] D-2 D, Surfactant El 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Organic Silane Coupling Agent Fl 44 576950 8310-pif2 Table 7 Nutrition: Example No. 29 30 31 32 33 34 Alkali-soluble resin [ A] A-1 A-2 100 100 100 100 A-3 100 100 A-4 Alkali-insoluble vinyl epoxy polymer [AIS] AIS-1 15 15 15 15 AIS-2 AIS-3 15 AIS-4 13 Compounds with ethylenic double bonds [B] Bl 60 60 30 30 30 30 B-2 30 30 B-3 30 B-4 Organic peracids with benzophenone structure [C] Cl 6 6 6 6 6 6 C -2 C-3 Photosensitizer with coumarin structure [D] Dl 3 3 3 3 3 3 D-2 D, Surfactant El 0.3 0. 3 0.3 0.3 0.3 0.3 Organic Silane Coupling Agent Fl 6 45 576950 Table 8 8310-pif2 Comparative Example No. 1 2 3 4 5 6 7 8 Alkali-soluble resin [A] A-1 100 100 100 100 100 100 A-2 100 100 A -3 100 100 A-4 Alkali-insoluble ethoxylated polymer [Ais] AIS-1 15 15 15 15 15 15 15 15 AIS-2 AIS-3 AIS-4 Compound with ethylenic double bond [B] Bl 60 60 100 100 60 100 60 100 B-2 B-3 B-4 Organic peracids with benzophenone structure [C] Cl 6 6 10 10 6 10 6 10 C-2 C-3 with coumarin Structured light sensitizer [D] Dl D-2 D, 3 3 1 1 3 1 3 1 Surfactant El 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Organic Silane Coupling Agent Fl 6 10 6 10 6 10 Using the above examples and The photosensitive resin composition obtained in the comparative example was formed into a coating film and a spacer, and its performance was evaluated. The methods and results are described below. < Formation method of spacer (a) > 46 576950 8310-pif2 A predetermined amount of Examples and Comparative Examples are loaded on a glass substrate or a glass substrate formed with a transparent electrode composed of an ITO film. The obtained photosensitive resin composition was spin-coated at 9000 rpm for 15 seconds, and then prebaked at 90 ° C. for 3 minutes with a hot pad to form a coating film. Thereafter, the obtained coating film was formed using a PLA-501F photomask aligner (Mask Aligne0 (manufactured by CANON)), and light in a grid pattern was formed with a light transmitting portion of 10 / ^ nix 10 / zm. The exposure is performed in the atmosphere, and the exposure is in full line (without color filter), and (ii) the g-line and the h-line (using a cut-off filter made by HOYA Co., Ltd. (Cut Filter) ), COLORD OPTICAL GLASS, GLASS TYPE L40, 2.5mm thick). While the exposure is measured by the cumulative light meter, the entire line is illuminated with 100mJ / cm2 in i conversion, and the g and h lines are g and h Mixed ultraviolet radiation with an energy of 100mJ / cm2. The exposure is measured using a total light meter UIT-102 (manufactured by USHIO Co., Ltd.). For a receiver, use a UVD- 365PD (manufactured by USHIO Co., Ltd.), g-line and h-line use UVD_405PD (manufactured by USHIO Co., Ltd.) with a sensitivity wavelength range of 33-490nm. Next, use 0.05% by weight potassium hydroxide at 23t. Development is performed at a predetermined time (30 seconds to 120 seconds) (shower development, shower pressure of 0.04 MPa), and then Wash with pure water for 15 seconds and dry. It is further cured by heating in a hot furnace at 200 ° C for 30 minutes, and a cured film of a photosensitive resin composition with a columnar shape of 10 / zmx 10 // m on a substrate ' A spacer with a thickness of 5 // m was formed in a patterned grid pattern. ≪ Formation method of spacer (b) > Spin coating was performed at 1,000 rpm, and the coating thickness was changed to other than 4.8 // m. (a) The same method is used. < The formation method of the spacer (c) > The exposure is performed by the same method as that of the formation method (a) except that the exposure method is 200 mj / cm2 of ultraviolet radiation, phase 47 576950 8310-pif2. With the spacer (coating film) obtained as described above, the following physical property survey was performed. ≪ Sensitivity> In the spacer obtained as described above, the residual film rate after development was measured ((film thickness after development / film after pre-baking) Thickness χ 100) and (ii) The residual film rate of the coating film obtained is determined based on the following criteria: ○: The residual film rate is 90% or more X: The residual film rate is less than 90% < Alkali resistance > The obtained glass substrate with a main pattern of 4 cmx 4 cm was immersed in a 5% by weight sodium hydroxide solution at 6 (TC for 10 minutes, and then subjected to a checkerboard tape method (JIS K54). 00, item 8 · 5.2, using a cross-cut guide 1mm angle X 100 pieces) for adhesion test. Furthermore, observe the change rate of the film thickness before and after the immersion treatment, and observe the coating with a 400 times optical microscope. The change of the film surface was judged by the following criteria. ○: There was no peeling by the checkerboard tape method, the change rate of the film thickness was less than 5%, and there was no change in the surface of the coating film before and after the treatment. X: In cases other than the above < Water resistance > The glass substrate with the 4cmx 4cm main pattern obtained above was immersed in ultrapure water at 80 ° C for 1 hour, and then further immersed in ultrapure water at 8 ° C. 〇 ° C After ultrasonic cleaning for 1 hour, the adhesiveness test was performed by the checkerboard tape method (JIS K5400, item 8.5.2, using a cross-cut guide 1mm angle X 100 pieces), and even more, The change rate of the film thickness before and after the treatment was observed, and the change in the surface of the coating film was observed with a 400-fold optical microscope, and judged by the following criteria. 48 576950 8310-pif2 ◦: After any treatment, there is no peeling by checkerboard tape, the change rate of film thickness is less than 5%, and there is no change in the surface of the coating film before and after treatment. X: Other than the above < Heat resistance> After the spacer formed on the substrate was reheated at 240 ° C for 1 hour, the residual film rate after reheating was measured ((film thickness after reheating / post-bake) (Film thickness) x 100), and determined based on the following criteria. 〇: Residual film rate after reheating is 95% or more X: Residual film rate after reheating is less than 95% < Solvent resistance > Spacer formed on substrate in N-methyl-2-pyrrolidone After immersion treatment at 25 ° C for 1 hour, the change rate of the film thickness before and after the treatment was observed, and the change of the surface of the coating film was observed with a 400-fold optical microscope, and judged by the following criteria. 〇: The change rate of the film thickness is less than 5%, and there is no change in the surface of the coating film before and after the treatment. X: The evaluation results of the spacers formed using the photosensitive resin composition obtained in the examples with a change rate of 5% or more of the film thickness are shown in Tables 9 to 11, and the results of using the photosensitive resin composition obtained in the comparative examples The evaluation results of the spacer are shown in Table 12. 49 576950 8310-pif2 Table 9 Formation of a photosensitive resin coating film (spacer) Moisture separator) Physical composition method Exposure sensitivity Alkali resistance Water resistance Heat resistance Solvent resistance 1st example ⑻ All lines 〇〇⑻gh line 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇 〇 〇 〇 〇 〇 〇 〇 00 Example ⑻ All lines 100,000 GH lines 0000 3rd embodiment (a) All lines 100,000 (a) gh lines 40,000 4th embodiment (a) All lines 0000 (a) gh line 50,000th embodiment (a) all lines 100,000 (a) gh line 0000th embodiment 6 (a) all lines 100,000 GH line 0000 7th example (a) All lines 100,000 (a) GH line 50,000 576950 Table 10 8310-pif2 Formation of photosensitive resin coating film (spacer) coating fi Mo Mo spacer) physical properties composition method exposure sensitivity alkali resistance water resistance 8th example of heat resistance and solvent resistance ⑻ All lines 100,000 gh lines 0000 ninth embodiment (a) All lines 100,000 (a) gh lines 100,000th implementation ( a) 100,000 cases across the line (a) gh line llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllii Rate generation resolution over the year (a) gh-line llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllsur gllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllurllurund Rates of Rates of 25%) will be reduced to 100%. (a) 10,000th line implementation (a) 10,000th line implementation (a) 10,000th line implementation (a) ghth line 12th implementation (a) full line. Example (a) gh line 0000th 13th implementation ⑻ all lines 0000 case (a) gh line 0000th implementation (a) gh line 100,000 cases ( a) gh line 0000 15th implementation (a) all 0000 cases gh line 0000th 16th implementation ⑻ all lines 0000 case (a) gh line 0000 〇 17th implementation (a) all lines 0000 examples (a) gh lines 0000th 18th implementation ⑻ all lines 0000th example (a) gh lines 000051 576950 8310-pif2 The 19th implementation ⑻ all lines of 20000 cases gh line 0000th 20th real ⑻ All lines of 100,000 cases (a) gh line 0000th 21st implementation (a) all lines of 0000th case (a) gh lines 〇0000052 576950 8310-pif2 Table 11 Photosensitivity Formation of Resin Coating Film (Separator) Application Method of Moisture Separator Female Composition Method Exposure Sensitivity Alkali Resistance Water Resistance 丨 Heat Resistance Solvent Resistance 22th Implementation ⑻ Full Line 100,000 Cases gh Line 〇〇〇〇〇〇 〇 23rd implementation ⑻ all lines 2000a (a) gh line 0000th 24th implementation ⑻ all lines 0000th example (a) gh line 0000th 25th implementation (a) all lines Example (a) gh line 0000th 26th implementation ⑻ all lines 0000 example (a) gh line 0000th 27th implementation (a) all 0000 lines ⑻ GH line 0000th implementation (a) The entire line of 100,000 cases (a) GH line 0000th The 29th implementation (a) The whole line 100,000 cases (a) The gh line. The 30th implementation (a) across the board (a) GH line 0000th implementation of the 31st (a) 100,000 full line cases (a) GH line 0.000 53 950 950 8310-pif2 32nd implementation ⑻ 20,000 full line examples ( a) GH line 0000th implementation of the 33rd line of the entire line of 100,000 cases (a) GH line 0000th 34th implementation of the (a) the full line of 0000th line (a) gh line 〇〇〇54 576950 Table 12 8310-pif2

感光性樹脂 塗膜(間隔件)的形成 塗月 莫澗隔件)物性 組成物 方法 曝光 感度 耐鹼性 耐水性 耐熱性 耐溶劑性 第1比較例 ⑻ 全線 〇 〇 〇 〇 〇 (a) gh線 X X X X X 第2比較例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 X X X X X 第3比較例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 X X X X X 第4比較例 ⑻ 全線 〇 〇 〇 〇 〇 (a) | gh線 X X X X X 第5比較例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 X X X X X 第6比較例 (a) 全線 〇 〇 〇 〇 〇 (a) gh線 X X X X X 第7比較例 ⑻ 全線 〇 〇 〇 〇 〇 ⑻ gh線 X X X X X 第8比較例 (a) 全線 〇 〇 〇 〇 〇 ⑻ gh線 X X X X X 其次，使用本發明的感光性樹脂組成物製作液晶元件用 間隔件，更加的製作具備此間隔件的液晶顯示元件。其實施 例如下所述。 第35實施例 在形成有以ITO膜構成透明電極的玻璃基板上，依照前 述的間隔件形成法（a)，經由旋轉塗佈、預烤、曝光、顯影以 55 576950 8310-pif2 及事後烤步驟，將10//mx 10//m的間隔件圖案，以格子狀於 縱方向間隔100// m、橫方向間隔50// m的形成。其次將液晶 配向劑（CHISSO(株）製「LIXON Aligner-PIA-5004」）塗佈於上 述形成有間隔件基板後，於熱墊板以70°C、1〇分鐘進行乾燥， 更加的於熱爐中以200°C進行60分鐘的加熱處理，而在附間 隔件基板上形成膜厚0.06//m的配向膜。此配向膜以具有包 覆尼龍布滾筒的硏磨裝置，滾筒的回轉數l〇〇〇rpm、平台（stage) 的移送速度爲59mm/秒的進行硏磨處理。在此具有經配向處 理的配向膜面的附間隔件基板之外緣，在塗佈混合有2%玻璃 纖維間隔件的環氧系密封劑後，將一對基板以液晶配向膜的 面相對向，並且其硏磨方向垂直的重合壓著，並加熱硬化。 並對此一對的基板之間由液晶注入口注入TFT用液晶組成物 (後述的FB01)，以光硬化性樹脂將注入口密封。其後，以n0 °C進行30分鐘的等向處理，並徐徐冷卻至室溫以得液晶顯示 元件。 依此所得的液晶顯示元件，其耐硏磨性、液晶配向性、 電壓保持率以及殘留直流電流(DC)以下述的方法評價。 <耐硏磨性> 在間隔件上形成配向膜，此配向膜面於硏磨處理時的狀 態以下述的基準判定。 〇：間隔件無削落、剝離的場合 X:此些之外的場合 <液晶配向性> 使用偏光板進行配向性的確認，以下述的基準判定。 〇：具有良好的配向性 X :配向不佳 56 576950 8310-pif2 <電壓保持率> 測定係外加閘脈衝幅69// s、頻率60Hz、波高± 4.5V的 矩形波於源極，並進行以示波器讀取汲極的變化。將此進行4 次並計算平均値，全部的電壓未減少的場合，以1〇〇%爲相對 値而作爲電壓保持率。尙且，測定係於60°C進行。 <殘留直流電流(DC)> 測定係以通常所使用方法的C-V曲線法進行。亦即是於 液晶元件外加25mV、ΙΚΗζ的交流電，更加的以頻率0.0036Hz 的直流偏壓電壓以± 10V的範圍進行淸除以去除直流的三角 波，並測定變化的電容C。尙且，測定係於6(TC進行。 各特性的測定以及測定結果如表13所示。 第36實施例〜第68實施例 如下記的表13以及表14所記載，第2實施例〜第34實 施例所得的感光性樹脂組成物與後述的液晶組合物組合，與 第35實施例相同的方法各別製作液晶顯示元件。所得的液晶 顯示元件其特性資料表示於表13以及表14。 57 576950 表13 8310-pif2 使用原料的組合 液晶顯示元件的特性 實施例 感光性樹脂 液晶 耐硏磨性 液晶 電壓保持 殘留DC 編號 組成物 組成物 配向性 率(％) (V) 第35實施例 第1實施例 FB01 〇 〇 97.4 0.28 第36實施例 第2實施例 FB01 〇 〇 97.5 0.25 第37實施例 第3實施例 FB01 〇 〇 97.5 0.23 第38實施例 第4實施例 FB01 〇 〇 97.7 0.29 第39實施例 第5實施例 FB01 〇 〇 97.5 0.25 第40實施例 第6實施例 FB01 〇 〇 97.5 0.29 第41實施例 第7實施例 FB01 〇 〇 97.4 0.28 第42實施例 第8實施例 FB01 〇 〇 97.4 0.28 第43實施例 第9實施例 LA 〇 〇 97.6 0.2 第44實施例 第10實施例 LB 〇 〇 97.6 0.22 第45實施例 第11實施例 LC 〇 〇 97.8 0.18 第46實施例 第12實施例 LD 〇 〇 97.8 0.2 第47實施例 第13實施例 LE 〇 〇 97.9 0.18 第48實施例 第14實施例 LA 〇 〇 97.5 0.21 第49實施例 第15實施例 LB 〇 〇 97.5 0.22 第50實施例 第16實施例 LC 〇 〇 97.7 0.17 第51實施例 第17實施例 LD 〇 〇 97.8 0.21 58 576950 表14 8310-pif2 使用原料的組合 液晶顯示元件的特性 實施例 感光性樹脂 液晶 耐硏磨性 液晶 電壓保持 殘留DC 編號 組成物 組成物 配向性 率(％) (V) 第52實施例 第18實施例 LE 〇 〇 97.9 0.19 第53實施例 第19實施例 FB01 〇 〇 97.6 0.29 第54實施例 第20實施例 FB01 〇 〇 97.6 0.21 第55實施例 第21實施例 FB01 〇 〇 97.6 0.21 第56實施例 第22實施例 FB01 〇 〇 97.8 0.17 第57實施例 第23實施例 LA 〇 〇 97.5 0.21 第58實施例 第24實施例 LA 〇 〇 97.5 0.22 第59實施例 第25實施例 LA 〇 〇 97.7 0.17 第60實施例 第26實施例 LA 〇 〇 97.8 0.21 第61實施例 第27實施例 LB 〇 〇 97.9 0.18 第62實施例 第28實施例 LB 〇 〇 97.5 0.21 第63實施例 第29實施例 LB 〇 〇 97.5 0.22 第64實施例 第30實施例 LB 〇 〇 97.7 0.17 第65實施例 第31實施例 LC 〇 〇 97.8 0.18 第66實施例 第32實施例 LC 〇 〇 97.8 0.2 第67實施例 第33實施例 LC 〇 〇 97.9 0.18 第68實施例 第34實施例 LC 〇 〇 97.5 0.21 上述實施例的液晶顯示元件所使用的液晶組成物的組成 如下所示。而且，此些組成物的物性値表示於表15。 59 576950 8310-pif2 <液晶組成物LA> C5Hl1"KZy)~C^_F 12 % 9 % C7Hl5~^Z)^C^"F 7 % C2H5-〇^〇-〇~ocf3 7 % C3H7H^)~h(^)~^^-〇CF3 7 % ~^^~0CF3 7 % 。2日4~C^"〇CF：3 4 % C5Hl 1 "KZ^(Z)~C2H4 ~C^~〇CF3 4 % C3H7 c3h7Formation of Photosensitive Resin Coating (Separator) Coated Momo Separator) Physical Composition Method Exposure Sensitivity Alkali Resistance Water Resistance Heat Resistance Solvent Resistance 1st Comparative Example ⑻ All lines 〇〇〇〇〇 (a) gh line XXXXX 2nd comparative example (a) All lines 100,000 (a) gh line XXXXX 3rd comparative example (a) All lines 0000 (00) gh line XXXXX 4th comparative example ⑻ All lines 100,000 (a) | gh line XXXXX 5th comparative example (a) all lines 000000 (a) gh line XXXXX 6th comparative example (a) all lines 000000 (a) gh line XXXXX 7th comparative example ⑻ All lines of GH line XXXXX 8th comparative example (a) All lines of GH line XXXXX XX line Next, a spacer for a liquid crystal element is produced using the photosensitive resin composition of the present invention, and it is further provided with this Spacer liquid crystal display element. The implementation is described below. Example 35 On a glass substrate formed with a transparent electrode composed of an ITO film, 55 576950 8310-pif2 and post-bake steps were performed in accordance with the aforementioned spacer formation method (a) through spin coating, pre-baking, exposure, and development. A spacer pattern of 10 // mx 10 // m was formed in a lattice pattern with a space of 100 // m in the vertical direction and a space of 50 // m in the horizontal direction. Next, a liquid crystal alignment agent ("LIXON Aligner-PIA-5004" manufactured by Chisso Co., Ltd.) was applied to the above-mentioned spacer-formed substrate, and then dried on a hot pad at 70 ° C for 10 minutes. Heat treatment was performed in a furnace at 200 ° C. for 60 minutes, and an alignment film having a thickness of 0.06 // m was formed on the substrate with a spacer. This alignment film was subjected to a honing process with a honing device including a nylon cloth-coated drum, a drum rotation number of 1000 rpm, and a stage transfer speed of 59 mm / sec. Here, the outer edge of the substrate with a spacer having an alignment film surface subjected to an alignment treatment is coated with an epoxy-based sealant mixed with a 2% glass fiber spacer, and then a pair of substrates are opposed to each other with the surfaces of the liquid crystal alignment film. , And its honing direction overlaps and presses, and heat hardens. A liquid crystal composition for TFT (FB01 described later) is injected between the pair of substrates through a liquid crystal injection port, and the injection port is sealed with a photocurable resin. Thereafter, an isotropic treatment was performed at n0 ° C for 30 minutes, and then slowly cooled to room temperature to obtain a liquid crystal display element. The thus obtained liquid crystal display element was evaluated for its honing resistance, liquid crystal alignment, voltage retention, and residual direct current (DC) by the following methods. < Honing resistance > An alignment film was formed on the spacer, and the state of the alignment film surface during the honing process was determined based on the following criteria. 〇: When the spacer is not chipped or peeled off X: In other cases < Liquid crystal alignment > Alignment was confirmed using a polarizing plate and judged based on the following criteria. 〇: Good alignment X: Poor alignment 56 576 950 8310-pif2 < Voltage holding ratio > The measurement system applies a rectangular wave with a gate pulse amplitude of 69 // s, a frequency of 60 Hz, and a wave height of ± 4.5 V to the source, and Make changes to read the drain with an oscilloscope. This was performed 4 times and the average value 値 was calculated. When all the voltages were not reduced, 100% was used as the relative value 値 as the voltage holding ratio. In addition, the measurement was performed at 60 ° C. < Residual direct current (DC) > The measurement was performed by a C-V curve method according to a commonly used method. In other words, an AC power of 25mV and 1KΗζ is applied to the liquid crystal element, and the DC bias voltage at a frequency of 0.0036Hz is further divided by ± 10V to remove the DC triangular wave, and the changed capacitance C is measured. In addition, the measurement was performed at 6 ° C. The measurement and measurement results of each characteristic are shown in Table 13. Examples 36 to 68 are described in Tables 13 and 14 below, and Examples 2 to 34 The photosensitive resin composition obtained in the example is combined with a liquid crystal composition described later, and a liquid crystal display element is separately produced in the same manner as in Example 35. The characteristics of the obtained liquid crystal display element are shown in Table 13 and Table 14. 57 576950 Table 13 Characteristics of 8310-pif2 combined liquid crystal display elements using raw materials Example photosensitive resin liquid crystals Anti-friction properties Liquid crystal voltage retention residual DC Number composition Composition Orientation (%) (V) 35th example First implementation Example FB01 〇97.4 0.28 36th embodiment 2nd embodiment FB01 〇97.5 0.25 37th embodiment 3rd embodiment FB01 〇97.5 0.23 38th embodiment 4th embodiment FB01 〇97.7 0.29 39th embodiment 5th embodiment FB01 〇97.5 0.25 40th embodiment 6th embodiment FB01 〇97.5 0.29 41st embodiment 7th embodiment FB01 〇97.4 0.28 42nd embodiment 8th embodiment Example FB01 〇97.4 0.28 43rd embodiment 9th embodiment LA 〇97.6 0.2 44th embodiment 10th embodiment LB 〇97.6 0.22 45th embodiment 11th LC LC 0099.8 0.18 46th embodiment 12th embodiment LD 〇0097.8 0.2 47th embodiment 13th embodiment LE 〇97.9 0.18 48th embodiment 14th embodiment LA 〇97.5 0.21 49th embodiment 15th embodiment LB 〇97.5 0.22 50th Example 16th example LC 〇0097.7 0.17 51st example 17th example LD 〇0097.8 0.21 58 576950 Table 14 Characteristics of a combination liquid crystal display element using raw materials 8310-pif2 Example photosensitive resin liquid crystal abrasion resistance Liquid crystal voltage retention residual DC number composition composition orientation ratio (%) (V) 52nd embodiment 18th embodiment LE 〇97.9 0.19 53rd embodiment 19th embodiment FB01 〇97.6 0.29 54th embodiment 20th embodiment FB01 〇97.6 0.21 55th embodiment 21st embodiment FB01 〇97.6 0.21 56th embodiment 22nd embodiment FB01 〇97.8 0.17 57th embodiment 23rd embodiment LA 〇〇97.5 0.21 58th embodiment 24th embodiment LA 〇97.5 0.22 59th embodiment 25th embodiment LA 〇97.7 0.17 60th embodiment 26th embodiment LA 〇97.8 0.21 61st embodiment 27th implementation Example LB 〇97.9 0.18 62nd embodiment 28th embodiment LB 〇97.5 0.21 63rd embodiment 29th embodiment LB 〇97.5 0.22 64th embodiment 30th embodiment LB 0099.7 0.17 65th embodiment 31 examples LC 0099.8 0.18 66th embodiment 32nd embodiment LC 009009.0.2 67th embodiment 33rd embodiment LC 〇97.9 0.18 68th embodiment 34th embodiment LC 〇97.5 0.21 The composition of the liquid crystal composition used for the liquid crystal display element is shown below. The physical properties 此 of these compositions are shown in Table 15. 59 576950 8310-pif2 < Liquid crystal composition LA > C5Hl1 " KZy) ~ C ^ _F 12% 9% C7Hl5 ~ ^ Z) ^ C ^ " F 7% C2H5-〇 ^ 〇-〇 ~ ocf3 7% C3H7H ^ ) ~ h (^) ~ ^^-〇CF3 7% ~ ^^ ~ 0CF3 7%. 2nd 4 ~ C ^ " 〇CF: 3 4% C5Hl 1 " KZ ^ (Z) ~ C2H4 ~ C ^ ~ 〇CF3 4% C3H7 c3h7

5 % 10 % 。3日7 C2H4 ~ 3 % C3H75% 10%. 3 days 7 C2H4 ~ 3% C3H7

3 %3%

C5H1~C^C^H7 c3h7~^^m^)~^^-0CF2H 3 % 4 % 7 %576950 8310-pif2 <液晶組成物lb>C5H1 ~ C ^ C ^ H7 c3h7 ~ ^^ m ^) ~ ^^-0CF2H 3% 4% 7% 576950 8310-pif2 < Liquid crystal composition lb >

F 8 % 10 % 5 % 9 % 9 % 15 % 15 %F 8% 10% 5% 9% 9% 15% 15%

C3H7-hG)^O~c00 2 % F 一 /=<Fg4h9-(3-c^~c〇0 一 /=<F〇δΗι i"KD~G^co° ~CJ~FC3H7^0^0~C〇〇 ~^0"F F c4H9—{^—C〇〇一 2 % 2 % 10 % 3 %C3H7-hG) ^ O ~ c00 2% F I / = &F; Fg4h9- (3-c ^ ~ c〇0 I / = &F; F〇δΗι i " KD ~ G ^ co ° ~ CJ ~ FC3H7 ^ 0 ^ 0 ~ C〇〇 ~ ^ 0 " FF c4H9 — {^ — C〇〇 一 2% 2% 10% 3%

F COOF COO

3 % 61 576950 C7H153% 61 576950 C7H15

F — C2H4— 8310-pif2 <液晶組成物LC>F — C2H4 — 8310-pif2 < Liquid crystal composition LC >

.F C3H7~h(^~^^~0C2H5 C3H7^CZ)~(^)~C4H9.F C3H7 ~ h (^ ~ ^^ ~ 0C2H5 C3H7 ^ CZ) ~ (^) ~ C4H9

C3H7-〇-〇^C^F 。5屮 i~hO^O~O"f C3H7-^3~ C2H4~ c2h5C3H7-〇-〇 ^ C ^ F. 5 屮 i ~ hO ^ O ~ O " f C3H7- ^ 3 ~ C2H4 ~ c2h5

C3H7C3H7

C5H11C5H11

c2h5 •Ό-c2h5 • Ό-

C2h4-h〇H^-F 5 % 5 % 10 % 5 % 10 % 10 % 10 % 5 % 3 % 3 % 6 % 5 % 6 % 8 % c3h7~~^ )~~^~~^-〇CH3 5 % C3H7H^^)~<^)~<^~^~C3H7 4 % 62 5 %576950 8310-pif2<液晶組成物LD> C4H9C2h4-h〇H ^ -F 5% 5% 10% 5% 10% 10% 10% 5% 3% 3% 6% 5% 6% 8% c3h7 ~~ ^) ~~ ^ ~~ ^ -〇CH3 5% C3H7H ^^) ~ < ^) ~ &^; ^ ~ ^ ~ C3H7 4% 62 5% 576950 8310-pif2 < liquid crystal composition LD > C4H9

12 % 10 % 10 % 5 % 10 %12% 10% 10% 5% 10%

.F C4H9—^~^~^ ^—COO- 卜 F 10 %.F C4H9— ^ ~ ^ ~ ^ ^ —COO- BU F 10%

3 %3%

C5H11 COO -一 C2H5'h〇^C^~C00"^{3/ F 3 % 3 %C5H11 COO -One C2H5'h〇 ^ C ^ ~ C00 " ^ {3 / F 3% 3%

C3H7 5 % 3 % t5 % 6 % 63 12 % 576950 C3H7~CZ)~ C2^4C3H7 5% 3% t5% 6% 63 12% 576950 C3H7 ~ CZ) ~ C2 ^ 4

8310-pif2 <液晶組成物LE> C&Hl1 C3H7^^)~^^~〇C2H58310-pif2 < Liquid crystal composition LE > C & Hl1 C3H7 ^^) ~ ^^ ~ 〇C2H5

Ό- C2H4_O~0"F C3H7-^^— C2H4—~ — C2H4—~ C3H7· C3H7~〇^O^CF2〇~^-〇CF3 c5Hi i_H(Z)~HC^-CF2a~HC^_CF3 7 % 20 % 8 % 8 % 6 % 5 % 5 % 5 % 2 % 1 % 2 % 4 % 4 % 4 % 3 % 4 % 64 576950 8310-pif2 <液晶組成物FB01〉Ό- C2H4_O ~ 0 " F C3H7-^^ — C2H4— ~ — C2H4— ~ C3H7 · C3H7 ~ 〇 ^ O ^ CF2〇 ~ ^ -〇CF3 c5Hi i_H (Z) ~ HC ^ -CF2a ~ HC ^ _CF3 7% 20% 8% 8% 6% 5% 5% 5% 2% 1% 2% 4% 4% 4% 3% 4% 64 576950 8310-pif2 < Liquid crystal composition FB01>

F 〇2Η5Ό~ 〇-〇~F 厂· _ \ CsH7 νΖ/ C5H11 (上述3種化合物的等量混合物) 表15 液晶組成物 NI 點(。C) 黏度W 20 △ n/25〇C 臨界電壓 Δ £ /25〇C (mPa*s) Vth(V) FB01 112.8 25.6 0.0791 1.97 4.8 LA 85.3 14.9 0.092 2.40 4.5 LB 81.3 31.9 0.092 1.72 11.3 LC 88.5 18.1 0.093 2.65 3.3 LD 75.7 34.4 0.084 1.39 13.1 LE 71.8 15.2 0.085 2.18 4.2 由上述的結果，使用本發明的感光性樹脂的塗膜，能夠 調製出可用g線以及h線曝光、高感度且無顯影殘渣、顯影 性優異，而且，耐鹼性、耐溶劑性、耐熱性等優異的間隔件， 然後，具備此間隔件的液晶顯示元件，係爲耐硏磨性、液晶 配向性、電壓保持率、殘留DC優異的液晶顯示元件。 65 576950 8310-pif2 其次，本發明的光硬化性著色組成物的調製例以及其使 用例如以下實施例所示，然而本發明並不限定於此些實施例。 尙且，各別實施例所得的事後烤後基板的評價使用下述的方 法。 <感度> 以下式所算出的殘膜率評價。此値在85%以上爲良好。 殘膜率=(於200°C-30分鐘事後烤後的膜厚/曝光後的膜厚）x 100(%) <表面粗糙度> 事後烤後的基板的表面粗糙度Ra(Roughness average)，使 用Tencor(株)製a step200，以針壓5mg、掃描速度5s/400 μ m 測定。RaS3〇A爲良好。 <殘渣> 殘渣係爲顯影去除未曝光部份所殘留，含顏料樹脂狀的 附著物。所得的曝後烤後的基板，以日立(株)製掃描式電子顯 微鏡FE-SEM S-800(以下簡稱SEM)以100000倍觀察，調查有 無殘渣。 第69實施例 量取作爲溶劑的丙二醇單甲基醚乙酸酯（以下略記爲 PGMEA。）79.8g、作爲顏料分散劑的高分子化合物系的 Zeneca(株）製 Solsperse32000(以下略記爲 Solsperse)5.0g、氟 代烷基聚羥基乙基醚系的非離子界面活性劑的NEOS製的 Ftergent521(以下略記爲Ftergent)0.2g，並將之混合溶解，且 於其中加入C.I.顏料紅254 13.5g，C.I·顏料黃139 1.5g，在勻 化器中處理5小時。此分散液移至玻璃容器，加入2mm氧化 66 576950 8310-pif2 锆小珠，使用混砂機以600rpm/20小時的條件處理。分散液與 小珠分離後，於分散液加入〇.6mm氧化锆小珠，由混砂機以 lOOOrpm/20小時的條件處理。將分散液與小珠分離後，於分 散液加入〇.3mm氧化锆小珠，由混砂機以500rpm/20小時的 條件處理。將分散液與小珠分離後，將分散液以細孔徑0.5// m的過濾器過濾，以得到紅色的顏料分散液。 其次，於具備攪拌子的l〇〇ml三角燒杯中，加入並混合 溶解PGMEA10.4g、苄基甲基丙烯酸酯/甲基甲基丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合物（莫耳比31.5 : 49·4 : 4.7 : 14.4，重量平均分子量6000)1.0g、T基甲基丙烯 酸酯/5-四氫呋喃甲基羥基羧基戊基（甲基）丙烯酸酯/2-羥基乙 基甲基丙烯酸酯/甲基丙烯酸共聚合物(莫耳比60 : 8.6 : 12.5 : 18.9，重量平均分子量7000)0.6g、苄基甲基丙烯酸酯/甲基甲 基丙烯酸酯共聚合物（莫耳比74: 26,重量平均分子量 6000)0_4g、二季戊四醇六丙烯酸酯以及二季戊四醇五丙烯酸 酯的混合物，東亞合成（株）製ARONIX M400(以下略記爲 M400)1.2g、3,3’-二（甲氧羰基)·4,4’_二(t_丁基過氧羰基)二苯甲 酮的20重量％甲苯溶液1.8g、3-苯醯-7-二乙胺基香豆素 0.18g、矽樹脂系的界面活性劑的Byk-Chemie · Japan (株）製 Byk-300之0.002g以及Byk-346之〇.〇〇2g，攪拌上述紅色的 顏料分散液14.4g的同時慢慢的滴入此些混合物中，以得到紅 色的光硬化性著色組成物。 上述的紅色光硬化性著色組成物，以700rpm、5秒鐘旋 轉塗佈於附有鉻的黑色矩陣的玻璃基板上，並置於60°C的熱 墊板上乾燥2分鐘。此基板以USHIO(株)製UI-501C超高壓水 銀燈，介由具20// m的條狀圖案光罩以及HOYA(株)製I線濾 67 576950 8310-pif2 色鏡L40(A $ 370nm切斷濾鏡），主要以400nm以上的波長爲 中心，在大氣中間隔200//m曝光。曝光量以USHIO(株)製的 累加光量計UIT-102、受光器UVD-405PD測定爲l〇〇mJ/cm2。 曝光後的基板，以在純水25Kg中溶解氫氧化鈉12.5g與十二 基苯磺酸鈉50g所形成的顯影液進行淋浴顯影，並去除未曝 光部。此基板於200°C事後烤30分鐘，殘膜率測定爲90%。 而且，事後烤之後的基板的表面粗糙度Ra爲10A。然後，事 後烤後的基板的玻璃板上與鉻上亦未見殘渣。 第70實施例 混合溶解 PGMEA79.8g、Solsperse5.0g、Ftergent0.2g，且 於其中加入C.I·顏料綠36 9,75g，C.I·顏料黃138 5.25g，在勻 化器中處理5小時。此分散液移至玻璃容器，加入2mm氧化 锆小珠，使用混砂機以1200rpm/20小時的條件處理。分散液 與小珠分離後，於分散液加入〇.6mm氧化锆小珠，由混砂機 以800rpm/20小時的條件處理。將分散液與小珠分離後，於分 散液加入〇.3mm氧化锆小珠，由混砂機以500rpm/30小時的 條件處理。將分散液與小珠分離後，將分散液以細孔徑〇·5// m的過濾器過濾，以得到綠色的顏料分散液。 其次，與第69實施例的場合相同，於具備攪拌子的100ml 三角燒杯中，加入並混合溶解PGMEA3.4g、苄基甲基丙烯酸 酯/甲基甲基丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共 聚合物（莫耳比31.5 : 49.4 : 4.7 : 14.4，重量平均分子量 6000)0.8g、苄基甲基丙烯酸酯/5-四氫呋喃甲基羥基羧基戊基 (甲基）丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合 物(莫耳比60 : 8.6 : 12.5 ·· 18.9，重量平均分子量7000)0.8g、 68 576950 8310-pif2 苄基甲基丙烯酸酯/甲基甲基丙烯酸酯共聚合物（莫耳比74: 26,重量平均分子量6000)0_4g、自由基聚合性單體M400 l.Og、 3,3’-二（甲氧羰基）-4,4’-二（t-丁基過氧羰基）二苯甲酮的20重 量％甲苯溶液2.5g、3-苯醯-7-二乙胺基香豆素0.3g、前述的 Byk-300與Byk-346皆爲0.002g，攪拌上述綠色的顏料分散液 18.6g的同時慢慢的滴入此些混合物中，以得到綠色的光硬化 性著色組成物。 上述的綠色光硬化性著色組成物，以與第69實施例同樣 的條件進行塗佈、乾燥、曝光、顯影、事後烤，殘膜率測定 爲90%。而且，事後烤之後的基板的表面粗糙度Ra爲10A。 然後，事後烤後的基板的玻璃板上與鉻上亦未見殘渣。 第71實施例 混合溶解 PGMEA84.8g、Solsperse5.0g、Ftergent0.2g，且 於其中加入C.I·顏料藍15 : 6 lO.Og，在勻化器中處理5小時。 此分散液移至玻璃容器，加入2mm氧化锆小珠，使用混砂機 以1500rpm/20小時的條件處理。分散液與小珠分離後，於分 散液加入〇.6mm氧化锆小珠，由混砂機以l〇〇〇rpm/20小時的 條件處理。將分散液與小珠分離後，於分散液加入0.3mm氧 化锆小珠，由混砂機以800rpm/20小時的條件處理。將分散液 與小珠分離後，將分散液以細孔徑0.5//m的過濾器過濾，以 得到藍色的顏料分散液。 其次，混合溶解PGMEA1.05g、苄基甲基丙烯酸酯/甲基 甲基丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合物 (莫耳比31.5 : 49.4 : 4.7 : 14.4，重量平均分子量6000)1.2g、 苄基甲基丙烯酸酯/5-四氫呋喃甲基羥基羧基戊基（甲基)丙烯酸 69 8310-pif 2 酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合物(莫耳比6〇 ·· 8·ό : 12·5 : 18.9，重量平均分子量7000)0.4g、苄基甲基丙烯 酸酯/甲基甲基丙烯酸酯共聚合物(莫耳比74 : 26，重量平均分 子量6000)〇_4g、自由基聚合性單體M400 1.4g、3,3，-二（甲氧 羯基)-4,4’-二（t_ 丁基過氧羰基)二苯甲酮的2〇重量％甲苯溶液 2.1g、3-本酿-7-二乙胺基香豆素〇.〇42g、前述的Byk_300與 Byk-346皆爲0.002g，攪拌上述藍色的顏料分散液2〇.9g的同 時慢慢的滴入此些混合物中，以得到藍色的光硬化性著色組 成物。 上述的藍色光硬化性著色組成物，以與第69實施例同樣 的條件進行塗佈、乾燥、曝光、顯影、事後烤，殘膜率測定 爲89%。而且，事後烤之後的基板的表面粗糙度Ra爲15a。 然後’事後烤後的基板的玻璃板上與鉻上亦未見殘渣。 第72實施例 在第69實施例的紅色光硬化性著色組成物的調製中，將 3,3’-一（甲氧羰基）_4,4’_二（t-丁基過氧羰基）二苯甲酮的2〇重 量％甲苯溶液，使用3,3，,4,4，-四（t_ 丁基過氧羰基)二苯甲酮的 25重量％甲苯溶液（日本油脂(株)製bttb25,以下略記爲bttb) 取代。其添加量由i.Sg變更爲M4g之外，以與第69實施例 同樣的條件調製紅色光硬化性著色組成物。使用此組成物進 行與第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤， 殘膜率測定爲90%。而且，事後烤之後的基板的表面粗糙度F 〇2Η5Ό ~ 〇-〇 ~ F Factory · _ \ CsH7 νZ / C5H11 (equivalent mixture of the above three compounds) Table 15 Liquid crystal composition NI point (.C) Viscosity W 20 △ n / 25〇C critical voltage Δ £ / 25〇C (mPa * s) Vth (V) FB01 112.8 25.6 0.0791 1.97 4.8 LA 85.3 14.9 0.092 2.40 4.5 LB 81.3 31.9 0.092 1.72 11.3 LC 88.5 18.1 0.093 2.65 3.3 LD 75.7 34.4 0.084 1.39 13.1 LE 71.8 15.2 0.085 2.18 4.2 From the above results, using the coating film of the photosensitive resin of the present invention, it is possible to prepare g-line and h-line exposure, high sensitivity, no development residue, and excellent developability, and also alkali resistance, solvent resistance, and heat resistance And the like, and the liquid crystal display element provided with the spacer is a liquid crystal display element having excellent abrasion resistance, liquid crystal alignment, voltage retention, and residual DC. 65 576950 8310-pif2 Next, examples of preparation and use of the photocurable coloring composition of the present invention are shown in the following examples, but the present invention is not limited to these examples. In addition, the following methods were used to evaluate the post-bake substrates obtained in the respective examples. < Sensitivity > Evaluation of the residual film rate calculated by the following formula. This ratio is good at 85% or more. Residual film rate = (film thickness after baking at 200 ° C-30 minutes / film thickness after exposure) x 100 (%) < surface roughness > surface roughness Ra (Roughness average) of the substrate after baking ), A step200 manufactured by Tencor Corporation was used for measurement at a needle pressure of 5 mg and a scanning speed of 5 s / 400 μm. RaS3OA is good. < Residues > Residues are pigment-like resin-like deposits which are left after development to remove unexposed portions. The obtained post-exposure baking substrate was observed at 100,000 times with a scanning electron microscope FE-SEM S-800 (hereinafter referred to as SEM) manufactured by Hitachi, Ltd., and the presence or absence of residue was investigated. In the 69th example, 79.8 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) as a solvent was measured, and Solsperse 32000 (hereinafter abbreviated as Solsperse) manufactured by Zeneca Corporation as a pigment dispersant polymer compound was measured. 5.0 g, 0.2 g of fluoroalkyl polyhydroxyethyl ether-based nonionic surfactant Ftergent521 (hereinafter abbreviated as Ftergent) made by NEOS, mixed and dissolved, and added CI Pigment Red 254 13.5g, CI -Pigment Yellow 139 1.5g, treated in a homogenizer for 5 hours. This dispersion was transferred to a glass container, 2 mm of oxidized 66 576950 8310-pif2 zirconium beads were added, and treated with a sand mixer at 600 rpm / 20 hours. After the dispersion liquid was separated from the beads, 0.6 mm of zirconia beads were added to the dispersion liquid, and treated by a sand mixer at 1,000 rpm / 20 hours. After the dispersion was separated from the beads, 0.3 mm of zirconia beads were added to the dispersion, and the mixture was processed at 500 rpm / 20 hours by a sand mixer. After separating the dispersion liquid from the beads, the dispersion liquid was filtered through a filter having a pore size of 0.5 // m to obtain a red pigment dispersion liquid. Next, in a 100 ml triangular beaker equipped with a stir bar, 10.4 g of PGMEA, benzyl methacrylate / methmethacrylate / 2-hydroxyethyl methacrylate / methacrylic acid were mixed and dissolved. Copolymer (Molar ratio 31.5: 49.4: 4.7: 14.4, weight average molecular weight 6000) 1.0 g, T-based methacrylate / 5-tetrahydrofuranmethylhydroxycarboxypentyl (meth) acrylate / 2- Hydroxyethyl methacrylate / methacrylic acid copolymer (Molar ratio 60: 8.6: 12.5: 18.9, weight average molecular weight 7000) 0.6 g, benzyl methacrylate / methmethacrylate copolymer (Mole ratio 74: 26, weight average molecular weight 6000) A mixture of 0-4 g, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, 1.2 g of ARONIX M400 (hereinafter abbreviated as M400) manufactured by Toa Synthetic Co., Ltd. -1.8 g of a 20% by weight toluene solution of bis (methoxycarbonyl) · 4,4'-bis (t-butylperoxycarbonyl) benzophenone, 3-phenylhydrazone-7-diethylaminocoumarin 0.18 g, 0.002 g of Byk-300 manufactured by Byk-Chemie Japan Co., Ltd., and Byk-346 of Byk-Chemie Japan Co., Ltd. Meanwhile 〇2g, stirring the red pigment dispersion was slowly added dropwise 14.4g of such mixture to obtain a photocurable colored composition of red. The red light-curable colored composition was spin-coated on a glass substrate with a black matrix with chromium at 700 rpm for 5 seconds, and dried on a hot pad at 60 ° C for 2 minutes. This substrate is a UI-501C ultra-high pressure mercury lamp made by USHIO Co., Ltd., with a stripe pattern mask with 20 // m and I line filter made by HOYA Co., Ltd. 67 576950 8310-pif2 color mirror L40 (A $ 370nm cut Filter), mainly with wavelengths above 400nm as the center, and exposed at intervals of 200 // m in the atmosphere. The exposure amount was measured at 100 mJ / cm2 using a total light meter UIT-102 and a UVD-405PD receiver made by USHIO. The exposed substrate was subjected to shower development with a developing solution in which 12.5 g of sodium hydroxide and 50 g of sodium dodecylbenzenesulfonate were dissolved in 25 kg of pure water, and the unexposed portions were removed. This substrate was baked at 200 ° C for 30 minutes afterwards, and the residual film rate was determined to be 90%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate or chromium of the substrate after the baking. Example 70 79.8 g of PGMEA, 5.0 g of Solsperse, and 0.2 g of Ftergent were added, and C.I. Pigment Green 36 9,75 g and C.I. Pigment Yellow 138 5.25 g were added thereto, and treated in a homogenizer for 5 hours. This dispersion was transferred to a glass container, and 2 mm of zirconia beads were added, and treated with a sand mixer at 1200 rpm / 20 hours. After the dispersion was separated from the beads, 0.6 mm of zirconia beads were added to the dispersion, and the mixture was processed by a sand mixer at 800 rpm / 20 hours. After the dispersion was separated from the beads, 0.3 mm of zirconia beads were added to the dispersion, and the mixture was processed at 500 rpm / 30 hours by a sand mixer. After the dispersion liquid was separated from the beads, the dispersion liquid was filtered through a filter having a pore size of 0.5 // m to obtain a green pigment dispersion liquid. Next, as in the case of the 69th embodiment, in a 100 ml triangular beaker with a stir bar, 3.4 g of PGMEA, benzyl methacrylate / methmethacrylate / 2-hydroxyethyl methyl were dissolved in the mixture. Acrylate / methacrylic acid copolymer (Molar ratio 31.5: 49.4: 4.7: 14.4, weight average molecular weight 6000) 0.8 g, benzyl methacrylate / 5-tetrahydrofuranmethylhydroxycarboxypentyl (meth) acrylic acid Ester / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (Molar ratio 60: 8.6: 12.5 · 18.9, weight average molecular weight 7000) 0.8 g, 68 576950 8310-pif2 benzyl methacrylate / Methmethacrylate copolymer (Mole ratio 74: 26, weight average molecular weight 6000) 0-4 g, radical polymerizable monomer M400 1.0 g, 3,3'-bis (methoxycarbonyl) -4, 2.5 g of a 20% by weight toluene solution of 4'-bis (t-butylperoxycarbonyl) benzophenone, 0.3 g of 3-phenylhydrazone-7-diethylaminocoumarin, the aforementioned Byk-300 and Byk -346 are all 0.002g. While stirring 18.6g of the above green pigment dispersion, slowly drip into these mixtures to obtain a green light hard Chemically colored composition. The green photocurable coloring composition described above was coated, dried, exposed, developed, and baked after the same conditions as in Example 69, and the residual film rate was measured to be 90%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate or chromium of the substrate after baking. Example 71 PGMEA 84.8 g, Solsperse 5.0 g, and Ftergent 0.2 g were mixed and dissolved, and C.I. Pigment Blue 15: 6 lO. Og was added thereto, and treated in a homogenizer for 5 hours. This dispersion was transferred to a glass container, and 2 mm zirconia beads were added, and the mixture was processed at 1500 rpm / 20 hours using a sand mixer. After the dispersion was separated from the beads, 0.6 mm of zirconia beads were added to the dispersion, and treated with a sand mixer at 1,000 rpm / 20 hours. After the dispersion was separated from the beads, 0.3 mm of zirconia beads were added to the dispersion, and the mixture was processed at 800 rpm / 20 hours by a sand mixer. After separating the dispersion liquid from the beads, the dispersion liquid was filtered through a filter having a pore size of 0.5 // m to obtain a blue pigment dispersion liquid. Next, 1.05 g of PGMEA, benzyl methacrylate / methmethacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 31.5: 49.4: 4.7: 14.4, Weight average molecular weight 6000) 1.2 g, benzyl methacrylate / 5-tetrahydrofuranmethylhydroxycarboxypentyl (meth) acrylic acid 69 8310-pif 2 ester / 2-hydroxyethyl methacrylate / methacrylic acid Polymer (mole ratio 6〇 ···: 12 · 5: 18.9, weight average molecular weight 7000) 0.4 g, benzyl methacrylate / methmethacrylate copolymer (mole ratio 74: 26. Weight average molecular weight 6000) 0-4 g, radical polymerizable monomer M400 1.4 g, 3,3, -bis (methoxyfluorenyl) -4,4'-bis (t-butylperoxycarbonyl) dibenzene 2.1 g of a 20% by weight toluene solution of methyl ketone, 0.042 g of 3-benjo-7-diethylaminocoumarin, 0.002 g of Byk_300 and Byk-346 described above, and stirring the blue pigment to disperse While 20.9 g of the liquid was slowly dropped into these mixtures, a blue photocurable coloring composition was obtained. The above-mentioned blue photocurable coloring composition was coated, dried, exposed, developed, and baked after the same conditions as in Example 69. The residual film ratio was measured to be 89%. The surface roughness Ra of the substrate after the baking was 15a. No residue was found on the glass plate or chromium of the substrate after the baking. Example 72 In the preparation of the red photocurable coloring composition of Example 69, 3,3'-mono (methoxycarbonyl) _4,4'_bis (t-butylperoxycarbonyl) dibenzene was prepared. A 20% by weight toluene solution of ketone is a 25% by weight toluene solution of 3,3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone (bttb25, manufactured by Nihon Oil Co., Ltd., or less It is abbreviated as bttb). The addition amount was changed from i.Sg to M4g, and a red photocurable coloring composition was prepared under the same conditions as in Example 69. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. Moreover, the surface roughness of the substrate after baking

Ra爲10A。然後，事後烤後的基板的玻璃板上與鉻上亦未見 殘渣。 、 576950 8310-pif2 第73實施例 在第70實施例的綠色光硬化性著色組成物的調製中，將 3,3’-二（甲氧擬基)-4,4’-二〇丁基過氧幾基）二苯甲酮的20重 量％甲苯溶液，使用前述的BTTB取代。其添加量由2.5g變 更爲2.0g之外，與第69實施例同樣的條件調製綠色光硬化性 著色組成物。使用此組成物進行與第69實施例同樣的塗佈、 乾燥、曝光、顯影、事後烤，殘膜率測定爲90%。而且，事 後烤之後的基板的表面粗糙度Ra爲l〇A。然後，事後烤後的 基板的玻璃板上與鉻上亦未見殘渣。 第74實施例 在第71實施例的藍色光硬化性著色組成物的調製中，將 3,3’-二（甲氧羰基)-4,4’-二（t-丁基過氧羰基）二苯甲酮的20重 量％甲苯溶液，使用前述的BTTB取代。其添加量由2.1g變 更爲1.68g之外，與第69實施例同樣的條件調製藍色光硬化 性著色組成物。使用此組成物進行與第69實施例同樣的塗佈、 乾燥、曝光、顯影、事後烤，殘膜率測定爲88%。而且，事 後烤之後的基板的表面粗糙度Ra爲15人。然後，事後烤後的 基板的玻璃板上與鉻上亦未見殘渣。 第75實施例 在第69實施例的紅色光硬化性著色組成物的調製中，紅 色顏料分散液的量由14.4g變爲8.45g，PGMEA的量由由10.4g 變爲15.14g以外，以與第69實施例相同的條件調製紅色光硬 化性著色組成物。使用此組成物進行與第69實施例同樣的塗 佈、乾燥、曝光、顯影、事後烤，殘膜率測定爲91%。而且， 71 576950 8310-pif2 事後烤之後的基板的表面粗糙度Ra爲l〇A。然後’事後烤後 的基板的玻璃板上與鉻上亦未見殘渣。 第76實施例 在第69實施例的綠色光硬化性著色組成物的調製中’綠 色顏料分散液的量由18.6g變爲10.59g，PGMEA的量由由3.39g 變爲9.81g以外，以與第70實施例相同的條件調製綠色光硬 化性著色組成物。使用此組成物進行與第69實施例同樣的塗 佈、乾燥、曝光、顯影、事後烤，殘膜率測定爲90%。而且， 事後烤之後的基板的表面粗糙度Ra爲10A。然後，事後烤後 的f基板的玻璃板上與鉻上亦未見殘渣。 第77實施例 在第71實施例的藍色光硬化性著色組成物的調製中，藍 色顏料分散液的量由20.89g變爲14.4g，PGMEA的量由由4.16g \66g以外，以與第71實施例相同的條件調製藍色光硬 化性著色組成物。使用此組成物進行與第69實施例同樣的塗 佈、乾燥、曝光、顯影、事後烤，殘膜率測定爲90%。而且， 事後烤之後的基板的表面粗糙度Ra爲10A。然後，事後烤後 板的玻璃板上與鉻上亦未見殘渣。 第78實施例 不使用苄基甲基丙烯酸酯/甲基甲基丙烯酸酯共聚合物（莫 耳比74 : 26，重量平均分子量6000)，苄基甲基丙烯酸酯/甲 基丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合 物(奠耳比 31.5 : 49.4 : 4.7 : 14.4，重量平均分子量6000)的使 72 576950 8310-pif2 用重由i.〇g變舄l 2Sg、苄基甲棊丙烯酸酯四氫呋喃甲基 羥基羧基戊基（甲_)珂烯酸酯/2_羥基乙基甲基丙烯酸酯/甲基 丙烯酸共聚合物（莫耳比60 : 8_6 ·· I2·5 ·· I8.9，重量平均分子 量8000)的使用量由〇 6g變爲〇.75g之外，以與第69實施例 相同的條件得到紅色光硬化性著色組成物。使用此組成物進 行與第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤， 殘膜率測定爲90%。而且，事後烤之後的基板的表面粗糙度 Ra爲10A。然後，事後烤後的基板的玻璃板上與鉻上亦未見 殘渣。 第79實施例 不使用苄基甲基丙烯酸酯/甲基甲基丙嫌酸酯共聚合物(莫 耳比74 : 26，重量平均分子量6000)，苄基甲基丙烯酸酯/甲 基甲基丙稀酸酯/2-經基乙基甲基丙稀酸酯/甲基丙稀酸共聚合 物(莫耳比31.5 : 49.4 : 4.7 : 14.4 ’重量平均分子量6000)的使 用量由0.8g變爲i.〇g、苄基甲基丙烯酸酯/5_四氫呋喃甲基羥 基羧基戊基（甲基）丙烯酸酯/2-經基乙基甲基丙烯酸酯/甲基丙 烯酸共聚合物（莫耳比60 : 8.6 : 12·5 : 18.9，重量平均分子量 8000)的使用量由〇·8§變爲LOg之外，以與第70實施例相同 的條件得到綠色光硬化性著色組成物。使用此組成物進行與 第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤，殘膜 率測定爲90%。而且’事後烤之後的基板的表面粗糙度Ra爲 10A。然後，事後烤後的基板的玻璃板上與鉻上亦未見殘渣。 第80實施例 不使用苄基甲基丙嫌酸酯/甲基甲基丙烯酸酯共聚合物（莫 73 576950 8310-pif2 耳比74 : 26，重量平均分子量6000)，苄基甲基丙烯酸酯/甲 基甲基丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙烯酸共聚合 物(莫耳比31.5 : 49.4 : 4.7 : 14.4，重量平均分子量6000)的使 用量由1.2g變爲1.5g、〒基甲基丙烯酸酯/5-四氫咲喃甲基經 基羧基戊基（甲基）丙烯酸酯/2-羥基乙基甲基丙烯酸酯/甲基丙 烯酸共聚合物（莫耳比60 : 8.6 : 12_5 : 18.9，重量平均分子量 8000)的使用量由0.4g變爲0.5g之外，以與第71實施例相同 的條件得到藍色光硬化性著色組成物。使用此組成物進行與 第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤，殘膜 率測定爲88%。而且，事後烤之後的基板的表面粗糙度Ra爲 10A。然後，事後烤後的基板的玻璃板上與鉻上亦未見殘渣。 第9比較例 將3-苯醯-7-二乙胺基香豆素，以保土谷化學(株)製EAB-F(化合物名：4,4’-雙（二乙胺基）香豆素）取代之外，以與第69 實施例相同的得到紅色的著色組成物。使用此組合物進行與 第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤，而無 法形成圖案且塗膜全部剝離。 第10比較例 將3-苯醯-7-二乙胺基香豆素，以前述的EAB-F取代之外， 以與第70實施例相同的得到綠色的著色組成物。使用此組合 物進行與第69實施例同樣的塗佈、乾燥、曝光、顯影、事後 烤，而無法形成圖案且塗膜全部剝離。 第11比較例 74 576950 8310-pif2 將3-苯醯-7-二乙胺基香豆素，以前述的EAB-F取代之外， 以與第71實施例相同的得到藍色的著色組成物。使用此組合 物進行與第69實施例同樣的塗佈、乾燥、曝光、顯影、事後 烤，而無法形成圖案且塗膜全部剝離。 第12比較例 將3,3’-二（甲氧羰基)_4,4’_二(t-丁基過氧羰基)二苯甲酮的 20重量％甲苯溶液，使用chiba sPecialty chemicals(株)製的 Irgacure 369(化合物名：2-苄基-2-二乙胺基-1-(4-嗎啉代苯基)- 丁烷-1-酮)取代’其添加量由L8g變爲〇.36S之外’以與第69 實施例相同的得到紅色的著色組成物。使用此組合物進行與 第69實施例同樣的塗佈、乾燥、曝光、顯影、事後烤，而無 法形成圖案且塗膜全部剝離。 第13比較例 將3,3’-二（甲氧羰基)-4,4’-二(t-丁基過氧羰基)二苯甲酮的 20重量％甲苯溶液，使用前述的Irgacure 369取代，其添加量 · 由2.5g變爲0.5g之外，以與第70實施例相同的得到綠色的 · 著色組成物。使用此組合物進行與第69實施例同樣的塗佈、 乾燥、曝光、顯影、事後烤，而無法形成圖案且塗膜全部剝 第14比較例 將3,3’-二（甲氧羰基)-4,4’-二(t-丁基過氧羰基)二苯甲酮的 20重量％甲苯溶液，使用前述的Irgacure 369取代，其添加量 由2.1g變爲0.42g之外，以與第71實施例相同的得到藍色的 75 576950 8310-pif2 著色組成物。翻此組合補行轉69實酬關的塗:布、 乾燥、曝光、目影、事後肖，而無法形成圖案且塗膜全部剝 離。 第15比較例 將3,3，-二（甲氧幾基)-4,4，-二(卜丁基過氧_)一苯甲酉同^ 20重量％甲苯溶液，使用Midori化學(株)製的TAZ 11〇(化口 物名：1，3_雙（三氯甲基)-5-(4，-甲氧基苯酚)-s一二連氮）取代’ 其添加量由1.8g變爲0.36g之外，以與第69實施例相同的得 到紅色的著色組成物。使用此組合物進行與第69實施例同樣 的塗佈、冑燥、_光、目影、雜烤，#法形成圖案且塗膜 全部剝離。 第16比較例 將3,3，-二（甲氧羰基)_4,4，-H(t_丁基過氧羰基)二苯甲酮的 20重量％甲苯溶液，使用前述的TAZ 110取代’其添加量由 2.5g變爲〇.5g之外，以與第7〇實施例相同的得到綠色的著色 組成物。使用此組合物進行與第69實施例同樣的塗佈、乾燥、 曝光、顯影、事後烤，無法形成圖案且塗膜全部剝離。 第17比較例 將3,3’-二（甲氧羰基)_4,4’·二（t-丁基過氧羰基）二苯甲酮的 20重量％甲苯溶液，使用前述的TAZ 110取代’其添加量由 2.lg變爲〇.42g之外，以與第70實施例相同的得到藍色的著 色組成物。使用此組合物進行與第69實施例同樣的塗佈、乾 燥、曝光、顯影、事後烤，無法形成圖案且塗膜全部剝離。 76 576950 8310-pif2 第18比較例 將3,3’-二（甲氧羰基)-4,4’-二(t-丁基過氧羰基)二苯甲酮的 20重量％甲苯溶液，使用黑金化成(株)製的Biimidazole(化合 物名：2,2’-雙（〇-氯苯基）-4,4’，5,5’-四苯基-1，2’-聯二咪唑）取 代，其添加量由1.8g變爲〇.36g之外，以與第69實施例相同 的得到紅色的著色組成物。使用此組合物進行與第69實施例 同樣的塗佈、乾燥、曝光、顯影、事後烤，無法形成圖案且 塗膜全部剝離。 第19比較例 將3,3’-二（甲氧幾基)-4,4’-二(t-丁基過氧擬基)二苯甲酮的 20重量％甲苯溶液，使用前述的Biimidazole取代，其添加量 由2.5g變爲〇.5g之外，以與第70實施例相同的得到綠色的 著色組成物。使用此組合物進行與第69實施例同樣的塗佈、 乾燥、曝光、顯影、事後烤，無法形成圖案且塗膜全部剝離。 第20比較例 將3,3’-一（甲氧羯基)-4,4’-一(t-丁基過氧幾基）二苯甲酮的 20重量％甲苯溶液，使用前述的Biimidazole取代，其添加量 由2.lg變爲〇.42g之外，以與第71實施例相同的得到藍色的 著色組成物。使用此組合物進行與第69實施例同樣的塗佈、 乾燥、曝光、顯影、事後烤，無法形成圖案且塗膜全部剝離。 產業上的利用性 依本發明的感光性樹脂組成物，能夠形成具備高感度、 77 576950 8310-pif2 無顯影殘渣(scum)顯影性優異、且耐鹼性、耐水性的液晶顯示 用間隔件。而且，依具備此間隔件，能夠形成硏磨耐性優異、 液晶的殘像現象、電壓保持率等的電器特性良好、機械強度 高且液晶層的膜厚均勻的液晶顯示元件。更加的’本發明的 感光性樹脂組成物的塗膜，由於能夠使用g線以及h線曝光’ 而能夠形成開口率或對比優異的液晶顯示元件° 而且，使用光硬化性著色組成物所得的濾色鏡塗膜二對 於g線以及h線液具有高感度，顯影、固化後的殘膜率闻’ 平坦性以及耐熱性亦良好，而且亦不會發生顯影殘渣。因此、’ 本發明的光硬化性著色組成物，適於應用於液晶顯示用的滅、 色鏡材料。 78Ra is 10A. Then, no residue was found on the glass plate or chromium of the substrate after baking. , 576950 8310-pif2 Example 73 In the preparation of the green photo-curable coloring composition of Example 70, 3,3'-bis (methoxycarbonyl) -4,4'-dibutyl A 20% by weight toluene solution of oxyquinyl) benzophenone was replaced with the aforementioned BTTB. The green light-curable coloring composition was prepared under the same conditions as in the 69th example, except that the amount of addition was changed from 2.5 g to 2.0 g. Using this composition, coating, drying, exposure, development, and post-bake were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. The surface roughness Ra of the substrate after the baking was 10 A. Then, no residue was found on the glass plate and chromium of the substrate after baking. Example 74 In the preparation of the blue photocurable coloring composition of Example 71, 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) di A 20% by weight toluene solution of benzophenone was replaced with the aforementioned BTTB. A blue light-curable coloring composition was prepared under the same conditions as in the 69th example, except that the amount of addition was changed from 2.1 g to 1.68 g. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 88%. The surface roughness Ra of the substrate after the baking was 15 persons. Then, no residue was found on the glass plate and chromium of the substrate after baking. Example 75 In the preparation of the red light-curable coloring composition of Example 69, the amount of the red pigment dispersion liquid was changed from 14.4 g to 8.45 g, and the amount of PGMEA was changed from 10.4 g to 15.14 g. In the 69th example, a red light-curable colored composition was prepared under the same conditions. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69. The residual film rate was measured to be 91%. Moreover, the surface roughness Ra of the substrate after 71 576950 8310-pif2 after baking was 10A. No residue was found on the glass plate or chromium of the substrate after the baking. Example 76 In the preparation of the green light-curable coloring composition of Example 69, the amount of the green pigment dispersion was changed from 18.6 g to 10.59 g, and the amount of PGMEA was changed from 3.39 g to 9.81 g. In the 70th example, a green light-curable coloring composition was prepared under the same conditions. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate of the f-substrate and chromium after the baking. Example 77 In the preparation of the blue photocurable coloring composition of Example 71, the amount of the blue pigment dispersion liquid was changed from 20.89 g to 14.4 g, and the amount of PGMEA was changed from 4.16 g to 66 g. The blue light-curable coloring composition was prepared under the same conditions as in Example 71. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate and chrome after baking. The 78th example did not use a benzyl methacrylate / methmethacrylate copolymer (Mole ratio 74:26, weight average molecular weight 6000), benzyl methacrylate / methacrylate / 2- The hydroxyethyl methacrylate / methacrylic acid copolymer (Mear ratio 31.5: 49.4: 4.7: 14.4, weight average molecular weight 6000) was used to change the weight of 72 576950 8310-pif2 from 1.0 g to 2Sg, Benzyl formamyl acrylate tetrahydrofuran methyl hydroxy carboxypentyl (methyl) ketoacrylate / 2 hydroxyethyl methacrylate / methacrylic acid copolymer (Molar ratio 60: 8_6 ·· I2 · 5 The red light-curable coloring composition was obtained under the same conditions as those in the 69th Example except that the amount of I8.9 (weight average molecular weight 8000) was changed from 0.06 g to 0.75 g. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate or chromium of the substrate after baking. In the 79th example, no benzyl methacrylate / methyl methyl propionate copolymer was used (Mole ratio 74:26, weight average molecular weight 6000), and benzyl methacrylate / methyl methyl propionate The amount of dilute ester / 2-Ethyl ethyl methyl acrylate / methacrylic acid copolymer (mole ratio 31.5: 49.4: 4.7: 14.4 'weight average molecular weight 6000) changed from 0.8 g to i.〇g, benzyl methacrylate / 5_tetrahydrofuranmethylhydroxycarboxypentyl (meth) acrylate / 2-lauryl ethyl methacrylate / methacrylic acid copolymer (Mole ratio 60 : 8.6: 12 · 5: 18.9, the weight-average molecular weight 8000) was used, except that the amount of use changed from 0.8 · § to LOg, and a green photo-curable coloring composition was obtained under the same conditions as in Example 70. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 90%. Further, the surface roughness Ra of the substrate after the post-bake was 10A. Then, no residue was found on the glass plate or chromium of the substrate after baking. The 80th example did not use a benzyl methacrylic acid ester / methacrylic acid ester copolymer (Mo 73 576950 8310-pif2 ear ratio 74:26, weight average molecular weight 6000), benzyl methacrylate / Methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 31.5: 49.4: 4.7: 14.4, weight average molecular weight 6000) used amount changed from 1.2 g to 1.5 g , Fluorenyl methacrylate / 5-tetrahydrofuranmethyl via carboxypentyl (meth) acrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (Molar ratio 60: 8.6: 12_5: 18.9 (with a weight average molecular weight of 8000), except that the amount used was changed from 0.4 g to 0.5 g, and a blue photocurable coloring composition was obtained under the same conditions as in the 71st Example. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, and the residual film rate was measured to be 88%. The surface roughness Ra of the substrate after the baking was 10A. Then, no residue was found on the glass plate or chromium of the substrate after baking. In the ninth comparative example, 3-phenylhydrazone-7-diethylaminocoumarin was manufactured by Hodogaya Chemical Co., Ltd. EAB-F (compound name: 4,4'-bis (diethylamino) coumarin) ) Except for the substitution, a red colored composition was obtained in the same manner as in the 69th embodiment. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, but no pattern was formed and the coating film was completely peeled. Tenth Comparative Example A green colored composition was obtained in the same manner as in Example 70 except that 3-phenylhydrazone-7-diethylaminocoumarin was substituted with the aforementioned EAB-F. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, but no pattern was formed and the coating film was completely peeled. Eleventh Comparative Example 74 576950 8310-pif2 A blue colored composition was obtained in the same manner as in Example 71 except that 3-phenylhydrazone-7-diethylaminocoumarin was substituted with the aforementioned EAB-F. . Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, but no pattern was formed and the coating film was completely peeled. Twelfth Comparative Example A 20% by weight toluene solution of 3,3'-bis (methoxycarbonyl) _4,4'_bis (t-butylperoxycarbonyl) benzophenone was produced using chiba sPecialty chemicals Co., Ltd. Irgacure 369 (compound name: 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butane-1-one) was replaced by its addition amount from L8g to 0.36S Other than the same as in the 69th embodiment, a red colored composition was obtained. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, but no pattern was formed and the coating film was completely peeled. In the thirteenth comparative example, a 20% by weight toluene solution of 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) benzophenone was substituted with the aforementioned Irgacure 369, The addition amount was changed from 2.5 g to 0.5 g, and a green coloring composition was obtained in the same manner as in Example 70. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in Example 69, but no pattern was formed and the coating film was peeled off. In Comparative Example 14, 3,3'-bis (methoxycarbonyl)- A 20% by weight toluene solution of 4,4'-bis (t-butylperoxycarbonyl) benzophenone was substituted with the aforementioned Irgacure 369, and the addition amount thereof was changed from 2.1 g to 0.42 g, in addition to the 71st In the same example, a blue 75 576950 8310-pif2 colored composition was obtained. Follow this combination to make up 69 coatings: cloth, dry, exposure, shadow, post-mortem, but can not form a pattern and peel off all the coating film. In the fifteenth comparative example, 3,3, -bis (methoxyquinyl) -4,4, -bis (butylbutylperoxy) -benzidine was used in a 20% by weight toluene solution, and a product made by Midori Chemical Co., Ltd. TAZ 11〇 (Chemical name: 1,3-bis (trichloromethyl) -5- (4, -methoxyphenol) -s-diazine) was substituted 'Its addition amount was changed from 1.8 g to 0.36 Except for g, a red colored composition was obtained in the same manner as in the 69th Example. Using this composition, coating, drying, light, shadow, and baking were performed in the same manner as in the 69th Example. Patterns were formed by the method and the coating film was completely peeled. In the sixteenth comparative example, a 20% by weight toluene solution of 3,3, -bis (methoxycarbonyl) _4,4, -H (t-butylperoxycarbonyl) benzophenone was replaced with the aforementioned TAZ 110 Except for the addition of 2.5 g to 0.5 g, a green colored composition was obtained in the same manner as in the 70th example. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in the 69th example, and no pattern was formed and the coating film was completely peeled. In the 17th comparative example, a 20% by weight toluene solution of 3,3′-bis (methoxycarbonyl) _4,4 ′ · bis (t-butylperoxycarbonyl) benzophenone was replaced with the aforementioned TAZ 110 ’ Except that the addition amount was changed from 2.lg to 0.42g, a blue colored composition was obtained in the same manner as in Example 70. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in the 69th Example, and no pattern was formed and the coating film was completely peeled. 76 576950 8310-pif2 18th Comparative Example A 20% by weight toluene solution of 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) benzophenone using black gold Biimidazole (compound name: 2,2'-bis (〇-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole) substituted by Kasei Co., Ltd., The addition amount was changed from 1.8 g to 0.36 g, and a red colored composition was obtained in the same manner as in the 69th Example. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in the 69th Example, and no pattern was formed and the coating film was completely peeled. In the 19th comparative example, a 20% by weight toluene solution of 3,3'-bis (methoxyquinyl) -4,4'-bis (t-butylperoxyamido) benzophenone was substituted with the aforementioned Biimidazole Except that the addition amount was changed from 2.5 g to 0.5 g, a green colored composition was obtained in the same manner as in Example 70. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in the 69th example, and no pattern was formed and the coating film was completely peeled. 20th Comparative Example A 20% by weight toluene solution of 3,3'-mono (methoxyfluorenyl) -4,4'-mono (t-butylperoxoyl) benzophenone was substituted with the aforementioned Biimidazole Except that the addition amount was changed from 2.lg to 0.42g, a blue colored composition was obtained in the same manner as in the 71st Example. Using this composition, coating, drying, exposure, development, and post-baking were performed in the same manner as in the 69th example, and no pattern was formed and the coating film was completely peeled. Industrial Applicability According to the photosensitive resin composition of the present invention, it is possible to form a spacer for a liquid crystal display having a high sensitivity, 77 576950 8310-pif2, excellent developability without development scum, and alkali resistance and water resistance. In addition, with this spacer, it is possible to form a liquid crystal display element having excellent honing resistance, good electrical characteristics such as the afterimage phenomenon of liquid crystals, and voltage holding ratio, high mechanical strength, and uniform film thickness of the liquid crystal layer. Furthermore, 'the coating film of the photosensitive resin composition of the present invention can form a liquid crystal display element having excellent aperture ratio and contrast because the g-line and h-line exposure can be used'. Furthermore, a color filter obtained using a photocurable coloring composition The coating film 2 has high sensitivity to the g-line and h-line liquids, and the residual film rate after development and curing is good. The flatness and heat resistance are also good, and development residues do not occur. Therefore, the photo-curable coloring composition of the present invention is suitable for use as a quenching and color mirror material for liquid crystal displays. 78

Claims (1)

576950 8310-pif2 公告本 拾、申請專利範圍： 1.一種感光性樹脂組成物，該感光性樹脂組成物含有一高 分子結合劑、一具乙烯性雙鍵化合物、一具二苯甲酮結構有 機過氧化物以及一具香豆素結構光增感劑，其中： 該高分子結合劑係爲一鹼可溶性樹脂、或是該鹼可溶性 樹脂與一鹼不溶性的具環氧基乙烯基聚合物的混合物； 且該高分子結合劑中的該鹼可溶性樹脂的比例爲40〜100 重量％左右，相對於該高分子結合劑，該具乙烯性雙鍵化合 物爲10〜200重量％左右，該具二苯甲酮結構有機過氧化物 爲0.1〜50重量％左右，以及該具香豆素結構光增感劑爲0.1 〜50重量％左右，組成物中全固形成份的含有量爲10〜50重 量％左右。 2·如申請專利範圍第1項所述之感光性樹脂組成物，其中 該鹼可溶性樹脂，係爲至少一種不飽和羧酸單體與至少一種 不飽和羧酸單體以外之自由基聚合性單體聚合所得的共聚合 物。 3·如申請專利範圍第2項所述之感光性樹脂組成物，其中 該不飽和羧酸單體以外之自由基聚合性單體，係爲包含如式（1) 所示化合物的至少一種的自由基聚合性單體的混合物。 Rl R ⑴ CH2=0l {〇-CH2CH2CH2CH2CH2l 、, Ο、 〇/η 0 (式中心爲H或是甲基，R2爲H或是碳數1〜5的院基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲0〜5的整數） 4·如申請專利範圍第3項所述之感光性樹脂組成物，其中 79 8310-pif2 在式（1)中，n爲1或是2，112爲H。 5. 如申請專利範圍第1項所述之感光性樹脂組成物，其中 該鹼不溶性的具環氧基乙烯基聚合物，係由一具環氧基自由 基聚合性單體的單獨聚合，兩種以上的該具環氧基自由基聚 合性單體的共聚合，或是至少一種具環氧基自由基聚合性單 體與至少一種非不飽和羧酸自由基聚合性單體且不具環氧基 的化合物，共聚合所得的聚合體。 6. 如申請專利範圍第1項所述之感光性樹脂組成物，其中 該其中具二苯甲酮結構有機過氧化物爲如式（2)所表示的化合 物0576950 8310-pif2 Announcement, patent application scope: 1. A photosensitive resin composition, the photosensitive resin composition contains a polymer binder, an ethylene double bond compound, and an organic benzophenone structure Peroxide and a coumarin structure photosensitizer, wherein: the polymer binder is an alkali-soluble resin, or a mixture of the alkali-soluble resin and an alkali-insoluble epoxy-based vinyl polymer And the proportion of the alkali-soluble resin in the polymer binder is about 40 to 100% by weight, relative to the polymer binder, the ethylenic double bond compound is about 10 to 200% by weight, and the dibenzene The ketone structure organic peroxide is about 0.1 to 50% by weight, and the coumarin structure light sensitizer is about 0.1 to 50% by weight. The content of the total solids in the composition is about 10 to 50% by weight. . 2. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the alkali-soluble resin is a radically polymerizable monomer other than at least one unsaturated carboxylic acid monomer and at least one unsaturated carboxylic acid monomer. Copolymer obtained by bulk polymerization. 3. The photosensitive resin composition according to item 2 of the scope of the patent application, wherein the radical polymerizable monomer other than the unsaturated carboxylic acid monomer is one containing at least one compound represented by the formula (1) A mixture of radical polymerizable monomers. Rl R ⑴ CH2 = 0l {〇-CH2CH2CH2CH2CH2l 、, 〇, 〇 / η 0 (where the center of the formula is H or methyl, R2 is H or a courtyard with 1 to 5 carbon atoms, and the 2 to 4 positions of the tetrahydrofuran ring are also (Can be bonded to carbon atoms, η is an integer from 0 to 5) 4. The photosensitive resin composition as described in item 3 of the scope of patent application, wherein 79 8310-pif2 In formula (1), n is 1 or 2 , 112 is H. 5. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the alkali-insoluble epoxy-based vinyl polymer is independently polymerized by an epoxy-radical polymerizable monomer, and two Copolymerization of more than one epoxy radical polymerizable monomer, or at least one epoxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical polymerizable monomer without epoxy A compound obtained by copolymerizing a radical-based compound. 6. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the organic peroxide having a benzophenone structure is a compound represented by the formula (2). ⑺ (式中，R3〜R6爲各別獨立的碳數1〜13的烷基，X1以及Χ2 爲各別獨立的_〇_、-〇_〇_或是-ΝΗ -，一苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與Ρ 位置的碳原子的其中任一個結合） 7. 如申請專利範圍第6項所述之感光性樹脂組成物，其中 在式（2)中，Xi以及Χ2爲-0-。 8. 如申請專利範圍第1項所述之感光性樹脂組成物，其中 該具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙烯酸酯。 9. 如申請專利範圍第1項所述之感光性樹脂組成物，其中 該具乙烯性雙鍵化合物爲3個以上的具乙烯性雙鍵化合物。 576950 8310-pif2 10.如申請專利範圍第1項所述之感光性樹脂組成物，其 中該鹼可溶性樹脂係爲至少一種不飽和羧酸單體與至少一種 不飽和羧酸單體以外之自由基聚合性單體聚合所得的共聚合 物，該不飽和羧酸單體以外之自由基聚合性單體，係爲包含 如式（1)所示化合物的至少一種的自由基聚合性單體的混合 物； CH2=C-C f〇-CH2CH2CH2CH2CH2-C 4-〇-CH2—\⑺ (wherein R3 to R6 are independent alkyl groups having 1 to 13 carbon atoms, and X1 and X2 are each independent _〇_, -〇_〇_ or -NΗ-, a benzophenone structure The carbonyl group may be bonded to any one of the carbon atoms at the P position with respect to the carbon atom of the substituent having a benzene ring. 7. The photosensitive resin composition according to item 6 of the patent application scope, wherein In formula (2), Xi and X2 are -0. 8. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the ethylenic double bond compound is an acrylate and a methacrylate. 9. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the ethylenic double bond compound is three or more ethylenic double bond compounds. 576950 8310-pif2 10. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the alkali-soluble resin is at least one unsaturated carboxylic monomer and at least one unsaturated carboxylic monomer A copolymer obtained by polymerizing a polymerizable monomer, and the radical polymerizable monomer other than the unsaturated carboxylic acid monomer is a mixture of radical polymerizable monomers including at least one kind of a compound represented by the formula (1) ; CH2 = CC f〇-CH2CH2CH2CH2CH2-C 4-〇-CH2— \ Η (1) (式中心爲Η或是甲基，112爲Η或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲0〜5的整數） 該鹼不溶性的具環氧基乙烯基聚合物，係由一具環氧基自由 基聚合性單體的單獨聚合，兩種以上的該具環氧基自由基聚 合性單體的共聚合，或是至少一種具環氧基自由基聚合性單 體與1少一種非不飽和羧酸自由基聚合性單體且不具環氧基 的化合物，共聚合所得的聚合體， 該具二苯甲酮結構有機過氧化物爲如式(2)所表示的化合物，Η (1) (The center of the formula is Η or methyl, 112 is Η or an alkyl group having 1 to 5 carbons, and the 2 to 4 positions of the tetrahydrofuran ring may also be bonded to a carbon atom, and η is an integer of 0 to 5) The alkali-insoluble epoxy-based vinyl polymer is independently polymerized from one epoxy-radical polymerizable monomer, and two or more of the epoxy-radical polymerizable monomers are copolymerized, or A polymer obtained by copolymerizing at least one compound having an epoxy radical polymerizable monomer and at least one unsaturated unsaturated carboxylic acid radical polymerizable monomer without an epoxy group, and having a benzophenone structure. The organic peroxide is a compound represented by formula (2), (式中，r;〜r6爲各別獨立的碳數丨〜13的烷基，Χι以及x2 爲各別獨立的或是—ΝΗ_，二苯甲酮結構 81 8310-pif2 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與P 位置的碳原子的其中任一個結合） 然後，該具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙燦酸酯。 11·一種塗膜，該塗膜以申請專利範圍第1項至第10項的 其中任一項所記載的感光性樹脂組成物作爲材料所形成。 12·—種液晶顯不兀件用間隔件，該液晶顯示元件用間隔 件以申請專利範圍第11項所記載的塗膜所形成。 13·如申請專利範圍第12項所述之液晶顯示元件用間隔 件，其中該液晶顯示元件用間隔件以申請專利範圍第11項所 記載的塗膜以微影步驟圖案化之後，熱硬化以形成。 I4·一種液晶顯7K兀件，該液晶顯示元件具備申請專利範 圍第12項或是第13項所記載的間隔件。 I5·—種光硬化性著色組成物，該光硬化性著色組成物係 於申請專漏_ 1麵記_-感光性_組成物中加入 著色4，其特徵爲相對於一高分子結合劑與一亘乙儲性雙 鍵化σ物的合δ十量，該著色劑含有5〜13〇重量％， 物中 全固形成份的含有毚爲1〇〜5〇重量％左右。 ’、 16·如申請專利範圍第ls項所述之光硬化性著色組成物， 其中該鹼可溶性樹脂，係爲至少一種不飽和羧酸單體與至少 -種不飽彳晴酸單n以外之自由基聚合性單體聚合所得的共 聚合物。 Π.如申請專利範圍第16項所述之光硬化性著色組成物， 其中該不飽和羧酸單體以外之自由基聚合性單體，係爲包含 如式（1)所不化口物的至少一種的自由基聚合性單體的混合 物。 (1) 576950 8310-pif2 Ri ch2=c_s 十〇—〇12〇12〇12〇12〇12_(^ o o (式中心爲11或是甲基，112爲11或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲0〜5的整數） 18. 如申請專利範圍第17項所述之光硬化性著色組成物， 其中在式（1)中，η爲1或是2，112爲Η。 19. 如申請專利範圍第15項所述之光硬化性著色組成物， 其中該鹼不溶性的具環氧基乙烯基聚合物，係由一具環氧基 自由基聚合性單體的單獨聚合，兩種以上的該具環氧基自由 基聚合性單體的共聚合，或是至少一種具環氧基自由基聚合 性單體與至少一種非不飽和羧酸自由基聚合性單體且不具環 氧基的化合物，共聚合所得的聚合體。 20. 如申請專利範圍第15項所述之光硬化性著色組成物， 其中該具二苯甲酮結構有機過氧化物爲如式（2)所表示的化合 物0 R3—0—0——C R5—Xi—C(In the formula, r; ~ r6 are each independent carbon number of 丨 ~ 13, X and x2 are each independently or -NΗ_, benzophenone structure 81 8310-pif2 carbonyl group, relative to The carbon atom of the substituent of the benzene ring may be individually bonded to any one of the carbon atoms at the P position.) Then, the compound having an ethylenic double bond is an acrylate and a methyl propionate. 11. A coating film formed using the photosensitive resin composition described in any one of claims 1 to 10 of the scope of patent application as a material. 12. A spacer for a liquid crystal display device, the spacer for a liquid crystal display element being formed with the coating film described in claim 11 of the scope of patent application. 13. The spacer for a liquid crystal display element according to item 12 in the scope of the patent application, wherein the spacer for the liquid crystal display element is patterned by the lithography step with the coating film described in the scope of the patent application in item 11 and then thermally cured to form. I4. A 7K element for a liquid crystal display, the liquid crystal display element having a spacer as described in the patent application scope item 12 or item 13. I5 · —A photocurable coloring composition, the photocurable coloring composition is added to the application _ 1 side _ _ photosensitivity _ composition added color 4, which is characterized by a polymer binder and The total δ amount of a double-stored double bond sigma compound is 5 to 130% by weight, and the total solid content of the content of 毚 is about 10 to 50% by weight. ', 16. The photocurable coloring composition according to item ls in the scope of the patent application, wherein the alkali-soluble resin is at least one kind of unsaturated carboxylic acid monomer and at least one kind of unsaturated acetic acid monomer n. A copolymer obtained by polymerizing a radical polymerizable monomer. Π. The photocurable coloring composition according to item 16 of the scope of the patent application, wherein the radically polymerizable monomer other than the unsaturated carboxylic acid monomer is a compound containing a chemical substance as shown in formula (1). A mixture of at least one radically polymerizable monomer. (1) 576950 8310-pif2 Ri ch2 = c_s ten-〇12〇12〇12〇12〇12 _ (^ oo (the formula center is 11 or methyl, 112 is 11 or 1 to 5 carbon alkyl group The 2 to 4 positions of the tetrahydrofuran ring may also be bonded to the carbon atom, and η is an integer of 0 to 5) 18. The photocurable coloring composition according to item 17 of the scope of patent application, wherein in formula (1), η is 1 or 2, and 112 is fluorene. 19. The photocurable coloring composition according to item 15 of the scope of patent application, wherein the alkali-insoluble epoxy-based vinyl polymer is made of an epoxy resin. Single radical polymerizable monomer, copolymerization of two or more of the epoxy radical polymerizable monomers, or at least one epoxy radical polymerizable monomer and at least one unsaturated A polymer obtained by copolymerizing a carboxylic acid radically polymerizable monomer and no epoxy group. 20. The photocurable coloring composition according to item 15 of the scope of patent application, wherein the benzophenone structure The organic peroxide is a compound represented by formula (2): 0 R3-0-0—C R5—Xi—C (2) (式中，R3〜R6爲各別獨立的碳數1〜13的烷基，Xi以及X2 爲各別獨立的-0-、-0-0-或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與P 位置的碳原子的其中任一個結合） 83 576950 8310-pif2 21. 如申請專利範圍第20項所述之光硬化性著色組成物， 其中在式(2)中，Xi以及义2爲-0-。 22. 如申請專利範圍第15項所述之光硬化性著色組成物， 其中該具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙烯酸酯。 23. 如申請專利範圍第15項所述之光硬化性著色組成物， 其特徵爲該鹼可溶性樹脂係爲至少一種不飽和羧酸單體與至 少一種不飽和羧酸單體以外之自由基聚合性單體聚合所得的 共聚合物，該不飽和羧酸單體以外之自由基聚合性單體，係 爲包含如式（1)所示化合物的至少一種的自由基聚合性單體的 混合物，(2) (wherein R3 to R6 are independent alkyl groups having 1 to 13 carbon atoms, and Xi and X2 are each independently -0-, -0-0-, or -NH-, dibenzoyl The carbonyl group of the ketone structure may be bonded to any one of the carbon atoms at the P position with respect to the carbon atom of the substituent having a benzene ring. 83 576950 8310-pif2 21. As described in item 20 of the scope of application In the photocurable coloring composition, in Formula (2), Xi and Yi 2 are -0-. 22. The photocurable coloring composition according to item 15 of the scope of the patent application, wherein the ethylenic double bond compound is an acrylate and a methacrylate. 23. The photocurable coloring composition according to item 15 of the scope of the patent application, wherein the alkali-soluble resin is a radical polymerization of at least one unsaturated carboxylic acid monomer and at least one unsaturated carboxylic acid monomer. A copolymer obtained by polymerizing a monomer, and the radical polymerizable monomer other than the unsaturated carboxylic acid monomer is a mixture of radical polymerizable monomers including at least one kind of a compound represented by formula (1). (式中心爲Η或是甲基，112爲Η或是碳數1〜5的烷基，四氫 呋喃環的2〜4位置亦可以與碳原子結合，η爲〇〜5的整數） 該鹼不溶性的具環氧基乙烯基聚合物，係由一具環氧基自由 基聚合性單體的單獨聚合，兩種以上的該具環氧基自由基聚 合性單體的共聚合，或是至少一種具環氧基自由基聚合性單 體與至少一種非不飽和羧酸自由基聚合性單體且不具環氧基 的化合物，共聚合所得的聚合體， 該具二苯甲酮結構有機過氧化物爲如式(2)所表示的化合物， 84 '1576950 8310-pif2(The center of the formula is fluorene or methyl, 112 is fluorene or an alkyl group having 1 to 5 carbons, and the 2 to 4 position of the tetrahydrofuran ring can also be bonded to a carbon atom, and η is an integer of 0 to 5) The base is insoluble Epoxy-based vinyl polymers are independently polymerized from one epoxy-based radically polymerizable monomer, two or more of the epoxy-based radically polymerizable monomers are copolymerized, or at least one is A polymer obtained by copolymerizing an epoxy radical polymerizable monomer and at least one unsaturated carboxylic acid radical polymerizable monomer and having no epoxy group. The organic peroxide having a benzophenone structure is Compound represented by formula (2), 84'1576950 8310-pif2 If (式中，R3〜R6爲各別獨立的碳數1〜13的烷基，Xi以及X2 爲各別獨立的或是-NH-，二苯甲酮結構 的羰基，相對於具苯環的置換基的碳原子，亦可以各別與P 位置的碳原子的其中任一個結合） 然後，該具乙烯性雙鍵化合物爲丙烯酸酯以及甲基丙烯 酸酯。 24. —種塗膜，該塗膜係以申請專利範圍第15項至第23 項的其中任一項所記載的光硬化性著色組成物塗佈於基板表 面，於30〜300°C乾燥，以得到膜厚爲0.1〜10//的該塗膜。 25. —種濾色鏡，適用於液晶顯示元件，該濾色鏡係以申 請專利範圍第24項所記載的塗膜，藉由描繪有圖案的罩幕， 以波長爲190nm〜450nm，照射能量爲1〜1000mJ/cm的放射 線照射，接著使用無機鹼或是有機鹼的水溶液顯影以去除不 要的部分，再於180〜250°C烘烤以形成。 26. 如申請專利範圍第25項所述之濾色鏡，其中該濾色鏡 以申請專利範圍第24項所記載的塗膜以微影步驟圖案化之 後，熱硬化以形成。 85If (In the formula, R3 to R6 are each independent alkyl groups having 1 to 13 carbons, Xi and X2 are each independent or -NH-, benzophenone structure carbonyl groups, compared to The carbon atom of the substituent may be individually bonded to any one of the carbon atoms at the P position.) Then, the ethylenic double bond compound is an acrylate and a methacrylate. 24. A coating film which is coated on the surface of a substrate with the photocurable coloring composition described in any one of claims 15 to 23 of the scope of patent application, and dried at 30 to 300 ° C. In order to obtain the coating film having a film thickness of 0.1 to 10 //. 25. A color filter suitable for a liquid crystal display device. The color filter is a coating film described in item 24 of the scope of patent application, a patterned mask, a wavelength of 190 nm to 450 nm, and an irradiation energy of 1 to 1000 mJ. / cm of radiation, followed by development with an inorganic or organic alkali aqueous solution to remove unnecessary parts, and then baked at 180 ~ 250 ° C to form. 26. The color filter as described in claim 25, wherein the color filter is patterned by a lithography step with the coating film described in claim 24, and then formed by heat curing. 85 爲第90124787號中文說明書無劃線修正本 修正日期 發明專利說明書 (本說明書格式、順序及粗體字，請勿任意更動，※記號部分請勿填寫 ※申請案號：％/二^^ 92年8月19臼576950 ) ※申請曰期：一岈 壹、發明名稱：（中文/英文) ※工卩。分類： f//337 感光性樹脂組成物、間隔件形成材料、瀘色鏡形成材料及 液晶顯示元件 PHOTOSENSITIVE RESIN COMPOUND, SPACER FORMING MATERIAL，COLORFILTER FORMING MATERIAL AND THE LIQUID CRYSTAL DISPLAY DEVICE 貳、申請人：（共1人) 姓名或名稱：（中文/英文） 智索股份有限公司/ CHISSO CORPORATION 代表人··（中文/英文）後藤舜吉/ShunkichiGOTO 住居所或營業所地址：（中文/英文） 曰本大阪府大阪市北區中之島三丁目6番32號 6-32,Nakanoshima 3-chome, Kita-ku, Osaka-shi, Osaka, JAPAN 國籍：（中文/英文）曰本/JAPAN 參、發明人：（共5人） 姓名：（中文/英文） 1. 大泉史貴/ FumitakaOIZUMI 2. 三谷清樹/SeikiMITANI 3·渡邊英司/EijiWATANABE 4·伊丹節男 /Setsuo ITAMI 5.大塚信之/NobuyukiOTSUKA 1Amendments to the Chinese Specification No. 90124787 without the underlined amendments. The invention patent specification (the format, order, and bold type of this specification, please do not change it arbitrarily. ※ Please do not fill in the marked part. ※ Application number:% / 二 ^^ 1992 August 19, 576950) ※ Application date: one day, one invention name: (Chinese / English) ※ Gongye. Category: f // 337 Photosensitive resin composition, spacer forming material, cyan lens forming material, and liquid crystal display element PHOTOSENSITIVE RESIN COMPOUND, SPACER FORMING MATERIAL, COLORFILTER FORMING MATERIAL AND THE LIQUID CRYSTAL DISPLAY DEVICE 申请人, applicant: (total 1 person) Name or name: (Chinese / English) Representative of Chisso Corporation / CHISSO CORPORATION · (Chinese / English) Goto Shunji / ShunkichiGOTO Address or office of business: (Chinese / English) Osaka Nakanoshima 3-chome, 6-32, Nakanoshima 3-chome, Kita-ku, Osaka-shi, Osaka, JAPAN, Kita-ku, Osaka Nationality: (Chinese / English) Japanese / JAPAN Participants and inventors: (Total 5 People) Name: (Chinese / English) 1. Oizumi Shiki / FumitakaOIZUMI 2. Mitani Kiyoshi / SeikiMITANI 3. · Watanabe Hideki / EijiWATANABE 4 · Itami Festival Male / Setsuo ITAMI 5. Otsuka Nobuyuki / NobuyukiOTSUKA 1
TW090124787A 2000-12-27 2001-10-08 Photosensitive resin compound, spacer, forming material, colorfilter forming material and the liquid crystal display device TW576950B (en)

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JPH0973171A (en) * 1995-09-05 1997-03-18 Kansai Paint Co Ltd Photosensitive colored composition and production of color filter
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