TWI407216B - Photosensitive resin composition for spacer - Google Patents
Photosensitive resin composition for spacer Download PDFInfo
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- TWI407216B TWI407216B TW094126722A TW94126722A TWI407216B TW I407216 B TWI407216 B TW I407216B TW 094126722 A TW094126722 A TW 094126722A TW 94126722 A TW94126722 A TW 94126722A TW I407216 B TWI407216 B TW I407216B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
- G03F7/0005—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
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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
-
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Liquid Crystal (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
本發明係有關一種間隔子用之感光性樹脂組成物，詳而言之，本發明係有關一種可減少因液晶滴下量而產生未充填的不良情況，亦可防止彩色濾光板因壓力而在板面上產生損傷，不僅可克服在製程時所產生的厚度偏差，亦可在離子、雜質不溶出至液晶中之情形下不降低電壓保持率且不會在液晶配向時產生影響，同時具有優異的耐摩擦性、充分的電壓保持率及液晶配向性，且形成有具顯像性、高感應性、熱穩定性、尺寸穩定性及優異的耐壓強度之間隔子的間隔子用感光性樹脂組成物。The present invention relates to a photosensitive resin composition for a spacer. In particular, the present invention relates to a problem that can reduce the unfilling due to the amount of liquid crystal dropping, and can prevent the color filter from being pressed on the plate due to pressure. Damage on the surface not only overcomes the thickness deviation generated during the process, but also does not lower the voltage holding ratio in the case where ions and impurities are not eluted into the liquid crystal, and does not affect the liquid crystal alignment, and has excellent effects. A spacer composed of a photosensitive resin having a friction resistance, a sufficient voltage holding ratio, and a liquid crystal alignment property, and having a spacer having high developability, high inductivity, thermal stability, dimensional stability, and excellent compressive strength. Things.
在液晶面板與觸碰式面板中使用間隔子顆粒，以維持彩色濾光板與薄膜電晶體之基板間一定的間隔，而該間隔子顆粒主要係使用特定顆粒大小的玻璃珠或塑膠珠。由於前述間隔子顆粒係任意散佈在基板上，因此當間隔子存在於有效像素部內時，會看到間隔子或因妨礙到液晶的移動而降低液晶面板的對比度。Spacer particles are used in the liquid crystal panel and the touch panel to maintain a certain interval between the color filter and the substrate of the thin film transistor, and the spacer particles mainly use glass beads or plastic beads of a specific particle size. Since the spacer particles are arbitrarily dispersed on the substrate, when the spacer is present in the effective pixel portion, the spacer is seen or the contrast of the liquid crystal panel is lowered by hindering the movement of the liquid crystal.
因此已提出以微影法在有效像素部外形成感光性間隔子的方法。該方法係利用旋轉速度而可自由調整晶胞間隔，因此不只可解決為了使用習知珠粒作為間隔子來調整液晶面板中晶胞間隔而必須買進新顆粒大小之珠粒的不便，亦具有可使用預定的遮罩來自由調整賦與決定物理特徵的圖案形狀及尺寸的優點。Therefore, a method of forming a photosensitive spacer outside the effective pixel portion by the lithography method has been proposed. The method can freely adjust the cell spacing by using the rotation speed, and therefore can not only solve the inconvenience of buying a new particle size bead in order to adjust the cell spacing in the liquid crystal panel by using the conventional bead as a spacer, and can also be used. The predetermined mask comes from the advantage of adjusting the shape and size of the pattern that determines the physical characteristics.
另一方面，在製造液晶面板與觸碰式面板之製程中，在基板上形成由感光性樹脂組成之間隔子之後，可利用各式各樣的方法來形成配向膜，但在一般地塗布、乾燥配向劑而形成配向塗膜之後，主要係使用摩擦的方法來形成配向膜。在該情況下，若因前述摩擦而使間隔子或配向膜剝離，則會發生顯示不良，而若在配向膜上有因感光性樹脂組成物所產生的殘留物，則液晶配向性也會發生異常。又，由於間隔子在液晶面板或觸碰式面板中係直接接觸液晶，因此若從間隔子中溶出離子性物質或雜質，則會降低電壓保持率。On the other hand, in the process of manufacturing a liquid crystal panel and a touch panel, after forming a spacer composed of a photosensitive resin on a substrate, an alignment film can be formed by various methods, but in general, After the alignment agent is dried to form an alignment coating film, the alignment film is mainly formed by a friction method. In this case, if the spacer or the alignment film is peeled off due to the rubbing, display failure occurs, and when there is a residue due to the photosensitive resin composition on the alignment film, liquid crystal alignment also occurs. abnormal. Further, since the spacer directly contacts the liquid crystal in the liquid crystal panel or the touch panel, if the ionic substance or the impurity is eluted from the spacer, the voltage holding ratio is lowered.
因此，由該感光性樹脂所組成的間隔子必須是一種不影響電壓保持率、具有高度的耐摩擦性及不影響液晶配向的間隔子，另外該間隔子也需要具有顯像性、高感應性、熱穩定性、尺寸穩定性。Therefore, the spacer composed of the photosensitive resin must be a spacer which does not affect the voltage holding ratio, has high abrasion resistance, and does not affect the alignment of the liquid crystal, and the spacer also needs to have developability and high sensitivity. , thermal stability, dimensional stability.
初期的間隔子樹脂組成物係利用環氧丙烯酸系樹脂與鹼溶性丙烯酸酯樹脂來提升圖案形狀、解析度、電壓保持率、耐摩擦性、顯像性、高感應性、熱穩定性及尺寸穩定性等特性及用以提升在薄膜電晶板與彩色濾光板結合時給予影響的變形量與復原力之硬化特性及硬化度。但過度重視可使如此間隔子因耐壓強度及外力而變形後恢復到原本的晶胞間隔之高度復原能力，因此該間隔子有變硬的傾向。由於堅硬的間隔子無法吸收外力，因此有損傷或破壞薄膜電晶板及彩色濾光板的缺點。The initial spacer resin composition utilizes an epoxy acrylic resin and an alkali-soluble acrylate resin to enhance pattern shape, resolution, voltage holding ratio, abrasion resistance, development, high sensitivity, thermal stability, and dimensional stability. Characteristics such as properties and hardening characteristics and hardening degree for improving the amount of deformation and restoring force which are affected when the thin film crystal plate is combined with the color filter. However, excessive attention is paid to the fact that the spacer can be deformed by the compressive strength and the external force and restored to the original cell spacing, so that the spacer tends to become hard. Since the hard spacer cannot absorb external force, it has the disadvantage of damaging or destroying the thin film crystal plate and the color filter.
又，以往，在薄膜電晶板與彩色濾光板結合之後，為了縮短以真空注入液晶之充填製程時間，已開發出可同時滴下液晶且結合薄膜電晶板與彩色濾光板之新製程。但由於習知間隔子的變形量不足，因此液晶滴下製程時的邊緣會不足而產生不良之情形。Further, in the related art, in order to shorten the filling process time for vacuum injection of liquid crystal after the combination of the thin film crystal plate and the color filter, a new process for simultaneously dropping the liquid crystal and combining the thin film crystal plate and the color filter has been developed. However, since the amount of deformation of the conventional spacer is insufficient, the edge at the time of the liquid crystal dropping process may be insufficient to cause a problem.
本發明之目的係在提供一種可解決前述習知中技術之問題，且可減少因液晶滴下量所產生的未充填範圍之不良，並且可防止彩色濾光板因壓力而在板面上產生損傷，亦可克服製程時所發生的厚度偏差的間隔子用之感光性樹脂組成物。SUMMARY OF THE INVENTION The object of the present invention is to provide a problem that can solve the above-mentioned prior art, and can reduce the defect of the unfilled range caused by the amount of liquid crystal dripping, and can prevent the color filter from being damaged on the board surface due to pressure. It is also possible to overcome the photosensitive resin composition for the spacer which varies in thickness during the process.
本發明之另一目的係在提供一種不會溶出離子、雜質至液晶中，且不會降低電壓保持率，亦不會在液晶配向時產生影響的感光性樹脂組成物。Another object of the present invention is to provide a photosensitive resin composition which does not elute ions or impurities into a liquid crystal, does not lower the voltage holding ratio, and does not affect the liquid crystal alignment.
又，本發明之其他目的係在提供一種具有優異的耐摩擦性、充分的電壓保持率及液晶配向性，並形成有具顯像性、高感應性、熱穩定性、尺寸穩定性及優異的耐壓強度之間隔子的間隔子用之感光性樹脂組成物。Further, another object of the present invention is to provide an excellent friction resistance, a sufficient voltage holding ratio, and a liquid crystal alignment property, and to have developability, high inductivity, thermal stability, dimensional stability, and excellent properties. A photosensitive resin composition for the spacer of the spacer of the pressure resistance.
又，本發明之另一目的係在提供由感光性樹脂組成物所形成之間隔子及該間隔子之製造方法。Further, another object of the present invention is to provide a spacer formed of a photosensitive resin composition and a method of producing the spacer.
又，本發明之又一目的係在提供可使用前述間隔子之液晶顯示元件。Still another object of the present invention is to provide a liquid crystal display element which can use the aforementioned spacer.
為了達到前述之目的，本發明係提供一種間隔子用之感光性樹脂組成物，包含有：a)選自於由i)鹼溶性丙烯酸酯樹脂、ii)光聚合物、及iii)其混合物所構成之群的樹脂；b)胺基甲酸酯樹脂；c)至少具有兩個以上乙烯系雙鍵的交聯性單體；d)光聚合引發劑；及e)溶劑。In order to achieve the above object, the present invention provides a photosensitive resin composition for a spacer comprising: a) selected from the group consisting of i) an alkali-soluble acrylate resin, ii) a photopolymer, and iii) a mixture thereof. a group of resins; b) a urethane resin; c) a crosslinkable monomer having at least two ethylene double bonds; d) a photopolymerization initiator; and e) a solvent.
又，本發明以包含有：a)選自於由i)鹼溶性丙烯酸酯樹脂、ii)光聚合物、及iii)其混合物所構成之群，且重量百分率為5至50的樹脂；b)重量百分率為1至10的胺基甲酸酯樹脂；c)重量百分率為5至50且至少具有兩個以上乙烯系雙鍵的交聯性單體；d)重量百分率為0.5至5的光聚合引發劑；及e)剩餘量的溶劑為佳。Further, the present invention comprises: a) a resin selected from the group consisting of i) an alkali-soluble acrylate resin, ii) a photopolymer, and iii), and a resin having a weight percentage of 5 to 50; b) a urethane resin having a weight percentage of 1 to 10; c) a crosslinkable monomer having a weight percentage of 5 to 50 and having at least two ethylene double bonds; d) photopolymerization having a weight percentage of 0.5 to 5 The initiator; and e) the remaining amount of solvent is preferred.
又，本發明係提供一種使用間隔子用之感光性樹脂組成物的間隔子之形成方法。Moreover, the present invention provides a method of forming a spacer using a photosensitive resin composition for a spacer.
又，本發明係提供一種由間隔子用之感光性樹脂組成物所形成的間隔子。Further, the present invention provides a spacer formed of a photosensitive resin composition for a spacer.
又，本發明係提供一種可使用間隔子之液晶顯示元件。Further, the present invention provides a liquid crystal display element which can use a spacer.
本發明之間隔子用感光性樹脂組成物具有可減少因液晶滴下量而產生未充填的不良情況，亦可防止彩色濾光板因壓力而在板面上產生損傷，不僅可克服在製程時所產生的厚度偏差，亦可在離子、雜質不溶出至液晶中之情形下不降低電壓保持率且不會在液晶配向時產生影響的效果。又，本發明之間隔子用感光性樹脂組成物具有優異的耐摩擦性、充分的電壓保持率及液晶配向性，亦具有顯像性、熱穩定性、尺寸穩定性、優異的耐壓強度及間隔子柔軟性的效果。The photosensitive resin composition for spacers of the present invention has the problem of reducing the unfilling due to the amount of liquid crystal dropping, and also preventing the color filter from being damaged on the surface due to pressure, and not only can be overcome during the process. The thickness deviation may not reduce the voltage holding ratio in the case where ions or impurities are not eluted into the liquid crystal, and does not have an effect of affecting the liquid crystal alignment. Moreover, the photosensitive resin composition for spacers of the present invention has excellent rubbing resistance, sufficient voltage holding ratio, and liquid crystal alignment, and also has developability, thermal stability, dimensional stability, and excellent pressure resistance. The effect of spacer softness.
以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.
本發明之間隔子用之感光性樹脂組成物係包含有：a)選自於由i)鹼溶性丙烯酸酯樹脂、ii)、及iii)其混合物所構成之群的樹脂；b)胺基甲酸酯樹脂；c)至少具有兩個以上乙烯系雙鍵的交聯性單體；d)光聚合引發劑；及e)溶劑。The photosensitive resin composition for a spacer of the present invention comprises: a) a resin selected from the group consisting of i) an alkali-soluble acrylate resin, ii), and iii); b) an amine group A An acid ester resin; c) a crosslinkable monomer having at least two ethylene double bonds; d) a photopolymerization initiator; and e) a solvent.
本發明所使用之前述a)之樹脂係可單獨使用鹼溶性丙烯酸酯樹脂、單獨使用光聚合物或混合使用鹼溶性丙烯酸酯樹脂與光聚合物，且以混合使用鹼溶性丙烯酸酯樹脂與光聚合物特佳。The resin of the above a) used in the present invention may be an alkali-soluble acrylate resin alone, a photopolymer alone or a mixture of an alkali-soluble acrylate resin and a photopolymer, and a mixture of an alkali-soluble acrylate resin and photopolymerization. Excellent.
前述a)i)之鹼溶性丙烯酸酯樹脂係在高分子鏈中具有乙烯系酸性基之單體與不具有乙烯系酸性基之單體的共聚體。The alkali-soluble acrylate resin of the above a) i) is a copolymer of a monomer having a vinyl-based acidic group and a monomer having no vinyl-based acidic group in the polymer chain.
作為前述具有乙烯系酸性基之單體之例有丙烯酸、甲基丙烯酸、依康酸、順丁烯二酸、延胡索酸、乙酸乙烯酯或其酸酐、2-丙烯醯氧乙基氫鄰苯二甲酸酯、2-丙烯醯氧丙基氫鄰苯二甲酸酯、及2-丙烯醯氧丙基六氫鄰苯二甲酸酯等。Examples of the monomer having a vinylic acid group include acrylic acid, methacrylic acid, isaconic acid, maleic acid, fumaric acid, vinyl acetate or an anhydride thereof, and 2-propenyloxyethyl hydrogen phthalate. An acid ester, 2-propenyl isopropyl propyl hydrogen phthalate, 2-propenyl oxypropyl hexahydrophthalate, and the like.
作為前述不具有乙烯酸性基之單體之例有丙烯酸異丁酯、丙烯酸叔丁酯、丙烯酸月桂酯、甲基丙烯酸甲酯、丙烯酸烷基酯、硬脂丙烯酸酯、丙烯酸環己酯、丙烯酸異冰片酯、甲基丙烯酸苄酯、丙烯酸苄酯、2-羥基丙烯酸酯、丙烯酸三甲氧丁酯、二甘醇一乙醚丙烯酸酯、丙烯酸苯氧乙酯、4-羥丁基丙烯酸酯、苯氧聚乙二醇丙烯酸酯、丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、2-丙烯醯氧乙基-2-羥丙基鄰苯二甲酸酯、丙烯酸2-羥基-3-苯氧丙酯及其甲基丙烯酸酯類；如丙烯酸3-氟乙酯、丙烯酸4-氟丙酯之含鹵素化合物的丙烯酸酯及其甲基丙烯酸酯類；如丙烯酸三乙基矽氧烷基乙酯之含矽氧烷基之丙烯酸酯及其甲基丙烯酸酯類；或是如苯乙烯、4-甲氧基苯乙烯之具有芳族的烯烴類等。又，其可單獨或混合兩種以上使用。Examples of the monomer having no ethylene acidic group include isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, stearic acrylate, cyclohexyl acrylate, and acrylic acid. Borneol ester, benzyl methacrylate, benzyl acrylate, 2-hydroxy acrylate, trimethyl butyl acrylate, diethylene glycol monoethyl acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy poly Ethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-propenyl oxiranyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropane acrylate Esters and their methacrylates; such as 3-fluoroethyl acrylate, 4-fluoropropyl acrylate, halogen-containing acrylates and methacrylates thereof; such as triethylsulfonyl acrylate A decyloxy group-containing acrylate and a methacrylate thereof; or an aromatic olefin such as styrene or 4-methoxystyrene. Further, these may be used alone or in combination of two or more.
前述鹼溶性丙烯酸酯樹脂特別係以聚合丙烯酸苄酯、甲基丙烯酸及甲基丙烯酸甲酯，且重量平均分子量為15000至35000為佳；尤以丙烯酸苄酯：甲基丙烯酸：甲基丙烯酸甲酯聚合的比率為60：20：20，且重量平均分子量為20000之共聚物最佳。The alkali-soluble acrylate resin is particularly polymerized with benzyl acrylate, methacrylic acid and methyl methacrylate, and preferably has a weight average molecular weight of 15,000 to 35,000; especially benzyl acrylate: methacrylic acid: methyl methacrylate The polymerization ratio is 60:20:20, and the copolymer having a weight average molecular weight of 20,000 is most preferable.
前述化學式1或化學式2中，R1 係各自獨立的氫或碳數為1~2之烷基，R2 係被或未被羥基取代之碳數為2~5之烷基。又，a＋b＋c＝1，且0.1<a<0.4、0<b<0.5、0.1<c<0.5。In the above Chemical Formula 1 or Chemical Formula 2, R 1 is each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and R 2 is an alkyl group having 2 to 5 carbon atoms which are or are not substituted with a hydroxyl group. Further, a+b+c=1, and 0.1<a<0.4, 0<b<0.5, and 0.1<c<0.5.
前述化學式3中，R係烷或羥，X係氫或甲基。In the above Chemical Formula 3, R is an alkane or a hydroxyl group, and X is a hydrogen or a methyl group.
前述光聚合物的重量平均分子量係以10000至80000為佳，而尤以15000至50000為佳。當前述光聚合物之重量平均分子量在前述範圍內時，對於顯像的時間與除去殘膜的程度更有幫助。The photopolymer preferably has a weight average molecular weight of from 10,000 to 80,000, particularly preferably from 15,000 to 50,000. When the weight average molecular weight of the aforementioned photopolymer is within the above range, it is more helpful for the time of development and the degree of removal of the residual film.
如此的鹼溶性丙烯酸酯樹脂光與聚合物係以含有重量百分比為5至50之各自單獨或混合的感光性樹脂組成物為佳。當該含量在前述範圍內時，可得到適當黏度的間隔子用之感光性樹脂組成物，具有容易調整厚度之優點。Such an alkali-soluble acrylate resin light and polymer are preferably contained in a photosensitive resin composition of 5 to 50% by weight or not. When the content is within the above range, a photosensitive resin composition for a spacer having an appropriate viscosity can be obtained, and the thickness can be easily adjusted.
本發明之間隔子用之感光性樹脂組成物係含有b)胺基甲酸酯樹脂，且前述胺基甲酸酯樹脂係以下述化學式4表示之化合物為佳。The photosensitive resin composition for a spacer of the present invention contains b) a urethane resin, and the urethane resin is preferably a compound represented by the following Chemical Formula 4.
前述化學式4中，R3 係脂肪族、環狀脂肪族或芳族化合物，x係1至20之整數，且R3 宜為亞甲基(x=1~6)或亞苯基(x=1~2)。又，R4 及R5 係各自獨立之氫、烷基或芳族化合物。In the above Chemical Formula 4, R 3 is an aliphatic, cyclic aliphatic or aromatic compound, x is an integer of 1 to 20, and R 3 is preferably a methylene group (x = 1 to 6) or a phenylene group (x = 1~2). Further, R 4 and R 5 are each independently a hydrogen, an alkyl group or an aromatic compound.
前述胺基甲酸酯樹脂係以含有重量百分比為1至10的感光性樹脂組成物為佳。當該含量不足重量百分比1時，會無法實現間隔子用之感光性樹脂組成物的柔軟度。又，當該含量超過重量百分比10時，則會降低顯像性及黏著力。The urethane resin is preferably a photosensitive resin composition containing from 1 to 10% by weight. When the content is less than the weight percentage of 1, the softness of the photosensitive resin composition for the spacer may not be achieved. Further, when the content exceeds 10% by weight, the developability and adhesion are lowered.
本發明所使用之前述c)之至少具有兩個以上乙烯系雙鍵的交聯性單體係可使用以下述化學式5表示之胺基甲酸酯單體、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、四丙烯酸季戊四醇酯、三甘醇二丙烯酸酯、聚乙二醇二丙烯酸酯、一縮二季戊四醇二丙烯酸酯、山糖醇三丙烯酸酯、雙酚A二丙烯酸酯衍生物、三甲基丙烷三丙烯酸酯、一縮二季戊四醇聚丙烯酸酯、及其甲基丙烯酸酯類等，且特別是以使用以下述化學式5表示之胺基甲酸酯單體為佳。The crosslinkable single system having at least two vinyl double bonds of the above c) used in the present invention may be a urethane monomer represented by the following Chemical Formula 5, 1,4-butanediol diacrylic acid. Ester, 1,3-butanediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, mountain sugar An alcohol triacrylate, a bisphenol A diacrylate derivative, a trimethylpropane triacrylate, a dipentaerythritol polyacrylate, a methacrylate thereof, and the like, and particularly, represented by the following Chemical Formula 5 A urethane monomer is preferred.
前述化學式5中，R6 係脂肪族、環狀脂肪族或芳族化合物，y及z係各自獨立的1至6之整數，且宜為亞甲基(y=1~6、z=1~6)或亞苯基(y=1~2、z=1~6)。又，R7 係-C(CH3 )2 C6 H4 C(CH3 )=CH2 、-O(R)X OC(O)C(R’)=CH2 、 -O(R)X OC(O)C(R’)=CH2 或-C6 H4 C(CH3 )=CH2 。In the above Chemical Formula 5, R 6 is an aliphatic, cyclic aliphatic or aromatic compound, and y and z are each independently an integer of 1 to 6, and preferably a methylene group (y=1 to 6, z=1~). 6) or phenylene (y = 1 ~ 2, z = 1 ~ 6). Further, R 7 is -C(CH 3 ) 2 C 6 H 4 C(CH 3 )=CH 2 , -O(R) X OC(O)C(R')=CH 2 , -O(R) X OC(O)C(R')=CH 2 or -C 6 H 4 C(CH 3 )=CH 2 .
前述至少具有兩個以上乙烯系雙鍵的交聯性單體係以含有重量百分比為5至20的感光性樹脂組成物為佳。當該含量不足重量百分比5時，會無法實現間隔子用之感光性樹脂組成物的柔軟度。又，當該含量超過重量百分比20時，則會降低顯像性及黏著力。The crosslinkable single system having at least two or more vinyl double bonds is preferably a photosensitive resin composition containing 5 to 20% by weight. When the content is less than 5 by weight, the softness of the photosensitive resin composition for the spacer cannot be achieved. Further, when the content exceeds 20% by weight, the developability and adhesion are lowered.
本發明所使用之前述d)之光聚合引發劑係可藉可見光、紫外線、遠紫外線等的波長而進行引發前述交聯性單體之聚合的作用。The photopolymerization initiator of the above d) used in the present invention can effect polymerization of the crosslinkable monomer by a wavelength such as visible light, ultraviolet light or far ultraviolet light.
又，前述光聚合引發劑係可使用三氮系化合物、安息香系化合物、苯乙酮系化合物、氧二苯甲酮系化合物或咪唑系化合物等。具體而言，前述光聚合引發劑係可使用2,4-雙三氯甲基-6-p-甲氧苯乙烯基-s-三氮、2-p-甲氧苯乙烯基-4,6-雙三氯甲基-s-三氮、2,4-三氯甲基-6-三氮、2,4-三氯甲基-4-甲萘基-6-三氮等的三氮系化合物；二苯甲酮、p-(二乙胺基)二苯甲酮等的安息香系化合物；2,2-二氯-4-苯氧基苯乙酮、2,2-二乙氧基苯乙酮、2,2-二丁氧基苯乙酮、2-羥基-2-甲基苯丙酮、p-t-丁基三氯苯乙酮等的苯乙酮系化合物；氧二苯甲酮、噻吨酮、2-甲基噻吨酮、2-異丁基噻吨酮、2-十二烷基噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮等的氧二苯甲酮系化合物；或2,2-雙-2-氯苯基-4,5,4,5-四苯基-2-1,2-雙咪唑、及2,2-雙(2,4,6-三氰基苯基)-4,4,5,5-四苯基-1,2-雙咪唑等的咪唑系化合物。Further, the photopolymerization initiator may be a trinitrogen A compound, a benzoin-based compound, an acetophenone-based compound, an oxybenzophenone-based compound, or an imidazole-based compound. Specifically, the photopolymerization initiator may be 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazo. 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazole 2,4-trichloromethyl-6-triazine 2,4-trichloromethyl-4-methylnaphthyl-6-triazo Trinitrogen a benzoin compound such as benzophenone or p-(diethylamino)benzophenone; 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxy An acetophenone compound such as acetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone or pt-butyltrichloroacetophenone; oxybenzophenone, Thioxanthone, 2-methylthioxanthone, 2-isobutylthioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthiophene An oxybenzophenone compound such as ton ketone; or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, and 2,2 An imidazole compound such as bis(2,4,6-tricyanophenyl)-4,4,5,5-tetraphenyl-1,2-bisimidazole.
前述光聚合引發劑係以含有重量百分比為0.5至5的感光性樹脂組成物為佳，且以含有重量百分比1至2更佳。當該含量不足重量百分比0.5時，硬化度會下降，且因靈敏度低而難以實現正常的間隔子形狀，並且圖案之直線傳播性亦不佳。又，若該含量超過重量百分比5時，則在封裝穩定性上會發生問題，且因硬化度高而使解析度降低，因此在形成有圖案以外的部分容易發生殘膜。The photopolymerization initiator is preferably a photosensitive resin composition containing 0.5 to 5 parts by weight, and more preferably 1 to 2 parts by weight. When the content is less than 0.5 by weight, the degree of hardening is lowered, and since the sensitivity is low, it is difficult to achieve a normal spacer shape, and the linearity of the pattern is also poor. In addition, when the content exceeds 5 by weight, problems occur in package stability, and since the degree of hardening is high, the resolution is lowered. Therefore, a film remaining in a portion other than the pattern is likely to occur.
本發明所使用之前述e)之溶劑係依溶解性、塗層性來選擇，具體而言，前述e)之溶劑係可使用丙二醇單乙醚乙酸酯、乙氧基丙酸乙酯、丁基乙酸、乙二醇單甲醚乙酸酯、丙二醇單甲醚、丙二醇甲醚乙酸酯、二乙二醇二甲醚、二乙二醇甲乙醚、環己酮、3－甲氧基丙酸乙酯或3－乙氧基丙酸甲酯等。其中特別係以使用丙二醇單乙醚乙酸酯、乙氧基丙酸乙酯或丁基乙酸為佳。The solvent of the above e) used in the present invention is selected depending on the solubility and coating properties. Specifically, the solvent of the above e) may be propylene glycol monoethyl ether acetate, ethyl ethoxy propionate or butyl. Acetic acid, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxypropionic acid Ethyl ester or methyl 3-ethoxypropionate. Among them, propylene glycol monoethyl ether acetate, ethyl ethoxy propionate or butyl acetic acid is particularly preferred.
前述溶劑之含量因黏度或組成物內總固體含量而有所不同，且當然可含有除去使用於間隔子用組成物之固體含量後所殘留的剩餘量。特別是對於使用溶劑的總量係以含有重量百分比為40~80的丙二醇單乙醚乙酸酯、重量百分比為15~40的乙氧基丙酸乙酯及重量百分比為1~20的丁基乙酸為最佳，且混合使用的比率以丙二醇單乙醚乙酸酯：乙氧基丙酸乙酯：丁基乙酸＝6：3：1為佳。當前述溶劑包含在前述範圍內時，由於無法克服厚度的偏差，因此會降低間隔子用感光性樹脂組成物的均等性。The content of the aforementioned solvent varies depending on the viscosity or the total solid content in the composition, and may of course contain the remaining amount remaining after removing the solid content used for the spacer composition. In particular, the total amount of solvent used is propylene glycol monoethyl ether acetate containing 40 to 80% by weight, ethyl ethoxypropionate in an amount of 15 to 40% by weight, and butyl acetic acid in an amount of 1 to 20% by weight. Most preferred, and the ratio used in combination is preferably propylene glycol monoethyl ether acetate: ethyl ethoxypropionate: butyl acetic acid = 6:3:1. When the solvent is contained in the above range, since the variation in thickness cannot be overcome, the uniformity of the photosensitive resin composition for spacers is lowered.
由該成分所組成的本發明之間隔子用感光性樹脂組成物係依需要而可更包含f)至少含有兩個以上雙鍵之交聯性丙烯基單體。又，前述至少含有兩個以上雙鍵之交聯性丙烯基單體係可使用1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、四丙烯酸季戊四醇酯、三甘醇二丙烯酸酯、聚乙二醇二丙烯酸酯、一縮二季戊四醇二丙烯酸酯、山糖醇三丙烯酸酯、雙酚A二丙烯酸酯衍生物、三甲基丙烷三丙烯酸酯、一縮二季戊四醇聚丙烯酸酯、或其甲基丙烯酸酯類。The photosensitive resin composition for a spacer of the present invention which is composed of the component may further contain, as needed, a crosslinkable propylene monomer having at least two double bonds. Further, the crosslinkable propylene-based single system containing at least two double bonds may be 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate or ethylene glycol diacrylate. Pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate Ester, dipentaerythritol polyacrylate, or a methacrylate thereof.
前述至少含有兩個以上雙鍵之交聯性丙烯基單體係以含有重量百分比為2至10之感光性樹脂為佳，且更以含有重量百分比5為佳。當該含量不足重量百分比2時，硬化度及黏著力會不足，而無法形成圖案。又，當該含量超過重量百分比10時，變形量會因硬化度的增加而減少，因此無法實現柔軟的間隔子。The crosslinkable propylene-based single system containing at least two double bonds is preferably a photosensitive resin containing 2 to 10 parts by weight, and more preferably 5 parts by weight. When the content is less than 2% by weight, the degree of hardening and adhesion may be insufficient to form a pattern. Further, when the content exceeds 10% by weight, the amount of deformation is reduced by the increase in the degree of hardening, so that a soft spacer cannot be realized.
又，本發明之間隔子用感光性樹脂組成物係可依需要而更包含表面活性劑、增減劑、硬化促進劑、顏料等添加劑。特別地，前述表面活性劑係可使用矽系或氟系的表面活性劑。Further, the photosensitive resin composition for a spacer of the present invention may further contain an additive such as a surfactant, a reducing agent, a curing accelerator, or a pigment, as needed. In particular, the aforementioned surfactant may be a lanthanide or fluorine-based surfactant.
前述添加劑係以含有最大重量百分比為2之感光性樹脂組成物為佳，且當該含量超過重量百分比2時，則會產生殘膜或產生離子、雜質溶出至液晶中的現象。The above additive is preferably a photosensitive resin composition containing a maximum weight percentage of 2, and when the content exceeds 2% by weight, a residual film or ions are generated and impurities are eluted into the liquid crystal.
又，本發明係提供使用含有如前述之成分的間隔子用感光性樹脂組成物的間隔子形成方法、可以前述方法得到的間隔子、及可使用前述間隔子的液晶顯示元件。又，前述間隔子形成方法如下。Moreover, the present invention provides a spacer forming method using a photosensitive resin composition for a spacer containing the above-described components, a spacer which can be obtained by the above method, and a liquid crystal display element which can use the spacer. Further, the spacer formation method is as follows.
首先，將本發明之間隔子用感光性樹脂組成物以旋轉塗層法、夾縫及旋轉式塗層法、夾縫塗層法等塗層在基板表面，再藉預烘除去溶劑而形成塗膜。此時，前述預烘係以在70~110℃的溫度下實施1~5分鐘為佳。First, the spacer resin composition of the present invention is coated on the surface of the substrate by a spin coating method, a nip, a spin coating method, a quilt coating method, or the like, and a solvent is formed by pre-baking to form a coating film. In this case, the prebaking is preferably carried out at a temperature of 70 to 110 ° C for 1 to 5 minutes.
接著，藉由事先準備的圖案而將g、h、I線組合波長的光照射在前述所形成之塗膜，再使用顯像液顯像並除去不要的部分，藉此形成預定的圖案。Next, light of a combined wavelength of g, h, and I lines is irradiated onto the formed coating film by a pattern prepared in advance, and a developing liquid is used to develop an image by removing the unnecessary portion, thereby forming a predetermined pattern.
前述顯像液宜使用鹼水溶液，具體的說前述顯像液係可使用氫氧化鈉、氫氧化鉀、碳酸鈉等的無機鹼類；乙胺、n－丙胺等的一級胺類；二乙胺、s－丙胺等的二級胺類；三甲胺、甲基二乙胺、二甲基乙胺、三乙胺等的三級胺類；二甲基乙醇胺、甲基乙醇胺、三乙醇胺等的醇胺類；或四甲基氫氧化銨、四乙基氫氧化銨等的四級銨鹽水溶液等。此時，前述顯像液係將鹼性化合物以重量百分比0.1~10的濃度溶解使用，亦可的量添加如甲醇、乙醇等的水溶性有機溶劑及表面活性劑。The above-mentioned developing solution is preferably an aqueous alkali solution. Specifically, the above-mentioned developing liquid can be an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate; a primary amine such as ethylamine or n-propylamine; and diethylamine. a secondary amine such as s-propylamine; a tertiary amine such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine; or an alcohol such as dimethylethanolamine, methylethanolamine or triethanolamine. An amine; or a quaternary ammonium salt aqueous solution such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. In this case, the developing solution is obtained by dissolving a basic compound in a concentration of 0.1 to 10 by weight, or a water-soluble organic solvent such as methanol or ethanol and a surfactant.
又，在以如前所述的顯像液顯像之後，再用超純水洗淨30~90秒鐘，將不要的部分除去並烘乾而形成圖案，再將圖案藉由烘箱等的加熱裝置以150~250℃的溫度進行30~90分鐘的加熱處理，而可得到最後的圖案。Further, after developing with the developing liquid as described above, it is washed with ultrapure water for 30 to 90 seconds, and the unnecessary portion is removed and dried to form a pattern, and the pattern is heated by an oven or the like. The device is heated at a temperature of 150 to 250 ° C for 30 to 90 minutes to obtain the final pattern.
本發明之間隔子用感光性樹脂組成物具有可減少因液晶滴下量而產生未充填的不良情況，亦可防止彩色濾光板因壓力而在板面上產生損傷，不僅可克服在製程時所產生的厚度偏差，亦可在離子、雜質不溶出至液晶中之情形下不降低電壓保持率且不會在液晶配向時產生影響的效果。又，本發明之間隔子用感光性樹脂組成物具有優異的耐摩擦性、充分的電壓保持率及液晶配向性，亦具有顯像性、高感應性、熱穩定性、尺寸穩定性及優異的耐壓強度的效果。The photosensitive resin composition for spacers of the present invention has the problem of reducing the unfilling due to the amount of liquid crystal dropping, and also preventing the color filter from being damaged on the surface due to pressure, and not only can be overcome during the process. The thickness deviation may not reduce the voltage holding ratio in the case where ions or impurities are not eluted into the liquid crystal, and does not have an effect of affecting the liquid crystal alignment. Further, the photosensitive resin composition for a spacer of the present invention has excellent rubbing resistance, sufficient voltage holding ratio, and liquid crystal alignment, and also has developability, high inductivity, thermal stability, dimensional stability, and excellent properties. The effect of compressive strength.
以下，揭示較佳實施例以理解本發明，但下述實施例只是舉例說明，本發明之範圍並不受限於下述實施例。The preferred embodiments are disclosed below to understand the present invention, but the following examples are merely illustrative, and the scope of the present invention is not limited to the following examples.
平均混合重量百分比為30的鹼溶性丙烯酸酯樹脂、重量百分比為5的以前述化學式4表示之胺基甲酸酯系樹脂、重量百分比為5的以前述化學式4表示且作為至少具有兩個以上乙烯系雙鍵的交聯性單體之胺基甲酸酯單體、重量百分比為0.5的作為光聚合引發劑之Irgacure907(Ciba Specialty Chemicals製造)及重量百分比為0.2的4,4－雙二乙胺基二苯甲酮、重量百分比為37的作為溶劑之丙二醇甲醚乙酸酯、3－乙氧基丙酸乙酯17重量份及重量百分比為5.3的丁基乙酸來製成液態的間隔子用感光性組成物。An alkali-soluble acrylate resin having an average mixing weight percentage of 30, a urethane-based resin represented by the above Chemical Formula 4 in a weight percentage of 5, and a weight percentage of 5 represented by the aforementioned Chemical Formula 4 and having at least two or more ethylene A urethane monomer of a crosslinkable monomer which is a double bond, Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 4,4-bisdiethylamine as a photopolymerization initiator in a weight percentage of 0.5 Base benzophenone, propylene glycol methyl ether acetate as a solvent, 17 parts by weight of ethyl 3-ethoxypropionate, and butyl acetic acid in a weight percentage of 5.3 by weight to form a liquid spacer Photosensitive composition.
實施例2~4及比較例1~3係將前述實施例1中除去使用如下述所表示之成分及比率的部分後，實施與前述實施例1相同的方法來製成液態的間隔子用感光性組成物。此時，表1的單位是重量百分比。In the examples 2 to 4 and the comparative examples 1 to 3, the parts of the components and ratios shown in the following Example 1 were removed, and the same method as in the above-mentioned Example 1 was carried out to prepare a liquid spacer. Sexual composition. At this time, the unit of Table 1 is a weight percentage.
【表1】
以下係利用以前述實施例1至4及比較例1至3所製成的間隔子用感光性樹脂組成物來評價下述的顯像特性、間隔子的變形量與復原力、及間隔子的壓縮破壞特性。In the following, the photosensitive resin composition for spacers prepared in the above Examples 1 to 4 and Comparative Examples 1 to 3 was used to evaluate the following development characteristics, the amount of deformation of the spacer, the restoring force, and the spacer. Compression damage characteristics.
1)顯像特性1) Imaging characteristics
將以前述實施例1至4及比較例1至3製造的間隔子用感光性樹脂組成物旋轉塗層在玻璃面上並使膜的厚度成為4μm之後，再以90℃的電熱板乾燥2分鐘而得到塗膜。The photosensitive resin composition for spacers produced in the above Examples 1 to 4 and Comparative Examples 1 to 3 was spin-coated on the glass surface to have a thickness of 4 μm, and then dried by a hot plate at 90 ° C for 2 minutes. A coating film is obtained.
之後，將光罩放置在得到的塗膜上，利用可發射200nm~400nm波長的超高壓水銀燈，依365nm為基準，使其可曝光約200Mj/cm2 的預定時間，再利用KOH顯像液(DCD－260CF、東進semicem公司製造)透過預定時間的噴嘴顯像。透過前述顯像的精細圖案之黏著力及圖案形狀來評價顯像性，其結果如下述表2所示。Thereafter, the photomask is placed on the obtained coating film, and an ultrahigh pressure mercury lamp capable of emitting a wavelength of 200 nm to 400 nm is used, and based on 365 nm, it can be exposed to a predetermined time of about 200 Mj/cm 2 , and then the KOH developing solution is used ( DCD-260CF, manufactured by Tojin Semicem Co., Ltd.) is developed through nozzles of a predetermined time. The developability was evaluated by the adhesion of the fine pattern of the above-described development and the shape of the pattern, and the results are shown in Table 2 below.
如前述表2所示，本發明之實施例1至4的感光性樹脂組成物在遮罩尺寸為30、20、10μm的情況下，所有的圖案形狀及黏著力良好，且更優於比較例1至3。As shown in the above Table 2, in the photosensitive resin compositions of Examples 1 to 4 of the present invention, in the case where the mask size was 30, 20, or 10 μm, all the pattern shapes and adhesion were good, and it was superior to the comparative example. 1 to 3.
2)間隔子之變形量及復原力特性將在測量前述1)之顯像特性時顯像的精細圖案以220℃的乾燥烘箱進行40分鐘的熱烘之後得到測量試片。再藉前述測量試片依遮罩圖案20μm為基準來測量測量間隔子，再利用DUH(dynamic ultra micro hardness tester、shimadzu)以5gf的力將間隔子按壓在50μm的圓形平面壓痕機上，而可測量因對於間隔子之外力而發生的反曲點，並可觀察壓縮時的變形量，其結果如下述表3所示。2) Deformation amount and restoring force characteristic of the spacer The measurement pattern was obtained after the fine pattern developed at the time of measuring the development characteristics of the above 1) was subjected to hot baking in a drying oven at 220 ° C for 40 minutes. The measuring spacer was measured on the basis of the mask pattern of 20 μm, and the spacer was pressed by a force of 5 gf by a DUH (dynamic ultra micro hardness tester, shimadzu) on a circular flat indenter of 50 μm. On the other hand, the inflection point which occurs due to the force other than the spacer can be measured, and the amount of deformation at the time of compression can be observed, and the results are shown in Table 3 below.
如前述表3所示，而可得知利用本發明之實施例1至4的感光性樹脂組成物所形成的間隔子具有比比較例1至3的間隔子更高的變形量與復原量。因提升變形量而產生的柔軟度係可抑制間隔子在製程時發生厚度偏差而均等的形成，因此可顯示優異的均勻性。藉由此點可與以往硬間隔子在薄膜電晶板與彩色濾光板之結合製程中因製程時產生的厚度偏差而造成晶胞間隔的不均等，及因過度的按壓而破壞彩色濾光板與薄膜電晶板的情況有所區別。As shown in the above Table 3, it was found that the spacer formed by the photosensitive resin compositions of Examples 1 to 4 of the present invention had higher deformation amount and recovery amount than the spacers of Comparative Examples 1 to 3. The softness due to the increase in the amount of deformation suppresses the formation of the thickness deviation of the spacer during the process, and thus exhibits excellent uniformity. By this point, it is possible to cause the unevenness of the cell spacing due to the thickness deviation caused by the process during the bonding process of the conventional hard spacer in the thin film crystal plate and the color filter, and to destroy the color filter due to excessive pressing and The situation of the thin film crystal plate is different.
又，上述柔軟度亦具有可減低在因液晶滴下量發生誤差而造成填滿晶胞間隔的液晶不足的情況下，因變形而產生未填充範圍之不良的優點。Moreover, the above-mentioned softness also has the advantage that the liquid crystal which fills the cell gap due to the error in the amount of liquid crystal dripping is insufficient, and the unfilled range is defective due to the deformation.
因此，可推測本發明所形成之間隔子係具有可在因耐壓強度及外力而變形之後回復到原來晶胞間隔的優異回復力。Therefore, it is presumed that the spacer formed by the present invention has an excellent restoring force which can be restored to the original cell spacing after being deformed by the withstand voltage and the external force.
3)間隔子之壓縮破壞特性利用在測量前述2)間隔子之變形量及復原力特性時得到的測量試片依遮罩圖案20μm為基準來測量測量間隔子，再利用DUH(dynamic ultra micro hardness tester、shimadzu)以100gf的力將間隔子按壓在50μm的圓形平面壓痕機上，而可測量在間隔子破壞時所產生在反折點之力與變形量，並可觀察壓縮時的變形量及復原力，其結果如下述表4所示。3) The compression-destructive characteristic of the spacer is measured by measuring the measurement spacer obtained by measuring the deformation amount and the restoring force characteristic of the above 2) spacer, and measuring the measurement spacer according to the mask pattern of 20 μm, and then using DUH (dynamic ultra micro hardness) Tester, shimadzu) pressed the spacer to a 50 μm circular flat creasing machine with a force of 100 gf, and measured the force and deformation at the inflection point when the spacer was broken, and observed the deformation at the time of compression. The amount and the restoring force are shown in Table 4 below.
如前述表4所示，而可得知即使壓縮100gf，利用本發明之實施例1至4的感光性樹脂組成物所形成的間隔子也比比較例1至3的間隔子更具有優異的變形量與。As shown in the above Table 4, it was found that the spacer formed by the photosensitive resin compositions of Examples 1 to 4 of the present invention was more excellent in deformation than the spacers of Comparative Examples 1 to 3 even when 100 gf was compressed. Quantity and.
4)間隔子之耐摩擦特性將藉由與前述1)之顯像特性方法相同方法而顯像的精密圖案以220℃的乾燥烘箱進行40分鐘的熱烘之後可得到測量試片，再藉前述側重是片依遮罩圖案10、20、30μm為基準來測量測量間隔子，並利用可自體製作且可調整旋轉速度、摩擦深度階段移動速度的摩擦試驗機來觀察耐摩擦面在經摩擦之後間隔子之黏著力與表面有無刮痕。其結果如下述表5與表6所示。4) The friction resistance of the spacer is obtained by a hot pattern which is developed by the same method as the development method of the above 1) by a hot oven in a drying oven at 220 ° C for 40 minutes, and then the measurement piece is obtained. The focus is on measuring the measurement spacers based on the mask patterns 10, 20, and 30 μm, and using a friction tester that can be self-made and adjustable in the rotational speed and the friction depth stage to observe the friction-resistant surface after rubbing. The adhesion of the spacer and the surface are scratched. The results are shown in Tables 5 and 6 below.
如前述表5及6所示，而可得知利用本發明之實施例1至4的感光性樹脂組成物所形成的間隔子具有優於比較例1至3的間隔子的黏著力與耐摩擦力。As shown in the above Tables 5 and 6, it is understood that the spacer formed by the photosensitive resin compositions of Examples 1 to 4 of the present invention has adhesion and friction resistance superior to those of Comparative Examples 1 to 3. force.
5)間隔子之電壓保持率特性將藉由與前述1)之顯像特性方法相同方法而顯像的精密圖案以220℃的乾燥烘箱進行40分鐘的熱烘之後可得到間隔子，再利用該間隔子結合有ITO圖案的上下板，並且製作可注入及測量液晶的晶胞，而可利用VHRM105(AUTRONIC COMPANY)得到電壓保持率。5) Voltage retention characteristic of the spacer A spacer which is developed by the same method as the development method of the above 1) is subjected to hot baking in a drying oven at 220 ° C for 40 minutes to obtain a spacer, and the spacer is used. The spacer is combined with the upper and lower plates of the ITO pattern, and a cell which can inject and measure the liquid crystal is fabricated, and the voltage holding ratio can be obtained by using VHRM105 (AUTRONIC COMPANY).
由前述表中，而可得知實施例之間隔子不會因離子溶出及雜質而降低電壓保持率。From the above table, it can be seen that the spacer of the example does not reduce the voltage holding ratio due to ion elution and impurities.
6)間隔子之厚度均勻性將藉由與前述1)之顯像特性方法相同方法而顯像的精密圖案以220℃的乾燥烘箱進行40分鐘的熱烘之後可得到間隔子，再利用表面輪廓儀(surface profiler P－15、TENCO)來測量厚度，而可得到基板內厚度之均勻性。其結果如表8所示。6) Thickness uniformity of the spacer A fine pattern developed by the same method as the developing characteristic method of the above 1) is subjected to hot baking in a drying oven at 220 ° C for 40 minutes to obtain a spacer, and the surface profile is reused. The surface profiler P-15, TENCO is used to measure the thickness, and the uniformity of the thickness in the substrate can be obtained. The results are shown in Table 8.
從前述表中與比較例相比之後，而可得知當單獨使用丙二醇甲醚乙酸酯、3－乙氧基丙酸乙酯、丁基乙酸時無法顯示優異的厚度均勻性，而在具有如實施例一定比例之結構的情況下，則可得到優異的厚度均勻性。From the foregoing table, it was found that when propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, and butyl acetic acid were used alone, excellent thickness uniformity was not exhibited, and In the case of a structure of a certain ratio of the examples, excellent thickness uniformity can be obtained.
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| JP4830310B2 (en) * | 2004-02-23 | 2011-12-07 | 三菱化学株式会社 | Oxime ester-based compound, photopolymerizable composition, and color filter using the same |
-
2005
- 2005-08-05 JP JP2005227393A patent/JP4864375B2/en not_active Expired - Fee Related
- 2005-08-08 TW TW094126722A patent/TWI407216B/en active
- 2005-08-08 KR KR1020050072120A patent/KR101247243B1/en active IP Right Grant
- 2005-08-09 CN CN2005100900241A patent/CN1734351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200408904A (en) * | 1998-03-05 | 2004-06-01 | Hitachi Chem Dupont Microsys | Patterning method using developer for photosensitive polyimide precursor |
| TW569043B (en) * | 2001-06-06 | 2004-01-01 | Jsr Corp | Radiation sensitive composition for color liquid crystal display devices |
| JP2004170609A (en) * | 2002-11-19 | 2004-06-17 | Mitsubishi Chemicals Corp | Bluish-purple laser photosensitive composition, and image forming material, image forming stuff and image forming method using the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1734351A (en) | 2006-02-15 |
| KR20060050296A (en) | 2006-05-19 |
| TW200613864A (en) | 2006-05-01 |
| CN1734351B (en) | 2010-04-21 |
| JP2006053557A (en) | 2006-02-23 |
| JP4864375B2 (en) | 2012-02-01 |
| KR101247243B1 (en) | 2013-03-25 |
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