JP2015191001A - Uv-shielding material and optical treatment method for substrate of display device - Google Patents
Uv-shielding material and optical treatment method for substrate of display device Download PDFInfo
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Abstract
Description
本発明は、液晶装置などの表示装置及び電子機器に関連し、具体的には、紫外線に暴露されると劣化する部分を有する基板を紫外線を用いた光学処理を行うに際し有用な紫外線遮光材と、その紫外線遮光材を用いた表示装置の光学処理方法、より特定的には、液晶表示装置の製造にあたり、液晶表示装置を構成する光配向膜を有する基板に紫外線を照射して処理する工程において、基板の紫外線にて劣化する部分を遮光するための好適な遮光材料とそれを用いた光配向処理方法を提供するものである。 The present invention relates to a display device such as a liquid crystal device and an electronic apparatus. Specifically, the present invention relates to an ultraviolet light shielding material useful for performing optical processing using ultraviolet rays on a substrate having a portion that deteriorates when exposed to ultraviolet rays. In an optical processing method of a display device using the ultraviolet light shielding material, more specifically, in the process of irradiating a substrate having a photo-alignment film constituting the liquid crystal display device by irradiating the substrate with ultraviolet rays. The present invention provides a suitable light-shielding material for shielding a part deteriorated by ultraviolet rays of a substrate and a photo-alignment processing method using the same.
液晶装置では、電場等の作用によって液晶の分子配列の状態を変化させ、この変化を光学的に利用することによって表示に活用している。液晶を特定の方向に配列させるためには配向処理が施されるが、従来のラビング法では微細な粉塵や静電気が発生するという問題があるので、近年、偏光紫外線を配向膜に照射して配向処理を行う光配向処理が提案され、実施されている(特許文献1,2)。 In the liquid crystal device, the state of the molecular arrangement of the liquid crystal is changed by the action of an electric field or the like, and this change is optically used for display. In order to align the liquid crystal in a specific direction, alignment treatment is performed. However, the conventional rubbing method has a problem that fine dust and static electricity are generated. A photo-alignment process for performing the process has been proposed and implemented (Patent Documents 1 and 2).
一方で、表示装置を構成する薄膜トランジスタ基板やカラーフィルター基板などには、強力な紫外線で劣化してしまう部分がある。例えば、薄膜トランジスタ基板の各画素に配置されたスイッチング回路や、低温ポリシリコンやIGZOなどの酸化物半導体を用いた時に採用されている有効表示エリアの外に配置されている論理回路は、紫外線が照射されると素子の劣化があり誤動作の原因となる。また、カラーフィルター基板のオーバーコート層が紫外線によって劣化し、劣化したオーバーコート層から液晶層への水分侵入を許してしまい、製品の信頼性を損なうと指摘されてきた。このため、光配向処理工程では、紫外線を当てたくない部分を遮光するマスクを使って処理をしていた。しかしながら、当該マスクは処理すべき基板と密着させて照射するのは困難で、どうしても0.1mm内外の隙間ができてしまい、紫外線の当てたくないところに紫外線が回り込んでしまい特性が劣化してしまう不具合が発生する問題があった。 On the other hand, a thin film transistor substrate, a color filter substrate, or the like constituting a display device has a portion that is deteriorated by strong ultraviolet rays. For example, switching circuits arranged on each pixel of a thin film transistor substrate and logic circuits arranged outside an effective display area employed when using an oxide semiconductor such as low-temperature polysilicon or IGZO are irradiated with ultraviolet rays. If this happens, the element will deteriorate and cause malfunction. Further, it has been pointed out that the overcoat layer of the color filter substrate is deteriorated by ultraviolet rays, allowing moisture to enter the liquid crystal layer from the deteriorated overcoat layer, thereby impairing the reliability of the product. For this reason, in the photo-alignment processing step, processing is performed using a mask that shields a portion that is not desired to be irradiated with ultraviolet rays. However, it is difficult to irradiate the mask in close contact with the substrate to be processed, and there is inevitably a gap of 0.1 mm inside and outside, and ultraviolet rays wrap around where you do not want to irradiate ultraviolet rays, and the characteristics deteriorate. There was a problem that a problem occurred.
図7を参照すると、基板11上の遮光されるべき部分(遮光部)12を紫外線UVから遮光するためにマスク13が用いられている。マスク13は基板11の上方に設置され、紫外線を遮るパターンを有している。一般的には、石英ガラスまたはパイレックス(登録商標)ガラスが用いられ、パターンは金属クロムによって形成されている。このようなマスクを使用すると、基板との隙間が問題となり、光の回り込みがあり、所望の遮光部分12を多くできないという問題がある。特に第5世代基板(1100x1300nm)以上になると、マスクも大型になり、マスクのたわみの無視できなくなり、さらに遮光部分の精度が悪くなる。 Referring to FIG. 7, a mask 13 is used to shield a portion (light shielding portion) 12 to be shielded on the substrate 11 from ultraviolet rays UV. The mask 13 is placed above the substrate 11 and has a pattern that blocks ultraviolet rays. In general, quartz glass or Pyrex (registered trademark) glass is used, and the pattern is formed of metallic chromium. When such a mask is used, there arises a problem that a gap with the substrate becomes a problem, light wraps around, and a desired light shielding portion 12 cannot be increased. In particular, when the substrate is a fifth generation substrate (1100 × 1300 nm) or more, the mask also becomes large, and the deflection of the mask cannot be ignored, and the accuracy of the light shielding portion is deteriorated.
本発明の目的は、光配向処理などの光学処理をする工程において、従来のマスクによる遮光での紫外線に暴露したくない部分に紫外線が回り込むような不具合を防いだ表示装置、電子機器にするための新たな工程とそれを可能にする材料を提供することにある。 An object of the present invention is to provide a display device and an electronic apparatus that prevent a problem in which ultraviolet rays wrap around a portion that is not desired to be exposed to ultraviolet rays by light shielding by a conventional mask in a process of optical processing such as photo-alignment treatment. It is to provide a new process and a material enabling it.
上記の課題を解決するため、本発明によれば、下記が提供される。
(1)表示装置または電子機器を構成する基板を紫外線照射して処理をする工程で、紫外線によって劣化をもたらす構成材料もしくは部品部分を、被覆して遮光するための材料であって、水溶性または水分散性樹脂と、水溶性染料とを含む水性溶液からなり、前記水性溶液で作られた遮光膜が5μm以下の厚さにおいて、波長240〜370nmの範囲内のいずれかの波長の紫外線に対する遮光度が1以上となることを特徴とする紫外線遮光材。
In order to solve the above problems, the present invention provides the following.
(1) In a process of irradiating a substrate that constitutes a display device or an electronic device by irradiating with ultraviolet rays, a constituent material or a component part that is deteriorated by ultraviolet rays is coated and shielded from light, and is water-soluble or A light-shielding film made of an aqueous solution containing a water-dispersible resin and a water-soluble dye, and a light-shielding film made of the aqueous solution having a thickness of 5 μm or less, shields against ultraviolet rays having a wavelength in the range of 240 to 370 nm. An ultraviolet light shielding material having a degree of 1 or more.
(2)水溶性紫外線吸収剤をさらに含むことを特徴とする請求項1に記載の水溶性遮光材。 (2) The water-soluble light-shielding material according to claim 1, further comprising a water-soluble ultraviolet absorber.
(3)有機溶剤をさらに含むことを特徴とする上記(1)または(2)に記載の水溶性遮光材。 (3) The water-soluble light-shielding material according to (1) or (2), further comprising an organic solvent.
(4)表示装置または電子機器を構成する基板の紫外線によって劣化をもたらす構成材料もしくは部品部分の上に直接に、上記(1)〜(3)に記載の水溶性遮光材を塗布・乾燥して遮光膜を選択的に形成して保護し、前記基板に紫外線を照射した後に、前記基板から前記遮光膜を除去することを特徴とする表示装置または電子機器の光学処理方法。 (4) Applying and drying the water-soluble light-shielding material described in the above (1) to (3) directly on the constituent material or component part that causes deterioration by ultraviolet rays of the substrate constituting the display device or electronic device. An optical processing method for a display device or an electronic apparatus, wherein a light shielding film is selectively formed and protected, and the light shielding film is removed from the substrate after the substrate is irradiated with ultraviolet rays.
(5)前記表示装置または電子機器を構成する基板が液晶表示装置の液晶配向膜であり、その液晶配向膜に紫外線を用いた光配向処理の前に、前記基板に具備されている紫外線への暴露を防ぐべきトランジスタ、配線および/または薄膜の上に直接に前記水溶性遮光材を塗布・乾燥して遮光膜を選択的に形成して保護し、前記光配向膜に紫外線を用いた光配向処理を施した後に、前記基板から前記遮光膜を除去することを特徴とする上記(4)に記載の表示装置のまたは電子機器光学処理方法。 (5) The substrate constituting the display device or electronic device is a liquid crystal alignment film of a liquid crystal display device, and before the photo-alignment treatment using ultraviolet light for the liquid crystal alignment film, the substrate is subjected to ultraviolet light. Applying and drying the water-soluble light-shielding material directly on the transistor, wiring and / or thin film to prevent exposure, and selectively forming a light-shielding film for protection, and photo-alignment using ultraviolet light for the photo-alignment film The display device or electronic apparatus optical processing method according to (4), wherein the light-shielding film is removed from the substrate after the processing.
(6)前記水溶性遮光材の塗布を印刷法で行うことを特徴とする上記(4)または(5)に記載の表示装置または電子機器の光学処理方法。 (6) The optical processing method for a display device or electronic device according to (4) or (5), wherein the water-soluble light shielding material is applied by a printing method.
本発明によれば、表示装置または電子機器を構成する基板の紫外線を照射したくない部分に水溶性樹脂と、水溶性染料、及び水溶性紫外線吸収剤からなる群より選択された溶液からなり、該溶液で作られた遮光膜が5μm以下の厚さにおいて、遮光度1以上となる遮光材を塗布することにより、紫外線照射での処理工程でも遮光材料を塗布した部分は紫外線での劣化は観察できず、また、精度よく紫外線をカットできるため、高信頼性の高精細表示装置を提供できた。本発明の遮光膜およびそれを用いた光学処理方法は、液晶表示装置に限定されず、光学処理によって劣化する部分を含む表示装置または電子機器の基板の光学処理に広く有用であることは明らかである。 According to the present invention, a portion of the substrate constituting the display device or the electronic device that is not desired to be irradiated with ultraviolet rays comprises a solution selected from the group consisting of a water-soluble resin, a water-soluble dye, and a water-soluble ultraviolet absorber, By applying a light shielding material with a light shielding degree of 1 or more when the light shielding film made of the solution is 5 μm or less, the portion coated with the light shielding material is observed to be deteriorated by ultraviolet rays even in the treatment process by ultraviolet irradiation. In addition, since ultraviolet rays can be cut with high accuracy, a highly reliable high-definition display device can be provided. The light-shielding film of the present invention and the optical processing method using the same are not limited to the liquid crystal display device, and are clearly useful for optical processing of a substrate of a display device or an electronic device including a portion deteriorated by the optical processing. is there.
(従来技術と本発明)
本発明は、背景技術の欄で述べたマスクを用いる遮光技術に伴う問題を解決するものであり、本発明によれば、表示装置または電子機器を構成する基板を紫外線照射して処理をする工程で、紫外線によって劣化をもたらす構成材料もしくは部品部分を、被覆して遮光するための材料であって、水溶性または水分散性樹脂と、水溶性染料とを含む水性溶液からなり、前記水性溶液で作られた遮光膜が5μm以下の厚さにおいて、波長240〜370nmの範囲内のいずれかの波長の紫外線に対する遮光度が1以上となることを特徴とする紫外線遮光材を提供する。
(Prior art and the present invention)
The present invention solves the problems associated with the light-shielding technology using a mask described in the background art section, and according to the present invention, a process of irradiating a substrate constituting a display device or an electronic apparatus with ultraviolet irradiation. And a material for covering and shielding a component material or part portion that is deteriorated by ultraviolet rays, comprising an aqueous solution containing a water-soluble or water-dispersible resin and a water-soluble dye. Provided is an ultraviolet light shielding material characterized in that when the produced light shielding film has a thickness of 5 μm or less, the degree of light shielding with respect to ultraviolet rays having any wavelength within the range of wavelengths of 240 to 370 nm is 1 or more.
本発明によれば、水溶性遮光材において水溶性樹脂に水溶性染料と任意に水溶性紫外線吸収剤を併用することにより、遮光膜の厚さ5μm以下において紫外線の遮光度を1以上、好ましくは1.3以上、さらには2以上である。ここで遮光度とは、吸光度(Absorbance)と同義であり、遮光度は所望の波長(例えば254nm、313nm、360nmなど240〜370nmの範囲内の波長)での媒体の吸光度になり、遮光度A=−log(T/100)[式中、Tは透過率(単位%)]である。遮光度あるいは吸光度の測定方法は、分光光度計(例えば島津製作所製)により測定できる。試料として石英基板上に塗布、乾燥した遮光材料の分光スペクトルをとり、結果として、紫外領域の波長(例えば254nm)で透過率Tが10%以下、吸光度(遮光度)で1以上あればよいということになる。遮光度の測定において紫外線としては光処理に通常用いられる1000mJ/cm2程度の場合、照射強度には影響されない。 According to the present invention, by using a water-soluble resin and optionally a water-soluble ultraviolet absorber in a water-soluble resin in a water-soluble light-shielding material, the degree of light-shielding of ultraviolet rays is preferably 1 or more, preferably at a thickness of 5 μm or less of the light-shielding film. 1.3 or more, and further 2 or more. Here, the light shielding degree is synonymous with absorbance (Absorbance), and the light shielding degree is the absorbance of the medium at a desired wavelength (for example, a wavelength within a range of 240 to 370 nm such as 254 nm, 313 nm, 360 nm, etc.). = -Log (T / 100) [where T is transmittance (unit%)]. The method for measuring the degree of shading or absorbance can be measured with a spectrophotometer (for example, manufactured by Shimadzu Corporation). A spectral spectrum of a light shielding material coated and dried on a quartz substrate as a sample is taken. As a result, the transmittance T is 10% or less and the absorbance (light shielding degree) is 1 or more at a wavelength in the ultraviolet region (for example, 254 nm). It will be. In the measurement of the light shielding degree, the ultraviolet ray is not affected by the irradiation intensity when it is about 1000 mJ / cm 2 which is usually used for light processing.
(水性溶媒)
本発明の紫外線遮光材は、水性溶液であり、溶媒は水性、すなわち、水だけか、水と有機溶剤の混合溶媒を用いる。有機溶媒を用いると作業環境として負荷があるので、溶媒は水だけが好ましく、本発明の紫外線遮光材は溶媒として水だけでよいという特徴があるが、必要に応じて有機溶剤を混合使用してもよい。有機溶剤の混合割合としては、50質量%未満、好ましくは20質量%以下、より好ましくは10質量%以下である。
(Aqueous solvent)
The ultraviolet light shielding material of the present invention is an aqueous solution, and the solvent is aqueous, that is, only water or a mixed solvent of water and an organic solvent is used. Since there is a load as a working environment when using an organic solvent, only water is preferable as the solvent, and the ultraviolet light shielding material of the present invention is characterized by only water as a solvent. Also good. The mixing ratio of the organic solvent is less than 50% by mass, preferably 20% by mass or less, more preferably 10% by mass or less.
水に混合して使用できる有機溶媒を例示すると、アルコール類、酢酸、テトラヒドロフラン(THF)、1,4−ジオキサン、アセトン、アクリロニトリル、ジメチルホルムアミド(DMF)、ピリジン、N−メチルピロリドン(NMP)を挙げることができる。 Examples of organic solvents that can be used by mixing with water include alcohols, acetic acid, tetrahydrofuran (THF), 1,4-dioxane, acetone, acrylonitrile, dimethylformamide (DMF), pyridine, and N-methylpyrrolidone (NMP). be able to.
このような水溶性溶媒は特に制限されないが、環境への影響の点からは、該水溶性溶媒はアルコールであることが好ましい。本発明において使用可能なアルコールを列挙すれば、メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、エチレングリコールがある。本発明においては、アルコール類の中でも、安全性、揮発性、ないし水溶性高分子等の「溶質」の溶解度の点からは、イソプロピルアルコール、エタノールが好適に使用可能である。すなわち、本発明においては、水とアルコールとの各種割合の混合物が、溶媒として好適に使用可能である。 Such a water-soluble solvent is not particularly limited, but from the viewpoint of influence on the environment, the water-soluble solvent is preferably an alcohol. Examples of alcohols that can be used in the present invention include methanol, ethanol, propanol, isopropyl alcohol, butanol, and ethylene glycol. In the present invention, among alcohols, isopropyl alcohol and ethanol can be suitably used from the viewpoint of the solubility of “solute” such as safety, volatile property, and water-soluble polymer. That is, in the present invention, a mixture of water and alcohol in various proportions can be suitably used as the solvent.
(水溶性樹脂)
本発明の水溶性遮光材においては、水性溶媒中の固形分として水溶性高分子(水溶性樹脂)を含有する。
(Water-soluble resin)
The water-soluble light-shielding material of the present invention contains a water-soluble polymer (water-soluble resin) as a solid content in the aqueous solvent.
前記水溶性高分子(水溶性樹脂)は、遮光材の基材となるものであり、水、さらにはアルコールなどの有機溶剤に溶解させて塗布及び乾燥させて膜を形成し得るものであれば、特に制限されず、例えばポリエチレングリコール、ポリアクリル酸、メチルセルロース、エチルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリグリセリン、その他澱粉、アラビアゴム、ゼラチン、メチルビニルエーテル/無水マレイン酸共重合体、サクローズオクタアセテート、アルギン酸アンモニウム、アルギン酸ナトリウム、ポリビニルアミンポリエチレンオキシド、ポリスチレンスルホン酸等が挙げられる。これらは単独で或いは混合して用いられる。 The water-soluble polymer (water-soluble resin) serves as a base material for the light-shielding material, and can be dissolved in water or an organic solvent such as alcohol and applied and dried to form a film. , Not particularly limited, for example, polyethylene glycol, polyacrylic acid, methyl cellulose, ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyglycerin, other starches, gum arabic, gelatin, methyl vinyl ether / maleic anhydride copolymer, sucrose octaacetate, Examples include ammonium alginate, sodium alginate, polyvinylamine polyethylene oxide, polystyrene sulfonic acid, and the like. These may be used alone or in combination.
また、本発明において、紫外線遮光膜は、光配向処理などの光学処理の後、水洗によって除去されるものであり、水洗性を考慮するならば、水溶性樹脂としてポリエチレングリコールをとして使用することが好ましく、さらにその(平均)重合度は、100〜500程度が好ましく、更には200〜400程度が好ましく、特に、250〜300(例えば300)程度が好ましい。 Further, in the present invention, the ultraviolet light shielding film is removed by washing with water after optical treatment such as photo-alignment treatment. If water washability is taken into consideration, polyethylene glycol can be used as a water-soluble resin. Preferably, the (average) degree of polymerization is preferably about 100 to 500, more preferably about 200 to 400, and particularly preferably about 250 to 300 (for example, 300).
本発明の水溶性遮光材において水溶性高分子(水溶性樹脂)の配合量は、固形分を基準に30質量%から70質量%が好ましく、30質量%から70質量%がより好ましい。本発明の紫外線遮光材の固形分は、典型的には、水溶性高分子(水溶性樹脂)と、水溶性染料と、任意に配合される水溶性紫外線吸収剤であり、これらの合計を基準とすることができる。 In the water-soluble light-shielding material of the present invention, the blending amount of the water-soluble polymer (water-soluble resin) is preferably 30% by mass to 70% by mass, and more preferably 30% by mass to 70% by mass based on the solid content. The solid content of the ultraviolet light-shielding material of the present invention is typically a water-soluble polymer (water-soluble resin), a water-soluble dye, and a water-soluble ultraviolet absorber that is optionally blended, based on the total of these. It can be.
(水溶性染料)
本発明の水溶性遮光材においては、上述した水溶性樹脂に水溶性染料を併用する。顔料では表示装置または電子機器の基板が汚染される可能性があり、また有機溶媒系の染料では作業場に防爆装置を必要とするなどの不便がある。すなわち、本発明の水溶性遮光材は、顔料および有機溶媒系の染料を用いないことを特徴とするが、本発明を阻害しない範囲であれば、顔料および有機溶媒系の染料を含んでもよい。その配合量は固形分基準で高々5質量%未満、さらには2質量%以下である。
(Water-soluble dye)
In the water-soluble light-shielding material of the present invention, a water-soluble dye is used in combination with the water-soluble resin described above. The pigment may contaminate the substrate of the display device or the electronic device, and the organic solvent-based dye has an inconvenience that an explosion-proof device is required in the workplace. That is, the water-soluble light-shielding material of the present invention is characterized by not using a pigment and an organic solvent-based dye, but may contain a pigment and an organic solvent-based dye as long as the present invention is not inhibited. The blending amount is at most less than 5% by mass and further 2% by mass or less based on the solid content.
水溶性染料としては、アゾ染料、アクリジン染料、アジン染料、アントラキノン染料、インジゴイド染料、オキシケトン染料、キノフタロン染料、キノリン染料、キノンイミン染料、スチルベン染料、トリフェニルメタン染料、ヒドラゾン染料、フタロシアニン染料、ポリメチン染料、ピラゾン染料、等の公知の染料を用いる事ができ、アゾ染料が好ましい。 Water-soluble dyes include azo dyes, acridine dyes, azine dyes, anthraquinone dyes, indigoid dyes, oxyketone dyes, quinophthalone dyes, quinoline dyes, quinoneimine dyes, stilbene dyes, triphenylmethane dyes, hydrazone dyes, phthalocyanine dyes, polymethine dyes, Known dyes such as pyrazone dyes can be used, and azo dyes are preferred.
本発明の水溶性遮光材において水溶性染料の配合量は、固形分を基準にして30質量%から70質量%が好ましく、30質量%から70質量%がより好ましい。 In the water-soluble light-shielding material of the present invention, the blending amount of the water-soluble dye is preferably 30% by mass to 70% by mass, more preferably 30% by mass to 70% by mass based on the solid content.
(水溶性紫外線吸収剤)
上述した水溶性樹脂と必要に応じて併用される水溶性紫外線吸収剤としては、2−(2'−ヒドロキシ−5'−メチルフェニル)ベンゾトリアゾール、2テトラヒドロキシベンゾフェノン、チルヘルペリジン、ジエタノールアミンp−メトキシシンナメート、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸ナトリウム等を用いることができ、2−(2'−ヒドロキシ−5'−メチルフェニル)ベンゾトリアゾールが好ましい。
(Water-soluble UV absorber)
Examples of water-soluble ultraviolet absorbers used in combination with the above-described water-soluble resins as needed include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2tetrahydroxybenzophenone, tilherperidine, diethanolamine p-methoxycinna. Mate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, and the like can be used, and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole is preferable.
本発明の水溶性遮光材において任意に配合される水溶性紫外線吸収剤の配合量は、固形分を基準に、0.001質量%から1.00質量%が好ましく、0.01質量%から0.5質量%がより好ましい。 The blending amount of the water-soluble UV absorber arbitrarily blended in the water-soluble light-shielding material of the present invention is preferably 0.001% by mass to 1.00% by mass, and 0.01% by mass to 0% based on the solid content. More preferable is 5% by mass.
(光照射処理工程および方法)
本発明によれば、表示装置または電子機器を製造する工程において、紫外線を照射することで基板への機能付加処理工程に関し、基板上の紫外線が照射されることにより機能劣化する部分を、紫外線照射する工程の前に、水溶性樹脂と、水溶性染料、及び任意に水溶性紫外線吸収剤を含む水性溶液を用いて基板上の紫外線が照射されることにより機能劣化する部分の上に直接に選択的に保護膜を作成し、該水性溶液で作られた遮光膜が5μm以下の厚さにおいて、紫外線の遮光度2以上となる遮光材を塗布することを特徴とする機能付加処理方法が提供される。
(Light irradiation treatment process and method)
According to the present invention, in a process of manufacturing a display device or an electronic device, a function addition processing step to a substrate by irradiating ultraviolet rays is performed. Select directly on the part where the function deteriorates by irradiating with ultraviolet rays on the substrate using an aqueous solution containing a water-soluble resin, a water-soluble dye, and optionally a water-soluble UV absorber. A function-adding treatment method is provided, in which a protective film is formed and a light-shielding material having a light-shielding degree of 2 or more is applied when the light-shielding film made of the aqueous solution has a thickness of 5 μm or less. The
本発明は、表示装置または電子機器を製造する際に表示装置または電子機器を構成する基板に紫外線を照射して処理をする工程において、従来の遮光マスクを用いるのではなく、紫外線の照射したくない部分の基板に直接下記の遮光材料を塗布することにより、精度よく紫外線照射の害を防ぐものである。 In the process of irradiating a substrate constituting a display device or electronic device with ultraviolet rays when manufacturing the display device or electronic device, the present invention does not use a conventional light-shielding mask but wants to irradiate with ultraviolet rays. By directly applying the following light-shielding material to the unexposed part of the substrate, the harm of ultraviolet irradiation is prevented with high accuracy.
遮光材は、水溶性樹脂と、水溶性染料、及び任意に水溶性紫外線吸収剤を含む水性溶液からなり、該溶液で作られた遮光膜が5μm以下の厚さにおいて、遮光度1以上となることを特徴とする。 The light shielding material is composed of an aqueous solution containing a water-soluble resin, a water-soluble dye, and optionally a water-soluble ultraviolet absorber, and the light shielding film made of the solution has a light shielding degree of 1 or more when the thickness is 5 μm or less. It is characterized by that.
これらの遮光材の直接の塗布方法は、紫外線の照射したくない部分に塗布するため、印刷法が望ましく、凹版印刷、凸版印刷、インクジェット方式、スクリーン印刷、スタンピングなど方式をいとわない。直接印刷にて遮光部分のパターンを作ることにより、従来の遮光マスクのたわみを考慮したパターンの補正設計は必要としない。 The direct coating method of these light-shielding materials is preferably a printing method because it is applied to a portion that is not desired to be irradiated with ultraviolet rays, and a method such as intaglio printing, letterpress printing, ink jet printing, screen printing, and stamping can be used. By creating the pattern of the light shielding part by direct printing, the pattern correction design considering the deflection of the conventional light shielding mask is not required.
固形分濃度が11.2%で13.7μmの膜厚で塗布し80℃3分焼成乾燥後、溶媒が蒸発し約1.1μmの膜厚を得ることができる。この遮光膜で1000mJ/cm2射しても遮光することが確認できている。一方、固形分濃度16%で30μmの膜厚で塗布し80℃3分焼成乾燥後、溶媒が蒸発し約4.1μmの膜厚を得ることができる。この遮光膜は、2000μmJ/cm2照射しても遮光することが確認できている。 After coating at a solid content concentration of 11.2% with a film thickness of 13.7 μm and baking and drying at 80 ° C. for 3 minutes, the solvent evaporates and a film thickness of about 1.1 μm can be obtained. It has been confirmed that this light-shielding film can shield light even when exposed to 1000 mJ / cm 2 . On the other hand, after coating at a solid content concentration of 16% and a film thickness of 30 μm and baking and drying at 80 ° C. for 3 minutes, the solvent evaporates and a film thickness of about 4.1 μm can be obtained. This light-shielding film has been confirmed to shield light even when irradiated with 2000 μmJ / cm 2 .
さらにこうして作成した遮光膜は水洗することで残渣なく完全に基板上から除去できた。すなわち遮光膜の剥離法は、シャワー洗浄でも、超音波洗浄でも数秒で剥離できることが確認できた。 Furthermore, the light-shielding film thus prepared could be completely removed from the substrate without residue by washing with water. That is, it was confirmed that the light-shielding film can be peeled in a few seconds by shower cleaning or ultrasonic cleaning.
本発明は、とりわけ、液晶表示装置の液晶配向膜を有する基板において、液晶配向膜を紫外線を用いて光配向処理する場合に、紫外線への暴露を防ぐべきトランジスタ、配線、薄膜(カラーフィルタのオーバーコートなど)などの構成要素を保護するために、特に有用である。トランジスタ、配線、薄膜などの構成要素の上に直接に水溶性遮光材を塗布・乾燥して遮光膜を形成して当該部分を保護してから、紫外線で光配向処理を行い、光配向処理後に遮光膜を除去することで、従来のマスクの場合の光の回り込みを防止することができる。トランジスタ、配線、薄膜などの紫外線への暴露を防ぐべき部分に遮光膜を形成するには、露光方法を用いてもよいが、印刷法を用いることで、遮光膜を形成するための露光工程も不要になり、配向膜への悪影響も防止できる。 In particular, the present invention relates to a transistor, wiring, and thin film (overflow of color filters) that should be prevented from being exposed to ultraviolet light when the liquid crystal alignment film is subjected to photo-alignment treatment using ultraviolet light on a substrate having a liquid crystal alignment film of a liquid crystal display device. Particularly useful for protecting components such as coats). After applying a water-soluble light-shielding material directly on components such as transistors, wiring, and thin films to form a light-shielding film by protecting the part, and then performing photo-alignment treatment with ultraviolet rays. By removing the light shielding film, it is possible to prevent light from wrapping around in the case of a conventional mask. An exposure method may be used to form a light-shielding film on a portion such as a transistor, wiring, or thin film that should be prevented from being exposed to ultraviolet rays, but an exposure process for forming the light-shielding film by using a printing method is also possible. It becomes unnecessary, and the adverse effect on the alignment film can also be prevented.
表示装置の基板に対する光配向処理などの光学処理は、公知の光学処理であることができる。 Optical processing such as optical alignment processing for the substrate of the display device can be a known optical processing.
<吸光係数の測定>
吸光度(abs):紫外線分光光度計(島津製作所UV−3150)により、波長254nmにおける試料溶液の吸光度を測定した。
<Measurement of extinction coefficient>
Absorbance (abs): The absorbance of the sample solution at a wavelength of 254 nm was measured with an ultraviolet spectrophotometer (Shimadzu UV-3150).
吸光係数:実測された上記吸光度から、試料溶液の吸光係数を求めた。 Absorption coefficient: The absorption coefficient of the sample solution was determined from the measured absorbance.
(実施例1)
図1〜6を参照すると、液晶表示装置を構成する2枚の基板の内の一方は、低温ポリシリコンを用いたTFT基板1であり、もう一方はカラーフィルター基板1’である。TFT基板1には有効表示エリアに形成された画素2、論理回路形成部3、カラーフィルター基板1’にはカラーフィルター形成部6が形成されている。この2枚の基板1,1’に光配向材料RN−2467(商品名:日産化学製)をフレキソ印刷法により、有効表示エリアを覆い周辺シール材に接するパターンで印刷し、230℃、30分オーブンで焼成することにより膜厚1000Åの光配向膜4を形成した。
(Example 1)
1 to 6, one of the two substrates constituting the liquid crystal display device is a TFT substrate 1 using low-temperature polysilicon, and the other is a color filter substrate 1 ′. The TFT substrate 1 is formed with the pixels 2 formed in the effective display area, the logic circuit forming portion 3, and the color filter substrate 1 ′ with the color filter forming portion 6. A photo-alignment material RN-2467 (trade name: manufactured by Nissan Chemical Co., Ltd.) is printed on the two substrates 1 and 1 'by a flexographic printing method in a pattern that covers the effective display area and is in contact with the peripheral sealing material. The photo-alignment film 4 having a thickness of 1000 mm was formed by baking in an oven.
また、質量比がポリビニルアルコール500(関東化学)10%、水溶性染料黒インク KAYACION BLACK P−GS(日本化薬)6%、紫外線吸収剤アデカスタブLA−46(アデカ)0.1%、イソプロピルアルコール5%、水78.9%からなる、固形分濃度が16%の塗布液を作成した。 In addition, the mass ratio is 10% of polyvinyl alcohol 500 (Kanto Chemical), water-soluble dye black ink KAYACION BLACK P-GS (Nippon Kayaku) 6%, UV absorber Adekastab LA-46 (Adeka) 0.1%, isopropyl alcohol A coating solution comprising 5% and water 78.9% and having a solid concentration of 16% was prepared.
上記により得た塗布液を、TFT基板の有効表示エリア以外に形成された論理回路部分3(図1〜2)を完全に覆うように塗布し、80℃、3分で乾燥を行い、厚さ1μmの遮光膜5を作成した(図3、図4)。 The coating solution obtained as described above is applied so as to completely cover the logic circuit part 3 (FIGS. 1 and 2) formed outside the effective display area of the TFT substrate, dried at 80 ° C. for 3 minutes, A light-shielding film 5 having a thickness of 1 μm was prepared (FIGS. 3 and 4).
なお、この遮光膜5の透光度(遮光度)として、上記塗布液から石英基板上に同様に塗布、乾燥して形成した材料について、分光光度計(例えば島津製作所製)により遮光材料の分光スペクトルをとり、紫外線の透過率を測定したところ、254nmにおける紫外線透過率は、1%以下であった。すなわち、UV領域の波長(254nm)で透過率Tが1%以下であり、吸光度(遮光度)は2以上であった。 In addition, as the light transmittance (light shielding degree) of the light shielding film 5, a material formed by applying the coating liquid onto the quartz substrate and drying it in the same manner is used. When the spectrum was taken and the transmittance of ultraviolet rays was measured, the ultraviolet transmittance at 254 nm was 1% or less. That is, the transmittance T was 1% or less at a wavelength in the UV region (254 nm), and the absorbance (light shielding degree) was 2 or more.
同様に、カラーフィルター基板1’においても、光配向材料4が塗布されていない部分にTFT基板に形成したものと同様の遮光膜5を形成した(図5、図6)。 Similarly, on the color filter substrate 1 ′, a light shielding film 5 similar to that formed on the TFT substrate was formed in a portion where the photo-alignment material 4 was not applied (FIGS. 5 and 6).
このようにして処理された2枚の基板1,1’に高圧水銀灯ランプから主波長254nmの紫外線を、少なくとも254nmの波長を偏光光にするワイヤーグリッド偏光板を通して偏光を作成し、照射した。照射量は1000mJ/cm2であった。 The two substrates 1 and 1 ′ thus treated were irradiated with ultraviolet rays having a main wavelength of 254 nm from a high pressure mercury lamp lamp through a wire grid polarizing plate having a wavelength of at least 254 nm as polarized light. The irradiation amount was 1000 mJ / cm 2 .
その後、この2枚の基板を純水シャワーで30秒流すと、遮光膜5は純水に溶解して完全に除去できた。 Thereafter, when the two substrates were allowed to flow for 30 seconds in a pure water shower, the light shielding film 5 was dissolved in pure water and could be completely removed.
その後の工程を経てこの2枚の基板1,1’から成る液晶表示装置を作成し表示特性を評価した。 Through the subsequent steps, a liquid crystal display device composed of the two substrates 1 and 1 'was prepared and the display characteristics were evaluated.
液晶分子は光配向膜の偏光方向に配列し、かつ、表示の誤動作などなく正常に動作することが確認できた。 It was confirmed that the liquid crystal molecules are aligned in the polarization direction of the photo-alignment film and operate normally without any display malfunction.
また、このようにして作成した液晶表示装置を80℃、90%の高温高湿試験に供したところ、1000時間の該試験に耐えた。これにより、本実施例装置の長寿命化が確認できた。この際、遮光マスクで発生するような問題は見られなかった。 Further, when the liquid crystal display device thus prepared was subjected to a high temperature and high humidity test at 80 ° C. and 90%, it could withstand the test for 1000 hours. Thereby, it was confirmed that the life of the apparatus of this example was extended. At this time, no problem occurred in the light shielding mask.
(実施例2)
実施例1と同様にして、ポリビニルアルコール500(関東化学)、水溶性染料黒インク KAYACION BLACK P−GS(日本化薬)、紫外線吸収剤アデカスタブLA−46(アデカ)、イソプロピルアルコール、水を表1に記載した質量比および固形分濃度で含む紫外線遮光コーティング剤CLB2を作成した。表1におけるCLB3が実施例1のである。
(Example 2)
In the same manner as in Example 1, polyvinyl alcohol 500 (Kanto Chemical), water-soluble dye black ink KAYACION BLACK P-GS (Nippon Kayaku), ultraviolet absorber Adeka Stub LA-46 (Adeka), isopropyl alcohol, and water are listed in Table 1. The ultraviolet light shielding coating agent CLB2 containing the mass ratio and the solid content concentration described in 1 was prepared. CLB3 in Table 1 is that of Example 1.
最初に紫外線照射量を変えてUVラベルの状況を確認し、遮光膜の紫外線透過量を測定した。 First, the UV irradiation amount was changed, the state of the UV label was confirmed, and the UV transmission amount of the light shielding film was measured.
寸法30×40mm、厚さ0.12−0.17mmのカバーグラス(MATUNAMI写生)を用い、このカバーグラスに紫外線遮光コーティング剤を塗布しないもの(未加工品)と、紫外線遮光コーティング剤Mask Liquid CLB2(固形分濃度11.2%、粘度17.2cp(15℃)、pH8.1)およびMask Liquid CLB3(固形分濃度16.0%)を所定膜厚に塗布した加工品を用意した。 Using a cover glass (MATUNAMI copy) with dimensions of 30 x 40 mm and thickness of 0.12-0.17 mm, this cover glass is not coated with an ultraviolet light shielding coating agent (unprocessed product), and an ultraviolet light shielding coating agent Mask Liquid CLB2 A processed product in which (solid content concentration 11.2%, viscosity 17.2 cp (15 ° C.), pH 8.1) and Mask Liquid CLB3 (solid content concentration 16.0%) were applied to a predetermined film thickness was prepared.
カバーグラスに紫外線遮光コーティング剤を塗布するとき、バーコーター(テスター産業社製、製品名:SA−203)に、バーコーター(テスター産業社製)#6(膜厚13.72)、#9(膜厚20.61μm)、#13(膜厚29.77μm)を用い、下記の条件で塗布および乾燥した。 When an ultraviolet light shielding coating agent is applied to the cover glass, a bar coater (manufactured by Tester Sangyo Co., Ltd., product name: SA-203) is applied to a bar coater (manufactured by Tester Sangyo Co., Ltd.) # 6 (film thickness 13.72), # 9 ( Using a film thickness of 20.61 μm) and # 13 (film thickness of 29.77 μm), coating and drying were performed under the following conditions.
上記紫外線カットコーティング剤を塗布しないカバーグラスと塗布したカバーグラスに、UVランプ(アズワンSLUV−4:波長254nm)を用いて、波長254nmの紫外線を一定時間照射した(表3を参照)。 The cover glass not coated with the ultraviolet cut coating agent and the coated cover glass were irradiated with ultraviolet light having a wavelength of 254 nm for a certain period of time using a UV lamp (As One SLUV-4: wavelength 254 nm) (see Table 3).
このとき市販の「UVラベル」(日油技研工業社製UV−H、超高感度(0〜2000mj/cm2))を用いて、試験品を透過する紫外線量を測定した。このときのUVラベルの色と照射量との関係を、図8に示す(以下、図8〜12に示すUVラベルの色は白黒表示であるが、実際には薄く着色している)。また、紫外線照射後のUVラベルの状況を図9に示す。このようなUVラベルの色と照射量との関係の詳細に関しては、必要に応じて、下記のURL(日油技研工業 紫外線インジケーター UVラベルのサイト)を参照することができる。 At this time, a commercially available “UV label” (UV-H manufactured by NOF Corporation, ultra-high sensitivity (0 to 2000 mj / cm 2 )) was used to measure the amount of ultraviolet light transmitted through the test product. The relationship between the color of the UV label and the dose at this time is shown in FIG. 8 (hereinafter, the color of the UV label shown in FIGS. 8 to 12 is monochrome display, but is actually lightly colored). Moreover, the state of the UV label after ultraviolet irradiation is shown in FIG. Regarding the details of the relationship between the color of the UV label and the irradiation amount, the following URL (Nippon Giken Kogyo UV Indicator UV Label site) can be referred to as necessary.
URL: http://ondolab.com/product/seal/thermolabel/uv.html
得られた試験結果(膜厚と紫外線照射量の関係)を、表3に示す。
URL: http://ondolab.com/product/seal/thermolabel/uv.html
Table 3 shows the obtained test results (relationship between the film thickness and the UV irradiation amount).
(実施例3〜4)
実施例1と同様にして、ポリビニルアルコール500(関東化学)、水溶性染料黒インク KAYACION BLACK P−GS(日本化薬)、紫外線吸収剤アデカスタブLA−46(アデカ)、イソプロピルアルコール、水を表1に記載した質量比および固形分濃度で含む紫外線遮光コーティング剤CLB4,CLB5を作成した。
(Examples 3 to 4)
In the same manner as in Example 1, polyvinyl alcohol 500 (Kanto Chemical), water-soluble dye black ink KAYACION BLACK P-GS (Nippon Kayaku), ultraviolet absorber Adeka Stub LA-46 (Adeka), isopropyl alcohol, and water are listed in Table 1. Ultraviolet light shielding coating agents CLB4 and CLB5 containing the mass ratio and the solid content concentration described in the above were prepared.
紫外線遮光コーティング剤(日油技研工業社製UV−H)として、Mask Liquid CLB4:(形分濃度20%)およびMask Liquid CLB5(固形分濃度30%(増粘タイプ)を用いて、実施例2と同様にして膜厚が0.5μm、0.7μm、1.0μmになる条件で塗布し、乾燥(80℃、3分)する以外は、実施例2と同様に試験した。 Example 2 using Mask Liquid CLB4: (form concentration 20%) and Mask Liquid CLB5 (solid content concentration 30% (thickening type)) as an ultraviolet light shielding coating agent (UV-H manufactured by NOF Corporation) The test was conducted in the same manner as in Example 2 except that the coating was applied under the conditions of film thicknesses of 0.5 μm, 0.7 μm, and 1.0 μm and dried (80 ° C., 3 minutes).
紫外線カットコーティング剤を塗布したカバーグラスに、UVランプを用いて波長254nmの紫外線を一定時間照射し、このときのUVラベルを用いて試験品を透過する紫外線量を測定した。照射した紫外線量と透過した紫外線量により紫外線透過率を算出したときの、UVラベルの色と照射量との関係を図10に示す。 The cover glass coated with the ultraviolet cut coating agent was irradiated with ultraviolet rays having a wavelength of 254 nm for a certain time using a UV lamp, and the amount of ultraviolet rays transmitted through the test article was measured using the UV label at this time. FIG. 10 shows the relationship between the color of the UV label and the irradiation amount when the ultraviolet transmittance is calculated from the irradiated ultraviolet ray amount and the transmitted ultraviolet ray amount.
上記により得られた、各コート液について紫外線照射後のUVラベルの状況を、図11(紫外線照射後のUVラベルの状況;CLB4)および図12(紫外線照射後のUVラベルの状況;CLB5)に示す。 FIG. 11 (Status of UV label after UV irradiation; CLB4) and FIG. 12 (Status of UV label after UV irradiation; CLB5) for each coating solution obtained above after UV irradiation are shown. Show.
ラベルの色の変化により透過量を目視で確認した。この結果により遮光膜の紫外線透過率を算出し、それらの結果を、図13および図14に示す。 The amount of transmission was visually confirmed by the change in the color of the label. Based on this result, the ultraviolet transmittance of the light shielding film was calculated, and the results are shown in FIG. 13 and FIG.
1 ガラス基板
2 有効表示エリアに形成された画素
3 論理回路形成部
4 光配向材料
5 遮光膜
6 カラーフィルター形成部
DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Pixel formed in effective display area 3 Logic circuit formation part 4 Photo-alignment material 5 Light-shielding film 6 Color filter formation part
Claims (6)
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