JP2008050917A - Luminous reflection material having photocatalytic function - Google Patents
Luminous reflection material having photocatalytic function Download PDFInfo
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Abstract
Description
本発明は、道路標識、路肩表示、ガードレール貼り付け表示、避難誘導表示などに用いられる光触媒機能を有する蓄光性反射材に関するものである。 The present invention relates to a phosphorescent reflective material having a photocatalytic function used for road signs, road shoulder display, guardrail pasting display, evacuation guidance display, and the like.
従来より道路標識や路肩表示については、光を光源に向けて再帰反射させる再帰反射シートを用いた標識や表示が多く用いられている。 Conventionally, for road signs and road shoulder displays, signs and displays using a retroreflective sheet that retroreflects light toward a light source are often used.
この再帰反射シートに関し、夜間等において、光源がない場合の視認性を改善するための方法として、再帰反射シートに夜光性物質（蓄光性蛍光体）をベースフィルム等に含有させることが提案されている（特許文献１）。 Regarding this retroreflective sheet, as a method for improving the visibility in the absence of a light source at night or the like, it is proposed that the retroreflective sheet contains a luminous material (phosphorescent phosphor) in a base film or the like. (Patent Document 1).
近年、道路標識等の汚れを容易に除去する技術が注目されている。例えば、再帰プリズム反射体に自浄機能を持たした自浄性再帰反射体が提案されている（特許文献２）。 In recent years, a technique for easily removing dirt such as road signs has attracted attention. For example, a self-cleaning retroreflector having a self-cleaning function in a retroprism reflector has been proposed (Patent Document 2).
しかしながら、特許文献２の反射体は、夜間等の光源のない時間帯において、自浄機能を有効に発揮することができない。
本発明は、夜間においても光媒機能を発揮して汚れの付着を防止し、良好な視認性を発揮できる、道路標識・路肩表示用機材等として好適に使用できる反射板を提供することを主な目的とする。 The present invention mainly provides a reflector that can be used suitably as a road sign / shoulder display equipment, etc. that can exhibit a light medium function to prevent adhesion of dirt even at night and exhibit good visibility. With a purpose.
本発明者は、従来技術の問題点を解決するために鋭意研究を重ねた結果、特定構造の反射板が上記目的を達成できることを見出し本発明を完成するに至った。 As a result of intensive studies in order to solve the problems of the prior art, the present inventor has found that a reflector having a specific structure can achieve the above object, and has completed the present invention.
すなわち、本発明は、下記の反射板に係る。
１． 再帰反射機能を有する基材上に、１）蓄光機能及び蛍光機能を有する層並びに２）光触媒機能を有する層が順に形成されてなる反射板であって、
蓄光機能及び蛍光機能を有する層が、３１０〜８００ｎｍの間に発光スペクトルを有する蓄光顔料を含む反射板。
２． 蓄光機能及び蛍光機能を有する層における蓄光顔料の含有量が、５重量％以上である上記項１に記載の反射板。
３． 蓄光機能及び蛍光機能を有する層が、独立した複数の凸部により構成された立体模様を有するものであって、該凸部が、蓄光顔料を含有する熱可塑性樹脂により形成される上記項１又は２に記載の反射材。
４． 光触媒機能を有する層が、蓄光機能及び蛍光機能を有する層に、ペルオキソチタン化合物を含む溶液を塗布又は含浸させることにより形成されたものであることを特徴とする上記項１〜３のいずれかに記載の反射材。
That is, the present invention relates to the following reflector.
1. On a substrate having a retroreflective function, 1) a reflecting plate in which a layer having a phosphorescent function and a fluorescent function and 2) a layer having a photocatalytic function are sequentially formed,
The reflector which contains the phosphorescent pigment in which the layer which has a luminous function and a fluorescence function has an emission spectrum between 310-800 nm.
2. Item 2. The reflector according to Item 1, wherein the content of the phosphorescent pigment in the layer having the phosphorescent function and the fluorescent function is 5% by weight or more.
3. Item 1 or 2 above, wherein the layer having a phosphorescent function and a fluorescent function has a three-dimensional pattern composed of a plurality of independent convex portions, and the convex portions are formed of a thermoplastic resin containing a phosphorescent pigment. The reflecting material according to 2.
4). The layer having a photocatalytic function is formed by applying or impregnating a solution containing a peroxotitanium compound to a layer having a phosphorescent function and a fluorescent function. The reflective material described.
本発明の反射板によれば、反射板表面に付着する汚れの蓄積を有効に防止できる。すなわち、本発明の反射板は、蓄光機能及び蛍光機能を有する層が紫外線（３１０〜３７０ｎｍ）を放射することにより、光触媒機能を有する層の光触媒機能を有効に発現させることができる。 According to the reflecting plate of the present invention, accumulation of dirt adhering to the reflecting plate surface can be effectively prevented. That is, the reflecting plate of the present invention can effectively develop the photocatalytic function of the layer having the photocatalytic function when the layer having the phosphorescent function and the fluorescent function emits ultraviolet rays (310 to 370 nm).
より具体的には、本発明の反射板は、蓄光機能及び蛍光機能を有する層に含まれる蓄光顔料が日中に蓄えた光（紫外線）を夜間に放出することにより、夜間に付着する汚れを効果的に分解することができる。また、本発明の反射板は、蓄光顔料が紫外線を夜間に放出することにより、光触媒機能を有する層表面の親水性を向上させることができる。よって、蓄光顔料が紫外線を放射することにより分解した反射板表面の汚れを雨等により容易に洗い流すことができる。すわわち、本発明の反射板は、セルフクリーニング機能を有する。 More specifically, the reflective plate of the present invention emits the light (ultraviolet rays) stored in the daytime by the phosphorescent pigment contained in the layer having the phosphorescent function and the fluorescent function, thereby removing the dirt adhering to the nighttime. It can be decomposed effectively. Moreover, the reflecting plate of this invention can improve the hydrophilic property of the layer surface which has a photocatalytic function, when a luminous pigment discharge | releases an ultraviolet-ray at night. Therefore, the stain on the reflecting plate surface decomposed by the phosphorescent pigment emitting ultraviolet rays can be easily washed away by rain or the like. That is, the reflector of the present invention has a self-cleaning function.
本発明の反射板の蓄光機能及び蛍光機能を有する層に含まれる蓄光顔料は、さらに、可視光線（４００〜８００ｎｍ）を放射する。そのため、本発明の反射板は、例えば夜間であっても、有効に再帰反射機能を発揮することができる。 The phosphorescent pigment contained in the layer having the phosphorescent function and the fluorescent function of the reflector of the present invention further emits visible light (400 to 800 nm). Therefore, the reflecting plate of the present invention can effectively exhibit a retroreflection function even at night, for example.
本発明の反射板は、再帰反射機能を有する基材上に、１）蓄光機能及び蛍光機能を有する層並びに２）光触媒機能を有する層が順に形成されてなる反射板であって、
蓄光機能及び蛍光機能を有する層が、３１０〜８００ｎｍの間に発光スペクトルを有する蓄光顔料を含む。
The reflector of the present invention is a reflector obtained by sequentially forming 1) a layer having a phosphorescent function and a fluorescence function and 2) a layer having a photocatalytic function on a substrate having a retroreflective function,
The layer having a phosphorescent function and a fluorescent function includes a phosphorescent pigment having an emission spectrum between 310 to 800 nm.
再帰反射機能を有する基材としては、特に限定されず、使用目的等に応じて適宜選択すればよいが、基材シートの一面に配設された硝子微小球の層に部分的に金属蒸着層を形成してなる再帰反射性シートや、光透過性トップフィルム及びベースフィルムからなり、ベースフィルムの裏面がプリズム加工されてなる再帰反射性シートが好ましい。 The base material having a retroreflective function is not particularly limited, and may be appropriately selected depending on the purpose of use, etc., but the metal vapor deposition layer is partially formed on the glass microsphere layer disposed on one surface of the base material sheet. A retroreflective sheet formed by forming a light-transmitting top film and a base film, and a retroreflective sheet formed by prism processing the back surface of the base film is preferable.
蓄光機能及び蛍光機能を有する層としては、特に限定されないが、独立した複数の凸部により構成された立体模様を有するものであって、該凸部が、蓄光顔料を含有する熱可塑性樹脂により形成されるものが好ましい。以下、この場合を代表例として、蓄光機能及び蛍光機能を有する層について具体的に説明する。 Although it does not specifically limit as a layer which has a luminous function and a fluorescence function, it has a three-dimensional pattern comprised by the several independent convex part, Comprising: This convex part is formed with the thermoplastic resin containing a luminous pigment Are preferred. Hereinafter, taking this case as a representative example, a layer having a phosphorescent function and a fluorescence function will be specifically described.
蓄光顔料は、光の吸収と発光を繰り返すことができる。蓄光顔料としては、例えば硫化亜鉛、珪酸亜鉛、硫化亜鉛カドミウム、硫化カルシウム、硫化ストロンチウム、タングステン酸カルシウム、アルミン酸塩系蓄光性蛍体等の無機系顔料、ジアミノスチルベン系染料等の有機系粉末顔料等が挙げられる。これら蓄光顔料は、１種又は２種以上で用いることができる。かかる蓄光顔料は、可視光や紫外光等の各種光を吸収し（励起源）、エネルギーとして蓄え、励起源が停止した後、前記エネルギーにより発光する。ちなみに、該発光は基本的に暗所でのみ視認できる。 The phosphorescent pigment can repeat light absorption and emission. Examples of phosphorescent pigments include inorganic pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfide, calcium sulfide, strontium sulfide, calcium tungstate, aluminate phosphorescent phosphors, and organic powder pigments such as diaminostilbene dyes. Etc. These luminous pigments can be used alone or in combination of two or more. Such a phosphorescent pigment absorbs various light such as visible light and ultraviolet light (excitation source), stores it as energy, and emits light by the energy after the excitation source is stopped. Incidentally, the emitted light is basically visible only in a dark place.
本発明において用いる蓄光顔料としては、輝度及び残光性の観点から、アルミン酸塩系蓄光性蛍体が好ましい。特に、アルミン酸塩系蓄光性蛍体の中でも、耐候性、耐薬品性（特に耐水性）及び発光特性（発光スペクトルが３３０ｎｍ〜８００ｎｍと広く又発光ピーク値が４９０ｎｍである）の観点から、「Ｓｒ４Ａｌ14 Ｏ25；Ｅｕ、Ｄｙ」の組成式で表されるストロンチウムアルミン酸塩が好ましく、より短い領域（発光スペクトル３１０ｎｍ〜８００ｎｍ）に発光特性を示す「Ｓｒ４Ａｌ14Ｏ25；Ｅｕ、Ｄｙ、Ｂｉ」の組成式で表されるストロンチウムアルミン酸塩がより好ましい。 The phosphorescent pigment used in the present invention is preferably an aluminate-based phosphorescent phosphor from the viewpoint of luminance and persistence. In particular, among aluminate-based phosphorescent phosphors, from the viewpoint of weather resistance, chemical resistance (particularly water resistance), and emission characteristics (emission spectrum is wide from 330 nm to 800 nm and emission peak value is 490 nm), Sr 4 Al 14 O 25 ; Eu, Dy ”is preferred, and strontium aluminate represented by the composition formula is preferred, and“ Sr 4 Al 14 O 25 ; Eu, which exhibits emission characteristics in a shorter region (emission spectrum 310 nm to 800 nm). Strontium aluminate represented by the composition formula of “Dy, Bi” is more preferable.
蓄光機能及び蛍光機能を有する層における蓄光顔料の含有量は、特に限定されないが、５重量％以上が好ましく、５〜５０重量％がより好ましい。蓄光顔料の含有量が５重量％未満の場合、残光性能が劣り後述する光触媒を励起するための光線を十分に発光させることができない。また、蓄光顔料の含有量が５０重量％を超える場合、光触媒作用が強くなりすぎてしまい、光触媒に接する他の部材を分解させ、反射板の劣化が進行するおそれがある。また、コストの面でも問題がある。 The content of the phosphorescent pigment in the layer having the phosphorescent function and the fluorescent function is not particularly limited, but is preferably 5% by weight or more, and more preferably 5 to 50% by weight. When the content of the phosphorescent pigment is less than 5% by weight, the afterglow performance is inferior, and light for exciting the photocatalyst described later cannot be emitted sufficiently. Moreover, when content of a luminous pigment exceeds 50 weight%, photocatalytic action will become strong too much, there exists a possibility that the other member which touches a photocatalyst may be decomposed | disassembled and deterioration of a reflecting plate may progress. There is also a problem in terms of cost.
熱可塑性樹脂としては、ポリプロピレン樹脂、ポリ塩化ビニル樹脂、ポリエチレン樹脂、ＥＶＡ樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、各種熱可塑性エラストマーなどを例示することができる。これらの樹脂は、１種又は２種以上で用いることができる。 Examples of the thermoplastic resin include polypropylene resin, polyvinyl chloride resin, polyethylene resin, EVA resin, polystyrene resin, ABS resin, and various thermoplastic elastomers. These resins can be used alone or in combination of two or more.
独立した複数の凸部により構成された立体模様を有する蓄光機能及び蛍光機能を有する層の形成方法としては、例えば、蓄光顔料を含有する溶融熱可塑性樹脂を、独立した複数の凹部を有する型に入れ、該型を用いて、基材シートに凸形状を形成させる方法が挙げられる。 As a method for forming a layer having a phosphorescent function and a fluorescent function having a three-dimensional pattern constituted by a plurality of independent convex portions, for example, a molten thermoplastic resin containing a phosphorescent pigment is formed into a mold having a plurality of independent concave portions. And a method of forming a convex shape on the substrate sheet using the mold.
光触媒機能を有する層に含まれる光触媒としては、例えばＴｉＯ2 ，ＺｎＯ，ＳｒＴｉＯ3，ＣｄＳ，ＣｄＯ，ＣａＰ，ＩｎＰ，Ｉｎ2Ｏ3 ，ＣａＡｓ，ＢａＴｉＯ3 ，Ｋ2ＮｂＯ3，Ｆｅ2Ｏ3，Ｔａ2Ｏ5 ，ＷＯ3 ，ＳａＯ2，Ｂｉ2Ｏ3 ，ＮｉＯ，Ｃｕ2Ｏ，ＳｉＣ，ＳｉＯ2 ，ＭｏＳ2，ＭｏＳ3 ，ＩｎＰｂ，ＲｕＯ2 ，ＣｅＯ2等が挙げられる。これらの光触媒は、可視光線よりも少し短波長である５０〜４００nmの紫外線を吸収することができる。また、上記例示の光触媒の中には、吸収波長が可視光線を領域とするものもある。例えば、ＳｉＣは４１３nm、ＣｄＳは４９６nm、Ｆｅ2Ｏ3は５３９nmの可視光線を吸収することができる。 Examples of the photocatalyst contained in the layer having a photocatalytic function include TiO 2 , ZnO, SrTiO 3 , CdS, CdO, CaP, InP, In 2 O 3 , CaAs, BaTiO 3 , K 2 NbO 3 , Fe 2 O 3 , Ta. 2 O 5 , WO 3 , SaO 2 , Bi 2 O 3 , NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , MoS 3 , InPb, RuO 2 , CeO 2 and the like. These photocatalysts can absorb ultraviolet rays of 50 to 400 nm that are slightly shorter than visible light. Some of the photocatalysts exemplified above have an absorption wavelength in the visible light region. For example, SiC can absorb visible light of 413 nm, CdS of 496 nm, and Fe 2 O 3 of 539 nm.
光触媒機能を有する層における光触媒の含有量に制限はないが、１０％以上９５％以下が好ましい。 Although there is no restriction | limiting in content of the photocatalyst in the layer which has a photocatalyst function, 10% or more and 95% or less are preferable.
このように光触媒を励起する光線の波長は、用いる光触媒の種類によって異なる。従って、紫外線供給源の発光スペクトル特性や用途に応じて、光触媒を選択したり、複数種類の光触媒を組み合わせて用いることができる。 Thus, the wavelength of the light beam that excites the photocatalyst varies depending on the type of photocatalyst used. Therefore, a photocatalyst can be selected or a plurality of types of photocatalysts can be used in combination depending on the emission spectrum characteristics of the ultraviolet light source and the application.
また、無機顔料や金属を添加することにより、光触媒機能を有する層の組成を調整したり、光触媒機能を有する層の製造過程での熱処理条件を調整することによって、光触媒機能の発揮に必要な紫外線の波長（吸収帯）を変えることができる。例えば、ＴｉＯ2にＣｒＯ3 を少量添加する場合、吸収帯は長波長側に移動する。 In addition, by adding inorganic pigments and metals, the composition of the layer having the photocatalytic function is adjusted, or the heat treatment conditions in the production process of the layer having the photocatalytic function are adjusted, so that an ultraviolet ray necessary for exerting the photocatalytic function is obtained. The wavelength (absorption band) can be changed. For example, when a small amount of CrO 3 is added to TiO 2 , the absorption band moves to the long wavelength side.
上記例示の光触媒の中でも、ＴｉＯ2（酸化チタン）は、市販されており、且つ、安価であるうえ、人体に無害であるため、利用しやすい。例えば、商品名「ＳＴ−０１」（石原産業株式会社製）は粉末として提供されており、商品名「ＴＯゾル」（株式会社田仲転写製）及び商品名「ＳＴＳ−０１」（石原産業株式会社製）はゾル状態で提供されている。このような粉末やゾルを構成しているＴｉＯ2は、粒径が７〜２０ｎｍであり非常に細かい。 Among the photocatalysts exemplified above, TiO 2 (titanium oxide) is easy to use because it is commercially available and is inexpensive and harmless to the human body. For example, the product name “ST-01” (manufactured by Ishihara Sangyo Co., Ltd.) is provided as a powder, and the product name “TO sol” (manufactured by Tanaka Transcript Co., Ltd.) and the product name “STS-01” (Ishihara Sangyo Co., Ltd.) are provided. Made in the sol state. TiO 2 constituting such a powder or sol has a particle size of 7 to 20 nm and is very fine.
また、窒素原子を３．３重量％以上含有する水酸化チタンは、他の光触媒よりも、上記蓄光顔料「Ｓｒ４Ａｌ14 Ｏ25；Ｅｕ、Ｄｙ」及び「Ｓｒ４Ａｌ14Ｏ25；Ｅｕ、Ｄｙ、Ｂｉ」の発光スペクトルの波長により近い、可視光域（４００ｎｍ〜８００ｎｍ）の波長の光でも十分に活性化される点で好ましい。この窒素原子を含有する水酸化チタンは、例えば空気中、水酸化チタンを４００℃で焼成することにより得ることができる。 Further, titanium hydroxide containing 3.3% by weight or more of nitrogen atoms is more preferable than other photocatalysts as the above phosphorescent pigments “Sr 4 Al 14 O 25 ; Eu, Dy” and “Sr 4 Al 14 O 25 ; Eu, Dy, Bi ”is preferable in that it is sufficiently activated even with light having a wavelength in the visible light range (400 nm to 800 nm) that is closer to the wavelength of the emission spectrum of“ Dy, Bi ”. The titanium hydroxide containing nitrogen atoms can be obtained, for example, by baking titanium hydroxide at 400 ° C. in the air.
光触媒機能を有する層の形成方法としては、特に限定されず、公知の方法を採用すればよい。例えば、スプレ-コーティング等の方法により、蓄光機能及び蛍光機能を有する層に、酸化チタン等の光触媒を含有する塗膜層を形成する方法が挙げられる。塗布する際に使用する原料、原料の配合割合、塗布後の後処理（例えば乾燥等）等は、常法に従って決定すればよい。具体的には、特開２００５−８９２１５に記載の方法、すなわち、蓄光機能及び蛍光機能を有する層に、ペルオキソチタン化合物を含む溶液を塗布又は含浸させることにより光触媒機能を有する層を形成することができる。前記溶液を調整する際に用いる溶媒としては、例えば水が挙げられる。 It does not specifically limit as a formation method of the layer which has a photocatalyst function, What is necessary is just to employ | adopt a well-known method. For example, there is a method of forming a coating layer containing a photocatalyst such as titanium oxide on a layer having a phosphorescent function and a fluorescent function by a method such as spray coating. The raw materials used at the time of application, the blending ratio of the raw materials, post-treatment after application (for example, drying, etc.), etc. may be determined according to conventional methods. Specifically, the method described in JP-A-2005-89215, that is, a layer having a photocatalytic function can be formed by applying or impregnating a layer having a phosphorescent function and a fluorescence function with a solution containing a peroxotitanium compound. it can. Examples of the solvent used when preparing the solution include water.
溶液中のペルオキソチタン化合物の濃度は、特に限定はないが、０．１重量％以上、６０重量％以下が好ましい。 The concentration of the peroxotitanium compound in the solution is not particularly limited, but is preferably 0.1% by weight or more and 60% by weight or less.
塗布又は含浸後、大気中に放置するか、熱処理により乾燥処理を行ってもよい。 After coating or impregnation, the substrate may be left in the atmosphere or may be dried by heat treatment.
光触媒機能を有する層中の光触媒は、蛍光灯の発する紫外線や太陽光による紫外線を受けることにより励起される。 The photocatalyst in the layer having the photocatalytic function is excited by receiving an ultraviolet ray emitted from a fluorescent lamp or an ultraviolet ray caused by sunlight.
また、蛍光灯の紫外線を受けない時間帯、太陽光の紫外線を受けることができない夜間等においては、蓄光機能及び蛍光機能を有する層が発する紫外線を受けることにより励起される。そして、光触媒による酸化、還元作用により自動車の排ガス等に含まれる窒素酸化物、硫黄酸化物等の環境汚染物質を分解し、反射板表面に付着する汚れの蓄積を有効に防止できる。 Further, in a time zone when the fluorescent lamp does not receive ultraviolet light, at night when it cannot receive ultraviolet light of sunlight, it is excited by receiving ultraviolet light emitted from a layer having a phosphorescent function and a fluorescent function. In addition, environmental pollutants such as nitrogen oxides and sulfur oxides contained in the exhaust gas of automobiles can be decomposed by the oxidation and reduction action by the photocatalyst, and accumulation of dirt adhering to the reflecting plate surface can be effectively prevented.
以下に、実施例及び比較例を示し、本発明を詳細に説明する。ただし、本発明は、これら実施例等に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.
実施例１
再帰反射機能を有する基材として、基材シートの一面に配設された硝子微小球の層に部分的に金属蒸着層を形成した再帰反射性シートを用いた。
Example 1
As a base material having a retroreflective function, a retroreflective sheet in which a metal vapor deposition layer was partially formed on a glass microsphere layer disposed on one surface of the base material sheet was used.
組成式Ｓｒ４Ａｌ14 Ｏ25；Ｅｕ、Ｄｙで表される蓄光顔料（イージーブライト株式会社製、商品名ＥＺＣＢ）を２０重量％含有する溶融した熱可塑性エラストマー樹脂を、独立した複数の凹部を有する型に入れ、該型を用いて、前記シート上に凸形状を形成させることにより蓄光機能及び蛍光機能を有する層を形成させた。
蓄光機能及び蛍光機能を有する層上に、株式会社デジック製光触媒（商品名「ＳＥチタンコート」）を塗布することにより光触媒機能を有する層（光触媒：ＴｉＯ２）を形成させた。塗布には、スピンコート法を用い、大気中、温度２５℃、湿度６０％で２４時間、乾燥させた。
A molten thermoplastic elastomer resin containing 20 wt% of a phosphorescent pigment represented by a composition formula Sr 4 Al 14 O 25 ; Eu and Dy (manufactured by Easy Bright Co., Ltd., trade name EZCB) has a plurality of independent recesses. A layer having a phosphorescent function and a fluorescence function was formed by forming a convex shape on the sheet using the mold.
A layer having a photocatalytic function (photocatalyst: TiO 2 ) was formed by applying a photocatalyst manufactured by Digic Co., Ltd. (trade name “SE Titanium Coat”) on the layer having a phosphorescent function and a fluorescent function. For the application, spin coating was used, and the coating was dried in the air at a temperature of 25 ° C. and a humidity of 60% for 24 hours.
以上の方法により、本発明の反射板を作製した。 The reflector of the present invention was produced by the above method.
実施例２
蓄光顔料として、組成式Ｓｒ４Ａｌ14Ｏ25；Ｅｕ、Ｄｙ、Ｂｉで表される蓄光顔料（イージーブライト株式会社製、商品名ＥＺＣＢＸ）を用い、さらに、光触媒機能を有する層を、空気中、水酸化チタンを４００℃で焼成することにより得られる窒素原子の含有量が３．５重量％である水酸化チタンを用いて形成した以外は、実施例１と同様にして、本発明の反射板を作製した。
Example 2
As a phosphorescent pigment, a phosphorescent pigment represented by the composition formula Sr 4 Al 14 O 25 ; Eu, Dy, Bi (manufactured by Easy Bright Co., Ltd., trade name EZCBX) is used. The reflector of the present invention is the same as Example 1 except that titanium hydroxide is obtained by baking titanium hydroxide at 400 ° C. and the content of nitrogen atoms is 3.5% by weight. Was made.
比較例１
蓄光機能及び蛍光機能を有する層を形成させずに、再帰反射性シートに直接光触媒機能を有する層を形成させる以外は、実施例１と同様の方法により、反射板を作製した。
Comparative Example 1
A reflector was produced in the same manner as in Example 1 except that a layer having a photocatalytic function was directly formed on the retroreflective sheet without forming a layer having a phosphorescent function and a fluorescence function.
試験例１（メチレンブルー脱色試験）
実施例１〜２及び比較例１にて得られた反射板の光触媒機能を有する層表面の汚れを光触媒により分解できるかどうかについて試験を行った。
Test Example 1 (Methylene blue decolorization test)
A test was conducted to determine whether or not the photocatalyst can degrade the dirt on the surface of the layer having the photocatalytic function of the reflectors obtained in Examples 1 and 2 and Comparative Example 1.
具体的には、実施例１〜２及び比較例１にて得られた反射板に対してメチレンブルー脱色試験を下記（１）〜（１０）に従って行い、メチレンブルーの分解の程度を肉眼観察により確認した。 Specifically, a methylene blue decoloration test was performed on the reflectors obtained in Examples 1 and 2 and Comparative Example 1 according to the following (1) to (10), and the degree of decomposition of methylene blue was confirmed by visual observation. .
メチレンブルーが全く分解しなかったものを１、メチレンブルーが少しだけ分解したものを２、メチレンブルーがほとんど分解したものを３と評価した。結果を表１に示す。
（１）比較例１にて得られた反射板の光触媒機能を有する層上にメチレンブルーを塗布した後、１０Ｗのブラックライトを２時間照射した。
（２）比較例１にて得られた反射板の光触媒機能を有する層上にメチレンブルーを塗布した後、暗室に２時間放置した。
（３）実施例１にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、１０Ｗのブラックライトを２時間照射した。
（４）実施例１にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。その後、この反射板を暗室に４８時間放置した場合、蓄光剤は発光しなくなった。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、１０Ｗのブラックライトを２時間照射した。
（５）実施例１にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、暗室に８時間放置した。
（６）実施例１にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。その後、この反射板を暗室に４８時間放置した場合、蓄光剤は発光しなくなった。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、暗室に８時間放置した。
（７）実施例２にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、１０Ｗのブラックライトを２時間照射した。
（８）実施例２にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。その後、この反射板を暗室に４８時間放置した場合、蓄光剤は発光しなくなった。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、１０Ｗのブラックライトを２時間照射した。
（９）実施例２にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、暗室に８時間放置した。
（１０）実施例２にて得られた反射板に４０Ｗの蛍光灯を２時間照射した場合、蓄光剤が紫外線及び可視光線を発光した。その後、この反射板を暗室に４８時間放置した場合、蓄光剤は発光しなくなった。この反射板の光触媒機能を有する層にメチレンブルーを塗布した後、暗室に８時間放置した。
The case where methylene blue was not decomposed at all was evaluated as 1, the case where methylene blue was slightly decomposed was evaluated as 2, and the case where methylene blue was almost decomposed was evaluated as 3. The results are shown in Table 1.
(1) After coating methylene blue on the layer having the photocatalytic function of the reflector obtained in Comparative Example 1, 10 W of black light was irradiated for 2 hours.
(2) Methylene blue was applied on the layer having the photocatalytic function of the reflector obtained in Comparative Example 1, and then left in a dark room for 2 hours.
(3) When the reflecting plate obtained in Example 1 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. After applying methylene blue to the layer having the photocatalytic function of the reflector, 10 W black light was irradiated for 2 hours.
(4) When the reflecting plate obtained in Example 1 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Thereafter, when this reflector was left in a dark room for 48 hours, the phosphorescent agent did not emit light. After applying methylene blue to the layer having the photocatalytic function of the reflector, 10 W black light was irradiated for 2 hours.
(5) When the reflecting plate obtained in Example 1 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Methylene blue was applied to the layer having the photocatalytic function of the reflector, and then left in a dark room for 8 hours.
(6) When the reflecting plate obtained in Example 1 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Thereafter, when this reflector was left in a dark room for 48 hours, the phosphorescent agent did not emit light. Methylene blue was applied to the layer having the photocatalytic function of the reflector, and then left in a dark room for 8 hours.
(7) When the reflecting plate obtained in Example 2 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. After applying methylene blue to the layer having the photocatalytic function of the reflector, 10 W black light was irradiated for 2 hours.
(8) When the reflecting plate obtained in Example 2 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Thereafter, when this reflector was left in a dark room for 48 hours, the phosphorescent agent did not emit light. After applying methylene blue to the layer having the photocatalytic function of the reflector, 10 W black light was irradiated for 2 hours.
(9) When the reflecting plate obtained in Example 2 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Methylene blue was applied to the layer having the photocatalytic function of the reflector, and then left in a dark room for 8 hours.
(10) When the reflecting plate obtained in Example 2 was irradiated with a 40 W fluorescent lamp for 2 hours, the phosphorescent agent emitted ultraviolet rays and visible rays. Thereafter, when this reflector was left in a dark room for 48 hours, the phosphorescent agent did not emit light. Methylene blue was applied to the layer having the photocatalytic function of the reflector, and then left in a dark room for 8 hours.
なお、上記（１）〜（１０）において、可視光線の発光は、目視にて確認できた。また、紫外線の発光は、蛍光体を近づけることによる蛍光体の発光により確認した。 In addition, in said (1)-(10), light emission of visible light was able to be confirmed visually. The emission of ultraviolet rays was confirmed by the emission of the phosphor by bringing the phosphor closer.
表１の（１）及び（２）の評価から、光触媒機能を有する層がメチレンブルーを分解する能力を有することがわかる。 From the evaluation of (1) and (2) in Table 1, it can be seen that the layer having a photocatalytic function has the ability to decompose methylene blue.
表１の（１）並びに（３）及び（７）の評価から、蓄光剤含有層は、光触媒の効果を阻害しないことがわかる。 From the evaluation of (1) and (3) and (7) in Table 1, it can be seen that the luminous agent-containing layer does not inhibit the effect of the photocatalyst.
表１の（３）及び（４）の評価、並びに（７）及び（８）の評価から、１０Ｗのブラックライトを照射することにより、光触媒機能を有する層は、蓄光剤の発光の有無に関わらず、同様の光触媒効果を発揮することがわかる。 From the evaluations of (3) and (4) in Table 1 and the evaluations of (7) and (8), the layer having a photocatalytic function is irradiated with 10 W of black light regardless of whether or not the phosphorescent agent emits light. It can be seen that the same photocatalytic effect is exhibited.
表１の（５）及び（６）の評価、並びに（９）及び（１０）の評価から、蓄光剤からの発光により光触媒機能が発現し、メチレンブルーが分解したことがわかる。 From the evaluations of (5) and (6) in Table 1 and the evaluations of (9) and (10), it can be seen that the photocatalytic function was expressed by the light emission from the phosphorescent agent and methylene blue was decomposed.
表１の（５）及び（９）の評価から、実施例２にて得られた反射板の方が、実施例１にて得られた反射板より、メチレンブルーをより分解できることがわかる。 From the evaluations of (5) and (9) in Table 1, it can be seen that the reflector obtained in Example 2 can decompose methylene blue more than the reflector obtained in Example 1.
Claims (4)
蓄光機能及び蛍光機能を有する層が、３１０〜８００ｎｍの間に発光スペクトルを有する蓄光顔料を含む反射板。 On a substrate having a retroreflective function, 1) a reflecting plate in which a layer having a phosphorescent function and a fluorescent function and 2) a layer having a photocatalytic function are sequentially formed,
The reflector which contains the phosphorescent pigment in which the layer which has a luminous function and a fluorescence function has an emission spectrum between 310-800 nm.
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| JP2006231220A JP2008050917A (en) | 2006-08-28 | 2006-08-28 | Luminous reflection material having photocatalytic function |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013166885A (en) * | 2012-02-16 | 2013-08-29 | Lintec Corp | Pressure-sensitive adhesive sheet for ultraviolet irradiation type sign and ultraviolet irradiation type sign device |
| JP2019049666A (en) * | 2017-09-12 | 2019-03-28 | クラレファスニング株式会社 | Luminous sheet |
| JP2020090594A (en) * | 2018-12-04 | 2020-06-11 | リンテック株式会社 | Luminescent film and manufacturing method therefor, and ultraviolet irradiation type luminescent sheet |
| JP2020171874A (en) * | 2019-04-08 | 2020-10-22 | 日鉄鋼板株式会社 | Covering material and inactivation method of germ or virus |
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2006
- 2006-08-28 JP JP2006231220A patent/JP2008050917A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013166885A (en) * | 2012-02-16 | 2013-08-29 | Lintec Corp | Pressure-sensitive adhesive sheet for ultraviolet irradiation type sign and ultraviolet irradiation type sign device |
| JP2019049666A (en) * | 2017-09-12 | 2019-03-28 | クラレファスニング株式会社 | Luminous sheet |
| JP7003511B2 (en) | 2017-09-12 | 2022-01-20 | クラレファスニング株式会社 | Luminescent sheet |
| JP2020090594A (en) * | 2018-12-04 | 2020-06-11 | リンテック株式会社 | Luminescent film and manufacturing method therefor, and ultraviolet irradiation type luminescent sheet |
| JP7185823B2 (en) | 2018-12-04 | 2022-12-08 | リンテック株式会社 | Luminescent film, manufacturing method thereof, and UV irradiation type luminescent sheet |
| JP2020171874A (en) * | 2019-04-08 | 2020-10-22 | 日鉄鋼板株式会社 | Covering material and inactivation method of germ or virus |
| JP7374605B2 (en) | 2019-04-08 | 2023-11-07 | 日鉄鋼板株式会社 | Dressing material and method for inactivating bacteria or viruses |
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