JP2003232018A - Material and execution method for photocatalytic road marking object, and photocatalytic road making object - Google Patents
Material and execution method for photocatalytic road marking object, and photocatalytic road making objectInfo
- Publication number
- JP2003232018A JP2003232018A JP2002031723A JP2002031723A JP2003232018A JP 2003232018 A JP2003232018 A JP 2003232018A JP 2002031723 A JP2002031723 A JP 2002031723A JP 2002031723 A JP2002031723 A JP 2002031723A JP 2003232018 A JP2003232018 A JP 2003232018A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytic
- road marking
- road
- coating
- marking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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Landscapes
- Catalysts (AREA)
- Road Signs Or Road Markings (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアスファルト、排水
性アスファルト、コンクリートなどの路面に適用できる
光触媒性路面標示物用材料、光触媒性路面標示物の施工
方法、及び光触媒性路面標示物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic road marking material applicable to road surfaces such as asphalt, drainage asphalt and concrete, a method for constructing a photocatalytic road marking, and a photocatalytic road marking.
【０００２】[0002]
【従来の技術】従来使用されている酸化チタン膜形成方
法には、酸化チタン粉体スラリーを基材に塗布後焼成す
るゾルゲル法、スパッタ法、ＣＶＤ法、プラズマ溶射法
等がある。酸化チタン粉末スラリーの塗布法は、緻密で
密着性良好な膜は得られ難く、有機物上に塗布した場合
は酸化チタンの光触媒活性により基材を劣化させる問題
がある。塩化チタンや硫酸チタン等の水溶液を塗布する
方法は有害なハロゲン化合物を生成し、また、焼成温度
も数１００℃以上を必要とするため、アスファルト、排
水性アスファルト、コンクリート等の路面には使用でき
ない。プラズマ溶射、スパッタ法、ＣＶＤ法などは大規
模な装置が必要となるため路面への応用には極めて難し
い。また、ゾルゲル法は原料の貯蔵安定性を維持するた
め強酸や強塩基性であることが多く、酸やアルカリで侵
されやすい材料には不向きであった。2. Description of the Related Art Conventionally used methods for forming a titanium oxide film include a sol-gel method, a sputtering method, a CVD method and a plasma spraying method in which a titanium oxide powder slurry is applied to a substrate and then baked. The titanium oxide powder slurry coating method has a problem that it is difficult to obtain a dense and good adhesive film, and when coated on an organic substance, the photocatalytic activity of titanium oxide deteriorates the substrate. The method of applying an aqueous solution of titanium chloride, titanium sulfate, etc. produces harmful halogen compounds and requires a firing temperature of several hundreds of degrees Celsius or higher, so it cannot be used for road surfaces such as asphalt, drainage asphalt, and concrete. . The plasma spraying, the sputtering method, the CVD method, and the like require a large-scale device and are extremely difficult to apply to the road surface. Further, the sol-gel method is often a strong acid or a strong base in order to maintain the storage stability of the raw material, and is not suitable for a material which is easily attacked by an acid or an alkali.
【０００３】[0003]
【発明が解決しようとする課題】これらの欠点を改良す
るため、例えば特開平９−７１４１８号公報に提案され
ているアモルファス型チタンゾルは、それ自体は光触媒
能をもたないため、基材に塗布後、加熱処理が必要であ
り、使用できる基材、用途は限られている。さらに、ア
モルファス型チタンゾルを約１００℃で２時間以上加熱
すると一部の酸化チタンがその前駆体をへてアナターゼ
結晶に結晶化してアナターゼ結晶／アモルファス混合酸
化チタンゾル溶液が得られるが、これを単独で塗布する
と基材上で液滴を形成しながら乾燥成膜されるため、緻
密で密着性良好な酸化チタン皮膜を形成できず干渉色が
でたり、光触媒能が上がらなかったりするという不具合
があった。In order to improve these drawbacks, for example, an amorphous titanium sol proposed in Japanese Patent Laid-Open No. 9-71418 has no photocatalytic activity by itself, and therefore is applied to a substrate. After that, heat treatment is required, and usable substrates and applications are limited. Further, when the amorphous titanium sol is heated at about 100 ° C. for 2 hours or more, a part of the titanium oxide is crystallized into anatase crystals by using its precursor to obtain anatase crystal / amorphous mixed titanium oxide sol solution. When applied, it forms a droplet on the substrate while forming a dry film, so a dense titanium oxide film with good adhesion could not be formed, resulting in interference colors and photocatalytic activity not increasing. .
【０００４】本発明の目的は、常温で成膜が可能であ
り、従来のアナターゼ結晶／アモルファス混合酸化チタ
ンゾル溶液を用いた酸化チタン膜よりも光触媒能が高
く、干渉色の出にくい、優れた特性を有する酸化チタン
膜を、塗布形成することにより、従来は高温加熱により
形成していた酸化チタン膜を、常温付近において路面標
示物上に形成し、酸化チタンの防汚染性を発現出来るよ
うにした光触媒性路面標示物の施工方法を提供すること
にある。また、本発明の目的は、前記施工方法に用いる
ことができ、上記のような優れた特性を有する酸化チタ
ン膜を形成できる光触媒性路面標示物用材料を提供する
ことにある。さらに、本発明の目的は、優れた特性の酸
化チタン膜が形成できる上記光触媒性路面標示物用材料
が用いられ、アスファルト、排水性アスファルト、コン
クリートに使用できる光触媒性路面標示物を提供するこ
とにある。The object of the present invention is that it is capable of forming a film at room temperature, has a higher photocatalytic ability than a conventional titanium oxide film using a mixed anatase crystal / amorphous titanium oxide sol solution, and is less likely to produce an interference color. By coating and forming a titanium oxide film having, the titanium oxide film, which was conventionally formed by heating at high temperature, is formed on the road marking near room temperature, so that the anti-staining property of titanium oxide can be expressed. It is to provide a construction method of a photocatalytic road marking. Another object of the present invention is to provide a photocatalytic road marking material that can be used in the above-mentioned construction method and can form a titanium oxide film having the above-mentioned excellent properties. Further, an object of the present invention is to provide a photocatalytic road marking that can be used for asphalt, drainage asphalt, and concrete, using the above-mentioned photocatalytic road marking material capable of forming a titanium oxide film having excellent characteristics. is there.
【０００５】[0005]
【課題を解決するための手段】本発明はこのような問題
に鑑み鋭意研究の結果、常温のような低温でも成膜が可
能であり従来のアナターゼ／アモルファス混合酸化チタ
ンゾル溶液を用いた酸化チタン膜よりも光触媒能が高い
光触媒コーティング膜を得られる光触媒コーティング液
を光触媒性路面標示物材料として用いることにより、干
渉色が目視で認められず、かつ視認性、反射輝度性をそ
こなわない本発明の光触媒性路面標示物を完成するに至
った。すなわち、本発明は次のものに関する。As a result of earnest research in view of the above problems, the present invention can form a film even at a low temperature such as room temperature, and a titanium oxide film using a conventional anatase / amorphous mixed titanium oxide sol solution. By using a photocatalyst coating liquid capable of obtaining a photocatalyst coating film having a higher photocatalytic ability as a photocatalytic road marking material, the interference color is not visually recognized, and the visibility and the reflection brightness are not impaired. The photocatalytic road marking was completed. That is, the present invention relates to the following.
【０００６】本発明における第１の発明は、チタン化合
物を含む塩基性溶液から作製した水酸化チタンゲルに過
酸化水素を作用させて得た無定形酸化チタンを含む酸化
チタンゾル溶液と、有機物質と、溶媒又は分散媒とを含
む光触媒性路面標示物用材料である。A first aspect of the present invention is a titanium oxide sol solution containing amorphous titanium oxide obtained by reacting hydrogen peroxide on a titanium hydroxide gel prepared from a basic solution containing a titanium compound, and an organic substance. A photocatalytic pavement marking material containing a solvent or a dispersion medium.
【０００７】前記酸化チタンゾル溶液は、酸化チタンの
一部がアナターゼ型結晶酸化チタン又はその前駆体を含
有するアナターゼ型結晶酸化チタン／無定形酸化チタン
混合物からなるのが好ましい。前記有機物質は、ポリエ
チレンオキサイド重合体変性ポリジメチルシロキサン又
はポリエチレンオキサイド−ポリプロピレンオキサイド
ブロック共重合体変性ポリジメチルシロキサンであるの
が好ましい。酸化チタンゾル溶液の固形分と有機物質の
比は、前者：後者の重量比で、１：０．０１〜１：１０
であるのが好ましい。前記溶媒又は分散媒は、水、有機
溶媒又は水−有機溶媒混合物であるのが好ましい。前記
有機溶媒はアルコール類を含むのが好ましい。The titanium oxide sol solution preferably comprises an anatase type crystalline titanium oxide / amorphous titanium oxide mixture in which a part of titanium oxide contains anatase type crystalline titanium oxide or a precursor thereof. The organic material is preferably polyethylene oxide polymer-modified polydimethylsiloxane or polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane. The ratio of the solid content of the titanium oxide sol solution to the organic substance is 1: 0.01 to 1:10 by weight ratio of the former to the latter.
Is preferred. The solvent or dispersion medium is preferably water, an organic solvent or a water-organic solvent mixture. The organic solvent preferably contains alcohols.
【０００８】本発明における第２の発明は、路面標示物
用塗料を基材上へ塗布して塗膜を形成する工程と、前記
塗膜を固化させる工程と、上記いずれかの光触媒性路面
標示物用材料を塗布して塗膜を形成する工程と、光触媒
性路面標示物用材料の塗膜を１００℃以下で固化させる
工程とを含む光触媒性路面標示物の施工方法である。A second aspect of the present invention is the step of applying a coating for a road marking material onto a substrate to form a coating film, the step of solidifying the coating film, and any one of the above photocatalytic road markings. It is a method of constructing a photocatalytic road marking, which includes a step of applying a material material to form a coating film and a step of solidifying the coating film of the photocatalytic road marking material at 100 ° C or lower.
【０００９】この施工方法において、光触媒性路面標示
物用材料の塗膜は１００℃〜外気温で乾燥して固化させ
るのが好ましい。また、路面標示物用塗料中に粒子状の
反射体を含有させ、かつ該路面標示物用塗料の塗膜が固
化する前に、さらに粒子状の反射体を前記塗膜表面に散
布するのが好ましい。路面標示物用塗料中に含有させる
反射体は、路面標示物用塗料に対して１０〜６０重量％
であるのが好ましい。塗膜表面に散布する前記反射体
は、路面標示物用塗料１００重量部に対して５．０〜３
０重量部であるのが好ましい。光触媒性路面標示物用材
料の塗布前に、路面標示物用塗料の塗膜上へ劣化を防ぐ
バリア層を形成する工程を含むのが好ましい。基材は、
アスファルト、排水性アスファルト、コンクリートの中
から選ばれるのが好ましい。In this construction method, the coating film of the photocatalytic road marking material is preferably dried and solidified at 100 ° C. to ambient temperature. Further, by incorporating a particulate reflector in the road marking paint, and before the coating film of the road marking coating solidifies, it is possible to further spray a particulate reflector on the coating surface. preferable. The reflector contained in the road marking paint is 10 to 60% by weight with respect to the road marking paint.
Is preferred. The reflector applied to the surface of the coating film is 5.0 to 3 with respect to 100 parts by weight of the road marking material coating material.
It is preferably 0 part by weight. Before applying the photocatalytic road marking material, it is preferable to include a step of forming a barrier layer on the coating film of the road marking paint to prevent deterioration. The base material is
It is preferably selected from asphalt, drainage asphalt and concrete.
【００１０】本発明における第３の発明は、上記いずれ
か記載の光触媒性路面標示物用材料が固化した光触媒性
コーティング膜で表面が被覆され、かつ路面標示物用塗
料が固化した路面標示塗膜を含む光触媒性路面標示物、
または、上記いずれかの施工方法により施工されてなる
光触媒性路面標示物であって、光触媒性路面標示物用材
料が固化した光触媒性コーティング膜で表面が被覆さ
れ、かつ路面標示物用塗料が固化した路面標示塗膜を含
む光触媒性路面標示物である。A third aspect of the present invention is a road marking coating film, the surface of which is coated with the photocatalytic coating film obtained by solidifying the photocatalytic road marking material according to any one of the above, and the coating material for road marking is solidified. A photocatalytic road marking including
Alternatively, a photocatalytic road marking material constructed by any of the above construction methods, the surface is coated with a photocatalytic coating film in which the photocatalytic road marking material is solidified, and the road marking paint is solidified. It is a photocatalytic road marking material containing the above-mentioned road marking coating film.
【００１１】この光触媒性路面標示物は、光触媒性コー
ティング膜と、路面標示塗膜との間に、バリア層を含む
のが好ましい。また、粒子状の反射体を含み、反射体の
少なくとも一部は、粒子の一部が前記路面標示塗膜内に
埋め込まれ、残部が該塗料膜表面に露出しかつ光触媒性
コーティング膜で被覆されているのが好ましい。反射体
は、屈折率１．５〜２．５であり、ガラスビーズおよび
透明な無機化合物粒子の少なくとも一方であるのが好ま
しい。前記反射体の粒径は５０〜１０００μｍであるの
が好ましい。路面標示塗膜は熱可塑性高分子を含有する
のが好ましい。熱可塑性高分子は、融点又は軟化点が６
０〜１６０℃である、熱可塑性ゴム、熱可塑性ポリエス
テル樹脂およびポリアミド樹脂のうちの一種以上であ
り、かつ路面標示塗膜総量の０．１〜２０重量％含有さ
れるのが好ましい。光触媒性路面標示物は、車線境界
線、車道中央線、車道外側線、横断歩道、文字、記号の
標示線、道路標識のいずれかに使用されるのが好まし
い。光触媒性コーティング膜は、水若しくは空気の浄
化、路面標示物の防汚染、防結露、防滴、防氷結、防着
雪、異物付着防止、抗菌、防カビ、防藻、路面標示物周
辺の防臭、有害ガス分解の機能の何れか一つ以上の機能
を有するのが好ましい。光触媒コーティング膜は、目視
による干渉色を呈しないのが好ましい。The photocatalytic pavement marking material preferably contains a barrier layer between the photocatalytic coating film and the pavement marking coating film. Further, including a particulate reflector, at least a portion of the reflector, a part of the particles are embedded in the road marking coating, the rest is exposed on the coating film surface and is coated with a photocatalytic coating film. Is preferred. The reflector has a refractive index of 1.5 to 2.5 and is preferably at least one of glass beads and transparent inorganic compound particles. The particle size of the reflector is preferably 50 to 1000 μm. The road marking coating preferably contains a thermoplastic polymer. Thermoplastic polymers have a melting point or softening point of 6
It is preferably one or more of a thermoplastic rubber, a thermoplastic polyester resin and a polyamide resin, which is 0 to 160 ° C., and is contained in an amount of 0.1 to 20% by weight based on the total amount of the road marking coating film. The photocatalytic road markings are preferably used for any of lane boundaries, roadway center lines, roadway outside lines, pedestrian crossings, letter and symbol marking lines, and road markings. Photocatalytic coating film purifies water or air, anti-contamination, anti-condensation, drip-proof, anti-frost, anti-snow, anti-fouling, anti-bacterial, anti-mold, algae, deodorant around road markings It is preferable to have any one or more functions of decomposing harmful gas. It is preferable that the photocatalyst coating film does not exhibit interference color by visual observation.
【００１２】[0012]
【発明の実施の形態】光触媒性路面標示物に用いられる
材料の一つである、本発明の光触媒性路面標示物用材料
について説明する。本発明の光触媒性路面標示物用材料
は、光触媒性コーティング液の性状であって、光触媒性
路面標示物に用いられるもう一つの材料である路面標示
物用塗料の塗膜を固化した表面に、もしくは該固化した
表面に形成されたバリア層の表面に、この光触媒性コー
ティング液を塗布した後、乾燥して光触媒性コーティン
グ膜を成膜できるもので、このコーティング膜のみで防
汚染性等の光触媒性能を発揮することができる。BEST MODE FOR CARRYING OUT THE INVENTION The photocatalytic road marking material of the present invention, which is one of the materials used for the photocatalytic road marking, will be described. The photocatalytic road marking material of the present invention is a property of the photocatalytic coating liquid, and the surface of the coating of the coating material for the road marking paint which is another material used for the photocatalytic road marking is solidified, Alternatively, the photocatalytic coating liquid can be applied to the surface of the barrier layer formed on the solidified surface and then dried to form a photocatalytic coating film. It can exert its performance.
【００１３】この目的を達成する意味で、本発明の光触
媒性路面標示物用材料は、チタン化合物を含む塩基性溶
液から作製した水酸化チタンゲルに過酸化水素を作用さ
せ合成した無定形酸化チタンを含む酸化チタンゾル溶液
と、有機物質と、溶媒または分散媒とを含有するもので
ある。In order to achieve this object, the photocatalytic pavement marking material of the present invention is an amorphous titanium oxide synthesized by reacting hydrogen peroxide on a titanium hydroxide gel prepared from a basic solution containing a titanium compound. It contains a titanium oxide sol solution containing an organic substance, and a solvent or a dispersion medium.
【００１４】チタン化合物を含む塩基性溶液としては、
四塩化チタンなどの塩化チタンや硫酸チタン水溶液から
選ばれるチタン化合物とアンモニアや苛性ソーダ等の水
溶液等の塩基性溶液が挙げられる。この塩基性溶液から
得た水酸化チタンをイオン交換と蒸留を併用した純水で
デカンテーションしてアンモニウムイオン及び塩素イオ
ン等の副生成物及び不純物を適宜取除き、沈殿した水酸
化チタンを分離し、これに過酸化水素水を作用させ、余
分な過酸化水素を分解することにより無定形酸化チタン
を含む酸化チタンゾル溶液を得ることができる。As the basic solution containing the titanium compound,
Titanium compounds such as titanium tetrachloride and titanium chloride and aqueous solutions of titanium sulfate and basic solutions such as aqueous solutions of ammonia and caustic soda can be mentioned. The titanium hydroxide obtained from this basic solution is decanted with pure water combined with ion exchange and distillation to appropriately remove by-products and impurities such as ammonium ions and chlorine ions, and the precipitated titanium hydroxide is separated. A titanium oxide sol solution containing amorphous titanium oxide can be obtained by causing hydrogen peroxide solution to act on this to decompose excess hydrogen peroxide.
【００１５】この無定形酸化チタンを含む酸化チタンゾ
ル溶液をさらに６５℃以上で加熱すると、一部の無定形
酸化チタンをアナターゼ型に結晶化することができる。
これにより、アナターゼ型結晶酸化チタン／無定形酸化
チタン混合物の無定形酸化チタンを含む酸化チタンゾル
溶液が得られる。この際、加熱する温度は、反応をすみ
やかに行うため、また副反応を押さえ、水等の揮発を抑
制するために好ましくは９０〜９５℃とされる。When this titanium oxide sol solution containing amorphous titanium oxide is further heated at 65 ° C. or higher, a part of the amorphous titanium oxide can be crystallized into anatase type.
As a result, a titanium oxide sol solution containing amorphous titanium oxide of the anatase-type crystalline titanium oxide / amorphous titanium oxide mixture is obtained. At this time, the heating temperature is preferably 90 to 95 ° C. in order to carry out the reaction promptly, suppress side reactions and suppress volatilization of water and the like.
【００１６】光触媒性路面標示物用材料に用いる有機物
質は、該有機物質を含む本発明における光触媒性路面標
示物用材料を塗布乾燥して固化した膜に紫外線をあてた
時に発現する光触媒能が、該有機物質を含まない光触媒
性路面標示物用材料を塗布乾燥して固化した膜に同じ紫
外線をあてた時に発現する光触媒能よりも高くできるも
のが好ましい。この有機物質としては、例えば、芳香族
炭化水素、脂肪族炭化水素、脂環式炭化水素、芳香族
系、脂肪族系及び脂環式の、アルコール類、ケトン類、
エステル類及びエーテル類、複素環含有化合物、これら
のアミン変性化合物、シリコーン変性化合物、各種重合
体等が挙げられるが、本発明はそれらに限定したもので
はない。これら有機物質の内、酸化チタンゾル等の水分
散体に混合することや、撥水性基材への濡れ性を向上さ
せること等の観点から、分子中にアルキルシリケート構
造を有する有機物質やポリエーテル構造を有する有機物
質が好ましく、特に分子中にアルキルシリケート構造
と、ポリエーテル構造の双方を有する有機物質がより好
ましい。The organic substance used for the photocatalytic road marking material has a photocatalytic activity which is exhibited when ultraviolet rays are applied to a film obtained by coating and drying the photocatalytic road marking material of the present invention containing the organic substance. It is preferable that the photocatalytic activity that is exhibited when the same ultraviolet rays are applied to the film obtained by applying and drying the photocatalytic road marking material that does not contain the organic substance and solidifying the material is applied. Examples of the organic substance include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic, aliphatic and alicyclic alcohols, ketones,
Examples thereof include esters and ethers, compounds containing a heterocyclic ring, amine-modified compounds thereof, silicone-modified compounds and various polymers, but the present invention is not limited thereto. Among these organic substances, from the viewpoint of mixing with an aqueous dispersion such as titanium oxide sol or improving wettability to a water-repellent substrate, an organic substance having an alkyl silicate structure in the molecule or a polyether structure Is preferred, and an organic material having both an alkyl silicate structure and a polyether structure in the molecule is more preferred.
【００１７】ここで、アルキルシリケート構造とは、シ
ロキサン骨格のシラン原子にアルキル基が付加した構造
をさす。具体的には、ポリジメチルシロキサンに代表さ
れるシロキサン結合（−Ｓｉ−Ｏ−）を主鎖とするもの
が好適であるがそれらに限定されるものではない。その
中でも、ポリエチレンオキサイド−ポリプロピレンオキ
サイドブロック共重合体はそのブロック度や分子量によ
り、濡れ性を制御できる観点からもさらに好適である。Here, the alkyl silicate structure means a structure in which an alkyl group is added to a silane atom of the siloxane skeleton. Specifically, those having a siloxane bond (-Si-O-) represented by polydimethylsiloxane as a main chain are preferable, but the present invention is not limited thereto. Among them, the polyethylene oxide-polypropylene oxide block copolymer is more preferable from the viewpoint of controlling the wettability depending on the block degree and the molecular weight.
【００１８】また、エーテル構造とは、ポリアルキレン
オキサイド等の、アルキレン基をエーテル結合で結合し
た構造をさす。具体的には、ポリエチレンオキサイド、
ポリプロピレンオキサイド、ポリテトラメチレンオキサ
イド、ポリエチレンオキサイド−ポリプロピレンオキサ
イドブロック共重合体、ポリエチレンポリテトラメチレ
ングリコール共重合体、ポリテトラメチレングリコール
−ポリプロピレンオキサイド共重合体等の構造を有する
ものが挙げられる。その中でも、ポリエチレンオキサイ
ド−ポリプロピレンオキサイドブロック共重合体はその
ブロック度や分子量により、濡れ性を制御できる観点か
らもさらに好適であるが、それらに限定されるわけでは
ない。アルキルシリケート構造と、ポリエーテル構造の
双方を有する有機物質としては、具体的には、ポリエー
テル変性ポリジメチルシロキサン等のポリエーテル変性
ポリシロキサン系塗料用添加剤が使用でき、例えば、両
末端メタリルポリエチレンオキサイド−ポリプロピレン
オキサイドブロック共重合体とジヒドロポリジメチルシ
ロキサンとを反応させて得られるポリエチレンオキサイ
ド−ポリプロピレンオキサイドブロック共重合体変性ポ
リジメチルシロキサン等が好適に用いられる。これらの
有機物質は単独で用いても、２種以上を併用してもよ
い。いずれにせよ、光触媒性路面標示物用材料に用いる
有機物質は、光触媒性路面標示物用材料中の溶媒又は分
散媒に、可溶であることが好ましい。The ether structure means a structure in which an alkylene group such as polyalkylene oxide is bonded by an ether bond. Specifically, polyethylene oxide,
Examples thereof include those having a structure such as polypropylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide block copolymer, polyethylene polytetramethylene glycol copolymer, and polytetramethylene glycol-polypropylene oxide copolymer. Among them, the polyethylene oxide-polypropylene oxide block copolymer is more preferable from the viewpoint of being able to control the wettability depending on the block degree and the molecular weight, but is not limited thereto. As the organic substance having both an alkyl silicate structure and a polyether structure, specifically, an additive for polyether-modified polysiloxane coating such as polyether-modified polydimethylsiloxane can be used. A polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane obtained by reacting a polyethylene oxide-polypropylene oxide block copolymer with dihydropolydimethylsiloxane is preferably used. These organic substances may be used alone or in combination of two or more. In any case, the organic substance used in the photocatalytic pavement marking material is preferably soluble in the solvent or dispersion medium in the photocatalytic pavement marking material.
【００１９】光触媒性路面標示物用材料内の酸化チタン
ゾル溶液の固形分と有機物質との比は、前者：後者の質
量比で、１：０．０１〜１：１０であるのが好ましく、
１：０．０５〜１：２がより好ましく、１：０．１〜
１：０．５がさらに好ましい。有機物質の割合が酸化チ
タンゾル溶液の固形分１に対して０．０１未満の場合、
濡れ性が悪く基材に塗布できないことがあり、また塗布
できたものでも干渉色があり、光触媒能の向上効果に劣
る傾向にある。一方、有機物質の割合が酸化チタンゾル
溶液の固形分１に対して１０を超える場合、常温での造
膜性が悪くなり、塗膜の耐久性が劣る傾向にある。The ratio of the solid content of the titanium oxide sol solution in the photocatalytic road marking material to the organic substance is preferably 1: 0.01 to 1:10 by mass ratio of the former to the latter,
1: 0.05 to 1: 2 is more preferable, and 1: 0.1 to 0.1
1: 0.5 is more preferable. When the ratio of the organic substance is less than 0.01 with respect to 1 of the solid content of the titanium oxide sol solution,
The wettability is poor, and it may not be possible to apply it to the substrate, and even if it is applied, there is an interference color, and the effect of improving the photocatalytic activity tends to be poor. On the other hand, when the ratio of the organic substance is more than 10 relative to 1 of the solid content of the titanium oxide sol solution, the film-forming property at room temperature becomes poor, and the durability of the coating film tends to be poor.
【００２０】光触媒性路面標示物用材料に含まれる溶媒
又は分散媒としては、特に制限はないが、酸化チタン膜
形成用液体の安定性の意味で水が最も好ましい。酸化チ
タンゾル分散性に優れる意味では、水、有機溶媒又は水
−有機溶媒混合物が好ましい。水／有機溶媒混合割合と
しては、総量のうち、水が４０〜９５重量％、有機溶媒
の量が５〜６０重量％であることが、ゲル化が起こり難
く好ましい。The solvent or dispersion medium contained in the photocatalytic road marking material is not particularly limited, but water is most preferable in terms of stability of the titanium oxide film forming liquid. Water, an organic solvent, or a water-organic solvent mixture is preferable in terms of excellent dispersibility in titanium oxide sol. Regarding the mixing ratio of water / organic solvent, it is preferable that the total amount of water is 40 to 95% by weight and the amount of organic solvent is 5 to 60% by weight because gelation hardly occurs.
【００２１】溶媒又は分散媒となる水は、光触媒性路面
標示物用材料の安定性の意味で、イオン等の不純物を含
んでいないことが好ましく、例えばイオン交換水が好ま
しく、イオン交換と蒸留を併用した純水が更に好まし
い。また、溶媒又は分散媒となる有機溶媒としては、ア
ルコール類やブチルセロソルブ、エチルセロソルブ等の
セロソルブ類、メチルカルビトール、エチルカルビトー
ル、ブチルカルビトール等のカルビトール類、γ−ブチ
ロラクトン等のラクトン類が好適に使用される。特にア
ルコール類を含むのが好ましい。前記アルコール類と
は、常温で液体でかつ水酸基（ただし、ベンゼン環に直
接結合しない。）を持つ炭化水素化合物を指し、その例
としては、エタノール、メタノール、イソプロパノー
ル、エチルセロソルブ、ブチルセロソルブ、カルビトー
ル等が挙げられるがそれらに限定するものではない。上
記溶媒又は分散媒の中でも安全性、貯蔵安定性の点か
ら、水およびエタノールが適している。Water serving as a solvent or a dispersion medium preferably does not contain impurities such as ions in the sense of stability of the photocatalytic pavement marking material. For example, ion-exchanged water is preferable, and ion-exchanged and distilled are used. Pure water used in combination is more preferable. Further, as the solvent or the organic solvent serving as a dispersion medium, alcohols and butyl cellosolve, cellosolves such as ethyl cellosolve, carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol, lactones such as γ-butyrolactone. It is preferably used. It is particularly preferable to contain alcohols. The alcohols refer to hydrocarbon compounds that are liquid at room temperature and have a hydroxyl group (but not directly bonded to the benzene ring), and examples thereof include ethanol, methanol, isopropanol, ethyl cellosolve, butyl cellosolve, carbitol and the like. But is not limited thereto. Among the above solvents or dispersion media, water and ethanol are suitable from the viewpoints of safety and storage stability.
【００２２】また光触媒性路面標示物用材料には必要に
応じて公知の界面活性剤、消泡剤、レベリング剤、カッ
プリング剤、防腐剤、染料、顔料、充填剤等を酸化チタ
ン膜の特性を損なわない程度に添加することもできる。
また、必要に応じて、アクリル樹脂、ポリエステル樹
脂、メラミン樹脂、尿素樹脂、ポリアミド樹脂、ポリイ
ミド樹脂、エポキシ樹脂、フェノール樹脂、ケトン樹
脂、ポリウレタン樹脂、フッ素樹脂、シリコーン樹脂、
セルロース等の多糖類及びそれらのシリコーン、アミ
ン、エポキシ変性樹脂等の各種樹脂類を光触媒性コーテ
ィング膜の特性を損なわない程度に添加することもでき
る。Further, if necessary, known materials such as surfactants, defoaming agents, leveling agents, coupling agents, preservatives, dyes, pigments and fillers for the photocatalytic road marking material can be used as characteristics of the titanium oxide film. Can also be added to the extent that it does not impair.
In addition, if necessary, acrylic resin, polyester resin, melamine resin, urea resin, polyamide resin, polyimide resin, epoxy resin, phenol resin, ketone resin, polyurethane resin, fluorine resin, silicone resin,
Polysaccharides such as cellulose and various resins thereof such as silicone, amine and epoxy modified resin may be added to such an extent that the characteristics of the photocatalytic coating film are not impaired.
【００２３】光触媒性路面標示物用材料を製造する方法
としては、上述したような材料を混合し、均一に分散混
合させうる方法であれば特に制限は無いが、例えば、混
合に使用する撹拌装置としては、デゾルバー、スタテッ
クミキサー、ホモジナイザー、ペイントシェイキング等
の攪拌装置が挙げられる。The method for producing the photocatalytic road marking material is not particularly limited as long as it is a method capable of mixing the above-mentioned materials and uniformly dispersing and mixing them. For example, a stirring device used for mixing. Examples of the stirring device include a dissolver, a static mixer, a homogenizer, and a stirring device such as paint shaking.
【００２４】本発明の路面標示物用材料（光触媒性コー
ティング液）は、光触媒性路面標示物およびその施工方
法に使用できる。次に本発明の光触媒性路面標示物の施
工方法について説明する。本発明の光触媒性路面標示物
の施工方法は、路面標示物用塗料を基材上へ塗布して塗
膜を形成する工程と、前記塗膜を固化させて路面標示塗
膜を得る工程と、光触媒性路面標示物用材料を塗布して
塗膜を形成する工程と、光触媒性路面標示物用材料の塗
膜を１００℃以下で固化させて光触媒性コーティング膜
を得る工程とを含むことを特徴とする。The road marking material (photocatalytic coating liquid) of the present invention can be used for a photocatalytic marking material and a method for constructing the same. Next, a method for constructing the photocatalytic road marking object of the present invention will be described. The method for constructing a photocatalytic road marking product of the present invention comprises a step of applying a road marking material coating material onto a substrate to form a coating film, and a step of solidifying the coating film to obtain a road marking film. The method comprises the steps of applying a photocatalytic road marking material to form a coating film, and solidifying the coating film of the photocatalytic road marking material at 100 ° C. or lower to obtain a photocatalytic coating film. And
【００２５】本発明においては、路面標示物は、熱溶融
型の材料を用いて施工してゆくことが好ましい。本発明
における路面標示物用塗料は、溶解釜で、例えば１７０
〜２２０℃に溶解し、基材である路面に、区画線用施工
機で塗膜厚さ０.５〜３.０ｍｍ、一般には１.５ｍｍ前
後に塗布することができる。基材である路面には、予め
下地処理、例えばプライマー等の塗布をしておくのが好
ましい。基材としては、アスファルト、排水性アスファ
ルト、コンクリートの中から選ばれるのが好ましい。In the present invention, it is preferable that the road marking object is constructed by using a heat melting type material. The paint for road marking in the present invention is a melting pot, for example, 170
It can be dissolved at ˜220 ° C. and can be applied to a road surface as a base material with a marking line construction machine to a coating film thickness of 0.5 to 3.0 mm, generally around 1.5 mm. It is preferable to preliminarily coat the road surface, which is a base material, with a primer, for example. The base material is preferably selected from asphalt, drainage asphalt and concrete.
【００２６】路面標示物用塗料の塗布時における温度
は、１７０〜２２０℃が好ましく、１８０〜２００℃が
より好ましい。１７０℃未満では反射体の接着性、塗膜
の表面仕上がりが劣る傾向にあり、一方２２０℃を超え
ると、表面仕上がりは良好であるが、高温により塗料の
色が退色する。The temperature at the time of applying the paint for road markings is preferably 170 to 220 ° C, more preferably 180 to 200 ° C. If it is lower than 170 ° C, the adhesiveness of the reflector and the surface finish of the coating film tend to be poor, while if it is higher than 220 ° C, the surface finish is good, but the color of the paint fades at high temperatures.
【００２７】塗料の膜厚は０．５〜３．０ｍｍが好まし
く、１．５〜２．０ｍｍがより好ましい。０．５ｍｍ未
満では膜厚が薄いため路面との接着力が劣る傾向にあ
り、３．０ｍｍを超えると、接着力は良好であるがこれ
以上は路面との段差が大きく、車両通行時の車両振動が
大きくなる。The coating film thickness is preferably 0.5 to 3.0 mm, more preferably 1.5 to 2.0 mm. If the thickness is less than 0.5 mm, the adhesion to the road surface tends to be poor due to the thin film thickness, and if it exceeds 3.0 mm, the adhesion is good, but beyond this, there is a large difference in level with the road surface, and the vehicle is in use when the vehicle is passing. Vibration increases.
【００２８】路面標示物用塗料の塗膜を固化させて路面
標示塗膜を得た後、該塗料膜上へ光触媒性路面標示物用
材料を塗布する。または、路面標示塗膜上へ、劣化を防
ぐバリア層を形成した後に、光触媒性路面標示物用材料
を該バリア層上へ塗布してもよい。バリア層の形成は、
バリア層用コーティング液を調製し、該コーティング液
を路面標示塗膜上に塗付し、乾燥または放冷等により該
コーティング液を固化させることが挙げられる。バリア
層用コーティング液としては、光触媒路面標示物用材料
の塗膜で劣化せず、路面標示物用塗料の塗膜との密着性
に優れるものであればよく、例えば、無定形酸化チタン
の分散液または溶液が有効に用いられる。After the coating film of the road marking material is solidified to obtain a road marking coating film, a photocatalytic road marking material is applied onto the coating film. Alternatively, a barrier layer for preventing deterioration may be formed on the road marking coating film, and then the photocatalytic road marking material may be coated on the barrier layer. The formation of the barrier layer is
Examples include preparing a coating liquid for a barrier layer, applying the coating liquid on a road marking film, and solidifying the coating liquid by drying or cooling. As the coating liquid for the barrier layer, it is sufficient that it does not deteriorate in the coating film of the photocatalyst road marking material and has excellent adhesion to the coating film of the road marking paint, for example, dispersion of amorphous titanium oxide. A liquid or solution is effectively used.
【００２９】光触媒性路面標示物用材料およびそれを固
化した光触媒性コーティング膜には、酸化チタンが含ま
れるため、紫外線を照射することで、塗膜強度を向上す
ることができる。十分な紫外線の照射量としては、２Ｊ
/ｃｍ２以上、好ましくは２．２〜５．４Ｊ/ｃｍ２で十
分な塗膜強度を得ることができる。紫外線照射の方法と
しては、太陽光、蛍光灯、ブラックライト、高圧水銀灯
などを用いることができる。また、光触媒性コーティン
グ膜の厚さは、特に制限はないが、乾燥後において０．
０５〜１．５μｍが好ましく、０．０５μｍ未満では、
十分な光触媒性能が得られない場合があり、また１．５
μｍを超えると、酸化チタンの色がでて透明性が低下し
たり、基材との密着性が低下して剥がれ易くなったりす
る場合がある。この意味で０．１〜１．０μｍがより好
ましく、０．２〜０．５μｍがさらに好ましい。Since the photocatalytic road marking material and the photocatalytic coating film obtained by solidifying the material include titanium oxide, the coating film strength can be improved by irradiating with ultraviolet rays. 2J for a sufficient amount of UV irradiation
/ cm 2 or more, preferably 2.2 to 5.4 J / cm 2 can provide sufficient coating strength. As a method of irradiating with ultraviolet rays, sunlight, a fluorescent lamp, a black light, a high pressure mercury lamp or the like can be used. Further, the thickness of the photocatalytic coating film is not particularly limited, but it is 0.
05-1.5 μm is preferable, and if less than 0.05 μm,
In some cases, sufficient photocatalytic performance may not be obtained, and 1.5
If the thickness exceeds μm, the titanium oxide may be colored and the transparency thereof may be reduced, or the adhesion to the substrate may be reduced and the titanium oxide may be easily peeled off. In this sense, 0.1 to 1.0 μm is more preferable, and 0.2 to 0.5 μm is further preferable.
【００３０】路面標示物用塗料、バリア層用コーティン
グ液および光触媒性路面標示物用材料の塗布方法は、被
塗布面が均一に被覆される方法であれば、通常の塗布の
他、含浸させてもよい。具体的な方法としては、スプレ
ーコーティング法、ディップコーティング法、フローコ
ーティング法、スピンコーティング法、ロールコーティ
ング法、カーテンコーティング法、バーコーティング
法、超音波コーティング法、スクリーン印刷法、刷毛塗
り、スポンジ塗り等が適用でき、粘度の低い光触媒性路
面標示物用材料の場合、スプレーコーティング法が好ま
しい。The coating method for the road marking material, the coating liquid for the barrier layer and the material for the photocatalytic road marking material are not limited to ordinary coating, but may be impregnated as long as the surface to be coated is uniformly coated. Good. Specific methods include spray coating, dip coating, flow coating, spin coating, roll coating, curtain coating, bar coating, ultrasonic coating, screen printing, brush coating, sponge coating, etc. In the case of a material for a photocatalytic pavement marking material having a low viscosity, a spray coating method is preferable.
【００３１】路面標示物用塗料およびバリア層用コーテ
ィング液は、塗布後の固化条件に特に制限はなく、常温
で放冷、乾燥させればいずれも固化させることができる
が、送風等を併用してもよい。光触媒性路面標示物用材
料の固化は、塗布後、１００℃以下の低温で乾燥するこ
とにより付着性に優れた緻密な塗膜を形成できる。この
意味で、乾燥温度は、室温域および外気温（例えば１０
〜５０℃）でも十分可能であり、乾燥時間は膜の厚さ
や、溶媒又は分散媒にもよるが、０．５〜２４時間で十
分である。The road marking paint and the barrier layer coating liquid are not particularly limited in solidification conditions after coating, and can be solidified by allowing to cool at room temperature and drying, but air blowing or the like may be used together. May be. For solidification of the photocatalytic road marking material, a dense coating film having excellent adhesion can be formed by drying at a low temperature of 100 ° C. or lower after coating. In this sense, the drying temperature is defined as the room temperature range and the outside temperature (for example, 10
˜50 ° C.) is sufficient, and a drying time of 0.5 to 24 hours is sufficient, depending on the thickness of the film and the solvent or dispersion medium.
【００３２】さらに、路面標示物用塗料中に予め粒子状
の反射体を含有させてから塗布したり、路面標示物用塗
料の塗膜が固化する前に塗膜表面へ反射体を散布した
り、またこれらの双方を併用したりすることができる。
反射体としてはガラスビーズもしくは透明な無機化合物
が好ましい。反射体の粒径は、５０〜１０００μｍの範
囲であるのが好ましい。大きすぎると路面標示物が厚く
なり、小さすぎると路面標示塗膜から露出しにくい。ま
た、反射体の粒子の形状は特に制限はなく、球体、多面
体、扁平体等、任意の形状のものを使用できる。なお、
反射体の粒径はメッシュ篩（標準篩）を用いて調整で
き、後述する実施例では、メッシュ篩を用いてＪＩＳ−
Ｋ３３０１に準じてガラスビーズの粒径を決定した。路
面標示物用塗料に含有される反射体は、路面標示物用塗
料に対して、１０〜６０重量％配合されることが好まし
く、２０〜５０重量％配合されることがより好ましい。
ここで、反射体の配合量が２０重量％未満であると効果
が低下する傾向にあり、５０重量％を超えると塗料バラ
ンスがくずれ、接着力、粘度、耐クラック性などが低下
する傾向にある。反射体の屈折率は反射光の効率の点か
ら１．５〜２．５が好ましい。Furthermore, the particulate paint may be incorporated into the road marking paint in advance, or the reflecting paint may be sprayed on the coating surface before the coating of the road marking paint solidifies. Also, both of them can be used together.
As the reflector, glass beads or transparent inorganic compounds are preferable. The particle size of the reflector is preferably in the range of 50 to 1000 μm. If it is too large, the road marking becomes thick, and if it is too small, it is difficult to expose it from the road marking coating film. The shape of the particles of the reflector is not particularly limited, and any shape such as a sphere, a polyhedron, or a flat body can be used. In addition,
The particle size of the reflector can be adjusted by using a mesh sieve (standard sieve), and in the examples described later, a mesh sieve is used for JIS-
The particle size of the glass beads was determined according to K3301. The reflector contained in the road marking paint is preferably contained in an amount of 10 to 60% by weight, more preferably 20 to 50% by weight, based on the road marking paint.
Here, if the compounding amount of the reflector is less than 20% by weight, the effect tends to be reduced, and if it exceeds 50% by weight, the paint balance is lost, and the adhesive force, the viscosity, the crack resistance, etc. tend to be reduced. . The refractive index of the reflector is preferably 1.5 to 2.5 from the viewpoint of the efficiency of reflected light.
【００３３】また、固化前の塗膜表面に散布する反射体
の散布量は、路面標示物用塗料１００重量部に対して、
５.０〜３０重量％散布することが好ましく、１０〜２
５重量部散布することがより好ましい。ここで反射体の
散布量が５.０重量部未満であると、夜間や、雨天時の
反射効果が低下する傾向にあり、３０重量部を超えると
特性は良好であるが散布量に対して効果が充分でないと
いう傾向にある。Further, the amount of the reflectors scattered on the surface of the coating film before solidification is as follows, based on 100 parts by weight of the road marking paint.
It is preferable to apply 5.0 to 30% by weight, 10 to 2
It is more preferable to spray 5 parts by weight. Here, if the amount of the reflector applied is less than 5.0 parts by weight, the reflection effect at night or in the rain tends to decrease, and if it exceeds 30 parts by weight, the characteristics are good but The effect tends to be insufficient.
【００３４】これらにより、施工後に、少なくとも一部
の反射体は、反射体粒子の一部が前記路面標示塗膜内に
埋め込まれ、残部が該塗料膜表面に露出しかつ光触媒性
コーティング膜で被覆されている状態であるのが好まし
く、反射体の全部において上記状態であるのがさらに好
ましい。なお、ここで、バリア層を形成する場合には、
反射体塗料膜表面に露出している部分はバリア層次いで
光触媒性コーティング膜で被覆される。According to these, at least a part of the reflector is embedded in the road marking coating film, and the rest is exposed on the coating film surface and covered with the photocatalytic coating film after the construction. It is preferable that all of the reflectors are in the above state. Here, when forming the barrier layer,
The exposed portion on the surface of the reflector coating film is covered with a barrier layer and then a photocatalytic coating film.
【００３５】上記本発明の光触媒性路面標示物用材料ま
たは上記本発明の光触媒性路面標示物の施工方法によ
り、光触媒性路面標示物を得ることができる。すなわ
ち、本発明の光触媒性路面標示物は、上記本発明の光触
媒性路面標示物用材料が固化した光触媒性コーティング
膜で表面が被覆され、かつ路面標示物用塗料が固化した
路面標示塗膜を含むものであるか、または上記本発明の
施工方法により施工されてなる光触媒性路面標示物であ
って、光触媒性コーティング膜で表面が被覆され、かつ
路面標示塗膜を含むものである。A photocatalytic road marking material can be obtained by the above-mentioned material for photocatalytic road marking material of the present invention or the method for constructing the photocatalytic road marking material of the present invention. That is, the photocatalytic road marking of the present invention, the surface of the photocatalytic road marking material of the present invention is coated with a solidified photocatalytic coating film, and the road marking coating material is a solidified road marking coating film. A photocatalytic pavement marking material which is either included or is constructed by the construction method of the present invention, the surface of which is coated with a photocatalytic coating film and which also contains a pavement marking film.
【００３６】本発明における路面標示物用塗料およびそ
れが固化してなる路面標示塗膜には、熱可塑性高分子を
含むのが好ましく、熱可塑性高分子は特に熱可塑性ゴ
ム、ポリアミド樹脂および熱可塑性ポリエステル樹脂の
内の一つ以上であることが、後述する反射体の剥離防止
の効果に優れ好ましい。前記熱可塑性ゴム、ポリアミド
樹脂、熱可塑性ポリエステル樹脂は、融点又は軟化点が
６０〜１６０℃であることが好ましく、６０〜１４０℃
であることがより好ましく、８０〜１２０℃であること
がさらに好ましい。ここで融点又は軟化点が６０℃未満
であると材料の圧縮強さの低下、混練材料のブロッキン
グ、塗料軟化点の低下、経日の汚染性の悪化等が起こり
やすくなり、１６０℃を超えると塗料の増粘、溶融不足
等が発生しやすくなる。It is preferable that the road marking coating material and the road marking coating film obtained by solidifying the same in the present invention contain a thermoplastic polymer, and the thermoplastic polymer is particularly a thermoplastic rubber, a polyamide resin or a thermoplastic resin. One or more of the polyester resins are preferable because they have an excellent effect of preventing the peeling of the reflector described later. The thermoplastic rubber, polyamide resin, or thermoplastic polyester resin preferably has a melting point or softening point of 60 to 160 ° C, and 60 to 140 ° C.
Is more preferable, and it is further preferable that the temperature is 80 to 120 ° C. If the melting point or softening point is lower than 60 ° C, the compressive strength of the material is lowered, the kneading material is blocked, the softening point of the coating is lowered, and the stain resistance is deteriorated over time. The viscosity of the paint and insufficient melting are likely to occur.
【００３７】熱可塑性ゴムとしては、末端相にポリスチ
レン相をもち、ゴムの中間相としてはポリブタジエン、
ポリイソプレン、ポリオレフィン（エチレン／ブチレ
ン、エチレン／プロピレン）等をもつスチレン系熱可塑
性エラストマー〈即ち、スチレン−ブタジエン−スチレ
ンブロック共重合体、スチレン−エチレン／ブチレン−
スチレンブロック共重合体、スチレン−イソプレン−ス
チレンブロック共重合体など〉、エチレン−酢酸ビニル
共重合体、エチレン−エチルアクリレート共重合体、エ
チレン―α―オレフィン共重合体、プロピレン―α―オ
レフィン共重合体などが好ましい。また、熱可塑性ポリ
エステルとしては、脂環式構造を有する脂環族ポリエス
テルなどが好ましい。ポリアミド樹脂としては、重合脂
肪酸系ポリアミド樹脂等が好ましい。前記熱可塑性ゴ
ム、ポリアミド樹脂および熱可塑性ポリエステルの配合
量は路面標示物用塗料の総量に対して、０.１〜２０重
量％配合することが好ましく、０.５〜３重量％配合す
ることがより好ましい。０.１重量％未満では反射体の
剥離性の向上が見られない傾向にあり、２０重量％を超
えると、材料粘度の上昇、圧縮強さの上昇、耐汚染性の
悪化等が生じる傾向にある。The thermoplastic rubber has a polystyrene phase in the terminal phase, and polybutadiene as the intermediate phase of the rubber.
Styrenic thermoplastic elastomer having polyisoprene, polyolefin (ethylene / butylene, ethylene / propylene), etc. <namely, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-
Styrene block copolymer, styrene-isoprene-styrene block copolymer, etc.>, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer Coalescence and the like are preferable. The thermoplastic polyester is preferably an alicyclic polyester having an alicyclic structure. As the polyamide resin, a polymerized fatty acid-based polyamide resin or the like is preferable. The thermoplastic rubber, polyamide resin and thermoplastic polyester are preferably blended in an amount of 0.1 to 20% by weight, preferably 0.5 to 3% by weight, based on the total amount of the road marking paint. More preferable. If it is less than 0.1% by weight, the peeling property of the reflector tends not to be improved, and if it exceeds 20% by weight, the material viscosity increases, the compressive strength increases, and the stain resistance tends to deteriorate. is there.
【００３８】本発明における路面標示塗膜を得るための
路面標示物用塗料は、取り扱いのしやすさ等から熱溶融
型のものであることが好ましい。熱溶融型の路面標示物
用塗料は、一般に上記熱可塑性高分子体と共にその他の
成分を充填又は混練して製造される。このような成分と
しては、粘結樹脂、可塑剤、充填材、顔料、反射材、添加剤
等がある。The coating material for a road marking material for obtaining the road marking coating film according to the present invention is preferably a heat-melting type in view of easy handling. The hot-melt type road marking material is generally manufactured by filling or kneading the thermoplastic polymer with other components. Such components include binder resins, plasticizers, fillers, pigments, reflectors, additives and the like.
【００３９】粘結樹脂としては、生ロジン、マレイン化
ロジン、マレイン化ロジンエステル樹脂、石油樹脂、水
添ロジン、水添石油樹脂、テルペン樹脂、ポリプロピレ
ン、ポリエチレン樹脂等があげられ、これらは単独又は
混合して用いることができ、その軟化点が９０〜１３０
℃のものが好ましく９５〜１２５℃のものがより好まし
い。粘結樹脂の配合量は、路面標示物用塗料中、９〜３
０重量％が好ましく、１０〜２２重量％がより好まし
く、１２〜１７重量％がさらに好ましい。９重量％未満
では作業性が劣る傾向にあり、一方３０重量％を超える
と可とう性が低下する傾向にある。Examples of the binder resin include raw rosin, maleinized rosin, maleinized rosin ester resin, petroleum resin, hydrogenated rosin, hydrogenated petroleum resin, terpene resin, polypropylene and polyethylene resin, which may be used alone or They can be used as a mixture and have a softening point of 90 to 130.
C., preferably 95 to 125.degree. C., and more preferably 95.degree. The content of the binder resin is 9 to 3 in the paint for road markings.
0 wt% is preferable, 10 to 22 wt% is more preferable, and 12 to 17 wt% is further preferable. If it is less than 9% by weight, workability tends to be poor, while if it exceeds 30% by weight, flexibility tends to be lowered.
【００４０】また、可塑剤としては、植物油、植物油変
性アルキド樹脂、鉱物油、エポキシ化油、液状の合成ゴ
ム類等があげられる。可塑剤の配合量は、路面標示物用
塗料中０.５〜５重量％が好ましく、１〜４重量％がよ
り好ましい。０.５重量％未満では低温時の可とう性、
作業性が劣る傾向にあり、一方５重量％を超えると乾燥
性、汚染性が劣る傾向にある。Examples of the plasticizer include vegetable oil, vegetable oil-modified alkyd resin, mineral oil, epoxidized oil, liquid synthetic rubber and the like. The plasticizer content is preferably 0.5 to 5% by weight, and more preferably 1 to 4% by weight in the road marking composition. If it is less than 0.5% by weight, flexibility at low temperature,
Workability tends to be inferior, while on the other hand, if it exceeds 5% by weight, drying properties and stain resistance tend to be inferior.
【００４１】充填材としては、炭酸カルシウムの微粉、
寒水石、タルク、硬質骨材（天然石、人工の焼成骨
材）、溶融アルミナ等があげられる。充填材の配合量
は、路面標示物用塗料中２５〜６５重量％が好ましく、
３０〜６０重量％がより好ましい。２５重量％未満で
は、圧縮強さ、摩耗性等が低下する傾向にあり、一方６
５重量％を超えると低温時の可とう性、作業性が劣る傾
向にある。As the filler, calcium carbonate fine powder,
Examples include cold water stone, talc, hard aggregate (natural stone, artificial fired aggregate), fused alumina and the like. The blending amount of the filler is preferably 25 to 65% by weight in the road marking paint,
30 to 60% by weight is more preferable. If it is less than 25% by weight, the compressive strength, wear resistance, etc. tend to be decreased, while 6
If it exceeds 5% by weight, flexibility and workability at low temperature tend to be poor.
【００４２】顔料としては、白色顔料として、二酸化チ
タン、亜鉛華、リトポン、鉛白等があり、黄色顔料とし
て、黄鉛、耐熱黄鉛、有機系黄色顔料等があげられる。
また、必要に応じ蓄光顔料、蛍光顔料、夜光顔料等を単
独、併用しても良い。顔料の配合量は前記白色顔料や黄
色顔料の場合、路面標示物用塗料中、１.５〜７重量％
が好ましく、２〜６重量％がより好ましい。１.５重量
％未満では、昼間、夜間とも視認性が劣る傾向にあり、
一方７重量％を超えると、視認性は良好であるがこれ以
上配合しても効果が少ない。Examples of the pigment include titanium dioxide, zinc white, lithopone, and lead white as white pigments, and yellow lead, heat-resistant yellow lead, organic yellow pigments, and the like as yellow pigments.
If necessary, a phosphorescent pigment, a fluorescent pigment, a luminescent pigment, etc. may be used alone or in combination. In the case of the white pigment or the yellow pigment, the amount of the pigment blended is 1.5 to 7% by weight in the road marking paint.
Is preferable, and 2 to 6% by weight is more preferable. If it is less than 1.5% by weight, the visibility tends to be poor both during the day and at night,
On the other hand, when it exceeds 7% by weight, the visibility is good, but the effect is small even if it is blended further.
【００４３】光触媒性能の評価方法は有機分解性として
は、例えば、酸化チタン膜に水で適宜希釈した水溶性イ
ンキ、メチレンブルー、マラカイトグリーン、ジニトロ
フェノール溶解等の染料をスプレー、ディップ等で塗装
し、常温で乾燥させた後、ブラックライトブルー等で紫
外線を照射し、その消失度合を目視観察又は色差、吸光
度等を測定することで確認することができる。また、タ
バコのヤニの分解性もアセトンに適宜希釈して溶出した
タバコのヤニをスプレー、ディップ等で塗装し、常温で
乾燥させた後、ブラックライトブルー等で紫外線を照射
し、その消失度合を目視観察又は色差、吸光度等を測定
することで確認することができる。The method for evaluating the photocatalytic performance is organic degradability. For example, a titanium oxide film is coated with a water-soluble ink appropriately diluted with water, a dye such as methylene blue, malachite green, or dinitrophenol dissolved by spraying or dipping. After drying at room temperature, it can be confirmed by irradiating with ultraviolet light such as black light blue and the degree of disappearance thereof by visual observation or by measuring color difference, absorbance and the like. In addition, the degradability of tobacco tar is also appropriately diluted with acetone, and the dissolved tobacco tar is sprayed, coated with a dip, etc., dried at room temperature, and then irradiated with ultraviolet rays such as black light blue to determine the degree of disappearance. It can be confirmed by visual observation or by measuring color difference, absorbance and the like.
【００４４】以上の方法により本発明の光触媒性路面標
示物が得られる。本発明の光触媒性路面標示物は、光触
媒コーティング膜が目視による干渉色を呈しないため、
路面上の標示線や道路標識等に有効に適用できる。例え
ば、路面上の車線境界線、車道中央線、車道外側線、横
断歩道、文字、記号等の標示線、道路標識などのいずれ
かに使用できる。また、本発明の光触媒性路面標示物の
光触媒性コーティング膜は、水若しくは空気の浄化、路
面標示物の防汚染、防結露、防滴、防氷結、防着雪、異
物付着防止、抗菌、防カビ、防藻、路面標示物周辺の防
臭、有害ガス分解の機能の何れか一つ以上の機能を有す
ることができる。The photocatalytic road marking material of the present invention can be obtained by the above method. The photocatalytic pavement marking material of the present invention, because the photocatalytic coating film does not exhibit interference color by visual observation,
It can be effectively applied to marking lines and road signs on the road surface. For example, it can be used for any of a lane boundary line on a road surface, a roadway center line, a roadway outside line, a pedestrian crossing, a marking line for characters, symbols, etc., a road sign, and the like. Further, the photocatalytic coating film of the photocatalytic road marking of the present invention is water or air purification, anti-contamination of the road marking, anti-condensation, drip-proof, anti-icing, snow-prevention, foreign matter adhesion prevention, antibacterial, anti-proof. It can have any one or more of the functions of mold, algae, deodorization around road markings, and decomposition of harmful gases.
【００４５】[0045]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明は実施例に何ら制限されるものではない。な
お実施例中、特にことわりのないかぎり、「％」は「重
量％」「部」は「重量部」を示す。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to the examples. In the examples, "%" means "% by weight" and "parts" means "parts by weight" unless otherwise specified.
【００４６】（合成例１）表１に示すＡ〜Ｈの成分をミ
キサーで混合した後、１８０℃で加熱溶融して路面標示
物用塗料（塗料１）を得た。(Synthesis Example 1) Components A to H shown in Table 1 were mixed by a mixer and then heated and melted at 180 ° C. to obtain a paint for road marking (paint 1).
【００４７】[0047]
【表１】 [Table 1]
【００４８】（合成例２）表２に示すＡ〜Ｆの成分をミ
キサーで混合した後、１８０℃で加熱溶融して路面標示
物用塗料（塗料２）を得た。(Synthesis Example 2) Components A to F shown in Table 2 were mixed by a mixer and then heated and melted at 180 ° C. to obtain a paint for road marking (paint 2).
【００４９】[0049]
【表２】 [Table 2]
【００５０】（合成例３：ポリエチレンオキサイド−ポ
リプロピレンオキサイドブロック共重合体変性ポリジメ
チルシロキサン（Ａ１））原料として、下記構造式(Synthesis Example 3: Polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane (A1))
【化１】
（ｎ＝５〜３０、ｍ＝０〜５）で示されるジメタアリル
ポリエーテル２９ｇ、トルエン３５０ｇ及び白金含量が
２０ｐｐｍになるようにクロル白金酸を３つ口フラスコ
中に仕込み十分撹拌後、窒素を２０ミリリットル/分を
流通しつつ１００℃に３０分で昇温した。その後１００
℃に保持しつつ、次に下記構造式[Chemical 1] (N = 5 to 30, m = 0 to 5) 29 g of dimethallyl polyether represented by (n = 5 to 30, m = 0 to 5), 350 g of toluene, and chloroplatinic acid were charged into a three-neck flask so that the platinum content was 20 ppm, and after sufficient stirring, nitrogen was added. Was heated to 100 ° C. in 30 minutes while circulating 20 ml / minute. Then 100
While maintaining at ℃, the following structural formula
【化２】
で示されるジヒドロポリジメチルシロキサン７３ｇを徐
々に加え２時間反応させた。その後、室温に冷却し、炭
酸水素ナトリウムを加えて中和した。その後、ロータリ
ーエバポレータによりこの内容物からトルエンを留去
し、ポリエチレンオキサイド−ポリプロピレンオキサイ
ドブロック共重合体変性ポリジメチルシロキサン（以
下、Ａ１という。）９６ｇを得た。Ａ１のゲルパーミエ
ーションクロマトグラフィ法により測定したところ重量
平均分子量は、ポリスチレン換算でおよそ４０，０００
であった。[Chemical 2] 73 g of dihydropolydimethylsiloxane represented by was gradually added and reacted for 2 hours. Then, it cooled to room temperature and neutralized by adding sodium hydrogencarbonate. Then, toluene was distilled off from the contents by a rotary evaporator to obtain 96 g of polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane (hereinafter referred to as A1). The weight average molecular weight measured by gel permeation chromatography of A1 is about 40,000 in terms of polystyrene.
Met.
【００５１】（光触媒性路面標示物用材料（Ｃ１）：調
製例１）室温（２５℃）で０．８％の四塩化チタン水溶
液1リットルに２．５％アンモニア水を滴下しながら反
応させると白色の水酸化チタンの沈殿を得た。これをイ
オン交換と蒸留を併用した水（以下、純水と称する。）
でデカンテーションを１０回繰り返すことによって、ア
ンモニウムイオン及び塩素イオン等の副生成物及び不純
物を適宜取除き、沈殿した水酸化チタン（ＨＴ−１）を
分離した。これに過酸化水素水３０％溶液を２０ミリリ
ットル加えて良くかき混ぜながら反応させ発泡と発熱に
注意しつつ液温を５℃に管理しながら、４時間反応させ
て、ペルオキソチタン酸イオンとして溶解、あるいは一
種のゾル状態の、黄褐色の透明粘性液体である無定形酸
化チタンゾル溶液を得、濃度が１．０％になるように純
水を加え、無定形酸化チタンゾル溶液（ＭＺ−１）とし
た。ＭＺ−１を１２時間静置した後、さらに９５℃で３
０分間保温して、無定形酸化チタンを含む淡黄色透明〜
微濁の液体（ＮＺ−１）を作製した。その後、酸化チタ
ンの濃度が１．０重量％になるように純水を加えて酸化
チタンゾル溶液（Ｔ１）を調製した（ｐＨ６．８）。こ
のＴ１ １００ｇに合成例３で得たＡ１ ０．２ｇ、エ
タノール １００ｇを加え、室温でＡ１が均一に溶解す
るまで十分攪拌して光触媒性路面標示物用材料（Ｃ１）
を調製した。Ｃ１は、ｐＨは６．０であった。(Photocatalytic Road Marking Material (C1): Preparation Example 1) At room temperature (25 ° C.), 1 liter of 0.8% titanium tetrachloride aqueous solution was added dropwise with 2.5% aqueous ammonia to cause a reaction. A white precipitate of titanium hydroxide was obtained. This is water that uses both ion exchange and distillation (hereinafter referred to as pure water).
By repeating decantation for 10 times, by-products and impurities such as ammonium ions and chloride ions were appropriately removed, and precipitated titanium hydroxide (HT-1) was separated. To this, add 20 ml of 30% hydrogen peroxide solution and stir well to react while controlling the liquid temperature at 5 ° C while paying attention to foaming and heat generation, and react for 4 hours to dissolve as peroxotitanate ion, or An amorphous titanium oxide sol solution, which was a kind of yellowish brown transparent viscous liquid in a sol state, was obtained, and pure water was added so that the concentration became 1.0% to obtain an amorphous titanium oxide sol solution (MZ-1). After allowing MZ-1 to stand for 12 hours, it is further heated at 95 ° C for 3 hours.
Keeps it warm for 0 minutes and is transparent with a pale yellow color containing amorphous titanium oxide.
A slightly turbid liquid (NZ-1) was prepared. Then, pure water was added so that the concentration of titanium oxide was 1.0% by weight to prepare a titanium oxide sol solution (T1) (pH 6.8). To 100 g of this T1 was added 0.2 g of A1 obtained in Synthesis Example 3 and 100 g of ethanol, and the mixture was sufficiently stirred at room temperature until A1 was uniformly dissolved. The material for photocatalytic road marking (C1)
Was prepared. C1 had a pH of 6.0.
【００５２】（光触媒性路面標示物用材料（Ｃ２）：調
製例２）調製例１で得たＭＺ−１を１２時間静置した
後、さらに９５℃で２．０時間保温して、アナターゼ型
結晶酸化チタン／無定形酸化チタン混合物からなる淡黄
色透明〜微濁の液体（ＮＺ−２）を作製した。その後、
酸化チタンの濃度が１．０重量％になるように純水を加
え酸化チタンゾル溶液を調製してｐＨ７．２の酸化チタ
ンゾル溶液（Ｔ２）を得た。このＴ２ １００ｇに合成
例３で得たＡ１ ０．２ｇ、エタノール１００ｇを加
え、室温でＡ１が均一に溶解するまで十分攪拌して光触
媒性路面標示物用材料（Ｃ２）を調製した。Ｃ２は、ｐ
Ｈは６．９であった。(Photocatalytic pavement marking material (C2): Preparation Example 2) The MZ-1 obtained in Preparation Example 1 was allowed to stand for 12 hours and then kept at 95 ° C. for 2.0 hours to obtain anatase type. A pale yellow transparent to slightly turbid liquid (NZ-2) consisting of a crystalline titanium oxide / amorphous titanium oxide mixture was prepared. afterwards,
Pure water was added so that the concentration of titanium oxide was 1.0% by weight to prepare a titanium oxide sol solution to obtain a titanium oxide sol solution (T2) having a pH of 7.2. To 100 g of this T2, 0.2 g of A1 obtained in Synthesis Example 3 and 100 g of ethanol were added and sufficiently stirred at room temperature until A1 was uniformly dissolved to prepare a photocatalytic road marking material (C2). C2 is p
H was 6.9.
【００５３】（実施例１）
（酸化チタン膜形成路面標示物および試験板の作製、光
触媒性路面標示物用材料の弾きの有無）合成例１の路面
標示物用塗料を路面上に塗布し、２５℃で１時間乾燥さ
せて厚さ１．５ｍｍの路面標示塗膜を得た。その上に、
光触媒路面標示物用材料（Ｃ１）を乾燥膜厚が約０.３
μｍになるようにエアーガン（アネスト岩田社製型番Ｒ
Ｇ−２、口径０.４ｍｍ）を用いて空気圧０.０９８ＭＰ
ａでスプレー塗装した。２５℃で１時間乾燥して酸化チ
タン膜形成路面標示物を得た。Example 1 (Preparation of Titanium Oxide Film-Forming Road Marking Material and Test Plate, Presence or Absence of Repulsion of Photocatalytic Road Marking Material) The road marking material paint of Synthesis Example 1 was applied on the road surface, It was dried at 25 ° C. for 1 hour to obtain a road marking film having a thickness of 1.5 mm. in addition,
Photocatalyst road marking material (C1) with a dry film thickness of about 0.3
Air gun to make it μm (Anest Iwata company model number R
G-2, caliber 0.4mm) and air pressure 0.098MP
Spray-painted in a. It was dried at 25 ° C. for 1 hour to obtain a titanium oxide film-formed road marking.
【００５４】一方、表面をエタノールで脱脂し、乾燥し
た厚さ１．７ｍｍのガラス平板に、乾燥膜厚が約０．３
μｍになるようにエアーガン（アネスト岩田社製型番Ｒ
Ｇ−２、口径０．４ｍｍ）を用い、空気圧０．０９８Ｍ
Ｐａで上記光触媒性路面標示物用材料Ｃ1をスプレー塗
装した。この時、基材であるガラス表面でのＣ１の塗膜
の弾き（表面に液滴が出来る現象）の有無を目視観察し
結果を表１に示した。次いで、２５℃で１時間乾燥した
後、５ｃｍの距離から２０Ｗのブラックライト（日本電
気製、型番ＦＬ２０ＳＢＬ−Ｂ）を２時間照射して、そ
の後、１週間室温にて静置して酸化チタン膜形成試験板
を得た。得られた試験板を下記（１）〜（５）の試験
（Ａ）に、また路面標示物を下記（６）〜（９）の試験
（Ｂ）に供した。On the other hand, the surface was degreased with ethanol and dried on a glass plate having a thickness of 1.7 mm to give a dry film thickness of about 0.3.
Air gun to make it μm (Anest Iwata company model number R
G-2, caliber 0.4mm), air pressure 0.098M
The above-mentioned photocatalytic road marking material C1 was spray-coated at Pa. At this time, the presence or absence of flipping of the C1 coating film (a phenomenon in which droplets are formed on the surface) on the surface of the glass substrate was visually observed, and the results are shown in Table 1. Then, after drying at 25 ° C. for 1 hour, 20 W of black light (manufactured by NEC, model number FL20SBL-B) is irradiated from a distance of 5 cm for 2 hours, and then left standing for 1 week at room temperature to form a titanium oxide film. A formation test plate was obtained. The obtained test plate was subjected to the test (A) of the following (1) to (5), and the road marking was subjected to the test (B) of the following (6) to (9).
【００５５】[試験（Ａ）]
（１：酸化チタン膜の干渉色の有無）上記の作製方法で
得られた酸化チタン膜形成試験板の酸化チタン膜を目視
観察して、干渉色（ギラツキ）の有無を評価し、結果を
表３に示した。
（２：酸化チタン膜の密着性）上記の作製方法で得られ
た酸化チタン膜形成試験板の酸化チタン膜をＪＩＳＫ
５４００の碁盤目試験法に準じ、基材との密着性を評価
し結果を表３に示した。
（３：酸化チタン膜の耐磨耗性）上記の作製方法で得ら
れた酸化チタン膜形成試験板の酸化チタン膜を小津産業
(株)製バインダー無しコットン（製品名ベンコット）で
摩擦し、目視で剥がれの有無の観察結果を表３に示し
た。
（４：酸化チタン膜の水接触角）上記の作製方法で得ら
れた酸化チタン膜形成試験板の酸化チタン膜の蒸留水接
触角を、協和界面科学社製接触角計ＣＡ−Ｘ型で測定し
結果を表３に示した。
（５：屋外暴露後の酸化チタン膜）上記の作製方法で得
られた酸化チタン膜形成試験板をＪＩＳ Z ２３８１
の屋外暴露試験方法通則に準じ、茨城県日立市の建物屋
上に正南面向きに暴露角度３０度に設置した直接暴露試
験装置に固定して１年間暴露し、酸化チタン膜を目視観
察して、酸化チタン膜の消失・劣化の度合いを評価し結
果を表３に示した。[Test (A)] (1: Presence or Absence of Interference Color of Titanium Oxide Film) The titanium oxide film of the titanium oxide film-forming test plate obtained by the above-described manufacturing method was visually observed and the interference color (glare) was observed. The presence / absence of the product was evaluated, and the results are shown in Table 3. (2: Adhesion of Titanium Oxide Film) The titanium oxide film of the titanium oxide film formation test plate obtained by the above-mentioned manufacturing method was JISK
According to the cross-cut test method of 5400, the adhesion to the substrate was evaluated, and the results are shown in Table 3. (3: Abrasion resistance of titanium oxide film) The titanium oxide film of the titanium oxide film-forming test plate obtained by the above-mentioned manufacturing method was used as the Ozu industry.
Table 3 shows the results of observation by rubbing with a binderless cotton (product name: Bencott) manufactured by Co., Ltd. and visually observing the presence or absence of peeling. (4: Water Contact Angle of Titanium Oxide Film) The distilled water contact angle of the titanium oxide film of the titanium oxide film formation test plate obtained by the above-mentioned production method was measured with a contact angle meter CA-X type manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 3. (5: Titanium oxide film after outdoor exposure) The titanium oxide film formation test plate obtained by the above-mentioned manufacturing method was JIS Z 2381.
According to the general rule of outdoor exposure test method, fixed to a direct exposure test device installed at an exposure angle of 30 degrees on the south side of the building roof in Hitachi City, Ibaraki Prefecture, and exposed for 1 year, visually observing the titanium oxide film, The degree of disappearance / deterioration of the titanium oxide film was evaluated, and the results are shown in Table 3.
【００５６】[試験（Ｂ）]
（６：赤インキの分解性）上記作製方法で得られた路面
標示物の表面に、アセトンで２０倍に希釈した赤インキ
(シャチハタ株式会社製)を０１７ｇ／ｃｍ2となるよう
にスプレー塗装した。その後、５ｃｍの距離から２０Ｗ
のブラックライト（日本電気製、型番ＦＬ２０ＳＢＬ−
Ｂ）を照射して、赤インキの退色の度合いを目視により
観察し結果を表４に示した。
（７：タバコのヤニの分解性）上記作製方法で得られた
路面標示物の表面に、５０ｍｌのアセトン中にタバコを
一本浸してアセトン中に溶出した液体を０.０１７ｇ／
ｃｍ2となるようにスプレー塗装した。その後、５ｃｍ
の距離から２０Ｗのブラックライト（日本電気製、型番
ＦＬ２０ＳＢＬ−Ｂ）を照射して、タバコのヤニの退色
の度合いを目視により観察し結果を表５に示した。
（８：視認性）20ｍ前方の湿潤状態における上記作製方
法で得られた路面標示物を、静止した自動車内において
電圧：12Ｖ、電力：60Ｗで照射されたヘッドライトにて
視認した結果を表３に示す。
（９：反射輝度）湿潤状態における上記作製方法で得ら
れた路面標示物を、ポッターズバロティーニ社製の反射
輝度測定器（ミロラックス７）にて入射角８６°３
０′、観測角１°３０′、測定面１５０×９０ｍｍ、光
源：赤色ＬＥＤ（1000ｍｃｄ）の仕様で測定した結果を
表３に示した。[Test (B)] (6: Decomposability of red ink) On the surface of the road marking obtained by the above-mentioned manufacturing method, red ink diluted 20 times with acetone
(Manufactured by Shachihata Co., Ltd.) was spray-coated so that the amount was 017 g / cm 2 . Then 20W from a distance of 5 cm
Black light (manufactured by NEC, model number FL20SBL-
B) was irradiated, and the degree of fading of the red ink was visually observed, and the results are shown in Table 4. (7: Decomposability of tobacco tar) On the surface of the road marking material obtained by the above-mentioned production method, one cigarette was soaked in 50 ml of acetone, and a liquid eluted in acetone was 0.017 g /
It was spray-painted so as to have a cm 2 . Then 5 cm
A black light of 20 W (manufactured by NEC Corporation, model number FL20SBL-B) was irradiated from a distance of 10 to visually observe the degree of discoloration of the tar of the cigarette, and the results are shown in Table 5. (8: Visibility) The results obtained by visually observing the road surface marking obtained by the above-described manufacturing method in a wet state 20 m ahead with a headlight irradiated with a voltage of 12 V and an electric power of 60 W in a stationary automobile are shown in Table 3. Shown in. (9: Reflection brightness) The road surface marking object obtained by the above-described manufacturing method in a wet state was measured with a reflection brightness measuring instrument (Mirolux 7) manufactured by Potters Ballotini Co., Ltd. at an incident angle of 86 ° 3.
Table 3 shows the results of measurement under the conditions of 0 ', observation angle 1 ° 30', measurement surface 150 × 90 mm, light source: red LED (1000 mcd).
【００５７】[0057]
【表３】 [Table 3]
【００５８】[0058]
【表４】 [Table 4]
【００５９】[0059]
【表５】 [Table 5]
【００６０】（実施例２）合成例１の路面標示物用塗料
の代わりに、合成例２の路面標示物用塗料（塗料２）を
使用した以外は実施例１と同様にして試験（Ｂ）を行っ
た。結果を表３〜５に併記する。Example 2 A test (B) was conducted in the same manner as in Example 1 except that the road marking paint of Synthesis Example 2 (paint 2) was used in place of the road marking paint of Synthesis Example 1. I went. The results are also shown in Tables 3-5.
【００６１】（実施例３）光触媒路面標示物用材料とし
て、Ｃ１の代わりにＣ２を用いた以外は実施例１と同様
に試験（Ａ）及び（Ｂ）を行った。結果を表３〜５に併
記する。Example 3 Tests (A) and (B) were performed in the same manner as in Example 1 except that C2 was used instead of C1 as the material for the photocatalyst road marking material. The results are also shown in Tables 3-5.
【００６２】（実施例４）光触媒路面標示物用材料とし
て、Ｃ１の代わりにＣ２を用いた以外は実施例２と同様
に試験（Ｂ）を行った。結果を表３〜５に併記する。Example 4 A test (B) was conducted in the same manner as in Example 2 except that C2 was used instead of C1 as the material for the photocatalyst road marking material. The results are also shown in Tables 3-5.
【００６３】（実施例５）ガラス板に調製例１で得たＭ
Ｚ−１を塗装した後、光触媒路面標示物用材料としてＣ
２を塗布した以外は実施例１と同様に試験（Ａ）を行っ
た。また、合成例１による路面標示塗膜上に、調製例１
で得たＭＺ−１を塗装した後、光触媒路面標示物用材料
としてＣ２を塗布した以外は実施例１と同様に試験
（Ｂ）を行った。結果を表３〜５に併記する。(Example 5) M obtained in Preparation Example 1 on a glass plate
After coating Z-1, C as a material for photocatalyst road markings
Test (A) was performed in the same manner as in Example 1 except that 2 was applied. In addition, Preparation Example 1 was formed on the road marking coating film according to Synthesis Example 1.
The test (B) was performed in the same manner as in Example 1 except that after coating the MZ-1 obtained in 1 above, C2 was coated as the material for the photocatalyst road marking material. The results are also shown in Tables 3-5.
【００６４】（比較例１）エタノールで脱脂し、乾燥し
たガラス板に何も塗装せず、試験（Ａ）のうち、水接触
角との試験を行った。合成例１による路面標示塗膜上に
何も塗装しなかった以外は実施例１と同様に試験（Ｂ）
を行った。結果を表３〜５に併記する。(Comparative Example 1) In the test (A), a test with a water contact angle was conducted without coating anything on a glass plate that had been degreased with ethanol and dried. Test (B) as in Example 1 except that nothing was coated on the road marking coating according to Synthesis Example 1.
I went. The results are also shown in Tables 3-5.
【００６５】（比較例２）合成例１の路面標示物用塗料
の代わりに合成例２の路面標示物用塗料を用いた以外は
比較例１と同様に試験（Ｂ）を行った。結果を表３〜５
に併記する。Comparative Example 2 A test (B) was conducted in the same manner as in Comparative Example 1 except that the road marking material coating composition of Synthesis Example 2 was used instead of the road marking material coating composition of Synthesis Example 1. The results are shown in Tables 3-5.
Also described in.
【００６６】（比較例３）Ｃ１の代わりに調製例１で得
たＭＺ−１を塗装した以外は実施例１と同様に試験
（Ａ）を行った。合成例１による路面標示塗膜の上に、
Ｃ１の代わりに調製例１で得たＭＺ−１を塗装した以外
は実施例１と同様に試験（Ｂ）を行った。結果を表３〜
５に併記する。Comparative Example 3 The test (A) was carried out in the same manner as in Example 1 except that the MZ-1 obtained in Preparation Example 1 was coated instead of C1. On the road marking coating according to Synthesis Example 1,
The test (B) was performed in the same manner as in Example 1 except that the MZ-1 obtained in Preparation Example 1 was coated instead of C1. The results are shown in Table 3 ~
Also described in 5.
【００６７】（比較例４）合成例１の路面標示物用塗料
の代わりに、合成例２の路面標示物用塗料を使用した以
外は比較例３と同様に試験（Ｂ）を行った。結果を表３
〜５に併記する。Comparative Example 4 A test (B) was conducted in the same manner as in Comparative Example 3 except that the road marking material coating composition of Synthesis Example 2 was used in place of the road marking material coating composition of Synthesis Example 1. The results are shown in Table 3.
It is also described in ~ 5.
【００６８】表３〜５の評価結果のように、光触媒性路
面標示物用材料を光触媒性路面標示物上に用いることに
より、光触媒性路面標示物用材料を基材へ塗布する際、
弾きがなく均一に塗工可能であり、これらを塗布して形
成された酸化チタン膜は、干渉色が無く、基材との密着
性、耐磨耗性に優れる。また水接触角も小さくなり光触
媒性路面標示物の防滴効果も期待できる。さらに有機物
分解性に優れることから、光触媒性路面標示物の汚染防
止効果が高いと言える。As shown in the evaluation results of Tables 3 to 5, when the photocatalytic pavement marking material is used on the photocatalytic pavement marking material, when the photocatalytic pavement marking material is applied to the substrate,
It can be applied uniformly without repelling, and the titanium oxide film formed by applying these has no interference color and is excellent in adhesion to the substrate and abrasion resistance. In addition, the contact angle with water becomes small, and the anti-drip effect of the photocatalytic road marking can be expected. Furthermore, it can be said that the photocatalytic road markings have a high contamination preventing effect because they are excellent in decomposing organic substances.
【００６９】[0069]
【発明の効果】本発明によれば、常温等の低温でも成膜
が可能であり、また従来のアナターゼ／アモルファス混
合酸化チタンゾル溶液を用いた酸化チタン膜よりも光触
媒能が高い酸化チタン膜を成膜できる光触媒路面標示物
用材料を路面標示物に用いることにより、干渉色が無
く、基材との密着性、耐磨耗性に優れ、防滴効果も期待
でき、さらに汚染防止効果、視認性、反射輝度性をそこ
なわない光触媒性路面標示物を提供することができる。According to the present invention, a titanium oxide film can be formed even at a low temperature such as room temperature and has a photocatalytic ability higher than that of a titanium oxide film using a conventional anatase / amorphous mixed titanium oxide sol solution. By using a photocatalyst road marking material that can be formed into a film as a road marking material, there is no interference color, it has excellent adhesion to the base material, excellent abrasion resistance, and it can be expected to have a drip-proof effect. It is possible to provide a photocatalytic road marking that does not impair the reflective brightness.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 郷 豊 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎事業所内 (72)発明者 村上 誠 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎事業所内 Ｆターム(参考） 2D064 AA05 BA06 BA11 CA04 EA01 EB26 4G069 AA03 AA08 BA04A BA04B BA48A CA01 CA10 DA06 EA08 EA11 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yutaka Go Hitachi, Ichiba, Ibaraki Prefecture Seikou Co., Ltd. Yamazaki Office (72) Inventor Makoto Murakami Hitachi, Ichiba, Ibaraki Prefecture Seikou Co., Ltd. Yamazaki Office F term (reference) 2D064 AA05 BA06 BA11 CA04 EA01 EB26 4G069 AA03 AA08 BA04A BA04B BA48A CA01 CA10 DA06 EA08 EA11
Claims (24)
した水酸化チタンゲルに過酸化水素を作用させて得た無
定形酸化チタンを含む酸化チタンゾル溶液と、有機物質
と、溶媒又は分散媒とを含む光触媒性路面標示物用材
料。1. A titanium oxide sol solution containing amorphous titanium oxide obtained by allowing hydrogen peroxide to act on a titanium hydroxide gel prepared from a basic solution containing a titanium compound, an organic substance, and a solvent or a dispersion medium. Materials for photocatalytic road markings.
の一部がアナターゼ型結晶酸化チタン又はその前駆体を
含有するアナターゼ型結晶酸化チタン／無定形酸化チタ
ン混合物からなる請求項１記載の光触媒性路面標示物用
材料。2. The photocatalytic road surface according to claim 1, wherein the titanium oxide sol solution comprises anatase type crystalline titanium oxide / amorphous titanium oxide mixture in which a part of titanium oxide contains anatase type crystalline titanium oxide or a precursor thereof. Material for marking materials.
ド重合体変性ポリジメチルシロキサン又はポリエチレン
オキサイド−ポリプロピレンオキサイドブロック共重合
体変性ポリジメチルシロキサンである請求項１または２
記載の光触媒性路面標示物用材料。3. The organic substance is polyethylene oxide polymer-modified polydimethylsiloxane or polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane.
The photocatalytic road marking material as described.
の比が、前者：後者の重量比で、１：０．０１〜１：１
０である請求項１〜３何れか記載の光触媒性路面標示物
用材料。4. The ratio of the solid content of the titanium oxide sol solution to the organic substance is 1: 0.01 to 1: 1 by weight ratio of the former to the latter.
It is 0, The material for photocatalytic road markings in any one of Claims 1-3.
は水−有機溶媒混合物である請求項１〜４何れか記載の
光触媒性路面標示物用材料。5. The photocatalytic pavement marking material according to claim 1, wherein the solvent or dispersion medium is water, an organic solvent or a water-organic solvent mixture.
項５記載の光触媒性路面標示物用材料。6. The photocatalytic road marking material according to claim 5, wherein the organic solvent contains alcohols.
膜を形成する工程と、前記塗膜を固化させる工程と、請
求項１〜６のいずれか記載の光触媒性路面標示物用材料
を塗布して塗膜を形成する工程と、光触媒性路面標示物
用材料の塗膜を１００℃以下で固化させる工程とを含む
ことを特徴とする光触媒性路面標示物の施工方法。7. The photocatalytic road marking material according to claim 1, wherein the coating material for a road marking material is applied onto a base material to form a coating film, the coating material is solidified. A method of applying a photocatalytic road marking, comprising: a step of applying a coating material to form a coating; and a step of solidifying the coating of the photocatalytic road marking material at 100 ° C. or lower.
０℃〜外気温で乾燥して固化させる請求項７記載の光触
媒性路面標示物の施工方法。8. A coating film of photocatalytic road marking material
The method for constructing a photocatalytic road marking according to claim 7, which is dried and solidified at 0 ° C to ambient temperature.
含有させ、かつ該路面標示物用塗料の塗膜が固化する前
に、さらに粒子状の反射体を前記塗膜表面に散布する請
求項７または８記載の光触媒性路面標示物の施工方法。9. A particulate reflector is contained in a paint for a road marking, and a particulate reflector is further sprayed on the surface of the coating before the coating of the paint for the marking is solidified. The method for constructing a photocatalytic road marking object according to claim 7 or 8.
が、路面標示物用塗料に対して１０〜６０重量％である
請求項９記載の光触媒性路面標示物の施工方法。10. The method for constructing a photocatalytic road marking according to claim 9, wherein the reflector contained in the paint for road marking is 10 to 60% by weight based on the paint for road marking.
面標示物用塗料１００重量部に対して５．０〜３０重量
部である請求項９または１０記載の光触媒性路面標示物
の施工方法。11. The construction of a photocatalytic road marking according to claim 9 or 10, wherein the reflector scattered on the surface of the coating film is 5.0 to 30 parts by weight based on 100 parts by weight of the coating for road marking. Method.
に、路面標示物用塗料の塗膜上へ劣化を防ぐバリア層を
形成する工程を含む請求項７〜１１のいずれか記載の光
触媒性路面標示物の施工方法。12. The photocatalytic property according to any one of claims 7 to 11, which comprises a step of forming a barrier layer for preventing deterioration on the coating film of the coating material for a road marking material before applying the photocatalytic road marking material. How to construct road markings.
ァルト、コンクリートの中から選ばれる請求項７〜１２
何れか記載の光触媒性路面標示物の施工方法。13. The base material is selected from among asphalt, drainage asphalt and concrete.
The method for constructing a photocatalytic road marking according to any one of claims.
路面標示物用材料が固化した光触媒性コーティング膜で
表面が被覆され、かつ路面標示物用塗料が固化した路面
標示塗膜を含むことを特徴とする光触媒性路面標示物。14. A road marking coating film, the surface of which is coated with a photocatalytic coating film having the photocatalytic road marking material according to any one of claims 1 to 6 solidified, and which has a solidified paint for road marking. A photocatalytic road surface marking material.
法により施工されてなる光触媒性路面標示物であって、
光触媒性路面標示物用材料が固化した光触媒性コーティ
ング膜で表面が被覆され、かつ路面標示物用塗料が固化
した路面標示塗膜を含むことを特徴とする光触媒性路面
標示物。15. A photocatalytic pavement marking constructed by the construction method according to claim 7.
A photocatalytic road marking material, characterized in that the surface of the photocatalytic marking material is coated with a solidified photocatalytic coating film, and the coating material for a road marking material is solidified.
塗膜との間に、バリア層を含む請求項１４または１５記
載の光触媒性路面標示物。16. The photocatalytic pavement marking product according to claim 14 or 15, further comprising a barrier layer between the photocatalytic coating film and the pavement marking coating film.
くとも一部は、粒子の一部が前記路面標示塗膜内に埋め
込まれ、残部が該塗料膜表面に露出しかつ光触媒性コー
ティング膜で被覆されている請求項１４〜１６のいずれ
か記載の光触媒性路面標示物。17. A particulate reflector, at least a part of the reflector having a part of the particles embedded in the road marking coating, the rest being exposed on the coating film surface and a photocatalytic coating film. The photocatalytic road marking according to any one of claims 14 to 16, which is coated with.
り、ガラスビーズおよび透明な無機化合物粒子の少なく
とも一方である請求項１７記載の光触媒性路面標示物。18. The photocatalytic pavement marking according to claim 17, wherein the reflector has a refractive index of 1.5 to 2.5 and is at least one of glass beads and transparent inorganic compound particles.
ｍの範囲内である請求項１７または１８記載の光触媒性
路面標示物。19. The particle size of the reflector is 50 to 1000 μm.
The photocatalytic road marking according to claim 17 or 18, which is within the range of m.
する請求項１４〜１９のいずれか記載の光触媒性路面標
示物。20. The photocatalytic road marking product according to claim 14, wherein the road marking coating film contains a thermoplastic polymer.
６０〜１６０℃である、熱可塑性ゴム、熱可塑性ポリエ
ステル樹脂およびポリアミド樹脂のうちの一種以上であ
り、かつ路面標示塗膜総量の０．１〜２０重量％含有さ
れる請求項２０記載の光触媒性路面標示物。21. The thermoplastic polymer is one or more of a thermoplastic rubber, a thermoplastic polyester resin and a polyamide resin having a melting point or a softening point of 60 to 160 ° C. and having a total road marking coating amount of 0. The photocatalytic pavement marking material according to claim 20, which is contained in an amount of 0.1 to 20% by weight.
線、横断歩道、文字、記号の標示線、道路標識のいずれ
かに使用される請求項１４〜２１のいずれか記載の光触
媒性路面標示物。22. The photocatalytic road marking according to any one of claims 14 to 21, which is used for any of a lane boundary line, a roadway center line, a roadway outside line, a pedestrian crossing, a marking line for letters and symbols, and a road sign. object.
は空気の浄化、路面標示物の防汚染、防結露、防滴、防
氷結、防着雪、異物付着防止、抗菌、防カビ、防藻、路
面標示物周辺の防臭、有害ガス分解の機能の何れか一つ
以上の機能を有する請求項１４〜２２何れか記載の光触
媒性路面標示物。23. The photocatalytic coating film is used for purification of water or air, anti-contamination of road markings, dew condensation prevention, drip-proofing, ice-prevention, snow-prevention, foreign matter adhesion prevention, antibacterial, antifungal, algae, road surface The photocatalytic road surface marking object according to any one of claims 14 to 22, which has one or more functions of deodorizing and degrading harmful gas around the marking object.
渉色を呈しない請求項１４〜２３何れか記載の光触媒性
路面標示物。24. The photocatalytic road marking according to any one of claims 14 to 23, wherein the photocatalyst coating film does not exhibit an interference color by visual observation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002031723A JP2003232018A (en) | 2002-02-08 | 2002-02-08 | Material and execution method for photocatalytic road marking object, and photocatalytic road making object |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002031723A JP2003232018A (en) | 2002-02-08 | 2002-02-08 | Material and execution method for photocatalytic road marking object, and photocatalytic road making object |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003232018A true JP2003232018A (en) | 2003-08-19 |
Family
ID=27775046
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002031723A Pending JP2003232018A (en) | 2002-02-08 | 2002-02-08 | Material and execution method for photocatalytic road marking object, and photocatalytic road making object |
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| Country | Link |
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| JP (1) | JP2003232018A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009525246A (en) * | 2006-02-01 | 2009-07-09 | コロロッビア イタリア ソシエタ ペル アチオニ | Method for producing aqueous dispersion of TiO2 in the form of nanoparticles, and dispersion obtained by this method |
| JP2010017696A (en) * | 2008-07-14 | 2010-01-28 | National Institute Of Advanced Industrial & Technology | Metal nano-particle catalyst and oxygen oxidation method |
| CN114958067A (en) * | 2022-05-07 | 2022-08-30 | 华南理工大学 | Hot-melt marking line modified material and preparation method and application thereof |
-
2002
- 2002-02-08 JP JP2002031723A patent/JP2003232018A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009525246A (en) * | 2006-02-01 | 2009-07-09 | コロロッビア イタリア ソシエタ ペル アチオニ | Method for producing aqueous dispersion of TiO2 in the form of nanoparticles, and dispersion obtained by this method |
| JP2010017696A (en) * | 2008-07-14 | 2010-01-28 | National Institute Of Advanced Industrial & Technology | Metal nano-particle catalyst and oxygen oxidation method |
| CN114958067A (en) * | 2022-05-07 | 2022-08-30 | 华南理工大学 | Hot-melt marking line modified material and preparation method and application thereof |
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