JP7089785B2 - Manufacturing method of hydrophilic material - Google Patents
Manufacturing method of hydrophilic material Download PDFInfo
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- JP7089785B2 JP7089785B2 JP2019220983A JP2019220983A JP7089785B2 JP 7089785 B2 JP7089785 B2 JP 7089785B2 JP 2019220983 A JP2019220983 A JP 2019220983A JP 2019220983 A JP2019220983 A JP 2019220983A JP 7089785 B2 JP7089785 B2 JP 7089785B2
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- aqueous solution
- acid
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- titanium
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- 239000000463 material Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 ore Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- Catalysts (AREA)
Description
本発明は、親水性材料及びその製造方法に関するものである。 The present invention relates to a hydrophilic material and a method for producing the same.
従来より、酸化チタンは、紫外線の作用によって脱臭や殺菌などに加えて防曇といった効能を発揮することが広く知られている。 Conventionally, it is widely known that titanium oxide exerts anti-fog effects in addition to deodorization and sterilization by the action of ultraviolet rays.
そのため、水蒸気などによって曇りやすいガラスや鏡などの表面に酸化チタンをコーティングして曇りを止めることが行われている（たとえば、特許文献１参照）。 Therefore, titanium oxide is coated on the surface of glass or a mirror, which is easily fogged by water vapor or the like, to stop the fog (see, for example, Patent Document 1).
ところが、酸化チタンは、紫外線が照射されることで防曇作用（コーティングされたガラスや鏡などの基材の表面を親水性にする作用）を発揮するため、屋内などの紫外線照射量が少ない場所においては、十分な紫外線が照射されずに防曇効果があまり得られないおそれがあった。 However, titanium oxide exerts an anti-fog effect (the effect of making the surface of a base material such as coated glass or a mirror hydrophilic) when irradiated with ultraviolet rays, so it is used indoors or in places where the amount of ultraviolet rays is low. In, there was a possibility that the anti-fog effect could not be obtained so much without being irradiated with sufficient ultraviolet rays.
そのため、可視光によっても基材の表面を親水性にする作用が長期間にわたって持続する材料の開発が望まれていた。 Therefore, it has been desired to develop a material that keeps the action of making the surface of the base material hydrophilic even with visible light for a long period of time.
そこで、本発明では、親水性材料の製造方法において、チタンを含む水溶液に塩基性物質を滴下して水酸化チタンを沈殿させた後に過酸化水素水を添加してペルオキソチタン酸溶液を生成し、生成したペルオキソチタン酸溶液をチタン酸水溶液として用いて、チタン酸水溶液とタングステン酸水溶液とを混合した後に、水熱処理することで酸化チタンと酸化タングステンとを複合結晶化させ、その後、スルホン酸とともにペルオキソチタン溶液を添加することにした。 Therefore, in the present invention, in the method for producing a hydrophilic material, a basic substance is added dropwise to an aqueous solution containing titanium to precipitate titanium hydroxide, and then a hydrogen peroxide solution is added to generate a peroxotitanic acid solution. Using the generated peroxotitanic acid solution as a titanic acid aqueous solution, the titanic acid aqueous solution and the tungsten acid aqueous solution are mixed, and then hydrothermally treated to form a composite crystallization of titanium oxide and tungsten oxide, and then peroxo together with the sulfonic acid. I decided to add a titanium solution .
そして、本発明では、以下に記載する効果を奏する。 Then, in the present invention, the effects described below are obtained.
すなわち、本発明では、酸化チタンと酸化タングステンとの複合結晶を含有しているために、可視光によってもコーティングした基材の表面を親水性にする作用を長期間にわたって持続させることができる。 That is, in the present invention, since the composite crystal of titanium oxide and tungsten oxide is contained, the action of making the surface of the base material coated with visible light hydrophilic can be maintained for a long period of time.
特に、スルホン酸又は／及びケイ酸とペルオキソチタン溶液とを含有させた場合には、コーティングする基材の表面への接着性が向上するとともに、透明性に優れており基材の表面が薄く曇った状態となることがなく、基材本来の表面の色や模様や反射を表出させることができる。 In particular, when sulfonic acid and / and silicic acid and a peroxotitanium solution are contained, the adhesiveness to the surface of the base material to be coated is improved, the transparency is excellent, and the surface of the base material is thinly clouded. It is possible to express the color, pattern, and reflection of the original surface of the base material without being in a state of being squeezed.
以下に、本発明に係る親水性材料及びその製造方法について具体的に説明する。 Hereinafter, the hydrophilic material according to the present invention and the method for producing the same will be specifically described.
本発明に係る親水性材料は、酸化チタンと酸化タングステンとの複合結晶を含有する（主成分とする）コーティング剤などとして利用される材料である。 The hydrophilic material according to the present invention is a material used as a coating agent (main component) containing a composite crystal of titanium oxide and tungsten oxide.
酸化チタンと酸化タングステンとの複合結晶は、たとえば、チタン酸水溶液とタングステン酸水溶液とを混合した後に、水熱処理することで酸化チタンと酸化タングステンとを複合結晶化させて製造することができる。 The composite crystal of titanium oxide and tungsten oxide can be produced, for example, by mixing an aqueous solution of titanium acid and an aqueous solution of tungstic acid and then hydrothermally treating the composite crystallization of titanium oxide and tungsten oxide.
チタン酸水溶液としては、たとえば、ペルオキソチタン酸溶液、又は、ペルオキソ基を含むアナターゼゾルを使用することができ、チタンを含む水溶液に、塩基性物質を滴下し、水酸化チタンを沈殿させた後、過酸化水素水を添加して得られるペルオキソチタン酸溶液、又は、８０℃以上において加熱処理或いはオートクレーブ中において加熱処理して得られるペルオキソ基を含むアナターゼゾルを生成することができる。 As the titanium acid aqueous solution, for example, a peroxotitanic acid solution or an anatase sol containing a peroxo group can be used, and a basic substance is added dropwise to the aqueous solution containing titanium to precipitate titanium hydroxide, and then the titanium hydroxide is precipitated. It is possible to produce a peroxotitanic acid solution obtained by adding a hydrogen peroxide solution, or an anatase sol containing a peroxo group obtained by heat treatment at 80 ° C. or higher or heat treatment in an autoclave.
タングステン酸水溶液としては、たとえば、三酸化タングステンの水和物の水溶液などのタングステンを含むオキソ酸溶液を使用することができる。 As the tungstic acid aqueous solution, for example, an oxoacid solution containing tungsten such as an aqueous solution of a hydrate of tungsten trioxide can be used.
水熱反応は、たとえば、オートクレーブ中にチタン酸水溶液とタングステン酸水溶液と水とを所定の比率で入れて加熱することで行わせることができる。 The hydrothermal reaction can be carried out, for example, by putting an aqueous solution of titanium acid, an aqueous solution of tungstic acid and water in a predetermined ratio in an autoclave and heating them.
このチタン酸水溶液とタングステン酸水溶液との水熱反応によって、高温高圧の熱水の存在下で酸化チタンと酸化タングステンとを複合結晶化させることができる。 By the hydrothermal reaction between the aqueous solution of titanium acid and the aqueous solution of tungstic acid, titanium oxide and tungsten oxide can be compositely crystallized in the presence of hot water at high temperature and high pressure.
酸化チタンと酸化タングステンとの複合結晶は、そのまま光触媒材料として利用することができる。 The composite crystal of titanium oxide and tungsten oxide can be used as it is as a photocatalytic material.
この酸化チタンと酸化タングステンとの複合結晶をコーティング剤として利用する場合には、基材表面への接着性を向上させるために、ケイ酸やスルホン酸のいずれか一種又は両方を添加することが好ましく、透明性を有するスルホン酸がより好ましい。この場合に、ケイ酸又は／及びスルホン酸とともにペルオキソチタン溶液とともに添加すると、基材表面への接着性や耐水性が向上する。 When this composite crystal of titanium oxide and tungsten oxide is used as a coating agent, it is preferable to add either one or both of silicic acid and sulfonic acid in order to improve the adhesiveness to the surface of the substrate. , Sulfonic acid having transparency is more preferable. In this case, when added together with a peroxotitanium solution together with silicic acid and / and sulfonic acid, the adhesiveness to the surface of the substrate and the water resistance are improved.
なお、基材としては、多種多様なものを用いることができ、たとえば、金属やコンクリートやガラスや鉱石やプラスチックや布などの材料を用いることができ、その用途も、各種壁材やガラスなどの建築基材でもよく、各種宝石やプラスチックなどの装身具でもよい。また、基材の表面にコーティング剤を付着させる方法としては、多種多様なものを用いることができ、たとえば、基材の表面にコーティング剤を刷毛で塗布してもよく、基材の表面にコーティング剤を噴霧してもよく、基材をコーティング剤に浸漬させてもよい。 As the base material, a wide variety of materials can be used, for example, materials such as metal, concrete, glass, ore, plastic, and cloth can be used, and the uses thereof are various wall materials, glass, and the like. It may be a building base material, or may be accessories such as various jewels and plastics. In addition, a wide variety of methods can be used to attach the coating agent to the surface of the base material. For example, the coating agent may be applied to the surface of the base material with a brush, and the surface of the base material is coated. The agent may be sprayed or the substrate may be immersed in the coating agent.
特に、酸化チタンと酸化タングステンとの複合結晶は、紫外線によって酸化チタンが光触媒活性され、可視光線によって酸化タングステンが光触媒活性されるため、屋外などの紫外線や可視光線が多量に照射される場所に限られず、屋内などの紫外線の照射が十分でない場所でも光触媒として機能させることができる。また、単結晶とは異なり複合結晶となっているために、長期間にわたって光触媒としての機能（親水性）を持続させることができる。そのため、特に室内のガラスや鏡などの防曇剤として有効に利用することができる。 In particular, the composite crystal of titanium oxide and tungsten oxide is limited to places where a large amount of ultraviolet rays or visible light is irradiated, such as outdoors, because titanium oxide is photocatalytically activated by ultraviolet rays and tungsten oxide is photocatalytically activated by visible light. Therefore, it can function as a photocatalyst even in a place where the irradiation of ultraviolet rays is not sufficient, such as indoors. Further, unlike a single crystal, it is a composite crystal, so that the function (hydrophilicity) as a photocatalyst can be maintained for a long period of time. Therefore, it can be effectively used as an anti-fog agent for indoor glass and mirrors.
以上に説明したように、本願発明に係る親水性材料は、酸化チタンと酸化タングステンとの複合結晶を含有しているために、紫外線によって酸化チタンが光触媒活性されるとともに、可視光線によって酸化タングステンが光触媒活性され、屋外などの紫外線や可視光線が多量に照射される場所に限られず、屋内などの紫外線の照射が十分でない場所でも光触媒として機能し、紫外光に限られず可視光によってもコーティングした基材の表面を親水性にする作用を長期間にわたって持続させることができる。 As described above, since the hydrophilic material according to the present invention contains a composite crystal of titanium oxide and tungsten oxide, titanium oxide is photocatalytically activated by ultraviolet rays and tungsten oxide is generated by visible light. A group that is photocatalytically activated and functions as a photocatalyst not only in places where a large amount of ultraviolet rays or visible light is irradiated, such as outdoors, but also in places where ultraviolet rays are not sufficiently irradiated, such as indoors, and is coated not only by ultraviolet light but also by visible light. The action of making the surface of the material hydrophilic can be maintained for a long period of time.
特に、スルホン酸又は／及びケイ酸とペルオキソチタン溶液とを含有させた場合には、コーティングする基材の表面への接着性が向上するとともに、透明性に優れており基材の表面が薄く曇った状態となることがなく、基材本来の表面の色や模様や反射を表出させることができる。 In particular, when sulfonic acid and / and silicic acid and a peroxotitanium solution are contained, the adhesiveness to the surface of the base material to be coated is improved, the transparency is excellent, and the surface of the base material is thinly clouded. It is possible to express the color, pattern, and reflection of the original surface of the base material without being in a state of being squeezed.
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| JP2019220983A JP7089785B2 (en) | 2019-12-06 | 2019-12-06 | Manufacturing method of hydrophilic material |
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| JP2019220983A JP7089785B2 (en) | 2019-12-06 | 2019-12-06 | Manufacturing method of hydrophilic material |
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| JP7089785B2 true JP7089785B2 (en) | 2022-06-23 |
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| JP7490895B2 (en) * | 2021-12-06 | 2024-05-27 | 三井金属鉱業株式会社 | Composite metal acid compound dispersing solution, composite metal acid compound powder, composite metal acid compound film, and methods for producing the same |
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