JP4652776B2 - Method for producing photocatalytic composite composition, and photocatalytic composite composition - Google Patents
Method for producing photocatalytic composite composition, and photocatalytic composite composition Download PDFInfo
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- JP4652776B2 JP4652776B2 JP2004327277A JP2004327277A JP4652776B2 JP 4652776 B2 JP4652776 B2 JP 4652776B2 JP 2004327277 A JP2004327277 A JP 2004327277A JP 2004327277 A JP2004327277 A JP 2004327277A JP 4652776 B2 JP4652776 B2 JP 4652776B2
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- 230000001699 photocatalysis Effects 0.000 title claims description 65
- 239000000203 mixture Substances 0.000 title claims description 52
- 239000002131 composite material Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000001506 calcium phosphate Substances 0.000 claims description 72
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 72
- 235000011010 calcium phosphates Nutrition 0.000 claims description 72
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 72
- 239000000758 substrate Substances 0.000 claims description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 20
- 108091005899 fibrous proteins Proteins 0.000 claims description 18
- 102000034240 fibrous proteins Human genes 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 108010022355 Fibroins Proteins 0.000 claims description 15
- 108010013296 Sericins Proteins 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 229910052586 apatite Inorganic materials 0.000 description 13
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000012890 simulated body fluid Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- -1 NaHCO 3 Chemical compound 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- UKXAGBYRVKMKEA-UHFFFAOYSA-N phosphoric acid trihydrochloride Chemical compound Cl.Cl.Cl.P(O)(O)(O)=O UKXAGBYRVKMKEA-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明は、悪臭物質や有害物質の吸着、分解作用を有する光触媒性複合組成物の製造方法、および光触媒性複合組成物に関するものである。 The present invention relates to a method for producing a photocatalytic composite composition having an action of adsorbing and decomposing malodorous substances and harmful substances, and a photocatalytic composite composition.
酸化チタンなどの光触媒は、光が照射されると、接触してくる悪臭物質や有害物質を酸化還元作用により分解、除去することができる。しかしながら、酸化チタン自身は、吸着能力がほとんど無いため、空間内などで使用しても、酸化チタンと悪臭成分との接触機会が少なく、悪臭成分などの分解効率が低い。そこで、酸化チタンを擬似体液に浸漬することにより、その表面をアパタイトで覆い、悪臭物質をアパタイトで吸着した後、酸化チタンで分解する技術が提案されている(例えば、特許文献１参照)。 Photocatalysts such as titanium oxide can decompose and remove malodorous substances and harmful substances that come into contact by oxidation-reduction when irradiated with light. However, since titanium oxide itself has almost no adsorption capability, even if it is used in a space or the like, there are few opportunities for contact between titanium oxide and malodorous components, and decomposition efficiency of malodorous components and the like is low. Therefore, a technique has been proposed in which titanium oxide is immersed in a simulated body fluid so that the surface is covered with apatite, malodorous substances are adsorbed with apatite, and then decomposed with titanium oxide (see, for example, Patent Document 1).
また、擬似体液に代えて、リン酸イオンを含まないカルシウム溶液と、カルシウムイオンを含まないリン酸溶液とに酸化チタンを交互に接触させて、酸化チタンの表面をアパタイトで覆う技術が提案されている(例えば、特許文献２参照)。
このようなアパタイト被覆光触媒(光触媒性複合組成物)は、酸化チタンの表面がアパタイトで完全に覆われていると、酸化チタンの光触媒作用を利用することができないため、酸化チタンの表面の一部のみをアパタイトで被覆しておくことが好ましい。 Such an apatite-coated photocatalyst (photocatalytic composite composition) cannot partially utilize the photocatalytic action of titanium oxide when the surface of titanium oxide is completely covered with apatite. It is preferable to coat only with apatite.
しかしながら、従来の方法でアパタイト被覆光触媒を製造すると、酸化チタン表面の略全体がアパタイトで覆われてしまい、アパタイトが有する細孔の底部でしか酸化チタンが露出していないため、悪臭物質などの分解能力が低いという問題点がある。また、従来の方法でアパタイト被覆光触媒を製造すると、酸化チタンの表面に形成されるのは、結晶化度の高いアパタイトであるため、その一部を除去して酸化チタンの表面を露出させるのが困難であり、悪臭物質などの分解能力が高いアパタイト被覆光触媒を製造するのが困難であるという問題点がある。 However, when an apatite-coated photocatalyst is produced by a conventional method, the entire surface of the titanium oxide is covered with apatite, and the titanium oxide is exposed only at the bottom of the pores of the apatite. There is a problem that ability is low. In addition, when an apatite-coated photocatalyst is produced by a conventional method, it is apatite with a high degree of crystallinity that is formed on the surface of titanium oxide. There is a problem that it is difficult to produce an apatite-coated photocatalyst having a high ability to decompose malodorous substances and the like.
以上の問題点に鑑みて、本発明の課題は、酸化チタンなどの光触媒機能を有する基材の表面の一部のみを吸着物質層で被覆した光触媒性複合組成物を製造するのに適した方法、およびこの方法で製造した光触媒性複合組成物を提供することにある。 In view of the above problems, the object of the present invention is to provide a method suitable for producing a photocatalytic composite composition in which only a part of the surface of a substrate having a photocatalytic function such as titanium oxide is coated with an adsorbent layer. And providing a photocatalytic composite composition produced by this method.
上記課題を解決するために、本発明では、光触媒機能を有する基材を多孔性リン酸カルシウム合成用の処理液と接触させて当該基材の表面を多孔性リン酸カルシウム(アパタイトあるいはその類縁化合物)で被覆した光触媒性複合組成物を製造する方法において、前記処理液中に繊維状蛋白質を含ませておくことを特徴とする。 In order to solve the above-mentioned problems, in the present invention, a substrate having a photocatalytic function is brought into contact with a treatment liquid for porous calcium phosphate synthesis, and the surface of the substrate is coated with porous calcium phosphate (apatite or an analogous compound thereof). In the method for producing a photocatalytic composite composition, a fibrous protein is contained in the treatment liquid.
本発明に係る光触媒性複合組成物の製造方法では、処理液中に繊維状蛋白質を添加したため、基材表面での多孔性リン酸カルシウムの生成が不完全であり、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態にある。また、処理液中に繊維状蛋白質を添加すると、基材表面での多孔性リン酸カルシウムの生成が不完全であり、リン酸カルシウムの結晶化度が低いため、基材表面の全体が多孔性リン酸カルシウムで覆われている場合でも、ボールミルで軽く攪拌した場合、あるいはボールミルよりも破砕力の小さな装置で攪拌した場合でも、多孔性リン酸カルシウムの一部が基材表面から脱落し、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態になる。 In the method for producing a photocatalytic composite composition according to the present invention, since fibrous protein is added to the treatment liquid, the formation of porous calcium phosphate on the substrate surface is incomplete, and only part of the substrate surface is porous. It is in the state of being coated with the calcium phosphate. In addition, when fibrous protein is added to the treatment liquid, the formation of porous calcium phosphate on the substrate surface is incomplete and the crystallinity of calcium phosphate is low, so the entire substrate surface is covered with porous calcium phosphate. Even when the sample is lightly stirred with a ball mill or with a device having a smaller crushing force than the ball mill, part of the porous calcium phosphate falls off the substrate surface, and only part of the substrate surface is porous. It becomes the state coat | covered with the property calcium phosphate.
本発明において、前記基材は、例えば、二酸化チタンである。 In the present invention, the base material is, for example, titanium dioxide.
本発明において、前記繊維状蛋白質は、例えば、絹からセリシンを除去して得たフィブロインである。本願明細書において、「絹」とは「生糸」も含む意味である。 In the present invention, the fibrous protein is, for example, fibroin obtained by removing sericin from silk. In this specification, “silk” means “raw silk”.
この場合、前記処理液によって前記基材の表面を前記多孔性リン酸カルシウムで被覆した後、焼成を行ってもよい。光触媒性複合組成物を製造する際、その処理液に繊維状蛋白質を添加しておくと、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態になる。また、焼成を行うと、多孔性リン酸カルシウムに含まれていた繊維状蛋白質が分解、除去される結果、空洞が生成され、かかる空洞によって、多孔性リン酸カルシウムの多孔性が高まり、吸着能力が向上する。また、空洞の底部において、光触媒機能を有する基材が露出するので、悪臭物質や有害物質の分解能力が向上するという利点がある。 In this case, firing may be performed after the surface of the base material is coated with the porous calcium phosphate with the treatment liquid. When producing a photocatalytic composite composition, if a fibrous protein is added to the treatment liquid, only a part of the substrate surface is coated with porous calcium phosphate. Moreover, when calcination is performed, the fibrous protein contained in the porous calcium phosphate is decomposed and removed. As a result, cavities are generated. The cavities increase the porosity of the porous calcium phosphate and improve the adsorption ability. Moreover, since the base material which has a photocatalytic function is exposed in the bottom part of a cavity, there exists an advantage that the decomposition capability of a malodorous substance and a harmful substance improves.
本発明においては、前記処理液に絹あるいは絹を加水分解したものを添加することにより、当該処理液に前記繊維状蛋白質を含ませておいてもよい。このように構成すると、光触媒性複合組成物にセリシンが保持されるので、生体とのなじみが向上するという利点がある。また、セリシンが保持されていると、光の吸収帯域が広がる傾向にある。 In the present invention, the fibrous protein may be contained in the treatment liquid by adding silk or silk hydrolyzed silk to the treatment liquid. If comprised in this way, since sericin is hold | maintained at a photocatalytic composite composition, there exists an advantage that familiarity with a biological body improves. If sericin is retained, the light absorption band tends to be widened.
本発明に係る方法で製造した光触媒性複合組成物は、従来の光触媒性複合組成物と比較して水などの溶媒への分散性が高い。それ故、スプレー剤として噴霧するのに適している。 The photocatalytic composite composition produced by the method according to the present invention has a higher dispersibility in a solvent such as water than a conventional photocatalytic composite composition. Therefore, it is suitable for spraying as a spray agent.
本発明に係る光触媒性複合組成物は、処理液中に繊維状蛋白質を添加したため、基材表面での多孔性リン酸カルシウムの生成が不完全であり、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態にある。また、処理液中に繊維状蛋白質を添加すると、基材表面での多孔性リン酸カルシウムの生成が不完全であり、リン酸カルシウムの結晶化度が低いため、基材表面の全体が多孔性リン酸カルシウムで覆われている場合でも、ボールミルで軽く攪拌した場合、あるいはボールミルよりも破砕力の小さな装置で攪拌した場合でも、多孔性リン酸カルシウムの一部が基材表面から脱落し、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態になる。従って、本発明に係る方法で製造した光触媒性複合組成物では、まず、多孔性リン酸カルシウムが悪臭物質や有害物質を吸着し、これらの悪臭物質や有害物質を二酸化チタンなどの基材が分解、除去するので、悪臭物質や有害物質を効率よく除去することができる。また、本発明に係る方法で製造した光触媒性複合組成物は、水などの溶媒への分散性が高いため、高濃度の分散液を調製できるとともに、スプレー液に低い濃度で配合した場合でも、均一に噴霧することができる。また、均一に塗布、噴霧できるので、塗布、噴霧した後、テーブルなどが白く汚れてしまうことを回避できる。また、透明基材に塗布、噴霧した場合でも、透明基材の透明度を低下させないという利点がある。 In the photocatalytic composite composition according to the present invention, since fibrous protein is added to the treatment liquid, the formation of porous calcium phosphate on the substrate surface is incomplete, and only part of the substrate surface is porous calcium phosphate. It is in a coated state. In addition, when fibrous protein is added to the treatment liquid, the formation of porous calcium phosphate on the substrate surface is incomplete and the crystallinity of calcium phosphate is low, so the entire substrate surface is covered with porous calcium phosphate. Even when the sample is lightly stirred with a ball mill or with a device having a smaller crushing force than the ball mill, part of the porous calcium phosphate falls off the substrate surface, and only part of the substrate surface is porous. It becomes the state coat | covered with the property calcium phosphate. Therefore, in the photocatalytic composite composition produced by the method according to the present invention, first, porous calcium phosphate adsorbs malodorous substances and harmful substances, and these malodorous substances and harmful substances are decomposed and removed by a substrate such as titanium dioxide. Therefore, malodorous substances and harmful substances can be efficiently removed. In addition, the photocatalytic composite composition produced by the method according to the present invention is highly dispersible in a solvent such as water, so that a high-concentration dispersion can be prepared, and even when blended at a low concentration in a spray solution, Can spray uniformly. Moreover, since it can apply | coat and spray uniformly, it can avoid that a table etc. become dirty after application | coating and spraying. Moreover, even when applied to and sprayed on a transparent substrate, there is an advantage that the transparency of the transparent substrate is not lowered.
［実施の形態１］
本形態では、二酸化チタンの粉体などの光触媒機能を有する基材を、処理液と接触させて当該基材の表面を多孔性リン酸カルシウムで被覆して光触媒性複合組成物を製造する際、前記処理液中に、絹からセリシンを除去して得たフィブロインなどの繊維状蛋白質を含ませておく。
[Embodiment 1]
In this embodiment, when the substrate having a photocatalytic function such as titanium dioxide powder is brought into contact with the treatment liquid to coat the surface of the substrate with porous calcium phosphate to produce the photocatalytic composite composition, A fibrous protein such as fibroin obtained by removing sericin from silk is contained in the liquid.
ここで、絹からセリシンを除去してフィブロインを得るには、絹を水酸化ナトリム溶液などに浸漬して加水分解を行い、その後、洗浄してフィブロインを得る。 Here, to remove sericin from silk to obtain fibroin, silk is immersed in a sodium hydroxide solution or the like to perform hydrolysis, and then washed to obtain fibroin.
また、二酸化チタンの粉体などの基材を処理液と接触させて当該基材の表面を多孔性リン酸カルシウムで被覆する際には、処理液として、例えば、擬似体液、あるいはこの擬似体液に対してリン酸イオンやカルシウム濃度を高めたものを用いる。 In addition, when a substrate such as titanium dioxide powder is brought into contact with the treatment liquid and the surface of the substrate is coated with porous calcium phosphate, the treatment liquid is, for example, simulated body fluid or the simulated body fluid. Use a phosphate ion or calcium concentration increased.
また、酸化チタンの粉体などの基材を処理液と接触させて当該基材の表面を多孔性リン酸カルシウムで被覆する際には、リン酸イオンを含まないカルシウム溶液と、カルシウムイオンを含まないリン酸溶液とを用い、これらの溶液に前記基材を交互に接触させてもよい。その際には、カルシウム溶液あるいはリン酸溶液に対して繊維状蛋白質を添加する。 In addition, when a base material such as titanium oxide powder is brought into contact with the treatment liquid and the surface of the base material is coated with porous calcium phosphate, a calcium solution not containing phosphate ions and phosphorous not containing calcium ions are used. An acid solution may be used, and the substrate may be alternately contacted with these solutions. At that time, a fibrous protein is added to the calcium solution or the phosphoric acid solution.
このような方法で製造した光触媒性複合組成物では、基材表面での多孔性リン酸カルシウムの生成が不完全であるため、基材表面の一部のみが多孔性リン酸カルシウムで被覆され、光触媒機能を有する基材が露出した状態にある。 In the photocatalytic composite composition produced by such a method, since the formation of porous calcium phosphate on the substrate surface is incomplete, only part of the substrate surface is coated with porous calcium phosphate and has a photocatalytic function. The substrate is in an exposed state.
また、本発明に係る方法で製造した光触媒性複合組成物では、基材表面での多孔性リン酸カルシウムの生成が不完全であり、リン酸カルシウムの結晶化度が低い。このため、本発明に係る方法で製造した光触媒性複合組成物については、ボールミルで軽く攪拌した場合、あるいはボールミルよりも破砕力の小さな装置で攪拌した場合でも、多孔性リン酸カルシウムの一部が基材表面から脱落し、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態になるので、光触媒機能を有する基材が露出した状態となる。 Moreover, in the photocatalytic composite composition produced by the method according to the present invention, the formation of porous calcium phosphate on the substrate surface is incomplete, and the crystallinity of calcium phosphate is low. Therefore, for the photocatalytic composite composition produced by the method according to the present invention, even when lightly stirred with a ball mill or with a device having a smaller crushing force than the ball mill, a part of the porous calcium phosphate is a base material. Since it falls off from the surface and only a part of the substrate surface is covered with porous calcium phosphate, the substrate having a photocatalytic function is exposed.
従って、本形態に係る方法で製造した光触媒性複合組成物を悪臭物質や有害物質を存在する空間に単独、または有機系あるいは無機系のバインダに分散させた状態で配置しておくと、まず、多孔性リン酸カルシウムがシックハウス症候群の原因となる有害物質など、各種の有害物質や悪臭物質を吸着する。また、光触媒性複合組成物は、蛍光灯、白熱灯、ブラックライト、ＵＶランプ、水銀灯、キセノンランプ、ハロゲンランプ、メタルハライドランプなどからの人工光や太陽光などを受けると、これらの悪臭物質や有害物質を二酸化チタンなどの基材が分解、除去する。それ故、悪臭物質や有害物質を効率よく除去することができる。 Therefore, when the photocatalytic composite composition produced by the method according to this embodiment is arranged in a space where malodorous substances and harmful substances are present alone or dispersed in an organic or inorganic binder, Porous calcium phosphate adsorbs various harmful substances and malodorous substances such as harmful substances causing sick house syndrome. In addition, the photocatalytic composite composition is toxic or harmful when it receives artificial light or sunlight from a fluorescent lamp, incandescent lamp, black light, UV lamp, mercury lamp, xenon lamp, halogen lamp, metal halide lamp, etc. The material is decomposed and removed by a substrate such as titanium dioxide. Therefore, malodorous substances and harmful substances can be efficiently removed.
また、本形態に係る方法で製造した光触媒性複合組成物は、水などの溶媒への分散性が高いため、水中の悪臭物質や有害物質の除去に用いることができる。また、水などの溶媒への分散性が高いため、高濃度の分散液を調製できるとともに、スプレー液に低い濃度で配合した場合でも、均一に噴霧することができる。また、コーティング剤やスプレー剤などとして用いた場合、均一に塗布、噴霧できるので、塗布、噴霧した後、テーブルやカーテンなどが白く汚れてしまうことを回避できる。また、ガラスなどの透明基材に塗布、噴霧した場合でも、透明基材の透明度を低下させないという利点がある。 Moreover, since the photocatalytic composite composition produced by the method according to this embodiment has high dispersibility in a solvent such as water, it can be used for removing malodorous substances and harmful substances in water. In addition, since the dispersibility in a solvent such as water is high, a high concentration dispersion can be prepared, and even when blended at a low concentration in the spray liquid, it can be sprayed uniformly. Further, when used as a coating agent or spray agent, it can be uniformly applied and sprayed, so that it is possible to avoid the table and curtains from becoming dirty after application and spraying. Moreover, even when applied to and sprayed on a transparent substrate such as glass, there is an advantage that the transparency of the transparent substrate is not lowered.
さらに、本形態の光触媒性複合組成物については、有用な微生物の活性を高める一方、不要な微生物の活性を低下させる土壌改質剤として利用できる。 Furthermore, the photocatalytic composite composition of the present embodiment can be used as a soil modifier that increases the activity of useful microorganisms while reducing the activity of unnecessary microorganisms.
さらにまた、ペットフードに添加しておけば、多孔性リン酸カルシウムが体内で分解される結果、光触媒機能を有する基材が剥き出しの状態で***されるので、***物の臭いを除去してくれる。 Furthermore, if it is added to pet food, the porous calcium phosphate is decomposed in the body. As a result, the base material having a photocatalytic function is excreted in a bare state, so that the odor of excrement is removed.
［実施の形態２］
本形態でも、実施の形態１と同様、二酸化チタンの粉体などの光触媒機能を有する基材を、処理液と接触させて当該基材の表面を多孔性リン酸カルシウムで被覆して光触媒性複合組成物を製造する際、前記処理液中に、絹からセリシンを除去して得たフィブロインなどの繊維状蛋白質を含ませておく。
[Embodiment 2]
Also in this embodiment, as in Embodiment 1, a photocatalytic composite composition in which a substrate having a photocatalytic function such as titanium dioxide powder is brought into contact with the treatment liquid and the surface of the substrate is coated with porous calcium phosphate. When manufacturing the above, the processing solution contains a fibrous protein such as fibroin obtained by removing sericin from silk.
本形態では、この方法で製造した光触媒性複合組成物を焼成する。 In this embodiment, the photocatalytic composite composition produced by this method is fired.
このような方法で製造した光触媒性複合組成物も、実施の形態１と同様な効果を奏する。また、本形態では、焼成工程を追加したため、多孔性リン酸カルシウムに含まれていた繊維状蛋白質が分解、除去される結果、空洞が生成される。かかる空洞によって、多孔性リン酸カルシウムの多孔性が高まるので、吸着能力が向上する。また、空洞の底部において光触媒機能を有する基材が露出するので、悪臭物質や有害物質の分解能力が向上する。 The photocatalytic composite composition produced by such a method also has the same effect as that of the first embodiment. Moreover, in this form, since the baking process was added, the fibrous protein contained in porous calcium phosphate is decomposed | disassembled and removed, As a result, a cavity is produced | generated. Such voids increase the porosity of the porous calcium phosphate, thus improving the adsorption capacity. Moreover, since the base material having a photocatalytic function is exposed at the bottom of the cavity, the ability to decompose malodorous substances and harmful substances is improved.
［実施の形態３］
本形態では、二酸化チタンの粉体などの光触媒機能を有する基材を、処理液と接触させて当該基材の表面を多孔性リン酸カルシウムで被覆して光触媒性複合組成物を製造する際、前記処理液中に、絹を水酸化ナトリム溶液などで加水分解したものを添加しておく。すなわち、処理液中に、絹に含まれていたセリシンとフィブロイン(繊維状蛋白質)とを含ませておく。
[Embodiment 3]
In this embodiment, when the substrate having a photocatalytic function such as titanium dioxide powder is brought into contact with the treatment liquid to coat the surface of the substrate with porous calcium phosphate to produce the photocatalytic composite composition, In the liquid, silk hydrolyzed with sodium hydroxide solution or the like is added. That is, sericin and fibroin (fibrous protein) contained in silk are included in the treatment liquid.
このような方法で製造した光触媒性複合組成物も、実施の形態１と同様、基材表面での多孔性リン酸カルシウムの生成が不完全であり、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態にある。また、基材表面での多孔性リン酸カルシウムの生成が不完全であり、リン酸カルシウムの結晶化度が低い。ボールミルで軽く攪拌した場合、さらにはボールミルよりも破砕力の小さな装置で攪拌した場合でも、多孔性リン酸カルシウムの一部が基材表面から脱落し、基材表面の一部のみが多孔性リン酸カルシウムで被覆された状態になる。従って、本発明に係る方法で製造した光触媒性複合組成物を悪臭物質や有害物質の存在する空間や液中に単独で、または有機系あるいは無機系のバインダに分散させた状態で配置しておくと、まず、多孔性リン酸カルシウムが悪臭物質や有害物質を吸着する。また、光触媒性複合組成物は、蛍光灯、白熱灯、ブラックライト、ＵＶランプ、水銀灯、キセノンランプ、ハロゲンランプ、メタルハライドランプなどからの人工光や太陽光などを受けると、これらの悪臭物質や有害物質を二酸化チタンなどの基材が分解、除去する。それ故、悪臭物質や有害物質を効率よく除去することができる。 Similarly to Embodiment 1, the photocatalytic composite composition produced by such a method has incomplete generation of porous calcium phosphate on the substrate surface, and only a part of the substrate surface is covered with porous calcium phosphate. It is in the state that was done. Moreover, the production | generation of the porous calcium phosphate on the base-material surface is incomplete, and the crystallinity degree of calcium phosphate is low. Even when agitated lightly with a ball mill or even with a device with less crushing force than a ball mill, part of the porous calcium phosphate falls off the substrate surface, and only part of the substrate surface is covered with porous calcium phosphate. It will be in the state. Therefore, the photocatalytic composite composition produced by the method according to the present invention is arranged alone in a space or liquid where malodorous substances and harmful substances are present, or dispersed in an organic or inorganic binder. First, porous calcium phosphate adsorbs malodorous substances and harmful substances. In addition, the photocatalytic composite composition is toxic or harmful when it receives artificial light or sunlight from a fluorescent lamp, incandescent lamp, black light, UV lamp, mercury lamp, xenon lamp, halogen lamp, metal halide lamp, etc. The material is decomposed and removed by a substrate such as titanium dioxide. Therefore, malodorous substances and harmful substances can be efficiently removed.
また、本形態の光触媒性複合組成物は、有用な微生物の活性を高める一方、不要な微生物の活性を低下させる土壌改質剤として利用できる。また、ペットフードに添加しておけば、多孔性リン酸カルシウムが体内で分解される結果、光触媒機能を有する基材が剥き出しの状態で***されるので、***物の臭いを除去してくれる。 Moreover, the photocatalytic composite composition of the present embodiment can be used as a soil modifier that increases the activity of useful microorganisms while decreasing the activity of unnecessary microorganisms. Moreover, if it is added to pet food, porous calcium phosphate is decomposed in the body. As a result, the substrate having a photocatalytic function is excreted in a bare state, so that the smell of excrement is removed.
さらに、光触媒性複合組成物にセリシンが保持されるので、生体とのなじみが高い。従って、繊維などに保持された場合に肌触りがよいなどの利点がある。 Furthermore, since sericin is held in the photocatalytic composite composition, it is highly compatible with living organisms. Therefore, there is an advantage that the touch is good when held by a fiber or the like.
しかも、光触媒性複合組成物にセリシンが保持されていると、光の吸収帯域が広がる傾向にある。 Moreover, when sericin is retained in the photocatalytic composite composition, the light absorption band tends to be widened.
次に、本発明の実施例に基づいて本発明をより詳細に説明する。 Next, based on the Example of this invention, this invention is demonstrated in detail.
（実施例１）
本例では、結晶形がアナターゼの二酸化チタンの粉体(光触媒機能を有する基材)を擬似体液に浸漬し、その表面に多孔性のリン酸カルシウムを生成させる。その際、処理液には、絹からセリシンを除去して得たフィブロインを０．１〜数％、添加しておく。
Example 1
In this example, a powder of titanium dioxide having a crystal form of anatase (a substrate having a photocatalytic function) is immersed in a simulated body fluid to generate porous calcium phosphate on the surface thereof. At that time, 0.1 to several percent of fibroin obtained by removing sericin from silk is added to the treatment liquid.
ここで用いられる擬似体液(処理液)の基本組成は、ＮａＣｌ、ＮａＨＣＯ3、ＫＣｌ、Ｋ2ＨＰＯ4、Ｈ2Ｏ、ＭｇＣｌ2・Ｈ2Ｏ、ＣａＣｌ2などを水に溶かすことで調製され、浸漬温度は、30〜100℃、浸漬時間は１時間から２０日間である。なお、処理液は、ＨＣｌなどでｐＨを７〜８に調整しておく。 The basic composition of the simulated body fluid (treatment liquid) used here is prepared by dissolving NaCl, NaHCO 3 , KCl, K 2 HPO 4 , H 2 O, MgCl 2 .H 2 O, CaCl 2, etc. in water, The immersion temperature is 30 to 100 ° C., and the immersion time is 1 hour to 20 days. The treatment liquid is adjusted to pH 7-8 with HCl or the like.
このように構成した処理液の組成は、概ね、
Ｎａ+＝１２０〜１６０ｍＭ
Ｋ+＝１〜２０ｍＭ
Ｃａ2+＝０．５〜５０ｍＭ
Ｍｇ2+＝０．５〜５０ｍＭ
Ｃｌ-＝８０〜２００ｍＭ
ＨＣＯ3-＝０．５〜３０ｍＭ
ＨＰＯ4 2-＝１〜２０ｍＭ
である。
The composition of the treatment liquid configured in this way is roughly
Na + = 120 to 160 mM
K + = 1-20 mM
Ca 2+ = 0.5 to 50 mM
Mg 2+ = 0.5-50 mM
Cl − = 80 to 200 mM
HCO 3− = 0.5 to 30 mM
HPO 4 2- = 1-20 mM
It is.
ここで、多孔性リン酸カルシウムの多孔性や膜厚などは、処理液の組成や温度、浸漬時間を変えることによって制御することができる。フィブロインの濃度が高い場合やリン酸イオンやカルシウムイオンの濃度が低い場合には、多孔性リン酸カルシウムの被覆度が低下する傾向にある。また、フィブロインの濃度が高い場合には多孔性リン酸カルシウムの結晶化度が低下する傾向にある。 Here, the porosity and film thickness of the porous calcium phosphate can be controlled by changing the composition, temperature, and immersion time of the treatment liquid. When the concentration of fibroin is high or when the concentration of phosphate ions or calcium ions is low, the coverage of porous calcium phosphate tends to decrease. Moreover, when the fibroin concentration is high, the crystallinity of the porous calcium phosphate tends to decrease.
なお、本例で製造した光触媒性複合組成物については、ボールミルによる攪拌などの処理を行って、多孔性リン酸カルシウムの一部を基材表面から脱落させ、多孔性リン酸カルシウムの被覆度を低下させてもよい。この場合でも、リン酸カルシウムの結晶化度が低いため、多孔性リン酸カルシウムの基材表面からの脱落を容易に行うことができる。 Note that the photocatalytic composite composition produced in this example may be subjected to a treatment such as stirring with a ball mill so that a part of the porous calcium phosphate is removed from the surface of the substrate and the coverage of the porous calcium phosphate is lowered. Good. Even in this case, since the crystallinity of calcium phosphate is low, the porous calcium phosphate can be easily detached from the substrate surface.
（実施例２）
本例では、結晶形がアナターゼの二酸化チタンの粉体(光触媒機能を有する基材)を、リン酸イオンを含まないカルシウム溶液と、カルシウムイオンを含まないリン酸溶液とに交互に接触させて、二酸化チタンの粉体の表面に多孔性リン酸カルシウムを生成させた後、100℃〜700℃で１０分から１２０分間、焼成する。例えば、リン酸溶液に二酸化チタンの粉体を浸漬、乾燥を行った後、二酸化チタンの粉体をカルシウム溶液に浸漬し、しかる後に焼成する。その際、例えば、カルシウム溶液(処理液)には、絹からセリシンを除去して得たフィブロインを０．１〜数％、添加しておく。
(Example 2)
In this example, a powder of titanium dioxide having a crystal form of anatase (a substrate having a photocatalytic function) is alternately brought into contact with a calcium solution not containing phosphate ions and a phosphate solution containing no calcium ions. After forming porous calcium phosphate on the surface of the titanium dioxide powder, it is fired at 100 to 700 ° C. for 10 to 120 minutes. For example, after a titanium dioxide powder is immersed in a phosphoric acid solution and dried, the titanium dioxide powder is immersed in a calcium solution and then fired. At that time, for example, 0.1 to several percent of fibroin obtained by removing sericin from silk is added to the calcium solution (treatment liquid).
ここで用いられるカルシウム溶液およびリン酸溶液は、例えば、以下の組成
カルシウム溶液＝１００〜３００ｍＭのＣａＣｌ2／Ｔｒｉｓ−ＨＣｌ
リン酸溶液＝５０〜２００ｍＭのＮａ2ＨＰＯ4溶液
を有する。
The calcium solution and phosphoric acid solution used here have, for example, the following composition: calcium solution = 100 to 300 mM CaCl 2 / Tris-HCl
Phosphate solution = 50-200 mM Na 2 HPO 4 solution.
本例でも、多孔性リン酸カルシウムの多孔性性や膜厚などは、処理液の組成や温度、浸漬時間を変えることによって制御することができる。フィブロインの濃度が高い場合やリン酸イオンやカルシウムイオンの濃度が低い場合には、多孔性リン酸カルシウムの被覆度が低下する傾向にある。また、フィブロインの濃度が高い場合には多孔性リン酸カルシウムの結晶化度が低下する傾向にある。 Also in this example, the porosity and film thickness of the porous calcium phosphate can be controlled by changing the composition, temperature and immersion time of the treatment liquid. When the concentration of fibroin is high or when the concentration of phosphate ions or calcium ions is low, the coverage of porous calcium phosphate tends to decrease. Moreover, when the fibroin concentration is high, the crystallinity of the porous calcium phosphate tends to decrease.
なお、本例で製造した光触媒性複合組成物については、焼成後、ボールミルによる攪拌などの処理を行って、多孔性リン酸カルシウムの一部を基材表面から脱落させ、多孔性リン酸カルシウムの被覆度を低下させてもよい。この場合でも、リン酸カルシウムの結晶化度が低いため、多孔性リン酸カルシウムの基材表面からの脱落を容易に行うことができる。 For the photocatalytic composite composition produced in this example, after firing, a treatment such as stirring with a ball mill is performed to remove a part of the porous calcium phosphate from the surface of the substrate, thereby reducing the coverage of the porous calcium phosphate. You may let them. Even in this case, since the crystallinity of calcium phosphate is low, the porous calcium phosphate can be easily detached from the substrate surface.
（実施例３）
本例では、実施の形態１、２と同様、結晶形がアナターゼの二酸化チタンの粉体(光触媒機能を有する基材)を擬似体液に浸漬し、その表面に多孔性のリン酸カルシウムを生成させた後、100℃〜700℃で１０分から１２０分間、焼成する。その際、処理液には、絹からセリシンを除去して得たフィブロインを０．１〜数％、添加しておく。
(Example 3)
In this example, after the powder of titanium dioxide whose crystal form is anatase (base material having a photocatalytic function) is immersed in a simulated body fluid to form porous calcium phosphate on the surface, as in the first and second embodiments. Baked at 100 to 700 ° C. for 10 to 120 minutes. At that time, 0.1 to several percent of fibroin obtained by removing sericin from silk is added to the treatment liquid.
なお、本例で製造した光触媒性複合組成物については、焼成後、ボールミルによる攪拌などの処理を行って、多孔性リン酸カルシウムの一部を基材表面から脱落させ、多孔性リン酸カルシウムの被覆度を低下させてもよい。この場合でも、リン酸カルシウムの結晶化度が低いため、多孔性リン酸カルシウムの基材表面からの脱落を容易に行うことができる。 For the photocatalytic composite composition produced in this example, after firing, a treatment such as stirring with a ball mill is performed to remove a part of the porous calcium phosphate from the surface of the substrate, thereby reducing the coverage of the porous calcium phosphate. You may let them. Even in this case, since the crystallinity of calcium phosphate is low, the porous calcium phosphate can be easily detached from the substrate surface.
（実施例４）
本例では、実施の形態１と同様、結晶形がアナターゼの二酸化チタンの粉体(光触媒機能を有する基材)を擬似体液に浸漬し、その表面に多孔性のリン酸カルシウムを生成させる。その際、処理液には、絹を水酸化ナトリム溶液などで加水分解したものを添加しておき、処理液中に、絹に含まれていたセリシンとフィブロイン(繊維状蛋白質)を含ませておく。その結果、セリシンが保持された光触媒性複合組成物を得ることができ、このような方法で製造した光触媒性複合組成物でも、実施の形態１と同様、基材表面での多孔性リン酸カルシウムの生成が不完全であり、リン酸カルシウムの結晶化度が低い。このため、そのままの状態、あるいは、さらに攪拌などの処理を行えば、光触媒機能を有する基材表面の一部のみが多孔性リン酸カルシウムで被覆され、基材が露出した光触媒性複合組成物を得ることができる。
Example 4
In this example, as in Embodiment 1, a titanium dioxide powder having a crystal form of anatase (a substrate having a photocatalytic function) is immersed in a simulated body fluid, and porous calcium phosphate is generated on the surface thereof. At that time, the hydrolyzed silk with a sodium hydroxide solution or the like is added to the treatment liquid, and sericin and fibroin (fibrous protein) contained in the silk are contained in the treatment liquid. . As a result, a photocatalytic composite composition retaining sericin can be obtained, and even in the photocatalytic composite composition produced by such a method, the formation of porous calcium phosphate on the surface of the substrate is the same as in the first embodiment. Is incomplete and the crystallinity of calcium phosphate is low. For this reason, if the treatment is carried out as it is or further with stirring, a photocatalytic composite composition in which only a part of the substrate surface having a photocatalytic function is coated with porous calcium phosphate and the substrate is exposed is obtained. Can do.
Claims (6)
前記処理液中に繊維状蛋白質を含ませておくことを特徴とする光触媒性複合組成物の製造方法。 In the method for producing a photocatalytic composite composition in which a substrate having a photocatalytic function is brought into contact with a treatment liquid for synthesizing porous calcium phosphate and the surface of the substrate is coated with porous calcium phosphate,
A method for producing a photocatalytic composite composition, characterized in that a fibrous protein is contained in the treatment liquid.
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| JP2010201301A (en) * | 2009-02-28 | 2010-09-16 | Kankyo Hozen Kenkyusho:Kk | Treatment method of wastewater and waste oil |
| JP2011020928A (en) * | 2009-07-13 | 2011-02-03 | Kankyo Hozen Kenkyusho:Kk | Cosmetic and cleansing agent having detox function |
| JP2011050874A (en) * | 2009-09-02 | 2011-03-17 | Uchu Kankyo Hozen Center:Kk | Photocatalyst ceramics |
| JP2012170381A (en) * | 2011-02-21 | 2012-09-10 | Uchu Kankyo Hozen Center:Kk | Food additive for environmental cleaning also serving as medicine for intestinal disorders and feed |
| JP5839722B2 (en) * | 2013-02-25 | 2016-01-06 | 株式会社宇宙環境保全センター | Process for producing calcium carbonate-containing photocatalytic composite composition containing metal ions |
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| JPH10244166A (en) * | 1997-03-03 | 1998-09-14 | Agency Of Ind Science & Technol | Environment cleaning material and its production |
| JPH11347407A (en) * | 1998-06-08 | 1999-12-21 | Toru Nakajima | Production of air cleaning material |
| JP2003275600A (en) * | 2002-03-19 | 2003-09-30 | National Institute Of Advanced Industrial & Technology | Visible ray responsive and adsorptive composite material |
| WO2004000018A1 (en) * | 2002-06-25 | 2003-12-31 | Fujitsu Limited | Pesticide composition and pesticide residue decomposing agent |
| JP2004051952A (en) * | 2002-05-30 | 2004-02-19 | Japan Science & Technology Corp | Hydroxyapatite complex, method for producing the same and medical material using the same |
| JP2004168601A (en) * | 2002-11-20 | 2004-06-17 | National Institute Of Advanced Industrial & Technology | Apatite compound material, its manufacturing process and environmental cleaning material |
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|---|---|---|---|---|
| JPH10244166A (en) * | 1997-03-03 | 1998-09-14 | Agency Of Ind Science & Technol | Environment cleaning material and its production |
| JPH11347407A (en) * | 1998-06-08 | 1999-12-21 | Toru Nakajima | Production of air cleaning material |
| JP2003275600A (en) * | 2002-03-19 | 2003-09-30 | National Institute Of Advanced Industrial & Technology | Visible ray responsive and adsorptive composite material |
| JP2004051952A (en) * | 2002-05-30 | 2004-02-19 | Japan Science & Technology Corp | Hydroxyapatite complex, method for producing the same and medical material using the same |
| WO2004000018A1 (en) * | 2002-06-25 | 2003-12-31 | Fujitsu Limited | Pesticide composition and pesticide residue decomposing agent |
| JP2004168601A (en) * | 2002-11-20 | 2004-06-17 | National Institute Of Advanced Industrial & Technology | Apatite compound material, its manufacturing process and environmental cleaning material |
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