JP2008081712A - Photocatalytic coating - Google Patents
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- JP2008081712A JP2008081712A JP2006288087A JP2006288087A JP2008081712A JP 2008081712 A JP2008081712 A JP 2008081712A JP 2006288087 A JP2006288087 A JP 2006288087A JP 2006288087 A JP2006288087 A JP 2006288087A JP 2008081712 A JP2008081712 A JP 2008081712A
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- titanium oxide
- photocatalytic
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- photocatalytic coating
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- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 83
- 238000000576 coating method Methods 0.000 title abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 6
- 239000000057 synthetic resin Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052586 apatite Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- -1 polymethylmethoxysiloxane Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000003973 paint Substances 0.000 description 16
- 230000003385 bacteriostatic effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006757 chemical reactions by type Methods 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000474 nursing effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、塗布された物体を、その表面に形成された塗膜で外界から遮断して保護するとともに、塗膜に含まれる紫外光型及び／又は可視光型光触媒としての微粒子状光触媒性酸化チタンが、波長が約４００ｎｍより短い紫外光を主とする光、及び／又は、波長が約３８０ｎｍより長い可視光を主とする光で励起されることで、塗膜表面に有機物分解能をもたらす光触媒性塗布剤に関するものである。The present invention protects a coated object by shielding it from the outside with a coating film formed on the surface, and particulate photocatalytic oxidation as an ultraviolet light type and / or visible light type photocatalyst contained in the coating film. Photocatalyst that provides organic substance resolution on the coating film surface when titanium is excited by light mainly composed of ultraviolet light having a wavelength shorter than about 400 nm and / or light mainly composed of visible light having a wavelength longer than about 380 nm. It relates to an adhesive coating agent.
ちなみに、有機物分解能とは、たとえば、塗膜表面での汚れ分解能や、細菌発育阻止能のことを指す。細菌発育阻止能は、可逆的であったり非可逆的であったりする。「静菌（制菌）」（菌を殺滅しないまでも、その活動を停止ないし低下させ、その増殖を抑制する作用）は可逆的細菌発育阻止能であり、「滅菌」は非可逆的細菌発育阻止能である。また、この光触媒性塗布剤については、従来の光触媒塗料の場合同様、屋内外の各種構造物への使用のみならず、例えば、屋内外、特に屋内で持続的な静菌・殺菌を必要とするが、化学的殺菌剤のように人畜への芳しからぬ影響の懸念される物質の散布が憚られる場所（例えば、病院、介護施設、託児所、幼稚園、公民館、宿泊施設、飲食店、調理施設、更衣室、公衆トイレ、食品工場、薬品工場、衛生関係の実験室、酪農場／施設、植物栽培場／施設など）での使用も想定される。このうち、特に植物栽培場／施設では、栽培農作物や花卉自体、土壌や人工的培地、付帯設備などへの散布や塗布が考えられる。Incidentally, the organic matter resolution refers to, for example, the soil resolution on the coating film surface and the ability to inhibit bacterial growth. The ability to inhibit bacterial growth can be reversible or irreversible. “Bacteriostatic (antibacterial)” (the action of stopping or reducing the activity and inhibiting its growth, even if the fungus is not killed) is the ability to prevent reversible bacterial growth, and “sterilization” is an irreversible bacterium. It is a growth inhibitory ability. In addition, the photocatalytic coating agent requires continuous bacteriostatic / sterilization, for example, indoors and outdoors, especially indoors, as well as for use in various indoor and outdoor structures, as in the case of conventional photocatalytic paints. However, where chemical substances such as chemical disinfectants are sprayed with substances that may have an unfavorable impact on human livestock (eg hospitals, nursing homes, day care centers, kindergartens, public halls, lodging facilities, restaurants, cooking Facilities, changing rooms, public toilets, food factories, pharmaceutical factories, hygiene laboratories, dairy farms / facilities, plant growing areas / facilities, etc.) are also envisaged. Among them, especially in plant cultivation sites / facilities, spraying and application to cultivated crops and florets themselves, soil, artificial culture media, and incidental facilities can be considered.
従来、この種の光触媒塗料においては、塗料液中に光触媒源としての酸化チタンを含有させるのに、次の▲１▼，▲２▼のような方法がとられた。
▲１▼塗料の液状成分が、水、有機溶媒、結合剤（例えば、ポリメチルメトキシシロキサンなど）、界面活性剤などの混ざった液剤の場合、その液剤に光触媒性酸化チタン微粉末を直接混ぜたり、光触媒性酸化チタン微粒子を分散相とする水性ゾル（スラリ）やアルコールゾル（スラリ）を混ぜたりする。
▲２▼塗料の液状成分がペルオキソチタン酸水溶液の場合、その液を８０℃以上の或る温度で数時間〜数十時間加熱して、その液中に酸化チタン微粒子を生成させ（特許公報第２８７５９９３号、第２９３８３７６号）、場合により、その液に別途光触媒性酸化チタン微粉末を混ぜたり、光触媒性酸化チタン微粒子を分散相とする水性ゾルやアルコールゾルを混ぜたりする（特開平７−２８６１１４明細書）。Conventionally, in this type of photocatalyst coating, the following methods (1) and (2) have been employed to contain titanium oxide as a photocatalyst source in the coating liquid.
(1) If the liquid component of the paint is a mixture of water, organic solvent, binder (for example, polymethylmethoxysiloxane, etc.), surfactant, etc., photocatalytic titanium oxide fine powder can be mixed directly into the solution. Then, an aqueous sol (slurry) or alcohol sol (slurry) containing photocatalytic titanium oxide fine particles as a dispersed phase is mixed.
(2) When the liquid component of the paint is an aqueous solution of peroxotitanic acid, the liquid is heated at a certain temperature of 80 ° C. or higher for several hours to several tens of hours to generate titanium oxide fine particles in the liquid (Patent Publication No. 1). 2875993, No. 2938376), and in some cases, a photocatalytic titanium oxide fine powder is separately mixed in the liquid, or an aqueous sol or alcohol sol having photocatalytic titanium oxide fine particles as a dispersed phase is mixed (JP-A-7-286114). Specification).
しかし、上記▲１▼の場合、水、有機溶媒、結合剤、界面活性剤などの混合液剤は、決して酸化チタン微粉末ないしは微粒子を懸濁させやすいものではなく、特に有機溶媒、就中アルコール含有量の多い場合には、酸化チタン微粒子の液剤中での沈殿を招きやすいものである。とはいえ、沈殿抑制のため、液剤に強力な界面活性剤を多量に添加したりすると、最終的に得られた光触媒塗料液が泡立ちやすくなったり、得られた塗膜の耐水性の劣化を招いたりする。したがって、水、有機溶媒、結合剤、界面活性剤などの混合液剤に、光触媒源としての光触媒性酸化チタン微粉末を直接添加したり、光触媒性酸化チタン微粒子を分散相とする水性ゾルやアルコールゾルを添加したりし、酸化チタン微粉末ないしは微粒子を安定的に懸濁させるのは困難である。However, in the case of (1) above, the mixed liquid such as water, organic solvent, binder and surfactant is never easy to suspend titanium oxide fine powder or fine particles. When the amount is large, precipitation of titanium oxide fine particles in the liquid agent is likely to occur. Nonetheless, if a large amount of a strong surfactant is added to the liquid to suppress precipitation, the final photocatalyst coating liquid tends to foam or the water resistance of the resulting coating is deteriorated. I invite you. Therefore, an aqueous sol or alcohol sol having a photocatalytic titanium oxide fine powder directly added to a mixed liquid agent such as water, an organic solvent, a binder, or a surfactant, or a photocatalytic titanium oxide fine particle as a dispersed phase. It is difficult to suspend titanium oxide fine powder or fine particles stably.
一方、▲２▼の場合、ペルオキソチタン酸水溶液を或る温度で或る時間加熱し、その水溶液中に光触媒性酸化チタン微粒子を生成させても、その量は僅少であるため、ペルオキソチタン酸水溶液、若しくは、生成酸化チタン微粒子を含むペルオキソチタン酸水溶液に、さら光触媒性酸化チタン微粉末を直接混ぜたり、光触媒性酸化チタン微粒子を分散相とする水性ゾルやアルコールゾルを混ぜたりする必要があった。しかし、ペルオキソチタン酸水溶液自体、酸化チタン微粉末や微粒子を懸濁させにくいものであるため、ペルオキソチタン酸水溶液中の全酸化チタン含有量（ペルオキソチタン酸水溶液から生成した酸化チタンと、別途添加された酸化チタンの総量）は、高々１重量％位にしかできなかった。On the other hand, in the case of (2), even if the peroxotitanic acid aqueous solution is heated at a certain temperature for a certain period of time to produce photocatalytic titanium oxide fine particles in the aqueous solution, the amount thereof is very small. Or, it was necessary to directly mix the photocatalytic titanium oxide fine powder with the peroxotitanic acid aqueous solution containing the generated titanium oxide fine particles, or to mix the aqueous sol or alcohol sol with the photocatalytic titanium oxide fine particles as the dispersed phase. . However, since the peroxotitanic acid aqueous solution itself is difficult to suspend the titanium oxide fine powder and fine particles, the total titanium oxide content in the peroxotitanic acid aqueous solution (titanium oxide generated from the peroxotitanic acid aqueous solution is added separately. The total amount of titanium oxide) could only be about 1% by weight.
この発明で意図される光触媒性塗布剤は、従来の光触媒塗料の場合同様、屋内外の各種構造物へも勿論使用可能であるが、さらに、例えば、屋内外、特に屋内で持続的な静菌・殺菌を必要とするが、人畜への芳しからぬ影響の懸念される化学的殺菌剤の散布が憚られる場所（例えば、病院、介護施設、託児所、幼稚園、公民館、宿泊施設、飲食店、調理施設、更衣室、公衆トイレ、食品工場、薬品工場、衛生関係実験室、酪農施設、植物栽培施設など）へも、人畜や環境に優しい一種の静菌・殺菌剤として使用可能なものである。The photocatalytic coating agent intended in the present invention can be used for various indoor and outdoor structures as in the case of conventional photocatalytic coatings.・ Places where chemical disinfectants are sprayed that require sterilization but are of concern for adverse effects on human livestock (eg hospitals, nursing homes, day care centers, kindergartens, public halls, lodging facilities, restaurants) , Cooking facilities, changing rooms, public toilets, food factories, pharmaceutical factories, hygiene-related laboratories, dairy farms, plant cultivation facilities, etc.) is there.
本発明の光触媒性塗布剤は、従来の光触媒塗料の場合と異なり、単に平坦な構造物面に塗装される塗料としてのみならず、様々な形状や面状態を備えた物に散布・塗布される一種の静菌・殺菌剤としても用いられる。したがって、当該光触媒性塗布剤については、それに含まれる光触媒性二酸化チタン量を、場合によっては、一般の光触媒の場合の高々１重量％位よりかなり高い量まで（たとえば、６重量％位まで）高めることが必要になり、また、光触媒性二酸化チタン含有量が従来の通念的レベルを超越していても、当該二酸化チタン微粒子を十分安定的に懸濁することができ、例えば半年間位は実質的に沈殿しないように調製することも必要になってくる。Unlike the conventional photocatalyst paint, the photocatalytic coating agent of the present invention is not only applied as a paint to be applied to a flat structure surface, but is also applied to an object having various shapes and surface states. It is also used as a kind of bacteriostatic and bactericide. Therefore, for the photocatalytic coating agent, the amount of photocatalytic titanium dioxide contained therein is increased to an amount considerably higher than about 1% by weight in the case of a general photocatalyst (for example, up to about 6% by weight). In addition, even if the photocatalytic titanium dioxide content exceeds the conventional level, the fine particles of titanium dioxide can be suspended sufficiently stably. It is also necessary to prepare so as not to precipitate.
本発明の光触媒性塗布剤の調製に際しては、まず合成樹脂を分散相とする水性エマルジョンに、光触媒剤（光触媒性酸化チタン微粉末や、光触媒性酸化チタン微粒子の懸濁された水性ゾル）を添加し、十分混合する。次いで、そうして得られた、光触媒微粒子の懸濁された一次液剤に、有機溶媒や無機結合剤などを含む液剤を徐々に添加し、十分混合する。そうすることで、光触媒性酸化チタン量が通念的レベルよりかなり高くても、光触媒性酸化チタン微粒子が長期間にわたり実質的に沈殿しない光触媒性塗布剤を二次的液剤として得ることができる。光触媒剤としての光触媒性酸化チタン微粉末や、水性ゾル中の光触媒性酸化チタン微粒子としては、波長が約４００ｎｍより短い光で励起されるもの（紫外光反応型品）、及び／又は、波長が約３８０ｎｍより長い光で励起されるもの（可視光反応型品）を用いることができ、また、表面がアパタイトで部分的に被覆されたものや、表面がペルオキソ基で修飾されたものなども用いることができる。In preparing the photocatalytic coating agent of the present invention, first, a photocatalytic agent (photocatalytic titanium oxide fine powder or aqueous sol in which photocatalytic titanium oxide fine particles are suspended) is added to an aqueous emulsion having a synthetic resin as a dispersed phase. And mix well. Next, a liquid agent containing an organic solvent, an inorganic binder, and the like is gradually added to the primary liquid agent in which the photocatalyst fine particles are suspended, and the mixture is sufficiently mixed. By doing so, even if the amount of photocatalytic titanium oxide is considerably higher than a conventional level, a photocatalytic coating agent in which the photocatalytic titanium oxide fine particles are not substantially precipitated over a long period of time can be obtained as a secondary liquid agent. As photocatalytic titanium oxide fine powder as a photocatalytic agent and photocatalytic titanium oxide fine particles in an aqueous sol, those which are excited by light having a wavelength shorter than about 400 nm (ultraviolet light reaction type product) and / or have a wavelength of Those excited by light longer than about 380 nm (visible light reaction type) can be used, and those whose surface is partially coated with apatite or whose surface is modified with a peroxo group are also used. be able to.
この本発明の光触媒性塗布剤は、光触媒剤（光触媒性酸化チタン微粉末ないしは光触媒性酸化チタン微粒子）を、従来のその種の塗布剤若しくは塗料において通念的な含有量を超越した量で、しかも、長期間にわたり沈殿を招かない状態で懸濁させる能力を備えたものである。したがって、この発明の光触媒性塗布剤については、従来の光触媒性塗料同様、単に屋内外で構造物の平坦面に塗装される塗料的用途のみならず、特に、人畜に必ずしも芳しくない化学的殺菌剤の散布が憚られる屋内外、特に屋内にて、様々な形状や表面状態を備えた物に散布・塗布され、持続的な静菌・殺菌を発揮し得る一種の静菌・殺菌剤としても利用可能なものとして位置づけられる。This photocatalytic coating agent of the present invention contains a photocatalytic agent (photocatalytic titanium oxide fine powder or photocatalytic titanium oxide fine particles) in an amount exceeding the conventional content of such coating agents or paints. , Having the ability to suspend in a state that does not cause precipitation over a long period of time. Therefore, the photocatalytic coating agent of the present invention is not only used for painting on a flat surface of a structure indoors and outdoors, but also a chemical disinfectant that is not necessarily good for human animals, as in the case of conventional photocatalytic coatings. It is used as a kind of bacteriostatic / disinfectant that can be sprayed and applied to objects with various shapes and surface conditions indoors and outdoors, especially indoors where it can be sprayed, and that can exert continuous bacteriostatic / sterilization Positioned as possible.
光触媒剤としては、波長が約４００ｎｍより短い紫外光を主とする光で励起される紫外光反応型のもの、及び／又は、波長が約３８０ｎｍより長い可視光を主とする光で励起される可視光反応型のものを、酸化チタン微粉末や、光触媒性酸化チタン微粒子の懸濁された水性ゾル（スラリ）の形で用いることができる。紫外光反応型の水性ゾルとしては、例えば、平均粒子径が１５〜３０ｎｍ程度のアパタイト被覆光触媒性酸化チタン微粒子を約２０重量％含むもの（昭和タイタニウム社製など）や、所定熱処理により自己内に生成せしめられた光触媒微粒子を含むペルオキソチタン酸溶液を挙げることができ、可視光反応型の水性ゾルとしては、例えば、可視光反応型酸化チタン微粒子を約１０重量％含むもの（住友チタニウム社製など）を挙げることができる。As a photocatalytic agent, an ultraviolet light reactive type that is excited by light mainly composed of ultraviolet light having a wavelength shorter than about 400 nm and / or excited by light mainly composed of visible light having a wavelength longer than about 380 nm. The visible light reactive type can be used in the form of fine powder of titanium oxide or an aqueous sol (slurry) in which photocatalytic titanium oxide fine particles are suspended. Examples of the ultraviolet light reactive aqueous sol include those containing about 20% by weight of apatite-coated photocatalytic titanium oxide fine particles having an average particle size of about 15 to 30 nm (made by Showa Titanium Co., Ltd.) A peroxotitanic acid solution containing the produced photocatalyst fine particles can be mentioned. Examples of the visible light reaction type aqueous sol include those containing about 10% by weight of visible light reaction type titanium oxide fine particles (manufactured by Sumitomo Titanium Co., Ltd., etc.) ).
ちなみに、アパタイト被覆光触媒性酸化チタンは、光触媒性酸化チタンの表面がアパタイトで部分的に（光触媒性酸化チタンに励起光が到達できる程度に）被覆されたものであり、塗膜や塗装されるべき構造物表面での、いわゆるチョーキング現象を起こしにくいとされているものである。光触媒剤が添加混合されるべき、合成樹脂を分散相とする水性エマルジョンにおける合成樹脂としては、アクリル樹脂、シリコーン樹脂、ポリエステル樹脂、ウレタン樹脂、フッ素樹脂、及び、これら樹脂のうちの少なくとも二種類の共重合体から選ばれる少なくとも一種類を用いることができる。また、有機溶媒としては、アルコール、ケトン、エステル、キシレン、トルエンから選ばれる少なくとも一種類を用いることができる。アルコールの例として、エチルアルコール、メチルアルコール、イソプロピルアルコール（ＩＰＡ）を挙げることができる。ケトンの例としてアセトン、エステルの例として酢酸エチル、アミルの例として酢酸アミルを挙げることができる。By the way, apatite-coated photocatalytic titanium oxide is a surface of photocatalytic titanium oxide that is partially coated with apatite (to the extent that excitation light can reach the photocatalytic titanium oxide). It is said that the so-called choking phenomenon is hardly caused on the surface of the structure. As a synthetic resin in an aqueous emulsion having a synthetic resin as a dispersed phase to which a photocatalytic agent should be added and mixed, acrylic resin, silicone resin, polyester resin, urethane resin, fluororesin, and at least two kinds of these resins At least one selected from copolymers can be used. Moreover, as an organic solvent, at least 1 sort (s) chosen from alcohol, a ketone, ester, xylene, and toluene can be used. Examples of the alcohol include ethyl alcohol, methyl alcohol, and isopropyl alcohol (IPA). Examples of ketones include acetone, examples of esters include ethyl acetate, and examples of amyl include amyl acetate.
光触媒剤源として、紫外光反応型アパタイト被覆光触媒性酸化チタン微粒子を約２０重量％含む水性ゾル（スラリ）（昭和電光社製）を用いて、光触媒性塗布剤Ａ，Ｂ，Ｃ（酸化チタン微粒子含有量０．５，０．３，０．４重量％）を試作した。分散相としてシリコーン・アクリル樹脂を含む水性エマルジョンに、上記、酸化チタン微粒子を含む水性ゾルを徐々に添加して十分混合し、「一次液剤」を得た。そしてこの一次液剤に「有機溶媒を含む液剤」を徐々に添加して十分混合し、本発明の光触媒性塗布剤Ａ，Ｂ，Ｃを二次液剤として得た。塗布剤Ａ，Ｂ，Ｃには一次液剤が、それぞれ６２，５，６２．５，１９．０重量％配合された。塗布剤Ａ，Ｂ，ＣのｐＨは９．０，９．０，８，０である。As a photocatalyst agent source, an aqueous sol (slurry) (made by Showa Denko) containing about 20% by weight of ultraviolet light reactive apatite-coated photocatalytic titanium oxide fine particles was used, and photocatalytic coating agents A, B, C (titanium oxide fine particles) Prototypes having a content of 0.5, 0.3, and 0.4 wt% were prepared. The above-mentioned aqueous sol containing titanium oxide fine particles was gradually added to an aqueous emulsion containing a silicone / acrylic resin as a dispersed phase and mixed well to obtain a “primary liquid”. Then, “a liquid containing an organic solvent” was gradually added to this primary liquid and mixed well to obtain the photocatalytic coating agents A, B and C of the present invention as secondary liquids. In the coating agents A, B and C, 62, 5, 62.5 and 19.0% by weight of the primary solution were blended, respectively. The pH of coating agents A, B, and C is 9.0, 9.0, 8, and 0.
光触媒性塗布剤Ａ，Ｂ，Ｃ用一次液剤の組成（重量比）は表１のとおりである。
光触媒性塗布剤Ａ，Ｂ，Ｃには「有機溶媒を含む液剤」が、それぞれ２５，３５，７７重量％配合された。光触媒性塗布剤Ａ，Ｂ，Ｃ用の「有機溶媒を含む液剤」の組成は表２のとおりである。
ただし、ここでの結合剤はポリメチルメトキシシランであり、アルコールは、エチルアルコール、メチルアルコール、イソプロピルアルコール（ＩＰＡ）の混合物である。各アルコールの割合は表３のとおりである。
なお、光触媒性塗布剤Ａ，Ｂ，Ｃ用として、それぞれ一次液剤と「有機溶媒を含む液剤」の混合によって得られた液に、水性シリカゾル（シリカ分２０重量％）が、２．５，１．５，２．０重量％配合された。シリカゾルは、塗膜面に親水性を与えるとともに、塗膜を強化するものである。光触媒性塗布剤Ａは、主として建物内装に用いられることを意図した塗布剤（実質的に塗料）であり、同Ｂ，Ｃは、主として建物外装に用いられることを意図した塗布剤（実質的に塗料）である。塗装試験において、いずれの塗布剤Ａ，Ｂ，Ｃも下塗りなしで、金属面、プラスチック面、塗装面に何ら問題なく（水性塗料に有りがちな“弾き”や“だれ”を生ずることなく）均一に塗装することができ、短時間で常温硬化した。塗布剤Ｂ，Ｃにおけるアセトンは、速乾性向上と、特にプラスチック面や塗装面における塗布剤の塗着性向上のために配合されている。For photocatalytic coating agents A, B, and C, aqueous silica sol (silica content 20% by weight) was added to the liquids obtained by mixing the primary liquid and the “liquid containing organic solvent”, respectively. .5,2.0 wt% was blended. Silica sol imparts hydrophilicity to the coating surface and strengthens the coating. The photocatalytic coating agent A is a coating agent (substantially paint) intended to be used mainly for building interiors, and B and C are coating agents (substantially used mainly for building exteriors). Paint). In coating tests, all coating agents A, B, and C have no undercoating, and have no problem on metal surfaces, plastic surfaces, or painted surfaces (without causing “bounce” or “sag” that is common in water-based paints) It was able to be coated and cured at room temperature in a short time. Acetone in coating agents B and C is blended in order to improve quick drying properties, and in particular, to improve the coating properties of the coating agent on plastic surfaces and painted surfaces.
光触媒源として、可視光反応型光触媒性酸化チタン微粒子を約１０重量％含む水性ゾル（住友チタニウム社製）を用いて、光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４（酸化チタン微粒子含有量０．５，１．０，２．０，６．０重量％）を試作した。分散相としてシリコーン・アクリル樹脂を含む水性エマルジョンに、上記、酸化チタン微粒子を含む水性ゾルを徐々に添加して十分混合し、「一次液剤」を得た。そして，この一次液剤に「有機溶媒を含む液剤」を徐々に添加して十分混合し、本発明の光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４を二次液剤として得た。塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４のｐＨは、９．０，８．５，７．５，５，５である。この実施例２の光触媒性塗布剤には、実施例１の塗布剤に配合されているコロイダルシリカが配合されていないが、それは、この実施例２の塗布剤が、主として塗膜における硬さ、親水性をさほど要しない場所で、一種の静菌・殺菌剤として用いられるべく想定されているからである。As a photocatalyst source, an aqueous sol (manufactured by Sumitomo Titanium Co., Ltd.) containing about 10% by weight of visible light reactive photocatalytic titanium oxide fine particles was used, and photocatalytic coating agents X1, X2, X3 and X4 (titanium oxide fine particle content 0. 5,1.0,2.0,6.0% by weight). The above-mentioned aqueous sol containing titanium oxide fine particles was gradually added to an aqueous emulsion containing a silicone / acrylic resin as a dispersed phase and mixed well to obtain a “primary liquid”. And the "liquid agent containing an organic solvent" was gradually added to this primary liquid agent, and it mixed sufficiently, and obtained photocatalytic coating agent X1, X2, X3, X4 of this invention as a secondary liquid agent. The pH of coating agent X1, X2, X3, X4 is 9.0, 8.5, 7.5, 5, 5. The photocatalytic coating agent of Example 2 does not contain colloidal silica that is blended with the coating agent of Example 1, but the coating agent of Example 2 is mainly composed of the hardness in the coating film, This is because it is supposed to be used as a kind of bacteriostatic / bactericidal agent at a place where hydrophilicity is not so required.
光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４には一次液剤が、それぞれ５１．５，５３．０，５９．０，６８．０重量％配合された。光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４用一次液剤の組成（重社比）は表４のとおりである。
光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４には「有機溶媒を含む液剤」が、それぞれ４８．５，４７．０，４１．０，３２．０重量％配合された。光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４用の「有機溶媒を含む液剤」の組成は表５のとおりである。
ただし、ここでの結合剤はポリメチルメトキシシランであり、アルコールは、エチルアルコール、メチルアルコール、イソプロピルアルコール（ＩＰＡ）の混合物である。各アルコールの割合は表６のとおりである。
塗装試験においては、吹き付け塗装、刷毛塗り塗装の場合とも、塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４のいずれにあっても下塗りなしで、金属面、プラスチック面、塗装面に何ら問題なく（水性塗料に有りがちな“弾き”や“だれ”を生ずることなく）均一に塗装することができ、形成された塗膜については、３０分以内に見掛け上の常温硬化が認められた。In the coating test, both spray coating and brush coating have no problem on the metal surface, plastic surface, or painted surface without any undercoating in any of the coating agents X1, X2, X3, and X4. The coating film thus formed was apparently cured at room temperature within 30 minutes.
実施例２で調製した光触媒性塗布剤Ｘ１，Ｘ２，Ｘ３，Ｘ４につき、ＪＩＳ−Ｚ２８０１（抗菌加工製品ー抗菌性試験方法・抗菌効果）に基づいて静菌・殺菌性を調べた。試験板としては、塗布剤Ｘ〜Ｘ４を５ｃｍ×５ｃｍの硬質塩化ビニル板に噴霧塗装機で均一に塗装後、常温で２４時間放置し、硬質塗膜を形成させたものを使用した。光照射実験は、無菌正圧チャンバー内で２０時間行った。光源はとしては１５ｃｍ間隔で列状に配置した１００ｗａｔｔ白熱灯を用いた。光源−試験板間の距離は約４０ｃｍとされた（試験塗膜上での照度は約４７００ｌｕｘ）。接種菌としては、ＪＩＳ法により培養、調製した大腸菌（Ｅ．ｃｏｌｉ−３１１０）を用いた。ただし、上記、光照射試験、細菌学的試験は、本特許出願人と共同研究を行っている千葉大学医学部で行われた。The photocatalytic coating agents X1, X2, X3 and X4 prepared in Example 2 were examined for bacteriostatic and bactericidal properties based on JIS-Z2801 (antibacterial processed product-antibacterial test method / antibacterial effect). As the test plate, coating agents X to X4 were uniformly coated on a 5 cm × 5 cm hard vinyl chloride plate with a spray coating machine, and then left at room temperature for 24 hours to form a hard coating film. The light irradiation experiment was performed for 20 hours in a sterile positive pressure chamber. As the light source, 100 watt incandescent lamps arranged in rows at intervals of 15 cm were used. The distance between the light source and the test plate was about 40 cm (the illuminance on the test coating was about 4700 lux). As an inoculum, Escherichia coli (E. coli-3110) cultured and prepared by the JIS method was used. However, the above-mentioned light irradiation test and bacteriological test were conducted at the Chiba University School of Medicine, which is conducting joint research with the applicant of this patent.
静菌・殺菌性の検定結果は表７のとおりである。
光触媒源として、二種類のもの、即ち、可視光反応型光触媒性酸化チタン微粒子を約１０重量％含む水性ゾル（Ａ）、及び、ペルオキソチタン酸溶液を出発原料とする液剤（紫外線反応型と可視光反応型の光触媒性酸化チタン微粒子が総量で約１重量％含まれるもの）（Ｂ）を用いて、光触媒性塗布剤Ｚ１を試作した。分散相としてシリコーン・アクリル樹脂を含む水性エマルジョンに、上記水性ゾル（Ａ）と液剤（Ｂ）を徐々に添加して十分混合し、「一次液剤」を得た。ただし、水性ゾル（Ａ）と液剤（Ｂ）の配合割合は重量比で１：５とされた。次いで、この一次液剤に「有機溶媒を含む液剤」を徐々に添加して十分混合し、本発明の光触媒性塗布剤を二次液剤として得た。光触媒性塗布剤Ｚ１には一次液剤が７８重量％配合された。There are two types of photocatalyst sources, namely, an aqueous sol (A) containing about 10% by weight of visible light reactive photocatalytic titanium oxide fine particles and a liquid agent starting from a peroxotitanic acid solution (ultraviolet reaction type and visible type). A photocatalytic coating agent Z1 was prototyped using a photoreactive photocatalytic titanium oxide fine particle (containing about 1% by weight in total) (B). The aqueous sol (A) and the liquid agent (B) were gradually added to an aqueous emulsion containing a silicone / acrylic resin as a dispersed phase and sufficiently mixed to obtain a “primary liquid agent”. However, the blending ratio of the aqueous sol (A) and the liquid agent (B) was 1: 5 by weight ratio. Subsequently, the “liquid agent containing an organic solvent” was gradually added to the primary liquid agent and mixed sufficiently to obtain the photocatalytic coating agent of the present invention as a secondary liquid agent. The photocatalytic coating agent Z1 was mixed with 78% by weight of the primary solution.
光触媒性塗布剤Ｚ１用一次液剤の組成（重量比）は表８のとおりである。ただし、表８において、「水溶液」とは、液剤（Ｂ）に由来する成分を含む水溶液のことをいう。
光触媒性塗布剤Ｚ１には「有機溶媒を含む液剤」が２２重量％配合された。光触媒性塗布剤Ｚ１用の「有機溶媒を含む液剤」の組成は表９のとおりである。
ただし、ここでの結合剤はポリメチルメトキシシランであり、アルコールは、エチルアルコール、メチルアルコール、イソプロピルアルコール（ＩＰＡ）の混合物である。各アルコールの割合は表１０のとおりである。
塗布剤Ｚ１は吹きつけ塗装においても、刷毛塗り塗装においても、下塗りなしで金属面、プラスチック面、塗装面に何ら問題なく（水性塗料に有りがちな“弾き”や“だれ”を生ずることなく）均一に塗装することができ、得られた塗膜は３０分以内に見掛け上、常温硬化した。また、静菌・殺菌性についても、実施例３に準じて行ったが、塗布剤Ｚ１にも殺菌効果が認められたが、上記一連の試験から示唆されるように、塗布剤Ｚ１が常温硬化塗布剤として用いられる場合、塗装性、静菌・殺菌性については、ペルオキソチタン酸溶液を出発原料とした液剤が配合されることに何ら意義が認められない。しかし、塗布剤Ｚ１による塗装部が２００〜５００℃で加熱される場合には、塗膜自体の緻密化と、塗膜の下地への密着強度の向上に期待する余地がある（特許第２８７５９９３号明細書）。The coating agent Z1 can be used for spray coating or brush coating without any undercoating on the metal surface, plastic surface, or painted surface (without causing any “slip” or “sag” common to water-based paints). It was possible to paint uniformly, and the obtained coating film was apparently cured at room temperature within 30 minutes. In addition, bacteriostatic and bactericidal properties were also carried out in accordance with Example 3. Although the bactericidal effect was also observed in the coating agent Z1, as suggested from the series of tests, the coating agent Z1 was cured at room temperature. When used as a coating agent, no significance is recognized in terms of paintability, bacteriostatic / bactericidal properties, and the addition of a liquid agent starting from a peroxotitanic acid solution. However, when the coating part by the coating agent Z1 is heated at 200 to 500 ° C., there is room for expectation for densification of the coating film itself and improvement of adhesion strength of the coating film to the ground (Japanese Patent No. 2875993). Specification).
実施例３と同様に調製された、酸化チタン微粒子含有量が０．１重量％の光触媒性塗布剤（ａ）、ペルオキソチタン酸を出発原料として調製された市販の屋内用・可視光反応型光触媒塗料（酸化チタン含有量約１重量％のもの）（ｂ）、光触媒性表面を備えた市販の抗菌タイル（ｃ）の三種類につき、実施例３の要領で静菌・殺菌性試験を行ったが、いずれの場合も静菌性すら見られなかった（実施例３の表７に示された＊に相当）。少なくとも、本発明の光触媒性塗布剤（ａ）の場合、酸化チタン微粒子含有量が０．１重量％では過少であること、市販の屋内用・可視光反応型光触媒塗料（ｂ）、市販の抗菌タイル（ｃ）については、静菌性が否定できないにしても、静菌性を発揮させるには使用条件にかなり制限が課されることがうかがえる。なお、市販の塗料（ｂ）については、実施例３の試験に用いた硬質塩化ビニル板に直接塗布しても付着が全く認められなかった。そのため、塗料（ｂ）については、硬質塩化ビニル板にシリコーン・アクリル樹脂塗料で下塗りを施し、下塗り塗膜が十分硬化した後、下塗り塗膜に対し塗装を行う必要があった。Photocatalytic coating agent (a) having a titanium oxide fine particle content of 0.1% by weight, which is prepared in the same manner as in Example 3, and a commercially available indoor / visible light reactive photocatalyst prepared using peroxotitanic acid as a starting material Bacteriostatic and bactericidal tests were conducted in the same manner as in Example 3 for three types of paint (with titanium oxide content of about 1% by weight) (b) and a commercially available antibacterial tile (c) having a photocatalytic surface. However, no bacteriostatic property was observed in any case (corresponding to * shown in Table 7 of Example 3). At least, in the case of the photocatalytic coating agent (a) of the present invention, the content of titanium oxide fine particles is too small at 0.1% by weight, a commercially available indoor / visible light reactive photocatalyst paint (b), a commercially available antibacterial agent Even if the bacteriostatic property cannot be denied for the tile (c), it can be seen that the use conditions are considerably limited in order to exert the bacteriostatic property. In addition, as for the commercially available paint (b), no adhesion was observed even when directly applied to the hard vinyl chloride plate used in the test of Example 3. Therefore, for paint (b), it was necessary to coat the hard vinyl chloride plate with a silicone / acrylic resin paint and to coat the undercoat film after the undercoat film was sufficiently cured.
Claims (8)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010168569A (en) * | 2008-12-22 | 2010-08-05 | Bekku Kk | Coating material |
| WO2011111800A1 (en) | 2010-03-12 | 2011-09-15 | 株式会社オハラ | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| CN104307543A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Preparation method of phosphoric acid modified titanium dioxide photocatalyst |
| KR20160004207A (en) * | 2014-07-01 | 2016-01-12 | 허니웰 인터내셔날 인코포레이티드 | Self-cleaning smudge-resistant structure and related fabrication methods |
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2006
- 2006-09-25 JP JP2006288087A patent/JP2008081712A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010168569A (en) * | 2008-12-22 | 2010-08-05 | Bekku Kk | Coating material |
| WO2011111800A1 (en) | 2010-03-12 | 2011-09-15 | 株式会社オハラ | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| KR20160004207A (en) * | 2014-07-01 | 2016-01-12 | 허니웰 인터내셔날 인코포레이티드 | Self-cleaning smudge-resistant structure and related fabrication methods |
| KR102417456B1 (en) * | 2014-07-01 | 2022-07-06 | 허니웰 인터내셔날 인코포레이티드 | Self-cleaning smudge-resistant structure and related fabrication methods |
| CN104307543A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Preparation method of phosphoric acid modified titanium dioxide photocatalyst |
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