JP2000302422A - Coating composition for forming photocatalyst film - Google Patents
Coating composition for forming photocatalyst filmInfo
- Publication number
- JP2000302422A JP2000302422A JP11108931A JP10893199A JP2000302422A JP 2000302422 A JP2000302422 A JP 2000302422A JP 11108931 A JP11108931 A JP 11108931A JP 10893199 A JP10893199 A JP 10893199A JP 2000302422 A JP2000302422 A JP 2000302422A
- Authority
- JP
- Japan
- Prior art keywords
- coating composition
- titanium
- water
- sol
- compound
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 33
- -1 titanium phosphate compound Chemical class 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 230000007935 neutral effect Effects 0.000 claims abstract description 16
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 20
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 4
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 235000010746 mayonnaise Nutrition 0.000 description 2
- 239000008268 mayonnaise Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 101000650817 Homo sapiens Semaphorin-4D Proteins 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 102100027744 Semaphorin-4D Human genes 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、基材の上に光触媒膜も
しくは層を形成するために用いるコーティング組成物に
関する。The present invention relates to a coating composition used for forming a photocatalytic film or layer on a substrate.
【０００２】[0002]
【従来技術とその問題点】酸化チタンは、酸素と水の存
在下そのバンドギャップ以上のエネルギーを持つ波長３
８０ｎｍ以下の光で照射すると物質を酸化分解する光触
媒反応を行うことは良く知られている。近年この現象を
利用して環境浄化に役立てる研究が盛んに行われてい
る。2. Description of the Related Art Titanium oxide has a wavelength of 3 or more in the presence of oxygen and water having an energy greater than its band gap.
It is well known that a photocatalytic reaction that oxidizes and decomposes a substance when irradiated with light of 80 nm or less is performed. In recent years, researches utilizing this phenomenon for environmental purification have been actively conducted.
【０００３】具体的には、自動車や工場の排気ガス中の
ＮＯx 、ＳＯx 、アンモニア，アルデヒド類、アミン
類、メルカプタン等の有害または悪臭物質の光分解、
油、タール、タバコのヤニなどの生活汚染物質の光分
解、工業排水に含まれる染料、糊剤などの光分解、細
菌、カビ、藻類等の有害微生物の殺滅等である。Specifically, photodecomposition of harmful or odorous substances such as NO x , SO x , ammonia, aldehydes, amines and mercaptan in exhaust gas of automobiles and factories,
Photodecomposition of living pollutants such as oil, tar and tobacco tar, photodecomposition of dyes and pastes contained in industrial wastewater, killing of harmful microorganisms such as bacteria, mold and algae.
【０００４】酸化チタン自体は固体の粉末または結晶で
あるからこれを前記の用途に用いるためには支持体もし
くは基材へ固定化し、支持しなければならない。そのた
めの種々の方法の一つとして、酸化チタン光触媒粒子を
含んでいるコーティング組成物を基材へ塗布もしくは含
浸し、基材上に光触媒の膜または層を形成するコーティ
ング法がある。コーティング法は膜の高温での焼成を必
要としないため、基材が耐熱性材料であることを要求せ
ず、かつ大面積の浄化膜を形成するのに適している。[0004] Since titanium oxide itself is a solid powder or a crystal, it must be immobilized and supported on a support or substrate in order to use it in the above-mentioned applications. As one of various methods therefor, there is a coating method in which a coating composition containing titanium oxide photocatalyst particles is applied or impregnated to a substrate to form a photocatalyst film or layer on the substrate. The coating method does not require baking the film at a high temperature, and therefore does not require the substrate to be a heat-resistant material and is suitable for forming a large-area purification film.
【０００５】しかしながら酸化チタンの光触媒作用は強
力で、実質上選択作用がないので、有機樹脂を光触媒粒
子のバインダーに用いるとバインダー自身が光化学反応
の標的となり、経時的に酸化分解されてバインダーとし
て役立たなくなる。そこで特開平８−１６４３３号は無
機物であるシリカゾルをバインダーとするコーティング
組成物を提案している。具体的にはこのゾルはテトラエ
トキシシランまたはテトラメトキシランのような加水分
解性ケイ素化合物の部分加水分解オリゴマーよりなる。
しかしながらこの組成物はアルコキシシランモノマーの
加水分解に用いた酸を含んでいるので基材がある程度耐
酸性であることを要求し、貯蔵中にオリゴマーの重縮合
反応が進行し、増粘ないしゲル化する傾向を有する。さ
らにオリゴマーの重縮合反応により副生するアルコール
および溶媒として含まれるアルコールが塗膜形成時に周
囲環境へ揮散する。However, since the photocatalytic action of titanium oxide is strong and has substantially no selective action, when an organic resin is used as a binder for photocatalytic particles, the binder itself becomes a target of a photochemical reaction, and is oxidatively decomposed with time to serve as a binder. Disappears. JP-A-8-16433 proposes a coating composition using silica sol, which is an inorganic substance, as a binder. Specifically, this sol consists of a partially hydrolyzed oligomer of a hydrolyzable silicon compound such as tetraethoxysilane or tetramethoxysilane.
However, since this composition contains the acid used for hydrolysis of the alkoxysilane monomer, the base material needs to have a certain level of acid resistance, and the polycondensation reaction of the oligomer proceeds during storage, and the viscosity increases or gelation occurs. Have a tendency to Further, alcohol by-produced by the polycondensation reaction of the oligomer and alcohol contained as a solvent volatilize into the surrounding environment during the formation of the coating film.
【０００６】そこで本発明は、バインダー成分が酸化チ
タンの光触媒反応の標的とならない上、酸化チタンとな
じみのよいチタン化合物であって、中性域において貯蔵
安定性を有し、透明で、高硬度の密着性にすぐれた酸化
チタン光触媒膜を形成するコーティング組成物を提案す
る。Accordingly, the present invention relates to a titanium compound which is not a target of the photocatalytic reaction of titanium oxide, is a titanium compound which is familiar with titanium oxide, has storage stability in a neutral region, is transparent and has high hardness. The present invention proposes a coating composition for forming a titanium oxide photocatalytic film having excellent adhesion.
【０００７】[0007]
【課題の解決方法】上記の課題は、本発明による光触媒
膜形成用コーティング組成物によって解決される。この
コーティング組成物は、水和リン酸チタン化合物の中性
領域にある透明な分散ゾル中に分散した酸化チタン光触
媒粒子を含んでいる。The above-mentioned problems are solved by the coating composition for forming a photocatalytic film according to the present invention. The coating composition includes titanium oxide photocatalyst particles dispersed in a transparent dispersion sol in the neutral region of the hydrated titanium phosphate compound.
【０００８】本発明のコーティング組成物の分散媒であ
る含水リン酸チタン化合物分散ゾルは、水溶性チタン化
合物とリン酸化合物をＴｉＯ2 ／Ｐ2 Ｏ5 に換算した重
量比０．５〜５．０で反応させ、反応液を中和、濾過、
水洗して得られるケーキを水性媒体に再分散することに
よって製造される。この分散ゾルをバインダーに使用し
た本発明のコーティング組成物は液性が中性であり、透
明で長い貯蔵寿命を有する。このコーティング組成物は
基材へ塗布し、乾燥することによって透明な、高硬度の
密着性にすぐれた光触媒膜を形成する。The hydrated titanium phosphate compound dispersion sol, which is the dispersion medium of the coating composition of the present invention, has a water-soluble titanium compound and a phosphate compound in a weight ratio of 0.5 to 5.0 in terms of TiO 2 / P 2 O 5 . 0, the reaction solution is neutralized, filtered,
It is manufactured by redispersing the cake obtained by washing with water in an aqueous medium. The coating composition of the present invention using this dispersion sol as a binder has a neutral liquidity, is transparent and has a long shelf life. This coating composition is applied to a substrate and dried to form a transparent, high-hardness photocatalytic film having excellent adhesion.
【０００９】[0009]
【具体的な実施方法】分散ゾルをつくるための水和リン
酸チタン化合物は、水溶性チタン化合物とリン酸化合物
との反応によってつくることができる。水溶性チタン化
合物の例は四塩化チタンおよび硫酸チタニルを含み、リ
ン酸化合物の例は各種のリンの酸素酸、例えば正リン酸
およびメタリン酸ならびにそれらの水溶性塩である。正
リン酸またはメタリン酸が好ましい。水溶性チタン化合
物のリン酸化合物に対する比は広範囲に変動し得る。し
かしながら本発明の分散ゾルを調製する目的に対して
は、チタン化合物をＴｉＯ2 に換算し、リン酸化合物を
Ｐ2 Ｏ5 に換算した重量比ＴｉＯ2 ／Ｐ2 Ｏ5 が一般に
０．５〜５．０、より好ましくは１．５〜３．５の範囲
が適している。分散ゾルは、この反応液を中和し、析出
物を濾過、水洗して得られるケーキを水性媒体に再分散
することにより調製し得る。任意の中和剤を使用できる
が、夾雑金属イオンを持ち込まないアンモニア水が好ま
しい。The hydrated titanium phosphate compound for preparing the dispersion sol can be prepared by reacting a water-soluble titanium compound with a phosphate compound. Examples of water-soluble titanium compounds include titanium tetrachloride and titanyl sulfate, and examples of phosphoric acid compounds are various oxyacids of phosphorus, such as orthophosphoric acid and metaphosphoric acid, and water-soluble salts thereof. Orthophosphoric acid or metaphosphoric acid is preferred. The ratio of water-soluble titanium compound to phosphate compound can vary over a wide range. However for the purpose of preparing a dispersion sol of the present invention, 0.5 to titanium compound in terms of TiO 2, a phosphate compound generally a weight ratio TiO 2 / P 2 O 5 in terms of P 2 O 5 A range of 5.0, more preferably 1.5 to 3.5 is suitable. The dispersion sol can be prepared by neutralizing the reaction solution, filtering the precipitate, washing the precipitate with water, and redispersing a cake obtained in an aqueous medium. Any neutralizing agent can be used, but ammonia water which does not bring in contaminant metal ions is preferred.
【００１０】この操作によってチタン化合物とリン酸化
合物の反応によって生成した水和リン酸チタン化合物の
分散ゾルが得られる。この場合生成物は単一化合物では
なく、チタンとリンの原子比の異なる多数の単一化合物
の混合物であろう。本発明でいう「水和リン酸チタン化
合物」とはこのような混合物を意味する。この水和リン
酸チタン化合物は、ボールミル、サンドミル、ホモミキ
サー、ペイントシェカーなどの慣用の機械を用いて平均
ミセル径が１０〜５００ｎｍの粒子に水中に分散するこ
とができる。得られた分散液は中性で、透明で、例えば
２５℃において２ケ月以上安定なゾルである。By this operation, a dispersion sol of the hydrated titanium phosphate compound produced by the reaction between the titanium compound and the phosphoric acid compound is obtained. In this case, the product will not be a single compound, but a mixture of multiple single compounds with different atomic ratios of titanium and phosphorus. The “hydrated titanium phosphate compound” in the present invention means such a mixture. This hydrated titanium phosphate compound can be dispersed in water into particles having an average micelle diameter of 10 to 500 nm using a conventional machine such as a ball mill, a sand mill, a homomixer, and a paint shaker. The resulting dispersion is a neutral, transparent, sol that is stable, for example, at 25 ° C. for more than 2 months.
【００１１】酸化チタン光触媒粒子は触媒活性が高いア
ナタース形が好ましい。微粒子酸化チタンと呼ばれる平
均形０．１μ以下の粉末を使用することもできるが、チ
タニアゾルを用いるのが好ましい。チタニアゾルは含水
酸化チタンを塩酸、硝酸のような強酸で解膠することに
よって製造され、強酸性である。本発明の目的に対して
はチタニアゾルも中性でなければならない。しかし酸性
チタニアゾルを単に中和によって中性化すると分散粒子
が凝集し、ゾルを形成しなくなる。そのため強酸で解膠
したチタニアゾルから陰イオンを除去した後に分散安定
剤を添加して得られる中性チタニアゾル（特開昭６４−
３０２０）や、水酸化チタンを過酸化水素で処理して得
られた溶液を加熱処理することによって表面をペルオキ
ソ基で修飾したアナタース形チタニアゾル（特開平１０
−６７５１６）を使用することができる。The titanium oxide photocatalyst particles are preferably in an anatase form having high catalytic activity. Although a powder having an average shape of 0.1 μ or less called fine particle titanium oxide can be used, titania sol is preferably used. Titania sol is produced by peptizing hydrous titanium oxide with a strong acid such as hydrochloric acid or nitric acid, and is strongly acidic. For the purposes of the present invention, the titania sol must also be neutral. However, if the acidic titania sol is simply neutralized by neutralization, the dispersed particles aggregate and no sol is formed. Therefore, neutral titania sol obtained by removing anions from titania sol peptized with a strong acid and then adding a dispersion stabilizer (Japanese Patent Laid-Open No.
3020) or an anatase-type titania sol whose surface is modified with a peroxo group by heat-treating a solution obtained by treating titanium hydroxide with hydrogen peroxide (Japanese Patent Application Laid-Open No.
-67516) can be used.
【００１２】最も好ましい中性チタニアゾルは、本発明
者らが特願平１１−１０１９１５号に開示した中性の被
覆チタニアゾルである。このゾルは、強酸で解膠したチ
タニアゾルを水溶性チタン化合物およびリン酸化合物の
水溶液と混合し、中和後、濾過、水洗して得られるケー
キを水性媒体に再分散することによって製造される。こ
のゾルの分散酸化チタン粒子は同じ水和リン酸チタン化
合物で被覆されているので、分散媒である本発明の水和
リン酸化合物と良くなじみ、透明で、貯蔵安定性にすぐ
れたコーティング組成物を生成する。The most preferred neutral titania sol is the neutral coated titania sol disclosed by the present inventors in Japanese Patent Application No. 11-101915. This sol is produced by mixing a titania sol peptized with a strong acid with an aqueous solution of a water-soluble titanium compound and a phosphoric acid compound, neutralizing, filtering and washing, and redispersing a cake obtained in an aqueous medium. Since the dispersed titanium oxide particles of this sol are coated with the same hydrated titanium phosphate compound, the coating composition is transparent, has excellent storage stability and is well compatible with the hydrated phosphate compound of the present invention, which is a dispersion medium. Generate
【００１３】バインダー成分は光触媒活性を持っていな
いので、コーティング組成物中の光触媒成分の割合はそ
れから形成した光触媒膜の触媒性能に影響する。そのた
め固形分に換算した重量比で、光触媒成分はバインダー
成分の少なくとも０．１倍でなければならない。しかし
ながらこの重量比があまり大きいと、換言すると組成物
のバインダー成分が少な過ぎると光触媒粒子が強固に固
着されず、膜の密着性も低くなるので５倍をこえるべき
ではない。好ましい重量比は０．５〜２．０倍である。
またコーティング組成物中のバインダー成分と触媒成分
を合計した固形分濃度は１回の塗布で形成し得る光触媒
膜もしくは層の厚みに関係する。このためコーティング
組成物の合計固形分濃度は少なくとも５重量％を必要と
するであろう。また、組成物は基材へ適用するのに適し
たレオロジー的性質を持たなければならないので、合計
固形分は１５重量％が限度であろう。Since the binder component has no photocatalytic activity, the proportion of the photocatalytic component in the coating composition affects the catalytic performance of the photocatalytic film formed therefrom. Therefore, the photocatalytic component must be at least 0.1 times the binder component in terms of the weight ratio converted to the solid content. However, if the weight ratio is too large, in other words, if the amount of the binder component in the composition is too small, the photocatalyst particles will not be firmly fixed and the adhesion of the film will be low. The preferred weight ratio is 0.5 to 2.0 times.
The total solid content of the binder component and the catalyst component in the coating composition is related to the thickness of the photocatalyst film or layer that can be formed by one application. Thus, the total solids concentration of the coating composition will require at least 5% by weight. Also, since the composition must have rheological properties suitable for application to a substrate, the total solids will be limited to 15% by weight.
【００１４】コーティング組成物は所望により界面活性
剤やエチレングリコール等の分散安定剤、水混和性の有
機溶剤、その他の慣用の添加剤を含んでもよい。The coating composition may optionally contain a surfactant, a dispersion stabilizer such as ethylene glycol, a water-miscible organic solvent, and other conventional additives.
【００１５】基材はガラス、セメント、金属、木材、
紙、セラミックス、スレート、石膏、石材、活性炭、プ
ラスチックなどを材質とし、板状、球状、繊維状、ハニ
カム状などの任意の形状のものを使用し得る。The base material is glass, cement, metal, wood,
The material may be paper, ceramics, slate, gypsum, stone, activated carbon, plastic, or the like, and may have any shape such as a plate, a sphere, a fiber, or a honeycomb.
【００１６】コーティング組成物の基材への塗布または
含浸は、基材の形状と寸法に適した任意の方法で行うこ
とができる。例えばハケ塗り、スプレー法、バーコータ
ー法、アプリケーター法、スピンコーティング、ディッ
プ法などである。スプレー法およびスピンコート法の場
合には他の方法より固形分濃度をやや低めに設定する必
要がある。The application or impregnation of the coating composition onto the substrate can be performed by any method suitable for the shape and dimensions of the substrate. For example, a brush coating, a spray method, a bar coater method, an applicator method, a spin coating, a dip method, and the like. In the case of the spray method and the spin coating method, it is necessary to set the solid concentration slightly lower than that of other methods.
【００１７】本発明のコーティング組成物は、基材へ塗
布または含浸後乾燥することによって基材上に透明な硬
い光触媒層を形成する。この際基材を加熱して水分の蒸
発を促進することができる。紙、不織布、セラミックペ
ーパーなどの多孔質基材を用いれば、空胴内にも光触媒
層が形成され、膜の有効面積を大きくすることができ
る。The coating composition of the present invention forms a transparent hard photocatalyst layer on a substrate by being applied or impregnated on the substrate and then dried. At this time, the substrate can be heated to promote the evaporation of moisture. If a porous substrate such as paper, nonwoven fabric, ceramic paper, or the like is used, a photocatalytic layer is also formed in the cavity, and the effective area of the film can be increased.
【００１８】このような酸化チタン光触媒を固定化した
基材は、酸化チタンの光触媒反応を利用して有害物質を
分解して浄化する光触媒エレメントとして有用である。
例えばＮＯx の分解またはセルフクリーニング機能を有
する窓ガラスまたは屋外建材、空気清浄機に組み込まれ
る悪臭物質分解用フィルター、病院や浴室に使用される
抗菌性タイルの製造などに使用することができる。また
ガラスビーズ、アルミナビーズ、活性炭などを基材に使
用し、生活排水または工業排水中に含まれる界面活性
剤、染料、糊料などの光浄化に使用することができる。The substrate having such a titanium oxide photocatalyst immobilized thereon is useful as a photocatalytic element for decomposing and purifying harmful substances by utilizing the photocatalytic reaction of titanium oxide.
For example it is possible to use glazing or outdoor building material having a decomposition or self-cleaning function of the NO x, malodorous material decomposition filter to be incorporated into the air purifier, etc. manufacture of antimicrobial tiles used in hospitals or bathroom. Further, glass beads, alumina beads, activated carbon and the like can be used as a base material, and can be used for light purification of surfactants, dyes, pastes and the like contained in domestic wastewater or industrial wastewater.
【００１９】[0019]
【実施例】以下に限定を意図しない実施例によって本発
明をさらに詳しく説明する。The following non-limiting examples illustrate the invention in more detail.
【００２０】実施例１水和リン酸チタン化合物の分散ゾル（バインダー成分） ＴｉＯ2 に換算して５０ｇ／Ｌの濃度の四塩化チタン水
溶液２Ｌに、Ｐ2 Ｏ5に換算して４０ｇの正リン酸を攪
拌下に添加した。この反応液へアンモニア水を添加して
ｐＨ５．５とし、析出物を濾過、水洗してケーキを得
た。このケーキへ水を添加して固形分５重量％とし、ペ
イントシェーカー（容器４００ｍＬマヨネーズびん：媒
体直径１．５ｍｍのガラスビーズ３００ｇ：サンプル１
００ｇ：回転数７２０ｒｐｍ：分散時間１０分）を用い
て再分散し、ｐＨ６．８の水和リン酸チタン化合物のゾ
ルを得た。この分散ゾルの平均分散粒子径は１８０ｎｍ
であった。Example 1 Dispersion sol of a hydrated titanium phosphate compound (binder component) 2 L of an aqueous solution of titanium tetrachloride having a concentration of 50 g / L in terms of TiO 2 and 40 g of normal phosphorus in terms of P 2 O 5 The acid was added with stirring. Aqueous ammonia was added to the reaction solution to adjust the pH to 5.5, and the precipitate was filtered and washed with water to obtain a cake. Water was added to this cake to make the solid content 5% by weight, and a paint shaker (400 mL mayonnaise bottle: 300 g of glass beads having a medium diameter of 1.5 mm: sample 1)
(00g: rotational speed: 720 rpm: dispersion time: 10 minutes) to obtain a sol of a hydrated titanium phosphate compound having a pH of 6.8. The average dispersion particle diameter of this dispersion sol is 180 nm.
Met.
【００２１】中性チタニアゾル（光触媒成分） 硫酸チタニル水溶液を熱加水分解して得た含水酸化チタ
ンスラリーをアンモニア水でｐＨ７に中和し、濾過、水
洗して得たケーキを、ケーキ中の酸化チタン（ＴｉＯ2
換算）に対して５重量％（ＨＣｌに換算）の塩酸で解膠
し、ｐＨ１．１のＴｉＯ2 に換算して３２重量％のアナ
タース形チタニアゾルを得た。 Neutral titania sol (photocatalytic component) A hydrous titanium oxide slurry obtained by hydrolyzing an aqueous solution of titanyl sulfate is neutralized to pH 7 with aqueous ammonia, filtered and washed with water to obtain a cake obtained by adding titanium oxide in the cake. (TiO 2
Peptide was deflocculated with 5% by weight (converted to HCl) of hydrochloric acid to obtain anatase-type titania sol of 32% by weight converted to TiO 2 of pH 1.1.
【００２２】上で得たアナタース形チタニアゾルをＴｉ
Ｏ2 換算で５０ｇ／Ｌの濃度に水で希釈し、この希釈ゾ
ル２ＬへＴｉＯ2 換算１５ｇの四塩化チタン水溶液を添
加し、次いでＰ2 Ｏ5 に換算して５ｇの正リン酸を添加
し、２時間反応させた。この反応液をアンモニア水でｐ
Ｈ５．５に中和し、濾過、水洗して得たケーキを固形分
が２５重量％になるように水と混合し、ペイントシェカ
ー（容器４００ｍＬマヨネーズびん：媒体直径１．５ｍ
ｍのガラスビーズ３００ｇ：サンプル１００ｇ：回転数
７２０ｒｐｍ：分散時間１０分）を用いて分散し、ｐＨ
６．８、平均分散粒子径６０ｎｍの中性チタニアゾルを
得た。The anatase-type titania sol obtained above was converted to Ti
It is diluted with water to a concentration of 50 g / L in terms of O 2, 2 g of the diluted sol is added with 15 g of an aqueous solution of titanium tetrachloride in terms of TiO 2 , and then 5 g of orthophosphoric acid in terms of P 2 O 5 is added. And reacted for 2 hours. This reaction solution is p
The cake obtained by neutralizing to H5.5, filtering and washing with water was mixed with water so that the solid content became 25% by weight, and the mixture was painted with a paint shaker (400 mL mayonnaise bottle: medium diameter 1.5 m).
m glass beads: 300 g: sample 100 g: rotation speed: 720 rpm: dispersion time: 10 minutes) and pH
6.8, a neutral titania sol having an average dispersed particle diameter of 60 nm was obtained.
【００２３】コーティング組成物 上のバインダー成分に対し光触媒成分を固形分として
１：０．５の割合で混合し、ｐＨ６．８で、固形分６．
８重量％のコーティング組成物を得た。The photocatalyst component was mixed with the binder component on the coating composition at a ratio of 1: 0.5 as a solid content, and at a pH of 6.8 and a solid content of 6.
8% by weight of the coating composition was obtained.
【００２４】実施例２ 実施例１において、バインダー成分と光触媒を固形分と
して１：０．２の割合で混合し、ｐＨ６．８で、固形分
５．８重量％のコーティング組成物を得た。Example 2 In Example 1, the binder component and the photocatalyst were mixed at a solid content of 1: 0.2 to obtain a coating composition having a pH of 6.8 and a solid content of 5.8% by weight.
【００２５】実施例３ 実施例１において、バインダー成分と光触媒成分を固形
分として１：４．８の割合で混合し、ｐＨ６．８で、固
形分１３．３重量％のコーティング組成物を得た。Example 3 In Example 1, the binder component and the photocatalyst component were mixed at a solid ratio of 1: 4.8 to obtain a coating composition having a pH of 6.8 and a solid content of 13.3% by weight. .
【００２６】実施例４水和リン酸チタン化合物の分散ゾル（バインダー成分） 実施例１において、正リン酸をＰ2 Ｏ5 換算で１８０ｇ
に変更した以外は実施例１に同じ。得られた分散ゾルは
ｐＨ７．１で、平均分散粒子径は３００ｎｍであった。Example 4 Dispersion sol of a hydrated titanium phosphate compound (binder component) In Example 1, 180 g of orthophosphoric acid was calculated as P 2 O 5.
Same as Example 1 except for changing to. The resulting dispersion sol had a pH of 7.1 and an average dispersed particle size of 300 nm.
【００２７】コーティング組成物 上のバインダー成分と実施例１の光触媒成分を固形分と
して１：０．５の割合で混合し、ｐＨ７．０で、固形分
が６．８重量％のコーティング組成物を得た。The binder component on the coating composition and the photocatalyst component of Example 1 were mixed at a solid content of 1: 0.5, and a coating composition having a pH of 7.0 and a solid content of 6.8% by weight was mixed. Obtained.
【００２８】実施例５水和リン酸チタン化合物の分散ゾル（バインダー成分） 実施例１において、正リン酸をＰ2 Ｏ5 換算で２５ｇに
変更した以外は実施例１に同じ。得られた分散ゾルはｐ
Ｈ６．３で、平均分散粒子径は４００ｎｍであった。Example 5 Dispersion sol (binder component) of hydrated titanium phosphate compound Same as Example 1 except that orthophosphoric acid was changed to 25 g in terms of P 2 O 5 . The resulting dispersion sol is p
H6.3, and the average dispersed particle size was 400 nm.
【００２９】コーティング組成物 上のバインダー成分と実施例１の光触媒成分を固形分と
して１：０．５の割合で混合し、ｐＨ６．５で、固形分
６．８重量％のコーティング組成物を得た。The binder component on the coating composition and the photocatalyst component of Example 1 were mixed at a solid content of 1: 0.5 to obtain a coating composition having a pH of 6.5 and a solid content of 6.8% by weight. Was.
【００３０】実施例６水和リン酸チタン化合物の分散ゾル（バインダー成分） 実施例１において、正リン酸に代えてＰ2 Ｏ5 に換算し
て４０ｇのメタリン酸を使用した以外は実施例１に同
じ。得られた分散ゾルはｐＨ６．９で、平均分散粒子径
は２２０ｎｍであった。Example 6 Dispersion sol of a hydrated titanium phosphate compound (binder component) Example 1 was repeated except that 40 g of metaphosphoric acid in terms of P 2 O 5 was used instead of orthophosphoric acid. Same as The resulting dispersion sol had a pH of 6.9 and an average dispersed particle size of 220 nm.
【００３１】コーティング組成物 上のバインダー成分と実施例１の光触媒成分を固形分と
して１：０．５の割合で混合し、ｐＨ６．９で、固形分
６．８重量％のコーティング組成物を得た。The binder component on the coating composition and the photocatalyst component of Example 1 were mixed at a ratio of 1: 0.5 as a solid content to obtain a coating composition having a pH of 6.9 and a solid content of 6.8% by weight. Was.
【００３２】実施例７水和リン酸チタン化合物の分散ゾル（バインダー成分） 実施例１において、四塩化チタン水溶液の代わりにＴｉ
Ｏ2 に換算して５０ｇ／Ｌの硫酸チタニル水溶液を使用
した以外は実施例１に同じ。得られた分散ゾルはｐＨ
６．７で、平均分散粒子径は２５０ｎｍであった。Example 7 Dispersion sol of a hydrated titanium phosphate compound (binder component) In Example 1, titanium tetrachloride was replaced with Ti aqueous solution.
Same as Example 1 except that a 50 g / L aqueous solution of titanyl sulfate in terms of O 2 was used. The resulting dispersion sol is pH
6.7, and the average dispersed particle size was 250 nm.
【００３３】コーティング組成物 上のバインダー成分と実施例１の光触媒成分を固形分と
して１：０．５の割合で混合し、ｐＨ６．７で、固形分
６．８重量％のコーティング組成物を得た。The binder component on the coating composition and the photocatalyst component of Example 1 were mixed at a ratio of 1: 0.5 as a solid content to obtain a coating composition having a pH of 6.7 and a solid content of 6.8% by weight. Was.
【００３４】比較例１ バインダー成分と光触媒成分を固形分として１：０．０
５の割合で混合した以外は実施例１に同じ。ｐＨ６．８
で、固形分５．２重量％のコーティング組成物を得た。Comparative Example 1 The binder component and the photocatalyst component were mixed at a solid content of 1: 0.0
Same as Example 1 except that they were mixed at a ratio of 5. pH 6.8
Thus, a coating composition having a solid content of 5.2% by weight was obtained.
【００３５】比較例２ バインダー成分と光触媒成分を固形分として１：６の割
合で混合した以外は実施例１に同じ。ｐＨ６．８で、固
形分１５．９重量％のコーティング組成物を得た。Comparative Example 2 Same as Example 1 except that the binder component and the photocatalyst component were mixed at a ratio of 1: 6 as solids. A coating composition having a pH of 6.8 and a solid content of 15.9% by weight was obtained.
【００３６】比較例３ 実施例１の水和リン酸チタン化合物の調製において、四
塩化チタン水溶液へ正リン酸を加えることなく直接アン
モニア水で中和し、酸化チタン水和物のスラリーを得
た。このスラリーのｐＨ６．０で、平均分散粒子径は９
００ｎｍであり、分散粒子は直ちに沈降した。Comparative Example 3 In the preparation of the hydrated titanium phosphate compound of Example 1, the aqueous solution of titanium oxide was directly neutralized with aqueous ammonia without adding orthophosphoric acid to obtain a slurry of titanium oxide hydrate. . At pH 6.0 of this slurry, the average dispersed particle size was 9
00 nm, and the dispersed particles immediately settled.
【００３７】このスラリーと実施例１の触媒成分を固形
分として１：０．５の割合で混合し、ｐＨ６．３で、固
形分６．８重量％のコーティング組成物を調製した。This slurry and the catalyst component of Example 1 were mixed at a ratio of 1: 0.5 as a solid content to prepare a coating composition having a pH of 6.3 and a solid content of 6.8% by weight.
【００３８】比較例４ 実施例１で製造した水和リン酸チタン化合物の分散ゾル
をコーティング組成物として用いた。Comparative Example 4 A dispersion sol of the hydrated titanium phosphate compound produced in Example 1 was used as a coating composition.
【００３９】比較例５ 実施例１で製造した中性チタニアゾルをコーティング組
成物として用いた。Comparative Example 5 The neutral titania sol prepared in Example 1 was used as a coating composition.
【００４０】実施例および比較例のコーティング組成物
の貯蔵安定性およびそれからつくった塗膜の性能につい
て評価した。The storage stability of the coating compositions of the Examples and Comparative Examples and the performance of the coating films formed therefrom were evaluated.
【００４１】貯蔵安定性 試料を固形分５重量％へ水で希釈し、１００ｇを蓋付き
のガラス容器に入れ、２５℃で２ケ月間静置し、沈降物
の有無について目視で評価した。 Storage stability The sample was diluted with water to a solid content of 5% by weight, 100 g was placed in a glass container with a lid, and allowed to stand at 25 ° C. for 2 months, and the presence or absence of sediment was visually evaluated.
【００４２】平均分散粒子径の測定 試料を固形分０．５重量％へ水で希釈し、粒度分布測定
器（Ｍｉｃｒｏｔｒａｃ ＵＰＡ 日機装（株））で分
散粒子径（体積平均径）を求めた。A sample of the average dispersed particle size was diluted with water to a solid content of 0.5% by weight, and the dispersed particle size (volume average size) was determined with a particle size distribution analyzer (Microtrac UPA Nikkiso Co., Ltd.).
【００４３】光触媒膜の性能評価 １．塗膜の作成方法 試料を固形分５重量％へ水で希釈し、スライドガラス板
（松波ガラス社製、サイズ７．６×２．６ｃｍ，厚み
１．３ｍｍ）へバーコーター＃１０（太佑機械社製）を
用いて塗布し、１１０℃で３０分間乾燥し、塗板を作成
した。 Performance Evaluation of Photocatalytic Film Preparation method of coating film A sample is diluted with water to a solid content of 5% by weight, and is applied to a slide glass plate (manufactured by Matsunami Glass Co., size 7.6 × 2.6 cm, thickness 1.3 mm) with a bar coater # 10 (Tayu Kikai Co., Ltd.) Co., Ltd.) and dried at 110 ° C. for 30 minutes to prepare a coated plate.
【００４４】２．透明性の測定 塗膜の透明性を透過率積分値（％Ｔ・ｎｍ）＝透過率
（％Ｔ）×（７００ｎｍ−４００ｎｍ）により測定し
た。また目視による判定も行った。透過率積分値が２６
０００％Ｔ・ｎｍ以上で目視で無色透明なものを良好と
し、２６０００％Ｔ・ｎｍ未満または目視で無色透明で
ないものを不良とした。2. Measurement of Transparency The transparency of the coating film was measured by integrating transmittance (% T · nm) = transmittance (% T) × (700 nm-400 nm). Visual determination was also performed. Transmittance integral value is 26
Those that were visually colorless and transparent at 000% T · nm or more were rated good, and those that were less than 26000% T · nm or visually colorless and transparent were rated poor.
【００４５】３．密着性 ＪＩＳ Ｋ５４００に従ったゴバン目テープ法によって
評価した。テープを剥がした後の塗膜剥離部分が総ゴバ
ン目の１０％未満を良好とし、１０％以上のものを不良
とした。3. Adhesion The adhesiveness was evaluated by the Goban-like tape method according to JIS K5400. When the peeled portion of the coating film after peeling off the tape was less than 10% of the total gross pattern, it was regarded as good, and when it was 10% or more, it was regarded as bad.
【００４６】４．塗膜硬度 ＪＩＳ Ｋ５４００に従った鉛筆硬度によって評価し
た。鉛筆硬度３Ｈ以上を良好とし、２Ｈ以下を不良とし
た。4. Film hardness was evaluated by pencil hardness according to JIS K5400. A pencil hardness of 3H or more was defined as good, and a pencil hardness of 2H or less was defined as poor.
【００４７】５．光触媒活性 塗板を内容積４００ｍｌのガラス容器へ入れ、その中に
１０ｐｐｍのＮＯガスを封入した。この容器を高圧水銀
灯（和光電気社製理化学用水銀灯起動装置Ｈ−４００−
Ａ／Ｂ、ランプ東芝Ｈ−４００Ｆ、ランプ消費電力４０
０Ｗ）の直下２５ｃｍに設置し、水銀灯の照射強度が
３．７ｍＷ／ｃｍ2 になるように微調整した。その後上
記ガラス容器を回転させながら高圧水銀灯で１０分間塗
板を照射した。5. Photocatalytic activity The coated plate was placed in a glass container having an internal volume of 400 ml, and 10 ppm of NO gas was sealed therein. This container is placed in a high-pressure mercury lamp (H-400- mercury lamp activator for physics and chemistry manufactured by Wako Electric Co., Ltd.).
A / B, Lamp Toshiba H-400F, Lamp power consumption 40
0 W), and finely adjusted so that the irradiation intensity of the mercury lamp was 3.7 mW / cm 2 . Thereafter, the coated plate was irradiated with a high-pressure mercury lamp for 10 minutes while rotating the glass container.
【００４８】照射後の残留ＮＯガス濃度をガス検知機
（ＧＡＳＴＥＣ社製ＧＶ−１００Ｓ検知管Ｎｏ．１１
Ｌ）により測定し、以下の式により光分解率を求めた。 光分解率（％）＝（初期ガス濃度−残留ガス濃度）／初
期ガス濃度×１００ 結果を表１に示す。The residual NO gas concentration after irradiation was measured with a gas detector (GV-100S detector tube No. 11 manufactured by GASTEC).
L), and the photodegradation rate was determined by the following equation. Photodecomposition rate (%) = (initial gas concentration−residual gas concentration) / initial gas concentration × 100 The results are shown in Table 1.
【００４９】[0049]
【表１】 [Table 1]
【００５０】表１に示すように、実施例１〜７の光触媒
透明コーティング組成物は貯蔵安定性か良好であった、
またスライドガラス板に塗布して作製したコーティング
液塗布ガラス板の塗膜は、膜透明性、膜密着性、膜硬度
が優れ、良好なＮＯガス光分解率を有していた。As shown in Table 1, the transparent coating compositions of Examples 1 to 7 had good storage stability.
Further, the coating film of the glass plate coated with the coating liquid prepared by applying the coating solution to the slide glass plate was excellent in film transparency, film adhesion, and film hardness, and had a good NO gas photolysis rate.
【００５１】しかし、比較例１〜５のコーティング液を
スライドガラス板に塗布して作製したコーティング液塗
布ガラス板の塗膜は、それぞれ以下に示すような問題を
有していた。比較例１については塗膜の光触媒能が低
い。比較例２については塗膜の密着性、膜硬度が不良で
あった。比較例３については分散安定性が不良で、塗膜
の透明性も不良であった。比較例４については塗膜の光
触媒能が存在しない。比較例５については塗膜の密着
性、膜硬度が不良であった。However, the coating films of the glass plates coated with the coating liquid prepared by applying the coating liquids of Comparative Examples 1 to 5 to the slide glass plate had the following problems. In Comparative Example 1, the photocatalytic ability of the coating film was low. In Comparative Example 2, the coating film had poor adhesion and film hardness. In Comparative Example 3, the dispersion stability was poor, and the transparency of the coating film was also poor. In Comparative Example 4, the coating had no photocatalytic ability. In Comparative Example 5, the adhesion and the film hardness of the coating film were poor.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 35/02 ３１１ Ｃ０３Ｃ 17/25 Ａ 37/02 ３０１ Ｃ０９Ｄ 5/00 Ｌ Ｃ０３Ｃ 17/25 7/12 Ｚ Ｃ０９Ｄ 5/00 Ａ６１Ｌ 9/01 Ｅ 7/12 Ｂ０１Ｄ 53/36 Ｊ // Ａ６１Ｌ 9/01 １０２Ｚ (72)発明者 長田 和久 大阪府大阪市大正区船町１丁目３番47号 テイカ株式会社内 Ｆターム(参考） 4C080 AA07 BB02 CC01 HH07 JJ03 KK08 LL03 MM02 NN09 QQ11 4D048 AA06 BA07X BA41X BA44X BB03 BB18 EA01 4G059 AA02 AC18 AC30 EA04 EA18 EB07 4G069 AA08 AA11 BA04A BA04B BA37 BA48A BA48C BB14A BB14B BD07A BD07B CA13 EA02X EA02Y EA07 ED05 FB23 4J038 EA011 HA216 KA04 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) B01J 35/02 311 C03C 17/25 A 37/02 301 C09D 5/00 L C03C 17/25 7/12 Z C09D 5 / 00 A61L 9/01 E 7/12 B01D 53/36 J // A61L 9/01 102Z (72) Inventor Kazuhisa Nagata 1-34, Funamachi, Taisho-ku, Osaka-shi, Osaka Prefecture F-term (reference) 4C080 AA07 BB02 CC01 HH07 JJ03 KK08 LL03 MM02 NN09 QQ11 4D048 AA06 BA07X BA41X BA44X BB03 BB18 EA01 4G059 AA02 AC18 AC30 EA04 EA18 EB07 4G069 AA08 AA11 BA04A23 EA07 EB07 EB07 EB07 EB07 EB07 BB07
Claims (5)
透明な分散ゾル中に分散した酸化チタン光触媒粒子を含
んでいることを特徴とする光触媒膜形成用コーティング
組成物。1. A coating composition for forming a photocatalyst film, comprising titanium oxide photocatalyst particles dispersed in a transparent dispersion sol in a neutral region of a hydrated titanium phosphate compound.
は、水溶性チタン化合物とリン酸化合物をＴｉＯ2 ／Ｐ
2 Ｏ5 に換算した重量比０．５〜５．０で反応させ、反
応液を中和、濾過、水洗して得られるケーキを水性媒体
に再分散することによって製造される請求項１のコーテ
ィング組成物。2. The dispersion sol of the hydrated titanium phosphate compound comprises a water-soluble titanium compound and a phosphate compound formed of TiO 2 / P.
Reacted in a weight ratio of 0.5 to 5.0 in terms of 2 O 5, neutralizing the reaction solution, filtered and coating of claim 1, the cake obtained by water washing is produced by re-dispersed in an aqueous medium Composition.
である請求項１または２のコーティング組成物。3. The coating composition according to claim 1, wherein the titanium oxide photocatalyst particles are neutral titania sol.
チタン酸化合物に対する固形分比は０．１〜５．０であ
る請求項１ないし３のいずれかのコーティング組成物。4. The coating composition according to claim 1, wherein the solid content ratio of the titanium oxide photocatalyst to the hydrated titanium phosphate compound is 0.1 to 5.0.
成物を基材に塗布し、乾燥することよりなる酸化チタン
光触媒膜の形成方法。5. A method for forming a titanium oxide photocatalyst film, comprising applying the coating composition according to claim 1 to a substrate and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10893199A JP3978636B2 (en) | 1999-04-16 | 1999-04-16 | Coating composition for photocatalyst film formation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10893199A JP3978636B2 (en) | 1999-04-16 | 1999-04-16 | Coating composition for photocatalyst film formation |
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| Publication Number | Publication Date |
|---|---|
| JP2000302422A true JP2000302422A (en) | 2000-10-31 |
| JP3978636B2 JP3978636B2 (en) | 2007-09-19 |
Family
ID=14497297
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|---|---|---|---|
| JP10893199A Expired - Lifetime JP3978636B2 (en) | 1999-04-16 | 1999-04-16 | Coating composition for photocatalyst film formation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053285A1 (en) * | 2000-12-28 | 2002-07-11 | Showa Denko K.K. | Powder exhibiting optical function and use thereof |
| JP2003093894A (en) * | 2001-09-26 | 2003-04-02 | Kawashima Textile Manuf Ltd | Odor decreasing fabric and method for odor decreasing finishing |
| JP2004130195A (en) * | 2002-10-09 | 2004-04-30 | Takeshi Ohara | Agent for reducing volatile organic compoumd, nox, or sox |
| US7060643B2 (en) | 2000-12-28 | 2006-06-13 | Showa Denko Kabushiki Kaisha | Photo-functional powder and applications thereof |
| RU2647304C1 (en) * | 2017-05-03 | 2018-03-15 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | Method for obtaining titanium phosphate |
| CN111359641A (en) * | 2020-03-27 | 2020-07-03 | 中触媒新材料股份有限公司 | Novel composite immobilized photocatalyst of three-dimensional porous foamed ceramic and preparation method thereof |
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1999
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053285A1 (en) * | 2000-12-28 | 2002-07-11 | Showa Denko K.K. | Powder exhibiting optical function and use thereof |
| US7060643B2 (en) | 2000-12-28 | 2006-06-13 | Showa Denko Kabushiki Kaisha | Photo-functional powder and applications thereof |
| US7169728B2 (en) | 2000-12-28 | 2007-01-30 | Showa Denko Kabushiki Kaisha | Photo-functional powder and applications thereof |
| JP2003093894A (en) * | 2001-09-26 | 2003-04-02 | Kawashima Textile Manuf Ltd | Odor decreasing fabric and method for odor decreasing finishing |
| JP2004130195A (en) * | 2002-10-09 | 2004-04-30 | Takeshi Ohara | Agent for reducing volatile organic compoumd, nox, or sox |
| RU2647304C1 (en) * | 2017-05-03 | 2018-03-15 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | Method for obtaining titanium phosphate |
| WO2020202874A1 (en) * | 2019-03-29 | 2020-10-08 | 日本電産株式会社 | Optical member and method for manufacturing same |
| CN113646084A (en) * | 2019-03-29 | 2021-11-12 | 日本电产株式会社 | Optical member and method for manufacturing the same |
| CN111359641A (en) * | 2020-03-27 | 2020-07-03 | 中触媒新材料股份有限公司 | Novel composite immobilized photocatalyst of three-dimensional porous foamed ceramic and preparation method thereof |
| CN113041965A (en) * | 2021-03-11 | 2021-06-29 | 廊坊师范学院 | Preparation method of titanium phosphate sol |
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