JP4542601B2 - Photocatalyst coating liquid manufacturing method, antibacterial deodorant dry cleaning coating liquid, and photocatalyst-processed clothing. - Google Patents
Photocatalyst coating liquid manufacturing method, antibacterial deodorant dry cleaning coating liquid, and photocatalyst-processed clothing. Download PDFInfo
- Publication number
- JP4542601B2 JP4542601B2 JP2009018829A JP2009018829A JP4542601B2 JP 4542601 B2 JP4542601 B2 JP 4542601B2 JP 2009018829 A JP2009018829 A JP 2009018829A JP 2009018829 A JP2009018829 A JP 2009018829A JP 4542601 B2 JP4542601 B2 JP 4542601B2
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- Prior art keywords
- silver
- particles
- mineral particles
- titanium oxide
- suspension
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- 239000007788 liquid Substances 0.000 title claims description 111
- 239000011248 coating agent Substances 0.000 title claims description 53
- 238000000576 coating method Methods 0.000 title claims description 52
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 46
- 239000011941 photocatalyst Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000005108 dry cleaning Methods 0.000 title claims description 20
- 239000002781 deodorant agent Substances 0.000 title claims description 14
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001773 titanium mineral Inorganic materials 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
本発明は、光触媒コーティング液の製造方法、並びに抗菌消臭ドライクリーニング用コーティング液及び光触媒加工衣料に関する。 The present invention relates to a method for producing a photocatalyst coating liquid, and coating liquid for antibacterial deodorizing dry cleaning and to a photocatalyst processing clothing.
銀イオンはバクテリアなどの下等生物（雑菌）に対して強い殺菌力を示すため、抗菌剤として使用されている。また、酸化チタン（二酸化チタン）は光を照射することで汚れを分解する光触媒活性物質として使用されている。近年、銀と酸化チタンと鉱物とを組み合わせた粒子を液中に分散させた懸濁液からなる光触媒コーティング液が実用化されている。この光触媒コーティング液は、抗菌作用や消臭作用を施す目的で、カーテン布、シーツ、衣料などの生地や不織布等の繊維に塗布される。ここで抗菌作用とは雑菌の繁殖を阻止する作用であり、消臭作用とは老廃物（脂質や雑菌の死骸等）を分解して臭いを消す作用である。また、抗菌加工製品の抗菌性試験方法と抗菌効果の評価方法としては、ＪＩＳ Ｌ１９０２が規定されている。 Silver ions are used as an antibacterial agent because they exhibit a strong bactericidal power against lower organisms (miscellaneous bacteria) such as bacteria. Titanium oxide (titanium dioxide) is used as a photocatalytically active substance that decomposes dirt when irradiated with light. In recent years, a photocatalytic coating liquid made of a suspension in which particles obtained by combining silver, titanium oxide, and mineral are dispersed in a liquid has been put into practical use. This photocatalyst coating solution is applied to fabrics such as curtain cloths, sheets, and clothing, and fibers such as nonwoven fabrics for the purpose of antibacterial action and deodorant action. Here, the antibacterial action is an action that inhibits the propagation of various bacteria, and the deodorizing action is an action that decomposes waste products (lipids, dead bodies of bacteria, etc.) and eliminates odors. Moreover, JIS L1902 is prescribed | regulated as an antibacterial test method and antibacterial effect evaluation method of an antibacterial processed product.
銀ナノ粒子を水に混ぜると凝集体を形成し均一な懸濁液とはならない。このため従来、銀をリン酸カルシウム（アパタイト）やアルミナシリカ等の鉱物粒子に担持させた銀担持鉱物粒子を水に混合して使用している。銀を鉱物に担持させる方法としては、銀を鉱物に練り込んで粒子を形成する方法や、イオン交換によって銀をアパタイトに担持させる方法が知られている（例えば特許文献２、特許文献４）。 When silver nanoparticles are mixed with water, aggregates are formed and the suspension is not uniform. For this reason, silver-supporting mineral particles in which silver is supported on mineral particles such as calcium phosphate (apatite) and alumina silica have been conventionally mixed with water. As a method for supporting silver on a mineral, a method of kneading silver into a mineral to form particles and a method of supporting silver on an apatite by ion exchange (for example, Patent Document 2 and Patent Document 4) are known.
しかしながら、銀を鉱物に練り込む方法は、鉱物粒子の内部に多くの銀が練り込まれてしまい、鉱物粒子の表層に出ている銀活性面が少ない。また、イオン交換によって銀をアパタイトに担持させる方法は、アパタイトの結晶構造が歪んだり破壊されるために担持された銀が脱落し易い。一部の商品では、コストを抑えるために高価な銀の使用量を少なくして、その結果、抗菌効果があると認められないような商品も市場に出回っているのが現状である。 However, in the method of kneading silver into minerals, a large amount of silver is kneaded inside the mineral particles, and there are few silver active surfaces appearing on the surface layer of the mineral particles. Further, in the method of supporting silver on apatite by ion exchange, the supported silver is easily dropped because the crystal structure of apatite is distorted or destroyed. In some products, the amount of expensive silver used is reduced to reduce costs, and as a result, there are products on the market that are not recognized as having an antibacterial effect.
銀担持鉱物粒子や酸化チタン粒子を水中に均一に分散させて懸濁液とするためには、これら粒子の粒径をナノサイズ（１μｍ未満）まで微粒化しなければならない。粒子を微粒化する方法としては、ボールミルなどの粉砕媒体を使用した湿式の機械的接触式粉砕（例えば特許文献２では単に湿式粉砕機と記述されている）や、同体摩擦粉砕（例えば特許文献４を参照）による方法が知られている。しかし、機械的接触式粉砕では、粒子自体が壊れる不具合や、粉砕媒体から発生するｃｏｎｔａｍｉｎａｎｔ（汚染物質：コンタミとも呼ばれる）が混入する不具合がある。また、同体摩擦粉砕では、粒子自体が壊れる危険がある。そこで、粒子の混合液をチャンバーノズルから高圧噴射することで、粒子自体を壊さず、コンタミの混入がない微粒化工法が開発され（特許文献８）、実用化された（非特許文献１）。 In order to uniformly disperse silver-carrying mineral particles and titanium oxide particles in water to form a suspension, the particle size of these particles must be atomized to nano size (less than 1 μm). As a method for atomizing the particles, wet mechanical contact pulverization using a pulverization medium such as a ball mill (for example, simply described as a wet pulverizer in Patent Document 2) or in-body friction pulverization (for example, Patent Document 4). Method) is known. However, the mechanical contact pulverization has a problem that the particles themselves are broken and a problem that contaminants (also called contaminants) generated from the pulverization medium are mixed. In the same body friction grinding, there is a risk that the particles themselves are broken. Therefore, a method of atomization by developing a mixture of particles from a chamber nozzle at a high pressure so as not to break the particles themselves and to prevent contamination (patent document 8) has been put into practical use (non-patent document 1).
衣料は、衛生面からクリーニング（洗濯）を行っており、クリーニング店では衣料の生地等を傷めない観点から、蒸気や揮発性の溶剤を用いて行うドライクリーニングが主流となっている。本明細書では、衣料を、衣服や下着に限定せずに、クリーニングが可能なタオル、カーテン、鞄等の繊維製品全般を衣料としている。 Clothing is cleaned (washed) from the hygiene aspect, and dry cleaning using steam or a volatile solvent has become the mainstream from the viewpoint of not damaging the clothing fabric and the like at a cleaning store. In this specification, clothes are not limited to clothes and underwear, and all textile products such as towels, curtains, and bags that can be cleaned are used as clothes.
従来の光触媒コーティング液では、銀を担持する担体として主にアパタイトが用いられている。これは、吸着力（付着力）の強いアパタイトを用いることで、繊維等の対象物にアパタイトを固着させて剥がれ難くさせるという考え方に基づいている。 In the conventional photocatalyst coating liquid, apatite is mainly used as a carrier for supporting silver. This is based on the idea that by using apatite having a strong adsorption force (adhesion force), the apatite is fixed to an object such as a fiber and is not easily peeled off.
特許文献１（特開２００２−２８４６１４号公報）には、光触媒活性成分である二酸化チタン粒子の一部が光不活性な無機化合物（アパタイト）で覆われた光触媒粉末を用い、該光触媒粉末を固定するための有機バインダー成分をさらに含んでなる抗菌消臭用加工液が記載されている。 Patent Document 1 (Japanese Patent Laid-Open No. 2002-284614) uses a photocatalyst powder in which a part of titanium dioxide particles as a photocatalytic active component is covered with a photoinert inorganic compound (apatite), and the photocatalyst powder is fixed. An antibacterial deodorant processing liquid further comprising an organic binder component is described.
特許文献２（特開２００２−３７０９１１号公報）には、無機担体に抗菌性金属を担持させてなる無機抗菌剤をホウ酸、ホウ酸アルカリ金属塩及びリン酸アルカリ金属塩から選ばれる無機分散剤にて水に分散させてなる繊維品の抗菌加工剤が記載されており、前記無機抗菌剤が抗菌性金属を担持させたゼオライト、銀を担持させたリン酸ジルコニウム、銀を担持させたシリカゲル、銀を担持させたアパタイト、銀を担持させた含水酸化チタン、銀を担持させたモンモリロナイト、銀を担持させたガラス粉末又は銀を担持させたチタン酸カリウムウィスカーから選ばれるとの記載がある。 Patent Document 2 (Japanese Patent Laid-Open No. 2002-370911) discloses an inorganic dispersant in which an inorganic antibacterial agent obtained by supporting an antibacterial metal on an inorganic carrier is selected from boric acid, alkali metal borate and alkali metal phosphate. An antibacterial finishing agent for textiles dispersed in water is described, and the inorganic antibacterial agent carries zeolite carrying an antibacterial metal, zirconium phosphate carrying silver, silica gel carrying silver, There is a description that it is selected from apatite supporting silver, hydrous titanium oxide supporting silver, montmorillonite supporting silver, glass powder supporting silver, or potassium titanate whisker supporting silver.
特許文献３（特開２００３−１９９８１０号公報）には、チタニア粒子の表面を光に不活性なセラミックス（アルミナ、シリカ、ジルコニア、チタン酸ジルコニウム、マグネシア、カルシア、リン酸カルシウム、リン酸チタン、酸化鉄、フェライト、石膏、及び非晶質のチタニアの内から選ばれた少なくとも一種）で部分的に被覆してなる被覆チタニア粒子を、多孔質材料（活性炭、発泡プラスチックス、ガラス繊維成形体、合成繊維成形体、ＦＲＰ成形体、プラスチックス−無機複合成形体、繊維成形体、活性アルミナ、ゼオライト、ガラス多孔体、金属多孔体、セラミックス多孔体、粘土成形体、及び無機層状化合物成形体の内から選ばれた少なくとも一種）に担持したことを特徴とする機能性吸着剤が記載されており、前記チタニア粒子が、白金、ロジウム、ルテニウム、パラジウム、銀、銅、鉄、及び亜鉛の内から選ばれた少なくとも一種の金属を、該チタニア粒子の表面に担持してなるチタニア粒子であるとの記載がある。 In Patent Document 3 (Japanese Patent Laid-Open No. 2003-199810), the surface of the titania particles is ceramics that are inert to light (alumina, silica, zirconia, zirconium titanate, magnesia, calcia, calcium phosphate, titanium phosphate, iron oxide, Coated titania particles partially coated with ferrite, gypsum, and amorphous titania) are made of porous materials (activated carbon, foamed plastics, glass fiber molded products, synthetic fiber molded products) Body, FRP molded body, plastics-inorganic composite molded body, fiber molded body, activated alumina, zeolite, porous glass body, porous metal body, ceramic porous body, clay molded body, and inorganic layered compound molded body. A functional adsorbent characterized in that it is supported on at least one kind) and said titania grains. But platinum, rhodium, ruthenium, palladium, silver, copper, iron, and at least one metal selected from among zinc, is described with the titania particles obtained by carried on the surface of the titania particles.
特許文献４（特開２００２−１８０３８５号公報）には、染色剤と酸化チタン水溶液の混合液を繊維布地に含浸させる酸化チタン水溶液染色処理方法が記載されている。 Patent Document 4 (Japanese Patent Application Laid-Open No. 2002-180385) describes a titanium oxide aqueous solution dyeing method in which a fiber cloth is impregnated with a mixed solution of a dyeing agent and a titanium oxide aqueous solution.
特許文献５（特開２００４−３５６７２号公報）には、全組成物量に対して、重量％表示で、光触媒作用を有する酸化チタンを３０〜６０％、珪酸アルカリ塩を１０〜３５％、シリカを３０〜５０％含むコーティング剤用組成物が記載されており、他の成分として金属、金属酸化物、リン酸塩、カルシウムシリケート、金属シリコン、アパタイト、フッ素成分の何れか１以上を１０重量％以下含むとの記載がある。 In Patent Document 5 (Japanese Patent Laid-Open No. 2004-35672), 30% to 60% of titanium oxide having a photocatalytic action, 10 to 35% of an alkali silicate salt, and silica in terms of% by weight with respect to the total amount of the composition. A composition for a coating agent containing 30 to 50% is described, and 10% by weight or less of any one or more of metal, metal oxide, phosphate, calcium silicate, metal silicon, apatite, and fluorine component as other components There is a description that it includes.
特許文献６（特開２００４−２８５４８５号公報）には、水に難溶性または不溶性で平均粒径０．００５〜４００μｍの粒子状吸着剤を０．００１〜５％含有し、臭気物質の吸着による消臭効果を繊維製品に付与する繊維製品処理剤が記載されており、前記粒子状吸着剤が、金属酸化物、金属複水酸化物、金属リン酸塩、金属ケイ酸塩、二酸化ケイ素、ケイ酸誘導体、合成ゼオライト、粘土鉱物から選ばれる１種以上の成分を５０％以上含有する単一組成物の粒子であって、二酸化ケイ素、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸カルシウム、ケイ酸ジルコニウム、酸化アルミニウムから選ばれる１種以上の成分を５０％以上含有する単一組成物であって平均粒径０．００５〜２００μｍの粒子、又は、リン酸ジルコニウム、リン酸チタン、リン酸カルシウム、酸化ジルコニウム、酸化ジルコニウム水和物、酸化銅、酸化銀から選ばれる１種以上の成分を７０％以上含有する単一組成物であって平均粒径０．００５〜２００μｍの粒子、又は、ハイドロタルサイト類、合成酸化チタン、雲母、シリカ被覆型酸化チタン、シリカ被覆型酸化亜鉛、アパタイト被覆型酸化チタン、酸化亜鉛よりなる群から選ばれる１種以上であって平均粒径０．００５〜２００μｍの粒子、又は、モルデナイト、クリノゾイサイト、チャバザイト、エリオナイト、セピオライト、モンモリロナイト、ベントナイト、タルク、パーライト、活性白土、珪藻土であって平均粒径０．００５〜２００μｍの粒子であるとの記載がある。 Patent Document 6 (Japanese Patent Laid-Open No. 2004-285485) contains 0.001 to 5% of a particulate adsorbent that is hardly soluble or insoluble in water and has an average particle size of 0.005 to 400 μm, and is based on adsorption of odorous substances. A fiber product treating agent that imparts a deodorizing effect to a fiber product is described, and the particulate adsorbent is a metal oxide, metal double hydroxide, metal phosphate, metal silicate, silicon dioxide, silica Particles of a single composition containing 50% or more of one or more components selected from acid derivatives, synthetic zeolites, and clay minerals, silicon dioxide, aluminum silicate, magnesium silicate, calcium silicate, zirconium silicate , A single composition containing 50% or more of one or more components selected from aluminum oxide and having an average particle size of 0.005 to 200 μm, or zirconium phosphate, phosphoric acid A single composition containing 70% or more of at least one component selected from titanium, calcium phosphate, zirconium oxide, zirconium oxide hydrate, copper oxide, and silver oxide, and having an average particle size of 0.005 to 200 μm, Or one or more selected from the group consisting of hydrotalcites, synthetic titanium oxide, mica, silica-coated titanium oxide, silica-coated zinc oxide, apatite-coated titanium oxide, and zinc oxide, with an average particle size of 0. 005-200 μm particles, or mordenite, clinozoite, chabazite, erionite, sepiolite, montmorillonite, bentonite, talc, perlite, activated clay, diatomaceous earth, and particles having an average particle size of 0.005-200 μm There is.
特許文献７（特開２００６−２０７１７号公報）には、膨潤性粘土鉱物のサポナイト、ヘクトライト、ベントナイト、モンモリロナイト、スメクタイト、バーミキュライト、雲母系層状珪酸塩鉱物、カオリン系層状珪酸塩鉱物又はタルク系層状珪酸塩鉱物と酸化チタンとが、同体摩擦粉砕によりナノ化された消臭材であって、銀イオン及び／又は銅イオンを含む消臭剤が記載されている。 Patent Document 7 (Japanese Patent Application Laid-Open No. 2006-20717) discloses swelling clay minerals saponite, hectorite, bentonite, montmorillonite, smectite, vermiculite, mica-based layered silicate mineral, kaolin-based layered silicate mineral, or talc-based layered layer. A deodorizing material in which a silicate mineral and titanium oxide are nano-sized by homogenous friction grinding, and a deodorizing agent containing silver ions and / or copper ions is described.
特許文献８（特許第３１５１７０６号公報）には、一対のノズル手段から噴射される高圧流体噴流同士を互いに衝突させることにより乳化分散流体又は／及び微粒子を得る噴流衝合装置が記載されており、前記第１と第２のノズル手段からの噴流を前記一点の先方で受け止めて噴流の流体力を分散させる噴流受け止め手段として回転自在な硬質ボールの記載がある。 Patent Document 8 (Patent No. 3151706) describes a jet collision device that obtains an emulsified dispersion fluid or / and fine particles by causing high-pressure fluid jets ejected from a pair of nozzle means to collide with each other. There is a description of a rotatable hard ball as jet receiving means for receiving a jet flow from the first and second nozzle means at the tip of the one point and dispersing the fluid force of the jet.
非特許文献１（湿式微粒化装置「スターバースト」によるナノ電子材料の微粒化, 原島謙一，工業調査会，電子材料 ２００８年９月号）には、株式会社スギノマシン製の湿式微粒化装置「スターバースト（装置の商品名）」による電子部品材料の微粒化の事例が記載されている。 Non-patent document 1 (Nanoelectronic material atomization by wet atomization device “Starburst”, Kenichi Harashima, Industrial Research Committee, Electronic Materials September 2008 issue) includes a wet atomization device manufactured by Sugino Machine Co., Ltd. “ An example of atomization of electronic component material by "Starburst (trade name of device)" is described.
しかしながら、銀を鉱物粒子に担持させる方法として上記特許文献に開示されている方法は、銀を鉱物に練り込んで粒子を形成する方法か、イオン交換によって銀をアパタイトに担持させる方法（特許文献２、特許文献４）であり、銀を鉱物に練り込む方法は、粒子の内部に多くの銀が練り込まれてしまい、イオン交換によって銀をアパタイトに担持させる方法は、アパタイトの結晶構造が歪んだり破壊されるために担持された銀が脱落し易い。そのため、鉱物粒子の表層に出ている銀活性面が少なくなってしまい、高価な銀を多く使用しないと抗菌効果が得られず、良質な銀担持鉱物粒子を経済的に製造することが難しいという問題点がある。 However, as a method of supporting silver on mineral particles, the method disclosed in the above-mentioned patent document is a method of kneading silver into mineral to form particles, or a method of supporting silver on apatite by ion exchange (Patent Document 2). 4), a method in which silver is kneaded into a mineral, a large amount of silver is kneaded inside the particles, and a method in which silver is supported on apatite by ion exchange causes distortion of the crystal structure of apatite. Since it is destroyed, the supported silver tends to fall off. Therefore, the silver active surface appearing on the surface layer of the mineral particles is reduced, the antibacterial effect is not obtained unless a lot of expensive silver is used, and it is difficult to economically produce high-quality silver-carrying mineral particles. There is a problem.
また、銀担持鉱物粒子や酸化チタン粒子を微粒化する方法として上記特許文献に開示されている方法は、粉砕媒体を使用した湿式の機械的接触式粉砕（特許文献２では単に湿式粉砕機と記述されている）か、同体摩擦粉砕（特許文献４）である。しかし、機械的接触式粉砕では、粒子自体が壊れる不具合や、粉砕媒体から発生するコンタミが混入する不具合がある。また、同体摩擦粉砕では、粒子自体が壊れる不具合がある。そして、銀担持鉱物粒子や酸化チタン粒子を水に均一に分散した懸濁液とすることが困難であるため、無機分散剤が添加されている（特許文献１、特許文献２）。しかし、無機分散剤を添加することで、触媒活性度の低下が懸念される。なお、特許文献４と５は、酸化チタン皮膜を形成するための方法であるから、粒子の微粒化とはその目的や構成が大きく異なる。
In addition, as a method for atomizing silver-carrying mineral particles and titanium oxide particles, the method disclosed in the above patent document is a wet mechanical contact type pulverization using a pulverization medium (described in Patent Document 2 as simply a wet pulverizer). Or the same body friction pulverization (Patent Document 4). However, the mechanical contact type pulverization has a problem that the particles themselves are broken and a problem that contamination generated from the pulverization medium is mixed. Moreover, in the same body friction grinding | pulverization, there exists a malfunction which particle | grains break. And since it is difficult to make it the suspension which disperse | distributed the silver carrying mineral particle | grains and the titanium oxide particle uniformly in water, the inorganic dispersing agent is added (patent document 1, patent document 2). However, there is a concern about the decrease in catalyst activity by adding an inorganic dispersant. Since
従来の光触媒コーティング液では、銀を担持する担体としてアパタイトが用いられている（特許文献３、特許文献６）。これは、吸着力（付着力）の強いアパタイトを用いることで、繊維等の対象物に固着させて剥がれ難くさせるという考え方に基づいている。
しかし、本発明者らは鋭意研究の結果、アパタイトは、銀を担持する担体として好ましくない場合があることが判明した。つまり、アパタイトは衣料の繊維に固着すると剥がれ難い性質があるが、銀や酸化チタンはクリーニング（ドライクリーニング）によって洗い流され易いため、クリーニング後は、抗菌作用や消臭作用のないアパタイトが衣料に残ることとなる。銀や酸化チタンが洗い流された衣料は、残ったアパタイトが老廃物等を吸着するため臭いが発生し易くなる。またアパタイトを使用した触媒コーティング液を繰り返し衣料に塗布すると、アパタイトの蓄積によって衣料が硬くこわばってしまい、着心地が悪くなってしまうという問題点を発見した。つまり、光触媒コーティング液をクリーニングによって除去したい場合には、アパタイトが銀担持鉱物粒子として適していないという新たな課題がみつかったのである。
In the conventional photocatalyst coating liquid, apatite is used as a carrier for supporting silver (
However, as a result of intensive studies, the present inventors have found that apatite may not be preferable as a carrier supporting silver. In other words, apatite has the property that it is difficult to peel off when it adheres to the fiber of clothing, but silver and titanium oxide are easily washed away by cleaning (dry cleaning), so after cleaning, apatite that has no antibacterial or deodorizing action remains in the clothing. It will be. In clothing from which silver or titanium oxide has been washed away, the remaining apatite adsorbs wastes and the like, so that odor is likely to occur. In addition, when a catalyst coating solution using apatite was repeatedly applied to clothing, it was found that the clothing became hard and stiff due to accumulation of apatite, resulting in poor comfort. That is, when the photocatalyst coating liquid is to be removed by cleaning, a new problem has been found that apatite is not suitable as silver-carrying mineral particles.
そこで本発明の目的は、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子と酸化チタン粒子を水に均一に分散させた懸濁液からなる光触媒コーティング液の製造方法、並びに抗菌消臭ドライクリーニング用コーティング液及び光触媒加工衣料を提供することにある。 Accordingly, an object of the present invention is to uniformly disperse silver-carrying mineral particles and titanium oxide particles in which silver is efficiently carried on the surface layer of mineral particles having an appropriate adsorptive property that adheres to clothing fibers but peels off by cleaning in water. and a method of manufacturing a photocatalytic coating liquid consisting of a suspension, as well as a coating solution and photocatalytic working clothes antibacterial deodorizing dry cleaning.
本発明の光触媒コーティング液の製造方法は、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませた粘土鉱物粒子を、硝酸銀と置換反応させて当該粘土鉱物粒子の表層に銀化合物を生成し、これを焼成温度が４００から５００℃で焼成し粉砕することで前記粘土鉱物粒子の表層に銀を担持させた銀担持鉱物粒子とし、前記銀担持鉱物粒子と酸化チタン粒子をそれぞれ微粒化手段によって微粒化するとともに分散手段によって水に均一に分散させて前記銀担持鉱物粒子と酸化チタン粒子と水との懸濁液を製造することを特徴とする。 The method for producing a photocatalyst coating liquid according to the present invention includes a clay mineral particle soaked with an aqueous sodium hydrogen carbonate solution or an aqueous sodium carbonate solution, and a silver nitrate is formed on the surface layer of the clay mineral particle by substitution reaction with silver nitrate. Is calcined at a firing temperature of 400 to 500 ° C. and pulverized to form silver-carrying mineral particles in which silver is supported on the surface layer of the clay mineral particles, and the silver-carrying mineral particles and titanium oxide particles are each atomized by atomization means. In addition, a suspension of the silver-carrying mineral particles, titanium oxide particles, and water is produced by uniformly dispersing in water by a dispersing means.
粘土鉱物粒子は、適度な吸着性を持つ。炭酸水素ナトリウム又は炭酸ナトリウムと、硝酸銀との置換反応によれば有害ガスが発生することがない。本発明によれば、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませた粘土鉱物粒子を、硝酸銀と置換反応させて当該粘土鉱物粒子の表層に銀化合物を生成し、これを所定の焼成温度で焼成し粉砕することで前記粘土鉱物粒子の表層に銀を担持させた銀担持鉱物粒子とするので、適度な吸着性を持つ粘土鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子とすることができる。そして、前記銀担持鉱物粒子と酸化チタン粒子をそれぞれ微粒化手段によって微粒化するとともに分散手段によって水に均一に分散させて前記銀担持鉱物粒子と酸化チタン粒子と水との懸濁液を製造する。前記微粒化手段としては、例えば同体摩擦粉砕が挙げられる。前記分散手段としては、例えば無機分散剤の添加が挙げられる。 Clay mineral particles have moderate adsorptivity. According to the substitution reaction between sodium hydrogen carbonate or sodium carbonate and silver nitrate, no harmful gas is generated. According to the present invention, a clay mineral particle soaked with a sodium hydrogen carbonate aqueous solution or a sodium carbonate aqueous solution is subjected to a substitution reaction with silver nitrate to produce a silver compound on the surface layer of the clay mineral particle, which is subjected to a predetermined firing temperature. The silver-carrying mineral particles in which silver is supported on the surface layer of the clay mineral particles by firing and pulverizing with the above, the silver-carrying mineral particles in which silver is efficiently supported on the surface layer of the clay mineral particles having moderate adsorptivity It can be. Then, the silver-carrying mineral particles and the titanium oxide particles are each atomized by the atomizing means and uniformly dispersed in water by the dispersing means to produce a suspension of the silver-carrying mineral particles, titanium oxide particles, and water. . Examples of the atomization means include in-body friction pulverization. Examples of the dispersing means include addition of an inorganic dispersant.
本発明の光触媒コーティング液の製造方法は、前記焼成温度が４００から５００℃であることを特徴とする。
前記粘土鉱物粒子上に吸着保持された炭酸水素ナトリウム（ＮａＨＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応により重炭酸銀（ＡｇＨＣＯ３）が生成される。重炭酸銀（ＡｇＨＣＯ３）が生成された前記粘土鉱物粒子を約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって水蒸気（Ｈ２Ｏ）と炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。
また、前記粘土鉱物粒子上に吸着保持された炭酸ナトリウム（Ｎａ２ＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応により炭酸銀（Ａｇ２ＣＯ３）が生成される。炭酸銀（Ａｇ２ＣＯ３）が生成された前記粘土鉱物粒子を約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。
そして、酸化銀（Ａｇ２Ｏ）が形成された前記粘土鉱物粒子を４００から５００℃の温度で焼成する。酸化銀（Ａｇ２Ｏ）を４００から５００℃の温度で加熱することで酸素（Ｏ２）が放出されて前記粘土鉱物粒子の表層に銀（Ａｇ）が担持された銀担持鉱物粒子となる。そして好ましくは前記焼成温度が４４０から４５０℃であり、さらに好ましくは前記焼成温度が４４２から４４４℃である。なお、上記化学反応過程について、発明を実施するための形態にてその詳細を説明する。
The method for producing a photocatalyst coating liquid of the present invention is characterized in that the baking temperature is 400 to 500 ° C.
Silver bicarbonate (AgHCO 3 ) is produced by a substitution reaction between sodium bicarbonate (NaHCO 3 ) adsorbed and held on the clay mineral particles and silver nitrate (AgNO 3 ). When the clay mineral particles in which silver bicarbonate (AgHCO 3 ) is produced are dried at a temperature of about 120 ° C. and heated at a temperature of about 200 ° C., water vapor (H 2 O) and carbon dioxide (CO 2 ) are produced by a thermal decomposition reaction. ) Is released to form silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles.
Further, silver carbonate (Ag 2 CO 3 ) is generated by a substitution reaction between sodium carbonate (Na 2 CO 3 ) adsorbed and held on the clay mineral particles and silver nitrate (AgNO 3 ). When the clay mineral particles in which silver carbonate (Ag 2 CO 3 ) is produced are dried at a temperature of about 120 ° C. and heated at a temperature of about 200 ° C., carbon dioxide gas (CO 2 ) is released by a thermal decomposition reaction, Silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles can be formed.
Then, the clay mineral particles on which silver oxide (Ag 2 O) is formed are fired at a temperature of 400 to 500 ° C. By heating silver oxide (Ag 2 O) at a temperature of 400 to 500 ° C., oxygen (O 2 ) is released to form silver-carrying mineral particles in which silver (Ag) is supported on the surface layer of the clay mineral particles. And preferably the said calcination temperature is 440 to 450 degreeC, More preferably, the said calcination temperature is 442 to 444 degreeC. The chemical reaction process will be described in detail in the form for carrying out the invention.
本発明の光触媒コーティング液の製造方法は、前記懸濁液に紫外線を照射することを特徴とする。
本発明によれば、前記懸濁液に紫外線を照射することで、前記焼成の過程で、充分熱の行き渡らない場所の前記粘土鉱物粒子、言い換えると所定の焼成温度に達していない場所の前記粘土鉱物粒子の表層で残留していた酸化銀（Ａｇ２Ｏ）を銀（Ａｇ）に還元できる。
The method for producing a photocatalyst coating liquid of the present invention is characterized in that the suspension is irradiated with ultraviolet rays.
According to the present invention, by irradiating the suspension with ultraviolet rays, the clay mineral particles in a place where heat is not sufficiently distributed in the firing process, in other words, the clay in a place where the predetermined firing temperature is not reached. Silver oxide (Ag 2 O) remaining on the surface layer of mineral particles can be reduced to silver (Ag).
本発明の光触媒コーティング液の製造方法は、前記微粒化手段及び前記分散手段を湿式微粒化装置が兼用しており、前記銀担持鉱物粒子と水との混合液と、前記酸化チタン粒子と水との混合液を、それぞれ前記湿式微粒化装置のチャンバーノズルからの圧力を３０から２４５ＭＰａの間で調整し高圧噴射することで微粒化するとともに水に均一に分散させることを特徴とする。 In the method for producing a photocatalyst coating liquid of the present invention, the atomization means and the dispersion means are also used by a wet atomization apparatus, and a mixed liquid of the silver-carrying mineral particles and water, the titanium oxide particles and water, The liquid mixture is atomized by adjusting the pressure from the chamber nozzle of the wet atomization apparatus between 30 and 245 MPa and spraying at high pressure, and is uniformly dispersed in water.
前記微粒化手段として同体摩擦粉砕を適用した場合には、粒子自体が壊れる危険がある。前記分散手段として無機分散剤を添加した場合には、触媒活性度しかし、無機分散剤を添加することで、触媒活性度の低下が懸念される。
本発明によれば、前記微粒化手段及び前記分散手段を湿式微粒化装置が兼用しており、前記銀担持鉱物粒子と水との混合液と、前記酸化チタン粒子と水との混合液を、それぞれ前記湿式微粒化装置のチャンバーノズルから所定の圧力で高圧噴射することで微粒化するとともに水に均一に分散させるので、粒子自体を壊さずコンタミの混入がない状態で、前記銀担持鉱物粒子と前記酸化チタン粒子をそれぞれ別個に微粒化し、水に均一に分散させる。したがって、無機分散剤を添加することが不要であり、触媒活性度を低下させ難い。
When the same body friction pulverization is applied as the atomizing means, there is a risk that the particles themselves are broken. When an inorganic dispersant is added as the dispersing means, catalyst activity, however, there is a concern that catalyst activity may be reduced by adding an inorganic dispersant.
According to the present invention, the atomization means and the dispersion means are also used in a wet atomization apparatus, the mixture liquid of the silver-supporting mineral particles and water, and the mixture liquid of the titanium oxide particles and water, Each of the silver-carrying mineral particles is atomized by high-pressure jetting at a predetermined pressure from the chamber nozzle of the wet atomization apparatus and uniformly dispersed in water, so that the particles themselves are not broken and contaminated. The titanium oxide particles are atomized separately and uniformly dispersed in water. Therefore, it is not necessary to add an inorganic dispersant and it is difficult to reduce the catalyst activity.
本発明の光触媒コーティング液の製造方法は、前記銀担持鉱物粒子と水との混合液を前記湿式微粒化装置によって第１の懸濁液とし、前記酸化チタン粒子と水との混合液を前記湿式微粒化装置によって第２の懸濁液とし、前記銀担持鉱物粒子のメジアン粒径と前記酸化チタン粒子のメジアン粒径とを異ならせ、前記第１の懸濁液と第２の懸濁液を所定比率で調合することを特徴とする。 In the method for producing a photocatalyst coating liquid of the present invention, a mixed liquid of the silver-carrying mineral particles and water is made into a first suspension by the wet atomization apparatus, and a mixed liquid of the titanium oxide particles and water is used as the wet liquid. A second suspension is obtained by a pulverization apparatus, the median particle diameter of the silver-carrying mineral particles and the median particle diameter of the titanium oxide particles are made different, and the first suspension and the second suspension are It mix | blends by a predetermined ratio, It is characterized by the above-mentioned.
本発明によれば、前記銀担持鉱物粒子と水との混合液を前記湿式微粒化装置によって第１の懸濁液とし、前記酸化チタン粒子と水との混合液を前記湿式微粒化装置によって第２の懸濁液とし、前記銀担持鉱物粒子のメジアン粒径と前記酸化チタン粒子のメジアン粒径とを異ならせ、前記第１の懸濁液と第２の懸濁液を所定比率で調合することで、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が効果的に発揮される。そして、前記第１の懸濁液と第２の懸濁液を所定比率で調合することで、銀の抗菌効果と酸化チタンの消臭効果の性能を適宜調整することができる。このようにして得られた前記懸濁液は、密封容器に入れて長期間（およそ１ヶ月間）放置した状態でも均一な分散状態を維持する。 According to the present invention, the liquid mixture of the silver-carrying mineral particles and water is made into the first suspension by the wet atomization apparatus, and the liquid mixture of the titanium oxide particles and water is changed by the wet atomization apparatus. 2, the median particle size of the silver-carrying mineral particles and the median particle size of the titanium oxide particles are made different, and the first suspension and the second suspension are prepared at a predetermined ratio. Thus, the silver-carrying mineral particles and the titanium oxide particles hardly overlap each other, and the antibacterial action of silver and the deodorizing action of titanium oxide are effectively exhibited. And the performance of the antibacterial effect of silver and the deodorizing effect of titanium oxide can be appropriately adjusted by blending the first suspension and the second suspension at a predetermined ratio. The suspension thus obtained maintains a uniform dispersion state even when left in a sealed container for a long period (approximately one month).
本発明の光触媒コーティング液の製造方法は、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径が７から９００ｎｍの範囲であり、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲となるよう前記湿式微粒化装置のチャンバーノズルからの圧力を調整し高圧噴射する作業を１回行うか又は複数回繰り返すことを特徴とする。 The method for producing a photocatalyst coating liquid of the present invention is such that the median particle size of the silver-carrying mineral particles and the titanium oxide particles is in the range of 7 to 900 nm, and the median particle size of the silver-carrying mineral particles is the median of the titanium oxide particles. and repeating or more times to adjust the pressure from the chamber nozzle of the wet atomization apparatus to be a range of 10 times 2 times the particle size carried out once the task of high-pressure injection.
本発明によれば、前記湿式微粒化装置のチャンバーノズルからの圧力を３０から２４５ＭＰａの間で調整することで、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径を７から９００ｎｍの範囲とし、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲とするので、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される。 According to the present invention, the median particle size of the silver-carrying mineral particles and the titanium oxide particles is in the range of 7 to 900 nm by adjusting the pressure from the chamber nozzle of the wet atomization apparatus between 30 and 245 MPa. Since the median particle size of the silver-carrying mineral particles is in the range of 2 to 10 times the median particle size of the titanium oxide particles, the silver-carrying mineral particles and the titanium oxide particles hardly overlap each other. Antibacterial action and deodorizing action of titanium oxide are fully exhibited.
本発明によれば、前記湿式微粒化装置のチャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を複数回繰り返すことで、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径を７から９００ｎｍの範囲とした上で粒径のばらつきを抑え、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲とするので、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される。前記湿式微粒化装置のチャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を繰り返す回数が多くなるに従って前記銀担持鉱物粒子（又は前記酸化チタン粒子）の粒径のばらつきが小さくなる。 According to the present invention, the median particle size of the silver-carrying mineral particles and the titanium oxide particles is set to 7 by repeating the operation of high-pressure injection of the mixed liquid at a predetermined pressure from the chamber nozzle of the wet atomizer. In addition, the dispersion of the particle size is suppressed in the range of 900 nm to 900 nm, and the median particle size of the silver-carrying mineral particles is in the range of 2 to 10 times the median particle size of the titanium oxide particles. And titanium oxide particles hardly overlap each other, and the antibacterial action of silver and the deodorizing action of titanium oxide are sufficiently exhibited. As the number of repetitions of the operation of high-pressure spraying the mixed liquid at a predetermined pressure from the chamber nozzle of the wet atomization apparatus increases, the variation in the particle diameter of the silver-supporting mineral particles (or the titanium oxide particles) decreases.
本発明によって得られた抗菌消臭用の光触媒コーティング液は、置換反応によって粘土鉱物からなる粒子の表層に銀を担持させた銀担持鉱物粒子と水との混合液と、酸化チタン粒子と水との混合液を、チャンバーノズルからの圧力を３０から２４５ＭＰａの間で調整し高圧噴射する湿式微粒化装置によって微粒化するとともに水に均一に分散させた銀担持鉱物粒子と酸化チタン粒子の懸濁液であって、前記粘土鉱物が、カオリナイト、ハロイサイト、スメクタイト、ベントナイト、雲母、バーミキュライト、緑泥石、モンモリロナイト、活性白土、シリカ、シリカゲル、アルミナゲル、珪藻土のうちいずれか１種、若しくは２種以上からなり、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径が７から９００ｎｍの範囲であり、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲である。そして好ましくは、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の５倍から１０倍の範囲であり、さらに好ましくは、前記銀担持鉱物粒子のメジアン粒径が約９００ｎｍであり、前記酸化チタン粒子のメジアン粒径が約９０ｎｍである。 The photocatalytic coating liquid for antibacterial deodorization obtained by the present invention is a mixed liquid of silver-carrying mineral particles and water in which silver is supported on the surface layer of particles made of clay mineral by a substitution reaction, titanium oxide particles and water, A suspension of silver-carrying mineral particles and titanium oxide particles in which the mixture liquid is atomized by a wet atomization apparatus that adjusts the pressure from the chamber nozzle between 30 to 245 MPa and sprayed at a high pressure and is uniformly dispersed in water. The clay mineral is any one or more of kaolinite, halloysite, smectite, bentonite, mica, vermiculite, chlorite, montmorillonite, activated clay, silica, silica gel, alumina gel, diatomaceous earth. The median particle size of the silver-carrying mineral particles and the titanium oxide particles is in the range of 7 to 900 nm, Median particle size of the carrier mineral particles is in the range from 10 times 2 times the median particle size of the titanium oxide particles. Preferably, the median particle size of the silver-carrying mineral particles is in the range of 5 to 10 times the median particle size of the titanium oxide particles, and more preferably, the median particle size of the silver-carrying mineral particles is about 900 nm. The median particle size of the titanium oxide particles is about 90 nm.
本発明によれば、粘土鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子と、酸化チタン粒子をそれぞれ微粒化して、無機分散剤を添加せずに水に均一に分散させた懸濁液であって、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される懸濁液となり、製造コストも抑えられる。 According to the present invention, the silver-carrying mineral particles that efficiently carry silver on the surface of the clay mineral particles and the titanium oxide particles are each atomized and dispersed uniformly in water without adding an inorganic dispersant. It is a turbid liquid, the silver-supporting mineral particles and the titanium oxide particles hardly overlap each other, and it becomes a suspension that sufficiently exhibits the antibacterial action of silver and the deodorizing action of titanium oxide, and the production cost can be reduced. .
これら本発明に係る前記粘土鉱物としては、カオリナイト、ハロイサイト、スメクタイト、ベントナイト、タルク、雲母、バーミキュライト、緑泥石、モンモリロナイト、活性白土、シリカ、シリカゲル、アルミナゲル、ゼオライト、珪藻土のうちいずれか１種、若しくは２種以上からなる粘土鉱物が適用される。 These clay minerals according to the present invention include any one of kaolinite, halloysite, smectite, bentonite, talc, mica, vermiculite, chlorite, montmorillonite, activated clay, silica, silica gel, alumina gel, zeolite, and diatomaceous earth. Alternatively, a clay mineral composed of two or more kinds is applied.
これらの前記粘土鉱物はアパタイトよりも吸着性が弱いが適度な吸着性があり、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する。そして、これら前記粘土鉱物は膨潤性を有するため、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませることが容易である。前記粘土鉱物の中では、特にスメクタイト、ベントナイト、モンモリロナイト、活性白土、シリカゲル、アルミナゲルが好ましい。前記懸濁液が薄い白色（又は薄い乳白色）となるので、衣料に塗布したときに目立たず、特にワイシャツやシーツなどの白色の衣料の外観を損ねることがない。 These clay minerals are moderately adsorbable but less adsorbable than apatite, and have moderate adsorbability that adheres to clothing fibers but peels off by cleaning. And since the said clay mineral has swelling property, it is easy to immerse the sodium hydrogencarbonate aqueous solution or the sodium carbonate aqueous solution. Among the clay minerals, smectite, bentonite, montmorillonite, activated clay, silica gel, and alumina gel are particularly preferable. Since the suspension becomes light white (or light milky white), it does not stand out when applied to clothing, and in particular, the appearance of white clothing such as shirts and sheets is not impaired.
本発明によって得られた光触媒コーティング液を抗菌消臭ドライクリーニング用コーティング液とし、また、当該抗菌消臭ドライクリーニング用コーティング液を衣料にスプレー塗布して前記銀担持鉱物粒子及び前記酸化チタン粒子を前記衣料の繊維に付着させた光触媒加工衣料とすることで、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子と酸化チタン粒子を微粒化して、無機分散剤を添加せずに水に均一に分散させた懸濁液からなる抗菌消臭ドライクリーニング用コーティング液及び光触媒加工衣料が実現する。 The photocatalyst coating liquid obtained by the present invention is used as an antibacterial deodorant dry cleaning coating liquid, and the antibacterial deodorant dry cleaning coating liquid is spray-applied on clothing to provide the silver-carrying mineral particles and the titanium oxide particles as described above. By making photocatalyst-treated garments attached to clothing fibers, silver-carrying mineral particles and titanium oxide that efficiently carry silver on the surface of the mineral particles that adhere to clothing fibers but have suitable adsorptive properties that peel off by cleaning A coating liquid for antibacterial deodorizing and dry cleaning and a photocatalyst-processed garment comprising a suspension in which particles are atomized and uniformly dispersed in water without adding an inorganic dispersant are realized.
本発明によれば、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませた粘土鉱物粒子を、硝酸銀と置換反応させて当該粘土鉱物粒子の表層に銀化合物を生成し、これを所定の焼成温度で焼成し粉砕することで前記粘土鉱物粒子の表層に銀を担持させた銀担持鉱物粒子とするので、適度な吸着性を持つ粘土鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子とすることができる。そして、前記銀担持鉱物粒子と酸化チタン粒子をそれぞれ微粒化手段によって微粒化するとともに分散手段によって水に均一に分散させて前記銀担持鉱物粒子と酸化チタン粒子と水との懸濁液を製造する。 According to the present invention, a clay mineral particle soaked with a sodium hydrogen carbonate aqueous solution or a sodium carbonate aqueous solution is subjected to a substitution reaction with silver nitrate to produce a silver compound on the surface layer of the clay mineral particle, which is subjected to a predetermined firing temperature. The silver-carrying mineral particles in which silver is supported on the surface layer of the clay mineral particles by firing and pulverizing with the above, the silver-carrying mineral particles in which silver is efficiently supported on the surface layer of the clay mineral particles having an appropriate adsorptivity It can be. Then, the silver-carrying mineral particles and the titanium oxide particles are each atomized by the atomizing means and uniformly dispersed in water by the dispersing means to produce a suspension of the silver-carrying mineral particles, titanium oxide particles, and water. .
前記粘土鉱物粒子上に吸着保持された炭酸水素ナトリウム（ＮａＨＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応により重炭酸銀（ＡｇＨＣＯ３）が生成される。重炭酸銀（ＡｇＨＣＯ３）が生成された前記粘土鉱物粒子を約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって水蒸気（Ｈ２Ｏ）と炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。
また、前記粘土鉱物粒子上に吸着保持された炭酸ナトリウム（Ｎａ２ＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応により炭酸銀（Ａｇ２ＣＯ３）が生成される。炭酸銀（Ａｇ２ＣＯ３）が生成された前記粘土鉱物粒子を約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。
そして、酸化銀（Ａｇ２Ｏ）が形成された前記粘土鉱物粒子を４００から５００℃の温度で焼成する。酸化銀（Ａｇ２Ｏ）を４００から５００℃の温度で加熱することで酸素（Ｏ２）が放出されて前記粘土鉱物粒子の表層に銀（Ａｇ）が担持された銀担持鉱物粒子となる。
本発明によれば、前記懸濁液に紫外線を照射することで、前記焼成の過程で、充分熱の行き渡らない場所の前記粘土鉱物粒子、言い換えると所定の焼成温度に達していない場所の前記粘土鉱物粒子の表層で残留していた酸化銀（Ａｇ２Ｏ）を銀（Ａｇ）に還元できる。
Silver bicarbonate (AgHCO 3 ) is produced by a substitution reaction between sodium bicarbonate (NaHCO 3 ) adsorbed and held on the clay mineral particles and silver nitrate (AgNO 3 ). When the clay mineral particles in which silver bicarbonate (AgHCO 3 ) is produced are dried at a temperature of about 120 ° C. and heated at a temperature of about 200 ° C., water vapor (H 2 O) and carbon dioxide (CO 2 ) are produced by a thermal decomposition reaction. ) Is released to form silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles.
Further, silver carbonate (Ag 2 CO 3 ) is generated by a substitution reaction between sodium carbonate (Na 2 CO 3 ) adsorbed and held on the clay mineral particles and silver nitrate (AgNO 3 ). When the clay mineral particles in which silver carbonate (Ag 2 CO 3 ) is produced are dried at a temperature of about 120 ° C. and heated at a temperature of about 200 ° C., carbon dioxide gas (CO 2 ) is released by a thermal decomposition reaction, Silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles can be formed.
Then, the clay mineral particles on which silver oxide (Ag 2 O) is formed are fired at a temperature of 400 to 500 ° C. By heating silver oxide (Ag 2 O) at a temperature of 400 to 500 ° C., oxygen (O 2 ) is released to form silver-carrying mineral particles in which silver (Ag) is supported on the surface layer of the clay mineral particles.
According to the present invention, by irradiating the suspension with ultraviolet rays, the clay mineral particles in a place where heat is not sufficiently distributed in the firing process, in other words, the clay in a place where the predetermined firing temperature is not reached. Silver oxide (Ag 2 O) remaining on the surface layer of mineral particles can be reduced to silver (Ag).
本発明によれば、前記微粒化手段及び前記分散手段を湿式微粒化装置が兼用しており、前記銀担持鉱物粒子と水との混合液と、前記酸化チタン粒子と水との混合液を、それぞれ前記湿式微粒化装置のチャンバーノズルから所定の圧力で高圧噴射することで微粒化するとともに水に均一に分散させるので、粒子自体を壊さずコンタミの混入がない状態で、前記銀担持鉱物粒子と前記酸化チタン粒子をそれぞれ別個に微粒化し、水に均一に分散させる。したがって、無機分散剤を添加することが不要であり、触媒活性度を低下させ難い。
本発明によれば、前記銀担持鉱物粒子と水との混合液を前記湿式微粒化装置によって第１の懸濁液とし、前記酸化チタン粒子と水との混合液を前記湿式微粒化装置によって第２の懸濁液とし、前記銀担持鉱物粒子のメジアン粒径と前記酸化チタン粒子のメジアン粒径とを異ならせ、前記第１の懸濁液と第２の懸濁液を所定比率で調合することで、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が効果的に発揮される。そして、前記第１の懸濁液と第２の懸濁液を所定比率で調合することで、銀の抗菌効果と酸化チタンの消臭効果の性能を適宜調整することができる。このようにして得られた前記懸濁液は、密封容器に入れて長期間（およそ１ヶ月間）放置した状態でも均一な分散状態を維持する。
本発明によれば、前記湿式微粒化装置のチャンバーノズルからの圧力を３０から２４５ＭＰａの間で調整することで、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径を７から９００ｎｍの範囲とし、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲とするので、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される。
本発明によれば、前記湿式微粒化装置のチャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を複数回繰り返すことで、前記銀担持鉱物粒子と前記酸化チタン粒子のメジアン粒径を７から９００ｎｍの範囲とした上で粒径のばらつきを抑え、前記銀担持鉱物粒子のメジアン粒径が前記酸化チタン粒子のメジアン粒径の２倍から１０倍の範囲とするので、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される。前記湿式微粒化装置のチャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を繰り返す回数が多くなるに従って前記銀担持鉱物粒子（又は前記酸化チタン粒子）の粒径のばらつきが小さくなる。
According to the present invention, the atomization means and the dispersion means are also used in a wet atomization apparatus, the mixture liquid of the silver-supporting mineral particles and water, and the mixture liquid of the titanium oxide particles and water, Each of the silver-carrying mineral particles and the silver-carrying mineral particles are in a state where they are atomized by high-pressure jetting from a chamber nozzle of the wet-type atomization apparatus at a predetermined pressure and are uniformly dispersed in water. The titanium oxide particles are atomized separately and uniformly dispersed in water. Therefore, it is not necessary to add an inorganic dispersant and it is difficult to reduce the catalyst activity.
According to the present invention, the liquid mixture of the silver-carrying mineral particles and water is made into the first suspension by the wet atomization apparatus, and the liquid mixture of the titanium oxide particles and water is changed by the wet atomization apparatus. 2, the median particle size of the silver-carrying mineral particles and the median particle size of the titanium oxide particles are made different, and the first suspension and the second suspension are prepared at a predetermined ratio. Thus, the silver-carrying mineral particles and the titanium oxide particles hardly overlap each other, and the antibacterial action of silver and the deodorizing action of titanium oxide are effectively exhibited. And the performance of the antibacterial effect of silver and the deodorizing effect of titanium oxide can be appropriately adjusted by blending the first suspension and the second suspension at a predetermined ratio. The suspension thus obtained maintains a uniform dispersion state even when left in a sealed container for a long period (approximately one month).
According to the present invention, the median particle size of the silver-carrying mineral particles and the titanium oxide particles is in the range of 7 to 900 nm by adjusting the pressure from the chamber nozzle of the wet atomization apparatus between 30 and 245 MPa. Since the median particle size of the silver-carrying mineral particles is in the range of 2 to 10 times the median particle size of the titanium oxide particles, the silver-carrying mineral particles and the titanium oxide particles hardly overlap each other. Antibacterial action and deodorizing action of titanium oxide are fully exhibited.
According to the present invention, the median particle size of the silver-carrying mineral particles and the titanium oxide particles is set to 7 by repeating the operation of high-pressure injection of the mixed liquid at a predetermined pressure from the chamber nozzle of the wet atomization apparatus. And the dispersion of the particle size is suppressed, and the median particle size of the silver-carrying mineral particles is in the range of 2 to 10 times the median particle size of the titanium oxide particles. And titanium oxide particles hardly overlap each other, and the antibacterial action of silver and the deodorizing action of titanium oxide are sufficiently exhibited. As the number of repetitions of the operation of high-pressure spraying the mixed liquid at a predetermined pressure from the chamber nozzle of the wet atomization apparatus increases, the variation in the particle diameter of the silver-supporting mineral particles (or the titanium oxide particles) decreases.
本発明によれば、粘土鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子と、酸化チタン粒子をそれぞれ微粒化して、無機分散剤を添加せずに水に均一に分散させた懸濁液であって、前記銀担持鉱物粒子と酸化チタン粒子とが重なり合うことが殆どなく、銀の抗菌作用と酸化チタンの消臭作用が十分に発揮される懸濁液となり、製造コストも抑えられる。 According to the present invention, the silver-carrying mineral particles that efficiently carry silver on the surface of the clay mineral particles and the titanium oxide particles are each atomized and dispersed uniformly in water without adding an inorganic dispersant. It is a turbid liquid, the silver-supporting mineral particles and the titanium oxide particles hardly overlap each other, and it becomes a suspension that sufficiently exhibits the antibacterial action of silver and the deodorizing action of titanium oxide, and the production cost can be reduced. .
これら本発明に係る前記粘土鉱物としては、カオリナイト、ハロイサイト、スメクタイト、ベントナイト、タルク、雲母、バーミキュライト、緑泥石、モンモリロナイト、活性白土、シリカ、シリカゲル、アルミナゲル、ゼオライト、珪藻土のうちいずれか１種、若しくは２種以上からなる粘土鉱物が適用される。
これらの前記粘土鉱物はアパタイトよりも吸着性が弱いが適度な吸着性があり、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する。そして、これら前記粘土鉱物は膨潤性を有するため、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませることが容易である。前記粘土鉱物の中では、特にスメクタイト、ベントナイト、モンモリロナイト、活性白土、シリカゲル、アルミナゲルが好ましい。前記懸濁液が薄い白色（又は薄い乳白色）となるので、衣料に塗布したときに目立たず、特にワイシャツやシーツなどの白色の衣料の外観を損ねることがない。
These clay minerals according to the present invention include any one of kaolinite, halloysite, smectite, bentonite, talc, mica, vermiculite, chlorite, montmorillonite, activated clay, silica, silica gel, alumina gel, zeolite, and diatomaceous earth. Alternatively, a clay mineral composed of two or more kinds is applied.
These clay minerals are moderately adsorbable but less adsorbable than apatite, and have moderate adsorbability that adheres to clothing fibers but peels off by cleaning. And since the said clay mineral has swelling property, it is easy to immerse the sodium hydrogencarbonate aqueous solution or the sodium carbonate aqueous solution. Among the clay minerals, smectite, bentonite, montmorillonite, activated clay, silica gel, and alumina gel are particularly preferable. Since the suspension becomes light white (or light milky white), it does not stand out when applied to clothing, and in particular, the appearance of white clothing such as shirts and sheets is not impaired.
本発明によって得られた光触媒コーティング液を抗菌消臭ドライクリーニング用コーティング液とし、また、当該抗菌消臭ドライクリーニング用コーティング液を衣料にスプレー塗布して前記銀担持鉱物粒子及び前記酸化チタン粒子を前記衣料の繊維に付着させた光触媒加工衣料とすることで、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する鉱物粒子の表層に効率良く銀を担持させた銀担持鉱物粒子と酸化チタン粒子を微粒化して、無機分散剤を添加せずに水に均一に分散させた懸濁液からなる抗菌消臭ドライクリーニング用コーティング液及び光触媒加工衣料が実現する。 The photocatalyst coating liquid obtained by the present invention is used as an antibacterial deodorant dry cleaning coating liquid, and the antibacterial deodorant dry cleaning coating liquid is spray-applied to clothing to provide the silver-supporting mineral particles and the titanium oxide particles as described above. Silver supported mineral particles and titanium oxide that efficiently carry silver on the surface layer of mineral particles that have moderate adsorbability that adheres to clothing fibers but peels off by cleaning by making photocatalyst-treated clothing attached to clothing fibers A coating liquid for antibacterial deodorizing and dry cleaning and a photocatalyst-processed garment comprising a suspension in which particles are atomized and uniformly dispersed in water without adding an inorganic dispersant are realized.
以下、本発明を実施するための最良の形態を説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
図１は、本発明を適用した実施形態の光触媒コーティング液の製造手順を示す製造工程フロー図である。図１のステップＳ１からステップＳ９は、本発明に係る銀担持鉱物粒子の製造工程を示しており、図１のステップＳ１０からステップＳ１４は、本発明に係る懸濁液の製造工程を示している。 FIG. 1 is a manufacturing process flow chart showing a manufacturing procedure of a photocatalyst coating liquid according to an embodiment to which the present invention is applied. Steps S1 to S9 in FIG. 1 show a process for producing silver-carrying mineral particles according to the present invention, and steps S10 to S14 in FIG. 1 show a process for producing a suspension according to the present invention. .
（本発明に係る銀担持鉱物粒子の製造方法）
本発明に係る銀担持鉱物粒子の製造方法について、以下に説明する。本発明に係る粘土鉱物としては、カオリナイト、ハロイサイト、スメクタイト、ベントナイト、タルク、雲母、バーミキュライト、緑泥石、モンモリロナイト、活性白土、シリカ、シリカゲル、アルミナゲル、珪藻土のうちいずれか１種、若しくは２種以上からなる粘土鉱物が適用される。これら前記粘土鉱物はアパタイトよりも吸着性が弱いが適度な吸着性があり、衣料の繊維に付着するがクリーニングによって剥がれる適度な吸着性を有する。そして、これら前記粘土鉱物は膨潤性を有するため、炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液を浸み込ませることが容易である。前記粘土鉱物の中では、特にスメクタイト、ベントナイト、モンモリロナイト、活性白土、シリカゲル、アルミナゲルが好ましい。前記懸濁液が薄い白色（又は薄い乳白色）となるので、衣料に塗布したときに目立たず、特にワイシャツやシーツなどの白色の衣料の外観を損ねることがない。
(Method for producing silver-carrying mineral particles according to the present invention)
The method for producing silver-carrying mineral particles according to the present invention will be described below. The clay mineral according to the present invention includes any one or two of kaolinite, halloysite, smectite, bentonite, talc, mica, vermiculite, chlorite, montmorillonite, activated clay, silica, silica gel, alumina gel, and diatomaceous earth. The clay mineral consisting of the above is applied. These clay minerals are moderately adsorbable but less adsorbable than apatite, and have moderate adsorbability that adheres to clothing fibers but peels off by cleaning. And since the said clay mineral has swelling property, it is easy to immerse the sodium hydrogencarbonate aqueous solution or the sodium carbonate aqueous solution. Among the clay minerals, smectite, bentonite, montmorillonite, activated clay, silica gel, and alumina gel are particularly preferable. Since the suspension becomes light white (or light milky white), it does not stand out when applied to clothing, and in particular, the appearance of white clothing such as shirts and sheets is not impaired.
図１に示す、本発明に係る銀担持鉱物粒子の製造工程は、容器に炭酸水素ナトリウム水溶液（又は炭酸ナトリウム水溶液）を入れて、粘土鉱物粒子を浸漬する浸漬工程（Ｓ１）と、濾紙等の濾過手段によって液体を濾過する濾過工程（Ｓ２）と、濾過されなかった物質として、炭酸水素ナトリウム水溶液（又は炭酸ナトリウム水溶液）を浸み込ませた粘土鉱物粒子を取り出して別の容器に移す取り出し工程（Ｓ３）と、前記物質に蒸留水を加えて攪拌液とする攪拌工程（Ｓ４）と、硝酸銀水溶液を前記攪拌液の攪拌下で滴下し置換反応させる置換反応工程（Ｓ５）と、液体を濾過する濾過工程（Ｓ６）と、濾過されなかった沈殿物として、重炭酸銀（又は炭酸銀）がその表層に生成された粘土鉱物粒子を取り出して水洗する取り出し工程（Ｓ７）と、沈殿物を焼成する焼成工程（Ｓ８）と、焼成物を粉砕する粉砕工程（Ｓ９）からなる。 The silver-carrying mineral particle production process according to the present invention shown in FIG. 1 includes an immersion process (S1) in which a sodium hydrogen carbonate aqueous solution (or sodium carbonate aqueous solution) is placed in a container and the clay mineral particles are immersed, Filtration step (S2) of filtering the liquid by filtration means, and extraction step of taking out clay mineral particles soaked with sodium hydrogen carbonate aqueous solution (or sodium carbonate aqueous solution) as an unfiltered substance and transferring it to another container (S3), a stirring step (S4) in which distilled water is added to the substance to make a stirring solution, a substitution reaction step (S5) in which a silver nitrate aqueous solution is dropped and stirred under stirring of the stirring solution, and the liquid is filtered Filtration step (S6), and as a precipitate that has not been filtered, silver bicarbonate (or silver carbonate) is taken out and the clay mineral particles produced on its surface are taken out and washed with water (S A) firing step of firing the precipitate and (S8), consists of pulverizing step of pulverizing the fired product (S9).
本発明に係る炭酸水素ナトリウム（ＮａＨＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応について図１に示すフロー図の工程順に説明する。まず前記粘土鉱物粒子を炭酸水素ナトリウム水溶液に浸漬して（Ｓ１）、濾紙等の濾過手段によって液体を濾過すると（Ｓ２）、前記粘土鉱物粒子（例えばスメクタイト）に炭酸水素ナトリウム（ＮａＨＣＯ３）が吸着保持された吸着物質が得られる。次にこの吸着物質を別の容器に移し、蒸留水を加えて（Ｓ４）、攪拌しながら硝酸銀（ＡｇＮＯ３）の水溶液を滴下すると、置換反応によって重炭酸銀（ＡｇＨＣＯ３）と硝酸ナトリウム（ＮａＮＯ３）が生成される（Ｓ５）。このときの化学反応式を（化式１）に記す。 The substitution reaction of sodium hydrogen carbonate (NaHCO 3 ) and silver nitrate (AgNO 3 ) according to the present invention will be described in the order of steps in the flowchart shown in FIG. First, the clay mineral particles are immersed in a sodium hydrogen carbonate aqueous solution (S1), and the liquid is filtered by a filtering means such as filter paper (S2). Then, sodium hydrogen carbonate (NaHCO 3 ) is adsorbed on the clay mineral particles (for example, smectite). A retained adsorbent is obtained. Next, this adsorbed material is transferred to another container, distilled water is added (S4), and an aqueous solution of silver nitrate (AgNO 3 ) is added dropwise with stirring, whereby silver bicarbonate (AgHCO 3 ) and sodium nitrate (NaNO) are added by a substitution reaction. 3 ) is generated (S5). The chemical reaction formula at this time is shown in (Formula 1).
（化式１）
ＡｇＮＯ３ ＋ ＮａＨＣＯ３ → ＡｇＨＣＯ３ ＋ ＮａＮＯ３
(Formula 1)
AgNO 3 + NaHCO 3 → AgHCO 3 + NaNO 3
上記の置換反応は、前記粘土鉱物粒子上に吸着保持された炭酸水素ナトリウム（ＮａＨＣＯ３）あるいは液中の炭酸水素ナトリウム（ＮａＨＣＯ３）と硝酸銀（ＡｇＮＯ３）との反応である。このうち、液中で生じた重炭酸銀（ＡｇＨＣＯ３）の微細粒子は、前記粘土鉱物粒子上に生じた重炭酸銀（ＡｇＨＣＯ３）上にその大部分が移動析出する。 The above substitution reaction, the clay mineral particles sodium hydrogen adsorbed held on (NaHCO 3) or sodium hydrogen carbonate solution (NaHCO 3) and the reaction of silver nitrate (AgNO 3). Among these, most of the fine particles of silver bicarbonate (AgHCO 3 ) generated in the liquid move and precipitate on the silver bicarbonate (AgHCO 3 ) generated on the clay mineral particles.
上記の置換反応（Ｓ５）によって前記粘土鉱物粒子上に重炭酸銀（ＡｇＨＣＯ３）が吸着保持された沈殿物が容器に沈殿するので、濾紙等により液体を濾過して硝酸ナトリウム（ＮａＮＯ３）を除去する（Ｓ６）。そして、濾過されなかった前記沈殿物を取り出して水洗し（Ｓ７）、約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって水蒸気（Ｈ２Ｏ）と炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。このときの化学反応式を（化式２）に記す。 The precipitate in which silver bicarbonate (AgHCO 3 ) is adsorbed and held on the clay mineral particles is precipitated in the container by the above substitution reaction (S5), so the liquid is filtered by filter paper or the like to remove sodium nitrate (NaNO 3 ). Remove (S6). Then, the unfiltered precipitate is taken out, washed with water (S7), dried at a temperature of about 120 ° C., and heated at a temperature of about 200 ° C. When steam (H 2 O) and carbon dioxide ( CO 2 ) is released to form silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles. The chemical reaction formula at this time is shown in (Formula 2).
（化式２）
２ＡｇＨＣＯ３ → Ａｇ２Ｏ ＋ ２ＣＯ２ ＋ Ｈ２Ｏ
(Formula 2)
2AgHCO 3 → Ag 2 O + 2CO 2 + H 2 O
そして、酸化銀（Ａｇ２Ｏ）が形成された前記粘土鉱物粒子を４００から５００℃の温度で焼成する（Ｓ８）。酸化銀（Ａｇ２Ｏ）を４００から５００℃の温度で加熱することで酸素（Ｏ２）が放出されるとともに、前記粘土鉱物粒子（担体）上での体積の急激な減少による微粒化によって、銀（Ａｇ）が微粒子として前記粘土鉱物粒子の表層に担持され固着する。 Then, the clay mineral particles formed with silver oxide (Ag 2 O) are fired at a temperature of 400 to 500 ° C. (S8). By heating silver oxide (Ag 2 O) at a temperature of 400 to 500 ° C., oxygen (O 2 ) is released, and by atomization due to a rapid decrease in volume on the clay mineral particles (support), Silver (Ag) is supported and fixed as fine particles on the surface layer of the clay mineral particles.
前記粘土鉱物粒子の表層に銀が担持され固定された状態で、ボールミル等の粉砕手段によって粉砕する（Ｓ９）。粉砕することで、前記粘土鉱物粒子の表層に銀を担持させ固定させた銀担持鉱物粒子となる。 In a state where silver is supported and fixed on the surface layer of the clay mineral particles, it is pulverized by a pulverizing means such as a ball mill (S9). By pulverizing, silver-carrying mineral particles in which silver is supported and fixed on the surface layer of the clay mineral particles are obtained.
次に、本発明に係る炭酸ナトリウム（Ｎａ２ＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応について図１に示すフロー図の工程順に説明する。まず前記粘土鉱物粒子を炭酸ナトリウム水溶液に浸漬して浸漬して（Ｓ１）、濾紙等の濾過手段によって液体を濾過すると（Ｓ２）、前記粘土鉱物粒子（例えばスメクタイト）に炭酸ナトリウム（Ｎａ２ＣＯ３）が吸着保持された吸着物質が得られる。次にこの吸着物質を別の容器に移し、蒸留水を加えて（Ｓ４）、攪拌しながら硝酸銀（ＡｇＮＯ３）の水溶液を滴下すると、置換反応によって炭酸銀（Ａｇ２ＣＯ３）と硝酸ナトリウム（ＮａＮＯ３）が生成される（Ｓ５）。このときの化学反応式を（化式３）に記す。 Next, the substitution reaction between sodium carbonate (Na 2 CO 3 ) and silver nitrate (AgNO 3 ) according to the present invention will be described in the order of steps in the flowchart shown in FIG. First, the clay mineral particles are immersed in an aqueous sodium carbonate solution (S1), and the liquid is filtered by a filtering means such as filter paper (S2). Then, sodium carbonate (Na 2 CO 3 ) is added to the clay mineral particles (for example, smectite). ) Is adsorbed and retained. Next, this adsorbed material is transferred to another container, distilled water is added (S4), and an aqueous solution of silver nitrate (AgNO 3 ) is added dropwise with stirring, and silver carbonate (Ag 2 CO 3 ) and sodium nitrate ( NaNO 3 ) is generated (S5). The chemical reaction formula at this time is shown in (Formula 3).
（化式３）
２ＡｇＮＯ３ ＋ Ｎａ２ＣＯ３ → Ａｇ２ＣＯ３ ＋ ２ＮａＮＯ３
(Formula 3)
2AgNO 3 + Na 2 CO 3 → Ag 2 CO 3 + 2NaNO 3
上記の置換反応は、前記粘土鉱物粒子上に吸着保持された炭酸ナトリウム（Ｎａ２ＣＯ３）あるいは液中の炭酸ナトリウム（Ｎａ２ＣＯ３）と硝酸銀（ＡｇＮＯ３）との反応である。このうち、液中で生じた炭酸銀（Ａｇ２ＣＯ３）の微細粒子は、前記粘土鉱物粒子上に生じた炭酸銀（Ａｇ２ＣＯ３）上にその大部分が移動析出する。 The above substitution reaction is the reaction of sodium carbonate of the clay adsorbent retained sodium carbonate on mineral particles (Na 2 CO 3) or in the liquid and (Na 2 CO 3) and silver nitrate (AgNO 3). Among these, most of the fine particles of silver carbonate (Ag 2 CO 3 ) generated in the liquid move and precipitate on the silver carbonate (Ag 2 CO 3 ) generated on the clay mineral particles.
上記の置換反応（Ｓ５）によって前記粘土鉱物粒子上に炭酸銀（Ａｇ２ＣＯ３）が吸着保持された沈殿物が容器に沈殿するので、濾紙等により濾過して硝酸ナトリウム（ＮａＮＯ３）を除去する（Ｓ６）。そして、濾過されなかった前記沈殿物を取り出して水洗し（Ｓ７）、約１２０℃の温度で乾燥させ、約２００℃の温度で加熱すると、熱分解反応によって炭酸ガス（ＣＯ２）が放出されて、前記粘土鉱物粒子の表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。このときの化学反応式を（化式４）に記す。 The precipitate in which silver carbonate (Ag 2 CO 3 ) is adsorbed and held on the clay mineral particles by the above substitution reaction (S5) precipitates in the container, and is filtered through filter paper to remove sodium nitrate (NaNO 3 ). (S6). Then, the unfiltered precipitate is taken out, washed with water (S7), dried at a temperature of about 120 ° C., and heated at a temperature of about 200 ° C. to release carbon dioxide (CO 2 ) by the thermal decomposition reaction. And silver oxide (Ag 2 O) supported and fixed on the surface layer of the clay mineral particles. The chemical reaction formula at this time is shown in (Formula 4).
（化式４）
Ａｇ２ＣＯ３ → Ａｇ２Ｏ ＋ ＣＯ２
(Formula 4)
Ag 2 CO 3 → Ag 2 O + CO 2
そして、酸化銀（Ａｇ２Ｏ）が形成された前記粘土鉱物粒子を４００から５００℃の温度で焼成する（Ｓ８）。酸化銀（Ａｇ２Ｏ）を４００から５００℃の温度で加熱することで酸素（Ｏ２）が放出されるとともに、前記粘土鉱物粒子（担体）上での体積の急激な減少による微粒化によって、銀（Ａｇ）が微粒子として前記粘土鉱物粒子の表層に担持され固着する。 Then, the clay mineral particles formed with silver oxide (Ag 2 O) are fired at a temperature of 400 to 500 ° C. (S8). By heating silver oxide (Ag 2 O) at a temperature of 400 to 500 ° C., oxygen (O 2 ) is released, and by atomization due to a rapid decrease in volume on the clay mineral particles (support), Silver (Ag) is supported and fixed as fine particles on the surface layer of the clay mineral particles.
前記粘土鉱物粒子の表層に銀が担持され固定された状態で、ボールミル等の粉砕手段によって粉砕する（Ｓ９）。粉砕することで、前記粘土鉱物粒子の表層に銀を担持させ固定させた銀担持鉱物粒子となる。 In a state where silver is supported and fixed on the surface layer of the clay mineral particles, it is pulverized by a pulverizing means such as a ball mill (S9). By pulverizing, silver-carrying mineral particles in which silver is supported and fixed on the surface layer of the clay mineral particles are obtained.
図２は、上述した炭酸水素ナトリウム（ＮａＨＣＯ３）と硝酸銀（ＡｇＮＯ３）との置換反応によってスメクタイト上に重炭酸銀（ＡｇＨＣＯ３）が吸着保持された沈殿物（吸着保持担体）を試料として、加熱しながら当該試料の重量変化を示唆熱天秤（ＴＧ−ＤＴＡ）によって測定し、示唆熱と重量変化の関係を表した測定データチャートである。図２の横軸は加熱温度（Ｔｅｍｐｅｒａｔｕｒｅ、単位：℃）を示しており、図２の縦軸は重量の微分値（ＤＴＧ、単位：％／ｓ）、重量変化率（Ｗｅｉｇｈｔ、単位：％）、並びに熱流の微分値（Ｈｅａｔ Ｆｌｏｗ、単位：μＶ）を示している。図２には上から順に、重量の微分曲線、重量減少率曲線、熱量の微分曲線が示される。 FIG. 2 shows, as a sample, a precipitate (adsorption holding carrier) in which silver bicarbonate (AgHCO 3 ) is adsorbed and held on smectite by the substitution reaction of sodium hydrogen carbonate (NaHCO 3 ) and silver nitrate (AgNO 3 ) described above. It is the measurement data chart which measured the weight change of the said sample with the suggestion thermobalance (TG-DTA), heating, and represented the relationship between suggestion heat and a weight change. The horizontal axis of FIG. 2 indicates the heating temperature (Temperature, unit: ° C.), and the vertical axis of FIG. 2 indicates the weight differential value (DTG, unit:% / s), weight change rate (Weight, unit:%). , And the differential value of heat flow (Heat Flow, unit: μV). FIG. 2 shows a weight differential curve, a weight loss rate curve, and a calorie differential curve in order from the top.
図２に示す示唆熱による重量変化について説明する。前記スメクタイト上に重炭酸銀（ＡｇＨＣＯ３）が吸着保持された吸着保持担体を試料として、加熱温度を１２０℃から１０００℃まで段階的に加熱しながら前記試料の重量を測定した。加熱温度が１９８．７℃にて、熱分解反応によって水蒸気（Ｈ２Ｏ）と炭酸ガス（ＣＯ２）が放出されて前記試料の重量が初期値よりも約８％減少し、前記スメクタイトの表層に担持され固定された酸化銀（Ａｇ２Ｏ）が出来る。前記急激な化学反応は、上述の（化式２）で表される化学反応であり、熱流の微分曲線の急峻な変化からも明らかである。そして、前記試料への加熱温度をさらに高くしてゆくと、前記試料の重量が僅かずつ減少してゆき、加熱温度が４４２．３℃では前記試料の重量が初期値よりも約１２％減少する。 The weight change due to the suggested heat shown in FIG. 2 will be described. Using the adsorption holding carrier in which silver bicarbonate (AgHCO 3 ) was adsorbed and held on the smectite as a sample, the weight of the sample was measured while heating the heating temperature stepwise from 120 ° C to 1000 ° C. When the heating temperature is 198.7 ° C., water vapor (H 2 O) and carbon dioxide (CO 2 ) are released by the pyrolysis reaction, and the weight of the sample is reduced by about 8% from the initial value. Silver oxide (Ag 2 O) supported and fixed on the substrate can be formed. The abrupt chemical reaction is a chemical reaction represented by the above (Formula 2), and is also apparent from a steep change in the differential curve of heat flow. As the heating temperature of the sample is further increased, the weight of the sample is gradually decreased. When the heating temperature is 442.3 ° C., the weight of the sample is reduced by about 12% from the initial value. .
前記試料への加熱温度をさらに高くしてゆくと、加熱温度が４４２．３℃から４４４．２℃にかけて急激な化学反応によって酸素ガス（Ｏ２）が放出されて、前記スメクタイトの表層に担持され固定された酸化銀（Ａｇ２Ｏ）が銀（Ａｇ）になる。この急激な化学反応は、熱流の微分曲線の急峻な変化からも明らかである。 When the heating temperature of the sample is further increased, oxygen gas (O 2 ) is released by a rapid chemical reaction from the heating temperature of 442.3 ° C. to 444.2 ° C., and is supported on the surface of the smectite. The fixed silver oxide (Ag 2 O) becomes silver (Ag). This abrupt chemical reaction is also evident from the steep change in the differential curve of heat flow.
（本発明に係る湿式微粒化装置について）
本発明に係る湿式微粒化装置について、以下に説明する。図３は、本発明にて使用する湿式微粒化装置１００の概略構成を示すブロック図である。原料液１０は、例えば銀担持鉱物粒子１ａと水との混合液１０である。湿式微粒化装置１００は、高圧ポンプ１０２を油圧駆動及び制御する油圧発生・制御部１０１と、原料液１を加圧する高圧ポンプ１０２と、原料液１０を投入する原料タンク１０３と、投入され加圧された原料液１０内の粒子１ａを噴射させ加速して衝突させることで銀担持鉱物粒子１ａを微細化して銀担持鉱物微粒子１ｂとするとともに分散させる衝突チャンバー４０と、衝突チャンバー４０にて微粒化され分散された銀担持鉱物微粒子１ｂを有する懸濁液２を冷却する熱交換器１０５からなる。湿式微粒化装置１００は、粒子１ａの混合液１０をチャンバーノズルから高圧噴射することで、粒子１ａ自体を壊さず、コンタミの混入がない状態で、微粒化して微粒子１ｂとするとともに均一に分散して懸濁液２０とする。
(About the wet atomization apparatus according to the present invention)
The wet atomization apparatus according to the present invention will be described below. FIG. 3 is a block diagram showing a schematic configuration of the
原料液１０は、例えば粒子１ａと水との混合液１０である。原料タンク１０３に混合液１０を投入し、高圧ポンプ１０２にて混合液１０を加圧して、衝突チャンバー４０内の微細ノズルから混合液１０を噴射させ加速して衝突させることで粒子１ａを微細化して微粒子１ｂとするとともに、微粒子１ｂが均一に分散した懸濁液２０とし、衝突チャンバー４０内の噴射によって温度が上昇した懸濁液２０を、熱交換器１０５にて常温まで冷却して排出する（図３）。衝突チャンバー４０には、用途によって、シングルノズルチャンバー、斜向衝突チャンバー、ボール衝突チャンバー、スリットチャンバー、多液噴射反応チャンバー、分離チャンバー等の種類がある。
The
図４は、シングルノズルチャンバー４１の概略構成を示す模式図である。シングルノズルチャンバー４１は、混合液１０を１つの微細ノズル４１１から液中に噴射させ粒子１ａを加速してチャンバー内壁に衝突させ、出口４１２から懸濁液２０を排出するタイプである。微細ノズル４１１は、単結晶ダイヤモンド等を使用しており、微細ノズル４１１を粒子１ａが通過するときの剪断力と、液中噴射によるキャビテーション衝撃力によって、微粒化と分散を行う。シングルノズルチャンバー４１は、局所的に力を加えると割れ易い粒子や板状の粒子が積層した粒子をほぐして分散させる。
FIG. 4 is a schematic diagram showing a schematic configuration of the
図５は、斜向衝突チャンバー４２の概略構成を示す模式図である。斜向衝突チャンバー４２は、混合液１０を対向配置された１対の微細ノズル４２１から液中に噴射させ粒子１ａを加速して互いに対向衝突（対面衝突）させ、出口４２２から懸濁液２０を排出するタイプである。微細ノズル４２１は、単結晶ダイヤモンド等を使用しており、微細ノズル４２１を粒子１ａが通過するときの剪断力と、液中噴射によるキャビテーション衝撃力と、粒子１ａ同士が対向衝突するときの衝撃力と、対向噴流での相対速度増加による剪断力によって、微粒化と分散を行う。斜向衝突チャンバー４２は、シングルノズルチャンバー４１よりも微粒化処理能力が高い。
FIG. 5 is a schematic diagram showing a schematic configuration of the
図６は、ボール衝突チャンバー４３の概略構成を示す模式図である。ボール衝突チャンバー４３は、混合液１０を１つの微細ノズル４３１から液中に噴射させ粒子１ａを加速してセラミックボール４３３に衝突させ、出口４３２から懸濁液２０を排出するタイプである。微細ノズル４３１は、単結晶ダイヤモンド等を使用しており、セラミックボール４３３は窒化珪素等からなる。微細ノズル４３１を粒子１ａが通過するときの剪断力と、液中噴射によるキャビテーション衝撃力と、粒子１ａがセラミックボール４３３に対向衝突するときの衝撃力によって、微粒化と分散を行う。ボール衝突チャンバー４３の微細ノズル４３１は、斜向衝突チャンバー４２の微細ノズル４２１よりもノズル径を大きくすることができるので、粒径の大きな粒子１ａの微粒化処理に適している。
FIG. 6 is a schematic diagram showing a schematic configuration of the
（本発明に係る懸濁液の製造方法）
図１は、本発明を適用した実施形態の光触媒コーティング液の製造手順を示す製造工程フロー図である。図１のステップＳ１からステップＳ９は、上述した本発明に係る銀担持鉱物粒子の製造工程を示しており、図１のステップＳ１０からステップＳ１４は、本発明に係る懸濁液の製造工程を示している。
(Method for producing suspension according to the present invention)
FIG. 1 is a manufacturing process flow chart showing a manufacturing procedure of a photocatalyst coating liquid according to an embodiment to which the present invention is applied. Steps S1 to S9 in FIG. 1 show the above-described production process of the silver-carrying mineral particles according to the present invention, and steps S10 to S14 in FIG. 1 show the production process of the suspension according to the present invention. ing.
本発明に係る懸濁液の製造方法について以下に説明する。図１に示す、本発明に係る懸濁液の製造工程は、粉砕工程（Ｓ９）にて粉砕された銀担持鉱物粒子１ａに蒸留水を所定の濃度となるように加えた混合液１１を湿式微粒化装置１００に投入して微粒化及び分散処理を行い銀担持鉱物微粒子１ｂが均一に分散した第１の懸濁液２１とする微粒化・分散工程（Ｓ１０）と、懸濁液２１に紫外線を照射して残留酸化銀を銀に還元する紫外線照射工程（Ｓ１１）と、別ラインにて、酸化チタン粒子２ａに蒸留水を所定の濃度となるように加えた混合液１２を湿式微粒化装置１００に投入して微粒化及び分散処理を行い酸化チタン微粒子２ｂが均一に分散した第２の懸濁液２２とする微粒化・分散工程（Ｓ１２）と、第１の懸濁液２１と第２の懸濁液２２を所定比率で調合し攪拌する調合・攪拌工程（Ｓ１３）と、第１の懸濁液１ｂと第２の懸濁液２ｂを所定比率で調合した第３の懸濁液２３を湿式微粒化装置１００に投入してさらなる微粒化及び分散処理を行い第４の懸濁液２４とする微粒化・分散工程（Ｓ１４）からなる。
The method for producing a suspension according to the present invention will be described below. In the suspension production process according to the present invention shown in FIG. 1, the
図１に示す、本発明に係る懸濁液の製造工程は、粉砕工程（Ｓ９）にて粉砕された銀担持鉱物粒子１ａに蒸留水を所定の濃度となるように加えた混合液１１を湿式微粒化装置１００に投入して、予め条件出しを行った設定圧力にて微粒化及び分散処理を行い銀担持鉱物微粒子１ｂが均一に分散した第１の懸濁液２１とする（Ｓ１０）。湿式微粒化装置１００にて微粒化及び分散処理を行うことで、銀担持鉱物微粒子１ｂにＯＨ基が付いて表面改質され、粒子１ｂ同士の斥力（反発力）が保たれ分散状態が安定する。１回の処理で目標の粒子径（メジアン粒径）に達しない場合や、上記表面改質が不十分な場合には、再度原料タンク１０３へ戻し、微粒化及び分散処理を必要回数まで繰り返す。そして、懸濁液２１に紫外線を照射して銀担持鉱物微粒子１ｂの表層の残留酸化銀を銀に還元する（Ｓ１１）。
In the suspension production process according to the present invention shown in FIG. 1, the
また別ラインにて、酸化チタン粒子２ａに蒸留水を所定の濃度となるように加えた混合液１２を湿式微粒化装置１００に投入して微粒化及び分散処理を行い酸化チタン微粒子２ｂが均一に分散した第２の懸濁液２２とする（Ｓ１２）。湿式微粒化装置１００にて微粒化及び分散処理を行うことで、酸化チタン微粒子２ｂにＯＨ基が付いて表面改質され、粒子２ｂ同士の斥力（反発力）が保たれ分散状態が安定する。１回の処理で目標の粒子径（メジアン粒径）に達しない場合や、上記表面改質が不十分な場合には、再度原料タンク１０３へ戻し、微粒化及び分散処理を必要回数まで繰り返す。
In a separate line, the
次に、第１の懸濁液２１と第２の懸濁液２２を用途に応じて所定比率で調合し攪拌して第３の懸濁液２３とする（Ｓ１３）。例えば抗菌能力を高めるためには、第１の懸濁液２１の比率を高めればよい。例えば光触媒活性度を高めるためには第２の懸濁液２２の比率を高めればよい。 Next, the first suspension 21 and the second suspension 22 are prepared at a predetermined ratio according to the application and stirred to obtain a third suspension 23 (S13). For example, in order to increase the antibacterial ability, the ratio of the first suspension 21 may be increased. For example, in order to increase the photocatalytic activity, the ratio of the second suspension 22 may be increased.
そして、第１の懸濁液２１と第２の懸濁液２２を所定比率で調合した第３の懸濁液２３を湿式微粒化装置１００に投入してさらなる微粒化及び分散処理を行い第４の懸濁液２４とする（Ｓ１４）。湿式微粒化装置１００にて微粒化及び分散処理を行うことで、上述した表面改質効果も期待できる。なお、ステップＳ１４は、懸濁液の条件によって適宜省略することができる。
Then, the third suspension 23 prepared by mixing the first suspension 21 and the second suspension 22 at a predetermined ratio is put into the
このようにして得られた懸濁液２３（２４）は、密封容器に入れて長期間（およそ１ヶ月間）放置した状態でも均一な分散状態を維持する。そして、用途に応じて懸濁液２３（２４）に適宜蒸留水を加えて濃度を調節し光触媒コーティング液２５とする。 The suspension 23 (24) thus obtained maintains a uniform dispersion state even when left in a sealed container for a long period (approximately one month). And according to a use, distilled water is added to suspension 23 (24) suitably, a density | concentration is adjusted, and it is set as the photocatalyst coating liquid 25. FIG.
本発明による光触媒コーティング液２５は、例えば市販のスプレー容器に入れて抗菌消臭ドライクリーニング用コーティング液２６とする。この抗菌消臭ドライクリーニング用コーティング液２６を衣料にスプレー塗布して前記銀担持鉱物微粒子１ｂ及び前記酸化チタン微粒子２ｂを前記衣料の繊維に付着させた光触媒加工衣料とする
The photocatalyst coating liquid 25 according to the present invention is used as an antibacterial deodorant dry cleaning coating liquid 26 in, for example, a commercially available spray container. This antibacterial and deodorant dry cleaning coating solution 26 is spray-applied on clothing to produce a photocatalyst-treated clothing in which the silver-carrying
（本発明の実施例）
炭酸水素ナトリウム水溶液にスメクタイトを浸漬し、硝酸銀と置換反応させてスメクタイト粒子の表層に重炭酸銀を生成し、アルミナ製の加熱容器に入れて、約４５０℃の焼成温度で焼成し、ボールミルで粉砕することでスメクタイト粒子の表層に銀を担持させた銀担持鉱物粒子１ａを作製した。この銀担持鉱物粒子１ａに蒸留水を加えて攪拌し混合液１１とした。
(Example of the present invention)
Smectite is immersed in an aqueous solution of sodium hydrogen carbonate, and substituted with silver nitrate to produce silver bicarbonate on the surface layer of the smectite particles, placed in a heating vessel made of alumina, fired at a firing temperature of about 450 ° C., and pulverized with a ball mill As a result, silver-carrying
図７は、混合液１１における銀の元素分布状態を観察した図である。銀の分布に塊が見られ、分布が不均一であることがわかる。図１２は、微粒化前の銀担持鉱物粒子１ａの粒径分布を示す分布図である。銀担持鉱物粒子１ａのメジアン粒径は６．１３８μｍである。粒径ばらつきが大きいことがわかる。
FIG. 7 is a diagram observing the element distribution state of silver in the
混合液１１を、湿式微粒化装置１００として株式会社スギノマシン製のスターバースト装置（装置商品名）に投入して微粒化及び分散処理を行い銀担持鉱物微粒子１ｂが均一に分散した第１の懸濁液２１とした。上記スターバースト装置の条件は、圧力２２０ＭＰａ、ノズル径φ０．１２ｍｍのシングルノズルチャンバーを用いて、チャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を５回繰り返した。そして得られた懸濁液２１に紫外線を照射して残留酸化銀を銀に還元した。
The
図８は、懸濁液２１における銀元素の分布状態を観察した図である。銀の分布が均一であることがわかる。図１３は、微粒化後の銀担持鉱物微粒子１ｂの粒径分布を示す分布図である。銀担持鉱物微粒子１ｂのメジアン粒径は０．８９６μｍである。粒径ばらつきが小さいことがわかる。図９は、上記銀担持鉱物粒子１ｂの表面状態を観察した図である。数十ｎｍの微粒子が揃っていることがわかる。
FIG. 8 is a diagram observing the distribution state of the silver element in the suspension 21. It can be seen that the distribution of silver is uniform. FIG. 13 is a distribution diagram showing the particle size distribution of the silver-carrying
別ラインにて、酸化チタン粒子２ａ（日本アエロジル株式会社製の商品名Ｐ２５）に蒸留水を加えて攪拌し混合液１２とした。図１４は、酸化チタン粒子２ａの粒径分布を示す分布図である。酸化チタン粒子２ａのメジアン粒径は２．５６７μｍである。粒径ばらつきが大きいことがわかる。
In another line, distilled water was added to the titanium oxide particles 2a (trade name P25 manufactured by Nippon Aerosil Co., Ltd.) and stirred to obtain a
混合液１２を、湿式微粒化装置１００として株式会社スギノマシン製のスターバースト装置（装置商品名）に投入して微粒化及び分散処理を行い酸化チタン微粒子２ｂが均一に分散した第２の懸濁液２２とした。上記スターバースト装置の条件は、圧力２２０ＭＰａ、ノズル径φ０．１２ｍｍのシングルノズルチャンバーを用いて、チャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を５回繰り返した。
A second suspension in which the titanium oxide fine particles 2b are uniformly dispersed by introducing the
図１５は、微粒化後の酸化チタン微粒子２ｂの粒径分布を示す分布図である。酸化チタン微粒子２ｂのメジアン粒径は０．０９６μｍである。粒径ばらつきが小さいことがわかる。 FIG. 15 is a distribution diagram showing the particle size distribution of the fine titanium oxide particles 2b after atomization. The median particle size of the titanium oxide fine particles 2b is 0.096 μm. It can be seen that the particle size variation is small.
そして、第１の懸濁液２１と第２の懸濁液２２を所定比率で調合した第３の懸濁液２３を、湿式微粒化装置１００として株式会社スギノマシン製のスターバースト装置（装置商品名）に投入して微粒化及び分散処理を行い第４の懸濁液２４とした。上記スターバースト装置の条件は、圧力２２０ＭＰａ、ノズル径φ０．１２ｍｍのシングルノズルチャンバーを用いて、チャンバーノズルから前記混合液を所定の圧力で高圧噴射する作業を５回繰り返した。図１０は、懸濁液２４におけるチタン元素の分布状態を観察した図である。酸化チタンの分布が均一であることがわかる。図１１は、懸濁液２４における銀元素の分布状態を観察した図である。銀の分布が均一であることがわかる。
Then, the third suspension 23 prepared by mixing the first suspension 21 and the second suspension 22 at a predetermined ratio is used as a
このようにして得られた懸濁液２４を、ガラス密封容器に入れて１ヶ月間放置したが、目視確認により沈殿物や凝集物がないことが確認できたので、均一な分散状態が維持されていると考えられる。懸濁液２４に適宜蒸留水を加えて濃度を調節し光触媒コーティング液２５とした。この光触媒コーティング液２５を市販のスプレー容器に入れて抗菌消臭ドライクリーニング用コーティング液２６とした。 The suspension 24 thus obtained was placed in a glass sealed container and allowed to stand for one month. However, since it was confirmed by visual confirmation that there was no precipitate or aggregate, a uniform dispersion state was maintained. It is thought that. Distilled water was appropriately added to the suspension 24 to adjust the concentration to obtain a photocatalyst coating solution 25. This photocatalyst coating solution 25 was put in a commercially available spray container to prepare an antibacterial deodorant dry cleaning coating solution 26.
（光触媒性能評価試験）
上記抗菌消臭ドライクリーニング用コーティング液２６を白布にスプレー塗布しコートした。図１６は、上記抗菌消臭ドライクリーニング用コーティング液２６を白布にスプレー塗布した状態を観察した図である。目視でコート後変化が認められない程度の量を均一に白布に塗布し、試料Ｎｏ．１と試料Ｎｏ．２を作成した。そして、紫外線を白布に照射して、吸光度測定器を用いて光触媒によるメチレンブルーの経時的分解を測定した。メチレンブルー分解試験を行った試験結果を図１７に示す。
(Photocatalyst performance evaluation test)
The antibacterial and deodorant dry cleaning coating liquid 26 was spray-coated on a white cloth and coated. FIG. 16 is a view observing a state in which the antibacterial and deodorant dry cleaning coating liquid 26 is sprayed on a white cloth. Apply an amount to the white cloth so that no change is observed after coating. 1 and sample no. 2 was created. Then, the white cloth was irradiated with ultraviolet rays, and the time-dependent degradation of methylene blue by the photocatalyst was measured using an absorbance meter. The test results of the methylene blue decomposition test are shown in FIG.
図１７の横軸は紫外線照射時間（ＵＶ照射時間）を表し、縦軸はメチレンブルー濃度（ＭＢ濃度）を表す。図１７に示す測定グラフの傾斜から、微量の二酸化チタンでも有機物分解が起こっていることが確かめられた。分解活性指数は１９．７４ ｎｍｏｌ／Ｌ／ｍｉｎ．であった。 The horizontal axis in FIG. 17 represents the ultraviolet irradiation time (UV irradiation time), and the vertical axis represents the methylene blue concentration (MB concentration). From the slope of the measurement graph shown in FIG. 17, it was confirmed that organic matter decomposition occurred even with a small amount of titanium dioxide. The degradation activity index was 19.74 nmol / L / min. Met.
上記試料Ｎｏ．１と試料Ｎｏ．２を、財団法人日本紡績協会に提出し、抗菌性試験を実施した。試験菌株は黄色ぶどう球菌ＡＴＣＣ６５３８Ｐ、試験方法はＪＩＳ Ｌ１９０２：２００８定量試験（菌液吸収法）による。試験結果を表１に示す。 Sample No. above. 1 and sample no. 2 was submitted to the Japan Spinning Association and an antibacterial test was conducted. The test strain is Staphylococcus aureus ATCC 6538P, and the test method is based on JIS L1902: 2008 quantitative test (bacterial fluid absorption method). The test results are shown in Table 1.
ＪＩＳ Ｌ１９０２によれば、抗菌と呼ぶためには黄色ぶどう球菌の静菌活性値が２．０以上であると規定されている。表１に示す試料Ｎｏ．１と試料Ｎｏ．２の静菌活性値は、それぞれ５．２以上、５．６以上となっており、抗菌性能が十分あると判断する。 According to JIS L1902, it is defined that the bacteriostatic activity value of Staphylococcus aureus is 2.0 or more in order to call it antibacterial. Sample No. shown in Table 1 1 and sample no. The bacteriostatic activity values of 2 are 5.2 or more and 5.6 or more, respectively, and it is judged that the antibacterial performance is sufficient.
以上、本発明は、上述した実施の形態に限定されるものではない。上記粘土鉱物としてシリカゲルを使用した場合でも、良好な実験結果が得られた。このように、本発明は、その趣旨を逸脱しない範囲で適宜変更が可能であることは言うまでもない。 As described above, the present invention is not limited to the embodiment described above. Even when silica gel was used as the clay mineral, good experimental results were obtained. Thus, it goes without saying that the present invention can be modified as appropriate without departing from the spirit of the present invention.
１０、１１、１２ 混合液（原料）、
２０、２１、２２、２３、２４ 懸濁液、
２５ 光触媒コーティング液、
１ａ 微粒化及び分散処理前の銀担持鉱物粒子（粒子）、
１ｂ 微粒化及び分散処理後の銀担持鉱物粒子（微粒子）、
２ａ 微粒化及び分散処理前の酸化チタン粒子、
２ｂ 微粒化及び分散処理後の酸化チタン粒子、
４０ 衝突チャンバー、
１００ 湿式微粒化装置
10, 11, 12 Mixed liquid (raw material),
20, 21, 22, 23, 24 suspension,
25 photocatalyst coating solution,
1a Silver-carrying mineral particles (particles) before atomization and dispersion treatment,
1b Silver-carrying mineral particles (fine particles) after atomization and dispersion treatment,
2a Titanium oxide particles before atomization and dispersion treatment,
2b Titanium oxide particles after atomization and dispersion treatment,
40 collision chamber,
100 Wet atomizer
Claims (7)
硝酸銀と置換反応させて前記粘土鉱物粒子の表層に銀化合物を生成し、これを焼成温度が４００から５００℃で焼成し粉砕することで前記粘土鉱物粒子の表層に銀を担持させた銀担持鉱物粒子とし、前記銀担持鉱物粒子と酸化チタン粒子をそれぞれ微粒化手段によって微粒化するとともに分散手段によって水に均一に分散させて前記銀担持鉱物粒子と酸化チタン粒子と水との懸濁液を製造することを特徴とする光触媒コーティング液の製造方法。 Soak sodium bicarbonate or sodium carbonate in clay mineral particles of kaolinite, halloysite, smectite, bentonite, talc, mica, vermiculite, chlorite, montmorillonite, activated clay, or two or more types. was written,
Silver nitrate and by substitution reaction to produce a silver compound on the surface layer of the clay mineral particles, supported silver minerals silver supported on the surface of the clay mineral particles by firing temperature which is fired pulverized at 500 ° C. 400 A suspension of the silver-carrying mineral particles, titanium oxide particles, and water is prepared by atomizing the silver-carrying mineral particles and titanium oxide particles by the atomization means and uniformly dispersing in water by the dispersion means. A method for producing a photocatalyst coating liquid, comprising:
A photocatalyst-processed garment in which the antibacterial and deodorant dry cleaning coating liquid according to claim 6 is spray-applied to the garment to adhere the silver-carrying mineral particles and the titanium oxide particles to the fibers of the garment.
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| JP2016002384A (en) * | 2014-06-18 | 2016-01-12 | ｎ−ｔｅｃｈ株式会社 | Antibacterial/deodorant composition |
| JP6632286B2 (en) * | 2015-09-18 | 2020-01-22 | アシザワ・ファインテック株式会社 | Method for lowering thermal expansion coefficient of resin molding |
| JP7064751B2 (en) * | 2017-02-27 | 2022-05-11 | 株式会社イリス | Titanium oxide coating method |
| JP6953965B2 (en) | 2017-09-29 | 2021-10-27 | 信越化学工業株式会社 | A member having a photocatalyst / alloy fine particle dispersion having antibacterial / antifungal properties, a method for producing the same, and a photocatalyst / alloy thin film on the surface. |
| JP7423840B1 (en) | 2023-03-22 | 2024-01-29 | 株式会社アデランス | Manufacturing method of photocatalyst coating agent |
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