JP3228035B2 - Manufacturing method of antibacterial material - Google Patents
Manufacturing method of antibacterial materialInfo
- Publication number
- JP3228035B2 JP3228035B2 JP31230994A JP31230994A JP3228035B2 JP 3228035 B2 JP3228035 B2 JP 3228035B2 JP 31230994 A JP31230994 A JP 31230994A JP 31230994 A JP31230994 A JP 31230994A JP 3228035 B2 JP3228035 B2 JP 3228035B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- antibacterial
- particles
- layer
- elution
- 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.)
- Expired - Fee Related
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 32
- 239000000463 material Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 71
- 239000004332 silver Substances 0.000 claims description 71
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 37
- 230000001699 photocatalysis Effects 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- 238000010828 elution Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 239000010410 layer Substances 0.000 description 28
- 239000003242 anti bacterial agent Substances 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- -1 silver ions Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 210000002700 urine Anatomy 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000000843 anti-fungal effect Effects 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 229940121375 antifungal agent Drugs 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000013268 sustained release Methods 0.000 description 4
- 239000012730 sustained-release form Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010014405 Electrocution Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001302584 Escherichia coli str. K-12 substr. W3110 Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910016003 MoS3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 108700024661 strong silver Proteins 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、汚水等の液体又はその
流路に載置、固定する抗菌材の製造方法に関する。The present invention relates to a liquid or placed on the flow path of the sewage or the like, relates to the manufacturing method of antibacterial material for fixing.
【０００２】[0002]
【従来技術】汚水等の液体およびその通路の抗菌方法と
しては、従来より光触媒を利用した方法、抗菌性金属を
利用した方法およびそれらを組み合わせた方法がある。
光触媒を利用した方法は、特公平５−５０２９４号にお
いて、光半導体微粒子を基材表面に固定化して成る光滅
菌性充填材を有することを特徴とする滅菌リアクターが
開示されており、それにより３時間で９９％以上の滅菌
に成功している。2. Description of the Related Art Antibacterial methods for liquids such as sewage and the like and passages thereof include a method using a photocatalyst, a method using an antibacterial metal, and a method combining them.
As a method using a photocatalyst, Japanese Patent Publication No. 5-50294 discloses a sterilization reactor characterized by having a photosterilizing filler made by immobilizing optical semiconductor fine particles on the surface of a base material. It has successfully sterilized more than 99% of the time.
【０００３】しかし、一方特公平６−７９０５号にはこ
の方法の欠点が指摘されている。特公平６−７９０５号
には、半導体からなる光触媒層と、それに対向して設け
られた紫外線灯および発熱体と、送風機からなり、光触
媒層全体が順次加熱されるように、光触媒層あるいは発
熱体、または光触媒層及び発熱体が移動する光触媒によ
る脱臭装置が開示されている。さらにこの装置を作成し
た目的として以下のことが記されている。すなわち、高
分子物質や塵芥の混合物が、光触媒反応を起こす触媒で
ある半導体表面に付着し、これを覆ってしまうため、触
媒まで紫外線が達せず、触媒がエネルギーを受けにくく
なり、光触媒反応が低下し、反応劣化を引き起こすので
ある。このような現象は抗菌に使用した場合にも生じる
と考えられ、特に汚水等の液体およびその通路、接触部
では、水がこれらの混合物を輸送媒体として働くため生
じやすいと考えられる。したがって上記に示すような装
置でも用いない限り、光触媒を利用した方法での長期の
使用は困難であると考えられる。[0003] On the other hand, Japanese Patent Publication No. 6-7905 points out a disadvantage of this method. Japanese Patent Publication No. 6-7905 discloses a photocatalyst layer or a heating element comprising a semiconductor photocatalyst layer, an ultraviolet lamp and a heating element provided opposite thereto, and a blower so that the entire photocatalyst layer is sequentially heated. Alternatively, a deodorizing apparatus using a photocatalyst in which a photocatalyst layer and a heating element move is disclosed. Further, the following is described as the purpose of creating this device. In other words, a mixture of polymer substances and dust adheres to and covers the surface of the semiconductor, which is the catalyst that causes the photocatalytic reaction, so that the ultraviolet light does not reach the catalyst, the catalyst is less likely to receive energy, and the photocatalytic reaction is reduced. This causes reaction degradation. This phenomenon is considered to occur even when used in antimicrobial, especially liquid and passage of the sewage or the like, the contact portion, the water is considered likely to occur to work these mixtures as transport medium. Therefore, it is considered that long-term use in a method using a photocatalyst is difficult unless the above-described apparatus is used.
【０００４】抗菌性金属を利用した方法は、特開平２−
１９３０８号等に開示されている。特開平２−１９３０
８号では、層状ケイ酸塩に含有されるイオン交換可能な
金属の少なくとも一部を銀、銅および亜鉛の中から選ば
れた少なくとも１種の金属で置換してなる被膜形成能を
有する抗菌性ケイ酸塩、具体的には銀モンモリロナイト
が開示されている。この銀モンモリロナイトは確かに初
期の抗菌性には優れている。また溶出する銀イオンによ
り殺菌されるので、接触を要件とする光触媒とは異な
り、効力が溶液にも及ぶ。A method using an antibacterial metal is disclosed in Japanese Unexamined Patent Publication No.
No. 19308 and the like. JP-A-2-1930
No. 8 discloses an antibacterial property having a film-forming ability in which at least a part of an ion-exchangeable metal contained in a layered silicate is replaced with at least one metal selected from silver, copper and zinc. Silicates, specifically silver montmorillonite, are disclosed. This silver montmorillonite certainly has excellent initial antimicrobial properties. In addition, since it is sterilized by the eluted silver ions, unlike a photocatalyst that requires contact, the effect extends to a solution.
【０００５】しかし特開平６−６５０１２号に示されて
いるように、モンモリロナイトへの銀の担持力が弱いた
め、溶出速度が速く長期の使用に耐えない。さらに汚水
等の液体およびその通路、接触部のように、多量のアル
カリ金属イオン、アルカリ土類金属イオンの存在する環
境では、かかるイオン交換法による銀の固定では、これ
らアルカリ金属イオン、アルカリ土類金属イオンと銀と
の交換が一気に生じ、銀の溶出が加速されるので、より
短期で効力を失ってしまうと考えられる。However, as disclosed in Japanese Patent Application Laid-Open No. 6-65012, since the supporting force of silver on montmorillonite is weak, the elution rate is high and it cannot withstand long-term use. Further, in an environment where a large amount of alkali metal ions or alkaline earth metal ions are present, such as a liquid such as sewage, a passage thereof, and a contact portion, the fixation of silver by such an ion exchange method requires the use of these alkali metal ions and alkaline earth ions. It is considered that the exchange between metal ions and silver occurs at once, and the elution of silver is accelerated, so that the effect is lost in a shorter time.
【０００６】そこで、光触媒と銀を組み合わせた方法
が、特開平６−６５０１２号に開示されている。特開平
６−６５０１２号では、銀、銅、亜鉛、白金の内から選
ばれた少なくとも１種の金属イオンを含有した酸化チタ
ン膜を基板に被覆した抗菌抗カビセラミックスが開示さ
れている。その効果は基本的には、酸化チタン膜による
光触媒作用と、銀、銅、亜鉛、白金の内から選ばれた少
なくとも１種の金属イオンによる抗菌作用であるが、そ
れに加え酸化チタン膜のもう１つの役割として以下のこ
とが開示されている。すなわち酸化チタン膜の厚さおよ
び含有金属量を変化させることにより、または白金膜を
さらに酸化チタン膜上に被覆し、その厚さを変化させる
ことにより含有金属の徐放（溶出）速度あるいは寿命を
制御できるとされている。Therefore, a method using a combination of a photocatalyst and silver is disclosed in JP-A-6-65012. JP-A-6-65012 discloses an antibacterial antifungal ceramic in which a substrate is coated with a titanium oxide film containing at least one metal ion selected from silver, copper, zinc and platinum. The effect is basically a photocatalytic action by the titanium oxide film and an antibacterial action by at least one metal ion selected from silver, copper, zinc, and platinum. The following are disclosed as one role. That is, by changing the thickness of the titanium oxide film and the content of the metal, or by further coating the platinum film on the titanium oxide film and changing the thickness, the sustained release (elution) rate or the life of the contained metal is changed. It is said that it can be controlled.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、特開平
６−６５０１２号に開示された方法には以下に示す問題
がある。酸化チタン膜の厚さおよび含有金属量の変化
は、いずれも膜に含まれる銀の絶対量の制御であり、確
かに抗菌抗カビセラミックスの寿命はそれにより支配さ
れる。しかし抗菌抗カビセラミックスの長寿命化を図る
には本質的には徐放（溶出）速度を効力のある範囲で最
小化すべきである。徐放（溶出）速度はむしろ銀が酸化
チタン膜へどの程度の強さで固定されるかに支配される
と解される。特開平６−６５０１２号ではその観点が開
示されていない。ただし白金膜をさらに酸化チタン膜上
に被覆し、その厚さを変化させる方法はその１つの実施
態様ではある。しかしこの方法では白金塗布という工程
が１つ増加するとともに高価な白金膜を塗布しなければ
ならず、コスト上問題がある。そこで本発明では、白金
を塗布することなく徐放（溶出）速度を最小化して抗菌
抗カビ材の長寿命化を図ることを目的とした。However, the method disclosed in JP-A-6-65012 has the following problems. Changes in the thickness of the titanium oxide film and the content of the metal are both controls of the absolute amount of silver contained in the film, and the life of the antibacterial and antifungal ceramics is certainly governed by it. However, in order to prolong the life of the antibacterial and antifungal ceramics, the sustained release (elution) rate should be essentially minimized within an effective range. It is understood that the sustained release (elution) rate is rather governed by how strong silver is fixed to the titanium oxide film. JP-A-6-65012 does not disclose that viewpoint. However, a method of further coating the platinum film on the titanium oxide film and changing its thickness is one embodiment thereof. However, in this method, the number of steps of platinum application is increased by one, and an expensive platinum film must be applied. Therefore, an object of the present invention is to minimize the sustained release (elution) rate without applying platinum and extend the life of the antibacterial and antifungal material.
【０００８】[0008]
【課題を解決するための手段】本発明では上記課題を解
決すべく、基材に光触媒作用を有する層を介して銀元素
を含む粒子を担持させ、次いでこれを塩素濃度３０ｐｐ
ｍ以上３０００ｐｐｍ未満の溶液に浸漬させることを特
徴とする抗菌材の製造方法とした。According to the present invention, in order to solve the above-mentioned problems, a silver element is provided on a substrate via a layer having a photocatalytic action.
And then the particles having a chlorine concentration of 30 pp
and as the manufacturing method of antibacterial material characterized by immersing in a solution of less than 3000ppm than m.
【０００９】また、光触媒作用を有する担体に、銀元素
を含む粒子を担持させ、次いでこれを塩素濃度３０ｐｐ
ｍ以上３０００ｐｐｍ未満の溶液に浸漬させることを特
徴とする抗菌材の製造方法とした。The carrier having a photocatalytic activity may contain a silver element.
And then the particles having a chlorine concentration of 30 pp
that is immersed in a 3000ppm less solution than m was prepared how the antibacterial material to JP <br/> symptoms.
【００１０】ここで汚水等の液体とは、例えば台所、風
呂場、洗面器等の洗浄後の汚水、尿水、浴槽水、人工噴
水の循環水、プールの水、空調の冷却水などである。汚
水等の液体の流路とは、上記の水が接触する部分のこと
で、例えば流し台のシンクやトラップ、風呂場の床タイ
ル、洗面器のシンクやトラップ、便器のサナ周辺、浴槽
の加熱ガスの給気部や排気部、人工噴水の循環経路内な
どである。Here, the liquid such as sewage is, for example, sewage, urine water, bathtub water, artificial fountain circulating water, pool water, cooling water for air conditioning, etc. after washing kitchens, bathrooms, basins and the like. . The flow path of liquid such as sewage is the part where the above water comes in contact with, for example, sinks and traps in sinks, floor tiles in bathrooms, sinks and traps in washbasins, around sana in toilets, and heated gas in bathtubs. In the circulation path of the artificial fountain.
【００１１】担体の材質は、セラミック、陶磁器材料、
金属、ガラス、熱硬化性樹脂、熱可塑性樹脂、あるいは
それらの複合物等基本的に何でもよい。ただし、光触媒
作用を有する層を酸化物半導体層から形成する場合は、
一般に３００℃以上の高温で熱処理する必要があること
から、熱的安定性に優れるセラミックあるいは陶磁器材
料が好ましい。またセラミック、陶磁器材料、金属の場
合は軽量化の観点から多孔質であることが好ましい。The material of the carrier is ceramic, ceramic material,
Basically, anything such as metal, glass, thermosetting resin, thermoplastic resin, or a composite thereof can be used. However, in the case where a layer having a photocatalytic action is formed from an oxide semiconductor layer,
Generally, it is necessary to perform heat treatment at a high temperature of 300 ° C. or more, and therefore, a ceramic or ceramic material having excellent thermal stability is preferable. In the case of ceramics, ceramic materials, and metals, it is preferable to be porous from the viewpoint of weight reduction.
【００１２】担体の形状は、球状、円柱状、円筒状、角
柱状、中空の角柱状、棒状、板状、粉状、塊状などいず
れでもよいが、コーナー及びエッジ部が尖っていないほ
うが好ましい。その理由は、コーナー及びエッジ部が存
在すると、その部分への銀の付着具合が変化しやすいこ
と、および機械的に弱く優先的に剥離や溶出が生じやす
いことが挙げられる。また、円筒状、中空の角柱状で
は、部材を軽量化できる利点がある。The shape of the carrier may be spherical, cylindrical, cylindrical, prismatic, hollow prismatic, rod-like, plate-like, powdery, massive, etc., but it is preferred that the corners and edges are not sharp. The reason is that if corners and edges exist, the degree of adhesion of silver to the parts is apt to change, and mechanical weakness tends to cause peeling and elution preferentially. In addition, the cylindrical shape and the hollow prism shape have an advantage that the weight of the member can be reduced.
【００１３】光触媒作用を有する層とは、主として光触
媒作用を有する粒子からなる層である。主として光触媒
作用を有する粒子が含まれていれば、他に少量の光触媒
作用を生じない粒子が含まれていてもよい。このような
粒子としては、層の強度を向上させるために加える焼結
助剤等が挙げられる。The layer having a photocatalytic action is a layer mainly composed of particles having a photocatalytic action. As long as particles mainly having a photocatalytic action are included, a small amount of particles that do not generate a photocatalytic action may be included. Such particles include sintering aids added to improve the strength of the layer.
【００１４】光触媒作用を有する層は担体の全面に塗布
してもよいし、一部に塗布してもよい。ただし全面塗布
のほうが、強固に担体に担持される銀の絶対量を増加さ
せることができ、また終端が存在しないのでその部分か
ら優先的に剥離や溶出が生じることがないので好まし
い。光触媒作用を有する層の担体への担持は直接担持さ
せてもよいし、接着層を介してもよい。ただし特に形状
が板状のときは接着層を介したほうが接合強度が向上す
るので好ましい。ここで接着層の材質としては、釉薬等
の無機質の熱可塑性材料、シリコン樹脂等の無機質の熱
硬化性材料、アクリル樹脂等の有機質の熱可塑性材料、
エポキシ樹脂等の有機質の熱硬化性材料のいずれでもよ
い。ただし、光触媒作用により分解されないこと、およ
び３００℃以上の高温で熱処理可能であることから釉薬
等の無機質の熱可塑性材料またはシリコン樹脂等の無機
質の熱硬化性材料のほうがより好ましい。The layer having a photocatalytic action may be applied to the entire surface of the carrier or to a part thereof. However, the whole-surface coating is preferred because the absolute amount of silver carried on the carrier can be increased firmly, and since there is no terminal, there is no preferential peeling or elution from that part. The photocatalytic layer may be directly supported on the carrier, or may be supported via an adhesive layer. However, especially when the shape is plate-like, it is preferable to interpose the adhesive layer because the bonding strength is improved. Here, as the material of the adhesive layer, an inorganic thermoplastic material such as glaze, an inorganic thermosetting material such as a silicone resin, an organic thermoplastic material such as an acrylic resin,
Any of organic thermosetting materials such as epoxy resin may be used. However, an inorganic thermoplastic material such as a glaze or an inorganic thermosetting material such as a silicone resin is more preferable because it is not decomposed by photocatalysis and can be heat-treated at a high temperature of 300 ° C. or more.
【００１５】光触媒作用を有する粒子は、基本的に光照
射時に銀塩から銀を析出しうる程度のバンド・ギャップ
があれば足りるが、より好ましくは自らも抗菌作用を有
するほうがよい。光触媒作用を有する半導体が抗菌作用
を有する理由は、所定以上の電圧が印加され感電死する
という説（特公平４−２９３９３号）もあるが、一般に
は光照射時に生じる活性酸素のためと考えられている。
活性酸素を生成するためには、半導体の伝導帯の位置が
バンドモデルで表すとき水素発生電位より上方にあり、
かつ価電子帯の上端が酸素発生電位より下方にあること
を要する。この条件を満たす半導体には、ＴｉＯ２、Ｓ
ｒＴｉＯ３、ＺｎＯ、ＳｉＣ、ＧａＰ、ＣｄＳ、ＣｄＳ
ｅ、ＭｏＳ３等がある。また微粒化すると伝導帯の位置
は上方に移行するので、１〜１０ｎｍ程度の微粒子で層
を構成できれば、ＳｎＯ２、Ｆｅ２Ｏ３、ＷＯ３、Ｂｉ
２Ｏ３等も抗菌性を有する可能性がある。なお光触媒作
用を有する層を構成する光触媒作用を有する粒子は１種
の物質から構成してもよいし、２種以上の物質で構成し
てもよい。It is sufficient for the particles having a photocatalytic function to have basically a band gap capable of precipitating silver from a silver salt upon irradiation with light, but it is more preferable that the particles themselves have an antibacterial effect. There is a theory that a semiconductor having a photocatalytic action has an antibacterial action (e.g., Japanese Patent Publication No. 4-29393), in which a voltage higher than a predetermined level is applied, resulting in electrocution. ing.
In order to generate active oxygen, the position of the conduction band of the semiconductor is above the hydrogen generation potential when represented by a band model,
In addition, the upper end of the valence band must be lower than the oxygen generation potential. Semiconductors satisfying this condition include TiO2, S
rTiO3, ZnO, SiC, GaP, CdS, CdS
e, MoS3 and the like. In addition, the position of the conduction band shifts upward when the particles are atomized. Therefore, if the layer can be composed of fine particles of about 1 to 10 nm, SnO2, Fe2O3, WO3, Bi
2O3 and the like may also have antibacterial properties. Note that the particles having a photocatalytic action that constitute the layer having a photocatalytic action may be composed of one kind of substance, or may be composed of two or more kinds of substances.
【００１６】銀元素を含む粒子の粒径は、基本的には問
わないが、平均粒径１０ｎｍ以下のほうが表面活性が高
く、そのため下層および隣接する銀に強固に担持される
ので好ましい。The particle size of the particles containing silver element is basically not limited, but it is preferable that the average particle size is 10 nm or less, since the surface activity is high and the silver is firmly supported by the lower layer and the adjacent silver.
【００１７】銀元素を含む粒子の担持方法は、熱処理に
よる方法、光還元による方法等があるが、基本的にどの
ような方法を用いてもよい。ただし銀元素を含む粒子を
担体または基材にある程度強固に結合するほうが好まし
く、そのためには光還元による方法のほうが好ましい。As a method for supporting particles containing silver element, there are a method by heat treatment, a method by photoreduction and the like, but basically any method may be used. However, it is preferable that the particles containing the silver element are firmly bound to the carrier or the substrate to some extent, and for that purpose, the method by photoreduction is more preferable.
【００１８】銀元素を含む粒子を基材にある程度強固に
結合する一態様を以下に示す。まず基材に光触媒作用を
有する粒子の前駆体を塗布し、焼成して複合部材を得
る。この複合部材を銀イオンを含む金属塩溶液中で、回
転させながら光照射して１０ｎｍ以下の超微粒の銀粒子
を基材表面に固定させる。その後超音波をかける等の方
法により、基材表面に多層に弱く吸着された部分を取り
除く。One embodiment in which particles containing silver element are firmly bonded to the substrate to some extent is described below. First, a precursor of particles having a photocatalytic action is applied to a base material and fired to obtain a composite member. The composite member is irradiated with light while rotating in a metal salt solution containing silver ions to fix ultrafine silver particles of 10 nm or less on the surface of the base material. After that, a part that is weakly adsorbed in multiple layers on the surface of the base material is removed by a method such as applying ultrasonic waves.
【００１９】更に、銀元素を含む粒子の層上に、銀と陰
イオンを反応させて難溶性の銀塩を生成させる。その陰
イオンとしては、例えば、塩素イオン、炭酸イオン、リ
ン酸イオン、ヨウ素イオン、臭素イオン、シュウ酸イオ
ン、酸素イオンなどが挙げられる。Further, silver and an anion are reacted on the layer of the particles containing the silver element to form a sparingly soluble silver salt. Examples of the anion include a chloride ion, a carbonate ion, a phosphate ion, an iodine ion, a bromine ion, an oxalate ion, and an oxygen ion.
【００２０】銀元素を含む粒子の層上に難溶性の銀塩を
生成させる方法は、予め銀元素を含む粒子が基材表面に
固定された部材に、上記陰イオンを含む溶液に浸漬させ
て抗菌剤表面に難溶性の銀塩を生成させてもよいし、銀
元素を含む粒子が基材表面に固定された抗菌剤を液体お
よびその流路に配置し、前記液体に上記陰イオンを含む
溶液を供給することにより銀と上記陰イオンを接触させ
てもよい。The method of forming a sparingly soluble silver salt on a layer of particles containing silver element is as follows: a member in which particles containing silver element are fixed in advance on a substrate surface is immersed in the above-mentioned solution containing anion. A hardly soluble silver salt may be generated on the antibacterial agent surface, or the antibacterial agent in which particles containing silver element are fixed on the substrate surface is arranged in a liquid and its flow path, and the liquid includes the anion. The silver and the above-mentioned anion may be brought into contact by supplying a solution.
【００２１】銀元素を含む粒子の層上に難溶性の銀塩を
生成させる方法は、予め銀元素を含む粒子が基材表面に
固定された部材に、上記陰イオンを含む溶液に浸漬させ
て抗菌剤表面に難溶性の銀塩を生成させる方法では、初
期から銀の溶出速度を最小化しうると共に、安定的に制
御しうる点で優れている。The method of forming a sparingly soluble silver salt on a layer of particles containing silver element is as follows: a member in which particles containing silver element are fixed in advance on a substrate surface is immersed in the above-mentioned solution containing anion. The method of forming a hardly soluble silver salt on the surface of the antibacterial agent is excellent in that the silver elution rate can be minimized from the beginning and that the silver salt can be stably controlled.
【００２２】また、銀元素を含む粒子が基材表面に固定
された抗菌剤を、液体およびその流路に配置し、前記液
体に上記陰イオンを含む溶液を供給することにより、銀
と上記陰イオンを接触させる方法では、初期の溶出速度
は大きく殺菌力に優れ、その後難溶性の銀塩が形成され
ていく過程で溶出速度が減少していき、難溶性の銀塩で
抗菌剤表面が覆われると、その後、最小化された一定の
溶出速度で制御されることになる。したがって、初期段
階で流路に菌が著しく繁殖している場合や、プールの水
等の静置した水の場合などのように、初期に菌数を減少
させることで菌の繁殖速度を著しく抑えることができる
状況では、むしろこのタイプの方が有利である。Further, an antibacterial agent having particles containing silver element fixed on the surface of a substrate is arranged in a liquid and its flow path, and a solution containing the above-mentioned anion is supplied to the liquid, whereby silver and the above-mentioned anion are added. In the method of contacting ions, the initial dissolution rate is large and excellent in bactericidal activity, and then the dissolution rate decreases in the process of formation of the hardly soluble silver salt, and the antibacterial agent surface is covered with the hardly soluble silver salt. Once controlled, it will then be controlled at a constant, minimized elution rate. Therefore, when bacteria are remarkably growing in the flow channel in the initial stage, or in the case of standing water such as pool water, by reducing the number of bacteria at the initial stage, the growth speed of the bacteria is significantly suppressed. In situations where this is possible, this type is rather advantageous.
【００２３】上記抗菌剤に紫外線を含む光が照射されて
いてもよい。それにより下層に存在する光触媒作用も活
用することができ、抗菌力が増すからである。陰イオン
が塩素イオンならば、数ｐｐｍ以上あれば銀の溶出速度
を抑制する効果がある。したがって水道水によっても効
果が生じるので、銀元素を含む粒子が基材表面に固定さ
れた抗菌剤を、液体およびその流路に配置し、前記液体
に上記陰イオンを含む溶液を供給することにより、銀と
上記陰イオンを接触させる方法において、山間部地域を
除き、水道以外の塩素供給手段を特に設けなくてもよい
ことになる。また銀の溶出速度抑制効果は、フッ化イオ
ンを除くハロゲン化イオンにおいて特に大きく、その中
で塩素イオンは最も安価に得られることからも好まし
い。The antibacterial agent may be irradiated with light containing ultraviolet rays. Thereby, the photocatalytic action existing in the lower layer can be utilized, and the antibacterial activity is increased. If the anion is a chloride ion, a concentration of several ppm or more has an effect of suppressing the elution rate of silver. Therefore, since the effect is also produced by tap water, the antibacterial agent in which the particles containing the silver element are fixed on the surface of the base material is arranged in the liquid and its flow path, and the solution containing the anion is supplied to the liquid. In the method of bringing silver and the anion into contact with each other, it is not necessary to provide any chlorine supply means other than the water supply except for the mountainous area. In addition, the effect of suppressing the dissolution rate of silver is particularly large in halide ions other than fluoride ions, and among them, chloride ions are preferable because they can be obtained at the lowest cost.
【００２４】陰イオン量は多いほど抗菌剤表面を完全に
覆うことになるので、銀の溶出速度を最小かつ一定にで
き好ましい。ただしあまり多く添加すると抗菌剤表面が
白色化し、かつ透光性を失うので光触媒作用を有する下
地層による抗菌効果を活用しにくくなり、好ましくな
い。例えば、塩素イオンの場合には３０ｐｐｍ添加すれ
ば、抗菌剤表面は塩素イオンで覆われるようになり、銀
の溶出速度は一定となる。ただし３０００ｐｐｍ以上添
加すると、抗菌剤表面は透光性を失うことになる。The larger the amount of anions, the more completely the surface of the antibacterial agent is covered, so that the elution rate of silver can be minimized and constant, which is preferable. However, if too much is added, the surface of the antibacterial agent becomes white and loses light transmission, so that it is difficult to utilize the antibacterial effect of the photocatalytic underlayer, which is not preferable. For example, in the case of chloride ions, if 30 ppm is added, the surface of the antibacterial agent will be covered with chloride ions, and the elution rate of silver will be constant. However, if 3000 ppm or more is added, the surface of the antibacterial agent loses light transmittance.
【００２５】[0025]
【作用】最外層の銀が陰イオンと反応して難溶性の銀塩
を形成することにより、銀の溶出速度を最小化させるこ
とができる。それにより抗菌性が長期に亘り維持され
る。The silver in the outermost layer reacts with the anion to form a sparingly soluble silver salt, so that the elution rate of silver can be minimized. Thereby, the antibacterial property is maintained for a long time.
【００２６】[0026]
実施例１ 直径５ｍｍのアルミナ製の多孔体ボールに平
均粒径０．０１μｍのＴｉＯ２ゾルのアンモニア解膠懸
濁液をスプレー・コーティング法により塗布し、７００
℃で１時間焼成する工程を２回くりかえした後、硝酸銀
水溶液に浸漬させ、ボールをよく回転させながらＢＬＢ
ランプを２０分照射する工程により銀粒子をボール全面
に固定させた後、超音波分散することにより過剰に付着
した銀を除去し、よく水洗することにより抗菌剤試料を
得た。このときのＴｉＯ２の結晶型はアナターゼであっ
た。また担持された銀粒子の粒径は数ｎｍ〜１０ｎｍ程
度であった。得られた試料について以下に示す方法によ
り、銀の溶出速度および抗菌性を評価した。Example 1 Ammonia peptized suspension of TiO2 sol having an average particle diameter of 0.01 μm was applied to a 5 mm-diameter porous alumina ball by a spray coating method, and the resulting mixture was coated with 700 μm.
After repeating the process of baking at 1 ° C. for 1 hour twice, immerse in an aqueous silver nitrate solution and rotate the ball
After the silver particles were fixed on the entire surface of the ball by a step of irradiating the lamp for 20 minutes, excessively adhered silver was removed by ultrasonic dispersion, and the sample was thoroughly washed with water to obtain an antibacterial agent sample. At this time, the crystal form of TiO2 was anatase. The particle size of the supported silver particles was about several nm to 10 nm. The obtained samples were evaluated for silver dissolution rate and antibacterial properties by the methods described below.
【００２７】銀の溶出速度は以下の方法により評価し
た。まず予め８０体積％エタノールに２時間浸漬後、５
０℃で２時間乾燥した抗菌剤試料５個を種々の溶媒１０
ｍｌとともに滅菌試験管に入れ、３０℃ふらん器で２４
時間放置した。その後０．４５μｍのメンブランフィル
タでろ過し、原子吸光（日立６０００フレーム式）によ
り分析した。The elution rate of silver was evaluated by the following method. First, immerse in 80% by volume ethanol for 2 hours beforehand.
Five antimicrobial samples dried at 0 ° C. for 2 hours in various solvents 10
and put it in a sterile test tube together with
Left for hours. Thereafter, the solution was filtered through a 0.45 μm membrane filter, and analyzed by atomic absorption (Hitachi 6000 flame method).
【００２８】抗菌性の評価は以下の方法により評価し
た。まず予め８０体積％エタノールに２時間浸漬後、５
０℃で２時間乾燥した抗菌剤試料５個を種々の溶媒１０
ｍｌとともに滅菌試験管に入れ、３０℃ふらん器で３時
間放置した。その後抗菌剤試料を取り出し、オートクレ
ーブ中１２１℃で２０分洗浄し、８０体積％エタノール
に２時間浸漬後、５０℃で乾燥させて表面を洗浄した。
次いで大腸菌（Ｅｓｃｈｅｒｉｃｈｉａ Ｃｏｌｉ Ｗ
３１１０株）の菌液を種々の培地で１０５ＣＦＵ／ｍｌ
に調整したものを、滅菌した１ｍｌ試料瓶に採取し、そ
こに抗菌剤試料を１個入れ、３０℃ふらん器で数時間放
置した後の菌数を調べた。なおここで用いた溶媒中の含
有塩素量は人工尿では約１０％、ブイヨンでは約１０ｐ
ｐｍ、超純水では１ｐｐｍ未満である。The antibacterial properties were evaluated by the following methods. First, immerse in 80% by volume ethanol for 2 hours beforehand.
Five antimicrobial samples dried at 0 ° C. for 2 hours in various solvents 10
The mixture was placed in a sterile test tube together with the ml, and allowed to stand for 3 hours in a 30 ° C. air shaker. Thereafter, the antibacterial agent sample was taken out, washed in an autoclave at 121 ° C. for 20 minutes, immersed in 80% by volume ethanol for 2 hours, and dried at 50 ° C. to wash the surface.
Then E. coli (Escherichia Coli W
3110 strain) at 105 CFU / ml in various media
The sample prepared in Example 1 was collected in a sterilized 1 ml sample bottle, one antibacterial agent sample was put in the sample bottle, and the number of bacteria was checked after standing for several hours at 30 ° C. in an air incubator. The amount of chlorine contained in the solvent used here was about 10% for artificial urine and about 10 p for broth.
pm and less than 1 ppm in ultrapure water.
【００２９】その結果、銀の溶出量は超純水で１６．７
ｐｐｍ、ブイヨン培地では９．１３ｐｐｍ、人工尿で
１．８４ｐｐｍであり、含有塩素量の多いものほど銀の
溶出量が小さくなった。また種々の溶媒中に抗菌剤試料
を放置したときの初期の抗菌性を表１に示す。その結
果、銀の溶出速度の小さな人工尿中に放置したものでも
残留菌数は１０ｃｅｌｌｓ／ｍｌ未満と良好な結果を示
した。As a result, the elution amount of silver was 16.7 with ultrapure water.
ppm, in the bouillon medium, 9.13 ppm, and in the artificial urine, 1.84 ppm. The higher the chlorine content, the smaller the amount of silver eluted. Table 1 shows the initial antibacterial properties when the antibacterial agent samples were left in various solvents. As a result, the number of residual bacteria was less than 10 cells / ml, which was a good result, even when the sample was left in artificial urine having a low silver elution rate.
【００３０】[0030]
【表１】 [Table 1]
【００３１】また、種々の溶媒中に抗菌剤試料を放置し
たときの２か月後の抗菌性を表１に示す。その結果、銀
の溶出速度の人工尿中に放置したものでも残留菌数は１
０ｃｅｌｌｓ／ｍｌ未満と変化が認められず、充分な抗
菌性を示した。以上の結果から含有塩素量の多いものほ
ど銀の溶出量が小さく、かつかかる少量の溶出量あるに
もかかわらず、長期にわたり充分な抗菌性を示すことが
判明した。Table 1 shows the antibacterial properties two months after the antibacterial agent samples were left in various solvents. As a result, the number of residual bacteria was 1 even when left in artificial urine with silver elution rate.
No change was observed below 0 cells / ml, indicating a sufficient antibacterial property. From the above results, it was found that the higher the chlorine content, the smaller the amount of silver eluted and, despite such a small amount of elution, exhibited sufficient antibacterial properties over a long period of time.
【００３２】比較例 直径５ｍｍのアルミナ製の多孔体
ボールに直接１重量％硝酸銀水溶液をスプレー・コーテ
ィング法にて塗布し乾燥させて得た固形物を作製した。
得られた固形物の上に固定された銀粒子の大きさは実施
例のものよりもやや大きく数ｎｍ〜１００ｎｍぐらいで
あった。この試料について、実施例１と同様の手法（ブ
イヨン培地にて）で２４時間後の銀の溶出量、初期抗菌
性および１か月後の抗菌性を評価した。その結果、２４
時間後の銀の溶出量は＞１００ｐｐｍと大きかった。ま
た初期抗菌性は１０１ｃｅｌｌｓ／ｍｌと良好だが、１
か月後の抗菌性は１０３〜１０４ｃｅｌｌｓ／ｍｌでほ
とんど効果を失っていることが判明した。COMPARATIVE EXAMPLE A 1% by weight aqueous solution of silver nitrate was applied directly to a 5 mm-diameter porous alumina ball by spray coating and dried to obtain a solid.
The size of the silver particles fixed on the obtained solid was slightly larger than that of the example and was about several nm to 100 nm. For this sample, the amount of silver eluted after 24 hours, the initial antibacterial property and the antibacterial property after one month were evaluated in the same manner as in Example 1 (in a bouillon medium). As a result, 24
The amount of silver eluted after time was as large as> 100 ppm. Although the initial antibacterial property is as good as 101 cells / ml, it is 1
It was found that the antibacterial property after months was almost ineffective at 103 to 104 cells / ml.
【００３３】実施例２ 実施例１で形成した抗菌剤試料
を用いて、塩素イオンの濃度による銀の溶出量を評価し
た。尚、塩素濃度は、塩化アンモニウム水溶液を作製
し、塩化アンモニウムの濃度を変化させることにより評
価した。その結果を表２に示す。Example 2 Using the antibacterial agent sample formed in Example 1, the amount of silver eluted depending on the chloride ion concentration was evaluated. The chlorine concentration was evaluated by preparing an aqueous ammonium chloride solution and changing the concentration of ammonium chloride. Table 2 shows the results.
【００３４】[0034]
【表２】 [Table 2]
【００３５】その結果、概念図１に示すように塩素イオ
ン濃度が３０ｐｐｍまでは溶出速度は急激に減少し、３
０ｐｐｍ以上ではほぼ一定になることが観察された。こ
の現象はつぎのように説明できる。まず３０ｐｐｍまで
（図１の 領域）は図２に示すようにＡｇ層からの速い
溶出とＡｇＣｌが形成された部分からの遅い溶出が同時
に生じる。そして塩素イオン濃度の増加に伴い、ＡｇＣ
ｌの形成部分が増加し、Ａｇ層からの速い溶出の生じる
割合が減少する。したがって塩素イオン濃度が増加する
と溶出速度は減少していく。それに対し、図３のように
３０ｐｐｍ以上（図１の の領域）ではＡｇ層はＡｇＣ
ｌに完全に覆われることになる。したがってＡｇＣｌか
らの遅い溶出しか生じなくなるので、銀の溶出速度は一
定となる。As a result, as shown in the conceptual diagram 1, the elution rate sharply decreases until the chloride ion concentration reaches 30 ppm,
It was observed that the concentration was almost constant at 0 ppm or more. This phenomenon can be explained as follows. First, up to 30 ppm (region in FIG. 1), as shown in FIG. 2, fast elution from the Ag layer and slow elution from the portion where AgCl is formed occur simultaneously. And with the increase of chloride ion concentration, AgC
The formation of 1 increases, and the rate of rapid elution from the Ag layer decreases. Therefore, the elution rate decreases as the chloride ion concentration increases. On the other hand, as shown in FIG. 3, when the concentration is 30 ppm or more (the region of FIG. 1), the Ag layer becomes AgC
1 will be completely covered. Thus, only a slow elution from AgCl occurs, and the silver elution rate is constant.
【００３６】３０ｐｐｍ以上で、銀の溶出量が少なくな
るのは、光触媒作用を有する層上に形成された銀元素粒
子を含む層上に塩化銀が膜上に形成され、その膜上塩化
銀からの溶出によると思われる。また、多少の変動は、
最表層の塩化銀の脱離により、銀元素粒子を含む層から
の溶出が多少起きているものと思われる。At 30 ppm or more, the amount of silver eluted is reduced because silver chloride is formed on a layer containing silver element particles formed on a layer having a photocatalytic action, and Probably due to the elution of Also, some fluctuations,
It is considered that the elution from the layer containing the silver element particles occurs to some extent due to the desorption of silver chloride in the outermost layer.
【００３７】[0037]
【発明の効果】基材に光触媒作用を有する層を介して銀
元素を含む粒子が担持されている抗菌剤と、銀と難溶性
の塩を形成する陰イオンとを接触させて難溶性の銀塩を
抗菌剤表面に形成することにより、前記抗菌剤上の銀の
溶出速度を抑えることができ、それにより前記抗菌剤の
長寿命化を図ることができる。According to the present invention, an antibacterial agent in which particles containing silver element are supported on a substrate via a layer having a photocatalytic action and an anion which forms a sparingly soluble salt with silver are brought into contact with the sparingly soluble silver. By forming the salt on the surface of the antibacterial agent, the elution rate of silver on the antibacterial agent can be suppressed, and the life of the antibacterial agent can be extended.
【図１】塩素濃度と銀の溶出速度との関係を表す図。FIG. 1 is a graph showing the relationship between chlorine concentration and silver elution rate.
【図２】塩素濃度３０ｐｐｍまでの銀の溶出状態を示す
図。FIG. 2 is a diagram showing a silver elution state up to a chlorine concentration of 30 ppm.
【図３】塩素濃度３０ｐｐｍ以上での銀の溶出状態を示
す図。FIG. 3 is a diagram showing the elution state of silver at a chlorine concentration of 30 ppm or more.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−65012（ＪＰ，Ａ) 特開 平４−83587（ＪＰ，Ａ) 特開 昭63−20090（ＪＰ，Ａ) 特開 平３−193191（ＪＰ，Ａ) 特開 平２−268103（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 59/16 B01J 21/00 - 38/74 C02F 1/50 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-65012 (JP, A) JP-A-4-83587 (JP, A) JP-A-63-20090 (JP, A) 193191 (JP, A) JP-A-2-268103 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A01N 59/16 B01J 21/00-38/74 C02F 1/50
Claims (2)
銀元素を含む粒子を担持させ、次いでこれを塩素濃度３
０ｐｐｍ以上３０００ｐｐｍ未満の溶液に浸漬させるこ
とを特徴とする抗菌材の製造方法。 Claims 1. A photocatalytic layer is provided on a substrate,
Particles containing silver element are supported, and then the particles having a chlorine concentration of 3
This <br/> a method for producing antibacterial material you characterized to be immersed in a solution of less than 3000ppm than 0 ppm.
む粒子を担持させ、次いでこれを塩素濃度３０ｐｐｍ以
上３０００ｐｐｍ未満の溶液に浸漬させることを特徴と
する抗菌材の製造方法。 2. A carrier having a photocatalytic action containing a silver element.
Particles are then supported, and this is then reduced to a chlorine concentration of 30 ppm or less.
Method for producing antibacterial material you <br/> characterized by immersing in a solution of less than the above 3000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31230994A JP3228035B2 (en) | 1994-11-10 | 1994-11-10 | Manufacturing method of antibacterial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31230994A JP3228035B2 (en) | 1994-11-10 | 1994-11-10 | Manufacturing method of antibacterial material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08133919A JPH08133919A (en) | 1996-05-28 |
| JP3228035B2 true JP3228035B2 (en) | 2001-11-12 |
Family
ID=18027701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31230994A Expired - Fee Related JP3228035B2 (en) | 1994-11-10 | 1994-11-10 | Manufacturing method of antibacterial material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3228035B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3856535B2 (en) * | 1997-08-01 | 2006-12-13 | シャープ株式会社 | Method for producing photocatalyst body |
| US6303183B1 (en) | 1999-11-08 | 2001-10-16 | Aos Holding Company | Anti-microbial porcelain enamel coating |
| DE10217649A1 (en) * | 2002-04-19 | 2004-01-08 | Stadelmann, Heinz W., Dr. | Disinfection system, especially for the disinfection of drinking and industrial water as well as the production and use of the disinfection system |
| JP2006231150A (en) * | 2005-02-23 | 2006-09-07 | Ebara Corp | Photocatalyst, method for manufacturing the same and method and apparatus for treating water by using the same |
| US8178120B2 (en) * | 2008-06-20 | 2012-05-15 | Baxter International Inc. | Methods for processing substrates having an antimicrobial coating |
| US8277826B2 (en) | 2008-06-25 | 2012-10-02 | Baxter International Inc. | Methods for making antimicrobial resins |
| US20100227052A1 (en) * | 2009-03-09 | 2010-09-09 | Baxter International Inc. | Methods for processing substrates having an antimicrobial coating |
| CN103997890B (en) * | 2011-07-08 | 2016-12-07 | 卡池公司 | Antimicrobial material of argentiferous and application thereof |
| CN103566954B (en) * | 2012-07-31 | 2016-08-17 | 华中科技大学 | A kind of for visible light-responded magnetic titanium dioxide composite material and preparation method thereof |
| CN103709858B (en) * | 2013-11-28 | 2016-03-02 | 内蒙古伊晨环境材料有限公司 | A kind of have Environment-friendlyinternal internal wall paint of purifying formaldehyde function and preparation method thereof |
| JP6510782B2 (en) * | 2014-09-18 | 2019-05-08 | 国立大学法人 筑波大学 | Photocatalyst, coating film and sterilization device |
| US9650265B2 (en) | 2015-03-04 | 2017-05-16 | Claire Technologies, Llc | Disinfection compositions and methods |
| CN106270479B (en) * | 2015-05-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of attapulgite-nano silver composite inorganic powder and preparation method |
-
1994
- 1994-11-10 JP JP31230994A patent/JP3228035B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08133919A (en) | 1996-05-28 |
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