JP3210544B2 - Antibacterial and antifungal aluminum building materials and fittings using the same - Google Patents
Antibacterial and antifungal aluminum building materials and fittings using the sameInfo
- Publication number
- JP3210544B2 JP3210544B2 JP11906395A JP11906395A JP3210544B2 JP 3210544 B2 JP3210544 B2 JP 3210544B2 JP 11906395 A JP11906395 A JP 11906395A JP 11906395 A JP11906395 A JP 11906395A JP 3210544 B2 JP3210544 B2 JP 3210544B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- antibacterial
- photocatalytic
- aluminum
- semiconductor
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims description 29
- 239000004566 building material Substances 0.000 title claims description 25
- 230000000844 anti-bacterial effect Effects 0.000 title description 56
- 230000000843 anti-fungal effect Effects 0.000 title description 32
- 229940121375 antifungal agent Drugs 0.000 title description 3
- 239000010408 film Substances 0.000 claims description 144
- 239000000463 material Substances 0.000 claims description 67
- 230000001699 photocatalysis Effects 0.000 claims description 60
- 239000004065 semiconductor Substances 0.000 claims description 44
- 239000010407 anodic oxide Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 36
- 239000011941 photocatalyst Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 229910000838 Al alloy Inorganic materials 0.000 claims description 29
- 239000010419 fine particle Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- 230000000845 anti-microbial effect Effects 0.000 claims description 7
- 239000005357 flat glass Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 239000002245 particle Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 206010029803 Nosocomial infection Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 208000037942 Methicillin-resistant Staphylococcus aureus infection Diseases 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 208000001388 Opportunistic Infections Diseases 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 or the like Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌・抗黴性のアルミ
ニウム又はアルミニウム合金製の建築材（以下、アルミ
建築材と略称する。）に関し、さらに詳しくは、その表
面に形成した陽極酸化皮膜上に光触媒作用を有する半導
体あるいはさらに抗菌性金属をコーティングしてなる抗
菌・抗黴性に優れたアルミ建築材、及びそれを用いた建
具に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building material made of aluminum or an aluminum alloy having antibacterial and antifungal properties (hereinafter abbreviated as "aluminum building material"), and more particularly to an anodized film formed on the surface thereof. The present invention relates to an aluminum building material having excellent antibacterial and antifungal properties obtained by coating a semiconductor having a photocatalytic action or an antibacterial metal thereon, and a fitting using the same.
【０００２】[0002]
【従来の技術】近年、ＭＲＳＡ（メチシリン耐性黄色ブ
ドウ球菌）等の院内感染が問題視されるようになってき
ている。院内感染の多くは日和見感染症であり、ウィル
ス、細菌、原虫、黴等が、抵抗力や免疫力が低下した人
体の中で急に活発化して発症する感染症である。例えば
ＭＲＳＡの感染に関して言えば、その菌は主に患者や院
内従事者の体、スリッパ、医療器具等を介して病院内に
広がるようだが、空気中の塵埃に菌が付着して空気感染
を起こすこともある。そのため、院内感染を防ぐには室
内空気全体を殺菌、浄化処理する必要があり、従来、薬
品による消毒や空気清浄器に頼ってきた。しかしながら
消毒においては、薬品を用いるため人体への影響も無視
できず、薬品の臭いも不快感を与えるといった問題があ
り、また、作業が容易でない等の理由から頻繁に行うわ
けにもいかなかった。一方、空気清浄器による院内の浄
化は比較的容易ではあるが、空気中の塵埃等を静電気に
より除去する原理であるため、細菌、黴、及びそれに付
随する臭気等は除去しにくいといった問題があった。ま
た、煙草のヤニがサッシ、パネル材等の建築部材表面に
付着し汚れた場合、美観を損ねるだけでなく、その部分
に細菌が付着し繁殖し易いという問題もあった。2. Description of the Related Art In recent years, nosocomial infections such as MRSA (methicillin-resistant Staphylococcus aureus) have been regarded as a problem. Most hospital-acquired infections are opportunistic infections, in which viruses, bacteria, protozoa, fungi, and the like suddenly become active and develop in a human body with reduced resistance and immunity. For example, with regard to MRSA infection, it seems that the bacterium spreads in the hospital mainly through the body of patients and hospital staff, slippers, medical equipment, etc., but causes bacteria to adhere to dust in the air and cause airborne infection Sometimes. Therefore, in order to prevent hospital-acquired infection, it is necessary to sterilize and purify the entire indoor air, and in the past, they have relied on chemical disinfection and air purifiers. However, in the disinfection, the use of chemicals has a problem that the effect on the human body cannot be neglected, and there is a problem that the smell of the chemicals gives uncomfortable feelings. Further, it cannot be performed frequently because of the difficulty of work. . On the other hand, cleaning of the hospital with an air purifier is relatively easy, but since it is based on the principle of removing dust and the like in the air by static electricity, there is a problem that it is difficult to remove bacteria, fungi, and odors associated therewith. Was. In addition, when tobacco tar adheres to the surface of a building member such as a sash or a panel material and becomes dirty, there is a problem that not only the aesthetic appearance is impaired but also bacteria adhere to the portion and easily propagate.
【０００３】ところで、ＴｉＯ2 に代表される光触媒作
用を有する半導体微粒子が抗菌・抗黴作用を有すること
は従来から知られており、最近ではそれらを利用して、
細菌や黴が繁殖しにくい様々な材料が研究、開発されて
いる。例えば、特開平２−６３３３号公報には酸化チタ
ンの粒子表面に銅、亜鉛等の抗菌性金属を担持させた抗
菌性粉末について開示されており、この粉末を樹脂、ゴ
ム、ガラス等に配合することによって抗菌性組成物が得
られ、また、公知の方法により、電機機器、家具調度
品、室内装飾材、食品等の包装資材等の抗菌性処理のほ
か、環境衛生施設、機器類の抗菌剤等として上記粉末を
利用できると教示している。特開平６−６５０１２号公
報には、銀、銅、亜鉛、白金等の金属を含有した酸化チ
タン膜をコンクリート、ガラス、プラスチック、セラミ
ックス、金属等の材質からなる基板にコーティングする
ことによって、該基板において雑菌及び黴の繁殖を防止
できる旨が開示されている。さらに特開平４−３０７０
６６号公報には、パネルの裏面に光触媒を付設し、該パ
ネルの裏側に短波長光ランプを配置し、このランプから
光触媒へ紫外線照射することによって、光触媒を活性化
し、パネルが設置された室内の脱臭を図るという、光触
媒による室内空気のリフレッシュ法が開示されている。[0003] By the way, it has been known that semiconductor fine particles having a photocatalytic action represented by TiO 2 have an antibacterial and antifungal action.
Various materials that make it difficult for bacteria and fungi to propagate have been researched and developed. For example, Japanese Patent Application Laid-Open No. 2-6333 discloses an antibacterial powder in which an antibacterial metal such as copper or zinc is supported on the surface of titanium oxide particles, and this powder is mixed with resin, rubber, glass, or the like. An antibacterial composition can be obtained by the method described above, and in addition to the antibacterial treatment of electrical equipment, furniture furniture, interior decoration materials, packaging materials such as food, etc., and an environmental sanitary facility, an antibacterial agent for equipment by a known method. It teaches that the above powder can be used as such. JP-A-6-65012 discloses that a titanium oxide film containing a metal such as silver, copper, zinc, platinum or the like is coated on a substrate made of a material such as concrete, glass, plastic, ceramics, metal, etc. Discloses that propagation of various bacteria and fungi can be prevented. Further, JP-A-4-3070
No. 66, a photocatalyst is attached to the back surface of the panel, a short-wavelength light lamp is arranged on the back side of the panel, and the photocatalyst is activated by irradiating the photocatalyst with ultraviolet light from the lamp, so that the room where the panel is installed is provided. There is disclosed a method of refreshing indoor air using a photocatalyst, which aims at deodorization of indoor air.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、特開平
４−３０７０６６号公報に記載の室内の脱臭を目的とし
た脱臭パネル機構は、前述した通り紫外線ランプを設置
する必要があり、この様に特別な光源を用いた場合、光
源のメンテナンスをしなければならない点や電気代など
のランニングコストがかかるという欠点がある。また、
紫外線ランプを室内に配置するのは危険であり、周りに
ある内装材や家具の色褪せを招くことにもなる。また、
アルミニウム又はアルミニウム合金（以下、アルミ合金
という）製の建築部材、例えばパネル材上に酸化チタン
等の光触媒をコーティングすると、アルミ合金基材と光
触媒の充分な密着性が得られず、コーティングした光触
媒の膜が剥離し易いという問題がある。However, the deodorizing panel mechanism described in JP-A-4-307066 for the purpose of deodorizing indoors requires the installation of an ultraviolet lamp as described above. When a light source is used, there are drawbacks in that maintenance of the light source is required and running costs such as electricity costs are required. Also,
Placing an ultraviolet lamp indoors is dangerous and can also lead to fading of the interior materials and furniture around it. Also,
Aluminum or aluminum alloy (hereinafter, referred to as aluminum alloy) building elements made of, for example, coating the photocatalyst such as titanium oxide on the panel material is not sufficient adhesion between A Rumi alloy base and the photocatalyst, which was coated There is a problem that the photocatalyst film is easily peeled off.
【０００５】従って、本発明の目的は、特別の装置を要
することなくメンテナンスフリーであり、しかも抗菌・
抗黴性の膜が高い密着強度でコーティングされた抗菌・
抗黴性のアルミ建築材を提供することにある。さらに本
発明の目的は、空気清浄器など特別な装置を必要とせ
ず、しかも薬品による消毒などを行わなくても、自己浄
化機能を有し、細菌や黴の繁殖を防いで室内環境を清浄
化する機能を有する建具ユニットを提供することにあ
る。Accordingly, it is an object of the present invention to provide a maintenance-free system that does not require a special device, and furthermore, has an antibacterial property.
Antimicrobial the antifungal the film is coated with adhesive strength have high-
An object of the present invention is to provide an anti-mold aluminum building material. Furthermore, an object of the present invention is to eliminate the need for special equipment such as an air purifier and have a self-purifying function without disinfecting with a chemical, etc., to prevent the propagation of bacteria and molds, and to purify the indoor environment. It is an object of the present invention to provide a fitting unit having a function of performing the above.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明の一側面によれば、アルミニウム又はアルミ
ニウム合金からなる基材の表面に陽極酸化皮膜を形成
し、さらに該陽極酸化皮膜上に光触媒作用を有する半導
体を含む薄膜をコーティングしてなり、該光触媒作用を
有する半導体を含む薄膜の膜厚が１μｍ以下であること
を特徴とするアルミ建築材が提供される。好適な態様に
おいては、前記光触媒作用を有する半導体を含む薄膜の
上にさらにＡｇ、Ｃｕ等の抗菌性の金属をコーティング
することにより、より一層抗菌・抗黴性に優れたアルミ
建築材が提供される。According to one aspect of the present invention, an anodic oxide film is formed on a surface of a substrate made of aluminum or an aluminum alloy, and the anodic oxide film is formed on the anodic oxide film. the Ri Na by coating a thin film including a semiconductor having a photocatalytic activity, a photocatalyst action
The thickness of the thin film containing the semiconductor contained is 1 μm or less
An aluminum building material is provided. In a preferred embodiment, an aluminum building material having more excellent antibacterial and antifungal properties is provided by further coating an antibacterial metal such as Ag or Cu on the thin film containing a semiconductor having a photocatalytic action. You.
【０００７】さらに本発明の他の側面によれば、このよ
うなアルミ建築材を用いた建具ユニットも提供される。
その一態様によれば、アルミニウム又はアルミニウム合
金からなる基材の表面に陽極酸化皮膜を形成し、さらに
該陽極酸化皮膜上に光触媒作用を有する半導体を含む薄
膜をコーティングしてなる框材もしくは枠材と、表面に
光触媒作用を有する半導体を含む薄膜をコーティングし
てなるパネル材と、光触媒作用を有する半導体微粒子を
含有する水密気密材とから構成される建具が提供され
る。好適な態様においては、上記パネル材が窓ガラスパ
ネル材である建具が提供される。According to still another aspect of the present invention, there is provided a fitting unit using such an aluminum building material.
According to one embodiment, a frame material or a frame material formed by forming an anodic oxide film on the surface of a substrate made of aluminum or an aluminum alloy, and further coating the anodic oxide film with a thin film containing a semiconductor having a photocatalytic action And a panel member formed by coating the surface with a thin film containing a semiconductor having a photocatalytic action, and a watertight and airtight material containing semiconductor fine particles having a photocatalytic action. In a preferred aspect, there is provided a fitting, wherein the panel material is a window glass panel material.
【０００８】[0008]
【発明の作用及び態様】前記したように、アルミ合金地
金に直接、光触媒作用を有する半導体を含む膜（以下、
光触媒膜という）をコーティングすると、光触媒膜とア
ルミ合金地金との密着性が悪く、衝撃を受けた場合に光
触媒膜が剥離してしまうという問題がある。このような
問題を解決するためには、光触媒膜とアルミ合金地金の
間に、光触媒膜とアルミ合金地金との密着性を強めるア
ンカー効果を有する膜を介在させる必要がある。このよ
うな中間膜として、本発明のアルミ建築材は、アルミ合
金表面に一体的に形成された微多孔質の陽極酸化皮膜を
利用するものである。すなわち、本発明のアルミ建築材
は、アルミ合金からなる基材の表面に陽極酸化皮膜を形
成し、さらに該陽極酸化皮膜上に光触媒膜をコーティン
グしたものである。陽極酸化皮膜は絶縁膜であり、しか
も表面に直径約５ｎｍ〜２５０ｎｍの細孔が無数に開い
た微多孔質で、しかも凹凸のある構造を有している。従
って、微多孔質構造によるアンカー効果によって、コー
ティングされる光触媒膜のアルミ合金地金に対する密着
性を向上させることができる。As described above, a film containing a semiconductor having a photocatalytic action directly on an aluminum alloy ingot (hereinafter referred to as a film).
When coating the) that photocatalyst film, adhesion to the photocatalyst film and an aluminum alloy ingots is poor, there is a problem that the photocatalytic film is peeled off in the event of an impact. In order to solve such a problem, it is necessary to interpose a film having an anchor effect for enhancing the adhesion between the photocatalyst film and the aluminum alloy metal between the photocatalytic film and the aluminum alloy metal. As such an intermediate film, the aluminum building material of the present invention utilizes a microporous anodic oxide film integrally formed on an aluminum alloy surface. That is, the aluminum building material of the present invention is obtained by forming an anodic oxide film on the surface of a base material made of an aluminum alloy, and further coating a photocatalytic film on the anodic oxide film. The anodic oxide film is an insulating film, and has a microporous structure with innumerable pores having a diameter of about 5 nm to 250 nm on the surface, and has a structure with irregularities. And slave Tsu <br/>, by the anchor effect of the microporous structure, it is possible to improve the adhesiveness to an aluminum alloy ingots of the photocatalyst film to be coated.
【０００９】このように、本発明のアルミ建築材は、光
触媒膜とアルミ合金地金との密着性を強めるアンカー効
果を有する微多孔質の陽極酸化皮膜の上に光触媒膜をコ
ーティングしたものであるため、光触媒膜の剥離といっ
た問題もなく、また、光が当たる材料表面の光触媒膜に
は充分な量の半導体が存在するため、優れた抗菌・抗黴
作用を示す。すなわち、材料表面に露出している半導体
微粒子、例えばＴｉＯ２に太陽光線や蛍光灯の光が照射
されると、ＴｉＯ２表面に正孔（ｈ＋）及び励起電子
（ｅ−）が生じ、光触媒作用を示す。すなわち、この電
子の作用により空気中の酸素が還元され、酸素ラジカル
を生じ、また正孔の作用によって水が酸化され、ＯＨラ
ジカルを生ずる。これらの活酸素は優れた殺菌作用を有
し、その結果、黴等が発生しにくくなる。As described above, the aluminum building material of the present invention comprises a photocatalyst film on a microporous anodized film having an anchor effect for enhancing the adhesion between the photocatalyst film and the aluminum alloy base metal. because the is obtained by coating, without problems such as peeling of the photocatalytic film, also, since a sufficient amount of the semiconductor is present in the photocatalyst film of a material surface which light impinges, exhibit excellent antibacterial and antifungal effects. That is, when semiconductor particles, for example, TiO 2 exposed on the surface of the material are irradiated with sunlight or a fluorescent lamp, holes (h + ) and excited electrons (e − ) are generated on the TiO 2 surface, and the photocatalyst is generated. Show action. In other words, this power
Oxygen in the air is reduced by the action of the child, the oxygen radicals raw Ji, also water is oxidized by the action of positive holes, OH La
Generates dicals. These active oxygens have an excellent bactericidal action, and as a result, mold and the like hardly occur.
【００１０】また、上記のように抗菌・抗黴性に優れる
アルミ建築材から框材もしくは枠材を作製し、これを、
同様に抗菌・抗黴性を付与した他の部材、例えば、表面
に光触媒作用を有する半導体を含む薄膜をコーティング
してなるパネル材や、光触媒作用を有する半導体微粒子
を含有する水密気密材と組み合わせて建具ユニットを構
成することにより、抗菌・抗黴効果が一層高まり、これ
らの部材の表面に限らず、このような建築部材で構成さ
れる室内空間全体を衛生的に保つことができる。すなわ
ち、建具内面全体に光触媒膜をコーティングすることに
より、日中は太陽光線が照射されるし、夜間でも蛍光灯
の光が照射されるため、コーティング面は常に光触媒機
能を発揮することになり、前記した原理によって抗菌・
抗黴作用を示す面となる。また、室内空気は、常に対流
しているため建具内面に接しており、このようにして建
具内面に触れることにより清浄化される。Further, as described above, a frame material or a frame material is produced from an aluminum building material having excellent antibacterial and antifungal properties, and
Similarly, in combination with other members provided with antibacterial and antifungal properties, for example, a panel material formed by coating a thin film containing a semiconductor having a photocatalytic action on the surface, or a watertight airtight material containing semiconductor fine particles having a photocatalytic action. By configuring the fitting unit, the antibacterial and antifungal effects are further enhanced, and the entire indoor space constituted by such building members can be kept hygienic, not limited to the surfaces of these members. In other words, by coating the entire interior surface of the fittings with a photocatalytic film, sunlight is radiated during the day and fluorescent light is illuminated at night, so the coated surface always exerts a photocatalytic function, Antibacterial and
The surface shows antifungal action. In addition, the room air is always in convection and is in contact with the inner surface of the fitting, and thus is cleaned by touching the inner surface of the fitting.
【００１１】アルミ合金表面に形成する陽極酸化皮膜の
膜厚としては、０．００１〜３０μｍが好ましい。膜厚
が０．００１μｍより薄いと充分なアンカー効果を発揮
できず、逆に、３０μｍより厚くなると、衝撃を受けた
ときに陽極酸化皮膜がアルミ合金地金から剥がれてしま
う恐れがある。陽極酸化処理は、硫酸、クロム酸、リン
酸等の無機酸やシュウ酸、スルホサリチル酸、マロン酸
等の有機酸、あるいはこれらの混酸からなる電解液を用
いて従来公知の方法に従って行うことができ、微細孔の
陽極酸化皮膜を形成できればよく、特に限定されるもの
ではない。The thickness of the anodic oxide film formed on the surface of the aluminum alloy is preferably 0.001 to 30 μm. If the thickness is less than 0.001 μm, a sufficient anchor effect cannot be exerted. Conversely, if the thickness is more than 30 μm, the anodic oxide film may peel off from the aluminum alloy base metal when subjected to impact. The anodizing treatment can be performed according to a conventionally known method using an electrolytic solution composed of an inorganic acid such as sulfuric acid, chromic acid, phosphoric acid, or the like, or an organic acid such as oxalic acid, sulfosalicylic acid, or malonic acid, or a mixed acid thereof. It is sufficient that an anodic oxide film having fine pores can be formed, and there is no particular limitation.
【００１２】上記アルミ合金表面に形成した陽極酸化皮
膜上にコーティングされる半導体としては、電子及び正
孔の移動度が比較的大きく、上記のような光触媒作用を
有する半導体であればいずれも使用可能であり、例えば
ＴｉＯ 2 、ＲｕＯ2、Ｃｓ3Ｓｂ、ＩｎＡｓ、ＩｎＳｂ、
ＧａＡｓ等が挙げられるが、これらの中でも特にＴｉＯ
2が好ましい。このような光触媒作用を有する半導体の
コーティング方法としては、スパッタ法、溶射法、レー
ザーアブレーション法、ゾル−ゲル法、メッキ法など種
々の方法を用いることができる。このような方法によっ
て、アルミ合金表面の陽極酸化皮膜上に光触媒膜がコー
ティングされると共に、光触媒膜の一部が陽極酸化皮膜
の微細孔内に析着・充填され、あるいは陽極酸化皮膜の
微細孔が封止され、極めて密着強度の高い光触媒膜が形
成される。As the semiconductor coated on the anodic oxide film formed on the aluminum alloy surface, any semiconductor can be used as long as it has a relatively high mobility of electrons and holes and has the above-mentioned photocatalytic action. , and the example, if
TiO 2 , RuO 2 , Cs 3 Sb, InAs, InSb,
GaAs and the like, among which TiO
2 is preferred. Various methods such as a sputtering method, a thermal spraying method, a laser ablation method, a sol-gel method, and a plating method can be used as a method for coating a semiconductor having such a photocatalytic action. By such a method, the photocatalytic film is coated on the anodic oxide film on the aluminum alloy surface, and a part of the photocatalytic film is deposited and filled in the fine pores of the anodic oxide film, or the fine pores of the anodic oxide film are formed. Is sealed, and a photocatalytic film having extremely high adhesion strength is formed.
【００１３】陽極酸化皮膜上への光触媒膜のコーティン
グ態様の幾つかの例を図１乃至図５に示す。図５に示す
ように、アルミ合金地金１表面に形成された陽極酸化皮
膜２は六角柱状のセル４の集合体である。セル４の中央
にはアルミ合金地金１に垂直な細孔３が形成されてお
り、細孔３の底部にはアルミ合金地金１と接して略椀状
のバリヤー層５が形成されている。このような構造の陽
極酸化皮膜上に光触媒膜をコーティングする場合、コー
ティング方法やコーティングする半導体微粒子の粒径等
により、図１乃至図５に示すような種々の態様のコーテ
ィング膜が得られる。図１は、陽極酸化皮膜２の細孔３
内に半導体微粒子が析着・充填されると共にその表面に
膜状にコーティングされ、このようにコーティングされ
た光触媒膜１０ａによって陽極酸化皮膜２の細孔３が封
止された態様を示している。図２及び図３は、陽極酸化
皮膜２の細孔３内に一部が入り込んでいるが、実質的に
陽極酸化皮膜２上にその細孔３を塞ぐように光触媒膜１
０ｂ、１０ｃがコーティングされた態様を示しており、
図２の場合は光触媒膜１０ｂの表面が平滑に、図３の場
合は光触媒膜１０ｃの表面が凹凸状に形成されている。Some examples of the mode of coating the photocatalytic film on the anodic oxide film are shown in FIGS. As shown in FIG. 5, the anodic oxide film 2 formed on the surface of the aluminum alloy base metal 1 is an aggregate of hexagonal column-shaped cells 4. At the center of the cell 4, pores 3 perpendicular to the aluminum alloy ingot 1 are formed. At the bottom of the pores 3, a substantially bowl-shaped barrier layer 5 is formed in contact with the aluminum alloy ingot 1. . When a photocatalytic film is coated on the anodic oxide film having such a structure, various types of coating films as shown in FIGS. 1 to 5 can be obtained depending on the coating method, the particle size of the semiconductor fine particles to be coated, and the like. FIG. 1 shows pores 3 of anodized film 2
In this embodiment, semiconductor fine particles are deposited and filled therein, and the surface thereof is coated in a film form, and the pores 3 of the anodic oxide film 2 are sealed by the photocatalytic film 10a coated in this manner. FIGS. 2 and 3 show that the photocatalyst film 1 partially enters the pores 3 of the anodic oxide film 2 so as to substantially close the pores 3 on the anodic oxide film 2.
0b, 10c show the coated aspect,
In the case of FIG. 2, the surface of the photocatalytic film 10b is formed smooth, and in the case of FIG. 3, the surface of the photocatalytic film 10c is formed unevenly.
【００１４】一方、図４及び図５は、陽極酸化皮膜２の
細孔３底部に半導体微粒子１０ｅが析着していると共
に、その表面に細孔３を完全に塞ぐことなく析着して、
多孔質の光触媒膜１０ｄがコーティングされている態様
を示している。このようなコーティング態様は、特にス
パッタ法を用いた場合に形成され易い。すなわち、陽極
酸化皮膜のセル壁は細孔に対して全ゆる方向から飛来す
るスパッタ粒子に対するバリヤーとして働き、細孔内へ
の粒子の堆積は少なくなる。逆に、陽極酸化皮膜２のセ
ル壁頂部に選択的に堆積し、図４及び図５に示すような
多孔質のコーティング膜が得られる。本発明による陽極
酸化皮膜上への光触媒膜のコーティング態様は前記した
例に限定されるものではなく、本発明の目的とする効果
が得られる限り、種々のコーティング態様を採用でき
る。On the other hand, FIGS. 4 and 5 show that the semiconductor fine particles 10e are deposited on the bottom of the pores 3 of the anodic oxide film 2 and are deposited on the surface thereof without completely closing the pores 3.
The aspect in which the porous photocatalyst film 10d is coated is shown. Such a coating mode is easily formed particularly when a sputtering method is used. That is, the cell wall of the anodic oxide film acts as a barrier against sputtered particles flying from all directions with respect to the pores, and the accumulation of particles in the pores is reduced. Conversely, the anodic oxide film 2 is selectively deposited on the top of the cell wall, and a porous coating film as shown in FIGS. 4 and 5 is obtained. The coating mode of the photocatalytic film on the anodic oxide film according to the present invention is not limited to the above-described example, and various coating modes can be adopted as long as the desired effects of the present invention can be obtained.
【００１５】陽極酸化皮膜を形成したアルミ合金基材上
にコーティングされる光触媒膜の膜厚は、数ｎｍ〜１μ
ｍが適当である。膜厚が厚いほど光触媒作用が高く、従
って抗菌・抗黴性が高くなるが、１μｍ以上の膜厚にな
ると基材表面から剥離し易くなるので好ましくない。特
に光触媒膜をコーティングした建築材に穴を開けたり、
切断したりする加工時や、施工時に剥離が起きやすくな
る。一方、膜厚が薄くなれば光触媒作用も弱まり、充分
な抗菌・抗黴作用を発揮できなくなるため、数ｎｍ以
上、好ましくは１０ｎｍ以上が望ましい。The thickness of the photocatalyst film coated on the aluminum alloy substrate on which the anodic oxide film is formed is several nm to 1 μm.
m is appropriate. The thicker the film thickness, the higher the photocatalytic action and thus the higher the antibacterial and antifungal properties. However, a film thickness of 1 μm or more is not preferred because it is easy to peel off from the substrate surface. In particular, drill holes in building materials coated with photocatalytic film,
Peeling is likely to occur during processing such as cutting or during construction. On the other hand, when the film thickness is reduced, the photocatalytic action is weakened, and a sufficient antibacterial and antifungal action cannot be exhibited. Therefore, the thickness is preferably several nm or more, preferably 10 nm or more.
【００１６】さらに本発明によれば、前記のようにアル
ミ合金基材表面の陽極酸化皮膜上に上記光触媒膜をコー
ティングした後、さらにＡｇ、Ｃｕ、Ｐｔ等の抗菌作用
を有する金属をコーティングすることにより、より一層
抗菌・抗黴効果に優れたアルミ建築材が提供される。そ
れによって、夜間、蛍光灯の明りが消えても抗菌性が維
持され、室内空間全体を常に衛生的に保つことができ
る。上記抗菌作用を有する金属のコーティング方法とし
ても、前記光触媒膜のコーティング方法と同様に、スパ
ッタ法、溶射法、レーザーアブレーション法、ゾルーゲ
ル法、メッキ法等種々の方法を用いることができる。According to the present invention, after the photocatalytic film is coated on the anodic oxide film on the surface of the aluminum alloy substrate as described above, a metal having an antibacterial action such as Ag, Cu , or Pt is further coated. As a result, an aluminum building material having even more excellent antibacterial and antifungal effects is provided. As a result, the antibacterial property is maintained even when the light of the fluorescent lamp is extinguished at night, and the entire indoor space can be always kept hygienic. Various methods such as a sputtering method, a thermal spraying method, a laser ablation method, a sol-gel method, and a plating method can be used as the coating method of the metal having the antibacterial action, similarly to the coating method of the photocatalytic film.
【００１７】コーティングされる抗菌性金属膜の膜厚
は、１μｍ以下とする必要がある。前記した光触媒膜の
場合と同様に、抗菌性金属膜の場合もその膜厚が厚いほ
ど抗菌作用は強くなるが、１μｍを超えると建築材表面
に金属色が付き始め、美観上の問題が生じるほか、光の
透過を遮断し、下地にある光触媒膜の抗菌・抗黴作用を
低下させることにもなる。従って、抗菌性金属膜の膜厚
は、１μｍ以下とする必要があり、好ましくは１〜１０
０ｎｍ、特に好ましくは１〜１０ｎｍである。また、こ
のような抗菌性金属は、必ずしも建築材表面に膜状に付
着させる必要はなく、下地の光触媒膜への光の透過性を
考慮した場合、島状に分散して付着させる方が好まし
い。The thickness of the antibacterial metal film to be coated must be 1 μm or less. As in the case of the photocatalytic film described above, in the case of the antibacterial metal film, the antibacterial effect increases as the film thickness increases, but if the thickness exceeds 1 μm, the surface of the building material starts to have a metallic color, which causes an aesthetic problem. In addition, it blocks light transmission and reduces the antibacterial and antifungal effects of the underlying photocatalytic film. Therefore, the thickness of the antibacterial metal film needs to be 1 μm or less, preferably 1 to 10 μm.
0 nm, particularly preferably 1 to 10 nm. Further, such antibacterial metal does not necessarily need to be adhered to the surface of the building material in the form of a film. In consideration of light transmission to the underlying photocatalytic film, it is preferable that the antibacterial metal is dispersed and adhered in the form of an island. .
【００１８】さらに本発明の他の態様によれば、このよ
うなアルミ建築材から作製した框材もしくは枠材と、表
面に光触媒作用を有する半導体を含む薄膜をコーティン
グしてなるパネル材と、光触媒作用を有する半導体微粒
子を含有する水密気密材とから構成される建具ユニット
が提供される。このような建築部材を組み合わせて建具
ユニットを構成することにより、抗菌・抗黴効果が一層
高まり、これらの部材の表面に限らず、このような建築
部材で構成される室内空間全体を衛生的に保つことがで
きる。上記パネル材としては種々の材質のものを用いる
ことができるが、前記したアルミ建築材と同様に、アル
ミ合金からなる基材の表面に陽極酸化皮膜を形成し、さ
らに該陽極酸化皮膜上に光触媒膜をコーティングしてな
るパネル材、あるいはまた、上記光触媒膜の上にさらに
Ａｇ、Ｃｕ、Ｐｔ等の抗菌性の金属をコーティングして
なる金属パネル材、合成樹脂からなる基材の表面に光触
媒膜又は光触媒膜と上記抗菌性金属をコーティングした
樹脂パネル材、ガラスからなる基材の表面に光触媒膜又
は光触媒膜と上記抗菌性金属をコーティングしたガラス
パネル材などを用いることが好ましい。According to still another aspect of the present invention, there is provided a frame material or a frame material made of such an aluminum building material, a panel material having a surface coated with a thin film containing a semiconductor having a photocatalytic action, and a photocatalyst. And a watertight and airtight material containing semiconductor fine particles having an effect. By constructing a fitting unit by combining such building members, the antibacterial and antifungal effects are further enhanced, and not only the surfaces of these members, but also the entire indoor space formed of such building members in a sanitary manner. Can be kept. As the panel material, various materials can be used. As in the case of the aluminum building material described above, an anodic oxide film is formed on the surface of a base material made of an aluminum alloy, and a photocatalyst is further formed on the anodic oxide film. panel material formed by coating the film or, alternatively, further Ag onto the photocatalyst film, Cu, metallic panels formed by coating the antimicrobial metals such as Pt, the photocatalyst on the surface of a substrate made of a synthetic resin film or photocatalyst film and the antimicrobial metals coated resin panel material, it is preferable to use the surface of a substrate made of glass photocatalyst film or photocatalyst film and the glass panels coated with the antimicrobial metals like.
【００１９】特に窓ガラスパネル材に光触媒膜をコーテ
ィングする方法としては、前記したようなスパッタ法等
の蒸着法や、ゾル−ゲル法、メッキ法などを用いること
ができ、その膜厚は数ｎｍ〜１μｍが適当である。膜厚
が厚いほど光触媒作用が高く、従って抗菌・抗黴性が高
くなるが、１μｍ以上の膜厚になるとガラス表面から剥
離し易くなるので好ましくない。一方、膜厚が薄くなれ
ば光触媒作用も弱まるため、数ｎｍ以上、好ましくは１
０ｎｍ以上が望ましい。また、このように光触媒膜がコ
ーティングされた窓ガラスパネル材の表面に、さらに
銅、銀、白金等の抗菌性を有する金属を、上記光触媒膜
のコーティングと同様の方法によりコーティングするこ
ともできる。それによって、夜間、蛍光灯の明りが消え
ても抗菌性が維持される。抗菌性金属膜の膜厚は、１〜
１０ｎｍが適当である。抗菌性金属膜の膜厚が厚いほど
抗菌作用は強くなるが、１０ｎｍを超えると光の透過性
が減少し、窓として機能しなくなる。また、下地にある
光触媒膜の抗菌・抗黴作用を低下させることにもなる。
従って、抗菌性金属膜の膜厚は、１〜１０ｎｍが適当で
ある。また、このような抗菌性金属は、必ずしも窓ガラ
スパネル材表面に膜状に付着させる必要はなく、光の透
過性を考慮した場合、島状に分散して付着させる方が好
ましい。In particular, as a method of coating a photocatalytic film on a window glass panel material, a vapor deposition method such as the above-mentioned sputtering method, a sol-gel method, a plating method, or the like can be used. １1 μm is appropriate. The thicker the film thickness, the higher the photocatalytic action and thus the higher the antibacterial and antifungal properties. However, a film thickness of 1 μm or more is not preferred because it is easy to peel off from the glass surface. On the other hand, when the film thickness is small, the photocatalytic action is also weakened.
0 nm or more is desirable. In addition, the surface of the window glass panel material coated with the photocatalyst film can be further coated with a metal having antibacterial properties such as copper, silver, and platinum by the same method as the above-described coating of the photocatalyst film. Thereby, the antibacterial property is maintained at night even when the light of the fluorescent lamp is extinguished. The thickness of the antibacterial metal film is 1 to
10 nm is appropriate. As the thickness of the antibacterial metal film increases, the antibacterial action increases. However, when the thickness exceeds 10 nm, the light transmittance decreases, and the film does not function as a window. Also, the antibacterial and antifungal effects of the underlying photocatalytic film are reduced.
Therefore, the appropriate thickness of the antibacterial metal film is 1 to 10 nm. Further, such antibacterial metal does not necessarily have to be adhered in the form of a film on the surface of the window glass panel material, and it is preferable that the antibacterial metal is dispersed and adhered in an island shape in consideration of light transmittance.
【００２０】前記水密気密材は、ゴムや樹脂等の高分子
材料基材中に半導体微粒子を分散させ、抗菌・抗黴性を
付与したものである。特に、窓ガラスパネル材の固定部
として用いられているガスケット部は、結露水や汚れ等
が溜り易く、それにより黴が生えて黒ずんでしまい、衛
生的でないだけでなく、美観的にも悪くなってしまうと
いう問題があったが、本発明の水密気密材を用いること
により、このような問題を解消できる。高分子基材中に
半導体微粒子を混在させる態様としては、光触媒作用を
有する半導体微粒子を基材の少なくとも一方の表面に向
かって多くなるように混在させたり、あるいは、光触媒
作用を有する半導体微粒子が混在した高分子材料からな
る層と上記半導体微粒子が混在していない高分子材料か
らなる層の二層構造とするなど、種々の態様を採用でき
る。このように、材料の表層部には充分な量の半導体微
粒子が存在するが、内部にはできるだけ存在しないよう
にすることにより、半導体微粒子の配合量を減らし、半
導体微粒子を多量に配合した時の材料の伸びや強度等の
機械的特性の低下といった問題を解決することができ
る。また、光が当たる材料の表層部には充分な量の半導
体微粒子が存在するため、優れた抗菌・抗黴作用を発揮
させることができる。The watertight and airtight material is obtained by dispersing semiconductor fine particles in a polymer material base material such as rubber or resin to impart antibacterial and antifungal properties. In particular, the gasket portion used as a fixing portion of the window glass panel material is liable to accumulate dew condensation water and dirt, thereby causing mold growth and darkening, which is not only unsanitary but also aesthetically bad. However, such a problem can be solved by using the watertight and airtight material of the present invention. As an embodiment in which semiconductor fine particles are mixed in a polymer base material, semiconductor fine particles having a photocatalytic effect are mixed so as to increase toward at least one surface of the base material, or semiconductor fine particles having a photocatalytic effect are mixed. Various modes can be adopted, such as a two-layer structure of a layer made of a polymer material and a layer made of a polymer material in which the semiconductor fine particles are not mixed. As described above, a sufficient amount of semiconductor fine particles is present in the surface layer portion of the material, but the amount of semiconductor fine particles is reduced by eliminating as much as possible inside the semiconductor fine particles. Problems such as deterioration of mechanical properties such as elongation and strength of the material can be solved. In addition, since a sufficient amount of semiconductor fine particles are present in the surface layer of the material to which light is applied, excellent antibacterial and antifungal effects can be exhibited.
【００２１】混合される半導体微粒子の割合は、高分子
基材に対し０．０１〜１０００重量％の範囲にあること
が好ましい。０．０１重量％より少なくなると光触媒特
性を発揮する半導体微粒子の量が不足し、ひいては水密
気密材の充分な抗菌・抗黴性が得られず、一方、１００
０重量％を超えると抗菌・抗黴性の発揮に関しては問題
ないが、水密気密材の機械的特性が著しく低下する。使
用する半導体微粉末の粒径は、１ｎｍ〜１００μｍ、好
ましくは５ｎｍ〜１０μｍが適当である。粒径が１ｎｍ
より小さくなると量子サイズ効果によりバンドキャップ
が大きくなり、低圧水銀ランプ等の短波長光を発生する
照明下でないと光触媒性能が得られないといった問題が
ある。また、粒径があまりに小さ過ぎると取り扱いが困
難であったり、分散性が悪くなるという問題も生じてく
る。取扱性の点からは５ｎｍ以上の粒径が好ましい。一
方、粒径が１００μｍを超えると、材料表面に比較的大
きな半導体微粒子が存在することになるため、表面の滑
らかさが乏しくなり、また材料表面に露出した粒子が脱
落し易くもなる。材料表面の平滑さ等を考慮すると１０
μｍ以下の粒径が好ましい。The proportion of the semiconductor fine particles to be mixed is preferably in the range of 0.01 to 1000% by weight based on the polymer base material. If the amount is less than 0.01% by weight, the amount of the semiconductor fine particles exhibiting photocatalytic properties becomes insufficient, and as a result, sufficient antibacterial and antifungal properties of the watertight and airtight material cannot be obtained.
If the amount exceeds 0% by weight, there is no problem in exhibiting antibacterial and antifungal properties, but the mechanical properties of the watertight and airtight material are significantly reduced. The particle size of the semiconductor fine powder used is 1 nm to 100 μm, preferably 5 nm to 10 μm. Particle size 1nm
As the size becomes smaller, the band gap becomes larger due to the quantum size effect , generating short-wavelength light such as a low-pressure mercury lamp.
There is a problem that the photocatalytic performance cannot be obtained unless it is under illumination . Further, if the particle size is too small, there arises a problem that handling is difficult and dispersibility deteriorates. A particle size of 5 nm or more is preferred from the viewpoint of handleability. On the other hand, if the particle size exceeds 100 μm, relatively large semiconductor fine particles will be present on the material surface, so that the surface will be poor in smoothness and particles exposed on the material surface will easily fall off. Considering the smoothness of the material surface, etc., 10
Particle sizes of less than μm are preferred.
【００２２】水密気密材の基材と、なる高分子材料とし
ては、塩化ビニル樹脂、アクリルゴム、ニトリルゴム
（ＮＢＲ）、ブチルゴム（ＩＩＲ）、スチレン・ブタジ
エンゴム（ＳＢＲ）、エチレンプロピレンターポリマー
（ＥＰＤＭ）等の適度の柔軟性と強度を有し、さらに光
触媒作用に対して安定なものであれば特に限定されず、
用途に応じて適宜選定することができる。本発明の水密
気密材をガスケット部材として用いる場合、上記高分子
材料としてもガスケットに従来用いられている各種樹脂
やゴムを好適に用いることができる。The polymer material used as the base material of the watertight airtight material includes vinyl chloride resin, acrylic rubber, nitrile rubber (NBR), butyl rubber (IIR), styrene / butadiene rubber (SBR), ethylene propylene terpolymer (EPDM) ) have a moderate flexibility and strength, such as further optical
It is not particularly limited as long as it is stable against the catalytic action ,
It can be appropriately selected according to the application. When the watertight airtight material of the present invention is used as a gasket member, various resins and rubbers conventionally used for gaskets can be suitably used as the above-mentioned polymer material.
【００２３】本発明の水密気密材には、さらに抗菌性を
向上させる材料として前記半導体微粒子以外に銅、銀、
白金等の抗菌性を有する金属微粒子を含有させてもよ
い。これらの金属は、光の照射がなくても抗菌性を発揮
するので、これらの抗菌性金属が表層部に存在する建築
用水密気密材は、夜間、蛍光灯の明りが消えても抗菌・
抗黴性が維持されることになる。尚、これらの抗菌性金
属の大きさ、形状や高分子材料への添加方法も前述した
光触媒作用を示す半導体微粒子の場合と同様であり、ま
た、その含有量は、一緒に混在する半導体微粒子との合
計量で、高分子材料に対し０．０１〜１０００重量％の
範囲にあることが望ましい。The watertight and airtight material of the present invention further comprises copper, silver,
Antimicrobial metal fine particles such as platinum may be contained. Since these metals exhibit antibacterial properties even without irradiation of light, the watertight and airtight materials for construction in which these antibacterial metals are present on the surface layer are antibacterial even at night when the light of fluorescent lamps disappears.
Antifungal properties will be maintained. The size, shape, and method of adding these antimicrobial metals to the polymer material are the same as in the case of the semiconductor fine particles exhibiting the photocatalytic action described above, and the content is the same as that of the semiconductor fine particles mixed together. Is preferably in the range of 0.01 to 1000% by weight with respect to the polymer material.
【００２４】[0024]
【実施例】以下、実施例及び比較例を示して本発明につ
いて具体的に説明するが、本発明が下記実施例に限定さ
れるものでないことはもとよりである。EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the following Examples.
【００２５】実施例１ 硫酸電解浴中で膜厚１０μｍの陽極酸化皮膜を形成した
Ａｌ板上に、光触媒であるＴｉＯ2 の膜を膜厚が０．１
μｍとなるようにコーティングした。コーティングに際
してはＲＦマグネトロンスパッタ装置を使用し、以下の
条件でコーティングを行った。 ターゲット：Ｔｉ スパッタガス：Ａｒ＋Ｏ2 ガス圧（全圧）：０．５Ｐａ（Ｏ2 分圧：５×１０-3Ｐ
ａ） スパッタ時間：３０分Example 1 A TiO 2 film as a photocatalyst having a thickness of 0.1 μm was formed on an Al plate on which an anodic oxide film having a thickness of 10 μm was formed in a sulfuric acid electrolytic bath.
It was coated to a thickness of μm. The coating was performed under the following conditions using an RF magnetron sputtering apparatus. Target: Ti Sputter gas: Ar + O 2 gas pressure (total pressure): 0.5 Pa (O 2 partial pressure: 5 × 10 −3 P)
a) Sputtering time: 30 minutes
【００２６】実施例２ 硫酸電解浴中で膜厚１５μｍの陽極酸化皮膜を形成した
Ａｌ板上に、光触媒であるＴｉＯ2 の膜を膜厚が０．１
μｍとなるようにコーティングした。コーティングは、
実施例１で用いたものと同じＲＦマグネトロンスパッタ
装置を使用し、スパッタ時間を２０分間とした以外は実
施例１と同じ条件で行った。EXAMPLE 2 A TiO 2 film as a photocatalyst having a thickness of 0.1 μm was formed on an Al plate on which an anodized film having a thickness of 15 μm was formed in a sulfuric acid electrolytic bath.
It was coated to a thickness of μm. The coating is
The same RF magnetron sputtering apparatus as that used in Example 1 was used, and the same conditions as in Example 1 were used except that the sputtering time was set to 20 minutes.
【００２７】比較例 陽極酸化皮膜を形成していないＡｌ板上に、光触媒であ
るＴｉＯ2 の膜を膜厚が０．１μｍとなるようにコーテ
ィングした。コーティングは、実施例１で用いたものと
同じＲＦマグネトロンスパッタ装置を使用し、同じ条件
でコーティングを行った。Comparative Example A TiO 2 film as a photocatalyst was coated on an Al plate having no anodized film so as to have a thickness of 0.1 μm. The coating was performed under the same conditions using the same RF magnetron sputtering apparatus as used in Example 1.
【００２８】抗黴性評価：実施例１、２及び比較例で得
られたＴｉＯ2 膜をコーティングしたＡｌ板の抗黴効果
を調べるため、温度２５℃、湿度９０％に保った大気雰
囲気に５０日間暴露した。ＴｉＯ2 コーティング面上の
黴の占有面積の経時変化を図６に示す。Evaluation of antifungal property: In order to examine the antifungal effect of the Al plates coated with the TiO 2 films obtained in Examples 1 and 2 and Comparative Example, a test was carried out in an air atmosphere maintained at a temperature of 25 ° C. and a humidity of 90%. Exposure for days. FIG. 6 shows the change over time in the area occupied by the mold on the TiO 2 coating surface.
【００２９】密着性評価：実施例１、２及び比較例で得
られたＴｉＯ2 膜をコーティングしたＡｌ板に対し、Ｊ
ＩＳ Ｈ ８６０２の５．８項に記載のセロハン粘着テ
ープを用いた塗膜の付着性試験（粘着テープ試験）を行
い、またＪＩＳ Ｈ ８５０４に規定する方法に従って
スクラッチ試験を行い、それぞれＴｉＯ2 膜の密着性を
テストした。その結果を表１に示す。Adhesion evaluation: The Al plates coated with the TiO 2 films obtained in Examples 1 and 2 and Comparative Example
Perform adhesion test of the coating film using the cellophane adhesive tape according to paragraph 5.8 of IS H 8602 (adhesive tape test), also performs a scratch test according to the method specified in JIS H 8504, respectively TiO 2 film The adhesion was tested. Table 1 shows the results.
【表１】 [Table 1]
【００３０】図６から分かるように、ＴｉＯ2 膜でコー
ティングされたＡｌ板はいずれも抗黴効果が有り、Ｔｉ
Ｏ2 膜がコーティングされるＡｌ板に陽極酸化皮膜が形
成されたかどうかは抗黴効果に影響していない。しかし
ながら、表１に示す密着性試験の結果から明らかなよう
に、陽極酸化皮膜が形成されていないＡｌ板に直接Ｔｉ
Ｏ2 膜が形成された場合には、その密着性が弱く、密着
性試験においてＴｉＯ2 膜の剥離が生じた。これに対し
て、実施例１及び２のように、Ａｌ板上に形成された陽
極酸化皮膜上にＴｉＯ2 膜をコーティングした場合、Ｔ
ｉＯ2 膜の密着強度が向上し、密着性試験においても全
く剥離を生ずることはなかった。As can be seen from FIG. 6, each of the Al plates coated with the TiO 2 film has an antifungal effect,
Whether the anodic oxide film is formed on the Al plate coated with the O 2 film does not affect the antifungal effect. However, as is clear from the results of the adhesion test shown in Table 1, the Ti plate was directly formed on the Al plate on which the anodic oxide film was not formed.
When the O 2 film was formed, the adhesion was weak, and peeling of the TiO 2 film occurred in the adhesion test. On the other hand, when the TiO 2 film is coated on the anodic oxide film formed on the Al plate as in Examples 1 and 2, the T
The adhesion strength of the iO 2 film was improved, and no peeling occurred even in the adhesion test.
【００３１】[0031]
【発明の効果】以上のように、本発明のアルミ建築材
は、アルミ合金からなる基材の表面に、光触媒膜の強い
酸化還元作用に対するバリヤーとして機能し、しかも光
触媒膜とアルミ合金地金との密着性を強めるアンカー効
果を有する微多孔質の陽極酸化皮膜を形成し、さらに該
陽極酸化皮膜上に光触媒膜をコーティングしたものであ
るため、アルミ合金地金表面の腐食（酸化）や光触媒膜
の剥離といった問題もなく、また、光が当たる材料表面
の光触媒膜には充分な量の半導体が存在するため、優れ
た抗菌・抗黴作用を示す。従って、本発明によれば、特
別の装置を要することなくメンテナンスフリーであり、
しかも抗菌・抗黴性の膜がアルミ合金基材表面を腐食す
ることなくかつ高い密着強度でコーティングされた自己
浄化性のアルミ建築材が提供される。また、上記のよう
に抗菌・抗黴性に優れるアルミ建築材から框材もしくは
枠材を作製し、これを、同様に抗菌・抗黴性を付与した
他のパネル材や水密気密材と組み合わせて建具ユニット
を構成することにより、抗菌・抗黴効果が一層高まり、
これらの部材の表面に限らず、このような建築部材で構
成される室内空間全体を清浄化でき、長期間に亘って衛
生的に保つことができる。さらに本発明によれば、前記
框材もしくは枠材や、パネル材及び水密気密材上に上記
光触媒膜をコーティングした後、さらにＡｇ、Ｃｕ等の
抗菌作用を有する金属をコーティングすることにより、
夜間、蛍光灯の明りが消えても抗菌性が維持され、室内
空間全体を常時衛生的に保つことができる。As described above, the aluminum building material of the present invention functions as a barrier against the strong oxidation-reduction effect of the photocatalyst film on the surface of the base material made of the aluminum alloy. A microporous anodic oxide film that has an anchor effect to enhance the adhesion of aluminum is formed, and a photocatalytic film is coated on the anodic oxide film. There is no problem of exfoliation, and a sufficient amount of semiconductor is present in the photocatalytic film on the surface of the material exposed to light, so that it exhibits excellent antibacterial and antifungal effects. Therefore, according to the present invention, it is maintenance-free without requiring a special device,
In addition, there is provided a self-cleaning aluminum building material in which an antibacterial / antifungal film is coated with high adhesion strength without corroding the surface of the aluminum alloy base material. In addition, as described above, a frame material or a frame material is manufactured from an aluminum building material having excellent antibacterial and antifungal properties, and this is combined with other panel materials and watertight and airtight materials similarly provided with antibacterial and antifungal properties. By configuring the fitting unit, the antibacterial and antifungal effects are further enhanced,
Not only the surfaces of these members, but also the entire indoor space composed of such building members can be cleaned and kept hygienic for a long period of time. Furthermore, according to the present invention, after coating the photocatalytic film on the frame material or the frame material, the panel material and the watertight and airtight material, and further coating a metal having an antibacterial action such as Ag and Cu,
Even at night, the antibacterial property is maintained even if the light of the fluorescent lamp is extinguished, so that the entire indoor space can be kept hygienic at all times.
【図１】陽極酸化皮膜上への光触媒膜のコーティング態
様の一例を示す部分断面図である。FIG. 1 is a partial cross-sectional view showing an example of a mode of coating a photocatalytic film on an anodized film.
【図２】陽極酸化皮膜上への光触媒膜のコーティング態
様の他の例を示す部分断面図である。FIG. 2 is a partial cross-sectional view showing another example of a mode of coating a photocatalytic film on an anodized film.
【図３】陽極酸化皮膜上への光触媒膜のコーティング態
様のさらに他の例を示す部分断面図である。FIG. 3 is a partial cross-sectional view showing still another example of a mode of coating a photocatalytic film on an anodized film.
【図４】陽極酸化皮膜上への光触媒膜のコーティング態
様の別の例を示す部分断面図である。FIG. 4 is a partial cross-sectional view showing another example of a mode of coating a photocatalytic film on an anodized film.
【図５】図４に示す態様の陽極酸化皮膜上に光触媒膜が
コーティングされた状態を示す部分断面斜視図である。5 is a partial cross-sectional perspective view showing a state in which a photocatalytic film is coated on the anodic oxide film in the mode shown in FIG.
【図６】実施例１、２及び比較例で得られたＴｉＯ2 膜
コーティングＡｌ板上の黴占有面積の経時変化を示すグ
ラフである。FIG. 6 is a graph showing the change over time in the area occupied by mold on the TiO 2 film-coated Al plates obtained in Examples 1 and 2 and Comparative Example.
１ アルミ合金地金 ２ 陽極酸化皮膜 ３ 細孔 ４ セル ５ バリヤー層 １０ａ，１０ｂ，１０ｃ，１０ｄ 光触媒膜 DESCRIPTION OF SYMBOLS 1 Aluminum alloy base metal 2 Anodized film 3 Pores 4 Cell 5 Barrier layer 10a, 10b, 10c, 10d Photocatalytic film
フロントページの続き (56)参考文献 特開 昭62−182298（ＪＰ，Ａ) 特開 平６−278241（ＪＰ，Ａ) 特開 平７−462（ＪＰ，Ａ) アルミニウム表面技術便覧編集委員会 編「アルミニウム表面技術便覧」（1980 年10月17日発行）軽金属出版株式会社 Ｐ．119−164 (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 11/18 A61L 2/16 E04F 13/12 E06B 1/00 B01J 35/02 Continuation of the front page (56) References JP-A-62-182298 (JP, A) JP-A-6-278241 (JP, A) JP-A-7-462 (JP, A) Aluminum Surface Technology Handbook Editing Committee "Handbook of Aluminum Surface Technology" (Issued October 17, 1980) Light Metal Publishing Co., Ltd. 119-164 (58) Field surveyed (Int.Cl. 7 , DB name) C25D 11/18 A61L 2/16 E04F 13/12 E06B 1/00 B01J 35/02
Claims (5)
なる基材の表面に陽極酸化皮膜を形成し、さらに該陽極
酸化皮膜上に光触媒作用を有する半導体を含む薄膜をコ
ーティングしてなり、該光触媒作用を有する半導体を含
む薄膜の膜厚が１μｍ以下であることを特徴とするアル
ミニウム建築材。1. A formed aluminum or anodized film on the surface of a substrate made of an aluminum alloy, Ri further name by coating a thin film containing a semiconductor having a photocatalytic activity in said positive on electrode oxide film having a photocatalyst action Including semiconductors
An aluminum building material characterized in that the thickness of the thin film is 1 μm or less .
３０μｍ、細孔径が５〜２５０ｎｍである請求項１記載
のアルミニウム建築材。2. The method according to claim 1, wherein the anodic oxide film has a thickness of 0.001 to 0.001.
The aluminum building material according to claim 1, wherein the aluminum building material has a diameter of 30 µm and a pore diameter of 5 to 250 nm.
膜の上にさらに抗菌性の金属がコーティングされている
請求項１又は２に記載のアルミニウム建築材。Wherein the aluminum building material according to claim 1 or 2 further antimicrobial metal on the thin film is a coating comprising a semiconductor having photocatalytic action.
なる基材の表面に陽極酸化皮膜を形成し、さらに該陽極
酸化皮膜上に光触媒作用を有する半導体を含む薄膜をコ
ーティングしてなる框材もしくは枠材と、表面に光触媒
作用を有する半導体を含む薄膜をコーティングしてなる
パネル材と、光触媒作用を有する半導体微粒子を含有す
る水密気密材とから構成される建具。4. A frame material or a frame material obtained by forming an anodic oxide film on a surface of a substrate made of aluminum or an aluminum alloy, and further coating the anodic oxide film with a thin film containing a semiconductor having a photocatalytic action. A fitting comprising a panel material having a surface coated with a thin film containing a semiconductor having a photocatalytic action, and a watertight and airtight material containing semiconductor fine particles having a photocatalytic action.
薄膜をコーティングしてなるパネル材が窓ガラスパネル
材である請求項４に記載の建具。5. The fitting according to claim 4 , wherein the panel material having a surface coated with a thin film containing a semiconductor having a photocatalytic action is a window glass panel material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11906395A JP3210544B2 (en) | 1995-04-21 | 1995-04-21 | Antibacterial and antifungal aluminum building materials and fittings using the same |
| US08/634,985 US5753322A (en) | 1995-04-21 | 1996-04-19 | Antibacterial, antifungal aluminum building materials and fixtures using the materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11906395A JP3210544B2 (en) | 1995-04-21 | 1995-04-21 | Antibacterial and antifungal aluminum building materials and fittings using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08296060A JPH08296060A (en) | 1996-11-12 |
| JP3210544B2 true JP3210544B2 (en) | 2001-09-17 |
Family
ID=14751989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11906395A Expired - Fee Related JP3210544B2 (en) | 1995-04-21 | 1995-04-21 | Antibacterial and antifungal aluminum building materials and fittings using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3210544B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3251475B2 (en) * | 1995-09-06 | 2002-01-28 | 昭 藤嶋 | Manufacturing method of antibacterial / antifungal / antifouling aluminum building material and colored aluminum building material |
| JP3856535B2 (en) * | 1997-08-01 | 2006-12-13 | シャープ株式会社 | Method for producing photocatalyst body |
| JP2001303296A (en) * | 2000-04-25 | 2001-10-31 | Chukin:Kk | Metallic material having photocatalytic function and producing method thereof |
| EP1445601A3 (en) | 2003-01-30 | 2004-09-22 | Fuji Photo Film Co., Ltd. | Localized surface plasmon sensor chips, processes for producing the same, and sensors using the same |
| WO2012054043A1 (en) | 2010-10-21 | 2012-04-26 | Hewlett-Packard Development Company, L.P. | Nano-structure and method of making the same |
| US20170267520A1 (en) | 2010-10-21 | 2017-09-21 | Hewlett-Packard Development Company, L.P. | Method of forming a micro-structure |
| US9410260B2 (en) | 2010-10-21 | 2016-08-09 | Hewlett-Packard Development Company, L.P. | Method of forming a nano-structure |
| CN103249873B (en) | 2010-10-21 | 2016-03-30 | 惠普发展公司，有限责任合伙企业 | Form the method for nanostructure |
| WO2012054044A1 (en) * | 2010-10-21 | 2012-04-26 | Hewlett-Packard Development Company, L. P. | Method of forming a micro-structure |
| JP6327242B2 (en) * | 2015-12-22 | 2018-05-23 | アイシン精機株式会社 | Aluminum molded product and manufacturing method thereof |
-
1995
- 1995-04-21 JP JP11906395A patent/JP3210544B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| アルミニウム表面技術便覧編集委員会編「アルミニウム表面技術便覧」（１９８０年１０月１７日発行）軽金属出版株式会社 Ｐ．１１９−１６４ |
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| Publication number | Publication date |
|---|---|
| JPH08296060A (en) | 1996-11-12 |
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