JP4201402B2 - Method for treating hardened concrete - Google Patents
Method for treating hardened concrete Download PDFInfo
- Publication number
- JP4201402B2 JP4201402B2 JP32205798A JP32205798A JP4201402B2 JP 4201402 B2 JP4201402 B2 JP 4201402B2 JP 32205798 A JP32205798 A JP 32205798A JP 32205798 A JP32205798 A JP 32205798A JP 4201402 B2 JP4201402 B2 JP 4201402B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- hardened concrete
- metal
- salt
- pores
- 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
- 239000004567 concrete Substances 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 58
- 230000000844 anti-bacterial effect Effects 0.000 claims description 49
- 239000011148 porous material Substances 0.000 claims description 25
- 230000000843 anti-fungal effect Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229940121375 antifungal agent Drugs 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- 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 claims description 2
- 150000002739 metals Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- -1 pulp Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001149955 Cladosporium cladosporioides Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 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 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Working Measures On Existing Buildindgs (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、鉄筋やＰＣ鋼材を補強材とする鉄筋コンクリート構造物やプレストレストコンクリート構造物などのコンクリート硬化体の処理方法、特に、コンクリート硬化体表面や内部に存在する細孔中に、表面が正（＋）に帯電した抗菌・抗カビ性金属含有物を充填し、コンクリート構造物の汚れや藻類などの付着を抑止する方法に関する。
【０００２】
【従来の技術とその課題】
最近、コンクリートに配合される減水剤や増粘剤などの有機化合物の影響によってコンクリート構造物にカビ類や藻類などが発生することが景観上好ましくないという課題があった。
【０００３】
一方、銀、銅、及び亜鉛等が抗菌・抗カビ性を有していることは古くから知られており、これらの抗菌・抗カビ性金属を含有する化合物が抗菌・抗カビ剤として種々提案されている（特開昭60−181002号公報、特開昭63−265809号公報、特開昭62−70221 号公報、特開平1−167212号公報、特開平2−180270号公報、特開昭62−158202号公報、及び特開昭62−210098号公報）。
これらの抗菌・抗カビ剤は、それ自身を、単独に、あるいは、樹脂組成物や繊維などに配合して、例えば、水処理分野、船舶・漁業分野、及び塗料・プラスチック分野等において広範に利用されるものであった。
しかしながら、これらの抗菌・抗カビ剤に含有される銀、銅、及び亜鉛といった抗菌・抗カビ性金属は、僅か数ppmであってもセメントの水和反応を著しく遅延するために、モルタル又はコンクリートに混和して使用することが難しいという課題があった。
【０００４】
本発明者はこのような状況に鑑み前記課題を解消すべく種々検討した結果、特定の処理方法を採用することにより、前記課題を解消し、コンクリート硬化体に抗菌・抗カビ性が付与できるという知見を得て本発明を完成するに至った。
【０００５】
【課題を解決するための手段】
即ち、本発明は、コンクリート硬化体の表面及び／又は内部の細孔中に、水溶性金属塩の水溶液中に抗菌・抗カビ性金属含有物を分散しカチオンを吸着させることにより表面が正（＋）に帯電した抗菌・抗カビ性金属含有物を充填するコンクリート硬化体の処理方法であり、水溶性金属塩が、カルシウム塩、マグネシウム塩、銅塩、亜鉛塩、及び銀塩のいずれかであるコンクリート硬化体の処理方法であり、コンクリート硬化体の表面及び／又は表面近傍に設置した電極を外部電極とし、コンクリート硬化体内部の鋼材を内部電極とし、外部電極間及び／又は外部電極と内部電極間に電流を流して、該細孔中に表面が正（＋）に帯電した抗菌・抗カビ性金属含有物を充填するコンクリート硬化体の処理方法である。
【０００６】
以下、本発明を詳細に説明する。
【０００７】
コンクリート硬化体の表面及び／又は内部の細孔とは、コンクリート硬化体の表面やコンクリート硬化体内部に存在する連通する細孔であり、コンクリート硬化時の水分蒸発や結晶水の消失などにより生じるものである。
この細孔の径は、数オングストローム（Å、10-10ｍ）〜数ミリ（10-3ｍ）の広範囲におよび、連通孔としては、通常、数十〜数百μｍ程度のものであるが、比較的大きな細孔同志を連通孔が繋いでいるようなものもある。
細孔量は、コンクリート材料の種類、配合、及び混練方法等によっても変化するものであり、配合時の水の配合量によって大きく変化するものである。
細孔量は、個数で表すことは困難であり、細孔の体積を全て合計した空隙量とコンクリート硬化体の全体積の割合である空隙率の大小で、細孔量の大小を示すことが通常行われており、通常のコンクリート配合で、水／セメント比（Ｗ／Ｃ）が50〜60％では空隙率が12％程度であり、Ｗ／Ｃが多くなると空隙率も高くなる。
【０００８】
本発明は、コンクリート硬化体の表面及び／又は内部の細孔中に表面が正（＋）に帯電した抗菌・抗カビ性金属含有物を供給し、それを細孔中に充填し、コンクリート硬化体に抗菌・抗カビ性を付与するものである。
【０００９】
本発明で使用する表面が正（＋）に帯電した抗菌・抗カビ性金属含有物（以下、カチオン化抗菌金属類という）とは、その表面電位がプラスに帯電した抗菌・抗カビ性金属類を意味するものである。
【００１０】
抗菌・抗カビ性金属含有物（以下、抗菌金属類という）とは特に限定されるものではないが、例えば、クロム、銅、亜鉛、銀、スズ、鉛、及びビスマス又はこれらの酸化物、並びに、これらを含有するガラス、ゼオライト類、アパタイト類、及びモンモリロナイト類等が挙げられ、本発明ではこれらのうちの一種又は二種以上が使用可能である。
抗菌金属類の粒度は、平均粒径が５μｍ以下が好ましく、１μｍ以下がより好ましい。平均粒径が５μｍを越えるとコンクリート硬化体の表面及び／又は内部の細孔中に抗菌金属類が充填されないおそれがある。
【００１１】
抗菌金属類の表面を正（＋）に帯電する（以下、カチオン化という）方法としては、例えば、抗菌金属類が水溶性の場合には、水に溶解し、抗菌金属類をイオン化することによりカチオン化が可能であり、また、金属や不溶性化合物の場合には、処理液として水溶性金属塩の水溶液を調製し、この処理液中に金属や不溶性化合物を分散させることにより、金属や不溶性化合物表面にカチオンを吸着させ、これによってカチオン化が可能となる。
この際、金属や不溶性化合物と水溶性金属塩の割合は、金属１mol に対して、水溶性金属塩１〜10mol程度が好ましく、２〜５mol程度がより好ましい。金属や不溶性化合物と水溶性金属塩の割合が前記の範囲外では金属や不溶性化合物の充填効果が充分に得られないおそれがある。
【００１２】
水溶性金属塩の金属としては、例えば、ナトリウム、カリウム、リチウム、カルシウム、及びマグネシウム等のアルカリ金属やアルカリ土類金属の他、アルミニウム、クロム、銅、亜鉛、銀、スズ、鉛、及びビスマス等が挙げられ、これらの塩化物、硝酸塩、亜硝酸塩、亜硫酸塩、硫酸塩、及び水酸化物等の水溶液が使用可能であるが、コンクリート硬化体の耐久性の面から、カルシウム塩、マグネシウム塩、銅塩、亜鉛塩、及び銀塩等が好ましい。
【００１３】
本発明は、コンクリート硬化体の表面や内部の細孔中にカチオン化抗菌金属類を供給し、細孔中に充填させることでコンクリート硬化体の処理を行うものであり、コンクリート硬化体内部の細孔中に抗菌金属類を充填するという物理的作用によりコンクリート硬化体が緻密化するため、中性化抵抗性や耐塩分浸透性は向上するなどの効果も得られる。
【００１４】
カチオン化抗菌金属類をコンクリート硬化体の表面や内部の細孔中に供給する方法は、カチオン化抗菌金属類が細孔中に充填されれば特に限定されるものではなく、いかなる方法でも可能であるが、カチオン化抗菌金属類がまんべんなくコンクリート硬化体表面や内部の細孔中に充填する面からコンクリート硬化体の表面及び／又は内部に電流を流すことが好ましい。
この時、カチオン化抗菌金属類を含む処理液の濃度は特に限定されるものではないが、0.001〜１mol/l 程度の範囲が好ましく、0.01〜0.1mol/l程度の範囲がより好ましい。
【００１５】
また、カチオン化抗菌金属類を、土中のコンクリート構造物に供給する場合は、通常、コンクリート構造物が土と接している境界部分にカチオン化抗菌金属類を含有する溶液を流し込み、常時供給する方法が考えられる。
しかしながら、コンクリート構造物が埋まっている箇所の土壌は区切りがなく、カチオン化抗菌金属類を含有する溶液が逸散する可能性があるため、コンクリート構造物から僅かに離れた箇所の土壌に溶液溜めを設けることが好ましい。溶液溜めを設けることが困難な場合は、カチオン化抗菌金属類を保持する保持材料を使用することが好ましい。
【００１６】
コンクリート硬化体の表面に設置した電極を外部電極とし、コンクリート硬化体内部の鋼材を内部電極とし、外部電極間及び／又は外部電極と内部電極間に電流を流す。
外部電極としては導電性のものであれば特に限定されるものではないが、金属を使用する場合は、腐食が発生しないように貴金属メッキ等の処理を行ったものが好ましい。
また、内部電極としては、コンクリート硬化体の内部鉄筋を使用することも可能であり、特別に導電性物質をコンクリート硬化体中に配置することも可能である。
【００１７】
本発明では、カチオン化抗菌金属類を外部電極間や、外部電極と内部電極間に存在させることが必要である。
カチオン化抗菌金属類を外部電極間や、外部電極と内部電極間に存在させる方法は特に限定されるものではないが、カチオン化抗菌金属類を含有する溶液をコンクリート硬化体表面に塗布したり吹き付けたり、コンクリート硬化体表面に容器を設けてその中にカチオン化抗菌金属類を含有する溶液を保持する方法などが可能である。
【００１８】
これらのうち、コンクリート硬化体表面に容器を設けて、その中にカチオン化抗菌金属類を含有する溶液を保持する方法が通常行われるが、その他、カチオン化抗菌金属類を含有する溶液を吸着又は保持する保持材料を用いてコンクリート硬化体表面に供給することが好ましい。
【００１９】
保持材料としては、パルプ、布、及び不織布等の繊維状物質又はそのシート、ゼオライト、シラスバルーン、及び発泡ビーズ等の多孔質材料、並びに、吸水性の有機高分子等の一種又は二種以上の使用が可能である。
【００２０】
カチオン化抗菌金属類を電気的にコンクリート硬化体内部の細孔中へ供給する方法としては、コンクリートの壁体の場合、壁をはさむように、カチオン化抗菌金属類の保持材料が存在する一方の表面に陽極を、他方の表面又はコンクリート硬化体内部の鉄筋に陰極を設ける。柱の場合、１つ以上の表面に陽極を、他の表面又は内部鉄筋に陰極を設ける。床の場合、上面に陽極を、下面又は内部鉄筋に陰極を設け、外部電極間及び／又は外部電極と内部電極間に電流を流す方法が可能である。
【００２１】
【実施例】
以下、本発明を実験例にもとづいて説明する。
【００２２】
実験例１
各材料の単位量が、セメント330kg/m3、細骨材748kg/m3、粗骨材1,041kg/m3、及び水165kg/m3の配合のコンクリートを調製し、断面の中心に公称径10mmの異形鉄筋を埋設するようにして、φ10×20cmの供試体を作製した。
この供試体を表１に示すカチオン化抗菌金属類（ＣＡＢ）の懸濁液に浸漬し、供試体の周囲にチタンメッシュを表面から10mmの間隔になるように設置した。
次に、チタンメッシュを陽極に、内部鉄筋を陰極にして、コンクリート硬化体表面積１m2当たり１Ａとなるように直流電流を流した。この状態で２週間電流を流した後、中性化深さ、塩分浸透量、及びカビ抵抗性を測定した。
【００２３】
＜使用材料＞
セメント ：普通ポルトランドセメント、電気化学工業社製
細骨材 ：姫川産川砂
粗骨材 ：姫川産砕石、Gmax20mm
水 ：水道水
ＡＥ減水剤：市販品、ポリカルボン酸系
処理液 ：塩化カルシウムの0.05mol/l水溶液
ＣＡＢイ ：銀を担持したゼオライトを処理液中に0.025mol分散させたもの、平均粒径0.5μｍ
ＣＡＢロ ：銀を担持したモンモリロナイトを処理液中に0.025mol分散させたもの、平均粒径0.5μｍ
ＣＡＢハ ：試薬１級のコロイダル銀を処理液中に0.025mol分散させたもの、平均粒径0.1μｍ
ＣＡＢニ ：試薬１級酸化亜鉛を処理液中に0.025mol分散させたもの、平均粒径１μｍ
ＣＡＢホ ：Ag2O含有量が１重量％のアルミノケイ酸ガラスを処理液中に0.025mol分散させたもの、平均粒径３μｍ
チタンメッシュ：エルテックコーポレーション社製、商品名「エルガードメッシュ＃２１０」
【００２４】
＜測定方法＞
中性化深さ：供試体を、30℃、相対湿度60％、炭酸ガス濃度10％の条件で２週間促進中性化させ、供試体を輪切りにして断面にフェノールフタレイン溶液を塗布して呈色反応より、中性化深さをノギスで計測
塩分浸透量: 供試体を、30℃、10％NaCl水溶液に 200日間浸漬した後、塩分量を測定
カビ抵抗性: 供試体を、30℃、炭酸ガス濃度５％の条件で７日間促進中性化させ、カビ種Ａアスペルギルス・ニゲルとカビ種Ｂクラドスポリウム・クラドスポリオイデスの胞子懸濁液を供試体上に塗布し４週間にわたってカビ抵抗性試験をJIS Z 2911に準じて行った。カビ抵抗性の×は供試体の１／３を越える面積においてカビ発生、△は１／３以下の面積においてカビ発生、○はカビ発生なし。
【００２５】
【表１】
実験例２
ＣＡＢ−ハを使用し、表２に示す処理液中の濃度のＣＡＢ−ハを用いたこと以外は実験例１と同様に行った。結果を表２に併記する。
【００２７】
【表２】
【発明の効果】
本発明では、コンクリート硬化体の表面又は内部の細孔中にカチオン化抗菌金属類を充填させることによりコンクリート硬化体に抗菌・抗カビ性を付与することができる。
そして、コンクリート硬化体の外部に電極を設置し、コンクリート硬化体内部の鉄筋を一方の電極とし、電極間に処理溶液を保持し電流を流すことにより、また、コンクリート硬化体表面及び／又は内部の細孔中にカチオン化抗菌金属類をより多くかつ深い位置にまで充填させることにより、コンクリート硬化体の抗菌・抗カビ性の持続性をより一層向上させることができる他、中性化抵抗性や耐塩分浸透性が向上するなどの効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for treating a hardened concrete body such as a reinforced concrete structure or a prestressed concrete structure using reinforcing steel or PC steel as a reinforcing material. This invention relates to a method for preventing adhesion of dirt and algae to a concrete structure by filling an antibacterial / antifungal metal-containing material charged to +).
[0002]
[Prior art and its problems]
Recently, there has been a problem that mold and algae are undesirably generated in a concrete structure due to the influence of organic compounds such as water reducing agents and thickeners mixed with concrete.
[0003]
On the other hand, it has long been known that silver, copper, zinc, and the like have antibacterial and antifungal properties, and various compounds containing these antibacterial and antifungal metals have been proposed as antibacterial and antifungal agents. (JP 60-181002, JP 63-265809, JP 62-70221, JP 1-167212, JP 2-180270, JP 62-158202 and JP-A 62-210098).
These antibacterial and antifungal agents can be used extensively, for example, in water treatment, ship / fishery, and paint / plastics fields, either alone or in combination with resin compositions or fibers. It was to be done.
However, antibacterial and antifungal metals such as silver, copper, and zinc contained in these antibacterial and antifungal agents significantly delay the hydration reaction of cement even at a few ppm, so mortar or concrete There was a problem that it was difficult to mix and use.
[0004]
As a result of various studies to solve the above problems in view of such a situation, the present inventor can solve the above problems by adopting a specific treatment method, and can impart antibacterial / antifungal properties to the hardened concrete. Obtaining knowledge, the present invention has been completed.
[0005]
[Means for Solving the Problems]
That is, the present invention has a positive surface by dispersing the antibacterial / antifungal metal-containing material in an aqueous solution of a water-soluble metal salt and adsorbing cations on the surface and / or internal pores of the hardened concrete. +) Is a method for treating a hardened concrete filled with an antibacterial / antifungal metal-containing material charged with water , and the water-soluble metal salt is one of calcium salt, magnesium salt, copper salt, zinc salt, and silver salt. a processing method of a concrete cured body, the surface and / or installation the electrodes near the surface of the concrete hardened body as an external electrode, the steel of the concrete hardened body portion and the internal electrodes, internal and external electrodes and / or between the external electrodes This is a method for treating a hardened concrete by passing an electric current between electrodes and filling the pores with a positive (+) charged antibacterial / antifungal metal-containing material.
[0006]
Hereinafter, the present invention will be described in detail.
[0007]
The pores on the surface and / or inside of the hardened concrete are pores that communicate with the surface of the hardened concrete and inside the hardened concrete, and are caused by evaporation of water and loss of crystal water during hardening of the concrete. It is.
The diameter of the pores ranges from a few angstroms (Å, 10 −10 m) to several millimeters (10 −3 m), and the communication holes are usually several tens to several hundreds μm. Some communication holes connect relatively large pores.
The amount of pores varies depending on the type of concrete material, blending, kneading method, and the like, and varies greatly depending on the blending amount of water during blending.
The amount of pores is difficult to express by number, and the amount of pores is the size of the void volume, which is the ratio of the total void volume and the total volume of the hardened concrete, and may indicate the size of the pore volume. It is usually carried out, and the porosity is about 12% when the water / cement ratio (W / C) is 50 to 60% in a normal concrete composition, and the porosity increases as W / C increases.
[0008]
The present invention supplies an antibacterial / antifungal metal-containing material whose surface is positively (+) charged into the surface and / or internal pores of the hardened concrete body, and fills the pores with the antibacterial / antifungal metal content. It imparts antibacterial and antifungal properties to the body.
[0009]
The antibacterial / antifungal metal-containing material (hereinafter referred to as cationized antibacterial metal) having a positive (+) charged surface used in the present invention is an antibacterial / antifungal metal having a positive surface potential. Means.
[0010]
The antibacterial / antifungal metal-containing material (hereinafter referred to as antibacterial metals) is not particularly limited, but includes, for example, chromium, copper, zinc, silver, tin, lead, and bismuth or oxides thereof, and , Glass containing these, zeolites, apatites, montmorillonites, and the like, and one or more of them can be used in the present invention.
The average particle size of the antibacterial metals is preferably 5 μm or less, and more preferably 1 μm or less. If the average particle size exceeds 5 μm, the surface of the hardened concrete and / or the pores inside may not be filled with antibacterial metals.
[0011]
As a method of charging the surface of antibacterial metal positively (+) (hereinafter referred to as cationization), for example, when the antibacterial metal is water-soluble, it is dissolved in water, and the antibacterial metal is ionized. In the case of a metal or insoluble compound, an aqueous solution of a water-soluble metal salt is prepared as a treatment liquid, and the metal or insoluble compound is dispersed in the treatment liquid, so that the metal or insoluble compound is dispersed. Cations are adsorbed on the surface, which enables cationization.
At this time, the ratio of the metal or insoluble compound to the water-soluble metal salt is preferably about 1 to 10 mol, more preferably about 2 to 5 mol, with respect to 1 mol of the metal. If the ratio of the metal or insoluble compound to the water-soluble metal salt is outside the above range, the filling effect of the metal or insoluble compound may not be sufficiently obtained.
[0012]
Examples of the metal of the water-soluble metal salt include aluminum, chromium, copper, zinc, silver, tin, lead, and bismuth in addition to alkali metals and alkaline earth metals such as sodium, potassium, lithium, calcium, and magnesium. Although aqueous solutions of these chlorides, nitrates, nitrites, sulfites, sulfates, and hydroxides can be used, in terms of durability of the hardened concrete, calcium salts, magnesium salts, Copper salts, zinc salts, silver salts and the like are preferable.
[0013]
In the present invention, a cationized antibacterial metal is supplied to the surface of a hardened concrete body or pores in the interior, and the hardened concrete body is processed by filling the pores. Since the concrete hardened body is densified by the physical action of filling the pores with antibacterial metals, effects such as improvement of neutralization resistance and salt penetration resistance can be obtained.
[0014]
The method of supplying the cationized antibacterial metal into the surface of the hardened concrete or inside pores is not particularly limited as long as the cationized antibacterial metal is filled in the pores, and any method is possible. However, it is preferable that a cationized antibacterial metal flows evenly through the surface and / or the inside of the hardened concrete body from the surface in which the hardened concrete body is uniformly filled into the surface of the hardened concrete body or inside pores.
At this time, the concentration of the treatment liquid containing the cationized antibacterial metal is not particularly limited, but is preferably in the range of about 0.001 to 1 mol / l, and more preferably in the range of about 0.01 to 0.1 mol / l.
[0015]
In addition, when supplying cationized antibacterial metals to concrete structures in the soil, a solution containing cationized antibacterial metals is usually poured into the boundary portion where the concrete structures are in contact with the soil and supplied constantly. A method is conceivable.
However, the soil where the concrete structure is buried is not separated, and the solution containing the cationized antibacterial metals may escape, so the solution is stored in the soil slightly away from the concrete structure. Is preferably provided. When it is difficult to provide a solution reservoir, it is preferable to use a holding material that holds cationized antibacterial metals.
[0016]
An electrode installed on the surface of the hardened concrete body is used as an external electrode, a steel material inside the hardened concrete body is used as an internal electrode, and a current is passed between the external electrodes and / or between the external electrodes and the internal electrodes.
The external electrode is not particularly limited as long as it is electrically conductive. However, when a metal is used, it is preferable to perform a treatment such as precious metal plating so that corrosion does not occur.
Further, as the internal electrode, it is possible to use an internal reinforcing bar of a hardened concrete body, and it is also possible to dispose a conductive material in the hardened concrete body.
[0017]
In the present invention, it is necessary that cationized antibacterial metals exist between external electrodes or between external electrodes and internal electrodes.
The method of allowing cationized antibacterial metals to exist between external electrodes or between external electrodes and internal electrodes is not particularly limited, but a solution containing cationized antibacterial metals is applied to or sprayed on the surface of a hardened concrete body. Alternatively, a method may be used in which a container is provided on the surface of the hardened concrete and a solution containing cationized antibacterial metals is held therein.
[0018]
Of these, a method is generally used in which a container is provided on the surface of a hardened concrete body and a solution containing a cationized antibacterial metal is held therein. It is preferable to supply to the hardened concrete surface using the holding material to hold.
[0019]
Examples of the holding material include fibrous materials such as pulp, cloth, and non-woven fabric or sheets thereof, porous materials such as zeolite, shirasu balloon, and foam beads, and one or more kinds of water-absorbing organic polymers. Can be used.
[0020]
As a method of electrically supplying cationized antibacterial metals into the pores in the concrete hardened body, in the case of a concrete wall, there is a holding material for cationized antibacterial metals so as to sandwich the wall. An anode is provided on the surface, and a cathode is provided on the other surface or the reinforcing bar inside the hardened concrete body. In the case of a column, an anode is provided on one or more surfaces and a cathode is provided on the other surface or internal rebar. In the case of a floor, it is possible to provide a method in which an anode is provided on the upper surface and a cathode is provided on the lower surface or the internal rebar, and current is passed between the external electrodes and / or between the external electrodes and the internal electrodes.
[0021]
【Example】
Hereinafter, the present invention will be described based on experimental examples.
[0022]
Experimental example 1
Unit amount of each material, cement 330 kg / m 3, fine aggregates 748kg / m 3, coarse aggregate 1,041kg / m 3, and the concrete formulation of water 165 kg / m 3 were prepared, a nominal diameter in the center of the cross section A specimen having a diameter of 10 × 20 cm was prepared so as to embed a 10 mm deformed reinforcing bar.
This specimen was immersed in a suspension of cationized antibacterial metals (CAB) shown in Table 1, and a titanium mesh was placed around the specimen so as to be 10 mm from the surface.
Next, a direct current was applied so as to be 1 A per 1 m 2 of the hardened concrete surface area with the titanium mesh as the anode and the internal rebar as the cathode. After passing an electric current for 2 weeks in this state, the neutralization depth, the amount of salt penetration, and the mold resistance were measured.
[0023]
<Materials used>
Cement: Ordinary Portland cement, fine aggregate made by Denki Kagaku Kogyo Co., Ltd .: Himekawa production river sand coarse aggregate: Himekawa production crushed stone, Gmax20mm
Water: tap water AE water reducing agent: commercial product, polycarboxylic acid-based treatment liquid: 0.05 mol / l aqueous solution of calcium chloride CAB b: 0.025 mol of silver-supported zeolite dispersed in the treatment liquid, average particle size 0.5 μm
CAB-ro: 0.025 mol of montmorillonite carrying silver dispersed in the treatment liquid, average particle size 0.5 μm
CAB C: Reagent grade 1 colloidal silver dispersed in 0.025 mol in the processing solution, average particle size 0.1 μm
CAB Ni: Reagent primary zinc oxide dispersed in 0.025 mol in the treatment liquid, average particle size 1 μm
CAB Ho: 0.025 mol of aluminosilicate glass with an Ag 2 O content of 1% by weight dispersed in the treatment liquid, average particle size of 3 μm
Titanium mesh: manufactured by Eltech Corporation, trade name "Elgard Mesh # 210"
[0024]
<Measurement method>
Neutralization depth: The specimen is neutralized for 2 weeks under the conditions of 30 ° C, 60% relative humidity and 10% carbon dioxide, and the specimen is cut and coated with a phenolphthalein solution on the cross section. Measure the neutralization depth with calipers from the color reaction. Salt penetration amount: Specimen was immersed in 30%, 10% NaCl solution for 200 days, then measured for salt content. Mold resistance: Specimen at 30 ° C Then, neutralize for 7 days under the condition of carbon dioxide concentration of 5%, and apply a spore suspension of mold species A Aspergillus niger and mold species B cladosporium cladosporioides on the specimen for 4 weeks. The mold resistance test was conducted according to JIS Z 2911. Mold resistance x indicates mold generation in an area exceeding 1/3 of the specimen, Δ indicates mold generation in an area of 1/3 or less, and ◯ indicates no mold generation.
[0025]
[Table 1]
Experimental example 2
It was carried out in the same manner as in Experimental Example 1 except that CAB-ha was used and CAB-ha having the concentration in the treatment liquid shown in Table 2 was used. The results are also shown in Table 2.
[0027]
[Table 2]
【The invention's effect】
In the present invention, antibacterial and antifungal properties can be imparted to the hardened concrete body by filling the surface of the hardened concrete body or pores inside thereof with cationized antibacterial metals.
Then, an electrode is installed outside the hardened concrete body, the reinforcing bar inside the hardened concrete body is used as one electrode, a treatment solution is held between the electrodes, and an electric current is passed between them. By filling the pores with more cationized antibacterial metals and deeper, the durability of antibacterial and antifungal properties of the hardened concrete can be further improved. It has effects such as improved salt penetration resistance.
Claims (3)
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|---|---|---|---|
| JP32205798A JP4201402B2 (en) | 1998-11-12 | 1998-11-12 | Method for treating hardened concrete |
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| JP32205798A JP4201402B2 (en) | 1998-11-12 | 1998-11-12 | Method for treating hardened concrete |
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| JP4201402B2 true JP4201402B2 (en) | 2008-12-24 |
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