JP2008100880A - Stain-proof and deterioration-preventive agent and method of stain proofing and deterioration prevention for concrete structure - Google Patents
Stain-proof and deterioration-preventive agent and method of stain proofing and deterioration prevention for concrete structure Download PDFInfo
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- JP2008100880A JP2008100880A JP2006285782A JP2006285782A JP2008100880A JP 2008100880 A JP2008100880 A JP 2008100880A JP 2006285782 A JP2006285782 A JP 2006285782A JP 2006285782 A JP2006285782 A JP 2006285782A JP 2008100880 A JP2008100880 A JP 2008100880A
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- water
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- powder
- deterioration
- fluororesin
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000006866 deterioration Effects 0.000 title claims description 25
- 230000002265 prevention Effects 0.000 title claims description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 19
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 37
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
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- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
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- 238000013329 compounding Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
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- 239000003973 paint Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 229910000431 copper oxide Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
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- 229910000765 intermetallic Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
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- 239000002519 antifouling agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 230000001684 chronic effect Effects 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Paints Or Removers (AREA)
- Sewage (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
Description
本発明は、護岸ブロック、冷却導入水路、養殖用水槽、上下水道のコンクリート管路、貯水槽等の水処理施設等に使用して、コンクリートの微生物による汚染や環境雰囲気による汚染を防止し、酸化劣化もしくは微生物等の付着繁殖による防汚及び劣化防止剤並びに防汚及び劣化防止方法防汚及び劣化を防止する劣化防止剤及び劣化防止方法に関する。 The present invention is used in water treatment facilities such as revetment blocks, cooling introduction channels, aquaculture tanks, concrete pipes for water supply and sewerage systems, water storage tanks, etc., to prevent contamination by concrete microorganisms and environmental atmosphere, and oxidation. The present invention relates to an antifouling and deterioration preventing agent due to deterioration or adhesion propagation of microorganisms, and an antifouling and deterioration preventing method.
近年、上下水道等水処理施設においては、コンクリートの腐食・劣化が問題となっているが、これらの原因は、下水処理施設においては、下水や下水汚泥中に嫌気性の硫酸塩還元細菌と硫黄酸化細菌が関与する硫酸による進行によること及びこの腐食過程で発生する硫化水素が主な原因となっていることが知られている。また、浄水場や魚介類の養殖場では、水藻や甲殻類の発生、付着により、その代謝物によって生成される有機酸によるものが多い。
このような現状に鑑みて日本下水道事業団からコンクリートの腐食・劣化を防止する対策として、次のことが提案されている。
（１）水の腐敗を防止して硫化物の生成を抑制する方法。
（２）発生した硫化物の大気中への放散を防止する方法。
（３）硫化水素を基に硫酸を生成する硫黄酸化細菌の活動を抑制する方法。
（４）防食性塗料をコンクリートや鉄の表面に塗装ライニングする方法。
（５）コンクリートの耐酸性を向上する方法。
（６）コンクリートに抗菌剤を配合して硫黄酸化細菌の活動を抑制する方法。
（７）水藻や甲殻類の付着を防止する方法。
In recent years, in water treatment facilities such as water and sewage systems, the corrosion and deterioration of concrete has become a problem. In sewage treatment facilities, anaerobic sulfate-reducing bacteria and sulfur are present in sewage and sewage sludge. It is known that the main cause is the hydrogen sulfide generated during the corrosion process due to the progress by sulfuric acid involving oxidizing bacteria. Also, in water purification plants and seafood farms, there are many organic acids produced by metabolites due to the generation and adhesion of algae and crustaceans.
In view of such a current situation, the following has been proposed as a measure to prevent corrosion and deterioration of concrete by the Japan Sewerage Corporation.
(1) A method for preventing the decay of water and suppressing the formation of sulfides.
(2) A method of preventing the generated sulfide from being released into the atmosphere.
(3) A method for suppressing the activity of sulfur-oxidizing bacteria that produce sulfuric acid based on hydrogen sulfide.
(4) A method of coating lining with an anticorrosive paint on the surface of concrete or iron.
(5) A method for improving the acid resistance of concrete.
(6) A method of suppressing the activity of sulfur-oxidizing bacteria by adding an antibacterial agent to concrete.
(7) A method for preventing adhesion of algae and crustaceans.
上記（１）の方法では、下水には汚泥が含まれているため、その汚泥を完全に除去することは不可能であり、満足すべき効果が得られていない。
（２）の方法は、酸化剤（過酸化水素等）の薬剤添加による硫化水素の固定化があるが、この方法は薬剤が高価であり、取扱に専門的注意が必要なため、経済的に問題がある。
（３）の方法では施設内の空気の吸、排気を行い、硫化水素を希釈処理する方法が知られているが、硫化水素ガスは悪臭防止法で定められている悪臭８物質のうちの一つであるために、公害問題があり、作業環境としても１０ｐｐｍ以上あると健康に問題があり、さらに高濃度になると、中毒の発生や爆発の危険性があるため、実施が困難である。
In the method (1), since sludge is contained in the sewage, it is impossible to completely remove the sludge, and a satisfactory effect is not obtained.
The method (2) involves immobilizing hydrogen sulfide by adding a chemical agent such as an oxidant (hydrogen peroxide, etc.). However, this method is expensive because the chemical is expensive and requires special care in handling. There's a problem.
In the method (3), there is known a method of sucking and exhausting air in a facility and diluting hydrogen sulfide. Hydrogen sulfide gas is one of eight odorous substances defined by the Odor Control Law. Therefore, there is a problem of pollution, and if the working environment is 10 ppm or more, there is a problem of health. If the concentration is higher, there is a risk of poisoning or explosion, which is difficult to implement.
（４）の方法としては、塗料としてエポキシ樹脂やポリエステル樹脂等が用いられているが、耐酸性と耐アルカリ性を兼ね備えることは困難で、コンクリート構造物や鉄にピンホールやクラックを発生したり、付着強度が不十分なため、腐食防止の効果が不十分となる問題がある。また更に沈澱槽内面のライニングに用いる場合、ＦＲＰやフレークライニング、シートライニングが知られているが、施行性が悪く、（例えば高温、高湿環境や含有水量の多いコンクリート構造物に施工しがたい等）しかも施工が高価であるので経済的にも問題がある。
（５）の方法は、下水汚泥溶融スラグ粉と珪酸ソーダを主構成材料とした耐酸セメントを用いたコンクリートを使用する方法であるが、現場打ちコンクリートとしての利用については課題が残されている。
（６）の方法は、種々のものがあるが、これのみで満足すべき成果を収めることは困難であり、低コストで効果のあるものを採用する必要がある。また、毒性についても配慮する必要がある。
（７）の方法は、藻類や甲殻類の付着を防止する手段として燐酸塩等の毒性のある薬剤をコンクリート等に混入させて、例えば船底に塗布し、徐々に毒物を溶出させる塗料が知られているが、近年は海洋汚染防止の見地から使用が控えられている。
As a method of (4), epoxy resin or polyester resin is used as a paint, but it is difficult to combine acid resistance and alkali resistance, and pinholes and cracks occur in concrete structures and iron, Since the adhesion strength is insufficient, there is a problem that the effect of preventing corrosion is insufficient. In addition, when used for lining the inner surface of the precipitation tank, FRP, flare lining, and sheet lining are known, but the effectiveness is poor, and it is difficult to apply to concrete structures with high temperature, high humidity environment and high water content. Etc.) Moreover, since construction is expensive, there is a problem economically.
The method (5) is a method using concrete using acid-resistant cement whose main constituent materials are sewage sludge melted slag powder and sodium silicate, but there remains a problem with its use as cast-in-place concrete.
Although there are various methods of (6), it is difficult to achieve satisfactory results with this alone, and it is necessary to adopt an effective method at low cost. It is also necessary to consider toxicity.
In the method (7), as a means for preventing the attachment of algae and crustaceans, a toxic chemical such as phosphate is mixed with concrete and applied to the bottom of the ship, for example, and a paint that gradually elutes the poison is known. However, in recent years it has been refrained from the viewpoint of preventing marine pollution.
特開昭６３−１６０７２号公報や、特開平２−２６５７０８号公報にはエポキシ樹脂やポリエステル樹脂のライニングによりコンクリートを保護する方法が記載されている。特開平１−５５４９３号公報には、ガラス材のライニングによりコンクリートを保護する方法が記載されている。これらの方法は、長期のうちにピンホールを通じて剥離し寿命が短い。特開平４−１４９０５３号公報には銅、ニッケル、スズ、鉛等の金属および／またはこれらの金属の酸化物をコンクリートに含有させてコンクリートの腐食を防ぐ方法が記載されているが、長期間の使用を目的とする場合金属の使用量を多く用いる必要があり、金属イオンの溶出が多過ぎて水質汚染の恐れがある。特開平１１−１８９４４９号公報には、金属錯体特にフタロシアニン化合物とチタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、モリブデン等の金属及び／金属酸化物との混合物を混合したものをコンクリートに含有させてコンクリートの腐食を防ぐ方法が記載されているが、特殊な錯体を用意するのでコスト高になる。また、ニッケルは発癌性があり、バナジウムは生化学的作用で急性、慢性の刺激症状があり得ること、クロムは化学活性が強く、生体への影響力も強く、潰瘍や、発癌性の危険があること、コバルトは人体への中毒症状、呼吸器疾患のおそれがあり、好ましくない。 Japanese Patent Application Laid-Open No. 63-16072 and Japanese Patent Application Laid-Open No. 2-265708 describe methods for protecting concrete by lining an epoxy resin or a polyester resin. Japanese Laid-Open Patent Publication No. 1-55493 describes a method for protecting concrete by lining a glass material. These methods peel off through pinholes over a long period of time and have a short life. Japanese Patent Laid-Open No. 4-149053 describes a method for preventing corrosion of concrete by containing a metal such as copper, nickel, tin, lead and / or an oxide of these metals in concrete. When intended for use, it is necessary to use a large amount of metal, and there is a risk of water pollution due to excessive elution of metal ions. Japanese Patent Application Laid-Open No. 11-189449 discloses a mixture of a metal complex, particularly a mixture of a phthalocyanine compound and a metal such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, and / or a metal oxide. Although a method for preventing the corrosion of concrete by containing it in concrete is described, a special complex is prepared, which increases the cost. Nickel is carcinogenic, vanadium is a biochemical effect that can cause acute and chronic irritation, and chromium has a strong chemical activity and a strong impact on the body, causing ulcers and carcinogenic risks Cobalt is not preferable because it may cause poisoning of the human body and respiratory diseases.
また、特開２００１−１０６６０７号公報にはチタン酸アルカリ金属のアルカリ金属イオンの一部ないし全部が、硫黄酸化細菌に対する防菌作用のある、銀、銅、亜鉛、ニッケル、コバルト、鉄、マンガン等等の各イオンとされた抗菌剤を用いたものであるが、効果を実証する記載はない。 Japanese Patent Application Laid-Open No. 2001-106607 discloses silver, copper, zinc, nickel, cobalt, iron, manganese, etc. in which some or all of alkali metal ions of alkali metal titanate have antibacterial action against sulfur-oxidizing bacteria. However, there is no description demonstrating the effect.
特許第２８０８０８７号は上記各種の問題点を解決し、コンクリートの腐食劣化の原因となる下水や汚泥中で発生する硫化物や、硫酸塩還元細菌・硫黄酸化細菌の代謝作用によって発生する硫化水素、この硫化水素から生成される硫酸、この硫酸とコンクリートの主成分である水酸化カルシウムの反応による硫酸カルシウム化によるコンクリートの膨張収縮による劣化等の問題を解決し、長期にわたる微生物、藻類、甲殻類、貝類等の悪影響を防止できた。 Patent No. 2880887 solves the above-mentioned various problems, sulfides generated in sewage and sludge that cause corrosion deterioration of concrete, hydrogen sulfide generated by the metabolic action of sulfate-reducing bacteria and sulfur-oxidizing bacteria, Solves problems such as deterioration due to expansion and contraction of concrete due to the reaction of sulfuric acid generated from this hydrogen sulfide, calcium sulfate, which is the main component of this sulfuric acid and concrete, due to expansion of calcium sulfate, long-term microorganisms, algae, crustaceans, The bad influence of shellfish etc. was prevented.
しかしながら、近時はニッケルが皮膚障害や肺癌などの発生の原因となる疑いが提起されており、ニッケルを用いないで前記従来の技術の問題点を解決することが求められているが、前記特許第２８０８０８７号は勿論、各参考特許文献に記載のものも、ニッケル等特定の金属の有害性に着目したものは見あたらない。 However, recently, there has been a suspicion that nickel may cause skin damage, lung cancer and the like, and there is a need to solve the problems of the conventional technology without using nickel. No. 2,808,087, as well as those described in each reference patent document, there is no one that pays attention to the toxicity of a specific metal such as nickel.
更にまた、特開２００４−３３１４２２号公報記載の発明は、発癌性の点から忌避されるニッケルを使用せずに、しかも長期間前記のコンクリートの劣化防止効果、生物の繁殖防止効果を発揮できる劣化防止剤を鋭意検討の結果生みだされたものであり、請求項１の発明は、少なくともフッ素樹脂と、銅粉末、チタン、亜鉛もしくは錫から選択された金属粉末の中の３成分と、未硬化のポルトランドセメントもしくはモルタルとを水に分散させたことを特徴とするコンクリート構造物の劣化防止剤である。
銅粉末、チタン、亜鉛もしくは錫から選択された金属粉末を用いているので、導電性があり、使用場所によっては電気装置による影響あるいは、水中でのイオン化傾向の相違による電気的腐食が考えられるので、この点を留意する必要がある。
Furthermore, the invention described in Japanese Patent Application Laid-Open No. 2004-331422 does not use nickel which is repelled from the point of carcinogenicity, and further can exhibit the above-mentioned concrete deterioration preventing effect and biological reproduction preventing effect for a long time. As a result of earnest study of the inhibitor, the invention of claim 1 comprises at least a fluororesin and three components in a metal powder selected from copper powder, titanium, zinc or tin, and uncured. It is an anti-degradation agent for concrete structures characterized by dispersing Portland cement or mortar in water.
Since metal powder selected from copper powder, titanium, zinc or tin is used, it is conductive, and depending on the place of use, it can be considered to be affected by electrical equipment or electrical corrosion due to differences in ionization tendency in water. It is necessary to keep this in mind.
本発明者は、コンクリートの腐食劣化の原因となる下水や汚泥中で発生する硫化物や、硫酸塩還元細菌・硫黄酸化細菌の代謝作用によって発生する硫化水素、この硫化水素から生成される硫酸、この硫酸とコンクリートの主成分である水酸化カルシウムの反応による硫酸カルシウム化によるコンクリートの膨張収縮による劣化等の問題を解決し、長期にわたる微生物、藻類、甲殻類、貝類等の悪影響を防止できた。
本発明は、下水道処理施設のみならず、一般建造物に用いても、低コストの配合物で、コンクリート構造物に塗装したときに、長期にわたり接着性がよく、しかも酸化による腐食環境でも酸化防止効果が十分で、微生物、藻類、甲殻類、貝類等の悪影響を受け難く、しかも発癌性がなく電気伝導性のないコンクリート構造物の防汚及び劣化防止剤並びに防汚及び劣化防止方法を提供することを目的とする。
The present inventor is a sulfide generated in sewage and sludge that causes corrosion deterioration of concrete, hydrogen sulfide generated by the metabolic action of sulfate reducing bacteria and sulfur oxidizing bacteria, sulfuric acid generated from this hydrogen sulfide, The problem of deterioration due to expansion and shrinkage of concrete due to calcium sulfate conversion by the reaction of sulfuric acid and calcium hydroxide, which is the main component of concrete, was solved, and adverse effects of microorganisms, algae, crustaceans, shellfish, etc. over the long term could be prevented.
The present invention is not only used for sewerage treatment facilities but also for general buildings. It is a low-cost compound and has good adhesion for a long time when it is applied to concrete structures, and also prevents oxidation even in corrosive environments caused by oxidation. To provide an antifouling and deterioration preventing agent and an antifouling and deterioration preventing method for a concrete structure which is sufficiently effective, hardly affected by adverse effects of microorganisms, algae, crustaceans, shellfish, etc., and which is not carcinogenic and has no electrical conductivity. For the purpose.
本発明はこのような観点からなされたもので、フッ素樹脂に、銅粉末、珪藻土粉末、酸化チタン粉末の３種類の殺菌、防汚作用のあるものを併用し、セメント、モルタルと水とによりコンクリート構造物の防汚を低コストで達成しようとするものである。 The present invention has been made from this point of view, and in combination with fluororesin, three types of sterilizing and antifouling actions of copper powder, diatomaceous earth powder, and titanium oxide powder are used in combination with cement, mortar and water. It is intended to achieve antifouling of structures at low cost.
具体的には、請求項項１の発明は、少なくともフッ素樹脂と、銅粉末、珪藻土粉末、酸化チタンと、未硬化のポルトランドセメントもしくはモルタルとを水に分散させたことを特徴とするコンクリート構造物の防汚及び劣化防止剤であり、請求項２の発明は、少なくともフッ素樹脂と、銅粉末、珪藻土粉末、酸化チタン粉末と、未硬化のポルトランドセメントもしくはモルタルとを水に分散させてなる、防汚及び劣化防止剤をコンクリート構造物の表面に塗布し、硬化させることを特徴とするコンクリート構造物の防汚及び劣化防止方法である。 Specifically, the invention of claim 1 is a concrete structure characterized in that at least a fluororesin, copper powder, diatomaceous earth powder, titanium oxide, and uncured Portland cement or mortar are dispersed in water. The antifouling and deterioration preventing agent according to claim 2 is characterized in that at least a fluororesin, copper powder, diatomaceous earth powder, titanium oxide powder and uncured Portland cement or mortar are dispersed in water. An antifouling and deterioration preventing method for a concrete structure, characterized in that an antifouling and deterioration preventing agent is applied to the surface of the concrete structure and cured.
上記において、各成分の好ましい配合比は以下のとおりである。
フッ素樹脂１０〜２５重量部、銅粉末５〜１０重量部、珪藻土粉末１０〜２０重量部、酸化チタン粉末５〜１０重量部。
水及びポルトランドセメントもしくはモルタルを塗布硬化に必要な量を適宜使用する、
また、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤等の添加剤は要求される硬化皮膜の性状あるいは硬化速度など必要に応じて添加が許される。
In the above, the preferable compounding ratio of each component is as follows.
10 to 25 parts by weight of fluororesin, 5 to 10 parts by weight of copper powder, 10 to 20 parts by weight of diatomaceous earth powder, and 5 to 10 parts by weight of titanium oxide powder.
Use water and Portland cement or mortar as necessary to cure the coating,
Additives such as cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and surfactant may be added as required, such as required properties of the cured film or curing rate.
本発明の実施にあたり使用されるフッ素樹脂は特に限定はないが、通常水でエマルジョンとしたものが容易に使用することができ、例えば旭ガラス社の商品名ルミフロン（モノクロロトリフルオロエチレンポリマー）、ダイキン社のゼッフレ（ジフルオロエチレンポリマー）、ＩＳＲ社のフローレン（ポリフッ化ビニリデン）等が適用可能である。
また、銅粉末は、イオン化により、防菌、防藻効果を長期に発揮することができる。特にコンクリート構造物の劣化防止に効果があり、ここに用いられる銅粉末は例えばチタン、亜鉛および錫の金属間化合物であってもよい。
同時に用いられる酸化チタンは光触媒作用で、活性酸素により有機物を分解し、抗菌、防カビ、臭気分解、防汚作用や大気、水質の浄化作用、劣化防止に長期間触媒効果を発揮できる。従って酸化チタンは表面側に存在することで効果が顕著であり、下地層に酸化チタンを含まないか、極めて少量含有するようにし、その表面層に酸化チタンの含有量の多いものを用いた塗布構造とするときは、酸化チタンの光触媒作用を効果的に活用することが出来る。しかし、本発明では珪藻土を用いているので、その微細孔を有する塗膜性質のゆえに前記酸化チタンは内部に存在するように見えても外部雰囲気との接触があり、触媒作用を発揮することが出来る。
なお、銅は、純粋な金属を粉末にして使用してもよいが、金属間化合物は勿論、自然状態において表面が酸化された酸化皮膜を有するものであってもよく、更には錯体を構成したものでもよい。
The fluororesin used in the practice of the present invention is not particularly limited, but it is usually easy to use an emulsion made with water. For example, trade name Lumiflon (monochlorotrifluoroethylene polymer) of Asahi Glass Co., Ltd., Daikin Zeffle (difluoroethylene polymer) from ISR, Florene (polyvinylidene fluoride) from ISR, etc. are applicable.
Further, the copper powder can exhibit antibacterial and algal control effects for a long time by ionization. In particular, it is effective in preventing deterioration of the concrete structure, and the copper powder used here may be, for example, an intermetallic compound of titanium, zinc and tin.
Titanium oxide used at the same time has a photocatalytic action, decomposes organic substances with active oxygen, and can exhibit a long-term catalytic effect in antibacterial, antifungal, odor decomposition, antifouling action, purification of air and water, and prevention of deterioration. Therefore, the effect of titanium oxide is remarkable because it exists on the surface side, so that the underlying layer contains no or very small amount of titanium oxide, and the surface layer is coated with a high titanium oxide content. When the structure is adopted, the photocatalytic action of titanium oxide can be effectively utilized. However, since diatomaceous earth is used in the present invention, the titanium oxide is in contact with the external atmosphere even if it appears to be present inside due to the properties of the coating film having the fine pores, and can exhibit a catalytic action. I can do it.
Copper may be used in the form of a pure metal powder, but may of course have an oxide film whose surface is oxidized in a natural state as well as an intermetallic compound, and further constitutes a complex. It may be a thing.
珪藻土はガラスと同じＳｉＯ２の殻で覆われており、この殻には無数の孔が開いているが、好ましく用いられるのは、自然乾燥し、食塩とソーダ灰を数％添加し、約１０００℃で焼成し、不純有機物を除去したものが用いられるが、ホルムアルデヒド等の有害化学物の分解に寄与し、また、同時に配合された銅及び酸化チタンの防汚作用を効果的にする効果を有する。 Diatomaceous earth is covered with the same SiO 2 shell as glass, and the shell has numerous holes, but it is preferable to dry it naturally, add several percent of salt and soda ash, and add about 1000%. Although it is used after baking at ℃ and removing impure organic substances, it contributes to the decomposition of harmful chemicals such as formaldehyde, and at the same time has the effect of making the antifouling action of the compounded copper and titanium oxide effective. .
本発明において、フッ素樹脂はコンクリート構造物に塗装した場合、銅粉末、珪藻土粉末、酸化チタン粉末、それぞれ耐食性があるが、これらの３成分の粉末が優れた防腐効果を発揮すると共に、塗布面の外観がよく、生物の付着がなく、酸化状況での変化もないことが確認された。
特に銅粉末を含む場合は、銅粉末を含まないものの組み合わせよりも水藻の付着が少なく、水藻除去に要する水圧も小さくて済むことが判った。
また、上記のように銅粉末を含む場合は勿論、比較的低い水圧で水藻を除去することができ、塗膜の付着強度も試験の前後で余り変化がなく、硫黄が塗膜内に侵入する程度が極めて少ないので、硫黄細菌による劣化を防止する効果があることが理解される。
好ましい銅粉末の配合量は前記したように５重量部〜１０重量部であり、５重量部未満では溶出する銅イオンが少ないため殺菌効果が不十分となり目的とする防食効果が得られにくく不利で、１０重量部を越えて多いと銅イオンの溶出量が多くなり過ぎ、水生生物の環境破壊となり、またコスト面で不利である。また、二酸化チタンが好ましい量は５重量部〜１０重量部であり、５重量部未満では活性酸素の発生が少なく防汚、抗菌効果に不利で、１０重量部を越えて多いと活性酸素が活発となり過ぎ、フッ素樹脂の組織を分解させ樹脂が劣化して耐久性に不利である。更に珪藻土は好ましい量は１０重量部〜２０重量部であり、１０重量部未満では防藻効果が少なく、また、コスト面でも不利である。２０重量部を越えて多いとコンクリートに塗布したときに付着強度が著しくわるくなり不利である。
In the present invention, when the fluororesin is applied to a concrete structure, the copper powder, diatomaceous earth powder, and titanium oxide powder each have corrosion resistance, but these three component powders exhibit an excellent antiseptic effect, It was confirmed that the appearance was good, there was no biological attachment, and there was no change in the oxidation situation.
In particular, when copper powder was included, it was found that the adhesion of water algae was less than the combination of those not containing copper powder, and the water pressure required to remove the water algae was small.
In addition, in the case of containing copper powder as described above, algae can be removed at a relatively low water pressure, and the adhesion strength of the coating film is not much changed before and after the test, and sulfur penetrates into the coating film. It is understood that since the degree is extremely small, there is an effect of preventing deterioration due to sulfur bacteria.
As described above, the preferred amount of copper powder is 5 to 10 parts by weight, and if it is less than 5 parts by weight, the amount of copper ions to be eluted is small, so the bactericidal effect is insufficient and the desired anticorrosive effect is difficult to obtain. If the amount exceeds 10 parts by weight, the elution amount of copper ions becomes too large, resulting in environmental destruction of aquatic organisms and disadvantageous in terms of cost. Further, the preferred amount of titanium dioxide is 5 to 10 parts by weight. If it is less than 5 parts by weight, the generation of active oxygen is small, which is disadvantageous for antifouling and antibacterial effects, and if it exceeds 10 parts by weight, the active oxygen is active. Therefore, the structure of the fluororesin is decomposed and the resin deteriorates, which is disadvantageous for durability. Further, the preferable amount of diatomaceous earth is 10 to 20 parts by weight. If it is less than 10 parts by weight, the algae-proofing effect is small and the cost is disadvantageous. When the amount exceeds 20 parts by weight, the adhesion strength is remarkably reduced when applied to concrete, which is disadvantageous.
本発明によれば、少なくともフッ素樹脂と、銅粉末と、酸化チタン粉末と、珪藻土粉末の３成分からなる粉末を、ポルトランドセメントもしくはモルタルとを水に分散させたことを特徴とするコンクリート構造物の劣化防止剤を用いることにより、低コストで、地球環境を汚染することなく、また、発癌性の成分を含むことなく、しかも長期にわたり、金属粉末とフッ素樹脂の好ましい皮膜構成効果により、セメント構造物の表面に塗布したときに強固に接着しながら、プールや護岸コンクリート等の水と接する場合のコンクリート建造物において、汚染状態で発生し易い硫酸菌等の酸基を中和し、毒性を消滅させるとともに、長期にわたり藻類など生物の付着や繁殖を防ぎ、コンクリートが劣化するのを防止することができる。 According to the present invention, there is provided a concrete structure characterized in that at least a fluororesin, copper powder, titanium oxide powder, and diatomaceous earth powder are dispersed in water with Portland cement or mortar. By using an anti-degradation agent, the cement structure can be manufactured at a low cost, without polluting the global environment, without containing carcinogenic components, and with a favorable film composition effect of metal powder and fluororesin over a long period of time. While adhering firmly to the surface of the concrete, neutralize acid groups such as sulfuric acid bacteria that are likely to occur in a contaminated state in a concrete structure that comes into contact with water such as pools and revetment concrete, thereby eliminating toxicity At the same time, it can prevent the adhesion and propagation of organisms such as algae over a long period of time, and can prevent the concrete from deteriorating.
実施例１
銅粉末１．５Ｋｇ，酸化チタン粉末１．５Ｋｇ，珪藻土粉末５Ｋｇ
フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し本発明の組成物を得、これをコンクリート表面に塗布した。
Example 1
Copper powder 1.5Kg, titanium oxide powder 1.5Kg, diatomaceous earth powder 5Kg
Fluorine resin 6Kg
An appropriate amount of water is added to make an emulsion-like composition, and to this is added 15 kg of cinnabar, silane-based water repellent, styrene-based water-soluble polymer and surfactant in total with an appropriate amount of water to obtain the composition of the present invention. Was applied to the concrete surface.
実施例２
銅粉末３Ｋｇ，酸化チタン粉末３Ｋｇ，珪藻土粉末３Ｋｇ
フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに未硬化のポルトランドセメントと水とを適量加えて本発明の組成物を得、これをコンクリート表面に塗布した。
Example 2
3 kg copper powder, 3 kg titanium oxide powder, 3 kg diatomaceous earth powder
Fluorine resin 6Kg
An appropriate amount of water was added to form an emulsion composition, and an uncured Portland cement and water were added to the appropriate amount to obtain the composition of the present invention, which was applied to the concrete surface.
実施例３
銅粉末２Ｋｇ，酸化チタン粉末２Ｋｇ，珪藻土粉末５Ｋｇ
フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１０Ｋｇを適量の水とともに添加し本発明の組成物を得、これをコンクリート表面に塗布した。
Example 3
2 kg copper powder, 2 kg titanium oxide powder, 5 kg diatomaceous earth powder
Fluorine resin 6Kg
An appropriate amount of water is added to make an emulsion composition, and to this is added 10 kg of cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and surfactant in total with an appropriate amount of water to obtain the composition of the present invention. Was applied to the concrete surface.
実施例４
銅粉末３Ｋｇ，酸化チタン粉末３Ｋｇ、珪藻土粉末５Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これを適量のモルタルを加えてコンクリート表面に塗布した後、その表面に銅粉末２Ｋｇ、酸化チタン粉末２Ｋｇ、フッ素樹脂４Ｋｇを適量のモルタル及び水とを加えた組成物を塗布して本発明の塗装物を得た。
Example 4
Copper powder 3Kg, titanium oxide powder 3Kg, diatomaceous earth powder 5Kg, fluororesin 6Kg
Add an appropriate amount of water to make an emulsion composition, add an appropriate amount of mortar and apply it to the concrete surface, then add 2Kg of copper powder, 2Kg of titanium oxide powder and 4Kg of fluororesin on the surface with an appropriate amount of mortar and water. The added composition was applied to obtain a coated product of the present invention.
実施例５
銅粉末３Ｋｇ，酸化チタン粉末３Ｋｇ、珪藻土粉末４Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これを適量のモルタルを加えてコンクリート表面に塗布した後、その表面に銅粉末２Ｋｇ、酸化チタン粉末２Ｋｇ、フッ素樹脂４Ｋｇを適量のモルタル及び水とを加えた組成物を塗布して本発明の塗装物を得た。
Example 5
Copper powder 3Kg, titanium oxide powder 3Kg, diatomaceous earth powder 4Kg, fluororesin 6Kg
Add an appropriate amount of water to make an emulsion composition, add an appropriate amount of mortar and apply it to the concrete surface, then add 2Kg of copper powder, 2Kg of titanium oxide powder and 4Kg of fluororesin on the surface with an appropriate amount of mortar and water. The added composition was applied to obtain a coated product of the present invention.
比較例１
銅粉末３Ｋｇ，ニッケル粉末３Ｋｇ，チタン粉末３Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これにセメント、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 1
Copper powder 3Kg, nickel powder 3Kg, titanium powder 3Kg, fluororesin 6Kg
An appropriate amount of water is added to make an emulsion-like composition, and cement, cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. This was applied to the concrete surface.
比較例２
白炭７Ｋｇ，酸化チタン粉末２Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これにセメント、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 2
7Kg of white charcoal, 2Kg of titanium oxide powder, 6Kg of fluororesin
An appropriate amount of water is added to make an emulsion-like composition, and cement, cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. This was applied to the concrete surface.
比較例３
銅粉末３Ｋｇ，チタン粉末３Ｋｇ，亜鉛粉末３Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これにセメント、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 3
Copper powder 3Kg, titanium powder 3Kg, zinc powder 3Kg, fluororesin 6Kg
An appropriate amount of water is added to make an emulsion-like composition, and cement, cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. This was applied to the concrete surface.
比較例４
銅粉末３Ｋｇ，亜酸化銅粉末３Ｋｇ，緑青粉末３Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これにセメント、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 4
Copper powder 3Kg, cuprous oxide powder 3Kg, patina powder 3Kg, fluororesin 6Kg
An appropriate amount of water is added to make an emulsion-like composition, and cement, cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. This was applied to the concrete surface.
比較例５
銅板
Comparative Example 5
Copper plate
比較例６
フッ素樹脂６Ｋｇ
これにセメント、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 6
Fluorine resin 6Kg
Cement, cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant were added together with an appropriate amount of water to obtain a composition of a comparative example, which was applied to the concrete surface.
比較例７：実施例１に対して珪藻土を配合しない場合
銅粉末３．５Ｋｇ，酸化チタン粉末２Ｋｇ
フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 7: When no diatomaceous earth was added to Example 1, copper powder 3.5 kg, titanium oxide powder 2 kg
Fluorine resin 6Kg
An appropriate amount of water is added to make an emulsion composition, and then, silica sand, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. Was applied to the concrete surface.
比較例８：実施例１に対して酸化チタンのない場合
銅粉末３．５Ｋｇ，珪藻土粉末２Ｋｇ
フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し比較例の組成物を得、これをコンクリート表面に塗布した。
Comparative Example 8: No titanium oxide compared to Example 1 3.5 kg copper powder, 2 kg diatomaceous earth powder
Fluorine resin 6Kg
An appropriate amount of water is added to make an emulsion composition, and then, silica sand, silane-based water repellent, styrene-based water-soluble polymer, and a total of 15 kg of surfactant are added together with an appropriate amount of water to obtain a comparative composition. Was applied to the concrete surface.
・・・・・以下の文案でよいか検討してください
比較例９：実施例１に対して銅粉末の銅のない場合
酸化チタン粉末１．５Ｋｇ，珪藻土粉末６Ｋｇ，フッ素樹脂６Ｋｇ
適量の水を加えてエマルジョン状組成物とし、これに硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤計１５Ｋｇを適量の水とともに添加し本発明の組成物を得、これをコンクリート表面に塗布した。
・ ・ ・ ・ ・ Please consider whether the following text is acceptable. Comparative Example 9: In the case of no copper powder compared to Example 1 Titanium oxide powder 1.5 kg, diatomaceous earth powder 6 kg, fluororesin 6 kg
An appropriate amount of water is added to make an emulsion-like composition, and to this is added 15 kg of cinnabar, silane-based water repellent, styrene-based water-soluble polymer and surfactant in total with an appropriate amount of water to obtain the composition of the present invention. Was applied to the concrete surface.
本発明において好ましい配合量は先に述べたように、フッ素樹脂１０〜２５重量部、銅粉末５〜１０重量部、珪藻土粉末１０〜２０重量部、酸化チタン粉末５〜１０重量部であるが、水及びポルトランドセメントもしくはモルタル塗布硬化に必要な量を適宜使用する。
また、硅砂、シラン系撥水剤、スチレン系水溶性高分子、界面活性剤等の添加剤は要求される硬化皮膜の性状あるいは硬化速度など必要に応じて添加が許される。
フッ素樹脂１００重量部に対して、銅粉末及び酸化チタン粉末が上記範囲より少ない場合は、金属相互の金属間結合の生成が少な過ぎて、遊離するイオンが少ないために殺菌効果が不十分となり、目的とする防食効果が得られない。逆に銅粉末及び酸化チタン粉末が上記範囲より多すぎる場合は、水中における分散性が悪く、コンクリートに塗布したときに付着性が悪くなり、取扱が困難となり、更に塗布膜に亀裂が入り易く、殺菌効果の点では過量であるためコストの上昇を来たし、実用効果が少なく、いずれにしても目的とする防食効果が得られない。珪藻土粉末が上記範囲を越えて少ない場合は、銅粉末及び酸化チタン粉末が硬化したコンクリートにおいて、銅粉末及び酸化チタン粉末の防食効果を発揮させるに十分な気孔を有せず、防藻、防菌効果が劣り好ましくない。
フッ素樹脂は勿論この配合範囲で他の成分を程よく分散させて、好ましい防食効果、防菌効果を奏するものである。
In the present invention, as described above, preferred blending amounts are 10 to 25 parts by weight of fluororesin, 5 to 10 parts by weight of copper powder, 10 to 20 parts by weight of diatomaceous earth powder, and 5 to 10 parts by weight of titanium oxide powder. The amount necessary for water and Portland cement or mortar coating and curing is appropriately used.
Additives such as cinnabar, silane-based water repellent, styrene-based water-soluble polymer, and surfactant may be added as required, such as required properties of the cured film or curing rate.
When the amount of copper powder and titanium oxide powder is less than the above range with respect to 100 parts by weight of the fluororesin, the production of intermetallic bonds between metals is too small, and the bactericidal effect is insufficient because there are few free ions. The intended anticorrosive effect cannot be obtained. Conversely, if the copper powder and titanium oxide powder are too much above the above range, the dispersibility in water is poor, the adhesion becomes poor when applied to concrete, handling becomes difficult, and the coating film is easily cracked, Since the amount is excessive in terms of sterilization effect, the cost is increased and the practical effect is small. In any case, the intended anticorrosion effect cannot be obtained. When the diatomaceous earth powder is less than the above range, the concrete in which the copper powder and the titanium oxide powder are hardened does not have sufficient pores to exert the anticorrosive effect of the copper powder and the titanium oxide powder. The effect is inferior.
Of course, other components in the blending range of the fluororesin are moderately dispersed to provide a preferable anticorrosive effect and antibacterial effect.
なお、本発明で特定された銅、酸化チタン、珪藻土の組み合わせは、いずれも公害問題を発生せず、殺菌、生物の付着防止、硫化物の生成防止に効果があるが、銅粉末はその銅イオンの殺菌効果と、下水処理施設の硫化水素対策、硫黄酸化細菌対策の点から、低コストで優れた効果を奏するので好ましい。珪藻土は、銅のみの場合よりも、防食防藻効果に加えて粗い気孔の存在で、酸化チタンの効果を高度に発揮させる作用を有し、これにより雰囲気中の汚染有機物を分解する防菌、防藻効果が向上し、好ましいことが判る。 In addition, the combination of copper, titanium oxide, and diatomaceous earth specified in the present invention does not cause any pollution problems and is effective in sterilization, prevention of biological adhesion, and prevention of sulfide formation. From the standpoints of sterilizing effect of ions and measures against hydrogen sulfide and sulfur-oxidizing bacteria in sewage treatment facilities, it is preferable because it provides excellent effects at low cost. Diatomaceous earth has the effect of highly exhibiting the effect of titanium oxide in the presence of coarse pores in addition to anti-corrosive and anti-algal effects, compared to the case of copper alone, thereby antibacterial that decomposes contaminating organic matter in the atmosphere, It can be seen that the anti-algae effect is improved and preferable.
また、銅粉末及び酸化チタン，珪藻土配合比は、先に述べた配合比が好ましいが、特に限定するものではない。なお、何れか一つを欠いても本発明で目的とするような殺菌効果や防食効果が得られがたいことは比較例から理解できるであろう。また、本発明で特定した各粉末を前記した所定の範囲で配合した場合、均一な分散塗布膜を得られやすく、常温でそれらの各成分が容易に結合して、軽くて堅牢な、結合体が構成され、安定した耐食性の皮膜を形成する。 In addition, the compounding ratio of copper powder, titanium oxide, and diatomaceous earth is preferably the compounding ratio described above, but is not particularly limited. It can be understood from the comparative example that even if any one of them is missing, it is difficult to obtain the bactericidal and anticorrosive effects as intended in the present invention. In addition, when each powder specified in the present invention is blended in the above-described predetermined range, it is easy to obtain a uniform dispersed coating film, and these components are easily combined at room temperature, and are light and robust. To form a stable corrosion-resistant film.
また、本発明では、組成の一つでも欠くときは調和の取れたコストではなくなり、発癌性、環境対策、防藻効果、防菌効果等の点からも好ましい結果を得がたいので採用することは困難である。 Further, in the present invention, when even one of the compositions is lacking, it is not a harmonious cost, and it is difficult to adopt because it is difficult to obtain favorable results from the viewpoint of carcinogenicity, environmental measures, algal control effect, antibacterial effect, etc. It is.
なお、フッ素樹脂は本来化学的に安定で、これに水溶性ポリマー例えばゴムラテックス、樹脂エマルジョン、混合ディスパージョンのほか、セルロース誘導体、ポリビニルアルコール、ポリアクリル酸塩などを添加することが出来る。
水溶性ポリマーを添加したものは、耐水性自体は低下することなく、粒子間では空気や水の存在を許すので、同時に配合するセメント、モルタル等の硬化性成分の硬化を進め、接着性を向上し、フッ素樹脂と水溶性ポリマーの協調した被膜により、腐食防止機能を高めることができる。すなわち、本発明における組成中、各金属粉末は水中で容易にイオンに遊離して金属酸化物が得やすく、塗膜が防食効果を挙げることと、藻類の付着や甲殻類の付着を防止し、併せて、嫌気性の硫酸塩還元細菌の作用により、発生する硫化水素によるコンクリートの劣化を防止できる。このことは一番効果が期待される銅、もしくは銅酸化物のみの殺菌作用では、前記の種々の効果を総合して発揮することはできないことを考えると、正に画期的な効果である。
The fluororesin is inherently chemically stable, and a water-soluble polymer such as rubber latex, resin emulsion, mixed dispersion, cellulose derivative, polyvinyl alcohol, polyacrylate and the like can be added thereto.
The addition of water-soluble polymers allows air and water to exist between the particles without lowering the water resistance itself, thus promoting the curing of curable components such as cement and mortar that are added at the same time to improve adhesion In addition, the corrosion prevention function can be enhanced by the coordinated coating of the fluororesin and the water-soluble polymer. That is, in the composition of the present invention, each metal powder is easily liberated into ions in water and easily obtains a metal oxide, and the coating film has an anticorrosive effect and prevents adhesion of algae and crustaceans, In addition, the deterioration of concrete due to the generated hydrogen sulfide can be prevented by the action of anaerobic sulfate-reducing bacteria. This is a truly epoch-making effect, considering that the most effective effects of copper or the sterilization action of copper oxide alone cannot provide the various effects described above. .
また、その他のシラン系撥水剤、水溶性高分子、界面活性剤の中の少なくともいずれか１種を添加配合することは、コンクリートやモルタル塗装の場合、常套手段であるが、シラン系撥水剤は硬化後の耐水性を増強し、水溶性高分子は、ワーカビリティー、保水性、ブリーディングに対する抵抗性を改善し、界面活性剤（ＡＥ剤）は陰イオン系、陽イオン系、両性系等種々のものがあるが、気泡効果があるので添加には十分検討して使用する。 In addition, adding and blending at least one of other silane-based water repellents, water-soluble polymers, and surfactants is a conventional method in the case of concrete or mortar coating. The agent enhances water resistance after curing, the water-soluble polymer improves workability, water retention, and resistance to bleeding, and the surfactant (AE agent) is various in anionic, cationic, amphoteric, etc. However, there is a bubble effect, so use it carefully after adding it.
その他使用されるポルトランドセメントもしくはモルタル構成成分はセメント以外に例えば砂では粒子径は０．１５〜１．２ｍｍ程度のものが使用されるが、微細な石や硅酸質材料も適用することができる。
上記のセメントおよび各種配合剤の配合量はフッ素樹脂１０〜３０重量部に対して７０〜８０重量部が作業性及び塗布膜の硬化性等の点から好ましい。
一方水は、フッ素樹脂として水分散塗料を使用するが、実際にはセメントの他各種の配合剤を添加し、均一にしてコンクリートに塗布するために、相当量の水が必要であるが、その量は混合塗装が容易な程度に適宜の量を添加すればよいことは通常のモルタルと同様である。
Other Portland cement or mortar constituents used are other than cement, for example, sand having a particle size of about 0.15 to 1.2 mm, but fine stones and oxalic materials can also be applied. .
The blending amount of the above cement and various compounding agents is preferably 70 to 80 parts by weight with respect to 10 to 30 parts by weight of the fluororesin from the viewpoints of workability and curability of the coating film.
Water, on the other hand, uses a water-dispersed paint as a fluororesin, but in reality, a considerable amount of water is required to add and uniformly apply various compounding agents in addition to cement. It is the same as ordinary mortar that an appropriate amount should be added to such an extent that mixing coating is easy.
本発明は、上記の組成物により構成された組成を有するのでセメントの硬化により強固にコンクリート構造物に接着すると共に、フッ素樹脂の強固な網目状被膜により構造物を保護するものである。また、銅は水中に溶出して、イオンを生成し、これが水中に発生している硫化物のイオンと反応して不溶性の銅化合物を生成することおよび生物の発生や細菌の発生を防止もしくは抑制して、例えば、上記金属のイオンにより殺菌して毒性のある硫化物の生成を防止することができる。また、同時に用いられるフッ素樹脂は水に難溶性で、セメント膜に強固な耐水防汚性を与える。
この場合、銅を含有する場合が他の金属よりも最も効果のあることは周知である。
Since the present invention has a composition constituted by the above composition, it firmly adheres to the concrete structure by hardening of the cement, and protects the structure with a strong network coating of fluororesin. Also, copper elutes in water to produce ions, which react with sulfide ions generated in water to produce insoluble copper compounds, and prevent or suppress the generation of organisms and bacteria. Thus, for example, the metal ions can be sterilized to prevent the formation of toxic sulfides. In addition, the fluororesin used at the same time is hardly soluble in water, and gives a strong waterproof and antifouling property to the cement film.
In this case, it is well known that the case of containing copper is most effective than other metals.
また、フッ素樹脂は本来化学的に安定で、これに水溶性ポリマーを添加することができるが、添加したものは、耐水性自体は低下することなく、粒子間では空気や水の存在を許すので、同時に配合するセメント、モルタル等の硬化性成分の硬化を速め、接着性を向上し、フッ素樹脂と水溶性ポリマーの協調した被膜により、腐食防止機能を高めることができる。
すなわち、本発明における組成物において、銅を用いた所以は、発癌性がなく、しかも水中で容易にイオンに遊離して金属酸化物が得易く、塗膜が長期にわたり防食効果を上げることと、藻類の付着や甲殻類の付着を防止し、併せて嫌気性の硫酸塩還元細菌の作用により発生する硫化水素によるコンクリートの劣化を防止できる点にある。
このことは従来技術のフッ素樹脂と、銅粉末とチタンとニッケル粉末とを併用した防食塗料に比べて、発癌性がなく、しかも長期にわたり、コンクリートの劣化を防止し、生物の付着をも防止するというものである点で、全く相違するものである。
Fluororesin is inherently chemically stable, and a water-soluble polymer can be added to it. However, the added resin allows the presence of air and water between the particles without reducing the water resistance itself. Further, the hardening of curable components such as cement and mortar to be blended at the same time can be accelerated, the adhesiveness can be improved, and the corrosion prevention function can be enhanced by the coordinated coating of the fluororesin and the water-soluble polymer.
That is, in the composition of the present invention, the reason for using copper is that it is not carcinogenic, and is easily liberated into ions in water and easily obtains a metal oxide, and the coating film has an anticorrosive effect over a long period of time, It prevents adhesion of algae and crustaceans, and also prevents deterioration of concrete due to hydrogen sulfide generated by the action of anaerobic sulfate-reducing bacteria.
This is less carcinogenic than conventional anti-corrosion paints that use a combination of fluororesin, copper powder, titanium and nickel powder, and also prevents concrete deterioration and biological adhesion over a long period of time. In that respect, it is completely different.
上記の実施例および比較例の各試料を以下の方法による比較試験を行なった。
実施例および比較例に示した各配合物を、下水処理場の最初沈澱池に１２ヵ月懸垂し、
・塗膜外観の評価は目視と指触とにより判断した。
・付着強度試験は、国土交通省建研式引張接着強さ試験法により測定した。
・コンクリート中性化進度は、ＥＰＭＡ（電子マイクロアナライザー）を用いて測定した。
・表面からの硫黄の侵入範囲を観察した。
・水藻の付着状況は肉眼で観察した。
・水藻除去の難易度および除去後の状況は、水圧洗浄機により水藻を除去し、その状態を肉眼で観察した。
なお、最初沈澱池に曝す試験体は、塗装後３０日間乾燥させ、硫化水素濃度の５〜３０ｐｐｍ下の気相部へ試験片の試料を懸垂した。
最終沈澱池に曝す試験体は、水面下３０ｃｍの所に浸漬して１２ケ月経過させた。
その結果は、最初沈澱池は表１、最終沈澱池は表２に示すとおりである。
Each sample of the above examples and comparative examples was subjected to a comparative test by the following method.
Each formulation shown in the examples and comparative examples was suspended in the first sedimentation basin of a sewage treatment plant for 12 months,
-Evaluation of the appearance of the coating film was judged by visual observation and finger touch.
-The adhesion strength test was measured by the Ministry of Land, Infrastructure, Transport and Tourism Kenken-type tensile bond strength test method.
-The concrete neutralization progress was measured using EPMA (electronic microanalyzer).
・ The invasion range of sulfur from the surface was observed.
-The algae adhesion was observed with the naked eye.
-The degree of difficulty in removing the water algae and the situation after the removal were determined by removing the water algae with a hydraulic washer and observing the state with the naked eye.
In addition, the test body exposed to a sedimentation basin first was dried for 30 days after coating, and the sample of the test piece was suspended in the gas phase part 5-30 ppm below hydrogen sulfide concentration.
The test body exposed to the final sedimentation basin was immersed in a place 30 cm below the water surface and allowed to elapse for 12 months.
The results are shown in Table 1 for the first sedimentation basin and Table 2 for the final sedimentation basin.
この試験結果から判るように、本発明によるものは最初沈澱池に曝す試験に於いて、塗膜が黒色化したが異常は認められず、付着強度も試験の前後で余り変化はなく、コンクリート中性化進度（硫黄侵入範囲）も０．３ｍｍ以下と極めて小さく、最終沈澱池に曝す試験では、水藻の付着が極めて少なく、水藻除去も水圧５ｋｇ／ｃｍ２程度で完全に除去され、付着強度は試験前と殆ど変わらないという成果を得た。これに対して、比較例のうち、ニッケルを使用するものは、藻の発生の防止等には有効であるが、毒性があるので、使用することはできない。
これに対して比較例１に示したように、銅粉末、ニッケル粉末、珪藻土粉末、フッ素樹脂粉末を用いたものは、ニッケルの存在で発癌性があり、水藻の除去には効果があるが、硫黄により黒色化するので、劣化が早いものと思われる。
比較例２は白炭、酸化チタン、、フッ素樹脂粉末を用いているので、防藻効果が不十分で、塗膜は硫黄により侵される。
比較例３は銅、チタン、亜鉛、フッ素樹脂を成分とするが水藻の付着が多いという問題がある。
比較例４は、銅、亜酸化銅、緑青、を含有するが、硫黄に侵されることと水藻の付着が多いという問題がある。
比較例５は、銅板のみであるから水藻の付着が多く、硫黄にも侵されるので、好ましくないことを示している。
比較例６は、フッ素樹脂のみで、格別防汚、防菌剤を含有していないので、水藻の付着が多く、硫黄にも侵されるので、好ましくないことを示している。
比較例７は、実施例１に対して、珪藻土を配合していないので、硫黄に対する作用はよいが、水藻の付着が多く適当でない。
比較例８は、実施例１に対して、酸化チタンを配合していないので、水藻の付着は少ないが、実施例１に対して、酸化チタンを配合していないので、水藻の付着は少ないが、硫黄に対する作用の性能が劣る。
比較例９は、実施例１に対して、銅を配合してないので、殺菌性が著しく劣り、硫黄に対する性能は劣悪である。
勿論本発明における各金属は毒性がなく、環境上も好ましいもので、しかも低コストで実施することができる。
As can be seen from the test results, in the test according to the present invention, in the first exposure to the settling basin, the coating film was blackened but no abnormality was observed, and the adhesion strength was not significantly changed before and after the test. The degree of acidification (sulfur intrusion range) is very small, 0.3 mm or less, and in the test exposed to the final sedimentation basin, there is very little adhesion of water algae, and water algae removal is completely removed at a water pressure of about 5 kg / cm 2. The result was almost the same as before the test. On the other hand, among the comparative examples, those using nickel are effective in preventing the generation of algae, but are toxic and cannot be used.
On the other hand, as shown in Comparative Example 1, those using copper powder, nickel powder, diatomaceous earth powder, and fluororesin powder are carcinogenic in the presence of nickel and are effective in removing water algae, It seems to deteriorate quickly because it is blackened by sulfur.
Since Comparative Example 2 uses white coal, titanium oxide, and fluororesin powder, the anti-algae effect is insufficient, and the coating is affected by sulfur.
Although the comparative example 3 has copper, titanium, zinc, and a fluororesin as a component, there exists a problem that there are many adhesions of water algae.
Although the comparative example 4 contains copper, cuprous oxide, and patina, there is a problem that there is much adhesion of algae with being invaded by sulfur.
Since the comparative example 5 is only a copper plate, it has shown that there are many adhesions of aquatic algae, and since it is also attacked by sulfur, it is not preferable.
Since Comparative Example 6 is only a fluororesin and does not contain any special antifouling or antibacterial agent, it shows that it is not preferable because a lot of algae adheres and is also affected by sulfur.
Since Comparative Example 7 does not contain diatomaceous earth compared to Example 1, the effect on sulfur is good, but adhesion of water algae is large and is not appropriate.
Since Comparative Example 8 does not contain titanium oxide with respect to Example 1, adhesion of water algae is small. , The performance of the action on sulfur is inferior.
Since the comparative example 9 does not mix | blend copper with respect to Example 1, its bactericidal property is remarkably inferior and the performance with respect to sulfur is inferior.
Of course, each metal in the present invention has no toxicity, is environmentally preferable, and can be implemented at low cost.
本発明によれば、低コストで、地球環境を汚染することなく、また、発癌性の成分を含むことなく、しかも長期にわたり、金属粉末とフッ素樹脂の好ましい皮膜構成効果により、セメント構造物の表面に塗布したときに強固に接着しながら、プールや護岸コンクリート等の水と接する場合のコンクリート建造物において、汚染状態で発生し易い硫酸菌等の酸基を中和し、毒性を消滅させるとともに、長期にわたり藻類など生物の付着や繁殖を防ぎ、コンクリートが劣化するのを防止することができる。また、建造物に使用しても酸化チタンの効果により環境汚染の影響が少なく、珪藻土を用いたことで低コストの劣化防止を実現できる。 According to the present invention, the surface of a cement structure can be obtained at a low cost without contaminating the global environment, without containing carcinogenic components, and for a long period of time because of a preferable film forming effect of the metal powder and the fluororesin. While adhering firmly when applied to the concrete structure, when it comes into contact with water such as pools and revetment concrete, neutralize acid groups such as sulfate bacteria that are likely to occur in a contaminated state, and eliminate the toxicity, It can prevent the adhesion and propagation of algae and other organisms over a long period of time and prevent concrete from deteriorating. Moreover, even if it is used in a building, there is little influence of environmental pollution due to the effect of titanium oxide, and the use of diatomaceous earth can realize low-cost deterioration prevention.
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